JP2005272443A - Insecticidal, miticidal, nematocidal, germicidal, or bacteriocidal composition and method for using the same - Google Patents
Insecticidal, miticidal, nematocidal, germicidal, or bacteriocidal composition and method for using the same Download PDFInfo
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- 0 CC1(CCC(*)(CC2)*C2(*)CCC1)c(cc1)ccc1NC(c1ccccc1)=N Chemical compound CC1(CCC(*)(CC2)*C2(*)CCC1)c(cc1)ccc1NC(c1ccccc1)=N 0.000 description 7
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本発明は、置換ベンズアニリド化合物と公知の殺虫剤、殺ダニ剤、殺線虫剤、殺菌剤又は殺バクテリア剤の有効成分化合物とを混合してなることを特徴とする病害虫防除組成物に関するものである。 The present invention relates to a pest control composition comprising a substituted benzanilide compound and a known insecticide, acaricide, nematicide, fungicide, or active ingredient compound of a bactericide. is there.
置換ベンズアニリド誘導体と公知の殺虫剤、殺ダニ剤又は殺線虫剤とを含有する組成物が知られている(例えば、特許文献1参照。)。
有害生物防除剤、例えば殺虫剤や殺菌剤の長年にわたる使用により、近年、病害虫が抵抗性を獲得し、従来用いられてきた殺虫剤や殺菌剤による防除が困難になっている。また、既存の有害生物防除剤の一部のものは毒性が高く、或いはあるものは長期の残留性により、生態系を乱しつつある。このような状況下、低毒性かつ低残留性の新規な有害生物防除剤の開発が常に期待されている。 Pest control agents such as insecticides and fungicides have been used for many years, and in recent years, pests have acquired resistance, making it difficult to control them with conventionally used insecticides and fungicides. Also, some of the existing pest control agents are highly toxic or some are disrupting the ecosystem due to long-term persistence. Under such circumstances, development of a novel pesticide with low toxicity and low persistence is always expected.
しかしその一方、生物群としての昆虫や病原菌の多様性、その加害様式、加害場面の多様性を考えれば、これら新規の薬剤、あるいは既存の公知薬剤を単独で使用するだけでは、全ての防除場面で全ての病害虫を有効に防除することははなはだ難しい。そこで、複数の殺虫、殺ダニ、殺線虫、殺菌または殺バクテリア剤を適切に組み合わせてより高い防除効力を誘導し、防除困難な有害生物を防除する新たな方法もまた、強く要望されるに至っている。 On the other hand, considering the diversity of insects and pathogens as a group of organisms, the mode of damage, and the variety of scenes of harm, all these control scenes can be achieved simply by using these new drugs or existing known drugs alone. It is very difficult to control all pests effectively. Therefore, there is a strong demand for a new method for controlling pests that are difficult to control by appropriately combining a plurality of insecticides, acaricides, nematicides, bactericides, or bactericides to induce higher control efficacy. Has reached.
本発明者らは、上記の課題解決を目標に鋭意研究を重ねた結果、以下の一般式(1)及び一般式(2)で表される置換ベンズアニリド化合物、公知の殺虫、殺ダニ、殺線虫、殺菌又は殺バクテリア化合物を含有する殺虫、殺ダニ、殺線虫、殺菌又は殺バクテリア組成物が、単独の使用からは予測し得ない優れた相乗的殺虫、殺ダニ、殺線虫、殺菌又は殺バクテリア効果を奏することを見いだし、本発明を完成した。 As a result of intensive studies aimed at solving the above-mentioned problems, the present inventors have found that substituted benzanilide compounds represented by the following general formula (1) and general formula (2), known insecticides, acaricides, and killings Insecticidal, acaricidal, nematicidal, bactericidal or bactericidal compositions containing insects, bactericidal or bactericidal compounds are excellent synergistic insecticidal, acaricidal, nematicidal, bactericidal that cannot be predicted from single use Alternatively, the inventors have found that a bactericidal effect is achieved, and completed the present invention.
即ち、本発明は下記〔1〕〜〔8〕の組成物(以下、本発明組成物と称する。)、及び〔9〕〜〔16〕の使用方法(以下、本発明方法と称する。)に関するものである。 That is, the present invention relates to the following compositions [1] to [8] (hereinafter referred to as the present composition) and methods for using [9] to [16] (hereinafter referred to as the present method). Is.
〔1〕 以下の一般式(1)で表される置換ベンズアニリド化合物及びその塩より選ばれる1種又は2種以上と、以下の化合物群Aより選ばれる化合物の1種又は2種以上を含有する殺虫、殺ダニ、殺線虫、殺菌又は殺バクテリア組成物。 [1] 1 type or 2 or more types selected from the substituted benzanilide compound and its salt represented by the following general formula (1), and 1 type or 2 or more types of compounds selected from the following compound group A are contained. Insecticidal, acaricidal, nematicidal, bactericidal or bactericidal compositions.
一般式(1): General formula (1):
[式中、Gは、酸素原子、硫黄原子及び窒素原子から選ばれる原子を少なくとも1個含み、且つ環内に少なくともひとつの二重結合が存在する5員又は6員の非芳香族複素環、酸素原子、硫黄原子及び窒素原子から選ばれる原子を2個含む5員又は6員の飽和複素環又は3員から6員のシクロアルキル環を表し、
W1及びW2は、各々独立して酸素原子又は硫黄原子を表し、
Xは、ハロゲン原子、シアノ、ニトロ、アジド、-SCN、-SF5、C1〜C6アルキル、R7によって任意に置換された(C1〜C6)アルキル、C3〜C8シクロアルキル、R7によって任意に置換された(C3〜C8)シクロアルキル、C2〜C6アルケニル、R7によって任意に置換された(C2〜C6)アルケニル、C3〜C8シクロアルケニル、C3〜C8ハロシクロアルケニル、C2〜C6アルキニル、R7によって任意に置換された(C2〜C6)アルキニル、-OH、-OR8、-OS(O)2R8、-SH、-S(O)rR8、-CHO、-C(O)R9、-C(O)OR9、-C(O)SR9、-C(O)NHR10、-C(O)N(R10)R9、-C(S)OR9、-C(S)SR9、-C(S)NHR10、-C(S)N(R10)R9、-CH=NOR11、-C(R9)=NOR11、-S(O)2OR9、-S(O)2NHR10、-S(O)2N(R10)R9、-Si(R13)(R14)R12、(Z1)p1によって置換されていてもよいフェニル、L又はMを表し、mが2、3又は4を表すとき、各々のXは互いに同一であっても又は互いに相異なっていてもよく、
さらに、2つのXが隣接する場合には、隣接する2つのXは-CH2CH2CH2-, -CH2CH2O-, -CH2OCH2-, -OCH2O-, -CH2CH2S-, -CH2SCH2-, -CH2CH2N(R15)-, -CH2N(R15)CH2-, -CH2CH2CH2CH2-, -CH2CH2CH2O-, -CH2CH2OCH2-, -CH2OCH2O-, -OCH2CH2O-, -OCH2CH2S-, -CH2CH=CH-, -OCH=CH-, -SCH=CH-, -N(R15)CH=CH-, -OCH=N-, -SCH=N-, -N(R15)CH=N-, -N(R15)N=CH-, -CH=CHCH=CH-, -OCH2CH=CH-, -N=CHCH=CH-, -N=CHCH=N-又は-N=CHN=CH-を形成することにより、2つのXのそれぞれが結合する炭素原子と共に5員環又は6員環を形成してもよく、このとき、環を形成する各々の炭素原子に結合した水素原子はZ1によって任意に置換されていてもよく、さらに、同時に2個以上のZ1で置換されている場合、各々のZ1は互いに同一であっても又は互いに相異なっていてもよく、
また、Gが酸素原子、硫黄原子及び窒素原子から選ばれる原子を少なくとも1個含み、且つ環内に少なくともひとつの二重結合が存在する5員又は6員の非芳香族複素環を表すとき、Xはさらに-N(R17)R16、-N=CHOR12又は-N=C(R9)OR12を表すこともでき、
Yは、ハロゲン原子、シアノ、ニトロ、アジド、-SCN、-SF5、C1〜C6アルキル、R7によって任意に置換された(C1〜C6)アルキル、C3〜C8シクロアルキル、R7によって任意に置換された(C3〜C8)シクロアルキル、-OH、-OR8、-OS(O)2R8、-SH、-S(O)rR8、-NH2、C1〜C6アルキルアミノ、ジ(C1〜C6アルキル)アミノ、-Si(R13)(R14)R12、(Z1)p1によって置換されていてもよいフェニル、L又はMを表し、nが2、3又は4を表すとき、各々のYは互いに同一であっても又は互いに相異なっていてもよく、
さらに、2つのYが隣接する場合には、隣接する2つのYは-CH2CH2CH2-, -CH2CH2O-, -CH2OCH2-, -OCH2O-, -CH2CH2S-, -CH2SCH2-, -SCH2S-, -CH2CH2CH2CH2-, -CH2CH2CH2O-, -CH2CH2OCH2-, -CH2OCH2O-, -OCH2CH2O-, -OCH2CH2S-, -SCH2CH2S-, -OCH=N-又は-SCH=N-を形成することにより、2つのYのそれぞれが結合する炭素原子と共に5員環又は6員環を形成してもよく、このとき、環を形成する各々の炭素原子に結合した水素原子はZ1によって任意に置換されていてもよく、さらに、同時に2個以上のZ1で置換されている場合、各々のZ1は互いに同一であっても又は互いに相異なっていてもよく、
R1、R2及びR3は、各々独立して水素原子、シアノ、C1〜C12アルキル、R18によって任意に置換された(C1〜C12)アルキル、C3〜C12シクロアルキル、R18によって任意に置換された(C3〜C12)シクロアルキル、C3〜C12アルケニル、R18によって任意に置換された(C3〜C12)アルケニル、C3〜C12シクロアルケニル、C3〜C12ハロシクロアルケニル、C3〜C12アルキニル、R18によって任意に置換された(C3〜C12)アルキニル、-OH、C1〜C8アルコキシ、C3〜C8アルケニルオキシ、C3〜C8ハロアルケニルオキシ、(Z1)p1によって置換されていてもよいフェノキシ、(Z1)p1によって置換されていてもよいフェニル(C1〜C4)アルコキシ、C1〜C6アルキルチオ、C1〜C6ハロアルキルチオ、(Z1)p1によって置換されていてもよいフェニルチオ、-S(O)2R9、-SN(R20)R19、-S(O)2N(R10)R9、-N(R22)R21、-C(O)R9、-C(O)OR9、-C(O)SR9、-C(O)N(R10)R9、-C(S)OR9、-C(S)SR9、-C(S)N(R10)R9、(Z1)p1によって置換されていてもよいフェニル、L又はMを表すか、或いは、R2とR3とが一緒になってC2〜C6アルキレン鎖を形成することにより、結合する窒素原子と共に3〜7員環を形成してもよいことを表し、このときこのアルキレン鎖は酸素原子、硫黄原子又は窒素原子を1個含んでもよく、且つハロゲン原子、C1〜C6アルキル基、C1〜C6ハロアルキル基、C1〜C6アルコキシ基、C1〜C6アルキルカルボニル基又はC1〜C6アルコキシカルボニル基によって任意に置換されていてもよく、
R4は、水素原子、ハロゲン原子、シアノ、C1〜C6アルキル、C1〜C6ハロアルキル、R23によって任意に置換された(C1〜C6)アルキル、R23によって任意に置換された(C1〜C6)ハロアルキル、C3〜C8シクロアルキル、C3〜C8ハロシクロアルキル、R23によって任意に置換された(C3〜C8)シクロアルキル、R23によって任意に置換された(C3〜C8)ハロシクロアルキル、C3〜C6アルケニル、C3〜C6ハロアルケニル、C3〜C6アルキニル、C3〜C6ハロアルキニル、-OR8、-S(O)rR8、-N(R10)R9、-CHO、-C(O)R9、-C(O)OR9、-C(O)SR9、-C(O)NHR10、-C(O)N(R10)R9、-C(S)OR9、-C(S)SR9、-C(S)NHR10、-C(S)N(R10)R9、-CH=NOR11、-C(R9)=NOR11、-Si(R13)(R14)R12、-P(O)(OR24)2、(Z2)p1によって置換されていてもよいフェニル、1-ナフチル、2-ナフチル、L又はMを表し、
R5は、
(a). Gが酸素原子、硫黄原子及び窒素原子から選ばれる原子を少なくとも1個含み、且つ環内に少なくともひとつの二重結合が存在する5員又は6員の非芳香族複素環又は酸素原子、硫黄原子及び窒素原子から選ばれる原子を2個含む5員又は6員の飽和複素環を表すとき、水素原子、ハロゲン原子、シアノ、C1〜C6アルキル、C1〜C6ハロアルキル、R23によって任意に置換された(C1〜C6)アルキル、R23によって任意に置換された(C1〜C6)ハロアルキル、C3〜C8シクロアルキル、C3〜C8ハロシクロアルキル、R23によって任意に置換された(C3〜C8)シクロアルキル、R23によって任意に置換された(C3〜C8)ハロシクロアルキル、C3〜C6アルケニル、C3〜C6ハロアルケニル、C3〜C6アルキニル、C3〜C6ハロアルキニル、-OR8、-S(O)rR8、-N(R10)R9、-CHO、-C(O)R9、-C(O)OR9、-C(O)SR9、-C(O)NHR10、-C(O)N(R10)R9、-C(S)OR9、-C(S)SR9、-C(S)NHR10、-C(S)N(R10)R9、-CH=NOR11、-C(R9)=NOR11、(Z2)p1によって置換されていてもよいフェニル、1-ナフチル、2-ナフチル、L又はMを表し、
(b). Gが3員から6員のシクロアルキル環を表し、且つR4が水素原子、ハロゲン原子、C1〜C6アルキル又はC1〜C6ハロアルキルを表すとき、シアノ、R23によって任意に置換された(C1〜C6)アルキル、R23によって任意に置換された(C1〜C6)ハロアルキル、C3〜C8シクロアルキル、C3〜C8ハロシクロアルキル、R23によって任意に置換された(C3〜C8)シクロアルキル、R23によって任意に置換された(C3〜C8)ハロシクロアルキル、C3〜C6アルケニル、C3〜C6ハロアルケニル、C3〜C6アルキニル、C3〜C6ハロアルキニル、-OR8、-S(O)rR8、-N(R10)R9、-CHO、-C(O)R9、-C(O)OR9、-C(O)SR9、-C(O)NHR10、-C(O)N(R10)R9、-C(S)OR9、-C(S)SR9、-C(S)NHR10、-C(S)N(R10)R9、-CH=NOR11、-C(R9)=NOR11、-Si(R13)(R14)R12、(Z2)p1によって置換されていてもよいフェニル、1-ナフチル、2-ナフチル、L又はMを表し、
(c). Gが3員から6員のシクロアルキル環を表し、且つR4がシアノ、R23によって任意に置換された(C1〜C6)アルキル、R23によって任意に置換された(C1〜C6)ハロアルキル、C3〜C8シクロアルキル、C3〜C8ハロシクロアルキル、R23によって任意に置換された(C3〜C8)シクロアルキル、R23によって任意に置換された(C3〜C8)ハロシクロアルキル、C3〜C6アルケニル、C3〜C6ハロアルケニル、C3〜C6アルキニル、C3〜C6ハロアルキニル、-OR8、-S(O)rR8、-N(R10)R9、-CHO、-C(O)R9、-C(O)OR9、-C(O)SR9、-C(O)NHR10、-C(O)N(R10)R9、-C(S)OR9、-C(S)SR9、-C(S)NHR10、-C(S)N(R10)R9、-CH=NOR11、-C(R9)=NOR11、-Si(R13)(R14)R12、-P(O)(OR24)2、(Z2)p1によって置換されていてもよいフェニル、1-ナフチル、2-ナフチル、L又はMを表すとき、水素原子、ハロゲン原子、シアノ、C1〜C6アルキル、C1〜C6ハロアルキル、R23によって任意に置換された(C1〜C6)アルキル、R23によって任意に置換された(C1〜C6)ハロアルキル、C3〜C8シクロアルキル、C3〜C8ハロシクロアルキル、R23によって任意に置換された(C3〜C8)シクロアルキル、R23によって任意に置換された(C3〜C8)ハロシクロアルキル、C3〜C6アルケニル、C3〜C6ハロアルケニル、C3〜C6アルキニル、C3〜C6ハロアルキニル、-OR8、-S(O)rR8、-N(R10)R9、-CHO、-C(O)R9、-C(O)OR9、-C(O)SR9、-C(O)NHR10、-C(O)N(R10)R9、-C(S)OR9、-C(S)SR9、-C(S)NHR10、-C(S)N(R10)R9、-CH=NOR11、-C(R9)=NOR11、-Si(R13)(R14)R12、(Z2)p1によって置換されていてもよいフェニル、1-ナフチル、2-ナフチル、L又はMを表し、
R6は、水素原子、ハロゲン原子、シアノ、C1〜C6アルキル、C1〜C6ハロアルキル、R23によって任意に置換された(C1〜C6)アルキル、R23によって任意に置換された(C1〜C6)ハロアルキル、C3〜C8シクロアルキル、C3〜C8ハロシクロアルキル、R23によって任意に置換された(C3〜C8)シクロアルキル、R23によって任意に置換された(C3〜C8)ハロシクロアルキル、C1〜C6アルコキシ、C1〜C6ハロアルコキシ、C1〜C6アルキルチオ、C1〜C6ハロアルキルチオ、-S(O)2R9、-C(O)R9、-C(O)OR9、-C(O)SR9、-C(S)OR9、-C(S)SR9、-C(O)N(R10)R9、-C(S)N(R10)R9、-P(O)(OR24)2、-P(S)(OR24)2、(Z2)p1によって置換されていてもよいフェニル、1-ナフチル、2-ナフチル、L又はMを表し、lが2以上の整数を表すとき、各々のR6は互いに同一であっても又は互いに相異なっていてもよく、
さらに、R6がR4と隣接する場合、隣接するR4とR6とが一緒になってC3〜C5アルキレン鎖を形成することにより、結合する原子と共に5〜7員環を形成してもよいことを表し、このときこのアルキレン鎖は酸素原子又は硫黄原子を1個含んでもよく、且つC1〜C6アルキル基によって任意に置換されていてもよく、
Lは、式L-1から式L-58までの何れかで表される芳香族複素環を表し、
[Wherein G is a 5-membered or 6-membered non-aromatic heterocyclic ring containing at least one atom selected from an oxygen atom, a sulfur atom and a nitrogen atom, and having at least one double bond in the ring, A 5- or 6-membered saturated heterocyclic ring containing 2 atoms selected from an oxygen atom, a sulfur atom and a nitrogen atom, or a 3- to 6-membered cycloalkyl ring;
W 1 and W 2 each independently represent an oxygen atom or a sulfur atom,
X is a halogen atom, cyano, nitro, azido, -SCN, -SF 5, C 1 ~C 6 alkyl, optionally substituted by R 7 (C 1 ~C 6) alkyl, C 3 -C 8 cycloalkyl , optionally substituted by R 7 (C 3 ~C 8) cycloalkyl, C 2 -C 6 alkenyl, optionally substituted by R 7 (C 2 ~C 6) alkenyl, C 3 -C 8 cycloalkenyl , C 3 -C 8 halocycloalkyl cycloalkenyl, C 2 -C 6 alkynyl, optionally substituted by R 7 (C 2 ~C 6) alkynyl, -OH, -OR 8, -OS ( O) 2 R 8, -SH, -S (O) r R 8 , -CHO, -C (O) R 9 , -C (O) OR 9 , -C (O) SR 9 , -C (O) NHR 10 , -C ( O) N (R 10 ) R 9 , -C (S) OR 9 , -C (S) SR 9 , -C (S) NHR 10 , -C (S) N (R 10 ) R 9 , -CH = NOR 11 , -C (R 9 ) = NOR 11 , -S (O) 2 OR 9 , -S (O) 2 NHR 10 , -S (O) 2 N (R 10 ) R 9 , -Si (R 13 ) (R 14) R 12, (Z 1) phenyl optionally substituted by p1, represents L or M, when m represents 2, 3 or 4, respectively X may be the even or different from each other the same as each other,
Further, when two Xs are adjacent to each other, the two adjacent Xs are -CH 2 CH 2 CH 2- , -CH 2 CH 2 O-, -CH 2 OCH 2- , -OCH 2 O-, -CH 2 CH 2 S-, -CH 2 SCH 2- , -CH 2 CH 2 N (R 15 )-, -CH 2 N (R 15 ) CH 2- , -CH 2 CH 2 CH 2 CH 2- , -CH 2 CH 2 CH 2 O-, -CH 2 CH 2 OCH 2- , -CH 2 OCH 2 O-, -OCH 2 CH 2 O-, -OCH 2 CH 2 S-, -CH 2 CH = CH-,- OCH = CH-, -SCH = CH-, -N (R 15 ) CH = CH-, -OCH = N-, -SCH = N-, -N (R 15 ) CH = N-, -N (R 15 By forming N = CH-, -CH = CHCH = CH-, -OCH 2 CH = CH-, -N = CHCH = CH-, -N = CHCH = N- or -N = CHN = CH- A 5-membered ring or a 6-membered ring may be formed together with the carbon atom to which each of two Xs is bonded. At this time, the hydrogen atom bonded to each carbon atom forming the ring is optionally substituted by Z 1 . Furthermore, when two or more Z 1 are substituted at the same time, each Z 1 may be the same as or different from each other,
When G represents a 5-membered or 6-membered non-aromatic heterocyclic ring containing at least one atom selected from an oxygen atom, a sulfur atom and a nitrogen atom and having at least one double bond in the ring, X may further represent -N (R 17 ) R 16 , -N = CHOR 12 or -N = C (R 9 ) OR 12
Y is a halogen atom, cyano, nitro, azido, -SCN, -SF 5, C 1 ~C 6 alkyl, optionally substituted by R 7 (C 1 ~C 6) alkyl, C 3 -C 8 cycloalkyl , optionally substituted by R 7 (C 3 ~C 8) cycloalkyl, -OH, -OR 8, -OS ( O) 2 R 8, -SH, -S (O) r R 8, -NH 2 , C 1 -C 6 alkylamino, di (C 1 -C 6 alkyl) amino, phenyl, L or M optionally substituted by -Si (R 13 ) (R 14 ) R 12 , (Z 1 ) p1 And when n represents 2, 3 or 4, each Y may be the same as or different from each other,
Further, when two Ys are adjacent to each other, the two adjacent Ys are —CH 2 CH 2 CH 2 —, —CH 2 CH 2 O—, —CH 2 OCH 2 —, —OCH 2 O—, —CH 2 CH 2 S-, -CH 2 SCH 2- , -SCH 2 S-, -CH 2 CH 2 CH 2 CH 2- , -CH 2 CH 2 CH 2 O-, -CH 2 CH 2 OCH 2 -,- By forming CH 2 OCH 2 O-, -OCH 2 CH 2 O-, -OCH 2 CH 2 S-, -SCH 2 CH 2 S-, -OCH = N- or -SCH = N- A 5-membered ring or a 6-membered ring may be formed together with the carbon atom to which each Y is bonded, and at this time, the hydrogen atom bonded to each carbon atom forming the ring may be optionally substituted by Z 1 In addition, in addition, when simultaneously substituted with two or more Z 1 , each Z 1 may be the same as or different from each other,
R 1 , R 2 and R 3 are each independently a hydrogen atom, cyano, C 1 -C 12 alkyl, (C 1 -C 12 ) alkyl optionally substituted by R 18 , C 3 -C 12 cycloalkyl , optionally substituted by R 18 (C 3 ~C 12) cycloalkyl, C 3 -C 12 alkenyl, optionally substituted by R 18 (C 3 ~C 12) alkenyl, C 3 -C 12 cycloalkenyl , C 3 -C 12 halo cycloalkenyl, C 3 -C 12 alkynyl, optionally substituted by R 18 (C 3 ~C 12) alkynyl, -OH, C 1 -C 8 alkoxy, C 3 -C 8 alkenyl oxy, C 3 -C 8 haloalkenyloxy, (Z 1) which may be substituted by p1 phenoxy, (Z 1) p1 phenyl optionally substituted by (C 1 ~C 4) alkoxy, C 1 ~ C 6 alkylthio, C 1 -C 6 haloalkylthio, (Z 1) p1 may be substituted by phenylthio, -S (O) 2 R 9 , -SN (R 20 ) R 19 , -S (O) 2 N (R 10 ) R 9 , -N (R 22 ) R 21 , -C (O) R 9 , -C (O) OR 9 , -C (O) SR 9 , -C (O) N (R 10 ) R 9 , -C (S) OR 9 , -C (S) SR 9 , -C (S) N (R 10 ) R 9 , (Z 1 ) by p1 Optionally substituted phenyl, L or M, or R 2 and R 3 together form a C 2 -C 6 alkylene chain to form a 3-7 member with the nitrogen atom to which it is attached indicates that may form a ring, this time the alkylene chain an oxygen atom, may contain one sulfur atom or a nitrogen atom, and a halogen atom, C 1 -C 6 alkyl group, C 1 -C 6 haloalkyl group may be optionally substituted by C 1 -C 6 alkoxy group, C 1 -C 6 alkylcarbonyl group or a C 1 -C 6 alkoxycarbonyl group,
R 4 is a hydrogen atom, a halogen atom, cyano, optionally substituted by C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, optionally substituted by R 23 (C 1 ~C 6) alkyl, R 23 and (C 1 ~C 6) haloalkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 halocycloalkyl, optionally substituted by R 23 (C 3 ~C 8) cycloalkyl, optionally by R 23 substituted (C 3 ~C 8) halocycloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 alkynyl, C 3 -C 6 haloalkynyl, -OR 8, -S (O) r R 8 , -N (R 10 ) R 9 , -CHO, -C (O) R 9 , -C (O) OR 9 , -C (O) SR 9 , -C (O) NHR 10 , -C (O) N (R 10 ) R 9 , -C (S) OR 9 , -C (S) SR 9 , -C (S) NHR 10 , -C (S) N (R 10 ) R 9 , -CH = NOR 11 , -C (R 9 ) = NOR 11 , -Si (R 13 ) (R 14 ) R 12 , -P (O) (OR 24 ) 2 , (Z 2 ) p1 May represent phenyl, 1-naphthyl, 2-naphthyl, L or M;
R 5 is
(a) a 5- or 6-membered non-aromatic heterocyclic ring or oxygen containing at least one atom selected from oxygen, sulfur and nitrogen, and having at least one double bond in the ring; atom, to represent a saturated 5- or 6-membered heterocyclic ring containing two atoms selected from sulfur atom and a nitrogen atom, a hydrogen atom, a halogen atom, cyano, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, optionally substituted by R 23 (C 1 ~C 6) alkyl, optionally substituted by R 23 (C 1 ~C 6) haloalkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 halocycloalkyl , optionally substituted by R 23 (C 3 ~C 8) cycloalkyl, optionally substituted by R 23 (C 3 ~C 8) halocycloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 alkynyl, C 3 -C 6 haloalkynyl, -OR 8, -S (O) r R 8, -N (R 1 0 ) R 9 , -CHO, -C (O) R 9 , -C (O) OR 9 , -C (O) SR 9 , -C (O) NHR 10 , -C (O) N (R 10 ) R 9 , -C (S) OR 9 , -C (S) SR 9 , -C (S) NHR 10 , -C (S) N (R 10 ) R 9 , -CH = NOR 11 , -C (R 9 ) = NOR 11 , (Z 2 ) represents phenyl, 1-naphthyl, 2-naphthyl, L or M optionally substituted by p1 ,
(b). G represents a cycloalkyl ring of 3 to 6-membered, and when R 4 represents a hydrogen atom, a halogen atom, C 1 -C 6 alkyl or C 1 -C 6 haloalkyl, cyano, by R 23 Optionally substituted (C 1 -C 6 ) alkyl, (C 1 -C 6 ) haloalkyl optionally substituted by R 23 , C 3 -C 8 cycloalkyl, C 3 -C 8 halocycloalkyl, R 23 optionally substituted by (C 3 ~C 8) cycloalkyl, optionally substituted by R 23 (C 3 ~C 8) halocycloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 alkynyl, C 3 -C 6 haloalkynyl, -OR 8, -S (O) r R 8, -N (R 10) R 9, -CHO, -C (O) R 9, -C (O) OR 9 , -C (O) SR 9 , -C (O) NHR 10 , -C (O) N (R 10 ) R 9 , -C (S) OR 9 , -C (S) SR 9 , -C (S) NHR 10 , -C (S) N (R 10 ) R 9 , -CH = NOR 11 , -C (R 9 ) = NOR 11 , -Si (R 13 ) (R 14 ) R 12 , (Z 2) which may be substituted by p1 phenylene Represents 1-naphthyl, 2-naphthyl, L or M,
(c). G represents a cycloalkyl ring of 3 to 6-membered, and R 4 is cyano, optionally substituted by optionally substituted by R 23 (C 1 ~C 6) alkyl, R 23 ( C 1 -C 6) haloalkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 halocycloalkyl, optionally substituted by R 23 (C 3 ~C 8) cycloalkyl, optionally substituted with R 23 and (C 3 ~C 8) halocycloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 alkynyl, C 3 -C 6 haloalkynyl, -OR 8, -S (O ) r R 8 , -N (R 10 ) R 9 , -CHO, -C (O) R 9 , -C (O) OR 9 , -C (O) SR 9 , -C (O) NHR 10 ,- C (O) N (R 10 ) R 9 , -C (S) OR 9 , -C (S) SR 9 , -C (S) NHR 10 , -C (S) N (R 10 ) R 9 ,- CH = NOR 11, -C (R 9) = NOR 11, -Si (R 13) (R 14) R 12, -P (O) (OR 24) 2, optionally substituted by (Z 2) p1 Good phenyl, 1-naphthyl, 2-naphthyl, L or M represents hydrogen atom, halogen Atom, cyano, optionally substituted by C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, optionally substituted by R 23 (C 1 ~C 6) alkyl, R 23 (C 1 ~C 6) haloalkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 halocycloalkyl, optionally substituted by R 23 (C 3 ~C 8) cycloalkyl, optionally substituted by R 23 (C 3 ~C 8) halocycloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 alkynyl, C 3 -C 6 haloalkynyl, -OR 8, -S (O) r R 8, - N (R 10 ) R 9 , -CHO, -C (O) R 9 , -C (O) OR 9 , -C (O) SR 9 , -C (O) NHR 10 , -C (O) N ( R 10 ) R 9 , -C (S) OR 9 , -C (S) SR 9 , -C (S) NHR 10 , -C (S) N (R 10 ) R 9 , -CH = NOR 11 ,- C (R 9 ) = NOR 11 , -Si (R 13 ) (R 14 ) R 12 , (Z 2 ) represents phenyl, 1-naphthyl, 2-naphthyl, L or M optionally substituted by p1 ,
R 6 is a hydrogen atom, a halogen atom, cyano, optionally substituted by C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, optionally substituted by R 23 (C 1 ~C 6) alkyl, R 23 and (C 1 ~C 6) haloalkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 halocycloalkyl, optionally substituted by R 23 (C 3 ~C 8) cycloalkyl, optionally by R 23 substituted (C 3 ~C 8) halocycloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 alkylthio, C 1 -C 6 haloalkylthio, -S (O) 2 R 9 , -C (O) R 9 , -C (O) OR 9 , -C (O) SR 9 , -C (S) OR 9 , -C (S) SR 9 , -C (O) N ( R 10 ) R 9 , -C (S) N (R 10 ) R 9 , -P (O) (OR 24 ) 2 , -P (S) (OR 24 ) 2 , (Z 2 ) p1 phenyl optionally, 1-naphthyl, 2-naphthyl, represents L or M, when l is an integer of 2 or more, also each of R 6 the same as each other or different from each other May have become, the
Further, R 6 may be adjacent to R 4, by R 4 and R 6 adjacent to form a C 3 -C 5 alkylene chain together, a 5- to 7-membered ring is formed together with the atoms connecting The alkylene chain may contain one oxygen or sulfur atom and may be optionally substituted with a C 1 -C 6 alkyl group,
L represents an aromatic heterocycle represented by any one of formulas L-1 to L-58,
Mは、式M-1から式M-28までの何れかで表される飽和複素環を表し、 M represents a saturated heterocyclic ring represented by any one of formulas M-1 to M-28;
Z1は、ハロゲン原子、シアノ、ニトロ、C1〜C6アルキル、C1〜C6ハロアルキル、C3〜C6シクロアルキル、C3〜C6ハロシクロアルキル、C2〜C6アルケニル、C2〜C6ハロアルケニル、C2〜C6アルキニル、C2〜C6ハロアルキニル、C1〜C6アルコキシ、C1〜C6ハロアルコキシ、C1〜C6アルキルチオ、C1〜C6ハロアルキルチオ、C1〜C6アルキルスルフィニル、C1〜C6ハロアルキルスルフィニル、C1〜C6アルキルスルホニル、C1〜C6ハロアルキルスルホニル、C1〜C6アルキルアミノ、ジ(C1〜C6アルキル)アミノ、C1〜C6アルコキシカルボニル、C1〜C6ハロアルコキシカルボニル又はハロゲン原子によって任意に置換されていてもよいフェニルを表し、p1, p2, p3又はp4が2以上の整数を表すとき、各々のZ1は互いに同一であっても又は互いに相異なっていてもよく、
Z2は、ハロゲン原子、シアノ、ニトロ、アミノ、アジド、-SCN、-SF5、C1〜C6アルキル、R7によって任意に置換された(C1〜C6)アルキル、C3〜C8シクロアルキル、R7によって任意に置換された(C3〜C8)シクロアルキル、C2〜C6アルケニル、R7によって任意に置換された(C2〜C6)アルケニル、C3〜C8シクロアルケニル、C3〜C8ハロシクロアルケニル、C2〜C6アルキニル、R7によって任意に置換された(C2〜C6)アルキニル、-OH、-OR8、-OS(O)2R8、-SH、-S(O)rR8、-N(R10)R9、-N(R10)CHO、-N(R10)C(O)R9、-N(R10)C(O)OR9、-N(R10)C(O)SR9、-N(R10)C(S)OR9、-N(R10)C(S)SR9、-N(R10)S(O)2R9、-CHO、-C(O)R9、-C(O)OR9、-C(O)NHR10、-C(O)N(R10)R9、-C(S)NHR10、-C(S)N(R10)R9、-S(O)2OR9、-S(O)2NHR10、-S(O)2N(R10)R9、-Si(R13)(R14)R12、(Z1)p1によって置換されていてもよいフェニル、L又はMを表し、p1が2以上の整数を表すとき、各々のZ2は互いに同一であっても又は互いに相異なっていてもよく、
さらに、2つのZ2が隣接する場合には、隣接する2つのZ2は-CH2CH2CH2-, -CH2CH2O-, -CH2OCH2-, -OCH2O-, -CH2CH2S-, -CH2SCH2-, -CH2CH2CH2CH2-, -CH2CH2CH2O-, -CH2CH2OCH2-, -CH2OCH2O-, -OCH2CH2O-又は-OCH2CH2S-を形成することにより、2つのZ2のそれぞれが結合する炭素原子と共に5員環又は6員環を形成してもよく、このとき、環を形成する各々の炭素原子に結合した水素原子はハロゲン原子又はC1〜C6アルキル基によって任意に置換されていてもよく、
R7は、ハロゲン原子、シアノ、C3〜C8シクロアルキル、C3〜C8ハロシクロアルキル、-OH、-OR8、-SH、-S(O)rR8、-N(R10)R9、-N(R10)CHO、-N(R10)C(O)R9、-N(R10)C(O)OR9、-N(R10)C(O)SR9、-N(R10)C(S)OR9、-N(R10)C(S)SR9、-N(R10)S(O)2R9、-C(O)OR9、-C(O)N(R10)R9、-Si(R13)(R14)R12、(Z1)p1によって置換されていてもよいフェニル、L又はMを表し、
R8は、C1〜C6アルキル、R27によって任意に置換された(C1〜C6)アルキル、C3〜C8シクロアルキル、R27によって任意に置換された(C3〜C8)シクロアルキル、C2〜C6アルケニル、R27によって任意に置換された(C2〜C6)アルケニル、C3〜C8シクロアルケニル、C3〜C8ハロシクロアルケニル、C3〜C6アルキニル、R27によって任意に置換された(C3〜C6)アルキニル、(Z1)p1によって置換されていてもよいフェニル、L又はMを表し、
R9は、C1〜C6アルキル、C1〜C6ハロアルキル、C3〜C6シクロアルキル(C1〜C4)アルキル、C1〜C6アルコキシ(C1〜C4)アルキル、C1〜C6アルキルチオ(C1〜C4)アルキル、シアノ(C1〜C6)アルキル、(Z1)p1によって置換されていてもよいフェニル(C1〜C4)アルキル、L-(C1〜C4)アルキル、M-(C1〜C4)アルキル、C3〜C8シクロアルキル、C3〜C8ハロシクロアルキル、C3〜C6アルケニル、C3〜C6ハロアルケニル、C3〜C6アルキニル又は(Z1)p1によって置換されていてもよいフェニルを表し、
R10は、水素原子又はC1〜C6アルキルを表すか、或いは、R9とR10とが一緒になってC2〜C6アルキレン鎖を形成することにより、結合する原子と共に3〜7員環を形成してもよいことを表し、このときこのアルキレン鎖は酸素原子、硫黄原子又は窒素原子を1個含んでもよく、且つハロゲン原子、C1〜C6アルキル基、C1〜C6アルコキシ基、ホルミル基、C1〜C6アルキルカルボニル基又はC1〜C6アルコキシカルボニル基によって任意に置換されていてもよく、
R11は、水素原子、C1〜C6アルキル、C1〜C6ハロアルキル、(Z1)p1によって置換されていてもよいフェニル(C1〜C4)アルキル、C3〜C6アルケニル、C3〜C6ハロアルケニル、C3〜C6アルキニル又はC3〜C6ハロアルキニルを表すか、或いは、R9とR11とが一緒になってC2〜C4アルキレン鎖を形成することにより、結合する原子と共に5〜7員環を形成してもよいことを表し、このときこのアルキレン鎖は酸素原子、硫黄原子又は窒素原子を1個含んでもよく、且つハロゲン原子又はC1〜C6アルキル基によって任意に置換されていてもよく、
R12は、C1〜C6アルキル、C1〜C6ハロアルキル、C3〜C6アルケニル又は(Z1)p1によって置換されていてもよいフェニルを表し、
R13及びR14は、各々独立してC1〜C6アルキル又はC1〜C6ハロアルキルを表し、
R15は、水素原子、C1〜C6アルキル、C1〜C6ハロアルキル、C1〜C6アルコキシカルボニル(C1〜C4)アルキル、C1〜C6ハロアルコキシカルボニル(C1〜C4)アルキル、(Z1)p1によって置換されていてもよいフェニル(C1〜C4)アルキル、C3〜C6アルケニル、C3〜C6ハロアルケニル、C3〜C6アルキニル、C3〜C6ハロアルキニル、C1〜C6アルコキシ、C1〜C6アルコキシカルボニル、C1〜C6ハロアルコキシカルボニル又は(Z1)p1によって置換されていてもよいフェニルを表し、
R16は、水素原子、C1〜C6アルキル、C1〜C6ハロアルキル、C3〜C6シクロアルキル(C1〜C4)アルキル、C1〜C4アルコキシ(C1〜C4)アルキル、C1〜C4アルキルチオ(C1〜C4)アルキル、(Z1)p1によって置換されていてもよいフェニルチオ(C1〜C4)アルキル、シアノ(C1〜C6)アルキル、C1〜C6アルコキシカルボニル(C1〜C4)アルキル、C1〜C6アルキルアミノカルボニル(C1〜C4)アルキル、ジ(C1〜C6アルキル)アミノカルボニル(C1〜C4)アルキル、(Z1)p1によって置換されていてもよいフェニル(C1〜C4)アルキル、L-(C1〜C4)アルキル、M-(C1〜C4)アルキル、C3〜C6シクロアルキル、C3〜C6アルケニル、C3〜C6ハロアルケニル、C3〜C6アルキニル、C3〜C6ハロアルキニル、-OH、C1〜C6アルキルカルボニルオキシ、C1〜C6アルキルチオ、C1〜C6ハロアルキルチオ、(Z1)p1によって置換されていてもよいフェニルチオ、C1〜C6アルキルスルホニル、C1〜C6ハロアルキルスルホニル、(Z1)p1によって置換されていてもよいフェニルスルホニル、-SN(R20)R19、C1〜C6アルキルアミノスルホニル、ジ(C1〜C6アルキル)アミノスルホニル、-CHO、-C(O)R9、-C(O)OR9、-C(O)SR9、-C(O)NHR10、-C(O)N(R10)R9、-C(S)OR9、-C(S)SR9、-C(S)NHR10、-C(S)N(R10)R9、-C(O)C(O)R9、-C(O)C(O)OR9、-P(O)(OR24)2又は-P(S)(OR24)2を表し、
R17は、水素原子、C1〜C6アルキル、C1〜C6ハロアルキル、C3〜C8シクロアルキル(C1〜C6)アルキル、C3〜C8シクロアルキル、C3〜C6アルケニル、C3〜C6ハロアルケニル、C3〜C6アルキニル、C3〜C6ハロアルキニル、-CHO、C1〜C6アルキルカルボニル、C1〜C6ハロアルキルカルボニル又はC1〜C6アルコキシカルボニルを表すか、或いは、R16とR17とが一緒になってC2〜C6アルキレン鎖を形成することにより、結合する窒素原子と共に3〜7員環を形成してもよいことを表し、このときこのアルキレン鎖は酸素原子、硫黄原子又は窒素原子を1個含んでもよく、且つハロゲン原子、C1〜C6アルキル基又はC1〜C6ハロアルキル基によって任意に置換されていてもよく、さらに或いは、R17がR2と一緒になってC1〜C2アルキレン鎖を形成することにより、結合する原子と共にベンゼン環と縮合する6員又は7員のヘテロ環を形成してもよいことを表し、このときこのアルキレン鎖は酸素原子又はC1〜C6アルキル基によって任意に置換されていてもよく、
R18は、ハロゲン原子、シアノ、ニトロ、C3〜C8シクロアルキル、C3〜C8ハロシクロアルキル、-OR28、-N(R29)R28、-SH、-S(O)rR30、-CHO、-C(O)R31、-C(O)OH、-C(O)OR31、-C(O)SR31、-C(O)NHR32、-C(O)N(R32)R31、-C(O)C(O)OR31、-C(R34)=NOH、-C(R34)=NOR33、-Si(R13)(R14)R12、-P(O)(OR24)2、-P(S)(OR24)2、-P(フェニル)2、-P(O)(フェニル)2、(Z1)p1によって置換されていてもよいフェニル、L又はMを表し、
R19は、C1〜C12アルキル、C1〜C12ハロアルキル、C1〜C12アルコキシ(C1〜C12)アルキル、シアノ(C1〜C12)アルキル、C1〜C12アルコキシカルボニル(C1〜C12)アルキル、(Z1)p1によって置換されていてもよいフェニル(C1〜C4)アルキル、C3〜C12アルケニル、C3〜C12ハロアルケニル、C3〜C12アルキニル、C3〜C12ハロアルキニル、C1〜C12アルキルカルボニル、C1〜C12アルコキシカルボニル又は(Z1)p1によって置換されていてもよいフェニルを表し、
R20は、C1〜C12アルキル、C1〜C12ハロアルキル、C1〜C12アルコキシ(C1〜C12)アルキル、シアノ(C1〜C12)アルキル、C1〜C12アルコキシカルボニル(C1〜C12)アルキル、(Z1)p1によって置換されていてもよいフェニル(C1〜C4)アルキル、C3〜C12アルケニル、C3〜C12ハロアルケニル、C3〜C12アルキニル、C3〜C12ハロアルキニル又は(Z1)p1によって置換されていてもよいフェニルを表すか、或いは、R19とR20とが一緒になってC4〜C7アルキレン鎖を形成することにより、結合する窒素原子と共に5〜8員環を形成してもよいことを表し、このときこのアルキレン鎖は酸素原子又は硫黄原子を1個含んでもよく、且つC1〜C4アルキル基又はC1〜C4アルコキシ基によって任意に置換されていてもよく、
R21は、水素原子、C1〜C6アルキル、C1〜C6ハロアルキル、(Z1)p1によって置換されていてもよいフェニル(C1〜C4)アルキル、C3〜C6アルケニル、C3〜C6ハロアルケニル、C3〜C6アルキニル、-CHO、C1〜C6アルキルカルボニル、C1〜C6ハロアルキルカルボニル、C1〜C6アルコキシカルボニル、C1〜C6ハロアルコキシカルボニル、(Z1)p1によって置換されていてもよいフェニル(C1〜C4)アルコキシカルボニル、(Z1)p1によって置換されていてもよいフェノキシカルボニル、(Z1)p1によって置換されていてもよいフェニルカルボニル又は(Z1)p1によって置換されていてもよいフェニルを表し、
R22は、水素原子、C1〜C6アルキル、-CHO、C1〜C6アルキルカルボニル、C1〜C6ハロアルキルカルボニル又はC1〜C6アルコキシカルボニルを表し、
R23は、シアノ、C3〜C8シクロアルキル、C3〜C8ハロシクロアルキル、-OH、-OR8、-SH、-S(O)rR8、-N(R10)R9、-N(R10)CHO、-N(R10)C(O)R9、-N(R10)C(O)OR9、-N(R10)C(O)SR9、-N(R10)C(S)OR9、-N(R10)C(S)SR9、-N(R10)S(O)2R9、-C(O)OR9、-C(O)N(R10)R9、-Si(R13)(R14)R12、(Z1)p1によって置換されていてもよいフェニル、L又はMを表し、
R24は、C1〜C6アルキル又はC1〜C6ハロアルキルを表し、
R25は、ハロゲン原子、シアノ、C1〜C6アルキル、C1〜C6ハロアルキル、ヒドロキシ(C1〜C6)アルキル、C1〜C4アルコキシ(C1〜C4)アルキル、C1〜C4アルコキシカルボニル(C1〜C4)アルキル、C1〜C6アルコキシ、C1〜C6アルコキシカルボニル又は(Z1)p1によって置換されていてもよいフェニルを表し、q1, q2, q3又はq4が2以上の整数を表すとき、各々のR25は互いに同一であっても、または互いに相異なっていてもよく、
R26は、水素原子、C1〜C6アルキル、C1〜C6ハロアルキル、-CHO、C1〜C6アルキルカルボニル、C1〜C6ハロアルキルカルボニル、(Z1)p1によって置換されていてもよいフェニル(C1〜C4)アルキルカルボニル、C1〜C6アルコキシカルボニル、C1〜C6ハロアルコキシカルボニル、(Z1)p1によって置換されていてもよいフェニル(C1〜C4)アルコキシカルボニル、C1〜C6アルキルアミノカルボニル、ジ(C1〜C6アルキル)アミノカルボニル、C1〜C6アルキルアミノチオカルボニル、ジ(C1〜C6アルキル)アミノチオカルボニル、(Z1)p1によって置換されていてもよいフェニルカルボニル、C1〜C6アルキルスルホニル、C1〜C6ハロアルキルスルホニル、(Z1)p1によって置換されていてもよいフェニルスルホニル、-P(O)(OR24)2又は-P(S)(OR24)2を表し、
R27は、ハロゲン原子、シアノ、C3〜C8シクロアルキル、C3〜C8ハロシクロアルキル、C1〜C6アルコキシ、C1〜C6ハロアルコキシ、C1〜C6アルキルチオ、C1〜C6ハロアルキルチオ、C1〜C6アルキルスルホニル、C1〜C6ハロアルキルスルホニル、C1〜C6アルキルアミノ、ジ(C1〜C6アルキル)アミノ、-CHO、C1〜C6アルキルカルボニル、C1〜C6ハロアルキルカルボニル、C1〜C6アルコキシカルボニル、C1〜C6ハロアルコキシカルボニル、-CH=NOR11、-C(R9)=NOR11、(Z1)p1によって置換されていてもよいフェニル、L又はMを表し、
R28は、水素原子、C1〜C8アルキル、R35によって任意に置換された(C1〜C8)アルキル、C3〜C8シクロアルキル、R35によって任意に置換された(C3〜C8)シクロアルキル、C3〜C8アルケニル、R35によって任意に置換された(C3〜C8)アルケニル、C3〜C8アルキニル、R35によって任意に置換された(C3〜C8)アルキニル、-CHO、-C(O)R31、-C(O)OR31、-C(O)SR31、-C(O)NHR32、-C(O)N(R32)R31、-C(O)C(O)R31、-C(O)C(O)OR31、-C(S)R31、-C(S)OR31、-C(S)SR31、-C(S)NHR32、-C(S)N(R32)R31、-S(O)2R31、-S(O)2N(R32)R31、-Si(R13)(R14)R12、-P(O)(OR24)2、-P(S)(OR24)2、(Z1)p1によって置換されていてもよいフェニル、L又はMを表し、
R29は、水素原子、C1〜C6アルキル、C1〜C6ハロアルキル、C3〜C6シクロアルキル又はC1〜C6アルコキシを表すか、或いは、R28とR29とが一緒になってC2〜C5アルキレン鎖を形成することにより、結合する窒素原子と共に3〜6員環を形成してもよいことを表し、このときこのアルキレン鎖は酸素原子又は硫黄原子を1個含んでもよく、且つハロゲン原子、C1〜C6アルキル基、C1〜C6アルコキシ基又は(Z1)p1によって置換されていてもよいフェニル基によって置換されていてもよく、
R30は、C1〜C8アルキル、R35によって任意に置換された(C1〜C8)アルキル、C3〜C8シクロアルキル、R35によって任意に置換された(C3〜C8)シクロアルキル、C3〜C8アルケニル、R35によって任意に置換された(C3〜C8)アルケニル、C3〜C8アルキニル、R35によって任意に置換された(C3〜C8)アルキニル、-SH、C1〜C6アルキルチオ、C1〜C6ハロアルキルチオ、(Z1)p1によって置換されていてもよいフェニルチオ、-CHO、-C(O)R31、-C(O)OR31、-C(O)SR31、-C(O)NHR32、-C(O)N(R32)R31、-C(O)C(O)R31、-C(O)C(O)OR31、-C(S)R31、-C(S)OR31、-C(S)SR31、-C(S)NHR32、-C(S)N(R32)R31、-P(O)(OR24)2、-P(S)(OR24)2、(Z1)p1によって置換されていてもよいフェニル、L-18、L-21、L-25、L-30〜L-35、L-45、L-48、L-49又はMを表し、
R31は、C1〜C6アルキル、C1〜C6ハロアルキル、C3〜C8シクロアルキル(C1〜C4)アルキル、C1〜C6アルコキシ(C1〜C4)アルキル、C1〜C6ハロアルコキシ(C1〜C4)アルキル、C1〜C6アルキルチオ(C1〜C4)アルキル、C1〜C6ハロアルキルチオ(C1〜C4)アルキル、C1〜C6アルキルスルホニル(C1〜C4)アルキル、C1〜C6ハロアルキルスルホニル(C1〜C4)アルキル、シアノ(C1〜C6)アルキル、C1〜C6アルキルカルボニル(C1〜C4)アルキル、C1〜C6ハロアルキルカルボニル(C1〜C4)アルキル、C1〜C6アルコキシカルボニル(C1〜C4)アルキル、ジ(C1〜C6アルキル)アミノカルボニル(C1〜C4)アルキル、トリ(C1〜C4アルキル)シリル(C1〜C4)アルキル、(Z1)p1によって置換されていてもよいフェニル(C1〜C4)アルキル、L-(C1〜C4)アルキル、M-(C1〜C4)アルキル、C3〜C8シクロアルキル、C3〜C8ハロシクロアルキル、C2〜C6アルケニル(C3〜C8)シクロアルキル、C2〜C6ハロアルケニル(C3〜C8)シクロアルキル、C2〜C6アルケニル、C2〜C6ハロアルケニル、C2〜C6アルキニル、C2〜C6ハロアルキニル、(Z1)p1によって置換されていてもよいフェニル、L又はMを表し、
R32は、水素原子、C1〜C6アルキル、C1〜C6ハロアルキル又は(Z1)p1によって置換されていてもよいフェニルを表すか、或いは、R31とR32とが一緒になってC2〜C5アルキレン鎖を形成することにより、結合する窒素原子と共に3〜6員環を形成してもよいことを表し、このときこのアルキレン鎖は酸素原子、硫黄原子又は窒素原子を1個含んでもよく、且つハロゲン原子、C1〜C6アルキル基、C1〜C6アルコキシ基、ホルミル基、C1〜C6アルキルカルボニル基、C1〜C6アルコキシカルボニル基又は(Z1)p1によって置換されていてもよいフェニル基によって任意に置換されていてもよく、
R33は、水素原子、C1〜C8アルキル、R35によって任意に置換された(C1〜C8)アルキル、C3〜C8シクロアルキル、C3〜C8アルケニル、R35によって任意に置換された(C3〜C8)アルケニル、C3〜C8アルキニル又はR35によって任意に置換された(C3〜C8)アルキニルを表し、
R34は、水素原子、C1〜C6アルキル、C1〜C6ハロアルキル、C3〜C8シクロアルキル(C1〜C4)アルキル、C1〜C6アルコキシ(C1〜C4)アルキル、C1〜C6ハロアルコキシ(C1〜C4)アルキル、C1〜C6アルキルチオ(C1〜C4)アルキル、C1〜C6ハロアルキルチオ(C1〜C4)アルキル、C1〜C6アルキルスルホニル(C1〜C4)アルキル、C1〜C6ハロアルキルスルホニル(C1〜C4)アルキル、(Z1)p1によって置換されていてもよいフェニル(C1〜C4)アルキル又は(Z1)p1によって置換されていてもよいフェニルを表し、
R35は、ハロゲン原子、シアノ、ニトロ、C3〜C8シクロアルキル、C3〜C8ハロシクロアルキル、-OH、-OR36、-SH、-S(O)rR36、-NHR37、-N(R37)R36、-CHO、-C(O)R31、-C(O)OR31、-C(O)SR31、-C(O)NHR32、-C(O)N(R32)R31、-C(O)C(O)OR31、-CH=NOR11、-C(R9)=NOR11、-Si(R13)(R14)R12、-P(O)(OR24)2、-P(S)(OR24)2、-P(フェニル)2、-P(O)(フェニル)2、(Z1)p1によって置換されていてもよいフェニル、L又はMを表し、
R36は、C1〜C6アルキル、C1〜C6ハロアルキル、C1〜C6アルコキシ(C1〜C4)アルキル、C1〜C6アルキルチオ(C1〜C4)アルキル、(Z1)p1によって置換されていてもよいフェニル(C1〜C4)アルキル、C3〜C8シクロアルキル、C3〜C8ハロシクロアルキル、C3〜C6アルケニル、C3〜C6ハロアルケニル、C3〜C8シクロアルケニル、C3〜C8ハロシクロアルケニル、C3〜C6アルキニル、C3〜C6ハロアルキニル、-CHO、C1〜C6アルキルカルボニル、C1〜C6ハロアルキルカルボニル、C1〜C6アルコキシカルボニル、C1〜C6ハロアルコキシカルボニル、C1〜C6アルキルアミノカルボニル、ジ(C1〜C6アルキル)アミノカルボニル、(Z1)p1によって置換されていてもよいフェニルカルボニル、C1〜C6アルキルアミノチオカルボニル、ジ(C1〜C6アルキル)アミノチオカルボニル、(Z1)p1によって置換されていてもよいフェニル、L又はMを表し、
R37は、水素原子、C1〜C6アルキル、C1〜C6ハロアルキル、C3〜C8シクロアルキル、C3〜C6アルケニル、C3〜C6アルキニル、C1〜C6アルキルカルボニル、C1〜C6ハロアルキルカルボニル、C1〜C6アルコキシカルボニル、C1〜C6ハロアルコキシカルボニル、(Z1)p1によって置換されていてもよいフェノキシカルボニル、(Z1)p1によって置換されていてもよいフェニルカルボニル、C1〜C6アルキルスルホニル、C1〜C6ハロアルキルスルホニル、(Z1)p1によって置換されていてもよいフェニル、L又はMを表すか、或いは、R36とR37とが一緒になってC2〜C5アルキレン鎖を形成することにより、結合する窒素原子と共に3〜6員環を形成してもよいことを表し、このときこのアルキレン鎖は酸素原子又は硫黄原子を1個含んでもよく、且つハロゲン原子又はメチル基によって置換されていてもよく、
lは、0〜9の整数を表し、
mは、0〜4の整数を表し、
nは、0〜4の整数を表し、
p1は、1〜5の整数を表し、
p2は、0〜4の整数を表し、
p3は、0〜3の整数を表し、
p4は、0〜2の整数を表し、
p5は、0又は1の整数を表し、
q1は、0〜3の整数を表し、
q2は、0〜5の整数を表し、
q3は、0〜7の整数を表し、
q4は、0〜9の整数を表し、
rは、0〜2の整数を表し、
tは、0又は1の整数を表す。]。
Z 1 is a halogen atom, cyano, nitro, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 alkylthio, C 1 -C 6 halo alkylthio, C 1 -C 6 alkylsulfinyl, C 1 -C 6 haloalkylsulfinyl, C 1 -C 6 alkylsulfonyl, C 1 -C 6 haloalkylsulfonyl, C 1 -C 6 alkylamino, di (C 1 -C 6 alkyl ) When amino, C 1 -C 6 alkoxycarbonyl, C 1 -C 6 haloalkoxycarbonyl or phenyl optionally substituted by a halogen atom, and p1, p2, p3 or p4 represents an integer of 2 or more Each Z 1 may be the same as or different from each other. It may be,
Z 2 is a halogen atom, cyano, nitro, amino, azido, -SCN, -SF 5, C 1 ~C 6 alkyl, optionally substituted by R 7 (C 1 ~C 6) alkyl, C 3 -C 8 cycloalkyl, substituted optionally substituted by R 7 (C 3 ~C 8) cycloalkyl, by C 2 -C 6 alkenyl, R 7 optionally (C 2 ~C 6) alkenyl, C 3 -C 8 cycloalkenyl, C 3 -C 8 halocycloalkyl cycloalkenyl, C 2 -C 6 alkynyl, optionally substituted by R 7 (C 2 ~C 6) alkynyl, -OH, -OR 8, -OS ( O) 2 R 8 , -SH, -S (O) r R 8 , -N (R 10 ) R 9 , -N (R 10 ) CHO, -N (R 10 ) C (O) R 9 , -N (R 10 ) C (O) OR 9 , -N (R 10 ) C (O) SR 9 , -N (R 10 ) C (S) OR 9 , -N (R 10 ) C (S) SR 9 , -N ( R 10 ) S (O) 2 R 9 , -CHO, -C (O) R 9 , -C (O) OR 9 , -C (O) NHR 10 , -C (O) N (R 10 ) R 9 , -C (S) NHR 10 , -C (S) N (R 10 ) R 9 , -S (O) 2 OR 9 , -S (O) 2 NHR 10 , -S (O) 2 N (R 10 ) R 9, -Si (R 13 ) (R 14) R 12, substituted by (Z 1) p1 Some represent phenyl, L or M, when p1 represents an integer of 2 or more, each of Z 2 may be also or different from each other the same as each other,
Further, when two Z 2 are adjacent, the two adjacent Z 2 are —CH 2 CH 2 CH 2 —, —CH 2 CH 2 O—, —CH 2 OCH 2 —, —OCH 2 O—, -CH 2 CH 2 S-, -CH 2 SCH 2- , -CH 2 CH 2 CH 2 CH 2- , -CH 2 CH 2 CH 2 O-, -CH 2 CH 2 OCH 2- , -CH 2 OCH 2 By forming O-, -OCH 2 CH 2 O- or -OCH 2 CH 2 S-, a 5-membered ring or a 6-membered ring may be formed with the carbon atom to which each of the two Z 2 is bonded, in this case, hydrogen atoms bonded to each carbon atom forming the ring may be optionally substituted by halogen atom or C 1 -C 6 alkyl group,
R 7 is a halogen atom, cyano, C 3 to C 8 cycloalkyl, C 3 to C 8 halocycloalkyl, —OH, —OR 8 , —SH, —S (O) r R 8 , —N (R 10 ) R 9 , -N (R 10 ) CHO, -N (R 10 ) C (O) R 9 , -N (R 10 ) C (O) OR 9 , -N (R 10 ) C (O) SR 9 , -N (R 10 ) C (S) OR 9 , -N (R 10 ) C (S) SR 9 , -N (R 10 ) S (O) 2 R 9 , -C (O) OR 9 ,- C (O) N (R 10 ) R 9 , -Si (R 13 ) (R 14 ) R 12 , (Z 1 ) represents phenyl, L or M optionally substituted by p1 ,
R 8 is optionally substituted by C 1 -C 6 alkyl, optionally substituted by R 27 (C 1 ~C 6) alkyl, C 3 -C 8 cycloalkyl, R 27 (C 3 ~C 8 ) cycloalkyl, C 2 -C 6 alkenyl, optionally substituted by R 27 (C 2 ~C 6) alkenyl, C 3 -C 8 cycloalkenyl, C 3 -C 8 halocycloalkyl cycloalkenyl, C 3 -C 6 It represents alkynyl, optionally substituted by R 27 (C 3 ~C 6) alkynyl, (Z 1) phenyl optionally substituted by p1, L or M,
R 9 is C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl (C 1 -C 4 ) alkyl, C 1 -C 6 alkoxy (C 1 -C 4 ) alkyl, C 1 -C 6 alkylthio (C 1 ~C 4) alkyl, cyano (C 1 ~C 6) alkyl, (Z 1) phenyl optionally substituted by p1 (C 1 ~C 4) alkyl, L-(C 1 -C 4) alkyl, M- (C 1 ~C 4) alkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 halocycloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, Represents C 3 -C 6 alkynyl or phenyl optionally substituted by (Z 1 ) p1 ,
R 10 represents a hydrogen atom or C 1 -C 6 alkyl, or R 9 and R 10 together form a C 2 -C 6 alkylene chain to form 3-7 together with the atoms to be bonded. indicates that the members may form a ring, this time the alkylene chain an oxygen atom, may contain one sulfur atom or a nitrogen atom, and a halogen atom, C 1 -C 6 alkyl group, C 1 -C 6 alkoxy group, a formyl group, may be optionally substituted by C 1 -C 6 alkylcarbonyl group or a C 1 -C 6 alkoxycarbonyl group,
R 11 is a hydrogen atom, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, phenyl (C 1 -C 4 ) alkyl optionally substituted by (Z 1 ) p 1 , C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, or represents C 3 -C 6 alkynyl or C 3 -C 6 haloalkynyl, or to form a C 2 -C 4 alkylene chain and R 9 and R 11 together Represents that a 5- to 7-membered ring may be formed together with the atoms to be bonded, in which case the alkylene chain may contain one oxygen atom, sulfur atom or nitrogen atom, and a halogen atom or C 1 -C Optionally substituted by 6 alkyl groups,
R 12 represents C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 alkenyl or phenyl optionally substituted by (Z 1 ) p 1 ;
R 13 and R 14 each independently represent C 1 -C 6 alkyl or C 1 -C 6 haloalkyl,
R 15 is a hydrogen atom, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxycarbonyl (C 1 -C 4 ) alkyl, C 1 -C 6 haloalkoxycarbonyl (C 1 -C 4) alkyl, (Z 1) phenyl optionally substituted by p1 (C 1 -C 4) alkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 alkynyl, C 3 -C 6 haloalkynyl, C 1 -C 6 alkoxy, C 1 -C 6 alkoxycarbonyl, C 1 -C 6 haloalkoxycarbonyl or (Z 1) p1 represents phenyl optionally substituted by,
R 16 is a hydrogen atom, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl (C 1 -C 4 ) alkyl, C 1 -C 4 alkoxy (C 1 -C 4 ) Alkyl, C 1 -C 4 alkylthio (C 1 -C 4 ) alkyl, phenylthio (C 1 -C 4 ) alkyl optionally substituted by (Z 1 ) p 1 , cyano (C 1 -C 6 ) alkyl, C 1 -C 6 alkoxycarbonyl (C 1 -C 4) alkyl, C 1 -C 6 alkylaminocarbonyl (C 1 -C 4) alkyl, di (C 1 -C 6 alkyl) aminocarbonyl (C 1 -C 4) alkyl, (Z 1) p1 phenyl optionally substituted by (C 1 ~C 4) alkyl, L- (C 1 ~C 4) alkyl, M- (C 1 ~C 4) alkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 alkynyl, C 3 -C 6 haloalkynyl, -OH, C 1 -C 6 alkylcarbonyloxy, C 1 -C 6 alkylthio, C 1 -C 6 haloalkylthio, (Z 1) which may be substituted by p1 phenylthio, C 1 -C 6 alkylsulfonyl, C 1 -C 6 haloalkylsulfonyl, (Z 1) p1 phenyl optionally substituted by sulfonyl, -SN (R 20) R 19 , C 1 ~C 6 alkylaminosulfonyl, di (C 1 -C 6 alkyl) aminosulfonyl, -CHO, -C (O) R 9, -C (O) OR 9 , -C (O) SR 9 , -C (O) NHR 10 , -C (O) N (R 10 ) R 9 , -C (S) OR 9 , -C (S) SR 9 , -C (S ) NHR 10 , -C (S) N (R 10 ) R 9 , -C (O) C (O) R 9 , -C (O) C (O) OR 9 , -P (O) (OR 24 ) 2 or -P (S) (OR 24 ) 2
R 17 is a hydrogen atom, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 8 cycloalkyl (C 1 -C 6 ) alkyl, C 3 -C 8 cycloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 alkynyl, C 3 -C 6 haloalkynyl, -CHO, C 1 ~C 6 alkyl carbonyl, C 1 -C 6 haloalkylcarbonyl or C 1 -C 6 alkoxy Represents carbonyl, or R 16 and R 17 together form a C 2 to C 6 alkylene chain to form a 3- to 7-membered ring with the nitrogen atom to which it is bonded. In this case, the alkylene chain may contain one oxygen atom, sulfur atom or nitrogen atom, and may be optionally substituted with a halogen atom, a C 1 -C 6 alkyl group or a C 1 -C 6 haloalkyl group. further alternatively, R 17 forms a C 1 -C 2 alkylene chain together with R 2 Optionally substituted by, indicates that may form a heterocyclic 6-membered or 7-membered benzene ring fused together with the binding atoms, by this time the alkylene chain is an oxygen atom or a C 1 -C 6 alkyl group and May have been
R 18 is a halogen atom, cyano, nitro, C 3 -C 8 cycloalkyl, C 3 -C 8 halocycloalkyl, -OR 28 , -N (R 29 ) R 28 , -SH, -S (O) r R 30 , -CHO, -C (O) R 31 , -C (O) OH, -C (O) OR 31 , -C (O) SR 31 , -C (O) NHR 32 , -C (O) N (R 32 ) R 31 , -C (O) C (O) OR 31 , -C (R 34 ) = NOH, -C (R 34 ) = NOR 33 , -Si (R 13 ) (R 14 ) R 12 , -P (O) (OR 24 ) 2 , -P (S) (OR 24 ) 2 , -P (phenyl) 2 , -P (O) (phenyl) 2 , (Z 1 ) p1 May represent phenyl, L or M;
R 19 is C 1 -C 12 alkyl, C 1 -C 12 haloalkyl, C 1 -C 12 alkoxy (C 1 -C 12 ) alkyl, cyano (C 1 -C 12 ) alkyl, C 1 -C 12 alkoxycarbonyl (C 1 -C 12 ) alkyl, (Z 1 ) phenyl (C 1 -C 4 ) alkyl optionally substituted by p 1 , C 3 -C 12 alkenyl, C 3 -C 12 haloalkenyl, C 3 -C 12 alkynyl, C 3 -C 12 haloalkynyl, C 1 -C 12 alkylcarbonyl, C 1 -C 12 alkoxycarbonyl or (Z 1) p1 represents phenyl optionally substituted by,
R 20 is C 1 -C 12 alkyl, C 1 -C 12 haloalkyl, C 1 -C 12 alkoxy (C 1 -C 12 ) alkyl, cyano (C 1 -C 12 ) alkyl, C 1 -C 12 alkoxycarbonyl (C 1 -C 12 ) alkyl, (Z 1 ) phenyl (C 1 -C 4 ) alkyl optionally substituted by p 1 , C 3 -C 12 alkenyl, C 3 -C 12 haloalkenyl, C 3 -C 12 alkynyl, C 3 -C 12 haloalkynyl or phenyl which may be substituted by (Z 1 ) p 1 , or R 19 and R 20 together form a C 4 -C 7 alkylene chain This means that a 5- to 8-membered ring may be formed together with the nitrogen atom to be bonded, in which case the alkylene chain may contain one oxygen atom or sulfur atom, and a C 1 -C 4 alkyl group or it may be optionally substituted by C 1 -C 4 alkoxy group,
R 21 is a hydrogen atom, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, phenyl (C 1 -C 4 ) alkyl optionally substituted by (Z 1 ) p 1 , C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 alkynyl, -CHO, C 1 ~C 6 alkyl carbonyl, C 1 -C 6 haloalkylcarbonyl, C 1 -C 6 alkoxycarbonyl, C 1 -C 6 haloalkoxycarbonyl , (Z 1) phenyl optionally substituted by p1 (C 1 ~C 4) alkoxycarbonyl, (Z 1) p1 good phenoxycarbonyl optionally substituted by optionally substituted by (Z 1) p1 Represents good phenylcarbonyl or phenyl optionally substituted by (Z 1 ) p1 ,
R 22 represents a hydrogen atom, C 1 -C 6 alkyl, -CHO, C 1 -C 6 alkylcarbonyl, a C 1 -C 6 haloalkylcarbonyl or C 1 -C 6 alkoxycarbonyl,
R 23 is cyano, C 3 -C 8 cycloalkyl, C 3 -C 8 halocycloalkyl, —OH, —OR 8 , —SH, —S (O) r R 8 , —N (R 10 ) R 9 , -N (R 10 ) CHO, -N (R 10 ) C (O) R 9 , -N (R 10 ) C (O) OR 9 , -N (R 10 ) C (O) SR 9 , -N (R 10 ) C (S) OR 9 , -N (R 10 ) C (S) SR 9 , -N (R 10 ) S (O) 2 R 9 , -C (O) OR 9 , -C (O ) N (R 10 ) R 9 , -Si (R 13 ) (R 14 ) R 12 , (Z 1 ) represents phenyl, L or M optionally substituted by p1 ,
R 24 represents C 1 -C 6 alkyl or C 1 -C 6 haloalkyl,
R 25 is a halogen atom, cyano, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, hydroxy (C 1 -C 6 ) alkyl, C 1 -C 4 alkoxy (C 1 -C 4 ) alkyl, C 1 -C 4 alkoxycarbonyl (C 1 ~C 4) alkyl, C 1 -C 6 alkoxy, C 1 -C 6 alkoxycarbonyl or (Z 1) represents a phenyl which is substituted by p1, q1, q2, q3 Or when q4 represents an integer of 2 or more, each R 25 may be the same as or different from each other;
R 26 is substituted by a hydrogen atom, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, -CHO, C 1 -C 6 alkylcarbonyl, C 1 -C 6 haloalkylcarbonyl, (Z 1 ) p1 also phenyl (C 1 ~C 4) alkylcarbonyl, C 1 -C 6 alkoxycarbonyl, C 1 -C 6 haloalkoxycarbonyl, (Z 1) p1 phenyl optionally substituted by (C 1 ~C 4) alkoxycarbonyl, C 1 -C 6 alkylaminocarbonyl, di (C 1 -C 6 alkyl) aminocarbonyl, C 1 -C 6 alkylamino thiocarbonyl, di (C 1 -C 6 alkyl) aminothiocarbonyl, (Z 1 ) phenyl carbonyl optionally substituted by p1, C 1 ~C 6 alkylsulfonyl, C 1 -C 6 haloalkylsulfonyl, (Z 1) p1 phenyl sulfonyl optionally substituted by, -P (O) (OR 24 ) represents 2 or -P (S) (OR 24 ) 2 ,
R 27 is a halogen atom, cyano, C 3 -C 8 cycloalkyl, C 3 -C 8 halocycloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 alkylthio, C 1 -C 6 haloalkylthio, C 1 -C 6 alkylsulfonyl, C 1 -C 6 haloalkylsulfonyl, C 1 -C 6 alkylamino, di (C 1 -C 6 alkyl) amino, -CHO, C 1 -C 6 alkyl substituted carbonyl, C 1 -C 6 haloalkylcarbonyl, C 1 -C 6 alkoxycarbonyl, C 1 -C 6 haloalkoxycarbonyl, -CH = NOR 11, -C ( R 9) = NOR 11, by (Z 1) p1 Represents optionally substituted phenyl, L or M;
R 28 is a hydrogen atom, C 1 -C 8 alkyl, optionally substituted by R 35 (C 1 ~C 8) alkyl, C 3 -C 8 cycloalkyl, optionally substituted by R 35 (C 3 -C 8) cycloalkyl, C 3 -C 8 alkenyl, optionally substituted by R 35 (C 3 ~C 8) alkenyl, optionally substituted by C 3 -C 8 alkynyl, R 35 (C 3 ~ C 8 ) alkynyl, -CHO, -C (O) R 31 , -C (O) OR 31 , -C (O) SR 31 , -C (O) NHR 32 , -C (O) N (R 32 ) R 31 , -C (O) C (O) R 31 , -C (O) C (O) OR 31 , -C (S) R 31 , -C (S) OR 31 , -C (S) SR 31 , -C (S) NHR 32 , -C (S) N (R 32 ) R 31 , -S (O) 2 R 31 , -S (O) 2 N (R 32 ) R 31 , -Si (R 13 ) (R 14 ) R 12 , -P (O) (OR 24 ) 2 , -P (S) (OR 24 ) 2 , (Z 1 ) represents phenyl, L or M optionally substituted by p1 ,
R 29 represents a hydrogen atom, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl or C 1 -C 6 alkoxy, or R 28 and R 29 together by now it forms a C 2 -C 5 alkylene chain, represents that may form a 3-6 membered ring together with the nitrogen atom to which they are attached this case the alkylene chain may contain one oxygen atom or a sulfur atom But often, and halogen atom, C 1 -C 6 alkyl group, C 1 -C 6 alkoxy group or (Z 1) may be substituted by a phenyl group optionally substituted by p1,
R 30 is, C 1 -C 8 alkyl, optionally substituted by R 35 (C 1 ~C 8) alkyl, optionally substituted by C 3 -C 8 cycloalkyl, R 35 (C 3 ~C 8 ) cycloalkyl, optionally substituted by C 3 -C 8 alkenyl, R 35 (C 3 ~C 8 ) alkenyl, optionally substituted by C 3 -C 8 alkynyl, R 35 (C 3 ~C 8 ) alkynyl, -SH, C 1 ~C 6 alkylthio, C 1 -C 6 haloalkylthio, (Z 1) which may be substituted by p1 phenylthio, -CHO, -C (O) R 31, -C (O) OR 31 , -C (O) SR 31 , -C (O) NHR 32 , -C (O) N (R 32 ) R 31 , -C (O) C (O) R 31 , -C (O) C (O) OR 31 , -C (S) R 31 , -C (S) OR 31 , -C (S) SR 31 , -C (S) NHR 32 , -C (S) N (R 32 ) R 31 , -P (O) (OR 24 ) 2 , -P (S) (OR 24 ) 2 , (Z 1 ) phenyl optionally substituted by p1 , L-18, L-21, L-25, L Represents -30 to L-35, L-45, L-48, L-49 or M;
R 31 is C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 8 cycloalkyl (C 1 -C 4 ) alkyl, C 1 -C 6 alkoxy (C 1 -C 4 ) alkyl, C 1 -C 6 haloalkoxy (C 1 ~C 4) alkyl, C 1 -C 6 alkylthio (C 1 ~C 4) alkyl, C 1 -C 6 haloalkylthio (C 1 ~C 4) alkyl, C 1 -C 6 alkylsulfonyl (C 1 ~C 4) alkyl, C 1 -C 6 haloalkylsulfonyl (C 1 ~C 4) alkyl, cyano (C 1 -C 6) alkyl, C 1 -C 6 alkylcarbonyl (C 1 -C 4) alkyl, C 1 -C 6 haloalkylcarbonyl (C 1 -C 4) alkyl, C 1 -C 6 alkoxycarbonyl (C 1 -C 4) alkyl, di (C 1 -C 6 alkyl) aminocarbonyl (C 1 -C 4) alkyl, tri (C 1 -C 4 alkyl) silyl (C 1 -C 4) alkyl, (Z 1) p1 phenyl optionally substituted by (C 1 -C 4) alkyl, L-( C 1 -C 4) alkyl, M - (C 1 ~C 4) alkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 halocycloalkyl, C 2 -C 6 alkenyl (C 3 ~C 8) cycloalkyl, C 2 -C 6 haloalkenyl (C 3 ~C 8) cycloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, optionally substituted by (Z 1) p1 May represent phenyl, L or M,
R 32 represents a hydrogen atom, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl or phenyl optionally substituted by (Z 1 ) p 1 , or R 31 and R 32 are taken together. By forming a C 2 -C 5 alkylene chain, a 3- to 6-membered ring may be formed together with the nitrogen atom to be bonded. At this time, this alkylene chain has 1 oxygen atom, sulfur atom or nitrogen atom. pieces comprise may, and halogen atom, C 1 -C 6 alkyl group, C 1 -C 6 alkoxy group, a formyl group, C 1 -C 6 alkylcarbonyl group, C 1 -C 6 alkoxycarbonyl group or (Z 1) optionally substituted by a phenyl group optionally substituted by p1 ,
R 33 is a hydrogen atom, C 1 -C 8 alkyl, (C 1 -C 8 ) alkyl optionally substituted by R 35 , C 3 -C 8 cycloalkyl, C 3 -C 8 alkenyl, optional by R 35 substituted a (C 3 ~C 8) alkenyl, optionally substituted by C 3 -C 8 alkynyl, or R 35 (C 3 ~C 8) alkynyl,
R 34 is a hydrogen atom, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 8 cycloalkyl (C 1 ~C 4) alkyl, C 1 -C 6 alkoxy (C 1 ~C 4) alkyl, C 1 -C 6 haloalkoxy (C 1 ~C 4) alkyl, C 1 -C 6 alkylthio (C 1 ~C 4) alkyl, C 1 -C 6 haloalkylthio (C 1 ~C 4) alkyl, C 1 -C 6 alkylsulfonyl (C 1 ~C 4) alkyl, C 1 -C 6 haloalkylsulfonyl (C 1 ~C 4) alkyl, (Z 1) phenyl optionally substituted by p1 (C 1 ~C 4 ) Alkyl or (Z 1 ) p1 which is optionally substituted by p1 ,
R 35 is a halogen atom, cyano, nitro, C 3 -C 8 cycloalkyl, C 3 -C 8 halocycloalkyl, —OH, —OR 36 , —SH, —S (O) r R 36 , —NHR 37 , -N (R 37 ) R 36 , -CHO, -C (O) R 31 , -C (O) OR 31 , -C (O) SR 31 , -C (O) NHR 32 , -C (O) N (R 32 ) R 31 , -C (O) C (O) OR 31 , -CH = NOR 11 , -C (R 9 ) = NOR 11 , -Si (R 13 ) (R 14 ) R 12 ,- Optionally substituted by P (O) (OR 24 ) 2 , -P (S) (OR 24 ) 2 , -P (phenyl) 2 , -P (O) (phenyl) 2 , (Z 1 ) p1 Represents phenyl, L or M;
R 36 is C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy (C 1 -C 4 ) alkyl, C 1 -C 6 alkylthio (C 1 -C 4 ) alkyl, (Z 1) p1 phenyl optionally substituted by (C 1 ~C 4) alkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 halocycloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 halo alkenyl, C 3 -C 8 cycloalkenyl, C 3 -C 8 halocycloalkyl cycloalkenyl, C 3 -C 6 alkynyl, C 3 -C 6 haloalkynyl, -CHO, C 1 ~C 6 alkyl carbonyl, C 1 -C 6 haloalkylcarbonyl, C 1 -C 6 alkoxycarbonyl, C 1 -C 6 haloalkoxycarbonyl, C 1 -C 6 alkylaminocarbonyl, di (C 1 -C 6 alkyl) aminocarbonyl, optionally substituted by (Z 1) p1 be phenyl carbonyl, C 1 -C 6 alkylamino thiocarbonyl, di (C 1 -C 6 alkyl) A Bruno thiocarbonyl, represents (Z 1) phenyl optionally substituted by p1, L or M,
R 37 is a hydrogen atom, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 8 cycloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, C 1 -C 6 alkylcarbonyl , C 1 -C 6 haloalkylcarbonyl, C 1 -C 6 alkoxycarbonyl, C 1 -C 6 haloalkoxycarbonyl, (Z 1) p1 good phenoxycarbonyl optionally substituted by optionally substituted by (Z 1) p1 phenyl carbonyl be, C 1 -C 6 alkylsulfonyl, C 1 -C 6 haloalkylsulfonyl, (Z 1) phenyl optionally substituted by p1, or represents L or M, or, R 36 and R 37 Together form a C 2 -C 5 alkylene chain to form a 3- to 6-membered ring with the nitrogen atom to which the alkylene chain is bonded, wherein the alkylene chain is an oxygen atom or a sulfur atom May contain one and halo It may be substituted by emissions atom or a methyl group,
l represents an integer of 0 to 9,
m represents an integer of 0 to 4,
n represents an integer of 0 to 4,
p1 represents an integer of 1 to 5,
p2 represents an integer of 0 to 4,
p3 represents an integer of 0 to 3,
p4 represents an integer of 0 to 2,
p5 represents an integer of 0 or 1,
q1 represents an integer of 0 to 3,
q2 represents an integer of 0 to 5,
q3 represents an integer of 0 to 7,
q4 represents an integer of 0 to 9,
r represents an integer of 0 to 2;
t represents an integer of 0 or 1. ].
化合物群A:アシベンゾラル−S−メチル(acibenzolar-S-methyl)、アシルアミノベンザミド(acylaminobenzamide)、アシペタックス(acypetacs)、アルジモルフ(aldimorph)、アンバム(amobam)、アムプロピルホス(ampropyfos)、アニラジン(anilazine)、アリルアルコール(allyl alcohol)、アウレロファンジン(aureofungin)、アザコナゾール(azaconazole)、アジチラム(azithiram)、アゾキシストロビン(azoxystrobin)、バリウムポリサルファイド(barium polysulfide)、ベナラキシル(benalaxyl)、ベノダニル(benodanil)、ベノミル(benomyl)、ベンキノックス(benquinox)、ベンタルロン(bentaluron)、ベンチアバリカルブ(benthiavalicarb)、ベンチアゾール(benthiazole)、ベンザルコニウムクロライド(benzalkonium chloride)、ベンザマクリル(benzamacril)、ベンズアモルフ(benzamorf)、ベンゾハイドロキサミックアシド(benzohydroxamic acid)、ビナパクリル(binapacryl)、ビフェニル(biphenyl)、ビテルタノール(bitertanol)、ビチオノール(bithionol)、ベトキサジン(bethoxazine)、ボルドー液(bordeaux mixture)、ブラストサイジン−S(blasticidin-S)、ブロモコナゾール(bromoconazole)、ブピリメート(bupirimate)、ブチオベート(buthiobate)、ブチルアミン(butylamine)、カルシウムポリスルフィド(calcium polysulfide)、キャプタフォール(captafol)、キャプタン(captan)、カッパーオキシクロリド(copper oxychloride)、カルプロパミド(carpropamid)、カルバモルフ(carbamorph)、カルベンダジン(carbendazim)、カルボキシン(carboxin)、カルボン(carvone)、チェシュントミクスチャ(Cheshunt mixture)、キノメチオネート(chinomethionat)、クロベンチアゾン(chlobenthiazone)、クロラニフォルメタン(Chloraniformethane)、クロラニル(Chloranil)、クロルフェナゾール(chlorfenazol)、クロロネブ(chloroneb)、クロロピクリン(Chloropicrin)、クロロタロニル(chlorothalonil)、クロロキノックス(Chlorquinox)、クロゾリネート(chlozolinate)、クリムバゾール(Climbazole)、クロトリマゾール(Clotrimazole)、カッパーアセテイト(copper acetate)、塩基性炭酸銅(copper carbonate, basic)、水酸化第二銅(copper hydroxide)、カッパーナフタレン(copper naphthenate)、カッパーオルアイト(copper oleate)、硫酸銅(copper sulfate)、塩基性硫酸銅(copper sulfate, basic)、カッパージンククロメイト(copper zinc chromate)、クレゾール(cresol)、クフラネブ(cufraneb)、クプロバム(cuprobam)、シアゾファミド(cyazofamid)、シクラフルアミド(cyclafuramid)、シクロヘキシミド(cycloheximide)、シフルフェナミド(cyflufenamid)、シモキサニル(cymoxanil)、サイペンダゾール(cypendazole)、シプロコナゾール(cyproconazol)、シプロジニル(cyprodinil)、シプロフラム(cyprofuram)、ダゾメット(dazomet)、デービーシーピー(DBCP)、デバカルブ(debacarb)、デカフェンチン(Decafentin)、デハイドロアセテイト(dehydroacetic acid)、ジクロン(dichlone)、ジクロロフェン(dichlorophen)、ジクロゾリン(dichlozoline)、ジクロブトラゾール(diclobutrazol)、ジクロフラニド(diclhlofluanid)、ジクロメジン(diclomedine)、ジクロラン(dicloran)、ジエトフェンカルブ(diethofencarb)、ジエチルピロカルボネイト(diethyl pyrocarbonate)、ジクロシメット(diclocymet)、ジフェノコナゾール(difenoconazole)、ジフルメトリン(diflumetorim)、ジメチリモール(dimethirimol)、ジメトモルフ(dimethomorph)、ジモキシストロビン(dimoxystrobin)、ジニコナゾール(diniconazole)、ジニコナゾール−M(diniconazole-M)、ジノブトン(dinobuton)、ジノカップ(dinocap)、ジノカップ−4(dinocap-4)、ジノカップー6(dinocap-6)、ジノクトン(dinocton)、ジノスルフォン(dinosulfon)、ジノテルボン(dinoterbon)、ジフェニルアミン(diphenylamine)、ジピリチオン(dipyrithione)、ジノスルフィラム(disulfiram)、ジタリムホス(ditalimfos)、ジチアノン(dithianon)、デーエヌオーシー(DNOC)、ドデモルフ(dodemorph)、ドジン(dodine)、ドラゾクソロン(drazoxolon)、エデフェノホス(edifenphos)、エポキシコナゾール(epoxiconazole)、エタコナゾール(etaconazole)、エチリモル(ethirimol)、エトリジアゾール(etridiazole)、エテム(Etem)、エトキシキン(Ethoxyquin)、エチルマーキュリーアセテイト(ethylmercury acetate)、エチルマーキュリーブロマイド(ethylmercury bromide)、塩化メチル水銀(ethylmercury chloride)、エチルマーキュリーフォスフェイト(ethylmercury phosphate)、ファモキサゾン(famoxadone)、フェナリモル(fenarimol)、フェブコナゾール(febuconazole)、フェナミドン(fenamidone)、フェンダゾスラム(fendazosulam)、フェンフラム(fenfuram)、フェンヘキサミド(fenhexamid)、フェノキサニル(fenoxanil)、フェンピクロニル(fenpiclonil)、フェンプロピジン(fenpropidin)、フェンプロピモルフ(fenpropimorph)、フェンチン(fentin)、フェルバン(ferbam)、フェリムゾン(ferimzone)、フルアジナム(fluazinam)、フルジオキソニル(fludioxonil)、フルオロイミド(fluoroimide)、フルキンコナゾール(fluquinconazole)、フルシラゾール(flusilazole)、フルスルファミド(flusulfamide)、フルトラニル(flutolanil)、フルトリアフォール(flutriafol)、フォルペット(folpet)、フォセチル−アルミニウム(fosetyl-aluminium)、フベリダゾール(fuberidazole)、フララキシル(furalaxyl)、フラメトピル(furametpyr)、フェナミノスルフ(fenaminosulf)、フェナパニル(fenapanil)、フェニトロパン(fenitropan)、フルメトバー(flumetover)、フルモルフ(flumorph)、フルオトリマゾール(fluotrimazole)、フルオキサストロビン(fluoxastrobin)、フルカルバニル(furcarbanil)、フルコナゾール(furconazole)、フルコナゾール−シス(furconazole-cis)、フルメシクロックス(furmecyclox)、フロファネート(furophanate)、グアザチン(guazatine)、グリオジン(glyodin)、グリセオフルビン(griseofulvin)、ヘキサクロロベンゼン(hexachlorobenzene)、ヘキサコナゾール(hexaconazole)、ヒメキサゾール(hymexazol)、ハラクリネイト(halacrinate)、ヘキサクロロブタジエン(hexachlorobutadiene)、ヘキシルチオフォス(hexylthiofos)、ハイドロキシキノリン サルフェイト(8-hydroxyquinoline sulfate)、イマザリル(imazalil)、イミベンコナゾール(imibenconazole)、イミノクタジン(iminoctadine)、イプコナゾール(ipconazole)、イプロベンホス(iprobenfos)、イプロジオン(iprodione)、イソプロチオラン(isoprothiolane)、イプロバリカルブ(iprovalicarb)、イソバレジオン(isovaledione)、カスガマイシン(kasugamycin)、クレソキシム−メチル(kresoxim-methyl)、マンカッパー(mancopper)、マンコゼブ(mancozeb)、マンネブ(maneb)、メパニピリム(mepanipyrim)、メプロニル(mepronil)、メタラキシル(metalaxyl)、メトコナゾール(metconazole)、メタスルホカルブ(methasulfocarb)、メチラム(metiram)、メトミノストロビン(metominostrobin)、ミクロブタニル(myclobutanil)、MTF−753(試験名)、メベニル(mebenil)、メカルビンジド(mecarbinzid)、塩化第二水銀(mercuric chloride)、酸化第二水銀(mercuric oxide)、塩化第一水銀(mercurous chloride)、メタラキシル−M(metalaxyl-M)、メタム(metam)、メタロキソロン(metazoxolon)、メスフロキサム(methfuroxam)、メチルブロマイド(methyl bromide)、メチルイソチアシアネイト(methyl isothiocyanate)、メチルマーキュリーベンゾエイト(methylmercury benzoate)、メチルマーキュリージシアンジアミド(methylmercury dicyandiamide)、メトラフェノン(metrafenone)、メトスルフォバックス(metsulfovax)、ミルネブ(milneb)、ミクロゾリン(myclozolin)、メトキシメチルマーキュリークロライド(2-methoxyethylmercury chloride)、ナバム(nabam)、ニッケルビス(ジメチルジチオカーバメート)(nickel bis(dimethyldithiocarbamate))、ニトロタール−イソプロピル(nitrothal-isopropyl)、ヌアリモル(nuarimol)、ナタマイシン(natamycin)、ニコビフェン(nicobifen)、ニトロスチレン(nitrostyrene)、オクチリノン(octhilinone)、オフレース(ofurace)、オキサジキシル(oxadixyl)、オキシカルボキシン(oxycarboxin)、オキポコナゾールフマール酸塩(oxpoconazole fumarate)、オーシーエイチ(OCH)、オリサストロビン(Orysastrobin)、有機銅(oxine copper)、ペフラゾエート(pefurzoate)、ペンコナゾール(penconazole)、ペンシクロン(pencycuron)、フタライド(phthalide)、ピペラリン(piperalin)、ポリオキシン(polyoxins)、炭酸水素カリウム(potassium hydrogen carbonate)、プロベナゾール(probenazole)、プロクロラズ(prochloraz)、プロシミドン(procymidone)、プロパモカルブ塩酸塩(propamocarb hydrochloride)、プロピコナゾール(propiconazole)、プロピネブ(propineb)、ピラゾホス(pyrazophos)、ピリフェノックス(pyrifenox)、ピリメタニル(pyrimethanil)、ピロキロン(pyroquilon)、ペンタクロロフェノール(pentachlorophenol(PCP))、尿素フェニル水銀(phenylmercuriurea)、フェニルマーキュリーアセテイト(phenylmercury acetate)、フェニルマーキュリークロライド(phenylmercury chloride)、フェニルマーキュリーナイトレイト(phenylmercury nitrate)、フェニルマーキュリーサリシレイト(phenylmercury salicylate)、フォスジフェン(phosdiphen)、ピコキシストロビン(picoxystrobin)、ポリカルバメイト(polycarbamate)、ポリオクソリム(polyoxorim)、ポタシウムアザイド(potassium azide)、ポタシウムポリサルファイド(potassium polysulfide)、プロキナジド(proquinazid)、プロチオカルブ(prothiocarb)、プロチオコナゾール(prothioconazole)、ピラカルボリド(pyracarbolid)、ピラクロストロビン(pyraclostrobin)、ピリジニトリル(pyridinitril)、ピロキシクロア(pyroxychlor)、ピロキシサルファ(pyroxyfur)、フェニルフェノール(2-phenylphenol)、キノメチオネート(quinomethionate)、キノキシフェン(quinoxyfen)、キントゼン(quintozene)、キナセトール(quinacetol)、キナザミド(quinazamid)、キンコナゾール(quinconazole)、ラベンザゾール(rabenzazole)、炭酸水素ナトリウム(sodium hydrogen carbonate)、次亜塩素酸ナトリウム(sodium hypochlorite)、硫黄(sulfur)、スピロキサミン(spiroxamine)、サリチルアニリド(salicylanilide)、シルチオファム(silthiofam)、シメコナゾール(simeconazole)、アジ化ナトリウム(sodium azide)、ソジウムオルトペニルペノキサイド(sodium orthophenylphenoxide)、ソジウムペンタクロロフェノキサイド(sodium pentachlorophenoxide)、ソジウムポリサルファイド(sodium polysulfide)、テブコナゾール(tebuconazole)、テクナゼン(tecnazene)、テトラコナゾール(tetraconazole)、チアベンダゾール(thiabendazole)、チアジアジン(thiadiazin/milneb)、チフルザミド(thifluzamide)、チオファネート−メチル(thiophanate-methyl)、チラム(thiram)、トルクロホス−メチル(tolclofos-methyl)、トリルフラニド(tolylfluanid)、トリアジメホン(triadimefon)、トリアジメノール(toriadimenol)、トリアゾキシド(triazoxide)、トリシクラゾール(tricyclazole)、トリデモルフ(tridemorph)、トリフルミゾール(triflumizole)、トリホリン(triforine)、トリチコナゾール(triticonazole)、テーシーエムテービー(TCMTB)、テコラム(tecoram)、チアジフルア(thiadif
luor)、チシオフェン(thicyofen)、チオクロルフェンフィム(thiochlorfenphim)、チオメルサム(thiomersal)、チオファネイト(thiophanate)、チオキノックス(thioquinox)、チアジニル(tiadinil)、チオキシミド(tioxymid)、トリマーキュリアセテイト(tolylmercury acetate)、トリアミフォス(triamiphos)、トリアリモル(triarimol)、トリアズブチル(triazbutil)、トリブチルチンオキサイド(tributyltin oxide)、トリクルアミド(trichlamide)、トリフロキシストロビン(trifloxystrobin)、バリダマイシン(validamycin)、ビンクロゾリン(vinclozolin)、硫酸亜鉛(zinc sulfate)、ジネブ(zineb)、ジラム(ziram)、ゾキサミド(zoxamide)、ザリルアミド(zarilamid)、ジンクナフテネイト(zinc naphthenate)、シイタケ菌糸体抽出物、ブロノポル(bronopol)、フォルムアルデハイド(formaldehyde)、ニトラピリン(nitrapyrin)、オキソリニックアシド(oxolinic acid)、オキシテトラサイクリン(oxyterracycline)、ストレプトマイシン(streptomycin)、テクロフタラム(tecloftalam)、チオメルサル(thiomersal)、イマニン(imanin)、ルバビリン(ribavirin)、アルドキシカルブ(aldoxycarb)、カズサホス(cadusafos)、ジクロフェンチオン(dichlofenthion)、DSP、エトプロホス(ethoprophos)、フェンスルホチオン(fensulfothion)、フォスチアゼート(fosthiazate)、フォスチエタン(fosthietan)、イサミドホス(isamidofos)、イサゾホス (isazofos)、オキサミル(oxamyl)、フェナミホス(fenamiphos)、チオナジン(thionazin)、アセキノシル(acequinocyl)、アクリナトリン(acrinathrin)、アミトラズ(amitraz)、ビフェナゼート(bifenazate)、ブロモプロピレート(bromopropylate)、チノメチオネート(chinomethionat)、クロロベンジラート(chlorobezilate)、クロフェンテジン(clofentezine)、サイヘキサチン(cyhexatine)、ジコフォール(dicofol)、ジエノクロール(dienochlor)、エトキサゾール(etoxazole)、フェナザキン(fenazaquin)、フェンブタチンオキシド(fenbutatin oxide)、フェンプロパトリン(fenpropathrin)、フェンピロキシメート(fenpyroximate)、フェノチオカルブ(fenothiocarb)、フルアクリピリム(fluacrypyrim)、ハルフェンプロックス(halfenprox)、ヘキシチアゾックス(hexythiazox)、ミルベメクチン(milbemectin)、プロパルギット(propargite)、ピリダベン(pyridaben)、ピリミジフェン(pyrimidifen)、スピロディクロフェン(spirodiclofen)、テブフェンピラド(tebufenpyrad)、アバメクチン(abamectin)、アセフェート(acephate)、アセタミピリド(acetamipirid)、アラニカルブ(alanycarb)、アルディカルブ(aldicarb)、アレスリン(allethrin)、アジンホス−メチル(azinphos-methyl)、バチルスチューリンゲシス(Bacillus thuringiensis)、ベンジオカルブ(bendiocarb)、ベンフラカルブ(benfuracarb)、ベンスルタップ(bensultap)、ビフェントリン(bifenthrin)、ブプロフェジン(buprofezin)、ブトカルボキシン(butocarboxim)、カルバリル(carbaryl)、カルボフラン(carbofuran)、カルボスルファン(carbosulfan)、カルタップ(cartap)、クロルフェナピル(chlorfenapyr)、クロルピリホス(chlorpyrifos)、クロルフェンビンホス(chlorfenvinphos)、クロルフルアズロン(chlorfluazuron)、クロチアニジン(clothianidin)、クロマフェノジド(chromafenozide)、クロピリホス−メチル(chlorpyrifos-methyl)、シクロプロトリン(cycloprothrin)、シフルトリン(cyfluthrin)、ベータ−シフルトリン(beta-cyfluthrin)、シペルメトリン(cypermethrin)、シロマジン(cyromazine)、シハロトリン(cyhalothrin)、ラムダ−シハロトリン(lambda-cyhalothrin)、デルタメトリン(deltamethrin)、ジアフェンチウロン(diafenthiuron)、ダイアジノン(diazinon)、ジアクロデン(diacloden)、ジフルベンズロン(diflubenzuron)、ジメチルビンホス(dimethylvinphos)、ジノテフラン(dinotefuran)、ジオフェノラン(diofenolan)、ジスルフォトン(disulfoton)、ジメトエート(dimethoate)、エマメクチンベンゾエート(emamectin-benzoate)、EPN、エスフェンバレレート(esfenvalerate)、エチオフェンカルブ(ethiofencarb)、エチプロール(ethiprole)、エトフェンプロックス(etofenprox)、エトリムホス(etrimfos)、フェニトロチオン(fenitrothion)、フェノブカルブ(fenobucarb)、フェノキシカーブ(fenoxycarb)、フェンチオン(fenthion)、フェンバレレート(fenvalerate)、フィプロニル(fipronil)、フルシトリネート(flucythrinate)、フルフェノクスロン(flufenoxuron)、フルフェンプロックス(flufenprox)、フルバリネート(fluvalinate)、タウ−フルバリネート(tau-fluvalinate)、ホノホス(fonophos)、フォルメタネート(formetanate)、フォルモチオン(formothion)、フラチオカルブ(furathiocarb)、ハロフェノジド(halofenozide)、ヘキサフルムロン(hexaflumuron)、ヒドラメチルノン(hydramethylnon)、イミダクロプリド(imidacloprid)、イソフェンホス(isofenphos)、インドキサカルブ(indoxacarb)、イソプロカルブ(isoprocarb)、イソキサチオン(isoxathion)、ルフェヌウロン(lufenuron)、マラチオン(malathion)、メタルデヒド(metaldehyde)、メタミドホス(methamidophos)、メチダチオン(methidathion)、メタクリホス(methacrifos)、メタルカルブ(metalcarb)、メソミル(methomyl)、メソプレン(methoprene)、メトキシクロール(methoxychlor)、メトキシフェノジド(methoxyfenozide)、モノクロトホス(monocrotophos)、ムスカルーレ(muscalure)、ニテンピラム(nitenpyram)、オメトエート(omethoate)、オキシデメトン−メチル(oxydemeton-methyl)、オキシデプロポス(oxydeprofos)、パラチオン(parathion)、パラチオン−メチル(parathion-methyl)、ペルメトリン(permethrin)、フェントエート(phenthoate)、フォキシム(phoxim)、ホレート(phorate)、ホサロン(phosalone)、ホスメット(phosmet)、ホスファミドン(phosphamidon)、ピリミカルブ(pirimicarb)、ピリミホス−メチル(pirimiphos-methyl)、プロフェノホス(profenofos)、プロチオホス(prothiofos)、プロパホス(propaphos)、プロトリフェンブト(protrifenbute)、ピリダリル(pyridalyl)、ピメトロジン(pymetrozine)、ピラクロホス(pyraclofos)、ピリプロキシフェン(pyriproxyfen)、ロテノン(rotenone)、スルプロホス(sulprofos)、シラフルオフェン(silafluofen)、スピノサド(spinosad)、スピロメシフェン(spiromesifen)、スルホテップ(sulfotep)、テブフェノジド(tebfenozide)、テフルベンズロン(teflubenzuron)、テフルトリン(tefluthorin)、テルブホス(terbufos)、テトラクロロビンホス(tetrachlorvinphos)、チアクロプリド(thiacloprid)、チオシクラム(thiocyclam)、チオジカルブ(thiodicarb)、チアメトキサム(thiamethoxam)、チオファノックス(thiofanox)、チオメトン(thiometon)、トルフェンピラド(tolfenpyrad)、トラロメトリン(tralomethrin)、トリクロルホン(trichlorfon)、トリアズロン(triazuron)、トリフルムロン(triflumuron)、バミドチオン(vamidothion)及びエチオン(ethion)。
Compound group A: acibenzolar-S-methyl, acylaminobenzamide, acypetacs, aldimorph, amobam, ampropyfos, anilazine ), Allyl alcohol, aureofungin, azaconazole, azithiram, azoxystrobin, barium polysulfide, benalaxyl, benodanil ), Benomyl, benquinox, bentaluron, benthiavalicarb, benthiazole, benzalkonium chloride, benzamacril, benzamorph benzamorf), benzohydroxamic acid, binapacryl, biphenyl, bitertanol, bithionol, bethoxazine, bordeaux mixture, blasticidin-S ( blasticidin-S), bromoconazole, bupirimate, buthiobate, butylamine, calcium polysulfide, captafol, captan, kappa oxychloride ( copper oxychloride, carpropamid, carbamorph, carbendazim, carboxin, carvone, cheshunt mixture, chinomethionat Clobenthiazone, chloraniformethane, chloranil, chlorfenazol, chloroneb, chloropicrin, chlorothalonil, chloroquinox, Clozolinate, Climbazole, Clotrimazole, Copper acetate, Copper carbonate, basic, Copper hydroxide, Copper naphthalene (copper) naphthenate, copper oleate, copper sulfate, copper sulfate, basic, copper zinc chromate, cresol, cufraneb, cuprobam (Cuprobam), cyazofamid , Cyclafuramid, cycloheximide, cyflufenamid, cymoxanil, cypendazole, cyproconazol, cyprodinil, cyprofuram, azoprofurad, metzomet ), Davy Ceep (DBCP), debacarb, decafentin, dehydroacetic acid, dichlone, dichlorophen, dichlozoline, diclobutrazol ), Diclhlofluanid, diclomedine, dicloran, dietofencarb, diethyl pyrocarbonate, diclocymet, difenocazole onazole), diflumetorim, dimethirimol, dimethomorph, dimoxystrobin, dinoxyazole, diniconazole-M, diniconazole-M, dinobuton, dinocap, dinocap Dinocap-4, dinocap-6, dinocton, dinosulfon, dinoterbon, diphenylamine, dipyrithione, disulfiram, ditalimphos ( ditalimfos), dithianon, DNOC, dodemorph, dodine, drazoxolon, edifenphos, epoxiconazole, etaconazole, etilimo Ethirimol, etridiazole, Etem, Ethoxyquin, ethylmercury acetate, ethylmercury bromide, ethylmercury chloride, ethylmercury phosphate ( ethylmercury phosphate, famoxadone, fenarimol, febuconazole, fenamidone, fendazosulam, fenfuram, fenhexamid, fenoxanil, Fenpiclonil, fenpropidin, fenpropimorph, fentin, ferbam, ferimzone, fluazinam, fludiochi Sonil (fludioxonil), fluoroimide, fluquinconazole, flusilazole, flusulfamide, flutolanil, flutriafol, folpet, fosetyl-aluminum ( fosetyl-aluminium, fuberidazole, fluralaxyl, furametpyr, fenaminosulf, fenaminosulf, fenapanil, fenitropan, flumetover, flumorph (flumorph), flutritriazole fluotrimazole, fluoxastrobin, furcarbanil, fluconazole, furconazole-cis, furmecyclox, furofanate (fu rophanate, guazatine, glyodin, griseofulvin, hexachlorobenzene, hexaconazole, hymexazol, halacrinate, hexachlorobutadiene, hexylthiophos (Hexylthiofos), hydroxyquinoline sulfate, imazalil, imibenconazole, iminoctadine, ipconazole, iprobenfos, iprodione, proprolane ), Iprovalicarb, isovaledione, kasugamycin, kresoxim-methyl, mancopper , Mancozeb, maneb, mepanipyrim, mepronil, metalaxyl, metconazole, metasulfocarb, metiram, metinominostrobin, metominostrobin Microbutanil, MTF-753 (test name), mebenil, mecarbinzid, mercuric chloride, mercuric oxide, mercurous chloride, Metalaxyl-M, metam, metazoxolon, methfuroxam, methyl bromide, methyl isothiocyanate, methylmercury benzoate, methyl Mercury dicyandiamide ( methylmercury dicyandiamide, metrafenone, metsulfovax, milneb, microzoline, 2-methoxyethylmercury chloride, nabam, nickel bis (dimethyldithiocarbamate) nickel bis (dimethyldithiocarbamate)), nitrothal-isopropyl, nuarimol, natamycin, nicobifen, nitrostyrene, octhilinone, offurace, oxadixil ( oxadixyl, oxycarboxin, oxpoconazole fumarate, OCH, Orysastrobin, oxine copper, pefurzoate, Penconazole, penencycuron, phthalide, piperalin, polyoxins, potassium hydrogen carbonate, probenazole, prochloraz, procymidone, propamocarb Propamocarb hydrochloride, propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, pentachlorophenol (PCP) , Urea phenylmercuriurea, Phenylmercury acetate, Phenylmercury chloride, Phenylmercury nitrate, Phenimercury nitrate, Phenylmercury nitrate, Phenylmercury nitrate, Phenylmercury nitrate, Phenylmercury nitrate Lumercury salicylate, phosdiphen, picoxystrobin, polycarbamate, polyoxorim, potassium azide, potassium polysulfide, potassium polysulfide Proquinazid, prothiocarb, prothioconazole, pyracarbolid, pyraclostrobin, pyridinitril, pyroxychlor, pyroxysulfur, phenylphenol (2) -phenylphenol, quinomethionate, quinoxyfen, quintozene, quinacetol, quinazamid, quinconazole, Benzazole (rabenzazole), sodium hydrogen carbonate, sodium hypochlorite, sulfur, spiroxamine, salicylanilide, silthiofam, simeconazole, Sodium azide, sodium orthophenylphenoxide, sodium pentachlorophenoxide, sodium polysulfide, tebuconazole, tecnazene, tetra Conazole (tetraconazole), thiabendazole, thiadiazin / milneb, thifluzamide, thiophanate-methyl, thiram, torquelophos-methyl (tolc lofos-methyl, tolylfluanid, triadimefon, triadimenol, triazoxide, triazoxide, tricyclazole, triridemorph, triflumizole, triforine, triforine Ticonadazole (triticonazole), TMC MTB (TCMTB), Tecolam (tecoram), thiadifurea (thiadif)
luor, thicyofen, thiochlorfenphim, thiomersal, thiophanate, thioquinox, tiadinil, thioxymid, tolylmercury acetate, Triamiphos, triarimol, triazbutil, tributyltin oxide, trichlamide, trifloxystrobin, validamycin, vinclozolin, zinc sulfate ( zinc sulfate, zineb, ziram, zoxamide, zarilamid, zinc naphthenate, shiitake mycelium extract, bronopol, formaldehyde Ideformaldehyde, nitrapyrin, oxolinic acid, oxyterracycline, streptomycin, tecloftalam, thiomersal, imanin, ribavirin, aldoxy Carb (aldoxycarb), cadusafos, dichlofenthion, DSP, ethoprophos, fensulfothion, fosthiazate, fosthietan, isamidophos (isamidofos), azophos ), Fenamiphos, thionazin, acequinocyl, acrinathrin, amitraz, bifenazate, bromopropi Bromopropylate, chinomethionat, chlorobezilate, clofentezine, cyhexatine, dicofol, dienochlor, etoxazole, fenazaquin, Fenbutatin oxide, fenpropathrin, fenpyroximate, fenothiocarb, fluacrypyrim, halfenprox, hexythiazox, milbemectin , Propargite, pyridaben, pyrimidifen, spirodiclofen, tebufenpyrad, abamectin, a Acephate, acetamipirid, alanamicarb, aldicarb, allethrin, azinphos-methyl, bacillus thuringiensis, bendiocarb, benfuracarb (Benfuracarb), bensultap, bifenthrin, buprofezin, butocarboxim, carbaryl, carbofuran, carbosulfan, cartap, chlorfenapir ( chlorfenapyr), chlorpyrifos, chlorfenvinphos, chlorfluazuron, clothianidin, chromafenozide, clopyrifos-methyl (ch lorpyrifos-methyl, cycloprothrin, cyfluthrin, beta-cyfluthrin, cypermethrin, cyromazine, cyhalothrin, lambda-cyhalothrin , Deltamethrin, diafenthiuron, diazinon, diacloden, diflubenzuron, dimethylvinphos, dinotefuran, diofenolan, disulfoton , Dimethoate, emamectin-benzoate, EPN, esfenvalerate, ethiofencarb, ethiprole, etofenprox, etofenprox, etofenprox, etofenprox, etofenprox, etofenprox Rimfos, fenitrothion, fenobucarb, fenoxycarb, fenthion, fenvalerate, fipronil, flucythrinate, flufenoxuron , Flufenprox, fluvalinate, tau-fluvalinate, fonophos, formetanate, formothion, furathiocarb, halofenozide , Hexaflumuron, hydramethylnon, imidacloprid, isofenphos, indoxacarb, isoprocarb, isoxathi on, lufenuron, malathion, metalaldehyde, metamidophos, methidathion, methacrifos, metalcarb, methomyl, methoprene, methoxychlor (Methoxychlor), methoxyfenozide, monocrotophos, muscalure, nitenpyram, omethoate, oxydemeton-methyl, oxydeprofos, parathion , Parathion-methyl, permethrin, phenthoate, phoxim, phorate, phosalone, phosmet, phosphamidone on), pirimicarb, pirimiphos-methyl, profenfos, prothiofos, propaphos, protrifenbute, pyridalyl, pymetrozine, Pyraclofos, pyriproxyfen, rotenone, sulprofos, silafluofen, spinosad, spiromesifen, sulfotep, tebufenozide, tebfenozide (Teflubenzuron), tefluthorin, terbufos, tetrachlorovinphos, thiacloprid, thiocyclam, thiodicarb, thiamethoxam , Thiofanox (thiofanox), thiometon (thiometon), tolfenpyrad (tolfenpyrad), tralomethrin (tralomethrin), trichlorfon (trichlorfon), Toriazuron (triazuron), triflumuron (triflumuron), vamidothion (vamidothion) and ethion (ethion).
〔2〕 上記〔1〕記載の一般式(1)において、Gは、式G-4、式G-5、式G-6、式G-7、式G-11、式G-13、式G-14、式G-15、式G-17、式G-18又は式G-23の何れかで表される非芳香族複素環、又は式G-71で表されるシクロアルキル環を表し、 [2] In the general formula (1) described in [1] above, G is a formula G-4, a formula G-5, a formula G-6, a formula G-7, a formula G-11, a formula G-13, a formula A non-aromatic heterocyclic ring represented by any of G-14, G-15, G-17, G-18 or G-23, or a cycloalkyl ring represented by G-71 ,
Xは、ハロゲン原子、ニトロ、C1〜C4アルキル、C1〜C4ハロアルキル、C1〜C4アルコキシ、C1〜C4ハロアルコキシ、C1〜C4アルキルチオ、C1〜C4ハロアルキルチオ、C1〜C4アルキルスルフィニル、C1〜C4ハロアルキルスルフィニル、C1〜C4アルキルスルホニル又はC1〜C4ハロアルキルスルホニルを表し、mが2を表すとき、各々のXは互いに同一であっても又は互いに相異なっていてもよく、
Yは、ハロゲン原子、C1〜C4アルキル、C1〜C4ハロアルキル、C1〜C4アルコキシ又はC1〜C4アルキルチオを表し、nが2を表すとき、各々のYは互いに同一であっても又は互いに相異なっていてもよく、
R1は、水素原子を表し、
R2は、水素原子又はC1〜C6アルキルを表し、
R3は、C1〜C8アルキル、R18によって任意に置換された(C1〜C8)アルキル、C3〜C8アルケニル又はC3〜C8アルキニルを表し、
R4は、C1〜C6アルキル、C1〜C6ハロアルキル、(Z2)p1によって置換されていてもよいフェニル、2-ナフチル、L-1〜L-4、L-15〜L-17、L-19、L-20、L-22、L-23、L-45、L-46又はL-47を表し、
R5は、
(a). R4がC1〜C6アルキル又はC1〜C6ハロアルキルを表すとき、(Z2)p1によって置換されていてもよいフェニル、1-ナフチル、2-ナフチル、L-1〜L-5、L-8〜L-24、L-28〜L-36、L-39、L-41、L-42、L-45〜L-47又はL-50を表し、
(b). R4が(Z2)p1によって置換されていてもよいフェニル、2-ナフチル、L-1〜L-4、L-15〜L-17、L-19、L-20、L-22、L-23、L-45、L-46又はL-47を表すとき、水素原子、ハロゲン原子、C1〜C6アルキル、C1〜C6ハロアルキル、C1〜C6アルコキシ、C1〜C6ハロアルコキシ、C1〜C6アルキルチオ、C1〜C6アルキルスルフィニル、C1〜C6アルキルスルホニル又はジ(C1〜C6)アルキルアミノを表し、
R6a、R6b、R6c及びR6dは、水素原子を表し、
R6eは、C1〜C6アルキルを表し、
R6iは、水素原子を表し、
R6j及びR6kは、各々独立して水素原子、ハロゲン原子又はシアノを表し、
Z2は、ハロゲン原子、シアノ、ニトロ、C1〜C6アルキル、C1〜C6ハロアルキル、C1〜C3アルコキシ(C1〜C3)アルキル、C1〜C3ハロアルコキシ(C1〜C3)アルキル、C1〜C3アルキルチオ(C1〜C3)アルキル、C1〜C3ハロアルキルチオ(C1〜C3)アルキル、C1〜C3アルキルスルフィニル(C1〜C3)アルキル、C1〜C3ハロアルキルスルフィニル(C1〜C3)アルキル、C1〜C3アルキルスルホニル(C1〜C3)アルキル、C1〜C3ハロアルキルスルホニル(C1〜C3)アルキル、シアノ(C1〜C6)アルキル、C1〜C6アルコキシ、C1〜C6ハロアルコキシ、C1〜C3ハロアルコキシ(C1〜C3)ハロアルコキシ、C1〜C6アルキルスルホニルオキシ、C1〜C6ハロアルキルスルホニルオキシ、(Z1)p1によって置換されていてもよいフェノキシ、-O(L-45)、C1〜C6アルキルチオ、C1〜C6ハロアルキルチオ、C3〜C8シクロアルキルチオ、C1〜C6アルキルスルフィニル、C1〜C6ハロアルキルスルフィニル、C3〜C8シクロアルキルスルフィニル、C1〜C6アルキルスルホニル、C1〜C6ハロアルキルスルホニル、C3〜C8シクロアルキルスルホニル、C1〜C6アルキルアミノスルホニル、ジ(C1〜C6アルキル)アミノスルホニル、-C(O)NH2、C1〜C6アルキルアミノカルボニル、ジ(C1〜C6アルキル)アミノカルボニル、-C(S)NH2又はトリ(C1〜C6アルキル)シリルを表し、p1が2以上の整数を表すとき、各々のZ2は互いに同一であっても又は互いに相異なっていてもよく、
さらに、2つのZ2が隣接する場合には、隣接する2つのZ2は-OCF2O-又は-OCF2CF2O-を形成することにより、それぞれが結合する炭素原子と共に5員環又は6員環を形成してもよく、
R15は、C1〜C6アルキル又は(Z1)p1によって置換されていてもよいフェニルを表し、
R18は、-OR28、-N(R29)R28、-S(O)rR30、-CH=NOH又は-CH=NOR33を表し、
R28は、C1〜C6アルキル、C1〜C6アルキルカルボニル、C1〜C6アルコキシカルボニル、C1〜C6アルキルアミノカルボニル、ジ(C1〜C6アルキル)アミノカルボニル又はC1〜C6アルキルスルホニルを表し、
R29は、水素原子又はC1〜C6アルキルを表し、
R30は、C1〜C6アルキルを表し、
R33は、C1〜C6アルキルを表し、
mは、0〜2の整数を表し、
nは、0〜2の整数を表す置換ベンズアニリド化合物及びその塩より選ばれる1種又は2種以上と、上記〔1〕記載の化合物群Aより選ばれる化合物の1種又は2種以上を含有する殺虫、殺ダニ、殺線虫、殺菌又は殺バクテリア組成物。
X is a halogen atom, nitro, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkylthio, C 1 -C 4 halo alkylthio, C 1 -C 4 alkylsulfinyl, C 1 -C 4 haloalkylsulfinyl, C 1 -C 4 alkyl sulfonyl or C 1 -C 4 haloalkylsulfonyl, when m represents 2, each X is the same with each other May be different from each other,
Y is a halogen atom, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy or C 1 -C 4 alkylthio, when n is 2, each Y is identical to each other May be different from each other,
R 1 represents a hydrogen atom,
R 2 represents a hydrogen atom or C 1 -C 6 alkyl,
R 3 represents C 1 -C 8 alkyl, (C 1 -C 8 ) alkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl optionally substituted by R 18 ,
R 4 is C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, phenyl optionally substituted by (Z 2 ) p 1 , 2-naphthyl, L-1 to L-4, L-15 to L- 17, L-19, L-20, L-22, L-23, L-45, L-46 or L-47,
R 5 is
(a). When R 4 represents C 1 -C 6 alkyl or C 1 -C 6 haloalkyl, (Z 2 ) phenyl optionally substituted by p 1, 1-naphthyl, 2-naphthyl, L-1 L-5, L-8 to L-24, L-28 to L-36, L-39, L-41, L-42, L-45 to L-47 or L-50
(b) R 4 is phenyl, 2-naphthyl, L-1 to L-4, L-15 to L-17, L-19, L-20, L optionally substituted by (Z 2 ) p1 -22, to represent a L-23, L-45, L-46 or L-47, a hydrogen atom, a halogen atom, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 alkylthio, C 1 -C 6 alkylsulfinyl, C 1 -C 6 alkylsulfonyl or di (C 1 ~C 6) alkyl amino,
R 6a , R 6b , R 6c and R 6d represent a hydrogen atom,
R 6e represents C 1 -C 6 alkyl;
R 6i represents a hydrogen atom,
R 6j and R 6k each independently represent a hydrogen atom, a halogen atom or cyano,
Z 2 is a halogen atom, cyano, nitro, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 3 alkoxy (C 1 -C 3) alkyl, C 1 -C 3 haloalkoxy (C 1 -C 3) alkyl, C 1 -C 3 alkylthio (C 1 ~C 3) alkyl, C 1 -C 3 haloalkylthio (C 1 ~C 3) alkyl, C 1 -C 3 alkylsulfinyl (C 1 -C 3 ) alkyl, C 1 -C 3 haloalkylsulfinyl (C 1 -C 3) alkyl, C 1 -C 3 alkylsulfonyl (C 1 -C 3) alkyl, C 1 -C 3 haloalkylsulfonyl (C 1 -C 3) alkyl , cyano (C 1 ~C 6) alkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 3 haloalkoxy (C 1 ~C 3) haloalkoxy, C 1 -C 6 alkylsulfonyl oxy, C 1 -C 6 haloalkylsulfonyloxy, (Z 1) p1 may be substituted by phenoxy, -O (L-45), C 1 ~C 6 alkylthio, C 1 -C 6 haloalkylthio, C 3 -C 8 cycloalkylthio, C 1 -C 6 alkylsulfinyl, C 1 -C 6 haloalkylsulfinyl, C 3 -C 8 cycloalkylsulfinyl, C 1 -C 6 alkylsulfonyl, C 1 -C 6 haloalkylsulfonyl, C 3 -C 8 cycloalkylsulfonyl, C 1 -C 6 alkylaminosulfonyl, di (C 1 -C 6 alkyl) aminosulfonyl, -C (O) NH 2, C 1 ~C 6 alkylaminocarbonyl, di (C 1 -C 6 alkyl) represents aminocarbonyl, -C (S) NH 2 or tri (C 1 -C 6 alkyl) silyl, when p1 represents an integer of 2 or more, each Z 2 may be the same as or different from each other;
Further, when two Z 2 are adjacent to each other, the two adjacent Z 2 form —OCF 2 O— or —OCF 2 CF 2 O— to form a 5-membered ring or a carbon atom to which each is bonded. A 6-membered ring may be formed,
R 15 represents C 1 -C 6 alkyl or phenyl optionally substituted by (Z 1 ) p 1 ,
R 18 represents -OR 28 , -N (R 29 ) R 28 , -S (O) r R 30 , -CH = NOH or -CH = NOR 33 ,
R 28 is C 1 -C 6 alkyl, C 1 -C 6 alkylcarbonyl, C 1 -C 6 alkoxycarbonyl, C 1 -C 6 alkylaminocarbonyl, di (C 1 -C 6 alkyl) aminocarbonyl or C 1 It represents -C 6 alkylsulfonyl,
R 29 represents a hydrogen atom or C 1 -C 6 alkyl,
R 30 represents C 1 -C 6 alkyl,
R 33 represents C 1 -C 6 alkyl;
m represents an integer of 0 to 2,
n contains 1 type or 2 or more types chosen from the substituted benzanilide compound and its salt which represent the integer of 0-2, and 1 type or 2 types or more of the compound chosen from the compound group A of said [1] description. Insecticidal, acaricidal, nematicidal, bactericidal or bactericidal composition.
〔3〕 以下の一般式(2)で表される置換ベンズアニリド化合物及びその塩より選ばれる1種又は2種以上と、上記〔1〕記載の化合物群Aより選ばれる化合物の1種又は2種以上を含有する殺虫、殺ダニ、殺線虫、殺菌又は殺バクテリア組成物。 [3] One or two or more kinds selected from the substituted benzanilide compound represented by the following general formula (2) and a salt thereof and one or two kinds of compounds selected from the compound group A described in [1] above An insecticidal, acaricidal, nematicidal, bactericidal or bactericidal composition comprising the above.
一般式(2): General formula (2):
[式中、W1及びW2は、各々独立して酸素原子又は硫黄原子を表し、
Xは、ハロゲン原子、シアノ、ニトロ、アジド、-SCN、-SF5、C1〜C6アルキル、R7によって任意に置換された(C1〜C6)アルキル、C3〜C8シクロアルキル、R7によって任意に置換された(C3〜C8)シクロアルキル、C2〜C6アルケニル、R7によって任意に置換された(C2〜C6)アルケニル、C3〜C8シクロアルケニル、C3〜C8ハロシクロアルケニル、C2〜C6アルキニル、R7によって任意に置換された(C2〜C6)アルキニル、-OH、-OR8、-OS(O)2R8、-SH、-S(O)rR8、-CHO、-C(O)R9、-C(O)OR9、-C(O)SR9、-C(O)NHR10、-C(O)N(R10)R9、-C(S)OR9、-C(S)SR9、-C(S)NHR10、-C(S)N(R10)R9、-CH=NOR11、-C(R9)=NOR11、-S(O)2OR9、-S(O)2NHR10、-S(O)2N(R10)R9、-Si(R13)(R14)R12、フェニル、(Z1)p1によって置換されたフェニル、L又はMを表し、mが2、3又は4を表すとき、各々のXは互いに同一であっても又は互いに相異なっていてもよく、
さらに、2つのXが隣接する場合には、隣接する2つのXは-CH2CH2CH2-, -CH2CH2O-, -CH2OCH2-, -OCH2O-, -CH2CH2S-, -CH2SCH2-, -CH2CH2N(R15)-, -CH2N(R15)CH2-, -CH2CH2CH2CH2-, -CH2CH2CH2O-, -CH2CH2OCH2-, -CH2OCH2O-, -OCH2CH2O-, -OCH2CH2S-, -CH2CH=CH-, -OCH=CH-, -SCH=CH-, -N(R15)CH=CH-, -OCH=N-, -SCH=N-, -N(R15)CH=N-, -N(R15)N=CH-, -CH=CHCH=CH-, -OCH2CH=CH-, -N=CHCH=CH-, -N=CHCH=N-又は-N=CHN=CH-を形成することにより、2つのXのそれぞれが結合する炭素原子と共に5員環又は6員環を形成してもよく、このとき、環を形成する各々の炭素原子に結合した水素原子はZ1によって任意に置換されていてもよく、さらに、同時に2個以上のZ1で置換されている場合、各々のZ1は互いに同一であっても又は互いに相異なっていてもよく、
Yは、ハロゲン原子、シアノ、ニトロ、C1〜C6アルキル、R7によって任意に置換された(C1〜C6)アルキル、C3〜C8シクロアルキル、-OR8、-S(O)rR8、-NH2、C1〜C6アルキルアミノ、ジ(C1〜C6アルキル)アミノ又は-Si(R13)(R14)R12を表し、nが2、3又は4を表すとき、各々のYは互いに同一であっても又は互いに相異なっていてもよく、
さらに、2つのYが隣接する場合には、隣接する2つのYは-CH2CH2CH2-, -CH2CH2O-, -CH2OCH2-, -OCH2O-, -CH2CH2S-, -CH2SCH2-, -SCH2S-, -CH2CH2CH2CH2-, -CH2CH2CH2O-, -CH2CH2OCH2-, -CH2OCH2O-, -OCH2CH2O-, -OCH2CH2S-, -SCH2CH2S-, -OCH=N-又は-SCH=N-を形成することにより、2つのYのそれぞれが結合する炭素原子と共に5員環又は6員環を形成してもよく、このとき、環を形成する各々の炭素原子に結合した水素原子はZ1によって任意に置換されていてもよく、さらに、同時に2個以上のZ1で置換されている場合、各々のZ1は互いに同一であっても又は互いに相異なっていてもよく、
R1及びR2は、各々独立して水素原子、シアノ、C1〜C12アルキル、R18によって任意に置換された(C1〜C12)アルキル、C3〜C12アルケニル、C3〜C12ハロアルケニル、C3〜C12アルキニル、C3〜C12ハロアルキニル、-OH、C1〜C8アルコキシ、C1〜C6アルキルチオ、C1〜C6ハロアルキルチオ、フェニルチオ、(Z1)p1によって置換されたフェニルチオ、-S(O)2R9、-SN(R20)R19、-S(O)2N(R10)R9、-N(R22)R21、-C(O)R9、-C(O)OR9、-C(O)SR9、-C(O)N(R10)R9、-C(S)OR9、-C(S)SR9、-C(S)N(R10)R9、フェニル又は(Z1)p1によって置換されたフェニルを表すか、或いは、R2はR3と一緒になってC2〜C6アルキレン鎖を形成することにより、結合する窒素原子と共に3〜7員環を形成してもよいことを表し、このときこのアルキレン鎖は酸素原子、硫黄原子又は窒素原子を1個含んでもよく、且つハロゲン原子、C1〜C6アルキル基、C1〜C6ハロアルキル基、C1〜C6アルコキシ基、C1〜C6アルキルカルボニル基又はC1〜C6アルコキシカルボニル基によって任意に置換されていてもよく、
R3は、水素原子、シアノ、C1〜C12アルキル、R18によって任意に置換された(C1〜C12)アルキル、C3〜C12シクロアルキル、R18によって任意に置換された(C3〜C12)シクロアルキル、C3〜C12アルケニル、R18によって任意に置換された(C3〜C12)アルケニル、C3〜C12シクロアルケニル、C3〜C12ハロシクロアルケニル、C3〜C12アルキニル、R18によって任意に置換された(C3〜C12)アルキニル、-OH、C1〜C8アルコキシ、C3〜C8アルケニルオキシ、C3〜C8ハロアルケニルオキシ、フェノキシ、(Z1)p1によって置換されたフェノキシ、フェニル(C1〜C4)アルコキシ、(Z1)p1によって置換されたフェニル(C1〜C4)アルコキシ、-N(R22)R21、フェニル、(Z1)p1によって置換されたフェニル、L又はMを表し、
R4は、C1〜C6アルキル、C1〜C6ハロアルキル、R23によって任意に置換された(C1〜C6)アルキル、R23によって任意に置換された(C1〜C6)ハロアルキル、C3〜C8シクロアルキル、C3〜C8ハロシクロアルキル、R23によって任意に置換された(C3〜C8)シクロアルキル、R23によって任意に置換された(C3〜C8)ハロシクロアルキル、C3〜C6アルケニル、C3〜C6ハロアルケニル、C3〜C6アルキニル、C3〜C6ハロアルキニル、フェニル、(Z1)p1によって置換されたフェニル、L又はMを表し、
R5は、シアノ、R23によって任意に置換された(C1〜C6)アルキル、R23によって任意に置換された(C1〜C6)ハロアルキル、R23によって任意に置換された(C3〜C8)シクロアルキル、R23によって任意に置換された(C3〜C8)ハロシクロアルキル、R23によって任意に置換された(C2〜C6)アルケニル、C3〜C8シクロアルケニル、C3〜C8ハロシクロアルケニル、R23によって任意に置換された(C2〜C6)アルキニル、-OR8、-S(O)rR8、-N(R10)R9、-CHO、-C(O)R9、-CH=NOR11、-C(R9)=NOR11、-C(O)OR9、-C(O)SR9、-C(O)NHR10、-C(O)N(R10)R9、-C(S)OR9、-C(S)SR9、-C(S)NHR10、-C(S)N(R10)R9、フェニル、(Z1)p1によって置換されたフェニル、ビフェニル、(Z1)p1によって置換されたビフェニル、フェノキシフェニル、(Z1)p1によって置換されたフェノキシフェニル、ピリジルオキシフェニル、(Z1)p1によって置換されたピリジルオキシフェニル、フェニルチオフェニル、(Z1)p1によって置換されたフェニルチオフェニル、フェニルスルフィニルフェニル、(Z1)p1によって置換されたフェニルスルフィニルフェニル、フェニルスルホニルフェニル、(Z1)p1によって置換されたフェニルスルホニルフェニル、L又はMを表すか、或いは、隣接位に存在するYと一緒になってC2〜C3アルキレン鎖を形成することにより、ベンゼン環と縮合する5〜6員環を形成してもよいことを表し、このときこのアルキレン鎖は酸素原子、硫黄原子又は窒素原子を1個含んでもよく、且つハロゲン原子又はC1〜C6ハロアルキル基によって任意に置換されていてもよく、
R6vは、水素原子、C1〜C6アルキル、C1〜C6ハロアルキル、R23によって任意に置換された(C1〜C6)アルキル、R23によって任意に置換された(C1〜C6)ハロアルキル、C3〜C8シクロアルキル、C3〜C6アルケニル、C3〜C6ハロアルケニル、フェニル(C3〜C6)アルケニル、(Z1)p1によって置換されたフェニル(C3〜C6)アルケニル、C3〜C8シクロアルケニル、C3〜C6アルキニル、C3〜C6ハロアルキニル、フェニル(C3〜C6)アルキニル、(Z1)p1によって置換されたフェニル(C3〜C6)アルキニル、-S(O)2R9、-C(O)R9、-C(O)OR9、-C(O)SR9、-C(S)OR9、-C(S)SR9、-C(O)NHR10、-C(O)N(R10)R9、-C(S)NHR10、-C(S)N(R10)R9、-Si(R13)(R14)R12、-P(O)(OR24)2、-P(S)(OR24)2又はMを表し、
Lは、式L-1から式L-58までの何れかで表される芳香族複素環を表し、
[Wherein, W 1 and W 2 each independently represent an oxygen atom or a sulfur atom,
X is a halogen atom, cyano, nitro, azido, -SCN, -SF 5, C 1 ~C 6 alkyl, optionally substituted by R 7 (C 1 ~C 6) alkyl, C 3 -C 8 cycloalkyl , optionally substituted by R 7 (C 3 ~C 8) cycloalkyl, C 2 -C 6 alkenyl, optionally substituted by R 7 (C 2 ~C 6) alkenyl, C 3 -C 8 cycloalkenyl , C 3 -C 8 halocycloalkyl cycloalkenyl, C 2 -C 6 alkynyl, optionally substituted by R 7 (C 2 ~C 6) alkynyl, -OH, -OR 8, -OS ( O) 2 R 8, -SH, -S (O) r R 8 , -CHO, -C (O) R 9 , -C (O) OR 9 , -C (O) SR 9 , -C (O) NHR 10 , -C ( O) N (R 10 ) R 9 , -C (S) OR 9 , -C (S) SR 9 , -C (S) NHR 10 , -C (S) N (R 10 ) R 9 , -CH = NOR 11 , -C (R 9 ) = NOR 11 , -S (O) 2 OR 9 , -S (O) 2 NHR 10 , -S (O) 2 N (R 10 ) R 9 , -Si (R 13 ) (R 14) R 12, phenyl, (Z 1) phenyl substituted by p1, represents L or M, when m represents 2, 3 or 4, respectively X may be the even or different from each other the same as each other,
Further, when two Xs are adjacent to each other, the two adjacent Xs are -CH 2 CH 2 CH 2- , -CH 2 CH 2 O-, -CH 2 OCH 2- , -OCH 2 O-, -CH 2 CH 2 S-, -CH 2 SCH 2- , -CH 2 CH 2 N (R 15 )-, -CH 2 N (R 15 ) CH 2- , -CH 2 CH 2 CH 2 CH 2- , -CH 2 CH 2 CH 2 O-, -CH 2 CH 2 OCH 2- , -CH 2 OCH 2 O-, -OCH 2 CH 2 O-, -OCH 2 CH 2 S-, -CH 2 CH = CH-,- OCH = CH-, -SCH = CH-, -N (R 15 ) CH = CH-, -OCH = N-, -SCH = N-, -N (R 15 ) CH = N-, -N (R 15 By forming N = CH-, -CH = CHCH = CH-, -OCH 2 CH = CH-, -N = CHCH = CH-, -N = CHCH = N- or -N = CHN = CH- A 5-membered ring or a 6-membered ring may be formed together with the carbon atom to which each of two Xs is bonded. At this time, the hydrogen atom bonded to each carbon atom forming the ring is optionally substituted by Z 1 . Furthermore, when two or more Z 1 are substituted at the same time, each Z 1 may be the same as or different from each other,
Y is a halogen atom, cyano, nitro, C 1 -C 6 alkyl, optionally substituted by R 7 (C 1 ~C 6) alkyl, C 3 -C 8 cycloalkyl, -OR 8, -S (O ) r R 8 , —NH 2 , C 1 -C 6 alkylamino, di (C 1 -C 6 alkyl) amino or —Si (R 13 ) (R 14 ) R 12 , n is 2, 3 or 4 Each Y may be the same as or different from each other;
Further, when two Ys are adjacent to each other, the two adjacent Ys are —CH 2 CH 2 CH 2 —, —CH 2 CH 2 O—, —CH 2 OCH 2 —, —OCH 2 O—, —CH 2 CH 2 S-, -CH 2 SCH 2- , -SCH 2 S-, -CH 2 CH 2 CH 2 CH 2- , -CH 2 CH 2 CH 2 O-, -CH 2 CH 2 OCH 2 -,- By forming CH 2 OCH 2 O-, -OCH 2 CH 2 O-, -OCH 2 CH 2 S-, -SCH 2 CH 2 S-, -OCH = N- or -SCH = N- A 5-membered ring or a 6-membered ring may be formed together with the carbon atom to which each Y is bonded, and at this time, the hydrogen atom bonded to each carbon atom forming the ring may be optionally substituted by Z 1 In addition, in addition, when simultaneously substituted with two or more Z 1 , each Z 1 may be the same as or different from each other,
R 1 and R 2 are each independently a hydrogen atom, cyano, C 1 -C 12 alkyl, (C 1 -C 12 ) alkyl optionally substituted with R 18 , C 3 -C 12 alkenyl, C 3- C 12 haloalkenyl, C 3 -C 12 alkynyl, C 3 -C 12 haloalkynyl, -OH, C 1 -C 8 alkoxy, C 1 -C 6 alkylthio, C 1 -C 6 haloalkylthio, phenylthio, (Z 1 ) phenylthio substituted by p1, -S (O) 2 R 9, -SN (R 20) R 19, -S (O) 2 N (R 10) R 9, -N (R 22) R 21, - C (O) R 9 , -C (O) OR 9 , -C (O) SR 9 , -C (O) N (R 10 ) R 9 , -C (S) OR 9 , -C (S) SR 9 represents -C (S) N (R 10 ) R 9 , phenyl or phenyl substituted by (Z 1 ) p 1 , or R 2 together with R 3 is a C 2 to C 6 alkylene chain Represents that a 3- to 7-membered ring may be formed together with the nitrogen atom to be bonded, and at this time, this alkylene chain is an oxygen atom, a sulfur atom or a nitrogen atom. It may contain one child, and a halogen atom, C 1 -C 6 alkyl group, C 1 -C 6 haloalkyl group, C 1 -C 6 alkoxy group, C 1 -C 6 alkylcarbonyl group or a C 1 -C 6 Optionally substituted by an alkoxycarbonyl group,
R 3 represents a hydrogen atom, cyano, optionally substituted by C 1 -C 12 alkyl, optionally substituted by R 18 (C 1 ~C 12) alkyl, C 3 -C 12 cycloalkyl, R 18 ( C 3 -C 12) cycloalkyl, C 3 -C 12 alkenyl, optionally substituted by R 18 (C 3 ~C 12) alkenyl, C 3 -C 12 cycloalkenyl, C 3 -C 12 halo cycloalkenyl, C 3 -C 12 alkynyl, optionally substituted by R 18 (C 3 ~C 12) alkynyl, -OH, C 1 -C 8 alkoxy, C 3 -C 8 alkenyloxy, C 3 -C 8 haloalkenyloxy , phenoxy, (Z 1) p1 phenoxy substituted by phenyl (C 1 ~C 4) alkoxy, (Z 1) phenyl substituted by p1 (C 1 ~C 4) alkoxy, -N (R 22) R 21 represents phenyl, phenyl, L or M substituted by (Z 1 ) p1 ,
R 4 is optionally substituted by C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, optionally substituted by R 23 (C 1 ~C 6) alkyl, R 23 (C 1 ~C 6) haloalkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 halocycloalkyl, optionally substituted by R 23 (C 3 ~C 8) cycloalkyl, optionally substituted by R 23 (C 3 ~C 8) halocycloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 alkynyl, C 3 -C 6 haloalkynyl, phenyl, phenyl substituted by (Z 1) p1, L Or M,
R 5 is cyano, substituted optionally substituted by R 23 (C 1 ~C 6) alkyl, optionally substituted by R 23 (C 1 ~C 6) haloalkyl, optionally by R 23 (C 3 -C 8) cycloalkyl, optionally substituted by optionally substituted by R 23 (C 3 ~C 8) halocycloalkyl, R 23 (C 2 ~C 6 ) alkenyl, C 3 -C 8 cycloalkyl alkenyl, C 3 -C 8 halocycloalkyl cycloalkenyl, optionally substituted by R 23 (C 2 ~C 6) alkynyl, -OR 8, -S (O) r R 8, -N (R 10) R 9, -CHO, -C (O) R 9 , -CH = NOR 11 , -C (R 9 ) = NOR 11 , -C (O) OR 9 , -C (O) SR 9 , -C (O) NHR 10 , -C (O) N (R 10 ) R 9 , -C (S) OR 9 , -C (S) SR 9 , -C (S) NHR 10 , -C (S) N (R 10 ) R 9 , phenyl, (Z 1) phenyl substituted by p1, biphenyl, (Z 1) biphenyl substituted by p1, phenoxyphenyl, phenoxyphenyl substituted by (Z 1) p1, pyridinium Oxy phenyl, (Z 1) pyridyloxy phenyl substituted by p1, phenylthiophenyl, (Z 1) phenylthio phenyl substituted by p1, phenylsulfinyl phenyl, phenylsulfinyl phenyl substituted by (Z 1) p1 , Phenylsulfonylphenyl, phenylsulfonylphenyl substituted by (Z 1 ) p1 , L or M, or together with Y present in the adjacent position to form a C 2 -C 3 alkylene chain Represents that it may form a 5- to 6-membered ring that is condensed with a benzene ring, in which case the alkylene chain may contain one oxygen atom, sulfur atom or nitrogen atom, and a halogen atom or C 1 -C Optionally substituted by a 6- haloalkyl group,
R 6v is hydrogen atom, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, optionally substituted by R 23 (C 1 ~C 6) alkyl, optionally substituted by R 23 (C 1 ~ C 6) haloalkyl, C 3 -C 8 cycloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, phenyl (C 3 ~C 6) alkenyl, (Z 1) phenyl substituted by p1 (C 3 -C 6) alkenyl, C 3 -C 8 cycloalkenyl, C 3 -C 6 alkynyl, C 3 -C 6 haloalkynyl, phenyl (C 3 ~C 6) alkynyl, phenyl substituted by (Z 1) p1 (C 3 ~C 6) alkynyl, -S (O) 2 R 9 , -C (O) R 9, -C (O) OR 9, -C (O) SR 9, -C (S) OR 9, -C (S) SR 9 , -C (O) NHR 10 , -C (O) N (R 10 ) R 9 , -C (S) NHR 10 , -C (S) N (R 10 ) R 9 , -Si (R 13 ) (R 14 ) R 12 , -P (O) (OR 24 ) 2 , -P (S) (OR 24 ) 2 or M
L represents an aromatic heterocycle represented by any one of formulas L-1 to L-58,
Mは、式M-1から式M-28までの何れかで表される飽和複素環を表し、 M represents a saturated heterocyclic ring represented by any one of formulas M-1 to M-28;
Z1は、ハロゲン原子、シアノ、ニトロ、アジド、-SCN、-SF5、C1〜C6アルキル、C1〜C6ハロアルキル、C1〜C3アルコキシ(C1〜C3)アルキル、C1〜C3ハロアルコキシ(C1〜C3)アルキル、シアノ(C1〜C6)アルキル、ヒドロキシ(C1〜C3)ハロアルキル、C1〜C3アルコキシ(C1〜C3)ハロアルキル、C1〜C3ハロアルコキシ(C1〜C3)ハロアルキル、C1〜C3アルキルチオ(C1〜C3)アルキル、C1〜C3ハロアルキルチオ(C1〜C3)アルキル、C1〜C3アルキルスルフィニル(C1〜C3)アルキル、C1〜C3ハロアルキルスルフィニル(C1〜C3)アルキル、C1〜C3アルキルスルホニル(C1〜C3)アルキル、C1〜C3ハロアルキルスルホニル(C1〜C3)アルキル、C3〜C8シクロアルキル、C3〜C8ハロシクロアルキル、C2〜C6アルケニル、C2〜C6ハロアルケニル、C3〜C8シクロアルケニル、C3〜C8ハロシクロアルケニル、C2〜C6アルキニル、C2〜C6ハロアルキニル、-OH、C1〜C6アルコキシ、C1〜C6ハロアルコキシ、C1〜C3ハロアルコキシ(C1〜C3)ハロアルコキシ、C2〜C6アルケニルオキシ、C2〜C6ハロアルケニルオキシ、C3〜C6アルキニルオキシ、C3〜C6ハロアルキニルオキシ、C1〜C6アルキルスルホニルオキシ、C1〜C6ハロアルキルスルホニルオキシ、-SH、C1〜C6アルキルチオ、C1〜C6ハロアルキルチオ、C1〜C6アルキルスルフィニル、C1〜C6ハロアルキルスルフィニル、C1〜C6アルキルスルホニル、C1〜C6ハロアルキルスルホニル、-NH2、C1〜C6アルキルアミノ、ジ(C1〜C6アルキル)アミノ、C1〜C6アルキルスルホニルアミノ、C1〜C6ハロアルキルスルホニルアミノ、C1〜C6アルコキシカルボニル、C1〜C6ハロアルコキシカルボニル、-C(O)NH2、C1〜C6アルキルアミノカルボニル、ジ(C1〜C6アルキル)アミノカルボニル、-C(S)NH2、C1〜C6アルキルアミノスルホニル、ジ(C1〜C6アルキル)アミノスルホニル又はトリ(C1〜C6アルキル)シリルを表し、p1, p2, p3又はp4が2以上の整数を表すとき、各々のZ1は互いに同一であっても又は互いに相異なっていてもよく、
さらに、2つのZ1が隣接する場合には、隣接する2つのZ1は-CH2CH2CH2-, -CH2CH2O-, -CH2OCH2-, -OCH2O-, -CH2CH2S-, -CH2SCH2-, -CH2CH2CH2CH2-, -CH2CH2CH2O-, -CH2CH2OCH2-, -CH2OCH2O-, -OCH2CH2O-, -OCH2CH2S-又は-CH=CHCH=CH-を形成することにより、2つのZ1のそれぞれが結合する炭素原子と共に5員環又は6員環を形成してもよく、このとき、環を形成する各々の炭素原子に結合した水素原子はハロゲン原子又はC1〜C6アルキル基によって任意に置換されていてもよく、
R7は、ハロゲン原子、シアノ、C3〜C8シクロアルキル、C3〜C8ハロシクロアルキル、-OH、-OR8、-SH、-S(O)rR8、-N(R10)R9、-N(R10)CHO、-N(R10)C(O)R9、-N(R10)C(O)OR9、-N(R10)C(O)SR9、-N(R10)C(S)OR9、-N(R10)C(S)SR9、-N(R10)S(O)2R9、-C(O)OR9、-C(O)N(R10)R9、-Si(R13)(R14)R12、フェニル、(Z1)p1によって置換されたフェニル、L又はMを表し、
R8は、C1〜C6アルキル、R27によって任意に置換された(C1〜C6)アルキル、C3〜C8シクロアルキル、R27によって任意に置換された(C3〜C8)シクロアルキル、C2〜C6アルケニル、R27によって任意に置換された(C2〜C6)アルケニル、C3〜C8シクロアルケニル、C3〜C8ハロシクロアルケニル、C3〜C6アルキニル、R27によって任意に置換された(C3〜C6)アルキニル、フェニル、(Z1)p1によって置換されたフェニル、L又はMを表し、
R9は、C1〜C6アルキル、C1〜C6ハロアルキル、C3〜C6シクロアルキル(C1〜C4)アルキル、C1〜C6アルコキシ(C1〜C4)アルキル、C1〜C6アルキルチオ(C1〜C4)アルキル、シアノ(C1〜C6)アルキル、フェニル(C1〜C4)アルキル、(Z1)p1によって置換されたフェニル(C1〜C4)アルキル、L-(C1〜C4)アルキル、M-(C1〜C4)アルキル、C3〜C8シクロアルキル、C3〜C8ハロシクロアルキル、C3〜C6アルケニル、C3〜C6ハロアルケニル、C3〜C6アルキニル、フェニル又は(Z1)p1によって置換されたフェニルを表し、
R10は、水素原子又はC1〜C6アルキルを表すか、或いは、R9とR10とが一緒になってC2〜C6アルキレン鎖を形成することにより、結合する原子と共に3〜7員環を形成してもよいことを表し、このときこのアルキレン鎖は酸素原子、硫黄原子又は窒素原子を1個含んでもよく、且つハロゲン原子、C1〜C6アルキル基、C1〜C6アルコキシ基、ホルミル基、C1〜C6アルキルカルボニル基又はC1〜C6アルコキシカルボニル基によって任意に置換されていてもよく、
R11は、水素原子、C1〜C6アルキル、C1〜C6ハロアルキル、フェニル(C1〜C4)アルキル、(Z1)p1によって置換されたフェニル(C1〜C4)アルキル、C3〜C6アルケニル、C3〜C6ハロアルケニル、C3〜C6アルキニル又はC3〜C6ハロアルキニルを表すか、或いは、R11はR9と一緒になってC2〜C4アルキレン鎖を形成することにより、結合する原子と共に5〜7員環を形成してもよいことを表し、このときこのアルキレン鎖は酸素原子、硫黄原子又は窒素原子を1個含んでもよく、且つハロゲン原子又はC1〜C6アルキル基によって任意に置換されていてもよく、
R12は、C1〜C6アルキル、C1〜C6ハロアルキル、C3〜C6アルケニル、フェニル又は(Z1)p1によって置換されたフェニルを表し、
R13及びR14は、各々独立してC1〜C6アルキル又はC1〜C6ハロアルキルを表し、
R15は、水素原子、C1〜C6アルキル、C1〜C6ハロアルキル、C1〜C6アルコキシカルボニル(C1〜C4)アルキル、C1〜C6ハロアルコキシカルボニル(C1〜C4)アルキル、フェニル(C1〜C4)アルキル、(Z1)p1によって置換されたフェニル(C1〜C4)アルキル、C3〜C6アルケニル、C3〜C6ハロアルケニル、C3〜C6アルキニル、C3〜C6ハロアルキニル、C1〜C6アルコキシ、C1〜C6アルコキシカルボニル、C1〜C6ハロアルコキシカルボニル、フェニル又は(Z1)p1によって置換されたフェニルを表し、
R18は、ハロゲン原子、シアノ、ニトロ、C3〜C8シクロアルキル、C3〜C8ハロシクロアルキル、-OR28、-N(R29)R28、-SH、-S(O)rR30、-SO2NHR32、-SO2N(R32)R31、-CHO、-C(O)R31、-C(O)OH、-C(O)OR31、-C(O)SR31、-C(O)NHR32、-C(O)N(R32)R31、-C(O)C(O)OR31、-C(R34)=NOH、-C(R34)=NOR33、-Si(R13)(R14)R12、-P(O)(OR24)2、-P(S)(OR24)2、-P(フェニル)2、-P(O)(フェニル)2、フェニル、(Z1)p1によって置換されたフェニル、L又はMを表し、
R19は、C1〜C12アルキル、C1〜C12ハロアルキル、C1〜C12アルコキシ(C1〜C12)アルキル、シアノ(C1〜C12)アルキル、C1〜C12アルコキシカルボニル(C1〜C12)アルキル、フェニル(C1〜C4)アルキル、(Z1)p1によって置換されたフェニル(C1〜C4)アルキル、C3〜C12アルケニル、C3〜C12ハロアルケニル、C3〜C12アルキニル、C3〜C12ハロアルキニル、C1〜C12アルキルカルボニル、C1〜C12アルコキシカルボニル、フェニル又は(Z1)p1によって置換されたフェニルを表し、
R20は、C1〜C12アルキル、C1〜C12ハロアルキル、C1〜C12アルコキシ(C1〜C12)アルキル、シアノ(C1〜C12)アルキル、C1〜C12アルコキシカルボニル(C1〜C12)アルキル、フェニル(C1〜C4)アルキル、(Z1)p1によって置換されたフェニル(C1〜C4)アルキル、C3〜C12アルケニル、C3〜C12ハロアルケニル、C3〜C12アルキニル、C3〜C12ハロアルキニル、フェニル又は(Z1)p1によって置換されたフェニルを表すか、或いは、R19とR20とが一緒になってC4〜C7アルキレン鎖を形成することにより、結合する窒素原子と共に5〜8員環を形成してもよいことを表し、このときこのアルキレン鎖は酸素原子又は硫黄原子を1個含んでもよく、且つC1〜C4アルキル基又はC1〜C4アルコキシ基によって任意に置換されていてもよく、
R21は、水素原子、C1〜C6アルキル、C1〜C6ハロアルキル、フェニル(C1〜C4)アルキル、(Z1)p1によって置換されたフェニル(C1〜C4)アルキル、C3〜C6アルケニル、C3〜C6ハロアルケニル、C3〜C6アルキニル、-CHO、C1〜C6アルキルカルボニル、C1〜C6ハロアルキルカルボニル、C1〜C6アルコキシカルボニル、C1〜C6ハロアルコキシカルボニル、フェニル(C1〜C4)アルコキシカルボニル、(Z1)p1によって置換されたフェニル(C1〜C4)アルコキシカルボニル、フェノキシカルボニル、(Z1)p1によって置換されたフェノキシカルボニル、フェニルカルボニル、(Z1)p1によって置換されたフェニルカルボニル、フェニル又は(Z1)p1によって置換されたフェニルを表し、
R22は、水素原子、C1〜C6アルキル、-CHO、C1〜C6アルキルカルボニル、C1〜C6ハロアルキルカルボニル又はC1〜C6アルコキシカルボニルを表し、
R23は、シアノ、C3〜C8シクロアルキル、C3〜C8ハロシクロアルキル、-OH、-OR8、-SH、-S(O)rR8、-N(R10)R9、-N(R10)CHO、-N(R10)C(O)R9、-N(R10)C(O)OR9、-N(R10)C(O)SR9、-N(R10)C(S)OR9、-N(R10)C(S)SR9、-N(R10)S(O)2R9、-C(O)OR9、-C(O)N(R10)R9、-Si(R13)(R14)R12、フェニル、(Z1)p1によって置換されたフェニル、L又はMを表し、
R24は、C1〜C6アルキル又はC1〜C6ハロアルキルを表し、
R25は、ハロゲン原子、シアノ、C1〜C6アルキル、C1〜C6ハロアルキル、ヒドロキシ(C1〜C6)アルキル、C1〜C4アルコキシ(C1〜C4)アルキル、C1〜C4アルコキシカルボニル(C1〜C4)アルキル、C1〜C6アルコキシ、C1〜C6アルコキシカルボニル、フェニル又は(Z1)p1によって置換されたフェニルを表し、q1, q2, q3又はq4が2以上の整数を表すとき、各々のR25は互いに同一であっても、または互いに相異なっていてもよく、
R26は、水素原子、C1〜C6アルキル、C1〜C6ハロアルキル、-CHO、C1〜C6アルキルカルボニル、C1〜C6ハロアルキルカルボニル、フェニル(C1〜C4)アルキルカルボニル、(Z1)p1によって置換されたフェニル(C1〜C4)アルキルカルボニル、C1〜C6アルコキシカルボニル、C1〜C6ハロアルコキシカルボニル、フェニル(C1〜C4)アルコキシカルボニル、(Z1)p1によって置換されたフェニル(C1〜C4)アルコキシカルボニル、C1〜C6アルキルチオカルボニル、C1〜C6アルコキシチオカルボニル、C1〜C6アルキルアミノカルボニル、ジ(C1〜C6アルキル)アミノカルボニル、C1〜C6アルキルアミノチオカルボニル、ジ(C1〜C6アルキル)アミノチオカルボニル、フェニルカルボニル、(Z1)p1によって置換されたフェニルカルボニル、C1〜C6アルキルスルホニル、C1〜C6ハロアルキルスルホニル、フェニルスルホニル、(Z1)p1によって置換されたフェニルスルホニル、-P(O)(OR24)2又は-P(S)(OR24)2を表し、
R27は、ハロゲン原子、シアノ、C3〜C8シクロアルキル、C3〜C8ハロシクロアルキル、C1〜C6アルコキシ、C1〜C6ハロアルコキシ、C1〜C6アルキルチオ、C1〜C6ハロアルキルチオ、C1〜C6アルキルスルホニル、C1〜C6ハロアルキルスルホニル、C1〜C6アルキルアミノ、ジ(C1〜C6アルキル)アミノ、-CHO、C1〜C6アルキルカルボニル、C1〜C6ハロアルキルカルボニル、C1〜C6アルコキシカルボニル、C1〜C6ハロアルコキシカルボニル、-CH=NOR11、-C(R9)=NOR11、フェニル、(Z1)p1によって置換されたフェニル、L又はMを表し、
R28は、水素原子、C1〜C8アルキル、R35によって任意に置換された(C1〜C8)アルキル、C3〜C8シクロアルキル、R35によって任意に置換された(C3〜C8)シクロアルキル、C3〜C8アルケニル、R35によって任意に置換された(C3〜C8)アルケニル、C3〜C8アルキニル、R35によって任意に置換された(C3〜C8)アルキニル、-CHO、-C(O)R31、-C(O)OR31、-C(O)SR31、-C(O)NHR32、-C(O)N(R32)R31、-C(O)C(O)R31、-C(O)C(O)OR31、-C(S)R31、-C(S)OR31、-C(S)SR31、-C(S)NHR32、-C(S)N(R32)R31、-S(O)2R31、-S(O)2N(R32)R31、-Si(R13)(R14)R12、-P(O)(OR24)2、-P(S)(OR24)2、フェニル、(Z1)p1によって置換されたフェニル、L又はMを表し、
R29は、水素原子、C1〜C6アルキル、C1〜C6ハロアルキル、C3〜C6シクロアルキル又はC1〜C6アルコキシを表すか、或いは、R28とR29とが一緒になってC2〜C5アルキレン鎖を形成することにより、結合する窒素原子と共に3〜6員環を形成してもよいことを表し、このときこのアルキレン鎖は酸素原子又は硫黄原子を1個含んでもよく、且つハロゲン原子、C1〜C6アルキル基、C1〜C6アルコキシ基、フェニル基又は(Z1)p1によって置換されたフェニル基によって置換されていてもよく、
R30は、C1〜C8アルキル、R35によって任意に置換された(C1〜C8)アルキル、C3〜C8シクロアルキル、R35によって任意に置換された(C3〜C8)シクロアルキル、C3〜C8アルケニル、R35によって任意に置換された(C3〜C8)アルケニル、C3〜C8アルキニル、R35によって任意に置換された(C3〜C8)アルキニル、-SH、C1〜C6アルキルチオ、C1〜C6ハロアルキルチオ、フェニルチオ、(Z1)p1によって置換されたフェニルチオ、-CHO、-C(O)R31、-C(O)OR31、-C(O)SR31、-C(O)NHR32、-C(O)N(R32)R31、-C(O)C(O)R31、-C(O)C(O)OR31、-C(S)R31、-C(S)OR31、-C(S)SR31、-C(S)NHR32、-C(S)N(R32)R31、-P(O)(OR24)2、-P(S)(OR24)2、フェニル、(Z1)p1によって置換されたフェニル、L-18、L-21、L-25、L-30〜L-35、L-45、L-48、L-49又はMを表し、
R31は、C1〜C6アルキル、C1〜C6ハロアルキル、C3〜C8シクロアルキル(C1〜C4)アルキル、C1〜C6アルコキシ(C1〜C4)アルキル、C1〜C6ハロアルコキシ(C1〜C4)アルキル、C1〜C6アルキルチオ(C1〜C4)アルキル、C1〜C6ハロアルキルチオ(C1〜C4)アルキル、C1〜C6アルキルスルホニル(C1〜C4)アルキル、C1〜C6ハロアルキルスルホニル(C1〜C4)アルキル、シアノ(C1〜C6)アルキル、C1〜C6アルキルカルボニル(C1〜C4)アルキル、C1〜C6ハロアルキルカルボニル(C1〜C4)アルキル、C1〜C6アルコキシカルボニル(C1〜C4)アルキル、ジ(C1〜C6アルキル)アミノカルボニル(C1〜C4)アルキル、トリ(C1〜C4アルキル)シリル(C1〜C4)アルキル、フェニル(C1〜C4)アルキル、(Z1)p1によって置換されたフェニル(C1〜C4)アルキル、L-(C1〜C4)アルキル、M-(C1〜C4)アルキル、C3〜C8シクロアルキル、C3〜C8ハロシクロアルキル、C2〜C6アルケニル、C2〜C6ハロアルケニル、C2〜C6アルキニル、C2〜C6ハロアルキニル、フェニル、(Z1)p1によって置換されたフェニル、L又はMを表し、
R32は、水素原子、C1〜C6アルキル、C1〜C6ハロアルキル、フェニル又は(Z1)p1によって置換されたフェニルを表すか、或いは、R31とR32とが一緒になってC2〜C5アルキレン鎖を形成することにより、結合する窒素原子と共に3〜6員環を形成してもよいことを表し、このときこのアルキレン鎖は酸素原子、硫黄原子又は窒素原子を1個含んでもよく、且つハロゲン原子、C1〜C6アルキル基、C1〜C6アルコキシ基、ホルミル基、C1〜C6アルキルカルボニル基、C1〜C6アルコキシカルボニル基、フェニル基又は(Z1)p1によって置換されたフェニル基によって任意に置換されていてもよく、
R33は、水素原子、C1〜C8アルキル、R35によって任意に置換された(C1〜C8)アルキル、C3〜C8シクロアルキル、C3〜C8アルケニル、R35によって任意に置換された(C3〜C8)アルケニル、C3〜C8アルキニル又はR35によって任意に置換された(C3〜C8)アルキニルを表し、
R34は、水素原子、C1〜C6アルキル、C1〜C6ハロアルキル、C3〜C8シクロアルキル(C1〜C4)アルキル、C1〜C6アルコキシ(C1〜C4)アルキル、C1〜C6ハロアルコキシ(C1〜C4)アルキル、C1〜C6アルキルチオ(C1〜C4)アルキル、C1〜C6ハロアルキルチオ(C1〜C4)アルキル、C1〜C6アルキルスルホニル(C1〜C4)アルキル、C1〜C6ハロアルキルスルホニル(C1〜C4)アルキル、フェニル(C1〜C4)アルキル、(Z1)p1によって置換されたフェニル(C1〜C4)アルキル、フェニル又は(Z1)p1によって置換されたフェニルを表し、
R35は、ハロゲン原子、シアノ、ニトロ、C3〜C8シクロアルキル、C3〜C8ハロシクロアルキル、-OH、-OR36、-SH、-S(O)rR36、-NHR37、-N(R37)R36、-CHO、-C(O)R31、-C(O)OR31、-C(O)SR31、-C(O)NHR32、-C(O)N(R32)R31、-C(O)C(O)OR31、-CH=NOR11、-C(R9)=NOR11、-Si(R13)(R14)R12、-P(O)(OR24)2、-P(S)(OR24)2、-P(フェニル)2、-P(O)(フェニル)2、フェニル、(Z1)p1によって置換されたフェニル、L又はMを表し、
R36は、C1〜C6アルキル、C1〜C6ハロアルキル、C1〜C6アルコキシ(C1〜C4)アルキル、C1〜C6アルキルチオ(C1〜C4)アルキル、フェニル(C1〜C4)アルキル、(Z1)p1によって置換されたフェニル(C1〜C4)アルキル、C3〜C8シクロアルキル、C3〜C8ハロシクロアルキル、C3〜C6アルケニル、C3〜C6ハロアルケニル、C3〜C8シクロアルケニル、C3〜C8ハロシクロアルケニル、C3〜C6アルキニル、C3〜C6ハロアルキニル、-CHO、C1〜C6アルキルカルボニル、C1〜C6ハロアルキルカルボニル、C1〜C6アルコキシカルボニル、C1〜C6ハロアルコキシカルボニル、C1〜C6アルキルアミノカルボニル、ジ(C1〜C6アルキル)アミノカルボニル、フェニルカルボニル、(Z1)p1によって置換されたフェニルカルボニル、C1〜C6アルキルアミノチオカルボニル、ジ(C1〜C6アルキル)アミノチオカルボニル、フェニル、(Z1)p1によって置換されたフェニル、L又はMを表し、
R37は、水素原子、C1〜C6アルキル、C1〜C6ハロアルキル、C3〜C8シクロアルキル、C3〜C6アルケニル、C3〜C6アルキニル、C1〜C6アルキルカルボニル、C1〜C6ハロアルキルカルボニル、C1〜C6アルコキシカルボニル、C1〜C6ハロアルコキシカルボニル、フェノキシカルボニル、(Z1)p1によって置換されたフェノキシカルボニル、フェニルカルボニル、(Z1)p1によって置換されたフェニルカルボニル、C1〜C6アルキルスルホニル、C1〜C6ハロアルキルスルホニル、フェニル、(Z1)p1によって置換されたフェニル、L又はMを表すか、或いは、R36とR37とが一緒になってC2〜C5アルキレン鎖を形成することにより、結合する窒素原子と共に3〜6員環を形成してもよいことを表し、このときこのアルキレン鎖は酸素原子又は硫黄原子を1個含んでもよく、且つハロゲン原子又はメチル基によって置換されていてもよく、
mは、0〜4の整数を表し、
nは、0〜4の整数を表し、
p1は、1〜5の整数を表し、
p2は、0〜4の整数を表し、
p3は、0〜3の整数を表し、
p4は、0〜2の整数を表し、
p5は、0又は1の整数を表し、
q1は、0〜3の整数を表し、
q2は、0〜5の整数を表し、
q3は、0〜7の整数を表し、
q4は、0〜9の整数を表し、
rは、0〜2の整数を表し、
tは、0又は1の整数を表す。]
〔4〕 上記〔3〕記載の一般式(2)において、W1及びW2は、酸素原子を表し、
Xは、ハロゲン原子、ニトロ、C1〜C4アルキル、C1〜C4ハロアルキル、C1〜C4アルキルチオ、C1〜C4アルキルスルフィニル又はC1〜C4アルキルスルホニルを表し、mが2を表すとき、各々のXは互いに同一であっても又は互いに相異なっていてもよく、
Yは、ハロゲン原子又はC1〜C4アルキルを表し、nが2を表すとき、各々のYは互いに同一であっても又は互いに相異なっていてもよく、
R1及びR2は、水素原子を表し、
R3は、C1〜C8アルキル、C1〜C4アルキルチオ(C1〜C4)アルキル、C1〜C4アルキルスルフィニル(C1〜C4)アルキル又はC1〜C4アルキルスルホニル(C1〜C4)アルキルを表し、
R4は、C1〜C6アルキル又はC1〜C6ハロアルキルを表し、
R5は、フェニル、(Z1)p1によって置換されたフェニル、(Z1)p1によって置換されたフェノキシフェニル、(Z1)p1によって置換されたピリジルオキシフェニル、L-1〜L-4、L-8〜L-13、L-15〜L-23、L-45〜L-52又はL-53を表し、
R6vは、水素原子を表し、
Z1は、ハロゲン原子、シアノ、ニトロ、C1〜C6アルキル、C1〜C6ハロアルキル、C1〜C3アルキルチオ(C1〜C3)アルキル、C1〜C3ハロアルキルチオ(C1〜C3)アルキル、C1〜C3アルキルスルフィニル(C1〜C3)アルキル、C1〜C3ハロアルキルスルフィニル(C1〜C3)アルキル、C1〜C3アルキルスルホニル(C1〜C3)アルキル、C1〜C3ハロアルキルスルホニル(C1〜C3)アルキル、C1〜C6アルコキシ、C1〜C6ハロアルコキシ、C1〜C3ハロアルコキシ(C1〜C3)ハロアルコキシ、C1〜C6アルキルスルホニルオキシ、C1〜C6ハロアルキルスルホニルオキシ、C1〜C6アルキルチオ、C1〜C6ハロアルキルチオ、C1〜C6アルキルスルフィニル、C1〜C6ハロアルキルスルフィニル、C1〜C6アルキルスルホニル、C1〜C6ハロアルキルスルホニル、-C(O)NH2又は-C(S)NH2を表し、p1, p2, p3又はp4が2以上の整数を表すとき、各々のZ1は互いに同一であっても又は互いに相異なっていてもよく、
さらに、2つのZ1が隣接する場合には、隣接する2つのZ1は-CF2CF2O-, -CF2OCF2-, -OCF2O-, -OCF2CHFO-, -OCF2CF2O-又は-CH=CHCH=CH-を形成することにより、2つのZ1のそれぞれが結合する炭素原子と共に5員環又は6員環を形成してもよく、
R15は、C1〜C6アルキル、C1〜C6ハロアルキル、フェニル(C1〜C4)アルキル、(Z1)p1によって置換されたフェニル(C1〜C4)アルキル、フェニル又は(Z1)p1によって置換されたフェニルを表し、
mは、0〜2の整数を表し、
nは、0〜2の整数を表し、
q2、q3及びq4は、各々独立して0〜2の整数を表す置換ベンズアニリド化合物及びその塩より選ばれる1種又は2種以上と、上記〔1〕記載の化合物群Aより選ばれる化合物の1種又は2種以上を含有する殺虫、殺ダニ、殺線虫、殺菌又は殺バクテリア組成物。
Z 1 is a halogen atom, cyano, nitro, azido, -SCN, -SF 5, C 1 ~C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 3 alkoxy (C 1 ~C 3) alkyl, C 1 -C 3 haloalkoxy (C 1 ~C 3) alkyl, cyano (C 1 ~C 6) alkyl, hydroxy (C 1 ~C 3) haloalkyl, C 1 -C 3 alkoxy (C 1 ~C 3) haloalkyl, C 1 -C 3 haloalkoxy (C 1 ~C 3) haloalkyl, C 1 -C 3 alkylthio (C 1 ~C 3) alkyl, C 1 -C 3 haloalkylthio (C 1 ~C 3) alkyl, C 1 ~ C 3 alkylsulfinyl (C 1 ~C 3) alkyl, C 1 -C 3 haloalkylsulfinyl (C 1 ~C 3) alkyl, C 1 -C 3 alkylsulfonyl (C 1 ~C 3) alkyl, C 1 -C 3 haloalkylsulfonyl (C 1 ~C 3) alkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 halocycloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 3 -C 8 cycloalkenyl, C 3 -C 8 halocycloalkyl cycloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, -OH, C 1 ~C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 3 haloalkoxy (C 1 -C 3) haloalkoxy, C 2 -C 6 alkenyloxy, C 2 -C 6 haloalkenyloxy, C 3 -C 6 alkynyloxy, C 3 -C 6 haloalkynyloxy, C 1 ~ C 6 alkylsulfonyloxy, C 1 -C 6 haloalkylsulfonyloxy, -SH, C 1 ~C 6 alkylthio, C 1 -C 6 haloalkylthio, C 1 -C 6 alkylsulfinyl, C 1 -C 6 haloalkylsulfinyl, C 1 -C 6 alkylsulfonyl, C 1 -C 6 haloalkylsulfonyl, -NH 2, C 1 ~C 6 alkyl amino, di (C 1 -C 6 alkyl) amino, C 1 -C 6 alkylsulfonylamino, C 1 ~ C 6 haloalkylsulfonyl amino, C 1 -C 6 an alkoxycarbonyl Carbonyl, C 1 -C 6 haloalkoxycarbonyl, -C (O) NH 2, C 1 ~C 6 alkylaminocarbonyl, di (C 1 -C 6 alkyl) aminocarbonyl, -C (S) NH 2, C 1 -C 6 alkylaminosulfonyl, di (C 1 -C 6 alkyl) aminosulfonyl or a tri (C 1 -C 6 alkyl) a silyl, when p1, p2, p3 or p4 represents an integer of 2 or more, each of the Z 1 may be the same as or different from each other,
Further, when two Z 1 are adjacent to each other, the two adjacent Z 1 are —CH 2 CH 2 CH 2 —, —CH 2 CH 2 O—, —CH 2 OCH 2 —, —OCH 2 O—, -CH 2 CH 2 S-, -CH 2 SCH 2- , -CH 2 CH 2 CH 2 CH 2- , -CH 2 CH 2 CH 2 O-, -CH 2 CH 2 OCH 2- , -CH 2 OCH 2 O-, -OCH 2 CH 2 O-, by forming a CH- -OCH 2 CH 2 S- or -CH = CHCH =, 5-membered ring or a 6-membered together with the carbon atom to which each of the two Z 1 is attached may form a ring, this time, the hydrogen atoms bonded to each carbon atom forming the ring may be optionally substituted by halogen atom or C 1 -C 6 alkyl group,
R 7 is a halogen atom, cyano, C 3 to C 8 cycloalkyl, C 3 to C 8 halocycloalkyl, —OH, —OR 8 , —SH, —S (O) r R 8 , —N (R 10 ) R 9 , -N (R 10 ) CHO, -N (R 10 ) C (O) R 9 , -N (R 10 ) C (O) OR 9 , -N (R 10 ) C (O) SR 9 , -N (R 10 ) C (S) OR 9 , -N (R 10 ) C (S) SR 9 , -N (R 10 ) S (O) 2 R 9 , -C (O) OR 9 ,- C (O) N (R 10 ) R 9 , -Si (R 13 ) (R 14 ) R 12 , phenyl, phenyl, L or M substituted by (Z 1 ) p1 ,
R 8 is optionally substituted by C 1 -C 6 alkyl, optionally substituted by R 27 (C 1 ~C 6) alkyl, C 3 -C 8 cycloalkyl, R 27 (C 3 ~C 8 ) cycloalkyl, C 2 -C 6 alkenyl, optionally substituted by R 27 (C 2 ~C 6) alkenyl, C 3 -C 8 cycloalkenyl, C 3 -C 8 halocycloalkyl cycloalkenyl, C 3 -C 6 It represents alkynyl, optionally substituted by R 27 (C 3 ~C 6) alkynyl, phenyl, phenyl, L or M, which is substituted by (Z 1) p1,
R 9 is C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl (C 1 -C 4 ) alkyl, C 1 -C 6 alkoxy (C 1 -C 4 ) alkyl, C 1 -C 6 alkylthio (C 1 ~C 4) alkyl, cyano (C 1 ~C 6) alkyl, phenyl (C 1 ~C 4) alkyl, (Z 1) phenyl substituted by p1 (C 1 ~C 4 ) alkyl, L- (C 1 ~C 4) alkyl, M- (C 1 ~C 4) alkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 halocycloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 alkynyl, represents phenyl substituted by phenyl or (Z 1) p1,
R 10 represents a hydrogen atom or C 1 -C 6 alkyl, or R 9 and R 10 together form a C 2 -C 6 alkylene chain to form 3-7 together with the atoms to be bonded. indicates that the members may form a ring, this time the alkylene chain an oxygen atom, may contain one sulfur atom or a nitrogen atom, and a halogen atom, C 1 -C 6 alkyl group, C 1 -C 6 alkoxy group, a formyl group, may be optionally substituted by C 1 -C 6 alkylcarbonyl group or a C 1 -C 6 alkoxycarbonyl group,
R 11 represents a hydrogen atom, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, phenyl (C 1 ~C 4) alkyl, (Z 1) phenyl substituted by p1 (C 1 ~C 4) alkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 alkynyl or C 3 -C 6 haloalkynyl, or R 11 together with R 9 is C 2 -C 4 By forming an alkylene chain, it indicates that a 5- to 7-membered ring may be formed together with the atoms to be bonded. At this time, the alkylene chain may contain one oxygen atom, sulfur atom or nitrogen atom, and halogen It may be optionally substituted by atom or a C 1 -C 6 alkyl group,
R 12 represents C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 alkenyl, phenyl or phenyl substituted by (Z 1 ) p 1 ,
R 13 and R 14 each independently represent C 1 -C 6 alkyl or C 1 -C 6 haloalkyl,
R 15 is a hydrogen atom, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxycarbonyl (C 1 -C 4 ) alkyl, C 1 -C 6 haloalkoxycarbonyl (C 1 -C 4) alkyl, phenyl (C 1 -C 4) alkyl, (Z 1) phenyl substituted by p1 (C 1 -C 4) alkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 alkynyl, C 3 -C 6 haloalkynyl, C 1 -C 6 alkoxy, C 1 -C 6 alkoxycarbonyl, C 1 -C 6 haloalkoxycarbonyl, phenyl substituted by phenyl or (Z 1) p1 Represent,
R 18 is a halogen atom, cyano, nitro, C 3 -C 8 cycloalkyl, C 3 -C 8 halocycloalkyl, -OR 28 , -N (R 29 ) R 28 , -SH, -S (O) r R 30 , -SO 2 NHR 32 , -SO 2 N (R 32 ) R 31 , -CHO, -C (O) R 31 , -C (O) OH, -C (O) OR 31 , -C (O ) SR 31 , -C (O) NHR 32 , -C (O) N (R 32 ) R 31 , -C (O) C (O) OR 31 , -C (R 34 ) = NOH, -C (R 34 ) = NOR 33 , -Si (R 13 ) (R 14 ) R 12 , -P (O) (OR 24 ) 2 , -P (S) (OR 24 ) 2 , -P (phenyl) 2 , -P (O) (phenyl) 2 , phenyl, phenyl substituted by (Z 1 ) p1 , L or M,
R 19 is C 1 -C 12 alkyl, C 1 -C 12 haloalkyl, C 1 -C 12 alkoxy (C 1 -C 12 ) alkyl, cyano (C 1 -C 12 ) alkyl, C 1 -C 12 alkoxycarbonyl (C 1 ~C 12) alkyl, phenyl (C 1 ~C 4) alkyl, (Z 1) phenyl substituted by p1 (C 1 ~C 4) alkyl, C 3 -C 12 alkenyl, C 3 -C 12 represents haloalkenyl, C 3 -C 12 alkynyl, C 3 -C 12 haloalkynyl, C 1 -C 12 alkylcarbonyl, C 1 -C 12 alkoxycarbonyl, phenyl substituted by phenyl or (Z 1) p1,
R 20 is C 1 -C 12 alkyl, C 1 -C 12 haloalkyl, C 1 -C 12 alkoxy (C 1 -C 12 ) alkyl, cyano (C 1 -C 12 ) alkyl, C 1 -C 12 alkoxycarbonyl (C 1 ~C 12) alkyl, phenyl (C 1 ~C 4) alkyl, (Z 1) phenyl substituted by p1 (C 1 ~C 4) alkyl, C 3 -C 12 alkenyl, C 3 -C 12 haloalkenyl, C 3 -C 12 alkynyl, C 3 -C 12 haloalkynyl, or represents phenyl which is substituted by phenyl or (Z 1) p1, or, C 4 ~ and R 19 and R 20 together by forming a C 7 alkylene chain, it represents that may form a 5- to 8-membered ring together with the nitrogen atom to which they are attached the alkylene chain at this time may contain one oxygen atom or sulfur atom, and C It may be optionally substituted by 1 -C 4 alkyl or C 1 -C 4 alkoxy group,
R 21 is a hydrogen atom, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, phenyl (C 1 ~C 4) alkyl, (Z 1) phenyl substituted by p1 (C 1 ~C 4) alkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 alkynyl, -CHO, C 1 ~C 6 alkyl carbonyl, C 1 -C 6 haloalkylcarbonyl, C 1 -C 6 alkoxycarbonyl, C 1 -C 6 haloalkoxycarbonyl, phenyl (C 1 ~C 4) alkoxycarbonyl, (Z 1) phenyl substituted by p1 (C 1 ~C 4) alkoxycarbonyl, phenoxycarbonyl, substituted by (Z 1) p1 It represents a phenoxycarbonyl, phenylcarbonyl, phenyl substituted by the (Z 1) phenylcarbonyl substituted by p1, phenyl or (Z 1) p1,
R 22 represents a hydrogen atom, C 1 -C 6 alkyl, -CHO, C 1 -C 6 alkylcarbonyl, a C 1 -C 6 haloalkylcarbonyl or C 1 -C 6 alkoxycarbonyl,
R 23 is cyano, C 3 -C 8 cycloalkyl, C 3 -C 8 halocycloalkyl, —OH, —OR 8 , —SH, —S (O) r R 8 , —N (R 10 ) R 9 , -N (R 10 ) CHO, -N (R 10 ) C (O) R 9 , -N (R 10 ) C (O) OR 9 , -N (R 10 ) C (O) SR 9 , -N (R 10 ) C (S) OR 9 , -N (R 10 ) C (S) SR 9 , -N (R 10 ) S (O) 2 R 9 , -C (O) OR 9 , -C (O ) N (R 10 ) R 9 , -Si (R 13 ) (R 14 ) R 12 , phenyl, phenyl substituted by (Z 1 ) p1 , L or M;
R 24 represents C 1 -C 6 alkyl or C 1 -C 6 haloalkyl,
R 25 is a halogen atom, cyano, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, hydroxy (C 1 -C 6 ) alkyl, C 1 -C 4 alkoxy (C 1 -C 4 ) alkyl, C 1 -C 4 alkoxycarbonyl (C 1 ~C 4) represents alkyl, C 1 -C 6 alkoxy, C 1 -C 6 alkoxycarbonyl, phenyl substituted by phenyl or (Z 1) p1, q1, q2, q3 or when q4 represents an integer of 2 or more, each R 25 may be the same as or different from each other;
R 26 is a hydrogen atom, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, -CHO, C 1 -C 6 alkylcarbonyl, C 1 -C 6 haloalkylcarbonyl, phenyl (C 1 -C 4 ) alkylcarbonyl , (Z 1) phenyl substituted by p1 (C 1 ~C 4) alkylcarbonyl, C 1 -C 6 alkoxycarbonyl, C 1 -C 6 haloalkoxycarbonyl, phenyl (C 1 -C 4) alkoxycarbonyl, ( Z 1) phenyl substituted by p1 (C 1 ~C 4) alkoxycarbonyl, C 1 -C 6 alkylthiocarbonyl, C 1 -C 6 alkoxythiocarbonyl, C 1 -C 6 alkylaminocarbonyl, di (C 1 ~ C 6 alkyl) aminocarbonyl, C 1 -C 6 alkylamino thiocarbonyl, di (C 1 -C 6 alkyl) aminothiocarbonyl, phenylcarbonyl, (Z 1) phenylcarbonyl substituted by p1, C 1 -C 6 Alkyls Represents Honiru, C 1 -C 6 haloalkylsulfonyl, phenylsulfonyl, and (Z 1) phenylsulfonyl substituted by p1, -P (O) (OR 24) 2 or -P (S) (OR 24) 2,
R 27 is a halogen atom, cyano, C 3 -C 8 cycloalkyl, C 3 -C 8 halocycloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 alkylthio, C 1 -C 6 haloalkylthio, C 1 -C 6 alkylsulfonyl, C 1 -C 6 haloalkylsulfonyl, C 1 -C 6 alkylamino, di (C 1 -C 6 alkyl) amino, -CHO, C 1 -C 6 alkyl carbonyl, C 1 -C 6 haloalkylcarbonyl, C 1 -C 6 alkoxycarbonyl, C 1 -C 6 haloalkoxycarbonyl, -CH = NOR 11, -C ( R 9) = NOR 11, phenyl, (Z 1) p1 Represents phenyl, L or M substituted by
R 28 is a hydrogen atom, C 1 -C 8 alkyl, optionally substituted by R 35 (C 1 ~C 8) alkyl, C 3 -C 8 cycloalkyl, optionally substituted by R 35 (C 3 -C 8) cycloalkyl, C 3 -C 8 alkenyl, optionally substituted by R 35 (C 3 ~C 8) alkenyl, optionally substituted by C 3 -C 8 alkynyl, R 35 (C 3 ~ C 8 ) alkynyl, -CHO, -C (O) R 31 , -C (O) OR 31 , -C (O) SR 31 , -C (O) NHR 32 , -C (O) N (R 32 ) R 31 , -C (O) C (O) R 31 , -C (O) C (O) OR 31 , -C (S) R 31 , -C (S) OR 31 , -C (S) SR 31 , -C (S) NHR 32 , -C (S) N (R 32 ) R 31 , -S (O) 2 R 31 , -S (O) 2 N (R 32 ) R 31 , -Si (R 13 ) (R 14 ) R 12 , -P (O) (OR 24 ) 2 , -P (S) (OR 24 ) 2 , phenyl, (Z 1 ) represents phenyl, L or M substituted by p1 ;
R 29 represents a hydrogen atom, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl or C 1 -C 6 alkoxy, or R 28 and R 29 together by now it forms a C 2 -C 5 alkylene chain, represents that may form a 3-6 membered ring together with the nitrogen atom to which they are attached this case the alkylene chain may contain one oxygen atom or a sulfur atom But often, and halogen atom, C 1 -C 6 alkyl group, C 1 -C 6 alkoxy group, a phenyl group or a (Z 1) p1 may be substituted by a phenyl group substituted by,
R 30 is, C 1 -C 8 alkyl, optionally substituted by R 35 (C 1 ~C 8) alkyl, optionally substituted by C 3 -C 8 cycloalkyl, R 35 (C 3 ~C 8 ) cycloalkyl, optionally substituted by C 3 -C 8 alkenyl, R 35 (C 3 ~C 8 ) alkenyl, optionally substituted by C 3 -C 8 alkynyl, R 35 (C 3 ~C 8 ) alkynyl, -SH, C 1 -C 6 alkylthio, C 1 -C 6 haloalkylthio, phenylthio, (Z 1) phenylthio substituted by p1, -CHO, -C (O) R 31, -C (O) OR 31 , -C (O) SR 31 , -C (O) NHR 32 , -C (O) N (R 32 ) R 31 , -C (O) C (O) R 31 , -C (O) C ( O) OR 31 , -C (S) R 31 , -C (S) OR 31 , -C (S) SR 31 , -C (S) NHR 32 , -C (S) N (R 32 ) R 31 , -P (O) (OR 24 ) 2 , -P (S) (OR 24 ) 2 , phenyl, phenyl substituted by (Z 1 ) p1 , L-18, L-21, L-25, L-30 ~ Represents L-35, L-45, L-48, L-49 or M,
R 31 is C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 8 cycloalkyl (C 1 -C 4 ) alkyl, C 1 -C 6 alkoxy (C 1 -C 4 ) alkyl, C 1 -C 6 haloalkoxy (C 1 ~C 4) alkyl, C 1 -C 6 alkylthio (C 1 ~C 4) alkyl, C 1 -C 6 haloalkylthio (C 1 ~C 4) alkyl, C 1 -C 6 alkylsulfonyl (C 1 ~C 4) alkyl, C 1 -C 6 haloalkylsulfonyl (C 1 ~C 4) alkyl, cyano (C 1 -C 6) alkyl, C 1 -C 6 alkylcarbonyl (C 1 -C 4) alkyl, C 1 -C 6 haloalkylcarbonyl (C 1 -C 4) alkyl, C 1 -C 6 alkoxycarbonyl (C 1 -C 4) alkyl, di (C 1 -C 6 alkyl) aminocarbonyl (C 1 -C 4) alkyl, tri (C 1 -C 4 alkyl) silyl (C 1 -C 4) alkyl, phenyl (C 1 -C 4) alkyl, (Z 1) phenyl substituted by p1 (C 1 -C 4 ) Alkyl, L- (C 1 -C 4) alkyl, M- (C 1 ~C 4) alkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 halocycloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, phenyl, phenyl, L or M, which is substituted by (Z 1) p1 represents,
R 32 represents a hydrogen atom, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, phenyl or phenyl substituted by (Z 1 ) p 1 , or R 31 and R 32 are taken together By forming a C 2 -C 5 alkylene chain, it indicates that a 3- to 6-membered ring may be formed together with the nitrogen atom to be bonded, and this alkylene chain has one oxygen atom, sulfur atom or nitrogen atom. comprise may, and halogen atom, C 1 -C 6 alkyl group, C 1 -C 6 alkoxy group, a formyl group, C 1 -C 6 alkylcarbonyl group, C 1 -C 6 alkoxycarbonyl group, a phenyl group or (Z 1 ) may be optionally substituted by a phenyl group substituted by p1 ,
R 33 is a hydrogen atom, C 1 -C 8 alkyl, (C 1 -C 8 ) alkyl optionally substituted by R 35 , C 3 -C 8 cycloalkyl, C 3 -C 8 alkenyl, optional by R 35 substituted a (C 3 ~C 8) alkenyl, optionally substituted by C 3 -C 8 alkynyl, or R 35 (C 3 ~C 8) alkynyl,
R 34 is a hydrogen atom, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 8 cycloalkyl (C 1 ~C 4) alkyl, C 1 -C 6 alkoxy (C 1 ~C 4) alkyl, C 1 -C 6 haloalkoxy (C 1 ~C 4) alkyl, C 1 -C 6 alkylthio (C 1 ~C 4) alkyl, C 1 -C 6 haloalkylthio (C 1 ~C 4) alkyl, C 1 -C 6 alkylsulfonyl (C 1 ~C 4) alkyl, C 1 -C 6 haloalkylsulfonyl (C 1 ~C 4) alkyl, phenyl (C 1 ~C 4) alkyl, substituted by (Z 1) p1 phenyl (C 1 ~C 4) represents alkyl, phenyl substituted by phenyl or (Z 1) p1,
R 35 is a halogen atom, cyano, nitro, C 3 -C 8 cycloalkyl, C 3 -C 8 halocycloalkyl, —OH, —OR 36 , —SH, —S (O) r R 36 , —NHR 37 , -N (R 37 ) R 36 , -CHO, -C (O) R 31 , -C (O) OR 31 , -C (O) SR 31 , -C (O) NHR 32 , -C (O) N (R 32 ) R 31 , -C (O) C (O) OR 31 , -CH = NOR 11 , -C (R 9 ) = NOR 11 , -Si (R 13 ) (R 14 ) R 12 ,- Phenyl substituted by P (O) (OR 24 ) 2 , -P (S) (OR 24 ) 2 , -P (phenyl) 2 , -P (O) (phenyl) 2 , phenyl, (Z 1 ) p1 , L or M
R 36 is C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy (C 1 -C 4 ) alkyl, C 1 -C 6 alkylthio (C 1 -C 4 ) alkyl, phenyl ( C 1 -C 4) alkyl, (Z 1) phenyl substituted by p1 (C 1 ~C 4) alkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 halocycloalkyl, C 3 -C 6 alkenyl , C 3 -C 6 haloalkenyl, C 3 -C 8 cycloalkenyl, C 3 -C 8 halocycloalkyl cycloalkenyl, C 3 -C 6 alkynyl, C 3 -C 6 haloalkynyl, -CHO, C 1 ~C 6 alkyl carbonyl, C 1 -C 6 haloalkylcarbonyl, C 1 -C 6 alkoxycarbonyl, C 1 -C 6 haloalkoxycarbonyl, C 1 -C 6 alkylaminocarbonyl, di (C 1 -C 6 alkyl) aminocarbonyl, phenylcarbonyl , (Z 1) phenylcarbonyl substituted by p1, C 1 ~C 6 alkyl amino thiocarboxamide It represents Le, di (C 1 -C 6 alkyl) aminothiocarbonyl, phenyl, phenyl, L or M, which is substituted by (Z 1) p1,
R 37 is a hydrogen atom, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 8 cycloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, C 1 -C 6 alkylcarbonyl , C 1 -C 6 haloalkylcarbonyl, C 1 -C 6 alkoxycarbonyl, C 1 -C 6 haloalkoxycarbonyl, phenoxycarbonyl, phenoxycarbonyl substituted by (Z 1) p1, phenylcarbonyl, by (Z 1) p1 substituted phenylcarbonyl, C 1 -C 6 alkylsulfonyl, C 1 -C 6 haloalkylsulfonyl, phenyl, phenyl substituted by (Z 1) p1, or represents L or M, or R 36 and R 37 Together form a C 2 -C 5 alkylene chain to form a 3- to 6-membered ring together with the nitrogen atom to which the alkylene chain is bonded, wherein the alkylene chain contains an oxygen atom or a sulfur atom. 1 May also do, may be substituted and the halogen atom or a methyl group,
m represents an integer of 0 to 4,
n represents an integer of 0 to 4,
p1 represents an integer of 1 to 5,
p2 represents an integer of 0 to 4,
p3 represents an integer of 0 to 3,
p4 represents an integer of 0 to 2,
p5 represents an integer of 0 or 1,
q1 represents an integer of 0 to 3,
q2 represents an integer of 0 to 5,
q3 represents an integer of 0 to 7,
q4 represents an integer of 0 to 9,
r represents an integer of 0 to 2;
t represents an integer of 0 or 1. ]
[4] In the general formula (2) described in [3] above, W 1 and W 2 represent an oxygen atom,
X represents a halogen atom, nitro, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkylthio, a C 1 -C 4 alkylsulfinyl or C 1 -C 4 alkylsulfonyl, m is 2 Each X may be the same as or different from each other;
Y represents a halogen atom or a C 1 -C 4 alkyl, when n is 2, each Y may be the even or different from each other the same as each other,
R 1 and R 2 represent a hydrogen atom,
R 3 is C 1 -C 8 alkyl, C 1 -C 4 alkylthio (C 1 -C 4 ) alkyl, C 1 -C 4 alkylsulfinyl (C 1 -C 4 ) alkyl or C 1 -C 4 alkylsulfonyl ( C 1 -C 4) alkyl,
R 4 represents C 1 -C 6 alkyl or C 1 -C 6 haloalkyl,
R 5 is phenyl, (Z 1) phenyl substituted by p1, (Z 1) phenoxyphenyl phenyl substituted by p1, (Z 1) pyridyloxy phenyl substituted by p1, L-1~L-4, L-8 to L-13, L-15 to L-23, L-45 to L-52 or L-53,
R 6v represents a hydrogen atom,
Z 1 is a halogen atom, cyano, nitro, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 3 alkylthio (C 1 -C 3 ) alkyl, C 1 -C 3 haloalkylthio (C 1 -C 3) alkyl, C 1 -C 3 alkylsulfinyl (C 1 ~C 3) alkyl, C 1 -C 3 haloalkylsulfinyl (C 1 ~C 3) alkyl, C 1 -C 3 alkylsulfonyl (C 1 -C 3) alkyl, C 1 -C 3 haloalkylsulfonyl (C 1 -C 3) alkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 3 haloalkoxy (C 1 -C 3) halo alkoxy, C 1 -C 6 alkylsulfonyloxy, C 1 -C 6 haloalkylsulfonyloxy, C 1 -C 6 alkylthio, C 1 -C 6 haloalkylthio, C 1 -C 6 alkylsulfinyl, C 1 -C 6 haloalkylsulfinyl , C 1 -C 6 alkylsulfonyl, C 1 -C 6 haloalkylsulfonyl, -C (O) NH 2 The Represents -C (S) NH 2, p1 , when p2, p3 or p4 represents an integer of 2 or more, each Z 1 may be the even or different from each other the same as each other,
Further, when two Z 1 are adjacent to each other, the two adjacent Z 1 are -CF 2 CF 2 O-, -CF 2 OCF 2- , -OCF 2 O-, -OCF 2 CHFO-, -OCF 2 By forming CF 2 O— or —CH═CHCH═CH—, a 5-membered ring or a 6-membered ring may be formed with the carbon atom to which each of the two Z 1 bonds,
R 15 is, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, phenyl (C 1 -C 4) alkyl, (Z 1) phenyl substituted by p1 (C 1 ~C 4) alkyl, phenyl or ( Z 1 ) represents phenyl substituted by p1 ,
m represents an integer of 0 to 2,
n represents an integer of 0 to 2,
q2, q3 and q4 each independently represents one or more selected from a substituted benzanilide compound and a salt thereof each representing an integer of 0 to 2, and 1 of a compound selected from the compound group A described in [1] above An insecticidal, acaricidal, nematicidal, bactericidal or bactericidal composition comprising a species or two or more species.
〔5〕 上記〔1〕記載の一般式(1)で表される置換ベンズアニリド化合物及びその塩より選ばれる1種又は2種以上と、以下の化合物群Bより選ばれる化合物の1種又は2種以上を含有する殺虫、殺ダニ又は殺線虫組成物。 [5] One or two or more kinds selected from the substituted benzanilide compound represented by the general formula (1) described in [1] and a salt thereof, and one or two kinds of compounds selected from the following compound group B An insecticidal, acaricidal or nematicidal composition containing the above.
化合物群B:ジフルベンズロン、フルフェノクスロン、テフルベンズロン、クロルフルアズロン、フェンプロパトリン、シハロトリン、シペルメトリン、ペルメトリン、トラロメトリン、フルバリネート、フェンバレレート、メチダチオン、フェントエート、プロチオホス、アラニカルブ、ニテンピラム、ジノテフラン、チアメトキサム、イミダクロプリド、クロチアニジン、チアクロプリド及びクロルフェナピル。 Compound group B: diflubenzuron, flufenoxuron, teflubenzuron, chlorfluazuron, fenpropatoline, cyhalothrin, cypermethrin, permethrin, tralomethrin, fulvalinate, fenvalerate, methidathion, phentoate, prothiophos, alaniccarb, nitenpyram, dinotepam, thiamethato Imidacloprid, clothianidin, thiacloprid and chlorfenapyr.
〔6〕 上記〔2〕記載の一般式(1)で表される置換ベンズアニリド化合物及びその塩より選ばれる1種又は2種以上と、上記〔5〕記載の化合物群Bより選ばれる化合物の1種又は2種以上を含有する殺虫、殺ダニ又は殺線虫組成物。 [6] One or two or more selected from the substituted benzanilide compound represented by the general formula (1) described in [2] and a salt thereof, and 1 of compounds selected from the compound group B described in [5] An insecticidal, acaricidal or nematicidal composition containing a species or two or more species.
〔7〕 上記〔3〕記載の一般式(2)で表される置換ベンズアニリド化合物及びその塩より選ばれる1種又は2種以上と、請求項5記載の化合物群Bより選ばれる化合物の1種又は2種以上を含有する殺虫、殺ダニ又は殺線虫組成物。 [7] One type or two or more types selected from the substituted benzanilide compound represented by the general formula (2) described in the above [3] and a salt thereof, and one type of compound selected from the compound group B according to claim 5 Or an insecticidal, acaricidal or nematicidal composition containing two or more species.
〔8〕 上記〔4〕記載の一般式(2)で表される置換ベンズアニリド化合物及びその塩より選ばれる1種又は2種以上と、請求項5記載の化合物群Bより選ばれる化合物の1種又は2種以上を含有する殺虫、殺ダニ又は殺線虫組成物。 [8] One or more compounds selected from the substituted benzanilide compounds represented by the general formula (2) according to the above [4] and salts thereof, and one compound selected from the compound group B according to claim 5 Or an insecticidal, acaricidal or nematicidal composition containing two or more species.
〔9〕 上記〔1〕記載の一般式(1)で表される置換ベンズアニリド化合物及びその塩より選ばれる1種又は2種以上と、上記〔1〕記載の化合物群Aより選ばれる化合物の1種又は2種以上を同時に、又は近接して処理することを特徴とする、虫、ダニ、線虫、菌又はバクテリアの防除方法。 [9] One or two or more selected from the substituted benzanilide compound represented by the general formula (1) described in [1] and a salt thereof, and 1 of compounds selected from the compound group A described in [1] A method for controlling insects, ticks, nematodes, fungi, or bacteria, characterized by treating species or two or more species simultaneously or in proximity.
〔10〕 上記〔2〕記載の一般式(1)で表される置換ベンズアニリド化合物及びその塩より選ばれる1種又は2種以上と、上記〔1〕記載の化合物群Aより選ばれる化合物の1種又は2種以上を同時に、又は近接して処理することを特徴とする、虫、ダニ、線虫、菌又はバクテリアの防除方法。 [10] One or two or more types selected from the substituted benzanilide compound represented by the general formula (1) described in [2] above and a salt thereof, and 1 of compounds selected from the compound group A described in [1] above A method for controlling insects, ticks, nematodes, fungi, or bacteria, characterized by treating species or two or more species simultaneously or in proximity.
〔11〕 上記〔3〕記載の一般式(2)で表される置換ベンズアニリド化合物及びその塩より選ばれる1種又は2種以上と、請求項1記載の化合物群Aより選ばれる化合物の1種又は2種以上を同時に、又は近接して処理することを特徴とする、虫、ダニ、線虫、菌又はバクテリアの防除方法。 [11] One or more compounds selected from the substituted benzanilide compounds represented by the general formula (2) described in [3] above and salts thereof, and one compound selected from the compound group A according to claim 1 Alternatively, a method for controlling insects, ticks, nematodes, fungi, or bacteria, wherein two or more species are treated simultaneously or in close proximity.
〔12〕 上記〔4〕記載の一般式(2)で表される置換ベンズアニリド化合物及びその塩より選ばれる1種又は2種以上と、請求項1記載の化合物群Aより選ばれる化合物の1種又は2種以上を同時に、又は近接して処理することを特徴とする、虫、ダニ、線虫、菌又はバクテリアの防除方法。 [12] One or more compounds selected from the substituted benzanilide compounds represented by the general formula (2) described in [4] above and salts thereof, and one compound selected from the compound group A according to claim 1 Alternatively, a method for controlling insects, ticks, nematodes, fungi, or bacteria, wherein two or more species are treated simultaneously or in close proximity.
〔13〕 上記〔1〕記載の一般式(1)で表される置換ベンズアニリド化合物及びその塩より選ばれる1種又は2種以上と、上記〔3〕記載の化合物群Bより選ばれる化合物の1種又は2種以上を同時に、又は近接して処理することを特徴とする、虫、ダニ又は線虫の防除方法。 [13] One or two or more selected from the substituted benzanilide compound represented by the general formula (1) described in [1] and a salt thereof, and 1 of compounds selected from the compound group B described in [3] A method for controlling insects, ticks or nematodes, characterized by treating species or two or more species simultaneously or in close proximity.
〔14〕 上記〔2〕記載の一般式(1)で表される置換ベンズアニリド化合物及びその塩より選ばれる1種又は2種以上と、上記〔3〕記載の化合物群Bより選ばれる化合物の1種又は2種以上を同時に、又は近接して処理することを特徴とする、虫、ダニ又は線虫の防除方法。 [14] One or two or more selected from the substituted benzanilide compound represented by the general formula (1) described in [2] and a salt thereof, and 1 of compounds selected from the compound group B described in [3] A method for controlling insects, ticks or nematodes, characterized by treating species or two or more species simultaneously or in close proximity.
〔15〕 上記〔3〕記載の一般式(2)で表される置換ベンズアニリド化合物及びその塩より選ばれる1種又は2種以上と、請求項1記載の化合物群Aより選ばれる化合物の1種又は2種以上を同時に、又は近接して処理することを特徴とする、虫、ダニ、線虫、菌又はバクテリアの防除方法。 [15] One or more compounds selected from the substituted benzanilide compounds represented by the general formula (2) described in [3] above and salts thereof, and one compound selected from the compound group A according to claim 1 Alternatively, a method for controlling insects, ticks, nematodes, fungi, or bacteria, wherein two or more species are treated simultaneously or in close proximity.
〔16〕 上記〔4〕記載の一般式(2)で表される置換ベンズアニリド化合物及びその塩より選ばれる1種又は2種以上と、請求項1記載の化合物群Aより選ばれる化合物の1種又は2種以上を同時に、又は近接して処理することを特徴とする、虫、ダニ、線虫、菌又はバクテリアの防除方法。 [16] One type or two or more types selected from the substituted benzanilide compound represented by the general formula (2) described in the above [4] and a salt thereof, and one type selected from the compound group A according to claim 1 Alternatively, a method for controlling insects, ticks, nematodes, fungi, or bacteria, wherein two or more species are treated simultaneously or in close proximity.
本発明組成物及び本発明方法は、各種病害虫に対して優れた相乗的防除効果を奏する。 The composition of the present invention and the method of the present invention exhibit an excellent synergistic control effect against various pests.
本発明の一般式(1)及び一般式(2)で表される化合物には、置換基の種類によってはE-体及びZ-体の幾何異性体が存在する場合があるが、本発明の一般式(1)及び一般式(2)で表される化合物はこれらE-体、Z-体又はE-体及びZ-体を任意の割合で含む混合物を包含するものである。また、本発明の一般式(1)及び一般式(2)で表される化合物は、1個又は2個以上の不斉炭素原子の存在に起因する光学活性体が存在するが、本発明の一般式(1)及び一般式(2)で表される化合物は全ての光学活性体又はラセミ体を包含する。さらに、一般式(1)及び一般式(2)で表される本発明化合物においては、R1或いはR2が水素原子であるときに、場合によっては次式で表される互変異性体の存在が考えられるが、本発明の一般式(1)及び一般式(2)で表される化合物はそれらの構造を有する化合物も包含するものである。 The compounds represented by the general formula (1) and the general formula (2) of the present invention may have E-isomers and Z-isomers depending on the type of substituents. The compounds represented by the general formula (1) and the general formula (2) include the E-form, the Z-form, or a mixture containing the E-form and the Z-form in an arbitrary ratio. The compounds represented by the general formula (1) and the general formula (2) of the present invention include optically active substances resulting from the presence of one or more asymmetric carbon atoms. The compounds represented by general formula (1) and general formula (2) include all optically active substances or racemates. Further, in the compounds of the present invention represented by the general formula (1) and the general formula (2), when R 1 or R 2 is a hydrogen atom, the tautomer represented by the following formula may be used in some cases. Although the existence is considered, the compounds represented by the general formula (1) and the general formula (2) of the present invention include compounds having these structures.
本発明の一般式(1)及び一般式(2)で表される化合物のうちで、常法に従って酸付加塩にすることができるものは、例えば、フッ化水素酸、塩酸、臭化水素酸、沃化水素酸等のハロゲン化水素酸の塩、硝酸、硫酸、燐酸、塩素酸、過塩素酸等の無機酸の塩、メタンスルホン酸、エタンスルホン酸、トリフルオロメタンスルホン酸、ベンゼンスルホン酸、p-トルエンスルホン酸等のスルホン酸の塩、ギ酸、酢酸、プロピオン酸、トリフルオロ酢酸、フマール酸、酒石酸、蓚酸、マレイン酸、リンゴ酸、コハク酸、安息香酸、マンデル酸、アスコルビン酸、乳酸、グルコン酸、クエン酸等のカルボン酸の塩又はグルタミン酸、アスパラギン酸等のアミノ酸の塩とすることができる。 Among the compounds represented by the general formulas (1) and (2) of the present invention, those that can be converted into acid addition salts according to a conventional method are, for example, hydrofluoric acid, hydrochloric acid, hydrobromic acid , Hydrohalic acid salts such as hydroiodic acid, inorganic acid salts such as nitric acid, sulfuric acid, phosphoric acid, chloric acid, perchloric acid, methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, Salts of sulfonic acids such as p-toluenesulfonic acid, formic acid, acetic acid, propionic acid, trifluoroacetic acid, fumaric acid, tartaric acid, succinic acid, maleic acid, malic acid, succinic acid, benzoic acid, mandelic acid, ascorbic acid, lactic acid, It can be a salt of a carboxylic acid such as gluconic acid or citric acid, or a salt of an amino acid such as glutamic acid or aspartic acid.
或いは、本発明の一般式(1)及び一般式(2)で表される化合物のうちで、常法に従って金属塩にすることができるものは、例えば、リチウム、ナトリウム、カリウムといったアルカリ金属の塩、カルシウム、バリウム、マグネシウムといったアルカリ土類金属の塩又はアルミニウムの塩とすることができる。 Alternatively, among the compounds represented by the general formula (1) and the general formula (2) of the present invention, those that can be converted into a metal salt according to a conventional method are, for example, alkali metal salts such as lithium, sodium, and potassium. , Alkaline earth metal salts such as calcium, barium and magnesium, or aluminum salts.
本発明組成物に含有される又は本発明方法で使用される一方の有効成分である一般式(1)及び一般式(2)で表される置換ベンズアニリド化合物は、作用性が従来の有機塩素系殺虫剤、有機リン系殺虫剤、カーバメート系殺虫剤およびピレスロイド系殺虫剤などの薬剤とは異なるものであり、既存の殺虫剤に対して抵抗性の発達した害虫に対しても有効である。また、一般式(1)及び一般式(2)で表される置換ベンズアニリド化合物は、ある種の害虫に対しては低薬量で死にいたらしめるとともに残効性も備え、結果的に顕著な防除効果を発揮するものである。しかしながら、いうまでもなくこの一般式(1)及び一般式(2)で表される置換ベンズアニリド化合物のみを使用することで全ての分野の全ての害虫、あるいは病害を防除することは不可能である。 The substituted benzanilide compounds represented by the general formula (1) and the general formula (2), which are one active ingredient contained in the composition of the present invention or used in the method of the present invention, have a conventional organochlorine-based activity. It is different from drugs such as insecticides, organophosphorus insecticides, carbamate insecticides, and pyrethroid insecticides, and is effective against pests that have developed resistance to existing insecticides. In addition, the substituted benzanilide compounds represented by the general formula (1) and the general formula (2) cause a certain amount of pests to die at a low dose and have a residual effect, resulting in remarkable control. It is effective. However, needless to say, it is impossible to control all pests or diseases in all fields by using only the substituted benzanilide compounds represented by the general formulas (1) and (2). .
本発明の一般式(1)で表される置換ベンズアニリド化合物の中で、殺虫、殺ダニ又は殺線虫効果が高く、かつ哺乳動物、魚類および天敵等の有用生物に対して悪影響が少ない点で好ましい化合物は、以下の第1表に示す化合物である。尚、第1表中のGは式G-7a、式G-13a又は式G-71aを表し、 Among the substituted benzanilide compounds represented by the general formula (1) of the present invention, it has a high insecticidal, acaricidal or nematicidal effect and has little adverse effect on useful organisms such as mammals, fish and natural enemies. Preferred compounds are those shown in Table 1 below. In Table 1, G represents Formula G-7a, Formula G-13a, or Formula G-71a,
また、第1表中のi-Prとの記載はイソプロピル基を、Phとの記載はフェニル基をそれぞれ表し、L-36a、L-45g、L-46d又はL-47eはそれぞれ下記の構造を表す。 In Table 1, “i-Pr” represents an isopropyl group, “Ph” represents a phenyl group, and L-36a, L-45g, L-46d, or L-47e each have the following structure. Represent.
〔第1表〕 [Table 1]
―――――――――――――――――――――――――――――――――――――――
No. X R3 G R4 R5 R6
―――――――――――――――――――――――――――――――――――――――
1 I i-Pr G-7a CF3 L-36a -
2 I i-Pr G-7a CF3 L-46d -
3 I i-Pr G-7a CF3 L-47e -
4 I i-Pr G-7a CH3 Ph-4-F -
5 I i-Pr G-7a CF3 Ph-4-Cl -
6 I i-Pr G-7a CF3 Ph-4-SCH3 -
7 I i-Pr G-7a CF3 Ph-4-SO2CH3 -
8 I i-Pr G-7a CF3 Ph-4-NO2 -
9 I i-Pr G-7a CF3 Ph-4-CN -
10 I CH(CH3)CH2SCH3 G-7a CF3 Ph-4-F -
11 I CH(CH3)CH2SCH3 G-7a CF3 Ph-4-Cl -
12 I CH(CH3)CH2SCH3 G-7a CF3 Ph-4-Br -
13 I CH(CH3)CH2SCH3 G-7a CF3 Ph-4-OCF3 -
14 I CH(CH3)CH2SO2CH3 G-7a CF3 Ph-4-F -
15 I CH(CH3)CH2SO2CH3 G-7a CF3 Ph-4-Cl -
16 I CH(CH3)CH2SO2CH3 G-7a CF3 Ph-4-Br -
17 I CH(CH3)CH2SO2CH3 G-7a CF3 Ph-4-OCF3 -
18 I C(CH3)2CH2SCH3 G-7a CF3 Ph-4-F -
19 I C(CH3)2CH2SCH3 G-7a CF3 Ph-4-Cl -
20 I C(CH3)2CH2SCH3 G-7a CF3 Ph-4-Br -
21 I C(CH3)2CH2SCH3 G-7a CF3 Ph-4-OCF3 -
22 I C(CH3)2CH2S(O)CH3 G-7a CF3 Ph-4-OCHF2 -
23 I C(CH3)2CH2SO2CH3 G-7a CF3 Ph-4-F -
24 I C(CH3)2CH2SO2CH3 G-7a CF3 Ph-4-Cl -
25 I C(CH3)2CH2SO2CH3 G-7a CF3 Ph-4-Br -
26 I C(CH3)2CH2SO2CH3 G-7a CF3 Ph-4-OCF3 -
27 CF3 i-Pr G-7a CF3 Ph-4-SO2CH3 -
28 I i-Pr G-7a Ph-4-Cl OCH3 -
29 I i-Pr G-7a Ph-4-OCF3 CH3 -
30 I i-Pr G-7a Ph-4-OCF2CHFCF3 CH3 -
31 I i-Pr G-7a Ph-4-OCF2CHFOCF2CF2CF3 CH3 -
32 I i-Pr G-7a Ph-4-O(L-45g) CH3 -
33 I CH(CH3)CH2SCH3 G-7a Ph-4-OCF2CHFOCF2CF2CF3 CH3 -
34 I CH(CH3)CH2SO2CH3 G-7a Ph-4-OCF3 CH3 -
35 I i-Pr G-13a CF3 Ph-4-SO2CH3 -
36 I CH(CH3)CH2SCH3 G-71a Ph-4-Cl - F
37 I CH(CH3)CH2SCH3 G-71a Ph-4-CF3 - F
38 I CH(CH3)CH2SCH3 G-71a Ph-4-OCF3 - F
39 I CH(CH3)CH2SCH3 G-71a Ph-4-OCF2Br - F
40 I CH(CH3)CH2SCH3 G-71a Ph-3,4-Cl2 - F
41 I CH(CH3)CH2SCH3 G-71a Ph-4-CF3 - Cl
42 I CH(CH3)CH2SCH3 G-71a Ph-4-OCF3 - Cl
43 I CH(CH3)CH2SO2CH3 G-71a Ph-4-Cl - F
44 I CH(CH3)CH2SO2CH3 G-71a Ph-4-CF3 - F
45 I CH(CH3)CH2SO2CH3 G-71a Ph-4-OCF3 - F
46 I CH(CH3)CH2SO2CH3 G-71a Ph-4-OCF2Br - F
47 I CH(CH3)CH2SO2CH3 G-71a Ph-3,4-Cl2 - F
48 I CH(CH3)CH2SO2CH3 G-71a Ph-4-OCF3 - Cl
49 I C(CH3)2CH2SCH3 G-71a Ph-4-Cl - F
50 I C(CH3)2CH2SCH3 G-71a Ph-4-CF3 - F
51 I C(CH3)2CH2SCH3 G-71a Ph-4-OCF3 - F
52 I C(CH3)2CH2SCH3 G-71a Ph-3,4-Cl2 - F
53 I C(CH3)2CH2SO2CH3 G-71a Ph-4-Cl - F
54 I C(CH3)2CH2SO2CH3 G-71a Ph-4-OCF3 - F
55 I C(CH3)2CH2SO2CH3 G-71a Ph-3,4-Cl2 - F
―――――――――――――――――――――――――――――――――――――――
本発明の一般式(2)で表される置換ベンズアニリド化合物の中で、殺虫、殺ダニ又は殺線虫効果が高く、かつ哺乳動物、魚類および天敵等の有用生物に対して悪影響が少ない点で好ましい化合物は、以下の第2表に示す化合物である。尚、第2表中のi-Prとの記載はイソプロピル基を、Phとの記載はフェニル基をAcとの記載はアセチル基をそれぞれ表し、L-45g又はL-45hはそれぞれ下記の構造を表す。
―――――――――――――――――――――――――――――――――――――――
No. XR 3 GR 4 R 5 R 6
―――――――――――――――――――――――――――――――――――――――
1 I i-Pr G-7a CF 3 L-36a-
2 I i-Pr G-7a CF 3 L-46d-
3 I i-Pr G-7a CF 3 L-47e-
4 I i-Pr G-7a CH 3 Ph-4-F-
5 I i-Pr G-7a CF 3 Ph-4-Cl-
6 I i-Pr G-7a CF 3 Ph-4-SCH 3-
7 I i-Pr G-7a CF 3 Ph-4-SO 2 CH 3-
8 I i-Pr G-7a CF 3 Ph-4-NO 2-
9 I i-Pr G-7a CF 3 Ph-4-CN-
10 I CH (CH 3 ) CH 2 SCH 3 G-7a CF 3 Ph-4-F-
11 I CH (CH 3 ) CH 2 SCH 3 G-7a CF 3 Ph-4-Cl-
12 I CH (CH 3 ) CH 2 SCH 3 G-7a CF 3 Ph-4-Br-
13 I CH (CH 3 ) CH 2 SCH 3 G-7a CF 3 Ph-4-OCF 3-
14 I CH (CH 3 ) CH 2 SO 2 CH 3 G-7a CF 3 Ph-4-F-
15 I CH (CH 3 ) CH 2 SO 2 CH 3 G-7a CF 3 Ph-4-Cl-
16 I CH (CH 3 ) CH 2 SO 2 CH 3 G-7a CF 3 Ph-4-Br-
17 I CH (CH 3 ) CH 2 SO 2 CH 3 G-7a CF 3 Ph-4-OCF 3-
18 IC (CH 3 ) 2 CH 2 SCH 3 G-7a CF 3 Ph-4-F-
19 IC (CH 3 ) 2 CH 2 SCH 3 G-7a CF 3 Ph-4-Cl-
20 IC (CH 3 ) 2 CH 2 SCH 3 G-7a CF 3 Ph-4-Br-
21 IC (CH 3 ) 2 CH 2 SCH 3 G-7a CF 3 Ph-4-OCF 3-
22 IC (CH 3 ) 2 CH 2 S (O) CH 3 G-7a CF 3 Ph-4-OCHF 2-
23 IC (CH 3 ) 2 CH 2 SO 2 CH 3 G-7a CF 3 Ph-4-F-
24 IC (CH 3 ) 2 CH 2 SO 2 CH 3 G-7a CF 3 Ph-4-Cl-
25 IC (CH 3 ) 2 CH 2 SO 2 CH 3 G-7a CF 3 Ph-4-Br-
26 IC (CH 3 ) 2 CH 2 SO 2 CH 3 G-7a CF 3 Ph-4-OCF 3-
27 CF 3 i-Pr G-7a CF 3 Ph-4-SO 2 CH 3-
28 I i-Pr G-7a Ph-4-Cl OCH 3-
29 I i-Pr G-7a Ph-4-OCF 3 CH 3-
30 I i-Pr G-7a Ph-4-OCF 2 CHFCF 3 CH 3-
31 I i-Pr G-7a Ph-4-OCF 2 CHFOCF 2 CF 2 CF 3 CH 3-
32 I i-Pr G-7a Ph-4-O (L-45g) CH 3-
33 I CH (CH 3 ) CH 2 SCH 3 G-7a Ph-4-OCF 2 CHFOCF 2 CF 2 CF 3 CH 3-
34 I CH (CH 3 ) CH 2 SO 2 CH 3 G-7a Ph-4-OCF 3 CH 3-
35 I i-Pr G-13a CF 3 Ph-4-SO 2 CH 3-
36 I CH (CH 3 ) CH 2 SCH 3 G-71a Ph-4-Cl-F
37 I CH (CH 3 ) CH 2 SCH 3 G-71a Ph-4-CF 3 -F
38 I CH (CH 3 ) CH 2 SCH 3 G-71a Ph-4-OCF 3 -F
39 I CH (CH 3 ) CH 2 SCH 3 G-71a Ph-4-OCF 2 Br-F
40 I CH (CH 3 ) CH 2 SCH 3 G-71a Ph-3,4-Cl 2 -F
41 I CH (CH 3 ) CH 2 SCH 3 G-71a Ph-4-CF 3 -Cl
42 I CH (CH 3 ) CH 2 SCH 3 G-71a Ph-4-OCF 3 -Cl
43 I CH (CH 3 ) CH 2 SO 2 CH 3 G-71a Ph-4-Cl-F
44 I CH (CH 3 ) CH 2 SO 2 CH 3 G-71a Ph-4-CF 3 -F
45 I CH (CH 3 ) CH 2 SO 2 CH 3 G-71a Ph-4-OCF 3 -F
46 I CH (CH 3 ) CH 2 SO 2 CH 3 G-71a Ph-4-OCF 2 Br-F
47 I CH (CH 3 ) CH 2 SO 2 CH 3 G-71a Ph-3,4-Cl 2 -F
48 I CH (CH 3 ) CH 2 SO 2 CH 3 G-71a Ph-4-OCF 3 -Cl
49 IC (CH 3 ) 2 CH 2 SCH 3 G-71a Ph-4-Cl-F
50 IC (CH 3 ) 2 CH 2 SCH 3 G-71a Ph-4-CF 3 -F
51 IC (CH 3 ) 2 CH 2 SCH 3 G-71a Ph-4-OCF 3 -F
52 IC (CH 3 ) 2 CH 2 SCH 3 G-71a Ph-3,4-Cl 2 -F
53 IC (CH 3 ) 2 CH 2 SO 2 CH 3 G-71a Ph-4-Cl-F
54 IC (CH 3 ) 2 CH 2 SO 2 CH 3 G-71a Ph-4-OCF 3 -F
55 IC (CH 3 ) 2 CH 2 SO 2 CH 3 G-71a Ph-3,4-Cl 2 -F
―――――――――――――――――――――――――――――――――――――――
Among the substituted benzanilide compounds represented by the general formula (2) of the present invention, it has a high insecticidal, acaricidal or nematicidal effect and has little adverse effect on useful organisms such as mammals, fish and natural enemies. Preferred compounds are those shown in Table 2 below. In Table 2, “i-Pr” represents an isopropyl group, “Ph” represents a phenyl group, “Ac” represents an acetyl group, and L-45g or L-45h represents the following structure, respectively. Represent.
〔第2表〕 [Table 2]
―――――――――――――――――――――――――――――――――――――――
No. R3 R4 R5 R6v
―――――――――――――――――――――――――――――――――――――――
56 i-Pr CH3 L-45g H
57 i-Pr CF3 L-45g H
58 i-Pr CF3 Ph-4-OCF3 H
59 i-Pr CF3 Ph-4-O(L-45h) H
60 i-Pr CF3 Ph(-3-OCF2CF2O-4-) H
61 i-Pr CF3 Ph-4-Cl Ac
62 CH(CH3)CH2SCH3 CF3 Ph-4-Cl H
63 CH(CH3)CH2SCH3 CF3 Ph-4-CF3 H
64 CH(CH3)CH2SCH3 CF3 Ph-4-OCF3 H
65 CH(CH3)CH2SCH3 CF3 Ph-4-OCF2CHFCF3 H
66 CH(CH3)CH2SCH3 CF3 Ph-2-F-4-Cl H
67 CH(CH3)CH2SCH3 CF3 Ph-3,4-Cl2 H
68 CH(CH3)CH2SCH3 CF3 Ph-3-Cl-4-OCF3 H
69 CH(CH3)CH2SCH3 CF3 Ph(-3-OCF2O-4-) H
70 CH(CH3)CH2SCH3 CF3 Ph(-3-OCF2CF2O-4-) H
71 CH(CH3)CH2SCH3 CF3 CF2O(Ph-4-Cl) H
72 CH(CH3)CH2SCH3 CF3 CH=CH(Ph-4-OCF3) H
73 CH(CH3)CH2SO2CH3 CF3 Ph-4-CF3 H
74 CH(CH3)CH2SO2CH3 CF3 Ph-4-OCF3 H
75 CH(CH3)CH2SO2CH3 CF3 Ph-4-OCF2Br H
76 CH(CH3)CH2SO2CH3 CF3 Ph-4-OCF2CHFOCF3 H
77 CH(CH3)CH2SO2CH3 CF3 Ph(-3-OCF2CF2O-4-) H
78 C(CH3)2CH2SCH3 CF3 Ph-4-OCF3 H
79 C(CH3)2CH2SO2CH3 CF3 Ph-4-OCF3 H
―――――――――――――――――――――――――――――――――――――――
また、一般式(1)及び一般式(2)で表される置換ベンズアニリド化合物と共に用いられる、もう一方の有効成分化合物は、殺虫、殺ダニ、殺線虫、殺菌又は殺バクテリア化合物として公知のものであり、以下の第3表に化合物No.と共に示す。そして、これらの化合物には抵抗性害虫あるいは耐性菌の出現、更に殺虫殺菌スペクトラムや残効性の不足により、薬剤の散布薬量、散布回数が増加する傾向にあり、防除効果のみならず、人畜あるいは水生生物に対する危険性の増加など、環境安全性の面からも改善が求められているものもある。
―――――――――――――――――――――――――――――――――――――――
No. R 3 R 4 R 5 R 6v
―――――――――――――――――――――――――――――――――――――――
56 i-Pr CH 3 L-45g H
57 i-Pr CF 3 L-45g H
58 i-Pr CF 3 Ph-4-OCF 3 H
59 i-Pr CF 3 Ph-4-O (L-45h) H
60 i-Pr CF 3 Ph (-3-OCF 2 CF 2 O-4-) H
61 i-Pr CF 3 Ph-4-Cl Ac
62 CH (CH 3 ) CH 2 SCH 3 CF 3 Ph-4-Cl H
63 CH (CH 3 ) CH 2 SCH 3 CF 3 Ph-4-CF 3 H
64 CH (CH 3 ) CH 2 SCH 3 CF 3 Ph-4-OCF 3 H
65 CH (CH 3 ) CH 2 SCH 3 CF 3 Ph-4-OCF 2 CHFCF 3 H
66 CH (CH 3 ) CH 2 SCH 3 CF 3 Ph-2-F-4-Cl H
67 CH (CH 3 ) CH 2 SCH 3 CF 3 Ph-3,4-Cl 2 H
68 CH (CH 3 ) CH 2 SCH 3 CF 3 Ph-3-Cl-4-OCF 3 H
69 CH (CH 3 ) CH 2 SCH 3 CF 3 Ph (-3-OCF 2 O-4-) H
70 CH (CH 3 ) CH 2 SCH 3 CF 3 Ph (-3-OCF 2 CF 2 O-4-) H
71 CH (CH 3 ) CH 2 SCH 3 CF 3 CF 2 O (Ph-4-Cl) H
72 CH (CH 3 ) CH 2 SCH 3 CF 3 CH = CH (Ph-4-OCF 3 ) H
73 CH (CH 3 ) CH 2 SO 2 CH 3 CF 3 Ph-4-CF 3 H
74 CH (CH 3 ) CH 2 SO 2 CH 3 CF 3 Ph-4-OCF 3 H
75 CH (CH 3 ) CH 2 SO 2 CH 3 CF 3 Ph-4-OCF 2 Br H
76 CH (CH 3 ) CH 2 SO 2 CH 3 CF 3 Ph-4-OCF 2 CHFOCF 3 H
77 CH (CH 3 ) CH 2 SO 2 CH 3 CF 3 Ph (-3-OCF 2 CF 2 O-4-) H
78 C (CH 3 ) 2 CH 2 SCH 3 CF 3 Ph-4-OCF 3 H
79 C (CH 3 ) 2 CH 2 SO 2 CH 3 CF 3 Ph-4-OCF 3 H
―――――――――――――――――――――――――――――――――――――――
The other active ingredient compound used together with the substituted benzanilide compound represented by the general formula (1) and the general formula (2) is known as an insecticidal, acaricidal, nematicidal, bactericidal or bactericidal compound. It is shown together with compound No. in Table 3 below. These compounds tend to increase the amount of sprayed medicine and the number of spraying due to the emergence of resistant pests or resistant bacteria, and the lack of insecticidal sterilization spectrum and residual effects. There are also cases where improvement is required from the aspect of environmental safety, such as an increase in the risk to aquatic organisms.
〔第3表〕
――――――――――――――――――――――――
No. 化合物名
――――――――――――――――――――――――
a アシベンゾラル−S−メチル
b アシルアミノベンザミド
c アンバム
d アムプロピルホス
e アニラジン
f アザコナゾール
g アゾキシストロビン
h ベナラキシル
i ベノダニル
j ベノミル
k ベンチアゾール
l ベンザマクリル
m ビナパクリル
n ビフェニル
o ビテルタノール
p ベトキサジン
q ボルドー液
r ブラストサイジン−S
s ブロモコナゾール
t ブピリメート
u ブチオベート
v カルシウムポリスルフィド
w キャプタフォール
x キャプタン
y カッパーオキシクロリド
z カルプロパミド
aa カルベンダジン
ab カルボキシン
ac トリフロキシストロビン
ad キノメチオネート
ae クロベンチアゾン
af クロルフェナゾール
ag クロロネブ
ah クロロタロニル
ai クロゾリネート
aj クフラネブ
ak シモキサニル
al シプロコナゾール
am シプロジニル
an シプロフラム
ao ダゾメット
ap デバカルブ
aq ジクロロフェン
ar ジクロブトラゾール
as ジクロフラニド
at ジクロメジン
au ジクロラン
av ジエトフェンカルブ
aw ジクロシメット
ax ジフェノコナゾール
ay ジフルメトリン
az ジメチリモール
ba ジメトモルフ
bb ジニコナゾール
bc ジニコナゾール−M
bd ジノカップ
be ジフェニルアミン
bf ジピリチオン
bg ジタリムホス
bh ジチアノン
bi ドデモルフ
bj ドジン
bk ドラゾクソロン
bl エデフェノホス
bm エポキシコナゾール
bn エタコナゾール
bo エチリモル
bp エトリジアノール
bq ファモキサゾン
br フェナリモル
bs フェブコナゾール
bt フェナミドン
bu フェンダゾスラム
bv フェンフラム
bw フェンヘキサミド
bx フェンピクロニル
by フェンプロピジン
bz フェンプロピモルフ
ca フェンチン
cb フェルバン
cc フェリムゾン
cd フルアジナム
ce フルジオキソニル
cf フルオロイミド
cg フルキンコナゾール
ch フルシラゾール
ci フルスルファミド
cj フルトラニル
ck フルトリアフォール
cl フォルペット
cm フォセチル−アルミニウム
cn フベリダゾール
co フララキシル
cp フラメトピル
cq グアザチン
cr ヘキサクロロベンゼン
cs ヘキサコナゾール
ct ヒメキサゾール
cu イマザリル
cv イミベンコナゾール
cw イミノクタジン
cx イプコナゾール
cy イプロベンホス
cz イプロジオン
da イソプロチオラン
db イプロバリカルブ
dc カスガマイシン
dd クレソキシム−メチル
de マンカッパー
df マンコゼブ
dg マンネブ
dh メパニピリム
di メプロニル
dj メタラキシル
dk メトコナゾール
dl メタスルホカルブ
dm メチラム
dn メトミノストロビン
do ミクロブタニル
dp MTF−753
dq ナバム
dr ニッケルビス(ジメチルジチオカーバメート)
ds ニトロタール−イソプロピル
dt ヌアリモル
du フェノキサニル
dv オクチリノン
dw オフレース
dx オキサジキシル
dy オキシカルボキシン
dz オキポコナゾールフマール酸塩
ea ペフラゾエート
eb ペンコナゾール
ec ペンシクロン
ed フタライド
ee ピペラリン
ef ポリオキシン
eg 炭酸水素カリウム
eh プロベナゾール
ei プロクロラズ
ej プロシミドン
ek プロパモカルブ塩酸塩
el プロピコナゾール
em プロピネブ
en ピラゾホス
eo ピリフェノックス
ep ピリメタニル
eq ピロキュロン
er キノメチオネート
es キノキシフェン
et キントゼン
eu ゾキサミド
ev 炭酸水素ナトリウム
ew 次亜塩素酸ナトリウム
ex 硫黄
ey スピロキサミン
ez テブコナゾール
fa テクナゼン
fb テトラコナゾール
fc チアベンダゾール
fd チアジアジン
fe チフルザミド
ff チオファネート−メチル
fg チラム
fh トルクロホス−メチル
fi トリルフラニド
fj トリアジメホン
fk トリアジメノール
fl トリアゾキシド
fm トリシクラゾール
fn トリデモルフ
fo トリフルミゾール
fp トリホリン
fq トリチコナゾール
fr バリダマイシン
fs ビンクロゾリン
ft 硫酸亜鉛
fu ジネブ
fv ジラム
fw シイタケ菌糸体抽出物
fx ストレプトマイシン
fy テクロフタラム
fz オキシテトラサイクリン
ga オキソリニックアシド
gb アルドキシカルブ
gc カズサホス
gd フォスチアゼート
ge フォスチエタン
gf オキサミル
gg フェナミホス
gh アセキノシル
gi アミトラズ
gj ビフェナゼート
gk ブロモプロピレート
gl チノメチオネート
gm クロロベンジラート
gn クロフェンテジン
go サイヘキサチン
gp ジコフォール
gq ジエノクロール
gr エトキサゾール
gs フェナザキン
gt フェンブタチンオキシド
gu フェンプロパトリン
gv フェンプロキシメート
gw ハルフェンプロックス
gx ヘキシチアゾックス
gy ミルベメクチン
gz プロパルギット
ha ピリダベン
hb ピリミジフェン
hc テブフェンピラド
hd アバメクチン
he アセフェート
hf アセタミピリド
hg アルディカルブ
hh アレスリン
hi アジンホス−メチル
hj ベンジオカルブ
hk ベンフラカルブ
hl ベンスルタップ
hm ビフェントリン
hn ブプロフェジン
ho ブトカルボキシン
hp カルバリル
hq カルボフラン
hr カルボスルファン
hs カルタップ
ht クロルフェナピル
hu クロルピリホス
hv クロルフェンビンホス
hw クロルフルアズロン
hx クロチアニジン
hy クロマフェノジド
hz クロピリホス−メチル
ia シクロプロトリン
ib シフルトリン
ic ベータ−シフルトリン
id シペルメトリン
ie シロマジン
if シハロトリン
ig ラムダ−シハロトリン
ih デルタメトリン
ii ジアフェンチウロン
ij ダイアジノン
ik ジアクロデン
il ジフルベンズロン
im ジメチルビンホス
in ジオフェノラン
io ジスルフォトン
ip ジメトエート
iq エマメクチンベンゾエート
ir EPN
is エスフェンバレレート
it エチオフェンカルブ
iu エチプロール
iv エトフェンプロックス
iw エトリムホス
ix フェニトロチオン
iy フェノブカルブ
iz フェノキシカーブ
ja フェンバレレート
jb フィプロニル
jc フルアクリピリム
jd フルシトリネート
je フルフェノクスロン
jf フルフェンプロックス
jg タウ−フルバリネート
jh ホノホス
ji フォルメタネート
jj フォルモチオン
jk フラチオカルブ
jl ハロフェノジド
jm ヘキサフルムロン
jn ヒドラメチルノン
jo イミダクロプリド
jp イソフェンホス
jq インドキサカルブ
jr イソプロカルブ
js イソキサチオン
jt ルフェヌウロン
ju マラチオン
jv メタルデヒド
jw メタミドホス
jx メチダチオン
jy メタクリホス
jz メタルカルブ
ka メソミル
kb メソプレン
kc メトキシクロール
kd メトキシフェノジド
ke モノクロトホス
kf ムスカルーレ
kg ジノテフラン
kh ニテンピラム
ki オメトエート
kj オキシデメトン−メチル
kk パラチオン
kl パラチオン−メチル
km ペルメトリン
kn フェントエート
ko フォキシム
kp ホレート
kq ホサロン
kr ホスメット
ks ホスファミドン
kt ピリミカルブ
ku ピリミホス−メチル
kv プロフェノホス
kw プロトリフェンブト
kx ピメトロジン
ky ピラクロホス
kz ピリプロキシフェン
la ロテノン
lb スルプロホス
lc シラフルオフェン
ld スピノサド
le スルホテップ
lf テブフェノジド
lg テフルベンズロン
lh テフルトリン
li テルブホス
lj テトラクロロビンホス
lk チアクロプリド
ll チオシクラム
lm チオジカルブ
ln チアメトキサム
lo チオファノックス
lp チオメトン
lq トルフェンピラド
lr トラロメトリン
ls トリクロルホン
lt トリアズロン
lu トリフルムロン
lv バミドチオン
lw エチオン
lx アシペタックス
ly アルジモルフ
lz アリルアルコール
ma アウレロファンジン
mb アジチラム
mc バリウムポリサルファイド
md ベンキノックス
me ベンタルロン
mf ベンチアバリカルブ
mg ベンザルコニウムクロライド
mh ベンズアモルフ
mi ベンゾハイドロキサミックアシド
mj ビチオノール
mk ブチルアミン
ml カルバモルフ
mm カルボン
mn チェシュントミクスチャ
mo クロラニフォルメタン
mp クロラニル
mq クロロピクリン
mr クロロキノックス
ms クリムバゾール
mt クロトリマゾール
mu カッパーアセテイト
mv 塩基性炭酸銅
mw 水酸化第二銅
mx カッパーナフタレン
my カッパーオルアイト
mz 硫酸銅
na 塩基性硫酸銅
nb カッパージンククロメイト
nc クレゾール
nd クプロバム
ne シアゾファミド
nf シクラフルアミド
ng シクロヘキシミド
nh シフルフェナミド
ni サイペンダゾール
nj デービーシーピー
nk デカフェンチン
nl デハイドロアセテイト
nm ジクロン
nn ジクロゾリン
no ジエチルピロカルボネイト
np ジモキシストロビン
nq ジノブトン
nr ジノカップ−4
ns ジノカップ−6
nt ジノクトン
nu ジノスルフォン
nv ジノテルボン
nw ジノスルフィラム
nx デーエヌオーシー
ny エテム
nz エトキシキン
oa エチルマーキュリーアセテイト
ob エチルマーキュリーブロマイド
oc 塩化メチル水銀
od エチルマーキュリーフォスフェイト
oe フェナミノスルフ
of フェナパニル
og フェニトロパン
oh フルメトバー
oi フルモルフ
oj フルオトリマゾール
ok フルオキサストロビン
ol フルカルバニル
om フルコナゾール
on フルコナゾール−シス
oo フルメシクロックス
op フロファネート
oq グリオジン
or グリセオフルビン
os ハラクリネイト
ot ヘキサクロロブタジエン
ou ヘキシルチオフォス
ov ハイドロキシキノリン サルフェイト
ow イソバレジオン
ox メベニル
oy メカルビンジド
oz 塩化第二水銀
pa 酸化第二水銀
pb 塩化第一水銀
pc メタラキシル−M
pd メタム
pe メタロキソロン
pf メスフロキサム
pg メチルブロマイド
ph メチルイソチアシアネイト
pi メチルマーキュリーベンゾエイト
pj メチルマーキュリージシアンジアミド
pk メトラフェノン
pl メトスルフォバックス
pm ミルネブ
pn ミクロゾリン
po メトキシメチルマーキュリークロライド
pp ナタマイシン
pq ニコビフェン
pr ニトロスチレン
ps オーシーエイチ
pt オリサストロビン
pu 有機銅
pv ペンタクロロフェノール
pw 尿素フェニル水銀
px フェニルマーキュリーアセテイト
py フェニルマーキュリークロライド
pz フェニルマーキュリーナイトレイト
qa フェニルマーキュリーサリシレイト
qb フォスジフェン
qc ピコキシストロビン
qd ポリカルバメイト
qe ポリオクソリム
qf ポタシウムアザイド
qg ポタシウムポリサルファイド
qh プロキナジド
qi プロチオカルブ
qj プロチオコナゾール
qk ピラカルボリド
ql ピラクロストロビン
qm ピリジニトリル
qn ピロキシクロア
qo ピロキシサルファ
qp フェニルフェノール
qq キナセトール
qr キナザミド
qs キンコナゾール
qt ラベンザゾール
qu サリチルアニリド
qv シルチオファム
qw シメコナゾール
qx アジ化ナトリウム
qy ソジウムオルトペニルペノキサイド
qz ソジウムペンタクロロフェノキサイド
ra ソジウムポリサルファイド
rb テーシーエムテービー
rc テコラム
rd チアジフルア
re チシオフェン
rf チオクロルフェンフィム
rg チオメルサム
rh チオファネイト
ri チオキノックス
rj チアジニル
rk チオキシミド
rl トリマーキュリアセテイト
rm トリアミフォス
rn トリアリモル
ro トリアズブチル
rp トリブチルチンオキサイド
rq トリクルアミド
rr ザリルアミド
rs ジンクナフテネイト
rt ブロノポル
ru フォルムアルデハイド
rv ニトラピリン
rw チオメルサル
rx イマニン
ry ルバビリン
rz ジクロフェンチオン
sa DSP
sb エトプロホス
sc フェンスルホチオン
sd イサミドホス
se イサゾホス
sf チオナジン
sg アクリナトリン
sh フェノチオカルブ
si スピロディクロフェン
sj アラニカルブ
sk バチルスチューリンゲシス
sl フェンチオン
sm フルバリネート
sn オキシデプロポス
so プロチオホス
sp プロパホス
sq ピリダリル
sr スピロメシフェン
――――――――――――――――――――――――
本発明組成物及び本発明方法の特徴は、第1に、各薬剤の単独での施用の場合に比べ、その殺虫、殺ダニ、殺線虫、殺菌又は殺バクテリア効力が明らかに増強されるとともに、即効的な殺虫、殺ダニ、殺線虫、殺菌又は殺バクテリア効果が付与されることである。第2に、既存の殺虫、殺ダニ、殺線虫、殺菌又は殺バクテリア剤に観られない広い殺虫、殺ダニ、殺線虫、殺菌又は殺バクテリアスペクトラムや、長い残効性が誘導されることである。第3に、各薬剤を単独で使用した場合に比べ、投下薬量を低下させうることである。
[Table 3]
――――――――――――――――――――――――
No. Compound name
――――――――――――――――――――――――
a Acibenzoral-S-methyl
b Acylaminobenzamide
c Ambum
d Ampropylphos
e Anilazine
f Azaconazole
g Azoxystrobin
h Benalaxyl
i benodanyl
j Benomyl
k Bench azole
l Benzmakrill
m Binapacryl
n Biphenyl
o Vitertanol
p Betoxazine
q Bordeaux fluid
r Blastsaidin-S
s Bromoconazole
t Bupirimate
u Buthiobate
v Calcium polysulfide
w Captor Fall
x Captan
y Copper oxychloride
z Carpropamide
aa Carbendazine
ab carboxin
ac trifloxystrobin
ad Kinomethionate
ae Cloventil Azone
af chlorphenazole
ag chloroneb
ah chlorothalonil
ai crozolinate
aj Kfulaneb
ak simoxanil
al cyproconazole
am cyprodinil
ancyprofram
ao dazomet
ap debacarb
aq dichlorophen
ar Diclobutrazol
as diclofuranide
at Dichromedin
au dichlorane
av dietofencarb
aw dicrocimet
ax difenoconazole
ay diflumethrin
az Zimetili Mall
ba dimethomorph
bb diniconazole
bc diniconazole-M
bd zino cup
be diphenylamine
bf dipyrithione
bg Ditalimphos
bh dithianon
bi dodemorph
bj dojin
bk drazoxolone
bl edefenophos
bm epoxyconazole
bn etaconazole
bo etilimol
bp Etridianol
bq famoxazone
br phenalimol
bs febuconazole
bt fenamidon
bu fendazo slam
bv fenfram
bw Fenhexamide
bx fenpiclonil
by Fenpropidin
bz Fenpropimorph
ca fentin
cb felvin
cc ferrimson
cd full azinam
ce Fludioxonil
cf fluoroimide
cg Fluquinconazole
ch flusilazole
ci fursulfamide
cj flutolanil
ck Furtoria Fall
cl folpet
cm fosetyl-aluminum
cn fuberidazole
co flaxil
cp Frametopil
cq guazatine
cr hexachlorobenzene
cs hexaconazole
ct Himexazole
cu imazaril
cv imibenconazole
cw iminotadine
cx ipconazole
cy iprobenphos
cz iprodione
da Isoprothiolane
db iprovaricarb
dc kasugamycin
dd Cresoxime-methyl
de Mankappa
df mancozeb
dg mannebu
dh mepanipyrim
di mepronil
dj metalaxyl
dk metconazole
dl metasulfocarb
dm Methylam
dn metminostrobin
do microbutanyl
dp MTF-753
dq nabam
dr nickel bis (dimethyldithiocarbamate)
ds nitrotar-isopropyl
dt nuarimol
du phenoxanyl
dv octirinon
dw off race
dx oxadixyl
dy oxycarboxin
dz okipoconazole fumarate
ea pefazoate
eb penconazole
ec pencyclon
ed phthalide
ee piperalin
ef polyoxin
eg Potassium bicarbonate
eh probenazole
ei prochloraz
ej prosimidone
ek propamocarb hydrochloride
el propiconazole
em propineb
en pyrazofos
eo pirifenox
ep pyrimethanil
eq pirocuron
er Kinomethionate
es Quinoxifen
et Kintozen
eu zoxamide
ev sodium bicarbonate
ew sodium hypochlorite
ex sulfur
ey spiroxamine
ez tebuconazole
fa technazen
fb tetraconazole
fc thiabendazole
fd thiadiazine
fe Tifluzamide
ff thiophanate-methyl
fg chiram
fh Torquelophos-methyl
fi trillfuranide
fj triazimehon
fk triazimenol
fl triazoxide
fm tricyclazole
fn tridemorph
fo triflumizole
fp triforin
fq triticonazole
fr validamycin
fs Vinclozoline
ft Zinc sulfate
fu Geneva
fv jiram
fw shiitake mycelium extract
fx streptomycin
fy Teclophthalam
fz oxytetracycline
ga oxolinic acid
gb aldoxicarb
gc kazusahos
gd fostiazate
ge Fostietan
gf oxamyl
gg Phenamifos
gh Acekinosyl
gi Amitraz
gj bifenazate
gk Bromopropylate
gl Chinomethionate
gm chlorobenzilate
gn clofentezin
go cyhexatin
gp Zicofall
gq dienochlor
gr etoxazole
gs phenazaquin
gt phenbutatin oxide
gu fenpropatoline
gv phen proxymate
gw Halfen Prox
gx hexithiazox
gy milbemectin
gz propargit
ha pyridaben
hb pyrimidifene
hc tebufenpyrad
hd Abamectin
he acephate
hf Acetamipiride
hg aldicarb
hh Areslin
hi azinephos-methyl
hj Bengiocarb
hk benfracarb
hl Bensultap
hm bifenthrin
hn Buprofezin
ho Butocarboxylin
hp carbaryl
hq carbofuran
hr Carbosulfur
hs kultap
ht chlorfenapyr
hu Chlorpyrifos
hv chlorfenvinphos
hw Chlorfluazuron
hx clothianidin
hy chromafenozide
hz Clopyrifos-methyl
ia Cycloproton
ib sifluthrin
ic beta-cyfluthrin
id Cypermethrin
ie cyromazine
if Cihalothrin
ig lambda-cyhalothrin
ih Deltamethrin
ii Diafenthiuron
ij Diazinon
ik Diacloden
il diflubenzuron
im dimethylvinphos
in Geofenolan
io disulfone
ip dimethoate
iq emamectin benzoate
ir EPN
is esfenvalerate
it Ethiophene Carb
iu etiprol
iv etofenprox
iw Etrimhos
ix Fenitrothion
iy fenocarb
iz phenoxy curve
ja fenvalerate
jb fipronil
jc Full Acripyrim
jd flucitrate
je Fulfenoxuron
jf fulfenprox
jg tau-fulvalinate
jh honohos
ji formethanate
jj Formothion
jk Fraciocarb
jl halofenozide
jm hexaflumuron
jn hydramethylnon
jo imidacloprid
jp isofenphos
jq indoxacarb
jr isoprocarb
js isoxathione
jt rufenuuron
ju malathion
jv metal dehydr
jw methamidophos
jx methidathione
jy methacrifos
jz metal carb
ka mesomil
kb mesoprene
kc methoxychlor
kd methoxyphenozide
ke monocrotophos
kf Muscarule
kg Zinotefuran
kh Nitenpyram
ki ometoate
kj oxydemeton-methyl
kk parathion
kl parathion-methyl
km permethrin
kn Fentate
ko foxime
kp holate
kq ho salon
kr Hosmet
ks fosfamidon
kt Pirimicarb
ku pyrimifos-methyl
kv profenofos
kw protrifen butto
kx pymetrozine
ky pyraclofos
kz pyriproxyfen
la Rotenon
lb Sulprophos
lc Silafluophene
ld spinosad
le sulfotep
lf tebufenozide
lg Teflubenzuron
lh Tefluthrin
li terbujos
lj tetrachlorobinphos
lk thiacloprid
ll thiocyclam
lm thiodicarb
ln thiamethoxam
lo thiophanox
lp thiometon
lq Torfenpyrad
lr tralomethrin
ls Trichlorphone
lt Triazuron
lu Triflumuron
lv bamidione
lw ethion
lx Ashipetax
ly Aldimorph
lz allyl alcohol
ma aurerofungin
mb azitiram
mc Barium Polysulfide
md Benkinox
me Ventallon
mf bench avari karub
mg Benzalkonium chloride
mh benz amorph
mi benzohydroxamic acid
mj bithionol
mk butylamine
ml Carbamorph
mm Carvone
mn chestnut mixture
mo Chloraniformane
mp chloranil
mq chloropicrin
mr Chloroquinox
ms Crimbazole
mt clotrimazole
mu Copper Acetate
mv basic copper carbonate
mw cupric hydroxide
mx copper naphthalene
my copper orite
mz copper sulfate
na basic copper sulfate
nb Copper zinc chromate
nc cresol
nd cupurobam
ne Ciazofamide
nf cyclafluamide
ng cycloheximide
nh cyflufenamide
ni Cypendazole
nj DbC
nk decafentin
nl Dehydroacetate
nm Zyklon
nn diclozoline
no diethyl pyrocarbonate
np dimoxystrobin
nq dinoton
nr Zinocup-4
ns Gino Cup-6
nt dinocton
nu ginosulfone
nv Ginoterbon
nw dinosulfiram
nx DNC
ny etem
nz ethoxyquin
oa Ethyl Mercury Acetate
ob ethyl mercury bromide
oc methylmercury chloride
od Ethyl Mercury Phosphate
oe phenaminosulf
of Fenapanil
og fenitropan
oh Full Met Bar
oi full morph
oj Fluotrimazole
ok fluoxastrobin
ol fullcarbanyl
om fluconazole
on Fluconazole-cis
oo Full Mecicyclos
op phlophanate
ok gliosine
or Griseofulvin
os Harakurinate
ot hexachlorobutadiene
ou hexyl thiophos
ov hydroxyquinoline sulfate
ow isovaredione
ox mebenil
oy mecarbinzide
oz mercuric chloride
pa mercuric oxide
pb mercuric chloride
pc metalaxyl-M
pd metam
pe metalloxolone
pf female floxam
pg methyl bromide
ph methyl isothiocyanate
pi Methyl Mercury Benzoate
pj Methyl Mercury Dicyandiamide
pk metraphenone
pl metsulfobax
pm Milneb
pn microzoline
po Methoxymethyl Mercury Chloride
pp natamycin
pq nicobifen
pr Nitrostyrene
ps oc h
pt orisatrobin
pu organic copper
pv pentachlorophenol
pw urea phenylmercury
px Phenyl Mercury Acetate
py phenyl mercury chloride
pz Phenyl Mercury Night Late
qa Phenyl Mercury salicylate
qb phosdiphene
qc picoxystrobin
qd polycarbamate
qe polyoxorim
qf potassium azide
qg potassium polysulfide
qh proquinazide
qi prothiocarb
qj prothioconazole
qk pyracarbollide
ql pyraclostrobin
qm pyridinitrile
qn Pyroxycycloa
qo piroxysulfa
qp phenylphenol
qq quinacetor
qr quinazamid
qs quinconazole
qt lavenzazole
qua salicylanilide
qv silthiofam
qw simeconazole
qx sodium azide
qy sodium orthopenyl penoxide
qz sodium pentachlorophenoxide
ra sodium polysulfide
rb TSMC
rc Tecolum
rd thiadiflua
re chisiophen
rf thiochlorfenfim
rg thiomersam
rh thiophanate
ri thioquinox
rj thiazinyl
rk thioximide
rl Trimmer Curia Setate
rm Triamifos
rn Triarimol
ro Triazbutyl
rp tributyltin oxide
rq trickle amide
rr zarylamide
rs zinc naphthenate
rt bronopol
ru form aldehide
rv nitrapirine
rw thiomersal
rx iminin
ry rubyvirin
rz Diclofenthion
sa DSP
sb etoprophos
sc fensulfothion
sd Isamidophos
se Isazofos
sf thionazine
sg acrinatrin
sh Fenothiocarb
si spirodiclofen
sj Aranicarb
sk bacillus thuringiensis
sl fenthion
sm Full Validate
sn Oxydepropos
so prothiofos
sp propaphos
sq pyridalyl
sr spiromesifen
――――――――――――――――――――――――
The composition of the present invention and the method of the present invention are characterized in that, firstly, the insecticidal, acaricidal, nematicidal, bactericidal or bactericidal efficacy is clearly enhanced compared to the case where each drug is applied alone. , Instant insecticidal, acaricidal, nematicidal, bactericidal or bactericidal effects. Secondly, it induces a broad spectrum of insecticidal, acaricidal, nematicidal, bactericidal or bactericidal spectrum not found in existing insecticides, acaricides, nematicides, bactericides or bactericides, and long residual effects. It is. Thirdly, compared to the case where each drug is used alone, the amount of dropped drug can be reduced.
即ち、本発明組成物及び本発明方法は、相乗的殺虫、殺ダニ、殺線虫、殺菌又は殺バクテリア効果を奏するものである。この相乗的殺虫、殺ダニ、殺線虫、殺菌又は殺バクテリア効果は、各単剤の有する殺虫、殺ダニ、殺線虫、殺菌又は殺バクテリア効果からは予測し得ぬものであり、本発明組成物及び本発明方法の有用性は各種病害虫に対して各化合物を単独で使用するよりも確実な防除効果を発揮し得る点にあるといえる。 That is, the composition of the present invention and the method of the present invention exhibit a synergistic insecticidal, acaricidal, nematicidal, bactericidal or bactericidal effect. This synergistic insecticidal, acaricidal, nematicidal, bactericidal or bactericidal effect cannot be predicted from the insecticidal, acaricidal, nematicidal, bactericidal or bactericidal effect of each single agent, and the present invention It can be said that the usefulness of the composition and the method of the present invention lies in that a more reliable control effect can be exerted than various compounds are used alone against various pests.
上記の第3表に示した化合物の中で、一般式(1)及び一般式(2)で表される置換ベンズアニリド化合物と組み合わせることにより、特にその防除効果が、相乗的により向上する化合物を、以下の第4表に示す。 Among the compounds shown in Table 3 above, a compound whose controlling effect is synergistically improved by combining with the substituted benzanilide compounds represented by the general formula (1) and the general formula (2), It is shown in Table 4 below.
〔第4表〕
―――――――――――――――――
No. 化合物名
―――――――――――――――――
gu フェンプロパトリン
ht クロルフェナピル
hw クロルフルアズロン
hx クロチアニジン
id シペルメトリン
if シハロトリン
il ジフルベンズロン
ja フェンバレレート
je フルフェノクスロン
jo イミダクロプリド
jx メチダチオン
kg ジノテフラン
kh ニテンピラム
km ペルメトリン
kn フェントエート
lg テフルベンズロン
lk チアクロプリド
ln チアメトキサム
lr トラロメトリン
sj アラニカルブ
sm フルバリネート
so プロチオホス
―――――――――――――――――
次に、相乗的病害虫防除効果を奏する化合物の組み合わせの具体例を以下に挙げる。以下の表記において、例えば「1+a」は第1表のNo.1の化合物と第3表のNo.aのアシベンゾラル−S−メチルの組み合わせを表している。
[Table 4]
―――――――――――――――――
No. Compound name
―――――――――――――――――
gu fenpropatoline
ht chlorfenapyr
hw Chlorfluazuron
hx clothianidin
id Cypermethrin
if Cihalothrin
il diflubenzuron
ja fenvalerate
je Fulfenoxuron
jo imidacloprid
jx methidathione
kg Zinotefuran
kh Nitenpyram
km permethrin
kn Fentate
lg Teflubenzuron
lk thiacloprid
ln thiamethoxam
lr tralomethrin
sj Aranicarb
sm Full Validate
so prothiofos
―――――――――――――――――
Next, specific examples of combinations of compounds having a synergistic pest control effect are listed below. In the following notation, for example, “1 + a” represents a combination of the No. 1 compound in Table 1 and the acibenzolar-S-methyl in No. a in Table 3.
化合物の組み合わせの例:1+a,1+b,1+c,1+d,1+e,1+f,1+g,1+h,1+i,1+j,1+k,1+l,1+m,1+n,1+o,1+p,1+q,1+r,1+s,1+t,1+u,1+v,1+w,1+x,1+y,1+z,1+aa,1+ab,1+ac,1+ad,1+ae,1+af,1+ag,1+ah,1+ai,1+aj,1+ak,1+al,1+am,1+an,1+ao,1+ap,1+aq,1+ar,1+as,1+at,1+au,1+av,1+aw,1+ax,1+ay,1+az,1+ba,1+bb,1+bc,1+bd,1+be,1+bf,1+bg,1+bh,1+bi,1+bj,1+bk,1+bl,1+bm,1+bn,1+bo,1+bp,1+bq,1+br,1+bs,1+bt,1+bu,1+bv,1+bw,1+bx,1+by,1+bz,1+ca,1+cb,1+cc,1+cd,1+ce,1+cf,1+cg,1+ch,1+ci,1+cj,1+ck,1+cl,1+cm,1+cn,1+co,1+cp,1+cq,1+cr,1+cs,1+ct,1+cu,1+cv,1+cw,1+cx,1+cy,1+cz,1+da,1+db,1+dc,1+dd,1+de,1+df,1+dg,1+dh,1+di,1+dj,1+dk,1+dl,1+dm,1+dn,1+do,1+dp,1+dq,1+dr,1+ds,1+dt,1+du,1+dv,1+dw,1+dx,1+dy,1+dz,1+ea,1+eb,1+ec,1+ed,1+ee,1+ef,1+eg,1+eh,1+ei,1+ej,1+ek,1+el,1+em,1+en,1+eo,1+ep,1+eq,1+er,1+es,1+et,1+eu,1+ev,1+ew,1+ex,1+ey,1+ez,1+fa,1+fb,1+fc,1+fd,1+fe,1+ff,1+fg,1+fh,1+fi,1+fj,1+fk,1+fl,1+fm,1+fn,1+fo,1+fp,1+fq,1+fr,1+fs,1+ft,1+fu,1+fv,1+fw,1+fx,1+fy,1+fz,1+ga,1+gb,1+gc,1+gd,1+ge,1+gf,1+gg,1+gh,1+gi,1+gj,1+gk,1+gl,1+gm,1+gn,1+go,1+gp,1+gq,1+gr,1+gs,1+gt,1+gu,1+gv,1+gw,1+gx,1+gy,1+gz,1+ha,1+hb,1+hc,1+hd,1+he,1+hf,1+hg,1+hh,1+hi,1+hj,1+hk,1+hl,1+hm,1+hn,1+ho,1+hp,1+hq,1+hr,1+hs,1+ht,1+hu,1+hv,1+hw,1+hx,1+hy,1+hz,1+ia,1+ib,1+ic,1+id,1+ie,1+if,1+ig,1+ih,1+ii,1+ij,1+ik,1+il,1+im,1+in,1+io,1+ip,1+iq,1+ir,1+is,1+it,1+iu,1+iv,1+iw,1+ix,1+iy,1+iz,1+ja,1+jb,1+jc,1+jd,1+je,1+jf,1+jg,1+jh,1+ji,1+jj,1+jk,1+jl,1+jm,1+jn,1+jo,1+jp,1+jq,1+jr,1+js,1+jt,1+ju,1+jv,1+jw,1+jx,1+jy,1+jz,1+ka,1+kb,1+kc,1+kd,1+ke,1+kf,1+kg,1+kh,1+ki,1+kj,1+kk,1+kl,1+km,1+kn,1+ko,1+kp,1+kq,1+kr,1+ks,1+kt,1+ku,1+kv,1+kw,1+kx,1+ky,1+kz,1+la,1+lb,1+lc,1+ld,1+le,1+lf,1+lg,1+lh,1+li,1+lj,1+lk,1+ll,1+lm,1+ln,1+lo,1+lp,1+lq,1+lr,1+ls,1+lt,1+lu,1+lv,1+lw,1+lx,1+ly,1+lz,1+ma,1+mb,1+mc,1+md,1+me,1+mf,1+mg,1+mh,1+mi,1+mj,1+mk,1+ml,1+mm,1+mn,1+mo,1+mp,1+mq,1+mr,1+ms,1+mt,1+mu,1+mv,1+mw,1+mx,1+my,1+mz,1+na,1+nb,1+nc,1+nd,1+ne,1+nf,1+ng,1+nh,1+ni,1+nj,1+nk,1+nl,1+nm,1+nn,1+no,1+np,1+nq,1+nr,1+ns,1+nt,1+nu,1+nv,1+nw,1+nx,1+ny,1+nz,1+oa,1+ob,1+oc,1+od,1+oe,1+of,1+og,1+oh,1+oi,1+oj,1+ok,1+ol,1+om,1+on,1+oo,1+op,1+oq,1+or,1+os,1+ot,1+ou,1+ov,1+ow,1+ox,1+oy,1+oz,1+pa,1+pb,1+pc,1+pd,1+pe,1+pf,1+pg,1+ph,1+pi,1+pj,1+pk,1+pl,1+pm,1+pn,1+po,1+pp,1+pq,1+pr,1+ps,1+pt,1+pu,1+pv,1+pw,1+px,1+py,1+pz,1+qa,1+qb,1+qc,1+qd,1+qe,1+qf,1+qg,1+qh,1+qi,1+qj,1+qk,1+ql,1+qm,1+qn,1+qo,1+qp,1+qq,1+qr,1+qs,1+qt,1+qu,1+qv,1+qw,1+qx,1+qy,1+qz,1+ra,1+rb,1+rc,1+rd,1+re,1+rf,1+rg,1+rh,1+ri,1+rj,1+rk,1+rl,1+rm,1+rn,1+ro,1+rp,1+rq,1+rr,1+rs,1+rt,1+ru,1+rv,1+rw,1+rx,1+ry,1+rz,1+sa,1+sb,1+sc,1+sd,1+se,1+sf,1+sg,1+sh,1+si,1+sj,1+sk,1+sl,1+sm,1+sn,1+so,1+sp,1+sq,1+sr,2+a,2+b,2+c,2+d,2+e,2+f,2+g,2+h,2+i,2+j,2+k,2+l,2+m,2+n,2+o,2+p,2+q,2+r,2+s,2+t,2+u,2+v,2+w,2+x,2+y,2+z,2+aa,2+ab,2+ac,2+ad,2+ae,2+af,2+ag,2+ah,2+ai,2+aj,2+ak,2+al,2+am,2+an,2+ao,2+ap,2+aq,2+ar,2+as,2+at,2+au,2+av,2+aw,2+ax,2+ay,2+az,2+ba,2+bb,2+bc,2+bd,2+be,2+bf,2+bg,2+bh,2+bi,2+bj,2+bk,2+bl,2+bm,2+bn,2+bo,2+bp,2+bq,2+br,2+bs,2+bt,2+bu,2+bv,2+bw,2+bx,2+by,2+bz,2+ca,2+cb,2+cc,2+cd,2+ce,2+cf,2+cg,2+ch,2+ci,2+cj,2+ck,2+cl,2+cm,2+cn,2+co,2+cp,2+cq,2+cr,2+cs,2+ct,2+cu,2+cv,2+cw,2+cx,2+cy,2+cz,2+da,2+db,2+dc,2+dd,2+de,2+df,2+dg,2+dh,2+di,2+dj,2+dk,2+dl,2+dm,2+dn,2+do,2+dp,2+dq,2+dr,2+ds,2+dt,2+du,2+dv,2+dw,2+dx,2+dy,2+dz,2+ea,2+eb,2+ec,2+ed,2+ee,2+ef,2+eg,2+eh,2+ei,2+ej,2+ek,2+el,2+em,2+en,2+eo,2+ep,2+eq,2+er,2+es,2+et,2+eu,2+ev,2+ew,2+ex,2+ey,2+ez,2+fa,2+fb,2+fc,2+fd,2+fe,2+ff,2+fg,2+fh,2+fi,2+fj,2+fk,2+fl,2+fm,2+fn,2+fo,2+fp,2+fq,2+fr,2+fs,2+ft,2+fu,2+fv,2+fw,2+fx,2+fy,2+fz,2+ga,2+gb,2+gc,2+gd,2+ge,2+gf,2+gg,2+gh,2+gi,2+gj,2+gk,2+gl,2+gm,2+gn,2+go,2+gp,2+gq,2+gr,2+gs,2+gt,2+gu,2+gv,2+gw,2+gx,2+gy,2+gz,2+ha,2+hb,2+hc,2+hd,2+he,2+hf,2+hg,2+hh,2+hi,2+hj,2+hk,2+hl,2+hm,2+hn,2+ho,2+hp,2+hq,2+hr,2+hs,2+ht,2+hu,2+hv,2+hw,2+hx,2+hy,2+hz,2+ia,2+ib,2+ic,2+id,2+ie,2+if,2+ig,2+ih,2+ii,2+ij,2+ik,2+il,2+im,2+in,2+io,2+ip,2+iq,2+ir,2+is,2+it,2+iu,2+iv,2+iw,2+ix,2+iy,2+iz,2+ja,2+jb,2+jc,2+jd,2+je,2+jf,2+jg,2+jh,2+ji,2+jj,2+jk,2+jl,2+jm,2+jn,2+jo,2+jp,2+jq,2+jr,2+js,2+jt,2+ju,2+jv,2+jw,2+jx,2+jy,2+jz,2+ka,2+kb,2+kc,2+kd,2+ke,2+kf,2+kg,2+kh,2+ki,2+kj,2+kk,2+kl,2+km,2+kn,2+ko,2+kp,2+kq,2+kr,2+ks,2+kt,2+ku,2+kv,2+kw,2+kx,2+ky,2+kz,2+la,2+lb,2+lc,2+ld,2+le,2+lf,2+lg,2+lh,2+li,2+lj,2+lk,2+ll,2+lm,2+ln,2+lo,2+lp,2+lq,2+lr,2+ls,2+lt,2+lu,2+lv,2+lw,2+lx,2+ly,2+lz,2+ma,2+mb,2+mc,2+md,2+me,2+mf,2+mg,2+mh,2+mi,2+mj,2+mk,2+ml,2+mm,2+mn,2+mo,2+mp,2+mq,2+mr,2+ms,2+mt,2+mu,2+mv,2+mw,2+mx,2+my,2+mz,2+na,2+nb,2+nc,2+nd,2+ne,2+nf,2+ng,2+nh,2+ni,2+nj,2+nk,2+nl,2+nm,2+nn,2+no,2+np,2+nq,2+nr,2+ns,2+nt,2+nu,2+nv,2+nw,2+nx,2+ny,2+nz,2+oa,2+ob,2+oc,2+od,2+oe,2+of,2+og,2+oh,2+oi,2+oj,2+ok,2+ol,2+om,2+on,2+oo,2+op,2+oq,2+or,2+os,2+ot,2+ou,2+ov,2+ow,2+ox,2+oy,2+oz,2+pa,2+pb,2+pc,2+pd,2+pe,2+pf,2+pg,2+ph,2+pi,2+pj,2+pk,2+pl,2+pm,2+pn,2+po,2+pp,2+pq,2+pr,2+ps,2+pt,2+pu,2+pv,2+pw,2+px,2+py,2+pz,2+qa,2+qb,2+qc,2+qd,2+qe,2+qf,2+qg,2+qh,2+qi,2+qj,2+qk,2+ql,2+qm,2+qn,2+qo,2+qp,2+qq,2+qr,2+qs,2+qt,2+qu,2+qv,2+qw,2+qx,2+qy,2+qz,2+ra,2+rb,2+rc,2+rd,2+re,2+rf,2+rg,2+rh,2+ri,2+rj,2+rk,2+rl,2+rm,2+rn,2+ro,2+rp,2+rq,2+rr,2+rs,2+rt,2+ru,2+rv,2+rw,2+rx,2+ry,2+rz,2+sa,2+sb,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78+gi,78+gj,78+gk,78+gl,78+gm,78+gn,78+go,78+gp,78+gq,78+gr,78+gs,78+gt,78+gu,78+gv,78+gw,78+gx,78+gy,78+gz,78+ha,78+hb,78+hc,78+hd,78+he,78+hf,78+hg,78+hh,78+hi,78+hj,78+hk,78+hl,78+hm,78+hn,78+ho,78+hp,78+hq,78+hr,78+hs,78+ht,78+hu,78+hv,78+hw,78+hx,78+hy,78+hz,78+ia,78+ib,78+ic,78+id,78+ie,78+if,78+ig,78+ih,78+ii,78+ij,78+ik,78+il,78+im,78+in,78+io,78+ip,78+iq,78+ir,78+is,78+it,78+iu,78+iv,78+iw,78+ix,78+iy,78+iz,78+ja,78+jb,78+jc,78+jd,78+je,78+jf,78+jg,78+jh,78+ji,78+jj,78+jk,78+jl,78+jm,78+jn,78+jo,78+jp,78+jq,78+jr,78+js,78+jt,78+ju,78+jv,78+jw,78+jx,78+jy,78+jz,78+ka,78+kb,78+kc,78+kd,78+ke,78+kf,78+kg,78+kh,78+ki,78+kj,78+kk,78+kl,78+km,78+kn,78+ko,78+kp,78+kq,78+kr,78+ks,78+kt,78+ku,78+kv,78+kw,78+kx,78+ky,78+kz,78+la,78+lb,78+lc,78+ld,78+le,78+lf,78+lg,78+lh,78+li,78+lj,78+lk,78+ll,78+lm,78+ln,78+lo,78+lp,78+lq,78+lr,78+ls,78+lt,78+lu,78+lv,78+lw,78+lx,78+ly,78+lz,78+ma,78+mb,78+mc,78+md,78+me,78+mf,78+mg,78+mh,78+mi,78+mj,78+mk,78+ml,78+mm,78+mn,78+mo,78+mp,78+mq,78+mr,78+ms,78+mt,78+mu,78+mv,78+mw,78+mx,78+my,78+mz,78+na,78+nb,78+nc,78+nd,78+ne,78+nf,78+ng,78+nh,78+ni,78+nj,78+nk,78+nl,78+nm,78+nn,78+no,78+np,78+nq,78+nr,78+ns,78+nt,78+nu,78+nv,78+nw,78+nx,78+ny,78+nz,78+oa,78+ob,78+oc,78+od,78+oe,78+of,78+og,78+oh,78+oi,78+oj,78+ok,78+ol,78+om,78+on,78+oo,78+op,78+oq,78+or,78+os,78+ot,78+ou,78+ov,78+ow,78+ox,78+oy,78+oz,78+pa,78+pb,78+pc,78+pd,78+pe,78+pf,78+pg,78+ph,78+pi,78+pj,78+pk,78+pl,78+pm,78+pn,78+po,78+pp,78+pq,78+pr,78+ps,78+pt,78+pu,78+pv,78+pw,78+px,78+py,78+pz,78+qa,78+qb,78+qc,78+qd,78+qe,78+qf,78+qg,78+qh,78+qi,78+qj,78+qk,78+ql,78+qm,78+qn,78+qo,78+qp,78+qq,78+qr,78+qs,78+qt,78+qu,78+qv,78+qw,78+qx,78+qy,78+qz,78+ra,78+rb,78+rc,78+rd,78+re,78+rf,78+rg,78+rh,78+ri,78+rj,78+rk,78+rl,78+rm,78+rn,78+ro,78+rp,78+rq,78+rr,78+rs,78+rt,78+ru,78+rv,78+rw,78+rx,78+ry,78+rz,78+sa,78+sb,78+sc,78+sd,78+se,78+sf,78+sg,78+sh,78+si,78+sj,78+sk,78+sl,78+sm,78+sn,78+so,78+sp,78+sq,78+sr,79+a,79+b,79+c,79+d,79+e,79+f,79+g,79+h,79+i,79+j,79+k,79+l,79+m,79+n,79+o,79+p,79+q,79+r,79+s,79+t,79+u,79+v,79+w,79+x,79+y,79+z,79+aa,79+ab,79+ac,79+ad,79+ae,79+af,79+ag,79+ah,79+ai,79+aj,79+ak,79+al,79+am,79+an,79+ao,79+ap,79+aq,79+ar,79+as,79+at,79+au,79+av,79+aw,79+ax,79+ay,79+az,79+ba,79+bb,79+bc,79+bd,79+be,79+bf,79+bg,79+bh,79+bi,79+bj,79+bk,79+bl,79+bm,79+bn,79+bo,79+bp,79+bq,79+br,79+bs,79+bt,79+bu,79+bv,79+bw,79+bx,79+by,79+bz,79+ca,79+cb,79+cc,79+cd,79+ce,79+cf,79+cg,79+ch,79+ci,79+cj,79+ck,79+cl,79+cm,79+cn,79+co,79+cp,79+cq,79+cr,79+cs,79+ct,79+cu,79+cv,79+cw,79+cx,79+cy,79+cz,79+da,79+db,79+dc,79+dd,79+de,79+df,79+dg,79+dh,79+di,79+dj,79+dk,79+dl,79+dm,79+dn,79+do,79+dp,79+dq,79+dr,79+ds,79+dt,79+du,79+dv,79+dw,79+dx,79+dy,79+dz,79+ea,79+eb,79+ec,79+ed,79+ee,79+ef,79+eg,79+eh,79+ei,79+ej,79+ek,79+el,79+em,79+en,79+eo,79+ep,79+eq,79+er,79+es,79+et,79+eu,79+ev,79+ew,79+ex,79+ey,79+ez,79+fa,79+fb,79+fc,79+fd,79+fe,79+ff,79+fg,79+fh,79+fi,79+fj,79+fk,79+fl,79+fm,79+fn,79+fo,79+fp,79+fq,79+fr,79+fs,79+ft,79+fu,79+fv,79+fw,79+fx,79+fy,79+fz,79+ga,79+gb,79+gc,79+gd,79+ge,79+gf,79+gg,79+gh,79+gi,79+gj,79+gk,79+gl,79+gm,79+gn,79+go,79+gp,79+gq,79+gr,79+gs,79+gt,79+gu,79+gv,79+gw,79+gx,79+gy,79+gz,79+ha,79+hb,79+hc,79+hd,79+he,79+hf,79+hg,79+hh,79+hi,79+hj,79+hk,79+hl,79+hm,79+hn,79+ho,79+hp,79+hq,79+hr,79+hs,79+ht,79+hu,79+hv,79+hw,79+hx,79+hy,79+hz,79+ia,79+ib,79+ic,79+id,79+ie,79+if,79+ig,79+ih,79+ii,79+ij,79+ik,79+il,79+im,79+in,79+io,79+ip,79+iq,79+ir,79+is,79+it,79+iu,79+iv,79+iw,79+ix,79+iy,79+iz,79+ja,79+jb,79+jc,79+jd,79+je,79+jf,79+jg,79+jh,79+ji,79+jj,79+jk,79+jl,79+jm,79+jn,79+jo,79+jp,79+jq,79+jr,79+js,79+jt,79+ju,79+jv,79+jw,79+jx,79+jy,79+jz,79+ka,79+kb,79+kc,79+kd,79+ke,79+kf,79+kg,79+kh,79+ki,79+kj,79+kk,79+kl,79+km,79+kn,79+ko,79+kp,79+kq,79+kr,79+ks,79+kt,79+ku,79+kv,79+kw,79+kx,79+ky,79+kz,79+la,79+lb,79+lc,79+ld,79+le,79+lf,79+lg,79+lh,79+li,79+lj,79+lk,79+ll,79+lm,79+ln,79+lo,79+lp,79+lq,79+lr,79+ls,79+lt,79+lu,79+lv,79+lw,79+lx,79+ly,79+lz,79+ma,79+mb,79+mc,79+md,79+me,79+mf,79+mg,79+mh,79+mi,79+mj,79+mk,79+ml,79+mm,79+mn,79+mo,79+mp,79+mq,79+mr,79+ms,79+mt,79+mu,79+mv,79+mw,79+mx,79+my,79+mz,79+na,79+nb,79+nc,79+nd,79+ne,79+nf,79+ng,79+nh,79+ni,79+nj,79+nk,79+nl,79+nm,79+nn,79+no,79+np,79+nq,79+nr,79+ns,79+nt,79+nu,79+nv,79+nw,79+nx,79+ny,79+nz,79+oa,79+ob,79+oc,79+od,79+oe,79+of,79+og,79+oh,79+oi,79+oj,79+ok,79+ol,79+om,79+on,79+oo,79+op,79+oq,79+or,79+os,79+ot,79+ou,79+ov,79+ow,79+ox,79+oy,79+oz,79+pa,79+pb,79+pc,79+pd,79+pe,79+pf,79+pg,79+ph,79+pi,79+pj,79+pk,79+pl,79+pm,79+pn,79+po,79+pp,79+pq,79+pr,79+ps,79+pt,79+pu,79+pv,79+pw,79+px,79+py,79+pz,79+qa,79+qb,79+qc,79+qd,79+qe,79+qf,79+qg,79+qh,79+qi,79+qj,79+qk,79+ql,79+qm,79+qn,79+qo,79+qp,79+qq,79+qr,79+qs,79+qt,79+qu,79+qv,79+qw,79+qx,79+qy,79+qz,79+ra,79+rb,79+rc,79+rd,79+re,79+rf,79+rg,79+rh,79+ri,79+rj,79+rk,79+rl,79+rm,79+rn,79+ro,79+rp,79+rq,79+rr,79+rs,79+rt,79+ru,79+rv,79+rw,79+rx,79+ry,79+rz,79+sa,79+sb,79+sc,79+sd,79+se,79+sf,79+sg,79+sh,79+si,79+sj,79+sk,79+sl,79+sm,79+sn,79+so,79+sp,79+sq,79+sr。
Examples of compound combinations: 1 + a, 1 + b, 1 + c, 1 + d, 1 + e, 1 + f, 1 + g, 1 + h, 1 + i, 1 + j, 1 + k, 1 + l, 1 + m, 1 + n, 1 + o, 1 + p, 1 + q, 1 + r, 1 + s, 1 + t, 1 + u, 1 + v, 1 + w, 1 + x, 1 + y, 1 + z, 1 + aa, 1 + ab, 1 + ac, 1 + ad, 1 + ae, 1 + af, 1 + ag, 1 + ah, 1 + ai, 1 + aj, 1 + ak, 1 + al, 1 + am, 1 + an, 1 + ao, 1 + ap, 1 + aq, 1 + ar, 1 + as, 1 + at, 1 + au, 1 + av, 1 + aw, 1 + ax, 1 + ay, 1 + az, 1 + ba, 1 + bb, 1 + bc, 1 + bd, 1 + be, 1 + bf, 1 + bg, 1 + bh, 1 + bi, 1 + bj, 1 + bk, 1 + bl, 1 + bm, 1 + bn, 1 + bo, 1 + bp, 1 + bq, 1 + br, 1 + bs, 1 + bt, 1 + bu, 1 + bv, 1 + bw, 1 + bx, 1 + by, 1 + bz, 1 + ca, 1 + cb, 1 + cc, 1 + cd, 1 + ce, 1 + cf, 1 + cg, 1 + ch, 1 + ci, 1 + cj, 1 + ck, 1 + cl, 1 + cm, 1 + cn, 1 + co, 1 + cp, 1 + cq, 1 + cr, 1 + cs, 1 + ct, 1 + cu, 1 + cv, 1 + cw, 1 + cx, 1 + cy, 1 + cz, 1 + da, 1 + db, 1 + dc, 1 + dd, 1 + de, 1 + df, 1 + dg, 1 + dh, 1 + di, 1 + dj, 1 + dk, 1 + dl, 1 + dm, 1 + dn, 1 + do, 1 + dp, 1 + dq, 1 + dr, 1 + ds, 1 + dt, 1 + du, 1 + dv, 1 + dw, 1 + dx, 1 + dy, 1 + dz, 1 + ea, 1 + eb, 1 + ec, 1 + ed, 1 + ee, 1 + ef, 1 + eg, 1 + eh, 1 + ei, 1 + ej, 1 + ek, 1 + el, 1 + em, 1 + en, 1 + eo, 1 + ep, 1 + eq, 1 + er, 1 + es, 1 + et, 1 + eu, 1 + ev, 1 + ew, 1 + ex, 1 + ey, 1 + ez, 1 + fa, 1 + fb, 1 + fc, 1 + fd, 1 + fe, 1 + ff, 1 + fg, 1 + fh, 1 + fi, 1 + fj, 1 + fk, 1 + fl, 1 + fm, 1 + fn, 1 + fo, 1 + fp, 1 + fq, 1 + fr, 1 + fs, 1 + ft, 1 + fu, 1 + fv, 1 + fw, 1 + fx, 1 + fy, 1 + fz, 1 + ga, 1 + gb, 1 + gc, 1 + gd, 1 + ge, 1 + gf, 1 + gg, 1 + gh, 1 + gi, 1 + gj, 1 + gk, 1 + gl, 1 + gm, 1 + gn, 1 + go, 1 + gp, 1 + gq, 1 + gr, 1 + gs, 1 + gt, 1 + gu, 1 + gv, 1 + gw, 1 + gx, 1 + gy, 1 + gz, 1 + ha, 1 + hb, 1 + hc, 1 + hd, 1 + he, 1 + hf, 1 + hg, 1 + hh, 1 + hi, 1 + hj, 1 + hk, 1 + hl, 1 + hm, 1 + hn, 1 + ho, 1 + hp, 1 + hq, 1 + hr, 1 + hs, 1 + ht, 1 + hu, 1 + hv, 1 + hw, 1 + hx, 1 + hy, 1 + hz, 1 + ia, 1 + ib, 1 + ic, 1 + id, 1 + ie, 1 + if, 1 + ig, 1 + ih, 1 + ii, 1 + ij, 1 + ik, 1 + il, 1 + im, 1 + in, 1 + io, 1 + ip, 1 + iq, 1 + ir, 1 + is, 1 + it, 1 + iu, 1 + iv, 1 + iw, 1 + ix, 1 + iy, 1 + iz, 1 + ja, 1 + jb, 1 + jc, 1 + jd, 1 + je, 1 + jf, 1 + jg, 1 + jh, 1 + ji, 1 + jj, 1 + jk, 1 + jl, 1 + jm, 1 + jn, 1 + jo, 1 + jp, 1 + jq, 1 + jr, 1 + js, 1 + jt, 1 + ju, 1 + jv, 1 + jw, 1 + jx, 1 + jy, 1 + jz, 1 + ka, 1 + kb, 1 + kc, 1 + kd, 1 + ke, 1 + kf, 1 + kg, 1 + kh, 1 + ki, 1 + kj, 1 + kk, 1 + kl, 1 + km, 1 + kn, 1 + ko, 1 + kp, 1 + kq, 1 + kr, 1 + ks, 1 + kt, 1 + ku, 1 + kv, 1 + kw, 1 + kx, 1 + ky, 1 + kz, 1 + la, 1 + lb, 1 + lc, 1 + ld, 1 + le, 1 + lf, 1 + lg, 1 + lh, 1 + li, 1 + lj, 1 + lk, 1 + ll, 1 + lm, 1 + ln, 1 + lo, 1 + lp, 1 + lq, 1 + lr, 1 + ls, 1 + lt, 1 + lu, 1 + lv, 1 + lw, 1 + lx, 1 + ly, 1 + lz, 1 + ma, 1 + mb, 1 + mc, 1 + md, 1 + me, 1 + mf, 1 + mg, 1 + mh, 1 + mi, 1 + mj, 1 + mk, 1 + ml, 1 + mm, 1 + mn, 1 + mo, 1 + mp, 1 + mq, 1 + mr, 1 + ms, 1 + mt, 1 + mu, 1 + mv, 1 + mw, 1 + mx, 1 + my, 1 + mz, 1 + na, 1 + nb, 1 + nc, 1 + nd, 1 + ne, 1 + nf, 1 + ng, 1 + nh, 1 + ni, 1 + nj, 1 + nk, 1 + nl, 1 + nm, 1 + nn, 1 + no, 1 + np, 1 + nq, 1 + nr, 1 + ns, 1 + nt, 1 + nu, 1 + nv, 1 + nw, 1 + nx, 1 + ny, 1 + nz, 1 + oa, 1 + ob, 1 + oc, 1 + od, 1 + oe, 1 + of, 1 + og, 1 + oh, 1 + oi, 1 + oj, 1 + ok, 1 + ol, 1 + om, 1 + on, 1 + oo, 1 + op, 1 + oq, 1 + or, 1 + os, 1 + ot, 1 + ou, 1 + ov, 1 + ow, 1 + ox, 1 + oy, 1 + oz, 1 + pa, 1 + pb, 1 + pc, 1 + pd, 1 + pe, 1 + pf, 1 + pg, 1 + ph, 1 + pi, 1 + pj, 1 + pk, 1 + pl, 1 + pm, 1 + pn, 1 + po, 1 + pp, 1 + pq, 1 + pr, 1 + ps, 1 + pt, 1 + pu, 1 + pv, 1 + pw, 1 + px, 1 + py, 1 + pz, 1 + qa, 1 + qb, 1 + qc, 1 + qd, 1 + qe, 1 + qf, 1 + qg, 1 + qh, 1 + qi, 1 + qj, 1 + qk, 1 + ql, 1 + qm, 1 + qn, 1 + qo, 1 + qp, 1 + qq, 1 + qr, 1 + qs, 1 + qt, 1 + qu, 1 + qv, 1 + qw, 1 + qx, 1 + qy, 1 + qz, 1 + ra, 1 + rb, 1 + rc, 1 + rd, 1 + re, 1 + rf, 1 + rg, 1 + rh, 1 + ri, 1 + rj, 1 + rk, 1 + rl, 1 + rm, 1 + rn, 1 + ro, 1 + rp, 1 + rq, 1 + rr, 1 + rs, 1 + rt, 1 + ru, 1 + rv, 1 + rw, 1 + rx, 1 + ry, 1 + rz, 1 + sa, 1 + sb, 1 + sc, 1 + sd, 1 + se, 1 + sf, 1 + sg, 1 + sh, 1 + si, 1 + sj, 1 + sk, 1 + sl, 1 + sm, 1 + sn, 1 + so, 1 + sp, 1 + sq, 1 + sr, 2 + a, 2 + b, 2 + c, 2 + d, 2 + e, 2 + f, 2 + g, 2 + h, 2 + i, 2 + j, 2 + k, 2 + l, 2 + m, 2 + n, 2 + o, 2 + p, 2 + q, 2 + r, 2 + s, 2 + t, 2 + u, 2 + v, 2 + w, 2 + x, 2 + y, 2 + z, 2 + aa, 2 + ab, 2 + ac, 2 + ad, 2 + ae, 2 + af, 2 + ag, 2 + ah, 2 + ai, 2 + aj, 2 + ak, 2 + al, 2 + am, 2 + an, 2 + ao, 2 + ap, 2 + aq, 2 + ar, 2 + as, 2 + at, 2 + au, 2 + av, 2+ aw, 2 + ax, 2 + ay, 2 + az, 2 + ba, 2 + bb, 2 + bc, 2 + bd, 2 + be, 2 + bf, 2 + bg, 2 + bh, 2 + bi, 2 + bj, 2 + bk, 2 + bl, 2 + bm, 2 + bn, 2 + bo, 2 + bp, 2 + bq, 2 + br, 2 + bs, 2 + bt, 2 + bu, 2+ bv, 2 + bw, 2 + bx, 2 + by, 2 + bz, 2 + ca, 2 + cb, 2 + cc, 2 + cd, 2 + ce, 2 + cf, 2 + cg, 2 + ch, 2 + ci, 2 + cj, 2 + ck, 2 + cl, 2 + cm, 2 + cn, 2 + co, 2 + cp, 2 + cq, 2 + cr, 2 + cs, 2 + ct, 2 + cu, 2 + cv, 2 + cw, 2 + cx, 2 + cy, 2 + cz , 2 + da, 2 + db, 2 + dc, 2 + dd, 2 + de, 2 + df, 2 + dg, 2 + dh, 2 + di, 2 + dj, 2 + dk, 2 + dl, 2 + dm, 2 + dn, 2 + do, 2 + dp, 2 + dq, 2 + dr, 2 + ds, 2 + dt, 2 + du, 2 + dv, 2 + dw, 2 + dx, 2 + dy , 2 + dz, 2 + ea, 2 + eb, 2 + ec, 2 + ed, 2 + ee, 2 + ef, 2 + eg, 2 + eh, 2 + ei, 2 + ej, 2 + ek, 2 + el, 2 + em, 2 + en, 2 + eo, 2 + ep, 2 + eq, 2 + er, 2 + es, 2 + et, 2 + eu, 2 + ev, 2 + ew, 2 + ex , 2 + ey, 2 + ez, 2 + fa, 2 + fb, 2 + fc, 2 + fd, 2 + fe, 2 + ff, 2 + fg, 2 + fh, 2 + fi, 2 + fj, 2 + fk, 2 + fl, 2 + fm, 2 + fn, 2 + fo, 2 + fp, 2 + fq, 2 + fr, 2 + fs, 2 + ft, 2 + fu, 2 + fv, 2 + fw , 2 + fx, 2 + fy, 2 + fz, 2 + ga, 2 + gb, 2 + gc, 2 + gd, 2 + ge, 2 + gf, 2 + gg, 2 + gh, 2 + gi, 2 + gj, 2 + gk, 2 + gl, 2 + gm, 2 + gn, 2 + go, 2 + gp, 2 + gq, 2 + gr, 2 + gs, 2 + gt, 2 + gu, 2 + gv , 2 + gw, 2 + gx, 2 + gy, 2 + gz, 2 + ha, 2 + hb, 2 + hc, 2 + hd, 2 + he, 2 + hf, 2 + hg, 2 + hh, 2 + hi, 2 + hj, 2 + hk, 2 + hl, 2 + hm, 2 + hn, 2 + ho, 2 + hp, 2 + hq, 2 + hr, 2 + hs, 2 + ht, 2 + hu , 2 + hv, 2 + hw, 2 + hx, 2 + hy, 2 + hz, 2 + ia, 2 + ib, 2 + ic, 2 + id, 2 + ie, 2 + if, 2 + ig, 2 + ih, 2 + ii, 2 + ij, 2 + ik, 2 + il, 2 + im, 2 + in, 2 + io, 2 + ip, 2 + iq, 2 + ir, 2 + is, 2 + it , 2 + iu, 2 + iv, 2 + iw, 2 + ix, 2 + iy, 2 + iz, 2 + ja, 2 + jb, 2 + jc, 2 + jd, 2 + je, 2 + jf, 2 + jg, 2 + jh, 2 + ji, 2 + jj, 2 + jk, 2 + jl, 2 + jm, 2 + jn, 2 + jo, 2 + jp, 2 + jq, 2 + jr, 2 + js , 2 + jt, 2 + ju, 2 + jv, 2 + jw, 2 + jx, 2 + jy, 2 + jz, 2 + ka, 2 + kb, 2 + kc, 2 + kd, 2 + ke, 2 + kf, 2 + kg, 2 + kh, 2 + ki, 2 + kj, 2 + kk, 2 + kl, 2 + km, 2 + kn, 2 + ko, 2 + kp, 2 + kq, 2 + kr , 2 + ks, 2 + kt, 2 + ku, 2 + kv, 2 + kw, 2 + kx, 2 + ky, 2 + kz, 2 + la, 2 + lb, 2 + lc, 2 + ld, 2 + le, 2 + lf, 2 + lg, 2 + lh, 2 + li, 2 + lj, 2 + lk, 2 + ll, 2 + lm, 2 + ln, 2 + lo, 2 + lp, 2 + lq , 2 + lr, 2 + ls, 2 + lt, 2 + lu, 2 + lv, 2 + lw, 2 + lx, 2 + ly, 2 + lz, 2 + ma, 2 + mb, 2 + mc, 2 + md, 2 + me, 2 + mf, 2 + mg, 2 + mh, 2 + mi, 2 + mj, 2 + mk, 2 + ml, 2 + mm, 2 + mn, 2 + mo, 2 + mp , 2 + mq, 2 + mr, 2 + ms, 2 + mt, 2 + mu, 2 + mv, 2 + mw, 2 + mx, 2 + my, 2 + mz, 2 + na, 2 + nb, 2 + nc, 2 + nd, 2 + ne, 2 + nf, 2 + ng, 2 + nh, 2 + ni, 2 + nj, 2 + nk, 2 + nl, 2 + nm, 2 + nn, 2 + no , 2 + np, 2 + nq, 2 + nr, 2 + ns, 2 + nt, 2 + nu, 2 + nv, 2 + nw, 2 + nx, 2 + ny, 2 + nz, 2 + oa, 2 + ob, 2 + oc, 2 + od, 2 + oe, 2 + of, 2 + og, 2 + oh, 2 + oi, 2 + oj, 2 + ok, 2 + ol, 2 + om, 2 + on , 2 + oo, 2 + op, 2 + oq, 2 + or, 2 + os, 2 + ot, 2 + ou, 2 + ov, 2 + ow, 2 + ox, 2 + oy, 2 + oz, 2 + pa, 2 + pb, 2 + pc, 2 + pd, 2 + pe, 2 + pf, 2 + pg, 2 + ph, 2 + pi, 2 + pj, 2 + pk, 2 + pl, 2 + pm , 2 + pn, 2 + po, 2 + pp, 2 + pq, 2 + pr, 2 + ps, 2 + pt, 2 + pu, 2 + pv, 2 + pw, 2 + px, 2 + py, 2 + pz, 2 + qa, 2 + qb, 2 + qc, 2 + qd, 2 + qe, 2 + qf, 2 + qg, 2 + qh, 2 + qi, 2 + qj, 2 + qk, 2 + ql , 2 + qm, 2 + qn, 2 + qo, 2 + qp, 2 + qq, 2 + qr, 2 + qs, 2 + qt, 2 + qu, 2 + qv, 2 + qw, 2 + qx, 2 + qy, 2 + qz, 2 + ra, 2 + rb, 2 + rc, 2 + rd, 2 + re, 2 + rf, 2 + rg, 2 + rh, 2 + ri, 2 + rj, 2 + rk , 2 + rl, 2 + rm, 2 + rn, 2 + ro, 2 + rp, 2 + rq, 2 + rr, 2 + rs, 2 + rt, 2 + ru, 2 + rv, 2 + rw, 2 + rx, 2 + ry, 2 + rz, 2 + sa, 2 + sb, 2 + sc, 2 + sd, 2 + se, 2 + sf, 2 + sg, 2 + sh, 2 + si, 2 + sj , 2 + sk, 2 + sl, 2 + sm, 2 + sn, 2 + so, 2 + sp, 2 + sq, 2 + sr, 3 + a, 3 + b, 3 + c, 3 + d, 3 + e, 3 + f, 3 + g, 3 + h, 3 + i, 3 + j, 3 + k, 3 + l, 3 + m, 3 + n, 3 + o, 3 + p, 3 + q , 3 + r, 3 + s, 3 + t, 3 + u, 3 + v, 3 + w, 3 + x, 3 + y, 3 + z, 3 + aa, 3 + ab, 3 + ac, 3 + ad, 3 + ae, 3 + af, 3 + ag, 3 + ah, 3 + ai, 3 + aj, 3 + ak, 3 + al, 3 + am, 3 + an, 3 + ao, 3 + ap , 3 + aq, 3 + ar, 3 + as, 3 + at, 3 + au, 3 + av, 3 + aw, 3 + ax, 3 + ay, 3 + az, 3 + ba, 3 + bb, 3 + bc, 3 + bd, 3 + be, 3 + bf, 3 + bg, 3 + bh, 3 + bi, 3 + bj, 3 + bk, 3 + bl, 3 + bm, 3 + bn, 3 + bo , 3 + bp, 3 + bq, 3 + br, 3 + bs, 3 + bt, 3 + bu, 3 + bv, 3 + bw, 3 + bx, 3 + by, 3 + bz, 3 + ca, 3 + cb, 3 + cc, 3 + cd, 3 + ce, 3 + cf, 3 + cg, 3 + ch, 3 + ci, 3 + cj, 3 + ck, 3 + cl, 3 + cm, 3 + cn , 3 + co, 3 + cp, 3 + cq, 3 + cr, 3 + cs, 3 + ct, 3 + cu, 3 + cv, 3 + cw, 3 + cx, 3 + cy, 3 + cz, 3 + da, 3 + db, 3 + dc, 3 + dd, 3 + de, 3 + df, 3 + dg, 3 + dh, 3 + di, 3 + dj, 3 + dk, 3 + dl, 3 + dm , 3 + dn, 3 + do, 3 + dp, 3 + dq, 3 + dr, 3 + ds, 3 + dt, 3 + du, 3 + dv, 3 + dw, 3 + dx, 3 + dy, 3 + dz, 3 + ea, 3 + eb, 3 + ec, 3 + ed, 3 + ee, 3 + ef, 3 + eg, 3 + eh, 3 + ei, 3 + ej, 3 + ek, 3 + el , 3 + em, 3 + en, 3 + eo, 3 + ep, 3 + eq, 3 + er, 3 + es, 3 + et, 3 + eu, 3 + ev, 3 + ew, 3 + ex, 3 + ey, 3 + ez, 3 + fa, 3 + fb, 3 + fc, 3 + fd, 3 + fe, 3 + ff, 3 + fg, 3 + fh, 3 + fi, 3 + fj, 3 + fk , 3 + fl, 3 + fm, 3 + fn, 3 + fo, 3 + fp, 3 + fq, 3 + fr, 3 + fs, 3 + ft, 3 + fu, 3 + fv, 3 + fw, 3 + fx, 3 + fy, 3 + fz, 3 + ga, 3 + gb, 3 + gc, 3 + gd, 3 + ge, 3 + gf, 3 + gg, 3 + gh, 3 + gi, 3 + gj, 3 + gk, 3 + gl, 3 + gm, 3 + gn, 3 + go, 3 + gp, 3 + gq, 3 + gr, 3 + gs, 3 + gt, 3 + gu, 3 + gv, 3 + gw, 3 + gx, 3 + gy, 3 + gz, 3 + ha, 3 + hb, 3 + hc, 3 + hd, 3 + he, 3 + hf, 3 + hg, 3 + hh, 3 + hi, 3 + hj, 3 + hk, 3 + hl, 3 + hm, 3 + hn, 3 + ho, 3 + hp, 3 + hq, 3 + hr, 3 + hs, 3 + ht, 3 + hu, 3 + hv, 3 + hw, 3 + hx, 3 + hy, 3 + hz, 3 + ia, 3 + ib, 3 + ic, 3 + id, 3 + ie, 3 + if, 3 + ig, 3 + ih, 3 + ii, 3 + ij, 3 + ik, 3 + il, 3 + im, 3 + in, 3 + io, 3 + ip, 3 + iq, 3 + ir, 3 + is, 3 + it, 3 + iu, 3 + iv, 3 + iw, 3 + ix, 3 + iy, 3 + iz, 3 + ja, 3 + jb, 3 + jc, 3 + jd, 3 + je, 3 + jf, 3 + jg, 3 + jh, 3 + ji, 3 + jj, 3 + jk, 3 + jl, 3 + jm, 3 + jn, 3 + jo, 3 + jp, 3 + jq, 3 + jr, 3 + js, 3 + jt, 3 + ju, 3 + jv, 3 + jw, 3 + jx, 3 + jy, 3 + jz, 3 + ka, 3 + kb, 3 + kc, 3 + kd, 3 + ke, 3 + kf, 3 + kg, 3 + kh, 3 + ki, 3 + kj, 3 + kk, 3 + kl, 3 + km, 3 + kn, 3 + ko, 3 + kp, 3 + kq, 3 + kr, 3 + ks, 3 + kt, 3 + ku, 3 + kv, 3 + kw, 3 + kx, 3 + ky, 3 + kz, 3 + la, 3 + lb, 3 + lc, 3 + ld, 3 + le, 3 + lf, 3 + lg, 3 + lh, 3 + li, 3 + lj, 3 + lk, 3 + ll, 3 + lm, 3 + ln, 3 + lo, 3 + lp, 3 + lq, 3 + lr, 3 + ls, 3 + lt, 3 + lu, 3 + lv, 3 + lw, 3 + lx, 3 + ly, 3 + lz, 3 + ma, 3 + mb, 3 + mc, 3 + md, 3 + me, 3 + mf, 3 + mg, 3 + mh, 3 + mi, 3 + mj, 3 + mk, 3 + ml, 3 + mm, 3 + mn, 3 + mo, 3 + mp, 3 + mq, 3 + mr, 3 + ms, 3 + mt, 3 + mu, 3 + mv, 3 + mw, 3 + mx, 3 + my, 3 + mz, 3 + na, 3 + nb, 3 + nc, 3 + nd, 3 + ne, 3 + nf, 3 + ng, 3 + nh, 3 + ni, 3 + nj, 3 + nk, 3 + nl, 3 + nm, 3 + nn, 3 + no, 3 + np, 3 + nq, 3 + nr, 3 + ns, 3 + nt, 3 + nu, 3 + nv, 3 + nw, 3 + nx, 3 + ny, 3 + nz, 3 + oa, 3 + ob, 3 + oc, 3 + od, 3 + oe, 3 + of, 3 + og, 3 + oh, 3 + oi, 3 + oj, 3 + ok, 3 + ol, 3 + om, 3 + on, 3 + oo, 3 + op, 3 + oq, 3 + or, 3 + os, 3 + ot, 3 + ou, 3 + ov, 3 + ow, 3 + ox, 3 + oy, 3 + oz, 3 + pa, 3 + pb, 3 + pc, 3 + pd, 3 + pe, 3 + pf, 3 + pg, 3 + ph, 3 + pi, 3 + pj, 3 + pk, 3 + pl, 3 + pm, 3 + pn, 3 + po, 3 + pp, 3 + pq, 3 + pr, 3 + ps, 3 + pt, 3 + pu, 3 + pv, 3 + pw, 3 + px, 3 + py, 3 + pz, 3 + qa, 3 + qb, 3 + qc, 3 + qd, 3 + qe, 3 + qf, 3 + qg, 3 + qh, 3 + qi, 3 + qj, 3 + qk, 3 + ql, 3 + qm, 3 + qn, 3 + qo, 3 + qp, 3 + qq, 3 + qr, 3 + qs, 3 + qt, 3 + qu, 3 + qv, 3 + qw, 3 + qx, 3 + qy, 3 + qz, 3 + ra, 3 + rb, 3 + rc, 3 + rd, 3 + re, 3 + rf, 3 + rg, 3 + rh, 3 + ri, 3 + rj, 3 + rk, 3 + rl, 3 + rm, 3 + rn, 3 + ro, 3 + rp, 3 + rq, 3 + rr, 3 + rs, 3 + rt, 3 + ru, 3 + rv, 3 + rw, 3 + rx, 3 + ry, 3 + rz, 3 + sa, 3 + sb, 3 + sc, 3 + sd, 3 + se, 3 + sf, 3 + sg, 3 + sh, 3 + si, 3 + sj, 3 + sk, 3 + sl, 3 + sm, 3 + sn, 3 + so, 3 + sp, 3 + sq, 3 + sr, 4 + a, 4 + b, 4 + c, 4 + d, 4 + e, 4 + f, 4 + g, 4 + h, 4 + i, 4 + j, 4 + k, 4 + l, 4 + m, 4 + n, 4 + o, 4 + p, 4 + q, 4 + r, 4 + s, 4 + t, 4 + u, 4 + v, 4 + w, 4 + x, 4 + y, 4 + z, 4 + aa, 4 + ab, 4 + ac, 4 + ad, 4 + ae, 4 + af, 4 + ag, 4 + ah, 4 + ai, 4 + aj, 4 + ak, 4 + al, 4 + am, 4 + an, 4 + ao, 4 + ap, 4 + aq, 4 + ar, 4 + as, 4 + at, 4 + au, 4 + av, 4 + aw, 4 + ax, 4 + ay, 4 + az, 4 + ba, 4 + bb, 4 + bc, 4 + bd, 4 + be, 4 + bf, 4 + bg, 4 + bh, 4 + bi, 4 + bj, 4 + bk, 4 + bl, 4 + bm, 4 + bn, 4 + bo, 4 + bp, 4 + bq, 4 + br, 4 + bs, 4 + bt, 4 + bu, 4 + bv, 4 + bw, 4 + bx, 4 + by, 4 + b z, 4 + ca, 4 + cb, 4 + cc, 4 + cd, 4 + ce, 4 + cf, 4 + cg, 4 + ch, 4 + ci, 4 + cj, 4 + ck, 4 + cl, 4 + cm, 4 + cn, 4 + co, 4 + cp, 4 + cq, 4 + cr, 4 + cs, 4 + ct, 4 + cu, 4 + cv, 4 + cw, 4 + cx, 4 + cy, 4 + cz, 4 + da, 4 + db, 4 + dc, 4 + dd, 4 + de, 4 + df, 4 + dg, 4 + dh, 4 + di, 4 + dj, 4 + dk, 4 + dl, 4 + dm, 4 + dn, 4 + do, 4 + dp, 4 + dq, 4 + dr, 4 + ds, 4 + dt, 4 + du, 4 + dv, 4 + dw, 4 + dx, 4 + dy, 4 + dz, 4 + ea, 4 + eb, 4 + ec, 4 + ed, 4 + ee, 4 + ef, 4 + eg, 4 + eh, 4 + ei, 4 + ej, 4 + ek, 4 + el, 4 + em, 4 + en, 4 + eo, 4 + ep, 4 + eq, 4 + er, 4 + es, 4 + et, 4 + eu, 4 + ev, 4 + ew, 4 + ex, 4 + ey, 4 + ez, 4 + fa, 4 + fb, 4 + fc, 4 + fd, 4 + fe, 4 + ff, 4 + fg, 4 + fh, 4 + fi, 4 + fj, 4 + fk, 4 + fl, 4 + fm, 4 + fn, 4 + fo, 4 + fp, 4 + fq, 4 + fr, 4 + fs, 4 + ft, 4 + fu, 4 + fv, 4 + fw, 4 + fx, 4 + fy, 4 + fz, 4 + ga, 4 + gb, 4 + gc, 4 + gd, 4 + ge, 4 + gf, 4 + gg, 4 + gh, 4 + gi, 4 + gj, 4 + gk, 4 + gl, 4 + gm, 4 + gn, 4 + go, 4 + gp, 4 + gq, 4 + gr, 4 + gs, 4 + gt, 4 + gu, 4 + gv, 4 + gw, 4 + gx, 4 + gy, 4 + gz, 4 + ha, 4 + hb, 4 + hc, 4 + hd, 4 + he, 4 + hf, 4 + hg, 4 + hh, 4 + hi, 4 + hj, 4 + hk, 4 + hl, 4 + 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16 + ni, 16 + nj, 16 + nk, 16 + nl, 16 + nm, 16 + nn, 16 + no, 16 + np, 16 + nq, 16 + nr, 16 + ns, 16 + nt, 16 + nu, 16 + nv, 16 + nw, 16 + nx, 16 + ny, 16 + nz, 16 + oa, 16 + ob, 16 + oc, 16 + od, 16 + oe, 16 + of, 16 + og, 16 + oh, 16 + oi, 16 + oj, 16 + ok, 16 + ol, 16 + om, 16 + on, 16 + oo, 16 + op, 16 + oq, 16 + or, 16 + os, 16 + ot, 16 + ou, 16 + ov, 16 + ow, 16 + ox, 16 + oy, 16 + oz, 16 + pa, 16 + pb, 16 + pc, 16 + pd, 16 + pe, 16 + pf, 16 + pg, 16 + ph, 16 + pi, 16 + pj, 16 + pk, 16 + pl, 16 + pm, 16 + pn, 16 + po, 16 + pp, 16 + pq, 16 + pr, 16 + ps, 16 + pt, 16 + pu, 16 + pv, 16 + pw, 16 + px, 16 + py, 16 + pz, 16 + qa, 16 + qb, 16 + qc, 16 + qd, 16 + qe, 16 + qf, 16 + qg, 16 + qh, 16 + qi, 16 + qj, 16 + qk, 16 + ql, 16 + qm, 16 + qn, 16 + qo, 16 + qp, 16 + qq, 16 + qr, 16 + qs, 16 + qt, 16 + qu, 16 + qv, 16 + qw, 16 + qx, 16 + qy, 16 + qz, 16 + ra, 16 + rb, 16 + rc, 16 + rd, 16 + re, 16 + rf, 16 + rg, 16 + rh, 16 + ri, 16 + rj, 16 + rk, 16 + rl, 16 + rm, 16 + rn, 16 + ro, 16 + rp, 16 + rq, 16 + rr, 16 + rs, 16 + rt, 16 + ru, 16 + rv, 16 + rw, 16 + rx, 16 + ry, 16 + rz, 16 + sa, 16 + sb, 16 + sc, 16 + sd, 16 + se, 16 + sf, 16 + sg, 16 + sh, 16 + si, 16 + sj, 16 + sk, 16 + sl, 16 + sm, 16 + sn, 16 + so, 16 + sp, 16 + sq, 16 + sr, 17 + a, 17 + b, 17 + c, 17 + d, 17 + e, 17 + f, 17 + g, 17 + h, 17 + i, 17 + j, 17 + k, 17 + l, 17 + m, 17 + n, 17 + o, 17 + p, 17 + q, 17 + r, 17 + s, 17 + t, 17 + u, 17 + v, 17 + w, 17 + x, 17 + y, 17 + z, 17 + aa, 17 + ab, 17 + ac, 17 + ad, 17 + ae, 17 + af, 17 + ag, 17 + ah, 17 + ai, 17 + aj, 17 + ak, 17 + al, 17 + am, 17 + an, 17 + ao, 17 + ap, 17 + aq, 17 + ar, 17 + as, 17 + at, 17 + au, 17 + av, 17 + aw, 17 + ax, 17 + ay, 17 + az, 17 + ba, 17 + bb, 17 + bc, 17 + bd, 17 + be, 17 + bf, 17 + bg, 17 + bh, 17 + bi, 17 + bj, 17 + bk, 17 + bl, 17 + bm, 17 + bn, 17 + bo, 17 + bp, 17 + bq, 17 + br, 17 + bs, 17 + bt, 17 + bu, 17 + bv, 17 + bw, 17 + bx, 17 + by, 17 + bz, 17 + ca, 17 + cb, 17 + cc, 17 + cd, 17 + ce, 17 + cf, 17 + cg, 17 + ch, 17 + ci, 17 + cj, 17 + ck, 17 + cl, 17 + cm, 17 + cn, 17 + co, 17 + cp, 17 + cq, 17 + cr, 17 + cs, 17 + ct, 17 + cu, 17 + cv, 17 + cw, 17 + cx, 17 + cy, 17 + cz, 17 + da, 17 + db, 17 + dc, 17 + dd, 17 + de, 17 + df, 17 + dg, 17 + dh, 17 + di, 17 + dj, 17 + dk, 17 + dl, 17 + dm, 17 + dn, 17 + do, 17 + dp, 17 + dq, 17 + dr, 17 + ds, 17 + dt, 17 + du, 17 + dv, 17 + dw, 17 + dx, 17 + dy, 17 + dz, 17 + ea, 17 + eb, 17 + ec, 17 + ed, 17 + ee, 17 + ef, 17 + eg, 17 + eh, 17 + ei, 17 + ej, 17 + ek, 17 + el, 17 + em, 17 + en, 17 + eo, 17 + ep, 17 + eq, 17 + er, 17 + es, 17 + et, 17 + eu, 17 + ev, 17 + ew, 17 + ex, 17 + ey, 17 + ez, 17 + fa, 17 + fb, 17 + fc, 17 + fd, 17 + fe, 17 + ff, 17 + fg, 17 + fh, 17 + fi, 17 + fj, 17 + fk, 17 + fl, 17 + fm, 17 + fn, 17 + fo, 17 + fp, 17 + fq, 17 + fr, 17 + fs, 17 + ft, 17 + fu, 17 + fv, 17 + fw, 17 + fx, 17 + fy, 17 + fz, 17 + ga, 17 + gb, 17 + gc, 17 + gd, 17 + ge, 17 + gf, 17 + gg, 17 + gh, 17 + gi, 17 + gj, 17 + gk, 17 + gl, 17 + gm, 17 + gn, 17 + go, 17 + g p, 17 + gq, 17 + gr, 17 + gs, 17 + gt, 17 + gu, 17 + gv, 17 + gw, 17 + gx, 17 + gy, 17 + gz, 17 + ha, 17 + hb, 17 + hc, 17 + hd, 17 + he, 17 + hf, 17 + hg, 17 + hh, 17 + hi, 17 + hj, 17 + hk, 17 + hl, 17 + hm, 17 + hn, 17 + ho, 17 + hp, 17 + hq, 17 + hr, 17 + hs, 17 + ht, 17 + hu, 17 + hv, 17 + hw, 17 + hx, 17 + hy, 17 + hz, 17 + ia, 17 + ib, 17 + ic, 17 + id, 17 + ie, 17 + if, 17 + ig, 17 + ih, 17 + ii, 17 + ij, 17 + ik, 17 + il, 17 + im, 17 + in, 17 + io, 17 + ip, 17 + iq, 17 + ir, 17 + is, 17 + it, 17 + iu, 17 + iv, 17 + iw, 17 + ix, 17 + iy, 17 + iz, 17 + ja, 17 + jb, 17 + jc, 17 + jd, 17 + je, 17 + jf, 17 + jg, 17 + jh, 17 + ji, 17 + jj, 17 + jk, 17 + jl, 17 + jm, 17 + jn, 17 + jo, 17 + jp, 17 + jq, 17 + jr, 17 + js, 17 + jt, 17 + ju, 17 + jv, 17 + jw, 17 + jx, 17 + jy, 17 + jz, 17 + ka, 17 + kb, 17 + kc, 17 + kd, 17 + ke, 17 + kf, 17 + kg, 17 + kh, 17 + ki, 17 + kj, 17 + kk, 17 + kl, 17 + km, 17 + kn, 17 + ko, 17 + kp, 17 + kq, 17 + kr, 17 + ks, 17 + kt, 17 + ku, 17 + kv, 17 + kw, 17 + kx, 17 + ky, 17 + kz, 17 + la, 17 + lb, 17 + lc, 17 + ld, 17 + le, 17 + lf, 17 + lg, 17 + lh, 17 + li, 17 + lj, 17 + lk, 17 + ll, 17 + lm, 17 + ln, 17 + lo, 17 + lp, 17 + lq, 17 + lr, 17 + ls, 17 + lt, 17 + lu, 17 + lv, 17 + lw, 17 + lx, 17 + ly, 17 + lz, 17 + ma, 17 + mb, 17 + mc, 17 + md, 17 + me, 17 + mf, 17 + mg, 17 + mh, 17 + mi, 17 + mj, 17 + mk, 17 + ml, 17 + mm, 17 + mn, 17 + mo, 17 + mp, 17 + mq, 17 + mr, 17 + ms, 17 + mt, 17 + mu, 17 + mv, 17 + mw, 17 + mx, 17 + my, 17 + mz, 17 + na, 17 + nb, 17 + nc, 17 + nd, 17 + ne, 17 + nf, 17 + ng, 17 + nh, 17 + ni, 17 + nj, 17 + nk, 17 + nl, 17 + nm , 17 + nn, 17 + no, 17 + np, 17 + nq, 17 + nr, 17 + ns, 17 + nt, 17 + nu, 17 + nv, 17 + nw, 17 + nx, 17 + ny, 17 + nz, 17 + oa, 17 + ob, 17 + oc, 17 + od, 17 + oe, 17 + of, 17 + og, 17 + oh, 17 + oi, 17 + oj, 17 + ok, 17 + ol , 17 + om, 17 + on, 17 + oo, 17 + op, 17 + oq, 17 + or, 17 + os, 17 + ot, 17 + ou, 17 + ov, 17 + ow, 17 + ox, 17 + oy, 17 + oz, 17 + pa, 17 + pb, 17 + pc, 17 + pd, 17 + pe, 17 + pf, 17 + pg, 17 + ph, 17 + pi, 17 + pj, 17 + pk , 17 + pl, 17 + pm, 17 + pn, 17 + po, 17 + pp, 17 + pq, 17 + pr, 17 + ps, 17 + pt, 17 + pu, 17 + pv, 17 + pw, 17 + px, 17 + py, 17 + pz, 17 + qa, 17 + qb, 17 + qc, 17 + qd, 17 + qe, 17 + qf, 17 + qg, 17 + qh, 17 + qi, 17 + qj , 17 + qk, 17 + ql, 17 + qm, 17 + qn, 17 + qo, 17 + qp, 17 + qq, 17 + qr, 17 + qs, 17 + qt, 17 + qu, 17 + qv, 17 + qw, 17 + qx, 17 + qy, 17 + qz, 17 + ra, 17 + rb, 17 + rc, 17 + rd, 17 + re, 17 + rf, 17 + rg, 17 + rh, 17 + ri , 17 + rj, 17 + rk, 17 + rl, 17 + rm, 17 + rn, 17 + ro, 17 + rp, 17 + rq, 17 + rr, 17 + rs, 17 + rt, 17 + ru, 17 + rv, 17 + rw, 17 + rx, 17 + ry, 17 + rz, 17 + sa, 17 + sb, 17 + sc, 17 + sd, 17 + se, 17 + sf, 17 + sg, 17 + sh , 17 + si, 17 + sj, 17 + sk, 17 + sl, 17 + sm, 17 + sn, 17 + so, 17 + sp, 17 + sq, 17 + sr, 18 + a, 18 + b, 18 + c, 18 + d, 18 + e, 18 + f, 18 + g, 18 + h, 18 + i, 18 + j, 18 + k, 18 + l, 18 + m, 18 + n, 18 + o , 18 + p, 18 + q, 18 + r, 18 + s, 18 + t, 18 + u, 18 + v, 18 + w , 18 + x, 18 + y, 18 + z, 18 + aa, 18 + ab, 18 + ac, 18 + ad, 18 + ae, 18 + af, 18 + ag, 18 + ah, 18 + ai, 18 + aj, 18 + ak, 18 + al, 18 + am, 18 + an, 18 + ao, 18 + ap, 18 + aq, 18 + ar, 18 + as, 18 + at, 18 + au, 18 + av , 18 + aw, 18 + ax, 18 + ay, 18 + az, 18 + ba, 18 + bb, 18 + bc, 18 + bd, 18 + be, 18 + bf, 18 + bg, 18 + bh, 18 + bi, 18 + bj, 18 + bk, 18 + bl, 18 + bm, 18 + bn, 18 + bo, 18 + bp, 18 + bq, 18 + br, 18 + bs, 18 + bt, 18 + bu , 18 + bv, 18 + bw, 18 + bx, 18 + by, 18 + bz, 18 + ca, 18 + cb, 18 + cc, 18 + cd, 18 + ce, 18 + cf, 18 + cg, 18 + ch, 18 + ci, 18 + cj, 18 + ck, 18 + cl, 18 + cm, 18 + cn, 18 + co, 18 + cp, 18 + cq, 18 + cr, 18 + cs, 18 + ct , 18 + cu, 18 + cv, 18 + cw, 18 + cx, 18 + cy, 18 + cz, 18 + da, 18 + db, 18 + dc, 18 + dd, 18 + de, 18 + df, 18 + dg, 18 + dh, 18 + di, 18 + dj, 18 + dk, 18 + dl, 18 + dm, 18 + dn, 18 + do, 18 + dp, 18 + dq, 18 + dr, 18 + ds , 18 + dt, 18 + du, 18 + dv, 18 + dw, 18 + dx, 18 + dy, 18 + dz, 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18 + mo, 18 + mp, 18 + mq, 18 + mr, 18 + m s, 18 + mt, 18 + mu, 18 + mv, 18 + mw, 18 + mx, 18 + my, 18 + mz, 18 + na, 18 + nb, 18 + nc, 18 + nd, 18 + ne, 18 + nf, 18 + ng, 18 + nh, 18 + ni, 18 + nj, 18 + nk, 18 + nl, 18 + nm, 18 + nn, 18 + no, 18 + np, 18 + nq, 18 + nr, 18 + ns, 18 + nt, 18 + nu, 18 + nv, 18 + nw, 18 + nx, 18 + ny, 18 + nz, 18 + oa, 18 + ob, 18 + oc, 18 + od, 18 + oe, 18 + of, 18 + og, 18 + oh, 18 + oi, 18 + oj, 18 + ok, 18 + ol, 18 + om, 18 + on, 18 + oo, 18 + op, 18 + oq, 18 + or, 18 + os, 18 + ot, 18 + ou, 18 + ov, 18 + ow, 18 + ox, 18 + oy, 18 + oz, 18 + pa, 18 + pb, 18 + pc, 18 + pd, 18 + pe, 18 + pf, 18 + pg, 18 + ph, 18 + pi, 18 + pj, 18 + pk, 18 + pl, 18 + pm, 18 + pn, 18 + po, 18 + pp, 18 + pq, 18 + pr, 18 + ps, 18 + pt, 18 + pu, 18 + pv, 18 + pw, 18 + px, 18 + py, 18 + pz, 18 + qa, 18 + qb, 18 + qc, 18 + qd, 18 + qe, 18 + qf, 18 + qg, 18 + qh, 18 + qi, 18 + qj, 18 + qk, 18 + ql, 18 + qm, 18 + qn, 18 + qo, 18 + qp, 18 + qq, 18 + qr, 18 + qs, 18 + qt, 18 + qu, 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so, 19 + sp, 19 + sq, 19 + sr,
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3 + gg, 23 + gh, 23 + gi, 23 + gj, 23 + gk, 23 + gl, 23 + gm, 23 + gn, 23 + go, 23 + gp, 23 + gq, 23 + gr, 23 + gs, 23 + gt, 23 + gu, 23 + gv, 23 + gw, 23 + gx, 23 + gy, 23 + gz, 23 + ha, 23 + hb, 23 + hc, 23 + hd, 23 + he, 23 + hf, 23 + hg, 23 + hh, 23 + hi, 23 + hj, 23 + hk, 23 + hl, 23 + hm, 23 + hn, 23 + ho, 23 + hp, 23 + hq, 23 + hr, 23 + hs, 23 + ht, 23 + hu, 23 + hv, 23 + hw, 23 + hx, 23 + hy, 23 + hz, 23 + ia, 23 + ib, 23 + ic, 23 + id, 23 + ie, 23 + if, 23 + ig, 23 + ih, 23 + ii, 23 + ij, 23 + ik, 23 + il, 23 + im, 23 + in, 23 + io, 23 + ip, 23 + iq, 23 + ir, 23 + is, 23 + it, 23 + iu, 23 + iv, 23 + iw, 23 + ix, 23 + iy, 23 + iz, 23 + ja, 23 + jb, 23 + jc, 23 + jd, 23 + je, 23 + jf, 23 + jg, 23 + jh, 23 + ji, 23 + jj, 23 + jk, 23 + jl, 23 + jm, 23 + jn, 23 + jo, 23 + jp, 23 + jq, 23 + jr, 23 + js, 23 + jt, 23 + ju, 23 + jv, 23 + jw, 23 + jx, 23 + jy, 23 + jz, 23 + ka, 23 + kb, 23 + kc, 23 + kd, 23 + ke, 23 + kf, 23 + kg, 23 + kh, 23 + ki, 23 + kj, 23 + kk, 23 + kl, 23 + km, 23 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23 + ou, 23 + ov, 23 + ow, 23 + ox, 23 + oy, 23 + oz, 23 + pa, 23 + pb, 23 + pc, 23 + pd, 23 + pe, 23 + pf, 23 + pg, 23 + ph, 23 + pi, 23 + pj, 23 + pk, 23 + pl, 23 + pm, 23 + pn , 23 + po, 23 + pp, 23 + pq, 23 + pr, 23 + ps, 23 + pt, 23 + pu, 23 + pv, 23 + pw, 23 + px, 23 + py, 23 + pz, 23 + qa, 23 + qb, 23 + qc, 23 + qd, 23 + qe, 23 + qf, 23 + qg, 23 + qh, 23 + qi, 23 + qj, 23 + qk, 23 + ql, 23 + qm , 23 + qn, 23 + qo, 23 + qp, 23 + qq, 23 + qr, 23 + qs, 23 + qt, 23 + qu, 23 + qv, 23 + qw, 23 + qx, 23 + qy, 23 + qz, 23 + ra, 23 + rb, 23 + rc, 23 + rd, 23 + re, 23 + rf, 23 + rg, 23 + rh, 23 + ri, 23 + rj, 23 + rk, 23 + rl , 23 + rm, 23 + rn, 23 + ro, 23 + rp, 23 + rq, 23 + rr, 23 + rs, 23 + rt, 23 + ru, 23 + rv, 23 + rw, 23 + rx, 23 + ry, 23 + rz, 23 + sa, 23 + sb, 23 + sc, 23 + sd, 23 + se, 23 + sf, 23 + sg, 23 + sh, 23 + si, 23 + sj, 23 + sk , 23 + sl, 23 + sm, 23 + sn, 23 + so, 23 + sp, 23 + sq, 23 + sr, 24 + a, 24 + b, 24 + c, 24 + d, 24 + e, 24 + f, 24 + g, 24 + h, 24 + i, 24 + 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24 + ds, 24 + dt , 24 + du, 24 + dv, 24 + dw, 24 + dx, 24 + dy, 24 + dz, 24 + ea, 24 + eb, 24 + ec, 24 + ed, 24 + ee, 24 + ef, 24 + eg, 24 + eh, 24 + ei, 24 + ej, 24 + ek, 24 + el, 24 + em, 24 + en, 24 + eo, 24 + ep, 24 + eq, 24 + er, 24 + es , 24 + et, 24 + eu, 24 + ev, 24 + ew, 24 + ex, 24 + ey, 24 + ez, 24 + fa, 24 + fb, 24 + fc, 24 + fd, 24 + fe, 24 + ff, 24 + fg, 24 + fh, 24 + fi, 24 + fj, 24 + fk, 24 + fl, 24 + fm, 24 + fn, 24 + fo, 24 + fp, 24 + fq, 24 + fr , 24 + fs, 24 + ft, 24 + fu, 24 + fv, 24 + fw, 24 + fx, 24 + fy, 24 + fz, 24 + ga, 24 + gb, 24 + gc, 24 + gd, 24 + ge, 24 + gf, 24 + gg, 24 + gh, 24 + gi, 24 + gj, 24 + gk, 24 + gl, 24 + gm, 24 + gn, 24 + go, 24 + gp, 24 + gq, 24 + gr, 24 + gs, 24 + gt, 24 + gu, 24 + gv, 24 + gw, 24 + gx, 24 + gy, 24 + gz, 24 + ha, 24 + hb, 24 + hc, 24 + hd, 24 + he, 24 + hf, 24 + hg, 24 + hh, 24 + hi, 24 + hj, 24 + hk, 24 + hl, 24 + hm, 24 + hn, 24 + ho, 24 + hp, 24 + hq, 24 + hr, 24 + hs, 24 + ht, 24 + hu, 24 + hv, 24 + hw, 24 + hx, 24 + 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25 + sg, 25 + sh, 25 + si, 25 + sj, 25 + sk, 25 + sl, 2 5 + sm, 25 + sn, 25 + so, 25 + sp, 25 + sq, 25 + sr, 26 + a, 26 + b, 26 + c, 26 + d, 26 + e, 26 + f, 26 + g, 26 + h, 26 + i, 26 + j, 26 + k, 26 + l, 26 + m, 26 + n, 26 + o, 26 + p, 26 + q, 26 + r, 26 + s, 26 + t, 26 + u, 26 + v, 26 + w, 26 + x, 26 + y, 26 + z, 26 + aa, 26 + ab, 26 + ac, 26 + ad, 26 + ae, 26 + af, 26 + ag, 26 + ah, 26 + ai, 26 + aj, 26 + ak, 26 + al, 26 + am, 26 + an, 26 + ao, 26 + ap, 26 + aq, 26 + ar, 26 + as, 26 + at, 26 + au, 26 + av, 26 + aw, 26 + ax, 26 + ay, 26 + az, 26 + ba, 26 + bb, 26 + bc, 26 + bd, 26 + be, 26 + bf, 26 + bg, 26 + bh, 26 + bi, 26 + bj, 26 + bk, 26 + bl, 26 + bm, 26 + bn, 26 + bo, 26 + bp, 26 + bq, 26 + br, 26 + bs, 26 + bt, 26 + bu, 26 + bv, 26 + bw, 26 + bx, 26 + by, 26 + bz, 26 + ca, 26 + cb, 26 + cc, 26 + cd, 26 + ce, 26 + cf, 26 + cg, 26 + ch, 26 + ci, 26 + cj, 26 + ck, 26 + cl, 26 + cm, 26 + cn, 26 + co, 26 + cp, 26 + cq, 26 + cr, 26 + cs, 26 + ct, 26 + cu, 26 + cv, 26 + cw, 26 + cx, 26 + cy, 26 + cz, 26 + da, 26 + db, 26 + dc, 26 + dd, 26 + de, 26 + df, 26 + dg, 26 + dh, 26 + di, 26 + dj, 26 + dk, 26 + dl, 26 + dm, 26 + dn, 26 + do, 26 + dp, 26 + dq, 26 + dr, 26 + ds, 26 + dt, 26 + du, 26 + dv, 26 + dw, 26 + dx, 26 + dy, 26 + dz, 26 + ea, 26 + eb, 26 + ec, 26 + ed, 26 + ee, 26 + ef, 26 + eg, 26 + eh, 26 + ei, 26 + ej, 26 + ek, 26 + el, 26 + em, 26 + en, 26 + eo, 26 + ep, 26 + eq, 26 + er, 26 + es, 26 + et, 26 + eu, 26 + ev, 26 + ew, 26 + ex, 26 + ey, 26 + ez, 26 + fa, 26 + fb, 26 + fc, 26 + fd, 26 + fe, 26 + ff, 26 + fg, 26 + fh, 26 + fi, 2 6 + fj, 26 + fk, 26 + fl, 26 + fm, 26 + fn, 26 + fo, 26 + fp, 26 + fq, 26 + fr, 26 + fs, 26 + ft, 26 + fu, 26 + fv, 26 + fw, 26 + fx, 26 + fy, 26 + fz, 26 + ga, 26 + gb, 26 + gc, 26 + gd, 26 + ge, 26 + gf, 26 + gg, 26 + gh, 26 + gi, 26 + gj, 26 + gk, 26 + gl, 26 + gm, 26 + gn, 26 + go, 26 + gp, 26 + gq, 26 + gr, 26 + gs, 26 + gt, 26 + gu, 26 + gv, 26 + gw, 26 + gx, 26 + gy, 26 + gz, 26 + ha, 26 + hb, 26 + hc, 26 + hd, 26 + he, 26 + hf, 26 + hg, 26 + hh, 26 + hi, 26 + hj, 26 + hk, 26 + hl, 26 + hm, 26 + hn, 26 + ho, 26 + hp, 26 + hq, 26 + hr, 26 + hs, 26 + ht, 26 + hu, 26 + hv, 26 + hw, 26 + hx, 26 + hy, 26 + hz, 26 + ia, 26 + ib, 26 + ic, 26 + id, 26 + ie, 26 + if, 26 + ig, 26 + ih, 26 + ii, 26 + ij, 26 + ik, 26 + il, 26 + im, 26 + in, 26 + io, 26 + ip, 26 + iq, 26 + ir, 26 + is, 26 + it, 26 + iu, 26 + iv, 26 + iw, 26 + ix, 26 + iy, 26 + iz, 26 + ja, 26 + jb, 26 + jc, 26 + jd, 26 + je, 26 + jf, 26 + jg, 26 + jh, 26 + ji, 26 + jj, 26 + jk, 26 + jl, 26 + jm, 26 + jn, 26 + jo, 26 + jp, 26 + jq, 26 + jr, 26 + js, 26 + jt, 26 + ju, 26 + jv, 26 + jw, 26 + jx, 26 + jy, 26 + jz, 26 + ka, 26 + kb, 26 + kc, 26 + kd, 26 + ke, 26 + kf, 26 + kg, 26 + kh, 26 + ki, 26 + kj, 26 + kk, 26 + kl, 26 + km, 26 + kn, 26 + ko, 26 + kp, 26 + kq, 26 + kr, 26 + ks, 26 + kt, 26 + ku, 26 + kv, 26 + kw, 26 + kx, 26 + ky, 26 + kz, 26 + la, 26 + lb, 26 + lc, 26 + ld, 26 + le, 26 + lf, 26 + lg, 26 + lh, 26 + li, 26 + lj, 26 + lk, 26 + ll, 26 + lm, 26 + ln, 26 + lo, 26 + lp, 26 + lq, 26 + lr, 26 + ls, 26 + lt , 26 + lu, 26 + lv, 26 + lw, 26 + lx, 26 + ly, 26 + lz, 26 + ma, 26 + mb, 26 + mc, 26 + md, 26 + me, 26 + mf, 26 + mg, 26 + mh, 26 + mi, 26 + mj, 26 + mk, 26 + ml, 26 + mm, 26 + mn, 26 + mo, 26 + mp, 26 + mq, 26 + mr, 26 + ms , 26 + mt, 26 + mu, 26 + mv, 26 + mw, 26 + mx, 26 + my, 26 + mz, 26 + na, 26 + nb, 26 + nc, 26 + nd, 26 + ne, 26 + nf, 26 + ng, 26 + nh,
26 + ni, 26 + nj, 26 + nk, 26 + nl, 26 + nm, 26 + nn, 26 + no, 26 + np, 26 + nq, 26 + nr, 26 + ns, 26 + nt, 26 + nu, 26 + nv, 26 + nw, 26 + nx, 26 + ny, 26 + nz, 26 + oa, 26 + ob, 26 + oc, 26 + od, 26 + oe, 26 + of, 26 + og, 26 + oh, 26 + oi, 26 + oj, 26 + ok, 26 + ol, 26 + om, 26 + on, 26 + oo, 26 + op, 26 + oq, 26 + or, 26 + os, 26 + ot, 26 + ou, 26 + ov, 26 + ow, 26 + ox, 26 + oy, 26 + oz, 26 + pa, 26 + pb, 26 + pc, 26 + pd, 26 + pe, 26 + pf, 26 + pg, 26 + ph, 26 + pi, 26 + pj, 26 + pk, 26 + pl, 26 + pm, 26 + pn, 26 + po, 26 + pp, 26 + pq, 26 + pr, 26 + ps, 26 + pt, 26 + pu, 26 + pv, 26 + pw, 26 + px, 26 + py, 26 + pz, 26 + qa, 26 + qb, 26 + qc, 26 + qd, 26 + qe, 26 + qf, 26 + qg, 26 + qh, 26 + qi, 26 + qj, 26 + qk, 26 + ql, 26 + qm, 26 + qn, 26 + qo, 26 + qp, 26 + qq, 26 + qr, 26 + qs, 26 + qt, 26 + qu, 26 + qv, 26 + qw, 26 + qx, 26 + qy, 26 + qz, 26 + ra, 26 + rb, 26 + rc, 26 + rd, 26 + re, 26 + rf, 26 + rg, 26 + rh, 26 + ri, 26 + rj, 26 + rk, 26 + rl, 26 + rm, 26 + rn, 26 + ro, 26 + rp, 26 + rq, 26 + rr, 26 + rs, 26 + rt, 26 + ru, 26 + rv, 26 + rw, 26 + rx, 26 + ry, 26 + rz, 26 + sa, 26 + sb, 26 + sc, 26 + sd, 26 + se, 26 + sf, 26 + sg, 26 + sh, 26 + si, 26 + sj, 26 + sk, 26 + sl, 26 + sm, 26 + sn, 26 + so, 26 + sp, 26 + sq, 26 + sr, 27 + a, 27 + b, 27 + c, 27 + d, 27 + e, 27 + f, 27 + g, 27 + h, 27 + i, 27 + j, 27 + k, 27 + l, 27 + m, 27 + n, 27 + o, 27 + p, 27 + q, 27 + r, 27 + s, 27 + t, 27 + u, 27 + v, 27 + w, 27 + x, 27 + y, 27 + z, 27 + aa, 27 + ab, 27 + ac, 27 + ad, 27 + ae, 27 + af, 27 + ag, 27 + ah, 27 + ai, 27 + aj, 27 + ak, 27 + al, 27 + am, 27 + an, 27 + ao, 27 + ap, 27 + aq, 27 + ar, 27 + as, 27 + at, 27 + au, 27 + av, 27 + aw, 27 + ax, 27 + ay, 27 + az, 27 + ba, 27 + bb, 27 + bc, 27 + bd, 27 + be, 27 + bf, 27 + bg, 27 + bh, 27 + bi, 27 + bj, 27 + bk, 27 + bl, 27 + bm, 27 + bn, 27 + bo, 27 + bp, 27 + bq, 27 + br, 27 + bs, 27 + bt, 27 + bu, 27 + bv, 27 + bw, 27 + bx, 27 + by, 27 + bz, 27 + ca, 27 + cb, 27 + cc, 27 + cd, 27 + ce, 27 + cf, 27 + cg, 27 + ch, 27 + ci, 27 + cj, 27 + ck, 27 + cl, 27 + cm, 27 + cn, 27 + co, 27 + cp, 27 + cq, 27 + cr, 27 + cs, 27 + ct, 27 + cu, 27 + cv, 27 + cw, 27 + cx, 27 + cy, 27 + cz, 27 + da, 27 + db, 27 + dc, 27 + dd, 27 + de, 27 + df, 27 + dg, 27 + dh, 27 + di, 27 + dj, 27 + dk, 27 + dl, 27 + dm, 27 + dn, 27 + do, 27 + dp, 27 + dq, 27 + dr, 27 + ds, 27 + dt, 27 + du, 27 + dv, 27 + dw, 27 + dx, 27 + dy, 27 + dz, 27 + ea, 27 + eb, 27 + ec, 27 + ed, 27 + ee, 27 + ef, 27 + eg, 27 + eh, 27 + ei, 27 + ej, 27 + ek, 27 + el, 27 + em, 27 + en, 27 + eo, 27 + ep, 27 + eq, 27 + er, 27 + es, 27 + et, 27 + eu, 27 + ev, 27 + ew, 27 + ex, 27 + ey, 27 + ez, 27 + fa, 27 + fb, 27 + fc, 27 + fd, 27 + fe, 27 + ff, 27 + fg, 27 + fh, 27 + fi, 27 + fj, 27 + fk, 27 + fl, 27 + fm, 27 + fn, 27 + fo, 27 + fp, 27 + fq, 27 + fr, 27 + fs, 27 + ft, 27 + fu, 27 + fv, 27 + fw, 27 + fx, 27 + fy, 27 + fz, 27 + ga, 27 + gb, 27 + gc, 27 + gd, 27 + ge, 27 + gf, 27 + gg, 27 + gh, 27 + gi, 27 + gj, 27 + gk, 27 + gl, 27 + gm, 27 + gn, 27 + go, 27 + g p, 27 + gq, 27 + gr, 27 + gs, 27 + gt, 27 + gu, 27 + gv, 27 + gw, 27 + gx, 27 + gy, 27 + gz, 27 + ha, 27 + hb, 27 + hc, 27 + hd, 27 + he, 27 + hf, 27 + hg, 27 + hh, 27 + hi, 27 + hj, 27 + hk, 27 + hl, 27 + hm, 27 + hn, 27 + ho, 27 + hp, 27 + hq, 27 + hr, 27 + hs, 27 + ht, 27 + hu, 27 + hv, 27 + hw, 27 + hx, 27 + hy, 27 + hz, 27 + ia, 27 + ib, 27 + ic, 27 + id, 27 + ie, 27 + if, 27 + ig, 27 + ih, 27 + ii, 27 + ij, 27 + ik, 27 + il, 27 + im, 27 + in, 27 + io, 27 + ip, 27 + iq, 27 + ir, 27 + is, 27 + it, 27 + iu, 27 + iv, 27 + iw, 27 + ix, 27 + iy, 27 + iz, 27 + ja, 27 + jb, 27 + jc, 27 + jd, 27 + je, 27 + jf, 27 + jg, 27 + jh, 27 + ji, 27 + jj, 27 + jk, 27 + jl, 27 + jm, 27 + jn, 27 + jo, 27 + jp, 27 + jq, 27 + jr, 27 + js, 27 + jt, 27 + ju, 27 + jv, 27 + jw, 27 + jx, 27 + jy, 27 + jz, 27 + ka, 27 + kb, 27 + kc, 27 + kd, 27 + ke, 27 + kf, 27 + kg, 27 + kh, 27 + ki, 27 + kj, 27 + kk, 27 + kl, 27 + km, 27 + kn, 27 + ko, 27 + kp, 27 + kq, 27 + kr, 27 + ks, 27 + kt, 27 + ku, 27 + kv, 27 + kw, 27 + kx, 27 + ky, 27 + kz, 27 + la, 27 + lb, 27 + lc, 27 + ld, 27 + le, 27 + lf, 27 + lg, 27 + lh, 27 + li, 27 + lj, 27 + lk, 27 + ll, 27 + lm, 27 + ln, 27 + lo, 27 + lp, 27 + lq, 27 + lr, 27 + ls, 27 + lt, 27 + lu, 27 + lv, 27 + lw, 27 + lx, 27 + ly, 27 + lz, 27 + ma, 27 + mb, 27 + mc, 27 + md, 27 + me, 27 + mf, 27 + mg, 27 + mh, 27 + mi, 27 + mj, 27 + mk, 27 + ml, 27 + mm, 27 + mn, 27 + mo, 27 + mp, 27 + mq, 27 + mr, 27 + ms, 27 + mt, 27 + mu, 27 + mv, 27 + mw, 27 + mx, 27 + my, 27 + mz, 27 + na, 27 + nb, 27 + nc, 27 + nd, 27 + ne, 27 + nf, 27 + ng, 27 + nh, 27 + ni, 27 + nj, 27 + nk, 27 + nl, 27 + nm , 27 + nn, 27 + no, 27 + np, 27 + nq, 27 + nr, 27 + ns, 27 + nt, 27 + nu, 27 + nv, 27 + nw, 27 + nx, 27 + ny, 27 + nz, 27 + oa, 27 + ob, 27 + oc, 27 + od, 27 + oe, 27 + of, 27 + og, 27 + oh, 27 + oi, 27 + oj, 27 + ok, 27 + ol , 27 + om, 27 + on, 27 + oo, 27 + op, 27 + oq, 27 + or, 27 + os, 27 + ot, 27 + ou, 27 + ov, 27 + ow, 27 + ox, 27 + oy, 27 + oz, 27 + pa, 27 + pb, 27 + pc, 27 + pd, 27 + pe, 27 + pf, 27 + pg, 27 + ph, 27 + pi, 27 + pj, 27 + pk , 27 + pl, 27 + pm, 27 + pn, 27 + po, 27 + pp, 27 + pq, 27 + pr, 27 + ps, 27 + pt, 27 + pu, 27 + pv, 27 + pw, 27 + px, 27 + py, 27 + pz, 27 + qa, 27 + qb, 27 + qc, 27 + qd, 27 + qe, 27 + qf, 27 + qg, 27 + qh, 27 + qi, 27 + qj , 27 + qk, 27 + ql, 27 + qm, 27 + qn, 27 + qo, 27 + qp, 27 + qq, 27 + qr, 27 + qs, 27 + qt, 27 + qu, 27 + qv, 27 + qw, 27 + qx, 27 + qy, 27 + qz, 27 + ra, 27 + rb, 27 + rc, 27 + rd, 27 + re, 27 + rf, 27 + rg, 27 + rh, 27 + ri , 27 + rj, 27 + rk, 27 + rl, 27 + rm, 27 + rn, 27 + ro, 27 + rp, 27 + rq, 27 + rr, 27 + rs, 27 + rt, 27 + ru, 27 + rv, 27 + rw, 27 + rx, 27 + ry, 27 + rz, 27 + sa, 27 + sb, 27 + sc, 27 + sd, 27 + se, 27 + sf, 27 + sg, 27 + sh , 27 + si, 27 + sj, 27 + sk, 27 + sl, 27 + sm, 27 + sn, 27 + so, 27 + sp, 27 + sq, 27 + sr, 28 + a, 28 + b, 28 + c, 28 + d, 28 + e, 28 + f, 28 + g, 28 + h, 28 + i, 28 + j, 28 + k, 28 + l, 28 + m, 28 + n, 28 + o , 28 + p, 28 + q, 28 + r, 28 + s, 28 + t, 28 + u, 28 + v, 28 + w , 28 + x, 28 + y, 28 + z, 28 + aa, 28 + ab, 28 + ac, 28 + ad, 28 + ae, 28 + af, 28 + ag, 28 + ah, 28 + ai, 28 + aj, 28 + ak, 28 + al, 28 + am, 28 + an, 28 + ao, 28 + ap, 28 + aq, 28 + ar, 28 + as, 28 + at, 28 + au, 28 + av , 28 + aw, 28 + ax, 28 + ay, 28 + az, 28 + ba, 28 + bb, 28 + bc, 28 + bd, 28 + be, 28 + bf, 28 + bg, 28 + bh, 28 + bi, 28 + bj, 28 + bk, 28 + bl, 28 + bm, 28 + bn, 28 + bo, 28 + bp, 28 + bq, 28 + br, 28 + bs, 28 + bt, 28 + bu , 28 + bv, 28 + bw, 28 + bx, 28 + by, 28 + bz, 28 + ca, 28 + cb, 28 + cc, 28 + cd, 28 + ce, 28 + cf, 28 + cg, 28 + ch, 28 + ci, 28 + cj, 28 + ck, 28 + cl, 28 + cm, 28 + cn, 28 + co, 28 + cp, 28 + cq, 28 + cr, 28 + cs, 28 + ct , 28 + cu, 28 + cv, 28 + cw, 28 + cx, 28 + cy, 28 + cz, 28 + da, 28 + db, 28 + dc, 28 + dd, 28 + de, 28 + df, 28 + dg, 28 + dh, 28 + di, 28 + dj, 28 + dk, 28 + dl, 28 + dm, 28 + dn, 28 + do, 28 + dp, 28 + dq, 28 + dr, 28 + ds , 28 + dt, 28 + du, 28 + dv, 28 + dw, 28 + dx, 28 + dy, 28 + dz, 28 + ea, 28 + eb, 28 + ec, 28 + ed, 28 + ee, 28 + ef, 28 + eg, 28 + eh, 28 + ei, 28 + ej, 28 + ek, 28 + el, 28 + em, 28 + en, 28 + eo, 28 + ep, 28 + eq, 28 + er , 28 + es, 28 + et, 28 + eu, 28 + ev, 28 + ew, 28 + ex, 28 + ey, 28 + ez, 28 + fa, 28 + fb, 28 + fc, 28 + fd, 28 + fe, 28 + ff, 28 + fg, 28 + fh, 28 + fi, 28 + fj, 28 + fk, 28 + fl, 28 + fm, 28 + fn, 28 + fo, 28 + fp, 28 + fq , 28 + fr, 28 + fs, 28 + ft, 28 + fu, 28 + fv, 28 + fw, 28 + fx, 28 + fy, 28 + fz, 28 + ga, 28 + gb, 28 + gc, 28 + gd, 28 + ge, 28 + gf, 28 + gg, 28 + gh, 28 + gi, 28 + gj, 28 + gk, 28 + gl, 28 + gm, 28 + gn, 28 + go, 28 + gp, 28 + gq, 28 + gr, 28 + gs, 28 + gt, 28 + gu, 28 + gv, 28 + gw, 28 + gx, 28 + gy, 28 + gz, 28 + ha, 28 + hb, 28 + hc, 28 + hd, 28 + he, 28 + hf, 28 + hg, 28 + hh, 28 + hi, 28 + hj, 28 + hk, 28 + hl, 28 + hm, 28 + hn, 28 + ho, 28 + hp, 28 + hq, 28 + hr, 28 + hs, 28 + ht, 28 + hu, 28 + hv, 28 + hw, 28 + hx, 28 + hy, 28 + hz, 28 + ia, 28 + ib, 28 + ic, 28 + id, 28 + ie, 28 + if, 28 + ig, 28 + ih, 28 + ii, 28 + ij, 28 + ik, 28 + il, 28 + im, 28 + in, 28 + io, 28 + ip, 28 + iq, 28 + ir, 28 + is, 28 + it, 28 + iu, 28 + iv, 28 + iw, 28 + ix, 28 + iy, 28 + iz, 28 + ja, 28 + jb, 28 + jc, 28 + jd, 28 + je, 28 + jf, 28 + jg, 28 + jh, 28 + ji, 28 + jj, 28 + jk, 28 + jl, 28 + jm, 28 + jn, 28 + jo, 28 + jp, 28 + jq, 28 + jr, 28 + js, 28 + jt, 28 + ju, 28 + jv, 28 + jw, 28 + jx, 28 + jy, 28 + jz, 28 + ka, 28 + kb, 28 + kc, 28 + kd, 28 + ke, 28 + kf, 28 + kg, 28 + kh, 28 + ki, 28 + kj, 28 + kk, 28 + kl, 28 + km, 28 + kn, 28 + ko, 28 + kp, 28 + kq, 28 + kr, 28 + ks, 28 + kt, 28 + ku, 28 + kv, 28 + kw, 28 + kx, 28 + ky, 28 + kz, 28 + la, 28 + lb, 28 + lc, 28 + ld, 28 + le, 28 + lf, 28 + lg, 28 + lh, 28 + li, 28 + lj, 28 + lk, 28 + ll, 28 + lm, 28 + ln, 28 + lo, 28 + lp, 28 + lq, 28 + lr, 28 + ls, 28 + lt, 28 + lu, 28 + lv, 28 + lw, 28 + lx, 28 + ly, 28 + lz, 28 + ma, 28 + mb, 28 + mc, 28 + md, 28 + me, 28 + mf, 28 + mg, 28 + mh, 28 + mi, 28 + mj, 28 + mk, 28 + ml, 28 + mm, 28 + mn, 28 + mo, 28 + mp, 28 + mq, 28 + mr, 28 + m s, 28 + mt, 28 + mu, 28 + mv, 28 + mw, 28 + mx, 28 + my, 28 + mz, 28 + na, 28 + nb, 28 + nc, 28 + nd, 28 + ne, 28 + nf, 28 + ng, 28 + nh, 28 + ni, 28 + nj, 28 + nk, 28 + nl, 28 + nm, 28 + nn, 28 + no, 28 + np, 28 + nq, 28 + nr, 28 + ns, 28 + nt, 28 + nu, 28 + nv, 28 + nw, 28 + nx, 28 + ny, 28 + nz, 28 + oa, 28 + ob, 28 + oc, 28 + od, 28 + oe, 28 + of, 28 + og, 28 + oh, 28 + oi, 28 + oj, 28 + ok, 28 + ol, 28 + om, 28 + on, 28 + oo, 28 + op, 28 + oq, 28 + or, 28 + os, 28 + ot, 28 + ou, 28 + ov, 28 + ow, 28 + ox, 28 + oy, 28 + oz, 28 + pa, 28 + pb, 28 + pc, 28 + pd, 28 + pe, 28 + pf, 28 + pg, 28 + ph, 28 + pi, 28 + pj, 28 + pk, 28 + pl, 28 + pm, 28 + pn, 28 + po, 28 + pp, 28 + pq, 28 + pr, 28 + ps, 28 + pt, 28 + pu, 28 + pv, 28 + pw, 28 + px, 28 + py, 28 + pz, 28 + qa, 28 + qb, 28 + qc, 28 + qd, 28 + qe, 28 + qf, 28 + qg, 28 + qh, 28 + qi, 28 + qj, 28 + qk, 28 + ql, 28 + qm, 28 + qn, 28 + qo, 28 + qp, 28 + qq, 28 + qr, 28 + qs, 28 + qt, 28 + qu, 28 + qv, 28 + qw, 28 + qx, 28 + qy, 28 + qz, 28 + ra, 28 + rb, 28 + rc, 28 + rd, 28 + re, 28 + rf, 28 + rg, 28 + rh, 28 + ri, 28 + rj, 28 + rk, 28 + rl, 28 + rm, 28 + rn, 28 + ro, 28 + rp, 28 + rq, 28 + rr, 28 + rs, 28 + rt, 28 + ru, 28 + rv, 28 + rw, 28 + rx, 28 + ry, 28 + rz, 28 + sa, 28 + sb, 28 + sc, 28 + sd, 28 + se, 28 + sf, 28 + sg, 28 + sh, 28 + si, 28 + sj, 28 + sk, 28 + sl, 28 + sm, 28 + sn, 28 + so, 28 + sp, 28 + sq, 28 + sr, 29 + a, 29 + b, 29 + c, 29 + d, 29 + e, 29 + f, 29 + g, 29 + h, 29 + i, 29 + j, 29 + k, 29 + l, 29 + m, 29 + n, 29 + o, 29 + p, 29 + q, 29 + r, 29 + s, 29 + t, 29 + u, 29 + v, 29 + w, 29 + x, 29 + y, 29 + z, 29 + aa, 29 + ab, 29 + ac, 29 + ad, 29 + ae, 29 + af, 29 + ag, 29 + ah, 29 + ai, 29 + aj, 29 + ak, 29 + al, 29 + am, 29 + an, 29 + ao, 29 + ap, 29 + aq, 29 + ar, 29 + as, 29 + at, 29 + au, 29 + av, 29 + aw, 29 + ax, 29 + ay, 29 + az, 29 + ba, 29 + bb, 29 + bc, 29 + bd, 29 + be, 29 + bf, 29 + bg, 29 + bh, 29 + bi, 29 + bj, 29 + bk, 29 + bl, 29 + bm, 29 + bn, 29 + bo, 29 + bp, 29 + bq, 29 + br, 29 + bs, 29 + bt, 29 + bu, 29 + bv, 29 + bw, 29 + bx, 29 + by, 29 + bz, 29 + ca, 29 + cb, 29 + cc, 29 + cd, 29 + ce, 29 + cf, 29 + cg, 29 + ch, 29 + ci, 29 + cj, 29 + ck, 29 + cl, 29 + cm, 29 + cn, 29 + co, 29 + cp, 29 + cq, 29 + cr, 29 + cs, 29 + ct, 29 + cu, 29 + cv, 29 + cw, 29 + cx, 29 + cy, 29 + cz, 29 + da, 29 + db, 29 + dc, 29 + dd, 29 + de, 29 + df, 29 + dg, 29 + dh, 29 + di, 29 + dj, 29 + dk, 29 + dl, 29 + dm, 29 + dn, 29 + do, 29 + dp, 29 + dq, 29 + dr, 29 + ds, 29 + dt, 29 + du, 29 + dv, 29 + dw, 29 + dx, 29 + dy, 29 + dz, 29 + ea, 29 + eb, 29 + ec, 29 + ed, 29 + ee, 29 + ef, 29 + eg, 29 + eh, 29 + ei, 29 + ej, 29 + ek, 29 + el, 29 + em, 29 + en, 29 + eo, 29 + ep, 29 + eq, 29 + er, 29 + es, 29 + et, 29 + eu, 29 + ev, 29 + ew, 29 + ex, 29 + ey, 29 + ez, 29 + fa, 29 + fb, 29 + fc, 29 + fd, 29 + fe, 29 + ff, 29 + fg, 29 + fh, 29 + fi, 29 + fj, 29 + fk, 29 + fl, 29 + fm, 29 + fn, 29 + fo, 29 + fp, 29 + fq, 29 + fr, 29 + fs, 29 + ft, 29 + fu, 29 + fv, 29 + fw, 29 + fx, 29 + fy, 29 + fz, 29 + ga, 29 + gb, 29 + gc, 29 + gd, 29 + ge, 29 + gf, 29 + gg, 29 + gh, 29 + gi, 29 + gj, 29 + gk, 29 + gl, 29 + gm , 29 + gn, 29 + go, 29 + gp, 29 + gq, 29 + gr, 29 + gs, 29 + gt, 29 + gu, 29 + gv, 29 + gw, 29 + gx, 29 + gy, 29 + gz, 29 + ha, 29 + hb, 29 + hc, 29 + hd, 29 + he, 29 + hf, 29 + hg, 29 + hh, 29 + hi, 29 + hj, 29 + hk, 29 + hl , 29 + hm, 29 + hn, 29 + ho, 29 + hp, 29 + hq, 29 + hr, 29 + hs, 29 + ht, 29 + hu, 29 + hv, 29 + hw, 29 + hx, 29 + hy, 29 + hz, 29 + ia, 29 + ib, 29 + ic, 29 + id, 29 + ie, 29 + if, 29 + ig, 29 + ih, 29 + ii, 29 + ij, 29 + ik , 29 + il, 29 + im, 29 + in, 29 + io, 29 + ip, 29 + iq, 29 + ir, 29 + is, 29 + it, 29 + iu, 29 + iv, 29 + iw, 29 + ix, 29 + iy, 29 + iz, 29 + ja, 29 + jb, 29 + jc, 29 + jd, 29 + je, 29 + jf, 29 + jg, 29 + jh, 29 + ji, 29 + jj , 29 + jk, 29 + jl, 29 + jm, 29 + jn, 29 + jo, 29 + jp, 29 + jq, 29 + jr, 29 + js, 29 + jt, 29 + ju, 29 + jv, 29 + jw, 29 + jx, 29 + jy, 29 + jz, 29 + ka, 29 + kb, 29 + kc, 29 + kd, 29 + ke, 29 + kf, 29 + kg, 29 + kh, 29 + ki , 29 + kj, 29 + kk, 29 + kl, 29 + km, 29 + kn, 29 + ko, 29 + kp, 29 + kq, 29 + kr, 29 + ks, 29 + kt, 29 + ku, 29 + kv, 29 + kw, 29 + kx, 29 + ky, 29 + kz, 29 + la, 29 + lb, 29 + lc, 29 + ld, 29 + le, 29 + lf, 29 + lg, 29 + lh , 29 + li, 29 + lj, 29 + lk, 29 + ll, 29 + lm, 29 + ln, 29 + lo, 29 + lp, 29 + lq, 29 + lr, 29 + ls, 29 + lt, 29 + lu, 29 + lv, 29 + lw, 29 + lx, 29 + ly, 29 + lz, 29 + ma, 29 + mb, 29 + mc, 29 + md, 29 + me, 29 + mf, 29 + mg , 29 + mh, 29 + mi, 29 + mj, 29 + mk, 29 + ml, 29 + mm, 29 + mn, 29 + mo, 29 + mp, 29 + mq, 29 + mr, 29 + ms, 29 + mt, 29 + mu, 29 + mv, 29 + mw, 29 + mx, 29 + my, 29 + mz, 29 + na, 29 + nb, 29 + nc, 29 + nd, 29 + ne, 29 + nf, 29 + ng, 29 + nh, 29 + ni, 29 + nj, 29 + nk, 29 + nl, 29 + nm, 29 + nn, 29 + no, 29 + np, 29 + nq, 29 + nr, 29 + ns, 29 + nt, 29 + nu, 29 + nv, 29 + nw, 29 + nx, 29 + ny, 29 + nz, 29 + oa, 29 + ob, 29 + oc, 29 + od, 29 + oe, 29 + of, 29 + og, 29 + oh, 29 + oi, 29 + oj, 29 + ok, 29 + ol, 29 + om, 29 + on, 29 + oo, 29 + op, 29 + oq, 29 + or, 29 + os, 29 + ot, 29 + ou, 29 + ov, 29 + ow, 29 + ox, 29 + oy, 29 + oz, 29 + pa, 29 + pb, 29 + pc, 29 + pd, 29 + pe, 29 + pf, 29 + pg, 29 + ph, 29 + pi, 29 + pj, 29 + pk, 29 + pl, 29 + pm, 29 + pn, 29 + po, 29 + pp, 29 + pq, 29 + pr, 29 + ps, 29 + pt, 29 + pu, 29 + pv, 29 + pw, 29 + px, 29 + py, 29 + pz, 29 + qa, 29 + qb, 29 + qc, 29 + qd, 29 + qe, 29 + qf, 29 + qg, 29 + qh, 29 + qi, 29 + qj, 29 + qk, 29 + ql, 29 + qm, 29 + qn, 29 + qo, 29 + qp, 29 + qq, 29 + qr, 29 + qs, 29 + qt, 29 + qu, 29 + qv, 29 + qw, 29 + qx, 29 + qy, 29 + qz, 29 + ra, 29 + rb, 29 + rc, 29 + rd, 29 + re, 29 + rf, 29 + rg, 29 + rh, 29 + ri, 29 + rj, 29 + rk, 29 + rl, 29 + rm, 29 + rn, 29 + ro, 29 + rp, 29 + rq, 29 + rr, 29 + rs, 29 + rt, 29 + ru, 29 + rv, 29 + rw, 29 + rx, 29 + ry, 29 + rz, 29 + sa, 29 + sb, 29 + sc, 29 + sd, 29 + se, 29 + sf, 29 + sg, 29 + sh, 29 + si, 29 + sj, 29 + sk, 29 + sl, 29 + sm, 29 + sn, 29 + so, 29 + sp, 29 + sq, 29 + sr,
30 + a, 30 + b, 30 + c, 30 + d, 30 + e, 30 + f, 30 + g, 30 + h, 30 + i, 30 + j, 30 + k, 30 + l, 30 + m, 30 + n, 30 + o, 30 + p, 30 + q, 30 + r, 30 + s, 30 + t, 30 + u, 30 + v, 30 + w, 30 + x, 30 + y, 30 + z, 30 + aa, 30 + ab, 30 + ac, 30 + ad, 30 + ae, 30 + af, 30 + ag, 30 + ah, 30 + ai, 30 + aj, 30 + ak, 30 + al, 30 + am, 30 + an, 30 + ao, 30 + ap, 30 + aq, 30 + ar, 30 + as, 30 + at, 30 + au, 30 + av, 30 + aw, 30 + ax, 30 + ay, 30 + az, 30 + ba, 30 + bb, 30 + bc, 30 + bd, 30 + be, 30 + bf, 30 + bg, 30 + bh, 30 + bi, 30 + bj, 30 + bk, 30 + bl, 30 + bm, 30 + bn, 30 + bo, 30 + bp, 30 + bq, 30 + br, 30 + bs, 30 + bt, 30 + bu, 30 + bv, 30 + bw, 30 + bx, 30 + by, 30 + bz, 30 + ca, 30 + cb, 30 + cc, 30 + cd, 30 + ce, 30 + cf, 30 + cg, 30 + ch, 30 + ci, 30 + cj, 30 + ck, 30 + cl, 30 + cm, 30 + cn, 30 + co, 30 + cp, 30 + cq, 30 + cr, 30 + cs, 30 + ct, 30 + cu, 30 + cv, 30 + cw, 30 + cx, 30 + cy, 30 + cz, 30 + da, 30 + db, 30 + dc, 30 + dd, 30 + de, 30 + df, 30 + dg, 30 + dh, 30 + di, 30 + dj, 30 + dk, 30 + dl, 30 + dm, 30 + dn, 30 + do, 30 + dp, 30 + dq, 30 + dr, 30 + ds, 30 + dt, 30 + du, 30 + dv, 30 + dw, 30 + dx, 30 + dy, 30 + dz, 30 + ea, 30 + eb, 30 + ec, 30 + ed, 30 + ee, 30 + ef, 30 + eg, 30 + eh, 30 + ei, 30 + ej, 30 + ek, 30 + el, 30 + em, 30 + en, 30 + eo, 30 + ep, 30 + eq, 30 + er, 30 + es, 30 + et, 30 + eu, 30 + ev, 30 + ew, 30 + ex, 30 + ey, 30 + ez, 30 + fa, 30 + fb, 30 + fc, 30 + fd, 30 + fe, 30 + ff, 30 + fg, 30 + fh, 30 + fi, 30 + fj, 30 + fk, 30 + fl, 30 + fm, 30 + fn, 30 + fo, 30 + fp, 30 + fq, 30 + fr, 30 + fs, 30 + ft, 30 + fu, 30 + fv, 30 + fw, 30 + fx, 30 + fy, 30 + fz, 30 + ga, 30 + gb, 30 + gc, 30 + gd, 30 + ge, 30 + gf, 30 + gg, 30 + gh, 30 + gi, 30 + gj, 30 + gk, 30 + gl, 30 + gm, 30 + gn, 30 + go, 30 + gp, 30 + gq, 30 + gr, 30 + gs, 30 + gt, 30 + gu, 30 + gv, 30 + gw, 30 + gx, 30 + gy, 30 + gz, 30 + ha, 30 + hb, 30 + hc, 30 + hd, 30 + he, 30 + hf, 30 + hg, 30 + hh, 30 + hi, 30 + hj, 30 + hk, 30 + hl, 30 + hm, 30 + hn, 30 + ho, 30 + hp, 30 + hq, 30 + hr, 30 + hs, 30 + ht, 30 + hu, 30 + hv, 30 + hw, 30 + hx, 30 + hy, 30 + hz, 30 + ia, 30 + ib, 30 + ic, 30 + id, 30 + ie, 30 + if, 30 + ig, 30 + ih, 30 + ii, 30 + ij, 30 + ik, 30 + il, 30 + im, 30 + in, 30 + io, 30 + ip, 30 + iq, 30 + ir, 30 + is, 30 + it, 30 + iu, 30 + iv, 30 + iw, 30 + ix, 30 + iy, 30 + iz, 30 + ja, 30 + jb, 30 + jc, 30 + jd, 30 + je, 30 + jf, 30 + jg, 30 + jh, 30 + ji, 30 + jj, 30 + jk, 30 + jl, 30 + jm, 30 + jn, 30 + jo, 30 + jp, 30 + jq, 30 + jr, 30 + js, 30 + jt, 30 + ju, 30 + jv, 30 + jw, 30 + jx, 30 + jy, 30 + jz, 30 + ka, 30 + kb, 30 + kc, 30 + kd, 30 + ke, 30 + kf, 30 + kg, 30 + kh, 30 + ki, 30 + kj, 30 + kk, 30 + kl, 30 + km, 30 + kn, 30 + ko, 30 + kp, 30 + kq, 30 + kr, 30 + ks, 30 + kt, 30 + ku, 30 + kv, 30 + kw, 30 + kx, 30 + ky, 30 + kz, 30 + la, 30 + lb, 30 + lc, 30 + ld, 30 + le, 30 + lf, 30 + lg, 30 + lh, 30 + li, 30 + lj, 30 + lk, 30 + ll, 30 + lm, 30 + ln, 30 + lo, 30 + lp, 30 + lq, 30 + lr, 30 + ls, 30 + lt, 30 + lu, 30 + lv, 30 + lw, 30 + lx, 30 + ly, 30 + l z, 30 + ma, 30 + mb, 30 + mc, 30 + md, 30 + me, 30 + mf, 30 + mg, 30 + mh, 30 + mi, 30 + mj, 30 + mk, 30 + ml, 30 + mm, 30 + mn, 30 + mo, 30 + mp, 30 + mq, 30 + mr, 30 + ms, 30 + mt, 30 + mu, 30 + mv, 30 + mw, 30 + mx, 30 + my, 30 + mz, 30 + na, 30 + nb, 30 + nc, 30 + nd, 30 + ne, 30 + nf, 30 + ng, 30 + nh, 30 + ni, 30 + nj, 30 + nk, 30 + nl, 30 + nm, 30 + nn, 30 + no, 30 + np, 30 + nq, 30 + nr, 30 + ns, 30 + nt, 30 + nu, 30 + nv, 30 + nw, 30 + nx, 30 + ny, 30 + nz, 30 + oa, 30 + ob, 30 + oc, 30 + od, 30 + oe, 30 + of, 30 + og, 30 + oh, 30 + oi, 30 + oj, 30 + ok, 30 + ol, 30 + om, 30 + on, 30 + oo, 30 + op, 30 + oq, 30 + or, 30 + os, 30 + ot, 30 + ou, 30 + ov, 30 + ow, 30 + ox, 30 + oy, 30 + oz, 30 + pa, 30 + pb, 30 + pc, 30 + pd, 30 + pe, 30 + pf, 30 + pg, 30 + ph, 30 + pi, 30 + pj, 30 + pk, 30 + pl, 30 + pm, 30 + pn, 30 + po, 30 + pp, 30 + pq, 30 + pr, 30 + ps, 30 + pt, 30 + pu, 30 + pv, 30 + pw, 30 + px, 30 + py, 30 + pz, 30 + qa, 30 + qb, 30 + qc, 30 + qd, 30 + qe, 30 + qf, 30 + qg, 30 + qh, 30 + qi, 30 + qj, 30 + qk, 30 + ql, 30 + qm, 30 + qn, 30 + qo, 30 + qp, 30 + qq, 30 + qr, 30 + qs, 30 + qt, 30 + qu, 30 + qv, 30 + qw, 30 + qx, 30 + qy, 30 + qz, 30 + ra, 30 + rb, 30 + rc, 30 + rd, 30 + re, 30 + rf, 30 + rg, 30 + rh, 30 + ri, 30 + rj, 30 + rk, 30 + rl, 30 + rm, 30 + rn, 30 + ro, 30 + rp, 30 + rq, 30 + rr, 30 + rs, 30 + rt, 30 + ru, 30 + rv, 30 + rw, 30 + rx, 30 + ry, 30 + rz, 30 + sa, 30 + sb, 30 + sc, 30 + sd, 30 + se, 30 + sf, 30 + sg, 30 + sh, 30 + si, 30 + sj, 30 + sk, 30 + sl, 30 + sm, 30 + sn, 30 + so, 30 + sp, 30 + sq, 30 + sr, 31 + a, 31 + b, 31 + c, 31 + d, 31 + e , 31 + f, 31 + g, 31 + h, 31 + i, 31 + j, 31 + k, 31 + l, 31 + m, 31 + n, 31 + o, 31 + p, 31 + q, 31 + r, 31 + s, 31 + t, 31 + u, 31 + v, 31 + w, 31 + x, 31 + y, 31 + z, 31 + aa, 31 + ab, 31 + ac, 31 + ad , 31 + ae, 31 + af, 31 + ag, 31 + ah, 31 + ai, 31 + aj, 31 + ak, 31 + al, 31 + am, 31 + an, 31 + ao, 31 + ap, 31 + aq, 31 + ar, 31 + as, 31 + at, 31 + au, 31 + av, 31 + aw, 31 + ax, 31 + ay, 31 + az, 31 + ba, 31 + bb, 31 + bc , 31 + bd, 31 + be, 31 + bf, 31 + bg, 31 + bh, 31 + bi, 31 + bj, 31 + bk, 31 + bl, 31 + bm, 31 + bn, 31 + bo, 31 + bp, 31 + bq, 31 + br, 31 + bs, 31 + bt, 31 + bu, 31 + bv, 31 + bw, 31 + bx, 31 + by, 31 + bz, 31 + ca, 31 + cb , 31 + cc, 31 + cd, 31 + ce, 31 + cf, 31 + cg, 31 + ch, 31 + ci, 31 + cj, 31 + ck, 31 + cl, 31 + cm, 31 + cn, 31 + co, 31 + cp, 31 + cq, 31 + cr, 31 + cs, 31 + ct, 31 + cu, 31 + cv, 31 + cw, 31 + cx, 31 + cy, 31 + cz, 31 + da , 31 + db, 31 + dc, 31 + dd, 31 + de, 31 + df, 31 + dg, 31 + dh, 31 + di, 31 + dj, 31 + dk, 31 + dl, 31 + dm, 31 + dn, 31 + do, 31 + dp, 31 + dq, 31 + dr, 31 + ds, 31 + dt, 31 + du, 31 + dv, 31 + dw, 31 + dx, 31 + dy, 31 + dz , 31 + ea, 31 + eb, 31 + ec, 31 + ed, 31 + ee, 31 + ef, 31 + eg, 31 + eh, 31 + ei, 31 + ej, 31 + ek, 31 + el, 31 + em, 31 + en, 31 + eo, 31 + ep, 31 + eq, 31 + er, 31 + es, 31 + et, 31 + eu, 31 + ev, 31 + ew, 31 + ex, 31 + ey , 31 + ez, 31 + fa, 31 + fb, 31 + fc, 31 + fd, 31 + fe, 31 + ff, 31 + fg, 31 + fh, 31 + fi, 31 + fj, 31 + fk, 31 + fl, 31 + fm, 31 + fn, 31 + fo, 31 + fp, 31 + fq, 31 + fr, 31 + fs, 31 + ft , 31 + fu, 31 + fv, 31 + fw, 31 + fx, 31 + fy, 31 + fz, 31 + ga, 31 + gb, 31 + gc, 31 + gd, 31 + ge, 31 + gf, 31 + gg, 31 + gh, 31 + gi, 31 + gj, 31 + gk, 31 + gl, 31 + gm, 31 + gn, 31 + go, 31 + gp, 31 + gq, 31 + gr, 31 + gs , 31 + gt, 31 + gu, 31 + gv, 31 + gw, 31 + gx, 31 + gy, 31 + gz, 31 + ha, 31 + hb, 31 + hc, 31 + hd, 31 + he, 31 + hf, 31 + hg, 31 + hh, 31 + hi, 31 + hj, 31 + hk, 31 + hl, 31 + hm, 31 + hn, 31 + ho, 31 + hp, 31 + hq, 31 + hr , 31 + hs, 31 + ht, 31 + hu, 31 + hv, 31 + hw, 31 + hx, 31 + hy, 31 + hz, 31 + ia, 31 + ib, 31 + ic, 31 + id, 31 + ie, 31 + if, 31 + ig, 31 + ih, 31 + ii, 31 + ij, 31 + ik, 31 + il, 31 + im, 31 + in, 31 + io, 31 + ip, 31 + iq , 31 + ir, 31 + is, 31 + it, 31 + iu, 31 + iv, 31 + iw, 31 + ix, 31 + iy, 31 + iz, 31 + ja, 31 + jb, 31 + jc, 31 + jd, 31 + je, 31 + jf, 31 + jg, 31 + jh, 31 + ji, 31 + jj, 31 + jk, 31 + jl, 31 + jm, 31 + jn, 31 + jo, 31 + jp , 31 + jq, 31 + jr, 31 + js, 31 + jt, 31 + ju, 31 + jv, 31 + jw, 31 + jx, 31 + jy, 31 + jz, 31 + ka, 31 + kb, 31 + kc, 31 + kd, 31 + ke, 31 + kf, 31 + kg, 31 + kh, 31 + ki, 31 + kj, 31 + kk, 31 + kl, 31 + km, 31 + kn, 31 + ko , 31 + kp, 31 + kq, 31 + kr, 31 + ks, 31 + kt, 31 + ku, 31 + kv, 31 + kw, 31 + kx, 31 + ky, 31 + kz, 31 + la, 31 + lb, 31 + lc, 31 + ld, 31 + le, 31 + lf, 31 + lg, 31 + lh, 31 + li, 31 + lj, 31 + lk, 31 + ll, 31 + lm, 31 + ln , 31 + lo, 31 + lp, 31 + lq, 31 + lr, 31 + ls, 31 + lt, 31 + lu, 31 + lv, 31 + lw, 31 + lx, 31 + ly, 31 + lz, 31 + ma, 31 + mb, 31 + mc, 31 + md, 31 + me, 31 + mf, 31 + mg, 31 + mh, 31 + mi, 31 + mj, 31 + mk, 31 + ml, 31 + mm, 31 + mn, 31 + mo, 31 + mp, 31 + mq, 31 + mr, 31 + ms, 31 + mt, 31 + mu, 31 + mv, 31 + mw, 31 + mx, 31 + my, 31 + mz, 31 + na, 31 + nb, 31 + nc, 31 + nd, 31 + ne, 31 + nf, 31 + ng, 31 + nh, 31 + ni, 31 + nj, 31 + nk, 31 + nl, 31 + nm, 31 + nn, 31 + no, 31 + np, 31 + nq, 31 + nr, 31 + ns, 31 + nt, 31 + nu, 31 + nv, 31 + nw, 31 + nx, 31 + ny, 31 + nz, 31 + oa, 31 + ob, 31 + oc, 31 + od, 31 + oe, 31 + of, 31 + og, 31 + oh, 31 + oi, 31 + oj, 31 + ok, 31 + ol, 31 + om, 31 + on, 31 + oo, 31 + op, 31 + oq, 31 + or, 31 + os, 31 + ot, 31 + ou, 31 + ov, 31 + ow, 31 + ox, 31 + oy, 31 + oz, 31 + pa, 31 + pb, 31 + pc, 31 + pd, 31 + pe, 31 + pf, 31 + pg, 31 + ph, 31 + pi, 31 + pj, 31 + pk, 31 + pl, 31 + pm, 31 + pn, 31 + po, 31 + pp, 31 + pq, 31 + pr, 31 + ps, 31 + pt, 31 + pu, 31 + pv, 31 + pw, 31 + px, 31 + py, 31 + pz, 31 + qa, 31 + qb, 31 + qc, 31 + qd, 31 + qe, 31 + qf, 31 + qg, 31 + qh, 31 + qi, 31 + qj, 31 + qk, 31 + ql, 31 + qm, 31 + qn, 31 + qo, 31 + qp, 31 + qq, 31 + qr, 31 + qs, 31 + qt, 31 + qu, 31 + qv, 31 + qw, 31 + qx, 31 + qy, 31 + qz, 31 + ra, 31 + rb, 31 + rc, 31 + rd, 31 + re, 31 + rf, 31 + rg, 31 + rh, 31 + ri, 31 + rj, 31 + rk, 31 + rl, 31 + rm, 31 + rn, 31 + ro, 31 + rp, 31 + rq, 31 + rr, 31 + rs, 31 + rt, 31 + ru, 31 + rv, 31 + rw, 31 + rx, 31 + ry, 31 + rz, 31 + sa, 31 + sb, 31 + s c, 31 + sd, 31 + se, 31 + sf, 31 + sg, 31 + sh, 31 + si, 31 + sj, 31 + sk, 31 + sl, 31 + sm, 31 + sn, 31 + so, 31 + sp, 31 + sq, 31 + sr, 32 + a, 32 + b, 32 + c, 32 + d, 32 + e, 32 + f, 32 + g, 32 + h, 32 + i, 32 + j, 32 + k, 32 + l, 32 + m, 32 + n, 32 + o, 32 + p, 32 + q, 32 + r, 32 + s, 32 + t, 32 + u, 32 + v, 32 + w, 32 + x, 32 + y, 32 + z, 32 + aa, 32 + ab, 32 + ac, 32 + ad, 32 + ae, 32 + af, 32 + ag, 32 + ah, 32 + ai, 32 + aj, 32 + ak, 32 + al, 32 + am, 32 + an, 32 + ao, 32 + ap, 32 + aq, 32 + ar, 32 + as, 32 + at, 32 + au, 32 + av, 32 + aw, 32 + ax, 32 + ay, 32 + az, 32 + ba, 32 + bb, 32 + bc, 32 + bd, 32 + be, 32 + bf, 32 + bg, 32 + bh, 32 + bi, 32 + bj, 32 + bk, 32 + bl, 32 + bm, 32 + bn, 32 + bo, 32 + bp, 32 + bq, 32 + br, 32 + bs, 32 + bt, 32 + bu, 32 + bv, 32 + bw, 32 + bx, 32 + by, 32 + bz, 32 + ca, 32 + cb, 32 + cc, 32 + cd, 32 + ce, 32 + cf, 32 + cg, 32 + ch, 32 + ci, 32 + cj, 32 + ck, 32 + cl, 32 + cm, 32 + cn, 32 + co, 32 + cp, 32 + cq, 32 + cr, 32 + cs, 32 + ct, 32 + cu, 32 + cv, 32 + cw, 32 + cx, 32 + cy, 32 + cz, 32 + da, 32 + db, 32 + dc, 32 + dd, 32 + de, 32 + df, 32 + dg, 32 + dh, 32 + di, 32 + dj, 32 + dk, 32 + dl, 32 + dm, 32 + dn, 32 + do, 32 + dp, 32 + dq, 32 + dr, 32 + ds, 32 + dt, 32 + du, 32 + dv, 32 + dw, 32 + dx, 32 + dy, 32 + dz, 32 + ea, 32 + eb, 32 + ec, 32 + ed, 32 + ee, 32 + ef, 32 + eg, 32 + eh, 32 + ei, 32 + ej, 32 + ek, 32 + el, 32 + em, 32 + en, 32 + eo, 32 + ep, 32 + eq, 32 + er, 32 + es, 32 + et, 32 + eu, 32 + ev, 32 + ew, 32 + ex, 32 + ey, 32 + e z, 32 + fa, 32 + fb, 32 + fc, 32 + fd, 32 + fe, 32 + ff, 32 + fg, 32 + fh, 32 + fi, 32 + fj, 32 + fk, 32 + fl, 32 + fm, 32 + fn, 32 + fo, 32 + fp, 32 + fq, 32 + fr, 32 + fs, 32 + ft, 32 + fu, 32 + fv, 32 + fw, 32 + fx, 32 + fy, 32 + fz, 32 + ga, 32 + gb, 32 + gc, 32 + gd, 32 + ge, 32 + gf, 32 + gg, 32 + gh, 32 + gi, 32 + gj, 32 + gk, 32 + gl, 32 + gm, 32 + gn, 32 + go, 32 + gp, 32 + gq, 32 + gr, 32 + gs, 32 + gt, 32 + gu, 32 + gv, 32 + gw, 32 + gx, 32 + gy, 32 + gz, 32 + ha, 32 + hb, 32 + hc, 32 + hd, 32 + he, 32 + hf, 32 + hg, 32 + hh, 32 + hi, 32 + hj, 32 + hk, 32 + hl, 32 + hm, 32 + hn, 32 + ho, 32 + hp, 32 + hq, 32 + hr, 32 + hs, 32 + ht, 32 + hu, 32 + hv, 32 + hw, 32 + hx, 32 + hy, 32 + hz, 32 + ia, 32 + ib, 32 + ic, 32 + id, 32 + ie, 32 + if, 32 + ig, 32 + ih, 32 + ii, 32 + ij, 32 + ik, 32 + il, 32 + im, 32 + in, 32 + io, 32 + ip, 32 + iq, 32 + ir, 32 + is, 32 + it, 32 + iu, 32 + iv, 32 + iw, 32 + ix, 32 + iy, 32 + iz, 32 + ja, 32 + jb, 32 + jc, 32 + jd, 32 + je, 32 + jf, 32 + jg, 32 + jh, 32 + ji, 32 + jj, 32 + jk, 32 + jl, 32 + jm, 32 + jn, 32 + jo, 32 + jp, 32 + jq, 32 + jr, 32 + js, 32 + jt, 32 + ju, 32 + jv, 32 + jw, 32 + jx, 32 + jy, 32 + jz, 32 + ka, 32 + kb, 32 + kc, 32 + kd, 32 + ke, 32 + kf, 32 + kg, 32 + kh, 32 + ki, 32 + kj, 32 + kk, 32 + kl, 32 + km, 32 + kn, 32 + ko, 32 + kp, 32 + kq, 32 + kr, 32 + ks, 32 + kt, 32 + ku, 32 + kv, 32 + kw, 32 + kx, 32 + ky, 32 + kz, 32 + la, 32 + lb, 32 + lc, 32 + ld, 32 + le, 32 + lf, 32 + lg, 32 + lh, 32 + li, 32 + lj, 32 + lk, 32 + ll, 32 + lm, 32 + ln, 32 + lo, 32 + lp, 32 + lq, 32 + lr, 32 + ls, 32 + lt, 32 + lu, 32 + lv, 32 + lw , 32 + lx, 32 + ly, 32 + lz, 32 + ma, 32 + mb, 32 + mc, 32 + md, 32 + me, 32 + mf, 32 + mg, 32 + mh, 32 + mi, 32 + mj, 32 + mk, 32 + ml, 32 + mm, 32 + mn, 32 + mo, 32 + mp, 32 + mq, 32 + mr, 32 + ms, 32 + mt, 32 + mu, 32 + mv , 32 + mw, 32 + mx, 32 + my, 32 + mz, 32 + na, 32 + nb, 32 + nc, 32 + nd, 32 + ne, 32 + nf, 32 + ng, 32 + nh, 32 + ni, 32 + nj, 32 + nk, 32 + nl, 32 + nm, 32 + nn, 32 + no, 32 + np, 32 + nq, 32 + nr, 32 + ns, 32 + nt, 32 + nu , 32 + nv, 32 + nw, 32 + nx, 32 + ny, 32 + nz, 32 + oa, 32 + ob, 32 + oc, 32 + od, 32 + oe, 32 + of, 32 + og, 32 + oh, 32 + oi, 32 + oj, 32 + ok, 32 + ol, 32 + om, 32 + on, 32 + oo, 32 + op, 32 + oq, 32 + or, 32 + os, 32 + ot , 32 + ou, 32 + ov, 32 + ow, 32 + ox, 32 + oy, 32 + oz, 32 + pa, 32 + pb, 32 + pc, 32 + pd, 32 + pe, 32 + pf, 32 + pg, 32 + ph, 32 + pi, 32 + pj, 32 + pk, 32 + pl, 32 + pm, 32 + pn, 32 + po, 32 + pp, 32 + pq, 32 + pr, 32 + ps , 32 + pt, 32 + pu, 32 + pv, 32 + pw, 32 + px, 32 + py, 32 + pz, 32 + qa, 32 + qb, 32 + qc, 32 + qd, 32 + qe, 32 + qf, 32 + qg, 32 + qh, 32 + qi, 32 + qj, 32 + qk, 32 + ql, 32 + qm, 32 + qn, 32 + qo, 32 + qp, 32 + qq, 32 + qr , 32 + qs, 32 + qt, 32 + qu, 32 + qv, 32 + qw, 32 + qx, 32 + qy, 32 + qz, 32 + ra, 32 + rb, 32 + rc, 32 + rd, 32 + re, 32 + rf, 32 + rg, 32 + rh, 32 + ri, 32 + rj, 32 + rk, 32 + rl, 32 + rm, 32 + rn, 32 + ro, 32 + rp, 32 + rq , 32 + rr, 32 + rs, 32 + rt, 32 + ru, 32 + rv, 32 + rw, 32 + rx, 32 + ry, 32 + rz, 32 + sa, 32 + sb, 32 + sc, 32 + sd, 32 + se, 32 + sf, 32 + sg, 32 + sh, 32 + si, 32 + sj, 32 + sk, 32 + sl, 32 + sm, 32 + sn, 32 + so, 32 + sp, 32 + sq, 32 + sr, 33 + a, 33 + b, 33 + c, 33 + d, 33 + e, 33 + f, 33 + g, 33 + h, 33 + i, 33 + j, 33 + k, 33 + l, 33 + m, 33 + n, 33 + o, 33 + p, 33 + q, 33 + r, 33 + s, 33 + t, 33 + u, 33 + v, 33 + w, 33 + x, 33 + y, 33 + z, 33 + aa, 33 + ab, 33 + ac, 33 + ad, 33 + ae, 33 + af, 33 + ag, 33 + ah, 33 + ai, 33 + aj, 33 + ak, 33 + al, 33 + am, 33 + an, 33 + ao, 33 + ap, 33 + aq, 33 + ar, 33 + as, 33 + at, 33 + au, 33 + av, 33 + aw, 33 + ax, 33 + ay, 33 + az, 33 + ba, 33 + bb, 33 + bc, 33 + bd, 33 + be, 33 + bf, 33 + bg, 33 + bh, 33 + bi, 33 + bj, 33 + bk, 33 + bl, 33 + bm, 33 + bn, 33 + bo, 33 + bp, 33 + bq, 33 + br, 33 + bs, 33 + bt, 33 + bu, 33 + bv, 33 + bw, 33 + bx, 33 + by, 33 + bz, 33 + ca, 33 + cb, 33 + cc, 33 + cd, 33 + ce, 33 + cf, 33 + cg, 33 + ch, 33 + ci, 33 + cj, 33 + ck, 33 + cl, 33 + cm, 33 + cn, 33 + co, 33 + cp, 33 + cq, 33 + cr, 33 + cs, 33 + ct, 33 + cu, 33 + cv, 33 + cw, 33 + cx, 33 + cy, 33 + cz, 33 + da, 33 + db, 33 + dc, 33 + dd, 33 + de, 33 + df, 33 + dg, 33 + dh, 33 + di, 33 + dj, 33 + dk, 33 + dl, 33 + dm, 33 + dn, 33 + do, 33 + dp, 33 + dq, 33 + dr, 33 + ds, 33 + dt, 33 + du, 33 + dv, 33 + dw, 33 + dx, 33 + dy, 33 + dz, 33 + ea, 33 + eb, 33 + ec, 33 + ed, 33 + ee, 33 + ef, 33 + eg, 33 + eh, 33 + ei, 33 + ej, 33 + ek, 33 + el, 33 + em, 33 + en, 33 + eo, 33 + ep, 33 + eq, 33 + er, 33 + es, 33 + et, 33 + eu, 33 + ev, 33 + ew, 33 + ex, 33 + ey, 33 + ez, 33 + fa, 33 + fb, 33 + fc, 33 + fd, 33 + fe, 33 + ff, 33 + fg, 33 + fh, 33 + fi, 33 + fj, 33 + fk, 33 + fl, 33 + fm, 33 + fn, 33 + fo, 33 + fp, 33 + fq, 33 + fr, 33 + fs, 33 + ft, 33 + fu, 33 + fv, 33 + fw, 33 + fx, 33 + fy, 33 + fz, 33 + ga, 33 + gb, 33 + gc, 33 + gd, 33 + ge, 33 + gf, 3
3 + gg, 33 + gh, 33 + gi, 33 + gj, 33 + gk, 33 + gl, 33 + gm, 33 + gn, 33 + go, 33 + gp, 33 + gq, 33 + gr, 33 + gs, 33 + gt, 33 + gu, 33 + gv, 33 + gw, 33 + gx, 33 + gy, 33 + gz, 33 + ha, 33 + hb, 33 + hc, 33 + hd, 33 + he, 33 + hf, 33 + hg, 33 + hh, 33 + hi, 33 + hj, 33 + hk, 33 + hl, 33 + hm, 33 + hn, 33 + ho, 33 + hp, 33 + hq, 33 + hr, 33 + hs, 33 + ht, 33 + hu, 33 + hv, 33 + hw, 33 + hx, 33 + hy, 33 + hz, 33 + ia, 33 + ib, 33 + ic, 33 + id, 33 + ie, 33 + if, 33 + ig, 33 + ih, 33 + ii, 33 + ij, 33 + ik, 33 + il, 33 + im, 33 + in, 33 + io, 33 + ip, 33 + iq, 33 + ir, 33 + is, 33 + it, 33 + iu, 33 + iv, 33 + iw, 33 + ix, 33 + iy, 33 + iz, 33 + ja, 33 + jb, 33 + jc, 33 + jd, 33 + je, 33 + jf, 33 + jg, 33 + jh, 33 + ji, 33 + jj, 33 + jk, 33 + jl, 33 + jm, 33 + jn, 33 + jo, 33 + jp, 33 + jq, 33 + jr, 33 + js, 33 + jt, 33 + ju, 33 + jv, 33 + jw, 33 + jx, 33 + jy, 33 + jz, 33 + ka, 33 + kb, 33 + kc, 33 + kd, 33 + ke, 33 + kf, 33 + kg, 33 + kh, 33 + ki, 33 + kj, 33 + kk, 33 + kl, 33 + km, 33 + kn, 33 + ko, 33 + kp, 33 + kq, 33 + kr, 33 + ks, 33 + kt, 33 + ku, 33 + kv, 33 + kw, 33 + kx, 33 + ky, 33 + kz, 33 + la, 33 + lb, 33 + lc, 33 + ld, 33 + le, 33 + lf, 33 + lg, 33 + lh, 33 + li, 33 + lj, 33 + lk, 33 + ll, 33 + lm, 33 + ln, 33 + lo, 33 + lp, 33 + lq, 33 + lr, 33 + ls, 33 + lt, 33 + lu, 33 + lv, 33 + lw, 33 + lx, 33 + ly, 33 + lz, 33 + ma, 33 + mb, 33 + mc, 33 + md, 33 + me, 33 + mf, 33 + mg, 33 + mh, 33 + mi, 33 + mj, 33 + mk, 33 + ml, 33 + mm, 33 + mn, 33 + mo, 33 + mp, 33 + mq , 33 + mr, 33 + ms, 33 + mt, 33 + mu, 33 + mv, 33 + mw, 33 + mx, 33 + my, 33 + mz, 33 + na, 33 + nb, 33 + nc, 33 + nd, 33 + ne, 33 + nf, 33 + ng, 33 + nh, 33 + ni, 33 + nj, 33 + nk, 33 + nl, 33 + nm, 33 + nn, 33 + no, 33 + np , 33 + nq, 33 + nr, 33 + ns, 33 + nt, 33 + nu, 33 + nv, 33 + nw, 33 + nx, 33 + ny, 33 + nz, 33 + oa, 33 + ob, 33 + oc, 33 + od, 33 + oe, 33 + of, 33 + og, 33 + oh, 33 + oi, 33 + oj, 33 + ok, 33 + ol, 33 + om, 33 + on, 33 + oo , 33 + op, 33 + oq, 33 + or, 33 + os, 33 + ot, 33 + ou, 33 + ov, 33 + ow, 33 + ox, 33 + oy, 33 + oz, 33 + pa, 33 + pb, 33 + pc, 33 + pd, 33 + pe, 33 + pf, 33 + pg, 33 + ph, 33 + pi, 33 + pj, 33 + pk, 33 + pl, 33 + pm, 33 + pn , 33 + po, 33 + pp, 33 + pq, 33 + pr, 33 + ps, 33 + pt, 33 + pu, 33 + pv, 33 + pw, 33 + px, 33 + py, 33 + pz, 33 + qa, 33 + qb, 33 + qc, 33 + qd, 33 + qe, 33 + qf, 33 + qg, 33 + qh, 33 + qi, 33 + qj, 33 + qk, 33 + ql, 33 + qm , 33 + qn, 33 + qo, 33 + qp, 33 + qq, 33 + qr, 33 + qs, 33 + qt, 33 + qu, 33 + qv, 33 + qw, 33 + qx, 33 + qy, 33 + qz, 33 + ra, 33 + rb, 33 + rc, 33 + rd, 33 + re, 33 + rf, 33 + rg, 33 + rh, 33 + ri, 33 + rj, 33 + rk, 33 + rl , 33 + rm, 33 + rn, 33 + ro, 33 + rp, 33 + rq, 33 + rr, 33 + rs, 33 + rt, 33 + ru, 33 + rv, 33 + rw, 33 + rx, 33 + ry, 33 + rz, 33 + sa, 33 + sb, 33 + sc, 33 + sd, 33 + se, 33 + sf, 33 + sg, 33 + sh, 33 + si, 33 + sj, 33 + sk , 33 + sl, 33 + sm, 33 + sn, 33 + so, 33 + sp, 33 + sq, 33 + sr, 34 + a, 34 + b, 34 + c, 34 + d, 34 + e, 34 + f, 34 + g, 34 + h, 34 + i, 34 + j, 34 + k, 34 + l, 34 + m, 34 + n, 34 + o, 34 + p, 34 + q, 34 + r, 34 + s, 34 + t, 34 + u, 34 + v, 34 + w, 34 + x , 34 + y, 34 + z, 34 + aa, 34 + ab, 34 + ac, 34 + ad, 34 + ae, 34 + af, 34 + ag, 34 + ah, 34 + ai, 34 + aj, 34 + ak, 34 + al, 34 + am, 34 + an, 34 + ao, 34 + ap, 34 + aq, 34 + ar, 34 + as, 34 + at, 34 + au, 34 + av, 34 + aw , 34 + ax, 34 + ay, 34 + az, 34 + ba, 34 + bb, 34 + bc, 34 + bd, 34 + be, 34 + bf, 34 + bg, 34 + bh, 34 + bi, 34 + bj, 34 + bk, 34 + bl, 34 + bm, 34 + bn, 34 + bo, 34 + bp, 34 + bq, 34 + br, 34 + bs, 34 + bt, 34 + bu, 34 + bv , 34 + bw, 34 + bx, 34 + by, 34 + bz, 34 + ca, 34 + cb, 34 + cc, 34 + cd, 34 + ce, 34 + cf, 34 + cg, 34 + ch, 34 + ci, 34 + cj, 34 + ck, 34 + cl, 34 + cm, 34 + cn, 34 + co, 34 + cp, 34 + cq, 34 + cr, 34 + cs, 34 + ct, 34 + cu , 34 + cv, 34 + cw, 34 + cx, 34 + cy, 34 + cz, 34 + da, 34 + db, 34 + dc, 34 + dd, 34 + de, 34 + df, 34 + dg, 34 + dh, 34 + di, 34 + dj, 34 + dk, 34 + dl, 34 + dm, 34 + dn, 34 + do, 34 + dp, 34 + dq, 34 + dr, 34 + ds, 34 + dt , 34 + du, 34 + dv, 34 + dw, 34 + dx, 34 + dy, 34 + dz, 34 + ea, 34 + eb, 34 + ec, 34 + ed, 34 + ee, 34 + ef, 34 + eg, 34 + eh, 34 + ei, 34 + ej, 34 + ek, 34 + el, 34 + em, 34 + en, 34 + eo, 34 + ep, 34 + eq, 34 + er, 34 + es , 34 + et, 34 + eu, 34 + ev, 34 + ew, 34 + ex, 34 + ey, 34 + ez, 34 + fa, 34 + fb, 34 + fc, 34 + fd, 34 + fe, 34 + ff, 34 + fg, 34 + fh, 34 + fi, 34 + fj, 34 + fk, 34 + fl, 34 + fm, 34 + fn, 34 + fo, 34 + fp, 34 + fq, 34 + fr , 34 + fs, 34 + ft, 34 + fu, 34 + fv, 34 + fw, 34 + fx, 34 + fy, 34 + fz, 34 + ga, 34 + gb, 34 + gc, 34 + gd, 34 + ge, 34 + gf, 34 + gg, 34 + gh, 34 + gi, 34 + gj, 34 + gk, 34 + gl, 34 + gm, 34 + gn, 34 + go, 34 + gp, 34 + gq, 34 + gr, 34 + gs, 34 + gt, 34 + gu, 34 + gv, 34 + gw, 34 + gx, 34 + gy, 34 + gz, 34 + ha, 34 + hb, 34 + hc, 34 + hd, 34 + he, 34 + hf, 34 + hg, 34 + hh, 34 + hi, 34 + hj, 34 + hk, 34 + hl, 34 + hm, 34 + hn, 34 + ho, 34 + hp, 34 + hq, 34 + hr, 34 + hs, 34 + ht, 34 + hu, 34 + hv, 34 + hw, 34 + hx, 34 + hy, 34 + hz, 34 + ia, 34 + ib, 34 + ic, 34 + id, 34 + ie, 34 + if, 34 + ig, 34 + ih, 34 + ii, 34 + ij, 34 + ik, 34 + il, 34 + im, 34 + in, 34 + io, 34 + ip, 34 + iq, 34 + ir, 34 + is, 34 + it, 34 + iu, 34 + iv, 34 + iw, 34 + ix, 34 + iy, 34 + iz, 34 + ja, 34 + jb, 34 + jc, 34 + jd, 34 + je, 34 + jf, 34 + jg, 34 + jh, 34 + ji, 34 + jj, 34 + jk, 34 + jl, 34 + jm, 34 + jn, 34 + jo, 34 + jp, 34 + jq, 34 + jr, 34 + js, 34 + jt, 34 + ju, 34 + jv, 34 + jw, 34 + jx, 34 + jy, 34 + jz, 34 + ka, 34 + kb, 34 + kc, 34 + kd, 34 + ke, 34 + kf, 34 + kg, 34 + kh, 34 + ki, 34 + kj, 34 + kk, 34 + kl, 34 + km, 34 + kn, 34 + ko, 34 + kp, 34 + kq, 34 + kr, 34 + ks, 34 + kt, 34 + ku, 34 + kv, 34 + kw, 34 + kx, 34 + ky, 34 + kz, 34 + la, 34 + lb, 34 + lc, 34 + ld, 34 + le, 34 + lf, 34 + lg, 34 + lh, 34 + li, 34 + lj, 34 + lk, 34 + ll, 34 + lm, 34 + ln, 34 + lo, 34 + lp, 34 + lq, 34 + lr, 34 + ls, 34 + lt, 34 + lu, 34 + lv, 34 + lw, 34 + lx, 34 + ly, 34 + lz, 34 + ma, 34 + mb, 34 + mc, 34 + md, 34 + me, 34 + mf, 34 + mg, 34 + mh, 34 + mi, 3 4 + mj, 34 + mk, 34 + ml, 34 + mm, 34 + mn, 34 + mo, 34 + mp, 34 + mq, 34 + mr, 34 + ms, 34 + mt, 34 + mu, 34 + mv, 34 + mw, 34 + mx, 34 + my, 34 + mz, 34 + na, 34 + nb, 34 + nc, 34 + nd, 34 + ne, 34 + nf, 34 + ng, 34 + nh, 34 + ni, 34 + nj, 34 + nk, 34 + nl, 34 + nm, 34 + nn, 34 + no, 34 + np, 34 + nq, 34 + nr, 34 + ns, 34 + nt, 34 + nu, 34 + nv, 34 + nw, 34 + nx, 34 + ny, 34 + nz, 34 + oa, 34 + ob, 34 + oc, 34 + od, 34 + oe, 34 + of, 34 + og, 34 + oh, 34 + oi, 34 + oj, 34 + ok, 34 + ol, 34 + om, 34 + on, 34 + oo, 34 + op, 34 + oq, 34 + or, 34 + os, 34 + ot, 34 + ou, 34 + ov, 34 + ow, 34 + ox, 34 + oy, 34 + oz, 34 + pa, 34 + pb, 34 + pc, 34 + pd, 34 + pe, 34 + pf, 34 + pg, 34 + ph, 34 + pi, 34 + pj, 34 + pk, 34 + pl, 34 + pm, 34 + pn, 34 + po, 34 + pp, 34 + pq, 34 + pr, 34 + ps, 34 + pt, 34 + pu, 34 + pv, 34 + pw, 34 + px, 34 + py, 34 + pz, 34 + qa, 34 + qb, 34 + qc, 34 + qd, 34 + qe, 34 + qf, 34 + qg, 34 + qh, 34 + qi, 34 + qj, 34 + qk, 34 + ql, 34 + qm, 34 + qn, 34 + qo, 34 + qp, 34 + qq, 34 + qr, 34 + qs, 34 + qt, 34 + qu, 34 + qv, 34 + qw, 34 + qx, 34 + qy, 34 + qz, 34 + ra, 34 + rb, 34 + rc, 34 + rd, 34 + re, 34 + rf, 34 + rg, 34 + rh, 34 + ri, 34 + rj, 34 + rk, 34 + rl, 34 + rm, 34 + rn, 34 + ro, 34 + rp, 34 + rq, 34 + rr, 34 + rs, 34 + rt, 34 + ru, 34 + rv, 34 + rw, 34 + rx, 34 + ry, 34 + rz, 34 + sa, 34 + sb, 34 + sc, 34 + sd, 34 + se, 34 + sf, 34 + sg, 34 + sh, 34 + si, 34 + sj, 34 + sk, 34 + sl, 34 + sm, 34 + sn, 34 + so, 34 + sp, 34 + sq, 34 + sr, 35 + a, 35 + b, 3 5 + c, 35 + d, 35 + e, 35 + f, 35 + g, 35 + h, 35 + i, 35 + j, 35 + k, 35 + l, 35 + m, 35 + n, 35 + o, 35 + p, 35 + q, 35 + r, 35 + s, 35 + t, 35 + u, 35 + v, 35 + w, 35 + x, 35 + y, 35 + z, 35 + aa, 35 + ab, 35 + ac, 35 + ad, 35 + ae, 35 + af, 35 + ag, 35 + ah, 35 + ai, 35 + aj, 35 + ak, 35 + al, 35 + am, 35 + an, 35 + ao, 35 + ap, 35 + aq, 35 + ar, 35 + as, 35 + at, 35 + au, 35 + av, 35 + aw, 35 + ax, 35 + ay, 35 + az, 35 + ba, 35 + bb, 35 + bc, 35 + bd, 35 + be, 35 + bf, 35 + bg, 35 + bh, 35 + bi, 35 + bj, 35 + bk, 35 + bl, 35 + bm, 35 + bn, 35 + bo, 35 + bp, 35 + bq, 35 + br, 35 + bs, 35 + bt, 35 + bu, 35 + bv, 35 + bw, 35 + bx, 35 + by, 35 + bz, 35 + ca, 35 + cb, 35 + cc, 35 + cd, 35 + ce, 35 + cf, 35 + cg, 35 + ch, 35 + ci, 35 + cj, 35 + ck, 35 + cl, 35 + cm, 35 + cn, 35 + co, 35 + cp, 35 + cq, 35 + cr, 35 + cs, 35 + ct, 35 + cu, 35 + cv, 35 + cw, 35 + cx, 35 + cy, 35 + cz, 35 + da, 35 + db, 35 + dc, 35 + dd, 35 + de, 35 + df, 35 + dg, 35 + dh, 35 + di, 35 + dj, 35 + dk, 35 + dl, 35 + dm, 35 + dn, 35 + do, 35 + dp, 35 + dq, 35 + dr, 35 + ds, 35 + dt, 35 + du, 35 + dv, 35 + dw, 35 + dx, 35 + dy, 35 + dz, 35 + ea, 35 + eb, 35 + ec, 35 + ed, 35 + ee, 35 + ef, 35 + eg, 35 + eh, 35 + ei, 35 + ej, 35 + ek, 35 + el, 35 + em, 35 + en, 35 + eo, 35 + ep, 35 + eq, 35 + er, 35 + es, 35 + et, 35 + eu, 35 + ev, 35 + ew, 35 + ex, 35 + ey, 35 + ez, 35 + fa, 35 + fb, 35 + fc, 35 + fd, 35 + fe, 35 + ff, 35 + fg, 35 + fh, 35 + fi, 35 + fj, 35 + fk, 35 + fl, 35 + fm, 35 + fn, 35 + fo, 35 + fp, 35 + fq , 35 + fr, 35 + fs, 35 + ft, 35 + fu, 35 + fv, 35 + fw, 35 + fx, 35 + fy, 35 + fz, 35 + ga, 35 + gb, 35 + gc, 35 + gd, 35 + ge, 35 + gf, 35 + gg, 35 + gh, 35 + gi, 35 + gj, 35 + gk, 35 + gl, 35 + gm, 35 + gn, 35 + go, 35 + gp , 35 + gq, 35 + gr, 35 + gs, 35 + gt, 35 + gu, 35 + gv, 35 + gw, 35 + gx, 35 + gy, 35 + gz, 35 + ha, 35 + hb, 35 + hc, 35 + hd, 35 + he, 35 + hf, 35 + hg, 35 + hh, 35 + hi, 35 + hj, 35 + hk, 35 + hl, 35 + hm, 35 + hn, 35 + ho , 35 + hp, 35 + hq, 35 + hr, 35 + hs, 35 + ht, 35 + hu, 35 + hv, 35 + hw, 35 + hx, 35 + hy, 35 + hz, 35 + ia, 35 + ib, 35 + ic, 35 + id, 35 + ie, 35 + if, 35 + ig, 35 + ih, 35 + ii, 35 + ij, 35 + ik, 35 + il, 35 + im, 35 + in , 35 + io, 35 + ip, 35 + iq, 35 + ir, 35 + is, 35 + it, 35 + iu, 35 + iv, 35 + iw, 35 + ix, 35 + iy, 35 + iz, 35 + ja, 35 + jb, 35 + jc, 35 + jd, 35 + je, 35 + jf, 35 + jg, 35 + jh, 35 + ji, 35 + jj, 35 + jk, 35 + jl, 35 + jm , 35 + jn, 35 + jo, 35 + jp, 35 + jq, 35 + jr, 35 + js, 35 + jt, 35 + ju, 35 + jv, 35 + jw, 35 + jx, 35 + jy, 35 + jz, 35 + ka, 35 + kb, 35 + kc, 35 + kd, 35 + ke, 35 + kf, 35 + kg, 35 + kh, 35 + ki, 35 + kj, 35 + kk, 35 + kl , 35 + km, 35 + kn, 35 + ko, 35 + kp, 35 + kq, 35 + kr, 35 + ks, 35 + kt, 35 + ku, 35 + kv, 35 + kw, 35 + kx, 35 + ky, 35 + kz, 35 + la, 35 + lb, 35 + lc, 35 + ld, 35 + le, 35 + lf, 35 + lg, 35 + lh, 35 + li, 35 + lj, 35 + lk , 35 + ll, 35 + lm, 35 + ln, 35 + lo, 35 + lp, 35 + lq, 35 + lr, 35 + ls, 35 + lt, 35 + lu, 35 + lv, 35 + lw, 35 + lx, 35 + ly, 35 + lz, 35 + ma, 35 + mb, 35 + mc, 35 + md, 35 + me, 35 + mf, 35 + mg, 35 + mh, 35 + mi, 35 + mj, 35 + mk, 35 + ml, 35 + mm, 35 + mn, 35 + mo, 35 + mp, 35 + mq, 35 + mr, 35 + ms, 35 + mt, 35 + mu, 35 + mv, 35 + mw, 35 + mx, 35 + my, 35 + mz, 35 + na, 35 + nb, 35 + nc, 35 + nd, 35 + ne, 35 + nf, 35 + ng, 35 + nh, 35 + ni, 35 + nj, 35 + nk, 35 + nl, 35 + nm, 35 + nn, 35 + no, 35 + np, 35 + nq, 35 + nr, 35 + ns, 35 + nt, 35 + nu, 35 + nv, 35 + nw, 35 + nx, 35 + ny, 35 + nz, 35 + oa, 35 + ob, 35 + oc, 35 + od, 35 + oe, 35 + of, 35 + og, 35 + oh, 35 + oi, 35 + oj, 35 + ok, 35 + ol, 35 + om, 35 + on, 35 + oo, 35 + op, 35 + oq, 35 + or, 35 + os, 35 + ot, 35 + ou, 35 + ov, 35 + ow, 35 + ox, 35 + oy, 35 + oz, 35 + pa, 35 + pb, 35 + pc, 35 + pd, 35 + pe, 35 + pf, 35 + pg, 35 + ph, 35 + pi, 35 + pj, 35 + pk, 35 + pl, 35 + pm, 35 + pn, 35 + po, 35 + pp, 35 + pq, 35 + pr, 35 + ps, 35 + pt, 35 + pu, 35 + pv, 35 + pw, 35 + px, 35 + py, 35 + pz, 35 + qa, 35 + qb, 35 + qc, 35 + qd, 35 + qe, 35 + qf, 35 + qg, 35 + qh, 35 + qi, 35 + qj, 35 + qk, 35 + ql, 35 + qm, 35 + qn, 35 + qo, 35 + qp, 35 + qq, 35 + qr, 35 + qs, 35 + qt, 35 + qu, 35 + qv, 35 + qw, 35 + qx, 35 + qy, 35 + qz, 35 + ra, 35 + rb, 35 + rc, 35 + rd, 35 + re, 35 + rf, 35 + rg, 35 + rh, 35 + ri, 35 + rj, 35 + rk, 35 + rl, 35 + rm, 35 + rn, 35 + ro, 35 + rp, 35 + rq, 35 + rr, 35 + rs, 35 + rt, 35 + ru, 35 + rv, 35 + rw, 35 + rx, 35 + ry, 35 + rz, 35 + sa, 35 + sb, 35 + sc, 35 + sd, 35 + se, 35 + sf, 35 + sg, 35 + sh, 35 + si, 35 + sj, 35 + sk, 35 + sl, 3 5 + sm, 35 + sn, 35 + so, 35 + sp, 35 + sq, 35 + sr, 36 + a, 36 + b, 36 + c, 36 + d, 36 + e, 36 + f, 36 + g, 36 + h, 36 + i, 36 + j, 36 + k, 36 + l, 36 + m, 36 + n, 36 + o, 36 + p, 36 + q, 36 + r, 36 + s, 36 + t, 36 + u, 36 + v, 36 + w, 36 + x, 36 + y, 36 + z, 36 + aa, 36 + ab, 36 + ac, 36 + ad, 36 + ae, 36 + af, 36 + ag, 36 + ah, 36 + ai, 36 + aj, 36 + ak, 36 + al, 36 + am, 36 + an, 36 + ao, 36 + ap, 36 + aq, 36 + ar, 36 + as, 36 + at, 36 + au, 36 + av, 36 + aw, 36 + ax, 36 + ay, 36 + az, 36 + ba, 36 + bb, 36 + bc, 36 + bd, 36 + be, 36 + bf, 36 + bg, 36 + bh, 36 + bi, 36 + bj, 36 + bk, 36 + bl, 36 + bm, 36 + bn, 36 + bo, 36 + bp, 36 + bq, 36 + br, 36 + bs, 36 + bt, 36 + bu, 36 + bv, 36 + bw, 36 + bx, 36 + by, 36 + bz, 36 + ca, 36 + cb, 36 + cc, 36 + cd, 36 + ce, 36 + cf, 36 + cg, 36 + ch, 36 + ci, 36 + cj, 36 + ck, 36 + cl, 36 + cm, 36 + cn, 36 + co, 36 + cp, 36 + cq, 36 + cr, 36 + cs, 36 + ct, 36 + cu, 36 + cv, 36 + cw, 36 + cx, 36 + cy, 36 + cz, 36 + da, 36 + db, 36 + dc, 36 + dd, 36 + de, 36 + df, 36 + dg, 36 + dh, 36 + di, 36 + dj, 36 + dk, 36 + dl, 36 + dm, 36 + dn, 36 + do, 36 + dp, 36 + dq, 36 + dr, 36 + ds, 36 + dt, 36 + du, 36 + dv, 36 + dw, 36 + dx, 36 + dy, 36 + dz, 36 + ea, 36 + eb, 36 + ec, 36 + ed, 36 + ee, 36 + ef, 36 + eg, 36 + eh, 36 + ei, 36 + ej, 36 + ek, 36 + el, 36 + em, 36 + en, 36 + eo, 36 + ep, 36 + eq, 36 + er, 36 + es, 36 + et, 36 + eu, 36 + ev, 36 + ew, 36 + ex, 36 + ey, 36 + ez, 36 + fa, 36 + fb, 36 + fc, 36 + fd, 36 + fe, 36 + ff, 36 + fg, 36 + fh, 36 + fi, 3 6 + fj, 36 + fk, 36 + fl, 36 + fm, 36 + fn, 36 + fo, 36 + fp, 36 + fq, 36 + fr, 36 + fs, 36 + ft, 36 + fu, 36 + fv, 36 + fw, 36 + fx, 36 + fy, 36 + fz, 36 + ga, 36 + gb, 36 + gc, 36 + gd, 36 + ge, 36 + gf, 36 + gg, 36 + gh, 36 + gi, 36 + gj, 36 + gk, 36 + gl, 36 + gm, 36 + gn, 36 + go, 36 + gp, 36 + gq, 36 + gr, 36 + gs, 36 + gt, 36 + gu, 36 + gv, 36 + gw, 36 + gx, 36 + gy, 36 + gz, 36 + ha, 36 + hb, 36 + hc, 36 + hd, 36 + he, 36 + hf, 36 + hg, 36 + hh, 36 + hi, 36 + hj, 36 + hk, 36 + hl, 36 + hm, 36 + hn, 36 + ho, 36 + hp, 36 + hq, 36 + hr, 36 + hs, 36 + ht, 36 + hu, 36 + hv, 36 + hw, 36 + hx, 36 + hy, 36 + hz, 36 + ia, 36 + ib, 36 + ic, 36 + id, 36 + ie, 36 + if, 36 + ig, 36 + ih, 36 + ii, 36 + ij, 36 + ik, 36 + il, 36 + im, 36 + in, 36 + io, 36 + ip, 36 + iq, 36 + ir, 36 + is, 36 + it, 36 + iu, 36 + iv, 36 + iw, 36 + ix, 36 + iy, 36 + iz, 36 + ja, 36 + jb, 36 + jc, 36 + jd, 36 + je, 36 + jf, 36 + jg, 36 + jh, 36 + ji, 36 + jj, 36 + jk, 36 + jl, 36 + jm, 36 + jn, 36 + jo, 36 + jp, 36 + jq, 36 + jr, 36 + js, 36 + jt, 36 + ju, 36 + jv, 36 + jw, 36 + jx, 36 + jy, 36 + jz, 36 + ka, 36 + kb, 36 + kc, 36 + kd, 36 + ke, 36 + kf, 36 + kg, 36 + kh, 36 + ki, 36 + kj, 36 + kk, 36 + kl, 36 + km, 36 + kn, 36 + ko, 36 + kp, 36 + kq, 36 + kr, 36 + ks, 36 + kt, 36 + ku, 36 + kv, 36 + kw, 36 + kx, 36 + ky, 36 + kz, 36 + la, 36 + lb, 36 + lc, 36 + ld, 36 + le, 36 + lf, 36 + lg, 36 + lh, 36 + li, 36 + lj, 36 + lk, 36 + ll, 36 + lm, 36 + ln, 36 + lo, 36 + lp, 36 + lq, 36 + lr, 36 + ls, 36 + lt , 36 + lu, 36 + lv, 36 + lw, 36 + lx, 36 + ly, 36 + lz, 36 + ma, 36 + mb, 36 + mc, 36 + md, 36 + me, 36 + mf, 36 + mg, 36 + mh, 36 + mi, 36 + mj, 36 + mk, 36 + ml, 36 + mm, 36 + mn, 36 + mo, 36 + mp, 36 + mq, 36 + mr, 36 + ms , 36 + mt, 36 + mu, 36 + mv, 36 + mw, 36 + mx, 36 + my, 36 + mz, 36 + na, 36 + nb, 36 + nc, 36 + nd, 36 + ne, 36 + nf, 36 + ng, 36 + nh,
36 + ni, 36 + nj, 36 + nk, 36 + nl, 36 + nm, 36 + nn, 36 + no, 36 + np, 36 + nq, 36 + nr, 36 + ns, 36 + nt, 36 + nu, 36 + nv, 36 + nw, 36 + nx, 36 + ny, 36 + nz, 36 + oa, 36 + ob, 36 + oc, 36 + od, 36 + oe, 36 + of, 36 + og, 36 + oh, 36 + oi, 36 + oj, 36 + ok, 36 + ol, 36 + om, 36 + on, 36 + oo, 36 + op, 36 + oq, 36 + or, 36 + os, 36 + ot, 36 + ou, 36 + ov, 36 + ow, 36 + ox, 36 + oy, 36 + oz, 36 + pa, 36 + pb, 36 + pc, 36 + pd, 36 + pe, 36 + pf, 36 + pg, 36 + ph, 36 + pi, 36 + pj, 36 + pk, 36 + pl, 36 + pm, 36 + pn, 36 + po, 36 + pp, 36 + pq, 36 + pr, 36 + ps, 36 + pt, 36 + pu, 36 + pv, 36 + pw, 36 + px, 36 + py, 36 + pz, 36 + qa, 36 + qb, 36 + qc, 36 + qd, 36 + qe, 36 + qf, 36 + qg, 36 + qh, 36 + qi, 36 + qj, 36 + qk, 36 + ql, 36 + qm, 36 + qn, 36 + qo, 36 + qp, 36 + qq, 36 + qr, 36 + qs, 36 + qt, 36 + qu, 36 + qv, 36 + qw, 36 + qx, 36 + qy, 36 + qz, 36 + ra, 36 + rb, 36 + rc, 36 + rd, 36 + re, 36 + rf, 36 + rg, 36 + rh, 36 + ri, 36 + rj, 36 + rk, 36 + rl, 36 + rm, 36 + rn, 36 + ro, 36 + rp, 36 + rq, 36 + rr, 36 + rs, 36 + rt, 36 + ru, 36 + rv, 36 + rw, 36 + rx, 36 + ry, 36 + rz, 36 + sa, 36 + sb, 36 + sc, 36 + sd, 36 + se, 36 + sf, 36 + sg, 36 + sh, 36 + si, 36 + sj, 36 + sk, 36 + sl, 36 + sm, 36 + sn, 36 + so, 36 + sp, 36 + sq, 36 + sr, 37 + a, 37 + b, 37 + c, 37 + d, 37 + e, 37 + f, 37 + g, 37 + h, 37 + i, 37 + j, 37 + k, 37 + l, 37 + m, 37 + n, 37 + o, 37 + p, 37 + q, 37 + r, 37 + s, 37 + t, 37 + u, 37 + v, 37+ w, 37 + x, 37 + y, 37 + z, 37 + aa, 37 + ab, 37 + ac, 37 + ad, 37 + ae, 37 + af, 37 + ag, 37 + ah, 37 + ai, 37 + aj, 37 + ak, 37 + al, 37 + am, 37 + an, 37 + ao, 37 + ap, 37 + aq, 37 + ar, 37 + as, 37 + at, 37 + au, 37 + av, 37 + aw, 37 + ax, 37 + ay, 37 + az, 37 + ba, 37 + bb, 37 + bc, 37 + bd, 37 + be, 37 + bf, 37 + bg, 37 + bh, 37 + bi, 37 + bj, 37 + bk, 37 + bl, 37 + bm, 37 + bn, 37 + bo, 37 + bp, 37+ bq, 37 + br, 37 + bs, 37 + bt, 37 + bu, 37 + bv, 37 + bw, 37 + bx, 37 + by, 37 + bz, 37 + ca, 37 + cb, 37 + cc, 37 + cd, 37 + ce, 37 + cf, 37 + cg, 37 + ch, 37 + ci, 37 + cj, 37 + ck, 37 + cl, 37 + cm, 37 + cn, 37 + co, 37 + cp, 37 + cq, 37 + cr, 37 + cs, 37 + ct, 37 + cu, 37 + cv, 37 + cw, 37 + cx, 37 + cy, 37 + cz, 37 + da, 37 + db, 37 + dc, 37 + dd, 37 + de, 37 + df, 37 + dg, 37 + dh, 37 + di, 37 + dj, 37 + dk, 37 + dl, 37 + dm, 37 + dn, 37 + do, 37 + dp, 37 + dq, 37 + dr, 37 + ds, 37 + dt, 37 + du, 37 + dv, 37 + dw, 37 + dx, 37 + dy, 37 + dz, 37 + ea, 37 + eb, 37 + ec, 37 + ed, 37 + ee, 37 + ef, 37 + eg, 37 + eh, 37 + ei, 37 + ej, 37 + ek, 37 + el, 37 + em, 37 + en, 37 + eo, 37 + ep, 37 + eq, 37 + er, 37 + es, 37 + et, 37 + eu, 37 + ev, 37 + ew, 37 + ex, 37 + ey, 37 + ez, 37 + fa, 37 + fb, 37 + fc, 37 + fd, 37 + fe, 37 + ff, 37 + fg, 37 + fh, 37 + fi, 37 + fj, 37 + fk, 37 + fl, 37 + fm, 37 + fn, 37 + fo, 37 + fp, 37 + fq, 37 + fr, 37 + fs, 37 + ft, 37 + fu, 37 + fv, 37 + fw, 37 + fx, 37 + fy, 37 + fz, 37 + ga, 37 + gb, 37 + gc, 37 + gd, 37 + ge, 37 + gf, 37 + gg, 37 + gh, 37 + gi, 37 + gj, 37 + gk, 37 + gl, 37 + gm, 37 + gn, 37 + go, 37 + g p, 37 + gq, 37 + gr, 37 + gs, 37 + gt, 37 + gu, 37 + gv, 37 + gw, 37 + gx, 37 + gy, 37 + gz, 37 + ha, 37 + hb, 37 + hc, 37 + hd, 37 + he, 37 + hf, 37 + hg, 37 + hh, 37 + hi, 37 + hj, 37 + hk, 37 + hl, 37 + hm, 37 + hn, 37 + ho, 37 + hp, 37 + hq, 37 + hr, 37 + hs, 37 + ht, 37 + hu, 37 + hv, 37 + hw, 37 + hx, 37 + hy, 37 + hz, 37 + ia, 37 + ib, 37 + ic, 37 + id, 37 + ie, 37 + if, 37 + ig, 37 + ih, 37 + ii, 37 + ij, 37 + ik, 37 + il, 37 + im, 37 + in, 37 + io, 37 + ip, 37 + iq, 37 + ir, 37 + is, 37 + it, 37 + iu, 37 + iv, 37 + iw, 37 + ix, 37 + iy, 37 + iz, 37 + ja, 37 + jb, 37 + jc, 37 + jd, 37 + je, 37 + jf, 37 + jg, 37 + jh, 37 + ji, 37 + jj, 37 + jk, 37 + jl, 37 + jm, 37 + jn, 37 + jo, 37 + jp, 37 + jq, 37 + jr, 37 + js, 37 + jt, 37 + ju, 37 + jv, 37 + jw, 37 + jx, 37 + jy, 37 + jz, 37 + ka, 37 + kb, 37 + kc, 37 + kd, 37 + ke, 37 + kf, 37 + kg, 37 + kh, 37 + ki, 37 + kj, 37 + kk, 37 + kl, 37 + km, 37 + kn, 37 + ko, 37 + kp, 37 + kq, 37 + kr, 37 + ks, 37 + kt, 37 + ku, 37 + kv, 37 + kw, 37 + kx, 37 + ky, 37 + kz, 37 + la, 37 + lb, 37 + lc, 37 + ld, 37 + le, 37 + lf, 37 + lg, 37 + lh, 37 + li, 37 + lj, 37 + lk, 37 + ll, 37 + lm, 37 + ln, 37 + lo, 37 + lp, 37 + lq, 37 + lr, 37 + ls, 37 + lt, 37 + lu, 37 + lv, 37 + lw, 37 + lx, 37 + ly, 37 + lz, 37 + ma, 37 + mb, 37 + mc, 37 + md, 37 + me, 37 + mf, 37 + mg, 37 + mh, 37 + mi, 37 + mj, 37 + mk, 37 + ml, 37 + mm, 37 + mn, 37 + mo, 37 + mp, 37 + mq, 37 + mr, 37 + ms, 37 + mt, 37 + mu, 37 + mv, 37 + mw, 37 + mx, 37 + my, 37 + mz, 37 + na, 37 + nb, 37 + nc, 37 + nd, 37 + ne, 37 + nf, 37 + ng, 37 + nh, 37 + ni, 37 + nj, 37 + nk, 37 + nl, 37 + nm , 37 + nn, 37 + no, 37 + np, 37 + nq, 37 + nr, 37 + ns, 37 + nt, 37 + nu, 37 + nv, 37 + nw, 37 + nx, 37 + ny, 37 + nz, 37 + oa, 37 + ob, 37 + oc, 37 + od, 37 + oe, 37 + of, 37 + og, 37 + oh, 37 + oi, 37 + oj, 37 + ok, 37 + ol , 37 + om, 37 + on, 37 + oo, 37 + op, 37 + oq, 37 + or, 37 + os, 37 + ot, 37 + ou, 37 + ov, 37 + ow, 37 + ox, 37 + oy, 37 + oz, 37 + pa, 37 + pb, 37 + pc, 37 + pd, 37 + pe, 37 + pf, 37 + pg, 37 + ph, 37 + pi, 37 + pj, 37 + pk , 37 + pl, 37 + pm, 37 + pn, 37 + po, 37 + pp, 37 + pq, 37 + pr, 37 + ps, 37 + pt, 37 + pu, 37 + pv, 37 + pw, 37 + px, 37 + py, 37 + pz, 37 + qa, 37 + qb, 37 + qc, 37 + qd, 37 + qe, 37 + qf, 37 + qg, 37 + qh, 37 + qi, 37 + qj , 37 + qk, 37 + ql, 37 + qm, 37 + qn, 37 + qo, 37 + qp, 37 + qq, 37 + qr, 37 + qs, 37 + qt, 37 + qu, 37 + qv, 37 + qw, 37 + qx, 37 + qy, 37 + qz, 37 + ra, 37 + rb, 37 + rc, 37 + rd, 37 + re, 37 + rf, 37 + rg, 37 + rh, 37 + ri , 37 + rj, 37 + rk, 37 + rl, 37 + rm, 37 + rn, 37 + ro, 37 + rp, 37 + rq, 37 + rr, 37 + rs, 37 + rt, 37 + ru, 37 + rv, 37 + rw, 37 + rx, 37 + ry, 37 + rz, 37 + sa, 37 + sb, 37 + sc, 37 + sd, 37 + se, 37 + sf, 37 + sg, 37 + sh , 37 + si, 37 + sj, 37 + sk, 37 + sl, 37 + sm, 37 + sn, 37 + so, 37 + sp, 37 + sq, 37 + sr, 38 + a, 38 + b, 38 + c, 38 + d, 38 + e, 38 + f, 38 + g, 38 + h, 38 + i, 38 + j, 38 + k, 38 + l, 38 + m, 38 + n, 38 + o , 38 + p, 38 + q, 38 + r, 38 + s, 38 + t, 38 + u, 38 + v, 38 + w , 38 + x, 38 + y, 38 + z, 38 + aa, 38 + ab, 38 + ac, 38 + ad, 38 + ae, 38 + af, 38 + ag, 38 + ah, 38 + ai, 38 + aj, 38 + ak, 38 + al, 38 + am, 38 + an, 38 + ao, 38 + ap, 38 + aq, 38 + ar, 38 + as, 38 + at, 38 + au, 38 + av , 38 + aw, 38 + ax, 38 + ay, 38 + az, 38 + ba, 38 + bb, 38 + bc, 38 + bd, 38 + be, 38 + bf, 38 + bg, 38 + bh, 38 + bi, 38 + bj, 38 + bk, 38 + bl, 38 + bm, 38 + bn, 38 + bo, 38 + bp, 38 + bq, 38 + br, 38 + bs, 38 + bt, 38 + bu , 38 + bv, 38 + bw, 38 + bx, 38 + by, 38 + bz, 38 + ca, 38 + cb, 38 + cc, 38 + cd, 38 + ce, 38 + cf, 38 + cg, 38 + ch, 38 + ci, 38 + cj, 38 + ck, 38 + cl, 38 + cm, 38 + cn, 38 + co, 38 + cp, 38 + cq, 38 + cr, 38 + cs, 38 + ct , 38 + cu, 38 + cv, 38 + cw, 38 + cx, 38 + cy, 38 + cz, 38 + da, 38 + db, 38 + dc, 38 + dd, 38 + de, 38 + df, 38 + dg, 38 + dh, 38 + di, 38 + dj, 38 + dk, 38 + dl, 38 + dm, 38 + dn, 38 + do, 38 + dp, 38 + dq, 38 + dr, 38 + ds , 38 + dt, 38 + du, 38 + dv, 38 + dw, 38 + dx, 38 + dy, 38 + dz, 38 + ea, 38 + eb, 38 + ec, 38 + ed, 38 + ee, 38 + ef, 38 + eg, 38 + eh, 38 + ei, 38 + ej, 38 + ek, 38 + el, 38 + em, 38 + en, 38 + eo, 38 + ep, 38 + eq, 38 + er , 38 + es, 38 + et, 38 + eu, 38 + ev, 38 + ew, 38 + ex, 38 + ey, 38 + ez, 38 + fa, 38 + fb, 38 + fc, 38 + fd, 38 + fe, 38 + ff, 38 + fg, 38 + fh, 38 + fi, 38 + fj, 38 + fk, 38 + fl, 38 + fm, 38 + fn, 38 + fo, 38 + fp, 38 + fq , 38 + fr, 38 + fs, 38 + ft, 38 + fu, 38 + fv, 38 + fw, 38 + fx, 38 + fy, 38 + fz, 38 + ga, 38 + gb, 38 + gc, 38 + gd, 38 + ge, 38 + gf, 38 + gg, 38 + gh, 38 + gi, 38 + gj, 38 + gk, 38 + gl, 38 + gm, 38 + gn, 38 + go, 38 + gp, 38 + gq, 38 + gr, 38 + gs, 38 + gt, 38 + gu, 38 + gv, 38 + gw, 38 + gx, 38 + gy, 38 + gz, 38 + ha, 38 + hb, 38 + hc, 38 + hd, 38 + he, 38 + hf, 38 + hg, 38 + hh, 38 + hi, 38 + hj, 38 + hk, 38 + hl, 38 + hm, 38 + hn, 38 + ho, 38 + hp, 38 + hq, 38 + hr, 38 + hs, 38 + ht, 38 + hu, 38 + hv, 38 + hw, 38 + hx, 38 + hy, 38 + hz, 38 + ia, 38 + ib, 38 + ic, 38 + id, 38 + ie, 38 + if, 38 + ig, 38 + ih, 38 + ii, 38 + ij, 38 + ik, 38 + il, 38 + im, 38 + in, 38 + io, 38 + ip, 38 + iq, 38 + ir, 38 + is, 38 + it, 38 + iu, 38 + iv, 38 + iw, 38 + ix, 38 + iy, 38 + iz, 38 + ja, 38 + jb, 38 + jc, 38 + jd, 38 + je, 38 + jf, 38 + jg, 38 + jh, 38 + ji, 38 + jj, 38 + jk, 38 + jl, 38 + jm, 38 + jn, 38 + jo, 38 + jp, 38 + jq, 38 + jr, 38 + js, 38 + jt, 38 + ju, 38 + jv, 38 + jw, 38 + jx, 38 + jy, 38 + jz, 38 + ka, 38 + kb, 38 + kc, 38 + kd, 38 + ke, 38 + kf, 38 + kg, 38 + kh, 38 + ki, 38 + kj, 38 + kk, 38 + kl, 38 + km, 38 + kn, 38 + ko, 38 + kp, 38 + kq, 38 + kr, 38 + ks, 38 + kt, 38 + ku, 38 + kv, 38 + kw, 38 + kx, 38 + ky, 38 + kz, 38 + la, 38 + lb, 38 + lc, 38 + ld, 38 + le, 38 + lf, 38 + lg, 38 + lh, 38 + li, 38 + lj, 38 + lk, 38 + ll, 38 + lm, 38 + ln, 38 + lo, 38 + lp, 38 + lq, 38 + lr, 38 + ls, 38 + lt, 38 + lu, 38 + lv, 38 + lw, 38 + lx, 38 + ly, 38 + lz, 38 + ma, 38 + mb, 38 + mc, 38 + md, 38 + me, 38 + mf, 38 + mg, 38 + mh, 38 + mi, 38 + mj, 38 + mk, 38 + ml, 38 + mm, 38 + mn, 38 + mo, 38 + mp, 38 + mq, 38 + mr, 38 + m s, 38 + mt, 38 + mu, 38 + mv, 38 + mw, 38 + mx, 38 + my, 38 + mz, 38 + na, 38 + nb, 38 + nc, 38 + nd, 38 + ne, 38 + nf, 38 + ng, 38 + nh, 38 + ni, 38 + nj, 38 + nk, 38 + nl, 38 + nm, 38 + nn, 38 + no, 38 + np, 38 + nq, 38 + nr, 38 + ns, 38 + nt, 38 + nu, 38 + nv, 38 + nw, 38 + nx, 38 + ny, 38 + nz, 38 + oa, 38 + ob, 38 + oc, 38 + od, 38 + oe, 38 + of, 38 + og, 38 + oh, 38 + oi, 38 + oj, 38 + ok, 38 + ol, 38 + om, 38 + on, 38 + oo, 38 + op, 38 + oq, 38 + or, 38 + os, 38 + ot, 38 + ou, 38 + ov, 38 + ow, 38 + ox, 38 + oy, 38 + oz, 38 + pa, 38 + pb, 38 + pc, 38 + pd, 38 + pe, 38 + pf, 38 + pg, 38 + ph, 38 + pi, 38 + pj, 38 + pk, 38 + pl, 38 + pm, 38 + pn, 38 + po, 38 + pp, 38 + pq, 38 + pr, 38 + ps, 38 + pt, 38 + pu, 38 + pv, 38 + pw, 38 + px, 38 + py, 38 + pz, 38 + qa, 38 + qb, 38 + qc, 38 + qd, 38 + qe, 38 + qf, 38 + qg, 38 + qh, 38 + qi, 38 + qj, 38 + qk, 38 + ql, 38 + qm, 38 + qn, 38 + qo, 38 + qp, 38 + qq, 38 + qr, 38 + qs, 38 + qt, 38 + qu, 38 + qv, 38 + qw, 38 + qx, 38 + qy, 38 + qz, 38 + ra, 38 + rb, 38 + rc, 38 + rd, 38 + re, 38 + rf, 38 + rg, 38 + rh, 38 + ri, 38 + rj, 38 + rk, 38 + rl, 38 + rm, 38 + rn, 38 + ro, 38 + rp, 38 + rq, 38 + rr, 38 + rs, 38 + rt, 38 + ru, 38 + rv, 38 + rw, 38 + rx, 38 + ry, 38 + rz, 38 + sa, 38 + sb, 38 + sc, 38 + sd, 38 + se, 38 + sf, 38 + sg, 38 + sh, 38 + si, 38 + sj, 38 + sk, 38 + sl, 38 + sm, 38 + sn, 38 + so, 38 + sp, 38 + sq, 38 + sr, 39 + a, 39 + b, 39 + c, 39 + d, 39 + e, 39 + f, 39 + g, 39 + h, 39 + i, 39 + j, 39 + k, 39 + l, 39 + m, 39 + n, 39 + o, 39 + p, 39 + q, 39 + r, 39 + s, 39 + t, 39 + u, 39 + v, 39 + w, 39 + x, 39 + y, 39 + z, 39 + aa, 39 + ab, 39 + ac, 39 + ad, 39 + ae, 39 + af, 39 + ag, 39 + ah, 39 + ai, 39 + aj, 39 + ak, 39 + al, 39 + am, 39 + an, 39 + ao, 39 + ap, 39 + aq, 39 + ar, 39 + as, 39 + at, 39 + au, 39 + av, 39 + aw, 39 + ax, 39 + ay, 39 + az, 39 + ba, 39 + bb, 39 + bc, 39 + bd, 39 + be, 39 + bf, 39 + bg, 39 + bh, 39 + bi, 39 + bj, 39 + bk, 39 + bl, 39 + bm, 39 + bn, 39 + bo, 39 + bp, 39 + bq, 39 + br, 39 + bs, 39 + bt, 39 + bu, 39 + bv, 39 + bw, 39 + bx, 39 + by, 39 + bz, 39 + ca, 39 + cb, 39 + cc, 39 + cd, 39 + ce, 39 + cf, 39 + cg, 39 + ch, 39 + ci, 39 + cj, 39 + ck, 39 + cl, 39 + cm, 39 + cn, 39 + co, 39 + cp, 39 + cq, 39 + cr, 39 + cs, 39 + ct, 39 + cu, 39 + cv, 39 + cw, 39 + cx, 39 + cy, 39 + cz, 39 + da, 39 + db, 39 + dc, 39 + dd, 39 + de, 39 + df, 39 + dg, 39 + dh, 39 + di, 39 + dj, 39 + dk, 39 + dl, 39 + dm, 39 + dn, 39 + do, 39 + dp, 39 + dq, 39 + dr, 39 + ds, 39 + dt, 39 + du, 39 + dv, 39 + dw, 39 + dx, 39 + dy, 39 + dz, 39 + ea, 39 + eb, 39 + ec, 39 + ed, 39 + ee, 39 + ef, 39 + eg, 39 + eh, 39 + ei, 39 + ej, 39 + ek, 39 + el, 39 + em, 39 + en, 39 + eo, 39 + ep, 39 + eq, 39 + er, 39 + es, 39 + et, 39 + eu, 39 + ev, 39 + ew, 39 + ex, 39 + ey, 39 + ez, 39 + fa, 39 + fb, 39 + fc, 39 + fd, 39 + fe, 39 + ff, 39 + fg, 39 + fh, 39 + fi, 39 + fj, 39 + fk, 39 + fl, 39 + fm, 39 + fn, 39 + fo, 39 + fp, 39 + fq, 39 + fr, 39 + fs, 39 + ft, 39 + fu, 39 + fv, 39 + fw, 39 + fx, 39 + fy, 39 + fz, 39 + ga, 39 + gb, 39 + gc, 39 + gd, 39 + ge, 39 + gf, 39 + gg, 39 + gh, 39 + gi, 39 + gj, 39 + gk, 39 + gl, 39 + gm , 39 + gn, 39 + go, 39 + gp, 39 + gq, 39 + gr, 39 + gs, 39 + gt, 39 + gu, 39 + gv, 39 + gw, 39 + gx, 39 + gy, 39 + gz, 39 + ha, 39 + hb, 39 + hc, 39 + hd, 39 + he, 39 + hf, 39 + hg, 39 + hh, 39 + hi, 39 + hj, 39 + hk, 39 + hl , 39 + hm, 39 + hn, 39 + ho, 39 + hp, 39 + hq, 39 + hr, 39 + hs, 39 + ht, 39 + hu, 39 + hv, 39 + hw, 39 + hx, 39 + hy, 39 + hz, 39 + ia, 39 + ib, 39 + ic, 39 + id, 39 + ie, 39 + if, 39 + ig, 39 + ih, 39 + ii, 39 + ij, 39 + ik , 39 + il, 39 + im, 39 + in, 39 + io, 39 + ip, 39 + iq, 39 + ir, 39 + is, 39 + it, 39 + iu, 39 + iv, 39 + iw, 39 + ix, 39 + iy, 39 + iz, 39 + ja, 39 + jb, 39 + jc, 39 + jd, 39 + je, 39 + jf, 39 + jg, 39 + jh, 39 + ji, 39 + jj , 39 + jk, 39 + jl, 39 + jm, 39 + jn, 39 + jo, 39 + jp, 39 + jq, 39 + jr, 39 + js, 39 + jt, 39 + ju, 39 + jv, 39 + jw, 39 + jx, 39 + jy, 39 + jz, 39 + ka, 39 + kb, 39 + kc, 39 + kd, 39 + ke, 39 + kf, 39 + kg, 39 + kh, 39 + ki , 39 + kj, 39 + kk, 39 + kl, 39 + km, 39 + kn, 39 + ko, 39 + kp, 39 + kq, 39 + kr, 39 + ks, 39 + kt, 39 + ku, 39 + kv, 39 + kw, 39 + kx, 39 + ky, 39 + kz, 39 + la, 39 + lb, 39 + lc, 39 + ld, 39 + le, 39 + lf, 39 + lg, 39 + lh , 39 + li, 39 + lj, 39 + lk, 39 + ll, 39 + lm, 39 + ln, 39 + lo, 39 + lp, 39 + lq, 39 + lr, 39 + ls, 39 + lt, 39 + lu, 39 + lv, 39 + lw, 39 + lx, 39 + ly, 39 + lz, 39 + ma, 39 + mb, 39 + mc, 39 + md, 39 + me, 39 + mf, 39 + mg , 39 + mh, 39 + mi, 39 + mj, 39 + mk, 39 + ml, 39 + mm, 39 + mn, 39 + mo, 39 + mp, 39 + mq, 39 + mr, 39 + ms, 39 + mt, 39 + mu, 39 + mv, 39 + mw, 39 + mx, 39 + my, 39 + mz, 39 + na, 39 + nb, 39 + nc, 39 + nd, 39 + ne, 39 + nf, 39 + ng, 39 + nh, 39 + ni, 39 + nj, 39 + nk, 39 + nl, 39 + nm, 39 + nn, 39 + no, 39 + np, 39 + nq, 39 + nr, 39 + ns, 39 + nt, 39 + nu, 39 + nv, 39 + nw, 39 + nx, 39 + ny, 39 + nz, 39 + oa, 39 + ob, 39 + oc, 39 + od, 39 + oe, 39 + of, 39 + og, 39 + oh, 39 + oi, 39 + oj, 39 + ok, 39 + ol, 39 + om, 39 + on, 39 + oo, 39 + op, 39 + oq, 39 + or, 39 + os, 39 + ot, 39 + ou, 39 + ov, 39 + ow, 39 + ox, 39 + oy, 39 + oz, 39 + pa, 39 + pb, 39 + pc, 39 + pd, 39 + pe, 39 + pf, 39 + pg, 39 + ph, 39 + pi, 39 + pj, 39 + pk, 39 + pl, 39 + pm, 39 + pn, 39 + po, 39 + pp, 39 + pq, 39 + pr, 39 + ps, 39 + pt, 39 + pu, 39 + pv, 39 + pw, 39 + px, 39 + py, 39 + pz, 39 + qa, 39 + qb, 39 + qc, 39 + qd, 39 + qe, 39 + qf, 39 + qg, 39 + qh, 39 + qi, 39 + qj, 39 + qk, 39 + ql, 39 + qm, 39 + qn, 39 + qo, 39 + qp, 39 + qq, 39 + qr, 39 + qs, 39 + qt, 39 + qu, 39 + qv, 39 + qw, 39 + qx, 39 + qy, 39 + qz, 39 + ra, 39 + rb, 39 + rc, 39 + rd, 39 + re, 39 + rf, 39 + rg, 39 + rh, 39 + ri, 39 + rj, 39 + rk, 39 + rl, 39 + rm, 39 + rn, 39 + ro, 39 + rp, 39 + rq, 39 + rr, 39 + rs, 39 + rt, 39 + ru, 39 + rv, 39 + rw, 39 + rx, 39 + ry, 39 + rz, 39 + sa, 39 + sb, 39 + sc, 39 + sd, 39 + se, 39 + sf, 39 + sg, 39 + sh, 39 + si, 39 + sj, 39 + sk, 39 + sl, 39 + sm, 39 + sn, 39 + so, 39 + sp, 39 + sq, 39 + sr,
40 + a, 40 + b, 40 + c, 40 + d, 40 + e, 40 + f, 40 + g, 40 + h, 40 + i, 40 + j, 40 + k, 40 + l, 40 + m, 40 + n, 40 + o, 40 + p, 40 + q, 40 + r, 40 + s, 40 + t, 40 + u, 40 + v, 40 + w, 40 + x, 40 + y, 40 + z, 40 + aa, 40 + ab, 40 + ac, 40 + ad, 40 + ae, 40 + af, 40 + ag, 40 + ah, 40 + ai, 40 + aj, 40 + ak, 40 + al, 40 + am, 40 + an, 40 + ao, 40 + ap, 40 + aq, 40 + ar, 40 + as, 40 + at, 40 + au, 40 + av, 40 + aw, 40 + ax, 40 + ay, 40 + az, 40 + ba, 40 + bb, 40 + bc, 40 + bd, 40 + be, 40 + bf, 40 + bg, 40 + bh, 40 + bi, 40 + bj, 40 + bk, 40 + bl, 40 + bm, 40 + bn, 40 + bo, 40 + bp, 40 + bq, 40 + br, 40 + bs, 40 + bt, 40 + bu, 40 + bv, 40 + bw, 40 + bx, 40 + by, 40 + bz, 40 + ca, 40 + cb, 40 + cc, 40 + cd, 40 + ce, 40 + cf, 40 + cg, 40 + ch, 40 + ci, 40 + cj, 40 + ck, 40 + cl, 40 + cm, 40 + cn, 40 + co, 40 + cp, 40 + cq, 40 + cr, 40 + cs, 40 + ct, 40 + cu, 40 + cv, 40 + cw, 40 + cx, 40 + cy, 40 + cz, 40 + da, 40 + db, 40 + dc, 40 + dd, 40 + de, 40 + df, 40 + dg, 40 + dh, 40 + di, 40 + dj, 40 + dk, 40 + dl, 40 + dm, 40 + dn, 40 + do, 40 + dp, 40 + dq, 40 + dr, 40 + ds, 40 + dt, 40 + du, 40 + dv, 40 + dw, 40 + dx, 40 + dy, 40 + dz, 40 + ea, 40 + eb, 40 + ec, 40 + ed, 40 + ee, 40 + ef, 40 + eg, 40 + eh, 40 + ei, 40 + ej, 40 + ek, 40 + el, 40 + em, 40 + en, 40 + eo, 40 + ep, 40 + eq, 40 + er, 40 + es, 40 + et, 40 + eu, 40 + ev, 40 + ew, 40 + ex, 40 + ey, 40 + ez, 40 + fa, 40 + fb, 40 + fc, 40 + fd, 40 + fe, 40 + ff, 40 + fg, 40 + fh, 40 + fi, 40 + fj, 40 + fk, 40 + fl, 40 + fm, 40 + fn, 40 + fo, 40 + fp, 40 + fq, 40 + fr, 40 + fs, 40 + ft, 40 + fu, 40 + fv, 40 + fw, 40 + fx, 40 + fy, 40 + fz, 40 + ga, 40 + gb, 40 + gc, 40 + gd, 40 + ge, 40 + gf, 40 + gg, 40 + gh, 40 + gi, 40 + gj, 40 + gk, 40 + gl, 40 + gm, 40 + gn, 40 + go, 40 + gp, 40 + gq, 40 + gr, 40 + gs, 40 + gt, 40 + gu, 40 + gv, 40 + gw, 40 + gx, 40 + gy, 40 + gz, 40 + ha, 40 + hb, 40 + hc, 40 + hd, 40 + he, 40 + hf, 40 + hg, 40 + hh, 40 + hi, 40 + hj, 40 + hk, 40 + hl, 40 + hm, 40 + hn, 40 + ho, 40 + hp, 40 + hq, 40 + hr, 40 + hs, 40 + ht, 40 + hu, 40 + hv, 40 + hw, 40 + hx, 40 + hy, 40 + hz, 40 + ia, 40 + ib, 40 + ic, 40 + id, 40 + ie, 40 + if, 40 + ig, 40 + ih, 40 + ii, 40 + ij, 40 + ik, 40 + il, 40 + im, 40 + in, 40 + io, 40 + ip, 40 + iq, 40 + ir, 40 + is, 40 + it, 40 + iu, 40 + iv, 40 + iw, 40 + ix, 40 + iy, 40 + iz, 40 + ja, 40 + jb, 40 + jc, 40 + jd, 40 + je, 40 + jf, 40 + jg, 40 + jh, 40 + ji, 40 + jj, 40 + jk, 40 + jl, 40 + jm, 40 + jn, 40 + jo, 40 + jp, 40 + jq, 40 + jr, 40 + js, 40 + jt, 40 + ju, 40 + jv, 40 + jw, 40 + jx, 40 + jy, 40 + jz, 40 + ka, 40 + kb, 40 + kc, 40 + kd, 40 + ke, 40 + kf, 40 + kg, 40 + kh, 40 + ki, 40 + kj, 40 + kk, 40 + kl, 40 + km, 40 + kn, 40 + ko, 40 + kp, 40 + kq, 40 + kr, 40 + ks, 40 + kt, 40 + ku, 40 + kv, 40 + kw, 40 + kx, 40 + ky, 40 + kz, 40 + la, 40 + lb, 40 + lc, 40 + ld, 40 + le, 40 + lf, 40 + lg, 40 + lh, 40 + li, 40 + lj, 40 + lk, 40 + ll, 40 + lm, 40 + ln, 40 + lo, 40 + lp, 40 + lq, 40 + lr, 40 + ls, 40 + lt, 40 + lu, 40 + lv, 40 + lw, 40 + lx, 40 + ly, 40 + l z, 40 + ma, 40 + mb, 40 + mc, 40 + md, 40 + me, 40 + mf, 40 + mg, 40 + mh, 40 + mi, 40 + mj, 40 + mk, 40 + ml, 40 + mm, 40 + mn, 40 + mo, 40 + mp, 40 + mq, 40 + mr, 40 + ms, 40 + mt, 40 + mu, 40 + mv, 40 + mw, 40 + mx, 40 + my, 40 + mz, 40 + na, 40 + nb, 40 + nc, 40 + nd, 40 + ne, 40 + nf, 40 + ng, 40 + nh, 40 + ni, 40 + nj, 40 + nk, 40 + nl, 40 + nm, 40 + nn, 40 + no, 40 + np, 40 + nq, 40 + nr, 40 + ns, 40 + nt, 40 + nu, 40 + nv, 40 + nw, 40 + nx, 40 + ny, 40 + nz, 40 + oa, 40 + ob, 40 + oc, 40 + od, 40 + oe, 40 + of, 40 + og, 40 + oh, 40 + oi, 40 + oj, 40 + ok, 40 + ol, 40 + om, 40 + on, 40 + oo, 40 + op, 40 + oq, 40 + or, 40 + os, 40 + ot, 40 + ou, 40 + ov, 40 + ow, 40 + ox, 40 + oy, 40 + oz, 40 + pa, 40 + pb, 40 + pc, 40 + pd, 40 + pe, 40 + pf, 40 + pg, 40 + ph, 40 + pi, 40 + pj, 40 + pk, 40 + pl, 40 + pm, 40 + pn, 40 + po, 40 + pp, 40 + pq, 40 + pr, 40 + ps, 40 + pt, 40 + pu, 40 + pv, 40 + pw, 40 + px, 40 + py, 40 + pz, 40 + qa, 40 + qb, 40 + qc, 40 + qd, 40 + qe, 40 + qf, 40 + qg, 40 + qh, 40 + qi, 40 + qj, 40 + qk, 40 + ql, 40 + qm, 40 + qn, 40 + qo, 40 + qp, 40 + qq, 40 + qr, 40 + qs, 40 + qt, 40 + qu, 40 + qv, 40 + qw, 40 + qx, 40 + qy, 40 + qz, 40 + ra, 40 + rb, 40 + rc, 40 + rd, 40 + re, 40 + rf, 40 + rg, 40 + rh, 40 + ri, 40 + rj, 40 + rk, 40 + rl, 40 + rm, 40 + rn, 40 + ro, 40 + rp, 40 + rq, 40 + rr, 40 + rs, 40 + rt, 40 + ru, 40 + rv, 40 + rw, 40 + rx, 40 + ry, 40 + rz, 40 + sa, 40 + sb, 40 + sc, 40 + sd, 40 + se, 40 + sf, 40 + sg, 40 + sh, 40 + si, 40 + sj, 40 + sk, 40 + sl, 40 + sm, 40 + sn, 40 + so, 40 + sp, 40 + sq, 40 + sr, 41 + a, 41 + b, 41 + c, 41 + d, 41 + e , 41 + f, 41 + g, 41 + h, 41 + i, 41 + j, 41 + k, 41 + l, 41 + m, 41 + n, 41 + o, 41 + p, 41 + q, 41 + r, 41 + s, 41 + t, 41 + u, 41 + v, 41 + w, 41 + x, 41 + y, 41 + z, 41 + aa, 41 + ab, 41 + ac, 41 + ad , 41 + ae, 41 + af, 41 + ag, 41 + ah, 41 + ai, 41 + aj, 41 + ak, 41 + al, 41 + am, 41 + an, 41 + ao, 41 + ap, 41 + aq, 41 + ar, 41 + as, 41 + at, 41 + au, 41 + av, 41 + aw, 41 + ax, 41 + ay, 41 + az, 41 + ba, 41 + bb, 41 + bc , 41 + bd, 41 + be, 41 + bf, 41 + bg, 41 + bh, 41 + bi, 41 + bj, 41 + bk, 41 + bl, 41 + bm, 41 + bn, 41 + bo, 41 + bp, 41 + bq, 41 + br, 41 + bs, 41 + bt, 41 + bu, 41 + bv, 41 + bw, 41 + bx, 41 + by, 41 + bz, 41 + ca, 41 + cb , 41 + cc, 41 + cd, 41 + ce, 41 + cf, 41 + cg, 41 + ch, 41 + ci, 41 + cj, 41 + ck, 41 + cl, 41 + cm, 41 + cn, 41 + co, 41 + cp, 41 + cq, 41 + cr, 41 + cs, 41 + ct, 41 + cu, 41 + cv, 41 + cw, 41 + cx, 41 + cy, 41 + cz, 41 + da , 41 + db, 41 + dc, 41 + dd, 41 + de, 41 + df, 41 + dg, 41 + dh, 41 + di, 41 + dj, 41 + dk, 41 + dl, 41 + dm, 41 + dn, 41 + do, 41 + dp, 41 + dq, 41 + dr, 41 + ds, 41 + dt, 41 + du, 41 + dv, 41 + dw, 41 + dx, 41 + dy, 41 + dz , 41 + ea, 41 + eb, 41 + ec, 41 + ed, 41 + ee, 41 + ef, 41 + eg, 41 + eh, 41 + ei, 41 + ej, 41 + ek, 41 + el, 41 + em, 41 + en, 41 + eo, 41 + ep, 41 + eq, 41 + er, 41 + es, 41 + et, 41 + eu, 41 + ev, 41 + ew, 41 + ex, 41 + ey , 41 + ez, 41 + fa, 41 + fb, 41 + fc, 41 + fd, 41 + fe, 41 + ff, 41 + fg, 41 + fh, 41 + fi, 41 + fj, 41 + fk, 41 + fl, 41 + fm, 41 + fn, 41 + fo, 41 + fp, 41 + fq, 41 + fr, 41 + fs, 41 + ft , 41 + fu, 41 + fv, 41 + fw, 41 + fx, 41 + fy, 41 + fz, 41 + ga, 41 + gb, 41 + gc, 41 + gd, 41 + ge, 41 + gf, 41 + gg, 41 + gh, 41 + gi, 41 + gj, 41 + gk, 41 + gl, 41 + gm, 41 + gn, 41 + go, 41 + gp, 41 + gq, 41 + gr, 41 + gs , 41 + gt, 41 + gu, 41 + gv, 41 + gw, 41 + gx, 41 + gy, 41 + gz, 41 + ha, 41 + hb, 41 + hc, 41 + hd, 41 + he, 41 + hf, 41 + hg, 41 + hh, 41 + hi, 41 + hj, 41 + hk, 41 + hl, 41 + hm, 41 + hn, 41 + ho, 41 + hp, 41 + hq, 41 + hr , 41 + hs, 41 + ht, 41 + hu, 41 + hv, 41 + hw, 41 + hx, 41 + hy, 41 + hz, 41 + ia, 41 + ib, 41 + ic, 41 + id, 41 + ie, 41 + if, 41 + ig, 41 + ih, 41 + ii, 41 + ij, 41 + ik, 41 + il, 41 + im, 41 + in, 41 + io, 41 + ip, 41 + iq , 41 + ir, 41 + is, 41 + it, 41 + iu, 41 + iv, 41 + iw, 41 + ix, 41 + iy, 41 + iz, 41 + ja, 41 + jb, 41 + jc, 41 + jd, 41 + je, 41 + jf, 41 + jg, 41 + jh, 41 + ji, 41 + jj, 41 + jk, 41 + jl, 41 + jm, 41 + jn, 41 + jo, 41 + jp , 41 + jq, 41 + jr, 41 + js, 41 + jt, 41 + ju, 41 + jv, 41 + jw, 41 + jx, 41 + jy, 41 + jz, 41 + ka, 41 + kb, 41 + kc, 41 + kd, 41 + ke, 41 + kf, 41 + kg, 41 + kh, 41 + ki, 41 + kj, 41 + kk, 41 + kl, 41 + km, 41 + kn, 41 + ko , 41 + kp, 41 + kq, 41 + kr, 41 + ks, 41 + kt, 41 + ku, 41 + kv, 41 + kw, 41 + kx, 41 + ky, 41 + kz, 41 + la, 41 + lb, 41 + lc, 41 + ld, 41 + le, 41 + lf, 41 + lg, 41 + lh, 41 + li, 41 + lj, 41 + lk, 41 + ll, 41 + lm, 41 + ln , 41 + lo, 41 + lp, 41 + lq, 41 + lr, 41 + ls, 41 + lt, 41 + lu, 41 + lv, 41 + lw, 41 + lx, 41 + ly, 41 + lz, 41 + ma, 41 + mb, 41 + mc, 41 + md, 41 + me, 41 + mf, 41 + mg, 41 + mh, 41 + mi, 41 + mj, 41 + mk, 41 + ml, 41 + mm, 41 + mn, 41 + mo, 41 + mp, 41 + mq, 41 + mr, 41 + ms, 41 + mt, 41 + mu, 41 + mv, 41 + mw, 41 + mx, 41 + my, 41 + mz, 41 + na, 41 + nb, 41 + nc, 41 + nd, 41 + ne, 41 + nf, 41 + ng, 41 + nh, 41 + ni, 41 + nj, 41 + nk, 41 + nl, 41 + nm, 41 + nn, 41 + no, 41 + np, 41 + nq, 41 + nr, 41 + ns, 41 + nt, 41 + nu, 41 + nv, 41 + nw, 41 + nx, 41 + ny, 41 + nz, 41 + oa, 41 + ob, 41 + oc, 41 + od, 41 + oe, 41 + of, 41 + og, 41 + oh, 41 + oi, 41 + oj, 41 + ok, 41 + ol, 41 + om, 41 + on, 41 + oo, 41 + op, 41 + oq, 41 + or, 41 + os, 41 + ot, 41 + ou, 41 + ov, 41 + ow, 41 + ox, 41 + oy, 41 + oz, 41 + pa, 41 + pb, 41 + pc, 41 + pd, 41 + pe, 41 + pf, 41 + pg, 41 + ph, 41 + pi, 41 + pj, 41 + pk, 41 + pl, 41 + pm, 41 + pn, 41 + po, 41 + pp, 41 + pq, 41 + pr, 41 + ps, 41 + pt, 41 + pu, 41 + pv, 41 + pw, 41 + px, 41 + py, 41 + pz, 41 + qa, 41 + qb, 41 + qc, 41 + qd, 41 + qe, 41 + qf, 41 + qg, 41 + qh, 41 + qi, 41 + qj, 41 + qk, 41 + ql, 41 + qm, 41 + qn, 41 + qo, 41 + qp, 41 + qq, 41 + qr, 41 + qs, 41 + qt, 41 + qu, 41 + qv, 41 + qw, 41 + qx, 41 + qy, 41 + qz, 41 + ra, 41 + rb, 41 + rc, 41 + rd, 41 + re, 41 + rf, 41 + rg, 41 + rh, 41 + ri, 41 + rj, 41 + rk, 41 + rl, 41 + rm, 41 + rn, 41 + ro, 41 + rp, 41 + rq, 41 + rr, 41 + rs, 41 + rt, 41 + ru, 41 + rv, 41 + rw, 41 + rx, 41 + ry, 41 + rz, 41 + sa, 41 + sb, 41 + s c, 41 + sd, 41 + se, 41 + sf, 41 + sg, 41 + sh, 41 + si, 41 + sj, 41 + sk, 41 + sl, 41 + sm, 41 + sn, 41 + so, 41 + sp, 41 + sq, 41 + sr, 42 + a, 42 + b, 42 + c, 42 + d, 42 + e, 42 + f, 42 + g, 42 + h, 42 + i, 42 + j, 42 + k, 42 + l, 42 + m, 42 + n, 42 + o, 42 + p, 42 + q, 42 + r, 42 + s, 42 + t, 42 + u, 42 + v, 42 + w, 42 + x, 42 + y, 42 + z, 42 + aa, 42 + ab, 42 + ac, 42 + ad, 42 + ae, 42 + af, 42 + ag, 42 + ah, 42 + ai, 42 + aj, 42 + ak, 42 + al, 42 + am, 42 + an, 42 + ao, 42 + ap, 42 + aq, 42 + ar, 42 + as, 42 + at, 42 + au, 42 + av, 42 + aw, 42 + ax, 42 + ay, 42 + az, 42 + ba, 42 + bb, 42 + bc, 42 + bd, 42 + be, 42 + bf, 42 + bg, 42 + bh, 42 + bi, 42 + bj, 42 + bk, 42 + bl, 42 + bm, 42 + bn, 42 + bo, 42 + bp, 42 + bq, 42 + br, 42 + bs, 42 + bt, 42 + bu, 42 + bv, 42 + bw, 42 + bx, 42 + by, 42 + bz, 42 + ca, 42 + cb, 42 + cc, 42 + cd, 42 + ce, 42 + cf, 42 + cg, 42 + ch, 42 + ci, 42 + cj, 42 + ck, 42 + cl, 42 + cm, 42 + cn, 42 + co, 42 + cp, 42 + cq, 42 + cr, 42 + cs, 42 + ct, 42 + cu, 42 + cv, 42 + cw, 42 + cx, 42 + cy, 42 + cz, 42 + da, 42 + db, 42 + dc, 42 + dd, 42 + de, 42 + df, 42 + dg, 42 + dh, 42 + di, 42 + dj, 42 + dk, 42 + dl, 42 + dm, 42 + dn, 42 + do, 42 + dp, 42 + dq, 42 + dr, 42 + ds, 42 + dt, 42 + du, 42 + dv, 42 + dw, 42 + dx, 42 + dy, 42 + dz, 42 + ea, 42 + eb, 42 + ec, 42 + ed, 42 + ee, 42 + ef, 42 + eg, 42 + eh, 42 + ei, 42 + ej, 42 + ek, 42 + el, 42 + em, 42 + en, 42 + eo, 42 + ep, 42 + eq, 42 + er, 42 + es, 42 + et, 42 + eu, 42 + ev, 42 + ew, 42 + ex, 42 + ey, 42 + e z, 42 + fa, 42 + fb, 42 + fc, 42 + fd, 42 + fe, 42 + ff, 42 + fg, 42 + fh, 42 + fi, 42 + fj, 42 + fk, 42 + fl, 42 + fm, 42 + fn, 42 + fo, 42 + fp, 42 + fq, 42 + fr, 42 + fs, 42 + ft, 42 + fu, 42 + fv, 42 + fw, 42 + fx, 42 + fy, 42 + fz, 42 + ga, 42 + gb, 42 + gc, 42 + gd, 42 + ge, 42 + gf, 42 + gg, 42 + gh, 42 + gi, 42 + gj, 42 + gk, 42 + gl, 42 + gm, 42 + gn, 42 + go, 42 + gp, 42 + gq, 42 + gr, 42 + gs, 42 + gt, 42 + gu, 42 + gv, 42 + gw, 42 + gx, 42 + gy, 42 + gz, 42 + ha, 42 + hb, 42 + hc, 42 + hd, 42 + he, 42 + hf, 42 + hg, 42 + hh, 42 + hi, 42 + hj, 42 + hk, 42 + hl, 42 + hm, 42 + hn, 42 + ho, 42 + hp, 42 + hq, 42 + hr, 42 + hs, 42 + ht, 42 + hu, 42 + hv, 42 + hw, 42 + hx, 42 + hy, 42 + hz, 42 + ia, 42 + ib, 42 + ic, 42 + id, 42 + ie, 42 + if, 42 + ig, 42 + ih, 42 + ii, 42 + ij, 42 + ik, 42 + il, 42 + im, 42 + in, 42 + io, 42 + ip, 42 + iq, 42 + ir, 42 + is, 42 + it, 42 + iu, 42 + iv, 42 + iw, 42 + ix, 42 + iy, 42 + iz, 42 + ja, 42 + jb, 42 + jc, 42 + jd, 42 + je, 42 + jf, 42 + jg, 42 + jh, 42 + ji, 42 + jj, 42 + jk, 42 + jl, 42 + jm, 42 + jn, 42 + jo, 42 + jp, 42 + jq, 42 + jr, 42 + js, 42 + jt, 42 + ju, 42 + jv, 42 + jw, 42 + jx, 42 + jy, 42 + jz, 42 + ka, 42 + kb, 42 + kc, 42 + kd, 42 + ke, 42 + kf, 42 + kg, 42 + kh, 42 + ki, 42 + kj, 42 + kk, 42 + kl, 42 + km, 42 + kn, 42 + ko, 42 + kp, 42 + kq, 42 + kr, 42 + ks, 42 + kt, 42 + ku, 42 + kv, 42 + kw, 42 + kx, 42 + ky, 42 + kz, 42 + la, 42 + lb, 42 + lc, 42 + ld, 42 + le, 42 + lf, 42 + lg, 42 + lh, 42 + li, 42 + lj, 42 + lk, 42 + ll, 42 + lm, 42 + ln, 42 + lo, 42 + lp, 42 + lq, 42 + lr, 42 + ls, 42 + lt, 42 + lu, 42 + lv, 42 + lw , 42 + lx, 42 + ly, 42 + lz, 42 + ma, 42 + mb, 42 + mc, 42 + md, 42 + me, 42 + mf, 42 + mg, 42 + mh, 42 + mi, 42 + mj, 42 + mk, 42 + ml, 42 + mm, 42 + mn, 42 + mo, 42 + mp, 42 + mq, 42 + mr, 42 + ms, 42 + mt, 42 + mu, 42 + mv , 42 + mw, 42 + mx, 42 + my, 42 + mz, 42 + na, 42 + nb, 42 + nc, 42 + nd, 42 + ne, 42 + nf, 42 + ng, 42 + nh, 42 + ni, 42 + nj, 42 + nk, 42 + nl, 42 + nm, 42 + nn, 42 + no, 42 + np, 42 + nq, 42 + nr, 42 + ns, 42 + nt, 42 + nu , 42 + nv, 42 + nw, 42 + nx, 42 + ny, 42 + nz, 42 + oa, 42 + ob, 42 + oc, 42 + od, 42 + oe, 42 + of, 42 + og, 42 + oh, 42 + oi, 42 + oj, 42 + ok, 42 + ol, 42 + om, 42 + on, 42 + oo, 42 + op, 42 + oq, 42 + or, 42 + os, 42 + ot , 42 + ou, 42 + ov, 42 + ow, 42 + ox, 42 + oy, 42 + oz, 42 + pa, 42 + pb, 42 + pc, 42 + pd, 42 + pe, 42 + pf, 42 + pg, 42 + ph, 42 + pi, 42 + pj, 42 + pk, 42 + pl, 42 + pm, 42 + pn, 42 + po, 42 + pp, 42 + pq, 42 + pr, 42 + ps , 42 + pt, 42 + pu, 42 + pv, 42 + pw, 42 + px, 42 + py, 42 + pz, 42 + qa, 42 + qb, 42 + qc, 42 + qd, 42 + qe, 42 + qf, 42 + qg, 42 + qh, 42 + qi, 42 + qj, 42 + qk, 42 + ql, 42 + qm, 42 + qn, 42 + qo, 42 + qp, 42 + qq, 42 + qr , 42 + qs, 42 + qt, 42 + qu, 42 + qv, 42 + qw, 42 + qx, 42 + qy, 42 + qz, 42 + ra, 42 + rb, 42 + rc, 42 + rd, 42 + re, 42 + rf, 42 + rg, 42 + rh, 42 + ri, 42 + rj, 42 + rk, 42 + rl, 42 + rm, 42 + rn, 42 + ro, 42 + rp, 42 + rq , 42 + rr, 42 + rs, 42 + rt, 42 + ru, 42 + rv, 42 + rw, 42 + rx, 42 + ry, 42 + rz, 42 + sa, 42 + sb, 42 + sc, 42 + sd, 42 + se, 42 + sf, 42 + sg, 42 + sh, 42 + si, 42 + sj, 42 + sk, 42 + sl, 42 + sm, 42 + sn, 42 + so, 42 + sp, 42 + sq, 42 + sr, 43 + a, 43 + b, 43 + c, 43 + d, 43 + e, 43 + f, 43 + g, 43 + h, 43 + i, 43 + j, 43 + k, 43 + l, 43 + m, 43 + n, 43 + o, 43 + p, 43 + q, 43 + r, 43 + s, 43 + t, 43 + u, 43 + v, 43 + w, 43 + x, 43 + y, 43 + z, 43 + aa, 43 + ab, 43 + ac, 43 + ad, 43 + ae, 43 + af, 43 + ag, 43 + ah, 43 + ai, 43 + aj, 43 + ak, 43 + al, 43 + am, 43 + an, 43 + ao, 43 + ap, 43 + aq, 43 + ar, 43 + as, 43 + at, 43 + au, 43 + av, 43 + aw, 43 + ax, 43 + ay, 43 + az, 43 + ba, 43 + bb, 43 + bc, 43 + bd, 43 + be, 43 + bf, 43 + bg, 43 + bh, 43 + bi, 43 + bj, 43 + bk, 43 + bl, 43 + bm, 43 + bn, 43 + bo, 43 + bp, 43 + bq, 43 + br, 43 + bs, 43 + bt, 43 + bu, 43 + bv, 43 + bw, 43 + bx, 43 + by, 43 + bz, 43 + ca, 43 + cb, 43 + cc, 43 + cd, 43 + ce, 43 + cf, 43 + cg, 43 + ch, 43 + ci, 43 + cj, 43 + ck, 43 + cl, 43 + cm, 43 + cn, 43 + co, 43 + cp, 43 + cq, 43 + cr, 43 + cs, 43 + ct, 43 + cu, 43 + cv, 43 + cw, 43 + cx, 43 + cy, 43 + cz, 43 + da, 43 + db, 43 + dc, 43 + dd, 43 + de, 43 + df, 43 + dg, 43 + dh, 43 + di, 43 + dj, 43 + dk, 43 + dl, 43 + dm, 43 + dn, 43 + do, 43 + dp, 43 + dq, 43 + dr, 43 + ds, 43 + dt, 43 + du, 43 + dv, 43 + dw, 43 + dx, 43 + dy, 43 + dz, 43 + ea, 43 + eb, 43 + ec, 43 + ed, 43 + ee, 43 + ef, 43 + eg, 43 + eh, 43 + ei, 43 + ej, 43 + ek, 43 + el, 43 + em, 43 + en, 43 + eo, 43 + ep, 43 + eq, 43 + er, 43 + es, 43 + et, 43 + eu, 43 + ev, 43 + ew, 43 + ex, 43 + ey, 43 + ez, 43 + fa, 43 + fb, 43 + fc, 43 + fd, 43 + fe, 43 + ff, 43 + fg, 43 + fh, 43 + fi, 43 + fj, 43 + fk, 43 + fl, 43 + fm, 43 + fn, 43 + fo, 43 + fp, 43 + fq, 43 + fr, 43 + fs, 43 + ft, 43 + fu, 43 + fv, 43 + fw, 43 + fx, 43 + fy, 43 + fz, 43 + ga, 43 + gb, 43 + gc, 43 + gd, 43 + ge, 43 + gf, 4
3 + gg, 43 + gh, 43 + gi, 43 + gj, 43 + gk, 43 + gl, 43 + gm, 43 + gn, 43 + go, 43 + gp, 43 + gq, 43 + gr, 43 + gs, 43 + gt, 43 + gu, 43 + gv, 43 + gw, 43 + gx, 43 + gy, 43 + gz, 43 + ha, 43 + hb, 43 + hc, 43 + hd, 43 + he, 43 + hf, 43 + hg, 43 + hh, 43 + hi, 43 + hj, 43 + hk, 43 + hl, 43 + hm, 43 + hn, 43 + ho, 43 + hp, 43 + hq, 43 + hr, 43 + hs, 43 + ht, 43 + hu, 43 + hv, 43 + hw, 43 + hx, 43 + hy, 43 + hz, 43 + ia, 43 + ib, 43 + ic, 43 + id, 43 + ie, 43 + if, 43 + ig, 43 + ih, 43 + ii, 43 + ij, 43 + ik, 43 + il, 43 + im, 43 + in, 43 + io, 43 + ip, 43 + iq, 43 + ir, 43 + is, 43 + it, 43 + iu, 43 + iv, 43 + iw, 43 + ix, 43 + iy, 43 + iz, 43 + ja, 43 + jb, 43 + jc, 43 + jd, 43 + je, 43 + jf, 43 + jg, 43 + jh, 43 + ji, 43 + jj, 43 + jk, 43 + jl, 43 + jm, 43 + jn, 43 + jo, 43 + jp, 43 + jq, 43 + jr, 43 + js, 43 + jt, 43 + ju, 43 + jv, 43 + jw, 43 + jx, 43 + jy, 43 + jz, 43 + ka, 43 + kb, 43 + kc, 43 + kd, 43 + ke, 43 + kf, 43 + kg, 43 + kh, 43 + ki, 43 + kj, 43 + kk, 43 + kl, 43 + km, 43 + kn, 43 + ko, 43 + kp, 43 + kq, 43 + kr, 43 + ks, 43 + kt, 43 + ku, 43 + kv, 43 + kw, 43 + kx, 43 + ky, 43 + kz, 43 + la, 43 + lb, 43 + lc, 43 + ld, 43 + le, 43 + lf, 43 + lg, 43 + lh, 43 + li, 43 + lj, 43 + lk, 43 + ll, 43 + lm, 43 + ln, 43 + lo, 43 + lp, 43 + lq, 43 + lr, 43 + ls, 43 + lt, 43 + lu, 43 + lv, 43 + lw, 43 + lx, 43 + ly, 43 + lz, 43 + ma, 43 + mb, 43 + mc, 43 + md, 43 + me, 43 + mf, 43 + mg, 43 + mh, 43 + mi, 43 + mj, 43 + mk, 43 + ml, 43 + mm, 43 + mn, 43 + mo, 43 + mp, 43 + mq , 43 + mr, 43 + ms, 43 + mt, 43 + mu, 43 + mv, 43 + mw, 43 + mx, 43 + my, 43 + mz, 43 + na, 43 + nb, 43 + nc, 43 + nd, 43 + ne, 43 + nf, 43 + ng, 43 + nh, 43 + ni, 43 + nj, 43 + nk, 43 + nl, 43 + nm, 43 + nn, 43 + no, 43 + np , 43 + nq, 43 + nr, 43 + ns, 43 + nt, 43 + nu, 43 + nv, 43 + nw, 43 + nx, 43 + ny, 43 + nz, 43 + oa, 43 + ob, 43 + oc, 43 + od, 43 + oe, 43 + of, 43 + og, 43 + oh, 43 + oi, 43 + oj, 43 + ok, 43 + ol, 43 + om, 43 + on, 43 + oo , 43 + op, 43 + oq, 43 + or, 43 + os, 43 + ot, 43 + ou, 43 + ov, 43 + ow, 43 + ox, 43 + oy, 43 + oz, 43 + pa, 43 + pb, 43 + pc, 43 + pd, 43 + pe, 43 + pf, 43 + pg, 43 + ph, 43 + pi, 43 + pj, 43 + pk, 43 + pl, 43 + pm, 43 + pn , 43 + po, 43 + pp, 43 + pq, 43 + pr, 43 + ps, 43 + pt, 43 + pu, 43 + pv, 43 + pw, 43 + px, 43 + py, 43 + pz, 43 + qa, 43 + qb, 43 + qc, 43 + qd, 43 + qe, 43 + qf, 43 + qg, 43 + qh, 43 + qi, 43 + qj, 43 + qk, 43 + ql, 43 + qm , 43 + qn, 43 + qo, 43 + qp, 43 + qq, 43 + qr, 43 + qs, 43 + qt, 43 + qu, 43 + qv, 43 + qw, 43 + qx, 43 + qy, 43 + qz, 43 + ra, 43 + rb, 43 + rc, 43 + rd, 43 + re, 43 + rf, 43 + rg, 43 + rh, 43 + ri, 43 + rj, 43 + rk, 43 + rl , 43 + rm, 43 + rn, 43 + ro, 43 + rp, 43 + rq, 43 + rr, 43 + rs, 43 + rt, 43 + ru, 43 + rv, 43 + rw, 43 + rx, 43 + ry, 43 + rz, 43 + sa, 43 + sb, 43 + sc, 43 + sd, 43 + se, 43 + sf, 43 + sg, 43 + sh, 43 + si, 43 + sj, 43 + sk , 43 + sl, 43 + sm, 43 + sn, 43 + so, 43 + sp, 43 + sq, 43 + sr, 44 + a, 44 + b, 44 + c, 44 + d, 44 + e, 44 + f, 44 + g, 44 + h, 44 + i, 44 + j, 44 + k, 44 + l, 44 + m, 44 + n, 44 + o, 44 + p, 44 + q, 44 + r, 44 + s, 44 + t, 44 + u, 44 + v, 44 + w, 44 + x , 44 + y, 44 + z, 44 + aa, 44 + ab, 44 + ac, 44 + ad, 44 + ae, 44 + af, 44 + ag, 44 + ah, 44 + ai, 44 + aj, 44 + ak, 44 + al, 44 + am, 44 + an, 44 + ao, 44 + ap, 44 + aq, 44 + ar, 44 + as, 44 + at, 44 + au, 44 + av, 44 + aw , 44 + ax, 44 + ay, 44 + az, 44 + ba, 44 + bb, 44 + bc, 44 + bd, 44 + be, 44 + bf, 44 + bg, 44 + bh, 44 + bi, 44 + bj, 44 + bk, 44 + bl, 44 + bm, 44 + bn, 44 + bo, 44 + bp, 44 + bq, 44 + br, 44 + bs, 44 + bt, 44 + bu, 44 + bv , 44 + bw, 44 + bx, 44 + by, 44 + bz, 44 + ca, 44 + cb, 44 + cc, 44 + cd, 44 + ce, 44 + cf, 44 + cg, 44 + ch, 44 + ci, 44 + cj, 44 + ck, 44 + cl, 44 + cm, 44 + cn, 44 + co, 44 + cp, 44 + cq, 44 + cr, 44 + cs, 44 + ct, 44 + cu , 44 + cv, 44 + cw, 44 + cx, 44 + cy, 44 + cz, 44 + da, 44 + db, 44 + dc, 44 + dd, 44 + de, 44 + df, 44 + dg, 44 + dh, 44 + di, 44 + dj, 44 + dk, 44 + dl, 44 + dm, 44 + dn, 44 + do, 44 + dp, 44 + dq, 44 + dr, 44 + ds, 44 + dt , 44 + du, 44 + dv, 44 + dw, 44 + dx, 44 + dy, 44 + dz, 44 + ea, 44 + eb, 44 + ec, 44 + ed, 44 + ee, 44 + ef, 44 + eg, 44 + eh, 44 + ei, 44 + ej, 44 + ek, 44 + el, 44 + em, 44 + en, 44 + eo, 44 + ep, 44 + eq, 44 + er, 44 + es , 44 + et, 44 + eu, 44 + ev, 44 + ew, 44 + ex, 44 + ey, 44 + ez, 44 + fa, 44 + fb, 44 + fc, 44 + fd, 44 + fe, 44 + ff, 44 + fg, 44 + fh, 44 + fi, 44 + fj, 44 + fk, 44 + fl, 44 + fm, 44 + fn, 44 + fo, 44 + fp, 44 + fq, 44 + fr , 44 + fs, 44 + ft, 44 + fu, 44 + fv, 44 + fw, 44 + fx, 44 + fy, 44 + fz, 44 + ga, 44 + gb, 44 + gc, 44 + gd, 44 + ge, 44 + gf, 44 + gg, 44 + gh, 44 + gi, 44 + gj, 44 + gk, 44 + gl, 44 + gm, 44 + gn, 44 + go, 44 + gp, 44 + gq, 44 + gr, 44 + gs, 44 + gt, 44 + gu, 44 + gv, 44 + gw, 44 + gx, 44 + gy, 44 + gz, 44 + ha, 44 + hb, 44 + hc, 44 + hd, 44 + he, 44 + hf, 44 + hg, 44 + hh, 44 + hi, 44 + hj, 44 + hk, 44 + hl, 44 + hm, 44 + hn, 44 + ho, 44 + hp, 44 + hq, 44 + hr, 44 + hs, 44 + ht, 44 + hu, 44 + hv, 44 + hw, 44 + hx, 44 + hy, 44 + hz, 44 + ia, 44 + ib, 44 + ic, 44 + id, 44 + ie, 44 + if, 44 + ig, 44 + ih, 44 + ii, 44 + ij, 44 + ik, 44 + il, 44 + im, 44 + in, 44 + io, 44 + ip, 44 + iq, 44 + ir, 44 + is, 44 + it, 44 + iu, 44 + iv, 44 + iw, 44 + ix, 44 + iy, 44 + iz, 44 + ja, 44 + jb, 44 + jc, 44 + jd, 44 + je, 44 + jf, 44 + jg, 44 + jh, 44 + ji, 44 + jj, 44 + jk, 44 + jl, 44 + jm, 44 + jn, 44 + jo, 44 + jp, 44 + jq, 44 + jr, 44 + js, 44 + jt, 44 + ju, 44 + jv, 44 + jw, 44 + jx, 44 + jy, 44 + jz, 44 + ka, 44 + kb, 44 + kc, 44 + kd, 44 + ke, 44 + kf, 44 + kg, 44 + kh, 44 + ki, 44 + kj, 44 + kk, 44 + kl, 44 + km, 44 + kn, 44 + ko, 44 + kp, 44 + kq, 44 + kr, 44 + ks, 44 + kt, 44 + ku, 44 + kv, 44 + kw, 44 + kx, 44 + ky, 44 + kz, 44 + la, 44 + lb, 44 + lc, 44 + ld, 44 + le, 44 + lf, 44 + lg, 44 + lh, 44 + li, 44 + lj, 44 + lk, 44 + ll, 44 + lm, 44 + ln, 44 + lo, 44 + lp, 44 + lq, 44 + lr, 44 + ls, 44 + lt, 44 + lu, 44 + lv, 44 + lw, 44 + lx, 44 + ly, 44 + lz, 44 + ma, 44 + mb, 44 + mc, 44 + md, 44 + me, 44 + mf, 44 + mg, 44 + mh, 44 + mi, 4 4 + mj, 44 + mk, 44 + ml, 44 + mm, 44 + mn, 44 + mo, 44 + mp, 44 + mq, 44 + mr, 44 + ms, 44 + mt, 44 + mu, 44 + mv, 44 + mw, 44 + mx, 44 + my, 44 + mz, 44 + na, 44 + nb, 44 + nc, 44 + nd, 44 + ne, 44 + nf, 44 + ng, 44 + nh, 44 + ni, 44 + nj, 44 + nk, 44 + nl, 44 + nm, 44 + nn, 44 + no, 44 + np, 44 + nq, 44 + nr, 44 + ns, 44 + nt, 44 + nu, 44 + nv, 44 + nw, 44 + nx, 44 + ny, 44 + nz, 44 + oa, 44 + ob, 44 + oc, 44 + od, 44 + oe, 44 + of, 44 + og, 44 + oh, 44 + oi, 44 + oj, 44 + ok, 44 + ol, 44 + om, 44 + on, 44 + oo, 44 + op, 44 + oq, 44 + or, 44 + os, 44 + ot, 44 + ou, 44 + ov, 44 + ow, 44 + ox, 44 + oy, 44 + oz, 44 + pa, 44 + pb, 44 + pc, 44 + pd, 44 + pe, 44 + pf, 44 + pg, 44 + ph, 44 + pi, 44 + pj, 44 + pk, 44 + pl, 44 + pm, 44 + pn, 44 + po, 44 + pp, 44 + pq, 44 + pr, 44 + ps, 44 + pt, 44 + pu, 44 + pv, 44 + pw, 44 + px, 44 + py, 44 + pz, 44 + qa, 44 + qb, 44 + qc, 44 + qd, 44 + qe, 44 + qf, 44 + qg, 44 + qh, 44 + qi, 44 + qj, 44 + qk, 44 + ql, 44 + qm, 44 + qn, 44 + qo, 44 + qp, 44 + qq, 44 + qr, 44 + qs, 44 + qt, 44 + qu, 44 + qv, 44 + qw, 44 + qx, 44 + qy, 44 + qz, 44 + ra, 44 + rb, 44 + rc, 44 + rd, 44 + re, 44 + rf, 44 + rg, 44 + rh, 44 + ri, 44 + rj, 44 + rk, 44 + rl, 44 + rm, 44 + rn, 44 + ro, 44 + rp, 44 + rq, 44 + rr, 44 + rs, 44 + rt, 44 + ru, 44 + rv, 44 + rw, 44 + rx, 44 + ry, 44 + rz, 44 + sa, 44 + sb, 44 + sc, 44 + sd, 44 + se, 44 + sf, 44 + sg, 44 + sh, 44 + si, 44 + sj, 44 + sk, 44 + sl, 44 + sm, 44 + sn, 44 + so, 44 + sp, 44 + sq, 44 + sr, 45 + a, 45 + b, 4 5 + c, 45 + d, 45 + e, 45 + f, 45 + g, 45 + h, 45 + i, 45 + j, 45 + k, 45 + l, 45 + m, 45 + n, 45 + o, 45 + p, 45 + q, 45 + r, 45 + s, 45 + t, 45 + u, 45 + v, 45 + w, 45 + x, 45 + y, 45 + z, 45 + aa, 45 + ab, 45 + ac, 45 + ad, 45 + ae, 45 + af, 45 + ag, 45 + ah, 45 + ai, 45 + aj, 45 + ak, 45 + al, 45 + am, 45 + an, 45 + ao, 45 + ap, 45 + aq, 45 + ar, 45 + as, 45 + at, 45 + au, 45 + av, 45 + aw, 45 + ax, 45 + ay, 45 + az, 45 + ba, 45 + bb, 45 + bc, 45 + bd, 45 + be, 45 + bf, 45 + bg, 45 + bh, 45 + bi, 45 + bj, 45 + bk, 45 + bl, 45 + bm, 45 + bn, 45 + bo, 45 + bp, 45 + bq, 45 + br, 45 + bs, 45 + bt, 45 + bu, 45 + bv, 45 + bw, 45 + bx, 45 + by, 45 + bz, 45 + ca, 45 + cb, 45 + cc, 45 + cd, 45 + ce, 45 + cf, 45 + cg, 45 + ch, 45 + ci, 45 + cj, 45 + ck, 45 + cl, 45 + cm, 45 + cn, 45 + co, 45 + cp, 45 + cq, 45 + cr, 45 + cs, 45 + ct, 45 + cu, 45 + cv, 45 + cw, 45 + cx, 45 + cy, 45 + cz, 45 + da, 45 + db, 45 + dc, 45 + dd, 45 + de, 45 + df, 45 + dg, 45 + dh, 45 + di, 45 + dj, 45 + dk, 45 + dl, 45 + dm, 45 + dn, 45 + do, 45 + dp, 45 + dq, 45 + dr, 45 + ds, 45 + dt, 45 + du, 45 + dv, 45 + dw, 45 + dx, 45 + dy, 45 + dz, 45 + ea, 45 + eb, 45 + ec, 45 + ed, 45 + ee, 45 + ef, 45 + eg, 45 + eh, 45 + ei, 45 + ej, 45 + ek, 45 + el, 45 + em, 45 + en, 45 + eo, 45 + ep, 45 + eq, 45 + er, 45 + es, 45 + et, 45 + eu, 45 + ev, 45 + ew, 45 + ex, 45 + ey, 45 + ez, 45 + fa, 45 + fb, 45 + fc, 45 + fd, 45 + fe, 45 + ff, 45 + fg, 45 + fh, 45 + fi, 45 + fj, 45 + fk, 45 + fl, 45 + fm, 45 + fn, 45 + fo, 45 + fp, 45 + fq , 45 + fr, 45 + fs, 45 + ft, 45 + fu, 45 + fv, 45 + fw, 45 + fx, 45 + fy, 45 + fz, 45 + ga, 45 + gb, 45 + gc, 45 + gd, 45 + ge, 45 + gf, 45 + gg, 45 + gh, 45 + gi, 45 + gj, 45 + gk, 45 + gl, 45 + gm, 45 + gn, 45 + go, 45 + gp , 45 + gq, 45 + gr, 45 + gs, 45 + gt, 45 + gu, 45 + gv, 45 + gw, 45 + gx, 45 + gy, 45 + gz, 45 + ha, 45 + hb, 45 + hc, 45 + hd, 45 + he, 45 + hf, 45 + hg, 45 + hh, 45 + hi, 45 + hj, 45 + hk, 45 + hl, 45 + hm, 45 + hn, 45 + ho , 45 + hp, 45 + hq, 45 + hr, 45 + hs, 45 + ht, 45 + hu, 45 + hv, 45 + hw, 45 + hx, 45 + hy, 45 + hz, 45 + ia, 45 + ib, 45 + ic, 45 + id, 45 + ie, 45 + if, 45 + ig, 45 + ih, 45 + ii, 45 + ij, 45 + ik, 45 + il, 45 + im, 45 + in , 45 + io, 45 + ip, 45 + iq, 45 + ir, 45 + is, 45 + it, 45 + iu, 45 + iv, 45 + iw, 45 + ix, 45 + iy, 45 + iz, 45 + ja, 45 + jb, 45 + jc, 45 + jd, 45 + je, 45 + jf, 45 + jg, 45 + jh, 45 + ji, 45 + jj, 45 + jk, 45 + jl, 45 + jm , 45 + jn, 45 + jo, 45 + jp, 45 + jq, 45 + jr, 45 + js, 45 + jt, 45 + ju, 45 + jv, 45 + jw, 45 + jx, 45 + jy, 45 + jz, 45 + ka, 45 + kb, 45 + kc, 45 + kd, 45 + ke, 45 + kf, 45 + kg, 45 + kh, 45 + ki, 45 + kj, 45 + kk, 45 + kl , 45 + km, 45 + kn, 45 + ko, 45 + kp, 45 + kq, 45 + kr, 45 + ks, 45 + kt, 45 + ku, 45 + kv, 45 + kw, 45 + kx, 45 + ky, 45 + kz, 45 + la, 45 + lb, 45 + lc, 45 + ld, 45 + le, 45 + lf, 45 + lg, 45 + lh, 45 + li, 45 + lj, 45 + lk , 45 + ll, 45 + lm, 45 + ln, 45 + lo, 45 + lp, 45 + lq, 45 + lr, 45 + ls, 45 + lt, 45 + lu, 45 + lv, 45 + lw, 45 + lx, 45 + ly, 45 + lz, 45 + ma, 45 + mb, 45 + mc, 45 + md, 45 + me, 45 + mf, 45 + mg, 45 + mh, 45 + mi, 45 + mj, 45 + mk, 45 + ml, 45 + mm, 45 + mn, 45 + mo, 45 + mp, 45 + mq, 45 + mr, 45 + ms, 45 + mt, 45 + mu, 45 + mv, 45 + mw, 45 + mx, 45 + my, 45 + mz, 45 + na, 45 + nb, 45 + nc, 45 + nd, 45 + ne, 45 + nf, 45 + ng, 45 + nh, 45 + ni, 45 + nj, 45 + nk, 45 + nl, 45 + nm, 45 + nn, 45 + no, 45 + np, 45 + nq, 45 + nr, 45 + ns, 45 + nt, 45 + nu, 45 + nv, 45 + nw, 45 + nx, 45 + ny, 45 + nz, 45 + oa, 45 + ob, 45 + oc, 45 + od, 45 + oe, 45 + of, 45 + og, 45 + oh, 45 + oi, 45 + oj, 45 + ok, 45 + ol, 45 + om, 45 + on, 45 + oo, 45 + op, 45 + oq, 45 + or, 45 + os, 45 + ot, 45 + ou, 45 + ov, 45 + ow, 45 + ox, 45 + oy, 45 + oz, 45 + pa, 45 + pb, 45 + pc, 45 + pd, 45 + pe, 45 + pf, 45 + pg, 45 + ph, 45 + pi, 45 + pj, 45 + pk, 45 + pl, 45 + pm, 45 + pn, 45 + po, 45 + pp, 45 + pq, 45 + pr, 45 + ps, 45 + pt, 45 + pu, 45 + pv, 45 + pw, 45 + px, 45 + py, 45 + pz, 45 + qa, 45 + qb, 45 + qc, 45 + qd, 45 + qe, 45 + qf, 45 + qg, 45 + qh, 45 + qi, 45 + qj, 45 + qk, 45 + ql, 45 + qm, 45 + qn, 45 + qo, 45 + qp, 45 + qq, 45 + qr, 45 + qs, 45 + qt, 45 + qu, 45 + qv, 45 + qw, 45 + qx, 45 + qy, 45 + qz, 45 + ra, 45 + rb, 45 + rc, 45 + rd, 45 + re, 45 + rf, 45 + rg, 45 + rh, 45 + ri, 45 + rj, 45 + rk, 45 + rl, 45 + rm, 45 + rn, 45 + ro, 45 + rp, 45 + rq, 45 + rr, 45 + rs, 45 + rt, 45 + ru, 45 + rv, 45 + rw, 45 + rx, 45 + ry, 45 + rz, 45 + sa, 45 + sb, 45 + sc, 45 + sd, 45 + se, 45 + sf, 45 + sg, 45 + sh, 45 + si, 45 + sj, 45 + sk, 45 + sl, 4 5 + sm, 45 + sn, 45 + so, 45 + sp, 45 + sq, 45 + sr, 46 + a, 46 + b, 46 + c, 46 + d, 46 + e, 46 + f, 46 + g, 46 + h, 46 + i, 46 + j, 46 + k, 46 + l, 46 + m, 46 + n, 46 + o, 46 + p, 46 + q, 46 + r, 46 + s, 46 + t, 46 + u, 46 + v, 46 + w, 46 + x, 46 + y, 46 + z, 46 + aa, 46 + ab, 46 + ac, 46 + ad, 46 + ae, 46 + af, 46 + ag, 46 + ah, 46 + ai, 46 + aj, 46 + ak, 46 + al, 46 + am, 46 + an, 46 + ao, 46 + ap, 46 + aq, 46 + ar, 46 + as, 46 + at, 46 + au, 46 + av, 46 + aw, 46 + ax, 46 + ay, 46 + az, 46 + ba, 46 + bb, 46 + bc, 46 + bd, 46 + be, 46 + bf, 46 + bg, 46 + bh, 46 + bi, 46 + bj, 46 + bk, 46 + bl, 46 + bm, 46 + bn, 46 + bo, 46 + bp, 46 + bq, 46 + br, 46 + bs, 46 + bt, 46 + bu, 46 + bv, 46 + bw, 46 + bx, 46 + by, 46 + bz, 46 + ca, 46 + cb, 46 + cc, 46 + cd, 46 + ce, 46 + cf, 46 + cg, 46 + ch, 46 + ci, 46 + cj, 46 + ck, 46 + cl, 46 + cm, 46 + cn, 46 + co, 46 + cp, 46 + cq, 46 + cr, 46 + cs, 46 + ct, 46 + cu, 46 + cv, 46 + cw, 46 + cx, 46 + cy, 46 + cz, 46 + da, 46 + db, 46 + dc, 46 + dd, 46 + de, 46 + df, 46 + dg, 46 + dh, 46 + di, 46 + dj, 46 + dk, 46 + dl, 46 + dm, 46 + dn, 46 + do, 46 + dp, 46 + dq, 46 + dr, 46 + ds, 46 + dt, 46 + du, 46 + dv, 46 + dw, 46 + dx, 46 + dy, 46 + dz, 46 + ea, 46 + eb, 46 + ec, 46 + ed, 46 + ee, 46 + ef, 46 + eg, 46 + eh, 46 + ei, 46 + ej, 46 + ek, 46 + el, 46 + em, 46 + en, 46 + eo, 46 + ep, 46 + eq, 46 + er, 46 + es, 46 + et, 46 + eu, 46 + ev, 46 + ew, 46 + ex, 46 + ey, 46 + ez, 46 + fa, 46 + fb, 46 + fc, 46 + fd, 46 + fe, 46 + ff, 46 + fg, 46 + fh, 46 + fi, 4 6 + fj, 46 + fk, 46 + fl, 46 + fm, 46 + fn, 46 + fo, 46 + fp, 46 + fq, 46 + fr, 46 + fs, 46 + ft, 46 + fu, 46 + fv, 46 + fw, 46 + fx, 46 + fy, 46 + fz, 46 + ga, 46 + gb, 46 + gc, 46 + gd, 46 + ge, 46 + gf, 46 + gg, 46 + gh, 46 + gi, 46 + gj, 46 + gk, 46 + gl, 46 + gm, 46 + gn, 46 + go, 46 + gp, 46 + gq, 46 + gr, 46 + gs, 46 + gt, 46 + gu, 46 + gv, 46 + gw, 46 + gx, 46 + gy, 46 + gz, 46 + ha, 46 + hb, 46 + hc, 46 + hd, 46 + he, 46 + hf, 46 + hg, 46 + hh, 46 + hi, 46 + hj, 46 + hk, 46 + hl, 46 + hm, 46 + hn, 46 + ho, 46 + hp, 46 + hq, 46 + hr, 46 + hs, 46 + ht, 46 + hu, 46 + hv, 46 + hw, 46 + hx, 46 + hy, 46 + hz, 46 + ia, 46 + ib, 46 + ic, 46 + id, 46 + ie, 46 + if, 46 + ig, 46 + ih, 46 + ii, 46 + ij, 46 + ik, 46 + il, 46 + im, 46 + in, 46 + io, 46 + ip, 46 + iq, 46 + ir, 46 + is, 46 + it, 46 + iu, 46 + iv, 46 + iw, 46 + ix, 46 + iy, 46 + iz, 46 + ja, 46 + jb, 46 + jc, 46 + jd, 46 + je, 46 + jf, 46 + jg, 46 + jh, 46 + ji, 46 + jj, 46 + jk, 46 + jl, 46 + jm, 46 + jn, 46 + jo, 46 + jp, 46 + jq, 46 + jr, 46 + js, 46 + jt, 46 + ju, 46 + jv, 46 + jw, 46 + jx, 46 + jy, 46 + jz, 46 + ka, 46 + kb, 46 + kc, 46 + kd, 46 + ke, 46 + kf, 46 + kg, 46 + kh, 46 + ki, 46 + kj, 46 + kk, 46 + kl, 46 + km, 46 + kn, 46 + ko, 46 + kp, 46 + kq, 46 + kr, 46 + ks, 46 + kt, 46 + ku, 46 + kv, 46 + kw, 46 + kx, 46 + ky, 46 + kz, 46 + la, 46 + lb, 46 + lc, 46 + ld, 46 + le, 46 + lf, 46 + lg, 46 + lh, 46 + li, 46 + lj, 46 + lk, 46 + ll, 46 + lm, 46 + ln, 46 + lo, 46 + lp, 46 + lq, 46 + lr, 46 + ls, 46 + lt , 46 + lu, 46 + lv, 46 + lw, 46 + lx, 46 + ly, 46 + lz, 46 + ma, 46 + mb, 46 + mc, 46 + md, 46 + me, 46 + mf, 46 + mg, 46 + mh, 46 + mi, 46 + mj, 46 + mk, 46 + ml, 46 + mm, 46 + mn, 46 + mo, 46 + mp, 46 + mq, 46 + mr, 46 + ms , 46 + mt, 46 + mu, 46 + mv, 46 + mw, 46 + mx, 46 + my, 46 + mz, 46 + na, 46 + nb, 46 + nc, 46 + nd, 46 + ne, 46 + nf, 46 + ng, 46 + nh,
46 + ni, 46 + nj, 46 + nk, 46 + nl, 46 + nm, 46 + nn, 46 + no, 46 + np, 46 + nq, 46 + nr, 46 + ns, 46 + nt, 46 + nu, 46 + nv, 46 + nw, 46 + nx, 46 + ny, 46 + nz, 46 + oa, 46 + ob, 46 + oc, 46 + od, 46 + oe, 46 + of, 46 + og, 46 + oh, 46 + oi, 46 + oj, 46 + ok, 46 + ol, 46 + om, 46 + on, 46 + oo, 46 + op, 46 + oq, 46 + or, 46 + os, 46 + ot, 46 + ou, 46 + ov, 46 + ow, 46 + ox, 46 + oy, 46 + oz, 46 + pa, 46 + pb, 46 + pc, 46 + pd, 46 + pe, 46 + pf, 46 + pg, 46 + ph, 46 + pi, 46 + pj, 46 + pk, 46 + pl, 46 + pm, 46 + pn, 46 + po, 46 + pp, 46 + pq, 46 + pr, 46 + ps, 46 + pt, 46 + pu, 46 + pv, 46 + pw, 46 + px, 46 + py, 46 + pz, 46 + qa, 46 + qb, 46 + qc, 46 + qd, 46 + qe, 46 + qf, 46 + qg, 46 + qh, 46 + qi, 46 + qj, 46 + qk, 46 + ql, 46 + qm, 46 + qn, 46 + qo, 46 + qp, 46 + qq, 46 + qr, 46 + qs, 46 + qt, 46 + qu, 46 + qv, 46 + qw, 46 + qx, 46 + qy, 46 + qz, 46 + ra, 46 + rb, 46 + rc, 46 + rd, 46 + re, 46 + rf, 46 + rg, 46 + rh, 46 + ri, 46 + rj, 46 + rk, 46 + rl, 46 + rm, 46 + rn, 46 + ro, 46 + rp, 46 + rq, 46 + rr, 46 + rs, 46 + rt, 46 + ru, 46 + rv, 46 + rw, 46 + rx, 46 + ry, 46 + rz, 46 + sa, 46 + sb, 46 + sc, 46 + sd, 46 + se, 46 + sf, 46 + sg, 46 + sh, 46 + si, 46 + sj, 46 + sk, 46 + sl, 46 + sm, 46 + sn, 46 + so, 46 + sp, 46 + sq, 46 + sr, 47 + a, 47 + b, 47 + c, 47 + d, 47 + e, 47 + f, 47 + g, 47 + h, 47 + i, 47 + j, 47 + k, 47 + l, 47 + m, 47 + n, 47 + o, 47 + p, 47 + q, 47 + r, 47 + s, 47 + t, 47 + u, 47 + v, 47 + w, 47 + x, 47 + y, 47 + z, 47 + aa, 47 + ab, 47 + ac, 47 + ad, 47 + ae, 47 + af, 47 + ag, 47 + ah, 47 + ai, 47 + aj, 47 + ak, 47 + al, 47 + am, 47 + an, 47 + ao, 47 + ap, 47 + aq, 47 + ar, 47 + as, 47 + at, 47 + au, 47 + av, 47 + aw, 47 + ax, 47 + ay, 47 + az, 47 + ba, 47 + bb, 47 + bc, 47 + bd, 47 + be, 47 + bf, 47 + bg, 47 + bh, 47 + bi, 47 + bj, 47 + bk, 47 + bl, 47 + bm, 47 + bn, 47 + bo, 47 + bp, 47 + bq, 47 + br, 47 + bs, 47 + bt, 47 + bu, 47 + bv, 47 + bw, 47 + bx, 47 + by, 47 + bz, 47 + ca, 47 + cb, 47 + cc, 47 + cd, 47 + ce, 47 + cf, 47 + cg, 47 + ch, 47 + ci, 47 + cj, 47 + ck, 47 + cl, 47 + cm, 47 + cn, 47 + co, 47 + cp, 47 + cq, 47 + cr, 47 + cs, 47 + ct, 47 + cu, 47 + cv, 47 + cw, 47 + cx, 47 + cy, 47 + cz, 47 + da, 47 + db, 47 + dc, 47 + dd, 47 + de, 47 + df, 47 + dg, 47 + dh, 47 + di, 47 + dj, 47 + dk, 47 + dl, 47 + dm, 47 + dn, 47 + do, 47 + dp, 47 + dq, 47 + dr, 47 + ds, 47 + dt, 47 + du, 47 + dv, 47 + dw, 47 + dx, 47 + dy, 47 + dz, 47 + ea, 47 + eb, 47 + ec, 47 + ed, 47 + ee, 47 + ef, 47 + eg, 47 + eh, 47 + ei, 47 + ej, 47 + ek, 47 + el, 47 + em, 47 + en, 47 + eo, 47 + ep, 47 + eq, 47 + er, 47 + es, 47 + et, 47 + eu, 47 + ev, 47 + ew, 47 + ex, 47 + ey, 47 + ez, 47 + fa, 47 + fb, 47 + fc, 47 + fd, 47 + fe, 47 + ff, 47 + fg, 47 + fh, 47 + fi, 47 + fj, 47 + fk, 47 + fl, 47 + fm, 47 + fn, 47 + fo, 47 + fp, 47 + fq, 47 + fr, 47 + fs, 47 + ft, 47 + fu, 47 + fv, 47 + fw, 47 + fx, 47 + fy, 47 + fz, 47 + ga, 47 + gb, 47 + gc, 47 + gd, 47 + ge, 47 + gf, 47 + gg, 47 + gh, 47 + gi, 47 + gj, 47 + gk, 47 + gl, 47 + gm, 47 + gn, 47 + go, 47 + g p, 47 + gq, 47 + gr, 47 + gs, 47 + gt, 47 + gu, 47 + gv, 47 + gw, 47 + gx, 47 + gy, 47 + gz, 47 + ha, 47 + hb, 47 + hc, 47 + hd, 47 + he, 47 + hf, 47 + hg, 47 + hh, 47 + hi, 47 + hj, 47 + hk, 47 + hl, 47 + hm, 47 + hn, 47 + ho, 47 + hp, 47 + hq, 47 + hr, 47 + hs, 47 + ht, 47 + hu, 47 + hv, 47 + hw, 47 + hx, 47 + hy, 47 + hz, 47 + ia, 47 + ib, 47 + ic, 47 + id, 47 + ie, 47 + if, 47 + ig, 47 + ih, 47 + ii, 47 + ij, 47 + ik, 47 + il, 47 + im, 47 + in, 47 + io, 47 + ip, 47 + iq, 47 + ir, 47 + is, 47 + it, 47 + iu, 47 + iv, 47 + iw, 47 + ix, 47 + iy, 47 + iz, 47 + ja, 47 + jb, 47 + jc, 47 + jd, 47 + je, 47 + jf, 47 + jg, 47 + jh, 47 + ji, 47 + jj, 47 + jk, 47 + jl, 47 + jm, 47 + jn, 47 + jo, 47 + jp, 47 + jq, 47 + jr, 47 + js, 47 + jt, 47 + ju, 47 + jv, 47 + jw, 47 + jx, 47 + jy, 47 + jz, 47 + ka, 47 + kb, 47 + kc, 47 + kd, 47 + ke, 47 + kf, 47 + kg, 47 + kh, 47 + ki, 47 + kj, 47 + kk, 47 + kl, 47 + km, 47 + kn, 47 + ko, 47 + kp, 47 + kq, 47 + kr, 47 + ks, 47 + kt, 47 + ku, 47 + kv, 47 + kw, 47 + kx, 47 + ky, 47 + kz, 47 + la, 47 + lb, 47 + lc, 47 + ld, 47 + le, 47 + lf, 47 + lg, 47 + lh, 47 + li, 47 + lj, 47 + lk, 47 + ll, 47 + lm, 47 + ln, 47 + lo, 47 + lp, 47 + lq, 47 + lr, 47 + ls, 47 + lt, 47 + lu, 47 + lv, 47 + lw, 47 + lx, 47 + ly, 47 + lz, 47 + ma, 47 + mb, 47 + mc, 47 + md, 47 + me, 47 + mf, 47 + mg, 47 + mh, 47 + mi, 47 + mj, 47 + mk, 47 + ml, 47 + mm, 47 + mn, 47 + mo, 47 + mp, 47 + mq, 47 + mr, 47 + ms, 47 + mt, 47 + mu, 47 + mv, 47 + mw, 47 + mx, 47 + my, 47 + mz, 47 + na, 47 + nb, 47 + nc, 47 + nd, 47 + ne, 47 + nf, 47 + ng, 47 + nh, 47 + ni, 47 + nj, 47 + nk, 47 + nl, 47 + nm , 47 + nn, 47 + no, 47 + np, 47 + nq, 47 + nr, 47 + ns, 47 + nt, 47 + nu, 47 + nv, 47 + nw, 47 + nx, 47 + ny, 47 + nz, 47 + oa, 47 + ob, 47 + oc, 47 + od, 47 + oe, 47 + of, 47 + og, 47 + oh, 47 + oi, 47 + oj, 47 + ok, 47 + ol , 47 + om, 47 + on, 47 + oo, 47 + op, 47 + oq, 47 + or, 47 + os, 47 + ot, 47 + ou, 47 + ov, 47 + ow, 47 + ox, 47 + oy, 47 + oz, 47 + pa, 47 + pb, 47 + pc, 47 + pd, 47 + pe, 47 + pf, 47 + pg, 47 + ph, 47 + pi, 47 + pj, 47 + pk , 47 + pl, 47 + pm, 47 + pn, 47 + po, 47 + pp, 47 + pq, 47 + pr, 47 + ps, 47 + pt, 47 + pu, 47 + pv, 47 + pw, 47 + px, 47 + py, 47 + pz, 47 + qa, 47 + qb, 47 + qc, 47 + qd, 47 + qe, 47 + qf, 47 + qg, 47 + qh, 47 + qi, 47 + qj , 47 + qk, 47 + ql, 47 + qm, 47 + qn, 47 + qo, 47 + qp, 47 + qq, 47 + qr, 47 + qs, 47 + qt, 47 + qu, 47 + qv, 47 + qw, 47 + qx, 47 + qy, 47 + qz, 47 + ra, 47 + rb, 47 + rc, 47 + rd, 47 + re, 47 + rf, 47 + rg, 47 + rh, 47 + ri , 47 + rj, 47 + rk, 47 + rl, 47 + rm, 47 + rn, 47 + ro, 47 + rp, 47 + rq, 47 + rr, 47 + rs, 47 + rt, 47 + ru, 47 + rv, 47 + rw, 47 + rx, 47 + ry, 47 + rz, 47 + sa, 47 + sb, 47 + sc, 47 + sd, 47 + se, 47 + sf, 47 + sg, 47 + sh , 47 + si, 47 + sj, 47 + sk, 47 + sl, 47 + sm, 47 + sn, 47 + so, 47 + sp, 47 + sq, 47 + sr, 48 + a, 48 + b, 48 + c, 48 + d, 48 + e, 48 + f, 48 + g, 48 + h, 48 + i, 48 + j, 48 + k, 48 + l, 48 + m, 48 + n, 48 + o , 48 + p, 48 + q, 48 + r, 48 + s, 48 + t, 48 + u, 48 + v, 48 + w , 48 + x, 48 + y, 48 + z, 48 + aa, 48 + ab, 48 + ac, 48 + ad, 48 + ae, 48 + af, 48 + ag, 48 + ah, 48 + ai, 48 + aj, 48 + ak, 48 + al, 48 + am, 48 + an, 48 + ao, 48 + ap, 48 + aq, 48 + ar, 48 + as, 48 + at, 48 + au, 48 + av , 48 + aw, 48 + ax, 48 + ay, 48 + az, 48 + ba, 48 + bb, 48 + bc, 48 + bd, 48 + be, 48 + bf, 48 + bg, 48 + bh, 48 + bi, 48 + bj, 48 + bk, 48 + bl, 48 + bm, 48 + bn, 48 + bo, 48 + bp, 48 + bq, 48 + br, 48 + bs, 48 + bt, 48 + bu , 48 + bv, 48 + bw, 48 + bx, 48 + by, 48 + bz, 48 + ca, 48 + cb, 48 + cc, 48 + cd, 48 + ce, 48 + cf, 48 + cg, 48 + ch, 48 + ci, 48 + cj, 48 + ck, 48 + cl, 48 + cm, 48 + cn, 48 + co, 48 + cp, 48 + cq, 48 + cr, 48 + cs, 48 + ct , 48 + cu, 48 + cv, 48 + cw, 48 + cx, 48 + cy, 48 + cz, 48 + da, 48 + db, 48 + dc, 48 + dd, 48 + de, 48 + df, 48 + dg, 48 + dh, 48 + di, 48 + dj, 48 + dk, 48 + dl, 48 + dm, 48 + dn, 48 + do, 48 + dp, 48 + dq, 48 + dr, 48 + ds , 48 + dt, 48 + du, 48 + dv, 48 + dw, 48 + dx, 48 + dy, 48 + dz, 48 + ea, 48 + eb, 48 + ec, 48 + ed, 48 + ee, 48 + ef, 48 + eg, 48 + eh, 48 + ei, 48 + ej, 48 + ek, 48 + el, 48 + em, 48 + en, 48 + eo, 48 + ep, 48 + eq, 48 + er , 48 + es, 48 + et, 48 + eu, 48 + ev, 48 + ew, 48 + ex, 48 + ey, 48 + ez, 48 + fa, 48 + fb, 48 + fc, 48 + fd, 48 + fe, 48 + ff, 48 + fg, 48 + fh, 48 + fi, 48 + fj, 48 + fk, 48 + fl, 48 + fm, 48 + fn, 48 + fo, 48 + fp, 48 + fq , 48 + fr, 48 + fs, 48 + ft, 48 + fu, 48 + fv, 48 + fw, 48 + fx, 48 + fy, 48 + fz, 48 + ga, 48 + gb, 48 + gc, 48 + gd, 48 + ge, 48 + gf, 48 + gg, 48 + gh, 48 + gi, 48 + gj, 48 + gk, 48 + gl, 48 + gm, 48 + gn, 48 + go, 48 + gp, 48 + gq, 48 + gr, 48 + gs, 48 + gt, 48 + gu, 48 + gv, 48 + gw, 48 + gx, 48 + gy, 48 + gz, 48 + ha, 48 + hb, 48 + hc, 48 + hd, 48 + he, 48 + hf, 48 + hg, 48 + hh, 48 + hi, 48 + hj, 48 + hk, 48 + hl, 48 + hm, 48 + hn, 48 + ho, 48 + hp, 48 + hq, 48 + hr, 48 + hs, 48 + ht, 48 + hu, 48 + hv, 48 + hw, 48 + hx, 48 + hy, 48 + hz, 48 + ia, 48 + ib, 48 + ic, 48 + id, 48 + ie, 48 + if, 48 + ig, 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48 + mo, 48 + mp, 48 + mq, 48 + mr, 48 + m s, 48 + mt, 48 + mu, 48 + mv, 48 + mw, 48 + mx, 48 + my, 48 + mz, 48 + na, 48 + nb, 48 + nc, 48 + nd, 48 + ne, 48 + nf, 48 + ng, 48 + nh, 48 + ni, 48 + nj, 48 + nk, 48 + nl, 48 + nm, 48 + nn, 48 + no, 48 + np, 48 + nq, 48 + nr, 48 + ns, 48 + nt, 48 + nu, 48 + nv, 48 + nw, 48 + nx, 48 + ny, 48 + nz, 48 + oa, 48 + ob, 48 + oc, 48 + od, 48 + oe, 48 + of, 48 + og, 48 + oh, 48 + oi, 48 + oj, 48 + ok, 48 + ol, 48 + om, 48 + on, 48 + oo, 48 + op, 48 + oq, 48 + or, 48 + os, 48 + ot, 48 + ou, 48 + ov, 48 + ow, 48 + ox, 48 + oy, 48 + oz, 48 + pa, 48 + pb, 48 + pc, 48 + pd, 48 + pe, 48 + pf, 48 + pg, 48 + ph, 48 + pi, 48 + pj, 48 + pk, 48 + pl, 48 + pm, 48 + pn, 48 + po, 48 + pp, 48 + pq, 48 + pr, 48 + ps, 48 + pt, 48 + pu, 48 + pv, 48 + pw, 48 + px, 48 + py, 48 + pz, 48 + qa, 48 + qb, 48 + qc, 48 + qd, 48 + qe, 48 + qf, 48 + qg, 48 + qh, 48 + qi, 48 + qj, 48 + qk, 48 + ql, 48 + qm, 48 + qn, 48 + qo, 48 + qp, 48 + qq, 48 + qr, 48 + qs, 48 + qt, 48 + qu, 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so, 49 + sp, 49 + sq, 49 + sr,
50 + a, 50 + b, 50 + c, 50 + d, 50 + e, 50 + f, 50 + g, 50 + h, 50 + i, 50 + j, 50 + k, 50 + l, 50 + m, 50 + n, 50 + o, 50 + p, 50 + q, 50 + r, 50 + s, 50 + t, 50 + u, 50 + v, 50 + w, 50 + x, 50 + y, 50 + z, 50 + aa, 50 + ab, 50 + ac, 50 + ad, 50 + ae, 50 + af, 50 + ag, 50 + ah, 50 + ai, 50 + aj, 50 + ak, 50 + al, 50 + am, 50 + an, 50 + ao, 50 + ap, 50 + aq, 50 + ar, 50 + as, 50 + at, 50 + au, 50 + av, 50 + aw, 50 + ax, 50 + ay, 50 + az, 50 + ba, 50 + bb, 50 + bc, 50 + bd, 50 + be, 50 + bf, 50 + bg, 50 + bh, 50 + bi, 50 + bj, 50 + bk, 50 + bl, 50 + bm, 50 + bn, 50 + bo, 50 + bp, 50 + bq, 50 + br, 50 + bs, 50 + bt, 50 + bu, 50 + bv, 50 + bw, 50 + bx, 50 + by, 50 + bz, 50 + ca, 50 + cb, 50 + cc, 50 + cd, 50 + ce, 50 + cf, 50 + cg, 50 + ch, 50 + ci, 50 + cj, 50 + ck, 50 + cl, 50 + cm, 50 + cn, 50 + co, 50 + cp, 50 + cq, 50 + cr, 50 + cs, 50 + ct, 50 + cu, 50 + cv, 50 + cw, 50 + cx, 50 + cy, 50 + cz, 50 + da, 50 + db, 50 + dc, 50 + dd, 50 + de, 50 + df, 50 + dg, 50 + dh, 50 + di, 50 + dj, 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aw, 51 + ax, 51 + ay, 51 + az, 51 + ba, 51 + bb, 51 + bc , 51 + bd, 51 + be, 51 + bf, 51 + bg, 51 + bh, 51 + bi, 51 + bj, 51 + bk, 51 + bl, 51 + bm, 51 + bn, 51 + bo, 51 + bp, 51 + bq, 51 + br, 51 + bs, 51 + bt, 51 + bu, 51 + bv, 51 + bw, 51 + bx, 51 + by, 51 + bz, 51 + ca, 51 + cb , 51 + cc, 51 + cd, 51 + ce, 51 + cf, 51 + cg, 51 + ch, 51 + ci, 51 + cj, 51 + ck, 51 + cl, 51 + cm, 51 + cn, 51 + co, 51 + cp, 51 + cq, 51 + cr, 51 + cs, 51 + ct, 51 + cu, 51 + cv, 51 + cw, 51 + cx, 51 + cy, 51 + cz, 51 + da , 51 + db, 51 + dc, 51 + dd, 51 + de, 51 + df, 51 + dg, 51 + dh, 51 + di, 51 + dj, 51 + dk, 51 + dl, 51 + dm, 51 + dn, 51 + do, 51 + dp, 51 + dq, 51 + dr, 51 + ds, 51 + dt, 51 + du, 51 + dv, 51 + dw, 51 + dx, 51 + dy, 51 + dz , 51 + ea, 51 + eb, 51 + ec, 51 + ed, 51 + ee, 51 + ef, 51 + eg, 51 + eh, 51 + ei, 51 + ej, 51 + ek, 51 + el, 51 + em, 51 + en, 51 + eo, 51 + ep, 51 + eq, 51 + er, 51 + es, 51 + et, 51 + eu, 51 + ev, 51 + ew, 51 + ex, 51 + ey , 51 + ez, 51 + fa, 51 + fb, 51 + fc, 51 + fd, 51 + fe, 51 + ff, 51 + fg, 51 + fh, 51 + fi, 51 + fj, 51 + fk, 51 + fl, 51 + fm, 51 + fn, 51 + fo, 51 + fp, 51 + fq, 51 + fr, 51 + fs, 51 + ft , 51 + fu, 51 + fv, 51 + fw, 51 + fx, 51 + fy, 51 + fz, 51 + ga, 51 + gb, 51 + gc, 51 + gd, 51 + ge, 51 + gf, 51 + gg, 51 + gh, 51 + gi, 51 + gj, 51 + gk, 51 + gl, 51 + gm, 51 + gn, 51 + go, 51 + gp, 51 + gq, 51 + gr, 51 + gs , 51 + gt, 51 + gu, 51 + gv, 51 + gw, 51 + gx, 51 + gy, 51 + gz, 51 + ha, 51 + hb, 51 + hc, 51 + hd, 51 + he, 51 + hf, 51 + hg, 51 + hh, 51 + hi, 51 + hj, 51 + hk, 51 + hl, 51 + hm, 51 + hn, 51 + ho, 51 + hp, 51 + hq, 51 + hr , 51 + hs, 51 + ht, 51 + hu, 51 + hv, 51 + hw, 51 + hx, 51 + hy, 51 + hz, 51 + ia, 51 + ib, 51 + ic, 51 + id, 51 + ie, 51 + if, 51 + ig, 51 + ih, 51 + ii, 51 + ij, 51 + ik, 51 + il, 51 + im, 51 + in, 51 + io, 51 + ip, 51 + iq , 51 + ir, 51 + is, 51 + it, 51 + iu, 51 + iv, 51 + iw, 51 + ix, 51 + iy, 51 + iz, 51 + ja, 51 + jb, 51 + jc, 51 + jd, 51 + je, 51 + jf, 51 + jg, 51 + jh, 51 + ji, 51 + jj, 51 + jk, 51 + jl, 51 + jm, 51 + jn, 51 + jo, 51 + jp , 51 + jq, 51 + jr, 51 + js, 51 + jt, 51 + ju, 51 + jv, 51 + jw, 51 + jx, 51 + jy, 51 + jz, 51 + ka, 51 + kb, 51 + kc, 51 + kd, 51 + ke, 51 + kf, 51 + kg, 51 + kh, 51 + ki, 51 + kj, 51 + kk, 51 + kl, 51 + km, 51 + kn, 51 + ko , 51 + kp, 51 + kq, 51 + kr, 51 + ks, 51 + kt, 51 + ku, 51 + kv, 51 + kw, 51 + kx, 51 + ky, 51 + kz, 51 + la, 51 + lb, 51 + lc, 51 + ld, 51 + le, 51 + lf, 51 + lg, 51 + lh, 51 + li, 51 + lj, 51 + lk, 51 + ll, 51 + lm, 51 + ln , 51 + lo, 51 + lp, 51 + lq, 51 + lr, 51 + ls, 51 + lt, 51 + lu, 51 + lv, 51 + lw, 51 + lx, 51 + ly, 51 + lz, 51 + ma, 51 + mb, 51 + mc, 51 + md, 51 + me, 51 + mf, 51 + mg, 51 + mh, 51 + mi, 51 + mj, 51 + mk, 51 + ml, 51 + mm, 51 + mn, 51 + mo, 51 + mp, 51 + mq, 51 + mr, 51 + ms, 51 + mt, 51 + mu, 51 + mv, 51 + mw, 51 + mx, 51 + my, 51 + mz, 51 + na, 51 + nb, 51 + nc, 51 + nd, 51 + ne, 51 + nf, 51 + ng, 51 + nh, 51 + ni, 51 + nj, 51 + nk, 51 + nl, 51 + nm, 51 + nn, 51 + no, 51 + np, 51 + nq, 51 + nr, 51 + ns, 51 + nt, 51 + nu, 51 + nv, 51 + nw, 51 + nx, 51 + ny, 51 + nz, 51 + oa, 51 + ob, 51 + oc, 51 + od, 51 + oe, 51 + of, 51 + og, 51 + oh, 51 + oi, 51 + oj, 51 + ok, 51 + ol, 51 + om, 51 + on, 51 + oo, 51 + op, 51 + oq, 51 + or, 51 + os, 51 + ot, 51 + ou, 51 + ov, 51 + ow, 51 + ox, 51 + oy, 51 + oz, 51 + pa, 51 + pb, 51 + pc, 51 + pd, 51 + pe, 51 + pf, 51 + pg, 51 + ph, 51 + pi, 51 + pj, 51 + pk, 51 + pl, 51 + pm, 51 + pn, 51 + po, 51 + pp, 51 + pq, 51 + pr, 51 + ps, 51 + pt, 51 + pu, 51 + pv, 51 + pw, 51 + px, 51 + py, 51 + pz, 51 + qa, 51 + qb, 51 + qc, 51 + qd, 51 + qe, 51 + qf, 51 + qg, 51 + qh, 51 + qi, 51 + qj, 51 + qk, 51 + ql, 51 + qm, 51 + qn, 51 + qo, 51 + qp, 51 + qq, 51 + qr, 51 + qs, 51 + qt, 51 + qu, 51 + qv, 51 + qw, 51 + qx, 51 + qy, 51 + qz, 51 + ra, 51 + rb, 51 + rc, 51 + rd, 51 + re, 51 + rf, 51 + rg, 51 + rh, 51 + ri, 51 + rj, 51 + rk, 51 + rl, 51 + rm, 51 + rn, 51 + ro, 51 + rp, 51 + rq, 51 + rr, 51 + rs, 51 + rt, 51 + ru, 51 + rv, 51 + rw, 51 + rx, 51 + ry, 51 + rz, 51 + sa, 51 + sb, 51 + s c, 51 + sd, 51 + se, 51 + sf, 51 + sg, 51 + sh, 51 + si, 51 + sj, 51 + sk, 51 + sl, 51 + sm, 51 + sn, 51 + so, 51 + sp, 51 + sq, 51 + sr, 52 + a, 52 + b, 52 + c, 52 + d, 52 + e, 52 + f, 52 + g, 52 + h, 52 + i, 52 + j, 52 + k, 52 + l, 52 + m, 52 + n, 52 + o, 52 + p, 52 + q, 52 + r, 52 + s, 52 + t, 52 + u, 52 + v, 52 + w, 52 + x, 52 + y, 52 + z, 52 + aa, 52 + ab, 52 + ac, 52 + ad, 52 + ae, 52 + af, 52 + ag, 52 + ah, 52 + ai, 52 + aj, 52 + ak, 52 + al, 52 + am, 52 + an, 52 + ao, 52 + ap, 52 + aq, 52 + ar, 52 + as, 52 + at, 52 + au, 52 + av, 52 + aw, 52 + ax, 52 + ay, 52 + az, 52 + ba, 52 + bb, 52 + bc, 52 + bd, 52 + be, 52 + bf, 52 + bg, 52 + bh, 52 + bi, 52 + bj, 52 + bk, 52 + bl, 52 + bm, 52 + bn, 52 + bo, 52 + bp, 52 + bq, 52 + br, 52 + bs, 52 + bt, 52 + bu, 52 + bv, 52 + bw, 52 + bx, 52 + by, 52 + bz, 52 + ca, 52 + cb, 52 + cc, 52 + cd, 52 + ce, 52 + cf, 52 + cg, 52 + ch, 52 + ci, 52 + cj, 52 + ck, 52 + cl, 52 + cm, 52 + cn, 52 + co, 52 + cp, 52 + cq, 52 + cr, 52 + cs, 52 + ct, 52 + cu, 52 + cv, 52 + cw, 52 + cx, 52 + cy, 52 + cz, 52 + da, 52 + db, 52 + dc, 52 + dd, 52 + de, 52 + df, 52 + dg, 52 + dh, 52 + di, 52 + dj, 52 + dk, 52 + dl, 52 + dm, 52 + dn, 52 + do, 52 + dp, 52 + dq, 52 + dr, 52 + ds, 52 + dt, 52 + du, 52 + dv, 52 + dw, 52 + dx, 52 + dy, 52 + dz, 52 + ea, 52 + eb, 52 + ec, 52 + ed, 52 + ee, 52 + ef, 52 + eg, 52 + eh, 52 + ei, 52 + ej, 52 + ek, 52 + el, 52 + em, 52 + en, 52 + eo, 52 + ep, 52 + eq, 52 + er, 52 + es, 52 + et, 52 + eu, 52 + ev, 52 + ew, 52 + ex, 52 + ey, 52 + e z, 52 + fa, 52 + fb, 52 + fc, 52 + fd, 52 + fe, 52 + ff, 52 + fg, 52 + fh, 52 + fi, 52 + fj, 52 + fk, 52 + fl, 52 + fm, 52 + fn, 52 + fo, 52 + fp, 52 + fq, 52 + fr, 52 + fs, 52 + ft, 52 + fu, 52 + fv, 52 + fw, 52 + fx, 52 + fy, 52 + fz, 52 + ga, 52 + gb, 52 + gc, 52 + gd, 52 + ge, 52 + gf, 52 + gg, 52 + gh, 52 + gi, 52 + gj, 52 + gk, 52 + gl, 52 + gm, 52 + gn, 52 + go, 52 + gp, 52 + gq, 52 + gr, 52 + gs, 52 + gt, 52 + gu, 52 + gv, 52 + gw, 52 + gx, 52 + gy, 52 + gz, 52 + ha, 52 + hb, 52 + hc, 52 + hd, 52 + he, 52 + hf, 52 + hg, 52 + hh, 52 + hi, 52 + hj, 52 + hk, 52 + hl, 52 + hm, 52 + hn, 52 + ho, 52 + hp, 52 + hq, 52 + hr, 52 + hs, 52 + ht, 52 + hu, 52 + hv, 52 + hw, 52 + hx, 52 + hy, 52 + hz, 52 + ia, 52 + ib, 52 + ic, 52 + id, 52 + ie, 52 + if, 52 + ig, 52 + ih, 52 + ii, 52 + ij, 52 + ik, 52 + il, 52 + im, 52 + in, 52 + io, 52 + ip, 52 + iq, 52 + ir, 52 + is, 52 + it, 52 + iu, 52 + iv, 52 + iw, 52 + ix, 52 + iy, 52 + iz, 52 + ja, 52 + jb, 52 + jc, 52 + jd, 52 + je, 52 + jf, 52 + jg, 52 + jh, 52 + ji, 52 + jj, 52 + jk, 52 + jl, 52 + jm, 52 + jn, 52 + jo, 52 + jp, 52 + jq, 52 + jr, 52 + js, 52 + jt, 52 + ju, 52 + jv, 52 + jw, 52 + jx, 52 + jy, 52 + jz, 52 + ka, 52 + kb, 52 + kc, 52 + kd, 52 + ke, 52 + kf, 52 + kg, 52 + kh, 52 + ki, 52 + kj, 52 + kk, 52 + kl, 52 + km, 52 + kn, 52 + ko, 52 + kp, 52 + kq, 52 + kr, 52 + ks, 52 + kt, 52 + ku, 52 + kv, 52 + kw, 52 + kx, 52 + ky, 52 + kz, 52 + la, 52 + lb, 52 + lc, 52 + ld, 52 + le, 52 + lf, 52 + lg, 52 + lh, 52 + li, 52 + lj, 52 + lk, 52 + ll, 52 + lm, 52 + ln, 52 + lo, 52 + lp, 52 + lq, 52 + lr, 52 + ls, 52 + lt, 52 + lu, 52 + lv, 52 + lw , 52 + lx, 52 + ly, 52 + lz, 52 + ma, 52 + mb, 52 + mc, 52 + md, 52 + me, 52 + mf, 52 + mg, 52 + mh, 52 + mi, 52 + mj, 52 + mk, 52 + ml, 52 + mm, 52 + mn, 52 + mo, 52 + mp, 52 + mq, 52 + mr, 52 + ms, 52 + mt, 52 + mu, 52 + mv , 52 + mw, 52 + mx, 52 + my, 52 + mz, 52 + na, 52 + nb, 52 + nc, 52 + nd, 52 + ne, 52 + nf, 52 + ng, 52 + nh, 52 + ni, 52 + nj, 52 + nk, 52 + nl, 52 + nm, 52 + nn, 52 + no, 52 + np, 52 + nq, 52 + nr, 52 + ns, 52 + nt, 52 + nu , 52 + nv, 52 + nw, 52 + nx, 52 + ny, 52 + nz, 52 + oa, 52 + ob, 52 + oc, 52 + od, 52 + oe, 52 + of, 52 + og, 52 + oh, 52 + oi, 52 + oj, 52 + ok, 52 + ol, 52 + om, 52 + on, 52 + oo, 52 + op, 52 + oq, 52 + or, 52 + os, 52 + ot , 52 + ou, 52 + ov, 52 + ow, 52 + ox, 52 + oy, 52 + oz, 52 + pa, 52 + pb, 52 + pc, 52 + pd, 52 + pe, 52 + pf, 52 + pg, 52 + ph, 52 + pi, 52 + pj, 52 + pk, 52 + pl, 52 + pm, 52 + pn, 52 + po, 52 + pp, 52 + pq, 52 + pr, 52 + ps , 52 + pt, 52 + pu, 52 + pv, 52 + pw, 52 + px, 52 + py, 52 + pz, 52 + qa, 52 + qb, 52 + qc, 52 + qd, 52 + qe, 52 + qf, 52 + qg, 52 + qh, 52 + qi, 52 + qj, 52 + qk, 52 + ql, 52 + qm, 52 + qn, 52 + qo, 52 + qp, 52 + qq, 52 + qr , 52 + qs, 52 + qt, 52 + qu, 52 + qv, 52 + qw, 52 + qx, 52 + qy, 52 + qz, 52 + ra, 52 + rb, 52 + rc, 52 + rd, 52 + re, 52 + rf, 52 + rg, 52 + rh, 52 + ri, 52 + rj, 52 + rk, 52 + rl, 52 + rm, 52 + rn, 52 + ro, 52 + rp, 52 + rq , 52 + rr, 52 + rs, 52 + rt, 52 + ru, 52 + rv, 52 + rw, 52 + rx, 52 + ry, 52 + rz, 52 + sa, 52 + sb, 52 + sc, 52 + sd, 52 + se, 52 + sf, 52 + sg, 52 + sh, 52 + si, 52 + sj, 52 + sk, 52 + sl, 52 + sm, 52 + sn, 52 + so, 52 + sp, 52 + sq, 52 + sr, 53 + a, 53 + b, 53 + c, 53 + d, 53 + e, 53 + f, 53 + g, 53 + h, 53 + i, 53 + j, 53 + k, 53 + l, 53 + m, 53 + n, 53 + o, 53 + p, 53 + q, 53 + r, 53 + s, 53 + t, 53 + u, 53 + v, 53 + w, 53 + x, 53 + y, 53 + z, 53 + aa, 53 + ab, 53 + ac, 53 + ad, 53 + ae, 53 + af, 53 + ag, 53 + ah, 53 + ai, 53 + aj, 53 + ak, 53 + al, 53 + am, 53 + an, 53 + ao, 53 + ap, 53 + aq, 53 + ar, 53 + as, 53 + at, 53 + au, 53 + av, 53 + aw, 53 + ax, 53 + ay, 53 + az, 53 + ba, 53 + bb, 53 + bc, 53 + bd, 53 + be, 53 + bf, 53 + bg, 53 + bh, 53 + bi, 53 + bj, 53 + bk, 53 + bl, 53 + bm, 53 + bn, 53 + bo, 53 + bp, 53 + bq, 53 + br, 53 + bs, 53 + bt, 53 + bu, 53 + bv, 53 + bw, 53 + bx, 53 + by, 53 + bz, 53 + ca, 53 + cb, 53 + cc, 53 + cd, 53 + ce, 53 + cf, 53 + cg, 53 + ch, 53 + ci, 53 + cj, 53 + ck, 53 + cl, 53 + cm, 53 + cn, 53 + co, 53 + cp, 53 + cq, 53 + cr, 53 + cs, 53 + ct, 53 + cu, 53 + cv, 53 + cw, 53 + cx, 53 + cy, 53 + cz, 53 + da, 53 + db, 53 + dc, 53 + dd, 53 + de, 53 + df, 53 + dg, 53 + dh, 53 + di, 53 + dj, 53 + dk, 53 + dl, 53 + dm, 53 + dn, 53 + do, 53 + dp, 53 + dq, 53 + dr, 53 + ds, 53 + dt, 53 + du, 53 + dv, 53 + dw, 53 + dx, 53 + dy, 53 + dz, 53 + ea, 53 + eb, 53 + ec, 53 + ed, 53 + ee, 53 + ef, 53 + eg, 53 + eh, 53 + ei, 53 + ej, 53 + ek, 53 + el, 53 + em, 53 + en, 53 + eo, 53 + ep, 53 + eq, 53 + er, 53 + es, 53 + et, 53 + eu, 53 + ev, 53 + ew, 53 + ex, 53 + ey, 53 + ez, 53 + fa, 53 + fb, 53 + fc, 53 + fd, 53 + fe, 53 + ff, 53 + fg, 53 + fh, 53 + fi, 53 + fj, 53 + fk, 53 + fl, 53 + fm, 53 + fn, 53 + fo, 53 + fp, 53 + fq, 53 + fr, 53 + fs, 53 + ft, 53 + fu, 53 + fv, 53 + fw, 53 + fx, 53 + fy, 53 + fz, 53 + ga, 53 + gb, 53 + gc, 53 + gd, 53 + ge, 53 + gf, 5
3 + gg, 53 + gh, 53 + gi, 53 + gj, 53 + gk, 53 + gl, 53 + gm, 53 + gn, 53 + go, 53 + gp, 53 + gq, 53 + gr, 53 + gs, 53 + gt, 53 + gu, 53 + gv, 53 + gw, 53 + gx, 53 + gy, 53 + gz, 53 + ha, 53 + hb, 53 + hc, 53 + hd, 53 + he, 53 + hf, 53 + hg, 53 + hh, 53 + hi, 53 + hj, 53 + hk, 53 + hl, 53 + hm, 53 + hn, 53 + ho, 53 + hp, 53 + hq, 53 + hr, 53 + hs, 53 + ht, 53 + hu, 53 + hv, 53 + hw, 53 + hx, 53 + hy, 53 + hz, 53 + ia, 53 + ib, 53 + ic, 53 + id, 53 + ie, 53 + if, 53 + ig, 53 + ih, 53 + ii, 53 + ij, 53 + ik, 53 + il, 53 + im, 53 + in, 53 + io, 53 + ip, 53 + iq, 53 + ir, 53 + is, 53 + it, 53 + iu, 53 + iv, 53 + iw, 53 + ix, 53 + iy, 53 + iz, 53 + ja, 53 + jb, 53 + jc, 53 + jd, 53 + je, 53 + jf, 53 + jg, 53 + jh, 53 + ji, 53 + jj, 53 + jk, 53 + jl, 53 + jm, 53 + jn, 53 + jo, 53 + jp, 53 + jq, 53 + jr, 53 + js, 53 + jt, 53 + ju, 53 + jv, 53 + jw, 53 + jx, 53 + jy, 53 + jz, 53 + ka, 53 + kb, 53 + kc, 53 + kd, 53 + ke, 53 + kf, 53 + kg, 53 + kh, 53 + ki, 53 + kj, 53 + kk, 53 + kl, 53 + km, 53 + kn, 53 + ko, 53 + kp, 53 + kq, 53 + kr, 53 + ks, 53 + kt, 53 + ku, 53 + kv, 53 + kw, 53 + kx, 53 + ky, 53 + kz, 53 + la, 53 + lb, 53 + lc, 53 + ld, 53 + le, 53 + lf, 53 + lg, 53 + lh, 53 + li, 53 + lj, 53 + lk, 53 + ll, 53 + lm, 53 + ln, 53 + lo, 53 + lp, 53 + lq, 53 + lr, 53 + ls, 53 + lt, 53 + lu, 53 + lv, 53 + lw, 53 + lx, 53 + ly, 53 + lz, 53 + ma, 53 + mb, 53 + mc, 53 + md, 53 + me, 53 + mf, 53 + mg, 53 + mh, 53 + mi, 53 + mj, 53 + mk, 53 + ml, 53 + mm, 53 + mn, 53 + mo, 53 + mp, 53 + mq , 53 + mr, 53 + ms, 53 + mt, 53 + mu, 53 + mv, 53 + mw, 53 + mx, 53 + my, 53 + mz, 53 + na, 53 + nb, 53 + nc, 53 + nd, 53 + ne, 53 + nf, 53 + ng, 53 + nh, 53 + ni, 53 + nj, 53 + nk, 53 + nl, 53 + nm, 53 + nn, 53 + no, 53 + np , 53 + nq, 53 + nr, 53 + ns, 53 + nt, 53 + nu, 53 + nv, 53 + nw, 53 + nx, 53 + ny, 53 + nz, 53 + oa, 53 + ob, 53 + oc, 53 + od, 53 + oe, 53 + of, 53 + og, 53 + oh, 53 + oi, 53 + oj, 53 + ok, 53 + ol, 53 + om, 53 + on, 53 + oo , 53 + op, 53 + oq, 53 + or, 53 + os, 53 + ot, 53 + ou, 53 + ov, 53 + ow, 53 + ox, 53 + oy, 53 + oz, 53 + pa, 53 + pb, 53 + pc, 53 + pd, 53 + pe, 53 + pf, 53 + pg, 53 + ph, 53 + pi, 53 + pj, 53 + pk, 53 + pl, 53 + pm, 53 + pn , 53 + po, 53 + pp, 53 + pq, 53 + pr, 53 + ps, 53 + pt, 53 + pu, 53 + pv, 53 + pw, 53 + px, 53 + py, 53 + pz, 53 + qa, 53 + qb, 53 + qc, 53 + qd, 53 + qe, 53 + qf, 53 + qg, 53 + qh, 53 + qi, 53 + qj, 53 + qk, 53 + ql, 53 + qm , 53 + qn, 53 + qo, 53 + qp, 53 + qq, 53 + qr, 53 + qs, 53 + qt, 53 + qu, 53 + qv, 53 + qw, 53 + qx, 53 + qy, 53 + qz, 53 + ra, 53 + rb, 53 + rc, 53 + rd, 53 + re, 53 + rf, 53 + rg, 53 + rh, 53 + ri, 53 + rj, 53 + rk, 53 + rl , 53 + rm, 53 + rn, 53 + ro, 53 + rp, 53 + rq, 53 + rr, 53 + rs, 53 + rt, 53 + ru, 53 + rv, 53 + rw, 53 + rx, 53 + ry, 53 + rz, 53 + sa, 53 + sb, 53 + sc, 53 + sd, 53 + se, 53 + sf, 53 + sg, 53 + sh, 53 + si, 53 + sj, 53 + sk , 53 + sl, 53 + sm, 53 + sn, 53 + so, 53 + sp, 53 + sq, 53 + sr, 54 + a, 54 + b, 54 + c, 54 + d, 54 + e, 54 + f, 54 + g, 54 + h, 54 + i, 54 + j, 54 + k, 54 + l, 54 + m, 54 + n, 54 + o, 54 + p, 54 + q, 54 + r, 54 + s, 54 + t, 54 + u, 54 + v, 54 + w, 54 + x , 54 + y, 54 + z, 54 + aa, 54 + ab, 54 + ac, 54 + ad, 54 + ae, 54 + af, 54 + ag, 54 + ah, 54 + ai, 54 + aj, 54 + ak, 54 + al, 54 + am, 54 + an, 54 + ao, 54 + ap, 54 + aq, 54 + ar, 54 + as, 54 + at, 54 + au, 54 + av, 54 + aw , 54 + ax, 54 + ay, 54 + az, 54 + ba, 54 + bb, 54 + bc, 54 + bd, 54 + be, 54 + bf, 54 + bg, 54 + bh, 54 + bi, 54 + bj, 54 + bk, 54 + bl, 54 + bm, 54 + bn, 54 + bo, 54 + bp, 54 + bq, 54 + br, 54 + bs, 54 + bt, 54 + bu, 54 + bv , 54 + bw, 54 + bx, 54 + by, 54 + bz, 54 + ca, 54 + cb, 54 + cc, 54 + cd, 54 + ce, 54 + cf, 54 + cg, 54 + ch, 54 + ci, 54 + cj, 54 + ck, 54 + cl, 54 + cm, 54 + cn, 54 + co, 54 + cp, 54 + cq, 54 + cr, 54 + cs, 54 + ct, 54 + cu , 54 + cv, 54 + cw, 54 + cx, 54 + cy, 54 + cz, 54 + da, 54 + db, 54 + dc, 54 + dd, 54 + de, 54 + df, 54 + dg, 54 + dh, 54 + di, 54 + dj, 54 + dk, 54 + dl, 54 + dm, 54 + dn, 54 + do, 54 + dp, 54 + dq, 54 + dr, 54 + ds, 54 + dt , 54 + du, 54 + dv, 54 + dw, 54 + dx, 54 + dy, 54 + dz, 54 + ea, 54 + eb, 54 + ec, 54 + ed, 54 + ee, 54 + ef, 54 + eg, 54 + eh, 54 + ei, 54 + ej, 54 + ek, 54 + el, 54 + em, 54 + en, 54 + eo, 54 + ep, 54 + eq, 54 + er, 54 + es , 54 + et, 54 + eu, 54 + ev, 54 + ew, 54 + ex, 54 + ey, 54 + ez, 54 + fa, 54 + fb, 54 + fc, 54 + fd, 54 + fe, 54 + ff, 54 + fg, 54 + fh, 54 + fi, 54 + fj, 54 + fk, 54 + fl, 54 + fm, 54 + fn, 54 + fo, 54 + fp, 54 + fq, 54 + fr , 54 + fs, 54 + ft, 54 + fu, 54 + fv, 54 + fw, 54 + fx, 54 + fy, 54 + fz, 54 + ga, 54 + gb, 54 + gc, 54 + gd, 54 + ge, 54 + gf, 54 + gg, 54 + gh, 54 + gi, 54 + gj, 54 + gk, 54 + gl, 54 + gm, 54 + gn, 54 + go, 54 + gp, 54 + gq, 54 + gr, 54 + gs, 54 + gt, 54 + gu, 54 + gv, 54 + gw, 54 + gx, 54 + gy, 54 + gz, 54 + ha, 54 + hb, 54 + hc, 54 + hd, 54 + he, 54 + hf, 54 + hg, 54 + hh, 54 + hi, 54 + hj, 54 + hk, 54 + hl, 54 + hm, 54 + hn, 54 + ho, 54 + hp, 54 + hq, 54 + hr, 54 + hs, 54 + ht, 54 + hu, 54 + hv, 54 + hw, 54 + hx, 54 + hy, 54 + hz, 54 + ia, 54 + ib, 54 + ic, 54 + id, 54 + ie, 54 + if, 54 + ig, 54 + ih, 54 + ii, 54 + ij, 54 + ik, 54 + il, 54 + im, 54 + in, 54 + io, 54 + ip, 54 + iq, 54 + ir, 54 + is, 54 + it, 54 + iu, 54 + iv, 54 + iw, 54 + ix, 54 + iy, 54 + iz, 54 + ja, 54 + jb, 54 + jc, 54 + jd, 54 + je, 54 + jf, 54 + jg, 54 + jh, 54 + ji, 54 + jj, 54 + jk, 54 + jl, 54 + jm, 54 + jn, 54 + jo, 54 + jp, 54 + jq, 54 + jr, 54 + js, 54 + jt, 54 + ju, 54 + jv, 54 + jw, 54 + jx, 54 + jy, 54 + jz, 54 + ka, 54 + kb, 54 + kc, 54 + kd, 54 + ke, 54 + kf, 54 + kg, 54 + kh, 54 + ki, 54 + kj, 54 + kk, 54 + kl, 54 + km, 54 + kn, 54 + ko, 54 + kp, 54 + kq, 54 + kr, 54 + ks, 54 + kt, 54 + ku, 54 + kv, 54 + kw, 54 + kx, 54 + ky, 54 + kz, 54 + la, 54 + lb, 54 + lc, 54 + ld, 54 + le, 54 + lf, 54 + lg, 54 + lh, 54 + li, 54 + lj, 54 + lk, 54 + ll, 54 + lm, 54 + ln, 54 + lo, 54 + lp, 54 + lq, 54 + lr, 54 + ls, 54 + lt, 54 + lu, 54 + lv, 54 + lw, 54 + lx, 54 + ly, 54 + lz, 54 + ma, 54 + mb, 54 + mc, 54 + md, 54 + me, 54 + mf, 54 + mg, 54 + mh, 54 + mi, 5 4 + mj, 54 + mk, 54 + ml, 54 + mm, 54 + mn, 54 + mo, 54 + mp, 54 + mq, 54 + mr, 54 + ms, 54 + mt, 54 + mu, 54 + mv, 54 + mw, 54 + mx, 54 + my, 54 + mz, 54 + na, 54 + nb, 54 + nc, 54 + nd, 54 + ne, 54 + nf, 54 + ng, 54 + nh, 54 + ni, 54 + nj, 54 + nk, 54 + nl, 54 + nm, 54 + nn, 54 + no, 54 + np, 54 + nq, 54 + nr, 54 + ns, 54 + nt, 54 + nu, 54 + nv, 54 + nw, 54 + nx, 54 + ny, 54 + nz, 54 + oa, 54 + ob, 54 + oc, 54 + od, 54 + oe, 54 + of, 54 + og, 54 + oh, 54 + oi, 54 + oj, 54 + ok, 54 + ol, 54 + om, 54 + on, 54 + oo, 54 + op, 54 + oq, 54 + or, 54 + os, 54 + ot, 54 + ou, 54 + ov, 54 + ow, 54 + ox, 54 + oy, 54 + oz, 54 + pa, 54 + pb, 54 + pc, 54 + pd, 54 + pe, 54 + pf, 54 + pg, 54 + ph, 54 + pi, 54 + pj, 54 + pk, 54 + pl, 54 + pm, 54 + pn, 54 + po, 54 + pp, 54 + pq, 54 + pr, 54 + ps, 54 + pt, 54 + pu, 54 + pv, 54 + pw, 54 + px, 54 + py, 54 + pz, 54 + qa, 54 + qb, 54 + qc, 54 + qd, 54 + qe, 54 + qf, 54 + qg, 54 + qh, 54 + qi, 54 + qj, 54 + qk, 54 + ql, 54 + qm, 54 + qn, 54 + qo, 54 + qp, 54 + qq, 54 + qr, 54 + qs, 54 + qt, 54 + qu, 54 + qv, 54 + qw, 54 + qx, 54 + qy, 54 + qz, 54 + ra, 54 + rb, 54 + rc, 54 + rd, 54 + re, 54 + rf, 54 + rg, 54 + rh, 54 + ri, 54 + rj, 54 + rk, 54 + rl, 54 + rm, 54 + rn, 54 + ro, 54 + rp, 54 + rq, 54 + rr, 54 + rs, 54 + rt, 54 + ru, 54 + rv, 54 + rw, 54 + rx, 54 + ry, 54 + rz, 54 + sa, 54 + sb, 54 + sc, 54 + sd, 54 + se, 54 + sf, 54 + sg, 54 + sh, 54 + si, 54 + sj, 54 + sk, 54 + sl, 54 + sm, 54 + sn, 54 + so, 54 + sp, 54 + sq, 54 + sr, 55 + a, 55 + b, 5 5 + c, 55 + d, 55 + e, 55 + f, 55 + g, 55 + h, 55 + i, 55 + j, 55 + k, 55 + l, 55 + m, 55 + n, 55 + o, 55 + p, 55 + q, 55 + r, 55 + s, 55 + t, 55 + u, 55 + v, 55 + w, 55 + x, 55 + y, 55 + z, 55 + aa, 55 + ab, 55 + ac, 55 + ad, 55 + ae, 55 + af, 55 + ag, 55 + ah, 55 + ai, 55 + aj, 55 + ak, 55 + al, 55 + am, 55 + an, 55 + ao, 55 + ap, 55 + aq, 55 + ar, 55 + as, 55 + at, 55 + au, 55 + av, 55 + aw, 55 + ax, 55 + ay, 55 + az, 55 + ba, 55 + bb, 55 + bc, 55 + bd, 55 + be, 55 + bf, 55 + bg, 55 + bh, 55 + bi, 55 + bj, 55 + bk, 55 + bl, 55 + bm, 55 + bn, 55 + bo, 55 + bp, 55 + bq, 55 + br, 55 + bs, 55 + bt, 55 + bu, 55 + bv, 55 + bw, 55 + bx, 55 + by, 55 + bz, 55 + ca, 55 + cb, 55 + cc, 55 + cd, 55 + ce, 55 + cf, 55 + cg, 55 + ch, 55 + ci, 55 + cj, 55 + ck, 55 + cl, 55 + cm, 55 + cn, 55 + co, 55 + cp, 55 + cq, 55 + cr, 55 + cs, 55 + ct, 55 + cu, 55 + cv, 55 + cw, 55 + cx, 55 + cy, 55 + cz, 55 + da, 55 + db, 55 + dc, 55 + dd, 55 + de, 55 + df, 55 + dg, 55 + dh, 55 + di, 55 + dj, 55 + dk, 55 + dl, 55 + dm, 55 + dn, 55 + do, 55 + dp, 55 + dq, 55 + dr, 55 + ds, 55 + dt, 55 + du, 55 + dv, 55 + dw, 55 + dx, 55 + dy, 55 + dz, 55 + ea, 55 + eb, 55 + ec, 55 + ed, 55 + ee, 55 + ef, 55 + eg, 55 + eh, 55 + ei, 55 + ej, 55 + ek, 55 + el, 55 + em, 55 + en, 55 + eo, 55 + ep, 55 + eq, 55 + er, 55 + es, 55 + et, 55 + eu, 55 + ev, 55 + ew, 55 + ex, 55 + ey, 55 + ez, 55 + fa, 55 + fb, 55 + fc, 55 + fd, 55 + fe, 55 + ff, 55 + fg, 55 + fh, 55 + fi, 55 + fj, 55 + fk, 55 + fl, 55 + fm, 55 + fn, 55 + fo, 55 + fp, 55 + fq , 55 + fr, 55 + fs, 55 + ft, 55 + fu, 55 + fv, 55 + fw, 55 + fx, 55 + fy, 55 + fz, 55 + ga, 55 + gb, 55 + gc, 55 + gd, 55 + ge, 55 + gf, 55 + gg, 55 + gh, 55 + gi, 55 + gj, 55 + gk, 55 + gl, 55 + gm, 55 + gn, 55 + go, 55 + gp , 55 + gq, 55 + gr, 55 + gs, 55 + gt, 55 + gu, 55 + gv, 55 + gw, 55 + gx, 55 + gy, 55 + gz, 55 + ha, 55 + hb, 55 + hc, 55 + hd, 55 + he, 55 + hf, 55 + hg, 55 + hh, 55 + hi, 55 + hj, 55 + hk, 55 + hl, 55 + hm, 55 + hn, 55 + ho , 55 + hp, 55 + hq, 55 + hr, 55 + hs, 55 + ht, 55 + hu, 55 + hv, 55 + hw, 55 + hx, 55 + hy, 55 + hz, 55 + ia, 55 + ib, 55 + ic, 55 + id, 55 + ie, 55 + if, 55 + ig, 55 + ih, 55 + ii, 55 + ij, 55 + ik, 55 + il, 55 + im, 55 + in , 55 + io, 55 + ip, 55 + iq, 55 + ir, 55 + is, 55 + it, 55 + iu, 55 + iv, 55 + iw, 55 + ix, 55 + iy, 55 + iz, 55 + ja, 55 + jb, 55 + jc, 55 + jd, 55 + je, 55 + jf, 55 + jg, 55 + jh, 55 + ji, 55 + jj, 55 + jk, 55 + jl, 55 + jm , 55 + jn, 55 + jo, 55 + jp, 55 + jq, 55 + jr, 55 + js, 55 + jt, 55 + ju, 55 + jv, 55 + jw, 55 + jx, 55 + jy, 55 + jz, 55 + ka, 55 + kb, 55 + kc, 55 + kd, 55 + ke, 55 + kf, 55 + kg, 55 + kh, 55 + ki, 55 + kj, 55 + kk, 55 + kl , 55 + km, 55 + kn, 55 + ko, 55 + kp, 55 + kq, 55 + kr, 55 + ks, 55 + kt, 55 + ku, 55 + kv, 55 + kw, 55 + kx, 55 + ky, 55 + kz, 55 + la, 55 + lb, 55 + lc, 55 + ld, 55 + le, 55 + lf, 55 + lg, 55 + lh, 55 + li, 55 + lj, 55 + lk , 55 + ll, 55 + lm, 55 + ln, 55 + lo, 55 + lp, 55 + lq, 55 + lr, 55 + ls, 55 + lt, 55 + lu, 55 + lv, 55 + lw, 55 + lx, 55 + ly, 55 + lz, 55 + ma, 55 + mb, 55 + mc, 55 + md, 55 + me, 55 + mf, 55 + mg, 55 + mh, 55 + mi, 55 + mj, 55 + mk, 55 + ml, 55 + mm, 55 + mn, 55 + mo, 55 + mp, 55 + mq, 55 + mr, 55 + ms, 55 + mt, 55 + mu, 55 + mv, 55 + mw, 55 + mx, 55 + my, 55 + mz, 55 + na, 55 + nb, 55 + nc, 55 + nd, 55 + ne, 55 + nf, 55 + ng, 55 + nh, 55 + ni, 55 + nj, 55 + nk, 55 + nl, 55 + nm, 55 + nn, 55 + no, 55 + np, 55 + nq, 55 + nr, 55 + ns, 55 + nt, 55 + nu, 55 + nv, 55 + nw, 55 + nx, 55 + ny, 55 + nz, 55 + oa, 55 + ob, 55 + oc, 55 + od, 55 + oe, 55 + of, 55 + og, 55 + oh, 55 + oi, 55 + oj, 55 + ok, 55 + ol, 55 + om, 55 + on, 55 + oo, 55 + op, 55 + oq, 55 + or, 55 + os, 55 + ot, 55 + ou, 55 + ov, 55 + ow, 55 + ox, 55 + oy, 55 + oz, 55 + pa, 55 + pb, 55 + pc, 55 + pd, 55 + pe, 55 + pf, 55 + pg, 55 + ph, 55 + pi, 55 + pj, 55 + pk, 55 + pl, 55 + pm, 55 + pn, 55 + po, 55 + pp, 55 + pq, 55 + pr, 55 + ps, 55 + pt, 55 + pu, 55 + pv, 55 + pw, 55 + px, 55 + py, 55 + pz, 55 + qa, 55 + qb, 55 + qc, 55 + qd, 55 + qe, 55 + qf, 55 + qg, 55 + qh, 55 + qi, 55 + qj, 55 + qk, 55 + ql, 55 + qm, 55 + qn, 55 + qo, 55 + qp, 55 + qq, 55 + qr, 55 + qs, 55 + qt, 55 + qu, 55 + qv, 55 + qw, 55 + qx, 55 + qy, 55 + qz, 55 + ra, 55 + rb, 55 + rc, 55 + rd, 55 + re, 55 + rf, 55 + rg, 55 + rh, 55 + ri, 55 + rj, 55 + rk, 55 + rl, 55 + rm, 55 + rn, 55 + ro, 55 + rp, 55 + rq, 55 + rr, 55 + rs, 55 + rt, 55 + ru, 55 + rv, 55 + rw, 55 + rx, 55 + ry, 55 + rz, 55 + sa, 55 + sb, 55 + sc, 55 + sd, 55 + se, 55 + sf, 55 + sg, 55 + sh, 55 + si, 55 + sj, 55 + sk, 55 + sl, 5 5 + sm, 55 + sn, 55 + so, 55 + sp, 55 + sq, 55 + sr, 56 + a, 56 + b, 56 + c, 56 + d, 56 + e, 56 + f, 56 + g, 56 + h, 56 + i, 56 + j, 56 + k, 56 + l, 56 + m, 56 + n, 56 + o, 56 + p, 56 + q, 56 + r, 56 + s, 56 + t, 56 + u, 56 + v, 56 + w, 56 + x, 56 + y, 56 + z, 56 + aa, 56 + ab, 56 + ac, 56 + ad, 56 + ae, 56 + af, 56 + ag, 56 + ah, 56 + ai, 56 + aj, 56 + ak, 56 + al, 56 + am, 56 + an, 56 + ao, 56 + ap, 56 + aq, 56 + ar, 56 + as, 56 + at, 56 + au, 56 + av, 56 + aw, 56 + ax, 56 + ay, 56 + az, 56 + ba, 56 + bb, 56 + bc, 56 + bd, 56 + be, 56 + bf, 56 + bg, 56 + bh, 56 + bi, 56 + bj, 56 + bk, 56 + bl, 56 + bm, 56 + bn, 56 + bo, 56 + bp, 56 + bq, 56 + br, 56 + bs, 56 + bt, 56 + bu, 56 + bv, 56 + bw, 56 + bx, 56 + by, 56 + bz, 56 + ca, 56 + cb, 56 + cc, 56 + cd, 56 + ce, 56 + cf, 56 + cg, 56 + ch, 56 + ci, 56 + cj, 56 + ck, 56 + cl, 56 + cm, 56 + cn, 56 + co, 56 + cp, 56 + cq, 56 + cr, 56 + cs, 56 + ct, 56 + cu, 56 + cv, 56 + cw, 56 + cx, 56 + cy, 56 + cz, 56 + da, 56 + db, 56 + dc, 56 + dd, 56 + de, 56 + df, 56 + dg, 56 + dh, 56 + di, 56 + dj, 56 + dk, 56 + dl, 56 + dm, 56 + dn, 56 + do, 56 + dp, 56 + dq, 56 + dr, 56 + ds, 56 + dt, 56 + du, 56 + dv, 56 + dw, 56 + dx, 56 + dy, 56 + dz, 56 + ea, 56 + eb, 56 + ec, 56 + ed, 56 + ee, 56 + ef, 56 + eg, 56 + eh, 56 + ei, 56 + ej, 56 + ek, 56 + el, 56 + em, 56 + en, 56 + eo, 56 + ep, 56 + eq, 56 + er, 56 + es, 56 + et, 56 + eu, 56 + ev, 56 + ew, 56 + ex, 56 + ey, 56 + ez, 56 + fa, 56 + fb, 56 + fc, 56 + fd, 56 + fe, 56 + ff, 56 + fg, 56 + fh, 56 + fi, 5 6 + fj, 56 + fk, 56 + fl, 56 + fm, 56 + fn, 56 + fo, 56 + fp, 56 + fq, 56 + fr, 56 + fs, 56 + ft, 56 + fu, 56 + fv, 56 + fw, 56 + fx, 56 + fy, 56 + fz, 56 + ga, 56 + gb, 56 + gc, 56 + gd, 56 + ge, 56 + gf, 56 + gg, 56 + gh, 56 + gi, 56 + gj, 56 + gk, 56 + gl, 56 + gm, 56 + gn, 56 + go, 56 + gp, 56 + gq, 56 + gr, 56 + gs, 56 + gt, 56 + gu, 56 + gv, 56 + gw, 56 + gx, 56 + gy, 56 + gz, 56 + ha, 56 + hb, 56 + hc, 56 + hd, 56 + he, 56 + hf, 56 + hg, 56 + hh, 56 + hi, 56 + hj, 56 + hk, 56 + hl, 56 + hm, 56 + hn, 56 + ho, 56 + hp, 56 + hq, 56 + hr, 56 + hs, 56 + ht, 56 + hu, 56 + hv, 56 + hw, 56 + hx, 56 + hy, 56 + hz, 56 + ia, 56 + ib, 56 + ic, 56 + id, 56 + ie, 56 + if, 56 + ig, 56 + ih, 56 + ii, 56 + ij, 56 + ik, 56 + il, 56 + im, 56 + in, 56 + io, 56 + ip, 56 + iq, 56 + ir, 56 + is, 56 + it, 56 + iu, 56 + iv, 56 + iw, 56 + ix, 56 + iy, 56 + iz, 56 + ja, 56 + jb, 56 + jc, 56 + jd, 56 + je, 56 + jf, 56 + jg, 56 + jh, 56 + ji, 56 + jj, 56 + jk, 56 + jl, 56 + jm, 56 + jn, 56 + jo, 56 + jp, 56 + jq, 56 + jr, 56 + js, 56 + jt, 56 + ju, 56 + jv, 56 + jw, 56 + jx, 56 + jy, 56 + jz, 56 + ka, 56 + kb, 56 + kc, 56 + kd, 56 + ke, 56 + kf, 56 + kg, 56 + kh, 56 + ki, 56 + kj, 56 + kk, 56 + kl, 56 + km, 56 + kn, 56 + ko, 56 + kp, 56 + kq, 56 + kr, 56 + ks, 56 + kt, 56 + ku, 56 + kv, 56 + kw, 56 + kx, 56 + ky, 56 + kz, 56 + la, 56 + lb, 56 + lc, 56 + ld, 56 + le, 56 + lf, 56 + lg, 56 + lh, 56 + li, 56 + lj, 56 + lk, 56 + ll, 56 + lm, 56 + ln, 56 + lo, 56 + lp, 56 + lq, 56 + lr, 56 + ls, 56 + lt , 56 + lu, 56 + lv, 56 + lw, 56 + lx, 56 + ly, 56 + lz, 56 + ma, 56 + mb, 56 + mc, 56 + md, 56 + me, 56 + mf, 56 + mg, 56 + mh, 56 + mi, 56 + mj, 56 + mk, 56 + ml, 56 + mm, 56 + mn, 56 + mo, 56 + mp, 56 + mq, 56 + mr, 56 + ms , 56 + mt, 56 + mu, 56 + mv, 56 + mw, 56 + mx, 56 + my, 56 + mz, 56 + na, 56 + nb, 56 + nc, 56 + nd, 56 + ne, 56 + nf, 56 + ng, 56 + nh,
56 + ni, 56 + nj, 56 + nk, 56 + nl, 56 + nm, 56 + nn, 56 + no, 56 + np, 56 + nq, 56 + nr, 56 + ns, 56 + nt, 56 + nu, 56 + nv, 56 + nw, 56 + nx, 56 + ny, 56 + nz, 56 + oa, 56 + ob, 56 + oc, 56 + od, 56 + oe, 56 + of, 56 + og, 56 + oh, 56 + oi, 56 + oj, 56 + ok, 56 + ol, 56 + om, 56 + on, 56 + oo, 56 + op, 56 + oq, 56 + or, 56 + os, 56 + ot, 56 + ou, 56 + ov, 56 + ow, 56 + ox, 56 + oy, 56 + oz, 56 + pa, 56 + pb, 56 + pc, 56 + pd, 56 + pe, 56 + pf, 56 + pg, 56 + ph, 56 + pi, 56 + pj, 56 + pk, 56 + pl, 56 + pm, 56 + pn, 56 + po, 56 + pp, 56 + pq, 56 + pr, 56 + ps, 56 + pt, 56 + pu, 56 + pv, 56 + pw, 56 + px, 56 + py, 56 + pz, 56 + qa, 56 + qb, 56 + qc, 56 + qd, 56 + qe, 56 + qf, 56 + qg, 56 + qh, 56 + qi, 56 + qj, 56 + qk, 56 + ql, 56 + qm, 56 + qn, 56 + qo, 56 + qp, 56 + qq, 56 + qr, 56 + qs, 56 + qt, 56 + qu, 56 + qv, 56 + qw, 56 + qx, 56 + qy, 56 + qz, 56 + ra, 56 + rb, 56 + rc, 56 + rd, 56 + re, 56 + rf, 56 + rg, 56 + rh, 56 + ri, 56 + rj, 56 + rk, 56 + rl, 56 + rm, 56 + rn, 56 + ro, 56 + rp, 56 + rq, 56 + rr, 56 + rs, 56 + rt, 56 + ru, 56 + rv, 56 + rw, 56 + rx, 56 + ry, 56 + rz, 56 + sa, 56 + sb, 56 + sc, 56 + sd, 56 + se, 56 + sf, 56 + sg, 56 + sh, 56 + si, 56 + sj, 56 + sk, 56 + sl, 56 + sm, 56 + sn, 56 + so, 56 + sp, 56 + sq, 56 + sr, 57 + a, 57 + b, 57 + c, 57 + d, 57 + e, 57 + f, 57 + g, 57 + h, 57 + i, 57 + j, 57 + k, 57 + l, 57 + m, 57 + n, 57 + o, 57 + p, 57 + q, 57 + r, 57 + s, 57 + t, 57 + u, 57 + v, 57 + w, 57 + x, 57 + y, 57 + z, 57 + aa, 57 + ab, 57 + ac, 57 + ad, 57 + ae, 57 + af, 57 + ag, 57 + ah, 57 + ai, 57 + aj, 57 + ak, 57 + al, 57 + am, 57 + an, 57 + ao, 57 + ap, 57 + aq, 57 + ar, 57 + as, 57 + at, 57 + au, 57 + av, 57 + aw, 57 + ax, 57 + ay, 57 + az, 57 + ba, 57 + bb, 57 + bc, 57 + bd, 57 + be, 57 + bf, 57 + bg, 57 + bh, 57 + bi, 57 + bj, 57 + bk, 57 + bl, 57 + bm, 57 + bn, 57 + bo, 57 + bp, 57 + bq, 57 + br, 57 + bs, 57 + bt, 57 + bu, 57 + bv, 57 + bw, 57 + bx, 57 + by, 57 + bz, 57 + ca, 57 + cb, 57 + cc, 57 + cd, 57 + ce, 57 + cf, 57 + cg, 57 + ch, 57 + ci, 57 + cj, 57 + ck, 57 + cl, 57 + cm, 57 + cn, 57 + co, 57 + cp, 57 + cq, 57 + cr, 57 + cs, 57 + ct, 57 + cu, 57 + cv, 57 + cw, 57 + cx, 57 + cy, 57 + cz, 57 + da, 57 + db, 57 + dc, 57 + dd, 57 + de, 57 + df, 57 + dg, 57 + dh, 57 + di, 57 + dj, 57 + dk, 57 + dl, 57 + dm, 57 + dn, 57 + do, 57 + dp, 57 + dq, 57 + dr, 57 + ds, 57 + dt, 57 + du, 57 + dv, 57 + dw, 57 + dx, 57 + dy, 57 + dz, 57 + ea, 57 + eb, 57 + ec, 57 + ed, 57 + ee, 57 + ef, 57 + eg, 57 + eh, 57 + ei, 57 + ej, 57 + ek, 57 + el, 57 + em, 57 + en, 57 + eo, 57 + ep, 57 + eq, 57 + er, 57 + es, 57 + et, 57 + eu, 57 + ev, 57 + ew, 57 + ex, 57 + ey, 57 + ez, 57 + fa, 57 + fb, 57 + fc, 57 + fd, 57 + fe, 57 + ff, 57 + fg, 57 + fh, 57 + fi, 57 + fj, 57 + fk, 57 + fl, 57 + fm, 57 + fn, 57 + fo, 57 + fp, 57 + fq, 57 + fr, 57 + fs, 57 + ft, 57 + fu, 57 + fv, 57 + fw, 57 + fx, 57 + fy, 57 + fz, 57 + ga, 57 + gb, 57 + gc, 57 + gd, 57 + ge, 57 + gf, 57 + gg, 57 + gh, 57 + gi, 57 + gj, 57 + gk, 57 + gl, 57 + gm, 57 + gn, 57 + go, 57 + g p, 57 + gq, 57 + gr, 57 + gs, 57 + gt, 57 + gu, 57 + gv, 57 + gw, 57 + gx, 57 + gy, 57 + gz, 57 + ha, 57 + hb, 57 + hc, 57 + hd, 57 + he, 57 + hf, 57 + hg, 57 + hh, 57 + hi, 57 + hj, 57 + hk, 57 + hl, 57 + hm, 57 + hn, 57 + ho, 57 + hp, 57 + hq, 57 + hr, 57 + hs, 57 + ht, 57 + hu, 57 + hv, 57 + hw, 57 + hx, 57 + hy, 57 + hz, 57 + ia, 57 + ib, 57 + ic, 57 + id, 57 + ie, 57 + if, 57 + ig, 57 + ih, 57 + ii, 57 + ij, 57 + ik, 57 + il, 57 + im, 57 + in, 57 + io, 57 + ip, 57 + iq, 57 + ir, 57 + is, 57 + it, 57 + iu, 57 + iv, 57 + iw, 57 + ix, 57 + iy, 57 + iz, 57 + ja, 57 + jb, 57 + jc, 57 + jd, 57 + je, 57 + jf, 57 + jg, 57 + jh, 57 + ji, 57 + jj, 57 + jk, 57 + jl, 57 + jm, 57 + jn, 57 + jo, 57 + jp, 57 + jq, 57 + jr, 57 + js, 57 + jt, 57 + ju, 57 + jv, 57 + jw, 57 + jx, 57 + jy, 57 + jz, 57 + ka, 57 + kb, 57 + kc, 57 + kd, 57 + ke, 57 + kf, 57 + kg, 57 + kh, 57 + ki, 57 + kj, 57 + kk, 57 + kl, 57 + km, 57 + kn, 57 + ko, 57 + kp, 57 + kq, 57 + kr, 57 + ks, 57 + kt, 57 + ku, 57 + kv, 57 + kw, 57 + kx, 57 + ky, 57 + kz, 57 + la, 57 + lb, 57 + lc, 57 + ld, 57 + le, 57 + lf, 57 + lg, 57 + lh, 57 + li, 57 + lj, 57 + lk, 57 + ll, 57 + lm, 57 + ln, 57 + lo, 57 + lp, 57 + lq, 57 + lr, 57 + ls, 57 + lt, 57 + lu, 57 + lv, 57 + lw, 57 + lx, 57 + ly, 57 + lz, 57 + ma, 57 + mb, 57 + mc, 57 + md, 57 + me, 57 + mf, 57 + mg, 57 + mh, 57 + mi, 57 + mj, 57 + mk, 57 + ml, 57 + mm, 57 + mn, 57 + mo, 57 + mp, 57 + mq, 57 + mr, 57 + ms, 57 + mt, 57 + mu, 57 + mv, 57 + mw, 57 + mx, 57 + my, 57 + mz, 57 + na, 57 + nb, 57 + nc, 57 + nd, 57 + ne, 57 + nf, 57 + ng, 57 + nh, 57 + ni, 57 + nj, 57 + nk, 57 + nl, 57 + nm , 57 + nn, 57 + no, 57 + np, 57 + nq, 57 + nr, 57 + ns, 57 + nt, 57 + nu, 57 + nv, 57 + nw, 57 + nx, 57 + ny, 57 + nz, 57 + oa, 57 + ob, 57 + oc, 57 + od, 57 + oe, 57 + of, 57 + og, 57 + oh, 57 + oi, 57 + oj, 57 + ok, 57 + ol , 57 + om, 57 + on, 57 + oo, 57 + op, 57 + oq, 57 + or, 57 + os, 57 + ot, 57 + ou, 57 + ov, 57 + ow, 57 + ox, 57 + oy, 57 + oz, 57 + pa, 57 + pb, 57 + pc, 57 + pd, 57 + pe, 57 + pf, 57 + pg, 57 + ph, 57 + pi, 57 + pj, 57 + pk , 57 + pl, 57 + pm, 57 + pn, 57 + po, 57 + pp, 57 + pq, 57 + pr, 57 + ps, 57 + pt, 57 + pu, 57 + pv, 57 + pw, 57 + px, 57 + py, 57 + pz, 57 + qa, 57 + qb, 57 + qc, 57 + qd, 57 + qe, 57 + qf, 57 + qg, 57 + qh, 57 + qi, 57 + qj , 57 + qk, 57 + ql, 57 + qm, 57 + qn, 57 + qo, 57 + qp, 57 + qq, 57 + qr, 57 + qs, 57 + qt, 57 + qu, 57 + qv, 57 + qw, 57 + qx, 57 + qy, 57 + qz, 57 + ra, 57 + rb, 57 + rc, 57 + rd, 57 + re, 57 + rf, 57 + rg, 57 + rh, 57 + ri , 57 + rj, 57 + rk, 57 + rl, 57 + rm, 57 + rn, 57 + ro, 57 + rp, 57 + rq, 57 + rr, 57 + rs, 57 + rt, 57 + ru, 57 + rv, 57 + rw, 57 + rx, 57 + ry, 57 + rz, 57 + sa, 57 + sb, 57 + sc, 57 + sd, 57 + se, 57 + sf, 57 + sg, 57 + sh , 57 + si, 57 + sj, 57 + sk, 57 + sl, 57 + sm, 57 + sn, 57 + so, 57 + sp, 57 + sq, 57 + sr, 58 + a, 58 + b, 58 + c, 58 + d, 58 + e, 58 + f, 58 + g, 58 + h, 58 + i, 58 + j, 58 + k, 58 + l, 58 + m, 58 + n, 58 + o , 58 + p, 58 + q, 58 + r, 58 + 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58 + mo, 58 + mp, 58 + mq, 58 + mr, 58 + m s, 58 + mt, 58 + mu, 58 + mv, 58 + mw, 58 + mx, 58 + my, 58 + mz, 58 + na, 58 + nb, 58 + nc, 58 + nd, 58 + ne, 58 + nf, 58 + ng, 58 + nh, 58 + ni, 58 + nj, 58 + nk, 58 + nl, 58 + nm, 58 + nn, 58 + no, 58 + np, 58 + nq, 58 + nr, 58 + ns, 58 + nt, 58 + nu, 58 + nv, 58 + nw, 58 + nx, 58 + ny, 58 + nz, 58 + oa, 58 + ob, 58 + oc, 58 + od, 58 + oe, 58 + of, 58 + og, 58 + oh, 58 + oi, 58 + oj, 58 + ok, 58 + ol, 58 + om, 58 + on, 58 + oo, 58 + op, 58 + oq, 58 + or, 58 + os, 58 + ot, 58 + ou, 58 + ov, 58 + ow, 58 + ox, 58 + oy, 58 + oz, 58 + pa, 58 + pb, 58 + pc, 58 + pd, 58 + pe, 58 + pf, 58 + pg, 58 + ph, 58 + pi, 58 + pj, 58 + pk, 58 + pl, 58 + pm, 58 + pn, 58 + po, 58 + pp, 58 + pq, 58 + pr, 58 + ps, 58 + pt, 58 + pu, 58 + pv, 58 + pw, 58 + px, 58 + py, 58 + pz, 58 + qa, 58 + qb, 58 + qc, 58 + qd, 58 + qe, 58 + qf, 58 + qg, 58 + qh, 58 + qi, 58 + qj, 58 + qk, 58 + ql, 58 + qm, 58 + qn, 58 + qo, 58 + qp, 58 + qq, 58 + qr, 58 + qs, 58 + qt, 58 + qu, 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59 + fu, 59 + fv, 59 + fw, 59 + fx, 59 + fy, 59 + fz, 59 + ga, 59 + gb, 59 + gc, 59 + gd, 59 + ge, 59 + gf, 59 + gg, 59 + gh, 59 + gi, 59 + gj, 59 + gk, 59 + gl, 59 + gm , 59 + gn, 59 + go, 59 + gp, 59 + gq, 59 + gr, 59 + gs, 59 + gt, 59 + gu, 59 + gv, 59 + gw, 59 + gx, 59 + gy, 59 + gz, 59 + ha, 59 + hb, 59 + hc, 59 + hd, 59 + he, 59 + hf, 59 + hg, 59 + hh, 59 + hi, 59 + hj, 59 + hk, 59 + hl , 59 + hm, 59 + hn, 59 + ho, 59 + hp, 59 + hq, 59 + hr, 59 + hs, 59 + ht, 59 + hu, 59 + hv, 59 + hw, 59 + hx, 59 + hy, 59 + hz, 59 + ia, 59 + ib, 59 + ic, 59 + id, 59 + ie, 59 + if, 59 + ig, 59 + ih, 59 + ii, 59 + ij, 59 + ik , 59 + il, 59 + im, 59 + in, 59 + io, 59 + ip, 59 + iq, 59 + ir, 59 + is, 59 + it, 59 + iu, 59 + iv, 59 + iw, 59 + ix, 59 + iy, 59 + iz, 59 + ja, 59 + jb, 59 + jc, 59 + jd, 59 + je, 59 + jf, 59 + jg, 59 + jh, 59 + ji, 59 + jj , 59 + jk, 59 + jl, 59 + jm, 59 + jn, 59 + jo, 59 + jp, 59 + jq, 59 + jr, 59 + js, 59 + jt, 59 + ju, 59 + jv, 59 + jw, 59 + jx, 59 + jy, 59 + jz, 59 + 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so, 59 + sp, 59 + sq, 59 + sr,
60 + a, 60 + b, 60 + c, 60 + d, 60 + e, 60 + f, 60 + g, 60 + h, 60 + i, 60 + j, 60 + k, 60 + l, 60 + m, 60 + n, 60 + o, 60 + p, 60 + q, 60 + r, 60 + s, 60 + t, 60 + u, 60 + v, 60 + w, 60 + x, 60 + y, 60 + z, 60 + aa, 60 + ab, 60 + ac, 60 + ad, 60 + ae, 60 + af, 60 + ag, 60 + ah, 60 + ai, 60 + aj, 60 + ak, 60 + al, 60 + am, 60 + an, 60 + ao, 60 + ap, 60 + aq, 60 + ar, 60 + as, 60 + at, 60 + au, 60 + av, 60 + aw, 60 + ax, 60 + ay, 60 + az, 60 + ba, 60 + bb, 60 + bc, 60 + bd, 60 + be, 60 + bf, 60 + bg, 60 + bh, 60 + bi, 60 + bj, 60 + bk, 60 + bl, 60 + bm, 60 + bn, 60 + bo, 60 + bp, 60 + bq, 60 + br, 60 + bs, 60 + bt, 60 + bu, 60 + bv, 60 + bw, 60 + bx, 60 + by, 60 + bz, 60 + ca, 60 + cb, 60 + cc, 60 + cd, 60 + ce, 60 + cf, 60 + cg, 60 + ch, 60 + ci, 60 + cj, 60 + ck, 60 + cl, 60 + cm, 60 + cn, 60 + co, 60 + cp, 60 + cq, 60 + cr, 60 + cs, 60 + ct, 60 + cu, 60 + cv, 60 + cw, 60 + cx, 60 + cy, 60 + cz, 60 + da, 60 + db, 60 + dc, 60 + dd, 60 + de, 60 + df, 60 + dg, 60 + dh, 60 + di, 60 + dj, 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60 + hr, 60 + hs, 60 + ht, 60 + hu, 60 + hv, 60 + hw, 60 + hx, 60 + hy, 60 + hz, 60 + ia, 60 + ib, 60 + ic, 60 + id, 60 + ie, 60 + if, 60 + ig, 60 + ih, 60 + ii, 60 + ij, 60 + ik, 60 + il, 60 + im, 60 + in, 60 + io, 60 + ip, 60 + iq, 60 + ir, 60 + is, 60 + it, 60 + iu, 60 + iv, 60 + iw, 60 + ix, 60 + iy, 60 + iz, 60 + ja, 60 + jb, 60 + jc, 60 + jd, 60 + je, 60 + jf, 60 + jg, 60 + jh, 60 + ji, 60 + jj, 60 + jk, 60 + jl, 60 + jm, 60 + jn, 60 + jo, 60 + jp, 60 + jq, 60 + jr, 60 + js, 60 + jt, 60 + ju, 60 + jv, 60 + jw, 60 + jx, 60 + jy, 60 + jz, 60 + ka, 60 + kb, 60 + kc, 60 + kd, 60 + ke, 60 + kf, 60 + kg, 60 + kh, 60 + ki, 60 + kj, 60 + kk, 60 + kl, 60 + km, 60 + kn, 60 + ko, 60 + kp, 60 + kq, 60 + kr, 60 + ks, 60 + kt, 60 + ku, 60 + kv, 60 + kw, 60 + kx, 60 + ky, 60 + kz, 60 + la, 60 + lb, 60 + lc, 60 + ld, 60 + le, 60 + lf, 60 + lg, 60 + lh, 60 + li, 60 + lj, 60 + lk, 60 + ll, 60 + lm, 60 + ln, 60 + lo, 60 + lp, 60 + lq, 60 + lr, 60 + ls, 60 + lt, 60 + lu, 60 + lv, 60 + lw, 60 + lx, 60 + ly, 60 + l z, 60 + ma, 60 + mb, 60 + mc, 60 + md, 60 + me, 60 + mf, 60 + mg, 60 + mh, 60 + mi, 60 + mj, 60 + mk, 60 + ml, 60 + mm, 60 + mn, 60 + mo, 60 + mp, 60 + mq, 60 + mr, 60 + ms, 60 + mt, 60 + mu, 60 + mv, 60 + mw, 60 + mx, 60 + my, 60 + mz, 60 + na, 60 + nb, 60 + nc, 60 + nd, 60 + ne, 60 + nf, 60 + ng, 60 + nh, 60 + ni, 60 + nj, 60 + nk, 60 + nl, 60 + nm, 60 + nn, 60 + no, 60 + np, 60 + nq, 60 + nr, 60 + ns, 60 + nt, 60 + nu, 60 + nv, 60 + nw, 60 + nx, 60 + ny, 60 + nz, 60 + oa, 60 + ob, 60 + oc, 60 + od, 60 + oe, 60 + of, 60 + og, 60 + oh, 60 + oi, 60 + oj, 60 + ok, 60 + ol, 60 + om, 60 + on, 60 + oo, 60 + op, 60 + oq, 60 + or, 60 + os, 60 + ot, 60 + ou, 60 + ov, 60 + ow, 60 + ox, 60 + oy, 60 + oz, 60 + pa, 60 + pb, 60 + pc, 60 + pd, 60 + pe, 60 + pf, 60 + pg, 60 + ph, 60 + pi, 60 + pj, 60 + pk, 60 + pl, 60 + pm, 60 + pn, 60 + po, 60 + pp, 60 + pq, 60 + pr, 60 + ps, 60 + pt, 60 + pu, 60 + pv, 60 + pw, 60 + px, 60 + py, 60 + pz, 60 + qa, 60 + qb, 60 + qc, 60 + qd, 60 + qe, 60 + qf, 60 + qg, 60 + qh, 60 + qi, 60 + qj, 60 + qk, 60 + ql, 60 + qm, 60 + qn, 60 + qo, 60 + qp, 60 + qq, 60 + qr, 60 + qs, 60 + qt, 60 + qu, 60 + qv, 60 + qw, 60 + qx, 60 + qy, 60 + qz, 60 + ra, 60 + rb, 60 + rc, 60 + rd, 60 + re, 60 + rf, 60 + rg, 60 + rh, 60 + ri, 60 + rj, 60 + rk, 60 + rl, 60 + rm, 60 + rn, 60 + ro, 60 + rp, 60 + rq, 60 + rr, 60 + rs, 60 + rt, 60 + ru, 60 + rv, 60 + rw, 60 + rx, 60 + ry, 60 + rz, 60 + sa, 60 + sb, 60 + sc, 60 + sd, 60 + se, 60 + sf, 60 + sg, 60 + sh, 60 + si, 60 + sj, 60 + sk, 60 + sl, 60 + sm, 60 + sn, 60 + so, 60 + sp, 60 + sq, 60 + sr, 61 + a, 61 + b, 61 + c, 61 + d, 61 + e , 61 + f, 61 + g, 61 + h, 61 + i, 61 + j, 61 + k, 61 + l, 61 + m, 61 + n, 61 + o, 61 + p, 61 + q, 61 + r, 61 + s, 61 + t, 61 + u, 61 + v, 61 + w, 61 + x, 61 + y, 61 + z, 61 + aa, 61 + ab, 61 + ac, 61 + ad , 61 + ae, 61 + af, 61 + ag, 61 + ah, 61 + ai, 61 + aj, 61 + ak, 61 + al, 61 + am, 61 + an, 61 + ao, 61 + ap, 61 + aq, 61 + ar, 61 + as, 61 + at, 61 + au, 61 + av, 61 + aw, 61 + ax, 61 + ay, 61 + az, 61 + ba, 61 + bb, 61 + bc , 61 + bd, 61 + be, 61 + bf, 61 + bg, 61 + bh, 61 + bi, 61 + bj, 61 + bk, 61 + bl, 61 + bm, 61 + bn, 61 + bo, 61 + bp, 61 + bq, 61 + br, 61 + bs, 61 + bt, 61 + bu, 61 + bv, 61 + bw, 61 + bx, 61 + by, 61 + bz, 61 + ca, 61 + cb , 61 + cc, 61 + cd, 61 + ce, 61 + cf, 61 + cg, 61 + ch, 61 + ci, 61 + cj, 61 + ck, 61 + cl, 61 + cm, 61 + cn, 61 + co, 61 + cp, 61 + cq, 61 + cr, 61 + cs, 61 + ct, 61 + cu, 61 + cv, 61 + cw, 61 + cx, 61 + cy, 61 + cz, 61 + da , 61 + db, 61 + dc, 61 + dd, 61 + de, 61 + df, 61 + dg, 61 + dh, 61 + di, 61 + dj, 61 + dk, 61 + dl, 61 + dm, 61 + dn, 61 + do, 61 + dp, 61 + dq, 61 + dr, 61 + ds, 61 + dt, 61 + du, 61 + dv, 61 + dw, 61 + dx, 61 + dy, 61 + dz , 61 + ea, 61 + eb, 61 + ec, 61 + ed, 61 + ee, 61 + ef, 61 + eg, 61 + eh, 61 + ei, 61 + ej, 61 + ek, 61 + el, 61 + em, 61 + en, 61 + eo, 61 + ep, 61 + eq, 61 + er, 61 + es, 61 + et, 61 + eu, 61 + ev, 61 + ew, 61 + ex, 61 + ey , 61 + ez, 61 + fa, 61 + fb, 61 + fc, 61 + fd, 61 + fe, 61 + ff, 61 + fg, 61 + fh, 61 + fi, 61 + fj, 61 + fk, 61 + fl, 61 + fm, 61 + fn, 61 + fo, 61 + fp, 61 + fq, 61 + fr, 61 + fs, 61 + ft , 61 + fu, 61 + fv, 61 + fw, 61 + fx, 61 + fy, 61 + fz, 61 + ga, 61 + gb, 61 + gc, 61 + gd, 61 + ge, 61 + gf, 61 + gg, 61 + gh, 61 + gi, 61 + gj, 61 + gk, 61 + gl, 61 + gm, 61 + gn, 61 + go, 61 + gp, 61 + gq, 61 + gr, 61 + gs , 61 + gt, 61 + gu, 61 + gv, 61 + gw, 61 + gx, 61 + gy, 61 + gz, 61 + ha, 61 + hb, 61 + hc, 61 + hd, 61 + he, 61 + hf, 61 + hg, 61 + hh, 61 + hi, 61 + hj, 61 + hk, 61 + hl, 61 + hm, 61 + hn, 61 + ho, 61 + hp, 61 + hq, 61 + hr , 61 + hs, 61 + ht, 61 + hu, 61 + hv, 61 + hw, 61 + hx, 61 + hy, 61 + hz, 61 + ia, 61 + ib, 61 + ic, 61 + id, 61 + ie, 61 + if, 61 + ig, 61 + ih, 61 + ii, 61 + ij, 61 + ik, 61 + il, 61 + im, 61 + in, 61 + io, 61 + ip, 61 + iq , 61 + ir, 61 + is, 61 + it, 61 + iu, 61 + iv, 61 + iw, 61 + ix, 61 + iy, 61 + iz, 61 + ja, 61 + jb, 61 + jc, 61 + jd, 61 + je, 61 + jf, 61 + jg, 61 + jh, 61 + ji, 61 + jj, 61 + jk, 61 + jl, 61 + jm, 61 + jn, 61 + jo, 61 + jp , 61 + jq, 61 + jr, 61 + js, 61 + jt, 61 + ju, 61 + jv, 61 + jw, 61 + jx, 61 + jy, 61 + jz, 61 + ka, 61 + kb, 61 + kc, 61 + kd, 61 + ke, 61 + kf, 61 + kg, 61 + kh, 61 + ki, 61 + kj, 61 + kk, 61 + kl, 61 + km, 61 + kn, 61 + ko , 61 + kp, 61 + kq, 61 + kr, 61 + ks, 61 + kt, 61 + ku, 61 + kv, 61 + kw, 61 + kx, 61 + ky, 61 + kz, 61 + la, 61 + lb, 61 + lc, 61 + ld, 61 + le, 61 + lf, 61 + lg, 61 + lh, 61 + li, 61 + lj, 61 + lk, 61 + ll, 61 + lm, 61 + ln , 61 + lo, 61 + lp, 61 + lq, 61 + lr, 61 + ls, 61 + lt, 61 + lu, 61 + lv, 61 + lw, 61 + lx, 61 + ly, 61 + lz, 61 + ma, 61 + mb, 61 + mc, 61 + md, 61 + me, 61 + mf, 61 + mg, 61 + mh, 61 + mi, 61 + mj, 61 + mk, 61 + ml, 61 + mm, 61 + mn, 61 + mo, 61 + mp, 61 + mq, 61 + mr, 61 + ms, 61 + mt, 61 + mu, 61 + mv, 61 + mw, 61 + mx, 61 + my, 61 + mz, 61 + na, 61 + nb, 61 + nc, 61 + nd, 61 + ne, 61 + nf, 61 + ng, 61 + nh, 61 + ni, 61 + nj, 61 + nk, 61 + nl, 61 + nm, 61 + nn, 61 + no, 61 + np, 61 + nq, 61 + nr, 61 + ns, 61 + nt, 61 + nu, 61 + nv, 61 + nw, 61 + nx, 61 + ny, 61 + nz, 61 + oa, 61 + ob, 61 + oc, 61 + od, 61 + oe, 61 + of, 61 + og, 61 + oh, 61 + oi, 61 + oj, 61 + ok, 61 + ol, 61 + om, 61 + on, 61 + oo, 61 + op, 61 + oq, 61 + or, 61 + os, 61 + ot, 61 + ou, 61 + ov, 61 + ow, 61 + ox, 61 + oy, 61 + oz, 61 + pa, 61 + pb, 61 + pc, 61 + pd, 61 + pe, 61 + pf, 61 + pg, 61 + ph, 61 + pi, 61 + pj, 61 + pk, 61 + pl, 61 + pm, 61 + pn, 61 + po, 61 + pp, 61 + pq, 61 + pr, 61 + ps, 61 + pt, 61 + pu, 61 + pv, 61 + pw, 61 + px, 61 + py, 61 + pz, 61 + qa, 61 + qb, 61 + qc, 61 + qd, 61 + qe, 61 + qf, 61 + qg, 61 + qh, 61 + qi, 61 + qj, 61 + qk, 61 + ql, 61 + qm, 61 + qn, 61 + qo, 61 + qp, 61 + qq, 61 + qr, 61 + qs, 61 + qt, 61 + qu, 61 + qv, 61 + qw, 61 + qx, 61 + qy, 61 + qz, 61 + ra, 61 + rb, 61 + rc, 61 + rd, 61 + re, 61 + rf, 61 + rg, 61 + rh, 61 + ri, 61 + rj, 61 + rk, 61 + rl, 61 + rm, 61 + rn, 61 + ro, 61 + rp, 61 + rq, 61 + rr, 61 + rs, 61 + rt, 61 + ru, 61 + rv, 61 + rw, 61 + rx, 61 + ry, 61 + rz, 61 + sa, 61 + sb, 61 + s c, 61 + sd, 61 + se, 61 + sf, 61 + sg, 61 + sh, 61 + si, 61 + sj, 61 + sk, 61 + sl, 61 + sm, 61 + sn, 61 + so, 61 + sp, 61 + sq, 61 + sr, 62 + a, 62 + b, 62 + c, 62 + d, 62 + e, 62 + f, 62 + g, 62 + h, 62 + i, 62 + j, 62 + k, 62 + l, 62 + m, 62 + n, 62 + o, 62 + p, 62 + q, 62 + r, 62 + s, 62 + t, 62 + u, 62 + v, 62 + w, 62 + x, 62 + y, 62 + z, 62 + aa, 62 + ab, 62 + ac, 62 + ad, 62 + ae, 62 + af, 62 + ag, 62 + ah, 62 + ai, 62 + aj, 62 + ak, 62 + al, 62 + am, 62 + an, 62 + ao, 62 + ap, 62 + aq, 62 + ar, 62 + as, 62 + at, 62 + au, 62 + av, 62 + aw, 62 + ax, 62 + ay, 62 + az, 62 + ba, 62 + bb, 62 + bc, 62 + bd, 62 + be, 62 + bf, 62 + bg, 62 + bh, 62 + bi, 62 + bj, 62 + bk, 62 + bl, 62 + bm, 62 + bn, 62 + bo, 62 + bp, 62 + bq, 62 + br, 62 + bs, 62 + bt, 62 + bu, 62 + bv, 62 + bw, 62 + bx, 62 + by, 62 + bz, 62 + ca, 62 + cb, 62 + cc, 62 + cd, 62 + ce, 62 + cf, 62 + cg, 62 + ch, 62 + ci, 62 + cj, 62 + ck, 62 + cl, 62 + cm, 62 + cn, 62 + co, 62 + cp, 62 + cq, 62 + cr, 62 + cs, 62 + ct, 62 + cu, 62 + cv, 62 + cw, 62 + cx, 62 + cy, 62 + cz, 62 + da, 62 + db, 62 + dc, 62 + dd, 62 + de, 62 + df, 62 + dg, 62 + dh, 62 + di, 62 + dj, 62 + dk, 62 + dl, 62 + dm, 62 + dn, 62 + do, 62 + dp, 62 + dq, 62 + dr, 62 + ds, 62 + dt, 62 + du, 62 + dv, 62 + dw, 62 + dx, 62 + dy, 62 + dz, 62 + ea, 62 + eb, 62 + ec, 62 + ed, 62 + ee, 62 + ef, 62 + eg, 62 + eh, 62 + ei, 62 + ej, 62 + ek, 62 + el, 62 + em, 62 + en, 62 + eo, 62 + ep, 62 + eq, 62 + er, 62 + es, 62 + et, 62 + eu, 62 + ev, 62 + ew, 62 + ex, 62 + ey, 62 + e z, 62 + fa, 62 + fb, 62 + fc, 62 + fd, 62 + fe, 62 + ff, 62 + fg, 62 + fh, 62 + fi, 62 + fj, 62 + fk, 62 + fl, 62 + fm, 62 + fn, 62 + fo, 62 + fp, 62 + fq, 62 + fr, 62 + fs, 62 + ft, 62 + fu, 62 + fv, 62 + fw, 62 + fx, 62 + fy, 62 + fz, 62 + ga, 62 + gb, 62 + gc, 62 + gd, 62 + ge, 62 + gf, 62 + gg, 62 + gh, 62 + gi, 62 + gj, 62 + gk, 62 + gl, 62 + gm, 62 + gn, 62 + go, 62 + gp, 62 + gq, 62 + gr, 62 + gs, 62 + gt, 62 + gu, 62 + gv, 62 + gw, 62 + gx, 62 + gy, 62 + gz, 62 + ha, 62 + hb, 62 + hc, 62 + hd, 62 + he, 62 + hf, 62 + hg, 62 + hh, 62 + hi, 62 + hj, 62 + hk, 62 + hl, 62 + hm, 62 + hn, 62 + ho, 62 + hp, 62 + hq, 62 + hr, 62 + hs, 62 + ht, 62 + hu, 62 + hv, 62 + hw, 62 + hx, 62 + hy, 62 + hz, 62 + ia, 62 + ib, 62 + ic, 62 + id, 62 + ie, 62 + if, 62 + ig, 62 + ih, 62 + ii, 62 + ij, 62 + ik, 62 + il, 62 + im, 62 + in, 62 + io, 62 + ip, 62 + iq, 62 + ir, 62 + is, 62 + it, 62 + iu, 62 + iv, 62 + iw, 62 + ix, 62 + iy, 62 + iz, 62 + ja, 62 + jb, 62 + jc, 62 + jd, 62 + je, 62 + jf, 62 + jg, 62 + jh, 62 + ji, 62 + jj, 62 + jk, 62 + jl, 62 + jm, 62 + jn, 62 + jo, 62 + jp, 62 + jq, 62 + jr, 62 + js, 62 + jt, 62 + ju, 62 + jv, 62 + jw, 62 + jx, 62 + jy, 62 + jz, 62 + ka, 62 + kb, 62 + kc, 62 + kd, 62 + ke, 62 + kf, 62 + kg, 62 + kh, 62 + ki, 62 + kj, 62 + kk, 62 + kl, 62 + km, 62 + kn, 62 + ko, 62 + kp, 62 + kq, 62 + kr, 62 + ks, 62 + kt, 62 + ku, 62 + kv, 62 + kw, 62 + kx, 62 + ky, 62 + kz, 62 + la, 62 + lb, 62 + lc, 62 + ld, 62 + le, 62 + lf, 62 + lg, 62 + lh, 62 + li, 62 + lj, 62 + lk, 62 + ll, 62 + lm, 62 + ln, 62 + lo, 62 + lp, 62 + lq, 62 + lr, 62 + ls, 62 + lt, 62 + lu, 62 + lv, 62 + lw , 62 + lx, 62 + ly, 62 + lz, 62 + ma, 62 + mb, 62 + mc, 62 + md, 62 + me, 62 + mf, 62 + mg, 62 + mh, 62 + mi, 62 + mj, 62 + mk, 62 + ml, 62 + mm, 62 + mn, 62 + mo, 62 + mp, 62 + mq, 62 + mr, 62 + ms, 62 + mt, 62 + mu, 62 + mv , 62 + mw, 62 + mx, 62 + my, 62 + mz, 62 + na, 62 + nb, 62 + nc, 62 + nd, 62 + ne, 62 + nf, 62 + ng, 62 + nh, 62 + ni, 62 + nj, 62 + nk, 62 + nl, 62 + nm, 62 + nn, 62 + no, 62 + np, 62 + nq, 62 + nr, 62 + ns, 62 + nt, 62 + nu , 62 + nv, 62 + nw, 62 + nx, 62 + ny, 62 + nz, 62 + oa, 62 + ob, 62 + oc, 62 + od, 62 + oe, 62 + of, 62 + og, 62 + oh, 62 + oi, 62 + oj, 62 + ok, 62 + ol, 62 + om, 62 + on, 62 + oo, 62 + op, 62 + oq, 62 + or, 62 + os, 62 + ot , 62 + ou, 62 + ov, 62 + ow, 62 + ox, 62 + oy, 62 + oz, 62 + pa, 62 + pb, 62 + pc, 62 + pd, 62 + pe, 62 + pf, 62 + pg, 62 + ph, 62 + pi, 62 + pj, 62 + pk, 62 + pl, 62 + pm, 62 + pn, 62 + po, 62 + pp, 62 + pq, 62 + pr, 62 + ps , 62 + pt, 62 + pu, 62 + pv, 62 + pw, 62 + px, 62 + py, 62 + pz, 62 + qa, 62 + qb, 62 + qc, 62 + qd, 62 + qe, 62 + qf, 62 + qg, 62 + qh, 62 + qi, 62 + qj, 62 + qk, 62 + ql, 62 + qm, 62 + qn, 62 + qo, 62 + qp, 62 + qq, 62 + qr , 62 + qs, 62 + qt, 62 + qu, 62 + qv, 62 + qw, 62 + qx, 62 + qy, 62 + qz, 62 + ra, 62 + rb, 62 + rc, 62 + rd, 62 + re, 62 + rf, 62 + rg, 62 + rh, 62 + ri, 62 + rj, 62 + rk, 62 + rl, 62 + rm, 62 + rn, 62 + ro, 62 + rp, 62 + rq , 62 + rr, 62 + rs, 62 + rt, 62 + ru, 62 + rv, 62 + rw, 62 + rx, 62 + ry, 62 + rz, 62 + sa, 62 + sb, 62 + sc, 62 + sd, 62 + se, 62 + sf, 62 + sg, 62 + sh, 62 + si, 62 + sj, 62 + sk, 62 + sl, 62 + sm, 62 + sn, 62 + so, 62 + sp, 62 + sq, 62 + sr, 63 + a, 63 + b, 63 + c, 63 + d, 63 + e, 63 + f, 63 + g, 63 + h, 63 + i, 63 + j, 63 + k, 63 + l, 63 + m, 63 + n, 63 + o, 63 + p, 63 + q, 63 + r, 63 + s, 63 + t, 63 + u, 63 + v, 63 + w, 63 + x, 63 + y, 63 + z, 63 + aa, 63 + ab, 63 + ac, 63 + ad, 63 + ae, 63 + af, 63 + ag, 63 + ah, 63 + ai, 63 + aj, 63 + ak, 63 + al, 63 + am, 63 + an, 63 + ao, 63 + ap, 63 + aq, 63 + ar, 63 + as, 63 + at, 63 + au, 63 + av, 63 + aw, 63 + ax, 63 + ay, 63 + az, 63 + ba, 63 + bb, 63 + bc, 63 + bd, 63 + be, 63 + bf, 63 + bg, 63 + bh, 63 + bi, 63 + bj, 63 + bk, 63 + bl, 63 + bm, 63 + bn, 63 + bo, 63 + bp, 63 + bq, 63 + br, 63 + bs, 63 + bt, 63 + bu, 63 + bv, 63 + bw, 63 + bx, 63 + by, 63 + bz, 63 + ca, 63 + cb, 63 + cc, 63 + cd, 63 + ce, 63 + cf, 63 + cg, 63 + ch, 63 + ci, 63 + cj, 63 + ck, 63 + cl, 63 + cm, 63 + cn, 63 + co, 63 + cp, 63 + cq, 63 + cr, 63 + cs, 63 + ct, 63 + cu, 63 + cv, 63 + cw, 63 + cx, 63 + cy, 63 + cz, 63 + da, 63 + db, 63 + dc, 63 + dd, 63 + de, 63 + df, 63 + dg, 63 + dh, 63 + di, 63 + dj, 63 + dk, 63 + dl, 63 + dm, 63 + dn, 63 + do, 63 + dp, 63 + dq, 63 + dr, 63 + ds, 63 + dt, 63 + du, 63 + dv, 63 + dw, 63 + dx, 63 + dy, 63 + dz, 63 + ea, 63 + eb, 63 + ec, 63 + ed, 63 + ee, 63 + ef, 63 + eg, 63 + eh, 63 + ei, 63 + ej, 63 + ek, 63 + el, 63 + em, 63 + en, 63 + eo, 63 + ep, 63 + eq, 63 + er, 63 + es, 63 + et, 63 + eu, 63 + ev, 63 + ew, 63 + ex, 63 + ey, 63 + ez, 63 + fa, 63 + fb, 63 + fc, 63 + fd, 63 + fe, 63 + ff, 63 + fg, 63 + fh, 63 + fi, 63 + fj, 63 + fk, 63 + fl, 63 + fm, 63 + fn, 63 + fo, 63 + fp, 63 + fq, 63 + fr, 63 + fs, 63 + ft, 63 + fu, 63 + fv, 63 + fw, 63 + fx, 63 + fy, 63 + fz, 63 + ga, 63 + gb, 63 + gc, 63 + gd, 63 + ge, 63 + gf, 6
3 + gg, 63 + gh, 63 + gi, 63 + gj, 63 + gk, 63 + gl, 63 + gm, 63 + gn, 63 + go, 63 + gp, 63 + gq, 63 + gr, 63 + gs, 63 + gt, 63 + gu, 63 + gv, 63 + gw, 63 + gx, 63 + gy, 63 + gz, 63 + ha, 63 + hb, 63 + hc, 63 + hd, 63 + he, 63 + hf, 63 + hg, 63 + hh, 63 + hi, 63 + hj, 63 + hk, 63 + hl, 63 + hm, 63 + hn, 63 + ho, 63 + hp, 63 + hq, 63 + hr, 63 + hs, 63 + ht, 63 + hu, 63 + hv, 63 + hw, 63 + hx, 63 + hy, 63 + hz, 63 + ia, 63 + ib, 63 + ic, 63 + id, 63 + ie, 63 + if, 63 + ig, 63 + ih, 63 + ii, 63 + ij, 63 + ik, 63 + il, 63 + im, 63 + in, 63 + io, 63 + ip, 63 + iq, 63 + ir, 63 + is, 63 + it, 63 + iu, 63 + iv, 63 + iw, 63 + ix, 63 + iy, 63 + iz, 63 + ja, 63 + jb, 63 + jc, 63 + jd, 63 + je, 63 + jf, 63 + jg, 63 + jh, 63 + ji, 63 + jj, 63 + jk, 63 + jl, 63 + jm, 63 + jn, 63 + jo, 63 + jp, 63 + jq, 63 + jr, 63 + js, 63 + jt, 63 + ju, 63 + jv, 63 + jw, 63 + jx, 63 + jy, 63 + jz, 63 + ka, 63 + kb, 63 + kc, 63 + kd, 63 + ke, 63 + kf, 63 + kg, 63 + kh, 63 + ki, 63 + kj, 63 + kk, 63 + kl, 63 + km, 63 + kn, 63 + ko, 63 + kp, 63 + kq, 63 + kr, 63 + ks, 63 + kt, 63 + ku, 63 + kv, 63 + kw, 63 + kx, 63 + ky, 63 + kz, 63 + la, 63 + lb, 63 + lc, 63 + ld, 63 + le, 63 + lf, 63 + lg, 63 + lh, 63 + li, 63 + lj, 63 + lk, 63 + ll, 63 + lm, 63 + ln, 63 + lo, 63 + lp, 63 + lq, 63 + lr, 63 + ls, 63 + lt, 63 + lu, 63 + lv, 63 + lw, 63 + lx, 63 + ly, 63 + lz, 63 + ma, 63 + mb, 63 + mc, 63 + md, 63 + me, 63 + mf, 63 + mg, 63 + mh, 63 + mi, 63 + mj, 63 + mk, 63 + ml, 63 + mm, 63 + mn, 63 + mo, 63 + mp, 63 + mq , 63 + mr, 63 + ms, 63 + mt, 63 + mu, 63 + mv, 63 + mw, 63 + mx, 63 + my, 63 + mz, 63 + na, 63 + nb, 63 + nc, 63 + nd, 63 + ne, 63 + nf, 63 + ng, 63 + nh, 63 + ni, 63 + nj, 63 + nk, 63 + nl, 63 + nm, 63 + nn, 63 + no, 63 + np , 63 + nq, 63 + nr, 63 + ns, 63 + nt, 63 + nu, 63 + nv, 63 + nw, 63 + nx, 63 + ny, 63 + nz, 63 + oa, 63 + ob, 63 + oc, 63 + od, 63 + oe, 63 + of, 63 + og, 63 + oh, 63 + oi, 63 + oj, 63 + ok, 63 + ol, 63 + om, 63 + on, 63 + oo , 63 + op, 63 + oq, 63 + or, 63 + os, 63 + ot, 63 + ou, 63 + ov, 63 + ow, 63 + ox, 63 + oy, 63 + oz, 63 + pa, 63 + pb, 63 + pc, 63 + pd, 63 + pe, 63 + pf, 63 + pg, 63 + ph, 63 + pi, 63 + pj, 63 + pk, 63 + pl, 63 + pm, 63 + pn , 63 + po, 63 + pp, 63 + pq, 63 + pr, 63 + ps, 63 + pt, 63 + pu, 63 + pv, 63 + pw, 63 + px, 63 + py, 63 + pz, 63 + qa, 63 + qb, 63 + qc, 63 + qd, 63 + qe, 63 + qf, 63 + qg, 63 + qh, 63 + qi, 63 + qj, 63 + qk, 63 + ql, 63 + qm , 63 + qn, 63 + qo, 63 + qp, 63 + qq, 63 + qr, 63 + qs, 63 + qt, 63 + qu, 63 + qv, 63 + qw, 63 + qx, 63 + qy, 63 + qz, 63 + ra, 63 + rb, 63 + rc, 63 + rd, 63 + re, 63 + rf, 63 + rg, 63 + rh, 63 + ri, 63 + rj, 63 + rk, 63 + rl , 63 + rm, 63 + rn, 63 + ro, 63 + rp, 63 + rq, 63 + rr, 63 + rs, 63 + rt, 63 + ru, 63 + rv, 63 + rw, 63 + rx, 63 + ry, 63 + rz, 63 + sa, 63 + sb, 63 + sc, 63 + sd, 63 + se, 63 + sf, 63 + sg, 63 + sh, 63 + si, 63 + sj, 63 + sk , 63 + sl, 63 + sm, 63 + sn, 63 + so, 63 + sp, 63 + sq, 63 + sr, 64 + a, 64 + b, 64 + c, 64 + d, 64 + e, 64 + f, 64 + g, 64 + h, 64 + i, 64 + j, 64 + k, 64 + l, 64 + m, 64 + n, 64 + o, 64 + p, 64 + q, 64 + r, 64 + s, 64 + t, 64 + u, 64 + v, 64 + w, 64 + x , 64 + y, 64 + z, 64 + aa, 64 + ab, 64 + ac, 64 + ad, 64 + ae, 64 + af, 64 + ag, 64 + ah, 64 + ai, 64 + aj, 64 + ak, 64 + al, 64 + am, 64 + an, 64 + ao, 64 + ap, 64 + aq, 64 + ar, 64 + as, 64 + at, 64 + au, 64 + av, 64 + aw , 64 + ax, 64 + ay, 64 + az, 64 + ba, 64 + bb, 64 + bc, 64 + bd, 64 + be, 64 + bf, 64 + bg, 64 + bh, 64 + bi, 64 + bj, 64 + bk, 64 + bl, 64 + bm, 64 + bn, 64 + bo, 64 + bp, 64 + bq, 64 + br, 64 + bs, 64 + bt, 64 + bu, 64 + bv , 64 + bw, 64 + bx, 64 + by, 64 + bz, 64 + ca, 64 + cb, 64 + cc, 64 + cd, 64 + ce, 64 + cf, 64 + cg, 64 + ch, 64 + ci, 64 + cj, 64 + ck, 64 + cl, 64 + cm, 64 + cn, 64 + co, 64 + cp, 64 + cq, 64 + cr, 64 + cs, 64 + ct, 64 + cu , 64 + cv, 64 + cw, 64 + cx, 64 + cy, 64 + cz, 64 + da, 64 + db, 64 + dc, 64 + dd, 64 + de, 64 + df, 64 + dg, 64 + dh, 64 + di, 64 + dj, 64 + dk, 64 + dl, 64 + dm, 64 + dn, 64 + do, 64 + dp, 64 + dq, 64 + dr, 64 + ds, 64 + dt , 64 + du, 64 + dv, 64 + dw, 64 + dx, 64 + dy, 64 + dz, 64 + ea, 64 + eb, 64 + ec, 64 + ed, 64 + ee, 64 + ef, 64 + eg, 64 + eh, 64 + ei, 64 + ej, 64 + ek, 64 + el, 64 + em, 64 + en, 64 + eo, 64 + ep, 64 + eq, 64 + er, 64 + es , 64 + et, 64 + eu, 64 + ev, 64 + ew, 64 + ex, 64 + ey, 64 + ez, 64 + fa, 64 + fb, 64 + fc, 64 + fd, 64 + fe, 64 + ff, 64 + fg, 64 + fh, 64 + fi, 64 + fj, 64 + fk, 64 + fl, 64 + fm, 64 + fn, 64 + fo, 64 + fp, 64 + fq, 64 + fr , 64 + fs, 64 + ft, 64 + fu, 64 + fv, 64 + fw, 64 + fx, 64 + fy, 64 + fz, 64 + ga, 64 + gb, 64 + gc, 64 + gd, 64 + ge, 64 + gf, 64 + gg, 64 + gh, 64 + gi, 64 + gj, 64 + gk, 64 + gl, 64 + gm, 64 + gn, 64 + go, 64 + gp, 64 + gq, 64 + gr, 64 + gs, 64 + gt, 64 + gu, 64 + gv, 64 + gw, 64 + gx, 64 + gy, 64 + gz, 64 + ha, 64 + hb, 64 + hc, 64 + hd, 64 + he, 64 + hf, 64 + hg, 64 + hh, 64 + hi, 64 + hj, 64 + hk, 64 + hl, 64 + hm, 64 + hn, 64 + ho, 64 + hp, 64 + hq, 64 + hr, 64 + hs, 64 + ht, 64 + hu, 64 + hv, 64 + hw, 64 + hx, 64 + hy, 64 + hz, 64 + ia, 64 + ib, 64 + ic, 64 + id, 64 + ie, 64 + if, 64 + ig, 64 + ih, 64 + ii, 64 + ij, 64 + ik, 64 + il, 64 + im, 64 + in, 64 + io, 64 + ip, 64 + iq, 64 + ir, 64 + is, 64 + it, 64 + iu, 64 + iv, 64 + iw, 64 + ix, 64 + iy, 64 + iz, 64 + ja, 64 + jb, 64 + jc, 64 + jd, 64 + je, 64 + jf, 64 + jg, 64 + jh, 64 + ji, 64 + jj, 64 + jk, 64 + jl, 64 + jm, 64 + jn, 64 + jo, 64 + jp, 64 + jq, 64 + jr, 64 + js, 64 + jt, 64 + ju, 64 + jv, 64 + jw, 64 + jx, 64 + jy, 64 + jz, 64 + ka, 64 + kb, 64 + kc, 64 + kd, 64 + ke, 64 + kf, 64 + kg, 64 + kh, 64 + ki, 64 + kj, 64 + kk, 64 + kl, 64 + km, 64 + kn, 64 + ko, 64 + kp, 64 + kq, 64 + kr, 64 + ks, 64 + kt, 64 + ku, 64 + kv, 64 + kw, 64 + kx, 64 + ky, 64 + kz, 64 + la, 64 + lb, 64 + lc, 64 + ld, 64 + le, 64 + lf, 64 + lg, 64 + lh, 64 + li, 64 + lj, 64 + lk, 64 + ll, 64 + lm, 64 + ln, 64 + lo, 64 + lp, 64 + lq, 64 + lr, 64 + ls, 64 + lt, 64 + lu, 64 + lv, 64 + lw, 64 + lx, 64 + ly, 64 + lz, 64 + ma, 64 + mb, 64 + mc, 64 + md, 64 + me, 64 + 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67 + ch, 67 + ci, 67 + cj, 67 + ck, 67 + cl, 67 + cm, 67 + cn, 67 + co, 67 + cp, 67 + cq, 67 + cr, 67 + cs, 67 + ct, 67 + cu, 67 + cv, 67 + cw, 67 + cx, 67 + cy, 67 + cz, 67 + da, 67 + db, 67 + dc, 67 + dd, 67 + de, 67 + df, 67 + dg, 67 + dh, 67 + di, 67 + dj, 67 + dk, 67 + dl, 67 + dm, 67 + dn, 67 + do, 67 + dp, 67 + dq, 67 + dr, 67 + ds, 67 + dt, 67 + du, 67 + dv, 67 + dw, 67 + dx, 67 + dy, 67 + dz, 67 + ea, 67 + eb, 67 + ec, 67 + ed, 67 + ee, 67 + ef, 67 + eg, 67 + eh, 67 + ei, 67 + ej, 67 + ek, 67 + el, 67 + em, 67 + en, 67 + eo, 67 + ep, 67 + eq, 67 + er, 67 + es, 67 + et, 67 + eu, 67 + ev, 67 + ew, 67 + ex, 67 + ey, 67 + ez, 67 + fa, 67 + fb, 67 + fc, 67 + fd, 67 + fe, 67 + ff, 67 + fg, 67 + fh, 67 + fi, 67 + fj, 67 + fk, 67 + fl, 67 + fm, 67 + fn, 67 + fo, 67 + fp, 67 + fq, 67 + fr, 67 + fs, 67 + ft, 67 + fu, 67 + fv, 67 + fw, 67 + fx, 67 + fy, 67 + fz, 67 + ga, 67 + gb, 67 + gc, 67 + gd, 67 + ge, 67 + gf, 67 + gg, 67 + gh, 67 + gi, 67 + gj, 67 + gk, 67 + gl, 67 + gm, 67 + gn, 67 + go, 67 + g p, 67 + gq, 67 + gr, 67 + gs, 67 + gt, 67 + gu, 67 + gv, 67 + gw, 67 + gx, 67 + gy, 67 + gz, 67 + ha, 67 + hb, 67 + hc, 67 + hd, 67 + he, 67 + hf, 67 + hg, 67 + hh, 67 + hi, 67 + hj, 67 + hk, 67 + hl, 67 + hm, 67 + hn, 67 + ho, 67 + hp, 67 + hq, 67 + hr, 67 + hs, 67 + ht, 67 + hu, 67 + hv, 67 + hw, 67 + hx, 67 + hy, 67 + hz, 67 + ia, 67 + ib, 67 + ic, 67 + id, 67 + ie, 67 + if, 67 + ig, 67 + ih, 67 + ii, 67 + ij, 67 + ik, 67 + il, 67 + im, 67 + in, 67 + io, 67 + ip, 67 + iq, 67 + ir, 67 + is, 67 + it, 67 + iu, 67 + iv, 67 + iw, 67 + ix, 67 + iy, 67 + iz, 67 + ja, 67 + jb, 67 + jc, 67 + jd, 67 + je, 67 + jf, 67 + jg, 67 + jh, 67 + ji, 67 + jj, 67 + jk, 67 + jl, 67 + jm, 67 + jn, 67 + jo, 67 + jp, 67 + jq, 67 + jr, 67 + js, 67 + jt, 67 + ju, 67 + jv, 67 + jw, 67 + jx, 67 + jy, 67 + jz, 67 + ka, 67 + kb, 67 + kc, 67 + kd, 67 + ke, 67 + kf, 67 + kg, 67 + kh, 67 + ki, 67 + kj, 67 + kk, 67 + kl, 67 + km, 67 + kn, 67 + ko, 67 + kp, 67 + kq, 67 + kr, 67 + ks, 67 + kt, 67 + ku, 67 + kv, 67 + kw, 67 + kx, 67 + ky, 67 + kz, 67 + la, 67 + lb, 67 + lc, 67 + ld, 67 + le, 67 + lf, 67 + lg, 67 + lh, 67 + li, 67 + lj, 67 + lk, 67 + ll, 67 + lm, 67 + ln, 67 + lo, 67 + lp, 67 + lq, 67 + lr, 67 + ls, 67 + lt, 67 + lu, 67 + lv, 67 + lw, 67 + lx, 67 + ly, 67 + lz, 67 + ma, 67 + mb, 67 + mc, 67 + md, 67 + me, 67 + mf, 67 + mg, 67 + mh, 67 + mi, 67 + mj, 67 + mk, 67 + ml, 67 + mm, 67 + mn, 67 + mo, 67 + mp, 67 + mq, 67 + mr, 67 + ms, 67 + mt, 67 + mu, 67 + mv, 67 + mw, 67 + mx, 67 + my, 67 + mz, 67 + na, 67 + nb, 67 + nc, 67 + nd, 67 + ne, 67 + nf, 67 + ng, 67 + nh, 67 + ni, 67 + nj, 67 + nk, 67 + nl, 67 + nm , 67 + nn, 67 + no, 67 + np, 67 + nq, 67 + nr, 67 + ns, 67 + nt, 67 + nu, 67 + nv, 67 + nw, 67 + nx, 67 + ny, 67 + nz, 67 + oa, 67 + ob, 67 + oc, 67 + od, 67 + oe, 67 + of, 67 + og, 67 + oh, 67 + oi, 67 + oj, 67 + ok, 67 + ol , 67 + om, 67 + on, 67 + oo, 67 + op, 67 + oq, 67 + or, 67 + os, 67 + ot, 67 + ou, 67 + ov, 67 + ow, 67 + ox, 67 + oy, 67 + oz, 67 + pa, 67 + pb, 67 + pc, 67 + pd, 67 + pe, 67 + pf, 67 + pg, 67 + ph, 67 + pi, 67 + pj, 67 + pk , 67 + pl, 67 + pm, 67 + pn, 67 + po, 67 + pp, 67 + pq, 67 + pr, 67 + ps, 67 + pt, 67 + pu, 67 + pv, 67 + pw, 67 + px, 67 + py, 67 + pz, 67 + qa, 67 + qb, 67 + qc, 67 + qd, 67 + qe, 67 + qf, 67 + qg, 67 + qh, 67 + qi, 67 + qj , 67 + qk, 67 + ql, 67 + qm, 67 + qn, 67 + qo, 67 + qp, 67 + qq, 67 + qr, 67 + qs, 67 + qt, 67 + qu, 67 + qv, 67 + qw, 67 + qx, 67 + qy, 67 + qz, 67 + ra, 67 + rb, 67 + rc, 67 + rd, 67 + re, 67 + rf, 67 + rg, 67 + rh, 67 + ri , 67 + rj, 67 + rk, 67 + rl, 67 + rm, 67 + rn, 67 + ro, 67 + rp, 67 + rq, 67 + rr, 67 + rs, 67 + rt, 67 + ru, 67 + rv, 67 + rw, 67 + rx, 67 + ry, 67 + rz, 67 + sa, 67 + sb, 67 + sc, 67 + sd, 67 + se, 67 + sf, 67 + sg, 67 + sh , 67 + si, 67 + sj, 67 + sk, 67 + sl, 67 + sm, 67 + sn, 67 + so, 67 + sp, 67 + sq, 67 + sr, 68 + a, 68 + b, 68 + c, 68 + d, 68 + e, 68 + f, 68 + g, 68 + h, 68 + i, 68 + j, 68 + k, 68 + l, 68 + m, 68 + n, 68 + o , 68 + p, 68 + q, 68 + r, 68 + s, 68 + t, 68 + u, 68 + v, 68 + w , 68 + x, 68 + y, 68 + z, 68 + aa, 68 + ab, 68 + ac, 68 + ad, 68 + ae, 68 + af, 68 + ag, 68 + ah, 68 + ai, 68 + aj, 68 + ak, 68 + al, 68 + am, 68 + an, 68 + ao, 68 + ap, 68 + aq, 68 + ar, 68 + as, 68 + at, 68 + au, 68 + av , 68 + aw, 68 + ax, 68 + ay, 68 + az, 68 + ba, 68 + bb, 68 + bc, 68 + bd, 68 + be, 68 + bf, 68 + bg, 68 + bh, 68 + bi, 68 + bj, 68 + bk, 68 + bl, 68 + bm, 68 + bn, 68 + bo, 68 + bp, 68 + bq, 68 + br, 68 + bs, 68 + bt, 68 + bu , 68 + bv, 68 + bw, 68 + bx, 68 + by, 68 + bz, 68 + ca, 68 + cb, 68 + cc, 68 + cd, 68 + ce, 68 + cf, 68 + cg, 68 + ch, 68 + ci, 68 + cj, 68 + ck, 68 + cl, 68 + cm, 68 + cn, 68 + co, 68 + cp, 68 + cq, 68 + cr, 68 + cs, 68 + ct , 68 + cu, 68 + cv, 68 + cw, 68 + cx, 68 + cy, 68 + cz, 68 + da, 68 + db, 68 + dc, 68 + dd, 68 + de, 68 + df, 68 + dg, 68 + dh, 68 + di, 68 + dj, 68 + dk, 68 + dl, 68 + dm, 68 + dn, 68 + do, 68 + dp, 68 + dq, 68 + dr, 68 + ds , 68 + dt, 68 + du, 68 + dv, 68 + dw, 68 + dx, 68 + dy, 68 + dz, 68 + ea, 68 + eb, 68 + ec, 68 + ed, 68 + ee, 68 + ef, 68 + eg, 68 + eh, 68 + ei, 68 + ej, 68 + ek, 68 + el, 68 + em, 68 + en, 68 + eo, 68 + ep, 68 + eq, 68 + er , 68 + es, 68 + et, 68 + eu, 68 + ev, 68 + ew, 68 + ex, 68 + ey, 68 + ez, 68 + fa, 68 + fb, 68 + fc, 68 + fd, 68 + fe, 68 + ff, 68 + fg, 68 + fh, 68 + fi, 68 + fj, 68 + fk, 68 + fl, 68 + fm, 68 + fn, 68 + fo, 68 + fp, 68 + fq , 68 + fr, 68 + fs, 68 + ft, 68 + fu, 68 + fv, 68 + fw, 68 + fx, 68 + fy, 68 + fz, 68 + ga, 68 + gb, 68 + gc, 68 + gd, 68 + ge, 68 + gf, 68 + gg, 68 + gh, 68 + gi, 68 + gj, 68 + gk, 68 + gl, 68 + gm, 68 + gn, 68 + go, 68 + gp, 68 + gq, 68 + gr, 68 + gs, 68 + gt, 68 + gu, 68 + gv, 68 + gw, 68 + gx, 68 + gy, 68 + gz, 68 + ha, 68 + hb, 68 + hc, 68 + hd, 68 + he, 68 + hf, 68 + hg, 68 + hh, 68 + hi, 68 + hj, 68 + hk, 68 + hl, 68 + hm, 68 + hn, 68 + ho, 68 + hp, 68 + hq, 68 + hr, 68 + hs, 68 + ht, 68 + hu, 68 + hv, 68 + hw, 68 + hx, 68 + hy, 68 + hz, 68 + ia, 68 + ib, 68 + ic, 68 + id, 68 + ie, 68 + if, 68 + ig, 68 + ih, 68 + ii, 68 + ij, 68 + ik, 68 + il, 68 + im, 68 + in, 68 + io, 68 + ip, 68 + iq, 68 + ir, 68 + is, 68 + it, 68 + iu, 68 + iv, 68 + iw, 68 + ix, 68 + iy, 68 + iz, 68 + ja, 68 + jb, 68 + jc, 68 + jd, 68 + je, 68 + jf, 68 + jg, 68 + jh, 68 + ji, 68 + jj, 68 + jk, 68 + jl, 68 + jm, 68 + jn, 68 + jo, 68 + jp, 68 + jq, 68 + jr, 68 + js, 68 + jt, 68 + ju, 68 + jv, 68 + jw, 68 + jx, 68 + jy, 68 + jz, 68 + ka, 68 + kb, 68 + kc, 68 + kd, 68 + ke, 68 + kf, 68 + kg, 68 + kh, 68 + ki, 68 + kj, 68 + kk, 68 + kl, 68 + km, 68 + kn, 68 + ko, 68 + kp, 68 + kq, 68 + kr, 68 + ks, 68 + kt, 68 + ku, 68 + kv, 68 + kw, 68 + kx, 68 + ky, 68 + kz, 68 + la, 68 + lb, 68 + lc, 68 + ld, 68 + le, 68 + lf, 68 + lg, 68 + lh, 68 + li, 68 + lj, 68 + lk, 68 + ll, 68 + lm, 68 + ln, 68 + lo, 68 + lp, 68 + lq, 68 + lr, 68 + ls, 68 + lt, 68 + lu, 68 + lv, 68 + lw, 68 + lx, 68 + ly, 68 + lz, 68 + ma, 68 + mb, 68 + mc, 68 + md, 68 + me, 68 + mf, 68 + mg, 68 + mh, 68 + mi, 68 + mj, 68 + mk, 68 + ml, 68 + mm, 68 + mn, 68 + mo, 68 + mp, 68 + mq, 68 + mr, 68 + m s, 68 + mt, 68 + mu, 68 + mv, 68 + mw, 68 + mx, 68 + my, 68 + mz, 68 + na, 68 + nb, 68 + nc, 68 + nd, 68 + ne, 68 + nf, 68 + ng, 68 + nh, 68 + ni, 68 + nj, 68 + nk, 68 + nl, 68 + nm, 68 + nn, 68 + no, 68 + np, 68 + nq, 68 + nr, 68 + ns, 68 + nt, 68 + nu, 68 + nv, 68 + nw, 68 + nx, 68 + ny, 68 + nz, 68 + oa, 68 + ob, 68 + oc, 68 + od, 68 + oe, 68 + of, 68 + og, 68 + oh, 68 + oi, 68 + oj, 68 + ok, 68 + ol, 68 + om, 68 + on, 68 + oo, 68 + op, 68 + oq, 68 + or, 68 + os, 68 + ot, 68 + ou, 68 + ov, 68 + ow, 68 + ox, 68 + oy, 68 + oz, 68 + pa, 68 + pb, 68 + pc, 68 + pd, 68 + pe, 68 + pf, 68 + pg, 68 + ph, 68 + pi, 68 + pj, 68 + pk, 68 + pl, 68 + pm, 68 + pn, 68 + po, 68 + pp, 68 + pq, 68 + pr, 68 + ps, 68 + pt, 68 + pu, 68 + pv, 68 + pw, 68 + px, 68 + py, 68 + pz, 68 + qa, 68 + qb, 68 + qc, 68 + qd, 68 + qe, 68 + qf, 68 + qg, 68 + qh, 68 + qi, 68 + qj, 68 + qk, 68 + ql, 68 + qm, 68 + qn, 68 + qo, 68 + qp, 68 + qq, 68 + qr, 68 + qs, 68 + qt, 68 + qu, 68 + qv, 68 + qw, 68 + qx, 68 + qy, 68 + qz, 68 + ra, 68 + rb, 68 + rc, 68 + rd, 68 + re, 68 + rf, 68 + rg, 68 + rh, 68 + ri, 68 + rj, 68 + rk, 68 + rl, 68 + rm, 68 + rn, 68 + ro, 68 + rp, 68 + rq, 68 + rr, 68 + rs, 68 + rt, 68 + ru, 68 + rv, 68 + rw, 68 + rx, 68 + ry, 68 + rz, 68 + sa, 68 + sb, 68 + sc, 68 + sd, 68 + se, 68 + sf, 68 + sg, 68 + sh, 68 + si, 68 + sj, 68 + sk, 68 + sl, 68 + sm, 68 + sn, 68 + so, 68 + sp, 68 + sq, 68 + sr, 69 + a, 69 + b, 69 + c, 69 + d, 69 + e, 69 + f, 69 + g, 69 + h, 69 + i, 69 + j, 69 + k, 69 + l, 69 + m, 69 + n, 69 + o, 69 + p, 69 + q, 69 + r, 69 + s, 69 + t, 69 + u, 69 + v, 69 + w, 69 + x, 69 + y, 69 + z, 69 + aa, 69 + ab, 69 + ac, 69 + ad, 69 + ae, 69 + af, 69 + ag, 69 + ah, 69 + ai, 69 + aj, 69 + ak, 69 + al, 69 + am, 69 + an, 69 + ao, 69 + ap, 69 + aq, 69 + ar, 69 + as, 69 + at, 69 + au, 69 + av, 69 + aw, 69 + ax, 69 + ay, 69 + az, 69 + ba, 69 + bb, 69 + bc, 69 + bd, 69 + be, 69 + bf, 69 + bg, 69 + bh, 69 + bi, 69 + bj, 69 + bk, 69 + bl, 69 + bm, 69 + bn, 69 + bo, 69 + bp, 69 + bq, 69 + br, 69 + bs, 69 + bt, 69 + bu, 69 + bv, 69 + bw, 69 + bx, 69 + by, 69 + bz, 69 + ca, 69 + cb, 69 + cc, 69 + cd, 69 + ce, 69 + cf, 69 + cg, 69 + ch, 69 + ci, 69 + cj, 69 + ck, 69 + cl, 69 + cm, 69 + cn, 69 + co, 69 + cp, 69 + cq, 69 + cr, 69 + cs, 69 + ct, 69 + cu, 69 + cv, 69 + cw, 69 + cx, 69 + cy, 69 + cz, 69 + da, 69 + db, 69 + dc, 69 + dd, 69 + de, 69 + df, 69 + dg, 69 + dh, 69 + di, 69 + dj, 69 + dk, 69 + dl, 69 + dm, 69 + dn, 69 + do, 69 + dp, 69 + dq, 69 + dr, 69 + ds, 69 + dt, 69 + du, 69 + dv, 69 + dw, 69 + dx, 69 + dy, 69 + dz, 69 + ea, 69 + eb, 69 + ec, 69 + ed, 69 + ee, 69 + ef, 69 + eg, 69 + eh, 69 + ei, 69 + ej, 69 + ek, 69 + el, 69 + em, 69 + en, 69 + eo, 69 + ep, 69 + eq, 69 + er, 69 + es, 69 + et, 69 + eu, 69 + ev, 69 + ew, 69 + ex, 69 + ey, 69 + ez, 69 + fa, 69 + fb, 69 + fc, 69 + fd, 69 + fe, 69 + ff, 69 + fg, 69 + fh, 69 + fi, 69 + fj, 69 + fk, 69 + fl, 69 + fm, 69 + fn, 69 + fo, 69 + fp, 69 + fq, 69 + fr, 69 + fs, 69 + ft, 69 + fu, 69 + fv, 69 + fw, 69 + fx, 69 + fy, 69 + fz, 69 + ga, 69 + gb, 69 + gc, 69 + gd, 69 + ge, 69 + gf, 69 + gg, 69 + gh, 69 + gi, 69 + gj, 69 + gk, 69 + gl, 69 + gm , 69 + gn, 69 + go, 69 + gp, 69 + gq, 69 + gr, 69 + gs, 69 + gt, 69 + gu, 69 + gv, 69 + gw, 69 + gx, 69 + gy, 69 + gz, 69 + ha, 69 + hb, 69 + hc, 69 + hd, 69 + he, 69 + hf, 69 + hg, 69 + hh, 69 + hi, 69 + hj, 69 + hk, 69 + hl , 69 + hm, 69 + hn, 69 + ho, 69 + hp, 69 + hq, 69 + hr, 69 + hs, 69 + ht, 69 + hu, 69 + hv, 69 + hw, 69 + hx, 69 + hy, 69 + hz, 69 + ia, 69 + ib, 69 + ic, 69 + id, 69 + ie, 69 + if, 69 + ig, 69 + ih, 69 + ii, 69 + ij, 69 + ik , 69 + il, 69 + im, 69 + in, 69 + io, 69 + ip, 69 + iq, 69 + ir, 69 + is, 69 + it, 69 + iu, 69 + iv, 69 + iw, 69 + ix, 69 + iy, 69 + iz, 69 + ja, 69 + jb, 69 + jc, 69 + jd, 69 + je, 69 + jf, 69 + jg, 69 + jh, 69 + ji, 69 + jj , 69 + jk, 69 + jl, 69 + jm, 69 + jn, 69 + jo, 69 + jp, 69 + jq, 69 + jr, 69 + js, 69 + jt, 69 + ju, 69 + jv, 69 + jw, 69 + jx, 69 + jy, 69 + jz, 69 + ka, 69 + kb, 69 + kc, 69 + kd, 69 + ke, 69 + kf, 69 + kg, 69 + kh, 69 + ki , 69 + kj, 69 + kk, 69 + kl, 69 + km, 69 + kn, 69 + ko, 69 + kp, 69 + kq, 69 + kr, 69 + ks, 69 + kt, 69 + ku, 69 + kv, 69 + kw, 69 + kx, 69 + ky, 69 + kz, 69 + la, 69 + lb, 69 + lc, 69 + ld, 69 + le, 69 + lf, 69 + lg, 69 + lh , 69 + li, 69 + lj, 69 + lk, 69 + ll, 69 + lm, 69 + ln, 69 + lo, 69 + lp, 69 + lq, 69 + lr, 69 + ls, 69 + lt, 69 + lu, 69 + lv, 69 + lw, 69 + lx, 69 + ly, 69 + lz, 69 + ma, 69 + mb, 69 + mc, 69 + md, 69 + me, 69 + mf, 69 + mg , 69 + mh, 69 + mi, 69 + mj, 69 + mk, 69 + ml, 69 + mm, 69 + mn, 69 + mo, 69 + mp, 69 + mq, 69 + mr, 69 + ms, 69 + mt, 69 + mu, 69 + mv, 69 + mw, 69 + mx, 69 + my, 69 + mz, 69 + na, 69 + nb, 69 + nc, 69 + nd, 69 + ne, 69 + nf, 69 + ng, 69 + nh, 69 + ni, 69 + nj, 69 + nk, 69 + nl, 69 + nm, 69 + nn, 69 + no, 69 + np, 69 + nq, 69 + nr, 69 + ns, 69 + nt, 69 + nu, 69 + nv, 69 + nw, 69 + nx, 69 + ny, 69 + nz, 69 + oa, 69 + ob, 69 + oc, 69 + od, 69 + oe, 69 + of, 69 + og, 69 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so, 69 + sp, 69 + sq, 69 + sr,
70 + a, 70 + b, 70 + c, 70 + d, 70 + e, 70 + f, 70 + g, 70 + h, 70 + i, 70 + j, 70 + k, 70 + l, 70 + m, 70 + n, 70 + o, 70 + p, 70 + q, 70 + r, 70 + s, 70 + t, 70 + u, 70 + v, 70 + w, 70 + x, 70 + y, 70 + z, 70 + aa, 70 + ab, 70 + ac, 70 + ad, 70 + ae, 70 + af, 70 + ag, 70 + ah, 70 + ai, 70 + aj, 70 + ak, 70 + al, 70 + am, 70 + an, 70 + ao, 70 + ap, 70 + aq, 70 + ar, 70 + as, 70 + at, 70 + au, 70 + av, 70 + aw, 70 + ax, 70 + ay, 70 + az, 70 + ba, 70 + bb, 70 + bc, 70 + bd, 70 + be, 70 + bf, 70 + bg, 70 + bh, 70 + bi, 70 + bj, 70 + bk, 70 + bl, 70 + bm, 70 + bn, 70 + bo, 70 + bp, 70 + bq, 70 + br, 70 + bs, 70 + bt, 70 + bu, 70 + bv, 70 + bw, 70 + bx, 70 + by, 70 + bz, 70 + ca, 70 + cb, 70 + cc, 70 + cd, 70 + ce, 70 + cf, 70 + cg, 70 + ch, 70 + ci, 70 + cj, 70 + ck, 70 + cl, 70 + cm, 70 + cn, 70 + co, 70 + cp, 70 + cq, 70 + cr, 70 + cs, 70 + ct, 70 + cu, 70 + cv, 70 + cw, 70 + cx, 70 + cy, 70 + cz, 70 + da, 70 + db, 70 + dc, 70 + dd, 70 + de, 70 + df, 70 + dg, 70 + dh, 70 + di, 70 + dj, 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77 + kv, 77 + kw, 77 + kx, 77 + ky, 77 + kz, 77 + la, 77 + lb, 77 + lc, 77 + ld, 77 + le, 77 + lf, 77 + lg, 77 + lh, 77 + li, 77 + lj, 77 + lk, 77 + ll, 77 + lm, 77 + ln, 77 + lo, 77 + lp, 77 + lq, 77 + lr, 77 + ls, 77 + lt, 77 + lu, 77 + lv, 77 + lw, 77 + lx, 77 + ly, 77 + lz, 77 + ma, 77 + mb, 77 + mc, 77 + md, 77 + me, 77 + mf, 77 + mg, 77 + mh, 77 + mi, 77 + mj, 77 + mk, 77 + ml, 77 + mm, 77 + mn, 77 + mo, 77 + mp, 77 + mq, 77 + mr, 77 + ms, 77 + mt, 77 + mu, 77 + mv, 77 + mw, 77 + mx, 77 + my, 77 + mz, 77 + na, 77 + nb, 77 + nc, 77 + nd, 77 + ne, 77 + nf, 77 + ng, 77 + nh, 77 + ni, 77 + nj, 77 + nk, 77 + nl, 77 + nm , 77 + nn, 77 + no, 77 + np, 77 + nq, 77 + nr, 77 + ns, 77 + nt, 77 + nu, 77 + nv, 77 + nw, 77 + nx, 77 + ny, 77 + nz, 77 + oa, 77 + ob, 77 + oc, 77 + od, 77 + oe, 77 + of, 77 + og, 77 + oh, 77 + oi, 77 + oj, 77 + ok, 77 + ol , 77 + om, 77 + on, 77 + oo, 77 + op, 77 + oq, 77 + or, 77 + os, 77 + ot, 77 + ou, 77 + ov, 77 + ow, 77 + ox, 77 + oy, 77 + oz, 77 + pa, 77 + pb, 77 + pc, 77 + pd, 77 + pe, 77 + pf, 77 + pg, 77 + ph, 77 + pi, 77 + pj, 77 + pk , 77 + pl, 77 + pm, 77 + pn, 77 + po, 77 + pp, 77 + pq, 77 + pr, 77 + ps, 77 + pt, 77 + pu, 77 + pv, 77 + pw, 77 + px, 77 + py, 77 + pz, 77 + qa, 77 + qb, 77 + qc, 77 + qd, 77 + qe, 77 + qf, 77 + qg, 77 + qh, 77 + qi, 77 + qj , 77 + qk, 77 + ql, 77 + qm, 77 + qn, 77 + qo, 77 + qp, 77 + qq, 77 + qr, 77 + qs, 77 + qt, 77 + qu, 77 + qv, 77 + qw, 77 + qx, 77 + qy, 77 + qz, 77 + ra, 77 + rb, 77 + rc, 77 + rd, 77 + re, 77 + rf, 77 + rg, 77 + rh, 77 + ri , 77 + rj, 77 + rk, 77 + rl, 77 + rm, 77 + rn, 77 + ro, 77 + rp, 77 + rq, 77 + rr, 77 + rs, 77 + rt, 77 + ru, 77 + rv, 77 + rw, 77 + rx, 77 + ry, 77 + rz, 77 + sa, 77 + sb, 77 + sc, 77 + sd, 77 + se, 77 + sf, 77 + sg, 77 + sh , 77 + si, 77 + sj, 77 + sk, 77 + sl, 77 + sm, 77 + sn, 77 + so, 77 + sp, 77 + sq, 77 + sr, 78 + a, 78 + b, 78 + c, 78 + d, 78 + e, 78 + f, 78 + g, 78 + h, 78 + i, 78 + j, 78 + k, 78 + l, 78 + m, 78 + n, 78 + o , 78 + p, 78 + q, 78 + r, 78 + 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79 + bn, 79 + bo, 79 + bp, 79 + bq, 79 + br, 79 + bs, 79 + bt, 79 + bu, 79 + bv, 79 + bw, 79 + bx, 79 + by, 79 + bz, 79 + ca, 79 + cb, 79 + cc, 79 + cd, 79 + ce, 79 + cf, 79 + cg, 79 + ch, 79 + ci, 79 + cj, 79 + ck, 79 + cl, 79 + cm, 79 + cn, 79 + co, 79 + cp, 79 + cq, 79 + cr, 79 + cs, 79 + ct, 79 + cu, 79 + cv, 79 + cw, 79 + cx, 79 + cy, 79 + cz, 79 + da, 79 + db, 79 + dc, 79 + dd, 79 + de, 79 + df, 79 + dg, 79 + dh, 79 + di, 79 + dj, 79 + dk, 79 + dl, 79 + dm, 79 + dn, 79 + do, 79 + dp, 79 + dq, 79 + dr, 79 + ds, 79 + dt, 79 + du, 79 + dv, 79 + dw, 79 + dx, 79 + dy, 79 + dz, 79 + ea, 79 + eb, 79 + ec, 79 + ed, 79 + ee, 79 + ef, 79 + eg, 79 + eh, 79 + ei, 79 + ej, 79 + ek, 79 + el, 79 + em, 79 + en, 79 + eo, 79 + ep, 79 + eq, 79 + er, 79 + es, 79 + et, 79 + eu, 79 + ev, 79 + ew, 79 + ex, 79 + ey, 79 + ez, 79 + fa, 79 + fb, 79 + fc, 79 + fd, 79 + fe, 79 + ff, 79 + fg, 79 + fh, 79 + fi, 79 + fj, 79 + fk, 79 + fl, 79 + fm, 79 + fn, 79 + fo, 79 + fp, 79 + fq, 79 + fr, 79 + fs, 79 + ft, 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ka, 79 + kb, 79 + kc, 79 + kd, 79 + ke, 79 + kf, 79 + kg, 79 + kh, 79 + ki , 79 + kj, 79 + kk, 79 + kl, 79 + km, 79 + kn, 79 + ko, 79 + kp, 79 + kq, 79 + kr, 79 + ks, 79 + kt, 79 + ku, 79 + kv, 79 + kw, 79 + kx, 79 + ky, 79 + kz, 79 + la, 79 + lb, 79 + lc, 79 + ld, 79 + le, 79 + lf, 79 + lg, 79 + lh , 79 + li, 79 + lj, 79 + lk, 79 + ll, 79 + lm, 79 + ln, 79 + lo, 79 + lp, 79 + lq, 79 + lr, 79 + ls, 79 + lt, 79 + lu, 79 + lv, 79 + lw, 79 + lx, 79 + ly, 79 + lz, 79 + ma, 79 + mb, 79 + mc, 79 + md, 79 + me, 79 + mf, 79 + mg , 79 + mh, 79 + mi, 79 + mj, 79 + mk, 79 + ml, 79 + mm, 79 + mn, 79 + mo, 79 + mp, 79 + mq, 79 + mr, 79 + ms, 79 + mt, 79 + mu, 79 + mv, 79 + mw, 79 + mx, 79 + my, 79 + mz, 79 + na, 79 + nb, 79 + nc, 79 + nd, 79 + ne, 79 + nf, 79 + ng, 79 + nh, 79 + ni, 79 + nj, 79 + nk, 79 + nl, 79 + nm, 79 + nn, 79 + no, 79 + np, 79 + nq, 79 + nr, 79 + ns, 79 + nt, 79 + nu, 79 + nv, 79 + nw, 79 + nx, 79 + ny, 79 + nz, 79 + oa, 79 + ob, 79 + oc, 79 + od, 79 + oe, 79 + of, 79 + og, 79 + oh, 79 + oi, 79 + oj, 79 + ok, 79 + ol, 79 + om, 79 + on, 79 + oo, 79 + op, 79 + oq, 79 + or, 79 + os, 79 + ot, 79 + ou, 79 + ov, 79 + ow, 79 + ox, 79 + oy, 79 + oz, 79 + pa, 79 + pb, 79 + pc, 79 + pd, 79 + pe, 79 + pf, 79 + pg, 79 + ph, 79 + pi, 79 + pj, 79 + pk, 79 + pl, 79 + pm, 79 + pn, 79 + po, 79 + pp, 79 + pq, 79 + pr, 79 + ps, 79 + pt, 79 + pu, 79 + pv, 79 + pw, 79 + px, 79 + py, 79 + pz, 79 + qa, 79 + qb, 79 + qc, 79 + qd, 79 + qe, 79 + qf, 79 + qg, 79 + qh, 79 + qi, 79 + qj, 79 + qk, 79 + ql, 79 + qm, 79 + qn, 79 + qo, 79 + qp, 79 + qq, 79 + qr, 79 + qs, 79 + qt, 79 + qu, 79 + qv, 79 + qw, 79 + qx, 79 + qy, 79 + qz, 79 + ra, 79 + rb, 79 + rc, 79 + rd, 79 + re, 79 + rf, 79 + rg, 79 + rh, 79 + ri, 79 + rj, 79 + rk, 79 + rl, 79 + rm, 79 + rn, 79 + ro, 79 + rp, 79 + rq, 79 + rr, 79 + rs, 79 + rt, 79 + ru, 79 + rv, 79 + rw, 79 + rx, 79 + ry, 79 + rz, 79 + sa, 79 + sb, 79 + sc, 79 + sd, 79 + se, 79 + sf, 79 + sg, 79 + sh, 79 + si, 79 + sj, 79 + sk, 79 + sl, 79 + sm, 79 + sn, 79 + so, 79 + sp, 79 + sq, 79 + sr.
本発明組成物及び本発明方法における一般式(1)及び一般式(2)で表される化合物と、化合物群Aより選ばれる化合物との好適な混合割合は、一般式(1)及び一般式(2)で表される化合物の1重量部に対して、化合物群Aから選ばれる化合物は通常0.001〜1000重量部、好ましくは0.01〜100重量部、より好ましくは0.1〜10重量部である。 Suitable mixing ratios of the compound represented by the general formula (1) and the general formula (2) in the composition of the present invention and the method of the present invention and the compound selected from the compound group A are the general formula (1) and the general formula. The compound selected from the compound group A is usually 0.001 to 1000 parts by weight, preferably 0.01 to 100 parts by weight, more preferably 0.1 to 1 part by weight of the compound represented by (2). 10 parts by weight.
本発明組成物及び本発明方法における有効成分化合物の好ましい処理量は、防除すべき対象病害虫の種類などにより左右されるが、通常一般式(1)及び一般式(2)で表される化合物が0.1〜1000gai/ha、化合物群Aから選ばれる化合物が0.1〜1000gai/haであり、好ましくは前者が1〜300gai/haであり、後者が1〜300gai/haである。 The preferred treatment amount of the active ingredient compound in the composition of the present invention and the method of the present invention depends on the type of the target pest to be controlled, but the compounds represented by the general formulas (1) and (2) are usually used. The compound selected from 0.1 to 1000 gai / ha and the compound group A is 0.1 to 1000 gai / ha, preferably the former is 1 to 300 gai / ha, and the latter is 1 to 300 gai / ha.
本発明組成物及び本発明方法は、農園芸作物および樹木などを加害するいわゆる農業害虫、農業病害、家畜家禽類に寄生するいわゆる家畜害虫、家屋等の人間の生活環境で悪影響を与えるいわゆる衛生害虫、および同様の場面で発生加害するダニ類や線虫類に対して適用できる。本発明組成物及び本発明方法を用いて防除しうる害虫、ダニ類、線虫類、病害には具体的には次に示すものがあるが、それらのみに限定されるものではない。 The composition of the present invention and the method of the present invention are so-called agricultural pests that harm agricultural and horticultural crops and trees, agricultural diseases, so-called livestock pests parasitic on livestock and poultry, and so-called sanitary pests that adversely affect human living environments such as houses. It can be applied to mites and nematodes that occur and harm in similar situations. Specific examples of pests, mites, nematodes, and diseases that can be controlled using the composition of the present invention and the method of the present invention include the following, but are not limited thereto.
害虫としては、コナガ(Plutella xylostella)、タマナヤガ(Agrotis ipsilon)、カブラヤガ(Agrotis segetum)、オオタバコガ(Helicoverpa armigera)、タバコガ(Helicoverpa assulta)、コットンボールワーム(Helicoverpa zea)、タバコバッドワーム(Heliothis virescens)、ヨトウガ(Mamestra brassicae)、フタオビコヤガ(Naranga aenescens)、タマナギンウワバ(Plusia nigrisigna)、アワヨトウ(Pseudaletia separata)、シロイチモジヨトウ(Spodoptera exigua)、ハスモンヨトウ(Spodoptera litura)、コットンリーフワーム(Spodoptera littoralis)、フォールアーミーワーム(Spodoptera frugiperda)、サザンアーミーワーム(Spodoptera eridania)、トマトホーンワーム(Manduca quinquemaculata)、タバコホーンワーム(Manduca sexta)、グレープベリーモス(Endopiza viteana)、ギンモンハモグリガ(Lyonetia prunifoliella malinella)、キンモンホソガ(Phyllonorycter ringoneella)、ミカンハモグリガ(Phyllocnistis citrella)、ワタアカミムシ(Pectinophora gossypiella)、モモシンクイガ(Carposina niponensis)、リンゴコカクモンハマキ(Adoxophyes orana faciata)、チャノコカクモンハマキ(Adoxophyes honmai)、チャハマキ(Homona magnamina)、コドリンガ(Cydla pomonella)、ナシヒメシンクイ(Grapholita molesta)、ニカメイガ(Chilo suppressalis)、コブノメイガ(Cnaphalocrocis medinalis)、ハイマダラノメイガ(Hellula undalis)、ヨーロピアンコーンボーラー(Ostrinia nubilalis)、ソイビーンルーパー(Pseudoplusia includens)、イラクサギンウワバ(Trichoplusia ni)、アメリカシロヒトリ(Hyphantria cunea)、モンシロチョウ(Pieris rapae crucivora)、イチモンジセセリ(Parnara guttata)等の鱗翅目害虫、
ドウガネブイブイ(Anomala cuprea)、ヒメコガネ(Anomala rufocuprea)、マメコガネ(Popillia japonica)、コロラドポテトビートル(Lepinotarsa decemlineata)、インゲンテントウ(Epilachna varivestis)、カンシャクシコメツキ(Melanotus tamsuyensis)、タバコシバンムシ(Lasioderma serricorne)、ヒメヒラタケシキスイ(Epuraea domina)、ニジュウヤホシテントウ(Henosepilachna vigintioctopunctata)、チャイロコメノゴミムシダマシ(Tenebrio molitor)、コクヌストモドキ(Tribolium castaneum)、ゴマダラカミキリ(Anoplophora malasiaca)、マツノマダラカミキリ(Monochamus alternatus)、アズキゾウムシ(Callosobruchus chinensis)、ウリハムシ(Aulacophora femoralis)、イネドロオイムシ(Oulema oryzae)、キスジノミハムシ(Phyllotreta striolata)、アリモドキゾウムシ(Cylas formicarius)、ワタミゾウムシ(Anthonomus grandis)、イネゾウムシ(Ethinocnemus squameus)、アルファルファタコゾウムシ(Hypera postica)、イネミズゾウムシ(Lissorhoptrus oryzophilus)、コクゾウ(Sitophilus zeamais)、シバオサゾウムシ(Sphenophrus venatus vestius)、グラナリーウィービル(Sitophilus granarius)、サザンコーンルートワーム(Diabrotica undecimpunctata)、ウエスタンコーンルートワーム(Diabrotica virgifera)、ノーザンコーンルートワーム(Diabrotica barberi)、アオバアリガタハネカクシ(Paederus fuscipes)等の鞘翅目害虫、
ナガメ(Eurydema rugosa)、シラホシカメムシ(Eysarcoris ventralis)、クサギカメムシ(Halyomorpha mista)、ミナミアオカメムシ(Nezara viridula)、クモヘリカメムシ(Leptocorisa chinensis)、ホソヘリカメムシ(Riptortus clavatus)、コバネヒョウタンナガカメムシ(Togo hemipterus)、ターニッシュドプラントバグ(Lygus lineolaris)、コットンフリーホッパー(Psuedatomoscelis seriatus)、ツツジグンバイ(Stephanitis pyrioides)、フタテンオオヨコバイ(Epiacanthus stramineus)、チャノミドリヒメヨコバイ(Empoasca onukii)、ポテトリーフホッパー(Empoasca fabae)、ツマグロヨコバイ(Nephotettix cinctinceps)、ヒメトビウンカ(Laodelphax striatellus)、トビイロウンカ(Nilaparvata lugens)、セジロウンカ(Sogatella furcifera)、ミカンキジラミ(Trioza erytreae)、ナシキジラミ(Psylla pyrisuga)、シルバーリーフコナジラミ(Bemisia argentifolii)、タバココナジラミ(Bemisia tabaci)、ミカンコナジラミ(Dialeurodes citri)、オンシツコナジラミ(Trialeurodes vaporariorum)、ワタアブラムシ(Aphis gossypii)、ユキヤナギアブラムシ(Aphis pomi)、モモアカアブラムシ(Myzus persicae)、オオワラジカイガラムシ(Drosicha corpulenta)、イセリアカイガラムシ(Icerya purchasi)、ミカンコナカイガラムシ(Planococcus citri)、クワコナカイガラムシ(Pseudococcus comstocki)、ルビーロウムシ(Ceroplastes rubens)、ヤノネカイガラムシ(Unaspis yanonensis)、トコジラミ(Cimex lectularius)等の半翅目害虫、
ミカンキイロアザミウマ(Frankliniella occidentalis)、ヒラズハナアザミウマ(Frankliniella intonsa)、チャノキイロアザミウマ(Scirtothrips dorsalis)、ミナミキイロアザミウマ(Thrips palmi)、ネギアザミウマ(Thrips tabaci)等の総翅目害虫、
ミカンコミバエ(Dacus dorsalis)、ウリミバエ(Dacus cucurbitae)、チチュウカイミバエ(Ceratitis capitata)、イネヒメハモグリバエ(Hydrellia griseola)、ナスハモグリバエ(Liriomyza bryoniae)、マメハモグリバエ(Liriomyza trifolii)、タネバエ(Hylemya platura)、アップルマゴット(Rhagoletis pomonella)、ヘシアンフライ(Mayetiola destructor)、イエバエ(Musca domestica)、サシバエ(Stomoxys calcitrans)、ヒツジシラミバエ(Melophagus ovinus)、ウシバエ(Hypoderma bovis)、キスジウシバエ(Hypoderma lineatum)、ヒツジバエ(Oestrus ovis)、ツェツェバエ(Glossina palpalis, Glossina morsitans)、キアシオオブユ(Prosimulium yezoensis)、ウシアブ(Tabanus trigonus)、オオチョウバエ(Telmatoscopus albipunctatus)、トクナガヌカカ(Leptoconops nipponensis)、アカイエカ(Culex pipiens pallens)、ネッタイシマカ(Aedes aegypti)、ヒトスジシマカ(Aedes albopicutus)、シナハマダラカ(Anopheles hyracanus sinesis)等の双翅目害虫、
クリハバチ(Apethymus kuri)、カブラハバチ(Athalia rosae japonensis)、マツノキハバチ(Neodiprion sertifer)、グンタイアリ(Eciton burchelli, Eciton schmitti)、クロオオアリ(Camponotus japonicus)、オオスズメバチ(Vespa mandarina)、ブルドックアント(Myrmecia spp.)、ファイヤーアント類(Solenopsis spp.)、ファラオアント(Monomorium pharaonis)等の膜翅目害虫、
クロゴキブリ(Periplaneta fuliginosa)、ヤマトゴキブリ(Periplaneta japonica)、チャバネゴキブリ(Blattella germanica)等の網翅目害虫、
エンマコオロギ(Teleogryllus emma)、ケラ(Gryllotalpa africana)、トノサマバッタ(Locusta migratoria)、コバネイナゴ(Oxya yezoensis)、サバクワタリバッタ(Schistocerca gregaria)等の直翅目害虫、
イエシロアリ(Coptotermes formosanus)、ヤマトシロアリ(Reticulitermes speratus)、タイワンシロアリ(Odontotermes formosanus)等のシロアリ目害虫、
ネコノミ(Ctenocephalidae felis)、ヒトノミ(Pulex irritans)、ケオプスネズミノミ(Xenopsylla cheopis)等の等翅目害虫、
ニワトリオオハジラミ(Menacanthus stramineus)、ウシハジラミ(Bovicola bovis)等のハジラミ目害虫、
ウシジラミ(Haematopinus eurysternus)、ブタジラミ(Haematopinus suis)、ウシホソジラミ(Linognathus vituli)、ケブカウシジラミ(Solenopotes capillatus)等のシラミ目害虫、
ミカンハダニ(Panonychus citri)、リンゴハダニ(Panonychus ulmi)、カンザワハダニ(Tetranychus kanzawai)、ナミハダニ(Tetranychus urticae)等のハダニ類、
チャノナガサビダニ(Acaphylla theae)、ミカンサビダニ(Aculops pelekassi)、ニセナシサビダニ(Eriophyes chibaensis)、チューリップサビダニ(Aceria tulipae)等のフシダニ類、
チャノホコリダニ(Polyphaotarsonemus latus)、シクラメンホコリダニ(Steneotarsonemus pallidus)等のホコリダニ類、
ケナガコナダニ(Tyrophagus putrescentiae)、ロビンネダニ(Rhizoglyphus robini)等のコナダニ類、
ミツバチヘギイタダニ(Varroa jacobsoni)等のハチダニ類、
オウシマダニ(Boophilus microplus)、フタトゲチマダニ(Haemaphysalis longicornis)等のマダニ類、
ヒツジキュウセンダニ(Psoroptes ovis)等のキュウセンダニ類、
ヒゼンダニ(Sarcoptes scabiei)等のヒゼンダニ類、
オカダンゴムシ(Armadillidium vulgare)等の甲殻類、
キタネグサレセンチュウ(Prathylenchus penetrans)、クルミネグサレセンチュウ(Prathylenchus vulnus)、ジャガイモシストセンチュウ(Globodera rostochiensis)、ダイズシストセンチュウ(Heterodera glycines)、キタネコブセンチュウ(Meloidogyne hapla)、サツマイモネコブセンチュウ(Meloidogyne incognita)、マツノザイセンチュウ(Bursaphelenchus lignicolus)等の線虫類、
スクミリンゴガイ(Ponacea canaliculata)、ナメクジ(Incilaria bilineata)、ウスカワマイマイ(Acusta despecta sieboldiana)、ミスジマイマイ(Euhadra peliomphala)等の軟体動物などが挙げられる。
Pests include Plutella xylostella, Agrotis ipsilon, Agrotis segetum, Helicoverpa armigera, Tobacco moth (Helicoverpa assulta), Cotton ball worm (Helicoverpa zea), Tobacco bad worm (senior vires) Mamestra brassicae, Naranga aenescens, Tamiaginu waiba (Plusia nigrisigna), Pseudaletia separata, Spodoptera exigua, Spodoptera litura, Spodoptera litura, Spodoptera litura ), Southern army worm (Spodoptera eridania), Tomato horn worm (Manduca quinquemaculata), Tobacco horn worm (Manduca sexta), Grapeberry moss (Endopiza viteana), Ginmon peach moth (Lyonetia prunifol) iella malinella, Phyllonorycter ringoneella, Phylocloctistis citrella, Cottonworm, Pectinophora gossypiella, Carposina niponensis, Adoxophyes orana faciata, Adoxophyes orana faciata Homona magnamina, Codlinga (Cydla pomonella), Nashihimeshinsukui (Grapholita molesta), Nikameiga (Chilo suppressalis), Cnaphalocrocis medinalis, Hamelula undalis, European corn borer (Ostrinia nubilis) Lepidopterous insects such as nettle butterfly (Trichoplusia ni), white butterfly (Hyphantria cunea), white butterfly (Pieris rapae crucivora), parrotara guttata, etc.,
Douganebububu (Anomala cuprea), Japanese beetle (Anomala rufocuprea), Japanese beetle (Popillia japonica), Colorado potato beetle (Lepinotarsa decemlineata), Green beetle (Epilachna varivestis), Japanese horned beetle (Mdernotsis serum) Pepper (Epuraea domina), Henosepilachna vigintioctopunctata, Tenebrio molitor, Tribobrium castaneum, Monstros brutum (Anoplophora malasiaca) ), Leaf beetle (Aulacophora femoralis), rice beetle (Oulema oryzae), Phyllotreta striolata, Cylas formicarius, cotton weevil Anthonomus grandis), weevil (Ethinocnemus squameus), alfalfa weevil (Hypera postica), rice weevil (Lissorhoptrus oryzophilus), horned weevil (Sitophilus zeamais), siberian weevil (Sphenophrus venatus vestius) Crustacea pests such as root worms (Diabrotica undecimpunctata), western corn root worms (Diabrotica virgifera), northern corn root worms (Diabrotica barberi), Paederus fuscipes, etc.
Sea turtle (Eurydema rugosa), White-headed bug (Eysarcoris ventralis), White-headed bug (Halyomorpha mista), Southern stink bug (Nezara viridula), Spider-headed bug (Leptocorisa chinensis), White-headed bug (Riptortus clam) hemipterus), tarnished plant bug (Lygus lineolaris), cotton-free hopper (Psuedatomoscelis seriatus), azalea, stephanitis pyrioides, Epiacanthus stramineus, Empoasca onukii, potato leaf Empoasca fabae), leafhopper leafhopper (Nephotettix cinctinceps), leafhopper (Laodelphax striatellus), leafhopper (Nilaparvata lugens), leafhopper (Sogatella furcifera), citrus leafworm (Trioza yltrera), pear Silver leaf whiteflies (Bemisia argentifolii), tobacco whiteflies (Bemisia tabaci), citrus whiteflies (Dialeurodes citri), white-footed whiteflies (Trialeurodes vaporariorum), cotton aphids (Aphis gossypii), snowy white aphids (Aphiszu pears) Drosicha corpulenta, Icerya purchasi, Pterococcus citri, Pseudococcus comstocki, Rubi rot (Ceroplastes rubens), Unis yanim Hemiptera pests, etc.
Thrips palmi, Thrips tabici, Thrips tabaci, Thrips tabaci, Thrips tabaci, Thrips tabaci, Thrips tabaci, Thrips tabaci
Fruit fly (Dacus dorsalis), fruit fly (Dacus cucurbitae), fruit fly (Ceratitis capitata), green leaf fly (Hydrellia griseola), eggplant fly (Liriomyza bryoniae), bean leaflet (Liriomyza flies) pomonella, Hessian flies (Mayetiola destructor), house flies (Musca domestica), flies (Stomoxys calcitrans), sheep flies (Melophagus ovinus), bullflies (Hypoderma bovis), duck flies (Hypoderma lineatum), sheep vis (Oest ovis vis) , Glossina morsitans), Prosimulium yezoensis, Cattle fly (Tabanus trigonus), Flyfly (Telmatoscopus albipunctatus), Leptoconops nipponensis, Culex pipiens pallens, Netta Island shape (Aedes aegypti), Aedes albopictus (Aedes albopicutus), Anopheles sinensis (Anopheles hyracanus sinesis) Diptera, such as,
Bumblebee (Apethymus kuri), Bee (Athalia rosae japonensis), Bee (Neodiprion sertifer), Guntai ant (Eciton burchelli, Eciton schmitti), Black-headed ant (Camponotus japonicus), Mystic ant (Vespa) Hymenoptera (Solenopsis spp.), Pharaoh ant (Monomorium pharaonis), etc.
Reticulate pests such as black cockroach (Periplaneta fuliginosa), cockroach (Periplaneta japonica), German cockroach (Blattella germanica),
Direct insect pests such as Teleogryllus emma, Gryllotalpa africana, Locusta migratoria, Oxya yezoensis, Sistocerca gregaria,
Termite pests such as termites (Coptotermes formosanus), Yamato termites (Reticulitermes speratus), Taiwan termites (Odontotermes formosanus),
Pests such as cat fleas (Ctenocephalidae felis), human fleas (Pulex irritans), Xenopsylla cheopis
White-eye pests such as chicken lice (Menacanthus stramineus), bovine lice (Bovicola bovis),
Lice insect pests such as cattle lice (Haematopinus eurysternus), pig lice (Haematopinus suis), cattle white lice (Linognathus vituli), horn beetle (Solenopotes capillatus),
Spider mites (Panonychus citri), apple spider mites (Panonychus ulmi), Kanzawa spider mites (Tetranychus kanzawai), spider mites (Tetranychus urticae) and other spider mites,
Scarlet mites (Acaphylla theae), Scarlet mites (Aculops pelekassi), Scarlet mite (Eriophyes chibaensis), Tulip mites (Aceria tulipae), etc.,
Dust mites such as tea dust mite (Polyphaotarsonemus latus), cyclamen dust mite (Steneotarsonemus pallidus),
Acarid mites (Tyrophagus putrescentiae), Robin mite (Rhizoglyphus robini),
Bee mites such as honeybee mite (Varroa jacobsoni),
Tick such as Boophilus microplus, Haemaphysalis longicornis,
Cucumber mites such as sheep cucumber mites (Psoroptes ovis),
Spider mites such as Scaroptes scabiei,
Crustaceans such as Armadillidium vulgare,
Kitty-necked nematode (Prathylenchus penetrans), Chermine-gulled nematode (Prathylenchus vulnus), Potato cyst nematode (Globodera rostochiensis), Soybean cyst nematode (Heterodera glycines), Kita-neko-nen-chu-sen-chu (Namida) Nematodes such as (Bursaphelenchus lignicolus),
Examples include molluscs such as Ponacea canaliculata, slug (Incilaria bilineata), Acusta despecta sieboldiana, and Euhadra peliomphala.
一方、病害としては、イネのいもち病(Pyricularia oryzae)、ごま葉枯病(Cochliobolus miyabeanus)、紋枯病(Rhizoctonia solani)、ムギ類のうどんこ病(Erysiphe graminis f.sp.hordei, f.sp.tritici)、斑葉病(Pyrenophoragraminea)、網斑病(Pyrenophora teres)、赤かび病(Gibberella zeae)、さび病(Puccinia striiformis, P.graminis, P.recondita, P.hordei)、雪腐病(Tipula sp., Micronectriella nivais)、裸黒穂病(Ustilago tritici, U.nuda)、アイスポット(Pseudocercosporella herpotrichoides)、雲形病(Rhynchosporium secalis)、葉枯病(Septoria tritici)、ふ枯病(Leptosphaeria nodorum)、カンキツの黒点病(Diaporthe citri)、そうか病(Elsinoe fawcetti)、果実腐敗病(Penicillium digitalum, P.italicum)、リンゴのモニリア病(Selerotinia mali)、腐らん病(Valsa mali)、うどんこ病(Podosphaera lcucotricha)、斑点落葉病(Alternaria mali)、黒星病(Venturia inaequalis)、ナシの黒星病(Venturia nashicola)、黒斑病(Alternaria kikuchiana)、赤星病(Gymnosporangium haracanum)、モモの灰星病(Sclerolinia cinerea)、黒星病(Cleadosporium carpophilum)、フォモプシス腐敗病(Phomopsis sp.)、ブドウのべと病(Plasmopara viticola)、黒とう病(Elsinoe ampelina)、晩腐病(Glomerella cingulata)、うどんこ病(Uncinula necator)、さび病(Phakopsora ampelopsidis)、カキの炭そ病(Gloeosporium kakj)、落葉病(Cercospora kakj,Mycosphaerella nawae)、ウリ類のべと病(Pseudoperenospora cubensis)、炭そ病(Colletotrichum lagenarium)、うどんこ病(Sphaerotheca fuliginea)、つる枯病(Mycosphaerella melonis)、トマトの疫病(Phytophthora infestans)、輪紋病(Alternaria solani)、葉かび病(Cladosporium fulvum)、ナスの褐紋病(Phomopsis vexans)、うどんこ病(Erysiphe cichoracoarum)、アブラナ科野菜の黒斑病(Alternaria japonica)、白斑病(Cercosporella brassicae)、ネギのさび病(Puccinia allii)、ダイズの紫斑病(Cercospora kikuchii)、黒とう病(Elsinoe glycines)、黒点病(Diaporthe phaseololum)、インゲンの炭そ病(Colletotrichum lindemuthianum)、ラッカセイの黒渋病(Mycosphaerella personatum)、褐斑病(Cercospora arachidicola)、エンドウのうどんこ病(Erysiphe pisi)、ジャガイモの夏疫病(Alternaria solani)、イチゴのうどんこ病(Sphaerotheca humuli)、チャの網もち病(Exobasidium reticulatum)、白星病(Elsinoe leucospila)、タバコの赤星病(Alternaria lingipes)、うどんこ病(Erysiphe cichoracearum)、炭そ病(Colletotrichum tabacum)、テンサイの褐斑病(Cercospora beticola)、バラの黒星病(Diplocarpon rosae)、うどんこ病(Sphaerotheca pannosa)、キクの褐斑病(Septoria chrysanthemiindici)、白さび病(Puccinia horiana)、種々の作物の灰色かび病(Botrytis cinerea)および種々の作物の菌核病(Sclerotinia sclerotiorum)等が挙げられる。 On the other hand, diseases include rice blast (Pyricularia oryzae), sesame leaf blight (Cochliobolus miyabeanus), blight (Rhizoctonia solani), wheat powdery mildew (Erysiphe graminis f.sp.hordei, f.sp. .tritici), leafy leaf disease (Pyrenophoragraminea), net leaf disease (Pyrenophora teres), leaf blight (Gibberella zeae), rust disease (Puccinia striiformis, P.graminis, P.recondita, P.hordei), snow rot ( Tipula sp., Micronectriella nivais), Bare Scab (Ustilago tritici, U.nuda), Eye spot (Pseudocercosporella herpotrichoides), Cloud disease (Rhynchosporium secalis), Leaf blight (Septoria tritici), Blight (Leptosphaeria nodorum), Citrus sunspot (Diaporthe citri), scab (Elsinoe fawcetti), fruit rot (Penicillium digitalum, P.italicum), apple monilia (Selerotinia mali), rot (Valsa mali), powdery mildew (Podosphaera) lcucotricha), spotted leaf disease (Alternaria mali) , Black streak (Venturia inaequalis), pear black streak (Venturia nashicola), black spot (Alternaria kikuchiana), red streak (Gymnosporangium haracanum), peach streak (Sclerolinia cinerea), black streak (Cleadosporium carpophilum), fomo Rot (Phomopsis sp.), Grape downy mildew (Plasmopara viticola), black scab (Elsinoe ampelina), late rot (Glomerella cingulata), powdery mildew (Uncinula necator), rust (Phakopsora ampelopsidis), oyster Anthracnose (Gloeosporium kakj), deciduous leaf disease (Cercospora kakj, Mycosphaerella nawae), downy mildew (Pseudoperenospora cubensis), anthracnose (Colletotrichum lagenarium), powdery mildew (Sphaerotheca fuliginea), vine blight Mycosphaerella melonis), plague of tomatoes (Phytophthora infestans), ring rot (Alternaria solani), leaf mold (Cladosporium fulvum), brown rot of eggplant (Phomopsis vexans), powdery mildew (Erysiphe cichora) coarum), cruciferous vegetable black spot (Alternaria japonica), white spot (Cercosporella brassicae), leek rust (Puccinia allii), soybean purple spot (Cercospora kikuchii), black scab (Elsinoe glycines), sunspot (Diaporthe phaseololum), bean anthracnose (Colletotrichum lindemuthianum), black peanut (Mycosphaerella personatum), brown spot (Cercospora arachidicola), pea powdery mildew (Erysiphe pisi), potato summer plague (Alternaria solani) ), Strawberry powdery mildew (Sphaerotheca humuli), tea net blast (Exobasidium reticulatum), white star disease (Elsinoe leucospila), tobacco red star disease (Alternaria lingipes), powdery mildew (Erysiphe cichoracearum), anthracnose ( Colletotrichum tabacum), sugar beet brown spot (Cercospora beticola), rose black spot (Diplocarpon rosae), powdery mildew (Sphaerotheca pannosa), chrysanthemum brown spot (Septoria ch rysanthemiindici), white rust (Puccinia horiana), various crops of gray mold (Botrytis cinerea) and various crops of mycosis (Sclerotinia sclerotiorum).
本発明の一般式(1)及び一般式(2)で表される置換ベンズアニリド化合物は、例えば以下の方法により製造することが出来る。 The substituted benzanilide compound represented by the general formula (1) and the general formula (2) of the present invention can be produced, for example, by the following method.
製造法A Manufacturing method A
一般式(4)[式中、G, W1, W2, X, Y, R4, R5, R6, l, m及びnは前記と同じ意味を表す。]で表される化合物と一般式(5)[式中、R2及びR3は前記と同じ意味を表す。]で表される化合物とを、該反応に対して不活性な溶媒中又は無溶媒にて、必要ならば触媒の存在下、反応させることにより、一般式(1)においてR1が水素原子である一般式(1-1)[式中、G, W1, W2, X, Y, R2, R3, R4, R5, R6, l, m及びnは前記と同じ意味を表す。]で表される本発明化合物を得ることができる。 General formula (4) [In the formula, G, W 1 , W 2 , X, Y, R 4 , R 5 , R 6 , l, m, and n represent the same meaning as described above. And a compound represented by the general formula (5): wherein R 2 and R 3 have the same meaning as described above. In a solvent inert to the reaction or in the absence of a solvent, if necessary, in the presence of a catalyst, R 1 is a hydrogen atom in the general formula (1). A general formula (1-1) wherein G, W 1 , W 2 , X, Y, R 2 , R 3 , R 4 , R 5 , R 6 , l, m and n have the same meaning as above. Represent. This invention compound represented by this can be obtained.
反応基質の量は、一般式(4)で表される化合物1当量に対して1〜50当量の一般式(5)で表される化合物を用いることができる。 As the amount of the reaction substrate, 1 to 50 equivalents of the compound represented by the general formula (5) can be used per 1 equivalent of the compound represented by the general formula (4).
溶媒を用いる場合、用いられる溶媒としては反応の進行を阻害しないものであれば何でもよく、例えばベンゼン、トルエン、キシレン等の芳香族炭化水素類、ヘキサン、ヘプタン等の脂肪族炭化水素類、シクロヘキサン等の脂環式炭化水素類、クロロベンゼン、ジクロロベンゼン等の芳香族ハロゲン化炭化水素類、ジクロロメタン、クロロホルム、四塩化炭素、1,2-ジクロロエタン、1,1,1-トリクロロエタン、トリクロロエチレン、テトラクロロエチレン等の脂肪族ハロゲン化炭化水素類、ジエチルエーテル、1,2-ジメトキシエタン、テトラヒドロフラン、1,4-ジオキサン等のエーテル類、酢酸エチル、プロピオン酸エチル等のエステル類、ジメチルホルムアミド、ジメチルアセトアミド、N-メチル-2-ピロリドン等のアミド類、ギ酸、酢酸、プロピオン酸等のカルボン酸類、トリエチルアミン、トリブチルアミン、N、N-ジメチルアニリン等のアミン類、ピリジン、ピコリン等のピリジン類、メタノール、エタノール、エチレングリコール等のアルコール類、アセトニトリル、ジメチルスルホキシド、スルホラン、1,3-ジメチル-2-イミダゾリジノン及び水等が挙げられる。これらの溶媒は単独で用いても、これらのうちの2種類以上を混合して用いてもよい。 In the case of using a solvent, any solvent may be used as long as it does not inhibit the progress of the reaction. For example, aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as hexane and heptane, cyclohexane, etc. Alicyclic hydrocarbons, aromatic halogenated hydrocarbons such as chlorobenzene and dichlorobenzene, fats such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,1,1-trichloroethane, trichloroethylene and tetrachloroethylene Group halogenated hydrocarbons, ethers such as diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran and 1,4-dioxane, esters such as ethyl acetate and ethyl propionate, dimethylformamide, dimethylacetamide, N-methyl- Amides such as 2-pyrrolidone, formic acid, acetic acid, propylene Carboxylic acids such as on acid, amines such as triethylamine, tributylamine, N, N-dimethylaniline, pyridines such as pyridine and picoline, alcohols such as methanol, ethanol and ethylene glycol, acetonitrile, dimethyl sulfoxide, sulfolane, 1 , 3-dimethyl-2-imidazolidinone and water. These solvents may be used alone or as a mixture of two or more thereof.
触媒を用いる場合、反応の触媒としては、例えば塩酸、硫酸、硝酸等の鉱酸類、ギ酸、酢酸、プロピオン酸、トリフルオロ酢酸、メタンスルホン酸、ベンゼンスルホン酸、p-トルエンスルホン酸等の有機酸類、トリエチルアミン塩酸塩、ピリジン塩酸塩等のアミン類の酸付加塩、塩化亜鉛、ヨウ化亜鉛、四塩化チタン、塩化セリウム、イッテルビウムトリフレート、三フッ化ホウ素-エーテル錯体等のルイス酸を、一般式(4)で表される化合物に対して0.001〜1当量用いることができる。 When using a catalyst, examples of the reaction catalyst include mineral acids such as hydrochloric acid, sulfuric acid, and nitric acid, and organic acids such as formic acid, acetic acid, propionic acid, trifluoroacetic acid, methanesulfonic acid, benzenesulfonic acid, and p-toluenesulfonic acid. Acid addition salts of amines such as triethylamine hydrochloride, pyridine hydrochloride, Lewis acids such as zinc chloride, zinc iodide, titanium tetrachloride, cerium chloride, ytterbium triflate, boron trifluoride-ether complex, 0.001 to 1 equivalent can be used with respect to the compound represented by (4).
反応温度は−60℃から反応混合物の還流温度までの任意の温度を設定することができ、反応時間は、反応基質の濃度、反応温度によって変化するが、通常5分から100時間の範囲で任意に設定できる。 The reaction temperature can be set to an arbitrary temperature from −60 ° C. to the reflux temperature of the reaction mixture, and the reaction time varies depending on the concentration of the reaction substrate and the reaction temperature, but is usually arbitrarily within the range of 5 minutes to 100 hours. Can be set.
一般的には、例えば一般式(4)で表される化合物1当量に対して1〜10当量の一般式(5)で表される化合物を用い、無溶媒か、或いはテトラヒドロフラン又は1,4-ジオキサン等の溶媒を用い、50℃から反応混合物の還流温度の温度範囲で、30分から24時間反応を行なうのが好ましい。 In general, for example, 1 to 10 equivalents of the compound represented by the general formula (5) is used per 1 equivalent of the compound represented by the general formula (4), and no solvent is used. The reaction is preferably carried out in a temperature range of 50 ° C. to the reflux temperature of the reaction mixture using a solvent such as dioxane for 30 minutes to 24 hours.
製造法B Manufacturing method B
一般式(6)[式中、G, W1, X, Y, R4, R5, R6, l, m及びnは前記と同じ意味を表す。]で表される化合物と一般式(5)[式中、R2及びR3は前記と同じ意味を表す。]で表される化合物とを製造法Aと同様な条件下反応させることにより、一般式(1)においてW2が酸素原子であり、R1が水素原子である一般式(1-2)[式中、G, W1, X, Y, R2, R3, R4, R5, R6, l, m及びnは前記と同じ意味を表す。]で表される本発明化合物を得ることができる。 General formula (6) [wherein G, W 1 , X, Y, R 4 , R 5 , R 6 , l, m and n represent the same meaning as described above. And a compound represented by the general formula (5): wherein R 2 and R 3 have the same meaning as described above. And a compound represented by the general formula (1-2) in which W 2 is an oxygen atom and R 1 is a hydrogen atom in the general formula (1). In the formula, G, W 1 , X, Y, R 2 , R 3 , R 4 , R 5 , R 6 , l, m and n represent the same meaning as described above. This invention compound represented by this can be obtained.
製造法C Manufacturing method C
一般式(7)[式中、W2, X, R3及びmは前記と同じ意味を表す。]で表される化合物と一般式(8)[式中、G, Y, R1, R4, R5, R6, l及びnは前記と同じ意味を表す。]で表される化合物とを製造法Aと同様な条件下反応させることにより、一般式(1)においてW2が酸素原子であり、R2が水素原子である一般式(1-3)[式中、G, W2, X, Y, R1, R3, R4, R5, R6, l, m及びnは前記と同じ意味を表す。]で表される本発明化合物を得ることができる。 General formula (7) [wherein W 2 , X, R 3 and m represent the same meaning as described above. And a compound represented by the general formula (8): wherein G, Y, R 1 , R 4 , R 5 , R 6 , l and n have the same meaning as described above. And a compound represented by the general formula (1-3) in which W 2 is an oxygen atom and R 2 is a hydrogen atom in the general formula (1). In the formula, G, W 2 , X, Y, R 1 , R 3 , R 4 , R 5 , R 6 , l, m and n represent the same meaning as described above. This invention compound represented by this can be obtained.
製造法D Manufacturing method D
一般式(9)[式中、G, W1, X, Y, R1, R4, R5, R6, l, m及びnは前記と同じ意味を表す。]で表される化合物と一般式(5)[式中、R2及びR3は前記と同じ意味を表す。]で表される化合物とを、該反応に対して不活性な溶媒中又は無溶媒にて、必要ならば塩基の存在下、縮合剤を用いて反応させることにより、一般式(1)においてW2が酸素原子である一般式(1-4)[式中、G, W1, X, Y, R1, R2, R3, R4, R5, R6, l, m及びnは前記と同じ意味を表す。]で表される本発明化合物を得ることができる。 General formula (9) [wherein G, W 1 , X, Y, R 1 , R 4 , R 5 , R 6 , l, m and n represent the same meaning as described above. And a compound represented by the general formula (5): wherein R 2 and R 3 have the same meaning as described above. In the general formula (1), the compound represented by the general formula (1) is reacted with a compound in a solvent inert to the reaction or without a solvent, if necessary, in the presence of a base. General formula (1-4) in which 2 is an oxygen atom [wherein G, W 1 , X, Y, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , l, m and n are Represents the same meaning as above. This invention compound represented by this can be obtained.
反応基質の量は、一般式(9)で表される化合物1当量に対して1〜100当量の一般式(5)で表される化合物を用いることができる。 The amount of the reaction substrate may be 1 to 100 equivalents of the compound represented by the general formula (5) with respect to 1 equivalent of the compound represented by the general formula (9).
縮合剤は、通常のアミド合成に使用されるものであれば特に制限はないが、例えば向山試薬(2-クロロ-N-メチルピリジニウム アイオダイド)、DCC(1,3-ジシクロヘキシルカルボジイミド)、WSC(1-エチル-3-(3-ジメチルアミノプロピル)-カルボジイミド 塩酸塩)、CDI(カルボニルジイミダゾール)、ジメチルプロピニルスルホニウム ブロマイド、プロパルギルトリフェニルホスホニウム ブロマイド、DEPC(シアノ燐酸ジエチル)等を、一般式(9)で表される化合物に対して1〜4当量用いることができる。 The condensing agent is not particularly limited as long as it is used for ordinary amide synthesis. For example, Mukaiyama reagent (2-chloro-N-methylpyridinium iodide), DCC (1,3-dicyclohexylcarbodiimide), WSC (1 -Ethyl-3- (3-dimethylaminopropyl) -carbodiimide hydrochloride), CDI (carbonyldiimidazole), dimethylpropynylsulfonium bromide, propargyltriphenylphosphonium bromide, DEPC (diethyl cyanophosphate), etc. 1-4 equivalent can be used with respect to the compound represented by these.
溶媒を用いる場合、用いられる溶媒としては反応の進行を阻害しないものであれば何でもよく、例えばベンゼン、トルエン、キシレン等の芳香族炭化水素類、ヘキサン、ヘプタン等の脂肪族炭化水素類、シクロヘキサン等の脂環式炭化水素類、クロロベンゼン、ジクロロベンゼン等の芳香族ハロゲン化炭化水素類、ジクロロメタン、クロロホルム、四塩化炭素、1,2-ジクロロエタン、1,1,1-トリクロロエタン、トリクロロエチレン、テトラクロロエチレン等の脂肪族ハロゲン化炭化水素類、ジエチルエーテル、1,2-ジメトキシエタン、テトラヒドロフラン、1,4-ジオキサン等のエーテル類、酢酸エチル、プロピオン酸エチル等のエステル類、ジメチルホルムアミド、ジメチルアセトアミド、N-メチル-2-ピロリドン等のアミド類、トリエチルアミン、トリブチルアミン、N、N-ジメチルアニリン等のアミン類、ピリジン、ピコリン等のピリジン類、アセトニトリル及びジメチルスルホキシド等が挙げられる。これらの溶媒は単独で用いても、これらのうちの2種類以上を混合して用いてもよい。 In the case of using a solvent, any solvent may be used as long as it does not inhibit the progress of the reaction. For example, aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as hexane and heptane, cyclohexane, etc. Alicyclic hydrocarbons, aromatic halogenated hydrocarbons such as chlorobenzene and dichlorobenzene, fats such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,1,1-trichloroethane, trichloroethylene and tetrachloroethylene Group halogenated hydrocarbons, ethers such as diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran and 1,4-dioxane, esters such as ethyl acetate and ethyl propionate, dimethylformamide, dimethylacetamide, N-methyl- Amides such as 2-pyrrolidone, triethylamine, Examples thereof include amines such as tributylamine and N, N-dimethylaniline, pyridines such as pyridine and picoline, acetonitrile and dimethyl sulfoxide. These solvents may be used alone or as a mixture of two or more thereof.
塩基の添加は必ずしも必要ではないが、塩基を用いる場合、用いられる塩基としては、例えば水酸化ナトリウム、水酸化カリウム等のアルカリ金属水酸化物、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム等のアルカリ金属炭酸塩、トリエチルアミン、トリブチルアミン、N、N-ジメチルアニリン、ピリジン、4-(ジメチルアミノ)ピリジン、イミダゾール、1,8-ジアザビシクロ[5,4,0]-7-ウンデセン等の有機塩基等を、一般式(9)で表される化合物に対して1〜4当量用いることができる。 Although the addition of a base is not always necessary, when a base is used, examples of the base used include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metals such as sodium carbonate, potassium carbonate and sodium hydrogen carbonate. Organic bases such as carbonate, triethylamine, tributylamine, N, N-dimethylaniline, pyridine, 4- (dimethylamino) pyridine, imidazole, 1,8-diazabicyclo [5,4,0] -7-undecene, etc. 1 to 4 equivalents can be used with respect to the compound represented by the general formula (9).
反応温度は−60℃から反応混合物の還流温度までの任意の温度を設定することができ、反応時間は、反応基質の濃度、反応温度によって変化するが、通常5分から100時間の範囲で任意に設定できる。 The reaction temperature can be set to an arbitrary temperature from −60 ° C. to the reflux temperature of the reaction mixture, and the reaction time varies depending on the concentration of the reaction substrate and the reaction temperature, but is usually arbitrarily within the range of 5 minutes to 100 hours. Can be set.
一般的には、例えば一般式(9)で表される化合物1当量に対して1〜20当量の一般式(5)で表される化合物及び1〜4当量のWSC(1-エチル-3-(3-ジメチルアミノプロピル)-カルボジイミド 塩酸塩)、CDI(カルボニルジイミダゾール)等の縮合剤を用い、必要ならば1〜4当量の炭酸カリウム、トリエチルアミン、ピリジン、4-(ジメチルアミノ)ピリジン等の塩基存在下にて、無溶媒か又はジクロロメタン、クロロホルム、ジエチルエーテル、テトラヒドロフラン、1,4-ジオキサン等の溶媒を用い、0℃からこれらの溶媒の還流温度の範囲で、10分から24時間反応を行なうのが好ましい。 In general, for example, 1 to 20 equivalents of the compound represented by the general formula (5) and 1 to 4 equivalents of WSC (1-ethyl-3-ethyl) with respect to 1 equivalent of the compound represented by the general formula (9). (3-dimethylaminopropyl) -carbodiimide hydrochloride), CDI (carbonyldiimidazole) and other condensing agents. If necessary, 1-4 equivalents of potassium carbonate, triethylamine, pyridine, 4- (dimethylamino) pyridine, etc. In the presence of a base, the reaction is carried out for 10 minutes to 24 hours using no solvent or a solvent such as dichloromethane, chloroform, diethyl ether, tetrahydrofuran, 1,4-dioxane, etc., in the range of 0 ° C. to the reflux temperature of these solvents. Is preferred.
製造法E Manufacturing method E
一般式(10)[式中、W2, X, R2, R3及びmは前記と同じ意味を表す。]で表される化合物と一般式(8)[式中、G, Y, R1, R4, R5, R6, l及びnは前記と同じ意味を表す。]で表される化合物とを製造法Dと同様な条件下反応させることにより、一般式(1)においてW1が酸素原子である一般式(1-5)[式中、G, W2, X, Y, R1, R2, R3, R4, R5, R6, l, m及びnは前記と同じ意味を表す。]で表される本発明化合物を得ることができる。 General formula (10) [wherein W 2 , X, R 2 , R 3 and m represent the same meaning as described above. And a compound represented by the general formula (8): wherein G, Y, R 1 , R 4 , R 5 , R 6 , l and n have the same meaning as described above. And a compound represented by the general formula (1-5) in which W 1 is an oxygen atom in the general formula (1) [wherein G, W 2 , X, Y, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , l, m and n have the same meaning as described above. This invention compound represented by this can be obtained.
製造法F Manufacturing method F
一般式(11)[式中、X, R3及びmは前記と同じ意味を表す。]で表される化合物を文献記載の公知の方法、例えばケミカル・レビューズ[Chem. Rev.]1990年、90巻、879頁等に記載の方法に準じて位置選択的リチオ化後、一般式(12)[式中、G, W1, Y, R4, R5, R6, l及びnは前記と同じ意味を表す。]で表される化合物と反応させることにより、一般式(1)においてW2が酸素原子であり、R1及びR2が水素原子である一般式(1-6)[式中、G, W1, X, Y, R3, R4, R5, R6, l, m及びnは前記と同じ意味を表す。]で表される本発明化合物を得ることができる。なお、R-Liはブチルリチウム等のアルキルリチウム試薬を表す。 Formula (11) [wherein X, R 3 and m represent the same meaning as described above. ] After regioselective lithiation according to a known method described in the literature, for example, the method described in Chemical Reviews [Chem. Rev.] 1990, 90, 879, etc. (12) [wherein, G, W 1 , Y, R 4 , R 5 , R 6 , l and n represent the same meaning as described above. In the general formula (1), W 2 is an oxygen atom, and R 1 and R 2 are hydrogen atoms. In the formula, G, W 1 , X, Y, R 3 , R 4 , R 5 , R 6 , l, m and n have the same meaning as described above. This invention compound represented by this can be obtained. R-Li represents an alkyl lithium reagent such as butyl lithium.
製造法G Manufacturing method G
一般式(13)[式中、G, X, Y, R4, R5, R6, l, m及びnは前記と同じ意味を表す。]で表される化合物と一般式(14)[式中、W2及びR3は前記と同じ意味を表す。]で表される化合物とを製造法Fと同様な条件下反応させることにより、一般式(1)において、W1が酸素原子であり、R1及びR2が水素原子である一般式(1-7)[式中、G, W2, X, Y, R3, R4, R5, R6, l, m及びnは前記と同じ意味を表す。]で表される本発明化合物を得ることができる。なお、R-Liはブチルリチウム等のアルキルリチウム試薬を表す。 General formula (13) [wherein G, X, Y, R 4 , R 5 , R 6 , l, m, and n represent the same meaning as described above. And a compound represented by the general formula (14): wherein W 2 and R 3 have the same meaning as described above. In the general formula (1), W 1 is an oxygen atom, and R 1 and R 2 are hydrogen atoms. -7) wherein G, W 2 , X, Y, R 3 , R 4 , R 5 , R 6 , l, m and n have the same meaning as described above. This invention compound represented by this can be obtained. R-Li represents an alkyl lithium reagent such as butyl lithium.
製造法H Manufacturing method H
一般式(1)においてW1が酸素原子であり、R1が水素原子である一般式(1-8)[式中、G, W2, X, Y, R2, R3, R4, R5, R6, l, m及びnは前記と同じ意味を表す。]で表される本発明化合物と一般式(15)[式中、R1は前記と同じ意味を表し、J1は塩素原子、臭素原子、ヨウ素原子、C1〜C4アルキルカルボニルオキシ基(例えば、ピバロイルオキシ基)、C1〜C4アルキルスルホネート基(例えば、メタンスルホニルオキシ基)、C1〜C4ハロアルキルスルホネート基(例えば、トリフルオロメタンスルホニルオキシ基)、アリールスルホネート基(例えば、ベンゼンスルホニルオキシ基、p-トルエンスルホニルオキシ基)又はアゾリル基(例えば、イミダゾール-1-イル基)のような良好な脱離基を表す。]で表される化合物とを、必要ならば塩基の存在下、必要ならば該反応に対して不活性な溶媒を用いて反応させることにより、一般式(1)においてW1が酸素原子である一般式(1-5)[式中、G, W2, X, Y, R1, R2, R3, R4, R5, R6, l, m及びnは前記と同じ意味を表す。]で表される本発明化合物を得ることができる。 In general formula (1), W 1 is an oxygen atom, and R 1 is a hydrogen atom. General formula (1-8) [wherein G, W 2 , X, Y, R 2 , R 3 , R 4 , R 5 , R 6 , l, m and n represent the same meaning as described above. The compound of the present invention represented by the general formula (15) [wherein R 1 represents the same meaning as described above, J 1 represents a chlorine atom, a bromine atom, an iodine atom, a C 1 -C 4 alkylcarbonyloxy group ( For example, pivaloyloxy group), C 1 -C 4 alkyl sulfonate group (e.g., methanesulfonyloxy group), C 1 -C 4 haloalkylsulfonate group (e.g., trifluoromethanesulfonyloxy group), an aryl sulfonate group (e.g., benzenesulfonyloxy Group, p-toluenesulfonyloxy group) or an azolyl group (for example, imidazol-1-yl group). In the general formula (1), W 1 is an oxygen atom by reacting the compound represented by the formula (1) with a solvent inert to the reaction if necessary in the presence of a base. General formula (1-5) [wherein G, W 2 , X, Y, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , l, m and n represent the same meaning as described above] . This invention compound represented by this can be obtained.
反応基質の量は、一般式(1-8)で表される化合物1当量に対して1〜50当量の一般式(15)で表される化合物を用いることができる。 As the amount of the reaction substrate, 1 to 50 equivalents of the compound represented by the general formula (15) can be used per 1 equivalent of the compound represented by the general formula (1-8).
溶媒を用いる場合、用いられる溶媒としては反応の進行を阻害しないものであれば何でもよく、例えばベンゼン、トルエン、キシレン等の芳香族炭化水素類、ヘキサン、ヘプタン等の脂肪族炭化水素類、シクロヘキサン等の脂環式炭化水素類、クロロベンゼン、ジクロロベンゼン等の芳香族ハロゲン化炭化水素類、ジクロロメタン、クロロホルム、四塩化炭素、1,2-ジクロロエタン、1,1,1-トリクロロエタン、トリクロロエチレン、テトラクロロエチレン等の脂肪族ハロゲン化炭化水素類、ジエチルエーテル、1,2-ジメトキシエタン、テトラヒドロフラン、1,4-ジオキサン等のエーテル類、酢酸エチル、プロピオン酸エチル等のエステル類、ジメチルホルムアミド、ジメチルアセトアミド、N-メチル-2-ピロリドン等のアミド類、トリエチルアミン、トリブチルアミン、N、N-ジメチルアニリン等のアミン類、ピリジン、ピコリン等のピリジン類、メタノール、エタノール、エチレングリコール等のアルコール類、アセトニトリル、ジメチルスルホキシド、スルホラン、1,3-ジメチル-2-イミダゾリジノン及び水等が挙げられる。これらの溶媒は単独で用いても、これらのうちの2種類以上を混合して用いてもよい。 In the case of using a solvent, any solvent may be used as long as it does not inhibit the progress of the reaction. For example, aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as hexane and heptane, cyclohexane, etc. Alicyclic hydrocarbons, aromatic halogenated hydrocarbons such as chlorobenzene and dichlorobenzene, fats such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,1,1-trichloroethane, trichloroethylene and tetrachloroethylene Group halogenated hydrocarbons, ethers such as diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran and 1,4-dioxane, esters such as ethyl acetate and ethyl propionate, dimethylformamide, dimethylacetamide, N-methyl- Amides such as 2-pyrrolidone, triethylamine, Amines such as tributylamine and N, N-dimethylaniline, pyridines such as pyridine and picoline, alcohols such as methanol, ethanol and ethylene glycol, acetonitrile, dimethyl sulfoxide, sulfolane, 1,3-dimethyl-2-imidazolide Non- and water are listed. These solvents may be used alone or as a mixture of two or more thereof.
塩基を用いる場合、用いられる塩基としては、例えば水素化ナトリウム、水素化カリウム等のアルカリ金属水素化物、水酸化ナトリウム、水酸化カリウム等のアルカリ金属水酸化物、ナトリウムエトキシド、カリウムターシャリーブトキシド等のアルカリ金属アルコキシド類、リチウムジイソプロピルアミド、リチウムヘキサメチルジシラザン、ナトリウムアミド等のアルカリ金属アミド類、ターシャリーブチルリチウム等の有機金属化合物、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム等のアルカリ金属炭酸塩、トリエチルアミン、トリブチルアミン、N,N-ジメチルアニリン、ピリジン、4-(ジメチルアミノ)ピリジン、イミダゾール、1,8-ジアザビシクロ[5,4,0]-7-ウンデセン等の有機塩基等を、一般式(1-8)で表される化合物に対して1〜4当量用いることができる。 When a base is used, examples of the base used include alkali metal hydrides such as sodium hydride and potassium hydride, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, sodium ethoxide, potassium tertiary butoxide and the like. Alkali metal alkoxides, alkali metal amides such as lithium diisopropylamide, lithium hexamethyldisilazane, sodium amide, organometallic compounds such as tertiary butyl lithium, alkali metal carbonates such as sodium carbonate, potassium carbonate, sodium bicarbonate Organic bases such as triethylamine, tributylamine, N, N-dimethylaniline, pyridine, 4- (dimethylamino) pyridine, imidazole, 1,8-diazabicyclo [5,4,0] -7-undecene, etc. 1 to the compound represented by (1-8) It can be used equivalents.
反応温度は−60℃から反応混合物の還流温度までの任意の温度を設定することができ、反応時間は、反応基質の濃度、反応温度によって変化するが、通常5分から100時間の範囲で任意に設定できる。 The reaction temperature can be set to an arbitrary temperature from −60 ° C. to the reflux temperature of the reaction mixture, and the reaction time varies depending on the concentration of the reaction substrate and the reaction temperature, but is usually arbitrarily within the range of 5 minutes to 100 hours. Can be set.
一般的には、例えば一般式(1-8)で表される化合物1当量に対して1〜10当量の一般式(15)で表される化合物を用い、テトラヒドロフラン、1,4-ジオキサン、アセトニトリルやN、N-ジメチルホルムアミド等の極性溶媒中、必要ならば塩基として水素化ナトリウム、カリウムターシャリーブトキシド、水酸化カリウム、炭酸カリウム、トリエチルアミンやピリジン等を一般式(1-8)で表される化合物1当量に対して1〜3当量用いて、0〜90℃の温度範囲で、10分から24時間反応を行なうのが好ましい。 In general, for example, 1 to 10 equivalents of the compound represented by the general formula (15) is used per 1 equivalent of the compound represented by the general formula (1-8), tetrahydrofuran, 1,4-dioxane, acetonitrile In a polar solvent such as N, N-dimethylformamide, if necessary, sodium hydride, potassium tertiary butoxide, potassium hydroxide, potassium carbonate, triethylamine, pyridine and the like are represented by the general formula (1-8) as a base. It is preferable to carry out the reaction for 10 minutes to 24 hours in a temperature range of 0 to 90 ° C. using 1 to 3 equivalents per 1 equivalent of the compound.
製造法I Manufacturing method I
一般式(1)においてW2が酸素原子であり、R2が水素原子である一般式(1-9)[式中、G, W1, X, Y, R1, R3, R4, R5, R6, l, m及びnは前記と同じ意味を表す。]で表される本発明化合物と一般式(16)[式中、R2及びJ1は前記と同じ意味を表す。]で表される化合物とを製造法Hと同様な条件下反応させることにより、一般式(1)においてW2が酸素原子である一般式(1-4)[式中、G, W1, X, Y, R1, R2, R3, R4, R5, R6, l, m及びnは前記と同じ意味を表す。]で表される本発明化合物を得ることができる。 In the general formula (1), W 2 is an oxygen atom, and R 2 is a hydrogen atom (1-9) [wherein G, W 1 , X, Y, R 1 , R 3 , R 4 , R 5 , R 6 , l, m and n represent the same meaning as described above. The compound of the present invention represented by general formula (16): wherein R 2 and J 1 represent the same meaning as described above. And a compound represented by the general formula (1-4) in which W 2 is an oxygen atom in the general formula (1) [wherein G, W 1 , X, Y, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , l, m and n have the same meaning as described above. This invention compound represented by this can be obtained.
製造法J Manufacturing method J
一般式(17)[式中、W1, W2, X, Y, R1, R2, R3, R4, R6a, R6b, m及びnは前記と同じ意味を表す。]で表される化合物と一般式(18)[式中、R5は前記と同じ意味を表し、J2は水素原子又は塩素原子、臭素原子等のハロゲン原子を表す。]で表される化合物とを文献記載の公知の方法、例えばヘテロサイクルズ[Heterocycles]1996年、43巻、1771頁、ジャーナル・オブ・ヘテロサイクリック・ケミストリー[J. Heterocyclic Chem.]1990年、27巻、769頁、ユスタス・リービッヒス・アンナーレン・デア・ヘミー[Justus Liebigs Ann. Chem.]1989年、985頁、テトラヘドロン:アシンメトリー[Tetrahedron:Asymmetry]1997年、8巻、245頁、テトラヘドロン・レターズ[Tetrahedron Lett.]1986年、27巻、4647頁、国際特許出願公報(WO 01/12613号公報、WO 02/076956号公報)等に記載の方法に準じて反応させるか、
或いは、一般式(17)で表される化合物と一般式(19)[式中、R5は前記と同じ意味を表す。]で表される化合物とを文献記載の公知の方法、例えばケミストリー・レターズ[Chem. Lett.]1990年、559頁、シンセシス[Synthesis]1997年、309頁、シンセティック・コミュニケーションズ[Synth. Commun.]1988年、18巻、2315頁等に記載の方法に準じて反応させることにより、一般式(1)においてGがG-7である一般式(1-010)[式中、W1, W2, X, Y, R1, R2, R3, R4, R5, R6a, R6, m及びnは前記と同じ意味を表す。]で表される化合物を得ることができる。
General formula (17) [wherein W 1 , W 2 , X, Y, R 1 , R 2 , R 3 , R 4 , R 6a , R 6b , m and n represent the same meaning as described above. And a compound represented by the general formula (18) [wherein R 5 represents the same meaning as described above, and J 2 represents a hydrogen atom or a halogen atom such as a chlorine atom or a bromine atom. And a known method described in the literature, for example, Heterocycles 1996, 43, 1771, Journal of Heterocyclic Chemistry [J. Heterocyclic Chem.] 1990, 27, 769, Justus Liebigs Ann. Chem. 1989, 985, Tetrahedron: Asymmetry 1997, 8, 245, Tetrahedron Letters [Tetrahedron Lett.], 1986, 27, 4647, international patent application publications (WO 01/12613, WO 02/076956) and the like,
Alternatively, the compound represented by the general formula (17) and the general formula (19) [wherein R 5 represents the same meaning as described above. The compounds represented by the above formulas are known methods described in the literature, for example, Chemistry Letters [Chem. Lett.] 1990, page 559, Synthesis 1997, page 309, Synth. Commun. 1988, Vol. 18, p. 2315, and the like, by reaction according to the general formula (1-010) in which G is G-7 in the general formula ( 1 ) [W 1 , W 2 , X, Y, R 1 , R 2 , R 3 , R 4 , R 5 , R 6a , R 6 , m and n have the same meaning as described above. The compound represented by this can be obtained.
製造法A〜製造法Jにおいて、反応終了後の反応混合物は、直接濃縮、又は有機溶媒に溶解し、水洗後濃縮、又は氷水に投入、有機溶媒抽出後濃縮といった通常の後処理を行ない、目的の一般式(1)で表される化合物を得ることができる。また、精製の必要が生じたときには、再結晶、カラムクロマトグラフ、薄層クロマトグラフ、液体クロマトグラフ分取等の任意の精製方法によって分離、精製することができる。 In production method A to production method J, the reaction mixture after completion of the reaction is directly concentrated or dissolved in an organic solvent, concentrated after washing with water, or poured into ice water, followed by usual post-treatment such as extraction after organic solvent extraction. A compound represented by the general formula (1) can be obtained. Moreover, when the necessity for purification arises, it can be separated and purified by any purification method such as recrystallization, column chromatograph, thin layer chromatograph, liquid chromatographic fractionation and the like.
製造法Aにおいて一般式(1)で表される化合物を製造するための原料化合物である一般式(4)で表される化合物、及び一般式(4)においてW1及びW2が酸素原子であり、(X)mが3位ニトロ基である一般式(2)で表される化合物は、次のようにして合成できる。 In production method A, the compound represented by general formula (4), which is a starting compound for producing the compound represented by general formula (1), and W 1 and W 2 in the general formula (4) are oxygen atoms The compound represented by the general formula (2) in which (X) m is a 3-position nitro group can be synthesized as follows.
反応式1 Reaction formula 1
すなわち、一般式(20)[式中、X及びmは前記と同じ意味を表す。]で表される化合物と一般式(8)においてR1が水素原子である一般式(8-1)[式中、G, Y, R4, R5, R6, l及びnは前記と同じ意味を表す。]で表される化合物とを文献記載の公知の方法、例えばベリヒテ・デア・ドイッチェン・ヘミッシェン・ゲゼルシャフト[Ber. Dtsch. Chem. Ges.]1907年、40巻、3177頁、ジャーナル・オブ・ザ・ケミカル・ソサイエティー [J. Chem. Soc.]1954年、2023頁、ジャーナル・オブ・ザ・ケミカル・ソサイエティー・パーキン・トランスアクションズ、1[J. Chem. Soc. Perkin Trans. 1]1994年、2975頁等に記載の方法に準じて反応させることにより、一般式(4)においてW1及びW2が酸素原子である一般式(4-1)[式中、G, X, Y, R4, R5, R6, l, m及びnは前記と同じ意味を表す。]で表される化合物を容易に合成することができる。 That is, general formula (20) [wherein X and m represent the same meaning as described above. And R 1 is a hydrogen atom in the general formula (8), wherein G, Y, R 4 , R 5 , R 6 , l and n are as defined above Represents the same meaning. And the compound represented by the literature, for example, Berichte der Deutschen Hemischen Gesellshaft [Ber. Dtsch. Chem. Ges.] 1907, 40, 3177, Journal of the. Chemical Society [J. Chem. Soc.] 1954, 2023, Journal of the Chemical Society Perkin Transactions, 1 [J. Chem. Soc. Perkin Trans. 1] 1994, 2975 In the general formula (4), W 1 and W 2 are oxygen atoms in the general formula (4-1) [wherein G, X, Y, R 4 , R 5 , R 6 , l, m and n represent the same meaning as described above. ] Can be easily synthesized.
製造法A、製造法B及び製造法Dで用いられる一般式(5)で表される化合物の或るものは公知化合物であり、一部は市販品として入手できる。また、それ以外のものも、例えばケミカル・アンド・ファーマシューティカル・ブレティン [Chem. Pharm. Bull.] 1982年、30巻、1921頁、ジャーナル・オブ・ジ・アメリカン・ケミカル・ソサイエティー[J. Am. Chem. Soc.]1986年、108巻、3811頁、国際特許出願公報(WO 01/23350号公報)等に記載の方法及び文献記載のその他1級又は2級アルキルアミン類それぞれの一般的な合成方法に準じて合成することができる。 Some of the compounds represented by the general formula (5) used in Production Method A, Production Method B, and Production Method D are known compounds, and some of them are commercially available. Others, for example, Chemical and Pharmaceutical Bulletin [Chem. Pharm. Bull.] 1982, 30, 1921, Journal of the American Chemical Society [J. Am Chem. Soc.] 1986, 108, 3811, the method described in International Patent Application Publication (WO 01/23350) and the like, and other primary or secondary alkylamines described in the literature. It can be synthesized according to the synthesis method.
製造法Bにおいて、一般式(1)で表される化合物を製造するための原料化合物である、一般式(6)で表される化合物は、次のようにして合成できる。 In production method B, the compound represented by general formula (6), which is a raw material compound for producing the compound represented by general formula (1), can be synthesized as follows.
反応式2 Reaction formula 2
すなわち、一般式(9)においてR1が水素原子である一般式(9-1)[式中、G, W1, X, Y, R4, R5, R6, l, m及びnは前記と同じ意味を表す。]で表される化合物を文献記載の一般的な脱水環化によるイソイミドの合成反応、例えばジャーナル・オブ・ジ・アメリカン・ケミカル・ソサイエティー[J. Am. Chem. Soc.]1975年、97巻、5582頁、ジャーナル・オブ・メディシナル・ケミストリー[J. Med. Chem.]1967年、10巻、982頁、ザ・ジャーナル・オブ・オーガニック・ケミストリー[J. Org. Chem.]1963年、28巻、2018頁等に記載の方法等に準じて環化することにより、一般式(6)[式中、G, W1, X, Y, R4, R5, R6, l, m及びnは前記と同じ意味を表す。]で表される化合物を容易に合成することができる。 That is, in the general formula (9), R 1 is a hydrogen atom, the general formula (9-1) [wherein G, W 1 , X, Y, R 4 , R 5 , R 6 , l, m and n are Represents the same meaning as above. ], For example, Journal of the American Chemical Society [J. Am. Chem. Soc.] 1975, Vol. 97, 5582, Journal of Medicinal Chemistry [J. Med. Chem.] 1967, 10, 982, The Journal of Organic Chemistry [J. Org. Chem.] 1963, 28, By cyclization according to the method described on page 2018, etc., general formula (6) [wherein G, W 1 , X, Y, R 4 , R 5 , R 6 , l, m and n are Represents the same meaning as above. ] Can be easily synthesized.
製造法Cにおいて、一般式(1)で表される化合物を製造するための原料化合物である、一般式(7)で表される化合物は、次のようにして合成できる。 In the production method C, the compound represented by the general formula (7), which is a raw material compound for producing the compound represented by the general formula (1), can be synthesized as follows.
反応式3 Reaction formula 3
すなわち、一般式(10)においてR2が水素原子である一般式(10-1)[式中、W2, X, R3及びmは前記と同じ意味を表す。]で表される化合物を反応式2と同様に反応させることにより、一般式(7)[式中、W2, X, R3及びmは前記と同じ意味を表す。]で表される化合物を容易に合成することができる。 That is, in general formula (10), R 2 is a hydrogen atom. General formula (10-1) [wherein W 2 , X, R 3 and m represent the same meaning as described above. The compound represented by the general formula (7) [wherein W 2 , X, R 3 and m are as defined above]. ] Can be easily synthesized.
製造法C及び製造法Eで用いられる一般式(8)で表される化合物は、例えば下記の反応式4〜反応式16で表される方法等を用いて合成することができる。 The compound represented by the general formula (8) used in the production method C and the production method E can be synthesized using, for example, the methods represented by the following reaction formulas 4 to 16.
反応式4 Reaction formula 4
一般式(21)[式中、Y, R1, R4, R6a, R6b及びnは前記と同じ意味を表し、Pはアセチル基、ピバロイル基、ベンゾイル基、ターシャリーブトキシカルボニル基、ベンジルオキシカルボニル基等の、一般に用いられるアミノ基の保護基を表す。]で表される化合物と一般式(18)[式中、R5及びJ2は前記と同じ意味を表す。]で表される化合物或いは一般式(19)[式中、R5は前記と同じ意味を表す。]で表される化合物とを製造法Jと同様な条件下反応させることによりイソオキサゾリン環を形成した後、各々の保護基について一般的に用いられる方法で脱保護することにより、一般式(8)においてGがG-7である一般式(8-2)[式中、Y, R1, R4, R5, R6a, R6b及びnは前記と同じ意味を表す。]で表される化合物を得ることができる。 General formula (21) [wherein Y, R 1 , R 4 , R 6a , R 6b and n represent the same meaning as described above, P represents an acetyl group, a pivaloyl group, a benzoyl group, a tertiary butoxycarbonyl group, benzyl Represents a commonly used amino protecting group such as an oxycarbonyl group. And a compound represented by the general formula (18): wherein R 5 and J 2 have the same meaning as described above. Or a compound represented by the general formula (19): wherein R 5 represents the same meaning as described above. The compound represented by formula (8) is reacted under the same conditions as in Production Method J to form an isoxazoline ring, and each of the protecting groups is then deprotected by a commonly used method to obtain a compound of the general formula (8 In general formula (8-2) wherein G is G-7, wherein Y, R 1 , R 4 , R 5 , R 6a , R 6b and n have the same meaning as described above. The compound represented by this can be obtained.
反応式5 Reaction formula 5
一般式(22)[式中、Y, R1, R4, R6a, R6b, n及びPは前記と同じ意味を表す。]で表される化合物と一般式(23)[式中、R5は前記と同じ意味を表し、Rはメチル、エチル等の低級アルキル基を表す。]で表される化合物とを文献記載の公知の方法、例えば、ケミッシェ・ベリヒテ[Chem. Ber. ]1958年、91巻、1098頁等に記載の方法に準じて縮合させた後、各々の保護基について一般的に用いられる方法で脱保護することにより、一般式(8)においてGがG-13である一般式(8-3)[式中、Y, R1, R4, R5, R6a, R6b及びnは前記と同じ意味を表す。]で表される化合物を得ることができる。 General formula (22) [wherein Y, R 1 , R 4 , R 6a , R 6b , n and P represent the same meaning as described above. And a compound represented by the general formula (23): wherein R 5 represents the same meaning as described above, and R represents a lower alkyl group such as methyl or ethyl. And the compound represented by the literature, for example, Chemische Berichte [Chem. Ber.] 1958, 91, 1098, etc. By deprotecting the group by a commonly used method, general formula (8-3) wherein G is G-13 in general formula (8) [wherein Y, R 1 , R 4 , R 5 , R 6a , R 6b and n represent the same meaning as described above. The compound represented by this can be obtained.
或いは、一般式(22)で表される化合物と公知の一般式(24)[式中、R5は前記と同じ意味を表し、J3はハロゲン原子、C1〜C4アルコキシ基(例えば、メトキシ基、エトキシ基)、アリールオキシ基(例えば、フェノキシ基)、C1〜C4アルキルカルボニルオキシ基(例えば、ピバロイルオキシ基)又はC1〜C4アルコキシカルボニルオキシ基(例えば、イソブチルオキシカルボニルオキシ基)のような脱離基を表す。]で表される化合物又は公知の一般式(25)[式中、R5は前記と同じ意味を表す。]で表される化合物とを文献記載の一般的なアミンのアシル化反応、例えばジャーナル・オブ・ジ・アメリカン・ケミカル・ソサイエティー[J. Am. Chem. Soc.]2000年、122巻、2149頁、テトラヘドロン:アシンメトリー[Tetrahedron:Asymmetry]1993年、4巻、205頁、国際特許出願公報(WO 99/24393号公報)等に記載の方法に準じて反応させることにより得られる一般式(26)[式中、Y, R1, R4, R5, R6a, R6b, n及びPは前記と同じ意味を表す。]で表される化合物を、文献記載の公知の方法、例えば、ベリヒテ・デア・ドイッチェン・ヘミッシェン・ゲゼルシャフト[Ber. Dtsch. Chem. Ges.]1940年、73巻、656頁、ジャーナル・オブ・ヘテロサイクリック・ケミストリー[J. Heterocyclic Chem.]2000年、37巻、343頁、ヨーロッパ特許出願公報(EP 0,895,992号公報)等に記載の方法に準じて脱水環化によりオキサゾリン環を形成した後、各々の保護基について一般的に用いられる方法で脱保護することにより、一般式(8-3)で表される化合物を得ることもできる。 Alternatively, the compound represented by the general formula (22) and a known general formula (24) [wherein R 5 represents the same meaning as described above, J 3 represents a halogen atom, a C 1 -C 4 alkoxy group (for example, methoxy group, ethoxy group), an aryloxy group (e.g., phenoxy group), C 1 -C 4 alkylcarbonyloxy group (e.g., pivaloyloxy group) or a C 1 -C 4 alkoxycarbonyloxy group (e.g., iso-butyloxycarbonyl group Represents a leaving group such as Or a known general formula (25) [wherein R 5 represents the same meaning as described above. And the general amine acylation reaction described in the literature, for example, Journal of the American Chemical Society [J. Am. Chem. Soc.] 2000, 122, 2149. Tetrahedron: Asymmetry, 1993, Vol. 4, p. 205, general formula (26) obtained by reacting according to the method described in International Patent Application Publication (WO 99/24393), etc. [Wherein, Y, R 1 , R 4 , R 5 , R 6a , R 6b , n and P represent the same meaning as described above. The compound represented by the above formula is converted into a known method described in the literature, for example, Berichte der Deutschen Hemischen Gezelshaft [Ber. Dtsch. Chem. Ges.] 1940, 73, 656, Journal of Hetero. Cyclic chemistry [J. Heterocyclic Chem.] 2000, 37, 343, after forming an oxazoline ring by dehydration cyclization according to the method described in European Patent Application Publication (EP 0,895,992), etc. The compound represented by the general formula (8-3) can also be obtained by deprotecting a protecting group of
ここで用いられる一般式(23)で表される化合物は公知化合物であり、一部は市販品として入手できる。また、それ以外のものも文献記載の公知の方法、例えば、ケミッシェ・ベリヒテ[Chem. Ber. ]1959年、92巻、330頁及び1985年、118巻、3089頁、ジャーナル・オブ・ジ・アメリカン・ケミカル・ソサイエティー[J. Am. Chem. Soc.]1948年、70巻、165頁等に記載の方法に準じて容易に合成することができる。 The compounds represented by the general formula (23) used here are known compounds, and some of them are available as commercial products. In addition, other methods known in the literature, for example, Chemische Berichte (Chem. Ber.) 1959, 92, 330 and 1985, 118, 3089, Journal of the American -Chemical Society [J. Am. Chem. Soc.] 1948, 70, 165, etc., can be easily synthesized according to the method described.
反応式6 Reaction formula 6
一般式(27)[式中、Y, R1, R4, R5, n及びPは前記と同じ意味を表し、J4は塩素原子、臭素原子、ヨウ素原子、C1〜C4アルキルスルホネート基(例えば、メタンスルホニルオキシ基)、C1〜C4ハロアルキルスルホネート基(例えば、トリフルオロメタンスルホニルオキシ基)又はアリールスルホネート基(例えば、ベンゼンスルホニルオキシ基、p-トルエンスルホニルオキシ基)のような良好な脱離基を表す。]で表される化合物を文献記載の公知の方法、例えば、ブレティン・オブ・ザ・ケミカル・ソサイエティー・オブ・ジャパン[Bull. Chem. Soc. Jpn.]1996年、69巻、3345頁、ドイツ国特許出願公報(DE 19528778号公報)等に記載の方法に準じてオキサゾリン環を形成した後、各々の保護基について一般的に用いられる方法で脱保護することにより、一般式(8)においてGがG-14でありR6e及びR6fは水素原子である一般式(8-4)[式中、Y, R1, R4, R5及びnは前記と同じ意味を表す。]で表される化合物を得ることができる。 General formula (27) [wherein Y, R 1 , R 4 , R 5 , n and P represent the same meaning as described above, J 4 represents a chlorine atom, a bromine atom, an iodine atom, a C 1 -C 4 alkyl sulfonate. Good as a group (eg methanesulfonyloxy group), C 1 -C 4 haloalkyl sulfonate group (eg trifluoromethanesulfonyloxy group) or aryl sulfonate group (eg benzenesulfonyloxy group, p-toluenesulfonyloxy group) Represents a leaving group. ], For example, Bulletin of the Chemical Society of Japan [Bull. Chem. Soc. Jpn.] 1996, 69, 3345, Germany. After forming the oxazoline ring according to the method described in the patent application publication (DE 19528778) and the like, deprotection of each protecting group by a commonly used method, G in the general formula (8) General formula (8-4) wherein G-14 and R 6e and R 6f are hydrogen atoms [wherein, Y, R 1 , R 4 , R 5 and n represent the same meaning as described above. The compound represented by this can be obtained.
反応式7 Reaction formula 7
一般式(26)[式中、Y, R1, R4, R5, R6a, R6b, n及びPは前記と同じ意味を表す。]で表される化合物を文献記載の公知の方法、例えば、ザ・ジャーナル・オブ・オーガニック・ケミストリー[J. Org. Chem.]1997年、62巻、1106頁等に記載の方法に準じて、五硫化二燐又はLawesson's Reagent等と反応させチアゾリン環を形成した後、各々の保護基について一般的に用いられる方法を用いて脱保護することにより、一般式(8)においてGがG-17である一般式(8-5)[式中、Y, R1, R4, R5, R6a, R6b及びnは前記と同じ意味を表す。]で表される化合物を得ることができる。 General formula (26) [wherein Y, R 1 , R 4 , R 5 , R 6a , R 6b , n and P represent the same meaning as described above. In accordance with a known method described in the literature, for example, the method described in The Journal of Organic Chemistry [J. Org. Chem.] 1997, 62, 1106, etc. After reacting with diphosphorus pentasulfide or Lawesson's Reagent, etc. to form a thiazoline ring, deprotection using a method generally used for each protecting group, G in General Formula (8) is G-17. A certain general formula (8-5) [wherein Y, R 1 , R 4 , R 5 , R 6a , R 6b and n represent the same meaning as described above. The compound represented by this can be obtained.
反応式8 Reaction formula 8
一般式(28)[式中、Y, R1, R4, R5, R6a, R6b, n及びPは前記と同じ意味を表す。]で表される化合物を文献記載の公知の方法、例えば、ドイツ国特許出願公報(DE 19528778号公報)等に記載の方法に準じて、五硫化二燐又はLawesson's Reagentと反応させチアゾリン環を形成した後、各々の保護基について一般的に用いられる方法を用いて脱保護することにより、一般式(8)においてGがG-18である一般式(8-6)[式中、Y, R1, R4, R5, R6a, R6b及びnは前記と同じ意味を表す。]で表される化合物を得ることができる。 General formula (28) [wherein Y, R 1 , R 4 , R 5 , R 6a , R 6b , n and P represent the same meaning as described above. In accordance with a known method described in the literature, for example, a method described in German Patent Application Publication (DE 19528778) etc., a thiazoline ring is formed by reacting with diphosphorus pentasulfide or Lawesson's Reagent Then, by deprotection using a method commonly used for each protecting group, general formula (8-6) wherein G is G-18 in general formula (8) [wherein Y, R 1 , R 4 , R 5 , R 6a , R 6b and n represent the same meaning as described above. The compound represented by this can be obtained.
或いは、一般式(29)[式中、Y, R1, R4, R6a, R6b, n及びPは前記と同じ意味を表す。]で表される化合物と公知の一般式(30)[式中、R5は前記と同じ意味を表す。]で表される化合物とを文献記載の公知の方法、例えば、ザ・ジャーナル・オブ・オーガニック・ケミストリー[J. Org. Chem.]1960年、25巻、1147頁等に記載の方法に準じてチアゾリン環を形成した後、各々の保護基について一般的に用いられる方法で脱保護することにより、一般式(8-6)で表される化合物を得ることもできる。 Alternatively, general formula (29) [wherein Y, R 1 , R 4 , R 6a , R 6b , n and P represent the same meaning as described above. And a known general formula (30), wherein R 5 represents the same meaning as described above. In accordance with a known method described in the literature, for example, the method described in The Journal of Organic Chemistry [J. Org. Chem.] 1960, 25, 1147, etc. After forming the thiazoline ring, each protecting group is deprotected by a commonly used method, whereby the compound represented by the general formula (8-6) can be obtained.
反応式9 Reaction formula 9
一般式(31)[式中、Y, R1, R4, R5, R6a, n及びPは前記と同じ意味を表す。]で表される化合物と公知の一般式(32)[式中、R6eは前記と同じ意味を表す。]で表されるヒドラジン化合物とを文献記載の公知の方法、例えば、ジャーナル・オブ・ザ・ケミカル・ソサイエティー [J. Chem. Soc.]1964年、6072頁等に記載の方法に準じて反応させピラゾリン環を形成した後、各々の保護基について一般的に用いられる方法を用いて脱保護することにより、一般式(8)においてGがG-11でありR6bが水素原子である一般式(8-7)[式中、Y, R1, R4, R5, R6a, R6e及びnは前記と同じ意味を表す。]で表される化合物を得ることができる。 General formula (31) [wherein Y, R 1 , R 4 , R 5 , R 6a , n and P represent the same meaning as described above. And a known general formula (32) [wherein R 6e represents the same meaning as described above. ] According to a known method described in the literature, for example, the method described in Journal of the Chemical Society [J. Chem. Soc.] 1964, page 6072, etc. After forming the pyrazoline ring, deprotection is performed using a method generally used for each protecting group, whereby in the general formula (8), G is G-11 and R 6b is a hydrogen atom ( 8-7) [wherein Y, R 1 , R 4 , R 5 , R 6a , R 6e and n represent the same meaning as described above. The compound represented by this can be obtained.
また、一般式(31)で表される化合物を公知の一般式(33)[式中、R6cは前記と同じ意味を表す。]で表されるアミジン化合物と文献記載の公知の方法、例えば、ジャーナル・オブ・ヘテロサイクリック・ケミストリー[J. Heterocyclic Chem.]1989年、26巻、251頁等に記載の方法に準じて反応させ3、4−ジヒドロピリミジン環を形成した後、各々の保護基について一般的に用いられる方法を用いて脱保護することにより、一般式(8)においてGがG-53でありR6eが水素原子である一般式(8-8)[式中、Y, R1, R4, R5, R6a, R6c及びnは前記と同じ意味を表す。]で表される化合物を得ることもできる。 Further, the compound represented by the general formula (31) is converted into a known general formula (33) [wherein R 6c represents the same meaning as described above. ] According to a known method described in the literature, for example, Journal of Heterocyclic Chemistry [J. Heterocyclic Chem.] 1989, Vol. 26, page 251, etc. And forming a 3,4-dihydropyrimidine ring, followed by deprotection using a method generally used for each protecting group, whereby G is G-53 and R 6e is hydrogen in general formula (8). General formula (8-8) which is an atom [wherein Y, R 1 , R 4 , R 5 , R 6a , R 6c and n represent the same meaning as described above. The compound represented by this can also be obtained.
反応式10 Reaction formula 10
一般式(34)[式中、Y, R1, R4, n及びPは前記と同じ意味を表す。]で表される化合物と一般式(18)[式中、R5及びJ2は前記と同じ意味を表す。]で表される化合物或いは一般式(19)[式中、R5は前記と同じ意味を表す。]で表される化合物とを製造法Jと同様な条件下反応させることによりジオキサゾリン環を形成した後、各々の保護基について一般的に用いられる方法で脱保護することにより、一般式(8)においてGがG-23である一般式(8-9)[式中、Y, R1, R4, R5及びnは前記と同じ意味を表す。]で表される化合物を得ることができる。 General formula (34) [wherein Y, R 1 , R 4 , n and P represent the same meaning as described above. And a compound represented by the general formula (18): wherein R 5 and J 2 have the same meaning as described above. Or a compound represented by the general formula (19): wherein R 5 represents the same meaning as described above. The compound represented by formula (8) is reacted under the same conditions as in Production Method J to form a dioxazoline ring, and each of the protecting groups is then deprotected by a commonly used method to obtain a compound of the general formula (8 ) In which G is G-23, wherein Y, R 1 , R 4 , R 5 and n are as defined above. The compound represented by this can be obtained.
反応式11 Reaction formula 11
一般式(34)[式中、Y, R1, R4, n及びPは前記と同じ意味を表す。]で表される化合物と一般式(35)[式中、R5は前記と同じ意味を表す。]で表される化合物とを文献記載の公知の方法、例えば、ケミストリー・レターズ[Chem. Lett.]1998年、119頁等に記載の方法に準じて反応させることにより得られる一般式(36)[式中、Y, R1, R4, R5, n及びPは前記と同じ意味を表す。]で表される化合物を、文献記載の公知の方法、例えば、テトラヘドロン・レターズ[Tetrahedron Lett.]1992年、33巻、7751頁等に記載の方法に準じて一般式(37)[式中、Y, R1, R4, R5, n及びPは前記と同じ意味を表す。]で表されるN−ハロゲン化合物を経由して1、5−ジヒドロオキサゾール環を形成し、各々の保護基について一般的に用いられる方法で脱保護することにより、一般式(8)においてGがG-15である一般式(8-10)[式中、Y, R1, R4, R5及びnは前記と同じ意味を表す。]で表される化合物を得ることができる。 General formula (34) [wherein Y, R 1 , R 4 , n and P represent the same meaning as described above. And a compound represented by the general formula (35), wherein R 5 represents the same meaning as described above. And a compound represented by the general formula (36) obtained by reacting according to a known method described in the literature, for example, the method described in Chemistry Letters [Chem. Lett.] 1998, p.119, etc. [Wherein, Y, R 1 , R 4 , R 5 , n and P represent the same meaning as described above. The compound represented by the general formula (37) [in the formula (37), in accordance with a method described in literature, for example, the method described in Tetrahedron Lett. 1992, 33, 7751, etc. , Y, R 1 , R 4 , R 5 , n and P have the same meaning as described above. To form a 1,5-dihydrooxazole ring via an N-halogen compound represented by the following formula, and deprotecting each protecting group by a commonly used method. General formula (8-10) which is G-15 [wherein Y, R 1 , R 4 , R 5 and n represent the same meaning as described above. The compound represented by this can be obtained.
ここで用いられる一般式(35)で表される化合物は公知化合物であり、一部は市販品として入手できる。また、それ以外のものも文献記載の公知の方法、例えばケミカル・アンド・ファーマシューティカル・ブレティン [Chem. Pharm. Bull.] 1965年、13巻、999頁等に記載の方法に準じて対応する公知のアミノ酸から容易に合成することができる。 The compounds represented by the general formula (35) used here are known compounds, and some of them are available as commercial products. Others correspond to known methods described in the literature, for example, the method described in Chemical and Pharmaceutical Bulletin [Chem. Pharm. Bull.] 1965, Vol. 13, p. 999, etc. It can be easily synthesized from known amino acids.
反応式12 Reaction formula 12
一般式(21)においてR6a及びR6bが水素原子である一般式(21-01)[式中、Y, R1, R4, n及びPは前記と同じ意味を表す。]で表される化合物と一般式(38)[式中、R5及びR6cは前記と同じ意味を表す。]で表される化合物とを文献記載の公知の方法、例えば、ジャーナル・オブ・ザ・ケミカル・ソサイエティー・ケミカル・コミュニケーションズ[J. Chem. Soc. Chem. Commun.]1987年、919頁等に記載の方法に準じて反応させることにより4、5−ジヒドロフラン環を形成し、各々の保護基について一般的に用いられる方法で脱保護することにより、一般式(8)においてGがG-1である一般式(8-11)[式中、Y, R1, R4, R5, R6c及びnは前記と同じ意味を表す。]で表される化合物を得ることができる。 In general formula (21), R 6a and R 6b are hydrogen atoms. General formula (21-01) [wherein Y, R 1 , R 4 , n, and P represent the same meaning as described above. And a compound represented by the general formula (38) [wherein R 5 and R 6c represent the same meaning as described above. And the compound represented by the literature, for example, in Journal of the Chemical Society Chemical Communications [J. Chem. Soc. Chem. Commun.] 1987, page 919, etc. To form a 4,5-dihydrofuran ring by reacting in accordance with the method of the above, and by deprotecting each protecting group by a method generally used, in the general formula (8), G is G-1 A certain general formula (8-11) [wherein Y, R 1 , R 4 , R 5 , R 6c and n represent the same meaning as described above. The compound represented by this can be obtained.
或いは一般式(21-01)で表される化合物と公知の一般式(39)[式中、R5は前記と同じ意味を表し、R6cはアルコキシカルボニル基、シアノ基等の電子吸引基を表す。]で表される化合物とを文献記載の公知の方法、例えば、テトラヘドロン・レターズ[Tetrahedron Lett.]1996年、37巻、4949頁等に記載の方法に準じて反応させることにより一般式(8-11)においてR6cが電子吸引基を表す化合物を得ることもできる。 Alternatively, the compound represented by the general formula (21-01) and a known general formula (39) [wherein R 5 represents the same meaning as described above, and R 6c represents an electron-withdrawing group such as an alkoxycarbonyl group or a cyano group. Represent. The compound represented by the general formula (8) is reacted according to a known method described in the literature, for example, the method described in Tetrahedron Lett. 1996, 37, 4949, etc. -11), a compound in which R 6c represents an electron-withdrawing group can also be obtained.
ここで用いられる一般式(38)で表される化合物のあるものは公知化合物であり、また、それ以外のものも文献記載の公知の方法、例えば、ケミストリー・レターズ[Chem. Lett.]1981年、1135頁、ザ・ジャーナル・オブ・オーガニック・ケミストリー[J. Org. Chem.]1992年、57巻、4555頁等に記載の方法に準じて容易に合成することができる。 Some of the compounds represented by the general formula (38) used here are known compounds, and others are known methods described in the literature, for example, Chemistry Letters [Chem. Lett.] 1981. 1135, The Journal of Organic Chemistry [J. Org. Chem.] 1992, 57, 4555, etc., and can be easily synthesized.
さらに、一般式(39)で表される化合物も公知化合物であり、一部は市販品として入手できる。また、それ以外のものも文献記載の公知の方法、例えば、ジャーナル・オブ・ヘテロサイクリック・ケミストリー[J. Heterocyclic Chem.]1984年、21巻、1849頁、ジャーナル・オブ・メディシナル・ケミストリー[J. Med. Chem.]1979年、22巻、1385頁等に記載の方法に準じて容易に合成することができる。 Furthermore, the compound represented by the general formula (39) is also a known compound, and a part thereof can be obtained as a commercial product. In addition, other methods known in the literature, for example, Journal of Heterocyclic Chemistry [J. Heterocyclic Chem.] 1984, 21, 1849, Journal of Medicinal Chemistry [J Med. Chem.] Can be easily synthesized according to the method described in 1979, Vol. 22, p.
反応式13 Reaction formula 13
一般式(34)[式中、Y, R1, R4, n及びPは前記と同じ意味を表す。]で表される化合物と一般式(40)[式中、R5は前記と同じ意味を表す。]で表される化合物或いは一般式(41)[式中、R5は前記と同じ意味を表す。]で表される化合物とを文献記載の公知の方法、例えば、シンセシス[Synthesis]1983年、203頁、日本国特許出願公報(JP 06/092957号公報)、ジャーナル・オブ・フルオリン・ケミストリー[J. Fluorine Chem.]1989年、44巻、377頁等に記載の方法に準じて反応させることによりジオキソラン環を形成した後、各々の保護基について一般的に用いられる方法で脱保護することにより、一般式(8)においてGがG-55である一般式(8-12)[式中、Y, R1, R4, R5及びnは前記と同じ意味を表す。]で表される化合物を得ることができる。 General formula (34) [wherein Y, R 1 , R 4 , n and P represent the same meaning as described above. And a compound represented by the general formula (40) [wherein R 5 represents the same meaning as described above. Or a compound represented by the general formula (41): wherein R 5 represents the same meaning as described above. And the compound represented by the literature, for example, synthesis, 1983, p. 203, Japanese Patent Application Publication (JP 06/092957), Journal of Fluorine Chemistry [J Fluorine Chem.] After forming a dioxolane ring by reacting according to the method described in 1989, vol. 44, page 377, etc., deprotecting each protecting group by a commonly used method, General formula (8-12) wherein G is G-55 in general formula (8) [wherein Y, R 1 , R 4 , R 5 and n represent the same meaning as described above. The compound represented by this can be obtained.
ここで用いられる一般式(40)で表される化合物は公知化合物であり、一部は市販品として入手できる。また、それ以外のものも文献記載の公知の方法、例えば、ジャーナル・オブ・ジ・アメリカン・ケミカル・ソサイエティー[J. Am. Chem. Soc.]1966年、88巻、2194頁、テトラヘドロン・レターズ[Tetrahedron Lett.]1995年、36巻、3277頁及び2000年、41巻、7847頁等に記載の方法に準じて容易に合成することができる。 The compounds represented by the general formula (40) used here are known compounds, and some of them are available as commercial products. Other methods are known methods described in the literature, for example, Journal of the American Chemical Society [J. Am. Chem. Soc.] 1966, 88, 2194, Tetrahedron Letters. [Tetrahedron Lett.] 1995, 36, 3277 and 2000, 41, 7847, etc., can be easily synthesized.
また、一般式(41)で表される化合物のあるものは公知化合物であり、また、それ以外のものも文献記載の公知の方法、例えば、ジャーナル・オブ・ザ・ケミカル・ソサイエティー・パーキン・トランスアクションズ 1 [J. Chem. Soc., Perkin Trans. 1]1983年、3020頁等に記載の方法に準じて容易に合成することができる。 Some of the compounds represented by the general formula (41) are known compounds, and others are known methods described in the literature, for example, Journal of the Chemical Society Parkin Trans Actions 1 [J. Chem. Soc., Perkin Trans. 1] can be easily synthesized according to the method described in 1983, p.
反応式14 Reaction formula 14
一般式(21)[式中、Y, R1, R4, R6a, R6b, n及びPは前記と同じ意味を表す。]で表される化合物と一般式(42)[式中、R6cは(Z2)p1によって置換されていてもよいフェニル基を表す。]で表される化合物とを文献記載の公知の方法、例えば、ザ・ジャーナル・オブ・オーガニック・ケミストリー[J. Org. Chem.]1971年、36巻、3316頁等に記載の方法に準じて反応させることにより3、4−ジヒドロ−2H−ピロール環を形成し、各々の保護基について一般的に用いられる方法で脱保護することにより、一般式(8)においてGがG-6であり、R5が水素原子である一般式(8-13)[式中、Y, R1, R4, R6a, R6b及びnは前記と同じ意味を表し、R6cは(Z2)p1によって置換されていてもよいフェニル基を表す。]で表される化合物を得ることができる。 General formula (21) [wherein Y, R 1 , R 4 , R 6a , R 6b , n and P represent the same meaning as described above. And a compound represented by the general formula (42): wherein R 6c represents a phenyl group which may be substituted by (Z 2 ) p1 . In accordance with a known method described in the literature, for example, the method described in The Journal of Organic Chemistry [J. Org. Chem.] 1971, 36, 3316, etc. 3,4-dihydro -2 H by reacting - pyrrole ring to form, by deprotection with commonly used methods for each of the protecting group, in the general formula (8) G is located in G-6 , R 5 is a hydrogen atom (8-13) [wherein Y, R 1 , R 4 , R 6a , R 6b and n represent the same meaning as described above, and R 6c represents (Z 2 ) p1 Represents a phenyl group optionally substituted by. The compound represented by this can be obtained.
ここで用いられる一般式(42)で表される化合物は公知化合物であり、一部は市販品として入手できる。また、それ以外のものも文献記載の公知の方法、例えば、アンゲバンテ・ヘミー[Angew. Chem.]1965年、77巻、492頁、ケミッシェ・ベリヒテ[Chem. Ber. ]1960年、93巻、239頁等に記載の方法に準じて容易に合成することができる。 The compound represented by the general formula (42) used here is a known compound, and a part thereof can be obtained as a commercial product. Other methods are known methods described in the literature, for example, Angelew. Chem. 1965, 77, 492, Chemische Berich [Chem. Ber.] 1960, 93, 239. It can be easily synthesized according to the method described on the page.
反応式15 Reaction formula 15
一般式(43)[式中、Y, R1, R4, R5, R6i, n及びPは前記と同じ意味を表す。]で表される化合物とジヨードメタンとを文献記載の公知の方法、例えばケミカル・アンド・ファーマシューティカル・ブレティン [Chem. Pharm. Bull.] 1992年、40巻、3189頁等に記載の方法に準じて反応させることによりシクロプロパン環を形成した後、各々の保護基について一般的に用いられる方法で脱保護することにより、一般式(8)においてGがG-71であり、R6j及びR6kが水素原子である一般式(8-14)[式中、Y, R1, R4, R5, R6i及びnは前記と同じ意味を表す。]で表される化合物を得ることができる。 General formula (43) [wherein Y, R 1 , R 4 , R 5 , R 6i , n and P represent the same meaning as described above. In accordance with a known method described in the literature, for example, Chemical and Pharmaceutical Bulletin [Chem. Pharm. Bull.] 1992, 40, 3189 In the general formula (8), G is G-71, and R 6j and R 6k are formed by deprotecting each protecting group by a method generally used. In general formula (8-14), wherein Y, R 1 , R 4 , R 5 , R 6i and n are as defined above. The compound represented by this can be obtained.
また、一般式(43)で表される化合物をフルオロジヨードメタンと文献記載の公知の方法、例えばテトラヘドロン[Tetrahedron]1979年、35巻、1919頁、テトラヘドロン・レターズ[Tetrahedron Lett.]1975年、1820頁等に記載の方法に準じて反応させるか、ジクロロメタン又はジブロモメタンと文献記載の公知の方法、例えばザ・ジャーナル・オブ・オーガニック・ケミストリー[J. Org. Chem.]1994年、59巻、4087頁、テトラヘドロン[Tetrahedron]1970年、26巻、4203頁、テトラヘドロン・レターズ[Tetrahedron Lett.]1987年、28巻、5075頁等に記載の方法に準じて反応させることにより、一般式(8)においてGがG-71であり、R6kが水素原子である一般式(8-15)[式中、Y, R1, R4, R5, R6i及びnは前記と同じ意味を表し、R6jはフッ素原子、塩素原子又は臭素原子を表す。]で表される化合物を得ることができる。 Further, the compound represented by the general formula (43) is converted to fluorodiiodomethane and a known method described in the literature, for example, tetrahedron [Tetrahedron] 1979, Vol. The reaction is carried out according to the method described on page 1820, etc., or a known method described in the literature with dichloromethane or dibromomethane, for example, The Journal of Organic Chemistry [J. Org. Vol. 4087, Tetrahedron 1970, 26, 4203, Tetrahedron Lett. 1987, 28, 5075, etc. General formula (8-15) wherein G is G-71 and R 6k is a hydrogen atom in formula (8) [wherein Y, R 1 , R 4 , R 5 , R 6i and n are the same as above Intention The stands, R 6j represents a fluorine atom, a chlorine atom or a bromine atom. The compound represented by this can be obtained.
或いは、一般式(43)で表される化合物とヘキサフルオロ-1、2-エポキシプロパン又は公知の一般式(44)[式中、R6j及びR6kは、各々独立してフッ素原子、塩素原子又は臭素原子を表し、J5は水素原子、塩素原子又は臭素原子等を表し、J6は塩素原子、臭素原子、カルボキシル基又はアルコキシカルボニル基等を表す。]で表される化合物とを文献記載の公知の方法、例えば、ジャーナル・オブ・ザ・ケミカル・ソサイエティー・パーキン・トランスアクションズ 1 [J. Chem. Soc., Perkin Trans. 1]1995年、653頁、ザ・ジャーナル・オブ・オーガニック・ケミストリー[J. Org. Chem.]1964年、29巻、1886頁、1986年、51巻、974頁及び1990年、55巻、5420頁、テトラヘドロン[Tetrahedron]1989年、45巻、2925頁、1990年、46巻、1911頁及び1999年、55巻、10325頁、テトラヘドロン・レターズ[Tetrahedron Lett.]1971年、3869頁、1988年、29巻、6749頁及び1998年、39巻、3013頁等に記載の方法に準じて反応させることにより、一般式(8)においてGがG-71である一般式(8-16)[式中、Y, R1, R4, R5, R6i及びnは前記と同じ意味を表し、R6j及びR6kは、各々独立してフッ素原子、塩素原子又は臭素原子を表す。]で表される化合物を得ることができる。 Alternatively, the compound represented by the general formula (43) and hexafluoro-1,2-epoxypropane or a known general formula (44) [wherein R 6j and R 6k are each independently a fluorine atom, a chlorine atom, Or represents a bromine atom, J 5 represents a hydrogen atom, a chlorine atom, a bromine atom or the like, and J 6 represents a chlorine atom, a bromine atom, a carboxyl group or an alkoxycarbonyl group. And a known method described in the literature, for example, Journal of the Chemical Society Perkin Transactions 1 [J. Chem. Soc., Perkin Trans. 1] 1995, page 653. The Journal of Organic Chemistry [J. Org. Chem.] 1964, 29, 1886, 1986, 51, 974 and 1990, 55, 5420, Tetrahedron 1989, 45, 2925, 1990, 46, 1911 and 1999, 55, 10325, Tetrahedron Lett. 1971, 3869, 1988, 29, 6749 And 1998, Vol. 39, p. 3013, etc., the reaction is carried out according to the general formula (8-16) wherein G is G-71 in the general formula (8). In the formula, Y, R 1 , R 4 , R 5 , R 6i and n represent the same meaning as described above, and R 6j and R 6k each independently represent a fluorine atom, a chlorine atom or a bromine atom. The compound represented by this can be obtained.
さらに、一般式(43)で表される化合物と公知のマロノニトリル誘導体とを文献記載の公知の方法、例えばジャーナル・オブ・ザ・ケミカル・ソサイエティー・ケミカル・コミュニケーションズ[J. Chem. Soc. Chem. Commun.]1989年、1286頁、テトラヘドロン・レターズ[Tetrahedron Lett.]1966年、1415頁等に記載の方法に準じて反応させることにより、一般式(8)においてGがG-71であり、R6j及びR6kがシアノ基である一般式(8-17)[式中、Y, R1, R4, R5, R6i及びnは前記と同じ意味を表す。]で表される化合物を得ることができる。 Further, the compound represented by the general formula (43) and a known malononitrile derivative are converted into known methods described in the literature, for example, Journal of the Chemical Society Chemical Communications [J. Chem. Soc. Chem. 1989, p. 1286, Tetrahedron Lett. 1966, p. 1415, etc., by reacting according to the method described in general formula (8), G is G-71, R General formula (8-17) wherein 6j and R 6k are cyano groups [wherein Y, R 1 , R 4 , R 5 , R 6i and n represent the same meaning as described above. The compound represented by this can be obtained.
反応式16 Reaction formula 16
一般式(45)[式中、Y, R1, R4, R6j, R6k, n及びPは前記と同じ意味を表す。]で表される化合物と一般式(46)[式中、R5は(Z2)p1によって置換されていてもよいフェニル基を表し、R6iは水素原子又はアルコキシカルボニル基等を表し、J7は=N+=N-基又は=NNHSO2Ph-4-CH3基等を表す。]で表される化合物とを文献記載の一般的なロジウム触媒を用いた付加反応、例えばジャーナル・オブ・ジ・アメリカン・ケミカル・ソサイエティー[J. Am. Chem. Soc.]2001年、123巻、2695頁、国際特許出願公報(WO 98/3470号公報)等に記載の方法に準じて反応させるか、或いは一般式(45)で表される化合物と一般式(47)[式中、R5は(Z2)p1によって置換されていてもよいフェニル基を表し、R6iはフッ素原子、塩素原子又は臭素原子を表し、J8は塩素原子又は臭素原子を表す。]で表される化合物とを文献記載の公知の方法、例えばザ・ジャーナル・オブ・オーガニック・ケミストリー[J. Org. Chem.]1962年、27巻、2685頁、テトラヘドロン・レターズ[Tetrahedron Lett.]1965年、3445頁及び1968年、11962頁等に記載の方法に準じて反応させることによりシクロプロパン環を形成した後、各々の保護基について一般的に用いられる方法で脱保護することにより、一般式(8)においてGがG-71である一般式(8-16)[式中、Y, R1, R4, R6j, R6k及びnは前記と同じ意味を表し、R5は(Z2)p1によって置換されていてもよいフェニル基を表し、R6iは水素原子、フッ素原子、塩素原子、臭素原子又はアルコキシカルボニル基を表す。]で表される化合物を得ることができる。 General formula (45) [wherein Y, R 1 , R 4 , R 6j , R 6k , n and P represent the same meaning as described above. And a compound represented by the general formula (46) [wherein R 5 represents a phenyl group optionally substituted by (Z 2 ) p1 , R 6i represents a hydrogen atom, an alkoxycarbonyl group, or the like; 7 = N + = N - represents a group or = NNHSO 2 Ph-4-CH 3 group or the like. ], For example, Journal of the American Chemical Society [J. Am. Chem. Soc.] 2001, Vol. 123, 2695 pages, international patent application publication (WO 98/3470) and the like, or a compound represented by the general formula (45) and the general formula (47) [wherein R 5 Represents a phenyl group which may be substituted by (Z 2 ) p1 , R 6i represents a fluorine atom, a chlorine atom or a bromine atom, and J 8 represents a chlorine atom or a bromine atom. And the compound represented by the literature, for example, The Journal of Organic Chemistry [J. Org. Chem.] 1962, 27, 2685, Tetrahedron Letters [Tetrahedron Lett. After forming a cyclopropane ring by reacting according to the method described in 1965, p. 3445 and 1968, p. 11962, etc., deprotecting each protecting group by a generally used method, General formula (8-16) wherein G is G-71 in general formula (8) [wherein Y, R 1 , R 4 , R 6j , R 6k and n represent the same meaning as described above, and R 5 represents (Z 2 ) represents a phenyl group which may be substituted by p1 , and R 6i represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an alkoxycarbonyl group. The compound represented by this can be obtained.
ここで用いられる一般式(46)で表される化合物及び一般式(47)で表される化合物は、それぞれ対応する上記文献記載の方法に準じて合成することができる。 The compound represented by the general formula (46) and the compound represented by the general formula (47) used here can be synthesized according to the corresponding methods described in the above documents.
製造法Dにおいて、一般式(1)で表される化合物を製造するための原料化合物である、一般式(9)で表される化合物は、例えば下記の反応式17又は反応式18で表される方法等を用いて合成できる。 In the production method D, the compound represented by the general formula (9), which is a raw material compound for producing the compound represented by the general formula (1), is represented by, for example, the following reaction formula 17 or reaction formula 18. Can be synthesized using a method such as
反応式17 Reaction formula 17
一般式(20)[式中、X及びmは前記と同じ意味を表す。]で表される化合物と一般式(8)[式中、G, Y, R1, R4, R5, R6, l及びnは前記と同じ意味を表す。]で表される化合物とを製造法Aと同様な条件下反応させることにより、一般式(9)においてW1が酸素原子である一般式(9-2)[式中、G, X, Y, R1, R4, R5, R6, l, m及びnは前記と同じ意味を表す。]で表される化合物を得ることができる。 Formula (20) [wherein X and m represent the same meaning as described above. And a compound represented by the general formula (8): wherein G, Y, R 1 , R 4 , R 5 , R 6 , l and n have the same meaning as described above. And a compound represented by the general formula (9-2) in which W 1 is an oxygen atom in the general formula (9) [wherein G, X, Y , R 1 , R 4 , R 5 , R 6 , l, m and n have the same meaning as described above. The compound represented by this can be obtained.
反応式18 Reaction formula 18
一般式(13)[式中、G, X, Y, R4, R5, R6, l, m及びnは前記と同じ意味を表す。]で表される化合物を文献記載の公知の方法、例えば、ケミカル・レビューズ[Chem. Rev.]1990年、90巻、879頁等に記載の方法に準じて、位置選択的リチオ化後、炭酸ガスと反応させることにより、一般式(9)においてW1が酸素原子であり、R1が水素原子である一般式(9-3)[式中、G, X, Y, R4, R5, R6, l, m及びnは前記と同じ意味を表す。]で表される化合物を得ることができる。なお、R-Liはブチルリチウム等のアルキルリチウム試薬を表す。 General formula (13) [wherein G, X, Y, R 4 , R 5 , R 6 , l, m, and n represent the same meaning as described above. In accordance with a known method described in the literature, for example, a method described in Chemical Reviews [Chem. Rev.] 1990, 90, 879, etc., after regioselective lithiation, By reacting with carbon dioxide, general formula (9-3) in which W 1 is an oxygen atom and R 1 is a hydrogen atom in general formula (9) [wherein G, X, Y, R 4 , R 5 , R 6 , l, m and n represent the same meaning as described above. The compound represented by this can be obtained. R-Li represents an alkyl lithium reagent such as butyl lithium.
製造法Eにおいて、一般式(1)で表される化合物を製造するための原料化合物である、一般式(10)で表される化合物は、例えば下記の反応式19又は反応式20で表される方法等を用いて合成できる。 In the production method E, the compound represented by the general formula (10), which is a raw material compound for producing the compound represented by the general formula (1), is represented by, for example, the following reaction formula 19 or reaction formula 20. Can be synthesized using a method such as
反応式19 Reaction formula 19
一般式(20)[式中、X及びmは前記と同じ意味を表す。]で表される化合物と一般式(5)[式中、R2及びR3は前記と同じ意味を表す。]で表される化合物とを製造法Aと同様な条件下反応させることにより、一般式(10)においてW2が酸素原子である一般式(10-2)[式中、X, R2, R3及びmは前記と同じ意味を表す。]で表される化合物を得ることができる。 Formula (20) [wherein X and m represent the same meaning as described above. And a compound represented by the general formula (5): wherein R 2 and R 3 have the same meaning as described above. And a compound represented by the general formula (10-2) in which W 2 is an oxygen atom in the general formula (10) [wherein X, R 2 , R 3 and m have the same meaning as described above. The compound represented by this can be obtained.
反応式20 Reaction formula 20
一般式(11)[式中、X, R3及びmは前記と同じ意味を表す。]で表される化合物を反応式12と同様に反応させることにより、一般式(10)においてW2が酸素原子であり、R2が水素原子である一般式(10-3)[式中、X, R3及びmは前記と同じ意味を表す。]で表される化合物を得ることができる。なお、R-Liはブチルリチウム等のアルキルリチウム試薬を表す。 Formula (11) [wherein X, R 3 and m represent the same meaning as described above. In the general formula (10), W 2 is an oxygen atom and R 2 is a hydrogen atom in the general formula (10-3) [wherein X, R 3 and m have the same meaning as described above. The compound represented by this can be obtained. R-Li represents an alkyl lithium reagent such as butyl lithium.
製造法Fにおいて、一般式(1)で表される化合物を製造するための原料化合物である一般式(11)で表される化合物の或るものは公知化合物であり、一部は市販品として入手できる。また、それ以外のものも文献記載の公知の方法、例えばブレティン・オブ・ザ・ケミカル・ソサイエティー・オブ・ジャパン[Bull. Chem. Soc. Jpn.]1985年、58巻、3291頁、ザ・ジャーナル・オブ・オーガニック・ケミストリー[J. Org. Chem.]1991年、56巻、2395頁、テトラヘドロン・レターズ[Tetrahedron Lett.]1994年、35巻、2113頁、国際特許出願公報(WO 98/23581号公報)等に記載の方法に準じて容易に合成することができる。 In the production method F, some of the compounds represented by the general formula (11), which are raw material compounds for producing the compounds represented by the general formula (1), are known compounds, and some are commercially available. Available. In addition, other methods known in the literature, for example, Bulletin of the Chemical Society of Japan [Bull. Chem. Soc. Jpn.] 1985, 58, 3291, The Journal Of organic chemistry [J. Org. Chem.] 1991, 56, 2395, Tetrahedron Lett. 1994, 35, 2113, International Patent Application Publication (WO 98/23581) It can be easily synthesized according to the method described in Japanese Patent Publication No.
製造法Fで用いられる一般式(12)で表される化合物は、次のようにして合成できる。 The compound represented by the general formula (12) used in production method F can be synthesized as follows.
反応式21 Reaction formula 21
すなわち、一般式(8)においてR1が水素原子である一般式(8-1)[式中、G, Y, R4, R5, R6, l及びnは前記と同じ意味を表す。]で表される化合物と一般式(48)[式中、W1は酸素原子又は硫黄原子を表す。]で表される市販のホスゲン、チオオスゲン又はそれらの等価体とを文献記載の公知の方法、例えばアンゲバンテ・ヘミー・インターナショナル・エディション・イン・イングリッシュ[Angew. Chem. Int. Ed. Engl.]1987年、26巻、894頁及び1995年、34巻、2497頁、ザ・ジャーナル・オブ・オーガニック・ケミストリー[J. Org. Chem.]1976年、41巻、2070頁、シンセシス[Synthesis]1988年、990頁、テトラヘドロン・レターズ[Tetrahedron Lett.]1997年、38巻、919頁等に記載の方法に準じて反応させることにより、一般式(12)[式中、G, W1, Y, R4, R5, R6, l及びnは前記と同じ意味を表す。]で表される化合物を容易に合成することができる。 That is, in general formula (8), R 1 is a hydrogen atom. General formula (8-1) [wherein, G, Y, R 4 , R 5 , R 6 , l and n represent the same meaning as described above. And a compound represented by the general formula (48): wherein W 1 represents an oxygen atom or a sulfur atom. And a commercially available phosgene, thioosgen or an equivalent thereof, for example, known methods described in the literature, for example, Angewante Chemie International Edition in English [Angew. Chem. Int. Ed. Engl.] 1987 26, 894 and 1995, 34, 2497, The Journal of Organic Chemistry [J. Org. Chem.] 1976, 41, 2070, Synthesis 1988, 990 Page, Tetrahedron Letters [1997], 38, 919, etc., by reaction according to the general formula (12) [wherein G, W 1 , Y, R 4 , R 5 , R 6 , l and n have the same meaning as described above. ] Can be easily synthesized.
製造法Gにおいて、一般式(1)で表される化合物を製造するための原料化合物である、一般式(13)で表される化合物は、次のようにして合成できる。 In production method G, the compound represented by general formula (13), which is a raw material compound for producing the compound represented by general formula (1), can be synthesized as follows.
反応式22 Reaction formula 22
すなわち、一般式(49)[式中、X及びmは前記と同じ意味を表す。]で表される化合物と一般式(8)においてR1が水素原子である一般式(8-1)[式中、G, Y, R4, R5, R6, l及びnは前記と同じ意味を表す。]で表される化合物とを製造法Dと同様な条件下反応させるか、或いは一般式(49)で表される化合物を公知の方法(例えば、塩化チオニル、五塩化リン又はオキザリルクロライド等のクロル化剤)を用いて対応するカルボン酸クロライドした後に、一般式(8-1)で表される化合物と反応させることにより、一般式(13)[式中、G, X, Y, R4, R5, R6, l, m及びnは前記と同じ意味を表す。]で表される化合物を容易に合成することができる。 That is, in the general formula (49) [wherein X and m represent the same meaning as described above. And R 1 is a hydrogen atom in the general formula (8), wherein G, Y, R 4 , R 5 , R 6 , l and n are as defined above Represents the same meaning. Or a compound represented by the general formula (49) by a known method (for example, thionyl chloride, phosphorus pentachloride or oxalyl chloride). The corresponding carboxylic acid chloride using a chlorinating agent) is reacted with a compound represented by the general formula (8-1) to give a general formula (13) [wherein G, X, Y, R 4 , R 5 , R 6 , l, m and n have the same meaning as described above. ] Can be easily synthesized.
ここで用いられる一般式(49)で表される化合物は公知化合物であり、一部は市販品として入手できる。 The compounds represented by the general formula (49) used here are known compounds, and some of them are available as commercial products.
製造法Gで用いられる一般式(14)で表される化合物の或るものは公知化合物であり、一部は市販品として入手できる。また、それ以外のものも文献記載の一般的な合成方法、例えばザ・ジャーナル・オブ・オーガニック・ケミストリー[J. Org. Chem.]1996年、61巻、3883頁、3929頁及び6575頁、テトラヘドロン・レターズ[Tetrahedron Lett.]1999年、40巻、363頁及び6121頁等に記載の方法に準じて容易に合成することができる。 Some of the compounds represented by the general formula (14) used in production method G are known compounds, and some of them are commercially available. Other than that, general synthesis methods described in the literature, for example, The Journal of Organic Chemistry [J. Org. Chem.] 1996, 61, 3883, 3929 and 6575, Tetra It can be easily synthesized according to the method described in Tetrahedron Lett. 1999, 40, 363, 6121, etc.
製造法Hで用いられる一般式(15)で表される化合物及び製造法Iで用いられる一般式(16)で表される化合物の或るものは公知化合物であり、一部は市販品として入手できる。また、それ以外のものも文献記載の一般的な合成方法、例えばケミストリー・レターズ[Chem. Lett.]1976年、373頁、ジャーナル・オブ・ジ・アメリカン・ケミカル・ソサイエティー[J. Am. Chem. Soc.]1964年、86巻、4383頁、ザ・ジャーナル・オブ・オーガニック・ケミストリー[J. Org. Chem.]1976年、41巻、4028頁及び1978年、43巻、3244頁、オーガニック・シンセシス[Org. Synth.]1988年、コレクティブボリューム6巻、101頁、テトラヘドロン・レターズ[Tetrahedron Lett.]1972年、4339頁、英国特許(GB 2,161,802号公報)、ヨーロッパ特許(EP 0,051,273号公報)等に記載の方法に準じて容易に合成することができる。 Some of the compounds represented by general formula (15) used in production method H and the compounds represented by general formula (16) used in production method I are known compounds, and some are obtained as commercial products. it can. Other than the above, general synthesis methods described in the literature, for example, Chemistry Letters [Chem. Lett.] 1976, 373 pages, Journal of the American Chemical Society [J. Am. Chem. Soc.] 1964, 86, 4383, The Journal of Organic Chemistry [J. Org. Chem.] 1976, 41, 4028 and 1978, 43, 3244, Organic Synthesis [Org. Synth.] 1988, Collective Volume 6, p. 101, Tetrahedron Lett. 1972, p. 4339, British Patent (GB 2,161,802), European Patent (EP 0,051,273), etc. It can be easily synthesized according to the method described in 1.
製造法Jにおいて、一般式(1)で表される化合物を製造するための原料化合物である、一般式(17)で表される化合物は、一般式(21)で表される化合物を一般的に用いられる方法で脱保護した後、製造法A〜製造法Gを用いて一般式(1)で表される化合物と同様に合成できる。 In production method J, the compound represented by general formula (17), which is a raw material compound for producing the compound represented by general formula (1), is generally the same as the compound represented by general formula (21). After deprotecting by the method used in the above, it can be synthesized in the same manner as the compound represented by the general formula (1) by using Production Method A to Production Method G.
製造法Jで用いられる一般式(18)で表される化合物及び一般式(19)で表される化合物の或るものは公知化合物であり、一部は市販品として入手できる。また、それ以外のものも文献記載の公知の方法、例えば一般式(18)で表される化合物はケミストリー・レターズ[Chem. Lett.]1986年、183頁、ザ・ジャーナル・オブ・オーガニック・ケミストリー[J. Org. Chem.]1980年、45巻、3916頁及び1990年、55巻、4585頁、テトラヘドロン・レターズ[Tetrahedron Lett.]1993年、34巻、2831頁及び1996年、37巻、5699頁等に記載の方法に準じて、一般式(19)で表される化合物はジャーナル・オブ・フルオリン・ケミストリー[J. Fluorine Chem.]1991年、55巻、149頁、ザ・ジャーナル・オブ・オーガニック・ケミストリー[J. Org. Chem.]1979年、44巻、3872頁等に記載の方法に準じて、各々容易に合成することができる。 Some of the compounds represented by the general formula (18) and the compounds represented by the general formula (19) used in the production method J are known compounds, and some of them are commercially available. Other than the above, known methods described in the literature, for example, the compound represented by the general formula (18) is Chemistry Letters [Chem. Lett.] 1986, p. 183, The Journal of Organic Chemistry. [J. Org. Chem.] 1980, 45, 3916 and 1990, 55, 4585, Tetrahedron Lett. 1993, 34, 2831 and 1996, 37, According to the method described on page 5699, the compound represented by the general formula (19) is Journal of Fluorine Chem. [J. Fluorine Chem.] 1991, 55, 149, The Journal of Organic chemistry [J. Org. Chem.] Each can be easily synthesized according to the method described in 1979, 44, 3872, etc.
一般式(20)で表される化合物の或るものは公知化合物であり、一部は市販品として入手できる。また、それ以外のものも、例えば次のようにして合成できる。 Some of the compounds represented by the general formula (20) are known compounds, and some of them are commercially available. Others can be synthesized as follows, for example.
反応式23 Reaction formula 23
すなわち、一般式(50)[式中、X及びmは前記と同じ意味を表し、Rはメチル基、エチル基等の低級アルキル基を表す。]で表される化合物を文献記載の一般的な加水分解反応、例えばアンゲバンテ・ヘミー[Angew. Chem.]1951年、63巻、329頁、ジャーナル・オブ・ジ・アメリカン・ケミカル・ソサイエティー[J. Am. Chem. Soc.]1929年、51巻、1865頁等に記載の方法に準じて一般式(51)[式中、X及びmは前記と同じ意味を表す。]で表されるフタル酸誘導体とした後、文献記載の一般的な脱水環化反応、例えばザ・ジャーナル・オブ・オーガニック・ケミストリー[J. Org. Chem.]1987年、52巻、129頁等に記載の方法に準じた条件下反応させることにより、一般式(20)[式中、X及びmは前記と同じ意味を表す。]で表される化合物を得ることができる。 That is, general formula (50) [wherein X and m represent the same meaning as described above, and R represents a lower alkyl group such as a methyl group or an ethyl group. ], The general hydrolysis reaction described in the literature, for example, Angewante Chem. 1951, 63, 329, Journal of the American Chemical Society [J. Am. Chem. Soc.], 1929, Vol. 51, p. 1865, etc., the general formula (51) [wherein X and m represent the same meaning as described above. ], Followed by a general dehydration cyclization reaction described in the literature, such as The Journal of Organic Chemistry [J. Org. Chem.] 1987, 52, 129, etc. In the general formula (20), wherein X and m represent the same meaning as described above. The compound represented by this can be obtained.
ここで用いられる一般式(50)で表される化合物は公知化合物であり、一部は市販品として入手できる。 The compounds represented by the general formula (50) used here are known compounds, and some of them are available as commercial products.
一般式(21)で表される化合物は、例えば次のようにして合成できる。 The compound represented by the general formula (21) can be synthesized, for example, as follows.
反応式24 Reaction formula 24
すなわち、一般式(52)[式中、Y, R1, n及びPは前記と同じ意味を表し、J9は臭素原子、ヨウ素原子、ハロスルホネート基(例えば、フルオロスルホニルオキシ基)、C1〜C4ハロアルキルスルホネート基(例えば、トリフルオロメタンスルホニルオキシ基)のような脱離基を表す。]で表される化合物と一般式(53)[式中、R4, R6a及びR6bは前記と同じ意味を表し、J10は臭素原子、ヨウ素原子等のハロゲン原子を表す。]で表される化合物とを文献記載の一般的なパラジウム等遷移金属触媒を用いたクロスカップリング反応、例えばザ・ジャーナル・オブ・オーガニック・ケミストリー[J. Org. Chem.]1991年、56巻、7336頁、テトラヘドロン・レターズ[Tetrahedron Lett.]2001年、42巻、4083頁等に記載の方法に準じて反応させることにより、一般式(21)[式中、Y, R1, R4, R6a, R6b, n及びPは前記と同じ意味を表す。]で表される化合物を得ることができる。 That is, in the general formula (52) [wherein Y, R 1 , n and P are as defined above, J 9 represents a bromine atom, an iodine atom, a halosulfonate group (for example, a fluorosulfonyloxy group), C 1 -C 4 haloalkyl sulfonate group (e.g., trifluoromethanesulfonyloxy group) represents a leaving group such as. And a compound represented by the general formula (53) [wherein R 4 , R 6a and R 6b represent the same meaning as described above, and J 10 represents a halogen atom such as a bromine atom or an iodine atom. And a compound represented by the above general cross-coupling reaction using a transition metal catalyst such as palladium described in the literature, for example, The Journal of Organic Chemistry [J. Org. Chem.] 1991, Vol. 7336, Tetrahedron Lett. 2001, 42, 4083, etc., by reacting in accordance with the general formula (21) [wherein Y, R 1 , R 4 , R 6a , R 6b , n and P have the same meaning as described above. The compound represented by this can be obtained.
ここで用いられる一般式(53)で表される化合物の或るものは公知化合物であり、一部は市販品として入手できる。また、それ以外のものも文献記載の公知の方法、例えばジャーナル・オブ・ジ・アメリカン・ケミカル・ソサイエティー[J. Am. Chem. Soc.]1971年、93巻、1925頁、テトラヘドロン・レターズ[Tetrahedron Lett.]1990年、31巻、1919頁等に記載の方法に準じて容易に合成することができる。 Some of the compounds represented by the general formula (53) used here are known compounds, and some of them are available as commercial products. Other methods are also known in the literature, such as Journal of the American Chemical Society [J. Am. Chem. Soc.] 1971, 93, 1925, Tetrahedron Letters [ Tetrahedron Lett.] It can be easily synthesized according to the method described in 1990, Vol. 31, p. 1919.
或いは、一般式(34)[式中、Y, R1, R4, n及びPは前記と同じ意味を表す。]で表される化合物を文献記載の公知なカルボニル基のオレフィン化反応、例えばザ・ジャーナル・オブ・オーガニック・ケミストリー[J. Org. Chem.]1986年、51巻、5252頁及び1994年、59巻、2898頁、シンセシス[Synthesis]1991年、29頁、テトラヘドロン・レターズ[Tetrahedron Lett.]1985年、26巻、5579頁等に記載の方法に準じて反応させることにより、一般式(21)で表される化合物を得ることもできる。 Alternatively, the general formula (34) [wherein Y, R 1 , R 4 , n and P represent the same meaning as described above. The olefination reaction of a known carbonyl group described in the literature, for example, The Journal of Organic Chemistry [J. Org. Chem.] 1986, 51, 5252 and 1994, 59 Volume 2, p. 2898, Synthesis 1991, p. 29, Tetrahedron Lett. 1985, Vol. 26, p. 5579, and the like, by reacting according to the general formula (21) The compound represented by these can also be obtained.
一般式(22)で表される化合物は、例えば次のようにして合成できる。 The compound represented by the general formula (22) can be synthesized, for example, as follows.
反応式25 Reaction formula 25
すなわち、一般式(54)[式中、Y, R1, R4, R6a, R6b, n及びPは前記と同じ意味を表す。]で表される化合物を文献記載の一般的な方法、例えばジャーナル・オブ・ジ・アメリカン・ケミカル・ソサイエティー[J. Am. Chem. Soc.]1951年、73巻、96頁及び1965年、87巻、1358頁等に記載の方法に準じてアンモニアと反応させるか、例えばヘテロサイクルズ[Heterocycles]1986年、24巻、931頁等に記載の方法に準じてアジドと反応させた後、還元することにより、一般式(22)[式中、Y, R1, R4, R6a, R6b, n及びPは前記と同じ意味を表す。]で表される化合物を得ることができる。 That is, in the general formula (54) [wherein Y, R 1 , R 4 , R 6a , R 6b , n and P have the same meaning as described above. The compounds represented by the general formulas described in the literature, for example, Journal of the American Chemical Society [J. Am. Chem. Soc.] 1951, 73, 96 and 1965, 87 React with ammonia according to the method described in Vol. 1358, etc., or react with azide according to the method described in Heterocycles 1986, Vol. 24, page 931, etc., and then reduce. Accordingly, in the general formula (22) [wherein, Y, R 1 , R 4 , R 6a , R 6b , n and P represent the same meaning as described above. The compound represented by this can be obtained.
一般式(27)で表される化合物は、例えば次のように合成できる。 The compound represented by the general formula (27) can be synthesized, for example, as follows.
反応式26 Reaction formula 26
すなわち、一般式(55)[式中、Y, R1, R4, J4, n及びPは前記と同じ意味を表す。]で表される化合物と公知の一般式(24)[式中、R5及びJ3は前記と同じ意味を表す。]で表される化合物又は公知の一般式(25)[式中、R5は前記と同じ意味を表す。]で表される化合物とを、反応式5と同様な条件下反応させることにより、一般式(27)[式中、Y, R1, R4, R5, J4, n及びPは前記と同じ意味を表す。]で表される化合物を得ることができる。 That is, the general formula (55) [wherein Y, R 1 , R 4 , J 4 , n and P represent the same meaning as described above. And a known general formula (24) [wherein R 5 and J 3 represent the same meaning as described above. Or a known general formula (25) [wherein R 5 represents the same meaning as described above. And a compound represented by the general formula (27) [wherein Y, R 1 , R 4 , R 5 , J 4 , n and P are the same as those described above] Means the same. The compound represented by this can be obtained.
或いは、一般式(28)においてR6a及びR6bが水素原子である一般式(28-1)[式中、Y, R1, R4, R5, n及びPは前記と同じ意味を表す。]で表される化合物を文献記載の公知の方法、例えば、ザ・ジャーナル・オブ・オーガニック・ケミストリー[J. Org. Chem.]2000年、65巻、9223頁、テトラヘドロン・レターズ[Tetrahedron Lett.]1995年、36巻、1223頁、ドイツ国特許出願公報(DE 19528778号公報)等に記載の方法に準じて反応させることにより、一般式(27)で表される化合物を得ることもできる。 Or, in general formula (28), R 6a and R 6b are hydrogen atoms, general formula (28-1) [wherein Y, R 1 , R 4 , R 5 , n and P represent the same meaning as described above. . ], The journal of organic chemistry [J. Org. Chem.] 2000, 65, 9223, Tetrahedron Letters [Tetrahedron Lett. The compound represented by the general formula (27) can also be obtained by reacting according to the method described in 1995, Vol. 36, p. 1223, German Patent Application Publication (DE 19528778) and the like.
一般式(28)で表される化合物は、例えば次のように合成できる。 The compound represented by the general formula (28) can be synthesized, for example, as follows.
反応式27 Reaction formula 27
すなわち、一般式(56)[式中、Y, R1, R4, n及びPは前記と同じ意味を表す。]で表される化合物と公知の一般式(24)[式中、R5及びJ6は前記と同じ意味を表す。]で表される化合物又は公知の一般式(25)[式中、R5は前記と同じ意味を表す。]で表される化合物とを文献記載の公知の方法、例えばアンゲバンテ・ヘミー・インターナショナル・エディション・イン・イングリッシュ[Angew. Chem. Int. Ed. Engl.]1996年、35巻、2487頁、ジャーナル・オブ・ジ・アメリカン・ケミカル・ソサイエティー[J. Am. Chem. Soc.]1953年、75巻、5896頁、シンセティック・コミュニケーションズ[Synth. Commun.]1998年、28巻、3317頁等に記載の方法に準じて反応させることにより、一般式(28)[式中、Y, R1, R4, R5, n及びPは前記と同じ意味を表す。]で表される化合物を得ることができる。 That is, the general formula (56) [wherein Y, R 1 , R 4 , n and P represent the same meaning as described above. And a known general formula (24) [wherein R 5 and J 6 represent the same meaning as described above. Or a known general formula (25) [wherein R 5 represents the same meaning as described above. ], A known method described in the literature, for example, Angewante Chemie Int. Ed. Engl. 1996, 35, 2487, Journal Of the American Chemical Society [J. Am. Chem. Soc.] 1953, 75, 5896, Synth. Commun. 1998, 28, 3317, etc. In the general formula (28), wherein Y, R 1 , R 4 , R 5 , n and P have the same meaning as described above. The compound represented by this can be obtained.
一般式(29)で表される化合物は、例えば次のように合成できる。 The compound represented by the general formula (29) can be synthesized, for example, as follows.
反応式28 Reaction formula 28
すなわち、一般式(54)[式中、Y, R1, R4, R6a, R6b, n及びPは前記と同じ意味を表す。]で表される化合物を文献記載の公知の方法、例えばケミカル・アンド・ファーマシューティカル・ブレティン [Chem. Pharm. Bull.] 1993年、41巻、1035頁、ジャーナル・オブ・ザ・ケミカル・ソサイエティー [J. Chem. Soc.]1951年、778頁及び1960年、2653頁等に記載の方法に準じて反応させることにより、一般式(29)[式中、Y, R1, R4, R6a, R6b, n及びPは前記と同じ意味を表す。]で表される化合物を得ることができる。 That is, in the general formula (54) [wherein Y, R 1 , R 4 , R 6a , R 6b , n and P have the same meaning as described above. ], For example, Chemical and Pharmaceutical Bulletin [Chem. Pharm. Bull.] 1993, 41, 1035, Journal of the Chemical Society. [J. Chem. Soc.] By reacting according to the method described in 1951, 778 pages and 1960, 2653 pages, etc., general formula (29) [wherein Y, R 1 , R 4 , R 6a , R 6b , n and P have the same meaning as described above. The compound represented by this can be obtained.
一般式(31)で表される化合物は、例えば次のように合成できる。 The compound represented by the general formula (31) can be synthesized, for example, as follows.
反応式29 Reaction formula 29
すなわち、公知の一般式(57)[式中、R5及びJ8は前記と同じ意味を表す。]で表される化合物を文献記載の公知の方法、例えば例えば、ザ・ジャーナル・オブ・オーガニック・ケミストリー[J. Org. Chem.]1998年、53巻、5558頁等に記載の方法に準じて、一般式(58)[式中、R5及びJ8は前記と同じ意味を表す。]で表されるホスホニウム塩とした後、公知の一般式(59)[式中、R4は前記と同じ意味を表す。]で表される化合物と反応させることにより得られる一般式(60)[式中、R4及びR5は前記と同じ意味を表す。]で表される化合物を、文献記載の公知の方法、例えば、ジャーナル・オブ・ザ・ケミカル・ソサイエティー・パーキン・トランスアクションズ 1 [J. Chem. Soc., Perkin Trans. 1]1996年、2531頁等に記載の方法に準じて、一般式(52)[式中、Y, R1, n及びPは前記と同じ意味を表し、J9は臭素原子又はヨウ素原子を表す。]で表される化合物のハロゲン-金属交換反応により得られるリチウム塩と反応させることにより、一般式(31)[式中、Y, R1, R4, R5, n及びPは前記と同じ意味を表す。]で表される化合物を得ることができる。 That is, the known general formula (57) [wherein R 5 and J 8 represent the same meaning as described above. ] According to a known method described in the literature, for example, the method described in The Journal of Organic Chemistry [J. Org. Chem.] 1998, 53, 5558, etc. General formula (58) [wherein R 5 and J 8 represent the same meaning as described above. ], And then a known general formula (59) [wherein R 4 represents the same meaning as described above. Formula (60) wherein the obtained by reacting a compound represented by], R 4 and R 5 are as defined above. ], A known method described in the literature, for example, Journal of the Chemical Society Perkin Transactions 1 [J. Chem. Soc., Perkin Trans. 1] 1996, page 2531. In the general formula (52), Y, R 1 , n and P have the same meaning as described above, and J 9 represents a bromine atom or an iodine atom. ] Is reacted with a lithium salt obtained by a halogen-metal exchange reaction of the compound represented by the general formula (31) [wherein Y, R 1 , R 4 , R 5 , n and P are the same as defined above] Represents meaning. The compound represented by this can be obtained.
また、一般式(52)で表される化合物と公知の一般式(61)[式中、R5は前記と同じ意味を表す。]で表される化合物を、文献記載の公知の方法、例えば、シンセシス[Synthesis]1989年、869頁等に記載の方法に準じて反応させることにより、一般式(31)においてが水素原子である一般式(31-01)[式中、Y, R1, R5, n及びPは前記と同じ意味を表す。]で表される化合物を得ることもできる。 Further, the compound represented by the general formula (52) and the known general formula (61) [wherein R 5 represents the same meaning as described above. In the general formula (31), the compound represented by formula (31) is a hydrogen atom by reacting according to a known method described in the literature, for example, a method described in Synthesis, 1989, page 869 General formula (31-01) [wherein Y, R 1 , R 5 , n and P represent the same meaning as described above. The compound represented by this can also be obtained.
一般式(34)で表される化合物は、例えば次のように合成できる。 The compound represented by the general formula (34) can be synthesized, for example, as follows.
反応式30 Reaction formula 30
すなわち、公知の一般式(62)[式中、Y, R1, n及びPは前記と同じ意味を表す。]で表される化合物と公知の一般式(63)[式中、R4は前記と同じ意味を表し、J11はハロゲン原子、トリフルオロメタンスルホニルオキシ基、2-ピリジルオキシ基等の脱離基を表す。]で表される化合物又は公知の一般式(59)[式中、R4は前記と同じ意味を表す。]で表される化合物とを文献記載の一般的な芳香環のアシル化反応、例えばケミストリー・レターズ[Chem. Lett.]1990年、783頁、ザ・ジャーナル・オブ・オーガニック・ケミストリー[J. Org. Chem.]1991年、56巻、1963頁等に記載の方法に準じて反応させることにより、一般式(34)[式中、Y, R1, R4, n及びPは前記と同じ意味を表す。]で表される化合物を得ることができる。 That is, the known general formula (62) [wherein Y, R 1 , n and P represent the same meaning as described above. And a known general formula (63) [wherein R 4 represents the same meaning as described above, and J 11 represents a leaving group such as a halogen atom, a trifluoromethanesulfonyloxy group, a 2-pyridyloxy group, etc. Represents. Or a known general formula (59) wherein R 4 represents the same meaning as described above. The general aromatic ring acylation reaction described in the literature, for example, Chemistry Letters [Chem. Lett.] 1990, p. 783, The Journal of Organic Chemistry [J. Org] Chem.] By reacting according to the method described in 1991, Vol. 56, 1963, etc., general formula (34) [wherein Y, R 1 , R 4 , n and P have the same meaning as described above] Represents. The compound represented by this can be obtained.
或いは、一般式(52)[式中、Y, R1, n及びPは前記と同じ意味を表し、J9は臭素原子又はヨウ素原子を表す。]で表される化合物を文献記載の一般的な方法、例えばリチオ化した後、公知の一般式(64)[式中、R4は前記と同じ意味を表し、J12はハロゲン原子、水酸基、金属塩(例えば、-OLi、-ONa)、C1〜C4アルコキシ基(例えば、メトキシ基、エトキシ基)、ジ(C1〜C4アルキル)アミノ基(例えば、ジエチルアミノ基)、C1〜C4アルコキシ(C1〜C4アルキル)アミノ基(例えば、O,N-ジメチルヒドロキシアミノ基)又は環状アミノ基(例えば、ピペリジン-1-イル基、モルホリン-4-イル基、4-メチルピペラジン-1-イル基)を表す。]で表される化合物又は公知の一般式(59)で表される化合物と反応させるジャーナル・オブ・ジ・アメリカン・ケミカル・ソサイエティー[J. Am. Chem. Soc.]1955年、77巻、3657頁、テトラヘドロン・レターズ[Tetrahedron Lett.]1980年、21巻、2129頁及び1991年、32巻、2003頁、アメリカ合衆国特許出願公報(US 5,514,816号公報)等に記載の方法、或いはグリニャール反応剤を形成した後、一般式(64)で表される化合物又は一般式(59)で表される化合物と反応させるヘテロサイクルズ[Heterocycles]1987年、25巻、221頁、シンセティック・コミュニケーションズ[Synth. Commun.]1985年、15巻、1291頁及び1990年、20巻、1469頁、ドイツ国特許出願公報(DE 19727042号公報)等に記載の方法に準じて反応させることにより、一般式(34)で表される化合物を得ることもできる。 Alternatively, general formula (52) [wherein Y, R 1 , n and P represent the same meaning as described above, and J 9 represents a bromine atom or an iodine atom. ] After lithiation of the compound represented by the literature, for example, known general formula (64) [wherein R 4 represents the same meaning as described above, J 12 represents a halogen atom, a hydroxyl group, metal salts (e.g., -OLi, -ONa), C 1 ~C 4 alkoxy group (e.g., methoxy group, ethoxy group), di (C 1 -C 4 alkyl) amino group (e.g., diethylamino group), C 1 ~ C 4 alkoxy (C 1 -C 4 alkyl) amino group (for example, O, N-dimethylhydroxyamino group) or cyclic amino group (for example, piperidin-1-yl group, morpholin-4-yl group, 4-methylpiperazine) -1-yl group). Or the known general formula (59), Journal of the American Chemical Society [J. Am. Chem. Soc.] 1955, 77, 3657 Tetrahedron Lett. 1980, 21, 2129 and 1991, 32, 2003, US Patent Application Publication (US 5,514,816), etc., or Grignard reactant Heterocycles 1987, Vol. 25, p. 221, Synth. Communities [Synth. Communication] after forming and reacting with the compound represented by the general formula (64) or the compound represented by the general formula (59) In accordance with the method described in 1985, 15, 1291 and 1990, 20, 1469, German Patent Application Publication (DE 19727042), etc. To obtain a compound represented by the general formula (34).
一般式(43)で表される化合物及び一般式(45)で表される化合物は、一般式(21)で表される化合物と同様にして合成できる。 The compound represented by the general formula (43) and the compound represented by the general formula (45) can be synthesized in the same manner as the compound represented by the general formula (21).
一般式(52)で表される化合物は、例えば次のように合成できる。 The compound represented by the general formula (52) can be synthesized, for example, as follows.
反応式31 Reaction formula 31
すなわち、公知の一般式(65)[式中、Y, R1, n及びJ9は前記と同じ意味を表す。]で表される置換アニリンを文献記載の一般的な方法、例えばジャーナル・オブ・メディシナル・ケミストリー[J. Med. Chem.]1996年、39巻、673頁及び1997年、40巻、3542頁等に記載の方法に準じてアミノ基を保護することにより、一般式(52)[式中、Y, R1, J9, n及びPは前記と同じ意味を表す。]で表される化合物を得ることができる。 That is, the known general formula (65) [wherein Y, R 1 , n and J 9 represent the same meaning as described above. The substituted aniline represented by the general method described in the literature, for example, Journal of Medicinal Chemistry [J. Med. Chem.] 1996, 39, 673 and 1997, 40, 3542, etc. In the general formula (52), Y, R 1 , J 9 , n and P represent the same meaning as described above. The compound represented by this can be obtained.
また、公知の一般式(66)[式中、Y, R1及びnは前記と同じ意味を表す。]で表される置換アミノフェノールを、同様な条件下にてアミノ基を保護することにより一般式(67)[式中、Y, R1, n及びPは前記と同じ意味を表す。]で表される化合物とした後、文献記載の一般的なスルホニル化反応、例えばザ・ジャーナル・オブ・オーガニック・ケミストリー[J. Org. Chem.]1991年、56巻、3493頁及び1994年、59巻、1216頁等に記載の方法に準じて無水トリフルオロメタンスルホン酸又は無水フルオロスルホン酸と反応させることにより、J9がトリフルオロメタンスルホニルオキシ基又はフルオロスルホニルオキシ基である一般式(52)で表される化合物を得ることもできる。 Further, the known general formula (66) [wherein Y, R 1 and n represent the same meaning as described above. In the general formula (67), Y, R 1 , n and P represent the same meaning as described above by protecting the amino group with a substituted aminophenol represented by the general formula (67). ], Then the general sulfonylation reaction described in the literature, for example, The Journal of Organic Chemistry [J. Org. Chem.] 1991, 56, 3493 and 1994, In accordance with the general formula (52) in which J 9 is a trifluoromethanesulfonyloxy group or a fluorosulfonyloxy group by reacting with trifluoromethanesulfonic anhydride or fluorosulfonic anhydride according to the method described in Volume 59, page 1216, etc. The compounds represented can also be obtained.
一般式(54)で表される化合物は、例えば次のように合成できる。 The compound represented by the general formula (54) can be synthesized, for example, as follows.
反応式32 Reaction formula 32
すなわち、一般式(21)[式中、Y, R1, R4, R6a, R6b, n及びPは前記と同じ意味を表す。]で表される化合物を文献記載の公知の方法、例えばアンゲバンテ・ヘミー・インターナショナル・エディション・イン・イングリッシュ[Angew. Chem. Int. Ed. Engl.]2000年、39巻、3473頁、ジャーナル・オブ・ジ・アメリカン・ケミカル・ソサイエティー[J. Am. Chem. Soc.]2001年、123巻、2933頁、シンセシス[Synthesis]1999年、249頁等に記載の方法に準じて酸化することにより、一般式(54)[式中、Y, R1, R4, R6a, R6b, n及びPは前記と同じ意味を表す。]で表される化合物を得ることができる。 That is, the general formula (21) [wherein Y, R 1 , R 4 , R 6a , R 6b , n and P represent the same meaning as described above. ], For example, Angelevante Hemy International Edition in English [Angew. Chem. Int. Ed. Engl.] 2000, 39, 3473, Journal of・ The American Chemical Society [J. Am. Chem. Soc.] 2001, 123, 2933, Synthesis 1999, p. 249, etc. Formula (54) [wherein Y, R 1 , R 4 , R 6a , R 6b , n and P represent the same meaning as described above. The compound represented by this can be obtained.
一般式(55)で表される化合物は、例えば次のように合成できる。 The compound represented by the general formula (55) can be synthesized, for example, as follows.
反応式33 Reaction formula 33
すなわち、一般式(56)においてR6a及びR6bが水素原子である一般式(56-1)[式中、Y, R1, R4, n及びPは前記と同じ意味を表す。]で表される化合物を文献記載の公知の方法、例えばザ・ジャーナル・オブ・オーガニック・ケミストリー[J. Org. Chem.]1959年、24巻、527頁、シンセシス[Synthesis]1987年、479頁、テトラヘドロン[Tetrahedron]1993年、49巻、1993頁等に記載の方法に準じて反応させることにより、一般式(55)[式中、Y, R1, R4, J4, n及びPは前記と同じ意味を表す。]で表される化合物を得ることができる。 That is, in the general formula (56), R 6a and R 6b are hydrogen atoms in the general formula (56-1) [wherein Y, R 1 , R 4 , n and P have the same meaning as described above. ], For example, The Journal of Organic Chemistry [J. Org. Chem.] 1959, 24, 527, Synthesis 1987, 479. Tetrahedron, 1993, 49, 1993, and the like, by reacting according to the general formula (55) [wherein Y, R 1 , R 4 , J 4 , n and P Represents the same meaning as described above. The compound represented by this can be obtained.
一般式(56)で表される化合物は、例えば次のように合成できる。 The compound represented by the general formula (56) can be synthesized, for example, as follows.
反応式34 Reaction formula 34
すなわち、一般式(68)[式中、Y, R1, R4, n及びPは前記と同じ意味を表し、Rは水素原子又はメチル、エチル等の低級アルキル基を表す。]で表される化合物を文献記載の公知の方法、例えばケミカル・アンド・ファーマシューティカル・ブレティン [Chem. Pharm. Bull.] 1965年、13巻、999頁、ザ・ジャーナル・オブ・オーガニック・ケミストリー[J. Org. Chem.]1993年、58巻、3568頁、ドイツ国特許出願公報(DE 19528778号公報)等に記載の方法に準じて還元することにより、一般式(56)においてR6a及びR6bが水素原子である一般式(56-1)[式中、Y, R1, R4, n及びPは前記と同じ意味を表す。]で表される化合物を得ることができる。 That is, in the general formula (68) [wherein, Y, R 1 , R 4 , n and P represent the same meaning as described above, and R represents a hydrogen atom or a lower alkyl group such as methyl or ethyl. ], A known method described in the literature, for example, Chemical and Pharmaceutical Bulletin [Chem. Pharm. Bull.] 1965, 13, 999, The Journal of Organic Chemistry. [J. Org. Chem.] 1993, 58, 3568, reduction according to the method described in the German Patent Application Publication (DE 19528778) and the like, R 6a in general formula (56) and General formula (56-1) wherein R 6b is a hydrogen atom [wherein Y, R 1 , R 4 , n and P represent the same meaning as described above. The compound represented by this can be obtained.
一般式(68)で表される化合物は、例えば次のように合成できる。 The compound represented by the general formula (68) can be synthesized, for example, as follows.
反応式35 Reaction formula 35
すなわち、一般式(34)[式中、Y, R1, R4, n及びPは前記と同じ意味を表す。]で表される化合物を文献記載のアミノ酸合成の一般的な方法、例えばジャーナル・オブ・ジ・アメリカン・ケミカル・ソサイエティー[J. Am. Chem. Soc.]1960年、82巻、698頁、テトラヘドロン・レターズ[Tetrahedron Lett.]1996年、37巻、8655頁等に記載の方法に準じて一般式(69)[式中、Y, R1, R4, n及びPは前記と同じ意味を表す。]で表されるアミノニトリルとした後、例えばジャーナル・オブ・ザ・ケミカル・ソサイエティー [J. Chem. Soc.]1962年、3979頁等に記載の方法に準じて加水分解するか、或いはジャーナル・オブ・ジ・アメリカン・ケミカル・ソサイエティー[J. Am. Chem. Soc.]1943年、65巻、324頁、テトラヘドロン:アシンメトリー[Tetrahedron:Asymmetry]1997年、8巻、2913頁、ドイツ国特許出願公報(DE 19528778号公報)等に記載の方法に準じて、一般式(70)[式中、Y, R1, R4, n及びPは前記と同じ意味を表す。]で表されるイミダゾリジンジオンとした後加水分解することにより、一般式(68)においてRが水素原子である一般式(68-1)[式中、Y, R1, R4, n及びPは前記と同じ意味を表す。]で表される化合物を得ることができる。 That is, in the general formula (34) [wherein Y, R 1 , R 4 , n and P represent the same meaning as described above. ], For example, Journal of the American Chemical Society [J. Am. Chem. Soc.] 1960, 82, 698, Tetra In accordance with the method described in Tetrahedron Lett. 1996, 37, 8655, etc., the general formula (69) [wherein Y, R 1 , R 4 , n and P have the same meaning as described above] Represent. ] And then hydrolyzing according to the method described in Journal of the Chemical Society [J. Chem. Soc.] 1962, page 3979, etc. Of The American Chemical Society [J. Am. Chem. Soc.] 1943, 65, 324, Tetrahedron: Asymmetry 1997, 8, 2913, German patent application According to the method described in the publication (DE 19528778) and the like, general formula (70) [wherein Y, R 1 , R 4 , n and P have the same meaning as described above. In the general formula (68), R is a hydrogen atom in the general formula (68-1) [wherein Y, R 1 , R 4 , n and P represents the same meaning as described above. The compound represented by this can be obtained.
これらの各反応においては、反応終了後、通常の後処理を行なうことにより製造法A〜製造法Jの原料化合物となる各々の製造中間体を得ることができる。 In each of these reactions, after the completion of the reaction, each of the production intermediates that will be the raw material compounds of Production Method A to Production Method J can be obtained by carrying out ordinary post-treatment.
また、これらの方法により製造された各々の製造中間体は、単離・精製することなく、それぞれそのまま次工程の反応に用いることもできる。
製造法K
In addition, each production intermediate produced by these methods can be used as it is in the subsequent step without isolation and purification.
Production method K
一般式(7)[式中、W2, X, R3及びmは前記と同じ意味を表す。]で表される化合物と一般式(3)[式中、Y, R1, R4, R5, R6v及びnは前記と同じ意味を表す。]で表される化合物とを製造法Aと同様な条件下反応させることにより、一般式(2)においてW1が酸素原子であり、R2が水素原子である一般式(2-3)[式中、W2, X, Y, R1, R3, R4, R5, R6v, m及びnは前記と同じ意味を表す。]で表される本発明化合物を得ることができる。 General formula (7) [wherein W 2 , X, R 3 and m represent the same meaning as described above. And a compound represented by the general formula (3) [wherein Y, R 1 , R 4 , R 5 , R 6v and n have the same meaning as described above]. And a compound represented by the general formula (2-3) in which W 1 is an oxygen atom and R 2 is a hydrogen atom in the general formula (2). In the formula, W 2 , X, Y, R 1 , R 3 , R 4 , R 5 , R 6v , m and n represent the same meaning as described above. This invention compound represented by this can be obtained.
製造法Kにおいて、反応終了後の反応混合物は、直接濃縮、又は有機溶媒に溶解し、水洗後濃縮、又は氷水に投入、有機溶媒抽出後濃縮といった通常の後処理を行ない、目的の本発明化合物を得ることができる。また、精製の必要が生じたときには、再結晶、カラムクロマトグラフ、薄層クロマトグラフ、液体クロマトグラフ分取等の任意の精製方法によって分離、精製することができる。 In Production Method K, the reaction mixture after completion of the reaction is directly concentrated or dissolved in an organic solvent, washed with water, concentrated in ice water, or subjected to usual post-treatment such as concentration after extraction with an organic solvent. Can be obtained. Moreover, when the necessity for purification arises, it can be separated and purified by any purification method such as recrystallization, column chromatograph, thin layer chromatograph, liquid chromatographic fractionation and the like.
製造法Kで用いられる一般式(3)で表される化合物は、例えば下記の反応式36〜反応式39で表される方法等を用いて合成することができる。 The compound represented by the general formula (3) used in the production method K can be synthesized using, for example, the methods represented by the following reaction formula 36 to reaction formula 39.
反応式36 Reaction formula 36
一般式(34)[式中、Y, R1, R4, n及びPは前記と同じ意味を表す。]で表される化合物と、一般式(72)[式中、R5は前記と同じ意味を表す。]で表されるリチウム反応剤又は一般式(73)[式中、R5は前記と同じ意味を表し、J13は臭素原子、ヨウ素原子等のハロゲン原子を表す。]で表されるグリニャール反応剤とを文献記載の公知の方法、例えば、ヘテロサイクルズ[Heterocycles]1994年、39巻、801頁、ジャーナル・オブ・ジ・アメリカン・ケミカル・ソサイエティー[J. Am. Chem. Soc.]1988年、110巻、1862頁、テトラヘドロン[Tetrahedron]1960年、11巻、252頁、テトラヘドロン・レターズ[Tetrahedron Lett.]1995年、36巻、9117頁等に記載の方法に準じて反応させた後、各々の保護基について一般的に用いられる方法で脱保護することにより、一般式(3)においてR6vが水素原子である一般式(3-2)[式中、Y, R1, R4, R5及びnは前記と同じ意味を表す。]で表される化合物を得ることができる。 General formula (34) [wherein Y, R 1 , R 4 , n and P represent the same meaning as described above. And a compound represented by the general formula (72) [wherein R 5 represents the same meaning as described above. Or a general formula (73) wherein R 5 represents the same meaning as described above, and J 13 represents a halogen atom such as a bromine atom or an iodine atom. And the Grignard reactant represented by the literature, for example, Heterocycles 1994, 39, 801, Journal of the American Chemical Society [J. Am. Chem. Soc.] 1988, 110, 1862, Tetrahedron 1960, 11, 252; Tetrahedron Lett. 1995, 36, 9117, etc. And then reacting according to the general formula (3-2) wherein R 6v is a hydrogen atom in the general formula (3). Y, R 1 , R 4 , R 5 and n have the same meaning as described above. The compound represented by this can be obtained.
また、一般式(71)[式中、Y, R1, R5, n及びPは前記と同じ意味を表す。]で表される化合物と、一般式(74)[式中、R4は前記と同じ意味を表す。]で表されるリチウム反応剤又は一般式(75)[式中、R4及びJ13は前記と同じ意味を表す。]で表されるグリニャール反応剤とを上記と同様な条件下反応させることによっても一般式(3-2)で表される化合物を得ることができる。 Further, general formula (71) [wherein Y, R 1 , R 5 , n and P represent the same meaning as described above. And a compound of the general formula (74), wherein R 4 represents the same meaning as described above. Or a general formula (75) wherein R 4 and J 13 represent the same meaning as described above. The compound represented by the general formula (3-2) can also be obtained by reacting with a Grignard reactant represented by the same conditions as described above.
ここで用いられる一般式(72)及び一般式(74)で表されるリチウム反応剤の或るものは公知化合物であり、一部は市販品として入手できる。また、それ以外のものも文献記載の一般的なハロゲン−メタル交換反応、例えばブレティン・オブ・ザ・ケミカル・ソサイエティー・オブ・ジャパン[Bull. Chem. Soc. Jpn.]1990年、63巻、3719頁、ザ・ジャーナル・オブ・オーガニック・ケミストリー[J. Org. Chem.]1983年、48巻、1449頁等に記載の方法に準じて対応する公知のハロゲン化物から容易に合成することができる。 Some of the lithium reactants represented by the general formula (72) and the general formula (74) used here are known compounds, and some of them are commercially available. In addition, other halogen-metal exchange reactions described in the literature, such as Bulletin of the Chemical Society of Japan [Bull. Chem. Soc. Jpn.] 1990, 63, 3719 Page, The Journal of Organic Chemistry [J. Org. Chem.] 1983, Vol. 48, p. 1449, etc., can be easily synthesized from the corresponding known halides.
また、一般式(73)及び一般式(75)で表されるグリニャール反応剤の或るものは公知化合物であり、一部は市販品として入手できる。また、それ以外のものも文献記載の一般的なグリニャール試薬の調製方法、例えばアンゲバンテ・ヘミー・インターナショナル・エディション・イン・イングリッシュ[Angew. Chem. Int. Ed. Engl.]1969年、8巻、279頁、ザ・ジャーナル・オブ・オーガニック・ケミストリー[J. Org. Chem.]1989年、54巻、4413頁等に記載の方法に準じて対応する公知のハロゲン化物から容易に合成することができる。 Some of the Grignard reagents represented by the general formula (73) and the general formula (75) are known compounds, and some of them are commercially available. In addition, other methods for preparing general Grignard reagents described in the literature, such as Angewante Chemie Int. Ed. Engl., 1969, Vol. 8, 279 Page, The Journal of Organic Chemistry [J. Org. Chem.] 1989, 54, 4413, etc., and can be easily synthesized from the corresponding known halides.
反応式37 Reaction formula 37
一般式(71)[式中、Y, R1, R5, n及びPは前記と同じ意味を表す。]で表される化合物を、式(76)で表される化合物と文献記載の公知の方法、例えば、シンレット[Synlett]2003年、233頁に記載の方法に準じて反応させるか、或いは公知の一般式(77)[式中、J14は水素原子、臭素原子、トリメチルシリル基等を表す。]で表される化合物と文献記載の公知の方法、例えば、ザ・ジャーナル・オブ・オーガニック・ケミストリー[J. Org. Chem.]2000年、65巻、8848頁及び2001年、66巻、1436頁、テトラヘドロン[Tetrahedron]1989年、45巻、1423頁等に記載の方法に準じて反応させた後、各々の保護基について一般的に用いられる方法で脱保護することにより、一般式(3)においてR4がトリフルオロメチル基であり、R6vが水素原子である一般式(3-3)[式中、Y, R1, R5及びnは前記と同じ意味を表す。]で表される化合物を得ることができる。 Formula (71) [wherein Y, R 1 , R 5 , n and P represent the same meaning as described above. The compound represented by the formula (76) is reacted with a known method described in the literature, for example, the method described in page 233 of Synlett 2003, or a known method. General formula (77) [wherein J 14 represents a hydrogen atom, a bromine atom, a trimethylsilyl group or the like. ] And known methods described in the literature, for example, The Journal of Organic Chemistry [J. Org. Chem.] 2000, 65, 8848 and 2001, 66, 1436 Tetrahedron, 1989, Vol. 45, p. 1423 and the like, and then deprotecting each protecting group by a commonly used method, thereby producing a compound represented by the general formula (3) In general formula (3-3), wherein R 4 is a trifluoromethyl group and R 6v is a hydrogen atom [wherein Y, R 1 , R 5 and n represent the same meaning as described above. The compound represented by this can be obtained.
反応式38 Reaction formula 38
一般式(52)[式中、Y, R1, n, J9及びPは前記と同じ意味を表す。]で表される化合物を文献記載の一般的な方法、例えばリチオ化した後、一般式(78)[式中、R4及びR5は前記と同じ意味を表す。]で表される化合物と反応させるテトラヘドロン・レターズ[Tetrahedron Lett.]1995年、36巻、9117頁等に記載の方法、或いはグリニャール反応剤を形成した後、一般式(78)で表される化合物と反応させるテトラヘドロン[Tetrahedron]1960年、11巻、252頁、ザ・ジャーナル・オブ・オーガニック・ケミストリー[J. Org. Chem.]1988年、53巻、754頁等に記載の方法に準じて反応させた後、各々の保護基について一般的に用いられる方法で脱保護することにより、一般式(3)においてR6vが水素原子である一般式(3-2)[式中、Y, R1, R4, R5及びnは前記と同じ意味を表す。]で表される化合物を得ることができる。なお、R-Liはブチルリチウム等のアルキルリチウム試薬を表す。 General formula (52) [wherein Y, R 1 , n, J 9 and P represent the same meaning as described above. ] After lithiation of the compound represented by the literature, for example, by lithiation, general formula (78) [wherein R 4 and R 5 represent the same meaning as described above. The method described in Tetrahedron Lett. 1995, 36, 9117, etc., or after forming a Grignard reactant, is represented by the general formula (78). According to the method described in Tetrahedron, 1960, 11, 252; The Journal of Organic Chemistry [J. Org. Chem.] 1988, 53, 754, etc. Then, each protecting group is deprotected by a commonly used method to obtain a general formula (3-2) in which R 6v is a hydrogen atom in the general formula (3) [wherein Y, R 1 , R 4 , R 5 and n have the same meaning as described above. The compound represented by this can be obtained. R-Li represents an alkyl lithium reagent such as butyl lithium.
反応式39 Reaction formula 39
反応式36、反応式37及び反応式38において中間体として得られる一般式(79)[式中、Y, R1, R4, R5, n及びPは前記と同じ意味を表す。]で表される化合物と一般式(80)[式中、R6v及びJ1は前記と同じ意味を表す。]で表される化合物とを製造法Hと同様な条件下反応させた後、各々の保護基について一般的に用いられる方法で脱保護することにより、一般式(3)[式中、Y, R1, R4, R5及びnは前記と同じ意味を表し、R6vは水素原子以外の前記の意味を表す。]で表される化合物を得ることができる。 General formula (79) obtained as an intermediate in the reaction formula 36, the reaction formula 37, and the reaction formula 38 [wherein, Y, R 1 , R 4 , R 5 , n and P represent the same meaning as described above. And a compound represented by the general formula (80), wherein R 6v and J 1 represent the same meaning as described above. And the compound represented by the general formula (3) [wherein Y, R 1 , R 4 , R 5 and n represent the same meaning as described above, and R 6v represents the above meaning other than a hydrogen atom. The compound represented by this can be obtained.
一般式(71)で表される化合物は一般式(34)で表される化合物と同様に合成することができる。 The compound represented by the general formula (71) can be synthesized in the same manner as the compound represented by the general formula (34).
これらの各反応においては、反応終了後、通常の後処理を行なうことにより製造法Kの原料化合物となる各々の製造中間体を得ることができる。 In each of these reactions, after the completion of the reaction, each of the production intermediates that are the raw material compounds of production method K can be obtained by carrying out ordinary post-treatment.
また、これらの方法により製造された各々の製造中間体は、単離・精製することなく、それぞれそのまま次工程の反応に用いることもできる。 In addition, each production intermediate produced by these methods can be used as it is in the subsequent step without isolation and purification.
本発明組成物は、一般式(1)及び一般式(2)で表される置換ベンズアニリド化合物及びその塩より選ばれる1種又は2種以上と、化合物群Aより選ばれる1種又は2種以上の化合物を混合物としてそのまま使用することもできるが、通常適当な固体担体又は液体担体と混合し、更に所望により界面活性剤、浸透剤、展着剤、増粘剤、凍結防止剤、結合剤、固結防止剤、崩壊剤、消泡剤、防腐剤および分解防止剤等を添加して、液剤(soluble concentrate)、乳剤(emulsifiable concentrate)、水和剤(wettable powder)、水溶剤(water soluble powder)、顆粒水和剤(water dispersible granule)、顆粒水溶剤(water soluble granule)、懸濁剤(suspension concentrate)、乳濁剤(concentrated emulsion)、サスポエマルジョン(suspoemulsion)、マイクロエマルジョン(microemulsion)、粉剤(dustable powder)、粒剤(granule)、錠剤(tablet)および乳化性ゲル剤(emulsifiable gel)等任意の剤型の製剤にて実用に供することができる。また、省力化および安全性向上の観点から、上記任意の剤型の製剤を、水溶性カプセルおよび水溶性フィルムの袋等の水溶性包装体に封入して供することもできる。 The composition of the present invention is one or more selected from the substituted benzanilide compounds represented by general formula (1) and general formula (2) and salts thereof, and one or more selected from compound group A. These compounds can be used as a mixture as they are, but are usually mixed with a suitable solid carrier or liquid carrier, and if desired, surfactants, penetrants, spreaders, thickeners, antifreeze agents, binders, Add anti-caking agent, disintegrating agent, antifoaming agent, antiseptic and anti-decomposition agent, etc. to add soluble concentrate, emulsion (emulsifiable concentrate), wettable powder, water-soluble solvent (water soluble powder) ), Water dispersible granule, water soluble granule, suspension concentrate, concentrated emulsion, suspoemulsion, microemulsion, powder It can be put to practical use in preparations of any dosage form such as dustable powder, granule, tablet, and emulsifiable gel. Further, from the viewpoint of labor saving and safety improvement, the preparations of any of the above dosage forms can be provided by being enclosed in a water-soluble package such as a water-soluble capsule and a bag of a water-soluble film.
固体担体としては、例えば石英、方解石、海泡石、ドロマイト、チョーク、カオリナイト、パイロフィライト、セリサイト、ハロサイト、メタハロサイト、木節粘土、蛙目粘土、陶石、ジークライト、アロフェン、シラス、きら、タルク、ベントナイト、活性白土、酸性白土、軽石、アタパルジャイト、ゼオライトおよび珪藻土等の天然鉱物質、例えば焼成クレー、パーライト、シラスバルーン、バーミキュライト、アタパルガスクレーおよび焼成珪藻土等の天然鉱物質の焼成品、例えば炭酸マグネシウム、炭酸カルシウム、炭酸ナトリウム、炭酸水素ナトリウム、硫酸アンモニウム、硫酸ナトリウム、硫酸マグネシウム、リン酸水素二アンモニウム、リン酸二水素アンモニウムおよび塩化カリウム等の無機塩類、例えばブドウ糖、果糖、しょ糖および乳糖などの糖類、例えば澱粉、粉末セルロースおよびデキストリン等の多糖類、例えば尿素、尿素誘導体、安息香酸および安息香酸の塩等の有機物、例えば木粉、コルク粉、トウモロコシ穂軸、クルミ殻およびタバコ茎等の植物類、フライアッシュ、ホワイトカーボン(例えば、含水合成シリカ、無水合成シリカおよび含水合成シリケート等)ならびに肥料等が挙げられる。 Examples of the solid carrier include quartz, calcite, gypsum, dolomite, chalk, kaolinite, pyrophyllite, sericite, halosite, metahalosite, kibushi clay, glazed clay, porcelain stone, siegrite, and allophane. Natural minerals such as shirasu, kira, talc, bentonite, activated clay, acid clay, pumice, attapulgite, zeolite and diatomaceous earth, for example, calcined clay, perlite, shirasu balloon, vermiculite, attapulgus clay and calcined diatomaceous earth Baked products such as magnesium carbonate, calcium carbonate, sodium carbonate, sodium bicarbonate, ammonium sulfate, sodium sulfate, magnesium sulfate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate and potassium chloride, such as glucose, fructose , And Saccharides such as sugar and lactose, polysaccharides such as starch, powdered cellulose and dextrin, organic materials such as urea, urea derivatives, benzoic acid and benzoic acid salts, such as wood flour, cork flour, corn cob, walnut shell and Examples include plants such as tobacco stalks, fly ash, white carbon (for example, hydrous synthetic silica, anhydrous synthetic silica, hydrous synthetic silicate, etc.) and fertilizers.
液体担体としては、例えばキシレン、アルキル(C9またはC10等)ベンゼン、フェニルキシリルエタンおよびアルキル(C1またはC3等)ナフタレン等の芳香族炭化水素類、マシン油、ノルマルパラフィン、イソパラフィンおよびナフテン等の脂肪族炭化水素類、ケロシン等の芳香族炭化水素と脂肪族炭化水素の混合物、エタノール、イソプロパノール、シクロヘキサノール、フェノキシエタノールおよびベンジルアルコール等のアルコール、エチレングリコール、プロピレングリコール、ジエチレングリコール、ヘキシレングリコール、ポリエチレングリコールおよびポリプロピレングリコール等の多価アルコール、プロピルセロソルブ、ブチルセロソルブ、フェニルセロソルブ、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテルおよびプロピレングリコールモノフェニルエーテル等のエーテル、アセトフェノン、シクロヘキサノンおよびγ−ブチロラクトン等のケトン、脂肪酸メチルエステル、コハク酸ジアルキルエステル、グルタミン酸ジアルキルエステル、アジピン酸ジアルキルエステルおよびフタル酸ジアルキルエステル等のエステル、N−アルキル(C1、C8またはC12等)ピロリドン等の酸アミド、大豆油、アマニ油、ナタネ油、ヤシ油、綿実油およびヒマシ油等の油脂、ジメチルスルホキシドならびに水が挙げられる。 Examples of the liquid carrier include xylene, alkyl (C 9 or C 10 etc.) benzene, phenyl xylyl ethane and alkyl (C 1 or C 3 etc.) naphthalene and other aromatic hydrocarbons, machine oil, normal paraffin, isoparaffin and Aliphatic hydrocarbons such as naphthene, mixtures of aromatic and aliphatic hydrocarbons such as kerosene, alcohols such as ethanol, isopropanol, cyclohexanol, phenoxyethanol and benzyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, hexylene glycol , Polyhydric alcohols such as polyethylene glycol and polypropylene glycol, propyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol monomethyl ether, propylene Ethers such as recall monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether and propylene glycol monophenyl ether, ketones such as acetophenone, cyclohexanone and γ-butyrolactone, fatty acid methyl esters, dialkyl esters of succinic acid, dialkyl esters of glutamic acid, adipine esters such as dialkyl ester and dialkyl phthalate esters, N- alkyl (C 1, C 8 or C 12, etc.) acid amide pyrrolidone, soybean oil, linseed oil, rapeseed oil, coconut oil, such as cottonseed oil and castor oil Examples include fats and oils, dimethyl sulfoxide and water.
これら固体および液体担体は、単独で用いても2種以上を併用してもよい。 These solid and liquid carriers may be used alone or in combination of two or more.
界面活性剤としては、例えばポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキル(モノまたはジ)フェニルエーテル、ポリオキシエチレン(モノ、ジまたはトリ)スチリルフェニルエーテル、ポリオキシエチレンポリオキシプロピレンブロックコポリマー、ポリオキシエチレン脂肪酸(モノまたはジ)エステル、ソルビタン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル、ヒマシ油エチレンオキサイド付加物、アセチレングリコール、アセチレンアルコール、アセチレングリコールのエチレンオキサイド付加物、アセチレンアルコールのエチレンオキサイド付加物およびアルキルグリコシド等のノニオン性界面活性剤、アルキル硫酸エステル塩、アルキルベンゼンスルホン酸塩、リグニンスルホン酸塩、アルキルスルホコハク酸塩、ナフタレンスルホン酸塩、アルキルナフタレンスルホン酸塩、ナフタレンスルホン酸のホルマリン縮合物の塩、アルキルナフタレンスルホン酸のホルマリン縮合物の塩、ポリオキシエチレンアルキルエーテル硫酸または燐酸エステル塩、ポリオキシエチレン(モノまたはジ)アルキルフェニルエーテル硫酸または燐酸エステル塩、ポリオキシエチレン(モノ、ジまたはトリ)スチリルフェニルエーテル硫酸または燐酸エステル塩、ポリカルボン酸塩(例えば、ポリアクリル酸塩、ポリマレイン酸塩およびマレイン酸とオレフィンとの共重合物等)およびポリスチレンスルホン酸塩等のアニオン性界面活性剤、アルキルアミン塩およびアルキル4級アンモニウム塩等のカチオン性界面活性剤、アミノ酸型およびベタイン型等の両性界面活性剤、シリコーン系界面活性剤ならびにフッ素系界面活性剤が挙げられる。 Examples of the surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl (mono or di) phenyl ether, polyoxyethylene (mono, di or tri) styryl phenyl ether, polyoxyethylene polyoxypropylene block copolymer, polyoxyethylene Ethylene fatty acid (mono or di) ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, castor oil ethylene oxide adduct, acetylene glycol, acetylene alcohol, ethylene oxide adduct of acetylene glycol, ethylene oxide adduct of acetylene alcohol and alkyl Nonionic surfactants such as glycosides, alkyl sulfate esters, alkylbenzene sulfonates, lignin sulfonates, Killsulfosuccinate, naphthalenesulfonate, alkylnaphthalenesulfonate, salt of formalin condensate of naphthalenesulfonic acid, salt of formalin condensate of alkylnaphthalenesulfonic acid, polyoxyethylene alkyl ether sulfate or phosphate ester salt, polyoxy Ethylene (mono or di) alkyl phenyl ether sulfate or phosphate ester salt, polyoxyethylene (mono, di or tri) styryl phenyl ether sulfate or phosphate ester salt, polycarboxylate (eg polyacrylate, polymaleate and Copolymers of maleic acid and olefins, etc.) and anionic surfactants such as polystyrene sulfonates, cationic surfactants such as alkylamine salts and alkyl quaternary ammonium salts, amino acid types and beties Amphoteric surfactants such as mold, and silicone-based surfactants and fluorinated surfactants.
これら界面活性剤の含有量は、特に限定されるものではないが、本発明組成物100重量部に対し、通常0.05〜20重量部の範囲が望ましい。また、これら界面活性剤は、単独で用いても2種以上を併用してもよい。 The content of these surfactants is not particularly limited, but is usually preferably in the range of 0.05 to 20 parts by weight with respect to 100 parts by weight of the composition of the present invention. These surfactants may be used alone or in combination of two or more.
次に本発明組成物を用いる場合の製剤の配合例を示す。但し本発明組成物は、これらのみに限定されるものではない。なお、以下の配合例において「部」は重量部を意味し、「有効成分化合物」は一般式(1)及び一般式(2)で表される置換ベンズアニリド化合物及びその塩より選ばれる1種又は2種以上と、化合物群Aより選ばれる1種又は2種以上の化合物の総称として使用している。 Next, formulation examples of preparations when using the composition of the present invention are shown. However, the composition of the present invention is not limited to these. In the following formulation examples, “part” means part by weight, and “active ingredient compound” is one or more selected from the substituted benzanilide compounds represented by the general formula (1) and the general formula (2) and salts thereof. It is used as a general term for two or more compounds and one or more compounds selected from compound group A.
〔水和剤(wettable powder)〕
有効成分化合物 0.1〜80部
固体担体 5〜98.9部
界面活性剤 1〜10部
その他 0〜 5部
その他として、例えば固結防止剤、分解防止剤等があげれらる。
[Wettable powder]
Active ingredient compound 0.1-80 parts Solid carrier 5-98.9 parts Surfactant 1-10 parts Others 0-5 parts Others include, for example, anti-caking agents and decomposition inhibitors.
〔乳 剤(emulsifiable concentrate)〕
有効成分化合物 0.1〜30部
液体担体 45〜95部
界面活性剤 4.9〜15部
その他 0〜10部
その他として、例えば展着剤、分解防止剤等が挙げられる。
[Emulsifiable concentrate]
Active ingredient compound 0.1-30 parts Liquid carrier 45-95 parts Surfactant 4.9-15 parts Others 0-10 parts Others include, for example, spreading agents, decomposition inhibitors and the like.
〔懸濁剤(suspension concentrate)〕
有効成分化合物 0.1〜70部
液体担体 15〜98.89部
界面活性剤 1〜12部
その他 0.01〜30部
その他として、例えば凍結防止剤、増粘剤等が挙げられる。
[Suspension concentrate]
Active ingredient compound 0.1 to 70 parts Liquid carrier 15 to 98.89 parts Surfactant 1 to 12 parts Others 0.01 to 30 parts Others include, for example, antifreezing agents and thickeners.
〔顆粒水和剤(water dispersible granule)〕
有効成分化合物 0.1〜90部
固体担体 0〜98.9部
界面活性剤 1〜20部
その他 0〜 10部
その他として、例えば結合剤、分解防止剤等が挙げられる。
[Granular wettable powder (water dispersible granule)]
Active ingredient compound 0.1 to 90 parts Solid carrier 0 to 98.9 parts Surfactant 1 to 20 parts Others 0 to 10 parts Others include, for example, binders and decomposition inhibitors.
〔液 剤(soluble concentrate)〕
有効成分化合物 0.01〜70部
液体担体 20〜99.99部
その他 0〜 10部
その他として、例えば凍結防止剤、展着剤等が挙げられる。
[Soluble concentrate]
Active ingredient compound 0.01 to 70 parts Liquid carrier 20 to 99.99 parts Others 0 to 10 parts Others include, for example, antifreezing agents and spreading agents.
〔粒 剤(granule)〕
有効成分化合物 0.01〜80部
固体担体 10〜99.99部
その他 0〜10部
その他として、例えば結合剤、分解防止剤等が挙げられる。
[Granule]
Active ingredient compound 0.01-80 parts Solid carrier 10-99.99 parts Others 0-10 parts Others include, for example, binders, decomposition inhibitors and the like.
〔粉 剤(dustable powder)〕
有効成分化合物 0.01〜30部
固体担体 65〜99.99部
その他 0〜5部
その他として、例えばドリフト防止剤、分解防止剤等が挙げられる。
[Dustable powder]
Active ingredient compound 0.01 to 30 parts Solid carrier 65 to 99.99 parts Others 0 to 5 parts Other examples include a drift inhibitor and a decomposition inhibitor.
〔製剤例〕
次に具体的に本発明組成物に含まれる農薬製剤例を示すが、これらのみに限定されるものではない。
[Formulation example]
Next, although the example of an agrochemical formulation contained in this invention composition is shown concretely, it is not limited only to these.
〔配合例1〕水和剤(wettable powder)
化合物No.1 10部
化合物No.a 10部
パイロフィライト 76部
ソルポール5039 2部
(非イオン性界面活性剤とアニオン性界面活性剤との混合物:東邦化学工業(株)商品名)
カープレックス#80D 2部
(合成含水珪酸:塩野義製薬(株)商品名)
以上を均一に混合粉砕して水和剤とする。
[Formulation 1] wettable powder
Compound No. 1 10 parts Compound No. 1 a 10 parts Pyrophyllite 76 parts Solpol 5039 2 parts (mixture of nonionic surfactant and anionic surfactant: Toho Chemical Co., Ltd. trade name)
Carplex # 80D 2 parts (Synthetic hydrous silicic acid: Shionogi & Co., Ltd. trade name)
The above is uniformly mixed and ground to obtain a wettable powder.
〔配合例2〕乳 剤(emulsifiable concentrate)
化合物No.2 3部
化合物No.b 2部
キシレン 75部
N−メチルピロリドン 15部
ソルポール2680 5部
(非イオン性界面活性剤とアニオン性界面活性剤との混合物:東邦化学工業(株)商品名)
以上を均一に混合して乳剤とする。
[Composition Example 2] Emulsifiable concentrate
Compound No. 2 3 parts compound no. b 2 parts xylene 75 parts N-methylpyrrolidone 15 parts Solpol 2680 5 parts (mixture of nonionic surfactant and anionic surfactant: Toho Chemical Co., Ltd. trade name)
The above is uniformly mixed to obtain an emulsion.
〔配合例3〕懸濁剤(suspension concentrate)
化合物No.3 15部
化合物No.c 10部
アグリゾールS−710 10部
(非イオン性界面活性剤:花王(株)商品名)
ルノックス1000C 0.5部
(アニオン性界面活性剤:東邦化学工業(株)商品名)
キサンタンガム 0.2部
水 64.3部
以上を均一に混合した後、湿式粉砕して懸濁剤とする。
[Composition Example 3] Suspension concentrate
Compound No. 3 15 parts Compound No. 3 c 10 parts Agrisol S-710 10 parts (nonionic surfactant: trade name of Kao Corporation)
Lnox 1000C 0.5 part (anionic surfactant: Toho Chemical Co., Ltd. trade name)
Xanthan gum 0.2 parts Water 64.3 parts After uniformly mixing the above, wet pulverize to make a suspension.
〔配合例4〕顆粒水和剤(water dispersible granule)
化合物No.4 40部
化合物No.d 35部
ハイテノールNE-15 5部
(アニオン性界面活性剤:第一工業製薬(株)商品名)
バニレックスN 10部
(アニオン性界面活性剤:日本製紙(株)商品名)
カープレックス#80D 10部
(合成含水珪酸:塩野義製薬(株)商品名)
以上を均一に混合粉砕した後、少量の水を加えて攪拌混合し、押出式造粒機で造粒し、乾燥して顆粒水和剤とする。
[Formulation 4] Granule wettable powder (water dispersible granule)
Compound No. 4 40 parts Compound No. 4 d 35 parts Hytenol NE-15 5 parts (anionic surfactant: Daiichi Kogyo Seiyaku Co., Ltd. trade name)
Vanillex N 10 parts (anionic surfactant: Nippon Paper Industries Co., Ltd. trade name)
Carplex # 80D 10 parts (Synthetic hydrous silicic acid: Shionogi Pharmaceutical Co., Ltd. trade name)
After uniformly mixing and pulverizing the above, a small amount of water is added, stirred and mixed, granulated with an extrusion granulator, and dried to obtain a granulated wettable powder.
〔配合例5〕粒 剤(granule)
化合物No.5 3部
化合物No.e 2部
ベントナイト 50部
タルク 45部
以上を均一に混合粉砕した後、少量の水を加えて攪拌混合し、押出式造粒機で造粒し、乾燥して粒剤とする。
[Formulation Example 5] Granule
Compound No. 5 3 parts Compound No. 5 e 2 parts bentonite 50 parts talc 45 parts After uniformly mixing and pulverizing the above, a small amount of water is added, stirred and mixed, granulated with an extrusion granulator, and dried to form granules.
〔配合例6〕粉 剤(dustable powder)
化合物No.6 2部
化合物No.f 1部
カープレックス#80D 0.5部
(ホワイトカーボン:塩野義製薬(株)商品名)
カオリナイト 95部
リン酸ジイソプロピル 1.5部
以上を均一に混合粉砕して粉剤とする。
[Formulation 6] dustable powder
Compound No. 6 2 parts Compound No. 6 f 1 part Carplex # 80D 0.5 part (white carbon: Shionogi & Co., Ltd. trade name)
Kaolinite 95 parts Diisopropyl phosphate 1.5 parts or more uniformly mixed and pulverized to obtain a powder.
使用に際しては上記水和剤、乳剤、フロアブル剤、粒状水和剤は水で50〜20000倍に希釈して各有効成分が1ヘクタール(ha)当たり0.005〜50kgになるように散布する。 In use, the wettable powder, emulsion, flowable powder, and granular wettable powder are diluted 50 to 20000 times with water and sprayed so that each active ingredient is 0.005 to 50 kg per hectare (ha).
以下に、本発明の一般式(1)及び一般式(2)で表される置換ベンズアニリド化合物の合成例を具体的に示す。 Below, the synthesis example of the substituted benzanilide compound represented by General formula (1) and General formula (2) of this invention is shown concretely.
〔合成例1〕
N1−[4−[3−(4−クロロフェニル)−5−トリフルオロメチル−4、5−ジヒドロイソオキサゾール−5−イル]−2−メチルフェニル]−3−ヨード−N2−(1−メチル−2−メチルチオエチル)フタル酸ジアミド(本発明化合物No.11)。
[Synthesis Example 1]
N 1 - [4- [3- ( 4- chlorophenyl) -5-trifluoromethyl-4,5-dihydro-isoxazol-5-yl] -2-methylphenyl] -3-iodo -N 2 - (1- Methyl-2-methylthioethyl) phthalic acid diamide (Compound No. 11 of the present invention).
工程1;4−ヨード−2−メチルカルバニリド酸−t−ブチルの製造
4−ヨード−2−メチルアニリン10.0gのトルエン30ml溶液に二炭酸ジ−t−ブチル14.0gを添加し、加熱還流下にて2時間攪拌した。反応完結後、水30mlを加えて15分間加熱還流した後室温まで放冷、ジエチルエーテル100mlにて抽出した。有機層を水洗後、無水硫酸マグネシウムで乾燥、減圧下にて溶媒を留去し、残留した固体をヘキサンにて洗浄し、目的物11.5gを白色結晶として得た。
融点101.0〜103.0℃
1H NMR (CDCl3, Me4Si, 300MHz) δ7.63 (d, J=8.4Hz, 1H), 7.45-7.5 (m, 2H), 6.22 (bs, 1H), 2.19 (s, 3H), 1.52 (s, 9H)。
Step 1; Preparation of 4-iodo-2-methylcarbanilic acid-tert-butyl 4-iodo-2-methylaniline 14.0 g of di-tert-butyl dicarbonate was added to a solution of 10.0 g of toluene in 30 ml of toluene. The mixture was stirred for 2 hours under heating to reflux. After completion of the reaction, 30 ml of water was added and the mixture was heated to reflux for 15 minutes, allowed to cool to room temperature, and extracted with 100 ml of diethyl ether. The organic layer was washed with water, dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the remaining solid was washed with hexane to obtain 11.5 g of the desired product as white crystals.
Melting point: 101.0-103.0 ° C
1 H NMR (CDCl 3 , Me 4 Si, 300 MHz) δ7.63 (d, J = 8.4 Hz, 1H), 7.45-7.5 (m, 2H), 6.22 (bs, 1H), 2.19 (s, 3H), 1.52 (s, 9H).
工程2;2−メチル−4−(1−トリフルオロメチルエテニル)カルバニリド酸−t−ブチルの製造
窒素雰囲気下、テトラヒドロフラン80ml中に分散させた、酢酸銀にて活性化した亜鉛粉末(テトラヘドロン・レターズ[Tetrahedron Lett.]1981年、22巻、649頁)9.5gにクロロトリメチルシラン2mlを添加し、室温にて10分間攪拌、次いで2−ブロモ−3、3、3−トリフルオロプロペン16.2g及びN、N、N'、N'−テトラメチルエチレンジアミン22mlを加え、60℃にて12時間攪拌を継続した。沈殿する不溶物をデカンテーションにて除去した後、反応混合物に4−ヨード−2−メチルカルバニリド酸−t−ブチル10.0g及びテトラキストリフェニルホスフィンパラジウム1.0gを添加し、60℃にてさらに4時間攪拌した。反応完結後、減圧下に溶媒を留去、水200mlを加え、ジエチルエーテルにて抽出(200mlx2)した。有機層を水洗後、無水硫酸マグネシウムで乾燥、減圧下にて溶媒を留去し、残留物をジエチルエーテルにて溶出するシリカゲルカラムクロマトグラフィー及びジエチルエーテルにて溶出するアルミナのカラムクロマトグラフィーにて精製し、目的物8.4gを淡黄色結晶として得た。
融点86.0〜88.0℃
1H NMR (CDCl3, Me4Si, 300MHz) δ7.89 (d, J=8.8Hz, 1H), 7.29 (d, J=8.8Hz, 1H), 7.24 (s, 1H), 6.32 (bs, 1H), 5.88 (s, 1H), 5.70 (s, 1H), 2.30 (s, 3H), 1.53 (s, 9H)。
Step 2: Preparation of 2-methyl-4- (1-trifluoromethylethenyl) carbanilide acid-t-butyl In a nitrogen atmosphere, silver acetate activated zinc powder (tetrahedron) dispersed in 80 ml of tetrahydrofuran (Letters [Tetrahedron Lett.] 1981, Vol. 22, p. 649) 2 ml of chlorotrimethylsilane was added to 9.5 g, stirred for 10 minutes at room temperature, and then 2-bromo-3,3,3-trifluoropropene 16 .2 g and 22 ml of N, N, N ′, N′-tetramethylethylenediamine were added and stirring was continued at 60 ° C. for 12 hours. After removing insoluble precipitates by decantation, 10.0 g of 4-iodo-2-methylcarbanilide-t-butyl and 1.0 g of tetrakistriphenylphosphine palladium were added to the reaction mixture, and the mixture was heated to 60 ° C. The mixture was further stirred for 4 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, 200 ml of water was added, and the mixture was extracted with diethyl ether (200 ml × 2). The organic layer is washed with water, dried over anhydrous magnesium sulfate, the solvent is distilled off under reduced pressure, and the residue is purified by silica gel column chromatography eluting with diethyl ether and alumina column chromatography eluting with diethyl ether. As a result, 8.4 g of the desired product was obtained as pale yellow crystals.
Melting point 86.0-88.0 ° C
1 H NMR (CDCl 3 , Me 4 Si, 300 MHz) δ 7.89 (d, J = 8.8Hz, 1H), 7.29 (d, J = 8.8Hz, 1H), 7.24 (s, 1H), 6.32 (bs, 1H), 5.88 (s, 1H), 5.70 (s, 1H), 2.30 (s, 3H), 1.53 (s, 9H).
工程3;4−クロロフェニルヒドロキシム酸クロライドの製造
4−クロロフェニルアルドキシム0.46gの1、4−ジオキサン8ml溶液に濃塩酸4mlを加え、氷冷攪拌下、8%次亜塩素酸ナトリウム水溶液3.0gを10分間かけて滴下した。滴下終了後、同温度にて10分間攪拌を継続した後、水30mlを加え、さらに30分攪拌した。反応完結後、生成した固体を濾別し水洗(30mlx2)、減圧下にて乾燥し、目的物0.4gを白色結晶として得た。
融点86.0〜87.0℃
1H NMR (CDCl3, Me4Si, 300MHz) δ8.00 (s, 1H), 7.75-7.85 (m, 2H), 7.35-7.40 (m, 2H)。
Step 3; Preparation of 4-chlorophenylhydroxymic acid chloride 4 ml of concentrated hydrochloric acid is added to 8 ml of 1,4-dioxane in 0.46 g of 4-chlorophenylaldoxime, and 8% aqueous sodium hypochlorite solution 3. 0 g was added dropwise over 10 minutes. After completion of the dropwise addition, stirring was continued for 10 minutes at the same temperature, 30 ml of water was added, and the mixture was further stirred for 30 minutes. After completion of the reaction, the produced solid was separated by filtration, washed with water (30 ml × 2) and dried under reduced pressure to obtain 0.4 g of the objective product as white crystals.
Melting point 86.0-87.0 ° C
1 H NMR (CDCl 3 , Me 4 Si, 300 MHz) δ 8.00 (s, 1H), 7.75-7.85 (m, 2H), 7.35-7.40 (m, 2H).
工程4;4−[3−(4−クロロフェニル)−5−トリフルオロメチル−4、5−ジヒドロイソオキサゾール−5−イル]−2−メチルカルバニリド酸−t−ブチルの製造
2−メチル−4−(1−トリフルオロメチルエテニル)カルバニリド酸−t−ブチル3.0gのN、N−ジメチルホルムアミド25ml溶液に4−クロロフェニルヒドロキシム酸クロライド2.33gを添加し、氷冷攪拌下、トリエチルアミン4.2mlを10分間かけて滴下した。室温にて5時間攪拌を継続した後、反応混合物を水100ml に注ぎ、酢酸エチルにて抽出(100mlx2)、有機層を水洗後、無水硫酸マグネシウムで乾燥、減圧下にて溶媒を留去した。残留固体を酢酸エチル−ヘキサン(1:1)にて溶出するシリカゲルカラムクロマトグラフィーにて精製し、目的物4.2gを白色結晶として得た。
1H NMR (CDCl3, Me4Si, 300MHz) δ7.95 (s, 1H), 7.5-7.6 (m, 2H), 7.3-7.4 (m, 4H), 6.33 (bs, 1H), 3.99 (d, J=16.8Hz, 1H), 3.68 (d, J=17.4Hz, 1H), 2.28 (s, 3H), 1.52 (s, 9H)。
Step 4; Preparation of 4- [3- (4-Chlorophenyl) -5-trifluoromethyl-4,5-dihydroisoxazol-5-yl] -2-methylcarbanilide acid t-butyl 2-Methyl- To a solution of 3.0 g of 4- (1-trifluoromethylethenyl) carbanilide-t-butyl in 25 ml of N, N-dimethylformamide was added 2.33 g of 4-chlorophenylhydroxymic acid chloride, and the mixture was stirred under ice-cooling and triethylamine. 4.2 ml was added dropwise over 10 minutes. After stirring for 5 hours at room temperature, the reaction mixture was poured into 100 ml of water, extracted with ethyl acetate (100 ml × 2), the organic layer was washed with water, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residual solid was purified by silica gel column chromatography eluting with ethyl acetate-hexane (1: 1) to obtain 4.2 g of the objective product as white crystals.
1 H NMR (CDCl 3 , Me 4 Si, 300 MHz) δ7.95 (s, 1H), 7.5-7.6 (m, 2H), 7.3-7.4 (m, 4H), 6.33 (bs, 1H), 3.99 (d , J = 16.8Hz, 1H), 3.68 (d, J = 17.4Hz, 1H), 2.28 (s, 3H), 1.52 (s, 9H).
工程5;4−[3−(4−クロロフェニル)−5−トリフルオロメチル−4、5−ジヒドロイソオキサゾール−5−イル]−2−メチルアニリンの製造
4−[3−(4−クロロフェニル)−5−トリフルオロメチル−4、5−ジヒドロイソオキサゾール−5−イル]−2−メチルカルバニリド酸−t−ブチル3.2gに、氷冷攪拌下、トリフルオロ酢酸15mlを滴下した。同温度にて10分攪拌を継続した後、減圧下にて溶媒を留去、残留した油状物質にジエチルエーテル100mlを加え、飽和炭酸水素ナトリウム水溶液100mlにて洗浄した。有機層を分取後、水層はジエチルエーテルにて抽出(100mlx2)、有機層を合わせて飽和炭酸水素ナトリウム水溶液100mlにて洗浄後、飽和食塩水次いで無水硫酸マグネシウムの順で脱水・乾燥、減圧下にて溶媒を留去した。残留固体を酢酸エチル−ヘキサン(1:3)にて溶出するシリカゲルカラムクロマトグラフィーにて精製し、目的物1.9gを白色結晶として得た。
融点117.5〜119.0℃
1H NMR (CDCl3, Me4Si, 300MHz) δ7.55-7.65 (m, 2H), 7.35-7.4 (m, 2H), 7.25 (s, 1H), 7.22 (d, J=8.1Hz, 1H), 6.69 (d, J=8.4Hz, 1H), 3.97 (d, J=17.1Hz, 1H), 3.69 (d, J=17.4Hz, 1H), 3.73 (bs, 2H), 2.18 (s, 3H)。
Step 5; Preparation of 4- [3- (4-chlorophenyl) -5-trifluoromethyl-4,5-dihydroisoxazol-5-yl] -2-methylaniline 4- [3- (4-Chlorophenyl)- 15 ml of trifluoroacetic acid was added dropwise to 3.2 g of 5-trifluoromethyl-4,5-dihydroisoxazol-5-yl] -2-methylcarbanilide acid-t-butyl with stirring under ice cooling. After stirring at the same temperature for 10 minutes, the solvent was distilled off under reduced pressure, 100 ml of diethyl ether was added to the remaining oily substance, and the mixture was washed with 100 ml of a saturated aqueous sodium hydrogen carbonate solution. After separating the organic layer, the aqueous layer was extracted with diethyl ether (100 ml x 2). The organic layers were combined and washed with 100 ml of saturated aqueous sodium hydrogen carbonate solution, then dehydrated and dried in the order of saturated brine and then anhydrous magnesium sulfate. The solvent was distilled off under. The residual solid was purified by silica gel column chromatography eluting with ethyl acetate-hexane (1: 3) to obtain 1.9 g of the desired product as white crystals.
Melting point 117.5-119.0 ° C.
1 H NMR (CDCl 3 , Me 4 Si, 300 MHz) δ7.55-7.65 (m, 2H), 7.35-7.4 (m, 2H), 7.25 (s, 1H), 7.22 (d, J = 8.1Hz, 1H ), 6.69 (d, J = 8.4Hz, 1H), 3.97 (d, J = 17.1Hz, 1H), 3.69 (d, J = 17.4Hz, 1H), 3.73 (bs, 2H), 2.18 (s, 3H ).
工程6;N1−[4−[3−(4−クロロフェニル)−5−トリフルオロメチル−4、5−ジヒドロイソオキサゾール−5−イル]−2−メチルフェニル]−3−ヨード−N2−(1−メチル−2−メチルチオエチル)フタル酸ジアミドの製造
3−ヨード−N−(1−メチル−2−メチルチオエチル)フタルアミド酸0.3gのジクロロメタン4ml溶液に、氷冷攪拌下、ピリジン0.12ml及びトリフルオロ酢酸無水物0.18gを添加し、同温度にて2時間攪拌した。次いで4−[3−(4−クロロフェニル)−5−トリフルオロメチル−4、5−ジヒドロイソオキサゾール−5−イル]−2−メチルアニリン0.28gを添加、室温にて12時間攪拌を継続した。反応完結後、反応混合物を水10mlに注ぎクロロホルムにて抽出(10mlx2)、有機層を水洗後、無水硫酸マグネシウムにて乾燥、減圧下に溶媒を留去した。残留した固体を酢酸エチル−ヘキサン(1:2)にて溶出するシリカゲルカラムクロマトグラフィーにて精製し、目的物0.11gを白色結晶として得た。
融点116.5〜120.3℃
1H NMR (CDCl3, Me4Si, 300MHz) δ8.39 (d, J=2.1Hz, 1H), 8.22 (dd, J=8.7, 2.1Hz, 1H), 7.96 (d, J=7.5Hz, 1H), 7.77 (d, J=7.8Hz, 1H), 7.55-7.65 (m, 2H), 7.35-7.5 (m, 4H), 7.20 (t, J=8.1Hz, 1H), 6.21 (d, J=8.1Hz, 1H), 4.25-4.35 (m, 1H), 4.04 (d, J=17.1Hz, 1H), 3.72 (d, J=17.4Hz, 1H), 2.5-2.65 (m, 2H), 2.36 (s, 3H), 1.91 (d, J=1.8Hz, 3H), 1.25 (d, J=6.6Hz, 3H)。
Step 6; N 1 - [4- [ 3- (4- chlorophenyl) -5-trifluoromethyl-4,5-dihydro-isoxazol-5-yl] -2-methylphenyl] -3-iodo -N 2 - Preparation of (1-methyl-2-methylthioethyl) phthalic acid diamide To a solution of 0.3 g of 3-iodo-N- (1-methyl-2-methylthioethyl) phthalamic acid in 4 ml of dichloromethane was added 0.1 ml of pyridine with stirring under ice-cooling. 12 ml and 0.18 g of trifluoroacetic anhydride were added and stirred at the same temperature for 2 hours. Then, 0.28 g of 4- [3- (4-chlorophenyl) -5-trifluoromethyl-4,5-dihydroisoxazol-5-yl] -2-methylaniline was added and stirring was continued at room temperature for 12 hours. . After completion of the reaction, the reaction mixture was poured into 10 ml of water and extracted with chloroform (10 ml × 2). The organic layer was washed with water, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The remaining solid was purified by silica gel column chromatography eluting with ethyl acetate-hexane (1: 2) to obtain 0.11 g of the desired product as white crystals.
Melting point 116.5-120.3 ° C
1 H NMR (CDCl 3 , Me 4 Si, 300 MHz) δ8.39 (d, J = 2.1 Hz, 1H), 8.22 (dd, J = 8.7, 2.1 Hz, 1H), 7.96 (d, J = 7.5 Hz, 1H), 7.77 (d, J = 7.8Hz, 1H), 7.55-7.65 (m, 2H), 7.35-7.5 (m, 4H), 7.20 (t, J = 8.1Hz, 1H), 6.21 (d, J = 8.1Hz, 1H), 4.25-4.35 (m, 1H), 4.04 (d, J = 17.1Hz, 1H), 3.72 (d, J = 17.4Hz, 1H), 2.5-2.65 (m, 2H), 2.36 (s, 3H), 1.91 (d, J = 1.8Hz, 3H), 1.25 (d, J = 6.6Hz, 3H).
〔合成例2〕
3−ヨード−N2−イソプロピル−N1−[4−[3−(1、2、4−トリアゾール−1−イル)−5−トリフルオロメチル−4、5−ジヒドロイソオキサゾール−5−イル]−2−メチルフェニル]フタル酸ジアミド(本発明化合物No.1)。
[Synthesis Example 2]
3-iodo -N 2 - isopropyl -N 1 - [4- [3- -5- (1,2,4- triazol-1-yl) -5-trifluoromethyl-4,5-dihydro-4-yl] -2-Methylphenyl] phthalic acid diamide (the present compound No. 1).
工程1;4−(3−クロロ−5−トリフルオロメチル−4、5−ジヒドロイソオキサゾール−5−イル)−2−メチルカルバニリド酸−t−ブチルの製造
ヒドロキシイミノ酢酸5.0gの1、2−ジメトキシエタン80ml溶液にN-クロロコハク酸イミド15.0gを添加し、75℃にて1時間攪拌した。反応混合物を室温まで冷却した後、合成例1の工程1〜工程2にて合成した2−メチル−4−(1−トリフルオロメチルエテニル)カルバニリド酸−t−ブチル3.0g及び炭酸水素カリウム20.0gを加え、室温にて、さらに18時間攪拌を継続した。反応完結後、減圧下にて溶媒を留去、クロロホルム50mlを加え不溶物を濾別し、クロロホルム層を1N塩酸にて洗浄後、飽和食塩水次いで無水硫酸マグネシウムの順で脱水・乾燥、減圧下にて溶媒を留去した。残留固体をクロロホルム−ヘキサン(4:6)にて溶出するシリカゲルカラムクロマトグラフィーにて精製し、目的物1.1gを白色結晶として得た。
融点83.0〜85.0℃
1H NMR (CDCl3, Me4Si, 300MHz) δ7.97 (d, J=8.5Hz, 1H), 7.2-7.3 (m, 2H), 6.34 (bs, 1H), 3.83 (d, J=17.5Hz, 1H), 3.55 (d, J=17.5Hz, 1H), 2.28 (s, 3H), 1.53 (s, 9H)。
Step 1; Preparation of 4- (3-Chloro-5-trifluoromethyl-4,5-dihydroisoxazol-5-yl) -2-methylcarbanilide acid-t-butyl Hydroxyiminoacetic acid 5.0 g 1 To the 80 ml solution of 2-dimethoxyethane, 15.0 g of N-chlorosuccinimide was added and stirred at 75 ° C. for 1 hour. After the reaction mixture was cooled to room temperature, 3.0 g of 2-methyl-4- (1-trifluoromethylethenyl) carbanilide acid-t-butyl synthesized in Step 1 to Step 2 of Synthesis Example 1 and potassium hydrogen carbonate 20.0 g was added and stirring was continued at room temperature for a further 18 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, 50 ml of chloroform was added and the insoluble matter was filtered off. The solvent was distilled off. The residual solid was purified by silica gel column chromatography eluting with chloroform-hexane (4: 6) to obtain 1.1 g of the objective product as white crystals.
Melting point 83.0-85.0 ° C
1 H NMR (CDCl 3 , Me 4 Si, 300 MHz) δ7.97 (d, J = 8.5 Hz, 1H), 7.2-7.3 (m, 2H), 6.34 (bs, 1H), 3.83 (d, J = 17.5 Hz, 1H), 3.55 (d, J = 17.5Hz, 1H), 2.28 (s, 3H), 1.53 (s, 9H).
工程2;2−メチル−4−[3−(1、2、4−トリアゾール−1−イル)−5−トリフルオロメチル−4、5−ジヒドロイソオキサゾール−5−イル]カルバニリド酸−t−ブチルの製造
1、2、4−トリアゾール0.23gのN、N−ジメチルホルムアミド20ml溶液に60%油性水素化ナトリウム0.13gを添加し、室温にて15分間攪拌した。水素ガスの発生が止んだ後、4−(3−クロロ−5−トリフルオロメチル−4、5−ジヒドロイソオキサゾール−5−イル)−2−メチルカルバニリド酸−t−ブチル0.5gを添加し、50℃にて90分間攪拌を継続した。反応完結後、反応混合物を水200mlに注ぎ、酢酸エチルにて抽出(100mlx2)、有機層を飽和食塩水次いで無水硫酸マグネシウムの順で脱水・乾燥、減圧下にて溶媒を留去した。残留固体を酢酸エチル−ヘキサン(3:7)にて溶出するシリカゲルカラムクロマトグラフィーにて精製し、目的物0.4gを白色結晶として得た。
融点46.0〜48.0℃
1H NMR (CDCl3, Me4Si, 300MHz) δ8.79 (s, 1H), 8.08 (s, 1H), 8.00 (d, J=8.8Hz, 1H), 7.3-7.4 (m, 2H), 6.36 (bs, 1H), 4.27 (d, J=17.8Hz, 1H), 4.01 (d, J=17.8Hz, 1H), 2.29 (s, 3H), 1.51 (s, 9H)。
Step 2; 2-methyl-4- [3- (1,2,4-triazol-1-yl) -5-trifluoromethyl-4,5-dihydroisoxazol-5-yl] carbanilide acid-t-butyl Preparation of 0.13 g of 60% oily sodium hydride was added to a solution of 0.23 g of 1,2,4-triazole in 20 ml of N, N-dimethylformamide and stirred at room temperature for 15 minutes. After evolution of hydrogen gas ceased, 0.5 g of 4- (3-chloro-5-trifluoromethyl-4,5-dihydroisoxazol-5-yl) -2-methylcarbanilide acid-t-butyl was added. The mixture was added and stirring was continued at 50 ° C. for 90 minutes. After completion of the reaction, the reaction mixture was poured into 200 ml of water and extracted with ethyl acetate (100 ml × 2). The organic layer was dehydrated and dried in the order of saturated brine and then anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residual solid was purified by silica gel column chromatography eluting with ethyl acetate-hexane (3: 7) to obtain 0.4 g of the desired product as white crystals.
Melting point: 46.0-48.0 ° C
1 H NMR (CDCl 3 , Me 4 Si, 300 MHz) δ8.79 (s, 1H), 8.08 (s, 1H), 8.00 (d, J = 8.8Hz, 1H), 7.3-7.4 (m, 2H), 6.36 (bs, 1H), 4.27 (d, J = 17.8Hz, 1H), 4.01 (d, J = 17.8Hz, 1H), 2.29 (s, 3H), 1.51 (s, 9H).
工程3;2−メチル−4−[3−(1、2、4−トリアゾール−1−イル)−5−トリフルオロメチル−4、5−ジヒドロイソオキサゾール−5−イル]アニリンの製造
2−メチル−4−[3−(1、2、4−トリアゾール−1−イル)−5−トリフルオロメチル−4、5−ジヒドロイソオキサゾール−5−イル]カルバニリド酸−t−ブチル0.4gに、氷冷攪拌下、トリフルオロ酢酸5mlを滴下した。室温にて10分攪拌を継続した後、減圧下にて溶媒を留去、残留物をジエチルエーテル50mlに溶解し、飽和炭酸水素ナトリウム水溶液50mlにて洗浄した。有機層を無水硫酸マグネシウムにて脱水後、減圧下にて溶媒を留去、粗製の目的物0.3gを淡黄色油状物質として得た。このものは、精製することなく次の反応に用いた。
Step 3; Preparation of 2-methyl-4- [3- (1,2,4-triazol-1-yl) -5-trifluoromethyl-4,5-dihydroisoxazol-5-yl] aniline To 0.4 g of -4- [3- (1,2,4-triazol-1-yl) -5-trifluoromethyl-4,5-dihydroisoxazol-5-yl] carbanilide acid in ice Under cold stirring, 5 ml of trifluoroacetic acid was added dropwise. After stirring at room temperature for 10 minutes, the solvent was distilled off under reduced pressure, and the residue was dissolved in 50 ml of diethyl ether and washed with 50 ml of saturated aqueous sodium hydrogen carbonate solution. The organic layer was dehydrated with anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain 0.3 g of a crude desired product as a pale yellow oily substance. This was used in the next reaction without purification.
工程4;3−ヨード−N2−イソプロピル−N1−[2−メチル−4−[3−(1、2、4−トリアゾール−1−イル)−5−トリフルオロメチル−4、5−ジヒドロイソオキサゾール−5−イル]フェニル]フタル酸ジアミドの製造
3−ヨード−N−イソプロピルフタルアミド酸0.35gのトルエン10ml溶液に、室温にて攪拌下、トリフルオロ酢酸無水物0.35gを滴下した。同温度にて30分攪拌した後、減圧下に溶媒を留去、残留物をテトラヒドロフラン10mlに溶解し、2−メチル−4−[3−(1、2、4−トリアゾール−1−イル)−5−トリフルオロメチル−4、5−ジヒドロイソオキサゾール−5−イル]アニリン0.3gを添加、室温にて18時間攪拌を継続した。反応完結後、減圧下に溶媒を留去、残留した固体を酢酸エチル−クロロホルム(4:6)にて溶出するシリカゲルカラムクロマトグラフィーにて精製し、目的物0.4gを白色結晶として得た。
融点131.0〜133.0℃
1H NMR (CDCl3, Me4Si, 300MHz) δ8.80 (s, 1H), 8.44 (bs, 1H), 8.21 (d, J=7.8Hz, 1H), 8.08 (s, 1H), 7.98 (d, J=6.8Hz, 1H), 7.82 (d, J=6.8Hz, 1H), 7.2-7.5 (m, 3H), 5.83 (d, J=8.0Hz, 1H), 4.29 (d, J=17.8Hz, 1H), 4.1-4.3 (m, 1H), 4.00 (d, J=17.8Hz, 1H), 2.38 (s, 3H), 1.16 (d, J=6.6Hz, 6H)。
Step 4: 3-Iodo -N 2 - isopropyl -N 1 - [2-methyl-4- [3- (1,2,4-triazol-1-yl) -5-trifluoromethyl-4,5-dihydro Preparation of isoxazol-5-yl] phenyl] phthalic acid diamide To a solution of 0.35 g of 3-iodo-N-isopropylphthalamic acid in 10 ml of toluene was added dropwise 0.35 g of trifluoroacetic anhydride with stirring at room temperature. . After stirring at the same temperature for 30 minutes, the solvent was distilled off under reduced pressure, the residue was dissolved in 10 ml of tetrahydrofuran, and 2-methyl-4- [3- (1,2,4-triazol-1-yl)- 0.3 g of 5-trifluoromethyl-4,5-dihydroisoxazol-5-yl] aniline was added and stirring was continued at room temperature for 18 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, and the remaining solid was purified by silica gel column chromatography eluting with ethyl acetate-chloroform (4: 6) to obtain 0.4 g of the desired product as white crystals.
Melting point: 131.0-133.0 ° C
1 H NMR (CDCl 3 , Me 4 Si, 300 MHz) δ8.80 (s, 1H), 8.44 (bs, 1H), 8.21 (d, J = 7.8Hz, 1H), 8.08 (s, 1H), 7.98 ( d, J = 6.8Hz, 1H), 7.82 (d, J = 6.8Hz, 1H), 7.2-7.5 (m, 3H), 5.83 (d, J = 8.0Hz, 1H), 4.29 (d, J = 17.8 Hz, 1H), 4.1-4.3 (m, 1H), 4.00 (d, J = 17.8Hz, 1H), 2.38 (s, 3H), 1.16 (d, J = 6.6Hz, 6H).
〔合成例3〕
N1−[4−(2、2−ジフルオロ−1−(4−クロロフェニル)シクロプロピル)−2−メチルフェニル]−3−ヨード−N2−(1−メチル−2−メチルチオエチル)フタル酸ジアミド(本発明化合物No.36)。
[Synthesis Example 3]
N 1 - [4- (2,2-difluoro-1- (4-chlorophenyl) cyclopropyl) -2-methylphenyl] -3-iodo -N 2 - (1-methyl-2-methylthioethyl) phthalic acid diamide (Invention compound No. 36).
工程1;4’−クロロ−3−メチル−4−ニトロベンゾフェノンの製造
3−メチル−4−ニトロ安息香酸50.0gのクロロベンゼン100ml懸濁液に塩化チオニル30.2ml及びN、N−ジメチルホルムアミド1mlを添加し、95℃にて1.5時間攪拌した後、過剰の塩化チオニルを減圧下にて留去した。反応混合物にクロロベンゼン30mlを加え、氷冷攪拌下、塩化アルミニウム44.0gを注意深く添加、次いで80℃にて2時間攪拌を継続した。反応完結後、室温まで放冷した反応混合物を氷水500mlに注ぎ、さらに濃塩酸50mlを加えた後、酢酸エチルにて抽出(150mlx2)した。有機層を水洗後、飽和食塩水次いで無水硫酸マグネシウムの順で脱水・乾燥、減圧下にて溶媒を留去した。残留した固体をジイソプロピルエーテルにて洗浄し、目的物63.5gを淡黄色結晶として得た。
融点105.0〜107.5℃
1H NMR (CDCl3, Me4Si, 300MHz) δ8.04 (d, J=8.1Hz, 1H), 7.65-7.8 (m, 4H), 7.50 (d, J=8.7Hz, 2H), 2.66 (s, 3H)。
Step 1: Preparation of 4'-chloro-3-methyl-4-nitrobenzophenone 30.2 ml of thionyl chloride and 1 ml of N, N-dimethylformamide in a suspension of 100 ml of chlorobenzene with 50.0 g of 3-methyl-4-nitrobenzoic acid Was added and stirred at 95 ° C. for 1.5 hours, and then excess thionyl chloride was distilled off under reduced pressure. To the reaction mixture, 30 ml of chlorobenzene was added, and 44.0 g of aluminum chloride was carefully added under ice-cooling and stirring was continued at 80 ° C. for 2 hours. After completion of the reaction, the reaction mixture was allowed to cool to room temperature, poured into 500 ml of ice water, 50 ml of concentrated hydrochloric acid was added, and the mixture was extracted with ethyl acetate (150 ml × 2). The organic layer was washed with water, dehydrated and dried in the order of saturated brine and then anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The remaining solid was washed with diisopropyl ether to obtain 63.5 g of the desired product as pale yellow crystals.
Melting point: 105.0-107.5 ° C
1 H NMR (CDCl 3 , Me 4 Si, 300MHz) δ8.04 (d, J = 8.1Hz, 1H), 7.65-7.8 (m, 4H), 7.50 (d, J = 8.7Hz, 2H), 2.66 ( s, 3H).
工程2;4−アミノ−4’−クロロ−3−メチルベンゾフェノンの製造
4’−クロロ−3−メチル−4−ニトロベンゾフェノン22.0gの酢酸エチル220ml溶液に、酢酸220ml、水220ml及び鉄粉26.4gを加え、加熱還流下に4.5時間攪拌した。反応完結後、反応混合物をセライト濾過、減圧下にて溶媒を留去した。残留物を酢酸エチル200mlに溶解し飽和炭酸水素ナトリウム水溶液200mlにて洗浄、有機層は、飽和食塩水次いで無水硫酸マグネシウムの順で脱水・乾燥、減圧下にて溶媒を留去した。残留物をジイソプロピルエーテルから結晶化させ、目的物16.5gを黄色結晶として得た。
融点113.0〜115.5℃
1H NMR (CDCl3, Me4Si, 300MHz) δ7.67 (d, J=8.4Hz, 2H), 7.60 (s, 1H), 7.53 (d, J=8.4Hz, 1H), 7.43 (d, J=8.4Hz, 2H), 6.66 (d, J=8.4Hz, 1H), 4.15 (bs, 2H), 2.19 (s, 3H)。
Step 2; Preparation of 4-amino-4'-chloro-3-methylbenzophenone 22.0 g of 4'-chloro-3-methyl-4-nitrobenzophenone in 220 ml of ethyl acetate, 220 ml of acetic acid, 220 ml of water and iron powder 26 .4 g was added, and the mixture was stirred for 4.5 hours while heating under reflux. After completion of the reaction, the reaction mixture was filtered through Celite, and the solvent was distilled off under reduced pressure. The residue was dissolved in 200 ml of ethyl acetate and washed with 200 ml of a saturated aqueous sodium hydrogen carbonate solution. The organic layer was dehydrated and dried in the order of saturated brine and then anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was crystallized from diisopropyl ether to obtain 16.5 g of the desired product as yellow crystals.
Melting point 113.0-115.5 ° C
1 H NMR (CDCl 3 , Me 4 Si, 300 MHz) δ7.67 (d, J = 8.4 Hz, 2H), 7.60 (s, 1H), 7.53 (d, J = 8.4 Hz, 1H), 7.43 (d, J = 8.4Hz, 2H), 6.66 (d, J = 8.4Hz, 1H), 4.15 (bs, 2H), 2.19 (s, 3H).
工程3;N−t−ブトキシカルボニル−4−(4−クロロベンゾイル)−2−メチルカルバニリド酸−t−ブチルの製造
4−アミノ−4’−クロロ−3−メチルベンゾフェノン42.5gのN、N−ジメチルホルムアミド500ml溶液に二炭酸ジ−t−ブチル105.0g及び炭酸カリウム72.0gを添加し、100℃にて3時間攪拌した。反応完結後室温まで放冷、氷水500mlに注ぎ酢酸エチルにて抽出(350mlx2)した。有機層を水洗(300mlx2)後、飽和食塩水次いで無水硫酸マグネシウムの順で脱水・乾燥、減圧下にて溶媒を留去した。残留物をヘキサンにて結晶化し、目的物70.0gを白色固体として得た。
1H NMR (CDCl3, Me4Si, 300MHz) δ7.74 (d, J=9.0Hz, 2H), 7.67 (s, 1H), 7.60 (d, J=8.1Hz, 1H), 7.47 (d, J=9.0Hz, 2H), 7.20 (d, J=8.1Hz, 1H), 2.27 (s, 3H), 1.43 (s, 18H)。
Step 3; Preparation of Nt-butoxycarbonyl-4- (4-chlorobenzoyl) -2-methylcarbanilide acid-t-butyl 4-amino-4'-chloro-3-methylbenzophenone 42.5 g N To a 500 ml solution of N-dimethylformamide were added 105.0 g of di-t-butyl dicarbonate and 72.0 g of potassium carbonate, and the mixture was stirred at 100 ° C. for 3 hours. After completion of the reaction, the mixture was allowed to cool to room temperature, poured into 500 ml of ice water and extracted with ethyl acetate (350 ml × 2). The organic layer was washed with water (300 ml × 2), dehydrated and dried in the order of saturated brine and then anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was crystallized from hexane to obtain 70.0 g of the desired product as a white solid.
1 H NMR (CDCl 3 , Me 4 Si, 300MHz) δ7.74 (d, J = 9.0Hz, 2H), 7.67 (s, 1H), 7.60 (d, J = 8.1Hz, 1H), 7.47 (d, J = 9.0Hz, 2H), 7.20 (d, J = 8.1Hz, 1H), 2.27 (s, 3H), 1.43 (s, 18H).
工程4;N−t−ブトキシカルボニル−4−[1−(4−クロロフェニル)エテニル]−2−メチルカルバニリド酸−t−ブチルの製造
t−ブトキシカリウム10.1gのテトラヒドロフラン300ml溶液にメチルトリフェニルホスホニウムブロミド32.15gを添加し、室温にて30分間攪拌、次いでN−t−ブトキシカルボニル−4−(4−クロロベンゾイル)−2−メチルカルバニリド酸−t−ブチル20.05gのテトラヒドロフラン50ml溶液を滴下し、同温度にてさらに90分攪拌を継続した。反応完結後、反応混合物を飽和塩化アンモニウム水溶液200mlに注ぎ、15分間攪拌した後、酢酸エチル150mlにて抽出した。有機層を飽和食塩水次いで無水硫酸マグネシウムの順で脱水・乾燥し、減圧下にて溶媒を留去、残留物を酢酸エチル−ヘキサン(1:9)にて溶出するシリカゲルカラムクロマトグラフィーにて精製し、目的物19.0gを黄色油状物質として得た。
nD 21.3℃1.5398
1H NMR (CDCl3, Me4Si, 300MHz) δ7.25-7.35 (m, 4H), 7.1-7.15 (m, 2H), 7.04 (d, J=7.8Hz, 1H), 5.46 (bs, 1H), 5.44 (bs, 1H), 2.18 (s, 3H), 1.44 (s, 18H)。
Step 4: Preparation of N-t-butoxycarbonyl-4- [1- (4-chlorophenyl) ethenyl] -2-methylcarbanilide acid-t-butyl
To a solution of 10.1 g of t-butoxy potassium in 300 ml of tetrahydrofuran was added 32.15 g of methyltriphenylphosphonium bromide, stirred at room temperature for 30 minutes, and then Nt-butoxycarbonyl-4- (4-chlorobenzoyl) -2- A solution of 20.05 g of methylcarbanilide acid-t-butyl in 50 ml of tetrahydrofuran was added dropwise, and stirring was continued for 90 minutes at the same temperature. After completion of the reaction, the reaction mixture was poured into 200 ml of saturated aqueous ammonium chloride solution, stirred for 15 minutes and then extracted with 150 ml of ethyl acetate. The organic layer is dehydrated and dried in the order of saturated brine and then anhydrous magnesium sulfate, the solvent is distilled off under reduced pressure, and the residue is purified by silica gel column chromatography eluting with ethyl acetate-hexane (1: 9). As a result, 19.0 g of the desired product was obtained as a yellow oily substance.
n D 21.3 ° C 1.5398
1 H NMR (CDCl 3 , Me 4 Si, 300 MHz) δ7.25-7.35 (m, 4H), 7.1-7.15 (m, 2H), 7.04 (d, J = 7.8Hz, 1H), 5.46 (bs, 1H ), 5.44 (bs, 1H), 2.18 (s, 3H), 1.44 (s, 18H).
工程5;4−[2、2−ジフルオロ−1−(4−クロロフェニル)シクロプロピル]−2−メチルアニリンの製造
N−t−ブトキシカルボニル−4−[1−(4−クロロフェニル)エテニル]−2−メチルカルバニリド酸−t−ブチル1.7gのジエチレングリコールジメチルエーテル5ml溶液に、170℃にて攪拌下、ジクロロフルオロ酢酸ナトリウム7.0gを30分間に渡って少量ずつ添加し、添加終了後180℃にてさらに30分間攪拌を継続した。反応完結後室温まで放冷、反応混合物を酢酸エチル50mlに溶解し水洗(50mlx1)、飽和食塩水次いで無水硫酸マグネシウムの順で脱水・乾燥後、減圧下にて溶媒を留去た。残留物に、室温にて攪拌下、トリフルオロ酢酸10mlを滴下し、同温度にてさらに15分攪拌を継続した。反応完結後、減圧下にて過剰のトリフルオロ酢酸を留去、残留した油状物質を酢酸エチル30mlに溶解し、飽和炭酸水素ナトリウム水溶液20mlにて洗浄した。有機層を飽和食塩水次いで無水硫酸マグネシウムの順で脱水・乾燥、減圧下にて溶媒を留去し、残留物をアセトニトリル−水(85:15)にて溶出する高速液体クロマトグラフィーにて精製し、目的物0.35gを淡黄色油状物質として得た。
nD 21.3℃1.5726
1H NMR (CDCl3, Me4Si, 300MHz) δ7.30 (d, J=8.7Hz, 2H), 7.24 (d, J=8.7Hz, 2H), 7.0-7.05 (m, 2H), 6.59 (d, J=8.7Hz, 1H), 3.53 (bs, 2H), 2.11 (s, 3H), 1.9-2.05 (m, 2H)。
Step 5; Preparation of 4- [2,2-difluoro-1- (4-chlorophenyl) cyclopropyl] -2-methylaniline Nt-butoxycarbonyl-4- [1- (4-chlorophenyl) ethenyl] -2 -7.0 g of sodium dichlorofluoroacetate was added to a solution of 1.7 g of methylcarbanilide-t-butyl in 5 ml of diethylene glycol dimethyl ether while stirring at 170 ° C over 30 minutes. The stirring was continued for another 30 minutes. After completion of the reaction, the mixture was allowed to cool to room temperature. The reaction mixture was dissolved in 50 ml of ethyl acetate, washed with water (50 ml × 1), saturated brine and then anhydrous magnesium sulfate. To the residue, 10 ml of trifluoroacetic acid was added dropwise with stirring at room temperature, and stirring was continued for another 15 minutes at the same temperature. After completion of the reaction, excess trifluoroacetic acid was distilled off under reduced pressure, and the remaining oily substance was dissolved in 30 ml of ethyl acetate and washed with 20 ml of saturated aqueous sodium hydrogen carbonate solution. The organic layer was dehydrated and dried in the order of saturated brine and then anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was purified by high performance liquid chromatography eluting with acetonitrile-water (85:15). The target product (0.35 g) was obtained as a pale yellow oily substance.
n D 21.3 ° C 1.5726
1 H NMR (CDCl 3 , Me 4 Si, 300 MHz) δ 7.30 (d, J = 8.7 Hz, 2H), 7.24 (d, J = 8.7 Hz, 2H), 7.0-7.05 (m, 2H), 6.59 ( d, J = 8.7Hz, 1H), 3.53 (bs, 2H), 2.11 (s, 3H), 1.9-2.05 (m, 2H).
工程6;N1−[4−(2、2−ジフルオロ−1−(4−クロロフェニル)シクロプロピル)−2−メチルフェニル]−3−ヨード−N2−(1−メチル−2−メチルチオエチル)フタル酸ジアミドの製造
3−ヨード−N−(1−メチル−2−メチルチオエチル)フタルアミド酸0.28gのトルエン8ml溶液に、室温にて攪拌下、トリフルオロ酢酸無水物0.2gを滴下した。同温度にて15分間攪拌した後、減圧下にて溶媒を留去、残留物をアセトニトリル2mlに溶解し、4−[2、2−ジフルオロ−1−(4−クロロフェニル)シクロプロピル]−2−メチルアニリン0.2gのアセトニトリル5ml溶液を滴下した。室温にて2時間攪拌を継続した後、反応混合物を氷冷、析出した固体を濾別、少量のアセトニトリルにて洗浄し、目的物0.32gを白色結晶として得た。
融点229.0〜232.0℃
1H NMR (CDCl3, Me4Si, 300MHz) δ8.26 (bs, 1H), 8.04 (d, J=8.7Hz, 1H), 7.94 (d, J=8.1Hz, 1H), 7.74 (d, J=7.5Hz, 1H), 7.15-7.35 (m, 7H), 6.22 (d, J=8.1Hz, 1H), 4.25-4.35 (m, 1H), 2.61 (dd, J=13.5, 6.0Hz, 1H), 2.52 (dd, J=13.5, 6.3Hz, 1H), 2.28 (s, 3H), 1.95-2.15 (m, 2H), 1.88 (s, 3H), 1.25 (d, J=6.6Hz, 3H)。
Step 6; N 1 - [4- ( 2,2- difluoro-1- (4-chlorophenyl) cyclopropyl) -2-methylphenyl] -3-iodo -N 2 - (1-methyl-2-methylthioethyl) Preparation of phthalic acid diamide 0.2 g of trifluoroacetic anhydride was added dropwise to a solution of 0.28 g of 3-iodo-N- (1-methyl-2-methylthioethyl) phthalamic acid in 8 ml of toluene at room temperature with stirring. After stirring for 15 minutes at the same temperature, the solvent was distilled off under reduced pressure, the residue was dissolved in 2 ml of acetonitrile, and 4- [2,2-difluoro-1- (4-chlorophenyl) cyclopropyl] -2- A solution of 0.2 g of methylaniline in 5 ml of acetonitrile was added dropwise. After stirring at room temperature for 2 hours, the reaction mixture was ice-cooled, and the precipitated solid was filtered off and washed with a small amount of acetonitrile to obtain 0.32 g of the desired product as white crystals.
Melting point 229.0-232.0 ° C
1 H NMR (CDCl 3 , Me 4 Si, 300 MHz) δ8.26 (bs, 1H), 8.04 (d, J = 8.7 Hz, 1H), 7.94 (d, J = 8.1 Hz, 1H), 7.74 (d, J = 7.5Hz, 1H), 7.15-7.35 (m, 7H), 6.22 (d, J = 8.1Hz, 1H), 4.25-4.35 (m, 1H), 2.61 (dd, J = 13.5, 6.0Hz, 1H ), 2.52 (dd, J = 13.5, 6.3Hz, 1H), 2.28 (s, 3H), 1.95-2.15 (m, 2H), 1.88 (s, 3H), 1.25 (d, J = 6.6Hz, 3H) .
〔合成例4〕
N1−[4−(2、2−ジフルオロ−1−(4−クロロフェニル)シクロプロピル)−2−メチルフェニル]−3−ヨード−N2−(1−メチル−2−メチルスルホニルエチル)フタル酸ジアミド(本発明化合物No.43)
合成例3にて合成したN1−[4−(2、2−ジフルオロ−1−(4−クロロフェニル)シクロプロピル)−2−メチルフェニル]−3−ヨード−N2−(1−メチル−2−メチルチオエチル)フタル酸ジアミド(本発明化合物No.1-36)0.15gのジクロロメタン20ml溶液に、氷冷攪拌下、3−クロロ過安息香酸0.12gを添加し、室温にて4.5時間攪拌を継続した。反応完結後、反応混合物を亜硫酸水素ナトリウム水溶液30ml次いで飽和炭酸水素ナトリウム水溶液30mlにて洗浄後、飽和食塩水次いで無水硫酸マグネシウムの順で脱水・乾燥、減圧下にて溶媒を留去し、目的物0.15gを無色樹脂状物質として得た。
1H NMR (CDCl3, Me4Si, 300MHz) δ8.26 (bs, 1H), 7.80 (d, J=7.8Hz, 1H), 7.74 (d, J=9.0Hz, 1H), 7.55 (d, J=7.5Hz, 1H), 7.05-7.35 (m, 7H), 6.94 (d, J=7.5Hz, 1H), 4.4-4.5 (m, 1H), 3.24 (dd, J=14.1, 4.2Hz, 1H), 3.00 (dd, J=14.1, 6.9Hz, 1H), 2.52 (s, 3H), 2.23 (s, 3H), 1.95-2.15 (m, 2H), 1.41 (d, J=6.3Hz, 3H)。
[Synthesis Example 4]
N 1 - [4- (2,2-difluoro-1- (4-chlorophenyl) cyclopropyl) -2-methylphenyl] -3-iodo -N 2 - (1-methyl-2-methylsulfonyl-ethyl) phthalate Diamide (the present compound No. 43)
N 1 synthesized in Synthesis Example 3 - [4- (2,2-difluoro-1- (4-chlorophenyl) cyclopropyl) -2-methylphenyl] -3-iodo -N 2 - (1-methyl-2 To a solution of 0.15 g of methylthioethyl) phthalic acid diamide (the present compound No. 1-36) in 20 ml of dichloromethane was added 0.12 g of 3-chloroperbenzoic acid with stirring under ice cooling, and 4.5 at room temperature. Stirring was continued for an hour. After completion of the reaction, the reaction mixture was washed with 30 ml of aqueous sodium hydrogen sulfite solution and then with 30 ml of saturated aqueous sodium hydrogen carbonate solution, dehydrated and dried in the order of saturated brine and then anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. 0.15 g was obtained as a colorless resinous material.
1 H NMR (CDCl 3 , Me 4 Si, 300 MHz) δ8.26 (bs, 1H), 7.80 (d, J = 7.8Hz, 1H), 7.74 (d, J = 9.0Hz, 1H), 7.55 (d, J = 7.5Hz, 1H), 7.05-7.35 (m, 7H), 6.94 (d, J = 7.5Hz, 1H), 4.4-4.5 (m, 1H), 3.24 (dd, J = 14.1, 4.2Hz, 1H ), 3.00 (dd, J = 14.1, 6.9Hz, 1H), 2.52 (s, 3H), 2.23 (s, 3H), 1.95-2.15 (m, 2H), 1.41 (d, J = 6.3Hz, 3H) .
〔合成例5〕
N1−[4−[2,2,2−トリフルオロ−1−ヒドロキシ−1−(4−トリフルオロメトキシフェニル)エチル]−2−メチルフェニル]−3−ヨード−N2−イソプロピルフタル酸ジアミド(本発明化合物No.58)。
[Synthesis Example 5]
N 1 - [4- [2,2,2- trifluoro-1-hydroxy-1- (4-trifluoromethoxyphenyl) ethyl] -2-methylphenyl] -3-iodo -N 2 - isopropyl phthalic acid diamide (Invention compound No. 58).
工程1;[2,2,2−トリフルオロ−1−メトキシ−1−(4−トリフルオロメトキシフェニル)エチル]トリメチルシランの製造
4−トリフルオロメトキシ安息香酸メチル10.0gの1,2−ジメトキシエタン55ml溶液に、氷冷攪拌下、(トリフルオロメチル)トリメチルシラン13.6g及びフッ化セシウム0.1gを添加し、攪拌下、2時間かけて室温まで昇温した。室温にてさらに1時間攪拌を継続した後、反応混合物を氷水200mlに注ぎ酢酸エチル200mlにて抽出、有機層を無水硫酸マグネシウムで乾燥後、減圧下にて溶媒を留去した。残留物をヘキサンにて溶出するシリカゲルカラムクロマトグラフィーにて精製し、目的物16.0gを無色油状物質として得た。
1H NMR (CDCl3, Me4Si, 300MHz) δ7.62 (d, J=8.5Hz, 2H), 7.23 (d, J=8.5Hz, 2H), 3.21 (s, 3H), 0.27 (s, 9H)。
Step 1: Preparation of [2,2,2-trifluoro-1-methoxy-1- (4-trifluoromethoxyphenyl) ethyl] trimethylsilane 10.0 g of 1,4-dimethoxymethyl 4-trifluoromethoxybenzoate To a 55 ml solution of ethane, 13.6 g of (trifluoromethyl) trimethylsilane and 0.1 g of cesium fluoride were added with stirring under ice cooling, and the temperature was raised to room temperature over 2 hours with stirring. After further stirring for 1 hour at room temperature, the reaction mixture was poured into 200 ml of ice water, extracted with 200 ml of ethyl acetate, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography eluting with hexane to obtain 16.0 g of the desired product as a colorless oil.
1 H NMR (CDCl 3 , Me 4 Si, 300 MHz) δ7.62 (d, J = 8.5Hz, 2H), 7.23 (d, J = 8.5Hz, 2H), 3.21 (s, 3H), 0.27 (s, 9H).
工程2;2,2,2−トリフルオロ−4'−トリフルオロメトキシアセトフェノンの製造
[2,2,2−トリフルオロ−1−メトキシ−1−(4−トリフルオロメトキシフェニル)エチル]トリメチルシラン16.0gのテトラヒドロフラン55ml溶液に、室温にて攪拌下、フッ化テトラブチルアンモニウムのテトラヒドロフラン1M溶液9.5mlを添加し、室温にて20分間攪拌した。反応完結後、反応混合物に飽和炭酸水素ナトリウム水溶液200mlを加え酢酸エチル200mlにて抽出、有機層を無水硫酸マグネシウムで乾燥後、減圧下にて溶媒を留去し、目的物10.8gを褐色油状物質として得た。
1H NMR (CDCl3, Me4Si, 300MHz) δ8.15 (d, J=8.8Hz, 2H), 7.37 (d, J=8.8Hz, 2H)。
Step 2: Production of 2,2,2-trifluoro-4′-trifluoromethoxyacetophenone
[2,2,2-trifluoro-1-methoxy-1- (4-trifluoromethoxyphenyl) ethyl] trimethylsilane (16.0 g) in tetrahydrofuran (55 ml) was stirred at room temperature with tetrahydrofuran of tetrabutylammonium fluoride. 9.5 ml of 1M solution was added and stirred at room temperature for 20 minutes. After completion of the reaction, 200 ml of saturated aqueous sodium hydrogen carbonate solution was added to the reaction mixture, extracted with 200 ml of ethyl acetate, the organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and 10.8 g of the desired product was obtained as a brown oil. Obtained as material.
1 H NMR (CDCl 3 , Me 4 Si, 300 MHz) δ8.15 (d, J = 8.8 Hz, 2H), 7.37 (d, J = 8.8 Hz, 2H).
工程3;4−[2,2,2−トリフルオロ−1−ヒドロキシ−1−(4−トリフルオロメトキシフェニル)エチル]−2−メチルカルバニリド酸−t−ブチルの製造
窒素雰囲気下の4−ヨード−2−メチルカルバニリド酸−t−ブチル10.0gのt−ブチルメチルエーテル130ml溶液に、−60℃にて攪拌下、n−ブチルリチウム(1.58Mヘキサン溶液)41.8mlを滴下し、滴下終了後0℃に昇温、さらに30分間攪拌した。次いで、この反応混合物を−78℃に冷却、2,2,2−トリフルオロ−4'−トリフルオロメトキシアセトフェノン7.75gを添加し、徐々に0℃まで昇温、さらに同温度にて30分間攪拌を継続した。反応完結後、反応混合物を飽和塩化アンモニウム水溶液300mlに注ぎ有機層を分取、水層は酢酸エチル100mlにて抽出した。有機層を合わせ無水硫酸マグネシウムで乾燥、減圧下にて溶媒を留去した。残留物を酢酸エチル−ヘキサン(1:19〜1:4)にて溶出するシリカゲルカラムクロマトグラフィーにて精製し、目的物9.0gを無色油状物質として得た。
1H NMR (CDCl3, Me4Si, 300MHz) δ7.87 (d, J=8.5Hz, 1H), 7.50 (d, J=8.8Hz, 2H), 7.1-7.35 (m, 4H), 6.31 (bs, 1H), 2.95 (bs, 1H), 2.23 (s, 3H), 1.52 (s, 9H)。
Step 3; Preparation of 4- [2,2,2-trifluoro-1-hydroxy-1- (4-trifluoromethoxyphenyl) ethyl] -2-methylcarbanilide acid-t-butyl 4 under nitrogen atmosphere -Iodo-2-methylcarbanilic acid-t-butyl 10.0 g of t-butyl methyl ether in 130 ml was stirred at -60 ° C and 41.8 ml of n-butyl lithium (1.58 M hexane solution) was added. After the dropwise addition, the temperature was raised to 0 ° C. after completion of the dropwise addition, and the mixture was further stirred for 30 minutes. The reaction mixture was then cooled to −78 ° C., and 2,2,2-trifluoro-4′-trifluoromethoxyacetophenone (7.75 g) was added, the temperature was gradually raised to 0 ° C., and the temperature was further increased for 30 minutes. Stirring was continued. After completion of the reaction, the reaction mixture was poured into 300 ml of saturated aqueous ammonium chloride solution, the organic layer was separated, and the aqueous layer was extracted with 100 ml of ethyl acetate. The organic layers were combined and dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography eluting with ethyl acetate-hexane (1: 19-1: 4) to obtain 9.0 g of the objective product as a colorless oil.
1 H NMR (CDCl 3 , Me 4 Si, 300 MHz) δ7.87 (d, J = 8.5Hz, 1H), 7.50 (d, J = 8.8Hz, 2H), 7.1-7.35 (m, 4H), 6.31 ( bs, 1H), 2.95 (bs, 1H), 2.23 (s, 3H), 1.52 (s, 9H).
工程4;1−(4−アミノ−3−メチルフェニル)−2,2,2−トリフルオロ−1−(4−トリフルオロメトキシフェニル)エタノールの製造
4−[2,2,2−トリフルオロ−1−ヒドロキシ−1−(4−トリフルオロメトキシフェニル)エチル]−2−メチルカルバニリド酸−t−ブチル9.0gに、氷冷攪拌下、トリフルオロ酢酸16.0mlを滴下した。室温にて30分攪拌を継続した後、氷冷下、飽和炭酸カリウム水溶液200mlを加えクロロホルム100ml及び酢酸エチル100mlにて抽出、有機層を併せて無水硫酸ナトリウムにて乾燥後、減圧下にて溶媒を留去し、目的物6.8gを黄色結晶として得た。
融点127.0〜128.5℃
1H NMR (CDCl3, Me4Si, 300MHz) δ7.51 (d, J=8.5Hz, 2H), 7.0-7.25 (m, 4H), 6.60 (d, J=8.3Hz, 1H), 3.06 (bs, 3H), 2.13 (s, 3H)。
Step 4: Production of 1- (4-amino-3-methylphenyl) -2,2,2-trifluoro-1- (4-trifluoromethoxyphenyl) ethanol 4- [2,2,2-trifluoro- 19.0 ml of trifluoroacetic acid was added dropwise to 9.0 g of 1-hydroxy-1- (4-trifluoromethoxyphenyl) ethyl] -2-methylcarbanilide acid-t-butyl under ice-cooling and stirring. After stirring for 30 minutes at room temperature, 200 ml of saturated aqueous potassium carbonate solution was added under ice cooling, extracted with 100 ml of chloroform and 100 ml of ethyl acetate, the organic layers were combined and dried over anhydrous sodium sulfate, and then the solvent was removed under reduced pressure. Was distilled off to obtain 6.8 g of the desired product as yellow crystals.
Melting point 127.0-128.5 ° C
1 H NMR (CDCl 3 , Me 4 Si, 300MHz) δ7.51 (d, J = 8.5Hz, 2H), 7.0-7.25 (m, 4H), 6.60 (d, J = 8.3Hz, 1H), 3.06 ( bs, 3H), 2.13 (s, 3H).
工程5;N1−[4−[2,2,2−トリフルオロ−1−ヒドロキシ−1−(4−トリフルオロメトキシフェニル)エチル]−2−メチルフェニル]−3−ヨード−N2−イソプロピルフタル酸ジアミドの製造
3−ヨード−N−イソプロピルフタルアミド酸0.2gのトルエン5ml溶液に、室温にて攪拌下、トリフルオロ酢酸無水物1.0gを滴下した。同温度にて30分間攪拌した後、減圧下に溶媒を留去、残留物をアセトニトリル5mlに溶解し、1−(4−アミノ−3−メチルフェニル)−2,2,2−トリフルオロ−1−(4−トリフルオロメトキシフェニル)エタノール0.2g及びトリフルオロ酢酸1滴を添加、室温にて4時間攪拌を継続した。反応完結後、減圧下にて溶媒を留去、残留物を酢酸エチル−ヘキサン(1:1)にて溶出するシリカゲルカラムクロマトグラフィーにて精製し、目的物0.33gを無色樹脂状物質として得た。
1H NMR (CDCl3, Me4Si, 400MHz) δ8.39 (bs, 1H), 8.10 (d, J=8.8Hz, 1H), 7.95 (d, J=7.6Hz, 1H), 7.80 (d, J=8.0Hz, 1H), 7.52 (d, J=8.0Hz, 2H), 7.2-7.35 (m, 5H), 5.90 (d, J=8.0Hz, 1H), 4.15-4.3 (m, 1H), 3.01 (s, 1H), 2.33 (s, 3H), 1.17 (d, J=6.6Hz, 6H)。
前記製造法及び合成例に準じて、前記の第1表に記載した一般式(1)及び前記の第2表に記載した一般式(2)で表される置換ベンズアニリド化合物を合成した。合成した化合物の物性を第5表に記載した。
Step 5; N 1- [4- [2,2,2-trifluoro-1-hydroxy-1- (4-trifluoromethoxyphenyl) ethyl] -2-methylphenyl] -3-iodo-N 2 -isopropyl Preparation of phthalic acid diamide 1.0 g of trifluoroacetic anhydride was added dropwise to a solution of 0.2 g of 3-iodo-N-isopropylphthalamic acid in 5 ml of toluene with stirring at room temperature. After stirring at the same temperature for 30 minutes, the solvent was distilled off under reduced pressure, the residue was dissolved in 5 ml of acetonitrile, and 1- (4-amino-3-methylphenyl) -2,2,2-trifluoro-1 -0.2 g of (4-trifluoromethoxyphenyl) ethanol and 1 drop of trifluoroacetic acid were added and stirring was continued for 4 hours at room temperature. After completion of the reaction, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography eluting with ethyl acetate-hexane (1: 1) to obtain 0.33 g of the objective product as a colorless resinous substance. It was.
1 H NMR (CDCl 3 , Me 4 Si, 400 MHz) δ 8.39 (bs, 1H), 8.10 (d, J = 8.8Hz, 1H), 7.95 (d, J = 7.6Hz, 1H), 7.80 (d, J = 8.0Hz, 1H), 7.52 (d, J = 8.0Hz, 2H), 7.2-7.35 (m, 5H), 5.90 (d, J = 8.0Hz, 1H), 4.15-4.3 (m, 1H), 3.01 (s, 1H), 2.33 (s, 3H), 1.17 (d, J = 6.6Hz, 6H).
A substituted benzanilide compound represented by the general formula (1) described in Table 1 and the general formula (2) described in Table 2 was synthesized according to the production method and synthesis examples. The physical properties of the synthesized compounds are shown in Table 5.
〔第5表〕
―――――――――――――――――――――――――――――――――――――――
No. m.p.(℃) No. m.p.(℃) No. m.p.(℃)
―――――――――――――――――――――――――――――――――――――――
1 131.0-133.0 28 123.0-126.0 55 135.0-136.0
2 108.0-112.0 29 115.0-118.5 56 樹脂状
3 196.0-198.0 30 樹脂状 57 107.0-110.0
4 108.0-112.0 31 110.0-112.0 58 樹脂状
5 140.0-142.0 32 174.5-176.0 59 107.0-109.0
6 134.0-136.0 33 樹脂状 60 樹脂状
7 257.0-259.0 34 122.0-126.5 61 212.0-214.0
8 145.0-153.0 35 132.0-134.0 62 95.5-99.0
9 132.0-135.0 36 229.0-232.0 63 101.0-103.0
10 103.5-110.0 37 205.0-208.0 64 112.0-115.0
11 116.5-120.3 38 219.0-220.0 65 91.0-95.0
12 124.5-129.5 39 185.0-186.0 66 116.0-120.0
13 113.5-120.5 40 199.0-200.0 67 99.0-103.0
14 114.0-124.0 41 175.0-177.0 68 83.0-89.0
15 140.0-150.0 42 樹脂状 69 樹脂状
16 138.0-147.0 43 樹脂状 70 樹脂状
17 123.0-129.5 44 樹脂状 71 樹脂状
18 115.0-116.0 45 213.0-214.0 72 樹脂状
19 113.0-115.0 46 169.0-170.0 73 111.0-113.0
20 157.0-167.0 47 130.0-132.0 74 123.0-126.0
21 113.5-117.5 48 190.0-191.0 75 115.0-117.5
22 117.0-122.0 49 216.5-218.5 76 102.0-105.0
23 116.0-124.5 50 208.0-211.0 77 樹脂状
24 108.5-112.0 51 212.0-213.0 78 樹脂状
25 117.0-137.0 52 196.0-197.5 79 樹脂状
26 124.0-132.0 53 197.0-200.5
27 270.0-272.0 54 175.0-176.0
―――――――――――――――――――――――――――――――――――――――
次に、本発明の有用性を明らかにするため、効力試験例を具体的に以下に示す。
[Table 5]
―――――――――――――――――――――――――――――――――――――――
No. mp (° C) No. mp (° C) No. mp (° C)
―――――――――――――――――――――――――――――――――――――――
1 131.0-133.0 28 123.0-126.0 55 135.0-136.0
2 108.0-112.0 29 115.0-118.5 56 Resinous
3 196.0-198.0 30 Resin-like 57 107.0-110.0
4 108.0-112.0 31 110.0-112.0 58 Resinous
5 140.0-142.0 32 174.5-176.0 59 107.0-109.0
6 134.0-136.0 33 Resin 60 Resin
7 257.0-259.0 34 122.0-126.5 61 212.0-214.0
8 145.0-153.0 35 132.0-134.0 62 95.5-99.0
9 132.0-135.0 36 229.0-232.0 63 101.0-103.0
10 103.5-110.0 37 205.0-208.0 64 112.0-115.0
11 116.5-120.3 38 219.0-220.0 65 91.0-95.0
12 124.5-129.5 39 185.0-186.0 66 116.0-120.0
13 113.5-120.5 40 199.0-200.0 67 99.0-103.0
14 114.0-124.0 41 175.0-177.0 68 83.0-89.0
15 140.0-150.0 42 Resinous 69 Resinous
16 138.0-147.0 43 Resin 70 Resin
17 123.0-129.5 44 Resin 71 Resin
18 115.0-116.0 45 213.0-214.0 72 Resinous
19 113.0-115.0 46 169.0-170.0 73 111.0-113.0
20 157.0-167.0 47 130.0-132.0 74 123.0-126.0
21 113.5-117.5 48 190.0-191.0 75 115.0-117.5
22 117.0-122.0 49 216.5-218.5 76 102.0-105.0
23 116.0-124.5 50 208.0-211.0 77 Resinous
24 108.5-112.0 51 212.0-213.0 78 Resinous
25 117.0-137.0 52 196.0-197.5 79 Resinous
26 124.0-132.0 53 197.0-200.5
27 270.0-272.0 54 175.0-176.0
―――――――――――――――――――――――――――――――――――――――
Next, in order to clarify the usefulness of the present invention, an efficacy test example is specifically shown below.
〔試験例1〕 モモシンクイガに対する効力試験
上記の第5表に記載された化合物を各々10%乳剤(化合物によっては25%水和剤)に製剤し、前記の第4表に記載された化合物(製剤)と合わせて、展着剤の入った水で希釈して、所定濃度の薬液を調製した。次に、モモシンクイガ雌成虫に1日産卵させたリンゴの幼果を準備した。実体顕微鏡下で1幼果当たり15卵になるように卵数を調製し、所定濃度の薬液に約20秒浸漬した。風乾後に腰高シャーレ(直径5.5cm×高さ6cm)に処理幼果を入れ、25℃の恒温室に収容した。処理後約20日後に、幼果内に侵入している幼虫数とシャーレ内に幼果から脱出した幼虫数を計数し、生存虫数とした。下記の計算式から死虫率を算出した。尚、試験は2区制で行なった。
[Test Example 1] Efficacy test against peach fruit moth Each of the compounds listed in Table 5 above was formulated into 10% emulsion (25% wettable powder depending on the compound), and the compounds described in Table 4 above (Formulation) ) And diluted with water containing a spreading agent to prepare a chemical solution with a predetermined concentration. Next, apple berries that were laid for 1 day by adult peach moth females were prepared. The number of eggs was adjusted to 15 eggs per juvenile under a stereomicroscope and immersed in a chemical solution of a predetermined concentration for about 20 seconds. After air drying, the treated fruit was placed in a waist-high petri dish (diameter: 5.5 cm × height: 6 cm) and housed in a thermostatic chamber at 25 ° C. About 20 days after the treatment, the number of larvae invading the larvae and the number of larvae that escaped from the larvae in the petri dish were counted to obtain the number of live worms. The death rate was calculated from the following formula. The test was conducted in a two-ward system.
死虫率(%)=(15-生存虫数)/15×100
各薬液濃度に対する死虫率から、プロビット法に基づいて半数致死濃度(LC50値)を求めた。更に共力効果(相乗効果)の程度を判定するために通常用いられているSun & Johnson法(ジャーナル オブ エコノミック エントモロジー誌、1960年、第55巻、887頁)の式を用いて、共力係数を計算した。共力係数は次に示す式で表される。
Mortality (%) = (15−number of surviving insects) / 15 × 100
A half lethal concentration (LC 50 value) was determined from the mortality rate for each chemical concentration based on the probit method. Furthermore, using the formula of the Sun & Johnson method (Journal of Economic Entomology, 1960, Vol. 55, page 887), which is commonly used to determine the degree of synergistic effect (synergistic effect), The coefficient was calculated. The synergistic coefficient is expressed by the following equation.
共力係数=混合剤の実際の毒性指数/混合剤の理論的毒性指数×100
但し、
混合剤の実際の毒性指数:[A]のLC50/[A][B]混合剤のLC50×100
混合剤の理論的毒性指数:([A]の毒性指数×[A][B]混合剤の中の[A]の%+[B]の毒性指数×[A][B]混合剤中の[B]の%)/100
[A]:一般式(1)及び一般式(2)で表される置換ベンズアニリド化合物
[B]:化合物群Aから選ばれる化合物
%:[A]と[B]の総重量に対する重量百分率
[A]の毒性指数:100
[B]の毒性指数:([A]のLC50/[B]のLC50)×100
である。
Co-efficiency factor = actual toxicity index of the admixture / theoretical toxicity index of the admixture x 100
However,
Actual toxicity index of admixtures: LC 50 × 100 of LC 50 / [A] [B ] admixture [A]
Theoretical toxicity index of the mixture: ([A] toxicity index x [A] [B]% of [A] + [B] toxicity index x [A] [B] % Of [B] / 100
[A]: Substituted benzanilide compound represented by general formula (1) and general formula (2)
[B]: Compound selected from compound group A
%: Weight percentage of the total weight of [A] and [B]
[A] Toxicity Index: 100
Toxicity index of [B]: (LC 50 of LC 50 / [B] of [A]) × 100
It is.
この共力係数の値が100より大きいほど相乗効果が高く、100に等しいときは相加的効果、100より小さくなるほど拮抗効果が高くなる、ということを示す。 It shows that the synergistic effect is higher as the value of the synergistic coefficient is larger than 100, the additive effect is greater than 100, and the antagonistic effect is higher as it is smaller than 100.
試験の結果、下記の化合物の組合わせにおいて、共力係数が100よりも大きくなった。 As a result of the test, the synergistic coefficient was larger than 100 in the combination of the following compounds.
共力係数が100よりも大きくなった組合せ:1+gu,1+ht,1+hw,1+hx,1+id,1+if,1+il,1+ja,1+je,1+jo,1+jx,1+kg,1+kh,1+km,1+kn,1+lg,1+lk,1+ln,1+lr,1+sj,1+sm,1+so,2+gu,2+ht,2+hw,2+hx,2+id,2+if,2+il,2+ja,2+je,2+jo,2+jx,2+kg,2+kh,2+km,2+kn,2+lg,2+lk,2+ln,2+lr,2+sj,2+sm,2+so,3+gu,3+ht,3+hw,3+hx,3+id,3+if,3+il,3+ja,3+je,3+jo,3+jx,3+kg,3+kh,3+km,3+kn,3+lg,3+lk,3+ln,3+lr,3+sj,3+sm,3+so,4+gu,4+ht,4+hw,4+hx,4+id,4+if,4+il,4+ja,4+je,4+jo,4+jx,4+kg,4+kh,4+km,4+kn,4+lg,4+lk,4+ln,4+lr,4+sj,4+sm,4+so,5+gu,5+ht,5+hw,5+hx,5+id,5+if,5+il,5+ja,5+je,5+jo,5+jx,5+kg,5+kh,5+km,5+kn,5+lg,5+lk,5+ln,5+lr,5+sj,5+sm,5+so,6+gu,6+ht,6+hw,6+hx,6+id,6+if,6+il,6+ja,6+je,6+jo,6+jx,6+kg,6+kh,6+km,6+kn,6+lg,6+lk,6+ln,6+lr,6+sj,6+sm,6+so,7+gu,7+ht,7+hw,7+hx,7+id,7+if,7+il,7+ja,7+je,7+jo,7+jx,7+kg,7+kh,7+km,7+kn,7+lg,7+lk,7+ln,7+lr,7+sj,7+sm,7+so,8+gu,8+ht,8+hw,8+hx,8+id,8+if,8+il,8+ja,8+je,8+jo,8+jx,8+kg,8+kh,8+km,8+kn,8+lg,8+lk,8+ln,8+lr,8+sj,8+sm,8+so,9+gu,9+ht,9+hw,9+hx,9+id,9+if,9+il,9+ja,9+je,9+jo,9+jx,9+kg,9+kh,9+km,9+kn,9+lg,9+lk,9+ln,9+lr,9+sj,9+sm,9+so,10+gu,10+ht,10+hw,10+hx,10+id,10+if,10+il,10+ja,10+je,10+jo,10+jx,10+kg,10+kh,10+km,10+kn,10+lg,10+lk,10+ln,10+lr,10+sj,10+sm,10+so,11+gu,11+ht,11+hw,11+hx,11+id,11+if,11+il,11+ja,11+je,11+jo,11+jx,11+kg,11+kh,11+km,11+kn,11+lg,11+lk,11+ln,11+lr,11+sj,11+sm,11+so,12+gu,12+ht,12+hw,12+hx,12+id,12+if,12+il,12+ja,12+je,12+jo,12+jx,12+kg,12+kh,12+km,12+kn,12+lg,12+lk,12+ln,12+lr,12+sj,12+sm,12+so,13+gu,13+ht,13+hw,13+hx,13+id,13+if,13+il,13+ja,13+je,13+jo,13+jx,13+kg,13+kh,13+km,13+kn,13+lg,13+lk,13+ln,13+lr,13+sj,13+sm,13+so,14+gu,14+ht,14+hw,14+hx,14+id,14+if,14+il,14+ja,14+je,14+jo,14+jx,14+kg,14+kh,14+km,14+kn,14+lg,14+lk,14+ln,14+lr,14+sj,14+sm,14+so,15+gu,15+ht,15+hw,15+hx,15+id,15+if,15+il,15+ja,15+je,15+jo,15+jx,15+kg,15+kh,15+km,15+kn,15+lg,15+lk,15+ln,15+lr,15+sj,15+sm,15+so,16+gu,16+ht,16+hw,16+hx,16+id,16+if,16+il,16+ja,16+je,16+jo,16+jx,16+kg,16+kh,16+km,16+kn,16+lg,16+lk,16+ln,16+lr,16+sj,16+sm,16+so,17+gu,17+ht,17+hw,17+hx,17+id,17+if,17+il,17+ja,17+je,17+jo,17+jx,17+kg,17+kh,17+km,17+kn,17+lg,17+lk,17+ln,17+lr,17+sj,17+sm,17+so,18+gu,18+ht,18+hw,18+hx,18+id,18+if,18+il,18+ja,18+je,18+jo,18+jx,18+kg,18+kh,18+km,18+kn,18+lg,18+lk,18+ln,18+lr,18+sj,18+sm,18+so,19+gu,19+ht,19+hw,19+hx,19+id,19+if,19+il,19+ja,19+je,19+jo,19+jx,19+kg,19+kh,19+km,19+kn,19+lg,19+lk,19+ln,19+lr,19+sj,19+sm,19+so,20+gu,20+ht,20+hw,20+hx,20+id,20+if,20+il,20+ja,20+je,20+jo,20+jx,20+kg,20+kh,20+km,20+kn,20+lg,20+lk,20+ln,20+lr,20+sj,20+sm,20+so,21+gu,21+ht,21+hw,21+hx,21+id,21+if,21+il,21+ja,21+je,21+jo,21+jx,21+kg,21+kh,21+km,21+kn,21+lg,21+lk,21+ln,21+lr,21+sj,21+sm,21+so,22+gu,22+ht,22+hw,22+hx,22+id,22+if,22+il,22+ja,22+je,22+jo,22+jx,22+kg,22+kh,22+km,22+kn,22+lg,22+lk,22+ln,22+lr,22+sj,22+sm,22+so,23+gu,23+ht,23+hw,23+hx,23+id,23+if,23+il,23+ja,23+je,23+jo,23+jx,23+kg,23+kh,23+km,23+kn,23+lg,23+lk,23+ln,23+lr,23+sj,23+sm,23+so,24+gu,24+ht,24+hw,24+hx,24+id,24+if,24+il,24+ja,24+je,24+jo,24+jx,24+kg,24+kh,24+km,24+kn,24+lg,24+lk,24+ln,24+lr,24+sj,24+sm,24+so,25+gu,25+ht,25+hw,25+hx,25+id,25+if,25+il,25+ja,25+je,25+jo,25+jx,25+kg,25+kh,25+km,25+kn,25+lg,25+lk,25+ln,25+lr,25+sj,25+sm,25+so,26+gu,26+ht,26+hw,26+hx,26+id,26+if,26+il,26+ja,26+je,26+jo,26+jx,26+kg,26+kh,26+km,26+kn,26+lg,26+lk,26+ln,26+lr,26+sj,26+sm,26+so,27+gu,27+ht,27+hw,27+hx,27+id,27+if,27+il,27+ja,27+je,27+jo,27+jx,27+kg,27+kh,27+km,27+kn,27+lg,27+lk,27+ln,27+lr,27+sj,27+sm,27+so,28+gu,28+ht,28+hw,28+hx,28+id,28+if,28+il,28+ja,28+je,28+jo,28+jx,28+kg,28+kh,28+km,28+kn,28+lg,28+lk,28+ln,28+lr,28+sj,28+sm,28+so,29+gu,29+ht,29+hw,29+hx,29+id,29+if,29+il,29+ja,29+je,29+jo,29+jx,29+kg,29+kh,29+km,29+kn,29+lg,29+lk,29+ln,29+lr,29+sj,29+sm,29+so,30+gu,30+ht,30+hw,30+hx,30+id,30+if,30+il,30+ja,30+je,30+jo,30+jx,30+kg,30+kh,30+km,30+kn,30+lg,30+lk,30+ln,30+lr,30+sj,30+sm,30+so,31+gu,31+ht,31+hw,31+hx,31+id,31+if,31+il,31+ja,31+je,31+jo,31+jx,31+kg,31+kh,31+km,31+kn,31+lg,31+lk,31+ln,31+lr,31+sj,31+sm,31+so,32+gu,32+ht,32+hw,32+hx,32+id,32+if,32+il,32+ja,32+je,32+jo,32+jx,32+kg,32+kh,32+km,32+kn,32+lg,32+lk,32+ln,32+lr,32+sj,32+sm,32+so,33+gu,33+ht,33+hw,33+hx,33+id,33+if,33+il,33+ja,33+je,33+jo,33+jx,33+kg,33+kh,33+km,33+kn,33+lg,33+lk,33+ln,33+lr,33+sj,33+sm,33+so,34+gu,34+ht,34+hw,34+hx,34+id,34+if,34+il,34+ja,34+je,34+jo,34+jx,34+kg,34+kh,34+km,34+kn,34+lg,34+lk,34+ln,34+lr,34+sj,34+sm,34+so,35+gu,35+ht,35+hw,35+hx,35+id,35+if,35+il,35+ja,35+je,35+jo,35+jx,35+kg,35+kh,35+km,35+kn,35+lg,35+lk,35+ln,35+lr,35+sj,35+sm,35+so,36+gu,36+ht,36+hw,36+hx,36+id,36+if,36+il,36+ja,36+je,36+jo,36+jx,36+kg,36+kh,36+km,36+kn,36+lg,36+lk,36+ln,36+lr,36+sj,36+sm,36+so,37+gu,37+ht,37+hw,37+hx,37+id,37+if,37+il,37+ja,37+je,37+jo,37+jx,37+kg,37+kh,37+km,37+kn,37+lg,37+lk,37+ln,37+lr,37+sj,37+sm,37+so,38+gu,38+ht,38+hw,38+hx,38+id,38+if,38+il,38+ja,38+je,38+jo,38+jx,38+kg,38+kh,38+km,38+kn,38+lg,38+lk,38+ln,38+lr,38+sj,38+sm,38+so,39+gu,39+ht,39+hw,39+hx,39+id,39+if,39+il,39+ja,39+je,39+jo,39+jx,39+kg,39+kh,39+km,39+kn,39+lg,39+lk,39+ln,39+lr,39+sj,39+sm,39+so,40+gu,40+ht,40+hw,40+hx,40+id,40+if,40+il,40+ja,40+je,40+jo,40+jx,40+kg,40+kh,40+km,40+kn,40+lg,40+lk,40+ln,40+lr,40+sj,40+sm,40+so,41+gu,41+ht,41+hw,41+hx,41+id,41+if,41+il,41+ja,41+je,41+jo,41+jx,41+kg,41+kh,41+km,41+kn,41+lg,41+lk,41+ln,41+lr,41+sj,41+sm,41+so,42+gu,42+ht,42+hw,42+hx,42+id,42+if,42+il,42+ja,42+je,42+jo,42+jx,42+kg,42+kh,42+km,42+kn,42+lg,42+lk,42+ln,42+lr,42+sj,42+sm,42+so,43+gu,43+ht,43+hw,43+hx,43+id,43+if,43+il,43+ja,43+je,43+jo,43+jx,43+kg,43+kh,43+km,43+kn,43+lg,43+lk,43+ln,43+lr,43+sj,43+sm,43+so,44+gu,44+ht,44+hw,44+hx,44+id,44+if,44+il,44+ja,44+je,44+jo,44+jx,44+kg,44+kh,44+km,44+kn,44+lg,44+lk,44+ln,44+lr,44+sj,44+sm,44+so,45+gu,45+ht,45+hw,45+hx,45+id,45+if,45+il,45+ja,45+je,45+jo,45+jx,45+kg,45+kh,45+km,45+kn,45+lg,45+lk,45+ln,45+lr,45+sj,45+sm,45+so,46+gu,46+ht,46+hw,46+hx,46+id,46+if,46+il,46+ja,46+je,46+jo,46+jx,46+kg,46+kh,46+km,46+kn,46+lg,46+lk,46+ln,46+lr,46+sj,46+sm,46+so,47+gu,47+ht,47+hw,47+hx,47+id,47+if,47+il,47+ja,47+je,47+jo,47+jx,47+kg,47+kh,47+km,47+kn,47+lg,47+lk,47+ln,47+lr,47+sj,47+sm,47+so,48+gu,48+ht,48+hw,48+hx,48+id,48+if,48+il,48+ja,48+je,48+jo,48+jx,48+kg,48+kh,48+km,48+kn,48+lg,48+lk,48+ln,48+lr,48+sj,48+sm,48+so,49+gu,49+ht,49+hw,49+hx,49+id,49+if,49+il,49+ja,49+je,49+jo,49+jx,49+kg,49+kh,49+km,49+kn,49+lg,49+lk,49+ln,49+lr,49+sj,49+sm,49+so,50+gu,50+ht,50+hw,50+hx,50+id,50+if,50+il,50+ja,50+je,50+jo,50+jx,50+kg,50+kh,50+km,50+kn,50+lg,50+lk,50+ln,50+lr,50+sj,50+sm,50+so,51+gu,51+ht,51+hw,51+hx,51+id,51+if,51+il,51+ja,51+je,51+jo,51+jx,51+kg,51+kh,51+km,51+kn,51+lg,51+lk,51+ln,51+lr,51+sj,51+sm,51+so,52+gu,52+ht,52+hw,52+hx,52+id,52+if,52+il,52+ja,52+je,52+jo,52+jx,52+kg,52+kh,52+km,52+kn,52+lg,52+lk,52+ln,52+lr,52+sj,52+sm,52+so,53+gu,53+ht,53+hw,53+hx,53+id,53+if,53+il,53+ja,53+je,53+jo,53+jx,53+kg,53+kh,53+km,53+kn,53+lg,53+lk,53+ln,53+lr,53+sj,53+sm,53+so,54+gu,54+ht,54+hw,54+hx,54+id,54+if,54+il,54+ja,54+je,54+jo,54+jx,54+kg,54+kh,54+km,54+kn,54+lg,54+lk,54+ln,54+lr,54+sj,54+sm,54+so,55+gu,55+ht,55+hw,55+hx,55+id,55+if,55+il,55+ja,55+je,55+jo,55+jx,55+kg,55+kh,55+km,55+kn,55+lg,55+lk,55+ln,55+lr,55+sj,55+sm,55+so,56+gu,56+ht,56+hw,56+hx,56+id,56+if,56+il,56+ja,56+je,56+jo,56+jx,56+kg,56+kh,56+km,56+kn,56+lg,56+lk,56+ln,56+lr,56+sj,56+sm,56+so,57+gu,57+ht,57+hw,57+hx,57+id,57+if,57+il,57+ja,57+je,57+jo,57+jx,57+kg,57+kh,57+km,57+kn,57+lg,57+lk,57+ln,57+lr,57+sj,57+sm,57+so,58+gu,58+ht,58+hw,58+hx,58+id,58+if,58+il,58+ja,58+je,58+jo,58+jx,58+kg,58+kh,58+km,58+kn,58+lg,58+lk,58+ln,58+lr,58+sj,58+sm,58+so,59+gu,59+ht,59+hw,59+hx,59+id,59+if,59+il,59+ja,59+je,59+jo,59+jx,59+kg,59+kh,59+km,59+kn,59+lg,59+lk,59+ln,59+lr,59+sj,59+sm,59+so,60+gu,60+ht,60+hw,60+hx,60+id,60+if,60+il,60+ja,60+je,60+jo,60+jx,60+kg,60+kh,60+km,60+kn,60+lg,60+lk,60+ln,60+lr,60+sj,60+sm,60+so,61+gu,61+ht,61+hw,61+hx,61+id,61+if,61+il,61+ja,61+je,61+jo,61+jx,61+kg,61+kh,61+km,61+kn,61+lg,61+lk,61+ln,61+lr,61+sj,61+sm,61+so,62+gu,62+ht,62+hw,62+hx,62+id,62+if,62+il,62+ja,62+je,62+jo,62+jx,62+kg,62+kh,62+km,62+kn,62+lg,62+lk,62+ln,62+lr,62+sj,62+sm,62+so,63+gu,63+ht,63+hw,63+hx,63+id,63+if,63+il,63+ja,63+je,63+jo,63+jx,63+kg,63+kh,63+km,63+kn,63+lg,63+lk,63+ln,63+lr,63+sj,63+sm,63+so,64+gu,64+ht,64+hw,64+hx,64+id,64+if,64+il,64+ja,64+je,64+jo,64+jx,64+kg,64+kh,64+km,64+kn,64+lg,64+lk,64+ln,64+lr,64+sj,64+sm,64+so,65+gu,65+ht,65+hw,65+hx,65+id,65+if,65+il,65+ja,65+je,65+jo,65+jx,65+kg,65+kh,65+km,65+kn,65+lg,65+lk,65+ln,65+lr,65+sj,65+sm,65+so,66+gu,66+ht,66+hw,66+hx,66+id,66+if,66+il,66+ja,66+je,66+jo,66+jx,66+kg,66+kh,66+km,66+kn,66+lg,66+lk,66+ln,66+lr,66+sj,66+sm,66+so,67+gu,67+ht,67+hw,67+hx,67+id,67+if,67+il,67+ja,67+je,67+jo,67+jx,67+kg,67+kh,67+km,67+kn,67+lg,67+lk,67+ln,67+lr,67+sj,67+sm,67+so,68+gu,68+ht,68+hw,68+hx,68+id,68+if,68+il,68+ja,68+je,68+jo,68+jx,68+kg,68+kh,68+km,68+kn,68+lg,68+lk,68+ln,68+lr,68+sj,68+sm,68+so,69+gu,69+ht,69+hw,69+hx,69+id,69+if,69+il,69+ja,69+je,69+jo,69+jx,69+kg,69+kh,69+km,69+kn,69+lg,69+lk,69+ln,69+lr,69+sj,69+sm,69+so,70+gu,70+ht,70+hw,70+hx,70+id,70+if,70+il,70+ja,70+je,70+jo,70+jx,70+kg,70+kh,70+km,70+kn,70+lg,70+lk,70+ln,70+lr,70+sj,70+sm,70+so,71+gu,71+ht,71+hw,71+hx,71+id,71+if,71+il,71+ja,71+je,71+jo,71+jx,71+kg,71+kh,71+km,71+kn,71+lg,71+lk,71+ln,71+lr,71+sj,71+sm,71+so,72+gu,72+ht,72+hw,72+hx,72+id,72+if,72+il,72+ja,72+je,72+jo,72+jx,72+kg,72+kh,72+km,72+kn,72+lg,72+lk,72+ln,72+lr,72+sj,72+sm,72+so,73+gu,73+ht,73+hw,73+hx,73+id,73+if,73+il,73+ja,73+je,73+jo,73+jx,73+kg,73+kh,73+km,73+kn,73+lg,73+lk,73+ln,73+lr,73+sj,73+sm,73+so,74+gu,74+ht,74+hw,74+hx,74+id,74+if,74+il,74+ja,74+je,74+jo,74+jx,74+kg,74+kh,74+km,74+kn,74+lg,74+lk,74+ln,74+lr,74+sj,74+sm,74+so,75+gu,75+ht,75+hw,75+hx,75+id,75+if,75+il,75+ja,75+je,75+jo,75+jx,75+kg,75+kh,75+km,75+kn,75+lg,75+lk,75+ln,75+lr,75+sj,75+sm,75+so,76+gu,76+ht,76+hw,76+hx,76+id,76+if,76+il,76+ja,76+je,76+jo,76+jx,76+kg,76+kh,76+km,76+kn,76+lg,76+lk,76+ln,76+lr,76+sj,76+sm,76+so,77+gu,77+ht,77+hw,77+hx,77+id,77+if,77+il,77+ja,77+je,77+jo,77+jx,77+kg,77+kh,77+km,77+kn,77+lg,77+lk,77+ln,77+lr,77+sj,77+sm,77+so,78+gu,78+ht,78+hw,78+hx,78+id,78+if,78+il,78+ja,78+je,78+jo,78+jx,78+kg,78+kh,78+km,78+kn,78+lg,78+lk,78+ln,78+lr,78+sj,78+sm,78+so,79+gu,79+ht,79+hw,79+hx,79+id,79+if,79+il,79+ja,79+je,79+jo,79+jx,79+kg,79+kh,79+km,79+kn,79+lg,79+lk,
79+ln,79+lr,79+sj,79+sm,79+so。
Combinations where the co-power coefficient is greater than 100: 1 + gu, 1 + ht, 1 + hw, 1 + hx, 1 + id, 1 + if, 1 + il, 1 + ja, 1 + je, 1 + jo, 1 + jx, 1 + kg, 1 + kh, 1 + km, 1 + kn, 1 + lg, 1 + lk, 1 + ln, 1 + lr, 1 + sj, 1 + sm, 1 + so, 2 + gu, 2 + ht, 2 + hw, 2 + hx, 2 + id, 2 + if, 2 + il, 2 + ja, 2 + je, 2 + jo, 2 + jx, 2 + kg, 2 + kh, 2 + km, 2 + kn, 2 + lg, 2 + lk, 2 + ln, 2 + lr, 2 + sj, 2 + sm, 2 + so, 3 + gu, 3 + ht, 3 + hw, 3 + hx, 3 + id, 3 + if, 3 + il, 3 + ja, 3 + je, 3 + jo, 3 + jx, 3 + kg, 3 + kh, 3 + km, 3 + kn, 3 + lg, 3 + lk, 3 + ln, 3 + lr, 3 + sj, 3 + sm, 3 + so, 4 + gu, 4 + ht, 4 + hw, 4 + hx, 4 + id, 4 + if, 4 + il, 4 + ja, 4 + je, 4 + jo, 4 + jx, 4 + kg, 4 + kh, 4 + km, 4 + kn, 4 + lg, 4 + lk, 4 + ln, 4 + lr, 4 + sj, 4 + sm, 4 + so, 5 + gu, 5 + ht, 5 + hw, 5 + hx, 5 + id, 5 + if, 5 + il, 5 + ja, 5 + je, 5 + jo, 5 + jx, 5 + kg, 5 + kh, 5 + km, 5 + kn, 5 + lg, 5 + lk, 5 + ln, 5 + lr, 5 + sj, 5 + sm, 5 + so, 6 + gu, 6 + ht, 6 + hw, 6 + hx, 6 + id, 6 + if, 6 + il, 6 + ja, 6 + je, 6 + jo, 6 + jx, 6 + kg, 6 + kh, 6 + km, 6 + kn, 6 + lg, 6 + lk, 6 + ln, 6 + lr, 6 + sj, 6 + sm, 6 + so, 7 + gu, 7 + ht, 7 + hw, 7 + hx, 7 + id, 7 + if, 7 + il, 7 + ja, 7 + je, 7 + jo, 7 + jx, 7 + kg, 7 + kh, 7 + km, 7 + kn, 7 + lg, 7 + lk, 7 + ln, 7 + lr, 7 + sj, 7 + sm, 7 + so, 8 + gu, 8 + ht, 8 + hw, 8 + hx, 8 + id, 8 + if, 8 + il, 8 + ja, 8 + je, 8 + jo, 8 + jx, 8 + kg, 8 + kh, 8 + km, 8 + kn, 8 + lg, 8 + lk, 8 + ln, 8 + lr, 8 + sj, 8 + sm, 8 + so, 9 + gu, 9 + ht, 9 + hw, 9 + hx, 9 + id, 9 + if, 9 + il, 9 + ja, 9 + je, 9 + jo, 9 + jx, 9 + kg, 9 + k h, 9 + km, 9 + kn, 9 + lg, 9 + lk, 9 + ln, 9 + lr, 9 + sj, 9 + sm, 9 + so, 10 + gu, 10 + ht, 10 + hw, 10 + hx, 10 + id, 10 + if, 10 + il, 10 + ja, 10 + je, 10 + jo, 10 + jx, 10 + kg, 10 + kh, 10 + km, 10 + kn, 10 + lg, 10 + lk, 10 + ln, 10 + lr, 10 + sj, 10 + sm, 10 + so, 11 + gu, 11 + ht, 11 + hw, 11 + hx, 11 + id, 11 + if, 11 + il, 11 + ja, 11 + je, 11 + jo, 11 + jx, 11 + kg, 11 + kh, 11 + km, 11 + kn, 11 + lg, 11 + lk, 11 + ln, 11 + lr, 11 + sj, 11 + sm, 11 + so, 12 + gu, 12 + ht, 12 + hw, 12 + hx, 12 + id, 12 + if, 12 + il, 12 + ja, 12 + je, 12 + jo, 12 + jx, 12 + kg, 12 + kh, 12 + km, 12 + kn, 12 + lg, 12 + lk, 12 + ln, 12 + lr, 12 + sj, 12 + sm, 12 + so, 13 + gu, 13 + ht, 13 + hw, 13 + hx, 13 + id, 13 + if, 13 + il, 13 + ja, 13 + je, 13 + jo, 13 + jx, 13 + kg, 13 + kh, 13 + km, 13 + kn, 13 + lg, 13 + lk, 13 + ln, 13 + lr, 13 + sj, 13 + sm, 13 + so, 14 + gu, 14 + ht, 14 + hw, 14 + hx, 14 + id, 14 + if, 14 + il, 14 + ja, 14 + je, 14 + jo, 14 + jx, 14 + kg, 14 + kh, 14 + km, 14 + kn, 14 + lg, 14 + lk, 14 + ln, 14 + lr, 14 + sj, 14 + sm, 14 + so, 15 + gu, 15 + ht, 15 + hw, 15 + hx, 15 + id, 15 + if, 15 + il, 15 + ja, 15 + je, 15 + jo, 15 + jx, 15 + kg, 15 + kh, 15 + km, 15 + kn, 15 + lg, 15 + lk, 15 + ln, 15 + lr, 15 + sj, 15 + sm, 15 + so, 16 + gu, 16 + ht, 16 + hw, 16 + hx, 16 + id, 16 + if, 16 + il, 16 + ja, 16 + je, 16 + jo, 16 + jx, 16 + kg, 16 + kh, 16 + km, 16 + kn, 16 + lg, 16 + lk, 16 + ln, 16 + lr, 16 + sj, 16 + sm, 16 + so, 17 + gu, 17 + ht, 17 + hw, 17 + hx, 17 + id , 17 + if, 17 + il, 17 + ja, 17 + je, 17 + jo, 17 + jx, 17 + kg, 17 + kh, 17 + km, 17 + kn, 17 + lg, 17 + lk, 17 + ln, 17 + lr, 17 + sj, 17 + sm, 17 + so, 18 + gu, 18 + ht, 18 + hw, 18 + hx, 18 + id, 18 + if, 18 + il, 18 + ja , 18 + je, 18 + jo, 18 + jx, 18 + kg, 18 + kh, 18 + km, 18 + kn, 18 + lg, 18 + lk, 18 + ln, 18 + lr, 18 + sj, 18 + sm, 18 + so, 19 + gu, 19 + ht, 19 + hw, 19 + hx, 19 + id, 19 + if, 19 + il, 19 + ja, 19 + je, 19 + jo, 19 + jx , 19 + kg, 19 + kh, 19 + km, 19 + kn, 19 + lg, 19 + lk, 19 + ln, 19 + lr, 19 + sj, 19 + sm, 19 + so, 20 + gu, 20 + ht, 20 + hw, 20 + hx, 20 + id, 20 + if, 20 + il, 20 + ja, 20 + je, 20 + jo, 20 + jx, 20 + kg, 20 + kh, 20 + km , 20 + kn, 20 + lg, 20 + lk, 20 + ln, 20 + lr, 20 + sj, 20 + sm, 20 + so, 21 + gu, 21 + ht, 21 + hw, 21 + hx, 21 + id, 21 + if, 21 + il, 21 + ja, 21 + je, 21 + jo, 21 + jx, 21 + kg, 21 + kh, 21 + km, 21 + kn, 21 + lg, 21 + lk , 21 + ln, 21 + lr, 21 + sj, 21 + sm, 21 + so, 22 + gu, 22 + ht, 22 + hw, 22 + hx, 22 + id, 22 + if, 22 + il, 22 + ja, 22 + je, 22 + jo, 22 + jx, 22 + kg, 22 + kh, 22 + km, 22 + kn, 22 + lg, 22 + lk, 22 + ln, 22 + lr, 22 + sj , 22 + sm, 22 + so, 23 + gu, 23 + ht, 23 + hw, 23 + hx, 23 + id, 23 + if, 23 + il, 23 + ja, 23 + je, 23 + jo, 23 + jx, 23 + kg, 23 + kh, 23 + km, 23 + kn, 23 + lg, 23 + lk, 23 + ln, 23 + lr, 23 + sj, 23 + sm, 23 + so, 24 + gu , 24 + ht, 24 + hw, 24 + hx, 24 + id, 24 + if, 24 + il, 24 + ja, 24 + je, 24 + jo, 24 + jx, 24 + kg, 24 + kh, 24 + km, 24 + kn, 24 + lg, 24 + lk, 24 + ln, 24 + lr, 24 + sj, 24 + sm, 24 + so, 25 + gu, 25 + ht, 25 + hw, 25 + hx, 25 + id, 25 + if, 25 + il, 25 + ja, 25 + je, 25 + jo, 25 + jx, 25 + kg, 25 + kh, 25 + km, 25 + kn, 25 + lg, 25 + lk, 25 + ln, 25 + lr, 25 + sj, 25 + sm, 25 + so, 26 + gu, 26 + ht, 26 + hw, 26 + hx, 26 + id, 26 + if, 26 + il, 26 + ja, 26 + je, 26 + jo, 26 + jx, 26 + kg, 26 + kh, 26 + km, 26 + kn, 26 + lg, 26 + lk, 26 + ln, 26 + lr, 26 + sj, 26 + sm, 26 + so, 27 + gu, 27 + ht, 27 + hw, 27 + hx, 27 + id, 27 + if, 27 + il, 27 + ja, 27 + je, 27 + jo, 27 + jx, 27 + kg, 27 + kh, 27 + km, 27 + kn, 27 + lg, 27 + lk, 27 + ln, 27 + lr, 27 + sj, 27 + sm, 27 + so, 28 + gu, 28 + ht, 28 + hw, 28 + hx, 28 + id, 28 + if, 28 + il, 28 + ja, 28 + je, 28 + jo, 28 + jx, 28 + kg, 28 + kh, 28 + km, 28 + kn, 28 + lg, 28 + lk, 28 + ln, 28 + lr, 28 + sj, 28 + sm, 28 + so, 29 + gu, 29 + ht, 29 + hw, 29 + hx, 29 + id, 29 + if, 29 + il, 29 + ja, 29 + je, 29 + jo, 29 + jx, 29 + kg, 29 + kh, 29 + km, 29 + kn, 29 + lg, 29 + lk, 29 + ln, 29 + lr, 29 + sj, 29 + sm, 29 + so, 30 + gu, 30 + ht, 30 + hw, 30 + hx, 30 + id, 30 + if, 30 + il, 30 + ja, 30 + je, 30 + jo, 30 + jx, 30 + kg, 30 + kh, 30 + km, 30 + kn, 30 + lg, 30 + lk, 30 + ln, 30 + lr, 30 + sj, 30 + sm, 30 + so, 31 + gu, 31 + ht, 31 + hw, 31 + hx, 31 + id, 31 + if, 31 + il, 31 + ja, 31 + je, 31 + jo, 31 + jx, 31 + kg, 31 + kh, 31 + km, 31 + kn, 31 + lg, 31 + lk, 31 + ln, 31 + lr, 31 + sj, 31 + sm, 31 + so, 32 + gu, 32 + ht, 32 + hw, 32 + hx, 32 + id, 32 + if, 32 + il, 32 + ja, 3 2 + je, 32 + jo, 32 + jx, 32 + kg, 32 + kh, 32 + km, 32 + kn, 32 + lg, 32 + lk, 32 + ln, 32 + lr, 32 + sj, 32 + sm, 32 + so, 33 + gu, 33 + ht, 33 + hw, 33 + hx, 33 + id, 33 + if, 33 + il, 33 + ja, 33 + je, 33 + jo, 33 + jx, 33 + kg, 33 + kh, 33 + km, 33 + kn, 33 + lg, 33 + lk, 33 + ln, 33 + lr, 33 + sj, 33 + sm, 33 + so, 34 + gu, 34 + ht, 34 + hw, 34 + hx, 34 + id, 34 + if, 34 + il, 34 + ja, 34 + je, 34 + jo, 34 + jx, 34 + kg, 34 + kh, 34 + km, 34 + kn, 34 + lg, 34 + lk, 34 + ln, 34 + lr, 34 + sj, 34 + sm, 34 + so, 35 + gu, 35 + ht, 35 + hw, 35 + hx, 35 + id, 35 + if, 35 + il, 35 + ja, 35 + je, 35 + jo, 35 + jx, 35 + kg, 35 + kh, 35 + km, 35 + kn, 35 + lg, 35 + lk, 35 + ln, 35 + lr, 35 + sj, 35 + sm, 35 + so, 36 + gu, 36 + ht, 36 + hw, 36 + hx, 36 + id, 36 + if, 36 + il, 36 + ja, 36 + je, 36 + jo, 36 + jx, 36 + kg, 36 + kh, 36 + km, 36 + kn, 36 + lg, 36 + lk, 36 + ln, 36 + lr, 36 + sj, 36 + sm, 36 + so, 37 + gu, 37 + ht, 37 + hw, 37 + hx, 37 + id, 37 + if, 37 + il, 37 + ja, 37 + je, 37 + jo, 37 + jx, 37 + kg, 37 + kh, 37 + km, 37 + kn, 37 + lg, 37 + lk, 37 + ln, 37 + lr, 37 + sj, 37 + sm, 37 + so, 38 + gu, 38 + ht, 38 + hw, 38 + hx, 38 + id, 38 + if, 38 + il, 38 + ja, 38 + je, 38 + jo, 38 + jx, 38 + kg, 38 + kh, 38 + km, 38 + kn, 38 + lg, 38 + lk, 38 + ln, 38 + lr, 38 + sj, 38 + sm, 38 + so, 39 + gu, 39 + ht, 39 + hw, 39 + hx, 39 + id, 39 + if, 39 + il, 39 + ja, 39 + je, 39 + jo, 39 + jx, 39 + kg, 39 + kh, 39 + km, 39 + kn, 39 + lg, 39 + lk, 39 + ln, 39 + lr, 39 + sj, 39 + sm , 39 + so, 40 + gu, 40 + ht, 40 + hw, 40 + hx, 40 + id, 40 + if, 40 + il, 40 + ja, 40 + je, 40 + jo, 40 + jx, 40 + kg, 40 + kh, 40 + km, 40 + kn, 40 + lg, 40 + lk, 40 + ln, 40 + lr, 40 + sj, 40 + sm, 40 + so, 41 + gu, 41 + ht , 41 + hw, 41 + hx, 41 + id, 41 + if, 41 + il, 41 + ja, 41 + je, 41 + jo, 41 + jx, 41 + kg, 41 + kh, 41 + km, 41 + kn, 41 + lg, 41 + lk, 41 + ln, 41 + lr, 41 + sj, 41 + sm, 41 + so, 42 + gu, 42 + ht, 42 + hw, 42 + hx, 42 + id , 42 + if, 42 + il, 42 + ja, 42 + je, 42 + jo, 42 + jx, 42 + kg, 42 + kh, 42 + km, 42 + kn, 42 + lg, 42 + lk, 42 + ln, 42 + lr, 42 + sj, 42 + sm, 42 + so, 43 + gu, 43 + ht, 43 + hw, 43 + hx, 43 + id, 43 + if, 43 + il, 43 + ja , 43 + je, 43 + jo, 43 + jx, 43 + kg, 43 + kh, 43 + km, 43 + kn, 43 + lg, 43 + lk, 43 + ln, 43 + lr, 43 + sj, 43 + sm, 43 + so, 44 + gu, 44 + ht, 44 + hw, 44 + hx, 44 + id, 44 + if, 44 + il, 44 + ja, 44 + je, 44 + jo, 44 + jx , 44 + kg, 44 + kh, 44 + km, 44 + kn, 44 + lg, 44 + lk, 44 + ln, 44 + lr, 44 + sj, 44 + sm, 44 + so, 45 + gu, 45 + ht, 45 + hw, 45 + hx, 45 + id, 45 + if, 45 + il, 45 + ja, 45 + je, 45 + jo, 45 + jx, 45 + kg, 45 + kh, 45 + km , 45 + kn, 45 + lg, 45 + lk, 45 + ln, 45 + lr, 45 + sj, 45 + sm, 45 + so, 46 + gu, 46 + ht, 46 + hw, 46 + hx, 46 + id, 46 + if, 46 + il, 46 + ja, 46 + je, 46 + jo, 46 + jx, 46 + kg, 46 + kh, 46 + km, 46 + kn, 46 + lg, 46 + lk , 46 + ln, 46 + lr, 46 + sj, 46 + sm, 46 + so, 47 + gu, 47 + ht, 47 + hw, 47 + hx, 47 + id, 47 + if, 47 + il, 47 + ja, 47 + je, 47 + jo, 47 + jx, 47 + kg, 47 + kh, 47 + km, 47 + kn, 47 + lg, 47 + lk, 47 + ln, 47 + lr, 47 + sj, 47 + sm, 47 + so, 48 + gu, 48 + ht, 48 + hw, 48 + hx, 48 + id, 48 + if, 48 + il, 48 + ja, 48 + je, 48 + jo, 48 + jx, 48 + kg, 48 + kh, 48 + km, 48 + kn, 48 + lg, 48 + lk, 48 + ln, 48 + lr, 48 + sj, 48 + sm, 48 + so, 49 + gu, 49 + ht, 49 + hw, 49 + hx, 49 + id, 49 + if, 49 + il, 49 + ja, 49 + je, 49 + jo, 49 + jx, 49 + kg, 49 + kh, 49 + km, 49 + kn, 49 + lg, 49 + lk, 49 + ln, 49 + lr, 49 + sj, 49 + sm, 49 + so, 50 + gu, 50 + ht, 50 + hw, 50 + hx, 50 + id, 50 + if, 50 + il, 50 + ja, 50 + je, 50 + jo, 50 + jx, 50 + kg, 50 + kh, 50 + km, 50 + kn, 50 + lg, 50 + lk, 50 + ln, 50 + lr, 50 + sj, 50 + sm, 50 + so, 51 + gu, 51 + ht, 51 + hw, 51 + hx, 51 + id, 51 + if, 51 + il, 51 + ja, 51 + je, 51 + jo, 51 + jx, 51 + kg, 51 + kh, 51 + km, 51 + kn, 51 + lg, 51 + lk, 51 + ln, 51 + lr, 51 + sj, 51 + sm, 51 + so, 52 + gu, 52 + ht, 52 + hw, 52 + hx, 52 + id, 52 + if, 52 + il, 52 + ja, 52 + je, 52 + jo, 52 + jx, 52 + kg, 52 + kh, 52 + km, 52 + kn, 52 + lg, 52 + lk, 52 + ln, 52 + lr, 52 + sj, 52 + sm, 52 + so, 53 + gu, 53 + ht, 53 + hw, 53 + hx, 53 + id, 53 + if, 53 + il, 53 + ja, 53 + je, 53 + jo, 53 + jx, 53 + kg, 53 + kh, 53 + km, 53 + kn, 53 + lg, 53 + lk, 53 + ln, 53 + lr, 53 + sj, 53 + sm, 53 + so, 54 + gu, 54 + ht, 54 + hw, 54 + hx, 54 + id, 54 + if, 54 + il, 54 + ja, 54 + je, 54 + jo, 54 + jx, 54 + kg, 54 + kh, 54 + km, 54 + kn, 54 + lg, 54 + lk, 54 + ln, 54 + lr, 54 + sj, 54 + sm, 54 + so, 55 + gu, 55 + ht, 5 5 + hw, 55 + hx, 55 + id, 55 + if, 55 + il, 55 + ja, 55 + je, 55 + jo, 55 + jx, 55 + kg, 55 + kh, 55 + km, 55 + kn, 55 + lg, 55 + lk, 55 + ln, 55 + lr, 55 + sj, 55 + sm, 55 + so, 56 + gu, 56 + ht, 56 + hw, 56 + hx, 56 + id, 56 + if, 56 + il, 56 + ja, 56 + je, 56 + jo, 56 + jx, 56 + kg, 56 + kh, 56 + km, 56 + kn, 56 + lg, 56 + lk, 56 + ln, 56 + lr, 56 + sj, 56 + sm, 56 + so, 57 + gu, 57 + ht, 57 + hw, 57 + hx, 57 + id, 57 + if, 57 + il, 57 + ja, 57 + je, 57 + jo, 57 + jx, 57 + kg, 57 + kh, 57 + km, 57 + kn, 57 + lg, 57 + lk, 57 + ln, 57 + lr, 57 + sj, 57 + sm, 57 + so, 58 + gu, 58 + ht, 58 + hw, 58 + hx, 58 + id, 58 + if, 58 + il, 58 + ja, 58 + je, 58 + jo, 58 + jx, 58 + kg, 58 + kh, 58 + km, 58 + kn, 58 + lg, 58 + lk, 58 + ln, 58 + lr, 58 + sj, 58 + sm, 58 + so, 59 + gu, 59 + ht, 59 + hw, 59 + hx, 59 + id, 59 + if, 59 + il, 59 + ja, 59 + je, 59 + jo, 59 + jx, 59 + kg, 59 + kh, 59 + km, 59 + kn, 59 + lg, 59 + lk, 59 + ln, 59 + lr, 59 + sj, 59 + sm, 59 + so, 60 + gu, 60 + ht, 60 + hw, 60 + hx, 60 + id, 60 + if, 60 + il, 60 + ja, 60 + je, 60 + jo, 60 + jx, 60 + kg, 60 + kh, 60 + km, 60 + kn, 60 + lg, 60 + lk, 60 + ln, 60 + lr, 60 + sj, 60 + sm, 60 + so, 61 + gu, 61 + ht, 61 + hw, 61 + hx, 61 + id, 61 + if, 61 + il, 61 + ja, 61 + je, 61 + jo, 61 + jx, 61 + kg, 61 + kh, 61 + km, 61 + kn, 61 + lg, 61 + lk, 61 + ln, 61 + lr, 61 + sj, 61 + sm, 61 + so, 62 + gu, 62 + ht, 62 + hw, 62 + hx, 62 + id, 62 + if, 62 + il, 62 + ja, 62 + je, 62 + jo, 62 + jx, 62 + kg, 62 + kh, 62 + km, 62 + kn , 62 + lg, 62 + lk, 62 + ln, 62 + lr, 62 + sj, 62 + sm, 62 + so, 63 + gu, 63 + ht, 63 + hw, 63 + hx, 63 + id, 63 + if, 63 + il, 63 + ja, 63 + je, 63 + jo, 63 + jx, 63 + kg, 63 + kh, 63 + km, 63 + kn, 63 + lg, 63 + lk, 63 + ln , 63 + lr, 63 + sj, 63 + sm, 63 + so, 64 + gu, 64 + ht, 64 + hw, 64 + hx, 64 + id, 64 + if, 64 + il, 64 + ja, 64 + je, 64 + jo, 64 + jx, 64 + kg, 64 + kh, 64 + km, 64 + kn, 64 + lg, 64 + lk, 64 + ln, 64 + lr, 64 + sj, 64 + sm , 64 + so, 65 + gu, 65 + ht, 65 + hw, 65 + hx, 65 + id, 65 + if, 65 + il, 65 + ja, 65 + je, 65 + jo, 65 + jx, 65 + kg, 65 + kh, 65 + km, 65 + kn, 65 + lg, 65 + lk, 65 + ln, 65 + lr, 65 + sj, 65 + sm, 65 + so, 66 + gu, 66 + ht , 66 + hw, 66 + hx, 66 + id, 66 + if, 66 + il, 66 + ja, 66 + je, 66 + jo, 66 + jx, 66 + kg, 66 + kh, 66 + km, 66 + kn, 66 + lg, 66 + lk, 66 + ln, 66 + lr, 66 + sj, 66 + sm, 66 + so, 67 + gu, 67 + ht, 67 + hw, 67 + hx, 67 + id , 67 + if, 67 + il, 67 + ja, 67 + je, 67 + jo, 67 + jx, 67 + kg, 67 + kh, 67 + km, 67 + kn, 67 + lg, 67 + lk, 67 + ln, 67 + lr, 67 + sj, 67 + sm, 67 + so, 68 + gu, 68 + ht, 68 + hw, 68 + hx, 68 + id, 68 + if, 68 + il, 68 + ja , 68 + je, 68 + jo, 68 + jx, 68 + kg, 68 + kh, 68 + km, 68 + kn, 68 + lg, 68 + lk, 68 + ln, 68 + lr, 68 + sj, 68 + sm, 68 + so, 69 + gu, 69 + ht, 69 + hw, 69 + hx, 69 + id, 69 + if, 69 + il, 69 + ja, 69 + je, 69 + jo, 69 + jx , 69 + kg, 69 + kh, 69 + km, 69 + kn, 69 + lg, 69 + lk, 69 + ln, 69 + lr, 69 + sj, 69 + sm, 69 + so, 70 + gu, 70 + ht, 70 + hw, 70 + hx, 70 + id, 70 + if, 70 + il, 70 + ja, 70 + je, 70 + jo, 70 + jx, 70 + kg, 70 + kh, 70 + km, 70 + kn, 70 + lg, 70 + lk, 70 + ln, 70 + lr, 70 + sj, 70 + sm, 70 + so, 71 + gu, 71 + ht, 71 + hw, 71 + hx, 71 + id, 71 + if, 71 + il, 71 + ja, 71 + je, 71 + jo, 71 + jx, 71 + kg, 71 + kh, 71 + km, 71 + kn, 71 + lg, 71 + lk, 71 + ln, 71 + lr, 71 + sj, 71 + sm, 71 + so, 72 + gu, 72 + ht, 72 + hw, 72 + hx, 72 + id, 72 + if, 72 + il, 72 + ja, 72 + je, 72 + jo, 72 + jx, 72 + kg, 72 + kh, 72 + km, 72 + kn, 72 + lg, 72 + lk, 72 + ln, 72 + lr, 72 + sj, 72 + sm, 72 + so, 73 + gu, 73 + ht, 73 + hw, 73 + hx, 73 + id, 73 + if, 73 + il, 73 + ja, 73 + je, 73 + jo, 73 + jx, 73 + kg, 73 + kh, 73 + km, 73 + kn, 73 + lg, 73 + lk, 73 + ln, 73 + lr, 73 + sj, 73 + sm, 73 + so, 74 + gu, 74 + ht, 74 + hw, 74 + hx, 74 + id, 74 + if, 74 + il, 74 + ja, 74 + je, 74 + jo, 74 + jx, 74 + kg, 74 + kh, 74 + km, 74 + kn, 74 + lg, 74 + lk, 74 + ln, 74 + lr, 74 + sj, 74 + sm, 74 + so, 75 + gu, 75 + ht, 75 + hw, 75 + hx, 75 + id, 75 + if, 75 + il, 75 + ja, 75 + je, 75 + jo, 75 + jx, 75 + kg, 75 + kh, 75 + km, 75 + kn, 75 + lg, 75 + lk, 75 + ln, 75 + lr, 75 + sj, 75 + sm, 75 + so, 76 + gu, 76 + ht, 76 + hw, 76 + hx, 76 + id, 76 + if, 76 + il, 76 + ja, 76 + je, 76 + jo, 76 + jx, 76 + kg, 76 + kh, 76 + km, 76 + kn, 76 + lg, 76 + lk, 76 + ln, 76 + lr, 76 + sj, 76 + sm, 76 + so, 77 + gu, 77 + ht, 77 + hw, 77 + hx, 77 + id, 77 + if, 77 + il, 77 + ja, 77 + je, 77 + jo, 77 + jx, 77 + kg, 77 + kh, 77 + km, 77 + kn, 77 + lg, 77 + lk, 77 + ln, 7 7 + lr, 77 + sj, 77 + sm, 77 + so, 78 + gu, 78 + ht, 78 + hw, 78 + hx, 78 + id, 78 + if, 78 + il, 78 + ja, 78 + je, 78 + jo, 78 + jx, 78 + kg, 78 + kh, 78 + km, 78 + kn, 78 + lg, 78 + lk, 78 + ln, 78 + lr, 78 + sj, 78 + sm, 78 + so, 79 + gu, 79 + ht, 79 + hw, 79 + hx, 79 + id, 79 + if, 79 + il, 79 + ja, 79 + je, 79 + jo, 79 + jx, 79 + kg, 79 + kh, 79 + km, 79 + kn, 79 + lg, 79 + lk,
79 + ln, 79 + lr, 79 + sj, 79 + sm, 79 + so.
本発明組成物及び本発明方法は、各種病害虫の防除に有用である。
The composition of the present invention and the method of the present invention are useful for controlling various pests.
Claims (16)
一般式(1):
W1及びW2は、各々独立して酸素原子又は硫黄原子を表し、
Xは、ハロゲン原子、シアノ、ニトロ、アジド、-SCN、-SF5、C1〜C6アルキル、R7によって任意に置換された(C1〜C6)アルキル、C3〜C8シクロアルキル、R7によって任意に置換された(C3〜C8)シクロアルキル、C2〜C6アルケニル、R7によって任意に置換された(C2〜C6)アルケニル、C3〜C8シクロアルケニル、C3〜C8ハロシクロアルケニル、C2〜C6アルキニル、R7によって任意に置換された(C2〜C6)アルキニル、-OH、-OR8、-OS(O)2R8、-SH、-S(O)rR8、-CHO、-C(O)R9、-C(O)OR9、-C(O)SR9、-C(O)NHR10、-C(O)N(R10)R9、-C(S)OR9、-C(S)SR9、-C(S)NHR10、-C(S)N(R10)R9、-CH=NOR11、-C(R9)=NOR11、-S(O)2OR9、-S(O)2NHR10、-S(O)2N(R10)R9、-Si(R13)(R14)R12、(Z1)p1によって置換されていてもよいフェニル、L又はMを表し、mが2、3又は4を表すとき、各々のXは互いに同一であっても又は互いに相異なっていてもよく、
さらに、2つのXが隣接する場合には、隣接する2つのXは-CH2CH2CH2-, -CH2CH2O-, -CH2OCH2-, -OCH2O-, -CH2CH2S-, -CH2SCH2-, -CH2CH2N(R15)-, -CH2N(R15)CH2-, -CH2CH2CH2CH2-, -CH2CH2CH2O-, -CH2CH2OCH2-, -CH2OCH2O-, -OCH2CH2O-, -OCH2CH2S-, -CH2CH=CH-, -OCH=CH-, -SCH=CH-, -N(R15)CH=CH-, -OCH=N-, -SCH=N-, -N(R15)CH=N-, -N(R15)N=CH-, -CH=CHCH=CH-, -OCH2CH=CH-, -N=CHCH=CH-, -N=CHCH=N-又は-N=CHN=CH-を形成することにより、2つのXのそれぞれが結合する炭素原子と共に5員環又は6員環を形成してもよく、このとき、環を形成する各々の炭素原子に結合した水素原子はZ1によって任意に置換されていてもよく、さらに、同時に2個以上のZ1で置換されている場合、各々のZ1は互いに同一であっても又は互いに相異なっていてもよく、
また、Gが酸素原子、硫黄原子及び窒素原子から選ばれる原子を少なくとも1個含み、且つ環内に少なくともひとつの二重結合が存在する5員又は6員の非芳香族複素環を表すとき、Xはさらに-N(R17)R16、-N=CHOR12又は-N=C(R9)OR12を表すこともでき、
Yは、ハロゲン原子、シアノ、ニトロ、アジド、-SCN、-SF5、C1〜C6アルキル、R7によって任意に置換された(C1〜C6)アルキル、C3〜C8シクロアルキル、R7によって任意に置換された(C3〜C8)シクロアルキル、-OH、-OR8、-OS(O)2R8、-SH、-S(O)rR8、-NH2、C1〜C6アルキルアミノ、ジ(C1〜C6アルキル)アミノ、-Si(R13)(R14)R12、(Z1)p1によって置換されていてもよいフェニル、L又はMを表し、nが2、3又は4を表すとき、各々のYは互いに同一であっても又は互いに相異なっていてもよく、
さらに、2つのYが隣接する場合には、隣接する2つのYは-CH2CH2CH2-, -CH2CH2O-, -CH2OCH2-, -OCH2O-, -CH2CH2S-, -CH2SCH2-, -SCH2S-, -CH2CH2CH2CH2-, -CH2CH2CH2O-, -CH2CH2OCH2-, -CH2OCH2O-, -OCH2CH2O-, -OCH2CH2S-, -SCH2CH2S-, -OCH=N-又は-SCH=N-を形成することにより、2つのYのそれぞれが結合する炭素原子と共に5員環又は6員環を形成してもよく、このとき、環を形成する各々の炭素原子に結合した水素原子はZ1によって任意に置換されていてもよく、さらに、同時に2個以上のZ1で置換されている場合、各々のZ1は互いに同一であっても又は互いに相異なっていてもよく、
R1、R2及びR3は、各々独立して水素原子、シアノ、C1〜C12アルキル、R18によって任意に置換された(C1〜C12)アルキル、C3〜C12シクロアルキル、R18によって任意に置換された(C3〜C12)シクロアルキル、C3〜C12アルケニル、R18によって任意に置換された(C3〜C12)アルケニル、C3〜C12シクロアルケニル、C3〜C12ハロシクロアルケニル、C3〜C12アルキニル、R18によって任意に置換された(C3〜C12)アルキニル、-OH、C1〜C8アルコキシ、C3〜C8アルケニルオキシ、C3〜C8ハロアルケニルオキシ、(Z1)p1によって置換されていてもよいフェノキシ、(Z1)p1によって置換されていてもよいフェニル(C1〜C4)アルコキシ、C1〜C6アルキルチオ、C1〜C6ハロアルキルチオ、(Z1)p1によって置換されていてもよいフェニルチオ、-S(O)2R9、-SN(R20)R19、-S(O)2N(R10)R9、-N(R22)R21、-C(O)R9、-C(O)OR9、-C(O)SR9、-C(O)N(R10)R9、-C(S)OR9、-C(S)SR9、-C(S)N(R10)R9、(Z1)p1によって置換されていてもよいフェニル、L又はMを表すか、或いは、R2とR3とが一緒になってC2〜C6アルキレン鎖を形成することにより、結合する窒素原子と共に3〜7員環を形成してもよいことを表し、このときこのアルキレン鎖は酸素原子、硫黄原子又は窒素原子を1個含んでもよく、且つハロゲン原子、C1〜C6アルキル基、C1〜C6ハロアルキル基、C1〜C6アルコキシ基、C1〜C6アルキルカルボニル基又はC1〜C6アルコキシカルボニル基によって任意に置換されていてもよく、
R4は、水素原子、ハロゲン原子、シアノ、C1〜C6アルキル、C1〜C6ハロアルキル、R23によって任意に置換された(C1〜C6)アルキル、R23によって任意に置換された(C1〜C6)ハロアルキル、C3〜C8シクロアルキル、C3〜C8ハロシクロアルキル、R23によって任意に置換された(C3〜C8)シクロアルキル、R23によって任意に置換された(C3〜C8)ハロシクロアルキル、C3〜C6アルケニル、C3〜C6ハロアルケニル、C3〜C6アルキニル、C3〜C6ハロアルキニル、-OR8、-S(O)rR8、-N(R10)R9、-CHO、-C(O)R9、-C(O)OR9、-C(O)SR9、-C(O)NHR10、-C(O)N(R10)R9、-C(S)OR9、-C(S)SR9、-C(S)NHR10、-C(S)N(R10)R9、-CH=NOR11、-C(R9)=NOR11、-Si(R13)(R14)R12、-P(O)(OR24)2、(Z2)p1によって置換されていてもよいフェニル、1-ナフチル、2-ナフチル、L又はMを表し、
R5は、
(a). Gが酸素原子、硫黄原子及び窒素原子から選ばれる原子を少なくとも1個含み、且つ環内に少なくともひとつの二重結合が存在する5員又は6員の非芳香族複素環又は酸素原子、硫黄原子及び窒素原子から選ばれる原子を2個含む5員又は6員の飽和複素環を表すとき、水素原子、ハロゲン原子、シアノ、C1〜C6アルキル、C1〜C6ハロアルキル、R23によって任意に置換された(C1〜C6)アルキル、R23によって任意に置換された(C1〜C6)ハロアルキル、C3〜C8シクロアルキル、C3〜C8ハロシクロアルキル、R23によって任意に置換された(C3〜C8)シクロアルキル、R23によって任意に置換された(C3〜C8)ハロシクロアルキル、C3〜C6アルケニル、C3〜C6ハロアルケニル、C3〜C6アルキニル、C3〜C6ハロアルキニル、-OR8、-S(O)rR8、-N(R10)R9、-CHO、-C(O)R9、-C(O)OR9、-C(O)SR9、-C(O)NHR10、-C(O)N(R10)R9、-C(S)OR9、-C(S)SR9、-C(S)NHR10、-C(S)N(R10)R9、-CH=NOR11、-C(R9)=NOR11、(Z2)p1によって置換されていてもよいフェニル、1-ナフチル、2-ナフチル、L又はMを表し、
(b). Gが3員から6員のシクロアルキル環を表し、且つR4が水素原子、ハロゲン原子、C1〜C6アルキル又はC1〜C6ハロアルキルを表すとき、シアノ、R23によって任意に置換された(C1〜C6)アルキル、R23によって任意に置換された(C1〜C6)ハロアルキル、C3〜C8シクロアルキル、C3〜C8ハロシクロアルキル、R23によって任意に置換された(C3〜C8)シクロアルキル、R23によって任意に置換された(C3〜C8)ハロシクロアルキル、C3〜C6アルケニル、C3〜C6ハロアルケニル、C3〜C6アルキニル、C3〜C6ハロアルキニル、-OR8、-S(O)rR8、-N(R10)R9、-CHO、-C(O)R9、-C(O)OR9、-C(O)SR9、-C(O)NHR10、-C(O)N(R10)R9、-C(S)OR9、-C(S)SR9、-C(S)NHR10、-C(S)N(R10)R9、-CH=NOR11、-C(R9)=NOR11、-Si(R13)(R14)R12、(Z2)p1によって置換されていてもよいフェニル、1-ナフチル、2-ナフチル、L又はMを表し、
(c). Gが3員から6員のシクロアルキル環を表し、且つR4がシアノ、R23によって任意に置換された(C1〜C6)アルキル、R23によって任意に置換された(C1〜C6)ハロアルキル、C3〜C8シクロアルキル、C3〜C8ハロシクロアルキル、R23によって任意に置換された(C3〜C8)シクロアルキル、R23によって任意に置換された(C3〜C8)ハロシクロアルキル、C3〜C6アルケニル、C3〜C6ハロアルケニル、C3〜C6アルキニル、C3〜C6ハロアルキニル、-OR8、-S(O)rR8、-N(R10)R9、-CHO、-C(O)R9、-C(O)OR9、-C(O)SR9、-C(O)NHR10、-C(O)N(R10)R9、-C(S)OR9、-C(S)SR9、-C(S)NHR10、-C(S)N(R10)R9、-CH=NOR11、-C(R9)=NOR11、-Si(R13)(R14)R12、-P(O)(OR24)2、(Z2)p1によって置換されていてもよいフェニル、1-ナフチル、2-ナフチル、L又はMを表すとき、水素原子、ハロゲン原子、シアノ、C1〜C6アルキル、C1〜C6ハロアルキル、R23によって任意に置換された(C1〜C6)アルキル、R23によって任意に置換された(C1〜C6)ハロアルキル、C3〜C8シクロアルキル、C3〜C8ハロシクロアルキル、R23によって任意に置換された(C3〜C8)シクロアルキル、R23によって任意に置換された(C3〜C8)ハロシクロアルキル、C3〜C6アルケニル、C3〜C6ハロアルケニル、C3〜C6アルキニル、C3〜C6ハロアルキニル、-OR8、-S(O)rR8、-N(R10)R9、-CHO、-C(O)R9、-C(O)OR9、-C(O)SR9、-C(O)NHR10、-C(O)N(R10)R9、-C(S)OR9、-C(S)SR9、-C(S)NHR10、-C(S)N(R10)R9、-CH=NOR11、-C(R9)=NOR11、-Si(R13)(R14)R12、(Z2)p1によって置換されていてもよいフェニル、1-ナフチル、2-ナフチル、L又はMを表し、
R6は、水素原子、ハロゲン原子、シアノ、C1〜C6アルキル、C1〜C6ハロアルキル、R23によって任意に置換された(C1〜C6)アルキル、R23によって任意に置換された(C1〜C6)ハロアルキル、C3〜C8シクロアルキル、C3〜C8ハロシクロアルキル、R23によって任意に置換された(C3〜C8)シクロアルキル、R23によって任意に置換された(C3〜C8)ハロシクロアルキル、C1〜C6アルコキシ、C1〜C6ハロアルコキシ、C1〜C6アルキルチオ、C1〜C6ハロアルキルチオ、-S(O)2R9、-C(O)R9、-C(O)OR9、-C(O)SR9、-C(S)OR9、-C(S)SR9、-C(O)N(R10)R9、-C(S)N(R10)R9、-P(O)(OR24)2、-P(S)(OR24)2、(Z2)p1によって置換されていてもよいフェニル、1-ナフチル、2-ナフチル、L又はMを表し、lが2以上の整数を表すとき、各々のR6は互いに同一であっても又は互いに相異なっていてもよく、
さらに、R6がR4と隣接する場合、隣接するR4とR6とが一緒になってC3〜C5アルキレン鎖を形成することにより、結合する原子と共に5〜7員環を形成してもよいことを表し、このときこのアルキレン鎖は酸素原子又は硫黄原子を1個含んでもよく、且つC1〜C6アルキル基によって任意に置換されていてもよく、
Lは、式L-1から式L-58までの何れかで表される芳香族複素環を表し、
Z2は、ハロゲン原子、シアノ、ニトロ、アミノ、アジド、-SCN、-SF5、C1〜C6アルキル、R7によって任意に置換された(C1〜C6)アルキル、C3〜C8シクロアルキル、R7によって任意に置換された(C3〜C8)シクロアルキル、C2〜C6アルケニル、R7によって任意に置換された(C2〜C6)アルケニル、C3〜C8シクロアルケニル、C3〜C8ハロシクロアルケニル、C2〜C6アルキニル、R7によって任意に置換された(C2〜C6)アルキニル、-OH、-OR8、-OS(O)2R8、-SH、-S(O)rR8、-N(R10)R9、-N(R10)CHO、-N(R10)C(O)R9、-N(R10)C(O)OR9、-N(R10)C(O)SR9、-N(R10)C(S)OR9、-N(R10)C(S)SR9、-N(R10)S(O)2R9、-CHO、-C(O)R9、-C(O)OR9、-C(O)NHR10、-C(O)N(R10)R9、-C(S)NHR10、-C(S)N(R10)R9、-S(O)2OR9、-S(O)2NHR10、-S(O)2N(R10)R9、-Si(R13)(R14)R12、(Z1)p1によって置換されていてもよいフェニル、L又はMを表し、p1が2以上の整数を表すとき、各々のZ2は互いに同一であっても又は互いに相異なっていてもよく、
さらに、2つのZ2が隣接する場合には、隣接する2つのZ2は-CH2CH2CH2-, -CH2CH2O-, -CH2OCH2-, -OCH2O-, -CH2CH2S-, -CH2SCH2-, -CH2CH2CH2CH2-, -CH2CH2CH2O-, -CH2CH2OCH2-, -CH2OCH2O-, -OCH2CH2O-又は-OCH2CH2S-を形成することにより、2つのZ2のそれぞれが結合する炭素原子と共に5員環又は6員環を形成してもよく、このとき、環を形成する各々の炭素原子に結合した水素原子はハロゲン原子又はC1〜C6アルキル基によって任意に置換されていてもよく、
R7は、ハロゲン原子、シアノ、C3〜C8シクロアルキル、C3〜C8ハロシクロアルキル、-OH、-OR8、-SH、-S(O)rR8、-N(R10)R9、-N(R10)CHO、-N(R10)C(O)R9、-N(R10)C(O)OR9、-N(R10)C(O)SR9、-N(R10)C(S)OR9、-N(R10)C(S)SR9、-N(R10)S(O)2R9、-C(O)OR9、-C(O)N(R10)R9、-Si(R13)(R14)R12、(Z1)p1によって置換されていてもよいフェニル、L又はMを表し、
R8は、C1〜C6アルキル、R27によって任意に置換された(C1〜C6)アルキル、C3〜C8シクロアルキル、R27によって任意に置換された(C3〜C8)シクロアルキル、C2〜C6アルケニル、R27によって任意に置換された(C2〜C6)アルケニル、C3〜C8シクロアルケニル、C3〜C8ハロシクロアルケニル、C3〜C6アルキニル、R27によって任意に置換された(C3〜C6)アルキニル、(Z1)p1によって置換されていてもよいフェニル、L又はMを表し、
R9は、C1〜C6アルキル、C1〜C6ハロアルキル、C3〜C6シクロアルキル(C1〜C4)アルキル、C1〜C6アルコキシ(C1〜C4)アルキル、C1〜C6アルキルチオ(C1〜C4)アルキル、シアノ(C1〜C6)アルキル、(Z1)p1によって置換されていてもよいフェニル(C1〜C4)アルキル、L-(C1〜C4)アルキル、M-(C1〜C4)アルキル、C3〜C8シクロアルキル、C3〜C8ハロシクロアルキル、C3〜C6アルケニル、C3〜C6ハロアルケニル、C3〜C6アルキニル又は(Z1)p1によって置換されていてもよいフェニルを表し、
R10は、水素原子又はC1〜C6アルキルを表すか、或いは、R9とR10とが一緒になってC2〜C6アルキレン鎖を形成することにより、結合する原子と共に3〜7員環を形成してもよいことを表し、このときこのアルキレン鎖は酸素原子、硫黄原子又は窒素原子を1個含んでもよく、且つハロゲン原子、C1〜C6アルキル基、C1〜C6アルコキシ基、ホルミル基、C1〜C6アルキルカルボニル基又はC1〜C6アルコキシカルボニル基によって任意に置換されていてもよく、
R11は、水素原子、C1〜C6アルキル、C1〜C6ハロアルキル、(Z1)p1によって置換されていてもよいフェニル(C1〜C4)アルキル、C3〜C6アルケニル、C3〜C6ハロアルケニル、C3〜C6アルキニル又はC3〜C6ハロアルキニルを表すか、或いは、R9とR11とが一緒になってC2〜C4アルキレン鎖を形成することにより、結合する原子と共に5〜7員環を形成してもよいことを表し、このときこのアルキレン鎖は酸素原子、硫黄原子又は窒素原子を1個含んでもよく、且つハロゲン原子又はC1〜C6アルキル基によって任意に置換されていてもよく、
R12は、C1〜C6アルキル、C1〜C6ハロアルキル、C3〜C6アルケニル又は(Z1)p1によって置換されていてもよいフェニルを表し、
R13及びR14は、各々独立してC1〜C6アルキル又はC1〜C6ハロアルキルを表し、
R15は、水素原子、C1〜C6アルキル、C1〜C6ハロアルキル、C1〜C6アルコキシカルボニル(C1〜C4)アルキル、C1〜C6ハロアルコキシカルボニル(C1〜C4)アルキル、(Z1)p1によって置換されていてもよいフェニル(C1〜C4)アルキル、C3〜C6アルケニル、C3〜C6ハロアルケニル、C3〜C6アルキニル、C3〜C6ハロアルキニル、C1〜C6アルコキシ、C1〜C6アルコキシカルボニル、C1〜C6ハロアルコキシカルボニル又は(Z1)p1によって置換されていてもよいフェニルを表し、
R16は、水素原子、C1〜C6アルキル、C1〜C6ハロアルキル、C3〜C6シクロアルキル(C1〜C4)アルキル、C1〜C4アルコキシ(C1〜C4)アルキル、C1〜C4アルキルチオ(C1〜C4)アルキル、(Z1)p1によって置換されていてもよいフェニルチオ(C1〜C4)アルキル、シアノ(C1〜C6)アルキル、C1〜C6アルコキシカルボニル(C1〜C4)アルキル、C1〜C6アルキルアミノカルボニル(C1〜C4)アルキル、ジ(C1〜C6アルキル)アミノカルボニル(C1〜C4)アルキル、(Z1)p1によって置換されていてもよいフェニル(C1〜C4)アルキル、L-(C1〜C4)アルキル、M-(C1〜C4)アルキル、C3〜C6シクロアルキル、C3〜C6アルケニル、C3〜C6ハロアルケニル、C3〜C6アルキニル、C3〜C6ハロアルキニル、-OH、C1〜C6アルキルカルボニルオキシ、C1〜C6アルキルチオ、C1〜C6ハロアルキルチオ、(Z1)p1によって置換されていてもよいフェニルチオ、C1〜C6アルキルスルホニル、C1〜C6ハロアルキルスルホニル、(Z1)p1によって置換されていてもよいフェニルスルホニル、-SN(R20)R19、C1〜C6アルキルアミノスルホニル、ジ(C1〜C6アルキル)アミノスルホニル、-CHO、-C(O)R9、-C(O)OR9、-C(O)SR9、-C(O)NHR10、-C(O)N(R10)R9、-C(S)OR9、-C(S)SR9、-C(S)NHR10、-C(S)N(R10)R9、-C(O)C(O)R9、-C(O)C(O)OR9、-P(O)(OR24)2又は-P(S)(OR24)2を表し、
R17は、水素原子、C1〜C6アルキル、C1〜C6ハロアルキル、C3〜C8シクロアルキル(C1〜C6)アルキル、C3〜C8シクロアルキル、C3〜C6アルケニル、C3〜C6ハロアルケニル、C3〜C6アルキニル、C3〜C6ハロアルキニル、-CHO、C1〜C6アルキルカルボニル、C1〜C6ハロアルキルカルボニル又はC1〜C6アルコキシカルボニルを表すか、或いは、R16とR17とが一緒になってC2〜C6アルキレン鎖を形成することにより、結合する窒素原子と共に3〜7員環を形成してもよいことを表し、このときこのアルキレン鎖は酸素原子、硫黄原子又は窒素原子を1個含んでもよく、且つハロゲン原子、C1〜C6アルキル基又はC1〜C6ハロアルキル基によって任意に置換されていてもよく、さらに或いは、R17がR2と一緒になってC1〜C2アルキレン鎖を形成することにより、結合する原子と共にベンゼン環と縮合する6員又は7員のヘテロ環を形成してもよいことを表し、このときこのアルキレン鎖は酸素原子又はC1〜C6アルキル基によって任意に置換されていてもよく、
R18は、ハロゲン原子、シアノ、ニトロ、C3〜C8シクロアルキル、C3〜C8ハロシクロアルキル、-OR28、-N(R29)R28、-SH、-S(O)rR30、-CHO、-C(O)R31、-C(O)OH、-C(O)OR31、-C(O)SR31、-C(O)NHR32、-C(O)N(R32)R31、-C(O)C(O)OR31、-C(R34)=NOH、-C(R34)=NOR33、-Si(R13)(R14)R12、-P(O)(OR24)2、-P(S)(OR24)2、-P(フェニル)2、-P(O)(フェニル)2、(Z1)p1によって置換されていてもよいフェニル、L又はMを表し、
R19は、C1〜C12アルキル、C1〜C12ハロアルキル、C1〜C12アルコキシ(C1〜C12)アルキル、シアノ(C1〜C12)アルキル、C1〜C12アルコキシカルボニル(C1〜C12)アルキル、(Z1)p1によって置換されていてもよいフェニル(C1〜C4)アルキル、C3〜C12アルケニル、C3〜C12ハロアルケニル、C3〜C12アルキニル、C3〜C12ハロアルキニル、C1〜C12アルキルカルボニル、C1〜C12アルコキシカルボニル又は(Z1)p1によって置換されていてもよいフェニルを表し、
R20は、C1〜C12アルキル、C1〜C12ハロアルキル、C1〜C12アルコキシ(C1〜C12)アルキル、シアノ(C1〜C12)アルキル、C1〜C12アルコキシカルボニル(C1〜C12)アルキル、(Z1)p1によって置換されていてもよいフェニル(C1〜C4)アルキル、C3〜C12アルケニル、C3〜C12ハロアルケニル、C3〜C12アルキニル、C3〜C12ハロアルキニル又は(Z1)p1によって置換されていてもよいフェニルを表すか、或いは、R19とR20とが一緒になってC4〜C7アルキレン鎖を形成することにより、結合する窒素原子と共に5〜8員環を形成してもよいことを表し、このときこのアルキレン鎖は酸素原子又は硫黄原子を1個含んでもよく、且つC1〜C4アルキル基又はC1〜C4アルコキシ基によって任意に置換されていてもよく、
R21は、水素原子、C1〜C6アルキル、C1〜C6ハロアルキル、(Z1)p1によって置換されていてもよいフェニル(C1〜C4)アルキル、C3〜C6アルケニル、C3〜C6ハロアルケニル、C3〜C6アルキニル、-CHO、C1〜C6アルキルカルボニル、C1〜C6ハロアルキルカルボニル、C1〜C6アルコキシカルボニル、C1〜C6ハロアルコキシカルボニル、(Z1)p1によって置換されていてもよいフェニル(C1〜C4)アルコキシカルボニル、(Z1)p1によって置換されていてもよいフェノキシカルボニル、(Z1)p1によって置換されていてもよいフェニルカルボニル又は(Z1)p1によって置換されていてもよいフェニルを表し、
R22は、水素原子、C1〜C6アルキル、-CHO、C1〜C6アルキルカルボニル、C1〜C6ハロアルキルカルボニル又はC1〜C6アルコキシカルボニルを表し、
R23は、シアノ、C3〜C8シクロアルキル、C3〜C8ハロシクロアルキル、-OH、-OR8、-SH、-S(O)rR8、-N(R10)R9、-N(R10)CHO、-N(R10)C(O)R9、-N(R10)C(O)OR9、-N(R10)C(O)SR9、-N(R10)C(S)OR9、-N(R10)C(S)SR9、-N(R10)S(O)2R9、-C(O)OR9、-C(O)N(R10)R9、-Si(R13)(R14)R12、(Z1)p1によって置換されていてもよいフェニル、L又はMを表し、
R24は、C1〜C6アルキル又はC1〜C6ハロアルキルを表し、
R25は、ハロゲン原子、シアノ、C1〜C6アルキル、C1〜C6ハロアルキル、ヒドロキシ(C1〜C6)アルキル、C1〜C4アルコキシ(C1〜C4)アルキル、C1〜C4アルコキシカルボニル(C1〜C4)アルキル、C1〜C6アルコキシ、C1〜C6アルコキシカルボニル又は(Z1)p1によって置換されていてもよいフェニルを表し、q1, q2, q3又はq4が2以上の整数を表すとき、各々のR25は互いに同一であっても、または互いに相異なっていてもよく、
R26は、水素原子、C1〜C6アルキル、C1〜C6ハロアルキル、-CHO、C1〜C6アルキルカルボニル、C1〜C6ハロアルキルカルボニル、(Z1)p1によって置換されていてもよいフェニル(C1〜C4)アルキルカルボニル、C1〜C6アルコキシカルボニル、C1〜C6ハロアルコキシカルボニル、(Z1)p1によって置換されていてもよいフェニル(C1〜C4)アルコキシカルボニル、C1〜C6アルキルアミノカルボニル、ジ(C1〜C6アルキル)アミノカルボニル、C1〜C6アルキルアミノチオカルボニル、ジ(C1〜C6アルキル)アミノチオカルボニル、(Z1)p1によって置換されていてもよいフェニルカルボニル、C1〜C6アルキルスルホニル、C1〜C6ハロアルキルスルホニル、(Z1)p1によって置換されていてもよいフェニルスルホニル、-P(O)(OR24)2又は-P(S)(OR24)2を表し、
R27は、ハロゲン原子、シアノ、C3〜C8シクロアルキル、C3〜C8ハロシクロアルキル、C1〜C6アルコキシ、C1〜C6ハロアルコキシ、C1〜C6アルキルチオ、C1〜C6ハロアルキルチオ、C1〜C6アルキルスルホニル、C1〜C6ハロアルキルスルホニル、C1〜C6アルキルアミノ、ジ(C1〜C6アルキル)アミノ、-CHO、C1〜C6アルキルカルボニル、C1〜C6ハロアルキルカルボニル、C1〜C6アルコキシカルボニル、C1〜C6ハロアルコキシカルボニル、-CH=NOR11、-C(R9)=NOR11、(Z1)p1によって置換されていてもよいフェニル、L又はMを表し、
R28は、水素原子、C1〜C8アルキル、R35によって任意に置換された(C1〜C8)アルキル、C3〜C8シクロアルキル、R35によって任意に置換された(C3〜C8)シクロアルキル、C3〜C8アルケニル、R35によって任意に置換された(C3〜C8)アルケニル、C3〜C8アルキニル、R35によって任意に置換された(C3〜C8)アルキニル、-CHO、-C(O)R31、-C(O)OR31、-C(O)SR31、-C(O)NHR32、-C(O)N(R32)R31、-C(O)C(O)R31、-C(O)C(O)OR31、-C(S)R31、-C(S)OR31、-C(S)SR31、-C(S)NHR32、-C(S)N(R32)R31、-S(O)2R31、-S(O)2N(R32)R31、-Si(R13)(R14)R12、-P(O)(OR24)2、-P(S)(OR24)2、(Z1)p1によって置換されていてもよいフェニル、L又はMを表し、
R29は、水素原子、C1〜C6アルキル、C1〜C6ハロアルキル、C3〜C6シクロアルキル又はC1〜C6アルコキシを表すか、或いは、R28とR29とが一緒になってC2〜C5アルキレン鎖を形成することにより、結合する窒素原子と共に3〜6員環を形成してもよいことを表し、このときこのアルキレン鎖は酸素原子又は硫黄原子を1個含んでもよく、且つハロゲン原子、C1〜C6アルキル基、C1〜C6アルコキシ基又は(Z1)p1によって置換されていてもよいフェニル基によって置換されていてもよく、
R30は、C1〜C8アルキル、R35によって任意に置換された(C1〜C8)アルキル、C3〜C8シクロアルキル、R35によって任意に置換された(C3〜C8)シクロアルキル、C3〜C8アルケニル、R35によって任意に置換された(C3〜C8)アルケニル、C3〜C8アルキニル、R35によって任意に置換された(C3〜C8)アルキニル、-SH、C1〜C6アルキルチオ、C1〜C6ハロアルキルチオ、(Z1)p1によって置換されていてもよいフェニルチオ、-CHO、-C(O)R31、-C(O)OR31、-C(O)SR31、-C(O)NHR32、-C(O)N(R32)R31、-C(O)C(O)R31、-C(O)C(O)OR31、-C(S)R31、-C(S)OR31、-C(S)SR31、-C(S)NHR32、-C(S)N(R32)R31、-P(O)(OR24)2、-P(S)(OR24)2、(Z1)p1によって置換されていてもよいフェニル、L-18、L-21、L-25、L-30〜L-35、L-45、L-48、L-49又はMを表し、
R31は、C1〜C6アルキル、C1〜C6ハロアルキル、C3〜C8シクロアルキル(C1〜C4)アルキル、C1〜C6アルコキシ(C1〜C4)アルキル、C1〜C6ハロアルコキシ(C1〜C4)アルキル、C1〜C6アルキルチオ(C1〜C4)アルキル、C1〜C6ハロアルキルチオ(C1〜C4)アルキル、C1〜C6アルキルスルホニル(C1〜C4)アルキル、C1〜C6ハロアルキルスルホニル(C1〜C4)アルキル、シアノ(C1〜C6)アルキル、C1〜C6アルキルカルボニル(C1〜C4)アルキル、C1〜C6ハロアルキルカルボニル(C1〜C4)アルキル、C1〜C6アルコキシカルボニル(C1〜C4)アルキル、ジ(C1〜C6アルキル)アミノカルボニル(C1〜C4)アルキル、トリ(C1〜C4アルキル)シリル(C1〜C4)アルキル、(Z1)p1によって置換されていてもよいフェニル(C1〜C4)アルキル、L-(C1〜C4)アルキル、M-(C1〜C4)アルキル、C3〜C8シクロアルキル、C3〜C8ハロシクロアルキル、C2〜C6アルケニル(C3〜C8)シクロアルキル、C2〜C6ハロアルケニル(C3〜C8)シクロアルキル、C2〜C6アルケニル、C2〜C6ハロアルケニル、C2〜C6アルキニル、C2〜C6ハロアルキニル、(Z1)p1によって置換されていてもよいフェニル、L又はMを表し、
R32は、水素原子、C1〜C6アルキル、C1〜C6ハロアルキル又は(Z1)p1によって置換されていてもよいフェニルを表すか、或いは、R31とR32とが一緒になってC2〜C5アルキレン鎖を形成することにより、結合する窒素原子と共に3〜6員環を形成してもよいことを表し、このときこのアルキレン鎖は酸素原子、硫黄原子又は窒素原子を1個含んでもよく、且つハロゲン原子、C1〜C6アルキル基、C1〜C6アルコキシ基、ホルミル基、C1〜C6アルキルカルボニル基、C1〜C6アルコキシカルボニル基又は(Z1)p1によって置換されていてもよいフェニル基によって任意に置換されていてもよく、
R33は、水素原子、C1〜C8アルキル、R35によって任意に置換された(C1〜C8)アルキル、C3〜C8シクロアルキル、C3〜C8アルケニル、R35によって任意に置換された(C3〜C8)アルケニル、C3〜C8アルキニル又はR35によって任意に置換された(C3〜C8)アルキニルを表し、
R34は、水素原子、C1〜C6アルキル、C1〜C6ハロアルキル、C3〜C8シクロアルキル(C1〜C4)アルキル、C1〜C6アルコキシ(C1〜C4)アルキル、C1〜C6ハロアルコキシ(C1〜C4)アルキル、C1〜C6アルキルチオ(C1〜C4)アルキル、C1〜C6ハロアルキルチオ(C1〜C4)アルキル、C1〜C6アルキルスルホニル(C1〜C4)アルキル、C1〜C6ハロアルキルスルホニル(C1〜C4)アルキル、(Z1)p1によって置換されていてもよいフェニル(C1〜C4)アルキル又は(Z1)p1によって置換されていてもよいフェニルを表し、
R35は、ハロゲン原子、シアノ、ニトロ、C3〜C8シクロアルキル、C3〜C8ハロシクロアルキル、-OH、-OR36、-SH、-S(O)rR36、-NHR37、-N(R37)R36、-CHO、-C(O)R31、-C(O)OR31、-C(O)SR31、-C(O)NHR32、-C(O)N(R32)R31、-C(O)C(O)OR31、-CH=NOR11、-C(R9)=NOR11、-Si(R13)(R14)R12、-P(O)(OR24)2、-P(S)(OR24)2、-P(フェニル)2、-P(O)(フェニル)2、(Z1)p1によって置換されていてもよいフェニル、L又はMを表し、
R36は、C1〜C6アルキル、C1〜C6ハロアルキル、C1〜C6アルコキシ(C1〜C4)アルキル、C1〜C6アルキルチオ(C1〜C4)アルキル、(Z1)p1によって置換されていてもよいフェニル(C1〜C4)アルキル、C3〜C8シクロアルキル、C3〜C8ハロシクロアルキル、C3〜C6アルケニル、C3〜C6ハロアルケニル、C3〜C8シクロアルケニル、C3〜C8ハロシクロアルケニル、C3〜C6アルキニル、C3〜C6ハロアルキニル、-CHO、C1〜C6アルキルカルボニル、C1〜C6ハロアルキルカルボニル、C1〜C6アルコキシカルボニル、C1〜C6ハロアルコキシカルボニル、C1〜C6アルキルアミノカルボニル、ジ(C1〜C6アルキル)アミノカルボニル、(Z1)p1によって置換されていてもよいフェニルカルボニル、C1〜C6アルキルアミノチオカルボニル、ジ(C1〜C6アルキル)アミノチオカルボニル、(Z1)p1によって置換されていてもよいフェニル、L又はMを表し、
R37は、水素原子、C1〜C6アルキル、C1〜C6ハロアルキル、C3〜C8シクロアルキル、C3〜C6アルケニル、C3〜C6アルキニル、C1〜C6アルキルカルボニル、C1〜C6ハロアルキルカルボニル、C1〜C6アルコキシカルボニル、C1〜C6ハロアルコキシカルボニル、(Z1)p1によって置換されていてもよいフェノキシカルボニル、(Z1)p1によって置換されていてもよいフェニルカルボニル、C1〜C6アルキルスルホニル、C1〜C6ハロアルキルスルホニル、(Z1)p1によって置換されていてもよいフェニル、L又はMを表すか、或いは、R36とR37とが一緒になってC2〜C5アルキレン鎖を形成することにより、結合する窒素原子と共に3〜6員環を形成してもよいことを表し、このときこのアルキレン鎖は酸素原子又は硫黄原子を1個含んでもよく、且つハロゲン原子又はメチル基によって置換されていてもよく、
lは、0〜9の整数を表し、
mは、0〜4の整数を表し、
nは、0〜4の整数を表し、
p1は、1〜5の整数を表し、
p2は、0〜4の整数を表し、
p3は、0〜3の整数を表し、
p4は、0〜2の整数を表し、
p5は、0又は1の整数を表し、
q1は、0〜3の整数を表し、
q2は、0〜5の整数を表し、
q3は、0〜7の整数を表し、
q4は、0〜9の整数を表し、
rは、0〜2の整数を表し、
tは、0又は1の整数を表す。]。
化合物群A:アシベンゾラル−S−メチル、アシルアミノベンザミド、アシペタックス、アルジモルフ、アンバム、アムプロピルホス、アニラジン、アリルアルコール、アウレロファンジン、アザコナゾール、アジチラム、アゾキシストロビン、バリウムポリサルファイド、ベナラキシル、ベノダニル、ベノミル、ベンキノックス、ベンタルロン、ベンチアバリカルブ、ベンチアゾール、ベンザルコニウムクロライド、ベンザマクリル、ベンズアモルフ、ベンゾハイドロキサミックアシド、ビナパクリル、ビフェニル、ビテルタノール、ビチオノール、ベトキサジン、ボルドー液、ブラストサイジン−S、ブロモコナゾール、ブピリメート、ブチオベート、ブチルアミン、カルシウムポリスルフィド、キャプタフォール、カッパーオキシクロリド、カルプロパミド、カルバモルフ、カルベンダジン、カルボキシン、カルボン、チェシュントミクスチャ、キノメチオネート、クロベンチアゾン、クロラニフォルメタン、クロラニル、クロルフェナゾール、クロロネブ、クロロピクリン、クロロキノックス、クロゾリネート、クリムバゾール、クロトリマゾール、カッパーアセテイト、塩基性炭酸銅、水酸化第二銅、カッパーナフタレン、カッパーオルアイト、硫酸銅、塩基性硫酸銅、カッパージンククロメイト、クレゾール、クフラネブ、クプロバム、シアゾファミド、シクラフルアミド、シクロヘキシミド、シフルフェナミド、サイペンダゾール、シプロコナゾール、シプロジニル、シプロフラム、ダゾメット、デービーシーピー、デバカルブ、デカフェンチン、デハイドロアセテイト、ジクロン、ジクロロフェン、ジクロゾリン、ジクロブトラゾール、ジクロフラニド、ジクロメジン、ジクロラン、ジエトフェンカルブ、ジエチルピロカルボネイト、ジフェノコナゾール、ジフルメトリン、ジメチリモール、ジメトモルフ、、ジモキシストロビン、ジニコナゾール、ジニコナゾール−M、ジノブトン、ジノカップ、ジノカップ−4、ジノカップー6、ジノクトン、ジノスルフォン、ジノテルボン、ジフェニルアミン、ジピリチオン、ジノスルフィラム、ジタリムホス、ジチアノン、デーエヌオーシー、ドデモルフ、ドジン、ドラゾクソロン、エデフェノホス、エポキシコナゾール、エタコナゾール、エチリモル、エトリジアゾール、エテム、エトキシキン、エチルマーキュリーアセテイト、エチルマーキュリーブロマイド、塩化メチル水銀、エチルマーキュリーフォスフェイト、フェブコナゾール、フェナミドン、フェンダゾスラム、フェンフラム、フェンヘキサミド、フェノキサニル、フェンピクロニル、フェンプロピジン、フェンプロピモルフ、フェンチン、フェルバン、フェリムゾン、フルアジナム、フルジオキソニル、フルオロイミド、フルキンコナゾール、フルシラゾール、フルスルファミド、フルトリアフォール、フォルペット、フォセチル−アルミニウム、フベリダゾール、フララキシル、フラメトピル、フェナミノスルフ、フェナパニル、フェニトロパン、フルメトバー、フルモルフ、フルオトリマゾール、フルオキサストロビン、フルカルバニル、フルコナゾール、フルコナゾール−シス、フルメシクロックス、フロファネート、グアザチン、グリオジン、グリセオフルビン、ヘキサクロロベンゼン、ヘキサコナゾール、ヒメキサゾール、ハラクリネイト、ヘキサクロロブタジエン、ヘキシルチオフォス、ハイドロキシキノリン サルフェイト、イマザリル、イミベンコナゾール、イミノクタジン、イプコナゾール、イプロベンホス、イソプロチオラン、イプロバリカルブ、イソバレジオン、カスガマイシン、マンカッパー、マンコゼブ、マンネブ、メパニピリム、メプロニル、メタラキシル、メトコナゾール、メタスルホカルブ、メチラム、メトミノストロビン、ミクロブタニル、MTF−753、メベニル、メカルビンジド、塩化第二水銀、酸化第二水銀、塩化第一水銀、メタラキシル−M、メタム、メタロキソロン、メスフロキサム、メチルブロマイド、メチルイソチアシアネイト、メチルマーキュリーベンゾエイト、メチルマーキュリージシアンジアミド、メトラフェノン、メトスルフォバックス、ミルネブ、ミクロゾリン、メトキシメチルマーキュリークロライド、ナバム、ニッケルビス(ジメチルジチオカーバメート)、ニトロタール−イソプロピル、ヌアリモル、ナタマイシン、ニコビフェン、ニトロスチレン、オクチリノン、オフレース、オキサジキシル、オキシカルボキシン、オキポコナゾールフマール酸塩、オーシーエイチ、オリサストロビン、有機銅、ペフラゾエート、ペンコナゾール、ペンシクロン、フタライド、ピペラリン、ポリオキシン、炭酸水素カリウム、プロベナゾール、プロシミドン、プロパモカルブ塩酸塩、プロピコナゾール、プロピネブ、ピラゾホス、ピリフェノックス、ピリメタニル、ピロキロン、ペンタクロロフェノール、尿素フェニル水銀、フェニルマーキュリーアセテイト、フェニルマーキュリークロライド、フェニルマーキュリーナイトレイト、フェニルマーキュリーサリシレイト、フォスジフェン、ピコキシストロビン、ポリカルバメイト、ポリオクソリム、ポタシウムアザイド、ポタシウムポリサルファイド、プロキナジド、プロチオカルブ、プロチオコナゾール、ピラカルボリド、ピラクロストロビン、ピリジニトリル、ピロキシクロア、ピロキシサルファ、フェニルフェノール、キノメチオネート、キノキシフェン、キントゼン、キナセトール、キナザミド、キンコナゾール、ラベンザゾール、炭酸水素ナトリウム、次亜塩素酸ナトリウム、硫黄、スピロキサミン、サリチルアニリド、シルチオファム、シメコナゾール、アジ化ナトリウム、ソジウムオルトペニルペノキサイド、ソジウムペンタクロロフェノキサイド、ソジウムポリサルファイド、テブコナゾール、テクナゼン、テトラコナゾール、チアベンダゾール、チアジアジン、チフルザミド、チオファネート−メチル、チラム、トルクロホス−メチル、トリルフラニド、トリアジメホン、トリアジメノール、トリアゾキシド、トリデモルフ、トリフルミゾール、トリホリン、トリチコナゾール、テーシーエムテービー、テコラム、チアジフルア、チシオフェン、チオクロルフェンフィム、チオメルサム、チオファネイト、チオキノックス、チアジニル、チオキシミド、トリマーキュリアセテイト、トリアミフォス、トリアリモル、トリアズブチル、トリブチルチンオキサイド、トリクルアミド、トリフロキシストロビン、バリダマイシン、ビンクロゾリン、硫酸亜鉛、ジネブ、ジラム、ゾキサミド、ザリルアミド、ジンクナフテネイト、シイタケ菌糸体抽出物、ブロノポル、フォルムアルデハイド、ニトラピリン、オキソリニックアシド、オキシテトラサイクリン、ストレプトマイシン、テクロフタラム、チオメルサル、イマニン、ルバビリン、アルドキシカルブ、カズサホス、ジクロフェンチオン、DSP、エトプロホス、フェンスルホチオン、フォスチアゼート、フォスチエタン、イサミドホス、イサゾホス、オキサミル、フェナミホス、チオナジン、アセキノシル、アクリナトリン、ブロモプロピレート、チノメチオネート、クロロベンジラート、サイヘキサチン、ジコフォール、ジエノクロール、エトキサゾール、フェナザキン、フェンブタチンオキシド、フェンプロパトリン、フェンピロキシメート、フェノチオカルブ、フルアクリピリム、ハルフェンプロックス、ヘキシチアゾックス、ミルベメクチン、プロパルギット、ピリダベン、ピリミジフェン、スピロディクロフェン、テブフェンピラド、アバメクチン、アセフェート、アセタミピリド、アラニカルブ、アルディカルブ、アレスリン、アジンホス−メチル、バチルスチューリンゲシス、ベンジオカルブ、ベンフラカルブ、ベンスルタップ、ブプロフェジン、ブトカルボキシン、カルバリル、カルボフラン、カルタップ、クロルフェナピル、クロルフェンビンホス、クロルフルアズロン、クロチアニジン、クロマフェノジド、クロピリホス−メチル、シクロプロトリン、シフルトリン、ベータ−シフルトリン、シペルメトリン、シロマジン、シハロトリン、ラムダ−シハロトリン、デルタメトリン、ジアフェンチウロン、ダイアジノン、ジアクロデン、ジフルベンズロン、ジメチルビンホス、ジノテフラン、ジオフェノラン、ジスルフォトン、ジメトエート、エマメクチンベンゾエート、EPN、エスフェンバレレート、エチオフェンカルブ、エチプロール、エトリムホス、フェノブカルブ、フェノキシカーブ、フェンチオン、フェンバレレート、フルシトリネート、フルフェノクスロン、フルフェンプロックス、フルバリネート、タウ−フルバリネート、ホノホス、フォルメタネート、フォルモチオン、フラチオカルブ、ハロフェノジド、ヘキサフルムロン、ヒドラメチルノン、イミダクロプリド、イソフェンホス、インドキサカルブ、イソプロカルブ、イソキサチオン、ルフェヌウロン、マラチオン、メタルデヒド、メタミドホス、メチダチオン、メタクリホス、メタルカルブ、メソミル、メソプレン、メトキシクロール、メトキシフェノジド、モノクロトホス、ムスカルーレ、ニテンピラム、オメトエート、オキシデメトン−メチル、オキシデプロポス、パラチオン、パラチオン−メチル、ペルメトリン、フェントエート、フォキシム、ホレート、ホサロン、ホスメット、ホスファミドン、ピリミカルブ、ピリミホス−メチル、プロフェノホス、プロチオホス、プロパホス、プロトリフェンブト、ピリダリル、ピメトロジン、ピラクロホス、ピリプロキシフェン、ロテノン、スルプロホス、シラフルオフェン、スピロメシフェン、スルホテップ、テブフェノジド、テフルベンズロン、テルブホス、テトラクロロビンホス、チアクロプリド、チオシクラム、チオジカルブ、チアメトキサム、チオファノックス、チオメトン、トルフェンピラド、トラロメトリン、トリクロルホン、トリアズロン、トリフルムロン、バミドチオン及びエチオン。 Insecticides and killings containing one or more selected from the following substituted benzanilide compounds represented by the following general formula (1) and salts thereof, and one or more selected from the following compound group A: Tick, nematicide, bactericidal or bactericidal composition.
General formula (1):
W 1 and W 2 each independently represent an oxygen atom or a sulfur atom,
X is a halogen atom, cyano, nitro, azido, -SCN, -SF 5, C 1 ~C 6 alkyl, optionally substituted by R 7 (C 1 ~C 6) alkyl, C 3 -C 8 cycloalkyl , optionally substituted by R 7 (C 3 ~C 8) cycloalkyl, C 2 -C 6 alkenyl, optionally substituted by R 7 (C 2 ~C 6) alkenyl, C 3 -C 8 cycloalkenyl , C 3 -C 8 halocycloalkyl cycloalkenyl, C 2 -C 6 alkynyl, optionally substituted by R 7 (C 2 ~C 6) alkynyl, -OH, -OR 8, -OS ( O) 2 R 8, -SH, -S (O) r R 8 , -CHO, -C (O) R 9 , -C (O) OR 9 , -C (O) SR 9 , -C (O) NHR 10 , -C ( O) N (R 10 ) R 9 , -C (S) OR 9 , -C (S) SR 9 , -C (S) NHR 10 , -C (S) N (R 10 ) R 9 , -CH = NOR 11 , -C (R 9 ) = NOR 11 , -S (O) 2 OR 9 , -S (O) 2 NHR 10 , -S (O) 2 N (R 10 ) R 9 , -Si (R 13 ) (R 14) R 12, (Z 1) phenyl optionally substituted by p1, represents L or M, when m represents 2, 3 or 4, respectively X may be the even or different from each other the same as each other,
Further, when two Xs are adjacent to each other, the two adjacent Xs are -CH 2 CH 2 CH 2- , -CH 2 CH 2 O-, -CH 2 OCH 2- , -OCH 2 O-, -CH 2 CH 2 S-, -CH 2 SCH 2- , -CH 2 CH 2 N (R 15 )-, -CH 2 N (R 15 ) CH 2- , -CH 2 CH 2 CH 2 CH 2- , -CH 2 CH 2 CH 2 O-, -CH 2 CH 2 OCH 2- , -CH 2 OCH 2 O-, -OCH 2 CH 2 O-, -OCH 2 CH 2 S-, -CH 2 CH = CH-,- OCH = CH-, -SCH = CH-, -N (R 15 ) CH = CH-, -OCH = N-, -SCH = N-, -N (R 15 ) CH = N-, -N (R 15 By forming N = CH-, -CH = CHCH = CH-, -OCH 2 CH = CH-, -N = CHCH = CH-, -N = CHCH = N- or -N = CHN = CH- A 5-membered ring or a 6-membered ring may be formed together with the carbon atom to which each of two Xs is bonded. At this time, the hydrogen atom bonded to each carbon atom forming the ring is optionally substituted by Z 1 . Furthermore, when two or more Z 1 are substituted at the same time, each Z 1 may be the same as or different from each other,
When G represents a 5-membered or 6-membered non-aromatic heterocyclic ring containing at least one atom selected from an oxygen atom, a sulfur atom and a nitrogen atom and having at least one double bond in the ring, X may further represent -N (R 17 ) R 16 , -N = CHOR 12 or -N = C (R 9 ) OR 12
Y is a halogen atom, cyano, nitro, azido, -SCN, -SF 5, C 1 ~C 6 alkyl, optionally substituted by R 7 (C 1 ~C 6) alkyl, C 3 -C 8 cycloalkyl , optionally substituted by R 7 (C 3 ~C 8) cycloalkyl, -OH, -OR 8, -OS ( O) 2 R 8, -SH, -S (O) r R 8, -NH 2 , C 1 -C 6 alkylamino, di (C 1 -C 6 alkyl) amino, phenyl, L or M optionally substituted by -Si (R 13 ) (R 14 ) R 12 , (Z 1 ) p1 And when n represents 2, 3 or 4, each Y may be the same as or different from each other,
Further, when two Ys are adjacent to each other, the two adjacent Ys are —CH 2 CH 2 CH 2 —, —CH 2 CH 2 O—, —CH 2 OCH 2 —, —OCH 2 O—, —CH 2 CH 2 S-, -CH 2 SCH 2- , -SCH 2 S-, -CH 2 CH 2 CH 2 CH 2- , -CH 2 CH 2 CH 2 O-, -CH 2 CH 2 OCH 2 -,- By forming CH 2 OCH 2 O-, -OCH 2 CH 2 O-, -OCH 2 CH 2 S-, -SCH 2 CH 2 S-, -OCH = N- or -SCH = N- A 5-membered ring or a 6-membered ring may be formed together with the carbon atom to which each Y is bonded, and at this time, the hydrogen atom bonded to each carbon atom forming the ring may be optionally substituted by Z 1 In addition, in addition, when simultaneously substituted with two or more Z 1 , each Z 1 may be the same as or different from each other,
R 1 , R 2 and R 3 are each independently a hydrogen atom, cyano, C 1 -C 12 alkyl, (C 1 -C 12 ) alkyl optionally substituted by R 18 , C 3 -C 12 cycloalkyl , optionally substituted by R 18 (C 3 ~C 12) cycloalkyl, C 3 -C 12 alkenyl, optionally substituted by R 18 (C 3 ~C 12) alkenyl, C 3 -C 12 cycloalkenyl , C 3 -C 12 halo cycloalkenyl, C 3 -C 12 alkynyl, optionally substituted by R 18 (C 3 ~C 12) alkynyl, -OH, C 1 -C 8 alkoxy, C 3 -C 8 alkenyl oxy, C 3 -C 8 haloalkenyloxy, (Z 1) which may be substituted by p1 phenoxy, (Z 1) p1 phenyl optionally substituted by (C 1 ~C 4) alkoxy, C 1 ~ C 6 alkylthio, C 1 -C 6 haloalkylthio, (Z 1) p1 may be substituted by phenylthio, -S (O) 2 R 9 , -SN (R 20 ) R 19 , -S (O) 2 N (R 10 ) R 9 , -N (R 22 ) R 21 , -C (O) R 9 , -C (O) OR 9 , -C (O) SR 9 , -C (O) N (R 10 ) R 9 , -C (S) OR 9 , -C (S) SR 9 , -C (S) N (R 10 ) R 9 , (Z 1 ) by p1 Optionally substituted phenyl, L or M, or R 2 and R 3 together form a C 2 -C 6 alkylene chain to form a 3-7 member with the nitrogen atom to which it is attached indicates that may form a ring, this time the alkylene chain an oxygen atom, may contain one sulfur atom or a nitrogen atom, and a halogen atom, C 1 -C 6 alkyl group, C 1 -C 6 haloalkyl group may be optionally substituted by C 1 -C 6 alkoxy group, C 1 -C 6 alkylcarbonyl group or a C 1 -C 6 alkoxycarbonyl group,
R 4 is a hydrogen atom, a halogen atom, cyano, optionally substituted by C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, optionally substituted by R 23 (C 1 ~C 6) alkyl, R 23 and (C 1 ~C 6) haloalkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 halocycloalkyl, optionally substituted by R 23 (C 3 ~C 8) cycloalkyl, optionally by R 23 substituted (C 3 ~C 8) halocycloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 alkynyl, C 3 -C 6 haloalkynyl, -OR 8, -S (O) r R 8 , -N (R 10 ) R 9 , -CHO, -C (O) R 9 , -C (O) OR 9 , -C (O) SR 9 , -C (O) NHR 10 , -C (O) N (R 10 ) R 9 , -C (S) OR 9 , -C (S) SR 9 , -C (S) NHR 10 , -C (S) N (R 10 ) R 9 , -CH = NOR 11 , -C (R 9 ) = NOR 11 , -Si (R 13 ) (R 14 ) R 12 , -P (O) (OR 24 ) 2 , (Z 2 ) p1 May represent phenyl, 1-naphthyl, 2-naphthyl, L or M;
R 5 is
(a) a 5- or 6-membered non-aromatic heterocyclic ring or oxygen containing at least one atom selected from oxygen, sulfur and nitrogen, and having at least one double bond in the ring; atom, to represent a saturated 5- or 6-membered heterocyclic ring containing two atoms selected from sulfur atom and a nitrogen atom, a hydrogen atom, a halogen atom, cyano, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, optionally substituted by R 23 (C 1 ~C 6) alkyl, optionally substituted by R 23 (C 1 ~C 6) haloalkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 halocycloalkyl , optionally substituted by R 23 (C 3 ~C 8) cycloalkyl, optionally substituted by R 23 (C 3 ~C 8) halocycloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 alkynyl, C 3 -C 6 haloalkynyl, -OR 8, -S (O) r R 8, -N (R 1 0 ) R 9 , -CHO, -C (O) R 9 , -C (O) OR 9 , -C (O) SR 9 , -C (O) NHR 10 , -C (O) N (R 10 ) R 9 , -C (S) OR 9 , -C (S) SR 9 , -C (S) NHR 10 , -C (S) N (R 10 ) R 9 , -CH = NOR 11 , -C (R 9 ) = NOR 11 , (Z 2 ) represents phenyl, 1-naphthyl, 2-naphthyl, L or M optionally substituted by p1 ,
(b). G represents a cycloalkyl ring of 3 to 6-membered, and when R 4 represents a hydrogen atom, a halogen atom, C 1 -C 6 alkyl or C 1 -C 6 haloalkyl, cyano, by R 23 Optionally substituted (C 1 -C 6 ) alkyl, (C 1 -C 6 ) haloalkyl optionally substituted by R 23 , C 3 -C 8 cycloalkyl, C 3 -C 8 halocycloalkyl, R 23 optionally substituted by (C 3 ~C 8) cycloalkyl, optionally substituted by R 23 (C 3 ~C 8) halocycloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 alkynyl, C 3 -C 6 haloalkynyl, -OR 8, -S (O) r R 8, -N (R 10) R 9, -CHO, -C (O) R 9, -C (O) OR 9 , -C (O) SR 9 , -C (O) NHR 10 , -C (O) N (R 10 ) R 9 , -C (S) OR 9 , -C (S) SR 9 , -C (S) NHR 10 , -C (S) N (R 10 ) R 9 , -CH = NOR 11 , -C (R 9 ) = NOR 11 , -Si (R 13 ) (R 14 ) R 12 , (Z 2) which may be substituted by p1 phenylene Represents 1-naphthyl, 2-naphthyl, L or M,
(c). G represents a cycloalkyl ring of 3 to 6-membered, and R 4 is cyano, optionally substituted by optionally substituted by R 23 (C 1 ~C 6) alkyl, R 23 ( C 1 -C 6) haloalkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 halocycloalkyl, optionally substituted by R 23 (C 3 ~C 8) cycloalkyl, optionally substituted with R 23 and (C 3 ~C 8) halocycloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 alkynyl, C 3 -C 6 haloalkynyl, -OR 8, -S (O ) r R 8 , -N (R 10 ) R 9 , -CHO, -C (O) R 9 , -C (O) OR 9 , -C (O) SR 9 , -C (O) NHR 10 ,- C (O) N (R 10 ) R 9 , -C (S) OR 9 , -C (S) SR 9 , -C (S) NHR 10 , -C (S) N (R 10 ) R 9 ,- CH = NOR 11, -C (R 9) = NOR 11, -Si (R 13) (R 14) R 12, -P (O) (OR 24) 2, optionally substituted by (Z 2) p1 Good phenyl, 1-naphthyl, 2-naphthyl, L or M represents hydrogen atom, halogen Atom, cyano, optionally substituted by C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, optionally substituted by R 23 (C 1 ~C 6) alkyl, R 23 (C 1 ~C 6) haloalkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 halocycloalkyl, optionally substituted by R 23 (C 3 ~C 8) cycloalkyl, optionally substituted by R 23 (C 3 ~C 8) halocycloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 alkynyl, C 3 -C 6 haloalkynyl, -OR 8, -S (O) r R 8, - N (R 10 ) R 9 , -CHO, -C (O) R 9 , -C (O) OR 9 , -C (O) SR 9 , -C (O) NHR 10 , -C (O) N ( R 10 ) R 9 , -C (S) OR 9 , -C (S) SR 9 , -C (S) NHR 10 , -C (S) N (R 10 ) R 9 , -CH = NOR 11 ,- C (R 9 ) = NOR 11 , -Si (R 13 ) (R 14 ) R 12 , (Z 2 ) represents phenyl, 1-naphthyl, 2-naphthyl, L or M optionally substituted by p1 ,
R 6 is a hydrogen atom, a halogen atom, cyano, optionally substituted by C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, optionally substituted by R 23 (C 1 ~C 6) alkyl, R 23 and (C 1 ~C 6) haloalkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 halocycloalkyl, optionally substituted by R 23 (C 3 ~C 8) cycloalkyl, optionally by R 23 substituted (C 3 ~C 8) halocycloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 alkylthio, C 1 -C 6 haloalkylthio, -S (O) 2 R 9 , -C (O) R 9 , -C (O) OR 9 , -C (O) SR 9 , -C (S) OR 9 , -C (S) SR 9 , -C (O) N ( R 10 ) R 9 , -C (S) N (R 10 ) R 9 , -P (O) (OR 24 ) 2 , -P (S) (OR 24 ) 2 , (Z 2 ) p1 phenyl optionally, 1-naphthyl, 2-naphthyl, represents L or M, when l is an integer of 2 or more, also each of R 6 the same as each other or different from each other May have become, the
Further, R 6 may be adjacent to R 4, by R 4 and R 6 adjacent to form a C 3 -C 5 alkylene chain together, a 5- to 7-membered ring is formed together with the atoms connecting The alkylene chain may contain one oxygen or sulfur atom and may be optionally substituted with a C 1 -C 6 alkyl group,
L represents an aromatic heterocycle represented by any one of formulas L-1 to L-58,
Z 2 is a halogen atom, cyano, nitro, amino, azido, -SCN, -SF 5, C 1 ~C 6 alkyl, optionally substituted by R 7 (C 1 ~C 6) alkyl, C 3 -C 8 cycloalkyl, substituted optionally substituted by R 7 (C 3 ~C 8) cycloalkyl, by C 2 -C 6 alkenyl, R 7 optionally (C 2 ~C 6) alkenyl, C 3 -C 8 cycloalkenyl, C 3 -C 8 halocycloalkyl cycloalkenyl, C 2 -C 6 alkynyl, optionally substituted by R 7 (C 2 ~C 6) alkynyl, -OH, -OR 8, -OS ( O) 2 R 8 , -SH, -S (O) r R 8 , -N (R 10 ) R 9 , -N (R 10 ) CHO, -N (R 10 ) C (O) R 9 , -N (R 10 ) C (O) OR 9 , -N (R 10 ) C (O) SR 9 , -N (R 10 ) C (S) OR 9 , -N (R 10 ) C (S) SR 9 , -N ( R 10 ) S (O) 2 R 9 , -CHO, -C (O) R 9 , -C (O) OR 9 , -C (O) NHR 10 , -C (O) N (R 10 ) R 9 , -C (S) NHR 10 , -C (S) N (R 10 ) R 9 , -S (O) 2 OR 9 , -S (O) 2 NHR 10 , -S (O) 2 N (R 10 ) R 9, -Si (R 13 ) (R 14) R 12, substituted by (Z 1) p1 Some represent phenyl, L or M, when p1 represents an integer of 2 or more, each of Z 2 may be also or different from each other the same as each other,
Further, when two Z 2 are adjacent, the two adjacent Z 2 are —CH 2 CH 2 CH 2 —, —CH 2 CH 2 O—, —CH 2 OCH 2 —, —OCH 2 O—, -CH 2 CH 2 S-, -CH 2 SCH 2- , -CH 2 CH 2 CH 2 CH 2- , -CH 2 CH 2 CH 2 O-, -CH 2 CH 2 OCH 2- , -CH 2 OCH 2 By forming O-, -OCH 2 CH 2 O- or -OCH 2 CH 2 S-, a 5-membered ring or a 6-membered ring may be formed with the carbon atom to which each of the two Z 2 is bonded, in this case, hydrogen atoms bonded to each carbon atom forming the ring may be optionally substituted by halogen atom or C 1 -C 6 alkyl group,
R 7 is a halogen atom, cyano, C 3 to C 8 cycloalkyl, C 3 to C 8 halocycloalkyl, —OH, —OR 8 , —SH, —S (O) r R 8 , —N (R 10 ) R 9 , -N (R 10 ) CHO, -N (R 10 ) C (O) R 9 , -N (R 10 ) C (O) OR 9 , -N (R 10 ) C (O) SR 9 , -N (R 10 ) C (S) OR 9 , -N (R 10 ) C (S) SR 9 , -N (R 10 ) S (O) 2 R 9 , -C (O) OR 9 ,- C (O) N (R 10 ) R 9 , -Si (R 13 ) (R 14 ) R 12 , (Z 1 ) represents phenyl, L or M optionally substituted by p1 ,
R 8 is optionally substituted by C 1 -C 6 alkyl, optionally substituted by R 27 (C 1 ~C 6) alkyl, C 3 -C 8 cycloalkyl, R 27 (C 3 ~C 8 ) cycloalkyl, C 2 -C 6 alkenyl, optionally substituted by R 27 (C 2 ~C 6) alkenyl, C 3 -C 8 cycloalkenyl, C 3 -C 8 halocycloalkyl cycloalkenyl, C 3 -C 6 It represents alkynyl, optionally substituted by R 27 (C 3 ~C 6) alkynyl, (Z 1) phenyl optionally substituted by p1, L or M,
R 9 is C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl (C 1 -C 4 ) alkyl, C 1 -C 6 alkoxy (C 1 -C 4 ) alkyl, C 1 -C 6 alkylthio (C 1 ~C 4) alkyl, cyano (C 1 ~C 6) alkyl, (Z 1) phenyl optionally substituted by p1 (C 1 ~C 4) alkyl, L-(C 1 -C 4) alkyl, M- (C 1 ~C 4) alkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 halocycloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, Represents C 3 -C 6 alkynyl or phenyl optionally substituted by (Z 1 ) p1 ,
R 10 represents a hydrogen atom or C 1 -C 6 alkyl, or R 9 and R 10 together form a C 2 -C 6 alkylene chain to form 3-7 together with the atoms to be bonded. indicates that the members may form a ring, this time the alkylene chain an oxygen atom, may contain one sulfur atom or a nitrogen atom, and a halogen atom, C 1 -C 6 alkyl group, C 1 -C 6 alkoxy group, a formyl group, may be optionally substituted by C 1 -C 6 alkylcarbonyl group or a C 1 -C 6 alkoxycarbonyl group,
R 11 is a hydrogen atom, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, phenyl (C 1 -C 4 ) alkyl optionally substituted by (Z 1 ) p 1 , C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, or represents C 3 -C 6 alkynyl or C 3 -C 6 haloalkynyl, or to form a C 2 -C 4 alkylene chain and R 9 and R 11 together Represents that a 5- to 7-membered ring may be formed together with the atoms to be bonded, in which case the alkylene chain may contain one oxygen atom, sulfur atom or nitrogen atom, and a halogen atom or C 1 -C Optionally substituted by 6 alkyl groups,
R 12 represents C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 alkenyl or phenyl optionally substituted by (Z 1 ) p 1 ;
R 13 and R 14 each independently represent C 1 -C 6 alkyl or C 1 -C 6 haloalkyl,
R 15 is a hydrogen atom, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxycarbonyl (C 1 -C 4 ) alkyl, C 1 -C 6 haloalkoxycarbonyl (C 1 -C 4) alkyl, (Z 1) phenyl optionally substituted by p1 (C 1 -C 4) alkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 alkynyl, C 3 -C 6 haloalkynyl, C 1 -C 6 alkoxy, C 1 -C 6 alkoxycarbonyl, C 1 -C 6 haloalkoxycarbonyl or (Z 1) p1 represents phenyl optionally substituted by,
R 16 is a hydrogen atom, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl (C 1 -C 4 ) alkyl, C 1 -C 4 alkoxy (C 1 -C 4 ) Alkyl, C 1 -C 4 alkylthio (C 1 -C 4 ) alkyl, phenylthio (C 1 -C 4 ) alkyl optionally substituted by (Z 1 ) p 1 , cyano (C 1 -C 6 ) alkyl, C 1 -C 6 alkoxycarbonyl (C 1 -C 4) alkyl, C 1 -C 6 alkylaminocarbonyl (C 1 -C 4) alkyl, di (C 1 -C 6 alkyl) aminocarbonyl (C 1 -C 4) alkyl, (Z 1) p1 phenyl optionally substituted by (C 1 ~C 4) alkyl, L- (C 1 ~C 4) alkyl, M- (C 1 ~C 4) alkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 alkynyl, C 3 -C 6 haloalkynyl, -OH, C 1 -C 6 alkylcarbonyloxy, C 1 -C 6 alkylthio, C 1 -C 6 haloalkylthio, (Z 1) which may be substituted by p1 phenylthio, C 1 -C 6 alkylsulfonyl, C 1 -C 6 haloalkylsulfonyl, (Z 1) p1 phenyl optionally substituted by sulfonyl, -SN (R 20) R 19 , C 1 ~C 6 alkylaminosulfonyl, di (C 1 -C 6 alkyl) aminosulfonyl, -CHO, -C (O) R 9, -C (O) OR 9 , -C (O) SR 9 , -C (O) NHR 10 , -C (O) N (R 10 ) R 9 , -C (S) OR 9 , -C (S) SR 9 , -C (S ) NHR 10 , -C (S) N (R 10 ) R 9 , -C (O) C (O) R 9 , -C (O) C (O) OR 9 , -P (O) (OR 24 ) 2 or -P (S) (OR 24 ) 2
R 17 is a hydrogen atom, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 8 cycloalkyl (C 1 -C 6 ) alkyl, C 3 -C 8 cycloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 alkynyl, C 3 -C 6 haloalkynyl, -CHO, C 1 ~C 6 alkyl carbonyl, C 1 -C 6 haloalkylcarbonyl or C 1 -C 6 alkoxy Represents carbonyl, or R 16 and R 17 together form a C 2 to C 6 alkylene chain to form a 3- to 7-membered ring with the nitrogen atom to which it is bonded. In this case, the alkylene chain may contain one oxygen atom, sulfur atom or nitrogen atom, and may be optionally substituted with a halogen atom, a C 1 -C 6 alkyl group or a C 1 -C 6 haloalkyl group. further alternatively, R 17 forms a C 1 -C 2 alkylene chain together with R 2 Optionally substituted by, indicates that may form a heterocyclic 6-membered or 7-membered benzene ring fused together with the binding atoms, by this time the alkylene chain is an oxygen atom or a C 1 -C 6 alkyl group and May have been
R 18 is a halogen atom, cyano, nitro, C 3 -C 8 cycloalkyl, C 3 -C 8 halocycloalkyl, -OR 28 , -N (R 29 ) R 28 , -SH, -S (O) r R 30 , -CHO, -C (O) R 31 , -C (O) OH, -C (O) OR 31 , -C (O) SR 31 , -C (O) NHR 32 , -C (O) N (R 32 ) R 31 , -C (O) C (O) OR 31 , -C (R 34 ) = NOH, -C (R 34 ) = NOR 33 , -Si (R 13 ) (R 14 ) R 12 , -P (O) (OR 24 ) 2 , -P (S) (OR 24 ) 2 , -P (phenyl) 2 , -P (O) (phenyl) 2 , (Z 1 ) p1 May represent phenyl, L or M;
R 19 is C 1 -C 12 alkyl, C 1 -C 12 haloalkyl, C 1 -C 12 alkoxy (C 1 -C 12 ) alkyl, cyano (C 1 -C 12 ) alkyl, C 1 -C 12 alkoxycarbonyl (C 1 -C 12 ) alkyl, (Z 1 ) phenyl (C 1 -C 4 ) alkyl optionally substituted by p 1 , C 3 -C 12 alkenyl, C 3 -C 12 haloalkenyl, C 3 -C 12 alkynyl, C 3 -C 12 haloalkynyl, C 1 -C 12 alkylcarbonyl, C 1 -C 12 alkoxycarbonyl or (Z 1) p1 represents phenyl optionally substituted by,
R 20 is C 1 -C 12 alkyl, C 1 -C 12 haloalkyl, C 1 -C 12 alkoxy (C 1 -C 12 ) alkyl, cyano (C 1 -C 12 ) alkyl, C 1 -C 12 alkoxycarbonyl (C 1 -C 12 ) alkyl, (Z 1 ) phenyl (C 1 -C 4 ) alkyl optionally substituted by p 1 , C 3 -C 12 alkenyl, C 3 -C 12 haloalkenyl, C 3 -C 12 alkynyl, C 3 -C 12 haloalkynyl or phenyl which may be substituted by (Z 1 ) p 1 , or R 19 and R 20 together form a C 4 -C 7 alkylene chain This means that a 5- to 8-membered ring may be formed together with the nitrogen atom to be bonded, in which case the alkylene chain may contain one oxygen atom or sulfur atom, and a C 1 -C 4 alkyl group or it may be optionally substituted by C 1 -C 4 alkoxy group,
R 21 is a hydrogen atom, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, phenyl (C 1 -C 4 ) alkyl optionally substituted by (Z 1 ) p 1 , C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 alkynyl, -CHO, C 1 ~C 6 alkyl carbonyl, C 1 -C 6 haloalkylcarbonyl, C 1 -C 6 alkoxycarbonyl, C 1 -C 6 haloalkoxycarbonyl , (Z 1) phenyl optionally substituted by p1 (C 1 ~C 4) alkoxycarbonyl, (Z 1) p1 good phenoxycarbonyl optionally substituted by optionally substituted by (Z 1) p1 Represents good phenylcarbonyl or phenyl optionally substituted by (Z 1 ) p1 ,
R 22 represents a hydrogen atom, C 1 -C 6 alkyl, -CHO, C 1 -C 6 alkylcarbonyl, a C 1 -C 6 haloalkylcarbonyl or C 1 -C 6 alkoxycarbonyl,
R 23 is cyano, C 3 -C 8 cycloalkyl, C 3 -C 8 halocycloalkyl, —OH, —OR 8 , —SH, —S (O) r R 8 , —N (R 10 ) R 9 , -N (R 10 ) CHO, -N (R 10 ) C (O) R 9 , -N (R 10 ) C (O) OR 9 , -N (R 10 ) C (O) SR 9 , -N (R 10 ) C (S) OR 9 , -N (R 10 ) C (S) SR 9 , -N (R 10 ) S (O) 2 R 9 , -C (O) OR 9 , -C (O ) N (R 10 ) R 9 , -Si (R 13 ) (R 14 ) R 12 , (Z 1 ) represents phenyl, L or M optionally substituted by p1 ,
R 24 represents C 1 -C 6 alkyl or C 1 -C 6 haloalkyl,
R 25 is a halogen atom, cyano, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, hydroxy (C 1 -C 6 ) alkyl, C 1 -C 4 alkoxy (C 1 -C 4 ) alkyl, C 1 -C 4 alkoxycarbonyl (C 1 ~C 4) alkyl, C 1 -C 6 alkoxy, C 1 -C 6 alkoxycarbonyl or (Z 1) represents a phenyl which is substituted by p1, q1, q2, q3 Or when q4 represents an integer of 2 or more, each R 25 may be the same as or different from each other;
R 26 is substituted by a hydrogen atom, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, -CHO, C 1 -C 6 alkylcarbonyl, C 1 -C 6 haloalkylcarbonyl, (Z 1 ) p1 also phenyl (C 1 ~C 4) alkylcarbonyl, C 1 -C 6 alkoxycarbonyl, C 1 -C 6 haloalkoxycarbonyl, (Z 1) p1 phenyl optionally substituted by (C 1 ~C 4) alkoxycarbonyl, C 1 -C 6 alkylaminocarbonyl, di (C 1 -C 6 alkyl) aminocarbonyl, C 1 -C 6 alkylamino thiocarbonyl, di (C 1 -C 6 alkyl) aminothiocarbonyl, (Z 1 ) phenyl carbonyl optionally substituted by p1, C 1 ~C 6 alkylsulfonyl, C 1 -C 6 haloalkylsulfonyl, (Z 1) p1 phenyl sulfonyl optionally substituted by, -P (O) (OR 24 ) represents 2 or -P (S) (OR 24 ) 2 ,
R 27 is a halogen atom, cyano, C 3 -C 8 cycloalkyl, C 3 -C 8 halocycloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 alkylthio, C 1 -C 6 haloalkylthio, C 1 -C 6 alkylsulfonyl, C 1 -C 6 haloalkylsulfonyl, C 1 -C 6 alkylamino, di (C 1 -C 6 alkyl) amino, -CHO, C 1 -C 6 alkyl substituted carbonyl, C 1 -C 6 haloalkylcarbonyl, C 1 -C 6 alkoxycarbonyl, C 1 -C 6 haloalkoxycarbonyl, -CH = NOR 11, -C ( R 9) = NOR 11, by (Z 1) p1 Represents optionally substituted phenyl, L or M;
R 28 is a hydrogen atom, C 1 -C 8 alkyl, optionally substituted by R 35 (C 1 ~C 8) alkyl, C 3 -C 8 cycloalkyl, optionally substituted by R 35 (C 3 -C 8) cycloalkyl, C 3 -C 8 alkenyl, optionally substituted by R 35 (C 3 ~C 8) alkenyl, optionally substituted by C 3 -C 8 alkynyl, R 35 (C 3 ~ C 8 ) alkynyl, -CHO, -C (O) R 31 , -C (O) OR 31 , -C (O) SR 31 , -C (O) NHR 32 , -C (O) N (R 32 ) R 31 , -C (O) C (O) R 31 , -C (O) C (O) OR 31 , -C (S) R 31 , -C (S) OR 31 , -C (S) SR 31 , -C (S) NHR 32 , -C (S) N (R 32 ) R 31 , -S (O) 2 R 31 , -S (O) 2 N (R 32 ) R 31 , -Si (R 13 ) (R 14 ) R 12 , -P (O) (OR 24 ) 2 , -P (S) (OR 24 ) 2 , (Z 1 ) represents phenyl, L or M optionally substituted by p1 ,
R 29 represents a hydrogen atom, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl or C 1 -C 6 alkoxy, or R 28 and R 29 together by now it forms a C 2 -C 5 alkylene chain, represents that may form a 3-6 membered ring together with the nitrogen atom to which they are attached this case the alkylene chain may contain one oxygen atom or a sulfur atom But often, and halogen atom, C 1 -C 6 alkyl group, C 1 -C 6 alkoxy group or (Z 1) may be substituted by a phenyl group optionally substituted by p1,
R 30 is, C 1 -C 8 alkyl, optionally substituted by R 35 (C 1 ~C 8) alkyl, optionally substituted by C 3 -C 8 cycloalkyl, R 35 (C 3 ~C 8 ) cycloalkyl, optionally substituted by C 3 -C 8 alkenyl, R 35 (C 3 ~C 8 ) alkenyl, optionally substituted by C 3 -C 8 alkynyl, R 35 (C 3 ~C 8 ) alkynyl, -SH, C 1 ~C 6 alkylthio, C 1 -C 6 haloalkylthio, (Z 1) which may be substituted by p1 phenylthio, -CHO, -C (O) R 31, -C (O) OR 31 , -C (O) SR 31 , -C (O) NHR 32 , -C (O) N (R 32 ) R 31 , -C (O) C (O) R 31 , -C (O) C (O) OR 31 , -C (S) R 31 , -C (S) OR 31 , -C (S) SR 31 , -C (S) NHR 32 , -C (S) N (R 32 ) R 31 , -P (O) (OR 24 ) 2 , -P (S) (OR 24 ) 2 , (Z 1 ) phenyl optionally substituted by p1 , L-18, L-21, L-25, L Represents -30 to L-35, L-45, L-48, L-49 or M;
R 31 is C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 8 cycloalkyl (C 1 -C 4 ) alkyl, C 1 -C 6 alkoxy (C 1 -C 4 ) alkyl, C 1 -C 6 haloalkoxy (C 1 ~C 4) alkyl, C 1 -C 6 alkylthio (C 1 ~C 4) alkyl, C 1 -C 6 haloalkylthio (C 1 ~C 4) alkyl, C 1 -C 6 alkylsulfonyl (C 1 ~C 4) alkyl, C 1 -C 6 haloalkylsulfonyl (C 1 ~C 4) alkyl, cyano (C 1 -C 6) alkyl, C 1 -C 6 alkylcarbonyl (C 1 -C 4) alkyl, C 1 -C 6 haloalkylcarbonyl (C 1 -C 4) alkyl, C 1 -C 6 alkoxycarbonyl (C 1 -C 4) alkyl, di (C 1 -C 6 alkyl) aminocarbonyl (C 1 -C 4) alkyl, tri (C 1 -C 4 alkyl) silyl (C 1 -C 4) alkyl, (Z 1) p1 phenyl optionally substituted by (C 1 -C 4) alkyl, L-( C 1 -C 4) alkyl, M - (C 1 ~C 4) alkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 halocycloalkyl, C 2 -C 6 alkenyl (C 3 ~C 8) cycloalkyl, C 2 -C 6 haloalkenyl (C 3 ~C 8) cycloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, optionally substituted by (Z 1) p1 May represent phenyl, L or M,
R 32 represents a hydrogen atom, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl or phenyl optionally substituted by (Z 1 ) p 1 , or R 31 and R 32 are taken together. By forming a C 2 -C 5 alkylene chain, a 3- to 6-membered ring may be formed together with the nitrogen atom to be bonded. At this time, this alkylene chain has 1 oxygen atom, sulfur atom or nitrogen atom. pieces comprise may, and halogen atom, C 1 -C 6 alkyl group, C 1 -C 6 alkoxy group, a formyl group, C 1 -C 6 alkylcarbonyl group, C 1 -C 6 alkoxycarbonyl group or (Z 1) optionally substituted by a phenyl group optionally substituted by p1 ,
R 33 is a hydrogen atom, C 1 -C 8 alkyl, (C 1 -C 8 ) alkyl optionally substituted by R 35 , C 3 -C 8 cycloalkyl, C 3 -C 8 alkenyl, optional by R 35 substituted a (C 3 ~C 8) alkenyl, optionally substituted by C 3 -C 8 alkynyl, or R 35 (C 3 ~C 8) alkynyl,
R 34 is a hydrogen atom, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 8 cycloalkyl (C 1 ~C 4) alkyl, C 1 -C 6 alkoxy (C 1 ~C 4) alkyl, C 1 -C 6 haloalkoxy (C 1 ~C 4) alkyl, C 1 -C 6 alkylthio (C 1 ~C 4) alkyl, C 1 -C 6 haloalkylthio (C 1 ~C 4) alkyl, C 1 -C 6 alkylsulfonyl (C 1 ~C 4) alkyl, C 1 -C 6 haloalkylsulfonyl (C 1 ~C 4) alkyl, (Z 1) phenyl optionally substituted by p1 (C 1 ~C 4 ) Alkyl or (Z 1 ) p1 which is optionally substituted by p1 ,
R 35 is a halogen atom, cyano, nitro, C 3 -C 8 cycloalkyl, C 3 -C 8 halocycloalkyl, —OH, —OR 36 , —SH, —S (O) r R 36 , —NHR 37 , -N (R 37 ) R 36 , -CHO, -C (O) R 31 , -C (O) OR 31 , -C (O) SR 31 , -C (O) NHR 32 , -C (O) N (R 32 ) R 31 , -C (O) C (O) OR 31 , -CH = NOR 11 , -C (R 9 ) = NOR 11 , -Si (R 13 ) (R 14 ) R 12 ,- Optionally substituted by P (O) (OR 24 ) 2 , -P (S) (OR 24 ) 2 , -P (phenyl) 2 , -P (O) (phenyl) 2 , (Z 1 ) p1 Represents phenyl, L or M;
R 36 is C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy (C 1 -C 4 ) alkyl, C 1 -C 6 alkylthio (C 1 -C 4 ) alkyl, (Z 1) p1 phenyl optionally substituted by (C 1 ~C 4) alkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 halocycloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 halo alkenyl, C 3 -C 8 cycloalkenyl, C 3 -C 8 halocycloalkyl cycloalkenyl, C 3 -C 6 alkynyl, C 3 -C 6 haloalkynyl, -CHO, C 1 ~C 6 alkyl carbonyl, C 1 -C 6 haloalkylcarbonyl, C 1 -C 6 alkoxycarbonyl, C 1 -C 6 haloalkoxycarbonyl, C 1 -C 6 alkylaminocarbonyl, di (C 1 -C 6 alkyl) aminocarbonyl, optionally substituted by (Z 1) p1 be phenyl carbonyl, C 1 -C 6 alkylamino thiocarbonyl, di (C 1 -C 6 alkyl) A Bruno thiocarbonyl, represents (Z 1) phenyl optionally substituted by p1, L or M,
R 37 is a hydrogen atom, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 8 cycloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, C 1 -C 6 alkylcarbonyl , C 1 -C 6 haloalkylcarbonyl, C 1 -C 6 alkoxycarbonyl, C 1 -C 6 haloalkoxycarbonyl, (Z 1) p1 good phenoxycarbonyl optionally substituted by optionally substituted by (Z 1) p1 phenyl carbonyl be, C 1 -C 6 alkylsulfonyl, C 1 -C 6 haloalkylsulfonyl, (Z 1) phenyl optionally substituted by p1, or represents L or M, or, R 36 and R 37 Together form a C 2 -C 5 alkylene chain to form a 3- to 6-membered ring with the nitrogen atom to which the alkylene chain is bonded, wherein the alkylene chain is an oxygen atom or a sulfur atom May contain one and halo It may be substituted by emissions atom or a methyl group,
l represents an integer of 0 to 9,
m represents an integer of 0 to 4,
n represents an integer of 0 to 4,
p1 represents an integer of 1 to 5,
p2 represents an integer of 0 to 4,
p3 represents an integer of 0 to 3,
p4 represents an integer of 0 to 2,
p5 represents an integer of 0 or 1,
q1 represents an integer of 0 to 3,
q2 represents an integer of 0 to 5,
q3 represents an integer of 0 to 7,
q4 represents an integer of 0 to 9,
r represents an integer of 0 to 2;
t represents an integer of 0 or 1. ].
Compound group A: acibenzoral-S-methyl, acylaminobenzamide, acipetax, aldimorph, ambam, ampropylphos, anilazine, allyl alcohol, aurerophandin, azaconazole, adithylam, azoxystrobin, barium polysulfide, benalaxyl, benodanyl , Benomyl, Benquinox, Ventallon, Bench Avaricarb, Bench Azol, Benzalkonium Chloride, Benzacryl, Benzamorph, Benzohydroxamic Acid, Vinapacryl, Biphenyl, Viteltanol, Bitionol, Betoxazine, Bordeaux, Blasticidin-S, Bromoconazole, bupirimate, butiobate, butylamine, calcium polysulfide, captafol, copper oxychloride , Carpropamide, carbamorph, carbendazine, carboxin, carvone, chestnut mixture, quinomethionate, clobenazone, chloraniformane, chloranil, chlorphenazole, chloronebu, chloropicrin, chloroquinox, clozolinate, crimbazole, clos Trimazole, Copper Acetate, Basic Copper Carbonate, Cupric Hydroxide, Copper Naphthalene, Copper Oleite, Copper Sulfate, Basic Copper Sulfate, Copper Zinc Chromate, Cresol, Cufuraneb, Cuprobam, Cyazofamid, Cyclamamide, Cycloheximide, cyflufenamide, cypendazole, cyproconazole, cyprodinil, cyproflam, dazomet, Davy Cee, debacarb, decafentin, dehydroacetate , Dicron, dichlorophen, diclozoline, diclobutrazole, diclofuranide, diclomedin, dichlorane, diethofencarb, diethylpyrocarbonate, diphenoconazole, diflumethrin, dimethymol, dimethomorph, dimoxtrobin, diniconazole, diniconazole-M, dinobutone Dinocup-4, Dinocup-6, Dinoctone, Dinosulfone, Dinoterbon, Diphenylamine, Dipyrithione, Dinosulfiram, Ditalimphos, Dithianone, DENOC, Dodemorph, Dodine, Drazoxolone, Edefenophos, Epoxyconazole, Etaconazole, Ethymol, Etridiazole, Etidiazole Ethyl mercury acetate, ethyl mercury bromide Methylmercury chloride, ethyl mercury phosphate, febuconazole, fenamidone, fendazoslam, fenflam, fenhexamide, phenoxanyl, fenpiclonil, fenpropidin, fenpropimorph, fentin, felban, ferrimzone, fluazinam, fludioxonil, fluoroimide, Fluquinconazole, flusilazole, flusulfamide, flutriafol, phorpetol, fosetyl-aluminum, fuberidazole, flaraxil, framethopyl, phenaminosulfur, phenapanyl, fenitropan, flumethover, flumorph, fluotrimazole, fluoxastrobin, furcarbanil, fluconazole, fluconazole Cis, flumeciclos, furophanate, guazatine, Gliodin, griseofulvin, hexachlorobenzene, hexaconazole, hymexazole, haracrinate, hexachlorobutadiene, hexylthiophos, hydroxyquinoline sulfate, imazalyl, imibenconazole, iminoctazine, ipconazole, iprobenphos, isoprothiolane, iprovalircarb, isovaradicaper, kasugamycin Mancozeb, mannebu, mepanipyrim, mepronil, metalaxyl, metconazole, metasulfocarb, methylam, metminostrobin, microbutanyl, MTF-753, mevenyl, mecarbinzide, mercuric chloride, mercuric oxide, mercuric chloride, metalaxyl-M , Metam, metalloxolone, mesufloxam, methyl bromide, methyl isothiocyanate, Methyl Mercury Benzoate, Methyl Mercury Dicyandiamide, Metraphenone, Metosulfobax, Milneb, Microzoline, Methoxymethyl Mercury Chloride, Nabum, Nickel Bis (Dimethyldithiocarbamate), Nitrotar-Isopropyl, Nuarimol, Natamycin, Nicobiphene, Nitrostyrene, Octyrinone, Off Race, Oxazixyl, Oxycarboxyl, Okipoconazole fumarate, OHC, Orissarobine, Organic copper, Pephrazoate, Penconazole, Pencyclone, Phthalide, Piperalin, Polyoxin, Potassium bicarbonate, Probenazole, Procimidone, Propamocarb hydrochloride, Propiconazole , Propinebu, pyrazophos, pyrifenox, pyrimethanil, Lokilone, pentachlorophenol, urea phenylmercury, phenylmercury acetate, phenylmercury chloride, phenylmercury nitrate, phenylmercury salicylate, fosdifen, picoxystrobin, polycarbamate, polyoxorim, potassium azide, potassium polysulfide, Proquinazide, prothiocarb, prothioconazole, pyracarbide, pyraclostrobin, pyridinitrile, pyroxicycloa, piroxysulfa, phenylphenol, quinomethionate, quinoxyphene, quintozene, quinacetol, quinazamide, quinconazole, rabenzazole, sodium bicarbonate, sodium hypochlorite, Sulfur, spiroxamine, salicylanilide, silthiofam, shime Nazole, sodium azide, sodium orthopenyl penoxide, sodium pentachlorophenoxide, sodium polysulfide, tebuconazole, technazen, tetraconazole, thiabendazole, thiadiazine, thifluzamide, thiophanate-methyl, thyram, tolcrophos-methyl, tolylfuranide , Triadimethone, Triadimenol, Triazoxide, Tridemorph, Triflumizole, Triphorine, Triticonazole, Tethym Taby, Tecolum, Thiadiflua, Tisiophene, Thiochlorfenfim, Thiomersam, Thiophanate, Thioquinox, Thiazinyl, Thioximide, Trimercuriacese Tate, Triamifos, Triarimol, Triazbutyl, Tributyltin oxide, Tricuramide , Trifloxystrobin, validamycin, vinclozolin, zinc sulfate, dineb, ziram, zoxamide, zarylamide, zinc naphthenate, shiitake mycelium extract, bronopol, formaldehyde, nitraprine, oxolinic acid, oxytetracycline, streptomycin, teclophthalam, thiomersal, Imanin, rubyvirin, aldoxycarb, kazusafos, diclofenthion, DSP, etoprophos, fensulfothione, fostiazeate, fostietane, isamidophos, isazophos, oxamyl, phenamiphos, thionadine, acequinosyl, acrinathrine, bromopropyrate, chinomethionate, chlorodithionate Dienochlor, etoxazole, phenazaquin Fenbutatin oxide, phenpropatoline, fenpyroximate, phenothiocarb, fluacrylpyrim, halfenprox, hexithiazox, milbemectin, propargite, pyridaben, pyrimidifen, spirodiclofen, tebufenpyrad, abamectin, acephate, acetamipiride, alanicarb, aldicarb Aresulin, Azinphos-methyl, Bacillus thuringiensis, Bengiocarb, Benfuracarb, Bensultap, Buprofezin, Butcarboxyne, Carbaryl, Carbofuran, Cartap, Chlorfenapyr, Chlorfenvinphos, Chlorfluazuron, Clothianidin, Chromafenozide, Clopyrifos-methyl, Cyclo Protorin, cyfluthrin, beta-cyfluthrin Cypermethrin, cyromazine, cyhalothrin, lambda-cyhalothrin, deltamethrin, diafenthiuron, diazinon, diacloden, diflubenzuron, dimethylvinphos, dinotefuran, diophenolan, disulfone, dimethoate, emamectin benzoate, EPN, esfenvalerate, etiofencarb etrimol , Fenobucarb, phenoxy curve, fenthion, fenvalerate, flucitrinate, flufenoxuron, flufenprox, fulvalinate, tau-fulvalinate, phonofos, formethanate, formothione, furthiocarb, halofenozide, hexaflumuron, hydramethylnon , Imidacloprid, isofenphos, indoxacarb, isoprocarb , Isoxathione, rufenuron, malathion, metaldehydride, methamidophos, metidathion, methaclifos, metalcarb, mesomil, mesoprene, methoxychlor, methoxyphenozide, monocrotophos, muscarule, nitenpyram, ometoate, oxydemeton-methyl, oxydeproposone, parathion, parathion, parathion, perthion , Fentoate, Foxime, Folate, Fosalone, Phosmet, Phosphamidone, Pirimicarb, Pirimiphos-methyl, Profenofos, Prothiophos, Propafos, Protrifenbut, Pyridalyl, Pymetrozine, Pyraclophos, Pyriproxyfen, Rotenone, Sulprophos, Silafluophene, Spiromesifene, Sulfotep, Tebufenozide, Teflubenzuron, Tell Phosphite, tetra black Robin phosphite, thiacloprid, thiocyclam, thiodicarb, thiamethoxam, thiofanox, thiometon, tolfenpyrad, tralomethrin, trichlorfon, Toriazuron, triflumuron, vamidothion and ethion.
Yは、ハロゲン原子、C1〜C4アルキル、C1〜C4ハロアルキル、C1〜C4アルコキシ又はC1〜C4アルキルチオを表し、nが2を表すとき、各々のYは互いに同一であっても又は互いに相異なっていてもよく、
R1は、水素原子を表し、
R2は、水素原子又はC1〜C6アルキルを表し、
R3は、C1〜C8アルキル、R18によって任意に置換された(C1〜C8)アルキル、C3〜C8アルケニル又はC3〜C8アルキニルを表し、
R4は、C1〜C6アルキル、C1〜C6ハロアルキル、(Z2)p1によって置換されていてもよいフェニル、2-ナフチル、L-1〜L-4、L-15〜L-17、L-19、L-20、L-22、L-23、L-45、L-46又はL-47を表し、
R5は、
(a). R4がC1〜C6アルキル又はC1〜C6ハロアルキルを表すとき、(Z2)p1によって置換されていてもよいフェニル、1-ナフチル、2-ナフチル、L-1〜L-5、L-8〜L-24、L-28〜L-36、L-39、L-41、L-42、L-45〜L-47又はL-50を表し、
(b). R4が(Z2)p1によって置換されていてもよいフェニル、2-ナフチル、L-1〜L-4、L-15〜L-17、L-19、L-20、L-22、L-23、L-45、L-46又はL-47を表すとき、水素原子、ハロゲン原子、C1〜C6アルキル、C1〜C6ハロアルキル、C1〜C6アルコキシ、C1〜C6ハロアルコキシ、C1〜C6アルキルチオ、C1〜C6アルキルスルフィニル、C1〜C6アルキルスルホニル又はジ(C1〜C6)アルキルアミノを表し、
R6a、R6b、R6c及びR6dは、水素原子を表し、
R6eは、C1〜C6アルキルを表し、
R6iは、水素原子を表し、
R6j及びR6kは、各々独立して水素原子、ハロゲン原子又はシアノを表し、
Z2は、ハロゲン原子、シアノ、ニトロ、C1〜C6アルキル、C1〜C6ハロアルキル、C1〜C3アルコキシ(C1〜C3)アルキル、C1〜C3ハロアルコキシ(C1〜C3)アルキル、C1〜C3アルキルチオ(C1〜C3)アルキル、C1〜C3ハロアルキルチオ(C1〜C3)アルキル、C1〜C3アルキルスルフィニル(C1〜C3)アルキル、C1〜C3ハロアルキルスルフィニル(C1〜C3)アルキル、C1〜C3アルキルスルホニル(C1〜C3)アルキル、C1〜C3ハロアルキルスルホニル(C1〜C3)アルキル、シアノ(C1〜C6)アルキル、C1〜C6アルコキシ、C1〜C6ハロアルコキシ、C1〜C3ハロアルコキシ(C1〜C3)ハロアルコキシ、C1〜C6アルキルスルホニルオキシ、C1〜C6ハロアルキルスルホニルオキシ、(Z1)p1によって置換されていてもよいフェノキシ、-O(L-45)、C1〜C6アルキルチオ、C1〜C6ハロアルキルチオ、C3〜C8シクロアルキルチオ、C1〜C6アルキルスルフィニル、C1〜C6ハロアルキルスルフィニル、C3〜C8シクロアルキルスルフィニル、C1〜C6アルキルスルホニル、C1〜C6ハロアルキルスルホニル、C3〜C8シクロアルキルスルホニル、C1〜C6アルキルアミノスルホニル、ジ(C1〜C6アルキル)アミノスルホニル、-C(O)NH2、C1〜C6アルキルアミノカルボニル、ジ(C1〜C6アルキル)アミノカルボニル、-C(S)NH2又はトリ(C1〜C6アルキル)シリルを表し、p1が2以上の整数を表すとき、各々のZ2は互いに同一であっても又は互いに相異なっていてもよく、
さらに、2つのZ2が隣接する場合には、隣接する2つのZ2は-OCF2O-又は-OCF2CF2O-を形成することにより、それぞれが結合する炭素原子と共に5員環又は6員環を形成してもよく、
R15は、C1〜C6アルキル又は(Z1)p1によって置換されていてもよいフェニルを表し、
R18は、-OR28、-N(R29)R28、-S(O)rR30、-CH=NOH又は-CH=NOR33を表し、
R28は、C1〜C6アルキル、C1〜C6アルキルカルボニル、C1〜C6アルコキシカルボニル、C1〜C6アルキルアミノカルボニル、ジ(C1〜C6アルキル)アミノカルボニル又はC1〜C6アルキルスルホニルを表し、
R29は、水素原子又はC1〜C6アルキルを表し、
R30は、C1〜C6アルキルを表し、
R33は、C1〜C6アルキルを表し、
mは、0〜2の整数を表し、
nは、0〜2の整数を表す置換ベンズアニリド化合物及びその塩より選ばれる1種又は2種以上と、請求項1記載の化合物群Aより選ばれる化合物の1種又は2種以上を含有する殺虫、殺ダニ、殺線虫、殺菌又は殺バクテリア組成物。 In the general formula (1) according to claim 1, G is a formula G-4, a formula G-5, a formula G-6, a formula G-7, a formula G-11, a formula G-13, a formula G-14, Represents a non-aromatic heterocyclic ring represented by any one of Formula G-15, Formula G-17, Formula G-18 or Formula G-23, or a cycloalkyl ring represented by Formula G-71;
Y is a halogen atom, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy or C 1 -C 4 alkylthio, when n is 2, each Y is identical to each other May be different from each other,
R 1 represents a hydrogen atom,
R 2 represents a hydrogen atom or C 1 -C 6 alkyl,
R 3 represents C 1 -C 8 alkyl, (C 1 -C 8 ) alkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl optionally substituted by R 18 ,
R 4 is C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, phenyl optionally substituted by (Z 2 ) p 1 , 2-naphthyl, L-1 to L-4, L-15 to L- 17, L-19, L-20, L-22, L-23, L-45, L-46 or L-47,
R 5 is
(a). When R 4 represents C 1 -C 6 alkyl or C 1 -C 6 haloalkyl, (Z 2 ) phenyl optionally substituted by p 1, 1-naphthyl, 2-naphthyl, L-1 L-5, L-8 to L-24, L-28 to L-36, L-39, L-41, L-42, L-45 to L-47 or L-50
(b) R 4 is phenyl, 2-naphthyl, L-1 to L-4, L-15 to L-17, L-19, L-20, L optionally substituted by (Z 2 ) p1 -22, to represent a L-23, L-45, L-46 or L-47, a hydrogen atom, a halogen atom, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 alkylthio, C 1 -C 6 alkylsulfinyl, C 1 -C 6 alkylsulfonyl or di (C 1 ~C 6) alkyl amino,
R 6a , R 6b , R 6c and R 6d represent a hydrogen atom,
R 6e represents C 1 -C 6 alkyl;
R 6i represents a hydrogen atom,
R 6j and R 6k each independently represent a hydrogen atom, a halogen atom or cyano,
Z 2 is a halogen atom, cyano, nitro, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 3 alkoxy (C 1 -C 3) alkyl, C 1 -C 3 haloalkoxy (C 1 -C 3) alkyl, C 1 -C 3 alkylthio (C 1 ~C 3) alkyl, C 1 -C 3 haloalkylthio (C 1 ~C 3) alkyl, C 1 -C 3 alkylsulfinyl (C 1 -C 3 ) alkyl, C 1 -C 3 haloalkylsulfinyl (C 1 -C 3) alkyl, C 1 -C 3 alkylsulfonyl (C 1 -C 3) alkyl, C 1 -C 3 haloalkylsulfonyl (C 1 -C 3) alkyl , cyano (C 1 ~C 6) alkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 3 haloalkoxy (C 1 ~C 3) haloalkoxy, C 1 -C 6 alkylsulfonyl oxy, C 1 -C 6 haloalkylsulfonyloxy, (Z 1) p1 may be substituted by phenoxy, -O (L-45), C 1 ~C 6 alkylthio, C 1 -C 6 haloalkylthio, C 3 -C 8 cycloalkylthio, C 1 -C 6 alkylsulfinyl, C 1 -C 6 haloalkylsulfinyl, C 3 -C 8 cycloalkylsulfinyl, C 1 -C 6 alkylsulfonyl, C 1 -C 6 haloalkylsulfonyl, C 3 -C 8 cycloalkylsulfonyl, C 1 -C 6 alkylaminosulfonyl, di (C 1 -C 6 alkyl) aminosulfonyl, -C (O) NH 2, C 1 ~C 6 alkylaminocarbonyl, di (C 1 -C 6 alkyl) represents aminocarbonyl, -C (S) NH 2 or tri (C 1 -C 6 alkyl) silyl, when p1 represents an integer of 2 or more, each Z 2 may be the same as or different from each other;
Further, when two Z 2 are adjacent to each other, the two adjacent Z 2 form —OCF 2 O— or —OCF 2 CF 2 O— to form a 5-membered ring or a carbon atom to which each is bonded. A 6-membered ring may be formed,
R 15 represents C 1 -C 6 alkyl or phenyl optionally substituted by (Z 1 ) p 1 ,
R 18 represents -OR 28 , -N (R 29 ) R 28 , -S (O) r R 30 , -CH = NOH or -CH = NOR 33 ,
R 28 is C 1 -C 6 alkyl, C 1 -C 6 alkylcarbonyl, C 1 -C 6 alkoxycarbonyl, C 1 -C 6 alkylaminocarbonyl, di (C 1 -C 6 alkyl) aminocarbonyl or C 1 It represents -C 6 alkylsulfonyl,
R 29 represents a hydrogen atom or C 1 -C 6 alkyl,
R 30 represents C 1 -C 6 alkyl,
R 33 represents C 1 -C 6 alkyl;
m represents an integer of 0 to 2,
n is an insecticide containing 1 or 2 or more types selected from a substituted benzanilide compound and an salt thereof representing an integer of 0 to 2 and a compound selected from the compound group A of claim 1 , Acaricidal, nematicidal, bactericidal or bactericidal composition.
一般式(2):
Xは、ハロゲン原子、シアノ、ニトロ、アジド、-SCN、-SF5、C1〜C6アルキル、R7によって任意に置換された(C1〜C6)アルキル、C3〜C8シクロアルキル、R7によって任意に置換された(C3〜C8)シクロアルキル、C2〜C6アルケニル、R7によって任意に置換された(C2〜C6)アルケニル、C3〜C8シクロアルケニル、C3〜C8ハロシクロアルケニル、C2〜C6アルキニル、R7によって任意に置換された(C2〜C6)アルキニル、-OH、-OR8、-OS(O)2R8、-SH、-S(O)rR8、-CHO、-C(O)R9、-C(O)OR9、-C(O)SR9、-C(O)NHR10、-C(O)N(R10)R9、-C(S)OR9、-C(S)SR9、-C(S)NHR10、-C(S)N(R10)R9、-CH=NOR11、-C(R9)=NOR11、-S(O)2OR9、-S(O)2NHR10、-S(O)2N(R10)R9、-Si(R13)(R14)R12、フェニル、(Z1)p1によって置換されたフェニル、L又はMを表し、mが2、3又は4を表すとき、各々のXは互いに同一であっても又は互いに相異なっていてもよく、
さらに、2つのXが隣接する場合には、隣接する2つのXは-CH2CH2CH2-, -CH2CH2O-, -CH2OCH2-, -OCH2O-, -CH2CH2S-, -CH2SCH2-, -CH2CH2N(R15)-, -CH2N(R15)CH2-, -CH2CH2CH2CH2-, -CH2CH2CH2O-, -CH2CH2OCH2-, -CH2OCH2O-, -OCH2CH2O-, -OCH2CH2S-, -CH2CH=CH-, -OCH=CH-, -SCH=CH-, -N(R15)CH=CH-, -OCH=N-, -SCH=N-, -N(R15)CH=N-, -N(R15)N=CH-, -CH=CHCH=CH-, -OCH2CH=CH-, -N=CHCH=CH-, -N=CHCH=N-又は-N=CHN=CH-を形成することにより、2つのXのそれぞれが結合する炭素原子と共に5員環又は6員環を形成してもよく、このとき、環を形成する各々の炭素原子に結合した水素原子はZ1によって任意に置換されていてもよく、さらに、同時に2個以上のZ1で置換されている場合、各々のZ1は互いに同一であっても又は互いに相異なっていてもよく、
Yは、ハロゲン原子、シアノ、ニトロ、C1〜C6アルキル、R7によって任意に置換された(C1〜C6)アルキル、C3〜C8シクロアルキル、-OR8、-S(O)rR8、-NH2、C1〜C6アルキルアミノ、ジ(C1〜C6アルキル)アミノ又は-Si(R13)(R14)R12を表し、nが2、3又は4を表すとき、各々のYは互いに同一であっても又は互いに相異なっていてもよく、
さらに、2つのYが隣接する場合には、隣接する2つのYは-CH2CH2CH2-, -CH2CH2O-, -CH2OCH2-, -OCH2O-, -CH2CH2S-, -CH2SCH2-, -SCH2S-, -CH2CH2CH2CH2-, -CH2CH2CH2O-, -CH2CH2OCH2-, -CH2OCH2O-, -OCH2CH2O-, -OCH2CH2S-, -SCH2CH2S-, -OCH=N-又は-SCH=N-を形成することにより、2つのYのそれぞれが結合する炭素原子と共に5員環又は6員環を形成してもよく、このとき、環を形成する各々の炭素原子に結合した水素原子はZ1によって任意に置換されていてもよく、さらに、同時に2個以上のZ1で置換されている場合、各々のZ1は互いに同一であっても又は互いに相異なっていてもよく、
R1及びR2は、各々独立して水素原子、シアノ、C1〜C12アルキル、R18によって任意に置換された(C1〜C12)アルキル、C3〜C12アルケニル、C3〜C12ハロアルケニル、C3〜C12アルキニル、C3〜C12ハロアルキニル、-OH、C1〜C8アルコキシ、C1〜C6アルキルチオ、C1〜C6ハロアルキルチオ、フェニルチオ、(Z1)p1によって置換されたフェニルチオ、-S(O)2R9、-SN(R20)R19、-S(O)2N(R10)R9、-N(R22)R21、-C(O)R9、-C(O)OR9、-C(O)SR9、-C(O)N(R10)R9、-C(S)OR9、-C(S)SR9、-C(S)N(R10)R9、フェニル又は(Z1)p1によって置換されたフェニルを表すか、或いは、R2はR3と一緒になってC2〜C6アルキレン鎖を形成することにより、結合する窒素原子と共に3〜7員環を形成してもよいことを表し、このときこのアルキレン鎖は酸素原子、硫黄原子又は窒素原子を1個含んでもよく、且つハロゲン原子、C1〜C6アルキル基、C1〜C6ハロアルキル基、C1〜C6アルコキシ基、C1〜C6アルキルカルボニル基又はC1〜C6アルコキシカルボニル基によって任意に置換されていてもよく、
R3は、水素原子、シアノ、C1〜C12アルキル、R18によって任意に置換された(C1〜C12)アルキル、C3〜C12シクロアルキル、R18によって任意に置換された(C3〜C12)シクロアルキル、C3〜C12アルケニル、R18によって任意に置換された(C3〜C12)アルケニル、C3〜C12シクロアルケニル、C3〜C12ハロシクロアルケニル、C3〜C12アルキニル、R18によって任意に置換された(C3〜C12)アルキニル、-OH、C1〜C8アルコキシ、C3〜C8アルケニルオキシ、C3〜C8ハロアルケニルオキシ、フェノキシ、(Z1)p1によって置換されたフェノキシ、フェニル(C1〜C4)アルコキシ、(Z1)p1によって置換されたフェニル(C1〜C4)アルコキシ、-N(R22)R21、フェニル、(Z1)p1によって置換されたフェニル、L又はMを表し、
R4は、C1〜C6アルキル、C1〜C6ハロアルキル、R23によって任意に置換された(C1〜C6)アルキル、R23によって任意に置換された(C1〜C6)ハロアルキル、C3〜C8シクロアルキル、C3〜C8ハロシクロアルキル、R23によって任意に置換された(C3〜C8)シクロアルキル、R23によって任意に置換された(C3〜C8)ハロシクロアルキル、C3〜C6アルケニル、C3〜C6ハロアルケニル、C3〜C6アルキニル、C3〜C6ハロアルキニル、フェニル、(Z1)p1によって置換されたフェニル、L又はMを表し、
R5は、シアノ、R23によって任意に置換された(C1〜C6)アルキル、R23によって任意に置換された(C1〜C6)ハロアルキル、R23によって任意に置換された(C3〜C8)シクロアルキル、R23によって任意に置換された(C3〜C8)ハロシクロアルキル、R23によって任意に置換された(C2〜C6)アルケニル、C3〜C8シクロアルケニル、C3〜C8ハロシクロアルケニル、R23によって任意に置換された(C2〜C6)アルキニル、-OR8、-S(O)rR8、-N(R10)R9、-CHO、-C(O)R9、-CH=NOR11、-C(R9)=NOR11、-C(O)OR9、-C(O)SR9、-C(O)NHR10、-C(O)N(R10)R9、-C(S)OR9、-C(S)SR9、-C(S)NHR10、-C(S)N(R10)R9、フェニル、(Z1)p1によって置換されたフェニル、ビフェニル、(Z1)p1によって置換されたビフェニル、フェノキシフェニル、(Z1)p1によって置換されたフェノキシフェニル、ピリジルオキシフェニル、(Z1)p1によって置換されたピリジルオキシフェニル、フェニルチオフェニル、(Z1)p1によって置換されたフェニルチオフェニル、フェニルスルフィニルフェニル、(Z1)p1によって置換されたフェニルスルフィニルフェニル、フェニルスルホニルフェニル、(Z1)p1によって置換されたフェニルスルホニルフェニル、L又はMを表すか、或いは、隣接位に存在するYと一緒になってC2〜C3アルキレン鎖を形成することにより、ベンゼン環と縮合する5〜6員環を形成してもよいことを表し、このときこのアルキレン鎖は酸素原子、硫黄原子又は窒素原子を1個含んでもよく、且つハロゲン原子又はC1〜C6ハロアルキル基によって任意に置換されていてもよく、
R6vは、水素原子、C1〜C6アルキル、C1〜C6ハロアルキル、R23によって任意に置換された(C1〜C6)アルキル、R23によって任意に置換された(C1〜C6)ハロアルキル、C3〜C8シクロアルキル、C3〜C6アルケニル、C3〜C6ハロアルケニル、フェニル(C3〜C6)アルケニル、(Z1)p1によって置換されたフェニル(C3〜C6)アルケニル、C3〜C8シクロアルケニル、C3〜C6アルキニル、C3〜C6ハロアルキニル、フェニル(C3〜C6)アルキニル、(Z1)p1によって置換されたフェニル(C3〜C6)アルキニル、-S(O)2R9、-C(O)R9、-C(O)OR9、-C(O)SR9、-C(S)OR9、-C(S)SR9、-C(O)NHR10、-C(O)N(R10)R9、-C(S)NHR10、-C(S)N(R10)R9、-Si(R13)(R14)R12、-P(O)(OR24)2、-P(S)(OR24)2又はMを表し、
Lは、式L-1から式L-58までの何れかで表される芳香族複素環を表し、
さらに、2つのZ1が隣接する場合には、隣接する2つのZ1は-CH2CH2CH2-, -CH2CH2O-, -CH2OCH2-, -OCH2O-, -CH2CH2S-, -CH2SCH2-, -CH2CH2CH2CH2-, -CH2CH2CH2O-, -CH2CH2OCH2-, -CH2OCH2O-, -OCH2CH2O-, -OCH2CH2S-又は-CH=CHCH=CH-を形成することにより、2つのZ1のそれぞれが結合する炭素原子と共に5員環又は6員環を形成してもよく、このとき、環を形成する各々の炭素原子に結合した水素原子はハロゲン原子又はC1〜C6アルキル基によって任意に置換されていてもよく、
R7は、ハロゲン原子、シアノ、C3〜C8シクロアルキル、C3〜C8ハロシクロアルキル、-OH、-OR8、-SH、-S(O)rR8、-N(R10)R9、-N(R10)CHO、-N(R10)C(O)R9、-N(R10)C(O)OR9、-N(R10)C(O)SR9、-N(R10)C(S)OR9、-N(R10)C(S)SR9、-N(R10)S(O)2R9、-C(O)OR9、-C(O)N(R10)R9、-Si(R13)(R14)R12、フェニル、(Z1)p1によって置換されたフェニル、L又はMを表し、
R8は、C1〜C6アルキル、R27によって任意に置換された(C1〜C6)アルキル、C3〜C8シクロアルキル、R27によって任意に置換された(C3〜C8)シクロアルキル、C2〜C6アルケニル、R27によって任意に置換された(C2〜C6)アルケニル、C3〜C8シクロアルケニル、C3〜C8ハロシクロアルケニル、C3〜C6アルキニル、R27によって任意に置換された(C3〜C6)アルキニル、フェニル、(Z1)p1によって置換されたフェニル、L又はMを表し、
R9は、C1〜C6アルキル、C1〜C6ハロアルキル、C3〜C6シクロアルキル(C1〜C4)アルキル、C1〜C6アルコキシ(C1〜C4)アルキル、C1〜C6アルキルチオ(C1〜C4)アルキル、シアノ(C1〜C6)アルキル、フェニル(C1〜C4)アルキル、(Z1)p1によって置換されたフェニル(C1〜C4)アルキル、L-(C1〜C4)アルキル、M-(C1〜C4)アルキル、C3〜C8シクロアルキル、C3〜C8ハロシクロアルキル、C3〜C6アルケニル、C3〜C6ハロアルケニル、C3〜C6アルキニル、フェニル又は(Z1)p1によって置換されたフェニルを表し、
R10は、水素原子又はC1〜C6アルキルを表すか、或いは、R9とR10とが一緒になってC2〜C6アルキレン鎖を形成することにより、結合する原子と共に3〜7員環を形成してもよいことを表し、このときこのアルキレン鎖は酸素原子、硫黄原子又は窒素原子を1個含んでもよく、且つハロゲン原子、C1〜C6アルキル基、C1〜C6アルコキシ基、ホルミル基、C1〜C6アルキルカルボニル基又はC1〜C6アルコキシカルボニル基によって任意に置換されていてもよく、
R11は、水素原子、C1〜C6アルキル、C1〜C6ハロアルキル、フェニル(C1〜C4)アルキル、(Z1)p1によって置換されたフェニル(C1〜C4)アルキル、C3〜C6アルケニル、C3〜C6ハロアルケニル、C3〜C6アルキニル又はC3〜C6ハロアルキニルを表すか、或いは、R11はR9と一緒になってC2〜C4アルキレン鎖を形成することにより、結合する原子と共に5〜7員環を形成してもよいことを表し、このときこのアルキレン鎖は酸素原子、硫黄原子又は窒素原子を1個含んでもよく、且つハロゲン原子又はC1〜C6アルキル基によって任意に置換されていてもよく、
R12は、C1〜C6アルキル、C1〜C6ハロアルキル、C3〜C6アルケニル、フェニル又は(Z1)p1によって置換されたフェニルを表し、
R13及びR14は、各々独立してC1〜C6アルキル又はC1〜C6ハロアルキルを表し、
R15は、水素原子、C1〜C6アルキル、C1〜C6ハロアルキル、C1〜C6アルコキシカルボニル(C1〜C4)アルキル、C1〜C6ハロアルコキシカルボニル(C1〜C4)アルキル、フェニル(C1〜C4)アルキル、(Z1)p1によって置換されたフェニル(C1〜C4)アルキル、C3〜C6アルケニル、C3〜C6ハロアルケニル、C3〜C6アルキニル、C3〜C6ハロアルキニル、C1〜C6アルコキシ、C1〜C6アルコキシカルボニル、C1〜C6ハロアルコキシカルボニル、フェニル又は(Z1)p1によって置換されたフェニルを表し、
R18は、ハロゲン原子、シアノ、ニトロ、C3〜C8シクロアルキル、C3〜C8ハロシクロアルキル、-OR28、-N(R29)R28、-SH、-S(O)rR30、-SO2NHR32、-SO2N(R32)R31、-CHO、-C(O)R31、-C(O)OH、-C(O)OR31、-C(O)SR31、-C(O)NHR32、-C(O)N(R32)R31、-C(O)C(O)OR31、-C(R34)=NOH、-C(R34)=NOR33、-Si(R13)(R14)R12、-P(O)(OR24)2、-P(S)(OR24)2、-P(フェニル)2、-P(O)(フェニル)2、フェニル、(Z1)p1によって置換されたフェニル、L又はMを表し、
R19は、C1〜C12アルキル、C1〜C12ハロアルキル、C1〜C12アルコキシ(C1〜C12)アルキル、シアノ(C1〜C12)アルキル、C1〜C12アルコキシカルボニル(C1〜C12)アルキル、フェニル(C1〜C4)アルキル、(Z1)p1によって置換されたフェニル(C1〜C4)アルキル、C3〜C12アルケニル、C3〜C12ハロアルケニル、C3〜C12アルキニル、C3〜C12ハロアルキニル、C1〜C12アルキルカルボニル、C1〜C12アルコキシカルボニル、フェニル又は(Z1)p1によって置換されたフェニルを表し、
R20は、C1〜C12アルキル、C1〜C12ハロアルキル、C1〜C12アルコキシ(C1〜C12)アルキル、シアノ(C1〜C12)アルキル、C1〜C12アルコキシカルボニル(C1〜C12)アルキル、フェニル(C1〜C4)アルキル、(Z1)p1によって置換されたフェニル(C1〜C4)アルキル、C3〜C12アルケニル、C3〜C12ハロアルケニル、C3〜C12アルキニル、C3〜C12ハロアルキニル、フェニル又は(Z1)p1によって置換されたフェニルを表すか、或いは、R19とR20とが一緒になってC4〜C7アルキレン鎖を形成することにより、結合する窒素原子と共に5〜8員環を形成してもよいことを表し、このときこのアルキレン鎖は酸素原子又は硫黄原子を1個含んでもよく、且つC1〜C4アルキル基又はC1〜C4アルコキシ基によって任意に置換されていてもよく、
R21は、水素原子、C1〜C6アルキル、C1〜C6ハロアルキル、フェニル(C1〜C4)アルキル、(Z1)p1によって置換されたフェニル(C1〜C4)アルキル、C3〜C6アルケニル、C3〜C6ハロアルケニル、C3〜C6アルキニル、-CHO、C1〜C6アルキルカルボニル、C1〜C6ハロアルキルカルボニル、C1〜C6アルコキシカルボニル、C1〜C6ハロアルコキシカルボニル、フェニル(C1〜C4)アルコキシカルボニル、(Z1)p1によって置換されたフェニル(C1〜C4)アルコキシカルボニル、フェノキシカルボニル、(Z1)p1によって置換されたフェノキシカルボニル、フェニルカルボニル、(Z1)p1によって置換されたフェニルカルボニル、フェニル又は(Z1)p1によって置換されたフェニルを表し、
R22は、水素原子、C1〜C6アルキル、-CHO、C1〜C6アルキルカルボニル、C1〜C6ハロアルキルカルボニル又はC1〜C6アルコキシカルボニルを表し、
R23は、シアノ、C3〜C8シクロアルキル、C3〜C8ハロシクロアルキル、-OH、-OR8、-SH、-S(O)rR8、-N(R10)R9、-N(R10)CHO、-N(R10)C(O)R9、-N(R10)C(O)OR9、-N(R10)C(O)SR9、-N(R10)C(S)OR9、-N(R10)C(S)SR9、-N(R10)S(O)2R9、-C(O)OR9、-C(O)N(R10)R9、-Si(R13)(R14)R12、フェニル、(Z1)p1によって置換されたフェニル、L又はMを表し、
R24は、C1〜C6アルキル又はC1〜C6ハロアルキルを表し、
R25は、ハロゲン原子、シアノ、C1〜C6アルキル、C1〜C6ハロアルキル、ヒドロキシ(C1〜C6)アルキル、C1〜C4アルコキシ(C1〜C4)アルキル、C1〜C4アルコキシカルボニル(C1〜C4)アルキル、C1〜C6アルコキシ、C1〜C6アルコキシカルボニル、フェニル又は(Z1)p1によって置換されたフェニルを表し、q1, q2, q3又はq4が2以上の整数を表すとき、各々のR25は互いに同一であっても、または互いに相異なっていてもよく、
R26は、水素原子、C1〜C6アルキル、C1〜C6ハロアルキル、-CHO、C1〜C6アルキルカルボニル、C1〜C6ハロアルキルカルボニル、フェニル(C1〜C4)アルキルカルボニル、(Z1)p1によって置換されたフェニル(C1〜C4)アルキルカルボニル、C1〜C6アルコキシカルボニル、C1〜C6ハロアルコキシカルボニル、フェニル(C1〜C4)アルコキシカルボニル、(Z1)p1によって置換されたフェニル(C1〜C4)アルコキシカルボニル、C1〜C6アルキルチオカルボニル、C1〜C6アルコキシチオカルボニル、C1〜C6アルキルアミノカルボニル、ジ(C1〜C6アルキル)アミノカルボニル、C1〜C6アルキルアミノチオカルボニル、ジ(C1〜C6アルキル)アミノチオカルボニル、フェニルカルボニル、(Z1)p1によって置換されたフェニルカルボニル、C1〜C6アルキルスルホニル、C1〜C6ハロアルキルスルホニル、フェニルスルホニル、(Z1)p1によって置換されたフェニルスルホニル、-P(O)(OR24)2又は-P(S)(OR24)2を表し、
R27は、ハロゲン原子、シアノ、C3〜C8シクロアルキル、C3〜C8ハロシクロアルキル、C1〜C6アルコキシ、C1〜C6ハロアルコキシ、C1〜C6アルキルチオ、C1〜C6ハロアルキルチオ、C1〜C6アルキルスルホニル、C1〜C6ハロアルキルスルホニル、C1〜C6アルキルアミノ、ジ(C1〜C6アルキル)アミノ、-CHO、C1〜C6アルキルカルボニル、C1〜C6ハロアルキルカルボニル、C1〜C6アルコキシカルボニル、C1〜C6ハロアルコキシカルボニル、-CH=NOR11、-C(R9)=NOR11、フェニル、(Z1)p1によって置換されたフェニル、L又はMを表し、
R28は、水素原子、C1〜C8アルキル、R35によって任意に置換された(C1〜C8)アルキル、C3〜C8シクロアルキル、R35によって任意に置換された(C3〜C8)シクロアルキル、C3〜C8アルケニル、R35によって任意に置換された(C3〜C8)アルケニル、C3〜C8アルキニル、R35によって任意に置換された(C3〜C8)アルキニル、-CHO、-C(O)R31、-C(O)OR31、-C(O)SR31、-C(O)NHR32、-C(O)N(R32)R31、-C(O)C(O)R31、-C(O)C(O)OR31、-C(S)R31、-C(S)OR31、-C(S)SR31、-C(S)NHR32、-C(S)N(R32)R31、-S(O)2R31、-S(O)2N(R32)R31、-Si(R13)(R14)R12、-P(O)(OR24)2、-P(S)(OR24)2、フェニル、(Z1)p1によって置換されたフェニル、L又はMを表し、
R29は、水素原子、C1〜C6アルキル、C1〜C6ハロアルキル、C3〜C6シクロアルキル又はC1〜C6アルコキシを表すか、或いは、R28とR29とが一緒になってC2〜C5アルキレン鎖を形成することにより、結合する窒素原子と共に3〜6員環を形成してもよいことを表し、このときこのアルキレン鎖は酸素原子又は硫黄原子を1個含んでもよく、且つハロゲン原子、C1〜C6アルキル基、C1〜C6アルコキシ基、フェニル基又は(Z1)p1によって置換されたフェニル基によって置換されていてもよく、
R30は、C1〜C8アルキル、R35によって任意に置換された(C1〜C8)アルキル、C3〜C8シクロアルキル、R35によって任意に置換された(C3〜C8)シクロアルキル、C3〜C8アルケニル、R35によって任意に置換された(C3〜C8)アルケニル、C3〜C8アルキニル、R35によって任意に置換された(C3〜C8)アルキニル、-SH、C1〜C6アルキルチオ、C1〜C6ハロアルキルチオ、フェニルチオ、(Z1)p1によって置換されたフェニルチオ、-CHO、-C(O)R31、-C(O)OR31、-C(O)SR31、-C(O)NHR32、-C(O)N(R32)R31、-C(O)C(O)R31、-C(O)C(O)OR31、-C(S)R31、-C(S)OR31、-C(S)SR31、-C(S)NHR32、-C(S)N(R32)R31、-P(O)(OR24)2、-P(S)(OR24)2、フェニル、(Z1)p1によって置換されたフェニル、L-18、L-21、L-25、L-30〜L-35、L-45、L-48、L-49又はMを表し、
R31は、C1〜C6アルキル、C1〜C6ハロアルキル、C3〜C8シクロアルキル(C1〜C4)アルキル、C1〜C6アルコキシ(C1〜C4)アルキル、C1〜C6ハロアルコキシ(C1〜C4)アルキル、C1〜C6アルキルチオ(C1〜C4)アルキル、C1〜C6ハロアルキルチオ(C1〜C4)アルキル、C1〜C6アルキルスルホニル(C1〜C4)アルキル、C1〜C6ハロアルキルスルホニル(C1〜C4)アルキル、シアノ(C1〜C6)アルキル、C1〜C6アルキルカルボニル(C1〜C4)アルキル、C1〜C6ハロアルキルカルボニル(C1〜C4)アルキル、C1〜C6アルコキシカルボニル(C1〜C4)アルキル、ジ(C1〜C6アルキル)アミノカルボニル(C1〜C4)アルキル、トリ(C1〜C4アルキル)シリル(C1〜C4)アルキル、フェニル(C1〜C4)アルキル、(Z1)p1によって置換されたフェニル(C1〜C4)アルキル、L-(C1〜C4)アルキル、M-(C1〜C4)アルキル、C3〜C8シクロアルキル、C3〜C8ハロシクロアルキル、C2〜C6アルケニル、C2〜C6ハロアルケニル、C2〜C6アルキニル、C2〜C6ハロアルキニル、フェニル、(Z1)p1によって置換されたフェニル、L又はMを表し、
R32は、水素原子、C1〜C6アルキル、C1〜C6ハロアルキル、フェニル又は(Z1)p1によって置換されたフェニルを表すか、或いは、R31とR32とが一緒になってC2〜C5アルキレン鎖を形成することにより、結合する窒素原子と共に3〜6員環を形成してもよいことを表し、このときこのアルキレン鎖は酸素原子、硫黄原子又は窒素原子を1個含んでもよく、且つハロゲン原子、C1〜C6アルキル基、C1〜C6アルコキシ基、ホルミル基、C1〜C6アルキルカルボニル基、C1〜C6アルコキシカルボニル基、フェニル基又は(Z1)p1によって置換されたフェニル基によって任意に置換されていてもよく、
R33は、水素原子、C1〜C8アルキル、R35によって任意に置換された(C1〜C8)アルキル、C3〜C8シクロアルキル、C3〜C8アルケニル、R35によって任意に置換された(C3〜C8)アルケニル、C3〜C8アルキニル又はR35によって任意に置換された(C3〜C8)アルキニルを表し、
R34は、水素原子、C1〜C6アルキル、C1〜C6ハロアルキル、C3〜C8シクロアルキル(C1〜C4)アルキル、C1〜C6アルコキシ(C1〜C4)アルキル、C1〜C6ハロアルコキシ(C1〜C4)アルキル、C1〜C6アルキルチオ(C1〜C4)アルキル、C1〜C6ハロアルキルチオ(C1〜C4)アルキル、C1〜C6アルキルスルホニル(C1〜C4)アルキル、C1〜C6ハロアルキルスルホニル(C1〜C4)アルキル、フェニル(C1〜C4)アルキル、(Z1)p1によって置換されたフェニル(C1〜C4)アルキル、フェニル又は(Z1)p1によって置換されたフェニルを表し、
R35は、ハロゲン原子、シアノ、ニトロ、C3〜C8シクロアルキル、C3〜C8ハロシクロアルキル、-OH、-OR36、-SH、-S(O)rR36、-NHR37、-N(R37)R36、-CHO、-C(O)R31、-C(O)OR31、-C(O)SR31、-C(O)NHR32、-C(O)N(R32)R31、-C(O)C(O)OR31、-CH=NOR11、-C(R9)=NOR11、-Si(R13)(R14)R12、-P(O)(OR24)2、-P(S)(OR24)2、-P(フェニル)2、-P(O)(フェニル)2、フェニル、(Z1)p1によって置換されたフェニル、L又はMを表し、
R36は、C1〜C6アルキル、C1〜C6ハロアルキル、C1〜C6アルコキシ(C1〜C4)アルキル、C1〜C6アルキルチオ(C1〜C4)アルキル、フェニル(C1〜C4)アルキル、(Z1)p1によって置換されたフェニル(C1〜C4)アルキル、C3〜C8シクロアルキル、C3〜C8ハロシクロアルキル、C3〜C6アルケニル、C3〜C6ハロアルケニル、C3〜C8シクロアルケニル、C3〜C8ハロシクロアルケニル、C3〜C6アルキニル、C3〜C6ハロアルキニル、-CHO、C1〜C6アルキルカルボニル、C1〜C6ハロアルキルカルボニル、C1〜C6アルコキシカルボニル、C1〜C6ハロアルコキシカルボニル、C1〜C6アルキルアミノカルボニル、ジ(C1〜C6アルキル)アミノカルボニル、フェニルカルボニル、(Z1)p1によって置換されたフェニルカルボニル、C1〜C6アルキルアミノチオカルボニル、ジ(C1〜C6アルキル)アミノチオカルボニル、フェニル、(Z1)p1によって置換されたフェニル、L又はMを表し、
R37は、水素原子、C1〜C6アルキル、C1〜C6ハロアルキル、C3〜C8シクロアルキル、C3〜C6アルケニル、C3〜C6アルキニル、C1〜C6アルキルカルボニル、C1〜C6ハロアルキルカルボニル、C1〜C6アルコキシカルボニル、C1〜C6ハロアルコキシカルボニル、フェノキシカルボニル、(Z1)p1によって置換されたフェノキシカルボニル、フェニルカルボニル、(Z1)p1によって置換されたフェニルカルボニル、C1〜C6アルキルスルホニル、C1〜C6ハロアルキルスルホニル、フェニル、(Z1)p1によって置換されたフェニル、L又はMを表すか、或いは、R36とR37とが一緒になってC2〜C5アルキレン鎖を形成することにより、結合する窒素原子と共に3〜6員環を形成してもよいことを表し、このときこのアルキレン鎖は酸素原子又は硫黄原子を1個含んでもよく、且つハロゲン原子又はメチル基によって置換されていてもよく、
mは、0〜4の整数を表し、
nは、0〜4の整数を表し、
p1は、1〜5の整数を表し、
p2は、0〜4の整数を表し、
p3は、0〜3の整数を表し、
p4は、0〜2の整数を表し、
p5は、0又は1の整数を表し、
q1は、0〜3の整数を表し、
q2は、0〜5の整数を表し、
q3は、0〜7の整数を表し、
q4は、0〜9の整数を表し、
rは、0〜2の整数を表し、
tは、0又は1の整数を表す。] 1 type (s) or 2 or more types chosen from the substituted benzanilide compound and its salt represented by the following General formula (2), and 1 type (s) or 2 or more types of the compound chosen from the compound group A of Claim 1 are contained Insecticidal, acaricidal, nematicidal, bactericidal or bactericidal composition.
General formula (2):
X is a halogen atom, cyano, nitro, azido, -SCN, -SF 5, C 1 ~C 6 alkyl, optionally substituted by R 7 (C 1 ~C 6) alkyl, C 3 -C 8 cycloalkyl , optionally substituted by R 7 (C 3 ~C 8) cycloalkyl, C 2 -C 6 alkenyl, optionally substituted by R 7 (C 2 ~C 6) alkenyl, C 3 -C 8 cycloalkenyl , C 3 -C 8 halocycloalkyl cycloalkenyl, C 2 -C 6 alkynyl, optionally substituted by R 7 (C 2 ~C 6) alkynyl, -OH, -OR 8, -OS ( O) 2 R 8, -SH, -S (O) r R 8 , -CHO, -C (O) R 9 , -C (O) OR 9 , -C (O) SR 9 , -C (O) NHR 10 , -C ( O) N (R 10 ) R 9 , -C (S) OR 9 , -C (S) SR 9 , -C (S) NHR 10 , -C (S) N (R 10 ) R 9 , -CH = NOR 11 , -C (R 9 ) = NOR 11 , -S (O) 2 OR 9 , -S (O) 2 NHR 10 , -S (O) 2 N (R 10 ) R 9 , -Si (R 13 ) (R 14) R 12, phenyl, (Z 1) phenyl substituted by p1, represents L or M, when m represents 2, 3 or 4, respectively X may be the even or different from each other the same as each other,
Further, when two Xs are adjacent to each other, the two adjacent Xs are -CH 2 CH 2 CH 2- , -CH 2 CH 2 O-, -CH 2 OCH 2- , -OCH 2 O-, -CH 2 CH 2 S-, -CH 2 SCH 2- , -CH 2 CH 2 N (R 15 )-, -CH 2 N (R 15 ) CH 2- , -CH 2 CH 2 CH 2 CH 2- , -CH 2 CH 2 CH 2 O-, -CH 2 CH 2 OCH 2- , -CH 2 OCH 2 O-, -OCH 2 CH 2 O-, -OCH 2 CH 2 S-, -CH 2 CH = CH-,- OCH = CH-, -SCH = CH-, -N (R 15 ) CH = CH-, -OCH = N-, -SCH = N-, -N (R 15 ) CH = N-, -N (R 15 By forming N = CH-, -CH = CHCH = CH-, -OCH 2 CH = CH-, -N = CHCH = CH-, -N = CHCH = N- or -N = CHN = CH- A 5-membered ring or a 6-membered ring may be formed together with the carbon atom to which each of two Xs is bonded. At this time, the hydrogen atom bonded to each carbon atom forming the ring is optionally substituted by Z 1 . Furthermore, when two or more Z 1 are substituted at the same time, each Z 1 may be the same as or different from each other,
Y is a halogen atom, cyano, nitro, C 1 -C 6 alkyl, optionally substituted by R 7 (C 1 ~C 6) alkyl, C 3 -C 8 cycloalkyl, -OR 8, -S (O ) r R 8 , —NH 2 , C 1 -C 6 alkylamino, di (C 1 -C 6 alkyl) amino or —Si (R 13 ) (R 14 ) R 12 , n is 2, 3 or 4 Each Y may be the same as or different from each other;
Further, when two Ys are adjacent to each other, the two adjacent Ys are —CH 2 CH 2 CH 2 —, —CH 2 CH 2 O—, —CH 2 OCH 2 —, —OCH 2 O—, —CH 2 CH 2 S-, -CH 2 SCH 2- , -SCH 2 S-, -CH 2 CH 2 CH 2 CH 2- , -CH 2 CH 2 CH 2 O-, -CH 2 CH 2 OCH 2 -,- By forming CH 2 OCH 2 O-, -OCH 2 CH 2 O-, -OCH 2 CH 2 S-, -SCH 2 CH 2 S-, -OCH = N- or -SCH = N- A 5-membered ring or a 6-membered ring may be formed together with the carbon atom to which each Y is bonded, and at this time, the hydrogen atom bonded to each carbon atom forming the ring may be optionally substituted by Z 1 In addition, in addition, when simultaneously substituted with two or more Z 1 , each Z 1 may be the same as or different from each other,
R 1 and R 2 are each independently a hydrogen atom, cyano, C 1 -C 12 alkyl, (C 1 -C 12 ) alkyl optionally substituted with R 18 , C 3 -C 12 alkenyl, C 3- C 12 haloalkenyl, C 3 -C 12 alkynyl, C 3 -C 12 haloalkynyl, -OH, C 1 -C 8 alkoxy, C 1 -C 6 alkylthio, C 1 -C 6 haloalkylthio, phenylthio, (Z 1 ) phenylthio substituted by p1, -S (O) 2 R 9, -SN (R 20) R 19, -S (O) 2 N (R 10) R 9, -N (R 22) R 21, - C (O) R 9 , -C (O) OR 9 , -C (O) SR 9 , -C (O) N (R 10 ) R 9 , -C (S) OR 9 , -C (S) SR 9 represents -C (S) N (R 10 ) R 9 , phenyl or phenyl substituted by (Z 1 ) p 1 , or R 2 together with R 3 is a C 2 to C 6 alkylene chain Represents that a 3- to 7-membered ring may be formed together with the nitrogen atom to be bonded, and at this time, this alkylene chain is an oxygen atom, a sulfur atom or a nitrogen atom. It may contain one child, and a halogen atom, C 1 -C 6 alkyl group, C 1 -C 6 haloalkyl group, C 1 -C 6 alkoxy group, C 1 -C 6 alkylcarbonyl group or a C 1 -C 6 Optionally substituted by an alkoxycarbonyl group,
R 3 represents a hydrogen atom, cyano, optionally substituted by C 1 -C 12 alkyl, optionally substituted by R 18 (C 1 ~C 12) alkyl, C 3 -C 12 cycloalkyl, R 18 ( C 3 -C 12) cycloalkyl, C 3 -C 12 alkenyl, optionally substituted by R 18 (C 3 ~C 12) alkenyl, C 3 -C 12 cycloalkenyl, C 3 -C 12 halo cycloalkenyl, C 3 -C 12 alkynyl, optionally substituted by R 18 (C 3 ~C 12) alkynyl, -OH, C 1 -C 8 alkoxy, C 3 -C 8 alkenyloxy, C 3 -C 8 haloalkenyloxy , phenoxy, (Z 1) p1 phenoxy substituted by phenyl (C 1 ~C 4) alkoxy, (Z 1) phenyl substituted by p1 (C 1 ~C 4) alkoxy, -N (R 22) R 21 represents phenyl, phenyl, L or M substituted by (Z 1 ) p1 ,
R 4 is optionally substituted by C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, optionally substituted by R 23 (C 1 ~C 6) alkyl, R 23 (C 1 ~C 6) haloalkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 halocycloalkyl, optionally substituted by R 23 (C 3 ~C 8) cycloalkyl, optionally substituted by R 23 (C 3 ~C 8) halocycloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 alkynyl, C 3 -C 6 haloalkynyl, phenyl, phenyl substituted by (Z 1) p1, L Or M,
R 5 is cyano, substituted optionally substituted by R 23 (C 1 ~C 6) alkyl, optionally substituted by R 23 (C 1 ~C 6) haloalkyl, optionally by R 23 (C 3 -C 8) cycloalkyl, optionally substituted by optionally substituted by R 23 (C 3 ~C 8) halocycloalkyl, R 23 (C 2 ~C 6 ) alkenyl, C 3 -C 8 cycloalkyl alkenyl, C 3 -C 8 halocycloalkyl cycloalkenyl, optionally substituted by R 23 (C 2 ~C 6) alkynyl, -OR 8, -S (O) r R 8, -N (R 10) R 9, -CHO, -C (O) R 9 , -CH = NOR 11 , -C (R 9 ) = NOR 11 , -C (O) OR 9 , -C (O) SR 9 , -C (O) NHR 10 , -C (O) N (R 10 ) R 9 , -C (S) OR 9 , -C (S) SR 9 , -C (S) NHR 10 , -C (S) N (R 10 ) R 9 , phenyl, (Z 1) phenyl substituted by p1, biphenyl, (Z 1) biphenyl substituted by p1, phenoxyphenyl, phenoxyphenyl substituted by (Z 1) p1, pyridinium Oxy phenyl, (Z 1) pyridyloxy phenyl substituted by p1, phenylthiophenyl, (Z 1) phenylthio phenyl substituted by p1, phenylsulfinyl phenyl, phenylsulfinyl phenyl substituted by (Z 1) p1 , Phenylsulfonylphenyl, phenylsulfonylphenyl substituted by (Z 1 ) p1 , L or M, or together with Y present in the adjacent position to form a C 2 -C 3 alkylene chain Represents that it may form a 5- to 6-membered ring that is condensed with a benzene ring, in which case the alkylene chain may contain one oxygen atom, sulfur atom or nitrogen atom, and a halogen atom or C 1 -C Optionally substituted by a 6- haloalkyl group,
R 6v is hydrogen atom, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, optionally substituted by R 23 (C 1 ~C 6) alkyl, optionally substituted by R 23 (C 1 ~ C 6) haloalkyl, C 3 -C 8 cycloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, phenyl (C 3 ~C 6) alkenyl, (Z 1) phenyl substituted by p1 (C 3 -C 6) alkenyl, C 3 -C 8 cycloalkenyl, C 3 -C 6 alkynyl, C 3 -C 6 haloalkynyl, phenyl (C 3 ~C 6) alkynyl, phenyl substituted by (Z 1) p1 (C 3 ~C 6) alkynyl, -S (O) 2 R 9 , -C (O) R 9, -C (O) OR 9, -C (O) SR 9, -C (S) OR 9, -C (S) SR 9 , -C (O) NHR 10 , -C (O) N (R 10 ) R 9 , -C (S) NHR 10 , -C (S) N (R 10 ) R 9 , -Si (R 13 ) (R 14 ) R 12 , -P (O) (OR 24 ) 2 , -P (S) (OR 24 ) 2 or M
L represents an aromatic heterocycle represented by any one of formulas L-1 to L-58,
Further, when two Z 1 are adjacent to each other, the two adjacent Z 1 are —CH 2 CH 2 CH 2 —, —CH 2 CH 2 O—, —CH 2 OCH 2 —, —OCH 2 O—, -CH 2 CH 2 S-, -CH 2 SCH 2- , -CH 2 CH 2 CH 2 CH 2- , -CH 2 CH 2 CH 2 O-, -CH 2 CH 2 OCH 2- , -CH 2 OCH 2 O-, -OCH 2 CH 2 O-, by forming a CH- -OCH 2 CH 2 S- or -CH = CHCH =, 5-membered ring or a 6-membered together with the carbon atom to which each of the two Z 1 is attached may form a ring, this time, the hydrogen atoms bonded to each carbon atom forming the ring may be optionally substituted by halogen atom or C 1 -C 6 alkyl group,
R 7 is a halogen atom, cyano, C 3 to C 8 cycloalkyl, C 3 to C 8 halocycloalkyl, —OH, —OR 8 , —SH, —S (O) r R 8 , —N (R 10 ) R 9 , -N (R 10 ) CHO, -N (R 10 ) C (O) R 9 , -N (R 10 ) C (O) OR 9 , -N (R 10 ) C (O) SR 9 , -N (R 10 ) C (S) OR 9 , -N (R 10 ) C (S) SR 9 , -N (R 10 ) S (O) 2 R 9 , -C (O) OR 9 ,- C (O) N (R 10 ) R 9 , -Si (R 13 ) (R 14 ) R 12 , phenyl, phenyl, L or M substituted by (Z 1 ) p1 ,
R 8 is optionally substituted by C 1 -C 6 alkyl, optionally substituted by R 27 (C 1 ~C 6) alkyl, C 3 -C 8 cycloalkyl, R 27 (C 3 ~C 8 ) cycloalkyl, C 2 -C 6 alkenyl, optionally substituted by R 27 (C 2 ~C 6) alkenyl, C 3 -C 8 cycloalkenyl, C 3 -C 8 halocycloalkyl cycloalkenyl, C 3 -C 6 It represents alkynyl, optionally substituted by R 27 (C 3 ~C 6) alkynyl, phenyl, phenyl, L or M, which is substituted by (Z 1) p1,
R 9 is C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl (C 1 -C 4 ) alkyl, C 1 -C 6 alkoxy (C 1 -C 4 ) alkyl, C 1 -C 6 alkylthio (C 1 ~C 4) alkyl, cyano (C 1 ~C 6) alkyl, phenyl (C 1 ~C 4) alkyl, (Z 1) phenyl substituted by p1 (C 1 ~C 4 ) alkyl, L- (C 1 ~C 4) alkyl, M- (C 1 ~C 4) alkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 halocycloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 alkynyl, represents phenyl substituted by phenyl or (Z 1) p1,
R 10 represents a hydrogen atom or C 1 -C 6 alkyl, or R 9 and R 10 together form a C 2 -C 6 alkylene chain to form 3-7 together with the atoms to be bonded. indicates that the members may form a ring, this time the alkylene chain an oxygen atom, may contain one sulfur atom or a nitrogen atom, and a halogen atom, C 1 -C 6 alkyl group, C 1 -C 6 alkoxy group, a formyl group, may be optionally substituted by C 1 -C 6 alkylcarbonyl group or a C 1 -C 6 alkoxycarbonyl group,
R 11 represents a hydrogen atom, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, phenyl (C 1 ~C 4) alkyl, (Z 1) phenyl substituted by p1 (C 1 ~C 4) alkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 alkynyl or C 3 -C 6 haloalkynyl, or R 11 together with R 9 is C 2 -C 4 By forming an alkylene chain, it indicates that a 5- to 7-membered ring may be formed together with the atoms to be bonded. At this time, the alkylene chain may contain one oxygen atom, sulfur atom or nitrogen atom, and halogen It may be optionally substituted by atom or a C 1 -C 6 alkyl group,
R 12 represents C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 alkenyl, phenyl or phenyl substituted by (Z 1 ) p 1 ,
R 13 and R 14 each independently represent C 1 -C 6 alkyl or C 1 -C 6 haloalkyl,
R 15 is a hydrogen atom, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxycarbonyl (C 1 -C 4 ) alkyl, C 1 -C 6 haloalkoxycarbonyl (C 1 -C 4) alkyl, phenyl (C 1 -C 4) alkyl, (Z 1) phenyl substituted by p1 (C 1 -C 4) alkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 alkynyl, C 3 -C 6 haloalkynyl, C 1 -C 6 alkoxy, C 1 -C 6 alkoxycarbonyl, C 1 -C 6 haloalkoxycarbonyl, phenyl substituted by phenyl or (Z 1) p1 Represent,
R 18 is a halogen atom, cyano, nitro, C 3 -C 8 cycloalkyl, C 3 -C 8 halocycloalkyl, -OR 28 , -N (R 29 ) R 28 , -SH, -S (O) r R 30 , -SO 2 NHR 32 , -SO 2 N (R 32 ) R 31 , -CHO, -C (O) R 31 , -C (O) OH, -C (O) OR 31 , -C (O ) SR 31 , -C (O) NHR 32 , -C (O) N (R 32 ) R 31 , -C (O) C (O) OR 31 , -C (R 34 ) = NOH, -C (R 34 ) = NOR 33 , -Si (R 13 ) (R 14 ) R 12 , -P (O) (OR 24 ) 2 , -P (S) (OR 24 ) 2 , -P (phenyl) 2 , -P (O) (phenyl) 2 , phenyl, phenyl substituted by (Z 1 ) p1 , L or M,
R 19 is C 1 -C 12 alkyl, C 1 -C 12 haloalkyl, C 1 -C 12 alkoxy (C 1 -C 12 ) alkyl, cyano (C 1 -C 12 ) alkyl, C 1 -C 12 alkoxycarbonyl (C 1 ~C 12) alkyl, phenyl (C 1 ~C 4) alkyl, (Z 1) phenyl substituted by p1 (C 1 ~C 4) alkyl, C 3 -C 12 alkenyl, C 3 -C 12 represents haloalkenyl, C 3 -C 12 alkynyl, C 3 -C 12 haloalkynyl, C 1 -C 12 alkylcarbonyl, C 1 -C 12 alkoxycarbonyl, phenyl substituted by phenyl or (Z 1) p1,
R 20 is C 1 -C 12 alkyl, C 1 -C 12 haloalkyl, C 1 -C 12 alkoxy (C 1 -C 12 ) alkyl, cyano (C 1 -C 12 ) alkyl, C 1 -C 12 alkoxycarbonyl (C 1 ~C 12) alkyl, phenyl (C 1 ~C 4) alkyl, (Z 1) phenyl substituted by p1 (C 1 ~C 4) alkyl, C 3 -C 12 alkenyl, C 3 -C 12 haloalkenyl, C 3 -C 12 alkynyl, C 3 -C 12 haloalkynyl, or represents phenyl which is substituted by phenyl or (Z 1) p1, or, C 4 ~ and R 19 and R 20 together by forming a C 7 alkylene chain, it represents that may form a 5- to 8-membered ring together with the nitrogen atom to which they are attached the alkylene chain at this time may contain one oxygen atom or sulfur atom, and C It may be optionally substituted by 1 -C 4 alkyl or C 1 -C 4 alkoxy group,
R 21 is a hydrogen atom, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, phenyl (C 1 ~C 4) alkyl, (Z 1) phenyl substituted by p1 (C 1 ~C 4) alkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 alkynyl, -CHO, C 1 ~C 6 alkyl carbonyl, C 1 -C 6 haloalkylcarbonyl, C 1 -C 6 alkoxycarbonyl, C 1 -C 6 haloalkoxycarbonyl, phenyl (C 1 ~C 4) alkoxycarbonyl, (Z 1) phenyl substituted by p1 (C 1 ~C 4) alkoxycarbonyl, phenoxycarbonyl, substituted by (Z 1) p1 It represents a phenoxycarbonyl, phenylcarbonyl, phenyl substituted by the (Z 1) phenylcarbonyl substituted by p1, phenyl or (Z 1) p1,
R 22 represents a hydrogen atom, C 1 -C 6 alkyl, -CHO, C 1 -C 6 alkylcarbonyl, a C 1 -C 6 haloalkylcarbonyl or C 1 -C 6 alkoxycarbonyl,
R 23 is cyano, C 3 -C 8 cycloalkyl, C 3 -C 8 halocycloalkyl, —OH, —OR 8 , —SH, —S (O) r R 8 , —N (R 10 ) R 9 , -N (R 10 ) CHO, -N (R 10 ) C (O) R 9 , -N (R 10 ) C (O) OR 9 , -N (R 10 ) C (O) SR 9 , -N (R 10 ) C (S) OR 9 , -N (R 10 ) C (S) SR 9 , -N (R 10 ) S (O) 2 R 9 , -C (O) OR 9 , -C (O ) N (R 10 ) R 9 , -Si (R 13 ) (R 14 ) R 12 , phenyl, phenyl substituted by (Z 1 ) p1 , L or M;
R 24 represents C 1 -C 6 alkyl or C 1 -C 6 haloalkyl,
R 25 is a halogen atom, cyano, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, hydroxy (C 1 -C 6 ) alkyl, C 1 -C 4 alkoxy (C 1 -C 4 ) alkyl, C 1 -C 4 alkoxycarbonyl (C 1 ~C 4) represents alkyl, C 1 -C 6 alkoxy, C 1 -C 6 alkoxycarbonyl, phenyl substituted by phenyl or (Z 1) p1, q1, q2, q3 or when q4 represents an integer of 2 or more, each R 25 may be the same as or different from each other;
R 26 is a hydrogen atom, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, -CHO, C 1 -C 6 alkylcarbonyl, C 1 -C 6 haloalkylcarbonyl, phenyl (C 1 -C 4 ) alkylcarbonyl , (Z 1) phenyl substituted by p1 (C 1 ~C 4) alkylcarbonyl, C 1 -C 6 alkoxycarbonyl, C 1 -C 6 haloalkoxycarbonyl, phenyl (C 1 -C 4) alkoxycarbonyl, ( Z 1) phenyl substituted by p1 (C 1 ~C 4) alkoxycarbonyl, C 1 -C 6 alkylthiocarbonyl, C 1 -C 6 alkoxythiocarbonyl, C 1 -C 6 alkylaminocarbonyl, di (C 1 ~ C 6 alkyl) aminocarbonyl, C 1 -C 6 alkylamino thiocarbonyl, di (C 1 -C 6 alkyl) aminothiocarbonyl, phenylcarbonyl, (Z 1) phenylcarbonyl substituted by p1, C 1 -C 6 Alkyls Represents Honiru, C 1 -C 6 haloalkylsulfonyl, phenylsulfonyl, and (Z 1) phenylsulfonyl substituted by p1, -P (O) (OR 24) 2 or -P (S) (OR 24) 2,
R 27 is a halogen atom, cyano, C 3 -C 8 cycloalkyl, C 3 -C 8 halocycloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 alkylthio, C 1 -C 6 haloalkylthio, C 1 -C 6 alkylsulfonyl, C 1 -C 6 haloalkylsulfonyl, C 1 -C 6 alkylamino, di (C 1 -C 6 alkyl) amino, -CHO, C 1 -C 6 alkyl carbonyl, C 1 -C 6 haloalkylcarbonyl, C 1 -C 6 alkoxycarbonyl, C 1 -C 6 haloalkoxycarbonyl, -CH = NOR 11, -C ( R 9) = NOR 11, phenyl, (Z 1) p1 Represents phenyl, L or M substituted by
R 28 is a hydrogen atom, C 1 -C 8 alkyl, optionally substituted by R 35 (C 1 ~C 8) alkyl, C 3 -C 8 cycloalkyl, optionally substituted by R 35 (C 3 -C 8) cycloalkyl, C 3 -C 8 alkenyl, optionally substituted by R 35 (C 3 ~C 8) alkenyl, optionally substituted by C 3 -C 8 alkynyl, R 35 (C 3 ~ C 8 ) alkynyl, -CHO, -C (O) R 31 , -C (O) OR 31 , -C (O) SR 31 , -C (O) NHR 32 , -C (O) N (R 32 ) R 31 , -C (O) C (O) R 31 , -C (O) C (O) OR 31 , -C (S) R 31 , -C (S) OR 31 , -C (S) SR 31 , -C (S) NHR 32 , -C (S) N (R 32 ) R 31 , -S (O) 2 R 31 , -S (O) 2 N (R 32 ) R 31 , -Si (R 13 ) (R 14 ) R 12 , -P (O) (OR 24 ) 2 , -P (S) (OR 24 ) 2 , phenyl, (Z 1 ) represents phenyl, L or M substituted by p1 ;
R 29 represents a hydrogen atom, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl or C 1 -C 6 alkoxy, or R 28 and R 29 together by now it forms a C 2 -C 5 alkylene chain, represents that may form a 3-6 membered ring together with the nitrogen atom to which they are attached this case the alkylene chain may contain one oxygen atom or a sulfur atom But often, and halogen atom, C 1 -C 6 alkyl group, C 1 -C 6 alkoxy group, a phenyl group or a (Z 1) p1 may be substituted by a phenyl group substituted by,
R 30 is, C 1 -C 8 alkyl, optionally substituted by R 35 (C 1 ~C 8) alkyl, optionally substituted by C 3 -C 8 cycloalkyl, R 35 (C 3 ~C 8 ) cycloalkyl, optionally substituted by C 3 -C 8 alkenyl, R 35 (C 3 ~C 8 ) alkenyl, optionally substituted by C 3 -C 8 alkynyl, R 35 (C 3 ~C 8 ) alkynyl, -SH, C 1 -C 6 alkylthio, C 1 -C 6 haloalkylthio, phenylthio, (Z 1) phenylthio substituted by p1, -CHO, -C (O) R 31, -C (O) OR 31 , -C (O) SR 31 , -C (O) NHR 32 , -C (O) N (R 32 ) R 31 , -C (O) C (O) R 31 , -C (O) C ( O) OR 31 , -C (S) R 31 , -C (S) OR 31 , -C (S) SR 31 , -C (S) NHR 32 , -C (S) N (R 32 ) R 31 , -P (O) (OR 24 ) 2 , -P (S) (OR 24 ) 2 , phenyl, phenyl substituted by (Z 1 ) p1 , L-18, L-21, L-25, L-30 ~ Represents L-35, L-45, L-48, L-49 or M,
R 31 is C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 8 cycloalkyl (C 1 -C 4 ) alkyl, C 1 -C 6 alkoxy (C 1 -C 4 ) alkyl, C 1 -C 6 haloalkoxy (C 1 ~C 4) alkyl, C 1 -C 6 alkylthio (C 1 ~C 4) alkyl, C 1 -C 6 haloalkylthio (C 1 ~C 4) alkyl, C 1 -C 6 alkylsulfonyl (C 1 ~C 4) alkyl, C 1 -C 6 haloalkylsulfonyl (C 1 ~C 4) alkyl, cyano (C 1 -C 6) alkyl, C 1 -C 6 alkylcarbonyl (C 1 -C 4) alkyl, C 1 -C 6 haloalkylcarbonyl (C 1 -C 4) alkyl, C 1 -C 6 alkoxycarbonyl (C 1 -C 4) alkyl, di (C 1 -C 6 alkyl) aminocarbonyl (C 1 -C 4) alkyl, tri (C 1 -C 4 alkyl) silyl (C 1 -C 4) alkyl, phenyl (C 1 -C 4) alkyl, (Z 1) phenyl substituted by p1 (C 1 -C 4 ) Alkyl, L- (C 1 -C 4) alkyl, M- (C 1 ~C 4) alkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 halocycloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, phenyl, phenyl, L or M, which is substituted by (Z 1) p1 represents,
R 32 represents a hydrogen atom, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, phenyl or phenyl substituted by (Z 1 ) p 1 , or R 31 and R 32 are taken together By forming a C 2 -C 5 alkylene chain, it indicates that a 3- to 6-membered ring may be formed together with the nitrogen atom to be bonded, and this alkylene chain has one oxygen atom, sulfur atom or nitrogen atom. comprise may, and halogen atom, C 1 -C 6 alkyl group, C 1 -C 6 alkoxy group, a formyl group, C 1 -C 6 alkylcarbonyl group, C 1 -C 6 alkoxycarbonyl group, a phenyl group or (Z 1 ) may be optionally substituted by a phenyl group substituted by p1 ,
R 33 is a hydrogen atom, C 1 -C 8 alkyl, (C 1 -C 8 ) alkyl optionally substituted by R 35 , C 3 -C 8 cycloalkyl, C 3 -C 8 alkenyl, optional by R 35 substituted a (C 3 ~C 8) alkenyl, optionally substituted by C 3 -C 8 alkynyl, or R 35 (C 3 ~C 8) alkynyl,
R 34 is a hydrogen atom, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 8 cycloalkyl (C 1 ~C 4) alkyl, C 1 -C 6 alkoxy (C 1 ~C 4) alkyl, C 1 -C 6 haloalkoxy (C 1 ~C 4) alkyl, C 1 -C 6 alkylthio (C 1 ~C 4) alkyl, C 1 -C 6 haloalkylthio (C 1 ~C 4) alkyl, C 1 -C 6 alkylsulfonyl (C 1 ~C 4) alkyl, C 1 -C 6 haloalkylsulfonyl (C 1 ~C 4) alkyl, phenyl (C 1 ~C 4) alkyl, substituted by (Z 1) p1 phenyl (C 1 ~C 4) represents alkyl, phenyl substituted by phenyl or (Z 1) p1,
R 35 is a halogen atom, cyano, nitro, C 3 -C 8 cycloalkyl, C 3 -C 8 halocycloalkyl, —OH, —OR 36 , —SH, —S (O) r R 36 , —NHR 37 , -N (R 37 ) R 36 , -CHO, -C (O) R 31 , -C (O) OR 31 , -C (O) SR 31 , -C (O) NHR 32 , -C (O) N (R 32 ) R 31 , -C (O) C (O) OR 31 , -CH = NOR 11 , -C (R 9 ) = NOR 11 , -Si (R 13 ) (R 14 ) R 12 ,- Phenyl substituted by P (O) (OR 24 ) 2 , -P (S) (OR 24 ) 2 , -P (phenyl) 2 , -P (O) (phenyl) 2 , phenyl, (Z 1 ) p1 , L or M
R 36 is C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy (C 1 -C 4 ) alkyl, C 1 -C 6 alkylthio (C 1 -C 4 ) alkyl, phenyl ( C 1 -C 4) alkyl, (Z 1) phenyl substituted by p1 (C 1 ~C 4) alkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 halocycloalkyl, C 3 -C 6 alkenyl , C 3 -C 6 haloalkenyl, C 3 -C 8 cycloalkenyl, C 3 -C 8 halocycloalkyl cycloalkenyl, C 3 -C 6 alkynyl, C 3 -C 6 haloalkynyl, -CHO, C 1 ~C 6 alkyl carbonyl, C 1 -C 6 haloalkylcarbonyl, C 1 -C 6 alkoxycarbonyl, C 1 -C 6 haloalkoxycarbonyl, C 1 -C 6 alkylaminocarbonyl, di (C 1 -C 6 alkyl) aminocarbonyl, phenylcarbonyl , (Z 1) phenylcarbonyl substituted by p1, C 1 ~C 6 alkyl amino thiocarboxamide It represents Le, di (C 1 -C 6 alkyl) aminothiocarbonyl, phenyl, phenyl, L or M, which is substituted by (Z 1) p1,
R 37 is a hydrogen atom, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 8 cycloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, C 1 -C 6 alkylcarbonyl , C 1 -C 6 haloalkylcarbonyl, C 1 -C 6 alkoxycarbonyl, C 1 -C 6 haloalkoxycarbonyl, phenoxycarbonyl, phenoxycarbonyl substituted by (Z 1) p1, phenylcarbonyl, by (Z 1) p1 substituted phenylcarbonyl, C 1 -C 6 alkylsulfonyl, C 1 -C 6 haloalkylsulfonyl, phenyl, phenyl substituted by (Z 1) p1, or represents L or M, or R 36 and R 37 Together form a C 2 -C 5 alkylene chain to form a 3- to 6-membered ring together with the nitrogen atom to which the alkylene chain is bonded, wherein the alkylene chain contains an oxygen atom or a sulfur atom. 1 May also do, may be substituted and the halogen atom or a methyl group,
m represents an integer of 0 to 4,
n represents an integer of 0 to 4,
p1 represents an integer of 1 to 5,
p2 represents an integer of 0 to 4,
p3 represents an integer of 0 to 3,
p4 represents an integer of 0 to 2,
p5 represents an integer of 0 or 1,
q1 represents an integer of 0 to 3,
q2 represents an integer of 0 to 5,
q3 represents an integer of 0 to 7,
q4 represents an integer of 0 to 9,
r represents an integer of 0 to 2;
t represents an integer of 0 or 1. ]
Xは、ハロゲン原子、ニトロ、C1〜C4アルキル、C1〜C4ハロアルキル、C1〜C4アルキルチオ、C1〜C4アルキルスルフィニル又はC1〜C4アルキルスルホニルを表し、mが2を表すとき、各々のXは互いに同一であっても又は互いに相異なっていてもよく、
Yは、ハロゲン原子又はC1〜C4アルキルを表し、nが2を表すとき、各々のYは互いに同一であっても又は互いに相異なっていてもよく、
R1及びR2は、水素原子を表し、
R3は、C1〜C8アルキル、C1〜C4アルキルチオ(C1〜C4)アルキル、C1〜C4アルキルスルフィニル(C1〜C4)アルキル又はC1〜C4アルキルスルホニル(C1〜C4)アルキルを表し、
R4は、C1〜C6アルキル又はC1〜C6ハロアルキルを表し、
R5は、フェニル、(Z1)p1によって置換されたフェニル、(Z1)p1によって置換されたフェノキシフェニル、(Z1)p1によって置換されたピリジルオキシフェニル、L-1〜L-4、L-8〜L-13、L-15〜L-23、L-45〜L-52又はL-53を表し、
R6vは、水素原子を表し、
Z1は、ハロゲン原子、シアノ、ニトロ、C1〜C6アルキル、C1〜C6ハロアルキル、C1〜C3アルキルチオ(C1〜C3)アルキル、C1〜C3ハロアルキルチオ(C1〜C3)アルキル、C1〜C3アルキルスルフィニル(C1〜C3)アルキル、C1〜C3ハロアルキルスルフィニル(C1〜C3)アルキル、C1〜C3アルキルスルホニル(C1〜C3)アルキル、C1〜C3ハロアルキルスルホニル(C1〜C3)アルキル、C1〜C6アルコキシ、C1〜C6ハロアルコキシ、C1〜C3ハロアルコキシ(C1〜C3)ハロアルコキシ、C1〜C6アルキルスルホニルオキシ、C1〜C6ハロアルキルスルホニルオキシ、C1〜C6アルキルチオ、C1〜C6ハロアルキルチオ、C1〜C6アルキルスルフィニル、C1〜C6ハロアルキルスルフィニル、C1〜C6アルキルスルホニル、C1〜C6ハロアルキルスルホニル、-C(O)NH2又は-C(S)NH2を表し、p1, p2, p3又はp4が2以上の整数を表すとき、各々のZ1は互いに同一であっても又は互いに相異なっていてもよく、
さらに、2つのZ1が隣接する場合には、隣接する2つのZ1は-CF2CF2O-, -CF2OCF2-, -OCF2O-, -OCF2CHFO-, -OCF2CF2O-又は-CH=CHCH=CH-を形成することにより、2つのZ1のそれぞれが結合する炭素原子と共に5員環又は6員環を形成してもよく、
R15は、C1〜C6アルキル、C1〜C6ハロアルキル、フェニル(C1〜C4)アルキル、(Z1)p1によって置換されたフェニル(C1〜C4)アルキル、フェニル又は(Z1)p1によって置換されたフェニルを表し、
mは、0〜2の整数を表し、
nは、0〜2の整数を表し、
q2、q3及びq4は、各々独立して0〜2の整数を表す置換ベンズアニリド化合物及びその塩より選ばれる1種又は2種以上と、請求項1記載の化合物群Aより選ばれる化合物の1種又は2種以上を含有する殺虫、殺ダニ、殺線虫、殺菌又は殺バクテリア組成物。 In the general formula (2) according to claim 3, W 1 and W 2 represent an oxygen atom,
X represents a halogen atom, nitro, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkylthio, a C 1 -C 4 alkylsulfinyl or C 1 -C 4 alkylsulfonyl, m is 2 Each X may be the same as or different from each other;
Y represents a halogen atom or a C 1 -C 4 alkyl, when n is 2, each Y may be the even or different from each other the same as each other,
R 1 and R 2 represent a hydrogen atom,
R 3 is C 1 -C 8 alkyl, C 1 -C 4 alkylthio (C 1 -C 4 ) alkyl, C 1 -C 4 alkylsulfinyl (C 1 -C 4 ) alkyl or C 1 -C 4 alkylsulfonyl ( C 1 -C 4) alkyl,
R 4 represents C 1 -C 6 alkyl or C 1 -C 6 haloalkyl,
R 5 is phenyl, (Z 1) phenyl substituted by p1, (Z 1) phenoxyphenyl phenyl substituted by p1, (Z 1) pyridyloxy phenyl substituted by p1, L-1~L-4, L-8 to L-13, L-15 to L-23, L-45 to L-52 or L-53,
R 6v represents a hydrogen atom,
Z 1 is a halogen atom, cyano, nitro, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 3 alkylthio (C 1 -C 3 ) alkyl, C 1 -C 3 haloalkylthio (C 1 -C 3) alkyl, C 1 -C 3 alkylsulfinyl (C 1 ~C 3) alkyl, C 1 -C 3 haloalkylsulfinyl (C 1 ~C 3) alkyl, C 1 -C 3 alkylsulfonyl (C 1 -C 3) alkyl, C 1 -C 3 haloalkylsulfonyl (C 1 -C 3) alkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 3 haloalkoxy (C 1 -C 3) halo alkoxy, C 1 -C 6 alkylsulfonyloxy, C 1 -C 6 haloalkylsulfonyloxy, C 1 -C 6 alkylthio, C 1 -C 6 haloalkylthio, C 1 -C 6 alkylsulfinyl, C 1 -C 6 haloalkylsulfinyl , C 1 -C 6 alkylsulfonyl, C 1 -C 6 haloalkylsulfonyl, -C (O) NH 2 The Represents -C (S) NH 2, p1 , when p2, p3 or p4 represents an integer of 2 or more, each Z 1 may be the even or different from each other the same as each other,
Further, when two Z 1 are adjacent to each other, the two adjacent Z 1 are -CF 2 CF 2 O-, -CF 2 OCF 2- , -OCF 2 O-, -OCF 2 CHFO-, -OCF 2 By forming CF 2 O— or —CH═CHCH═CH—, a 5-membered ring or a 6-membered ring may be formed with the carbon atom to which each of the two Z 1 bonds,
R 15 is, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, phenyl (C 1 -C 4) alkyl, (Z 1) phenyl substituted by p1 (C 1 ~C 4) alkyl, phenyl or ( Z 1 ) represents phenyl substituted by p1 ,
m represents an integer of 0 to 2,
n represents an integer of 0 to 2,
q1, q3 and q4 each independently represents one or more selected from a substituted benzanilide compound and a salt thereof each representing an integer of 0 to 2, and one compound selected from the compound group A according to claim 1 Or an insecticidal, acaricidal, nematicidal, bactericidal or bactericidal composition containing two or more.
化合物群B:ジフルベンズロン、フルフェノクスロン、テフルベンズロン、クロルフルアズロン、フェンプロパトリン、シハロトリン、シペルメトリン、ペルメトリン、トラロメトリン、フルバリネート、フェンバレレート、メチダチオン、フェントエート、プロチオホス、アラニカルブ、ニテンピラム、ジノテフラン、チアメトキサム、イミダクロプリド、クロチアニジン、チアクロプリド及びクロルフェナピル。 1 type or 2 or more types chosen from the substituted benzanilide compound and its salt represented by General formula (1) of Claim 1 and 1 type or 2 or more types of the compound chosen from the following compound groups B are contained. Insecticidal, acaricidal or nematicidal composition.
Compound group B: diflubenzuron, flufenoxuron, teflubenzuron, chlorfluazuron, fenpropatoline, cyhalothrin, cypermethrin, permethrin, tralomethrin, fulvalinate, fenvalerate, methidathion, phentoate, prothiophos, alaniccarb, nitenpyram, dinotepam, thiamethato Imidacloprid, clothianidin, thiacloprid and chlorfenapyr.
One or more compounds selected from the substituted benzanilide compounds represented by the general formula (2) according to claim 4 and salts thereof, and one or more compounds selected from the compound group B according to claim 5. A method for controlling insects, ticks or nematodes, characterized in that the above are simultaneously or in close proximity.
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RU2798075C2 (en) * | 2018-11-02 | 2023-06-14 | Нихон Нохияку Ко., Лтд. | Pest composition and method of its use |
JP7408564B2 (en) | 2018-11-02 | 2024-01-05 | 日本農薬株式会社 | Pesticide composition and method of use thereof |
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