CN1285827A - 取代的胍衍生物 - Google Patents
取代的胍衍生物 Download PDFInfo
- Publication number
- CN1285827A CN1285827A CN98812980A CN98812980A CN1285827A CN 1285827 A CN1285827 A CN 1285827A CN 98812980 A CN98812980 A CN 98812980A CN 98812980 A CN98812980 A CN 98812980A CN 1285827 A CN1285827 A CN 1285827A
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- CN
- China
- Prior art keywords
- alkyl
- group
- represent
- alkenyl
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 150000002357 guanidines Chemical class 0.000 title abstract description 5
- 229940083094 guanine derivative acting on arteriolar smooth muscle Drugs 0.000 title abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 126
- -1 halogen alkane Chemical group 0.000 claims abstract description 79
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 31
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 24
- 239000001257 hydrogen Substances 0.000 claims abstract description 24
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 18
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 17
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 17
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 15
- 150000002367 halogens Chemical class 0.000 claims abstract description 15
- 125000005843 halogen group Chemical group 0.000 claims abstract description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 8
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 8
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims abstract description 8
- 125000003302 alkenyloxy group Chemical group 0.000 claims abstract description 7
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 7
- 125000004644 alkyl sulfinyl group Chemical group 0.000 claims abstract description 7
- 125000004390 alkyl sulfonyl group Chemical group 0.000 claims abstract description 7
- 125000004414 alkyl thio group Chemical group 0.000 claims abstract description 7
- 125000003118 aryl group Chemical group 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- 125000005108 alkenylthio group Chemical group 0.000 claims abstract description 4
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims abstract description 4
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims abstract description 4
- 125000000278 alkyl amino alkyl group Chemical group 0.000 claims abstract description 4
- 125000003282 alkyl amino group Chemical group 0.000 claims abstract description 4
- 125000003806 alkyl carbonyl amino group Chemical group 0.000 claims abstract description 4
- 125000004448 alkyl carbonyl group Chemical group 0.000 claims abstract description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 4
- 125000001769 aryl amino group Chemical group 0.000 claims abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims abstract description 4
- 125000004985 dialkyl amino alkyl group Chemical group 0.000 claims abstract description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 4
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 4
- 125000005346 substituted cycloalkyl group Chemical group 0.000 claims abstract description 4
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- 239000011737 fluorine Substances 0.000 claims description 32
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 31
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 25
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 22
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 22
- 229910052794 bromium Inorganic materials 0.000 claims description 22
- 125000001424 substituent group Chemical group 0.000 claims description 21
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- 125000006656 (C2-C4) alkenyl group Chemical group 0.000 claims description 4
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- 125000006526 (C1-C2) alkyl group Chemical group 0.000 claims description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 2
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 claims description 2
- 125000001376 1,2,4-triazolyl group Chemical group N1N=C(N=C1)* 0.000 claims description 2
- 125000004517 1,2,5-thiadiazolyl group Chemical group 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
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- 125000003226 pyrazolyl group Chemical group 0.000 claims 1
- 125000006193 alkinyl group Chemical group 0.000 abstract 2
- 125000004070 6 membered heterocyclic group Chemical group 0.000 abstract 1
- 125000005110 aryl thio group Chemical group 0.000 abstract 1
- 125000004663 dialkyl amino group Chemical group 0.000 abstract 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 abstract 1
- 125000000262 haloalkenyl group Chemical group 0.000 abstract 1
- 125000004438 haloalkoxy group Chemical group 0.000 abstract 1
- 150000002431 hydrogen Chemical class 0.000 abstract 1
- 239000002904 solvent Substances 0.000 description 38
- 230000000694 effects Effects 0.000 description 27
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- 239000003995 emulsifying agent Substances 0.000 description 18
- 239000000126 substance Substances 0.000 description 17
- 238000012360 testing method Methods 0.000 description 17
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 13
- 239000012141 concentrate Substances 0.000 description 13
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- 239000005936 tau-Fluvalinate Substances 0.000 description 1
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- WWJZWCUNLNYYAU-UHFFFAOYSA-N temephos Chemical compound C1=CC(OP(=S)(OC)OC)=CC=C1SC1=CC=C(OP(=S)(OC)OC)C=C1 WWJZWCUNLNYYAU-UHFFFAOYSA-N 0.000 description 1
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- HYVWIQDYBVKITD-UHFFFAOYSA-N tolylfluanid Chemical compound CN(C)S(=O)(=O)N(SC(F)(Cl)Cl)C1=CC=C(C)C=C1 HYVWIQDYBVKITD-UHFFFAOYSA-N 0.000 description 1
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- BAZVSMNPJJMILC-UHFFFAOYSA-N triadimenol Chemical compound C1=NC=NN1C(C(O)C(C)(C)C)OC1=CC=C(Cl)C=C1 BAZVSMNPJJMILC-UHFFFAOYSA-N 0.000 description 1
- NKNFWVNSBIXGLL-UHFFFAOYSA-N triazamate Chemical compound CCOC(=O)CSC1=NC(C(C)(C)C)=NN1C(=O)N(C)C NKNFWVNSBIXGLL-UHFFFAOYSA-N 0.000 description 1
- FFSJPOPLSWBGQY-UHFFFAOYSA-N triazol-4-one Chemical compound O=C1C=NN=N1 FFSJPOPLSWBGQY-UHFFFAOYSA-N 0.000 description 1
- AMFGTOFWMRQMEM-UHFFFAOYSA-N triazophos Chemical compound N1=C(OP(=S)(OCC)OCC)N=CN1C1=CC=CC=C1 AMFGTOFWMRQMEM-UHFFFAOYSA-N 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- NFACJZMKEDPNKN-UHFFFAOYSA-N trichlorfon Chemical compound COP(=O)(OC)C(O)C(Cl)(Cl)Cl NFACJZMKEDPNKN-UHFFFAOYSA-N 0.000 description 1
- DQJCHOQLCLEDLL-UHFFFAOYSA-N tricyclazole Chemical compound CC1=CC=CC2=C1N1C=NN=C1S2 DQJCHOQLCLEDLL-UHFFFAOYSA-N 0.000 description 1
- RROQIUMZODEXOR-UHFFFAOYSA-N triforine Chemical compound O=CNC(C(Cl)(Cl)Cl)N1CCN(C(NC=O)C(Cl)(Cl)Cl)CC1 RROQIUMZODEXOR-UHFFFAOYSA-N 0.000 description 1
- YNWVFADWVLCOPU-MAUPQMMJSA-N uniconazole P Chemical compound C1=NC=NN1/C([C@@H](O)C(C)(C)C)=C/C1=CC=C(Cl)C=C1 YNWVFADWVLCOPU-MAUPQMMJSA-N 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- JARYYMUOCXVXNK-IMTORBKUSA-N validamycin Chemical compound N([C@H]1C[C@@H]([C@H]([C@H](O)[C@H]1O)O[C@H]1[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O1)O)CO)[C@H]1C=C(CO)[C@H](O)[C@H](O)[C@H]1O JARYYMUOCXVXNK-IMTORBKUSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000004563 wettable powder Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- WCJYTPVNMWIZCG-UHFFFAOYSA-N xylylcarb Chemical compound CNC(=O)OC1=CC=C(C)C(C)=C1 WCJYTPVNMWIZCG-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- AMHNZOICSMBGDH-UHFFFAOYSA-L zineb Chemical compound [Zn+2].[S-]C(=S)NCCNC([S-])=S AMHNZOICSMBGDH-UHFFFAOYSA-L 0.000 description 1
- DUBNHZYBDBBJHD-UHFFFAOYSA-L ziram Chemical compound [Zn+2].CN(C)C([S-])=S.CN(C)C([S-])=S DUBNHZYBDBBJHD-UHFFFAOYSA-L 0.000 description 1
- JLYXXMFPNIAWKQ-UHFFFAOYSA-N γ Benzene hexachloride Chemical compound ClC1C(Cl)C(Cl)C(Cl)C(Cl)C1Cl JLYXXMFPNIAWKQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N51/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds having the sequences of atoms O—N—S, X—O—S, N—N—S, O—N—N or O-halogen, regardless of the number of bonds each atom has and with no atom of these sequences forming part of a heterocyclic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明涉及式(Ⅰ)的新的胍衍生物,其中R1代表包含1,2,3或4个氮原子和/或一个或两个氧或硫原子作为杂原子成环原子-其中杂原子数是1,2,3或4-并且任选被卤素,氰基,硝基,烷基,卤代烷基,链烯基,卤代链烯基,炔烃基,烷氧基,卤代烷氧基,链烯基氧基,卤代链烯基氧基,炔烃基氧基,烷硫基,卤代烷硫基,链烯基硫基,卤代链烯基硫基,炔烃基硫基,烷基亚磺酰基,卤代烷基亚磺酰基,烷基磺酰基,卤代烷基磺酰基,氨基,烷基氨基,二烷基氨基,芳基,芳基硫基,芳基氨基,芳基烷基,甲酰基氨基,烷基羰基氨基,甲酰基,氨基甲酰基,烷基羰基和/或烷氧羰基取代的5-或6-元杂环基团;R2代表氢或烷基,R3代表基团-OR4,-OCOR5,-OCOOR6,-OCONR7R8和-OSO2R9,其中R4,R5和R6各自独立地代表烷基,烷氧基烷基,卤代烷基,链烯基,炔烃基,烷基氨基烷基,二烷基氨基烷基,任选被取代的环烷基和各种情况下任选被取代的苯基或苄基,R7和R8各自独立地代表氢,烷基,链烯基和各种情况下任选被取代的苯基或苄基,和R9代表烷基或任选被取代的苯基,A代表基团-CH2CH2-,(CH2)3和-CH=CH-,和Z代表氰基或硝基,条件是,如果Z代表NO2和A代表-CH2CH2-,则R2代表氢;以及排除其中R1相应于式(Ⅱ)、R2=H、R3=OCH3、A=-CH2CH2-和Z=NO2的式(Ⅰ)的化合物。
Description
本申请涉及新的胍衍生物,它们的制备方法和它们防治动物害虫的用途。
已知一些杂环化合物具有杀虫性能(例如参见EP-A0192060,EP-A0277317,根据CA125,188277;121,255796;121,157642的参考文献)。
但是,特别是在低施用比例和浓度下,这些化合物的活性和/或活性谱不是在所有使用领域都完全令人满意。
因此,本发明提供式(Ⅰ)的新的胍衍生物其中R1代表包含1,2,3或4个氮原子和/或一个或两个氧或硫原子作为杂原子成环原子-其中杂原子数是1,2,3或4-并且任选被卤素,氰基,硝基,烷基,卤代烷基,链烯基,卤代链烯基,炔烃基,烷氧基,卤代烷氧基,链烯基氧基,卤代链烯基氧基,炔烃基氧基,烷硫基,卤代烷硫基,链烯基硫基,卤代链烯基硫基,炔烃基硫基,烷基亚磺酰基,卤代烷基亚磺酰基,烷基磺酰基,卤代烷基磺酰基,氨基,烷基氨基,二烷基氨基,芳基,芳基硫基,芳基氨基,芳基烷基,甲酰基氨基,烷基羰基氨基,甲酰基,氨基甲酰基,烷基羰基和/或烷氧羰基取代的5-或6-元杂环基团;R2代表氢或烷基,R3代表基团-OR4,-OCOR5,-OCOOR6,-OCONR7R8和-OSO2R9,其中R4,R5和R6各自独立地代表烷基,烷氧基烷基,卤代烷基,链烯基,炔烃基,烷基氨基烷基,二烷基氨基烷基,任选被取代的环烷基和各种情况下任选被取代的苯基或苄基,R7和R8各自独立地代表氢,烷基,链烯基和各种情况下任选被取代的苯基或苄基,和R9代表烷基或任选被取代的苯基,A代表基团-CH2CH2-,(CH2)3和-CH=CH-,和Z代表氰基或硝基,条件是,如果Z代表NO2和A代表-CH2CH2-,则R2代表氢;并排除下面的式(Ⅰ)的化合物R2 H,R3 OCH3,A -CH2CH2-和Z NO2
最后发现,式(Ⅰ)的新的化合物具有非常显著的生物性能,并且特别适合防治农业,林业,贮存品和材料的保护和卫生领域所遇到的动物害虫,特别是昆虫,蜘蛛纲和线虫。
式(Ⅰ)提供了根据本发明的化合物的一般定义。
下面详细说明上面和下面提到的结构式中列出的基团的优选取代基或范围。R1优选代表选自吡唑基,1,2,4-三唑基,噁唑基,异噁唑基,噻唑基,异噻唑基,1,2,5-噻二唑基,吡啶基,哌嗪基和嘧啶基,并且任选被氟,氯,溴,氰基,硝基,C1-C2-烷基(任选被氟和/或氯取代的),C1-C2-烷氧基(任选被氟和/或氯取代的),C1-C2-烷硫基(任选被氟和/或氯取代的),或C1-C2-烷基磺酰基(任选被氟和/或氯取代的)取代的5-至6-元杂环基团;R2优选代表氢或C1-C6-烷基,R3优选代表基团-OR4,-OCOR5,-OCOOR6,-OCONR7R8和-OSO2R9,其中R4,R5和R6各自独立地优选代表C1-C12-烷基,C1-C4-烷氧基-C1-C4-烷基,具有1-5个相同或不同的卤原子例如氟,氯和溴原子的C1-C4-卤代烷基;C2-C4-链烯基,C2-C4-炔烃基,C1-C4-烷基氨基-C1-C4-烷基,二(C1-C4)-烷基氨基-C1-C4-烷基,代表任选被相同或不同的取代基一-至三取代的C3-C6-环烷基,优选的取代基可以提到:卤素,C1-C4-烷基和具有1-5个相同或不同的卤原子例如氟,氯和溴原子的C1-C4-卤代烷基,或者代表苯基或苄基,其各自任选被相同或不同的取代基一-至三取代,各种情况下,优选的苯基取代基是:卤素,C1-C4-烷基,C1-C4-烷氧基和各种情况下具有1-5个相同或不同的卤原子例如氟,氯和溴原子的C1-C4-卤代烷基和C1-C4-卤代烷氧基和硝基,R7和R8各自独立地优选代表氢,C1-C6-烷基,C2-C4-链烯基或者代表苯基或苄基,其各自任选被相同或不同的取代基一-至三取代,各种情况下,优选的苯基取代基是:卤素,C1-C4-烷基,C1-C4-烷氧基和各种情况下具有1-5个相同或不同的卤原子例如氟,氯和溴原子的C1-C4-卤代烷基和C1-C4-卤代烷氧基,和R9优选代表C1-C4-烷基或代表苯基,其被相同或不同的取代基一-至三取代,可能的取代基是:卤素,C1-C4-烷基,C1-C4-烷氧基和各种情况下具有1-5个相同或不同的卤原子例如氟,氯和溴原子的C1-C4-卤代烷基和C1-C4-卤代烷氧基,A优选代表基团-CH2CH2-,-(CH2)3-和-CH=CH-,Z优选代表氰基或硝基,条件是,如果Z代表NO2和A代表-CH2CH2-,则基团R2代表氢;并且排除下面的式(Ⅰ)的化合物R2 H,R3 OCH3,A -CH2CH2-和Z NO2R1特别优选代表6-氯-3-吡啶基(6-氯-吡啶-3-基)或代表2-氯-5-噻唑基(2-氯-噻唑基-5-基),R2特别优选代表氢或C1-C5-烷基,R3特别优选代表基团-OR4,-OCOR5,-OCOOR6,-OCONR7R8和-OSO2R9,其中R4,R5和R6各自独立地特别优选代表C1-C8-烷基,C1-C2-烷氧基-C1-C2-烷基,具有1-2个相同或不同的卤原子例如氟,氯和溴原子的C1-C2-卤代烷基;烯丙基,炔丙基,C1-C2-烷基氨基-C1-C2-烷基,二(C1-C2)-烷基氨基-C1-C2-烷基,环丙基,环戊基,环己基,或者代表苯基或苄基,其各自任选被相同或不同的取代基一-至二取代,各种情况下可能的苯基取代基是:氟,氯,溴,甲基,甲氧基,三氟甲基,三氟甲氧基和硝基,R7和R8各自独立地特别优选代表氢,C1-C4-烷基,乙烯基,烯丙基,或者代表苯基或苄基,其各自任选被相同或不同的取代基一-至二取代,各种情况下可能的苯基取代基是:氟,氯,溴,甲基,甲氧基,三氟甲基和三氟甲氧基,和R9特别优选代表甲基,乙基或任选被相同或不同的取代基一-至二取代的苯基,可能的取代基是:氟,氯,溴,甲基,甲氧基,三氟甲基和三氟甲氧基,A特别优选代表基团-CH2CH2-和-CH=CH-,Z特别优选代表氰基或硝基,条件是,如果Z代表NO2和A代表-CH2CH2-,则基团R2代表氢;并且排除下面的式(Ⅰ)的化合物R2 H,R3 OCH3,A -CH2CH2-和Z NO2
上述一般或优选的基团定义或说明适用于终产物,并且相应地适用于起始物和中间体。这些基团定义可以根据需要相互组合,即包括各优选范围之间的组合。
根据本发明优选包括上面作为优选(优选的)定义的组合的式(Ⅰ)的化合物。
根据本发明特别优选包括上面作为特别优选定义的组合的式(Ⅰ)的化合物。
在上面和下面给出的基团定义中,烃链,例如烷基-包括与杂原子的组合,例如烷氧基-在各种情况下只要有可能,是直链或支链的。
需要用作进行本发明方法的起始物的式(Ⅱ)的化合物是已知的(参见,例如EP-A0192060,EP-A0235725,EP-A0259738和EP-A0315826),和/或它们可以以这里所描述的方法获得。
进行本发明方法还需要用作起始物的式(Ⅲ)的卤代化合物一般是已知的有机化学化合物和/或可通过一般已知的方法制备。
制备式(Ⅰ)的新的化合物的本发明方法优选使用稀释剂进行。合适的稀释剂基本上是所有惰性有机溶剂。优选包括:脂肪族和芳香族的、任意卤化的烃,例如戊烷,己烷,庚烷,环己烷,石油醚,汽油,ligroin,苯,甲苯,二甲苯,二氯甲烷,二氯乙烷,氯仿,四氯化碳,氯苯和邻-二氯苯,醚类,例如乙醚和丁醚,乙二醇二甲基醚和二甘醇二甲基醚,四氢呋喃,和二噁烷,酮类,例如丙酮,甲基乙基酮,甲基异丙基酮和甲基异丁基酮,酯类,例如乙酸甲酯和乙酸乙酯,腈类,例如乙腈和丙腈,酰胺类,例如二甲基甲酰胺,二甲基乙酰胺和N-甲基吡咯烷酮,还有二甲亚砜,四亚甲基砜和六甲基磷酸三酰胺。
在根据本发明方法中使用的碱是所有常规质子受体。优选使用碱金属或碱土金属氢氧化物,碱金属或碱土金属氢化物,碱金属或碱土金属碳酸盐或碳酸氢盐或含氮碱。可以提到的例子是氢氧化钠,氢氧化钙,氢化钠,碳酸钾,碳酸氢钠,三乙胺,二苄基胺,二异丙基胺,吡啶,喹啉,二氮杂双环辛烷(DABCO),二氮杂双环壬烯(DBN)和二氮杂双环十一烯(DBU)。
进行本发明方法的反应温度可以在相当宽的范围内变化。一般情况下,该方法在-40℃和+200℃之间的温度,优选在-10℃至100℃之间的温度下进行。
进行制备式(Ⅰ)的化合物的本发明方法时,对于每摩尔式(Ⅱ)的化舍合一般使用1-3摩尔,优选1-2摩尔式(Ⅲ)的卤代化合物。
通过常规方法进行终产物的后处理和分离。
本发明化合物适于防治动物害虫,特别是农业,林业,储藏品保护和材料保护以及卫生领域所遇到的昆虫,蛛形纲和线虫,并且具有好的植物耐受性和对温血动物具有低毒性。它们可以优选被用作农作物保护剂。它们对于一般敏感性和抗性物种都是有活性的,并且抗发育的所有阶段或部分阶段。上述害虫包括:等足目(Isopoda),例如Oniscus aselluse,鼠妇(Armadillidiumvulgare)和Porcellio scaber。多足纲目(Diplopoda),例如Blaniulus gutttulatus。唇足亚纲目(Chilopoda),例如Geophilus carpophagus和蛐蜒目种(Scutigera spec.)。综合纲目(Symphyla),例如Scutigerella immaculata。缨尾目(Thysanura),例如西洋衣鱼(Lepisma saccharina)。弹尾目(Collembola),例如Onychiurus armatus。直翅目(Orthoptera),例如东方非蠊(Blatta orientalis),美洲大蠊(Periplaneta americana),马德拉非蠊(Leucophaea maderae),德国小蠊(Blattella germanica),灶马(Acheta domesticus),蝼蛄属(Gryllotalpa spp.),热带飞蝗(Locusta migratoriamigratorioides),长额负蝗(Melanoplus differentialis)和Schistocerca gregaria。革翅目(Dermaptera),例如欧洲球螋(Forficula auricularia)。等翅目(Isoptera),例如白蚁属(Reticulitermes spp.)。虱目(Anoplura),例如头虱(Pediculus humanus corporis),盲虱属(Haematopinus spp.)和长额虱(Linognathus spp.)。食毛目(Mallophaga),例如羽虱属(Trichodectes spp.)和Damalinea spp.。缨翅目(Thysanoptera),例如温室条蓟马(Hercinothrips femoralis)和棉蓟马(Thrips tabaci)。异翅亚目(Heteroptera),例如褐盾蝽属(Eurygaster spp.),Dysdercus intermedius,甜菜拟网蝽(Piesma quadrata),臭虫(Cimex lectularius),Rhodnius prolixus和吸血猎蝽属(Triatomaspp.)。同翅亚目(Homoptera),例如Aleurodes brassicae,棉粉虱(Bemisiatabaci),温室白粉虱(Trialeurodes vaporariorum),棉蚜(Aphisgossypii),甘蓝蚜(Brevicoryne brassicae),茶鹿隐瘤额蚜(Cryptomyzus ribis),蚕豆蚜(Aphis fabae),Aphis pomi,苹果绵蚜(Eriosoma lanigerum),桃大尾蚜(Hyalopterus arundinis),Phylloxera vastatrix,Pemphigus spp.,Macrosiphum avenae,瘤额蚜(Myzus spp.),忽布瘤额蚜(Phorodon humuli),粟缢管蚜(Rhopasiphum padi),叶蝉属(Empoasca spp.),Euscelisbilobatus,黑尾叶蝉(Nephotettix cincticeps),李蜡蚧(Lecaniumcorni),油橄榄盔(Saissetia oleae),稻灰飞虱(Laodelphaxstriatellus),褐稻虱(Nilaparvata lugens),红圆蚧(Aonidiellaaurantii),Aspidiotus hederae,粉蚧属(Pseudococcus spp.)和木虱属(Psylla spp.)。鳞翅目(Lepidoptera),例如,红铃虫(Pectinophora gossypiella),松尺蠖(Bupalus piniarius),Cheimatobia brumata,Lithocolletisblancardella,樱桃巢蛾(Hyponomeuta padella),小菜蛾(Plutellamaculipennis),天幕毛虫(Malacosoma neustria),Euproctischrysorrhoea,毒蛾属(Lymantria spp.),棉叶穿孔潜蛾(Bucculatrix thurberiella),Phyllocnisti citrella,地老虎(Agrotis spp.),切根虫(Euxoa spp.),褐夜蛾(Feltia spp.),埃及金刚钻(Earias insulana),夜蛾属(Heliothis spp.),甜菜夜蛾(Spodoptera exigua),甘蓝夜蛾(Mamestra brassicae),Panolisflammea,斜纹夜蛾(Prodenia litura),夜蛾属(Spodoptera spp.),粉纹夜蛾(Trichoplusia ni),苹果蠹蛾(Carpocapsa pomonella),粉蝶属(Pieris spp.),螟(Chilo spp.),Pyrausta nubilalis,Ephestia kuehniella,大黄螟(Galleria mellonella),袋衣蛾(Tineola bisselliella),网衣蛾(Tinea pellionella),褐织叶蛾(Hofmannophila pseudospretella),Cacoecia podana,Capuareticulana,云杉卷叶蛾(Choristoneura fumiferana),葡萄果蠹蛾(Clysia ambiguella),茶黄卷叶蛾(Homona magnanima)和栎绿卷叶蛾(Tortrix viridana)。鞘翅目(Coleoptera),例如,家具窃蠹(Anobium punctatum),Rhizopertha dominica,Bruchidius obtectus,大豆象(Acanthoscelides obtectus),家天牛(Hylotrupes bajulus),Agelastica alni,甲铃薯甲虫(Leptinotarsa decemlineata),Phaedon cochleariae,叶甲属(Diabrotica spp.),油菜兰跳甲(Psylliodes chrysocephala),墨西哥豆瓢虫(Epilachnavarivestis),Atomaria spp.,锯胸谷盗(Oryzaephilussurinamens),象甲属(Anthonomus spp.),米象属(Sitophilusspp.),Otiorrhynchus sulcatus,香蕉蛛基象甲(Cosmopolitessordidus),Ceuthorrhynchus assimilis,苜宿叶象甲(Hyperaposttica),皮蠹属(Dermestes spp.),皮蠹属(Trogoderma spp.),皮蠹属(Anthrenus spp.),黑皮蠹(Attagenue spp.),粉蠹(Lyctusspp.),Meligethes aeneus,蛛甲属(Ptinus spp.),金黄蛛甲(Niptushololeucus),麦蛛甲(Gibbium psylliodes),拟谷稻属(Triboliumspp.),黄粉甲(Tenebrio molitor),扣甲属(Agriotes spp.),金针虫属(Conoderus spp.),Melolontha meiolontha,六月金龟子(Amphimallon solstitialis)和Costelytra zealandica。膜翅属(Hymenoptera),例如锯角叶蜂属(Diprion spp.),叶蜂属(Hoplocampa app.),蚁(Lasius spp.),厨蚁(Monomoriumpharaonis),和胡蜂(Vespa spp.)。双翅属(Diptera),例如,咿蚊(Aedes spp.),斑按蚊属(Anophelesspp.),库蚊(Culex spp.),黄猩猩果蝇(Drosophilamelanogaster),家蝇(Musca spp.),厩蝇(Fannia spp.),红头丽蝇(Calliphora erythrocephala),丝光绿蝇(Lucilia spp.),Chrysomyia spp.,疽蝇属(Cuterebra spp.),Gastrophilus spp.,Hyppobosca spp.,螫蝇属(Stomoxys spp.),鼻蝇属(Oestrus spp.),皮蝇属(Hypoderma spp.),牛虻属(Tabanus spp.),Tannia spp.,Bibio hortulanus,瑞典麦杆蝇(Oscinella frit),麦蝇(Phorbiaspp.),甜菜潜叶花蝇(Pegomyia hyoscyami),地中海实蝇(Ceratitiscapitata),油橄榄实蝇(Dacus oleae)和欧洲大蚊(Tipulapaludosa)。蚤目(Siphonaptera),例如,东方鼠蚤(Xenopsylla cheopis),和角叶蚤属(Ceratophyllus spp.)。蛛形纲(Arachnida),例如Scorpio maurus,黑寡妇球腹蛛(Latrodectus mactans)。蜱螨目(Acarina),例如,粗脚粉螨(Acarus siro),隐喙蚍(Argasspp.),喙蜱属(Ornithodoros spp.),鸡皮刺螨(Dermanyssusgallinae),Eriophyes ribis,橘锈螨(Phyllocoptruta oleivora),牛蜱属(Boophilus spp.),头蜱属(Rhipicephalus spp.),花蜱属(Amblyomma spp.),Hyalomma spp.,硬蚍(Ixodes spp.),蛘螨属(Psoroptes spp.),恙螨属(Chorioptes spp.),疥螨(Sarcoptesspp.),线螨属(Tarsonemus spp.),苜宿苔螨(Bryobia praetiosa),红蜘蛛(Panonychus spp.),和红叶螨属(Tetranychus spp.)。
植物寄生线虫包括短体线虫属(Pratylenchus spp.),相似穿孔线虫(Radopholus similis),起绒草茎线虫(Ditylenchusdipsaci),半穿刺线虫(Tylenchulus semipenetrans),异皮线虫属(Heterodera spp.),球异皮线虫属(Globodera spp.),根结线虫属(Meloidogyne spp.),滑刃线虫属(Aphelenchoides spp.),长针线虫属(Longidorus spp.),剑线虫属(Xiphinema spp.)和毛刺线虫属(Trichodorus spp.)。
本发明的式(Ⅰ)的化合物特别具有高的杀昆虫活性。
本发明的化合物特别成功地用于防治伤害植物的叶子和土壤的昆虫,例如抗蝽幼虫(Aedes aegypti),抗甜菜蚜(Aphis fabae),抗葱蝇(Hylemyia antiqua)的卵,抗桃蚜(Myzus persicae),抗黑尾叶蝉(Neophotettix cincticeps),抗辣根猿叶甲(Phaedoncochleariae)幼虫,和抗草地粘虫(Spodoptera frugiperda)幼虫。
此外,本发明的化合物还具有根系作用。
活性化合物可以转化成常规制剂,例如溶液、乳剂、可湿性粉末剂、悬浮剂、粉剂、细粉剂、糊剂、可溶性粉末剂、颗粒剂、混悬乳油、浸有活性化合物的天然和合成材料和在聚合物中的非常细的胶囊。
这些制剂可以用已知的方式制备,例如,将活性化合物与扩充剂即液体溶剂和/或固体载体混合,如果适当,使用表面活性剂,即乳化剂和/或分散剂和/或起泡剂。
如果使用的扩充剂是水,则也可以用例如有机溶剂作助溶剂。合适的液体溶剂主要有:芳香族化合物,如二甲苯,甲苯或烷基萘,氯代芳香族化合物或氯代脂肪烃,如氯代苯类、氯乙烯类或二氯甲烷,脂族烃,如环己烷或石蜡,例如矿物油馏份,矿物油和植物油,醇类,如丁醇或乙二醇以及其醚和酯,酮类,如丙酮、甲乙酮、甲基异丁基酮或环己酮,强极性溶剂,如二甲基甲酰胺和二甲亚砜,还有水。
合适的固体载体是:
例如铵盐和磨碎的天然矿物质,如高岭土、粘土、滑石、白垩、石英、硅镁土、蒙脱石或硅藻土,和磨碎的合成矿物质,如高分散二氧化硅、矾土和硅酸盐;用于颗粒剂的适合的固体载体是:例如压碎和破碎的天然矿物质如方解石、大理石、浮石、海泡石和白云石,和有机和无机粉的合成颗粒,和如下有机物的颗粒:例如锯木屑、椰壳、玉米穗轴和烟茎;适合的乳化剂和/或起泡剂是:例如非离子和阴离子乳化剂,如聚氧乙烯脂肪酸酯、聚氧乙烯脂肪醇醚,例如,烷基芳基聚乙二醇醚,烷基磺酸盐,烷基硫酸盐,芳基磺酸盐和蛋白质水解产物;适合的分散剂是:例如,木素亚硫酸盐废液和甲基纤维素。
制剂中,可以使用增粘剂,如羧甲基纤维素、天然和合成的粉状、颗粒或乳胶形式的聚合物,如阿拉伯胶、聚乙烯醇和聚乙酸乙烯酯,和天然磷脂,如脑磷脂和卵磷脂和合成磷脂。其它添加剂可以是矿物油和植物油。
可以使用着色剂,如无机颜料,例如氧化铁、氧化钛和普鲁士蓝,和有机染料,如茜素染料、偶氮染料和金属酞菁染料,和痕量营养素如铁、锰、硼、铜、钴、钼和锌的盐。
一般情况下,制剂含有0.1-95%重量的活性化合物,优选0.5-90%。
本发明活性化合物可以以其商业上可得的制剂和以从这些制剂制备的使用形式作为与其它活性化合物的混合物存在,所述的其它活性化合物是例如杀昆虫剂,引诱剂,消毒剂,杀细菌剂,杀螨剂、杀线虫剂,杀真菌剂,生长调节物质或除草剂。杀昆虫剂包括例如磷酸酯,氨基甲酸酯,羧酸酯,氯代烃,苯基脲和特别是微生物产生的物质。
特别有利的混合成分是下面的化合物:
杀真菌剂:
aldimorph,氨丙磷酸,氨丙磷酸钾盐,andoprim,敌菌灵,戊环唑,azoxystrobin,
苯霜灵,邻碘酰苯胺,苯菌灵,benzamacril,benzamacril-isobutyl,双丙氨酰磷,乐杀螨,联苯,双苯三唑醇,灭瘟素,糠菌唑,乙嘧酚磺酸酯,丁赛特,
石硫合剂,capsimycin,敌菌丹,克菌丹,多菌灵,萎锈灵,carvon,灭螨猛,灭瘟唑,chlorfenazole,地茂散,氯化苦,百菌消,乙菌利,clozylacon,代森盐,霜尿氰,环唑醇,cyprodinil,酯菌胺,debacarb,双氯酚,苄氯三唑醇,diclofluanid,哒菌清,氯硝胺,乙霉威,噁醚唑,二甲嘧吩,烯酸吗啉,烯唑醇(diniconazole),烯唑醇(diniconazole-M),二硝巴豆酸酯,二苯胺,吡菌硫,灭菌磷,二噻农,十二环吗啉,多果定,联氨噁唑酮,
克瘟散,epoxyconazole,乙环唑,乙嘧酚,土菌灵,
famoxadon,咪菌腈,氯苯嘧啶醇,fenbuconazole,甲呋酰苯胺,种衣酯,拌种咯,苯锈啶,丁苯吗啉,三苯基醋酸锡,三苯基氢氧化锡,福美铁,嘧菌腙,氟啶胺,flumetover,氟氯菌核利,fluquinconazole,调嘧醇,氟硅唑,磺菌胺,氟酰胺,粉唑醇,灭菌丹,乙磷铝,乙磷钠,四氯苯酞,麦穗宁,呋霜灵,furametpyr,二甲呋酰苯胺,呋菌唑,呋醚唑,拌种胺,
谷种定,
六氯苯,己唑醇,噁霉灵,
抑霉唑,酰胺唑,双胍辛醋酸盐(iminoctadine,iminoctadinealbesilate,iminoctadine triacetate),iodocarb,ipconazole,异稻瘟净(IBP),异菌脲,irumamycin,稻瘟灵,isovaledione,
春雷霉素,kresoxim-methyl,铜制剂,例如:氢氧化铜,环烷酸铜,氯氧化铜,硫酸铜,氧化铜,8-羟基喹啉铜和波尔多液,
代森锰铜,代森锰,代森锰锌,meferimzone,嘧菌胺,灭锈胺,甲霜灵,metconazole,磺菌威,呋菌胺,代森联,氯苯咯菌胺,噻菌胺,米多霉素,腈菌唑,甲菌利,
二甲基二硫氨基甲酸镍,nitrothal-isopropyl,氟苯嘧啶醇,甲呋酰胺,噁霜灵,oxamocarb,喹菌酮,氧化萎锈灵,oxyfenthiin,
稻瘟酯,戊菌唑,戊菌隆,稻瘟磷,四氯苯酞,多马霉素,病花灵,聚氨基甲酸酯,多氧霉素,烯病异噻唑,味鲜安,腐霉利,丙酰胺,propanosine-sodium,环丙唑,丙森锌,吡嘧磷,啶斑肟,pyrimethanil,咯喹酮,氯吡呋醚,quinconazole,五氯硝基苯(PCNB),
硫和硫制剂,
戊唑醇,叶枯酞,四氯硝基苯,调环烯,氟嘧唑,噻菌灵,噻菌腈,thifluzamide,甲基硫菌灵,福美双,tioxymid,甲基立枯磷,甲基氟磺胺,三唑酮,三唑醇,triazbutil,唑菌嗪,杨菌胺,三环唑,十三吗啉,氟菌唑,嗪氨灵,triticonazole,
烯效唑,
稻纹散,乙烯菌核利,烯霜苄唑,
zarilamide,代森锌,福美锌,还有
Dagger G,
OK-8705,
OK-8801,
α-(1,1-二甲基乙基)-β-(2-苯氧基乙基)-1H-1,2,4-三唑-1-乙醇,
α-(2,4-二氯苯基)-β-氟-b-丙基-1H-1,2,4-三唑-1-乙醇,
α-(2,4-二氯苯基)-β-甲氧基-a-甲基-1H-1,2,4-三唑-1-乙醇,
α-(5-甲基-1,3-二噁烷-5-基)-β-[[4-(三氟甲基)-苯基]-亚甲基]-1H-1,2,4-三唑-1-乙醇,
(5RS,6RS)-6-羟基-2,2,7,7-四甲基-5-(1H-1,2,4-三唑-1-基)-3-辛酮,
(E)-a-(甲氧基亚氨基)-N-甲基-2-苯氧基-苯基乙酰胺,
{2-甲基-1-[[[1-(4-甲基苯基)-乙基]-氨基]-羰基]-丙基}-氨基甲酸异丙酯,1-(2,4-二氯苯基)-2-(1H-1,2,4-三唑-1-基)-乙酮O-(苯基甲基)-肟,
1-(2-甲基-1-萘基)-1H-吡咯-2,5-二酮,
1-(3,5-二氯苯基)-3-(2-丙烯基)-2,5-吡咯烷二酮,
1-[(二碘代甲基)-磺酰基]-4-甲基-苯,
1-[[2-(2,4-二氯苯基)-1,3-二氧戊环-2-基]-甲基]-1H-咪唑,
1-[[2-(4-氯苯基)-3-苯基环氧乙烷基]-甲基]-1H-1,2,4-三唑,
1-[2-[2-[(2,4-二氯苯基)-甲氧基]-苯基]-乙烯基]-1H-咪唑,
1-甲基-5-壬基-2-(苯基甲基)-3-吡咯烷酮,
2’,6’-二溴-2-甲基-4’-三氟甲氧基-4’-三氟-甲基-1,3-噻唑-5-N-碳酰苯胺,
2,2-二氯-N-[1-(4-氯苯基)-乙基]-1-乙基-3-甲基-环丙烷甲酰胺,
2,6-二氯-5-(甲硫基)-4-嘧啶基-硫代氰酸酯,
2,6-二氯-N-(4-三氟甲基苄基)-苯甲酰胺,
2,6-二氯-N-[[4-(三氟甲基)-苯基]-甲基]-苯甲酰胺,
2-(2,3,3-三碘代-2-丙烯基)-2H-四唑,
2-[(1-甲基乙基)磺酰基]-5-(三氯甲基)-1,3,4-噻二唑,
2-[[6-脱氧-4-O-(4-O-甲基-β-D-吡喃葡糖基)-a-D-吡喃葡糖基]-氨基]-4-甲氧基-1H-吡咯并[2,3-d]嘧啶-5-腈,
2-氨基丁烷,
2-溴-2-(溴代甲基)戊烷二腈,
2-氯-N-(2,3-二氢-1,1,3-三甲基-1H-茚-4-基)-3-吡啶甲酰胺,
2-氯-N-(2,6-二甲基苯基)-N-(异硫代氰酰甲基)-乙酰胺,
2-苯基苯酚(OPP),
3,4-二氯-1-[4-(二氟甲氧基)-苯基]-1H-吡咯-2,5-二酮,
3,5-二氯-N-[氰基-[(1-甲基-2-丙炔基)-氧基]-甲基]-苯甲酰胺,
3-(1,1-二甲基丙基-1-氧代-1H-茚-2-腈),
3-[2-(4-氯苯基)-5-乙氧基-3-异噁唑烷基]-吡啶,
4-氯-2-氰基-N,N-二甲基-5-(4-甲基苯基)-1H-咪唑-1-磺酰胺,
4-甲基-四唑并[1,5-a]喹唑啉-5(4H)-酮,
8-(1,1-二甲基乙基)-N-乙基-N-丙基-1,4-二氧杂螺[4.5]癸烷-2-甲烷胺,
8-羟基喹啉硫酸盐,
9H-呫吨-2-[(苯基氨基)-羰基]-9-羧酸酰肼,
双-(1-甲基乙基)-3-甲基-4-[(3-甲基苯甲酰基)氧基]-2,5-噻吩二羧酸酯,
顺-1-(4-氯代苯基)-2-(1H-1,2,4-三唑-1-基)-环庚醇,
顺-4-[3-[4-(1,1-二甲基丙基)-苯基-2-甲基丙基]-2,6-二甲基-吗啉]盐酸盐,
[(4-氯苯基)-偶氮]-氰基乙酸乙酯,
碳酸氢钾,
甲烷四硫醇钠盐,
1-(2,3-二氢-2,2-二甲基-1H-茚-1-基)-1H-咪唑-5-羧酸甲酯,
N-(2,6-二甲基苯基)-N-(5-异噁唑基羰基)-DL-丙氨酸甲酯,
N-(氯代乙酰基)-N-(2,6-二甲基苯基)-DL-丙氨酸甲酯,
N-(2,3-二氯-4-羟基苯基)-1-甲基-环己烷甲酰胺,
N-(2,6-二甲基苯基)-2-甲氧基-N-(四氢-2-氧代-3-呋喃基)-乙酰胺,
N-(2,6-二甲基苯基)-2-甲氧基-N-(四氢-2-氧代-3-噻吩基)-乙酰胺,
N-(2-氯-4-硝基苯基)-4-甲基-3-硝基-苯磺酰胺,
N-(4-环己基苯基)-1,4,5,6-四氢-2-嘧啶胺,
N-(4-己基苯基)-1,4,5,6-四氢-2-嘧啶胺,
N-(5-氯-2-甲基苯基)-2-甲氧基-N-(2-氧代-3-噁唑啉基)-乙酰胺,
N-(6-甲氧基)-3-吡啶基)-环丙烷甲酰胺,
N-[2,2,2-三氯-1-[(氯代乙酰基)-氨基]-乙基]-苯甲酰胺,
N-[3-氯代-4,5-双(2-丙炔基氧基)-苯基]-N’-甲氧基-甲亚氨酰胺,
N-甲酰基-N-羟基-DL-丙氨酸钠盐,
O,O-二乙基[2-(二丙基氨基)-2-氧代乙基]-乙基硫代氨基磷酸酯,
O-甲基S-苯基苯基丙基硫代氨基磷酸酯,
S-甲基1,2,3-苯并噻二唑-7-硫代甲酸酯,
螺[2H]-1-苯并吡喃-2,1’(3’H)-异苯并呋喃-3’-酮。
杀细菌剂:
bromopol,双氯酚,氯甲基吡啶,二甲基二硫氨基甲酸镍,春雷霉素,异噻唑酮,呋喃羧酸,oxytetracycline,烯异丙噻唑,链霉素,叶枯酞,硫酸铜和其它铜制剂。
杀昆虫剂/杀螨剂/杀线虫剂:
齐墩螨素,AC303630,乙酰甲胺磷,氟酯菊酯,棉铃威,涕灭威,甲体氯氰菊酯,双虫脒,阿凡曼菌素,AZ60541,azadirachtin,azinphos-A,azinphos-M,保棉磷,三唑锡,AKD1022,
苏云金杆菌,噁虫威,丙硫克百威,杀虫磺,氟氯氰菊酯,氟氯菊酯,BPMC,brofenprox,溴硫磷,合杀威,噻嗪酮,丁酮威,butylpyridaben,
硫线磷,甲萘威,克百威,三硫磷,丁硫克百威,杀螟丹,CGA157419,CGA184699,chloethocarb,chlorethoxyfos,chlorfenvinphos,毒虫畏,定虫隆,氯甲硫磷,毒死蜱,甲基毒死蜱,顺式-苄呋菊酯,clocythrin,四螨嗪,杀螟腈,乙氰菊酯,氟氯氰菊酯-β,cyhalothrin,cyfluthrin,三环锡,氯氰菊酯,灭蝇胺,
溴氰菊酯,内吸磷-M,内吸磷-S,甲基内吸磷,diaeloden,杀螨隆,二嗪磷,酚线磷,敌敌畏,dicliphos,百治磷,乙硫磷,除虫脲,乐果,甲基毒虫畏,敌噁磷,乙拌磷,
克瘟散,emamectin,高氰戊菊酯,乙硫苯威,乙硫磷,醚菊酯,灭线磷,乙嘧硫磷,
虫胺磷,喹螨醚,苯丁锡,杀螟硫磷,仲丁威,苯硫威,双氧威,氯氰菊酯,fenpyrad,唑螨酯,倍硫磷,氰戊菊酯,fipronil,氟定胺,氟螨脲,氟氰戊菊酯,氟虫脲,flufenprox,氟胺氰菊酯,地虫硫磷,安果,噻唑磷,fubfenprox,呋线威,
HCH,庚烯磷,氟铃脲,噻螨酮,
吡虫啉,异稻瘟净,氯唑磷,异丙胺磷,叶蝉散,噁唑磷,异阿凡曼菌素,
氯氟氰菊酯,lufenuron,
马拉硫磷,灭蚜蜱,速灭磷,mesulfenphos,蜗牛敌,虫螨畏,甲胺磷,杀扑磷,灭梭威,灭多威,速灭威,milbemectin,久效磷,moxidectin,
二溴磷,NC184,NI25,nitenpyram,
氧乐果,杀线威,亚砜吸磷,异砜磷,
对硫磷-A,对硫磷-M,氯菊酯,稻丰散,甲拌磷,伏杀硫磷,亚胺硫磷,磷胺,辛硫磷,抗芽威,甲基嘧啶磷,嘧啶磷-A,丙溴磷,猛杀威,丙虫磷,残杀威,丙硫磷,发果,pymetrozin,吡唑硫磷,pyradaphenthion,pyresmethrin,除虫菊酯,哒螨酮,pyrimidifen,蚊蝇醚,
喹硫磷,
RH5992,
蔬果磷,sebufos,silafluofen,治螟硫磷,甲丙硫磷,tebufenozid,tebufenpyrad,tebupirimiphos,伏草隆,七氟菊酯,双硫磷,特灭威,特丁磷,杀虫畏,thiafenox,硫双威,久效磷,二甲硫吸磷,虫线磷,thuringiensin,四溴菊酯,苯噻螨,三唑磷,triazuron,敌百虫,杀虫隆,混灭威,TI435,
芽灭多,XMC,灭杀威,YI5301/5302,zetamethrin。
也可能是与其它已知的活性化合物例如除草剂,或肥料和生长调节物质的混合物。
当用作杀昆虫剂时,本发明的活性化合物还可以以它们的商售制剂和从这些制剂制备的作为与增效剂的混合物的使用形式存在。增效剂是提高活性化合物的活性,而加入的增效剂自身不必是活性的化合物。
从商售制剂制备的使用形式的活性化合物含量可以在宽范围内变化。使用形式的活性化合物浓度可以是0.0000001-95%重量的活性化合物,优选在0.0001%和1%重量之间。
以适合这些使用形式的方式进行施用。
当用来抗卫生领域害虫和储存产品害虫时,这些活性化合物的特征在于对木材和粘土的极好的有后效的活性,以及对用石灰处理过的物质上的碱的好的稳定性。
本发明活性化合物不仅对抗植物,卫生领域和储存产品害虫有作用,而且还用于兽药领域抗动物寄生虫(定居寄生虫),例如硬蜱,软蜱,马痒螨,恙螨,蝇(叮和吮),寄生蝇幼虫,虱,头虱,鸟虱和蚤。这样的寄生虫包括:
虱目(Anolpurida),例如,血虱属(Haematopinus spp.),长颚虱(Linognathus spp.),虱属(Pediculus spp.),阴虱属(Phtirusspp.),管虱属(Solenopotes spp.)。
食毛目咬虱(Mallophagida)和Amblycerina及Ischnocerina亚目,例如毛羽虱属(Trimenopon spp.),Menopon spp.,巨羽虱属(Trinoton spp.),牛羽虱属(Boyicola spp.),Werneckiella spp.,Lepikentron spp.,Damalina spp.,Trichodectes spp.,Felcolaspp.。
双翅目(Diptera)和长角亚目(Nematocerina)和Brachycerina亚目,例如伊蚊(Aedes spp.),斑按蚊属(Anopheles spp.),库蚊(Culexspp.),蚋属(Simulium spp.),全毛真蚋(Eusimulium spp.),白蛉(Phlebotomus spp.),罗蛉属(Lutzomyia spp.),库蠓(Culicoidesspp.),斑虻(Chrysops spp.),瘤虻(Hybomitra spp),Atylotusspp.,虻属(Tabanus spp),麻虻(Haematopota spp),Philipomyiaspp.,Braula spp.,Musca spp.,齿股蝇属(Hydrotuea spp.),螫蝇(Stomoxys spp.),Haematobia spp.,Morellia spp.,厕蝇(Fanniaspp.),Glossina spp.,Calliphora spp.,Lucilia spp.,Chrysomyiaspp.,Wohlfahrtia spp.,别麻蝇(Sarcophaga spp.),Oestrusspp.,皮蝇(Hypoderma spp.),Gasterophilus spp.,虱蝇(Hippobosca spp.),Lipoptena spp.,和Melophagus spp.。
蚤目(Siphonapterida),例如,蚤属(Pulex spp.),Ctenocephalides spp.,鼠蚤(Xenopsylla spp.),和角叶蚤(Ceratophyllus spp.)。
异翅亚目(Heteropterida),例如,臭虫属(Cimex spp.),吸血猎蝽属(Triatoma spp.),Rhodnius spp.,和全圆蝽属(Panstrongylusspp.)。
非蠊目(Blattarida),例如东方非蠊(Blatta orientalis),美洲大蠊(Periplaneta americana),德国小蠊(Blattela germanica),非蠊属(Supella spp.)。
螨亚类(Acarida),和后胸气门目(Metastigmata)和中胸气门目(Mesostigmata),例如,隐喙蜱属(Argas spp.),喙蜱属(Ornithodorus spp.),耳残喙蜱(Otabius spp.),硬蜱(Ixodesspp.),花蜱属(Amblyomma spp.),牛蜱属(Boophilus spp.),矩头蜱(Dermacentor spp.),Haemophysalis spp.,璃眼蜱(Hyalommaspp.),头蜱属(Rhipicephalus spp.),鸡皮刺螨(Dermanyssusspp.),瑞立绦虫(Raillietia spp.),Pneumonyssus spp.,Sternostoma spp.,和Varroa spp.。
Actinedida(恙螨亚目,Prostigmata)和Acaridida(Astigmata),例如Acarapis spp.,姬螯螨属(Cheyletiella spp.),Ornithocheyletia spp.,Myobia spp.,疥螨(Psorergates spp.),蠕形螨(Demodex spp.),恙螨(Trombiculaspp.),Listrophorus spp.,粗脚粉螨(Acarus spp.),酪螨(Tyrophagus spp.),嗜木螨(Caloglyphus spp.),Hypodectesspp.,翼衣螨属(Pterolichus spp.),恙螨(Psoroptes spp.),恙螨(Chorioptes spp.),Octodectes spp.,疥螨(Sarcoptes spp.),Notoedres spp.,足螨(Knemidocoptes spp.,),Cytodites spp.,和Laminosioptes spp.。
例如本发明化合物具有好的杀丝光绿蝇(Lucilla cuprina fly)幼虫的发育抑制作用。
本发明式(Ⅰ)的活性化合物也适于杀死侵染农业生产家畜的节肢动物门,所述家畜是例如牛,绵羊,山羊,马,猪,驴,骆驼,水牛,兔子,鸡,火鸡,鸭,鹅和蜜蜂,其它宠物,例如狗,猫,茏养的鸟和鱼缸养殖鱼,还有试验用动物,例如仓鼠,豚鼠,大鼠和小鼠。
在兽药领域,本发明活性化合物以已知方式通过肠给药,例如以片剂,胶囊,顿服水剂,顿服药,颗粒剂,糊剂,巨丸剂,通过进食方法的形式,通过以例如浸渍或浸浴,喷洒,倒施和点施,洗用和撒粉的形式皮肤使用,也可以借助于含有活性化合物的用模子做的物品,例如颈圈,耳饰,尾饰,腿带,笼头,标记物等而使用。
当对牲畜,家禽,宠物等使用时,本发明式(Ⅰ)的活性化合物可以作为以1-80%重量的量含有活性化合物的制剂(例如粉末剂,乳剂,可流动性组合物)而被使用,直接使用或者稀释100-10000倍后使用,或者可以用作化学浴。
另外,还发现本发明式(Ⅰ)的化合物还具有杀破坏工业材料的昆虫的强的杀昆虫作用。
作为例子和作为优选可以提到下面的昆虫,但是不受此限制:甲虫,例如
家天牛(Hylotrupes bajulus),Chlorophorus pilosis,家具窃蠹(Anobium punctatum),Xestobium rufovillosum,Ptilinuspecticornis,Dendrobium pertinex,Ernobius mollis,Priobiumcarpini,欧洲竹粉蠹(Lyctus brunneus),Lyctus africanus,平颈粉蠹(Lyctus planicollis),Lyctus linearis,Lyctuspubescens,Trogoxylon aequale,Minthes rugicollis,小蠹虫种(Xyleborus spec.),Tryptodendron spec.,Apate monachus,Bostrychus capucins,Heterobostrychus brunneus,Sinoxylonspec.,和竹长蠹(Dinoderus minutus)。
膜翅目(Hymenopterans),例如
钢青小树蜂(Sirex juvencus),枞大树蜂(Urocerus gigas),Urocerus gigas taignus和Urocerus augur。
白蚁,例如
Kalotermes flavicollis,Cryptotermes brevis,Heterotermesindicola,Reticulitermes flavipes,Reticulitermessantonensis,Reticulitermes lucifugus,澳洲白蚁(Mastotermesdarwiniensis),Zootermopsis nevadensis和台湾家白蚁(Coptotermes formosanus)。
Bristle-tail,例如西洋衣鱼(Lepisma saccharina)。
本发明中所涉及的工业材料理解为非生命材料,优选塑料,粘合剂,胶料,纸和纸板,皮革,木材和木材加工产品以及涂料组合物。
要保护的、特别优选是不被昆虫侵染的材料是木材和木材加工产品。
可以用本发明试剂和含有这样试剂的混合物保护的木材和木材加工产品应理解为是指,例如建筑木材加工品,木梁,铁轨枕木,建桥木料,码头,木制运载工具,箱子,制模板,容器,电线杆,木桶,木窗,木门,胶合板,颗粒板,接合物,或者在房屋建筑或细木工行业很普通使用的木产品。
本发明活性化合物可以以其自身,乳油形式或者一般的常规制剂使用,例如粉末剂,颗粒剂,溶液,混悬剂,乳剂或糊剂。
提到的制剂可以以本身已知的方法制备,例如通过混合活性化合物和至少一种溶剂或稀释剂,乳化剂,分散剂和/或粘合剂或固定剂,水驱避剂,如果合适,干燥剂和UV稳定剂和,如果合适,着色剂和颜料和其它加工助剂。
用于保护木料和木制品的杀虫剂组合物或浓缩物以0.0001-95%重量浓度含有本发明活性化合物,特别是0.001-60%重量。
使用的组合物或浓缩物的量取决于害虫的物种和发生,并取决于基质。施用的最佳比例可以通过试验系列根据每种情况下的使用来决定。但是,一般情况下,使用以要保护的材料为基础的0.0001-20%重量,优选0.001-10%重量的活性化合物足够了。
使用的溶剂和/或稀释剂是有机化学溶剂或溶剂混合物和/或低挥发性的油或类油有机化学溶剂或溶剂混合物和/或极性有机化学溶剂或溶剂混合物和/或水和,如果合适,一种乳化剂和/或湿润剂。
优选使用的有机化学溶剂是具有大于35的挥发数和高于30℃,优选高于45℃的闪点的油或类油溶剂。作为具有低挥发性并且在水中不溶解的油或类油溶剂而使用的物质是合适的矿物油或其芳香烃级分,或者含有矿物油的溶剂混合物,优选石油溶剂,石油和/或烷基苯。
有利地使用的物质是沸点范围是170-220℃的矿物油,沸点范围是170-220℃的石油溶剂,沸点范围是250-350℃的锭子油,沸点范围是160-280℃的石油或芳香烃,松节油等。
在一个优选的实施方案中,使用了沸点范围是180-210℃的液体脂肪烃或者沸点范围是180-220℃的芳香烃和脂肪烃的高沸点混合物和/或锭子油和/或一氯代萘,优选α-一氯代萘。
具有大于35的挥发数和高于30℃,优选高于45℃的闪点的低挥发性有机油或类油溶剂可以部分替换成高挥发性或中等挥发性的有机化学溶剂,前提是该溶剂混合物也具有大于35的挥发数和高于30℃,优选高于45℃的闪点,并且杀昆虫剂/杀真菌剂混合物在该溶剂混合物中是可溶解的或可乳化的。
根据一个优选的实施方案,部分有机化学溶剂或溶剂混合物或脂肪族极性有机化学溶剂或溶剂混合物被替换。优选使用具有羟基和/或酯基和/或醚基的脂肪族有机化学溶剂,例如乙二醇醚,酯等。
本发明范围内使用的有机化学粘合剂是本身已知的合成树脂和/或粘合干燥油,并且是水可稀释和/或在使用的有机化学溶剂中是可溶解的或可分散的或可乳化的,特别是粘合剂由下面的物质组成或者含有下面的物质:丙烯酸树脂,乙烯树脂,例如聚乙酸乙烯酯,聚酯树脂,缩聚或加聚树脂,聚尿烷树脂,醇酸树脂或改性的醇酸树脂,苯酚树脂,烃类树脂,例如茚/苯并呋喃树脂,有机硅树脂,干燥植物油和/或干燥油和/或以天然和/或合成树脂为基础的物理干燥粘合剂。
作为粘合剂使用的合成树脂可以以乳液,分散液或溶液的形式使用。最多10%重量的沥青或沥青状物质也可以作为粘合剂使用。还可以使用本身已知的染料,颜料,水驱避剂,气味掩蔽物质和抑制剂或防腐蚀剂等。
根据本发明,组合物或浓缩物优选含有至少一种醇酸树脂或改性的醇酸树脂和/或干燥植物油作为有机化学粘合剂。根据本发明,优选使用油含量大于45%重量,优选50-68%重量的醇酸树脂。
上面提到的粘合剂的所有或部分粘合剂可以替换成固定剂(混合物或增塑剂(混合物)。这些添加剂是为了防止活性化合物的挥发和结晶或沉淀。优选替换0.01-30%的粘合剂(以使用的100%粘合剂为基础)。
增塑剂来自邻苯二甲酸酯类,例如邻苯二甲酸二丁酯,邻苯二甲酸二辛酯或邻苯二甲酸苄酯丁酯,磷酸酯类例如磷酸三丁酯,己二酸酯,例如己二酸二-(2-乙基己基)酯,硬脂酸酯,例如硬脂酸丁酯或硬脂酸戊酯,油酸酯例如油酸丁酯,甘油醚或较高分子量的乙二醇醚,甘油酯和对甲苯磺酸酯。
固定剂的化学基础是聚乙烯基烷基醚,例如,聚乙烯基甲基醚,或酮类,例如二苯酮或二苯乙酮(ethylenebenzophenone)。
可能的溶剂或稀释剂特别是水,如果合适,作为与一种或几种上述有机化学溶剂或稀释剂,乳化剂和分散剂的混合物。
特别有效的木材保护作用是通过大量的工业规模浸入方法实现的,例如真空,双真空或加压方法。
如果合适,即用型组合物可以还含有其它的杀虫剂和,如果合适,另外一种或几种杀真菌剂。
可能的另外的混合成分优选是WO94/29268中提到的杀昆虫剂和杀真菌剂。该文献中提到的化合物明确地引入本申请。
可以提到的特别优选的混合成分是杀昆虫剂,例如毒死稗,辛硫磷,silafluofin,甲体氯氰菊酯,氟氯氰菊酯,氯氰菊酯,溴氰菊酯,氯菊酯,吡虫啉,NI-25,氟虫脲,氟铃脲和杀虫隆,还有杀真菌剂,例如epoxyconazole,己唑醇,戊环唑,环丙唑,戊唑醇,环唑醇,metconazole,抑霉唑,苯氟磺胺,甲苯氟磺胺,氨基甲酸3-碘代-2-丙炔基丁酯,N-辛基-异噻唑啉-3-酮和4,5-二氯-N-辛基异噻唑啉-3-酮。
本发明活性化合物的制备和应用可以通过下面的实施例中详细说明。制备实施例
实施例1
5℃下,搅拌下,25ml无水二甲基甲酰胺中的1.5g(0.0063mol)1-(6-氯-吡啶-3-基-甲基)-2-氰基亚氨基咪唑烷与0.25g(0.0063mol)氢化钠一次一点地混合。室温下搅拌1小时后,0℃下加入0.7ml(0.0063mol)异丙氧基甲基氯,将混合物搅拌过夜。通过蒸馏出溶剂浓缩反应混合物,并且残余物溶解于石油醚并过滤。滤波通过硅胶柱色谱纯化(二氯甲烷/甲醇∶15/0.5)。
得到熔点85-87℃的0.57g(理论量的29%)1-(6-氯-吡啶-3-基-甲基)-2-氰基亚氨基-3-异丙氧基甲基-咪唑烷。实施例2
搅拌下,5ml无水二甲基甲酰胺中的1.5g(5.7mmol)1-(2-氯-噻唑-5-基-甲基)-2-硝基亚氨基咪唑烷与0.26g(6.5mmol)氢化钠一次一点地混合。混合物在室温下搅拌一会儿,冷却下加入0.70g(6.5mmol)正丙氧基甲基氯并将混合物搅拌过夜。减压浓缩反应混合物,残余物与水混合并且用二氯甲烷萃取。有机相用硫酸钠干燥并浓缩,残余物与二异丙基醚搅拌并再浓缩。
得到计算指数n20 D=1.5781的1.54g(理论量的76%)1-(2-氯-噻唑-5-基-甲基)-2-硝基亚氨基-3-正丙氧基甲基-咪唑烷。
实施例3
室温下,10ml无水二甲基甲酰胺中的2.54g(0.01mol)1-(6-氯-吡啶-3-基-甲基)-2-硝基亚氨基咪唑啉与0.44g(0.011mol)氢化钠一次一点地混合。将混合物搅拌一会儿,冷却下加入2.17g(0.0125mol)溴代乙氧基甲基氯并将混合物在室温下搅拌过夜。减压浓缩反应混合物,残余物与水混合并且用二氯甲烷萃取。有机相用硫酸钠干燥并浓缩,残余物与二异丙基醚搅拌并过滤。滤液通过硅胶柱色谱纯化(二氯甲烷/甲醇∶10/1)。
得到熔点90-92℃的2.3g(理论量的53%)1-(6-氯-吡啶-3-基-甲基)-2-硝基亚氨基-3-溴代乙氧基甲基-咪唑啉。
类似于制备实施例1-3并且根据关于式(Ⅰ)的化合物的制备的一般性说明,获得下面表1中列出的化合物: [通过HPLC根据EEC Directive79/831 AnnexV.A8测定logP值(梯度方法,乙腈/0.1%磷酸水溶液]应用实施例
实施例A伊蚊(Aedes)试验溶剂: 1000份重量甲醇
为了制备活性化合物的合适的制剂,将1份重量的活性化合物与所述量溶剂混合,用水将浓缩物稀释到期望的浓度。
将蚊子幼虫(Aedes aegypti)放置在期望浓度的活性化合物的制剂中。
一定时间后,测定对幼虫的作用.100%表示所有的动物表现出严重症状或者已经被杀死;0%表示没有杀死动物。
在该项试验中,在例示的0.0016%活性化合物浓度下,制备实施例4,5和7的化合物在各种情况下在4小时后杀死效果100%。
实施例B蚜虫(Aphis)试验(系统性作用)溶剂: 7份重量的二甲基甲酰胺乳化剂: 1份重量的烷基芳基聚乙二醇醚
为了制备活性化合物的合适的制剂,将1份重量的活性化合物与所述量溶剂和所述量的乳化剂混合,用水将浓缩物稀释到期望的浓度。
各种情况下用20ml期望浓度的活性化合物的制剂浇灌被蚕豆蚜(Aphis fabae)严重侵染的大豆植物(蚕豆)(Vicia faba),使得活性化合物的制剂渗透到土壤中而不湿润发出的芽。活性化合物由根吸收并转移到芽部。
一定时间后,测定杀死百分率。100%表示所有的蚜虫都已经被杀死;0%表示没有杀死一只蚜虫。
在该项试验中,在例示的0.01%活性化合物浓度下,制备实施例4和9的化合物各种情况下在4天后杀死效果100%,制备实施例5的化合物各种情况下在4天后杀死效果95%。
实施例C黑蝇(Hylemyia)试验溶剂: 100份重量的丙酮
1900份重量的甲醇
为了制备活性化合物的合适的制剂,将1份重量的活性化合物与所述量溶剂混合,用甲醇将浓缩物稀释到期望的浓度。
将一定量的期望浓度的活性化合物的制剂移液到标准化定量人工食物上。甲醇蒸发后,将大约20只葱蝇(Hylemyia antiqua)卵放置在食物上。
一定时间后,测定卵或幼虫的杀死百分率。100%表示所有的动物都已经被杀死;0%表示没有杀死一只动物。
在该项试验中,在例示的0.05%活性化合物浓度下,制备实施例4的化合物在7天后杀死效果100%。实施例D瘤额蚜(Myzus)试验溶剂: 7份重量二甲基甲酰胺乳化剂: 1份重量烷基芳基聚乙二醇醚
为了制备活性化合物合适的制剂,将1份重量活性化合物与所述量溶剂和所述量乳化剂混合,用水将浓缩物稀释到需要的浓度。
将桃赤蚜(Myzus persicae)严重侵染的甘蓝叶(Brassicaoleracea)浸入到期望浓度的活性化合物的制剂中。
一定时间后,测定杀死百分率。100%表示所有的蚜虫都已经被杀死;0%表示没有杀死一只蚜虫。
在该项试验中,以例示的0.1%活性化合物浓度,制备实施例10,11,12,13,14,15,16,17,18,20,25和36的化合物在各种情况下6天后杀死率100%。
实施例E叶蝉(Nephotettix)试验溶剂: 7份重量二甲基甲酰胺乳化剂: 1份重量烷基芳基聚乙二醇醚
为了制备活性化合物合适的制剂,将1份重量活性化合物与所述量溶剂和所述量乳化剂混合,用水将浓缩物稀释到需要的浓度。
通过浸入到期望浓度的活性化合物的制剂中处理稻苗(Oryzasativa),并且在籽苗还湿润的时候用黑尾叶蝉(Nephotettixcincticeps)的幼虫侵染。
一定时间后,测定杀死百分率。100%表示所有的叶蝉都已经被杀死;0%表示没有杀死一只叶蝉。
在该项试验中,以例示的0.1%活性化合物浓度,制备实施例4,10,12,13,14,15,18,19,21,24,25,26,33和36的化合物在各种情况下6天后杀死率100%。实施例F叶虫(Phaedon)幼虫试验溶剂: 7份重量二甲基甲酰胺乳化剂: 1份重量烷基芳基聚乙二醇醚
为了制备活性化合物合适的制剂,将1份重量活性化合物与所述量溶剂和所述量乳化剂混合,用水将浓缩物稀释到需要的浓度。
通过浸入到期望浓度的活性化合物的制剂中来处理甘蓝叶(Brassica oleracea),并在叶子还湿润的时候用辣根猿叶甲幼虫(Phaedon cochleariae)侵染。
一定时间后,测定杀死百分率。100%表示所有的甲虫幼虫都已经被杀死;0%表示没有杀死一只甲虫幼虫。
在该项试验中,以例示的0.1%活性化合物浓度,制备实施例4,10,12,17,18,19,21,25,33,34,35和36的化合物在各种情况下7天后产生100%杀死率。
实施例G草地粘虫(Spodoptera frugiperda)试验溶剂: 7份重量二甲基甲酰胺乳化剂: 1份重量烷基芳基聚乙二醇醚
为了制备活性化合物合适的制剂,将1份重量活性化合物与所述量溶剂和乳化剂混合,用水将浓缩物稀释到需要的浓度。
通过浸入到期望浓度的活性化合物的制剂中来处理甘蓝叶(Brassica oleracea),并在叶子还湿润的时候用草地粘虫(Spodoptera frugiperda)幼虫侵染。
一定时间后,测定杀死百分率。100%表示所有的幼虫都已经被杀死;0%表示没有杀死一只幼虫。
在该项试验中,以例示的0.1%活性化合物浓度,制备实施例2,10,12,13,17,18,20,25,33,35和36的化合物在各种情况下7天后杀死率100%。
实施例H草地粘虫(Spodoptera frugiperda)试验/人工食物溶剂: 100份重量丙酮
1900份重量甲醇
为了制备活性化合物合适的制剂,将1份重量活性化合物与所述量溶剂混合,用甲醇将浓缩物稀释到需要的浓度。
将所述量的期望浓度的活性化合物的制剂移液到标准化定量人工食物上。甲醇蒸发后,各种情况下,将一只草地粘虫(Spodopterafrugiperda)幼虫(L2-L3)放在食物上,重复3次。
所需时间后,测定杀死百分率。100%表示所有的动物都已经被杀死;0%表示没有杀死一只动物。
在该项试验中,以例示的0.05%活性化合物浓度,制备实施例4的化合物在7天后杀死率100%。
实施例Ⅰ极限浓度试验/根系作用试验用昆虫: 蚕豆蚜(Aphis fabae)溶剂: 4份重量的丙酮乳化剂: 1份重量的烷基芳基聚乙二醇醚
为了制备活性化合物的合适的制剂,将1份重量的活性化合物与所述量溶剂和所述量的乳化剂混合,用水将浓缩物稀释到期望的浓度。
活性化合物制剂与土壤充分混合。制剂中活性化合物的浓度不是最重要的,只有每单位体积土壤的活性化合物的重量(以ppm表示(=mg/l))是关键的。将处理过的土壤装入小盆,种上发芽前的宽豆角。这样,活性化合物可以由植物根吸收并转移到叶。
为了证明根系作用,7天后叶子上侵染上述试验动物。又6天后,通过计数或估计死亡的动物进行评价。从被杀死的动物数目推导出活性化合物的根系作用。当所有的试验动物都已经被杀死时是100%,当存活昆虫与未处理对照物相等时是0%。
在该项试验中,在例示的20ppm活性化合物浓度下,制备实施例4和5的化合物杀死效果为100%。
实施例J丽蝇(Blowfly)幼虫试验/发育抑制作用试验动物: 丝光绿蝇(Lucilia cuprina)幼虫溶剂: 二甲亚砜
20mg活性化合物溶解于1ml二甲亚砜中,通过用Dest.H2O稀释制备更稀的浓缩物。
将大约20只丝光绿蝇(Lucilia cuprina)幼虫引入到盛有大约1cm3马肉和0.5ml要测试的活性化合物的制剂的试验管中。24小时和48小时后测定活性化合物的制剂的药效。将试验管转移到底部覆盖砂子的烧杯中。又过2天后,取出试验管并计数蛹。
通过未处理对照物发育期1.5倍后孵化的蝇数评价活性化合物的制剂的效果。100%表示没有孵化出蝇;0%表示所有的蝇都正常孵化出。
在该项试验中,以例示的100ppm活性化合物浓度,制备实施例9,10,11,12和13的化合物表现出100%的发育抑制效果。
Claims (7)
1.式(Ⅰ)的化合物其中R1代表包含1,2,3或4个氮原子和/或一个或两个氧或硫原子作为杂原子成环原子-其中杂原子数是1,2,3或4-并且任选被卤素,氰基,硝基,烷基,卤代烷基,链烯基,卤代链烯基,炔烃基,烷氧基,卤代烷氧基,链烯基氧基,卤代链烯基氧基,炔烃基氧基,烷硫基,卤代烷硫基,链烯基硫基,卤代链烯基硫基,炔烃基硫基,烷基亚磺酰基,卤代烷基亚磺酰基,烷基磺酰基,卤代烷基磺酰基,氨基,烷基氨基,二烷基氨基,芳基,芳基硫基,芳基氨基,芳基烷基,甲酰基氨基,烷基羰基氨基,甲酰基,氨基甲酰基,烷基羰基和/或烷氧羰基取代的5-或6-元杂环基团;R2代表氢或烷基,R3代表基团-OR4,-OCOR5,-OCOOR6,-OCONR7R8和-OSO2R9,其中R4,R5和R6各自独立地代表烷基,烷氧基烷基,卤代烷基,链烯基,炔烃基,烷基氨基烷基,二烷基氨基烷基,任选被取代的环烷基和各种情况下任选被取代的苯基或苄基,R7和R8各自独立地代表氢,烷基,链烯基和各种情况下任选被取代的苯基或苄基,和R9代表烷基或任选被取代的苯基,A代表基团-CH2CH2-,-(CH2)3-和-CH=CH-,和Z代表氰基或硝基,条件是,如果Z代表NO2和A代表-CH2CH2-,则R2代表氢;并且排除下面的式(Ⅰ)的化合物R2 H,R3 OCH3,A -CH2CH2-和Z NO2
2.权利要求1的式(Ⅰ)的化合物的制备方法:其中R1代表包含1,2,3或4个氮原子和/或一个或两个氧或硫原子作为杂原子成环原子-其中杂原子数是1,2,3或4-并且任选被卤素,氰基,硝基,烷基,卤代烷基,链烯基,卤代链烯基,炔烃基,烷氧基,卤代烷氧基,链烯基氧基,卤代链烯基氧基,炔烃基氧基,烷硫基,卤代烷硫基,链烯基硫基,卤代链烯基硫基,炔烃基硫基,烷基亚磺酰基,卤代烷基亚磺酰基,烷基磺酰基,卤代烷基磺酰基,氨基,烷基氨基,二烷基氨基,芳基,芳基硫基,芳基氨基,芳基烷基,甲酰基氨基,烷基羰基氨基,甲酰基,氨基甲酰基,烷基羰基和/或烷氧羰基取代的5-或6-元杂环基团;R2代表氢或烷基,R3代表基团-OR4,-OCOR5,-OCOOR6,-OCONR7R8和-OSO2R9,其中R4,R5和R6各自独立地代表烷基,烷氧基烷基,卤代烷基,链烯基,炔烃基,烷基氨基烷基,二烷基氨基烷基,任选被取代的环烷基和各种情况下任选被取代的苯基或苄基,R7和R8各自独立地代表氢,烷基,链烯基和各种情况下任选被取代的苯基或苄基,和R9代表烷基或任选被取代的苯基,A代表基团-CH2CH2-,-(CH2)3-和-CH=CH-,和Z代表氰基或硝基,条件是,如果Z代表NO2和A代表-CH2CH2-,则R2代表氢;并且排除下面的式(Ⅰ)的化合物R2 H,R3 OCH3,A -CH2CH2-和Z NO2所述方法的特征在于,在碱存在下和如果适当在稀释剂存在下,使式(Ⅱ)的化合物与式(Ⅲ)的卤代化合物反应,其中R1,A和Z如上定义,其中R2和R3如上定义,和X代表卤素(特别是氯或溴)。
3.权利要求1的式(Ⅰ)的化合物,其中R1代表选自吡唑基,1,2,4-三唑基,噁唑基,异噁唑基,噻唑基,异噻唑基,1,2,5-噻二唑基,吡啶基,哌嗪基和嘧啶基,并且任选被氟,氯,溴,氰基,硝基,C1-C2-烷基(任选被氟和/或氯取代的),C1-C2-烷氧基(任选被氟和/或氯取代的),C1-C2-烷硫基(任选被氟和/或氯取代的),或C1-C2-烷基磺酰基(任选被氟和/或氯取代的)取代的5-至6-元杂环基团;R2代表氢或C1-C6-烷基,R3代表基团-OR4,-OCOR5,-OCOOR6,-OCONR7R8和-OSO2R9,其中R4,R5和R6各自独立地代表C1-C12-烷基,C1-C4-烷氧基-C1-C4-烷基,具有1-5个相同或不同的卤原子例如氟,氯和溴原子的C1-C4-卤代烷基;C2-C4-链烯基,C2-C4-炔烃基,C1-C4-烷基氨基-C1-C4-烷基,二(C1-C4)-烷基氨基-C1-C4-烷基,代表任选被相同或不同的取代基一-至三取代的C3-C6-环烷基,优选的取代基可以提到:卤素,C1-C4-烷基和具有1-5个相同或不同的卤原子例如氟,氯和溴原子的C1-C4-卤代烷基,或者代表苯基或苄基,其各自任选被相同或不同的取代基一-至三取代,各种情况下,可能的苯基取代基是:卤素,C1-C4-烷基,C1-C4-烷氧基和各种情况下具有1-5个相同或不同的卤原子例如氟,氯和溴原子的C1-C4-卤代烷基和C1-C4-卤代烷氧基和硝基,R7和R8各自独立地优选代表氢,C1-C6-烷基,C2-C4-链烯基或者代表苯基或苄基,其各自任选被相同或不同的取代基一-至三取代,各种情况下,可能的苯基取代基是:卤素,C1-C4-烷基,C1-C4-烷氧基和各种情况下具有1-5个相同或不同的卤原子例如氟,氯和溴原子的C1-C4-卤代烷基和C1-C4-卤代烷氧基,和R9代表C1-C4-烷基或代表苯基,其被相同或不同的取代基一-至三取代,可能的取代基是:卤素,C1-C4-烷基,C1-C4-烷氧基和各种情况下具有1-5个相同或不同的卤原子例如氟,氯和溴原子的C1-C4-卤代烷基和C1-C4-卤代烷氧基,A代表基团-CH2CH2-,-(CH2)3-和-CH=CH-,Z代表氰基或硝基,条件是,如果Z代表NO2和A代表-CH2CH2-,则基团R2代表氢;并且排除下面的式(Ⅰ)的化合物R2 H,R3 OCH3,A -CH2CH2-和Z NO2
4.权利要求1的式(Ⅰ)的化合物,其中R1代表6-氯-3-吡啶基(6-氯-吡啶-3-基)或代表2-氯-5-噻唑基(2-氯-噻唑-5-基),R2代表氢或C1-C5-烷基,R3代表基团-OR4,-OCOR5,-OCOOR6,-OCONR7R8和-OSO2R9,其中R4,R5和R6各自独立地代表C1-C8-烷基,C1-C2-烷氧基-C1-C2-烷基,具有1-2个相同或不同的卤原子例如氟,氯和溴原子的C1-C2-卤代烷基;烯丙基,炔丙基,C1-C2-烷基氨基-C1-C2-烷基,二(C1-C2)-烷基氨基-C1-C2-烷基,环丙基,环戊基,环己基,或者代表苯基或苄基,其各自任选被相同或不同的取代基一-至二取代,各种情况下可能的苯基取代基是:氟,氯,溴,甲基,甲氧基,三氟甲基,三氟甲氧基和硝基,R7和R8各自独立地代表氢,C1-C4-烷基,乙烯基,烯丙基,或者代表苯基或苄基,其各自任选被相同或不同的取代基一-至二取代,各种情况下可能的苯基取代基是:氟,氯,溴,甲基,甲氧基,三氟甲基和三氟甲氧基,和R9代表甲基,乙基或任选被相同或不同的取代基一-至二取代的苯基,可能的取代基是:氟,氯,溴,甲基,甲氧基,三氟甲基和三氟甲氧基,A代表基团-CH2CH2-和-CH=CH-,Z代表氰基或硝基,条件是,如果Z代表NO2和A代表-CH2CH2-,则基团R2代表氢;并且排除下面的式(Ⅰ)的化合物R2 H,R3 OCH3,A -CH2CH2-和Z NO2
5.防治动物害虫的组合物,特征在于,它们含有至少一种权利要求1的式(Ⅰ)的化合物。
6.权利要求1的式(Ⅰ)的化合物防治动物害虫的用途。
7.防治动物害虫的组合物的制备方法,特征在于,将权利要求1的式(Ⅰ)的化合物与稀释剂和/或表面活性剂混合。
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DE19800400A DE19800400A1 (de) | 1998-01-08 | 1998-01-08 | Substituierte Guanidin-Derivate |
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CNA200410039993XA Pending CN1550498A (zh) | 1998-01-08 | 1998-12-24 | 取代的胍衍生物 |
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JP (1) | JP2002500222A (zh) |
KR (1) | KR20010033372A (zh) |
CN (3) | CN1191247C (zh) |
AU (1) | AU2275999A (zh) |
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US6376548B1 (en) | 2000-01-28 | 2002-04-23 | Rohm And Haas Company | Enhanced propertied pesticides |
EP1940282B1 (en) * | 2005-10-26 | 2009-06-10 | REBUFFAT, Carlo | Anoscope for ano-rectal diagnostic and surgery |
AU2007348492B9 (en) | 2007-03-07 | 2013-04-18 | Covidien Ag | Stapler for mucosectomy |
US8181838B2 (en) | 2008-09-10 | 2012-05-22 | Tyco Healthcare Group Lp | Surgical stapling device |
US9204789B2 (en) | 2009-10-08 | 2015-12-08 | Covidien Lp | Asymmetrical anoscope |
US20180360040A1 (en) * | 2015-12-03 | 2018-12-20 | Syngenta Participations Ag | Pesticidal compounds and their uses |
DE102016108551B3 (de) * | 2016-05-09 | 2017-11-02 | Fritz Egger Gmbh & Co. Og | Faserplatte mit erhöhter Beständigkeit gegen Pilzbefall sowie Verfahren zu deren Herstellung |
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DE3681465D1 (zh) * | 1985-02-04 | 1991-10-24 | Nihon Bayer Agrochem K.K., Tokio/Tokyo, Jp | |
JPH0784461B2 (ja) * | 1986-12-19 | 1995-09-13 | 日本バイエルアグロケム株式会社 | 殺虫性ニトロイミノ又はシアノイミノ化合物 |
JPH0717621B2 (ja) * | 1986-03-07 | 1995-03-01 | 日本バイエルアグロケム株式会社 | 新規ヘテロ環式化合物 |
JPH07121909B2 (ja) | 1986-09-10 | 1995-12-25 | 日本バイエルアグロケム株式会社 | 新規複素環式化合物及び殺虫剤 |
JP2583429B2 (ja) * | 1987-11-06 | 1997-02-19 | 日本バイエルアグロケム株式会社 | イミダゾリン類及び殺虫剤 |
US5192778A (en) * | 1990-04-03 | 1993-03-09 | Mitsui Toatsu Chemicals, Inc. | Dialkoxymethylimidazolidine derivatives, preparation thereof, insecticides containing same as an effective ingredient and intermediates therefor |
JPH06100557A (ja) * | 1992-09-21 | 1994-04-12 | Mitsui Toatsu Chem Inc | 置換ニトログアニジン誘導体、その製造法、該誘導体を有効成分として含有する殺虫剤および中間体、その製造法 |
JPH06122680A (ja) * | 1992-10-12 | 1994-05-06 | Mitsui Toatsu Chem Inc | 置換ニトログアニジン誘導体類、その製造法、該誘導体類を有効成分として含有する殺虫剤および中間体、その製造法 |
JPH06122681A (ja) * | 1992-10-12 | 1994-05-06 | Mitsui Toatsu Chem Inc | 置換ニトログアニジン誘導体、その製造方法、該誘導体を有効成分として含有する殺虫剤および中間体、その製造方法 |
WO1994029268A1 (de) | 1993-06-07 | 1994-12-22 | Bayer Aktiengesellschaft | Iodpropargylcarbamate und ihre verwendung als biozide im pflanzen- und materialschutz |
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- 1998-12-24 EP EP98966405A patent/EP1047689A1/de not_active Withdrawn
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- 1998-12-24 CN CNB988129809A patent/CN1191247C/zh not_active Expired - Fee Related
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CN108440519A (zh) * | 2018-04-03 | 2018-08-24 | 青岛科技大学 | 一种噁二唑邻苯乙氧基类化合物与用途 |
CN108440519B (zh) * | 2018-04-03 | 2020-10-23 | 青岛科技大学 | 一种噁二唑邻苯乙氧基类化合物与用途 |
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EP1047689A1 (de) | 2000-11-02 |
CN1191247C (zh) | 2005-03-02 |
DE19800400A1 (de) | 1999-07-15 |
WO1999035141A1 (de) | 1999-07-15 |
CN1810807A (zh) | 2006-08-02 |
CN1550498A (zh) | 2004-12-01 |
US20030119828A1 (en) | 2003-06-26 |
BR9813241A (pt) | 2001-01-02 |
KR20010033372A (ko) | 2001-04-25 |
AU2275999A (en) | 1999-07-26 |
US6667310B2 (en) | 2003-12-23 |
US6503912B1 (en) | 2003-01-07 |
JP2002500222A (ja) | 2002-01-08 |
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