TW201043139A - Triazole compounds carrying a sulfur substituent III - Google Patents

Triazole compounds carrying a sulfur substituent III Download PDF

Info

Publication number
TW201043139A
TW201043139A TW099113196A TW99113196A TW201043139A TW 201043139 A TW201043139 A TW 201043139A TW 099113196 A TW099113196 A TW 099113196A TW 99113196 A TW99113196 A TW 99113196A TW 201043139 A TW201043139 A TW 201043139A
Authority
TW
Taiwan
Prior art keywords
group
compound
formula
hydrogen
alkyl
Prior art date
Application number
TW099113196A
Other languages
Chinese (zh)
Inventor
Jochen Dietz
Alice Glaettli
Thomas Grote
Wassilios Grammenos
Bernd Mueller
Jan Klaas Lohmann
Jens Renner
Sarah Ulmschneider
Marianna Vrettou-Schultes
Original Assignee
Basf Se
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Basf Se filed Critical Basf Se
Publication of TW201043139A publication Critical patent/TW201043139A/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D249/00Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/081,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C07D249/101,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D249/12Oxygen or sulfur atoms
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61PSPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P31/00Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
    • A61P31/10Antimycotics
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61PSPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P31/00Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
    • A61P31/12Antivirals
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61PSPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P35/00Antineoplastic agents

Abstract

The present invention relates to novel triazole compounds of the formulae I and II as defined in the claims and description which carry a sulfur substituent, to agricultural compositions containing them, to their use as fungicides and to intermediate compounds used in the method of producing them.

Description

201043139 六、發明說明: 【發明所屬之技術領域】 本發明係關於一種如下定義之具有硫取代基的式I及式II 之新穎三唑化合物、含有該等化合物之農業組合物、其作 ‘ 為殺真菌劑之用途及其製備方法中所用之中間化合物。 •【先前技術】 防治由植物病原性真菌引起之植物病害對於實現高作物 效率極其重要。觀賞作物、蔬菜作物、大田作物、穀類作 Ο 物及水果作物之植物病害(Plant disease damage)可導致生 產力顯著降低且由此導致對費者之價格提高。 DE 19520098、DE 19617282、DE 19620407、DE 19620590 及WO 97/43269描述硫化三唑基衍生物。該等化合物係用 於對抗有害真菌。 持續需要更有效、成本更低、毒性更低、環境上更安全 及/或具有不同作用模式之新穎化合物。 【發明内容】 〇 w 因此,本發明之目標在於提供具有較好殺真菌活性及/ 或較好作物植物相容性之化合物。 令人驚訝地,此等目標可藉由下文定義之通式I及II之三 屬 < 唑化合物及藉由化合物I及II之農業上可接受之鹽來達成。 因此,本發明係關於式I及式II三唑化合物及其農業上適 用之鹽, 147475.doc 201043139201043139 6. INSTRUCTIONS OF THE INVENTION: TECHNICAL FIELD The present invention relates to a novel triazole compound of the formula I and formula II having a sulfur substituent as defined below, an agricultural composition containing the same, which is The use of fungicides and intermediate compounds used in the preparation thereof. • [Prior Art] Controlling plant diseases caused by phytopathogenic fungi is extremely important for achieving high crop efficiency. Plant disease damage from ornamental crops, vegetable crops, field crops, cereals and fruit crops can result in a significant reduction in productivity and thus an increase in the price of the consumer. The triazolyl derivatives are described in DE 19520098, DE 19617282, DE 19620407, DE 19620590 and WO 97/43269. These compounds are used against harmful fungi. There is a continuing need for novel compounds that are more effective, less costly, less toxic, safer in the environment, and/or have different modes of action. SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide compounds having better fungicidal activity and/or better crop plant compatibility. Surprisingly, such targets can be achieved by the <3> azole compounds of the general formula I and II as defined below and by the agriculturally acceptable salts of the compounds I and II. Accordingly, the present invention relates to triazole compounds of formula I and formula II and their agriculturally acceptable salts, 147475.doc 201043139

其中 L及L彼此獨立地選自氫、氟、溴、碘、烷基、 。齒烧基、Cl_Ci^氧基及Ci_CiQ鹵院氧基; L2及L3彼此獨立地選自氫、函素、c「Ci。絲、Ci_Ci。 鹵烧基、q-c滅氧基及Ci_Ci〇函烧氧基; 限制條2件為Ll、L2、L3及中至少一者不為氫; R及R彼此獨立地選自氫、Ci_Ci〇烷基、Ci_Ci〇鹵垸 基Cl-Cl0院氧基及鹵烧氧基; R3係選自氫、Cl_ClG烷基、Ci_CiQ[fi烷基、Ci_Ci〇烷氧基 及Cl-C10鹵烷氧基; R係選自氫、CVC!。烷基、Cl_Ci〇鹵烷基、c2_Ci〇烯基、 C2-C1G _缚基、c2_CiG快基、❶齒炔基、CyCiQ環烷 基、C3-C10鹵環烷基、苯基、苯基_Ci_c4烷基,其中最後2 個提及之基團中之苯基部分可具有丨、2、3、4或5個取代 ,R8,及含有Ϊ、2或3個選自N、〇及S之雜原子作為環成 貝的5員46員飽和、部分不飽和或芳族雜環,其中該 可具有1、2或3個取代基R8 ;或在„為〇 ^ < If況下,亦玎選 147475.doc 201043139 自-C(=〇)R5、-C(=S)R、-S(〇)2R5、-CN、-P(=Q)R6r7、μ 及式III基團,Wherein L and L are independently selected from the group consisting of hydrogen, fluorine, bromine, iodine, and alkyl. a dentate group, a Cl_Ci oxy group, and a Ci_CiQ halogen oxy group; L2 and L3 are independently selected from the group consisting of hydrogen, a nutrient, c "Ci. Silk, Ci_Ci. a halogen group, a qc alkoxy group, and a Ci_Ci 烧 alkoxy The restriction strip 2 is L1, L2, L3 and at least one of them is not hydrogen; R and R are independently selected from hydrogen, Ci_Ci 〇 alkyl, Ci_Ci 〇 垸 Cl Cl Cl-Cl0 oxy and halogen氧基; R3 is selected from the group consisting of hydrogen, Cl_ClG alkyl, Ci_CiQ [fi alkyl, Ci_Ci decyloxy and Cl-C10 haloalkoxy; R is selected from hydrogen, CVC!. Alkyl, Cl_Ci 〇 haloalkyl , c2_Ci decyl, C2-C1G _ linkage, c2_CiG fast radical, decyl alkynyl, CyCiQ cycloalkyl, C3-C10 halocycloalkyl, phenyl, phenyl-Ci_c4 alkyl, of which the last two The phenyl moiety in the group may have 丨, 2, 3, 4 or 5 substituents, R8, and 5 members containing ruthenium, 2 or 3 heteroatoms selected from N, oxime and S as ring-shaped shells 46-membered saturated, partially unsaturated or aromatic heterocyclic ring wherein the group may have 1, 2 or 3 substituents R8; or in the case of 〇^ < If, also selected 147475.doc 201043139 from -C( =〇)R5, -C(=S)R, -S(〇)2R5, -CN, -P(=Q)R6r7, μ and Formula I II group,

〇 其中 L1、L2、L3、L4、Rl、R2及R3係如對於式I及式π所定 義;且 #為與分子之其餘部分的連接點; R4a係選自氫、ci-ci〇烷基、CVCw鹵烷基、c2_Ci〇烯 基、C2-C10鹵稀基、C2-C10快基、C2-Ci0鹵快基' C3-Ci0環 烷基、(:3_(:10鹵環烷基、苯基、苯基-CrC4烷基,其中最 後2個提及之基團中之苯基部分可具有1、2、3、4或5個取 ❹ 代基R8’含有1、2或3個選自N、〇及S之雜原子作為環成 員的5員或6員飽和、部分不飽和或芳族雜環,其中該雜環可 具有 1、2或 3個取代基 R8,-C(=0)R5、-C(=S)R5、_SCC〇2R5、 -CN、-P(=Q)R6R7及 Μ ; R係選自氫、CVCm烷基、CVCm鹵烧基、烷氧 基、CVCw鹵烷氡基、Cl_Cl〇胺基烷基、c3_Ci〇環烷基、 C3-C10_環烧基、苯基、苯基—c^C4院基、笨氧基,其中 最後3個提及之基團中之苯基部分可具有丨、2、3、 147475.doc 201043139 取代基R8,含有1、2或3個選自N、〇及S之雜原子作為環 成員的5員或6員飽和、部分不飽和或芳族雜環,其中該= %可具有1、2或3個取代基尺8,&nr9rig ; '、 R6及R7彼此獨立地選自Ci_Ci〇烷基、c〗_Ci〇齒烷基、 c10烯基、c2-c10_ 烯基、C2_Cio炔基、C2_Ci〇自炔基、 c10^烷基、C3_Cl〇_烷基、Ci_Ci〇烷氧基、Ci_Ci〇鹵烷 氧基、c「C4燒氧基_Cl_Ci()烧基、Ci_C4烧氧基4·^成氧 基、CrCu炫硫基、Ci,CiGli烧硫基、c2_Ci。烯氧基、 C10稀硫基、c2_Ci。快氧基、c2_Ci。炔硫基、c3_Ci❹環烷氧 基、<^-(:1()環烷硫基、苯基、苯基_Ci_C4烷基 '苯氧基、 苯硫基、苯基-Ci-C4烷氧基及NRnR12 ; 各R8獨立地選自鹵素、硝基、CN、Ci_C4烷基、Ci_C4_ 烧基、CVC4燒氧基、c丨-c4鹵烷氧基及NR13R14 ; R9係選自氫及(^(:8烷基·, R10係選自氫、Ci_C8烷基、苯基及苯基_Ci_C4烷基; 或R9與RW 一起形成直鏈匕或^伸烷基橋或基團 -CH2CH2OCH2CH2-或-CH2CH2NR15CH2CH2-;Wherein L1, L2, L3, L4, R1, R2 and R3 are as defined for formula I and formula π; and # is the point of attachment to the rest of the molecule; R4a is selected from hydrogen, ci-ci〇 alkyl , CVCw haloalkyl, c2_Ci nonenyl, C2-C10 halo, C2-C10 fast radical, C2-Ci0 halo fast radical 'C3-Ci0 cycloalkyl, (: 3_(:10 halocycloalkyl, benzene a phenyl-CrC4 alkyl group, wherein the phenyl moiety in the last two mentioned groups may have 1, 2, 3, 4 or 5 substituents. R8' contains 1, 2 or 3 selected from a 5- or 6-membered saturated, partially unsaturated or aromatic heterocyclic ring of a hetero atom of N, hydrazine and S, wherein the heterocyclic ring may have 1, 2 or 3 substituents R8, -C(=0) R5, -C(=S)R5, _SCC〇2R5, -CN, -P(=Q)R6R7 and Μ; R is selected from hydrogen, CVCm alkyl, CVCm haloalkyl, alkoxy, CVCw haloalkyl , Cl_Cl 〇 aminoalkyl, c3_Ci 〇 cycloalkyl, C3-C10_cycloalkyl, phenyl, phenyl-c^C4, phenyl, of which the last three are mentioned The phenyl moiety may have an anthracene, 2, 3, 147475.doc 201043139 substituent R8 containing 1, 2 or 3 heteroatoms selected from N, anthracene and S. a 5- or 6-membered saturated, partially unsaturated or aromatic heterocyclic ring of a ring member, wherein the % can have 1, 2 or 3 substituent bases 8, &nr9rig; ', R6 and R7 are independently selected from each other Ci_Ci 〇 alkyl, c _Ci dentate alkyl, c10 alkenyl, c2-c10_ alkenyl, C 2 —Cio alkynyl, C 2 —Ci 〇 alkynyl, c 10 —alkyl, C 3 —Cl〇—alkyl, Ci—Ci decyloxy, Ci_Ci 〇 haloalkoxy, c "C4 alkoxy _Cl_Ci () alkyl, Ci_C4 alkoxy 4 ethoxy, CrCu sulphur, Ci, CiGli sulphur, c2_Ci. oxy, C10 Dilute sulfur group, c2_Ci, alkoxy group, c2_Ci, alkynylthio group, c3_Ci❹cycloalkoxy group, <^-(:1()cycloalkylthio group, phenyl group, phenyl-Ci_C4 alkyl 'phenoxy group, Phenylthio, phenyl-Ci-C4 alkoxy and NRnR12; each R8 is independently selected from the group consisting of halogen, nitro, CN, Ci_C4 alkyl, Ci_C4_alkyl, CVC4 alkoxy, c丨-c4 haloalkoxy And NR13R14; R9 is selected from hydrogen and (^(:8 alkyl·, R10 is selected from hydrogen, Ci_C8 alkyl, phenyl and phenyl-Ci_C4 alkyl; or R9 and RW together form a linear 匕 or ^ An alkyl bridge or group -CH2CH2OCH2CH2- or -CH2CH2NR15CH2CH2-;

Rn係選自氫及cvc8烷基; R12係選自氫、Cl_c8烷基、苯基及苯基_Cl_c4烷基; 或1111與1112 —起形成直鏈c4或c5伸烷基橋或基團 -CH2CH2OCH2CH2-或-CH2CH2NR15CH2CH2-;Rn is selected from the group consisting of hydrogen and cvc8 alkyl; R12 is selected from the group consisting of hydrogen, Cl_c8 alkyl, phenyl and phenyl-Cl_c4 alkyl; or 1111 and 1112 together form a linear c4 or c5 alkyl bridge or group - CH2CH2OCH2CH2- or -CH2CH2NR15CH2CH2-;

Rl3在每次出現時獨立地選自氫及Ci-C8烷基; R14在每次出現時獨立地選自氫、Cl-C8烷基、苯基及笨 基-C 1 -C4烧基; 147475.doc 201043139 或尺13與R14—起形成直鏈c4或c5伸烷基橋或基團 -ch2ch2och2ch2-或-ch2ch2nr15ch2ch2-; R15在每次出現時獨立地選自氫及(^-(:4烷基; Q為0或S ; Μ為金屬陽離子相等物或式(NRaRbReRd)+之銨陽離子, 其中Ra、Rb、Rc及Rd彼此獨立地選自氫、CrCl〇烧基、苯 基及苯曱基,其中最後2個提及之基團中之苯基部分可具 有1 ' 2或3個獨立地選自以下之取代基:鹵素、cn、硝 基、cvq烷基、Cl_C4_烷基、Cl_C4烷氧基、Cl_c4鹵烷 氧基及NR13R14 ; η為0、1、2或3 ;且 二二(鍵/點鍵組合)為單鍵或雙鍵。 本發明亦係關於式Ϊ及式^三唑化合物及其農業上適用之 鹽,Rl3 is independently selected from hydrogen and Ci-C8 alkyl at each occurrence; R14 is independently selected from hydrogen, Cl-C8 alkyl, phenyl, and styryl-C1-C4 alkyl at each occurrence; 147475 .doc 201043139 or ruler 13 and R14 together form a linear c4 or c5 alkylene bridge or group -ch2ch2och2ch2- or -ch2ch2nr15ch2ch2-; R15 is independently selected from hydrogen and (^-(:4 alkane) at each occurrence Q is 0 or S; Μ is a metal cation equivalent or an ammonium cation of the formula (NRaRbReRd)+, wherein Ra, Rb, Rc and Rd are independently selected from hydrogen, CrCl decyl, phenyl and phenyl fluorenyl Wherein the phenyl moiety of the last two mentioned groups may have 1 '2 or 3 substituents independently selected from the group consisting of halogen, cn, nitro, cvq alkyl, Cl_C4_alkyl, Cl_C4 alkane Oxyl, Cl_c4 haloalkoxy and NR13R14; η is 0, 1, 2 or 3; and bis (bond/dot bond combination) is a single bond or a double bond. The present invention also relates to a formula and a triazole Compounds and their agriculturally applicable salts,

L2 Η 其中 L及L彼此獨立地選自氫、氟、溴、蛾、烧基 Cl_Cl〇鹵烧基、Ci-C10烷氧基及(^-〇10鹵烷氧基; 147475.doc 201043139 L及L3彼此獨立地選自氫、函素、c]_Ci〇烷基、Ci_Cu 鹵烧基、Ci-Cio烧氧基及^-匸⑺鹵烷氧基; 限制條件為L1、L2、L3及L4中至少一者不為氫; R1及R2彼此獨立地選自氫' Cl_Ci〇烷基、Ci_Ci〇南烷 基、匸〗-(:10烷氧基及(:〗_(:!〇鹵烷氧基; R3係選自氫、(:,-(:!〇烷基、(^-(^。鹵烷基、Ci_Ci〇烷氧基 及Cl-Ci〇_^氧基; R係選自氫、CVCw烷基、(^-0:1〇鹵烷基、c2_Ci〇烯基、 C2-C1G i| 烯基、c2-C1()炔基、c2-c1() _ 炔基、c3_Ci❹環烧 基、C3-C10_環烷基、苯基、苯基-Ci-C4烷基,其中最後2 個提及之基團中之苯基部分可具有i、2、3、4或5個取代 基R8,及含有i、2或3個選自N、〇及s之雜原子作為環成 員的5員或6員飽和、部分不飽和或芳族雜環,其中該雜環 可具有1、2或3個取代基R8 ;或在η為〇之情況下,亦可選 自-C(=〇)R5 ' _C(=S)r5、_S(0)2R5、_p(=q)r6r7 Μ 及式III基團,L2 Η wherein L and L are independently selected from the group consisting of hydrogen, fluorine, bromine, moth, alkyl Cl_Cl oxime, Ci-C10 alkoxy and (^-〇10 haloalkoxy; 147475.doc 201043139 L and L3 is independently of each other selected from the group consisting of hydrogen, a functional element, c]-Ci 〇 alkyl, a Ci_Cu halogen group, a Ci-Cio alkoxy group, and a hydrazine (7) haloalkoxy group; the limiting conditions are L1, L2, L3 and L4. At least one of them is not hydrogen; R1 and R2 are independently of each other selected from the group consisting of hydrogen 'Cl_Ci 〇 alkyl, Ci_Ci 〇 烷基 匸, 匸 - - (: 10 alkoxy and (: _ _ (:! 〇 haloalkoxy) R3 is selected from the group consisting of hydrogen, (:, -(:!〇alkyl, (^-(^.haloalkyl, Ci_Ci〇alkoxy, and Cl-Ci〇_^oxy; R is selected from hydrogen, CVCw Alkyl, (^-0:1〇 haloalkyl, c2_Ci〇 alkenyl, C2-C1G i|alkenyl, c2-C1()alkynyl, c2-c1() _alkynyl, c3_Ci❹cycloalkyl, C3 -C10_cycloalkyl, phenyl, phenyl-Ci-C4 alkyl, wherein the phenyl moiety of the last two mentioned groups may have i, 2, 3, 4 or 5 substituents R8, and a 5- or 6-membered saturated, partially unsaturated or aromatic heterocyclic ring containing i, 2 or 3 heteroatoms selected from the group consisting of N, hydrazine and s, wherein the heterocyclic ring may have 1, 2 or 3 substituents R8; or in the case where η is 〇, may also be selected from -C(=〇)R5 ' _C(=S)r5, _S(0)2R5, _p(=q)r6r7 Μ and a group of formula III,

其中 L1 、 L2 、 L3 、 L‘Where L1, L2, L3, L'

R R & R係如對於式I及式II所定 147475.doc 201043139 義;且 #為與分子之其餘部分的連接點; R4a係選自氫、Ci-C^烧基、Cl-C1() _烧基、c2_Ci。稀 基、C2-c1()鹵烯基、C2-C1()炔基 ' c2-c1()_ 炔基、c3_Ci〇 環 烷基、Cs-Cio鹵環烷基、苯基、苯基-CVC4烷基,其中最 後2個提及之基團中之苯基部分可具有1、2、3、4或5個取 代基R8,含有i、2或3個選自N、〇及S之雜原子作為環成 〇 員的5員或6員飽和、部分不飽和或芳族雜環,其中該雜環 可具有 1、2 或 3 個取代基 R8,-C(=0)R5、、_s(〇)2r5 衣 •CN、-P(=Q)R6R7及 Μ ; R係選自氫、C^-Cio烧基、(^-Cw鹵燒基、c Γ 土 Ci-C丨0鹵烧氧基、Ci-Ci〇胺基烧基、c3-C10環烧義 C^Cio鹵環烷基、苯基、苯基_Cl_C:4烷基、苯氧基,其中 取後3個提及之基團中之苯基部分可具有1、 〇、4或5個 取代基R8,含有i、2或3個選自N、〇及8之雜原子作為環 〇 成員的5員或6員飽和、部分不飽和或芳族雜環,其中該雜 環可具有1、2或3個取代基R8,及NR9R10 ; R6及R7彼此獨立地選自Cl_Cl0烷基、Ci_c〗〇齒烷基、 • Cl。烯基、c2-Cl-稀基、c2_ClQ炔基、C2_Ci一 块基、^ ,環烷基、C3_Cl。函環烷基、Ci_Ci。烷氧基、Μ“烷 氧基、C1-C4烷氧基-Cl-Cl()烷基、Cl_C4烷氧基烷氧 Cl C1Q烧硫基、(VCw鹵娱(硫基、C2-C1()婦氧基、c2_ “婦硫基、C2-Cl0炔氧基、c2_Cla硫基、C3_CiQ環^ 基、h-Cio環烷硫基、苯基、苯基-Cl-C4烷基、苯氧基、 147475.doc 201043139 苯硫基、苯基-CVC4烷氧基及nr1!r12 ; 各R8獨立地選自鹵素、硝基、CN、C〗-C4烷基、Ci_c4^ 烧基、CVC4烷氧基、CVC4鹵烷氧基及NR13R14 ; R9係選自氫及CVCs烷基; R10係選自CkCs烷基、苯基及苯基_Cl_C4烷基; 或R9與R1G—起形成直鏈(^或^伸烷基橋或基圏 -CH2CH2OCH2CH2-或-CH2CH2NR15CH2CH2-; R11係選自氫及CVC8烷基; R12係選自Ci-C:8烷基、苯基及苯基_Cl_c4烷基; 或R11與R12—起形成直鏈C4或Cs伸烷基橋或基團 -CH2CH2OCH2CH2-或-CH2CH2NR15CH2CH2-; R13在每次出現時獨立地選自氫及匸广。烷基; R14在每次出現時獨立地選自Ci_C8烷基、苯基及笨基 -CVC4烷基; 或R13及R14—起形成直鏈C4或Cs伸烷基橋或基團 -ch2ch2och2ch2-或-ch2ch2nr15ch2ch2-; R在每次出現時獨立地選自氫及烷基; Q為Ο或S ; Μ為金屬陽離子相等物或式(NRaRbReRd)+之銨陽離子, 其中R、R、RC^Rd彼此獨立地選自氫、c〗-c10烷基、苯 基及苯曱基’其中最後2個提及之基團中之苯基部分可具 有1、2或3個獨立地選自以下之取代基:鹵素、cN、硝 基Ci-C4烧基、Ci_c4_烷基、C「C4烧氧基、Ci_c4鹵烷 氧基及NR13R14 ; 147475.doc 201043139 η為0、ι、2或3 ;且 =(鍵/點鍵組合)為單鍵或雙鍵。 該 等結構 因此’式I及式II為表示以下結構之統一方式 亦命名為式ΙΑ、IIA、IB及IIB化合物: ΟRR & R is as defined for 147475.doc 201043139 of Formula I and Formula II; and # is the point of attachment to the rest of the molecule; R4a is selected from hydrogen, Ci-C^alkyl, Cl-C1() _ Burning base, c2_Ci. Dilute, C2-c1()haloenyl, C2-C1()alkynyl' c2-c1()-alkynyl, c3_Ci〇cycloalkyl, Cs-Cio halocycloalkyl, phenyl, phenyl-CVC4 An alkyl group, wherein the phenyl moiety of the last two mentioned groups may have 1, 2, 3, 4 or 5 substituents R8 containing i, 2 or 3 heteroatoms selected from N, fluorene and S a 5- or 6-membered saturated, partially unsaturated or aromatic heterocyclic ring as a cyclist, wherein the heterocyclic ring may have 1, 2 or 3 substituents R8, -C(=0)R5, _s(〇 2r5 clothing • CN, -P(=Q)R6R7 and Μ; R is selected from hydrogen, C^-Cio alkyl, (^-Cw halogen, c ΓCi-C丨0 halogen oxy, Ci-Ci amidinoalkyl, c3-C10 ring-activated C^Cio halocycloalkyl, phenyl, phenyl-Cl_C: 4 alkyl, phenoxy, wherein the latter three groups are taken The phenyl moiety may have 1, 〇, 4 or 5 substituents R8, containing i, 2 or 3 heteroatoms selected from N, fluorene and 8 as a member of the ring oxime, 5 or 6 members saturated, partially unsaturated Or an aromatic heterocyclic ring wherein the heterocyclic ring may have 1, 2 or 3 substituents R8, and NR9R10; R6 and R7 are independently of each other selected from the group consisting of Cl_Cl0 alkyl, Ci_c, dentate alkyl, • C l. alkenyl, c2-Cl-dense, c2_ClQ alkynyl, C2_Ci, benzyl, cycloalkyl, C3_Cl, cycloalkyl, Ci_Ci, alkoxy, decyl alkoxy, C1-C4 alkoxy ke-Cl-Cl() alkyl, Cl_C4 alkoxyalkoxy Cl C1Q sulphur-based, (VCw thiol (thiol, C2-C1() ethoxylate, c2_" thiol, C2-Cl0 alkyne Base, c2_Clathio group, C3_CiQ ring group, h-Cio cycloalkylthio group, phenyl group, phenyl-Cl-C4 alkyl group, phenoxy group, 147475.doc 201043139 phenylthio group, phenyl-CVC4 alkoxy group And nr1!r12; each R8 is independently selected from the group consisting of halogen, nitro, CN, C-C4 alkyl, Ci_c4^ alkyl, CVC4 alkoxy, CVC4 haloalkoxy and NR13R14; R9 is selected from hydrogen and CVCs Alkyl; R10 is selected from CkCs alkyl, phenyl and phenyl-Cl_C4 alkyl; or R9 and R1G together form a straight chain (^ or ^alkyl bridge or hydrazine-CH2CH2OCH2CH2- or -CH2CH2NR15CH2CH2-; R11 Is selected from the group consisting of hydrogen and CVC8 alkyl; R12 is selected from the group consisting of Ci-C: 8-alkyl, phenyl and phenyl-Cl_c4 alkyl; or R11 and R12 together form a linear C4 or Cs alkylene bridge or group -CH2CH2OCH2CH2- or -CH2CH2NR15CH2CH2-; R13 is independently selected from the group consisting of hydrogen and hydrazine at each occurrence. An alkyl group; R14 is independently selected from the group consisting of Ci_C8 alkyl, phenyl and phenyl-CVC4 alkyl at each occurrence; or R13 and R14 together form a linear C4 or Cs alkylene bridge or group -ch2ch2och2ch2- or -ch2ch2nr15ch2ch2-; R is independently selected from hydrogen and alkyl at each occurrence; Q is ruthenium or S; ruthenium is a metal cation equivalent or an ammonium cation of formula (NRaRbReRd)+, wherein R, R, RC^Rd are each other The phenyl moiety independently selected from the group consisting of hydrogen, c--c10 alkyl, phenyl and phenylhydrazine, wherein the last two of the groups mentioned may have 1, 2 or 3 substituents independently selected from : halogen, cN, nitro Ci-C4 alkyl, Ci_c4_alkyl, C "C4 alkoxy, Ci_c4 haloalkoxy and NR13R14; 147475.doc 201043139 η is 0, ι, 2 or 3; and = ( The bond/point key combination) is a single bond or a double bond. The structures of the formulas I and II are thus represented by the following structures: ΙΑ, IIA, IB and IIB compounds: Ο

NN

Η (ΙΑ) R4a I ,ΝΗ (ΙΑ) R4a I , Ν

I R43 I ,Ν ^ γ^(〇)η^ Ν-ΝI R43 I , Ν ^ γ^(〇)η^ Ν-Ν

丄2 Ή丄2 Ή

L2 Η Ο (旧) 若在化合物ΙΑ中,R4為式III基團,則其為式ΙΙΙΑ基團, #L2 Η Ο (old) If R4 is a group of formula III in the compound oxime, it is a hydrazine group, #

(IHA) Η 147475.doc 201043139 方在化口物IB中’ R4為式111基團,則其為式IIIB基團(IHA) Η 147475.doc 201043139 In the IB, 'R4 is a group of formula 111, then it is a group of formula IIIB

本發月亦提供式1及式11三嗤化合物及/或其農業上適用 之鹽用於防治有害真菌之用途。 本發明進一步提供却Αι t、殺真卤組合物’其包含式I及/或式 11(及/或亦式IV,參看下文)之此等三唾化合物及/或其農業 上可接受之鹽及適合载劑。下文描述適合之農業上可接受 之載劑。 化5物I及II可以—或多種立體異構體形式存在。各種立 體異構體包括對映異構體、非對映異構體、滞轉異構體及 成何異構體。熟習此項技術者應瞭解,一種立體異構體當 相對於其他立體異構體增濃時或當他立 時可更具活性及,或可顯示有利作用…卜,熟習此 術者已知如何分離、增濃及/或選擇性製備該等立體異構 體。本發明之化合物可以立體異構體之混合物(例如外消 旋體)、個別立體異構體形式或以光學活性形式存在。特 定言之,式IA及IIA化合物可關於環戊烷環上〇H基團與其 R3 L1 ^ 團^X^CH之相對位置以異構體形式存在,其可為順式或 L3 147475.doc -12- 201043139 ; 本毛月'函蓋順式異構體、反式異構體及其混合物。 然而’較佳4 j噴式異構體(式IA-順式及式ιΙΑ_順式化合 物): 〇This month also provides the use of the triterpenoids of formula 1 and formula 11 and/or their agriculturally suitable salts for the control of harmful fungi. The present invention further provides such trisodium compounds and/or agriculturally acceptable salts thereof comprising the formula I and/or formula 11 (and/or also formula IV, see below) And suitable for carriers. Suitable agriculturally acceptable carriers are described below. The compounds I and II may exist in the form of one or more stereoisomers. The various stereoisomers include enantiomers, diastereomers, ligation isomers, and any isomers. Those skilled in the art will appreciate that a stereoisomer may be more active when it is enriched relative to other stereoisomers or when it is immediate, or may exhibit beneficial effects... well, it is known to those skilled in the art how to separate Enriching and/or selectively preparing the stereoisomers. The compounds of the invention may exist as a mixture of stereoisomers (e.g., racemates), as individual stereoisomers, or as optically active forms. In particular, the compounds of the formulae IA and IIA may exist in isomeric form with respect to the relative position of the hydrazine H group of the cyclopentane ring to its R3 L1 ^ group ^X^CH, which may be cis or L3 147475.doc - 12- 201043139; This Maoyue's cover is a cis isomer, a trans isomer and a mixture thereof. However, the preferred 4j spray isomer (formula IA-cis and formula ιΙΑ_cis compound): 〇

至少在基團R4/R4a相同之情況下,可將化合物I及Η彼此 視為位置/雙鍵異構體。在R4(當然以及R4a)為氫之情況 下,各別化合物I及丨丨為互變異構體。Compound I and hydrazine can be regarded as position/double bond isomers at least in the case where the groups R4/R4a are the same. In the case where R4 (and of course R4a) is hydrogen, the respective compounds I and hydrazine are tautomers.

適合辰業上適用之鹽尤其為彼等陽離子之鹽或彼等酸之 酸加成鹽’其陽離子及陰離子分別對化合殺真菌 作用不具有不良影響。因此,適合陽離子尤其為鹼金屬 (較佳為鈉及鉀)、鹼土金屬(較佳為鈣、鎂及鋇)及過渡金 屬(較佳為錳、銅、鋅及鐵)之離子,以及銨離子,該銨離 子必要時可具有一至四個Ci_C4烷基取代基及/或一個苯基 或苯甲基取代基,較佳為二異丙銨、四甲銨、四丁銨、三 甲基苯甲基銨,此外為鱗離子、鎳離子,較佳為三(C丨_C4 烷基)銃及氧化銕離子,較佳為三(Ci_C4烷基)氧化錡。 適用酸加成鹽之陰離子主要為氯離子、溴離子、氟離 子、硫酸氫根、硫酸根、磷酸二氫根、磷酸氫根、磷酸 根、硝酸根、碳酸氳根、碳酸根、六氟矽酸根、六氟磷酸 147475.doc •13· 201043139 根、苯曱酸根,以及烷酸之陰離子,較佳為甲酸 根、乙酸根、丙酸根及丁酸根。其可藉由使I或II與相應陰 離子之酸(較佳為鹽酸、氫溴酸、硫酸、磷酸或硝酸)反應 來形成。 在上文式中給出之變數的定義中,使用一般代表所討論 之取代基的集合術語。術語cn-cm指示在各情況下在所討 論之取代基或取代部分中可能之碳原子數: 鹵素:氟、氯、溴及碘; 烷基及烷氧基、烷基羰基、烷基硫基羰基、烷基胺基、 二烷基胺基、烷基胺基羰基、二烷基胺基羰基、烷硫基、 烧基績醯基及其類似基團中之烧基部分:具有1至2個(Cr C2烧基)、2或3個(C2-C3烧基)、1至4個((^-04烧基)、1至6 個(CVC6烷基)、1至8個(CVCs烷基)或1至1〇個(Cl-C1Q烷基) 碳原子之飽和直鏈或分支鏈烴基。c2-c3烧基為乙基、正 丙基或異丙基。Ci-C2烧基為曱基或乙基。c「C4炫基另外 亦為丙基、異丙基、丁基、1-甲基丙基(第二丁基)、2-甲 基丙基(異丁基)或1,1-二曱基乙基(第三丁基)。Ci-C^烷基 另外亦為例如戊基、1-曱基丁基、2-曱基丁基、3 -曱基丁 基、2,2-二曱基丙基、1-乙基丙基、1,1-二甲基丙基、1,2_ 二甲基丙基、己基、卜甲基戊基、2-甲基戊基、3 -甲基戊 基、4-甲基戊基、1,1-二曱基丁基、ι,2_二甲基丁基、I% 二甲基丁基、2,2-二甲基丁基、2,3-二甲基丁基、3,3-二甲 基丁基、1-乙基丁基、2-乙基丁基、112_三曱基丙基、 1,2,2-三曱基丙基、卜乙基-1-甲基丙基或卜乙基_2_甲基丙 147475.doc 14- 201043139 基。c^-c:8烷基另外亦為例如庚基 '辛基、2_乙基己基及其 位置異構體。C^-Cm烧基另外亦為例如壬基、癸基、丙 基庚基、3 -丙基庚基及其位置異構體。 鹵烷基:具有1至2個(CVC2鹵烷基)、1至3個鹵烷 基)、1至4個(CrCUi烷基)、1至6個(Ci-Ce鹵烷基)、1至8 個(Ci-C8_院基)、1至10個(Ci-Ci。函烧基)或2至1〇個(c2· C10函烷基)碳原子之直鏈或分支鏈烷基(如上所述),其中 此等基團中之一些或全部氫原子可經如上所述之齒素原子 Ο 置換..特定言之為Ci-C2鹵烧基,諸如氯甲基、溴甲基、 二氯甲基、三氣甲基、氟甲基、二氟甲基、三氟甲基、氯 乱甲基、二氯敗甲基、二氟氣甲基、1_氯乙基、1_漠乙 基、1-氟乙基、2-氟乙基' 2,2-二氟乙基、2,2,2-三氟乙 基、2-氣-2-氟乙基、2-氯-2,2-二氟乙基、2,2-二氯-2-氟乙 基、2,2,2 -二乳乙基或五乱乙基。Ci-C〗鹵炫》基另外為例如 1,1,1-三氟丙-2-基、3,3,3-三氟丙基或七氟丙基。Cl-C4鹵 q 烷基另外為例如1-氣丁基、2-氯丁基、3-氯丁基或4-氯丁 基。Suitable salts for use in the industry are, in particular, the salts of their cations or the acid addition salts of their acids. The cations and anions thereof have no adverse effects on the combined fungicidal action, respectively. Thus, suitable cations are especially alkali metal (preferably sodium and potassium), alkaline earth metals (preferably calcium, magnesium and barium) and transition metal (preferably manganese, copper, zinc and iron) ions, and ammonium ions. The ammonium ion may have one to four Ci_C4 alkyl substituents and/or one phenyl or benzyl substituent, if desired, preferably diisopropylammonium, tetramethylammonium, tetrabutylammonium, trimethylbenzene The amide is further a scaly ion or a nickel ion, preferably a tris(C丨_C4 alkyl) fluorene and a cerium oxide ion, preferably a tri(Ci_C4 alkyl) cerium oxide. The anion of the acid addition salt is mainly chloride ion, bromide ion, fluoride ion, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, strontium carbonate, carbonate, hexafluoroantimony. Acid, hexafluorophosphate 147475.doc •13· 201043139 Root, benzoate, and anion of alkanoic acid, preferably formate, acetate, propionate and butyrate. It can be formed by reacting I or II with an acid of the corresponding anion (preferably hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid). In the definition of the variables given in the above formula, collective terms that generally represent the substituents in question are used. The term cn-cm indicates the number of possible carbon atoms in each case in the substituent or substituted moiety in question: halogen: fluorine, chlorine, bromine and iodine; alkyl and alkoxy, alkylcarbonyl, alkylthio a carbonyl group, an alkylamino group, a dialkylamino group, an alkylaminocarbonyl group, a dialkylaminocarbonyl group, an alkylthio group, a decyl group, and the like in the group: 1 to 2 (Cr C2 alkyl), 2 or 3 (C2-C3 alkyl), 1 to 4 ((^-04 alkyl), 1 to 6 (CVC6 alkyl), 1 to 8 (CVCs alkane) a saturated linear or branched hydrocarbon group of 1 to 1 (Cl-C1Q alkyl) carbon atom. The c2-c3 alkyl group is ethyl, n-propyl or isopropyl. The Ci-C2 alkyl group is hydrazine. Base or ethyl. c "C4 leucoyl is also propyl, isopropyl, butyl, 1-methylpropyl (second butyl), 2-methylpropyl (isobutyl) or 1, 1-dimercaptoethyl (t-butyl). Ci-C^alkyl is also additionally, for example, pentyl, 1-decylbutyl, 2-mercaptobutyl, 3-nonylbutyl, 2, 2-Dimercaptopropyl, 1-ethylpropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, hexyl, benzyl Pentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-didecylbutyl, iota, 2-dimethylbutyl, I% dimethylbutyl Base, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 112_triterpene Propyl, 1,2,2-trimethylpropyl, ethyl-1-methylpropyl or ethyl-2-methylpropene 147475.doc 14- 201043139. c^-c:8 alkyl For example, heptyl 'octyl, 2-ethylhexyl and positional isomers thereof. C^-Cm alkyl is also additionally, for example, anthracenyl, fluorenyl, propylheptyl, 3-propylheptyl and their positions Haloalkyl: having 1 to 2 (CVC2 haloalkyl), 1 to 3 haloalkyl groups, 1 to 4 (CrCUi alkyl), 1 to 6 (Ci-Ce haloalkyl) ), 1 to 8 (Ci-C8_hospital), 1 to 10 (Ci-Ci. calcination) or 2 to 1 (c2·C10) alkyl or a straight chain or branched chain An alkyl group (as described above) wherein some or all of the hydrogen atoms of the groups may be replaced by a dentate atom 如上 as described above. Specifically, it is a Ci-C2 halogen group such as chloromethyl or bromine Methyl, dichloro Base, trimethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloro-methyl, difluoromethyl, 1-chloroethyl, 1-methyl 1-fluoroethyl, 2-fluoroethyl ' 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-gas-2-fluoroethyl, 2-chloro-2,2- Difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-dilactoethyl or five chaotic ethyl. Ci-C 〗 〖Huanxuan base is additionally for example 1,1,1 -Trifluoropropan-2-yl, 3,3,3-trifluoropropyl or heptafluoropropyl. The Cl-C4 halo q alkyl group is additionally, for example, 1-cyclobutyl, 2-chlorobutyl, 3-chlorobutyl or 4-chlorobutyl.

Ci-C1()經烧基:具有1至2個(Ci-C2經烧基)、1至4個(Cr * c4羥烧基)、2至4個(C2-C4羥烧基)、1至6個((^-(^羥烧 . 基)、2至6個(C2-C6羥烷基)、1至8個(CVCs羥烷基)、2至8 個(C2-C8羥烷基)、1至1〇個(cvCw羥烷基)或2至10個(C2-Ci〇幾烧基)碳原子之直鏈或分支鏈烧基(如上所述),其中 至少一個氫原子經羥基置換,諸如2-羥乙基或3-羥丙基。 烯基及烯氧基、烯基羰基及其類似基團中之烯基部分: 147475.doc •15- 201043139 具有2至4個(C2-C4烯基)、2至6個(C2-C6烯基)、2至8個(C2- C8^基)、3至8個(C3-C8烯基)、2至10個(C2-C10烯基)或3至 10個(C3_C1G烯基)碳原子及在任何位置之雙鍵的單不飽和 直鏈或分支鏈烴基’例如CrC6烯基,諸如乙烯基、卜丙烯 基、2_丙烯基、1-甲基乙烯基、1-丁烯基、2-丁烯基、3_ 丁烯基、1-曱基-1-丙烯基、2-曱基-1-丙烯基、甲基 丙烯基、2-曱基-2-丙烯基、卜戊烯基、2-戊烯基、3_戊烯 基、4-戊浠基、ι_甲基-丨_ 丁稀基、2_甲基-^丁烯基、3 基-1-丁烯基、1-甲基_2_ 丁稀基、2 -曱基-2-丁稀基、3 基-2-丁烯基、!_甲基_3_丁烯基、2_曱基_3_丁烯基、3 基-3-丁烯基、二曱基_2_丙烯基 ' 丨,2_二甲基_1_内 基、1,2-二曱基_2_丙烯基、丨_乙基_丨_丙烯基、“乙基〈 烯基、1-己烯基、2-己烯基、3-己烯基、4-已烯基、5 烯基、1-曱基-^戊烯基、2_甲基-N戊烯基' 3甲基] 1- 曱基-2-戊烯基 4-甲基-2_戊烯基 3-甲基-3-戊稀基 2- 曱基-4-戊稀基 1,1-二甲基-2-丁烯基、 基-3-丁烯基、^-二甲基-i丁烯基、li2_二甲基_2-了 基、1,2-二曱基_3_丁烯基、込弘二甲基丁烯基、丄3 甲基-2-丁烯基、U3_二甲基_3_丁烯基、2,2_二甲基 基、2,3-_甲基_ι_ 丁烯基、2,3-二曱基_2_ 丁烯基、2 3 甲基-3-丁烯基、3,3_二甲基丁烯基、3,3·二甲基 烯基 烯基 烯基 烯基 烯基 4-甲基-1-戊烯基 3- 甲基-2-戊烯基 2-曱基-3-戊烯基 ^曱基-4-戊烯基 4- 甲基-4-戊烯基 2_曱基-2 1-甲基-3 4_曱基-3 3_甲基-4 甲 甲 甲 埽 .丙 己 .戊 .戍 .戊 .戊 -戊 .甲 烯 -—* 一1 —» .烯 _ 一 '场 147475.doc -16· 201043139 基、1-乙基-1-丁烯基、1_乙基_2_ 丁浠基、1_乙基丁歸 基、2-乙基-1-丁烯基、2_乙基_2_丁烯基、2_乙基·^丁烯 基、1,1,2-二甲基-2-丙烯基、1-乙基_ι_甲基丙烯基、^ 乙基-2-甲基-1-丙烯基、丨_乙基_2_甲基_2_丙烯基及其類似 基團; 鹵稀基及_烯氧基、鹵烯基羰基及其類似基團中之齒稀 基部分.具有2至4個(C2-C4函烯基)、2至6個(C2-C6鹵稀 基)、2至8個(C2-C8 _烯基)或2至10個(C2-C1() _烯基)碳原 子及在任何位置之雙鍵的不飽和直鏈或分支鏈烴基(如上 所述)’其中此等基團中之一些或全部氫原子可經如上所 述之鹵素原子(尤其氟、氯及溴)置換,例如氯乙烯基、氯 烯丙基及其類似基團; 快基及炔氧基、炔基羰基及其類似基團中之炔基部分: 具有2至4個(C2-C4炔基)、2至6個(C2-C6炔基)、2至8個(C2-Cg块基)、3至8個(C3-Cs炔基)、2至10個(C2-CW炔基)或3至 1 0個(C3_C1()炔基)碳原子及一或兩個在任何位置之參鍵的 直鏈或分支鏈烴基’例如C2-C6炔基,諸如乙炔基、1_丙炔 基、2-丙炔基、1_ 丁炔基、2_ 丁炔基、3-丁炔基、1-甲基_ 2-丙块基、1-戊炔基、2-戊炔基、3-戊炔基、4-戊炔基、1-曱基-2-丁炔基、1_曱基_3_ 丁炔基、2_甲基_3_ 丁炔基、3_ 甲基-1-丁炔基、1,1-二甲基_2-丙炔基、1-乙基-2-丙炔基、 1-己炔基、2-己炔基、3-己炔基、4-己炔基、5-己炔基、1-甲基-2-戊炔基、1_曱基_3-戊炔基、1-曱基_4-戊炔基、2-甲基-3-戊炔基、2-甲基-4-戊炔基、3-甲基-1-戊炔基、3- 147475.doc •17- 201043139 曱基-4-戊炔基、4-甲基-1-戊炔基、4-甲基-2-戊炔基、ι,ΐ-二甲基-2-丁炔基、1,1-二甲基-3-丁炔基、1,2-二甲基-3-丁 炔基、2,2-二曱基-3-丁炔基、3,3-二曱基-1-丁炔基、^乙 基-2-丁快基、1 -乙基-3-丁炔基、2-乙基-3-丁炔基、1 -乙 基-1-甲基-2-丙炔基及其類似基團; 鹵炔基及_炔氧基、i炔基羰基及其類似基團中之鹵炔 基部分:具有2至4個(C2-C4 _炔基)、2至6個(C2-C6鹵炔 基)、2至8個(C2-C8_炔基)或2至10個(C2-C1G_炔基)碳原 子及一或兩個在任何位置之參鍵的不飽和直鏈或分支鏈烴 基(如上所述),其中此等基團中之一些或全部氫原子可經 如上所述之鹵素原子(尤其氟、氣及溴)置換; %炫基及J哀烧氧基、環烧基魏基及其類似基團中之環烧 基部分:具有3至6個(CVC6環烷基)、3至8個(C3_C8環烷基) 或3至10個(C3-C1G環烧基)碳環成員之單環飽和烴基,諸如 環丙基、環丁基、環戊基、環己基、環庚基、環辛基、環 壬基及環癸基; 函環烷基及i環烷氧基、齒環烷基羰基及其類似基團中 之鹵環烷基部分:具有3至6個(CrC6鹵環烷基)、3至8個 (C3_CS鹵環烷基)或3至丨〇個(C3_c1〇鹵環烷基)碳環成員之單 環飽和烴基(如上所述),其中一些或全部氫原子可經如上 所述之画素原子(尤其氟、氯及溴)置換; 烷氧基.經由氧連接之烷基。Ci_C2烷氧基為甲氧基或 乙氧基。Ci-C4烷氧基另外為例如正丙氧基 ' 丨_甲基乙氧基 (異丙氧基)、丁氧基、i•甲基丙氧基(第二丁氧基)' 2_子基 147475.doc 201043139 丙氧基(異丁氧基)或u_二甲基乙氧基(第三丁氧基p Ci_ C6烷氧基另外為例如戊氧基、i-甲基丁氧基、2_甲基丁氧 基、%甲基丁氧基、二甲基丙氧基、丨,2_二甲基丙氧 基、2,2-二甲基丙氧基' 1-乙基丙氧基、己氧基、1-曱基 戊氧基、2-f基戊氧基、3 -甲基戊氧基、4_甲基戊氧基、 二甲基丁氧基、1,2-二甲基丁氧基、丨,3_二甲基丁氧 基、2,2-二甲基丁氧基、2,3_二甲基丁氧基、3,3-二甲基丁 氧基、1-乙基丁氧基、2-乙基丁氧基、ι,ι,2_三甲基丙氧 基二曱基丙氧基、1-乙基-i_甲基丙氧基或丨_乙基_ 2-曱基丙氧基。C^-Cs烷氧基另外為例如庚氧基、辛氧基、 2·乙基己氧基及其位置異構體。Cl_Ci〇烷氧基另外為例如 壬氧基、癸氧基及其位置異構體。C2-C1G烷氧基係如Cl_ C10烷氧基,曱氧基除外。 鹵烷氧基:部分或完全經氟、氯、溴及/或碘取代,較 佳經氟取代之如上所述之烷氧基^ 鹵烷氧基例如為 〇ch2f、ochf2、OCF3、OCH2(M、OCHCl2、occi3、氯氟 曱氧基、二氣氟曱氧基、氯二氟甲氧基、2-氟乙氧基、2-乳乙氧基、2 -漠乙氧基、蛾乙氧基、2,2_二氟乙氧基、 2,2,2-三氟乙氧基、2-氣-2-氟乙氧基、2-氯-2,2-二氟乙氧 基、2,2-二氯-2-氟乙氧基、2,2,2-三氯乙氧基或〇C2F5。 鹵烷氧基另外為例如2-氟丙氧基、3-氟丙氧基、2,2-二氟丙氧基、2,3 -二氟丙氧基、2-氣丙氧基、3 -氣丙氧 基、2,3-二氯丙氧基、2-溴丙氧基、3-溴丙氧基、3,3,3-三 氟丙氧基、3,3,3-三氯丙氧基、OCH2-C2F5、〇CF2-C2F5、 147475.doc -19- 201043139 1- (CH2F)-2-鼠乙氧基 2 . , . . , , ( 2C1)'2'^^^^ ' l-(CH2Br)- 2- 溴乙乳基4_鼠丁氧基、4-氣丁备1 風1 丁虱基、4-溴丁氧基或九 乱丁乳基Cl_C6鹵烷氧基另外&amp;也丨l r 畜…、… 騎另外為例如5·氟戊氧基、5-氣戊 軋基、5-&gt;臭戍氧基、5_碰士与 童…… 峨戍乳基、十-氟戊氧基、6-1己 軋基、6-氣己氣基、6_溴己急 “ ,昊己氧基、6,己氧基或十二氟己 氧基。 烯氧基:經由氧原子連 χ ^ ▲ 如上所述之烯基,例如C2- C 1 〇 氧^基’諸如1 _ 7膝备贫 乙烯礼基、1-丙烯氧基、2_丙烯氧基、 I -甲基乙稀氧基、1-丁嫌氮其 丁烯虱基、2-丁烯氧基、3_ 丁烯氧 土 =甲基小丙稀氧基、2_甲基+丙婦氧基、ι_甲基_2_ p乳基、2_甲基_2_㈣氧基、丨_戊烯氧基、2_戍稀氧 土、3_戍稀乳基、4,戊烯氧基、1-甲基-1-丁稀氧基、2_曱 =小丁烯氧基、”基·1·丁稀氧基、1_甲基·2-丁烯氧 基:2二甲基_2_ 丁稀氧基、3_甲基士 丁烯氧基、卜甲基丄 稀氧基2甲基_3_ 丁婦氧基、3甲基_3· 丁稀基、I,】·二 甲基-2-丙烯氧基、以:甲基小丙烯氧基、仏二甲基| 丙婦氧基、1_乙基-1·丙稀氧基、1-乙基-2-丙烯氧基、卜己 ,氧基、2-己烯氧基、3_己稀氧基、心己烯氧基、5_己烯 孔基、1_甲基小戊稀氧基、2_甲基」·戊烯氧基、3^基_ 1_戊稀氧基、4·甲基-1·戊稀氧基、1-甲基·2-戊烯氧基、2_ :基_2_戊歸氧基、3rn-戊烯氧基、4·甲基_2-戊烯氧 土、^甲基-3-戊烯氧基、2_甲基_3_戊稀氧基、3_甲基 戊烯氧基、4_甲基-3_戊烯氧基、1-甲基-4-戊烯氧基、2_甲 基·4-戊婦氧基、3-甲基_4_戊稀氧基、4_甲基冰戊烯氧 W475.doc -20- 201043139 ❹Ci-C1 () burned base: has 1 to 2 (Ci-C2 burned base), 1 to 4 (Cr * c4 hydroxyalkyl), 2 to 4 (C2-C4 hydroxyalkyl), 1 Up to 6 ((^-(^ hydroxy).), 2 to 6 (C2-C6 hydroxyalkyl), 1 to 8 (CVCs hydroxyalkyl), 2 to 8 (C2-C8 hydroxyalkyl) a linear or branched alkyl group (as described above) of 1 to 1 (cvCw hydroxyalkyl) or 2 to 10 (C2-Ci oxime) carbon atoms, wherein at least one hydrogen atom is via a hydroxyl group Substitution, such as 2-hydroxyethyl or 3-hydroxypropyl. Alkenyl and alkenyl groups in alkenyloxy, alkenylcarbonyl and the like: 147475.doc •15- 201043139 with 2 to 4 (C2 -C4 alkenyl), 2 to 6 (C2-C6 alkenyl), 2 to 8 (C2-C8-yl), 3 to 8 (C3-C8 alkenyl), 2 to 10 (C2-C10) Alkenyl) or 3 to 10 (C3_C1G alkenyl) carbon atoms and a monounsaturated linear or branched hydrocarbon group at the position of a double bond such as a CrC6 alkenyl group such as a vinyl group, a propylene group or a 2-propenyl group , 1-methylvinyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-mercapto-1-propenyl, 2-mercapto-1-propenyl, methacryl, 2-mercapto-2-propenyl, prepentenyl, 2-pentenyl, 3-pentenyl, 4-pentanyl, iota-methyl-hydrazine-butanyl, 2-methyl-^ Butenyl, 3-yl-1-butenyl, 1-methyl-2-butylenyl, 2-indenyl-2-butenyl, 3-yl-2-butenyl, !_methyl_3_ Butenyl, 2_fluorenyl_3-butenyl, 3-yl-3-butenyl, diindolyl-2-propenyl' fluorene, 2-dimethyl-1-enyl, 1,2- Dimercapto-2-propenyl, 丨_ethyl_丨-propenyl, "ethyl < alkenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5 alkenyl, 1-indolyl-^pentenyl, 2-methyl-N-pentenyl '3 methyl] 1-decyl-2-pentenyl 4-methyl-2-pentenyl 3- Methyl-3-pentyl 2-mercapto-4-pentyl 1,1-dimethyl-2-butenyl, -3-butenyl, ^-dimethyl-ibutenyl , li2_dimethyl-2-yl, 1,2-diindenyl-3-butenyl, indole dimethylbutenyl, indole-3-methyl-2-butenyl, U3_dimethyl _3_butenyl, 2,2-dimethyl, 2,3-methyl-butenyl, 2,3-diindenyl-2-butenyl, 2 3 methyl-3-butene Alkenyl, 3,3-dimethylbutenyl, 3,3·dimethyl alkenyl alkenyl Alkenyl 4-methyl-1-pentenyl 3-methyl-2-pentenyl 2-mercapto-3-pentenyl fluorenyl-4-pentenyl 4-methyl-4-pentene Base 2_mercapto-2 1-methyl-3 4_mercapto-3 3_methyl-4 methylmethyl hydrazine. propylene. pent. pent. pentane-pentyl. methylene--* a 1 —» .烯_一' field 147475.doc -16· 201043139 base, 1-ethyl-1-butenyl, 1-ethyl-2-butanthyl, 1-ethylbutyl group, 2-ethyl 1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-2-butenyl, 1,1,2-dimethyl-2-propenyl, 1-ethyl_ι_ a methacryl group, an ethyl-2-methyl-1-propenyl group, a hydrazine-ethyl 2-methyl-2-propenyl group and the like; a halogenated group and an oxyalkylene group a dentate moiety in a carbonyl group and the like. It has 2 to 4 (C2-C4 functional alkenyl) groups, 2 to 6 (C2-C6 halogenated groups), 2 to 8 (C2-C8 _ Alkenyl) or 2 to 10 (C2-C1()-alkenyl) carbon atoms and an unsaturated linear or branched hydrocarbon group at the position of a double bond at any position (as described above) wherein some of these groups Or all of the hydrogen atoms may be replaced by a halogen atom (especially fluorine, chlorine and bromine) as described above, for example a vinyl chloride group, a chloroallyl group, and the like; an alkynyl moiety in a fast and alkynyloxy group, an alkynylcarbonyl group, and the like: having 2 to 4 (C2-C4 alkynyl groups), 2 to 6 (C2-C6 alkynyl), 2 to 8 (C2-Cg block), 3 to 8 (C3-Cs alkynyl), 2 to 10 (C2-CW alkynyl) or 3 to 1 0 a (C3_C1()alkynyl) carbon atom and one or two straight or branched chain hydrocarbon groups at any position, such as a C2-C6 alkynyl group, such as ethynyl, 1-propynyl, 2-propyne Base, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-cyano, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentyl Alkynyl, 1-mercapto-2-butynyl, 1-hydrazino-3-butynyl, 2-methyl-3-butynyl, 3-methyl-1-butynyl, 1,1-dimethyl Base 2 -propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1 -Methyl-2-pentynyl, 1_fluorenyl-3-cycloynyl, 1-indenyl- 4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4- Pentynyl, 3-methyl-1-pentynyl, 3-147475.doc •17- 201043139 decyl-4-pentynyl, 4-methyl-1-pentynyl 4-methyl-2-pentynyl, iota, ΐ-dimethyl-2-butynyl, 1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butene Alkynyl, 2,2-dimercapto-3-butynyl, 3,3-dimercapto-1-butynyl, ethyl-2-butanyl, 1-ethyl-3-butyne , 2-ethyl-3-butynyl, 1-ethyl-1-methyl-2-propynyl and the like; haloalkynyl and ethynyloxy, i-alkynylcarbonyl and the like a haloalkyne moiety in the group: 2 to 4 (C2-C4-alkynyl), 2 to 6 (C2-C6 haloalkynyl), 2 to 8 (C2-C8-alkynyl) or 2 Up to 10 (C2-C1G-alkynyl) carbon atoms and one or two unsaturated linear or branched hydrocarbon groups (as described above) at any position, wherein some or all of these groups are hydrogen The atom may be replaced by a halogen atom (especially fluorine, gas, and bromine) as described above; a cyclodyl moiety in the hexyl group and the sulphonyloxy group, the cycloalkyl group, and the like: having 3 to 6 Monocyclic saturated hydrocarbon groups (CVC6 cycloalkyl), 3 to 8 (C3_C8 cycloalkyl) or 3 to 10 (C3-C1G cycloalkyl) carbocyclic members, such as cyclopropyl, cyclobutyl, ring Pentyl, cyclohexyl, ring a cyclyl group, a cyclooctyl group, a cycloalkyl group and a cycloalkyl group; a halocycloalkyl moiety in a cycloalkyl group and an i cycloalkoxy group, a ring cycloalkylcarbonyl group, and the like: having 3 to 6 (CrC6) Halocycloalkyl), 3 to 8 (C3_CS halocycloalkyl) or 3 to fluorene (C3_c1 fluorenylcycloalkyl) carbocyclic ring members of a monocyclic saturated hydrocarbon group (as described above), some or all of which are hydrogen The atom may be replaced by a pixel atom as described above (especially fluorine, chlorine and bromine); an alkoxy group. The Ci_C2 alkoxy group is a methoxy group or an ethoxy group. Further, the Ci-C4 alkoxy group is, for example, n-propoxy 'indole-methylethoxy (isopropoxy), butoxy, i-methylpropoxy (second butoxy)' 2_ Base 147475.doc 201043139 Propoxy (isobutoxy) or u-dimethylethoxy (t-butoxy p Ci_C6 alkoxy is additionally, for example, pentyloxy, i-methylbutoxy, 2-methylbutoxy, %methylbutoxy, dimethylpropoxy, hydrazine, 2-dimethylpropoxy, 2,2-dimethylpropoxy' 1-ethylpropoxy , hexyloxy, 1-decylpentyloxy, 2-fylpentyloxy, 3-methylpentyloxy, 4-methylpentyloxy, dimethylbutoxy, 1,2-di Methylbutoxy, hydrazine, 3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, ι,ι,2-trimethylpropoxydimercaptopropoxy, 1-ethyl-i-methylpropoxy or hydrazine Ethyl-2-nonylpropoxy. C^-Cs alkoxy is additionally, for example, heptyloxy, octyloxy, ethyl-2-hexyloxy and positional isomers thereof. Cl_Ci decyloxy is additionally For example, decyloxy, decyloxy and their positions The C2-C1G alkoxy group is, for example, a Cl_C10 alkoxy group, other than a decyloxy group. A haloalkoxy group: partially or completely substituted by fluorine, chlorine, bromine and/or iodine, preferably substituted by fluorine as described above. The alkoxy group haloalkoxy is, for example, 〇ch2f, ochf2, OCF3, OCH2 (M, OCHCl2, occi3, chlorofluoromethoxy, difluorofluoromethoxy, chlorodifluoromethoxy, 2-fluoroethyl) Oxyl, 2-lactylethoxy, 2-ethoxyethoxy, moth ethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-gas-2- Fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy or hydrazine C2F5. The oxy group is additionally, for example, 2-fluoropropoxy, 3-fluoropropoxy, 2,2-difluoropropoxy, 2,3-difluoropropoxy, 2-propoxy, 3-propane. Oxyl, 2,3-dichloropropoxy, 2-bromopropoxy, 3-bromopropoxy, 3,3,3-trifluoropropoxy, 3,3,3-trichloropropoxy , OCH2-C2F5, 〇CF2-C2F5, 147475.doc -19- 201043139 1- (CH2F)-2-murine ethoxy 2 . , . . , , ( 2C1)'2'^^^^ ' l-( CH2Br)- 2-Bromoethyl lactyl 4_murineoxy, 4-gas butyl 1 wind 1 Butyl, 4-bromobutoxy or 9 The milk-based Cl_C6 haloalkoxy group &amp; also 丨lr animal ..., ... ride another for example 5 · fluoropentyloxy, 5-air pentylene, 5-> skox oxy, 5 _ 士 and children峨戍 峨戍 峨戍, 十-Fluoropentyloxy, 6-1 hexyl, 6-gas hexane, 6 bromohexidine, hexyloxy, 6, hexyloxy or decyl Oxygen. Alkenyloxy: via an oxygen atom χ ^ ▲ an alkenyl group as described above, for example, C2-C 1 oxime oxyl group such as 1 _ 7 knee vinylidene, 1-propenyloxy, 2-propenyloxy , I-methylethyleneoxy, 1-butane nitrogen, butenyl, 2-butenyloxy, 3-butene oxide = methyl propyleneoxy, 2-methyl + propylene oxide Base, ι_methyl_2_p-milyl, 2-methyl-2-(4-)oxy, quinolyloxy, 2_戍 sulphur, 3 戍 乳, 4, penteneoxy, 1 -Methyl-1-butenyloxy, 2_曱=small butenyloxy, "yl·1·butanoxy, 1-methyl-2-butenyloxy: 2 dimethyl-2-indene Dilute oxy, 3-methyl-butenyloxy, benzyl oximeoxy 2 methyl _3_butoxy, 3 methyl _3 · butyl, I, dimethyl methacrylate Oxyl, with: methyl propylene oxy, decyl dimethyl | propyl ethoxy, 1-ethyl-1- propyloxy, 1-ethyl-2-propenyloxy, hexyl, oxy , 2-hexenyloxy, 3-hexamethoxyoxy, hexenyloxy, 5-hexeneporyl, 1-methylpentaloxy, 2-methyl"penteneoxy, 3 ^基_1_pentenyloxy, 4·methyl-1·pentyloxy, 1-methyl 2-pentenyloxy, 2_:yl-2-pentyloxy, 3rn-pentenyloxy, 4·methyl-2-penteneoxycoxide, methyl-3-pentenyloxy, 2 _Methyl_3_pentamethoxy, 3-methylpentenyloxy, 4-methyl-3-pentenyloxy, 1-methyl-4-pentenyloxy, 2-methyl-4 -Valentyloxy, 3-methyl-4 pentyloxy, 4-methylpentene oxide W475.doc -20- 201043139 ❹

、,-二f基-2-丁埽氧基、u&lt;f基_3_ 丁稀氧基、 1,2-一曱基丁烯氧基、二甲基I 丁稀氧基、I;.二 甲基-3-丁烯氧基、仏二甲基小丁婦氧基、以二甲基_2_ 丁烯氧基、1,3-二甲基_3_丁稀氧基、2,2_二甲基_3•丁婦氧 基、2,3-二甲基小丁烯氧基、2,3_二曱基_2_丁烯氧基、 2,3-二甲基-3_丁稀氧基、3,3_二甲基_卜丁稀氧基、3,3_二 甲基丁婦氧基、卜乙基_卜丁烯氧基、1·乙基丁稀氧 基、1-乙基-3-丁焊氧基、2_乙基小丁烯氧基、2_乙基1 丁婦氧基、2-乙基_3_丁稀氧基、u,2jf基·2_丙稀氧 基、1-乙基-1-甲基-2_丙烯氧基、i•乙基_2_甲基小丙稀氧 基及1-乙基-2-甲基-2-丙烯氧基及其類似基團; 鹵烯氧基:部分或完全經氟、氯、溴/或及碘取代,較 佳經氟取代之如上所述之烯氧基。 炔氧基:經由氧原子連接之如上所述之炔基,例如c2_ c10炔氧基,諸如2-丙炔氧基、2-丁炔氧基、3_ 丁炔氧基、 1-甲基-2-丙炔氧基、2_戊快氧基、%戊炔氧基、4_戊炔氧 基、1-甲基-2-丁炔氧基、基·3_ 丁炔氧基、2_甲基-&gt; 丁炔氧基、1-乙基-2-丙炔氧基、2_己炔氧基、%己炔氧 基、4·己炔氧基、5_己炔氧基、1-甲基-2-戊炔氧基、卜甲 基-3-戊炔氧基及其類似基團; 鹵炔氧基:部分或完全經氟、氣、溴/或及碘取代,較 佳經氟取代之如上所述之炔氧基。 環烷氧基.經由氧原子連接之如上所述之環烧氧基,例 如C3-C1Gi哀炫乳基或C3_CS環烧氧基,諸如環丙氧基、環戊 147475.doc -21 - 201043139 氧基、環己氧基、環庚氧基、環辛氧基、環壬氧基、環癸 氧基及其類似基團; 環烯氧基.經由氧原子連接之如上所述之環稀氧基,例 如C3_C1?環烯氧基、C3_Cs環烯氧基,或較佳為c5_C6環烯 氧基,諸如環戊-1·烯氧基、環戊-2-烯氧基、環己_1_烯氧 基及環己-2-烯氧基; 烷氧基烷基:具有1至10個、1至8個、1至6個或1至4 個,尤其1至3個碳原子之如上定義之烷基,其中一個氫原 子經具有1至8個、1至6個或尤其丨至4個碳原子之烷氧基置 換,例如甲氧基甲基、2-曱氧基乙基、乙氧基曱基、3_曱 氧基丙基、3 -乙氧基丙基及其類似基團。 烧氧基烧氧基:具有1至1〇個、1至8個、丨至6個或〖至4 個,尤其1至3個碳原子之如上定義之烷氧基,其中一個氫 原子經具有1至8個、1至6個或尤其丨至4個碳原子之烷氧基 置換,例如2-甲氧基乙氧基、2_乙氧基乙氧基、3_甲氧基 丙氧基、3 -乙氧基丙氧基及其類似基團。 烷基羰基:式R-CO-之基團,其中R為如上定義之烷 基’例如cvc〗。烧基、cvc8院基、Cl_C6烧基、Ci_c^ 基、Ci-C2烷基或Cs-C4烷基。實例為乙醯基、丙醯基及其 類似基團。CrC4烷基羰基之實例為丙基羰基、異丙基羰 基、正丁基羰基、第二丁基羰基、異丁基羰基及第三丁基 羰基。 烷氧羰基:式R-c〇-之基團,其中R為如上定義之烷氧 基’例WCVCio烧氧基、CVC8烷氧基、Cl_c^氧基、Cl_ 147475.doc -22- 201043139 G烷氧基或心^2烷氧基^ Cl_C4烷氧幾基之實例為甲氧羰 基、乙氧羰基、丙氧羰基、異丙氧羰基、正丁氧幾某、第 二丁氧羰基、異丁氧羰基及第三丁氧羰基。 烷基磺醯基:式R-S(0)2-之基團,其中R為如上定義之 炫基’例如CrCw烧基、Cl-C8烧基、Ci_c6燒基、Ci_Cj 基或CrC:2烷基。Cl_(:4烷氧基磺醯基之實例為甲磺醯基、 乙磺醯基、丙磺醯基、異丙磺醯基、正丁磺醯基、第二丁 磺醯基、異丁磺醯基及第三丁磺醯基。 烧硫基:經由硫原子連接之如上定義之炫基。 齒烷硫基:經由硫原子連接之如上定義之_烷基。 烯硫基:經由硫原子連接之如上定義之婦基。 i烯硫基:經由硫原子連接之如上定義之Α烯基。 炔硫基:經由硫原子連接之如上定義之炔基。 鹵炔硫基:經由硫原子連接之如上定義之齒炔基。 環烷硫基:經由硫原子連接之如上定義之環烷基。 苯基-CrC4烷基:氫原子經苯基置換之Ci_c4烷基(如上 定義),諸如苯甲基、苯乙基及其類似基團。 苯基-Ci-C:4烷氧基:一個氫原子經苯基置換烷氧 基(如上定義),諸如苯曱基氧基、苯乙基氧基及其類似基 團。 3員、4員、5員、6員、7員、8員、9員或1〇員飽和、部 分不飽和或芳族雜環,其含有1、2、3或4個來自由氧、氮 (呈N或NR形式)及硫(呈s、8〇或§〇2形式)組成之群的雜原 子及視情況選用之1或2個選自c(=〇)及c(=s)之基團作為環 147475.doc -23- 201043139 成員: -二員、四員、五員或六員飽和或部分不飽和雜環(下 文中亦稱作雜環基)’其含有一、二、三或四個來自由 氧、氮(呈N或NR形式)及硫(呈S、SO或S〇2形式)組成之群 的雜原子及視情況選用之1或2個選自C(=0)及C(=S)之基團 作為環成員:例如單環飽和或部分不飽和雜環,其除碳環 成員之外還含有一至二個氣原子及/或一個氧或硫原子或 一或兩個氧及/或硫原子及視情況選用之1或2個選自c(=〇) 及C(=S)之基團,例如2-環氧乙烷基、2-硫雜環丙烷基、^ 氮丙啶基或2-氮丙啶基、1-氮雜環丁基、2_氮雜環丁基或 3-氮雜環丁基、2-四氫呋喃基、3·四氫呋喃基、3_四氫呋 喃-2-酮基、4-四氫呋喃-2-酮基、5_四氫呋喃_2_酮基、2_ 四氫呋喃_3_酮基、4-四氫呋喃-3·酮基、5_四氫呋喃_3_酮 基、2-四氫噻吩基、3-四氫噻吩基、3_四氫噻吩_2•酮基、 4_四氫噻吩-2-酮基、5-四氫噻吩_2_酮基、2_四氫噻吩_3_ 酮基、4-四氫噻吩-3-酮基、5-四氯噻吩_3_酮基、2_吡咯啶 基、3-吡咯啶基、吡咯啶_2_酮基、3_吡咯啶·2_酮基、4_ 吡咯啶-2-酮基、5-吡咯啶-2-_基、卜吡咯啶_3_酮基、2_ 吡咯啶-3-酮基、4-吡咯啶-3-¾基、5_吡咯啶_3_酮基、卜 吡咯啶-2,5-二酮基、3-吡咯啶、2,5_二酮基、3_異噁唑啶 基、4-異噁唑啶基、5-異噁唑啶基、3_異噻唑咬基、4異 噻唑啶基、5-異噻唑啶基、3-吡唑啶基、‘吡唑啶基、5_ 吡唑啶基、2-噁唑啶基、4-噁唑啶基、5_噁唑啶基、2_噻 唑啶基、4-噻唑啶基、5-噻唑啶基、2_咪唑啶基、[咪唑 147475.doc •24· 201043139 啶基、1,2,4-噁二唑啶-3-基、1,2,4-噁二唑啶-5-基、1,2,4-噻二唑啶-3-基、1,2,4-噻二唑啶-5-基、1,2,4-三哇啶-3-基、1,3,4-噁二唑啶-2-基、1,3,4-噻二唑啶-2-基、1,3,4-三 。坐咬-2 -基、2,3 -二氯咬喃·2-基、2,3 -二氮°夫喃-3 -基、2,4_ 二氣11夫喃-2 -基、2,4 -二氮α夫喃-3 -基、2,3 -二氮π塞吩-2-基、 2,3 -二氣嘆吩-3-基、2,4 -二氮嘆吩-2 -基、2,4 -二氮α塞吩-3-基、2 -α比口各#木-2 -基、2 - ntb 咐 - 3 -基、3 - ^比略·嚇&gt; -2 -基、3 - °比 咯啉-3-基、2-異噁唑啉-3-基、3-異噁唑啉-3-基、4-異噁 唑啉-3-基、2-異噁唑啉-4-基、3-異噁唑啉-4-基、4-異噁 唑啉-4-基、2-異噁唑啉-5-基、3-異噁唑啉-5-基、4-異噁 唑啉-5-基、2-異噻唑啉-3-基、3-異噻唑啉-3-基、4-異噻 唑啉-3-基、2-異噻唑啉-4-基、3-異噻唑啉-4-基、4-異噻 唑啉-4-基、2-異噻唑啉-5-基、3-異噻唑啉-5-基、4-異噻 β坐琳-5-基、2,3-二氫。比。坐-1-基、2,3-二氫。比°坐-2-基、2,3-二氫°比°坐-3-基、2,3-二氫吼吐-4-基、2,3-二氫°比。坐-5-基、 3,4-二氫吼。坐-1-基、3,4-二氫°比。坐-3-基、3,4-二氳。比吐-4-基、3,4-二氫°比。坐-5-基、4,5-二氫°比吐-1-基、4,5-二氫°比 °坐-3-基、4,5-二氫°比峻-4-基、4,5-二氫°比吐-5-基、2,3-二 氫噁唑-2-基、2,3-二氫噁唑-3-基、2,3-二氫噁唑-4-基、 2,3-二氫°惡唆-5-基、3,4-二氫&quot;惡。坐-2-基、3,4-二氫°惡。坐-3-基、3,4-二氫噁唑-4-基、3,4-二氫噁唑-5-基、3,4-二氫噁 α坐-2-基、3,4 -二氮π惡唾-3-基、3,4 -二氯。惡唾-4-基、2-旅咬 基、3 - η底咬基、4-派咬基、1,3 -二π惡炫-5 -基、2-四氫。底喃 基、4-四氫略喃基、2-四氫噻吩基、3 -六氫璉嗪基、4-六 147475.doc -25- 201043139 氫噠嗪基、2-六氫嘯啶基、4_六氫嘧啶基、5_六氫嘧啶 基、2-旅嗓基、U,5_六氮三。秦^基及…-六氮三嗓、% 基以及相應亞基; -七員飽和或部分不飽和雜環,其含有—、二、三或 四個來自由氧、氮及硫組成之群的雜原子作為環成員:例 ^具有7個%成貝之單環及雙環雜環,其除碳環成員之外 ,含有-至三個氮原子及/或一個氧或硫原子或一或兩個 氧及/或硫原子,例如 备备 J如四風SL呼基及六氫氮呼基,諸如 ⑽四氫_氮呼小…_3、_4、_5、各或_7_ 基 ’ 3,4,5,6-四氫[2H] m…3-、_4_、_5_、冬或 _7_ 基,2,3,4,7,氫 _ 氮呼-1-、-2— -3_、_4·、_5_、_6_或 7-基,2,3,6,7,四氫fl戦呼小、_2_、_3_、m =基’六氫氮呼小、_2·、…·基;四氫氧呼基及六 風斗基,諸如2,3,4,5-四氫_氧呼-2-、-3_、_4_、_5_ 、冬或'7_ 基,2,3,4,7·四氫 ΠΗ]氧呼 _2·、-3·、·4·、-5-、_ 6_ 或 _7·基,2,3,6,7,氫_ 氧呼-2…3·、-4_、-5-、6 或-7-基,·六氫氮呼+、 卜 _6- I…基,四氫心氫…或氮:…六氫_ Μ·氮呼基,四氫及一 ™基,四風_及六氯_ I3 ,、虱-1,4_噁氮呼基,四氫-及六氫_ 氧呼基,四氫 &quot; 虱 -五員d, ,-—乳平基,及相應亞基; 二、三或四個來自:雜環Γ芳族基團”其含有一、 經由碳連接且含有—至^硫組成之群之雜原子,例如 個硫或氧原子作為環-::子::-或兩個氮原子及- 攻員之5員雜方基,諸如2_咳喃基、夂 147475.doc -26- 201043139 呋喃基、2-噻吩基、3·噻吩基、2-吡咯基、3-吡咯基、3-異噁唑基、4-異噁唑基、5-異噁唑基、3-異噻唑基、4-異 噻唑基、5-異噻唑基、3_吡唑基、4-吡唑基、5-吡唑基、 2- 噁唾基、4-噁唑基、5-噁唑基、2-噻唑基、4-噻唑基、5-°塞0坐基、2-咪唾基、4-ρ米η坐基、1,2,4-°惡二°坐-3-基、1,2,4-°惡二 °坐-5_ 基、1,2,4-喧二唑-3-基、1,2,4-嘆二唑-5-基、 1,2,4-二嗤-3-基、1,3,4-°惡二唾-2-基、1,3,4-β塞二峻-2-基及 1,3,4_二唾_2-基;經由氮連接且含有一至三個氮原子作為 環成員之5員雜芳基,諸如吡咯_丨基、吡唑_丨_基、咪唑_丄_ 基、1,2,3-三唑-卜基及124_三唑-丨基;含有一、二或三 個氣原子作為環成員之6員雜芳基,諸如吡啶-2-基、吡啶- 3- 基、D比咬-4-基、3-噠嗪基、4-噠嗪基、2-嘧啶基、4-嘧 啶基、5-嘧啶基、2-吡嗪基、三嗪_2基及丨,2,4三 嗓-3 -基; (:2_〇5伸烷基:具有2至5個碳原子之二價分支鏈或較佳未 〇 分支鍵’例如 CH2CH2、、(¾¾¾、(:、 CH2CH(CH3)、CH2CH2CH2CH2、ch2ch2ch2ch2ch2。 基團-SM更確切而言為基團S-M+,其中M+為如上定義之 • I屬陽料相等物或㈣料。金屬陽離子㈣物更確切 而言為1/a Ma+,其中s ^ μ 〃、甲a马孟屬之原子價且一般為丨、2或3。 下文關於本發明化合物之摘入芬表 取代基 m、R4、R4a、R,、m、R9、 Rl°、R,1、Rl2、〜14、〜、〜、L4、Ra Rb、Re、Rd及指數从其用途之陳述本料效,且尤其在 口锊之過口及較佳特徵,尤其關於 士 仔 nl R2、p3、六· 147475.doc -27- 201043139 每一可能之相互組合中有效。 較佳為化合物IA及IIA。 在化合物IB及IIB中,較佳為以下異構體IB-1及IIB-2, ^Ny^S(0)nR4 n〜n,,-di-f-yl-2-butenyloxy, u&lt;f-based _3-butenoxy, 1,2-monodecylbutenyloxy, dimethyl-1-butyloxy, I. Methyl-3-butenyloxy, decyldimethylbutanyloxy, dimethyl-2-butenyloxy, 1,3-dimethyl-3-indoxy, 2,2_ Dimethyl-3-butanyloxy, 2,3-dimethylbutenyloxy, 2,3-diindolyl-2-butenyloxy, 2,3-dimethyl-3-indene Dilute oxy, 3,3-dimethyl-dibutyloxy, 3,3-dimethylbutanyloxy, ethylidene-butenyloxy, 1·ethylbutoxyoxyl, 1-B Alkyl-3-butadienyloxy, 2-ethylbutylbutenyloxy, 2-ethyl-1-butenyloxy, 2-ethyl-3-butenoxy, u, 2jf-based 2-propene Oxyl, 1-ethyl-1-methyl-2-propenyloxy, i•ethyl-2-methylpropanoxyoxyl and 1-ethyl-2-methyl-2-propenyloxyl A similar group; haloalkenyloxy: an alkenyloxy group as defined above, partially or completely substituted with fluorine, chlorine, bromine and/or iodine, preferably substituted by fluorine. Alkynyloxy: alkynyl group as described above attached via an oxygen atom, for example c2_c10 alkynyloxy, such as 2-propynyloxy, 2-butynyloxy, 3-butynyloxy, 1-methyl-2 -propynyloxy, 2-pentopentoxy, %pentynyloxy, 4-pentynyloxy, 1-methyl-2-butynyloxy, benzyl-3-butynyloxy, 2-methyl -&gt; butynyloxy, 1-ethyl-2-propynyloxy, 2-hexynyloxy, %hexynyloxy, 4·hexynyloxy, 5-hexynyloxy, 1-methyl Alk-2-pentynyloxy, benzyl-3-pentynyloxy and the like; a haloalkoxy group: partially or completely substituted by fluorine, gas, bromine and/or iodine, preferably by fluorine The alkynyloxy group. Cycloalkoxy. A ring alkoxy group as described above attached via an oxygen atom, such as a C3-C1Gi succinyl or a C3_CS ring alkoxy group, such as cyclopropoxy, cyclopentane 147475.doc -21 - 201043139 Oxygen a group, a cyclohexyloxy group, a cycloheptyloxy group, a cyclooctyloxy group, a cyclodecyloxy group, a cyclodecyloxy group, and the like; a cycloalkenyloxy group; a cyclooxyl group as described above attached via an oxygen atom For example, C3_C1?cycloalkenyloxy, C3_Cscycloalkenyloxy, or preferably c5_C6cycloalkenyloxy, such as cyclopent-1-enyloxy, cyclopent-2-enyloxy, cyclohexyl-1-ene Oxyl and cyclohex-2-enyloxy; alkoxyalkyl: having 1 to 10, 1 to 8, 1 to 6 or 1 to 4, especially 1 to 3, carbon atoms as defined above An alkyl group in which one hydrogen atom is replaced by an alkoxy group having from 1 to 8, from 1 to 6, or especially from 4 to 4 carbon atoms, such as methoxymethyl, 2-methoxyethyl, ethoxy Indenyl, 3-methoxypropyl, 3-ethoxypropyl and the like. Alkoxy alkoxy: an alkoxy group as defined above having 1 to 1 、, 1 to 8, 丨 to 6 or 至4, especially 1 to 3, carbon atoms, wherein one hydrogen atom has Substitution of 1 to 8, 1 to 6 or especially alkoxy groups up to 4 carbon atoms, for example 2-methoxyethoxy, 2-ethoxyethoxy, 3-methoxypropoxy , 3-ethoxypropoxy and the like. Alkylcarbonyl: a group of the formula R-CO- wherein R is an alkyl group as defined above, e.g., cvc. An alkyl group, a cvc8 building group, a Cl_C6 alkyl group, a Ci_c^ group, a Ci-C2 alkyl group or a Cs-C4 alkyl group. Examples are ethyl acetyl, propyl thiol and the like. Examples of the CrC4 alkylcarbonyl group are a propylcarbonyl group, an isopropylcarbonyl group, a n-butylcarbonyl group, a second butylcarbonyl group, an isobutylcarbonyl group and a tert-butylcarbonyl group. Alkoxycarbonyl: a group of the formula Rc〇- wherein R is an alkoxy group as defined above. Example WCVCio alkoxy, CVC8 alkoxy, Cl_coxy, Cl_147475.doc -22-201043139 G alkoxy Or an example of alkoxyl^Cl_C4 alkoxyalkyl group is methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, n-butoxyx, second butoxycarbonyl, isobutoxycarbonyl and Third butoxycarbonyl. Alkylsulfonyl: a group of the formula R-S(0)2- wherein R is a cyclyl group as defined above, for example, a CrCw alkyl group, a Cl-C8 alkyl group, a Ci_c6 alkyl group, a Ci_Cj group or a CrC: 2 alkyl group. Examples of Cl_(:4 alkoxysulfonyl are methanesulfonyl, ethylsulfonyl, propanesulfonyl, isopropylsulfonyl, n-butylsulfonyl, second butasulfonyl, isobutylsulfonate Sulfhydryl group and tert-butylsulfonyl group. Sulfur-based group: a thiol group as defined above via a sulfur atom. Tetraalkylthio group: an alkyl group as defined above via a sulfur atom. Alkylthio group: linked via a sulfur atom The aryl group as defined above: i-enylthio: a decyl group as defined above attached via a sulfur atom. alkynylthio: an alkynyl group as defined above attached via a sulfur atom. A defined alkynyl group. A cycloalkylthio group: a cycloalkyl group as defined above attached via a sulfur atom. A phenyl-CrC4 alkyl group: a Ci_c4 alkyl group (as defined above) in which a hydrogen atom is replaced by a phenyl group, such as a benzyl group, Phenylethyl and the like. Phenyl-Ci-C: 4 alkoxy: a hydrogen atom substituted by a phenyl alkoxy group (as defined above), such as phenylhydrinyloxy, phenethyloxy and Similar group. 3, 4, 5, 6, 7 or 8 members, 9 members or 1 employee saturated, partially unsaturated or aromatic a ring containing 1, 2, 3 or 4 heteroatoms from a group consisting of oxygen, nitrogen (in the form of N or NR) and sulfur (in the form of s, 8 or § 〇 2) and optionally 1 Or 2 groups selected from c(=〇) and c(=s) as a ring 147475.doc -23- 201043139 Members: - two, four, five or six members of saturated or partially unsaturated heterocyclic rings ( Also referred to hereinafter as heterocyclyl), it contains one, two, three or four impurities from a group consisting of oxygen, nitrogen (in the form of N or NR) and sulfur (in the form of S, SO or S〇2). One or two groups selected from C(=0) and C(=S) as a ring member, such as a monocyclic saturated or partially unsaturated heterocyclic ring, which is contained in addition to the carbon ring member. One to two gas atoms and/or one oxygen or sulfur atom or one or two oxygen and/or sulfur atoms and optionally one or two groups selected from the group consisting of c(=〇) and C(=S), For example, 2-oxiranyl, 2-thietyl, aziridine or 2-aziridine, 1-azetidinyl, 2-azetidinyl or 3-aza Cyclobutyl, 2-tetrahydrofuranyl, 3·tetrahydrofuranyl, 3-tetrahydrofuran-2-one, 4-tetrahydrofuran- 2-keto, 5-tetrahydrofuran-2-keto, 2-tetrahydrofuran-3-yl, 4-tetrahydrofuran-3.one, 5-tetrahydrofuran-3-yl, 2-tetrahydrothiophenyl, 3-tetra Hydrothienyl, 3_tetrahydrothiophene-2 keto, 4_tetrahydrothiophen-2-one, 5-tetrahydrothiophene-2-keto, 2_tetrahydrothiophene-3-olone, 4-four Hydrothiophen-3-one, 5-tetrachlorothiophene-3-ylketone, 2-pyrrolidinyl, 3-pyrrolidinyl, pyrrolidine-2-one, 3-pyrrolidine-2-one, 4_ Pyrrolidin-2-one, 5-pyrrolidin-2-yl, bupyridyl-3-yl-keto, 2-pyrrolidin-3-one, 4-pyrrolidin-3-ylyl, 5-pyrrolidine _3_keto, bupyrolidine-2,5-dione, 3-pyrrolidine, 2,5-dione, 3-isoxazolidine, 4-isoxazolidinyl, 5-iso Oxazolidine, 3-isothiazole, 4-isothiazolidinyl, 5-isothiazolidinyl, 3-pyrazolidinyl, 'pyrazolidine, 5-pyrazolidyl, 2-oxazolidine , 4-oxazolidinyl, 5-oxazolidinyl, 2-thiazolyl, 4-thiazolidinyl, 5-thiazolidinyl, 2-imidazolidinyl, [imidazole 147475.doc •24· 201043139 pyridine 1,2,4-oxadiazolidine-3-yl, 1,2,4-oxadiazolidine-5-yl, 1,2,4- Thiazolidine-3-yl, 1,2,4-thiadiazolidin-5-yl, 1,2,4-triwax-3-yl, 1,3,4-oxadiazolidine-2 -yl, 1,3,4-thiadiazolidin-2-yl, 1,3,4-tri. Sitting bite 2-yl, 2,3-dichloro-butan-2-yl, 2,3-dinitro-indolyl-3,yl, 2,4_dioxifufan-2-yl, 2,4 -diaza-α-furan-3-yl, 2,3-diaza π-phenant-2-yl, 2,3-dioxanthin-3-yl, 2,4-diazin-2-yl , 2,4-dinitro-α-cetin-3-yl, 2-α-specific ratio #木-2-yl, 2 - ntb 咐- 3 -yl, 3 - ^ 比略·吓与 > 2- base , 3 - °, morpholin-3-yl, 2-isoxazolin-3-yl, 3-isoxazolin-3-yl, 4-isoxazolin-3-yl, 2-isoxazole Borano-4-yl, 3-isoxazolin-4-yl, 4-isoxazolin-4-yl, 2-isoxazolin-5-yl, 3-isoxazolin-5-yl, 4-isoxazolin-5-yl, 2-isothiazolin-3-yl, 3-isothiazolin-3-yl, 4-isothiazolin-3-yl, 2-isothiazolin-4-yl , 3-isothiazolin-4-yl, 4-isothiazolin-4-yl, 2-isothiazolin-5-yl, 3-isothiazolin-5-yl, 4-isothiaphetyl-5 -yl, 2,3-dihydrogen. ratio. Sitting on a 1-yl, 2,3-dihydrogen. The ratio of 2-yl, 2,3-dihydrogen is lower than that of -3-yl, 2,3-dihydroindole-4-yl, 2,3-dihydrogen. Take 5-amino, 3,4-dihydroanthracene. Sitting on a -1-base, 3,4-dihydrogen ratio. Take -3- group, 3,4-dione. Specific ratio of 4-butyl to 3,4-dihydrogen. Sitting on -5-yl, 4,5-dihydrogen ratio to -1-yl, 4,5-dihydrogen ratio °-3-yl, 4,5-dihydrogen ratio quaternary-4-yl, 4 ,5-dihydrogen ratio thio-5-yl, 2,3-dihydrooxazol-2-yl, 2,3-dihydrooxazol-3-yl, 2,3-dihydrooxazole-4- Base, 2,3-dihydro oxime-5-yl, 3,4-dihydro &quot; evil. Sit-2-yl, 3,4-dihydrogen. 3-O-, 3,4-dihydrooxazol-4-yl, 3,4-dihydrooxazol-5-yl, 3,4-dihydrooxo-y-yl, 3,4- Diazo π oxasin-3-yl, 3,4-dichloro. Ethylene-4-yl, 2-Benbite, 3-N-Bottom, 4-bite, 1,3-dioxax-5-yl, 2-tetrahydro. Decanyl, 4-tetrahydrofuranyl, 2-tetrahydrothiophenyl, 3-hexahydropyridazinyl, 4-hexa 147475.doc -25- 201043139 hydropyridazinyl, 2-hexahydropyridinyl, 4_hexahydropyrimidinyl, 5-hexahydropyrimidinyl, 2-brenyl, U,5-hexanitrogen. a group of saturated or partially unsaturated heterocyclic rings containing -, two, three or four from a group consisting of oxygen, nitrogen and sulfur A hetero atom as a ring member: a compound having 7 % of a ring of monocyclic and bicyclic heterocycles containing, in addition to a carbocyclic ring member, - to three nitrogen atoms and/or an oxygen or sulfur atom or one or two Oxygen and/or sulfur atoms, for example, J, such as the four-wind SL group and hexahydro-hydrogen group, such as (10) tetrahydro-nitrogen, _3, _4, _5, each or _7_ group '3, 4, 5 , 6-tetrahydro[2H] m...3-, _4_, _5_, winter or _7_ group, 2,3,4,7, hydrogen_azepine-1-, -2 - -3_, _4·, _5_, _6_ or 7-base, 2,3,6,7, tetrahydrofl戦, small, _2_, _3_, m = kiln 'hexahydroazepine small, _2 ·, ... base; tetrahydrooxo group and six Duct base, such as 2,3,4,5-tetrahydro-oxo-2-, -3, _4_, _5_, winter or '7_ base, 2,3,4,7·tetrahydroanthracene] 2·,-3·,·4·,-5-,_6_ or _7·yl, 2,3,6,7, hydrogen_oxo-2...3·,-4_,-5-,6 or -7-based, hexahydroazepine +, _6-I... group, tetrahydrogen hydrogen... or nitrogen: ...hexahydro _ Μ ·Nitrogen-based, tetrahydrogen and a TM-based, four winds and hexachloro-I3, 虱-1,4-oxo-oxime, tetrahydro- and hexahydro-oxo-h, oxy-quot; Five members d, ,-- ipidyl, and corresponding subunits; two, three or four from: heterocyclic oxime aromatic groups, which contain a group of carbon-linked and containing - to sulfur An atom, such as a sulfur or an oxygen atom, acts as a ring-::::- or two nitrogen atoms and a 5-membered heteroaryl group, such as 2_coughyl, 夂147475.doc -26- 201043139 furanyl , 2-thienyl, 3-thiophenyl, 2-pyrrolyl, 3-pyrrolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4- Isothiazolyl, 5-isothiazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxanyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl , 4-thiazolyl, 5-°-sodium-based, 2-meridino, 4-ρ米η, 1,2,4-° dioxin-3-yl, 1,2,4- °恶二° sit-5_ base, 1,2,4-oxadiazol-3-yl, 1,2,4- oxadiazole-5-yl, 1,2,4-dioxin-3-yl, 1,3,4-° dioxa-2-yl, 1,3,4-β-dithio-2-yl and 1,3,4-disindol-2-yl a 5-membered heteroaryl group which is bonded via a nitrogen and contains one to three nitrogen atoms as a ring member, such as pyrrole-fluorenyl, pyrazole-indenyl, imidazolium-hydrazino, 1,2,3-triazole-b And 124-triazole-fluorenyl; 6-membered heteroaryl containing one, two or three gas atoms as ring members, such as pyridin-2-yl, pyridine-3-yl, D-bit-4-yl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, triazine-2-yl and anthracene, 2,4triazin-3-yl (: 2_〇5 alkylene: a divalent branched chain having 2 to 5 carbon atoms or preferably an untwisted branching bond such as CH2CH2, (3⁄43⁄4⁄4, (:, CH2CH(CH3), CH2CH2CH2CH2, ch2ch2ch2ch2ch2). The group -SM is more specifically the group S-M+, wherein M+ is as defined above. I is a positive equivalent or a (four) material. The metal cation (tetra) is more specifically 1/a Ma+, where s ^ μ 〃, the valence of the genus A. genus and is generally 丨, 2 or 3. In the following, the fenfen substituents m, R4, R4a, R, m, R9, R1°, R, 1, Rl2, 〜14, 〜, 〜, L4, Ra Rb, Re, Rd and The index is effective from the statement of its use, and especially in the mouthfuls and better characteristics of the mouth, especially in the possible combination of each of the possible combinations of the pair of nl R2, p3, liu 147475.doc -27- 201043139. Preferred are compounds IA and IIA. Among the compounds IB and IIB, the following isomers IB-1 and IIB-2, ^Ny^S(0)nR4 n~n are preferred.

因此’較佳為基團ΙΠΒ之以下異構體,Therefore, it is preferably the following isomer of the group ,,

(IMB-1)(IMB-1)

祀據本發明之—較佳實施例’ l2及彼此獨立地選 氯、幽素、Cl-c4貌基、Cl咖基、Ci铺氧基及( C4i烷氧基’更佳選自氫、齒素、C1_C3烷基、㈣齒 土 Cl C3炫*氧基及Cl~C3函烧氧基,特定言之選自氫、 ,、曱基' 氟甲基、二氣甲基、三狀甲基、甲氧基、氣 氧土 一氟乙氧基、2,2,2·三氟乙氧基、1,1,2,2.四氟乙 基及五氟乙氧基’且特別選自氫及氣。特定言之,L2與 兩者均為氫’或—者為氫且另一者為氣。 147475.doc -28- 201043139 根據本發明之一較佳實施例,L1及L4彼此獨立地選自 气氟’臭、Ct-C4烧基、C1-C4鹵烧基、Ci-C^燒氧基及 Cl C4鹵烷氧基,更佳選自氫、氟、溴、CVC3烷基、(^_C3 函烧基、C1_C3烷氧基及(^-(:3鹵烷氧基,特定言之選自 虱、氟、溴、曱基、氟甲基、二氟甲基、三氟曱基、 ,一氟乙基、2-四氣乙基、五敗乙基、曱氧基、 氟曱氧基、二氟甲氧基、三氟甲氧基、2,2,2-三氟乙氧基、 四氟乙氧基及五氟乙氧基,且特別選自氟、溴、甲 基、三氟曱基及三氟甲氧基,且特別選自氫、氟及CF3。 根據本發明之另一較佳實施例,Ll、L2、l3&amp;L4中一者 或兩者不為氫,且特定言之LjL4中至少—者不為氯。 根據本發明之一更佳實施例,L1及L4中一者不為氫且另 一者為氯。 根據本發明之另一較佳實施例,L2及l3中至少一者為 氫。 , 根據本發明之一更佳實施例 〇 較佳為氯’且另-者為氫;或L2及L3均為氳_ ,根據本發明之一尤其較佳實施例,L丨及1/中一者不為氫 且尤其為款或cf3) ’且所有其他取代基L(亦即l2、LiLi 或广為氫,或加中一者不為氫(且尤其為氣或㈣, 3者不為氫(且尤其為氯),且所有其他取代基 F |即%或L及L2或0為氫(尤其Ll不為氫(且尤其為氣或 CF3),L為氯,且L3&amp;L4為氫卜 L及L之尤其較佳的組合彙編於下表中: 147475.doc -29· 201043139 編號 L1 L2 L3 L4 1 F H H H 2 Br H H H 3 ch3 H H H 4 ch2ch3 H H H 5 CH(CH3)2 H H H 6 cf3 H H H 7 ch2cf3 H H H 8 CF2CHF2 H H H 9 OCF3 H H H 10 OCH2CF3 H H H 11 OCH3 H H H 12 OCH2CH3 H H H 13 F Cl H H 14 F H Cl H 15 ch3 H Cl H 16 ch2ch3 H Cl H 17 CH(CH3)2 H Cl H 18 cf3 H Cl H 19 ch2cf3 H Cl H 20 CF2CHF2 H Cl H 21 OCF3 H Cl H 22 OCH2CF3 H Cl H 23 och3 H Cl H 24 OCH2CH3 H Cl H 25 ch3 Cl H H 26 CH2CH3 Cl H H 27 CH(CH3)2 Cl H H 28 cf3 Cl H H 29 ch2cf3 Cl H H 30 CF2CHF2 Cl H H 31 OCF3 Cl H H 32 OCH2CF3 Cl H H 33 och3 Cl H H 34 OCH2CH3 Cl H H 在以上組合中,較佳為如下組合,其中L2、L3及L4為 氫,或其中L2為Cl且L3及L4為氫。尤其較佳為第1、6及13 號組合。 較佳地,R1及R2彼此獨立地選自氫、(VC4烷基、(VC2 147475.doc -30- 201043139 函烧基、Cl-C4烧氧基及Cl_C2i院氧基。更佳地 R2 彼此獨立地選自氯、甲基、乙基及三說甲基。甚至更佳 地,彼此獨立地選自氫及甲基。特定言之 均為甲基。 及尺 較佳地,R3係選自氲、CA院基、Cl.c2i燒基、Cl_c 烷乳基及^2画貌氧基。更佳地,以選自氯、甲夷4 Ο 〇 乙基及三氣曱基。甚至更佳地,r3係選自氯及甲基^ 言之,R3為氫。 基團脅〇)R5及-S(0)2R5中之R5較佳選自Cl-C道基、 烧基、Cl-C4烧氧基、Ci_c2_燒氧基、苯基 基及NRV〇,更佳選自Ci_C4院基、Ci_c^烧基、以道 氧基、CVC2齒烷氧基及NR9Rl〇且甚至更佳選自^ 及顺V。。在基團-C(=0)R5中,R5特定言之為心: 基,更特定言之為異丙基、異丁基或第三丁基,且在基 團部此中,R5特定言之為曱基。較佳地,R9為氫且 係垃自氫、q-C4烷基及苯基,較佳選自氫及C1_C4烷基。 R 較佳選自氫、CVC4烷基、_c(=〇)R5、_s(〇)2R5、 、Μ及式III基團’丨中R5具有上述通用含義之一或特定言 之上述較佳含義之一,且Μ具有上述通用含義之—或特2 言之下文給出之較佳含義之一。 R4更佳選自氫、Cl-C4烷基、C3_C4烷基羰基、Ci_C4烷氧 羰基、-CPCONODCVC4烷基、Cl_C4烷基磺醯基、CN及式 III基團且甚至更佳選自氫及Ci_C4烷基。特定言之,R4係 選自氫、CN及甲基。R4特別為氫。 、 147475.doc •31- 201043139 Μ較佳選自鹼金屬陽離子、鹼土金屬陽離子相等物、 Cu、Zn、Fe或Ni之陽離子相等物,或式(NRaRbRCRd)+之敍 陽離子,其中Ra、Rb、Rd中之一者為氫且Ra、Rb、Rc 及R中之二者彼此獨立地選自q-Cm院基。]VI更佳係選自 Li、Na、K+、WMg2.,Cu、Zn、Fe 或 Ni 之陽離子相等 物,及式(NRaRbRcRd)+之銨陽離子,其中Ra、Rb、RC&amp; Rd 中之一者為氫且Ra、Rb、尺。及Rd中之三者彼此獨立地選自 CVC丨。烷基。Μ 甚至更佳選自 Na+、K+、1/2Mg2+、1/2Cu2+、 !/2Zn2+、WFeh、ΖΝβ、三乙銨及三甲銨。 在式III之基團中,變數較佳具有與分子1之其餘部分中 相同之含義。因此,上文關於基團之較佳含義所作之陳述 亦適用於此部分。 R4a較佳選自氫、Cl_Cl0烷基、Cl_C4鹵烷基 '苯基、苯 基-C]-C4烷基及_C(=〇)R5,其中r5具有上文給出之通用含 義之一或特定言之上文給出之較佳含義之一。R4a更佳選 自氫、CVC4烷基、Cl_c4鹵烷基、苯基、苯曱基、·c(=〇)r5 及-s(o)2r5,纟中R5具有上文給出之通用含義之—或特定 言之上文給出之較佳含義之一,且更佳選自氫、Cl_C4烷 基、及,)2R5’其中r5具有上文給出之通用 含義之一或特定言之上文給出之較佳含義之一。特定言 之,R為氫、Ci-C:4烷基或CrC4鹵烷基,更特定言之為氫 或匸丨-匕烷基’且特別為氫。 若η為1,則氧原子較佳經由雙鍵鍵結於硫原子,基團 -S(〇)n-R4因此產生基團_s(哪r4。若福2,貝,】兩個氧原 147475.doc •32- 201043139 〇_r4。 為 3 ’ 則基團-S(0)n-R4為基團-S(=〇)2- n較佳為〇。 在化合物I及II中,仆a私τ± ΙΑ較佳。 化s物1較佳。在化合物I中,化合物 特定化合物IA為以下: Ο Ο 5-(2-氟-苯甲基 甲基環戊醇; 絲'⑴以]三嗤]·基曱基)-2,2-二 5-(2_二氣甲基_笨甲其、1 苴、Λ Τ丞)·1^5-巯基-[1,2,4]三唑-1-基甲 土)_2,2 - 一曱基環戊醇;及 5-(2-氟-3-氯-苯甲基1 2 )-(5'巯基-[1,2,4]三唑-1-基甲基)- !-二甲基環戊醇。 較佳化合物I及11之實你丨去上、 貫例為式1.1至1.16及II.1至Π.8化合 物,其中變數具有通用含義 ^ ^ _ &amp; 義之一或特定言之上文給出之較 佳含義之一。較佳化合物 實例為下文表1至688中彙編之 個別化合物。此外,下表中 Γ衣中關於個別變數提及之含義本身 為所討論之取代基的尤其軔 、較佳的貫施例,與提及其之組合 無關。According to the preferred embodiment of the present invention, l2 and independently of each other, chlorine, spectroscopy, Cl-c4 appearance, Cl, Ki, and (C4i alkoxy) are more preferably selected from hydrogen, teeth. a C1_C3 alkyl group, (4) a toothed earth Cl C3 ** oxy group and a Cl~C3 functional alkoxy group, specifically selected from the group consisting of hydrogen, , fluorenyl 'fluoromethyl, di-methyl methyl, tri-methyl, Methoxy, oxyfluoride-fluoroethoxy, 2,2,2·trifluoroethoxy, 1,1,2,2.tetrafluoroethyl and pentafluoroethoxy' and especially selected from hydrogen and In particular, L2 and both are hydrogen' or both are hydrogen and the other is gas. 147475.doc -28- 201043139 According to a preferred embodiment of the invention, L1 and L4 are selected independently of each other. Self-gas fluorine odor, Ct-C4 alkyl group, C1-C4 halogen group, Ci-C^ alkoxy group and Cl C4 haloalkoxy group, more preferably selected from hydrogen, fluorine, bromine, CVC3 alkyl group, (^ _C3 calcinyl group, C1_C3 alkoxy group and (^-(:3 haloalkoxy group, specifically selected from the group consisting of hydrazine, fluorine, bromine, fluorenyl, fluoromethyl, difluoromethyl, trifluoromethyl, Monofluoroethyl, 2-tetraqiethyl, penta-ethyl, decyloxy, fluoromethoxy, difluoromethoxy, trifluoromethyl a 2,2,2-trifluoroethoxy group, a tetrafluoroethoxy group, and a pentafluoroethoxy group, and is particularly selected from the group consisting of fluorine, bromine, methyl, trifluoromethyl and trifluoromethoxy, and Selected from hydrogen, fluorine, and CF 3. According to another preferred embodiment of the present invention, one or both of L1, L2, L3 &amp; L4 are not hydrogen, and in particular, at least - not chlorine in LjL4. In a preferred embodiment of the present invention, one of L1 and L4 is not hydrogen and the other is chlorine. According to another preferred embodiment of the present invention, at least one of L2 and L3 is hydrogen. According to the present invention A preferred embodiment is preferably chlorine and the other is hydrogen; or both L2 and L3 are 氲_, and according to a particularly preferred embodiment of the invention, L丨 and 1/1 are not hydrogen. And especially for the formula or cf3) 'and all other substituents L (ie, l2, LiLi or widely hydrogen, or one of the additions are not hydrogen (and especially gas or (d)), 3 are not hydrogen (and especially Chlorine), and all other substituents F | ie % or L and L2 or 0 are hydrogen (especially Ll is not hydrogen (and especially gas or CF3), L is chlorine, and L3 &amp; L4 is hydrogen L and L Particularly preferred combinations are compiled in the table below: 14 7475.doc -29· 201043139 No. L1 L2 L3 L4 1 FHHH 2 Br HHH 3 ch3 HHH 4 ch2ch3 HHH 5 CH(CH3)2 HHH 6 cf3 HHH 7 ch2cf3 HHH 8 CF2CHF2 HHH 9 OCF3 HHH 10 OCH2CF3 HHH 11 OCH3 HHH 12 OCH2CH3 HHH 13 F Cl HH 14 FH Cl H 15 ch3 H Cl H 16 ch2ch3 H Cl H 17 CH(CH3)2 H Cl H 18 cf3 H Cl H 19 ch2cf3 H Cl H 20 CF2CHF2 H Cl H 21 OCF3 H Cl H 22 OCH2CF3 H Cl H 23 och3 H Cl H 24 OCH2CH3 H Cl H 25 ch3 Cl HH 26 CH2CH3 Cl HH 27 CH(CH3)2 Cl HH 28 cf3 Cl HH 29 ch2cf3 Cl HH 30 CF2CHF2 Cl HH 31 OCF3 Cl HH 32 OCH2CF3 Cl HH 33 Och3 Cl HH 34 OCH2CH3 Cl HH In the above combination, a combination is preferred in which L2, L3 and L4 are hydrogen, or wherein L2 is Cl and L3 and L4 are hydrogen. Particularly preferred are combinations of Nos. 1, 6, and 13. Preferably, R1 and R2 are independently of each other selected from the group consisting of hydrogen, (VC4 alkyl, (VC2 147475.doc -30-201043139 decyl, Cl-C4 alkoxy, and Cl_C2i). More preferably, R2 is independent of each other. It is selected from the group consisting of chlorine, methyl, ethyl and trimethyl. Even more preferably, it is independently selected from hydrogen and methyl. It is specifically a methyl group. And preferably, R3 is selected from hydrazine. , CA hospital base, Cl.c2i alkyl group, Cl_c alkane base and ^2 morphine oxy group. More preferably, it is selected from the group consisting of chlorine, methyl sulfonium ethyl ester and trimethyl sulfhydryl group. Even more preferably, R3 is selected from the group consisting of chlorine and methyl, and R3 is hydrogen. R5 in the group R5 and -S(0)2R5 are preferably selected from the group consisting of Cl-C group, alkyl group, and Cl-C4 oxygen. a base, a Ci_c2_ alkoxy group, a phenyl group and an NRV〇, more preferably selected from the group consisting of Ci_C4, Ke_c^, oxy, CVC2, and NR9R1, and even more preferably selected from the group consisting of V. In the group -C(=0)R5, R5 is specifically defined as a radical: a radical, more specifically an isopropyl group, an isobutyl group or a tert-butyl group, and in the group, R5 is specifically referred to as a fluorenyl group. Preferably, R9 is hydrogen and is derived from hydrogen, q-C4 alkyl and phenyl, preferably selected From hydrogen and C1_C4 alkyl. R is preferably selected from the group consisting of hydrogen, CVC4 alkyl, _c(=〇)R5, _s(〇)2R5, Μ, and the group of formula III, R5, having one or more of the above general meanings. One of the above preferred meanings, and one of the above-mentioned general meanings - or one of the preferred meanings given below in particular. R4 is more preferably selected from the group consisting of hydrogen, Cl-C4 alkyl, C3_C4 alkylcarbonyl, Ci_C4 alkoxycarbonyl, -CPCONODCVC4 alkyl, Cl_C4 alkylsulfonyl, CN and a group of formula III and even more preferably selected from hydrogen and Ci_C4 alkyl. In particular, R4 is selected from the group consisting of hydrogen, CN and methyl. R4 is especially hydrogen. 147475.doc • 31- 201043139 Μ is preferably selected from the group consisting of an alkali metal cation, an alkaline earth metal cation equivalent, a cation equivalent of Cu, Zn, Fe or Ni, or a cation of the formula (NRaRbRCRd)+. Wherein one of Ra, Rb, and Rd is hydrogen and two of Ra, Rb, Rc, and R are independently selected from the group of q-Cm. The VI is preferably selected from the group consisting of Li, Na, K+, and WMg2. a cation equivalent of Cu, Zn, Fe or Ni, and an ammonium cation of the formula (NRaRbRcRd)+, wherein one of Ra, Rb, RC&amp; Rd is hydrogen and Ra, Rb, ruler, and Rd The three are independently selected from each other by CVC. The alkyl group is even more preferably selected from the group consisting of Na+, K+, 1/2Mg2+, 1/2Cu2+, !/2Zn2+, WFeh, ΖΝβ, triethylammonium and trimethylammonium. In the group, the variable preferably has the same meaning as in the rest of the molecule 1. Therefore, the above statements regarding the preferred meaning of the group also apply to this section. R4a is preferably selected from the group consisting of hydrogen, Cl_Cl0 alkyl, Cl_C4 haloalkyl 'phenyl, phenyl-C]-C4 alkyl and _C(=〇)R5, wherein r5 has one of the general meanings given above or One of the preferred meanings given above in specific terms. R4a is more preferably selected from the group consisting of hydrogen, CVC4 alkyl, Cl_c4 haloalkyl, phenyl, benzoinyl, ·c(=〇)r5 and -s(o)2r5, and R5 in the oxime has the general meaning given above. Or one of the preferred meanings given above, and more preferably selected from the group consisting of hydrogen, Cl_C4 alkyl, and, 2R5', wherein r5 has one of the general meanings given above or specifically stated above Give one of the better meanings. In particular, R is hydrogen, Ci-C:4 alkyl or CrC4 haloalkyl, more specifically hydrogen or fluorenyl-decyl&apos; and especially hydrogen. If η is 1, the oxygen atom is preferably bonded to the sulfur atom via a double bond, and the group -S(〇)n-R4 thus produces a group _s (which is r4. 147475.doc •32- 201043139 〇_r4. For 3 ' then the group -S(0)n-R4 is a group -S(=〇)2- n is preferably 〇. In compounds I and II, servant a private τ ± ΙΑ is preferred. The s material 1 is preferred. In the compound I, the compound specific compound IA is as follows: Ο Ο 5-(2-fluoro-benzylmethylcyclopentanol; silk '(1) to]三嗤]·基曱基)-2,2-二5-(2_二气methyl_笨甲甲,1 苴,Λ Τ丞)·1^5-巯基-[1,2,4]三Oxazol-1-ylethane)_2,2-tetramethylcyclopentanol; and 5-(2-fluoro-3-chloro-benzyl 1 2 )-(5' fluorenyl-[1,2,4] Triazol-1-ylmethyl)-!-dimethylcyclopentanol. Preferred compounds I and 11 are the compounds of the formulae 1.1 to 1.16 and II.1 to Π.8, wherein the variables have the general meaning ^ ^ _ &amp; One of the preferred meanings. Preferred compounds are exemplified by the individual compounds compiled in Tables 1 to 688 below. In addition, the meanings mentioned in the table below for individual variables are in themselves a particularly preferred embodiment of the substituents discussed, irrespective of the combination referred to.

147475.doc -33. 201043139147475.doc -33. 201043139

ΟΟ

147475.doc -34- 201043139147475.doc -34- 201043139

表1 式Ll化合物’其中化合物之R1、R2、L1、[2、^及。之 組合在各情況下對應於表A之一列,且R4為Η 表2 式h 1化合物,其中化合物之R1、R2、L1、L2、L3及L4之 口在各情況下對應於表A之一列,且R4為甲基 〇 夂3 j1.1化合物,其中化合物之尺1、r2、Ll、L2、[3及[4之 在各障況下對應於表A之一列,且R4為乙基 式L1化合物 組合在各情況 表5 ’其中化合物之R1、R2、Ll、L2、L3&amp;L4之 下對應於表A之一列,且R4為丙基 ^ — L3,L^ 子應於表A之一列,且R4為異丙基 147475.doc -35- 201043139 表6 式L1化合物,其中化合物2Rl、r2、Ll、l2、匕3及匕4之 組合在各情況下對應於表A之一列,且R4為正丁基 表7 ^ 式1.1化合物,其中化合物之尺1、r2、Ll、、匕3及[4之 組合在各情況下對應於表A之一列,且R4為第二丁基 表8 ^ 式1.1化合物,其中化合物之Rl、r2、L]、[2、[3及^4之 組合在各情況下對應於表A之一列,且R4為異丁基 表9 式1.1化合物’其中化合物之Rl、r2、Ll、L2、^及^之 組合在各情況下對應於表A之一列,且R4為第三丁基 表10 式L1化合物,其中化合物之R1、R2、L1、L2、L3及L4之 組合在各情況下對應於表A之一列,且R4為苯基 表11 式^ 1化合物’其中化合物之R1、R2、L1、L2、L3及L4之 組合在各情況下對應於表A之一列,且R4為4_曱基苯基 表12 式1.1化合物’其中化合物之尺1、r2、Li、L2、。及以之 組合在各情況下對應於表A之一列,且R4為Li+ 表13 式1.1化合物,其中化合物之汉1、R2、L1、L2、L3及[4之 組合在各情況下對應於表A之一列,且R4為Na+ 147475.doc -36- 201043139 表14 式Ll化合物’其中化合物之R1、R2、L1、L2、L3及L4之 、且S在各彳月況下對應於表A之一列,且R4為κ+ 表15 式Ll化合物’其中化合物之R1、R2、L1、L2、L3及L4之 、,且口在各情況下對應於表A之一列,且r/為/2Mg2+ 表16 式U化合物,其中化合物之R1、R2、L1、L2、L3及L4之 組合在各情況下對應於表A之一列,且尺4為1/2(:112+ 表17 式丁.1化合物’其中化合物之R1、R2、L1、L2、L3及L4之 、’且〇在各情况下對應於表A之一列,且尺4為ι/2Ζη2+ 表18 式1.1化合物’其中化合物之Ri、r2、L1、L2、L3及L4之 、’且〇在各情況下對應於表A之一列,且R4為i/2Fe2+ 表19 式化合物,其中化合物之r!、R2、Ll、L2、&quot;及^之 、·且σ在各情況下對應於表A之一列,且尺4為i/2Ni2+ 表20 式1,1化合物’其中化合物之R1、R2、L1、L2、L3及L4之 組〇在各情況下對應於表A之一列,且R4為nH(CH3)3 + 表21 式Ϊ.1化合物,其中化合物之、R2、Ll、L2、L3及L4之 組〇在各情況下對應於表A之一列,且r4為NH(C2H5)3+ 147475.doc -37- 201043139 表22 式1.1化合物,其中化合物之R1 之組合在各情況下對應於表 NH(CH2CH2CH2)3+ 表23 式1.1化合物,其中化合物之ri 之組合在各情況下對應於表 nh(ch(ch3)2)3+ 表24 式1.1化合物’其中化合物之Ri 之組合在各情況下對應於表 nh(ch2ch2ch2ch2)3+ 表25 式1.1化合物,其中化合物之ri、 組合在各情況下對應於表A之一列 表26 式Μ化合物,其中化合物之ri、 組合在各情況下對應於表A之一列 表27 式hi化合物,其中化合物之Rl、 組合在各情況下對應於表A之一列 表28 式Ι·1化合物,其中化合物之ri、 組合在各情況下對應於表A之一列 147475.doc 、R2、Li、L2、L3 及 L4 A之一列,且R4為 、R2、1/、L2、L3及 L4 A之一列,且R4為 、R2、I/、L2 ' L3 及 L4 A之一列,且R4為 R2 、 L! 、 L2 、 及L4之 ,且R4為曱基羰基 R2 、 1/ 、 L2 、 L3及L4之 ,且R4為乙基羰基 R2 、 L1 、 L2 、 L3及L4之 且R4為丙基羰基 R2 、 L1 、 L2 、 L3及 L4之 且R為異丙基叛基 -38- 201043139 表29 式Ι·1化合物,其中化合物之Rl、r2、Ll、ρρ及以之 組合在各情況下對應於表A之一列’且R4為曱氧叛美 表30 ^ 式1.1化合物,其中化合物之R1、R2、L1、L2、L3及L4之 組合在各情況下對應於表A之一列,且R4為乙氧羰基 表31 ΟTable 1 is a compound of the formula L1 wherein R1, R2, L1, [2, ^ and are the compounds. The combination corresponds in each case to one of the columns of Table A, and R4 is Η Table 2 Formula h 1 compound, wherein the mouths of the compounds R1, R2, L1, L2, L3 and L4 correspond in each case to one of the tables A And R4 is a methyl hydrazone 3 j1.1 compound, wherein the compound of the ruler 1, r2, L1, L2, [3 and [4 in each case corresponds to one of the tables A, and R4 is an ethyl group The combination of L1 compounds in each case Table 5 'where the compounds R1, R2, L1, L2, L3 & L4 correspond to one of the columns of Table A, and R4 is propyl^-L3, and L^ should be in one of Table A And R4 is isopropyl 147475.doc -35- 201043139 Table 6 Formula L1 compound, wherein the combination of compounds 2R1, r2, L1, l2, 匕3 and 匕4 corresponds in each case to one of Table A, and R4 Is a n-butyl group 7 ^ Formula 1.1 compound, wherein the compound of the ruler 1, r2, Ll, 匕 3 and [4 combination in each case corresponds to one of the tables A, and R4 is the second butyl table 8 ^ a compound of the formula 1.1, wherein the compound R1, r2, L], [2, [3 and ^4 combinations in each case correspond to one of the tables A, and R4 is an isobutyl group 9 formula 1.1 compound 'wherein the compound Rl The combination of r2, L1, L2, ^ and ^ corresponds in each case to one of the columns of Table A, and R4 is a compound of the third butyl group 10 formula L1, wherein the compounds are R1, R2, L1, L2, L3 and L4 The combination corresponds in each case to one of the columns of Table A, and R4 is a phenyl group. The compound of formula 1 wherein the combination of R1, R2, L1, L2, L3 and L4 of the compound corresponds in each case to Table A. One column, and R4 is a 4-mercaptophenyl group, the compound of the formula 1.1, wherein the compound is a ruler 1, r2, Li, L2. And combinations thereof correspond in each case to one of the columns of Table A, and R4 is Li+ Table 13 Formula 1.1 compound, wherein the combination of the compound of the compound 1, R2, L1, L2, L3 and [4 corresponds to the table in each case. Column A, and R4 is Na+ 147475.doc -36- 201043139 Table 14 Formula L1 compound 'where R1, R2, L1, L2, L3 and L4 of the compound, and S corresponds to Table A in each month One column, and R4 is κ+ Table 15 Formula L1 Compound 'where R1, R2, L1, L2, L3 and L4 of the compound, and the mouth corresponds to one of the tables A in each case, and r/ is 2Mg2+ A compound of the formula U wherein the combination of R1, R2, L1, L2, L3 and L4 of the compound corresponds in each case to one of the columns of Table A, and the rule 4 is 1/2 (: 112 + Table 17 formula. 'wherein the R1, R2, L1, L2, L3 and L4 of the compound' and the 〇 in each case corresponds to one of the tables A, and the rule 4 is ι/2Ζη2+. Table 18 The compound of the formula 1.1 wherein the compound Ri, r2 , L1, L2, L3, and L4, and 〇 in each case corresponds to one of the columns of Table A, and R4 is i/2Fe2+, a compound of the formula 19, wherein the compound is r!, R2, L1, L2, &quot; ^之And σ corresponds to one of the tables in each case, and the ruler 4 is i/2Ni2+. Table 20 Formula 1, Compound 1 where the compound R1, R2, L1, L2, L3 and L4 are in each case. The lower one corresponds to one of the columns of Table A, and R4 is nH(CH3)3 + Table 21 Formula Ϊ.1 compound, wherein the group of compounds, R2, L1, L2, L3 and L4 corresponds to Table A in each case. One column, and r4 is NH(C2H5)3+ 147475.doc -37- 201043139 Table 22 Compound of formula 1.1, wherein the combination of R1 of the compound corresponds in each case to the compound of formula NH(CH2CH2CH2)3+, Table 23, wherein The combination of the compounds ri corresponds in each case to the table nh(ch(ch3)2)3+ Table 24 The compound of the formula 1.1 wherein the combination of the compounds Ri corresponds in each case to the table nh(ch2ch2ch2ch2)3+ 1.1 A compound wherein the ri of the compound, in each case corresponds to a compound of the formula 26 in Table A, wherein the ri of the compound, in each case corresponds to a compound of the formula 27 in the form of a formula A, wherein the compound Rl, the combination corresponds in each case to a compound of the formula 28 in the formula A, wherein the ri of the compound is combined In this case, it corresponds to one of columns 147475.doc, R2, Li, L2, L3, and L4 A in Table A, and R4 is one of columns R2, 1/, L2, L3, and L4 A, and R4 is R2, R2. /, L2 'L3 and L4 A, and R4 is R2, L!, L2, and L4, and R4 is a fluorenylcarbonyl group R2, 1/, L2, L3, and L4, and R4 is an ethylcarbonyl group R2 And L1, L2, L3 and L4 and R4 are propylcarbonyl R2, L1, L2, L3 and L4 and R is isopropyl tracing-38-201043139 Table 29 Formula Ι·1 compound, wherein compound R1, R2, Ll, ρρ and combinations thereof correspond in each case to one of the columns of Table A and R4 is a compound of the formula 1.1, wherein the combination of the compounds R1, R2, L1, L2, L3 and L4 In each case corresponds to one of the columns of Table A, and R4 is an ethoxycarbonyl table 31 Ο

式1.1化合物,其中化合物之尺1、R2、Ll、匕2、[3及[4之 組合在各情況下對應於表A之一列,且R4為丙氧羰基 表32 ^ 式1.1化合物,其中化合物之仗1、R2、Ll、L2、[3及[4之 組合在各情況下對應於表A之一列,且R4為異丙氧羰基 表33 式Ι·1化合物,其中化合物之、r2、Li、l2、&quot;及“之 組合在各情況下對應於表A之一列,且Μ為苯氧羰基 表34 式化合物,其中化合物之尺1、R2、Ll、L2、&quot;及“之 組σ在各情況下對應於表A之一列,且R4為甲基胺基羰基 表35 式U化合物,其中化合物之R1、R2、L1、L2、L3及L4之 組口在各情況下對應於表A之一列,且R4為乙基胺基羰基 表36 式1.1化合物’其中化合物之R1、R2、L1、L2、L3及L4之 、〇在各情況下對應於表A之一列,且R4為丙基胺基羰基 147475.doc -39- 201043139 表37 式1.1化合物,其中化合物之R丨、R2、L1、L2、L3及L4之組 合在各情況下對應於表A之一列,且R4為異丙基胺基羰基 表38 式1.1化合物,其中化合物之Rl、r2、Ll、、&quot;及以之 組合在各情況下對應於表A之一列,且R4為苯基胺基羰基 表39 式1.1化合物’其中化合物之Rl、r2、Ll、L2、^及^之 組合在各情況下對應於表A之一列,且R4為甲磺醯基 表40 式L1化合物,其中化合物之R1、R2、L1 ' L2、L3及L4之 組合在各情況下對應於表A之一列,且R4為乙磺醯基 表41 式Ι·1化合物’其中化合物之Rl、r2、L1、L2、L3&amp;L4之 組合在各情況下對應於表A之一列,且r4為丙磺醯基 表42 式L1化合物,其中化合物之R1、R2、L1、P、L3及L4之 組合在各情況下對應於表A之一列,且R4為異丙磺醯基 表43 式U化合物,其中化合物之R1、R2、L1、L2、L3及L4之 組合在各情況下對應於表A之一列,且r4為苯磺醯基 表44 式U化合物,其中化合物之R1、R2、L]、L2、ρ及。之 在各It况下對應於表八之_列,且尺4為曱氧基磺醯基 147475.doc -40- 201043139 表45 R2 ' L1 ^ T 2 T 3 Λ L、L3及L4之 1且R4為乙氧基磺醯基 R2、Ll、L2、L3及L4之 且R為丙氧基磺醯基 式1.1化合物,其中化合物之Ri 組合在各情況下對應於表A之一列 表46 式1.1化合物,其中化合物之Ri 組合在各情況下對應於表A之一列 表47 Οa compound of the formula 1.1 wherein the compound of the rule 1, R2, L1, 匕2, [3 and [4 combinations in each case corresponds to one of the tables A, and R4 is a propoxycarbonyl group 32^ a compound of the formula 1.1, wherein the compound Then, the combination of R1, R2, L1, L2, [3 and [4 corresponds in each case to one of the tables A, and R4 is a compound of the formula isopropoxycarbonyl group 33, wherein the compound, r2, Li , l2, &quot; and "the combination in each case corresponds to one of the tables A, and Μ is a phenoxycarbonyl group of the formula 34 compound, wherein the compound of the rule 1, R2, Ll, L2, &quot; and "group σ In each case corresponds to one of the columns of Table A, and R4 is a methylaminocarbonyl group 35 compound of the formula U, wherein the group of R1, R2, L1, L2, L3 and L4 of the compound corresponds in each case to Table A One of the columns, and R4 is ethylaminocarbonyl. Table 36 Compound of formula 1.1 ' wherein R1, R2, L1, L2, L3 and L4 of the compound, 〇 in each case corresponds to one of Table A, and R4 is propyl Aminocarbonyl 147475.doc -39- 201043139 Table 37 Compound of formula 1.1 wherein the combination of R丨, R2, L1, L2, L3 and L4 of the compound corresponds in each case to a column of Table A, and R4 is an isopropylaminocarbonyl group of the compound of formula 1.1 wherein R1, r2, L1, &quot; of the compound, and combinations thereof, in each case correspond to one of Table A, and R4 is Phenylaminocarbonyl Table 39 Compound of formula 1.1 wherein the combination of R1, r2, L1, L2, ^ and ^ of the compound corresponds in each case to one of Table A, and R4 is a methylsulfonyl group. Wherein the combination of R1, R2, L1 'L2, L3 and L4 of the compound corresponds in each case to one of the columns of Table A, and R4 is an ethylsulfonyl group, and the compound of the formula, wherein R1, r2, The combination of L1, L2, L3 &amp; L4 corresponds in each case to one of the columns of Table A, and r4 is a compound of the formula L1, wherein the combination of R1, R2, L1, P, L3 and L4 of the compound is In each case corresponds to one of the columns of Table A, and R4 is a compound of the formula U of the isopropylsulfonyl group, wherein the combination of the compounds R1, R2, L1, L2, L3 and L4 corresponds in each case to one of the tables A And r4 is a phenylsulfonyl group of the compound of the formula U, wherein the compound is R1, R2, L], L2, ρ and . In each case, it corresponds to the column of Table 8, and the rule 4 is methoxysulfonyl 147475.doc -40- 201043139 Table 45 R2 ' L1 ^ T 2 T 3 Λ L, L3 and L4 1 and R4 is ethoxysulfonyl R2, L1, L2, L3 and L4 and R is a propoxysulfonyl formula 1.1 compound wherein the Ri combination of the compounds corresponds in each case to one of the tables A. Compounds in which the Ri combination of compounds correspond in each case to list 47 of Table A Ο

式U化合物,其中化合物之R1、R2、L1、L2、L3及L4之組 合在各情況下對應於表八之一列,且R4為異丙氧基磺醯基、、且 表48 式Ι·1化合物,其中化合物之尺1、r2、L丨、l2、^及“之 組合在各情況下對應於表A之—列,且苯氧基確酿基 表49 式工.1化合物,其中化合物之R1、R2、L1、L2、L3及L4之 組合在各情況下對應於表A之一列,且R4為CN 表50至98 式L2化合物,其中化合物之R1、R2、L1、L2、L3及L4之 組合在各情況下對應於表八之一列且R4係如在表丨至钧中任 一者中所定義 表99至147 式1.3化合物’其中化合物之尺丨、r2、Ll、L2、L3及广之 組0在各情況下對應於表A之一列且R4係如在表1至49中任 一者中所定義 表148至196 147475.doc 201043139 式L4化合物,其中化合物之R1、R2、L1、Τ 2 τ 3 a τ L、L及L之 組合在各情況下對應於表Α之一列且R4係如在表1至钩中任 一者中所定義 表197至245 式1.5化合物,其中化合物之…、r2、Ll、l2、^及“之 組合在各情況下對應於表A之一列且尺4係如在表丨至的中任 一者中所定義 表246至294 式1.6化合物’其中化合物之R1、r2、乙1 2 3 l、L·及L·之 組合在各情況下對應於表A之一列且R 4係如在表1至钩中任 一者中所定義 表295至343 式1.7化合物’其肀化合物之Rl、r2、^1、T2 3 a τ 4 h L、L及L之 組合在各情況下對應於表a之一列且R 4係如在表!至4 9中任 一者中所定義 表344至392 式1.8化合物’其中化合物之Rl、r2丨 τ 3 α τ 4 ι L、L及L之 組合在各情況下對應於表A之一列且]^係如在表1至49中任 一者中所定義 表393 式1.9化合物’其中化合物之Rl、r2、Ll τ 3 β τ 4 ^ ι、L及L之 組合在各情況下對應於表Α之一列 表394 式1.10化合物,其中化合物之R1、R2、Ll、l2、^及匕4 147475.doc -42- 201043139 之組合在各情況下對應於表A之一列 表395 式Ι·11化合物,其中化合物之R1、R2、L1、L2、L3及L4 之組合在各情況下對應於表Α之一列 表396 ' 式1_12化合物,其中化合物之R1、R2、L1、L2、L3及L4 之組合在各情況下對應於表A之一列 表397 〇 式1.13化合物,其中化合物之R1、R2、L1、L2、L3及L4 之組合在各情況下對應於表A之一列 表398 式1.14化合物,其中化合物之111、112、1^1、1^、1^3及1/ 之組合在各情況下對應於表A之一列 表399 式1.15化合物,其中化合物之111、112、[1、1^2、乙3及1/ 0 之組合在各情況下對應於表A之一列 表400 式1.16化合物,其中化合物之111、112、1^1、12、1^3及1/ • 之組合在各情況下對應於表A之一列 表401 式II.1化合物,其中化合物之R1、R2、L1、L2、L3及L4 之組合在各情況下對應於表A之一列且1143為Η 表402 式ΙΙ.1化合物,其中化合物之R1、R2、L1、L2、L3及L4 147475.doc -43 201043139 之組。在各情況下對應於表A之一列且R4a為曱基 表403 式化1化合物’其中化合物之R1、R2、L1、L2 ' L3及L4 之組合在各情況下對應於表A之一列且為乙基 表404 式Π.1化合物,其中化合物之以、r2、Ll、l2、&quot;及以 之、,且a在各情況下對應於表A之一列且R4a為丙基 表405 式II.1化合物,其中化合物之…、r2、Ll、l2、。及^ 之組σ在各情況下對應於表a之一列且R4a為異丙基 表406 式Π.1化合物,其中化合物之Rl、r2、Ll、y、。及以 之組合在各情況下對應於表a之一列且Rh為正丁基 表407 式II.1化合物’其中化合物之尺1、r2、Ll、L2、L3及L4 之組合在各情況下對應於表A之一列且R 4 a為第二丁基 表408 式IL1化合物’其中化合物之R1、R2、L1、L2、L3及L4 之組合在各情況下對應於表A之一列且R4a為異丁基 表409 式II.1化合物,其中化合物之Rl、r2、L1、L2、[3及L4 之組合在各情況下對應於表A之一列且R4a為第三丁基 表41 〇 式II.1化合物,其中化合物之Rl、r2、、L2、L3及l4 147475.doc •44- 201043139 之組合在各情況下對應於表A之一列且R4a為苯基 表411 式II.1化合物’其中化合物之ri、r2、[I、l2、l3及L4 之組合在各情況下對應於表A之一列且R4a為4_甲基苯基 表412 式II.1化合物,其中化合物之ri、r2、、l2、l3及L·4 之組合在各情況下對應於表A之一列且R4a為甲基幾基 表413 ❹ 式II.1化合物,其中化合物之Rl、r2、、L2、L3及L4 之組合在各情況下對應於表A之一列且R4a為乙基羰基 表414 式II.1化合物’其中化合物之Rl、r2、L1、L2、。及L4 之組合在各情況下對應於表A之一列且R“為丙基羰基 表415 式IL1化合物’其中化合物之R1、R2、L1、L2、L3及L4 Q 之組合在各情況下對應於表A之一列且R4a為異丙基羰基 表416 式IL1化合物’其中化合物之R1、R2、L1、L2、L3及L4 - 之組合在各情況下對應於表A之一列且R4a為甲氧羰基 表417 式IL1化合物,其中化合物之R1、R2、L1、L2、L3及L4 之組合在各情況下對應於表A之一列且R4a為乙氧羰基 表418 、L1、L2、L3及 L4 式Π.1化合物,其中化合物之Ri、r2 147475.doc -45- 201043139 之組合在各情況下對應於表A之一列且R4a為丙氧羰基 表419 式IL1化合物’其中化合物之R1、R2、L1、L2、L3及L4 之組合在各情況下對應於表A之一列且R4a為異丙氧羰基 表420 式1化合物,其中化合物之R〗、R2、L1、L2、L3及L4 之組合在各情況下對應於表A之一列且R4a為苯氧羰基 表421 式IL1化合物’其中化合物之R1、R2、L1、L2、L3及L4 之組合在各情況下對應於表A之一列且R4a為甲基胺基羰基 表422 式Π.1化合物,其中化合物之R1、R2、L〗、L2、[3及L4 之組合在各情況下對應於表八之一列且R4a為乙基胺基羰基 表423 式II.1化合物,其中化合物之Rl、r2、Ll、L2、[3及[4 之組合在各情況下對應於表入之一列且R4a為丙基胺基羰基 表424 式IL1化合物’其中化合物之R1、R2、L1、L2、L3及L4之 組合在各情況下對應於表A之一列且R 4 a為異丙基胺基羰基 表425 式IL1化合物,其中化合物之Ri ' R2、l1、L2、L3及L·4 之組合在各情況下對應於表A之一列且R4a為苯基胺基羰基 表426 式IL1化合物,其中化合物之Ri、R2、L1、L2、L3及L·4 147475.doc •46· 201043139 之組合在各情況下對應於表A之一列且汉4 酿基 表427 式IL1化合物,其中化合物之R1、R2、L1、L2、L3及L4 之組合在各情況下對應於表故—列且R4a為 基 表 428 ' 式H·1化5物,其中化合物之R1、R2、L1、l2、L3及L4 之組合在各情況下對應於表A之一列且R4a為丙磺醯基 表439 〇 式Π·1化合物,其中化合物之以、r2、Ll、匕2、l3&amp;l4 之組合在各情況下對應於表A之一列且R4a為異丙績酿基 表430 式IL1化合物,其中化合物之R1、R2、L1、l2、L3及L4 之組合在各情況下對應於表A之一列且為苯磺醯基 表431 式II.1化合物,其中化合物之Ri、R2、匕1、[2、l3及l4 〇 之組合在各情況下對應於表A之一列且R4a為甲氧基磺醯基 表432 式Π· 1化合物’其中化合物之R1、r2、L1、l2、[3及L4 - 之組合在各情況下對應於表A之一列且尺“為乙氧基磺醯基 表433 式Π.1化合物,其中化合物之尺丨、R2、[I、[2、l3&amp;l4 之組合在各情況下對應於表A之一列且R4a為丙氧基磺醯基 表434 式II.1化合物’其中化合物之R1、r2、L1、L2、13及广之 147475.doc -47- 201043139 組合在各情況下對應於表A之一列且R 4 a為異丙氧基磺醯基 表435 式IL1化合物,其中化合物之R丨、R2、L1、L2、L3及L4 之組合在各情況下對應於表A之一列且反“為苯氧基磺醯基 表436 式IL1化合物’其中化合物之R1、R2、L1、L2、L3及L4 之組合在各情況下對應於表A之一列且R4a為CN 表437至472 式Π.2化合物,其中化合物之R1、R2、L1、L2、L3及L4 之組合在各情況下對應於表Α之一列且尺“係如在表401至 436中任一者中所定義 表473至508 式Π·3化合物’其中化合物之R1、R2、L1、L2、L3及L4 之組合在各情況下對應於表Α之一列且R4a係如在表401至 436中任一者中所定義 表509至544 式Π·4化合物,其中化合物之R1、R2、L丨、L2、L3及L4 之組合在各情況下對應於表Α之一列且R4a係如在表4〇1至 436中任一者中所定義 表545至580 式Π.5化合物,其中化合物之Ri、R2、L1、l2、l3及L4 之組合在各情況下對應於表A之一列且R4a係如在表4〇1至 436中任一者中所定義 表581至616 147475.doc • 48 · 201043139 式II.6化合物,其中化合物之R1、R2、L1、L2、L3及L4 之組合在各情況下對應於表A之一列且R4aS如在表401至 436中任一者中所定義 表617至652 式ΙΙ·7化合物,其中化合物之R1、R2、L1、L2、L3及L4 之組合在各情況下對應於表Α之一列且1143係如在表401至 436中任一者中所定義 表653至688A compound of the formula U wherein the combination of R1, R2, L1, L2, L3 and L4 of the compound corresponds in each case to one of the columns of Table 8, and R4 is isopropoxysulfonyl, and the formula 48 is Ι·1 The compound, wherein the combination of the ruler 1, r2, L, l2, ^ and "in the case corresponds to the column of Table A, and the phenoxy group is a compound of the formula. The combination of R1, R2, L1, L2, L3 and L4 corresponds in each case to one of the columns of Table A, and R4 is a compound of the formula L2, wherein the compounds are R1, R2, L1, L2, L3 and L4. The combination in each case corresponds to one of the columns of Table 8 and R4 is as defined in any of Tables 99 to 147, the compound of formula 1.3, wherein the compound is in the range of 丨, r2, L1, L2, L3 and The broad group 0 corresponds in each case to one of the columns of Table A and R4 is as defined in any of Tables 1 to 49, in the formula 148 to 196 147475.doc 201043139, the compound of the formula L4, wherein the compound R1, R2, L1 , Τ 2 τ 3 a τ L, L and L combinations in each case correspond to one of the columns and R4 is as defined in any of Tables 1 to H, Tables 197 to 245 a compound of 1.5, wherein the combination of the compound, r2, L1, l2, ^ and "in each case corresponds to one of the columns of Table A and the ruler 4 is as defined in any of Tables 246 to 294. The compound of formula 1.6 wherein the combination of R1, r2, B1 2 3 l, L· and L· of the compound corresponds in each case to one of the columns of Table A and R 4 is as in any of Tables 1 to H. The combination of R1, r2, ^1, T2 3 a τ 4 h L, L and L of the compound of formula 295 to 343 of formula 295 to 343 is defined in each case corresponding to one of the tables a and R 4 is as shown in the table. ! Tables 344 to 392 of formula 1.8 as defined in any one of 4' wherein the combination of R1, r2丨τ 3 α τ 4 ι L, L and L of the compound corresponds in each case to one of Table A and] ^ is a compound of formula 393, formula 1.9 as defined in any of Tables 1 to 49, wherein the combination of R1, r2, Ll τ 3 β τ 4 ^ ι, L and L of the compound corresponds in each case to the expression A list of compounds of formula 1.10, wherein the combination of compounds R1, R2, L1, l2, ^, and 匕4 147475.doc-42-201043139 corresponds in each case to one of Table A, List 395, Formula Ι11 compounds, Wherein the combination of R1, R2, L1, L2, L3 and L4 of the compound corresponds in each case to the list 396 ' of the formula 1-12 compound, wherein the combination of R1, R2, L1, L2, L3 and L4 of the compound is In each case corresponds to a list 397 of the formula A, a compound of formula 1.13, wherein the combination of R1, R2, L1, L2, L3 and L4 of the compound corresponds in each case to the compound of the formula 144, formula 1.14, wherein the compound The combination of 111, 112, 1^1, 1^, 1^3, and 1 in each case corresponds to one of the tables A, 399, and the formula 1.15. Wherein the combination of 111, 112, [1, 1^2, B3, and 1/0 of the compound corresponds in each case to the compound of formula 1.16 of Table A, wherein 111, 112, 1^1 of the compound The combination of 12, 1^3 and 1/• corresponds in each case to the compound of formula ll. II.1 of Table A, wherein the combination of R1, R2, L1, L2, L3 and L4 of the compound corresponds in each case. Listed in one of Table A and 1143 is a group of the formula .1, wherein the compound is R1, R2, L1, L2, L3 and L4 147475.doc-43 201043139. In each case corresponds to one of the columns of Table A and R4a is a thiol table 403 Formula 1 compound wherein the combination of R1, R2, L1, L2' L3 and L4 of the compound corresponds in each case to one of the columns of Table A and is Ethyl table 404 is a compound of the formula 1.1, wherein the compound is, r2, L1, l2, &quot; and, and a in each case corresponds to one of the columns of Table A and R4a is a propyl form 405 Formula II. A compound wherein the compound is ..., r2, L1, l2. The group σ of ^ and ^ corresponds in each case to one of the columns of Table a and R4a is an isopropyl group 406. The compound of the formula ,.1, wherein the compound is R1, r2, L1, y. And combinations thereof in each case correspond to one of the tables a and Rh is a n-butyl group 407. The compound of the formula II.1, wherein the combination of the ruler 1, r2, L1, L2, L3 and L4 of the compound corresponds in each case In a column of Table A and R 4 a is a second butyl group 408 compound of formula IL1 wherein the combination of R1, R2, L1, L2, L3 and L4 of the compound corresponds in each case to one of the columns of Table A and R4a is different. Butyl Table 409 Compound of formula II.1 wherein the combination of R1, r2, L1, L2, [3 and L4 of the compound corresponds in each case to one of Table A and R4a is a third butyl group. a compound wherein the combination of R1, r2, L2, L3 and 14 147475.doc • 44- 201043139 of the compound corresponds in each case to one of the columns of Table A and R 4a is a phenyl group 411. The compound of the formula II. The combination of ri, r2, [I, l2, l3 and L4 corresponds in each case to one of the columns of Table A and R4a is a 4-methylphenyl group 412 compound of the formula II.1, wherein the compound ri, r2, The combination of l2, l3 and L·4 corresponds in each case to one of the columns of Table A and R4a is a methyl group table 413 化合物 a compound of the formula II.1, wherein the compound R1, r2, L2 The combination of L3 and L4 correspond in each case to one row of Table A and R4a is ethylcarbonyl Table II.1 compound of Formula 414 'of the compound wherein Rl, r2, L1, L2 ,. The combination of L4 and L4 corresponds in each case to one of the columns of Table A and R "is a propylcarbonyl table 415 compound of formula IL1" wherein the combination of R1, R2, L1, L2, L3 and L4 Q of the compound corresponds in each case to Column A and R4a are isopropylcarbonyl Table 416 Formula IL1 compound 'wherein the combination of R1, R2, L1, L2, L3 and L4 - of the compound corresponds in each case to one of Table A and R4a is methoxycarbonyl Table 417 Compounds of the formula IL1 wherein the combination of R1, R2, L1, L2, L3 and L4 of the compound corresponds in each case to one of the columns of Table A and R4a is ethoxycarbonyl table 418, L1, L2, L3 and L4 The compound of the formula 1, wherein the combination of the compound Ri, r2 147475.doc -45- 201043139 corresponds in each case to one of the columns of Table A and R4a is a propoxycarbonyl group 419. The compound of the formula IL1 wherein R1, R2, L1 of the compound The combination of L2, L3 and L4 corresponds in each case to one of the columns of Table A and R4a is a compound of formula 1 of isopropoxycarbonyl table 420, wherein the combination of R, R2, L1, L2, L3 and L4 of the compound is in each case. The lower one corresponds to one of the columns of Table A and R4a is a phenoxycarbonyl group 421. The compound of the formula IL1, wherein the compound R1, R2 The combination of L1, L2, L3 and L4 corresponds in each case to one of the columns of Table A and R4a is a methylaminocarbonyl group 422 formula Π.1 compound wherein R1, R2, L, L2, [3 and The combination of L4 corresponds in each case to one of the columns of Table 8 and R4a is a compound of the formula II.1 of the ethylaminocarbonyl group, wherein the combination of the compounds R1, r2, L1, L2, [3 and [4 in each case) The lower one corresponds to one of the columns and R4a is a propylaminocarbonyl group 424. The compound of formula IL1' wherein the combination of R1, R2, L1, L2, L3 and L4 of the compound corresponds in each case to one of the columns of Table A and R 4 a is an isopropylaminocarbonyl group 425 compound of the formula IL1 wherein the combination of the compounds Ri' R2, l1, L2, L3 and L·4 corresponds in each case to one of the columns of Table A and R4a is a phenylaminocarbonyl group. Table 426 Compounds of the formula IL1, wherein the combination of the compounds Ri, R2, L1, L2, L3 and L·4 147475.doc • 46· 201043139 corresponds in each case to one of the tables A and the Han 4 base table 427 formula IL1 a compound wherein the combination of R1, R2, L1, L2, L3 and L4 of the compound corresponds in each case to the taberin-column and R4a is the base table 428 'H·1 5, wherein the combination of R1, R2, L1, L2, L3 and L4 of the compound corresponds in each case to one of the columns of Table A and R4a is a compound of the formula 439 〇 Π·1, wherein the compound The combination of r2, L1, 匕2, l3&amp;l4 corresponds in each case to one of the columns of Table A and R4a is a compound of the formula 430, wherein the compounds are R1, R2, L1, L2, L3 and L4. The combination in each case corresponds to one of the columns of Table A and is a compound of the formula 4-1, formula II.1, wherein the combination of the compound Ri, R2, 匕1, [2, l3 and l4 在 corresponds in each case Included in Table A and R4a is a methoxysulfonyl group 432 Formula Π 1 compound 'wherein the combination of R1, r2, L1, l2, [3 and L4 - of the compound corresponds in each case to one of Table A And the ruler "is a compound of the formula 433 Π.1, wherein the compound of the formula R, R2, [I, [2, l3 &amp; l4 combination in each case corresponds to one of the table A and R4a is Propoxy sulfonyl group 434 Formula II.1 compound 'wherein the compound R1, r2, L1, L2, 13 and 147475.doc -47- 201043139 combination in each case corresponds to And a combination of R丨, R2, L1, L2, L3 and L4 of the compound in each case corresponds to one of the tables A, and R 4 a is an isopropoxysulfonyl group 435 formula IL1 compound The reverse is "phenoxysulfonyl group 436 formula IL1 compound" wherein the combination of compounds R1, R2, L1, L2, L3 and L4 corresponds in each case to one of the columns of Table A and R4a is CN Tables 437 to 472 A compound of Π.2, wherein the combination of R1, R2, L1, L2, L3 and L4 of the compound corresponds in each case to one of the columns and the ruler "is as defined in any of Tables 401 to 436. The combination of R1, R2, L1, L2, L3 and L4 of the compound 508 is in each case corresponding to one of the columns and R4a is as defined in any of Tables 401 to 436. Table 509 to 544 Compounds of the formula ,4, wherein the combination of R1, R2, L丨, L2, L3 and L4 of the compound corresponds in each case to one of the columns and R4a is as in Tables 〇1 to 436. Tables 545 to 580 are defined as compounds of formula 545 to 580, wherein the combination of Ri, R2, L1, l2, l3 and L4 of the compound corresponds in each case to one of the columns of Table A and R4a Tables 581 to 616 147475.doc • 48 · 201043139 Compounds of the formula II.6, wherein the combination of R1, R2, L1, L2, L3 and L4 of the compound is in each of Tables 〇1 to 436 In the case of a column corresponding to Table A and R4aS, as defined in any of Tables 401 to 436, a compound of the formula 617 to 652, wherein a combination of R1, R2, L1, L2, L3 and L4 of the compound is Each case corresponds to one of the columns and 1143 is as defined in any of Tables 401 to 436, tables 653 to 688

式II.8化合物,其中化合物之R1、R2、L1、L2、L3及L4 之組合在各情況下對應於表A之一列且尺43係如在表401至 436中任一者中所定義 表AA compound of formula II.8 wherein the combination of R1, R2, L1, L2, L3 and L4 of the compound corresponds in each case to one of the columns of Table A and Rule 43 is as defined in any of Tables 401 to 436. A

編號 R1 R2 L1 L2 L3 L4 A-1. ch3 ch3 F H H H A-2. ch3 ch3 Br H H H A-3. ch3 ch3 ch3 H H H A-4. ch3 ch3 CH2CH3 H H H A-5. ch3 ch3 CH(CH3)2 H H H A-6. ch3 ch3 cf3 H H H A-7. ch3 ch3 CH2CF3 H H H A-8. ch3 ch3 CF2CHF2 H H H A-9. ch3 ch3 OCF3 H H H A-10. ch3 ch3 OCH2CF3 H H H A-11. ch3 ch3 och3 H H H A-12. ch3 ch3 OCH2CH3 H H H A-13. ch3 ch3 F Cl H H A-14. ch3 ch3 F H Cl H A-15. ch3 ch3 ch3 H Cl H A-16. ch3 ch3 CH2CH3 H Cl H A-17. ch3 ch3 CH(CH3)2 H Cl H A-18. ch3 ch3 cf3 H Cl H A-19. ch3 ch3 CH2CF3 H Cl H A-20. ch3 ch3 CF2CHF2 H Cl H A-21. ch3 ch3 OCF3 H Cl H A-22. ch3 ch3 OCH2CF3 H Cl H A-23. ch3 ch3 OCH3 H Cl H 147475.doc •49- 201043139No. R1 R2 L1 L2 L3 L4 A-1. ch3 ch3 FHHH A-2. ch3 ch3 Br HHH A-3. ch3 ch3 ch3 HHH A-4. ch3 ch3 CH2CH3 HHH A-5. ch3 ch3 CH(CH3)2 HHH A-6. ch3 ch3 cf3 HHH A-7. ch3 ch3 CH2CF3 HHH A-8. ch3 ch3 CF2CHF2 HHH A-9. ch3 ch3 OCF3 HHH A-10. ch3 ch3 OCH2CF3 HHH A-11. ch3 ch3 och3 HHH A- 12. ch3 ch3 OCH2CH3 HHH A-13. ch3 ch3 F Cl HH A-14. ch3 ch3 FH Cl H A-15. ch3 ch3 ch3 H Cl H A-16. ch3 ch3 CH2CH3 H Cl H A-17. ch3 ch3 CH(CH3)2 H Cl H A-18. ch3 ch3 cf3 H Cl H A-19. ch3 ch3 CH2CF3 H Cl H A-20. ch3 ch3 CF2CHF2 H Cl H A-21. ch3 ch3 OCF3 H Cl H A- 22. ch3 ch3 OCH2CF3 H Cl H A-23. ch3 ch3 OCH3 H Cl H 147475.doc •49- 201043139

編號 R1 R2 L1 L2 L3 L4 A-24. ch3 ch3 OCH2CH3 H Cl H A-25. ch3 ch3 ch3 Cl H H A-26. ch3 ch3 CH2CH3 Cl H H A-27. ch3 ch3 ch(ch3)2 Cl H H A-28. ch3 ch3 cf3 Cl H H A-29. ch3 ch3 ch2cf3 Cl H H A-30. ch3 ch3 cf2chf2 Cl H H A-31. ch3 ch3 ocf3 Cl H H A-32. ch3 ch3 OCH2CF3 Cl H H A-33. ch3 ch3 OCH3 Cl H H A-34. ch3 ch3 OCH2CH3 Cl H H A-35. H ch3 F H H H A-36. H ch3 Br H H H A-37. H ch3 ch3 H H H A-38. H ch3 ch2ch3 H H H A-39. H ch3 CH(CH3)2 H H H A-40. H ch3 cf3 H H H A-41. H ch3 CH2CF3 H H H A-42. H ch3 CF2CHF2 H H H A-43. H ch3 OCF3 H H H A-44. H ch3 OCH2CF3 H H H A-45. H ch3 0CH3 H H H A-46. H ch3 OCH2CH3 H H H A-47. H ch3 F Cl H H A-48. H ch3 F H Cl H A-49. H ch3 ch3 H Cl H A-50. H ch3 CH2CH3 H Cl H A-51. H ch3 CH(CH3)2 H Cl H A-52. H ch3 cf3 H Cl H A-53. H ch3 CH2CF3 H Cl H A-54. H ch3 CF2CHF2 H Cl H A-55. H ch3 OCF3 H Cl H A-56. H ch3 OCH2CF3 H Cl H A-57. H ch3 OCH3 H Cl H A-58. H ch3 OCH2CH3 H Cl H A-59. H ch3 ch3 Cl H H A-60. H ch3 CH2CH3 Cl H H A-61. H ch3 CH(CH3)2 Cl H H A-62. H ch3 cf3 Cl H H A-63. H ch3 CH2CF3 Cl H H A-64. H ch3 cf2chf2 Cl H H A-65. H ch3 ocf3 Cl H H A-66. H ch3 OCH2CF3 Cl H H A-67. H ch3 OCH3 Cl H H A-68. H ch3 OCH2CH3 Cl H H A-69. H H F H H H A-70. H H Br H H H A-71. H H ch3 H H H 147475.doc -50- 201043139No. R1 R2 L1 L2 L3 L4 A-24. ch3 ch3 OCH2CH3 H Cl H A-25. ch3 ch3 ch3 Cl HH A-26. ch3 ch3 CH2CH3 Cl HH A-27. ch3 ch3 ch(ch3)2 Cl HH A- 28. ch3 ch3 cf3 Cl HH A-29. ch3 ch3 ch2cf3 Cl HH A-30. ch3 ch3 cf2chf2 Cl HH A-31. ch3 ch3 ocf3 Cl HH A-32. ch3 ch3 OCH2CF3 Cl HH A-33. ch3 ch3 OCH3 Cl HH A-34. ch3 ch3 OCH2CH3 Cl HH A-35. H ch3 FHHH A-36. H ch3 Br HHH A-37. H ch3 ch3 HHH A-38. H ch3 ch2ch3 HHH A-39. H ch3 CH( CH3)2 HHH A-40. H ch3 cf3 HHH A-41. H ch3 CH2CF3 HHH A-42. H ch3 CF2CHF2 HHH A-43. H ch3 OCF3 HHH A-44. H ch3 OCH2CF3 HHH A-45. H ch3 0 CH3 HHH A-46. H ch3 OCH2CH3 HHH A-47. H ch3 F Cl HH A-48. H ch3 FH Cl H A-49. H ch3 ch3 H Cl H A-50. H ch3 CH2CH3 H Cl H A- H ch3 CH(CH3)2 H Cl H A-52. H ch3 cf3 H Cl H A-53. H ch3 CH2CF3 H Cl H A-54. H ch3 CF2CHF2 H Cl H A-55. H ch3 OCF3 H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H ch3 CH2CF3 Cl HH A-64. H ch3 cf2chf2 Cl HH A-65. H ch3 ocf3 Cl HH A- 66. H ch3 OCH2CF3 Cl HH A-67. H ch3 OCH3 Cl HH A-68. H ch3 OCH2CH3 Cl HH A-69. HHFHHH A-70. HH Br HHH A-71. HH ch3 HHH 147475.doc -50- 201043139

編號 R1 R2 L1 L2 L3 L4 A-72. H H CH2CH3 H H H A-73. H H ch(ch3)2 H H H A-74. H H cf3 H H H A-75. H H CH2CF3 H H H A-76. H H CF2CHF2 H H H A-77. H H OCF3 H H H A-78. H H OCH2CF3 H H H A-79. H H OCH3 H H H A-80. H H OCH2CH3 H H H A-81. H H F Cl H H A-82. H H F H Cl H A-83. H H ch3 H Cl H A-84. H H CH2CH3 H Cl H A-85. H H CH(CH3)2 H Cl H A-86. H H cf3 H Cl H A-87. H H CH2CF3 H Cl H A-88. H H CF2CHF2 H Cl H A-89. H H OCF3 H Cl H A-90. H H OCH2CF3 H Cl H A-91. H H OCH3 H Cl H A-92. H H OCH2CH3 H Cl H A-93. H H ch3 Cl H H A-94. H H CH2CH3 Cl H H A-95. H H ch(ch3)2 Cl H H A-96. H H cf3 Cl H H A-97. H H CH2CF3 Cl H H A-98. H H cf2chf2 Cl H H A-99. H H ocf3 Cl H H A-100. H H OCH2CF3 Cl H H A-101. H H OCH3 Cl H H A-102. H H OCH2CH3 Cl H H A-103. H cf3 F H H H A-104. H cf3 Br H H H A-105. H cf3 ch3 H H H A-106. H cf3 CH2CH3 H H H A-107. H cf3 ch(ch3)2 H H H A-108. H cf3 cf3 H H H A-109. H cf3 CH2CF3 H H H A-110. H cf3 cf2chf2 H H H A-lll. H cf3 ocf3 H H H A-112. H cf3 OCH2CF3 H H H A-113. H cf3 OCH3 H H H A-114. H cf3 OCH2CH3 H H H A-115. H cf3 F Cl H H A-116. H cf3 F H Cl H A-117. H cf3 ch3 H Cl H A-118. H cf3 CH2CH3 H Cl H A-119. H cf3 CH(CH3)2 H Cl H 147475.doc •51 . 201043139HR CH2CH3 HHH A-73. HH cf3 HHH A-74. HH CH2CF3 HH OCH3 HHH A-78. HH OCH3 HHH A-80. HH OCH2 HHH A-80. HH OCH2CH3 HHH A-81. HHF Cl HH A-82. HHFH Cl H A-83. HH ch3 H Cl H A-84 HH CH2CH3 H Cl H A-85. HH CH(CH3)2 H Cl H A-86. HH cf3 H Cl H A-87. HH CH2CF3 H Cl H A-88. HH CF2CHF2 H Cl H A-89. HH OCH3 HCH H A-91. HH OCH3 H Cl H A-92. HH OCH2CH3 H Cl H A-93. HH ch3 Cl HH A-94. HH CH2CH3 Cl HH A- HH cf3 Cl HH A-97. HH cf2chf2 Cl HH A-99. HH ocf3 Cl HH A-100. HH OCH2CF3 Cl HH H-OCH2Cl HH A-103. H cf3 FHHH A-104. H cf3 Br HHH A-105. H cf3 ch3 HHH A-106. H cf3 CH2CH3 HHH A-107 H cf3 ch(ch3)2 HHH A-108. H cf3 cf3 HHH A-109. H cf3 CH2CF3 HHH A-110. H cf3 cf2chf2 HHH A-lll. H cf3 ocf3 HHH H cf3 OCH3 HHH A-114. H cf3 OCH2CH3 HHH A-115. H cf3 F Cl HH A-116. H cf3 FH Cl H A-117. H cf3 ch3 H Cl H A-118. H cf3 CH2CH3 H Cl H A-119. H cf3 CH(CH3)2 H Cl H 147475.doc •51 . 201043139

編號 R1 R2 L1 L2 L3 L4 A-120. H cf3 cf3 H Cl H A-121. H cf3 ch2cf3 H Cl H A-122. H cf3 CF2CHF2 H Cl H A-123. H cf3 OCF3 H Cl H A-124. H cf3 OCH2CF3 H Cl H A-125. H cf3 0CH3 H Cl H A-126. H cf3 OCH2CH3 H Cl H A-127. H cf3 ch3 Cl H H A-128. H cf3 CH2CH3 Cl H H A-129. H cf3 ch(ch3)2 Cl H H A-130. H cf3 cf3 Cl H H A-131. H cf3 ch2cf3 Cl H H A-132. H cf3 CF2CHF2 Cl H H A-133. H cf3 OCF3 Cl H H A-134. H cf3 OCH2CF3 Cl H H A-135. H cf3 OCH3 Cl H H A-136. H cf3 OCH2CH3 Cl H H A-137. H CH2CH3 F H H H A-138. H CH2CH3 Br H H H A-139. H CH2CH3 ch3 H H H A-140. H CH2CH3 CH2CH3 H H H A-141. H CH2CH3 CH(CH3)2 H H H A-142. H CH2CH3 cf3 H H H A-143. H CH2CH3 CH2CF3 H H H A-144. H CH2CH3 CF2CHF2 H H H A-145. H CH2CH3 OCF3 H H H A-146. H CH2CH3 OCH2CF3 H H H A-147. H CH2CH3 och3 H H H A-148. H CH2CH3 OCH2CH3 H H H A-149. H CH2CH3 F Cl H H A-150. H ch2ch3 F H Cl H A-151. H CH2CH3 ch3 H Cl H A-152. H CH2CH3 CH2CH3 H Cl H A-153. H CH2CH3 ch(ch3)2 H Cl H A-154. H CH2CH3 cf3 H Cl H A-155. H CH2CH3 ch2cf3 H Cl H A-156. H CH2CH3 CF2CHF2 H Cl H A-157. H CH2CH3 OCF3 H Cl H A-158. H CH2CH3 OCH2CF3 H Cl H A-159. H CH2CH3 OCH3 H Cl H A-160. H CH2CH3 OCH2CH3 H Cl H A-161. H CH2CH3 ch3 Cl H H A-162. H CH2CH3 CH2CH3 Cl H H A-163. H CH2CH3 CH(CH3)2 Cl H H A-164. H CH2CH3 cf3 Cl H H A-165. H CH2CH3 CH2CF3 Cl H H A-166. H CH2CH3 cf2chf2 Cl H H A-167. H CH2CH3 ocf3 Cl H H 147475.doc -52- 201043139No. R1 R2 L1 L2 L3 L4 A-120. H cf3 cf3 H Cl H A-121. H cf3 ch2cf3 H Cl H A-122. H cf3 CF2CHF2 H Cl H A-123. H cf3 OCF3 H Cl H A-124 H cf3 OCH2CF3 H Cl H A-125. H cf3 0CH3 H Cl H A-126. H cf3 OCH2CH3 H Cl H A-127. H cf3 ch3 Cl HH A-128. H cf3 CH2CH3 Cl HH A-129. H Cf3 ch(ch3)2 Cl HH A-130. H cf3 cf3 Cl HH A-131. H cf3 ch2cf3 Cl HH A-132. H cf3 CF2CHF2 Cl HH A-133. H cf3 OCF3 Cl HH A-134. H cf3 H CH2CH3 Cl HH A-137. H CH2CH3 FHHH A-138. H CH2CH3 Br HHH A-139. H CH2CH3 ch3 HHH A-140. H CH2CH3 CH2CH3 HHH A-141. H CH2CH3 CH(CH3)2 HHH A-142. H CH2CH3 cf3 HHH A-143. H CH2CH3 CH2CF3 HHH A-144. H CH2CH3 CF2CHF2 HHH A-145. H CH2CH3 OCF3 HHH A-146. H CH2CH3 OCH2CF3 HHH A-147. H CH2CH3 och3 HHH A-148. H CH2CH3 OCH2CH3 HHH A-149. H CH2CH3 F Cl HH A-150. H ch2ch3 FH Cl H A-151. H CH2CH3 ch3 H Cl H A- 152. H CH2CH3 CH2CH3 H Cl H A-153. H CH2CH3 ch(ch3)2 H Cl H A-154. H CH2CH3 c H CH2CH3 CH2CHF2 H Cl H A-157. H CH2CH3 OCF3 H Cl H A-158. H CH2CH3 OCH2CF3 H Cl H A-159. H CH2CH3 OCH3 H Cl H A-160. H CH2CH3 OCH2CH3 H Cl H A-161. H CH2CH3 ch3 Cl HH A-162. H CH2CH3 CH2CH3 Cl HH A-163. H CH2CH3 CH(CH3)2 Cl HH A-164. HCH2CH3 CH2CF3 Cl HH A-166. H CH2CH3 cf2chf2 Cl HH A-167. H CH2CH3 ocf3 Cl HH 147475.doc -52- 201043139

編號 R1 R2 L1 L2 L3 L4 A-168. H CH2CH3 OCH2CF3 Cl H H A-169. H CH2CH3 OCH3 Cl H H A-170. H CH2CH3 OCH2CH3 Cl H H A-171. ch3 cf3 F H H H A-172. ch3 cf3 Br H H H A-173. ch3 cf3 ch3 H H H A-174. ch3 cf3 CH2CH3 H H H A-175. ch3 cf3 CH(CH3)2 H H H A-176. ch3 cf3 cf3 H H H A-177. ch3 cf3 CH2CF3 H H H A-178. ch3 cf3 CF2CHF2 H H H A-179. ch3 cf3 OCF3 H H H A-180. ch3 cf3 OCH2CF3 H H H A-181. ch3 cf3 OCH3 H H H A-182. ch3 cf3 OCH2CH3 H H H A-183. ch3 cf3 F Cl H H A-184. ch3 cf3 F H Cl H A-185. ch3 cf3 ch3 H Cl H A-186. ch3 cf3 CH2CH3 H Cl H A-187. ch3 cf3 CH(CH3)2 H Cl H A-188. ch3 cf3 cf3 H Cl H A-189. ch3 cf3 CH2CF3 H Cl H A-190. ch3 cf3 CF2CHF2 H Cl H A-191. ch3 cf3 OCF3 H Cl H A-192. ch3 cf3 OCH2CF3 H Cl H A-193. ch3 cf3 OCH3 H Cl H A-194. ch3 cf3 OCH2CH3 H Cl H A-195. ch3 cf3 ch3 Cl H H A-196. ch3 cf3 CH2CH3 Cl H H A-197. ch3 cf3 CH(CH3)2 Cl H H A-198. ch3 cf3 cf3 Cl H H A-199. ch3 cf3 CH2CF3 Cl H H A-200‘ ch3 cf3 CF2CHF2 Cl H H A-201. ch3 cf3 OCF3 Cl H H A-202. ch3 cf3 OCH2CF3 Cl H H A-203. ch3 cf3 OCH3 Cl H H A-204. ch3 cf3 OCH2CH3 Cl H H A-205. ch3 CH2CH3 F H H H A-206. ch3 CH2CH3 Br H H H A-207. ch3 CH2CH3 ch3 H H H A-208. ch3 ch2ch3 CH2CH3 H H H A-209. ch3 CH2CH3 CH(CH3)2 H H H A-210. ch3 CH2CH3 cf3 H H H A-211. ch3 ch2ch3 ch2cf3 H H H A-212. ch3 CH2CH3 CF2CHF2 H H H A-213. ch3 CH2CH3 OCF3 H H H A-214. ch3 CH2CH3 OCH2CF3 H H H A-215. ch3 CH2CH3 OCH3 H H H 147475.doc -53- 201043139No. R1 R2 L1 L2 L3 L4 A-168. H CH2CH3 OCH2CF3 Cl HH A-169. H CH2CH3 OCH3 Cl HH A-170. H CH2CH3 OCH2CH3 Cl HH A-171. ch3 cf3 FHHH A-172. ch3 cf3 Br HHH A -173. ch3 cf3 ch3 HHH A-174. ch3 cf3 CH2CH3 HHH A-175. ch3 cf3 CH(CH3)2 HHH A-176. ch3 cf3 cf3 HHH A-177. ch3 cf3 CH2CF3 HHH A-178. ch3 cf3 CF2CHF2 HHH A-179. ch3 cf3 OCF3 HHH A-180. ch3 cf3 OCH2CF3 HHH A-181. ch3 cf3 OCH3 HHH A-182. ch3 cf3 OCH2CH3 HHH A-183. ch3 cf3 F Cl HH A-184. ch3 cf3 FH Cl H A-185. ch3 cf3 ch3 H Cl H A-186. ch3 cf3 CH2CH3 H Cl H A-187. ch3 cf3 CH(CH3)2 H Cl H A-188. ch3 cf3 cf3 H Cl H A-189. ch3 Cf3 CH2CF3 H Cl H A-190. ch3 cf3 CF2CHF2 H Cl H A-191. ch3 cf3 OCF3 H Cl H A-192. ch3 cf3 OCH2CF3 H Cl H A-193. ch3 cf3 OCH3 H Cl H A-194. ch3 Cf3 OCH2CH3 H Cl H A-195. ch3 cf3 ch3 Cl HH A-196. ch3 cf3 CH2CH3 Cl HH A-197. ch3 cf3 CH(CH3)2 Cl HH A-198. ch3 cf3 cf3 Cl HH A-199. ch3 Cf3 CH2CF3 Cl HH A-200' ch3 cf3 CF2CHF2 Cl HH A-201. ch3 cf3 OCF3 Cl HH A-202. ch3 cf3 OCH2CF3 Cl HH A-203. ch3 cf3 OCH3 Cl HH A-204. ch3 cf3 OCH2CH3 Cl HH A-205. ch3 CH2CH3 FHHH A-206. ch3 CH2CH3 Br HHH A-207. ch3 CH2CH3 ch3 HHH A-208. ch3 ch2ch3 CH2CH3 HHH A-209. ch3 CH2CH3 CH(CH3)2 HHH A-210. ch3 CH2CH3 cf3 HHH A-211. ch3 ch2ch3 ch2cf3 HHH A-212. ch3 CH2CH3 CF2CHF2 HHH A-213. CH2CH3 OCF3 HHH A-214. ch3 CH2CH3 OCH2CF3 HHH A-215. ch3 CH2CH3 OCH3 HHH 147475.doc -53- 201043139

編號 R1 R2 L1 L2 L3 L4 A-216. ch3 CH2CH3 OCH2CH3 H H H A-217. ch3 CH2CH3 F Cl H H A-218. ch3 CH2CH3 F H Cl H A-219. ch3 CH2CH3 ch3 H Cl H A-220. ch3 CH2CH3 CH2CH3 H Cl H A-221. ch3 CH2CH3 CH(CH3)2 H Cl H A-222. ch3 CH2CH3 cf3 H Cl H A-223. ch3 CH2CH3 CH2CF3 H Cl H A-224. ch3 CH2CH3 CF2CHF2 H Cl H A-225. ch3 CH2CH3 OCF3 H Cl H A-226. ch3 CH2CH3 OCH2CF3 H Cl H A-227. ch3 CH2CH3 OCH3 H Cl H A-228. ch3 CH2CH3 OCH2CH3 H Cl H A-229. ch3 CH2CH3 ch3 Cl H H A-230. ch3 CH2CH3 CH2CH3 Cl H H A-231. ch3 CH2CH3 CH(CH3)2 Cl H H A-232. ch3 CH2CH3 cf3 Cl H H A-233. ch3 CH2CH3 ch2cf3 Cl H H A-234. ch3 CH2CH3 CF2CHF2 Cl H H A-235. ch3 CH2CH3 OCF3 Cl H H A-236. ch3 ch2ch3 OCH2CF3 Cl H H A-237. ch3 CH2CH3 OCH3 Cl H H A-238. ch3 CH2CH3 OCH2CH3 Cl H H A-239. cf3 cf3 F H H H A-240. cf3 cf3 Br H H H A-241. cf3 cf3 ch3 H H H A-242. cf3 cf3 CH2CH3 H H H A-243. cf3 cf3 ch(ch3)2 H H H A-244. cf3 cf3 cf3 H H H A-245. cf3 cf3 CH2CF3 H H H A-246. cf3 cf3 CF2CHF2 H H H A-247. cf3 cf3 OCF3 H H H A-248. cf3 cf3 OCH2CF3 H H H A-249. cf3 cf3 OCH3 H H H A-250. cf3 cf3 OCH2CH3 H H H A-251. cf3 cf3 F Cl H H A-252. cf3 cf3 F H Cl H A-253. cf3 cf3 ch3 H Cl H A-254. cf3 cf3 CH2CH3 H Cl H A-255. cf3 cf3 CH(CH3)2 H Cl H A-256. cf3 cf3 cf3 H Cl H A-257. cf3 cf3 CH2CF3 H Cl H A-258. cf3 cf3 CF2CHF2 H Cl H A-259. cf3 cf3 OCF3 H Cl H A-260. cf3 cf3 OCH2CF3 H Cl H A-261. cf3 cf3 OCH3 H Cl H A-262. cf3 cf3 OCH2CH3 H Cl H A-263. cf3 cf3 ch3 Cl H H 147475.doc -54- 201043139No. R1 R2 L1 L2 L3 L4 A-216. ch3 CH2CH3 OCH2CH3 HHH A-217. ch3 CH2CH3 F Cl HH A-218. ch3 CH2CH3 FH Cl H A-219. ch3 CH2CH3 ch3 H Cl H A-220. ch3 CH2CH3 CH2CH3 CH3CH2CH3 CH(CH3)2HClH A-222. ch3 CH2CH3 cf3 H Cl H A-223. ch3 CH2CH3 CH2CF3 H Cl H A-224. ch3 CH2CH3 CF2CHF2 H Cl H A-225 Ch3 CH2CH3 OCF3 H Cl H A-226. ch3 CH2CH3 OCH2CF3 H Cl H A-227. ch3 CH2CH3 OCH3 H Cl H A-228. ch3 CH2CH3 OCH2CH3 H Cl H A-229. ch3 CH2CH3 ch3 Cl HH A-230. Ch3 CH2CH3 CH2CH3 Cl HH A-231. ch3 CH2CH3 CH(CH3)2 Cl HH A-232. ch3 CH2CH3 cf3 Cl HH A-233. ch3 CH2CH3 ch2cf3 Cl HH A-234. ch3 CH2CH3 CF2CHF2 Cl HH A-235. CH2CH3 OCF3 Cl HH A-236. ch3 ch2ch3 OCH2CF3 Cl HH A-237. ch3 CH2CH3 OCH3 Cl HH A-238. ch3 CH2CH3 OCH2CH3 Cl HH A-239. cf3 cf3 FHHH A-240. cf3 cf3 Br HHH A-241. Cf3 cf3 ch3 HHH A-242. cf3 cf3 CH2CH3 HHH A-243. cf3 cf3 ch(ch3)2 HHH A-244. cf3 cf3 cf3 HHH A-245. cf3 cf3 CH2CF3 HHH A-246. cf3 cf3 CF2CHF2 HHH A- 247. cf3 cf3 OCF3 HHH A-248. cf3 cf3 OCH2CF3 HHH A-249. cf3 cf3 OCH3 HHH A-250. cf3 cf3 OCH2CH3 HHH A-251. cf3 cf3 F Cl HH A-252. cf3 cf3 FH Cl H A-253. cf3 cf3 Ch3 H Cl H A-254. cf3 cf3 CH2CH3 H Cl H A-255. cf3 cf3 CH(CH3)2 H Cl H A-256. cf3 cf3 cf3 H Cl H A-257. cf3 cf3 CH2CF3 H Cl H A- 258. cf3 cf3 CF2CHF2 H Cl H A-259. cf3 cf3 OCF3 H Cl H A-260. cf3 cf3 OCH2CF3 H Cl H A-261. cf3 cf3 OCH3 H Cl H A-262. cf3 cf3 OCH2CH3 H Cl H A- 263. cf3 cf3 ch3 Cl HH 147475.doc -54- 201043139

編號 R1 R2 L1 L2 L3 L4 A-264. cf3 cf3 CH2CH3 Cl H H A-265. cf3 cf3 CH(CH3)2 Cl H H A-266. cf3 cf3 cf3 Cl H H A-267. cf3 cf3 CH2CF3 Cl H H A-268. cf3 cf3 CF2CHF2 Cl H H A-269. cf3 cf3 OCF3 Cl H H A-270. cf3 cf3 OCH2CF3 Cl H H A-271. cf3 cf3 och3 Cl H H A-272. cf3 cf3 OCH2CH3 Cl H H A-273. cf3 CH2CH3 F H H H A-274. cf3 CH2CH3 Br H H H A-275. cf3 CH2CH3 ch3 H H H A-276. cf3 CH2CH3 CH2CH3 H H H A-277. cf3 CH2CH3 CH(CH3)2 H H H A-278. cf3 CH2CH3 cf3 H H H A-279. cf3 CH2CH3 ch2cf3 H H H A-280. cf3 CH2CH3 cf2chf2 H H H A-281. cf3 CH2CH3 ocf3 H H H A-282. cf3 CH2CH3 OCH2CF3 H H H A-283. cf3 CH2CH3 OCH3 H H H A-284. cf3 CH2CH3 OCH2CH3 H H H A-285. cf3 CH2CH3 F Cl H H A-286. cf3 CH2CH3 F H Cl H A-287. cf3 CH2CH3 ch3 H Cl H A-288. cf3 CH2CH3 CH2CH3 H Cl H A-289. cf3 ch2ch3 ch(ch3)2 H Cl H A-290. cf3 CH2CH3 cf3 H Cl H A-291. cf3 CH2CH3 CH2CF3 H Cl H A-292. cf3 ch2ch3 CF2CHF2 H Cl H A-293. cf3 CH2CH3 OCF3 H Cl H A-294. cf3 CH2CH3 OCH2CF3 H Cl H A-295. cf3 CH2CH3 OCH3 H Cl H A-296. cf3 CH2CH3 OCH2CH3 H Cl H A-297. cf3 CH2CH3 ch3 Cl H H A-298. cf3 CH2CH3 CH2CH3 Cl H H A-299. cf3 CH2CH3 CH(CH3)2 Cl H H A-300. cf3 CH2CH3 cf3 Cl H H A-301. cf3 CH2CH3 CH2CF3 Cl H H A-302. cf3 CH2CH3 cf2chf2 Cl H H A-303. cf3 CH2CH3 ocf3 Cl H H A-304. cf3 CH2CH3 OCH2CF3 Cl H H A-305. cf3 CH2CH3 OCH3 Cl H H A-306. cf3 CH2CH3 OCH2CH3 Cl H H A-307. CH2CH3 CH2CH3 F H H H A-308. CH2CH3 CH2CH3 Br H H H A-309. CH2CH3 CH2CH3 ch3 H H H A-310. CH2CH3 CH2CH3 CH2CH3 H H H A-311. CH2CH3 CH2CH3 ch(ch3)2 H H H 147475.doc -55- 201043139No. R1 R2 L1 L2 L3 L4 A-264. cf3 cf3 CH2CH3 Cl HH A-265. cf3 cf3 CH(CH3)2 Cl HH A-266. cf3 cf3 cf3 Cl HH A-267. cf3 cf3 CH2CF3 Cl HH A-268 Cf3 cf3 CF2CHF2 Cl HH A-269. cf3 cf3 OCF3 Cl HH A-270. cf3 cf3 OCH2CF3 Cl HH A-271. cf3 cf3 och3 Cl HH A-272. cf3 cf3 OCH2CH3 Cl HH A-273. cf3 CH2CH3 FHHH A - 274. cf3 CH2CH3 Br HHH A-275. cf3 CH2CH3 ch3 HHH A-276. cf3 CH2CH3 CH2CH3 HHH A-277. cf3 CH2CH3 CH(CH3)2 HHH A-278. cf3 CH2CH3 cf3 HHH A-279. cf3 CH2CH3 ch2cf3 HHH A-280. cf3 CH2CH3 cf2chf2 HHH A-281. cf3 CH2CH3 ocf3 HHH A-282. cf3 CH2CH3 OCH2CF3 HHH A-283. cf3 CH2CH3 OCH3 HHH A-284. cf3 CH2CH3 OCH2CH3 HHH A-285. cf3 CH2CH3 F Cl HH A-286. cf3 CH2CH3 FH Cl H A-287. cf3 CH2CH3 ch3 H Cl H A-288. cf3 CH2CH3 CH2CH3 H Cl H A-289. cf3 ch2ch3 ch(ch3)2 H Cl H A-290. cf3 CH2CH3 cf3 H Cl H A-291. cf3 CH2CH3 CH2CF3 H Cl H A-292. cf3 ch2ch3 CF2CHF2 H Cl H A-293. cf3 CH2CH3 OCF3 H Cl H A-294. cf3 CH2CH3 OCH2CF3 H Cl H A-295. cf3 CH2CH3 OC H3 H Cl H A-296. cf3 CH2CH3 OCH2CH3 H Cl H A-297. cf3 CH2CH3 ch3 Cl HH A-298. cf3 CH2CH3 CH2CH3 Cl HH A-299. cf3 CH2CH3 CH(CH3)2 Cl HH A-300. cf3 CH2CH3 cf3 Cl HH A-301. cf3 CH2CH3 CH2CF3 Cl HH A-302. cf3 CH2CH3 cf2chf2 Cl HH A-303. cf3 CH2CH3 ocf3 Cl HH A-304. cf3 CH2CH3 OCH2CF3 Cl HH A-305. cf3 CH2CH3 OCH3 Cl HH A -306. cf3 CH2CH3 OCH2CH3 Cl HH A-307. CH2CH3 CH2CH3 FHHH A-308. CH2CH3 CH2CH3 Br HHH A-309. CH2CH3 CH2CH3 ch3 HHH A-310. CH2CH3 CH2CH3 CH2CH3 HHH A-311. CH2CH3 CH2CH3 ch(ch3)2 HHH 147475.doc -55- 201043139

編號 R1 R2 L1 L2 L3 L4 Α-312. CH2CH3 CH2CH3 cf3 H H H Α-313. CH2CH3 CH2CH3 ch2cf3 H H H Α-314. CH2CH3 CH2CH3 CF2CHF2 H H H Α-315. CH2CH3 CH2CH3 OCF3 H H H Α-316. CH2CH3 CH2CH3 OCH2CF3 H H H Α-317. CH2CH3 CH2CH3 och3 H H H Α-318. CH2CH3 ch2ch3 OCH2CH3 H H H Α-319. CH2CH3 CH2CH3 F Cl H H Α-320. CH2CH3 CH2CH3 F H Cl H Α-321. CH2CH3 CH2CH3 ch3 H Cl H Α-322. CH2CH3 ch2ch3 CH2CH3 H Cl H Α-323. CH2CH3 CH2CH3 ch(ch3)2 H Cl H Α-324. CH2CH3 CH2CH3 cf3 H Cl H Α-325. CH2CH3 CH2CH3 CH2CF3 H Cl H Α-326. CH2CH3 CH2CH3 CF2CHF2 H Cl H Α-327. ch2ch3 CH2CH3 OCF3 H Cl H Α-328. CH2CH3 CH2CH3 OCH2CF3 H Cl H Α-329. ch2ch3 CH2CH3 OCH3 H Cl H Α-330. CH2CH3 CH2CH3 OCH2CH3 H Cl H Α-331. ch2ch3 CH2CH3 ch3 Cl H H Α-332. CH2CH3 CH2CH3 ch2ch3 Cl H H Α-333. CH2CH3 CH2CH3 CH(CH3)2 Cl H H Α-334. ch2ch3 CH2CH3 cf3 Cl H H Α-335. ch2ch3 CH2CH3 CH2CF3 Cl H H Α-336. CH2CH3 CH2CH3 CF2CHF2 Cl H H Α-337. ch2ch3 CH2CH3 OCF3 Cl H H Α-338. CH2CH3 CH2CH3 OCH2CF3 Cl H H Α-339. ch2ch3 CH2CH3 OCH3 Cl H H Α-340. CH2CH3 CH2CH3 OCH2CH3 Cl H H 式I及式II化合物可藉由一或多種如下文在流程1至13中 及在合成描述中所述之以下方法及變化形式來製備。變數 係如上文對於式I及式II所定義。 可如流程1中所概述藉由將相應三唑衍生物7硫化來製備 式IA化合物,其中R4為Η且η為0(=化合物IA’)(或化合物 11八,其中尺4&quot;為11)。硫化可與例如在\¥0 96/3 8423中所述 之已知方法類似地進行。舉例而言,可首先以強鹼(例如 有機鋰鹼,諸如正丁基鋰、第三丁基鋰或第二丁基鋰、二 異丙基胺化鋰,氫化鈉、胺化鈉或第三丁醇鉀與四甲基乙 147475.doc •56· 201043139 二唾基環去質子化,且接著使 硫一般係以粉末形式使用。該 鍵’例如乙醚、甲基第三丁基 一胺(TMEDA)之混合物)將 所得陰離子與元素硫反應。 反應一般在惰性溶劑(諸如 驗、四氫吱喃或H,二甲氧基乙烧、液氨、二甲亞颯 或二甲基甲醯胺)中進杆。;5 、, 反應/皿度亚不非常關鍵且可在 ΟNo. R1 R2 L1 L2 L3 L4 Α-312. CH2CH3 CH2CH3 cf3 HHH Α-313. CH2CH3 CH2CH3 ch2cf3 HHH Α-314. CH2CH3 CH2CH3 CF2CHF2 HHH Α-315. CH2CH3 CH2CH3 OCF3 HHH Α-316. CH2CH3 CH2CH3 OCH2CF3 HHH Α-317 CH2CH3 CH2CH3 och3 HHH Α-318. CH2CH3 ch2ch3 OCH2CH3 HHH Α-319. CH2CH3 CH2CH3 FCl HH Α-320. CH2CH3 CH2CH3 FH Cl H Α-321. CH2CH3 CH2CH3 ch3 H Cl H Α-322. CH2CH3 ch2ch3 CH2CH3 H Cl H Α-323. CH2CH3 CH2CH3 ch(ch3)2 H Cl H Α-324. CH2CH3 CH2CH3 cf3 H Cl H Α-325. CH2CH3 CH2CH3 CH2CF3 H Cl H Α-326. CH2CH3 CH2CH3 CF2CHF2 H Cl H Α-327. ch2ch3 CH2CH3 OCF3 H Cl H Α-328. CH2CH3 CH2CH3 OCH2CF3 H Cl H Α-329. ch2ch3 CH2CH3 OCH3 H Cl H Α-330. CH2CH3 CH2CH3 OCH2CH3 H Cl H Α-331. ch2ch3 CH2CH3 ch3 Cl HH Α-332. CH2CH3 CH2CH3 Ch2ch3 Cl HH Α-333. CH2CH3 CH2CH3 CH(CH3)2 Cl HH Α-334. ch2ch3 CH2CH3 cf3 Cl HH Α-335. ch2ch3 CH2CH3 CH2CF3 Cl HH Α-336. CH2CH3 CH2CH3 CF2CHF2 Cl HH Α-337. ch2ch3 CH2CH3 OCF3 Cl HH Α-338. CH2CH3 CH2CH3 OCH2CF3 Cl HH Α-33 9. ch2ch3 CH2CH3 OCH3 Cl HH Α-340. CH2CH3 CH2CH3 OCH2CH3 Cl HH The compounds of formula I and formula II can be obtained by one or more of the following methods and variations as described below in Schemes 1 to 13 and in the synthetic description. preparation. The variables are as defined above for Formula I and Formula II. The compound of formula IA can be prepared by vulcanizing the corresponding triazole derivative 7 as outlined in Scheme 1, wherein R4 is deuterium and η is 0 (=compound IA') (or compound 11 VIII, where ft 4&quot; is 11) . Vulcanization can be carried out similarly to the known methods described, for example, in \¥0 96/3 8423. For example, a strong base (for example, an organic lithium base such as n-butyllithium, a third butyllithium or a second butyllithium, a lithium diisopropylamide, a sodium hydride, a sodium azide or a third may be used first. Potassium butoxide and tetramethylethyl 147475.doc • 56· 201043139 The di-sial ring is deprotonated, and then the sulfur is generally used in powder form. The bond 'eg diethyl ether, methyl tert-butyl monoamine (TMEDA) The mixture of the resulting anion is reacted with elemental sulfur. The reaction is generally carried out in an inert solvent such as tetrahydrofuran or H, dimethoxyethane, liquid ammonia, dimethylhydrazine or dimethylformamide. ;5,, reaction / dish is not very critical and can be found in Ο

例如-7代至+50。(:,較佳鐵至代之範圍内。或者,可 在無驗存在下藉由在加熱之同時使7與元素硫在高濟點溶 劑(諸如Ν-甲基料咬酮、二嚼烧或Ν,Ν-二甲基甲酿胺)中 反應來進行硫化。在反應完成後,例如藉由添加水或酸水 溶液,諸如無機酸(例如稀硫酸或鹽酸)、乙酸或氣化銨, 從而使所得混合物水解以得到化合物^。 可以類似於諸如ερ_α_0267778中所述之已知方法製備三 。坐化合物7。舉例而言,可使環氧乙烧化合物轉以又仆 1Η-三唑在鹼存在下反應,該鹼諸如鹼金屬氫化物(例如氫 化鈉、氫化鉀)、鹼金屬氫氧化物(例如氫氧化鈉、氫氧化 鉀)或鹼金屬碳酸鹽(例如碳酸鈉、碳酸鉀、碳酸鉋)。該反 應適合在溶劑中進行。適合溶劑為例如甲苯、Ν_甲基吡咯啶 酮、醚(例如乙醚、四氫呋喃)、乙腈或Ν,Ν-二甲基甲醯胺。 可以類似於諸如 EP-A_0267778, 〇rg. Syn 49, 78 (1968) 或J. Am· Chem. Soc. 1975,1353中所述之已知方法製備環 氧乙烷6。舉例而言,可使環戊酮5與亞烷基錡(sulf〇nium ylide)或亞院基氧錄(ox〇suif〇njum yHde)(諸如二甲基亞曱 基氧疏或一甲基亞甲基鎮)在溶劑中反應。或者,可以類 似於 Tetrahedron Lett. 23, 5283 (1982)或 EP-A-0655443 中所 147475.doc •57· 201043139 述之方法在環氧化反應中藉由5與三甲绩鹽(諸如淳化三甲 鍈、峨化三甲銃或硫酸曱基三甲錄)在金屬氧化物(諸如驗 金屬氧化物(例如氧化鈉、氧化鉀)' 驗土金屬氧化物(例如 氧化鎂、氧㈣、氧化⑹或氧化辞)及視情況驗(諸如驗金 屬氫化物(例如氫化納、氫化鉀)、鹼金屬氯氧化物(例如氯 氧化鈉、氫氧化鉀)、鹼金屬碳酸鹽(例如碳酸鈉、碳酸 鉀、碳酸鉋))存在下在包含有機溶劑(諸如甲苯、n_甲基吼 咯啶酮、醚(例如乙醚、四氫呋喃)、乙腈或n,n_二甲^甲 醯胺)之兩相固/液系統中反應來製備環氧乙烷6。或者,可 以類似於Tetrahedron 1985,1259中所述之方法藉由以三甲 銃鹽(諸如溴化三甲鏟、碘化三甲锍或硫酸甲基三甲錡)或 二曱基氧化銕(sulfoxonium)鹽(諸如溴化三甲基氧化錡、碘 化二甲基氧化銃或硫酸甲基三甲基氧化銃)及硫酸鉀/氧化 銘將S環氧化來製備環氧乙烷6。 可由環戊酮4酯水解及後續脫除羧基作用獲得環戊酮5。 醋水解可在標準條件下,諸如使用適合鹼(諸如鹼金屬氫 氧化物(例如氫氧化鈉、氫氧化鉀)或鹼金屬碳酸鹽(例如碳 酸鈉、碳酸鉀、碳酸铯))在水中鹼水解進行。當所得酸在 驗(例如上述鹼之一;)存在下加熱時發生脫除羧基作用。 可自環戊酮3藉由使環戊酮3與化合物R2X(其中X為脫離 基’諸如鹵基(例如Cl、Br、I)、曱苯磺酸酯基或甲磺酸酯 基)在鹼存在下反應來製備環戊酮4。適合鹼為例如鹼金屬 烧醇鹽(例如甲醇鈉、甲醇鉀、甲醇鈉、乙醇鉀、第三丁 醇鉀)及鹼金屬氫化物(例如氫化鈉、氫化鉀)。該反應一般 147475.doc -58- 201043139 在溶劑(諸如醇(例如曱醇、乙醇)、醚(例如乙醚、四氫呋 喃)、N-曱基吡咯啶酮或n,N-二曱基甲醯胺)中進行。 可自環戊酮1藉由在鹼存在下以化合物2將其烷基化來製 備環戊酮3 ’其中γ為脫離基,諸如鹵基(例如Cl ' Br、I)、 曱苯績酸酯基或曱續酸酯基。適合驗為例如驗金屬烧醇鹽 (例如甲醇鈉、甲醇鉀、甲醇鈉、乙醇鉀、第三丁醇鉀)及 驗金屬氫化物(例如氫化納、氫化鉀)。該反應一般在溶劑 (諸如醇(例如甲醇、乙醇)、醚(例如乙謎、四氫D夫喃)、N_ 曱基π比咯啶酮、n,n-二曱基甲醯胺或二氣曱烷)中進行。 流程1For example, -7 generations to +50. (:, preferably in the range of iron to the next. Or, in the absence of the test, by heating 7 while the elemental sulfur is in a high-point solvent (such as Ν-methyl ketone, two chewing or Vulcanization is carried out by reaction in hydrazine, hydrazine-dimethyl dimethylamine. After completion of the reaction, for example, by adding water or an aqueous acid solution such as a mineral acid (for example, dilute sulfuric acid or hydrochloric acid), acetic acid or ammonium sulfate, The resulting mixture is hydrolyzed to give the compound. The compound III can be prepared analogously to the known methods such as those described in ερ_α_0267778. For example, the epoxy ethene compound can be converted to a servone 1 Η-triazole in the presence of a base. In reaction, the base is such as an alkali metal hydride (e.g., sodium hydride, potassium hydride), an alkali metal hydroxide (e.g., sodium hydroxide, potassium hydroxide) or an alkali metal carbonate (e.g., sodium carbonate, potassium carbonate, carbonic acid). The reaction is suitably carried out in a solvent. Suitable solvents are, for example, toluene, hydrazine-methylpyrrolidone, ethers (for example diethyl ether, tetrahydrofuran), acetonitrile or hydrazine, hydrazine-dimethylformamide. It can be similar to, for example, EP-A_0267778. , 〇rg. Sy Ethylene oxide 6 is prepared by a known method described in n 49, 78 (1968) or J. Am. Chem. Soc. 1975, 1353. For example, cyclopentanone 5 and alkylene sulfonium (sulfonate) can be obtained. 〇nium ylide) or ox〇suif〇njum yHde (such as dimethyl fluorenyloxy or monomethylmethylene) is reacted in a solvent. Alternatively, it can be similar to Tetrahedron Lett. 23, 5283 (1982) or EP-A-0655443, 147475.doc • 57· 201043139 The method described in the epoxidation reaction by 5 and trisodium salt (such as trimethyl sulfonium trimethoate, trimethyl hydrazine or barium sulphate) Base three) in metal oxides (such as metal oxides (such as sodium oxide, potassium oxide)' soil metal oxides (such as magnesium oxide, oxygen (four), oxidation (6) or oxidation) and depending on the case (such as metal Hydride (such as sodium hydride, potassium hydride), alkali metal oxychloride (such as sodium oxychloride, potassium hydroxide), alkali metal carbonate (such as sodium carbonate, potassium carbonate, carbonic acid planing) in the presence of organic solvents ( Such as toluene, n-methylpyrrolidone, ether (such as ether, tetrahydrofuran), B Or a two-phase solid/liquid system of n, n-dimethyl carbamide to react to produce ethylene oxide 6. Alternatively, it may be similar to the method described in Tetrahedron 1985, 1259 by trimethyl sulfonium salt ( Such as tribromide bromide, trimethylsulfonium iodide or methyltrimethylsulfate) or sulfoxonium salts (such as trimethylsulfoxonium bromide, dimethylphosphonium iodide or methyltrimethyl sulfate) The ruthenium oxyhydroxide) and the potassium sulphate/oxidized sulphur are epoxidized to prepare the oxirane 6. The cyclopentanone 5 can be obtained by hydrolysis of the cyclopentanone 4 ester and subsequent removal of the carboxyl group. The vinegar can be hydrolyzed under standard conditions, such as by using a suitable base such as an alkali metal hydroxide (such as sodium hydroxide, potassium hydroxide) or an alkali metal carbonate (such as sodium carbonate, potassium carbonate, cesium carbonate) in water. get on. Decarboxylation occurs when the resulting acid is heated in the presence of a test (e.g., one of the above bases;). From cyclopentanone 3 by reacting cyclopentanone 3 with compound R2X (wherein X is a cleavage group such as a halo group (e.g., Cl, Br, I), an anthracenyl sulfonate group or a mesylate group) The reaction is carried out to prepare cyclopentanone 4. Suitable bases are, for example, alkali metal alkoxides (e.g., sodium methoxide, potassium methoxide, sodium methoxide, potassium ethoxide, potassium t-butoxide) and alkali metal hydrides (e.g., sodium hydride, potassium hydride). The reaction is generally 147475.doc -58- 201043139 in a solvent (such as an alcohol (such as decyl alcohol, ethanol), an ether (such as diethyl ether, tetrahydrofuran), N-decylpyrrolidone or n,N-dimercaptocarboxamide) In progress. The cyclopentanone 3 can be prepared from cyclopentanone 1 by alkylating it with compound 2 in the presence of a base, wherein γ is a leaving group, such as a halogen group (e.g., Cl ' Br, I), a phthalic acid ester Base or a thiol group. Suitable for testing, for example, metal alkoxides (e.g., sodium methoxide, potassium methoxide, sodium methoxide, potassium ethoxide, potassium butoxide) and metal hydrides (e.g., sodium hydride, potassium hydride). The reaction is generally carried out in a solvent such as an alcohol (e.g., methanol, ethanol), an ether (e.g., sigma, tetrahydrofuran), N-decyl pi-pyridinone, n, n-dimercaptocaramine or a gas. In decane). Process 1

琉化Suihua

SHSH

可如下文流程2中所概述與j. 0rg. chem. 1983,48(7), 1125中所述之方法類似地製備化合物1 ^在鹼存在下在狄 克曼縮合(Dieckmann condensation)中使己二酸8環化為9。 適合鹼為例如鹼金屬烷醇鹽(例如甲酵鈉、甲醇鉀、甲醇 147475.doc -59· 201043139 Μ ' &amp; 醇鉀)。該縮合—般在適合溶劑⑽如 酵(例如甲醇、乙醇)、鱗(例如乙_、四氫咬詗心·甲基 吡咯呒酮)中進行。或者,在路易斯酸acid)(諸如氣 化鋁或三溴化硼)、過渡金屬鹽(諸如銀鹽、鐵鹽、銅鹽、 金鹽、姑鹽、始鹽(例如 Ag2〇、AgCi〇4、FeCi3、Nici2、Compound 1 can be prepared analogously to the method described in Scheme 2, J. 0rg. chem. 1983, 48(7), 1125, as described below in Scheme 2, in a Dieckmann condensation in the presence of a base. The diacid 8 is cyclized to 9. Suitable bases are, for example, alkali metal alkoxides (e.g., sodium methoxide, potassium methoxide, methanol 147475.doc - 59. 201043139 Μ ' &amp; potassium alkoxide). The condensation is generally carried out in a solvent (10) such as a leaven (e.g., methanol, ethanol) or a scale (e.g., B-, tetrahydrobine, methylpyrrolidone). Alternatively, in the Lewis acid acid (such as vaporized aluminum or boron tribromide), transition metal salts (such as silver salt, iron salt, copper salt, gold salt, gu salt, starting salt (such as Ag2 〇, AgCi 〇 4, FeCi3, Nici2

CuBr2、CuCl2、Cu(0Ae)2、CuS〇4、μ》及驗(尤其為有 機鋰鹼(例如一異丙胺鋰))存在下在適合溶劑(諸如醚(例如 乙緃W氫夫南)、甲苯、N_曱基吡咯啶酮或二氣甲烷)中 進行環化。接著使9與化合物Rlx(其中χ為脫離基,諸如函 基(例如Cl、Br、I)、甲苯磺酸酯基或甲磺酸酯基)在適合 鹼(諸如鹼金屬烷醇鹽(例如甲醇鈉、甲醇鉀、甲醇鈉、乙 特、第三丁醇鉀))存在下反應。院基化反應—般在適合 溶劑(諸如醇(例如甲醢、7辟、 ^ 乙醇)、喊(例如乙趟、四氫吱喃) 或N-甲基吡咯啶酮)中進行。 流程2CuBr2, CuCl2, Cu(0Ae)2, CuS〇4, μ" and in the presence of an organic lithium base (such as lithium isopropoxide) in a suitable solvent (such as ether (such as acetamidine W) Cyclization is carried out in toluene, N-decylpyrrolidone or di-methane. Subsequent to 9 and compound Rlx (wherein deuterium is a leaving group, such as a functional group (such as Cl, Br, I), tosylate or mesylate group) in a suitable base (such as an alkali metal alkoxide (such as methanol) The reaction is carried out in the presence of sodium, potassium methoxide, sodium methoxide, ethyl, potassium t-butoxide). The home-based reaction is generally carried out in a suitable solvent such as an alcohol (e.g., formazan, 7 amp, ^ ethanol), a shout (e.g., acetamidine, tetrahydrofuran) or N-methylpyrrolidone. Process 2

,〇R 5 c〇zR 驗 或金屬鹽w v_y — 9, 〇R 5 c〇zR test or metal salt w v_y — 9

R1X ΟR1X Ο

•co2r•co2r

中作為流程1中所述之方法的替代方案,亦1可如下文⑸ S :二使:/:10與苯甲_生物U在標準條件下在醇 二:反應。錢應一般在驗性條件 金屬虱氧化物(例如氫氧化納、氫氧 = (例如甲醇納、甲醇鉀、乙醇納、乙醇:屬:: 驗金屬氫化物(例如氫化納、 :醇钟) r ;在適合溶劑(諸如丨 J47475.doc •60· 201043139 (例如.甲醇、乙醇、第三丁醇)或醚(例如四氫呋喃))中進 行。例如使用鈀或鎳催化劑在標準氫化條件下還原醇醛縮 合物12得到5。 流程3As an alternative to the method described in Scheme 1, 1 can be as follows (5) S: two: /: 10 and benzene - bio-U under standard conditions in the alcohol two: reaction. The money should generally be in the test condition of metal ruthenium oxide (such as sodium hydroxide, hydrogen oxide = (such as methanol, potassium methoxide, ethanol, ethanol: genus:: metal hydride (such as sodium hydride, alcohol clock) r In a suitable solvent (such as 丨J47475.doc • 60· 201043139 (eg, methanol, ethanol, tert-butanol) or ether (such as tetrahydrofuran). For example, using palladium or nickel catalyst to reduce aldols under standard hydrogenation conditions Condensate 12 gives 5. Flow 3

可如下文流程4所概述與Tetrahedron 1998, 54 (28), 8075 中所述之方法類似地製備化合杨10。使4_氣丁醛與鹼金屬 氰化物MtN(諸如NaCN或KCN)反應以得到相應氰醇,其 接著經Ο保護以得到氰醇醚13。在鹼(尤其為有機鋰鹼(例 如二異丙胺鋰),或六曱基二矽氮烷鈉)存在下,在醚溶劑 (例如乙醚、四氫呋喃)中環化得到14,首先將其選擇性還 原為15,接著還原為16。脫除羥基之保護基得到17且進行 氧化擴環反應最終得到1 〇。 流程4Compound Yang 10 can be prepared analogously to the method described in Tetrahedron 1998, 54 (28), 8075, as outlined in Scheme 4 below. The 4-butyralaldehyde is reacted with an alkali metal cyanide MtN such as NaCN or KCN to give the corresponding cyanohydrin, which is then protected with hydrazine to give the cyanohydrin ether 13. Cyclization in an ether solvent (eg diethyl ether, tetrahydrofuran) in the presence of a base (especially an organolithium base (eg lithium diisopropylamide) or sodium hexyldiazoxide) affords 14 which is first selectively reduced to 15, then restored to 16. The protecting group for removing the hydroxyl group gives 17 and undergoes an oxidative ring expansion reaction to finally obtain 1 Torr. Process 4

147475.doc -61- 201043139 或者可如下文流程5中所概述與WO 95/09830中所述之方 法類似地製備R1為CH3之化合物1〇(=1〇,)。丁二烯衍生物 18與乙醯乙酸酯衍生物17(其中Ri為Cl_c6烷基或烷氧 基且尺為CrC6烷基)之催化C-C偶合得到雙鍵異構體19及 20。適合催化劑為铑與膦配位體之錯合物,其主要自以下 現場產生:鍺化合物,諸如Rh2〇3、RhCl3、RhBr3、147475.doc -61- 201043139 Alternatively, a compound 1 〇 (=1 〇,) wherein R1 is CH3 can be prepared analogously to the method described in Scheme 5, as described in WO 95/09830. Catalytic C-C coupling of butadiene derivative 18 with acetamidine acetate derivative 17 (wherein Ri is a Cl_c6 alkyl group or an alkoxy group and a CrC6 alkyl group) gives double bond isomers 19 and 20. Suitable catalysts are complexes of ruthenium and phosphine ligands, which are mainly produced from the following sites: ruthenium compounds such as Rh2〇3, RhCl3, RhBr3,

Rh2(S〇4)3、(Rh(CO)4)4、(Rh(CO)2Cl)2、Rh(CH3C02)3、Rh2(S〇4)3, (Rh(CO)4)4, (Rh(CO)2Cl)2, Rh(CH3C02)3,

Rh(N〇3)3或Rh(C8H】2Cl)2 ’及膦鹽,諸如三苯膦、(磺酸基 苯基)二苯膦、二(磺酸基苯基)苯膦或三(磺酸基苯基)膦之 納鹽、鉀鹽、鈣鹽、鋇鹽、銨鹽、四甲銨鹽或四乙銨鹽。 該反應一般在兩相水性/有機溶劑系統中進行。宜在鹼性 &quot;質中進行加成反應以有助於乙醯乙酸酯衍生物j 7之亞甲 基去質子化。適合鹼為例如水溶性無機鹼,諸如鹼金屬氫 氧化物(例如氫氧化鈉、氫氧化鉀)、碳酸鹽(例如碳酸鈉、 碳駄鉀、碳酸铯)或碳酸氫鹽(例如礙酸氫鈉、碳酸氫鉀、 石厌魷氫鉋),其係以水溶液形式使用。在r,為烷基之情況 下,使所彳于化合物19及20經受鹼性去醯化。適合鹼尤其為 鹼金屬醇化物’諸如於各別醇中之曱醇鈉、乙醇鈉或第三 丁醇鉀。去醯化化合物21及22接著水解為各別酸23及24。 水解-般在驗性介質中’使用例如與上文關於加成反應所 述^同之驗來進行。在R,為燒氧基之情況下,首先水解兩 固西曰基且接著將所得二酸脫除羧基以得到一元酸23及24更 有在存在強酸(例如鹽酸、氫漠酸、硝酸、硫酸)或強 (氫氧化納、氫氧化鉀)作為催化劑下,使用甲酸及水或 147475.doc •62· 201043139 氣態CO對23及24進行氫甲醯化,得到二酸25。在酸性條 件(諸如鹽酸、氫漠酸、硫酸、琐酸)下,在極性溶劑(諸如 甲醇、乙醇、異丙醇或第三丁醇)中將25環化最終得到環 戊酮10’。 流程5Rh(N〇3)3 or Rh(C8H]2Cl)2' and a phosphonium salt such as triphenylphosphine, (sulfonylphenyl)diphenylphosphine, bis(sulfophenyl)phenylphosphine or tris(sulfonate) A sodium salt, a potassium salt, a calcium salt, a phosphonium salt, an ammonium salt, a tetramethylammonium salt or a tetraethylammonium salt of an acid phenyl)phosphine. This reaction is generally carried out in a two-phase aqueous/organic solvent system. The addition reaction is preferably carried out in an alkaline &quot;quality to aid in the deprotonation of the methylene group of the acetamidine acetate derivative j7. Suitable bases are, for example, water-soluble inorganic bases such as alkali metal hydroxides (for example sodium hydroxide, potassium hydroxide), carbonates (for example sodium carbonate, potassium cesium carbonate, cesium carbonate) or hydrogencarbonates (for example sodium sulphate) , potassium bicarbonate, stone anaerobic hydrogen planing, which is used in the form of an aqueous solution. In the case where r is an alkyl group, the compounds 19 and 20 are subjected to alkaline deuteration. Suitable bases are especially alkali metal alkoxides such as sodium decoxide, sodium ethoxide or potassium t-butoxide in the respective alcohols. The deuterated compounds 21 and 22 are then hydrolyzed to the respective acids 23 and 24. The hydrolysis is generally carried out in an assay medium using, for example, the same as described above for the addition reaction. In the case where R is an alkoxy group, the two solid groups are first hydrolyzed and then the resulting diacid is removed to obtain a monobasic acid 23 and 24, more preferably in the presence of a strong acid (for example, hydrochloric acid, hydrogen desert acid, nitric acid, sulfuric acid). Or strong (sodium hydroxide, potassium hydroxide) as a catalyst, using formic acid and water or 147475.doc • 62· 201043139 gaseous CO to hydrogenate 23 and 24 to obtain diacid 25. Cyclization of 25 in a polar solvent such as methanol, ethanol, isopropanol or tert-butanol under acidic conditions such as hydrochloric acid, hydrochloric acid, sulfuric acid, tribasic acid affords the cyclopentanone 10'. Process 5

作為流程1中所述之方法的替代方案,可與Org. Syn. 40, 66, 1966 i J. Org. Chem. 28, 1 128, 1963及 Org. Syn. Coll. 第4卷,552, 1963中所述之方法類似地,如下文流程6中所 概述藉由首先對環戊酮5進行維蒂希反應(Wittig reaction),因此得到相應外亞曱基化合物41,且接著對其 進行環氧化反應來製備環氧乙烷6。維蒂希反應可在標準 條件下,諸如使用溴化曱基三苯鱗或碘化甲基三苯鱗,在 鹼金屬鹼(諸如正丁基鋰、第二丁基鋰或第三丁基鋰)存在 147475.doc -63 - 201043139 下進仃。亦可用諸如過氧乙酸'過苯曱酸、間氣過苯甲 酸、過鄰苯二曱酸及其類似物之標準試劑進行環氧化。$ 之烯化(亦即將C=〇轉化為C=CH2基團)或者可藉由使用特 伯試劑(Tebbe,s reagent)((C5H5)2TiCH2ClAl(CH3)2)來達 成。 流程6As an alternative to the method described in Scheme 1, it is possible with Org. Syn. 40, 66, 1966 i J. Org. Chem. 28, 1 128, 1963 and Org. Syn. Coll., Vol. 4, 552, 1963 The method described in the above is similarly, as outlined in Scheme 6 below, by first performing a Wittig reaction on cyclopentanone 5, thereby obtaining the corresponding outer mercapto compound 41, and then subjecting it to epoxidation. The reaction was carried out to prepare ethylene oxide 6. The Wittig reaction can be carried out under standard conditions, such as the use of sulfonium triphenyl sulphate or methyl iodide scales, in alkali metal bases (such as n-butyllithium, second butyllithium or tert-butyllithium) ) exists in 147475.doc -63 - 201043139. Epoxidation can also be carried out using standard reagents such as peroxyacetic acid 'perbenzoic acid, meta-perbenzoic acid, per-phthalic acid and the like. The alkylation of $ (i.e., conversion of C=〇 to a C=CH2 group) can be achieved by using a Tebbe, s reagent ((C5H5)2TiCH2ClAl(CH3)2). Process 6

稀化Thinning

環氧化Epoxidation

作為流程1中所述之方法的卷你古安 ,__ I K乃凌的朁代方案,亦可與下文流程 7 中所述之方法類似地製備化合物7。在使環戊酮12環氧化 (可如上文流程!中所述來進行)之後,可與流程i中關於㈣ 述之程序類似地使所得環氧化物26與[l,2,4l·lH三唑反 應。所得化合物27之還原可如上文關於流程3所述在鈀或 鎳催化劑存在下以標準氫化形式進行,或可藉由使用金屬 氫化物(例如硼氫化鈉、氫化鋰鋁)來進行以得到7。環戊酮 12可如上文流程3中所述來製備。 流程7As a method of the process described in Scheme 1, you can also prepare compound 7 similarly to the method described in Scheme 7 below. After epoxidizing cyclopentanone 12 (as described in Scheme above!), the resulting epoxide 26 can be similar to [l, 2, 4l·lH, similar to the procedure described in Scheme i for (d). Oxazole reaction. The reduction of the resulting compound 27 can be carried out in the form of a standard hydrogenation in the presence of a palladium or nickel catalyst as described above for Scheme 3, or can be carried out by using a metal hydride such as sodium borohydride or lithium aluminum hydride. Cyclopentanone 12 can be prepared as described in Scheme 3 above. Process 7

I47475.doc 64- 201043139 作為流程1中所述之方法的替找方垒 代方案’亦可如下文流程8 t,^«#EP-A-0357404 .EP-A-0576834^EP-A-0648751 中所述之方法類似地製備化合物7。以2(其中γ為脫離基, 诸如鹵基(例如Cl、Br、I)、甲笑并祕*匕甘上 } T本化酸酯基或甲磺酸酯基) Ο Ο 將28烷基化,在適合溶劑中以鹼使活化亞甲基去質子化之 後得到29。適合鹼為例如鹼金屬烷醇鹽(例如甲醇鈉、甲 醇卸、乙醇鈉、乙醇鉀、第三丁醇鉀)、驗金屬氫化物(例 如氫化鈉、氫化鉀)或鹼金屬碳酸鹽(例如碳酸鈉、碳酸 鉀、碳酸鉋)。適合溶劑為例如醇(例如甲醇、乙醇、第三 丁醇)、itG列如四氫呋喊)、N,N_二甲基甲醯胺或义甲基吡 咯啶酮。在酸(例如鹽酸、氫溴酸、硫酸 '對甲苯磺酸)存 在下’ S醇(諸如甲醇、乙醇、丙醇、異丙醇、丁醇或第 三丁醇,尤其為曱醇或乙醇)來轉化為相應烯醇醚3〇(其中 尺為心^4烷基,尤其為甲基或乙基),且例如用錯合金屬 氫化物(諸如硼氫化鈉或氫化鋰鋁)進行後續還原,得到環 己烯酮31。在酸(例如氫溴酸、乙酸)存在下以溴或碘進行 鹵化得到32,其中A及B為Br或I。接著用鹼金屬醇化物(諸 如甲醇納、乙醇鈉、甲醇卸或乙醇卸)在相應醇(亦即μ、 例如Na或K ; R,=例如曱基、乙基)中對其進行法沃斯基重 排(Favorskii rearrangement)以得到醋取代之環戊烯33。例 如用過氧乙酸、過苯曱酸、間氯過苯甲酸或過鄰苯二甲 酸,在標準條件下將環戊烯雙鍵環氧化得到34,例如使用 錯合金屬氫化物(諸如硼氫化鈉或氫化經鋁)將其還原為二 醇35。在將結合於亞甲基之羥基轉化為脫離基(諸如鹵基 147475.doc -65- 201043139 (例如Cl、Br、I)、甲苯罐酸酯基或曱績酸酯基)之後,與 流程1中所述之6之反應類似地使所得化合物36(D=脫離 基,例如鹵基(例如Cl、Br、I)、曱苯磺酸酯基或甲磧酸酯 基)與[1,2,4]-1Η-三唑反應以得到化合物7。 流程8I47475.doc 64- 201043139 The alternative method for the method described in the process 1 can also be as follows: Process 8 t, ^«#EP-A-0357404 .EP-A-0576834^EP-A-0648751 Compound 7 was prepared analogously to the method described. By 2 (wherein γ is a cleavage group, such as a halogen group (for example, Cl, Br, I), a serotonin, or a mesylate group) Ο 烷基 alkylation of 28 29 is obtained after deprotonation of the activated methylene group with a base in a suitable solvent. Suitable bases are, for example, alkali metal alkoxides (for example sodium methoxide, methanol unloading, sodium ethoxide, potassium ethoxide, potassium butoxide), metal hydrides (for example sodium hydride, potassium hydride) or alkali metal carbonates (for example carbonic acid) Sodium, potassium carbonate, carbonic acid planing). Suitable solvents are, for example, alcohols (e.g., methanol, ethanol, butanol), itG columns such as tetrahydrofuran, N,N-dimethylformamide or m-methylpyrrolidone. 'S alcohol (such as methanol, ethanol, propanol, isopropanol, butanol or tert-butanol, especially decyl alcohol or ethanol) in the presence of an acid such as hydrochloric acid, hydrobromic acid, sulfuric acid 'p-toluenesulfonic acid To convert to the corresponding enol ether 3〇 (wherein the square is a tetraalkyl group, especially a methyl or ethyl group), and for example, a subsequent metal reduction using a miscible metal hydride such as sodium borohydride or lithium aluminum hydride, Cyclohexenone 31 was obtained. Halogenation with bromine or iodine in the presence of an acid such as hydrobromic acid, acetic acid affords 32 wherein A and B are Br or I. Subsequent to an alkali metal alkoxide (such as sodium methoxide, sodium ethoxide, methanol or ethanol), the corresponding alcohol (ie, μ, such as Na or K; R, = for example, decyl, ethyl) Favorskii rearrangement to obtain cyclopentene 33 substituted with vinegar. For example, by peracetic acid, perbenzoic acid, m-chloroperbenzoic acid or perphthalic acid, the cyclopentene double bond is epoxidized under standard conditions to give 34, for example using a miscible metal hydride such as sodium borohydride. Or hydrogenation is reduced to diol 35 via aluminum). After converting a hydroxyl group bonded to a methylene group to a leaving group (such as a halogen group 147475.doc-65-201043139 (for example, Cl, Br, I), a toluene group or a phthalate group), and Scheme 1 The reaction of 6 described above similarly gives the resulting compound 36 (D = a cleavage group such as a halo group (e.g., Cl, Br, I), a tosylate group or a formate group) with [1, 2, 4]-1Η-triazole reaction to give compound 7. Process 8

作為流程1中所述之方法的替代方案,亦可與下文流程9 中所述之方法類似地製備化合物36。首先在水中之酸性條 件(例如鹽酸、氫溴酸、乙酸、硫酸或對甲笨磺酸)下將環 147475.doc -66- 201043139 氧化物6開環w π μ 衣乂付到35,接著如上文關於流程8所述將其轉 化為36 ’或藉由使用Cr、Br·或Γ之適合來源將6直接開環 得到36。 流程9As an alternative to the process described in Scheme 1, compound 36 can also be prepared analogously to the process described in Scheme 9 below. First, under the acidic conditions in water (such as hydrochloric acid, hydrobromic acid, acetic acid, sulfuric acid or p-toluenesulfonic acid), the ring 147475.doc -66-201043139 oxide 6 open-loop w π μ clothing is paid to 35, then as above It is converted to 36' as described in Scheme 8 or 6 is directly opened by using a suitable source of Cr, Br or hydrazine to give 36. Process 9

作為机程1中所述之方法的替代方案,亦可如下文流程 1 〇中所概述與wo 99/18088中所述之方法類似地製備化合 物1A ’其中R4為Hj*n為〇(或化合物ΠΑ,其中R4、h)。視 2况在酸(例如鹽酸、氫溴酸、乙酸、硫酸或對甲苯磺酸) 或鹼(例如_乙胺、二異丙基乙胺、碳酸鈉或碳酸鉀)存在 下,在適合溶劑(諸如醇(例如甲醇、乙醇、異丙醇、第三 丁醇)、N-甲基吡洛咬酮、醚(例如乙醚、四氫咬喃、二噁 烷、二甲氧基乙烷)、6猜、N,N_二甲基甲醯胺或二甲 ,硬)中用肼將6環氧化物開;裒,得到37。其接著藉由與硫 氰酸鹽(諸如硫氰酸鈉、硫氰酸鉀或硫氰酸銨(亦即例 如Na、K、NH/))在適合溶劑(諸如醇(例如甲醇、乙醇、 異丙醇、第三丁醇)、N_甲基吡咯啶酮、醚(例如乙醚、四 氫呋喃、二噁烷、i,2-二甲氧基乙烷)、乙腈、n,n•二甲基 甲醯胺、〕甲亞砜、甲苯或二甲苯)中反應來轉化為半卡 肼(SemiCarbaZide)38。半卡肼接著經由與甲酸烷醋(例如甲 酸甲酯、甲酸乙醋)在溶劑中反應轉化為IA,。適合溶劑為 147475.doc -67- 201043139 、第三丁醇)、Ν-曱基吡 '二噁烷、1,2-二曱氧基 、二甲亞颯、曱苯或二 例如醇(例如甲醇、乙醇、異丙醇、 各疋(例如乙醚、四氫°夫η南、 乙烧)、乙腈、Ν,Ν_二曱基曱醯胺 甲苯。或者,可使37與硫氰酸氫鹽及曱醛在溶劑中反應。 適合溶劑為例如醇(例如甲醇、乙醇、異丙醇、第三丁 醇)、Ν·甲基吡咯啶酮、醚(例如乙醚、四氫呋喃、二噁 烷I,2 一甲氧基乙烷)、乙腈、Ν,Ν-二甲基甲醯胺、二甲 亞砜甲苯或二甲苯。接著在鹼金屬氫氧化物(例如氫氧 化納氫氧化卸)及元素硫存在下使用例如含Feci3之酸水溶 液(例如鹽酸)或氧氣將所得三唑啶硫酮(triaz〇lidinthi〇ne)39 氧化為ΙΑ。在又一替代方案中,使37與二烷基酮(例如丙 _、二乙酮、甲基乙基酮)及硫氰酸鹽(例如硫氰酸鈉、硫 氰酸鉀、硫氰酸銨)在溶劑中反應得到三唑啶硫酮4〇。適 合溶劑為例如醇(例如甲醇、乙醇、異丙醇、第三丁醇)、 Ν-甲基吡咯啶酮、醚(例如乙醚、四氫呋喃、二噁烷、n 二曱氧基乙烷)、乙腈、Ν,Ν-二曱基甲醢胺、二曱亞砜、 甲苯或二甲苯。三唑啶硫酮4〇接著藉由在酸(例如鹽酸、 氫溴酸、乙酸、硫酸、對甲苯磺酸)或金屬氧化物(例如非 晶型Ti〇2)存在下與甲酸反應轉化為ΐΑ,。 147475.doc •68· 201043139 流程ίοAs an alternative to the method described in Scheme 1, compound 1A can also be prepared analogously to the method described in Scheme 1 与, as described in WO 99/18088, wherein R4 is Hj*n is 〇 (or compound) ΠΑ, where R4, h). In the presence of an acid (such as hydrochloric acid, hydrobromic acid, acetic acid, sulfuric acid or p-toluenesulfonic acid) or a base (such as _ethylamine, diisopropylethylamine, sodium carbonate or potassium carbonate) in a suitable solvent ( Such as alcohol (such as methanol, ethanol, isopropanol, tert-butanol), N-methylpyrrolidone, ether (such as ether, tetrahydroanion, dioxane, dimethoxyethane), 6 Guess, N, N-dimethylformamide or dimethyl, hard) with 6 epoxide with hydrazine; hydrazine, to give 37. It is then passed with a thiocyanate such as sodium thiocyanate, potassium thiocyanate or ammonium thiocyanate (ie, for example Na, K, NH/) in a suitable solvent (such as an alcohol (eg methanol, ethanol, iso) Propyl alcohol, tert-butanol), N-methylpyrrolidone, ether (eg diethyl ether, tetrahydrofuran, dioxane, i,2-dimethoxyethane), acetonitrile, n, n•dimethyl The reaction is carried out in decylamine, dimethylsulfoxide, toluene or xylene to convert to SemiCarbaZide 38. The semi-calendar is then converted to IA by reaction with alkane vinegar (e.g., methyl formate, ethyl formate) in a solvent. Suitable solvents are 147475.doc -67- 201043139, tert-butanol), fluorenyl-mercaptopyridine dioxane, 1,2-dimethoxy, dimethyl hydrazine, toluene or di-alcohol (eg methanol) , ethanol, isopropanol, each hydrazine (such as diethyl ether, tetrahydro sulphate, acetonitrile), acetonitrile, hydrazine, hydrazine hydrazine hydrazine toluene. Alternatively, 37 and thiocyanate can be used. Furfural is reacted in a solvent. Suitable solvents are, for example, alcohols (e.g., methanol, ethanol, isopropanol, tert-butanol), hydrazine methylpyrrolidone, ethers (e.g., diethyl ether, tetrahydrofuran, dioxane I, 2 Methoxyethane), acetonitrile, hydrazine, hydrazine-dimethylformamide, dimethyl sulfoxide toluene or xylene, followed by the presence of an alkali metal hydroxide (for example, sodium hydroxide hydroxide) and elemental sulfur The resulting triazulalidinthi〇ne 39 is oxidized to ruthenium using, for example, an aqueous solution of acid containing Feci3 (e.g., hydrochloric acid) or oxygen. In yet another alternative, 37 is made with a dialkyl ketone (e.g., propylene _) , diethyl ketone, methyl ethyl ketone) and thiocyanate (such as sodium thiocyanate, potassium thiocyanate, ammonium thiocyanate) in solvent The reaction gives triazolidine thione 4 〇. Suitable solvents are, for example, alcohols (such as methanol, ethanol, isopropanol, tert-butanol), Ν-methylpyrrolidone, ethers (such as diethyl ether, tetrahydrofuran, dioxane, n Dimethoxyethane), acetonitrile, hydrazine, hydrazine-dimercaptocarboxamide, disulfoxide, toluene or xylene. Triazolidine thione 4 〇 followed by acid (eg hydrochloric acid, hydrobromine The reaction with formic acid in the presence of acid, acetic acid, sulfuric acid, p-toluenesulfonic acid) or a metal oxide (for example, amorphous Ti〇2) is converted to hydrazine. 147475.doc •68· 201043139 Process ίο

Ο Ο 作為流程1中所述之方法的替 11中所概述與WO 99/1_中2方案’亦可如下文流程 物IA及IB,其中Μ為14且11為 I備4 、化〇物ΙΑ及ΙΒ,)(或化合物 ΙΙΑ及ΙΙΒ ’其中R“為Η)。視情況在酸(例如鹽酸、氫溴 酸、乙酸、硫酸或對甲苯磺酸)或鹼(例如三乙胺、二異丙 基乙胺、碳酸納或碳酸鉀)存在下’在適合溶劑(諸如醇(例 如甲醇、乙醇、異丙醇、第三丁醇)、Ν-甲基吡咯咬_、 鍵(例如乙謎、四氫咬喃、二°惡院、1,2-二甲氧基乙烧)、 乙腈、Ν,Ν-二甲基甲醯胺或二甲亞砜)中用肼將26環氧化 147475.doc -69- 201043139 物開j衣*到42。《接著冑由與硫氮酸鹽(諸如硫氛酸 鈉、硫氰酸鉀或硫氰酸鍵(亦即Μ+=例如Na+、Κ+、NIV)) 在適合溶劑(諸如醇(例如曱醇、乙醇、*丙醇、第三丁 醇)、沁甲基吡咯啶酮、醚(例如乙醚、目氫呋喃、二噁 烷I,2 —甲氧基乙烷)、乙腈、ν,Ν-二甲基甲醯胺、二甲 亞硬、甲苯或二甲笨)中反應來轉化為半卡肼43(;半卡骄 接著、..工由與甲酸烧g旨(例如甲酸甲醋、甲酸乙自旨)在溶劑中 反應轉化為IB,。適合溶劑為例如醇(例如甲醇、乙醇、異 丙醇、第二丁醇)、N_曱基吡咯啶酮、醚(例如乙醚、四氫 夫喃一噁烷、丨,2-二曱氧基乙烷)、乙腈、ν,ν-二曱基甲 醯月女、一甲亞砜、甲苯或二甲苯。或者’可使42與硫氰酸 氫鹽及曱醛在溶劑中反應。適合溶劑為例如醇(例如曱 醇、乙醇、異丙醇、第三丁醇)、Ν·甲基吡咯啶酮、醚(例 如乙醚、四氫呋喃、二噁烷、i,2_二甲氧基乙烷)、乙腈、 N,N-二曱基甲醯胺、二曱亞砜、甲苯或二甲苯。接著在鹼 金屬氫氧化物(例如氫氧化鈉、氫氧化鉀)及元素硫存在下 使用例如含FeCh之酸水溶液(例如鹽酸)或氧氣將所得三唑 0疋硫酮44氧化為IBf。在又一替代方案中,使42與二烧基 酮(例如丙酮、二乙酮、甲基乙基酮)及硫氰酸鹽(例如硫氰 酸鈉、硫氰酸鉀、硫氰酸銨)在溶劑中反應得到三唑啶硫 _ 45。適合溶劑為例如醇(例如曱醇、乙醇、異丙醇、第 三丁醇)、N-甲基吡咯啶酮、醚(例如乙醚、四氫呋喃、二 噁烷、1,2-二甲氧基乙烷)、乙腈、N,N_二曱基甲醯胺、二 甲亞砜、甲苯或二曱笨。三唑啶硫鲷45接著藉由在酸(例 147475.doc •70· 201043139 如鹽酸、氫溴酸、乙酸、硫酸、對甲苯磺酸)或金屬氧化 物(例如非晶型Ti〇2)存在下與甲酸反應轉化為IB,。IB,可 藉由使用鈀或鎳催化劑進行氫化或藉由用錯合金屬氫化物 (例如硼氫化鈉、氫化鋰鋁)進行還原轉化為IA,。 流程11Ο Ο as outlined in the method described in Scheme 1 and in the WO 99/1_2 scheme' can also be as follows IA and IB, where Μ is 14 and 11 is I 4 4, phlegm ΙΑ and ΙΒ,) (or compounds ΙΙΑ and ΙΙΒ 'where R' is Η). Depending on the acid (eg hydrochloric acid, hydrobromic acid, acetic acid, sulfuric acid or p-toluenesulfonic acid) or base (eg triethylamine, diiso) In the presence of propylethylamine, sodium carbonate or potassium carbonate) in a suitable solvent (such as alcohol (such as methanol, ethanol, isopropanol, tert-butanol), Ν-methylpyrrole biting, key (such as the puzzle, Oxidation of 26 with hydrazine in tetrahydroethylene, dioxin, 1,2-dimethoxyethane, acetonitrile, hydrazine, hydrazine-dimethylformamide or dimethyl sulfoxide) 147475.doc -69- 201043139 Open J coat * to 42. "Then with sulphate (such as sodium sulphate, potassium thiocyanate or thiocyanate bond (ie Μ + = for example Na+, Κ+, NIV )) in suitable solvents (such as alcohol (such as decyl alcohol, ethanol, * propanol, tert-butanol), hydrazine methyl pyrrolidone, ether (such as ether, hydrogen, methane, dioxane I, 2-methoxy) Base ethane), In a nitrile, ν, Ν-dimethylformamide, dimethyl sulfite, toluene or dimethyl strepamine, the reaction is converted into a semi-calendar 43 (a half-calorie followed by a work-and a formic acid) For example, formic acid methyl vinegar, formic acid B) is converted to IB by reaction in a solvent, and suitable solvents are, for example, alcohols (for example, methanol, ethanol, isopropanol, second butanol), N-decylpyrrolidone, ether ( For example, diethyl ether, tetrahydrofuran monooxane, hydrazine, 2-dimethoxy ethane), acetonitrile, ν, ν-dimercaptomethyl hydrazine, monomethyl sulfoxide, toluene or xylene. 42 is reacted with hydrogen thiocyanate and furfural in a solvent. Suitable solvents are, for example, alcohols (for example, decyl alcohol, ethanol, isopropanol, tert-butanol), hydrazine methylpyrrolidone, ethers (such as diethyl ether). , tetrahydrofuran, dioxane, i,2-dimethoxyethane), acetonitrile, N,N-dimercaptocarbamide, disulfoxide, toluene or xylene, followed by an alkali metal hydroxide ( Oxidation of the resulting triazole 0 thione 44 to IB using, for example, an aqueous solution of an acid containing FeCh (for example, hydrochloric acid) or oxygen in the presence of elemental sulfur, for example, sodium hydroxide or potassium hydroxide. f. In yet another alternative, 42 is combined with a dialkyl ketone (eg, acetone, diethyl ketone, methyl ethyl ketone) and a thiocyanate (eg, sodium thiocyanate, potassium thiocyanate, thiocyanate) Ammonium) is reacted in a solvent to give triazolidine sulfur _ 45. Suitable solvents are, for example, alcohols (e.g., decyl alcohol, ethanol, isopropanol, tert-butanol), N-methylpyrrolidone, ethers (e.g., diethyl ether, tetrahydrofuran). , dioxane, 1,2-dimethoxyethane), acetonitrile, N,N-dimercaptomethylamine, dimethyl sulfoxide, toluene or dioxane. Triazolidine thioindole 45 is then It is converted to IB by reaction with formic acid in the presence of an acid (for example, 147475.doc • 70·201043139 such as hydrochloric acid, hydrobromic acid, acetic acid, sulfuric acid, p-toluenesulfonic acid) or a metal oxide (for example, amorphous Ti〇2). IB can be converted to IA by hydrogenation using a palladium or nickel catalyst or by reduction with a mismatched metal hydride such as sodium borohydride or lithium aluminum hydride. Process 11

〇 作為流程11中所述之方法的替代方案,亦可如下文流程 12中所概述藉由與流程i中將7轉化為μ,所述之方法類似 地將化口物27硫化來製備化合物把,其中R4gH&amp;n為〇卜 化合物IB,)(或化合物Im,其中R4a為印。 147475.doc •71- 201043139 流程12As an alternative to the method described in Scheme 11, the compound can also be prepared by vulcanizing the hydration compound 27 similarly to that described in Scheme 12 below by converting 7 to μ in Scheme i. Wherein R4gH&amp;n is the indole compound IB,) (or compound Im, wherein R4a is imprinted. 147475.doc •71- 201043139 Scheme 12

可如流程7或下文流程13中所示,藉由首先在水中之酸 性條件(例如鹽酸、氫溴酸、乙酸、硫酸或對甲笨磺酸)下 將%氧化物26開環得到46,接著如上文關於流程8所述將 其轉化為47,或藉由使用cr、ΒΓ或Γ之適合來源將26直接 開環得47,來製備化合物27。接著使47與流程i中所述之6 之反應類似地與[1,2,4]-1H-三唑反應以得到27。 流程1 3The % oxide 26 can be opened 46 under the acidic conditions of water (eg, hydrochloric acid, hydrobromic acid, acetic acid, sulfuric acid, or p-toluenesulfonic acid) as shown in Scheme 7 or Scheme 13 below, followed by 46 Compound 27 was prepared by converting it to 47 as described above for Scheme 8, or by directly opening 26 to a suitable source using cr, hydrazine or hydrazine. Subsequent reaction of 47 with the reaction of 6 described in Scheme i was carried out similarly to [1,2,4]-1H-triazole to give 27. Process 1 3

上述反應中所用之苯甲基化合物2及經羰基取代苯化合 物11可購得或可藉由熟習此項技術者已知之標準方法來製 備。 式认及式m化合物(其中為氫且4〇)可自化合物^ 及IB’(其中R4=H且n=0)來製備。 147475.doc •72· 201043139 可與de-a_1952_w所述之方法類似地藉由使化合物 ia,wb.與化合物r4_lg(其中R4具有上述含義之—且^為 脫離基,諸如函基(例如Cl'Br])、甲苯石黃酸醋基或甲績 酸醋基)在鹼存在下反應來製備式IA及式IB化合物(其中n 為0且尺4為Cl_Cl〇院基、^10_烧基、C2_Ci〇稀基、C2_ c10齒烯基、c2_ClG炔基、C2_Cig_快基、C3_Cig環烷基、 環院基、苯基、苯基{a烧基,其中最後2個提 ❹ &amp;之基團中之苯基部分可如上所述經取A,及含有卜2或 3個選自心〇及8之雜原子作為環成員的5員或”飽和、 部分不飽和或芳族雜環,其中雜環可如上所述經取代)。 適合鹼為例如鹼金屬氫化物(例如氫化鈉、氫化鉀)、鹼金 屬氫氧化物(例如氫氧化鈉、氫氧化鉀)、鹼金屬碳酸鹽(例 如碳酸鈉、碳酸鉀、碳酸铯)、鹼金屬烷醇鹽(例如甲醇 納' 甲醇钟、乙醇鈉、乙醇卸、第三丁醇卸)或有機㈣ (例如正丁基鋰、第二丁基鋰、第三丁基鋰及二異丙胺 〇 鋰)。一般在適合溶劑中進行反應。適合溶劑為例如曱 苯、N-曱基吡咯啶酮、醚(例如乙醚、四氫呋喃、二噁 烷、1,2-一甲氧基乙烷)、乙腈、N,N_二甲基曱醯胺或二曱 亞碾。 可與DE-A-19617461中所述之方法類似地藉由使化合物 IA 或 IB 與化合物 r5_c(=〇)_w、R5-C(;=S)-W、R5,-lsi=C:=C) 或r5'-n=c=s(其中R5具有上述含義之一,R5.為Ci_Ci〇烷基 或匕-匚⑺鹵烷基且w為良好脫離基,諸如鹵基(例如C1、 Br、I)、烷氧化物(例如甲氧化物、乙氧化物)或五氟苯氧 147475.doc •73- 201043139 化修驗在了反應來製備式IA及式IB化合物(其中…且 R為-C(=〇)R或·C(=S)R5)。適合驗為例如驗金屬氫化物 (例如氫化鈉、氫化鉀)、鹼金屬氫氧化物(例如氫氧化鈉、 氫氧化鉀)、驗金屬碳酸鹽(例如碳酸鈉、碳酸卸、碳酸 鉋)、鹼金屬烷醇鹽(例如甲醇鈉、甲醇鉀、乙醇鈉、:醇 鉀、第三丁醇鉀)或有機鋰鹼(例如正丁基鋰、第二丁基 裡、第三丁基鐘、二里丙脸相、 . 八内胺鋰)。一般在適合溶劑中進行 反應。適合溶劑為例如甲苯、N•甲基料相、喊(例如 乙喊、四氫吱喃、二嗔烧、❻二甲氧基乙烧)、乙腈、 Ν,Ν-二甲基甲醯胺或二甲亞石風。 可與DE-A指20590中所逑之方法類似地藉由使化合物 ία,或m,與化合物r5_s〇2_w(其中r5具有上述含義之一且w 為良好脫離基’諸如函基(例如a、Br、…烷氧化物⑽ 如甲氧化物、乙氧化物)或五氟苯氧化物)在驗存在下反應 來製備式ΙΑ及式ΙΒ化合物(其中11為〇且114為_8〇#5)。適合 驗為例如驗金屬氫化物(例如氫化鈉、氫化鉀)、驗金屬^ 氧化物(例如氫氧化鈉、氫氡化_)、驗金屬碳酸鹽(例如碳 酸納、碳酸钟、碳酸鉋)、鹼金屬烷醇鹽(例如甲醇鈉、甲 醇鉀、乙醇鈉、乙醇鉀、笛二-pfM、);,, 弟一丁 S子鉀)或有機链驗(例如正 丁基锂、第二丁基鐘、第三丁基鐘、二異丙胺鐘)。—般 在適合溶劑中進行反應。適合溶劑為例如甲笨、N_甲基吡 咯啶酮、醚(例如乙醚、四氫呋喃、二噁烷 ' 丨,2_二甲氧基 乙烷)、乙腈、N,N-二甲基甲醯胺或二甲亞颯。 可與DE-A-19620407中所述之方法類似地藉由使化合物 147475.doc •74- 201043139 ΙΑ或IB’與化合物CN_W(其中w為良好脫離基,諸如鹵 基’例如Cl、Br、I)在鹼存在下反應來製備式IA及式圯化 σ物(其中η為0且R4為_CN)。適合鹼為例如鹼金屬氫化物 (例如氫化鈉、氫化鉀)、鹼金屬氫氧化物(例如氫氧化鈉、 氫氧化鉀)、驗金屬碳酸鹽(例如碳酸納、碳酸斜、碳酸 铯)、鹼金屬烷醇鹽(例如甲醇鈉、曱醇鉀、乙酵鈉、乙醇 鉀、第三丁醇鉀)或有機鋰鹼(例如正丁基鋰、第二丁基 ◎ 鋰第—丁基鋰、二異丙胺鋰)。一般在適合溶劑中進行 反應。適合洛劑為例如曱苯、N_甲基吡咯啶酮、醚(例如 乙轉、四氫吱喃、二。惡烧、i,2_二甲氧基乙烧)、乙猜、 N,N-二甲基曱醯胺或二甲亞颯。 可與DE-A-196 17282中所述之方法類似地藉由使化合物 IA’或IB'與胺NRaRbRc (其中Ra、r1^rC係如上所定義)或與 金屬鹽(諸如氫氧化鈉、氫氧化㈣乙酸銅)反應來製備式 IA及式IB化合物(其中n為〇且尺4為M)。 〇 ▼與W〇 97/43269中所述之方法類似地藉由使化合物IA, 或IB與鹵素(尤其為碘)在鹼存在下反應來製備式ia及式 化合物,其為為式m之基團。適合驗為例如驗金 屬氫化物(例如氫仙、氫化鉀)、驗金屬氫氧化物(例如氫 氧化鈉、氫氧化鉀)、鹼金屬碳酸鹽(例如碳酸鈉、碳酸 鉀、碳酸鉋)、鹼金屬烷醇鹽(例如甲醇鈉、甲醇鉀、乙醇 鈉、乙醇鉀、第三丁醇鉀)或有機鋰鹼(例如正丁基鋰、第 一丁基鋰、第二丁基鋰、二異丙胺鋰)。一般在適合溶劑 中進行反應。適合溶劑為例如甲苯、N_甲基吡咯啶酮、醚 147475.doc •75- 201043139 (例如乙驗、四氫^、二嚼燒叫^二甲氧基乙烧卜乙 腈、N,N-二甲基甲醯胺或二甲亞颯。 可’、WO今今心⑷中所述之方法類似地製備式认及式汨 化合物’其中n為 可與W〇 99/1議中所述之方法類似地藉由使三«硫 酮39或44與氧化劑視情況在催化劑存在下反應來製備式μ 及式1B化合物’其中R4為氫(或化合物IIA及ΠΒ,其中R4a 為氫)。適合氧化劑為例如氧氣、硫及超氧化鉀。尤其在 使用氧氣作為氧化劑之情況下,宜在催化劑存在下進行氧 化反應。適合催化劑為例如粉狀硫與k〇h之混合物。一般 在適合溶劑中進行反應。適合溶劑為例如脂族烴(例如戊 烷、己烷)、環脂族烴(例如環己烷)、芳族烴(例如苯、曱 苯、二曱苯)、醚(例如乙鱗、曱基第三丁基⑷及醋⑼如 乙酸乙酯、乙酸丙酯、乙酸正丁醋)。 亦可用含氯化鐵(FeCl3)之酸性水溶液與貿〇 〇ι/46ΐ58中 所述之方法類似地進行三唑啶硫酮39或44之氧化。一般在 適合溶劑中進行反應。適合溶劑為例如乙醇、乙酸乙酯及 乙酵與曱苯之混合物。 亦可與WO 99/18086或%〇 99/18〇88中所述之方法類似 地’視情況在催化劑存在下用甲酸進行三如定硫酮外或料 之氧化。適合催化劑為例如酸,如鹽酸、硫酸或對曱苯磺 酸;及金屬氧化物,如非晶型二氧化鈦。—般在適合溶: 中進行反應。適合溶劑為弱極性溶劑,如例如醇,諸如丙 醇、丁醇及戍醇;酯’如乙酸乙酯 乙酸丁酯及甲酸異丁 147475.doc -76- 201043139 酯;醚,如1,2-二甲氧基乙烷、曱基第三丁基醚及甲基第 三戊基醚;及過量使用之甲酸。 與上述將R4為Η之化合物IA'及IB,轉化為R4不為Η之化合 , 物類似’可藉由使NR4a基團(其中R4a為η)反應來製備式ΙΙΑ 及式IIB化合物(其中R4a不為氫)。 可藉由氧化自η為0之各別化合物製備η為1或2之化合物 I。或者,可自化合物7或27藉由首先將三唑基環去質子化 〇 且接著與磺醯氯r4S〇2C1反應來製備η為2之化合物I。11為3 之化合物I可自化合物7或27藉由首先將三唑基環去質子化 且接著與硫酸氯或式R4〇S〇2Cl之硫酸酯氣化物反應來製 備’其中R4係選自氫、d-Cio烧基、(:「(:!〇函烧基、c2-c10 烯基、c2-c1()齒稀基、C2_ClQ块基、c2_CiG鹵炔基、c3_Ci〇 環烷基、&lt;:3_(:10鹵環烷基、苯基、苯基_Ci_c4烷基,其中 最後2個提及之基團中之苯基部分可如上所述經取代,及 含有1、2或3個選自N、〇及8之雜原子的5員或6員飽和、 〇 部分不飽和或芳族雜環,其中該雜環可如上所述經取代。 若個別化合物不可經由上述途徑製備,則其可藉由其他 化合物I及II之衍生化或藉由所述合成途徑之慣用修改形式 -來製備。 .以償用方式,例如藉由與水混合、分離各相及適當時利 用層析(例如氧化鋁或矽膠層析)純化粗產物來處理反應混 合物。-些中間物及最終產物可以無色或淡褐色黏性油狀 物形式獲得’其可在減壓下及在適度高溫下自揮發性組分 釋放或純化。若中間物及最終產物係以固體形式獲得,則 147475.doc -77- 201043139 其可藉由再結晶或浸提來純化。 本發明之另一態樣係關於式iv化合物,The benzyl compound 2 and the carbonyl-substituted benzene compound 11 used in the above reaction are commercially available or can be prepared by standard methods known to those skilled in the art. Compounds of the formula m (wherein hydrogen and 4 Å) can be prepared from the compounds ^ and IB' (wherein R4 = H and n = 0). 147475.doc • 72· 201043139 can be similar to the method described in de-a_1952_w by making the compound ia, wb. and the compound r4_lg (wherein R4 has the above meaning - and ^ is a leaving group, such as a functional group (eg Cl' Br]), toluene oleic acid acetonate or acetoacetate) is prepared by reacting in the presence of a base to prepare a compound of the formula IA and the formula IB (wherein n is 0 and the rule 4 is a Cl_Cl 〇 院, ^10_alkyl, C2_Ci〇, C2_c10 dentyl, c2_ClG alkynyl, C2_Cig_ fast radical, C3_Cig cycloalkyl, ring-based, phenyl, phenyl {a alkyl, the last two of which are oxime &amp; The phenyl moiety may be taken as described above, and contains 5 or 3 hetero-atoms selected from the group consisting of ganglia and 8 as a member of the ring or a "saturated, partially unsaturated or aromatic heterocyclic ring, wherein The ring may be substituted as described above. Suitable bases are, for example, alkali metal hydrides (e.g., sodium hydride, potassium hydride), alkali metal hydroxides (e.g., sodium hydroxide, potassium hydroxide), alkali metal carbonates (e.g., sodium carbonate). , potassium carbonate, barium carbonate), alkali metal alkoxide (such as methanol sodium 'methanol clock, sodium ethoxide, ethanol unloading, third Butanol unloading) or organic (iv) (for example, n-butyllithium, dibutyllithium, tert-butyllithium, and lithium diisopropylamine). The reaction is generally carried out in a suitable solvent. Suitable solvents are, for example, toluene, N- Mercaptopyrrolidone, ether (eg diethyl ether, tetrahydrofuran, dioxane, 1,2-methoxyethane), acetonitrile, N,N-dimethylguanamine or diterpene. The method described in -A-19617461 is similarly by reacting compound IA or IB with compound r5_c(=〇)_w, R5-C(;=S)-W, R5, -lsi=C:=C) or r5 '-n=c=s (wherein R5 has one of the above meanings, R5. is Ci_Ci〇alkyl or 匕-匚(7)haloalkyl and w is a good leaving group such as a halo group (eg C1, Br, I), Alkoxides (eg, methoxide, ethoxylate) or pentafluorophenoxy 147475.doc • 73- 201043139 The modification proceeds to prepare compounds of formula IA and formula IB (wherein... and R is -C(=〇) R or · C (= S) R5). For example, it is suitable to test metal hydride (such as sodium hydride, potassium hydride), alkali metal hydroxide (such as sodium hydroxide, potassium hydroxide), metal carbonate ( Such as sodium carbonate, carbonic acid unloading, carbonic acid Planing), alkali metal alkoxide (such as sodium methoxide, potassium methoxide, sodium ethoxide, potassium alkoxide, potassium butoxide) or organic lithium base (such as n-butyl lithium, second butyl, tert-butyl) Clock, ri-propyl face, octa-amine lithium). Generally, the reaction is carried out in a suitable solvent. Suitable solvents are, for example, toluene, N-methyl phase, shouting (eg, yoke, tetrahydrofuran, bismuth) , ❻ dimethoxyethane), acetonitrile, hydrazine, hydrazine-dimethylformamide or dimethyl sulphite. It can be similar to the method described in DE-A No. 20590 by the compound ία, or m, and the compound r5_s〇2_w (wherein r5 has one of the above meanings and w is a good leaving group such as a functional group (for example, a, Br, ... alkoxide (10) such as methoxide, ethoxylate or pentafluorophenoxide) is reacted in the presence of a test to prepare a compound of the formula ΙΒ and ΙΒ (where 11 is 〇 and 114 is _8 〇 #5) . Suitable for testing, for example, metal hydrides (such as sodium hydride, potassium hydride), metal oxides (such as sodium hydroxide, hydroquinone), metal carbonates (such as sodium carbonate, carbonic acid, carbonic acid), Alkali metal alkoxide (such as sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, flute-pfM,);,,,,,,,,,,,,,,,,,,,,, Clock, third butyl clock, diisopropylamine clock). The reaction is carried out in a suitable solvent. Suitable solvents are, for example, methyl, N-methylpyrrolidone, ethers (e.g., diethyl ether, tetrahydrofuran, dioxane 'oxime, 2-dimethoxyethane), acetonitrile, N,N-dimethylformamide Or dimethyl hydrazine. It can be similar to the method described in DE-A-19620407 by compound 147475.doc •74- 201043139 ΙΑ or IB′ with compound CN_W (where w is a good leaving group such as a halogen group such as Cl, Br, I The reaction is carried out in the presence of a base to prepare a formula IA and a deuterated sigma (where n is 0 and R4 is _CN). Suitable bases are, for example, alkali metal hydrides (e.g., sodium hydride, potassium hydride), alkali metal hydroxides (e.g., sodium hydroxide, potassium hydroxide), metal carbonates (e.g., sodium carbonate, rhodium carbonate, cesium carbonate), bases. a metal alkoxide (such as sodium methoxide, potassium decoxide, sodium ethoxide, potassium ethoxide, potassium butoxide) or an organic lithium base (such as n-butyl lithium, second butyl ◎ lithium butyl lithium, two Lithium isopropylamine). The reaction is usually carried out in a suitable solvent. Suitable agents are, for example, toluene, N-methylpyrrolidone, ether (for example, ethylene, tetrahydrofuran, di., cautery, i,2-dimethoxyethane), B guess, N, N - dimethyl decylamine or dimethyl hydrazine. It can be similar to the method described in DE-A-196 17282 by reacting compound IA' or IB' with amine NRaRbRc (wherein Ra, r1^rC is as defined above) or with a metal salt (such as sodium hydroxide, hydrogen) Oxidation of (tetra) copper acetate) to prepare compounds of formula IA and formula IB (wherein n is oxime and rule 4 is M). 〇▼ is similar to the method described in W〇97/43269 by reacting compound IA, or IB with a halogen (especially iodine) in the presence of a base to prepare a compound of formula ia and formula, which is a group of formula m group. Suitable for testing, for example, metal hydrides (such as hydrogen hydride, potassium hydride), metal hydroxides (such as sodium hydroxide, potassium hydroxide), alkali metal carbonates (such as sodium carbonate, potassium carbonate, carbonic acid planing), alkali a metal alkoxide (such as sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, potassium butoxide) or an organic lithium base (such as n-butyl lithium, first butyl lithium, second butyl lithium, diisopropylamine) lithium). The reaction is usually carried out in a suitable solvent. Suitable solvents are, for example, toluene, N-methylpyrrolidone, ether 147475.doc • 75- 201043139 (eg, test, tetrahydrogen, two chews, ^dimethoxyethane, acetonitrile, N, N-di Methylformamide or dimethyl hydrazine. The method described in WO, present and present (4) similarly prepares the formula 汨 compound 'where n is a method which can be discussed with W〇99/1 Similarly, a compound of formula μ and formula 1B wherein R4 is hydrogen (or compound IIA and hydrazine wherein R4a is hydrogen) is prepared by reacting tris-thione 39 or 44 with an oxidizing agent, optionally in the presence of a catalyst. For example, oxygen, sulfur and potassium superoxide. Especially in the case of using oxygen as the oxidizing agent, it is preferred to carry out the oxidation reaction in the presence of a catalyst. Suitable catalysts are, for example, a mixture of powdered sulfur and k〇h. The reaction is generally carried out in a suitable solvent. Suitable solvents are, for example, aliphatic hydrocarbons (e.g., pentane, hexane), cycloaliphatic hydrocarbons (e.g., cyclohexane), aromatic hydrocarbons (e.g., benzene, toluene, diphenyl), ethers (e.g., hexascale, fluorenyl). Third butyl (4) and vinegar (9) such as ethyl acetate, propyl acetate, and n-butyl acetate Vinegar) Oxidation of triazopyridine ketone 39 or 44 can also be carried out analogously to the method described in 〇〇ι/46ΐ58 using an acidic aqueous solution containing ferric chloride (FeCl3). It is generally carried out in a suitable solvent. The solvent is, for example, ethanol, ethyl acetate and a mixture of ethyl acetate and toluene. It can also be similarly used in the presence of a catalyst in the presence of a catalyst similar to the method described in WO 99/18086 or % 99/18〇88. For example, the oxidation of the thione is suitable for the catalyst. For example, the catalyst is, for example, an acid such as hydrochloric acid, sulfuric acid or p-toluenesulfonic acid; and a metal oxide such as amorphous titanium dioxide is generally reacted in a suitable solvent: suitable solvent Is a weakly polar solvent such as, for example, an alcohol such as propanol, butanol and decyl alcohol; an ester such as ethyl butyl acetate and isobutyl 147475.doc -76- 201043139; an ether such as 1,2-dimethyl Oxyethane, decyl-tert-butyl ether and methyl-tert-butyl ether; and formic acid used in excess. In combination with the above-mentioned compounds IA' and IB in which R4 is hydrazine, it is converted into a compound in which R4 is not hydrazine. Similar to 'can be prepared by reacting an NR4a group (wherein R4a is η) And a compound of the formula IIB (wherein R4a is not hydrogen). The compound I having η of 1 or 2 can be prepared by oxidizing a respective compound having a η of 0. Alternatively, the triazolyl ring can be firstly obtained from the compound 7 or 27. Deprotonation of hydrazine and subsequent reaction with sulfonium chloride r4S〇2C1 to prepare compound I with η of 2. Compound I of 11 can be derived from compound 7 or 27 by first deprotonating the triazolyl ring and then with sulfuric acid. Chlorine or a sulfuric acid ester of the formula R4〇S〇2Cl is reacted to prepare 'where R4 is selected from hydrogen, d-Cio alkyl, (: "(:! 〇 烧, c2-c10 alkenyl, c2-c1) () a dilute base, a C2_ClQ block group, a c2_CiG haloalkynyl group, a c3_Ci〇cycloalkyl group, &lt;:3_(:10 halocycloalkyl, phenyl, phenyl-Ci_c4 alkyl, the last two of which are mentioned The phenyl moiety in the group may be substituted as described above, and a 5- or 6-membered saturated, fluorene-saturated or aromatic heterocyclic ring containing 1, 2 or 3 heteroatoms selected from N, fluorene and 8. Wherein the heterocyclic ring can be substituted as described above. If individual compounds are not prepared by the above routes, they may be prepared by derivatization of other compounds I and II or by conventional modifications of the synthetic route. The reaction mixture is treated, for example, by mixing with water, isolating the phases and, if appropriate, purifying the crude product by chromatography (e.g., alumina or silica gel chromatography). - Some intermediates and final products may be obtained in the form of a colorless or light brown viscous oil which can be released or purified from volatile components under reduced pressure and at moderately elevated temperatures. If the intermediate and final product are obtained in solid form, then 147475.doc-77-201043139 can be purified by recrystallization or leaching. Another aspect of the invention pertains to a compound of formula iv,

N-NN-N

L2 Η (IV) 其中 Rl、R2、R3、L1 2 3 L及[具有通用含義之一或 特定言之上文對於化合物給出之較佳含義之 如下化合物除外,其中 ’ CF3,且rrrr為雙鍵; “甲氧基或 R1 及 R2 均為 CH3,R3、l2、L3 及 l4a — 曱氧基或CF3,且rrrr為雙鍵; ’、、、虱,L!為氟、溴、 R1、R2、R3、L1、L\L4為氫,L 鍵。 ,-、CF3,且二T為單 較佳化合物IV為化合物】VA,L2 Η (IV) wherein R1, R2, R3, L1 2 3 L and [the following compounds having one of the general meanings or in particular the preferred meanings given above for the compound, wherein 'CF3, and rrrr are double Key; "methoxy or R1 and R2 are both CH3, R3, l2, L3 and l4a - decyloxy or CF3, and rrrr is a double bond; ',, 虱, L! is fluorine, bromine, R1, R2 , R3, L1, L\L4 are hydrogen, L bond, -, CF3, and the second T is a single preferred compound IV is a compound] VA,

(IVA) 147475.doc •78· 201043139 其中Rl、R2、R3、Ll、L·2、L3及L4具有通用含義之—或 特定言之上文對於化合物給出之較佳含義之—. 如下化合物除外,其中R〗、R2、R3、L!、L3&amp;L4為氫 L2為 CF3 化合物IV及IVA—方面為製備化合物1及11中之有價值中 間物(參看化合物7及27),但另一方面亦顯示顯著殺真菌活 性。 ❹ 2尤其較佳化合物以為式1¥1至1¥8化合物,其中y、 R、L、L、L3及L4之組合在各情況下對應於上文表a中 之一列。 〇(IVA) 147475.doc •78· 201043139 where R1, R2, R3, L1, L·2, L3 and L4 have the general meaning — or specifically the preferred meaning given above for the compound —. Except where R, R2, R3, L!, L3 &amp; L4 are hydrogen L2 is CF3 Compound IV and IVA are aspects of the preparation of valuable intermediates in compounds 1 and 11 (see compounds 7 and 27), but another Aspects also showed significant fungicidal activity. Particularly preferred compounds are compounds of the formula 1 ¥1 to 1 ¥8, wherein the combination of y, R, L, L, L3 and L4 corresponds in each case to one of the above Tables a. 〇

本發明之另一態樣係關於式V化合物,Another aspect of the invention pertains to a compound of formula V,

201043139 其中R、R、R3、L1、L2、l3及L4具有通用含義之一或 特定言之上文對於化合物邮給出之較佳含義之一; 如下化合物除外,其中 R1 ' R2 ' R3 ' 12 λ τ 3 κ τ 4 * ^ ,, 及L為虱’l為氟或CF3,且τττΓ 為雙鍵; …、以^及^為氫’^及以為氟’且二為單 鍵; 亦較佳地,如下化合物除外,其中 R R、R、L、L3及L4為氫,L1為漠或甲氧基,且 —為雙鍵; R及R2均為CH3 ’ R3、l2、P及L4為氫,Ll為氟、 甲氧基或CF3 ’且二τ為雙鍵; R1、R2、R3、L1、L3 及 L4 為氫,L2 為 CF3,且= 鍵0 溴、 為單 較佳化合物V為化合物VA,201043139 wherein R, R, R3, L1, L2, l3 and L4 have one of the general meanings or specifically one of the preferred meanings given above for the compound; except for the following compounds, wherein R1 'R2 'R3 ' 12 λ τ 3 κ τ 4 * ^ , , and L are 虱 'l is fluorine or CF3, and τττΓ is a double bond; ..., ^ and ^ are hydrogen '^ and are considered to be fluorine' and two are single bonds; Except for the following compounds, wherein RR, R, L, L3 and L4 are hydrogen, L1 is desert or methoxy, and - is a double bond; R and R2 are both CH3 'R3, l2, P and L4 are hydrogen, Ll is fluorine, methoxy or CF3' and diτ is a double bond; R1, R2, R3, L1, L3 and L4 are hydrogen, L2 is CF3, and = bond 0 is bromine, which is a single preferred compound V is compound VA ,

’、中R R、R 及L4具有通用含義之—或 特疋δ之上文對於化合物〗及Η給出之較佳含義之一 · 如下化合物除外’其〜^^^為氫…丨 及L4為氟。 147475.doc 80· 201043139 化合物V及VA為製備化合物I及II中之有價值中間物(參 看化合物6及26)。 本發明之另一態樣係關於式VI化合物,', RR, R and L4 have the general meaning - or characteristic δ above one of the preferred meanings given for the compound and · · except for the following compounds 'its ~ ^ ^ ^ is hydrogen ... 丨 and L4 is fluorine. 147475.doc 80· 201043139 Compounds V and VA are valuable intermediates in the preparation of compounds I and II (see compounds 6 and 26). Another aspect of the invention pertains to a compound of formula VI,

CH R3 LCH R3 L

Ο 其中Rl、R2、R3、Ll、L2、L3及L4具有通用含義之一或 特定言之上文對於化合物丨及丨〗給出之較佳含義之一; 如下化合物除外,其中、r2、r3、[2、L3及L4為氫, L1為溴,且ΤΓΓ7為單鍵; 亦較佳地’如下化合物除外,其中 R、R2、R3、L2、L3及L4為氫’ L1為氟、溴、曱氧基或 CF3,且—為雙鍵; 3 , 、 L2 、Ο wherein R1, R2, R3, L1, L2, L3 and L4 have one of the general meanings or specifically one of the preferred meanings given above for the compound 丨 and 丨; except for the following compounds, wherein r2, r3 , [2, L3 and L4 are hydrogen, L1 is bromine, and ΤΓΓ7 is a single bond; also preferably 'except for the following compounds, wherein R, R2, R3, L2, L3 and L4 are hydrogen' L1 is fluorine, bromine, Alkoxy or CF3, and - is a double bond; 3, , L2,

R1及R2均為CHR1 and R2 are both CH

較佳化合物vi為化合物VIA, 、L3及L4為氫,l1為氟、溴、 L為CF3,且Τ7ΓΓ為單Preferred compound vi is compound VIA, L3 and L4 are hydrogen, l1 is fluorine, bromine, L is CF3, and Τ7ΓΓ is a single

147475.doc -81 - 201043139 其中R1、R2、R3、L1、L2、L3及L4具有通用含義之一或 特定言之上文對於化合物I及Π給出之較佳含義之_ . 如下化合物除外,其中R1、R2、R3、L2、。及l4 , 且L1為溴。 乳 化合物VI及VIA為製備化合物1及1](中之有價值中間物 (參看化合物41)。 本發明之另一態樣係關於式VII化合物,147475.doc -81 - 201043139 wherein R1, R2, R3, L1, L2, L3 and L4 have one of the general meanings or, in particular, the preferred meanings given above for the compounds I and hydrazine. Wherein R1, R2, R3, L2. And l4, and L1 is bromine. Milk Compounds VI and VIA are the preparation of compounds 1 and 1] (the valuable intermediates thereof (see compound 41). Another aspect of the invention pertains to compounds of formula VII,

其中…、“'。、〜^具有通用含義之一或 特定言之上文對於化合物1及11給出之較佳含義之一,且 R14為 Η或 C(0)〇R15,其中 R15係選自氫、Cl-Cl0炫基、Cl_c“院基、C3_Ci〇環烧 基、環烧基、苯基、苯基_Ci_C4烷基,其中最後2 個提及之基團中之苯基部分可具有卜2、3、4或5個取代 基118,及含有卜2或3個選自N、〇及S之雜原子作為環成 貝的5員或6員飽和、部分不飽和或芳族雜環,其中該雜广 可具有卜2或3個取代#,其中R8係如上文所定義;衣 如下化合物除外,其中 R:、R2、R3、Rl4、L2、L3mwL、CF3n …、…、…、加為氫’以脚甲氣 147475.doc 201043139 基或IL ; R1、R2、R3、L〖及l4為氫,P及l3為第三丁基,且r14為 氫或 cooch3。 化合物VII為製備化合物{及Η中之有價值中間物(參看化 合物4) ^ 本發明之另一態樣係關於式VIII化合物,Wherein, "'., ~^ have one of the general meanings or specifically one of the preferred meanings given above for compounds 1 and 11, and R14 is Η or C(0) 〇 R15, wherein R15 is selected From hydrogen, Cl-Cl0 ndyl, Cl_c "homogeneous, C3_Ci 〇 cycloalkyl, cycloalkyl, phenyl, phenyl-Ci_C4 alkyl, wherein the phenyl moiety of the last two mentioned groups may have 2, 3, 4 or 5 substituents 118, and a 5- or 6-membered saturated, partially unsaturated or aromatic heterocyclic ring containing 2 or 3 heteroatoms selected from N, fluorene and S. Wherein the heteropoly can have 2 or 3 substitutions #, wherein R8 is as defined above; except for the following compounds, wherein R:, R2, R3, Rl4, L2, L3mwL, CF3n ..., ..., ..., plus It is hydrogen 147475.doc 201043139 or IL; R1, R2, R3, L and 14 are hydrogen, P and l3 are tributyl, and r14 is hydrogen or cooch3. Compound VII is a valuable intermediate for the preparation of the compound {and oxime (see Compound 4). ^ Another aspect of the invention pertains to a compound of formula VIII,

L2 (VIII) Η 其中R1、R3、L1、L2、L3AL4具有通用含義之—或特定 言之上文對於化合物丨及丨!給出之較佳含義之一,且係 如上文所定義; 如下化合物除外,其中 , J.L24CF3^ f 氟; R1、R3、L1及1/為氫,L2AL3為第三丁基,且r14為氨或 COOCH3 ο 化合物νΐΠ為製備化合物中之有價值中間物(參看 化合物3)。 本發明之另一態樣係關於式IX化合物, 147475.doc -83· (IX) 201043139 M R3 L1L2 (VIII) Η where R1, R3, L1, L2, L3AL4 have the general meaning - or specifically the above for the compound 丨 and 丨! One of the preferred meanings given, and is as defined above; except for the following compounds, wherein J.L24CF3^ f is fluorine; R1, R3, L1 and 1 are hydrogen, L2AL3 is a third butyl group, and r14 is Ammonia or COOCH3 ο Compound ν is a valuable intermediate in the preparation of compounds (see Compound 3). Another aspect of the invention pertains to a compound of formula IX, 147475.doc-83· (IX) 201043139 M R3 L1

其中 ^ 義之一; /、有通用合義夕一為 特定言之上文對於化合物1及11給出之較佳含 孰 〆 如下化合物除外,其中 為CF3或溴,且 111、112、113、1^、1^^3及1/為氫,1; ΤΤΤΓ為單鍵; R1、R2、R3、R14、L1、L3 及 ι/Α 气 τ2 上产 為虱’ L2為CF3、曱氧基 或氟,且二ΓΓ為單鍵; 為第三丁基,R14為氫 R1、R2、R3、L1及 L4為氫,L2及 L: 或COOCH3,且二為單鍵; 亦較佳地,如下化合物除外,其中Wherein one of the meanings; /, there is a general meaning of the first one is specified above for compounds 1 and 11 except for the following compounds, including CF3 or bromine, and 111, 112, 113, 1 ^, 1^^3 and 1/ are hydrogen, 1; ΤΤΤΓ is a single bond; R1, R2, R3, R14, L1, L3 and ι/Α gas τ2 are produced as 虱' L2 is CF3, decyloxy or fluorine And diterpene is a single bond; is a third butyl group, R14 is hydrogen, R1, R2, R3, L1 and L4 are hydrogen, L2 and L: or COOCH3, and two are single bonds; preferably, the following compounds are excluded ,among them

Ri 、 R2 、 R3 、 L2 、 CF3,且 為雙鍵; L及L為氫,Li為氟、溴、曱氧基或 R 及 R 均為 CH3,R3、L2、L3τ 4 &amp; . L及L為氬,L!為氟、溴、 甲氧基或CF3’且ττττ為雙鍵; R R R、L、L3及L4為氫’ L2為Cf3,且二為單 鍵 化口物IX為製備化合物ΙΑΠ中之有價值中間物(參看化 合物5及12)。 當然,化合物I及Π之上述限制條件(亦即Ll、U、L3及 L中至y者不為鼠)對於化合物IV、iva、V、VA、VI、 147475.doc -84- 201043139 VIA、VII、VIII及 IX亦有效。 本發明進一步係關於一種農業組合物,其包含至少一種 如上定義之式I、II及/或IV化合物或其農業上可接受之 鹽,及液體或固體載劑。下文定義本發明之組合物中亦可 含有之適合載劑以及助劑及其他活性化合物。 本發明之化合物I及II以及IV及組合物分別適用作殺真菌 劑。其因可對抗廣泛範圍植物病原性真菌之突出效用而著Ri, R2, R3, L2, CF3, and are double bonds; L and L are hydrogen, Li is fluorine, bromine, decyloxy or R and R are both CH3, R3, L2, L3τ 4 &amp; L and L Is argon, L! is fluorine, bromine, methoxy or CF3' and ττττ is a double bond; RRR, L, L3 and L4 are hydrogen 'L2 is Cf3, and two are single-bonded IX for preparing compound ΙΑΠ Valuable intermediates (see compounds 5 and 12). Of course, the above-mentioned limitations of Compound I and hydrazine (ie, L1, U, L3, and L to y are not rats) for Compounds IV, iva, V, VA, VI, 147475.doc-84-201043139 VIA, VII , VIII and IX are also effective. The invention further relates to an agricultural composition comprising at least one compound of formula I, II and/or IV as defined above, or an agriculturally acceptable salt thereof, and a liquid or solid carrier. Suitable carriers and auxiliaries and other active compounds which may also be included in the compositions of the invention are defined below. The compounds I and II and IV and compositions of the invention are each suitable for use as a fungicide. It is resistant to the outstanding effects of a wide range of phytopathogenic fungi.

❹ 名’該等植物病原性真菌包括土壤傳播之真菌,尤其來源 於根腫 綱(Plasmodiophoromycetes)、霜黴 _ 菌綱 (Peron〇Sp0romycetes)(同義詞卵菌綱(〇〇inycetes))、壺菌綱 (Chytridiomycetes)、接合菌綱(ZygomyCetes)、子囊菌綱 (ASCOmycetes)、擔子菌綱(Basidi〇mycetes)及半知菌綱 (DeUteromycetes)(同義詞不完全菌綱(Fungi …。 一些具有全身效用且其可在作物保護中用作葉面殺真菌 劑、拌種殺真菌劑及土壤殺真_。此外,其適用於防治 尤其出現於木材或植物之根的有害真菌。 冬發明之化合物!、„纽及組合物在防治各種裁培㈣ (諸如穀類,例如小麥、黑麥、大麥、里❹ 'These plant pathogenic fungi include soil-borne fungi, especially from Plasmodiophoromycetes, Peron 〇Sp0romycetes (synonym 〇〇inycetes), and chytrids (Chytridiomycetes), ZygomyCetes, ASCOmycetes, Basidi〇mycetes, and DeUteromycetes (synonymous fungi (Fungi .... Some have systemic utility and It can be used as a foliar fungicide, seed dressing fungicide and soil killing in crop protection. In addition, it is suitable for controlling harmful fungi which are especially found in the roots of wood or plants. And the composition is in the control of various cuts (4) (such as cereals, such as wheat, rye, barley,

稻;甜菜’例如甜菜或飼料甜菜;水果,諸如梨果燕=2 及無核果,例如蘋果、t、李子、桃子、杏仁 X 莓、樹莓、黑莓或醋栗;豆科植物,例 _、:卓 备、苜卷或大豆;油料植物,例如油 豌豆 葵、椰子、可可豆、萬麻、油標、落花生或大=、/曰 植物,例如+爪立A七扭 丑,葫蘆科 』如南瓜、,瓜或甜瓜;纖維植 仲化、亞 147475.doc -85- 201043139 匕、大麻或黃麻’·柑橘類水果,例如燈子、檸檬、葡萄柚 蔬菜,例如获菜、萬莖、董荀、卷心菜、胡蘿 〜、、番蘇、馬鈴薯、葫蘆或辣椒;月桂科植物,例 如鱷梨、肉桂或樟腦:能源及原料植物,例如玉米、大 豆、油菜、甘蔗或油棕;玉米;於草;堅果;咖哪;苹 葉;香蕉;藤本植物(鮮食葡萄⑽le g卿e)及葡萄汁葡二 :),蛇麻子,·草’·天然橡膠植物或觀賞植物及森林植 ’例如花 '灌木、闊葉樹或常綠樹’例如針葉樹心 及植物繁殖材料(諸如種子)及此等植物之作物材料上之眾 多植物病原性真菌中尤其重要。 化合物卜nhv及其組合物較佳分別用於防治大田作物 上之眾多真菌,該等大田作物諸如為馬鈴薯、甜菜、菸 草:小麥、黑麥、大麥、燕麥、稻、玉米、棉花、大豆、、 :菜、豆科植物、向曰葵、咖啡或甘薦;水果;藤本植 物,觀賞植物·,或蔬菜,諸如黃瓜、番祐、豆類或南瓜。 應瞭解術語「植物繁殖材料」表示可用於繁殖植物之植 物之所有生殖部分(諸如種子)及營養性植物材料諸如插 枝及塊莖(例如馬鈴薯)。其包括種子、根、果實、塊贫、 球莖'根莖、嫩芽、芽及其他植物部分,包括軒苗:幼 ^其在發芽後或露土後移植。亦可在移植之前藉由藉由 汉潰或澆注進行整體或局部處理來保護此等幼苗。 以化合物卜11及1Μ其組合物處理植物繁殖材料較佳分 別用於防治縠類(諸如小麥、黑麥、大麥及燕麥);稻、玉 米、棉花及大豆上之眾多真菌。 147475.doc • 86 · 201043139 術語「栽培植物」應理解為包括已藉由育種、 突變誘發或遺傳工程進行改造之植物,包括(但 不限於)市售或研發中之生物技術農產品(參看 http://www.bio.org/speeches/pubs/er/agri_products.asp) 〇 經 遺傳改造之植物為遺傳物質已藉由使用重組DNA技術進行 改造從而在天然情形下不能藉由雜交育種、突變或天然重 組容易地獲得之植物。通常已將一或多個基因整合至經遺 傳改造之植物的遺傳物質中以改良植物之某些特性。此等 遺傳改造亦包括(但不限於)例如藉由糖基化或聚合物添加 對蛋白質、寡肽或多肽進行靶向轉譯後修飾,諸如異戊烯 化、乙薩化或法呢基化(farnesylated)部分或PEG部分。 作為育種或遺傳工程之習知方法之結果,使得已藉由育 種、突變誘發或遺傳工程進行改造之植物例如耐受特定類 別除草劑之施用,該等除草劑諸如為羥基苯基丙酮酸二加 氧酶(HPPD)抑制劑;乙醯乳酸合成酶(ALS)抑制劑,諸如 磺醯脲(例如參看 US 6,222,100、WO 01/82685、WO 00/26390、WO 97/41218、WO 98/02526、WO 98/02527 ' WO 04/106529、WO 05/20673、WO 03/14357、WO 03/13225、WO 03/143 56、WO 04/16073)或咪唑啉酮(例如 參看 US 6,222,100 ' WO 01/82685、WO 00/026390、WO 97/41218、WO 98/002526、WO 98/02527、WO 04/106529、 WO 05/20673、WO 03/014357、WO 03/13225、WO 03/14356、WO 04/16073);烯醇丙酮醯莽草酸-3-磷酸合成 酶(enolpyruvylshikimate-3-phosphate synthase,EPSPS)抑 147475.doc -87 - 201043139 制劑,諸如草甘膦(glyphosate)(例如參看WO 92/00377); 楚胺酸胺合成酶(GS)抑制劑,諸如草銨膦(glufosinate)(例 如參看EP-A 242 236、EP-A 242 246)或二苯甲腈除草劑 (oxynil herbicide)(例如參看US 5,559,024)。藉由育種(突 變誘發)之習知方法已使得若干栽培植物财受除草劑,例 如使得 Clearfield®夏季油菜(Canola, BASF SE,Germany)而于 受味峻琳酮,例如曱氧σ米草於(imazamox)。遺傳工程改造 方法已用以使得諸如大豆、棉花、玉米、甜菜及油菜之栽 培植物耐受諸如草甘膦及草銨膦之除草劑,其中一些可以 商標名 RoundupReady®(草甘膦对受型,Monsanto, U.S.A.) 及 LibertyLink®(草銨膦财受型,Bayer CropScience, Germany)購得。 此外,亦涵蓋藉由使用重組DNA技術能夠合成一或多種 殺昆蟲蛋白之植物,該一或多種殺昆蟲蛋白尤其為自細菌 桿菌屬(genus ,尤其自蘇雲金芽孢桿菌 已知者,諸如δ-内毒素,例如CrylA(b)、 CrylA(c)、CrylF、CryIF(a2)、CryIIA(b)、CrylllA、 CrylllB(bl)或Cry9c ;營養期殺昆蟲蛋白(VIP),例如 VIP1、VIP2、VIP3或VIP3A ;拓殖線蟲之細菌的殺昆蟲蛋 白,例如光桿菌屬(尸spp.)或嗜線蟲桿菌屬 spp.);由動物產生之毒素,諸如蛾毒素、虫知 蛛毒素、黃蜂毒素或其他昆蟲特異性神經毒素;由真菌產 生之毒素,諸如鏈黴菌毒素,植物凝集素(plant lectin), 諸如婉豆或大麥凝集素;凝集素(agglutinin);蛋白酶抑制 147475.doc -88- 201043139 劑,諸如胰蛋白酶抑制劑、絲胺酸蛋白酶抑制劑、塊莖儲 藏蛋白(patatin)、胱抑素(cystatin)或木瓜蛋白酶抑制劑; 核糖體去活蛋白(RIP),諸如蓖麻毒素、玉蜀黍-RIP、相思 子毒素(abrin)、絲瓜籽毒蛋白(luffin)、沙泊寧(saporin)或 欖香膠素(bryodin);類固醇代謝酶,諸如3-羥基類固醇氧 化酶、蛻皮素-IDP-糖基-轉移酶、膽固醇氧化酶、蜆皮激 素抑制劑或HMG-CoA還原酶;離子通道阻斷劑,諸如鈉 或鈣通道之阻斷劑;保幼激素酯酶;利尿激素受體(異株 又寫根毒蛋白受體(helicokinin receptor));笑合成酶(stilben synthase)、聯节合成酶(bibenzyl synthase)、殼質酶 (chitinase)或葡聚糖酶(glucanase)。在本發明之上下文 中,亦應明確瞭解,此等殺昆蟲蛋白或毒素為前毒素(pretoxin) 、 雜交蛋白 、經截短或 以其他方式修 飾之蛋 白質。 雜交蛋白之特徵在於蛋白質域之新組合(例如參看WO 02/015701)。例如在EP-A 374 753、WO 93/007278 ' WO 95/34656、EP-A 427 529、EP-A 451 878、WO 03/18810及 WO 03/52073中揭示此等毒素或能夠合成此等毒素之經遺 傳改造之植物的其他實例。產生此等經遺傳改造之植物的 方法一般為熟習此項技術者所已知且描述於例如上述公開 案中。經遺傳改造之植物中所含之此等殺昆蟲蛋白使產生 此等蛋白質之植物具有對來自節肢動物(athropod)之所有 分類群之有害害蟲,尤其對甲蟲(鞠翅目(Coeloptera))、兩 翼昆蟲(雙翅目(Diptera))及蛾(鱗翅目(Lepidoptera))及對線 蟲(線蟲綱(Nematoda))之财受性。能夠合成一或多種殺昆 147475.doc -89- 201043139 蟲蛋白之經遺傳改造之植物例如描述於上述公開案中,且 其中一些可購得,諸如YieldGard®(產生CrylAb毒素之玉 米栽培品種)、YieldGard® Plus(產生 Cryl Ab及 Cry3Bbl 毒 素之玉米栽培品種)、Starlink®(產生Cry9c毒素之玉米栽培 品種)、Herculex® RW(產生Cry34Abl、Cry35Abl及酶草胺 膦-N-乙醯基轉移酶[Phosphinothricin-N-Acetyltransferase, PAT]之玉米栽培品種);NuCOTN® 33B(產生CrylAc毒素之 棉花栽培品種)、Bollgard® 1(產生CrylAc毒素之棉花栽培 品種)、Bollgard® 11(產生Cry 1 Ac及Cry2Ab2毒素之棉花栽 培品種);VIPCOT®(產生VIP毒素之棉花栽培品種); NewLeaf®(產生Cry3 A毒素之馬鈴薯栽培品種);Bt-Xtra®、 NatureGard®、KnockOut®、BiteGard®、Protecta®、 Btll(例如 Agrisure® CB)及來自 Syngenta Seeds SAS,France 之Btl76(產生CrylAb毒素及PAT酶之玉米栽培品種)、來自 Syngenta Seeds SAS,France之 MIR604(產生經修飾型 Cry3 A 毒素之玉米栽培品種,參看WO 03/018810)、來自Monsanto Europe S.A., Belgium之MON 863(產生Cry3Bbl毒素之玉米 栽培品種)、來自 Monsanto Europe S.A·,Belgium 之 IPC 53 1 (產生經修飾型Cry 1 Ac毒素之棉花栽培品種)及來自 Pioneer Overseas Corporation,Belgium之 1507(產生 CrylF 毒素及PAT酶之玉米栽培品種)。 此外’亦涵蓋藉由使用重組DNA技術能夠合成一或多種 蛋白質以增強彼等植物對細菌、病毒或真菌病原體之抗性 或耐受性之植物。此等蛋白質之實例為所謂「發病機制相 147475.doc -90- 201043139 關性蛋白質」(PR蛋白質,例如參看EP-A 392 225)、植物 疾病抗性基因(例如表現來源於墨西哥野生馬鈴薯抗晚疫 馬铃薯之對抗馬铃薯腐疫菌 起作用之抗性基因的馬鈴薯栽培品 種)或Τ4溶菌酶(例如能夠合成此等具有較強針對細菌(諸如 梨火疫病菌awy/vora))之抗性之蛋白質的馬鈴薯 栽培品種)。產生此等經遺傳改造之植物的方法一般為熟 習此項技術者所已知且描述於例如上述公開案中。 此外,亦涵蓋藉由使用重組DNA技術能夠合成一或多種 蛋白質以提高生產力(例如生物質量產量、榖粒產率、澱 粉含量、油含量或蛋白質含量)、對乾旱、鹽度或其他生 長限制環境因素之耐受性或對彼等植物之害蟲及真菌、細 菌或病毒病原體之财受性的植物。 此外,亦涵蓋藉由使用重組DNA技術含有改變量之内含 物質或新穎内含物質,尤其改良人類或動物營養之植物, 例如產生促健康長鏈ω-3脂肪酸或不飽和ω-9脂肪酸之油料 作物(例如 Nexera®油菜,DOW Agro Sciences, Canada)。 此外,亦涵蓋藉由使用重組DNA技術含有改變量之内含 物質或新穎内含物質,尤其提高原料產量之植物,例如產 生增加量之支鏈澱粉之馬鈴薯(例如ΑιηΠ or a®馬鈴薯, BASF SE,Germany)。 化合物I、II及IV及其組合物分別尤其適用於防治以下植 物疾病· 觀賞植物、蔬菜(例如白色念珠菌(丄Cfl/7山·ί/α))及向曰蔡 147475.doc -91 - 201043139 (例如婆羅門參白銹菌(丄ir&lt;3go;?ogo„b))上之白銹菌屬 sPP.)(白銹病);蔬菜、油菜(芸苔生交鏈孢(丄 或芸苔交鏈孢(丄心、甜菜(細交鏈孢 (A ie⑽u))、水果、稻、大豆、馬鈴薯(例如茄交鏈孢(丄 或互隔交鏈孢(儿a/ier仙ίβ))、番茄(例如茄交鏈孢 或互隔交鏈孢)及小麥上之交鏈孢屬(j/ier⑽η·α spp)(交鏈 孢菌葉斑病);甜菜及蔬菜上之絲囊黴屬㈠如⑽⑽打打 SPP·),毅類及蔬菜上之殼二孢屬Spp ),例如小 麥上之小麥殼二孢(儿炭疽病)及大麥上之大麥殼二 孢(丄/zorc/ez·),平臍轉孢屬Spp )及内臍蹲孢屬 spp.)(有性型:旋孢腔菌屬(c〇c/^.〇w似 SPP·)) ’例如玉米上之南方葉枯病(玉蜀黍内臍蠕孢(乃 讲吵山·〇)及北方葉枯病(玉米平臍蠕孢(凡,例如穀 類上之斑點病(小麥根腐平臍蠕孢Μ s〇r〇jb.m•训a))及例如 稻及草皮上之稻平臍蠕孢;穀類(例如小麥或大 麥)上之小麥白粉菌(价wwerz.a grawz.m))(原名:雀麥白粉菌 (£WZ&gt;/Ze ^⑽&amp;&amp;))(白粉病);水果及漿果(例如草莓)、蔬 菜(例如萵苣、胡蘿蔔、根芹菜及甘藍)、油菜、花、藤本 植物森林植物及小麥上之灰徽菌(Boiryi/s ckerea)(有性 t 田氏葡萄孢盤菌(Boir少οίζϋ /wcAre/z.a/ia):灰黴病); 葛宜上之萵苣路囟病菌(万rewia /aciwcae)(霜徽病);闊葉樹 及$、、彔樹上之青變真菌同義詞長嗓殼黴 (ph/osiowa))屬(腐爛或〉周萎病),例如榆樹上之榆青變真 菌(C. 荷蘭榆樹病(Dutch elm disease));玉米(例如灰 147475.doc •92· 201043139 葉斑病.玉米灰斑病菌(c· ⑼、稻、甜菜(例如 甜菜褐斑病菌(c. 、甘蔗、蔬菜、咖啡、大豆(例 如大丑灰斑病菌(c. μ力即)或菊池氏斑點病菌(Chmc/^·)) 及稻上之斑點病菌屬(Cercoworaf Spp.)(斑點病菌葉斑病广 番加(例如番茄葉黴病菌(C.:葉黴病)及穀類上之 刀枝孢子菌屬(C/ai/owor/ww spp.),例如小麥上之禾累芽 枝黴(C_ 黑耳(biack ear));榖類上之黑麥角菌 〇 (.WC^ 卿)(麥角);玉米(圓斑病菌(C. ⑽細))、縠類(例如禾旋孢腔菌(Cm.v⑽),無性型: 小麥根腐平臍螺抱)及稻(例如宮部旋孢腔菌 狀似),無性型:水稻潛根線蟲⑽上之旋 孢腔菌(CW/^’oh/似)(無性型:平臍蠕孢之長蠕孢 of &amp;&gt;0/π以))屬(葉斑病);棉(例如棉花 刺盤孢(c.职巧种·))、玉米(例如禾生刺盤孢(c : 抗炭症莖腐病(Anthracnose stalk rot))、無核果、馬鈴薯 〇 (例如球刺盤孢(c. COCCOi5^):黑斑病)、豆類(例如豆刺盤 孢(C.⑸心則⑹⑽請))及大豆(例如平頭刺盤孢 或膠孢刺盤孢(C. 上之刺盤孢 - 謂)(有性型:炭疽病菌(G/〇were/⑷)屬(炭疽 病);伏革菌屬(C〇ri/c〜m spp.),例如稻上之紋枯伏革菌 (C. wwHi)(外鞘枯萎病);大豆及觀賞植物上之多主棒孢 病菌_此—)(葉斑病);環錐孢屬心士⑼⑴·謂 spp·),例如撖欖樹上之油撖欖孔雀斑菌(c· 〇/gflgz•⑽w); 果樹、藤本植物(例如鵝掌楸柱孢菌(c. /ζ&gt;ζ·Μπ办〇,有性 147475.doc -93- 201043139 型:鹤掌楸新叢赤殼菌(iVeo«ecir/a :黑足病 (Black Foot Disease))及觀賞植物上之柱孢菌屬(Qy/k办OCfl/po„ spp.)(例如果樹潰瘍或幼藤衰退,有性型:叢赤殼屬 spp.)或新叢赤殼菌屬(jVeonecirifl spp·));大豆上 之半知菌(Demaio/?/zora necairix)(有性型:白紋病菌屬 (/?οπ//—·ύί))(根及莖腐爛);腐皮殼菌屬spp.), 例如大且上之大立黑點病菌(Ζ). 摔倒病 (damping off));玉米、穀類(諸如大麥(例如大麥網斑病菌 (Ζλ kra)、網斑病)及小麥(例如小麥德氏菌(D repen山):褐斑病))、稻及草皮上之内臍蠕孢(同義詞長螺 孢’有性型:核腔菌(Pyrenop/zora))屬;藤本植物上之埃 斯卡病(五Mo dheaw)(頂枯病、乾枯病),其由斑點嗜蘭孢 孔菌(F〇r»n’n&gt;〇Wa (同義詞松針層孔菌(/ϊ/2β//ζ•⑽$ 、地中海層臥孔菌(jp.咖士以厂训〜)、厚孢普可 見&amp;溘(Phaeomoniella 原名厚抱瓶徵 (P/zaeoacremom'wm c/z/awj/c/osporz^))、寄生瓶徽菌 {Phaeoacremonium 及 / 或扁葡萄座腔菌 (如外―/merk 0心咖)引起;仁果(梨痂囊腔菌(五. 尸厂0)、無核果(樹莓疮囊腔菌(凡:炭症病)及藤本 植物(黑痘痂囊腔菌(五· 郎):炭疽病)上之痂囊腔菌 屬(幻SPP.) ’稻上之稻葉黑粉菌orjvzae)(葉 黑穗病);小麥上之黑附球菌屬(五p/c〇ccwm spp)(黑黴病); 甜菜(甜菜白粉菌(五· ^&amp;e))、蔬菜(例如豌豆白粉菌(£ p⑸)),諸如葫蘆科植物(例如二孢白粉菌(£ cich〇mcear謂))、 147475.doc -94- 201043139 甘藍、油菜(例如十字化科白粉菌(五.上之白 粉菌屬(£r&gt;^z&gt;/ze spp.)(白粉病);果樹、藤本植物及觀賞樹 木上之側彎孢菌(五/α?α)(葡萄腐病或頂枯病,無性 型:拉塔假孢囊/αία),同義詞百簕盤針孢 (Libertdla blepharis));玉米上之突臍蠕孢(Exser〇hi〖um)(同義 詞長蠕孢)屬(例如玉米大斑突臍蠕孢(£,turcicum));各種 植物上之鐮刀菌(FMwri請)(有性型:赤黴菌(GiMere//a)) 屬(凋萎病、根或莖腐爛),諸如榖類(例如小麥或大麥)上之 禾穀鐮刀菌(F. gra/m&gt;2ear«m)或黃色鐮刀菌(厂CM/worMm)(根 腐爛、斑點病或頭枯萎)、番茄上之尖孢鐮刀菌(P. 、大豆上之茄病鐮刀菌(F s〇/am·)及玉米上之串 珠鐮刀菌(F. veriz’e////〇WeiS);穀類(例如小麥或大麥)及玉 米上之禾頂囊设卤(尽全钮病 (take-all));穀類(例如禾縠赤黴菌(G. “邮))及稻(例如稻惡 黴赤徽囷(G. /WA:wroi):惡苗病(Bakanae disease))上之赤 黴菌屬spp.);藤本植物、仁果及其他植物上之 圍小叢设函(C?/omere//a 及棉上之棉花炭疸菌(g· gossxpii),稻上之毅粒染色(Grainstajning)複合症;藤本植 物上之葡萄球座菌⑴(黑腐病);薔薇科 植物及檜柏上之胳錢_屬(办Spp.),例如 梨上之沙賓膠銹菌(G. 銹病);玉米、穀類及稻上 之長蠕孢屬(同義詞内膦蠕孢屬,有性型:旋孢腔菌);鑷 病囷屬spp.),例如咖啡上之咖缚跪抱錄菌(打 vaiiairzx)(咖啡葉銹病);藤本植物上之葡萄褐斑病菌 147475.doc •95- 201043139 (/顯娜咖咖ra)(同義詞葡萄分枝抱子菌謂讎 ;大豆及棉上之菜.殼球孢菌(她⑽# 二—)(同義詞菜豆球蛋白(户w㈣)(根及莖腐爛); #類(例如小麥或大麥)上之雪徽嫌抱菌⑽㈣而咖㈣ mva/e)(同義„司夺腐鐮刀菌(心.,·___))(粉紅雪黴病 (pmk snow m〇ld));大豆上之白粉病菌(減㈣咖“㈣ 心//似《)(白粉病);褐腐病菌屬(从⑽出⑴4 spp),例如核果 類及其他薔薇科植物上之核果褐腐菌(M 、果生叢梗 孢(M·州⑶⑷及仁果褐腐菌(M花及小枝枯 病,褐腐病);榖類、香蕉、無核果及落花生上之球腔菌 屬spp.),諸如小麥上之禾草根結線蟲(m gramk/C0/a)(無性型··小麥殼針孢(&amp;pi〇ria ir^c〇、殼針 孢屬斑點病(Septoria blotch))或香蕉上之斐濟球腔菌(M /(/化似⑷(香蕉葉斑病(biack sigatoka disease));甘藍(例如 芸苔根腫菌(凡6rimiCaeh、油菜(例如寄生霜黴菌(p. '洋蔥(例如洋葱霜黴菌(户· 、於草 (菸草霜黴菌(凡iahci«a))及大豆(例如大豆霜黴菌(尸 maws/zwrica))上之霜黴菌屬(per〇„〇^p〇ra Spp )(霜黴病);大 瓦上之大i錄蟲(Phakopsora pachyrhizi)反3~集層鱗儀(j&gt;. (大立銹病);例如藤本植物(例如檸檬乾枯病菌 (户.irac/ze/p/n./a)及四抱藻瓶黴(户.加raiSp0ra))及大豆(例如 豆莖褐腐病菌(户·听职叫··莖腐爛)上之瓶梗黴屬(i%.a/〇_〇ra spp.) ’油菜及甘藍上之甘藍黑腐菌//.«gam)(根及莖 腐爛)及甜菜上之甜菜多黏菌(尸6eiae)(根腐爛、葉斑及猝 147475.doc -96· 201043139 倒病);向曰葵、藤本植物(例如葡萄生單軸黴(八vzYz,co/a): 样及葉斑)及大豆(例如莖腐爛:菜豆疫徽有 性型:大豆黑點病菌(D咖〇以/ze抑似扣—謂))上之擬莖點 黴屬(P/zomo/wb spp.);玉米上之玉米褐斑病菌 褐斑病);各種植物’諸如辣椒及葫蘆科植物(例 如辣椒疫黴菌(户· 、大豆(例如大雄疫黴菌(户. wegawerwa) ’同義詞大豆疫黴菌(八似))、馬鈐薯及番 茄(例如致病疫黴菌(P. :晚疫病)及闊葉樹(例如 橡樹疫黴菌(户·〜worwm):橡木猝死)上之疫黴菌屬 (P/^io/?/2i/zora spp.)(凋萎病、根、葉、果實及莖腐病);甘 藍、油菜、蘿萄及其他植物上之十字花科植物根瘤病菌 (Plasmodiophora brassicae)(裉瘤病),.,單軸黴屬(P/izsmopara spp.),例如藤本植物上之葡萄生單轴黴(尸.Wiico/a)(葡萄 藤霜黴病)及向日葵上之向日葵露菌病菌(P. ;薔 薇科植物、蛇麻子、梨果及無核果上之叉絲單囊殼屬 (Poi/oi/7/merii spp.)(白粉病),例如蘋果上之蘋果白粉病菌 (P. /ewcoiric/m);例如榖類(諸如大麥及小麥(禾穀多黏菌 (P. gra/w/m··?))及甜菜(甜菜多黏菌(尸.Z&gt;eioe)))上之多黏菌屬 (Po/ywyxa spp.)及由此傳播之病毒性疾病;穀類(例如小麥 或大麥)上之基腐病菌(·f^eMi/ocercoworeZ/ci /lerpoiric/io^fes)(眼 點,有性型:惡苗病菌(Γαρα/α ;各種植物上 之假霜黴霜黴病)’例如葫蘆科植物 上之古巴假霜黴(P. cwZjenhs)或蛇麻子上之漳草假霜黴(P. Zzwwz7z·);藤本植物上之葡萄角斑葉焦病菌 147475.doc -97- 201043139 irac/2ezp/n/a)(紅火病(red flre disease)或羅氏病(r〇tbrenner,), 無性型.瓶梗黴(P/n’a/op/i〇ra));各種植物上之銹菌屬 sPP.)(錢病)’例如穀類(諸如小麥、大麥或黑麥) 及蘆旬(例如天門科柄鏽菌(/&gt;. 幻·))上之褐銹菌(p ⑽)(褐銹病或葉銹病)、條形柄銹菌(p你砂(條銹 病或黃銹病)、大麥柄銹菌(尸· (矮銹病)、禾柄銹菌 (户· 莖銹病或黑銹病)或葉銹菌(p (褐 銹病或葉銹病)·’小麥上之偃麥草核腔菌Rice; beet 'eg beet or fodder beet; fruit, such as pear fruit swallow = 2 and non-nuclear, such as apple, t, plum, peach, almond X raspberry, raspberry, blackberry or gooseberry; legume, _ : Zhuo, 苜 or soy; oil plants, such as oil peas, coconut, cocoa beans, marijuana, oil labels, groundnuts or large =, / 曰 plants, such as + claws A seven twisted ugly, cucurbitaceae such as Pumpkin, melon or melon; fiber phytochemical, 147475.doc -85- 201043139 匕, marijuana or jute' citrus fruits, such as lamps, lemons, grapefruit vegetables, such as vegetables, stalks, Dongsong, Cabbage, carrot, gourd, potato, gourd or pepper; laurel plant, such as avocado, cinnamon or camphor: energy and raw plant, such as corn, soybean, canola, sugar cane or oil palm; corn; Nuts; café; apple leaves; bananas; vines (fresh grapes (10) le gqing e) and grape juices: (2), hops, grasses, 'natural rubber plants or ornamental plants and forest plants' such as flower shrubs, Broadleaf or evergreen tree It is especially important in many phytopathogenic fungi such as conifers and plant propagation materials such as seeds and crop materials of such plants. The compound nhv and the composition thereof are preferably used for controlling a plurality of fungi on the field crops, such as potatoes, beets, tobacco: wheat, rye, barley, oats, rice, corn, cotton, soybeans, : vegetables, legumes, hollyhocks, coffee or ginseng; fruit; vines, ornamental plants, or vegetables, such as cucumbers, guava, beans or pumpkins. It should be understood that the term "plant propagation material" means all reproductive parts (such as seeds) and vegetative plant materials such as cuttings and tubers (e.g., potatoes) that can be used to propagate plants. It includes seeds, roots, fruits, lumps, bulbs, rhizomes, shoots, buds and other plant parts, including Xuan Miao: young, which is transplanted after germination or after emergence. These seedlings can also be protected prior to transplantation by whole or partial treatment by crushing or pouring. Treatment of plant propagation material with the compositions of Compounds 11 and 1 is preferably used to control mites (such as wheat, rye, barley, and oats); and numerous fungi on rice, corn, cotton, and soybeans. 147475.doc • 86 · 201043139 The term “cultivated plants” is understood to include plants that have been modified by breeding, mutation induction or genetic engineering, including (but not limited to) biotech agricultural products that are commercially available or under development (see http: //www.bio.org/speeches/pubs/er/agri_products.asp) Genetically engineered plants have been genetically modified by using recombinant DNA techniques so that they cannot be crossed, mutated or naturally in nature. A plant that is easily obtained by recombination. One or more genes have typically been integrated into the genetic material of a genetically engineered plant to modify certain characteristics of the plant. Such genetic engineering also includes, but is not limited to, targeted post-translational modifications of proteins, oligopeptides or polypeptides, such as prenylation, acetalization or farnesylation, by glycosylation or polymer addition ( Farnesylated) part or PEG moiety. As a result of conventional methods of breeding or genetic engineering, plants that have been engineered by breeding, mutation induction or genetic engineering, for example, are tolerant to the application of a particular class of herbicides such as hydroxyphenylpyruvate Oxygenase (HPPD) inhibitor; acetate lactate synthase (ALS) inhibitor, such as sulfonium urea (see, for example, US 6,222,100, WO 01/82685, WO 00/26390, WO 97/41218, WO 98/02526, WO 98/02527 'WO 04/106529, WO 05/20673, WO 03/14357, WO 03/13225, WO 03/143 56, WO 04/16073) or imidazolinones (for example see US 6,222,100 'WO 01/82685, WO 00/026390, WO 97/41218, WO 98/002526, WO 98/02527, WO 04/106529, WO 05/20673, WO 03/014357, WO 03/13225, WO 03/14356, WO 04/16073) Enolpyruvylshikimate-3-phosphate synthase (EPSPS) 147475.doc -87 - 201043139 Formulations, such as glyphosate (see, for example, WO 92/00377); An amine amine synthase (GS) inhibitor, such as glufosinate (see, for example, EP-A 242 236, EP-A 242 246) Or oxynil herbicide (see, for example, US 5,559,024). A number of cultivated plants have been subjected to herbicides by conventional methods of breeding (mutation induced), for example, Clearfield® summer rapeseed (Canola, BASF SE, Germany) and scented lincolone, such as 曱 σ σ 于(imazamox). Genetic engineering methods have been used to make cultivated plants such as soybean, cotton, corn, sugar beet and canola tolerant to herbicides such as glyphosate and glufosinate, some of which are available under the trade name RoundupReady® (glyphosate versus type). Monsanto, USA) and LibertyLink® (Glufosinate, Bayer CropScience, Germany). Also encompassed is the ability to synthesize one or more insecticidal proteins by using recombinant DNA techniques, in particular from the genus Genus, especially from Bacillus thuringiensis, such as δ- Toxins such as CrylA(b), CrylA(c), CrylF, CryIF(a2), CryIIA(b), CrylllA, CrylllB(bl) or Cry9c; vegetative insecticidal proteins (VIP), such as VIP1, VIP2, VIP3 or VIP3A; an insecticidal protein of a bacterium that colonizes nematodes, such as the genus Bacillus (spor.) or the genus X. elegans spp.); a toxin produced by an animal, such as moth toxin, insect toxin, wasptoxin or other insect-specific Sexual neurotoxin; a toxin produced by a fungus, such as streptomyces toxin, plant lectin, such as cowpea or barley agglutinin; agglutinin; protease inhibition 147475.doc -88- 201043139 agent, such as pancreas Protease inhibitor, serine protease inhibitor, patatin, cystatin or papain inhibitor; ribosome deactivated protein (RIP), such as ricin, jade蜀黍-RIP, abrin, abuffin, saporin or bryodin; steroid metabolism enzymes such as 3-hydroxysteroid oxidase, quercetin-IDP - Glycosyl-transferase, cholesterol oxidase, ecdysone inhibitor or HMG-CoA reductase; ion channel blockers, such as sodium or calcium channel blockers; juvenile hormone esterase; diuretic hormone receptor ( The heterologous strain also writes the helicokinin receptor; stilben synthase, bibenzyl synthase, chitinase or glucanase. In the context of the present invention, it should also be clear that such insecticidal proteins or toxins are pretoxins, hybrid proteins, truncated or otherwise modified proteins. Hybrid proteins are characterized by a new combination of protein domains (see, for example, WO 02/015701). Such toxins or the ability to synthesize such toxins are disclosed, for example, in EP-A 374 753, WO 93/007278 'WO 95/34656, EP-A 427 529, EP-A 451 878, WO 03/18810 and WO 03/52073. Other examples of genetically engineered plants. Methods of producing such genetically engineered plants are generally known to those skilled in the art and are described, for example, in the above publication. Such insecticidal proteins contained in genetically engineered plants cause plants producing such proteins to have harmful pests to all taxa from arthropods, especially to beetles (Coeloptera), two wings Insects (Diptera) and moths (Lepidoptera) and the susceptibility to nematodes (Nematoda). Genetically engineered plants capable of synthesizing one or more kelins 147475.doc -89- 201043139 worm proteins are described, for example, in the above publication, and some of them are commercially available, such as YieldGard® (a corn cultivar producing CrylAb toxin), YieldGard® Plus (a corn cultivar producing Cryl Ab and Cry3Bbl toxins), Starlink® (a corn cultivar producing Cry9c toxin), Herculex® RW (producing Cry34Abl, Cry35Abl and enzymatic phosphonium-N-acetyltransferase [ Phosphinothricin-N-Acetyltransferase, PAT] maize cultivar); NuCOTN® 33B (cotton cultivar producing CrylAc toxin), Bollgard® 1 (cotton cultivar producing CrylAc toxin), Bollgard® 11 (production of Cry 1 Ac and Cry2Ab2) Cotton cultivar of toxin); VIPCOT® (cotton cultivar producing VIP toxin); NewLeaf® (potato cultivar producing Cry3 A toxin); Bt-Xtra®, NatureGard®, KnockOut®, BiteGard®, Protecta®, Btll (eg Agrisure® CB) and Btl76 from Syngenta Seeds SAS, France (corn cultivar producing CrylAb toxin and PAT enzyme) MIR604 from Syngenta Seeds SAS, France (corn cultivar producing modified Cry3 A toxin, see WO 03/018810), MON 863 from Monsanto Europe SA, Belgium (corn cultivar producing Cry3Bbl toxin), from Monsanto Europe SA, Belgium IPC 53 1 (cotton cultivar producing modified Cry 1 Ac toxin) and 1507 from Pioneer Overseas Corporation, Belgium (corn cultivar producing CrylF toxin and PAT enzyme). Furthermore, plants which are capable of synthesizing one or more proteins by using recombinant DNA techniques to enhance the resistance or tolerance of their plants to bacterial, viral or fungal pathogens are also encompassed. Examples of such proteins are the so-called "pathogenesis phase 147475.doc -90-201043139 related proteins" (PR proteins, see for example EP-A 392 225), plant disease resistance genes (for example, performance derived from Mexican wild potato late Potato cultivar of Phytophthora infestans against the resistance gene of Phytophthora sojae) or Τ4 lysozyme (for example, capable of synthesizing such strong against bacteria (such as Aphi/vora) Potato cultivar of resistant protein). Methods of producing such genetically engineered plants are generally known to those skilled in the art and are described, for example, in the above publication. In addition, it is also possible to synthesize one or more proteins by using recombinant DNA technology to increase productivity (eg, biomass yield, grain yield, starch content, oil content or protein content), to drought, salinity or other growth limiting environments. Tolerance of factors or plants for the pests of their plants and the fungi of fungal, bacterial or viral pathogens. In addition, it also encompasses plants which contain varying amounts of inclusions or novel inclusions, particularly for improving human or animal nutrition, by the use of recombinant DNA techniques, for example to produce healthy long-chain omega-3 fatty acids or unsaturated omega-9 fatty acids. Oil crops (eg Nexera® canola, DOW Agro Sciences, Canada). In addition, plants that contain varying amounts of inclusions or novel inclusions, particularly by increasing the yield of the raw materials, such as potatoes that produce increased amounts of amylopectin (eg, ΑιηΠ or a® potato, BASF SE) are also encompassed by the use of recombinant DNA technology. , Germany). Compounds I, II and IV and their compositions are especially suitable for controlling the following plant diseases, ornamental plants, vegetables (such as Candida albicans (丄Cfl/7山·ί/α)) and Xiang Cai 147475.doc-91 - 201043139 (eg, white rust sPP.) (white rust) on white rust fungus (丄ir&lt;3go;?ogo„b); vegetables, rapeseed (aspergillus oryzae) Cyclosporin (heart, beet (A ie (10) u)), fruit, rice, soybean, potato (such as Solanum lycopersicata (丄 or 链, a / ί ί 儿 儿), tomato (eg, Solanum solani or Intersprayed spores) and Alternaria (j/ier (10) η·α spp) on wheat (Alternaria alternata); sugar beet and snails on vegetables (1) (10) (10) hitting SPP·), the genus Sporococcus sp. on the genus and vegetables, such as wheat husks (baby anthracnose) on wheat and barley snail (丄/zorc/ez·) on barley,脐 转 ) 及 及 及 及 及 及 及 及 及 及 及 及 及 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有Umbilical umbilical cord spore Mountain 〇) and northern leaf blight (Cornus umbellatus) (such as, for example, the spot disease on cereals (wheat root rot 平 〇 〇 〇 〇 b b b ) ) ) ))) and such as rice and turf Helminthosporium variabilis; wheat powdery mildew (valley wwerz.a grawz.m) on cereals (such as wheat or barley) (formerly known as: buckwheat powder (£WZ&gt;/Ze ^(10)&amp;&amp;)) (powdery mildew); fruits and berries (such as strawberries), vegetables (such as lettuce, carrots, celery and cabbage), rapeseed, flowers, vine forest plants and wheat worms (Boiryi/s ckerea) (sexual t Botrytis cinerea (Boir less οίζϋ /wcAre/za/ia): gray mold); Phytophthora sinensis (Wan huiia / aciwcae) (Frost disease); broadleaf tree and $, 彔The genus of the fungus synonym (ph/osiowa) in the tree (rot or arboreal), such as the eucalyptus fungus on the eucalyptus (C. Dutch elm disease); For example, ash 147475.doc •92· 201043139 leaf spot. Corn leaf spot (c·(9), rice, sugar beet (eg beet brown spot disease (c., sugar cane, vegetables) , coffee, soybeans (such as C. sphaeroides (c. μ) or K. sphaeroides (Chmc/^·)) and the genus Cercoworaf Spp. (species of spotted pathogens) Add (for example, tomato leaf mold fungus (C.: leaf mold) and genus Phytophthora (C/ai/owor/ww spp.) on cereals, such as Phytophthora infestans on wheat (C_ black ear ( Biack ear)); ryegrass 〇 (.WC^ qing) (ergot) on the mites; corn (C. (10) fine), mites (such as Helminthosporium (Cm. v(10)), asexual: wheat root rot flat umbilical snail) and rice (eg uterus genus), asexual type: Helicobacter pylori (10) on C. cerevisiae (CW/^'oh/ Like) (asexual type: Helminthosporium umbellatus &&gt;0/π)) genus (leaf leaf spot); cotton (for example, cotton thorn spore (c. cultivar)), Maize (eg, Anthracnose stalk rot), non-nuclear fruit, potato mash (eg c. COCCOi 5^: black spot), beans (eg beans) Prickly ash (C. (5) heart (6) (10) please)) Soybean (eg, sphaeroides or sphaeroides) (C. sphaeroides) (sexual type: anthrax (G/〇were/(4)) genus (anthrax); genus C〇ri/c~m spp.), for example, C. wwHi (external sheath blight); P. sphaeroides on soybeans and ornamental plants _ this-) Disease); Cyclospora genus (9) (1) · spp ·), such as the genus Phytophthora capsici (C· 〇 / gflgz • (10) w); fruit trees, vines (such as Liriodendron (c. /ζ&gt;ζ·Μπ〇, sexual 147475.doc -93- 201043139 type: erythropoietin (iVeo«ecir/a: Black Foot Disease) and ornamental plants Helicobacter genus (Qy/k OCfl/po „ spp.) (eg if the tree ulcer or young vine declines, there is a genus: C. striata spp.) or the new genus Phytophthora (jVeonecirifl spp·) ); Demycophagus (Demaio/?/zora necairix) on soybean (sex type: Phytophthora (/?οπ//-·ύί)) (root and stem rot); Phytophthora spp. ), for example, the big black spot disease (Ζ), the falling off); jade Rice, cereals (such as barley (such as barley bacillus, net plaque), and wheat (such as D. cerevisiae (Drepen Mountain): brown spot)), Helminthosporium umbellata on rice and turf (synonymous spirospores 'sexual type: genus genus (Pyrenop/zora)) genus; vines on the vines (five Mo dheaw) (top blight, dry blight) Bacteria (F〇r»n'n&gt;〇Wa (synonym: Pseudomonas sinensis (/ϊ/2β//ζ•(10)$, Mediterranean porphyrit (jp. 咖士以厂训~), thick spores visible & 溘 (Phaeomoniella formerly known as thick bottle sign (P / zaeoacremom 'wm c / z / awj / c / osporz ^)), parasitic bottle bacteria {Phaeoacremonium and / or platyces genus (such as outside - / merk 0 heart Caffe); renju (Pear sputum bacillus (5. nectar 0), non-nuclear fruit (Raspberry sclerotia (Wan: charcoal disease) and vine (black acne cysts) ): anthracnose) on the genus Cysticer (Spiritual SPP.) 'Indica sphaeroides orjvzae' (leaf smut); Black genus on the wheat (five p/c〇ccwm spp) (black mold); beet (sweet Powdery mildew (5·^&amp;e)), vegetables (such as pea powdery mildew (£ p(5)))), such as Cucurbitaceae (eg, C. sphaeroides), 147475.doc -94- 201043139 Brassica napus, Brassica napus (for example, Rhizoctonia solani (5. Phytophthora (£r&gt;^z&gt;/ze spp.) (powder disease); Curvularia on fruit trees, vines and ornamental trees (5 /α?α) (Grape rot or top blight, asexual type: Lata pseudocyst / αία), synonym of Libertdla blepharis); Exos〇hi on corn 〖um) (synonym for Helminthosporium) genus (such as turcicum); Fusarium oxysporum (FMwri) on various plants (sex type: GiMere//a) Genus (wild wilt, root or stem rot), such as Fusarium graminearum (F. gra/m > 2ear«m) or yellow Fusarium (factory CM/worMm) on roots (eg wheat or barley) Rotten, spotted or head withered), Fusarium oxysporum on tomato (P., Fusarium solani (F s〇/am·) on soybean and Fusarium oxysporum on corn (F. veriz'e// // 〇WeiS); cereals (such as wheat or barley) and corn on the top of the sac with halogen (take-all); cereals (such as Gibberella serrata (G. "poster)) and rice (for example) G. /WA: wroi: Phytophthora spp.); vines, pome fruit and other plants on the small clusters (C? /omere//a and cotton anthracis (g·gossxpii) on cotton, Grainsajning complex on rice; Staphylococcus aureus on vine (1) (black rot); Rosaceae and胳 上 上 上 上 上 上 上 上 上 上 上 上 上 上 上 上 上 上 上 上 上 上 上 上 上 上 上 上 上 上 上 上 上 上 上 上 上 上 上 上 上 上 上 上 上 上 上 上 上 上 上 上 上 上 上 上Type: Helminthosporium); 镊 囷 s spp.), such as coffee on the glutinous 跪 录 ( ( playing vaiiairzx) (coffee leaf rust); vines on the plant brown spot pathogen 147475.doc • 95- 201043139 (/ 显娜咖咖ra) (synonym grape branching sputum 雠 雠; soy and cotton vegetables. Coccidioides (she (10) # 二 -) (synonym Bean globulin (house w (four)) (root and stem Rotten); #类 (for example, wheat or barley) on the snow emblem suspected bacteria (10) (four) and coffee (four) mva / e) (synonym „ 司 腐 腐 腐 腐 (心.,·___)) (Pink snow mold (pmk snow M〇ld)); powdery mildew on soybeans (minus (four) coffee" (four) heart / / like " powdery mildew"; brown rot fungus (from (10) out (1) 4 spp), such as stone fruit and other Rosaceae plants Brown fruit rot fungus (M, fruit plexus spores (M·State (3) (4) and brown rot fungus (M flower and blight, brown rot); sputum, banana, non-nuclear and ground fungus Genus spp.), such as the grass root knot nematode (m gramk/C0/a) on wheat (asexual type · wheat sphaeroides (&amp;pi〇ria ir^c〇, genus genus Sepia) Blotch)) or Filipino globosa on bananas (M / (/like (4) (biack sigatoka disease); cabbage (such as Brassica oleracea) (where 6rimiCaeh, rapeseed (such as parasitic downy mildew ( p. 'Onions (eg, onion downy mildew (household, in grass (tobacco downy mildew (where iahci«a)) and soy (such as soybean downy mildew (corpse maws/zwrica)) on the downy mildew (per〇„〇 ^p Ra Spp ) (downy mildew); Phakopsora pachyrhizi anti-3~ squamous squam (j&gt;. (Dalian rust); for example, vines (eg lemon dry blight (household. irac) /ze/p/n./a) and the genus Bacillus algae (household plus raiSp0ra)) and soybeans (such as the bean stem brown rot fungus (household, call the stem rot) on the genus i%.a/〇_〇ra spp.) 'Brassica oleifera black on the rapeseed and cabbage//.«gam) (root and stem rot) and sugar beet on the beet (corpse 6eiae) (root rot, Leaf spot and cockroach 147475.doc -96· 201043139 Inverted disease; geranium, vine (eg Phytophthora platensis (8 vzYz, co/a): leaf and leaf spot) and soybean (eg stem rot: kidney bean) The epidemic emblem has a sexual type: P. sylvestris (P/zomo/wb spp.) on soybean black spot disease (D 〇 〇 / ze ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ( ( ( ( Disease); various plants 'such as pepper and cucurbitaceae plants (such as Phytophthora capsici (household, soybean (such as Phytophthora sinensis (hu. wegawerwa) 'synonym Phytophthora sojae (eight)), horse yam and tomato (for example) To Phytophthora (P.: late blight) and broad-leaved trees (such as Phytophthora ssp. var. var. var. var. var. var. var. var. var. var. var. var. var.) (P/^io/?/2i/zora spp.) Root, leaf, fruit and stem rot); Plasmodiophora brassicae (Tumor disease), of the Brassica, Brassica napus and other plants, P/izsmopara spp. ), for example, Phytophthora platensis on vines (K. Wiico/a) (vine vine downy mildew) and sunflower bacillus on sunflower (P.; Rosaceae, hops, pears and non-nuclear) Poi/oi/7/merii spp. (powdery mildew), such as apple powdery mildew on apples (P. /ewcoiric/m); for example, alfalfa (such as barley and wheat) Polymyxa (P. gra/w/m··?)) and polysaccharides (Po/ywyxa spp.) on sugar beet (Polygonum (Z&gt;eioe)) and spread from it Viral disease; base rot fungus on cereals (eg wheat or barley) (·f^eMi/ocercoworeZ/ci /lerpoiric/io^fes) (eye point, sexual type: blast fungus (Γαρα/α; various Fake cream on plants Mildew mildew] 'For example, P. cwZjenhs on Cucurbitaceae or Pseudomonas sinensis on P. chinensis (P. Zzwwz 7z·); P. variabilis on vine plant 147475. Doc -97- 201043139 irac/2ezp/n/a) (red flre disease or Roche disease (r〇tbrenner,), anamorphic. Phytophthora (P/n'a/op/i〇ra) )); rust genus sPP.) (money disease) on various plants, such as cereals (such as wheat, barley or rye) and Lu Xun (such as genus Puccinia (/&gt;. Magic)) Brown rust (p (10)) (brown rust or leaf rust), stalk rust (p sand (strip rust or yellow rust), barley rust (corpse (dwarf rust), rust rust (household) · stem rust or black rust) or leaf rust (p (brown rust or leaf rust) · ' wheat sclerotium

Wk卬⑽仏)(無性型:内臍蠕孢)(褐斑病)或大麥上之圓 核腔菌(ρ·⑽叫(網斑病);梨胞黴屬(/v—kspp ),例 如稻上之水稻稻瘟病菌(/J 〇〇;zae)(有性型:稻瘟病菌 (从叹”叩〇Γί/2β以⑹幻,稻熱病)及草皮及穀類上之稻瘟病 菌(P.的卿);草皮、n米、小麥、棉、油菜、向日 六大丑甜菜、蔬菜及各種其他植物上之腐黴菌屬 (尔/Π謂spp.)(猝倒病)(例如終極腐黴菌(户m則所)或瓜 果腐黴菌(P. aphamderniaf麵));杈隔孢屬(尺㈣山❿ spp.W列如大麥上之膠西格寧柱隔孢㈣(柱隔 孢葉斑、生理學葉斑)及甜菜上之甜菜才主隔抱^ ϋ也); 2稻馬鈴薯、草皮、玉米、油菜、馬铃著、甜菜、蔬 菜及各種其他植物上之絲核菌屬J,例如 大旦上之立枯絲核菌(兄以/im/)(根及莖腐爛)、稻上之立枯 4核菌(外鞘枯萎病)或小麥或大麥上之禾穀絲核菌(及 ⑽;^)(絲核菌彈簀枯萎病(RhiZ〇Ct〇nia spring blight)); 草每胡蘿蔔、甘藍、藤本植物及番茄上之葡枝根黴 147475.doc -98- 201043139 {Rhizopus st〇lonifer从黑黴病、氡蔵病y,大參、禀、參反黑、 小麥上之大麥雲紋病菌(及(雲紋斑病 (scald)),稻上之帚梗柱孢(以及葉勒腐敗 菌(51· ⑼waiww)(鞘腐病);蔬菜及田間作物上之核盤菌屬 OSc/eroikM spp·)(莖腐爛或白黴病),諸如油菜、向曰葵 (例如函核病卤(iSWeroi/ηία ·5£;/βΓ〇ί!’〇ΓΜ»2))及大豆(例如齊整 小核菌(51. ro//Wi)或菌核病菌);各種植物上之殼針孢屬 spp.),例如大豆上之大豆褐紋菌(&amp; glebes)(褐 斑病)、小麥上之小麥殼針抱(^. iriiicz’)(殼針抱斑病)及穀 類上之穎枯殼針孢(S. «οί/orww)(同義詞穎枯殼針孢 (及agowwpora «ocforwm))(長穗菅茅斑葉病菌斑(Stagonospora blotch));藤本植物上之葡萄白粉病(t/«cz'«M/a «ecaior)(同 義詞粉黴病菌weeflior))(白粉病,無性型:葡萄 粉孢((%/iww iwcferz·));玉米(例如玉米大斑病菌(*S. iMrdcww), 同義詞玉米大斑病菌iwrc/cww))及草皮 上之刺球腔菌屬(《Seiospaer/a spp.)(葉枯病);玉米(例如絲 黑粉病菌(*S· re出απα):絲黑穗病(A:erneZ smwi))、高粱及甘 蔗上之軸黑粉菌屬(《S/7/zace/oi/zeca spp.)(黑穗病);葫蘆科 植物上之蒼耳單絲殼(&lt;S/?/zaer£?i/2eca/wngf«ea)(白粉病);馬 铃薯上之馬鈐薯粉痂菌(5^o«gO«sporc3! sMierrawea)(粉痂病) 及由此傳播之病毒性疾病;穀類上之長穗菅茅斑葉病菌屬 spp.),例如小麥上之穎枯殼針孢(51· «Οί/orww)(長 穗营茅斑葉病菌斑,有性型:小麥子囊菌(iepiojp/mer/a nodorum)[ 1¾ ^ =¾ /J&gt; ^ H ^ g (Phaeosphaeria nodorum)]; 147475.doc -99- 201043139 馬鈐薯上之馬鈴薯癌腫病菌Wohcwm)(馬 鈴薯癌腫病);外囊菌屬(rap/irha spp.),例如桃上之畸形 外囊菌(Γ· a?e/ormi^)(卷葉病)及李子上之李外囊菌(广 prw«z·)(李袋杲病);菸草、仁果、蔬菜、大豆及棉上之根 串珠黴屬(TTnWaWopWi spp.)(黑根腐病),例如根腐黴(τ\ Zjo^co/α)(同義詞根串珠徽(C/ia/ara ;穀類上之膜 黑粉菌屬(77//eii'G spp.)(普通黑穗病(common bunt)或腥黑 穗病(stinking smut)),諸如小麥上之小麥腥黑粉菌(厂 (同義詞小麥網腥黑穗病菌(r· Car/ej·),小麥腰黑穗 病(wheat bunt))及矮腰黑稳病菌(J·. ccmiroversa)(矮腫.黑穗 病(dwarf bunt));大麥或小麥上之麥類雪腐褐色小粒菌核 病菌(7&gt;p/2M/a z_«car„aM)(灰色雪黴病);條黑粉菌屬 (t/r〇Cp沿spp.),例如黑麥上之黑麥桿黑穗病菌(t/· (莖黑粉病);蔬菜上之單孢銹菌屬(〜⑽ SPP·)(錄病),e亥荨蔬菜為諸如豆(例如菜豆錄菌(y· 叩山·,同義詞豆單胞銹菌(ί/.如_〇/⑴及甜菜 (例如甜菜單孢銹菌(t/. ^仏勾);穀類(例如大麥散黑粉菌 (C/·⑽心)及燕麥散黑粉菌(r 、玉米(例如玉蜀黍 黑粉菌(t/. m叮山:玉米黑穗病)及甘蔗上之黑粉菌屬 (CAm/a抑spp·)(散黑穗病);蘋果(例如蘋果黑星菌(厂 小及梨上之黑星菌屬(R— spp)(恭病”及各 種植物(諸如水果及觀賞植物、藤本植物、無核果、蔬菜 及田間作物)上之輪枝菌屬·咖謂spp )⑺萎病),例 如草莓、油菜、馬鈴薯及番茄上 1为考汉隹力口上炙大理輪枝菌 147475.doc 201043139 dahliae)。 化合物I、II及IV及其組合物亦分別適用於在保護儲存之 產品或及收穫物及保護材料中防治有害真菌。術語「保護 材料」應理解為表示保護工業材料及非生活材料,諸如黏 著劑、膠、木材、紙及紙板、紡織品、皮革、油漆分散 液、塑膠、冷卻潤滑劑、纖維及織物以防有害微生物(諸 如真菌及細菌)侵染及破壞。在保護木材及其他材料時, 以下有害真菌尤其值得注意:子囊菌類(Ascomycetes),諸 如長喙殼黴屬則spp.)、青變真菌屬治 spp.)、出芽短梗徽(dwreoftasWM/w 、擬莖點黴屬 {Sclerophoma spp.)、毛殼菌屬(C/meio所z'ww spp.)、腐質黴 屬(T/wmz’co/α spp.)、彼得殼屬(Peirz'e//a spp.)、針葉莧屬 (TWc/zwrws spp.);擔子菌類(Basidiomycetes),諸如粉孢革 菌屬(Com’op/zora spp.)、革蓋菌屬(CoWo/ws spp.)、密褐褶 孔菌屬spp.)、香菇屬(Zewkws Spp·)、側耳 屬(P/ewroiw spp.)、茯苓屬(Ρ〇η·α spp.)、龍介蟲屬 (Serpw/a spp.)及乾齡·菌屬(Γ少romyce.·? spp.),半知菌類 (Deuteromycetes) ’ 諸如麴菌屬spp.)、分枝孢 子菌屬、青黴屬(户spp.)、木黴屬(7Wc/2〇rwa SPP·)、交鏈孢屬spp·)、擬青徽屬(尸 spp.),及接合菌類(Zygomycetes),諸如毛黴菌屬(Mweor spp.),且另外,在保護儲存之產品及收穫物中,以下酵母 真菌值得注意:念珠菌屬spp.)及釀酒酵母 (iSacc/zaromyce·? cerevbiie)。 147475.doc -101- 201043139 化合物I、II及IV及其組合物可分別用於改良植物健康。 本發明亦係關於一種藉由分別用有效量之化合物J、π及/ 或IV及其組合物處理植物、其繁殖材料及/或植物生長地 或預定生長地來改良植物健康的方法。 術語「植物健康」應理解為表示植物及/或其收穫物之 狀況,該狀況係根據數個指標(單獨或彼此組合)判定,該 等指標諸如產量(例如生物量提高及/或有價值成分含量提 间)、植物活力[例如植物生長加快及/或葉子更綠(「變綠 效應」)]、質(例如某些成分之含量或組成提高)及對非 生物及/或生物逆境之耐受性。以上鑑別之植物健康狀況 指標可互相依存或可互為因果。 式I、II及IV化合物可以可具有π生物活性之不同晶體 憂體存在。其同樣為本發明之標的。 化S物I II及IV可原樣或以組合物形式用於以殺真菌有 效量之活性物質處理真菌、欲保護以防真菌侵襲之或植 物、植物繁殖材料(諸如種子)、土壤、表面、材料或空 間。可在真菌感染植物、植物繁殖材料(諸如種子)、土 壌、表面、材料或空間之前與之後進行施用。 之前用化合物I、II及/或IV本身 π及/或IV之組合物預防性處理 可在種植或移植期間或 或包含至少一種化合物J、 植物繁殖材料。 本發明亦係關於包含溶劑或固體載劑及至少一種化合物 I、II及/或IV之農用化學組合物,及其防治有害真菌之用 途0 147475.doc •102- 201043139 農用化學組合物包含殺真菌有效量之化合物I、II及/或 IV。術語「有效量」表示組合物或化合物I、II及/或IV之 量足以防治栽培植物上之有害真菌或保護材料且不對所處 理之植物產生實質性損害。此量可在寬範圍内變化且視多 種因素而定,該等因素諸如欲防治之真菌物種、所處理之 栽培植物或材料、氣候條件及所使用之特定化合物。 化合物I、II及IV及其鹽可轉化成常用類型之農用化學組 合物,例如溶液、乳液、懸浮液、撒粉、粉劑、糊劑及顆 ® 粒劑。組合物類型視特定預定目的而定;在各情況下,其 應確保本發明化合物之精細且均一的分佈。 組合物類型之實例為懸浮液(SC、OD、FS)、可乳化濃 縮物(EC)、乳液(EW、EO、ES)、糊劑 '片劑、可濕性粉 劑或撒粉(WP、SP、SS、WS、DP、DS)或顆粒劑(GR、 FG、GG、MG)(其可具水溶性或可濕性),以及用於處理諸 如種子之植物繁殖材料之凝膠調配物(GF)。 ^ 組合物類型(例如 SC、OD、FS、EC、WG、SG、WP、 〇 SP、SS、WS、GF)通常稀釋後使用。諸如DP、DS、GR、 FG、GG及MG之組合物類型通常不稀釋即使用。 . 組合物係以已知方式製備(參看US 3,〇6〇,084、EP-A 707Wk卬(10)仏) (asexual type: umbilical cord blood snail) (brown spot disease) or nucleus on the barley (ρ·(10) called (net spot disease); Pythium genus (/v-kspp), For example, rice blast fungus (/J 〇〇; zae) on rice (sex type: rice blast fungus (from sigh) 叩〇Γί/2β to (6) illusion, rice fever) and blast fungus on turf and cereal ( P. qing); turf, n meters, wheat, cotton, rapeseed, six ugly beets, vegetables and various other plants on the genus Pythium (or / Π spp.) (such as the disease) (such as the ultimate Pythium (household m) or Pythium pyogenes (P. aphamderniaf)); genus sphaeroides (small (four) hawthorn spp. W column such as barley on the gelatin sigma column (4) Leaf spot, physiological leaf spot) and sugar beet on beet are separated by ^ ^ ϋ also); 2 rice potato, turf, corn, rape, horse bell, beet, vegetables and various other plants on the genus Rhizoctonia J For example, Rhizoctonia solani (Brother's /im/) (root and stem rot), Rhizoctonia solani (Sheath wilt) on rice or Rhizoctonia cerealum on wheat or barley (and (10); ^) (silk core Rhizoctonia wilt (RhiZ〇Ct〇nia spring blight)); Rhizopus oryzae per carrot, cabbage, vine and tomato 147475.doc -98- 201043139 {Rhizopus st〇lonifer from black mold, 氡蔵Disease y, ginseng, medlar, ginseng, black, wheat barley algae (and (scald)), onion on the rice stalk (and spleen spores (51 · (9) waiww) ( Sheath rot); Sclerotinia sp. OSc/eroikM spp·) on vegetables and field crops (stalk rot or white mold), such as rapeseed, hollyhock (eg, nucleus nucleus (iSWeroi/ηία · 5£; /βΓ〇ί!'〇ΓΜ»2)) and soybeans (eg, sclerotium (51. ro//Wi) or Sclerotinia sclerotiorum); various plants on the genus Septoria spp.), such as soybeans & glebes (brown spots), wheat husks on wheat (^. iriiicz') (shell stalk disease) and sclerotium on cereals (S. «οί/ Orww) (synonym sphaeroides (and agowwpora «ocforwm)) (Stagonospora blotch); grape powdery mildew on vine (t/«cz'«M/a «ecaior ) "Flycacum, asexual type: grape powder spore ((%/iww iwcferz)); corn (such as corn leaf spot (*S. iMrdcww), synonymous with I. cerevisiae iwrc/ Cww)) and the genus of the genus (Seiospaer/a spp.) (leaf blight); corn (eg, smut (*S·re out απα): smut (A: erneZ) Smwi)), sorghum and sugarcane on the genus Sphaerotheca (S/7/zace/oi/zeca spp.) (smut); the scorpion monofilament shell on the cucurbitaceae (&lt;S/? /zaer£?i/2eca/wngf«ea) (powder disease); potato meal on the potato (5^o«gO«sporc3! sMierrawea) (Powder disease) and the virus transmitted thereby Sexually transmitted diseases; the genus Sporotrichum spp.) on cereals, such as the genus Astragalus membranaceus (51· «Οί/orww) (Saccharomyces cerevisiae plaque, sexual type: wheat Ascomycetes (iepiojp/mer/a nodorum) [ 13⁄4 ^ =3⁄4 /J&gt; ^ H ^ g (Phaeosphaeria nodorum)]; 147475.doc -99- 201043139 Potato disease on the potato (Wohcwm) (potato cancer) ; rap/irha spp., such as peach Outer sclerotia (Γ· a?e/ormi^) (curved leaf disease) and Lee sclerotia on the plum (Guang prw«z·) (Li bag disease); tobacco, pome fruit, vegetables, soybeans and TTnWaWopWi spp. (black root rot) on cotton, such as Pythium fulvum (τ\ Zjo^co/α) (synonym string beaded emblem (C/ia/ara; film black powder on cereals) Genus (77//eii'G spp.) (common bunt or stinking smut), such as wheat smut on wheat (plant (synonym wheat net 腥 black spike) Pathogens (r· Car/ej·), wheat smut (wheat bunt) and dwarf steadily (J. ccmiroversa) (dwarf bunt); barley or wheat Wheat snow rot brown sclerotia (7&gt;p/2M/a z_«car„aM) (grey snow mold); genus genus (t/r〇Cp along spp.), such as rye Ryegrass smut (t/· (stem smut); Phytophthora ssp. (~(10) SPP·) on vegetables (recorded), ehai 荨 vegetables such as beans (eg, peas ( y· 叩山·, the synonym of Phytophthora sojae (ί/.such as _〇/(1) and beets (such as sweet-type spore rust t/. ^仏)); cereals (such as barley powdery mildew (C / · (10) heart) and oat powder black powder (r, corn (such as maize black powder fungus (t /. m叮 mountain: corn black ear Disease) and the genus Phytophthora (CAm/a spp·) on the sugar cane (san smut); apple (such as the black bacterium of the apple (plant small and the genus of the genus R. spp) Diseases and various plants (such as fruits and ornamental plants, vines, non-seeds, vegetables and field crops) on the genus Verticillium sp.) (7) wilting), such as strawberries, canola, potatoes and tomatoes. Kaohan 隹 炙 炙 炙 炙 炙 147 147 147 147 147475.doc 201043139 dahliae). Compounds I, II and IV and combinations thereof are also suitable for controlling harmful fungi in protected storage products or in harvested and protective materials, respectively. The term "protective material" is understood to mean the protection of industrial and non-living materials such as adhesives, glues, wood, paper and cardboard, textiles, leather, paint dispersions, plastics, cooling lubricants, fibres and fabrics to prevent harmful microorganisms. Infection and destruction (such as fungi and bacteria). In the protection of wood and other materials, the following harmful fungi are particularly noteworthy: Ascomycetes (such as the genus Aspergillus sp.), the genus of the fungus (spp.), the dwarf stalk (dwreoftasWM/w, {Sclerophoma spp.), Chaetomium (C/meio z'ww spp.), Humicola (T/wmz'co/α spp.), Peerz'e //a spp.), TWc/zwrws spp.; Basidiomycetes, such as Com'op/zora spp., Cochleobacter (CoWo/ws spp) .), Pleurotus spp.), Zewkws Spp·, P/ewroiw spp., Ρ〇η·α spp., genus Serpw/a Spp.) and dry age · genus (Γ romyce.·? spp.), deuteromycetes (Deuteromycetes) 'such as sputum spp.), mycobacteria, Penicillium (spp.), wood Mycorrhizal (7Wc/2〇rwa SPP·), Alternaria spp.), Pseudostellaria (Spp.), and Zygomycetes, such as Mweor spp., and additionally, In the protection of stored products and harvests, the following yeast fungi Notable: Candida spp.) and Saccharomyces cerevisiae (iSacc/zaromyce·? cerevbiie). 147475.doc -101- 201043139 Compounds I, II, and IV, and combinations thereof, can be used to improve plant health, respectively. The invention is also directed to a method of improving plant health by treating plants, their propagation material and/or plant growth or intended growth with an effective amount of Compound J, π and/or IV, and combinations thereof, respectively. The term "plant health" is understood to mean the condition of a plant and/or its harvest, which is determined on the basis of several indicators, either alone or in combination with one another, such as yield (eg biomass increase and/or valuable components). (extraction), plant vigor [eg plant growth accelerated and / or greener leaves ("greening effect")], quality (such as increased content or composition of certain ingredients) and resistance to abiotic and / or biological stress Receptive. The plant health indicators identified above may be interdependent or interdependent. The compounds of formulae I, II and IV may exist in different crystals with π biological activity. It is also the subject of the invention. The S substances I II and IV can be used as such or in the form of a composition for treating fungi with a fungicidally effective amount of an active substance, to protect against fungal attack or plants, plant propagation materials (such as seeds), soil, surface, materials Or space. Administration can be carried out before and after the fungal infection of the plant, plant propagation material (such as seeds), soil, surface, material or space. Prophylactic treatment with a combination of compounds I, II and/or IV itself π and/or IV may be followed by or during the implantation or transplantation of at least one compound J, a plant propagation material. The invention also relates to an agrochemical composition comprising a solvent or solid carrier and at least one compound I, II and/or IV, and the use thereof for controlling harmful fungi. 0 147475.doc • 102- 201043139 Agrochemical composition comprising fungicidal An effective amount of Compound I, II and/or IV. The term "effective amount" means that the amount of the composition or compound I, II and/or IV is sufficient to control harmful fungi or protective materials on cultivated plants without substantial damage to the treated plant. This amount can vary widely and depends on a number of factors such as the species of fungus to be controlled, the cultivated plant or material being treated, the climatic conditions and the particular compound employed. The compounds I, II and IV and their salts can be converted into a common type of agrochemical composition such as solutions, emulsions, suspensions, dusting powders, powders, pastes and granules. The type of composition will depend on the particular intended purpose; in each case it should ensure a fine and uniform distribution of the compounds of the invention. Examples of composition types are suspensions (SC, OD, FS), emulsifiable concentrates (EC), emulsions (EW, EO, ES), pastes 'tablets, wettable powders or dusting powders (WP, SP) , SS, WS, DP, DS) or granules (GR, FG, GG, MG) (which may be water soluble or wettable), and gel formulations for treating plant propagation materials such as seeds (GF ). ^ Composition type (eg SC, OD, FS, EC, WG, SG, WP, 〇 SP, SS, WS, GF) is usually used after dilution. Composition types such as DP, DS, GR, FG, GG, and MG are usually used without dilution. The composition is prepared in a known manner (see US 3, 〇6〇, 084, EP-A 707)

445(關於液體濃縮物);Browning:「Agglomeration」, Chemical Engineering,1967 年 12 月 4 日,147-48,Perry's Chemical Engineer's Handbook,第 4 版,McGraw-Hill, New York,1963,第 8-57 頁及其後内容;WO 91/13546、 US 4,172,714 &gt; US 4,144,050 ' US 3,920,442、US 147475.doc -103- 201043139 5,180,587、US 5,232,701、US 5,208,030、GB 2,095,558、 US 3,299,566 ; Klingman: Weed Control as a Science (J. Wiley &amp; Sons, New York, 1961) ; Hance等人:Weed Control Handbook(第 8 版,Blackwell Scientific,Oxford, 1989)及 Mollet,H_及Grubemann, A·: Formulation technology (Wiley VCH Verlag,Weinheim,2001))。 農用化學組合物亦可包含農用化學組合物中常用之助 劑。分別視特定施用形式及活性物質選擇所使用之助劑。 適合助劑之實例為溶劑、固體載劑、分散劑或乳化劑 (諸如其他增溶劑、保護性膠體、界面活性劑及黏著劑)、 有機及無機增稠劑、殺細菌劑、防珠劑、消泡劑、(適當 時)著色劑及增黏劑或黏合劑(例如用於種子處理調配物)。 適合溶劑為水、有機溶劑,諸如具有中等沸點至高沸點 之礦物油鶴份,諸如煤油或柴油,此外為煤焦油及植物或 動物來源之油;脂族烴、環烴及芳族烴,例如曱苯、二曱 基、石蝶、四氫萘、烧基化萘或其衍生物;醇,諸如曱 醇、乙醇、丙醇、丁醇及環己醇;二醇;酮,諸如環己 酮;及γ- 丁内酯、脂肪酸二甲醯胺、脂肪酸及脂肪酸酯及 強極性溶劑,例如胺,諸如Ν-甲基α比略α定酮。 固體載劑為礦質土,諸如矽酸鹽、矽膠、滑石、高嶺 土、石灰石、石灰、白堊、紅玄武土、黃土、黏土、白雲 石、矽藻土、硫酸鈣、硫酸鎂、氧化鎂、經研磨合成材 料、肥料,諸如硫酸銨、填酸銨、确酸銨、尿素,及植物 來源之產品,諸如穀粕、樹皮粕、木屑及堅果殼粕、纖維 147475.doc -104- 201043139 素粉及其他固體載劑。 適合界面活性劑(佐劑、濕潤劑、增黏劑、分散劑或乳 化劑)為芳族續酸(諸如木質素續酸(Borresperse®型, Borregard, Norway)、苯朌石黃酸、萘石黃酸(Morwet®型, Akzo Nobel,U.S.A.)及二丁基萘磺酸(Nekal® 型,BASF, Germany))及脂肪酸之驗金屬鹽、驗土金屬鹽及銨鹽;烧 基石黃酸S旨、烧基芳基績酸目旨、烧基硫酸醋、月桂基醚硫酸 酯、脂肪醇硫酸酯,及硫酸化十六醇鹽、硫酸化十七醇鹽 π ^ 及硫酸化十八醇鹽、硫酸化脂肪醇二醇醚;此外以及萘或 萘磺酸與苯酚及甲醛之縮合物;聚氧化乙烯辛基苯基醚、 乙氧基化異辛基苯酚、辛基苯酚、壬基苯酚、烷基苯基聚 二醇醚、三丁基苯基聚二醇醚、三硬脂醯基苯基聚二醇 醚、烷基芳基聚醚醇、醇及脂肪醇/環氧乙烷縮合物、乙 氧基化萬麻油、聚氧化乙稀烧基醚、乙氧基化聚氧化丙 烯、月桂醇聚二醇醚縮醛、山梨糖醇酯、木質素亞硫酸鹽 ^ 廢液,及蛋白質、變性蛋白質、多醣(例如曱基纖維素)、 疏水性改質澱粉、聚乙烯醇(Mowiol®型,Clariant, Switzerland)、聚叛酸醋(Sokolan®型,BASF, Germany)、 聚炫氧基化物、聚乙烯胺(Lupasol®型,BASF, Germany)、 聚乙烯吡咯啶酮及其共聚物。 增稠劑(亦即賦予組合物改良之流動性(亦即靜止條件下 具高黏度及攪拌期間具低黏度)的化合物)之實例為多醣及 有機及無機黏土,諸如三仙膠(Xanthan gum)(Kelzan®,CP Kelco, U.S.A.) ' Rhodopol® 23(Rhodia, France) ' Veegum® 147475.doc -105- 201043139 (R.T. Vanderbilt, U.S.Α·)或 Attaclay® (Engelhard Corp·,NJ, USA)。 可添加殺細菌劑以保存及安定組合物。適合殺細菌劑之 貝例為基於以下之极細鹵劑:雙氯紛(dichlorophene)及苯 甲醇半曱縮醛(ICI 之 Proxel®,或 Thor Chemie 之 Acticide® RS,及Rohm &amp; Haas之Kathon® MK),及異噻唑啉_衍生 物,諸如烧基異嗟嗤啉酮及苯并異噻唑啉酮(Th〇r chemie 之 Acticide® MBS)。 適合防凍劑之實例為乙二醇、丙二醇、尿素及甘油。 消泡劑之實例為聚矽氧乳液(諸如Siiikon® SRE, Wacker,445 (About Liquid Concentrates); Browning: "Agglomeration", Chemical Engineering, December 4, 1967, 147-48, Perry's Chemical Engineer's Handbook, 4th Edition, McGraw-Hill, New York, 1963, 8-86 Pages and subsequent content; WO 91/13546, US 4,172,714 &gt; US 4,144,050 ' US 3,920,442, US 147475.doc -103-201043139 5,180,587, US 5,232,701, US 5,208,030, GB 2,095,558, US 3,299,566; Klingman: Weed Control as a Science (J. Wiley &amp; Sons, New York, 1961); Hance et al.: Weed Control Handbook (8th edition, Blackwell Scientific, Oxford, 1989) and Mollet, H_ and Grubemann, A: Formulation technology (Wiley VCH Verlag , Weinheim, 2001)). The agrochemical composition may also contain adjuvants commonly used in agrochemical compositions. The adjuvants used are selected depending on the particular application form and the active substance. Examples of suitable auxiliaries are solvents, solid carriers, dispersants or emulsifiers (such as other solubilizers, protective colloids, surfactants and adhesives), organic and inorganic thickeners, bactericides, anti-beads, Defoamers, (where appropriate) colorants and tackifiers or binders (for example for seed treatment formulations). Suitable solvents are water, organic solvents, such as mineral oil cranes with medium to high boiling points, such as kerosene or diesel, in addition to coal tar and oils of vegetable or animal origin; aliphatic hydrocarbons, cyclic hydrocarbons and aromatic hydrocarbons such as hydrazine a benzene, a dimercapto group, a stone butterfly, a tetrahydronaphthalene, an alkylated naphthalene or a derivative thereof; an alcohol such as decyl alcohol, ethanol, propanol, butanol and cyclohexanol; a diol; a ketone such as cyclohexanone; And γ-butyrolactone, fatty acid dimethylamine, fatty acids and fatty acid esters and strong polar solvents such as amines, such as hydrazine-methyl alpha ratio serotonin. The solid carrier is mineral soil, such as silicate, tannin, talc, kaolin, limestone, lime, chalk, red basalt, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground Synthetic materials, fertilizers, such as ammonium sulphate, ammonium sulphate, ammonium sulphate, urea, and plant-derived products such as gluten, bark, wood chips and nut clams, fiber 147475.doc -104- 201043139 plain powder and others Solid carrier. Suitable surfactants (adjuvants, wetting agents, tackifiers, dispersants or emulsifiers) are aromatic acid (such as lignin continuous acid (Borresperse® type, Borregard, Norway), benzoquinic acid, naphthalene Yellow acid (Morwet® type, Akzo Nobel, USA) and dibutylnaphthalenesulfonic acid (Nekal® type, BASF, Germany)) and metal salts, soil test metal salts and ammonium salts of fatty acids; , aryl aryl hydroxy acid, burnt sulphuric acid vinegar, lauryl ether sulfate, fatty alcohol sulphate, and sulfated cetyl salt, sulfated heptadecyl π ^ and sulfated stearyl salt, Sulfated fatty alcohol glycol ether; in addition to condensate of naphthalene or naphthalenesulfonic acid with phenol and formaldehyde; polyoxyethylene octylphenyl ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkane Phenyl polyglycol ether, tributyl phenyl polyglycol ether, tristearyl nonyl phenyl polyglycol ether, alkyl aryl polyether alcohol, alcohol and fatty alcohol / ethylene oxide condensate, Ethoxylated cannabis oil, polyoxyethylene ether alkyl ether, ethoxylated polypropylene oxide, lauryl alcohol polyglycol ether acetal, mountain Sugar alcohol esters, lignin sulfites ^ waste liquids, and proteins, denatured proteins, polysaccharides (such as mercapto cellulose), hydrophobic modified starch, polyvinyl alcohol (Mowiol® type, Clariant, Switzerland), polyphenolic acid Vinegar (Sokolan® type, BASF, Germany), polydecyloxylate, polyvinylamine (Lupasol® type, BASF, Germany), polyvinylpyrrolidone and copolymers thereof. Examples of thickeners (i.e., compounds which impart improved fluidity to the composition (i.e., compounds having high viscosity at rest and low viscosity during agitation) are polysaccharides and organic and inorganic clays such as Xanthan gum. (Kelzan®, CP Kelco, USA) 'Rhodopol® 23 (Rhodia, France) ' Veegum® 147475.doc -105- 201043139 (RT Vanderbilt, USΑ·) or Attaclay® (Engelhard Corp., NJ, USA). A bactericide can be added to preserve and stabilize the composition. Suitable bactericides are based on the following very fine halogens: dichlorophene and benzyl alcohol hemiacetal (Proxel® from ICI, or Acticide® RS from Thor Chemie, and Kathon from Rohm &amp; Haas) ® MK), and isothiazoline derivatives such as ketone isoindolinone and benzisothiazolinone (Acticide® MBS from Th〇r chemie). Examples of suitable antifreeze agents are ethylene glycol, propylene glycol, urea and glycerin. An example of a defoamer is a polyoxyl emulsion (such as Siiikon® SRE, Wacker,

Germany 或 Rhodorsil,Rhodia, France)、長鏈醇、脂肪 酸、脂肪酸之鹽、氟有機化合物及其混合物。 適合著色劑為低水溶性顏料及水溶性染料。可提及之實 例有以下名稱:若丹明B(rhodamin B)、C. I.顏料紅112、 C. L溶劑紅1、顏料藍15:4、顏料藍15:3、顏料藍15:2、顏 料藍15:1、顏料藍8〇、顏料黃i、顏料黃13、顏料紅丨丨之、 顏料紅48:2、顏料紅48:1、顏料紅57:1、顏料紅53:',、 料橙43、顏料橙34、顏料橙5、顏料綠%、顏料綠7、顏料 白6顏料杬25、驗性紫1 〇、驗性紫49、酸性紅5 1、酸性 紅52、酸性紅14、酸性藍9、酸性黃23、鹼性紅1〇、鹼怡 紅 108。 曰站齊|或黏合劑之實例為聚乙烯吡咯啶酮、聚乙酸乙烯 醋、聚乙烯醇及纖維㈣(Tyl〇se⑧,Shin_Etsu, Japan)。 粉劑、展佈用物質及撒粉可藉由將化合物I及適當時其 147475.doc -106- 201043139 他質與至少一種固體載劑混合或同時研磨來製備。 «由使活性物質與固體载劑黏結來製備顆粒 包覆包衣之顆粒劑、浸潰顆粒劑及均質顆粒劑。固體裁 之實例為料丨,諸如㈣、料鹽、滑石 1 :活性广石灰石、石灰、白耍、紅玄武土、黃土 :; 白农石、矽藻土、硫酸鈣、硫酸鎂、氧化鎂、經研磨 之合成材料、肥料,諸如硫酸銨'磷酸銨、硝酸銨、尿 ΟGermany or Rhodorsil, Rhodia, France), long chain alcohols, fatty acids, salts of fatty acids, fluoroorganic compounds and mixtures thereof. Suitable colorants are low water soluble pigments and water soluble dyes. Examples which may be mentioned are the following names: rhodamin B, CI Pigment Red 112, C. L Solvent Red 1, Pigment Blue 15:4, Pigment Blue 15:3, Pigment Blue 15:2, Pigment Blue 15:1, pigment blue 8〇, pigment yellow i, pigment yellow 13, pigment red 丨丨, pigment red 48:2, pigment red 48:1, pigment red 57:1, pigment red 53: ',, orange 43, Pigment Orange 34, Pigment Orange 5, Pigment Green%, Pigment Green 7, Pigment White 6 Pigment 杬25, Authentic Violet 1 〇, Verification Violet 49, Acid Red 5 1, Acid Red 52, Acid Red 14, Acidity Blue 9, acid yellow 23, alkaline red 1 〇, alkali euphoria 108. Examples of the binders or binders are polyvinylpyrrolidone, polyvinyl acetate vinegar, polyvinyl alcohol and fibers (T) (Tyl〇se8, Shin_Etsu, Japan). Powders, spreading materials and dusting can be prepared by mixing Compound I and, if appropriate, 147475.doc-106-201043139 with at least one solid carrier or simultaneously grinding. «Preparation of granules coated with granules, impregnated granules and homogeneous granules by bonding the active substance to a solid carrier. Examples of solid cutting are materials, such as (four), salt, talc 1: active limestone, lime, white play, red basalt, loess:; white agro-stone, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, Grinded synthetic materials, fertilizers, such as ammonium sulfate 'ammonium phosphate, ammonium nitrate, urinary hydrazine

,,及植物來源之產品,諸如榖粕、樹皮粕、木屑及堅果 喊粕、纖維素粉及其他固體載劑。 組合物類型之實例為: 1 ·用水稀釋之組合物類型 i)水溶性濃縮物(SL、LS) 1〇重量份本發明化合物溶解於9〇重量份水或水溶性溶劑 中。作為替代,添加濕潤劑或其他助劑。以水稀釋後,活 性物質溶解。以此方式獲得活性物質含量為1〇重量%之組 合物。 可分散濃縮物(DC) 2〇重ΐ份本發明化合物在添加丨〇重量份分散劑(例如聚 乙烯吡咯啶酮)下溶解於70重量份環己酮中。用水稀釋得 到分散液。活性物質含量為20重量。/t^ ’ iii)可乳化濃縮物(EC) 1 5重量份本發明化合物在添加十二烷基苯磺酸鈣及蓖麻 油乙氧基化物(各5重量份)下溶解於75重量份二曱苯中。用 水稀釋得到乳液。組合物之活性物質含量為15重量%。 147475.doc -107- 201043139 iv) 乳液(EW、EO、ES) 25重量份本發明化合物在添加十二烷基苯磺酸鈣及蓖麻 油乙氧基化物(各為5重量份)下溶解於35重量份之二甲苯 中。藉助於乳化機(Ultraturrax)將此混合物引入3〇重量份 水中且製成均質乳液。用水稀釋得到乳液。組合物之活性 物質含量為25重量%。 v) 懸浮液(SC、OD、FS;) 在攪拌式球磨機中,在添加1〇重量份分散劑及濕潤劑及 重量份水或有機溶劑下,磨碎2〇重量份本發明化合物, 得到精細活性物質懸浮液。用水稀釋得到活性物質之穩定 懸〉于液。組合物之活性物質含量為20重量%。 V1)水可分散性顆粒劑及水溶性顆粒劑(WG、Sg) 在添加50重量份分散劑及濕潤劑下,精細研磨5〇重量份 月化s物’且藉助於技術設備(例如擠壓、喷霧级、 抓體化床)製成水可分散或水溶性顆粒劑。用水稀釋得到 t物質之穩定分散液或溶液。組合物之活性物質含量為 5 0重量。/。。 vl〇水可分散性粉劑及水溶性粉劑(wp、、μ、 劍ΓΗ-定子研磨機中’在添加25重量份分散劑、濕潤 膠下,研磨75重量份本發明化合物。用水稀釋 活性物皙夕接〜、 τ %、疋为散液或溶液。組合物之活性物質含 75重量。里為 viii)凝膠(GF) 在授拌式球磨機中,在添加1G重量份分散劑、^重量份 147475.doc 201043139 膝喊劑濕潤劑及70重量份水或有機溶劑下,研磨2〇重量份 本發明化合物’得到活性物質之精細懸浮液。用水稀釋得 到活性物質之穩定懸浮液,藉此獲得含2〇% (w/w)活性物 質之組合物。 2.不經稀.釋即施用之組合物類型 可撒佈粉劑(DP、DS) 精細研磨5重量份本發明化合物且與95重量份細粉狀高 q 嶺土緊密混合。由此得到活性物質含量為5重量%之可撒 佈組合物。 X)顆粒劑(GR、FG、GG、MG) 精細研磨〇.5重量份本發明化合物且與99.5重量份載劑合 併。目丽方法為擠壓、噴霧乾燥或流體化床。由此得到活 性物質含量為〇·5重量%之不經稀釋即施用之顆粒劑。 xi) ULV溶液(UL) 1 〇重里伤本發明化合物溶解於90重量份有機溶劑(例如 〇 二甲苯)中。由此得到活性物質含量為10重量%之不經稀釋 即施用之組合物。 農用化學組合物—般包含0.01重量%至95重量%、較佳 0’1重里%至90重置%、最佳〇 5重量%至9〇重量。之活性物 . 質。活性物質係以90%至100%,車交佳95〇/〇至100%之純度, and plant-derived products such as alfalfa, bark, wood chips and nuts shouting, cellulose powder and other solid carriers. Examples of the type of the composition are: 1) Type of the composition diluted with water i) Water-soluble concentrate (SL, LS) 1 part by weight of the compound of the present invention is dissolved in 9 parts by weight of water or a water-soluble solvent. Instead, a wetting agent or other auxiliaries are added. After dilution with water, the active substance dissolves. In this way, a composition having an active substance content of 1% by weight was obtained. Dispersible Concentrate (DC) 2 〇 The compound of the present invention is dissolved in 70 parts by weight of cyclohexanone with the addition of a hydrazine dispersant (e.g., polyvinylpyrrolidone). Dilute with water to obtain a dispersion. The active substance content was 20% by weight. /t^ ' iii) emulsifiable concentrate (EC) 15 parts by weight of the compound of the invention dissolved in 75 parts by weight of the calcium dodecylbenzene sulfonate and castor oil ethoxylate (each 5 parts by weight) In benzene. Dilute with water to give an emulsion. The active substance content of the composition was 15% by weight. 147475.doc -107- 201043139 iv) Emulsion (EW, EO, ES) 25 parts by weight of a compound of the invention dissolved in calcium dodecylbenzenesulfonate and castor oil ethoxylate (each 5 parts by weight) 35 parts by weight of xylene. This mixture was introduced into 3 parts by weight of water by means of an emulsifier (Ultraturrax) and a homogeneous emulsion was prepared. Dilute with water to give an emulsion. The active substance content of the composition was 25% by weight. v) suspension (SC, OD, FS;) in agitated ball mill, adding 1 part by weight of dispersant and wetting agent and parts by weight of water or organic solvent, grinding 2 parts by weight of the compound of the invention, to obtain fine Active substance suspension. Dilute with water to obtain a stable suspension of the active substance. The active substance content of the composition was 20% by weight. V1) Water-dispersible granules and water-soluble granules (WG, Sg) finely grind 5 parts by weight of a sulphate s by adding 50 parts by weight of a dispersant and a wetting agent and by means of technical equipment (for example, extrusion) , spray grade, grabbed bed) made of water-dispersible or water-soluble granules. Dilute with water to obtain a stable dispersion or solution of the t substance. The composition has an active substance content of 50% by weight. /. . Vl water-dispersible powder and water-soluble powder (wp, μ, shovel-stator grinder) under the addition of 25 parts by weight of a dispersant, a wet gel, grinding 75 parts by weight of the compound of the invention. The active substance is diluted with water 皙Evening ~, τ %, 疋 is a dispersion or solution. The active substance of the composition contains 75 parts. The inside is viii) gel (GF) in the mixing ball mill, adding 1G parts by weight of dispersant, ^ parts by weight 147475.doc 201043139 Kneeling agent wetting agent and 70 parts by weight of water or organic solvent, grinding 2 parts by weight of the compound of the invention 'to obtain a fine suspension of the active substance. A stable suspension of the active substance is obtained by dilution with water, whereby a composition containing 2% by weight (w/w) of the active substance is obtained. 2. Type of composition to be applied without dilution. The powder (DP, DS) can be finely ground to 5 parts by weight of the compound of the present invention and intimately mixed with 95 parts by weight of fine powdery high q-casting clay. Thus, a spreadable composition having an active material content of 5% by weight was obtained. X) Granules (GR, FG, GG, MG) Finely ground. 5 parts by weight of a compound of the invention and combined with 99.5 parts by weight of a carrier. The method is extrusion, spray drying or fluidized bed. Thus, granules which were applied without dilution at an active substance content of 〇·5% by weight were obtained. Xi) ULV solution (UL) 1 〇 Heavy injury The compound of the present invention is dissolved in 90 parts by weight of an organic solvent (e.g., xylene). Thus, a composition which was applied without dilution at an active substance content of 10% by weight was obtained. The agrochemical composition generally comprises from 0.01% to 95% by weight, preferably from 0'1% by weight to 90% by weight, most preferably from 5% by weight to 9% by weight. Active substance. Quality. The active substance is 90% to 100%, and the car is 95%/〇 to 100% pure.

(根據NMR光譜)使用。. A 水溶性濃縮物(LS)、可流動濃縮物(FS)、乾燥處理用粉 劑(DS)'漿液處理用水可分散性粉劑(ws)、可溶性粉劑 ()乳液(ES)、可乳化濃縮物(EC)及凝膠(GF)通常用於 147475.doc •109- 201043139 處理植物繁殖材料(尤其種子)之目的。此等組合物可在稀 釋後或不經稀釋即施用於植物繁殖材料(尤其種子)。所討 論之組合物在稀釋2至10倍後,即用型製劑之活性物質濃 度為〇·〇1重量%至60重量%,較佳為〇」重量%至4〇重量%。 可在播種之前或播種期間進行施用。將農用化學化合物及 其組合物分別施用或處理於植物繁殖材料(尤其種子)上之 方法為此項技術中所已知,且包括繁殖材料之敷裹、塗 覆、成粒、撒粉、浸潰及溝内(in_furr〇w)施用方法。在一 較佳實施例巾,利不誘導發芽之方法(例如摔種、成 粒、塗覆及撒粉)在植物繁殖材料上分別施用化合物或其 組合物。 在一較佳實施例中,使用懸浮液型(FS)組合物進行種子 處理。FS組合物通常包含⑴⑻…活性物質、a2〇〇 界面活性劑、〇至20〇 Μ防凍劑、〇至400 g/1黏合劑、〇至 200 g/Ι顏料及至多}公升溶劑(較佳為水)。 5亥等活性物質可藉助於噴m、霧化、撒粉、展佈、刷 塗、浸潰或傾倒按原樣使用A以其組合物形式使用,例如 以可直接喷灑之溶液、粉劑、懸浮液、分散液、乳液、油 刀政液、糊劑、可撤佈產品、展佈用物質或顆粒劑之形式 使用施用形式^全視預^目的而^ ;意欲4保在各情況 下本發明之活性物質得以儘可能精細地分佈。 水性施用形式可自乳液濃縮物、糊劑或可濕性粉劑(可 喷灑粉劑、油分散液)藉由添加水來製備。為製備乳液、 糊劑或油分散液’可藉助於濕潤劑、增黏劑、分散劑或乳 147475.doc •110- 201043139 化劑將物貝(原樣或已溶解於油或溶劑中)均質化於水中。 或者,可製備由活性物質、濕潤劑、增黏劑、分散劑或乳 化劑及適當時溶劑或油構成之濃縮物,且此等濃縮物適於 用水稀釋。 /舌性物質在即用型製劑中之濃度可在相對較寬之範圍内 羑化活丨生物質一般佔0‘0001重量%至1 〇重量❶/。,較佳為 0.001重量%至丨重量。。(According to NMR spectrum) used. A water-soluble concentrate (LS), flowable concentrate (FS), powder for drying treatment (DS)' slurry treatment water dispersible powder (ws), soluble powder () emulsion (ES), emulsifiable concentrate (EC) and gel (GF) are commonly used for the purpose of treating plant propagation material (especially seeds) 147475.doc •109- 201043139. These compositions can be applied to plant propagation material (especially seeds) after dilution or without dilution. The composition in question is diluted from 2 to 10 times, and the active ingredient concentration of the ready-to-use preparation is from 1% by weight to 60% by weight, preferably from 3% by weight to 4% by weight. Administration can be carried out before or during sowing. Methods of applying or treating agrochemical compounds and compositions thereof to plant propagation materials, particularly seeds, are known in the art and include the application, coating, granulation, dusting, dipping of the propagation material. The method of application in the intrusion (in_furr〇w). In a preferred embodiment, the compound or composition thereof is applied separately to the plant propagation material by methods which do not induce germination (e.g., seeding, granulation, coating, and dusting). In a preferred embodiment, the suspension type (FS) composition is used for seed treatment. The FS composition typically comprises (1) (8) active material, a2 〇〇 surfactant, 〇 to 20 〇Μ antifreeze, 〇 to 400 g / 1 binder, 〇 to 200 g / Ι pigment and up to liters of solvent (preferably water). The active substance such as 5 hai can be used in the form of its composition by spraying, atomizing, dusting, spreading, brushing, dipping or pouring as the original, for example, a solution which can be directly sprayed, powder, suspension The liquid form, the dispersion, the emulsion, the oil knife liquid, the paste, the releasable product, the spreading material or the granules are used in the form of application, and the present invention is intended to be used in all cases. The active substances are distributed as finely as possible. The aqueous application form can be prepared from an emulsion concentrate, a paste or a wettable powder (sprayable powder, oil dispersion) by adding water. For the preparation of emulsions, pastes or oil dispersions, the shellfish (as is or dissolved in oil or solvent) can be homogenized by means of a wetting agent, tackifier, dispersant or milk 147475.doc •110- 201043139 In the water. Alternatively, a concentrate composed of an active substance, a wetting agent, a tackifier, a dispersing agent or an emulsifier and, if appropriate, a solvent or oil may be prepared, and such concentrates are suitable for dilution with water. / The concentration of the tongue substance in the ready-to-use preparation can be in a relatively wide range. The biomass of the sputum is generally from 0 '0001% by weight to 1 〇 by weight. Preferably, it is from 0.001% by weight to 丨 by weight. .

該等活性物質亦可成功用於超低容量方法(uhralow_ volume process 物質之組合物, ,ULV)中,可施用包含95重量%以上活性 或甚至施用無添加劑之活性物質。 當用於植物保護時,視所需效果之種類而定,活性物質 之施用量為每公頃〇.⑼i kg至2 kg,較佳每公頃〇祕^至 2 kg’更佳每公頃〇.〇5k#〇9kg,特定言之每公頃叫 至 0.75 kg。 ▲例如藉由撤粉、塗覆或浸透種子來處理植物繁瘦材料 (諸如種子)時,每100公斤植物繁殖材料(較佳種子)一般需 要0.1至I000 g,較佳H〇〇〇g,更佳H〇〇g,且最 5至1 00 g之量的活性物質。 當用於保護材料或儲存產品時活性物質之施用量視施 用區域之種類及所需效果而定。保護材料時施用量通常為 例如每立方公尺處理材料找2 kg,較佳Q加⑷ kg活性物質。 之組合物中添加各種類型 殺細菌劑、其他殺真菌劑 可向活性物質或包含活性物質 之油、濕潤劑、佐劑、除草劑、 147475.doc •111- 201043139 及/或殺有害生物劑,適當時直至使用之前即刻方添加(槽 混)°此等試劑可與本發明組合物以h i 〇〇至丨〇〇: 1,較佳 1:10至10:1之重量比混合。 可使用之佐劑特定言之為:有機改質聚矽氧烷,諸如 Break Thru S 240® ;醇烷氧化物,諸如 Atplus 245®、 Atplus MBA 1303®、Plurafac lf 300®及 Lutensol ON 30® ; EO/PO嵌段聚合物,例如piur〇nic RpE 2035®及Genapol B® ;醇乙氧化物,諸如Lutens〇1 χρ 8〇® ;及二辛基磺基丁 二酸鈉’諸如LeophenRA®。 呈殺真菌劑使用形式的本發明組合物亦可與其他活性物 質(例如除草劑、殺昆蟲劑、生長調節劑、殺真菌劑或肥 料)一起呈預混物形式存在或適當時直至使用之前即刻方 混合(槽混)。 在許多情況下,混合呈殺真菌劑使用形式之化合物I、n 及/或IV或包含該等化合物之組合物與其他殺真菌劑可拓 寬所獲得之殺真菌活性範圍或防止發展出殺真菌劑耐藥 性。此外,在許多情況下,獲得協同效應。 可與本發明化合物聯合使用之活性物質之以下清單意欲 說明可能之組合,但不限於此: A)嗜毯果伞素(strobilurin) 亞托敏(azoxystrobin)、醚菌胺(dimoxystrobin)、婦特菌 酯(enestroburin)、氟嘧菌酯(fluoxastr〇bin)、克收欣 (kresoxim-methyl) ' 苯氧菌胺(metomin〇str〇bin)、聘鱗菌 胺(orysastrobin)、啶氧菌胺(picoxystr〇bin)、百克敏 147475.doc -112- 201043139 (pyraclostrobin)、°比本卡(pyribencarb)、三就敏(trifloxystrobin) ; 2-(2-(6-(3-氯-2-曱基-苯氧基)-5-氟-嘧啶-4-基氧基)-苯基)-2-曱氧基亞胺基-N-甲基-乙醯胺、3-曱氧基-2-(2-(N-(4-甲氧 基-苯基)-環丙烷-甲醯亞胺基硫基甲基)-苯基)-丙烯酸甲 酯、(2-氯-5·[1-(3-曱基苯曱氧基亞胺基)乙基]苯甲基)胺基 曱酸甲酯及2-(2-(3-(2,6-二氯苯基)-1-曱基-亞烯丙基胺基 氧基甲基)-苯基)-2 -甲氧基亞胺基-N-甲基-乙酿胺; B)羧醯胺 -甲醯替苯胺(carboxanilide):本達樂(benalaxyl)、右 本達樂(benalaxyl-M)、麥鏽靈(benodanil)、百克芬 (bixafen)、白克利(boscalid)、萎鏽靈(carboxin)、曱呋醯 胺(fenfuram)、環醯菌胺(fenhexamid)、氟多寧(flutolanil)、 福拉比(furametpyr)、異哌劄美(isopyrazani)、異天尼 (isotianil)、開達樂(kiralaxyl)、滅普寧(mepronil)、滅達樂 (metalaxyl)、右滅達樂(metalaxyl-M/mefenoxam))、σ夫醯胺 (ofurace)、歐殺斯(oxadixyl)、嘉保信(oxycarboxin)、°比嗟 菌胺(penthiopyrad)、色達安(sedaxane)、克枯爛(teci〇ftaiam)、 賽氟滅(thifluzamide)、汰敵寧(tiadinil)、2-胺基-4-甲基·噻 。坐-5-甲醯替苯胺、2-氣-N-(l,l,3-三曱基-茚滿-4-基)-菸鹼 酿胺、N-(3,,4’,5,-三氟聯苯_2_基)-3-二氟曱基-1-曱基-1H-吼唾-4-甲醯胺、N-(4'-三氟甲基硫基聯苯_2_基)_3_二氟曱 基-1-甲基-1H-吡唑-4-甲醯胺、N-(2-(l,3-二甲基·丁基)-苯 基)-1,3-二甲基-5-氟-1H-吡唑-4-曱醯胺及N-(2-(l,3,3-三曱 基-丁基)-苯基)_1,3-二曱基-5-氟-1H-吡唑-4-曱醯胺; 147475.doc 113 - 201043139 - 缓酸基嗎琳(carboxylic morpholide): 達滅芬 (dimethomorph)、氟嗎琳(flumorph)、0比嗎琳(pyrimorph); - 苯甲酸醯胺:氟醯菌胺(flumetover)、氟D比菌胺 (fluopicolide)、氟吼菌醯胺(fluopyram)、座赛胺(zoxamide)、 1^-(3-乙基-3,5,5-三甲基-環己基)-3-甲醯胺基-2-羥基-苯甲 醯胺; - 其他叛酿胺:加普胺(carpropamid)、二氯西莫 (diclocymet)、雙块酿菌胺(mandiproamid)、土徽素 (oxytetracyclin)、石夕喧菌胺(silthiofarm)及 N-(6-甲氧基-0比 啶-3-基)環丙烷曱醯胺; C) 唑 -三0坐:阿紮康 °坐(azaconazole)、比多農(bitertanol)、 溴克座(bromuconazole)、環克座(cyproconazole)、待克利 (difenoconazole)、達克利(diniconazole)、右達克利(diniconazole-M)、依普座(epoxicbnazole)、芬克座(fenbuconazole)、氟 嗤。坐(fluquinconazole)、護石夕得(flusilazole)、護汰芬 (flutriafole)、菲克利(hexaconazole)、易胺座(imibenconazole)、依 普克嗤(ipconazole)、滅特座(metconazole)、邁克尼 (myclobutanil)、惡咪唾(oxpoconazole)、巴克素(paclobutrazole)、 平克座(penconazole)、普克利(propiconazole)、丙硫菌0坐 (prothioconazole)、石夕氟唾(simeconazole)、得克利(tebuconazole)、 四克利(tetraconazole)、三泰芬(triadimefon)、三泰隆 (triadimenol)、滅菌口坐(triticonazole)、稀效0垒(uniconazole)、 1-(4-氣-苯基)-2-([1,2,4]三唑-1-基)-環庚醇; 147475.doc -114- 201043139 -σ米唾:賽座滅(cyazofamid)、依滅列(ima.zalil)、稻痕 酉旨(peflirazoate)、撲克拉(prochloraz)、赛福座(triflumizole); - 苯并咪唾:免賴得(benomyl)、貝芬替(carbendazim)、 麥穗寧(fuberidazole)、腐絕(thiabendazole); -其他:嗔0坐菌胺(ethaboxam)、依得利(etridiazole)、 惡黴靈(hymexazole)及 2-(4-氣-苯基)-N-[4-(3,4-二曱氧基-苯基)-異噁唑-5-基]-2-丙-2-炔氧基-乙醯胺; D)雜環化合物 -。比 σ定:扶吉胺(fluazinam)、比芬諾(pyrifenox)、3-[5-(4-氯-苯基)-2,3-二曱基-異噁唑啶-3-基]-吡啶、3-[5-(4-甲 基-苯基)-2,3_二甲基-異噁唑啶-3-基]-吡啶、2,3,5,6-四氯-4-曱烷磺醯基-吡啶、3,4,5-三氣吡啶-2,6-二曱腈、N-(l-(5-溴-3-氯-吡啶-2-基)-乙基)-2,4-二氣菸鹼醯胺、N-[(5-溴-3-氣-D比咬-2-基)-二風^-2,4-二氣-於驗酿胺, -痛咬:布瑞莫(bupirimate)、賽普洛(cyprodinil)、二氟 林(diflumetorim)、芬瑞莫(fenarimol)、富瑞综(ferimzone)、 滅派林(mepanipyrim)、氣咬(nitrapyrin)、尼瑞莫(nuarimol)、 派美尼(pyrimethanil); - 旅唤:賽福寧(triforine); -°比 D各:拌種洛(fludioxonil)、護汰寧(fludioxonil); - 嗎琳:阿迪嗎琳(aldimorph)、嗎菌靈(dodemorph)、 乙酸嗎菌靈(dodemorph-acetate)、芬普福(fenpropimorph)、三 得芬(tridemorph); -D底 °定:苯鏽咬(fenpropidin); 147475.doc -115- 201043139 - 二曱醢亞胺:峻咬草(fluoroimide)、依普同 (iprodione)、撲滅寧(procymidone)、免克寧(vinclozolin); - 非芳族5員雜環:凡殺同(famoxadone)、咪吐菌酮 (fenamidone)、福天尼(flutianil)、辛嘆酮(octhilinone)、撲 殺熱(probenazole)、5-胺基-2-異丙基-3-側氧基-4-鄰甲苯 基-2,3-二氫吡唑-1-硫代曱酸S-烯丙酯; - 其他:酸化苯并0塞二0坐-S-甲ϊ旨(acibenzolar-S-methyl)、°引 D坐石黃菌胺(amisulbrom)、敵菌靈(anilazine)、 保米黴素(blasticidin-S)、四氯丹(captafol)、蓋普丹 (captan)、滅蜗猛(chinomethionate)、邁隆(dazomet)、口米菌 威(debacarb)、達滅淨(diclomezine)、野燕枯(difenzoquat)、 曱基硫酸野燕枯(difenzoquat-methylsulfate)、氰菌胺 (fenoxanil)、福爾培(folpet)、歐索林酸(oxolinic acid)、粉 病靈(piperalin)、普奎那兹(proquinazid)、百快隆(pyroquilone)、 快諾芬(quinoxyfen)、咪唾嗪(triazoxide)、三賽口坐 (tricyclazole)、2-丁氧基-6-蛾-3 -丙基咣烯-4-酮、5-氯-1-(4,6-二曱氧基-嘧啶-2-基)-2-曱基-1H-苯并咪唑、5-氯-7-(4-曱基哌啶-1-基)-6-(2,4,6-三氟苯基)-[1,2,4]三唑并[1,5-a]嘴咬及5 -乙基-6-辛基-[1,2,4]三唾并[1,5-a]哺咬-7-基胺; E)胺基曱酸酯 &quot;硫胺基甲酸醋及二硫胺基甲酸醋,諸如福美鐵 (ferbam)、辞猛乃浦(mancozeb)、猛乃浦(maneb)、威百故 (metam)、續菌威(methasulfocarb)、免得爛(metiram)、曱 基鋅乃浦(propineb)、得恩地(thiram)、鋅乃浦(zineb)、益 147475.doc -116- 201043139 穗(ziram); - 胺基甲酸酯:苯°塞菌胺(benthiavalicarb)、乙黴威 (diethofencarb)、顯黴威(iprovalicarb)、霜黴威(propamocarb)、 霜黴威鹽酸鹽、瓦芬那(valiphenal)及N-(l-(l-(4-氰基-苯 基)乙烷磺醯基)-丁-2-基)胺基甲酸-(4-氟苯基)酯; F)其他活性物質Such active substances can also be successfully used in ultra low volume methods (ULV), which can be applied with more than 95% by weight of active or even without additives. When used for plant protection, depending on the type of effect required, the application rate of the active substance is 〇.(9)i kg to 2 kg per hectare, preferably per hectare ^2 to 2 kg' more per hectare. 5k#〇9kg, specifically called 0.75 kg per hectare. ▲ When treating plant lean materials (such as seeds) by withdrawing powder, coating or soaking seeds, for example, 0.1 to 1 000 g, preferably H〇〇〇g, is generally required per 100 kg of plant propagation material (preferred seed). More preferably H〇〇g, and an active substance in an amount of from 5 to 100 g. The amount of active substance applied when used to protect or store the product depends on the type of application area and the desired effect. The amount of the protective material to be applied is usually, for example, 2 kg per cubic meter of treated material, preferably Q plus (4) kg of active material. Adding various types of bactericides and other fungicides to the active composition or oils containing the active substances, wetting agents, adjuvants, herbicides, 147475.doc •111- 201043139 and/or pesticides, These agents may be added to the composition of the present invention in a weight ratio of hi to 丨〇〇: 1, preferably 1:10 to 10:1, as appropriate, until the time of use. The adjuvants that can be used are specifically: organically modified polyoxyalkylenes such as Break Thru S 240®; alcohol alkoxylates such as Atplus 245®, Atplus MBA 1303®, Plurafac lf 300® and Lutensol ON 30®; EO/PO block polymers such as piur〇nic RpE 2035® and Genapol B®; alcohol ethoxylates such as Lutens〇1 χρ 8〇®; and sodium dioctylsulfosuccinate such as LeophenRA®. The compositions of the invention in the form of fungicides may also be present in the form of a premix with other active substances, such as herbicides, insecticides, growth regulators, fungicides or fertilizers, or as appropriate, until immediately prior to use. Square mixing (slot mixing). In many cases, the combination of the compounds I, n and/or IV in the form of a fungicide or the composition comprising the compounds with other fungicides broadens the range of fungicidal activity obtained or prevents the development of fungicides. Drug resistance. In addition, in many cases, synergies are obtained. The following list of active substances which may be used in combination with the compounds of the present invention is intended to illustrate possible combinations, but is not limited thereto: A) strobilurin, azoxystrobin, dimoxystrobin, fete Estrostrobin, fluoxastr〇, kresoxim-methyl 'metomin〇 str〇bin, orysastrobin, oxystrobin Picoxystr〇bin), baikemin 147475.doc -112- 201043139 (pyraclostrobin), ° pyribencarb, trifloxystrobin; 2-(2-(6-(3-chloro-2-indenyl) -phenoxy)-5-fluoro-pyrimidin-4-yloxy)-phenyl)-2-oxooxyimido-N-methyl-acetamide, 3-decyloxy-2-( 2-(N-(4-methoxy-phenyl)-cyclopropane-formamidothiomethyl)-phenyl)-methyl acrylate, (2-chloro-5.[1-(3) - mercaptobenzoyloxyimino)ethyl]benzyl)amino decanoate and 2-(2-(3-(2,6-dichlorophenyl)-1-indenyl-arylene Allylaminooxymethyl)-phenyl)-2-methoxyimino-N-methyl-ethenylamine; B) Carboxamide-methylhydrazine Carboxanilide): benalaxyl, benalaxyl-M, benodanil, bixafen, boscalid, carboxin, furfuryl Amine (fenfuram), fenhexamid, flutolanil, furametpyr, isopyrazani, isotianil, kiralaxyl, extinction Mepronil, metalaxyl, metalaxyl-M/mefenoxam, ofurace, oxadixyl, oxycarboxin, bacterium Amine (penthiopyrad), sedaxane, teci〇ftaiam, thifluzamide, tiadinil, 2-amino-4-methyl-thiophene. Sitting on -5-formaldehyde aniline, 2-gas-N-(l,l,3-tridecyl-indan-4-yl)-nicotine-brown amine, N-(3,,4',5, -Trifluorobiphenyl-2-yl)-3-difluorodecyl-1-indenyl-1H-indole-4-carboxamide, N-(4'-trifluoromethylthiobiphenyl_2 _ base)_3_difluorodecyl-1-methyl-1H-pyrazole-4-carboxamide, N-(2-(l,3-dimethylbutyl)-phenyl)-1, 3-Dimethyl-5-fluoro-1H-pyrazole-4-decylamine and N-(2-(l,3,3-tridecyl-butyl)-phenyl)-1,3-dioxin 5--5-fluoro-1H-pyrazole-4-decylamine; 147475.doc 113 - 201043139 - carboxylic morpholide: dimethomorph, flumorph, 0 ratio Pyrimorph; - benzoyl benzoate: flumetover, fluocicolide, fluopyram, zoxamide, 1^-(3 -ethyl-3,5,5-trimethyl-cyclohexyl)-3-carboxamido-2-hydroxy-benzamide; - other apoemic amines: carpropamid, dichlorocis Diclocymet, mandiproamid, oxytetracyclin, silthiofarm, and N-(6-methoxy-0 Bipyridin-3-yl)cyclopropane decylamine; C) azole-three-zero sitting: azaconazole, bitertanol, bromuconazole, cyproconazole , difenoconazole, diniconazole, diniconazole-M, epoxicbnazole, fenbuconazole, fluoroquinone. Fluquinconazole, flusilazole, flutriafole, hexaconazole, imibenconazole, ipconazole, metconazole, micney (myclobutanil), oxpoconazole, paclobutrazole, penconazole, propiconazole, prothioconazole, simeconazole, derkeley Tebuconazole), tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole, 1-(4-gas-phenyl)-2- ([1,2,4]triazol-1-yl)-cycloheptanol; 147475.doc -114- 201043139 - σ米唾: cyazofamid, ima.zalil, rice mark Peflirazoate, prochloraz, triflumizole; - benzopyrene: benomyl, carbendazim, fuberidazole, thiabendazole ); other: eth0 ethaboxam, etridiazole, evil Hymexazole and 2-(4-a-phenyl)-N-[4-(3,4-dimethoxy-phenyl)-isoxazole-5-yl]-2-prop-2- Alkynyloxy-acetamide; D) heterocyclic compound-. Ratio σ: fluazinam, pyrifenox, 3-[5-(4-chloro-phenyl)-2,3-didecyl-isoxazol-3-yl]- Pyridine, 3-[5-(4-methyl-phenyl)-2,3-dimethyl-isoxazol-3-yl]-pyridine, 2,3,5,6-tetrachloro-4- Decanesulfonyl-pyridine, 3,4,5-tripyridine-2,6-dicarbonitrile, N-(l-(5-bromo-3-chloro-pyridin-2-yl)-ethyl) -2,4-di-nicotinine decylamine, N-[(5-bromo-3-gas-D ratio bit-2-yl)-two winds^-2,4-digas-in the test amine, - Bite bite: bupirimate, cyprodinil, diflumetorim, fenarimol, ferimzone, mepanipyrim, nitrapyrin , nuarimol, pyrimethanil; - brigade: triforine; - ° ratio D: fludioxonil, fludioxonil; - linlin: Aldimorph, dodemorph, dodemorph-acetate, fenpropimorph, tridemorph; -D bottom: fenpropidin ; 147475.doc -115- 201043139 - Diterpenoid Fluoroimide, iprodione, procymidone, vinclozolin; - non-aromatic 5-membered heterocyclic ring: famoxadone, fenamidone , flutianil, octhilinone, probenazole, 5-amino-2-isopropyl-3-oxo-4-o-tolyl-2,3-dihydro Pyrazole-1-thiodecanoic acid S-allyl ester; - Others: acidified benzoxoxane-s-a-sodium-S-methyl-A-benzoate-s-methyl ), anilazine, blasticidin-S, captafol, captan, chinomethionate, dazomet, minocycline (debacarb), diclomezine, difenzoquat, difenzoquat-methylsulfate, fenoxanil, folpet, oxolinic Acid), piperalin, proquinazid, pyroquilone, quinoxyfen, triazoxide, tricyclazole ), 2-butoxy-6-moth-3-propyl decen-4-one, 5-chloro-1-(4,6-dimethoxy-pyrimidin-2-yl)-2-fluorenyl -1H-benzimidazole, 5-chloro-7-(4-mercaptopiperidin-1-yl)-6-(2,4,6-trifluorophenyl)-[1,2,4]triazole And [1,5-a] mouth bite and 5-ethyl-6-octyl-[1,2,4]tris-[1,5-a]-doped-7-ylamine; E) amine group Phthalate &quot;thiamine carboxylic acid vinegar and dithiocarbamate formic acid vinegar, such as ferbate, mancozeb, maneb, metam, continuum (methasulfocarb), metiram, propineb, thiram, zineb, 147475.doc -116- 201043139 ziram; - urethane Ester: benthiavalicarb, diethofencarb, iprovalicarb, propamocarb, propamocarb hydrochloride, valiphenal and N-l -(l-(4-cyano-phenyl)ethanesulfonyl)-butan-2-yl)carbamic acid-(4-fluorophenyl) ester; F) other active substances

- 胍類:脈(guanidine)、多寧(dodine)、多寧游離驗、雙 胍鹽(guazatine)、乙酸雙胍鹽、雙胍辛胺(iminoctadine)、 三乙酸雙脈辛胺、參(烧基苯續酸)雙胍辛胺(iminoctadine-tris(albesilate)) i -抗生素:喜賜黴素(kasugamycin)、水合鹽酸喜賜黴 素、鏈黴素(streptomycin)、多氧菌素(polyoxin)、有效黴 素 A(validamycin A); - 硝基苯基衍生物:百蜗克(binapacryl)、消蜗通 (dinobuton)、白粉克(dinocap)、欧菌醋(nitrothal isopropyl)、四 氯确基苯(tecnazene); - 有機金屬化合物:三苯錫鹽(fentin salts),諸如三苯 醋錫(fentin acetate)、三苯錫氣(fentin chloride)、三笨經 錫(fentin hydroxide); - 含硫雜環基化合物:腈硫酿(dithianon)、稻痕靈 (isoprothiolane); - 有機鱗化合物_·護粒松(edifenphos)、福赛得 (fosetyl)、乙鱗 IS (fosetyl-aluminum)、丙基喜樂松 (iprobenfos)、亞麟酸及其鹽、白粉松(pyrazophos)、脫克 147475.doc 、-117- 201043139 松(tolclofos-methyl); - 有機氯化合物:四氯異苯腈(chlorothalonil)、益發靈 (dichlofluanid)、二氯酉分(dichlorophen)、續菌胺(flusulfamide)、 六氯苯(hexachlorobenzene)、賓克隆(pencycuron)、五氣盼 (pentachlorphenole)及其鹽、熱必斯(phthalide)、五氯頌基 苯(quintozene)、甲基多保淨(thiophanate methyl)、甲基益 發靈(tolylfluanid)、N-(4-氯-2-硝基-苯基)-N-乙基-4-曱基-苯磺醯胺; - 無機活性物質:波爾多混合液(Bordeaux mixture)、 乙酸銅、氫氧化銅、氣氧化銅、鹼式硫酸銅、硫; - 其他:聯苯、溴确丙二醇(bronopol)、環氟菌胺 (cyflufenamid)、克絕(cymoxanil)、二苯胺(diphenyl-amin)、 滅芬農(metrafenone)、滅粉黴素(mildiomy-cin)、快得寧 (oxine-copper)、調環酸約(prohexadione-calcium)、螺惡茂 胺(spiroxamine)、曱基益發靈、N-(環丙基甲氧基亞胺基-(6-二氟-甲氧基-2,3-二氟-苯基)-曱基)-2-苯基乙醯胺、N'-(4-(4-氯-3-三氟甲基-苯氧基)-2,5-二甲基-苯基)-N-乙基-N-曱基曱脒、N'-(4-(4-氟-3-三氟甲基-苯氧基)-2,5-二甲基-苯 基)-N-乙基-N-甲基甲脒、Ν·-(2-曱基-5-三氟甲基-4-(3-三 甲基矽烷基-丙氧基)-苯基)-N-乙基-N-甲基甲脒、Ν·-(5-二 氟曱基-2-曱基-4-(3-三曱基矽烷基-丙氧基)-苯基)-Ν-乙基-Ν-甲基曱脒、2-{1-[2-(5-甲基-3-三氟甲基-吡唑-1-基)-乙 醯基]-哌啶-4-基}-噻唑-4-曱酸甲基-(1,2,3,4-四氫萘-1-基)-酿胺、2-{1-[2-(5 -曱基-3-三氟曱基-0比哇-1-基)-乙酿基]底 147475.doc -118- 201043139 咬-4-基卜噻唑-4-甲酸甲基-(1〇-1,2,3,4-四氫萘-1-基-醯 月女、乙自文6 -第二丁基_8_氟_2,3_二甲基_B奎淋_4_基g旨及甲氧 基-乙酸6-第三丁基_8_氟_2,3_二甲基-喹啉-4-基酯。 G) 生長調節劑 脫落酸(abscisic acid)、先甲草胺(amidochlor)、嘧啶醇 (ancymidol)、6-笨甲基胺基嘌呤、蕓苔素内酯(bras_sin〇lide)、 比達甲(butralin)、克滅則(chlormequat)(克美素(chlormequat chloride))、氯化膽驗(ch〇line chl〇ride)、環丙酸醯胺 (cyclanilide)、亞拉生長素(daminozide)、調咬酸(dikegulac)、 穫萎得(dimethi-pin)、2,6-二甲基。比。定、益收生長素 (ethephon)、乳節胺(f|umetraiin)、β夫嘴醇(fjUIprimid〇i)、氟嗟草 酯(flu-thiacet)、福芬素(forchl〇rfenuron)、赤黴酸(gibberellic acid)、依.納素(inabenfid)、0弓丨0朵-3-乙酸、抑芽素(maleic hydrazide)、氟磺醯草胺(mefluidide)、壯棉素(mepiquat)(縮 節胺(mepiquat chloride))、萘乙酸、N-6-苯甲基腺嘌呤、 巴克素(paclobutrazol)、調環酸(pro-hexadione)(調環酸 4弓)、茉莉酸丙醋(prohydro-jasmon)、嘆苯隆(thidiazuron)、抑 芽唑(triapen-thenol)、三硫磷酸三丁酯、2,3,5-三蛾苯曱 酸、抗倒醋(trinexapac-ethyl)及稀效°坐; H) 除草劑 -乙酿胺•·乙草胺(acetochlor)、曱草胺(alachlor)、丁 草胺(butachlor)、二甲草胺(dimethachlor)、汰草滅 (dimethenamid)、氟嘆草胺(flufenacet)、苯售酿草胺 (mefenacet)、滅多草(metolachlor)、滅草胺(metazachlor)、 147475.doc -119- 201043139 萘丙醯草胺(napropamide)、萘丙胺(naproanilide)、烯草胺 (pethoxamid)、丙草胺(pretilachlor)、毒草安(propachlor)、 曱氧嘆草胺(thenylchlor); - 胺基酸衍生物:雙丙胺鱗(bilanafos)、草甘膦、草敍 膦、草硫膦(sulfosate); - 芳氧基苯氧基丙酸酯:炔草酸(clodinafop)、氰氟草 醋(cyhalofop-butyl)、°惡 °坐禾草靈(fenoxaprop)、°比氟禾草 靈(fluazifop)、》比氟氣禾靈(haloxyfop)、°惡》坐醯草胺 (metamifop)、惡草酸(propaquizafop)、喹禾靈(quizalofop)、 喧·禾糠醋(quizalofop-P-tefuryl); - 聯°比°定:敵草快(diquat)、百草枯(paraquat); -(硫代)胺基甲酸醋:續草靈(asulam)、丁草特 (butylate)、卡草胺(carbetamide)、甜菜安(desmedipham)、 0底草丹(dimepiperate)、撲草滅(eptam)(EPTC)、戊草丹 (esprocarb)、得草滅(molinate)、坪草丹(orbencarb)、甜菜 寧(phenmedipham)、苄草丹(prosulfocarb)、稗草畏(pyributicarb)、 殺丹(thiobencarb)、野麥畏(triallate); - 環己二酮:丁苯草酮(butroxydim)、稀草酮 (clethodim)、環殺草(cycloxydim)、環苯草酮(profoxydim)、 西殺草(sethoxydim)、得殺草(tepraloxydim)、三甲苯草酮 (tralkoxydim); - 二硝基苯胺:倍尼芬(benfluralin)、乙丁烯氟靈 (ethalfluralin)、安績靈(oryzalin)、二曱戊樂靈(pendimethalin)、 苯胺靈(prodiamine)、氟樂靈(trifluralin); 147475.doc •120- 201043139 - 二苯醚:三氟&gt; 叛草醚(acifluorfen)、苯草醚 (aclonifen)、必芬諾(bifenox)、禾草靈(diclofop)、氣氟草 醚(ethoxyfen)、氟確胺草謎(fomesafen)、乳氟禾草靈 (lactofen)、乙氧氟草醚(oxyfluorfen); - 經基苯甲腈:漠苯腈(bromoxynil)、敵草腈(dichlobenil)、 蛾苯腈(ioxynil); -咪0坐琳酮:味草S旨(imazamethabenz)、甲氧口米草於、 甲基p米草於(imazapic)、°米β坐於酸(imazapyr)、咪嗤啥琳酸 (imazaquin)、口米唾乙終酸(imazethapyr); - 苯氧基乙酸:稗草胺〇1〇11^1)1:〇卩)、2,4-二氣苯氧基乙 酸(2,4-D)、2,4-DB、滴丙酸(dichlorprop)、MCPA、MCPA-硫乙基、MCPB、2 -甲-4-氣丙酸(mecoprop); -°比 °秦:氯草敏(chloridazone)、氣噠 π秦草醋(flufenpyr-ethyl)、氟 °塞草 S旨(fluthiacet)、達草滅(norflurazone)、噠草 特(pyridate); -°比 °定:胺草 α定(aminopyralid)、克草立特(clopyralid)、 0比氟草胺(diflufenican)、氟硫草定(dithiopyr)、I η定草 _ (fluridone)、氟草終(fluroxypyr)、毒莠定(picloram)、氟0比 醯草胺(picolinafen)、唉草咬(thiazopyr); - 續醢脲:醢鳴績隆(amidosulfuron)、四唾喷續隆 (azimsulfuron)、苄嘧磺隆(bensulfuron)、氣嘧磺隆 (chlorimuron-ethyl)、氯磺隆(chl〇rsulfuron)、醚磺隆 (cinosulfuron)、環丙嘴項隆(CyCi〇suifaniuron)、乙氧癌石黃 隆(ethoxysulfuron)、嘧啶磺隆(flazasuifuron)、氟吡磺隆 147475.doc • 121 - 201043139- steroids: guanidine, dodine, tannin, guazatine, bismuth sulphate, iminoctadine, dioctylamine triacetate, ginseng Acid) diinoctylamine (iminoctadine-tris (albesilate)) i - antibiotics: kasugamycin, hydrated salbutamycin, streptomycin, polyoxin, tyrosin A (validamycin A); - Nitrophenyl derivatives: binapacryl, dinobuton, dinocap, nitrothal isopropyl, tecnazene - Organometallic compounds: fentin salts, such as fentin acetate, fentin chloride, fentin hydroxide; - sulfur-containing heterocyclic compounds : dithianon, isoprothiolane; - organic scale compounds _ edifenphos, fosetyl, fosetyl-aluminum, propyl sheisson (iprobenfos) ), arsenic acid and its salt, white pine (pyrazophos), gram 147 475.doc,-117- 201043139 pine (tolclofos-methyl); - organochlorine compounds: chlorothalonil, dichlofluanid, dichlorophen, flusulfamide, Hexachlorobenzene, pencycuron, pentachlorphenole and its salts, phthalide, quintozene, thiophanate methyl, Tolylfluanid, N-(4-chloro-2-nitro-phenyl)-N-ethyl-4-mercapto-benzenesulfonamide; - Inorganic active substance: Bordeaux mixture , copper acetate, copper hydroxide, copper oxide, basic copper sulfate, sulfur; - other: biphenyl, bromopol, cyflufenamid, cymoxanil, diphenylamine -amin), metrafenone, mildiomy-cin, oxine-copper, prohexadione-calcium, spiroxamine, sulfhydryl Yifaling, N-(cyclopropylmethoxyimino-(6-difluoro-methoxy-2,3-difluoro-phenyl) -mercapto)-2-phenylacetamide, N'-(4-(4-chloro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N- Ethyl-N-mercaptopurine, N'-(4-(4-fluoro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl- N-methylformamidine, Ν-(2-mercapto-5-trifluoromethyl-4-(3-trimethyldecyl-propoxy)-phenyl)-N-ethyl-N- Methylformamide, Ν·-(5-difluorodecyl-2-mercapto-4-(3-tridecylfluorenyl-propoxy)-phenyl)-indole-ethyl-hydrazine-methyl 2-(1-[2-(5-methyl-3-trifluoromethyl-pyrazol-1-yl)-ethinyl]-piperidin-4-yl}-thiazole-4-oxime Acid methyl-(1,2,3,4-tetrahydronaphthalen-1-yl)-bristamine, 2-{1-[2-(5-fluorenyl-3-trifluoromethyl-p-wow- 1-yl)-ethylidene] bottom 147475.doc -118- 201043139 bite-4-ylthiazole-4-carboxylic acid methyl-(1〇-1,2,3,4-tetrahydronaphthalen-1-yl -醯月女,乙自文6 -Secondyl _8_Fluorine 2,3_dimethyl-B Queron _4_yl g and methoxy-acetic acid 6-t-butyl _8 _Fluoro-2,3-dimethyl-quinolin-4-yl ester. G) growth regulators abscisic acid, amidochlor, ancymidol, 6-stactylaminoguanidine, brassinolide (bras_sin〇lide), bismuth ( Butralin), chlormequat (chlormequat chloride), chloramphenicol (ch〇line chl〇ride), cyclanilide, daminozide, bite Acid (dikegulac), dimethi-pin, 2,6-dimethyl. ratio. Ethephon, f;umetraiin, β-frozen (fjUIprimid〇i), flu-thiacet, forchl〇rfenuron, Gibberellium Acid (gibberellic acid), inabenfid, 0 bow-3-acetic acid, maleic hydrazide, mefluidide, mepiquat Mepiquat chloride, naphthaleneacetic acid, N-6-benzyl adenine, paclobutrazol, pro-hexadione (4 bows), prohydro-jasmon ), thidiazuron, triapen-thenol, tributyl trithiophosphate, 2,3,5-trimo-benzoic acid, trinexapac-ethyl and thinning H) Herbicide - acetochlor, alachlor, butachlor, dimethachlor, dimethenamid, snail Flufenacet, benzene, mefenacet, metolachlor, metazachlor, 147475.doc -119- 201043139 napropamide Naproanilide, pethoxamid, pretilachlor, propachlor, thenylchlor; - amino acid derivatives: biarylfos, grass Glyphosate, glyphosate, sulfosate; - aryloxyphenoxypropionate: clodinafop, cyhalofop-butyl, °°°草草灵(fenoxaprop ), ° fluazifop, haloxyfop, ° evil, metamife, oxalic acid Vinegar (quizalofop-P-tefuryl); - 联°°°: diquat, paraquat; -(thio)amino carboxylic acid vinegar: asulam, butachlor (butula) Butylate), carbeamide, desmedipham, dimepiperate, eptam (EPTC), esprocarb, molate, pingcao Orbencarb, phenmedipham, prosulfocarb, pyributicarb, thiobencarb Trilate (triallate); - cyclohexanedione: butroxydim, clethodim, cycloxydim, profoxydim, sethoxydim, Tepulaloxydim, tralkoxydim; - dinitroaniline: benfluralin, ethalfluralin, oryzalin, diterpenoid Pendimethalin), prodiamine, trifluralin; 147475.doc •120- 201043139 - diphenyl ether: trifluoro&gt; acifluorfen, aclofenf, bifenfen ( Bifenox), diclofop, ethoxyfen, fomesafen, lactofen, oxyfluorfen; Nitrile: bromoxynil, dichlobenil, ioxynil; - oxime ketone: imazamethabenz, methoxymetazone, methyl p rice (imazapic), °m β sitting in acid (imazapyr), imazaquin acid (imazaquin), mouth rice salic acid (imazethapyr); - benzene Oxyacetic acid: oxachlorin 〇1〇11^1)1: 〇卩), 2,4-diphenoxyacetic acid (2,4-D), 2,4-DB, dichlorprop , MCPA, MCPA-thioethyl, MCPB, 2-methyl-4-propionic acid (mecoprop); -° ratio ° Qin: chloridazone, flufenpyr-ethyl, flu ° fluthiacet, norflurazone, pyridate; -° ratio: aminopyralid, clopyralid, 0 vs. fluramide (diflufenican), dithiopyr, fluridone, fluroxypyr, picloram, picolinafen, thiazopyr - Continued carbamide: amidosulfuron, azimsulfuron, bensulfuron, chlorimuron-ethyl, chlorsulfuron (chl〇rsulfuron), Cinosulfuron, CyCi〇suifaniuron, ethoxysulfuron, flazasuifuron, flumasulfuron 147475.doc • 121 - 201043139

(flucetosulfuron)、氟口定喊續隆(flupyrsulfuron)、曱醯胺績 隆(foramsulfuron)、氯 °比喊續隆(halosulfuron)、〇坐 °比 β密橫 隆(imazosulfuron)、破甲石黃隆(iodosulfuron)、甲石夤胺績隆 (mesosulfuron)、曱項隆(metsulfuron-methyl)、於嘴績隆 (nicosulfuron)、環氧 °密磺隆(oxasulfuron)、氟 '•密續隆 (primisulfuron)、氟確隆(prosulfuron)、。比 °密續隆 (pyrazosulfuron)、颯0密石黃隆(rimsulfuron)、曱喷續隆 (sulfometuron)、石黃喊續隆(sulfosulfuron)、°塞吩續隆 (thifensulfuron)、醚苯續隆(triasulfuron)、苯石黃隆 (tribenuron)、三氟咬石黃隆(trifloxysulfuron)、氟胺績隆 (triflusulfuron)、三氟甲續隆(tritosulfuron)、1-((2-氯-6-丙 基-咪唑并[1,2-b]噠嗪-3-基)磺醯基)-3-(4,6-二甲氧基-嘧啶-2-基)脲;(flucetosulfuron), flu port, flupyrsulfuron, foramsulfuron, chlorine, halosulfuron, squatting, imazosulfuron, scutellaria (iodosulfuron), mesosulfuron, metsulfuron-methyl, nicosulfuron, oxasulfuron, fluoroprime primisulfuron , prosulfuron, (prosulfuron). Pyrosulfuron, rimsulfuron, sulfometuron, sulfosulfuron, thifensulfuron, ether benzene sulphide Triasulfuron), tribenuron, trifloxysulfuron, triflusulfuron, tritosulfuron, 1-((2-chloro-6-propyl) -imidazo[1,2-b]pyridazin-3-yl)sulfonyl)-3-(4,6-dimethoxy-pyrimidin-2-yl)urea;

- 三嗪:草殺淨(ametryn)、草脫淨(atrazine)、氰乃淨 (cyanazine)、異戊乙淨(dimethametryn)、乙琉津(ethiozin)、 六 °秦酮(hexazinone)、苯嗓草 _ (metamitron)、滅必淨 (metribuzin)、撲草淨(prometryn)、西瑪津(simazine)、特 丁津(terbuthylazine)、去草淨(terbutryn)、三嗓氟草胺 (triaziflam); -脲:綠麥隆(chlorotoluron)、殺草隆(daimuron)、敵 草隆(diuron)、伏草隆(fluometuron)、異丙隆(isoproturon)、 利榖隆(linuron)、甲苯》塞隆(methabenzthiazuron)、丁0塞隆 (tebuthiuron); - 其他乙酿乳酸合成酶抑制劑:雙草醚納(bi spy rib ac- 147475.doc -122- 201043139- Triazine: ametryn, atrazine, cyanazine, dimethametryn, ethiozin, hexazinone, benzoquinone Grass _ (metamitron), metribuzin, prometryn, simazine, terbuthylazine, terbutryn, triaziflam; -urea: chlorotoluron, daimuron, diuron, fluometuron, isoproturon, linuron, toluene Methabenzthiazuron), tebuthiuron; - other lactic acid synthase inhibitors: bispyridinose (bi spy rib ac- 147475.doc -122- 201043139

sodium)、氯S旨續草胺(cloransulam-methyl)、雙氯續草胺 (diclosulam)、雙氟磺草胺(florasulam) '氟酿I確隆 (flucarbazone)、唾嘴續草胺(flumetsulam)、績草。坐胺 (metosulam)、β密苯胺磺隆(ortho-sulfamuron)' 五氟磧草胺 (penoxsulam)、丙氧績隆(propoxycarbazone)、丙 ϊ旨草驗 (pyribambenz-propyl)、°密 °定月亏草謎(pyribenzoxim)、環醋 草趟(pyriftalid)、《密草鍵(pyriminobac-methyl)、痛沙泛 (pyrimisulfan) &gt; 嘴硫草謎(pyrithiobac)、普硫芬 (pyroxasulfone)、甲氧續草胺(pyroxsulam); -其他:胺°坐草酮(amicarbazone)、胺基三0坐 (aminotriazole)、莎稗麟(anilofos)、氟 丁草胺(beflubutamid)、 草除靈(benazolin)、苯卡巴松(bencarbazone)、β夫草黃 (benfluresate)、口比草酮(benzofenap)、苯達松(bentazone)、 苯并雙環酮(benzobicyclon)、克草(bromacil)、漠丁酿草胺 (bromobutide)、氟丙鳴草醋(butafenacil)、抑草麟(butamifos)、 0坐草胺(cafenstrole)、〇坐 _ 草醋(carfentrazone)、0引 D朵酮草 醋(cinidon-ethlyl)、敵草索(chlorthal)、環庚草醚(cinmethylin)、 可滅縱(clomazone)、苄草隆(cumyluron)、環丙績酿胺 (cyprosulfamide)、麥草畏(dicamba)、野燕枯、二氟 D比隆 (diflufenzopyr)、稗内腾螺孢菌(Drechslera monoceras)、草 多索(endothal)、乙0夫草石黃(ethofumesate)、乙氧苯草胺 (etobenzanid)、四唾醯草胺(fentrazamide)、氣烯草酸 (flumiclorac-pentyl)、丙快敗草胺(flumioxazin)、氟胺草嗤 (flupoxam)、氟 B各草酮(fluorochloridone)、吱草酮(flurtamone)、 147475.doc -123- 201043139 茚草_ (indanofan)、異β惡草胺(isoxaben)、異°惡°坐草嗣 (isoxaflutole)、環草定(lenacil)、敵稗(propanil)、戊炔草胺 (propyzamide)、二氣啥淋酸(quinclorac)、嗜草酸(quinmerac)、 甲基石黃草酿| (mesotrione) '甲基珅酸、萘草胺(naptalam)、炔 惡草酮(oxadiargyl)、惡草 _ (oxadiazon)、惡嗓草 _ (oxaziclomefone)、環戊 °惡草酮(pentoxazone)、。坐琳草醋 (pinoxaden)、雙 α坐草腈(pyraclonil)、σ比草鍵(pyraflufen-ethyl)、匹拉續托(pyrasulfotol)、苄草唾(pyrazoxyfen)、比拉 π坐諾(pyrazolynate)、滅藻酿(quinoclamine)、嘴 α定將草醚 (saflufenacil)、石夤草酮(sulcotrion)、甲續草胺(sulfentrazone)、 特草定(terbacil)、特咬 _ (tefbryltrione) ' 特伯酮(tembotrione)、 嘆卡巴腙(thiencarbazone)、托潘膝(topramezone)、4-羥基-3-[2-(2-甲氧基-乙氧基曱基)-6-三氟甲基比啶-3-羰基]-雙 環[3.2.1]辛-3-烯-2-酮、(3-[2-氯-4-氟-5-(3-甲基-2,6-二側 氧基-4-三氟甲基-3,6-二氫-2H-嘧啶-1-基)-苯氧基]比啶-2-基氧基)-乙酸乙酯、6-胺基-5-氣-2-環丙基-嘧啶-4-曱酸曱 酯、6-氣-3-(2-環丙基-6-曱基-苯氧基)-噠嗪-4-醇、4-胺基-3 -氯-6-(4 -氯-苯基)-5 -氟-0比0定-2-甲酸、4 -胺基-3-氣- 6- (4-氯-2-氟-3-曱氧基-苯基)-吡啶-2-曱酸曱酯及4-胺基-3-氣-6-(4_氣_3_二曱胺基_2_氟-苯基)-吡啶_2_甲酸曱酯。 I) 殺昆蟲劑 - 有機(硫代)磷酸酯:歐殺松(acephate)、亞滅松 (azamethiphos)、穀速松(azinphos-methyl)、陶斯松 (chlorpyrifos)、甲基陶斯松(chlorpyrifos-methyl)、克芬松 147475.doc •124· 201043139 ΟSodium), chlorine S, cloransulam-methyl, diclosulam, flusarusm, 'flucarbazone, flumetsulam , performance grass. Metasulam, ortho-sulfamuron, penoxsulam, propoxycarbazone, pyribambenz-propyl, ° Pyribenzoxim, pyrifalid, pyriminobac-methyl, pyrimisulfan &gt; pyrithiobac, pyroxasulfone, methoxy Pyromycin (pyroxsulam); - Others: amine amicarbazone, aminotriazole, anilofos, beflubutamid, benazolin, Bencarbazone, benfluresate, benzofenap, bentazone, benzobicyclon, bromacil, chlorfenapyr Bromobutide), butifenacil, butamifos, butamifos, cafenstrole, carfentrazone, cinidon-ethlyl, enemy Chlorothal, cinmethylin, clomazone, benzyl Cuyluron, cyprosulfamide, dicamba, wild swallow, diflufenzopyr, drechslera monoceras, endothal , ethofumesate, etobenzanid, fentrazamide, flumiclorac-pentyl, flumioxazin, flufenacil Flupoxam, fluorochloridone, flurtamone, 147475.doc -123- 201043139 indanofan, isoxaben, isoxaben Isoxaflutole, lenacil, propanil, propyzamide, quinclorac, quinmerac, methyl stone yellow grass | (mesotrione) ) 'Methyl decanoic acid, naptalam, oxadiargyl, oxadiazon, oxaziclomefone, pentoxazone, pentoxazone. Sitting on pinoxaden, pyraclonil, pyraflufen-ethyl, pyrasulfotol, pyrazoxyfen, pyrazolynate , quinoclamine, saprofenacil, sulcotrion, sulfentrazone, terbacil, tefbryltrione 'teber Ketone (tembotrione), thiencarbazone, topramezone, 4-hydroxy-3-[2-(2-methoxy-ethoxyindolyl)-6-trifluoromethylpyridinium 3-carbonyl]-bicyclo[3.2.1]oct-3-en-2-one, (3-[2-chloro-4-fluoro-5-(3-methyl-2,6-di-oxyl) 4-trifluoromethyl-3,6-dihydro-2H-pyrimidin-1-yl)-phenoxy]pyridin-2-yloxy)-acetate, 6-amino-5-gas 2-cyclopropyl-pyrimidine-4-decanoate, 6-gas-3-(2-cyclopropyl-6-mercapto-phenoxy)-pyridazin-4-ol, 4-amino group -3 -Chloro-6-(4-chloro-phenyl)-5-fluoro-0 to 0-but-2-carboxylic acid, 4-amino-3-gas-6-(4-chloro-2-fluoro-3 -nonyloxy-phenyl)-pyridin-2-indole decyl ester and 4-amino-3-gas-6-(4_gas_3_dioxanyl-2-fluoro-benzene ) - pyridine _2_ Yue acid ester. I) Insecticides - Organic (thio) phosphates: acephate, azamethiphos, azinphos-methyl, chlorpyrifos, chlorpyrifos-methyl Kefensong 147475.doc •124· 201043139 Ο

(chlorfenvinphos)、大利松(diazinon)、二氯松(dichlorvos)、 雙特松(dicrotophos)、大滅松(dimethoate)、二硫松 (disulfoton)、愛殺松(ethion)、撲滅松(fenitrothion)、芬殺 松(fenthion)、加福松(isoxathion)、馬拉松(malathion)、達 馬松(methamidophos)、滅大松(methidathion)、曱基巴拉 松(methyl-parathion)、美文松(mevinphos)、亞素靈 (monocrotophos)、滅多松(oxydemeton-methyl)、巴拉奥克 松(paraoxon)、巴拉松(parathion)、賽達松(phenthoate)、 裕必松(phosalone)、益滅松(phosmet)、福賜米松 (phosphamidon)、福瑞松(phorate)、巴賽松(phoxim)、亞特 松(pirimiphos-methyl)、布飛松(profenofos)、普硫松 (prothiofos)、殺普松(sulprophos)、樂本松(tetrachlorvinphos)、託 福松(terbufos)、三落松(triazophos)、三氣松(trichlorfon); - 胺基曱酸酯:棉靈威(alanycarb)、得滅克(aldicarb)、 免敵克(bendiocarb)、本夫克(benfbracarb)、加保利(carbaryl)、 加保扶(carbofuran)、丁基加保扶(carbosulfan) '芬諾克 (fenoxycarb)、D夫線威(furathiocarb)、滅賜克(methiocarb)、 納乃得(methomyl)、歐殺滅(oxamyl)、比加普(pirimicarb)、 安丹(propoxur)、硫雙威(thiodicarb)、β坐財威(triazamate); - 擬除蟲菊醋(pyrethroid):雅列寧(allethrin)、畢芬寧 (bifenthrin)、赛扶寧(cyfluthrin)、赛洛寧(cyhalothrin)、賽 紛寧(cyphenothrin)、賽滅寧(cypermethrin)、亞滅寧(alpha-cypermethrin)、β-賽滅寧、ξ-赛滅寧(zeta-cypermethrin)、第 滅寧(deltamethrin)、益化利(esfenvalerate)、依芬寧 147475.doc -125- 201043139 (etofenprox)、芬普寧(fenpropathrin)、芬化利(fenvalerate)、 依普寧(imiprothrin)、λ-赛洛寧(lambda-cyhalothrin)、百滅 寧(permethrin)、普亞列寧(prallethrin)、除蟲菊酯 I及 II、 異列滅寧(resmethrin)、石夕護芬(silafluofen)、福化利(tau-fluvalinate)、七氟菊 S旨(tefluthrin)、治滅寧(tetramethrin)、 泰滅寧(tralomethrin)、拜富寧(transfluthrin)、丙 I 菊酉旨 (profluthrin)、四敗曱醚菊醋(dimefluthrin); - 昆蟲生長調節劑:a)甲殼素(chitin)合成抑制劑:苯 甲醯脲:克福隆(chlorfluazuron)、賽滅淨(cyromazine)、 二福隆(diflubenzuron)、氟環脲(flucycloxuron)、I 芬隆 (flufenoxuron)、六伏隆(hexaflumuron)、祿芬隆(lufenuron)、 諾瓦隆(novaluron)、得福隆(teHubenzuron).、三福隆 (triflumuron);布芬淨(buprofezin)、苯蟲醚(diofenolan)、 合賽多(hexythiazox)、依殺蜗(etoxazole)、克芬瞒(clofentazin); b) 銳皮激素拮抗劑:合芬隆(halofenozide)、滅芬諾 (methoxyfenozide)、得芬諾(tebufenozide)、印楝素(azadirachtin); c) 保幼激素類似物(juvenoid):百利普芬(pyriproxyfen)、 美賜平(methoprene)、芬諾克(fenoxycarb) ; d)脂質生物合 成抑制劑:賜派芬(spirodiclofen)、螺曱蛾S旨(spiromesifen)、 螺蟲乙酿(spirotetramat); - 於驗受體促效劑/拮抗劑化合物:可尼丁(clothianidin)、 達特南(dinotefuran)、益達胺(imidacloprid)、賽速安 (thiamethoxam)、稀咬蟲胺(nitenpyram)、亞滅培(acetamiprid)、 赛果培(thiacloprid)、1-(2-氣-噻唑-5-基曱基)-2-硝亞胺基- 147475.doc -126· 201043139 3,5-二甲基-[1,3,5]三氮雜環己烷; -GABA拮抗劑化合物:安殺番(endosulfan)、乙蟲清 (ethiprol)、芬普尼(fipronii)、凡尼普羅(vanjiipr〇i)、氟蟲 腈(PyrafluPro1)、派瑞樂(pyriprol)、5-胺基-1-(2,6-二氯-4-曱基-苯基)_4-胺亞磺醯基-1H-吡唑-3-硫代曱酸醯胺; - 巨環内酯殺昆蟲劑:阿巴江(abamectin)、因滅汀 (emamectin)、密滅 j;丁(milbemectin)、林皮沒丁(lepimectin)、 賜諾殺(spinosad)、斯平托蘭(spinetoram); -粒線體電子傳輸抑制劑(METI)I殺蟎劑:芬殺蟎 (fenazaquin)、畢達本(pyridaben)、得芬瑞(tebufenpyrad)、 脫芬瑞(tolfenpyrad)、氟芬内林(flufenerim); -METI II及ΠΙ化合物:亞酿蜗(acequinocyl)、福瑞姆 (fluacyprim)、愛美松(hydramethylnon); -解偶聯劑(Uncoupler):克凡派(chlorfenapyr); - 氧化碟酸化抑制劑:錫蜗丹(cyhexatin)、汰芬諾克 (diafenthiuron)、芬布錫(fenbutatin oxide)、殿蜗多(propargite); -蜆皮干擾化合物(moulting disruptor compound):賽 滅淨(cryomazine); - 混合功能氧化酶抑制劑:協力精(piperonyl butoxide); - 納通道阻斷劑:因得克(indoxacarb)、氰說蟲腙 (metaflumizone); -其他··苯氯嗟嗓(benclothiaz)、畢芬載(bifenazate)、 培丹(cartap)、氟尼胺(flonicamid)、咬蟲丙醚(pyridalyl)、 派滅淨(pymetrozine)、硫、硫賜安(thiocyclam)、氟蟲酿胺 147475.doc -127· 201043139 (flubendiamide)、剋安勃(chlorantraniliprol)、賽培(cyazypyr) (HGW86);塞諾 °比芬(cyenopyrafen)、比 l 硫鱗(flupyrazofos)、 丁氟蟎酯(cyflumetofen)、安米氟美(amidoflumet)、菸鹼硫 磷(imicyafos)、雙三氟蟲脲(bistrifiuron)及柏亞羅 (pyrifluquinazon) 〇 本發明此外係關於農用化學組合物,其包含至少一種化 合物I、II及/或IV(組分1)與至少一種適用於植物保護之例 如選自A)組至I)組之其他活性物質(組分2)(尤其為另一殺 真菌劑,例如一或多種來自如上所述之A)組至F)組的殺真 菌劑)及必要時一種適合溶劑或固體載劑的混合物。因為 許多彼等混合物在相同施用量下顯示較高之對抗有害真菌 之效率,所以其尤其受關注。此外,以化合物 IV與至少一種如上所述來自Α)組至F)組之殺真菌劑的混合 物對抗有害真菌比以個別化合物I、II或IV或來自A)組至F) 、且之们真菌劑對抗彼等真菌更有效。藉由施用化合物 I、II及/或IV連同至少一種來自Α組至川且之活性物質可 達成協同效應,亦即達成大於個別作用之簡單加和(協同 混合物)。 I、根據本發明,應瞭解,施用化合物卜11及/或1¥連同至 少—種其他活性物質表示至少-種式I、II及/或IV化合物 及至少—種其他活性物質以殺真菌有效量同時出現於作用 即待防治之有害真菌或其生境,諸如感染植物、 :殖材料(尤其為種子)、表面、材料或土壤,以及待 免真囷知襲之植物、植物繁殖材料(尤其為種 147475.doc -128· 201043139 子)土壤、表面、材料或空間)。此可藉由同時(聯合(例 &amp;以槽犯合物之形式)或分別地))或連續地施用化合物I、II 及/或IV及至少—種其他活性物質來達成,其中在個別施 - 肖之間的時間間隔經選擇以確保首先施用之活性物質在施 肖其他性物質之時仍以足量存在於作用部位。施用順序 對於本發明之工作並不重要。 在一元混合物,亦即包含一種化合物I、II或IV(組分1) ❹ 及另/舌性物質(組分2)(例如一種來自A)組至〗)組之活性 物質)的本發明組合物中,組分丨與組分2之重量比一般視 所用活性物質之特性而定,其通常在1:1⑽至·i之範圍 内,經常在1:50至50:1之範圍内,較佳在1:2〇至2〇:1之範 圍内,更佳在1:10至10:1之範圍内且特定言之在1:3至3:1 之範圍内。 在三元混合物,亦即包含一種化合物j、π&amp;/4ΐν(組分 υ及第一其他活性物質(組分2)及第二其他活性物質(組分 〇 3)(例如兩種來自Α)組至I)組之活性物質)的本發明組合物 中,組分1與組分2之重量比視所用活性物質之特性而定, 其較佳在1:50至50:1之範圍内且尤其在1:1〇至1〇:1之範圍 .内,且組分1與組分3之重量比較佳在1:5〇至5〇:1之範圍内 且尤其在1:10至10:1之範圍内。 組分可個別地或彼此部分或完全混合後用來製備本發明 之組合物。其亦可進一步以組合組合物(諸如分裝部分之 套組)之形式封裝及使用。 在本發明之一個實施例中,套組可包括一或多種(包括 147475.doc •129- 201043139 所有)可用以製備標的農用化學組合物之組分。舉例而 5,套組可包含一或多種殺真菌劑組分及/或佐劑組分及/ 或殺昆蟲劑組分及/或生長調節劑組分及/或除草劑。一或 多種組分可已組合在一起或經預調配。在套組中提供兩種 以上組分之彼等實施例中,組分可已組合在一起且按原樣 封裝於諸如小瓶、瓶、罐、小袋、袋或小罐之單一容器 中。在其他實施例中,可將套組之兩種或兩種以上組分分 ,封裝,亦即不預調配。因此,套組可包括一或多個個別 ”器諸如小瓶、罐、瓶、小袋、袋或小罐,各容器含有 農用化學組合物之個別組分。在兩種形式中,套組之一種 $分可與其他組分分開施用或一起施用或以製備本發明組 α物之本發明組合組合物的組分之形式施用。 使用者通常自前劑量裝置(predosage device)、背負式噴 霧益、噴霧槽或喷灑機施用本發明之組合物。此處,農用 ♦予..且σ物係由水及/或緩衝液補足至所需施用濃度,適 夺可添加其他助劑,且因此獲得本發明之即用型喷霧液 體或農用化學組合物。每公頃農業有效面積通常施用5〇公 升’較佳100公升至4〇〇公升即用型噴霧液體。 根據個實施例,本發明組合物之個別組分,諸如套組 之部分式-二』_ 70或二凡混合物之部分’可由使用者本人在喷 霧槽中'昆合,且適當時可添加其他助劑(槽混)。 另 官 貫施例中’本發明組合物之個別組分或部分預混 .刀例如包含化合物I、II及/或〗乂及/或來自A)組至〗)組 之活性物曾沾&amp;人 γ , 、的、、且刀’可由使用者在喷霧槽中混合且適當時 147475.doc -130- 201043139 可添加其他助劑及添加劑(槽混)。 在另κ施例中,本發明組合物之個別組分或部分預混 、、且刀,例如包含化合物丨、π及/或…及/或來自Α)組至U組 之/舌〖生物質的組分,可聯合(例如在槽混之後)施用或連續 施用。 包含化合物I、Π及/或1¥(組分〇及至少一種選自Α)組之 a毬果傘素且尤其選自以下之活性物質(組分2)的混合物亦 較佳:亞托敏、醚菌胺、氟嘧菌酯、克收欣、肟醚菌胺、 啶氧菌胺、百克敏及三氟敏。 包含化合物I、II及/或IV(組分〇及至少一種選自組之 羧醯胺且尤其選自以下之活性物質(組分2)的混合物亦較 佳:百克芬、白克列' 色達安、環醯菌胺、滅達樂、異哌 劄美、右滅達樂、呋醯胺、達滅芬、氟嗎啉、氟TI比菌胺 (η比考苯胺(picobenzamid))、座賽胺、加普胺、雙炔醯菌胺 及N-(3’,4’,5’-三氟聯苯-2-基)-3-二氟甲基甲基_1H_吡唑_ 4-甲醯胺。 包含化合物I、II及/或IV(組分1)及至少一種選自c)組之 吐且尤其選自以下之活性物質(組分2)的混合物較佳:環克 座、待克利、依普座、氟喹唑、護矽得、護汰芬、滅特 座、邁克尼、平克座、普克利、丙硫菌唑、三泰芬、三泰 隆、得克利、四克利、滅菌唑、撲克拉、賽座滅、免賴 得、貝芬替及噻唑菌胺。 包含化合物I、II及/或IV(組分1)及至少一種選自D)組之 雜環化合物且尤其選自以下之活性物質(組分2)的混合物亦 147475.doc •131- 201043139 較佳:扶吉胺、赛普洛、芬瑞莫、滅派林、派美尼、賽福 寧D蔓汰寧、嗎菌靈、芬普福、三得芬、苯鏽啶、依普 同、免克寧、凡殺同、咪唑菌酮、撲殺熱、普奎那茲、酸 化苯并塞一唑_s_甲酯、四氯丹、福爾培、氰菌胺、快諾 芬及5-乙基-6、辛基_π,2,4]三唑并嘧啶_7_基胺。 包含化合物I、π及/或…(組分丨)及至少一種選自E)組之 胺基曱酸酯且尤其選自鋅錳乃浦、免得爛、曱基辞乃浦、 得恩地、纈黴威、苯噻菌胺及霜黴威之活性物質(組分幻的 混合物亦較佳。 包含化合物I、π及/或1¥(組分丨)及至少一種選自組之 救真菌劑且尤其選自以下之活性物質(組分2)的混合物亦較 佳.腈硫醌 '三苯錫鹽(諸如三苯醋錫)、福賽得、福賽得 鋁、H3P〇3及其鹽、四氣異苯腈、益發靈、甲基多保淨、 乙酸銅、氫氧化銅、氣氧化銅、硫酸銅、硫、克絕、滅芬 農及螺惡戊胺。 因此本發明此外係關於組合物,其包含一種化合物 I、II及/或IV(組分1)及另一活性物質(組分2),該另一活性 物質係選自表B之第B-1至b_346行之「組分2」一攔。 另一貫施例係關於表B中所列之組合物1至b-346,其 中表B之一列在各情況下對應於包含一種在本說明書中之 個別化式I、II或IV化合物(組分1)及所討論之列中所述的 來自A)組至I)組之各別其他活性物質(組分2)的殺真菌組合 物。所述組合物較佳包含協同有效量之活性物質。 表B :包含一種個別化化合物〖、^或…及來自a)組至〇 147475.doc •132- 201043139 組之另一活性物質的組合物 混合物 組分1 組分2 B-1 一種個別化化合物I、II或IV 亞托敏 B-2 一種個別化化合物I、II或IV 醚菌胺 B-3 一種個別化化合物I、II或IV 烯肟菌酯 B-4 一種個別化化合物I、II或IV 氟嘧菌酯 B-5 一種個別化化合物I、II或IV 克收欣 B-6 一種個別化化合物I、II或IV 苯氧菌胺 B-7 一種個別化化合物I、II或IV 肟醚菌胺 B-8 一種個別化化合物I、II或IV 啶氧菌胺 B-9 一種個別化化合物I、II或IV 百克敏 B-10 一種個別化化合物I、II或IV 口比本卡 B-11 一種個別化化合物I、II或IV 三氟敏 B-12 一種個別化化合物I、II或IV 2-(2-(6-(3-氣-2-甲基-苯氧基)-5-氟-嘯咬_ 4-基氧基)-苯基)-2-甲氧基亞胺基-N-曱 基-乙酿胺 B-13 一種個別化化合物I、II或IV 2- (鄰((2,5-二甲基苯氧基亞甲基)苯基)- 3- 甲氧基丙烯酸甲酯 B-14 一種個別化化合物I、II或IV 3-曱氧基-2-(2-(N-(4-甲氧基-苯基)-環丙 烷曱醯亞胺醯基硫基曱基)-苯基)-丙烯 酸曱酯 B-15 一種個別化化合物I、II或IV 2-(2-(3-(2,6-二氣苯基)-1 -曱基-亞烯丙[ 胺基氧基曱基)-苯基)-2-甲氧基亞胺基_ N-甲基-乙醯胺 B-16 一種個別化化合物I、II或IV 本達樂 B-17 一種個別化化合物I、II或IV 右本達樂 ~~ B-18 一種個別化化合物I、II或IV 麥鏽靈 B-19 一種個別化化合物I、II或IV 百克芬 ~~ B-20 一種個別化化合物I、II或IV 白克利 B-21 一種個別化化合物I、II或IV 萎鏽靈 B-22 一種個別化化合物I、II或IV 曱呋醯胺 ~~ B-23 一種個別化化合物I、II或IV 環酿菌胺 —~~ B-24 一種個別化化合物I、II或rv 氟多寧 — B-25 一種個別化化合物I、II或IV 福拉比 ~~ B-26 一種個別化化合物I、II或IV 異派劄美 B-27 一種個別化化合物I、π或rv 異天尼 B-28 一種個別化化合物I、π或rv 開達樂 ' B-29 一種個別化化合物I、II或rv 3普寧 B-30 一種個別化化合物I、π或rv 滅達樂 ――— B-31 一種個別化化合物I、II或IV 右滅達樂 B-32 一種個別化化合物I、II或IV 呋醯胺 ~ B-33 一種個別化化合物I、Π或IV 歐殺斯 一 147475.doc •133· 201043139 混合物 組分1 組分2 B-34 一種個別化化合物I、II或IV 嘉保信 B-35 一種個別化化合物I、II或IV B-36 一種個別化化合物I、II或IV 色達安 B-37 一種個別化化合物I、Π或IV 克枯煳 ' B-38 一種個別化化合物I、II或IV —--- B-39 一種個別化化合物I、Π或IV 汰敵寧 B-40 一種個別化化合物I、II或IV 胺基-4-甲基ϋ5_甲酿笑胳 B-41 一種個別化化合物I、II或IV 土查^-(1,1,3-:曱基·茚滿冰幕)·菸鹼醯胺 B-42 一種個別化化合物I、II或IV Ν-(3·,4ΐ,5,-三氟聯苯基)_3·二氟甲基_;1 _ 吡唑-4-甲醯脸 B-43 一種個別化化合物I、II或IV 1(4'-三氟曱基硫基聯苯_2_基)_3_二氟甲 n甲基-lH-n比唾-4-甲醯胺 B-44 一種個別化化合物I、II或IV N-(2-(l,3-二曱基-丁基)_ 苯基)·13_ 二 f 一基-5-氟-1Η-»比嗤-4-曱醯胺 B-45 一種個別化化合物I、II或IV 叫2-(1,3,3-三曱基-丁基)_苯基二曱 -基-5-lt-lH·0比峻-4·甲醯胺 B-46 一種個別化化合物I、II或IV 達滅芬 B-47 一種個別化化合物I、II或IV 氟嗎琳 B-48 一種個別化化合物I、II或IV 丁°比嗎琳 B-49 一種個別化化合物I、II或IV 氟醯菌胺 B-50 一種個別化化合物I、II或IV 亂°比菌胺 B-51 一種個別化化合物I、Π或IV 氟吡菌醯胺 B-52 一種個別化化合物I、II或IV 座賽胺 B-53 一種個別化化合物I、Π或IV N-(3-乙基-3,5,5-三甲基-環己基)-3-曱醯 胺基-2-羥基-苯甲醢胺 B-54 一種個別化化合物I、II或IV 加普胺 B-55 一種個別化化合物I、II或IV 二氣西莫 B-56 一種個別化化合物I、II或IV 雙炔醯菌胺 B-57 一種個別化化合物I、II或IV 土黴素 B-58 一種個別化化合物I、II或IV 矽噻菌胺 B-59 一種個別化化合物I、Π或IV N-(6-曱氧基-吡啶-3-基)環丙烷曱酸醯胺 B-60 一種個別化化合物I、II或IV 阿紮康α坐 B-61 一種個別化化合物I、II或IV 比多農 B-62 一種個別化化合物I、Π或IV 溴克座 B-63 一種個別化化合物I、II或IV 環克座 B-64 一種個別化化合物I、II或IV 待克利 B-65 一種個別化化合物I、Π或IV 達i利 B-66 一種個別化化合物I、II或IV 右達克利 B-67 一種個別化化合物I、II或rv 依普座 B-68 一種個別化化合物I、Π或IV 芬克座 B-69 一種個別化化合物I、II或IV 氟喹唑 B-70 一種個別化化合物I、II或IV m矽得 B-71 一種個別化化合物I、Π或IV 護汰芬 •134· 147475.doc 201043139 混合物 組分1 組分2 B-72 一種個別化化合物I、II或IV 菲克利 B-73 一種個別化化合物I、II或IV 易胺座 B-74 一種個別化化合物I、II或IV 依普克嗤 B-75 一種個別化化合物I、II或IV 滅特座 B-76 一種個別化化合物I、II或IV 邁克尼 B-77 一種個別化化合物I、II或IV 惡咪嗤 B-78 一種個別化化合物I、II或IV 巴克素 B-79 一種個別化化合物I、II或IV 平克座 B-80 一種個別化化合物I、II或IV 普克利 B-81 一種個別化化合物I、II或IV 丙硫菌。坐 B-82 一種個別化化合物I、II或IV 矽氟唑 B-83 一種個別化化合物I、II或IV 得克利 B-84 一種個別化化合物I、II或IV 四克利 B-85 一種個別化化合物I、II或IV 二泰分 B-86 一種個別化化合物I、II或IV 三泰隆 B-87 一種個別化化合物I' II或IV 滅菌。坐 B-88 一種個別化化合物I、II或IV 浠效°坐 B-89 一種個別化化合物I、II或IV 1-(4-氣-苯基)-2-([1,2,4]三唑-1-基)-環庚醇 B-90 一種個別化化合物I、II或IV 賽座滅 B-91 一種個別化化合物I、II或IV 依滅列 B-92 一種個別化化合物I、II或IV 硫酸依滅列 B-93 一種個別化化合物I、II或IV 稻盘酯 B-94 一種個別化化合物I、II或IV 撲克拉 B-95 一種個別化化合物I、II或IV 賽福座 B-96 一種個別化化合物I、II或IV 免賴得 B-97 一種個別化化合物I、II或IV 貝芬替 B-98 一種個別化化合物I、II或IV 麥穗寧 B-99 一種個別化化合物I、II或IV 腐絕 B-100 一種個別化化合物I、II或IV 噻唑菌胺 B-101 一種個別化化合物I、II或IV 依得利 B-102 一種個別化化合物I、II或IV 惡黴靈 B-103 一種個別化化合物I、II或IV 2-(4-氯-苯基)-N-[4-(3,4-二甲氧基-苯基)-異噁唑-5-基]-2-丙-2-炔氧基-乙醯胺 B-104 一種個別化化合物I、II或IV 扶吉胺 B-105 一種個別化化合物I、II或IV 比芬諾 B-106 一種個別化化合物I、II或IV 3-[5-(4-氣-苯基)-2,3-二甲基-異噁唑啶-3-基]-°比嗓 B-107 一種個別化化合物I、II或IV 3-[5-(4-曱基-苯基)-2,3-二曱基-異噁唑 嗓-3-基]-α比淀 B-108 一種個別化化合物I、II或IV 2,3,5,6-四氣_4_曱烧續酿基-〇比受 B-109 一種個別化化合物I、II或IV 3,4,5-二氯-°比咬-2,6-二曱腈 B-110 一種個別化化合物I、II或IV 1^-(1-(5-&gt;臭-3-氯-0比淀-2-基)-乙基)-2,4-二 氣-於驗醯胺 147475.doc -135 - 201043139 混合物 組分1 組分2 B-lll 一種個別化化合物I、II或IV N-((5-溴-3-氯-。比啶-2-基)-甲基)-2,4-二 氯_終驗醢胺 B-112 一種個別化化合物I、II或IV 布瑞莫 B-113 一種個別化化合物I、II或IV 賽普洛 B-114 一種個別化化合物I、II或IV 二氣林 B-115 一種個別化化合物I、II或IV 芬瑞莫 B-116 一種個別化化合物I、II或IV 富瑞綜 B-117 一種個別化化合物I、II或IV 滅派林 B-118 一種個別化化合物I、II或IV 氣啶 B-119 一種個別化化合物I、II或IV 尼瑞莫 B-120 一種個別化化合物I、II或IV 派美尼 B-121 一種個別化化合物I、II或IV 賽福寧 B-122 一種個別化化合物I、II或IV 拌種咯 B-123 一種個別化化合物I、II或IV 護汰寧 B-124 一種個別化化合物I、II或IV 阿迪嗎淋 B-125 一種個別化化合物I、II或IV 嗎菌靈 B-126 一種個別化化合物I、II或IV 乙酸嗎菌靈 B-127 一種個別化化合物I、II或IV 芬普福 B-128 一種個別化化合物I、II或IV 三得芬 B-129 一種個別化化合物I、II或IV 苯鏽咬 B-130 一種個別化化合物I、II或IV °坐吱草 B-131 一種個別化化合物I、II或IV 依普同 B-132 一種個別化化合物I、II或IV 撲滅寧 B-133 一種個別化化合物I、II或IV 免克寧 B-134 一種個別化化合物I、II或IV 凡殺同 B-135 一種個別化化合物I、II或IV 喃°坐菌酮 B-136 一種個別化化合物I、II或IV 福天尼 B-137 一種個別化化合物I、II或IV 辛噻酮 B-138 一種個別化化合物I、II或IV 撲殺熱 B-139 一種個別化化合物I、II或IV 5·胺基-2-異丙基-4-鄰曱苯基-2,3-二氮-吡唑-1·硫代甲酸S-烯丙酯 B-140 一種個別化化合物I、Π或IV 酸化苯并噻二唑-S-甲酯 B-141 一種個別化化合物I、II或IV 吲唑磺菌胺 B-142 一種個別化化合物I、II或rv 敵菌靈 B-143 一種個別化化合物I、II或IV 保米黴素 B-144 一種個別化化合物I、II或IV 四氯丹 B-145 一種個別化化合物I、II或IV 蓋普丹 B-146 一種個別化化合物I、II或IV 滅瞒猛 B-147 一種個別化化合物I、II或IV 邁隆 B-148 一種個別化化合物I、II或IV 15米菌威 B-149 一種個別化化合物I、II或IV 達滅淨 B-150 一種個別化化合物I、II或IV 野燕枯 B-151 一種個別化化合物I、II或IV 曱基硫酸野燕枯 147475.doc -136- 201043139 混合物 組分1 組分2 B-152 一種個別化化合物I、Π或IV 氰菌胺 B-153 一種個別化化合物I、II或IV 福爾培 B-154 一種個別化化合物I、II或IV 歐索林酸(OxolinsSure) B-155 一種個別化化合物I、Π或IV 粉病靈 B-156 一種個別化化合物I、π或IV 普奎那茲 B-157 一種個別化化合物I、II或IV 百快隆 __ B-158 一種個別化化合物I、Π或IV 快諾芬 B-159 一種個別化化合物I、II或IV 咪唑嗪 B-160 一種個別化化合物I &gt; II或IV 三赛唑 B-161 一種個別化化合物I、II或IV 2-丁氧基-6-蛾-3-丙基-咬稀-4-酮 B-162 一種個別化化合物I、II或IV 5_氣-1-(4,6-二曱氧基-嘯咬_2_基)_2_甲 基-1H-笨并咪唑 B-163 一種個別化化合物I、II或IV 5-氯-7-(4-甲基-π辰咬-1-基)_6-(2,4,6-三 氟-苯基)-[1,2,4]三唾并[l,5-al响咬 B-164 一種個別化化合物I、II或IV 5·乙基_6·辛基-[I,2,4]三唾并[l,5-a]°®咬-7-基胺 B-165 一種個別化化合物I、II或rv 福美鐵 B-166 一種個別化化合物I、II或IV 鋅錳乃浦 B-167 一種個別化化合物I、II或IV 錳乃浦 B-168 一種個別化化合物I、II或IV 威百故 B-169 一種個別化化合物I、II或IV 磺菌威 B-170 一種個別化化合物I、II或IV 免得爛 B-171 一種個別化化合物I、II或IV 甲基鋅乃浦 B-172 一種個別化化合物I、II或IV 得恩地 B-173 一種個別化化合物I、II或IV 鋅乃浦 B-174 一種個別化化合物I、II或IV 益穗 B-175 一種個別化化合物I、II或IV 乙黴威 B-176 一種個別化化合物I、II或IV 苯噻菌胺 B-177 一種個別化化合物I、II或IV 纈黴威 B-178 一種個別化化合物I、II或IV 霜黴威 B-179 一種個別化化合物I、II或IV 霜黴威鹽酸鹽 B-180 一種個別化化合物I、II或IV 瓦芬那 B-181 一種個別化化合物I、II或IV N_(l -(1 -(4-氰基苯基)6烷磺醯基)-丁 J-基)胺基甲S复-(4-氟苯基)酯 B-182 一種個別化化合物I、II或IV 多寧 B-183 一種個別化化合物I、II或IV 多寧游離鹼 B-184 一種個別化化合物I、II或IV 雙胍鹽 . B-185 一種個別化化合物I、II或IV 乙酸雙胍鹽 — B-186 一種個別化化合物I、II或IV 雙胍辛胺 B-187 一種個別化化合物I、II或IV 二乙酸雙胍辛胺 — B-188 一種個別化化合物I、II或IV 參(烷基笨確酸)雙胍辛胺 B-189 一種個別化化合物I、II或IV 喜賜黴素___ B-190 一種個別化化合物I、II或IV 水合鹽酸喜賜黴素 -137- 147475.doc 201043139 混合物 組分1 組分2 B-191 一種個別化化合物I、II或IV 多氧菌素 B-192 一種個別化化合物I、II或IV 鏈黴素 B-193 一種個別化化合物I、II或IV 有效黴素A B-194 一種個別化化合物I、II或IV 百蟎克 B-195 一種個別化化合物I、II或IV 大克爛(Dicloran) B-196 一種個別化化合物I、II或IV 消蟎通 B-197 一種個別化化合物I、II或IV 白粉克 B-198 一種個別化化合物I、II或IV 欣菌醋(Nitrothal-isopropyl) B-199 一種個別化化合物I、II或IV 四氣硝基苯 B-200 一種個別化化合物I、II或IV 三苯錫鹽 B-201 一種個別化化合物I、II或IV 腈硫醌 B-202 一種個別化化合物I、II或IV 稻痕靈 B-203 一種個別化化合物I、II或IV 護粒松 B-204 一種個別化化合物I、II或IV 福赛得、福賽得鋁 B-205 一種個別化化合物I、II或IV 丙基喜樂松 B-206 一種個別化化合物I、II或IV 亞填S曼(H3PO3)及衍生物 B-207 一種個別化化合物I、II或IV 白粉松 B-208 一種個別化化合物I、II或IV 脫克松 B-209 一種個別化化合物I、II或IV 四氣異苯腈 B-210 一種個別化化合物I、II或IV 益發靈 B-211 一種個別化化合物I、II或IV 二氯酚 B-212 一種個別化化合物I、II或IV 磺菌胺 B-213 一種個別化化合物I、II或IV 六氣苯 B-214 一種個別化化合物I、II或IV 賓克隆 B-215 一種個別化化合物I、II或IV 五氣苯酚及鹽 B-216 一種個別化化合物I、II或IV 熱必斯 B-217 一種個別化化合物I、II或IV 五氣硝基苯 B-218 一種個別化化合物I、II或IV 曱基多保淨 B-219 一種個別化化合物I、II或IV 甲基益發靈 B-220 一種個別化化合物I、II或IV N-(4-乳·2_硝基-苯基)-N-乙基-4-曱基-苯 磺醯胺 B-221 一種個別化化合物I、II或IV 波多混合液 B-222 一種個別化化合物I、II或IV 乙酸銅 B-223 一種個別化化合物I、II或IV 氫氧化銅 B-224 —種個別化化合物I、II或IV 氯氧化銅 B-225 一種個別化化合物I、II或IV 鹼式硫酸銅 B-226 一種個別化化合物I、II或IV 硫 B-227 一種個別化化合物I、II或IV 聯苯 B-228 一種個別化化合物I、II或IV 溴硝丙二醇 B-229 一種個別化化合物I、II或IV 環氟菌胺 B-230 一種個別化化合物I、II或IV 克絕 B-231 一種個別化化合物I、II或IV 二苯胺 B-232 一種個別化化合物I、II或IV 滅分晨 147475.doc •138- 201043139 混合物 組分1 組分2 B-233 一種個別化化合物I、II或IV 滅粉黴素 B-234 一種個別化化合物I、II或IV 快得寧 B-235 一種個別化化合物I、II或IV 調環酸鈣 B-236 一種個別化化合物I、II或IV 螺惡茂胺 B-237 一種個別化化合物I、II或IV 甲基益發靈 B-238 一種個別化化合物I、II或IV N-(溱丙基曱氧基亞胺基-(6-二氟甲氧 基-2,3-二IL-苯基)-甲基)-2-苯基乙醯胺 B-239 一種個別化化合物I、II或IV NH4-(4-氯-3-三氟曱基-苯氧基)-2,5-二 甲基-苯基)-N-乙基-N-曱基甲脒 B-240 一種個別化化合物I、II或IV 1 Ν·-(4-(4-氟-3-三氟甲基-苯氧基)-2,5-二 甲基-苯基)-Ν-乙基-Ν-甲基甲脒 B-241 一種個別化化合物I、II或IV Ν'-(2-曱基-5-三氟甲基-4-(3-三曱基梦烷 基-丙氧基)-苯基)-N-乙基-N-曱基甲脒 B-242 一種個別化化合物I、II或IV N'-(5-二氟甲基-2-甲基-4-(3-三甲基矽烷 基-丙氧基)-苯基)-N-乙基-N-甲基甲脎 B-243 一種個別化化合物I、II或IV 2-{1-[2-(5-甲基-3-三氟曱基-咣嗤-1-基)-乙醯基]-〇底咬-4-基}-嗓嗤-4-曱酸甲基-(1,2,3,4-四風秦-1-基)-釀胺 B-244 一種個別化化合物I、II或IV 2-{1-[2-(5-甲基-3-三氟甲基-吡唑-1-基)-乙醯基]-哌啶-4-基}-噻唑-4-甲酸曱基-(R)-l,2,3,4-四氫萘-1-基-醯胺 B-245 一種個別化化合物I、II或IV 乙酸6-第三丁基-8-氟-2,3-二甲基-啥淋-4-基酯 B-246 一種個別化化合物I、II或IV 甲氧基-乙酸6-第三丁基-8-氟-2,3-二甲 基-喹琳-4-基酯 B-247 一種個別化化合物I、II或IV 加保利 B-248 一種個別化化合物I、II或IV 加保扶 B-249 一種個別化化合物I、II或IV 丁基加保扶 B-250 一種個別化化合物I、II或IV 納乃得硫雙威(Methomylthiodicarb) B-251 一種個別化化合物I、II或IV 畢芬寧 B-252 一種個別化化合物I、II或IV 賽扶寧 B-253 一種個別化化合物I、II或IV 賽滅寧 B-254 一種個別化化合物I、II或IV 亞滅寧 B-255 一種個別化化合物I、II或IV ξ-賽滅寧 B-256 一種個別化化合物I、II或IV 第滅寧 B-257 一種個別化化合物I、II或IV 益化利 B-258 一種個別化化合物I、II或IV λ-賽洛寧 B-259 一種個別化化合物I、II或IV 百滅寧 B-260 一種個別化化合物I、II或IV 七氟菊酯 B-261 一種個別化化合物I、II或IV 二福隆 B-262 一種個別化化合物I、II或IV 氣芬隆 B-263 一種個別化化合物I、II或IV 祿芬隆 B-264 一種個別化化合物I、II或IV 得福隆 147475.doc •139· 201043139 混合物 組分1 組分2 B-265 一種個別化化合物I、II或IV 螺蟲乙酯 B-266 一種個別化化合物I、II或IV 可尼丁 B-267 一種個別化化合物I、Π或IV 達特南 B-268 一種個別化化合物I、Π或IV 益達胺 B-269 一種個別化化合物I、II或IV 賽速安 B-270 一種個別化化合物I、II或IV 亞滅培 B-271 一種個別化化合物I、II或IV 賽果培 B-272 一種個別化化合物I、II或IV 安殺番 B-273 一種個別化化合物I、II或IV 芬普尼 B-274 一種個別化化合物I、Π或IV 阿巴汀 B-275 一種個別化化合物I、II或IV 因滅汀 B-276 一種個別化化合物I、II或IV 賜諾殺 B-277 一種個別化化合物I、II或IV 斯平托蘭 B-278 一種個別化化合物I、Π或IV 愛美松 B-279 一種個別化化合物I、Π或IV 克凡派 B-280 一種個別化化合物I、II或IV 芬布錫 B-281 一種個別化化合物I、π或rv 因得克 B-282 一種個別化化合物I、Π或IV 氛氟蟲月宗 B-283 一種個別化化合物I、II或IV 氣尼胺 B-284 一種個別化化合物I、II或IV 氟蟲醯胺 B-285 一種個別化化合物I、Π或IV 剋安勃 B-286 一種個別化化合物I、II或IV 賽培(HGW86) B-287 一種個別化化合物I、II或IV 丁氟蟎酯 B-288 一種個別化化合物I、π或rv 乙草胺 B-289 一種個別化化合物I、II或IV 汰草滅 B-290 一種個別化化合物I、Π或IV 滅多草 B-291 一種個別化化合物I、Π或IV 滅草胺 B-292 一種個別化化合物I、II或IV 草甘膦 B-293 一種個別化化合物I、II或IV 草銨膦 B-294 一種個別化化合物I、II或rv 草硫膦 B-295 一種個別化化合物I、II或IV 炔草酸 B-296 一種個別化化合物I、II或IV 01 惡σ坐禾草靈 B-297 一種個別化化合物I、Π或IV 吡氟禾草靈 B-298 一種個別化化合物I、II或IV °比氟氣禾靈 B-299 一種個別化化合物I、Π或IV 百草枯 B-300 一種個別化化合物I、II或IV 甜菜寧 B-301 一種個別化化合物I、II或IV 烯草酮 B-302 一種個別化化合物I、Π或IV 環殺草 B-303 一種個別化化合物I、II或IV 環苯草酮 B-304 一種個別化化合物I、II或IV 西殺草 B-305 一種個別化化合物I、II或IV 得殺草 B-306 一種個別化化合物I、Π或IV 二曱戊樂靈 B-307 一種個別化化合物I、Π或IV 苯胺靈 147475.doc -140- 201043139 混合物 組分1 組分2 B-308 一種個別化化合物I、II或IV 氟樂靈 B-309 一種個別化化合物I、II或IV 三氟羧草醚 B-310 一種個別化化合物I、II或IV 溴苯腈 B-311 一種個別化化合物I、II或IV 咪草酯 B-312 一種個別化化合物I、II或IV 曱氧咪草菸 B-313 一種個別化化合物I、II或IV 甲基咪草菸 B-314 一種個別化化合物I、II或IV 味0坐於酸 B-315 一種個別化化合物I、II或IV °米°坐啥淋酸 B-316 一種個別化化合物I、II或IV 咪唑乙菸酸 B-317 一種個別化化合物I、II或IV 2,4-二氣苯氧基乙酸(2,4-D) B-318 一種個別化化合物I、II或IV 氯草敏 B-319 一種個別化化合物I、II或IV 克草立特 B-320 一種個別化化合物I、II或IV 氟草菸 B-321 一種個別化化合物I、II或IV 毒莠定 B-322 一種個別化化合物I、II或IV 氟吡醯草胺 B-323 一種個別化化合物I、II或IV 苄嘧磺隆 B-324 一種個別化化合物I、II或IV 氣嘧磺隆 B-325 一種個別化化合物I、II或IV 環丙嘧磺隆 B-326 一種個別化化合物I、II或IV 碘甲磺隆 B-327 一種個別化化合物I、II或IV 曱磺胺磺隆 B-328 一種個別化化合物I、II或IV 甲磺隆 B-329 一種個別化化合物I、II或IV 菸嘧磺隆 B-330 一種個別化化合物I、II或IV 砜嘧磺隆 B-331 一種個別化化合物I、II或IV 氟胺磺隆 B-332 一種個別化化合物I、II或IV 草脫淨 B-333 一種個別化化合物I、II或IV 六嗪酮 B-334 一種個別化化合物I、II或IV 敵草隆 B-335 一種個別化化合物I、II或IV 雙氟磺草胺 B-336 一種個別化化合物I、II或IV 普硫芬 B-337 一種個別化化合物I、II或IV 苯達松 B-338 一種個別化化合物I、II或IV α弓丨喝酮草醋 B-339 一種個別化化合物I、II或IV 環庚草醚 B-340 一種個別化化合物I、II或IV 麥草畏 B-341 一種個別化化合物I、II或IV 二氟吡隆 B-342 一種個別化化合物I、II或IV 二氣01琳酸 B-343 一種個別化化合物I、II或IV 草酸 B-344 一種個別化化合物I、II或IV 曱基磺草酮 B-345 一種個別化化合物I、II或IV 嘧啶肟草醚 B-346 一種個別化化合物I、II或IV 托潘腙 已知稱作組分2之活性物質、其製備及其對抗有害真菌 147475.doc •141- 201043139 之活性(參考:http://www.alanwood.net/pesticides/);此等 物質可購得。亦已知藉由IUPAC命名法描述之化合物、其 製備及其殺真菌活性(參考Can. J_ Plant Sci. 48(6), 587-94, 1968 ; EP-A 141 3 17; EP-A 1 52 03 1 ; EP-A 226 917 ; EP-A 243 970 ; EP-A 256 503 ; EP-A 428 941 ; EP-A 532 022 ; EP-A 1 028 125 ; EP-A 1 035 122 ; EP-A 1 201 648 ; EP-A 1 122 244 &gt; JP 2002316902 ; DE 19650197 ; DE 10021412 ; DE 102005009458 ; US 3,296,272 ; US 3,325,503 ; WO 98/46608 ; WO 99/14187 ; WO 99/24413 ; WO 99/27783 ; WO 00/29404 ; WO 00/46148 ; WO 00/65913 ; WO 01/54501 ; WO 01/56358 ; WO 02/22583 ; WO 02/40431 ; WO 03/10149 ; WO 03/11853 ; WO 03/14103 ; WO 03/16286 ; WO 03/53145 ; WO 03/61388 ; WO 03/66609 ; WO 03/74491 ; WO 04/49804 ; WO 04/83193 ; WO 05/120234 ; WO 05/123689 ; WO 05/123690 ; WO 05/63721 ; WO 05/87772 ; WO 05/87773 ; WO 06/15866 ; WO 06/87325 ; WO 06/87343 ; WO 07/82098 ; WO 07/90624) ° 可將活性物質之混合物藉由常見方式,例如藉由對於化 合物I、II及/或IV之組合物既定之方式製備為除活性成分 之外亦包含至少一種惰性成分之組合物。 關於此等組合物之常見成分,參考對於含有化合物I、II 及/或IV之組合物給出之說明。 如式I、II及IV化合物,本發明之活性物質的混合物適用 作殺真菌劑。其因對抗廣泛範圍之植物病原性真菌之突出 效用而著名,該等植物病原性真菌尤其來自子囊菌綱、擔 147475.doc -142- 201043139 子菌綱、半知菌綱及霜黴㈣綱㈤義詞㈣綱)。另外, 提及關於化合物及分別含有化合物I、歷/㈣之組合物 的殺真菌活性之說明。 . 本發明之另―態樣係關於種子,其每⑽kg種子包含 g至10kg之量的至少式I、Π及/或…化合物。 化合物卜11及1V及其醫藥學上可接受之鹽亦適於治療人 類及動物之疾病(尤其作為抗黴劑之用途),適於治療癌症 &amp;治療病毒感染。如不同於術語「殺真菌劑」之術語「抗 ί數劑」係指-種對抗動物病原性或人類病原性真菌,亦即 對抗動物、尤其哺乳動物及鳥類中之真菌的藥物。 因此,本發明之另一態樣係關於一種包含至少一種式 I、II及/或IV化合物及/或至少一種其醫藥學上可接受之鹽 及醫藥學上可接受之載劑的藥物。 適合醫藥學上可接受之鹽尤其為化合物卜π&amp;/或1¥之 生理上耐受之鹽’特定言之為與生理上可接受之酸形成的 〇 酸加成鹽。適合有機酸及無機酸的實例為鹽酸、氫溴酸、 磷酸、&amp; 、C^C:4烷基磺酸(諸如甲烷磺酸)、芳族磺酸 (諸如苯磺酸及甲苯磺酸)、乙二酸、順丁烯二酸、反丁烯 -二酸、乳酸、酒石酸、己二酸及苯甲酸。其他適合酸描述 於例如 Fortschritte der Arzneimittelforschung,第 1〇卷,第 224頁及其後内容,Birkhauser Verlag,Bas丨6及以加碚 1966中,其全部内容係以引用的方式明確併入本文中。 適合載劑為例如溶劑、載劑、賦形劑、黏合劑及通常用 於醫藥調配物之類似物,下文就個別投藥類型以例示性方 147475.doc -143 - 201043139 式加以描述。 本發明之另—態樣係關於化合物I、II及IV或其醫藥學上 可接文之鹽用於製備抗黴藥物;亦即用於製備治療及/或 預防人類病原性及/或動物病原性真菌感染之藥物的用 途。本發明之另一態樣係關於式I、II及/或IV化合物或其 醫藥學上可接受之鹽用於製備治療癌症之藥物的用途。本 發明之另一態樣係關於式I、π及/或IV化合物或其醫藥學上 可接又之鹽用於製備治療或預防病毒感染之藥物的用途。 、弋I 11及/或1V化合物及/或其醫藥學上可接受之鹽適用 於治療、抑制或控制腫瘤細胞之生長及/或增殖及2其相 關之病症。因此,其適用於治療溫血脊椎動物之癌症/,、該 寺溫血脊椎動物例如為哺乳動物及鳥|員,特定言之為人 類,以及其他哺乳動物,特定言之為有用家畜諸如犬、 L豬、反离動物(牛羊、山羊、野牛等)、馬及鳥類, =、火雞、鴻、鶴、珍珠雞及其類似動物。 二式I、π及合物及/或其醫藥學上可接受之鹽適用於 :療以下器官之癌症或癌性病症:乳房、肺、腸、前列 j皮膚(黑色素瘤)、腎臟 '膀胱、口、喉、食道、胃、 印巢、胰腺、肝臟及腦或CNS。 月 1!謂化合物及’或其醫藥學上可接受之鹽適用於 :、:血脊椎動物之病毒感染’該等溫金脊椎動物例如 自礼動物及鳥類,特定言之為 為 特定言之為有用家畜,諸如犬其他哺乳動物, 菜 黏、豬、反舞動物(牛、 平、山羊、野牛等)、馬及鳥類,諸如雞、火雞、鴨、 147475.doc • 144- 201043139 鶴、珍珠雞及其類似動物。其適用於治療病毒感染,如反 轉錄病毒感染(諸如HIV及HTLV)、流感病毒感染、鼻病毒 感染、疱疹及其類似病毒。 可以常用方式(例如經口、靜脈内、肌肉内或皮下)投與 本發明之化合物。對於經口投與,可將活性化合物例如與 惰性稀釋劑或與可食用載劑混合;可將其包埋於硬明膠膠 囊或軟明膠膠囊中,可將其壓縮為錠劑或可將其直接與食 〇 物/飼料混合。活性化合物可與賦形劑混合且以不可消化 錠劑、口腔錠、片劑、丸劑、膠囊、懸浮液、飲劑、糖漿 及其類似物之形式投與。此等製劑應含有至少〇丨%活性化 δ物製劑之組成當然可變化。以所討論之製劑(劑量單 位)的總重量計,其通常包含2重量%至6〇重量%活性化合 物。本發明之化合物I的較佳製劑每經口劑量單位包含1 〇 至1000 mg活性化合物。 錠劑、片劑、丸劑、膠囊及其類似物可另外包含以下組 〇 分:黏合劑,諸如黃蓍膠、阿拉伯膠(gum arabic)、玉米 澱粉或明膠;賦形劑,諸如磷酸二鈣;崩解劑,諸如玉米 殿粉、馬鈴薯殺粉、褐藻酸及其類似物;滑動劑,諸如硬 • 脂酸鎂;甜味劑,諸如蔗糖、乳糖或糖精;及/或香料, ,冑如胡椒薄荷、香草及其類似物。膠囊可另外包含液體載 劑。亦可使用修改劑量單位之特性的其他物質。舉例而 言,錠劑、丸劑及膠囊可塗有謝蘭克(schellack)、糖或其 混合物。除活性化合物之外,糖裝或飲劑亦可包含糖(或 其他甜味劑)、龍基苯甲酸甲或對㈣苯甲酸丙醋(作 147475.doc -145- 201043139 為方腐对Ο、著色劑及/或香料。活性化合物製劑之組分在 所用量下當,然必須為醫藥級純且無毒。此外,可將活性化 口物為配為控制釋放活性化合物之製劑,例如調配為延遲 釋放製劑。 亦可非經腸或腹膜内投與活性化合物。可用水,使用適 合濕潤劑(諸如羥丙基纖維素)來製備活性化合物或其鹽之 溶液或懸浮液。亦可使用甘油、液體聚乙二醇及其混合物 在油中製備分散液。此等製劑經常另外包含防腐劑以防止 微生物生長。 …欲用於注射之製劑包含無菌水溶液及分散液,以及供 製備無菌溶液及分散液之無菌散劑。該製劑必須足夠液化 則更注射。其在製備及儲存條件下必須穩定且其必須受保 羞以防文微生物污染。載劑可為溶劑或分散介質,例如 jc乙醇多&amp;醇(例如甘油、丙二醇或液體聚乙二醇)、 其混合物及/或植物油。 【實施方式】 由以下非限制性實例進一步說明本發明。 I.合成實例 1·製備5-(2 -三氣甲其贫田甘、 土本曱基)-1-(5-巯基-[1,2,4]-三唑_1_基 甲基)-2,2-二曱基環戊醇 [。(2 —氟曱基苯基)_甲_(£)_亞基]_2,2_二曱基環戊酮 向在C下冷卻的2,2-二甲基環戊酮〇〇 g,44 57 匪〇1)及2 —三氣甲基笨甲酸(6.97g,49.03 mm。⑽乙醇⑼ 叫中之溶液中緩慢添加⑽氫氧化鈉水溶液⑼mL)。使 147475.doc •146· 201043139 反應混合物升溫至室溫’且繼續攪拌隔夜。在真空中濃縮 混合物,且添加二氣曱烷(100 mL)。用鹽酸酸化水相,且 分離各相。水相用二氣甲烷(2x100 mL)萃取,且合併之有 機萃取物經硫酸鎂乾燥。在減壓下移除溶劑,得到標題產 物(11.30 g,41.89 mmol,94%)。 1·2 5-(2 -二氣曱基本甲基)-2,2-二甲基環戊酉同 實例1_1中所獲得之化合物(11.90 g,44.36 mmol)溶解於 Θ 四氫呋喃(110 mL)中,且在標準氫化條件下在阮尼鎳 (Raney-Nickel)(10% mmol)存在下在周圍溫度下還原隔 夜。反應混合物經矽藻土過濾,且固體用二氯甲烷(丨〇〇 mL)洗滌。在減壓下濃縮濾液,得到標題產物(7 5〇 §, 27.75 mmol,62%)。 1.3 5-(2-三氟甲基苯曱基)_2,2_二曱基三唑-卜 基甲基-環戊醇 向3氫化鈉(2.33 g,97.12 mmol)之N-曱基吡咯啶酮(35 ❹ mL)中緩慢添加碘化三甲氧化锍(9.16 g,4l.62 mmol)。當 起泡停止時,逐份添加Π,2,4]-1Η-三唑(3.83 g,55.50 mm〇1),且繼續再攪拌3〇分鐘。接著,添加實例1.2中所獲 得之化σ物(7.50 g ’ 27.75 mmol),接著添加異丙醇(35 mL),且加熱混合物至。反應完成後,添加水(1〇〇 mL) ’接著添加甲I第三丁基醚(250 mL)及氯化链(1-2刮 勺)。分離各相’且用甲基第三丁基醚(2x100 mL)洗滌水 相用水(3x50 mL)洗滌合併之萃取物,經硫酸鎂乾燥且 t真工中移除溶劑。使用急驟層析純化殘餘物,得到標題 147475.doc -147- 201043139 產物(2.45 g,6.94 mmol,25%)。 1.4 5-(2-三氟曱基苯曱基)_i_(5_巯基_[12,4]三唑_丨基曱 基)-2,2-二甲基環戊醇 向實例1.3中所獲得之化合物(〇 5〇 g,1 41 mmol)於N-曱 基吼咯啶酮(15 mL)中之溶液中添加元素硫(〇 345 g,ι415 mmol),且在180°C下加熱混合物隔夜。冷卻至室溫後,添 加曱基弟二丁基醚(50 mL) ’且混合物經短二氧化石夕墊過 滤。在減壓下》辰縮滤'液’且向殘餘物中添加氣化鐘水溶液 (20 mL)。用乙酸乙酯(3X5〇 mL)洗滌水相,且用氣化鋰水 溶液(3X10 mL)洗務合併之有機萃取物,之後經硫酸鎂乾 燥。在真空中濃縮混合物,且利用急驟層析純化殘餘物, 得到標題產物(0.16 g,〇_42 mmol,30%;)。 HPLC-MS滯留時間(質量):3 542 min (386) 類似地製備實例2及3之化合物。 2. 5-(2-氟苯甲基)毓基_[12 4]_三唑基曱基)_2,2_ 二曱基環戊醇 HPLC-MS滯留時間(質量):3 274 min (336) 3_ 5_(2·氟氯苯甲基)-1-(5-巯基-[1,2,4]-三唑-1-基曱基)_ 2,2-二曱基環戊醇 HPLC-MS 滯留時間(質量):3 477 min(352) Π.對抗有害真菌之作用之實例 藉由以下實驗證明式I及式II化合物之殺真菌作用: A) 溫室測試 將活性物質分別或一起調配成包含25 mg活性物質之儲 147475.doc -148- 201043139 備溶液,使用丙酮及/或二甲亞礙(DMS〇)混合物及乳化劑 ttol EM 3 1 (基於乙氧基化炫基龄之具有乳化及分散作用 之濕肩劑)補足該錯備溶液至1G W,其中溶劑/乳化劑之體 積為991。^後使用水補足該溶液至1 〇〇 ml。用所述溶 背J /乳化劑/水混合物稀釋該儲備溶液至下文給出之活性物 質濃度。 使用實例1 :冑對大豆上由大豆鏽菌引起之大互錄病的治 癒作用 Ο(chlorfenvinphos), dizizon, dichlorvos, dicrotophos, dimethoate, disulfoton, ethion, fenitrothion , fenthion, isoxathion, malathion, methamidophos, methidathion, methyl-parathion, mevinphos, ya Monocrotophos, oxydemeton-methyl, paraoxon, parathion, phenthoate, phosalone, phosmet , phosphamidon, phorate, phoxim, pirimiphos-methyl, profenofos, prothiofos, sulprophos, Tetrachlorvinphos, terbufos, triazophos, trichlorfon; - amino phthalate: alanycarb, aldicarb, invulnerable Ben (bendiocarb), Benfke (benfbra) Carb), carbaryl, carbofuran, carbosulfan 'fenoxycarb', fenoxycarb, furathiocarb, metiocarb, nanet (methomyl), oxamyl, pirimicarb, propoxur, thiodicarb, triazamate; - pyrethroid: Allethrin, bifenthrin, cyfluthrin, cyhalothrin, cyphenothrin, cypermethrin, alpha-cypermethrin, beta-race Zingning, ξ-赛pernin (zeta-cypermethrin), deltamethrin, esfenvalerate, effenin 147475. Doc -125- 201043139 (etofenprox), fenpropathrin, fenvalerate, imiprothrin, lambda-cyhalothrin, permethrin, puarinin Prallethrin), pyrethrins I and II, resmethrin, silafluofen, tau-fluvalinate, tefluthrin, tetramethrin ), tralomethrin, transfluthrin, profluthrin, dimefluthrin; - insect growth regulator: a) chitin synthesis inhibition Agent: Benzamidine urea: chlorfluazuron, cyromazine, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, locust Lufenuron, novaluron, teHubenzuron. , triflumuron; buprofezin, diofenolan, hexythiazox, etoxazole, clofentazin; b) ecdysone antagonist : hafenofozide, methoxyfenozide, tebufenozide, azadirachtin; c) juvenoid: pyriproxyfen, beauty Mesoprene, fenoxycarb; d) lipid biosynthesis inhibitors: spirodiclofen, spiromesifen, spirotetramat; Agent/antagonist compounds: clothianidin, dinotefuran, imidacloprid, thiamethoxam, nitenpyram, acetamiprid, Thiacloprid, 1-(2-gas-thiazol-5-ylindenyl)-2-niminoimido- 147475. Doc -126· 201043139 3,5-Dimethyl-[1,3,5]triazide; -GABA antagonist compound: endosulfan, ethiprol, fenapini (fipronii), vanipipr〇i, fiyrazil (PyrafluPro1), pyriprol, 5-amino-1-(2,6-dichloro-4-indolyl-phenyl) _4-Aminosulfinyl-1H-pyrazole-3-thiodecanoic acid decylamine; - Macrolide lactone: abacitin, emamectin, smectin; (milbemectin), lepimectin, spinosad, spinetoram; - mitochondrial electron transport inhibitor (METI) I acaricide: fenazaquin, Pyridaben, tebufenpyrad, tolfenpyrad, flufenerim; -METI II and bismuth compounds: acequinocyl, fluacyprim, Hydramethylnon; Uncoupler: chlorfenapyr; - Oxidation acidification inhibitors: cyhexatin, diafenthiuron, fenbutatin oxide ), Propargite; - moulting disruptor compound: cryomazine; - mixed-function oxidase inhibitor: piperonyl butoxide; - nanochannel blocker: Indek ( Indoxacarb), metaflumizone; -benbeniaz, bifenazate, cartap, flonicamid, pyridalyl , pymetrozine, sulfur, thiocyclam, flubendiamide 147475. Doc -127· 201043139 (flubendiamide), chlorantraniliprol, cyazypyr (HGW86); cyenopyrafen, flupyrazofos, cyflumetofen, Amidoflumet, imicyafos, bistrifiuron, and pyrifluquinazon 〇 The present invention further relates to an agrochemical composition comprising at least one compound I, II And/or IV (component 1) and at least one other active substance (component 2) suitable for plant protection, for example selected from the group A) to group I) (especially another fungicide, for example one or more from A fungicide according to group A) to group F) as described above and, if appropriate, a mixture of suitable solvents or solid carriers. Because many of their mixtures show higher efficiency against harmful fungi at the same application rate, they are of particular interest. Furthermore, a mixture of compound IV and at least one fungicide from the group of Α) to F) as described above against harmful fungi is compared to individual compounds I, II or IV or from groups A) to F) The agents are more effective against their fungi. A synergistic effect can be achieved by the application of the compounds I, II and/or IV together with at least one active substance from the guanidine group to the Sichuan, i.e. a simple addition (co-mixture) is achieved which is greater than the individual effects. I. According to the present invention, it is to be understood that the application of the compound 11 and/or 1 000 together with at least one other active substance means at least one compound of the formula I, II and/or IV and at least one other active substance in a fungicidal effective amount. At the same time, it occurs in harmful fungi or their habitats that are to be controlled, such as infected plants, materials (especially seeds), surfaces, materials or soils, as well as plants and plant propagation materials (especially species) 147475. Doc -128· 201043139 Sub) soil, surface, material or space). This can be achieved by simultaneous (combination (in the form of a septic compound) or separately) or continuous application of the compounds I, II and/or IV and at least one other active substance, wherein - The time interval between the chords is selected to ensure that the active substance applied first is still present in sufficient quantity at the site of action when the other substances are applied. The order of application is not critical to the work of the present invention. A combination of the invention in a one-component mixture, i.e., an active substance comprising a compound I, II or IV (component 1) ❹ and a further/tongue substance (component 2) (for example, a group from group A) The weight ratio of component 丨 to component 2 generally depends on the nature of the active substance used, and is usually in the range of 1:1 (10) to · i, often in the range of 1:50 to 50:1. Preferably, it is in the range of 1:2〇 to 2〇:1, more preferably in the range of 1:10 to 10:1 and in particular in the range of 1:3 to 3:1. In a ternary mixture, ie comprising a compound j, π &amp; /4ΐν (component υ and the first other active substance (component 2) and a second other active substance (component 〇 3) (for example two from Α) The weight ratio of component 1 to component 2 in the composition of the invention of the active substance of group I) is dependent on the nature of the active substance used, preferably in the range of 1:50 to 50:1 and Especially in the range of 1:1〇 to 1〇:1. The weight of component 1 and component 3 is preferably in the range of 1:5 Torr to 5 Å:1 and especially in the range of 1:10 to 10:1. The components can be used to prepare the compositions of the present invention either individually or in part or in combination with each other. It may also be further packaged and used in the form of a combination composition such as a kit of dispensing parts. In one embodiment of the invention, the kit may include one or more (including 147475. Doc • 129- 201043139 All) can be used to prepare the components of the standard agrochemical composition. For example, the kit may comprise one or more fungicide components and/or adjuvant components and/or insecticide components and/or growth regulator components and/or herbicides. One or more components may have been combined or pre-formulated. In embodiments in which two or more components are provided in a kit, the components may have been combined and packaged as such in a single container such as a vial, bottle, can, sachet, pouch or can. In other embodiments, two or more components of the kit may be packaged, ie, not pre-formulated. Thus, the kit may include one or more individual devices such as vials, cans, bottles, sachets, bags or cans, each containing an individual component of the agrochemical composition. In either form, one of the sets is $ The fraction may be administered separately or separately from the other components or in the form of a component of the combination composition of the invention for preparing the alpha compound of the invention. The user typically has a predosage device, a backpack spray, a spray tank. Or a sprayer to apply the composition of the invention. Here, the agricultural use ♦. . Further, the σ system is made up of water and/or a buffer to a desired application concentration, and it is appropriate to add other auxiliaries, and thus obtain a ready-to-use spray liquid or agrochemical composition of the present invention. The agricultural effective area per hectare is usually applied to 5 liters of 'preferably 100 liters to 4 liters of ready-to-use spray liquid. According to one embodiment, the individual components of the composition of the invention, such as part of the formula - two _ 70 or a portion of the mixture, may be 'incorporated by the user' in the spray tank and may be added as appropriate Other additives (slot mixing). In other embodiments, the individual components or portions of the compositions of the invention are premixed. The knives comprise, for example, the compounds I, II and/or 乂 and/or the actives from the group A) to the group), and the knives can be mixed by the user in the spray tank and When appropriate 147475. Doc -130- 201043139 Other additives and additives (tank mix) can be added. In another κ embodiment, the individual components or portions of the compositions of the present invention are premixed, and the knives, for example, comprise the compound 丨, π and/or ... and/or from the Α) group to the U group / tongue 〖biomass The components may be administered in combination (e.g., after tank mixing) or continuously. A mixture comprising the compound I, hydrazine and/or 1 part (component hydrazine and at least one selected from the group consisting of hydrazine) and especially the active substance (component 2) selected from the group consisting of: , ethenamide, fluoxastrobin, kexinxin, acesulfame, oxystrobin, kekemin and trifluoro-sensitive. Mixtures comprising Compounds I, II and/or IV (component quinone and at least one selected from the group consisting of carboguanamines and especially selected from the following active substances (Component 2) are also preferred: baikefen, baikele' Sedative, cycloheximide, chlordane, isopizamide, dextromethorphan, furosemide, dapren, flumorph, flu TI bismuth (picobenzamid), Hydrazine, gupamine, dipropionin and N-(3',4',5'-trifluorobiphenyl-2-yl)-3-difluoromethylmethyl_1H_pyrazole 4-carbamamine. A mixture comprising the compounds I, II and/or IV (component 1) and at least one excipient selected from group c) and especially selected from the following active substances (component 2) is preferably: cyclohexyl Block, Waiting Klip, Ep, fluoroquinazole, hydrazine, defoliation, chlorpyrifos, micney, pingke, pugli, prothioconazole, three taifen, three tailong, dekli, Four Klee, Sterilization, Poker, Race, Free, Beffen and Ethaboxam. Mixtures comprising a compound I, II and/or IV (component 1) and at least one heterocyclic compound selected from the group D) and especially selected from the group consisting of the following active substances (component 2) are also 147475. Doc •131- 201043139 Preferred: chlorpromazine, cypro, fenremo, chlorpyrifos, pimeni, safranin D vine, carbendazim, fenfluster, didefine, benzene rust Pyridine, Yiputong, Xikening, Fanzhitong, Imidazolidone, chlorpyrifos, Puquinaz, acidified benzoxazole-s-methyl ester, tetrachlordane, fore, cyanamide, Vonofol and 5-ethyl-6, octyl-π, 2,4]triazolopyrimidine-7-ylamine. Included are compounds I, π and/or ... (component 丨) and at least one amine decanoate selected from the group E) and are especially selected from the group consisting of zinc manganese, smear, sputum, sylvestre, dermatology, sputum An active substance of a mildew, a phenothiamine and a propamocarb (a mixture of phantom components is also preferred. It comprises a compound I, π and/or 1 ¥ (component 丨) and at least one fungicide selected from the group and Mixtures of especially active substances (component 2) selected from the following are also preferred. Nitrile sulphide 'triphenyltin salt (such as triphenyl vinegar), forsythia, forsylate aluminum, H3P 〇 3 and its salts, tetra-isophthalonitrile, Yifaling, methyl chlorhexate, copper acetate, Copper hydroxide, copper oxide, copper sulfate, sulfur, gram, fenfennon and snail pentylamine. The invention therefore further relates to a composition comprising a compound I, II and/or IV (component 1) and another active substance (component 2) selected from the group B of Table B- 1 to b_346 line "Component 2" one stop. Further consistent examples relate to compositions 1 to b-346 listed in Table B, wherein one of the tables B is in each case corresponding to a compound (component) comprising an individualized formula I, II or IV in the present specification. 1) and fungicidal compositions of the individual active substances (component 2) from groups A) to I) as described in the discussion. The composition preferably comprises a synergistically effective amount of active material. Table B: Contains an individualized compound 〖, ^ or ... and from group a) to 〇 147475. Doc • 132- 201043139 Composition of another active substance in a mixture of components 1 Component 2 B-1 An individualized compound I, II or IV Atomin B-2 An individualized compound I, II or IV Amine B-3 An individualized compound I, II or IV enestrobin B-4 An individualized compound I, II or IV fluoxastrobin B-5 An individualized compound I, II or IV 克收欣 B- 6 An individualized compound I, II or IV phenoxybamine B-7 an individualized compound I, II or IV acesulfame B-8 an individualized compound I, II or IV oxystrobin B-9 Individualized compound I, II or IV 100g-sensitive B-10 an individualized compound I, II or IV than Benka B-11 an individualized compound I, II or IV trifluoro-sensitive B-12 an individualized compound I, II or IV 2-(2-(6-(3-Gas-2-methyl-phenoxy)-5-fluoro-bitter _ 4-yloxy)-phenyl)-2-methoxy Amino-N-mercapto-ethinamine B-13 An individualized compound I, II or IV 2-(o-((2,5-dimethylphenoxymethylene)phenyl)-3-yl Methyl methacrylate B-14 An individualized compound I, II or IV 3-decyloxy-2-(2-(N -(4-Methoxy-phenyl)-cyclopropanimide fluorenylthioindolyl)-phenyl)-decyl acrylate B-15 An individualized compound I, II or IV 2-(2- (3-(2,6-diphenyl)-1-indenyl-allylpropenyl [aminooxyindenyl)-phenyl)-2-methoxyimino] N-methyl-B Indole B-16 An individualized compound I, II or IV Bendula B-17 An individualized compound I, II or IV 右本达乐~~ B-18 An individualized compound I, II or IV B-19 An Individualized Compound I, II or IV Baikefen~~ B-20 An Individualized Compound I, II or IV Baikly B-21 An Individualized Compound I, II or IV Brassin B-22 Individualized compound I, II or IV oxifenamide ~~ B-23 An individualized compound I, II or IV Cycloheximide -~~ B-24 An individualized compound I, II or rv Fludonine - B -25 An individualized compound I, II or IV Folabi ~~ B-26 An individualized compound I, II or IV Idezed Zami B-27 An individualized compound I, π or rv Ivory B-28 An individualized compound I, π or rv Kaida Le ' B-29 an individualized compound I, II or r v 3 Puning B-30 An individualized compound I, π or rv 灭达-- B-31 An individualized compound I, II or IV dextromethorphan B-32 an individualized compound I, II or IV Indoleamine ~ B-33 An individualized compound I, hydrazine or IV octopus 147475. Doc •133· 201043139 Mixture Component 1 Component 2 B-34 An Individualized Compound I, II or IV Jia Baoxin B-35 An Individualized Compound I, II or IV B-36 An Individualized Compound I, II or IV色达安B-37 An individualized compound I, hydrazine or IV gram 煳 'B-38 an individualized compound I, II or IV —--- B-39 an individualized compound I, hydrazine or IV B-40 An individualized compound I, II or IV Amino-4-methyl ϋ5_甲酿笑 B-41 An individualized compound I, II or IV 查^-(1,1,3-:曱基·茚满冰幕)·Nicotine guanamine B-42 An individualized compound I, II or IV Ν-(3·,4ΐ,5,-trifluorobiphenyl)_3·difluoromethyl _; _ Pyrazole-4-methyl guanidine face B-43 An individualized compound I, II or IV 1 (4'-trifluoromethylthiobiphenyl-2-yl)_3_difluoromethyl n-methyl-lH- n ratio sal-4-carboxamide B-44 an individualized compound I, II or IV N-(2-(l,3-dimercapto-butyl)phenyl)13_dif-yl-5 -Fluoro-1Η-»比嗤-4-曱醯amine B-45 An individualized compound I, II or IV is called 2-(1,3,3-tridecyl-butyl)-phenyldifluorenyl-yl -5-lt-lH·0 Jun-4·carbamamine B-46 An individualized compound I, II or IV daxanphene B-47 an individualized compound I, II or IV fluocillin B-48 an individualized compound I, II or IV °比林林 B-49 An individualized compound I, II or IV fluoxetine B-50 An individualized compound I, II or IV chaotic bacteriocin B-51 an individualized compound I, hydrazine or IV fluoro Pyridoxamine B-52 An individualized compound I, II or IV saponin B-53 An individualized compound I, hydrazine or IV N-(3-ethyl-3,5,5-trimethyl-ring Hexyl)-3-indenyl-2-hydroxy-benzimidamine B-54 an individualized compound I, II or IV gupamine B-55 an individualized compound I, II or IV dioxazole B -56 An individualized compound I, II or IV Dipropionin B-57 An individualized compound I, II or IV oxytetracycline B-58 an individualized compound I, II or IV thiastrobin B-59 An individualized compound I, hydrazine or IV N-(6-decyloxy-pyridin-3-yl)cyclopropanoic acid decylamine B-60 An individualized compound I, II or IV Azagon alpha sitting B-61 An individualized compound I, II or IV than Dorong B-62 An individualized compound I, hydrazine or IV bromoxene B-63 an individualized compound I, II or IV Cyclosyl-B-64 an individualized compound I, II or IV holly B-65 an individualized compound I, Π or IV 达利 B-66 an individualized compound I, II or IV dextran B-67 an individualized compound I, II or rv Eppia B-68 an individualized compound I, hydrazine or IV fen Block B-69 An individualized compound I, II or IV Fluoroquinazole B-70 An individualized compound I, II or IV m矽 B-71 An individualized compound I, hydrazine or IV Ref. 134· 147475 . Doc 201043139 Mixture component 1 Component 2 B-72 An individualized compound I, II or IV Fickley B-73 An individualized compound I, II or IV Easy amine block B-74 An individualized compound I, II or IV依普克嗤B-75 An individualized compound I, II or IV Cyclones B-76 An individualized compound I, II or IV McAfee B-77 An individualized compound I, II or IV oxazide B- 78 An individualized compound I, II or IV Bark B-79 An individualized compound I, II or IV Dink B-80 An individualized compound I, II or IV Puckley B-81 an individualized compound I, II or IV prothiotoxin. S-B-82 an individualized compound I, II or IV fluorazole B-83 An individualized compound I, II or IV De Klee B-84 An individualized compound I, II or IV Si Keli B-85 An individualization Compound I, II or IV Ditai B-86 An individualized compound I, II or IV Santarem B-87 An individualized compound I' II or IV sterilized. S-B-88 An individualized compound I, II or IV 坐 ° 坐 B-89 An individualized compound I, II or IV 1-(4-gas-phenyl)-2-([1,2,4] Triazol-1-yl)-cycloheptanol B-90 An individualized compound I, II or IV saponin B-91 an individualized compound I, II or IV thiophene B-92 an individualized compound I, II or IV Sulfate Sulfate B-93 An Individualized Compound I, II or IV Rice Dip B-94 An Individualized Compound I, II or IV Poker La B-95 An Individualized Compound I, II or IV Safford Block B-96 an individualized compound I, II or IV free of B-97 an individualized compound I, II or IV befenfen B-98 an individualized compound I, II or IV wheat spike B-99 Individualized compound I, II or IV rotted B-100 an individualized compound I, II or IV ethaboxam B-101 an individualized compound I, II or IV eduli B-102 an individualized compound I, II Or IV carbendazim B-103 an individualized compound I, II or IV 2-(4-chloro-phenyl)-N-[4-(3,4-dimethoxy-phenyl)-isoxazole -5-yl]-2-prop-2-ynyloxy-acetamide B-104 an individualized I, II or IV GIJ-B-105 An individualized compound I, II or IV Tefino B-106 An individualized compound I, II or IV 3-[5-(4-gas-phenyl)- 2,3-Dimethyl-isoxazol-3-yl]-° 嗓B-107 an individualized compound I, II or IV 3-[5-(4-indolyl-phenyl)-2, 3-Dimercapto-isoxazol-3-yl]-α than lake B-108 an individualized compound I, II or IV 2,3,5,6-tetraqi_4_曱 续 酿 - - 〇 is subjected to B-109 an individualized compound I, II or IV 3,4,5-dichloro-° ratio biting 2,6-dicarbonitrile B-110 an individualized compound I, II or IV 1^- (1-(5-&gt;Smelly-3-chloro-0-precipitate-2-yl)-ethyl)-2,4-dioxane-in the case of decylamine 147475. Doc -135 - 201043139 Mixture component 1 Component 2 B-lll An individualized compound I, II or IV N-((5-bromo-3-chloro-.pyridin-2-yl)-methyl)-2 ,4-Dichloro_final amine A-II-II An individualized compound I, II or IV Bremer B-113 An individualized compound I, II or IV Cypro B-114 An individualized compound I, II Or IV gas forest B-115 an individualized compound I, II or IV fenrimyl B-116 an individualized compound I, II or IV Furui comprehensive B-117 an individualized compound I, II or IV B-118 An individualized compound I, II or IV anhydropyridine B-119 an individualized compound I, II or IV Nymimo B-120 An individualized compound I, II or IV Pimenic B-121 An individualization Compound I, II or IV Safranine B-122 An individualized compound I, II or IV Seed dressing B-123 An individualized compound I, II or IV 护宁B-124 An individualized compound I, II or IV Adoniline B-125 An individualized compound I, II or IV carbendazim B-126 An individualized compound I, II or IV carbendazim B-127 An individualized compound I, II or IV Fenford B-128 An individualized compound I, II or IV Sanden B-129 An individualized compound I, II or IV Benzene bite B-130 An individualized compound I, II or IV ° sedge B -131 An individualized compound I, II or IV Isoprofen B-132 An individualized compound I, II or IV Fighting N-B-133 An individualized compound I, II or IV Free Kein B-134 An individualized compound I, II or IV singly with B-135 an individualized compound I, II or IV sputum ketone B-136 an individualized compound I, II or IV Futinib B-137 an individualized compound I, II Or IV octyl ketone B-138 an individualized compound I, II or IV chilling heat B-139 an individualized compound I, II or IV 5 -amino-2-isopropyl-4-o-phenylene phenyl-2 ,3-Diazin-pyrazole-1·S-allyl ester of thioformic acid B-140 An individualized compound I, hydrazine or IV acidified benzothiadiazole-S-methyl ester B-141 An individualized compound I , II or IV carbazolam bromide B-142 an individualized compound I, II or rv carbendazim B-143 an individualized compound I, II or IV poliomycin B-144 an individualized compound I II or IV Tetrachlorin B-145 An individualized compound I, II or IV Captan B-146 An individualized compound I, II or IV 瞒 瞒 B B-147 An individualized compound I, II or IV B-148 An individualized compound I, II or IV 15 militaris B-149 an individualized compound I, II or IV chlorpyrifos B-150 an individualized compound I, II or IV Individualized compound I, II or IV sulfhydryl sulfate wild swallow 147475. Doc -136- 201043139 Mixture Component 1 Component 2 B-152 An individualized compound I, hydrazine or IV cyanamide B-153 An individualized compound I, II or IV Forbes B-154 An individualized compound I , II or IV Oxolins Sure B-155 An individualized compound I, hydrazine or IV powder disease B-156 An individualized compound I, π or IV Puccinaz B-157 An individualized compound I , II or IV 百 隆 __ B-158 an individualized compound I, hydrazine or IV veprofen B-159 an individualized compound I, II or IV imidazoline B-160 an individualized compound I &gt; II or IV Tribendazole B-161 An individualized compound I, II or IV 2-butoxy-6-moth-3-propyl-benzo-4-one B-162 An individualized compound I, II or IV 5_ Gas-1-(4,6-dimethoxy-chito-2_yl)_2-methyl-1H-benzoimidazole B-163 an individualized compound I, II or IV 5-chloro-7-( 4-methyl-π chen-1-yl)_6-(2,4,6-trifluoro-phenyl)-[1,2,4]tris-[l,5-al ringing B-164 An individualized compound I, II or IV 5 · ethyl _ 6 · octyl-[I, 2, 4] tris-[1,5-a]°® -7-ylamine B-165 Compound I, II or rv Family B-166 An individualized compound I, II or IV Zinc Manganese B-167 An individualized compound I, II or IV Manganese B-168 An individualized compound I, II Or IV Weibai B-169 an individualized compound I, II or IV sulfacarbin B-170 an individualized compound I, II or IV free of rot B-171 an individualized compound I, II or IV methyl zinc Pu B-172 An individualized compound I, II or IV Dean B-173 An individualized compound I, II or IV Zinc Napo B-174 An individualized compound I, II or IV Yisui B-175 An individualization Compound I, II or IV Ethylbutabol B-176 An individualized compound I, II or IV Bethicillin B-177 An individualized compound I, II or IV Anthraquinone B-178 An individualized compound I, II Or IV propamocarb B-179 an individualized compound I, II or IV downyzil hydrochloride B-180 an individualized compound I, II or IV Waffenella B-181 an individualized compound I, II or IV N_(l -(1 -(4-Cyanophenyl)6-alkylsulfonyl)-butyl-J)-aminomethyl S- complex-(4-fluorophenyl) ester B-182 Was I, II or IV efavirenz B-183 a discretionary compounds I, II or IV efavirenz free base B-184 one kind of individual compounds I, II or IV guazatine.   B-185 An individualized compound I, II or IV biguanide salt - B-186 An individualized compound I, II or IV Bis-octylamine B-187 An individualized compound I, II or IV diammonium diacetate - B -188 An individualized compound I, II or IV (alkyl stearic acid) bis-octylamine B-189 An individualized compound I, II or IV Xisinmycin ___ B-190 An individualized compound I, II Or IV hydrated citric acid hydrochloride -137- 147475. Doc 201043139 Mixture Component 1 Component 2 B-191 An Individualized Compound I, II or IV Polyoxin B-192 An Individualized Compound I, II or IV Streptomycin B-193 An Individualized Compound I, II Or IV Aminomycin A B-194 An individualized compound I, II or IV Baikeke B-195 An individualized compound I, II or IV Dicloran B-196 An individualized compound I, II or IV 消螨通 B-197 An individualized compound I, II or IV 白克克 B-198 An individualized compound I, II or IV Nitrothal-isopropyl B-199 An individualized compound I, II or IV Tetranitrobenzene B-200 An individualized compound I, II or IV Triphenyltin salt B-201 An individualized compound I, II or IV Nitrile sulfonium B-202 An individualized compound I, II or IV Ling B-203 An individualized compound I, II or IV Pleurotus ostreatus B-204 An individualized compound I, II or IV Forsythia, Fossex aluminum B-205 An individualized compound I, II or IV propyl喜乐松 B-206 An individualized compound I, II or IV sub-filled Sman (H3PO3) and derivative B-207 Compound I, II or IV White Pine B-208 An Individualized Compound I, II or IV Dexamethasone B-209 An Individualized Compound I, II or IV Tetraisophthalonitrile B-210 An Individualized Compound I, II or IV Yifaling B-211 An individualized compound I, II or IV Dichlorophenol B-212 An individualized compound I, II or IV Sulfasamine B-213 An individualized compound I, II or IV hexabenzene B-214 An individualized compound I, II or IV Bin clone B-215 An individualized compound I, II or IV Pentaphenol and salt B-216 An individualized compound I, II or IV Thermos B-217 Individualized compound I, II or IV five gas nitrobenzene B-218 an individualized compound I, II or IV thiol polybutanyl B-219 an individualized compound I, II or IV methyl valproate B-220 Individualized compound I, II or IV N-(4-milo-2-nitro-phenyl)-N-ethyl-4-mercapto-benzenesulfonamide B-221 An individualized compound I, II or IV Bodo Mix B-222 An Individualized Compound I, II or IV Copper B-223 An Individualized Compound I, II or IV Copper Hydroxide B-224 - Individualized Compound I , II or IV Copper oxychloride B-225 An individualized compound I, II or IV Basic copper sulphate B-226 An individualized compound I, II or IV sulphur B-227 An individualized compound I, II or IV biphenyl B-228 An individualized compound I, II or IV bromide B-229 an individualized compound I, II or IV cycloflufen B-230 an individualized compound I, II or IV gram B-231 an individual Compound I, II or IV Diphenylamine B-232 An individualized compound I, II or IV annihilation morning 147475. Doc •138- 201043139 Mixture Component 1 Component 2 B-233 An Individualized Compound I, II or IV Dymphalin B-234 An Individualized Compound I, II or IV Quicken B-235 An Individualized Compound I, II or IV calcium cyclate B-236 an individualized compound I, II or IV spirooxamine B-237 an individualized compound I, II or IV methyl valproate B-238 an individualized compound I, II or IV N-(Mercaptopropyloxyimino-(6-difluoromethoxy-2,3-di-I-phenyl)-methyl)-2-phenylacetamidamine B-239 An individualized compound I, II or IV NH4-(4-chloro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-indenyl脒B-240 An individualized compound I, II or IV 1 Ν·-(4-(4-fluoro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-fluorene -ethyl-indole-methylformamidine B-241 an individualized compound I, II or IV Ν'-(2-mercapto-5-trifluoromethyl-4-(3-tridecyl)-alkyl- Propoxy)-phenyl)-N-ethyl-N-mercaptomethylhydrazine B-242 An individualized compound I, II or IV N'-(5-difluoromethyl-2-methyl-4- (3-trimethyldecyl-propoxy)-phenyl)-N-ethyl-N-methyl Hyperthyroid B-243 An individualized compound I, II or IV 2-{1-[2-(5-methyl-3-trifluoromethyl-inden-1-yl)-ethenyl]-purine O--4-yl}-indole-4-decanoic acid methyl-(1,2,3,4-tetrahydroqin-1-yl)-bristamine B-244 an individualized compound I, II or IV 2 -{1-[2-(5-Methyl-3-trifluoromethyl-pyrazol-1-yl)-ethinyl]-piperidin-4-yl}-thiazole-4-carboxylic acid thiol-( R)-l,2,3,4-tetrahydronaphthalen-1-yl-decylamine B-245 An individualized compound I, II or IV 6-tert-butyl-8-fluoro-2,3-diacetic acid Methyl-indol-4-yl ester B-246 an individualized compound I, II or IV methoxy-acetic acid 6-tert-butyl-8-fluoro-2,3-dimethyl-quinoline-4 -Base ester B-247 An individualized compound I, II or IV plus Poly B-248 An individualized compound I, II or IV plus Bao B-249 An individualized compound I, II or IV butyl plus Bao B -250 An individualized compound I, II or IV Nathomylthiodicarb B-251 An individualized compound I, II or IV Bifenin B-252 An individualized compound I, II or IV Sai Fanning B- 253 An individualized compound I, II or IV Sai Ning B-254 An individualized Substance I, II or IV Sub-Ning B-255 An individualized compound I, II or IV ξ-赛宁宁 B-256 An individualized compound I, II or IV Difenin B-257 An individualized compound I, II or IV 益化利 B-258 An individualized compound I, II or IV λ-赛洛宁 B-259 An individualized compound I, II or IV Baisinning B-260 An individualized compound I, II or IV Tefluthrin B-261 An individualized compound I, II or IV Fufulon B-262 An individualized compound I, II or IV Qifenlong B-263 An individualized compound I, II or IV Ruffin B -264 An individualized compound I, II or IV Defolon 147475. Doc •139· 201043139 Mixture Component 1 Component 2 B-265 An Individualized Compound I, II or IV Spirotetraethyl Ester B-266 An Individualized Compound I, II or IV Cotinide B-267 An Individualized Compound I, Π or IV 达特南 B-268 An individualized compound I, Π or IV 达达amine B-269 An individualized compound I, II or IV 赛速安 B-270 An individualized compound I, II or IV亚灭培B-271 An individualized compound I, II or IV Sai Bai B-272 An individualized compound I, II or IV Anthony B-273 An individualized compound I, II or IV Fenpney B- 274 An individualized compound I, hydrazine or IV Abatine B-275 An individualized compound I, II or IV Inhibitor B-276 An individualized compound I, II or IV Anoxin B-277 An individual compound I, II or IV Spintolan B-278 An individualized compound I, hydrazine or IV Amesson B-279 An individualized compound I, hydrazine or IV kefanita B-280 An individualized compound I, II or IV Fenbuxet B-281 An individualized compound I, π or rv Indek B-282 An individualized compound I, hydrazine or IV Flurfluent sinensis B-283 An individualized compound I, II or IV Cyclosamine B-284 An individualized compound I, II or IV flufenamide B-285 An individualized compound I, hydrazine or IV gram B-286 An individualized compound I, II or IV 赛培(HGW86) B-287 An individualized compound I, II or IV Butylated fluoro ester B-288 An individualized compound I, π or rv acetochlor B- 289 An individualized compound I, II or IV oxacin B-290 an individualized compound I, hydrazine or IV chlorpyrifos B-291 an individualized compound I, hydrazine or IV chlorpyrifos B-292 an individualized compound I , II or IV glyphosate B-293 an individualized compound I, II or IV glufosinate B-294 an individualized compound I, II or rv oxathiophosphine B-295 an individualized compound I, II or IV alkyne Oxalic acid B-296 an individualized compound I, II or IV 01 oxazole oxacillin B-297 an individualized compound I, hydrazine or IV fluazifop-butyl B-298 an individualized compound I, II or IV ° An individualized compound I, hydrazine or IV paraquat B-300 an individualized compound I, II or IV beet Ning B-301 An individualized compound I, II or IV ketene B-302 An individualized compound I, hydrazine or IV Cycloheximide B-303 An individualized compound I, II or IV Cyclopentanone B-304 An individualized compound I, II or IV chlorpyrifos B-305 an individualized compound I, II or IV from chlorpyrifos B-306 an individualized compound I, hydrazine or IV bismuthine B-307 Compound I, hydrazine or IV aniline 147475. Doc -140- 201043139 Mixture component 1 Component 2 B-308 An individualized compound I, II or IV Trifluralin B-309 An individualized compound I, II or IV Acifluorfen B-310 An individualization Compound I, II or IV bromoxynil B-311 An individualized compound I, II or IV Imazethin B-312 An individualized compound I, II or IV Amphetamine B-313 An individualized compound I, II or IV methyl imazethapyr B-314 an individualized compound I, II or IV taste 0 sitting in acid B-315 an individualized compound I, II or IV ° ° ° 啥 啥 acid B-316 an individualization Compound I, II or IV Imidazoic acid B-317 An individualized compound I, II or IV 2,4-diphenoxyacetic acid (2,4-D) B-318 An individualized compound I, II or IV Chlorophyll Min B-319 An individualized compound I, II or IV 克草特特 B-320 An individualized compound I, II or IV Fluroxypyr B-321 An individualized compound I, II or IV chlorpyrifos B-322 Individualized compound I, II or IV fluroxypyramine B-323 an individualized compound I, II or IV bensulfuron-B-324 an individualized compound I II or IV Qisulfuron-B-325 An individualized compound I, II or IV Cyclopropsulfuron-B-326 An individualized compound I, II or IV Iodomethylsulfuron B-327 An individualized compound I, II Or IV Sulfonamide B-328 An Individualized Compound I, II or IV Methsulfuron B-329 An Individualized Compound I, II or IV Nicosulfuron B-330 An Individualized Compound I, II or IV Sulfone Sulfoxsulfuron B-331 An individualized compound I, II or IV flucarbazone B-332 An individualized compound I, II or IV Astragalus B-333 An individualized compound I, II or IV hexazinone B -334 An individualized compound I, II or IV diuron B-335 an individualized compound I, II or IV diflufenacil B-336 an individualized compound I, II or IV profenofin B-337 Individualized compound I, II or IV Bentazon B-338 An individualized compound I, II or IV α 丨 ketone vinegar B-339 An individualized compound I, II or IV Cycloheptyl B-340 Individualized compound I, II or IV dicamba B-341 an individualized compound I, II or IV diflupiron B-342 an individualized combination I, II or IV Dioxin 01 Linic acid B-343 An individualized compound I, II or IV Oxalic acid B-344 An individualized compound I, II or IV Sulfosone B-345 An individualized compound I, II Or IV pyrimidine ether B-346 an individualized compound I, II or IV Topan is known as the active substance of component 2, its preparation and its resistance to harmful fungi 147475. Doc • 141- 201043139 Activity (Reference: http://www. Alanwood. Net/pesticides/); these materials are commercially available. Compounds described by the IUPAC nomenclature, their preparation and their fungicidal activity are also known (see Can.  J_ Plant Sci.  48(6), 587-94, 1968; EP-A 141 3 17; EP-A 1 52 03 1 ; EP-A 226 917 ; EP-A 243 970 ; EP-A 256 503 ; EP-A 428 941 ; EP-A 532 022; EP-A 1 028 125; EP-A 1 035 122; EP-A 1 201 648; EP-A 1 122 244 &gt; JP 2002316902; DE 19650197; DE 10021412; DE 102005009458; US 3,296,272; US 3,325,503; WO 98/46608; WO 99/14187; WO 99/24413; WO 99/27783; WO 00/29404; WO 00/46148; WO 00/65913; WO 01/54501; WO 01/56358; WO 02/40431; WO 03/10149; WO 03/11853; WO 03/14103; WO 03/16286; WO 03/53145; WO 03/61388; WO 03/66609; WO 03/74491; WO 04 WO 04/83193; WO 05/120234; WO 05/123689; WO 05/123690; WO 05/63721; WO 05/87772; WO 05/87773; WO 06/15866; WO 06/87325; WO 07/82098; WO 07/90624) ° A mixture of active substances can be prepared in a conventional manner, for example by means of a combination of the compounds I, II and/or IV, in addition to the active ingredient. Also included to A composition of an inert ingredient. With regard to the common ingredients of such compositions, reference is made to the description given for compositions containing compounds I, II and/or IV. As the compounds of the formulae I, II and IV, mixtures of the active substances according to the invention are suitable as fungicides. It is known for its outstanding utility against a wide range of phytopathogenic fungi, especially from the Ascomycetes, 147475. Doc -142- 201043139 Subspecies, deuteromycetes and downy mildew (four) (5) (4). Further, reference is made to the description of the fungicidal activity of the compound and the composition containing the compound I and the calendar / (4), respectively. .  Another aspect of the invention relates to a seed comprising at least one of formula I, hydrazine and/or ... compounds per g of 10 kg of seed. Compounds 11 and 1V and their pharmaceutically acceptable salts are also suitable for the treatment of diseases in humans and animals (especially as antifungal agents), for the treatment of cancer &amp; treatment of viral infections. The term "anti-counter" as used in the term "fungicide" refers to a drug that is resistant to animal pathogenic or human pathogenic fungi, i.e., against fungi in animals, particularly mammals and birds. Thus, another aspect of the invention pertains to a medicament comprising at least one compound of formula I, II and/or IV and/or at least one pharmaceutically acceptable salt thereof and a pharmaceutically acceptable carrier. Suitable pharmaceutically acceptable salts are, in particular, the physiologically tolerated salts of the compounds π &amp; / or 1 'specifically, the phthalic acid addition salts formed with physiologically acceptable acids. Examples of suitable organic and inorganic acids are hydrochloric acid, hydrobromic acid, phosphoric acid, &amp; C^C:4 alkylsulfonic acid (such as methanesulfonic acid), aromatic sulfonic acids (such as benzenesulfonic acid and toluenesulfonic acid). , oxalic acid, maleic acid, transbutene-diacid, lactic acid, tartaric acid, adipic acid and benzoic acid. Other suitable acids are described, for example, in Fortschritte der Arzneimittelforschung, Vol. 1, pp. 224 et seq., in Birkhauser Verlag, Bas. 6 and in 1966, the entire contents of which are hereby incorporated by reference. Suitable carriers are, for example, solvents, carriers, excipients, binders, and the like which are commonly used in pharmaceutical formulations, exemplified by the individual dosage forms 147475. Doc -143 - 201043139 The formula is described. Another aspect of the invention relates to the use of the compounds I, II and IV or their pharmaceutically acceptable salts for the preparation of antifungal agents; that is, for the preparation of a therapeutic and/or prophylactic human pathogenic and/or animal pathogen. Use of drugs for fungal infections. Another aspect of the invention is the use of a compound of formula I, II and/or IV, or a pharmaceutically acceptable salt thereof, for the manufacture of a medicament for the treatment of cancer. Another aspect of the invention is the use of a compound of formula I, π and/or IV, or a pharmaceutically acceptable salt thereof, for the manufacture of a medicament for the treatment or prevention of a viral infection. The 弋I 11 and/or 1V compound and/or its pharmaceutically acceptable salt are suitable for the treatment, inhibition or control of growth and/or proliferation of tumor cells and its associated disorders. Therefore, it is suitable for treating cancer of warm-blooded vertebrates/, the warm-blooded vertebrates of the temple are, for example, mammals and bird members, specifically humans, and other mammals, specifically useful domestic animals such as dogs, L pigs, reverse animals (bovine sheep, goats, bison, etc.), horses and birds, =, turkey, hong, crane, guinea fowl and similar animals. Formula I, π and pharmaceutically and/or pharmaceutically acceptable salts thereof are suitable for: cancer or cancerous conditions of the following organs: breast, lung, intestine, prosthetic j skin (melanoma), kidney 'bladder, Mouth, throat, esophagus, stomach, nest, pancreas, liver and brain or CNS. Month 1! The compound and 'or its pharmaceutically acceptable salt are suitable for::: viral infection of blood vertebrates'. The isothermal gold vertebrates, such as self-cultivating animals and birds, are specifically stated as Useful livestock, such as dogs and other mammals, vegetable sticks, pigs, anti-dance animals (bovine, flat, goat, bison, etc.), horses and birds, such as chicken, turkey, duck, 147475. Doc • 144- 201043139 Cranes, guinea fowls and similar animals. It is suitable for the treatment of viral infections such as retroviral infections (such as HIV and HTLV), influenza virus infections, rhinovirus infections, herpes and the like. The compounds of the invention may be administered in a conventional manner, for example, orally, intravenously, intramuscularly or subcutaneously. For oral administration, the active compound can be mixed, for example, with an inert diluent or with an edible carrier; it can be enclosed in a hard gelatin capsule or a soft gelatin capsule, which can be compressed into a tablet or can be directly Mix with chyme/feed. The active compound may be mixed with excipients and administered in the form of non-digestible lozenges, troches, tablets, pills, capsules, suspensions, liquids, syrups and the like. The composition of such preparations which should contain at least 〇丨% of the active δ-formulation may of course vary. It typically comprises from 2% to 6% by weight, based on the total weight of the formulation (dosing unit) in question, of the active compound. Preferred formulations of Compound I of the present invention comprise from 1 to 1000 mg of active compound per oral dosage unit. Tablets, tablets, pills, capsules and the like may additionally comprise the following group of ingredients: a binder such as tragacanth, gum arabic, corn starch or gelatin; an excipient such as dicalcium phosphate; Disintegrating agents, such as corn house powder, potato powder, alginic acid and the like; slip agents such as magnesium stearate; sweeteners such as sucrose, lactose or saccharin; and/or spices, such as pepper Mint, vanilla and the like. The capsule may additionally comprise a liquid carrier. Other substances that modify the characteristics of the dosage unit can also be used. For example, lozenges, pills and capsules may be coated with schellack, sugar or mixtures thereof. In addition to the active compound, the sugar or drink may also contain sugar (or other sweetener), thiol benzoic acid or p-tetracarboxylic propyl vinegar (for 147475. Doc -145- 201043139 For square rot, coloring agents and/or fragrances. The components of the active compound formulation, when used in amounts, must be pharmaceutically pure and non-toxic. In addition, the active ingredient can be formulated as a controlled release active compound, for example, as a delayed release formulation. The active compound can also be administered parenterally or intraperitoneally. A solution or suspension of the active compound or a salt thereof can be prepared in water using a suitable wetting agent such as hydroxypropylcellulose. Glycerin, liquid polyethylene glycol, and mixtures thereof can also be used to prepare dispersions in oil. These formulations often additionally contain a preservative to prevent microbial growth. The preparation to be used for injection contains a sterile aqueous solution and dispersion, and a sterile powder for the preparation of a sterile solution and dispersion. The formulation must be sufficiently liquefied to be injected more. It must be stable under the conditions of manufacture and storage and must be kept shy to prevent microbial contamination. The carrier can be a solvent or dispersion medium such as jc ethanol &amp; alcohol (e.g., glycerol, propylene glycol or liquid polyethylene glycol), mixtures thereof and/or vegetable oils. [Embodiment] The present invention is further illustrated by the following non-limiting examples. I. Synthesis Example 1·Preparation of 5-(2-three gas, methicillin, sulfenyl)-1-(5-fluorenyl-[1,2,4]-triazol-1-ylmethyl)-2 , 2-dimercaptocyclopentanol [. (2 -fluorononylphenyl)_methyl-(£)_subunit]_2,2-didecylcyclopentanone to 2,2-dimethylcyclopentanone 〇〇g, 44 cooled at C 57 匪〇1) and 2—three gas methyl benzoic acid (6. 97g, 49. 03 mm. (10) Ethanol (9) A solution of (10) aqueous sodium hydroxide (9 mL) was slowly added to the solution. Make 147475. Doc • 146· 201043139 The reaction mixture was allowed to warm to room temperature and stirring was continued overnight. The mixture was concentrated in vacuo and dioxane (100 mL) was added. The aqueous phase was acidified with hydrochloric acid and the phases were separated. The aqueous phase was extracted with di-methane (2 x 100 mL) and the combined organic extracts dried over magnesium sulfate. The solvent was removed under reduced pressure to give the title product (11. 30 g, 41. 89 mmol, 94%). 1·2 5-(2-dihydroquinone basic methyl)-2,2-dimethylcyclopentanyl as the compound obtained in Example 1_1 (11. 90 g, 44. 36 mmol) was dissolved in hydrazine tetrahydrofuran (110 mL) and reduced under ambient hydrogenation conditions in the presence of Raney-Nickel (10% mmol) at ambient temperature overnight. The reaction mixture was filtered through EtOAc (EtOAc)EtOAc. The filtrate was concentrated under reduced pressure to give the title product (75. 75 mmol, 62%). 1. 3 5-(2-Trifluoromethylphenylindenyl)_2,2-didecyltriazole-b-methyl-cyclopentanol to sodium hydride (2. 33 g, 97. 9 mmol) of N-decylpyrrolidone (35 ❹ mL) was slowly added with cesium iodide (9. 16 g, 4l. 62 mmol). When the foaming stops, add hydrazine, 2,4]-1 Η-triazole (3. 83 g, 55. 50 mm 〇 1) and continue to stir for another 3 minutes. Next, add instance 1. The sigma obtained in 2 (7. 50 g ’ 27. 75 mmol), followed by the addition of isopropanol (35 mL) and heating the mixture. After completion of the reaction, water (1 〇〇 mL) was added followed by the addition of methyl I butyl ether (250 mL) and a chlorinated chain (1-2 scoop). The phases were separated and the aqueous phase was washed with methyl tert-butyl ether (2 x 100 mL). The combined extracts were washed with water (3×50 mL) and dried over magnesium sulfate. The residue was purified using flash chromatography to give the title 147475. Doc -147- 201043139 Product (2. 45 g, 6. 94 mmol, 25%). 1. 4- 5-(2-Trifluoromethylphenylindenyl)_i_(5-fluorenyl_[12,4]triazole-indolyl)-2,2-dimethylcyclopentanol To Example 1. Addition of elemental sulfur (〇345 g, ι415 mmol) to a solution of the compound obtained in 3 (〇5〇g, 1 41 mmol) in N-decylpyrrolidone (15 mL) at 180 ° C The mixture was heated overnight. After cooling to room temperature, hydrazino dibutyl ether (50 mL) was added and the mixture was filtered through a short celite pad. Under reduced pressure, the liquid was filtered, and an aqueous solution of a gasification clock (20 mL) was added to the residue. The aqueous phase was washed with ethyl acetate (3×5 mL), and the combined organic extracts were washed with EtOAc (3×10 mL). The mixture was concentrated in vacuo and the residue was purified eluting elut 16 g, 〇_42 mmol, 30%;). HPLC-MS residence time (mass): 3 542 min (386) The compounds of Examples 2 and 3 were prepared analogously. 2.  5-(2-Fluorobenzyl)indenyl_[12 4]-triazolylhydrazyl)_2,2_didecylcyclopentanol HPLC-MS retention time (mass): 3 274 min (336) 3_ 5_ (2. fluorochlorobenzyl)-1-(5-fluorenyl-[1,2,4]-triazol-1-ylindenyl)_ 2,2-dimercaptocyclopentanol HPLC-MS residence time (Quality): 3 477 min (352) Π. Examples of the action against harmful fungi The fungicidal action of the compounds of the formulae I and II is demonstrated by the following experiments: A) Greenhouse test The active substances are separately or together formulated into a reservoir containing 25 mg of active substance. Doc -148- 201043139 Preparation of a solution using acetone and / or dimethyl sulfoxide (DMS 〇) mixture and emulsifier ttol EM 3 1 (wet shoulder with emulsification and dispersion based on ethoxylated base age) The solution was prepared to 1 G W with a solvent/emulsifier volume of 991. ^ Then use water to make up the solution to 1 〇〇 ml. The stock solution was diluted with the dissolved J / emulsifier / water mixture to the active substance concentration given below. Use example 1: The cure effect of cockroaches on soybeans caused by soybean rust bacteria Ο

用大丑銹病(大豆鏽菌)之孢子懸浮液接種盆栽大豆籽苗 之葉子。隨後將植物置放於大氣濕度高(9〇%至95%)且溫 度為20-24t之腔室中24小時。在此期間,孢子萌發且芽 管穿透至葉組織中。隨後在溫度在23它與27t之間且相對 大氣濕度為60%至80%之溫室中再培養測試植物。兩天 後,用具有下述活性物質濃度之上述水溶液噴灑植物至溢 流點(runoff p〇int)。乾燥懸浮液後,在溫度在23。〇與27 之間且相對大氣濕度為60%至80%之溫室中再培養植物1〇 天。隨後目測判定葉子上銹病發展之程度。 活性化合物 濃度[ppm] 星長[%1 -(對照組) 70 實例1 300 0 實例2 300 0 實例3 300 使用貫例2 .針對小麥上由小麥殼針孢引起之殼針孢屬斑 點病之保護作用 用具有下述活性物質濃度之水性懸浮液喷灑盆栽小麥籽 147475.doc -149- 201043139 田之葉子至溢流點。乾燥懸浮液後24小時,用小麥殼針孢 之孢子懸浮液接種經處理之植物。隨後將植物置放於大氣 濕度高(約100%)且溫度為18_饥之腔室中4天,且隨後置 放於相對大乳滿度為約70%且溫度為18_22。〇之腔室中 天後,目測判定葉子f 1 Λ + ^ 上銹病I展之程度,表示為佔 子表面之百分比。 t1111葉 活性^匕合物 對照組)¥5ϊ3The leaves of potted soybean seedlings were inoculated with a spore suspension of large rust (soybean rust). The plants were then placed in a chamber with a high atmospheric humidity (9〇% to 95%) and a temperature of 20-24t for 24 hours. During this time, the spores germinate and the germ cells penetrate into the leaf tissue. The test plants were then incubated in a greenhouse at a temperature between 23 and 27 t and a relative atmospheric humidity of 60 to 80%. Two days later, the plants were sprayed to the overflow point (runoff p〇int) with the above aqueous solution having the following active substance concentration. After drying the suspension, the temperature is at 23. The plants were incubated for another 1 day in a greenhouse between 〇 and 27 and at a relative atmospheric humidity of 60% to 80%. The degree of rust development on the leaves was then visually determined. Active compound concentration [ppm] Star length [%1 - (control group) 70 Example 1 300 0 Example 2 300 0 Example 3 300 Use example 2. For the case of the genus Septoria spp. caused by the wheat sphaeroides Protection The potted wheat seeds 147475.doc - 149 - 201043139 field leaves were sprayed to the overflow point with an aqueous suspension having the following active substance concentrations. 24 hours after the suspension was dried, the treated plants were inoculated with a spore suspension of S. cerevisiae. The plants were then placed in a chamber with a high atmospheric humidity (about 100%) and a temperature of 18 hunger for 4 days, and then placed at a relatively large milk fullness of about 70% and a temperature of 18-22. After the day in the chamber of the cockroach, the degree of rust on the leaf f 1 Λ + ^ was visually determined and expressed as a percentage of the surface of the occupant. T1111 leaf active compound: control group) ¥5ϊ3

生長[%] 90~ Ί〇~~Growth [%] 90~ Ί〇~~

147475.doc -150-147475.doc -150-

Claims (1)

201043139 七、申請專利範圍: 1.式I及式II之三唾化合物,201043139 VII. Patent application scope: 1. The three salivation compounds of formula I and formula II, L1及L4彼此獨立地選自氫、氟、溴、碘、㈣。炫 基、Cl_ClGi燒基'Cl-CiQ垸氧基及CVC1()鹵烧氧基; L及L3彼此獨立地選自氫、南素、Ci_Ci。烧基、LG。 齒院基、Cl_Cl成氧基及。自烧氧基; 限制條件為L1、L2、L、L4中至少一者不為氮; 〇 R1及R2彼此獨立地選自氫、Ci_Ci〇烧基、Ci-Ci〇函烧 基、C1-C10烷氧基及(^-(:10鹵烷氧基; R係選自氫、Cl_Ci〇烷基、。广。。鹵烷基、Ci_Ci〇烷氧 基及Ci-C10鹵烷氧基; R係選自氫、Cl_ClG烷基、Ci_CiG _烷基、C2_Ci〇烯 基、C2-C1G _ 烯基、c2_CiG快基、c2_Ci。鹵快基、c3_Ci〇 環烧基、C3_C1(^環烷基、苯基、苯基_C1_C4烷基,其中 最後2個提及之基團中之苯基部分可具有1、2、3、4或5 個取代基尺8,及含有1、2或3個選自N、0及S之雜原子作 147475.doc 201043139 為5衣成員的5員或6員飽和、部分不飽和或芳族雜環, 其中該雜環可具有i、2或3個取代基R8 ;或在η為〇之情 況下,亦可選自·C( = 〇)R5、_C( = S)R5、_s(〇)2R5、CN、 -P(=Q)R6R7、M及式 m基團,L1 and L4 are independently selected from hydrogen, fluorine, bromine, iodine, and (iv). A thiol group, a Cl_ClGi alkyl group, a 'Cl-CiQ methoxy group, and a CVC1 () halogen alkoxy group; and L and L3 are independently selected from the group consisting of hydrogen, sulfhydryl, and Ci_Ci. Burning base, LG. The base of the tooth, Cl_Cl to oxy group and. Self-activating oxy; limiting condition is that at least one of L1, L2, L, L4 is not nitrogen; 〇R1 and R2 are independently selected from hydrogen, Ci_Ci fluorene, Ci-Ci 〇, C1-C10 Alkoxy and (^-(:10 haloalkoxy; R is selected from the group consisting of hydrogen, Cl_Ci 〇 alkyl, widely. Haloalkyl, Ci_Ci decyloxy and Ci-C10 haloalkoxy; R system Selected from hydrogen, Cl_ClG alkyl, Ci_CiG_alkyl, C2_Ci-decenyl, C2-C1G-alkenyl, c2_CiG fast radical, c2_Ci. Halo fast radical, c3_Ci〇 cycloalkyl, C3_C1 (cycloalkyl, phenyl) a phenyl-C1_C4 alkyl group, wherein the phenyl moiety in the last two mentioned groups may have 1, 2, 3, 4 or 5 substituent bases 8, and contain 1, 2 or 3 selected from N a hetero atom of 0 and S as 147475.doc 201043139 is a 5- or 6-membered saturated, partially unsaturated or aromatic heterocyclic ring of a 5 member, wherein the heterocyclic ring may have i, 2 or 3 substituents R8; In the case where η is 〇, it may also be selected from the group consisting of C(= 〇)R5, _C(=S)R5, _s(〇)2R5, CN, -P(=Q)R6R7, M and a group of formula m, L]、L·2、L·3、L4、R1、R2及R3係如式【及式π所定 其中 #為與該分子之其餘部分的連接點; R4a係選自氫、(VCm烷基、(^-(:10鹵烷基、c2_Cl0烯 基、C2-C丨〇鹵烯基、C2-C10炔基、C2-C10鹵炔基、c3-Ci〇 環拔基、6-(:10鹵環烷基、苯基、苯基-Cl_c4烷基,其中 最後2個提及之基團中之苯基部分可具有1、2、3、4或5 個取代基R8 ’含有i、2或3個選自N、Ο及S之雜原子作為 環成員的5員或6員飽和、部分不飽和或芳族雜環,其中 該雜環可具有1、2或3個取代基R8,-C(=0)R5、_C(=s)R5 、-S(〇)2R5、-CN、-P(=Q)R6R7及 Μ ; R5係選自氫、(Vq❶烷基、烷基、Cl-c1()烷氧 基、Ci-Cio鹵烧氧基、(^-(210胺基烧基' (33-匚10環炫基、 147475.doc -2- 201043139 〇3_〇:10鹵環烷基、苯基、苯基_Ci_C4烷基、苯氧基,其中 最後3個提及之基團中之苯基部分可具有1、2、3、4或5 個取代基尺8,含有1、2或3個選自N、Ο及S之雜原子作為 環成員的5員或6員飽和、部分不飽和或芳族雜環,其中 該雜環可具有1、2或3個取代基R8,及NR9R10 ; R6及R7彼此獨立地選自Cl-ClQ烷基、Ci_Cig_烷基、 c2-c1Q稀基、c2_ClG鹵烯基、C2_CiG炔基、c2_Ci❶齒炔 基、c3-c1Q環院基、C3_ClG鹵環炫基、Ci_Ci〇規氧基、 cvcw齒烧氧基、Ci-C4燒氧基_Ci_Ci〇烧基、Ci_C4烧氧 基-CVCw烧氧基、Cl_ClG院硫基、Ci_Ci()i^硫基、Cy Cio稀氧基、C2-C1G婦硫基、c2-C1Q炔氧基、C2-C1Q炔硫 基、C3_C1()-環烷氧基、C3_C1G環烷硫基、苯基、苯基_ q-C4烷基、苯氧基、苯硫基、苯基_Ci_C4烷氧基及 NRnR12 ; 各R8獨立地選自鹵素、硝基、CN、Ci_C4烷基、Ci_C4 鹵烷基、0^-(:4烧氧基、Ci-C^鹵烧氧基及NR13R14 ; R9係選自氫及c〗-c8烷基; R10係選自氫、Ci-C8烷基、苯基及苯基_Ci_C4烷基; 或R9與R1G—起形成直鏈C4或〇5伸烷基橋或基團 -CH2CH2OCH2CH2-或-CH2CH2NR15CH2CH2-; R&quot;係選自氳及CVCs烷基; R12係選自氫、c^-c:8烷基、笨基及苯基_Ci_c4烷基; 或R11與R12—起形成直鏈C:4或(^伸烷基橋或基團 -CH2CH2OCH2CH2-或-CH2CH2NR15CH2CH2·; 147475.doc 201043139 Rl3在每次出現時獨立地選自氫及以烧基; 苯基及 RM在每次出現時獨立地選自t、Cl-C8烧基 苯基-CVC4烷基; 或R與11“_起形成直鍵^或^伸烧基橋或基團 ^€Η2€Η2〇〇Η2€Η2-^ -CH2CH2NR15CH2CH2-; R15在每次出現時獨立地選自氣ACi_C4烷基; Q為0或S ; Μ為金屬陽離子相等物或式(NRaRbRcRd)+之銨陽離 子,其中Ra、Rb、…及Rd彼此獨立地選自氫、烷 基、苯基及笨甲基,其中最後2個提及之基團中之苯基 4刀可具有丨、2或3個獨立地選自以下之取代基:鹵 素、CN、確基、Ci_C4烧基、C〗_C4齒烧基、Ci_C4院氧 基、C〗-C4鹵烷氧基及nr”Ri4 ; n為〇、1、2或3 ;且 ----為單鍵或雙鍵; 及其農業上可接受之鹽。 2. 如清求項1之式I及式II化合物,其具有式ΙΑ及ΙΙΑ, R4aL], L·2, L·3, L4, R1, R2 and R3 are as defined in the formula [and π where # is the point of attachment to the rest of the molecule; R4a is selected from hydrogen, (VCm alkyl, (^-(:10 haloalkyl, c2_Cl0 alkenyl, C2-C丨〇 haloalkenyl, C2-C10 alkynyl, C2-C10 haloalkynyl, c3-Ci〇cyclohexyl, 6-(:10 halo) a cycloalkyl, phenyl, phenyl-Cl_c4 alkyl group, wherein the phenyl moiety in the last two mentioned groups may have 1, 2, 3, 4 or 5 substituents R8' containing i, 2 or 3 a 5- or 6-membered saturated, partially unsaturated or aromatic heterocyclic ring selected from the group consisting of a hetero atom of N, hydrazine and S as a ring member, wherein the heterocyclic ring may have 1, 2 or 3 substituents R8, -C ( =0) R5, _C(=s)R5, -S(〇)2R5, -CN, -P(=Q)R6R7 and Μ; R5 is selected from hydrogen, (Vq❶ alkyl, alkyl, Cl-c1 ( Alkoxy, Ci-Cio halooxy, (^-(210-aminoalkyl) (33-匚10cyclodecyl, 147475.doc -2- 201043139 〇3_〇: 10-halocycloalkyl, Phenyl, phenyl-Ci_C4 alkyl, phenoxy, wherein the phenyl moiety of the last three mentioned groups may have 1, 2, 3, 4 or 5 substituent bases 8, containing 1, 2 or 3 out of N, Ο a 5- or 6-membered saturated, partially unsaturated or aromatic heterocyclic ring of a hetero atom of S, wherein the heterocyclic ring may have 1, 2 or 3 substituents R8, and NR9R10; R6 and R7 are independently selected from each other. From Cl-ClQ alkyl, Ci_Cig_alkyl, c2-c1Q dilute, c2_ClG haloalkenyl, C2_CiG alkynyl, c2_Ci decyl alkynyl, c3-c1Q ring, C3_ClG halocyclo, Ci_Ci 〇 oxy , cvcw tooth alkoxy, Ci-C4 alkoxy _Ci_Ci oxime, Ci_C4 alkoxy-CVCw alkoxy, Cl_ClG thiol, Ci_Ci()i thio, Cy Cio dioxy, C2- C1G thiol, c2-C1Q alkynyloxy, C2-C1Q alkynylthio, C3_C1()-cycloalkoxy, C3_C1G cycloalkylthio, phenyl, phenyl_q-C4 alkyl, phenoxy, a phenylthio group, a phenyl-Ci_C4 alkoxy group and NRnR12; each R8 is independently selected from the group consisting of halogen, nitro, CN, Ci_C4 alkyl, Ci_C4 haloalkyl, 0^-(:4 alkoxy, Ci-C^ a halogen alkoxy group and NR13R14; R9 is selected from hydrogen and c--c8 alkyl; R10 is selected from hydrogen, Ci-C8 alkyl, phenyl and phenyl-Ci_C4 alkyl; or R9 forms a straight line with R1G Chain C4 or 〇5 stretch alkyl bridge or group -CH2CH2OCH2CH2- or -CH2CH2NR15CH2CH2-; R&q Uot; is selected from the group consisting of hydrazine and CVCs alkyl; R12 is selected from the group consisting of hydrogen, c^-c:8 alkyl, strepyl and phenyl-Ci_c4 alkyl; or R11 and R12 together form a straight chain C: 4 or ( ^alkylene bridge or group -CH2CH2OCH2CH2- or -CH2CH2NR15CH2CH2·; 147475.doc 201043139 Rl3 is independently selected from hydrogen and alkyl at each occurrence; phenyl and RM are independently selected from each occurrence , Cl-C8 alkylphenyl-CVC4 alkyl; or R and 11" to form a direct bond ^ or ^ stretch-base bridge or group ^ 2 Η 2 Η 2 〇〇Η 2 € Η 2-^ -CH2CH2NR15CH2CH2-; R15 Each occurrence is independently selected from the group consisting of a gas ACi_C4 alkyl; Q is 0 or S; Μ is a metal cation equivalent or an ammonium cation of the formula (NRaRbRcRd)+, wherein Ra, Rb, ... and Rd are independently selected from hydrogen An alkyl group, a phenyl group, and a stupid methyl group, wherein the phenyl 4 knives in the last two mentioned groups may have an anthracene, 2 or 3 substituents independently selected from the group consisting of halogen, CN, an exact group, Ci_C4 alkyl, C _C4 dentate, Ci_C4 alkoxy, C--C4 haloalkoxy and nr"Ri4; n is 〇, 1, 2 or 3; and --- is a single bond or a double bond And its agriculturally acceptable salts. 2. For the compound of formula I and formula II of claim 1, which has the formula ΙΙΑ and ΙΙΑ, R4a (ΙΑ) L2 Η iVs N—N(ΙΑ) L2 Η iVs N-N (ΠΑ) 147475.doc 201043139 其中 R1、R2、R3、R4、R4a、Ll、L2、L3、Lin係如請 求項1中所定義。 3.如前述請求項中任一項之式i及式π化合物,其中l2&amp;l3 彼此獨立地選自氫、鹵素、Cl_c3烷基、q-Cs鹵烷基、 Ci-C3院氧基&amp;Cl_C3鹵烷氧基。 4·如請求項3之式〗及式„化合物,其中L2及L3彼此獨立地 選自氫、鹵素、甲基、CH2F、CHF2、CF3、曱氧基、 0 〇CH2F、〇CHF2、2,2,2_三氟乙氧基、1,1,2,2_四氟乙氧 基及五I乙氧基,較佳選自氫及氣。 5·如則述請求項中任一項之式I及式II化合物,其中L1及L4 彼此獨立地選自氫、氟、溴、CVC3烷基、Cl-C3鹵烷 基、ci_C3烧氧基&amp;Cl_c3鹵烷氧基。 6·如吻求項5之式I及式II化合物,其中L1及L4彼此獨立地 選自氫、氟、溴、甲基、CH2F、CHF2、CF3、曱氧基、 〇CH2F、〇CHF2、0CF3、2,2,2-三氟乙氧基、1,1,2,2-四 〇 氟乙氧基及五氟乙氧基。 如味求項6之式1及式II化合物,其中L1及L4彼此獨立地 選自氫、氟及cf3。 8·如2則述請求項中任一項之式I及式II化合物,其中L1、 L、'及L4中之一者或兩者不為氫。 9. 求項8之式I及式Π化合物,其中L1及L4中一者不為 氫,而另一者為氫。 1〇·如刚述凊求項中任一項之式I及式II化合物,其中L2及L3 中至少-者為氫。 147475.doc 201043139 11 _如請求項10之式I及式II化合物,其中L2及L3兩者均為 氫,或一者為氫,而另一者為氣。 12·如前述請求項中任一項之式I及式Π化合物,其中Ri及r2 彼此獨立地選自氫、甲基、乙基及三氟曱基,較佳兩者 均為甲基》 13 ·如前述請求項中任一項之式I及式II化合物,其中R3係選 自氫、甲基、乙基及三氟甲基,較佳為氫。 14.如前述請求項中任一項之式I及式π化合物,其中R5係選 自CVC4烷基、Cl_C4烷氧基、苯基、苯氧基及nr9r1〇, 其中R9為氫,R10係選自氫、Ci-Q烷基及苯基。 1 5 ·如前述請求項中任一項之式I及式II化合物,其中R4係選 自氫、CVQ烷基、_c(=〇)R5、-S(0)2R5、-CN、Μ及式 III基團。 16. 如請求項15中任一項之式i及式π化合物,其中R4係選自 氫、CVC4烷基、c3-C4烷基羰基、(VC4烷氧基羰基、 -CbCONCHKrC^烷基、CVC4烷基磺醯基、CN及式III基 團,較佳選自氫、CN及曱基。 17. 如前述請求項中任一項之式I及式π化合物,其中係選 自氫、CVC4烷基及鹵烷基。 1 8.如前述請求項中任一項之式I及式II化合物,其中η為0。 19. 一種式IV化合物, 147475.doc -6- 201043139 Μ(ΠΑ) 147475.doc 201043139 wherein R1, R2, R3, R4, R4a, L1, L2, L3, and Lin are as defined in claim 1. 3. The compound of formula i and formula π according to any of the preceding claims, wherein l2 &amp;l3 are independently of each other selected from the group consisting of hydrogen, halogen, Cl_c3 alkyl, q-Cs haloalkyl, Ci-C3 alkoxy &amp; Cl_C3 haloalkoxy. 4. The formula of claim 3 and the compound of the formula wherein L2 and L3 are independently selected from the group consisting of hydrogen, halogen, methyl, CH2F, CHF2, CF3, decyloxy, 0 〇CH2F, 〇CHF2, 2,2 2—Trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy and penta-I ethoxy, preferably selected from the group consisting of hydrogen and gas. And a compound of formula II, wherein L1 and L4 are, independently of each other, selected from the group consisting of hydrogen, fluorine, bromine, CVC3 alkyl, Cl-C3 haloalkyl, ci_C3 alkoxy&amp;Cl_c3 haloalkoxy. And a compound of the formula II, wherein L1 and L4 are independently selected from the group consisting of hydrogen, fluorine, bromine, methyl, CH2F, CHF2, CF3, decyloxy, 〇CH2F, 〇CHF2, 0CF3, 2,2,2 -Trifluoroethoxy, 1,1,2,2-tetrahydrofluoroethoxy and pentafluoroethoxy. The compound of formula 1 and formula II, wherein L1 and L4 are independently selected from each other Hydrogen, fluorine, and cf3. The compound of Formula I and Formula II of any one of the claims, wherein one or both of L1, L, ', and L4 are not hydrogen. And a compound of the formula I, wherein one of L1 and L4 is not hydrogen and the other is hydrogen. A compound of formula I and formula II, wherein at least one of L2 and L3 is hydrogen. 147475.doc 201043139 11 _A compound of formula I and formula II according to claim 10, wherein L2 and L3 are both hydrogen, or one is hydrogen, and the other is a gas. The compound of formula I and the formula of any one of the preceding claims, wherein Ri and r2 are independently selected from hydrogen And a compound of the formula I and the formula II according to any one of the preceding claims, wherein the R3 is selected from the group consisting of hydrogen, methyl, and B. And a trifluoromethyl group, preferably a hydrogen. 14. A compound of formula I and formula π according to any of the preceding claims, wherein R5 is selected from the group consisting of CVC4 alkyl, Cl_C4 alkoxy, phenyl, phenoxy And nr9r1〇, wherein R9 is hydrogen, and R10 is selected from the group consisting of hydrogen, a Ci-Q alkyl group, and a phenyl group. The compound of formula I and formula II according to any one of the preceding claims, wherein R4 is selected from the group consisting of hydrogen, CVQ alkyl, _c(=〇)R5, -S(0)2R5, -CN, hydrazine, and a group of formula III. 16. The compound of formula i and formula π according to any one of claims 15 wherein R4 is selected From hydrogen, CVC4 alkyl, c3-C4 alkyl A carbonyl group, (VC4 alkoxycarbonyl, -CbCONCHKrC^alkyl, CVC4 alkylsulfonyl, CN, and a group of formula III, preferably selected from the group consisting of hydrogen, CN, and fluorenyl. 17. Any of the foregoing claims The compound of formula I and formula π, wherein is selected from the group consisting of hydrogen, CVC4 alkyl, and haloalkyl. A compound of formula I and formula II according to any of the preceding claims, wherein n is zero. 19. A compound of formula IV, 147475.doc -6- 201043139 Μ Ν〜Ν’Ν~Ν’ 任一項所定義; Ο 如下化合物除外,其中 R1 ' R2 ' R3 ' L2 ' L3 ^ τ 4 ^ ^ τ 1 L及L為虱,l1為氟 '溴、甲氧基 或CF3,且rrrr為雙鍵; 及L為氫,L1為氟、溴、 R1 及 R2均為 CH3,R3、L2、L: 曱氧基或CF3’且二rr為雙鍵; R1 ' R2 ' R3 ' L1 ^ 鍵。 20. —種式IVA化合物, 及L4為氫,L2為cf3,且 為單 ΟAny one of the following; Ο except for the following compounds, where R1 ' R2 ' R3 ' L2 ' L3 ^ τ 4 ^ ^ τ 1 L and L are 虱, l1 is fluoro 'bromo, methoxy or CF3, and rrrr is double Key; and L is hydrogen, L1 is fluorine, bromine, R1 and R2 are both CH3, R3, L2, L: decyloxy or CF3' and two rr are double bonds; R1 'R2 'R3 ' L1 ^ bond. 20. A compound of the formula IVA, and L4 is hydrogen, L2 is cf3, and is mono- Ο N〜NN~N L2 Η (IVA) 其中 Rl、R2、R3、L1、L2、 任一項所定義; 如下化合物除外,其中R1、R2、 氫,且L2為CF3。 L及L4係如請求項 R3 、 L1 、 1至13中 L3及L4為 147475.doc 201043139 21. —種式V化合物,L2 Η (IVA) wherein R1, R2, R3, L1, L2 are as defined in any one of the following; except for the following compounds, wherein R1, R2, hydrogen, and L2 are CF3. L and L4 are as claimed in the claims R3, L1, 1 to 13 L3 and L4 are 147475.doc 201043139 21. The compound of the formula V, L2、L3及L4係如請求項1至13中 其中 Rl、R2、R3、L1、 任一項所定義; 如下化合物除外 Ri、R2、R3、L2、L3及 L4 盔气 τ 1 Λ 久L為虱,l1為氟或CF3,且 為雙鍵; 且L及L4為氟,且—為 R1、R2、R3、L2及 L3 為氫 單鍵。 22. —種式VA化合物,L2, L3 and L4 are as defined in any one of claims 1 to 13 wherein R1, R2, R3, L1; except for the following compounds Ri, R2, R3, L2, L3 and L4 helmet gas τ 1 Λ long L is虱, l1 is fluorine or CF3, and is a double bond; and L and L4 are fluorine, and - is R1, R2, R3, L2, and L3 are hydrogen single bonds. 22. a compound of the formula VA, 其中R、R、113、1^、[2、1^3及1/係如請求項1至13中 任一項所定義; 如下化合物除外’其中R1、R2、R3、乙2及。為氫,且 L1及L4為氟。 23· —種式VI化合物, 147475.doc (VI)201043139 9H2 r3Wherein R, R, 113, 1^, [2, 1^3 and 1/ are as defined in any one of claims 1 to 13; except for the following compounds wherein R1, R2, R3, and B2 are. It is hydrogen, and L1 and L4 are fluorine. 23·—Formula VI Compound, 147475.doc (VI)201043139 9H2 r3 其中 Ri、R2、r3 任一項所定義; L、l2、L3及L4係如請求項1至13中Where Ri, R2, r3 are defined; L, l2, L3 and L4 are as in claims 1 to 13 如下化合物除外 JL ’ L1為漠’且 24. —種式VIA化合物, ,其中 Ri、n2、R3 為單鍵。 L2、L3 及 L4 為Except for the following compounds, JL 'L1 is a desert' and 24. a compound of the formula VIA, wherein Ri, n2, and R3 are single bonds. L2, L3 and L4 are 任一項所定義; R/ R3、L2、L3 及 L4 為 如下化合物除外,其中R】 Q 氫,且L1為溴。 25. —種式VII化合物,R/R3, L2, L3 and L4 are excluded from the following compounds, wherein R] Q hydrogen and L1 is bromine. 25. a compound of formula VII, 、L2、L3及L4係如請求項u13中 其中 Ri、R2、R3、L1 任一項所定義; R14為 Η或 C(〇)OR15,其中 147475.doc -9· 201043139 e R係選自氫、Cl-Cl〇燒基、Ci-Cw函烧基、c3-C10 %烷基C3-C!。函環炫基、苯基、苯基_C1_C4烧基,其 中最後2個提及之基團中之苯基部分可具有卜2、3、 4或5個取代叙8,及含有1、2或3個選自N、〇及S之雜 原子作為%成員的5員或6員飽和、部分不飽和或芳族 雜8環’其中該雜環可具有卜2或3個取代紅8,其中 R8係如請求項1中所定義; 如下化合物除外,其中 R1、R2、R3、T? 14 τ 2 , . 、L 、L及L4為氫,且l1為CF3或 溴; 八 Λ K 、K/ 、L 、T3kt4^&gt;* 。 L及L為氫,且L2為CF3、甲 氧基或氟; Ri、R2、R3、L1 及 L4 盔备 τ 2 , 及L為虱’ L2及L3為第三丁基且 為氫或cooch3。 26. —種式νΙΙΗί:合物,, L2, L3, and L4 are as defined in any one of Ri, R2, R3, and L1 in claim u13; R14 is Η or C(〇)OR15, wherein 147475.doc -9· 201043139 e R is selected from hydrogen , Cl-Cl oxime, Ci-Cw functional base, c3-C10% alkyl C3-C!. a cyclyl, phenyl, phenyl-C1_C4 alkyl group, wherein the phenyl moiety of the last two mentioned groups may have 2, 3, 4 or 5 substituents, and contain 1, 2 or 3 heterocyclic atoms selected from N, oxime and S as a member of 5 or 6 members of a saturated, partially unsaturated or aromatic hetero 8 ring 'wherein the heterocyclic ring may have 2 or 3 substituted red 8 wherein R 8 Is as defined in claim 1; except for the following compounds, wherein R1, R2, R3, T? 14 τ 2 , . , L, L and L4 are hydrogen, and l1 is CF3 or bromine; gossip K, K/, L, T3kt4^&gt;*. L and L are hydrogen, and L2 is CF3, methoxy or fluorine; Ri, R2, R3, L1 and L4 are prepared as τ 2 , and L is 虱' L2 and L3 is a third butyl group and is hydrogen or cooch3. 26. —Formula νΙΙΗί: Compound, (VIII) ”中R R L、l2、l3及L4係如請求項α13中任一 項所定義’且R14係如請求項122中所定義; 如下化合物除外,其中 R1 ' R3 ' R14 &gt; L2 &gt; I 3 U τ 4¾ . , L及[為虱,且L1為CF3或溴; R1、R3、R14、L1、4 L及為虱,且L2為cf3、甲氧基 147475.doc •10- 201043139 或敗; 丁基,且R14為氫 R1、R3、Li及L4為氫,。及。為第 或cooch3。 27. —種式IX化合物(VIII) "RRL, l2, l3, and L4 are as defined in any one of claims [alpha]13 and R14 is as defined in claim 122; except for the following compounds, where R1 'R3 'R14 &gt; L2 &gt; I 3 U τ 43⁄4 . , L and [is 虱, and L1 is CF3 or bromine; R1, R3, R14, L1, 4 L and 虱, and L2 is cf3, methoxy 147475.doc •10- 201043139 or Derivative; butyl, and R14 is hydrogen, R1, R3, Li and L4 are hydrogen, and are or cooch3. 27. - compound of formula IX 如下化合物除外,其中 Ri、R2、R3、RW、L2、L: ❹ 且7ΓΓ7為單鍵; 及L4為氫,L1為CF3或溴, Rl、R2、R3、RW、Ll 3 4 及L為氫,l2為CF3、甲氧 基或氟’且二rr為單鍵; &quot;R1、R2、R3、Li及!/為氫,。及。為第三丁基,r&quot;為 氫或COOCH3 ’且二Γ為單鍵。 28. -種農業組合物’其包含至少一種如請求項中任 -項之式I ' II及/或IV及/或IVA化合物或其農業上可接受 之鹽,及液體或固體載劑。 29· -種如請求項U20中任一項之式及/或iva/或Μ 化合物的用途’其係用於防治有害真菌。 30. —種防治有害真菌之方法,其中用有效量之至少式卜u 及/或IV及/或IVA化合物處理該等真菌、其生境,或欲保 147475.doc •11 - 201043139 31 32. 33. 34. «蒦以免又真® 襲之材料或植物,或土壤或繁殖材料, 其中化合物I、π及1¥及/或IVA係如請求項中任一 項所定義。 一種種子,每HK)kg種子包如」之量的至少式 I II及/或IV及/或IVA化合物,其中化合物J、狀…及/ 或IVA係如請求項1至2〇中任一項所定義。 一種醫藥組合物’其包含至少—種如請求項中任 項之式I、II及/或IV及/或IVA化合物或其醫藥學上可接 受之鹽,及至少一種醫藥學上可接受之載劑。 一種如請求項1至20中任一項之式工、^或…及/或IVA化 口物或其醫藥學上可接受之鹽的用途,其係用於製備治 療癌症或病毒感染之藥物或用於製備抗黴藥物。 一種治療癌症或病毒感染或對抗動物病原性或人類病原 性真菌之方法,其包含以至少—種如請求項i至2〇中任 一項之式I、II及/或IV及/或IVA化合物、以至少一種其醫 藥學上可接受之鹽或以如請求項3 2之醫藥組合物治療有 需要之個體。 147475.doc 12- 201043139 四、指定代表圖: (一) 本案指定代表圖為:(無) (二) 本代表圖之元件符號簡單說明: 五、本案若有化學式時,請揭示最能顯示發明特徵的化學式:Except for the following compounds, wherein Ri, R2, R3, RW, L2, L: ❹ and 7ΓΓ7 are single bonds; and L4 is hydrogen, L1 is CF3 or bromine, and Rl, R2, R3, RW, Ll 3 4 and L are hydrogen. , l2 is CF3, methoxy or fluorine ' and two rr is a single bond; &quot;R1, R2, R3, Li and !/ are hydrogen. and. It is a third butyl group, and r&quot; is hydrogen or COOCH3' and the diterpene is a single bond. 28. An agricultural composition comprising at least one compound of the formula I'II and/or IV and/or IVA, or an agriculturally acceptable salt thereof, as claimed in any one of the claims, and a liquid or solid carrier. 29. The use of any of the claims U20 and/or the use of the iva/ or Μ compound for the control of harmful fungi. 30. A method of controlling harmful fungi, wherein the fungus, its habitat is treated with an effective amount of at least a compound of formula and/or IV and/or IVA, or 147475.doc •11 - 201043139 31 32. 33 34. «The substance or plant, or soil or propagation material, of which the compound I, π and 1 and/or IVA are as defined in any of the claims. A seed, per HK) kg of seed, in an amount of at least a compound of formula I II and / or IV and / or IVA, wherein compound J, form ... and / or IVA is as claimed in any one of claims 1 to 2 Defined. A pharmaceutical composition comprising at least one of the compounds of formula I, II and/or IV and/or IVA, or a pharmaceutically acceptable salt thereof, as claimed in any one of the claims, and at least one pharmaceutically acceptable carrier Agent. A use of a formula, or a ... and/or an IVA pharmaceutically acceptable salt, or a pharmaceutically acceptable salt thereof, according to any one of claims 1 to 20, for the manufacture of a medicament for treating cancer or a viral infection or Used to prepare antifungal drugs. A method of treating a cancer or a viral infection or against an animal pathogenic or human pathogenic fungus, comprising at least one of the compounds of formula I, II and/or IV and/or IVA according to any one of claims 1 to 2 The individual in need thereof is treated with at least one pharmaceutically acceptable salt thereof or a pharmaceutical composition as claimed in claim 32. 147475.doc 12- 201043139 IV. Designated representative map: (1) The representative representative of the case is: (none) (2) The symbolic symbol of the representative figure is simple: 5. If there is a chemical formula in this case, please reveal the best display invention. Characteristic chemical formula: 147475.doc147475.doc
TW099113196A 2009-04-24 2010-04-26 Triazole compounds carrying a sulfur substituent III TW201043139A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP09158757 2009-04-24

Publications (1)

Publication Number Publication Date
TW201043139A true TW201043139A (en) 2010-12-16

Family

ID=41716332

Family Applications (1)

Application Number Title Priority Date Filing Date
TW099113196A TW201043139A (en) 2009-04-24 2010-04-26 Triazole compounds carrying a sulfur substituent III

Country Status (3)

Country Link
AR (1) AR076428A1 (en)
TW (1) TW201043139A (en)
WO (1) WO2010122169A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013084770A1 (en) * 2011-12-05 2013-06-13 株式会社クレハ Azole derivative, method for producing azole derivative, intermediate compound, drug for agricultural and horticultural applications, and industrial material protectant

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07614B2 (en) * 1986-08-08 1995-01-11 呉羽化学工業株式会社 Novel tricyclic azole derivative, method for producing the same, and agricultural / horticultural fungicide containing the derivative as an active ingredient
JPH0625140B2 (en) * 1986-11-10 1994-04-06 呉羽化学工業株式会社 Novel azole derivative, method for producing the same and agricultural / horticultural drug of the derivative
JPH0762001B2 (en) * 1988-02-16 1995-07-05 呉羽化学工業株式会社 Process for producing azolylmethylcycloalkanol derivative
US5071853A (en) * 1989-03-23 1991-12-10 Bigge Christopher F Polycyclic amines useful as cerebrovascular agents
JPH03197464A (en) * 1989-12-16 1991-08-28 Basf Ag Substituted azolylmethylcycloalkanol and bactericide containing same
US5250735A (en) * 1992-04-03 1993-10-05 University Of Pittsburgh 2-(N-substituted-aminoalkyl)-5-(E)-alkylidene cyclopentanones, 2-(N-substituted-aminoalkyl)-5-(E)-arylalkylidene cyclopentanones, and derivatives thereof
JPH07138234A (en) * 1993-11-11 1995-05-30 Kureha Chem Ind Co Ltd Production of azolymethylcycloalkanol derivative
DK0736018T3 (en) * 1993-12-20 2000-09-18 Fujisawa Pharmaceutical Co 4,5-Diaryloxazole derivatives
US5420343A (en) * 1994-08-31 1995-05-30 G. D. Searle & Co. Derivatives of aromatic cyclic alkylethers
DE19520098A1 (en) * 1995-06-01 1996-12-05 Bayer Ag Triazolylmethyl-cyclopentanols
DE19520096A1 (en) * 1995-06-01 1996-12-05 Bayer Ag Cycloalkane benzylidene derivatives
DE19617282A1 (en) * 1996-04-30 1997-11-06 Bayer Ag Triazolyl mercaptide
DE19617461A1 (en) * 1996-05-02 1997-11-06 Bayer Ag Acylmercapto triazolyl derivatives
DE19619544A1 (en) * 1996-05-15 1997-11-20 Bayer Ag Triazolyl disulfides
DE19620407A1 (en) * 1996-05-21 1997-11-27 Bayer Ag Thiocyano-triazolyl derivatives
DE19620590A1 (en) * 1996-05-22 1997-11-27 Bayer Ag Sulfonyl-mercapto-triazolyl derivatives
BRPI0616263A2 (en) * 2005-09-23 2011-06-14 Janssen Pharmaceutica Nv cannabinoid modulators of the tetrahydro-cyclopentyl pyrazole type

Also Published As

Publication number Publication date
WO2010122169A1 (en) 2010-10-28
AR076428A1 (en) 2011-06-08

Similar Documents

Publication Publication Date Title
US10442777B2 (en) Use of substituted oxadiazoles for combating phytopathogenic fungi
TW201103920A (en) Triazole compounds carrying a sulfur substituent X
CA3003952A1 (en) Substituted oxadiazoles for combating phytopathogenic fungi
EP3373734A1 (en) Substituted oxadiazoles for combating phytopathogenic fungi
US20180317490A1 (en) Substituted oxadiazoles for combating phytopathogenic fungi
EA024331B1 (en) USE OF STROBILURIN TYPE COMPOUNDS FOR COMBATING PHYTOPATHOGENIC FUNGI RESISTANT TO Qo INHIBITORS
CA2939865A1 (en) Substituted [1,2,4]triazole and imidazole compounds as fungicides
TW201103429A (en) Triazole compounds carrying a sulfur substituent XI
BR112014000319B1 (en) USES OF FORMULA I COMPOUNDS, COMPOUNDS, PHYTOPATHOGENIC FUNGI METHODS, FORMULA I COMPOUND PREPARATION PROCESSES AND AGROCHEMICAL COMPOSITION
TW201103430A (en) Triazole compounds carrying a sulfur substituent XII
CA2950802A1 (en) Substituted [1,2,4]triazole and imidazole compounds as fungicides
US20120088660A1 (en) Antifungal 1,2,4-triazolyl Derivatives
CA3056347A1 (en) Substituted oxadiazoles for combating phytopathogenic fungi
TW200930293A (en) Pyridylmethyl-sulfonamide compounds
TW201103921A (en) Fungicidal mixtures
BR112019011293A2 (en) compounds of formula I, intermediates, agrochemical composition, use and method for combating phytopathogenic harmful fungi
CA2948208A1 (en) Substituted [1,2,4]triazole and imidazole compounds as fungicides
US20110015065A1 (en) Substituted Sulfonic Acid Amide Compounds
TW200924645A (en) Fungicidal compounds, processes for their preparation and their use for controlling harmful fungi, and compositions comprising them
TW201041514A (en) Triazole compounds carrying a sulfur substituent II
US20110003691A1 (en) Substituted Pyrazinylmethyl Sulfonamides For Use As Fungicides
US20120108422A1 (en) Antifungal 1,2,4-triazolyl Derivatives
WO2018210660A1 (en) Heteroaryl compounds as agrochemical fungicides
TW201043139A (en) Triazole compounds carrying a sulfur substituent III
US20100317516A1 (en) Sulfonamide Compounds And Their Use As Fungicide