CN101184747B - Cyano anthranilamide insecticides - Google Patents

Cyano anthranilamide insecticides Download PDF

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CN101184747B
CN101184747B CN2006800183129A CN200680018312A CN101184747B CN 101184747 B CN101184747 B CN 101184747B CN 2006800183129 A CN2006800183129 A CN 2006800183129A CN 200680018312 A CN200680018312 A CN 200680018312A CN 101184747 B CN101184747 B CN 101184747B
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cyclopropyl
ccn
alkyl
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CN101184747A (en
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A·简格纳特
A·奥苏里万
M·姆哈尔巴什
S·特拉
R·G·霍尔
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Syngenta Participations AG
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Abstract

Compounds of formula (I) wherein the substituents are as defined in claim 1 , and the agrochemically acceptable salts and all stereoisomers and tautomeric forms of the compounds of formula I can be used as agrochemical active ingredients and can be prepared in a manner known per se.

Description

Cyano anthranilamide insecticides
The present invention relates to new anthranilamide derivatives, the purposes of its preparation method, the composition containing the compound, and its canonical biometric of preventing and treating insect or Acarina.
Anthranilamide derivatives with insecticidal properties are known, are described in such as WO04/067528.It has now been found that with insecticidal properties, particularly for the member that prevents and treats insect and Acarina new cyano group substitution anthranilamide derivatives.
Therefore, the present invention relates to compound of formula I
Figure S2006800183129D00011
Wherein
Each E and Z, can represent oxygen or sulphur with identical or different；
A is C1-C6Alkylidene, C2-C6Alkenylene, C2-C6Alkynylene, or the ternary of divalence is to ten unit monocycles or condensed-bicyclic system, the ring can be fractional saturation or full saturation and the hetero atoms of nitrogen, oxygen and sulphur can be selected from containing 1-4, and each ring system, which can not contain, has more than the oxygen atom of two and the sulphur atom more than two；
Ternary to ten-ring system in itself and C1-C6Alkylidene, C2-C6Alkenylene and C2-C6Alkynylene may be by halogen, cyano group, nitro, hydroxyl, C1-C6Alkyl, C2-C6Alkenyl, C2-C6Alkynyl, C3-C6Cycloalkyl, C5-C7Cycloalkenyl group, C5-C8Cycloalkynyl radical, C1-C6Haloalkyl, C2-C6Haloalkenyl group, C2-C6Halo alkynyl, C3-C6Halogenated cycloalkyl, C5-C7Halo cycloalkenyl group, C5-C8Halo cycloalkynyl radical, C1-C4Alkoxy, C1-C4Halogenated alkoxy, C1-C4Alkylthio group, C1-C4Halogenated alkylthio, C1-C4Alkyl sulphinyl, C1-C4Alkyl sulphonyl, C1-C4Alkyl amino, C2-C4Dialkyl amido, C3-C6Cycloalkyl amino, C1-C6Alkyl-C3-C6Cycloalkyl amino, C2-C4Alkyl-carbonyl, C2-C6Alkoxy carbonyl, C2-C6Alkyl amino-carbonyl, C3-C6Dialkyl amino carbonyl, C2-C6Alkoxy carbonyloxy group, C2-C6Alkyl amino carbonyl oxy, C3-C6Dialkyl amido carbonyloxy group or C3-C6Trialkylsilkl is single-, two- or three substitutions, or can quilt
Ternary is to ten unit monocycles or condensed-bicyclic system are single-, two- or three substitutions, described monocyclic or condensed-bicyclic system can be aromatics, fractional saturation or full saturation and can be containing the 1-4 hetero atoms for being selected from nitrogen, oxygen and sulphur, each ring system, which can not contain, has more than the oxygen atom of 2 and the sulphur atom more than 2, the ternary to ten unit monocycles or condensed-bicyclic system in itself can be by halogen, cyano group, nitro, hydroxyl, C1-C6Alkyl, C2-C6Alkenyl, C2-C6Alkynyl, C3-C6Cycloalkyl, C5-C7Cycloalkenyl group, C5-C8Cycloalkynyl radical, C1-C6Haloalkyl, C2-C6Haloalkenyl group, C2-C6Halo alkynyl, C3-C6Halogenated cycloalkyl, C5-C7Halo cycloalkenyl group, C5-C8Halo cycloalkynyl radical, C1-C4Alkoxy, C1-C4Halogenated alkoxy, C1-C4Alkylthio group, C1-C4Halogenated alkylthio, C1-C4Alkyl sulphinyl, C1-C4Alkyl sulphonyl, C1-C4Alkyl amino, C2-C4Dialkyl amido, C3-C6Cycloalkyl amino, C1-C6Alkyl-C3-C6Cycloalkyl amino, C2-C4Alkyl-carbonyl, C2-C6Alkoxy carbonyl, C2-C6Alkyl amino-carbonyl, C3-C6Dialkyl amino carbonyl, C2-C6Alkoxy carbonyloxy group, C2-C6Alkyl amino carbonyl oxy, C3-C6Dialkyl amido carbonyloxy group, C3-C6Trialkylsilkl or phenyl list-, two or three substitutions, the phenyl may be again by hydroxyl, C1-C6Alkyl, C1-C6Haloalkyl, C1-C6- alkylthio group, C1-C6Halogenated alkylthio, C3-C6Alkenylthio group, C3-C6Halo alkenylthio group, C3-C6Alkynes sulfenyl, C1-C3Alkoxy -C1-C3Alkylthio group, C2-C4Alkyl-carbonyl-C1-C3Alkylthio group, C2-C4Alkoxy carbonyl-C1-C3Alkylthio group, cyano group-C1-C3Alkylthio group, C1-C6Alkyl sulphinyl, C1-C6Alkylsulfinyl, C1-C6Alkyl sulphonyl, C1-C6Halogenated alkyl sulfonyl, amino-sulfonyl, C1-C2Alkyl amino sulfonyl, the N, (C of N- bis-1-C2Alkyl) amino-sulfonyl, two (C1-C4Alkyl) amino, halogen, cyano group or nitro substitution；The substituent on nitrogen-atoms in ring system is not halogen；
X is oxygen, NH or C1-C4Alkyl-N；
Y be ternary to ten unit monocycles or condensed-bicyclic system, described monocyclic or condensed-bicyclic can be fractional saturation or full saturation and the hetero atoms of nitrogen, oxygen and sulphur can be selected from containing 1-4, and each ring system, which can not contain, has more than the oxygen atom of 2 and the sulphur atom more than 2；
The ternary to ten-ring system in itself can be by halogen, cyano group, nitro, hydroxyl, C1-C6Alkyl, C2-C6Alkenyl, C2-C6Alkynyl, C3-C6Cycloalkyl, C5-C7Cycloalkenyl group, C5-C8Cycloalkynyl radical, C1-C6Haloalkyl, C2-C6Haloalkenyl group, C2-C6Halo alkynyl, C3-C6Halogenated cycloalkyl, C5-C7Halo cycloalkenyl group, C5-C8Halo cycloalkynyl radical, C1-C4Alkoxy, C1-C4Halogenated alkoxy, C1-C4Alkylthio group, C1-C4Halogenated alkylthio, C1-C4Alkyl sulphinyl, C1-C4Alkyl sulphonyl, C1-C4Alkyl amino, C2-C4Dialkyl amido, C3-C6Cycloalkyl amino, C1-C6Alkyl-C3-C6Cycloalkyl amino, C2-C4Alkyl-carbonyl, C2-C6Alkoxy carbonyl, C2-C6Alkyl amino-carbonyl, C3-C6Dialkyl amino carbonyl, C2-C6Alkoxy carbonyloxy group, C2-C6Alkyl amino carbonyl oxy, C3-C6Dialkyl amido carbonyloxy group or C3-C6Trialkylsilkl it is single-, two- or three substitution, or by ternary to ten unit monocycles or condensed-bicyclic system be single-, two- or three substitutions, the ternary or ten unit monocycles or condensed-bicyclic system can be aromatics, fractional saturation or full saturation and can be selected from the hetero atoms of nitrogen, oxygen and sulphur containing 1-4, each ring system, which can not contain, has more than the oxygen atom of 2 and the sulphur atom more than 2, the ternary to ten-ring system in itself can be by halogen, cyano group, nitro, hydroxyl, C1-C6Alkyl, C2-C6Alkenyl, C2-C6Alkynyl, C3-C6Cycloalkyl, C5-C7Cycloalkenyl group, C5-C8Cycloalkynyl radical, C1-C6Haloalkyl, C2-C6Haloalkenyl group, C2-C6Halo alkynyl, C3-C6Halogenated cycloalkyl, C5-C7Halo cycloalkenyl group, C5-C8Halo cycloalkynyl radical, C1-C4Alkoxy, C1-C4Halogenated alkoxy, C1-C4Alkylthio group, C1-C4Halogenated alkylthio, C1-C4Alkyl sulphinyl, C1-C4Alkyl sulphonyl, C1-C4Alkyl amino, C2-C4Dialkyl amido, C3-C6Cycloalkyl amino, C1-C6Alkyl-C3-C6Cycloalkyl amino, C2-C4Alkyl-carbonyl, C2-C6Alkoxy carbonyl, C2-C6Alkyl amino-carbonyl, C3-C6Dialkyl amino carbonyl, C2-C6Alkoxy carbonyloxy group, C2-C6Alkyl amino carbonyl oxy, C3-C6Dialkyl amido carbonyloxy group, C3-C6Trialkylsilkl or phenyl is single-, two- or three substitutions, the phenyl may be again by hydroxyl, C1-C6Alkyl, C1-C6Haloalkyl, C1-C6Alkylthio group, C1-C6Halogenated alkylthio, C3-C6Alkenylthio group, C3-C6Halo alkenylthio group, C3-C6Alkynes sulfenyl, C1-C3Alkoxy -C1-C3Alkylthio group, C2-C4Alkyl-carbonyl-C1-C3Alkylthio group, C2-C4Alkoxy carbonyl-C1-C3Alkylthio group, cyano group-C1-C3Alkylthio group, C1-C6Alkyl sulphinyl, C1-C6Alkylsulfinyl, C1-C6Alkyl sulphonyl, C1-C6Halogenated alkyl sulfonyl, amino-sulfonyl, C1-C2Alkyl amino sulfonyl, the N, (C of N- bis-1-C2Alkyl) amino-sulfonyl, two (C1-C4Alkyl) amino, halogen, cyano group or nitro substitution；The substituent on nitrogen-atoms in ring system is not halogen；
P is 0 or 1；
Q is 0 or 1；
B be ternary to quaternary ring system, the ring system is all or part of saturation and can contain the hetero atom selected from nitrogen, oxygen and sulphur, and the ternary to quaternary ring system in itself can be by halogen, cyano group, nitro, hydroxyl, C1-C6Alkyl, C2-C6Alkenyl, C2-C6Alkynyl, C3-C6Cycloalkyl, C5-C7Cycloalkenyl group, C5-C8Cycloalkynyl radical, C1-C6Haloalkyl, C2-C6Haloalkenyl group, C2-C6Halo alkynyl, C3-C6Halogenated cycloalkyl, C5-C7Halo cycloalkenyl group, C5-C8Halo cycloalkynyl radical, C1-C4Alkoxy, C1-C4Halogenated alkoxy, C1-C4Alkylthio group, C1-C4Halogenated alkylthio, C1-C4Alkyl sulphinyl, C1-C4Alkyl sulphonyl, C1-C4Alkyl amino, C2-C4Dialkyl amido, C1-C6Cycloalkyl amino, C1-C6Alkyl-C3-C6Cycloalkyl amino, C2-C4Alkyl-carbonyl, C2-C6Alkoxy carbonyl, C2-C6Alkyl amino-carbonyl, C3-C6Dialkyl amino carbonyl, C2-C6Alkoxy carbonyloxy group, C2-C6Alkyl amino carbonyl oxy, C3-C6Dialkyl amido carbonyloxy group, C3-C6Trialkylsilkl it is single-, two- or three substitution, or by ternary to ten unit monocycles or condensed-bicyclic system be single-, two- or three substitutions, the ternary to ten unit monocycles or condensed-bicyclic system can be aromatics, fractional saturation or full saturation and can be selected from the hetero atoms of nitrogen, oxygen and sulphur containing 1-4, each ring system, which can not contain, has more than the oxygen atom of 2 and the sulphur atom more than 2, the ternary to ten unit monocycles or condensed-bicyclic system in itself can be by halogen, cyano group, nitro, hydroxyl, C1-C6Alkyl, C2-C6Alkenyl, C2-C6Alkynyl, C3-C6Cycloalkyl, C5-C7Cycloalkenyl group, C5-C8Cycloalkynyl radical, C1-C6Haloalkyl, C2-C6Haloalkenyl group, C2-C6Halo alkynyl, C3-C6Halogenated cycloalkyl, C5-C7Halo cycloalkenyl group, C5-C8Halo cycloalkynyl radical, C1-C4Alkoxy, C1-C4Halogenated alkoxy, C1-C4Alkylthio group, C1-C4Halogenated alkylthio, C1-C4Alkyl sulphinyl, C1-C4Alkyl sulphonyl, C1-C4Alkyl amino, C2-C4Dialkyl amido, C3-C6Cycloalkyl amino, C1-C6Alkyl-C3-C6Cycloalkyl amino, C2-C4Alkyl-carbonyl, C2-C6Alkoxy carbonyl, C2-C6Alkyl amino-carbonyl, C3-C6Dialkyl amino carbonyl, C2-C6Alkoxy carbonyloxy group, C2-C6Alkyl amino carbonyl oxy, C3-C6Dialkyl amido carbonyloxy group, C3-C6Trialkylsilkl or phenyl is single-, two- or three substitutions, the phenyl may be again by hydroxyl, C1-C6Alkyl, C1-C6Haloalkyl, C1-C6Alkylthio group, C1-C6Halogenated alkylthio, C3-C6Alkenylthio group, C3-C6Halo alkenylthio group, C3-C6Alkynes sulfenyl, C1-C3Alkoxy -C1-C3Alkylthio group, C2-C4Alkyl-carbonyl-C1-C3Alkylthio group, C2-C4Alkoxy carbonyl-C1-C3Alkylthio group, cyano group-C1-C3Alkylthio group, C1-C6Alkyl sulphinyl, C1-C6Alkylsulfinyl, C1-C6Alkyl sulphonyl, C1-C6Halogenated alkyl sulfonyl, amino-sulfonyl, C1-C2Alkyl amino sulfonyl, the N, (C of N- bis-1-C2Alkyl) amino-sulfonyl, two (C1-C4Alkyl) amino, halogen, cyano group or nitro substitution；The substituent on nitrogen-atoms in ring system is not halogen；
Each R1It is independently halogen, nitro, cyano group, hydroxyl, C1-C6Alkyl, C2-C6Alkenyl, C2-C6Alkynyl, C3-C6Cycloalkyl, C1-C6Haloalkyl, C2-C6Haloalkenyl group, C2-C6Halo alkynyl, C3-C6Halogenated cycloalkyl, C1-C4Alkoxy, C1-C4Halogenated alkoxy, C1-C4Alkylthio group, C1-C4Halogenated alkylthio, C1-C4Alkylsulfinyl, C1-C4Halogenated alkyl sulfonyl, C1-C4Alkyl sulphinyl, C1-C4Alkyl sulphonyl, C1-C4Alkyl amino, C2-C4Dialkyl amido, C3-C6Cycloalkyl amino, C1-C6Alkyl-C3-C6Cycloalkyl amino, C2-C4Alkyl-carbonyl, C2-C6Alkoxy carbonyl, C2-C6Alkyl amino-carbonyl, C3-C6Dialkyl amino carbonyl, C2-C6Alkoxy carbonyloxy group, C2-C6Alkyl amino carbonyl oxy, C3-C6Dialkyl amido carbonyloxy group or C3-C6Trialkylsilkl, phenyl, benzyl or phenoxy group, or by halogen, cyano group, nitro, halogen, C1-C6Alkyl, C2-C6Alkenyl, C2-C6Alkynyl, C3-C6Cycloalkyl, C1-C6Haloalkyl, C2-C6Haloalkenyl group, C2-C6Halo alkynyl, C3-C6Halogenated cycloalkyl, C1-C4Alkoxy, C1-C4Halogenated alkoxy, C1-C4Alkylthio group, C1-C4Halogenated alkylthio, C1-C4Alkyl sulphinyl, C1-C4Alkyl sulphonyl, C1-C4Alkyl amino, C2-C4Dialkyl amido, C3-C6Cycloalkyl amino, C1-C6Alkyl-C3-C6Cycloalkyl amino, C2-C4Alkyl-carbonyl, C2-C6Alkoxy carbonyl, C2-C6Alkyl amino-carbonyl, C3-C6Dialkyl amino carbonyl, C2-C6Alkoxy carbonyloxy group, C2-C6Alkyl amino carbonyl oxy, C3-C6Dialkyl amido carbonyloxy group or C3-C6Trialkylsilkl is single-, two- or trisubstd phenyl, benzyl or phenoxy group；
N is 0,1,2 or 3；
R2And R3Hydrogen, C each can be represented with identical or different1-C6Alkyl, C2-C6Alkenyl, C2-C6Alkynyl or C3-C8Cycloalkyl；Or it is selected from halogen, nitro, cyano group, hydroxyl, C by one or more1-C4Alkoxy, C1-C4Halogenated alkoxy, C1-C4Alkylthio group, C1-C4Halogenated alkylthio, C1-C4Alkyl sulphinyl, C1-C4Alkyl sulphonyl, C1-C4Alkyl amino, C2-C4Dialkyl amido, C3-C6Cycloalkyl amino and C1-C6Alkyl-C3-C6The C of the substituent substitution of cycloalkyl amino1-C6Alkyl, C2-C6Alkenyl, C2-C6Alkynyl or C3-C8Cycloalkyl；
D is phenyl, 2- pyridine radicals, 3- pyridine radicals or 4- pyridine radicals；Or by C1-C6Alkyl, C3-C6Cycloalkyl, C1-C6Haloalkyl, halogen, cyano group, C1-C4Alkoxy, C1-C4Halogenated alkoxy, C1-C4Alkylthio group, C1-C4Halogenated alkylthio, C1-C4Alkyl sulphinyl, C1-C4Alkyl sulphonyl, C1-C4Alkylsulfinyl or C1-C4Halogenated alkyl sulfonyl is single-, two- or trisubstd phenyl, 2- pyridine radicals, 3- pyridine radicals or 4- pyridine radicals；
Or D is following group
Figure S2006800183129D00061
R4, R4', R10, R17, and R19It is hydrogen, C independently of one another1-C6Alkyl, C3-C6Cycloalkyl, C1-C6Haloalkyl, halogen, cyano group, C1-C4Alkoxy, C1-C4Halogenated alkoxy, C2-C4Alkoxy carbonyl, C1-C4Alkylthio group, C1-C4Halogenated alkylthio, C1-C4Alkyl sulphinyl, C1-C4Alkyl sulphonyl, C1-C4Alkylsulfinyl or C1-C4Halogenated alkyl sulfonyl；
R5, R6, R8, R11, R12, R15, R16And R18It is C independently of one another1-C6Alkyl, or by halogen, cyano group, nitro, hydroxyl, C1-C4Alkoxy, C2-C4Alkoxy carbonyl, C1-C4Alkylthio group, C1-C4Alkyl sulphinyl, C1-C4Alkyl sulphonyl, C1-C4Alkyl amino, C2-C4Dialkyl amido or C3-C6Cycloalkyl amino is single-, two- or trisubstituted C1-C6Alkyl；Or phenyl, 2- pyridine radicals, 3- pyridine radicals, 4- pyridine radicals；Or by C1-C6Alkyl, C3-C6Cycloalkyl, C1-C6Haloalkyl, halogen, cyano group, C1-C4Alkoxy, C1-C4Halogenated alkoxy, C1-C4Alkylthio group, C1-C4Halogenated alkylthio, C1-C4Alkyl sulphinyl, C1-C4Alkyl sulphonyl, C1-C4Alkylsulfinyl or C1-C4Halogenated alkyl sulfonyl is single-, two- or trisubstd phenyl, 2- pyridine radicals, 3- pyridine radicals or 4- pyridine radicals；
R7, R9, R13And R14It is hydrogen, C independently of one another1-C6Alkyl, C1-C6Haloalkyl, C2-C6Alkenyl, C2-C6Haloalkenyl group, C3-C6Alkenyl or C3-C6Agriculturally acceptable salt/isomers/enantiomter/dynamic isomer/N- oxides of halo alkynyl and these compounds.
Compound I with least one basic center can form such as acid-addition salts, such as with strong inorganic acid such as ore deposit acid, such as perchloric acid, sulfuric acid, nitric acid, nitrous acid, phosphoric acid or halogen acids, with strong organic carboxyl acid, such as unsubstituted or substituted C1-C4Alkyl carboxylic acid, for example it is optionally substituted by halogen, such as acetic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid, such as hydroxycarboxylic acid, such as ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or such as benzoic acid, or and organic sulfonic acid, such as unsubstituted or substituted C1-C4Alkyl or aryl sulfonic acid, for example, be optionally substituted by halogen, such as methane-or p- toluenesulfonic acid.Compound I with least one acidic-group can for example with alkali forming salt, such as rock salt such as alkali metal or alkali salt, such as sodium salt, sylvite or magnesium salts, or with ammoniacal liquor or organic amine forming salt, the organic amine such as morpholine, piperidines, pyrrolidines, single-, two- or three-low-grade alkylamine, for example ethyl-, diethyl-, triethyl group-or dimethyl propyl amine, or single-, two- or trihydroxy-Iower-alky amine, such as single-, two- or three-monoethanolamine.Where appropriate, can also form corresponding inner salt.Within the scope of the present invention, salt favourable preferably on agriculture chemistry；However, present invention additionally comprises unfavorable salt, such as salt poisonous to honeybee and fish is applied for agriculture chemistry, the unfavorable salt is used for available salt on such as free compound I of isolated or purified or its agriculture chemistry.Due to the substantial connection between compound I free form and its salt form, for purposes of the invention, free cpds I or its salt in the above and below are interpreted as including corresponding salt or free compound I in due course respectively.This is equally applicable to compound I dynamic isomer and its salt.Generally, free form is preferred in all cases.
The alkyl occurred in the definition of substituent can be straight or branched, for example methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, amyl group, hexyl, heptyl and octyl group and its branched chain isomer.Alkoxy, alkenyl and alkynyl are derived from the alkyl.It is list-or how unsaturated that alkenyl and alkynyl, which can be,.
Halogen is typically fluorine, chlorine, bromine or iodine.Correspondingly, this is also applied for the halogen with reference to other implications, such as haloalkyl or halogenophenyl.
Haloalkyl preferably has the chain length of 1-6 carbon atom.Haloalkyl is such as methyl fluoride, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2- trifluoroethyls, 2- fluoro ethyls, 2- chloroethyls, pentafluoroethyl group, 1,1- bis- fluoro- 2,2,2- trichloroethyls, 2,2,3,3- tetra- fluoro ethyls and 2,2,2- trichloroethyls；It is preferred that trichloromethyl, difluorochloromethyl, difluoromethyl, trifluoromethyl and dichlorofluoromethyl.
Suitable haloalkenyl group is the alkenyl being mono-or polysubstituted with halogens, and halogen is fluorine, chlorine, bromine and iodine, particularly fluorine and chlorine, the fluoro- 1- methyl ethylenes of such as 2,2- bis-, 3- fluoropropene bases, chlorallylene base, 3- bromopropenyls, 2,3,3- trifluoro-propenyls, 2,3,3- tri chloropropenes base and 4,4,4- trifluoro but-2-ene -1- bases.In single-, two- by halogen or trisubstituted C3-C20 alkenyls, preferably with 3-5 carbon atom chain length.
Suitable halo alkynyl is the alkynyl being mono-or polysubstituted with halogens, and halogen is fluorine, chlorine, bromine and iodine, particularly fluorine and chlorine, such as 3- fluorine propinyl, 3- propargyl chloride bases, 3- propargyl bromide bases, 3,3,3- trifluoropropyl alkynyls and 4,4,4- trifluoro butyl- 2- alkynes -1- bases.In by halogen list-or polysubstituted alkynyl, preferably with 3-5 carbon atom chain length.
Alkoxy preferably has the chain length of 1-6 carbon atom.Alkoxy is such as methoxyl group, ethyoxyl, propoxyl group, isopropoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy and isomeric amoxy and hexyloxy；It is preferred that methoxyl group and ethyoxyl.
Alkoxy carbonyl is such as methoxycarbonyl, ethoxy carbonyl, propoxycarbonyl, isopropoxy carbonyl, n-butoxycarbonyl, isobutoxy carbonyl, s-butoxycarbonyl or tert-butoxycarbonyl；It is preferred that methoxycarbonyl or ethoxy carbonyl.Halogenated alkoxy preferably has the chain length of 1-6 carbon atom.Halogenated alkoxy is such as fluorine methoxyl group, difluoro-methoxy, trifluoromethoxy, 2,2,2- trifluoro ethoxies, 1,1,2,2- tetrafluoro ethyoxyl, 2- fluorine ethyoxyls, 2- chloroethoxies, 2,2- difluoroethoxies and 2,2,2- tri-chloroethoxy bases；It is preferred that difluoro-methoxy, 2- chloroethoxies and trifluoromethoxy.Alkylthio group preferably has the chain length of 1-6 carbon atom.Alkylthio group is such as methyl mercapto, ethylmercapto group, rosickyite base, isopropyisulfanyl, positive butylthio, isobutylthio, secondary butylthio or tertiary butylthio, preferably methyl mercapto and ethylmercapto group.Alkyl sulphinyl is such as methylsulfinyl, ethylsulfinyl, propylsulfenyl, isopropylsulphinyl, n-butylsulfinyl, isobutyl group sulfinyl, sec-butyl sulfinyl, terf-butylsulfinyl；It is preferred that methylsulfinyl and ethylsulfinyl.
Alkyl sulphonyl is such as methyl sulphonyl, ethylsulfonyl, sulfonyl propyl base, isopropelsulfonyl, normal-butyl sulfonyl, iso-butylsulfonyl, sec-butylsulfonyl or tert. butylsulfonyl；It is preferred that methyl sulphonyl or ethylsulfonyl.Alkyloxy-alkoxy preferably has the chain length of 1-8 carbon atom.The example of alkyloxy-alkoxy is：Methoxymethoxy, methoxy ethoxy, methoxy propoxy, (ethoxymethyl) epoxide, ethoxy ethoxy, propoxymethoxy or butoxybutoxy.Alkyl amino is such as methylamino, ethylamino, n-propyl amino, isopropylamino or isomeric butylamine.Dialkyl amido is such as dimethylamino, methylethylamine, diethylamino, n-propyl-methylamino, dibutylamino and diisopropylaminoethyl.It is preferred that alkyl amino there is the chain length of 1-4 carbon atom.Alkoxyalkyl preferably has the chain length of 1-6 carbon atom.Alkoxyalkyl is such as methoxy, methoxy ethyl, ethoxyl methyl, ethoxyethyl group, n-propoxymethyl, positive propoxy ethyl, i-propoxymethyl or isopropoxyethyl.Alkylthio alkyl preferably has the chain length of 1-8 carbon atom.Alkylthio alkyl is such as methylthiomethyl, methylmercaptoethyl, Ethylsulfanylmethyl, ethylthio-ethyl, positive rosickyite base methyl, positive rosickyite base ethyl, isopropylthiomethyl, isopropylthioethyl, Butylthiomethyl, butylthio ethyl or butylthiobutyl.Cycloalkyl preferably has 3-6 ring carbon atom, such as cyclopropyl, cyclobutyl, cyclopenta and cyclohexyl.Phenyl, also as a part for substituent such as phenoxy group, benzyl, benzyloxy, benzoyl, thiophenyl, phenylalkyl, phenoxyalkyl, can be substituted.In this case, substituent can be in ortho position, meta and/or contraposition.It is preferred that substituting group position be ortho position and contraposition relative to ring tie point.
As the ternary of optionally substituted full saturation or fractional saturation to quaternary ring system, and the ring system example that can contain the heteroatomic B selected from nitrogen, oxygen and sulphur be cyclopropyl, methyl-cyclopropyl, cyclopropanyl, cyclobutyl, cyclobutane base,
Figure S2006800183129D00091
Or
Figure S2006800183129D00092
According to the present invention, the ternary of fractional saturation or full saturation is to be selected from the following group according to the number of annular atom to ten unit monocycles or condensed-bicyclic system
Figure S2006800183129D00093
Cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, wherein the cycloalkyl moiety is preferably unsubstituted or by C1-C6Alkyl or halogen substitution, either
Figure S2006800183129D00094
Wherein each R26It is methyl, each R27With each R28It is independently hydrogen, C1-C3Alkyl, C1-C3Alkoxy, C1-C3Alkylthio group or trifluoromethyl, X4It is oxygen or sulphur, r=1,2,3 or 4.
When not showing free valence bond in definition, for example, exist
Figure S2006800183129D00102
In, link position is located at the carbon atom of mark " CH " or for example
Figure S2006800183129D00103
In the case of, at the binding site shown in lower left quarter.Second valency of substituent A or Y divalence ring system can be located at any suitable location of ring.
According to the present invention it is possible to which the ternary for being aromatics, fractional saturation or full saturation to ten unit monocycles or condensed-bicyclic system is to be selected from the following group according to the number of annular atom
Cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, wherein the cycloalkyl moiety be preferably it is unsubstituted or by C1-C6Alkyl or halogen substitution, or phenyl, benzyl, naphthyl or heterocycle base：Pyrrole radicals；Pyridine radicals；Pyrazolyl；Pyrimidine radicals；Pyrazinyl；Imidazole radicals；Thiadiazolyl group；Quinazolyl；Furyl；
Figure 2006800183129_0
Di azoly；Indolizine base；Pyranose；Isobenzofuran-base；Thienyl；1,5- phthalazinyl；(1- methyl isophthalic acid H- pyrazole-3-yls)-；(1- ethyl -1H- pyrazole-3-yls) -；(1- propyl group -1H- pyrazole-3-yls) -；(1H- pyrazole-3-yls)-；(the H- pyrazole-3-yls of 1,5- dimethyl -1) -；(the chloro- 1- methyl isophthalic acids H- pyrazole-3-yls of 4-)-；(1H- pyrazol-1-yls)-；(3- methyl isophthalic acid H- pyrazol-1-yls)-；(3,5- dimethyl -1H- pyrazol-1-yls) -；(3- is different
Figure 2006800183129_1
Oxazolyl)-；(5- methyl -3- is different
Figure 2006800183129_2
Oxazolyl)-；(3- methyl -5- is different
Figure 2006800183129_3
Oxazolyl)-；(5- is different
Figure 2006800183129_4
Oxazolyl)-；(1H- pyrroles -2- bases) -；(1- methyl isophthalic acid H- pyrroles -2- bases) -；(1H- pyrroles -1- bases) -；(1- methyl isophthalic acid H- pyrroles -3- bases) -；(2- furyls)-；(5- methyl -2- furyls) -；(3- furyls)-；(5- methyl -2- thienyls) -；(2- thienyls)-；(3- thienyls)-；(1- methyl isophthalic acid H- imidazoles -2- bases) -；(1H- imidazoles -2- bases) -；(1- methyl isophthalic acid H- imidazol-4 yls)-；(1- methyl isophthalic acid H- imidazoles -5- bases) -；(4- methyl -2-
Figure 2006800183129_5
Oxazolyl)-；(5- methyl -2-
Figure 2006800183129_6
Oxazolyl)-；(2-
Figure 2006800183129_7
Oxazolyl)-；(2- methyl -5-Oxazolyl)-；(2- methyl -4-Oxazolyl)-；(4- methyl -2- thiazolyls) -；(5- methyl -2- thiazolyls) -；(2- thiazolyls)-；(2- methyl-5-thiazoles base)-；(2- methyl -4- thiazolyls) -；(3- methyl -4- isothiazolyls) -；(3- methyl -5- isothiazolyls) -；(5- methyl -3- isothiazolyls) -；(1- methyl isophthalic acids H-1,2,3- triazole-4-yls)-；(2- methyl -2H-1,2,3- triazole-4-yls) -；(4- methyl -2H-1,2,3- triazole -2- bases) -；(1- methyl isophthalic acids H-1,2,4- triazole -3- bases) -；(1,5- dimethyl -1H-1,2,4- triazole -3- bases) -；(3- methyl isophthalic acids H-1,2,4- triazol-1-yls)-；(5- methyl isophthalic acids H-1,2,4- triazol-1-yls)-；(4,5- dimethyl -4H-1,2,4- triazole -3- bases) -；(4- methyl -4H-1,2,4- triazole -3- bases) -；(4H-1,2,4- triazole-4-yls)-；(5- methyl isophthalic acids, 2,3-
Figure 2006800183129_10
Diazole -4- bases) -；(1,2,3-
Figure 2006800183129_11
Diazole -4- bases) -；(3- methyl isophthalic acids, 2,4-
Figure 2006800183129_12
Diazole -5- bases) -；(5- methyl isophthalic acids, 2,4-
Figure 2006800183129_13
Diazole -3- bases) -；(4- methyl -3- furazanyls) -；(3- furazanyls)-；(5- methyl isophthalic acids, 2,4-
Figure 2006800183129_14
Diazole -2- bases) -；(5- methyl isophthalic acids, 2,3- thiadiazoles -4- bases) -；(1,2,3- thiadiazoles -4- bases) -；(3- methyl isophthalic acids, 2,4- thiadiazoles -5- bases) -；(5- methyl isophthalic acids, 2,4- thiadiazoles -3- bases) -；(4- methyl isophthalic acids, 2,5- thiadiazoles -3- bases) -；(5- methyl isophthalic acids, 3,4- thiadiazoles -2- bases) -；(1- methyl isophthalic acid H- tetrazolium -5- bases) -；(1H-TETRAZOLE -5- bases) -；(5- methyl isophthalic acid H- tetrazolium -1- bases) -；(2- methyl -2H- tetrazolium -5- bases) -；(2- ethyl -2H- tetrazolium -5- bases) -；(5- methyl -2H- tetrazolium -2- bases) -；(2H- tetrazolium -2- bases) -；(2- pyridine radicals)-；(6- methyl -2- pyridine radicals) -；(4- pyridine radicals)-；(3- pyridine radicals)-；(6- methyl -3- pyridazinyls) -；(5- methyl -3- pyridazinyls) -；(3- pyridazinyls)-；(4,6- dimethyl -2- pyrimidine radicals) -；(4- methyl -2- pyrimidine radicals) -；(2- pyrimidine radicals)-；(2- methyl -4- pyrimidine radicals) -；(the chloro- 4- pyrimidine radicals of 2-)-；(2,6- dimethyl -4- pyrimidine radicals) -；(4- pyrimidine radicals)-；(2- methyl -5- pyrimidine radicals) -；(6- methyl -2- pyrazinyls) -；(2- pyrazinyls)-；(4,6- dimethyl -1,3,5-triazines -2- bases) -；(4,6- bis- chloro-1,3,5-triazines -2- bases) -；(1,3,5-triazines -2- bases) -；(4- methyl isophthalic acids, 3,5- triazine -2- bases) -；(3- methyl isophthalic acids, 2,4- triazine -5- bases) -；(3- methyl isophthalic acids, 2,4- triazine -6- bases) -；
Figure S2006800183129D00121
Figure S2006800183129D00131
Wherein each R26It is methyl, each R27With each R28It is independently hydrogen, C1-C3Alkyl, C1-C3Alkoxy, C1-C3Alkylthio group or trifluoromethyl, X4It is oxygen or sulphur, r=1,2,3 or 4.
When not showing free valency in definition, for example, exist
Figure S2006800183129D00132
In, link position is located at the carbon atom of mark " CH " or for example
Figure S2006800183129D00133
In the case of, at the binding site shown in lower left quarter.
It is preferred that the sub-groups compounds of compound of formula I be wherein
A) p and/or q are 0；
B) E and/or Z are oxygen；And/or
c)R2And/or R3Be hydrogen and/or
D) A is divalence ternary to the monocyclic system of hexa-atomic saturation.
X is preferably oxygen, NH；N- methyl or N- ethyls.
Y is preferably C3-C6Cycloalkyl, particularly cyclopropyl.
R4' it is preferably hydrogen.
Especially it should be mentioned that these compound of formula I, wherein R1Selected from C1-C4Alkyl, halogen, C1-C5Haloalkyl, nitro, C1-C4Alkoxy, C1-C4- halogenated alkoxy, C1-C4Alkylthio group, C1-C4Alkyl sulphinyl, C1-C4Alkyl sulphonyl, C1-C4Halogenated alkylthio, C1-C4Alkylsulfinyl and C1-C4Halogenated alkyl sulfonyl, is especially selected from halogen and C1-C6Alkyl, is preferably selected from methyl and halogen, is most preferably selected from methyl and chlorine, and n is 1 or 2, preferably 1.R1It is preferred that position be and group-C (Z)-N (R3)-A-X-Y-B metas.
Preferred group of compound of formula I includes these compounds, and wherein A is C1-C6Alkylidene, the alkylidene can be by C3-C6Cycloalkyl, C2-C6Alkenyl, cyano group, C1-C4Alkylthio group, C1-C4Alkyl sulphonyl, C1-C4Alkoxy, halogen or C1-C6Haloalkyl replaces；Or A is C3-C6Cycloalkylidene.It is preferred that A is C3-C6Cycloalkylidene, most preferably cyclopropylidene.
In preferred compound of formula I, B is cyclopropyl, oxetanylmethoxy or cyclobutyl, preferably cyclopropyl.
These compound of formula I are also especially emphasized, wherein D is group D1, wherein R5It is the 2- pyridine radicals that can be optionally substituted by halogen, the R monosubstituted by chlorine preferably on the 3- positions of the pyridine ring4It is halogen, preferably chlorine or bromine, C1-C6Haloalkyl, C1-C4Halogenated alkoxy, preferably 2,2,2- trifluoro ethoxies, preferably C1-C6Haloalkyl, most preferably trifluoromethyl.
Further preferably these compound of formula I, wherein B is cyclopropyl or cyclobutyl, and the cyclopropyl or cyclobutyl can be by halogens, C1-C4Alkyl, hydroxyl, cyano group, C1-C4Alkoxy or C1-C4Alkylthio group it is single-, two- or three substitution；Or B is CH (CH2O), CH (CHMeO), CH- (CMe2O), CH (CH2S), CH (CH2OCH2), CH (CHMeOCH2), CH (CMe2OCH2), CH (CH2S-(O)2CH2), CH (CHMeS (O)2CH2), CH (CMe2S(O)2CH2), C (Me)-(CH2O), C (Me) (CHMeO), C (Me)-(CMe2O), C (Me)-(CH2S), C (Me)-(CH2OCH2), C (Me) (CHMeOCH2), C (Me)-(CMe2OCH2), C (Me)-(CH2S(O)2CH2), C (Me)-(CHMe-S (O)2CH2) or C (Me)-(CMe2-S(O)2CH2).In particularly preferred compound of formula I, B is can particularly to be replaced by halogen or methyl substituted cyclopropyl or cyclobutyl by chlorine, bromine or methyl；It is preferred that B is cyclopropyl.
The method that the present invention prepares compound of formula I is similarly carried out with known method, such as in WO 01/70671, WO 03/016284, WO 03/015518, method described in WO 04/033468 and WO04/067528.
Prepare free form in all cases or salt form compound of formula I or it is appropriate when its dynamic isomer method include, for example
A) it is preparation compound of formula I, wherein R2It is hydrogen and E and Z is oxygen, or where appropriate, its dynamic isomer and/or its salt,
By Formula II compound
Figure S2006800183129D00141
Wherein R1, n, and D have the implication in Formulas I, or its dynamic isomer and/or its salt when appropriate
With formula III compound or it is appropriate when with its dynamic isomer and/or its reactant salt
HN(R3)-(A)q-(X)p- Y-B (III),
Wherein R3, p, q, A, X, Y and B have the implication provided in Formulas I,
B) in order to prepare compound of formula I, or its dynamic isomer and/or its salt when appropriate, by formula IV compound
Figure S2006800183129D00151
Wherein R1, R2, n, Z and D have the implication that Formulas I is provided；And X1It is leaving group, or its dynamic isomer and/or its salt when appropriate
With the compound of formula III or it is appropriate when with its dynamic isomer and/or its reactant salt
HN(R3)-(A)q-(X)p- Y-B (III),
Wherein R3, p, q, A, X, Y and B have the implication provided in Formulas I, or
C) in order to prepare compound of formula I, or its dynamic isomer and/or its salt when appropriate,
By Formula V compound
Wherein R1, R2, R3, n, p, q, A, X, Y, Z and B have the implication that Formulas I is provided, or its dynamic isomer and/or its salt when appropriate
With Formula IV compound or it is appropriate when with its dynamic isomer and/or its reactant salt
X2C (=O) D (VI),
Wherein D has the implication that Formulas I is provided；And X2It is leaving group,
And/or by be in all cases free form or salt form compound of formula I or it is appropriate when its dynamic isomer change into another compound of formula I or be appropriate when its dynamic isomer, separate obtainable isomer mixture in the method, with the isomers for isolating needs and/or by free compound of formula I or it is appropriate when its dynamic isomer change into salt, by the salt of compound of formula I or it is appropriate when its dynamic isomer change into free compound of formula I or be appropriate when its dynamic isomer or change into another salt.
Formula II compound is new, and be in order to prepare the present invention compound of formula I and especial manufacture.Therefore Formula II compound constitutes another theme of the present invention.Formula II compound can be similarly prepared according to method described in WO 04/111030.
Formula V compound is also new, and be in order to prepare the present invention compound of formula I and especial manufacture.Therefore Formula V compound constitutes another theme of the present invention.Formula V compound is preferred, wherein
R1It is C1-C4Alkyl, halogen, C1-C5Haloalkyl, nitro, C1-C4Alkoxy, C1-C4- halogenated alkoxy, C1-C4Alkylthio group, C1-C4Alkyl sulphinyl, C1-C4Alkyl sulphonyl, C1-C4Halogenated alkylthio, C1-C4Alkylsulfinyl or C1-C4Halogenated alkyl sulfonyl；
R2And R3It is hydrogen；
A is C1-C6Alkylidene, it can be by C3-C6Cycloalkyl, C2-C6Alkenyl, cyano group, C1-C4Alkylthio group, C1-C4Alkyl sulphonyl, C1-C4Alkoxy, halogen or C1-C6Haloalkyl replaces；Or A is C3-C6Cycloalkylidene；
P and q are 0 or 1 independently of one another；
X is oxygen, NH；NCH3Or NC2H5；
Y is C1-C4Alkylidene, C2-C6Alkenylene or C3-C6Alkynylene or, by halogen, C3-C6Cycloalkyl, C1-C4Alkyl sulphonyl or C1-C4The C of alkoxy substitution1-C4Alkylidene, C2-C6Alkenylene or C3-C6Alkynylene；Being with B can be by halogen, C1-C4Alkyl, hydroxyl, cyano group, C1-C4Alkoxy or C1-C4Alkylthio group is single-, two- or trisubstituted cyclopropyl or cyclobutyl；Or B is CH (CH2O), CH (CHMeO), CH- (CMe2O), CH (CH2S), CH (CH2OCH2), CH (CHMeOCH2), CH (CMe2OCH2), CH (CH2S-(O)2CH2), CH (CHMeS (O)2CH2), CH (CMe2S(O)2CH2), C (Me)-(CH2O), C (Me) (CHMeO), C (Me)-(CMe2O), C (Me)-(CH2S), C (Me)-(CH2OCH2), C (Me) (CHMeOCH2), C (Me)-(CMe2OCH2), C (Me)-(CH2S(O)2CH2), C (Me)-(CHMe-S (O)2CH2) or C (Me)-(CMe2-S(O)2CH2), preferably B is can be by halogen, C1-C4Alkyl, hydroxyl, cyano group, C1-C4Alkoxy or C1-C4Alkylthio group is single-, two- or trisubstituted cyclopropyl or cyclobutyl.
Formula V compound in all cases for free form or salt form or it is appropriate when its dynamic isomer preparation method include, for example
In order to formula V compounds or it is appropriate when its dynamic isomer and/or its salt, by Formula VII compound
Figure S2006800183129D00171
Wherein R1, R2, n has the definition in Formulas I, with formula III compound or it is appropriate when its dynamic isomer and/or its reactant salt
HN(R3)-(A)q-(X)p- Y-B (III),
Wherein R3, p, q, A, X, Y and B have the definition in Formulas I.
The dynamic isomer and/or its salt of starting material mentioned in the above and below are equally applicable to for the content described in compound I dynamic isomer and/or salt.
Reaction is carried out in a way known described in above and below, for example it is being not present or generally in the case where there is suitable solvent or diluent or its mixture, as needed cooling, at room temperature or heating, for example in about -80 DEG C of boiling point temperature ranges to reactant mixture, it is preferred that from about -20 DEG C to about+150 DEG C, and if necessary in closed container, under decompression, normal pressure or high pressure, carry out under inert gas atmosphere and/or in anhydrous conditions.Particularly advantageous reaction condition is found in embodiment.
Unless otherwise indicated, the raw material of its dynamic isomer is known or can for example prepared by method known per se according to information described below when being used for of mentioning in the above and below prepares compound of formula I in all cases for free form or salt form or be appropriate.
Political reform a)
Reactant can directly react to each other, i.e., need not add solvent or diluent, such as with molten state.However, addition atent solvent or diluent or its mixture are usually favourable.The solvent or the example of diluent that can be mentioned that be：Aromatics, aliphatic series and cycloaliphatic hydrocarbons and halogenated hydrocarbon, such as benzene, toluene, dimethylbenzene, mesitylene, tetralin, chlorobenzene, dichloro-benzenes, bromobenzene, petroleum ether, hexane, hexamethylene, dichloromethane, chloroform, tetrachloromethane, dichloroethanes, trichloro ethylene or tetrachloro-ethylene；Esters such as ethyl acetate；Ethers such as diethyl ether, dipropyl ether, diisopropyl ether, butyl oxide, t-butyl methyl ether, glycol monoethyl ether, ethylene glycol monoethyl ether, glycol dimethyl ether, dimethoxy Anaesthetie Ether, tetrahydrofuran or dioxane；Ketone such as acetone, MEK or methylisobutylketone；Alcohols such as methanol, ethanol, propyl alcohol, isopropanol, butanol, ethylene glycol or glycerine；Amide-type such as DMF, N, N- diethylformamides, DMA, 1-METHYLPYRROLIDONE or HMPA；Nitrile, such as acetonitrile or propionitrile；And sulfoxide type, such as dimethyl sulfoxide (DMSO).
Reaction is carried out advantageously in about -80 DEG C to about+140 DEG C temperature ranges, preferably approximately -30 DEG C to about+100 DEG C, in most cases in room temperature in the range of about+80 DEG C.
Political reform b)
Suitable leaving group X in compound IV1Example be hydroxyl, C1-C8Alkoxy, halo-C1-C8Alkoxy, C1-C8Alkanoyloxy, sulfydryl, C1-C8Alkylthio group, halo-C1-C8Alkylthio group, C1-C8Alkylsulfonyloxy, halo-C1-C8Alkylsulfonyloxy, phenylsulfonyloxy, tosyloxy and halogen, such as chlorine.It is preferred that hydroxyl, C1-C8Alkoxy and chlorine.
Reactant can directly react to each other, i.e., need not add solvent or diluent.However, addition atent solvent or diluent or its mixture are usually favourable.Suitable solvent or the example of diluent are the types described in change a).
Reaction is carried out advantageously in about -80 DEG C to about+140 DEG C temperature ranges, preferably approximately -20 DEG C to about+100 DEG C, in most cases in the reflow temperature range of room temperature to reactant mixture.
Political reform c)
Suitable leaving group X in Formula IV compound2Example be hydroxyl, C1-C8Alkoxy, halo-C1-C8Alkoxy, C1-C8Alkanoyloxy, sulfydryl, C1-C8Alkylthio group, halo-C1-C8Alkylthio group, C1-C8Alkylsulfonyloxy, halo-C1-C8Alkylsulfonyloxy, phenylsulfonyloxy, tosyloxy and halogen, such as chlorine.It is preferred that hydroxyl and chlorine.
Reactant can react in the presence of base.Suitable for promoting HX2The example of the alkali of disengaging is alkali metal or alkaline earth metal hydroxide, alkali metal or alkaline earth metal hydride, alkali metal or alkaline earth metal amides, alkali metal or alkaline-earth alkoxides, alkali metal or alkaline earth metal acetates, alkali metal or alkaline earth metal carbonate, alkali metal or alkaline-earth metal dialkylamides or alkali metal or alkaline-earth metal alkylsilyl-amides, alkyl amine, Alkylenediamine class, the saturation or unsaturation ring alkyl amine, basic heterocycles, ammonium hydroxide and carbocyclic ring amine of free or N- alkylations.The example that can be mentioned that is sodium hydroxide, sodium hydride, Sodamide, sodium methoxide, sodium acetate, sodium carbonate, potassium tert-butoxide, potassium hydroxide, potassium carbonate, hydrofining, lithium diisopropylamine, double (trimethyl silyl) potassamides, calcium hydride, triethylamine, diisopropyl ethyl amine, triethylenediamine, cyclohexylamine, N- cyclohexyl-N, N- dimethyl amines, N, N- diethylanilines, pyridine, 4- (N, N- dimethylaminos) pyridine, quinuclidine, N-methylmorpholine, benzyl trimethylammonium hydroxide and 1, carbon -7- the alkene (DBU) of 8- diazabicylos [5.4.0] 11.
Reactant can directly react to each other, i.e., need not add solvent or diluent.However, addition atent solvent or diluent or its mixture are usually favourable.Suitable solvent or the example of diluent are the types described in change a).If reaction is carried out in the presence of base, the alkali being excessively used such as triethylamine, pyridine, N-methylmorpholine or N, N- diethylaniline can also act as solvent or diluent.
Reaction is carried out advantageously in about -80 DEG C to about+140 DEG C temperature ranges, preferably approximately -30 DEG C to about+100 DEG C, in most cases in room temperature in the range of about+80 DEG C.
By replacing initial compounds I one or more substituents with other substituents of the present invention in a usual manner, compound I can be changed into another compound I in a way known.
For example,
- in compound I, wherein R2It is hydrogen, this is the R of hydrogen2It can be the substituent R of hydrogen2Instead of；Or
- in compound I, wherein R3It is hydrogen, this is the R of hydrogen3It can be the substituent R of hydrogen3Instead of.
According to the selection of to reaction condition and in all cases applicable raw material, a substituent can be replaced with another substituent of the present invention for example only in a reactions steps, or with other substituents of the present invention multiple substituents are replaced in same step.
Compound I salt can be prepared in a way known.Obtain, can be obtained with the salt of alkali formation by using suitable alkali or the processing of suitable ion exchange reagent thus, for example compound I acid-addition salts can be handled by using suitable sour or suitable ion exchange reagent.
Compound I salt can change into free compound I in a usual manner, and acid-addition salts are for example handled by using suitable alkali compounds or suitable ion exchange reagent, for example be handled with the salt of alkali formation by using suitable sour or suitable ion exchange reagent.
Compound I salt can change into compound I other salt in a way known, acid-addition salts are for example changed into other acid-addition salts, the salt in suitable solvent with a kind of sour suitable metal salt such as sodium salt, barium salt or silver salt such as silver acetate processing inorganic acid such as hydrochloric acid can be passed through, the inorganic salts formed in the solvent are insoluble such as silver chlorate, therefore are precipitated out from reactant mixture.
According to method or reaction condition, the compound I with salt performance of free form or salt form can be obtained.
The configuration of the number and relative configuration of the asymmetric carbon atom according to present in molecule and/or the non-aromatic double bond according to present in molecule, compound I in all cases for free form or salt form and it is appropriate when its dynamic isomer using in the form of one of possible isomers or the presence of its mixture can be used as, for example in the form of pure isomer, such as enantiomer and/or diastereomer, or it is used as isomer mixture, such as enantiomeric mixture, such as racemate, non-enantiomer mixture or racemate mixture are present；The present invention relates to pure isomer and all possible isomer mixture, and all should so it understand in the above and below, even if stereochemical details are not referred to clearly in all cases.
The free form or the compound I of salt form non-enantiomer mixture or racemic mixture that can be obtained according to the raw material and method of selection, pure diastereomer or racemate can be separated into known manner according to the physical chemical differences of each composition, for example, pass through fractional crystallization, distillation and/or chromatography.
The enantiomeric mixture that can be obtained in a similar manner such as racemate can be split as optical antipode by known method, for example by being recrystallized from optically-active solvent, pass through the chromatographic isolation on chiral sorbent, high performance liquid chromatography (HPLC) for example on cellulose acetate, by suitable microorganism, by using specific immobilised enzymes, by forming inclusion compound, for example using chiral crown ether, in this case a kind of enantiomer is complexed, or by changing into diastereomeric salt, for example pass through basic termini product racemate and optically-active acid reaction, such as carboxylic acid, such as camphoric acid, tartaric acid or malic acid, or sulfonic acid, such as camphorsulfonic acid, with separation obtainable non-enantiomer mixture in this way, fractional crystallization for example by being carried out based on its different solubility, produce diastereomer, therefrom dissociated desired enantiomer by the effect of suitable reagent such as alkaline reagent.
The pure diastereomer or enantiomer of the present invention can not only be obtained by separating suitable isomer mixture, it can also be obtained by commonly known cis-selectivity or enantioselective synthesis method, for example, implement the method for the present invention by using suitable stereochemical raw material.
In all cases, if there is individual compound more effectively isomers in different bioactivity, separation or synthetic biology to be favourable, such as enantiomer or diastereomer or isomer mixture, such as mixture of enantiomers or non-enantiomer mixture.
Compound I in all cases for free form or salt form and it is appropriate when its dynamic isomer can also obtain hydrate forms if necessary and/or comprising other solvents, such as solvent for crystallizing the compound existed in solid form.
The compound of the present invention is the active component for having prevention and/or therapeutic value in field of pest control, even under low consumption, it has very favorable biocidal spectrum and is resistant to well by warm blooded species, fish and plant.The active component of the present invention is not only effective to all or individual development stages conventional sensitive animal pests, and the insect of antagonism animal pest, such as Acarina or canonical biometric are effective.The desinsection or acaricidal activity of the active component of the present invention can be directly displayed, shown with the Mortality of insect for occurring immediately or occurring for example during cast off a skin merely through a period of time, or show that excellent activity is equivalent to elimination rate (death rate) at least 50 to 60% indirectly for example to reduce spawning and/or incubation rate.
The example of above-mentioned animal pest is：
Acarina (Acarina), for example
Acarus siro (Acarus siro),Citrus aceria (Aceria sheldoni),Steinman pin thorn goitre mite (Aculus schlechtendali),Amblyomma (Amblyomma spp.),Hidden beak ant belongs to (Argas spp.),Boophilus (Boophilus spp.),Short whisker Acarapis (Brevipalpus spp.),Lucerne place tongue mite (Bryobia praetiosa),Calipitrimerus spp.,Trombiculid (Chorioptes spp.),Dermanyssus gallinae (Dermanyssus gallinae),Eotetranychus carpini (Eotetranychus carpini),Eriophyes (Eriophyes spp.),Hyalommaspp (Hyalomma spp.),Hard ant category (Ixodes spp.),Olygonychus pratensis,Beak tick belongs to (Orni thodorosspp.),Red spider belongs to (Panonychus spp.),Citrus rust mite (Phyllocoptrutaoleivora),Polyphagotarsonemus latus Banks (Polyphagotarsonemus latus),Overworked mite belongs to (Psoroptes spp.),Rh (Rhipicephalus spp.),Root mite belongs to (Rhizoglyphus spp.),Sarcoptesspp (Sarcoptes spp.),Line mite belongs to (Tarsonemus spp.) and tetranychus telarius category (Tetranychus spp.)；
Anoplura (Anoplura), for example
Haematopinus (Haematopinus spp.), Linognathus (Linognathus spp.), Pediculus (Pediculus spp.), Pemphigus (Pemphigus spp.) and Phylloxera spp (Phylloxera spp.)；
Coleoptera (Coleoptera), for example
Click beetle belongs to (Agriotes spp.),Anthonomus spp belongs to (Anthonomus spp.),Atomaria linearis (Atomaria linearis),Chaetocnema tibialis (Chaetoenema tibialis),Banana root weevil belongs to (Cosmopolites spp.),Curculio (Curculio spp.),Khapra beetle belongs to (Dermestes spp.),The chrysomelid category (Diabrotica spp.) of bar,Plant ladybug category (Epilachna spp.),Eremnus spp.,Colorado potato bug (Leptinotarsadecemlineata),Lissorhoptrus oryzophilus Kuschel belongs to (Lissorhoptrus spp.),Gill cockchafer belongs to (Melolontha spp.),Orycaephilus spp.,Otiorhynchus spp (Otiorhynchusspp.),Phlyctinus spp.,Rutelian belongs to (Popillia spp.),Phyllotreta (Psylliodes spp.),Dynamic root moth category (Rhizopertha spp.),Scarabeidae (Scarabeidae),Sitophilus (Sitophilus spp.),Gelechiid belongs to (Sitotrogaspp.),Tenebrio (Tenebrio spp.),Intend paddy temperature category (Tribolium spp.) and khapra beetle category (Trogoderma spp.)；
Diptera (Diptera), for example
Aedes (Aedes spp.),Antherigona soccata,Bibio hortulanus,Calliphora (Calliphora erythrocephala),Anastrepha (Ceratitis spp.),Carysomyia (Chrysomyia spp.),Culex (Culex spp.),Cuterbrid belongs to (Cuterebraspp.),Anastrepha (Dacus spp.),Drosophila yellow gorilla (Drosophilamelanogaster),Fannia (Fannia spp.),Horse botfly belongs to (Gastrophilusspp.),Glossina (Glossina spp.),Hypoderma (Hypoderma spp.),Hyppobosca spp.,Hippelates (Liriomyza spp.),Lucilia (Lucilia spp.),The black Hippelates of dried bean curd (Melanagromyza spp.),Fly belongs to (Musca spp.),Oestrus (Oestrus spp.),Orseolia spp.,Sweden's wheat stem chloropid fly (Oscinella frit),Kmangold fly (Pegomyia hyoscyami),Spring wheat fly belongs to (Phorbia spp.),Apple trypetid (Rhagoletis pomonella),Gill fungus fly belongs to (Sciara spp.),Genus Stomoxys (Stomoxysspp.),Gadfly (Tabanus spp.),Tannia spp. and big uranotaenia (Tipula spp.)；
Heteroptera (Heteroptera), for example
Cimex (Cimex spp.), Distantiella theobroma (Distantiella theobroma), red stinkbug belongs to (Dysdercus spp.), Euchistus spp., brown scutteleerid belongs to (Eurygasterspp.), Leptocorisa spp belongs to (Leptocorisa spp.), Bemisia spp (Nezara spp.), lace bug belongs to (Piesma spp.), red abdomen Reduvius (Rhodnius spp.), Sahlbergella singularis (Sahlbergella singularis), scotinophora lurida belongs to (Scotinophara spp.) and Triatoma (Triatoma spp.)；
Homoptera (Homoptera), for example
Continuous confused lice (Aleurothrixus floccosus),Aleyrodes (Aleyrodesbrassicae),Circle helmet a red-spotted lizard category (Aonidiella spp.),Aphidiadae (Aphididae),Aphis (Aphis spp.),Aspidiotus belongs to (Aspidiotus spp.),Sweet potato whitefly (Bemisiatabaci),Lecanium belongs to (Ceroplaster spp.),Chrysomphalus aonidium (Chrysomphalusaonidium),Dictyospermum scale (Chrysomphalus dictyospermi),Coccushesperidum (Coccushesperidum),Empoasca spp belongs to (Empoasca spp.),Eriosoma lanigerum (Eriosomalarigerum),Erythema leafhopper belongs to (Erythroneura spp.),Gascardia spp.,Small brown-back rice plant-hopper belongs to (Laodelphax spp.),The hard ball a red-spotted lizard of Europe fruit,Lepidosaphes belongs to (Lepidosaphesspp.),Macrosiphus spp.,Knurl volume Aphis (Myzus spp.),Rice green leafhopper belongs to,Brown paddy plant hopper belongs to (Nilaparvata spp.),Parlatoria,Pemphigus (Pemphigusspp.),Stern line mealybug belongs to (Planococcus spp.),White peach scale belongs to (Pseudaulacaspisspp.),Mealybug belongs to (Pseudococcus spp.),Leaf Pediculus (Psylla spp.),Cotton a red-spotted lizard (Pulvinaria aethiopica),Aspidiotus belongs to (Quadraspidiotus spp.),Pipe of hanging belongs to (Rhopalosiphum spp.),Helmet a red-spotted lizard belongs to (Saissetia spp.),Leafhopper belongs to (Scaphoideus spp.),Green bugs belongs to (Schizaphis spp.),Sitobion spp.,Greenhouse whitefly (Trialeurodes vaporariorum),Wood louse (Tr ioza erytreae) and Unaspis citri (Unaspis citri)；
Hymenoptera (Hymenoptera), for example
Acromyrmex, Myrmecina (Atta spp.), stem honeybee belongs to (Cephus spp.), tenthredinidae (Diprion spp.), Diprionidae (Diprionidae), Gilpinia polytoma (Gilpiniapolytoma), tenthredinidae (Hoplocampa spp.), field ant category (Lasius spp.), ant belongs to (Monomorium pharaonis), Neodiprion spp belongs to (Neodiprion spp.), Solenopsis (Solenopsis spp.) and Vespa (Vespa spp.)；
Isoptera (Isoptera), for example
Reticulitermes；
Lepidoptera (Lepidoptera), for example
Acleris spp belongs to (Acleris spp.),Steinernema belongs to (Adoxophyes spp.),Clearwing moth belongs to (Aegeria spp.),Agrotis (Agrotis spp.),Cotton leaf ripple noctuid (Alabama argillaceae),Amylois spp.,Anticarsia (Anticarsiagemmatalis),Archips spp (Archips spp.),Argyrotaenia belongs to (Argyrotaeniaspp.),Noctua (Autographa spp.),Corn pattern noctuid (Busseola fusca),Meal moth (Cadra cautella),Small heart-eating peach worm (Carposina nipponensis),Straw borer spp (Chilo spp.),Roll up moth category (Choristoneura spp.),Grape codling moth (Clysia ambiguella) (Clysia ambiguella),The vertical volume snout moth's larva category (Cnaphalocrocis spp.) of rice,Leaf roller belongs to (Cnephasia spp.),Cochylis spp.,Casebearer moth (Coleophora spp.),General non-fine hair snout moth's larva,Cryptophlebia leucotreta (Cryptophlebia leucotreta),Beans steinernema belongs to (Cydia spp.),Different Crambus Fabricius (Diatraea spp.),Diparopsis castanea (Diparopsis castanea),Earias (Earias spp.),Meal moth belongs to (Ephestia spp.),Preserved egg steinernema belongs to (Eucosma spp.),Eupoeciliaambiguella,Euproctis (Euproctis spp.),Cutworm belongs to (Euxoa spp.),Small leaf volume belongs to (Grapholita spp.),Hedya nubiferana,Genus heliothis (Heliothis spp.),Hellula undalis (Hellula undalis),Fall webworms (Hyphantria cunea),Tomato pinworm moth (Keiferia lycopersicella),Pear leaf blister moth (Leucoptera scitella),Thin moth category (Lithocollethis spp.),Flower wing steinernema (Lobesia botrana),Euproctis (Lymantria spp.),Lyonetiaspp (Lyonetia spp.),Malacosoma (Malacosoma spp.),Lopper worm (Mamestra brassicae),Maduca sexta (Manduca sexta),Winter geometrid moth belongs to (Operophtera spp.),Corn borer (Ostrinia nubilalis),Super steinernema belongs to (Pammene spp.),Brown epiblema (Pandemis spp.),Small noctuid (Panolisflammea),Pink bollworm (Pectinophora gossypiela),Potato tuberworm (Phthorimaea operculella),Cabbage butterfly (Pieris rapae),Pieris spp (Pieris spp.),Diamondback moth (Plutella xylostella),Yponomeuta (Prays spp.),Yellow rice borer belongs to (Scirpophaga spp.),Pink rice borer belongs to (Sesamia spp.),Long hair volume moth category (Sparganothis spp.),Spodoptera (Spodoptera spp.),Clearwing moth belongs to (Synanthedon spp.),Band moth category (Thaumetopoea spp.),Leaf roller belongs to (Tortrix spp.),Cabbage looper (Trichoplusia ni) and Yponomeuta (Yponomeutaspp.)；
Mallophaga (Mallophaga), for example
Damalinea spp. and Trichodectes (Trichodectes spp.)；
Orthoptera (Orthoptera), for example
Blattaria category (Blatta spp.), Blatella (Blattella spp.), Gryllotalpa spp (Gryllotalpa spp.), Ma get La blattarias (Leucophaea maderae), migratory locusts category (Locusta spp.), Periplaneta (Periplaneta spp.) and grasshopper category (Schistocercaspp.)；
Corrodentia (Psocoptera), for example
Powder corrodent belongs to (Liposcelis spp.)；
Siphonaptera (Siphonaptera), for example
Ceratophyllus (Ceratophyllus spp.), Ctenocephalus (Ctenocephalidesspp.) and Xanthopsyllacheopis (Xenopsylla cheopis)；
Thysanoptera (Thysanoptera), for example
Flower thrips category (Frankliniella spp.), Hercinothrips spp category (Hercinothripsspp.), Scirtothrips aurantii (Scirtothrips aurantii), Taeniothrips (Taeniothrips spp.), pale brown thrips (Thrips palmi) and cotton thrips (Thripstabaci)；
Thysanoptera (Thysanura), for example
Silverfiss (Lepisma saccharina).
The active component of the present invention can be used for preventing and treating; suppress or eliminate the plant especially occurred from agricultural, gardening and forestry; the insect of the above-mentioned type especially on useful plants and ornamental plant or on organ such as fruit, flower, leaf, stem, stem tuber or root; in some cases, or even the organ of the useful plants formed later can be protected from the infringement of these insects.
Suitable Target crops are to be particularly, cereal, such as wheat, barley, rye, oat, rice, corn or jowar；Beet, such as sugar beet and fodder beet；Fruit, such as the operatic circle, drupe or soft fruit, such as apple, pears, plum, peach, apricot, cherry or berry, such as strawberry, raspberry or blackberry, blueberry；Legume, such as Kidney bean, lens, pea or soybean；Oilseed plant, such as rape, leaf mustard, opium poppy, olive, sunflower, coconut, castor-oil plant, cocoa bean or peanut；Muskmelon platymiscium, such as pumpkin, cucumber or muskmelon；Fibre plant, such as cotton, flax, hemp or jute；Citrus fruit, such as orange, lemon, liana shaddock or orange；Vegetables, such as spinach, lettuce, asparagus, cabbage, carrot, onion, tomato, potato or bell pepper；Lauraceae, such as avocado, Chinese cassia tree or camphor；And tobacco；Nut；Coffee；Eggplant, sugarcane, tea, pepper；Liana, hop, plantago, latex plant and ornamental plant.
The active component of the present invention is particularly suitable for use in preventing and treating the bean aphid in cotton, vegetables, corn, rice and soybean crops, and band spot cucumber is chrysomelid, tobacco budworm, black peach aphid, diamondback moth and Spodoptera littoralis.The active component of the present invention is also particularly suitable preventing and treating lopper worm and belonged to (preferably in vegetables), codling moth (preferably in apple), Empoasca is (preferably in vegetables, in vineyard), thin instep is chrysomelid to be belonged to (preferably in potato) and striped rice borer (preferably in rice).
Term " crop " is interpreted as also including because conventional breeding methods or gene engineering method make its herbicide-tolerant such as Brominal or multiclass herbicide (such as HPPD inhibitor, ALS inhibitor, such as primisulfuronmethyl, prosulfuron and trifloxysulfuron, EPSPS (5- enol-pyrovyl-shikimate -3- phosphate synthases) inhibitor, GS (glutamine synthelase) inhibitor) crop.The example of the crop of its resistance to imidazolone type such as imazamox is set to be Clearfield by conventional breeding methods (mutation is formed)
Figure 2006800183129_15
Summer rape (Canola).The example of the crop of herbicide-resistant or classes of herbicides is allowed to by gene engineering method includes resistance glyphosate and the corn of glufosinate-resistant, and the kind can be according to trade name RoundupReady
Figure 2006800183129_16
, Herculex I
Figure 2006800183129_17
And LibertyLink
Figure 2006800183129_18
Commercially.
Term " crop " is interpreted as also including that the crop of one or more selectively acting toxin can be synthesized by using recombinant DNA technology conversion, and the toxin comes from those bacteriums that toxin produces bacterium, particularly bacillus as known.
It can be included by the toxin of the Expressed in Transgenic Plant, such as insect-killing protein for example comes from the insect-killing protein of bacillus subtilis or Japanese beetle bacillus；Or come from the insect-killing protein of bacillus thuringiensis, such as delta-endotoxin, such as CryIA (b), CryIA (c), CryIF, CryIF (a2), CryIIA (b), CryIIIA, CryIIIB (b1) or Cry9c, or vegetative insecticidal proteins matter (VIP), such as VIP1, VIP2, VIP3 or VIP3A；Or the insect-killing protein of bacteria paragenesis nematode, such as Photorhabdus or Xenorhabdus, such as luminous light rod bacterium, Xenorhabdus nematophilus；The toxin produced by animal, such as scorpion toxin, spider toxin, wasp toxin and other insect-specific neurotoxins；By mycetogenetic toxin, such as strepto- verticillium toxin；Phytolectin, such as pisum sativum agglutinin, barley lectin element or GNA；Pleurotus Ostreatus；Protease inhibitors, such as trypsin inhibitor, serpin, potato storage protein (patatin), cystatin, antipain；Ribosome inactivating protein (RIP), such as ricin, corn-RIP, abrin, Luffin, Saponaria officinalis toxin protein or red bryony toxalbumin；Steroid metabolism enzyme, such as 3- hydroxy steroids oxidizing ferment, ecdysteroid-UDP- glycosyls-transferase, cholesterol oxidase, moulting hormone inhibitor, HMG-COA- reductases, ion channel blocking agent, such as sodium channel or calcium channel blocker, JH esterase, diuretic hormone acceptor, stilbene synthase, bibenzyl synthases, chitinase and dextranase.
Within the scope of the present invention, delta-endotoxin such as CryIA (b), CryIA (c), CryIF, CryIF (a2), CryIIA (b), CryIIIA, CryIIIB (b1) or Cry9c, or vegetative insecticidal proteins (VIP), such as VIP1, VIP2, VIP3 or VIP3A are interpreted as obviously also including mixing toxin, truncate (truncated) toxin and modified toxins.Mixing toxin is (see such as WO02/15701) produced by the Combination nova restructuring in the difference in functionality area of those protein.The CryIA (b) of truncated toxins such as truncation is known.For modified toxins, one or more amino acid of naturally occurring toxin are replaced.In this amino acid replacement, preferably non-naturally occurring protease recognition sequence is inserted in toxin, such as in the case of CryIIIA055, a kind of cathepsin-D- recognition sequences are inserted into CryIIIA toxin (see WO 03/018810).
Above-mentioned toxin or the example for the genetically modified plants that can synthesize above-mentioned toxin are disclosed in such as EP-A-0 374 753, WO 93/07278, WO 95/34656, EP-A-0 427 529, EP-A-451878 and WO 03/052073.
The preparation method of above-mentioned genetically modified plants is generally known to those skilled in the art, is described in for example above-mentioned publication.CryI- types DNA and its preparation are known in such as WO95/34656, EP-A-0 367 474, EP-A-0 401 979 and WO 90/13651.
Contained toxin causes plant to have tolerance to harmful insect in genetically modified plants.The insect may reside in any classification of insect group, but especially be that typically in what is found in beetle (coleoptera), dipteran (Diptera) and butterfly (Lepidoptera).
The genetically modified plants of gene containing one or more coded insect-killing agent resistances and the one or more toxin of expression are known, and some of them are commercially available.The example of the plant is：YieldGard
Figure 2006800183129_19
(corn variety expresses CryIA (b) toxin)；YieldGard Rootworm
Figure 2006800183129_20
(corn variety expresses CryIIIB (b1) toxin)；YieldGard Plus
Figure 2006800183129_21
(corn variety, expression CryIA (b) and CryIIIB (b1) toxin)；Starlink
Figure 2006800183129_22
(corn variety expresses Cry9 (c) toxin)；HerculexI
Figure 2006800183129_23
(the enzyme phosphinothricine N- acetyltransferases (PAT) of corn variety, expression CryIF (a2) toxin and acquisition to herbicide glufosinate ammonium drug resistance)；NuCOTN 33B
Figure 2006800183129_24
(cotton variety expresses CryIA (c) toxin)；Bollgard I
Figure 2006800183129_25
(cotton variety expresses CryIA (c) toxin)；Bollgard II
Figure 2006800183129_26
(cotton variety, expression CryIA (c) and CryIIA (b) toxin)；VIPCOT
Figure 2006800183129_27
(cotton variety, expression VIP toxin)；NewLeaf
Figure 2006800183129_28
(Potato Cultivars, expression CryIIIA toxin)；NatureGard
Figure 2006800183129_29
Agrisure
Figure 2006800183129_30
GT Advantage (GA21 glyphosate tolerants character), Agrisure
Figure 2006800183129_31
CB Advantage (Bt11 corn borers (CB) character) and Protecta
Figure 2006800183129_32
。
Other examples of the genetically modified crops are：
1.Bt11 corns, from Syngenta Seeds SAS, Chemin de l ' Hobit 27, the St.Sauveur of F-31 790, France, registration number C/FR/96/05/10.Genetically altered maize, CryI A (b) toxin truncated by transgene expression makes it to resist the invasion and attack of European corn borer (Ostrinia nubilalis and Sesamia nonagrioides).Bt11 corns also transgene expression PAT enzymes are to obtain the tolerance to herbicide glufosinate ammonium.
2.Bt176 corns, from Syngenta Seeds SAS, Chemin de l ' Hobit27, F-31 790 St.Sauveur, France, registration number C/FR/96/05/10.Genetically altered maize, makes it to resist the invasion and attack of European corn borer (Ostrinia nubilalis and Sesamia nonagrioided) by transgene expression CryIA (b) toxin.Bt176 corns also transgene expression PAT enzymes are to obtain the tolerance to herbicide glufosinate ammonium.
3.MI R604 corns, from the St.Sauveur of Syngenta Seeds SAS, Chemin de l ' Hobit27, F-31 790, France, registration number C/FR/96/05/10.Corn of the CryIIIA toxin being modified by transgene expression with insect-resistant.This toxin is the Cry3A055 by inserting cathepsin-D-protease recognition sequence and modification.The preparation of the transgenic corns is described in WO 03/018810.
The corns of 4.MON 863, from Monsanto Europe S.A.270-272 Avenuede Tervuren, B-1150 Brussels, Belgium, registration number C/DE/02/9.MON 863 expresses CryIIIB (b1) toxin, and resistant to some coleopterons.
The cottons of 5.IPC 531, from Monsanto Europe S.A.270-272 Avenuede Tervuren, B-1150 Brussels, Belgium, registration number C/ES/96/02.
6.1507 corns, from Pioneer Overseas Corporation, AvenueTedesco, 7 B-1160 Brussels, Belgium, registration number C/NL/00/10.Genetically altered corn, marking protein Cry1F is to obtain resistance and PAT protein to some lepidopterous insects to obtain the tolerance to herbicide glufosinate ammonium.
7.NK603 × MON810 corns, from Monsanto Europe S.A.270-272Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/GB/02/M3/03.Hybridized by genetically altered kind NK603 and MON810, be made up of the hybrid corn variety of conventional breeding.The CP4 EPSPS protein that the expression of the corn genes of 603 × MON of NK 810 is obtained by Agrobacterium strains CP4, is allowed to herbicide-resistant Roundup
Figure 2006800183129_33
(containing glyphosate), and CryIA (b) toxin obtained by B. thuringiensis subspecies, it is allowed to resistance to some lepidopterous insects, including European corn borer.
The genetically modified crops of insect-resistant plants are also described in BATS (Zentrum f ü rBiosicherheit und Nachhaltigkeit, Zentrum BATS, Clarastrasse13,4058 Basel, Switzerland) Report 2003, (http://bats.ch)。
Term " crop ", which is interpreted as also including converting by using recombinant DNA technology, to be made it synthesis (PRP s is shown in such as crops of EP-A-0 392 225) with the antipathogen for example so-called " pathogenesis related protein " of selectively acting.The antipathogen and the example for the genetically modified plants that can synthesize the antipathogen are known in such as EP-A-0 392 225, WO95/33818 and EP-A-0 353 191.The manufacture method of the genetically modified plants is generally known to those skilled in the art, and is described in for example above-mentioned publication.
Such as ion channel blocking agent, the blocking agent of such as sodium and calcium channel, such as viral KP1, KP4 or KP6 toxin can be included by the antipathogen of the Expressed in Transgenic Plant；Stilbene synthase；Bibenzyl synthases；Chitinase；Dextranase；So-called " pathogenesis related protein " (PRPs；See that for example EP-A-0 392 is 225)；The albumen or polypeptide factor (so-called " Plant Genes Conferring Resistance To Pathogens ", as described in WO 03/000906) being related in the antipathogen produced by microorganism such as peptide antibiotic or heterocyclic antibiotics (see such as WO 95/33818) or plant pathogen defence.
The other application field of the present composition is protection Stored Product and storeroom; and protect raw material; such as timber, textile, mulching material or building, and health field is additionally operable to, human body, domestic animal and productive livestock is especially protected to resist the insect of the type.
In health field, composition of the invention is effective to ectoparasite such as hardware tick, software tick, itch mite, trombiculid, flies (sting to sting and lick and sting), parasitic screwworm, louse, head louse, bird lice and flea.
The example of this kind of parasite is：
Anoplura (Anoplurida)：Blind pediculus (Haematopinus spp.), Linognathus (Linognathus spp.), Pediculus (Pediculus spp.) and Pthirus (Phtirusspp.), pipe Pediculus (Solenopotes spp.).
Mallophaga stings lice (Mallophagida)：Filoplume Pediculus (Trimenopon spp.), Menopon spp., huge Trichodectes (Trinoton spp.), Bovicola (Bovicolaspp.), Werneckiella spp., Lepikentron spp., Damalinia (Damalinaspp.), Trichodectes (Trichodectes spp.) and Felicola (Felicola spp.).
Diptera (Diptera) and the short beak of Nematocera (Nematocerina) and right angle are as suborder (Brachycerina),Such as Aedes (Aedes spp.),Spot Anopheles (Anophelesspp.),Culex (Culex spp.),Simulium (Simulium spp.),The true buffalo gnat of all woolen (Eusimulium spp.),Sand fly (Phlebotomus spp.),Lutzomyia (Lutzomyiaspp.),Storehouse midge (Culicoides spp.),Spot horsefly (Chrysops spp.),Knurl horsefly (Hybomitra spp.),Atylotus (Atylotus spp.),Gadfly (Tabanus spp.),Chrysozona (Haematopota spp.),Philipomyia spp.,Honeybee Hippobosca (Braulaspp.),Fly belongs to (Musca spp.),Hydrotaea (Hydrotaea spp.),Sting fly (Stomoxys spp.),Haematobia (Haematobia spp.),Fly does not belong to,Latrine fly (Fanniaspp.),Glossina (Glossina spp.),Calliphora (Calliphora spp.),Lucilia (Lucilia spp.),Carysomyia (Chrysomyia spp.),Wohlfahrtia (Wohlfahrtia spp.),Sarcophaga (Sarcophaga spp.),Oestrus (Oestrusspp.),Torsalo (Hypoderma spp.),Gasterophilus (Gasterophilus spp.),Hippoboscid (Hippobosca spp.),Deer Lipoptena (Lipoptena spp.) and Melophagus (Melophagus spp.).
Siphonaptera (Siphonapterida), for example, flea category (Pulex spp.), Ctenocephalus (Ctenocephalides spp.), mouse flea (Xenopsylla spp.), and c. leaf flea (Ceratophyllus spp.).
Heteroptera (Heteropterida), for example, Cimex (Cimex spp.), triatoma sanguisuga category (Triatoma spp.), Rhodnius spp., and Panstrongylus (Panstrongylusspp.).
Blattaria (Blattarida), such as oriental cockroach (Blatta orientalis), American cockroach (Periplaneta americana), Groton bug (Blattelagermanica) and Supella spp..
Mite subclass (Acarida) and metaspiracle mesh (Metastigmata) and mesostigma mesh (Mesostigmata), for example, hidden beak tick belongs to (Argas spp.), beak tick belongs to (Ornithodorusspp.), ear tick (Otobius spp.), hard tick (Ixodes spp.), Amblyomma (Amblyomma spp.), Boophilus (Boophilus spp.), Dermacentor (Dermacentorspp.), Haemolaelaps (Haemophysalis spp.), glass eye tick (Hyalomma spp.), carrapato belongs to (Rhipicephalus spp.), Dermanyssus gallinae (Dermanyssus spp.), auspicious vertical tapeworm (Raillietia spp.), Pneumonyssus (Pneumonyssus spp.), Sternostoma (Sternostoma spp.) and Varroa (Varroa spp.).
Spoke mite suborder (preceding valve suborder (Prostigmata)) and Sarcoptiformes (Acaridida (Astigmata)), such as mite category (Acarapis spp.), Cheyletiella (Cheyletiellaspp.), Ornithocheyletia spp., Myobia, itch mite (Psorergates spp.), compacted mite belongs to (Demodex spp.), sandmite belongs to (Trombicula spp.), rabbit yak mite belongs to (Listrophorus spp.), Tyroglyphus (Acarus spp.), junket mite belongs to (Tyrophagusspp.), thermophilic wooden mite (Caloglyphus spp.), Hypodectes spp., wing clothing mite belongs to (Pterolichus spp.), overworked mite belongs to (Psoroptes spp.), skin Psoroptes (Chorioptes spp.), ear leprosy mite belongs to (Otodectes spp.), Sarcoptesspp (Sarcoptesspp.), scab mite belongs to (Notoedres spp.), lump mite belongs to (Knemidocoptes spp.), Cytodites (Cytodites spp.) and Laminosioptes (Laminosioptes spp.).
The present composition applies also for invasion and attack of the protection materials from insect, for example timber, textile, plastics, adhesive, glue, paint, paper and with plate, leather, mulching material and building.
Therefore, the invention further relates to composition pesticide, as missible oil, suspending agent, can Direct spraying or dilution solution, paintable paste, diluting emulsion, soluble powder, dispersible powder, wettable powder, pulvis, granule or the capsule of polymeric material encapsulating, wherein containing at least one inventive compound, and to dosage form selection to adapt to the target to be applied and main environment.
In these compositions, active component is used in a pure form, for example with the solid active agent of specific particle diameter, or the conven-tional adjuvants preferably with least one preparation in industrial, such as bulking agent, such as solvent or solid carrier, or as surface active cpd (surfactant) is used together.
The example of suitable solvent is：Unhydrogenated or partially hydrogenated aromatic hydrocarbons, preferably C8-C12Alkylbenzene part, such as xylene mixture, alkylated naphthalene or tetrahydronaphthalene, aliphatic or alicyclic hydro carbons, such as alkane or hexamethylene, alcohols, such as ethanol, propyl alcohol or butanol, glycol and its ether and esters, such as propane diols, dipropylene glycol, ethylene glycol or ethylene glycol monomethyl or single ethylether, ketone, such as cyclohexanone, isophorone or diacetone alcohol, intensive polar solvent class, such as N- methyi-pyrrofidiniums -2- ketone, dimethyl sulfoxide or N, dinethylformamide, water, unepoxidized or epoxidised vegetable oil, for example unepoxidized or epoxidised rapeseed oil, castor oil, coconut oil or soybean oil, and silicone oil.
It is usually the natural minerals of crushing for the solid carrier in such as pulvis and dispersible powder, such as calcite, talcum, kaolin, montmorillonite or Attagel.In order to improve its physical property, the silicic acid of polymolecularity or the adsorbability polymer of polymolecularity can also be added.Suitable granulated adsorbent carrier is cellular type, for example float stone, brickbat, sepiolite or bentonite；Suitable non-adsorptive support is calcite or sand.In addition it is possible to use the plant residue of substantial amounts of inorganic or organic particulate material, especially dolomite or crushing.
According to the property of active component to be prepared, suitable surface active cpd is the nonionic with good emulsifiability, dispersive property and wet performance, cation and/or anion surfactant or surfactant mixture.Surfactant listed below should be regarded solely as example；Other surfaces activating agent that many formulation arts are commonly used and suitable for the present invention is described in pertinent literature.
The polyglycol ether derivative of suitable nonionic surfactant particularly aliphatic series or alicyclic alcohol, saturation or unrighted acid or alkyl phenol, described derivative contains about 3 to about 30 ethylene glycol ether groups and has about 8 to about 20 carbon atoms in (ring) aliphatic hydrocarbon moieties, or has about 6 to about 18 carbon atoms in the moieties of alkyl phenol.Other suitable nonionic surfactants are PEO and polypropylene glycol, vinyl diaminourea polypropylene glycol and the water-soluble addition thing of the alkyl polypropylene glycol containing 1 to about 10 carbon atom in alkyl chain, and wherein addition product contains about 20 to about 250 ethylene glycol ether groups and about 10 to about 100 propylene glycol ether groups.Above-claimed cpd usually contains 1 to about 5 ethylene glycol unit/propylene glycol units.The example that can be mentioned that is nonylphenoxy polyethoxy ethanol, castor oil polyglycol ether, PPOX/polyethylene oxide adducts, tributyl phenoxypolyethoxy ethanols, polyethylene glycol and octylphenoxy polyethoxy ethanol.The fatty acid ester of polyoxyethylene sorbitan, such as polyoxyethylene sorbitan trioleate are also suitable nonionic surfactant.
Cationic surfactant particularly quaternary ammonium salt, the quaternary ammonium salt usually contains at least one C as substituent8-C22Alkyl group, and it is used as (non-halo or halo) the low alkyl or low hydroxy alkyl or benzyl group of other substituents.The salt is preferably halide, Methylsulfate or ethyl sulfuric acid salt form.The example is stearyl trimethyl ammonium chloride and benzyl two (2- chloroethyls) ethyl phosphonium bromide ammonium.
The example of suitable anion surfactant is the surface active cpd of water-soluble soaps and water-soluble synthesis.The example of suitable soaps is the sodium salt or sylvite of the alkali metal salt, alkali salt or (be unsubstituted or be substituted) ammonium salt of the aliphatic acid containing about 10 to about 22 carbon atoms, such as oleic acid or stearic sodium salt or sylvite or the natural acid mixture that can be obtained from such as coconut oil or pine tar；It can be mentioned that also have aliphatic acid methyl taurate.However, more generally using the surfactant of synthesis, especially fatty acid sulfonate, fatty acid sulfates, the benzimidizole derivatives or alkylaryl sulfonates of sulfonation.Fatty acid sulfonate and fatty acid sulfates generally exist with alkali metal, alkaline-earth metal or (be unsubstituted or be substituted) ammonium salt; and generally there is the alkyl group containing about 8 to about 22 carbon atoms, alkyl is also understood as including the moieties of carboxyl groups；It can be mentioned that example be lignin sulfonic acid, dodecyl sulphate or the fatty alcohol sulphuric acid admixture obtained by natural acid sodium salt or calcium salt.The salt of salt and fatty alcohol sulfonic acid/ethylene oxide adduct of this group also including sulfuric ester.Sulphonated benzimidazole derivative preferably comprises 2 sulfonyls and 1 fatty acid group containing about 8 to about 22 carbon atoms.The example of alkylaryl sulfonates is DBSA, the sodium salt of dibutyl naphthalenesulfonic acid or naphthalene sulfonic acids/formaldehyde condensation products, calcium salt or tri ethanol ammonium salt.Furthermore, it is also possible to use be suitable phosphate, such as the salt or the salt of phosphatide of the phosphate of p- nonyl phenol/(4-14) ethylene oxide adduct.
Composition usually contains 0.1 to 99%, especially 0.1 to 95% active component and 1 to 99.9%, especially 5 to 99.9% at least one solid or liquid adjuvants, 0 to 25%, preferably 0.1 to 20% (percentage is by weight) of usual composition is probably surfactant.However, composition in a concentrated form is preferred commercially available prod, end user will have significantly lower activity component concentration usually using dilution preparation, the dilution preparation.
It is preferred that composition especially as follows constitute (%=percentage by weights)：
Missible oil
Mixture of active principles：1 to 95%, preferably 5 to 20%
Surfactant：1 to 30%, preferably 10 to 20%
Solvent：5 to 98%, preferably 70 to 85%
Pulvis：
Mixture of active principles：0.1 to 10%, preferably 0.1 to 1%
Solid carrier：99.9 to 90%, preferably 99.9 to 99%
Suspending agent：
Mixture of active principles：5 to 75%, preferably 10 to 50%
Water：94 to 24%, preferably 88 to 30%
Surfactant：1 to 40%, preferably 2 to 30%
Wettable powder：
Mixture of active principles：0.5 to 90%, preferably 1 to 80%
Surfactant：0.5 to 20%, preferably 1 to 15%
Solid carrier：5 to 99%, preferably 15 to 98%
Granule：
Mixture of active principles：0.5 to 30%, preferably 3 to 15%
Solid carrier：99.5 to 70%, preferably 97 to 85%
Composition can also contain other solids or liquid adjuvants, such as stabilizer is for example unepoxidized or epoxidised vegetable oil (such as epoxidised coconut oil, rapeseed oil or soya-bean oil), defoamer such as silicone oil, preservative, viscosity modifier, adhesive and/or tackifier, fertilizer or the other active components for obtaining special-effect, such as bactericide, fungicide, nematicide, plant activator, invertebrate poison or herbicide.
The present composition is prepared in natively known method, in the case of auxiliary agent is lacked, for example prepared by crushing, sieving and/or extrusion solid active component, in the case of there is at least one auxiliary agent, for example, prepared by mixing and/or grinding closely mixture of active principles with auxiliary agent (a variety of auxiliary agents).The purposes that the preparation method and compound I of these compositions prepare these compositions is also subject of the present invention.
The application process of composition, that is the method for the insect of control the above-mentioned type, such as spraying, atomizing, the method dusted, coat, dress seed, broadcast sowing or poured into a mould-according to expected purpose or main environment come selection-and the purposes of insect of composition for preventing and controlling the above-mentioned type be other themes of the invention.Typical concentration rate is 0.1 to 1000ppm, preferably 0.1 to 500ppm active component.The amount of application of per hectare is usually 1 to 2000g active components hectare, especially 10 to 1000g/ha, preferably 10 to 600g/ha.
In crop protection field, preferred application process is the blade (leaf portion administration) for being applied to plant, can select application times and amount of application with being matched by the danger of the pest attacks.Alternatively, plant location can be impregnated with by using fluid composition or mixture of active principles is mixed into plant location in solid form, soil is for example mixed into, for example in granular form (soil application), active component is reached plant by root system (systemic action).For rice crop, the granule can be applied to the rice field of immersion with amount of calculation.
The present composition is also applied to the invasion and attack for protecting plant propagation material from the insect of the above-mentioned type, such as seed material, such as fruit, stem tuber or benevolence, or rice shoot.Propagating materials can be handled with said composition before planting：Seed can be for example handled prior to seeding.Alternatively, benevolence can also be impregnated by using fluid composition or composition is applied to by benevolence (coating) by coating solid composition layer.When planting propagating materials, said composition can also be applied to plantation place, for example, kind of a furrow are applied to during sowing.The processing method of these plant propagation materials and so processed plant propagation material are also subject of the present invention.
Prepare embodiment
Embodiment P1：Prepare 2- (the chloro- pyridine -2- bases of 3-) -5- trifluoromethyl -2H- pyrazoles -3- Carboxylic acid [2- (Bicyclopropyl -1- bases carbamyl) -4- cyano group -6- methylphenyls]-acid amides (A.1.1)：
Figure S2006800183129D00361
To 2- [2- (the chloro- pyridine -2- bases of 3-) -5- trifluoromethyl -2H- pyrazole-3-yls] -8- methyl -4- oxo -4H- benzos [d] [1,3]
Figure 2006800183129_34
Piperazine -6- nitriles (1.2 g, 2, Bicyclopropyl -1- base amine hydrochlorates (0.6g is added in tetrahydrofuran (40ml) solution 8mmol) (prepared according to WO04/067528), 4.2mmol) with 1.2ml (8.4mmol) triethylamine, solution is heated 8 hours at a temperature of 60 DEG C.Solution is cooled to room temperature, evaporation solvent.Then mixture is developed in 100ml water, crystallization is washed with water and ether, obtains 0.85g title compounds.By mother liquid evaporation, second batch crystallization is obtained by being crystallized in diisopropyl ether, 0.46g title compounds (F is obtained：270-272℃).
Embodiment P2：Prepare 2- (the chloro- pyridine -2- bases of 3-) -5- trifluoromethyl -2H- pyrazoles -3- Carboxylic acid [2- (Bicyclopropyl -1- bases carbamyl) -4- cyano group -6- methylphenyls]-acid amides (A.1.1)：
Figure S2006800183129D00371
1.19g (6.25mmol) CuI, 0.30g tetrakis triphenylphosphine palladiums and 2.78g (31.0mmol) CuCN are added into the 50ml tetrahydrofuran solutions of 3.29g (5.23mmol) 2- (the chloro- pyridine -2- bases of 3-) -5- trifluoromethyl -2H- pyrazoles -3- carboxylic acids [2- (Bicyclopropyl -1- bases carbamyl) the iodo- 6- methylphenyls of -4-]-acid amides.Mixture is heated 1 hour at 80 DEG C, becomes bottle green.After cooling, mixture is filtered and evaporated on Hyflo.Residue is dissolved in 15ml DMF, and pours into NaHCO containing 5g3100ml water in.After stirring 30 minutes, filtering for crystallizing is washed with water and hexane/acetone (1: 3) mixture, obtains 2.8g title compounds.
Prepare 2- (the chloro- pyridine -2- bases of 3-) -5- trifluoromethyl -2H- pyrazoles -3- carboxylic acids [2- (Bicyclopropyl -1- bases carbamyl) the iodo- 6- methylphenyls of -4-]-acid amides
Figure S2006800183129D00381
2.08g (3.91mmo l) (2- [2- (the chloro- pyridine -2- bases of 3-) -5- trifluoromethyl -2H- pyrazole-3-yls] iodo- benzos of -8- hydroxyls -6- [d] [1,3]
Figure 2006800183129_35
The mixture of piperazine -4- ketone (being prepared according to WO04/067528), 0.6g (4.50mmo l) Bicyclopropyl -1- bases amine hydrochlorate and 0.63ml (4.50mmol) triethylamines in 20ml THF is heated 20 hours at a reflux temperature.After cooling, filtering precipitation evaporates mother liquor.Residue is dissolved in 5ml DMF and poured into 40ml water.The crystallization of formation is filtered out and purified by flash chromatography (dichloromethane 40, ether 1), 1.85g title compounds are obtained.1H-NMR(CDCl3, 400MHz, ppm)：0.11 (q, 2H), 0.45 (q, 2H), 0.62 (s, 4H), 1.4 (m, 1H), 2.10 (s, 3H), 6.50 (s, 1H), 7.40 (m, 2H), 7.51 (s, 1H), 7.77 (s, 1H), 7.85 (dd, 1H), 8.49 (m, 1H), 10.45 (s, 1H)
Prepare 2- amino-N- Bicyclopropyl -1- base -5- cyano group -3- methyl-benzamides
Figure S2006800183129D00382
The iodo- 8- methyl isophthalic acids H- benzos [d] [1,3] of 600mg (1.98mmol) 6-
Figure 2006800183129_36
Piperazine -2,4- diketone (is prepared according to known methods, see G.M.Coppola, Synthesis, 1980,505), solution of 212mg (2.37mmol) CuCN, 377mg (1.98mmol) CuI the and 114mg tetrakis triphenylphosphine palladiums in 60ml THF is heated 5 hours at a reflux temperature.After cooling, mixture is filtered on Hyflo.Organic phase is washed with water and evaporated.Residue is crystallized from the mixture of dichloromethane, ethyl acetate and hexane, obtains 245mg 8- methyl -2,4- dioxo-Isosorbide-5-Nitrae-dihydro -2H- benzos [d] [1,3]
Figure 2006800183129_37
Piperazine -6- nitriles, the compound can be directly used for next step.
By 236mg (1.16mmol) 8- methyl -2,4- dioxo-Isosorbide-5-Nitrae-dihydro -2H- benzos [d] [1,3]
Figure 2006800183129_38
Piperazine -6- nitriles, 234mg (1.75mmol)Bicyclopropyl -1- base amine hydrochlorates With mixture of 177mg (1.75mmol) triethylamines in 25ml THF in backflow temperature The lower heating of degree 4 hours.Mixture is cooled down and evaporated.In residue dissolving dry ethyl acetate simultaneously Extracted with water.After short distance is isolated and purified on silica gel, 63mg title compounds are isolated, are Yellow crystal.F：171-172℃.
Prepare Bicyclopropyl -1- base amine：
Figure S2006800183129D00391
By 93.2ml (328mmol) Ti (OiPr)4It is added in solution of 20g (298mmol) cyclopropylniitriles in 300ml ether.Then solution is cooled to -78 DEG C, is slowly added to 199ml (596mmol) ethyl phosphonium bromides magnesium solution (3 M are in ether).After 10 minutes, thin pulp is made to warm to room temperature and stir 1 hour at -78 DEG C.Then 84.6g (595mmol) BF is added3.OEt2, mixture is stirred at room temperature 18 hours.At 0 DEG C, 600ml NaOH 2N are slowly added into this mixture.Separate organic phase and extracted with 600ml HCl2 N.Aqueous phase is evaporated, residue is developed in ether, obtains 30.9g title compounds, be hydrochloride.
The following examples, which are intended to illustrate, invents and shows preferred compound of formula I.Me represents methyl.Et represents ethyl.Definition is not provided if instead of base X, then p is 0, if X is substituent, p is 1.Definition is not provided if instead of base A, then q is 0, if A is substituent, q is 1.Substituent Y is C (CH2CH2) when represent the cyclopropyl with two free valence bonds：
Figure S2006800183129D00392
Table A：Formulas I a compounds：
Compound number R91  R93  A  X  Y  B
A.1.1  Me  CF3 - -  C(CH2CH2) Cyclopropyl
A.1.2  Cl  CF3 - -  C(CH2CH2) Cyclopropyl
A.1.3  Br  CF3 - -  C(CH2CH2) Cyclopropyl
A.1.4  Me  Cl - -  C(CH2CH2) Cyclopropyl
A.1.5  Cl  Cl - -  C(CH2CH2) Cyclopropyl
A.1.6  Br  Cl - -  C(CH2CH2) Cyclopropyl
A.1.7  Me  Br - -  C(CH2CH2) Cyclopropyl
A.1.8  Cl  Br - -  C(CH2CH2) Cyclopropyl
A.1.9  Br  Br - -  C(CH2CH2) Cyclopropyl
A.1.10  Me  OCHF2 - -  C(CH2CH2) Cyclopropyl
A.1.11  Cl  OCHF2 - -  C(CH2CH2) Cyclopropyl
A.1.12  Br  OCHF2 - -  C(CH2CH2) Cyclopropyl
A.1.13  Me  OCH2CF3 - -  C(CH2CH2) Cyclopropyl
A.1.14  Cl  OCH2CF3 - -  C(CH2CH2) Cyclopropyl
A.1.15  Br  OCH2CF3 - -  C(CH2CH2) Cyclopropyl
A.1.16  Me  CHF2 - -  C(CH2CH2) Cyclopropyl
A.1.17  Cl  CHF2 - -  C(CH2CH2) Cyclopropyl
A.1.18  Br  CHF2 - -  C(CH2CH2) Cyclopropyl
A.1.19  Me  CH2CF3 - -  C(CH2CH2) Cyclopropyl
A.1.20  Cl  CH2CF3 - -  C(CH2CH2) Cyclopropyl
A.1.21  Br  CH2CF3 - -  C(CH2CH2) Cyclopropyl
A.1.22  Me  CF3 - - CH (cyclopropyl) Cyclopropyl
A.1.23  Me  CF3 - -  C(CH2CH2) Cyclopropyl
A.1.24  Me  CF3 - -  C(CH2CHF) Cyclopropyl
A.1.25  Me  CF3 - -  C(CH2CF2) Cyclopropyl
Compound number R91  R93  A  X  Y  B
A.1.26  Me  CF3 - -  C(CH2CHCl) Cyclopropyl
A.1.27  Me  CF3 - -  C(CH2CFCl) Cyclopropyl
A.1.28  Me  CF3 - -  C(CH2CCl2) Cyclopropyl
A.1.29  Me  CF3 - -  C(CH2CHBr) Cyclopropyl
A.1.30  Me  CF3 - -  C(CH2CBr2) Cyclopropyl
A.1.31  Me  CF3 C(CH2CHMe) -  C(CH2CHMe) Cyclopropyl
A.1.32  Me  CF3 -  C(CH2CMe2) Cyclopropyl
A.1.33  Me  CF3 -  C(CH2CHEt) Cyclopropyl
A.1.34  Me  CF3 -  C(CH2CEt2) Cyclopropyl
A.1.35  Me  CF3 -  C(CH2OCH2) Cyclopropyl
A.1.36  Me  CF3 -  C(CH2S(O)2-CH2 Cyclopropyl
A.1.37  Me  CF3 C(CH2CH2) O  C(CH2CH2) Cyclopropyl
A.1.38  Me  CF3 CH2 CH2  C(CH2CH2) Cyclopropyl
A.1.39  Me  CF3 CH2 O CH- (cyclopropyl) Cyclopropyl
A.1.40  Me  CF3 CH2 O  CH(CH2S-(O)2Me) Cyclopropyl
A.1.41  Me  CF3 CH2 O  CH(CH2O-Me) Cyclopropyl
A.1.42  Me  CF3 CH2 O  C(CH2CH2) Cyclopropyl
A.1.43  Me  CF3 CH2 O  C(CH2CHF) Cyclopropyl
A.1.44  Me  CF3 CH2 O  C(CH2CF2) Cyclopropyl
A.1.45  Me  CF3 CH2 O  C(CH2CHCl) Cyclopropyl
A.1.46  Me  CF3 CH2 O  C(CH2CFCl) Cyclopropyl
A.1.47  Me  CF3 CH2 O  C(CH2CCl2) Cyclopropyl
A.1.48  Me  CF3 CH2 O  C(CH2CHBr) Cyclopropyl
A.1.49  Me  CF3 CH2 O  C(CH2CBr2) Cyclopropyl
A.1.50  Me  CF3 CH2 O  C(CH2CHMe) Cyclopropyl
A.1.51  Me  CF3 CH2 O  C(CH2CMe2) Cyclopropyl
A.1.52  Me  CF3 CH2 O  C(CH2CHEt) Cyclopropyl
A.1.53  Me  CF3 CH2 O  C(CH2C-Et2) Cyclopropyl
A.1.54  Me  CF3 - -  C(CH2CH2) The fluoro- cyclopropyl of 1-
A.1.55  Me  CF3 - -  C(CH2CH2) The chloro- cyclopropyl of 1-
A.1.56  Me  CF3 - -  C(CH2CH2) The bromo- cyclopropyl of 1-
A.1.57  Me  CF3 - -  C(CH2CH2) 1- methyl-cyclopropyls
A.1.58  Me  CF3 - -  C(CH2CH2) 1- ethyl-cyclopropyl bases
A.1.59  Me  CF3 - -  C(CH2CH2) 1- cyano-cyclopropyls
A.1.60  Me  CF3 - -  C(CH2CH2) 1- methyl-thiacyclopropyl
A.1.61  Me  CF3 - -  C(CH2CH2) 1- methoxyl groups-cyclopropyl
Compound number R91  R93  A  X  Y  B
A.1.62  Me  CF3 - -  C(CH2CH2) 1- hydroxy-cyclopropyls
A.1.63  Me  CF3 - -  C(CH2CH2) 1- trifluoromethyls-cyclopropyl
A.1.64  Me  CF3 - -  C(CH2CH2) The fluoro- cyclopropyl of 2-
A.1.65  Me  CF3 - -  C(CH2CH2) 2,2- bis- fluoro- cyclopropyl
A.1.66  Me  CF3 - -  C(CH2CH2) The chloro- cyclopropyl of 2-
A.1.67  Me  CF3 - -  C(CH2CH2) 2,2- bis- chloro- cyclopropyl
A.1.68  Me  CF3 - -  C(CH2CH2) The bromo- cyclopropyl of 2-
A.1.69  Me  CF3 - -  C(CH2CH2) 2,2- bis- bromo- cyclopropyl
A.1.70  Me  CF3 - -  C(CH2CH2) The fluoro- cyclopropyl of the chloro- 2- of 2-
A.1.71  Me  CF3 - -  C(CH2CH2) 2- methyl-cyclopropyls
A.1.72  Me  CF3 - -  C(CH2CH2) 2,2- Dimethyl-cyclopropyls
A.1.73  Me  CF3 - -  C(CH2CH2) 2- ethyl-cyclopropyl bases
A.1.74  Me  CF3 - -  C(CH2CH2) 2,2- diethyl-cyclopropyls
A.1.75  Me  CF3 - -  C(CH2CH2) 2- cyano-cyclopropyls
A.1.76  Me  CF3 - -  C(CH2CH2) 2- methyl-thiacyclopropyl
A.1.77  Me  CF3 - -  C(CH2CH2) 2- methoxyl groups-cyclopropyl
A.1.78  Me  CF3 - -  C(CH2CH2) 2- hydroxy-cyclopropyls
A.1.79  Me  CF3 - -  C(CH2CH2) 2- trifluoromethyls-cyclopropyl
A.1.80  Me  CF3 - -  C(CH2CH2) Cyclobutyl
A.1.81  Me  CF3 - -  C(CH2CH2) The fluoro- cyclobutyl of 2-
A.1.82  Me  CF3 - -  C(CH2CH2) 2,2- bis- fluoro- cyclobutyl
A.1.83  Me  CF3 - -  C(CH2CH2) The chloro- cyclobutyl of 2-
A.1.84  Me  CF3 - -  C(CH2CH2) 2,2- bis- chloro- cyclobutyl
A.1.85  Me  CF3 - -  C(CH2CH2) The bromo- cyclobutyl of 2-
A.1.86  Me  CF3 - -  C(CH2CH2) 2,2- bis- bromo- cyclobutyl
A.1.87  Me  CF3 - -  C(CH2CH2) The fluoro- cyclobutyl of the chloro- 2- of 2-
A.1.88  Me  CF3 - -  C(CH2CH2) 2- methyl-cyclobutyls
A.1.89  Me  CF3 - -  C(CH2CH2) 2,2- dimethyl-cyclobutyls
A.1.90  Me  CF3 - -  C(CH2CH2) 2- ethyl-cyclobutyls
A.1.91  Me  CF3 - -  C(CH2CH2) 2,2- diethyl-cyclobutyl
A.1.92  Me  CF3 - -  C(CH2CH2) 2- cyano group-cyclobutyl
A.1.93  Me  CF3 - -  C(CH2CH2) 2- methyl-thiacyclobutyl group
A.1.94  Me  CF3 - -  C(CH2CH2) 2- methoxyl groups-cyclobutyl
A.1.95  Me  CF3 - -  C(CH2CH2) 2- hydroxy-cyclobutyls
A.1.96  Me  CF3 - -  C(CH2CH2) 2- trifluoromethyls-cyclobutyl
A.1.97  Me  CF3 - -  C(CH2CH2) 3- methyl-cyclobutyls
Compound number  R91  R93  A X  Y  B
A.1.98  Me  CF3 - -  C(CH2CH2) 3,3- dimethyl-cyclobutyls
A.1.99  Me  CF3 - -  C(CH2CH2) The chloro- cyclobutyl of 3-
A.1.100  Me  CF3 - -  C(CH2CH2) 3,3- bis- chloro- cyclobutyl
A.1.101  Me  CF3 - -  C(CH2CH2) CH(CH2O)
A.1.102  Me  CF3 - -  C(CH2CH2) CH(CH-MeO)
A.1.103  Me  CF3 - -  C(CH2CH2) CH(C-Me2O)
A.1.104  Me  CF3 - -  C(CH2CH2) CH(CH2S)
A.1.105  Me  CF3 - -  C(CH2CH2) CH(CH2OCH2)
A.1.106  Me  CF3 - -  C(CH2CH2) CH(CHMeOCH2)
A.1.107  Me  CF3 - -  C(CH2CH2) CH(CMe2OCH2)
A.1.108  Me  CF3 - -  C(CH2CH2) CH(CH2-S(O)2CH2)
A.1.109  Me  CF3 - -  C(CH2CH2) CH(CHMeS(O)2CH2)
A.1.110  Me  CF3 - -  C(CH2CH2) CH(CMe2S(O)2CH2)
A.1.111  Me  CF3 - -  C(CH2CH2) C(Me)-(CH2O)
A.1.112  Me  CF3 - -  C(CH2CH2) C(Me)-(CHMeO)
A.1.113  Me  CF3 - -  C(CH2CH2) C(Me)-(CMe2O)
A.1.114  Me  CF3 - -  C(CH2CH2) C(Me)-(CH2S)
A.1.115  Me  CF3 - -  C(CH2CH2) C(Me)-(CH2OCH2)
A.1.116  Me  CF3 - -  C(CH2CH2) C(Me)-(CHMeO-CH2)
A.1.117  Me  CF3 - -  C(CH2CH2) C(Me)-(C-Me2OCH2)
A.1.118  Me  CF3 - -  C(CH2CH2) C(Me)-(CH2S(O)2CH2)
A.1.119  Me  CF3 - -  C(CH2CH2) C(Me)-(CH-MeS(O)2CH2)
A.1.120  Me  CF3 - -  C(CH2CH2) CMe(C-Me2S(O)2CH2)
A.1.121  Me  CF3 - -  C(CH2CH2) 1- (COOEt)-cyclopropyl
A.1.122  Me  SMe - -  C(CH2CH2) Cyclopropyl
A.1.123  Cl  SMe - -  C(CH2CH2) Cyclopropyl
A.1.124  Br  SMe - -  C(CH2CH2) Cyclopropyl
A.1.125  Me  SOMe - -  C(CH2CH2) Cyclopropyl
A.1.126  Cl  SOMe - -  C(CH2CH2) Cyclopropyl
A.1.127  Br  SOMe - -  C(CH2CH2) Cyclopropyl
A.1.128  Me  SO2Me - -  C(CH2CH2) Cyclopropyl
A.1.129  Cl  SO2Me - -  C(CH2CH2) Cyclopropyl
A.1.130  Br  SO2Me - -  C(CH2CH2) Cyclopropyl
A.1.131  Me  OCF2-  CFHCF3 - -  C(CH2CH2) Cyclopropyl
A.1.132  Cl  OCF2-  CFHCF3 - -  C(CH2CH2) Cyclopropyl
Compound number R91  R93  A  X  Y  B
A.1.133  Br  OCF2-  CFHCF3 - -  C(CH2CH2) Cyclopropyl
A.1.134  Me  OCH2CF2CF3 - -  C(CH2CH2) Cyclopropyl
A.1.135  Cl  OCH2CF2CF3 - -  C(CH2CH2) Cyclopropyl
A.1.136  Br  OCH2CF2CF3 - -  C(CH2CH2) Cyclopropyl
Table B：Formulas I b compounds：
Figure S2006800183129D00441
Compound Numbering  R91  R93  R94  A  X  Y  B
B.1.1  Me  CF3  Br - -  C(CH2CH2) Cyclopropyl
B.1.2  Cl  CF3  Br - -  C(CH2CH2) Cyclopropyl
B.1.3  Br  CF3  Br - -  C(CH2CH2) Cyclopropyl
B.1.4  Me  Cl  Br - -  C(CH2CH2) Cyclopropyl
B.1.5  Cl  Cl  Br - -  C(CH2CH2) Cyclopropyl
B.1.6  Br  Cl  Br - -  C(CH2CH2) Cyclopropyl
B.1.7  Me  Br  Br - -  C(CH2CH2) Cyclopropyl
B.1.8  Cl  Br  Br - -  C(CH2CH2) Cyclopropyl
B.1.9  Br  Br  Br - -  C(CH2CH2) Cyclopropyl
B.1.10  Me  CF3  Cl - -  C(CH2CH2) Cyclopropyl
B.1.11  Cl  CF3  Cl - -  C(CH2CH2) Cyclopropyl
B.1.12  Br  CF3  Cl - -  C(CH2CH2) Cyclopropyl
B.1.13  Me  Cl  Cl - -  C(CH2CH2) Cyclopropyl
B.1.14  Cl  Cl  Cl - -  C(CH2CH2) Cyclopropyl
B.1.15  Br  Cl  Cl - -  C(CH2CH2) Cyclopropyl
B.1.16  Me  Br  Cl - -  C(CH2CH2) Cyclopropyl
Compound Numbering  R91  R93  R94  A  X  Y  B
B.1.17  Cl  Br Cl - -  C(CH2CH2) Cyclopropyl
B.1.18  Br  Br Cl - -  C(CH2CH2) Cyclopropyl
B.1.19  Me  CF3 Me - -  C(CH2CH2) Cyclopropyl
B.1.20  Cl  CF3 Me - -  C(CH2CH2) Cyclopropyl
B.1.21  Br  CF3 Me - -  C(CH2CH2) Cyclopropyl
B.1.22  Me  Cl Me - -  C(CH2CH2) Cyclopropyl
B.1.23  Cl  Cl Me - -  C(CH2CH2) Cyclopropyl
B.1.24  Br  Cl Me - -  C(CH2CH2) Cyclopropyl
B.1.25  Me  Br Me - -  C(CH2CH2) Cyclopropyl
B.1.26  Cl  Br Me - -  C(CH2CH2) Cyclopropyl
B.1.27  Br  Br Me - -  C(CH2CH2) Cyclopropyl
B.1.28  Me  OCH2CF3 Br - -  C(CH2CH2) Cyclopropyl
B.1.29  Cl  OCH2CF3 Br - -  C(CH2CH2) Cyclopropyl
B.1.30  Br  OCH2CF3 Br - -  C(CH2CH2) Cyclopropyl
B.1.31  Me  OCH2CF3 Cl - -  C(CH2CH2) Cyclopropyl
B.1.32  Cl  OCH2CF3 Cl - -  C(CH2CH2) Cyclopropyl
B.1.33  Br  OCH2CF3 Cl - -  C(CH2CH2) Cyclopropyl
B.1.34  Me  OCH2CF3 Me - -  C(CH2CH2) Cyclopropyl
B.1.35  Cl  OCH2CF3 Me - -  C(CH2CH2) Cyclopropyl
B.1.36  Br  OCH2CF3 Me - -  C(CH2CH2) Cyclopropyl
Table C：The physical data of Table A and B compound：
Compound number Fusing point [DEG C]
 A.1.1  270-272
 A.1.13  175-178
 A.1.4  249-255
 A.1.7  254-260
 B.1.28  169-174
 A.1.122  243-244
 A.1.131  170-172
Compound number Fusing point [DEG C]
 A.1.134  200-205
 A.1.16  250-251
 A.1.72  158-160
 A.1.57  247-249
Table D：Formula V a compounds：
Figure S2006800183129D00461
Compound number  R91   Y   B Fusing point   [℃]
  D1   Me   C(CH2CH2) Cyclopropyl   171-172
  D2   Me CH (cyclopropyl) Cyclopropyl
  D3   Me   C(CH2CHF) Cyclopropyl
  D4   Me   C(CH2CF2) Cyclopropyl
  D4   Me   C(CH2CHCl) Cyclopropyl
  D6   Me   C(CH2CFCl) Cyclopropyl
  D7   Me   C(CH2CCl2) Cyclopropyl
  D8   Me   C(CH2CHBr) Cyclopropyl
  D9   Me   C(CH2CBr2) Cyclopropyl
  D11   Me   C(CH2CMe2) Cyclopropyl
  D12   Me   C(CH2CHEt) Cyclopropyl
  D13   Me   C(CH2CEt2) Cyclopropyl
  D14   Me   C(CH2OCH2) Cyclopropyl
  D15   Me   C(CH2S(O)2-CH2 Cyclopropyl
  D16   Me   C(CH2CH2) The fluoro- cyclopropyl of 1-
  D17   Me   C(CH2CH2) The chloro- cyclopropyl of 1-
  D18   Me   C(CH2CH2) The bromo- cyclopropyl of 1-
  D19   Me   C(CH2CH2) 1- methyl -- cyclopropyl
  D20   Me   C(CH2CH2) 1- ethyl-cyclopropyl bases
  D21   Me   C(CH2CH2) 1- cyano-cyclopropyls
  D22   Me   C(CH2CH2) 1- methyl -- thiacyclopropyl
Compound number R91  Y  B Fusing point [℃]
D23  Me  C(CH2CH2) 1- methoxyl groups-cyclopropyl
D24  Me  C(CH2CH2) 1- hydroxy-cyclopropyls
D25  Me  C(CH2CH2) 1- trifluoromethyls-cyclopropyl
D26  Me  C(CH2CH2) The fluoro- cyclopropyl of 2-
D27  Me  C(CH2CH2) 2,2- bis- fluoro- cyclopropyl
D28  Me  C(CH2CH2) The chloro- cyclopropyl of 2-
D29  Me  C(CH2CH2) 2,2- bis- chloro- cyclopropyl
D30  Me  C(CH2CH2) The bromo- cyclopropyl of 2-
D31  Me  C(CH2CH2) 2,2- bis- bromo- cyclopropyl
D32  Me  C(CH2CH2) The fluoro- cyclopropyl of the chloro- 2- of 2-
D33  Me  C(CH2CH2) 2- methyl-cyclopropyls
D34  Me  C(CH2CH2) 2,2- Dimethyl-cyclopropyls
D35  Me  C(CH2CH2) 2- ethyl-cyclopropyl bases
D36  Me  C(CH2CH2) 2,2- diethyl-cyclopropyls
D37  Me  C(CH2CH2) 2- cyano-cyclopropyls
D38  Me  C(CH2CH2) 2- methyl-thiacyclopropyl
D39  Me  C(CH2CH2) 2- methoxyl groups-cyclopropyl
D40  Me  C(CH2CH2) 2- hydroxy-cyclopropyls
D41  Me  C(CH2CH2) 2- trifluoromethyls -- cyclopropyl
D42  Me  C(CH2CH2) Cyclobutyl
D43  Me  C(CH2CH2) The fluoro- cyclobutyl of 2-
D44  Me  C(CH2CH2) 2,2- bis- fluoro- cyclobutyl
D45  Me  C(CH2CH2) The chloro- cyclobutyl of 2-
D46  Me  C(CH2CH2) 2,2- bis- chloro- cyclobutyl
D47  Me  C(CH2CH2) The bromo- cyclobutyl of 2-
D48  Me  C(CH2CH2) 2,2- bis- bromo- cyclobutyl
D49  Me  C(CH2CH2) The fluoro- cyclobutyl of the chloro- 2- of 2-
D50  Me  C(CH2CH2) 2- methyl-cyclobutyls
D51  Me  C(CH2CH2) 2,2- dimethyl -- cyclobutyl
D52  Me  C(CH2CH2) 2- ethyl-cyclobutyls
D53  Me  C(CH2CH2) 2,2- diethyl-cyclobutyl
D54  Me  C(CH2CH2) 2- cyano group-cyclobutyl
D55  Me  C(CH2CH2) 2- methyl-thiacyclobutyl group
D56  Me  C(CH2CH2) 2- methoxyl groups-cyclobutyl
D57  Me  C(CH2CH2) 2- hydroxy-cyclobutyls
Compound number R91  Y  B Fusing point [℃]
D58  Me  C(CH2CH2) 2- trifluoromethyls-cyclobutyl
D59  Me  C(CH2CH2) 3- methyl-cyclobutyls
D60  Me  C(CH2CH2) 3,3- dimethyl -- cyclobutyl
D61  Me  C(CH2CH2) The chloro- cyclobutyl of 3-
D62  Me  C(CH2CH2) 3,3- bis- chloro- cyclobutyl
D63  Me  C(CH2CH2) CH(CH2O)
D64  Me  C(CH2CH2) CH(CH-MeO)
D65  Me  C(CH2CH2) CH(C-Me2O)
D66  Me  C(CH2CH2) CH(CH2S)
D67  Me  C(CH2CH2) CH(CH2OCH2)
D68  Me  C(CH2CH2) CH(CHMeOCH2)
D69  Me  C(CH2CH2) CH(CMe2OCH2)
D70  Me  C(CH2CH2) CH(CH2-S(O)2CH2)
D71  Me  C(CH2CH2) CH(CHMeS(O)2CH2)
D72  Me  C(CH2CH2) CH(CMe2S(O)2CH2)
D73  Me  C(CH2CH2) C(Me)-(CH2O)
D74  Me  C(CH2CH2) C(Me)-(CHMeO)
D75  Me  C(CH2CH2) C(Me)-(CMe2O)
D76  Me  C(CH2CH2) C(Me)-(CH2S)
D77  Me  C(CH2CH2) C(Me)-(CH2OCH2)
D78  Me  C(CH2CH2) C(Me)-(CHMeO-CH2)
D79  Me  C(CH2CH2) C(Me)-(C-Me2OCH2)
D80  Me  C(CH2CH2) C(Me)-(CH2S(O)2CH2)
D81  Me  C(CH2CH2) C(Me)-(CH-MeS(O)2CH2)
D82  Me  C(CH2CH2) CMe(C-Me2S(O)2CH2)
D83  Me  C(CH2CH2) 1- (COOEt)-cyclopropyl
D84  Cl  C(CH2CH2) Cyclopropyl
D85  Br  C(CH2CH2) Cyclopropyl
D86  Cl  C(CH2CH2) 1- methyl-cyclopropyls
D87  Br  C(CH2CH2) 1- methyl-cyclopropyls
D88  Cl  C(CH2CH2) 2,2- Dimethyl-cyclopropyls
D89  Br  C(CH2CH2) 2,2- Dimethyl-cyclopropyls
Example of formulations(%=percentage by weights)
Embodiment F1：Missible oil                    a)        b)       c)
Active component 25% 40% 50%
Calcium dodecyl benzene sulfonate 5% 8% 6%
Castor oil polyglycol ether (36 moles of EO) 5%--
Tributyl phenoxy group polyglycol ether (30 moles of EO) -12% 4%
Cyclohexanone -15% 20%
Xylene mixture 65% 25% 20%
Thus any emulsion for wishing concentration can be made by concentrate by being diluted with water.
Embodiment F2：Solution            a)    b)    c)    d)
Active component 80% 10% 5% 95%
Glycol monoethyl ether 20%---
Polyethylene glycol MW 400-70%--
NMP -20%--
Epoxidised coconut oil--1% 5%
Petroleum ether (boiling range：160-190 °)--94% -
The solution is adapted to use with droplet form.
Embodiment F 3：Granule         a)    b)    c)    d)
Active component 5% 10% 8% 21%
Kaolin 94% -79% 54%
Aerosil 200 1% -13% 7%
Attagel -90% -18%
Active component is dissolved in dichloromethane, solution is sprayed onto on carrier, subsequent vacuum evaporating solvent.
Embodiment F4：Pulvis      a)     b)
Active component 2% 5%
Aerosil 200 1% 5%
Talcum 97%-
Kaolin -90%
It is by the way that carrier and active component are closely mixed into acquisition i.e. with pulvis.
Embodiment F5：Wettable powder    a)      b)      c)
Active component 25% 50% 75%
Sodium lignin sulfonate 5% 5%-
NaLS 3% -5%
Diisobutyl sodium naphthalene sulfonate -6% 10%
Octylphenoxy polyglycol ether
(7-8 moles of EO) -2% -
Aerosil 200 5% 10% 10%
Kaolin 62% 27%-
Active component is mixed with additive, mixture is fully ground in suitable mill.Wettable powder is thus produced, is diluted with water and produces any suspension for wishing concentration.
Embodiment F6：Extrude granule
Active component 10%
Sodium lignin sulfonate 2%
Carboxymethyl cellulose 1%
Kaolin 87%
Active component is mixed with additive, and mixture is ground, is soaked with water, extrudes and dries in the air stream.
Embodiment F7：Coated particle agent
Active component 3%
Polyethylene glycol (MW 200) 3%
Kaolin 94%
In a mixer, by the active component even spread of fine lapping to the kaolin soaked with polyethylene glycol.The dustless coated particle agent thus produced.
Embodiment F8：Colloidal suspending agent
Active component 40%
Ethylene glycol 10%
Nonylphenoxy polyglycol ether (15 moles of EO) 6%
Sodium lignin sulfonate 10%
Carboxymethyl cellulose 1%
37% formalin 0.2%
Silicone oil (75% aqueous emulsion) 0.8%
Water 32%
The active component of fine lapping is closely mixed with additive.Any suspension for wishing concentration can be prepared by the way that so obtained colloidal suspending agent is diluted with water.
The activity of the present composition can significantly be widened by adding other desinsections, mite killing and/or Fungicidal active ingredient and main environment is adapted it to.The active component suitably added herein is the representative of the active component of for example following classification：Organic phosphorus compound, nitrophenol derivative, Thiourea; juvenile hormone, formamidine, benzophenone; ureas, azole derivatives, carbamates; pyrethroid; chlorinated hydrocarbon, acyl group ureas, pyridylmethylene amino derivative; macrolides, anabasine (neonicotinoids) and sporeine preparation.
The following mixture of compound of formula I and other active components is preferred (abbreviation " TX " expression " compound in the compound group specifically described in a kind of Table A and B selected from the present invention ")：
Auxiliary agent+TX selected from oil (petroleum, alias) (628),
It is selected from the group the acaricide of material：1,1- bis- (4- chlorphenyls)-cellosolvo (I UPAC titles) (910)+TX,2,4- dichlorophenyls benzene sulfonate (IUPAC/ chemical abstracts name) (1 059)+TX,The fluoro- N- methyl-N-1- NADs of 2- (IUPAC titles) (1295)+TX,4- chlorophenyl phenyl sulfones (IUPAC titles) (981)+TX,AVM (1)+TX,Acequinocyl (3)+TX,Acetyl worm nitrile [CCN]+TX,Acrinathrin (9)+TX,Aldicarb (16)+TX,Aldoxycarb (863)+TX,α-cypermethrin (202)+TX,Amidithion (870)+TX,amidoflumet[CCN]+TX,amidothioate(872)+TX,Citram (875)+TX,Citram binoxalate (875)+TX,Amitraz (24)+TX,Aramite (881)+TX,Arsenic trioxide (882)+TX,AVI 382 (compound code)+TX,AZ 60541 (compound code)+TX,Azinphos ethyl (44)+TX,Azinphos-methyl (45)+TX,Azobenzene (IUPAC titles) (888)+TX,Azacyclotin (46)+TX,Alamos (889)+TX,Benomyl (62)+TX,Benoxafos (alias) [CCN]+TX,Citrazon (71)+TX,Ergol (I UPAC titles) [CCN]+TX,Bifenazate (74)+TX,Bifenthrin (76)+TX,Binapacryl (907)+TX,Brofenxalerate (alias)+TX,Bromocyclne (918)+TX,Bromophos (920)+TX,Rilariol (921)+TX,Fenisobromolate (94)+TX,Buprofezin (99)+TX,Butocarboxim (103)+TX,Butanone sulfone prestige (104)+TX,Butylpyridaben (alias)+TX,Lime sulfur (IUPAC titles) (111)+TX,Toxaphene (941)+TX,Sok (943)+TX,Carbaryl (115)+TX,Carbofuran (118)+TX,Carbophenothion (947)+TX,CGA 50 ' 439 (research code) (125)+TX,Chinomethionat (126)+TX,Neotran (959)+TX,Spanon (964)+TX,Chlordimeform-hydrochloride (964)+TX,Chlorfenapyr (130)+TX,Qikron (968)+TX,Chlorfenizon (970)+TX,Chlorfensulphide (971)+TX,Chlorfenviphos (131)+TX,Chlorobenzilate (975)+TX,Yi Tuoming (977)+TX,Chloromethiuron (978)+TX,Acaralate (983)+TX,Chlopyrifos (145)+TX,Chlorpyrifos-methyl (146)+TX,Actellic (994)+TX,Cinerin (696)+TX,Cinerin I (696)+TX,II cinerin II (696)+TX,Clofentezine (158)+TX,Closantel (alias) [CCN]+TX,Resistox (174)+TX,Crotonocyl toluidines (alias) [CCN]+TX,Crotoxyphos (1010)+TX,Cufraneb (1013)+TX,Cyanthoate (1020)+TX,CyFLumetofen (CAS registration numbers：400882-07-7)+TX,Lambda-cyhalothrin (196)+TX,Plictran (199)+TX,Cypermethrin (201)+TX,DCPM(1032)+TX,DDT(219)+TX,Demephion (1037)+TX,Demephion-O (1037)+TX,Demephion-S (1037)+TX,Demeton (1038)+TX,Demeton-methyl (224)+TX,Demeton-O (1038)+TX,Demeton-methyl-O (224)+TX,Demeton-S (1038)+TX,Demeton-methyl-S (224)+TX,Metilomerkaptofosoksid-S (1039)+TX,Diafenthiuron (226)+TX,Dialifos (1042)+TX,Diazinon (227)+TX,Dichlofluanid (230)+TX,DDVP (236)+TX,Dicliphos (alias)+TX,Dicofol (242)+TX,Carbicron (243)+TX,Gram (1071)+TX everywhere,BFPO (1081)+TX,Rogor (262)+TX,Diformazan polynactin (alias) (653)+TX,Dinitrocyclohexylphenol (1089)+TX,Dinitrocyclohexylphenol (dinex-diclexine) (1089)+TX,Dinobuton (269)+TX,Dinocap (270)+TX,Dinocap -4 [CCN]+TX,Dinocap -6 [CCN]+TX,Dinitro ester (109O)+TX,Dinopenton (1092)+TX,Nitre monooctyl ester (1097)+TX,Dinoterbon (1098)+TX,EnemyPhosphorus (1102)+TX,Diphenyl sulphone (DPS) (IUPAC titles) (1103)+TX,Abstinyl (alias) [CCN]+TX,Disulfoton (278)+TX,DNOC(282)+TX,Benzene oxycetylene mite (1113)+TX,Doractin (alias) [CCN]+TX,5a,6,9,9a-hexahydro-6,9-methano-2,4 (294)+TX,Endothion (1121)+TX,EPN(297)+TX,According to general rhzomorph (alias) [CCN]+TX,Ethodan (309)+TX,Ethoate methyl (1134)+TX,Etoxazole (320)+TX,Etrimfos (1142)+TX,Fenazaflor (1147)+TX,Fenazaquin (328)+TX,Fenbutatin oxide (330)+TX,Fenothiocarb (337)+TX,Fenpropathrin (342)+TX,Tebufenpyrad (alias)+TX,Fenpyroximate (345)+TX,Fenson (1157)+TX,Fluorine nitre diphenylamines (1161)+TX,Fenvalerate (349)+TX,Ethiprole (354)+TX,Fluacrypyrim (360)+TX,Fluazuron (1166)+TX,Fluorine mite thiophene (1167)+TX,Flucycloxuron (366)+TX,Flucythrinate (367)+TX,Fluenyl (1169)+TX,Flufenoxuron (370)+TX,Flumethrin (372)+TX,Fluoraracide (1174)+TX,Taufluvalinate (1184)+TX,FMC 1137 (research code) (1185)+TX,Carzol (405)+TX,Carzol SP (405)+TX,Formothion (1192)+TX,Amine first prestige (1193)+TX,γ-HCH(430)+TX,Glyodin (1205)+TX,Halfenprox (424)+TX,Heptene ether (432)+TX,Hexadecane basic ring carboxylate (IUPAC/ chemical abstracts name) (1216)+TX,Hexythiazox (441)+TX,Iodomethane (IUPAC titles) (542)+TX,Isocarbophos (alias) (473)+TX,Isopropyl O- (Methoxyamino thiophosphoryl) salicylate (IUPAC titles) (473)+TX,Olivomitecidin (alias) [CCN]+TX,Jasmolin I (696)+TX,Jasmolin ii (696)+TX,Iodfenphos (1248)+TX,Lindane (430)+TX,Lufenuron (490)+TX,Malathion (492)+TX,Benzyl malononitrile (1254)+TX,Afos (502)+TX,Mephosfolan (1261)+TX,Mesulfen (alias) [CCN]+TX,Methacrifos (1266)+TX,Acephatemet (527)+TX,Methidathion (529)+TX,Methiocarb (530)+TX,Methomyl (531)+TX,Bromomethane (537)+TX,MTMC (550)+TX,Menite (556)+TX,Mexacarbate (1290)+TX,Milbemectin (557)+TX,Polynactin oxime (alias) [CCN]+TX,Mipafox (1293)+TX,Azodrin (561)+TX,Morphothion (1300)+TX,Moxidectin (alias) [CCN]+TX,2-dichloroethylk dimethyl phosphate (567)+TX,NC-184 (compound code)+TX,NC-512 (compound code)+TX,Fluorine mosquito spirit (1 309)+TX,Nikkomycin (alias) [CCN]+TX,Nitrilacarb (1313)+TX,The zinc chloride complex compound of nitrilacarb 1: 1 (1313)+TX,NNI-0101 (compound code)+TX,NNI-0250 (compound code)+TX,Omethoate (594)+TX,Oxamyl (602)+TX,Sub- Thiometan (1 324)+TX,Disystom-s (1 325)+TX,pp′-DDT(219)+TX,Parathion (615)+TX,Permethrin (626)+TX,Oil (alias) (628)+TX,Phenkapton (1330)+TX,Phenthoate dimephenthoate cidial (631)+TX,Thimet (636)+TX,Phosalone (637)+TX,Phosfolan (1338)+TX,Phosmet (638)+TX,Phosphamidon (639)+TX,Phoxim (642)+TX,Pirimiphos-methyl (652)+TX,Citicide (traditional title) (1347)+TX,Polynactin (alias) (653)+TX,Go out mite alcohol (1350)+TX,Profenofos (662)+TX,Promacyl (1354)+TX,Propargite (671)+TX,Propetamphos (673)+TX,Arprocarb (678)+TX,Prothidathion (1360)+TX,Prothoate (1362)+TX,Pyrethrins I (696)+TX,Pyrethrins I I (696)+TX,Pyrethrin (696)+TX,Pyridaben (699)+TX,Pyridaphethione (701)+TX,Pyrimidifen (706)+TX,Diothyl (1370)+TX,Quinalphos (711)+TX,Quinoline tears good fortune (1381)+TX,R-1492 (research code) (1382)+TX,RA-17 (research code) (1383)+TX,Rotenone (722)+TX,Schradane (1389)+TX,Cadusafos (alias)+TX,Selamectin (alias) [CCN]+TX,SI-0009 (compound code)+TX,Sophamide (1402)+TX,Envidor (738)+TX,Spiromesifen (739)+TX,SSI-121 (research code) (1404)+TX,Sulfiram (alias) [CCN]+TX,Sulfluramid (7 5 0)+TX,Sulfotep (753)+TX,Sulfur (754)+TX,SZI-121 (research code) (757)+TX,τ-taufluvalinate (398)+TX,Tebufenpyrad (763)+TX,TEPP(1417)+TX,Terbam (alias)+TX,Ravap (777)+TX,Tetradiphon (786)+TX,Polynactin (alias) (653)+TX,Mite killing thioether (1425)+TX,Thiafenox (alias)+TX,Talcord (1431)+TX,Thiofanox (800)+TX,Thiometon (801)+TX,Eradex (1436)+TX,Su Li rhzomorphs (alias) [CCN]+TX,Triamiphos (1441)+TX,Benzene thiophene mite (1443)+TX,Hostathion (820)+TX,Triazuron (alias)+TX,Metrifonate (824)+TX,The phosphorus of chlorobenzene second third (1455)+TX,- first polynactin (alias) (653)+TX,Vamidothion (847)+TX,Fluorine pyrazoles worm [CCN] and YI-5302 (compound code)+TX,
The algicide being selected from the group：Bethoxazin [CCN]+TX, two cupric octoates (IUPAC titles) (170)+TX, copper sulphate (172)+TX, cybutryne [CCN]+TX, dihydro naphthoquinones (1052)+TX, double hydrogen phenol (232)+TX, bacterium polyacid (295)+TX, fentin (347)+TX, white lime [CCN]+TX, Dithane A40 (566)+TX, quinoclamine (714)+TX, quinone duckweed amine (1379)+TX, Simanex (730)+TX, fentin acetate (IUPAC titles) (347) and fentin hydrochloride (IUPAC titles) (347)+TX,
The anthelmintic being selected from the group：AVM (1)+TX, Ruelene (1011)+TX, doractin (alias) [CCN]+TX, emaricin (291)+TX, emaricin benzoic ether (291)+TX, according to general rhzomorph (alias) [CCN]+TX, Olivomitecidin (alias) [CCN]+TX, polynactin oxime (alias) [CCN]+TX, moxidectin (alias) [CCN]+TX, piperazine [CCN]+TX, selamectin (alias) [CCN]+TX, pleocidin (737) and thiophanate (1435)+TX
The avicide being selected from the group：Chloralose (127)+TX, endrin (1122)+TX, Entex (346)+TX, pyridine -4- amine (IUPAC titles) (23) and strychnine (745)+TX,
The bactericide being selected from the group：1- hydroxyls -1H- pyridine -2- thioketones (IUPAC titles) (1222)+TX, 4- (quinoxaline -2- bases amino) benzsulfamide (IUPAC titles) (748)+TX, 8-hydroxyquinoline sulfate (446)+TX, bronopol (97)+TX, two cupric octoates (IUPAC titles) (170)+TX, Kocide SD (IUPAC titles) (169)+TX, cresols [CCN]+TX, double hydrogen phenol (232)+TX, pyrrole bacterium sulphur (1105)+TX, many enemy bacterium (1112)+TX, fenaminosulf (1144)+TX, formaldehyde (404)+TX, conotrane (alias) [CCN]+TX, kasugarnycin (483)+TX, kasugamycin hydrochloride hydrate (483)+TX, two (dimethyl dithiocarbamate) nickel (IUPAC titles) (1308)+TX, trichloromethyl pyridine (580)+TX, octhilinone (590)+TX, oxolinic acide (606)+TX, terramycin (611)+TX, oxyquinoline potassium sulfate (446)+TX, probenazole (658)+TX, streptomysin (744)+TX, streptomysin sesquisulfate (744)+TX, tecloftalam (766)+TX and merthiolate (alias) [CCN]+TX,
The biological reagent being selected from the group：Adoxophyes moth PuGV (alias) (12)+TX,Jia Teluo (alias) (13)+TX,Predatory Mites (alias) (19)+TX,Celery looper nucleopolyhedrosis virus (alias) (28)+TX,Anagrus atomus (alias) (29)+TX,Aphid parasitic wasp (alias) (33)+TX,Cotten aphid parasitic wasp (alias) (34)+TX,Eat aphid cecidomyiia (alias) (35)+TX,Autographa californica nuclear polyhedrosis virus (alias) (38)+TX,Bacillus firmus (alias) (48)+TX,Bacillus sphaericus (scientific name) (49)+TX,Dipel (scientific name) (51)+TX,Dipel a. (scientific name) (51)+TX,Dipel I. (scientific name) (51)+TX,Dipel Japan subspecies (scientific name) (51)+TX,Dipel k. (scientific name) (51)+TX,Dipel t. (scientific name) (51)+TX,Beauveria bassiana (alias) (53)+TX,Muscardine (alias) (54)+TX,Lacewing (alias) (151)+TX,Cryptolaemus montrouzieri (alias) (178)+TX,Carpocapsa pomonella granulosis virus (alias) (191)+TX,Dacnusa sibirica (alias) (212)+TX,Diglyphus isaea (alias) (254)+TX,Encarsia formosa (scientific name) (293)+TX,Eretmocerus SP (alias) (300)+TX,Corn earworm nucleopolyhedrosis virus (alias) (431)+TX,Heterorhabditis bacteriophora-NJ and H.megidis (alias) (433)+TX,Assemble considerable ladybug (alias) (442)+TX,Tangerine powder scale insect parasitic wasp (alias) (488)+TX,Fleahopper (alias) (491)+TX,Lopper worm nucleopolyhedrosis virus (alias) (494)+TX,Metaphycus helvolus (alias) (522)+TX,Yellowish green green muscardine fungus (scientific name) (523)+TX,Metarhizium anisopliae var. Anisopliae (scientific name) (523)+TX,Neodiprion sertifer nucleopolyhedrosis virus and reddish tone pine bark procyanidins nucleopolyhedrosis virus (alias) (575)+TX,Minute pirate bugs (alias) (596)+TX,Paecilomyces fumosoroseus (alias) (613)+TX,Plant mite (alias) (644)+TX catches in Chile,Many nucleocapsid nucleopolyhedrosis virus (scientific name) (the 741)+TX of beet armyworm,March fly nematode (alias) (742)+TX,Nematode Steinernema carpocapsae (alias) (742)+TX,Steinernema feltiae (alias) (742)+TX,Steinernema glaseri (alias) (742)+TX,Steinernema riobrave (alias) (742)+TX,Steinernemariobravis (alias) (742)+TX,Steinernema scapterisci (alias) (742)+TX,Steinernema Carpocapsae (alias) (742)+TX,Trichogramma (alias) (826)+TX,West it is blind walk mite (alias) (844) and Verticillium lecanii (alias) (848)+TX,
The soil sterilants being selected from the group：Iodomethane (IUPAC titles) (542) and bromomethane (537)+TX,
The chemosterilants being selected from the group：Apholate [CCN]+TX, bisazir (alias) [CCN]+TX, sulphur butane (alias) [CCN]+TX, diflubenzuron (250)+TX, dimatif (alias) [CCN]+TX, hemel [CCN]+TX, hempa [CCN]+TX, metepa [CCN]+TX, Metapside [CCN]+TX, aphamide piperazine [CCN]+TX, infertile pyridine [CCN]+TX, penfluron (alias) [CCN]+TX, tepa [CCN]+TX, thio hempa (alias) [CCN]+TX, thio-tepa (alias) [CCN]+TX, tretamine (alias) [CCN] and uredepa (alias) [CCN]+TX,
It is selected from the group the insect pheromone of material：(E)-decyl- 5- alkene -1- yl acetates (IUPAC titles) (222)+TX with (E)-decyl- 5- alkene -1- alcohol,(E)-ten three -4- alkene -1- yl acetates (IUPAC titles) (829)+TX,(E) -6- methyl hept-2-ene" -4- alcohol (IUPAC titles) (541)+TX,(E+TX,Z)-ten four -4+TX,10- diene -1- yl acetates (IUPAC titles) (779)+TX,(Z)-ten two -7- alkene -1- yl acetates (IUPAC titles) (285)+TX,(Z)-ten six -11- olefine aldehydrs (IUPAC titles) (4 36)+TX,(Z)-ten six -11- alkene -1- yl acetates (IUPAC titles) (437)+TX,(Z)-ten six -13- alkene -11- alkynes -1- yl acetates (IUPAC titles) (438)+TX,(Z)-two ten -13- alkene -10- ketone (IUPAC titles) (448)+TX,(Z)-ten four -7- alkene -1- aldehyde (IUPAC titles) (782)+TX,(Z)-ten four -9- alkene -1- alcohol (IUPAC titles) (783)+TX,(Z)-ten four -9- alkene -1- yl acetates (IUPAC titles) (784)+TX,(7E+TX,9Z)-ten two -7+TX,9- diene -1- yl acetates (IUPAC titles) (28 3)+TX,(9Z+TX,11E)-ten four -9+TX,11- diene -1- yl acetates (IUPAC titles) (780)+TX,(9Z+TX,12E)-ten four -9+TX,12- diene -1- yl acetates (IUPAC titles) (781)+TX,- 1- the alkene of 14- methyl 18 (IUPAC titles) (545)+TX,4- methyl nonyl- 5- alcohol (IUPAC titles) (544)+TX with 4- methyl nonyl- 5- ketone,α-multistriatin (alias) [CCN]+TX,Western pine bark beetle assembly pheromone (alias) [CCN]+TX,Pherocon CM (codlelure) (alias) [CCN]+TX,Pherocon CM (codlemone) (alias) (167)+TX,Cue-lure (alias) (179)+TX,Disparmone (277)+TX,12-8- alkene-1- yl acetates (IUPAC titles) (286)+TX,12-9- alkene-1- yl acetates (IUPAC titles) (287)+TX,12-8+TX,10- diene -1- yl acetates (IUPAC titles) (284)+TX,Dominicalure (alias) [CCN]+TX,4- methyloctanoic acids ethyl ester (IUPAC titles) (317)+TX,Eugenol (alias) [CCN]+TX,Dendroctonus frontalis assembly pheromone (alias) [CCN]+TX,Gossyplure (alias) (420)+TX,Grandemone (421)+TX,Grandemone I (alias) (421)+TX,Grandemone II (alias) (421)+TX,Grandemone III (alias) (421)+TX,Grandemone IV (alias) (421)+TX,Hexalure [CCN]+TX,Ipsdienol (alias) [CCN]+TX,Ipsenol (alias) [CCN]+TX,Chafer gyplure (alias) (481)+TX,Lineatin (alias) [CCN]+TX,Litlure (alias) [CCN]+TX,Looplure (alias) [CCN]+TX,medlure[CCN]+TX,Megatomoic acid (alias) [CCN]+TX,Allylveratrole (alias) (540)+TX,Muscalure (563)+TX,18-2+TX,13- diene -1- yl acetates (IUPAC titles) (588)+TX,18-3+TX,13- diene -1- yl acetates (IUPAC titles) (589)+TX,He Kangbi (alias) [CCN]+TX,Oryctalure (alias) (317)+TX,Fei Lekang (alias) [CCN]+TX,Siglure [CCN]+TX,Sordidin (alias) (736)+TX,Sulcatol (alias) [CCN]+TX,14-11- alkene-1- yl acetates (IUPAC titles) (785)+TX,Spy lures ketone (839)+TX,Spy lures ketone A (alias) (839)+TX,Spy lures ketone B1 (alias) (839)+TX,Spy lures ketone B2 (alias) (839)+TX,Spy lures ketone C (alias) (839) and trunc-call (alias) [CCN]+TX,
It is selected from the group the insect repellent of material：2- (octylsulfo) ethanol (IUPAC titles) (591)+TX, dihydropyrone (933)+TX, butoxy (polypropylene glycol) (936)+TX, dibutyl adipate (IUPAC titles) (1046)+TX, dibutyl phthalate (1047)+TX, dibutyl succinate (IUPAC titles) (1048)+TX, Metadelphene [CCN]+TX, dimethyl carbate [CCN]+TX, dimethyl phthalate [CCN]+TX, Rutgers 612 (1137)+TX, hexamide [CCN]+TX, first quinoline fourth (1276)+TX, methylneodecanamide [CCN]+TX, oxamic acid ester [CCN] and picaridin [CCN]+TX,
It is selected from the group the insecticide of material：1+TX,The chloro- 1- nitroethanes of 1- bis- (IUPAC/ chemical abstracts name) (1058)+TX,1+TX,The chloro- 2+TX of 1- bis-,2- bis- (4- ethylphenyls) ethane (IUPAC titles) (1056)+TX,1+TX,2- dichloropropanes (IUPAC/ chemical abstracts name) (1062)+TX,With 1+TX,The 1+TX of 3- dichloropropylenes,2- dichloropropanes (I UPAC titles) (1063)+TX,The bromo- 2- chloroethanes of 1- (I UPAC/ chemical abstracts name) (916)+TX,2+TX,2+TX,Chloro- 1- (the 3+TX of 2- tri-,4- dichlorophenyls) ethylhexoate (IUPAC titles) (1451)+TX,2+TX,2- dichloroethylenes 2- ethylsulfinyl ethyl-methyls phosphate (IUPAC titles) (1066)+TX,2-(1+TX,The amyl- 2- yls of 3- dithia rings) pheiiyldimetliyl carbamate (IUPAC/ chemical abstracts name) (1109)+TX,2- (2- Butoxyethoxies) ethylenebis dithiocarbamate cyanate (IUPAC/ chemical abstracts name) (935)+TX,2-(4+TX,5- dimethyl -1+TX,3- dioxolan 2 yls) phenol methylcarbamate (I UPAC/ chemical abstracts name) (1084)+TX,2- (the chloro- 3+TX of 4-,5- xylyls epoxide) ethanol (IUPAC titles) (986)+TX,2- chlorovinyls diethylphosphate (IUPAC titles) (984)+TX,2- imidazolones (IUPAC titles) (1225)+TX,2- isovaleryl indanes -1+TX,3- diketone (IUPAC titles) (1246)+TX,2- methyl (Propargyl) aminophenyl methyl carbamate (IUPAC titles) (1284)+TX,The thio cyanato- ethyl laurates of 2- (IUPAC titles) (1433)+TX,The bromo- 1- chlorine propyl- 1- alkene of 3- (IUPAC titles) (917)+TX,3- methyl isophthalic acids-Phenylpyrazole -5- bases dimethylcarbamate (IUPAC titles) (1283)+TX,4- methyl (Propargyl) amino -3+TX,5- xylyls methyl carbamate (IUPAC titles) (1285)+TX,5+TX,5- dimethyl -3- epoxides hexamethylene -1- alkenyls dimethylcarbamate (IUPAC titles) (1085)+TX,AVM (1)+TX,Orthene (2)+TX,Acetamiprid (4)+TX,Acethion (alias) [CCN]+TX,Acetyl worm nitrile [CCN]+TX,Acrinathrin (9)+TX,Acrylonitrile (IUPAC titles) (861)+TX,Alanycarb (15)+TX,Aldicarb (16)+TX,Aldoxycarb (863)+TX,Drinox (864)+TX,Allethrin (17)+TX,Allosamidin (alias) [CCN]+TX,Allyxycarb (866)+TX,α-cypermethrin (202)+TX,α-ecdysone (alias) [CCN]+TX,Aluminum phosphate (640)+TX,Amidithion (870)+TX,amidothioate(872)+TX,Aminocarb (873)+TX,Citram (875)+TX,Citram binoxalate (875)+TX,Amitraz (24)+TX,Anabasine (877)+TX,Ai Saidasong (883)+TX,AVI 382 (compound code)+TX,AZ 60541 (compound code)+TX,Nimbin (alias) (41)+TX,Methyl pyrrole
Figure 2006800183129_40
Phosphorus (42)+TX, azinphos ethyl (44)+TX, azinphos-methyl (45)+TX, Alamos (889)+TX, bacillus thuringiensis crystalline substance toxalbumin (alias) (52)+TX, hexafluoro barium silicate (alias) [CCN]+TX, solbar (IUPAC/ chemical abstracts name) (892)+TX, barthrin [CCN]+TX, Bayer 22/190 (research code) (893)+TX, Bayer 22408 (research code) (894)+TX,
Figure 2006800183129_41
Worm prestige (58)+TX,Benfuracard micro (60)+TX,Bensultap (66)+TX,β-cyfloxylate (194)+TX,β-cypermethrin (203)+TX,Bifenthrin (76)+TX,Bioallethrin (78)+TX,Bioallethrin S- cyclopentenyls isomers (alias) (79)+TX,bioethanomethrin[CCN]+TX,Biopermethrin (908)+TX,Bioresmethrin (80)+TX,Two (2- chloroethyls) ether (IUPAC titles) (909)+TX,Bistrifluron (83)+TX,Borax (86)+TX,Brofenxalerate (alias)+TX,Bromobenzene alkene phosphorus (914)+TX,Bromocyclne (918)+TX,Bromo- DDT (alias) [CCN]+TX,Bromophos (920)+TX,Rilariol (921)+TX,Conjunction must prestige (924)+TX,Buprofezin (99)+TX,Butacarb (926)+TX,Special Pyrimitate (927)+TX,Butocarboxim (103)+TX,Butyl ester phosphine (932)+TX,Butanone sulfone prestige (104)+TX,Butylpyridaben (alias)+TX,Cadusafos (109)+TX,Calcium arsenate [CCN]+TX,Cyanogas (444)+TX,Lime sulfur (IUPAC titles) (111)+TX,Toxaphene (941)+TX,Sok (943)+TX,Carbaryl (115)+TX,Carbofuran (118)+TX,Carbon disulfide (IUPAC/ chemical abstracts name) (945)+TX,Carbon tetrachloride (IUPAC titles) (946)+TX,Carbophenothion (947)+TX,Carbosulfan (119)+TX,Padan (123)+TX,Padan's hydrochloride (123)+TX,Cevadilla (alias) (725)+TX,Chlorbicyclen (960)+TX,Niran (128)+TX,Kepone (963)+TX,Spanon (964)+TX,Chlordimeform-hydrochloride (964)+TX,Chlorethoxyfos (129)+TX,Chlorfenapyr (130)+TX,Chlorfenviphos (131)+TX,Chlorfluazuron (132)+TX,Chlormephos (136)+TX,Chloroform [CCN]+TX,Chloropicrin (141)+TX,Chlorophoxim (989)+TX,Chlorine pyrazoxon (990)+TX,Chlopyrifos (145)+TX,Chlorpyrifos-methyl (146)+TX,Actellic (994)+TX,Ring tebufenozide (150)+TX,Cinerin (696)+TX,Cinerin I (696)+TX,II cinerin II (696)+TX,Cis-resmethrin (alias)+TX,Bioresmethrin (80)+TX,Cyhalothrin (alias)+TX,Cloethocarb (999)+TX,Closantel (alias) [CCN]+TX,Clothianadin (165)+TX,Paris green [CCN]+TX,Copper arsenate [CCN]+TX,Copper oleate [CCN]+TX,Resistox (174)+TX,Dithion (1006)+TX,Crotonocyl toluidines (alias) [CCN]+TX,Crotoxyphos (1010)+TX,Ruelene (1011)+TX,Ice crystal (alias) (177)+TX,CS 708 (research code) (1012)+TX,Surecide (1019)+TX,Cynock (184)+TX,Cyanthoate (1020)+TX,Cyclethrin [CCN]+TX,Cycloprothrin (188)+TX,Cyfloxylate (193)+TX,Lambda-cyhalothrin (196)+TX,Cypermethrin (201)+TX,Cyphenothrin (206)+TX,Cyromazine (209)+TX,Cythioate (alias) [CCN]+TX,(R)-4-isopropenyl-1-methyl-1-cyclohexene (alias) [CCN]+TX,D- tetramethrins (alias) (788)+TX,DAEP(1031)+TX,Dazomet (216)+TX,DDT(219)+TX,One first Furadan (1034)+TX,Decis (223)+TX,Demephion (1037)+TX,Demephion-O (1037)+TX,Demephion-S (1037)+TX,Demeton (1038)+TX,Demeton-methyl (224)+TX,Demeton-O (1038)+TX,Demeton-methyl-O (224)+TX,Demeton-S (1038)+TX,Demeton-methyl-S (224)+TX,Metilomerkaptofosoksid-S (1039)+TX,Diafenthiuron (226)+TX,Dialifos (1042)+TX,diamidafos(1044)+TX,Diazinon (227)+TX,Di-captan (1050)+TX,Dichlofenthion (1051)+TX,DDVP (236)+TX,Dicliphos (alias)+TX,Dicresyl (alias) [CCN]+TX,Carbicron (243)+TX,CGA 183893 (244)+TX,Dieldrite (1070)+TX,Diethyl 5- methylpyrazole -3- bases phosphate (IUPAC titles) (1076)+TX,Diflubenzuron (250)+TX,Neutraphylline (dilor) (alias) [CCN]+TX,Dimefluthrin [CCN]+TX,BFPO (1081)+TX,Dimetan (1085)+TX,Rogor (262)+TX,Dimethrin (1083)+TX,Dimethylvinphos (265)+TX,Dimetilan (1086)+TX,Dinitrocyclohexylphenol (1089)+TX,Dinitrocyclohexylphenol (dinex-diclexine) (1089)+TX,Dinoprop (1093)+TX,Dinosam (1094)+TX,Dinoseb (1095)+TX,MTI-446 (271)+TX,Difenolan (1099)+TX,Salithion (1100)+TX,Elacron (1101)+TX,Enemy
Figure 2006800183129_42
Phosphorus (1102)+TX,Disulfoton (278)+TX,Thiapyran phosphorus (1108)+TX,DNOC(282)+TX,Doractin (alias) [CCN]+TX,DSP(1115)+TX,β-ecdysone (alias) [CCN]+TX,EI 1642 (research code) (1118)+TX,Emaricin (291)+TX,Emaricin benzoic ether (291)+TX,EMPC(1120)+TX,Empenthrin (292)+TX,5a,6,9,9a-hexahydro-6,9-methano-2,4 (294)+TX,Endothion (1121)+TX,Endrin (1122)+TX,EPBP(1123)+TX,EPN(297)+TX,Protect children ether (1124)+TX,According to general rhzomorph (alias) [CCN]+TX,S- fenvalerates (302)+TX,Etaphos (alias) [CCN]+TX,Ethiofencarb (308)+TX,Ethodan (309)+TX,Ethiprole (310)+TX,Ethoate methyl (1134)+TX,Phonamiphos (312)+TX,Ethyl formate (I UPAC titles) [CCN]+TX,Perthane (alias) (1056)+TX,Bromofume (316)+TX,Dichloroethanes (chemical name) (1136)+TX,Oxirane [CCN]+TX,Ethofenprox (319)+TX,Etrimfos (1142)+TX,EXD(1143)+TX,Famphur (323)+TX,Fenamiphos (326)+TX,Fenazaflor (1147)+TX,Nankor (1148)+TX,Ethylbenzene prestige (1149)+TX,Fenfluthrin (1150)+TX,Fenifrothion (335)+TX,Bassa (336)+TX,fenoxacrim(1153)+TX,Fenoxycarb (340)+TX,Fenpirithrin (1155)+TX,Fenpropathrin (342)+TX,Tebufenpyrad (alias)+TX,Fensulfothion (1158)+TX,Entex (346)+TX,Entex [CCN]+TX,Fenvalerate (349)+TX,Ethiprole (354)+TX,Flonicamid (358)+TX,Flubendiamide (CAS registration numbers：272451-65-7)+TX,Grand (the 1168)+TX of the double benzene of fluorine chlorine,Flucycloxuron (366)+TX,Flucythrinate (367)+TX,Fluenyl (1169)+TX,flufenerim[CCN]+TX,Flufenoxuron (370)+TX,Trifluoro ethofenprox (1171)+TX,Flumethrin (372)+TX,Taufluvalinate (1184)+TX,FMC 1137 (research code) (1185)+TX,Fonofos (1191)+TX,Carzol (405)+TX,Carzol SP (405)+TX,Formothion (1192)+TX,Amine first prestige (1193)+TX,Fosmethilan (1194)+TX,Chlorpyrifos-methyl (1195)+TX,Lythidathion (408)+TX,Fosthietan (1196)+TX,Furathiocarb (412)+TX,Furethrin (1200)+TX,Gamma-cyhalothrin (197)+TX,γ-HCH(430)+TX,Guanoctine (422)+TX,Biguanides acetate (422)+TX,GY-81 (research code) (423)+TX,Halfenprox (424)+TX,Chlorine tebufenozide (425)+TX,HCH(430)+TX,HEOD(1070)+TX,Heptachlor (1211)+TX,Heptene ether (432)+TX,Speed kills sulphur phosphorus [CCN]+TX,HEXAFLUMURON (439)+TX,HHDN(864)+TX,Hydramethylnon Bait (443)+TX,Hydrogen cyanide (444)+TX,Hydroprene (445)+TX,Quinoline prestige (1223)+TX,Imidacloprid (458)+TX,Miaow alkynes chrysanthemum ester (460)+TX,Indoxacarb (465)+TX,Iodomethane (IUPAC titles) (542)+TX,IPSP(1229)+TX,Isazofos (1231)+TX,Telodrin (1232)+TX,Isocarbophos (alias) (473)+TX,Isodrin (1235)+TX,Isofenphos (1236)+TX,Isolan (1237)+TX,Mobucin (472)+TX,Isopropyl O- (Methoxyamino thiophosphoryl) salicylate (IUPAC titles) (473)+TX,Isoprothiolane (474)+TX,Isothioate (1244)+TX,
Figure 2006800183129_43
Azoles phosphorus (480)+TX,Olivomitecidin (alias) [CCN]+TX,Jasmolin I (696)+TX,Jasmolin ii (696)+TX,Iodfenphos (1248)+TX,Juvenile hormone I (alias) [CCN]+TX,Juvenile hormone II (alias) [CCN]+TX,Juvenile hormone III (alias) [CCN]+TX,Ke Laifan (1249)+TX,Kinoprene (484)+TX,λ-lambda-cyhalothrin (198)+TX,Lead arsenate [CCN]+TX,lepimectin(CCN)+TX,Leptophos (1250)+TX,Lindane (430)+TX,Pyridine worm phosphorus (1251)+TX,Lufenuron (490)+TX,Lythidathion (1253)+TX,Between cumenyl methyl carbamate (IUPAC titles) (1014)+TX,Magnesium phosphide (IUPAC titles) (640)+TX,Malathion (492)+TX,Benzyl malononitrile (1254)+TX,Mazidox (1255)+TX,Afos (502)+TX,Mecarphon (1258)+TX,Menazon (1260)+TX,Mephosfolan (1261)+TX,Calogreen (513)+TX,First oxydemeton_methyl (1263)+TX,metaflumizone(CCN)+TX,Hundred mu of (519)+TX,Hundred mu-sylvite (alias) (519)+TX,Hundred mu-sodium salt (519)+TX,Methacrifos (1266)+TX,Acephatemet (527)+TX,Methanesulfonyl fluoride (IUPAC/ chemical abstracts name) (1268)+TX,Methidathion (529)+TX,Methiocarb (530)+TX,Butenylamine phosphorus (1273)+TX,Methomyl (531)+TX,Methoprene (532)+TX,First quinoline fourth (1276)+TX,Methothrin (alias) (533)+TX,Methoxychlor (534)+TX,Methoxyfenozide (535)+TX,Bromomethane (537)+TX,Methyl-isorhodanate (543)+TX,Methyl chloroform (alias) [CCN]+TX,Dichloromethane [CCN]+TX,Metofluthrin [CCN]+TX,MTMC (550)+TX,
Figure 2006800183129_44
Worm ketone (1288)+TX,Menite (556)+TX,Mexacarbate (1290)+TX,Milbemectin (557)+TX,Polynactin oxime (alias) [CCN]+TX,Mipafox (1293)+TX,Mirex (1294)+TX,Azodrin (561)+TX,Morphothion (1300)+TX,Moxidectin (alias) [CCN]+TX,How peptide phosphorus (alias) [CCN]+TX,2-dichloroethylk dimethyl phosphate (567)+TX,Naphthalene (IUPAC/ chemical abstracts name) (1303)+TX,NC-170 (research code) (1306)+TX,NC-184 (compound code)+TX,Nicotine (578)+TX,Nicotine sulfate (578)+TX,Fluorine mosquito spirit (1309)+TX,Nitenpyram (579)+TX,Nithiazine (1311)+TX,Nitrilacarb (1313)+TX,The zinc chloride complex compound of nitrilacarb 1: 1 (1313)+TX,NNI-0101 (compound code)+TX,NNI-0250 (compound code)+TX,Ninicotine (traditional title) (1319)+TX,Novaluron (585)+TX,Noviflumuron (586)+TX,O-2,The chloro- 4- iodine substituted phenyls O- ethyl diethyldithiocarbamates thiophosphates of 5- bis- (IUPAC titles) (1057)+TX,0,O- diethyl O-4- methyl -2- oxos -2H- chromene -7- bases thiophosphate (IUPAC titles) (1074)+TX,O,O- diethyl O-6- methyl-2-propyl pyrimidine-4-yls thiophosphate (IUPAC titles) (1075)+TX,O,O,O′,The thiopyrophosphate of O '-tetrapropyl two (IUPAC titles) (1424)+TX,Oleic acid (IUPAC titles) (593)+TX,Omethoate (594)+TX,Oxamyl (602)+TX,Metilomerkaptofosoksid (609)+TX,Sub- Thiometan (1324)+TX,Disystom-s (1325)+TX,pp′-DDT(219)+TX,Paracide [CCN]+TX,Parathion (615)+TX,Parathion-methyl (616)+TX,Penfluron (alias) [CCN]+TX,Pentachlorophenol (623)+TX,Pentachlorophenyl laurate (IUPAC titles) (623)+TX,Permethrin (626)+TX,Oil (alias) (628)+TX,PH 60-38 (research code) (1328)+TX,Phenkapton (1330)+TX,Phenothrin (630)+TX,Phenthoate dimephenthoate cidial (631)+TX,Thimet (636)+TX,Phosalone (637)+TX,Phosfolan (1338)+TX,Phosmet (638)+TX,Nichlorfos (1339)+TX,Phosphamidon (639)+TX,Hydrogen phosphide (IUPAC titles) (640)+TX,Phoxim (642)+TX,Phoxiom_methyl (1340)+TX,The phonetic phosphorus of methylamine (1344)+TX,Aphox (651)+TX,Ethyl-pyrimidine phosphorus (1345)+TX,Pirimiphos-methyl (652)+TX,Many chlorine bicyclopentadiene isomers (IUPAC titles) (1346)+TX,Citicide (traditional title) (1347)+TX,Potassium arsenite [CCN]+TX,Potassium thiocyanate [CCN]+TX,Prallethrin (655)+TX,Precocene I (alias) [CCN]+TX,Precocene II (alias) [CCN]+TX,Precocene III (alias) [CCN]+TX,Acid amides Diothyl (1349)+TX,Profenofos (662)+TX,profluthrin[CCN]+TX,Promacyl (1354)+TX,Carbamult (1355)+TX,Kayaphos (1356)+TX,Propetamphos (673)+TX,Arprocarb (678)+TX,Prothidathion (1360)+TX,Toyodan (686)+TX,Prothoate (1362)+TX,protrifenbute[CCN]+TX,Pymetrozine (688)+TX,Pyraclofos (689)+TX,Pyrazophos (693)+TX,Anti- Chryson (1367)+TX,Pyrethrins I (696)+TX,Chrysanthemumdicarboxylic acid monomethyl ester pyrethrolone ester (696)+TX,Pyrethrin (696)+TX,Pyridaben (699)+TX,Pyridalyl (700)+TX,Pyridaphethione (701)+TX,Pyrimidifen (706)+TX,Diothyl (1370)+TX,Nylar (708)+TX,Quassia (alias) [CCN]+TX,Quinalphos (711)+TX,Methyl quinalphos (1376)+TX,High (the 1380)+TX of quinoline match,Quinoline tears good fortune (1381)+TX,R-1492 (research code) (1382)+TX,Iodo-ether salicylamine (alias) [CCN]+TX,Resmethrin (719)+TX,Rotenone (722)+TX,RU 15525 (research code) (723)+TX,RU 25475 (research code) (1386)+TX,Ryanicide (alias) (1387)+TX,Ryanicide (traditional title) (1387)+TX,Jervine (alias) (725)+TX,Schradane (1389)+TX,Cadusafos (alias)+TX,Selamectin (alias) [CCN]+TX,SI-0009 (compound code)+TX,SI-0205 (compound numbers)+TX,SI-0404 (compound code)+TX,SI-0405 (compound code)+TX,Silafluofene (728)+TX,SN 72129 (research code) (1397)+TX,Sodium arsenite [CCN]+TX,Cymag (444)+TX,Sodium fluoride (IUPAC/ chemical abstracts name) (1399)+TX,Sodium hexafluorisilicate (1400)+TX,Pentachlorobenzene sodium oxide molybdena (623)+TX,Sodium selenate (IUPAC titles) (1401)+TX,Thiocyanic acid sodium [CCN]+TX,Sophamide (1402)+TX,Pleocidin (737)+TX,Spiromesifen (739)+TX,spirotetrmat(CCN)+TX,Grand (the 746)+TX of sulphur phenylate,The grand sodium salt of sulphur phenylate (746)+TX,Sulfluramid (750)+TX,Sulfotep (753)+TX,Vikane (756)+TX,Sulprofos (1408)+TX,Tar (alias) (758)+TX,τ-taufluvalinate (398)+TX,Tazimcarb (1412)+TX,TDE(1414)+TX,Tebufenozide (762)+TX,Tebufenpyrad (763)+TX,Butyl pyrimidine phosphorus (764)+TX,Fluorobenzene urea (768)+TX,Tefluthrin (769)+TX,Swebate (770)+TX,TEPP(1417)+TX,Terallethrin (1418)+TX,Terbam (alias)+TX,Terbufos (773)+TX,Tetrachloroethanes [CCN]+TX,Ravap (777)+TX,Tetramethrin (787)+TX,θ-cypermethrin (204)+TX,Thiacloprid (791)+TX,Thiafenox (alias)+TX,Diacloden (792)+TX,Thiophene chlorine phosphorus (1428)+TX,Talcord (1431)+TX,Thiocyclam (798)+TX,Thiocyclam binoxalate (798)+TX,Thiodicarb (799)+TX,Thiofanox (800)+TX,Thiometon (801)+TX,Thionazin (1434)+TX,Dimehypo (803)+TX,Desinsection double sodium salt (803)+TX,Su Li rhzomorphs (alias) [CCN]+TX,Tolfenpyrad (809)+TX,Tralomethrin (812)+TX,Transfluthrin (813)+TX,Anti- Permethrin (1440)+TX,Triamiphos (1441)+TX,Triaguron (818)+TX,Hostathion (820)+TX,Triazuron (alias)+TX,Metrifonate (824)+TX,Trichloromethyl 1605-3 (alias) [CCN]+TX,Trichloronate (1452)+TX,The phosphorus of chlorobenzene second third (1455)+TX,Triflumuron (835)+TX,Landrin (840)+TX,Triprene (1459)+TX,Vamidothion (8 4 7)+TX,Fluorine pyrazoles worm [CCN]+TX,Veratridine (alias) (725)+TX,Jervine (alias) (725)+TX,XMC(853)+TX,Meobal (854)+TX,YI-5302 (compound code)+TX,ζ-cypermethrin (205)+TX,Zetamethrin (alias)+TX,Zinc phosphide (640)+TX,Zolaprofos (1469) and ZXI 8901 (research code) (858)+TX,
It is selected from the group the invertebrate poison of material：Two (tributyl tin) oxide (IUPAC titles) (913)+TX, acetbromamide [CCN]+TX, calcium arsenate [CCN]+TX, cloethocarb (999)+TX, Paris green [CCN]+TX, copper sulphate (172)+TX, fentin (347)+TX, ferric phosphate (IUPAC titles) (352)+TX, the methaldehyde (518)+TX, methiocarb (530)+TX, niclosamide (576)+TX, niclosamide ethanolamine salt (576)+TX, pentachlorophenol (623)+TX, pentachlorobenzene sodium oxide molybdena (623)+TX, tazimcarb (1412)+TX, thiodicarb (799)+TX, Butinox (913)+TX, trifenmorph (1454)+TX, Landrin (840)+TX, fentin acetate (IUPAC titles) (347) and fentin hydrochloride (IUPAC titles) (347)+TX,
It is selected from the group the nematicide of material：AKD-3088 (compound code)+TX,1+TX,The bromo- 3- chloropropanes of 2- bis- (I UPAC/ chemical abstracts name) (1045)+TX,1+TX,2- dichloropropanes (IUPAC/ chemical abstracts name) (1062)+TX,With 1+TX,The 1+TX of 3- dichloropropylenes,2- dichloropropanes (IUPAC titles) (1063)+TX,1+TX,3- dichloropropylenes (233)+TX,3+TX,4- dichloro thiophanes 1+TX,1- dioxide (I UPAC/ chemical abstracts name) (1065)+TX,3- (4- chlorphenyls) -5- methyl rhodanine (IUPAC titles) (980)+TX,Thio-the 1+TX of 5- methyl -6-,3+TX,5- thiadiazine alkane -3- guanidine-acetic acids (IUPAC titles) (1286)+TX,6- isopentene groups adenine phosphate (alias) (210)+TX,AVM (1)+TX,Acetyl worm nitrile [CCN]+TX,Alanycarb (15)+TX,Aldicarb (16)+TX,Aldoxycarb (863)+TX,AZ 60541 (compound code)+TX,benclothiaz[CCN]+TX,Benomyl (62)+TX,Butylpyridaben (alias)+TX,Cadusafos (109)+TX,Carbofuran (118)+TX,Carbon disulfide (945)+TX,Carbosulfan (119)+TX,Chloropicrin (141)+TX,Chlopyrifos (145)+TX,Cloethocarb (999)+TX,The basic element of cell division (alias) (210)+TX,Dazomet (216)+TX,DBCP(1045)+TX,DCIP(218)+TX,diamidafos(1044)+TX,Dichlofenthion (1051)+TX,Dicliphos (alias)+TX,Rogor (262)+TX,Doractin (alias) [CCN]+TX,Emaricin (291)+TX,Emaricin benzoic ether (291)+TX,According to general rhzomorph (alias) [CCN]+TX,Phonamiphos (312)+TX,Bromofume (316)+TX,Fenamiphos (326)+TX,Tebufenpyrad (alias)+TX,Fensulfothion (1158)+TX,Lythidathion (408)+TX,Fosthietan (1196)+TX,Furfural (alias) [CCN]+TX,GY-81 (research code) (423)+TX,Speed kills sulphur phosphorus [CCN]+TX,Iodomethane (IUPAC titles) (542)+TX,isamidofos(1230)+TX,Isazofos (1231)+TX,Olivomitecidin (alias) [CCN]+TX,Chaff adenine phosphate (alias) (210)+TX,Mecarphon (1258)+TX,Hundred mu of (519)+TX,Hundred mu-sylvite (alias) (519)+TX,Hundred mu-sodium salt (519)+TX,Bromomethane (537)+TX,Methyl-isorhodanate (543)+TX,Polynactin oxime (alias) [CCN]+TX,Moxidectin (alias) [CCN]+TX,Myrothecium verrucaria component (alias) (565)+TX,NC-184 (compound code)+TX,Oxamyl (602)+TX,Thimet (636)+TX,Phosphamidon (639)+TX,Phosphorus worm prestige [CCN]+TX,Cadusafos (alias)+TX,Selamectin (alias) [CCN]+TX,Pleocidin (737)+TX,Terbam (alias)+TX,Terbufos (773)+TX,Penphene (IUPAC/ chemical abstracts name) (1422)+TX,Thiafenox (alias)+TX,Thionazin (1434)+TX,Hostathion (820)+TX,Triazuron (alias)+TX,Xylenols [CCN]+TX,YI-5302 (compound code) and zeatin (alias) (210)+TX,
It is selected from the group the nitrification inhibitor of material：Ehtyl potassium xanthate [CCN] and trichloromethyl pyridine (580)+TX,
It is selected from the group the plant activator of material：Thiadiazoles element (6)+TX, thiadiazoles element-S- methyl (6)+TX, probenazole (658) and big Gentrin Knotweed P.E (alias) (720)+TX,
It is selected from the group the rat poison of material：2- isovaleryl indanes -1+TX,3- diketone (IUPAC titles) (1246)+TX,4- (quinoxaline -2- bases amino) benzsulfamide (I UPAC titles) (748)+TX,α-chloropharin [CCN]+TX,Aluminum phosphate (640)+TX,ANTU (880)+TX,Arsenic trioxide (882)+TX,Barium carbonate (891)+TX,Double mouse urea (912)+TX,Brodifacoum (89)+TX,Bromadiolone (91)+TX,Bromethalin (92)+TX,Cyanogas (444)+TX,Chloralose (127)+TX,Chloradion (140)+TX,Vitamin D3 (alias) (850)+TX,Coumachlor (1004)+TX,Coumafuryl (1005)+TX,Coumatetralyl (175)+TX,Crimidine (1009)+TX,Difenacoum (246)+TX,Difethialone (249)+TX,Diphacinone (273)+TX,Ergocalciferol (301)+TX,Flocoumafen (357)+TX,Fluorakil 100 (379)+TX,Flupropadine (1183)+TX,Flupropadine hydrochloride (1183)+TX,γ-HCH(430)+TX,HCH(430)+TX,Hydrogen cyanide (444)+TX,Iodomethane (I UPAC titles) (542)+TX,Lindane (430)+TX,Magnesium phosphide (IUPAC titles) (640)+TX,Bromomethane (537)+TX,Shoxin (1318)+TX,Malicious mouse spirit (1336)+TX,Hydrogen phosphide (IUPAC titles) (640)+TX,Phosphorus [CCN]+TX,Duocide (1341)+TX,Potassium arsenite [CCN]+TX,Pyrinuron (1371)+TX,Red squill (1390)+TX,Sodium arsenite [CCN]+TX,Cymag (444)+TX,Fratol (735)+TX,Strychnine (745)+TX,Thallium sulfate [CCN]+TX,Warfarin (851) and zinc phosphide (640)+TX,
It is selected from the group the synergist of material：2- (2- Butoxyethoxies) ethyl pepper base ester (IUPAC titles) (934)+TX, 5- (1+TX, 3- benzodioxole -5- bases) -3- hexyl hexamethylene -2- ketenes (IUPAC titles) (903)+TX, fanesol (alias) (324)+TX with nerolidol, MB-599 (research code) (498)+TX, MGK 264 (research code) (296)+TX, Butacide (649)+TX, Piprotal (1343)+TX, propyl isome (1358)+TX, S421 (research code) (724)+TX, Safroxan (1393)+TX, sesasmolin (1394) and sulfoxide (1406)+TX,
It is selected from the group the animal repellant of material：Anthraquinone (32)+TX, chloralose (127)+TX, copper naphthenate [CCN]+TX, Cupravit (171)+TX, diazinon (227)+TX, bicyclopentadiene (chemical name) (1069)+TX, Guanoctine (422)+TX, biguanides acetate (422)+TX, methiocarb (530)+TX, pyridine -4- amine (I UPAC titles) (23)+TX, thiram (804)+TX, Landrin (840)+TX, zinc naphthenate [CCN] and ziram (856)+TX
It is selected from the group the virucide of material：Imanin (alias) [CCN] and virazole (alias) [CCN]+TX,
And it is selected from the group the wound protective agent of material：Mercury oxide (512)+TX, octhilinone (590) and thiophanate-methyl (802)+TX,
Formula A-1 compounds
Figure S2006800183129D00681
Formula A-2 compounds
Figure S2006800183129D00682
Formula A-3 compounds
Figure S2006800183129D00683
Formula A-4 compounds
Formula A-5 compounds
Figure S2006800183129D00691
Formula A-6 compounds
Figure S2006800183129D00692
Formula A-7 compounds
Figure S2006800183129D00693
Formula A-8 compounds
Figure S2006800183129D00694
Formula A-9 compounds
Figure S2006800183129D00701
Formula A-10 compounds
Figure S2006800183129D00702
Formula A-11 compounds
Figure S2006800183129D00703
Formula A-12 compounds
Figure S2006800183129D00704
Formula A-13 compounds
Figure S2006800183129D00711
Formula A-14 compounds
Figure S2006800183129D00712
Formula A-15 compounds
Figure S2006800183129D00713
Formula A-16 compounds
Figure S2006800183129D00714
Formula A-17 compounds
Figure S2006800183129D00721
Formula A-18 compounds
Figure S2006800183129D00722
Formula A-19 compounds
Formula A-20 compounds
Figure S2006800183129D00731
Formula A-21 compounds
Figure S2006800183129D00732
Formula A-22 compounds
Formula A-23 compounds
Formula A-24 compounds
Formula A-25 compounds
Figure S2006800183129D00743
Formula A-26 compounds
With oxygen ring azoles (60207-31-0)+TX, bitertanol [70585-36-3]+TX, bromuconazole [116255-48-2]+TX, Cyproconazole [94361-06-5]+TX,
Figure 2006800183129_45
Ether azoles [119446-68-3]+TX,Olefin conversion [83657-24-3]+TX,Epoxy bacterium azoles [106325-08-0]+TX,RH-7592 [114369-43-6]+TX,Fluquinconazole [136426-54-5]+TX,Flusilazole [85509-19-9]+TX,Flutriafol [76674-21-0]+TX,Hexaconazole [79983-71-4]+TX,Imazalil [35554-44-0]+TX,Glyoxalin [86598-92-7]+TX,Kind bacterium azoles [125225-28-7]+TX,Metconazole [125116-23-6]+TX,Nitrile bacterium azoles [88671-89-0]+TX,Pefurazoate [101903-30-4]+TX,Penconazole [66246-88-6]+TX,Prothioconazoles [178928-70-6]+TX,Pyrifenox [88283-41-4]+TX,Prochloraz [67747-09-5]+TX,Propiconazole [60207-90-1]+TX,Simeconazoles [149508-90-7]+TX,Tebuconazole [107534-96-3]+TX,Tetraconazole [112281-77-3]+TX,Triazolone [43121-43-3]+TX,Triadimenol [55219-65-3]+TX,Fluorine bacterium azoles [99387-89-0]+TX,Triticonazole [131983-72-7]+TX,Ancymidol [12771-68-5]+TX,Fenarimol [60168-88-9]+TX,Nuarimol [63284-71-9]+TX,Bupirimate [41483-43-6]+TX,Dimethirimol [5221-53-4]+TX,Ethirimol [23947-60-6]+TX,Dodemorph [1593-77-7]+TX,Fenpropidin [67306-00-7]+TX,Third bacterium spirit [67564-91-4]+TX,Volution bacterium amine [118134-30-8]+TX,Tridemorph [81412-43-3]+TX,Cyprodinil [121552-61-2]+TX,Mepanipyrim [110235-47-7]+TX,Pyrimethanil [53112-28-0]+TX,Fenpiclonil [74738-17-3]+TX,Fludioxonil [131341-86-1]+TX,M 9834 [71626-11-4]+TX,Furalaxyl [57646-30-7]+TX,Metalaxyl [57837-19-1]+TX,R- metalaxyls [70630-17-0]+TX,Ofurace [58810-48-3]+TX,
Figure 2006800183129_46
White spirit [77732-09-3]+TX,Benomyl [17804-35-2]+TX,Carbendazim [10605-21-7]+TX,Debacarb [62732-91-6]+TX,Furidazol [3878-19-1]+TX,Probenazole [148-79-8]+TX,Chlozolinate [84332-86-5]+TX,Sclex [24201-58-9]+TX,Iprodione [36734-19-7]+TX,Myclozoline[54864-61-8]+TX,Procymidone [32809-16-8]+TX,Vinclozolin [50471-44-8]+TX,Niacinamide [188425-85-6]+TX,Carboxin [5234-68-4]+TX,Fenfuram [24691-80-3]+TX,Flutolanil [66332-96-5]+TX,Mebenil [55814-41-0]+TX,Oxycarboxin [5259-88-1]+TX,Pyrrole metsulfovax [183675-82-3]+TX,Thiophene fluorine bacterium amine [130000-40-7]+TX,Guanoctine [108173-90-6]+TX,Dodine [2439-10-3] [112-65-2] (freieBase)+TX,Iminoctadine [13516-27-3]+TX,Fluoxastrobin [131860-33-8]+TX,Dimoxystrobin [149961-52-4]+TX,Enestroburin { Proc.BCPC+TX,Int.Congr.+TX,Glasgow+TX,2003+TX,1+TX,93}+TX,Fluoxastrobin [361377-29-9]+TX,Kresoxim-methyl [143390-89-0]+TX,SSF 126 [133408-50-1]+TX,Trifloxystrobin [141517-21-7]+TX,Orysastrobin [248593-16-0]+TX,ZEN 90160 [117428-22-5]+TX,Pyraclostrobin [175013-18-0]+TX,Fervam [14484-64-1]+TX,Mancozeb [8018-01-7]+TX,Maneb [12427-38-2]+TX,Carbatene [9006-42-2]+TX,Propineb [12071-83-9]+TX,Thiram [137-26-8]+TX,Zineb [12122-67-7]+TX,Ziram [137-30-4]+TX,Difoltan [2425-06-1]+TX,Captan [133-06-2]+TX,Dichlofluanid [1085-98-9]+TX,Fluoromide [41205-21-4]+TX,Folpet [133-07-3]+TX,Tolylfluanid [731-27-1]+TX,Bordeaux mixture [8011-63-0]+TX,Kocide SD [20427-59-2]+TX,Cupravit [1332-40-7]+TX,Copper sulphate [7758-98-7]+TX,Cupric oxide [1317-39-1]+TX,Mancopper [53988-93-5]+TX,Copper 8-hydroxyquinolinate [10380-28-6]+TX,Dinitro ester [131-72-6]+TX,Nitrothalisopropyl [10552-74-6]+TX,Edifenphos [17109-49-8]+TX,Different rice blast net [26087-47-8]+TX,Isoprothiolane [50512-35-1]+TX,Phosdiphen [36519-00-3]+TX,Pyrazophos [13457-18-6]+TX,Tolelofos-methyl [57018-04-9]+TX,Acibenzolar [135158-54-2]+TX,Anilazine [101-05-3]+TX,Benzene metsulfovax [413615-35-7]+TX,Blasticidin S [2079-00-7]+TX,Chinomethionat [2439-01-2]+TX,Chloroneb [2675-77-6]+TX,Bravo [1897-45-6]+TX,Cyflufenamid [180409-60-3]+TX,Cymoxanil [57966-95-7]+TX,Dichlone [117-80-6]+TX,Double chlorine zarilamid [139920-32-4]+TX,Diclomezin [62865-36-5]+TX,Botran [99-30-9]+TX,Diethofencarb [87130-20-9]+TX,Dimethomorph [110488-70-5]+TX,SYP-LI90 (flumorph) [211867-47-9]+TX,Dithianon [3347-22-6]+TX,Guardian [162650-77-3]+TX,Grandox fumigant [2593-15-9]+TX,
Figure 2006800183129_47
Cycloheximide triazole [131807-57-3]+TX, Fenamidone [161326-34-7]+TX, zarilamid [115852-48-7]+TX, fentin [668-34-8]+TX, ferimzone [89269-64-7]+TX, fluazinam [79622-59-6]+TX, fluopicolide [239110-15-7]+TX, flusulfamide [106917-52-6]+TX, fenhexamid [126833-17-8]+TX, aliette [39148-24-8]+TXMould spirit [10004-44-1]+TX, iprovalicarb [140923-17-7]+TX, IKF-916 (cyazofamid) [120116-88-3]+TX, kasugarnycin [6980-18-3]+TX, methasulfocarb [66952-49-6]+TX, Metrafenone [220899-03-6]+TX, luxuriant grand [the 66063-05-6]+TX of bacterium, Rabcide [27355-22-2]+TX, polyoxin [11113-80-7]+TX, probenazole [27605-76-1]+TX, Propamocarb [25606-41-1]+TX, Proquinazid [189278-12-4]+TX, pyroquilon [57369-32-1]+TX, quinoxyfen [124495-18-7]+TX, pentachloronitrobenzene [82-68-8]+TX, Schwefel [7704-34-9]+TX, Tiadinil [223580-51-6]+TX, triazoxide [72459-58-6]+TX, tricyclazole [41814-78-2]+TX, triforine [26644-46-2]+TX, valida [37248-47-8]+TX, zoxamide (RH7281) [156052-68-5]+TX, Mandipropamid [374726-62-2]+TX, formula F-1 compounds
Figure S2006800183129D00781
Wherein Ra5It is trifluoromethyl or difluoromethyl (WO2004/058723)+TX,；Formula F-2 compounds
Figure S2006800183129D00782
Wherein Ra6It is trifluoromethyl or difluoromethyl (WO2004/058723)+TX,；Formula F-3 racemic compound (cis)
Wherein Ra7It is trifluoromethyl or difluoromethyl (WO2004/035589)+TX, formula F-4 racemic compound (trans)
Wherein Ra7It is trifluoromethyl or difluoromethyl (WO2004/035589)+TX, formula F-5 compounds
Figure S2006800183129D00792
This is the epimeric mixture of formula F-3 (cis) and F-4 (trans) racemic compound, the ratio of wherein formula F-3 (cis) racemic compounds and formula F-4 (trans) racemic compound is 1000: 1 to 1: 1000, wherein Ra7It is trifluoromethyl or difluoromethyl (WO2004/035589)+TX, formula F-6 compounds
Figure S2006800183129D00793
Wherein Ra8It is trifluoromethyl or difluoromethyl (WO2004/035589)+TX, formula F-7 racemic compound (trans)
Figure S2006800183129D00794
Wherein Ra9It is trifluoromethyl or difluoromethyl (WO03/074491)+TX, formula F-8 racemic compound (cis)
Figure S2006800183129D00801
Wherein Ra9It is trifluoromethyl or difluoromethyl (WO03/074491)+TX, formula F-9 compounds
This is the mixture of formula F-7 (trans) and F-8 (cis) racemic compound, and the ratio of wherein formula F-7 (trans) racemic compounds and formula F-8 (cis) racemic compound is 2: 1 to 100: 1,
Wherein Ra9It is trifluoromethyl or difluoromethyl (WO03/074491)+TX,
Formula F-10 compounds
Figure S2006800183129D00803
Wherein R10It is trifluoromethyl or difluoromethyl (WO2004/058723)+TX, formula F-11 racemic compound (trans)
Wherein R11It is trifluoromethyl or difluoromethyl (WO03/074491)+TX, formula F-12 racemic compound (cis)
Figure S2006800183129D00812
Wherein R11It is trifluoromethyl or difluoromethyl (WO03/074491)+TX, formula F-13 compounds
Figure S2006800183129D00813
This is formula F-11 (trans) and F-12 (cis) racemic mixture, wherein R11It is trifluoromethyl or difluoromethyl (WO 03/074491)+TX, and formula F-14 compounds
Figure S2006800183129D00814
(WO2004/058723)+TX, and formula F-15 compounds
Figure S2006800183129D00821
Compound of formula I selected from Table A and B contains with the mixture of above-mentioned active component is preferably selected from Table A and B compound and active component as described above with what 100: 1 to 1: 6000 mixing ratio was mixed, particularly 50: 1 to 1: 50, more particularly 20: 1 to 1: 20, more it is particularly 10: 1 to 1: 10, it is particularly very much 5: 1 to 1: 5, particularly preferred ratio is 2: 1 to 1: 2, 4: 1 to 2: 1 ratio also, it is preferred that, especially ratio 1: 1, or 5: 1, or 5: 2, or 5: 3, or 5: 4, or 4: 1, or 4: 2, or 4: 3, or 3: 1, or 3: 2, or 2: 1, or 1: 5, or 2: 5, or 3: 5, or 4: 5, or 1: 4, or 2: 4, or 3: 4, or 1: 3, or 2: 3, or 1: 2, or 1: 600, or 1: 300, or 1: 150, or 1: 35, or 2: 35, or 4: 35, or 1: 75, or 2: 75, or 4: 75, or 1: 6000, or 1: 3000, or 1: 1500, or 1: 350, or 2: 350, or 4: 350, or 1: 750, or 2: 750, or 4: 750.These mixing ratios are understood to include weight ratio and mol ratio.
Containing the compound of formula I selected from Table A and B and-kind or the mixtures of a variety of active components as described above can such as single " can be used " form, applied in spraying mixture such as " tank mix " form being made up of the independent preparation of each active component, applied with the combining form applied with single active component order, that is, be spaced reasonable short period such as a few houres or several days one after the other apply.The order of administration of compound of formula I and active component as described above selected from Table A and B is not the key for realizing the present invention.
Index in the right square bracket of active component, such as [3878-19-1] refer to chemical abstracts registry no.Formula A-1 is described in WO 03/015518 or WO 04/067528 to A-26 compounds.Above-mentioned mixing pairing composition is known.Wherein active component is included in " The PesticideManual " (agricultural chemicals handbook) [The Pesticide Manual-A World Compendium；13rd edition；Editor: C.D.S.Tomlin；The British Crop ProtectionCouncil] in, they are described with the numbering gone out given in the round parentheses of specific compound above wherein；Such as compound " AVM " is described with numbering (1).Wherein " [CCN] " is added for specific compound above, and described compound is included in " Compendiumof Pesticide Common Names" in (agricultural chemicals common name summary), they can be in Internet [A.Wood；Compendium of Pesticide Common Names,Copyright1995-2004] in find；For example, compound " acetyl worm nitrile " is described in the Internet addresshttp://www.alanwood.net/pesticides/acetoprole.html.In.
Most active components are represented by above so-called " common name ", and corresponding " ISO common names " or other " common name " is used in different situations.If its title is not " common name ", title that used title species goes out given in the round parentheses with specific compound is replaced；In this case, using IUPAC titles, IUPAC/ chemical abstracts name, " chemical name ", " traditional title ", " chemical combination name " or " research code ", if or both without using specified title or without using " common name ", use alias." CAS registration numbers " represents chemical abstracts registry no.
Biological Examples(%=total amount percentages, unless otherwise indicated)
Embodiment B1：To codling moth (Cydia pomonella) activity：
The steinernema of standard is eaten into hay block (1.5cm is wide) surely to be passed through and be immersed in atoleine (about 80 DEG C) with toothpick.After after paraffin coating hardening, the aqueous emulsion containing 400ppm active components is applied using De Vilbis sprayers (25ml, 1 bar).After layer to be sprayed is dried, hay block is put into plastic containers, 2 steinernemas (1 age) newly hatched then are added.Then vinyl cover closed vessel is used.After being incubated 14 days under 26 DEG C and 40-60% relative humidity, the survival rate and its growth regulating of caterpillar are determined.In this test, listed compound shows good activity in table C.Particularly A.1.1 compound, A.1.13, A.1.7 and A.1.4 has the activity more than 80%.
Embodiment B2：To the activity with spot cucumber chrysomelid (Diabrotica balteata)
Corn seedling is sprayed with the aqueous emulsion spraying mixture containing 400ppm active components, after layer to be sprayed is dried, 10 (2 age) band chrysomelid larva of spot cucumber is migrated, is placed in plastic containers.After 6 days, determine that population reduces percentage (active %) by the number of dead larvae between relatively more treated and untreated plant.
In this test, listed compound shows good activity in table C.Particularly A.1.13 compound, A.1.1, A.1.4, B.1.28, A.1.122 and A.1.7 has the activity more than 80%.
Embodiment B3：To tobacco budworm (Heliothis virescens) (foliage applying) Activity
Soybean seedling is sprayed with the aqueous emulsion spraying mixture containing 400ppm active components, after layer to be sprayed is dried, 10 (1 age) tobacco budworm caterpillars is migrated, is placed in plastic containers.After 6 days, determine that population and Feeding damage reduce percentage (active %) by the number and Feeding damage of dead caterpillars between relatively more treated and untreated plant.
In this test, listed compound shows good activity in table C.Particularly A.1.13 compound, A.1.4, A.1.1 and A.1.7 has the activity more than 80%.
Embodiment B4：To the activity of tobacco budworm (being applied to ovum)
The tobacco budworm ovum on cotton has been attached to the aqueous emulsion spraying mixture sprinkling containing 400ppm active components.After 8 days, the hatching percentage of ovum and the survival rate (active %) of caterpillar are evaluated by comparing untreated fish group.
In this test, listed compound shows good activity in table C.Particularly A.1.13 compound, A.1.1, A.1.4, B.1.28, A.1.122, A.1.57, A.1.131 and A.1.7 has the activity more than 80%.
Embodiment B5：To the activity of black peach aphid (Myzus persicae) (foliage applying)
Pea seedlings is infected with black peach aphid, is then sprayed with the spraying mixture containing 400ppm active components, afterwards in 20 ° of cultures.After 3 and 6 days, determine that population reduces percentage (active %) by the number of dead aphid between relatively more treated and untreated plant.
In this test, listed compound shows good activity in table C.Particularly A.1.13 compound, A.1.4, A.1.122 and A.1.7 has the activity more than 80%.
Embodiment B6：To the activity of black peach aphid (interior suction administration)
Pea seedlings is infected with black peach aphid, and then its root is placed in the spraying mixture containing 400ppm active components.Afterwards by seedling in 20 ° of cultures.After 3 and 6 days, determine that population reduces percentage (active %) by the number of dead aphid between relatively more treated and untreated plant.
In this test, listed compound shows good activity in table C.Particularly A.1.4 compound, A.1.122 and A.1.7 has the activity more than 8 0%.
Embodiment B7：To diamondback moth (Plutella xylostella) activity
Cabbage seedling is sprayed with the aqueous emulsion spraying mixture containing 400ppm active components, after layer to be sprayed is dried, 10 (3 age) diamondback moth caterpillars is migrated, is placed in plastic containers.After 3 days, determine that population and Feeding damage reduce percentage (active %) by the number and Feeding damage of dead caterpillars between relatively more treated and untreated plant.
In this test, listed compound shows good activity in table C.Particularly A.1.13 compound, A.1.1, A.1.4, B.1.28, A.1.122, A.1.57, A.1.131, A.1.134 and A.1.7 has the activity more than 80%.
Embodiment B8：To the activity of Spodoptera littoralis
Soybean seedling is sprayed with the aqueous emulsion spraying mixture containing 400ppm active components, after layer to be sprayed is dried, 10 (1 age) Spodoptera littoralis caterpillars is migrated, is placed in plastic containers.After 3 days, determine that population and Feeding damage reduce percentage (active %) by the number and Feeding damage of dead caterpillars between relatively more treated and untreated plant.
In this test, listed compound shows good activity in table C.Particularly A.1.13 compound, A.1.1, A.1.4, B.1.28, A.1.122, A.1.57, A.1.131 and A.1.7 has the activity more than 80%.
Embodiment B9：To Spodoptera littoralis (Spodoptera littoralis) systemic insecticide Test：
The corn seedling (Zea mais, kind Stoneville) in four day age is individually placed in the bottle containing 24ml water, dilution has 12.5ppm compound in water.Make growth of seedling 6 days.Then cut blade and be placed in training Ti Shi culture dishes (5cm diameters), 12-15 1 age Spodoptera littoralis larvas of inoculation and (25 DEG C, 50% relative humidity, 18: 6 L: D illumination periods) incubation 4 days in growth room.Count the number of insect living and calculate the death rate.Experiment is once repeated.In this test, listed compound shows good activity in table C.Particularly A.1.131 A.1.13 compound, A.1.1, A.1.4, A.1.7, A.1.13, A.1.122, have the activity more than 80% with B1.28.
Activity of the embodiment B10 to Frankliniella occidentalis (Frankliniella occidentalis)：
With the Kidney bean leaf dish on the agar in the test solution processing training Ti Shi wares of dilution or the Kidney bean plant in spray chamber.After drying, leaf dish is cut, is placed in the agar layer surface in plastic cup, is infected with mixed population.6 days after infection (leaf dish) or 14 days (plant), check sample process after population reduction and compared with untreated population.In this test, listed compound shows good activity in table C.Particularly A.1.1 compound, A.1.4, A.1.13, A.1.122 and A.1.7 has the activity more than 80%.

Claims (6)

  1. Formula 1. (Ib) compound
    Figure FSB00000676914600011
    Wherein
    R91It is C1-C6Alkyl；
    R93It is C1-C4Halogenated alkoxy, C1-C4Alkylthio group；
    R94It is hydrogen or halogen；
    A is C1-C6Alkylidene；
    Q is 0 or 1；
    X is oxygen, NH or C1-C4Alkyl-N；
    P is 0；
    Y is C3-C6Cycloalkyl；
    B is cyclopropyl, and the cyclopropyl can be by C1-C6Alkyl list-or di-substituted；
    With agriculturally acceptable salt/dynamic isomer of these compounds.
  2. 2. a kind of composition pesticide, contain at least one claim 1 Formulas I b compounds or it is appropriate when its dynamic isomer as active component and at least one auxiliary agent, the compound is free form or the available salt form of agricultural chemicals in all cases.
  3. 3. composition described in claim 2, the canonical biometric for preventing and treating insect and Acarina.
  4. 4. a kind of method of pest control, including composition described in claim 2 is applied to insect or its environment, wherein not including the directly diagnosis using lived human body or animal body as the disease of objective for implementation and therapeutic process.
  5. 5. claim 4 methods described, the canonical biometric for preventing and treating insect or Acarina.
  6. 6. claim 4 methods described, for protecting plant propagation material from the invasion and attack of insect, this method includes handling the propagating materials or plants the place of the propagating materials.
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