TW202035404A - Pesticidally active heterocyclic derivatives with sulfoximine containing substituents - Google Patents

Abstract

Compounds of the formula (I)

, wherein the substituents are as defined in claim 1. Furthermore, the present invention relates to agrochemical compositions which comprise compounds of formula (I), to preparation of these compositions, and to the use of the compounds or compositions in agriculture or horticulture for combating, preventing or controlling animal pests, including arthropods and in particular insects or representatives of the orderAcarina .

Description

Harmful biologically active heterocyclic derivatives with substituents containing sulfoximine

The present invention relates to heterocyclic derivatives with harmful biological activity (especially insecticidal activity) containing sulfoximine substituents, preparation methods thereof, compositions containing these compounds, and their use in the control of animal pests (Including arthropods and especially insects or representatives of the order Acarina ).

Pesticidal active heterocyclic sulfoximine derivatives have previously been described in the literature, for example in WO 2015/071180, WO 2018/206348 and WO 2019/065568.

It has now been unexpectedly discovered that certain novel phenyl and pyridinyl derivatives containing cyanoalkoxy groups have beneficial properties as pesticides.

(I)， 其中 A係CH或N； R₁ 係C₁ -C₄ 烷基； R₇ 和R₈ 彼此獨立地是氫、鹵素或C₁ -C₆ 烷基； R₉ 係氫或C₁ -C₄ 烷基； R₁₀ 係氫、氰基、-C(O)R₂₅ 、-C(O)OR₂₆ 或C₁ -C₆ 烷基； R₂₅ 係氫、C₁ -C₆ 烷基或C₁ -C₆ 鹵代烷基； R₂₆ 係C₁ -C₆ 烷基或C₁ -C₆ 鹵代烷基； n係0或1； Q係選自以下群組的基團，該群組由以下各項組成：式Q₁ 至Q₅

其中箭頭指示與摻入有基團A的環的附接點； 並且其中 X₁ 係O、S或NR₃ ； R₃ 係C₁ -C₄ 烷基； R₂ 係鹵素、C₁ -C₆ 鹵代烷基、C₁ -C₄ 鹵代烷基氫硫基、C₁ -C₄ 鹵代烷基亞磺醯基、C₁ -C₄ 鹵代烷基磺醯基或C₁ -C₆ 鹵代烷氧基； G₁ 和G₂ 彼此獨立地是N或CH； R₄ 係C₁ -C₄ 烷基、C₁ -C₄ 鹵代烷基、C₃ -C₆ 環烷基或C₁ -C₄ 烷氧基；和 該等式I的化合物的農用化學上可接受的鹽、立體異構物、鏡像異構物、互變異構物和N-氧化物。Therefore the present invention provides a compound of formula I,

(I), wherein A is CH or N; R ₁ is C ₁ -C ₄ alkyl; R ₇ and R ₈ are independently of each other hydrogen, halogen or C ₁ -C ₆ alkyl; R ₉ is hydrogen or C ₁ -C ₄ alkyl; R ₁₀ is hydrogen, cyano, -C(O)R ₂₅ , -C(O)OR ₂₆ or C ₁ -C ₆ alkyl; R ₂₅ is hydrogen, C ₁ -C ₆ alkyl Or C ₁ -C ₆ haloalkyl; R ₂₆ is C ₁ -C ₆ alkyl or C ₁ -C ₆ haloalkyl; n is 0 or 1; Q is a group selected from the following group consisting of Composition: formula Q ₁ to Q ₅

The arrow indicates the attachment point to the ring incorporating the group A; and wherein X ₁ is O, S or NR ₃ ; R ₃ is a C ₁ -C ₄ alkyl group; R ₂ is a halogen, C ₁ -C ₆ Haloalkyl, C ₁ -C ₄ haloalkylsulfanyl, C ₁ -C ₄ haloalkylsulfinyl, C ₁ -C ₄ haloalkylsulfinyl or C ₁ -C ₆ haloalkoxy; G ₁ and G ₂ is N or CH independently of each other; R ₄ is C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₃ -C ₆ cycloalkyl or C ₁ -C ₄ alkoxy; and the formula Agrochemically acceptable salts, stereoisomers, enantiomers, tautomers and N-oxides of the compound of I.

Compounds of formula I having at least one basic center can form, for example, acid addition salts with strong mineral acids (such as mineral acids, such as perchloric acid, sulfuric acid, nitric acid, nitrose acid, phosphoric acid, or hydrogen halide). Acids), strong organic carboxylic acids (such as unsubstituted or, for example, halogen-substituted C ₁ -C ₄ alkanoic acids, such as acetic acid; such as saturated or unsaturated dicarboxylic acids, such as oxalic 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 organic sulfonic acid (such as unsubstituted or, for example, halogenated Substituted C ₁ -C ₄ alkanesulfonic acid or arylsulfonic acid, such as methanesulfonic acid or p-toluenesulfonic acid). The compound of formula I having at least one acidic group can for example form a salt with a base, such as a mineral salt, such as an alkali metal or alkaline earth metal salt, such as sodium, potassium or magnesium; or with ammonia or an organic amine (such as , Piperidine, pyrrolidine, mono-, di- or tri-lower alkylamines, such as ethylamine, diethylamine, triethylamine or dimethylpropylamine, or mono-, di- or tri-hydroxy lower alkylamines, such as mono Ethanolamine, diethanolamine or triethanolamine) form a salt.

Alkyl groups appearing in the definition of substituents can be linear or branched, and are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, secondary butyl, isobutyl, tri Butyl, pentyl, hexyl and their branched isomers. The alkylsulfinyl group, alkylsulfinyl group, alkylsulfinyl group and alkoxy group are derived from the mentioned alkyl groups.

Halogen is usually fluorine, chlorine, bromine or iodine. Correspondingly, this also applies to halogens in combination with other meanings, such as haloalkyl.

The haloalkyl group preferably has a chain length of from 1 to 6 carbon atoms. Halogenated alkyl groups such as fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2 -Chloroethyl, pentafluoroethyl, 1,1-difluoro-2,2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl and 2,2,2-trichloroethyl Group; preferably trichloromethyl, difluorochloromethyl, difluoromethyl, trifluoromethyl and dichlorofluoromethyl.

The alkoxy group preferably has a preferred chain length of from 1 to 6 carbon atoms. Alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, secondary butoxy and tertiary butoxy, as well as isomers The pentoxy and hexyloxy groups; preferably methoxy and ethoxy.

The alkoxyalkyl group preferably has a chain length of 1 to 6 carbon atoms, and more preferably a chain length of 1 to 4 carbon atoms. Alkoxyalkyl systems such as methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n-propoxymethyl, n-propoxyethyl, isopropoxymethyl Group or isopropoxyethyl.

The alkylsulfanyl group is, for example, methylsulfanyl, ethylsulfanyl, propylsulfanyl, isopropylsulfanyl, butylsulfanyl, pentylsulfanyl, and hexylsulfanyl.

Alkylsulfinyl groups such as methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, butylsulfinyl, pentylsulfinyl , And hexylsulfinyl.

The alkylsulfonyl groups are, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, pentylsulfonyl, and hexylsulfonyl.

Cycloalkyl groups preferably have from 3 to 6 ring carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

The haloalkylsulfanyl group preferably has a chain length of from 1 to 4 carbon atoms. The halogenated alkylsulfanyl group is, for example, difluoromethylsulfanyl, trifluoromethylsulfanyl, or 2,2,2-trifluoroethylsulfanyl. Similar considerations apply to the groups C ₁ -C ₄ haloalkylsulfinyl and C ₁ -C ₄ haloalkylsulfinyl, which can be, for example, trifluoromethylsulfinyl, trifluoromethylsulfinyl Or 2,2,2-trifluoroethylsulfonyl.

The compounds of formula I according to the present invention also include hydrates that may be formed during salt formation.

As listed below, embodiments according to the present invention are provided.

Embodiment 1 provides a compound of formula I as defined above or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof.

Embodiment 2 provides a compound according to Embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein: A is CH or N; R ₁ is ethyl, propyl or isopropyl; R ₁₀ is hydrogen, cyano or -C(O)R ₂₅ , where R ₂₅ is C ₁ -C ₂ haloalkyl; R ₉ is hydrogen, methyl or ethyl ; And n is 1.

Embodiment 3a provides a compound according to Embodiment 1 or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein: A is CH or N; R ₁ is ethyl; R ₁₀ is hydrogen; R ₉ is hydrogen or methyl; and n is 1.

Embodiment 3b provides a compound according to Embodiment 1 or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein: A series N; R ₁ series Ethyl; R ₁₀ is hydrogen; R ₉ is hydrogen or methyl; and n is 1.

Embodiment 4a provides a compound according to Embodiment 1 or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein: A is CH or N; R ₁ is ethyl; R ₁₀ is hydrogen; R ₉ is hydrogen; and n is 1.

Embodiment 4b provides a compound according to Embodiment 1 or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein: A series N; R ₁ series Ethyl; R ₁₀ is hydrogen; R ₉ is hydrogen; and n is 1.

Embodiment 5a provides a compound according to embodiment 1 or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein: A is CH or N; R ₁ is ethyl; R ₁₀ is hydrogen; R ₉ is methyl; and n is 1.

Embodiment 5b provides a compound according to Embodiment 1 or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein: A series N; R ₁ series Ethyl; R ₁₀ is hydrogen; R ₉ is methyl; and n is 1.

Embodiment 6 provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein: R ₇ is hydrogen or C ₁ -C ₄ alkyl; and R ₈ is C ₁ -C ₄ alkyl.

Embodiment 7 provides the compound according to Embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein: R ₇ is hydrogen, methyl Or ethyl; and R ₈ is methyl or ethyl.

Embodiment 8a provides a compound according to Embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein: R ₇ is methyl or ethyl And R ₈ is a methyl group or an ethyl group.

Embodiment 8b provides a compound according to Embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein: R ₇ is a methyl group; and R ₈ is methyl or ethyl.

Embodiment 8c provides a compound according to embodiment 1 or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein: R ₇ is a methyl group; and R ₈ is a methyl group.

其中箭頭指示與摻入有基團A的環的附接點； 並且其中 R₂ 係C₁ -C₂ 鹵代烷基、C₁ -C₂ 鹵代烷基氫硫基、C₁ -C₂ 鹵代烷基亞磺醯基或C₁ -C₂ 鹵代烷基磺醯基； X₁ 係氧或NCH₃ ； R₃ 係C₁ -C₂ 烷基； R₄ 係C₁ -C₂ 烷基、C₁ -C₂ 鹵代烷基、C₁ -C₂ 烷氧基或環丙基；並且 G₁ 和G₂ 彼此獨立地是N或CH。Embodiment 9 provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein: Q is selected from Q ₁ , Q ₂ , Q ₄ and Q ₅ groups

Where the arrow indicates the point of attachment to the ring incorporating the group A; and where R ₂ is a C ₁ -C ₂ haloalkyl group, a C ₁ -C ₂ haloalkyl hydrosulfide group, a C ₁ -C ₂ haloalkylsulfinyl group Alkyl or C ₁ -C ₂ haloalkylsulfonyl; X ₁ is oxygen or NCH ₃ ; R ₃ is C ₁ -C ₂ alkyl; R ₄ is C ₁ -C ₂ alkyl, C ₁ -C ₂ haloalkane Group, C ₁ -C ₂ alkoxy or cyclopropyl; and G ₁ and G ₂ are independently N or CH.

其中箭頭指示與摻入有基團A的環的附接點； 並且其中 R₂ 係C₁ -C₂ 氟烷基、三氟甲基氫硫基、三氟甲基亞磺醯基、三氟甲基磺醯基、二氟甲基氫硫基、二氟甲基亞磺醯基、或二氟甲基磺醯基； X₁ 係NCH₃ ； R₃ 係甲基； R₄ 係甲基、乙基、2,2,2-三氟乙基、甲氧基或環丙基；並且 G₁ 和G₂ 彼此獨立地是N或CH。Embodiment 10 provides the compound according to Embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein: Q is selected from Q ₁ , Q ₂ and Q ₅ groups

Wherein the arrow indicates the attachment point to the ring incorporating the group A; and where R ₂ is a C ₁ -C ₂ fluoroalkyl group, a trifluoromethylsulfinyl group, a trifluoromethylsulfinyl group, and a trifluoromethyl group. Methylsulfonyl, difluoromethylsulfinyl, difluoromethylsulfinyl, or difluoromethylsulfinyl; X ₁ is NCH ₃ ; R ₃ is methyl; R ₄ is methyl, Ethyl, 2,2,2-trifluoroethyl, methoxy or cyclopropyl; and G ₁ and G ₂ are N or CH independently of each other.

其中箭頭指示與摻入有基團A的環的附接點； 並且其中 R₂ 係三氟甲基、五氟乙基、三氟甲基氫硫基、三氟甲基亞磺醯基或三氟甲基磺醯基； X₁ 係NCH₃ ； R₃ 係甲基； R₄ 係乙基、甲氧基或環丙基； 當Q係Q₁ 時，G₁ 係N並且G₂ 係CH，或G₁ 係CH並且G₂ 係N，或G₁ 和G₂ 均是N；並且 當Q係Q₂ 時，G₂ 係CH或N。Embodiment 11a provides a compound according to Embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein: Q is selected from Q ₁ , Q ₂ and Q ₅ groups

Where the arrow indicates the point of attachment to the ring incorporating the group A; and where R ₂ is a trifluoromethyl, pentafluoroethyl, trifluoromethylsulfinyl, trifluoromethylsulfinyl or trifluoromethyl Fluoromethylsulfonyl; X ₁ is NCH ₃ ; R ₃ is methyl; R ₄ is ethyl, methoxy or cyclopropyl; when Q is Q ₁ , G ₁ is N and G ₂ is CH, Or G ₁ is CH and G ₂ is N, or both G ₁ and G ₂ are N; and when Q is Q ₂ , G ₂ is CH or N.

其中箭頭指示與摻入有基團A的環的附接點； 並且其中 R₂ 係三氟甲基、五氟乙基或三氟甲基氫硫基； X₁ 係NCH₃ ； R₃ 係甲基； R₄ 係乙基或環丙基； 當Q係Q₁ 時，G₁ 係N並且G₂ 係CH，或G₁ 係CH並且G₂ 係N，或G₁ 和G₂ 均是N；並且 當Q係Q₂ 時，G₂ 係CH或N。Embodiment 11b provides a compound according to Embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein: Q is selected from Q ₁ , Q ₂ and Q ₅ groups

Wherein the arrow indicates the point of attachment to the ring incorporating the group A; and where R ₂ is a trifluoromethyl, pentafluoroethyl or trifluoromethyl sulfhydryl group; X ₁ is NCH ₃ ; R ₃ is methyl R ₄ is ethyl or cyclopropyl; when Q is Q ₁ , G ₁ is N and G ₂ is CH, or G ₁ is CH and G ₂ is N, or both G ₁ and G ₂ are N; And when Q is Q ₂ , G ₂ is CH or N.

其中箭頭指示與摻入有基團A的環的附接點； 並且其中 R₂ 係三氟甲基； X₁ 係NCH₃ ； 當Q係Q₁ 時，G₁ 係N並且G₂ 係CH，或G₁ 係CH並且G₂ 係N，或G₁ 和G₂ 均是N；並且 當Q係Q₂ 時，G₂ 係CH或N。Embodiment 12 provides a compound according to Embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein: Q series group Q ₁

Where the arrow indicates the attachment point to the ring incorporating the group A; and where R ₂ is a trifluoromethyl group; X ₁ is NCH ₃ ; when Q is Q ₁ , G ₁ is N and G ₂ is CH, Or G ₁ is CH and G ₂ is N, or both G ₁ and G ₂ are N; and when Q is Q ₂ , G ₂ is CH or N.

其中箭頭指示與摻入有基團A的環的附接點； 並且其中 R₂ 係三氟甲基、五氟乙基、三氟甲基氫硫基、三氟甲基亞磺醯基或三氟甲基磺醯基；並且 G₂ 係CH或N。Embodiment 13a provides a compound according to Embodiment 1 or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein: Q series group Q ₂

Where the arrow indicates the point of attachment to the ring incorporating the group A; and where R ₂ is a trifluoromethyl, pentafluoroethyl, trifluoromethylsulfinyl, trifluoromethylsulfinyl or trifluoromethyl Fluoromethylsulfonyl; and G ₂ is CH or N.

其中箭頭指示與摻入有基團A的環的附接點； 並且其中 R₂ 係三氟甲基、五氟乙基或三氟甲基氫硫基；並且 G₂ 係CH或N。Embodiment 13b provides a compound according to Embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein: Q series group Q ₂

Where the arrow indicates the point of attachment to the ring incorporating the group A; and where R ₂ is a trifluoromethyl, pentafluoroethyl, or trifluoromethyl sulfhydryl group; and G ₂ is CH or N.

其中箭頭指示與摻入有基團A的環的附接點； 並且其中 R₂ 係三氟甲基； R₃ 係甲基；並且 R₄ 係乙基或環丙基。Embodiment 14 provides a compound according to Embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein: Q series group Q ₅

Where the arrow indicates the point of attachment to the ring incorporating the group A; and where R ₂ is trifluoromethyl; R ₃ is methyl; and R ₄ is ethyl or cyclopropyl.

其中箭頭指示與摻入有基團A的環的附接點； 並且其中 R₂ 係C₁ -C₂ 鹵代烷基、C₁ -C₂ 鹵代烷基氫硫基、C₁ -C₂ 鹵代烷基亞磺醯基或C₁ -C₂ 鹵代烷基磺醯基； X₁ 係氧或NCH₃ ； R₃ 係C₁ -C₂ 烷基； R₄ 係C₁ -C₂ 烷基、C₁ -C₂ 鹵代烷基、C₁ -C₂ 烷氧基或環丙基；並且 G₁ 和G₂ 彼此獨立地是N或CH。Embodiment 15 provides a compound according to embodiment 1 or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein: A is CH or N; R ₁ is ethyl, propyl or isopropyl; R ₁₀ is hydrogen, cyano or -C(O)R ₂₅ , where R ₂₅ is C ₁ -C ₂ haloalkyl; R ₉ is hydrogen, methyl or ethyl ; N is 1; R ₇ is hydrogen or C ₁ -C ₄ alkyl and R ₈ is C ₁ -C ₄ alkyl; Q is a group selected from Q ₁ , Q ₂ , Q ₄ and Q ₅

Where the arrow indicates the point of attachment to the ring incorporating the group A; and where R ₂ is a C ₁ -C ₂ haloalkyl group, a C ₁ -C ₂ haloalkyl hydrosulfide group, a C ₁ -C ₂ haloalkylsulfinyl group Alkyl or C ₁ -C ₂ haloalkylsulfonyl; X ₁ is oxygen or NCH ₃ ; R ₃ is C ₁ -C ₂ alkyl; R ₄ is C ₁ -C ₂ alkyl, C ₁ -C ₂ haloalkane Group, C ₁ -C ₂ alkoxy or cyclopropyl; and G ₁ and G ₂ are independently N or CH.

其中箭頭指示與摻入有基團A的環的附接點； 並且其中 R₂ 係C₁ -C₂ 氟烷基、三氟甲基氫硫基、三氟甲基亞磺醯基、三氟甲基磺醯基、二氟甲基氫硫基、二氟甲基亞磺醯基、或二氟甲基磺醯基； X₁ 係NCH₃ ； R₃ 係甲基； R₄ 係甲基、乙基、2,2,2-三氟乙基、甲氧基或環丙基；並且 G₁ 和G₂ 彼此獨立地是N或CH。Embodiment 16 provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof according to embodiment 1, wherein: A is CH or N; R ₁ is ethyl; R ₁₀ is hydrogen; R ₉ is hydrogen or methyl; n is 1; R ₇ is hydrogen, methyl or ethyl and R ₈ is methyl or ethyl; Q is selected from Q ₁ , Q ₂ and Q ₅ groups

Wherein the arrow indicates the attachment point to the ring incorporating the group A; and where R ₂ is a C ₁ -C ₂ fluoroalkyl group, a trifluoromethylsulfinyl group, a trifluoromethylsulfinyl group, and a trifluoromethyl group. Methylsulfonyl, difluoromethylsulfinyl, difluoromethylsulfinyl, or difluoromethylsulfinyl; X ₁ is NCH ₃ ; R ₃ is methyl; R ₄ is methyl, Ethyl, 2,2,2-trifluoroethyl, methoxy or cyclopropyl; and G ₁ and G ₂ are N or CH independently of each other.

其中箭頭指示與摻入有基團A的環的附接點； 並且其中 R₂ 係C₁ -C₂ 氟烷基、三氟甲基氫硫基、三氟甲基亞磺醯基、三氟甲基磺醯基、二氟甲基氫硫基、二氟甲基亞磺醯基、或二氟甲基磺醯基； X₁ 係NCH₃ ； R₃ 係甲基； R₄ 係甲基、乙基、2,2,2-三氟乙基、甲氧基或環丙基；並且 G₁ 和G₂ 彼此獨立地是N或CH。Embodiment 17 provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof according to embodiment 1, wherein: A is CH or N; R ₁ is ethyl; R ₁₀ is hydrogen; R ₉ is hydrogen or methyl; n is 1; R ₇ is methyl and R ₈ is methyl; Q is a group selected from Q ₁ , Q ₂ and Q ₅

Wherein the arrow indicates the attachment point to the ring incorporating the group A; and where R ₂ is a C ₁ -C ₂ fluoroalkyl group, a trifluoromethylsulfinyl group, a trifluoromethylsulfinyl group, and a trifluoromethyl group. Methylsulfonyl, difluoromethylsulfinyl, difluoromethylsulfinyl, or difluoromethylsulfinyl; X ₁ is NCH ₃ ; R ₃ is methyl; R ₄ is methyl, Ethyl, 2,2,2-trifluoroethyl, methoxy or cyclopropyl; and G ₁ and G ₂ are N or CH independently of each other.

其中箭頭指示與摻入有基團A的環的附接點； 並且其中 R₂ 係三氟甲基、五氟乙基、三氟甲基氫硫基、三氟甲基亞磺醯基或三氟甲基磺醯基； X₁ 係NCH₃ ； R₃ 係甲基； R₄ 係乙基、甲氧基或環丙基； 當Q係Q₁ 時，G₁ 係N並且G₂ 係CH，或G₁ 係CH並且G₂ 係N，或G₁ 和G₂ 均是N；並且 當Q係Q₂ 時，G₂ 係CH或N。Embodiment 18 provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof according to embodiment 1, wherein: A series N; R ₁ series Ethyl; R ₁₀ is hydrogen; R ₉ is hydrogen or methyl; n is 1; R ₇ is methyl and R ₈ is methyl; Q is a group selected from Q ₁ , Q ₂ and Q ₅

Where the arrow indicates the point of attachment to the ring incorporating the group A; and where R ₂ is a trifluoromethyl, pentafluoroethyl, trifluoromethylsulfinyl, trifluoromethylsulfinyl or trifluoromethyl Fluoromethylsulfonyl; X ₁ is NCH ₃ ; R ₃ is methyl; R ₄ is ethyl, methoxy or cyclopropyl; when Q is Q ₁ , G ₁ is N and G ₂ is CH, Or G ₁ is CH and G ₂ is N, or both G ₁ and G ₂ are N; and when Q is Q ₂ , G ₂ is CH or N.

其中箭頭指示與摻入有基團A的環的附接點； 並且其中 R₂ 係三氟甲基、五氟乙基或三氟甲基氫硫基； X₁ 係NCH₃ ； R₃ 係甲基； R₄ 係乙基或環丙基； 當Q係Q₁ 時，G₁ 係N並且G₂ 係CH，或G₁ 係CH並且G₂ 係N，或G₁ 和G₂ 均是N；並且 當Q係Q₂ 時，G₂ 係CH或N。Embodiment 19 provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof according to embodiment 1, wherein: A is N; R ₁ is Ethyl; R ₁₀ is hydrogen; R ₉ is hydrogen or methyl; n is 1; R ₇ is methyl and R ₈ is methyl; Q is a group selected from Q ₁ , Q ₂ and Q ₅

Wherein the arrow indicates the point of attachment to the ring incorporating the group A; and where R ₂ is a trifluoromethyl, pentafluoroethyl or trifluoromethyl sulfhydryl group; X ₁ is NCH ₃ ; R ₃ is methyl R ₄ is ethyl or cyclopropyl; when Q is Q ₁ , G ₁ is N and G ₂ is CH, or G ₁ is CH and G ₂ is N, or both G ₁ and G ₂ are N; And when Q is Q ₂ , G ₂ is CH or N.

其中箭頭指示與摻入有基團A的環的附接點； 並且其中 R₂ 係三氟甲基； X₁ 係NCH₃ ；並且 G₁ 係N並且G₂ 係CH，或者G₁ 係CH並且G₂ 係N，或者G₁ 和G₂ 都是N。Embodiment 20 provides a compound according to embodiment 1 or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof according to embodiment 1, wherein: A is N; R ₁ is Ethyl; R ₁₀ is hydrogen; R ₉ is hydrogen or methyl; n is 1; R ₇ is methyl and R ₈ is methyl; Q is group Q ₁

Where the arrow indicates the point of attachment to the ring incorporating the group A; and where R ₂ is trifluoromethyl; X ₁ is NCH ₃ ; and G ₁ is N and G ₂ is CH, or G ₁ is CH and G ₂ is N, or both G ₁ and G ₂ are N.

其中箭頭指示與摻入有基團A的環的附接點； 並且其中 R₂ 係三氟甲基； X₁ 係NCH₃ ；並且 G₁ 係N並且G₂ 係CH，或者G₁ 係CH並且G₂ 係N，或者G₁ 和G₂ 都是N。Embodiment 21 provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof according to embodiment 1, wherein: A is N; R ₁ is Ethyl; R ₁₀ is hydrogen; R ₉ is hydrogen; n is 1; R ₇ is methyl and R ₈ is methyl; Q is group Q ₁

Where the arrow indicates the point of attachment to the ring incorporating the group A; and where R ₂ is trifluoromethyl; X ₁ is NCH ₃ ; and G ₁ is N and G ₂ is CH, or G ₁ is CH and G ₂ is N, or both G ₁ and G ₂ are N.

其中箭頭指示與摻入有基團A的環的附接點； 並且其中 R₂ 係三氟甲基； X₁ 係NCH₃ ；並且 G₁ 係N並且G₂ 係CH，或者G₁ 係CH並且G₂ 係N，或者G₁ 和G₂ 都是N。Embodiment 22 provides a compound according to embodiment 1 or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein: A is N; R ₁ is Ethyl; R ₁₀ is hydrogen; R ₉ is methyl; n is 1; R ₇ is methyl and R ₈ is methyl; Q is group Q ₁

Where the arrow indicates the point of attachment to the ring incorporating the group A; and where R ₂ is trifluoromethyl; X ₁ is NCH ₃ ; and G ₁ is N and G ₂ is CH, or G ₁ is CH and G ₂ is N, or both G ₁ and G ₂ are N.

其中箭頭指示與摻入有基團A的環的附接點； 並且其中 R₂ 係三氟甲基、五氟乙基、三氟甲基氫硫基、三氟甲基亞磺醯基或三氟甲基磺醯基；並且 G₂ 係CH或N。Embodiment 23 provides a compound according to Embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein: A is N; R ₁ is Ethyl; R ₁₀ is hydrogen; R ₉ is hydrogen; n is 1; R ₇ is methyl and R ₈ is methyl; Q is group Q ₂

Where the arrow indicates the point of attachment to the ring incorporating the group A; and where R ₂ is a trifluoromethyl, pentafluoroethyl, trifluoromethylsulfinyl, trifluoromethylsulfinyl or trifluoromethyl Fluoromethylsulfonyl; and G ₂ is CH or N.

其中箭頭指示與摻入有基團A的環的附接點； 並且其中 R₂ 係三氟甲基、五氟乙基或三氟甲基氫硫基；並且 G₂ 係CH或N。Embodiment 24 provides a compound according to embodiment 1 or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein: A is N; R ₁ is Ethyl; R ₁₀ is hydrogen; R ₉ is hydrogen; n is 1; R ₇ is methyl and R ₈ is methyl; Q is group Q ₂

Where the arrow indicates the point of attachment to the ring incorporating the group A; and where R ₂ is a trifluoromethyl, pentafluoroethyl, or trifluoromethyl sulfhydryl group; and G ₂ is CH or N.

其中箭頭指示與摻入有基團A的環的附接點； 並且其中 R₂ 係三氟甲基、五氟乙基、三氟甲基氫硫基、三氟甲基亞磺醯基或三氟甲基磺醯基；並且 G₂ 係CH或N。Embodiment 25 provides a compound according to embodiment 1 or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein: A is CH; R ₁ is Ethyl; R ₁₀ is hydrogen; R ₉ is hydrogen; n is 1; R ₇ is methyl and R ₈ is methyl; Q is group Q ₂

Where the arrow indicates the point of attachment to the ring incorporating the group A; and where R ₂ is a trifluoromethyl, pentafluoroethyl, trifluoromethylsulfinyl, trifluoromethylsulfinyl or trifluoromethyl Fluoromethylsulfonyl; and G ₂ is CH or N.

其中箭頭指示與摻入有基團A的環的附接點； 並且其中 R₂ 係三氟甲基、五氟乙基或三氟甲基氫硫基；並且 G₂ 係CH或N。Embodiment 26 provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof according to embodiment 1, wherein: A series CH; R ₁ series Ethyl; R ₁₀ is hydrogen; R ₉ is hydrogen; n is 1; R ₇ is methyl and R ₈ is methyl; Q is group Q ₂

Where the arrow indicates the point of attachment to the ring incorporating the group A; and where R ₂ is a trifluoromethyl, pentafluoroethyl, or trifluoromethyl sulfhydryl group; and G ₂ is CH or N.

其中箭頭指示與摻入有基團A的環的附接點； 並且其中 R₂ 係三氟甲基； R₃ 係甲基；並且 R₄ 係乙基或環丙基。Embodiment 27 provides a compound according to embodiment 1 or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof according to embodiment 1, wherein: A is N; R ₁ is Ethyl; R ₁₀ is hydrogen; R ₉ is hydrogen; n is 1; R ₇ is methyl and R ₈ is methyl; Q is group Q ₅

Wherein the arrow indicates the point of attachment to the ring incorporating the group A; and where R ₂ is a trifluoromethyl group; R ₃ is a methyl group; and R ₄ is an ethyl group or a cyclopropyl group.

Embodiment 28 provides according to Embodiment 1, 2, 3a, 3b, 4a, 4b, 6, 7, 8a, 8b, 8c, 9, 10, 11a, 11b, 13a, 13b, 14, 15, 16, 17, The compound of any one of 18, 19, 23 or 24, or its agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide, condition: exclude 2- [[5-(Ethylsulfonylimino)-6-[7-(1,1,2,2,2-pentafluoroethyl)imidazo[1,2-c]pyrimidin-2-yl] -3-pyridyl]oxy]-2-methyl-propionitrile; and 2-[[5-(ethylsulfonylimino)-6-[7-(trifluoromethyl)imidazo[1 ,2-c]pyrimidin-2-yl]-3-pyridyl]oxy]-2-methyl-propionitrile.

(I-1)； 其中R₁ 、R₂ 、R₃ 、R₇ 、R₈ 、R₉ 、R₁₀ 、A和n係如上式I所定義的。A preferred group of compounds of formula I is represented by compounds of formula I-1

(I-1); wherein R ₁ , R ₂ , R ₃ , R ₇ , R ₈ , R ₉ , R ₁₀ , A and n are as defined in Formula I above.

In a preferred group of compounds of formula I-1, A is CH or N; R ₁ is ethyl, propyl or isopropyl; R ₂ is C ₁ -C ₂ haloalkyl, C ₁ -C ₂ haloalkyl Sulfanyl group, C ₁ -C ₂ haloalkylsulfinyl or C ₁ -C ₂ haloalkylsulfinyl; R ₃ is C ₁ -C ₂ alkyl; R ₉ is hydrogen, methyl or ethyl; R ₁₀ is hydrogen, cyano or -C(O)R ₂₅ , wherein R ₂₅ is a C ₁ -C ₂ haloalkyl group and n is 1.

In another preferred group of compounds of formula I-1, A is CH or N; R ₁ is ethyl; R ₂ is C ₁ -C ₂ fluoroalkyl, trifluoromethylsulfanyl, trifluoromethyl Sulfinyl, trifluoromethylsulfinyl, difluoromethylsulfanyl, difluoromethylsulfinyl, or difluoromethylsulfinyl; R ₃ is methyl; R ₉ is hydrogen Or methyl, preferably R ₉ is hydrogen; R ₁₀ is hydrogen; and n is 1.

In another preferred group of compounds of formula I-1, R ₇ is hydrogen or C ₁ -C ₄ alkyl; and R ₈ is C ₁ -C ₄ alkyl.

In another preferred group of compounds of formula 1-1, R ₇ is hydrogen, methyl or ethyl; and R ₈ is methyl or ethyl; preferably R ₇ is methyl; and R ₈ is methyl.

In all preferred embodiments of the compound of formula I-1 and the compound of formula I-1 above, unless otherwise specified, R ₁ , R ₂ , R ₃ , R ₇ , R ₈ , R ₉ , R ₁₀ , A and n are as defined in the above formula I; A is CH or N, preferably A is N; R ₂ is trifluoromethyl, pentafluoroethyl or trifluoromethylsulfanyl; preferably R ₂ is trifluoromethyl; R ₃ is methyl; R ₇ is methyl or ethyl, preferably R ₇ is methyl; R ₈ is methyl or ethyl, preferably R ₈ is Methyl; R ₉ is hydrogen; R ₁₀ is hydrogen; and n is 1.

(I-2)； 其中R₁ 、R₂ 、R₃ 、R₇ 、R₈ 、R₉ 、R₁₀ 、A和n係如上式I所定義的。Another preferred group of compounds of formula I is represented by compounds of formula I-2

(I-2); wherein R ₁ , R ₂ , R ₃ , R ₇ , R ₈ , R ₉ , R ₁₀ , A and n are as defined in Formula I above.

In a preferred group of compounds of formula I-2, A is CH or N; R ₁ is ethyl, propyl or isopropyl; R ₂ is C ₁ -C ₂ haloalkyl, C ₁ -C ₂ haloalkyl Sulfanyl group, C ₁ -C ₂ haloalkylsulfinyl or C ₁ -C ₂ haloalkylsulfinyl; R ₃ is C ₁ -C ₂ alkyl; R ₉ is hydrogen, methyl or ethyl; R ₁₀ is hydrogen, cyano or -C(O)R ₂₅ , wherein R ₂₅ is a C ₁ -C ₂ haloalkyl group and n is 1.

In another preferred group of compounds of formula I-2, A is CH or N; R ₁ is ethyl; R ₂ is C ₁ -C ₂ fluoroalkyl, trifluoromethylsulfanyl, trifluoromethyl Sulfinyl, trifluoromethylsulfinyl, difluoromethylsulfanyl, difluoromethylsulfinyl, or difluoromethylsulfinyl; R ₃ is methyl; R ₉ is hydrogen Or methyl, preferably R ₉ is hydrogen; R ₁₀ is hydrogen; and n is 1.

In another preferred group of compounds of formula I-2, R ₇ is hydrogen or C ₁ -C ₄ alkyl; and R ₈ is C ₁ -C ₄ alkyl.

In another preferred group of compounds of formula I-2, R ₇ is hydrogen, methyl or ethyl; and R ₈ is methyl or ethyl; preferably R ₇ is methyl; and R ₈ is methyl.

In all preferred embodiments of the compound of formula I-2 and the compound of formula I-2 above, unless otherwise specified, R ₁ , R ₂ , R ₃ , R ₇ , R ₈ , R ₉ , R ₁₀ , A and n are as defined in the above formula I; preferably A is CH or N, more preferably A is N; R ₂ is trifluoromethyl, pentafluoroethyl or trifluoromethyl hydrogen sulfide R ₂ is preferably trifluoromethyl; R ₃ is methyl; R ₇ is methyl or ethyl, preferably R ₇ is methyl; R ₈ is methyl or ethyl, preferably Where R ₈ is methyl; R ₉ is hydrogen; R ₁₀ is hydrogen; and n is 1.

(I-3) 其中R₁ 、R₂ 、R₃ 、R₇ 、R₈ 、R₉ 、R₁₀ 、A和n係如上式I所定義的。Another preferred group of compounds of formula I is represented by compounds of formula I-3

(I-3) wherein R ₁ , R ₂ , R ₃ , R ₇ , R ₈ , R ₉ , R ₁₀ , A and n are as defined in Formula I above.

In a preferred group of compounds of formula I-3, A is CH or N; R ₁ is ethyl, propyl or isopropyl; R ₂ is C ₁ -C ₂ haloalkyl, C ₁ -C ₂ haloalkyl Sulfanyl group, C ₁ -C ₂ haloalkylsulfinyl or C ₁ -C ₂ haloalkylsulfinyl; R ₃ is C ₁ -C ₂ alkyl; R ₉ is hydrogen, methyl or ethyl; R ₁₀ is hydrogen, cyano or -C(O)R ₂₅ , wherein R ₂₅ is a C ₁ -C ₂ haloalkyl group and n is 1.

In another preferred group of compounds of formula I-3, A is CH or N; R ₁ is ethyl; R ₂ is C ₁ -C ₂ fluoroalkyl, trifluoromethylsulfanyl, trifluoromethyl Sulfinyl, trifluoromethylsulfinyl, difluoromethylsulfanyl, difluoromethylsulfinyl, or difluoromethylsulfinyl; R ₃ is methyl; R ₉ is hydrogen Or methyl, preferably R ₉ is hydrogen; R ₁₀ is hydrogen; and n is 1.

In another preferred group of compounds of formula I-3, R ₇ is hydrogen or C ₁ -C ₄ alkyl; and R ₈ is C ₁ -C ₄ alkyl.

In another preferred group of compounds of formula I-3, R ₇ is hydrogen, methyl or ethyl; and R ₈ is methyl or ethyl; preferably R ₇ is methyl; and R ₈ is methyl.

In all preferred embodiments of the compound of formula I-3 and the compound of formula I-3 above, unless otherwise specified, R ₁ , R ₂ , R ₃ , R ₇ , R ₈ , R ₉ , R ₁₀ , A and n are as defined in the above formula I; preferably A is CH or N, more preferably A is N; R ₂ is trifluoromethyl, pentafluoroethyl or trifluoromethyl hydrogen sulfide R ₂ is preferably trifluoromethyl; R ₃ is methyl; R ₇ is methyl or ethyl, preferably R ₇ is methyl; R ₈ is methyl or ethyl, preferably Where R ₈ is methyl; R ₉ is hydrogen; R ₁₀ is hydrogen; and n is 1.

(I-4) 其中R₁ 、R₂ 、R_{3 、} R₄ 、R₇ 、R₈ 、R₉ 、R₁₀ 、A和n係如上式I所定義的。Another preferred group of compounds of formula I is represented by compounds of formula I-4

(I-4) wherein R ₁ , R ₂ , R _{3 ,} R ₄ , R ₇ , R ₈ , R ₉ , R ₁₀ , A and n are as defined in Formula I above.

In a preferred group of compounds of formula I-4, A is CH or N; R ₁ is ethyl, propyl or isopropyl; R ₂ is C ₁ -C ₂ haloalkyl, C ₁ -C ₂ haloalkyl Sulfhydryl group, C ₁ -C ₂ haloalkylsulfinyl or C ₁ -C ₂ haloalkylsulfinyl; R ₃ is C ₁ -C ₂ alkyl; R ₄ is C ₁ -C ₂ alkyl, C ₁ -C ₂ haloalkyl, C ₁ -C ₂ alkoxy or cyclopropyl; R ₉ is hydrogen, methyl or ethyl; R ₁₀ is hydrogen, cyano or -C(O)R ₂₅ , where R ₂₅ is C ₁ -C ₂ haloalkyl and n is 1.

In another preferred group of compounds of formula I-4, A is CH or N; R ₁ is ethyl; R ₂ is C ₁ -C ₂ fluoroalkyl, trifluoromethylsulfanyl, trifluoromethyl Sulfinyl, trifluoromethylsulfinyl, difluoromethylsulfinyl, difluoromethylsulfinyl, or difluoromethylsulfinyl; R ₃ is methyl; R ₄ is methyl R ₉ is hydrogen or methyl, preferably R ₉ is hydrogen; R ₁₀ is hydrogen; and n is 1.

In another preferred group of compounds of formula I-4, R ₄ is ethyl or cyclopropyl.

In another preferred group of compounds of formula I-4, R ₇ is hydrogen or C ₁ -C ₄ alkyl; and R ₈ is C ₁ -C ₄ alkyl.

In another preferred group of compounds of formula I-4, R ₇ is hydrogen, methyl or ethyl; and R ₈ is methyl or ethyl; preferably R ₇ is methyl; and R ₈ is methyl.

In all preferred embodiments of the compound of formula I-4 and the compound of formula I-4 above, unless otherwise specified, R ₁ , R ₂ , R ₃ , R ₄ , R ₇ , R ₈ , R ₉ , R ₁₀ , A and n are as defined in the above formula I; preferably A is CH or N, more preferably A is N; R ₂ is trifluoromethyl, pentafluoroethyl or trifluoromethyl R ₂ is trifluoromethyl; R ₃ is methyl; R ₄ is ethyl or cyclopropyl; R ₇ is methyl or ethyl, preferably R ₇ is methyl R ₈ is methyl or ethyl, preferably R ₈ is methyl; R ₉ is hydrogen; R ₁₀ is hydrogen; and n is 1.

(I-5) 其中R₁ 、R₂ 、R₇ 、R₈ 、R₉ 、R₁₀ 、A和n係如上式I所定義的。Another preferred group of compounds of formula I is represented by compounds of formula I-5

(I-5) wherein R ₁ , R ₂ , R ₇ , R ₈ , R ₉ , R ₁₀ , A and n are as defined in Formula I above.

In a preferred group of compounds of formula I-5, A is CH or N; R ₁ is ethyl, propyl or isopropyl; R ₂ is C ₁ -C ₂ haloalkyl, C ₁ -C ₂ haloalkyl Sulfhydryl, C ₁ -C ₂ haloalkylsulfinyl or C ₁ -C ₂ haloalkylsulfinyl; R ₉ is hydrogen, methyl or ethyl; R ₁₀ is hydrogen, cyano or -C( O) R ₂₅ , wherein R ₂₅ is a C ₁ -C ₂ haloalkyl group and n is 1.

In another preferred group of compounds of formula I-5, A is CH or N; R ₁ is ethyl; R ₂ is C ₁ -C ₂ fluoroalkyl, trifluoromethylsulfanyl, trifluoromethyl Sulfinyl, trifluoromethylsulfinyl, difluoromethylsulfinyl, difluoromethylsulfinyl, or difluoromethylsulfinyl; R ₉ is hydrogen or methyl, preferably R ₉ is hydrogen; R ₁₀ is hydrogen; and n is 1.

In another preferred group of compounds of formula I-5, R ₇ is hydrogen or C ₁ -C ₄ alkyl; and R ₈ is C ₁ -C ₄ alkyl.

In another preferred group of compounds of formula I-5, R ₇ is hydrogen, methyl or ethyl; and R ₈ is methyl or ethyl; preferably R ₇ is methyl; and R ₈ is methyl.

In all preferred embodiments of the compound of formula I-5 and the compound of formula I-5 above, unless otherwise specified, R ₁ , R ₂ , R ₇ , R ₈ , R ₉ , R ₁₀ , A and n is as defined in the above formula I; preferably A is CH or N, more preferably A is N; R ₂ is trifluoromethyl, pentafluoroethyl or trifluoromethylsulfanyl; Preferably, R ₂ is trifluoromethyl; R ₇ is methyl or ethyl, preferably R ₇ is methyl; R ₈ is methyl or ethyl, preferably R ₈ is methyl; R ₉ is hydrogen; R ₁₀ is hydrogen; and n is 1.

(I-6) 其中R₁ 、R₂ 、R₇ 、R₈ 、R₉ 、R₁₀ 、A和n係如上式I所定義的。Another preferred group of compounds of formula I is represented by compounds of formula I-6

(I-6) wherein R ₁ , R ₂ , R ₇ , R ₈ , R ₉ , R ₁₀ , A and n are as defined in Formula I above.

In a preferred group of compounds of formula I-6, A is CH or N; R ₁ is ethyl, propyl or isopropyl; R ₂ is C ₁ -C ₂ haloalkyl, C ₁ -C ₂ haloalkyl Sulfhydryl, C ₁ -C ₂ haloalkylsulfinyl or C ₁ -C ₂ haloalkylsulfinyl; R ₉ is hydrogen, methyl or ethyl; R ₁₀ is hydrogen, cyano or -C( O) R ₂₅ , wherein R ₂₅ is a C ₁ -C ₂ haloalkyl group and n is 1.

In another preferred group of compounds of formula I-6, A is CH or N; R ₁ is ethyl; R ₂ is C ₁ -C ₂ fluoroalkyl, trifluoromethylsulfanyl, trifluoromethyl Sulfinyl, trifluoromethylsulfinyl, difluoromethylsulfinyl, difluoromethylsulfinyl, or difluoromethylsulfinyl; R ₉ is hydrogen or methyl, preferably R ₉ is hydrogen; R ₁₀ is hydrogen; and n is 1.

In another preferred group of compounds of formula I-6, R ₇ is hydrogen or C ₁ -C ₄ alkyl; and R ₈ is C ₁ -C ₄ alkyl.

In another preferred group of compounds of formula I-6, R ₇ is hydrogen, methyl or ethyl; and R ₈ is methyl or ethyl; preferably R ₇ is methyl; and R ₈ is methyl.

In all preferred embodiments of the compound of formula I-6 and the compound of formula I-6 above, unless otherwise specified, R ₁ , R ₂ , R ₇ , R ₈ , R ₉ , R ₁₀ , A and n is as defined in the above formula I; preferably A is CH or N, more preferably A is N; R ₂ is trifluoromethyl, pentafluoroethyl or trifluoromethylsulfanyl; Preferably, R ₂ is trifluoromethyl; R ₇ is methyl or ethyl, preferably R ₇ is methyl; R ₈ is methyl or ethyl, preferably R ₈ is methyl; R ₉ is hydrogen; R ₁₀ is hydrogen; and n is 1.

(I-7) 其中R₁ 、R₂ 、R₇ 、R₈ 、R₉ 、R₁₀ 、A和n係如上式I所定義的。Another preferred group of compounds of formula I is represented by compounds of formula I-7

(I-7) wherein R ₁ , R ₂ , R ₇ , R ₈ , R ₉ , R ₁₀ , A and n are as defined in Formula I above.

In a preferred group of compounds of formula I-7, A is CH or N; R ₁ is ethyl, propyl or isopropyl; R ₂ is C ₁ -C ₂ haloalkyl, C ₁ -C ₂ haloalkyl Sulfhydryl, C ₁ -C ₂ haloalkylsulfinyl or C ₁ -C ₂ haloalkylsulfinyl; R ₉ is hydrogen, methyl or ethyl; R ₁₀ is hydrogen, cyano or -C( O) R ₂₅ , wherein R ₂₅ is a C ₁ -C ₂ haloalkyl group and n is 1.

In another preferred group of compounds of formula I-7, A is CH or N; R ₁ is ethyl; R ₂ is C ₁ -C ₂ fluoroalkyl, trifluoromethylsulfanyl, trifluoromethyl Sulfinyl, trifluoromethylsulfinyl, difluoromethylsulfinyl, difluoromethylsulfinyl, or difluoromethylsulfinyl; R ₉ is hydrogen or methyl, preferably R ₉ is hydrogen; R ₁₀ is hydrogen; and n is 1.

In another preferred group of compounds of formula I-7, R ₇ is hydrogen or C ₁ -C ₄ alkyl; and R ₈ is C ₁ -C ₄ alkyl.

In another preferred group of compounds of formula I-7, R ₇ is hydrogen, methyl or ethyl; and R ₈ is methyl or ethyl; preferably R ₇ is methyl; and R ₈ is methyl.

In all preferred embodiments of the compound of formula I-7 and the compound of formula I-7 above, unless otherwise specified, R ₁ , R ₂ , R ₇ , R ₈ , R ₉ , R ₁₀ , A and n is as defined in the above formula I; preferably A is CH or N, more preferably A is N; R ₂ is trifluoromethyl, pentafluoroethyl or trifluoromethylsulfanyl; Preferably, R ₂ is trifluoromethyl; R ₇ is methyl or ethyl, preferably R ₇ is methyl; R ₈ is methyl or ethyl, preferably R ₈ is methyl; R ₉ is hydrogen; R ₁₀ is hydrogen; and n is 1.

(I-8) 其中R₁ 、R₂ 、R₇ 、R₈ 、R₉ 、R₁₀ 、A和n係如上式I所定義的。Another preferred group of compounds of formula I is represented by compounds of formula I-8

(I-8) wherein R ₁ , R ₂ , R ₇ , R ₈ , R ₉ , R ₁₀ , A and n are as defined in Formula I above.

In a preferred group of compounds of formula I-8, A is CH or N; R ₁ is ethyl, propyl or isopropyl; R ₂ is C ₁ -C ₂ haloalkyl, C ₁ -C ₂ haloalkyl Sulfhydryl, C ₁ -C ₂ haloalkylsulfinyl or C ₁ -C ₂ haloalkylsulfinyl; R ₉ is hydrogen, methyl or ethyl; R ₁₀ is hydrogen, cyano or -C( O) R ₂₅ , wherein R ₂₅ is a C ₁ -C ₂ haloalkyl group and n is 1.

In another preferred group of compounds of formula I-8, A is CH or N; R ₁ is ethyl; R ₂ is C ₁ -C ₂ fluoroalkyl, trifluoromethylsulfanyl, trifluoromethyl Sulfinyl, trifluoromethylsulfinyl, difluoromethylsulfinyl, difluoromethylsulfinyl, or difluoromethylsulfinyl; R ₉ is hydrogen or methyl, preferably R ₉ is hydrogen; R ₁₀ is hydrogen; and n is 1.

In another preferred group of compounds of formula I-8, R ₇ is hydrogen or C ₁ -C ₄ alkyl; and R ₈ is C ₁ -C ₄ alkyl.

In another preferred group of compounds of formula I-8, R ₇ is hydrogen, methyl or ethyl; and R ₈ is methyl or ethyl; preferably R ₇ is methyl; and R ₈ is methyl.

In all preferred embodiments of the compound of formula I-8 and the compound of formula I-8 above, unless otherwise specified, R ₁ , R ₂ , R ₇ , R ₈ , R ₉ , R ₁₀ , A and n is as defined in the above formula I; preferably A is CH or N, more preferably A is N; R ₂ is trifluoromethyl, pentafluoroethyl or trifluoromethylsulfanyl; Preferably, R ₂ is trifluoromethyl; R ₇ is methyl or ethyl, preferably R ₇ is methyl; R ₈ is methyl or ethyl, preferably R ₈ is methyl; R ₉ is hydrogen; R ₁₀ is hydrogen; and n is 1.

(I-9) 其中R₁ 、R₂ 、R₇ 、R₈ 、R₉ 、R₁₀ 、A和n係如上式I所定義的。Another preferred group of compounds of formula I is represented by compounds of formula I-9

(I-9) wherein R ₁ , R ₂ , R ₇ , R ₈ , R ₉ , R ₁₀ , A and n are as defined in Formula I above.

In a preferred group of compounds of formula I-9, A is CH or N; R ₁ is ethyl, propyl or isopropyl; R ₂ is C ₁ -C ₂ haloalkyl, C ₁ -C ₂ haloalkyl Sulfhydryl, C ₁ -C ₂ haloalkylsulfinyl or C ₁ -C ₂ haloalkylsulfinyl; R ₉ is hydrogen, methyl or ethyl; R ₁₀ is hydrogen, cyano or -C( O) R ₂₅ , wherein R ₂₅ is a C ₁ -C ₂ haloalkyl group and n is 1.

In another preferred group of compounds of formula I-9, A is CH or N; R ₁ is ethyl; R ₂ is C ₁ -C ₂ fluoroalkyl, trifluoromethylsulfanyl, trifluoromethyl Sulfinyl, trifluoromethylsulfinyl, difluoromethylsulfinyl, difluoromethylsulfinyl, or difluoromethylsulfinyl; R ₉ is hydrogen or methyl, preferably R ₉ is hydrogen; R ₁₀ is hydrogen; and n is 1.

In another preferred group of compounds of formula I-9, R ₇ is hydrogen or C ₁ -C ₄ alkyl; and R ₈ is C ₁ -C ₄ alkyl.

In another preferred group of compounds of formula I-9, R ₇ is hydrogen, methyl or ethyl; and R ₈ is methyl or ethyl; preferably R ₇ is methyl; and R ₈ is methyl.

In all preferred embodiments of the compound of formula I-9 and the compound of formula I-9 above, unless otherwise specified, R ₁ , R ₂ , R ₇ , R ₈ , R ₉ , R ₁₀ , A and n is as defined in the above formula I; preferably A is CH or N, more preferably A is N; R ₂ is trifluoromethyl, pentafluoroethyl or trifluoromethylsulfanyl; Preferably, R ₂ is trifluoromethyl; R ₇ is methyl or ethyl, preferably R ₇ is methyl; R ₈ is methyl or ethyl, preferably R ₈ is methyl; R ₉ is hydrogen; R ₁₀ is hydrogen; and n is 1.

(I-10) 其中R₁ 、R₂ 、R₇ 、R₈ 、R₉ 、R₁₀ 、A和n係如上式I所定義的。Another preferred group of compounds of formula I is represented by compounds of formula I-10

(I-10) wherein R ₁ , R ₂ , R ₇ , R ₈ , R ₉ , R ₁₀ , A and n are as defined in Formula I above.

In a preferred group of compounds of formula I-10, A is CH or N; R ₁ is ethyl, propyl or isopropyl; R ₂ is C ₁ -C ₂ haloalkyl, C ₁ -C ₂ haloalkyl Sulfhydryl, C ₁ -C ₂ haloalkylsulfinyl or C ₁ -C ₂ haloalkylsulfinyl; R ₉ is hydrogen, methyl or ethyl; R ₁₀ is hydrogen, cyano or -C( O) R ₂₅ , wherein R ₂₅ is a C ₁ -C ₂ haloalkyl group and n is 1.

In another preferred group of compounds of formula I-10, A is CH or N; R ₁ is ethyl; R ₂ is C ₁ -C ₂ fluoroalkyl, trifluoromethylsulfanyl, trifluoromethyl Sulfinyl, trifluoromethylsulfinyl, difluoromethylsulfinyl, difluoromethylsulfinyl, or difluoromethylsulfinyl; R ₉ is hydrogen or methyl, preferably R ₉ is hydrogen; R ₁₀ is hydrogen; and n is 1.

In another preferred group of compounds of formula I-10, R ₇ is hydrogen or C ₁ -C ₄ alkyl; and R ₈ is C ₁ -C ₄ alkyl.

In another preferred group of compounds of formula I-10, R ₇ is hydrogen, methyl or ethyl; and R ₈ is methyl or ethyl; preferably R ₇ is methyl; and R ₈ is methyl.

In all preferred embodiments of the compound of formula I-10 and the compound of formula I-10 above, unless otherwise specified, R ₁ , R ₂ , R ₇ , R ₈ , R ₉ , R ₁₀ , A and n is as defined in the above formula I; preferably A is CH or N, more preferably A is N; R ₂ is trifluoromethyl, pentafluoroethyl or trifluoromethylsulfanyl; Preferably, R ₂ is trifluoromethyl; R ₇ is methyl or ethyl, preferably R ₇ is methyl; R ₈ is methyl or ethyl, preferably R ₈ is methyl; R ₉ is hydrogen; R ₁₀ is hydrogen; and n is 1.

Another particularly preferred group of compounds of formula I is composed of formula I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8, I-9 or Those represented by compounds of I-10, where A is CH or N, preferably A is N; R ₁ is ethyl, propyl or isopropyl; preferably ethyl; R ₂ is trifluoromethyl R ₂ is a trifluoromethyl group; R ₉ and R ₁₀ are both hydrogen; and n is 1; and in formula I-1, I- 2. In the case of the compounds of I-3, and I-4, R ₃ is a methyl group; and in the case of the compound of formula I-4, R ₄ is an ethyl or cyclopropyl group; and wherein in the particular Among the preferred group of compounds of formula I, preferably R ₇ is hydrogen, methyl or ethyl; and R ₈ is methyl or ethyl; preferably R ₇ is methyl; and R ₈ is methyl.

The compounds according to the present invention may have any number of benefits, especially including a favorable level of biological activity for protecting plants from insects or excellent properties for use as an agrochemical active ingredient (eg, larger biological activity, favorable range of activity , Increased safety features, improved physical and chemical properties, or increased biodegradability or environmental features). In particular, it has been unexpectedly discovered that for non-target arthropods, especially pollinators (such as honeybees, solitary honeybees, and bumblebees), certain compounds of formula (I) can show advantageous safety characteristics. Most particularly, it is for Apis mellifera.

In another aspect, the present invention provides a composition comprising an effective amount of insecticidal, acaricidal, nematicidal or molluscicidal effective amount as in any one of the embodiments 1-28 (above) or formula I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8, I-9, or I-10 are the compounds defined in any one of the formula ( The compound of I) or its agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide, and optionally auxiliary or diluent.

In another aspect, the present invention provides a method for combating and controlling insects, mites, nematodes or molluscs, the method comprising adding an effective amount of insecticidal, acaricidal, nematicidal or molluscicidal as in the embodiment 1-28 (Above) or any one of formula I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8, I-9 or I-10 (above The compound of formula (I) or its agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide as defined by any one of the compounds in the embodiment of ), or as above The defined composition is applied to pests, pest sites, or plants vulnerable to pest attack.

In yet another aspect, the present invention provides a method for protecting plant propagation material from insects, mites, nematodes or mollusks, the method comprising treating the propagation material or planting the propagation material with a composition as defined above Location.

The method for preparing the compound of formula I according to the present invention is carried out by methods known to those skilled in the art.

可以藉由以下方式來製備（流程1）：使其中R₉ 、R₁ 、R₇ 、R₈ 、A和Q係如式I中所定義的式II的硫化物與合適的氮源（例如像氨、胺基甲酸銨或乙酸銨（較佳的是胺基甲酸銨））在諸如二乙醯氧基碘苯的超價碘試劑的存在下在諸如甲苯、乙腈或甲醇的溶劑中在0°C與100°C之間的溫度下（較佳的是在室溫附近）反應，類似於例如在Chem. Commun. [化學通訊] 53, 348-351; 2017（和其中引用的參考文獻）中找到的描述。A subgroup of compounds of formula I (defining compounds of formula Ia) wherein R ₁₀ is hydrogen and n is 1, wherein R ₉ , R ₁ , R ₇ , R ₈ , A and Q are as defined in formula I, Process 1:

It can be prepared by the following method (Scheme 1): where R ₉ , R ₁ , R ₇ , R ₈ , A and Q are the sulfides of formula II as defined in formula I and a suitable nitrogen source (such as Ammonia, ammonium carbamate or ammonium acetate (preferably ammonium carbamate) in the presence of a supervalent iodine reagent such as diacetoxy iodobenzene in a solvent such as toluene, acetonitrile or methanol at 0° The reaction is at a temperature between C and 100°C (preferably around room temperature), similar to, for example, in Chem. Commun. [Chemical Communications] 53, 348-351; 2017 (and references cited therein) The description found.

可以藉由以下方式來製備（流程2）：在以上針對將式II的化合物轉化為式Ia的化合物所說明的類似條件下使其中R₉ 、R₁ 、R₇ 、R₈ 、A和Q係如式I中所定義的式IIa的亞碸化合物反應，類似於例如Angewandte Chemie, International Edition [德國應用化學國際版], 55, 7203-7207; 2016（和其中引用的參考文獻）中找到的描述。Alternatively, the compound of formula Ia, wherein R ₉ , R ₁ , R ₇ , R ₈ , A and Q are as defined in formula I, Scheme 2:

It can be prepared in the following way (Scheme 2): Under similar conditions as described above for the conversion of a compound of formula II to a compound of formula Ia, where R ₉ , R ₁ , R ₇ , R ₈ , A and Q are The reaction of the sulfenite compound of formula IIa as defined in formula I is similar to the description found in, for example, Angewandte Chemie, International Edition [German Applied Chemistry International Edition], 55, 7203-7207; 2016 (and references cited therein) .

Wherein R ₉ , R ₁ , R ₇ , R ₈ , A and Q are as defined in formula I. The compound of formula IIa can be obtained by the oxidation reaction of the corresponding sulfide compound of formula II, which involves the addition of other oxidants Other reagents such as m-chloroperoxybenzoic acid (mCPBA), hydrogen peroxide, potassium peroxymonosulfate (oxone), sodium periodate, sodium hypochlorite or tertiary butyl hypochlorite. The oxidation reaction is usually carried out in the presence of a solvent. Examples of the solvent used in the reaction include aliphatic halogenated hydrocarbons such as dichloromethane and chloroform; alcohols such as methanol and ethanol; acetic acid; water; and mixtures thereof. The amount of the oxidizing agent used in the reaction is preferably 1 to 1.2 mol relative to 1 mol of the sulfide compound II to produce the sulfite compound IIa.

可以藉由以下方式來製備（流程3）：使其中R₉ 、R₁ 、R₇ 、R₈ 、A和Q係如式I中所定義的式IIa的化合物經受亞胺化反應條件，如例如在H. Okamura, C. Bolm, Org. Lett. [有機快報] 2004, 6, 1305-1307；H. Okamura, C. Bolm, Chem. Lett. [化學快報] 2004, 33, 482-487；D. Leca, K. Song, M. Amatore, L. Fensterbank, E. Lacôte, M. Malacria, Chem. Eur [歐洲化學]. J. 2004, 10, 906-916；或M. Reggelin, C. Zur, Synthesis [合成], 2000, 1-64中所描述的。典型的亞胺化試劑/條件可以定義為NaN₃ /H₂ SO₄ 、O-均三甲苯磺醯基-羥胺（MSH）或金屬催化方法 [參見O.G. Mancheno, C. Bolm, Chem. Eur. [歐洲化學] J. 2007, 13, 6674-6681]，諸如R₁₀ -N₃ /FeCl₂ 、R₁₀ -NH₂ /Fe(acac)₃ /PhI=O、PhI=N-R₁₀ /Fe(OTf)₂ 、PhI=N-R₁₀ /CuOTf、PhI=N-R₁₀ /Cu(OTf)₂ 、PhI=N-R₁₀ /CuPF₆ 、PhI(OAc)₂ /R₁₀ -NH₂ /MgO/Rh₂ (OAc)₄ 或氧氮環丙烷（oxaziridine）（例如，3-(4-氰基-苯基)-氧氮環丙烷-2-甲酸三級丁酯）。Wherein n is a subgroup of the compound of formula I (defined as the compound of formula Ib), wherein R ₉ , R ₁₀ , R ₁ , R ₇ , R ₈ , A and Q are as defined in formula I, scheme 3 :

It can be prepared by the following method (Scheme 3): subjecting the compound of formula IIa wherein R ₉ , R ₁ , R ₇ , R ₈ , A and Q are as defined in formula I to imidization reaction conditions, such as In H. Okamura, C. Bolm, Org. Lett. [Organic Letters] 2004, 6, 1305-1307; H. Okamura, C. Bolm, Chem. Lett. [Chemical Letters] 2004, 33, 482-487; D . Leca, K. Song, M. Amatore, L. Fensterbank, E. Lacôte, M. Malacria, Chem. Eur [European Chemistry]. J. 2004, 10, 906-916; or M. Reggelin, C. Zur, Synthesis [Synthesis], 2000, described in 1-64. Typical imidization reagents/conditions can be defined as NaN ₃ /H ₂ SO ₄ , O-mesitylenesulfonyl-hydroxylamine (MSH) or metal catalyzed methods [see OG Mancheno, C. Bolm, Chem. Eur. [ European Chemistry] J. 2007, 13, 6674-6681], such as R ₁₀ -N ₃ /FeCl ₂ , R ₁₀ -NH ₂ /Fe(acac) ₃ /PhI=O, PhI=NR ₁₀ /Fe(OTf) ₂ , PhI=NR ₁₀ /CuOTf, PhI=NR ₁₀ /Cu(OTf) ₂ , PhI=NR ₁₀ /CuPF ₆ , PhI(OAc) ₂ /R ₁₀ -NH ₂ /MgO/Rh ₂ (OAc) ₄ or oxygen nitrogen Cyclopropane (oxaziridine) (for example, 3-(4-cyano-phenyl)-oxaziridine-2-carboxylic acid tertiary butyl ester).

Of particular interest is the metal-free imidization process, which involves R ₁₀ -NH ₂ and an oxidizing agent, such as PhI(OAc) ₂ /R ₁₀ -NH ₂ , such as GY Cho, C. Bolm, Tetrahedron Lett. [Tetrahedron Letters ] 2005, 46, 8007-8008; or N-bromosuccinimide (NBS)/R ₁₀ -NH ₂ and alkalis such as sodium tertiary butoxide or potassium tertiary butoxide, such as C. Bolm Et al. Synthesis [Synthesis] 2010, Issue 17, 2922-2925. An oxidizing agent such as N-iodosuccinimide (NIS) or iodine may alternatively be used, as described, for example, in OG Mancheno, C. Bolm, Org. Lett. [Organic Express] 2007, 9, 3809-3811 . Examples of hypochlorites used as oxidants are described in WO 2008/1060, such as sodium hypochlorite NaOCl or calcium hypochlorite Ca(OCl) ₂ .

The formula Ib wherein R ₉ , R ₁ , R ₇ , R ₈ , A and Q are as defined above and wherein R ₁₀ is CN can be treated with trifluoroacetic anhydride in a solvent such as dichloromethane The compound is converted into a compound of formula Ib in which R ₁₀ is C(O)CF ₃ , as described, for example, in OG Mancheno, C. Bolm, Org. Lett. [Organic Letters] 2007, 9, 3809-3811.

R ₉ , R ₁ , R ₇ , R ₈ , A and Q can be as defined above by treatment with a base such as sodium carbonate or potassium carbonate in a polar protic solvent such as methanol or ethanol, and wherein R ₁₀ is the conversion of a compound of formula Ib of C(O)CF ₃ into a compound of formula Ib in which R ₁₀ is hydrogen (R _{10 is} cleaved), as for example in H. Okamura, C. Bolm, Org. Lett. [Organic Express] As described in 2004, 6, 1305-1307.

式Ic的化合物（為其中n係0並且其中其他取代基係如流程3中所定義的式I的化合物的亞組）的氧化，以提供式Ib的化合物，可以在以上已經描述的條件下實現或者可替代地涉及例如KMnO₄ 、NaMnO₄ 、mCPBA、NaIO₄ /RuO₂ 、NaIO₄ /RuCl₃ 、H₂ O₂ 、過氧單硫酸鉀鹽。具體而言，WO 2008/097235和WO 2008/106006中描述了使用與鹼金屬過碘酸鹽組合的釕鹽和可替代地使用鹼金屬過錳酸鹽。Instead, the sequence of the two oxidation/imination steps can be restored, as shown in Scheme 4. Process 4:

The oxidation of compounds of formula Ic (which is a subgroup of compounds of formula I where n is 0 and where other substituents are as defined in Scheme 3) to provide compounds of formula Ib can be achieved under the conditions already described above Or it may alternatively involve, for example, KMnO ₄ , NaMnO ₄ , mCPBA, NaIO ₄ /RuO ₂ , NaIO ₄ /RuCl ₃ , H ₂ O ₂ , potassium peroxymonosulfate. Specifically, WO 2008/097235 and WO 2008/106006 describe the use of a ruthenium salt in combination with an alkali metal periodate and alternatively the use of an alkali metal permanganate.

Wherein R ₉ , R ₁₀ , R ₁ , R ₇ , R ₈ , A and Q are as defined in formula I. The compound of formula Ic can be prepared by the following method: wherein R ₉ , R ₁ , R ₇ , R ₈ , A and Q are the compounds of formula II as defined in formula I and are subjected to imidization reaction conditions, as described in Scheme 3 above.

可以藉由以下方式來製備（流程5）：在例如像碳酸鉀、碳酸銫、六甲基二矽氮烷鋰或二異丙基胺基鋰的鹼的存在下在諸如乙腈、四氫呋喃或N,N-二甲基甲醯胺的合適溶劑中在-78°C與100°C之間、較佳的是在-10°C與80°C之間的溫度下使其中R₉ 、R₁ 、A和Q係如式I中所定義的式III的化合物與其中R₇ 和R₈ 係如式I中所定義的並且其中Xa係脫離基（例如像氯、溴或碘（較佳的是碘或溴），或芳基-、烷基-或鹵代烷基磺酸酯（諸如三氟甲磺酸酯））的式IV的化合物反應，如例如在Bioorganic & Medicinal Chemistry [生物有機及藥物化學], 20(18), 5600-5615; 2012中所描述的。較佳的是，用通式IV的R₇ Xa和R₈ Xa的烷基化試劑依次處理式III的化合物。在R7和R8同等的特定情況下，可以使式III的化合物經受過量的上述鹼和試劑R'Xa IV，其中Xa係如上所定義的並且其中R₇ =R₈ =R'。 其中R₉ 、R₁ 、A和Q係如式I中所定義的式III的化合物 流程6：

可以藉由以下方式來製備（流程6）：在例如像碳酸鉀、碳酸銫或氫化鈉的鹼的存在下視需要在催化劑量的諸如碘化鈉或碘化鉀的添加劑的存在下在諸如丙酮、四氫呋喃、乙腈、二甲基亞碸或N,N-二甲基甲醯胺的合適溶劑中在-10°C與100°C之間、較佳的是在0°C與80°C之間的溫度下使其中R₉ 、R₁ 、A和Q係如式I中所定義的式V的化合物與其中Xa係脫離基（例如像氯、溴或碘（較佳的是氯或溴），或芳基-、烷基-或鹵代烷基磺酸酯（諸如三氟甲磺酸酯））的式VI的化合物反應，如例如在Tetrahedron Letters [四面體快報], 34(47), 7567-8; 1993中所描述的。Wherein R ₉ , R ₁ , R ₇ , R ₈ , A and Q are as defined in formula I, and the compound of formula II is shown in Scheme 5:

It can be prepared by the following method (Scheme 5): in the presence of a base such as potassium carbonate, cesium carbonate, lithium hexamethyldisilazane or lithium diisopropylamide in the presence of such as acetonitrile, tetrahydrofuran or N, N-dimethylformamide in a suitable solvent is between -78°C and 100°C, preferably at a temperature between -10°C and 80°C, where R ₉ , R ₁ , A and Q are compounds of formula III as defined in formula I and wherein R ₇ and R ₈ are as defined in formula I and wherein Xa is free from a group (such as chlorine, bromine or iodine (preferably iodine) Or bromine), or aryl-, alkyl- or haloalkyl sulfonates (such as trifluoromethanesulfonate) with compounds of formula IV, as for example in Bioorganic & Medicinal Chemistry [Bioorganic & Medicinal Chemistry], 20(18), 5600-5615; described in 2012. Preferably, the compound of formula III is treated sequentially with an alkylating agent of R ₇ Xa and R ₈ Xa of general formula IV. In particular R7 and R8 are the same case, the compound of Formula III is subjected to the above-described base and excess reagent R'Xa IV, wherein Xa-based as defined above and wherein _{R 7 = R 8 = R '} . Wherein R ₉ , R ₁ , A and Q are the compound of formula III as defined in formula I. Scheme 6:

It can be prepared in the following way (Scheme 6): in the presence of a base such as potassium carbonate, cesium carbonate or sodium hydride, in the presence of a catalytic amount of additives such as sodium iodide or potassium iodide, in the presence of additives such as acetone, tetrahydrofuran , Acetonitrile, dimethyl sulfide or N, N-dimethylformamide in a suitable solvent between -10 °C and 100 °C, preferably between 0 °C and 80 °C The compound of formula V in which R ₉ , R ₁ , A and Q are as defined in formula I and Xa are separated from the group (such as chlorine, bromine or iodine (preferably chlorine or bromine)) at temperature, or Aryl-, alkyl- or haloalkyl sulfonates (such as triflate) are reacted with compounds of formula VI, as for example in Tetrahedron Letters [Tetrahedron Letters], 34(47), 7567-8; Described in 1993.

可以在脫水條件下藉由以下方式來製備（流程7）：視需要在諸如三乙胺或吡啶的鹼的存在下在例如像二氯甲烷、二㗁𠮿或N,N-二甲基甲醯胺的適當溶劑中在0°C與180°C之間、較佳的是在5°C與80°C之間的溫度下使其中R₉ 、R₁ 、R₇ 、R₈ 、A和Q係如式I中所定義的式VII的化合物與諸如三氟乙酸、三氟乙酸酐、五氧化二磷、亞硫醯氯或三氯氧磷的脫水劑反應，如例如在US 20100267738中所描述的。 其中R₉ 、R₁ 、R₇ 、R₈ 、A和Q係如式I中所定義的式VII的化合物 流程8：

可以藉由以下方式來製備（流程8）：在例如像氫氧化鋰、氫氧化鈉或氫氧化鉀，氫化鈉，碳酸鉀或碳酸銫的鹼的存在下在諸如丙酮、二㗁𠮿、乙腈、N,N-二甲基甲醯胺或N,N-二甲基乙醯胺的合適溶劑中在-10°C與100°C之間、較佳的是在0°C與80°C之間的溫度下使其中R₉ 、R₁ 、A和Q係如式I中所定義的式V的化合物與其中R₇ 和R₈ 係如式I中所定義的並且其中Xa係脫離基（例如像氯、溴或碘（較佳的是溴），或芳基-、烷基-或鹵代烷基磺酸酯（諸如三氟甲磺酸酯））的式VIII的化合物反應，如例如在WO 2014071044中所描述的。Alternatively, wherein R ₉ , R ₁ , R ₇ , R ₈ , A, and Q are as defined in Formula I, the compound of Formula II, Scheme 7:

It can be prepared in the following manner under dehydration conditions (Scheme 7): If necessary, in the presence of a base such as triethylamine or pyridine, in the presence of, for example, dichloromethane, dimethymethane or N,N-dimethylformamide The suitable solvent of amine is between 0 °C and 180 °C, preferably at a temperature between 5 °C and 80 °C, wherein R ₉ , R ₁ , R ₇ , R ₈ , A and Q The compound of formula VII as defined in formula I reacts with a dehydrating agent such as trifluoroacetic acid, trifluoroacetic anhydride, phosphorus pentoxide, sulfite chloride or phosphorus oxychloride, as described for example in US 20100267738 of. Wherein R ₉ , R ₁ , R ₇ , R ₈ , A and Q are the compound of formula VII as defined in formula I. Scheme 8:

It can be prepared by the following method (Process 8): in the presence of a base such as lithium hydroxide, sodium hydroxide or potassium hydroxide, sodium hydride, potassium carbonate or cesium carbonate in the presence of bases such as acetone, diacetone, acetonitrile, N,N-dimethylformamide or N,N-dimethylacetamide in a suitable solvent between -10°C and 100°C, preferably between 0°C and 80°C The compound of formula V where R ₉ , R ₁ , A and Q are as defined in formula I and the compound of formula V where R ₇ and R ₈ are as defined in formula I and where Xa is free from the group (eg Reactions of compounds of formula VIII like chlorine, bromine or iodine (preferably bromine), or aryl-, alkyl- or haloalkyl sulfonates (such as trifluoromethanesulfonate), as for example in WO 2014071044 Described in.

可以藉由以下方式來製備（流程9）：在諸如碳酸鉀或碳酸銫的鹼的存在下，視需要在鈀催化劑（諸如RockPhos-G3-環鈀配合物（[(2-二-三級丁基膦基-3-甲氧基-6-甲基-2',4',6'-三異丙基-1,1'-二苯基)-2-(2-胺基二苯基)]甲磺酸鈀(II)）的存在下在諸如乙腈或N,N-二甲基甲醯胺DMF的非質子溶劑中在0與100°C之間、較佳的是在室溫與80°C之間的溫度下使其中R₉ 、R₁ 、A和Q係如式I中所定義的並且其中X係脫離基（例如像氯、溴或碘（較佳的是溴），或芳基-、烷基-或鹵代烷基磺酸酯（諸如三氟甲磺酸酯））的式IX的化合物與例如苯甲醛肟PhC=NOH（較佳的是(E)-苯甲醛肟）反應，如例如在Angew. Chem. Int. Ed [應用化學國際版]. 56 (16), 4478-4482, 2017中所描述的。Wherein R ₉ , R ₁ , A and Q are the compound of formula V as defined in formula I. Scheme 9:

It can be prepared by the following method (Scheme 9): in the presence of a base such as potassium carbonate or cesium carbonate, optionally over a palladium catalyst such as RockPhos-G3-cyclopalladium complex ([(2-di-tertiary butyl) Phosphonyl-3-methoxy-6-methyl-2',4',6'-triisopropyl-1,1'-diphenyl)-2-(2-aminodiphenyl) ] In the presence of palladium (II) methanesulfonate) in an aprotic solvent such as acetonitrile or N,N-dimethylformamide DMF between 0 and 100 ° C, preferably at room temperature and 80 At a temperature between °C, where R ₉ , R ₁ , A and Q are as defined in formula I and where X is free from a group (such as chlorine, bromine or iodine (preferably bromine), or aromatic The compound of formula IX of a group-, alkyl- or haloalkylsulfonate (such as trifluoromethanesulfonate) is reacted with, for example, benzaldehyde oxime PhC=NOH (preferably (E)-benzaldehyde oxime), As described in, for example, Angew. Chem. Int. Ed [Applied Chemistry International Edition]. 56 (16), 4478-4482, 2017.

Alternatively, where R _9, R _1, a compound of formula V, A and Q lines as in formula I as defined herein may be, R _1, A and Q lines as in formula I is defined by wherein R ₉ and where X The compound of formula IX leaving the group (such as chlorine, bromine or iodine (preferably bromine), or aryl-, alkyl- or haloalkyl sulfonate (such as triflate)) is sequentially Run the following to prepare: 1) Boronylation reaction, in which the compound of formula IX is typically reacted with bispinacol diborane (Bpin) 2 under palladium catalysis. The introduction of such pinacol borate functional groups can be carried out in the presence of a base (preferably a weak base, such as potassium acetate KOAc) in an aprotic solvent such as dioxane. [1,1'-Bis(diphenylphosphino)ferrocene]palladium(II) dichloride, also known as palladium dichloride dppf or Pd(dppf)Cl2, is a commonly used catalyst for such reactions . Other palladium source/ligand combinations involve, for example, tris(dibenzylideneacetone) second target and tricyclohexylphosphine. The temperature of the reaction is preferably between 0°C and the boiling point of the reaction mixture, or the reaction can be carried out under microwave irradiation. The intermediate product of this borosylation reaction is then further subjected to 2) an oxidation step, in which it is typically between 0 and 100° C., preferably at a temperature around room temperature, in an inert state such as tetrahydrofuran or bis-㗁𠮿 The intermediate product is treated with hydrogen peroxide H ₂ O ₂ (for example, a 30% H ₂ O ₂ solution in water) in a solvent. The method for preparing the compound of the formula V from the compound of the formula IX may include the isolation and purification of the boronated intermediate, but this method is also advantageously performed by incorporating the crude intermediate into the oxidation step 2.

Wherein R ₉ , R ₁ , A and Q are as defined in formula I and wherein X is free from the group, especially those compounds in which X is halogen, are known compounds, or can be known by The method is prepared, or can be synthesized similarly to the described method found in the literature. See especially WO 2016/071214 (Q series Q ₂ , G ₂ series N) and WO 2015/000715 (Q series Q ₂ , G ₂ series CH), WO 2016/026848 and WO 2016/005263 (Q series Q ₁ , G ₁ series CH, G ₂ series N), WO 2016/059145 (Q series Q ₁ , G ₁ series N, G ₂ series N), WO 2016/020286 and WO 2017/134066 (Q series Q ₄ ), WO 2017/ 089190, WO 2017/084879 and WO 2016/023954 (Q series Q ₅ ), WO 2015/000715 (Q series Q ₃ ), and WO 2012/086848, WO 2013/018928 (Q series Q ₁ , G ₁ series N or CH, G ₂ is CH).

Wherein R ₇ and R ₈ are as defined in formula I and where Xa is a leaving group (such as chlorine, bromine or iodine (preferably iodine or bromine), or aryl-, alkyl- or haloalkylsulfonate Acid esters (such as triflate)); and in the specific case where R ₇ =R ₈ =R', wherein R ₇ and R ₈ are as defined in Formula I and wherein Xa is the formula R'leaving a group (such as chlorine, bromine or iodine (preferably chlorine or bromine), or aryl-, alkyl- or haloalkylsulfonate (such as trifluoromethanesulfonate)) -Xa IV compounds; and wherein Xa is free from groups (such as chlorine, bromine or iodine (preferably bromine), or aryl-, alkyl- or haloalkylsulfonates (such as triflate) )) Compounds of formula VI; and wherein R ₇ and R ₈ are as defined in formula I and wherein Xa is a leaving group (such as chlorine, bromine or iodine (preferably bromine)), or aryl-, Alkyl- or haloalkyl sulfonates (such as triflate) are compounds of formula VIII; all are either known compounds, commercially available, or can be prepared by known methods described in the literature .

可以由其中R₁ 、A和Q係如式I中所定義的並且其中Xb係鹵素，較佳的是氯、溴或碘的式Vb的化合物借助典型地在鈀催化（可替代地是鎳催化）的交叉偶合條件下的C-C鍵生成反應來製備（流程10）。式Vb的化合物與其中R₉ 係如式I中所定義的式R₉ B(OH)₂ 的C₁ -C₄ 烷基硼酸、或相應的C₁ -C₄ 烷基硼酸酯衍生物、或其中R₉ 係如式I中所定義的式(R₉ BO)₃ 的相應的6元三(C₁ -C₄ 烷基)硼氧六環（boroxine）衍生物之間的此類鈴木-宮浦（Suzuki-Miyaura）交叉偶合反應係熟悉該項技術者熟知的。在R₉ 係甲基的特定情況下，可以在諸如四(三苯基膦)-鈀(0)或[1,1'-雙(二苯基膦基)二茂鐵]二氯化鈀(II)二氯甲烷錯合物的鈀催化劑和諸如碳酸鈉或碳酸鉀的鹼的存在下在諸如N,N-二甲基甲醯胺、二㗁𠮿或二㗁𠮿-水混合物的溶劑中在室溫與160°C之間的溫度下、視需要在微波加熱條件下並且較佳的是在惰性氣氛下使式Vb的化合物例如與三甲基硼氧六環（也稱為2,4,6-三甲基-1,3,5,2,4,6-三氧雜硼環己烷）反應。例如在Tetrahedron Letters [四面體通訊] (2000), 41(32), 6237-6240中描述了此類條件。Wherein R ₉ is a subgroup of compounds of formula V (defined as compounds of formula Vc) in which R ₉ is a C ₁ -C ₄ alkyl group, wherein R ₁ , A and Q are as defined in formula I, Scheme 10:

The compound of formula Vb in which R ₁ , A and Q are as defined in formula I and in which Xb is halogen, preferably chlorine, bromine or iodine, can be made with the aid of being typically catalyzed by palladium (alternatively nickel catalyzed ) Under the cross-coupling conditions of CC bond formation reaction to prepare (Scheme 10). The compound of formula Vb and wherein R ₉ is a C ₁ -C ₄ alkyl boronic acid of formula R ₉ B(OH) ₂ as defined in formula I, or the corresponding C ₁ -C ₄ alkyl boronic acid ester derivative, Or where R ₉ is the corresponding 6-membered tris (C ₁ -C ₄ alkyl) boroxine derivative of formula (R ₉ BO) ₃ as defined in formula I, such Suzuki- The Suzuki-Miyaura cross-coupling reaction is familiar to those familiar with the technology. In the specific case where R ₉ is a methyl group, it can be used such as tetrakis(triphenylphosphine)-palladium(0) or [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride ( II) The presence of a palladium catalyst of the dichloromethane complex and a base such as sodium carbonate or potassium carbonate in a solvent such as N,N-dimethylformamide, diethyl or di-water mixture At a temperature between room temperature and 160 ° C, optionally under microwave heating conditions and preferably under an inert atmosphere, the compound of formula Vb, for example, with trimethylboroxine (also known as 2,4, 6-Trimethyl-1,3,5,2,4,6-trioxaborocyclohexane) reaction. Such conditions are described in Tetrahedron Letters [Tetrahedron Communication] (2000), 41(32), 6237-6240, for example.

可以藉由以下方式來製備（流程11）：例如藉由在0°C與180°C之間、較佳的是在20°C與150°C之間的溫度下，視需要在微波照射下在乙酸或三氟乙酸中加熱（較佳的是當X₁ 係其中R₃ 係C₁ -C₄ 烷基的NR₃ 時），使其中R₁ 、R₉ 、R₇ 、R₈ 、A、X₁ 、G₁ 、G₂ 和R₂ 係如式I中所定義的式 (XX) 之化合物環化。也可以在25°C-180°C之間、較佳的是100°C-170°C的溫度下在諸如N-甲基吡咯啶酮、甲苯或二甲苯的惰性溶劑中在酸催化劑（例如甲磺酸或對甲苯磺酸p-TsOH）的存在下實現式 (XX) 之化合物的環化。此類方法先前已經描述於例如WO 2010/125985中。可替代地，可以在20°C-50°C之間的溫度下在諸如四氫呋喃THF的惰性溶劑中，使用三苯基膦、偶氮二甲酸二異丙酯（或偶氮二甲酸二乙酯）將式 (XX) 之化合物轉化成式II-Q1的化合物（較佳的是當X₁ 係O時）。先前已經針對該等轉化描述了此類光延反應條件（參見WO 2009/131237）。The compound of formula Vb in which R ₁ , A and Q are as defined in formula I and wherein Xb is halogen, preferably chlorine, bromine or iodine, can be prepared by halogenation reaction, which involves, for example, optionally In the presence of a base such as sodium carbonate, potassium carbonate or cesium carbonate, the subgroup of compounds of formula V (defined as compounds of formula Va) in which R ₉ is hydrogen (wherein R ₁ , A and Q are as in formula I As defined) and halogenating reagents (such as N-chlorosuccinimide (NCS), N-bromosuccinimide (NBS) or N-iodo-succinimide (NIS), or alternatively chlorine, bromine Or iodine) reaction. This type of halogenation reaction is in an inert solvent such as chloroform, carbon tetrachloride, 1,2-dichloroethane, acetic acid, ether, N,N-dimethylformamide, acetonitrile or acetonitrile-water mixture at 20° The temperature is between C-200°C, preferably from room temperature to 100°C. Alternatively, the compound of formula II where Q is Q ₁ (defined as the compound of formula II-Q ₁ ), wherein R ₁ , R ₉ , R ₇ , R ₈ , A, X ₁ , G ₁ , G ₂ and R ₂ is as defined in formula I, flow 11:

It can be prepared by the following method (process 11): for example, by at a temperature between 0°C and 180°C, preferably at a temperature between 20°C and 150°C, and optionally under microwave irradiation Heating in acetic acid or trifluoroacetic acid (preferably when X ₁ is NR ₃ in which R ₃ is a C ₁ -C ₄ alkyl group), so that R ₁ , R ₉ , R ₇ , R ₈ , A, X ₁ , G ₁ , G ₂ and R ₂ are cyclizations of the compound of formula (XX) as defined in formula I. It can also be used in an acid catalyst (such as N-methylpyrrolidone, toluene or xylene) at a temperature between 25°C-180°C, preferably 100°C-170°C, in an inert solvent such as N-methylpyrrolidone, toluene or xylene The cyclization of the compound of formula (XX) is realized in the presence of methanesulfonic acid or p-toluenesulfonic acid (p-TsOH). Such methods have previously been described in, for example, WO 2010/125985. Alternatively, triphenylphosphine, diisopropyl azodicarboxylate (or diethyl azodicarboxylate can be used in an inert solvent such as tetrahydrofuran THF at a temperature between 20°C-50°C ) Convert the compound of formula (XX) into the compound of formula II-Q1 (preferably when X ₁ is O). Such Mitsunobu reaction conditions have been previously described for these transformations (see WO 2009/131237).

Wherein R ₁ , R ₉ , R ₇ , R ₈ , A, X ₁ , G ₁ , G ₂ and R ₂ are as defined in formula I. The compound of formula (XX) can be prepared by acylation in the following manner : I) By methods known to those skilled in the art and described in Tetrahedron [tetrahedron], 2005, 61 (46), 10827-10852, R ₁ , R ₉ , R ₇ , R ₈ and A The compound of formula (XXIII) as defined in formula I is activated to form wherein R ₁ , R ₉ , R ₇ , R ₈ and A are as defined in formula I and wherein X ₀₀ is halogen, preferably It is an activated substance of chlorine (XXII). For example, the compound (XXII) in which X ₀₀ is a halogen, preferably chlorine, is obtained by using dichloromethane CH ₂ Cl at a temperature between 20°C and 100°C, preferably 25°C. ₂ or tetrahydrofuran THF in an inert solvent in the presence of a catalytic amount of N,N-dimethylformamide DMF, for example, treated with oxalyl chloride (COCl) ₂ or sulfite chloride SOCl ₂ (XXIII). Alternatively, at a temperature between 50°C and 180°C, if necessary, in the presence of a base such as triethylamine in an inert solvent such as pyridine or tetrahydrofuran THF, for example, 1-ethyl-3- (3-Dimethylaminopropyl) carbodiimide EDC or dicyclohexylcarbodiimide DCC treatment of the compound of formula (XXIII) will generate an activated substance (XXII) where X ₀₀ is X ₀₁ or X ₀₂ , respectively ; Then ii) at a temperature between 0 ° C and 50 ° C, such as dichloromethane, tetrahydrofuran, two 㗁 𠮿, N,N-dimethylformamide, N,N-dimethylacetamide , Acetonitrile, ethyl acetate or toluene in the presence of a base such as triethylamine, N,N-diisopropylethylamine or pyridine, where X ₁ , G ₂ , G ₂ and R ₂ are such as The compound of formula (XI) as defined in formula I treats the activated substance (XXII) to form the compound of formula (XX).

可以藉由以下方式來製備（流程12）：在熟悉該項技術者已知的條件下（例如使用諸如以下的條件：甲醇、乙醇、四氫呋喃或二㗁𠮿中的氫氧化鈉、氫氧化鉀或氫氧化鋰水溶液，在室溫下或直至回流條件下）將其中R₁ 、R₉ 、R₇ 、R₈ 和A係如式I中所定義的並且其中R₀₀ 係C₁ -C₆ 烷基式 (XXIV) 之化合物皂化。Wherein R ₁ , R ₉ , R ₇ , R ₈ and A are compounds of formula (XXIII) as defined in formula I. Scheme 12:

It can be prepared in the following way (Scheme 12): Under conditions known to those skilled in the art (for example, using conditions such as the following: methanol, ethanol, tetrahydrofuran, or sodium hydroxide, potassium hydroxide or Lithium hydroxide aqueous solution, at room temperature or until reflux conditions) wherein R ₁ , R ₉ , R ₇ , R ₈ and A are as defined in formula I and wherein R ₀₀ is a C ₁ -C ₆ alkyl group The compound of formula (XXIV) is saponified.

The compound of formula (XXIV) wherein R ₁ , R ₉ , R ₇ , R ₈ and A are as defined in formula I and wherein R ₀₀ is a C ₁ -C ₆ alkyl group can be prepared by the following method: Under the conditions described above (see Scheme 5, conversion of compound III to II), the formula wherein R ₉ , R ₁ and A are as defined in formula I and wherein R ₀₀ is a C ₁ -C ₆ alkyl group) The compound of (XXV-b) and wherein R ₇ and R ₈ are as defined in formula I and wherein Xa is a free radical (such as chlorine, bromine or iodine (preferably iodine or bromine)), or aryl- , Alkyl- or halogenated alkyl sulfonate (such as triflate) to react with a compound of formula IV.

The compound of formula (XXV-b) where R ₉ , R ₁ and A are as defined in formula I and where R ₀₀ is a C ₁ -C ₆ alkyl group can be prepared by the following method: Conditions (see Scheme 6, converting compound V to III) are such that R ₁ , R ₉ and A are as defined in formula I and where R ₀₀ is a C ₁ -C ₆ alkyl group (XXV-a) The compound of which Xa is separated from the group (such as chlorine, bromine or iodine (preferably chlorine or bromine), or aryl-, alkyl- or haloalkylsulfonate (such as triflate)) The compound of formula VI reacts.

Alternatively, the compound of formula (XXIV) wherein R ₁ , R ₉ , R ₇ , R ₈ and A are as defined in formula I and wherein R ₀₀ is a C ₁ -C ₆ alkyl group can be obtained by To prepare: subject the compound of formula (XXV-c) wherein R ₁ , R ₉ , R ₇ , R ₈ and A are as defined in formula I and wherein R ₀₀ is a C ₁ -C ₆ alkyl group Describe the dehydration conditions (see Scheme 7, Conversion of Compound VII to II).

The compound of formula (XXV-c) wherein R ₁ , R ₉ , R ₇ , R ₈ and A are as defined in formula I and wherein R ₀₀ is a C ₁ -C ₆ alkyl group can be prepared by the following method : Under the conditions described above (see Scheme 8, converting compound V to VII), wherein R ₁ , R ₉ and A are as defined in formula I and wherein R ₀₀ is a C ₁ -C ₆ alkyl group The compound of formula (XXV-a) and wherein R ₇ and R ₈ are as defined in formula I and wherein Xa is a leaving group (such as chlorine, bromine or iodine (preferably bromine)), or aryl-, Alkyl- or haloalkylsulfonates (such as triflate) are reacted with compounds of formula VIII.

The compound of formula (XXV-a) where R ₁ , R ₉ and A are as defined in formula I and where R ₀₀ is a C ₁ -C ₆ alkyl group can be prepared by the following method: the conditions described above (Refer to Scheme 9, convert compound IX to V), where R ₁ , R ₉ and A are as defined in formula I and where R ₀₀ is a C ₁ -C ₆ alkyl group and where Xc is a free radical ( For example, like chlorine, bromine or iodine (preferably bromine), or aryl-, alkyl- or haloalkyl-sulfonate (such as triflate), the compound of formula (XXV) and, for example, benzene Formaldehyde oxime PhC=NOH (preferably (E)-benzaldehyde oxime) reaction. Alternatively, the method for preparing the compound of formula (XXV-a) from the compound of formula (XXV) can also involve the boronation/oxidation conditions that have also been described in Scheme 9.

Wherein R ₁ , R ₉ and A are as defined in formula I and where R ₀₀ is a C ₁ -C ₆ alkyl group and where Xc is a leaving group (such as chlorine, bromine or iodine, or aryl-, alkyl -Or halogenated alkyl sulfonate (such as trifluoromethanesulfonate), compounds of formula (XXV), especially those compounds where Xc is halogen (even more preferably chlorine, bromine or iodine), or Known compounds are commercially available or can be prepared by known methods described in the literature (such as, for example, in WO 2016/005263, WO 2016/023954, WO 2016/026848 and WO 2016/104746).

可以藉由以下方式來製備（流程13）：在例如乙醇或乙腈的惰性溶劑中，視需要在諸如碳酸鈉、碳酸鉀或碳酸銫、或氧化鎂的合適鹼的存在下在50°C與150°C之間的溫度下，視需要在微波加熱條件下，其中R₁ 、R₉ 、R₇ 、R₈ 和A係如式I中所定義的並且其中Xd係脫離基（例如像氯、溴或碘（較佳的是氯或溴））的式 (XXVI) 之化合物與其中G₂ 和R₂ 係如式I中所定義的式 (XXVII) 化合物縮合。此類方法先前已經描述於例如WO 2012/49280或WO 2003/031587中。其中G₂ 和R₂ 係如式I中所定義的式 (XXVII) 之化合物或者是已知化合物，可商購獲得，或者可藉由熟悉該項技術者已知的已知方法製備，特別參見WO 2016/071214。Alternatively, the compound of formula II where Q is Q ₂ (defined as the compound of formula II-Q ₂ ), wherein R ₁ , R ₉ , R ₇ , R ₈ , A, G ₂ and R ₂ are as in formula I As defined, process 13:

It can be prepared in the following way (process 13): in an inert solvent such as ethanol or acetonitrile, if necessary, in the presence of a suitable base such as sodium carbonate, potassium carbonate or cesium carbonate, or magnesium oxide at 50°C and 150°C °C, optionally under microwave heating conditions, where R ₁ , R ₉ , R ₇ , R ₈ and A are as defined in formula I and where Xd is free of radicals (such as chlorine, bromine) Or iodine (preferably chlorine or bromine)) is condensed with a compound of formula (XXVI) in which G ₂ and R ₂ are as defined in formula I. Such methods have previously been described in, for example, WO 2012/49280 or WO 2003/031587. Wherein G ₂ and R ₂ are compounds of formula (XXVII) as defined in formula I or are known compounds, which are commercially available, or can be prepared by known methods known to those skilled in the art, see in particular WO 2016/071214.

可以藉由以下方式來製備（流程14）：典型地在諸如甲醇、乙腈、四氫呋喃、乙酸乙酯、氯仿或二氯甲烷、或其混合物的溶劑中在0°C與150°C之間、較佳的是在室溫與120°C之間的溫度下，視需要在微波加熱條件下，用鹵化試劑（「Xd⁺ 」源）（例如N-溴琥珀醯亞胺、N-碘琥珀醯亞胺、N-氯琥珀醯亞胺、I₂ 、CuBr₂ 、在乙酸中的Br₂ 、或三甲基(苯基)三溴化銨PhNMe₃ ⁺ Br₃ ^- ）處理其中R₁ 、R₉ 、R₇ 、R₈ 和A係如式I中所定義的式 (XXVIII) 之化合物。此類方法先前已經描述於例如WO 2016/071214中。Formula (XXVI) wherein R ₁ , R ₉ , R ₇ , R ₈ and A are as defined in formula I and wherein Xd is a free radical (such as chlorine, bromine or iodine (preferably chlorine or bromine)) Compound Flow 14:

It can be prepared by the following method (Scheme 14): typically in a solvent such as methanol, acetonitrile, tetrahydrofuran, ethyl acetate, chloroform or dichloromethane, or a mixture thereof at a temperature between 0°C and 150°C. It is better to use halogenating reagents ("Xd ⁺ " source) (such as N-bromosuccinimide, N-iodosuccinimide) under microwave heating conditions at a temperature between room temperature and 120°C. amine, N- chlorosuccinimide (PEI), I _2, CuBr _2, Br ₂ in acetic acid, or trimethyl (phenyl) ammonium tribromide PhNMe ₃ ⁺ Br ₃ ^-) processing wherein R _1, R _9, R ₇ , R ₈ and A are compounds of formula (XXVIII) as defined in formula I. Such methods have previously been described in, for example, WO 2016/071214.

Wherein R ₁ , R ₉ , R ₇ , R ₈ and A are as defined in formula I. The compound of formula (XXVIII) can be prepared by the following method: under the conditions described above (see Scheme 5, compound III Under conversion to II), the compound of formula (XXIX-b) where R ₉ , R ₁ and A are as defined in formula I and where R ₇ and R ₈ are as defined in formula I and where Xa is Reaction of the compound of formula IV leaving the group (such as chlorine, bromine or iodine (preferably iodine or bromine), or aryl-, alkyl- or haloalkylsulfonate (such as triflate)) .

Wherein R ₉ , R ₁ and A are the compounds of formula (XXIX-b) as defined in formula I can be prepared by the following method: under the conditions described above (see Scheme 6 to convert compound V to III) Next, the compound of formula (XXIX-a) where R ₁ , R ₉ and A are as defined in formula I and Xa are separated from groups (such as chlorine, bromine or iodine (preferably chlorine or bromine) , Or aryl-, alkyl- or haloalkyl sulfonate (such as trifluoromethanesulfonate) of the compound of formula VI.

Alternatively, the compound of formula (XXVIII) wherein R ₁ , R ₉ , R ₇ , R ₈ and A are as defined in formula I can be prepared by the following method: wherein R ₁ , R ₉ , R ₇ , R ₈ and A are the compounds of formula (XXIX-c) as defined in formula I and are subjected to the dehydration conditions already described above (see Scheme 7 to convert compound VII to II).

Wherein R ₁ , R ₉ , R ₇ , R ₈ and A are as defined in formula I. The compound of formula (XXIX-c) can be prepared by the following method: under the conditions described above (see Scheme 8, the Under the conversion of compound V to VII), the compound of formula (XXIX-a) wherein R ₁ , R ₉ and A are as defined in formula I and wherein R ₇ and R ₈ are as defined in formula I and wherein Xa is the reaction of the compound of formula VIII leaving the group (such as chlorine, bromine or iodine (preferably bromine), or aryl-, alkyl- or haloalkyl sulfonate (such as triflate)) .

Wherein R ₁ , R ₉ and A are compounds of formula (XXIX-a) as defined in formula I can be prepared by the following method: under the conditions already described above (see Scheme 9 for converting compound IX to V) Next, where R ₁ , R ₉ and A are as defined in formula I and where Xf is free from groups (such as chlorine, bromine or iodine (preferably bromine), or aryl-, alkyl- or The compound of formula (XXIX) of halogenated alkyl-sulfonate (such as triflate) is reacted with, for example, benzaldehyde oxime PhC=NOH, preferably (E)-benzaldehyde oxime. Alternatively, the method for preparing the compound of formula (XXIX-a) from the compound of formula (XXIX) may also involve the boronation/oxidation conditions also described in Scheme 9.

Wherein R ₁ , R ₉ and A are as defined in formula I and where Xf is a leaving group (such as chlorine, bromine or iodine, or aryl-, alkyl- or haloalkylsulfonate (such as trifluoromethyl) Sulfonate)) compounds of formula (XXIX), especially those compounds in which Xf is a halogen (even more preferably chlorine, bromine or iodine; particularly preferably chlorine or bromine), or known compounds , Are commercially available or can be prepared by known methods described in the literature (such as, for example, in WO 2016/071214).

可以藉由以下方式來製備（流程15）：在上面已描述的條件（參見流程11，將化合物 (XX) 轉化為II-Q1）下，將其中R₁ 、R₉ 、R₇ 、R₈ 、A、R₃ 、R₄ 和R₂ 係如式I中所定義的式 (XXXa) 之化合物或具有相同的取代基定義的式 (XXXb) 之區域異構物或其任何比率的混合物環化。Alternatively, the compound of formula II wherein Q is Q ₅ (defined as the compound of formula II-Q ₅ ), wherein R ₁ , R ₉ , R ₇ , R ₈ , A, R ₃ , R ₄ and R ₂ are as As defined in formula I, process 15:

It can be prepared by the following method (Scheme 15): Under the conditions described above (see Scheme 11, the compound (XX) is converted to II-Q1), R ₁ , R ₉ , R ₇ , R ₈ , A, R ₃ , R ₄ and R ₂ are compounds of formula (XXXa) as defined in formula I or regioisomers of formula (XXXb) with the same substituent definition or mixtures of any ratio cyclized.

Wherein R ₁ , R ₉ , R ₇ , R ₈ , A, R ₃ , R ₄ and R ₂ are compounds of formula (XXXa) as defined in formula I or regions of formula (XXXb) defined by the same substituents The isomers or mixtures in any ratio can be prepared by the following method: under the conditions already described above (see Scheme 11, the conversion of compounds (XXII) and (XI) to compound (XX)), using R ₃ , R ₄ and R ₂ are the compounds of formula (XXXI) as defined in formula I to treat the above-mentioned active substance (XXII).

Wherein R ₃ , R ₄ and R ₂ are compounds of formula (XXXI) as defined in formula I have previously been described in, for example, WO 2016/023954, WO 2016/142326 and WO 2017/133994.

可以藉由以下方式製備（流程16）：在例如乙醇、甲苯或乙腈的惰性溶劑中，視需要在諸如碳酸鈉、碳酸鉀或碳酸銫（或碳酸氫鈉或碳酸氫鉀）的合適鹼的存在下在50°C與150°C之間的溫度下，視需要在微波加熱條件下，使其中R₁ 、R₉ 、R₇ 、R₈ 和A係如式I中所定義的並且其中Xd係脫離基（例如像氯、溴或碘（較佳的是氯或溴））的上述式 (XXVI) 之化合物與其中R₂ 係如式I中所定義的式 (XXXII) 之化合物縮合。此類方法先前已經描述於例如WO 2011/074658中。其中R₂ 係如式I中所定義的式 (XXXII) 之化合物或者是已知化合物，可商購獲得，或者可藉由熟悉該項技術者已知的已知方法來製備（參見例如WO 2011/074658和WO 2010/083145）。Alternatively, the compound of formula II where Q is Q ₃ (defined as the compound of formula II-Q ₃ ), wherein R ₁ , R ₉ , R ₇ , R ₈ , A and R ₂ are as defined in formula I, Process 16:

It can be prepared by the following method (Scheme 16): In an inert solvent such as ethanol, toluene or acetonitrile, if necessary in the presence of a suitable base such as sodium carbonate, potassium carbonate or cesium carbonate (or sodium bicarbonate or potassium bicarbonate) At a temperature between 50°C and 150°C, optionally under microwave heating conditions, where R ₁ , R ₉ , R ₇ , R ₈ and A are as defined in formula I and where Xd is The compound of the above formula (XXVI) leaving the group (such as chlorine, bromine or iodine (preferably chlorine or bromine)) is condensed with the compound of the formula (XXXII) wherein R ₂ is as defined in formula I. Such methods have previously been described in, for example, WO 2011/074658. Wherein R ₂ is a compound of formula (XXXII) as defined in formula I or is a known compound, commercially available, or can be prepared by a known method known to those skilled in the art (see, for example, WO 2011 /074658 and WO 2010/083145).

可以藉由以下方式來製備（流程17）：在諸如亞磷酸三烷基酯（更具體地，例如，亞磷酸三乙酯）、三烷基膦或三苯基膦的還原劑的存在下，還原環化其中R₁ 、R₉ 、R₇ 、R₈ 、A、G₁ 、G₂ 和R₂ 係如式I中所定義的式 (XXXIII) 之化合物。此還原環化的原理類似於已知的卡多根（Cadogan）反應。可替代地，此反應可以在金屬催化劑的存在下進行，該金屬催化劑例如鉬(VI)催化劑（諸如MoO₂ Cl₂ (dmf)₂ [氯化氧鉬-雙(二甲基甲醯胺)]，或更通常地用與諸如亞磷酸三乙酯、三苯基膦或CO的還原劑組合的過渡金屬錯合物。合適的溶劑可以包括在室溫與200°C之間、較佳的是在50°C與160°C之間的溫度下，視需要在微波加熱條件下，使用過量的還原劑（諸如亞磷酸三乙酯），或例如甲苯或二甲苯。此類還原環化反應條件描述於例如WO 2017/134066中。Alternatively, the compound of formula II wherein Q is Q ₄ (defined as the compound of formula II-Q ₄ ), wherein R ₁ , R ₉ , R ₇ , R ₈ , A, G ₁ , G ₂ and R _{2 are} as in formula As defined in I, process 17:

It can be prepared in the following manner (Scheme 17): In the presence of a reducing agent such as trialkyl phosphite (more specifically, for example, triethyl phosphite), trialkylphosphine or triphenylphosphine, Reductive cyclization wherein R ₁ , R ₉ , R ₇ , R ₈ , A, G ₁ , G ₂ and R ₂ are compounds of formula (XXXIII) as defined in formula I. The principle of this reductive cyclization is similar to the known Cadogan reaction. Alternatively, this reaction can be carried out in the presence of a metal catalyst, such as a molybdenum (VI) catalyst (such as MoO ₂ Cl ₂ (dmf) ₂ [molybdenum oxychloride-bis(dimethylformamide)] , Or more commonly a transition metal complex combined with a reducing agent such as triethyl phosphite, triphenylphosphine or CO. Suitable solvents may be included between room temperature and 200°C, preferably At a temperature between 50°C and 160°C, an excess of reducing agent (such as triethyl phosphite), or, for example, toluene or xylene, is used under microwave heating as needed. Such reductive cyclization reaction conditions It is described in, for example, WO 2017/134066.

Wherein R ₁ , R ₉ , R ₇ , R ₈ , A, G ₁ , G ₂ and R ₂ are as defined in formula I. The compound of formula (XXXIII) can be prepared by the following method: usually at room temperature and Between 200 °C, preferably at a temperature between 40 °C and 160, if necessary, under microwave heating conditions, in a suitable solvent to make R ₁ , R ₉ , R ₇ , R ₈ and A is the reaction between the compound of formula (XXXIV) as defined in formula I and the compound of formula (XXXV) where G ₁ , G ₂ and R ₂ are as defined in formula I, and the suitable solvent may include For example, toluene or xylene °C. The formation of compounds of formula (XXXIII) may require removal of water by azeotropic distillation or by means of desiccants such as TiCl ₄ or molecular sieves. This formation of the Schiff base of formula (XXXIII) is known to those skilled in the art, and is described in, for example, WO 2017/134066.

Wherein G ₁ , G ₂ and R ₂ are compounds of formula (XXXV) as defined in formula I or are known compounds, which are commercially available or can be prepared by known methods known to those skilled in the art preparation.

可以藉由以下方式來製備（流程18）：使上述式 (XXIII) 之化合物（或也上述的其相應的活化物質 (XXII)）經受熟悉該項技術者已知的庫爾提斯（Curtius）重排/降解條件。例如，在WO 2009099086和Journal of Medicinal Chemistry [藥物化學雜誌], 55(22), 9589-9606; 2012中已經描述了此類條件。Wherein R ₁ , R ₉ , R ₇ , R ₈ and A are the compound of formula (XXXIV) as defined in formula I. Scheme 18:

It can be prepared by the following method (Scheme 18): subjecting the compound of the above formula (XXIII) (or the corresponding activating substance (XXII) also above) to Curtius known to those skilled in the art Rearrangement/degradation conditions. For example, such conditions have been described in WO 2009099086 and Journal of Medicinal Chemistry, 55(22), 9589-9606; 2012.

The reactant can be reacted in the presence of a base. Examples of suitable bases are alkali metal or alkaline earth metal hydroxides, alkali metal or alkaline earth metal hydrides, alkali metal or alkaline earth metal amides, alkali metal or alkaline earth metal alkoxides, alkali metal or alkaline earth metal acetates, alkali metal or Alkaline earth metal carbonates, alkali metal or alkaline earth metal dialkyl amides or alkali metal or alkaline earth metal alkylsilyl amines, alkyl amines, alkylene diamines, free or N-alkylated saturated or non- Saturated cycloalkylamines, basic heterocycles, ammonium hydroxide and carbocyclic amines. Examples that may be mentioned are sodium hydroxide, sodium hydride, sodium amide, sodium methoxide, sodium acetate, sodium carbonate, potassium tertiary butoxide, potassium hydroxide, potassium carbonate, potassium hydride, lithium diisopropylamide, Potassium bis(trimethylsilyl)amine, calcium hydride, triethylamine, diisopropylethylamine, triethylenediamine, cyclohexylamine, N-cyclohexyl-N,N-dimethylamine , N,N-diethylaniline, pyridine, 4-(N,N-dimethylamino)pyridine, quinidine, N-methyl pyridine, benzyltrimethylammonium hydroxide and 1,8 -Diazabicyclo[5.4.0]undec-7-ene (DBU).

(XXXVI)， 其中 R₁ 、R₇ 、R₈ 、R₉ 和A係如上式I所定義的並且R₁₀₀ 係OH、氯或C₁ -C₄ 烷氧基，Compound of formula XXXVI

(XXXVI), wherein R ₁ , R ₇ , R ₈ , R ₉ and A are as defined in formula I above and R ₁₀₀ is OH, chlorine or C ₁ -C ₄ alkoxy,

It is novel, was specially developed for the preparation of the compound of formula I according to the present invention and therefore represents another object of the present invention. The preferred items and preferred embodiments of the substituents of the compound of formula I are also effective for the compound of formula XXXVI.

The reactants can react with each other themselves, that is, no solvent or diluent is added. However, in most cases, it is advantageous to add an inert solvent or diluent or a mixture of these substances. If the reaction is carried out in the presence of a base, the base used in excess, such as triethylamine, pyridine, N-methyl pyridine or N,N-diethylaniline, can also serve as a solvent or diluent.

The reaction is advantageously in the temperature range from about -80°C to about +140°C, preferably from about -30°C to about +100°C, in many cases at ambient temperature and about +80°C. The range between °C.

The compound of formula I can be converted into another compound of formula I in a manner known per se by using one or more substituents of the starting compound of formula I with another or other according to the present invention in a customary manner. One or more substituents are substituted.

Depending on the selected reaction conditions and starting materials suitable for the respective situation, it is possible, for example, to replace only one substituent with another substituent according to the present invention in one reaction step, or to replace it in the same reaction step. Multiple substituents are replaced with multiple other substituents according to the present invention.

The salt of the compound of formula I can be prepared in a manner known per se. Therefore, for example, the acid addition salt of the compound of formula I is obtained by treatment with a suitable acid or a suitable ion exchanger reagent, and the salt with a base is obtained by using a suitable base or a suitable ion. Exchanger reagents are processed to obtain.

The salt of the compound of formula I can be converted into the free compound I, acid addition salt (for example by treatment with a suitable basic compound or with a suitable ion exchanger reagent) and a salt with a base (for example By treating with a suitable acid or with a suitable ion exchanger reagent).

The salt of the compound of formula I can be converted into other salts, acid addition salts of the compound of formula I, for example into other acid addition salts, for example by using a suitable acid in a suitable solvent in a manner known per se Metal salts (such as sodium, barium or silver salts, for example, with silver acetate) are treated with inorganic acid salts (such as hydrochloride) in which the inorganic salts (such as silver chloride) formed are insoluble and therefore Precipitated from the reaction mixture.

Depending on the procedure or reaction conditions, the compound of formula I having salt-forming properties can be obtained in free form or in salt form.

Depending on the number, absolute and relative configuration of the asymmetric carbon atoms present in the molecule and/or the configuration of the non-aromatic double bond present in the molecule, the compound of formula I and its tautomers (in In each case in free form or in salt form) may exist as one of the possible isomers or as a mixture of these, for example as pure isomers (such as enantiomers and/or diastereomers) Or as a mixture of isomers, such as a mixture of enantiomers (for example, a racemate, a mixture of diastereomers, or a mixture of racemates); the present invention relates to pure isomers and all possible A mixture of isomers, and in each case above and below should be understood in this sense, even when the stereochemical details are not explicitly mentioned in each case.

The diastereomer mixtures or racemate mixtures of the compounds of formula I in free form or in salt form (their acquisition may depend on the selected starting materials and procedures) can be used in the physical On the basis of chemical differences, for example, fractional crystallization, distillation, and/or chromatography can be separated into pure diastereomers or racemates in a known manner.

A mixture of enantiomers (such as racemates) that can be obtained in a similar manner can be resolved into optical enantiomers by known methods, for example, by recrystallization from an optically active solvent; Chromatography, such as high performance liquid chromatography (HPLC) on acetyl cellulose; by means of suitable microorganisms, by cleavage with specific immobilized enzymes; by formation of containing compounds, for example by using chiral crown ethers , Where only one of the enantiomers is complexed; or by conversion into a diastereoisomer salt, for example, by making the racemate of the basic final product and optically active acid (such as carboxylic acid, such as camphoric acid, Tartaric acid or malic acid, or sulfonic acid, such as camphorsulfonic acid) react, and separate the diastereomer mixtures obtained in this way by, for example, stepwise crystallization based on their different solubility to give diastereomers The desired enantiomers can be freed from these diastereomers by the action of suitable reagents (such as alkaline reagents).

Pure diastereomers or spiegelmers can be obtained according to the present invention, not only by separating suitable mixtures of isomers, but also by commonly known non-spiegel image stereoselective or mirror image selective synthesis. The method, for example, by carrying out the method according to the invention with starting materials with suitable stereochemistry.

The N-oxide can be prepared by reacting the compound of formula I with a suitable oxidizing agent (for example H ₂ O ₂ /urea adduct) in the presence of an acid anhydride (for example trifluoroacetic anhydride). Such oxidation is known from the literature, for example from J. Med. Chem. [Journal of Medicinal Chemistry] 32 (12), 2561-73, 1989 or WO 00/15615.

Wherein R ₂ is a C ₁ -C ₄ haloalkylsulfinyl or C ₁ -C ₄ haloalkylsulfinyl compound, for example, a suitable oxidation method described in WO 19/008115 can be obtained from wherein R ₂ is C ₁ -C ₄ haloalkylsulfanyl corresponding compounds are prepared.

If the individual components have different biological activities, it is advantageous to separate or synthesize biologically more effective isomers in each case, such as enantiomers or diastereomers or mixtures of isomers, for example A mixture of enantiomers or a mixture of diastereomers.

The compound of formula I and, where appropriate, its tautomers (in free form or in salt form in each case), if appropriate, may also be obtained in the form of hydrates and/or include other solvents, for example, may be used to make solid Those in the form of crystalline compounds.

(I) 索引 n A R₉ R₇ R₈ 1 1 N H H CH₃ 2 1 N H CH₃ CH₃ 3 1 N CH₃ CH₃ CH₃ 4 1 CH H H CH₃ 5 1 CH H CH₃ CH₃ 6 1 CH CH₃ CH₃ CH₃ 表A-1提供了6種式I的化合物A-1.001至A-1.006，其中R₁ 係乙基，R₁₀ 係氫，並且n、A、R₉ 、R₇ 和R₈ 係如在表X中所定義的，並且Q取自式Q₁ 的基團，為

例如，化合物A-1.006具有以下結構：

(A-1.006) 表A-2提供了6種式I的化合物A-2.001至A-2.006，其中R₁ 係乙基，R₁₀ 係氫，並且n、A、R₉ 、R₇ 和R₈ 係如在表X中所定義的，並且Q取自式Q₁ 的基團，為

表A-3提供了6種式I的化合物A-3.001至A-3.006，其中R₁ 係乙基，R₁₀ 係氫，並且n、A、R₉ 、R₇ 和R₈ 係如在表X中所定義的，並且Q取自式Q₁ 的基團，為

表A-4提供了6種式I的化合物A-4.001至A-4.006，其中R₁ 係乙基，R₁₀ 係氫，並且n、A、R₉ 、R₇ 和R₈ 係如在表X中所定義的，並且Q取自式Q₂ 的基團，為

表A-5提供了6種式I的化合物A-5.001至A-5.006，其中R₁ 係乙基，R₁₀ 係氫，並且n、A、R₉ 、R₇ 和R₈ 係如在表X中所定義的，並且Q取自式Q₂ 的基團，為

表A-6提供了6種式I的化合物A-6.001至A-6.006，其中R₁ 係乙基，R₁₀ 係氫，並且n、A、R₉ 、R₇ 和R₈ 係如在表X中所定義的，並且Q取自式Q₃ 的基團，為

表A-7提供了6種式I的化合物A-7.001至A-7.006，其中R₁ 係乙基，R₁₀ 係氫，並且n、A、R₉ 、R₇ 和R₈ 係如在表X中所定義的，並且Q取自式Q₁ 的基團，為

表A-8提供了6種式I的化合物A-8.001至A-8.006，其中R₁ 係乙基，R₁₀ 係氫，並且n、A、R₉ 、R₇ 和R₈ 係如在表X中所定義的，並且Q取自式Q₁ 的基團，為

表A-9提供了6種式I的化合物A-9.001至A-9.006，其中R₁ 係乙基，R₁₀ 係氫，並且n、A、R₉ 、R₇ 和R₈ 係如在表X中所定義的，並且Q取自式Q₄ 的基團，為

表A-10提供了6種式I的化合物A-10.001至A-10.006，其中R₁ 係乙基，R₁₀ 係氫，並且n、A、R₉ 、R₇ 和R₈ 係如在表X中所定義的，並且Q取自式Q₄ 的基團，為

表A-11提供了6種式I的化合物A-11.001至A-11.006，其中R₁ 係乙基，R₁₀ 係氫，並且n、A、R₉ 、R₇ 和R₈ 係如在表X中所定義的，並且Q取自式Q₅ 的基團，為

表A-12提供了6種式I的化合物A-12.001至A-12.006，其中R₁ 係乙基，R₁₀ 係氫，並且n、A、R₉ 、R₇ 和R₈ 係如在表X中所定義的，並且Q取自式Q₅ 的基團，為

表A-13提供了6種式I的化合物A-13.001至A-13.006，其中R₁ 係乙基，R₁₀ 係氫，並且n、A、R₉ 、R₇ 和R₈ 係如在表X中所定義的，並且Q取自式Q₅ 的基團，為

表A-14提供了6種式I的化合物A-14.001至A-14.006，其中R₁ 係乙基，R₁₀ 係氫，並且n、A、R₉ 、R₇ 和R₈ 係如在表X中所定義的，並且Q取自式Q₂ 的基團，為

表A-15提供了6種式I的化合物A-15.001至A-15.006，其中R₁ 係乙基，R₁₀ 係氫，並且n、A、R₉ 、R₇ 和R₈ 係如在表X中所定義的，並且Q取自式Q₂ 的基團，為

表A-16提供了6種式I的化合物A-16.001至A-16.006，其中R₁ 係乙基，R₁₀ 係氫，並且n、A、R₉ 、R₇ 和R₈ 係如在表X中所定義的，並且Q取自式Q₂ 的基團，為

表A-17提供了6種式I的化合物A-17.001至A-17.006，其中R₁ 係乙基，R₁₀ 係氫，並且n、A、R₉ 、R₇ 和R₈ 係如在表X中所定義的，並且Q取自式Q₂ 的基團，為

The compounds of formula I according to the following table X and A-1 to A-17 can be prepared according to the method described above. The following examples are intended to illustrate the invention and show preferred compounds of formula I. [Table X]: The definition of the substituents of n, A, R ₉ , R ₇ and R ₈ in the compound of formula I:

(I) index n A R ₉ R ₇ R ₈ 1 1 N H H CH ₃ 2 1 N H CH ₃ CH ₃ 3 1 N CH ₃ CH ₃ CH ₃ 4 1 CH H H CH ₃ 5 1 CH H CH ₃ CH ₃ 6 1 CH CH ₃ CH ₃ CH ₃ Table A-1 provides 6 compounds A-1.001 to A-1.006 of formula I, wherein R ₁ is ethyl, R ₁₀ is hydrogen, and n, A, R ₉ , R ₇ and R ₈ are as shown in Table X And Q is taken from the group of formula Q ₁ , which is

For example, compound A-1.006 has the following structure:

(A-1.006) Table A-2 provides 6 compounds A-2.001 to A-2.006 of formula I, wherein R ₁ is ethyl, R ₁₀ is hydrogen, and n, A, R ₉ , R ₇ and R ₈ Is as defined in Table X, and Q is taken from the group of formula Q ₁ , which is

Table A-3 provides 6 compounds A-3.001 to A-3.006 of formula I, wherein R ₁ is ethyl, R ₁₀ is hydrogen, and n, A, R ₉ , R ₇ and R ₈ are as shown in Table X And Q is taken from the group of formula Q ₁ , which is

Table A-4 provides 6 compounds A-4.001 to A-4.006 of formula I, wherein R ₁ is ethyl, R ₁₀ is hydrogen, and n, A, R ₉ , R ₇ and R ₈ are as shown in Table X And Q is taken from the group of formula Q ₂ , which is

Table A-5 provides 6 compounds A-5.001 to A-5.006 of formula I, wherein R ₁ is ethyl, R ₁₀ is hydrogen, and n, A, R ₉ , R ₇ and R ₈ are as shown in Table X And Q is taken from the group of formula Q ₂ , which is

Table A-6 provides six compounds A-6.001 to A-6.006 of formula I, wherein R ₁ is ethyl, R ₁₀ is hydrogen, and n, A, R ₉ , R ₇ and R ₈ are as shown in Table X And Q is taken from the group of formula Q ₃ , which is

Table A-7 provides 6 compounds A-7.001 to A-7.006 of formula I, wherein R ₁ is ethyl, R ₁₀ is hydrogen, and n, A, R ₉ , R ₇ and R ₈ are as shown in Table X And Q is taken from the group of formula Q ₁ , which is

Table A-8 provides 6 compounds A-8.001 to A-8.006 of formula I, wherein R ₁ is ethyl, R ₁₀ is hydrogen, and n, A, R ₉ , R ₇ and R ₈ are as shown in Table X And Q is taken from the group of formula Q ₁ , which is

Table A-9 provides 6 compounds A-9.001 to A-9.006 of formula I, wherein R ₁ is ethyl, R ₁₀ is hydrogen, and n, A, R ₉ , R ₇ and R ₈ are as shown in Table X And Q is taken from the group of formula Q ₄ , which is

Table A-10 provides 6 compounds A-10.001 to A-10.006 of formula I, wherein R ₁ is ethyl, R ₁₀ is hydrogen, and n, A, R ₉ , R ₇ and R ₈ are as shown in Table X And Q is taken from the group of formula Q ₄ , which is

Table A-11 provides 6 compounds A-11.001 to A-11.006 of formula I, wherein R ₁ is ethyl, R ₁₀ is hydrogen, and n, A, R ₉ , R ₇ and R ₈ are as shown in Table X And Q is taken from the group of formula Q ₅ , which is

Table A-12 provides 6 compounds A-12.001 to A-12.006 of formula I, wherein R ₁ is ethyl, R ₁₀ is hydrogen, and n, A, R ₉ , R ₇ and R ₈ are as shown in Table X And Q is taken from the group of formula Q ₅ , which is

Table A-13 provides 6 compounds A-13.001 to A-13.006 of formula I, wherein R ₁ is ethyl, R ₁₀ is hydrogen, and n, A, R ₉ , R ₇ and R ₈ are as shown in Table X And Q is taken from the group of formula Q ₅ , which is

Table A-14 provides 6 compounds A-14.001 to A-14.006 of formula I, wherein R ₁ is ethyl, R ₁₀ is hydrogen, and n, A, R ₉ , R ₇ and R ₈ are as shown in Table X And Q is taken from the group of formula Q ₂ , which is

Table A-15 provides 6 compounds A-15.001 to A-15.006 of formula I, wherein R ₁ is ethyl, R ₁₀ is hydrogen, and n, A, R ₉ , R ₇ and R ₈ are as shown in Table X And Q is taken from the group of formula Q ₂ , which is

Table A-16 provides 6 compounds A-16.001 to A-16.006 of formula I, wherein R ₁ is ethyl, R ₁₀ is hydrogen, and n, A, R ₉ , R ₇ and R ₈ are as shown in Table X And Q is taken from the group of formula Q ₂ , which is

Table A-17 provides 6 compounds A-17.001 to A-17.006 of formula I, wherein R ₁ is ethyl, R ₁₀ is hydrogen, and n, A, R ₉ , R ₇ and R ₈ are as shown in Table X And Q is taken from the group of formula Q ₂ , which is

The compounds of formula I according to the present invention are active ingredients with preventive and/or therapeutic value in the field of pest control (even at low application rates). These ingredients have a very favorable biocidal spectrum and are warm-blooded. Well tolerated by species, fish and plants. The active ingredients according to the present invention act on all or individual developmental stages of animal pests (such as insects or representatives of the order Acarina, nematodes or molluscs) that are generally sensitive and also resistant. The insecticidal, nematicidal, molluscicidal or acaricidal activity of the active ingredients according to the present invention can manifest itself directly, that is, manifest as the death or destruction of harmful organisms, which can occur immediately or only after a period of time, such as in molting. Occurs during the process, or manifests indirectly as, for example, reduced spawning and/or hatching rates, antifeeding effects, and/or growth inhibition.

Examples of the above-mentioned animal pests are: from the order Acarina, such as Acalitus spp, Aculus spp, Acaricalus spp., Acaricalus spp. (Aceria spp.), Acarus siro, Amblyomma spp., Argas spp., Boophilus spp., Short hair mite Genus species (Brevipalpus spp.), Bryobia spp., Calipitrimerus spp., Chorioptes spp., Dermanyssus gallinae, Epidermal mites Genus species (Dermatophagoides spp), Eotetranychus spp, Eriophyes spp., Hemitarsonemus spp, Hyalomma spp., Hyalomma spp. Ixodes (Ixodes spp.), Olygonychus spp, Ornithodoros spp., Polyphagotarsone latus, Panonychus spp. ), Phyllocoptruta oleivora, Phytonemus spp., Polyphagotarsonemus spp, Psoroptes spp., Rhipicephalus spp. ( Rhipicephalus spp.), Rhizoglyphus spp., Sarcoptes spp., Steneotarsonemus spp, Tarsonemus spp., and Tetranychus Species (Tetranychus spp.); from the order of the Anopus, such as Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp.) and Phylloxera spp.; from the order Coleoptera, such as Agriotes spp., Amphima llon majale, Anomala orientalis, Anthonomus spp., Aphodius spp, Astylus atromaculatus, Ataenius spp, sugar beet Atomaria linearis, Chaetocnema tibialis, Cerotoma spp, Conoderus spp, Cosmopolites spp., Green Cotinis nitida, Curculio spp., Cyclocephala spp, Dermestes spp., Diabrotica spp., Diloboderus abderus, Epilachna spp., Eremnus, Heteronychus arator, Hypothenemus hampei, Lagria vilosa, Leptinotarsa decemLineata), Lissorhoptrus spp., Liogenys, Maecolaspis, Maladera castanea, Megascelis spp, Melighetes aeneus, Melolontha spp., Myochrous armatus, Orycaephilus spp., Otiorhynchus spp., Phyllophaga spp., Phyllophaga spp. (Phlyctinus spp.), Popillia spp., Psylliodes spp., Rhyssomatus aubtilis, Rhizopertha spp., Scarabeidae, Rice Elephant Genus species (Sitophilus spp.), wheat moth species (Sitotroga spp.), pseudo-cut rootworm species (Somaticus spp.), tipped cryptorhynchus species (Sph enophorus spp), Sternechus subsignatus, Tenebrio spp., Tribolium spp. and Trogoderma spp.; from Diptera, For example, Aedes spp., Anopheles spp, Antherigona soccata., Bactrocea oleae, Bibio hortulanus, and Anopheles spp. Species (Bradysia spp.), Calliphora erythrocephala, Ceratitis spp., Chrysomyia spp., Culex spp., Yellow fly Species (Cuterebra spp.), Dacus spp., Delia spp, Drosophila melanogaster, Fannia spp., Stomach fly Genus species (Gastrophilus spp.), Geomyza tripunctata, Glossina spp., Hypoderma spp., Hyppobosca spp., Liriomyza spp. ), Lucilia spp., Melanagromyza spp., Musca spp., Oestrus spp., Orseolia spp .), Oscinella frit, Pegomyia hyoscyami, Phorbia spp., Rhagoletis spp, Riveria quadrifasciata, Scatella species, Sharp eyes Sciara spp., Stomoxys spp., Tabanus spp., Tannia spp. and Tipula spp.; from half From the order of the Pterans, such as Acanthocoris scabrator, Acrosternum spp, Adel phocoris lineolatus, Amblypelta nitida, Bathycoelia thalassina, Blissus spp, Cimex spp., Clavigralla tomentosdesicollis, Creontia spp.), Distantiella theobroma, Dichelops furcatus, Dysdercus spp., Edessa spp, Euschistus spp., Six-spotted bug Eurydema pulchrum, Eurygaster spp., Halyomorpha halys, Horcias nobilellus, Leptocorisa spp., Lygus Genus species (Lygus spp), tropical giant scale species (Margarodes spp), cabbage spotted bug (Murgantia histrionic), Neomegalotomus spp, tobacco bug (Nesidiocoris tenuis), green stink bug ( Nezara spp., Nysius simulans, Oebalus insularis, Piesma spp., Piezodorus spp, Rhodnius spp. , Cocoa brown bug (Sahlbergella singularis), chestnut bug (Scaptocoris castanea), black bug (Scotinophara spp.), Thyanta species, Triatoma spp., cassava bug (Vatiga illudens) ; Acyrthosium pisum (Acyrthosium pisum), Adalges species, Agalliana ensigera, Agonoscena targionii, Aleurodicus spp., Aleurocanthus spp. , Sugarcane whitefly (Aleurolobus barodensis), soft whitefly (Aleurothrixus floccosus), cabbage whitefly (Aleyr odes brassicae), cotton leafhopper (Amarasca biguttula), lemon fruit leafhopper (Amritodus atkinsoni), kidney scale (Aonidiella spp.), Aphididae (Aphididae), Aphis spp., Scale species (Aspidiotus spp.), Aulacorthum solani, potato/tomato psyllid (Bactericera cockerelli), Bemisia spp, Brachycaudus spp., Cabbage aphid (Brevicoryne brassicae), Cacopsylla spp, Cavariella aegopodii Scop., Ceroplaster spp., Chrysomphalus aonidium, Orange brown circle Chrysomphalus dictyospermi (Chrysomphalus dictyospermi), Cicadella spp, Cofana spectra, Cryptomyzus spp, Cicadulina spp, Coccus hesperidum , Corn yellow-winged leafhopper (Dalbulus maidis), nude whitefly species (Dialeurodes spp), citrus psyllid (Diaphorina citri), wheat double-tailed aphid (Diuraphis noxia), western ringworm (Dysaphis spp), small green leaf Cicada species (Empoasca spp.), Apple cotton aphid (Eriosoma larigerum), Grape leafhopper (Erythroneura spp.), Gascardia species, Glycaspis brimblecombei (Glycaspis brimblecombei), Hyadaphis pseudobrassicae (Hyadaphis pseudobrassicae) , Hyalopterus spp., Hyperomyzus pallidus, Idioscopus clypealis, African leafhopper (Jacobiasca lybica), Laodelphax spp., soil and water Lecanium corni, Lepidosaphes spp., Lopaphis erysimi, Lyog enys maidis, Macrosiphum spp., Mahanarva spp, Metcalfa pruinosa, Metopolophium dirhodum, Myndus crudus, Tumor Aphid species (Myzus spp.), Neotoxoptera sp., Nephotettix spp., Nilaparvata spp., Nippolachnus piri Mats ), Odonaspis ruthae, Oregma lanigera Zehnter (Oregma lanigera Zehnter), Parabemisia myricae (Parabemisia myricae), Paratrioza cockerelli (Paratrioza cockerelli), Parlatoria spp., Pemphigus spp.), Peregrinus maidis, Perkinsiella spp, Phorodon humuli, Phylloxera spp, Planococcus spp. ), Pseudaulacaspis spp., Pseudococcus spp., Pseudatomoscelis seriatus, Psylla spp., Cotton scale (Pulvinaria aethiopica), Quadraspidiotus spp., Quesada gigas, Recilia dorsalis (Recilia dorsalis), Rhopalosiphum spp., Saissetia spp., Saissetia spp. Scaphoideus spp., Schizaphis spp., Sitobion spp., Sogatella furcifera, Spissistilus festinus, Tarophagus Proserpina), Toxoptera spp, Trialeurodes spp, Tridiscus sporoboli, Trialeurodes spp (Trio nymus spp., Trioza erytreae, Unaspis citri, Zygina flammigera, Zyginidia scutellaris; from the order Hymenoptera, such as Acromyrmex, Three Sawfly species (Arge spp.), Leaf-cutting ants (Atta spp.), Cephus spp., Diprion spp., Diprionidae (Diprionidae) , Gilpinia polytoma (Gilpinia polytoma), Hoplocampa spp., Lasius spp., Monomorium pharaonis, Neodiprion spp., Agricultural Pogonomyrmex spp, Slenopsis invicta, Solenopsis spp. and Vespa spp.; from the order of the Isoptera, such as Coptotermes spp, termites (Corniternes cumulans), Incisitermes spp, Macrotermes spp, Mastotermes spp, Microtermes spp, Reticulitermes spp. ; Tropical fire ant (Solenopsis geminate) comes from Lepidoptera ( Lepidoptera ), for example, Acleris spp., Adoxophyes spp., Aegeria spp. ), Agrotis spp., Cotton leaf insect (Alabama argillaceae), Amylois species, Anticarsia gemmatalis, Archips spp., Silver moth ( Argyresthia spp.), Argyrotaenia spp., Autographa spp., Bucculatrix thurberiella, Busseola fusca, Meadow moth (Bucculatrix thurberiella) Cadra cautella), peach fruit moth (Carpos ina nipponensis), Chilo spp., Choristoneura spp., Chrysoteuchia topiaria, Clysia ambiguella, Clysia spp. (Cnaphalocrocis spp.), Cnephasia spp., Cochylis spp., Coleophora spp., Colias lesbia, Xiaozaoqiaoye Moth (Cosmophila flava), Crambus spp, Chinese cabbage borer (Crocidolomia binotalis), Apple shaped small curl moth (Cryptophlebia leucotreta), boxwood moth (Cydalima perspectalis), Cydia spp. , Diaphania perspectalis (Diaphania perspectalis), Diatraea spp., Sudan cotton bollworm (Diparopsis castanea), Earias spp., Eldana saccharina, pink spot Ephestia spp., Epinotia spp., Estigmene acrea, Etiella zinckinella, Eucosma spp., Eucosma spp. Moths (Eupoecilia ambiguella), Euproctis spp., Euproca spp., Feltia jaculiferia, Grapholita spp., Hedya nubiferana , Heliothis spp., Heliothis spp., Hellula undalis, Herbetogramma spp., Hyphantria cunea, Keiferia lycopersicella, Lasmopalpus lignosellus, Leaf miner (Leucoptera scitella), leaf miner species (Lithocollethis spp.), grape flower-winged moth (Lobesia botrana), Loxostege bifidalis, Lymantria spp., Lyonetia spp., Malacosoma spp., Mamestra brassicae, Manduca sexta, Light belly Species of the genus Mythimna (Mythimna spp.), Noctua spp, Operophtera spp., Orniodes indica, European Corn Borer (Ostrinia nubilalis), Pammene spp .), brown roll moth (Pandemis spp.), small eye moth (Panolis flammea), stem borer (Papaipema nebris), red bell wheat moth (Pectinophora gossypiela), coffee leaf miner (Perileucoptera coffeella), Pseudaletia unipuncta (Pseudaletia unipuncta), Potato wheat moth (Phthorimaea operculella), Pieris rapae (Pieris rapae), Pieris spp., Plutella xylostella (Plutella xylostella), Prays spp. ), Pseudoplusia spp, Rachiplusia nu, Richia albicosta, Scirpophaga spp., Sesamia spp .), Sparganothis spp., Spodoptera spp., Cotton Leaf Roller (Sylepta derogate), Synanthedon spp., Different Boat Moths (Thaumetopoea spp.), Tortrix spp., Trichoplusia ni, Tuta absoluta, and Yponomeuta spp.; from food From the order of the Mallophaga ( Mallophaga ), for example, Damalina spp. and Trichodectes spp.; from the order Orthoptera , for example, Blatta spp., Blatta Species (Blattella spp.), mole cricket species (Gryllotalpa spp.), Madeira cockroach (Leucophaea maderae), Locusta spp., Northern mole cricket (Neocurtilla hexadactyla), Periplaneta spp., Scapteriscus spp .), and desert locust species (Schistocerca spp.); from the order Psocoptera ( Psocoptera ), for example, Liposcelis spp.; from the order Siphonaptera , for example, Ceratophyllus spp.), Ctenocephalides spp., and Xenopsylla cheopis; from the order Thysanoptera , for example, Calliothrips phaseoli, Frankliniella spp., Sun thistle Equine species (Heliothrips spp), brown thrips (Hercinothrips spp.), uniparental thrips (Parthenothrips spp.), African orange hard thrips (Scirtothrips aurantii), soybean thrips (Sericothrips variabilis), Thrips species (Taeniothrips spp.), Thrips spp;

From the order Thysanura , for example, Lepisma saccharina.

The active ingredients according to the present invention can be used to control (ie contain or destroy) the above-mentioned types of harmful organisms, which are particularly present on plants, especially useful plants and ornamental plants in agriculture, horticulture, and forestry On plants, or on the organs of such plants (such as fruits, flowers, leaves, stems, tubers, or roots), and in some cases, even plant organs formed at a later point in time remain protected against such Pests.

In particular, suitable target crop lines, grains, such as wheat, barley, rye, oats, rice, corn or sorghum; sugar beets, such as sugar beets or fodder beets; fruits, such as pome, stone fruit or seedless fruit, Such as apples, pears, plums, peaches, almonds, cherries or berries such as strawberries, raspberries or blackberries; leguminous crops such as kidney beans, lentils, peas or soybeans; oil crops such as rapeseed, mustard, poppy, olive, sunflower , Coconut, castor, cocoa or groundnut; melon crops, such as pumpkin, cucumber or melon; fibrous plants, such as cotton, flax, hemp or jute; citrus fruits, such as orange, lemon, grapefruit or tangerine; vegetables, such as Spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes or sweet peppers; Lauraceae, such as avocado, cinnamon (Cinnamonium) or camphor; and tobacco, nuts, coffee, eggplant, sugar cane, tea, pepper, Vines, hops, plantain and latex plants.

The composition and/or method of the present invention can also be used on any ornamental plants and/or vegetable crops (including flowers, shrubs, broad-leaved trees and evergreen plants).

For example, the present invention can be used in any of the following ornamental plant species: Ageratum spp., Alonsoa spp., Anemone spp., South Africa Kwai (Anisodontea capsenisis), chamomile species (Anthemis spp.), snapdragon species (Antirrhinum spp.), Aster species (Aster spp.), begonia species (Begonia spp.) (for example, Rieger Begonia (B elatior , B. semperflorens , B. tubéreux ), Bougainvillea ( Bougainvillea spp.), Brachycome spp., Brassica spp. ) (Ornamental plants), Calceolaria species ( Calceolaria spp.), Pepper ( Capsicum annuum ), Catharanthus roseus ( Catharanthus roseus ), Canna spp., Centaurea spp., Centaurea spp. ( Chrysanthemum spp.), Cineraria spp. ( C. maritime ), Coreopsis spp., Rhodiola ( Crassula coccinea ), and Cuphea ignea ), Dahlia spp., Delphinium spp., Dicentra spectabilis, Dorotheantus spp., Eustoma grandiflorum , Forsythia spp.), Fuchsia spp., Geranium gnaphalium , Gerbera spp., Gomphrena globosa , Heliotrope Heliotropium spp., Helianthus spp., Hibiscus spp., Hortensia spp., Hydrangea spp., Hydrangea spp. Hypoestes phyllostachya ), Impatiens spp. ( I. Walleriana ), Iresines spp., Kalanchoe spp., Lantana ( Lantana camara ), March flower sunflower ( Lavatera trimestris ), Lion’s ear flower ( Leonotis leonurus ), Lilium spp., Mesembryanthemum spp., Mimulus spp., American peppermint ( Monarda spp.), Nemesia spp., Tagetes spp., Dianthus spp. (carnation), Canna spp., syrup Oxalis spp., Bellis spp., Pelargonium spp. ( P. peltatum , P. Zonale ), Viola ( Viola spp.) (Panthera), Petunia spp., Phlox spp., Plecthranthus spp., Poinsettia spp. ), Parthenocissus spp. ( P. quinquefolia , Parthenocissus ( P. tricuspidata )), Primula spp., Ranunculus spp., Rhododendron ( Rhododendron spp.), Rosa spp. (rose), Yellow daisy ( Rudbeckia spp.), Saintpaulia spp., Sage ( Salvia spp.), Purple Scaevola aemola , Schizanthus wisetonensis , Sedum spp., Solanum spp., Surfinia spp., Longevity Chrysanthemum species ( Tagetes spp.), tobacco Genus species ( Nicotinia spp.), Verbena spp. ( Verbena spp.), Zinnia spp. ( Zinnia spp.) and other flower bed plants.

For example, the present invention can be used in any of the following vegetable species: Allium spp. (garlic ( A. sativum ) , onion ( A.. cepa ), A. oschaninii , leeks ( A. Porrum) ), fire onion ( A. ascalonicum ), green onion ( A. fistulosum ), fennel celery ( Anthriscus cerefolium ), dry celery ( Apium graveolus ), asparagus ( Asparagus officinalis ), beet ( Beta vulgarus ), Brassica species ( Brassica) spp.) (Brassica oleracea ( B. Oleracea ), Chinese cabbage ( B. Pekinensis ), Turnip ( B. rapa )), Pepper ( Capsicum annuum ), Chickpea ( Cicer arietinum ), Chicory ( Cichorium endivia ), Cichorium species ( Cichorum spp.) (chicory ( C. intybus ), bittern ( C. endivia )), watermelon ( Citrillus lanatus ), Cucumis spp. (cucumber ( C. sativus ), melon ( C. melo ) ), Cucurbita spp. ( Cucurbita ( C. pepo ), Indian Pumpkin ( C. maxima )) , Cyanara spp. (Artichoke ( C. scolymus ), Cardoon ( C. scolymus )) C. cardunculus ), wild carrot ( Daucus carota ), fennel ( Foeniculum vulgare ), Hypericum spp., lettuce ( Lactuca sativa ), Lycopersicon spp. ( L. esculentum) ), cherry tomato ( L. lycopersicum )), mint ( Mentha spp.), basil ( Ocimum basilicum ), parsley ( Petroselinum crispum ), phaseolus spp. ( Phaseolus spp.) ( P. vulgaris ), P. coccineus ), peas ( Pisum sativum ), radish ( Raphanus sativus ), edible rhubarb ( Rheum rhaponticum), rosemary species (Rosemarinus spp.), species Salvia (Salvia spp.), black salsify (Scorzonera hispanica), eggplant (Solanum melongena), spinach (Spinacea oleracea), a new species of Valeriana ( Valerianella spp.) (lettuce valerian ( V. locusta ), V. eriocarpa ) and broad bean ( Vicia faba ) .

Preferred ornamental plant species, including African violet (African violet), Begonia (Begonia), Dahlia (Dahlia), gerbera (Gerbera), Hydrangea (Hydrangea), verbena (Verbena), Rosa ( Rosa ), Kalanchoe ( Kalanchoe ), Poinsettia ( Poinsettia ), Aster ( Aster ), Centaurea , Coreopsis , Delphinium , Monarda , Grass oleander genus (Phlox), rudbeckia (rudbeckia), sedum (Sedum), Petunia (Petunia), Viola (Viola), Impatiens (Impatiens), Geranium (Geranium), chrysanthemum Genus ( Chrysanthemum ), Ranunculus ( Ranunculus ), Fuchsia ( Fuchsia ), Sage ( Salvia ), Hydrangea ( Hortensia ), Rosemary, Sage, St. Johnswort (St. Johnswort) , Mint, sweet pepper, tomato and cucumber.

The active ingredients according to the present invention are particularly suitable for controlling Aphis craccivora (Aphis craccivora), cucumber striped leaf beetle (Diabrotica balteata), tobacco budworm (Heliothis virescens) and peach on cotton, vegetables, corn, rice and soybean crops. Aphid (Myzus persicae), Plutella xylostella (Plutella xylostella), and Spodoptera littoralis (Spodoptera littoralis). The active ingredients according to the present invention are additionally particularly suitable for controlling Mamestra (preferably on vegetables), codling moth (Cydia pomonella) (preferably on apples), small green leafhoppers Empoasca (preferably in vegetables and vineyards), Leptinotarsa (preferably on potatoes) and Chilo supressalis (preferably on rice) ).

The active ingredients according to the present invention are particularly suitable for controlling Aphis craccivora (Aphis craccivora), cucumber striped leaf beetle (Diabrotica balteata), tobacco budworm (Heliothis virescens) and peach on cotton, vegetables, corn, rice and soybean crops. Aphid (Myzus persicae), Plutella xylostella (Plutella xylostella), and Spodoptera littoralis (Spodoptera littoralis). The active ingredients according to the present invention are additionally particularly suitable for controlling Mamestra (preferably on vegetables), codling moth (Cydia pomonella) (preferably on apples), small green leafhoppers Empoasca (preferably in vegetables and vineyards), Leptinotarsa (preferably on potatoes) and Chilo supressalis (preferably on rice) ).

In another aspect, the present invention can also relate to a method for preventing damage to plants and parts thereof by plant parasitic nematodes (endoparasitic nematodes, semi-endoparasitic nematodes and ectoparasitic nematodes), especially the following plant parasitic nematodes, such as roots Root knot nematodes (Meloidogyne hapla), Southern root knot nematodes (Meloidogyne incognita), Java root knot nematodes (Meloidogyne javanica), peanut root knot nematodes (Meloidogyne arenaria) and other root knot nematode species Cyst-forming nematodes (cyst-forming nematodes), potato golden nematodes (Globodera rostochiensis) and other Globodera species; cereal cyst nematodes (Heterodera avenae), soybean cyst nematodes (Heterodera glycines), Heterodera schachtii, Heterodera trifolii, and other Heterodera species; Seed gall nematodes, Anguina species; stems and Stem and foliar nematodes (Stem and foliar nematodes), Aphelenchoides (Aphelenchoides) species; Sting nematodes (Sting nematodes), Belonolaimus longicaudatus and other Belonolaimus species; Pine nematodes (Pine nematodes) , Bursaphelenchus xylophilus and other Bursaphelenchus species; Ring nematodes, Criconema species, Criconemella species, and Criconemoides species , Mesocriconema species; Stem and bulb nematodes (Stem and bulb nematodes), Ditylenchus destructor (Ditylenchus destructor), Ditylenchus dipsaci (Ditylenchus dipsaci) and other Ditylenchus species; Awl nematodes), Trypanosoma (Dolichodorus) species; Spiral nematodes, Heli ocotylenchus multicinctus and other Helicotylenchus species; Sheath and sheathoid nematodes, Hemicycliophora and Hemicycliophora species and Hemicriconemoides; Hirsshmanniella species ; Branch nematodes (Lance nematodes), Crown nematodes (Hoploaimus) species; false rootknot nematodes (false rootknot nematodes), Pearl nematodes (Nacobbus) species; Needle nematodes (Needle nematodes), Longidorus elongatus (Longidorus elongatus) And other Longidorus species; Pin nematodes, Pratylenchus species; Lesion nematodes, Pratylenchus neglectus, Pratylenchus penetrans ), Pratylenchus curvitatus, Pratylenchus goodeyi, and other Pratylenchus species; Burrowing nematodes, Radopholus similis, and other species within the genus Pratylenchus; Radopholus species; Reniform nematodes, Rotylenchus robustus, Rotylenchus reniformis, and other Rotylenchus species; Scutellonema ; Stubby root nematodes (Stubby root nematodes), Trichodorus primitivus and other Trichodorus species, Paratrichodorus species; Stunt nematodes, Purslane dwarf Tylenchorhynchus claytoni, Tylenchorhynchus dubius and other Tylenchorhynchus species; Citrus nem atodes), Tylenchulus species; Dagger nematodes, Xiphinema species; and other plant parasitic nematode species, such as Subanguina spp., Hypsoperine spp.), Macroposthonia spp., Melinius spp., Punctodera spp., and Quinisulcius spp.

The compounds of the present invention may also have activity against molluscs. Examples thereof include, for example, Ampullariidae; Arion (A. ater, A. circumscriptus), A. hortensis, A. rufus, Arion (black slug (A. ater), A. circumscriptus) ); Bradybaenidae (Bradybaena fruticum); Cepaea (C. hortensis, C. Nemoralis); ochlodina; Wild slugs (C. hortensis) Deroceras (D. agrestis), D. empiricorum, smooth wild slug (D. laeve), reticulated wild slug (D. reticulatum)); Discus (circular disc snail (D) rotundatus)); Euomphalia; Galba (G. trunculata); Helicelia (H. itala), Buvi snail (H. obvia)); Helicidae (Helicigona arbustorum); Helicodiscus; Helix (H. aperta); Limax (L. cinereoniger), yellow Slugs (L. flavus), marginal slugs (L. marginatus), large slugs (L. maximus), soft slugs (L. tenellus); Lymnaea; Milax (small slugs) (black small slugs) (M. gagates), marginal slug (M. marginatus), M. sowerbyi (M. sowerbyi)); Opeas; Pomacea (P. canaticulata); Wallou Snails (Vallonia) and Zanitoides.

The term "crop" should be understood to also include crop plants that have been transformed by using recombinant DNA technology so that they can synthesize one or more selectively acting toxins, such toxins as known, for example, from toxin-producing bacteria, Especially those bacteria of the genus Bacillus.

Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins, such as insecticidal proteins from Bacillus cereus or Bacillus popilliae; or insecticidal proteins from Bacillus thuringiensis Proteins, such as delta-endotoxins, such as Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or plant insecticidal proteins (Vip), such as Vip1, Vip2, Vip3 or Vip3A; Insecticidal proteins, such as Photorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens, Xenorhabdus nematophilus; Toxins produced by animals, such as scorpion toxin, spider toxin, melittin, and other insect-specific neurotoxins; toxins produced by fungi, such as streptotoxin, plant lectins, such as pea lectin, barley lectin or Snowdrop lectin; agglutinin; protease inhibitors, such as trypsin inhibitor, serine protease inhibitor, potato glycoprotein, cystatin, papain inhibitor; ribosome inactivating protein (RIP), Such as ricin, corn-RIP, acacia toxin, loofah seed protein, saponin or allotoxin; steroid metabolism enzymes, such as 3-hydroxysteroid oxidase, ecdysteroid-UDP-glycosidyl-transfer Enzymes, cholesterol oxidase, ecdysin inhibitors, HMG-COA-reductase, ion channel blockers such as sodium channel or calcium channel blockers, juvenile hormone esterase, diuretic hormone receptor, stilbene synthase, linked Benzyl synthase, chitinase and glucanase.

In the context of the present invention, delta-endotoxin (such as Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C) or plant insecticidal protein (Vip) (such as Vip1, Vip2, Vip3 or Vip3A) should be understood It obviously also includes mixed toxins, truncated toxins and modified toxins. Mixed toxins are produced recombinantly by new combinations of different domains of those proteins (see, for example, WO 02/15701). Truncated toxins, such as truncated Cry1Ab are known. In the case of a modified toxin, one or more amino acids of the naturally occurring toxin are replaced. In this amino acid substitution, it is preferable to insert a non-naturally occurring protease recognition sequence into the toxin. For example, as in the case of Cry3A055, the cathepsin-G-recognition sequence is inserted into the Cry3A toxin (see WO 03/ 018810).

Examples of such toxins or transgenic plants capable of synthesizing such toxins are disclosed in, for example, EP-A-0 374 753, WO 93/07278, WO 95/34656, EP-A-0 427 529, EP-A-451 878 and WO 03/052073.

The methods for preparing such transgenic plants are generally known to those skilled in the art and are described, for example, in the publications mentioned above. CryI type deoxyribonucleic acid and its preparation are known, for example, from WO 95/34656, EP-A-0 367 474, EP-A-0 401 979 and WO 90/13651.

The toxins contained in transgenic plants make the plants resistant to harmful insects. Such insects can exist in any insect taxa, but are especially common in beetles (Coleoptera), dipterans (Diptera), and moths (Lepidoptera).

Transgenic plant lines containing one or more genes encoding insecticide resistance and expressing one or more toxins are known and some of them are commercially available. Examples of such plant lines: YieldGard® (corn variety, expressing Cry1Ab toxin); YieldGard Rootworm® (corn variety, expressing Cry3Bb1 toxin); YieldGard Plus® (maize variety, expressing Cry1Ab and Cry3Bb1 toxin); Starlink® (corn variety, It expresses Cry9C toxin); Herculex I® (a corn variety that expresses Cry1Fa2 toxin and the enzyme phosphinothricin N-acetyltransferase (PAT) that gains tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® ( Cotton variety, expressing Cry1Ac toxin); Bollgard I® (cotton variety, expressing Cry1Ac toxin); Bollgard II® (cotton variety, expressing Cry1Ac and Cry2Ab toxins); VipCot® (cotton variety, expressing Vip3A and Cry1Ab toxins); NewLeaf® ( Potato varieties, expressing Cry3A toxin); NatureGard®, Agrisure® GT Advantage (GA21 glyphosate-tolerant traits), Agrisure® CB Advantage (Bt11 corn borer (CB) traits) and Protecta®. Other examples of such genetically modified crops are:

1. Bt11 corn , from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/ 96/05/10. Genetically modified maize ( Zea mays ) has been genetically modified to express the truncated Cry1Ab toxin, making it resistant to the European corn borer (corn borer and Sesamia nonagrioides ). Bt11 maize is also transgenic to express PAT enzyme to gain tolerance to the herbicide glufosinate ammonium.

2. Bt176 corn , from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/ 96/05/10. The genetically modified maize expresses the Cry1Ab toxin by transgene to make it resistant to the invasion of European corn borer (corn borer and mealy stem borer). Bt176 maize is also transgenic to express PAT enzyme to gain tolerance to the herbicide glufosinate ammonium.

3. MIR604 corn , from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/ 96/05/10. The modified Cry3A toxin is expressed by genetically modified corn to make it insect resistant. This toxin is Cry3A055 modified by inserting a cathepsin-G-protease recognition sequence. The preparation of such transgenic corn plants is described in WO 03/018810.

4. MON 863 corn , from Monsanto Europe SA, 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/DE/02/9. MON 863 expresses Cry3Bb1 toxin and is resistant to certain coleopteran insects.

5. IPC 531 cotton , from Monsanto Europe SA, 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/ES/96/02.

6. 1507 corn , from Pioneer Overseas Corporation, Avenue Tedesco, 7 B-1160 Brussels, Belgium, registration number C/NL/00/10. The genetically modified corn expresses the protein Cry1F for resistance to certain lepidopteran insects, and expresses the PAT protein for resistance to the herbicide glufosinate ammonium.

7. NK603 × MON 810 corn , from Monsanto Europe SA, 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/GB/02/M3/03. It consists of conventionally bred hybrid corn varieties (by crossing genetically modified varieties NK603 and MON 810). NK603 × MON 810 maize is genetically modified to express the protein CP4 EPSPS obtained from the Agrobacterium sp. strain CP4 (this protein makes it resistant to the herbicide Roundup® (containing glyphosate)) and also the protein produced by Suyunjin Cry1Ab toxin obtained from Bacillus thuringiensis subsp. kurstaki (this toxin brings tolerance to certain Lepidoptera (including European corn borer)).

Genetically modified crops of insect-resistant plants are also described in BATS (Zentrum für Biosicherheit und Nachhaltigkeit), BATS Center (Zentrum BATS), Clarastrasse 13, Basel 4058, Switzerland) report 2003 (http://bats.ch).

The term "crop" should be understood to also include crop plants that have been transformed by using recombinant DNA technology so that they can synthesize selective antipathogenic substances, such as the so-called " Disease-related proteins" (PRP, see for example EP-A-0 392 225). Examples of such anti-pathogenic substances and transgenic plants capable of synthesizing such anti-pathogenic substances are known, for example, from EP-A-0 392 225, WO 95/33818 and EP-A-0 353 191. Methods of producing such transgenic plants are generally known to those skilled in the art and are described, for example, in the publications mentioned above.

Crops can also be modified to increase resistance to fungi (such as Fusarium, anthracnose or Phytophthora), bacteria (such as Pseudomonas) or viruses (such as potato leaf roll virus, tomato spotted wilt virus, cucumber mosaic virus). Virus) pathogen resistance.

Crops also include those crops that have increased resistance to nematodes, such as Heterodera sojae.

Crops with tolerance to abiotic stress include, for example, increased tolerance to drought, high salt, high temperature, cold, frost or light radiation by expressing NF-YB or other proteins known in the art Those crops.

Anti-pathogenic substances that can be expressed by such transgenic plants include, for example, ion channel blockers, such as blockers of sodium and calcium channels, such as viral KP1, KP4 or KP6 toxins; stilbene synthase; bibenzyl synthase; chitin Plasmase; glucanase; so-called "disease-related protein" (PRP; see, for example, EP-A-0 392 225); antipathogenic substances produced by microorganisms, such as peptide antibiotics or heterocyclic antibiotics (see, for example, WO 95/ 33818) or protein or polypeptide factors involved in the defense of plant pathogens (the so-called "plant disease resistance genes", as described in WO 03/000906).

Other uses of the composition according to the present invention are the protection of stored items and storage rooms and the protection of raw materials, such as wood, textiles, floors or buildings, and also in the field of hygiene, especially the protection of humans, livestock and productive livestock Protection from the mentioned types of pests.

The invention also provides a method for controlling harmful organisms (such as mosquitoes and other disease vectors; see also http://www.who.int/malaria/vector_control/irs/en/). In one embodiment, the method for controlling pests includes applying the composition of the present invention to target pests, their locations or surfaces, or substrates by brushing, rolling, spraying, coating, or dipping. By way of example, the method of the present invention allows for IRS (Indoor Residual Spray) application on surfaces such as walls, ceilings or floor surfaces. In another embodiment, it is contemplated that such compositions are applied to substrates such as nonwovens or textile materials in the form of nets, coverings, bedding, curtains, and tents (or can be used to make such article).

In one embodiment, the method for controlling such pests includes applying a pesticidal effective amount of the composition of the present invention to the target pest, their location or surface or substrate, so as to provide on the surface or substrate. Effective retention of pesticidal activity. Such application can be carried out by brushing, rolling, spraying, coating or dipping the pesticidal composition of the present invention. By way of example, the method of the present invention allows for the application of IRS on a surface (such as a wall, ceiling or floor surface) in order to provide effective retained pesticidal activity on the surface. In another embodiment, it is contemplated to apply such a composition for the retention and control of pests on a substrate such as a textile material in the form of netting, covering, bedding, curtains and tents (or may be Used to manufacture such items).

The substrate to be processed (including nonwovens, fabrics or nets) can be made of natural fibers such as cotton, raffia leaf fiber, jute, flax, sisal, burlap or wool, or synthetic fibers, Such as polyamide, polyester, polypropylene, polyacrylonitrile, etc. Polyester series are particularly suitable. Methods of textile treatment are known, for example WO 2008/151984, WO 2003/034823, US 563172, WO 2005/64072, WO 2006/128870, EP 1724392, WO 2005113886 or WO 2007/090739.

Other applications of the composition according to the present invention are in the field of tree injection/trunk treatment for all ornamental trees as well as all kinds of fruit and nut trees. In the field of tree injection/trunk treatment, the compounds according to the invention are particularly suitable for combating wood borers from the Lepidoptera and Coleoptera mentioned above, especially against the wood borers listed in the following tables A and B: [ Table A]. Examples of exotic wood borers of economic importance. Branch Species Infested host or crop Gitinidae Agrilus planipennis ( Agrilus planipennis ) Ash Cerambycidae (Cerambycidae) Anoplura glabripennis ( Anoplura glabripennis ) hardwood Toxidae Leymus crassiusculus ( Xylosandrus crassiusculus ) hardwood X. mutilatus ( X. mutilatus ) hardwood Tomicus piniperda ( Tomicus piniperda ) Conifers [Table B]. Examples of local wood borers of economic importance. Branch Species Infested host or crop Gitinidae Birch Copper Narrow Gidding ( Agrilus anxius ) birch Polished Narrow Gidding ( Agrilus politus ) Willow and maple Agrilus sayi Bayberry, Fragrant Fern Agrilus vittaticolllis Apple tree, pear tree, cranberry, tangdi, hawthorn Chrysobothris femorata ( Chrysobothris femorata ) Apple, apricot, beech, ash, cherry tree, chestnut, red currant, elm, hawthorn, hackberry, hickory, horse chestnut, linden, maple, rowan, oak, American mountain Walnut tree, pear tree, peach tree, persimmon tree, plum tree, poplar tree, quince, American bauhinia, dondi, sycamore, walnut tree, willow tree Texania campestris Basswood, beech, maple, oak, sycamore, willow, boxwood Cerambycidae (Cerambycidae) Pair of Beech Longhorn ( Goes pulverulentus ) Beech, Elm, Nuttall, Willow, Black Oak, Sakura Bark, Sickle Oak, Black Oak, Sycamore Tiger Oak Beetle ( Goes tigrinus ) oak Black-bellied Necropolis ( Noclytus acuminatus ) Ash, pecan, oak, walnut, birch, beech, maple, American ironwood (Eastern hophornbeam), dogwood, persimmon tree, American bauhinia, holly, hackberry, acacia, American honeylocust (Honeylocust), Boxwood, chestnut tree, Osage-orange, sassafras, lilac, mountain-mahogany, pear tree, cherry tree, plum tree, peach tree, apple tree, elm tree, linden tree, maple Fragrant Neoptychodes trilineatus ( Neoptychodes trilineatus ) Fig tree, alder tree, mulberry tree, willow tree, Netleaf hackberry Oberea ocellata ( Oberea ocellata ) Sumac, apple, peach, plum, pear, red currant, blackberry Oberea tripunctata ( Oberea tripunctata ) Dogwood, viburnum, elm, sorrel, blueberry, rhododendron, rhododendron, laurel, poplar, willow, mulberry Oncideres cingulata ( Oncideres cingulata ) Pecan tree, pecan tree, persimmon tree, elm tree, sorrel tree, linden tree, acacia tree, dogwood, eucalyptus, oak, hackberry, maple, fruit tree Saperda calcarata ( Saperda calcarata ) Poplar Strophiona nitens Chestnut, oak, pecan, walnut, beech, and maple Toxidae Corthylus columbianus Maple, oak, boxwood, beech, ash maple, sycamore, birch, linden, chestnut, elm Southern pine beetle ( Dendroctonus frontalis ) pine Dryocoetes betulae ( Dryocoetes betulae ) Birch, Liquidambar, Wild Cherry, Beech, Pear Monarthrum fasciatum ( Monarthrum fasciatum ) Oak, maple, birch, chestnut, sweetgum, blue fruit, poplar, hickory, mimosa, apple, peach, pine Phloeotribus liminaris ( Phloeotribus liminaris ) Peach tree, cherry tree, plum tree, black cherry tree, elm tree, mulberry tree, rowan tree Pseudopityophthorus pruinosus Oak, American beech, black cherry, Chickasaw plum, chestnut, maple, hickory, hornbeam, ironwood Pteropteridae Paranthrene simulans ( Paranthrene simulans ) Oak, American Chestnut Sannina uroceriformis Persimmon tree Synanthedon exitiosa ( Synanthedon exitiosa ) Peach trees, plum trees, nectarine trees, cherry trees, apricot trees, almond trees, black cherry trees Plum Peach Wing Moth ( Synanthedon pictipes ) Peach trees, plum trees, cherry trees, beech trees, black cherry trees Synanthedon rubrofascia Blue Fruit Tree Synanthedon scitula Dogwood, pecan, pecan, oak, chestnut, beech, birch, black cherry, elm, rowan, viburnum, willow, apple, loquat, nine-layer bark, bayberry Grape root penetrating moth ( Vitacea polistiformis ) Vine

The present invention can also be used to control any insect pests that may exist in turfgrass, including for example beetles, caterpillars, fire ants, ground pearls, millipedes, woodlouses, mites, mole crickets, scale insects, mealybugs Ticks, foam cicadas, southern wheat bugs and grubs. The invention can be used to control insect pests at various stages of their life cycle, including eggs, larvae, nymphs and adults.

Specifically, the present invention can be used to control insect pests that feed on the roots of turfgrass, including grubs (such as Cyclocephala spp. ) (such as masked chafer, C. lurida ) , Species of the genus Rhizotrogus (eg European beetle, R. majalis ), Cotinus spp. (eg Green June beetle, C. nitida ) ), Popillia spp. (e.g. Japanese beetle, P. japonica ), Phyllophaga spp. (e.g. May/June beetle) , spp. Species ( Ataenius spp. ) (for example, Black turfgrass ataenius, A. spretulus ), Maladera spp. (for example, Asian garden beetle (Asiatic garden beetle), sorrel velvet) Golden tortoise ( M. castanea ) and Tomarus species), ground pearls ( Margarodes spp.), mole crickets (brown yellow, southern, and short-winged; mole crickets ( Scapteriscus spp. ) , African mole crickets ( Gryllotalpa africana ) and leatherjackets (European crane fly, Tipula spp. ).

The present invention can also be used to control insect pests of lawn grass in thatched houses, including armyworms (such as fall armyworm Spodoptera frugiperda ), and common armyworm, Pseudaletia unipuncta . , Cut rootworms, weevils ( Sphenophorus spp. , such as S. venatus verstitus and S. parvulus ), and grass borers (such as Crambus spp.) ) And tropical grass borer, Herpetogramma phaeopteralis ).

The present invention can also be used to control pests of turf grass insects that live on the ground and feed on turf grass leaves, including wheat bugs (such as southern wheat bugs, southern stem bugs ( Blissus insularis )), and Bermudagrass mite (Bermudagrass mite) ) ( Eriophyes cynodoniensis ) , Gai's tiger-tailed mealy bugs ( Antonina graminis ), two-line foam cicadas ( Propsapia bicincta ), leafhoppers, root-cutting insects ( Noctuidae family), and Mai Er Fork aphid.

The present invention can also be used to control other turfgrass pests, such as red fire ants ( Solenopsis invicta ) that create nests in the lawn.

In the field of hygiene, the composition according to the present invention has resistance to ectoparasites such as hard ticks, soft ticks, scabies mites, autumn mites, flies (bites and licks), parasitic fly larvae, lice, hair lice, bird lice and Flea activity. Examples of such parasites are: Order Anatomy: Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp.).

Trichophagous order: Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Weneckiella, Lepikentron species, Damalina spp., Trichodectes spp., and Felicola spp.

Diptera and Nematocerina and Brachycerina, such as Aedes spp., Anopheles spp., Culex spp.), Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp .), Chrysops spp., Humpback fly (Hybomitra spp.), Atylotus spp., Tabanus spp., Haematopota spp. ), Philipomyia species, Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Blackhorn Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Green Lucilia spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Drosophila Genus species (Hypoderma spp.), Gasterophilus spp., Hippobosca spp., Lipoptena spp. and Melophagus spp.

From the order of the Siphonapterida, for example, Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp.

From the order of the Heteropterida, such as Cimex spp., Triatoma spp., Rhodnius spp., and Panstrongylus spp.

From the order of the Blatta (Blattarida), such as Oriental cockroach (Blatta orientalis), American cockroach (Periplaneta americana), German cockroach (Blattelagermanica) and Supella spp.

Acaria subclass (Acarida), Meta-stigmata and Meso-stigmata, such as Argas spp., Ornithma spp. (Ornithodorus spp.), Otobius spp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacenta Species (Dermacentor spp.), Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp., Pneumonyssus spp., Sternostoma spp. and Varroa spp.

Actinedida (Prostigmata) and Acaridida (Astigmata), such as Acarapis spp., Cheyletiella spp.), Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Chigger (Trombicula spp.), Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Neck Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp., and Laminosioptes spp. .

The composition according to the present invention is also suitable for protecting materials such as wood, textiles, plastics, adhesives, glues, paints, paper and cards, leather, floor coverings and construction from insects.

The composition according to the present invention can be used, for example, against the following pests: beetles, such as Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum), Ptilinuspecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus (Lyctus africanus), Lyctus africanus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthesrugicollis, Xyleborus spec., Xyleborus spec. Tryptodendron spec., Apate monachus, Bostrychus capucins, Heterobostrychus brunneus (Heterobostrychus brunneus), Sinoxylon spec., and bamboo length Beetles (Dinoderus minutus), as well as hymenoptera, such as blue-black tree wasp (Sirex juvencus), big tree wasp (Urocerus gigas), Urocerus gigas taignus and Urocerus augu, and termites, such as European wood termite (Kalotermes flavicollis), Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus ), Darwin’s Australian termites (Mastotermes darwiniensis), Nevada ancient termites (Zootermopsis nevadensis) and house termites (Coptotermes formosanus), and borers, such as silverfish (Lepisma saccharina).

The compounds according to the present invention can be used as pesticidal agents in an unmodified form, but they are usually formulated into compositions using formulation adjuvants (such as carriers, solvents, and surface-active substances) in various ways. These formulations can be in a variety of physical forms, for example, in the following forms: dusting, gel, wettable powder, water dispersible granules, water dispersible tablets, effervescent tablets, emulsifiable concentrates Substances, microemulsifiable concentrates, oil-in-water emulsions, flowable oils, aqueous dispersions, oily dispersions, suspoemulsions, capsule suspensions, emulsifiable granules, soluble liquids, water-soluble concentrates (mixed with water or water) Soluble organic solvents as a carrier), impregnated polymer membranes or, for example, from Manual on Development and Use of FAO and WHO Specifications for Pesticides [Manual on Development and Use of Pesticides of FAO and WHO Standards], United Nations, Article First edition, other forms known in the second revision (2010). Such formulations can be used directly or diluted before use. It can be diluted with, for example, water, liquid fertilizers, micronutrients, biological organisms, oils or solvents.

These formulations can be prepared by, for example, mixing the active ingredient with a formulation adjuvant in order to obtain a composition in the form of a finely divided solid, particle, solution, dispersion or emulsion. The active ingredients can also be formulated with other adjuvants (such as finely dispersed solids, mineral oils, oils of vegetable or animal origin, modified oils of vegetable or animal origin, organic solvents, water, surface active substances, or combinations thereof) .

These active ingredients can also be contained in very fine microcapsules. Microcapsules contain the active ingredients in a porous carrier. This allows the active ingredient to be released into the environment in a controlled amount (for example, slow release). Microcapsules generally have a diameter from 0.1 to 500 microns. They contain active ingredients in amounts ranging from 25% to 95% by weight of the capsule weight. The active ingredients may be in the form of a monolithic solid, in the form of fine particles in a solid or liquid dispersion, or in the form of a suitable solution. The encapsulation membrane may include, for example, natural or synthetic rubber, cellulose, styrene/butadiene copolymer, polyacrylonitrile, polyacrylate, polyester, polyamide, polyurea, polyurethane or chemically modified polymers And starch xanthate, or other polymers known to those skilled in the art. Alternatively, very fine microcapsules can be formed in which the active ingredient is contained in the solid matrix of the basic substance in the form of finely dispersed particles, but the microcapsules themselves are not encapsulated.

The formulation adjuvants suitable for preparing the composition according to the invention are known per se. As a liquid carrier, you can use: water, toluene, xylene, petroleum ether, vegetable oil, acetone, methyl ethyl ketone, cyclohexanone, acid anhydride, acetonitrile, acetonitrile, pentyl acetate, 2-butanone, butyl carbonate Ester, chlorobenzene, cyclohexane, cyclohexanol, alkyl acetate, diacetone alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylenedipine rosinate Alcohol ester, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N -dimethylformamide, dimethyl sulfide, 1,4-diethylene glycol, dipropylene glycol , Dipropylene glycol methyl ether, dipropylene glycol dibenzoate, dipropylene glycol, alkyl pyrrolidone, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1,1,1-trichloroethane, 2 -Heptanone, α-pinene, d-limonene, ethyl lactate, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, γ-butyrolactone, glycerol, glycerol acetate, two Glyceryl acetate, glyceryl triacetate, hexadecane, hexanediol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, cumene, isopropyl myristate Ester, lactic acid, laurylamine, isopropylidene acetone, methoxypropanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl caprylate, methyl oleate, methylene chloride , M-xylene, n-hexane, n-octylamine, octadecanoic acid, octylamine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol, propionic acid, propyl lactate, propylene carbonate , Propylene glycol, propylene glycol methyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylene sulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate , Butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether, methanol, ethanol, isopropanol and higher molecular weight alcohols, such as pentanol, tetrahydrofuranol, hexanol, octanol, ethylene glycol, propylene glycol , Glycerin, N -Methyl-2-pyrrolidone, etc.

Suitable solid carrier systems such as talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, diatomaceous earth, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed husk, wheat flour, soybean flour, pumice , Wood flour, ground walnut shells, lignin and similar substances.

Many surface-active substances can be advantageously used in both solid and liquid formulations, especially those formulations that can be diluted with a carrier before use. Surface-active substances can be anionic, cationic, nonionic or polymeric and they can be used as emulsifiers, wetting agents or suspending agents or for other purposes. Typical surface-active substances include, for example, salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; salts of alkyl aryl sulfonates, such as calcium dodecylbenzene sulfonate; alkylphenol/alkylene oxide additions Products, such as ethoxylated nonylphenol; alcohol/alkylene oxide addition products, such as ethoxylated tridecyl alcohol; soaps, such as sodium stearate; salts of alkyl naphthalene sulfonates, such as dibutyl Sodium naphthalene sulfonate; dialkyl esters of sulfosuccinates, such as sodium bis(2-ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryl Trimethylammonium chloride; polyethylene glycol esters of fatty acids, such as polyethylene stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono- and di-alkyl phosphates ; And there are other substances, such as described in: McCutcheon's Detergents and Emulsifiers Annual [McCutcheon Detergents and Emulsifiers Annual], MC Publishing Corp. (MC Publishing Corp.), Ridgewood, New Jersey (Ridgewood New Jersey) ( 1981).

Other adjuvants that can be used in pesticidal formulations include crystallization inhibitors, viscosity modifiers, suspending agents, dyes, antioxidants, foaming agents, light absorbers, mixing aids, defoamers, complexing agents, neutralization Or substances and buffers that change pH, corrosion inhibitors, fragrances, wetting agents, absorption enhancers, micronutrients, plasticizers, glidants, lubricants, dispersants, thickeners, antifreeze, microbicides , And liquid and solid fertilizers.

The composition according to the present invention may contain additives including oils of vegetable or animal origin, mineral oils, alkyl esters of such oils, or mixtures of such oils and oil derivatives. The amount of oil additives in the composition according to the invention is generally from 0.01% to 10% based on the mixture to be applied. For example, the oil additive can be added to the spray tank in the desired concentration after the spray mixture has been prepared. Preferred oil additives include mineral oil or oils of vegetable origin, such as rapeseed oil, olive oil or sunflower oil; emulsified vegetable oils; alkyl esters of vegetable oils, such as methyl derivatives; or oils of animal origin, Such as fish oil or tallow. Preferred oil additives include alkyl esters of C ₈ -C ₂₂ fatty acids, especially methyl derivatives of C ₁₂ -C ₁₈ fatty acids, such as methyl esters of lauric acid, palmitic acid and oleic acid (respectively methyl lauric acid Esters, methyl palmitate and methyl oleate). Many oil derivatives are known from Compendium of Herbicide Adjuvants [Herbicide Adjuvants Compendium], 10th edition, Southern Illinois University, 2010.

The composition of the present invention generally comprises from 0.1% to 99% by weight, especially from 0.1% to 95% by weight of the compound of the present invention, and from 1% to 99.9% by weight of a formulated adjuvant, the formulation The adjuvant preferably contains from 0% to 25% by weight of surface active substance. While commercial products can preferably be formulated as concentrates, end users will usually use dilute formulations.

The application rate varies within a wide range and depends on the nature of the soil, application method, crop plants, pests to be controlled, main climatic conditions, and other factors governed by application method, application time and target crop. As a general guide, the compound can be applied at a rate of from 1 l/ha to 2000 l/ha, especially from 10 l/ha to 1000 l/ha. A preferred formulation may have the following composition (weight %): Emulsifiable concentrate: Active ingredient: 1% to 95%, preferably 60% to 90% Surfactant: 1% to 30%, preferably 5% to 20% Liquid carrier: 1% to 80%, preferably 1% to 35% Dust agent: Active ingredient: 0.1% to 10%, preferably 0.1% to 5% Solid carrier: 99.9% to 90%, preferably 99.9% to 99% Suspension concentrate: Active ingredient: 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: Active ingredient: 0.5% to 90%, preferably 1% to 80% Surfactant: 0.5% to 20%, preferably 1% to 15% Solid carrier: 5% to 95%, preferably 15% to 90% Granules: Active ingredient: 0.1% to 30%, preferably 0.1% to 15% Solid carrier: 99.5% to 70%, preferably 97% to 85%

The following examples further illustrate (but do not limit) the invention. Wettable powder a) b) c) Active ingredient 25% 50% 75% Sodium Lignosulfonate 5% 5% - Sodium lauryl sulfate 3% - 5% Sodium diisobutyl naphthalene sulfonate - 6% 10% Phenol polyglycol ether (7-8 mol of ethylene oxide) - 2% - Highly dispersed silicic acid 5% 10% 10% Kaolin 62% 27% -

The combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable grinder to obtain a wettable powder, which can be diluted with water to give a suspension of the desired concentration. Powder for dry seed treatment a) b) c) Active ingredient 25% 50% 75% Light mineral oil 5% 5% 5% Highly dispersed silicic acid 5% 5% - Kaolin 65% 40% - talc - 20%

The combination is thoroughly mixed with the adjuvant and the mixture is thoroughly ground in a suitable grinder to obtain a powder, which can be used directly for seed treatment. Emulsifiable concentrate Active ingredient 10% Octylphenol polyethylene glycol ether (4-5 mol of ethylene oxide) 3% Calcium dodecylbenzene sulfonate 3% Castor oil polyglycol ether (35 mol of ethylene oxide) 4% Cyclohexanone 30% Xylene mixture 50%

Emulsions with any desired dilution that can be used for plant protection can be obtained from this concentrate by dilution with water. Dust agent a) b) c) Active ingredient 5% 6% 4% talc 95% - - Kaolin - 94% - Mineral filler - - 96% The ready-to-use dust agent is obtained by mixing the combination with the carrier and grinding the mixture in a suitable grinder. Such powders can also be used for dry dressing of seeds. Extruder pellets Active ingredient 15% Sodium Lignosulfonate 2% Carboxymethyl cellulose 1% Kaolin 82%

The combination is mixed with the adjuvants and ground, and the mixture is moistened with water. The mixture is extruded and then dried in a stream of air. Coated granules Active ingredient 8% Polyethylene glycol (molecular weight 200) 3% Kaolin 89%

This finely ground combination is applied uniformly to the kaolin moistened with polyethylene glycol in a mixer. In this way, dust-free coated granules are obtained. Suspension concentrate Active ingredient 40% Propylene Glycol 10% Nonylphenol polyglycol ether (15 mol of ethylene oxide) 6% Sodium Lignosulfonate 10% Carboxymethyl cellulose 1% Silicone oil (in the form of a 75% emulsion in water) 1% water 32%

The finely ground combination is intimately mixed with the adjuvant to give a suspension concentrate from which a suspension of any desired dilution can be obtained by dilution with water. Using such dilutions, it is possible to treat live plants together with plant propagation material and protect them from microbial infestation by spraying, watering or dipping. Flowable concentrate for seed treatment Active ingredient 40% Propylene Glycol 5% Copolymer butanol PO/EO 2% Tristyrenol with 10-20 mol EO 2% 1,2-Benzisothiazolin-3-one (in the form of a 20% solution in water) 0.5% Monoazo-pigment calcium salt 5% Silicone oil (in the form of a 75% emulsion in water) 0.2% water 45.3%

The finely ground combination is intimately mixed with the adjuvant to give a suspension concentrate from which a suspension of any desired dilution can be obtained by dilution with water. Using such dilutions, it is possible to treat live plants together with plant propagation material and protect them from microbial infestation by spraying, watering or dipping. Sustained release capsule suspension

Mix 28 parts of the combination with 2 parts of aromatic solvent and 7 parts of toluene diisocyanate/polymethylene-polyphenylisocyanate-mixture (8:1). This mixture was emulsified in a mixture of 1.2 parts polyvinyl alcohol, 0.05 parts defoamer and 51.6 parts water until the desired particle size was reached. To this emulsion was added 2.8 parts of a mixture of 1,6-diaminohexane in 5.3 parts of water. The mixture is stirred until the polymerization reaction is complete. The obtained capsule suspension was stabilized by adding 0.25 parts of thickener and 3 parts of dispersant. The capsule suspension formulation contains 28% active ingredient. The medium capsule diameter is 8-15 microns. The resulting formulation is applied to the seeds as an aqueous suspension, carried out in a device suitable for this purpose.

Types of formulations include emulsion concentrate (EC), suspension concentrate (SC), suspoemulsion (SE), capsule suspension (CS), water dispersible granules (WG), emulsifiable granules (EG), Water-in-oil emulsion (EO), oil-in-water emulsion (EW), microemulsion (ME), oil dispersion (OD), oil suspension (OF), oil-soluble liquid (OL), soluble concentrate (SL) , Ultra-low volume suspension (SU), ultra-low volume liquid (UL), mother drug (TK), dispersible concentrate (DC), wettable powder (WP), soluble granule (SG) or Any technically feasible formulation of an agriculturally acceptable adjuvant combination. Preparation Example: "Mp" means the melting point in °C. Free radical means methyl. ¹ H NMR measurements were recorded on a Brucker 400 MHz spectrometer, and the chemical shifts are given in ppm relative to the TMS standard. The spectra are measured in deuterated solvents as specified. Use any of the following LCMS methods to characterize these compounds. The characteristic LCMS value obtained for each compound is the retention time ("Rt", recorded in minutes) and the measured molecular ion (M+H) ⁺ or (MH) ^- . LCMS and GCMS methods: Method 1:

(P1) 步驟1：2-[[5-乙基氫硫基-6-[3-甲基-6-(三氟甲基)咪唑并[4,5-c]吡啶-2-基]-3-吡啶基]氧基]乙腈（化合物I7）的製備

(I7)Record spectra on a mass spectrometer (ZQ single quadrupole mass spectrometer) from Waters, which is equipped with an electrospray source (polarity: positive or negative ion, capillary voltage: 3.00 kV, cone range: 30 -60 V, extractor: 2.00 V, source temperature: 150°C, desolvation temperature: 350°C, cone gas flow rate: 0 L/h, desolvation gas flow rate: 650 L/h, mass range: 100 Da to 900 Da) and Acquity UPLC from Waters: Binary pump, heated column chamber, and diode array detector. Solvent degassing device, binary pump, heated column chamber, and diode array detector. Column: Waters UPLC HSS T3, 1.8 µm, 30 x 2.1 mm, temperature: 60°C, DAD wavelength range (nm): 210 to 500, solvent gradient: A = water + 5% MeOH + 0.05% HCOOH, B = Acetonitrile + 0.05% HCOOH: gradient: 0 min 0% B, 100% A; 1.2-1.5 min 100% B; flow (ml/min) 0.85. Method 2: Record the spectrum on a mass spectrometer (SQD or ZQ single quadrupole mass spectrometer) from Waters, which is equipped with an electrospray source (polarity: positive ion or negative ion, capillary voltage: 3.00 kV, cone range) : 30-60 V, extractor: 2.00 V, source temperature: 150°C, desolvation temperature: 350°C, cone gas flow rate: 0 L/h, desolvation gas flow rate: 650 L/h, mass Range: 100 Da to 900 Da) and Acquity UPLC from Waters: Binary pump, heated column chamber, and diode array detector. Solvent degassing device, binary pump, heated column chamber, and diode array detector. Column: Waters UPLC HSS T3, 1.8 µm, 30 x 2.1 mm, temperature: 60°C, DAD wavelength range (nm): 210 to 500, solvent gradient: A = water + 5% MeOH + 0.05% HCOOH, B = Acetonitrile + 0.05% HCOOH; gradient: 0 min 0% B, 100% A; 2.7-3.0 min 100% B; flow (ml/min) 0.85. Method 3: Record spectra on a mass spectrometer (6410 triple quadrupole mass spectrometer) from Agilent Technologies, which is equipped with an electrospray source (polarity: positive and negative polarity conversion, capillary: 4.00 kV, voltage: 100.00 V, gas temperature: 350 ^o C, gas flow rate: 11 L/min, nebulizer gas: 45 psi, mass range: 110-1000 Da; DAD wavelength range: 210-400 nm). Column: KINETEX EVO C18, length 50 mm, diameter 4.6 mm, particle size 2.6 µm. The column oven temperature is 40°C. Solvent gradient: A = 0.1% formic acid in water: acetonitrile (95: 5 v/v). B = Acetonitrile with 0.1% formic acid. Gradient = 0 min 90% A, 10% B; 0.9-1.8 min 0% A, 100% B, 2.2-2.5 min 90% A, 10% B. The flow rate is 1.8 mL/min. Method 4: Record the spectrum on a mass spectrometer (Acquity SDS mass spectrometer) from Waters, which is equipped with an electrospray source (polarity: positive and negative polarity conversion, capillary: 3.00 kV, cone voltage: 41.00 V, Source temperature: 150 ^o C, desolvation gas flow: 1000 L/h, desolvation temperature: 500 ^o C, gas flow at the cone hole: 50 L/h, mass range: 110-800 Da; PDA wavelength Range: 210-400 nm. Column: Acquity UPLC HSS T3 C18, length 30 mm, diameter 2.1 mm, particle size 1.8 µm. Column oven temperature 40°C. Solvent gradient: A = water containing 0.1% formic acid: acetonitrile ( 95: 5 v/v). B = acetonitrile containing 0.05% formic acid. Gradient = 0 min 90% A, 10% B; 0.2 min 50% A, 50% B; 0.7-1.3 min 0% A, 100% B 1.4-1.6 min 90% A, 10% B. Flow rate 0.8 mL/min. Method 5: Record the spectrum on a mass spectrometer (SQ detector 2 single quadrupole mass spectrometer) from Waters, which is equipped with Electrospray source (polarity: positive or negative ion, capillary voltage: 2.50 kV, cone voltage: 41 V, extractor: 3.00 V, source temperature: 150°C, desolvation temperature: 500°C, cone gas flow : 50 L/h, desolvation gas flow: 1000 L/h, mass range: 100 Da to 600 Da) and Acquity UPLC from Waters: quaternary pump, heated column chamber, and diode Array detector. The column uses Waters UPLC HSS T3, 1.8 μm, 30 x 2.1 mm. The column oven temperature is 40°C. DAD wavelength range (nm): 200 to 350. Solvent gradient: A = water + 5% acetonitrile + 0.05% HCOOH, B = acetonitrile + 0.05% HCOOH. Gradient = 0 min 90% A, 10% B; 0.2 min 50% A, 50% B; 0.7-1.3 min 0% A, 100% B; 1.4-1.6 min 90% A, 10% B. Flow rate 0.6 mL/min. Preparation of examples of compounds of formula (I): Example P1 : 2-[[5-(Ethylsulfonylimino)-6-[3 -Methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propionitrile (Compound P1)

(P1) Step 1: 2-[[5-Ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]- Preparation of 3-pyridyl]oxy]acetonitrile (compound I7)

(I7)

Treat 5-ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine- under the same conditions as described in step 2 of Example P3 2-yl]pyridin-3-ol (prepared according to WO 16096584) to give the desired compound.

(I8)LCMS (Method 1): m/z 394 [M+H] ⁺ ; Retention time: 0.94 min. Step 2: 2-[[5-Ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridine Preparation of yl]oxy]-2-methyl-propionitrile (Compound I8)

(I8)

Under the same conditions described in step 3 of Example P3, 2-[[5-ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5- c]pyridin-2-yl]-3-pyridyl]oxy]acetonitrile (compound I7 prepared as described above) to give 2-[[5-ethylsulfanyl-6-[3-methyl -6-(Trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridinyl]oxy]-2-methyl-propionitrile.

(P1)LCMS (Method 1): m/z 422 [M+H] ⁺ ; Retention time: 1.02 min. Step 3: 2-[[5-(Ethylsulfonylimino)-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl] Preparation of -3-pyridyl]oxy]-2-methyl-propionitrile (compound P1)

(P1)

Under the same conditions as described in step 4 of Example P3, 2-[[5-ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5- c]pyridin-2-yl]-3-pyridinyl]oxy]-2-methyl-propionitrile (compound I8) to give the desired compound.

(P2) 步驟1：5-乙基氫硫基-6-[7-甲基-3-(三氟甲基)咪唑并[4,5-c]嗒𠯤-6-基]吡啶-3-醇（化合物I1）的製備

(I1) ¹ H NMR (400 MHz, chloroform-d) δ ppm 1.40 (t, J =7.34Hz, 3H) 1.93 (s, 6H) 3.89-3.74 (m, 2H) 3.90 (s, 3H) 8.12 (s, 1H) 8.40 (d, J =2.57Hz, 1H) 8.81 (d, J =2.57Hz, 1H) 8.99 (s, 1H). Example P2 : 2-[[5-(Ethylsulfonylimino)-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]da𠯤-6- Yl]-3-pyridyl]oxy]-2-methyl-propionitrile (Compound P2)

(P2) Step 1: 5-Ethylhydrosulfanyl-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pada-6-yl]pyridine-3- Preparation of alcohol (compound I1)

(I1)

Cesium carbonate (19.5 g, 59.8 mmol, 2.50 equivalents) and (E)-benzaldehyde oxime (3.4 mL, 31.1 mmol, 1.30 equivalents) were added to 6-(5-bromo-3-ethylhydrothio-2- (Pyridinyl)-7-methyl-3-(trifluoromethyl)imidazo[4,5-c]ta𠯤 (prepared according to WO 2016059145) (10.0 g, 23.9 mmol) in acetonitrile (240 mL) in. The resulting suspension was stirred at 50°C for 42 hours. After cooling to room temperature, the reaction mixture was concentrated under reduced pressure, the crude residue was partitioned between ethyl acetate and water, and the pH of the aqueous phase was adjusted to 1-2 by adding 1 N hydrochloric acid solution. The aqueous phase was extracted twice with ethyl acetate, and the combined organic phases were dried over sodium sulfate, filtered and concentrated. The crude material was purified by flash chromatography (0-10% methanol in dichloromethane) on silica gel to give the desired product (6.90 g, 19.0 mmol) as a yellow solid.

(I2) ¹ H NMR (400 MHz, dimethyl sulfide-d6) δ ppm 1.25 (t, J =7.34Hz, 3H) 2.99 (q, J =7.34Hz, 2H) 4.13 (s, 3H) 7.38 (d, J =2.20Hz, 1H) 8.17 (d, J =2.20Hz, 1H) 8.55 (s, 1H) 10.94 (s, 1H). Step 2: 2-[[5-Ethylhydrosulfanyl-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]ta𠯤-6-yl]-3- Preparation of pyridyl]oxy]-2-methyl-propanamide (compound I2)

(I2)

Cesium carbonate (303 mg, 0.93 mmol, 1.10 equivalents) was added to 5-ethylsulfanyl-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]ta𠯤 -6-yl]pyridin-3-ol (compound I1 prepared as described above) (300 mg, 0.84 mmol) in acetonitrile (8.4 mL). The resulting suspension was stirred for 5 min, then 2-bromo-2-methyl-propanamide (294 mg, 1.77 mmol, 2.10 equivalents) was added, and the reaction mixture was heated and stirred at 70°C overnight. After cooling to room temperature, the reaction mixture was concentrated under reduced pressure, the crude residue was partitioned between ethyl acetate and water, and the pH of the aqueous phase was adjusted to 1 by adding 1 N hydrochloric acid solution. The aqueous phase was extracted three times with ethyl acetate and once with dichloromethane, the combined organic phases were dried over sodium sulfate, filtered and concentrated. The crude material was purified by flash chromatography on silica gel (0-10% methanol in dichloromethane) to give the desired product (156 mg, 0.56 mmol) as a yellow solid.

(I3) ¹ H NMR (400 MHz, dimethyl sulfide-d6) δ ppm 1.26 (t, J =7.34Hz, 3H) 1.60 (s, 6H) 2.96 (q, J =7.34Hz, 2H) 4.15 (s, 3H ) 7.30 (s broad, 1H) 7.41 (d, J =2.20Hz, 1H) 7.49 (m, 1H) 8.23 (d, J =2.20Hz, 1H) 8.69 (s, 1H). Step 3: 2-[[5-Ethylhydrosulfanyl-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]ta𠯤-6-yl]-3- Preparation of pyridyl]oxy]-2-methyl-propionitrile (compound I3)

(I3)

Add trifluoroacetic anhydride (182 μL, 1.30 mmol, 3.00 equivalents) to 2-[[5-ethylsulfanyl-6-[7-methyl-3-(trifluoromethyl) at 0°C ) Imidazo[4,5-c]pada-6-yl]-3-pyridyl]oxy]-2-methyl-propanamide (Compound I2 prepared as described above) (317 mg, 0.43 mmol ) In dichloromethane (4.30 mL) and triethylamine (243 μL, 1.73 mmol, 4.00 equivalents). After stirring overnight at room temperature, the addition of trifluoroacetic anhydride (182 μL, 1.30 mmol, 3.00 equivalents) and triethylamine (243 μL, 1.73 mmol, 4.00 equivalents) was completed again, and the reaction mixture was additionally stirred at room temperature 2 hours. The reaction mixture was carefully quenched by adding methanol and then saturated sodium bicarbonate solution. The aqueous phase was extracted twice with dichloromethane, the combined organic layer was dried over sodium sulfate, filtered and concentrated. The crude material was purified by flash chromatography on silica gel (0-10% methanol in dichloromethane) to give the desired product (156 mg, 0.37 mmol) as a yellow oil.

(P2) ¹ H NMR (400 MHz, chloroform-d) δ ppm 1.42 (t, J =7.34Hz, 3H) 1.88 (s, 6H) 3.03 (q, J =7.34Hz, 2H) 4.31 (s, 3H) 7.72 (d , J =2.57Hz, 1H) 8.26 (s, 1H) 8.39 (d, J =2.57Hz, 1H). Step 4: 2-[[5-(Ethylsulfonylimino)-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]ta𠯤-6-yl ]-3-pyridyl]oxy]-2-methyl-propionitrile (Compound P2)

(P2)

Diacetyloxy iodobenzene (257 mg, 0.78 mmol, 3.00 equivalents) and ammonium carbamate (52 mg, 0.65 mmol, 2.50 equivalents) were added to 2-[[5-ethylhydrosulfanyl-6-[ 7-Methyl-3-(trifluoromethyl)imidazo[4,5-c]ta𠯤-6-yl]-3-pyridyl]oxy]-2-methyl-propionitrile (as described above The prepared compound I3) (110 mg, 0.26 mmol) was suspended in methanol (0.78 mL). After stirring for 30 min at room temperature, the reaction mixture was quenched with ice water and then saturated aqueous sodium thiosulfate. Control any presence of peroxide in the water phase, and then extract twice with ethyl acetate. The combined organic layer was washed with brine, dried over anhydrous sodium sulfate, filtered and concentrated under vacuum. The crude product was purified by flash chromatography on silica gel (0-15% methanol in dichloromethane) to obtain the desired compound (98 mg, 0.22 mmol) as a white solid.

(P3) 步驟1：5-乙基氫硫基-6-[3-甲基-6-(三氟甲基)咪唑并[4,5-b]吡啶-2-基]吡啶-3-醇（化合物I4）的製備

(I4) ¹ H NMR (400 MHz, dimethylsulfene-d6) δ ppm 1.18 (t, J =7.52Hz, 3H) 1.60 (s, 6H) 3.69-3.49 (m, 2H) 3.91 (s, 3H) 4.63 ( s, 1H) 8.30 (d, J =2.57Hz, 1H) 8.74 (s, 1H) 8.93 (d, J =2.57Hz, 1H). Example P3 : 2-[[5-(Ethylsulfonylimino)-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl ]-3-pyridyl]oxy]-2-methyl-propionitrile (Compound P3)

(P3) Step 1: 5-Ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]pyridin-3-ol (Compound I4) Preparation

(I4)

Cesium carbonate (12.9 g, 39.5 mmol, 2.20 equivalents) and (E)-benzaldehyde oxime (2.55 mL, 23.4 mmol, 1.30 equivalents) were added to 2-(5-bromo-3-ethylhydrosulfide-2- Pyridyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine (CAS 1421955-74-9) (7.50 g, 18.0 mmol) in N,N-dimethyl Formamide (36 mL) in solution. The resulting suspension was stirred at 80°C overnight. After cooling to room temperature, the reaction mixture was diluted with dichloromethane (500 mL), the organic phase was washed with water (3*200 mL), and the pH of the aqueous phase was adjusted to 1-2 by adding 1 N hydrochloric acid solution. The aqueous phase was extracted with dichloromethane (5*300 mL), the combined organic phases were dried over sodium sulfate, filtered and concentrated. The crude material was purified by flash chromatography on silica gel (ethyl acetate in cyclohexane) to give the desired product (5.80 g, 16.4 mmol).

(I5)LCMS (Method 1): m/z 355 [M+H] ⁺ ; Retention time: 0.94 min. Step 2: 2-[[5-Ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridine Preparation of yl]oxy]acetonitrile (compound I5)

(I5)

At room temperature, under argon, potassium carbonate (1.21 g, 8.47 mmol, 1.50 equivalents) and then bromoacetonitrile (608 μL, 8.47 mmol, 1.50 equivalents) were added to 5-ethylsulfanyl-6-[ 3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]pyridin-3-ol (compound I4 prepared as described above) (2.00 g, 5.64 mmol) in N,N-dimethylformamide (40 mL) in solution. After stirring for 5 hours, the reaction mixture was poured on water (300 mL), and the aqueous phase was extracted twice with ethyl acetate (300 mL). The combined organic phases were washed with water (3*200 mL), dried over sodium sulfate, filtered and concentrated. The crude material was purified by chromatography on silica gel (ethyl acetate in cyclohexane) to give the desired compound (2.08 g, 5.28 mmol) as a yellow solid.

(I6)LCMS (Method 1): m/z 394 [M+H] ⁺ ; Retention time: 1.01 min. Step 3: 2-[[5-Ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridine Preparation of yl]oxy]-2-methyl-propionitrile (Compound I6)

(I6)

A 1 M lithium hexamethyldisilazane solution in tetrahydrofuran (15.8 mL, 15.8 mmol, 3.00 equivalents) was added dropwise to 2-[[5-ethylhydrothio-6-[ 3-Methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]oxy]acetonitrile (Compound I5 prepared as described above) (2.07 g , 5.26 mmol) and methyl iodide (1.31 mL, 21.0 mmol, 4.00 equivalents) in a solution of tetrahydrofuran (32 mL) cooled at 0°C. After the addition was complete, the reaction mixture was stirred with an ice bath for 1 hour, then warmed to room temperature and stirred overnight. The reaction mixture was quenched by pouring onto saturated aqueous sodium bicarbonate solution at 0°C (50 mL). The aqueous phase was extracted with ethyl acetate (2*50 mL). The combined organic phases were dried over sodium sulfate, filtered and evaporated. The crude material was purified by flash chromatography on silica gel (ethyl acetate in cyclohexane) to obtain the desired compound (700 mg, 1.66 mmol).

(P3)LCMS (Method 1): m/z 422 [M+H] ⁺ ; Retention time: 1.11 min. Step 4: 2-[[5-(Ethylsulfonylimino)-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl] Preparation of -3-pyridyl]oxy]-2-methyl-propionitrile (compound P3)

(P3)

2-[[5-Ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl] A solution of oxy]-2-methyl-propionitrile (compound I6 prepared as described above) (400 mg, 0.95 mmol) in methanol (2.85 mL) was added to diacetoxyiodobenzene (917 mg, 2.85 mmol, 3.00 equivalents) and ammonium carbamate (185 mg, 2.37 mmol, 2.50 equivalents) in a solid mixture. After stirring overnight at room temperature, the reaction mixture was quenched with saturated aqueous sodium thiosulfate. Control any presence of peroxide in the water phase, and then extract twice with ethyl acetate. The combined organic layer was dried over anhydrous sodium sulfate, filtered and concentrated under vacuum. The crude product was purified by flash chromatography on silica gel (ethyl acetate in cyclohexane) to obtain the desired compound (295 mg, 0.65 mmol) as a yellow solid.

(P5) 步驟1：5-乙基氫硫基-2-碘-6-[3-甲基-6-(三氟甲基)咪唑并[4,5-c]吡啶-2-基]吡啶-3-醇（化合物I9）的製備

(I9)LCMS (Method 1): m/z 453 [M+H] ⁺ ; Retention time: 0.93 min. Example P5 : 2-[[5-(Ethylsulfonylimino)-2-methyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c] Preparation of pyridin-2-yl]-3-pyridinyl]oxy]-2-methyl-propionitrile (compound P5)

(P5) Step 1: 5-Ethylsulfanyl-2-iodo-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]pyridine Preparation of -3-ol (Compound I9)

(I9)

At room temperature, under argon, molecular iodine (6.95 g, 27.4 mmol, 1.20 equivalents) was added to 5-ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl ) Imidazo[4,5-c]pyridin-2-yl]pyridin-3-ol (prepared according to WO 16096584) (8.08 g, 22.8 mmol) and sodium carbonate (5.07 g, 47.9 mmol, 2.10 equivalents) in water ( 68 mL) and acetonitrile (68 mL). After stirring for 5 hours, the reaction mixture was quenched with 20% w/w sodium thiosulfate aqueous solution to control the presence of peroxide in the aqueous phase, and then extracted with ethyl acetate. The combined organic phase was washed with brine, dried over sodium sulfate, filtered and concentrated. The crude material can be purified by flash chromatography on silica gel (ethyl acetate in cyclohexane) to provide the desired product, but it can also be used directly in the next step.

(I10)LCMS (Method 1): m/z 481 [M+H] ⁺ ; retention time: 0.96 min. Step 2: 5-Ethylsulfanyl-2-methyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]pyridine-3 -Preparation of alcohol (compound I10)

(I10)

At room temperature, under argon, add trimethylboroxine (6.63 mL, 46.7 mmol, 2.50 equivalents) to 5-ethylhydrosulfanyl-2-iodo-6-[3-methyl- 6-(Trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]pyridin-3-ol (compound I9 prepared as described above) (9.76 g, 18.7 mmol), potassium carbonate (8.16 g , 56.1 mmol, 3.00 equivalents) and [1,1'-bis(diphenylphosphino)ferrocene] dichloride palladium(II) dichloromethane complex (3.85 g, 4.67 mmol, 0.25 equivalent) in 1,4-Di㗁𠮿 (140 mL) in the mixture. The reaction mixture was heated to 100°C and stirred for 3 hours. After cooling to room temperature, the crude mixture was filtered through a pad of Celite and washed with ethyl acetate. The filtrate was concentrated under vacuum to give 12.5 g crude product, which was purified by flash chromatography on silica gel (ethyl acetate in cyclohexane) to give the desired product (2.77 g, 7.52 mmol) .

(I11)LCMS (Method 1): m/z 369 [M+H] ⁺ ; Retention time: 0.87 min. Step 3: 2-[[5-Ethylsulfanyl-2-methyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl ]-3-pyridyl]oxy]acetonitrile (Compound I11)

(I11)

At room temperature, under argon, potassium carbonate (1.45 g, 10.2 mmol, 1.50 equivalents) and then bromoacetonitrile (731 μL, 10.2 mmol, 1.50 equivalents) were added to 5-ethylhydrosulfan-2-methyl 6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]pyridin-3-ol (compound I10 prepared as described above) (2.50 g , 6.79 mmol) in N,N-dimethylformamide (34 mL). After stirring for 2 hours, the reaction mixture was poured on water, and the aqueous phase was extracted twice with ethyl acetate. The combined organic phase was washed with brine, dried over sodium sulfate, filtered and concentrated. The crude material was used without further purification.

(I12)LCMS (Method 1): m/z 408 [M+H] ⁺ ; Retention time: 0.96 min. Step 4: 2-[[5-Ethylsulfanyl-2-methyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl ]-3-pyridyl]oxy]-2-methyl-propionitrile (Compound I12)

(I12)

A 1 M lithium hexamethyldisilazane solution in tetrahydrofuran (18.8 mL, 18.8 mmol, 3.00 equivalents) was added dropwise to 2-[[5-ethylhydrosulfanyl-2-methyl] via a dropping funnel. Yl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]oxy]acetonitrile (compound prepared as described above I11) (2.55 g, 6.26 mmol) and methyl iodide (1.17 mL, 18.8 mmol, 3.00 equivalents) in a solution of tetrahydrofuran (12.5 mL) cooled at 0°C. After the addition was complete, the reaction mixture was slowly warmed to room temperature and stirred for 2.5 hours. The reaction mixture was quenched by pouring onto saturated aqueous sodium bicarbonate solution, and the aqueous phase was extracted with ethyl acetate. The combined organic phases were dried over sodium sulfate, filtered and evaporated. The crude material was purified by flash chromatography on silica gel (ethyl acetate in cyclohexane) to obtain the desired compound.

(P5)LCMS (Method 1): m/z 436 [M+H] ⁺ ; Retention time: 1.06 min. Step 5: 2-[[5-(Ethylsulfonylimino)-2-methyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine -2-yl]-3-pyridyl]oxy]-2-methyl-propionitrile (Compound P5)

(P5)

The 2-[[5-ethylhydrosulfanyl-2-methyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]- A solution of 3-pyridyl]oxy]-2-methyl-propionitrile (compound I12 prepared as described above) (800 mg, 1.34 mmol) in methanol (6.89 mL) was added to diacetoxy iodobenzene (1.36 g, 4.13 mmol, 3.00 equivalents) and ammonium carbamate (274 mg, 3.44 mmol, 2.50 equivalents) in a solid mixture. After stirring for 2 hours at room temperature, the reaction mixture was quenched with saturated aqueous sodium thiosulfate. Control any presence of peroxide in the water phase, and then extract twice with ethyl acetate. The combined organic layer was washed with brine, dried over anhydrous sodium sulfate, filtered and concentrated under vacuum. The crude product was purified by flash chromatography on silica gel (ethyl acetate in cyclohexane), and then subjected to a second purification by reverse phase chromatography (water/acetonitrile) to obtain the desired compound (186 mg, 0.40 mmol).

(P4) 步驟1：5-乙基氫硫基-2-碘-6-[3-甲基-6-(三氟甲基)咪唑并[4,5-b]吡啶-2-基]吡啶-3-醇（化合物I13）的製備

(I13)LCMS (Method 1): m/z 467 [M+H] ⁺ ; Retention time: 0.91 min. Example P4 : 2-[[5-(Ethylsulfonylimino)-2-methyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b] Preparation of pyridin-2-yl]-3-pyridinyl]oxy]-2-methyl-propionitrile (compound P4)

(P4) Step 1: 5-Ethylhydrosulfanyl-2-iodo-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]pyridine Preparation of -3-ol (Compound I13)

(I13)

Treat 5-ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine- under the same conditions as described in step 1 of Example P5 2-yl]pyridin-3-ol (Compound I4 prepared as described in step 1 of Example P3) to give the desired compound.

(I14)LCMS (Method 1): m/z 480 [M+H] ⁺ ; Retention time: 1.06 min. Step 2: 5-Ethylsulfanyl-2-methyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]pyridine-3 -Preparation of alcohol (compound I14)

(I14)

Treat 5-ethylhydrosulfanyl-2-iodo-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-] under the same conditions as described in step 2 of Example P5 b]pyridin-2-yl]pyridin-3-ol (Compound I13 prepared as described above) to give the desired compound.

(I15)LCMS (Method 1): m/z 369 [M+H] ⁺ ; Retention time: 0.96 min. Step 3: 2-[[5-Ethylsulfanyl-2-methyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl ]-3-pyridyl]oxy]acetonitrile (Compound I15)

(I15)

Treat 5-ethylhydrosulfanyl-2-methyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5] under the same conditions as described in step 3 of Example P5 -b]pyridin-2-yl]pyridin-3-ol (compound I14 prepared as described above) to give the desired compound.

(I16)LCMS (Method 1): m/z 408 [M+H] ⁺ ; Retention time: 1.05 min. Step 4: 2-[[5-Ethylsulfanyl-2-methyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl ]-3-pyridyl]oxy]-2-methyl-propionitrile (Compound I16)

(I16)

Treat 2-[[5-ethylsulfanyl-2-methyl-6-[3-methyl-6-(trifluoromethyl)imidazo] under the same conditions described in step 4 of Example P5 [4,5-b]pyridin-2-yl]-3-pyridyl]oxy]acetonitrile (compound I15 prepared as described above) to give the desired compound.

(P4)LCMS (Method 1): m/z 436 [M+H] ⁺ ; Retention time: 1.16 min. Step 5: 2-[[5-(Ethylsulfonylimino)-2-methyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine -2-yl]-3-pyridyl]oxy]-2-methyl-propionitrile (Compound P4)

(P4)

Treat 2-[[5-ethylsulfanyl-2-methyl-6-[3-methyl-6-(trifluoromethyl)imidazo] under the same conditions as described in step 5 of Example P5 [4,5-b]pyridin-2-yl]-3-pyridinyl]oxy]-2-methyl-propionitrile (compound I16 prepared as described above) to give the desired compound.

(P7) 步驟1：5-環丙基-2-(3-乙基氫硫基-5-羥基-2-吡啶基)-3-甲基-6-(三氟甲基)咪唑并[4,5-c]吡啶-4-酮（化合物I17）的製備

(I17)LCMS (Method 1): m/z 467 [M+H] ⁺ ; Retention time: 0.97 min. Example P7 : 2-[[6-[5-cyclopropyl-3-methyl-4- pendant oxy-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl ]-5-(Ethylsulfonylimino)-3-pyridyl]oxy]-2-methyl-propionitrile (Compound P7)

(P7) Step 1: 5-cyclopropyl-2-(3-ethylhydrosulfanyl-5-hydroxy-2-pyridyl)-3-methyl-6-(trifluoromethyl)imidazo[4 ,5-c]Pyridin-4-one (Compound I17) Preparation

(I17)

Cesium carbonate (2.75 g, 8.43 mmol, 3.00 equivalents) and (E)-benzaldehyde oxime (614 μL, 5.62 mmol, 2.00 equivalents) were added to 2-(5-bromo-3-ethylsulfanyl-2- Pyridyl)-5-cyclopropyl-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-4-one (prepared as described in WO 2017089190) (1.33 g, 2.81 mmol) in a solution of N,N-dimethylformamide (12 mL). The resulting suspension was stirred at 45°C overnight. After cooling to room temperature, the reaction mixture was diluted with water, and the pH of the aqueous phase was adjusted to 1 by adding a 2 N hydrochloric acid solution. The aqueous phase was extracted with ethyl acetate, and the combined organic phases were dried over sodium sulfate, filtered and concentrated. The crude material was purified by flash chromatography on silica gel (ethyl acetate in cyclohexane) to give the desired product (1.00 g, 2.44 mmol) as a white solid.

LCMS (Method 1): m/z 355 [M+H] ⁺ ; Retention time: 0.94 min.

(I18) ¹ H NMR (400 MHz, chloroform-d) δ ppm 1.06 (br s, 2H) 1.18-1.37 (m, 5H) 2.75 (q, J =7.38Hz, 2H) 3.07-3.16 (m, 1H) 4.04 (s , 3H) 7.06 (d, J =2.45Hz, 1H) 7.28 (m, 1H) 7.98 (d, J =2.45Hz, 1H). Step 2: 2-[[6-[5-Cyclopropyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl] Preparation of -5-ethylhydrosulfanyl-3-pyridyl]oxy]acetonitrile (compound I18)

(I18)

At 0°C, under argon, potassium carbonate (404 mg, 2.92 mmol, 1.50 equivalents) and then bromoacetonitrile (177 μL, 2.53 mmol, 1.30 equivalents) was added to 5-cyclopropyl after stirring for 10 min -2-(3-Ethylsulfanyl-5-hydroxy-2-pyridyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-4-one( The compound I17) (800 mg, 1.95 mmol) prepared as described above was in a solution of N,N-dimethylformamide (8.0 mL). After stirring for 2 hours at room temperature, the reaction mixture was poured onto ice water, and the aqueous phase was extracted twice with ethyl acetate. The combined organic phases were washed with water, dried over sodium sulfate, filtered and concentrated. The crude material was used without further purification.

(I19)LCMS (Method 3): m/z 450 [M+H] ⁺ ; Retention time: 1.481 min. Step 3: 2-[[6-[5-Cyclopropyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl] Preparation of -5-ethylhydrosulfanyl-3-pyridyl]oxy]-2-methyl-propionitrile (compound I19)

(I19)

A 2 M lithium hexamethyldisilazane solution in tetrahydrofuran (2.50 mL, 5.00 mmol, 3.00 equivalents) was added dropwise to the 2-[[6-[5-cyclopropyl-3-methyl-4- Pendant oxy-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-5-ethylsulfanyl-3-pyridyl]oxy]acetonitrile (prepared as described above The compound I18) (750 mg, 1.67 mmol) and methyl iodide (418 μL, 6.68 mmol, 4.00 equivalents) in tetrahydrofuran (20 mL) cooled at 0°C. The reaction mixture was stirred with an ice bath for 2 hours, and then quenched by pouring onto a saturated aqueous sodium bicarbonate solution. The aqueous phase was extracted with ethyl acetate. The combined organic phase was washed with brine, dried over sodium sulfate, filtered and evaporated. The crude material was purified by flash chromatography on silica gel (ethyl acetate in cyclohexane) to obtain the desired compound (700 mg, 1.66 mmol).

(P7)LCMS (Method 3): m/z 478 [M+H] ⁺ ; Retention time: 1.54 min. Step 4: 2-[[6-[5-Cyclopropyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl] Preparation of -5-(ethylsulfonylimino)-3-pyridyl]oxy]-2-methyl-propionitrile (compound P7)

(P7)

Diacetoxy iodobenzene (275 mg, 0.84 mmol, 2.50 equivalents) and ammonium carbamate (52 mg, 0.67 mmol, 2.00 equivalents) were added to 2-[[6-[5-cyclopropyl-3- Methyl-4- pendant oxy-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-5-ethylhydrothio-3-pyridyl]oxy]- A solution of 2-methyl-propionitrile (compound I19 prepared as described above) (160 mg, 0.34 mmol) in methanol (5.0 mL). After stirring overnight at room temperature, the reaction mixture was quenched with saturated aqueous sodium thiosulfate solution. Control any presence of peroxide in the water phase, then extract three times with ethyl acetate. The combined organic layer was dried over anhydrous sodium sulfate, filtered and concentrated under vacuum. The crude product was purified by flash chromatography (ethyl acetate) on silica gel to obtain the desired compound (120 mg, 0.24 mmol) as a white solid.

LCMS (Method 4): m/z 509 [M+H] ⁺ ; Retention time: 0.92 min.

(P6) 步驟1：5-乙基-2-(3-乙基氫硫基-5-羥基-2-吡啶基)-3-甲基-6-(三氟甲基)咪唑并[4,5-c]吡啶-4-酮（化合物I20）的製備

(I20) ¹ H NMR (400 MHz, chloroform-d) δ ppm 8.76 (d, J =2.69Hz, 1H) 8.35 (d, J =2.69Hz, 1H) 7.19 (s, 1H) 4.00-4.05 (m, 3H) 3.69 -3.85 (m, 2H) 3.10 (br d, J = 3.67Hz) 1.87-1.91 (m, 6H) 1.21-1.42 (m, 8H) 1.07 (br s, 2H). Example P6 : 2-[[6-[5-Ethyl-3-methyl-4- pendant oxy-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl] Preparation of -5-(ethylsulfonylimino)-3-pyridyl]oxy]-2-methyl-propionitrile (compound P6)

(P6) Step 1: 5-Ethyl-2-(3-ethylhydrosulfanyl-5-hydroxy-2-pyridyl)-3-methyl-6-(trifluoromethyl)imidazo[4, 5-c] Preparation of pyridin-4-one (Compound I20)

(I20)

Under the same conditions described in step 1 of Example P7, 2-(5-bromo-3-ethylhydrosulfanyl-2-pyridyl)-5-ethyl-3-methyl-6-(tri Fluoromethyl)imidazo[4,5-c]pyridin-4-one (prepared as described in WO 2017084879) to give the desired compound.

LCMS (Method 3): m/z 399 [M+H] ⁺ ; Retention time: 1.38 min. ¹ H NMR (400 MHz, chloroform-d) δ ppm 7.99 (m, 1H) 7.29 (m, 1H) 7.06 (m, 1H) 4.26 (q, J =6.89Hz,

(I21)2H) 4.08 (s, 3H) 2.75 (q, J =7.46Hz, 2H) 1.42-1.37 (m, 3H) 1.18-1.23 (m, 3 H). Step 2: 2-[[6-[5-Ethyl-3-methyl-4- pendant oxy-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]- Preparation of 5-ethylhydrosulfanyl-3-pyridyl]oxy]acetonitrile (compound I21)

(I21)

Treat 5-ethyl-2-(3-ethylhydrosulfanyl-5-hydroxy-2-pyridyl)-3-methyl-6-(trimethyl) under the same conditions as described in step 2 of Example P7 Fluoromethyl)imidazo[4,5-c]pyridin-4-one (compound I20 prepared as described above) to give the desired compound.

LCMS (Method 4): m/z 438 [M+H] ⁺ ; Retention time: 1.01 min. ¹ H NMR (400 MHz, chloroform-d) δ ppm 8.25 (m, 1H) 7.33 (m, 1H) 7.31 (m, 1H) 4.93 (m,

(I22)2H) 4.28 (m, 2H) 4.20 (m, 3H) 2.95 (m, 2H) 1.41-1.34 (m, 6H). Step 3: 2-[[6-[5-Ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]- Preparation of 5-ethylhydrosulfanyl-3-pyridyl]oxy]-2-methyl-propionitrile (compound I22)

(I22)

Treat 2-[[6-[5-ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[ under the same conditions as described in step 3 of Example P7 4,5-c]pyridin-2-yl]-5-ethylsulfanyl-3-pyridyl]oxy]acetonitrile (compound I21 prepared as described above) to give the desired compound.

LCMS (Method 4): m/z 466 [M+H] ⁺ ; Retention time: 1.10 min.

(P6) ¹ H NMR (400 MHz, chloroform-d) δ ppm 8.31 (m, 1H) 7.65 (m, 1H) 7.32 (m, 1H) 4.25 (m, 6H) 2.96 (m, 2H) 1.81-1.84 (m, 6H) ). Step 4: 2-[[6-[5-Ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]- Preparation of 5-(ethylsulfonylimino)-3-pyridyl]oxy]-2-methyl-propionitrile (compound P6)

(P6)

Treat 2-[[6-[5-ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[ under the same conditions as described in step 4 of Example P7 4,5-c]pyridin-2-yl]-5-ethylsulfanyl-3-pyridinyl]oxy]-2-methyl-propionitrile (compound I22 prepared as described above) to give the desired compound of.

LCMS (Method 4): m/z 497 [M+H] ⁺ ; Retention time: 0.93 min.

(P9) 步驟1：1-(3-乙基氫硫基-5-羥基-2-吡啶基)乙酮（化合物I23）的製備

(I23) ¹ H NMR (400 MHz, chloroform-d) δ ppm 8.77 (m, 1H) 8.35 (m, 1H) 7.21 (m, 1H) 4.25 (m, 3H) 4.07 (m, 3H) 3.76 (m, 2H) 1.87 -1.92 (m, 6H). Example P9 : 2-[[5-(Ethylsulfonylimino)-6-[7-(1,1,2,2,2-pentafluoroethyl)imidazo[1,2-c] Preparation of pyrimidin-2-yl]-3-pyridyl]oxy]-2-methyl-propionitrile (compound P9)

(P9) Step 1: Preparation of 1-(3-ethylhydrosulfanyl-5-hydroxy-2-pyridyl)ethanone (Compound I23)

(I23)

Cesium carbonate (6.65 g, 20.40 mmol, 2.20 equivalents) and (E)-benzaldehyde oxime (1.32 mL, 12.1 mmol, 1.30 equivalents) were added to 1-(5-chloro-3-ethylhydrosulfanyl-2- Pyridyl) ethyl ketone (prepared as described in WO 2016071214) (2.00 g, 9.27 mmol) in N,N-dimethylformamide (18 mL). The resulting suspension was stirred overnight at room temperature. The reaction mixture was diluted with water, and the pH of the aqueous phase was adjusted to 1 by adding 1N hydrochloric acid solution. The aqueous phase was extracted with ethyl acetate, and the combined organic phases were dried over sodium sulfate, filtered and concentrated. The crude material was purified by flash chromatography on silica gel (ethyl acetate in cyclohexane) to give the desired product (1.47 g, 2.44 mmol) as a white solid.

(I24) ¹ H NMR (400 MHz, dimethylsulfide-d6) δ ppm 1.28 (t, J =7.34Hz, 3H) 2.86 (q, J =7.34Hz, 2H) 3.33 (s, 3H) 7.15 (d, J =2.20Hz, 1H) 7.98 (d, J =2.20Hz, 1H) 10.94 (s br, 1H). Step 2: Preparation of 2-[(6-Acetyl-5-ethylsulfanyl-3-pyridyl)oxy]-2-methyl-propanamide (Compound I24)

(I24)

Cesium carbonate (9.2 g, 28 mmol, 1.5 equivalents) was added to 1-(3-ethylhydrosulfanyl-5-hydroxy-2-pyridyl)ethanone (compound I23 prepared as described above) (3.7 g, 19 mmol) in acetonitrile (94 mL). The resulting suspension was stirred for 5 min, then 2-bromo-2-methyl-propanamide (5.0 g, 30 mmol, 1.6 equivalents) was added, and the reaction mixture was heated and stirred at room temperature overnight. After cooling to room temperature, the reaction mixture was poured onto water, and the aqueous phase was extracted three times with ethyl acetate. The combined organic phases were dried over sodium sulfate, filtered and concentrated. The crude material can be used in the next step without further purification.

(I25) ¹ H NMR (400 MHz, dimethyl sulfide-d6) δ ppm 1.28 (t, J =7.34Hz, 3H) 1.56 (s, 6H) 1.85 (s, 3H) 2.83 (q, J =7.34Hz, 2H ) 7.15 (d, J =2.20Hz, 1H) 7.33 (s, 1H) 7.45 (s, 1H) 8.04 (d, J =2.20Hz, 1H). Step 3: Preparation of 2-[(6-Acetyl-5-ethylsulfanyl-3-pyridyl)oxy]-2-methyl-propionitrile (Compound I25)

(I25)

At 0°C, trifluoroacetic anhydride (6.27 mL, 44.6 mmol, 3.00 equivalents) was added to 2-[(6-acetyl-5-ethylhydrosulfanyl-3-pyridyl)oxy]- 2-Methyl-propylamide (compound I24 prepared as described above) (6.0 g, 14.9 mmol) in dichloromethane (149 mL) and triethylamine (8.38 mL, 59.5 mmol, 4.00 equivalents) in solution . After stirring for 2 hours at room temperature, the reaction mixture was carefully quenched by adding methanol and then saturated sodium bicarbonate solution. The aqueous phase was extracted twice with dichloromethane, the combined organic layer was dried over sodium sulfate, filtered and concentrated. The crude material was purified by flash chromatography (0-100% ethyl acetate in cyclohexane) on silica gel to give the desired product (3.69 g) as a yellow oil.

(I26) ¹ H NMR (400 MHz, chloroform-d) δ ppm 1.44 (t, J =7.34Hz, 3H) 1.83 (s, 6H) 2.71 (s, 3H) 2.93 (q, J =7.34Hz, 2H) 7.57 (d , J =2.20Hz, 1H) 8.22 (d, J =2.20Hz, 1H). Step 4: Preparation of 2-[[6-(2-Bromoacetinyl)-5-ethylsulfanyl-3-pyridyl]oxy]-2-methyl-propionitrile (Compound I26)

(I26)

Trimethyl(phenyl)ammonium tribromide (1.43 g, 3.78 mmol) was added to 2-[(6-acetyl-5-ethylsulfanyl-3-pyridyl)oxy]-2- Methyl-propionitrile (compound I25 prepared as described above) (1.00 g, 3.78 mmol) in tetrahydrofuran (14.4 mL, freshly opened bottle) in a 0°C cooled solution. The resulting orange suspension was stirred at room temperature for 42 hours, and then the reaction was quenched with water. The aqueous phase was extracted three times with ethyl acetate, the combined organic phases were washed with brine, dried over sodium sulfate, filtered and concentrated. The crude yellow oil was triturated in cold cyclohexane (15 mL) containing some dichloromethane (1.0 mL) to obtain a precipitate, which was filtered and washed with cyclohexane to give the desired compound as a yellow solid (812 mg). The filtrate was purified by flash chromatography (ethyl acetate in cyclohexane) on silica gel to give a second fraction of the desired compound (500 mg) as a yellow oil with lower purity.

(I27) ¹ H NMR (400 MHz, chloroform-d) δ ppm 1.45 (t, J =7.34Hz, 3H) 1.85 (s, 6H) 2.96 (q, J =7.34Hz, 2H) 4.82 (s, 2H) 7.59 (d , J =2.57z, 1H) 8.21 (d, J =2.57Hz, 1H). Step 5: 2-[[5-Ethylsulfanyl-6-[7-(1,1,2,2,2-pentafluoroethyl)imidazo[1,2-c]pyrimidin-2-yl ]-3-pyridyl]oxy]-2-methyl-propionitrile (Compound I27)

(I27)

(P9)The 2-[[6-(2-bromoacetinyl)-5-ethylhydrosulfanyl-3-pyridyl]oxy]-2-methyl-propionitrile (compound I26 prepared as described above) ( 250 mg, 0.73 mmol) and 6-(1,1,2,2,2-pentafluoroethyl)pyrimidin-4-amine (prepared according to WO 2016071214) (163 mg, 0.76 mmol) in acetonitrile (5.5 mL) The suspension was heated at 70°C and stirred overnight. After cooling to room temperature, the mixture was poured on water, and the aqueous phase was extracted with ethyl acetate. The combined organic phase was washed with brine, dried over sodium sulfate, filtered and concentrated. The crude material was partially purified by flash chromatography (ethyl acetate in cyclohexane) on silica gel to give the desired product mixture, which contained some 6-(1,1,2,2,2 -Pentafluoroethyl)pyrimidin-4-amine, which can be used in the next step without further purification. Step 6: 2-[[5-(Ethylsulfonylimino)-6-[7-(1,1,2,2,2-pentafluoroethyl)imidazo[1,2-c]pyrimidine -2-yl]-3-pyridyl]oxy]-2-methyl-propionitrile (Compound P9)

(P9)

Diacetoxy iodobenzene (194 mg, 0.59 mmol, 2.95 equivalents) and ammonium carbamate (39 mg, 0.49 mmol, 2.45 equivalents) were added to 2-[[5-ethylhydrosulfanyl-6-[ 7-(1,1,2,2,2-Pentafluoroethyl)imidazo[1,2-c]pyrimidin-2-yl]-3-pyridinyl]oxy]-2-methyl-propionitrile (Compound I27 prepared as described above) (90 mg, 0.20 mmol) in methanol (0.59 mL). After stirring for 30 min at room temperature, the reaction mixture was quenched with saturated aqueous sodium thiosulfate solution. Control any presence of peroxide in the water phase, and then extract twice with ethyl acetate. The combined organic layer was washed with brine, dried over anhydrous sodium sulfate, filtered and concentrated under vacuum. The crude product was purified by flash chromatography on silica gel (methanol in dichloromethane), followed by two reverse phase separations to obtain the desired compound (36 mg) as a white solid.

(P8) 步驟1：2-[[5-乙基氫硫基-6-[7-(三氟甲基)咪唑并[1,2-a]吡啶-2-基]-3-吡啶基]氧基]-2-甲基-丙腈（化合物I28）的製備

(I28) ¹ H NMR (400 MHz, chloroform-d) δ ppm 1.40 (t, J =7.34Hz, 3H) 1.87 (s, 3H) 1.89 (s, 3H) 3.81-4.00 (m, 2H) 8.03 (s, 1H) 8.40 (s, 1H) 8.42 (d, J =2.57Hz, 1H) 8.75 (d, J =2.57Hz, 1H) 9.20 (s, 1H). Example P8 : 2-[[5-(Ethylsulfonylimino)-6-[7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-3-pyridine Preparation of yl]oxy]-2-methyl-propionitrile (compound P8)

(P8) Step 1: 2-[[5-Ethylsulfanyl-6-[7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-3-pyridyl] Preparation of oxy]-2-methyl-propionitrile (Compound I28)

(I28)

Add 2-[[6-(2-bromoacetinyl)-5-ethylhydrosulfanyl-3-pyridyl]oxy]-2-methyl-propionitrile (as described in step 4 of Example P9 above) Description: A suspension of compound I26 (100 mg, 0.20 mmol) and 4-(trifluoromethyl)pyridin-2-amine (commercially available) (35 mg, 0.21 mmol) in acetonitrile (1.5 mL) Heat at 70°C and stir overnight. Magnesium oxide (8 mg, 0.20 mmol) was added to the reaction mixture, and heating was continued for 3 hours to reach the completion of the reaction. After cooling to room temperature, the mixture was poured onto water, and the aqueous phase was extracted twice with ethyl acetate. The combined organic phase was washed with brine, dried over sodium sulfate, filtered and concentrated. The crude material was partially purified by flash chromatography on silica gel (ethyl acetate in cyclohexane) to obtain the desired product (60 mg) as a yellow oil.

(P8) ¹ H NMR (400 MHz, chloroform-d) δ ppm 1.44 (t, J =7.34Hz, 3H) 1.81(s, 6H) 3.04 (q, J =7.34Hz, 2H) 7.02 (dd, J1 =7.34; J2 =1.65Hz, 1H) 7.65 (d, J =2.57Hz, 1H) 8.06 (s, 1H) 8.29 (d, J =7.34Hz, 1H) 8.32 (d, J =2.57Hz, 1H) 8.37 (d, J =1.65Hz, 1H). Step 2: 2-[[5-(Ethylsulfonylimino)-6-[7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-3-pyridyl ]Oxy]-2-methyl-propionitrile (Compound P8)

(P8)

Treat 2-[[5-ethylsulfanyl-6-[7-(trifluoromethyl)imidazo[1,2-a]pyridine- under the same conditions as described in step 6 of Example P9 2-yl]-3-pyridyl]oxy]-2-methyl-propionitrile (compound I28 prepared as described above) to give the desired compound.

(P10) 步驟1：2-[[5-乙基氫硫基-6-[7-(三氟甲基)咪唑并[1,2-c]嘧啶-2-基]-3-吡啶基]氧基]-2-甲基-丙腈（化合物I29）的製備

(I29) ¹ H NMR (400 MHz, chloroform-d) δ ppm 1.37 (t, J =7.34Hz, 3H) 1.85 (s, 3H) 1.87 (s, 3H) 3.80 (dq, J1 =14.12Hz; J2 =7.34Hz, 1H) 3.97 (dq, J1 =14.12Hz; J2 =7.34Hz, 1H) 7.08 (dd, J1 =6.97; J2 =1.83Hz, 1H) 7.98 (m, 1H) 8.32 (d, J =7.34Hz, 1H) 8.38 (s, 1H) 8.40 (d, J =2.57Hz, 1H) 8.73 (d, J =2.57Hz, 1H). Example P10 : 2-[[5-(Ethylsulfonylimino)-6-[7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-2-yl]-3-pyridine Preparation of yl]oxy]-2-methyl-propionitrile (compound P10)

(P10) Step 1: 2-[[5-Ethylsulfanyl-6-[7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-2-yl]-3-pyridyl] Preparation of oxy]-2-methyl-propionitrile (compound I29)

(I29)

Under the same conditions as described in step 5 of Example P9, 2-[[6-(2-bromoacetinyl)-5-ethylhydrothio-3-pyridyl]oxy]-2- Methyl-propionitrile (compound I26 prepared as described in step 4 of Example P9 above) and 6-(trifluoromethyl)pyrimidin-4-amine (prepared according to WO 2016071214) were mixed to obtain the desired compound.

(P10) ¹ H NMR (400 MHz, chloroform-d) δ ppm 1.44 (t, J =7.34Hz, 3H) 1.81 (s, 6H) 3.04 (q, J =7.34Hz, 2H) 7.67 (s, 1H) 8.05 (s , 1H) 8.34 (s, 1H) 8.45 (s, 1H) 9.18 (s, 1H). Step 2: 2-[[5-(Ethylsulfonylimino)-6-[7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-3-pyridyl ]Oxy]-2-methyl-propionitrile (Compound P8)

(P10)

Treat 2-[[5-ethylsulfanyl-6-[7-(trifluoromethyl)imidazo[1,2-a]pyridine- under the same conditions as described in step 6 of Example P9 2-yl]-3-pyridyl]oxy]-2-methyl-propionitrile (compound I28 prepared as described above) to give the desired compound.

(P11) 步驟1：2-[[5-乙基氫硫基-6-[7-(三氟甲基氫硫基)咪唑并[1,2-c]嘧啶-2-基]-3-吡啶基]氧基]-2-甲基-丙腈（化合物I30）的製備

(I30) ¹ H NMR (400 MHz, chloroform-d) δ ppm 1.40 (t, J =7.52Hz, 3H) 1.87 (s, 3H) 1.89 (s, 3H) 3.80-4.00 (m, 2H) 7.99 (s, 1H) 8.41 (s, 1H) 8.75 (s, 1H) 9.19 (s, 1H). Example P11 : 2-[[5-(Ethylsulfonylimino)-6-[7-(trifluoromethylsulfanyl)imidazo[1,2-c]pyrimidin-2-yl]- Preparation of 3-pyridyl]oxy]-2-methyl-propionitrile (compound P11)

(P11) Step 1: 2-[[5-Ethylsulfanyl-6-[7-(trifluoromethylsulfanyl)imidazo[1,2-c]pyrimidin-2-yl]-3- Preparation of pyridyl]oxy]-2-methyl-propionitrile (compound I30)

(I30)

Under the same conditions as described in step 5 of Example P9, 2-[[6-(2-bromoacetinyl)-5-ethylhydrothio-3-pyridyl]oxy]-2- Methyl-propionitrile (compound I26 prepared as described in step 4 of Example P9 above) and 6-(trifluoromethylsulfanyl)pyrimidin-4-amine (prepared according to WO 2016071214) were mixed to obtain the desired compound .

(P11) ¹ H NMR (400 MHz, chloroform-d) δ ppm 1.44 (m, 3H) 1.82 (s, 6H) 3.05 (m, 2H) 7.66 (d, J =2.20Hz, 1H) 8.02 (s, 1H) 8.34 ( d, J =2.20Hz, 1H) 8.39 (s, 1H) 9.10 (s, 1H). Step 2: 2-[[5-(Ethylsulfonylimino)-6-[7-(trifluoromethylsulfanyl)imidazo[1,2-c]pyrimidin-2-yl]-3 -Pyridyl]oxy]-2-methyl-propionitrile (Compound P11)

(P11)

Treat 2-[[5-ethylsulfanyl-6-[7-(trifluoromethylsulfanyl)imidazo[1,2-c] under the same conditions as described in step 6 of Example P9 ]Pyrimidin-2-yl]-3-pyridyl]oxy]-2-methyl-propionitrile (compound I30 prepared as described above) to give the desired compound.

0.86 453 1 90-99 1) P2 2-[[5-(乙基磺醯亞胺基)-6-[7-甲基-3-(三氟甲基)咪唑并[4,5-c]嗒𠯤-6-基]-3-吡啶基]氧基]-2-甲基-丙腈

0.89 454 1 197-199 2) P3 2-[[5-(乙基磺醯亞胺基)-6-[3-甲基-6-(三氟甲基)咪唑并[4,5-b]吡啶-2-基]-3-吡啶基]氧基]-2-甲基-丙腈

0.93 453 1 155-156    P4 2-[[5-(乙基磺醯亞胺基)-2-甲基-6-[3-甲基-6-(三氟甲基)咪唑并[4,5-b]吡啶-2-基]-3-吡啶基]氧基]-2-甲基-丙腈

0.97 467 1 177-179    P5 2-[[5-(乙基磺醯亞胺基)-2-甲基-6-[3-甲基-6-(三氟甲基)咪唑并[4,5-c]吡啶-2-基]-3-吡啶基]氧基]-2-甲基-丙腈

0.91 467 1 185-187    P6 2-[[6-[5-乙基-3-甲基-4-側氧基-6-(三氟甲基)咪唑并[4,5-c]吡啶-2-基]-5-(乙基磺醯亞胺基)-3-吡啶基]氧基]-2-甲基-丙腈

0.93 497 4 110-112    P7 2-[[6-[5-環丙基-3-甲基-4-側氧基-6-(三氟甲基)咪唑并[4,5-c]吡啶-2-基]-5-(乙基磺醯亞胺基)-3-吡啶基]氧基]-2-甲基-丙腈

0.92 509 4 211-213    P8 2-[[5-(乙基磺醯亞胺基)-6-[7-(三氟甲基)咪唑并[1,2-a]吡啶-2-基]-3-吡啶基]氧基]-2-甲基-丙腈

0.88 438 1    3) P9 2-[[5-(乙基磺醯亞胺基)-6-[7-(1,1,2,2,2-五氟乙基)咪唑并[1,2-c]嘧啶-2-基]-3-吡啶基]氧基]-2-甲基-丙腈

0.93 489 1 75-80 4) P10 2-[[5-(乙基磺醯亞胺基)-6-[7-(三氟甲基)咪唑并[1,2-c]嘧啶-2-基]-3-吡啶基]氧基]-2-甲基-丙腈

0.84 439 1 75-78 5) P11 2-[[5-(乙基磺醯亞胺基)-6-[7-(三氟甲基氫硫基)咪唑并[1,2-c]嘧啶-2-基]-3-吡啶基]氧基]-2-甲基-丙腈

0.89 471 1    6) ^{1) 1} H NMR (400 MHz, 氯仿-d) δ ppm 1.40 (t,J =7.34Hz, 3H) 1.93 (s, 6H) 3.89-3.74 (m, 2H) 3.90 (s, 3H) 8.12 (s, 1H) 8.40 (d,J =2.57Hz, 1H) 8.81 (d,J =2.57Hz, 1H) 8.99 (s, 1H)^{2) 1} H NMR (400 MHz, 二甲基亞碸-d6) δ ppm 1.18 (t,J =7.52Hz, 3H) 1.60 (s, 6H) 3.69-3.49 (m, 2H) 3.91 (s, 3H) 4.63 (s, 1H) 8.30 (d,J =2.57Hz, 1H) 8.74 (s, 1H) 8.93 (d,J =2.57Hz, 1H)^{3) 1} H NMR (400 MHz, 氯仿-d) δ ppm 1.37 (t,J =7.34Hz, 3H) 1.85 (s, 3H) 1.87 (s, 3H) 3.80 (dq,J1 =14.12Hz;J2 =7.34Hz, 1H) 3.97 (dq,J1 =14.12Hz;J2 =7.34Hz, 1H) 7.08 (dd,J1 =6.97;J2 =1.83Hz, 1H) 7.98 (m, 1H) 8.32 (d,J =7.34Hz, 1H) 8.38 (s, 1H) 8.40 (d,J =2.57Hz, 1H) 8.73 (d,J =2.57Hz, 1H)^{4) 1} H NMR (400 MHz, 氯仿-d) δ ppm 1.40 (t,J =7.34Hz, 3H) 1.87 (s, 3H) 1.89 (s, 3H) 3.81-4.00 (m, 2H) 8.03 (s, 1H) 8.40 (s, 1H) 8.42 (d,J =2.57Hz, 1H) 8.75 (d,J =2.57Hz, 1H) 9.20 (s, 1H)^{5) 1} H NMR (400 MHz, 氯仿-d) δ ppm 1.40 (t,J =7.52Hz, 3H) 1.87 (s, 3H) 1.89 (s, 3H) 3.80-4.00 (m, 2H) 7.99 (s, 1H) 8.41 (s, 1H) 8.75 (s, 1H) 9.19 (s, 1H)^{6) 1} H NMR (400 MHz, 氯仿-d) δ ppm 1.38 (t,J =7.34Hz, 3H) 1.88 (2*s, 2*3H) 3.74 - 4.00 (m, 2H) 7.94 (s, 1H) 8.35 (d,J =0.73Hz, 1H) 8.41 (d,J =2.93Hz, 1H) 8.75 (d,J =2.93Hz, 1H) 9.11 (d,J =1.47Hz, 1H) [表I]：式 (II)、(III)、(V)、(Va)、(Vb)、(Vc)、(VII)、(XXII)、(XXIII)、(XXIV)、(XXV-c)、(XXV-a)、(XXVI)、(XXVIII)、(XXIX-a) 和 (XXIX-c) 之中間體化合物的實施例 編號 IUPAC名稱 結構 LCMS Mp（°C）   ¹ H NMR R_t （min） [M+H]⁺ （測量的） 方法 I1 5-乙基氫硫基-6-[7-甲基-3-(三氟甲基)咪唑并[4,5-c]嗒𠯤-6-基]吡啶-3-醇

0.86 356 1 216-218 1) I2 2-[[5-乙基氫硫基-6-[7-甲基-3-(三氟甲基)咪唑并[4,5-c]嗒𠯤-6-基]-3-吡啶基]氧基]-2-甲基-丙醯胺

         163-165    I3 2-[[5-乙基氫硫基-6-[7-甲基-3-(三氟甲基)咪唑并[4,5-c]嗒𠯤-6-基]-3-吡啶基]氧基]-2-甲基-丙腈

1.04 423 1    2) I4 5-乙基氫硫基-6-[3-甲基-6-(三氟甲基)咪唑并[4,5-b]吡啶-2-基]吡啶-3-醇

0.94 355 1 194-195    I5 2-[[5-乙基氫硫基-6-[3-甲基-6-(三氟甲基)咪唑并[4,5-b]吡啶-2-基]-3-吡啶基]氧基]乙腈

1.01 394 1       I6 2-[[5-乙基氫硫基-6-[3-甲基-6-(三氟甲基)咪唑并[4,5-b]吡啶-2-基]-3-吡啶基]氧基]-2-甲基-丙腈

1.11 422 1       I7 2-[[5-乙基氫硫基-6-[3-甲基-6-(三氟甲基)咪唑并[4,5-c]吡啶-2-基]-3-吡啶基]氧基]乙腈

0.94 394 1       I8 2-[[5-乙基氫硫基-6-[3-甲基-6-(三氟甲基)咪唑并[4,5-c]吡啶-2-基]-3-吡啶基]氧基]-2-甲基-丙腈

1.02 422 1       I9 5-乙基氫硫基-2-碘-6-[3-甲基-6-(三氟甲基)咪唑并[4,5-c]吡啶-2-基]吡啶-3-醇

0.96 481 1       I10 5-乙基氫硫基-2-甲基-6-[3-甲基-6-(三氟甲基)咪唑并[4,5-c]吡啶-2-基]吡啶-3-醇

0.87 369 1       I11 2-[[5-乙基氫硫基-2-甲基-6-[3-甲基-6-(三氟甲基)咪唑并[4,5-c]吡啶-2-基]-3-吡啶基]氧基]乙腈

0.96 408 1       I12 2-[[5-乙基氫硫基-2-甲基-6-[3-甲基-6-(三氟甲基)咪唑并[4,5-c]吡啶-2-基]-3-吡啶基]氧基]-2-甲基-丙腈

1.06 436 1       I13 5-乙基氫硫基-2-碘-6-[3-甲基-6-(三氟甲基)咪唑并[4,5-b]吡啶-2-基]吡啶-3-醇

1.06 480 1       I14 5-乙基氫硫基-2-甲基-6-[3-甲基-6-(三氟甲基)咪唑并[4,5-b]吡啶-2-基]吡啶-3-醇

0.96 369 1       I15 2-[[5-乙基氫硫基-2-甲基-6-[3-甲基-6-(三氟甲基)咪唑并[4,5-b]吡啶-2-基]-3-吡啶基]氧基]乙腈

1.05 408 1       I16 2-[[5-乙基氫硫基-2-甲基-6-[3-甲基-6-(三氟甲基)咪唑并[4,5-b]吡啶-2-基]-3-吡啶基]氧基]-2-甲基-丙腈

1.16 436 1       I17 5-環丙基-2-(3-乙基氫硫基-5-羥基-2-吡啶基)-3-甲基-6-(三氟甲基)咪唑并[4,5-c]吡啶-4-酮

1.36 411 3    3) I18 2-[[6-[5-環丙基-3-甲基-4-側氧基-6-(三氟甲基)咪唑并[4,5-c]吡啶-2-基]-5-乙基氫硫基-3-吡啶基]氧基]乙腈

1.48 450 3       I19 2-[[6-[5-環丙基-3-甲基-4-側氧基-6-(三氟甲基)咪唑并[4,5-c]吡啶-2-基]-5-乙基氫硫基-3-吡啶基]氧基]-2-甲基-丙腈

1.54 478 3       I20 5-乙基-2-(3-乙基氫硫基-5-羥基-2-吡啶基)-3-甲基-6-(三氟甲基)咪唑并[4,5-c]吡啶-4-酮

1.38 399 3       I21 2-[[6-[5-乙基-3-甲基-4-側氧基-6-(三氟甲基)咪唑并[4,5-c]吡啶-2-基]-5-乙基氫硫基-3-吡啶基]氧基]乙腈

1.01 438 4       I22 2-[[6-[5-乙基-3-甲基-4-側氧基-6-(三氟甲基)咪唑并[4,5-c]吡啶-2-基]-5-乙基氫硫基-3-吡啶基]氧基]-2-甲基-丙腈

1.10 466 4       I23 1-(3-乙基氫硫基-5-羥基-2-吡啶基)乙酮

            4) I24 2-[(6-乙醯基-5-乙基氫硫基-3-吡啶基)氧基]-2-甲基-丙醯胺

            5) I25 2-[(6-乙醯基-5-乙基氫硫基-3-吡啶基)氧基]-2-甲基-丙腈

            6) I26 2-[[6-(2-溴乙醯基)-5-乙基氫硫基-3-吡啶基]氧基]-2-甲基-丙腈

            7) I27 2-[[5-乙基氫硫基-6-[7-(1,1,2,2,2-五氟乙基)咪唑并[1,2-c]嘧啶-2-基]-3-吡啶基]氧基]-2-甲基-丙腈

1.10 458 1       I28 2-[[5-乙基氫硫基-6-[7-(三氟甲基)咪唑并[1,2-a]吡啶-2-基]-3-吡啶基]氧基]-2-甲基-丙腈

1.02 407 1    8) I29 2-[[5-乙基氫硫基-6-[7-(三氟甲基)咪唑并[1,2-c]嘧啶-2-基]-3-吡啶基]氧基]-2-甲基-丙腈

1.03 408 1    9) I30 2-[[5-乙基氫硫基-6-[7-(三氟甲基氫硫基)咪唑并[1,2-c]嘧啶-2-基]-3-吡啶基]氧基]-2-甲基-丙腈

1.06 440 1    10) I31 2-[[5-乙基氫硫基-6-[3-甲基-6-(三氟甲基)咪唑并[4,5-b]吡啶-2-基]-3-吡啶基]氧基]-2-甲基-丙醯胺

0.96 440 1 228-230    I32 5-(1-氰基-1-甲基-乙氧基)-3-乙基氫硫基-吡啶-2-碳醯氯

；對於對應的N,N-二甲基甲醯胺（C₁₄ H₁₉ N₃ O₂ S，293.38）的數據 0.83 294 1       I33 3-乙基氫硫基-5-羥基-吡啶-2-甲酸甲酯

0.68 214 1       I34 5-(2-胺基-1,1-二甲基-2-側氧基-乙氧基)-3-乙基氫硫基-吡啶-2-甲酸甲酯

0.71 299 1       I35 5-(1-氰基-1-甲基-乙氧基)-3-乙基氫硫基-吡啶-2-甲酸甲酯

0.90 281 1       I36 5-(1-氰基-1-甲基-乙氧基)-3-乙基氫硫基-吡啶-2-甲酸

0.82 267 4       ^{1) 1} H NMR (400 MHz, 二甲基亞碸-d6) δ ppm 1.25 (t,J =7.34Hz, 3H) 2.99 (q,J =7.34Hz, 2H) 4.13 (s, 3H) 7.38 (d,J =2.20Hz, 1H) 8.17 (d,J =2.20Hz, 1H) 8.55 (s, 1H) 10.94 (s, 1H)^{2) 1} H NMR (400 MHz, 氯仿-d) δ ppm 1.42 (t,J =7.34Hz, 3H) 1.88 (s, 6H) 3.03 (q,J =7.34Hz, 2H) 4.31 (s, 3H) 7.72 (d,J =2.57Hz, 1H) 8.26 (s, 1H) 8.39 (d,J =2.57Hz, 1H)^{3) 1} H NMR (400 MHz, 氯仿-d) δ ppm 1.06 (br s, 2H) 1.18-1.37 (m, 5H) 2.75 (q,J =7.38Hz, 2H) 3.07-3.16 (m, 1H) 4.04 (s, 3H) 7.06 (d,J =2.45Hz, 1H) 7.28 (m, 1H) 7.98 (d,J =2.45Hz, 1H)^{4) 1} H NMR (400 MHz, 二甲基亞碸-d6) δ ppm 1.28 (t,J =7.34Hz, 3H) 2.86 (q,J =7.34Hz, 2H) 3.33 (s, 3H) 7.15 (d,J =2.20Hz, 1H) 7.98 (d,J =2.20Hz, 1H) 10.94 (s br, 1H)^{5) 1} H NMR (400 MHz, 二甲基亞碸-d6) δ ppm 1.28 (t,J =7.34Hz, 3H) 1.56 (s, 6H) 1.85 (s, 3H) 2.83 (q,J =7.34Hz, 2H) 7.15 (d,J =2.20Hz, 1H) 7.33 (s, 1H) 7.45 (s, 1H) 8.04 (d,J =2.20Hz, 1H)^{6) 1} H NMR (400 MHz, 氯仿-d) δ ppm 1.44 (t,J =7.34Hz, 3H) 1.83 (s, 6H) 2.71 (s, 3H) 2.93 (q,J =7.34Hz, 2H) 7.57 (d,J =2.20Hz, 1H) 8.22 (d,J =2.20Hz, 1H)^{7) 1} H NMR (400 MHz, 氯仿-d) δ ppm 1.45 (t,J =7.34Hz, 3H) 1.85 (s, 6H) 2.96 (q,J =7.34Hz, 2H) 4.82 (s, 2H) 7.59 (d,J =2.57z, 1H) 8.21 (d,J =2.57Hz, 1H)^{8) 1} H NMR (400 MHz, 氯仿-d) δ ppm 1.44 (t,J =7.34Hz, 3H) 1.81(s, 6H) 3.04 (q,J =7.34Hz, 2H) 7.02 (dd,J1 =7.34;J2 =1.65Hz, 1H) 7.65 (d,J =2.57Hz, 1H) 8.06 (s, 1H) 8.29 (d,J =7.34Hz, 1H) 8.32 (d,J =2.57Hz, 1H) 8.37 (d,J =1.65Hz, 1H)^{9) 1} H NMR (400 MHz, 氯仿-d) δ ppm 1.44 (t,J =7.34Hz, 3H) 1.81 (s, 6H) 3.04 (q,J =7.34Hz, 2H) 7.67 (s, 1H) 8.05 (s, 1H) 8.34 (s, 1H) 8.45 (s, 1H) 9.18 (s, 1H)^{10) 1} H NMR (400 MHz, 氯仿-d) δ ppm 1.44 (m, 3H) 1.82 (s, 6H) 3.05 (m, 2H) 7.66 (d,J =2.20Hz, 1H) 8.02 (s, 1H) 8.34 (d,J =2.20Hz, 1H) 8.39 (s, 1H) 9.10 (s, 1H)。 實施例I32：5-(1-氰基-1-甲基-乙氧基)-3-乙基氫硫基-吡啶-2-碳醯氯（化合物I32）的製備

(I32) 步驟1：3-乙基氫硫基-5-羥基-吡啶-2-甲酸甲酯（化合物I33）的製備

(I33) ¹ H NMR (400 MHz, chloroform-d) δ ppm 1.38 (t, J =7.34Hz, 3H) 1.88 (2*s, 2*3H) 3.74-4.00 (m, 2H) 7.94 (s, 1H) 8.35 ( d, J =0.73Hz, 1H) 8.41 (d, J =2.93Hz, 1H) 8.75 (d, J =2.93Hz, 1H) 9.11 (d, J =1.47Hz, 1H). [Table P]: Examples of compounds of formula (I) and (Ia) Numbering IUPAC name structure LCMS Mp (°C) ¹ H NMR R _t (min) [M+H] ⁺ (measured) method P1 2-[[5-(Ethylsulfonylimino)-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3- Pyridyl]oxy]-2-methyl-propionitrile

0.86 453 1 90-99 1) P2 2-[[5-(Ethylsulfonylimino)-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]ta𠯤-6-yl]-3 -Pyridyl]oxy]-2-methyl-propionitrile

0.89 454 1 197-199 2) P3 2-[[5-(Ethylsulfonylimino)-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3- Pyridyl]oxy]-2-methyl-propionitrile

0.93 453 1 155-156 P4 2-[[5-(Ethylsulfonylimino)-2-methyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine-2- Yl]-3-pyridyl]oxy]-2-methyl-propionitrile

0.97 467 1 177-179 P5 2-[[5-(Ethylsulfonylimino)-2-methyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine-2- Yl]-3-pyridyl]oxy]-2-methyl-propionitrile

0.91 467 1 185-187 P6 2-[[6-[5-Ethyl-3-methyl-4- pendant oxy-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-5-( (Ethylsulfonylimino)-3-pyridyl)oxy)-2-methyl-propionitrile

0.93 497 4 110-112 P7 2-[[6-[5-Cyclopropyl-3-methyl-4- pendant oxy-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-5- (Ethylsulfonylimino)-3-pyridyl)oxy)-2-methyl-propionitrile

0.92 509 4 211-213 P8 2-[[5-(Ethylsulfonylimino)-6-[7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-3-pyridinyl]oxy ]-2-Methyl-propionitrile

0.88 438 1 3) P9 2-[[5-(Ethylsulfonylimino)-6-[7-(1,1,2,2,2-pentafluoroethyl)imidazo[1,2-c]pyrimidine-2- Yl]-3-pyridyl]oxy]-2-methyl-propionitrile

0.93 489 1 75-80 4) P10 2-[[5-(Ethylsulfonylimino)-6-[7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-2-yl]-3-pyridinyl]oxy ]-2-Methyl-propionitrile

0.84 439 1 75-78 5) P11 2-[[5-(Ethylsulfonylimino)-6-[7-(trifluoromethylsulfanyl)imidazo[1,2-c]pyrimidin-2-yl]-3-pyridyl ]Oxy]-2-methyl-propionitrile

0.89 471 1 6) ^{1) 1} H NMR (400 MHz, chloroform-d) δ ppm 1.40 (t, J =7.34Hz, 3H) 1.93 (s, 6H) 3.89-3.74 (m, 2H) 3.90 (s, 3H) 8.12 (s, 1H) 8.40 (d, J =2.57Hz, 1H) 8.81 (d, J =2.57Hz, 1H) 8.99 (s, 1H) ^{2) 1} H NMR (400 MHz, dimethylsulfide-d6) δ ppm 1.18 (t, J =7.52Hz, 3H) 1.60 (s, 6H) 3.69-3.49 (m, 2H) 3.91 (s, 3H) 4.63 (s, 1H) 8.30 (d, J =2.57Hz, 1H) 8.74 (s , 1H) 8.93 (d, J =2.57Hz, 1H) ^{3) 1} H NMR (400 MHz, chloroform-d) δ ppm 1.37 (t, J =7.34Hz, 3H) 1.85 (s, 3H) 1.87 (s, 3H) 3.80 (dq, J1 =14.12Hz; J2 =7.34Hz, 1H) 3.97 (dq, J1 =14.12Hz; J2 =7.34Hz, 1H) 7.08 (dd, J1 =6.97; J2 =1.83Hz, 1H) 7.98 (m, 1H) 8.32 (d, J =7.34Hz, 1H) 8.38 (s, 1H) 8.40 (d, J =2.57Hz, 1H) 8.73 (d, J =2.57Hz, 1H) ^{4) 1} H NMR ( 400 MHz, chloroform-d) δ ppm 1.40 (t, J =7.34Hz, 3H) 1.87 (s, 3H) 1.89 (s, 3H) 3.81-4.00 (m, 2H) 8.03 (s, 1H) 8.40 (s, 1H) 8.42 (d, J =2.57Hz, 1H) 8.75 (d, J =2.57Hz, 1H) 9.20 (s, 1H) ^{5) 1} H NMR (400 MHz, chloroform-d) δ ppm 1.40 (t, J =7.52Hz, 3H) 1.87 (s, 3H) 1.89 (s, 3H) 3.80-4.00 (m, 2H) 7.99 (s, 1H) 8.41 (s, 1H) 8.75 (s, 1H) 9.19 (s, 1H) ^{6) 1} H NMR (400 MHz, chloroform-d) δ ppm 1.38 (t, J =7.34Hz, 3H) 1.88 (2*s, 2*3H) 3.74-4.00 (m, 2H) 7.94 (s, 1H) 8.35 (d, J =0.73Hz, 1H) 8.41 (d, J =2.93Hz, 1H) 8.75 (d, J =2.93Hz, 1H) 9.11 (d, J =1.47Hz, 1H) [Table I]: Formula (II), ( III), (V), (Va), (Vb), (Vc), (VII), (XXII), (XXIII), (XXIV), (XXV-c), (XXV-a), (XXVI) Examples of intermediate compounds of, (XXVIII), (XXIX-a) and (XXIX-c) Numbering IUPAC name structure LCMS Mp (°C) ¹ H NMR R _t (min) [M+H] ⁺ (measured) method I1 5-Ethyl hydrogensulfanyl-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]ta𠯤-6-yl]pyridin-3-ol

0.86 356 1 216-218 1) I2 2-[[5-Ethylsulfanyl-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]ta𠯤-6-yl]-3-pyridyl] Oxy]-2-methyl-propanamide

163-165 I3 2-[[5-Ethylsulfanyl-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]ta𠯤-6-yl]-3-pyridyl] Oxy]-2-methyl-propionitrile

1.04 423 1 2) I4 5-Ethyl hydrogensulfanyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]pyridin-3-ol

0.94 355 1 194-195 I5 2-[[5-Ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]oxy Base] Acetonitrile

1.01 394 1 I6 2-[[5-Ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]oxy Yl]-2-methyl-propionitrile

1.11 422 1 I7 2-[[5-Ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridinyl]oxy Base] Acetonitrile

0.94 394 1 I8 2-[[5-Ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridinyl]oxy Yl]-2-methyl-propionitrile

1.02 422 1 I9 5-ethylhydrosulfanyl-2-iodo-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]pyridin-3-ol

0.96 481 1 I10 5-ethylhydrosulfanyl-2-methyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]pyridin-3-ol

0.87 369 1 I11 2-[[5-Ethylsulfanyl-2-methyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3 -Pyridyl]oxy]acetonitrile

0.96 408 1 I12 2-[[5-Ethylsulfanyl-2-methyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3 -Pyridyl]oxy]-2-methyl-propionitrile

1.06 436 1 I13 5-ethylhydrosulfanyl-2-iodo-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]pyridin-3-ol

1.06 480 1 I14 5-Ethylsulfanyl-2-methyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]pyridin-3-ol

0.96 369 1 I15 2-[[5-Ethylsulfanyl-2-methyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3 -Pyridyl]oxy]acetonitrile

1.05 408 1 I16 2-[[5-Ethylsulfanyl-2-methyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3 -Pyridyl]oxy]-2-methyl-propionitrile

1.16 436 1 I17 5-cyclopropyl-2-(3-ethylhydrosulfanyl-5-hydroxy-2-pyridyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine -4-one

1.36 411 3 3) I18 2-[[6-[5-Cyclopropyl-3-methyl-4- pendant oxy-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-5- Ethylsulfanyl-3-pyridyl]oxy]acetonitrile

1.48 450 3 I19 2-[[6-[5-Cyclopropyl-3-methyl-4- pendant oxy-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-5- Ethyl hydrogensulfanyl-3-pyridyl]oxy]-2-methyl-propionitrile

1.54 478 3 I20 5-Ethyl-2-(3-ethylhydrosulfanyl-5-hydroxy-2-pyridyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine- 4-ketone

1.38 399 3 I21 2-[[6-[5-Ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-5-ethyl Sulfanyl-3-pyridyl]oxy]acetonitrile

1.01 438 4 I22 2-[[6-[5-Ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-5-ethyl Sulfanyl-3-pyridyl]oxy]-2-methyl-propionitrile

1.10 466 4 I23 1-(3-Ethylsulfanyl-5-hydroxy-2-pyridyl)ethanone

4) I24 2-[(6-Acetyl-5-ethylsulfanyl-3-pyridyl)oxy]-2-methyl-propanamide

5) I25 2-[(6-Acetyl-5-ethylsulfanyl-3-pyridyl)oxy]-2-methyl-propionitrile

6) I26 2-[[6-(2-Bromoacetinyl)-5-ethylhydrosulfanyl-3-pyridyl]oxy]-2-methyl-propionitrile

7) I27 2-[[5-Ethylsulfanyl-6-[7-(1,1,2,2,2-pentafluoroethyl)imidazo[1,2-c]pyrimidin-2-yl]-3 -Pyridyl]oxy]-2-methyl-propionitrile

1.10 458 1 I28 2-[[5-Ethylsulfanyl-6-[7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-3-pyridinyl]oxy]-2- Methyl-propionitrile

1.02 407 1 8) I29 2-[[5-Ethylsulfanyl-6-[7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-2-yl]-3-pyridinyl]oxy]-2- Methyl-propionitrile

1.03 408 1 9) I30 2-[[5-Ethylsulfanyl-6-[7-(trifluoromethylsulfanyl)imidazo[1,2-c]pyrimidin-2-yl]-3-pyridinyl]oxy] -2-methyl-propionitrile

1.06 440 1 10) I31 2-[[5-Ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]oxy Yl]-2-methyl-propanamide

0.96 440 1 228-230 I32 5-(1-cyano-1-methyl-ethoxy)-3-ethylhydrosulfanyl-pyridine-2-carbochloride

; For the corresponding N,N-dimethylformamide (C ₁₄ H ₁₉ N ₃ O ₂ S, 293.38) data 0.83 294 1 I33 3-Ethyl hydrogensulfanyl-5-hydroxy-pyridine-2-carboxylic acid methyl ester

0.68 214 1 I34 5-(2-Amino-1,1-dimethyl-2-oxo-ethoxy)-3-ethylsulfanyl-pyridine-2-carboxylic acid methyl ester

0.71 299 1 I35 5-(1-cyano-1-methyl-ethoxy)-3-ethylhydrosulfanyl-pyridine-2-carboxylic acid methyl ester

0.90 281 1 I36 5-(1-cyano-1-methyl-ethoxy)-3-ethylhydrosulfanyl-pyridine-2-carboxylic acid

0.82 267 4 ^{1) 1} H NMR (400 MHz, dimethylsulfoxide-d6) δ ppm 1.25 (t, J =7.34Hz, 3H) 2.99 (q, J =7.34Hz, 2H) 4.13 (s, 3H) 7.38 (d , J =2.20Hz, 1H) 8.17 (d, J =2.20Hz, 1H) 8.55 (s, 1H) 10.94 (s, 1H) ^{2) 1} H NMR (400 MHz, chloroform-d) δ ppm 1.42 (t, J =7.34Hz, 3H) 1.88 (s, 6H) 3.03 (q, J =7.34Hz, 2H) 4.31 (s, 3H) 7.72 (d, J =2.57Hz, 1H) 8.26 (s, 1H) 8.39 (d , J =2.57Hz, 1H) ^{3) 1} H NMR (400 MHz, chloroform-d) δ ppm 1.06 (br s, 2H) 1.18-1.37 (m, 5H) 2.75 (q, J =7.38Hz, 2H) 3.07 -3.16 (m, 1H) 4.04 (s, 3H) 7.06 (d, J =2.45Hz, 1H) 7.28 (m, 1H) 7.98 (d, J =2.45Hz, 1H) ^{4) 1} H NMR (400 MHz, Dimethyl sulfide-d6) δ ppm 1.28 (t, J =7.34Hz, 3H) 2.86 (q, J =7.34Hz, 2H) 3.33 (s, 3H) 7.15 (d, J =2.20Hz, 1H) 7.98 (d, J =2.20Hz, 1H) 10.94 (s br, 1H) ^{5) 1} H NMR (400 MHz, dimethyl sulfide-d6) δ ppm 1.28 (t, J =7.34Hz, 3H) 1.56 (s , 6H) 1.85 (s, 3H) 2.83 (q, J =7.34Hz, 2H) 7.15 (d, J =2.20Hz, 1H) 7.33 (s, 1H) 7.45 (s, 1H) 8.04 (d, J =2.20 Hz, 1H) ^{6) 1} H NMR (400 MHz, chloroform-d) δ ppm 1.44 (t, J =7.34Hz, 3H) 1.83 (s, 6H) 2.71 (s, 3H) 2.93 (q, J =7.34Hz) , 2H) 7.57 (d, J =2.20Hz, 1 H) 8.22 (d, J =2.20Hz, 1H) ^{7) 1} H NMR (400 MHz, chloroform-d) δ ppm 1.45 (t, J =7.34Hz, 3H) 1.85 (s, 6H) 2.96 (q, J =7.34Hz, 2H) 4.82 (s, 2H) 7.59 (d, J =2.57z, 1H) 8.21 (d, J =2.57Hz, 1H) ^{8) 1} H NMR (400 MHz, chloroform-d) δ ppm 1.44 (t, J =7.34Hz, 3H) 1.81(s, 6H) 3.04 (q, J =7.34Hz, 2H) 7.02 (dd, J1 =7.34; J2 =1.65Hz, 1H) 7.65 (d, J =2.57Hz , 1H) 8.06 (s, 1H) 8.29 (d, J =7.34Hz, 1H) 8.32 (d, J =2.57Hz, 1H) 8.37 (d, J =1.65Hz, 1H) ^{9) 1} H NMR (400 MHz , Chloroform-d) δ ppm 1.44 (t, J =7.34Hz, 3H) 1.81 (s, 6H) 3.04 (q, J =7.34Hz, 2H) 7.67 (s, 1H) 8.05 (s, 1H) 8.34 (s , 1H) 8.45 (s, 1H) 9.18 (s, 1H) ^{10) 1} H NMR (400 MHz, chloroform-d) δ ppm 1.44 (m, 3H) 1.82 (s, 6H) 3.05 (m, 2H) 7.66 ( d, J =2.20Hz, 1H) 8.02 (s, 1H) 8.34 (d, J =2.20Hz, 1H) 8.39 (s, 1H) 9.10 (s, 1H). Example I32: Preparation of 5-(1-cyano-1-methyl-ethoxy)-3-ethylsulfanyl-pyridine-2-carbochloride (compound I32)

(I32) Step 1: Preparation of 3-ethylhydrosulfanyl-5-hydroxy-pyridine-2-carboxylic acid methyl ester (Compound I33)

(I33)

(I34)To a solution of 5-bromo-3-ethylhydrosulfanyl-pyridine-2-carboxylic acid methyl ester (prepared as described in WO 2016/026848) (10.0 g, 36.21 mmol) in acetonitrile (72 ml) was added carbonic acid Cesium (25.96 g, 79.67 mmol) and (E)-benzaldehyde oxime (5.7 g, 47.08 mmol), and the suspension was heated to 80°C overnight. The solvent was evaporated in vacuum, and the residue was dissolved with ethyl acetate and water. The separated aqueous layer was acidified with 1 M aqueous hydrochloric acid solution and extracted with ethyl acetate (3x) and once with dichloromethane. The combined organic phase was dried over sodium sulfate, filtered and concentrated. The residue was purified by flash chromatography on silica gel (gradient 0-10% methanol in dichloromethane) to obtain methyl 3-ethylhydrothio-5-hydroxy-pyridine-2-carboxylate ( Compound I33). LCMS (Method 1): m/z 214 [M+H] ⁺ ; Retention time: 0.68 min. Step 2: 5-(2-Amino-1,1-dimethyl-2-oxo-ethoxy)-3-ethylsulfanyl-pyridine-2-carboxylic acid methyl ester (compound I34) preparation

(I34)

(I35)After 5 minutes, to a solution of 3-ethylhydrosulfanyl-5-hydroxy-pyridine-2-carboxylic acid methyl ester (compound I33) (2.5 g, 11.72 mmol) in acetonitrile (59 ml) was added cesium carbonate ( 5.7 g, 17.49 mmol) and 2-bromo-2-methyl-propanamide (3.1 g, 18.67 mmol). The reaction mixture was stirred at room temperature overnight and poured into water and ethyl acetate. The separated aqueous layer was extracted with ethyl acetate (3x), the combined organic layer was dried over sodium sulfate, filtered and evaporated to give crude 5-(2-amino-1,1-dimethyl-2- Pendant oxy-ethoxy)-3-ethylsulfanyl-pyridine-2-carboxylic acid methyl ester (compound I34). This material can be used in the next step without further purification. LCMS (Method 1): m/z 299 [M+H] ⁺ ; retention time: 0.71 min. Step 3: Preparation of 5-(1-cyano-1-methyl-ethoxy)-3-ethylsulfanyl-pyridine-2-carboxylic acid methyl ester (Compound I35)

(I35)

(I36)At 0°C, the crude 5-(2-amino-1,1-dimethyl-2-oxo-ethoxy)-3-ethylsulfanyl-pyridine-2-carboxylic acid methyl ester (Compound I34 prepared above) (4.18 g, 14.0 mmol) and triethylamine (5.73 g, 7.89 ml, 56.0 mmol) in dichloromethane (140 ml) were added dropwise to a mixture of trifluoroacetic anhydride (8.92 g , 5.90 ml, 42.0 mmol). The resulting suspension was stirred at room temperature for two hours. The reaction mixture was carefully quenched with methanol and then aqueous sodium bicarbonate. The aqueous layer was extracted twice with dichloromethane, the combined organic layer was dried with sodium sulfate, filtered and evaporated. The residue was purified by combiflash (0-45% gradient ethyl acetate in cyclohexane) to give 5-(1-cyano-1-methyl-ethoxy)-3-ethyl hydrogen sulfide Methyl-pyridine-2-carboxylate (Compound I35). LCMS (Method 1): m/z 281 [M+H] ⁺ ; Retention time: 0.90 min. ¹ H NMR (400 MHz, CDCl ₃ ) δ ppm 1.43 (t, J=7.40 Hz, 3H), 1.80 (s, 6H), 2.95 (q, J=7.40 Hz, 2H), 3.99 (s, 3H), 7.58 (d, J=2.32 Hz, 1H), 8.22 (d, J=2.32 Hz, 1H). Step 4: Preparation of 5-(1-cyano-1-methyl-ethoxy)-3-ethylsulfanyl-pyridine-2-carboxylic acid (compound I36)

(I36)

(I32)To 5-(1-cyano-1-methyl-ethoxy)-3-ethylhydrosulfanyl-pyridine-2-carboxylic acid methyl ester (compound I35) (6.0 g, 21.41 mmol) in tetrahydrofuran (60 ml Add lithium hydroxide hydrate (1.8 g, 42.81 mmol) and water (10 ml) to the solution in ). The reaction mixture was stirred at room temperature until completion (TLC monitoring), and then concentrated under reduced pressure. The residue was diluted with water (100 ml), acidified with 2 N aqueous hydrochloric acid, and the aqueous phase was extracted with ethyl acetate (3×100 ml). The combined organic layers were dried over sodium sulfate, filtered, and concentrated in vacuo. The crude product was washed twice with n-pentane (50 ml), filtered and evaporated to dryness to give 5-(1-cyano-1-methyl-ethoxy)-3-ethyl hydrogen as a solid Sulfuryl-pyridine-2-carboxylic acid (Compound I36). LCMS (Method 4): m/z 267 [M+H] ⁺ and m/z 265 [MH] ^- ; retention time: 0.82 min. ¹ H NMR (400 MHz, DMSO-d ₆ ) δ ppm 1.27 (t, J=7.21 Hz, 3H), 1.78 (s, 6H), 2.97 (q, J=7.21 Hz, 2H), 7.58 (d, J =2.32 Hz, 1H), 8.24 (d, J=2.32 Hz, 1H). Step 5: Preparation of 5-(1-cyano-1-methyl-ethoxy)-3-ethylsulfanyl-pyridine-2-carbochloride (compound I32)

(I32)

At 0°C-5°C, add 5-(1-cyano-1-methyl-ethoxy)-3-ethylhydrosulfanyl-pyridine-2-carboxylic acid (compound I36) (771 mg, To a solution of 2.90 mmol) and N,N-dimethylformamide (one drop) in tetrahydrofuran (19 ml) was added oxalic chloride (0.328 ml, 3.76 mmol) and the mixture was stirred at room temperature for 2 hours. The solution was concentrated under reduced pressure, diluted twice with tetrahydrofuran and evaporated to dryness. Used with 5-(1-cyano-1-methyl-ethoxy)-3-ethylhydrosulfanyl-N,N-dimethyl-pyridine-2-carboxamide (C ₁₄ H ₁₉ N ₃ O ₂ S, 293.38) Consistent LCMS data of dimethylamine quenched aliquots: LCMS (Method 1): m/z 294 [M+H] ⁺ ; retention time: 0.83 min.

The following mixtures of the compound of formula I and the active ingredient are preferred (the abbreviation "TX" means "a compound selected from the group consisting of the compounds described in Tables A-1 to A-17 and Table P of the present invention") : Adjuvant, the adjuvant is selected from the following substance group: petroleum (alias) (628) + TX, acaricide, the acaricide is selected from the group consisting of the following substances: 1,1-bis(4- Chlorophenyl)-2-ethoxyethanol (IUPAC name) (910) + TX, 2,4-dichlorophenylbenzenesulfonate (IUPAC/Chemical Abstracts name) (1059) + TX, 2-fluoro- N-methyl-N-1-naphthaleneacetamide (IUPAC name) (1295) + TX, 4-chlorophenyl phenyl sulfide (IUPAC name) (981) + TX, abamectin (1) + TX , Acequinocyl (3) + TX, acetoprole [CCN] + TX, acrinathrin (9) + TX, aldicarb (16) + TX , Aldoxycarb (863) + TX, alpha-cypermethrin (202) + TX, amidithion (870) + TX, amidoflumet [CCN] + TX, amidothioate (872) + TX, amiton (875) + TX, amiton hydrogen oxalate (875) + TX, amitraz ) (24) + TX, aramite (881) + TX, arsenic trioxide (882) + TX, AVI 382 (compound code) + TX, AZ 60541 (compound code) + TX, Eminophos (44) + TX, azinphos-methyl (45) + TX, azobenzene (IUPAC name) (888) + TX, azacyclotin (46) + TX, azothoate (889 ) + TX, benomyl (62) + TX, benoxafos (alias) [CCN] + TX, benzoximate (71) + TX, benzyl benzoate (IUPAC name) [ CCN] + TX, bifenazate (74) + TX, bifenthrin (76) + TX, binapacryl (907) + TX, brofenvalerate (Alias) + TX, bromide ( bromocyclene) (918) + TX, bromophos (920) + TX, ethyl bromphos (921) + TX, bromopropylate (94) + TX, buprofezin ( 99) + TX, butoxycarboxim (103) + TX, butoxycarboxim (104) + TX, butylpyridaben (alias) + TX, calcium polysulfide ) (IUPAC name) (111) + TX, campheechlor (941) + TX, carbanolate (943) + TX, carbaryl (115) + TX, carbofuran (118) + TX, carbophenothion (947) + TX, CGA 50' 439 (development code) (125) + TX, chinomethionat (126) + TX, chlorbenside ) (959) + TX, chlordimeform (964) + TX, chlordimeform hydrochloride (964) + TX, chlorfenapyr (130) + TX, chlorfenethol (968) ) + TX, chlorfenson (970) + TX, chlorfensulfide (971) + TX, clofenphos (131) + TX, chlorobenzilate (975) + TX , Chloromebuform (977) + TX, chloromethiuron (978) + TX, chloropropylate (983) + TX, chlorpyrifos (145) + TX, A Chlorpyrifos (146) + TX, chlorthiophos (994) + TX, cinerin I (696) + TX, cinerrin 11 (696) + TX, cinerins ( 696) + TX, clofentezine (158) + TX, clofentezine [CCN] (alias) + TX, coumaphos (174) + TX, clomiton (alias) [CCN] + TX, crotoxyphos (1010) + TX, thiazolene (1013) + TX, fruit Cyanthoate (1020) + TX, butflufenofen (CAS registration number: 400882-07-7) + TX, cyhalothrin (196) + TX, tricyclic tin (199) + TX, cypermethrin (201) + TX, DCPM (1032) + TX, DDT (219) + TX, demephion (1037) + TX, demephion -O (1037) + TX, Tian Le Phosphorus-S (1037) + TX, demeton (1038) + TX, methyl demeton (224) + TX, demeton -O (1038) + TX, methyl demeton -O (224) + TX, systemic phosphorus -S (1038) + TX, methyl systemic phosphorus -S (224) + TX, systemic phosphorus -S-methylsulfon (demeton-S-methylsulfon) ( 1039) + TX, diafenthiuron (226) + TX, dimpropyridaz + TX, dialifos (1042) + TX, diazinon (227) + TX, sulfonamide (230) + TX, dichlorvos (236) + TX, dicliphos (alias) + TX, kailesan (242) + TX, dichlorvos (243) + TX, pendigram (1071) + TX , Dimefox (1081) + TX, dimethoate (262) + TX, dinacti (alias) (653) + TX, dinex (1089) ) + TX, dinex-diclexine (1089) + TX, dinobuton (269) + TX, dinocap (270) + TX, dinocap-4 [CCN] + TX, dinosulfon-6 [CCN] + TX, dinitroester (1090) + TX, dinopenton (1092) + TX, dinosulfon (1097) + TX, nitrobutyl (Dinoterbon) (1098) + TX, dioxaphos (1102) + TX, diphenyl sulfide (IUPAC name) (1103) + TX, disulfiram [CCN] + TX, foxate (278) + TX, DNOC (282) + TX, dofenapyn (1113) + TX, doramectin (alias) [CCN] + TX, endosulfan (294) + TX, endothion (1121) + TX, EPN (297) + TX, Eprinomectin (alias) [CCN] + TX, Ethion (309) + TX, Ethoate-methyl (1134) + TX, Etoconazole ( etoxazole (320) + TX, etrimfos (1142) + TX, fenazaflor (1147) + TX, fenazaquin (328) + TX, fenbutatin oxide ( 330) + TX, fenothiocarb (337) + TX, fenpropathrin (342) + TX, fenpyrad (alias) + TX, fenpyroximate (345) + TX , Fenson (1157) + TX, fentrifanil (1161) + TX, fenvalerate (349) + TX, fipronil (354) + TX, fluacrypyrim ) (360) + TX, fluzolone (1166) + TX, flubenzimine (1167) + TX, flufenuron (366) + TX, flucythrinate (367) + TX , Fluenetil (1169) + TX, flufenoxuron (370) + TX, flumethrin (372) + TX, fluorbenside (1174) + TX, fluorine amine Fenprothrin (fluvalinate) (1184) + TX, FMC 1137 (development code) (1185) + TX, anti-mitamidine (405) + TX, anti-mitamidine hydrochloride (405) + TX, formothion ) (1192) + TX, formparanate (1193) + TX, γ-HCH (430) + TX, glyodin (1205) + TX, halfenprox (424) + TX, heptenophos (432) + TX, hexadecyl cyclopropane carboxylate (IUPAC/Chemical Abstracts name) (1216) + TX, hexothiazolone (441) + TX, methyl iodide (IUPAC Name) (542) + TX, isocarbophos (alias) (473) + TX, O- (methoxyaminothiophosphoryl) isopropyl salicylate (IUPAC name) (473 ) + TX, Evermacsu (alias) [CCN] + TX, jasmolin I (696) + TX, jasmolin II (696) + TX , Jodfenphos (1248) + TX, lingdan (430) + TX, lufenuron (490) + TX, marathon (492) + TX, malonoben (1254) + TX, mecarbam (502) + TX, mephosfolan (1261) + TX, mesulfen (alias) [CCN] + TX, methacrifos (1266) ) + TX, methamidophos (527) + TX, methidathion (529) + TX, methomyl (530) + TX, methomyl (531) + TX, methyl bromide (537) + TX, metolcarb (550) + TX, mevin pine (556) + TX, mexacarbate (1290) + TX, milbemectin (557) + TX, miticidin Milbemycin oxime (alias) [CCN] + TX, mipafox (1293) + TX, monocrotophos (561) + TX, morphothion (1300) + TX, Moxidectin (alias) [CCN] + TX, naled (567) + TX, NC-184 (compound code) + TX, NC-512 (compound code) + TX, Fluoxin Nifluridide (1309) + TX, Nicomycin (alias) [CCN] + TX, nitrilacarb (1313) + TX, nitrilacarb 1: 1 zinc chloride complex (1313) + TX, NNI-0101 (compound code) + TX, NNI-0250 (compound code) + TX, omethoate (594) + TX, oxamyl (602) + TX, Oxydeprofos (1324) + TX, oxydisulfoton (1325) + TX, pp'-DDT (219) + TX, parathion (615) + TX, permethrin (626) + TX, petroleum (alias) (628) + TX, fenthion (1330) + TX, Daofengsan (631) + TX, phorate (636) + TX, thiophos (637) + TX, Phosfolan (1338) + TX, imidophos (638) + TX , Phosphoamine (639) + TX, Phoxim (642) + TX, Methyl pyrimidinhos (652) + TX, polychloroterpenes (common name) (1347) + TX, polynactins ) (Alias) (653) + TX, prochlornol (1350) + TX, profenofos (662) + TX, promacyl (1354) + TX, ketone (671) + TX, amine Propetamphos (673) + TX, propacarb (678) + TX, prothidathion (1360) + TX, prothoate (1362) + TX, pyrethrin I (696) ) + TX, pyrethrin II (696) + TX, pyrethrins (696) + TX, pyridaphenthion (699) + TX, pyridaphenthion (701) + TX, Pyrimidifen (706) + TX, Pyrimphos (1370) + TX, Quinalphos (711) + TX, Quintiofos (1381) + TX, R-1492 (Development Code) (1382) + TX, RA-17 (development code) (1383) + TX, rotenone (722) + TX, schradan (1389) + TX, sebufos (alias) + TX, selamectin (alias) [CCN] + TX, SI-0009 (compound code) + TX, sophamide (1402) + TX, quaternary ketone (738) + TX, Spiromethiconin (739) + TX, SSI-121 (development code) (1404) + TX, sufelene (alias) [CCN] + TX, sulfluramid (750) + TX, sulphuramid (Sulfotep) (753) + TX, sulfur (754) + TX, SZI-121 (development code) (757) + TX, fluvalinate (398) + TX, pyraclosporin (763) + TX, TEPP (1417) + TX, terbam (alias) + TX, stirrofos (777) + TX, tetradifon (786) + TX, tetranactin ) (Alias) (653) + TX, tetrasul (1425) + TX, thiafenox (alias) + TX, thiocarboxime (1 431) + TX, thiofanox (800) + TX, thiometon (801) + TX, mites (1436) + TX, thuringiensin (alias) [CCN] + TX, triamiphos (1441) + TX, triarathene (1443) + TX, triazophos (820) + TX, triazuron (alias) + TX , Trichlorfon (824) + TX, trifenofos (1455) + TX, trinactin (alias) (653) + TX, trifenofos (847) + TX , Vaniliprole (vaniliprole) [CCN] and YI-5302 (compound code) + TX, an algicide, which is selected from the following substance group: bethoxazin (bethoxazin) [CCN] + TX, Copper dioctanoate (IUPAC name) (170) + TX, copper sulfate (172) + TX, cybutryne [CCN] + TX, dichlone (1052) + TX, dichlorophenol (232) + TX, Bacteriostatic acid (295) + TX, fentin (347) + TX, slaked lime [CCN] + TX, nabam (566) + TX, quinoclamine (714) + TX, quinonamid (1379) + TX, simazine (730) + TX, triphenyl tin acetate (IUPAC name) (347) and triphenyl tin hydroxide (IUPAC name) (347) + TX, worm repellent, the worm repellent is selected from the following substance group: abamectin (1) + TX, clefosfate (1011) + TX, doramectin (alias) [CCN] + TX, Emaketin (291) + TX, Emaketin benzoate (291) + TX, Eprinomectin (alias) [CCN] + TX, Ivermectin (alias) [CCN] + TX , Milbex oxime (alias) [CCN] + TX, moxidectin (alias) [CCN] + TX, piper[CCN] + TX, selamectin (alias) [CCN] + TX, Spinosyn (737) and thiophanate (1435) + TX, avianicides, which are selected from the group consisting of chloralose (127) + TX, endrin (1122) + TX, fenthion (346) + TX, pyridine-4-amine (IUPAC name) (23) and strychnine (745) + TX, A bactericide, the bactericide is selected from the following substance group: 1-hydroxy-1 H -pyridine-2-thione (IUPAC name) (1222) + TX, 4-(quinoline-2-ylamine Benzenesulfonamide (IUPAC name) (748) + TX, 8-hydroxyquinoline sulfate (446) + TX, bronopol (97) + TX, copper dioctanoate (IUPAC name) (170) + TX , Copper hydroxide (IUPAC name) (169) + TX, cresol [CCN] + TX, dichlorophen (232) + TX, dipyrithione (1105) + TX, dodecine (1112) + TX, Fenaminosulf (1144) + TX, formaldehyde (404) + TX, mercury plus fen (alias) [CCN] + TX, kasugamycin (483) + TX, kasugamycin hydrochloride hydrate (483) + TX, bis(dimethyldithiocarbamic acid) nickel (IUPAC name) (1308) + TX, nitrapyrin (580) + TX, octhilinone (590) + TX, oxolic acid (606) + TX, oxytetracycline (611) + TX, quinolinol potassium sulfate (446) + TX, probenazole (658) + TX, streptomycin (744) + TX, streptomycin sesquisulfate (744) + TX, cumin (766) + TX, and thimerosal (alias) [CCN] + TX, biological reagent, the biological reagent is selected from the following substance group: Adoxophyes orana GV (alias) (12) + TX, Agrobacterium radiobacter (alias) (13) + TX, Amblyseius spp. (alias) (19) ) + TX, Anagrapha falcifera nuclear polyhedrosis virus ( Anagrapha falcifera NPV) (alias) (28) + TX, Anagrus atomus (alias) (29) + TX, Aphelinus abdominalis (alias) (33 ) + TX, Aphidius colemani (alias) (34) + TX, Aphidoletes aphidimyza (alias) (35) + TX, Autographa californica nuclear polyhedrosis virus ( Autographa californica) NPV) (alias) (38) + TX, Bacillus firmus (alias) (48) + TX, Bacillus sphaericus Neide (scientific name) ( 49) + TX, Bacillus thuringiensis Berliner (scientific name) (51) + TX, Bacillus thuringiensis subsp. aizawai (scientific name) (51) + TX, Bacillus thuringiensis Berliner (scientific name) (51) + TX, Bacillus thuringiensis subsp. Species ( Bacillus thuringiensis subsp. israelensis ) (scientific name) (51) + TX, Bacillus thuringiensis subsp. japonensis (scientific name) (51) + TX, Bacillus thuringiensis subsp. Bacillus thuringiensis subsp. kurstaki ) (scientific name) (51) + TX, Bacillus thuringiensis subsp. tenebrionis (scientific name) (51) + TX, Beauveria bassiana (alias) ) (53) + TX, Beauveria brongniartii (alias) (54) + TX, Chrysoperla carnea (alias) (151) + TX, Cryptolaemus montrouzieri (Alias) (178) + TX, Cydia pomonella GV (alias) (191) + TX, Dacnusa sibirica (alias) (212) + TX, pea leaf miner Diglyphus isaea (alias) (254) + TX, Encarsia formosa (scientific name) (293) + TX, Eretmocerus eremicus (alias) (300) + TX, Helicoverpa zea NPV (alias) (431) + TX, Heterorhabditis bacteriophora and H. megidis (alias) (433) + TX, convergent long- legged scoop Hippodamia convergens (alias) (442) + TX, Leptomastix dactylopii (alias) (488) + TX, Macro lophus caliginosus (alias) (491) + TX, Mamestra brassicae NPV (alias) (494) + TX, Metaphycus helvolus (alias) (522) + TX, Metarhizium anisopliae var. acridum ) (scientific name) (523) + TX, Metarhizium anisopliae var. anisopliae (scientific name) (523) + TX, Neodiprion sertifer nuclear polyhedrosis virus and Red-headed pine leaf wasp ( N. lecontei ) nuclear polyhedrosis virus (alias) (575) + TX, small flower bugs (alias) (596) + TX, Paecilomyces fumosoroseus (alias) (613) + TX, Chilean plant mite ( Phytoseiulus persimilis ) (alias) (644) + TX, Spodoptera exigua multicapsid ( Spodoptera exigua multicapsid) polynuclear capsid nuclear polyhedrosis virus (scientific name) (741) + TX, Steinernema bibionis ) (Alias) (742) + TX, Steinernema carpocapsae (alias) (742) + TX, Steinernema carpocapsae (alias) (742) + TX, Steinernema glaseri (alias) (742 ) + TX, Steinernema riobrave (alias) (742) + TX, Steinernema riobravis (alias) (742) + TX, Steinernema scapterisci (alias) (742) + TX, Steinernema spp. (alias) (742) + TX, Trichogramma species (alias) (826) + TX, Typhlodromus occidentalis (alias) (844) and Verticillium lecanii (alias) (848) + TX, soil disinfectant, the soil disinfectant is selected from the following substance group: methyl iodide (IUPAC name) (542) and methyl bromide (537) + TX, chemical sterilizer, the chemical sterilizer is selected from the following composition Substance group: azophos 𠯤 (apholate) [CCN] + TX , Bis (aziridine) methylamino phosphine sulfide (bisazir) (alias) [CCN] + TX, Busulfan (alias) [CCN] + TX, diflubenzuron (250) + TX, Dimetif (Dimatif) (alias) [CCN] + TX, hemel [CCN] + TX, hempa [CCN] + TX, metepa [CCN] + TX, methyl sulfide Methiotepa [CCN] + TX, methyl apholate [CCN] + TX, morzid [CCN] + TX, penfluron (alias) [CCN] + TX, Tepa (alias) [CCN] + TX, thiohempa (alias) [CCN] + TX, Thiopa (alias) [CCN] + TX, Tratamide (alias) [CCN ] And urethane imine (alias) [CCN] + TX, insect pheromone, the insect pheromone is selected from the following substance group: ( E )-dec-5-en-1-yl acetate and ( E )-Dec-5-en-1-ol (IUPAC name) (222) + TX, ( E )-Tridec-4-en-1-yl acetate (IUPAC name) (829) + TX, ( E )-6-methylhept-2-en-4-ol (IUPAC name) (541) + TX, ( E, Z )-tetradeca-4,10-dien-1-yl acetate ( IUPAC name) (779) + TX, ( Z )-dodec-7-en-1-yl acetate (IUPAC name) (285) + TX, ( Z )-hexadec-11-enal ( IUPAC name) (436) + TX, ( Z )-hexadec-11-en-1-yl acetate (IUPAC name) (437) + TX, ( Z )-hexadec-13-ene-11 -Alkyn-1-yl acetate (IUPAC name) (438) + TX, ( Z )-eicos-13-en-10-one (IUPAC name) (448) + TX, (Z)-fourteen carbon -7-en-1-al (IUPAC name) (782) + TX, (Z )-tetradecen-9-en-1-ol (IUPAC name) (783) + TX, (Z)-tetradecane -9-en-1-yl acetate (IUPAC name) (784) + TX, (7 E ,9 Z )-dodeca-7,9-dien-1-yl acetate (IUPAC name) (283) + TX, (9 Z , 11 E )-tetradecane-9,11-dien-1-yl acetate (IUPAC name) (780) + TX, (9 Z, 12 E )-ten Tetracarbon-9,12-diene- 1-yl acetate (IUPAC name) (781) + TX, 14-methyloctadec-1-ene (IUPAC name) (545) + TX, 4-methylnon-5-ol and 4-methyl Nonan-5-one (IUPAC name) (544) + TX, alpha-multistriatin (alias) [CCN] + TX, western pine beetle brevicomin (alias) [CCN ] + TX, codlelure (alias) [CCN] + TX, codlemone (alias) (167) + TX, cuelure (alias) (179) + TX, disparlure (disparlure) (277) + TX, dodec-8-en-1-yl acetate (IUPAC name) (286) + TX, dodec-9-ene-1- Acetate (IUPAC name) (287) + TX, dodeca-8 + TX, 10-dien-1-yl acetate (IUPAC name) (284) + TX, dominicalure (alias) [CCN] + TX, ethyl 4-methyloctanoate (IUPAC name) (317) + TX, eugenol (alias) [CCN] + TX, southern pine beetle frontalin (alias) [CCN] + TX, Gossyplure (alias) (420) + TX, grandlure (421) + TX, decoy mixture I (alias) (421) + TX, decoy mixture II ( Alias) (421) + TX, booby-trapene mixture III (alias) (421) + TX, booby-trapene mixture IV (alias) (421) + TX, hexalure [CCN] + TX, small teeth Ipsdienol (alias) [CCN] + TX, ipsenol (alias) [CCN] + TX, japonilure (alias) (481) + TX, Trijia Dioxacyclononane (alias) [CCN] + TX, litlure (alias) [CCN] + TX, looplure (alias) [CCN] + TX, medlure [CCN] + TX, megatomoic acid (alias) [CCN] + TX, methyl eugenol (alias) (540) + TX, muscalure (563) + TX, octadec-2 ,13-dien-1-yl acetate (IUPAC name) (588) + TX, octadec-3,13-dien-1-yl acetic acid Ester (IUPAC name) (589) + TX, orfralure (alias) [CCN] + TX, oryctalure (alias) (317) + TX, ostramone ) (Alias) [CCN] + TX, siglure [CCN] + TX, sordidin (alias) (736) + TX, sulcatol (alias) [CCN] + TX, ten Four carbon-11-en-1-yl acetate (IUPAC name) (785) + TX, Mediterranean fruit fly attractant (839) + TX, Mediterranean fruit fly attractant A (alias) (839) + TX, Mediterranean Fruit fly attractant B ₁ (alias) (839) + TX, Mediterranean fruit fly attractant B ₂ (alias) (839) + TX, Mediterranean fruit fly attractant C (alias) (839) and trunc-call (alias) [CCN] + TX, insect repellent, the insect repellent is selected from the following substance group: 2-(octylthio)ethanol (IUPAC name) (591) + TX, butopyronoxyl ( 933) + TX, butoxy (polypropylene glycol) (936) + TX, dibutyl adipate (IUPAC name) (1046) + TX, dibutyl phthalate (1047) + TX, succinic acid Dibutyl ester (IUPAC name) (1048) + TX, DEET [CCN] + TX, dimethyl carbate [CCN] + TX, dimethyl phthalate [CCN] + TX, ethyl Hexanediol (1137) + TX, hexylurea [CCN] + TX, methoquin-butyl (1276) + TX, methyl neodecylamide [CCN] + TX, oxamate ) [CCN] and hydroxypiperate [CCN] + TX, insecticide, the insecticide is selected from the following substance group: 1-dichloro-1-nitroethane (IUPAC/Chemical Abstracts name) (1058 ) + TX, 1,1-dichloro-2,2-bis(4-ethylphenyl)ethane (IUPAC name) (1056) + TX, 1,2-dichloropropane (IUPAC/Chemical Abstracts name) (1062) + TX, 1,2-dichloropropane with 1,3-dichloropropene (IUPAC name) (1063) + TX, 1-bromo-2-chloroethane (IUPAC/Chemical Abstracts name) ( 916) + TX, 2,2,2-trichloro-1-(3,4-dichlorophenyl) ethyl acetate (IUPAC name) (1451) + TX, 2,2-dichlorovinyl 2- Ethylsulfinyl ethyl methyl phosphate (IUPAC name) (1066) + TX, 2-(1,3-dithiolan-2-yl)phenyl dimethylaminocarboxylate (IUPAC/Chemical Abstracts name) (1109) + TX, 2-(2) thiocyanate -Butoxyethoxy) ethyl ester (IUPAC/Chemical Abstracts name) (935) + TX, methylamino acid 2-(4,5-dimethyl-1,3-dioxolane- 2-yl) phenyl ester (IUPAC/Chemical Abstracts name) (1084) + TX, 2-(4-chloro-3,5-dimethylphenyloxy)ethanol (IUPAC name) (986) + TX, 2- Chlorovinyl diethyl phosphate (IUPAC name) (984) + TX, 2-imidazolinone (IUPAC name) (1225) + TX, 2-isopentyl indene-1,3-dione ( IUPAC name) (1246) + TX, 2-methyl (prop-2-ynyl) aminophenyl methyl amino formate (IUPAC name) (1284) + TX, 2-thiocyanoethyl lauric acid Ester (IUPAC name) (1433) + TX, 3-bromo-1-chloroprop-1-ene (IUPAC name) (917) + TX, dimethylaminocarboxylic acid 3-methyl-1-phenylpyrazole -5-yl ester (IUPAC name) (1283) + TX, 4-methyl (prop-2-ynyl) amino-3,5-dimethylamino formate (IUPAC name) (1285) + TX, 5,5-dimethyl-3-oxocyclohex-1-enyl dimethylaminocarboxylate (IUPAC name) (1085) + TX, abamectin (1) + TX, Acetaminophos (2) + TX, Acetamiprid (4) + TX, Muscaphos (alias) [CCN] + TX, Acetonitrile [CCN] + TX, Flumethrin (9) + TX, Acrylonitrile (IUPAC name) (861) + TX, Aldicarb (15) + TX, Aldicarb (16) + TX, Aldicarb (863) + TX, Chloropin (864) + TX , Allethrin (17) + TX, Alloxan (alias) [CCN] + TX, Chibawei (866) + TX, α-cypermethrin (202) + TX, α-ecdysone (alias) [CCN] + TX, aluminum phosphide (640) + TX, thiophos (870) + TX, thioamide (872) + TX, methocarb (873) + TX, amine phosphate (875) + TX, Amidophos hydrogen oxalate (875) + TX, bisformamidine (24) + TX, neonicotine (877) + TX, ethoxypyr (883) + TX, AVI 382 (compound code) + TX, AZ 60541 (compound code) + TX, azadirachtin (alias) (41) + TX, picoline (42) + TX, azinphos-ethyl (44) + TX, azinphos-methyl Base (45) + TX, azo phosphorus (889) + TX, Bacillus thuringiensis δ endotoxin (alias) (52) + TX, barium hexafluorosilicate (alias) [CCN] + TX, barium polysulfide (IUPAC/Chemical Abstracts name) (892) + TX, Permethrin [CCN] + TX, Bayer 22/190 (Development Code) (893) + TX, Bayer 22408 (Development Code) (894) + TX, Dimethocarb (58) + TX, Benfuracarb Carbinol (60) + TX, Difenthrin (66) + TX, β-cypermethrin (194) + TX, β-cypermethrin (203) + TX, bifenthrin (76) + TX, bio-allethrin ( 78) + TX, bio-allethrin S-cyclopentenyl isomer (alias) (79) + TX, bioethanomethrin (bioethanomethrin) [CCN] + TX, bio-permethrin (908) + TX, pyrethrin (80) + TX, bis (2-chloroethyl) ether (IUPAC name) (909) + TX, diflufenazone (83) + TX, borax (86) + TX, Deltamethrin (alias) + TX, Bromofenphos (914) + TX, Bromide (918) + TX, Bromo-DDT (alias) [CCN] + TX, Bromphos (920) + TX, Bromphos-Ethyl (921) + TX, Hexacarb (924) + TX, Thioxacarb (99) + TX, Beechcarb (926) + TX, butathiofos (927) ) + TX, Butacarb (103) + TX, Butyl phosphine (932) + TX, Butaprocarb (104) + TX, Butylpyridaben (alias) + TX, Thionophos (109)+ TX, calcium arsenate [CCN] + TX, calcium cyanide (444) + TX, calcium polysulfide (IUPAC name) (111) + TX, toxaphene (941) + TX, chlorfenacarb (943) + TX , Carbcarb (115) + TX, Carbofuran (118) + TX, Carbon Disulfide (IUPAC/Chemical Abstracts Name) (945) + TX, Carbon Tetrachloride (IUPAC Name) (946) + TX, Phosphorus Trithion (947) + TX, carbosulfuron Baicheng (119) + TX, Shazhudan (123) + TX, Shazhudan hydrochloride (123) + TX, Simvadin (alias) (725) + TX, Borneol (960) + TX, Chlordane (128) + TX, Chloramphenicol (963) + TX, Fenoxamidine (964) + TX, Fenoxamidine hydrochloride (964) + TX, Phosphorus oxychloride (129) ) + TX, chlorfenapyr (130) + TX, chlorfenapyr (131) + TX, chlorfenapyr (132) + TX, chlormethphos (136) + TX, chloroform [CCN] + TX, chloropicrin Alkane (141)+ TX, Chlorphoxim (989) + TX, Dipyridine (990) + TX, Chlorpyrifos (145) + TX, Chlorpyrifos-Methyl (146) + TX, Carbophos (994) + TX, Cyclofenac Hydrazine (150) + TX, gray chrysanthemum I (696) + TX, gray chrysanthemum II (696) + TX, gray chrysanthemum (696) + TX, cis-resmethrin (alias) ) + TX, cismethrin (80) + TX, Kungfu pyrethrin (alias) + TX, Chuanwei (999) + TX, cismethrin (alias) [CCN] + TX , Clothianidin (165) + TX, acetyl copper arsenite [CCN] + TX, copper arsenate [CCN] + TX, copper oleate [CCN] + TX, coumaphos (174) + TX, livestock Tetrophos (1006) + TX, Crotamiton (alias) [CCN] + TX, Paltophos (1010) + TX, Clufofen (1011) + TX, Cryolite (alias) (177) + TX , CS 708 (development code) (1012) + TX, benzonitrile (1019) + TX, fenpyridine (184) + TX, carofenphos (1020) + TX, cyphthrin [CCN] + TX, Cypermethrin (188) + TX, Cyfluthrin (193) + TX, Cypermethrin (196) + TX, Cypermethrin (201) + TX, Cypermethrin (206) + TX, Cypromethrin Qin (209) + TX, bezophos (alias) [CCN] + TX, d-limonene (alias) [CCN] + TX, d-tetramethrin (alias) (788) + TX, DAEP (1031) + TX, Mianlong (216) + TX, DDT (219) + TX, monomethyl carbofuran (decarbofuran) (1034) + TX, deltamethrin (223) + TX, Tian Le Pho (1037) + TX, Tianle Phosphorus-O (1037) + TX, Tianle Phosphorus-S (1037) + TX, Systemic Phosphorus (1038) + TX, Systemic Phosphorus-Methyl (224) + TX, Systemic Phosphorus-O (1038) + TX, systemic phosphorus-O-methyl (224) + TX, systemic phosphorus-S (1038) + TX, systemic phosphorus-S-methyl (224) + TX, systemic phosphorus-S -Methyl sulfide (1039) + TX, diafenthiuron (226) + TX, chlorimidophos (1042) + TX, diamine phosphorus (1044) + TX, diphosphine (227) + TX, isochloride Phosphorus (1050) + TX, In addition to linear phosphorus (1051) + TX, Dichlorvos (236) + TX, dicliphos (alias) + TX, dicresyl (alias) [ CCN] + TX, Bactophos (243) + TX, Dexionil (244) + TX, Dieldrin (1070) + TX, Diethyl 5-methylpyrazole-3-yl phosphate (IUPAC Name) (1076) + TX, diflubenzuron (250) + TX, dihydroxypropyl theophylline (dilor) (alias) [CCN] + TX, permethrin [CCN] + TX, metflufen ( 1081) + TX, Dimacarb (1085) + TX, Dimethoate (262) + TX, Permethrin (1083) + TX, Methoxypyr (265) + TX, Difencarb (1086) + TX , Diclexine (1089) + TX, dinex-diclexine (1089) + TX, propionol (1093) + TX, pentrol (1094) + TX, dinex-diclexine (1095) + TX , Dinotefuran (271) + TX, Fenfenpyr (1099) + TX, Fruit and Vegetable Phosphorus (1100) + TX, Dioxacarb (1101) + TX, Dioxaphos (1102) + TX, Ethidium (278) ) + TX, dithicrofos (1108) + TX, DNOC (282) + TX, doramectin (alias) [CCN] + TX, DSP (1115) + TX, ecdysone (alias) [CCN] + TX, EI 1642 (development code) (1118) + TX, imaktin (291) + TX, imakbutin benzoate (291) + TX, EMPC (1120) + TX, dimethoate Ester (292) + TX, Endosulfan (294) + TX, Intophos (1121) + TX, Endrin (1122) + TX, EPBP (1123) + TX, EPN (297) + TX, Babysitting Ether (1124) + TX, irinomectin (alias) [CCN] + TX, perfenvalerate (302) + TX, Oxfordshire etaphos (alias) [CCN] + TX, B Thiofencarb (308) + TX, Ethion (309) + TX, Ethiprole (310) + TX, Ethion-methyl (1134) + TX, Methamphet (312) + TX, ethyl formate Ester (IUPAC name) [CCN] + TX, ethyl-DDD (alias) (1056) + TX, ethylene dibromide (316) + TX, ethylene dichloride (chemical name) (1136) + TX, epoxy Ethane [CCN] + TX, Ethofenprox (319) + TX, Ethion (1142) + TX, EXD (1143) + TX, Amamisulfon (323) + TX, Fenamiphos (326) + TX, Anti-Mixazole (1147) + TX, Cyclofen (1148) + TX, Fenthiocarb (1149) + T X, Fenflusrine (1150) + TX, Fenoxaphos (335) + TX, Bufencarb (336) + TX, Fenoxacrim (1153) + TX, Fenoxycarb (340) + TX, cypermethrin (1155) + TX, fenpromethrin (342) + TX, fenpyrad (alias) + TX, fenpyrad (1158) + TX, fenthion (346) + TX , Fenthion-Ethyl [CCN] + TX, Fenvalerate (349) + TX, Fipronil (354) + TX, Sulfoxamide (358) + TX, Fipronil (CAS registered No.: 272451-65-7) + TX, flucofuron (1168) + TX, fluorocyclourea (366) + TX, fenvalerate (367) + TX, difluoromite (1169) + TX, pyrflufenapyr [CCN] + TX, flufenoxuron (370) + TX, flufluthrin (1171) + TX, flumethrin (372) + TX, fluvalinate (1184) + TX, FMC 1137 (development code) (1185) + TX, chlorfenaphos (1191) + TX, valfenamidine (405) + TX, valfenamidine hydrochloride (405) + TX, Enthion (1192) ) + TX, formparanate (1193) + TX, bufenthion (1194) + TX, forspiramate (1195) + TX, thiazolone (408) + TX, bufenphos (1196) ) + TX, Foroxacarb (412) + TX, Pyrethrum (1200) + TX, γ-cyhalothrin (197) + TX, γ-HCH (430) + TX, biguanide salt (422) + TX, biguanide acetate (422) + TX, GY-81 (development code) (423) + TX, benzfenox (424) + TX, chlorfenazone (425) + TX, HCH (430) + TX , HEOD (1070) + TX, Febuda (1211) + TX, heptenyl phos (432) + TX, acesulfame [CCN] + TX, hexaflumuron (439) + TX, HHDN (864) + TX, hydrazone (443) + TX, hydrocyanic acid (444) + TX, methoprene (445) + TX, hyquincarb (1223) + TX, imidacloprid (458) + TX, alkyne Fipthrin (460) + TX, indoxacarb (465) + TX, methyl iodide (IUPAC name) (542) + TX, IPSP (1229) + TX, chlorfenaphos (1231) + TX, carbachlor ( 1232) + TX, hydrocarbophos (alias) (473) + TX, isoaldrin (1235) + TX, iso Willfos (1236) + TX, Yizailing (1237) + TX, Isoprocarb (472) + TX, O-(Methoxyaminothiophosphoryl) isopropyl salicylate (IUPAC name) (473) + TX, rice blast (474) + TX, isoprate (1244) + TX, oxazophos (480) + TX, ivermectin (alias) [CCN] + TX, jasmine I (696) + TX, jasperanthrin II (696) + TX, iodophos (1248) + TX, juvenile hormone I (alias) [CCN] + TX, juvenile hormone II (alias) [CCN] + TX, juvenile hormone III (alias) [CCN] + TX, chlorpentane (1249) + TX, methoprene (484) + TX, lambda-cyhalothrin (198) + TX, arsenic Lead acid [CCN] + TX, rapamectin (CCN) + TX, parabromophos (1250) + TX, lindane (430) + TX, lirimfos (1251) + TX, lice mite Urea (490) + TX, thiazophos (1253) + TX, m-isopropyl phenyl methyl carbamate (IUPAC name) (1014) + TX, magnesium phosphide (IUPAC name) (640) + TX , Malathion (492) + TX, Benzalmalononitrile (1254) + TX, Phosphorus azide (1255) + TX, Metgasone (502) + TX, Tetramethphos (1258) + TX, Aphid Thiophos (1260) + TX, Diamphos (1261) + TX, Mercurous chloride (513) + TX, Mesulfenfos (1263) + TX, Cyanoflurzone (CCN) + TX, Valber Acres (519) + TX, metabolite potassium (alias) (519) + TX, metabolite sodium (519) + TX, paraben (1266) + TX, methamidophos (527) + TX, methanesulfonate Fluorine (IUPAC/Chemical Abstracts name) (1268) + TX, chlorpheniramine (529) + TX, methophos (530) + TX, methenophos (1273) + TX, methomyl (531) + TX , Methoprene (532) + TX, methaquine (1276) + TX, methothrin (alias) (533) + TX, methoxetin (534) + TX, methenol (535) + TX , Methyl bromide (537) + TX, methyl isothiocyanate (543) + TX, methyl chloroform (alias) [CCN] + TX, dichloromethane [CCN] + TX, metofluthrin [CCN] + TX, sulfacarb (550) + TX, oxadione (1288) + TX, mevansone (556) + TX, Zikewei (1290) + TX, mimectin (557) + TX, Milbemycin Prime (alias) [CCN] + TX, Alanoflophos (1293) + TX, Mirex (1294) + TX, Monocrotophos (561) + TX, Thiophos (1300) + TX, Moxidectin (alias) [CCN] + TX, Naphthalophosphorus (alias) [CCN] + TX, Dibromophosphorus (567) + TX, Naphthalene (IUPAC/Chemical Abstracts name) (1303) + TX, NC-170 (development code) (1306) + TX, NC-184 (Compound Code) + TX, Nicotine (578) + TX, Nicotine Sulfate (578) + TX, Fluormethalin (1309) + TX, Nitenpyram (579) + TX, Nitrodithiazole (Nithiazine) (1311) + TX, cyanocarb (1313) + TX, cyanocarb 1:1 zinc chloride complex (1313) + TX, NNI-0101 (compound code) + TX, NNI-0250 ( Compound code) + TX, nornicotine (common name) (1319) + TX, diflubenzuron (585) + TX, polyfluzuron (586) + TX, O-5-dichloro-4-iodophenyl O-ethyl ethyl thiophosphonate (IUPAC name) (1057) + TX, O, O-diethyl O-4-methyl-2-side oxy-2H-chromene-7-yl sulfide Phosphonate (IUPAC name) (1074) + TX, O, O-diethyl O-6-methyl-2-propylpyrimidin-4-yl thiophosphonate (IUPAC name) (1075) + TX, O, O, O', O'-tetrapropyl dithio pyrophosphate (IUPAC name) (1424) + TX, oleic acid (IUPAC name) (593) + TX, omethoate (594) + TX, oxacarb (602) + TX, sulfonate absorption-methyl (609) + TX, heterothionite (1324) + TX, sulfonate (1325) + TX, pp'-DDT (219) + TX, p-dichlorobenzene [CCN] + TX, parathion (615) + TX, parathion-methyl (616) + TX, chlorfenuron (alias) [CCN] + TX, pentachlorophenol ( 623) + TX, pentachlorophenyl laurate (IUPAC name) (623) + TX, permethrin (626) + TX, petroleum oils (alias) (628) + TX, PH 60-38 (development code ) (1328) + TX, fenthion (1330) + TX, phenothrin (630) + TX, Daofengsan (631) + TX, phorate (636) + TX, phenathion (637) ) + TX, thiocyclophosphate (1338) + TX, imidophos (638) + TX, parachlorothion (1339) + TX, phosphoramine (639) + TX, phosphine (IUPAC name) (640 ) + TX, phoxim (642) + TX, phoxim Phosphorus-Methyl (1340) + TX, Pirimetaphos (1344) + TX, Pirimicarb (651) + TX, Carbophos-ethyl (1345) + TX, Carbophos-A Base (652) + TX, polychlorodicyclopentadiene isomers (IUPAC name) (1346) + TX, polychloroterpenoids (common name) (1347) + TX, potassium arsenite [CCN] + TX, potassium thiocyanate [CCN] + TX, proparginate (655) + TX, precocious element I (alias) [CCN] + TX, precocious element II (alias) [CCN] + TX, precocious element III ( Alias) [CCN] + TX, primidophos (1349) + TX, profenofos (662) + TX, profluthrin [CCN] + TX, timophos (1354) + TX, Meng Procarb (1355) + TX, Profenofos (1356) + TX, Amprocarb (673) + TX, Procarb (678) + TX, Ethiazole (1360) + TX, Profenofos (686) + TX, protrifenbute (1362) + TX, protrifenbute [CCN] + TX, pymetrozine (688) + TX, pyrazophos (689) + TX, protrifenbute (693) + TX, pyresmethrin (1367) + TX, pyrethrin I (696) + TX, pyrethrin II (696) + TX, pyrethrins (696) + TX, da Pyridoxine (699) + TX, acetamiprid (700) + TX, pyriproxyphos (701) + TX, pyrimidine (706) + TX, pyrimthion (1370) + TX, pyriproxyfen ( 708) + TX, quassia extract (alias) [CCN] + TX, quinalphos (711) + TX, quinalphos-methyl (1376) + TX, quinalphos (1380) ) + TX, quintiofos (1381) + TX, R-1492 (development code) (1382) + TX, Refoxanide (alias) [CCN] + TX, mefurthrin (719) + TX, rotenone (722) + TX, RU 15525 (development code) (723) + TX, RU 25475 (development code) (1386) + TX, ryania (alias) (1387) + TX, Lia Nordin (common name) (1387) + TX, Veratrum sambac (alias) (725) + TX, octamethphos (1389) + TX, thiophanate (alias) + TX, seramycin (alias) [ CCN] + TX, SI-0009 (compound code) + TX, S I-0205 (compound code) + TX, SI-0404 (compound code) + TX, SI-0405 (compound code) + TX, silfluthrin (728) + TX, SN 72129 (development code) (1397) + TX, sodium arsenite [CCN] + TX, sodium cyanide (444) + TX, sodium fluoride (IUPAC/Chemical Abstracts name) (1399) + TX, sodium hexafluorosilicate (1400) + TX, pentachloro Sodium phenate (623) + TX, sodium selenate (IUPAC name) (1401) + TX, sodium thiocyanate [CCN] + TX, thiophos (1402) + TX, spinosad (737) + TX, snail Mesifenphosate (739) + TX, Spirotetramat (CCN) + TX, Sulcofuron (746) + TX, Sulcofuron-sodium (746) + TX, Sulfluramid (750) + TX, Pyramiphos (753) + TX, Sulfonamide (756) + TX, Thiopropion (1408) + TX, Tar (alias) (758) + TX, τ-Fluorine Telamethrin (398) + TX, thiadicarb (1412) + TX, TDE (1414) + TX, fenthiazine (762) + TX, pyrazamethon (763) + TX, pyrimidin butyl (764) ) + TX, flufenuron (768) + TX, tefluthrin (769) + TX, dithion (770) + TX, TEPP (1417) + TX, cyfluthrin (1418) + TX , Terbam (terbam) (alias) + TX, terbuthion (773) + TX, tetrachloroethane [CCN] + TX, dimephos (777) + TX, tetramethrin (787) + TX, θ cypermethrin (204) + TX, thiacloprid (791) + TX, thiafenox (alias) + TX, clothia worm (792) + TX, thicrofos (1428) + TX, Carmethocarb (1431) + TX, Moxa Ring (798) + TX, Moxa Ring Bioxalate (798) + TX, Thiodicarb (799) + TX, Jiuxiaowei (800) ) + TX, methyl acetophos (801) + TX, wormwood (1434) + TX, thiosultap (803) + TX, thiosultap-sodium (803) + TX, Thuringigen (alias) [CCN] + TX, Tofenpyramide (809) + TX, Permethrin (812) + TX, Perfluthrin (813) + TX, transpermethrin (transpermethrin) ) (1440) + TX, Veraphos (1441) + TX, Trichlormetaphos (818) + TX, triazophos (820) + TX, zodiacarb (alias) + TX, trichlorfon (824) + TX, trichlormetaphos-3 (alias) [CCN] + TX, Toxicin (1452) + TX, Triclosan (1455) + TX, Triflumuron (835) + TX, Coxacarb (840) + TX, Methoprene (1459) ) + TX, aphid (847) + TX, vaniliprole [CCN] + TX, veratridine (alias) (725) + TX, veratrine (alias) (725) + TX , XMC (853) + TX, metoxacarb (854) + TX, YI-5302 (compound code) + TX, ζ-cypermethrin (205) + TX, zetamethrin (alias) + TX, phosphorus Zinc (640) + TX, zolaprofos (1469) and ZXI 8901 (development code) (858) + TX, cyantraniliprole [736994-63-19] + TX, chlorantraniliprole [500008-45-7] + TX, cyenopyrafen (cyenopyrafen) [560121-52-0] + TX, bufenofen [400882-07-7] + TX, pyrifluquinazon [337458- 27-2] + TX, spinetoram [187166-40-1 + 187166-15-0] + TX, spirotetramat [203313-25-1] + TX, sulfoxaflor ) [946578-00-3] + TX, flufiprole [704886-18-0] + TX, cyfluthrin [915288-13-0] + TX, tetramethylfluthrin [84937-88-2] + TX, triflumezopyrim (disclosed in WO 2012/092115) + TX, fluxametamide (WO 2007/026965) + TX, epsilon-metofluthrin (epsilon-metofluthrin) [240494-71 -7] + TX, ε-cyfluthrin [1065124-65-3] + Tx, fluazaindolizine (fluazaindolizine) [1254304-22-7] + TX, chloroprallethrin [399572- 87-3] + TX, fluxametamide [9 28783-29-3] + TX, cyhalodiamide [1262605-53-7] + TX, tioxazafen [330459-31-9] + Tx, broflanilide [1207727-04- 5] + TX, butene fipronil (flufiprole) [704886-18-0] + TX, cyclaniliprole (cyclaniliprole) [1031756-98-5] + TX, flufiprole [1229654-66 -3] + TX, pentopyridine (described in WO 2010/060231) + TX, epoxifen (described in WO 2005/077934) + TX, tetramer acid insecticide (spiropidion) + TX, Flupyrimin + TX, flupyrimin + TX, Momfluorothrin + TX, κ-bifenthrin + TX, κ-tefluthrin + TX, Dichloromezotiaz + TX, Tetrachloraniliprole + TX, benzpyrimoxan + TX; killing molluscs The molluscicide is selected from the following substance group: bis(tributyltin) oxide (IUPAC name) (913) + TX, bromoacetamide [CCN] + TX, calcium arsenate [CCN] + TX , Cloethocarb (999) + TX, copper acetyl arsenite [CCN] + TX, copper sulfate (172) + TX, triphenyltin (347) + TX, iron phosphate (IUPAC name) (352 ) + TX, Tetraacetaldehyde (518) + TX, Metsike (530) + TX, Niclosamide (576) + TX, Niclosamide ethanolamine salt (576) + TX, Pentachlorophenol (623) ) + TX, sodium pentachlorobenzene oxide (623) + TX, tazimcarb (1412) + TX, thiodicarb (799) + TX, tributyltin oxide (913) + TX, snail 𠰌 Trifenmorph (1454) + TX, trimethacarb (840) + TX, triphenyl tin acetate (IUPAC name) (347) and triphenyl tin hydroxide (IUPAC name) (347) + TX , Pyriprole [394730-71-3] + TX, nematicide, the nematicide is selected from the following substance group: AKD-3088 (compound code) + TX, 1,2-dibromo -3-Chloropropane (IUPAC/Chemical Abstract Name) (1045)+TX, 1,2-Dichloropropane (IUPAC/Chemical Abstract Name) (1062) +TX, 1,2-dichloropropane and 1,3-dichloropropene (IUPAC name) (1063) +TX, 1,3-dichloropropene (233) +TX, 3,4-dichloro Tetrahydrothiophene 1,1-dioxide (IUPAC/Chemical Abstracts name) (1065) + TX, 3-(4-chlorophenyl)-5-methylrhodanine (IUPAC name) (980) + TX, 5 -Methyl-6-thio-1,3,5-thiadiazepine-3-ylacetic acid (IUPAC name) (1286) + TX, 6-isopentenyl aminopurine (alias) (210) + TX, abamectin (1) + TX, acetophenone [CCN] + TX, albamol (15) + TX, aldicarb (16) + TX, aldicarb (863) + TX, AZ 60541 (compound code) + TX, benclothiaz [CCN] + TX, benomyl (62) + TX, butyl pyridaben (alias) + TX, thionphos (109) + TX, carbofuran (118) + TX, carbon disulfide (945) + TX, carbofuran (119) + TX, chloropicrin (141) + TX, chlorpyrifos (145) + TX, de-thread Wei (cloethocarb) (999) + TX, cytokinin (alias) (210) + TX, Mianlong (216) + TX, DBCP (1045) + TX, DCIP (218) + TX, diamidos (diamidafos) (1044)+TX, in addition to linear phosphorus (1051)+TX, dicliphos (alias) +TX, dimethoate (262) +TX, doramectin (alias) [CCN]+TX , Emamectin (291) + TX, Emamectin benzoate (291) + TX, Eprinomectin (alias) [CCN] + TX, Methophos (312) + TX, Dibromide Fenpyrad (316) + TX, fenpyrad (326) + TX, fenpyrad (alias) + TX, fenpyrad (1158) + TX, thiazolyl (408) + TX, buthion (1196) +TX, furfural (alias) [CCN] + TX, GY-81 (development code) (423) + TX, sulfoxaphos [CCN] + TX, methyl iodide (IUPAC name) (542) + TX , Isamidofos (1230) + TX, clozophos (1231) + TX, Ivermycin (alias) [CCN] + TX, kinetin (alias) (210) + TX, methyl Phosphorus reduction (1258) + TX, metabolite (519) + TX, metabolite (alias) (519) + TX, sodium salt of metabolite (519) + TX, methyl bromide (537) + TX, methyl isothiocyanate (543) + TX, Milbex oxime (alias) [CC N]+TX, moxidectin (alias) [CCN]+TX, composition of Myrothecium verrucaria (alias) (565) + TX, NC-184 (compound code) + TX, oxamine醯(602)+TX, phorate (636)+TX, Phospamine (639)+TX, Phospoxcarb [CCN]+TX, Kexiandan (alias) +TX, Selaketin (alias) [CCN ]+TX, spinosyn (737)+TX, tertiary carbohydrate (alias)+TX, terbufos (773)+TX, tetrachlorothiophene (IUPAC/Chemical Abstracts name) (1422)+TX, thiafenox ( Alias) +TX, thiophos (1434) +TX, triazophos (820) +TX, triazophos (alias) +TX, xylenol [CCN]+TX, YI-5302 (compound code) and corn (Alias) (210) + TX, fluensulfone [318290-98-1] + TX, fluopyram + TX, nitrification inhibitor, the nitrification inhibitor can be selected from the following composition Substance group: Potassium ethylxanthogenate [CCN] and nitrapyrin (580) + TX, plant activator, the plant activator is selected from the following group of substances: acibenzolar (6) + TX, thiadiazolin- S -methyl (6) + TX, probenazole (658) and Reynoutria sachalinensis extract (alias) (720) + TX, kill Rodenticide, the rodenticide is selected from the material group consisting of: 2-isopentylindane-1,3-dione (IUPAC name) (1246) + TX, 4-(quinoline-2-yl Amino) benzenesulfonamide (IUPAC name) (748) + TX, α-chlorohydrin [CCN] + TX, aluminum phosphide (640) + TX, Anto (880) + TX, arsenic trioxide (882) + TX , Barium carbonate (891) + TX, bisfamus urea (912) + TX, bromadiolone (89) + TX, bromadiolone (91) + TX, bromadiolate (92) + TX, calcium cyanide (444) ) + TX, aldose (127) + TX, chlorphethanone (140) + TX, cholecalciferol (850) + TX, chlordiazepine (1004) + TX, grammon (1005) + TX, Tetrafamol (175) + TX, Tetrafamol (1009) + TX, Tetradex (246) + TX, Thiacrine (249) + TX, Diquat sodium (273) + TX, Vitamin D2 (301) + TX, flufafax (357) + TX, flufaxamine (379) + TX, flufafaxine hydrochloride (1183) + TX, flufaxamine hydrochloride (1 183) + TX, γ-HCH (430) + TX, HCH (430) + TX, hydrocyanic acid (444) + TX, methyl iodide (IUPAC name) (542) + TX, Lin Dan (430) + TX, Magnesium phosphide (IUPAC name) (640) + TX, methyl bromide (537) + TX, rattelin (1318) + TX, tetramine (1336) + TX, phosphine (IUPAC name) (640) + TX, Phosphorus [CCN] + TX, Tridentone (1341) + TX, Potassium Arsenite [CCN] + TX, Mimoyou (1371) + TX, Scallion Glycoside (1390) + TX, Arsenite Sodium [CCN] + TX, sodium cyanide (444) + TX, sodium fluoroacetate (735) + TX, strychnine (745) + TX, thallium sulfate [CCN] + TX, warfarin (851) and phosphorus Zinc (640) + TX, synergist, the synergist is selected from the group of substances consisting of: 2-(2-butoxyethoxy) ethyl piperonyl ester (IUPAC name) (934) + TX , 5-(1,3-Benzodioxol-5-yl)-3-hexylcyclohex-2-enone (IUPAC name) (903) + TX, bacteria with neroli tertiary alcohol Chlorenol (alias) (324) + TX, MB-599 (development code) (498) + TX, MGK 264 (development code) (296) + TX, piperonyl butoxide (649) + TX, Piprotal (1343) + TX, propyl isomer (1358) + TX, S421 (development code) (724) + TX, sesamex (1393) + TX, sesame forest Sesasmolin (1394) and subsulfite (1406) + TX, animal repellent, the animal repellent is selected from the following substance group: anthraquinone (32) + TX, chloralose (127) + TX , Copper naphthenate [CCN] + TX, copper king (171) + TX, diphosphorus (227) + TX, dicyclopentadiene (chemical name) (1069) + TX, biguanide octyl salt (guazatine) ( 422) + TX, biguanine octyl acetate (422) + TX, methamphet (530) + TX, pyridin-4-amine (IUPAC name) (23) + TX, salen (804) + TX, coxacarb (Trimethacarb) (840) + TX, zinc naphthenate [CCN] and thiram (856) + TX, a viricide, the viricide selected from the group consisting of: Imanin (alias) [CCN ] And ribavirin (alias) [CCN] + TX, a wound protectant, which is selected from the following materials Group: Mercury oxide (512) + TX, octhilinone (590) and thiophanate-methyl (802) + TX, and biologically active compounds, which are selected from the group consisting of the following substances: Aza Conazole [60207-31-0] + TX, Bifentriconazole [70585-36-3] + TX, Furconazole [116255-48-2] + TX, Cyproconazole [94361-06-5] + TX, difenoconazole [119446-68-3] + TX, diniconazole [83657-24-3] + TX, epoxiconazole [106325-08-0] + TX, niconazole [114369- 43-6] + TX, fluquinconazole [136426-54-5] + TX, fluquinconazole [85509-19-9] + TX, fluconazole [76674-21-0] + TX, hexyl Conazole [79983-71-4] + TX, imazalil [35554-44-0] + TX, imidazole [86598-92-7] + TX, inoconazole [125225-28-7] + TX, Meconazole [125116-23-6] + TX, Myclobutanil [88671-89-0] + TX, Pyriculare [101903-30-4] + TX, Penconazole [66246-88-6] + TX, prothioconazole [178928-70-6] + TX, pyrifenox [88283-41-4] + TX, prochlorphene [67747-09-5] + TX, propiconazole [60207 -90-1] + TX, simeconazole (simeconazole) [149508-90-7] + TX, tebuconazole [107534-96-3] + TX, simeconazole [112281-77-3] + TX, Triadimefon [43121-43-3] + TX, Triadimefon [55219-65-3] + TX, Fluconazole [99387-89-0] + TX, Triadazole [131983-72-7] + TX , Tricyclic Phenyl Alcohol [12771-68-5] + TX, Chlorophenimidine Alcohol [60168-88-9] + TX, Fluorochloro Phenimidine Alcohol [63284-71-9] + TX, Ethidium sulfonic acid Esters (bupirimate) [41483-43-6] + TX, dimethirimol [5221-53-4] + TX, ethirimol [23947-60-6] + TX, twelve ring𠰌 Morpholine [1593-77-7] + TX, fenpropidine [67306-00-7] + TX , Butyl benzene [67564-91-4] + TX, spirulina[118134-30-8] + TX, thirteen benzene [81412-43-3] + TX, cyprodinil [121552- 61-2] + TX, pyrimethanil [110235-47-7] + TX, pyrimethanil [53112-28-0] + TX, seed dressing [74738-17-3] + TX, pyrimethanil Fludioxonil [131341-86-1] + TX, benalaxyl [71626-11-4] + TX, furalaxyl [57646-30-7] + TX, metalaxyl [57837-19-1] + TX, R-Metalaxyl [70630-17-0] + TX, Furamide [58810-48-3] + TX, Oxadixyl [77732-09-3 ] + TX, benomyl [17804-35-2] + TX, carbendazim [10605-21-7] + TX, debacarb [62732-91-6] + TX, Mai Suining [ 3878-19-1] + TX, thiabendazole [148-79-8] + TX, chlozolinate [84332-86-5] + TX, dichlozoline [24201-58- 9] + TX, iprodione [36734-19-7] + TX, myclozoline[54864-61-8] + TX, procymidone [32809-16-8] + TX, vinyl bacteria Vinclozoline [50471-44-8] + TX, boscalid [188425-85-6] + TX, vinclozoline [5234-68-4] + TX, metfuraniline [ 24691-80-3] + TX, flutolanil [66332-96-5] + TX, methafenamine [55814-41-0] + TX, oxychloranil [5259-88-1] + TX, penthiopyrad [183675-82-3] + TX, penthiopyrad [130000-40-7] + TX, biguanide salt [108173-90-6] + TX, dodine ) [2439-10-3][112-65-2] (free base) + TX, iminoctadine [13516-27-3] + TX, azoxystrobin [13186 0-33-8] + TX, Kresoxim [149961-52-4] + TX, Entristrobin {Proc. BCPC,Int. Congr., Glasgow, 2003, 1 , 93} + TX, fluoxastrobin Ester [361377-29-9] + TX, methyl oxystrobin [143390-89-0] + TX, fenoxystrobin [133408-50-1] + TX, trifloxystrobin [141517-21-7] + TX, orysastrobin [248593-16-0] + TX, picoxystrobin [117428-22-5] + TX, pyraclostrobin [175013-18-0] + TX, thiram [14484- 64-1] + TX, Mancozeb [8018-01-7] + TX, Mancozeb [12427-38-2] + TX, Mancozeb [9006-42-2] + TX, Mancozeb Zinc (propineb) [12071-83-9] + TX, Salem [137-26-8] + TX, Daisenzine [12122-67-7] + TX, Thiram [137-30-4] + TX , Captafol [2425-06-1] + TX, captafol [133-06-2] + TX, beflusulfonamide [1085-98-9] + TX, fluoroimide [ 41205-21-4] + TX, Sanitizer [133-07-3] + TX, Toluenesulfonamide [731-27-1] + TX, Bordeaux mixture [8011-63-0] + TX, copper hydroxide (Copperhydroxid) [20427-59-2] + TX, copper chloride (copperoxychlorid) [1332-40-7] + TX, copper sulfate (coppersulfat) [7758-98-7] + TX, copper oxide (copperoxid)[ 1317-39-1] + TX, mancopper [53988-93-5] + TX, oxine-copper [10380-28-6] + TX, dinocap [131-72-6] + TX, nitrothal-isopropyl [10552-74-6] + TX, Kefensan [17109-49-8] + TX, iprobenphos [26087 -47-8] + TX, isoprothiolane (isoprothiolane) [50512-35-1] + TX, phosdiphen (phosdiphen) [36519-00-3] + TX, grams Pyrazophos [13457-18-6] + TX, tolclofos-methyl [57018-04-9] + TX, pyrazophos-S-methyl [135158-54-2 ] + TX, Dibendazim [101-05-3] + TX, Benthiasamide [413615-35-7] + TX, blasticidin-S [2079-00-7] + TX, Chinomethionat [2439-01-2] + TX, chloroneb [2675-77-6] + TX, chlorothalonil [1897-45-6] + TX, fluflunomide [180409 -60-3] + TX, cymoxanil [57966-95-7] + TX, dichlone (dichlone) [117-80-6] + TX, diclocymet (diclocymet) [139920-32 -4] + TX, diclomezine (diclomezine) [62865-36-5] + TX, dicloran (dicloran) [99-30-9] + TX, diethofencarb [87130-20-9 ] + TX, dithianon [110488-70-5] + TX, SYP-LI90 (Flumorph) [211867-47-9] + TX, dithianon [3347-22-6] + TX, Ethaboxam (ethaboxam) [162650-77-3] + TX, etridiazole [2593-15-9] + TX, oxaconazole [131807-57-3] + TX, fiddlehead ( fenamidone) [161326-34-7] + TX, fenoxanil [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, Cyclofenac [126833-17-8] + TX, fosetyl-aluminium [39148-24-8] + TX, hymexazol [10004 -44-1] + TX, propane zinc [140923-17-7] + TX, IKF-916 (Cyazofamid) [120116-88-3] + TX, kasugamycin [6980-18-3] + TX, methasulfocarb [66952-49 -6] + TX, benzophenone [220899-03-6] + TX, pencycuron (pencycuron) [66063-05-6] + TX, phthalide [27355-22-2] + TX, polyoxin Polyoxins [11113-80-7] + TX, probenazole [27605-76-1] + TX, propamocarb [25606-41-1] + TX, iodoquinazole (Proquinazid) [189278-12-4] + TX, pyroquilon [57369-32-1] + TX, quinoxaline [124495-18-7] + TX, pentachloronitrobenzene [82-68 -8] + TX, sulfur [7704-34-9] + TX, tithiamid [223580-51-6] + TX, triazoxide (triazoxide) [72459-58-6] + TX, tricyclazole [ 41814-78-2] + TX, triforine (triforine) [26644-46-2] + TX, effective mycin [37248-47-8] + TX, zoxamide (RH7281) [156052 -68-5] + TX, mandipropamid (mandipropamid) [374726-62-2] + TX, pymetrozine (isopyrazam) [881685-58-1] + TX, sedaxane [874967 -67-6] + TX, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (9-dichloromethylene-1,2,3,4-tetrahydro-1 ,4-Methyl bridge-naphthalene-5-yl)-amide (disclosed in WO 2007/048556) + TX, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (3 ',4',5'-Trifluoro-biphenyl-2-yl)-amide (disclosed in WO 2006/087343) + TX, [(3 S ,4 R ,4a R ,6 S ,6a S ,12 R ,12a S ,12b S )-3-[(cyclopropylcarbonyl)oxy]-1,3,4,4a,5,6,6a,12,12a,12b-decahydro-6,12 -Dihydroxy-4,6a,12b-trimethyl-11-side oxy-9-(3-pyridyl)-2H,11H naphtho[2,1- b]piperano[3,4-e]piperan-4-yl]methyl-cyclopropanoate [915972-17-7] + TX and 1,3,5-trimethyl-N-( 2-Methyl-1-oxopropyl)-N-[3-(2-methylpropyl)-4-[2,2,2-trifluoro-1-methoxy-1-(trifluoromethyl Yl)ethyl]phenyl]-1H-pyrazole-4-carboxamide [926914-55-8] + TX; lancotrione [1486617-21-3] + TX; chlorofluoropyridine ester [943832-81-3 ] + TX; ipfentrifluconazole [1417782-08-1] + TX; mefentrifluconazole [1417782-03-6] + TX; quinofumelin [861647-84-9] + TX; dextro-trans-chlorine Propithrin [399572-87-3] + TX; chlorfluranil [1262605-53-7] + TX; trifluoroimididine [1254304-22-7] + Tx; fluxametamide [928783- 29-3] + TX; ε-Methfluthrin [240494-71-7] + TX; ε-momfluorothrin [1065124-65-3] + TX; pydiflumetofen [1228284-64 -7] + TX; κ-bifenthrin [439680-76-9] + TX; broflanilide [1207727-04-5] + TX; dicloromezotiaz [1263629-39-5] + TX; dipymetitrone [16114-35- 5] + Tx; pyraziflumid [942515-63-1] + TX; κ-tefluthrin [391634-71-2] + TX; fenpicoxamid (fenpicoxamid) [517875-34-2] + TX; Fluindapyr [1383809-87-7] + TX; alpha-bromadiolone [28772-56-7] + TX; flupyrimin [1689566-03-7] + TX; benzene Benzpyrimoxan [1449021-97-9] + TX; acynonapyr [1332838-17-1] + TX; inpyrfluxam [1352994-67-2] + Tx, isoflucypram [1255734-28-1] + TX; red round scale insect attractant (rescalure) [64309-03-1] + TX; aminopyrifen (aminopyrifen) [1531626-08-0] + TX; tyclopyrazoflor [1477919- 27-9] + TX; and tetramer acid insecticide (spiropidion) [1229023-00-0] + TX; and microbial agents, including: Acinetobacter ruckeri + TX, Acremonium fungi + TX + TX, Cephalosporium acremonium + TX + TX, Acremonium diospyri+ TX, Acremonium obclavatum + TX, AdoxGV (Capex®) + TX, Agrobacterium radiobacter strain K84 (Galltrol-A®) + TX, Alternaria destruens + TX, Alternaria destruens + TX, Alternaria destruens (Smolder®) + TX, Alternaria destruens (AQ10®) + TX, Aspergillus flavus AF36 (AF36®) + TX , Aspergillus flavus NRRL 21882 (Aflaguard®) + TX, Aspergillus species + TX, Aureobasidium pullulans + TX, Azospirillum + TX, (MicroAZ® + TX, TAZO B®) + TX, Azotobacter + TX, Azotobacter chroocuccum (Azotomeal®) + TX, Azotobacter cysts (Bionatural Blooming Blossoms®) + TX, Bacillus amyloliquefaciens + TX, Bacillus cereus + TX, Bacillus eross strains ( Bacillus chitinosporus strain) CM-1 + TX, Bacillus chitinosporus strain AQ746 + TX, Bacillus licheniformis strain HB-2 (Biostart™ Rhizoboost®) + TX, Bacillus licheniformis strain 3086 (EcoGuard® + TX, Green Releaf®) + TX, Bacillus circulans + TX, Bacillus firmus (BioSafe®+ TX, BioNem-WP®+ TX, VOTiVO®) + TX, Bacillus firmus strain I-1582 + TX, dip Bacillus hepus + TX, Bacillus marismortui + TX, Bacillus megaterium + TX, Bacillus mycoides strain AQ726 + TX, Bacillus lactis (Milky Sp ore Powder®) + TX, Bacillus pumilus species + TX, Bacillus pumilus strain GB34 (Yield Shield®) + TX, Bacillus pumilus strain AQ717 + TX, Bacillus pumilus strain QST 2808 (Sonata® + TX, Ballad Plus ®) + TX, Bacillus spahericus (VectoLex®) + TX, Bacillus species + TX, Bacillus strain AQ175 + TX, Bacillus strain AQ177 + TX, Bacillus strain AQ178 + TX, Bacillus subtilis strain QST 713 (CEASE® + TX, Serenade® + TX, Rhapsody®) + TX, Bacillus subtilis strain QST 714 (JAZZ®) + TX, Bacillus subtilis strain AQ153 + TX, Bacillus subtilis strain AQ743 + TX, Bacillus subtilis strain QST3002 + TX, Bacillus subtilis strain QST3004 + TX, Bacillus subtilis variant strain FZB24 (Taegro® + TX, Rhizopro®) + TX, Bacillus thuringiensis Cry 2Ae + TX, Bacillus thuringiensis Cry1Ab + TX, Bacillus thuringiensis aizawai (Bacillus thuringiensis aizawai) GC 91 (Agree®) + TX, Bacillus thuringiensis israelensis (BMP123® + TX, Aquabac® + TX, VectoBac®) + TX, Bacillus thuringiensis Bacillus thuringiensis kurstaki (Javelin® + TX, Deliver® + TX, CryMax® + TX, Bonide® + TX, Scutella WP® + TX, Turilav WP ® + TX, Astuto® + TX, Dipel WP® + TX, Biobit® + TX, Foray®) + TX, Bacillus thuringiensis Kurstark BMP 123 (Baritone®) + TX, Bacillus thuringiensis Kurstark HD-1 (Bioprotec-CAF / 3P ®) + TX, Bacillus thuringiensis strain BD#32 + TX, Bacillus thuringiensis strain AQ52 + TX, Bacillus thuringiensis var. aizawai (XenTari® + TX, DiPel®) + TX, bacteria spp. (GROWMEND® + TX, GROWSWEET® + TX, Shootup®) + TX, Clavivacter michiganensis phage (AgriPhage®) + TX, Bakflor® + TX, ball Beauveria bassiana (Beaugenic® + TX, Brocaril WP®) + TX, Beauveria bassiana GHA (Mycotrol ES® + TX, Mycotrol O® + TX, BotaniGuard®) + TX, Beauveria bassiana (Beauveria brongniartii) (Engerlingspilz® + TX, Schweizer Beauveria® + TX, Melocnt®) + TX, Beauveria spp. + TX, Botrytis cineria + TX, slow growth of soybean Type Rhizobium (Bradyrhizobium japonicum) (TerraMax®) + TX, Brevibacillus brevis + TX, Bacillus thuringiensis tenebrionis (Novodor®) + TX, BtBooster + TX, Onion Burke Burkholderia cepacia (Deny® + TX, Intercept® + TX, Blue Circle®) + TX, Burkholderia gladii + TX, Burkholderia gladioli ) + TX, Burkholderia spp. + TX, Canadian thistle fungus (CBH Canadian Bioherbicide®) + TX, Candida butyri + TX, Anonymous Candida famata + TX, Candida fructus + TX, Candida glabrata + TX, Candida guilliermondii + TX, Candida melibiosica + TX, Candida olive Candida oleophila) strain O + TX, Candida parapsilosis + TX, Candida pelliculosa + TX, Candida pulcherrima + TX, Candida reesei reukaufii) + TX, Candida saitoana (Bio-Coat® + TX, Biocure®) + TX, Candida sake + TX, Candida spp. + TX , Candida tenius (Candida tenius) + TX, Cedecea dravisae + TX, Cellulomonas flavigena + TX, Chaetomium cochliodes (Nova-Cide) ®) + TX, Chaetomium globosum (Nova-Cide®) + TX, Chromobacterium subtsugae strain PRAA4-1T (Grandevo®) + TX, Cladosporium cladosporioides + TX, Cladosporium oxysporum + TX, Cladosporium chlorocephalum + TX, Cladosporium spp. + TX, Cladosporium tenuissimum + TX, pink stick Clonostachys rosea (EndoFine®) + TX, Colletotrichum acutatum + TX, Coniothyrium minitans (Cotans WG®) + TX, Coniothyrium spp. + TX, Cryptococcus albidus (YIELDPLUS®) + TX, Cryptococcus humicola + TX, Cryptococcus infirmo-miniatus + TX, Cryptococcus laurentii (Cryptococcus laurentii) + TX, Apple Cryptophlebia leucotreta granule virus ovirus) (Cryptex®) + TX, Cupriavidus campinensis+ TX, Cydia pomonella granulovirus (CYD-X®) + TX, Codling moth granulovirus (Madex® + TX, Madex Plus® + TX , Madex Max/ Carpovirusine® + TX, Cylindrobasidium laeve (Stumpout®) + TX, Cylindrocladium + TX, Debaryomyces hansenii + TX, Drechslera hawaiinensis + TX, Enterobacter cloacae (Enterobacter cloacae) + TX, Enterobacteriaceae + TX, Entomophtora virulenta (Vektor®) + TX, Epicoccum nigrum + TX, Epicoccum purpurascens + TX, Epicococcus species + TX, Filobasidium floriforme + TX, Fusarium acuminata + TX, Fusarium vulgaris + TX, Fusaclean® / Biofox C® + TX, Fusarium floriforme + TX, Fusarium Genus species + TX, Galactomyces geotrichum + TX, Gliocladium catenulatum (Primastop® + TX, Prestop®) + TX, Gliocladium roseum + TX, Gliocladium catenulatum Genus species (SoilGard®) + TX, Gliocladium virens (Soilgard®) + TX, Granupom® + TX, Halobacillus halophilus + TX, Halobacillus litoralis ) + TX, Halobacillus trueperi + TX, Halomonas species + TX, Halomonas subglaciescola + TX, Halovibrio variabilis + TX, Hansenula spores + TX, Helicovex nucleopolyhedrosis virus (Helicovex®) + TX, Spodoptera exigua Nuclear Polyhedrosis Virus (Gemstar®) + TX, Isoflavones-Formononet (Myconate®) + TX, Lemon Klerk yeast + TX, Klerk yeast species + TX, Lagenidium giganteum (Laginex®) + TX, Lecanicillium longisporum (Vertiblast®) + TX, Lecanicillium muscarium (Vertikil®) + TX, Gypsy moth nuclear polyhedrosis virus (Disparvirus®) ) + TX, halophilic seacoccus + TX, Meira geulakonigii + TX, Metarhizium anisopliae (Met52®) + TX, Metarhizium anisopliae (Destruxin WP®) + TX, Metschnikowia fruticola (Shemer®) + TX, Metschnikowia pulcherrima (Metschnikowia pulcherrima) + TX, Microdochium dimerum (Antibot®) + TX, Micromonospora coerulea + TX, Microsphaeropsis ochracea + TX, odorous white fungus (Muscodor albus) 620 (Muscudor®) + TX, Muscodor roseus strain A3-5 + TX, Mycorrhizae species (Mycorrhizae spp.) (AMykor® + TX, Root Maximizer®) + TX, Mycorrhiza verrucosa strain AARC-0255 (DiTera® ) + TX, BROS PLUS® + TX, Ophiostoma piliferum strain D97 (Sylvanex®) + TX, Paecilomyces farinosus + TX, Paecilomyces farinosus + TX, Paecilomyces farinosus (PFR-97® + TX, PreFeRal®) + TX , Paecilomyces lilacinus (Biostat WP®) + TX, Paecilomyces lilacinus strain 251 (MeloCon WG®) + TX, Bacillus polymyxa + TX, Pantoea agglomerans (BlightBan C9-1®) ) + TX, Pantoea species + TX, Pasteurella species (Econem®) + TX, Pasteuria nishizawae (Pasteuria nishizawae) + TX, Penicillium chrysogenum + TX, Penicillium belayi ( Penicillium billai) (Jumpsta rt® + TX, TagTeam®) + TX, Penicillium brevifolia + TX, Penicillium breviflora + TX, Penicillium griseoicum + TX, Penicillium violaceum + TX, Penicillium species + TX, pure green Ken mold + TX, large Phlebiopsis gigantean (Rotstop®) + TX, Phosphomeal® + TX, Cryptophyte + TX, Phytophthora palmitos (Devine®) + TX, Pichia pastoris + TX, Ji Ye Pichia guilermondii + TX, Pichia guilermondii + TX, Pichia nails + TX, Pichia stipitis + TX, Pseudomonas aeruginosa + TX, Pseudomonas aureus aureofasciens (Spot-Less Biofungicide®) + TX, Pseudomonas cepacia + TX, Pseudomonas chlorophylla (AtEze®) + TX, Pseudomonas corrugate + TX, Fluorescent pseudomonas BlightBan A506® + TX, Pseudomonas putida + TX, Pseudomonas reactans + TX, Pseudomonas species + TX, Pseudomonas syringae (Bio-Save®) + TX, green yellow Pseudomonas + TX, Pseudomonas fluorescens (Zequanox®) + TX, Pseudozyma flocculosa strain PF-A22 UL (Sporodex L®) + TX, Puccinia canaliculata + TX, Puccinia thlaspeos ( Wood Warrior® + TX, Pythium oligandrum + TX, Pythium oligandrum (Polygandron® + TX, Polyversum®) + TX, Pythium aquaticum + TX, Rhanella aquatilis + TX, Rhanella spp. + TX, Rhizobia (Dormal® + TX, Vault®) + TX, Rhizoctonia + TX, Rhodococcus globerulus strains AQ719 + TX, Rhodosporidium diobovatum + TX, Rhodosporidium toruloides + TX, Rhodotorula spp. + TX, Rhodosporidium toruloides (Rhodotorula glutinis) + TX, Rhodotorula graminis + TX, Rhodotorula mucilagnosa + TX, Rhodotorula rubra + TX, Saccharomyces cerevisiae + TX, Rose salt coccus (Salinococcus roseus) + TX, Sclerotinia minor + TX, SARRITOR® + TX, Scytalidium spp. + TX, Scytalidium uredinicola + TX, beet night Moth nuclear polyhedrosis virus (Spodoptera exigua nuclear polyhedrosis virus) (Spod-X® + TX, Spexit®) + TX, Serratia marcescens + TX, Serratia plymuthica + TX, Serratia spp. + TX, Sordaria fimicola + TX, Spodoptera littoralis nucleopolyhedrovirus (Littovir®) + TX, Sporobolomyces roseus + TX, Stenotrophomonas maltophilia + TX, Streptomyces ahygroscopicus + TX, Streptomyces albaduncus + TX, defoliation Streptomyces exfoliates + TX, Streptomyces galbus + TX, Streptomyces griseoplanus + TX, Streptomyces griseoviridis (Mycostop®) + TX, Streptomyces lydia (Streptomyces lydicus) (Actinovate®) + TX, Streptomyces lydicus WYEC-108 (ActinoGrow®) + TX, Streptomyces violaceus + TX, Tilletiopsi s minor) + TX, Tilletiopsis spp. + TX, Trichoderma asperellum (T34 Biocontrol®) + TX, Trichoderma gamsii (Tenet®) + TX , Trichoderma atroviride (Plantmate®) + TX, Trichoderma hamatum TH 382 + TX, Trichoderma harzianum rifai (Mycostar®) + TX, Trichoderma harzianum ) T-22 (Trianum-P® + TX, PlantShield HC® + TX, RootShield® + TX, Trianum-G®) + TX, Trichoderma harzianum T-39 (Trichodex®) + TX, non-hook Trichoderma inhamatum + TX, Trichoderma koningii + TX, Trichoderma spp. LC 52 (Sentinel®) + TX, Trichoderma lignorum + TX, Long handle wood Mold (Trichoderma longibrachiatum) + TX, Trichoderma polysporum (Binab T®) + TX, Yew mold (Trichoderma taxi) + TX, Trichoderma virens + TX, Trichoderma virens (originally called It is Gliocladium virens GL-21) (SoilGuard®) + TX, Trichoderma viride + TX, Trichoderma viride strain ICC 080 (Remedier®) + TX, Trichosporon pullulans) + TX, Trichosporon spp. + TX, Trichothecium spp. + TX, Trichothecium roseum + TX, Typhula phacorrhiza strain 94670 + TX, Typhula phacorrhiza strain 94671 + TX, black Ulocladium atrum + TX, Ulocladium oudemansii (Botry-Zen®) + TX, Ustilago maydis + TX, various bacteria and supplementary micronutrients (Natural) II®) + TX, various fungi (Millennium Microbes®) + TX, Verticillium chlamydosporium + TX, Verticillium lecanii (Mycotal® + TX, Vertalec®) + TX, Vip3Aa20 (VIPtera®) + TX, Mycobacterium dead sea (Virgibaclillus marismortui) + TX, Xanthomonas campestris pv.Poae (Camperico®) + TX, X. berghei + TX, X. nematophilus; and Plant extracts, including: pine oil (Retenol®) + TX, azadirachtin (Plasma Neem Oil® + TX, AzaGuard® + TX, MeemAzal® + TX, Molt-X® + TX, plant IGR (Neemazad® + TX) , Neemix® + TX, canola oil (Lilly Miller Vegol®) + TX, Chenopodium ambrosioides near ambrosioides (Requiem®) + TX, chrysanthemum extract (Crisant®) + TX, neem oil extract ( Trilogy® + TX, Labiatae essential oil (Botania®) + TX, clove-rosemary-pepper mint and thyme oil extract (Garden insect killer®) + TX, betaine (Greenstim®) + TX , Garlic + TX, lemongrass oil (GreenMatch®) + TX, neem oil + TX, catnip (Nepeta cataria) (catnip oil) + TX, Nepeta catarina + TX, nicotine + TX, oregano oil (MossBuster ®) + TX, Pedaliaceae oil (Nematon®) + TX, Pyrethrum + TX, Quillaja saponaria (NemaQ®) + TX, Reynoutria sachalinensis (Regalia®+ TX, Sakalia®) + TX, Rotenone (Eco Roten®) + TX, Rutaceae plant extracts (Soleo®) + TX, soybean oil (Ortho ecosense®) + TX, tea tree oil (Timorex Gold®) + TX, thyme oil + TX, AGNIQUE® MMF+ TX, BugOil®+ TX, rosemary-sesame-peppermint-thyme and cinnamon extract mixture (EF 300®) + TX, clove-rosemary and peppermint extract mixture (EF 400®) + TX, clove-peppermint-garlic Oil and peppermint mixture (Soil Shot®) + TX, kaolin (Screen®) + TX, brown algae storage glucan (Laminarin®); and pheromone, including: 3M Sprayable Blackheaded Fireworm Pheromone® + TX, codling moth pheromone (Paramount dispenser-(CM)/ Isomate C-Plus®) + TX, grape leaf roller pheromone (3M MEC-GBM Sprayable Pheromone®) + TX, leaf roll pheromone (3M MEC – LR Sprayable Pheromone® + TX, Muscamone (Snip7 Fly Bait® + TX, Starbar Premium Fly Bait®) + TX, 3M oriental fruit moth sprayable pheromone® + TX , Peachtree Borer pheromone (Isomate-P®) + TX, Tomato Pinworm (Tomato Pinworm) pheromone (3M Sprayable pheromone®) + TX, Entostat powder (from palm Tree extract) (Exosex CM®) + TX, (E + TX, Z + TX, Z)-3 + TX, 8 + TX, 11 tetradecatriene acetate + TX, (Z + TX, Z + TX, E) -7 + TX, 11 + TX, 13-hexatrienal + TX, (E + TX, Z)-7 + TX, 9-dodecadien-1-yl acetic acid Ester + TX, 2-methyl-1-butanol + TX, calcium acetate + TX, Scenturion® + TX, Biolure® + TX, Check-Mate® + TX, Lavandulyl senecioate; and Macrobio Macrobial, including : Short-distance aphids + TX, Aphidius ervi (Aphelinus-System®) + TX, Acerophagus papaya + TX, two-star ladybug (Adalia-System®) + TX, two-star ladybug (Adaline®) + TX, Aphidalia® + TX, Ageniaspis citricola + TX, Amblyseius andersoni + TX, Amblyseius andersoni (Anderline® + TX, Andersoni) -System® + TX, Amblyseius californicus (Amblyline® + TX, Spical®) + TX, Thripex® + TX, Bugline cucumeris® + TX, Fallacis ®) + TX, Bugline swirskii® + TX, Swirskii-Mite® + TX, WomerMite® + TX, Amitus hesperidum + TX, Original cherry mymarids wings (Anagrus atomus) + TX, dark ventral cord length Encyrtidae (Anagyrus fusciventris) + TX, Karma long cable Encyrtidae (Anagyrus kamali) + TX, Anagyrus loecki + TX, mealybugs long jump rope small Bee ( Anagyrus pseudococci ) (Citripar®) + TX, Anicetus benefices + TX, Golden Bee ( Anisopteromalus calandrae ) + TX, Anthocoris nemoralis (Anthocoris-System®) + TX, Apheline® + TX, Aphiline® + TX, Aphelinus asychis + TX, Aphidius colemani (Aphipar®) + TX, Aphiline Bee (Ervipar®) + TX, Myzus persicae + TX, Myzus persicae (Aphipar-M®) + TX, Aphidend® + TX, Aphidoline® + TX, Lingnan Yellow Aphid + TX, India and Pakistan Yellow Aphid + TX, Aprostocetus hagenowii ( Aprostocetus hagenowii ) + TX, Atheta coriaria (Staphyline®) + TX, Bombus species + TX, European bumblebee (Natupol Beehive®) + TX, European bumblebee (Beeline® + TX, Tripol®) + TX, Cephalonomia stephanoderis + TX, Chilocorus nigritus + TX, common lacewing ( Chrysoperla carnea ) (Chrysoline®) + TX, common lacewing (Chrysopa®) + TX, Chrysoperla rufilabris ( Chrysoperla rufilabris ) + TX, Cirrospilus ingenuus + TX, Cirrospilus quadristriatus + TX, Citrostichus phyllocnistoides + TX, Closterocerus chamaeleon + TX, Closterocerus chamaeleon + TX, Closterocerus chamaeleonus species + TX, Coccidoxenoides perminutus (Planopar®) + TX, Park wasps (Coccophagus cowperi) + TX, Lai food Kuwana aphid wasps (Coccophagus lycimnia) + TX, yellow borer foot Cotesia + TX, diamondback moth cashmere Braconi + TX, Monteggia crypto-lipped ladybug (Cryptobug® + TX, Cryptoline®) + TX, Japanese square head armor + TX, Siberian cocoon+ TX, Siberian cocoon (Minusa®) + TX, Diminex® + TX, Delphastus catalinae (Delphastus®) + TX, Delphastus pusillus + TX, Diachasmimorpha krausii + TX, Liriomyza krausii + TX, Diaparsis jucunda + TX, Ali eating lice Encyrtidae (Diaphorencyrtus aligarhensis) + TX, the pea leaf miner wasp + TX, pea leaf miner wasp (Miglyphus® + TX, Digline®) + TX, from Siberia jaw Ashmead ( DacDigline® + TX, Minex®) + TX, Qimai Eretmocerus species + TX, Eretmocerus eremicus + TX, Encarsia max® + TX, Encarline® + TX, En-Strip® + TX, Eretmocerus eremicus (Enermix®) + TX, Encarsia guadeloupae + TX, Encarsia haitiensis + TX, Syrphidend® + TX, Eretmoceris siphonini + TX, California pulp Eretmocerus californicus + TX, Eretmocerus eremicus (Ercal® + TX, Eretline e®) + TX, Eretmocerus eremicus (Bemimix®) + TX, sea Eretmocerus siphonini + TX, Bemipar® + TX, Eretline m® + TX, Eretmocerus siphonini + TX, Exochomus quadripustulatus + TX, mite galls Mosquitoes ( Feltiella acarisuga ) (Spidend®) + TX, Mite-eating Gall Midge (Feltiline®) + TX, Alishan Liriomyza + TX, Fopius ceratitivorus + TX, Formononetin (Wirless Beehome®) + TX, Vespop® + TX, Galendromus occidentalis + TX, Goniozus legneri + TX, Cotesia vulgaris + TX, HarmoBeetle® ) + TX, Heterodactylus species (Lawn Patrol®) + TX, Heterodactylophilus (NemaShield HB® + TX, Nemaseek® + TX, Terranem-Nam® + TX, Terranem® + TX, Larvanem® + TX, B-Green® + TX, NemAttack ® + TX, Nematop®) + TX, Heterorhabditis megidis (Nemasys H® + TX, BioNem H® + TX, Exhibitline hm ® + TX, Larvanem-M®) + TX, Hippodamia convergens + TX, Hypoaspis aculeifer (Aculeifer-System® + TX, Entomite-A®) + TX, Bingxia Shield mite ( Hypoaspis miles ) (Hypoline m® + TX, Entomite-M®) + TX, black branch tarsal bee + TX, Lecanoideus floccissimus + TX, Lemophagus errabundus + TX, Leptomastidea abnormis + TX, Leptomastix dactylopii (Leptopar®) + TX, Leptomastix epona + TX, Lindorus lophanthae + TX, Lipolexis oregmae + TX, Natufly® + TX, Mesoseiulus longipes + TX, Macrolophus caliginosus (Mirical-N® + TX, Macroline c® + TX, Mirical®) + TX, Mesoseiulus longipes + TX, Yellow Broadstalked Bee ( Macrolophus caliginosus ) Metaphycus flavus + TX, Metaphycus lounsburyi + TX, Milacewing® + TX, Microterys flavus + TX, Muscidifurax raptorellus and Spalangia cameroni (Biopar®) + TX, Neodryinus typhlocybae + TX, California Neoseius + TX, Cucumber Neoseiulus (THRYPEX®) + TX, Pseudo Neoseiulus fallacis ( Noseiulus fallacis ) + TX, Nesideocoris tenuis (NesidioBug® + TX, Nesibug®) + TX, bronze Black fly (Biofly®) + TX, Orius insidiosus (Thripor-I® + TX, Oriline i®) + TX, Orius laevigatus (Thripor-L® + TX, O riline l® + TX, Orius majusculus (Oriline m®) + TX, Thripor-S® + TX, Pauesia juniperorum + TX, Pediobius foveolatus ) + TX, Phasmarhabditis hermaphrodita (Nemaslug®) + TX, Phymastichus coffea + TX, Phytoseiulus macropilus + TX, Chilean phytoseiulus (Spidex® + TX, Phytoline p®) + TX, spot Yi abdominal stab bug (Podisus®) + TX, parasitic phoridae (Pseudacteon) curvatus + TX, parasitic phoridae (Pseudacteon) obtusus + TX, parasitic phoridae (Pseudacteon) tricuspis + TX, Pseudaphycus maculipennis + TX, Pseudleptomastix mexicana + TX, Psyllaephagus pilosus + TX, Psyttalia concolor (composite) + TX, Quadrastichus spp. + TX, Rhyzobius lophanthae + TX, Australian ladybug + TX, Rumina decollate + TX, Semielacher petiolatus + TX, Pipe aphid (Ervibank®) + TX, Nematac C® + TX, Millenium® + TX, BioNem C® + TX, NemAttack® + TX, Nemastar® + TX, Capsanem®) + TX, Steinernema-System® + TX (NemaShield® + TX, Nemasys F® + TX, BioNem F® + TX, Steinernema-System® + TX , NemAttack® + TX, Nemaplus® + TX, Exhibitline sf® + TX, Scia-rid® + TX, Entonem®) + TX, Steinernema kraussei (Nemasys L® + TX, BioNem L® + TX, Exhibitline srb®) + TX, Steinernema riobrave (BioVector® + TX, BioVektor®) + TX, Steinernema scapterisci (Nematac S®) + TX, Steinernematid species + TX, Steinernematid species (Guardian Nematodes®) + TX, Stethorus® + TX, Steinernematid + TX, Tetrastichus setifer + TX , Thripobius semiluteus + TX, Torymus sinensis + TX, Tricholine b® + TX, Tricho-Strip® + TX, Trichogramma vulgaris + TX, Trichogramma minus + TX, Trichogramma platneri + TX, Trichogramma platneri + TX, Trichogramma platneri + TX, Xanthopimpla stemmator (Xanthopimpla stemmator); and Other biological preparations include: abscisic acid + TX, bioSea® + TX, Chondrostereum purpureum (Chontrol Paste®) + TX, Collego® + TX, copper caprylate (Cueva®) ) + TX, Delta trap (Trapline d®) + TX, Harpin (ProAct® + TX, Ni-HIBIT Gold CST®) + TX, high iron phosphate (Ferramol®) + TX, Funnel trap (Trapline y®) + TX, Gallex® + TX, Grower's Secret® + TX, Homo-brassonolide + TX, iron phosphate (Lilly Miller Worry Free Ferramol Slug) & Snail Bait® + TX, MCP hail trap (Trapline f®) + TX, parasitic insect Microctonus hyperodae + TX, Mycoleptodiscus terrestris (De sX® + TX, BioGain® + TX, Aminomite® + TX, Zenox® + TX, Thripline ams® + TX, potassium bicarbonate (MilStop®) + TX, potassium salt of fatty acid (Sanova®) + TX, potassium silicate solution (Sil-Matrix®) + TX, potassium iodide + potassium thiocyanate (Enzicur®) + TX, SuffOil-X® + TX, spider poison + TX, locust microsporidian (Semaspore Organic Grasshopper Control) ®) + TX, Trapline YF® + TX, Rebell Amarillo® + TX and Takitrapline y + b® + TX; or a biologically active compound or reagent selected from the following: deltafluthrin + TX, Diflovidazine + TX, Flometoquin + TX, Fluhexafon + TX, Diamondback moth granulovirus + TX, Codling moth granulovirus + TX, Imicyafos + TX, Tobacco budworm nucleus Polyhedrosis virus + TX, Heliothis punctigera nuclear polyhedrosis virus + TX, Spodoptera frugiperda nuclear polyhedrosis virus + TX, Spodoptera frugiperda nuclear polyhedrosis virus + TX, Plutella xylostella nuclear polyhedrosis virus + TX, p-cymene + TX, Pyflubumide + TX, Pyrafluprole + TX, QRD 420 + TX, QRD 452 + TX, QRD 460 + TX, terpenoid mixture + TX, terpenoids + TX, Tetraniliprole + TX and α- Terpinene + TX or the active substance mentioned by the following code + TX: code AE 1887196 (BSC-BX60309) + TX, code NNI-0745 GR + TX, code IKI-3106 + TX, code JT-L001 + TX, Code ZNQ-08056 + TX, code IPPA152201 + TX, code HNPC-A9908 (CAS: [660411-21-2]) + TX, code HNPC-A2005 (CAS: [860028-12-2]) + TX, code JS118 + TX, code ZJ0967 + TX, code ZJ2242 + TX, code JS7119 (CAS: [929545-74-4]) + TX, code SN-1172 + TX, code HNPC-A9835 + TX, code HNPC-A9955 + TX, generation Code HNPC-A3061 + TX, code Chuanhua 89-1 + TX, code IPP-10 + TX, code ZJ3265 + TX, code JS9117 + TX, code ZJ3757 + TX, code ZJ4042 + TX, code ZJ4014 + TX, code ITM- 121 + TX, code DPX-RAB55 (DKI-2301) + TX, code NA-89 + TX, code MIE-1209 + TX, code MCI-8007 + TX, code BCS-CL73507 + TX, code S-1871 + TX , Code DPX-RDS63 + TX, Quinofumelin + TX, mefentrifluconazol + TX, fenpicoxamid + TX, fluindapyr + TX, inpyrfluxam + TX or indiflumetpyr + TX, isofulcypram + TX, pyrapropoyne + TX, florylpicoxamid + TX, metyltetraprole + TX, ipflufenoquin + TX, pyridachlometyl + TX or chlopyridiflu + TX, Tetrachlorantraniliprole + TX, tetrachloraniliprole + TX, Tyclopyrazoflor + TX, flupyrimin + TX or pyrifluramide + TX, benzpyrimoxan + TX, Benzosufyl + TX or oxazosulfyl + TX, etpyrafen + TX, acynonapyr + TX or pyrinonafen + TX, oxotrione + TX, bixlozone + TX or clofendizone + TX or diclofendizone + TX or dicloroxizone + TX , Cyclopyranil + TX or pyrazocyclonil + TX or cyclopyrazonil + TX, α-bromodiolone + TX, code AKD-1193 + TX, Oxathiapiprolin + TX , Fluopyram + TX , Penflufen + TX, Fluoxopyrosad + TX, and Flupyradifurone + TX.

References in parentheses after the active ingredient, for example [3878-19-1] refer to the Chemical Abstracts registration number. The mixed compatibility described above is known. When the active ingredients are included in "The Pesticide Manual [Pesticide Manual]" The Pesticide Manual-A World Compendium [Pesticide Manual-A World Compendium]; 13th edition; Editor: CDS TomLin; The British Crop Protection Coimcil [ In the British Crop Protection Commission], they are described by the number given in parentheses of the specific compound above; for example, the compound "abamectin" is described by the number (1). Among them, "[CCN]" is added to the above specific compounds, which are included in "Compendium of Pesticide Common Names", which can be found on the Internet [A. Wood; Compendium of Pesticide Common Names, Copyright (c) 1995-2004]; for example, the compound "acetoprole" is described in the Internet address http://www.alanwood.net/pesticides/acetoprole.html.

Most active ingredients are represented by the so-called "common name" above, and the corresponding "ISO common name" or other "common name" is used in different situations. If the name is not the "generic name", the type of name used is replaced by the name given in the parentheses of the specific compound; in this case, the IUPAC name, IUPAC/Chemical Abstract name, "chemical name", "Common name", "compound name" or "development code", or if neither of those names nor the "generic name" is used, the "alias" is used. "CAS Registry Number" means the Chemical Abstracts Registry Number.

The active ingredient mixture of the compound of formula I selected from Tables A-1 to A-17 and Table P and the active ingredient described above comprises a compound selected from Tables A-1 to A-17 and Table P and the activity as described above The mixing ratio of the ingredients is preferably from 100:1 to 1:6000, especially from 50:1 to 1:50, more especially from 20:1 to 1:20, even more especially from 10 : 1 to 1:10, very particularly from 5:1 and 1:5, it is particularly preferred to give a ratio from 2:1 to 1:2, and it is also preferred to give a ratio from 4:1 to 2:1 ratio, especially 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 ratio. The mixing ratios are by weight.

The mixture as described above can be used in a method for controlling pests. The method includes applying a composition containing the mixture as described above to pests or their environment, and used to treat the human body by surgery or therapy. Animal methods and diagnostic methods performed on humans or animals are excluded.

A mixture comprising a compound of formula I selected from Tables A-1 to A-17 and Table P and one or more active ingredients as described above can be applied, for example, as follows: in the form of a single "ready to mix and use" form, In combination spray mixtures consisting of separate formulations of single active ingredient components (such as "tank mixes"), and in a sequential manner (that is, in a reasonably short period of time (such as hours or days) one after another In the case of ground) application, the single active ingredients are used in combination. The order of application of the compounds of formula I selected from Tables A-1 to A-17 and Table P and the active ingredients as described above is not critical to the practice of the present invention.

The composition according to the present invention may also contain additional solid or liquid additives, such as stabilizers, such as unepoxidized or epoxidized vegetable oils (such as epoxidized coconut oil, rapeseed oil or soybean oil), Foaming agents (such as silicone oil), preservatives, viscosity modifiers, binders and/or tackifiers, fertilizers or other active ingredients used to obtain specific effects, such as bactericides, fungicides, nematicides, plant activation Agents, molluscicides or herbicides.

The composition according to the invention is in a manner known per se, in the absence of auxiliary agents, for example by grinding, screening and/or compressing solid active ingredients; and in the presence of at least one auxiliary agent, for example by It is prepared by intimately mixing and/or grinding the active ingredient with one or more auxiliary agents. The methods for preparing the composition and the use of compound I for preparing the composition are also the subject of the present invention.

The application methods used for the compositions (ie methods to control the above-mentioned types of pests) such as spraying, atomizing, dusting, brushing, seed dressing, sowing or watering-they are selected according to the intended purpose suitable for the general situation -And the use of these compositions to control the aforementioned types of pests are other subjects of the present invention. A typical concentration ratio is between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm of active ingredient. The application rate per common item is generally 1 g to 2000 g active ingredient per common item, particularly 10 to 1000 g/ha, preferably 10 to 600 g/ha.

In the field of crop protection, the preferred application method is to apply to the leaves of plants (foliar application). The frequency and amount of application can be selected to match the risk of infestation by the pest in question. Alternatively, it can be achieved by impregnating the site of the plant with a liquid composition or by incorporating the active ingredient in solid form into the site of the plant (for example, in the soil, for example in the form of granules (soil application)) The active ingredients reach the plant via the root system (systemic action). In the case of rice crops, such granules can be metered into flooded rice fields.

The compounds of the present invention and their compositions are also suitable for protecting plant propagation materials (for example seeds, such as fruits, tubers or kernels, or nursery plants) from the above-mentioned types of harmful organisms. The propagation material can be treated with the compound before planting, for example the seeds can be treated before sowing. Alternatively, the compound can be applied to the seed kernel (coating) by dipping the kernel into a liquid composition or by applying a layer of a solid composition. The composition is also applied when the propagation material is planted at the application site, for example, the composition is applied to the seed furrow during drilling. Such treatment methods for plant propagation material and the plant propagation material thus treated are additional subjects of the present invention. The typical treatment amount will depend on the plants to be controlled and the pests/fungi, and is generally between 1 and 200 g/100 kg of seeds, preferably between 5 and 150 g/100 kg of seeds, such as Between 10 to 100 grams/100 kg of seeds.

The term seed includes all kinds of seeds and plant propagules, including but not limited to true seeds, seed pieces, suckers, corn, corms, fruits, tubers, grains, Rhizomes, cuttings, cut shoots, etc. and in a preferred embodiment mean seedlings.

The present invention also includes seeds coated or treated with the compound of Formula I or containing the same. The term "coated or treated and/or containing it" usually means that at the time of application, the active ingredient is mainly on the surface of the seed, although more or less of the ingredient may penetrate into the seed material, depending on Method of application. When the seed product is (re)planted, it can absorb the active ingredients. In one embodiment, the present invention can provide a plant propagation material having a compound of Formula I attached thereto, and the compound of Formula I includes those selected from Tables A-1 to A-17 and Table P. In addition, a composition can thus be provided, which comprises a plant propagation material treated with a compound of formula I, and the compound of formula I includes those selected from Tables A-1 to A-17 and Table P.

Seed treatment includes all suitable seed treatment techniques known in the art, such as seed dressing, seed coating, seed dusting, seed soaking, and seed granulation. The seed treatment application of the compound of formula I (including those selected from Tables A-1 to A-17 and Table P) can be carried out by any known method, such as spraying the seeds before sowing or during sowing/planting seeds Or dusting. Biological Examples: Example B1: Activity against Spodoptera exigua (Egyptian cotton leafworm)

The cotton leaf discs were placed on agar in a 24-well microtiter plate and sprayed with an aqueous test solution prepared from a 10'000 ppm DMSO stock solution. After drying, the leaf discs were infested with five L1 stage larvae. Three days after infection, the samples were evaluated for mortality, antifeedant effect, and growth inhibition compared to untreated samples. When at least one of these categories (mortality, antifeedant effect, and growth inhibition) is higher than that of the untreated sample, the control of the test sample against Spodoptera exigua is given.

The following compounds produced at least 80% control at an application rate of 200 ppm: P1, P3, P4, P5, P6, P7, P8, P9, P10. Activity against diamondback moth (Plutella xylostella) (Plutella xylostella (Diamond back moth)): Example B2

A 24-well microtiter plate with artificial diet was processed by pipetting with an aqueous test solution prepared from a 10'000 ppm DMSO stock solution. After drying, the plates are infested with L2 stage larvae (10 to 15 per well). Five days after infection, the samples were evaluated for mortality and growth inhibition compared to untreated samples.

The following compounds gave at least 80% effects in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm: P1, P2, P3, P4, P5, P6, P7, P8, P9, P10. Example B3: Activity against cucumber leaf beetle (corn rootworm)

The corn sprouts placed on the agar layer in a 24-well microtiter plate were treated by spraying with an aqueous test solution prepared from a 10'000 ppm DMSO stock solution. After drying, the plates are infested with L2 stage larvae (6 to 10 per well). Four days after infection, the samples were evaluated for mortality and growth inhibition compared to untreated samples.

The following compounds gave at least 80% effect in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm: P1, P2, P3, P4, P6, P7, P8, P9, P10, P11. Example B4: Activity against green peach aphid (green peach aphid)

The sunflower leaf discs were placed on agar in a 24-well microtiter plate and sprayed with an aqueous test solution prepared from a 10'000 ppm DMSO stock solution. After drying, the leaf discs are infested with aphids of mixed age. After 6 days after infection, the samples were evaluated for mortality.

The following compounds produced at least 80% mortality at an application rate of 200 ppm: P1, P2, P3, P4, P5, P6, P7, P8, P9, P10, P11. Example B5: Activity against green peach aphid (green peach aphid)

The roots of pea seedlings infested by aphids populations of mixed ages were directly placed in an aqueous test solution prepared from a 10'000 DMSO stock solution. The samples were evaluated for mortality 6 days after the seedlings were placed in the test solution.

The following compounds produced at least 80% mortality at 24 ppm tested: P1, P2, P3, P4, P5, P6, P7, P9, P10. Example B6: Activity against Bemisia tabaci (Cotton whitefly)

The cotton leaf discs were placed on agar in a 24-well microtiter plate and sprayed with an aqueous test solution prepared from a 10'000 ppm DMSO stock solution. After drying, the leaf discs are infested with adult whiteflies. After 6 days of culture, the samples were checked for mortality.

The following compounds produced at least 80% mortality at an application rate of 200 ppm: P1, P2, P3, P4, P5, P6, P7, P9, P10, P11. Example B7: Activity against Euschistus heros (neotropical brown stink bug)

Soybean leaves on agar in a 24-well microtiter plate were sprayed with an aqueous test solution prepared from a 10'000 ppm DMSO stock solution. After drying, the leaves were infested with N-2 stage nymphs. Five days after infection, the samples were evaluated for mortality and growth inhibition compared to untreated samples.

The following compounds gave an effect of at least 80% in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm: P1, P2, P3, P4, P6, P7, P9, P11. Example B8: Activity against Frankliniella occidentalis (Western flower thrips)

The sunflower leaf discs were placed on agar in a 24-well microtiter plate and sprayed with an aqueous test solution prepared from a 10'000 DMSO stock solution. After drying, the leaf discs were infested with a population of thrips of mixed age. The samples were evaluated for mortality 7 days after infection.

The following compounds produce at least 80% mortality at an application rate of 200 ppm: P7, P9, P11. Activity against diamondback moth (Plutella xylostella) (Plutella xylostella (Diamond back moth)): Example B9

A 24-well microtiter plate with artificial diet was processed by pipetting with an aqueous test solution prepared from a 10'000 ppm DMSO stock solution. After drying, the Plutella eggs were pipetted through a plastic stencil onto the gel blotting paper and the plate was sealed with it. After 8 days after infection, the samples were evaluated for mortality and growth inhibition compared to untreated samples.

The following compounds gave at least 80% effect in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm: P11. Example B10: Activity against two-spotted spider mite ( Tetranychus urticae ) (Two-spotted spider mite)

Bean leaf discs on agar in a 24-well microtiter plate were sprayed with an aqueous test solution prepared from a 10'000 ppm DMSO stock solution. After drying, the leaf discs are infested with a population of mites of mixed age. After 8 days of infection, the samples were evaluated for mortality in the mixed population (active phase).

The following compounds produced at least 80% mortality at an application rate of 200 ppm: P1, P11. Example B11: Activity against Nilaparvata lugens (Brown plant hopper)

The rice plants are treated in a spray chamber with the diluted test solution. After drying, the plants were infected with about 20 N3 stage nymphs. Seven days after the treatment, the adults were taken out and 15 days after the treatment, the samples were evaluated for the effect on the F1 generation.

The following compounds produce at least 80% mortality at an application rate of 50 ppm: P1, P2, P3, P9. Example B12: Activity against Nilaparvata lugens (Brown plant hopper)

The rice plants cultivated in the nutrient solution are treated with the diluted test solution that enters the nutrient cultivation system. One day after application, the plants were infested with about 20 N3 stage nymphs. After 7 days after infection, the samples were evaluated for mortality and growth regulation.

The following compounds produced at least 80% mortality at an application rate of 12.5 ppm: P1, P2, P3, P6, P7, P9. Example B13: Activity against beet cyst nematode ( Heterodera schachtii ) (in vitro analysis of larval activity in a 96-well plate)

A TECAN robot was used to prepare test solutions from 10'000 ppm DMSO stock solutions to obtain 20 µL of 500 ppm, 100 ppm, 50 ppm, 25 ppm, 12.5 ppm, and 6.25 ppm. Three replicas are produced for each concentration. Add 80 µL of nematode solution to each well, which contains 100 to 150 newly harvested second stage larvae of beet cyst nematodes. The plate was covered and stored in the dark at room temperature and incubated for 48 hours. An imaging tool was used to measure the activity of the exposed larvae in the treated wells and compared to the average of 12 untreated replicas.

The following compounds achieve at least 60% control after 48 h at 100 ppm: P2, P3, P9. Example B14: Activity against Melodoigyne incognita (in vitro analysis of larval activity in 96-well plates)

A TECAN robot was used to prepare test solutions from 10'000 ppm DMSO stock solutions to obtain 20 µL of 1000 ppm, 200 ppm, 100 ppm, 50 ppm, 25 ppm and 12.5 ppm. Three replicas are produced for each concentration. Add 80 µL of nematode solution to each well, which contains 100 to 150 newly harvested second stage larvae of Meloidogyne incognita. The plate was covered and stored in the dark at room temperature and incubated for 48 hours. An imaging tool was used to measure the activity of the exposed larvae in the treated wells and compared with the average of 12 untreated replicas.

The following compound achieved at least 60% control after 48 h at 200 ppm: P9.

no

no

Claims (20)

A compound of formula (I),

(I), wherein A is CH or N; R ₁ is C ₁ -C ₄ alkyl; R ₇ and R ₈ are independently of each other hydrogen, halogen or C ₁ -C ₆ alkyl; R ₉ is hydrogen or C ₁ -C ₄ alkyl; R ₁₀ is hydrogen, cyano, -C(O)R ₂₅ , -C(O)OR ₂₆ or C ₁ -C ₆ alkyl; R ₂₅ is hydrogen, C ₁ -C ₆ alkyl Or C ₁ -C ₆ haloalkyl; R ₂₆ is C ₁ -C ₆ alkyl or C ₁ -C ₆ haloalkyl; n is 0 or 1; Q is a group selected from the following group consisting of Composition: formula Q ₁ to Q ₅

The arrow indicates the attachment point to the ring incorporating the group A; and wherein X ₁ is O, S or NR ₃ ; R ₃ is a C ₁ -C ₄ alkyl group; R ₂ is a halogen, C ₁ -C ₆ Haloalkyl, C ₁ -C ₄ haloalkylsulfanyl, C ₁ -C ₄ haloalkylsulfinyl, C ₁ -C ₄ haloalkylsulfinyl or C ₁ -C ₆ haloalkoxy; G ₁ and G ₂ is N or CH independently of each other; R ₄ is C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₃ -C ₆ cycloalkyl or C ₁ -C ₄ alkoxy; or these compounds One of the agrochemically acceptable salts, stereoisomers, enantiomers, tautomers or N-oxides. The compound described in item 1 of the scope of patent application, wherein A is CH or N; R ₁ is ethyl, propyl or isopropyl; preferably ethyl R ₁₀ is hydrogen, cyano or -C(O ) R ₂₅ , wherein R ₂₅ is C ₁ -C ₂ haloalkyl; preferably hydrogen R ₉ is hydrogen, methyl or ethyl; preferably hydrogen or methyl; and n is 1. The compound described in item 1 of the scope of the patent application, wherein Q is a group selected from Q ₁ , Q ₂ and Q ₅

Wherein the arrow indicates the attachment point to the ring incorporating the group A; and where R ₂ is a C ₁ -C ₂ fluoroalkyl group, a trifluoromethylsulfinyl group, a trifluoromethylsulfinyl group, and a trifluoromethyl group. Methylsulfonyl, difluoromethylsulfinyl, difluoromethylsulfinyl, or difluoromethylsulfinyl; X ₁ is NCH ₃ ; R ₃ is methyl; R ₄ is methyl, Ethyl, 2,2,2-trifluoroethyl, methoxy or cyclopropyl; and G ₁ and G ₂ are N or CH independently of each other. The compound described in item 3 of the scope of patent application, wherein R ₂ is trifluoromethyl, pentafluoroethyl, trifluoromethylsulfinyl, trifluoromethylsulfinyl or trifluoromethylsulfinyl ; X ₁ is NCH ₃ ; R ₃ is methyl; R ₄ is ethyl, methoxy or cyclopropyl; and G ₁ is N and G ₂ is CH, or G ₁ is CH and G ₂ is N, or Both G ₁ and G ₂ are N. The compound of formula I as described in item 1 of the scope of patent application, which is represented by the compound of formula I-1

(I-1); Wherein R ₁ , R ₂ , R ₃ , R ₇ , R ₈ , R ₉ , R ₁₀ , A and n are as defined in formula I in item 1 of the scope of patent application. The compound of formula I as described in item 1 of the scope of patent application, which is represented by the compound of formula I-2

(I-2); wherein R ₁ , R ₂ , R ₃ , R ₇ , R ₈ , R ₉ , R ₁₀ , A and n are as defined in formula I in item 1 of the scope of patent application. The compound of formula I as described in item 1 of the scope of the patent application, which is represented by the compound of formula I-3

(I-3) Wherein R ₁ , R ₂ , R ₃ , R ₇ , R ₈ , R ₉ , R ₁₀ , A and n are as defined in formula I in item 1 of the scope of patent application. The compound of formula I as described in item 1 of the scope of patent application, which is represented by the compound of formula I-4

(I-4) Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₇ , R ₈ , R ₉ , R ₁₀ , A and n are as defined in formula I in item 1 of the scope of patent application. The compound of formula I as described in item 1 of the scope of the patent application, which is represented by the compound of formula I-5

(I-5) Wherein R ₁ , R ₂ , R ₇ , R ₈ , R ₉ , R ₁₀ , A and n are as defined in formula I in item 1 of the scope of patent application. The compound of formula I as described in item 1 of the scope of patent application, which is represented by the compound of formula I-6

(I-6) Wherein R ₁ , R ₂ , R ₇ , R ₈ , R ₉ , R ₁₀ , A and n are as defined in formula I in item 1 of the scope of patent application. The compound of formula I as described in item 1 of the scope of patent application, which is represented by the compound of formula I-7

(I-7) Wherein R ₁ , R ₂ , R ₇ , R ₈ , R ₉ , R ₁₀ , A and n are as defined in formula I in item 1 of the scope of patent application. The compound of formula I as described in item 1 of the scope of the patent application, which is represented by the compound of formula I-8

(I-8) Wherein R ₁ , R ₂ , R ₇ , R ₈ , R ₉ , R ₁₀ , A and n are as defined in formula I in item 1 of the scope of patent application. The compound of formula I as described in item 1 of the scope of the patent application, which is represented by the compound of formula I-9

(I-9) Wherein R ₁ , R ₂ , R ₇ , R ₈ , R ₉ , R ₁₀ , A and n are as defined in formula I in item 1 of the scope of patent application. The compound of formula I as described in item 1 of the scope of the patent application, which is represented by the compound of formula I-10

(I-10) where R ₁ , R ₂ , R ₇ , R ₈ , R ₉ , R ₁₀ , A and n are as defined in formula I in item 1 of the scope of patent application. The compound of formula I as described in any one of items 5-14 of the scope of the patent application, wherein A is CH or N, preferably A is N; R ₁ is ethyl, propyl or isopropyl; Preferably, it is ethyl; R ₂ is trifluoromethyl, pentafluoroethyl or trifluoromethyl sulfanyl; preferably R ₂ is trifluoromethyl; R ₇ is hydrogen, methyl or ethyl, Preferably, it is methyl; R ₈ is methyl or ethyl, preferably methyl; R ₉ and R ₁₀ are both hydrogen; n is 1; and in formula I-1, I-2, I-3 In the case of the compound of, and I-4: R ₃ is methyl; and in the case of the compound of formula I-4: R ₄ is ethyl or cyclopropyl. The compound of formula I as described in item 1 of the scope of patent application, the compound is selected from the group consisting of: 2-[[5-(Ethylsulfonylimino)-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3- Pyridyl]oxy]-2-methyl-propionitrile (compound P1); 2-[[5-(Ethylsulfonylimino)-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]ta𠯤-6-yl]-3 -Pyridyl]oxy]-2-methyl-propionitrile (compound P2); 2-[[5-(Ethylsulfonylimino)-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3- Pyridyl]oxy]-2-methyl-propionitrile (compound P3); 2-[[5-(Ethylsulfonylimino)-2-methyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine-2- Yl]-3-pyridyl]oxy]-2-methyl-propionitrile (compound P4); 2-[[5-(Ethylsulfonylimino)-2-methyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine-2- Yl]-3-pyridyl]oxy]-2-methyl-propionitrile (compound P5); 2-[[6-[5-Ethyl-3-methyl-4- pendant oxy-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-5-( (Ethylsulfonylimino)-3-pyridyl]oxy]-2-methyl-propionitrile (compound P6); 2-[[6-[5-Cyclopropyl-3-methyl-4- pendant oxy-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-5- (Ethylsulfonylimino)-3-pyridyl]oxy]-2-methyl-propionitrile (compound P7); 2-[[5-(Ethylsulfonylimino)-6-[7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-3-pyridyl]oxy ]-2-methyl-propionitrile (compound P8); 2-[[5-(Ethylsulfonylimino)-6-[7-(1,1,2,2,2-pentafluoroethyl)imidazo[1,2-c]pyrimidine-2- Yl]-3-pyridyl]oxy]-2-methyl-propionitrile (compound P9); 2-[[5-(Ethylsulfonylimino)-6-[7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-2-yl]-3-pyridinyl]oxy ]-2-methyl-propionitrile (compound P10); and 2-[[5-(Ethylsulfonylimino)-6-[7-(trifluoromethylsulfanyl)imidazo[1,2-c]pyrimidin-2-yl]-3-pyridyl ]Oxy]-2-methyl-propionitrile (compound P11). A pesticidal composition comprising as an active ingredient at least one in free form or in the form of agrochemically usable salt as an active ingredient such as any one of items 1-16 in the scope of patent application The compound of formula I or its tautomers, as defined in item 1, and at least one auxiliary agent. A method for preventing and controlling pests, the method comprises adding a pesticidal effective amount of a compound of formula I as defined in any one of the scope of patent application 1-16 or as described in item 17 of the scope of patent application The composition is applied to pests, pest sites or plants vulnerable to pest attack. A method for protecting plant propagation material from harmful organisms, the method comprising treating the propagation material or the place where the propagation material is grown with the composition as described in item 17 of the scope of the patent application. A compound of formula XXXVI,

(XXXVI) wherein R ₁ , R ₇ , R ₈ , R ₉ and A are as defined in formula I above, and R ₁₀₀ is OH, chlorine or C ₁ -C ₄ alkoxy.