TW201625522A - Imidazopyridazine compound or salts thereof and agricultural and horticultural insecticide containing said compound and method of using same - Google Patents

Abstract

The purpose of the present invention is to develop and provide an agricultural and horticultural insecticide that is novel in terms of factors such as the occurrence of pests resistant to existing chemicals and the like because significant damage still occurs due to pests and the like in crop production such as agriculture and horticulture; provided are an imidazopyridazine compound represented by general formula (I) {in the formula, A1, A2, A3, or A4 may be the same or different and represent a nitrogen atom or CH group, R1 represents an alkyl group, R2 represents an alkyl group, R3 represents a haloalkyl group, R4 represents a hydrogen atom, Z represents a haloalkyl group or the like, A represents S, SO, SO2, S=N-R5group, or S(O)=N-R5 group, and n represents 1.} or salts thereof, an agricultural and horticultural insecticide having the same as an active ingredient, and a method of use thereof.

Description

Imidazolium compound or salt thereof, agricultural and horticultural insecticide containing same, and use method thereof

The present invention relates to novel imidazolium A pesticide for agricultural and horticultural use of a compound or a salt thereof as an active ingredient, and a method of using the same.

Various compounds have been studied as insecticides for agricultural and horticultural use, and some fused heterocyclic compounds have been reported to be useful as insecticides (see, for example, Patent Documents 1 to 6). Imidazolium is not disclosed in the relevant literature. a compound composed.

Prior technical literature Patent literature

Patent Document 1 Japanese Patent Laid-Open Publication No. 2009-280574

Patent Document 2 Japanese Patent Laid-Open Publication No. 2010-275301

Patent Document 3 Japanese Patent Laid-Open Publication No. 2011-79774

Patent Document 4 Japanese Patent Laid-Open Publication No. 2012-131780

Patent Document 5 International Publication No. 2012/086848

Patent Document 6 International Publication No. 2013/018928

In the production of crops such as agriculture and horticulture, the damage caused by pests and the like is still large, and the main factors such as the production of pests resistant to existing agents, and a novel agricultural and horticultural insecticide is expected. Development of agents that reduce toxicity.

In order to solve the above problems, the inventors of the present invention have found that the imidazolium represented by the general formula (I) is found. The compound or a salt thereof has an excellent control effect against agricultural and horticultural pests, and has reduced toxicity to organisms other than the control target, and completed the present invention.

That is, the present invention relates to: [1] an imidazolium represented by the general formula (I) a compound or a salt thereof, Wherein R ¹ represents (a1)(C ₁ -C ₆ )alkyl, (a2)(C ₂ -C ₆ )alkenyl, (a3)(C ₂ -C ₆ )alkynyl, (a4)( C ₃ -C ₆ )cycloalkyl or (a5)(C ₃ -C ₆ )cycloalkyl(C ₁ -C ₆ )alkyl; R ² represents (b1) hydrogen atom, (b2) (C ₁ -C ₆ ) alkyl, (b3) (C ₂ -C ₆ )alkenyl, (b4)(C ₂ -C ₆ )alkynyl, (b5)(C ₃ -C ₆ )cycloalkyl or (b6)(C _3- C ₆ )cycloalkyl(C ₁ -C ₆ )alkyl; R ³ represents (c1)(C ₁ -C ₆ )alkyl, (c2)(C ₁ -C ₆ )alkoxy, (c3 Halogen (C ₁ -C ₆ )alkyl, (c4)halo(C ₁ -C ₆ )alkoxy, (c5)(C ₁ -C ₆ )alkylthio, (c6)(C ₁ -C ₆ Alkylsulfinyl, (c7) (C ₁ -C ₆ ) alkanesulfonyl, (c8) halo(C ₁ -C ₆ )alkylthio, (c9)halo(C ₁ -C ₆ ) alkane Sulfonyl or (c10) halo(C ₁ -C ₆ ) alkanesulfonyl; R ⁴ represents (d1) a hydrogen atom, (d2) a halogen atom, (d3) a cyano group, a (d4) nitro group, (d5) (C ₁ -C ₆ )alkyl or (d6)(C ₁ -C ₆ )alkoxy; A represents S, SO, SO ₂ , S=NR ⁵ group, or S(O)=NR ⁵ group (this Wherein R ⁵ represents (e1) a hydrogen atom, (e2) a cyano group, (e3) (C ₁ -C ₆ ) alkylcarbonyl group, (e4) a halogen (C ₁ -C ₆ ) alkylcarbonyl group, (e5) benzenesulfonate The group or (e6) having the same or different ring on the ring is selected from the group consisting of (a) a halogen atom (b) cyano, (c) nitro, (d) (C ₁ -C ₆ )alkyl, (e) halo(C ₁ -C ₆ )alkyl, (f)(C ₁ -C ₆ ) Alkoxy and (g) _1-5 phenylsulfonyl groups of the group of (C ₁ -C ₆ ) alkoxy groups; A ¹ , A ² , A ³ and A ⁴ may be the same or Different, indicating a nitrogen atom or CH; Z may be the same or different, and represents (f1) a hydrogen atom, (f2) a halogen atom, (f3) a cyano group, a (f4) nitro group, a (f5) hydroxylamine group, and a (f6) amine group. (f7)hydroxyl, (f8)(C ₁ -C ₆ )alkyl, (f9)(C ₁ -C ₆ )alkoxy, (f10)(C ₂ -C ₆ )alkenyloxy, (f11) (C ₂ -C ₆ ) alkynyloxy, (f12)(C ₃ -C ₆ )cycloalkyl, (f13)halo(C ₁ -C ₆ )alkyl, (f14)halo(C ₁ -C ₆ ) Alkoxy, (f15) halo(C ₂ -C ₆ )alkenyloxy, (f16)halo(C ₂ -C ₆ )alkynyloxy, (f17)halo(C ₃ -C ₆ )cycloalkoxy, (f18) (C ₁ -C ₆ )alkylthio, (f19)(C ₁ -C ₆ )alkylsulfinyl, (f20)(C ₁ -C ₆ )alkylsulfonyl, (f21)halide C ₁ -C ₆ )alkylthio, (f22)halo(C ₁ -C ₆ )alkylsulfinyl or (f23)halo(C ₁ -C ₆ )alkylsulfonyl; n represents an integer from 1 to 4 }; [2] as described in [1] a compound or a salt thereof, wherein R ¹ represents (a1)(C ₁ -C ₆ )alkyl; R ² represents (b1) a hydrogen atom or (b2)(C ₁ -C ₆ )alkyl; and R ³ represents (c3) a halogen (C ₁ -C ₆ )alkyl group or (c8)halogen (C ₁ -C ₆ )alkylthio group; R ⁴ represents a (d1) hydrogen atom; A represents S, SO, SO ₂ , S=NR ⁵ group Or S(O)=NR ⁵ group (wherein R ⁵ represents (e1) a hydrogen atom; (e2) a cyano group; (e4) a halogen (C ₁ -C ₆ ) alkylcarbonyl group or (e6) has a ring on the ring The same or different ones selected from (a) a halogen atom, (b) a cyano group, (c) a nitro group, a (d) (C ₁ -C ₆ ) alkyl group, and (e) a halogen (C ₁ -C ₆ ) alkane. a group of (f)(C ₁ -C ₆ )alkoxy and (g) 1 to 5 substituents of the phenylsulfonyl group in the group of halogen (C ₁ -C ₆ )alkoxy groups; A ¹ And A ² , A ³ and A ⁴ may be the same or different and represent a nitrogen atom or CH; Z may be the same or different and represents (f1) a hydrogen atom, (f2) a halogen atom, (f4) a nitro group, (f5) a hydroxylamine group. , (f6) amine group, (f7) hydroxyl group, (f8) (C ₁ -C ₆ ) alkyl group, (f12) (C ₃ -C ₆ ) cycloalkyl group, (f13) halogen (C ₁ -C ₆ ) An alkyl group, (f14) halo(C ₁ -C ₆ )alkoxy, (f18)(C ₁ -C ₆ )alkylthio or (f21)halo(C ₁ -C ₆ )alkylthio;[3] Imidazolium as described in [1] or [2] a compound or a salt thereof, wherein A ¹ , A ² and A ³ are CH, and A ⁴ is a nitrogen atom; [4] The imidazole oxime described in any one of [1] to [3] Use of a compound or a salt thereof as an agricultural and horticultural insecticide; [5] A method for using a pesticide for agriculture and horticulture, characterized by comprising the active ingredient of the agricultural and horticultural insecticide described in [4] Treating plants or soils; [6] A method for controlling pests in agriculture and horticulture, characterized in that plants or soils are treated with an effective amount of the agricultural and horticultural insecticides described in [4]; [7] an external parasite control The imidazole oxime described in any one of [1] to [3] a compound or a salt thereof as an active ingredient; [8] A method for controlling an external parasite characterized by contacting an external parasite with an effective amount of an external parasite controlling agent described in [7]; [9] a general formula (II) Compound or its salts: Wherein R ² represents (b1) a hydrogen atom or (b2) (C ₁ -C ₆ )alkyl; R ³ represents (c9) halo(C ₁ -C ₆ )alkyl, (c4)halo (C ₁ -C ₆ ) alkoxy or (c8) halo(C ₁ -C ₆ )alkylthio; R ⁴ represents (d1) a hydrogen atom, (d2) a halogen atom, (d5) (C ₁ -C ₆ )alkyl Or (d6) (C ₁ -C ₆ ) alkoxy; R represents (g1) a hydrogen atom, (g2) a halogen atom or (g3) an amine group; [10] a group represented by the formula (III) Amine compounds or their salts: Wherein R ¹ represents (a1)(C ₁ -C ₆ )alkyl; R ² represents (b1) a hydrogen atom or (b2)(C ₁ -C ₆ )alkyl; A ¹ , A ² , A ³ And A ⁴ may be the same or different and represent a nitrogen atom or CH; Z may be the same or different and represents (f1) a hydrogen atom, (f2) a halogen atom, (f13) a halogen (C ₁ -C ₆ ) alkyl group, (f14) Halogen (C ₁ -C ₆ )alkoxy, (f21)halo(C ₁ -C ₆ )alkylthio, (f22)halo(C ₁ -C ₆ )alkylsulfinyl or (f23)halide (C) ₁ - C ₆ ) alkanesulfonyl, n represents an integer from 1 to 4.

The imidazolium of the present invention The compound or its salt has an excellent effect not only as an insecticide for agricultural and horticultural purposes, but also for insects in dogs and cats, or pests in vitro or in vivo of domestic animals such as cows and sheep.

Form for implementing the invention

Imidazolium in the present invention In the definition of the formula (I) of the compound or a salt thereof, "halogen" means "halogen atom" and means a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

"(C ₁ -C ₆ )alkyl" means, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-butyl, n-pentyl , isoamyl, third amyl, neopentyl, 2,3-dimethylpropyl, 1-ethylpropyl, 1-methylbutyl, 2-methylbutyl, n-hexyl, isohexyl Straight or branched chain such as 2-hexyl, 3-hexyl, 2-methylpentyl, 3-methylpentyl, 1,1,2-trimethylpropyl, 3,3-dimethylbutyl The alkyl group having 1 to 6 carbon atoms; "(C ₂ -C ₆ ) alkenyl" means, for example, vinyl, allyl, isopropenyl, 1-butenyl, 2-butenyl , 2-methyl-2-propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl, pentenyl, 1-hexenyl, 3,3-dimethyl-1 a linear or branched alkenyl group having 2 to 6 carbon atoms such as a butenyl group; "(C ₂ -C ₆ ) alkynyl group" means, for example, an ethynyl group, a 1-propynyl group, a 2-propene group; Alkynyl, 1-butynyl, 2-butynyl, 3-butynyl, 3-methyl-1-propynyl, 2-methyl-3-propynyl, pentynyl, 1-hexyl a linear or branched carbon atom such as an alkynyl group, a 3-methyl-1-butynyl group or a 3,3-dimethyl-1-butynyl group 2 to 6 alkynyl groups.

"(C ₃ -C ₆₎ cycloalkyl" denotes system example: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like having 3 to 6 carbon atoms of a cyclic alkyl group; on "(C ₁ - The C ₆ ) alkoxy group means, for example, a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, a second butoxy group, a third butoxy group, and a positive Pentyloxy, isopentyloxy, third pentyloxy, neopentyloxy, 2,3-dimethylpropoxy, 1-ethylpropoxy, 1-methylbutoxy, n-hexyloxy a linear or branched alkoxy group having 1 to 6 carbon atoms such as isohexyloxy or 1,1,2-trimethylpropoxy; "(C ₂ -C ₆ )alkenyloxy" , the system indicates, for example: number of 2 to 6 carbon alkenyl group of a straight-chain or branched propylene group, butylene group, pentenyl group, hexenyl group and the like atoms; on "(C ₂ -C ₆ ) alkynyl group means, for example, a straight or branched carbon atom such as propynyloxy, butynyloxy, pentynyloxy or hexynyloxy is 2 to 6 carbon atoms. Alkynyloxy.

In the case of "(C ₁ -C ₆ )alkylthio", it means, for example, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, second butylthio, Tributylthio, n-pentylthio, isopentylthio, third pentylthio, neopentylthio, 2,3-dimethylpropylthio, 1-ethylpropylthio, 1-methylbutyl carbon atoms group, n-hexyl group, isohexyl group, 1,1,2-trimethyl propyl group are straight chain or branched chain of 1 to 6 alkylthio group; on "(C ₁ -C ₆ ) alkanesulfinyl group means, for example, a sulfinyl group, an sulfinyl group, a propyl sulfinyl group, a isopropyl sulfinyl group, a n-butyl sulfinyl group, and a second Butasulfinyl, tributylsulfinyl, n-pentylenesulfonyl, isopentylsulfinyl, third sulfinyl, neopentylsulfenyl, 2,3-dimethyl Propyl sulfinyl, 1-ethylpropoxysulfonyl, 1-methylbutylsulfinyl, n-hexylsulfinyl, isohexylsulfinyl, 1,1,2-trimethylpropanesulfin a straight or branched alkylenesulfonyl group having 1 to 6 carbon atoms; and a "(C ₁ -C ₆ ) alkanesulfonyl group" means, for example, a methylsulfonyl group, Ethyl sulfonyl , n-propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, butyl sulfonyl, butyl sulfonyl, n-pentanesulfonyl, isovaleryl, third pentanesulfonate Base, neopentylsulfonyl, 2,3-dimethylpropanesulfonyl, 1-ethylpropanesulfonyl, 1-methylbutsulfonyl, n-hexylsulfonyl, isohexylsulfonyl, 1, A linear or branched alkanesulfonyl group having 1 to 6 carbon atoms such as 1,2-trimethylpropanesulfonyl.

In the above "(C ₁ -C ₆ )alkyl", "(C ₂ -C ₆ )alkenyl", "(C ₂ -C ₆ )alkynyl", "(C ₃ -C ₆ )cycloalkyl" , "(C ₁ -C ₆ ) alkoxy", "(C ₂ -C ₆ )alkenyloxy", "(C ₂ -C ₆ ) alkynyloxy", "(C ₁ -C ₆ ) alkanethio group "," (C ₁ -C ₆₎ alkyl sulfinyl group "," (C ₁ -C ₆₎ alkyl sulfonic acyl "of substitutable positions, also substituted two or more halogen atoms, When two or more halogen atoms are substituted, the halogen atoms may be the same or different.

The above "substituent having one or two or more halogen atoms substituted at a substitutable position" is represented by "halo(C ₁ -C ₆ )alkyl" or "halo(C ₂ -C ₆ )alkenyl, respectively. "Halogen (C ₂ -C ₆ ) alkynyl", "halo (C ₃ -C ₆ )cycloalkyl", "halo (C ₁ -C ₆ ) alkoxy", "halo (C ₂ -C) ₆ ) alkenyloxy", "halo(C ₂ -C ₆ )alkynyloxy", "halo(C ₁ -C ₆ )alkylthio", "halo(C ₁ -C ₆ )alkylsulfinyl) Or "halo(C ₁ -C ₆ ) alkanesulfonyl).

The expressions "(C ₁ -C ₆ )", "(C ₂ -C ₆ )", and "(C ₃ -C ₆ )" represent the range of the number of carbon atoms of various substituents. Further, the group to which the substituent is bonded may be represented by the above definition, for example, the case of "(C ₃ -C ₆ )cycloalkyl(C ₁ -C ₆ )alkyl" means a carbon number of 3~ The six cycloalkyl groups are bonded to a linear or branched alkyl group having 1 to 6 carbon atoms.

The imidazolium represented by the general formula (I) of the present invention Examples of the salts of the compounds include inorganic acid salts such as hydrochlorides, sulfates, nitrates, and phosphates; acetates, fumarates, maleates, oxalates, and methanesulfonates. An organic acid salt such as a benzenesulfonate or a p-toluenesulfonate; or a salt of an inorganic or organic base such as sodium ion, potassium ion, calcium ion or trimethylammonium.

Imidazolium represented by the general formula (I) of the present invention The compound or a salt thereof may have one or a plurality of asymmetric centers in its structural formula, and two or more optical isomers and non-image isomers may be present, and the present invention is also All optical isomers are included and those containing such mixtures are included in any ratio. Further, the compound represented by the formula (I) and a salt thereof of the present invention may also have two geometric isomers derived from a carbon-carbon double bond in the structural formula, but the present invention is also All geometric isomers are included and those containing such mixtures are included in any proportion.

In the present invention, R ¹ represents (a1)(C ₁ -C6)alkyl; R ² represents (b1) hydrogen atom or (b2)(C ₁ -C ₆ )alkyl; R ³ represents (c3) a halogen (C ₁ -C ₆ )alkyl group or (c8)halo(C ₁ -C ₆ )alkylthio group; R ⁴ represents a (d1) hydrogen atom; A represents S, SO, SO ₂ , S=NR ⁵ group, Or S(O)=NR ⁵ group (here, R ⁵ represents (e1) hydrogen atom, (e2) cyano group, (e4) halogen (C ₁ -C ₆ ) alkylcarbonyl group or (e6) has a ring The same or different ones selected from the group consisting of (a) a halogen atom, (b) a cyano group, (c) a nitro group, a (d) (C ₁ -C ₆ ) alkyl group, and (e) a halogen (C ₁ -C ₆ ) alkane. a phenylsulfonyl group of 1 to 5 substituents in the group of (f) (C ₁ -C ₆ ) alkoxy group and (g) halogen (C ₁ -C ₆ ) alkoxy group. ¹ , A ² , A ³ and A ⁴ may be the same or different and represent a nitrogen atom or CH; Z may be the same or different and represents (f1) a hydrogen atom, (f2) a halogen atom, (f4) a nitro group, (f5) a hydroxylamine. Base, (f6) amine group, (f7) hydroxyl group, (f8) (C ₁ -C ₆ ) alkyl group, (f12) (C ₃ -C ₆ ) cycloalkyl group, (f13) halogen (C ₁ -C ₆ An alkyl group, (f14) halo(C ₁ -C ₆ )alkoxy, (f18)(C ₁ -C ₆ )alkylthio or (f21)halo(C ₁ -C ₆ )alkylthio; n is 1.

Further preferably, in the present invention, R ¹ represents (a1)(C1-C ₆ )alkyl; R ² represents (b1) a hydrogen atom or (b2)(C ₁ -C ₆ )alkyl; and R ³ represents (c3) a halogen (C ₁ -C ₆ )alkyl group or (c8)halogen (C ₁ -C ₆ )alkylthio group; R ⁴ represents a (d1) hydrogen atom; A represents S, SO, SO ₂ , S=NR ⁵ group Or S(O)=NR ⁵ group (wherein R ⁵ represents (e1) hydrogen atom, (e2) cyano group, (e4) halogen (C ₁ -C ₆ ) alkylcarbonyl group or (e6) has a ring on the ring The same or different ones selected from the group consisting of (a) a halogen atom, (b) a cyano group, a (c) nitro group, a (d) (C ₁ -C ₆ ) alkyl group, and (e) a halogen (C ₁ -C ₆ ) Alkyl, (f)(C ₁ -C ₆ )alkoxy and (g) 1 to 5 substituents of the phenylsulfonyl group in the group of halogen (C ₁ -C ₆ )alkoxy groups; A ¹ , A ² and A ³ are CH; A ⁴ is a nitrogen atom; Z may be the same or different and represents (f1) a hydrogen atom, (f2) a halogen atom, (f4) a nitro group, (f5) a hydroxylamine group, (f6) Amine, (f7) hydroxy, (f8) (C ₁ -C ₆ )alkyl, (f12)(C ₃ -C ₆ )cycloalkyl, (f13)halo(C ₁ -C ₆ )alkyl, ( F14) halo(C ₁ -C ₆ )alkoxy, (f18)(C ₁ -C ₆ )alkylthio or (f21)halo(C ₁ -C ₆ )alkylthio; n is 1.

The imidazolium of the present invention The compound or a salt thereof can be produced, for example, by the following production method, but the present invention is not limited thereto.

Manufacturing method 1

In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , A ¹ , A ² , A ³ , A ⁴ , Z, and n are the same as defined above, X represents a halogen atom, and m represents 0 to 2 An integer, m1 represents 0 or 1}.

Manufacturing method of step [a]

The hydrazine amide compound represented by the formula (III-1) and the hydrazine represented by the formula (II-1) The compound is reacted in the presence of a metal catalyst, a base and an inert solvent to produce a carboxylic acid guanamine compound represented by the formula (IV-1). This reaction can be carried out according to the method described in the literature (Org. Synth. 78:23,; Org. Synth. Coll. Vol. 10: 423, JACS (1999), 121 (18), 4369-4378).

As the metal catalyst which can be used in the present invention, [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride, [1,1'-bis(diphenylphosphine) can be cited. Propane]palladium dichloride, [1,1'-bis(diphenylphosphino)butane]palladium dichloride, bis(dibenzylideneacetone)palladium, ginseng (dibenzylideneacetone) Palladium, palladium acetate, palladium chloride, bis(acetonitrile) palladium dichloride, bis(benzonitrile)palladium dichloride, allyl palladium chloride dimer, cyclopentadienylallyl palladium, etc. A well-known palladium catalyst. Further, two or more of these may be used as needed. The amount of the palladium catalyst to be used in the present invention is usually selected in the range of from about 0.001 to about 0.1 moles per mole of the carboxylic acid amide compound represented by the formula (III-1). . When palladium acetate, palladium chloride or the like is used, a known ligand such as triphenylphosphine or Xantphos may be used in combination.

The inert solvent to be used in the reaction may be an aromatic hydrocarbon such as benzene, toluene or xylene, or a halogenated aromatic hydrocarbon such as chlorobenzene or dichlorobenzene, as long as it does not significantly hinder the progress of the reaction. Class; diethyl ether, methyl tertiary butyl ether, two Chain or cyclic ethers such as alkane, tetrahydrofuran and 2-methyltetrahydrofuran; esters such as ethyl acetate; decylamines such as dimethylformamide and dimethylacetamide; ketones such as acetone and methyl ethyl ketone; An inert solvent such as a polar solvent such as dimethyl sulfonium or 1,3-dimethyl-2-imidazolidinone may be used alone or in combination of two or more.

Examples of the base which can be used in the present invention include hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; lithium carbonate, lithium hydrogencarbonate, sodium carbonate, sodium hydrogencarbonate, potassium carbonate, and potassium hydrogencarbonate; a carbonate such as cesium carbonate; Acetate such as lithium acetate, sodium acetate or potassium acetate; alkoxide such as sodium methoxide, sodium ethoxide or potassium t-butoxide; metal hydride such as sodium hydride or potassium hydride; pyridine, pyrithion, lutidine, and tri An organic base such as ethylamine, tributylamine or diisopropylethylamine. The amount of the base to be used may be appropriately selected from the range of 0.5 times by mole to 5.0 times the molar amount of the compound represented by the formula (III-1). The dehydration condensation reaction for the next step may also be carried out in this manufacturing step as the case may be, and the next step is omitted.

Manufacturing method of step [b]

Imidazolium represented by the formula (I-3) The compound can be produced by reacting a carboxylic acid amide compound represented by the formula (IV-1) in the presence of a condensing agent, a base and an inert solvent.

As the condensing agent used in the reaction, for example, diethyl phosphorocyanidate (DEPC), carbonyldiimidazole (CDI), 1,3-dicyclohexylcarbodiimide can be exemplified. (dicyclohexyl carbodiimide) (DCC), chlorocarbonic ester, 2-chloro-1-methylpyridinium iodide, etc., and the amount thereof is as long as expressed by the formula (IV-1) The carboxylic acid amide compound is preferably used in a range of from 1 to 2 moles per mole.

Examples of the alkali include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, and potassium hydrogencarbonate; acetates such as sodium acetate and potassium acetate; and third butanol. Potassium, sodium methoxide, sodium ethoxide Alkali metal alkoxides; tertiary amines such as triethylamine, diisopropylethylamine, 1,8-diazabicyclo[5.4.0]undec-7-ene; pyridine, dimethylamino A nitrogen-containing aromatic compound such as pyridine is used in an amount of usually 1 to 8 moles per mole of the carboxylic acid amide compound represented by the formula (IV-1).

The inert solvent to be used in the reaction may be an aromatic hydrocarbon such as benzene, toluene or xylene as long as it does not significantly hinder the progress of the reaction; methane chloride, chloroform, carbon tetrachloride Halogenated hydrocarbons; halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene; diethyl ether, methyl tertiary butyl ether, Chain or cyclic ethers such as alkane and tetrahydrofuran; esters such as ethyl acetate; decylamines such as dimethylformamide and dimethylacetamide; ketones such as acetone and methyl ethyl ketone; An inert solvent such as a polar solvent such as 1,3-dimethyl-2-imidazolidinone may be used alone or in combination of two or more.

Since this reaction is an equimolar reaction, it is only necessary to use each reaction agent in the form of a molar, but any of the reactants may be used excessively. The reaction temperature can be carried out from the room temperature to the boiling point range of the inert solvent to be used, and the reaction time is not fixed depending on the reaction scale and the reaction temperature, but it can be carried out in the range of several minutes to 48 hours.

After the reaction is completed, the target product may be separated from the reaction system containing the target product by a usual method such as: dissolution, concentration, distillation, crystallization, etc., by using recrystallization, column chromatography, if necessary. The object is purified by a method or the like to produce a target.

Manufacturing method of step [c]

This reaction can be carried out by using the imidazolium represented by the formula (I-3) The compound is reacted with an oxidizing agent in an inert solvent to produce an imidazolium represented by the formula (I-1). Compound.

The oxidizing agent used in the reaction may, for example, be a peroxide such as hydrogen peroxide water, peroxybenzoic acid or m-chloroperoxybenzoic acid. These oxidizing agents may be in the form of imidazolium represented by the formula (I-3). The compound is suitably selected in the range of 0.8 to 5 moles, but preferably in the range of 1 to 2 moles.

The inert solvent which can be used in the present reaction is not particularly limited as long as it does not significantly hinder the reaction, and examples thereof include diethyl ether, tetrahydrofuran, and Chain or cyclic ethers such as alkane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as chlorinated methane, chloroform and carbon tetrachloride; halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene; Nitriles; esters such as ethyl acetate; organic acids such as formic acid and acetic acid; N,N-dimethylformamide, N,N-dimethylacetamide, 1,3-dimethyl-2- A polar solvent such as imidazolinone or water may be used alone or in combination of two or more.

The reaction temperature in the reaction may be appropriately selected from the range of from -10 ° C to the reflux temperature of the inert solvent to be used. The reaction time varies depending on the reaction scale, the reaction temperature, and the like, and is not fixed, but may be appropriately selected in the range of several minutes to 48 hours. After the reaction, the target The reaction system containing the target product can be isolated by a usual method such as conversion, concentration, distillation, or crystallization, and can be purified by recrystallization or column chromatography as needed. Things.

Manufacturing method of step [d]

The reaction system can be obtained by using the imidazolium represented by the formula (I-3) The compound, the oxidizing agent in an inert solvent and the amine represented by R ⁵ NH ₂ are as described in the literature (Synthesis 2000, 1, 1; J. Chem. Soc. Chem. Commun. 1983, 329; J. Am .Chem. Soc. 1967, 89, 1959; Tetrahedron Lett. 1998, 39, 4805; Tetrahedron Lett. 1998, 39, 5015; J. Org. Chem. 1974, 39, 2458; Tetrahedron Lett. 2002, 43, 2749; Organic Letters 2004, 6, 1305; Organic Letters 2005, 7, 4983; Tetrahedron Lett. 2005, 46, 8007) to produce imidazolium represented by the general formula (I-2) Compound.

Examples of the oxidizing agent used in the reaction include peroxides such as iodobenzene diacetate, hydrogen peroxide water, peroxybenzoic acid, and m-chloroperoxybenzoic acid. These oxidizing agents may be in the form of imidazolium represented by the formula (I-3). The compound is suitably selected in the range of 0.8 to 5 moles, but preferably in the range of 1 to 2 moles.

The inert solvent which can be used in the present reaction is not particularly limited as long as it does not significantly hinder the reaction, and examples thereof include diethyl ether, tetrahydrofuran, and Chain or cyclic ethers such as alkane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as chlorinated methane, chloroform and carbon tetrachloride; halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene; Nitriles; esters such as ethyl acetate; organic acids such as formic acid and acetic acid; N,N-dimethylformamide, N,N-dimethylacetamide, 1,3-dimethyl-2- A polar solvent such as imidazolinone or water may be used alone or in combination of two or more.

Since this reaction is an equimolar reaction, it is only necessary to use each reaction agent in the form of a molar, but any of the reactants may be used excessively. The reaction temperature can be carried out from the room temperature to the boiling point range of the inert solvent to be used, and the reaction time is not fixed depending on the reaction scale and the reaction temperature, but it can be carried out in the range of several minutes to 48 hours.

The reaction temperature in the reaction may be appropriately selected from the range of from -10 ° C to the reflux temperature of the inert solvent to be used. The reaction time varies depending on the reaction scale, the reaction temperature, and the like, and is not fixed, but may be appropriately selected in the range of several minutes to 48 hours. After the reaction is completed, the target product may be separated from the reaction system containing the target product by a usual method such as: dissolution, concentration, distillation, crystallization, etc., by using recrystallization, column chromatography, if necessary. The object is purified by a method or the like to produce a target.

Further, the compound of the present invention can be produced by the method exemplified below.

Manufacturing method 2

In the formula, R ¹ , R ² , R ³ , R ⁴ , A ¹ , A ² , A ³ , A ⁴ , Z and n are the same as defined above, and X represents a halogen atom}.

Manufacturing method of step [e]

By using the carboxylic acid compound represented by the formula (III-2) and the hydrazine represented by the formula (II-2) The compound is reacted in the presence of a condensing agent, a base and an inert solvent to produce a carboxylic acid guanamine compound represented by the formula (IV-2).

As the condensing agent used in the reaction, for example, diethyl cyanophosphate (DEPC), carbonyl diimidazole (CDI), 1,3-dicyclohexylcarbodiimide (DCC), chlorocarbonate can be exemplified. , iodinated 2-chloro-1-methylpyridinium, etc., and used in an amount of 1 to 2 times as much as 1.5 moles relative to the carboxylic acid amide compound represented by the formula (III-2) The range of the ear can be selected and used.

Examples of the base include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, and potassium hydrogencarbonate; and acetic acid; Acetate salts such as sodium and potassium acetate; alkali metal alkoxides such as potassium butoxide, sodium methoxide and sodium ethoxide; triethylamine, diisopropylethylamine and 1,8-diazabicyclo[5.4. 0] a tertiary amine such as eleven-7-ene; a nitrogen-containing aromatic compound such as pyridine or dimethylaminopyridine, and the like, and the amount thereof is based on the compound represented by the formula (III-2). Usually used in the range of 1x mole to 10x mole.

The inert solvent to be used in the reaction may be an aromatic hydrocarbon such as benzene, toluene or xylene as long as it does not significantly hinder the progress of the reaction; methane chloride, chloroform, carbon tetrachloride Halogenated hydrocarbons; halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene; diethyl ether, methyl tertiary butyl ether, Chain or cyclic ethers such as alkane and tetrahydrofuran; esters such as ethyl acetate; decylamines such as dimethylformamide and dimethylacetamide; ketones such as acetone and methyl ethyl ketone; An inert solvent such as a polar solvent such as 1,3-dimethyl-2-imidazolidinone may be used alone or in combination of two or more.

Since this reaction is an equimolar reaction, it is only necessary to use each reaction agent in the form of a molar, but any of the reactants may be used excessively. The reaction temperature can be carried out from the room temperature to the boiling point range of the inert solvent to be used, and the reaction time is not fixed depending on the reaction scale and the reaction temperature, but it can be carried out in the range of several minutes to 48 hours. After the reaction is completed, the target product may be separated from the reaction system containing the target product by a usual method such as: dissolution, concentration, distillation, crystallization, etc., by using recrystallization, column chromatography, if necessary. The object is purified by a method or the like to produce a target.

Manufacturing method of step [b]

This reaction can be produced in the same manner as the production method described in the step [b] of the production method 1.

Manufacturing method of step [f]

By using the imidazolium represented by the general formula (V) The imidazole oxime represented by the formula (I-3) is produced by reacting a compound with a thiol compound represented by the formula (VI) in the presence of a base in an inert solvent. Compound.

Examples of the base which can be used in the reaction include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydrogencarbonate, and potassium hydrogencarbonate; sodium hydride and potassium hydride; Anhydrous alkali metal; an alkoxide such as sodium methoxide, sodium ethoxide or potassium butoxide. The amount of the base to be used is usually in the range of usually 1 to 5 moles per mole of the compound represented by the formula (V). Further, commercially available sodium thiomethoxide or sodium ethanethiolate may be used, and in this case, the compound (VI) may not be used.

The inert solvent which can be used in the present reaction is not particularly limited as long as it does not significantly hinder the reaction, and examples thereof include alcohols such as methanol, ethanol, propanol, butanol, and 2-propanol; and diethyl ether. Tetrahydrofuran, two Chain or cyclic ethers such as alkane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as chlorinated methane, chloroform and carbon tetrachloride; halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene; Nitriles; esters such as ethyl acetate; N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl hydrazine, 1,3-dimethyl-2-imidazole A polar solvent such as ketone or the like may be used alone or in combination of two or more.

The reaction temperature in the reaction may be carried out usually from about 0 ° C to the boiling point of the solvent to be used, and the reaction time is not fixed depending on the reaction scale and the reaction temperature, but is suitably selected in the range of several minutes to 48 hours. can. The compound represented by the formula (VI) is an imidazolium represented by the formula (V). The compound is used in a range of usually about 1 to 5 moles. Further, the reaction can also be carried out in a gas atmosphere such as an inert gas such as nitrogen or argon. After the reaction is completed, the target product may be separated from the reaction system containing the target product by a usual method such as: dissolution, concentration, distillation, crystallization, etc., by using recrystallization, column chromatography, if necessary. The object is purified by a method or the like to produce a target.

The imidazolium represented by the formula (I-3) produced by the method of the production method 2 The compound can be used for the imidazolium represented by the formula (I-1) or (I-2) according to the method described in the production method 1. Manufacture of compounds.

The raw material substance or intermediate of the present invention can be produced, for example, by the following method.

Intermediate manufacturing method

[Wherein, R ^2, R ³ and R ⁴ with the same system, X represents a halogen atom].

The general formulae (II-1) and (II-2) for producing an intermediate of the compound of the present invention can be produced by the following method.

First, iodine represented by the general formula (II-5) produced by the method described in the literature (Tetrahedron 1999, 55, 15067) can be obtained. Compounds and alkyl iodides in the presence of metal catalysts, bases and inert solvents according to the methods described in the literature (Organic Synthetic Chemistry Association Vol.69 No. 7 2011; Chem. Rev. 2011, 4475; WO 2013/018928 In the specification), a cross-coupling reaction is carried out to produce a crucible represented by the general formula (II-4) Compound.

For the catalyst which can be used in the reaction, a palladium compound such as a zero-valent or a divalent palladium metal or a salt (including a complex) which can be used can be used, and the catalyst can be supported on activated carbon or the like. Palladium (0) / carbon, palladium (II) acetate, palladium (II) chloride, bis (triphenylphosphine) palladium (II) chloride, ruthenium (triphenylphosphine) are preferred examples of the palladium compound to be used. Palladium (0) and the like.

The reaction may also be carried out by adding a ligand. Examples of the ligand include triphenylphosphine (PPh ₃ ), methyl diphenylphosphine (Ph ₂ PCH ₃ ), trifurylphosphine (P(2-furyl) ₃ ), and tris(orthofuryl). Phosphine (P(o-tol) ₃ ), tris(cyclohexyl)phosphine (PCy ₃ ), dicyclohexylphenylphosphine (PhPCy ₂ ), tris(tert-butyl)phosphine (P ^t Bu ₃ ), 2 , 2'-bis(diphenylphosphino)-1,1'-binaphthyl (BINAP), diphenylphosphinoferrocene (DPPF), 1,1'-bis(di-tertiary butylphosphine Ferrocenyl (D ^t BPF), N,N-dimethyl-1-[2-(diphenylphosphino)ferrocenyl]ethylamine, 1-[2-(diphenylphosphino) a phosphine mimic ligand such as ferrocene-methylether, Xantphos or the like; or a phosphine mimic ligand such as an imidazole-2-ylidene carbene (refer to the Applied Chemistry Journal International Edition (Angewandte Chemie International Edition) In English) Vol. 36, p. 2163 (1997)).

Examples of the base which can be used in the present invention include hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; lithium carbonate, lithium hydrogencarbonate, sodium carbonate, sodium hydrogencarbonate, potassium carbonate, and potassium hydrogencarbonate; Carbonate such as cesium carbonate; acetate such as lithium acetate, sodium acetate or potassium acetate; alkoxide such as sodium methoxide, sodium ethoxide or potassium t-butoxide; metal hydrides such as sodium hydride and potassium hydride; pyridine and pyridyl, An organic base such as lutidine, triethylamine, tributylamine or diisopropylethylamine. The amount of the base to be used may be appropriately selected as long as it is in the range of from 1 mol to 5.0 mol per mol of the compound represented by the formula (II-5).

The reaction temperature in the reaction may be carried out usually from about 0 ° C to the boiling point of the solvent to be used, and the reaction time is not fixed depending on the reaction scale and the reaction temperature, but is suitably selected in the range of several minutes to 48 hours. can.

By the formula (II-4) The compound is reacted with an amine compound (R ² NH ₂ ) to produce an amine group represented by the formula (II-3). .

The inert solvent to be used in the reaction may be an aromatic hydrocarbon such as benzene, toluene or xylene as long as it does not significantly hinder the progress of the reaction; methane chloride, chloroform, carbon tetrachloride Halogenated hydrocarbons; halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene; diethyl ether, methyl tertiary butyl ether, Chain or cyclic ethers such as alkane and tetrahydrofuran; esters such as ethyl acetate; decylamines such as dimethylformamide and dimethylacetamide; ketones such as acetone and methyl ethyl ketone; An inert solvent such as a polar solvent such as 1,3-dimethyl-2-imidazolidinone may be used alone or in combination of two or more.

The base may be used as needed. Examples of the alkali include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, and potassium hydrogencarbonate; sodium acetate, potassium acetate, and the like. Acetate; alkali metal alkoxides such as potassium t-butoxide, sodium methoxide, sodium ethoxide; triethylamine, diisopropylethylamine, 1,8-diazabicyclo[5.4.0] eleven- a tertiary amine such as 7-ene; a nitrogen-containing aromatic compound such as pyridine or dimethylaminopyridine; The amount thereof to be used is usually in the range of 1 to 8 moles per mole of the compound represented by the formula (II-4).

The reaction temperature in the reaction may be appropriately selected from the range of from -10 ° C to the reflux temperature of the inert solvent to be used. The reaction time varies depending on the reaction scale, the reaction temperature, and the like, and is not fixed, but may be appropriately selected in the range of several minutes to 48 hours. The amine compound (R ² NH ₂ ) can be expressed relative to the formula (II-4) The compound is suitably selected in the range of 1 mole to 5 moles.

After the reaction is completed, the target product may be separated from the reaction system containing the target product by a usual method such as: dissolution, concentration, distillation, crystallization, etc., by using recrystallization, column chromatography, if necessary. The object is purified by a method or the like to produce a target.

By using the amine group represented by the formula (II-3) The compound is reacted with a halogenating agent to produce a hydrazine represented by the formula (II-1) Compound.

The inert solvent which can be used in the present reaction is not particularly limited as long as it does not significantly hinder the reaction, and examples thereof include alcohols such as methanol, ethanol, propanol, butanol, and 2-propanol; and diethyl ether. Tetrahydrofuran, two Chain or cyclic ethers such as alkane; aromatic hydrocarbons such as benzene, toluene and xylene; esters such as ethyl acetate; N,N-dimethylformamide, N,N-dimethylacetamide, A polar solvent such as 1,3-dimethyl-2-imidazolidinone, water, or acetic acid may be used alone or in combination of two or more.

Examples of the halogenating agent to be used in the reaction include halogen molecules of chlorine, bromine and iodine; halogenated amber imines such as NCS and NBS; and DBDMH (1,3-dibromo-5,5-dimethyl). Ethyl halides such as carbendazim, DIH, etc.; thiol chloride;

The reaction temperature in the reaction may be appropriately selected from the range of from -30 ° C to the reflux temperature of the inert solvent to be used. The reaction time varies depending on the reaction scale, the reaction temperature, and the like, and is not fixed, but may be appropriately selected in the range of several minutes to 48 hours.

After the reaction is completed, the target product may be separated from the reaction system containing the target product by a usual method such as: dissolution, concentration, distillation, crystallization, etc., by using recrystallization, column chromatography, if necessary. The object is purified by a method or the like to produce a target.

By using the halogen hydrazine represented by the general formula (II-1) The compound is reacted with ammonia in the presence of a copper catalyst and a solvent to produce an amine hydrazine. Compound (II-2).

As the inert solvent which can be used in the present reaction, as long as the progress of the reaction is not significantly inhibited, examples thereof include alcohols such as methanol, ethanol, propanol, butanol, and 2-propanol; benzene and toluene; , aromatic hydrocarbons such as xylene; halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene; diethyl ether, methyl tertiary butyl ether, Chain or cyclic ethers such as alkane and tetrahydrofuran; decylamines such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone; dimethyl sulfoxide and 1,3-dimethyl An inert solvent such as benzyl-2-imidazolidinone may be used alone or in combination of two or more. As the copper catalyst used in the reaction, copper oxide, copper bromide, copper chloride or the like can be used. The amount used may be relative to the hydrazine represented by the formula (II-1). The compound is suitably selected in the range of 1 mole to 5 moles.

The reaction temperature in the reaction may be appropriately selected from the range of from -10 ° C to the reflux temperature of the inert solvent to be used. The reaction time varies depending on the reaction scale, the reaction temperature, and the like, and is not fixed, but may be appropriately selected in the range of several minutes to 48 hours. The ammonia system can be expressed in relation to the hydrazine represented by the formula (II-1) The compound is suitably selected in the range of 1 mole to 5 moles. Further, in order to carry out the reaction efficiently, an autoclave can be used.

After the reaction is completed, the target product may be separated from the reaction system containing the target product by a usual method such as: dissolution, concentration, distillation, crystallization, etc., by using recrystallization, column chromatography, if necessary. The object is purified by a method or the like to produce a target.

Next, specific examples of the compound of the present invention are shown below. In the following table, Me represents a methyl group, Et represents an ethyl group, c-Pr represents a cyclopropyl group, and c-Pent represents a cyclopentyl group. The physical property shows a melting point (° C.), or an NMR data or a refractive index (measured temperature).

Imidazolium represented by the general formula (I) of the present invention An agricultural and horticultural insecticide containing a compound or a salt thereof as an active ingredient, and is suitable for pests such as various agricultural, forestry, horticultural, grain-retaining pests or sanitary pests or nematodes which are harmful to rice, fruit trees, vegetables, other crops and flowers. Prevention and treatment.

The following are exemplified as the above-mentioned pests or nematodes.

Examples of the Lepidoptera pest include, for example, Parasa consocia, Anomis mesogona, Papilio xuthus, Matsumuraeses azukivora, and brown winged rods. Ostrinia scapulalis, Spodoptera exempta, Hyphantria cunea, Ostrinia furnacalis, Pseudaletia separata, Tinea translucens, small winged wings Bactra furfurana, Parnara guttata, Marasmia exigua, Parnara guttata, large Es (Sesamia inferens), Brachmia triannulella, Monema flavescens, Trichoplusia ni, Pleuroptya ruralis, Cystidia couaggaria, Lampides boeticus, Cephonodes hylas, Helicoverpa armigera, Phalerodonta manleyi, Eumeta japonica, and Pieris brassicae , Malacosoma neustria testacea, Stathmopoda masinissa, Cuphodes diospyrosella, Archiples xylosteanus, Agrotis segetum, Tetramoera Schistaceana), Papilio machaon hippocrates, Endoclyta sinensis, Lyonetia prunifoliella, Phyllonycter ringoneella, Cydia kurokoi , Eucoenogenes aestuosa, Lobesia botrana, Latoia sinica, Euzophera bat Angensis), Phalonidia mesotypa, Spilosoma imparilis, Glyphodes pyloalis, Olethreutes mori, Tineola bisselliella, bat moth (Endoclyta excrescens), Nemapogon granellus, Synanthedon hector, Cydia pomonella, Plutella xylostella, Cnaphalocrocis medinalis, Africa Es (Sesamia calamistis), Scirpophaga incertulas, Pediasia teterrellus, Phthorimaea operculella, Stauropus fagi persimilis, Etiella zinckenella, beet armyworm (Spodoptera exigua), Palpifer sexnotata, Spodoptera mauritia, Scirpophaga innotata, Xestia c-nigrum, Spodoptera depravata , Ephestia kuehniella, Angerona prunaria, Clostera anastomosis, Pseudoplusia includens, Matsumuraeses falcana, Tobacco moth (Helicoverpa assulta) ), Autographa nigrisigna, Agrotis ipsilon, Euproctis pseudoconspersa, Adoxophyes orana, Caloptilia theivora, Homona magnanima, Ephestia elutella, Eumeta minuscula, Clostera anachoreta, and Spodoptera litura (H) Eliothis maritima), Sparganothis pilleriana, Busseola fusca, Euproctis subflava, Biston robustum, Heliothis zea , Aedia leucomelas, Narosoideus flavidorsalis, Viminia rumicis, Bucculatrix pyrivorella, Grapholita molesta, Spulerina astaurota Pear (Ectomyelois pyrivorella), Chilo suppressalis, Acrolepiopsis sapporensis, Plodia interpunctella, Hellula undalis, Sitotroga cerealella, Spodoptera litura ), Eucosma aporema, Acleris comariana, Scopelodes contractus, Orgyia thyellina, Spodoptera frugiperda, 仟Ostrinia zaguliaevi, Naranga aenescens, Andraca bipunctata, Paranthrene regalis, Acosmeryx castanea, Phyllocnistis toparcha, vines Moth (Endopiza viteana), Eupocelilla ambiguella, Anticarsia gemmatalis, Cnephasia cinereipalpana, Lymantria dispar, Dendrolimus spectabilis, Leguminivora glycinivorella, Maruca testulalis, Matsumuraeses phaseoli, Caloptilia soyella, Phyllocnistis citrella, Omiodes indicata, Archips fuscocupreanus, Acanthoplusia agnata, and moth Bambalina sp.), Carposina niponensis, Conogethes punctiferalis, Synanthedon sp., Lyonetia clerkella, Papilio Helenus) Yellow butterfly (Colias erate poliographus), Phalera flavescens, Pieris rapae crucivora, Pieris rapae, etc., Euproctis similis, Acrolepiopsis suzukiella ), Ostrinia nubilalis, Mamestra brassicae, Ascotis selenaria, Phtheochroides clandestina, Hoshinoa adumbratana, Odonestis Pruni japonensis), Triaena intermedia, Adoxophyes orana fasciata, Grapholita inopinata, Spironota ocellana, Spironota lechriaspis , Illiberis pruni, Argyresthia conjugella, Caloptilia zachrysa, Archips breviplicanus, Anomis flava, Red worm (Pectinophora) Gossypiella), Notarcha derogata, Diaphania indica, Heliothis vire Scens), and Daria point tumor moth (Earias cupreoviridis).

Examples of the Hemiptera pest include, for example, Nezara antennata, Stenotus rubrovittatus, Graphosoma rubrolineatum, and Trigonotylus coelestialium. Etc., Aeschynteles maculatus, red star blind (Creontiades pallidifer), Dysdercus cingulatus, Chrysomphalus ficus, Aonidiella aurantii, Graptopsaltria nigrofuscata, Blissusleucopterus, Icerya purchasi, Piezodorus hybneri, Lagynotomus elongatus, Thaia subrufa, Scotinophara lurida, Sitobion ibarae, Iwasaki Stariodes iwasakii), Aspidiotus destructor, Taylorilygus pallidulus, Myzusmumecola, Pseudaulacaspis prunicola, Acyrthosiphon pisum, and whisker (Anacanthocoris striicornis), Ectometopterus micantulus, Eysarcoris lewisi, Molipteryx fuliginosa, Cicadella viridis, Rhopalosophum rufiabdominalis, hard ridge Scaletis oleae, greenhouse whitefly (Trialeurodes vaporariorum), oak leaf bee (Aguriah Ana quercus), Lygus spp., Euceraphis punctipennis, Andaspis kashicola, Coccus pseudomagnoliarum, Caveretius saccharivorus, leaves Galeatus spinifrons, Macrosiphoniella sanborni, Aonidiella citrina, Halyomorpha mista, Stephanitis fasciicarina, Trioza Camphorae), Leptocorisa chinensis, Trioza quercicola, Uhlerites latius, Erythroneura comes, Paromius exiguus, Tamarix Duplaspidiotus claviger, Nephotettix nigropictus, Halticiellus insularis, Perkinsiella saccharicida, Psylla malivorella, Anomomeura Mori), Pseudococcus longispinis, Pseudaulacaspis pentagona, Pulvinaria kuwacola, Apolygus lucorum, Togo hemipterus, Toxoptera Aurantii), Saccharicoccus sacchari, Geoica lucifuga, Numata muiri, Comstockaspis perniciosa, Unaspis citri, Potato 蚜(Aulacorthum solani), Eysarcoris ventralis, Bemisia argentifolii, Cicadella spectra, Aspidiotus hederae, Liorhyssus hyalinus, Calophya nigridorsalis, Sogatella furcifera, Megoura crassicau da, rapeseed (Brevicoryne brassicae), Aphis glycines, Leptocorisa oratorius, Nephotettix virescens, Uroeucon formosanum, Tobacco blind Like (Cyrtopeltis tennuis), Bemisia tabaci, Lecanium persicae, Parlatoria theae, Pseudaonidia paeoniae, Daguan small green leafhopper Empoasca onukii), Plautia stali, Dysaphis tulipae, Macrosiphum euphorbiae, Stephanitis pyrioides, Ceroplastes ceriferus, Camellia Shield Parlatoria camelliae, Apolygus spinolai, Nephotettix cincticeps, Glaucias subpunctatus, Orthotylus flavosparsus, Rhopalosiphum maidis , Peregrinus maidis, Eysarcoris parvus, Cimex lectularius, Psylla abieti, Nilaparvata lugens, Psylla tobirae, wrinkles (Eurydema rugosum), Schizaphis piricola, Psylla pyricola, Parlatoreopsis pyri, pear Stephanitis nashi, Dysmicoccus wistariae, Lepholeucaspis japonica, Sappaphis piri, Lipaphis erysimi, Neotoxoptera formosana, Rhopalosophum nymphaeae, Edwardsianarosae, Pinnaspisaspidistrae, Psylla alni, A. arborescens (Speusotettix) Subfusculus), Alnetoidia alneti, Sogatella panicicola, Adelphocoris lineolatus, Dysdercus poecilus, Parlatoria ziziphi, brown shoulder net Uhlerites debile, Laodelphax striatella, Eurydema pulchrum, Cletus trigonus, Clovia punctata, Empoasca sp. , Coccus hesperidum, Pachybrachius luridus, Planococcus kraunhiae, Stenotus binotatus, Arboridia apicalis, Aster (Macrosteles fascifrons), Dolycoris baccarum, Adelphocoris triannulatus, Viteus vitifolii, Acanthocoris sordidus, Leptocorisa acuta, Tumor Macropes obnubilus, Cletus punctiger, Riptortus clavatus, Paratrioza cockerelli, Willow Aphrophora costalis, Lygus disponsi, Lygus saundersi, Crisicoccus pini, Emppoasca abietis, Crisicoccus matsumotoi ), Aphis craccivora, Megacopta punctatissimum, Eysarcoris guttiger, Oyster scale insect (Lepidosaphes) Beckii), Diaphorina citri, Toxoptera citricidus, Planococcus citri, Dialeurodes citri, Aleurocanthus spiniferus, Citrus powder shell Pseudococcus citriculus, Zyginella citri, Pulvinaria citricola, Coccus discrepans, Pseudaonidia duplex, Pulvinaria aurantii , Lecanium corni, Nezara viridula, Stenodema calcaratum, Rhopalosiphum padi, Sitobion akebiae, Mai bifurcation Schizaphis graminum), Sorhoanus tritici, Brachycaudus helichrysi, Carpocoris purpureipennis, Myzus persicae, Hyalopterus pruni, Amaranth pear Subspecies (Aphis farinose yanagicola), Metasalis populi, Unaspis yanonensis, Mesohomotoma camphorae, Aphis spiraec Ola), Aphis pomi, Lepidosaphes ulmi, Psylla mali, Heterocordylus flavipes, Myzus malisuctus, apple claw cotton Aphidonuguis mali, Orientus ishidai, Ovatus malicolens, Eriosoma lanigerum, Ceroplastes rubens, and Aphis gossypii.

Examples of Coleoptera pests include Xystrocera globosa, Paederus fuscipes, Eucetonia roelofsi, Callosobruchus chinensis, and sweet potato ant elephants. (Cylas formicarius), Hypera postica, Echinocnemus squameus, Oulema oryzae, Donacia provosti, Rice water weevil (Lissorhoptrus oryzophilus ), Colasposoma dauricum, Euscepes postfasciatus, Epilachna varivestis, Acanthoscelides obtectus, Diabrotica virgifera virgifera, Li Huxiang ( Involvulus cupreus), Aulacophora femoralis, Bruchus pisorum, Epilachna vigintioctomaculata, Carpophilus dimidiatus, Cassida nebulosa, rough back bristles Luperomorpha tunebrosa, Phyllotreta striolata, Psacothea hilaris, Taiwan Macular Mountain Aeolesthes chrysothrix, Curculio sikkimensis, Carpophilus hemipterus, Oxycetonia jucunda, Diabrotica spp., Mimela splendens, Sitophilus zeamais, Tribolium castaneum, Sitophilus oryzae, Palorus subdepressus, Melolontha japonica, star Anoplophora malasiaca, Neatus picipes, Leptinotarsa decemlineata, Diabrotica undecimpunctata howardi, Sphenophorus venatus, fourteen-spot narrow neck Flower worm (Crioceris quatuordecimpunctata), Conotrachelus nenuphar, Ceuthorhynchidius albosuturalis, Phaedon brassicae, Lasioderma serricorne, Sitona japonicus , Adoretus tenuimaculatus, Tenebrio molitor, Basilepta balyi, Hypera nigrirostris, Chaetocnema concinna, Bronze Anomala cuprea, Heptophylla picea, Epilachna vigintioctopunctata, Diabrotica longicornis, Eucetonia pilifera, Agriotes spp. , Artagenus unicolor japonicus, Pagria signata, Soybean red turtle (An Omala rufocuprea), Palorus ratzeburgii, Alphitobius laevigatus, Anthrenus verbasci, Lyctus brunneus, Tribolium confusum, black barley Medythia nigrobilineata, Xylotrechus pyrrhoderus, Epitrix cucumeris, Tomicus piniperda, pine spotted days Bovine (Monochamus alternatus), Japanese porpoise (Popillia japonica), Epicauta gorhami, Sitophilus zeamais, Rhynchites heros, Listroderes costirostris, four-grain bean (Callosobruchus maculatus), Phylbolius armatus, Anthonomus pomorum, Linaeidea aenea, and Anthonomus grandis.

Examples of the Diptera pest include Culex pipiens pallens, Pegomya hyoscyami, Liriomyza huidobrensis, Musca domestica, and rice straw. Chlorops oryzae, Hydrellia sasakii, Agromyza oryzae, Hydrellia griseola, Hydrellia griseola, Ophiomyia phaseoli , Drosophila (Dacus cucurbitae), Drosophila suzukii, Japanese cherry fruit fly (Rhacochlaena japonica), Muscina stabulans, Megaselia spiracularis, etc. Phoridae), Clogmia albipunctata, Tipula aino, Phormia regina, Culex tritaeniorhynchus, Anopheles sinensis, Hylemya brassicae , Asphondylia sp., Delia platura, Delia antiqua, Rhagoletis cerasi, Culex pipiens molestus Forskal, Ceratitis capitata, Bradysia agrestis, Pegomya cunicularia , Liriomyza sativae, Liriomyza bryoniae, Chromatomyia horticola, Liriomyza chinensis, Culex quinquefasciatus, Aedes aegypti ), Aedes albopictus, Liriomyza trifolii, Liriomyza sativae, Dacus dorsalis, Dacus tsuneonis, and wheat red-sucking worm ( Sitodiplosis mosellana), Meromuza nigriventris, Anastrepha ludens, and Rhagoletis pomonella.

Examples of the Hymenoptera pest include, for example, Pristomyrmex pungens, Bethylidae, Monomorium pharaonis, Pheidole noda, and red. Athalia rosae, Dryocosmus kuriphilus, Formica fusca japonica, Vespinae, Athalia infumata, Arde Pagana), Athalia japonica, Acromyrmex spp., Solenopsis spp., Arge mali, and Ochetellus glaber.

Examples of the Orthoptera pest include, for example, the southern rice straw (Homorocoryphus lineosus), the genus Gryllotalpa sp., the Oxya hyla intricata, the Oxya yezoensis, and the oriental migratory locust. (Locusta migratoria), Oxya japonica, Homorocoryphus jezoensis, and Teleogryllus emma.

Examples of the Thysanoptera pest include, for example, Selenothrips rubrocinctus, Stenchaethrips biformis, Haplothrips aculeatus, Ponticulothrips diospyrosi, and pale colors. Thrips flavus, Anaphothrips obscurus, Liothrips floridensis, Thrips simplex, Thrips nigropilosus, variegated pheasant Heliothrips haemorrhoidalis), Pseudodendrothrips mori, Microcephalothrips abdominalis, Leeuwenia pasanii, Litotetothrips pasaniae, Scirtothrips citri, Chinese hummer Haplothrips chinensis), Mycterothrips glycines, Thrips setosus, Scirtothrips dorsalis, Dendrothrips minowai, Haplothrips niger ), Thrips tabaci, Thrips alliorum, Thrips hawaiiensis, Beans and Horses (Haplothrips kurdjumovi), Chirothrips manicatus, Frankliniella intonsa, Thrips coloratus, Franklinella occidentalis, Thrips palmi, Lily 蓟Horse (Frankliniella lilivora) and Lithrips vaneeckei.

Examples of the Acarina pest include, for example, Leptotrombidium akamushi, Tetranychus ludeni, Dermacentor variabilis, Tetranychus truncatus, and Berth Ornithonyssus bacoti, Demodex canis, Tetranychus viennensis, Tetranychus kanzawai, Rhipicephalus sanguineus, etc. (Ixodidae) , Cheyletus malaccensis, Tyrophagus putrescentiae, Dermatophagoides farinae, Latrodectus hasseltii, Dermacentor taiwanicus, Acaphylla theavagrans, Polyphagotarsonemus latus, Aculops lycopersici, Ornithonyssus sylvairum, Tetranychus urticac, Eriophyes chibaensis, Brevipalus Sp.), Sarcoptes scabiei, Haemaphysalis longicornis, Ixodes scapularis, Tyrophagus (Tyrophagus similis), Cheyletus eruditus, Panonychus citri, Cheyletus moorei, Brevipalpus phoenicis, Octodectes cynotis, Dermatophagoides ptrenyssnus, brown Haemaphysalis flava, Ixodes ovatus, Phyllocoptruta citri, Aculus schlechtendali, Panonychus ulmi, Amblyomma americanum And Dermanyssus gallinae, Rhizoglyphus robini, one of Sancassania sp.

Examples of the Isoptera pest include, for example, Reticulitermes miyatakei, Incisitermes minor, Coptotermes formosanus, Hodotermopsis japonica, and Termites ( Reticulitermes sp.), Reticulitermes flaviceps amamianus, Glyptotermes kushimensis, Coptotermes guangzhoensis, Neotermes koshunensis, Glyptotermes kodamai, Glyptotermes Satsumensis), Cryptotermes domesticus, Odontotermes formosanus, Glyptotermes nakajimai, Pericapritermes nitobei, and Reticulitermes speratus.

Examples of the insects of the genus Blattaria include, for example, Periplaneta fuliginosa, Blattella germanica, Blatta orientalis, Periplaneta brunnea, and Forked Flycatcher. (Blattella lituricollis), Japanese cockroach (Periplaneta japonica), and American cockroach (Periplaneta americana).

Examples of the Siphonaptera include Pulex irritans, Ctenocephalides felis, and Ceratophyllus gallinae.

Examples of the nematode include: Nothotylenchus acris, Aphelenchoides besseyi, Pratylenchus penetrans, Meloidogyne hapla, Meloidogyne incognita, and golden nematode (Globodera rostochiensis), Meloidogyne javanica, Heterodera glycines, Pratylenchus coffeae, Pratylenchus neglectus, and Tylenchus semipenetrans )Wait.

Examples of mollusks (Mollusca) include: Pomacea canaliculata, Achatina fulica, Meghimatium bilineatum, and Valencia Lennon. (Lehmannina valentiana), Astragalus (Limax flavus), and Acusta despecta sieboldiana.

Further, the agricultural and horticultural insecticide of the present invention is also a potent insecticidal effect against the other pests of the genus Tapa absoluta.

Further, as an animal parasitic cockroach which is one of the objects to be controlled, for example, Boophilus microplus, Rhipicephalus sanguineus, Haemaphysalis longicornis, and brown blood scorpion ( Haemaphysalis flava), Haemaphysalis campanulata, Haemaphysalis concinna, Haemaphysalis japonica, Haemaphysalis kitaokai, Haemaphysalis ias, eggs Ixodes ovatus, Ixodes nipponensis, Ixodes persulcatus, Amblyomma testudinarium, Haemaphysalis megaspinosa, Dermacentor reticulatus ), and Ixodidae of Dermacentor taiwanesis, such as Dermanyssus gallinae, Ornithonyssus sylviarum, and tropical locust (Ornithonyssus bursa), such as apple locusts, Eutrombicula wichmanni, Leptotrombidium akamushi, Leptotrombidium pallidum, Fuji (Le Ptotrombidium fuji), Leptotrombidium tosa, Neotrombicula autumnalis, North American (Eutrombicula alfreddugesi), and the genus of Helenicula miyagawai, such as Cheyletiella yasguri, Cheyletiella parasitivorax, and Cheyletiella blakei Cheyletidae, such as Psoroptes cuniculi, Chorioptes bovis, Otodectes cynotis, Sarcoptes scabiei, and Notoedres Cati), and Demodicidae such as Demodex canis.

Examples of the other object to be controlled by the present invention include an external parasitic wingless insect belonging to the genus Siphonaptera, and more specifically, it belongs to the genus Pulicidae and the European cockroach (Ceratephyllus) and the like. For fleas belonging to the genus Aphididae, for example, Ctenocephalides canis, Ctenocephalides felis, Pulex irritans, Echidnophaga gallinacea, Xenopsylla cheopis ), Leptopsylla segnis, Nosopsyllus fasciatus, and Monopsyllus anisus.

Further, for the external parasites of other animals to be controlled, for example, Haematopinus eurysternus, Haematopinus asini, Dalmalinia ovis, and long-nosed calf (Linognathus vituli) may be mentioned. ), piglet (Haematopinus) Suis), Phthirus pubis, and Anoplura of Pediculus capitis, and Mallophaga such as Trichodectes canis, such as Tabanus trigonus, sharp scorpion Ciliicoides schultzei, and the blood-sucking Diptera pests of Simulium ornatum. Further, as for the internal parasite of the animal, for example, a nematode such as a lungworm, a whipworm, a nodular worm, a stomach parasite, a mites, and a filamentous worm, such as a mites , Aphis gossypii, melon aphids, polychaetes, aphids, and aphids of multi-atrial hydatid, such as schistosomiasis in Japan, and trematodes of the liver, and coccidia, malaria parasites Intestinal fungus, Toxoplasma gondii, and protozoa of Cryptosporidium.

Further, it is clear from the above that the compound of the present invention can not only repel agricultural and horticultural pests, but also widely removes sanitary pests.

Since the imidazolium represented by the general formula (I) of the present invention The agricultural and horticultural insecticide containing the compound or its salt as an active ingredient has a significant control effect on the aforementioned pests which are harmful to paddy crops, dry crops, fruit trees, vegetables, other crops and flowers, and is in accordance with the predicted The period during which the pests are produced, and the cultivation of seedlings, paddy fields, dry fields, fruit trees, vegetables, other crops, flowers, seeds, paddy water, stems, leaves, soil, etc. before the pests are produced or confirmed. The cultivation carriers and the like are treated to achieve the desired effects of the agricultural and horticultural insecticides of the invention. In addition, the seedling soil of crops, flowers, etc., the planting soil at the time of transplantation, the roots of the plants, the irrigation water, the cultivation water of the hydroponic cultivation, etc. are treated so that the roots are absorbed from the roots via or without the soil. The so-called osmotic mobility application of the inventive compound is a preferred mode of use.

A useful plant which can use the agricultural and horticultural insecticide of the present invention is not particularly limited, but examples thereof include cereals (for example, rice, barley, wheat, rye, oats, corn, etc.), and beans (soybeans, Red beans, broad beans, peas, kidney beans, groundnuts, etc.), fruit trees/fruits (apples, citrus, pears, grapes, peaches, plums, cherries, walnuts, chestnuts, almonds, bananas, etc.), leaves/fruits (cabbage, tomatoes) , spinach, broccoli, lettuce, onion, shallots (fine chives, green onions), green peppers, eggplant, strawberries, peppers, okra, leeks, etc.), root vegetables (carrots, potatoes, sweet potatoes, taro, radish, turnips, Lotus root, burdock, garlic, taro, etc., processed for use (cotton, hemp, leeks, hops, sugar cane, beets, olives, rubber, coffee, tobacco, tea, etc.), melons (pumpkin, gherkin, watermelon, oriental Melon, cantaloupe, etc., pasture (orchard grass, sorghum, steppe grass, clover, alfalfa, etc.), dwarf grass (Gorley, Bentgrass, etc.), spices, etc. Appreciation (lavender, rosemary, thyme , celery, pepper Ginger, etc.), flowers (juju, rose, carnation, orchid, tulip, lily, etc.), garden trees (ginkgo, cherry, aoki, etc.), trees (Abiessachalinensis, Piceajezoensis, Plants such as pines, arborvitae, cedar, eucalyptus, eucalyptus, etc.).

The above-mentioned "plants" also include the use of traditional breeding methods to give different HPPD inhibitors such as isoxaflutole; ALS inhibitors such as imazethapyr and Thifensulfuronmethyl; EPSP synthetase inhibitors such as jiaphos; glutamate synthase such as chlorpyrifos Inhibitors; acetaminophen coenzyme A carboxylase inhibitors such as chlorpyrifos; plants resistant to herbicides such as bromoxynil, ricket, 2,4-D, etc., or have been endowed by genetic recombination techniques Resistant plant.

As an example of a "plant" to which resistance is imparted by a conventional breeding method, there is a rapeseed which is resistant to an imidazolinone ALS-inhibiting herbicide such as imazethapyr. Wheat, sunflower and rice, and rice has been sold under the trade name Clearfield (registered trademark). Soybeans which are resistant to sulfonylurea ALS-inhibiting herbicides such as Thifensulfuronmethyl by conventional breeding methods are commercially available under the trade name STS soybean. An example of a plant which is endowed with resistance to an acetamidine coenzyme A carboxylase inhibitor such as trione oxime or aryloxyphenoxypropionic acid herbicide by a conventional breeding method. There are SR corn and so on.

Further, a plant which is rendered resistant to an acetamyl CoA carboxylase inhibitor is described in Proceedings of the National Academy of Sciences of the United States of America (Proc. Natl. Acad. Sci. USA), 87. Volume, 7175-7179 (1990) and so on. Further, the variant acetamyl coenzyme A carboxylase which is resistant to the acetaminophen coenzyme A carboxylase inhibitor has been reported in WeedScience, Vol. 53, pp. 728-746 (2005), etc. Introducing the variant acetamidine coenzyme A carboxylase gene into a plant by genetic recombination technology, or The resistance-related variation is introduced into the plant's acetaminophen coenzyme A carboxylase, thereby producing a plant resistant to the acetaminophen coenzyme A carboxylase inhibitor, and further, by introducing a representative in the plant cell Introducing a nucleic acid into a base substitution mutation of a chimeraplasty technique (Gura T. 1999. Repairing the Genome's Spelling Mistakes. Science 285: 316-318.), and introducing it into a plant such as an acetaminophen coenzyme A carboxylase gene or an ALS gene. The specific amino acid substitution mutation is made into a plant resistant to an acetaminophen coenzyme A carboxylase inhibitor or an ALS inhibitor, and the agricultural and horticultural insecticide of the present invention can also be used for such plants.

Further, as the toxin expressed by the genetically recombinant plant, an insecticidal protein derived from Bacillus cereus or Bacillus popilliae; Cry1Ab and Cry1Ac derived from Bacillus thuringiensis can be cited. Δ -endotoxin such as Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C; insecticidal proteins such as VIP1, VIP2, VIP3 or VIP3A: insecticidal proteins derived from nematodes; scorpion toxin, spider toxin, melittin or insect specificity Neurotoxins and other toxins produced by animals; filamentous toxoids; plant lectins; lectins; trypsin inhibitors; serine protease inhibitors; patatin, cystatin, papain Protease inhibitors such as (Papain) inhibitors; Ricin, corn-RIP, Abrin, Rufin, Saporin, and diarrhea protein Bryodin) and other ribosome-inactivating proteins (RIP); 3-hydroxysteroid oxidase, ecdysteroid-UDP-glucosyltransferase, cholesterol oxidation And other steroid metabolic enzymes; Ecdysone inhibitor; HMG-CoA reductase; sodium channel, calcium channel inhibitor and other ion channel inhibitors; juvenile hormone esterase; diuretic hormone receptor; stilbene synthesis Enzyme; bibenzyl synthase; chitinase; glucanase (glucanase) and the like.

Moreover, as a toxin expressed by such a genetically recombinant plant, a δ-endotoxin protein such as Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1, Cry9C, Cry34Ab or Cry35Ab is also included; VIP1, VIP2, VIP3 or VIP3A are killed. Hybrid toxin; partially deficient toxin; modified toxin. Mixed toxins are made using recombinant techniques by a new combination of different domains of such proteins. For some defective toxins, Cry1Abs lacking a partial amino acid sequence are known. In the case of a modified toxin, one or more amino acids of the natural toxin are substituted.

Examples of such toxins and recombinant plants which can synthesize such toxins are described in EP-A-0 374 753, WO 93/07278, WO 95/34656, EP-A-0 427 529, EP-A-451 878 WO 03/052073.

The toxins contained in such recombinant plants confer resistance to plants, especially to the species Coleoptera, Hemiptera, Diptera, Lepidoptera, and Nematodes. The agricultural and horticultural insecticides of the present invention can be used in combination with such techniques or systemized.

The agricultural and horticultural insecticide of the present invention is used for controlling various pests, directly or by water or the like, or suspended in the form of water, for use in plants which are expected to have the production of the pest and nematode. For pests or nematodes, it is effective to control pests and nematodes such as in fruit trees, cereals, vegetables, etc., in addition to spreading on stems and leaves, seeds may be immersed in chemicals, seed coating, Seed treatment such as Calper treatment, soil full-layer mixing, planting row application, bed soil mixing, cell seedling treatment, planting point treatment, plant root treatment, top dressing, rice box treatment, water surface application, etc. The soil is treated to absorb it from the roots. In addition, it may be used by application of a nutrient solution in a culture (hydroponic) cultivation, smoking, or trunk injection.

Furthermore, the agricultural and horticultural insecticide of the present invention is directly or diluted with water or the like, or suspended in the form of water, and the pest control is used in a place where the pest is expected to be produced. The effective amount may be used in addition to, for example, storage of pests, house pests, sanitary pests, forest pests, etc., as well as coating, smoking, bait, etc. of building materials.

The method of the seed treatment may, for example, be a method in which a liquid or solid preparation is diluted or not diluted to impregnate a seed in a liquid state to infiltrate the agent; and the solid preparation or the liquid preparation is mixed with the seed and coated. A method of adhering to the surface of the seed, a method of mixing with an adhesive carrier such as a resin or a polymer, and applying it to the seed; a method of spreading the seed in the vicinity of the seed at the same time as the planting.

The "seed" of the seed treatment refers to a plant body in the initial stage of cultivation used for plant propagation, and examples of the object to be treated by the insecticidal composition in the present invention include, for example, bulbs and tubers. Plant seeds for planting, seedlings, propagules, bulbs, or vegetative propagation for cuttings.

The "soil" or "cultivation carrier" of the plant in the case of carrying out the method of use of the present invention means a support for cultivating a crop, in particular, a support for growing the root, and the material is not particularly limited, but is a plant. The material that can be grown and developed may be a so-called soil, a nursery mat, water, etc., and for specific materials, for example, sand, pumice, vermiculite, diatomaceous earth, agar, Colloidal substances, high molecular substances, rock wool, glass wool, wood chips, bark, etc.

For the method of dispersing crop stems or leaves, or pests, house pests, sanitary pests, or forest pests, liquid preparations such as emulsions, flowables, or wettable powders or wettable particles may be mentioned. a method of dispersing a solid preparation such as a powder; a method of dispersing a powder; or smoking.

The method of applying the soil may, for example, be a method of applying a liquid preparation to a plant root or a seedling seedling bed of a plant body by diluting or not diluting the liquid preparation; or dispersing the granules on the plant roots of the plant body or a method for seedling bed, etc.; a method of dispersing a powder, a wettable powder, a granule wettable powder, a granule, etc., and mixing it with the soil before or before the seeding; before planting or before planting the plant Powders, wettable powders, granule wettable powders, granules, and the like are dispersed in a planting row, a planting row, and the like.

For the method of applying the rice seedling box, the dosage form may also be different depending on the application period such as application at the time of sowing, application during the greening period, application at the time of transplantation, but as long as it is a powder, a granule wettable powder, or a granule. The dosage form or the like can be administered. The mixture may be applied by mixing with the soil, and the soil may be mixed with a powder, a granule wettable powder or a granule, and the like, for example, bed soil mixing, soil covering mixing, and mixing of the whole soil may be carried out. It is also possible to apply only the soil and the various preparations in a layered manner.

For the method of applying the paddy field, a solid preparation such as a jumbo agent, a pack aget, a granule, or a granule wettable powder; a liquid preparation such as a sol or an emulsion is dispersed in a usual form. It is a paddy field in the state of Zhanshui. In addition, when inserting, the appropriate preparation may be directly or mixed with fertilizer to be dispersed and injected into the soil. Further, it is also possible to use a chemical solution such as an emulsion or a sol by an inflow source of water to the paddy field such as a water inlet or a filling device, and to apply it with labor.

In the case of a dry field crop, a cultivation carrier or the like that is close to the seed or plant body can be treated from the sowing to the seedling stage. For plants directly sown in dry fields, in addition to direct treatment of the seeds, treatment of the plant roots of the plants under cultivation is suitable. A granule may be used for the dispersion treatment, or a drug diluted or not diluted with water may be perfused in a liquid state or the like. It is also preferred to carry out the seeding after mixing the granules with the cultivation carrier before sowing. In the seeding and seedling treatment of the transplanted cultivated plant, in addition to the direct treatment of the seed, it is preferably a perfusion treatment or a granule for the liquid preparation of the nursery seedbed. Spray treatment. Further, it is also preferred to treat the granules at the time of planting or to mix the cultivation carriers in the vicinity of the transplant site.

The agricultural and horticultural insecticide of the present invention is generally used in a form of a convenient form for use according to a conventional method such as dissolving, concentrating, distilling, or crystallization on a pesticide preparation.

That is, the imidazolium represented by the general formula (I) of the present invention The compound or a salt thereof is prepared by dissolving, separating, suspending, mixing, impregnating, adsorbing or adhering it in an appropriate inert carrier or, if necessary, together with an adjuvant, in an appropriate ratio to dissolve, separate, suspend, mix, impregnate, adsorb or adhere. The dosage form, for example, a suspending agent, an emulsion, a liquid preparation, a wettable powder, a granule wettable powder, a granule, a powder, a tablet, a package, or the like can be used.

The agricultural and horticultural insecticide or the animal parasitic control agent of the composition of the present invention may contain, in addition to the active ingredient, an additive component which is usually used in a pesticide preparation or an animal parasitic control agent, as needed. Examples of the component to be added include a solid carrier, a carrier such as a liquid carrier, a surfactant, a dispersing agent, a wetting agent, a binder, an adhesion-imparting agent, a tackifier, a coloring agent, a developing agent, a spreading agent, and an antifreezing agent. , anti-caking agents, breakers, stabilizers, etc. Others may also use preservatives, plant debris, etc., as needed. These additional components may be used singly or in combination of two or more.

Examples of the solid carrier include quartz, clay, kaolinite, pyrophyllite, sericite, talc, bentonite, and acid. Natural minerals such as clay, magnesia, zeolite, diatomaceous earth; inorganic salts such as calcium carbonate, ammonium sulfate, sodium sulfate, potassium chloride; synthetic tannic acid, synthetic citrate, starch, cellulose, plants Organic solid carrier such as powder (such as sawdust, coconut shell, corn cob, tobacco stem, etc.); plastic carrier such as polyethylene, polypropylene, polyvinylidene chloride; urea, inorganic hollow body, plastic hollow body, Fumed silica (white carbon) and so on. These may be used alone or in combination of two or more.

The liquid carrier may, for example, be a monohydric alcohol such as methanol, ethanol, propanol, isopropanol or butanol; or such as ethylene glycol, diethylene glycol, propylene glycol, hexanediol or polyethylene glycol. Polyols such as polypropylene glycol and glycerin; polyol compounds such as propylene glycol ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone and cyclohexanone; diethyl ether; Alkanes, ethylene glycol monoethyl ether, dipropyl ether, tetrahydrofuran and other ethers; normal paraffin, cycloalkane, isoparaffin, kerosene, mineral oil and other aliphatic hydrocarbons; benzene, toluene, xylene, solvent Aromatic hydrocarbons such as naphtha and alkylnaphthalene; halogenated hydrocarbons such as dichloromethane, chloroform and carbon tetrachloride; ethyl acetate, diisopropyl phthalate, dibutyl phthalate , esters such as dioctyl phthalate and dimethyl adipate; lactones such as γ-butyrolactone; dimethylformamide, diethylformamide, dimethylacetamide Amidamines such as amines and N-alkylpyrrolidone; nitriles such as acetonitrile; sulfur compounds such as dimethyl hydrazine; vegetable oils such as soybean oil, rapeseed oil, cottonseed oil and castor oil; water and the like. These may be used alone or in combination of two or more.

Examples of the surfactant used as the dispersing agent or the wet spreading agent include sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, sucrose fatty acid ester, and polyoxyethylene fatty acid. Ester, polyoxyethylene resin ester, polyoxyethylene fatty acid diester, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene dialkyl phenyl ether , polyoxyethylene alkylphenyl ether formalin condensate, polyoxyethylene polyoxypropylene block copolymer, polystyrene polyoxyethylene block polymer, alkyl polyoxyethylene polypropylene block copolymer ether, poly Oxyethylene alkylamine, polyoxyethylene fatty acid decylamine, polyoxyethylene fatty acid bisphenyl ether, polyalkylene benzyl phenyl ether, polyoxyalkylene styryl phenyl ether, acetylene glycol, polyoxygen a nonionic surfactant such as alkyl acetylene glycol, polyoxyethylene ether fluorenone, ester fluorenone, fluorine surfactant, polyoxyethylene castor oil, polyoxyethylene hardened castor oil; Alkyl sulfate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl phenyl ether Acid salt, polyoxyethylene styryl phenyl ether sulfate, alkyl benzene sulfonate, alkyl aryl sulfonate, lignosulfonate, alkyl sulfosuccinate, naphthalene sulfonate, alkyl Naphthalene sulfonate, a salt of a formalin condensate of naphthalenesulfonic acid, a salt of a formalin condensate of an alkylnaphthalenesulfonic acid, a fatty acid salt, a polycarboxylate, a polyacrylate, an N-methyl-fatty acid creatinine Anionic surfactants such as salts, resinates, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkylphenyl ether phosphates; laurylamine hydrochloride, stearylamine hydrochloride, oleylamine salt An alkylamine salt such as an acid salt, stearylamine acetate, stearyl propylamine acetate, alkyltrimethylammonium chloride or alkyl dimethyl benzalkonium choloride Cation Surfactant; amphoteric surfactant such as amino acid type or betaine type. These surfactants may be used singly or in combination of two or more.

The binding agent or the adhesion-imparting agent may, for example, be carboxymethylcellulose or a salt thereof, dextrin, water-soluble starch, celery gum, guar gum, sucrose, polyvinylpyrrolidone, gum arabic, Polyvinyl alcohol, polyvinyl acetate, sodium polyacrylate, polyethylene glycol with an average molecular weight of 6000 to 20000, polyethylene oxide with an average molecular weight of 100,000 to 5 million, cellulose with phospholipids (such as cephalin, lecithin, etc.) Powder, dextrin, processed starch, polyaminocarboxylic acid chelating compound, crosslinked polyvinylpyrrolidone, copolymer of maleic acid and styrene, (meth)acrylic copolymer, polymerization comprising polyol Condensation of a half ester of a dicarboxylic anhydride, a water-soluble salt of polystyrenesulfonic acid, a paraffin, a terpene, a polyamidamide resin, a polyacrylate, a polyoxyethylene, a wax, a polyvinyl alkane, an alkylphenol fumarin Materials, synthetic resin emulsions, etc.

Examples of the tackifier include, for example, Sanxian gum, guar gum, Diutan Gum, carboxymethyl cellulose, polyvinylpyrrolidone, carboxyvinyl polymer, acrylic polymerization. A water-soluble polymer of a substance, a starch compound or a polysaccharide, such as a high-purity bentonite, an inorganic fine powder of fumed silica (white carbon), or the like.

The coloring agent may, for example, be an inorganic pigment such as iron oxide, titanium oxide or Prussian blue, an organic dye such as a halogen dye, an azo dye or a metal phthalocyanine dye.

Examples of the antifreezing agent include polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and glycerin.

Examples of the adjuvant for preventing agglomeration or promoting collapse include polysaccharides such as starch, alginic acid, mannose, and galactose, polyvinylpyrrolidone, fumed silica, and white carbon. ), ester gum, petroleum resin, sodium tripolyphosphate, sodium hexametaphosphate, metal stearate, cellulose powder, dextrin, copolymer of methacrylate, polyvinylpyrrolidone, polyaminocarboxylic acid Chelating compounds, sulfonated styrene/isobutylene/maleic anhydride copolymers, starch/polyacrylonitrile graft copolymers, and the like.

Examples of the stabilizer include ultraviolet absorption such as an antioxidant such as zeolite, quicklime, magnesia, a phenol compound, an amine compound, a sulfur compound, a phosphoric acid compound, a salicylic acid compound, and a benzophenone compound. Agents, etc.

Examples of the preservative include potassium sorbate and 1,2-benzothiazolin-3-one.

Further, an activity enhancer such as a functional exhibiting agent, a metabolic decomposition inhibitor such as Piperonyl Butoxide, an antifreezing agent such as propylene glycol, an antioxidant such as BHT, or other auxiliary agent such as a UV absorber may be used as needed. Agent.

The blending ratio of the active ingredient compound can be adjusted as needed. The 100 parts by weight of the agricultural and horticultural insecticide of the present invention may be appropriately selected and used in the range of 0.01 to 90 parts by weight, for example, as a powder or a granule. In the case of an emulsion or a wettable powder, 0.01 to 50 parts by weight is suitable.

The amount of the agricultural and horticultural insecticide used in the present invention may be due to various factors such as the purpose, the target pest, the growth and development of the crop, the tendency of the pest to produce, the weather, the environmental conditions, the dosage form, the application method, the application site, and the application. In the range of 0.001 g to 10 kg, preferably 0.01 g to 1 kg per 10 ares, it is preferable to select a compound as an active ingredient in accordance with the purpose.

The agricultural and horticultural insecticide of the invention can also be used for controlling the pests and diseases of the target, the expansion of the control period, or for the purpose of reducing the dose, and other agricultural and horticultural insecticides, acaricides, nematicides A fungicide, a biological pesticide, or the like may be used in combination, and may be used in combination with a herbicide, a plant growth regulator, a fertilizer, or the like depending on the occasion of use.

As other agricultural and horticultural insecticides, acaricides, nematicides used for the purpose of association, for example, 3,5-xylyl methylcarbamate (XMC) can be exemplified. Bacillus thuringienses (eg, Bacillus thuringienses aizawai, Bacillus thuringienses israelensis, Bacillus thuringienses japonensis, Suli Bacillus thuringienses kurstaki, crystalline protein toxin produced by Bacillus thuringienses tenebrionis, etc.; BPMC, Bt toxin-based insecticidal compound; chlorfenson (CPCBS) ), dichlorodiisopropyl ether (DCIP), 1,3-dichloropropene (DD), DDT, NAC, O-4-dimethylaminesulfonylphenyl O , O-4-dimethylsulfamoylphenyl O (O-diethyl phosphorothioate, DSP), O-ethyl O-4-nitrophenyl phenyl thiophosphate (O-ethyl O- 4-nitrophenyl phenylphosphonothioate, EPN), tripropyl isocyanurate (t Ripropylisocyanurate, TPIC), acrinathrin, azadirachtin, azinphos-methyl, acequinocyl, acetamiprid, acetoprole, anthraquinone Acephate, abamectin, avermectin-B, amidoflumet, amitraz, alanycarb, aldicarb ), aldoxycarb, aldrin, alpha-endosulfan, alpha-cypermethrin, albendazole, allethrin , isazofos, organothiophosphate nematicides (isamidofos), isoamidofos, isoxathion, isofenphos, isoprocarb (MIPC) , ivermectin, imicyafos, imidacloprid, imiprothrin, indoxacarb, esfenvalerate, ethiofencarb, Ethion, ethiprole, etoxazole, ethofenprox, ethoprophos, Etrimfos, emamectin, emamectin-benzoate, endosulfan, empenthrin, oxamyl, methotrexate Oxydemeton-methyl), oxydeprofos (ESP), oxibendazole, oxfendazole, Potassium oleate, sodium oleate, and pine (cadusafos), cartap, carbaryl, carbosulfan, carbofuran, gamma-cyhalothrin, xylylcarb, Quinalphos, kinoprene, chinomethionat, cloethocarb, clothianidin, clofentezine, chromafenozide, Chlorantraniliprole, chlorethoxyfos, chlordimeform, chlordane, chlorpyrifos, chlorpyrifos-methyl, chlorphenapyr, kill Chlorfenson, chlorfenvinphos, chlorfluazuron, chlorobenzi Late), chlorobenzoate, dicofol, salithion, cyanophos (CYAP), diafenthiuron, diamidafos, cyanide Cyantraniliprole, theta-cypermethrin, dienochlor, cyenopyrafen, dioxabenzofos, diofenolan, cypermethrin (sigma- Cypermethrin), deichlofenthion (ECP), cycloprothrin, dichlorvos (DDVP), disulfoton, dinotefuran, cyhalothrin, Cyphenothrin, cyfluthrin, diflubenzuron, cyflumetofen, diflovidazin, cyhexatin, cypermethrin, A Dimethylvinphos, dimethoate, dimefluthrin, silafluofen, cyromazine, spinetoram, sinister ( Spinosad), spirodiclofen, spirotetramat, spiromesifen, Sulfuramid, sulprofos, sulfoxaflor, zeta-cypermethrin, diazinon, tau-fluvalinate, Dazomet, thiacloprid, thiamethoxam, thiodicarb, thiocyclam, thiosultap, thiosultap-sodium, Lined phosphorus (thionazin), thiometon, deet, dieldrin, tetrachlorvinphos, tetradifon, tetramethylfluthrin , tetramethrin, tebupirimfos, tebufenozide, tebufenpyrad, tefluthrin, teflubenzuron, demeton -S-methyl), temephos, deltamethrin, terbufos, tramopyril, tralmethrin, transfluthrin, oxazolidine Triazamate, triazuron, trichlamide, trichlorphon (DEP), triflumuron, Tolfenpyrad, naled (BRP), nithiazine, nitenpyram, novaluron, noififlumuron, enestrobin Hydroprene), vaniliprole, vamidothion, parathion, parathion-methyl, halfenprox, halofenozide , bistrifluron, bisultap, hydramethylnon, hydroxy propyl starch, binapacryl, bifenazate, bifenthrin ), pymetrozine, pyracolphos, pyrafluprole, pyridafenthion, pyridaben, pyridalyl, aniline (pyrifluquinazon), pyriprole, pyriproxyfen, pirimicarb, Pyrimidifen, pirimiphos-methyl, pyrethrins, fen Fipronil, fenazaquin, fenamiphos, bromopropylate, extinguish (fenitrothion, MEP), fenoxycarb, fenothiocarb, phenothrin, fenobucarb, fensulfothion, fenthion, MPP ), phenothoate (PAP), fenvalerate, fenpyroximate, fenpropathrin, fenbendazole, fosthiazate, formetanate ), butathiofos, buprofezin, furathiocarb, prallethrin, fluacrypyrim, fluazinam, fluzuron , fluensulfone, flucycloxuron, flucythrinate, fluvalinate, flupyrazofos, flufenerim, flufenoxuron ), flufenzine, flufenoprox, fluproxyfen, flubrocythrinate, flubendiamide, flumethrin, Flurimfen, prothiofos, protrifenbute, fluniline Icamid), propaphos, propargite (BPPS), profenofos, profluthrin, propoxur (PHC), new bromopropylate, beta- Beta-cyfluthrin, hexaflumuron, hexythiazox, heptenophos, permethrin, benclothiaz, bendiocarb ), benzultap, benzoximate, benfuracarb, phoxim, phosalone, fosthiazate, fosthietan, blessing Phomamidon, phosphocarb, phosmet (PMP), polynactins, formetanate, formothion, phorate, Machine oil, malathion, milbemycin, milbemycin-A, milbemectin, mecarbam, mesulfenfos ,methomyl, metaldehyde, metaflumizone, methamidophos, weibaimu ammonium (m Etam-ammonium), metam-sodium, metiocarb, methidathion (DMTP), methylisothiocyanate, methylneodecanamide, Methyl bastathon (methylparathion), Metoxadiazone, methoxychlor, methoxyfenozide, metofluthrin, methoprene, metolcarb, meperfluthrin, Mevinphos, monocrotophos, monosultap, lambda-cyhalothrin, ryanodine, lufenuron, resmethrin , lepimectin, rotenone, levamisol hydrochloride, fenbutatin oxide, morantel tartarate, methyl bromide, Cyhexatin, calcium cyanamide, calcium polysulfide, sulfur, and nicotine-sulfate.

Examples of agricultural and horticultural fungicides to be used for the same purpose include, for example, aureofungin, azaconazole, azimutram, acypetacs, and aric acid. Acibenzolar, acibenzolar-S-methyl, azoxystrobin, anilazine, amisulbrom, 1-aminopropylphosphoric acid (ampropylfos), ametoctradin, allyl alcohol, aldimorph, amobam, isotianil, isovalidone ), isopyrazam, isoprothiolane, ipconazole, iprodione, iprovalicarb, iprobenfos, imipenem (imazalil), iminoctadine, iminoctadine-albesilate, iminoctadine-triacetate, imibenconazole, uniconazole , Uniconazole-P, echlomezole, edifenphos, ethiazole (eta Conazole), ethaboxam, ethirimol, etem, ethoxyquin, etridiazole, enestroburin, yup Epoxiconazole, oxadixyl, oxycarboxin, copper-8-quinolinolate, oxytetracycline, copper-oxinate , Ixazole (oxpoconazole), Oxpoconazole-fumarate, oxolinic acid, octhilinone, ofurace, oressastrobin, metam-sodium , kasugamycin, carbamorph, carpropamid, carbendazim, carboxin, carvone, quinazamid , quinacetol, quinoxyfen, quinomethionate, captafol, captan, kiralaxyl, quinconazole, five Quintozene, guazatine, cufraneb, cuprobam, glyodin, griseofulvin, climbbazole , cresol, kresoxim-methyl, chlozolinate, clottrimazole, chlobenthiazone, chloraniformethan, chloranil Tetrachloroquine Chlorquinox, chloropicrin, chlorfenazole, chlorodinitronaphthalene, chlorothalonil, chloroneb, zarilamid , salicylanilide, cyazofamid, diethyl pyrocarbonate, diethofencarb, cyclafuramid, diclocymet, bacteria Dichlozoline, diclobutrazol, dichlofluanid, cycloheximide, diclomezine, dicloran, dichlorophen, large Dichlone, disulfiram, ditalimfos, dithianon, diniconazole, diniconazole-M, zineb, white powder (dinocap), dinocton, dinosulfon, dinoterbon, dinobuton, dinopenton, dipyrithione, Diphenylamine, difenoconazole, cyflufenamid , diflumetorim, cyproconazole, cyprodinil, cyprofuram, cypendazole, simeconazole, dimethirimol , dimethomorph, cymoxanil, dimoxystrobin, methyl bromide, ziram, silthiofam, streptomycin, screw Spiroxamine, sultropen, sedaxane, zoxamide, dazome, thiadiazin, tiadinil, fluorothiazide Thiadifluor, thiabendazole, tioxymid, thiochlorfenphim, thiophanate, thiophanate-methyl, Thiicyofen, thioquinox, chinomethionat, thifluzamide, thiram, decafintin, tecnazene, Tecloftalam, tecoram, tetraconazole, debacarb, dehydroacetic acid, tebuconazole, tebufloquin , dodicin, dodine, dodecyl benzensulfonate bis-ethylene diamine copper (II) (DBEDC), bacteria Dodemorph, drazoxolon, triadimenol, triadimefon, triazbutil, triazophos Zoxide), triamiphos, triarimol, trichlamide, tricyclazole, triticonazole, tridemorph, tributyl oxide Trityltin oxide, triflumizole, trifloxystrobin, triforine, tolylfluanid, tolclofos-methyl, natamycin , nabam, nitrothal-isopropyl, nitrostyrene, nuarimol, copper nonylphenol sulfonate, halacrinate ), validamycin, valifenalate, harpin protein, bixafen, picoxystrobin, picobenzamide, Bis-dichlorophenol (bithionol), bitertanol, Methylisoxazole, hydroxyl difference Hydroisoxazole-potassium, binapacryl, biphenyl, piperalin, hymexazol, pyraoxystrobin, pyracarbolid, Pyraclostrobin, pyrazophos, pyrametostrobin, pyriofenone, pyridinitril, pyrifenox, pyribencarb , pyrimethanil, pyroxychlor, pyroxyfur, pyroquilon, vinclozolin, famoxadone, fenapanil , fenamidone, fenaminosulf, fenarimol, fenitropan, fenoxanil, ferimzone, ferbam, tri Phentin, fenpiclonil, fenpyrazamine, fenbuconazole, fenfuram, fenpropidin, fenpropimorph ), fenhexamid, phthalide, buthiobate, butylamine, Bray (bupirimate), fuberidazole, blasticidin-S, furametpyr, furalaxyl, fluacrypyrim, fluazinam, fluoride Fluoxastrobin, fluotrimazole, fluopicolide, fluopyram, fluoroimide, furcarbanil, fluoxazole Fluxapyroxad, fluquinconazole, furconazole, furconazole-cis, fludioxonil, flusilazole, flusulfamide , flutianil, flutolanil, flutriafol, furfural, furmecyclox, flumetover, flumorph, propyl Proquinazid, prochloraz, procymidone, prothiocarb, prothioconazole, propamocarb, propiconazole, methyl zinc Propineb, furophanate, probenazole, bromuconazole, hexachloro Hexachlorobutadiene, hexaconazole, hexylthiofos, bethoxazin, benalaxyl, benaxyl-M, benodanil ), benomyl, pefurazoate, benquinox, penconazole, benzamorf, pencycuron, benzohydroxamic Acid), bentaroron, bethithiazole, benthiavalicarb-isopropyl, penthiopyrad, penflufen, boscalid , phosdiphen, fosetyl, fosetyl-Al, polyoxins, polyoxorim, polycarbamate, Folpet, formaldehyde, machine oil, maneb, mancozeb, mandipropamid, myclozolin, micney Myclobutanil), mildiomycin, milneb, mecarbinzid, methasulfocarb, m-citronellone (meta) Zoxolon), metam, metam-sodium, metalaxyl, metalaxyl-M, metiram, methyl isothiocyanate Methyl isothiocyanate), mepthyldinocap, metconazole, metsulfovax, methfuroxam, metominostrobin, metrafenone, extinction Forest (mepanipyrim), mefenoxam, meptyldinocap, mepronil, mebenil, iodomethane, rabenzazole, benzalkonium chloride Benzalkonium chloride, such as basic copper chloride, basic copper sulfate, copper sulfate anhydride, copper sulfate pentahydrate, hydrogen Cupric hydroxide, copper compound of oxine copper, nickel dimethyldithiocarbamate, zinc sulfate, silver, etc. Inorganic fungicide, sodium hypochlorote, wettability Agent (wettable sulfur), mixture of lime sulfur (calcium polysulfide), potassium bicarbonate (potassium hydrogen carbonate), sodium bicarbonate (sodium hydrogen carbonate), inorganic sulfur (sulfur).

Similarly, as the herbicide, for example, 1-naphthylacetamide, 2,4-PA, 2,3,6-TBA, 2,4,5-T, 2,4, 5-TB, 2,4-D, 2,4-DB, 2,4-DEB, 2,4-DEP, 3,4-DA, 3,4-DB, 3,4-DP, 4-CPA, 4-CPB, 4-CPP, MCP, MCPA, MCPA-thioethyl, MCPB, ioxynil, aclenifen, azafenidin, acifluorfen ), azuprotryne, azimsulfuron, asulam, acetochlor, atrazine, attraton, oxaloquinone (anisuron), anilofos, avidycine, abscisic acid, amicarbazone, amidosulfuron, amitrol, Aminocyclopyrachlor, aminopyralid, amibuzin, amiprophos-methyl, amethidione, ametryn, pull Alachlor, allidochlor, alloxydim, aloac, auron, butanamine (isoc) Arbamid), different Isoxachlortole, different Grass ether (isoxapyrifop), different Isooxaflutole, different Isoxaben, isocil, isororuron, isoproturon, isopropalin, isopolinate, isomethiozin , inabenfide, ipazine, ipfencarbazone, iprymidam, imazaquin, imazapic, and imazapic Imazapyr), imazamethapyr, imazamethabenz, imazamethabenz-methyl, imazamox, imazethapyr, imazosulfuron , indaziflam, indanofan, indolebutyric acid, uniconazole-P, eglinazine, esprocarb, Ethametsulfuron, ethametsulfuron-methyl, ethalfluralin, ethiolate, ethychlozate ethyl, ethidomuron , etinofen, ethephon, ethoxysulfuron, ethoxyfen, ethylamine Ether (etnipromid), ethofumesate, etobenzanid, epronaz, erbon, endothal, oxadiazon Propyne Oxadiargyl, oxaziclomefone, oxasulfuron, oxapyrazon, oxyfluorfen, oryzalin, orthosulfamuron , orbencarb, cafenstrole, cambendichlor, carbasulam, carfentrazone, carfentrazone-ethyl, carbendazim (karbutilate), grass carbetamide, special Carboxazole, quizalofop, quizalofop-P, quizalofop-ethyl, xylachlor, quinoclamine , quinonamid, quinclorac, quinmerac, cumyluron, cloodinate, glyphosate, chlorpyrifos Glufosinate), glufosinate-P, cedazine, clethodim, cloxyfonac, clodinafop, clodinafop-propargyl , chlorotoluron, clopyralid, cloproxydim, cloprop, chlorbromuron, clofop, clomazone ), chlomethoxynil, chlomethoxyfen, clomeprop, chlorazifop, chlorazine, cloransulam, earth Chloranocryl, chloramben, cloransulam-methyl, chloridazon, chlorimuron Chlorimuron-ethyl, chlorsulfuron, chlorthal, chlorthiamid, chlortoluron, chlornitrofen, valac ( Chlorfenac), chlorfenprop, chlorbufam, chlorflurazole, chlorflurenol, chlorprocarb, chlorpropham, chlormequat, Chloreturon, chloroxynil, chloroxuron, chloropon, saflufenacil, cyanazine, cyanacex ), di-allate, diuron, diethamquat, dicamba, cycluron, cycloate, ringworm (cycloxydim), diclosulam, cyclosulfamuron, 2,4-dipropionic acid, di 2,4-dipropionic acid-P (dichlorprop-P), dichlorvos (dichlobenil), diclofop, diclofop-methyl, dichlormate, dichloralurea, diquat, Cisanilide, 2,4-disodium sulphate, siduron, dithiopyr, dinitramine, cinidon-ethyl, pentane Dinosam, cinosulfuron, dinoseb, dinoterb, dinofenate, dinoprop, cyhalofop-butyl ), diphenamid, difenoxuron, difenopenten, difenzoquat, cybutryne, cyprazine, tricyclic sage Cyprazole, diflufenican, diflufenzopyr, dipropetryn, cypromid, cyperquat, gibberellin, Simazine, dimexano, dimethachlor, dimidazon, dimethametryn, dimethenamid, simetryn , simeton, dimepiperate, Dimefuron, cinmethylin, swep, sulglycapin, sulcotrione, sulfallate, sulfentrazone , sulfosulfuron, sulfometuron, sulfometuron-methyl, secbumeton, sethoxydim, sebuthylazine, Terbacil, daimuron, dazomet, dalapon, thiazafluron, thiazopyr, thiencarbazone, Thiencarbazone-methyl, tiocarbazil, tioclorim, thiobencarb, thidiazimin, thidiazuron, thifensulfuron (thifensulfuron), thifensulfuron-methyl, desmedipham, desmetryn, tetrafluron, thenylchlor, tebutam, Tebuthiuron, terbumeton, tepraloxydim, tefuryltrione, tembot Rione), delachlor, terbacil, terbucarb, terbuchlor, terbuthylazine, terbutryn, phenylpyrazole Topramezone, tralkoxydim, triaziflam, triasulfuron, tri-allate, trietazine, herbicide ( Tricamba), triclopyr, tridiphane, tritac, tritosulfuron, triflusulfuron, triflusulfuron -methyl), trifluralin, trifloxysulfuron, tripropindan, tribenuron-methyl, tribenuron, trifluorobenzene Trifop, trifopsime, trimeturon, naptalam, naproanilide, napropamide, nicosulfuron , nitralin, nitrofen, nitrofluorfen, nipyraclofen, neburon, flufenapyr (norfl) Urazon), noruron, barban, paclobutrazol, paraquat, parafluron, haloxydine, haloxyfop, Heloxyfop-P, haloxyfop-methyl, halosafen, halosulfuron, halosulfuron-methyl, Picloram, picolinafen, bicyclopyrone, bispyribac, bispyribac-sodium, pydanon, oxazolin (pinoxaden), bifenox, piperophos, hymexazol, pyraclonil, pyrasulfotole, pyrazoxyfen, pyridinium Pyrazolsulfuron, pyrazoosulfuron-ethyl, pyrazolate, bilanafos, pyraflufen-ethyl, pyridinol , pyridafol, pyrithiobac, pyrithiobac-sodium, pyridate, pyrifalid, pyrib Uticarb), pyribenzoxim, pyrimisulfulan, primisulfuron, pyriminobac-methyl, pyroxasulfone, acesulfame Pyroxsulam), fenasulam, phenisopham, fenuron, different Benzosulfone, Fenoxaprop, pyraclostrobin-P (fenoxaprop-P), fine Fenoxaprop-ethyl, phenothiol, fenoprop, phenobenzuron, fenthiaprop, fenteracol, tetrazole Fentrazamide, phenmedipham, phenmedipham-ethyl, butachlor, butafenacil, butamifos, buthiuron, butadiene Buthimidazole, butarate, buturon, butenachlor, butroxydim, butralin, flazasulfuron , flamprop, furyloxyfen, prynachlor, primisulfuron-methyl, fluazifop, fluazifop- P), fluazifop-butyl, fluazolate, fluroxypyr, fluothiuron, fluometuron, acesulfame Fluoroglycofen), flurochloridone, fluorodifen, fluoronitrofen, fluoromidine, flurazepam (flucarbazone), flucarbazone-sodium, fluchloralin, flucetosulfuron, fluthiacet, fluthiacet-methyl, flurazine Flupyrsulfuron, flufenacet, flufenican, fluoroquinone Flufenpyr, flupropacil, flupropanate, flupoxam, flumioxazin, flumiclorac, flumethacic acid (flumiclorac-pentyl), fluamipropyn, trifluoro Flumezin, fluometuron, flumetsulam, fluridone, flurtamone, fluroxypyr, pretilachlor ), proxan, proglinazine, procyazine, prodiamine, prosulfalin, prosulfuron, benzathine ( Prosulfocarb), propaquizafop, propachlor, propazine, propanil, propyzamide, propisochlor, propyl jasmonate (prohydrojasmon), propyrisulfuron, propham, profluazol, profluralin, prohexadione-calcium, propylsulfuron (propoxycarbazone), propoxycarbazone-sodium, profoxydim, bromacil, brompyrazon, prometryn, prometon , bromoxynil, bromofenoxim, bromobutide, bromobo Nil), flostulalam, hexachloroacetone, hexazinone, pethoxamid, benazolin, penoxsulam, grass enemies (pebulate), beflubutamid, vernolate, perfluidone, bencarbazone, benzadox, benzipram, benignin (benzylaminopurine), benzthiazuron, benzfendizone, bensulide, bensulfuron-methyl, benzoylprop, benzobicyclon , benzofenap, benzofluor, bentazone, pentanochlor, benthiocarb, pendimethalin, cyclopentane Penoxoxazone, benfluralin, benfuresate, fosamine, fomesafen, foramsulfuron, forchlorfenuron , maleic hydrazide, mecoprop, mecoprop-P, medinoterb, mesosulfuron, Mesosulfuron-methyl, mesotrione, mesoprazine, methoprotryne, metazachlor, methazole, diether chloride Metazosulfuron, methabenzthiazuron, metamitron, Melamifop, metam, methalpropalin, methiuron, different Methiozolin, metiobencarb, methyldymron, metoxuron, metosulam, metsulfuron, metsulfuron, Methsulfuron-methyl, metflurazon, metobromuron, metobenzuron, metometon, metolachlor, chlorhexidine (metsulfuron-methyl) Meribuzin), mepiquat-chloride, mefenacet, mefluidide, monalide, special Monisouron, monuron, monochloroacetic acid, monolinuron, mollusd, morfamquat, iodosulfuron (folate) (iodosulfuron), iodosulfuron-methyl-sodium, iodobonil, iodomethane, lactofen, linuron, ruthenium sulfonate Rumsulfuron, lenacil, rhodetanil, calcium peroxide, methyl bromide, and the like.

Further, as a biological pesticide, for example, a nuclear polyhedrosis virus (NPV), a granulosis virus (GV), a cytoplasmic polyhedrosis virus (CPV), an insect poxvirus ( Entomopoxi virus (EPV) and other viral preparations; Monacrosporium phymatophagum, Steinernema carpocapsae, Steinernema kushidai, Pasteuria penetrans, etc. Microbial pesticides used by insects or nematicides; Trichoderma lignorum, Agrobacterium radiobactor, non-pathogenic Erwinia carotovora, Bacillus subtilis, etc. The microbial pesticide used in the fungicide; a biological pesticide used as a herbicide such as Xanthomonas campestris, etc., can be used in combination, and the same effect can be expected.

Furthermore, as a biological pesticide, for example, Encarsia formosa, Aphidius colemani, Aphidoletes aphidimyza, Diglyphus isaea, and Dacnusa sibirica, Chilean plantation (Phytoseiulus persimilis), Amboseseius cucumeris, Orius sauteri and other natural enemies; microbial pesticides such as Beauveria brongniartii; (Z)-10-tetradecene Base = acetate, (E,Z)-4,10-tetradecadienyl=acetate, (Z)-8-dodecenyl=acetate, (Z)-11-fourteen Alkenyl = acetate, (Z)-13-eicosene-10-one, 14-methyl-1-octadecene and the like are used in combination.

The production examples of the representative compounds and the intermediates of the present invention are described in more detail below, but the present invention is not limited to the examples.

Example Intermediate manufacturing example 1.

3-methylamino-6-pentafluoroethyl hydrazine Synthesis (Compound No. 20-2)

3-chloro-6-iodonium synthesized according to the method described in the literature under argon (7.2g), copper iodide (2.86g), 1,10-morpholine (2.7g), and adjusted by the method of the 94th Spring Annual Meeting Summary (Speech No. 2B1-17, page 1229) A solution of N-methylpyrrolidone (NMP) (0.33 M, 80 ml) of a difluoroalkyl zinc reagent was stirred at 90 ° C for 40 minutes, and then cooled to room temperature to obtain a reaction solution. Under ice cooling, the above reaction solution was gradually added dropwise to a mixed solution of tetrahydrofuran (THF, 30 ml) and methylamine (10 M in 30 ml of methanol) prepared in another container. The temperature was raised to room temperature and stirred for 1 hour. Water and ethyl acetate were added, and after stirring for 5 minutes, the mixed solution was filtered with tetracalcium lanthanum aluminate. The filtrate was extracted three times with ethyl acetate. The organic phase was dried over sodium sulfate, concentrated, and subjected to column chromatography to obtain the desired 3-methylamino-6-pentafluoroethylhydrazine. (6.36g).

Physical properties: Melting point: 141-143 ° C

Intermediate manufacturing example 2.

4-bromo-3-methylamino-6-pentafluoroethyl hydrazine Synthesis (Compound No. 20-6)

3-methylamino-6-pentafluoroethyl hydrazine (6.05 g) was dissolved in acetic acid (50 ml), and 1,3-dibromo-5,5-dimethylhydantoin (8.4 g) was added, and the mixture was stirred under heating at 95 ° C for 3 hours. The reaction solution was concentrated and water was added. After neutralizing with potassium carbonate, it was extracted three times with ethyl acetate. The organic phase was dried over sodium sulfate, concentrated, and subjected to column chromatography to give the desired 4-bromo-3-methylamino-6-pentafluoroethylhydrazine. (6.16g, 76%).

Physical properties: Melting point: 41-43 ° C

Intermediate manufacturing example 3.

4-amino-3-methylamino-6-pentafluoroethyl hydrazine Synthesis (Compound No. 20-10)

4-Bromo-3-methylamino-6-pentafluoroethyl hydrazine was added sequentially to the autoclave. (6.16 g), copper (I) oxide (1.44 g), N-methylpyrrolidone (NMP, 30 ml), and 28% aqueous ammonia (30 ml) were sealed while blowing argon gas. The mixture was stirred under heating at 80 ° C for 3 hours and cooled to room temperature. Water and ethyl acetate were added, and after stirring for 5 minutes, the mixed solution was filtered with tetracalcium lanthanum aluminate. The filtrate was extracted three times with ethyl acetate. The organic phase was dried over sodium sulfate, concentrated, and subjected to column chromatography to give the desired 4-amino-3-methylamino-6-pentafluoroethylhydrazine. (3.39g, 69%).

Physical properties: ¹ H-NMR (CDCl ₃ ): 6.75 (s, 1H), 5.18 (s, 1H), 4.59 (s, 2H), 2.85 (s, 3H)

Intermediate manufacturing example 4.

Synthesis of 2-ethylthio-4-trifluoromethylbenzoate decylamine (Compound No. 21-1)

2-Ethylthio-4-trifluoromethylbenzoic acid (1 g) was dissolved in toluene (1.7 ml), and then sulfinium chloride (0.9 ml) and acetone (dimethyl formaldehyde) (DMF, 0.5 ml) were sequentially added. Stir at 70 ° C for 1 hour. After cooling at room temperature, 28% aqueous ammonia (10 ml) prepared in another container was slowly added under ice cooling. The precipitated solid was filtered and dried under reduced pressure to give the desired ethyl 2-ethyldithio-4-trifluoromethylbenzoate (0.8 g, 88%).

Physical properties: Melting point: 174-179°C

Intermediate manufacturing example 5.

Synthesis of methyl 3-chloro-5-trifluoromethylpyridine-2-carboxylate

2,3-Dichloro-5-trifluoromethylpyridine (30 g, 0.14 mol), triethylamine (21 mL, 0.15 mol, 1.1 eq.), PdCl ₂ (tpp) ₂ (0.97 g, 1.4 mmol, 1 mol%) ), DPPB (0.59 g, 1.38 mmol, 1 mol%) and methanol (70 mL) were added to a 200 mL autoclave. The mixture was substituted three times with 3 MPa of carbon monoxide, and the reaction was started at an initial pressure of 3.0 MPa, a set temperature of 85 ° C, and a stirring speed of 600 rpm. When the internal pressure is not less than 3.0 MPa, carbon monoxide is preferably added, and the temperature is raised by 10 ° C per hour to rise to 115 ° C. After the absorption of carbon monoxide was stopped, it was cooled to room temperature. After suspending it in ethyl acetate, it was filtered under reduced pressure, and the resulting solution was concentrated under reduced pressure. The obtained residue was redissolved in ethyl acetate, washed with 1N hydrochloric acid and brine, and dried over anhydrous sodium sulfate. The obtained organic layer was concentrated to give the desired methyl ester (35.4 g).

Physical properties: ¹ H-NMR (CDCl ₃ ): 8.65 (1H, d), 7.86 (1H, d), 4.04 (3H, s), 2.99 (2H, q), 1.43 (3H, t)

Intermediate manufacturing example 6.

Synthesis of methyl 3-ethylthio-5-trifluoromethylpyridine-2-carboxylate

The methyl ester (1 g, 4.1 mmol) synthesized by the method described above was dissolved in DMF (4.1 mL), and 80% NaSEt (460 mg, 4.4 mmol, 1.1 eq. After the reaction solution was diluted with ethyl acetate, it was washed with saturated sodium bicarbonate, saturated brine, water and saturated brine, and dried over anhydrous sodium sulfate. Purification by column chromatography gave the title compound ( 818 mg, 3.1 mmol, 74%).

The same procedure was carried out, and ethyl ester and butyl ester corresponding to the methyl ester were synthesized. The physical properties are shown below.

Ethyl ester: ¹ H-NMR (CDCl ₃ ): 8.67 (1H, s), 7.86 (1H, s), 4.51 (3H, q), 2.99 (2H, q), 1.46 (3H, t), 1.42 ( 3H, t); butyl ester: ¹ H-NMR (CDCl ₃ ): 8.67 (1H, d), 7.86 (1H, s), 4.45 (2H, t), 2.99 (2H, q), 1.82 (2H, m), 1.53-1.40 (5H, m), 0.98 (3H, t)

Manufacturing Example 1.

2-(2-Ethylthio-4-trifluoromethylphenyl)-3-methyl-6-heptafluoropropyl-3H-imidazole [4,5-C]嗒 Synthesis (Compound No. 1-91)

Palladium acetate (5.3 mg) was added to 4-bromo-3-methylamino-6-heptafluoropropyl hydrazine under an argon atmosphere. (170 mg), 2-ethylthio-4-trifluoromethylbenzoate decylamine (139 mg), Xantphos (55 mg), cesium carbonate (234 mg), two A mixed solution of alkane (4 ml). After refluxing at 100 ° C for 3 hours, it was cooled to room temperature and filtered with tetracalcium phthalate. After the residue was washed with ethyl acetate and acetone, the filtrate was concentrated. Toluene (5 ml) and acetic acid (5 ml) were added to the residue, and the mixture was stirred at 100 ° C for 3 hours. The reaction solution was concentrated, and ethyl acetate was added thereto and concentrated again. The obtained residue was subjected to column chromatography to obtain the desired 2-(2-ethylthio-4-trifluoromethylphenyl)-3-methyl-6-heptafluoropropyl-3H-imidazole [ 4,5-C]嗒 (76 mg, 32%).

Physical properties: Melting point: 83-84 ° C

Manufacturing Example 2.

2-(2-ethanesulfonyl-4-trifluoromethylphenyl)-3-methyl-6-heptafluoropropyl-3H-imidazole [4,5-C]嗒 Synthesis (Compound No. 1-93)

2-(2-Ethylthio-4-trifluoromethylphenylthio)-3-methyl-6-heptafluoropropyl-3H-imidazole [4,5-C]嗒 (44 mg) was dissolved in chloroform (2 ml), and m-chloroperoxybenzoic acid (55 mg) was slowly added under ice cooling. Warm to room temperature and stir overnight. A few drops of dimethyl hydrazine (DMSO) and triethylamine (about 3 ml) were added to the reaction solution and concentrated. The obtained residue was subjected to column chromatography to obtain the desired 2-(2-ethanesulfonyl-4-trifluoromethylphenyl)-3-methyl-6-heptafluoropropyl-3H- Imidazole [4,5-C]嗒 (45 mg, 96%).

Physical properties: Melting point: 160-162 ° C

Manufacturing Example 3-1.

N-(3-methylamino-6-pentafluoroethyl hydrazine Synthesis of -4-yl)-3-chloro-5-trifluoromethylpyridine-2-carboxylic acid decylamine

2-Chloro-1-methylpyridinium iodide (3.5 g) was added to 4-amino-3-methylamino-6-pentafluoroethyl hydrazine (3.15 g), a mixed solution of 3-chloro-5-trifluoromethylpyridine-2-carboxylic acid (3.24 g), dimethylaminopyridine (160 mg), tetrahydrofuran (THF, 40 ml), and pyridine (10 ml). After stirring at room temperature overnight, water and ethyl acetate were added. After extracting three times with ethyl acetate, the organic phase was dried over sodium sulfate and concentrated, and then subjected to column chromatography to obtain the desired N-(3-methylamino-6-pentafluoroethylhydrazine. 4-yl)-3-chloro-5-trifluoromethylpyridine-2-carboxylic acid decylamine (2.43 g, 41%).

Physical properties: ¹ H-NMR (CDCl ₃ ): 9.85 (brs, 1H), 8.28 (s, 1H), 8.22 (s, 1H), 8.20 (s, 1H), 4.90 (brs, 1H), 3.28 (d, 3H)

Manufacturing Example 3.

2-(3-Ethylthio-5-trifluoromethylpyridin-2-yl)-3-methyl-6-pentafluoroethyl-3H-imidazole [4,5-C]indole Synthesis (Compound No. 3-1)

N-(3-methylamino-6-pentafluoroethyl hydrazine A mixed solution of -4-yl)-3-chloro-5-trifluoromethylpyridine-2-carboxylic acid decylamine (2.6 g), toluene (20 ml), and acetic acid (20 ml) was heated and stirred at 100 ° C for 2 hours. The reaction solution was concentrated, and toluene was added to concentrate again. Dimethyl formaldehyde (DMF, 6 ml) and sodium thiothiolate (760 mg) were added to the residue, and the mixture was stirred under heating at 100 ° C for 2 hours. After cooling to room temperature, it was subjected to column chromatography to obtain 2-(3-ethylthio-5-trifluoromethylpyridin-2-yl)-3-methyl-6-pentafluoroethyl-3H. -imidazole [4,5-C]嗒 (2.78g, quantitative).

Physical properties: ¹ H-NMR (CDCl ₃ ): 8.79 (s, 1H), 8.31 (s, 1H), 7.78 (s, 1H), 4.31 (s, 3H), 3.05 (dd, 2H), 1.40 (t, 3H)

Manufacturing Example 4.

2-(3-Ethylsulfonyl-5-trifluoromethylpyridin-2-yl)-3-methyl-6-pentafluoroethyl-3H-imidazole [4,5-C]indole Synthesis (Compound No. 3-3)

2-(3-Ethylthio-5-trifluoromethylpyridin-2-yl)-3-methyl-6-pentafluoroethyl-3H-imidazole [4,5-C]嗒 (2.78 g) was dissolved in ethyl acetate (30 ml), and m-chloroperoxybenzoic acid (3.5 g) was slowly added under ice cooling. Warm to room temperature and stir overnight. A few drops of dimethyl hydrazine (DMSO) and triethylamine (about 3 ml) were added to the reaction solution and concentrated. The obtained residue was subjected to column chromatography to obtain the desired 2-(3-ethanesulfonyl-5-trifluoromethylpyridin-2-yl)-3-methyl-6-pentafluoroethyl- 3H-imidazole [4,5-C]嗒 (2.71 g, 91%).

Physical properties: Melting point: 191-194 ° C

Manufacturing Example 5.

N-(cyano)-S-[5-trifluoromethyl-2-(6-pentafluoroethyl-3-methyl-3H-imidazole[4,5-C]indole Synthesis of 2-yl)phenyl-S-ethylsulfonamide (Compound No. 2-1)

2-(2-Ethylthio-4-trifluorophenyl)-3-methyl-6-pentafluoroethyl-3H-imidazole [4,5] was produced in the same manner as in the method of Production Example 3. -C]嗒 (229 mg) was dissolved in tetrahydrofuran (THF, 3 ml), and then hydrogenamine (32 mg) and iodobenzene diacetate (177 mg) were added, and the mixture was stirred at room temperature for 1 hour. The reaction solution was concentrated, and the obtained residue was subjected to column chromatography to obtain the desired N-(cyano)-S-[5-trifluoromethyl-2-(6-pentafluoroethyl-3-) methyl-3H-imidazole [4,5-C]嗒 Benzyl-S-ethylsulfonamide (96 mg, 39%).

Physical properties: ¹ H-NMR (CDCl ₃ ): 8.74 (s, 1H), 8.23 (s, 1H), 8.14 (d, 1H), 8.12 (d, 1H), 4.28 (s, 3H), 3.87-3.82 ( m, 1H), 3.35-3.29 (m, 1H), 1.56 (t, 3H)

Manufacturing Example 6.

N-(cyano)-S-[5-trifluoromethyl-2-(6-pentafluoroethyl-3-methyl-3H-imidazole[4,5-C]indole Synthesis of 2-yl)phenyl]-S-ethylsulfonimide-S-oxide (Compound No. 2-2)

N-(cyano)-S-[5-trifluoromethyl-2-(6-pentafluoroethyl-3-methyl-3H-imidazole[4,5-C]indole 2-Benzyl)phenyl]-S-ethylsulfonamide (467 mg) was dissolved in ethanol (10 ml), and potassium carbonate (414 mg) and m-chloroperoxybenzoic acid (400 mg) were added and stirred at room temperature overnight. A few drops of dimethyl hydrazine (DMSO) and triethylamine (about 3 ml) were added to the reaction solution, followed by concentration. The resulting residue was subjected to column chromatography to obtain N-(cyano)-S-[5-trifluoromethyl-2-(6-pentafluoroethyl-3-methyl-3H-imidazole [4] ,5-C]嗒 -2-yl)phenyl]-S-ethylsulfonimide-S-oxide (27 mg, 6%).

Physical properties: ¹ H-NMR (CDCl ₃ ): 8.54 (s, 1H), 8.21 (s, 1H), 7.96 (d, 1H), 7.88 (d, 1H), 4.11 (s, 3H), 3.98-3.91 ( m, 2H), 1.48 (t, 3H)

Manufacturing Example 7-1.

N-(3-methylamino-6-pentafluoroethyl hydrazine Synthesis of -4-yl)-3-ethylthio-5-trifluoromethylpyridine-2-carboxylic acid decylamine

4-amino-3-methylamino-6-pentafluoroethyl hydrazine (200 mg, 0.83 mmol) in THF (10 mL) was added 60 wt% NaH (32 mg, 0.86 mmol). After confirming the completion of the foaming, methyl 3-ethylthio-5-trifluoromethylpyridine-2-carboxylate (242 mg, 0.87 mmol) was added. After stirring at room temperature for 2 hours, 1N hydrochloric acid was added and diluted with ethyl acetate. It was washed with saturated brine and the obtained aqueous layer was extracted with ethyl acetate. The organic layers were combined and dried over anhydrous sodium sulfate. The residue obtained by concentration under reduced pressure was purified by column chromatography to give phthalamide (283 mg, 72%).

Manufacturing Example 7.

2-(3-Ethylthio-5-trifluoromethylpyridin-2-yl)-3-methyl-6-pentafluoroethyl-3H-imidazole [4,5-C]indole Synthesis (Compound No. 3-1)

N-(3-methylamino-6-pentafluoroethyl hydrazine a mixed solution of -4-yl)-3-ethylthio-5-trifluoromethylpyridine-2-carboxylic acid decylamine (500 mg, 1.05 mmol), toluene (5 ml), acetic acid (5 ml) was heated and stirred at 100 ° C 3 hours. The reaction solution was concentrated, and toluene was added to concentrate again. The obtained residue was subjected to column chromatography to obtain the desired 2-(3-ethylthio-5-trifluoromethylpyridin-2-yl)-3-methyl-6-pentafluoropropyl-3H. -imidazole [4,5-C]嗒 (480 mg, quantitative).

Physical properties: ¹ H-NMR (CDCl ₃ ): 8.79 (s, 1H), 8.31 (s, 1H), 7.78 (s, 1H), 4.31 (s, 3H), 3.05 (dd, 2H), 1.40 (t, 3H)

The examples of the formulations are shown below, but are not limited thereto. In the formulation examples, the parts represent parts by weight.

Formulation Example 1.

The above was uniformly mixed and dissolved to form an emulsion.

Formulation Example 2.

The above was uniformly mixed and pulverized to form a powder.

Formulation Example 3.

The above is uniformly mixed, and an appropriate amount of water is added to knead, granulate, and dried to form a granulating agent.

Formulation Example 4.

The above was uniformly mixed and pulverized to form a wettable powder.

Next, the test examples of the present invention are shown, but are not limited thereto.

Test Example 1. Control efficiency of Myzus persicae

The cabbage was planted in a plastic pot with a diameter of 8 cm and a height of 8 cm to propagate the peach aphid, and the number of parasites in each pot was investigated. The imidazolium represented by the general formula (I) of the present invention The compound or its salt is dispersed in water and diluted to 500 ppm of the drug solution. The drug solution is sprayed on the stems and leaves of the potted cabbage and air-dried. The pot is stored in the greenhouse, and the parasite is investigated on the 6th day after the spraying of the agent. The number of parasites of the peach aphid of each cabbage was calculated from the following formula, and the judgment was made according to the following criteria.

Control efficiency = 100-{(T×Ca)/(Ta×C)}×100

Ta: Number of parasites before spraying in the treatment area

T: number of parasites after spraying in the treatment area

Ca: Number of parasites before spraying without treatment

C: number of parasites after spraying without treatment

Judging criteria

A... control efficiency 100%

B... control efficiency 99%~90%

C... control efficiency 89%~80%

D... control efficiency 79%~50%

As a result, 1-3, 1-4, 1-5, 1-6, 1-33, 1-42, 1-45, 1-51, 1-54, 1-57, 1-60 of the compound of the present invention , 1-63, 1-66, 1-72, 1-75, 1-78, 1-84, 1-90, 1-91, 1-93, 2-1, 2-2, 2-3, 2 -9, 2-11, 2-13, 2-17, 2-19, 3-3, 3-6, 4-3, 6-2, 6-3, 6-7, 6-8, and 6- The 9 line shows the activity of A.

Test Example 2. Insecticide test for Laodelphax striatella

The imidazolium represented by the formula (I) of the present invention The compound or a salt thereof was dispersed in water, and diluted to 500 ppm of the drug solution, and the rice seedlings (variety: Nipponbare, Nihonbare) were immersed in the drug solution for 30 seconds, placed in a glass test tube after air drying, and each was inoculated. After 10 larvae of the third instar larvae, they were covered with cotton plugs, and the number of live insects and dead insects was investigated after 8 days of inoculation, and the corrected mortality rate was calculated from the following formula, according to the judgment standard of Test Example 1. A decision was made.

As a result, 1-3, 1-4, 1-5, 1-6, 1-33, 1-42, 1-51, 1-54, 1-57, 1-60, 1-66 of the compound of the present invention , 1-70, 1-71, 1-72, 1-75, 1-78, 1-91, 1-93, 2-1, 2-2, 2-3, 2-9, 2-11, 2 The activities of A, -3, 3-3, 3-6, 4-3, 6-1, 6-2, 6-3, 6-6, 6-7, 6-8, and 6-9 are shown.

Test Example 3. Insecticidal test against Plutella xylostella

The adults of the diamondback moth are stocked in the cabbage seedlings to lay eggs, and the cabbage seedlings with the laid eggs are immersed in the imidazole hydrazine represented by the general formula (I) of the present invention after 2 days of stocking. The compound as an active ingredient was diluted to a drug solution of 500 ppm for about 30 seconds, and after air drying, it was left to stand in a constant temperature room at 25 °C. Six days after the immersion of the chemical solution, the number of hatching insects was examined, and the mortality rate was calculated from the following formula, and the judgment was made according to the criteria of Test Example 1. 10 in the 1st district was repeated 3 times.

As a result, 1-3, 1-4, 1-5, 1-6, 1-33, 1-42, 1-45, 1-51, 1-54, 1-57, 1-60 of the compound of the present invention , 1-63, 1-66, 1-70, 1-71, 1-72, 1-75, 1-78, 1-84, 1-91, 1-93, 2-1, 2-2, 2 -3, 2-9, 2-11, 2-13, 2-17, 2-19, 3-3, 3-6, 4-3, 6-4, 6-6, 6-7, 6-8 And 6-9 lines show the activity of A.

Industrial availability

The compound to which the present invention relates is a group of compounds which have an excellent control effect against a wide range of agricultural and horticultural pests and which have little effect on the organism other than the control target.

Claims (10)

An imidazolium represented by the general formula (I) a compound or a salt thereof, Wherein R ¹ represents (a1)(C ₁ -C ₆ )alkyl, (a2)(C ₂ -C ₆ )alkenyl, (a3)(C ₂ -C ₆ )alkynyl, (a4)( C ₃ -C ₆ )cycloalkyl or (a5)(C ₃ -C ₆ )cycloalkyl(C ₁ -C ₆ )alkyl; R ² represents (b1) hydrogen atom, (b2) (C ₁ -C ₆ ) alkyl, (b3) (C ₂ -C ₆ )alkenyl, (b4)(C ₂ -C ₆ )alkynyl, (b5)(C ₃ -C ₆ )cycloalkyl or (b6)(C _3- C ₆ )cycloalkyl(C ₁ -C ₆ )alkyl; R ³ represents (c1)(C ₁ -C ₆ )alkyl, (c2)(C ₁ -C ₆ )alkoxy, (c3 Halogen (C ₁ -C ₆ )alkyl, (c4)halo(C ₁ -C ₆ )alkoxy, (c5)(C ₁ -C ₆ )alkylthio, (c6)(C ₁ -C ₆ Alkylsulfinyl, (c7) (C ₁ -C ₆ ) alkanesulfonyl, (c8) halo(C ₁ -C ₆ )alkylthio, (c9)halo(C ₁ -C ₆ ) alkane Sulfonyl or (c10) halo(C ₁ -C ₆ ) alkanesulfonyl; R ⁴ represents (d1) a hydrogen atom, (d2) a halogen atom, (d3) a cyano group, a (d4) nitro group, (d5) (C ₁ -C ₆ )alkyl or (d6)(C ₁ -C ₆ )alkoxy; A represents S, SO, SO ₂ , S=NR ⁵ group, or S(O)=NR ⁵ group (this Wherein R ⁵ represents (e1) a hydrogen atom, (e2) a cyano group, (e3) (C ₁ -C ₆ ) alkylcarbonyl group, (e4) a halogen (C ₁ -C ₆ ) alkylcarbonyl group, (e5) benzenesulfonate The group or (e6) having the same or different ring on the ring is selected from the group consisting of (a) a halogen atom (b) cyano, (c) nitro, (d) (C ₁ -C ₆ )alkyl, (e) halo(C ₁ -C ₆ )alkyl, (f)(C ₁ -C ₆ ) Alkoxy and (g) _1-5 phenylsulfonyl groups of the group of (C ₁ -C ₆ ) alkoxy groups; A ¹ , A ² , A ³ and A ⁴ may be the same or Different, indicating a nitrogen atom or CH; Z may be the same or different, and represents (f1) a hydrogen atom, (f2) a halogen atom, (f3) a cyano group, a (f4) nitro group, a (f5) hydroxylamine group, and a (f6) amine group. (f7)hydroxyl, (f8)(C ₁ -C ₆ )alkyl, (f9)(C ₁ -C ₆ )alkoxy, (f10)(C ₂ -C ₆ )alkenyloxy, (f11) (C ₂ -C ₆ ) alkynyloxy, (f12)(C ₃ -C ₆ )cycloalkyl, (f13)halo(C ₁ -C ₆ )alkyl, (f14)halo(C ₁ -C ₆ ) Alkoxy, (f15) halo(C ₂ -C ₆ )alkenyloxy, (f16)halo(C ₂ -C ₆ )alkynyloxy, (f17)halo(C ₃ -C ₆ )cycloalkoxy, (f18) (C ₁ -C ₆ )alkylthio, (f19)(C ₁ -C ₆ )alkylsulfinyl, (f20)(C ₁ -C ₆ )alkylsulfonyl, (f21)halide C ₁ -C ₆ )alkylthio, (f22)halo(C ₁ -C ₆ )alkylsulfinyl or (f23)halo(C ₁ -C ₆ )alkylsulfonyl; n represents an integer from 1 to 4 }. Imidazole 请求 as in claim 1 a compound or a salt thereof, wherein R ¹ represents (a1)(C ₁ -C ₆ )alkyl; R ² represents (b1) a hydrogen atom or (b2)(C ₁ -C ₆ )alkyl; and R ³ represents (c3) a halogen (C ₁ -C ₆ )alkyl group or (c8)halogen (C ₁ -C ₆ )alkylthio group; R ⁴ represents a (d1) hydrogen atom; A represents S, SO, SO ₂ , S=NR ⁵ group Or S(O)=NR ⁵ group (wherein R ⁵ represents (e1) a hydrogen atom; (e2) a cyano group; (e4) a halogen (C ₁ -C ₆ ) alkylcarbonyl group or (e6) has a ring on the ring The same or different ones selected from the group consisting of (a) a halogen atom, (b) a cyano group, a (c) nitro group, a (d) (C ₁ -C ₆ ) alkyl group, and (e) a halogen (C ₁ -C ₆ ) Alkyl, (f)(C ₁ -C ₆ )alkoxy and (g) 1 to 5 substituents of the phenylsulfonyl group in the group of halogen (C ₁ -C ₆ )alkoxy groups; A ¹ , A ² , A ³ and A ⁴ may be the same or different and represent a nitrogen atom or CH; Z may be the same or different and represents (f1) a hydrogen atom, (f2) a halogen atom, (f4) a nitro group, (f5) a hydroxylamine. Base, (f6) amine group, (f7) hydroxyl group, (f8) (C ₁ -C ₆ ) alkyl group, (f12) (C ₃ -C ₆ ) cycloalkyl group, (f13) halogen (C ₁ -C ₆ And an alkyl group, (f14) halo(C ₁ -C ₆ )alkoxy, (f18)(C ₁ -C ₆ )alkylthio or (f21)halo(C ₁ -C ₆ )alkylthio. Imidazole 请求 as requested in item 1 or 2 A compound or a salt thereof, wherein A ¹ , A ² and A ³ are CH, and A ⁴ is a nitrogen atom. An imidazole hydrazine according to any one of claims 1 to 3 The use of a compound or a salt thereof as an agricultural and horticultural insecticide. A method of using an agricultural and horticultural insecticide, characterized in that the plant or soil is treated with the active ingredient of the agricultural and horticultural insecticide according to claim 4. A method for controlling pests for agricultural and horticultural, characterized in that plants or soil are treated with an effective amount of the agricultural and horticultural insecticide of claim 4. An external parasite controlling agent characterized by containing the imidazolium of any one of claims 1 to 3 The compound or a salt thereof is used as an active ingredient. A method of controlling an external parasite characterized by contacting an external parasite with an effective amount of an external parasite controlling agent according to claim 7. a 表示 represented by the general formula (II) a compound or a salt thereof, Wherein R ² represents (b1) a hydrogen atom or (b2) (C ₁ -C ₆ )alkyl; R ³ represents (c9) halo(C ₁ -C ₆ )alkyl, (c4)halo (C ₁ -C ₆ ) alkoxy or (c8) halo(C ₁ -C ₆ )alkylthio; R ⁴ represents (d1) a hydrogen atom, (d2) a halogen atom, (d5) (C ₁ -C ₆ )alkyl Or (d6) (C ₁ -C ₆ ) alkoxy; R represents (g1) a hydrogen atom, (g2) a halogen atom or (g3) an amine group}. An indoleamine compound represented by the formula (III) or a salt thereof, Wherein R ¹ represents (a1)(C ₁ -C ₆ )alkyl; R ² represents (b1) a hydrogen atom or (b2)(C ₁ -C ₆ )alkyl; A ¹ , A ² , A ³ And A ⁴ may be the same or different and represent a nitrogen atom or CH; Z may be the same or different and represents (f1) a hydrogen atom, (f2) a halogen atom, (f13) a halogen (C ₁ -C ₆ ) alkyl group, (f14) Halogen (C ₁ -C ₆ )alkoxy, (f21)halo(C ₁ -C ₆ )alkylthio, (f22)halo(C ₁ -C ₆ )alkylsulfinyl or (f23)halogen (C) ₁ - C ₆ ) alkanesulfonyl, n represents an integer from 1 to 4.