WO1999044993A1

WO1999044993A1 - Acryronitrile-based compound, method for producing the same and pest controlling agent comprising the same

Info

Publication number: WO1999044993A1
Application number: PCT/JP1999/001047
Authority: WO
Inventors: Toru Koyanagi; Yuji Nakamura; Masayuki Morita; Tsuyoshi Ikeda
Original assignee: Ishihara Sangyo Kaisha Ltd.
Priority date: 1998-03-06
Filing date: 1999-03-04
Publication date: 1999-09-10
Also published as: AU3274899A

Abstract

A novel compound which is useful as an active constituent of a pest controlling agent is provided. The compound is an acrylonitrile-based compound represented by formula (I), wherein Q is a substituted or unsubstituted phenyl or the like, X is a substituted or unsubstituted naphthyl or -J, Y is -C(=O)R1, -C(=S)R2 or the like, R1 is a substituted or unsubstituted alkynyl or -SR3, R2 is a substituted or unsubstituted alkyl or the like, R3 is a substituted or unsubstituted alkyl or the like, and J is a 5 or 6-membered heterocyclic group having 1 to 4 atoms of at least one heteroatom selected from the group consisting of O, S and N, with the proviso that X is not a pyridyl group, and a salt thereof.

Description

Specification

Acrylonitrile compounds, methods for their production and pesticides containing them

The present invention relates to a novel acrylonitrile compound useful as an active ingredient of a pesticide.

Background art

(1) U.S. Pat. No. 3,337,565 and U.S. Pat. No. 3,337,566 disclose an acrylonitrile derivative similar to the compound of the present invention, and the derivative and the compound of the present invention have different chemical structures. I do.

(2) WO97 / 40009 describes an ethylene derivative similar to the compound of the present invention, but the derivative and the compound of the present invention have different chemical structures.

(3) WO098 / 42683 describes a triazole compound power ⁵ 'similar to the compound of the present invention. The compound and the compound of the present invention have different chemical structures.

Disclosure of the invention

The present inventors have conducted various studies focusing on acrylonitrile-based compounds in order to find an excellent pesticide, and as a result, completed the present invention. That is, the present invention provides a compound represented by the formula (I):

Q O-Y

… (I)

NC X

Wherein Q is an optionally substituted phenyl, an optionally substituted benzyl, an optionally substituted naphthyl or 1 J, X is an optionally substituted naphthyl or 1 J, and Y is Kenyl, haloalkenyl, alkynyl, haloalkynyl, one C (= 0) or one C (= S) R ₂ and R! Is an alkynyl or one SR ₃ be substituted, R ₂ is alkyl which may be substituted, alkenyl which may be substituted, alkynyl which may be substituted, substitution which may be alkoxy, substituted Alkenyloxy, optionally substituted alkynyloxy, optionally substituted alkylthio, optionally substituted alkenylthio, optionally substituted alkynylthio, optionally substituted cycloalkyl, optionally substituted ぃ cycloalkyloxy, cycloalkylthio which may be substituted, phenyl which may be substituted, phenoxy which may be substituted, phenylthio which may be substituted, benzyl which may be substituted, benzyl which may be substituted Benzyloxy, optionally substituted benzylthio,

J, 10-J or 1S-J, and R ₃ is an optionally substituted alkyl, an optionally substituted alkenyl, an optionally substituted alkynyl, an optionally substituted cycloalkyl, an optionally substituted Is a benzyl or 1 J, wherein J is a 5- or 6-membered heterocyclic group containing at least one kind of 1 to 4 atoms selected from the group consisting of 0, S and N. Or a 6- to 11-membered condensed heterocyclic group containing at least one atom selected from the group consisting of 0, S and N (condensed heterocyclic groups are substituted Wherein X does not contain a pyridyl group], an acrylonitrile compound or a salt thereof, a production method thereof, and a pesticide containing the same.

In the formula (I), optionally substituted alkynyl, R ₂ optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted alkoxy, optionally substituted Good alkenyloxy, optionally substituted alkynyloxy, optionally substituted alkylthio, optionally substituted alkenylthio and optionally substituted alkynylthio, and optionally substituted alkyl of R ₃ , substituted Examples of the substituent of alkenyl and alkynyl which may be substituted include nodogen, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, nitro, cyano, and amino. , Monoalkylamino, Arukiruamino, etc. alkoxycarbonyl 'like et be. The number of substitutions may be one or more, and when two or more, they may be the same or different.

Q optionally substituted phenyl, optionally substituted benzyl and optionally substituted naphthyl, X optionally substituted naphthyl, R ₂ optionally substituted phenyl, optionally substituted Phenoxy, optionally substituted phenylthio, optionally substituted benzyl, optionally substituted benzyloxy and optionally substituted benzylthio, optionally substituted benzyl of R ₃ and heterocycle of J Group and its substituent of the fused heterocyclic group include, for example, -

Three

Rogen, alkyl optionally substituted with, alkoxy optionally substituted with, alkylthio optionally substituted with, alkylsulfinyl optionally substituted with, alkylsulfonyl optionally substituted with, nitro, cyano, amino, monoalkyl amino, dialkyl § amino, alkenyl, haloalkenyl, alkynyl, haloalkynyl, cycloalkyl, optionally phenyl substituted with w _2, may Fuenoki sheet be substituted with w _2, be substituted with w ₂ good benzyl, w ₂ may be substituted by pyrrolyl, furyl which may be substituted with w _2, which may be substituted by w ₂ thienyl, w ₂ which may be substituted with Imida Zoriru, substituted with w ₂ which may be pyrazolyl, which may be substituted by w ₂ Okisazoriru, which may be substituted by w ₂ Isookisazoriru, it is substituted with w ₂ There thiazolyl, optionally isothiazolyl be substituted with w _2, 1 may be substituted with W _2, 2, 3- Toriazoriru, 1 may be substituted with W _2, 2, 4 one Toriazoriru, substituted with W ₂ and may be 1, 2, 3 - Okisajiazoriru, 1 may be substituted with W _2, 2, 4-Okisajiazoriru, 1 may be substituted with W _2, 3, 4 one Okisajiazoriru, be substituted with W ₂ good 1, 2, 3 - thiadiazolyl, 1 may be substituted with W _2, 2, 4 Chiajiazoriru, 1 may be replacement by W _2, 3, 4 Chiajiazoriru, 1 may be substituted with W _2, 2, 3, 4 - tetrazolyl, pyridyl which may be substituted with W _2, good pyrimidyl sulfonyl be substituted with W _2, which may be optionally substituted pyrazinyl substituted with W _2, in W ₂ pyridazinyl, W 1 may be substituted with _2, 2, 4 - triazinyl, it is substituted with W ₂ May be 1, 3, 5 - triazinyl, 1 may be substituted with W _2, 2, 3, 5-tetrazinyl, may be substituted with W ₂ 1, 2, 4, 5-tetrazinyl, W which may be substituted by _{2-imidazolinyl,} optionally substituted with W ₂ Birazoriniru, optionally substituted with W ₂ Okisazoriniru, good iso O hexa benzoisothiazolyl sulfonyl be substituted with W _2, which may be substituted with W ₂ good thiazolinyl, optionally substituted with W ₂ isothiazolinyl, it may be substituted with W ₂ 1 - pyrrolidinyl, W ₂ which may be substituted with 1 Piberijiniru may be substituted with W ₂ 4 - morpholino, W ₂ in an optionally substituted indolyl, optionally substituted with W ₂ benzofuranyl, good isobenzofuranyl be substituted with W _2, base may be substituted with W ₂ Nzocheniru, be replacement by W ₂ It is replaced by Yoibe Nzoimidazoriru, W ₂ Which may be indazolyl, still at W ₂ Conversion to base may be Nzookisazoriru, W emission zone I base may be substituted with ₂ Soki no doubt Lil, which may be substituted by w ₂ Benzochiazoriru, are base may be Nzoisochiazo Lil replaced by w _2, replaced by w ₂ which may be quinolyl, w ₂ isoquinolyl which may be substituted by, may be substituted by w ₂ cinnolyl, w ₂ may be substituted by phthalazyl, w ₂ may be substituted by Kinazariniru, substituted with w ₂ Quinoxalinyl, acyl, alkoxy, luponyl and the like which may be used. The number of substitutions may be one or more, and when two or more, they may be the same or different. Is halogen, alkoxy, alkylthio, amino, monoalkylamino, dialkylamino, phenyl, cycloalkyl, alkoxycarbonyl, trialkylsilyl or cyano. W ₂ is a halogen, an alkyl, a noroalkyl, an alkoxy, a haloalkoxy, an alkylthio, a haloalkylthio, a phenyl, a nitro or a cyano.

R ₂ of a substituted or unsubstituted cycloalkyl, as the substituent of the optionally substituted cycloalkyl good cycloalkylthio and R ₃ may be substituted which may cycloalkyl O carboxymethyl及beauty substituted, for example halogen, Alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxycarbonyl, alkylthio, haloalkylthio, cyano and the like. The number of substitutions may be one or more, and in the case of two or more, they may be the same or different.

Examples of the heterocyclic group of J include pyrrolyl, furyl, phenyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, 1,2,3- Oxadiazolyl, 1,2,4 Oxadiazolyl, 1,3,4 Oxadiazolyl, 1,2,3_thiadiazolyl, 1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl, 1,2,3,4-tetra Zolyl, pyridyl, pyrimidinyl, birazinyl, pyridazinyl, 1,2,4-triazinyl, 1,3,5-triazinyl, 1,2,3,5-tetrazinyl, 1,2,4,5-tetrazinyl, imidazolinyl, birazolinyl , Oxazolinyl, isooxazolinyl, thiazolinyl, isothiazolinyl, 1-pyrrolidinyl, 1-pibe Examples of the condensed heterocyclic group include indolyl, benzofuranyl, and the like. Examples include sobenzofuranyl, benzothenyl, benzimidazolyl, indazolyl, benzoxazolyl, benzisoxazolyl, benzothiazolyl, benzisothiazolyl, quinolyl, isoquinolyl, cinnolyl, phthalazyl, quinazalinyl, and quinoxalinyl.

In the formula (I), an alkyl or an alkyl moiety contained in R ₂ or R ₃ or Q, X,

The alkyl or alkyl moiety as a substituent contained in R ₂ , R ₃ or J is a straight-chain or branched one having 1 to 6 carbon atoms, for example, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl and the like. Y, R _P alkenyl contained in R ₂ or R _3, alkynyl, alkenyl moiety or alkynyl moiety, or Q, X, alkenyl as a substituent contained in R _2, R ₃ or J, alkenyl moiety, alkynyl or alkynyl moiety Examples thereof include linear or branched ones having 2 to 6 carbon atoms, for example, vinyl, aryl, butadienyl, isopropyl, ethynyl, propynyl, 2-penten-4-ynyl and the like. The cycloalkyl or cycloalkyl moiety contained in R ₂ or R ₃ or the cycloalkyl as a substituent contained in Q, X, R ₂ , R ₃ or J has 3 to 6 carbon atoms, for example, cyclopropyl , Cyclopentyl, cyclohexyl and the like.

In the formula (I), halogen as a substituent contained in Y or halogen as a substituent contained in Q, X, R ₂ , R ₃ or J is an atom of fluorine, chlorine, bromine or iodine. The number of halogen substituents as a substituent may be 1 or 2 or more. In the case of 2 or more, they may be the same or different.

Acrylonitrile compounds of the formula (I) are possible force to form a salt, is a salt thereof forces such as the hydrochloride salt include everything force ⁵ 'so long as it is agriculturally acceptable, sulfate, inorganic acid salts such as ^nitrates;? acetates, and organic acid salts force be mentioned up as main evening Nsuruhon acid salt.

The acrylonitrile compound of the formula (I) has a geometrical isomer (E-form and Z-form), and the present invention includes all of these isomers and mixtures thereof. In addition, depending on the type of the substituent, the optical isomer force 'existing force ⁵ ' may be used. And mixtures thereof.

Desirable compounds among the acrylonitrile compounds of the formula (I) or salts thereof are as follows.

[a] The heterocyclic group of J is pyrrolyl, furyl, chenyl, imidazolyl, vilazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, 1,2,3 —Oxadizazolyl, 1,2,4-oxodazolyl, 1,3,4-thoxadiazolyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl, 1,2,3 , 4-tetrazolyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, 1,2,4-triazinyl, 1,3,5-triazinyl, 1,2,3,5-tetrazinyl, 1,2,4,5-tetrazinyl, imidazolinyl , Virazolinyl, oxazolinyl, isoxazolinyl, thiazolinyl, isothiazolinyl, 1-pyrrolidinyl, 1-piperidinyl Is 4-morpholino and the fused heterocyclic group is indolyl, benzofuranyl, isobenzofuranyl, benzoenyl, benzimidazolyl, indazolyl, benzoxazolyl, benzoisoxazolyl, benzothiazolyl, benzoisothiazolyl, quinolyl, isoquinolyl An acrylonitrile compound of the above formula (I), which is cinnolyl, phthalazyl, quinazalinyl or quinoxalinyl, or a salt thereof.

[B] 0 ^months? Substituted one good phenyl or be J, a X gar J, Y is an C (= 〇) or one C (= S) R _2, is be replaced A good alkynyl or one SR ₃ , wherein R ₂ is an optionally substituted alkyl, an optionally substituted alkenyl, an optionally substituted alkynyl, an optionally substituted alkoxy, an optionally substituted alkenyloxy, Alkynyloxy, alkylthio which may be substituted, alkylthio which may be substituted, alkenylthio which may be substituted, cycloalkyl which may be substituted, cycloalkyl which may be substituted, cycloalkyloxy which may be substituted An optionally substituted cycloalkylthio, an optionally substituted phenyl, an optionally substituted phenoxy, an optionally substituted phenylthio, an optionally substituted benzyl, an optionally substituted Njiruokishi, it may also be substituted Ibe Njiruchio is one J, one 0- J or one S- J, R ₃ is optionally substituted alkyl Or an optionally substituted alkenyl, an optionally substituted alkynyl, an optionally substituted cycloalkyl, an optionally substituted benzyl or 1 J, wherein J is selected from the group consisting of 0, S and N Or a 5- or 6-membered heterocyclic group containing at least one atom selected from the group consisting of at least one atom selected from the group consisting of 〇, S and N. Or a salt thereof, wherein the acrylonitrile compound of the above formula (I) is a 6-11 membered fused heterocyclic group (the fused heterocyclic group may be substituted) containing 1-10.

[C] The heterocyclic group of J is pyrrolyl, furyl, phenyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, 1,2,3 —Oxadiazolyl, 1,2,4-oxadiazolyl, 1,3,4-thiadiazolyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl, 1,2,3,4 —Tetrazolyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, 1,2,4-triazinyl, 1,3,5-triazinyl, 1,2,3,5-tetrazinyl, 1,2,4,5-tetrazinyl, imidazolinyl, Birazolinyl, oxazolinyl, isoxazolinyl, thiazolinyl, isothiazolinyl, 1-pyrrolidinyl, 1-piperidini Or 4-morpholino, and the condensed heterocyclic group is indolyl, benzofuranyl, isobenzofuranyl, benzoenyl, benzimidazolyl, indazolyl, benzoxazolyl, benzisoxazolyl, benzothiazolyl, benzoisothiazolyl, quinolyl, isoquinolyl, The compound of the above-mentioned [b], which is cinnolyl, phthalazyl, quinazalinyl or quinoxalinyl, or a salt thereof.

[D] 0 ^months? Optionally substituted phenyl, imidazolyl optionally substituted, pyrazolyl which may be substituted, an optionally substituted Okisazoriru, optionally substituted Isookisazori Le, thiazolyl or substituted optionally substituted a good isothiazolyl be, X force ^s' replacement which may be imidazolyl, pyrazolyl optionally substituted, optionally substituted Okisa Zoriru, optionally substituted Isookisazoriru, thiazolyl optionally substituted or substituted Is optionally substituted alkynyl or —SR ₃ , wherein Y is one C (= 0) 1 ^ or —C (= S) R ₂ , and R ₂ is substituted Alkyl which may be substituted, alkenyl which may be substituted, alkynyl which may be substituted, a Alkoxy, optionally substituted alkenyloxy, optionally substituted alkynyloxy, optionally substituted alkylthio, optionally substituted alkenylthio, optionally substituted alkynylthio, optionally substituted cycloalkyl An optionally substituted cycloalkyloxy, an optionally substituted cycloalkylthio, an optionally substituted phenyl, an optionally substituted phenoxy, an optionally substituted phenylthio, an optionally substituted benzyl, Optionally substituted benzyloxy, optionally substituted benzylthio, 1 J, 1 0-J or

^-? S- is J, ₃ months optionally substituted alkyl, alkenyl which may be substituted, substitution which may be alkynyl, optionally substituted cycloalkyl, optionally benzyl substituted or mono- J A 5- or 6-membered heterocyclic group containing 1 to 4 at least one atom selected from the group consisting of 0, S and N (the heterocyclic group may be substituted); , A 6- to 11-membered condensed heterocyclic group containing at least one kind of atom selected from the group consisting of S and N, wherein the condensed heterocyclic group may be substituted. The acrylonitrile compound of (I) or a salt thereof.

[E] The compound of the above-mentioned [d], which is an optionally substituted phenyl, or a salt thereof.

[f] The heterocyclic group of J is pyrrolyl, furyl, chenyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, 1,2,3 —Oxadiazolyl, 1,2,4-oxodazolyl, 1,3,4-oxadiazolyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl, 1,2,3,4 —Tetrazolyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, 1,2,4-triazinyl, 1,3,5-triazinyl, 1,2,3,5-tetrazinyl, 1,2,4,5-tetrazinyl, imidazolinyl, Birazolinyl, oxazolinyl, isooxazolinyl, thiazolinyl, isothiazolinyl, 1-pyrrolidinyl, 1-piperidinyl Is 4-morpholino, and the condensed heterocyclic group is indolyl, benzofuranyl, isobenzofuranyl, benzoenyl, benzoimidazolyl, indazolyl, benzoxazolyl, benzisoxazolyl, benzothiazolyl, or benzothiazolyl The compound of the above (d) or (e), which is azolyl, quinolyl, isoquinolyl, cinnolyl, phthalazyl, quinazalinyl or quinoxalinyl, or Is its salt.

The acrylonitrile-based compound of the formula (I) or a salt thereof (hereinafter abbreviated as the compound of the present invention) can be produced, for example, according to the reaction [A], [B] and a usual method for producing a salt.

[A]

, (I)

(ID

The reaction [A] is described below. In the reaction [A], Q, X, Y and the formula (I) are as described above, and L is a halogen.

Reaction [A] is usually performed in the presence of a base. Bases include, for example, alkali metals such as sodium and potassium; alcoholates of alkali metals such as potassium tert-butoxide; carbonates such as potassium carbonate and sodium carbonate; potassium bicarbonate and sodium bicarbonate. Bicarbonates such as thorium; metal hydroxides such as potassium hydroxide and sodium hydride; metal hydrides such as potassium hydride and sodium hydride; trimethylamine, triethylamine, pyridine, 4-dimethyl One or more tertiary amines such as aminopyridine are appropriately selected.

Reaction [A] is performed in the presence of a solvent, if necessary. The solvent may be any solvent as long as it is inert to the reaction, for example, aromatic hydrocarbons such as benzene, toluene, xylene, and benzene; E-carbon chloride, methyl chloride, chloroform, and dichloromethane. Cyclic or acyclic aliphatic hydrocarbons such as dichloromethane, dichloroethane, trichloroethane, hexane and cyclohexane; ethers such as dioxane, tetrahydrofuran and getyl ether; esters such as methyl acetate and ethyl acetate Apolar aprotic solvents such as dimethyl sulfoxide, sulfolane, N, N-dimethylacetamide, N, N-dimethylformamide, N-methylpyrrolidone, pyridine; acetonitrile, pionitrile Nitriles such as acrylonitrile; acetone, methylethylketo One or two or more kinds are appropriately selected from ketones such as tertiary amines such as trimethylamine and triethylamine; water and the like. The reaction temperature of the reaction [A] is usually from 180 to 150 ° C (: desirably from 150 to 120 ° C), and the reaction time is usually from 0.1 to 48 hours, preferably from 0.2 to 24 hours. In the formula (I), when Y is-C (= 0) 1 ^ or 1 C (= S) R ₂

(B) Q O-T-Cl

1st step

(II) + C1-T-C1

(IV)

NC X

(V)

(1-1) The reaction [B] is described below. In the reaction (B), Q, X and the formula (II) are as described above, T is one C (= 0) one or —C (= S) —, and G is hydrogen, Na, Li, a mg B r, mg C 1 or mg I, 1 ^ ₄ 1 ^ or 1¾ ₂ (R i and R ₂ are as defined above) is.

The first step of the reaction [B] is performed in the presence of a base, if necessary. As the base, one or more tertiary amines such as trimethylamine, triethylamine, pyridine and 4-dimethylaminopyridine are appropriately selected.

The first step of the reaction [B] is usually performed in the presence of a solvent. The solvent may be any solvent as long as it is inert to the reaction, for example, aromatic hydrocarbons such as benzene, toluene, xylene, and benzene; carbon tetrachloride, methyl chloride, and chloroform. Cyclic or acyclic aliphatic hydrocarbons such as dichloromethane, dichloroethane, trichloroethane, hexane, and cyclohexane; ethers such as dioxane, tetrahydrofuran, and getyl ether; esters such as methyl acetate and ethyl acetate One or two or more are appropriately selected from the above.

The reaction temperature of the first step of the reaction (B) is usually from 1 to 80 to + 150 ° C, preferably from 1 to 50 to + 80 ° C, and the reaction time is usually from 0.1 to 48 hours, preferably from 0. In 5-24 hours is there.

The compound represented by the formula (V) ′ prepared in the first step of the reaction [B] is a novel useful intermediate compound in the present invention.

The second step of the reaction [B] is performed in the presence of a base, if necessary. Examples of the base include one or more of tertiary amines such as carbonates such as potassium carbonate and sodium carbonate; tertiary amines such as trimethylamine, triethylamine, pyridine and 4-dimethylaminopyridine. It is appropriately selected.

The second step of the reaction [B] is usually performed in the presence of a solvent. The solvent may be any solvent as long as it is inert to the reaction, for example, aromatic hydrocarbons such as benzene, toluene, xylene, and benzene; carbon tetrachloride, methyl chloride, and chloroform. Cyclic or acyclic aliphatic hydrocarbons such as dichloromethane, dichloroethane, trichloroethane, hexane, and cyclohexane; ethers such as dioxane, tetrahydrofuran, and getyl ether; esters such as methyl acetate and ethyl acetate One or two or more of nitriles such as acetonitrile, propionitrile and acrylonitrile; and ketones such as acetone and methylethylketone are appropriately selected.

The reaction temperature of the second step of the reaction (B) is usually 180 to 150 ° C, preferably _80 to + 80 ° C, and the reaction time is usually 0.1 to 48 ° C. Hours, preferably 0.5 to 24 hours.

The compound represented by the formula (II) in the above reactions (A) and (B) is an intermediate compound useful for producing the compound of the present invention, and includes a novel compound. .

Compounds of formula (II) are capable of forming salts, including any agriculturally acceptable salts, for example, inorganic salts such as hydrochlorides, sulfates, and nitrates. Acid salts; organic acid salts such as acetic acid salts and methanesulfonate salts; alkaline metal salts such as sodium salts and potassium salts; alkaline earth metal salts such as magnesium salts and calcium salts; dimethylammonium Quaternary ammonium salts such as triethylammonium, etc .;

In the compound of the formula (II), the force in which geometric isomers (E-form and Z-form) exist And all of these isomers and mixtures thereof. Further, the compound of the formula (II) has the formula:

When Q or X is a heterocyclic group or a fused heterocyclic group containing two or more N atoms, a compound represented by the formula:

In force which can exist as tautomers ^{represented?,} In the present invention embraces all of these individual Isomers and mixtures thereof. Further, the compound of the formula (Π) has optical isomers, and the present invention includes all of these isomers and mixtures thereof. The compounds of the formula (II) include those having pest control activity.

The compound of the formula (II) or a salt thereof can be produced, for example, according to the reaction [c] and a conventional method for producing a salt.

^[C] _{Q - CH 2 CN + X -} COZ ^ (II)

(VII) (VIII) Reaction [C] is described below. In the reaction [C], Q, X and the formula (II) are as described above, and Z is halogen or alkoxy.

Reaction [C] is usually performed in the presence of a base and a solvent.

Examples of the base include alkali metal such as sodium and potassium; alkali metal alcoholates such as sodium methylate, sodium methoxide and potassium tert-butoxide; and metal hydrogen such as potassium hydride and sodium hydride. Organic compounds such as methyllithium, n-butyllithium, tert-butyllithium, and phenyllithium; carbonates such as potassium carbonate and sodium carbonate; heavy compounds such as potassium bicarbonate and sodium bicarbonate Carbonates; metal hydroxides such as lithium hydroxide and sodium hydroxide; Amines such as nomethylamine, dimethylamine, and triethylamine; one or more amines are appropriately selected from pyridines, pyridines such as 4-dimethylaminopyridine, and the like.

The solvent may be any solvent as long as it is inert to the reaction, for example, aromatic hydrocarbons such as benzene, toluene, xylene, and benzene benzene; dioxane, tetrahydrofuran, and getyl ether. Ethers; alcohols such as methanol, ethanol, propanol, and tert-butanol; cyclic or cyclic such as carbon tetrachloride, methyl chloride, chloroform, dichloromethane, dichloroethane, trichloroethane, hexane, and cyclohexane Acyclic aliphatic hydrocarbons; esters such as methyl acetate and ethyl acetate; dimethyl sulfoxide, sulfolane, N, N-dimethylacetamide, N, N-dimethylformamide, N-methylpyrrolidone, pyridine Polar aprotic solvents such as acetone; Ketones such as ketones; Monomechiruamin, dimethylcarbamoyl Ruamin, amines such as Toryechiruamin; and one or more water is needed selection.

The reaction temperature of the reaction (C) is usually -80 to 10: I 50 ° C, desirably _ 50 to 120 ° C, and the reaction time is usually 0.1 to 48 hours, Preferably, it is 0.5 to 24 hours. In the reaction [C], when Z is a halogen, after reacting the formula (VII) with the formula (VIII), a hydrolysis reaction is carried out if necessary. In order to improve the yield of the target compound of formula (II), it is desirable to carry out this hydrolysis reaction.

The compound represented by the formula (VII) in the reaction [C] can be produced by the method described in WO97 / 40009, particularly, pages 85 to 86, or a method analogous thereto.

The compound of the present invention is useful as an active ingredient of a pesticide. In particular, it is useful as an active ingredient of pesticides such as insecticides, acaricides, nematicides, soil pesticides, fungicides, and pesticides in water.

Desirable embodiments of the pesticidal composition containing the compound of the present invention are described below. First, describe pesticides such as insecticides, acaricides, nematicides, soil pesticides, and fungicides. The pest control agent containing the compound of the present invention is useful as an insecticide, acaricide, nematocide, or soil insecticide (hereinafter abbreviated as a pesticide). For example, Namihada two, Nisenamihada two, Kanzahada two , Plant parasitic mites such as Citrus red mite, Apple tick mites, Cyanophoridae, Citrus saccharidum, Nedani, etc .; Animal parasitic mites such as ticks; Aphid such as peach aphid, Petra aphid, Konaga, Spiny beetles, Lotus leafworms, Codling moths, Ball worms, Tobacco bad worms, Gypsy moths, Konomeiga, Chinokokaku monmonaki, Colorado potato beetle, Scotch beetle, Bolui building, Scarabaeidae, Scarabaeidae, Scarabaeidae, Codworm , Grasshoppers, flies, Agricultural pests such as caterpillars, tamanayaga, power brallaga, ari, etc .; such as root-knotweeds, cysts-census, negusarecentiyu, rice singaressenchu, strawberry-medium-chestnuts, matsunoza-centiyu, etc. Plant parasitic nematodes; gastropods, such as slugs and scabies; soil pests, such as duckweeds and scabies; sanitary pests, such as gadani, cockroaches, gadfly, acaie Storing pests such as Bakuga, Azukizombushi, Kokunusutomodoki, Tenebrionidae, etc .; Clothing, house pests such as Iga, Himechabushibushi, Termites, etc .; Species; other fleas, lice, It is effective for controlling flies. Above all, pesticides containing the compounds of the present invention can be used to control plant parasitic mites, animal parasitic mites, agricultural pests, sanitary pests, clothing, house pests, indoor dust mites, etc. Especially effective. The pesticides containing the compound of the present invention are also effective for controlling various insect pests which are resistant to drugs such as organophosphorus agents, carbamate agents and synthetic pyrethroid agents. Further, since the compound of the present invention has excellent systemic translocation, by treating a soil with a pesticide containing the compound of the present invention, soil harmful insects, mites, nematodes, abdomen At the same time as controlling insects and isopods, pests in the foliage can be controlled.

Further, the pesticides containing the compounds of the present invention, the force is useful as fungicides, For example rice blast, sheath blight, Gomaha ^blight;? Wheat powdery mildew, scab, Rust, snow rot, naked smut, eye spot, leaf blight, wilt; citrus black spot, scab; apple moss Nilia disease, powdery mildew, spot leaf spot, scab; pear scab, black scab; peach scab, scab, phomopsis rot; grape scab, scab, powdery mildew, Downy mildew; Oyster anthracnose, deciduous disease; Persimmon anthracnose, powdery mildew, vine blight, Downy mildew; Tomato ring spot, leaf mold, plague; Brassica vegetable black It is effective for controlling diseases such as spot blight; potato summer blight; blight; strawberry powdery mildew; gray mold and sclerotium on various crops; and Fusarium, picidum, and rhizoctonia. It is also effective in controlling soil diseases caused by fungi such as Verticillium and Plasmodiophylla.

Other desirable embodiments of the pesticidal agent containing the compound of the present invention include the above-mentioned plant parasitic mites, agricultural pests, plant parasitic nematodes, gastropods, soil pests, various diseases, various soil diseases, and the like. And pest control agents for agricultural and horticultural use that comprehensively control harmful substances.

Pest control agents such as pesticides and fungicides containing the compound of the present invention are usually mixed with the compound and various agricultural auxiliaries to prepare powders, granules, water dispersible granules, wettable powders, aqueous solutions. Forces used in the form of suspensions, oily suspensions, aqueous solvents, emulsions, pastes, aerosols, micro-sprays, etc. s', as long as they meet the purpose of the present invention, It can be in any formulation form used in the art. Auxiliaries used in the formulation include diatomaceous earth, slaked lime, calcium carbonate, talc, white wool, kaolin, bentonite, mixtures of kaolinite and sericite, clay, sodium carbonate, baking soda, sodium sulfate, zeolite, starch, etc. Solid carrier; water, toluene, xylene, solvent naphtha, dioxane, acetone, isophorone, methyl isobutyl ketone, benzene, cyclohexane, dimethyl sulfoxide, N, N-dimethylformamide, N, N — Solvents such as dimethylacetamide, N-methyl-2-pyrrolidone, and alcohol; fatty acid salts, benzoates, alkylsulfosuccinates, dialkylsulfosuccinates, polycarboxylates, alkyl sulfates, alkyl sulfates Salt, alkylaryl sulfate, a Kildiglycol ether sulfate, alcohol sulfate, alkyl sulfonate, alkyl aryl sulfonate, aryl sulfonate, lignin sulfonate, alkyl diphenyl ether disulfonate, polystyrene sulfonate, Alkyl phosphate ester, alkyl aryl phosphate, styryl aryl phosphate, polyoxyethylene alkyl ether Sulfate, polyoxyethylene alkyl aryl ether sulfate, polyoxyethylene alkyl aryl ether sulfate, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl aryl phosphate, formalin naphthalene sulfonate Anionic surfactants and spreading agents such as salts of condensates; sorbitan fatty acid esters, glycerin fatty acid esters, fatty acid polyglycerides, fatty acid alcohol polyglycol ethers, acetylene glycol, acetylene alcohol, and oxyalkyl Len block polymer, polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, polyoxyethylene styrylaryl ether, polyoxyethylene glycol alcohol Nonionic surfactants such as kill ethers, polyoxyethylene fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene glycerin fatty acid esters, polyoxyethylene hardened castor oil, and polyoxypropylene fatty acid esters Agents and spreading agents: olive oil, kapok oil, castor oil, palm oil, camellia oil, coconut oil, sesame oil, corn oil, rice bran oil, peanut oil, cottonseed oil, soybean oil, rapeseed oil, linseed oil, cutting oil, liquid paraffin and the like force ^s such as vegetable oil or mineral oil such as. These adjuvants can be selected from those known in the art without departing from the purpose of the present invention. In addition, various commonly used auxiliaries such as a bulking agent, a thickening agent, an anti-settling agent, an antifreezing agent, a dispersion stabilizer, a safener, and a fungicide can be used. The compounding ratio of the compound of the present invention and various auxiliaries is 0.001: 99.999 to 95: 5, preferably 0.005: 99.995 to 90:10. In the actual use of these preparations, they can be used as they are, or diluted to a predetermined concentration with a diluent such as water, and can be used by adding various spreading agents as necessary.

The application of pesticides such as pesticides and fungicides containing the compound of the present invention cannot be specified unconditionally due to differences in meteorological conditions, formulation, application time, place of application, types and occurrence of pests, etc. The active ingredient concentration is generally 0.05 to 800,000 ppm, desirably 0.5 to 5000 000 ppm, and the application rate per unit area is 0.05 to 10,000 g of the compound of the present invention per hectare. However, it is preferably 1 to 5000 g. The application of the pesticide, which is a desirable embodiment of the pesticide containing the compound of the present invention, is the same as described above. Although it cannot be specified unconditionally due to differences in various conditions, it is generally carried out at an active ingredient concentration of 0.1 to 500,000 ppm, preferably 1 to 100,000 ppm, and the amount of application per unit area is based on the present invention per hectare. The compound is 0.1 to 10000 g, preferably 10 to 1000 g, and the application of the bactericide cannot be unconditionally specified due to the difference in various conditions as described above. Generally, 0.1 to 500,000 ppm is desirable. Is carried out at an effective component concentration of from l to 100,000 ppm, and the application rate per unit area is from 0.1 to 10,000 g, preferably from 10 to 1,000 g, of the compound of the present invention per hectare. Further, the application of the pesticidal composition for agricultural and horticultural use, which is another desirable embodiment of the pesticidal composition containing the compound of the present invention, is performed according to the above-mentioned application of the pesticide and the fungicide. The present invention also includes a method for controlling harmful pests by such an application method.

Various formulations of pesticides such as insecticides and fungicides containing the compound of the present invention, or application of dilutions thereof, are usually applied by the general application method, that is, spraying (for example, spraying, spraying, Misting, atomizing, granulation, surface application, etc.), soil application (mixing, irrigation, etc.), surface application (application, dressing, coating, etc.), immersion bait etc. Further, it is also possible to feed the livestock with the above-mentioned active ingredient mixed with feed and control the occurrence and development of harmful insects, particularly harmful insects, in the excrement. It can also be applied by the so-called ultra-low volume spray method. In this method, it is possible to contain 100% of the active ingredient.

In addition, pesticides such as pesticides and fungicides containing the compound of the present invention can be mixed with or used in combination with other pesticides, fertilizers, and safeners. , May show action. Other pesticides include herbicides, insecticides, acaricides, nematicides, soil pesticides, fungicides, antivirals, attractants, antibiotics, plant hormones, plant growth regulators, etc. Can be In particular, a mixed pest control composition in which the compound of the present invention and one or more of the active ingredient compounds of other pesticides are mixed or used in combination, the application range, timing of chemical treatment, control activity, etc. in a favorable direction. that force ^is? possible to improve. The compound of the present invention and the active ingredient compound of another pesticide may be prepared separately and mixed at the time of spraying, or both may be prepared together and used. The present invention also includes such a mixed pest control composition. It is.

The mixing ratio of the compound of the present invention to the active ingredient compound of another pesticide cannot be specified unconditionally due to differences in weather conditions, formulation, application time, place of application, types of pests and occurrence, but generally 1: 1. 300 to 300: 1, preferably 1: 100 to 00: 1. The appropriate amount of application is 0.1 to 5000 g, preferably 10 to 3000 g, as the total amount of the active ingredient compound per hectare. The present invention also includes a method for controlling pests and pests by a method for applying such a mixed pest control composition.

Examples of the pesticides, acaricides, nematicides or soil pesticides in the above-mentioned other pesticides, ie, active ingredient compounds of the pesticides (generic names; including some applications) include, for example, profenophos (P rofenofos) ゝ dichlorvos (D ichiorvos), fenamiphos (Fen am iphos), funitrothion (F enitrothion), EPN, diazinone (D iazin 0 n), chlorpyrifos methyl (Ch iorpyrifos- me thyl), acephate (Ac ephate), Organophosphate compounds such as Prothiofos, Phosthiazate, Phosphocarb, etc .;

Carbaryl (Carbary 1), Provoxur (Propoxur), Aldicarb (A1 dicarb), Carbofuran (Carbofuran), Thiodicarb (Thiodicarb), Methomil (Meth omyl), Oxamil (◦xamy1), Echioffencarp Carbamate compounds such as (E thiofencarb), Pirimicarb, and Fenobubucarb;

Neraist toxin derivatives such as cartap (Cartap), thiocyclam (Thiocyc1am);

Organic chlorinated compounds such as dicophor (Dic0f01) and tetradiphone (Tetradifon);

Organometallic compounds such as fenbutatin oxide (Fenbutatatin Oxide);

Fenvalerate, Permethrin n), pyrethroids such as cypermethrin, deltamethrin (De1 tamethrin), cyhalothrin (Cyha1 othrin), tefluthrin (Tef1 uthrin), etofenprox (Ethofen nprox) C-based compounds;

Benzoyl perylene compounds such as difluvenzuron (Diflubenzenzuron), chlorfluazuron (Ch1orrfluazazuron), tefluvenzuron (Teflubenzuron), and nonolulone (Novarulon);

Juvenile hormone-like compounds such as methoprene (Methaoprene);

Pyridazinone compounds such as pyrigben (Pyridaben);

Pyrazole-based compounds such as fenpyroximate (Fenpyroximate), fipronil (Fipronyl), and tebufenpyrad (Tebufenpyrad);

Neonicotinoids such as imidacloprid (I midac 1 oprid) ゝ nitenpyram, acetamiprid, diacloden (Diac 1 ode _n ), thiacloprid (T hiac 1 oprid);

Hydrazine-based compounds such as tebufenozide (Tebufenozid), methoxfenozide (Methoxyfenozid), and chromafenozide (Chromomafenozid);

Dinitro compounds, organic sulfur compounds, urea compounds, triazine compounds, hydrazone compounds, and other compounds, such as buprofezin, hexthiazox (Hexythiaz0X), and amitraz ), Chlordimeform, Chiladomofen, Triazamate (T riaz ama te), Pimetrozine (Pyme trozine), Pyrimidifen, Chlorfenapyr, I Compounds such as ndoxacarb, acequinocyl (A cequinocy 18 etoxazole), cilomasine (Cyroma zine); and BT agents, insect pathogen virus agents, etc. It can be mixed and used with any microbial pesticide, antibiotics such as avermectin (AV ermectin), milbemycin (Mi bemycin), and spinosad (S pinosad).

Examples of the active ingredient compound of the fungicide (generic name; including some applications) in the other pesticides include, for example, mepanipyrim, pyrimesanil (Pyrimethani 1), and cyprodinil (Cyprodini 1). Pyrimidinamine compounds; Triadimefone (T riadimef 0 n), bitertanol (Bitertano 1), triflumizol (T riflum izole), etaconazole (E taconazo 1 e), propiconazol (P ropiconazo 1 e), Penconazo 1 (Penconazo 1 e), Flusilazol (Flusi 1 azo 1 e), Microbutanil (Myc 1 obutani 1), Cyproconazole (Cyproconazo 1 e), Terbuconazole (Terbuconazole) ), Hexaconazole (Hexaconazole), Furconazole (Furconazol e_c is Prochloraz (Pro azole compounds such as chlorconaz), metconazole (Metconazole), epoxyconazole (Epoxiconconazle1e, tetraconazole (Tetraconaz01e);

Quinoxaline-based compounds such as quinomethionate (Quinomethionate);

Dithiocarbamate compounds such as maneb (Maneb), zineb (Zineb), manzeb (Mancozeb), polycarbamate (Polycarbamate), and propineb (Propine);

Organochlorine compounds such as husalide (Fthalide), chlorothalonil (Chororothalon1), and quintozene (Quint0zene);

Benomyl (Benomyl), Thiophanate-Methyl, Carbendazim, 4-Chloro-2-cyano 1 _Dimethylsulfamoyl-1-5- (4-Methylphenyl) Imidazo-I Imidazole-based compounds such as Pyridinamine compounds such as fluazinam (F 1 uazin am);

Cyanoacetamide-based compounds such as cimoxanil (Cymo Xani 1); metalaxyl (Meta 1 a Xy 1), oxadixyl (〇xadixy 1), ofures (O furace), benalaxyl (Benalaxyl), and furalaxil ( Phenylamide-based compounds such as Fu ra 1 a X y 1) and Cyprofuram;

Sulfenic acid-based compounds such as diclofluoride (Dich10f1uanid); Copper-based compounds such as cupric hydroxide (Cuprichydroxide) and organic copper (OxineCopper);

Isoxazol-based compounds such as hydroxysoxazole (Hydroxyisoxazole);

Fosetylaluminum (Fostyyl_Al), turquophosmethyl (Tolcfos—Methy1), S-benzyl 0,0-diisopropyl phosphorothioate,

Organophosphorus compounds such as 0-ethyl S, S-diphenyl phosphorodithioate, aluminum ethylhydrido genphosphonate;

N-halogenothioalkyl compounds such as captan (Captan), captaphor (Captafo1), and phthalate (Fo1pet);

Dicarboxyimide compounds such as procymidone (Procymidone), iprodione (I prodione), and hinclozolin (Vinc10z01in); such as flutolanil (Flutolani1) and mepronil (Meproni1) Benzanilide compounds;

Piperazine compounds such as trifoline (Triffine);

Pyridine compounds such as pyrifenox (Pyrifenox);

Carbinol-based compounds such as fenarimol (Fenarimol) and furtriafluor (Fiutriafil);

Piberidine compounds such as fenpropidine; morpholine compounds such as fenpropimorph; Organotin compounds such as fentin hydroxide, fentin acetate, etc .;

Urea-based compounds such as Penciclone (Pencycuron);

Cinamic acid-based compounds such as dimethomorph (Dimethomol ph); felucca-based compounds such as jetfencalp (Diet fofencarb);

Cyanopyrroyl compounds such as fludioxonil (Fludioxoni1) and fenpiclonil (Fenpicloni1);

Methoxyacrylate-based compounds such as azoxis trobin (Az0Xystr0bin), kresoximmethyl (Kresosim—Methyl), metominophen (Metominofen);

Oxazolidinone compounds such as famoxadone; atraquinone compounds; crotonic acid compounds; antibiotics and other compounds such as isoprothiolane (Is0pr0thi01ane) and tricyclazole (Tricyclazole). , Pyroquilon (Pyro qu ilon), Diclomedine (Diclom ezine), Probenazole (Probenazo 1 e), Quinoxyfen (Quinoxyfen), Propamorocarb hydrochloride (Prop amo carb Hy drochloride), Spiroxamine (Sp irox am ine);

Next, pest control agents such as biofouling agents in water are described.

Underwater biofouling agents containing the compound of the present invention can be used for ships and underwater structures (for example, harbor facilities, buoys, pipelines, bridges, submarine bases, offshore oilfield drilling facilities, power plant headraces, stationary nets) Control of harmful water-borne organisms against marine water, etc., specifically, plants such as green algae and brown algae, animals such as fujibo, selbra, sea squirt, mussels, oysters, etc., and slime It is effective in preventing aquatic organisms such as various bacteria, molds, diatoms, etc. from adhering to the ship's bottom and underwater structures and preventing their propagation.

The underwater organism-controlling agent containing the compound of the present invention provides an antifouling property and a slime resistance for a long period of time, and has an excellent effect of preventing harmful underwater organisms from adhering to ships and underwater structures and preventing their propagation. Demonstrate fruit.

The water-borne biocontrol agent containing the compound of the present invention is usually formulated as a coating composition, and may be used in the form of a force, and in some cases, in another dosage form (solution, emulsion, pellet, etc.). it can. Examples of the paint vehicle used when formulating the compound of the present invention as a paint composition include resin vehicle ^s that are usually used, such as 'powers to be mentioned', for example, vinyl chloride resins, vinyl chloride-vinyl acetate copolymers, and the like. Vinyl chloride-vinyl isobutyl ether copolymer, chlorinated rubber resin, chlorinated polyethylene resin, chlorinated polypropylene resin, acrylic resin, styrene-butadiene resin, polyester resin, epoxy resin, phenolic resin, synthetic rubber, Silicone rubber, silicone resin, petroleum resin, oil and fat resin, rosin ester resin, rosin stone, rosin, etc. Further, as an antifouling vehicle, an organotin of unsaturated mono- or dicarboxylic acid obtained by a condensation reaction of (meth) acrylic acid with an organotin compound such as bis (triptyltin) oxide or triphenyltinhydroxide. An acrylyl copolymer resin composition containing a compound salt as a constituent unit, a resin containing a metal element such as copper, zinc, and tellurium in a side chain can also be used. When the compound of the present invention is formulated as a coating composition, the compounding ratio is 0.1 to 60% by weight, preferably 1 to 40% by weight of the compound of the present invention. Prepared.

The coating composition containing the compound of the present invention can be prepared, for example, using a ball mill, a pebble mill, a roll mill, a sand glider mill, or the like according to a method well known in the field of paint production. In addition, the coating composition can contain a plasticizer, a coloring pigment, an extender, an organic solvent, and the like, which are generally used in the art.

The coating composition containing the compound of the present invention can further contain other known inorganic or organic antifouling agents, if necessary. Such antifouling agents include, for example, cuprous oxide, copper rhodanide, copper hydroxide, copper naphthenate, metallic copper, various tin compounds and dithiolrubamic acid derivatives such as tetramethylthiuram monosulfide, Tetramethylthiuram disulphide, bis-bis (dimethyldithiocarbamate) zinc, ethylene-bis (dithioflavin) zinc, ethylene-bis (dithiocarbamic acid) manganese, bis-dimethy Ludici talent rubamic acid) Copper.

As described in detail above, the compound of the present invention is effective as an active ingredient of a pesticidal agent.

[1] A method for controlling pests using a pest controlling agent containing the above formula (I) or a salt thereof as an active ingredient or a compound thereof.

[2] A pest control agent for agricultural and horticultural use containing the formula (I) or a salt thereof as an active ingredient, or a method for controlling pests in the agricultural and horticultural field using the compound.

[3] A pesticide containing the above formula (I) or a salt thereof as an active ingredient or a method for controlling pests using the compound.

[4] An insecticide containing the above formula (I) or a salt thereof as an active ingredient or a method for controlling harmful insects using the compound.

[5] An acaricide containing the above formula (I) or a salt thereof as an active ingredient or a method for controlling mites using the compound.

[6] A nematicide containing the above formula (I) or a salt thereof as an active ingredient or a method for controlling nematodes using the compound.

[7] A method for controlling soil pests using a soil pesticide containing the above formula (I) or a salt thereof as an active ingredient or a compound thereof.

[8] A fungicide containing the above formula (I) or a salt thereof as an active ingredient or a method for controlling harmful bacteria using the compound.

[9] A method for controlling underwater organisms using the above-mentioned formula (I) or a salt thereof as an active ingredient, or a method of controlling underwater organisms using these compounds.

Then the force of describing embodiments of the present ^invention?, The present invention is not limited thereto. First, synthesis examples of the compound of the present invention will be described.

Synthesis example 1

a — (4-tert-butylphenyl) — β— (5-chloro-1-methyl_3_trifluoromethylpyrazole-14-yl) — β— (S-methylthiocarbonyloxy) a acrylonitrile No.210) 1) 4-(tert-butyl) benzyl cyanide 1. Og, 5 _ 1-methyl 3- 3-trifluoromethylpyrazole 4-1.57 g of rubonic chloride 1.57 g of tetrahydrofuran 20m Then, 1.0 g of potassium tert-butoxide was added thereto under ice-cooling. Thereafter, the reaction was carried out for 3 hours while gradually raising the temperature to room temperature.

After completion of the reaction, water was added to the reaction solution, and the solution was acidified with 6N-hydrochloric acid, and then extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure. The residue was dissolved in 50 ml of ethanol, and 7 ml of a 5% aqueous sodium hydroxide solution was added dropwise thereto with stirring at room temperature. Then, the mixture was stirred at room temperature for 2 hours, ethanol was distilled off under reduced pressure, and the residue was extracted with ether and water. The aqueous layer was adjusted to pH 5 with 6N hydrochloric acid and extracted with methylene chloride. The organic layer is washed with water, dried over anhydrous magnesium sulfate, and the solvent is distilled off under reduced pressure. A— (4-tert-butylphenyl) —β— (5-chloro-1-1-methyl-1-3-trifluoro Methylpyrazole (41-yl) _ / 9-hydroxyatarilonitrile (4 g) was obtained.

2) a- (4-tert-butylphenyl) -β- (5-chloro-1-1-methyl-3-trifluoromethylpyrazole-14-yl) -1-hydroxyacrylonitrile 0.5 _g and triethylamine 0.2 g was dissolved in 20 ml of tetrahydrofuran, and 0.16 g of S-methyl chlorothioformate was gradually added dropwise thereto under ice-cooling. After the completion of the dropwise addition, the reaction was carried out for 2 hours while gradually raising the temperature to room temperature.

After completion of the reaction, ethyl acetate and water were added to the reaction solution for extraction. The organic layer is washed with water, dried over anhydrous sodium sulfate, the solvent is distilled off under reduced pressure, and the residue is purified by silica gel column chromatography (developing solvent: n-hexane Z ethyl acetate = 9-1). This gave 0.35 g of the desired product having a melting point of 43.5 ° C. The NMR spectrum of this product is as follows.o

Ή-image R δ ppm (solvent: CDCy400MHz):

1.35 (s, 9H), 2.37 (s, 3H), 3.80 (s, 3H), 7.38 (d, 2H), 7.50 (d, 2H)

Synthesis example 2

a-(4-tert-Butylphenyl) — β- (5-chloro-1-1-methyl-13-tri Synthesis of Fluoromethylpyrazole-4-yl) -β- (S-methyldithiocarbonyloxy) acrylonitrile (Compound No.215)

a-(4-tert-butylphenyl)-β-(5-chloro-1-methyl-3-trifluoromethylpyrazole-1-4-yl) 1-hydroxyacrylonitrile 0.8 g of N, N-dimethyl It was dissolved in 10 ml of formamide, and 0.09 g of 60% sodium hydride was gradually added thereto under ice cooling. Stirring was continued under ice-cooling, and after confirming that the generation of hydrogen gas had ended, 0.29 g of methyl chlorodithioformate was gradually added dropwise. After completion of the dropwise addition, the reaction was carried out for 2 hours while gradually raising the temperature to room temperature.

After completion of the reaction, ether and water were added to the reaction solution for extraction. The organic layer was washed with water, dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (developing solvent: n-hexane Z ethyl acetate = 91) to give a melting point. 0.2 g of the desired product at 50.9 ° C was obtained. The NMR spectrum data of this is as follows.

¾-NMR δ ppm (solvent: CD Cy400MHz):

1.30 (s, 9H), 2.49 (s, 3H), 3.89 (s, 3H), 7.38 (d, 2H), 7.51 (d, 2H)

Synthesis example 3

a- (4-tert-Butylphenyl) -1-β- [ethoxy (thiocarbonyl) oxy] -1-β- (3,5-dimethylisoxazole-14-yl) acrylonitrile (Compound No., 419) Synthesis of

1) Dissolve 0.5 g of 3,5-dimethylisoxazole-14-carbonyl chloride in 12 ml of tetrahydrofuran, add 0.6 g of 4-tert-butylbenzyl cyanide and cool on ice. Then, 0.63 g of potassium tert-butoxide was added, and the mixture was returned to room temperature and reacted for 1 hour.

After completion of the reaction, the reaction mixture was poured into water and extracted with methylene chloride. The aqueous layer was acidified with hydrochloric acid and extracted with methylene chloride. The resulting organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure to give an oily (4-tert-butylphenyl) 1 / 3-hydroxy There was obtained 66 g of 1β- (3,5-dimethylisoxazol-1-yl) acrylonitrile. The NMR spectrum data of this is as follows. Ή-image R δ ppm (solvent: CDCy400MHz):

1.35 (s, 9H), 2.32 (s, 3H), 2.55 (s, 3H), 7.49 (d, 2H), 7.59 (d, 2H)

2) α- (4 tert-butylphenyl) 1 / 3-hydroxy-1,3- (3,5-dimethylisoxazole_ 4-yl) A mixture of 0.2 g of acrylonitrile and 5m1 of dichloroethane 0.1 g of triethylamine was added to the mixture, and the mixture was ice-cooled. 0.12 g of ethyl chloroformate was added, and the mixture was returned to room temperature and reacted for 3 hours.

After completion of the reaction, water was added to the reaction mixture, extracted with methylene chloride, washed with water, and the organic layer was dried over anhydrous sodium sulfate. Then, the mixture is concentrated under reduced pressure, and the obtained residue is purified by silica gel column chromatography (developing solvent: n-hexane Z ethyl acetate = 4/1) to obtain 0.2 g of the desired product having a melting point of 93 to 94 ° C. I got The NMR spectrum data of this is as follows.

Ή-NMR δ ppm (solvent: CDCU400MHz):

1.27 (s, 9H), 1.40 (t, 3H), 1.97 (s, 3H), 2.09 (s, 3H), 4.52 (q, 2H), 7.43 (d, 2H), 7.53 (d, 2H) Synthesis example Four

a-(4-tert-Butylphenyl)-β- (3_cyclo-1--1-cyclopropylpyrazole-14-yl)-β-[(methylthio) carbonyloxy] acrylonitrile (Compound No. 420 and below) 42 Synthesis of 1)

1) To a mixture of 0.95 g of 3-cyclopropylpyrazole-4-carboxylic acid and 10 ml of dichloroethane, 0.73 g of thionyl chloride and a catalytic amount of dimethylformamide were added. Allowed to react for hours.

After completion of the reaction, the reaction mixture was concentrated under reduced pressure to obtain 0.95 g of 3-chloro-1-cyclopropylpyrazol-4-carbonyl chloride.

2) 0.5 g of 3-chloro-1-cyclopropylpyrazole-14-carbonyl chloride obtained in the previous step was dissolved in 10 ml of tetrahydrofuran without purification, and 0.4 g of 4-tert-butylbenzyl cyanide was purified. After adding g, the mixture was cooled on ice, 0.49 g of potassium tert-butoxide was added, and the mixture was returned to room temperature and reacted for 1 hour.

After completion of the reaction, the reaction mixture was poured into water and washed with methylene chloride. Hydrochloric acid in the aqueous layer The mixture was acidified, extracted with methylene chloride, and the obtained organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure to give oily 4- (tert-butylphenyl) -β- (3-chloro-1- —Cyclopropylpyrazole-4-yl) -1-hydroxyacrylonitrile 0.45 g was obtained. The NMR spectrum data of this is as follows.

匪 -band R δ ppm (solvent: CDCl3 / 400MHz):

1.09 (m, 2H), 1.15 (m, 2H), 1.31 (s, 9H), 3.56 (m, lH), 7.33 (d, 2H), 7.42 (d, 2H), 8.01 (s, lH) 3) Mixture of 0.15 g of α- (4-tert-butylphenyl) -β- (3-chloro-1--1-cyclopropylpyrazole-4-yl) -1-/-hydroxyacrylonitrile obtained in the previous step and 8m1 of dichloroethane After adding 58 mg of triethylamine to the mixture, the mixture was cooled with ice, 58 mg of methylchlorothiol formate was added, and the mixture was returned to room temperature and reacted for 0.5 hour. After completion of the reaction, water was added to the reaction mixture, extracted with methylene chloride, and washed with water. The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (developing solvent: n-hexane Z ethyl acetate = 85/15) to give the oily target product. (Compound N 0.420) 0.11 g and the desired product (Compound No. 421) 0.06 g each having a melting point of 128 to 130 were obtained. Its NMR spectrum data is as follows.

匪 -band R δ ppm (solvent: CDCl3 / 400MHz):

Compound No. 420

1.08 (m, 2H), 1.20 (m, 2H), 1.33 (s, 9H), 2.32 (s, 3H), 3.62 (m, lH), 7.44 (d, 2H), 7.49 (d, 2H), 8.15 (s, lH)

Compound No. 421

0.93 (m, 4H), 1.29 (s, 9H), 2.42 (s, 3H), 3.41 (m, lH), 7.06 (s, lH), 7.24 (d, 2H), 7.36 (d, 2H) Table 1 shows typical examples of the compound of the present invention represented by the above formula (I). These compounds may be synthesized based on the above synthesis examples or the above-mentioned various methods for producing the compound of the present invention. I can ^do it.

The abbreviations used in Table 1 have the following meanings.

Me: methyl group, Et: ethyl group, Pr: propyl group, Bu: butyl group, Pen: pen Tyl group, He x: hexyl group, P h: phenyl group, t: tertiary, Cy: cyclo

Q22:

Q28: Q29

: O ^ ^CH3

, ^CF 3 _ _ CH ₃

X63: A N X64:

NCH ₂ C ヽ fsjz CI ヽ〇z

CH ₃

In addition, benzyl (4-CI) represents a 4-cycloalkyl benzyl group. The same applies to other similar descriptions.

Table 1 (I)

Compound No Q Y X Physical properties (melting point Z refractive index)

1 Q 1 -COSMe X 1 oily

2 Q 1 -COSEt X 2 Oily

3 Q 1 -CSOMe X 4 147-149 ° C

4 Q 1 -CSOEt X 5

5 Q 1 -CSOPh xio

6 Q 1 -CSzMe X ll

7 Q 1 -CSzEt X 12

8 Q 1 -COSMe X 3 95 98 ° C

9 Q 1 -COSEt X 3

10 Q 1 -CSOMe X 3

11 Q 1 -CSOEt X 3 88 90 ° C

12 Q 1 -CSOPh X 3

13 Q 1 -CS ₂ Me X 3

14 Q 1 -CS ₂ Et X 3

15 Q 1 -CxisCH: then xls X 3

16 Q 1 -COSMe X 6

17 Q 1 -COSEt X 6

18 Q 1 -CS ₂ Me X 6

19 Q 1 -CS ₂ Et X 6

20 Q 1 CH ₂ C≡CI X 6

21 Q 1 -COSMe X 7 146 148 ° C

22 Q 1 -COSEt X 7 Oily

23 Q 1 -CS ₂ Me X 7 n _D 4 ₈ .e 1.5926

_{24 Q 1 -CS 2 Et X 7} no 47 - 8 1.6291 Table 1 (continued)

Table 1 (continued:

Table 1 (continuation;

Table 1 (continued)

Table 1 (continued)

Table 1 (continued)

Compound NQ Q Y X Physical properties (melting point, refractive index)

155 Q 3 -COSEt X 3

156 Q 3 -CSOMe X 3

157 Q 3 -CSOEt X 3

158 Q 3 -CSOPh X 3

159 Q 3 -CS ₂ Me X 3

160 Q 3 -CS ₂ Et X 3

161 Q 3 -COSMe X 8

162 Q 3 -COSEt X 8

163 Q 3 -CSOMe X 8

164 Q 3 -CSOEt X 8

165 Q 3 -CSOPh X 8

166 Q 3 -CS ^ Me X 8

167 Q 3 -CSaEt X 8

168 Q 3 -COSMe X 9 94-96. C

169 Q 3 -COSEt X 9

170 Q 3 -CSOMe X 9

171 Q 3 -CSOEt X 9

172 Q 3 -CSOPh X 9

173 Q 3 -CS ₂ Me X 9

174 Q 3 -CS.Et X 9

175 Q 4 -COSMe X23

176 Q 4 -COSEt X25

177 Q 4 -CSOMe X26

178 Q 4 -CSOEt X28

179 Q 4 -CSOPh X29

180 Q 4 -CS ^ Me X31 Table 1 (continued)

Compound NQ Q Y X Physical properties (melting point Z refractive index)

181 Q4 -CS ^ Et X32

182 Q4 -COSMe X34

183 Q4 -CS ^ Me X35

184 Q4 -COSMe X3 87-88. C

185 Q4 -COSEt X3 Oily

186 Q 4 -CSOMe X 3

187 Q4 -CSOEt X3 Oily

188 Q 4 -CSOPh X3

189 Q4 -CS ₂ Me X 3

190 Q4 -CS ₂ Et X3

191 Q4 -CSO-,,,, (4-S0 ₂ Me) X3

192 Q4 -COSMe X 6

193 Q4 -COSEt X 6

194 Q4 -CS ₂ Me X 6

195 Q4 -CS ₂ Et X 6

196 Q4 -CS ₂ - to ,, Nshi ,, le (4-N0 ₂₎ X 6

197 Q4 -COSMe X 7 oily

198 Q4 -COSEt X 7 Oily

199 Q4 -CS ₂ Me X 7 53.4 ° C

200 Q4 -CS ₂ Et X 7

201 Q4 -CS-2-Piricil "X 7

202 Q4 -COSMe X 8 109 ~ 113 ° C

203 Q4 -COSEt X8 Oily

204 Q4 -CSOMe X 8

205 Q4 -CSOEt X 8 Oily

206 Q4 -CSOPh X 8 Table 1 (continued)

Compound No Q Y X Physical properties (melting point z refractive index)

207 Q 4 -CS ^ Me X 8 52.2 ° C

208 Q4 -CSaEt X 8

209 Q4 -CS-2-chill X 8

210 Q4 -COSMe X 9 43.5 ° C

211 Q4 -COSEt X 9 Oily

212 Q 4 -CSOMe X 9

213 Q4 -CSOEt X 9 Oily

214 Q4 -CSOPh X 9 55-57

215 Q4 -CS ₂ Me X 9 50.9. C

216 Q 4 -CS ₂ Et X 9

217 Q4 -CS-7-quinolyl X 9

218 Q 4 -COSMe X13

219 Q 4 -COSEt X13

220 Q 4 -CS ^ Me X13

221 Q4 -CS ₂ Et X13

222 Q4 -CSO-2-Pyryl X13

223 Q4 -COSMe X18

224 Q4 -COSEt X18

225 Q4 -CS ₂ Me X18

226 Q4 -CS ₂ Et X18

227 Q4 -CSO-5-Pyrazo, Ril (1-Me) X18

228 Q4 -COSMe X21

229 Q 4 -COSEt X21

230 Q4 -CS ₂ Me X21

231 Q4 -CS ₂ Et X21

232 Q4 -CSO-2-chill X21 Table 1 (continued)

Compound NQ Q Y X Physical properties (melting point / refractive index)

233 Q4 -COSMe X24

234 Q4 -COSEt X24

235 Q4 -CS ₂ Me X24

236 Q 4 -CS ₂ Et X24

237 Q4 -CS ₂ -2-h. Rishiru X24

238 Q4 -COSMe X27

239 Q4 -COSEt X27

240 Q 4 -CS ^ Me X27

241 Q4 -CS ₂ Et X27

242 Q4 -CS ₂ -5-Pyrazo, Ril (1-Me) X27

243 Q 4 -COSMe X30

244 Q4 -COSEt X30

245 Q4 -CS ₂ Me X30

246 Q4 -CS ₂ Et X30

247 Q4 -CS ₂ -2-chill X30

248 Q4 -COSMe X33

249 Q4 -COSEt X33

250 Q4 -CS ₂ Me X33

251 Q4 -CS ₂ Et X33

252 Q 4 -COSCH ₂ CF ₃ X33

253 Q4 -COSMe X36

254 Q4 -COSEt X36

255 Q4 -CS ₂ Me X36

256 Q4 -CS ₂ Et X36

257 Q4 -COSCH.CN X36

258 Q 5 -COSMe X 6 Table 1 (continued)

Compound NQ Q Y X Physical properties (melting point z refractive index)

259 Q 5 -COSEt X 6

260 Q 5 -CSOMe X 6

261 Q 5 -CSOEt X 6

262 Q 5 -CSOPh X 6

263 Q 5 -CS ^ Me X 6

264 Q 5 -CS ₂ Et X 6

265 Q 5 -COSMe X 7 98 ~: LOO ° C

266 Q 5 -COSEt X 7

267 Q 5 -CSOMe X 7

268 Q 5 -CSOEt X 7

269 Q 5 -CSOPh X 7

270 Q 5 -CS ₂ Me X 7

271 Q 5 -CS ₂ Et X 7

272 Q 5 -COSMe X13

273 Q 5 -COSEt X13

274 Q 5 -CSOMe X13

275 Q 5 -CSOEt X13

276 Q 5 -CSOPh X13

277 Q 5 -CS ₂ Me X13

278 Q 5 -CS ₂ Et X13

279 Q 6 -COSMe X18

280 Q 6 -COSEt X18

281 Q 6 -CSOMe X18

282 Q 6 -CSOEt X18

283 Q 6 -CSOPh X18

284 Q 6 -CS ₂ Me X18 Table 1 (continued)

Compound NQ Q Y X Physical properties (melting point z refractive index)

285 Q 6 -CS ₂ Et X18

286 Q 6 -COSMe X21

287 Q 6 -COSEt X21

288 Q 6 -CSOMe X21

289 Q 6 -CSOEt X21

290 Q 6 -CSOPh X21

291 Q 6 -CS ^ Me X21

292 Q 6 -CS ₂ Et X21

293 Q 7 -COSMe X24

294 Q 7 -COSEt X24

295 Q 7 -CSOMe X24

296 Q 7 -CSOEt X24

297 Q 7 -CSOPh X24

298 Q 7 -CSaMe X24

299 Q 7 -CS ₂ Et X24

300 Q 7 -COSMe X27

301 Q 7 -COSEt X27

302 Q 7 -CSOMe X27

303 Q 7 -CSOEt X27

304 Q 7 -CSOPh X27

305 Q 7 -CS ₂ Me X27

306 Q 7 -CS ₂ Et X27

307 Q 8 -COSMe X30

308 Q 8 -COSEt X30

309 Q 8 -CSOMe X30

310 Q 8 -CSOEt X30 Table 1 (continued)

Compound NQ Q Y X Physical properties (melting point z refractive index)

311 Q 8 -CSOPh X30

312 Q 8 -CS ₂ Me X30

313 Q 8 -CS ₂ Et X30

314 Q 8 -COSMe X33

315 Q 8 -COSEt X33

316 Q 8 -CSOMe X33

317 Q 8 -CSOEt X33

318 Q 8 -CSOPh X33

319 Q 8 -CS ₂ Me X33

320 Q 8 -CS ₂ Et X33

321 Q 9 -COSMe X36

322 Q 9 -COSEt X36

323 Q 9 -CSOMe X36

324 Q 9 -CSOEt X36

325 Q 9 -CSOPh X36

326 Q 9 -CS ₂ Me X36

327 Q 9 -CS ₂ Et X36

328 Q 1 -COSEt X 1 Oily

329 Q 1 -CSOEt X 1

330 Q 1 -COSMe X 2 Oily

331 Q 1 -CSOEt X 2 Oily

332 Q 1 -CSOEt X 7

333 Q l -COSMe Xll oily

334 Q 1 -COSEt Xll oily

335 Q 1 -CSOEt Xll oily

336 Q 1 -COSMe X12 1 table (continued)

Compound No Q Y X Physical properties (refractive index of melting point)

337 Q 1 -COSEt X 12

338 Q 1 -CSOEt X 12

339 Q 1 -COSMe X35

340 Q 1 -COSEt X35

341 Q 1 -CSOEt X35

342 Q 1 -COSMe X37 oily

343 Q 1 -COSEt X37 72 ~ 74 ° C

344 Q 1 -CS ₂ Me X37 Oily

345 Q 1 -COSMe X38 E body 155 ~: 158 ° C

346 Q 1 -COSMe X38 Z body Oily

347 Q 1 -COSEt X38 Oily

348 Q 1 -CS ^ Me X38 oily

349 Q 1 -COSMe X39 oily

350 Q 1 -COSEt X39 oily

351 Q 1 -COSMe X40 oily

_{352 Q 1 -CS 2 Et X43 no} 35 - 4 1.5508

^{353 Q 1 -COSMe X44 ηο 34 -} ° 1.5730

354 Q 1 -CS ₂ Me X44 48.2 ° C

355 Q 1 -COSMe X45

356 Q 1 -COSEt X45

357 Q 1 -CSOEt X45

358 Q 1 -COSMe X46

359 Q 1 -COSEt X46

360 Q 1 -CSOEt X46

361 Q 1 -COSMe X47

362 Q 1 -COSEt X47 Table 1 (continued)

Compound NQ Q Y X Physical properties (melting point, refractive index)

363 Q 1 -CSOEt X47

364 Q 1 -COSMe X48

365 Q 1 -COSEt X48

366 Q 1 -CSOEt X48

367 Q 1 -COSMe X49

368 Q 1 -COSEt X49

369 Q l -CSOEt X49

370 Q 1 -COSMe X50

371 Q 1 -COSEt X50

372 Q l -CSOEt X50

373 Q 1 -COSMe X51

374 Q 1 -COSEt X51

375 Q 1 -CSOEt X51

376 Q 1 -COSMe X52

377 Q 1 -COSEt X52

378 Q 1 -CSOEt X52

379 Q 1 -COSMe X53

380 Q 1 -COSEt X53

381 Q 1 -CSOEt X53

382 Q 1 -CS ₂ Me X54

383 Q 1 -CS ₂ Et X56

384 Q 1 -CS ₂ Et X59

385 Q 1 -CS ₂ Me X60

386 Q 1 -COSMe X64

387 Q 1 -COSEt X64

388 Q 1 -CSOEt X64 Table 1 (continued)

Compound NQ Q Y X Physical properties (melting point z refractive index)

389 Q 2 -COSMe X4 124 ~ 126 ° C

390 Q 2 -CS ₂ Et X62

391 Q 2 -CS ₂ Me X63

392 Q4 -COSMe X 1 Oily

393 Q4 -COSEt X 1 Oily

394 Q4 -CSOEt X 1 122 ~ 124 ° C

395 Q4 -COSMe X 2 Oily

396 Q4 -COSEt X2 Oily

397 Q4 -CSOEt X2 110 ~ 112 ° C

398 Q4 -COSMe X4 oily

399 Q 4 -COSEt X 4 Oily

400 Q 4 -CSOEt X 7 oily

401 Q4 -COSMe Xll oily

402 Q4 -COSEt Xll Oily

403 Q 4 -CSOEt Xll Oily

404 Q4 -COSMe X12

405 Q4 -COSEt X12

406 Q4 -CSOEt X12

407 Q4 -COSMe X35

408 Q4 -COSEt X35

409 Q4 -CSOEt X35

410 Q4 -COSMe X37 oily

411 Q4 -COSEt X37 61-62. C

412 Q4 -CS ^ Me X37 56.8 ° C

413 Q4 -COSMe X38 E body 115-117 ° C

414 Q4 -COSMe X38 Z body Oily Table 1 (continued:

Compound NQ Q Y X Physical properties (melting point Z refractive index)

415 Q 4 -COSEt X38 E body Oily

416 Q4 -CS ₂ Et X38 Oily

417 Q 4 -COSMe X39 oily

418 Q4 -COSEt X39 Oily

419 Q4 -CSOEt X39 93 ~ 94

420 Q4 -COSMe X40 E body Oily

421 Q 4 -COSMe X40 Z body 128 ~: 130 ° C

422 Q4 -COSMe X41 oily

423 Q 4 -COSMe X42 90 ~ 91t

^{^{424 Q4 -COSMe X44 no 34 - 2}} 1.5582

425 Q4 -CS ₂ Me X44 56.7 ° C

426 Q 4 -COSMe X45

427 Q 4 -COSEt X45

428 Q4 -CSOEt X45

429 Q4 -COSMe X46

430 Q4 -COSEt X46

431 Q 4 -CSOEt X46

432 Q 4 -COSMe X47

433 Q4 -COSEt X47

434 Q4 -CSOEt X47

435 Q4 -COSMe X48

436 Q4 -COSEt X48

437 Q4 -CSOEt X48

438 Q4 -COSMe X49

439 Q4 -COSEt X49

440 Q 4 -CSOEt X49 Table 1 (continued)

Compound No Q Y X Physical properties (melting point z refractive index)

441 Q 4 -COSMe X50

442 Q4 -COSEt X50

443 Q 4 -CSOEt X50

444 Q4 -COSMe X51

445 Q 4 -COSEt X51

446 Q 4 -CSOEt X51

447 Q 4 -COSMe X52

448 Q 4 -COSEt X52

449 Q4 -CSOEt X52

450 Q4 -COSMe X53

451 Q4 -COSEt X53

452 Q4 -CSOEt X53

453 Q 4 -CS ₂ Me X55

454 Q4 -CS ₂ Et X61

455 Q4 -COSMe X64

456 Q 4 -COSEt X64

457 Q 4 -CSOEt X64

458 Q 5 -COSMe X8 87 ~ 91 ° C

459 Q 5 -COSEt X 8 Oily

^{460 Q 5 -COSMe X 9 no 31} - 8 1.5318

461 Q 5 -COSEt X 9 Oily

^{462 Q 5 -CSaMe X 9 ηο 28} - ° 1.5704

463 Q 5 -CS ₂ Et X57

464 Q 5 -CSaMe X58

465 Q10 -COSMe X 7 86-88. C

466 Q10 -COSMe X 8 88 ~ 90 ° C Table 1 (continued)

Compound NQ Q Y X Physical properties (melting point / refractive index)

467 Qll -COSMe X 1

468 Qll -CSOEt X 2

469 Q12 -COSMe X 3

470 Q12 -CSOEt X 7

471 Q13 -COSMe X 8

472 Q13 -CSOEt X 9

473 Q14 -COSMe Xll

474 Q14 -CSOEt X12

475 Q15 -COSMe X 1

476 Q15 -CSOEt X2

477 Q16 -COSMe X 3

478 Q16 -CSOEt X 7

479 Q17 -COSMe X 8

480 Q17 -CSOEt X 9

481 Q18 -COSMe Xll

482 Q18 -CSOEt X12

483 Q19 -COSMe X 9 Oily

484 Q19 -COSEt X 9

485 Q19 -CSOEt X 9

486 Q20 -COSMe X 1

487 Q20 -COSEt X 2

488 Q20 -CSOEt X3

489 Q20 -COSMe X 7

490 Q20 -COSEt X 8

491 Q20 -COSMe X 9 133-137. C

492 Q20 -COSEt X 9 Table 1 (continued)

Compound No Q Y X Physical properties (melting point z refractive index)

493 Q20 -CSOEt X 9

494 Q20 -COSMe X ll

495 Q20 -COSEt X 12

496 Q21 -COSMe X9

497 Q21 -COSEt X9

498 Q21 -CS ^ Me X9

499 Q21 -CS ₂ Et X9

500 Q21 -CSOMe X9

501 Q21 -CSOEt X9

502 Q21 -COSMe X8

503 Q21 -COSMe X7

504 Q22 -COSMe X9

505 Q23 -COSEt X9

506 Q24 -COSMe X9

507 Q25 -COSMe X9

508 Q25 -CS ₂ Me X8

509 Q25 -CSOMe X7

510 Q25 -COSMe X8

511 Q25 -CS ₂ Me X9

512 Q26 -COSMe X9

513 Q27 -COSMe X9

514 Q27 -COSMe X8

515 Q28 -COSMe X9

516 Q29 -COSMe X9

Next, test examples will be described.

Test Example 1 Adult spider mite killing test

A drug solution prepared so that the concentration of the compound of the present invention was 800 ppm was prepared. The leaves of only one primary leaf of the squid were transplanted into a cup (8 cm in diameter, 7 cm in height), and about 30 adult Nami-Nada two were inoculated. This was immersed in the above-mentioned chemical solution together with kidney leaves for about 10 seconds, air-dried, and left in a constant temperature room with lighting at 26 ° C. On the second day after the treatment, viability was determined, and the adult kill ratio was determined by the following formula.

Adult kill rate (%) = Number of dead insects Number of released insects X 100

As a result, Compound Nos. 1-3, 8, 11, 12, 21-24, 26, 27, 31, 32, 34, 35, 38, 39, 89, 99, 104, 109, 168, 184, 185, 187, 197-199, 202, 203, 207, 210, 211, 213-215, 265, 328, 330, 331, 333-335, 349- 35 1, 389, 392, 393, 395-399, 401-403, 417-420, 422, 423, 458-462, 465, 466, and 491 showed 90% or more adult kill rate .

Test example 2

A drug solution prepared so that the concentration of the compound of the present invention was 800 ppm was prepared. The leaves of only the primary leaves of kidney beans were transplanted into cups (8 cm in diameter and 7 cm in height), inoculated with adults of Nami-nada, and spawned for 24 hours to remove the adults. This was immersed in the above-mentioned chemical solution for about 10 seconds together with the ingen leaves, air-dried, and allowed to stand in a constant temperature room at 26 ° C with illumination. On the 7th day after the treatment, the hatching state of the eggs was investigated, and the ovicidal rate was calculated by the following formula.

Egg kill rate (%) = Number of eggs killed Number of eggs laid X 100

As a result, Compound Nos. 1-3, 8, 11, 12, 21-24, 26, 27, 31, 32, 34, 35, 38, 39, 89, 99, 104, 109, 168, 184, 185, 187, 197 to 199, 202, 203, 207, 210, 211, 213 to 215, 265, 328, 330, 331, 333 to 335, 349 ~ 35 1, 389, 392, 393, 395-399, 401-403, 417-420, 422, 423, 458-462, 465, 466, and 491 each have an ovicidal rate of 90% or more Indicated. Test example 3

Rice seedlings are immersed in a chemical solution prepared so that the concentration of the compound of the present invention becomes 800 ppm for about 10 seconds, air-dried, and the roots are wrapped with moist absorbent cotton and placed in a test tube. Then, release 10 larvae of the larvae into this, cover the tube with gauze, and leave them in a constant temperature room with illumination at 26 ° C. When the survival of the insects is determined thereafter, the compound of the present invention shows an effective control effect.

Test Example 4 Peach aphid insecticidal test

A drug solution prepared so that the concentration of the compound of the present invention was 800 ppm was prepared. Pot with only one true leaf left (8 cm in diameter, 7 cm in height) After applying adhesive to the petiole of the planted eggplant, two to three adult females of the peach aphid wingless embryo were applied to the true leaf. Inoculated and bred. Two days after inoculation, the adults were removed and the number of larvae was counted. The eggplant leaves infested with the larvae were immersed in the above-mentioned chemical solution for about 10 seconds, air-dried, and allowed to stand in a constant temperature room at 26 ° C with illumination. On the 5th day after the treatment, viability was determined, and the mortality was calculated by the following formula. The withdrawn insects were considered dead.

Mortality (%) = Number of dead insects / Number of treated larvae X 1 0 0

As a result, Compound Nos. 26, 34, 109 and 465 each showed a mortality of 90% or more.

Test example 5

Cabbage leaf pieces are immersed in a chemical solution prepared so that the concentration of the compound of the present invention becomes 800 ppm for about 10 seconds, and air-dried. Spread wet filter paper on a 9 cm diameter petri dish and place the air-dried leaf pieces on it. There, 10 larvae of the 2nd or 3rd instar are released, covered, and left in 26 illuminated constant temperature rooms. When the survival of the insects is determined thereafter, the compound of the present invention shows an effective control effect. Test Example 6 Tomato disease prevention effect test

Tomato (cultivar: Bontelosa) is cultivated in a plastic bowl having a diameter of 7.5 cm. When the 4 leaf stage is reached, 10 ml of a drug solution prepared so that the compound of the present invention becomes 500 ppm is sprayed using a spray gun. After the drug solution has dried, spray inoculate the suspension of the zoospores of the disease-causing fungus, and keep them in 20 constant temperature chambers. When the lesion area is examined thereafter, the compound of the present invention shows an effective control effect. Test Example 7 Wheat powdery mildew prevention effect test

Wheat (cultivar: Norin 61) is grown in a 7.5 cm diameter plastic pot, and when it reaches the 1.5 leaf stage Spray 10 ml of a drug solution prepared so that the compound of the present invention becomes 500 ppm using a spray gun. After the drug solution dries, sprinkle and inoculate the conidiospores of powdery mildew fungus and keep in a constant temperature room at 20T :. When the spore-forming area is subsequently examined, the compound of the present invention shows an effective control effect. Test Example 8 Test for prevention of crown rust

Cultivate the enpark (cultivar: forward) in a plastic bowl with a diameter of 7.5 cm, and spray it with a spray gun using 10 ml of a chemical solution prepared so that the present compound becomes 500 ppm when the 1.5 leaf stage is reached. After the chemical has dried, sprinkle and inoculate the conidia of the crown rust fungus. When the area of spore formation is subsequently examined, the compound of the present invention shows an effective control effect.

Test Example 9 Green algae control test

A green alga (① Selenastrum capricornutum or ② Chlorella vulgaris) cultured in advance for 7 days is inoculated into an algal growth medium containing a drug solution prepared so that the concentration of the compound of the present invention is 100 ppm, and the temperature is kept constant at 20 ° C under illumination. When the growth of green algae is examined after being left indoors for 8 days, the compound of the present invention shows an effective control effect.

Next, formulation examples will be described.

Formulation Example 1

(1) 20 parts by weight of the compound of the present invention

(2) Clay 7 2 parts by weight

(3) Lignin sulfonate soda

The above components are uniformly mixed to obtain a wettable powder.

Formulation Example 2

(1) 5 parts by weight of the compound of the present invention

(2) 95 parts by weight or more of talc is uniformly mixed to make a powder.

Formulation Example 3

(1) 20 parts by weight of the compound of the present invention

(2) N, Ν'-dimethylacetamide 20 parts by weight

(3) Polyoxyethylene alkyl phenyl ether 10 parts by weight (4) Xylene 50 parts by weight or more is uniformly mixed and dissolved to form an emulsion.

Formulation Example 4

(1) 68 parts by weight of clay

(2) Sodium lignin sulfonate

(3) Polyoxyethylene alkyl sulfate

(4) Finely divided silica 25 parts by weight A mixture of the above components and the compound of the present invention are mixed in a weight ratio of 4: 1 to obtain a wettable powder. Formulation Example 5

(1) 50 parts by weight of the compound of the present invention

(2) Oxidated polyalkylphenyl phosphate monoethanolamine

(3) Silicone 0

(4) Water 47

The above ingredients are uniformly mixed and pulverized.

(5) Sodium polycarboxylate

(6) Add 42.8 parts by weight of anhydrous sodium sulfate, mix uniformly, and dry to obtain a wettable powder.

Formulation Example 6

(1) Compound of the present invention

(2) 1 part by weight of polyoxyethylene octylphenyl ether

(3) Polyoxyethylene phosphate 0

(4) Granulated calcium carbonate 93 μR

(1) to (3) are uniformly mixed in advance, and diluted with an appropriate amount of acetone.

Formulation Example 7

(1) Compound of the present invention 2.5 parts by weight (2) N-methyl-2-pyrrolidone 2.5 parts by weight

(3) Soybean oil 95.0 parts by weight or more are uniformly mixed and dissolved to make an ultra low volume formulation.

Formulation Example 8

(1) Compound of the present invention

(2) N, N'—Dimethylacetamide 15 parts by weight

(3) Polyoxyethylene alkylaryl ether 10 parts by weight

(4) Xylene 70 parts by weight or more is uniformly mixed to form an emulsion.

Formulation Example 9

(1) 40 parts by weight of the compound of the present invention

(2) Oxilated polyalkylphenol phosphate triethanolamine

(3) Silicon 0.2 parts by weight

(4) Xanthan gum 0.1 parts by weight

(5) Ethylene glycol

(6) Water 52

The above components are uniformly mixed and pulverized to obtain an aqueous suspension.

Claims

The scope of the claims

1. Formula (I);

Q 0-Y

(I)

NC X

Wherein Q is an optionally substituted phenyl, an optionally substituted benzyl, an optionally substituted naphthyl or _J, X is an optionally substituted naphthyl or 1 J, and Y is Kenyir, haloalkenyl, alkynyl, haloalkynyl, is an C (= 〇) R! or one C (= S) R _2, is an alkynyl or one SR ₃ be substituted, R ₂ is substituted Alkyl which may be substituted, alkenyl which may be substituted, alkynyl which may be substituted, alkoxy which may be substituted, alkenyloxy which may be substituted, alkynyloxy which may be substituted, alkylthio which may be substituted Alkenylthio which may be substituted, alkynylthio which may be substituted, cycloalkyl which may be substituted, cycloalkyloxy which may be substituted, cycloalkyl which may be substituted Optionally substituted phenyl, optionally substituted phenoxy, optionally substituted phenylthio, optionally substituted benzyl, optionally substituted benzyloxy, optionally substituted benzylthio, J, —0—J or one S—J, and R ₃ is optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, substituted Is a benzyl or 1 J, wherein J is a 5- or 6-membered heterocyclic group containing at least one atom selected from the group consisting of 0, S and N. Or a 6- to 11-membered condensed heterocyclic group containing at least one atom selected from the group consisting of 0, S, and N (condensed heterocyclic group is substituted) Where X is pyridyl An acrylonitrile compound represented by the formula: or a salt thereof.

2. The heterocyclic group of J is pyrrolyl, furyl, phenyl, imidazolyl, virazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, 1,2,3-triazolyl, 1,2,4-1triazolyl, 1,2,3_oxaziazolyl , 1,2,4-Oxaziazolyl, 1,3,4-Oxaziazolyl, 1,2,3-Thiadiazolyl, 1,2,4- Thiadiazolyl, 1,3,4-thiadiazolyl, 1,2,3,4-tetrazolyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, 1,2,4-triazinyl, 1,3,5_triazinyl, 1,2,3, 5-tetrazinyl, 1,2,4,5-tetrazinyl, imidazolinyl, birazolinyl, oxazolinyl, isooxazolinyl, thiazolinyl, isothiazolinyl, 1-pyrrolidinyl, 1-piperidinyl or 4-morpholino, and the fused heterocyclic group is indolyl , Benzofuranyl, isobenzofuranyl, benzochenyl, benzimidazolyl, indazolyl, benzoxazolyl, benzoisoxazolyl, benzothiazolyl, benzoisothiazolyl, quinolyl, isoquinolyl, cinnolyl, fuazyl, quinazalinyl or quinoxalinyl Akurironitoriru compound or its salt is claim 1.

3. Formula (I);

Q O-Y

… (I)

NC X

Wherein Q is an optionally substituted phenyl, an optionally substituted benzyl, an optionally substituted naphthyl or 1 J, X is an optionally substituted naphthyl or 1 J, and Y is Kenyir, haloalkenyl, alkynyl, haloalkynyl, _ c (= 0) or one _{C (= S) R 2,} R is an alkynyl or one SR ₃ be substituted, R ₂ is substituted Alkyl which may be substituted, alkenyl which may be substituted, alkynyl which may be substituted, alkoxy which may be substituted, alkenyloxy which may be substituted, alkynyloxy which may be substituted, alkylthio which may be substituted, Alkenylthio which may be substituted, alkynylthio which may be substituted, cycloalkyl which may be substituted, cycloalkyloxy which may be substituted, cycloalkyl which may be substituted Alkylthio, optionally substituted phenyl, optionally substituted phenoxy, optionally substituted phenylthio, optionally substituted benzyl, optionally substituted benzyloxy, optionally substituted benzylthio, one J , —0_J or one S—J, and R ₃ is optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, substituted Or a J, wherein J is a 5- or 6-membered heterocyclic group containing 1 to 4 at least one atom selected from the group consisting of 0, S and N (heterocyclic group May be substituted) or a 6 to 11-membered fused heterocyclic group containing 1 to 10 at least one atom selected from the group consisting of 0, S and N (the fused heterocyclic group is substituted Wherein X does not contain a pyridyl group], wherein X is a acrylonitrile compound or a salt thereof, which is represented by the formula (II);

Q 0H

… (Π)

NC X

Wherein Q and X are as defined above, and a compound represented by the formula (III):

Y-L-(III)

[Wherein Y is as defined above and L is halogen].

4. A harmful organism controlling agent comprising the acrylonitrile compound of claim 1 or a salt thereof as an active ingredient.

5. An insecticide, acaricide or nematicide containing the acrylonitrile compound or a salt thereof according to claim 1 as an active ingredient.

6. A method for controlling pests, which comprises causing the acrylonitrile compound or a salt thereof according to claim 1 to act on pests as an active ingredient.