JPH0776577A - Diphenyltriazole derivative and insecticide and acaricide - Google Patents

Abstract

PURPOSE:To obtain a compound useful as an insecticide and an acaricide for controlling, especially insect pests of the order Lepidoptera and tetranychids. CONSTITUTION:This compound is expressed by formula I [R<1> is a 1-4C alkyl; X is a halogen, methyl or nitro; (n) is 1-5; Y is an F-substituted >=2C alkyl or an F-substituted >=2C alkoxy], e. g. 3-(2-chloro-6fluorophenyl)-1-methyl-5-(3- perfluoropropylphenyl)-IH-1, 2, 4-triazole. The compound expressed by formula I is obtained by reacting an N-(benzenesulfonyl)benzohydrazonoyl chloride derivative, an N-(alkylsulfonyl)benzohydrazonoyl chloride derivative or an N-(alkylbenzenesulfonyl)benzohydrazonoyl chloride derivative expressed by formula II (R<2>is phenyl or a 1-4C alkyl) with a benzonitrile derivative expressed by formula III in the presence a Lewis acid (e.g. ferric chloride) in a solvent (e.g., chloroform) at 0 deg.C to the refluxing temperature.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a triazole derivative and an insecticidal and acaricidal agent containing the same as an active ingredient.

[0002]

2. Description of the Related Art Japanese Patent Application Laid-Open No. 56-154464 describes that a triazole derivative has insecticidal and acaricidal activity against aphids and spider mites. In addition, US Pat. No. 4,788,210 (US47882)
It is described in 10) that the triazole derivative has high insecticidal and acaricidal activity against aphids, whiteflies and spider mites. However, the insecticidal and acaricidal activity of the compounds specifically described in these publications is not sufficient, and in particular, the insecticidal activity against lepidopteran pests typified by diamondback moth and Spodoptera litura is not described. RD278004 describes that a triazole derivative has insecticidal and acaricidal activity. However, the published technical report does not describe any specific insecticidal or acaricidal activity.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides a triazole derivative having further improved insecticidal and acaricidal activities and having excellent insecticidal activity against lepidopteran pests typified by diamondback moth and Spodoptera litura. Is.

[0004]

[Means for Solving the Problems] In recent years, the drug sensitivity of pests has been remarkably reduced due to the heavy use of drugs, which has been a problem in control. In particular, it is serious in the acaricide and the lepidopteran pest control agent. The present inventors have synthesized various triazole derivatives in order to develop new and useful insecticides against these harmful insects, and conducted repeated studies on their physiological activities. When the biological data of the compounds of the present invention were compared with the compounds specifically described in various specifications such as JP-A-56-154464, the triazole was particularly at the 3-position or 4-position on the 5-position benzene ring. C2 or more alkyl group substituted by at least two or more fluorine atoms, C2 or more alkoxy group, C2 or more alkylthio group, C2 or more alkylcarbonyloxy group, C2 or more A triazole derivative having an alkylcarbonylamino group, an alkenyl having 2 or more carbon atoms, an alkylsulfinyl group having 2 or more carbon atoms, an alkylsulfonyl group having 2 or more carbon atoms, an alkoxyalkyl group, or an alkoxyalkoxy group, is a substance that causes a remarkable decrease in drug sensitivity Mite species such as kanzawa mites, mandarin mites, and diamondback moth,
The present invention has been completed by finding that they have extremely excellent insecticidal and acaricidal activity against lepidopteran pests such as Spodoptera litura.

That is, the present invention has the general formula [I]

[0006]

[Chemical 2] [In the formula, R ¹ represents an alkyl group having 1 to 4 carbon atoms, X represents a halogen atom, a methyl group, a nitro group, a cyano group or a trifluoromethyl group, and n represents an integer of 1 to 5,
Y is an alkyl group having 2 or more carbon atoms substituted by at least 2 or more fluorine atoms (the group may contain different halogen atoms), and 2 carbon atoms substituted by at least 2 or more fluorine atoms. The above alkoxy groups (the groups may contain different halogen atoms), the number of carbon atoms substituted by at least two or more fluorine atoms is 2
The above alkylthio group (the group may contain different halogen atoms), the alkylcarbonyloxy group having 2 or more carbon atoms substituted by at least two or more fluorine atoms (the group may contain a chlorine atom). ), An alkylcarbonylamino group having 2 or more carbon atoms substituted by at least two or more fluorine atoms (in the group, the alkyl moiety may be substituted with a chlorine atom, and the amino moiety may be substituted with an alkyl group). ), An alkenyl group having 2 or more carbon atoms substituted by at least 2 or more fluorine atoms, an alkylsulfinyl group having 2 or more carbon atoms substituted by at least 2 or more fluorine atoms, at least 2
An alkylsulfonyl group having 2 or more carbon atoms substituted by one or more fluorine atoms, an alkoxyalkyl group substituted by at least two or more fluorine atoms, or an alkoxyalkoxy group substituted by at least two or more fluorine atoms is shown. ] The triazole derivative represented by this, and an insecticidal and acaricidal agent containing this as an active ingredient.

In the present specification, the alkyl group having 2 or more carbon atoms is a linear or branched alkyl group having 2 to 30 carbon atoms, such as ethyl, n-propyl, isopropyl, n-butyl, Isobutyl, sec-butyl, t-butyl, n-pentyl, isoamyl, neopentyl, n-hexyl, isohexyl, 3,3-dimethylbutyl, n-heptyl, 5-methylhexyl, 4-methylhexyl, 3-methylhexyl, 4,4-dimethylpentyl, n-octyl, 6-methylheptyl, n-nonyl, 7-methyloctyl, n-decyl, 8-methylnonyl, n-undecyl, 9-methyldecyl, n-dodecyl, 10-methylundecyl , N-tridecyl, 11-
Examples thereof include methyldodecyl, n-tetradecyl, 12-methyltridecyl, n-pentadecyl, 13-methyl-tetradecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl and n-eicosyl groups.

The alkoxy group having a carbon number of 2 or more, the alkylthio group having a carbon number of 2 or more, the alkylcarbonyloxy group having a carbon number of 2 or more and the alkylcarbonylamino group having a carbon number of 2 or more each have an alkyl portion as defined above. (Alkyl having 2 or more carbon atoms) -O- group, (Alkyl having 2 or more carbon atoms) -S- group, (Alkyl having 2 or more carbon atoms)-
CO-O- group, (alkyl having 2 or more carbon atoms) -CO-N
H-group and (alkyl having 2 or more carbon atoms) -CO-N (alkyl) -group.

The alkenyl group having 2 or more carbon atoms is a linear or branched alkenyl group having 2 to 30 carbon atoms, for example, vinyl group, propenyl group, isopropenyl group, butenyl group, pentenyl group, hexenyl group. , A heptenyl group, an octenyl group, a 3-methyl-1-butenyl group,
4-methyl-1-pentenyl group and the like can be mentioned.

The alkylsulfinyl group having 2 or more carbon atoms and the alkylsulfonyl group having 2 or more carbon atoms respectively have an alkyl portion having the above meaning (alkyl having 2 or more carbon atoms) -SO- group and (alkyl having 2 or more carbon atoms). Alkyl)-
It is a group - SO _2.

The alkoxyalkyl group and the alkoxyalkoxy group are an (alkoxy)-(alkyl) group and an (alkoxy)-(alkoxy) group, and examples thereof include an ethoxymethyl group and an ethoxyethoxy group.

Preferred compounds in the present invention are:
In the general formula [I], R ¹ is a methyl group or an ethyl group, X is a halogen atom, n is an integer of 1 to 2, and Y is an alkyl group having 2 or more carbon atoms and substituted by at least 2 or more fluorine atoms. The thing having a group is mentioned.

The compounds of the present invention represented by the general formula [I] are shown in Tables 1-5. The compound numbers will be referred to in the following description.

[0014]

[Table 1]

[0015]

[Table 2]

[0016]

[Table 3]

[0017]

[Table 4]

[0018]

[Table 5] The compound of the present invention can be produced according to the following method, but is not limited to this method. Manufacturing method 1

[0019]

[Chemical 3] (In the formula, R ² represents a phenyl group, an alkyl group having 1 to 4 carbon atoms or a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms, and R ¹ , X, n and Y have the same meanings as described above. That is, the compound of the present invention represented by the general formula [I] is
N- (benzenesulfonyl) represented by the general formula [II]
A benzohydrazonoyl chloride derivative, an N- (alkylsulfonyl) benzohydrazonoyl chloride derivative or an N- (alkylbenzenesulfonyl) benzohydrazonoyl chloride derivative and a benzonitrile derivative represented by the general formula [III] are converted into Lewis acids. It can be obtained by reacting in the presence of an inert solvent.

Any solvent can be used as long as it does not inhibit the reaction, for example, ethers such as diethyl ether, tetrahydrofuran, dioxane and diglyme, aromatic hydrocarbons such as benzene and toluene, pentane, hexane and petroleum ether. Such as aliphatic hydrocarbons, dichloromethane, dichloroethane, chloroform, carbon tetrachloride, chlorobenzene, halogenated hydrocarbons such as o-dichlorobenzene, aprotic polar solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide and the like. A mixed solvent in which selected solvents are combined can be used.

Examples of Lewis acids that can be used include aluminum bromide, aluminum chloride, ferric chloride, boron trifluoride, titanium tetrachloride, tin chloride and zinc chloride.

The amount of the reaction reagent used is usually 1.0 to 2.0 times the amount of the compound represented by the general formula [III] with respect to 1 mol of the compound represented by the general formula [II]. At the same time, the Lewis acid is 1.0 to 2.0 times the molar amount. The reaction temperature is in the range of 0 ° C. to the reflux temperature of the reaction system. Although the reaction time varies depending on the compound, the purpose can usually be reached in 15 minutes to 8 hours.

A specific example of this reaction is described in, for example, Japanese Patent Application No. 5-1.
No. 32431 Publication and Bulletin of the
Chemical Society of Japan (Bull.
Chem. Soc. Jpn. ) 56, p. 545 (1
983). Manufacturing method 2

[0024]

[Chemical 4] {In the formula, m represents 0 or an integer from 1 to 15, and k represents 0 or 1. However, when m is 0, k is 0. A represents an oxygen atom or a sulfur atom, B represents an oxygen atom or a sulfur atom, R ³ is an alkyl group having 1 to 15 carbon atoms and substituted by at least two or more fluorine atoms (the group is a chlorine atom or a bromine atom). Or an alkenyl group having 2 to 15 carbon atoms (which may be substituted with a chlorine atom or a bromine atom) substituted with at least two fluorine atoms. ¹ is a chlorine atom, a bromine atom, an iodine atom or a group-
OSO ₂ R ² is shown, and R ¹ , R ² , X and n have the same meanings as described above. The compound of the present invention represented by the general formula [Ia] can be produced by Production Process 1
It can be obtained by reacting the compound represented by the general formula [IV] and the compound represented by the general formula [V] synthesized by the method in the presence of a suitable base in an inert solvent.

Examples of the base that can be used here include inorganic bases such as sodium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate, and alkali metal alkoxides such as potassium tert-butoxide.

Any solvent can be used as long as it does not inhibit the reaction, for example, ethers such as diethyl ether, tetrahydrofuran, dioxane and diglyme, aromatic hydrocarbons such as benzene, toluene and nitrobenzene, pentane, hexane and the like. Aliphatic hydrocarbons such as petroleum ether, halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene and o-dichlorobenzene, amides such as dimethylformamide and dimethylacetamide, and A mixed solvent in which solvents selected from these are combined can be used.

The amount of the reaction reagent used is usually 1.0 to 2.0 times that of the compound represented by the general formula [V] with respect to 1 mol of the compound represented by the general formula [IV]. Mole,
At the same time, the base is 1.0 to 2.0 times mol. The reaction temperature is in the range of 0 ° C. to the reflux temperature of the reaction system. Although the reaction time varies depending on the compound, the purpose can usually be reached in 1 hour to 16 hours. Manufacturing method 3

[0028]

[Chemical 5] (In the formula, Z ¹ and Z ² represent a chlorine atom or a fluorine atom, and R ¹ , X, A, B, k, m and n have the same meanings as described above.) Represented by the general formula [Ib]. The compound of the present invention is
Can be obtained by reacting the compound represented by the general formula [IV] and the compound represented by the general formula [VI] synthesized in the presence of a suitable base such as sodium hydride in an inert solvent. it can.

Any solvent can be used as long as it does not inhibit the reaction, and examples thereof include ethers such as diethyl ether, tetrahydrofuran, dioxane and diglyme, aromatic hydrocarbons such as benzene, toluene and nitrobenzene, pentane and hexane. Aliphatic hydrocarbons such as petroleum ether, amides such as dimethylformamide and dimethylacetamide, and mixed solvents obtained by combining solvents selected from these can be used.

The amount of the reaction reagent used is usually 1.0 to 5.0 times the amount of the compound represented by the general formula [VI] with respect to 1 mol of the compound represented by the general formula [IV]. Molar, and at the same time 0.01 to 1.0 times the molar amount of the base. The reaction temperature is in the range of -30 ° C to the reflux temperature of the reaction system. Although the reaction time varies depending on the compound, the purpose can usually be reached in 1 hour to 8 hours.

A specific example of this reaction is, for example, the Journal of the American Chemical Society (JA
m. Chem. Soc. ) Vol. 82, p. 5116 (1960) or Journal of Organic Chemistry (J. Org. Chem.) No. 29.
Vol., P. 895 (1964) and the like. Manufacturing method 4

[0032]

[Chemical 6] (In the formula, p represents an integer of 1 or 2, and X, R ¹ ,
Z ¹ , Z ² , m and n have the same meanings as described above. The compound of the present invention represented by the general formula [Id] can be produced by the production method 1
It can be obtained by reacting the compound represented by the general formula [Ic] synthesized by the above with an appropriate oxidizing agent.

Examples of the oxidizing agent include permanganates such as potassium permanganate, chromic acids such as chromic anhydride, hydrogen peroxide, peracetic acid, perbenzoic acid, organic peracids such as metachloroperbenzoic acid, and peroxidation. Nickel, sodium metaperiodate, etc. can be used.

Any solvent can be used as long as it does not inhibit the reaction, for example, alcohols such as methanol and ethanol, ethers such as diethyl ether, tetrahydrofuran, dioxane and diglyme, aromatic compounds such as benzene, toluene and nitrobenzene. Hydrocarbons,
Aliphatic hydrocarbons such as pentane, hexane, petroleum ether, dichloromethane, dichloroethane, chloroform,
Halogenated hydrocarbons such as carbon tetrachloride, 1,2-dichloroethane, chlorobenzene and o-dichlorobenzene,
A mixed solvent obtained by combining carboxylic acids such as acetic acid, amides such as dimethylformamide and dimethylacetamide, water, and a solvent selected from these can be used.

The amount of the reaction reagent used is usually 1 mol of the compound represented by the general formula [Ic].
The oxidizing agent is 1.0 to 5.0 times mol. Reaction temperature is 0 ℃
To the reflux temperature of the reaction system. Although the reaction time varies depending on the compound, the purpose can be usually reached from 1 hour to 48 hours.

Specific examples of this reaction are described, for example, in Shin Jikken Kagaku Koza (Maruzen), Vol. 14, [III], page 1749. Manufacturing method 5

[0037]

[Chemical 7] (In the formula, R ¹ , R ³ , X, m and n have the same meanings as described above.) The compound of the present invention represented by the general formula [If] can be produced by the production method 1.
It can be obtained by catalytic hydrogenation of the compound represented by the general formula [Ie] synthesized according to the above in the presence of a palladium catalyst in an inert solvent.

Any solvent can be used so long as it does not inhibit the reaction, for example, ethers such as diethyl ether, tetrahydrofuran, dioxane, diglyme, alcohols such as methanol and ethanol, esters such as ethyl acetate, pentane, A mixed solvent in which aliphatic hydrocarbons such as hexane, cyclohexane and petroleum ether, amides such as dimethylformamide, water and a solvent selected from these can be used.

The reaction temperature is in the range of 0 ° C. to the reflux temperature of the reaction system. Reaction time varies depending on the compound, but is usually 1
It can reach its purpose in hours to 16 hours.

Specific examples of this reaction are described, for example, in Shin Jikken Kagaku Koza (Maruzen), Vol. 15- [II], page 390 and the like. Manufacturing method 6

[0041]

[Chemical 8] (In the formula, L ² represents a halogen atom, and R ¹ , R ³ , X and n have the same meanings as described above.) The compound of the present invention represented by the general formula [Ig] is referred to as Reference Example 1
Can be obtained by reacting the compound represented by the general formula [VII] and the compound represented by the general formula [VIII] synthesized in the presence of a suitable base in an inert solvent.

Examples of the base that can be used here include amines such as ammonia and triethylamine, pyridines such as pyridine, inorganic bases such as sodium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate, and tertiary butoxy. Examples thereof include alkali metal alkoxides such as potassium.

Any solvent can be used as long as it does not inhibit the reaction, for example, ethers such as diethyl ether, tetrahydrofuran, dioxane and diglyme, aromatic hydrocarbons such as benzene, toluene and nitrobenzene, pentane, hexane, etc. Aliphatic hydrocarbons such as petroleum ether, esters such as ethyl acetate, dichloromethane, dichloroethane, chloroform, carbon tetrachloride,
It is possible to use a halogenated hydrocarbon such as 1,2-dichloroethane, chlorobenzene, or o-dichlorobenzene, an amide such as dimethylformamide or dimethylacetamide, and a mixed solvent in which a solvent selected from these is combined.

The amount of the reaction reagent used is usually 1 mol of the compound represented by the general formula [VII].
The compound represented by the general formula [VIII] is 1.0 to 2.0.
Double mole, and at the same time, 1.0 to 2.0 moles of base. The reaction temperature is in the range of 0 ° C. to the reflux temperature of the reaction system. Although the reaction time varies depending on the compound, the purpose can usually be reached in 1 hour to 16 hours.

Specific examples of this reaction are described, for example, in Shin Jikken Kagaku Koza (Maruzen), Vol. 14- [II], page 1142, etc.

[0046]

EXAMPLES Next, the production method, formulation method and use of the compound of the present invention will be specifically described with reference to examples. Production Example 1 3- (2-chloro-6-fluorophenyl)
-1-Methyl-5- (3-perfluoropropylphenyl) -1H-1,2,4-triazole (Compound No. 1
4) Preparation of N-methyl-N- (p-toluenesulfonyl) -2-chloro-6-fluorobenzohydrazonoyl chloride (1.2 g), 3-perfluoropropylbenzonitrile (0.9 g), chloride A mixture of diiron (0.6 g) and o-dichlorobenzene (5 ml) was stirred at an oil bath temperature of 130 ° C for 1 hour. After cooling, chloroform (200 ml)
, Washed with dilute hydrochloric acid, dilute aqueous sodium hydroxide solution, and brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. This concentrate was purified by silica gel column chromatography using a mixed solvent of hexane-ethyl acetate as a developing solvent to obtain 0.76 g of the desired product as a pale yellow viscous liquid (melting point 78.
0-80.0) was obtained.

NMR data (60 MHz, CDCl ₃ solvent, δ value: ppm) 4.07 (3H, s) 6.9 to 8.0 (7H, m)

Production Example 2 3- (2-chlorophenyl)-
1-methyl-5- (3-perfluorobutylphenyl)
-1H-1,2,4-triazole (Compound No. 16)
Preparation of N-methyl-N- (benzenesulfonyl) -2-chlorobenzohydrazonoyl chloride (2.00 g), 3-perfluorobutylbenzonitrile (2.00 g), anhydrous aluminum chloride (0.80 g), o A mixture of dichlorobenzene (5 ml) was stirred for 30 minutes at 100 ° C. oil bath temperature. After cooling, it was dissolved in chloroform (200 ml), washed with dilute hydrochloric acid, dilute aqueous sodium hydroxide solution and brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure.
The concentrate hexane - ethyl acetate mixed solvent was purified by silica gel column chromatography as a developing solvent, the desired product as a yellow viscous liquid 1.60g (n D 20 ₌ ^1.
5239) was obtained.

NMR data (60 MHz, CDCl ₃ solvent, δ value: ppm) 4.05 (3H, s) 7.1 to 8.0 (8H, m)

Production Example 3 Production of 3- (2-chloro-6-fluorophenyl) -1-methyl-5- (3-perfluorobutylphenyl) -1H-1,2,4-triazole (Compound No. 24) N-methyl-N- (p-toluenesulfonyl) -2-chloro-6-fluorobenzohydrazonoyl chloride (3.80 g), 3-perfluorobutylbenzonitrile (3.50 g), anhydrous aluminum chloride (1. Fifty
A mixture of g) and o-dichlorobenzene (5 ml) was stirred at an oil bath temperature of 100 ° C for 30 minutes. After cooling, it was dissolved in chloroform (200 ml), washed with dilute hydrochloric acid, dilute aqueous sodium hydroxide solution and brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. This concentrate was purified by silica gel column chromatography using a mixed solvent of hexane-ethyl acetate as a developing solvent to obtain the desired product 2.6 as a yellow viscous liquid.
0 g (n _D ²⁰ = 1.5120) was obtained.

NMR data (60 MHz, CDCl ₃ solvent, δ value: ppm) 4.05 (3H, s) 6.9 to 8.1 (7H, m)

Production Example 4 3- (2-chloro-6-fluorophenyl) -1-methyl-5- [4- (perfluoro-3-methylbutyl) phenyl] -1H-1,2,4-
Preparation of triazole (Compound No. 69) N-methyl-N- (p-toluenesulfonyl) -2-chloro-6-fluorobenzohydrazonoyl chloride (3.91 g), 4- (perfluoro-3-methylbutyl) benzo Nitrile (2.89 g), ferric chloride (1.
A mixture of 9 g) and o-dichlorobenzene (10 ml) was stirred at an oil bath temperature of 130 ° C for 1 hour. After cooling, it was dissolved in chloroform (200 ml), washed with dilute hydrochloric acid, dilute aqueous sodium hydroxide solution and brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography using a mixed solvent of hexane-ethyl acetate as a developing solvent to obtain the target substance as colorless granular crystals.2.
33 g (melting point 100.0-101.5 ° C.) were obtained.

NMR data (60 MHz, CDCl ₃ solvent, δ value: ppm) 4.01 (3H, s) 6.9 to 8.0 (7H, m)

Production Example 5 3- (2-chloro-6-fluorophenyl) -1-methyl-5- [4- [2- (1,
Preparation of 1,2,2-tetrafluoroethoxy) ethoxy] phenyl] -1H-1,2,4-triazole (Compound No. 117) 3- (2-chloro-6-fluorophenyl) -5- [4
-(2-Hydroxyethoxy) phenyl] -1-methyl-
1H-1,2,4-triazole (1.57 g) was added to N,
It was dissolved in a mixed solvent of N-dimethylformamide (20 ml) and tetrahydrofuran (20 ml), and 60% sodium hydride (0.18 g) was added at room temperature. Tetrafluoroethylene gas was introduced into this mixture at room temperature. After completion of the reaction, water was added to the reaction mixture and extracted with ethyl acetate,
It was washed with water. The ethyl acetate extract was dried over anhydrous magnesium sulfate and then concentrated under reduced pressure to obtain a crude reaction product. This reaction crude product was subjected to silica gel column chromatography using a mixed solvent of hexane-ethyl acetate as a developing solvent to give 1.75 g of the desired product as colorless granular crystals (melting point: 89-94).
C) was obtained.

NMR data (60 MHz, CDCl ₃ solvent, δ value: ppm) 4.00 (3H, s) 4.27 (4H, s) 6.70 (1H, tt) 6.9 to 7.7. (7H, m)

Production Example 6 3- (2-chloro-6-fluorophenyl) -1-methyl-5- [4- (1,1,2,2
2-Tetrafluoroethylthio) phenyl] -1H-
Preparation of 1,2,4-triazole (Compound No. 121) N-methyl-N- (p-toluenesulfonyl) -2-chloro-6-fluorobenzohydrazonoyl chloride (3.90 g), 4- (1, 1,2,2-Tetrafluoroethylthio) benzonitrile (2.60 g), ferric chloride (1.78 g), o-dichlorobenzene (10 m
The mixture of l) was stirred at 130 ° C. for 1 hour. After cooling to room temperature, the reaction mixture was dissolved in chloroform and washed with 5% aqueous sodium hydroxide solution and water. The chloroform extract was dried over anhydrous magnesium sulfate and then concentrated under reduced pressure to obtain a reaction crude product. The reaction crude product was subjected to silica gel column chromatography using a mixed solvent of hexane-ethyl acetate as a developing solvent to obtain 2.40 g of the target substance as colorless granular crystals.
(Melting point 150-153 ° C.) was obtained.

NMR data (60 MHz, CDCl ₃ solvent, δ value: ppm) 4.07 (3H, s) 5.73 (1H, tt) 6.9 to 7.4 (3H, m) 7.73 (4H, s)

Production Example 7 3- (2-chloro-6-fluorophenyl) -1-methyl-5- [4- (1,1,2,2
2-Tetrafluoroethanesulfinyl) phenyl]-
1H-1,2,4-triazole (Compound No. 122)
Preparation of 3- (2-chloro-6-fluorophenyl) -1-methyl-5- [4- (1,1,2,2-tetrafluoroethylthio) phenyl] -1H-1,2,4-triazole A mixture of (0.80 g), 55% pure m-chloroperbenzoic acid (1.04 g) and dichloromethane (50 ml) was stirred at room temperature for 48 hours. Dichloromethane (100 ml) was added to the reaction mixture, a 5% aqueous sodium hydroxide solution,
It was washed with water. The dichloromethane layer was dried over anhydrous magnesium sulfate and then concentrated under reduced pressure to obtain a reaction crude product. This reaction crude product was subjected to silica gel column chromatography using a mixed solvent of hexane-ethyl acetate as a developing solvent to give 0.66 g of the desired product as colorless granular crystals (melting point: 128-1).
31 ° C.) was obtained.

NMR data (60 MHz, CDCl ₃ solvent, δ value: ppm) 4.10 (3H, s) 6.16 (1H, m) 7.0 to 8.1 (7H, m) IR data (KBr, ν value: cm ⁻¹ ) 1070

Production Example 8 3- (2-chloro-6-fluorophenyl) -1-methyl-5- [4- (1,1,2,
2-Tetrafluoroethanesulfonyl) phenyl] -1
Production of H-1,2,4-triazole (Compound No. 123) 3- (2-chloro-6-fluorophenyl) -1-methyl-5- [4- (1,1,2,2-tetrafluoroethyl) A mixture of thio) phenyl] -1H-1,2,4-triazole (0.80 g), 55% pure m-chloroperbenzoic acid (2.50 g) and dichloromethane (50 ml) was stirred at room temperature for 48 hours. Dichloromethane (100 ml) was added to the reaction mixture, a 5% aqueous sodium hydroxide solution,
It was washed with water. The dichloromethane layer was dried over anhydrous magnesium sulfate and then concentrated under reduced pressure to obtain a reaction crude product. This reaction crude product was subjected to silica gel column chromatography using a mixed solvent of hexane-ethyl acetate as a developing solvent to give 0.69 g of the desired product as colorless granular crystals (melting point: 159 to 1).
64 ° C.) was obtained.

NMR data (60 MHz, CDCl ₃ solvent, δ value: ppm) 4.13 (3H, s) 6.27 (1H, m) 7.0 to 7.5 (3H, m) 8.07 (4H, s) IR data (KBr, ν value: cm ⁻¹ ) 1160 1370

Production Example 9 3- (2-chloro-6-fluorophenyl) -1-methyl-5- [3- (3,3,3-
Trifluoropropenyl) phenyl] -1H-1,2,
Preparation of 4-triazole (Compound No. 128) N-methyl-N-methanesulfonyl-2-chloro-6-
Fluorobenzohydrazonoyl chloride (2.78
g), 3- (3,3,3-trifluoropropenyl) benzonitrile (2.04 g), ferric chloride (1.68)
g) and a mixture of chlorobenzene (10 ml) at 130 ° C.
It was stirred for 1 hour. After cooling to room temperature, the reaction mixture was dissolved in chloroform and washed with 5% aqueous sodium hydroxide solution and water. The chloroform extract was dried over anhydrous magnesium sulfate and then concentrated under reduced pressure to obtain a reaction crude product. This reaction crude product was subjected to silica gel column chromatography using a mixed solvent of hexane-ethyl acetate as a developing solvent to give 2.17 g of the desired product as a light brown oily substance (refractive index = 1.5695).
Got

NMR data (60 MHz, CDCl ₃ solvent, δ value: ppm) 4.15 (3H, s) 6.21 (1H, dq) 6.9 to 7.9 (8H, m)

Production Example 10 3- (2-chloro-6-fluorophenyl) -1-methyl-5- [3- (3,3,3
3, -trifluoropropyl) phenyl] -1H-1,
Preparation of 2,4-triazole (Compound No. 132) 3- (2-chloro-6-fluorophenyl) -1-methyl-5- [3- (3,3,3-trifluoropropenyl) phenyl] -1H- 1,2,4-triazole (1.10 g), 10% palladium-carbon (0.1
Hydrogen gas was introduced into a mixture of g) and ethanol (50 ml) with stirring at room temperature. After completion of the reaction, the reaction mixture was filtered and the filtrate was concentrated under reduced pressure to obtain a reaction crude product. This reaction crude product was subjected to silica gel column chromatography using a mixed solvent of hexane-ethyl acetate as a developing solvent to give 0.99 g of the target product as a pale yellow liquid (refractive index = 1.55).
85) was obtained.

NMR data (60 MHz, CDCl ₃ solvent, δ value: ppm) 2.0 to 3.1 (4H, m) 4.03 (3H, s) 6.9 to 7.7 (7H, m) )

Production Example 11 3- (2-chloro-6-fluorophenyl) -1-methyl-5- [4- (3,5,6)
-Trichlorooctafluorohexanoyl) amino]-
1H-1,2,4-triazole (Compound No. 129)
Preparation of 5- (4-aminophenyl) -3- (2-chloro-6-
Fluorophenyl) -1-methyl-1H-1,2,4-
Triazole (0.64 g), 3,5,6-trichlorooctafluorohexanoyl chloride (0.90 g),
Triethylamine (0.5g), toluene (100m
The mixture of l) was stirred at 60 ° C. for 5 hours. The reaction mixture was washed with 5% aqueous sodium hydroxide solution and water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to give a crude reaction product. This reaction crude product was subjected to silica gel column chromatography using a mixed solvent of hexane-ethyl acetate as a developing solvent to obtain 0.76 g of the desired product as a colorless candy-like substance.

NMR data (60 MHz, CDCl ₃ solvent, δ value: ppm) 4.00 (3H, s) 7.9 to 8.7 (7H, m) 9.23 (1H, br)

Production Example 12 3- (2-chloro-6-fluorophenyl) -1-methyl-5- [4- (2,2,2)
-Trifluoroethoxy) phenyl] -1H-1,2,
Preparation of 4-triazole (Compound No. 46) 3- (2-chloro-6-fluorophenyl) -5- (4
-Hydroxyphenyl) -1-methyl-1H-1,2,
4-Triazole (0.91 g) was dissolved in N, N-dimethylformamide (20 ml), and 60% sodium hydride (0.13 g) was added under ice cooling. 3 of this mixture
After stirring for 0 minutes, 2,2,2-trifluoroethyl tosylate (0.80 g) was added at room temperature, and the mixture was stirred at 100 ° C for 8 hours. The reaction mixture was cooled to room temperature, water was added, the mixture was extracted with ethyl acetate and washed with 5% aqueous sodium hydroxide solution and water. The ethyl acetate extract was dried over anhydrous magnesium sulfate and then concentrated under reduced pressure to obtain a crude reaction product. This reaction crude product was subjected to silica gel column chromatography using a mixed solvent of hexane-ethyl acetate as a developing solvent to obtain 0.80 g of the target product as a pale yellow liquid (refractive index = 1.5550).

NMR data (60 MHz, CDCl ₃ solvent, δ value: ppm) 4.03 (3H, s) 4.39 (2H, q) 7.0 to 7.8 (7H, m)

Reference Example 1 Preparation of 3- (2-chloro-6-fluorophenyl) -5- [4- (2-hydroxyethoxy) phenyl] -1-methyl-1H-1,2,4-triazole 3- (2-chloro-6-fluorophenyl) -5- (4
-Hydroxyphenyl) -1-methyl-1H-1,2,
4-triazole (3.04 g), 2-bromoethanol (2,50 g), potassium carbonate (1.40 g), N,
Add a mixture of N-dimethylformamide (30 ml) to 80
The mixture was stirred at 0 ° C for 16 hours. The reaction mixture was cooled to room temperature, water was added, the mixture was extracted with ethyl acetate and washed with 5% aqueous sodium hydroxide solution and water. The ethyl acetate extract was dried over anhydrous magnesium sulfate and then concentrated under reduced pressure to obtain a reaction crude product.
This reaction crude product was subjected to silica gel column chromatography using a mixed solvent of hexane-ethyl acetate as a developing solvent to obtain 1.64 g of the target product as pale yellow granular crystals.

Reference Example 2 Preparation of 3- (3,3,3-trifluoropropenyl) benzonitrile 3-bromobenzonitrile (9.1 g), 3,3,3-
A mixture of trifluoropropene (6.0 g), sodium acetate (4.5 g), palladium acetate (22.4 mg), triphenylphosphine (108 mg) and N, N-dimethylformamide (30 ml) was autoclaved in an oil bath at a temperature of The mixture was stirred at 120 ° C to 140 ° C for 48 hours. The reaction mixture was cooled to room temperature, water was added, the mixture was extracted with ethyl acetate and washed with water. The ethyl acetate extract was dried over anhydrous magnesium sulfate and then concentrated under reduced pressure to obtain a crude reaction product. The reaction crude product was subjected to silica gel column chromatography using hexane as a developing solvent to obtain 7.6 g of the desired product.

NMR data (60 MHz, CDCl ₃ solvent, δ value: ppm) 6.21 (1H, d) 7.10 (1H, d) 7.4 to 7.7 (4H, m)

Reference Example 3 5- (4-aminophenyl)-
Preparation of 3- (2-chloro-6-fluorophenyl) -1-methyl-1H-1,2,4-triazole N-methyl-N- (p-toluenesulfonyl) -2-chloro-6-fluorobenzohydra Zonoyl chloride (2
0.0 g), 4-nitrobenzonitrile (7.9 g),
Ferric chloride (7.5 g), o-dichlorobenzene (10
0 ml) was stirred at 130 ° C. for 1 hour. After cooling to room temperature, the reaction mixture was dissolved in chloroform and washed with 5% aqueous sodium hydroxide solution and water. The chloroform extract was dried over anhydrous magnesium sulfate and then concentrated under reduced pressure to obtain a reaction crude product. The reaction crude product was subjected to silica gel column chromatography using a hexane-ethyl acetate mixed solvent as a developing solvent. The obtained crystals were recrystallized from a mixed solvent of hexane and acetone to give colorless granular crystals of 3- (2-chloro-6-fluorophenyl) -1.
-Methyl-5- (4-nitrophenyl) -1H-1,
12.4-g 2,4-triazole (melting point 140-143
C) was obtained.

Tin (II) chloride dihydrate (25.0
g), 12N-hydrochloric acid (35 ml) mixture with stirring under ice-cooling 3- (2-chloro-6-fluorophenyl)
-1-Methyl-5- (4-nitrophenyl) -1H-
1,2,4-Triazole (11.5 g) was gradually added, and the mixture was stirred at room temperature for 7 hours. The reaction mixture was ice-cooled, 10% aqueous sodium hydroxide solution was added to make the mixture weakly alkaline, and the mixture was extracted with ethyl acetate. The ethyl acetate layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to give a crude reaction product. The crude product was crystallized from a mixed solvent of ethyl acetate and hexane to obtain 10.4 g of the desired product as pale yellow granular crystals (melting point: 173 to 176 ° C).

NMR data (60 MHz, CDCl ₃ solvent, δ value: ppm) 3.97 (3H, s) 4.00 (2H, s) 6.5 to 7.5 (7H, m)

Reference Example 4 Production of 3-perfluorobutylbenzonitrile 3-iodobenzonitrile (10.2 g), perfluorobutyl iodide (23.1 g), copper powder (5.7 g)
A mixture of g) and dimethyl sulfoxide (100 ml) was stirred at 130 degrees for 6 hours. After cooling the reaction mixture to room temperature, water was added, the insoluble matter was filtered, the filtrate was extracted with chloroform, and washed with water. The chloroform extract was dried over anhydrous magnesium sulfate and then concentrated under reduced pressure to obtain a reaction crude product. The reaction crude product was subjected to silica gel column chromatography using hexane as a developing solvent to obtain 9.5 g of a target product as a pale yellow liquid.

The insecticidal and acaricidal agent of the present invention has the general formula [I]
The triazole derivative represented by is used as an active ingredient.
In order to use the compound of the present invention as an insecticide or acaricide, the compound of the present invention may be used as it is, but a carrier, a surfactant, a dispersant or an auxiliary agent or the like generally used for formulation is blended. It can also be used by formulating into a powder, a wettable powder, an emulsion, a fine granule or a granule. As a carrier used in the formulation, solid carrier such as Sieglite, talc, bentonite, clay, kaolin, diatomaceous earth, white carbon, vermiculite, slaked lime, silica sand, ammonium sulfate, urea, isopropyl alcohol, xylene, cyclohexane, methylnaphthalene, etc. Examples include liquid carriers. Surfactants and dispersants include alkylbenzene sulfonic acid metal salts, dinaphthylmethane disulfonic acid metal salts, alcohol sulfate ester salts, alkylaryl sulfonates, lignin sulfonates, polyoxyethylene glycol ethers, polyoxyethylene alkylaryls. Examples thereof include ether and polyoxyethylene sorbitan monoalkylate. Examples of the auxiliary agent include carboxymethyl cellulose, polyethylene glycol, gum arabic and the like. Before use, dilute to an appropriate concentration and spray or apply directly.

The insecticidal and acaricidal agent of the present invention can be used by foliage spraying, soil application, nursery box application or water surface application. The mixing ratio of the active ingredient is appropriately selected as necessary, but when it is a powder or granule, it is 0.05.
-20% (weight), preferably 0.1% to 10% (weight). When used as an emulsion or wettable powder, 0.5 to 80% (by weight) is suitable. It is preferable to appropriately select from the range of 1 to 60% (weight).

The application rate of the insecticidal and acaricidal agent of the present invention depends on the kind of compound used, the target pest, the tendency of occurrence, the degree of damage,
Depending on environmental conditions, dosage form used, etc., when used as it is, such as powder and granules, 0.05 g to 5 kg per 10 are as an active ingredient, preferably 0.
It is preferable to appropriately select from the range of 1 g to 1 kg. Also, when used in liquid form, such as when used as an emulsion and wettable powder,
0.1 to 5,000 ppm, preferably 1 to 1,000
It is preferable to appropriately select from the range of ppm. Insecticide of the present invention,
As the acaricide, other insecticides, other acaricides, fungicides, fertilizers and plant growth regulators can be mixed and used.

Next, the formulation method will be specifically described with reference to typical formulation examples. The types and compounding ratios of the compounds and additives are not limited to these, and can be changed in a wide range. In the following description,% indicates weight percentage. Formulation Example 1 Emulsion Compound (14) 30%, cyclohexanone 20%, polyoxyethylene alkylaryl ether 11%, calcium alkylbenzene sulfonate 4% and methylnaphthalene 35% were uniformly dissolved to obtain an emulsion.

Formulation Example 2 Wettable powder Compound (24) 40%, diatomaceous earth 15%, clay 15%,
White carbon 25%, dinaphthylmethane disulfonate sodium 2% and lignin sulfonate sodium 3
% Was uniformly mixed and pulverized to obtain a wettable powder.

Formulation Example 3 Dust formulation A powder formulation was prepared by uniformly mixing and grinding 2% of compound (123), 5% of diatomaceous earth and 93% of clay.

Formulation Example 4 Granules Compound (14) 5%, lauryl alcohol sulfate sodium salt 2%, sodium lignin sulfonate 5
%, Carboxymethylcellulose 2% and clay 86%
Are uniformly mixed and pulverized. 100 parts by weight of this mixture are mixed with 2 parts of water.
Add 0 parts by weight and knead.
It was processed into 32 mesh granules and then dried to obtain granules.

[0084]

INDUSTRIAL APPLICABILITY The triazole derivative of the present invention is used for lepidopteran pests such as diamondback moth, Spodoptera litura, and Spodoptera litura, spider mites such as spider mites, kanzawa mites, citrus mites, aphids such as cotton aphids, peach aphids, and aphids of radish, whiteflies of white peach and the like. Whiteflies such as whiteflies, brown planthoppers, white-necked planthoppers, and planthoppers, leafhoppers such as leafhoppers and leafhoppers, scale insects such as stag beetles and stink bugs such as stag beetles, and other insects such as housefly It is effective for the control of Coleoptera insect pests such as Diptera, Weevils, Azuki bean weevils and urchin beetles and Orthoptera insects such as American cockroaches and German cockroaches.

In particular, an extremely excellent controlling effect is exerted against lepidopteran such as diamondback moth, white-spotted armyworm, Spodoptera litura, spider mites such as spider mites, kanzawa mites, citrus mites, aphids such as cotton aphids, green peach aphids, and aphids of Japanese radish aphids. Show.

Next, the effect of the compound of the present invention will be described with reference to test examples. The used comparative drug a and the comparative drug b are the compounds described in JP-A-56-154464, and the comparative drug c and the comparative drug d are described in US Pat. No. 4,788,210. The compounds described are comparative drugs e and f as RD278.
It is the compound described in No. 004. These comparative drugs were used by formulating them in the same manner as the test compounds.

Comparative drug a: 3,5-bis (2-chlorophenyl) -1-methyl-1H-1,2,4-triazole Comparative drug b: 3- (2-chlorophenyl) -1-methyl-5- ( 3-Methylphenyl) -1H-1,2,4-triazole Comparative drug c: 3- (2-chloro-6-fluorophenyl) -1-methyl-5- (2-trifluoromethylphenyl) -1H-1 , 2,4-Triazole Comparative drug d: 3- (2,6-difluorophenyl) -1
-Methyl-5- (2-trifluoromethyl) -1H-
1,2,4-triazole comparative drug e: 3- (2-chlorophenyl) -1-methyl-5- (2-methyl-3-chlorophenyl) -1H-
1,2,4-Triazole comparative agent f: 3- (2-chloro-6-fluorophenyl) -1-methyl-5- (2,4-dichlorophenyl)
-1H-1,2,4-triazole

Test Example 1 Diamondback moth insecticidal test A wettable powder prepared according to Formulation Example 2 was diluted with water to a concentration of 500 ppm. Cabbage leaves were dipped in the chemical solution, air-dried, and then placed in a vinyl chloride cup. Ten larvae of Plutella xylostella were released therein and the lid was closed. Then, it was placed in a constant temperature room at 25 ° C., and after 6 days, the number of dead insects was investigated and the dead insect rate was calculated. The determined mortality was evaluated according to the criteria in Table 6, and the results are shown in Table 7. The test was carried out in a two-series system.

[0089]

[Table 6]

[0090]

[Table 7]

Test Example 2 Nikameiga insecticidal test A wettable powder prepared according to Formulation Example 2 was diluted with water to a concentration of 500 ppm. Rice bud buds were soaked in the solution, air-dried, and put in a vinyl chloride cup. Ten larvae of Nikameiga were released in it and the lid was closed. After that, it was placed in a constant temperature room at 25 ° C., and after 6 days, the number of dead insects was investigated and the dead insect rate was calculated. The mortality obtained was evaluated according to the criteria in Table 6, and the results are shown in Table 8. The test was carried out in a two-series system.

[0092]

[Table 8]

Test Example 3 Insecticidal test for Spodoptera litura L. A wettable powder prepared according to Formulation Example 2 was diluted with water to a concentration of 500 ppm. Cabbage leaves were dipped in the chemical solution, air-dried, and then placed in a vinyl chloride cup. Ten larvae of Spodoptera litura were released in it and the lid was closed. Then 25
It was placed in a thermostatic chamber at 0 ° C., and 6 days later, the number of dead insects was examined and the dead insect rate was calculated. The determined mortality was evaluated according to the criteria in Table 6, and the results are shown in Table 9. The test was carried out in a two-series system.

[0094]

[Table 9]

Test Example 4 Nymphalid mite insecticidal test A wettable powder prepared according to Formulation Example 2 was diluted with water to a concentration of 500 ppm. Soybean seedlings, which had been previously inoculated with adult spider mites, were immersed in the chemical solution and air-dried. The treated soybean seedlings were placed in a constant temperature room at 25 ° C., the number of surviving insects was examined 14 days later, and the control value was calculated by the equation 1. The obtained control value was evaluated according to the criteria in Table 10, and the results are shown in Table 11. The test was carried out in a two-series system.

[0096]

[Equation 1]

[0097]

[Table 10]

[0098]

[Table 11]

Test Example 5 Cotton Aphid Insecticidal Test A wettable powder prepared according to Formulation Example 2 was diluted with water to a concentration of 100 ppm. Cucumber seedlings, which had been inoculated with cotton aphid larvae in advance, were dipped in the drug solution and air-dried. The treated cucumber seedlings were placed in a constant temperature room at 25 ° C., and the number of dead insects was investigated 3 days later, and the dead insect rate was calculated. The mortality obtained was evaluated according to the criteria in Table 6, and the results are shown in Table 12. The test was carried out in a two-series system.

[0100]

[Table 12]

Front Page Continuation (72) Inventor Atsuhiko Ikeda 1 Shioshinta, Fukuda-cho, Iwata-gun, Shizuoka 1 408 IK Lab Co., Ltd. (72) Inventor Takashi Yumida, 408 Shiionta, Fukuda-cho, Iwata-gun, Shizuoka 1 KAI Co., Ltd. (72) Inventor Yuyuki Yano 1809 Kamo Kikugawa-cho, Ogasa-gun, Shizuoka Prefecture (72) Inventor Yuki Nakano 6 2353 Shimouchida, Kikugawa-cho, Ogasa-gun, Shizuoka Prefecture (72) Inventor Hiroshi Kurihara Shizuoka 4-6, Aobadai, Kikugawa-cho, Ogasa-gun, Fukushima Prefecture (72) Inventor Tadami Hirano 3-9-2, Katsurugaoka, Kakegawa-shi, Shizuoka

Claims (2)

[Claims] 1. A general formula: [In the formula, R ¹ represents an alkyl group having 1 to 4 carbon atoms, X represents a halogen atom, a methyl group, a nitro group, a cyano group or a trifluoromethyl group, and n represents an integer of 1 to 5,
Y is an alkyl group having 2 or more carbon atoms substituted by at least 2 or more fluorine atoms (the group may contain different halogen atoms), and 2 carbon atoms substituted by at least 2 or more fluorine atoms. The above alkoxy groups (the groups may contain different halogen atoms), the number of carbon atoms substituted by at least two or more fluorine atoms is 2
The above alkylthio group (the group may contain different halogen atoms), the alkylcarbonyloxy group having 2 or more carbon atoms substituted by at least two or more fluorine atoms (the group may contain a chlorine atom). ), An alkylcarbonylamino group having 2 or more carbon atoms substituted by at least two or more fluorine atoms (in the group, the alkyl moiety may be substituted with a chlorine atom, and the amino moiety may be substituted with an alkyl group). ), An alkenyl group having 2 or more carbon atoms substituted by at least 2 or more fluorine atoms, an alkylsulfinyl group having 2 or more carbon atoms substituted by at least 2 or more fluorine atoms, at least 2
An alkylsulfonyl group having 2 or more carbon atoms substituted by one or more fluorine atoms, an alkoxyalkyl group substituted by at least two or more fluorine atoms, or an alkoxyalkoxy group substituted by at least two or more fluorine atoms is shown. ] The triazole derivative represented by these. 2. An insecticide and acaricide containing the triazole derivative according to claim 1 as an active ingredient.