JP3443134B2 - Triazole derivatives and insecticides and acaricides - Google Patents

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 Unexamined Patent Publication No. 56-154464 and German Unexamined Patent Publication No. 3631511 (DE36)
31511), it is described that the triazole derivative has insecticidal and acaricidal activity. However, it is difficult to say that the compounds described in the specification of the publication have sufficient insecticidal and acaricidal activity.

[0003]

[Problems to be Solved by the Invention]
Various compounds such as organic phosphorus compounds and organic tin compounds have been used for controlling mites. However, due to the long-term use of these drugs, the pests mentioned above have developed drug resistance in recent years, making it difficult to control them. This tendency is particularly remarkable in the lepidopteran pests, spider mites and aphids, and the situation is becoming alarming, and the emergence of new types of insecticides and acaricides having different actions is desired. The present inventors have developed new insecticidal and acaricidal agents having different actions, which cannot be found in the conventional techniques and are highly effective against a wide range of pests and can be safely used. The research was conducted for the purpose of creating.

[0004]

[Means for Solving the Problems] In order to solve the above-mentioned problems, the present inventors have synthesized various triazole derivatives and conducted repeated studies on their physiological activities. As a result, the triazole derivative represented by the following general formula [I] is effective against a wide range of agricultural and horticultural pests, particularly lepidopteran pests, aphids, and mites, and eggs of mites with further developed drug resistance are shown. The present invention has been completed by finding that it exhibits extremely high effects on larvae and aphid nymphs.

The present invention has the general formula [I]

[0006]

[Chemical 3]

[In the formula, R ¹ represents an alkyl group, X represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, a nitro group, a cyano group or a trifluoromethyl group, and n is 1 to 5 When n is 2 or more, X may be the same or different combination. Y is an alkenyl group, alkynyl group, alkoxyalkyl group, alkoxyalkoxy group, alkylthioalkyl group, cycloalkyl group, cycloalkylalkoxy group, cycloalkylalkyl group, cycloalkylalkenyl group, cycloalkylalkynyl group, trialkylsilylalkyl. Group, trialkylsilylalkoxy group, alkyl group having 7 or more carbon atoms, alkoxy group having 7 or more carbon atoms, alkylthio group having 7 or more carbon atoms, alkylsulfinyl group having 7 or more carbon atoms, alkylsulfonyl group having 7 or more carbon atoms, or formula

[0008]

[Chemical 4]

(In the formula, A represents an oxygen atom, a sulfur atom, a lower alkylene group, a lower alkyleneoxy group, an oxy lower alkylene group, a lower alkyleneoxyalkylene group,
k represents 0 or 1, and Q represents a CH group or a nitrogen atom. R ² represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or a trifluoromethyl group, a trifluoromethoxy group, m represents an integer of 1 to 5, and m
When is 2 or more, R ² may be the same or different combination. ) Represents a group represented by. } And the insecticide and acaricide containing this as an active ingredient.

In the present invention, the term lower means that the group to which this term is attached has 6 or less carbon atoms. Also,
The alkyl group means a linear or branched alkyl group having 1 to 30 carbon atoms, and includes, for example, methyl, 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, 1
1-methyldodecyl, n-tetradecyl, 12-methyltridecyl, n-pentadecyl, 13-methyl-tetradecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl group and the like are included.

The alkoxy group, the alkylthio group, the alkylsulfinyl group and the alkylsulfonyl group each have an alkyl moiety having the above meaning (alkyl) -O-.
A group - group, (alkyl) -S- group, (alkyl) -SO- group and (alkyl) -SO _2. The halogen atom includes each atom of fluorine, chlorine, bromine and iodine. The alkenyl group means a linear or branched alkenyl group having 2 to 20 carbon atoms, and examples thereof include vinyl, propenyl, isopropenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, 3-methyl-1-butenyl, 4 −
It includes a methyl-1-pentenyl group and the like. The alkynyl group means a linear or branched alkynyl group having 2 to 20 carbon atoms, for example, ethynyl, propynyl, butynyl,
Pentynyl, hexynyl, 3,3-dimethyl-1-butynyl, 4-methyl-1-pentynyl, 3-methyl-1-
Pentynyl, 5-methyl-1-hexynyl, 4-methyl-1-hexynyl, 3-methyl-1-hexynyl, heptynyl, octynyl, nonynyl, decynyl, undecynyl, dodecynyl, tridecynyl, tetradecynyl, pentadecynyl, hexadecynyl group and the like. .

The cycloalkyl group means a cycloalkyl group having 3 to 12 carbon atoms, and includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl groups and the like. The cycloalkylalkyl group means a cycloalkylalkyl group having 6 to 12 carbon atoms, and includes, for example, cyclopentylmethyl, cyclohexylmethyl, cyclopentylethyl, cyclohexylethyl, cyclopentylpropyl, cyclohexylpropyl, cyclohexylpentyl groups and the like. A cycloalkylalkoxy group has a cycloalkylalkyl moiety having the above meaning (cycloalkylalkyl)
Indicates an —O— group. The cycloalkylalkenyl group means a cycloalkylalkenyl group having 5 to 12 carbon atoms, for example, cyclopentyl vinyl, cyclohexyl vinyl, 3
-Cyclopentyl-1-propenyl, 3-cyclohexyl-1-propenyl, 5-cyclohexyl-1-pentenyl group and the like are included. The cycloalkylalkynyl group means a cycloalkylalkynyl group having 5 to 12 carbon atoms and includes, for example, a cyclopentylethynyl group, a cyclohexylethynyl group, a 3-cyclopentyl-1-propynyl group, a 3-cyclohexyl-1-propynyl group and the like.

The tri (lower alkyl) silyl lower alkyl group is, for example, a trimethylsilylmethyl, dimethylethylsilylmethyl, butyldimethylsilylmethyl group or the like. The tri (lower alkyl) silyl lower alkoxy group means a [tri (lower alkyl) silyl lower alkyl] -O- group in which the tri (lower alkyl) silyl lower alkyl moiety has the above meaning. The lower alkylene group has 1 to 1 carbon atoms.
4 means a linear or branched alkylene group, such as methylene, ethylene, methylmethylene, trimethylene,
1-methylethylene, dimethylmethylene, tetramethylene, 1-methyltrimethylene, 2-methyltrimethylene and the like are included. The lower alkyleneoxy group means that the lower alkylene moiety has the above meaning-(lower alkylene) -O.
Represents a group. An oxy-lower alkylene group is a lower alkylene moiety having the above meaning -O- (lower alkylene)-
Indicates a group. The lower alkyleneoxyalkylene group represents a-(lower alkylene) -O- (lower alkylene)-group in which the lower alkylene part has the above-mentioned meaning.

In the above-mentioned general formula [I], as a preferable compound group, R ¹ represents a linear or branched alkyl group having 1 to 6 carbon atoms, particularly preferably a methyl group, X represents a hydrogen atom, a halogen atom, A linear or branched alkyl group having 1 to 4 carbon atoms, a nitro group, a cyano group or a trifluoromethyl group is shown, n is an integer of 1 to 3 (n is 2 or 3
Then X may optionally be the same or a different combination. ), And Y is a linear or branched alkyl group having 7 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkylalkyl group having 6 to 12 carbon atoms, and 7 to 1 carbon atoms.
6 straight-chain or branched-chain alkoxy group, having 7 to 12 carbon atoms
Cycloalkylalkoxy group, C 7-16 linear or branched alkylthio group, alkylsulfinyl group, alkylsulfonyl group, C 3-16 linear or branched alkenyl group, C 5-12 Cycloalkylalkenyl group, linear or branched alkynyl group having 3 to 16 carbon atoms, cycloalkylalkynyl group having 5 to 12 carbon atoms, tri (lower alkyl) silyl lower alkyl group, tri (lower alkyl) silyl lower alkoxy group , Or Formula 4 (in the formula, A is an oxygen atom, a sulfur atom, and a carbon number 1)
~ 4 lower alkylene group, methyleneoxy group or oxymethylene group, k is 0 or 1, Q is CH group or nitrogen atom, R ² is hydrogen atom, halogen atom, lower alkyl group, lower alkoxy group, tri A fluoromethyl group or a trifluoromethoxy group, and m is an integer of 1 to 3. When m is 2 or 3, R ² may be the same or different combination. ) The compound which is a group represented by these.

Next, typical examples of the compounds of the present invention represented by the general formula [I] are shown in Tables 1 to 25. The compound numbers will be referred to in the following description.

[0016]

[Table 1]

[0017]

[Table 2]

[0018]

[Table 3]

[0019]

[Table 4]

[0020]

[Table 5]

[0021]

[Table 6]

[0022]

[Table 7]

[0023]

[Table 8]

[0024]

[Table 9]

[0025]

[Table 10]

[0026]

[Table 11]

[0027]

[Table 12]

[0028]

[Table 13]

[0029]

[Table 14]

[0030]

[Table 15]

[0031]

[Table 16]

[0032]

[Table 17]

[0033]

[Table 18]

[0034]

[Table 19]

[0035]

[Table 20]

[0036]

[Table 21]

[0037]

[Table 22]

[0038]

[Table 23]

[0039]

[Table 24]

[0040]

[Table 25]

The compound of the present invention can be produced according to the following method, but is not limited to this method. Manufacturing method A

[0042]

[Chemical 5]

(In the formula, W represents a sulfur atom or an oxygen atom, L represents an alkyl group having 1 to 4 carbon atoms, R ¹ and
X, n and Y have the same meanings as described above. )

The compound of the present invention represented by the general formula [I] is
It can be obtained by reacting an N-acyl (thio) imidate derivative represented by the general formula [II] with a hydrazine derivative represented by the general formula [III] in an inert solvent.

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, and aromatics such as benzene, toluene and chlorobenzene. Group hydrocarbons,
Aliphatic hydrocarbons such as pentane, hexane, petroleum ether, dichloromethane, dichloroethane, chloroform,
It is possible to use halogenated hydrocarbons such as carbon tetrachloride, nitriles such as acetonitrile, aprotic polar solvents such as dimethylformamide, dimethylacetamide and dimethylsulfoxide, water, and a mixed solvent obtained by combining solvents selected from these. it can. The amount of the raw material compound used is usually 1.0 to 5.0 for the compound represented by the general formula [III] with respect to 1 mol of the compound represented by the general formula [II].
It is twice the mole.

The reaction temperature is arbitrary between 0 ° C. and the boiling point of the solvent, but the reaction is preferably carried out in the range of 0 ° C. to 50 ° C. The reaction time varies depending on the compound, but is usually 1 hour to 72 hours.
You can reach that goal in time.

Specific examples of this reaction are described in, for example, Synthesis, page 483 (1983).

Next, the starting compound represented by the general formula [II] can be produced by the method B shown below. Manufacturing method B

[0049]

[Chemical 6]

(In the formula, Z represents a halogen atom, L,
W, X, n and Y have the same meanings as described above. )

The compound represented by the general formula [II] can be obtained by reacting the compound represented by the general formula [IV] with the compound represented by [V] in the presence of a base in an inert solvent. The compound represented by the general formula [IV] may be used as an acid addition salt, for example, a salt with boron tetrafluoride, hydrogen chloride, hydrogen bromide, hydrogen iodide and the like. As the base, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, sodium hydroxide, an inorganic base such as potassium hydroxide, diethylamine,
Organic bases such as triethylamine, pyridine and 4- (N, N-dimethylamino) pyridine can be used.

As the solvent that can be used, ketones such as acetone and methyl ethyl ketone, ethers such as diethyl ether, tetrahydrofuran, dioxane and diglyme, aromatic hydrocarbons such as benzene, toluene and chlorobenzene, pentane, hexane and petroleum ether. Etc., aliphatic hydrocarbons such as dichloromethane, halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform and carbon tetrachloride, nitriles such as acetonitrile, aprotic polar solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide and the like It is possible to use a mixed solvent in which the above-mentioned solvents are combined.

The amount of the reaction reagent to be used is usually 1 mole of the compound of the general formula [IV],
The compound represented by is 0.8 to 1.3 times by mole. The amount of the base used is 1.0 to 2.0 times mol with respect to 1 mol of the compound represented by the general formula [IV]. The reaction time varies depending on the compound, but is usually in the range of 1 hour to 24 hours. The reaction temperature is between 0 ° C. and the boiling point of the solvent.

Production Method C

[0055]

[Chemical 7]

(In the formula, R ¹ , X, n and Y have the same meanings as described above, and R ³ is unsubstituted benzene or has 1 to 4 carbon atoms.
Shows benzene substituted with the alkyl group of. )

The compound of the present invention represented by the general formula [I] is represented by the general formula [VII] in the presence of the N- (phenylsulfonyl) benzohydrazonoyl chloride derivative represented by the general formula [VI] and Lewis acid. It can be obtained by reacting a benzonitrile derivative represented by

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, chlorobenzene and dichlorobenzene, and pentane. , Hexane, petroleum ether, and other aliphatic hydrocarbons, dichloromethane, dichloroethane, chloroform, carbon tetrachloride, and other halogenated hydrocarbons, nitrobenzene, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, and other aprotic polar solvents, and these A mixed solvent in which selected solvents are combined can be used.

As the Lewis acid used, aluminum bromide, aluminum chloride, ferric chloride, borane trifluoride, titanium tetrachloride, etc. can be used. The amount of the raw material compound used is usually 1.0 to 1.0 mol of the compound represented by the general formula [VII] with respect to 1 mol of the compound represented by the general formula [VI].
The amount is 2.0 times mol, and the Lewis acid is 1.0 to 2.0 times mol. The reaction temperature is arbitrary between 0 ° C and the boiling point of the solvent, but the reaction is preferably carried out in the range of 50 ° C to 180 ° C.
Although the reaction time varies depending on the compound, the purpose can usually be reached in 15 minutes to 8 hours.

Specific examples of this reaction include, for example, bulletin.
56 of the Chemical Society of Japan (Bull.Chem.Soc.Jpn.), P.547 (1983).
Year).

Production Method D

[0062]

[Chemical 8]

(In the formula, R ¹ , R ³ , X, n, Y and Z have the same meanings as described above.)

The compound of the present invention represented by the general formula [I] comprises the N- (phenylsulfonyl) benzamidrazone derivative represented by the general formula [VIII] and the benzoyl halide derivative represented by the general formula [V] in the absence or presence of a solvent. It can be obtained by reacting in an active 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, toluene and chlorobenzene, pentane, hexane and the like. Aliphatic hydrocarbons such as petroleum ether, halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform and carbon tetrachloride, aprotic polar solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidinone and the like. A mixed solvent in which selected solvents are combined can be used.

The amount of the raw material compound used is usually represented by the general formula [VII
The amount of the compound represented by the general formula [V] is 1.0 to 2.0 times the mole of the compound represented by the formula [I]. Reaction temperature is 0
Any temperature between 0 ° C and the boiling point of the solvent, but preferably 50
The reaction is performed in the range of ℃ to 250 ℃. Although the reaction time varies depending on the compound, the purpose can usually be reached in 30 minutes to 5 hours.

Specific examples of this reaction include, for example, bulletin.
56 of the Chemical Society of Japan (Bull.Chem.Soc.Jpn.), P. 548 (1983)
Year). The compound represented by the general formula [VIII] as a raw material can be produced by the method E shown below. Manufacturing method E

[0068]

[Chemical 9]

(In the formula, R ¹ , R ³ and X, n have the same meanings as described above.)

The compound represented by the general formula [VIII] can be obtained by reacting the compound represented by the general formula [VI] with ammonia gas in an inert solvent. As the solvent that can be used, any solvent that does not inhibit the reaction may be used, and examples thereof include ethers such as diethyl ether, tetrahydrofuran, dioxane, and diglyme, benzene, toluene, aromatic hydrocarbons such as chlorobenzene, pentane, and hexane.
Aliphatic hydrocarbons such as petroleum ether, dichloromethane,
It is possible to use halogenated hydrocarbons such as dichloroethane, chloroform, carbon tetrachloride, and dichlorobenzene, aprotic polar solvents such as dimethylformamide, dimethylacetamide, and dimethylsulfoxide, and mixed solvents in which solvents selected from these are combined. .

The amount of the raw material compound used is usually represented by the general formula [VI]
Ammonia gas is 5.0 with respect to 1 mol of the compound represented by
It is 1 to 10 times the mole. The reaction temperature is arbitrary between 0 ° C and the boiling point of the solvent, but the reaction is preferably carried out in the range of 20 ° C to 150 ° C. Although the reaction time varies depending on the compound, the purpose can be usually reached in 1 hour to 24 hours.

Specific examples of this reaction include, for example, bulletin.
56 of the Chemical Society of Japan (Bull.Chem.Soc.Jpn.), P.547 (1983).
Year).

[0073]

EXAMPLES Next, the production method, the formulation method and the 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- (4-octylphenyl) -1H-1,2,4-triazole (Compound No. 1
Process 5) Ethyl 2-chloro-6-fluorobenzimidate (2.20 g) and triethylamine (1.10 g) are dissolved in toluene (100 ml) and stirred at 5 ° C to 10 ° C for 4 hrs.
-Octylbenzoyl chloride (2.53 g) was added dropwise,
The mixture was stirred at room temperature for 1 hour and further heated under reflux for 2 hours. After cooling to room temperature, toluene (100 ml) was added to the reaction solution,
After washing with diluted hydrochloric acid and brine, the toluene layer was dried over anhydrous magnesium sulfate. Monomethylhydrazine (3.00 g) was added to the reaction solution, and the mixture was stirred at room temperature for 8 hours. After completion of the reaction, the reaction mixture was washed with a dilute hydrochloric acid solution and saturated saline,
The extract was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography using a mixed solution of hexane / ethyl acetate as a developing solvent to obtain 1.34 g of the desired product (refractive index n _D ²⁰ = 1.5652).

NMR data (60 MHz, CDCl ₃ solvent, δ value) 0.77 (3H, t) 1.00 to 1.79 (12H, m) 2.57 (2H, t) 3.95 (3H, s) ) 6.83-7.67 (7H, m)

Production Example 2 3- (2-chlorophenyl)-
1-methyl-5- [4- (5-methylhexyl) phenyl] -1H-1,2,4-triazole (Compound No. 6
Method 7) N-methyl-N-phenylsulfonyl-2-chlorobenzohydrazonoyl chloride (2.06 g), 4- (5-methylhexyl) benzonitrile (1.30 g), anhydrous aluminum chloride (0.30 g). 93g), o-dichlorobenzene 5ml
The mixture was stirred at an oil bath temperature of 140 ° 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. The concentrate was purified by silica gel column chromatography using a mixed solvent of hexane / ethyl acetate as a developing solvent to obtain 1.52 g of the desired product (melting point: 64.0 to 67.0 ° C).

NMR data (60 MHz, CDCl ₃ solution, δ value) 0.86 (6H, d) 1.15 to 1.80 (7H, m) 2.67 (2H, t) 4.00 (3H, s) ) 7.17-8.00 (8H, m)

Production Example 3 3- (2-chlorophenyl)-
1-methyl-5- (4-tridecylphenyl) -1H-
Method for producing 1,2,4-triazole (Compound No. 42) N-methyl-N-phenylsulfonyl-2-chlorobenzohydrazonoyl chloride (0.82 g), 4-tridecylbenzonitrile (0.70 g), A mixture of anhydrous aluminum chloride (0.4 g) and o-dichlorobenzene (3 ml) was stirred at an oil bath temperature of 140 ° C for 30 minutes. After cooling, it was dissolved in chloroform (100 ml), washed with dilute hydrochloric acid solution, dilute 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 solution of hexane / ethyl acetate as a developing solvent to give 0.70 g of the desired product (melting point: 55.
0-57.0 ° C) was obtained.

NMR data (60 MHz, CDCl ₃ solution, δ value) 0.67 to 1.80 (25H, m) 2.67 (2H, t) 4.00 (3H, s) 7.16 to 8.03 (8H, m)

Production Example 4 3- (2-chlorophenyl)-
1-methyl-5- (4-pentadecylphenyl) -1H
Method for producing -1,2,4-triazole (Compound No. 50) A mixture of N-methyl-N-phenylsulfonyl-2-chlorobenzamidrazone (3.24 g) and 4-pentadecylbenzoyl chloride (3.50 g) Oil bath temperature 170 ℃
Stir at ~ 180 ° C for 4 hours. After cooling, water was added and the mixture was extracted with ethyl acetate (200 ml × 2). The organic layer was washed with 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 and washed with n-hexane to give 0.34 g of the desired product (melting point: 6).
2.0-65.0 ° C) was obtained.

NMR data (60 MHz, CDCl ₃ solvent, δ value) 0.77 to 1.73 (29H, m) 2.67 (2H, t) 4.00 (3H, s) 7.17 to 7.97 (8H, m)

Production Example 5 Production Method N of 5- (4-decyloxyphenyl) -3- (2,6-dichlorophenyl) -1-methyl-1H-1,2,4-triazole (Compound No. 85) -Methyl-N-phenylsulfonyl-2,6-dichlorobenzohydrazonoyl chloride (1.10 g), 4-decyloxybenzonitrile (0.70 g), anhydrous aluminum chloride (0.4 g), o-dichlorobenzene ( 3 ml) was stirred at an oil bath temperature of 140 ° C. for 30 minutes. After cooling
It was dissolved in chloroform (100 ml), washed with dilute hydrochloric acid solution, dilute 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 solution of hexane / ethyl acetate as a developing solvent to obtain 0.40 g of the desired product (melting point: 60.0 to 64.0 ° C).

NMR data (60 MHz, CDCl ₃ solution, δ value) 0.77 to 1.90 (19H, m) 3.98 (2H, t) 4.04 (3H, s) 6.88 to 7.73 (7H, m)

Production Example 6 3- (2-chloro-6-fluorophenyl) -5- [4- (3-chloro-5-trifluoromethylpyridin-2-yloxy) phenyl] -1
-Methyl-1H-1,2,4-triazole (Compound No. 429) -Production method N-methyl-N-phenylsulfonyl-2-chloro-6
-Fluorobenzohydrazonoyl chloride (1.30
g), 4- (3-chloro-5-trifluoromethylpyridin-2-yloxy) benzonitrile (1.00 g),
A mixture of anhydrous aluminum chloride (0.50 g) and o-dichlorobenzene (3 ml) was stirred at an oil bath temperature of 140 ° C for 30 minutes. After cooling, it was dissolved in chloroform (100 ml), washed with dilute hydrochloric acid solution, dilute 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 hexane / ethyl acetate mixed solution as a developing solvent to obtain 0.70 g of the desired product (refractive index n _D ²⁰ = not measurable).

NMR data (60 MHz, CDCl ₃ solution, δ value) 4.07 (3H, s) 6.75 to 8.58 (9H, m)

Production Example 7 Method for producing N-methyl-N-phenylsulfonyl-2-chlorobenzamidrazone N-methyl-N-phenylsulfonyl-2-chlorobenzhydrazonoyl chloride (17.2 g) was added to N, N. -Dissolved in dimethylformamide (100 ml) and stirred at 60-70 ° C for 3 hours while introducing ammonia gas.
After cooling, it was dissolved in 500 ml of ethyl acetate, washed with water, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The obtained crystals were washed with n-hexane to give 15.4 g of the desired product (melting point: 9).
4.0-96.0 ° C) was obtained.

NMR data (60 MHz, CDCl ₃ solution, δ value) 2.75 (3H, s) 5.80 (2H, s) 7.10 to 8.00 (9H, m)

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.

The carriers used for formulation include
Examples thereof include solid carriers such as dichrite, talc, bentonite, clay, kaolin, diatomaceous earth, white carbon, vermiculite, slaked lime, silica sand, ammonium sulfate and urea, and liquid carriers such as isopropyl alcohol, xylene, cyclohexane and methylnaphthalene.

Examples of the surfactant and dispersant include alkylbenzene sulfonic acid metal salt, dinaphthylmethane disulfonic acid metal salt, alcohol sulfate ester salt, alkylaryl sulfonate, lignin sulfonate, polyoxyethylene glycol ether, polyoxy. Examples thereof include ethylene alkyl aryl ether and polyoxyethylene sorbitan monoalkylate.

Examples of the auxiliaries 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 blending ratio of the active ingredient is appropriately selected according to need, but in the case of powder or granule, it is 0.05
~ 20% (weight), preferably 0.1% to 10% (weight) in range. 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 type of compound used, the target pest, the tendency of occurrence, the degree of damage,
Depending on the environmental conditions, dosage form used, etc., when used as it is for powders and granules, it is used as an active ingredient in an amount of 0.05 g to 5 kg, preferably 0.1 g to 10 g per 10 ares.
It is recommended to select it appropriately from the range of 1 kg. When it is used as a liquid such as an emulsion or a wettable powder, it is 0.1-
It may be appropriately selected from the range of 5,000 ppm, preferably 1 to 1,000 ppm. The insecticide and acaricide of the present invention can also be used by mixing with other insecticides, fungicides, fertilizers and plant growth regulators.

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 (55) 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 (38) 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 compound (120) 2%, diatomaceous earth 5% and clay 93% were uniformly mixed and ground to give a powder.

Formulation Example 4 Granule compound (71) 5%, lauryl alcohol sulfate sodium salt 2%, sodium ligninsulfonate 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.

[0099]

INDUSTRIAL APPLICABILITY The triazole derivative of the present invention is used for planthoppers such as brown planthoppers, white-necked planthoppers, and brown leafhoppers, leafhoppers such as green leafhoppers and leafhoppers, aphids such as cotton aphid, green peach aphid, radish aphid, whitefly whitefly and the like. Hemiptera such as insects, scale insects such as Pseudococcidae and stink bugs such as spider helicopter, Hemiptera pests such as diamondback moth, Pleurotus spp. Coleopteran pests such as corn rootworm, American cockroaches, Orthoptera pests such as German cockroaches, and spider mites such as spider mites, kanzawa mites, citrus spider mites and organotins, synthetic pyrethroids, organophosphoruses, etc. Agent to be effective for the control of reduced spider mites susceptibility. Particularly, it shows an extremely excellent control effect against spider mites such as spider mites, kanzawa mites and citrus mites.

Next, the effect of the compound of the present invention will be described with reference to test examples. Among the comparative drugs used,
For a, the compound described in JP-A-56-154464 was formulated and used in the same manner as the test compound. Further, as b, a commercially available agent generally used for controlling mites was used.

Comparative drug a: 3,5-bis (o-chlorophenyl) -1-methyl-1H-1,2,4-triazole Comparative drug b: hexithiazox (generic name)

Test Example 1 The wettable powder prepared according to the formulation example 2 of the diamondback moth insecticidal test had an active ingredient concentration of 50.
Diluted with water to 0 ppm. Cabbage leaves were dipped in this chemical solution, air-dried, and then placed in a vinyl chloride cup having a volume of 60 ml. Ten third-instar larvae of Plutella xylostella were released therein 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 test was conducted in two consecutive cycles.
Comparative a was used as the comparative drug. The results are shown in Table 2.
6 shows.

[0103]

[Table 26]

Test Example 2 Cotton larvae larvicidal test A wettable powder prepared in accordance with Preparation Example 2 had an active ingredient concentration of 10
Diluted with water to 0 ppm. Cucumber seedlings, which had been inoculated with cotton aphid nymphs in advance, were dipped in this drug solution and air-dried. The treated cucumber seedlings were placed in a constant temperature room at 25 ° C., and three days later, the number of dead insects was examined to calculate the mortality rate. The test was conducted in two consecutive cycles. The results are shown in Table 27.

[0105]

[Table 27]

Test Example 3 Nymphalid mite ovicidal test [0106] Female adult worms were released in advance on three kidney leaf discs (15 mm in diameter) to lay eggs for 24 hours, and then the female adults were removed. A wettable powder prepared according to Formulation Example 2 was diluted with water so that the concentration of the active ingredient was 0.16 ppm, and a leaf disk of kidney bean was immersed in this chemical solution for 10 seconds. The treated leaf disc was placed in a constant temperature room at 25 ° C., and the number of unhatched eggs was examined 7 days later, and the egg killing rate was calculated. The test was conducted in two consecutive cycles. Comparative a and comparative b were used as comparative drugs. The results are shown in Table 28.

[0107]

[Table 28]

Test Example 4 Oxidation test of resistant Kanzawa mites Oxidized female mites of Kanzawa mites showing resistance to commercially available drugs were released on three kidney leaf discs (15 mm in diameter) and allowed to lay eggs for 2 days, and then female adults were removed. A wettable powder prepared according to Formulation Example 2 was diluted with water so that the concentration of the active ingredient was 4 ppm, and a kidney leaf disc was immersed in this chemical solution for 10 seconds. The treated kidney leaf disc was placed in a constant temperature room at 25 ° C., and after 7 days, the number of unhatched eggs was examined and the egg kill rate was calculated. The test was conducted in two consecutive cycles. Comparative a and comparative b were used as comparative drugs. The results are shown in Table 29 to Table 3.
It was shown at 0.

[0109]

[Table 29]

[0110]

[Table 30]

Test Example 5 Resistant kanzawa mites larva killing test Adult female kanzawa mites showing resistance to commercially available drugs were released on three kidney leaf discs (15 mm in diameter) and allowed to lay eggs for 2 days. Thereafter, the adult females were removed and left in a thermostatic chamber at 25 ° C. After 5 days, the number of hatched larvae was examined, and formulation example 2
The wettable powder prepared in accordance with the above is sprayed with a chemical solution diluted with water so that the concentration of the active ingredient is 20 ppm and placed in a constant temperature room at 25 ° C. After 7 days, the number of adults is examined and the mortality rate against hatched larvae is determined. It was calculated. The test was conducted in two consecutive cycles. Comparative a and comparative b were used as comparative drugs. The results are shown in Table 31.

[0112]

[Table 31]

Test Example 6 Citrus spider mite ovulation test Two citrus leaf pieces (diameter 10 m
After laying eggs in m) for 2 days to lay eggs, female adults were removed. A wettable powder prepared according to Formulation Example 2 has an active ingredient concentration of 4 ppm.
Diluted with water so that 1 part of citrus leaf is added to this chemical solution.
It was immersed for 0 seconds. The treated citrus leaf pieces were placed in a constant temperature room at 25 ° C., and after 7 days, the number of unhatched eggs was examined and the ovicidal rate was calculated. The test was conducted in two consecutive cycles. In addition, as a comparative drug,
Comparison a and comparison b were used. The results are shown in Table 32.

[0114]

[Table 32]

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Takashi Yumida 1 Shioshinta, Fukuda-cho, Iwata-gun, Shizuoka Prefecture 1 408, Keiai Research Co., Ltd. (72) Inventor Naokazu Minoguchi Kamo Kikugawa-cho, Ogasa-gun, Shizuoka 1809 (72) Inventor Yuyuki Yano Kamo, Kikugawa-cho, Ogasa-gun, Shizuoka 1809 Address (72) Norihiko Izawa 1-17 Aobadai, Kikugawa-cho, Ogasa-shi, Shizuoka 5 (72) Inventor Tadami Hirano Kuzukawa-shi, Shizuoka Prefecture 2 of 9-9, Kugaoka (56) Reference JP-A-56-154464 (JP, A) British Patent 1351430 (GB, B) (58) Fields investigated (Int.Cl. ⁷ , DB name) C07D 249 / 08 A01N 43/653 CA (STN)

Claims (4)

(57) [Claims] 1. A general formula: {In the formula, R ¹ represents an alkyl group, X represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, a nitro group, a cyano group or a trifluoromethyl group, and n represents an integer of 1 to 5. When n is 2 or more, X may be the same or different combination. Also, Y
Is an alkenyl group, an alkynyl group, an alkoxyalkyl group, an alkoxyalkoxy group, an alkylthioalkyl group, a cycloalkyl group, a cycloalkylalkoxy group,
Cycloalkylalkyl group, cycloalkylalkenyl group, cycloalkylalkynyl group, trialkylsilylalkyl group, trialkylsilylalkoxy group, alkyl group having 7 or more carbon atoms, alkoxy group having 7 or more carbon atoms, alkylthio group having 7 or more carbon atoms , An alkylsulfinyl group having 7 or more carbon atoms, an alkylsulfonyl group having 7 or more carbon atoms, or a compound represented by the formula: (In the formula, A is an oxygen atom, a sulfur atom, a lower alkylene group,
A lower alkyleneoxy group, an oxy lower alkylene group and a lower alkyleneoxyalkylene group are shown, k is 0 or 1 and Q is a CH group or a nitrogen atom. Also, R
² represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a trifluoromethyl group or a trifluoromethoxy group, m represents an integer of 1 to 5, and when m is 2 or more, R ² is the same or different. May be a combination of. )
Represents a group represented by. } The triazole derivative represented by these. 2. In the above formula 1, R ¹ Has 1 to 6 carbon atoms
Represents a linear or branched alkyl group of X is a hydrogen atom, a halogen atom, a straight chain having 1 to 4 carbon atoms, or
Is a branched chain alkyl group, nitro group, cyano group, trifru
Indicates an oromethyl group, n represents an integer of 1 to 3 (when n is 2 or 3, X is
The same kind or a combination of different kinds may be arbitrarily used. ), Y is a linear or branched alkyl group having 7 to 20 carbon atoms,
C3-C12 cycloalkyl group, C6-C12
Cycloalkylalkyl group, straight chain having 7 to 16 carbon atoms,
Is a branched-chain alkoxy group, cycloalkyl having 7 to 12 carbon atoms
Killalkoxy group, straight or branched chain having 7 to 16 carbon atoms
Alkylthio group, alkylsulfinyl group, alkyl
Sulfonyl group, straight-chain or branched-chain C3-16
Lucenyl group, cycloalkylalkenyl having 5 to 12 carbon atoms
Group, linear or branched alkynyl having 3 to 16 carbon atoms
Group, cycloalkylalkynyl group having 5 to 12 carbon atoms,
Li (lower alkyl) silyl lower alkyl group, tri (lower
Alkyl) silyl lower alkoxy group, or a compound of formula 2 (formula
Among them, A is an oxygen atom, a sulfur atom, or a lower alkyl group having 1 to 4 carbon atoms.
Xylene group, methyleneoxy group or oxymethylene group
, K is 0 or 1, Q is a CH group or nitrogen atom
Indicates a child, R ^Two Is hydrogen atom, halogen atom, lower alkyl
Group, lower alkoxy group, trifluoromethyl group or
Represents a trifluoromethoxy group, m represents an integer of 1 to 3
You R when m is 2 or 3 ^Two Are the same or different types
May be combined. ) Is a group represented by
Triazole derivative of. 3. In the above formula 1, R ¹ Is a methyl group
The triazole derivative according to claim 1 or 2. 4. An insecticide and acaricide containing the triazole derivative according to claim 1 as an active ingredient.