JPH0892224A - 3,5-Substituted phenyltriazole derivatives and insecticides and acaricides - Google Patents

Abstract

(57) [Summary] [Structure] General formula [I] {In the formula, R ¹ represents an alkyl group, X represents a halogen atom, n represents an integer of 1 to 5, Y represents a halogen atom, a nitro group, a cyano group, an alkyl group, an alkoxy group or a haloalkyl group. , M represents 0 or an integer of 1 to 4, A represents a methylaminomethyl group, a methylamino group, an aminomethyl group or an amino group, and R ² represents a hydrogen atom or an alkyl group. } And the insecticides and acaricides which contain this as an active ingredient. [Effect] Various harmful insects, especially aphids and spider mites can be killed and controlled without adversely affecting the crops.

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art The following compounds have been known as triazole derivatives having insecticidal and acaricidal activity. For example, 3,5-bis (2-chlorophenyl) -1-methyl-1H-1,2,4-triazole (JP-A-56-
154464) and 3- (2-chloro-).
6-Fluorophenyl) -5- (2,4-dichlorophenyl) -1-methyl-1H-1,2,4-triazole (Research Disclosure (Research D
isclosure) 278004). Furthermore,
3,5-diphenyl-1-alkyl-1H-1,2,4
-Triazole derivatives (Japanese Patent Application Laid-Open Nos. 5-310712 and 6-97946) are known.

[0003]

However, the degree of activity of these two compounds is not satisfactory.

The present inventors have developed 3,5-diphenyl-1-alkyl-1H in order to develop new and useful insecticides.
Synthetic development was vigorously carried out for the substituent on the 5-position phenyl ring of the -1,2,4-triazole derivative, and the physiological activity thereof was intensively studied. As a result, certain substituents are against various harmful insects and harmful mites, particularly, diamondback moth, Pleurotus cornucopiae, aphids such as Lepidoptera, aphids such as cotton aphid, spider mites such as spider mites, kanzawa mites and citrus mites. Furthermore, they have found that they also have extremely excellent insecticidal and acaricidal activity, and completed the present invention.

[0005]

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

[0006]

[Chemical 4]

[In the formula, R ¹ represents an alkyl group, X represents a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, a nitro group, a cyano group or a haloalkyl group,
n represents 0 or an integer of 1 to 5, and when n is 2 or more, X
May optionally be the same or different combinations. Y represents a halogen atom, nitro group, cyano group, alkyl group, alkoxy group, alkylthio group, haloalkyl group or haloalkoxy group, m represents 0 or an integer of 1 to 4,
When m is 2 or more, Y may be the same or different combination. A is the formula

[0008]

[Chemical 5]

(Wherein R ³ represents a hydrogen atom, an alkyl group or a cycloalkyl group, and j and k each represent an integer of 0 or 1). R ² is a hydrogen atom, an alkyl group or a formula

[0010]

[Chemical 6]

(In the formula, Q and Q'represent a methine group or a nitrogen atom, and R ⁴ is a halogen atom, a nitro group, a cyano group, an alkyl group, an alkoxy group, an alkylthio group, an alkylsulfinyl group, an alkylsulfonyl group or a haloalkyl. Group, haloalkoxy group, haloalkylthio group, haloalkylsulfinyl group, haloalkylsulfonyl group,
Represents an alkylamino group or a dialkylamino group, p
Represents an integer of 0 or 1 to 3, and when p is 2 or more, R ⁴
May optionally be the same or different combinations. ). } And the insecticide and acaricide containing this as an active ingredient.

In the present specification, the alkyl group means
A linear or branched alkyl group having 1 to 6 carbon atoms is shown, and examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group. Group, n-pentyl group, isoamyl group, neopentyl group, n-hexyl group, isohexyl group, 3,3-dimethylbutyl group and the like.

An alkoxy group, an alkylthio group, an alkylsulfinyl group and an alkylsulfonyl group each have an alkyl moiety as defined above (alkyl) -O.
- group - group, (alkyl) -S- group, (alkyl) -SO- group and (alkyl) -SO _2.

Halogen atom means fluorine, chlorine, bromine,
Indicates an iodine atom.

The haloalkyl group means an alkyl group substituted with a halogen atom, and examples thereof include a difluoromethyl group, a trifluoromethyl group and a pentafluoroethyl group.

The haloalkoxy group is a (haloalkyl) -O- group in which the haloalkyl moiety has the above meaning.
For example, a difluoromethoxy group, a trifluoromethoxy group, a pentafluoroethoxy group, etc. can be mentioned.

The haloalkylthio group, haloalkylsulfonyl group and haloalkylsulfinyl group respectively represent an alkylthio group, an alkylsulfonyl group and an alkylsulfinyl group in which an alkyl part is substituted with a halogen atom.

The term "alkylamino group" means a linear or branched alkylamino group having 1 to 3 carbon atoms, and examples thereof include a methylamino group and an ethylamino group.

The dialkylamino group means an amino group in which two linear or branched alkyl groups having 1 to 3 carbon atoms are bonded, and examples thereof include dimethylamino group, diethylamino group,
A methyl ethylamino group etc. can be mentioned.

The cycloalkyl group means a cycloalkyl group having 3 to 6 carbon atoms, and examples thereof include a cyclopropyl group, a cyclopentyl group and a cyclohexyl group.

Specific examples of A in the above general formula [I] include (A-1) as, for example, a methylaminomethyl group, a methylamino group, an aminomethyl group, an amino group and a methyl-N-methylaminomethyl group. , Methyl-N-methylamino group, N-methylaminomethyl group, N-methylamino group and the like. Examples of (A-2) include a methylcarbonylmethyl group, a methylcarbonyl group, a carbonylmethyl group, and a carbonyl group.

Examples of (A-3) include a methylcarbonylaminomethyl group, a methylcarbonylamino group, a carbonylaminomethyl group, a carbonylamino group, a methylcarbonyl-N-methylaminomethyl group, a methylcarbonyl-N-methylamino group, Examples thereof include a carbonyl-N-methylaminomethyl group and a carbonyl-N-methylamino group. Examples of (A-4) include a methylcarbamoylmethyl group, a methylcarbamoyl group, a carbamoylmethyl group, a carbamoyl group, a methyl-N-methylcarbamoylmethyl group, a methyl-N-methylcarbamoyl group,
Examples thereof include N-methylcarbamoylmethyl group and N-methylcarbamoyl group.

Examples of (A-5) include a methylcarbamoyloxymethyl group, a methylcarbamoyloxy group, a carbamoyloxymethyl group, a carbamoyloxy group, a methyl-N-methylcarbamoyloxymethyl group, a methyl-N-methylcarbamoyloxy group, Examples thereof include N-methylcarbamoyloxymethyl group and N-methylcarbamoyloxy group. Examples of (A-6) include a methylcarbamoylaminomethyl group, a methylcarbamoylamino group, a carbamoylaminomethyl group, a carbamoylamino group, a methyl-N-methylcarbamoyl-N-methylaminomethyl group, and a methyl-N-methylcarbamoylaminomethyl group. Group, a methylcarbamoyl-N-methylaminomethyl group, and the like.

Examples of (A-7) include a methylcarbonyloxymethyl group, a methylcarbonyloxy group, a carbonyloxymethyl group and a carbonyloxy group. Examples of (A-8) include a methyloxycarbonylmethyl group, a methyloxycarbonyl group, an oxycarbonylmethyl group and an oxycarbonyl group.

Examples of (A-9) include ethylideneaminomethyl group, ethylideneamino group, methylideneaminomethyl group and methylideneamino group.
Examples of (A-10) include a methyliminoethyl group, a methyliminomethyl group, an iminoethyl group, and an iminomethyl group.

Examples of (A-11) include methylmethylideneaminooxymethyl group, methylmethylideneaminooxy group, methylideneaminooxymethyl group, methylideneaminooxy group, methyl-1-ethylideneaminooxymethyl group and methyl. -1-ethylidene aminooxy group, 1
-Ethylideneaminooxymethyl group, 1-ethylideneaminooxy group, methylcyclopropylmethylideneaminooxymethyl group, methylcyclopropylmethylideneaminooxy group, cyclopropylmethylideneaminooxymethyl group, cyclopropylmethylideneaminooxy group, etc. Can be mentioned.

As a preferred compound group, in the above-mentioned general formula [I], R ¹ is a linear or branched alkyl group having 1 to 6 carbon atoms, X is a halogen atom, and n is 1.
Is an integer of 2 to 2, when n is 2, X may be the same or different combination, Y is a halogen atom,
When m is an integer of 0 to 2, and when m is 2, Y may be the same or different combination, and A is

[0028]

[Chemical 7]

(Wherein R ³ is a linear or branched alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms, and j and k are 0 or 1). R ² is a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or

[0030]

Embedded image

(In the formula, Q and Q ′ are methine groups or nitrogen atoms, R ⁴ is a halogen atom, a linear or branched alkoxy group having 1 to 6 carbon atoms, a straight chain having 1 to 6 carbon atoms or A branched haloalkyl group or a linear or branched haloalkoxy group having 1 to 6 carbon atoms, p is an integer of 0 to 3, and when p is 2 or 3, R ⁴ is the same or different. And a compound represented by the formula (1) may be mentioned.

Next, typical examples of the compounds of the present invention represented by the general formula [I] are shown in Tables 1 to 26. The compound numbers will be referred to in the following description.

[0033]

[Table 1]

[0034]

[Table 2]

[0035]

[Table 3]

[0036]

[Table 4]

[0037]

[Table 5]

[0038]

[Table 6]

[0039]

[Table 7]

[0040]

[Table 8]

[0041]

[Table 9]

[0042]

[Table 10]

[0043]

[Table 11]

[0044]

[Table 12]

[0045]

[Table 13]

[0046]

[Table 14]

[0047]

[Table 15]

[0048]

[Table 16]

[0049]

[Table 17]

[0050]

[Table 18]

[0051]

[Table 19]

[0052]

[Table 20]

[0053]

[Table 21]

[0054]

[Table 22]

[0055]

[Table 23]

[0056]

[Table 24]

[0057]

[Table 25]

[0058]

[Table 26] The compound of the present invention can be produced according to the following production methods 1 to 12, but is not limited to this method. Manufacturing method 1

[0059]

[Chemical 9]

(In the formula, R ⁵ represents an alkyl group or a phenyl group which may be substituted with an alkyl group, and A, R ¹ , R
² , X, Y, m, and n have the same meanings as described above. ) In the production method 1, the benzohydrazonoyl chloride derivative represented by the general formula [II] and the benzonitrile derivative represented by the general formula [III] are reacted in the presence of a Lewis acid in an inert solvent to give a general compound. The compound of the present invention represented by the formula [I] can be obtained.

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, hexane and the like. Aliphatic hydrocarbons such as petroleum ether, halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, o-dichlorobenzene, N, N-dimethylformamide, N, N -A mixed solvent obtained by combining amides such as dimethylacetamide, and a solvent selected from these can be used.

The Lewis acid used is aluminum bromide, aluminum chloride, ferric chloride, boron trifluoride,
Titanium tetrachloride or the like can be used. The amount of the reaction reagent used is usually 1.0 mol of the compound represented by the general formula [III] per 1 mol of the compound represented by the general formula [II].
˜2.0 times mole and Lewis acid is 1.0 to 2.0 times mole.

The reaction temperature can be set to any temperature between 0 ° C. and the boiling point of the solvent. The reaction time varies depending on the compound, but can usually be set between 30 minutes and 5 hours.

Specific examples of this reaction include, for example, the Bulletin of the Chemical Society of Japan (B
all. Chem. Soc. Jpn) Volume 56, 54
P. 5 (1983).

Manufacturing Method 2 In Manufacturing Method 2, the general formulas [V], [VI], [VII]
The compounds represented by [I] and [X] are the compounds of the present invention contained in the compounds represented by the general formula [I].

[0066]

[Chemical 10]

(In the formula, L represents a halogen atom, a methanesulfonyloxy group or a p-toluenesulfonyloxy group, R ⁶ represents an alkyl group or a cycloalkyl group, and R ¹ , R ² , X, Y, j, k, m, and n have the same meanings as described above.) In the step A of the production method 2, the compound of the general formula [IV] is represented by the general formula [V] by reacting with a reducing agent in a solvent. The compound of the present invention can be obtained.

As the reducing agent, metals such as tin and iron and metal salts such as stannous chloride can be used. As the solvent, hydrochloric acid, acetic acid, water or alcohols such as ethanol can be used.

The amount of the reducing agent is the compound 1 of the general formula [IV].
It is preferably 1.0 to 10 times the molar amount.

The reaction temperature can be set to any temperature between 0 ° C. and the boiling point of the solvent, but it is preferably 0 ° C. to 50 ° C. The reaction time is between 30 minutes and 8 hours.

In step B, the compound of formula [VI] is reacted with a formylating agent to form a compound of formula [VI].
The compound of the present invention represented by can be obtained. Formic acid can be used as the formylating agent, for example.

The amount of the formylating agent used is preferably 1.0 to 50 times with respect to 1 mol of the compound represented by the general formula [V].

The reaction temperature is any temperature between 0 ° C. and the boiling point of the solvent, but is preferably between 40 ° C. and the boiling point.

In step C, the compound represented by the general formula [V] or the general formula [VI] is reacted with the compound represented by the general formula [VII] in the presence of a base in an inert solvent, The compound of the present invention represented by the general formula [VIII] can be obtained.

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

As the solvent which can be used here, alcohols such as methanol and ethanol, aromatic hydrocarbons such as benzene and toluene, ethers such as tetrahydrofuran, 1,4-dioxane and 1,2-dimethoxyethane,
A combination of halogenated hydrocarbons such as chloroform and 1,2-dichloroethane, amides such as N, N-dimethyformamide and N, N-dimethylacetamide, sulfoxides such as dimethylsulfoxide, and a solvent selected from them. Mixed solvents can be used.

The reaction temperature is optional between 0 ° C. and the boiling point of the solvent, but is preferably 50 ° C. and the boiling point of the solvent. The reaction time is optional between 1 hour and 40 hours.

In step D, the compound represented by the general formula [VIII] is reacted with the compound represented by the general formula [IX] in the presence of a base in an inert solvent to give the compound represented by the general formula [X]. The compounds of the invention represented can be obtained.

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

As the solvent that can be used here, alcohols such as methanol and ethanol, aromatic hydrocarbons such as benzene and toluene, tetrahydrofuran, 1,4-
Ethers such as dioxane and 1,2-dimethoxyethane, halogenated hydrocarbons such as chloroform and 1,2-dichloroethane, N, N-dimethylformamide, N,
An amide such as N-dimethylacetamide, a sulfoxide such as dimethyl sulfoxide, and a mixed solvent obtained by combining a solvent selected from these can be used.

The reaction temperature can be set to any temperature between 0 ° C. and the boiling point of the solvent. The reaction time is optional between 1 hour and 40 hours.

Production Method 3 In Production Method 3, the compounds of the general formulas [V], [XII] and [XI] are used.
The compound represented by II] is the compound of the present invention contained in the compound represented by the general formula [I].

[0083]

[Chemical 11]

(In the formula, Z represents a halogen atom or a 1-imidazolyl group, and R ¹ , R ² , X, Y, j, k, m and n have the same meanings as described above.) Process 3 In A, the compound represented by the general formula [XI] is reacted by reacting the compound represented by the general formula [V] with the compound represented by the general formula [XI] in the presence of a base in an inert solvent.
The compound of the present invention represented by I] can be obtained.

Examples of the base that can be used here include organic bases such as triethylamine, pyridine and 4-N, N-dimethylaminopyridine, and inorganic bases such as sodium hydroxide and potassium hydroxide, sodium carbonate, potassium carbonate and sodium hydride. Examples thereof include bases and metal alkoxides such as potassium tert-butoxide.

As the solvent which can be used here, ketones such as acetone and methyl ethyl ketone, esters such as methyl acetate and ethyl acetate, aromatic hydrocarbons such as benzene and toluene, diethyl ether, tetrahydrofuran and 1,4-dioxane. , Ethers such as 1,2-dimethoxyethane, halogenated hydrocarbons such as chloroform and 1,2-dichloroethane, amides such as N, N-dimethylformamide and N, N-dimethylacetamide, sulfoxides such as dimethylsulfoxide It is possible to use a mixed solvent in which the solvents and solvents selected from these are combined.

The reaction temperature can be set to any temperature between 0 ° C. and the boiling point of the solvent. The reaction time can be set between 30 minutes and 40 hours.

In step B, the compound of the general formula [XIII] can be obtained by reacting the compound of the general formula [XII] with a reducing agent in an inert solvent. As the reducing agent that can be used here, a metal hydride such as lithium aluminum hydride can be used. As the solvent that can be used here, ethers such as diethyl ether and tetrahydrofuran can be used.

The reaction temperature can be set to any temperature between 0 ° C. and the boiling point of the solvent, but is preferably 0 ° C. to 50 ° C. The reaction time can be set between 30 minutes and 20 hours.

Production Method 4 In Production Method 4, the compounds represented by the general formulas [V] and [XV] are the compounds of the present invention contained in the compounds represented by the general formula [I].

[0091]

[Chemical 12]

(Wherein R ¹ , R ² , X, Y, j, k, m
And n have the same meanings as described above. ) By reacting the compound represented by the general formula [V] with the compound represented by the general formula [XIV] in the production method 4 in the presence of a catalytic amount of a Lewis acid in a solvent or without a solvent,
The compound of the present invention represented by the general formula [XV] can be obtained.

Examples of the Lewis acid that can be used here include titanium tetrachloride, zinc chloride, boron trifluoride, benzenesulfonic acid, p-toluenesulfonic acid and the like.

As the solvent that can be used here, alcohols such as methanol and ethanol, aromatic hydrocarbons such as benzene and toluene, tetrahydrofuran, 1,4-
A mixed solvent in which ethers such as dioxane and 1,2-dimethoxyethane and a solvent selected from these are combined can be used.

The reaction temperature can be set to any temperature between 0 ° C. and the boiling point of the solvent. The reaction time can be set between 1 hour and 40 hours.

Production Method 5 In Production Method 5, the compound represented by the general formula [XVIII] is the compound of the present invention contained in the compound represented by the general formula [I].

[0097]

[Chemical 13]

(Wherein R ¹ , R ² , X, Y, Z, j,
k, m and n have the same meanings as described above. In the production method 5, the compound represented by the general formula [XVI] is reacted with the compound represented by the general formula [XVII] in the presence of a base in an inert solvent to give the compound represented by the general formula [XVI].
The compound of the present invention represented by II] can be obtained. Examples of the base that can be used here include organic bases such as triethylamine, pyridine and 4-N, N-dimethylaminopyridine, and inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and sodium hydride. To be

As the solvent which can be used here, ketones such as acetone and methyl ethyl ketone, aromatic hydrocarbons such as benzene and toluene, diethyl ether, tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane and diglyme. Ethers such as, methyl acetate,
Esters such as ethyl acetate, halogenated hydrocarbons such as chloroform and 1,2-dichloroethane, amides such as N, N-dimethylformamide and N, N-dimethylacetamide, sulfoxides such as dimethylsulfoxide, and a selection thereof. It is possible to use a mixed solvent in which the above solvents are combined.

The reaction temperature can be set to any temperature between 0 ° C. and the boiling point of the solvent. The reaction time can be set between 1 hour and 40 hours.

Production Method 6 In Production Method 6, the compound represented by the general formula [XX] is the compound of the present invention contained in the compound represented by the general formula [I].

[0102]

Embedded image

(Wherein R ¹ , R ² , X, Y, j, k, m
And n have the same meanings as described above. In the production method 6, the compound represented by the general formula [XVI] is reacted with the compound represented by the general formula [XIX] in the absence of a catalyst or in the presence of a catalytic amount of an acid or a base in an inert solvent or without a solvent. By doing so, the compound of the present invention represented by the general formula [XX] can be obtained. Examples of the acid that can be used here include hydrochloric acid, aluminum chloride, boron trifluoride etherate, and the like, and examples of the base include triethylamine, pyridine, sodium acetate, and the like.

As the solvent that can be used here, aromatic hydrocarbons such as benzene and toluene, diethyl ether, tetrahydrofuran, 1,4-dioxane, 1,2
-Ethers such as dimethoxyethane, dichloromethane,
Hydrocarbons such as chloroform, ketones such as acetone and methyl ethyl ketone, esters such as methyl acetate and ethyl acetate, and mixed solvents obtained by combining solvents selected from these can be used.

The reaction temperature can be set to any temperature between 0 ° C. and the boiling point of the solvent. The reaction time can be set between 1 hour and 40 hours.

Production Method 7 In Production Method 7, the compound represented by the general formula [XXIII] is the compound of the present invention contained in the compound represented by the general formula [I].

[0107]

[Chemical 15]

(Wherein R ¹ , R ³ , R ⁴ , X, Y, L,
Q, Q ', k, m, n and p have the same meanings as described above. In the production method 7, the compound represented by the general formula [XXI] is reacted with the compound represented by the general formula [XXII] in the presence of a base in an inert solvent to give a compound represented by the general formula [XXI:
The compound of the present invention represented by II] can be obtained.

As the base which can be used here, inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and sodium hydride, potassium ter
Examples include alkali metal alkoxides such as t-butoxide.

As the solvent which can be used here, ketones such as acetone and methyl ethyl ketone, aromatic hydrocarbons such as benzene and toluene, diethyl ether, tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane and diglyme. Ethers such as, methyl acetate,
Esters such as ethyl acetate, halogenated hydrocarbons such as chloroform and 1,2-dichloroethane, amides such as N, N-dimethylformamide and N, N-dimethylacetamide, sulfoxides such as dimethylsulfoxide, and a selection thereof. It is possible to use a mixed solvent in which the above solvents are combined.

The reaction temperature can be set to any temperature between 0 ° C. and the boiling point of the solvent. The reaction time can be set between 1 hour and 40 hours.

Production Method 8 The compound represented by the general formula [XXV] in the production method 8 is the compound of the present invention contained in the compound represented by the general formula [I].

[0113]

[Chemical 16]

(In the formula, R ¹ , X, Y, j, m and n have the same meanings as described above.) In the production method 8, the compound represented by the general formula [XXIV] is
By oxidizing, the compound of the present invention represented by the general formula [XXV] can be obtained.

Examples of the oxidation method mentioned here include methods using chromates such as pyridinium chlorochromate and pyridinium dichromate, methods using manganese dioxide, and methods using dimethyl sulfoxide typified by Swern oxidation. can give.

Production Method 9 In Production Method 9, the compounds of the general formulas [XXV] and [XXVI]
The compound represented by I] is the compound of the present invention contained in the compound represented by the general formula [I].

[0117]

[Chemical 17]

(Wherein R ¹ , R ² , X, Y, k, j,
m and n have the same meanings as described above. In the production method 9, a compound represented by the general formula [XXVII] is reacted with a compound represented by the general formula [XXVI] in the presence of a catalytic amount of a Lewis acid in a solvent or without a solvent. ] The compound of the present invention represented by

Examples of the Lewis acid that can be used here include titanium tetrachloride, zinc chloride, boron trifluoride, benzenesulfonic acid, p-toluenesulfonic acid and the like.

As the solvent that can be used here, alcohols such as methanol and ethanol, aromatic hydrocarbons such as benzene and toluene, tetrahydrofuran, 1,4-
A mixed solvent obtained by combining ethers such as dioxane and 1,2-dimethoxyethane and a solvent selected from these can be used.

The reaction temperature can be set to any temperature between 0 ° C. and the boiling point of the solvent. The reaction time can be set between 1 hour and 40 hours.

Production Method 10 In Production Method 10, the compounds of the general formulas [XII] and [XXVI]
The compound represented by II] is the compound of the present invention contained in the compound represented by the general formula [I].

[0123]

[Chemical 18]

(Wherein R ¹ , R ² , R ⁶ , X, Y, L,
k, j, m, and n have the same meanings as described above. ) In the production method 10, the compound represented by the general formula [XXII] is reacted with the compound represented by the general formula [IX] in the presence of a base in an inert solvent to give a compound represented by the general formula [XXVI]
The compound of the present invention represented by II] can be obtained.

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

As the solvent that can be used here, alcohols such as methanol and ethanol, aromatic hydrocarbons such as benzene and toluene, tetrahydrofuran, 1,4-
Ethers such as dioxane and 1,2-dimethoxyethane, halogenated hydrocarbons such as chloroform and 1,2-dichloroethane, N, N-dimethylformamide, N,
An amide such as N-dimethylacetamide, a sulfoxide such as dimethyl sulfoxide, and a mixed solvent obtained by combining a solvent selected from these can be used.

The reaction temperature can be set to any temperature between 0 ° C. and the boiling point of the solvent. The reaction time can be set between 1 hour and 40 hours.

Production Method 11 In the production method 11, general formulas [V] and [XXIX] are used.
The compound represented by is the compound of the present invention contained in the compound represented by the general formula [I].

[0129]

[Chemical 19]

(Wherein R ¹ , R ² , X, Y, j, k, m
And n have the same meanings as described above. In the production method 11, the compound represented by the general formula [V] and the compound represented by the general formula [XIX] are reacted in the absence of a catalyst or in the presence of a catalytic amount of an acid or a base in an inert solvent or without a solvent. By doing so, the compound of the present invention represented by the general formula [XXIX] can be obtained. Examples of the acid that can be used here include hydrochloric acid, aluminum chloride, boron trifluoride etherate, and the like, and examples of the base include triethylamine, pyridine, sodium acetate, and the like.

As the solvent that can be used here, aromatic hydrocarbons such as benzene and toluene, diethyl ether, tetrahydrofuran, 1,4-dioxane, 1,2
-Ethers such as dimethoxyethane, dichloromethane,
Hydrocarbons such as chloroform, ketones such as acetone and methyl ethyl ketone, esters such as methyl acetate and ethyl acetate, and mixed solvents obtained by combining solvents selected from these can be used.

The reaction temperature can be set to any temperature between 0 ° C. and the boiling point of the solvent. The reaction time is optional between 1 hour and 40 hours.

Production Method 12 In Production Method 12, the compound represented by the general formula [XXX] is the compound of the present invention contained in the compound represented by the general formula [I].

[0134]

Embedded image

(Wherein R ¹ , R ² , X, Y, L, k, m
And n have the same meanings as described above. ) In the production method 12, the compound represented by the general formula [XXI] and the compound represented by the general formula [XXVI] are added in the presence of a base,
By reacting in an inert solvent, the compound of the general formula [XX
The compound of the present invention represented by X] can be obtained.

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

As the solvent which can be used here, ketones such as acetone and methyl ethyl ketone, aromatic hydrocarbons such as benzene and toluene, diethyl ether, tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane and diglyme. Ethers such as, methyl acetate,
Esters such as ethyl acetate, halogenated hydrocarbons such as chloroform and 1,2-dichloroethane, amides such as dimethylformamide and dimethylacetamide, sulfoxides such as dimethylsulfoxide, and mixed solvents in which solvents selected from these are combined. Can be used.

The reaction temperature can be set to any temperature between 0 ° C. and the boiling point of the solvent. The reaction time can be set between 1 hour and 40 hours.

[0139]

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 5- (4-aminophenyl) -3- (2-chloro-6-fluorophenyl) -1-methyl-1H-
Production of 1,2,4-triazole (Compound No. 24) Stannous chloride dihydrate (25.
0 g) was added, and the mixture was stirred at room temperature until completely dissolved. 3- (2-chloro-6-fluorophenyl) -1-methyl-5- (4-nitrophenyl) -1H-1,2,4-triazole (11.5 g) was added to this mixture at room temperature with stirring.
Was added, and the mixture was stirred at room temperature for 7 hours. After the reaction was completed, the reaction mixture solution was neutralized with a 10% aqueous sodium hydroxide solution, and 300 ml of ethyl acetate was added. The organic layer was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue is ethyl acetate
The product was recrystallized from a mixed solvent of hexane to obtain the target product (10.4 g, melting point 173.0 to 176.0 ° C.) as pale yellow granular crystals. NMR data (60 MHz, CDCl ₃ solvent, δ value) 3.97 (2H, s) 4.00 (3H, s) 6.00 to 7.50 (7H, m)

Production Example 2 3- (2-chloro-6-fluorophenyl) -5- (4-formamidophenyl) -1
Preparation of -Methyl-1H-1,2,4-triazole (Compound No. 145) 5- (4-Aminophenyl) -3- (2-chloro-6-
Fluorophenyl) -1-methyl-1H-1,2,4-
Triazole (4.0g) and 90% formic acid (100ml)
The mixture was heated to reflux with stirring for 5 hours. After cooling to room temperature, the solvent was distilled off under reduced pressure, the residue was purified by silica gel column chromatography, and the desired product as colorless granular crystals (4.1
g, melting point 76.0-81.0 ° C). NMR data (60 MHz, CDCl ₃ solvent, δ value) 4.06 (3H, s) 6.87 to 7.87 (7H, m) 8.20 (1H, s) 9.37 (1H, s)

Production Example 3 3- (2-chloro-6-fluorophenyl) -1-methyl-5- [4- (5-trifluoromethylpyridin-2-ylamino) phenyl)]-
Production of 1H-1,2,4-triazole (Compound No. 66) 3- (2-chloro-6-fluorophenyl) -5- (4
-Formamidophenyl) -1-methyl-1H-1,
2,4-triazole (1.39 g), potassium ter
t-butoxide (0.6 g), 2-methanesulfonyl-
5-trifluoromethylpyridine (1.00 g) was added to N,
N-Dimethylformamide (DMF) (10 ml) was added, and the mixture was heated with stirring at 60 ° C to 70 ° C for 5 hours. After cooling to room temperature, the reaction mixture was poured into water, extracted with 200 ml of ethyl acetate, washed with water, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography to give the desired product (0.80 as colorless feather-like crystals).
g, melting point 171.0-173.0 ° C). NMR data (60 MHz, CDCl ₃ solvent, δ value) 4.07 (3H, s) 6.60 to 8.10 (11H, m)

Production Example 4 5- (2-chloro-4-aminophenyl) -3- (2-chloro-6-fluorophenyl) -1-methyl-1H-1,2,4-trizole (Compound No. 25) Preparation of Stannous chloride dihydrate (20.3 g) was added to 36% concentrated hydrochloric acid (30 ml), and the mixture was stirred at room temperature until completely dissolved. 3- (2-chloro-6-fluorophenyl) -5- (2-chloro-4-nitrophenyl) -1 was added to this mixture.
-Methyl-1H-1,2,4-triazole (11.0
g) was added and the mixture was stirred at room temperature for 3 hours. After completion of the reaction, 10% aqueous sodium hydroxide solution was added to the reaction mixture to neutralize the reaction solution, ethyl acetate (300 ml) was added, and the mixture was stirred at room temperature for 30 minutes.
Stir for minutes. The ethyl acetate layer was separated from the mixed solution,
After washing with water, it was dried over anhydrous magnesium sulfate. The solvent was evaporated under reduced pressure, and the residue was purified by silica gel column chromatography to obtain the target product (8.5 g, melting point 51.0-55.0 ° C) as a tan candy-like substance. NMR data (60 MHz, CDCl ₃ solvent, δ value) 3.90 (3H, s) 4.23 (2H, s) 6.30 to 7.60 (6H, m)

Production Example 5 3- (2-chloro-6-fluorophenyl) -5- (2-chloro-4-formamidophenyl) -1-methyl-1H-1,2,4-triazole (Compound No. 144) Preparation of 5- (2-chloro-4-aminophenyl) -3- (2-
Chloro-6-fluorophenyl) -1-methyl-1H-
A mixture of 1,2,4-trizole (1.00 g) and 90% formic acid (10 ml) was heated under reflux for 1 hour. After completion of the reaction, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography to obtain the desired product (0.65 g, melting point 81.0-85.0 ° C) as yellowish white powder crystals. NMR data (60 MHz, CDCl ₃ solvent, δ value) 3.83 (3H, s) 7.00 to 7.60 (6H, m) 8.10 (1H, s) 9.17 (1H, s)

Production Example 6 3- (2-chloro-6-fluorophenyl) -5- [2-chloro-4- (5-trifluoromethylpyridin-2-ylamino) phenyl] -1
Preparation of -Methyl-1H-1,2,4-triazole (Compound No. 67) 3- (2-chloro-6-fluorophenyl) -5- (2
-Chloro-4-formamidophenyl) -1-methyl-
1H-1,2,4-triazole (0.50 g) and potassium tert-butoxide (0.18 g) were added to DMF.
(10 ml) and heated to 50 ° C. to dissolve. After dissolution, 2-methanesulfonyl-5-trifluoromethylpyridine (0.37 g) was added, and the mixture was heated with stirring at 140 ° C for 3 hours. After checking the completion of the reaction, the reaction mixture was poured into water, extracted with ethyl acetate (200 ml), washed with water and dried over anhydrous magnesium sulfate. The solvent was evaporated under reduced pressure, and the obtained residue was purified by silica gel column chromatography to give the object product (0.50 g, melting point 88.0-9) as yellowish white powder crystals.
2.0 ° C.) was obtained. NMR data (60 MHz, CDCl ₃ solvent, δ value) 3.83 (3H, s) 6.50 to 8.30 (10H, m)

Production Example 7 3- (2-chloro-6-fluorophenyl) -5- [2-chloro-4- (3-chloro-
Preparation of 5-trifluoromethylpyridin-2-ylamino) phenyl] -1-methyl-1H-1,2,4-triazole (Compound No. 44) 3- (2-chloro-6-fluorophenyl) -5- ( Two
-Chloro-4-aminophenyl) -1-methyl-1H-
1,2,4-triazole (0.50 g) was added to DMF (1
0 ml) and 60% sodium hydride (0.0
7 g) was added and the mixture was stirred at room temperature for 30 minutes. 2, to this mixture
3-dichloro-5-trifluoromethylpyridine (0.
35 g), sodium p-toluenesulfinate (0.
13 g) was added and heated at 140 ° C. for 3 hours. After cooling to room temperature, the reaction solution was poured into water and ethyl acetate (200
(ml), the extract was washed with 5% hydrochloric acid, dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography to give the desired product (0.32 g, melting point 239.0 to 241.0) as yellowish white powdery crystals.
C) was obtained. NMR data (60 MHz, CDCl ₃ solvent, δ value) 3.98 (3H, s) 7.00 to 8.50 (9H, m)

Production Example 8 3- (2-chloro-6-fluorophenyl) -5- [4- (2-chloro-4-trifluoromethylbenzoylamino) phenyl] -1-methyl-1H-1,2, 4-triazole (Compound No. 15
Preparation of 3) 5- (4-aminophenyl) -3- (2-chloro-6-
Fluorophenyl) -1-methyl-1H-1,2,4-
Triazole (0.91 g), 2-chloro-4-trifluoromethylbenzoic acid chloride (0.80 g) and triethylamine (0.50 g) were dissolved in toluene (30 ml), and the mixture was heated with stirring at 60 ° C. for 3 hours. After cooling to room temperature,
Toluene (200 ml) was added for extraction, and the organic layer was 5%.
It was washed with hydrochloric acid, washed with water, and dried over anhydrous sodium sulfate. The solvent was evaporated under reduced pressure, and the residue was recrystallized from a mixed solvent of ethyl acetate-hexane to obtain the target substance (1.37 g, melting point 204.0-205.0 ° C) as colorless feathery crystals. NMR data (60 MHz, CDCl ₃ solvent, δ value) 4.04 (3H, s) 6.90 to 7.90 (10H, m) 10.13 (1H, s)

Production Example 9 3- (2-chloro-6-fluorophenyl) -5- {4- [N- (2-chloro-4-trifluoromethylbenzoyl) -N-methylamino] phenyl} -1- Preparation of Methyl-1H-1,2,4-triazole (Compound No. 161) 3- (2-chloro-6-fluorophenyl) -5- [4
-(2-Chloro-4-trifluoromethylbenzoylamino) phenyl] -1-methyl-1H-1,2,4-triazole (0.96 g) was dissolved in DMF (50 ml), and 60% sodium hydride ( 0.10 g) was added at room temperature. After the generation of hydrogen gas was completed, methyl iodide (1.0 g) was added and the mixture was heated with stirring at 60 ° C. for 5 hours. After cooling to room temperature, the reaction mixture is poured into water and ethyl acetate 200m
It was extracted with l, washed with water, and dried over anhydrous sodium sulfate.
The solvent was evaporated under reduced pressure, the residue was purified by silica gel column chromatography, and recrystallized from a mixed solvent of ethyl acetate-hexane to give the desired product as colorless powdery crystals (0.58 g, melting point 221.0- 222.0 ° C.) was obtained. NMR data (60 MHz, CDCl ₃ solvent, δ value) 3.49 (3H, s) 3.97 (3H, s) 6.90 to 7.80 (10H, m)

Production Example 10 3- (2-chloro-6-fluorophenyl) -5- [4- (4-trifluoromethylbenzoylamino) phenyl] -1-methyl-1H-
Preparation of 1,2,4-triazole (Compound No. 156) 3- (2-chloro-6-fluorophenyl) -5- (4
-Aminophenyl) -1-methyl-1H-1,2,4-
Triazole (0.50 g), triethylamine (0.
20 g) was dissolved in toluene (20 ml). 4-Trifluoromethylbenzoyl chloride (0.40 g) was added dropwise to this mixture under ice cooling, and the mixture was stirred at room temperature for 3 hours. The reaction solution was washed with water and dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography to obtain the target product (0.67 g, melting point 197.0-200.0 ° C) as colorless granular crystals. NMR data (60 MHz, CDCl ₃ solvent, δ value) 3.97 (3H, s) 6.80 to 8.00 (11H, m) 9.57 (1H, s)

Production Example 11 3- (2-chloro-6-fluorophenyl) -5- [4- (4-trifluoromethylbenzylamino) phenyl] -1-methyl-1H-1,
Preparation of 2,4-triazole (Compound No. 131) 3- (2-chloro-6-fluorophenyl) -5- [4
-(4-Trifluoromethylbenzoylamino) phenyl] -1-methyl-1H-1,2,4-triazole (0.67 g) was added to diethyl ether (20 ml), and the mixture was stirred at room temperature and dissolved. A suspension of lithium aluminum hydride (0.06 g) in diethyl ether (10 ml) was added dropwise to this mixture at room temperature, and after completion of the dropwise addition, the mixture was stirred at room temperature for 3 hours. After confirming the completion of the reaction, a small amount of ethyl acetate was added to the reaction mixture, the mixture was stirred at room temperature for 30 minutes, water was added to the reaction mixture, extracted with ether (200 ml), washed with water and dried over anhydrous magnesium sulfate. The solvent was evaporated under reduced pressure, and the obtained residue was purified by silica gel column chromatography to give the desired product as a milky white powder crystal (0.47 g, melting point 157).
˜162 ° C.) was obtained. NMR data (60 MHz, CDCl ₃ solvent, δ value) 3.97 (3H, s) 4.45 (2H, d) 4.78 (1H, t) 6.50 to 8.00 (11H, m)

Production Example 12 3- (2-chloro-6-fluorophenyl) -1-methyl-5- [4- (4-trifluoromethylbenzylideneamino) phenyl] -1H-
Preparation of 1,2,4-triazole (Compound No. 351) 5- (4-aminophenyl) -3- (2-chloro-6-
Fluorophenyl) -1-methyl-1H-1,2,4-
Triazole (1.0 g), 4-trifluoromethylbenzaldehyde (0.8 g) and p-toluenesulfonic acid (0.1 g) were added to toluene (300 ml), and the mixture was heated under reflux for 5 hours with stirring. After cooling to room temperature, the organic layer is 5%
It was washed with hydrochloric acid, washed with water, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, the residue was purified by silica gel column chromatography, and recrystallized from a mixed solvent of acetone-hexane to give the desired product of pale yellow prismatic crystals (0.65 g, melting point 126.0 to 126.0). 128.0
C) was obtained. NMR data (60 MHz, CDCl ₃ solvent, δ value) 4.07 (3H, s) 7.20 to 8.10 (11H, m) 8.47 (1H, s)

Production Example 13 3- (2-chloro-6-fluorophenyl) -5- [3-chloro-4- (2-fluoro-4-trifluoromethylbenzoyloxymethyl)
Production of Phenyl] -1-methyl-1H-1,2,4-triazole (Compound No. 300) 3- (2-chloro-6-fluorophenyl) -5- (3
-Chloro-4-hydroxymethylphenyl) -1-methyl-1H-1,2,4-triazole (0.50 g),
Pyridine (0.13 g) was dissolved in 20 ml of benzene, a 10 ml solution of 2-fluoro-4-trifluoromethylbenzoyl chloride (0.34 g) in benzene was added dropwise at room temperature, and the mixture was stirred at room temperature for 5 hours. The reaction solution was washed with water and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography to give the desired product as a white powder (0.62 g, melting point 105.0).
˜110.0 ° C.) was obtained. NMR data (60 MHz, CDCl ₃ solvent, δ value) 4. 10 (3H, s) 5. 57 (2H, s) 7. 90-8. 20 (9H, m)

Production Example 14 3- (2-chloro-6-fluorophenyl) -1-methyl-5- {4- [N- (4-
Preparation of trifluoromethoxyphenyl) carbamoyl] oxyphenyl} -1H-1,2,4-triazole (Compound No. 212) 3- (2-chloro-6-fluorophenyl) -5- (4
-Hydroxyphenyl) -1-methyl-1H-1,2,
4-Triazole (0.76 g) and 4-trifluoromethoxyphenyl isocyanate (0.60 g) were dissolved in tetrahydrofuran (10 ml), 3 drops of triethylamine was added, and the mixture was heated under reflux for 30 hr with stirring. After cooling to room temperature, ethyl acetate (200 ml) was added, and the organic layer was added to 5
% Aqueous sodium hydroxide solution, washed with water, and dried over anhydrous sodium sulfate. The solvent was evaporated under reduced pressure, the residue was purified by silica gel column chromatography, and the target product as pale yellow powdery crystals (0.38 g, melting point 138.0-1) was obtained.
40.5 ° C.) was obtained. NMR data (60 MHz, CDCl ₃ solvent, δ value) 4.07 (3H, s) 7.00 to 7.80 (11H, m) 9.77 (1H, s)

Production Example 15 3- (2-chloro-6-fluorophenyl) -5- [4- (2-chloro-4-trifluoromethylbenzoyloxy) phenyl] -1-methyl-1H-1,2, 4-triazole (Compound No. 25
Preparation of 2) 3- (2-chloro-6-fluorophenyl) -5- (4
-Hydroxyphenyl) -1-methyl-1H-1,2,
4-triazole (0.52 g), 2-chloro-4-trifluoromethylbenzoyl chloride (0.42 g),
Triethylamine (0.2g) with benzene (10ml)
And was heated to reflux for 4 hours. After cooling to room temperature, ethyl acetate (200 ml) was added, the organic layer was washed with a 5% aqueous sodium hydroxide solution, washed with water, and dried over anhydrous sodium sulfate. The solvent was evaporated under reduced pressure, the residue was purified by silica gel column chromatography, and the obtained crude crystals were washed with hexane to give the desired product as colorless granular crystals (0.62 g, melting point 1
31.0-135.0 ° C) was obtained. NMR data (60 MHz, CDCl ₃ solvent, δ value) 4.07 (3H, s) 6.90 to 8.20 (10H, m)

Production Example 16 3- (2-chloro-6-fluorophenyl) -5- [4- (3-chloro-5-trifluoromethylpyridin-2-ylaminomethyl) phenyl] -1-methyl-1H Preparation of -1,2,4-triazole (Compound No. 111) 3- (2-chloro-6-fluorophenyl) -1-methyl-5- (4-methylphenyl) -1H-1,2,4-
Triazole (3.20 g), N-bromosuccinimide (2.40 g), azobisisobutyronitrile (50
(mg) was added to carbon tetrachloride (100 ml), and the mixture was heated under reflux for 1 hour. After cooling to room temperature, insoluble matter was filtered off, the filtrate was washed with water and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to give 5- (4-bromomethylphenyl) -3.
A crude product of-(2-chloro-6-fluorophenyl) -1-methyl-1H-1,2,4-triazole was obtained.

2-Amino-3-chloro-5-trifluoromethylpyridine (0.66 g) was dissolved in N, N-dimethylformamide (30 ml), and 60% sodium hydride (0.15 g) was added at room temperature. Stir for 30 minutes. The above crude product (1.1 g) was added to this mixture, and the mixture was stirred at room temperature for 8 hours. Pour the reaction solution into water and add toluene (200 m
It was extracted with l), washed with water and dried over anhydrous sodium sulfate. The solvent was evaporated under reduced pressure, and the residue was purified by silica gel column chromatography to obtain the desired product (0.38 g, melting point 111.0-114.0 ° C) as brown granular crystals. NMR data (60 MHz, CDCl ₃ solvent, δ value) 4.06 (3H, s) 4.80 (2H, d) 5.87 (1H, t) 6.90 to 8.30 (9H, m)

Production Example 17 O- {4- [3- (2-chloro-6-fluorophenyl) -1-methyl-1H-1,
Preparation of 2,4-triazol-5-yl] benzyl} -4-chlorophenylcyclopropylketone oxime (Compound No. 369) 4-chlorophenylcyclopropylketone oxime (1.4g) was added to 1,2-dimethoxyethane (20ml).
Dissolve in 60% sodium hydride (0.15 g)
Add at ~ 3 ° C and stir for 1 hour. 3 to this mixed solution
(2-chloro-6-fluorophenyl) -5- (4-chloromethylphenyl) -1-methyl-1H-1,2,4
-Triazole (1.70 g) was added and at room temperature for 1 hour,
The mixture was stirred at 50 ° C for 10 hours. The reaction mixture was poured into water, extracted with diethyl ether (200 ml), washed with water, and dried over anhydrous sodium sulfate. The solvent was evaporated under reduced pressure, the residue was purified by silica gel column chromatography, and the desired product as a colorless candy-like substance (0.95 g, n _D ²⁰
= 1.6155) was obtained. NMR data (60 MHz, CDCl ₃ solvent, δ value) 0.50 to 2.40 (5H, m) 4.07 (3H, s) 5.17 (2H, d) 6.80 to 7.90 (11H, m)

Production Example 18 3- (2-chloro-6-fluorophenyl) -5- [4- (2,4-dichloroanilinocarbonyl) phenyl] -1-methyl-1H-1,
Preparation of 2,4-triazole (Compound No. 186) N-methyl-N- (p-toluenesulfonyl) -2-chloro-6-fluorobenzhydrazonoyl chloride (1.70 g), 4-cyano-2'- 4'-dichlorobenzanilide (1.40 g), anhydrous ferric chloride (0.7
5 g) was dissolved in o-dichlorobenzene (10 ml),
The mixture was heated and stirred at an oil bath temperature of 130 to 140 ° C. for 1 hour. The reaction mixture was poured into water, extracted with chloroform (200 ml), washed with water and dried over anhydrous sodium sulfate. The solvent was evaporated under reduced pressure, the residue was purified by silica gel column chromatography, and the target product (0.13
g, melting point 161.0-166.0 ° C.). NMR data (60 MHz, CDCl ₃ solvent, δ value) 4.08 (3H, s) 6.90 to 8.50 (11H, m)

Production Example 19 3- (2-chloro-6-fluorophenyl) -5- [4- (4-trifluoromethylphenoxycarbonyl) phenyl] -1-methyl-1H
Preparation of -1,2,4-triazole (Compound No. 335) N-methyl-N- (p-toluenesulfonyl) -2-chloro-6-fluorobenzhydrazonoyl chloride (0.97 g), 4- (4 -Trifluoromethylbenzoyloxy) benzonitrile (0.88 g), anhydrous ferric chloride (0.46 g) and o-dichlorobenzene (10 m
It was dissolved in 1) and heated and stirred at an oil bath temperature of 130 to 140 ° C. for 3 hours. The reaction mixture was poured into water, extracted with chloroform (200 ml), washed with water and dried over anhydrous sodium sulfate. The solvent was evaporated under reduced pressure, and the residue was purified by silica gel column chromatography to obtain the desired product as white powder crystals (0.72 g, melting point 142.0 to 146.0 ° C). NMR data (60 MHz, CDCl ₃ solvent, δ value) 4.16 (3H, s) 7.00 to 8.40 (11H, m)

Production Example 20 3- (2-chloro-6-fluorophenyl) -5- (4-formylphenyl) -1-
Production of Methyl-1H-1,2,4-triazole (Compound No. 137) Pyridinium dichromate (5.60 g) was dissolved in dichloromethane (20 ml), and 3- (2-chloro-6-fluoro) was added to this mixed solution. Phenyl) -5- (4-hydroxymethylphenyl) -1-methyl-1H-1,2,4-triazole (3.30 g) in dichloromethane (25 m
l) The solution was added dropwise at room temperature and stirred at room temperature for 15 hours. The insoluble matter of the reaction mixture was filtered, and further ether (30 m
It was washed with l) and the filtrate was concentrated. Concentrate the ether (2
(00 ml), washed with water, and dried over anhydrous sodium sulfate. The solvent was evaporated under reduced pressure, and the residue was purified by silica gel column chromatography to obtain the desired product as white powder crystals (2.60 g, melting point 97.0-102.0 ° C). NMR data (60 MHz, CDCl ₃ solvent, δ value) 4.10 (3H, s) 6.90 to 7.40 (3H, m) 8.00 (4H, s) 10.10 (1H, s)

Production Example 21 N- {4- [3- (2-chloro-6-fluorophenyl) -1-methyl-1H-1,
2,4-triazol-5-yl] benzylidene}-
Preparation of 2,4-dichloroaniline (Compound No. 353) 3- (2-chloro-6-fluorophenyl) -5- (4
-Formylphenyl) -1-methyl-1H-1,2,4
-Dissolve triazole (0.33g) and 2,4-dichloroaniline (0.16g) in toluene (20ml),
Titanium tetrachloride (0.5 ml) (10 mol dichloromethane solution) was added, and the mixture was heated under reflux for 8 hours with stirring. After cooling
It was washed with water and dried over anhydrous magnesium sulfate. The solvent was evaporated under reduced pressure, the residue was purified by silica gel column chromatography, and the target product as pale yellow powdery crystals (0.27 g,
Melting point 150.0-152.0 ° C). NMR data (60 MHz, CDCl ₃ solvent, δ value) 4.10 (3H, s) 6.80 to 8.10 (10H, m) 8.35 (1H, s)

Reference Example 1 Preparation of 3- (2-chloro-6-fluorophenyl) -1-methyl-5- (4-nitrophenyl) -1H-1,2,4-triazole N-methyl-N- ( p-toluenesulfonyl) -2-chloro-6-fluorobenzohydrazonoyl 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 purified by silica gel column chromatography to obtain 12.1 g of the desired product as colorless granular crystals (melting point: 140-143 ° C). NMR data (60 MHz, CDCl ₃ solvent, δ value: p
pm) 3.97 (3H, s) 4.00 (2H, s) 6.5 to 7.5 (7H, m)

Reference Example 2 Preparation of 3- (2-chloro-6-fluorophenyl) -5- (3-chloro-4-methylphenyl) -1-methyl-1H-1,2,4-triazole N-methyl -N- (p-toluenesulfonyl) -2-chloro-6-fluorobenzohydrazonoyl chloride (1
5.0 g), 3-chloro-4-methylbenzonitrile (6.7 g), anhydrous aluminum chloride (6.0 g), o
A mixture of dichlorobenzene (30 ml) at an oil bath temperature of 1
The mixture was stirred at 40 ° C for 1 hour. After cooling, it was washed with brine.
Next, it was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The obtained concentrate was purified by silica gel column chromatography to obtain 7.4 g of the desired product.

Reference Example 3 5- (4-bromomethyl-3-
Preparation of chlorophenyl) -3- (2-chloro-6-fluorophenyl) -1-methyl-1,2,4-triazole 3- (2-chloro-6-fluorophenyl) -5 on carbon tetrachloride (100 ml). -(3-Chloro-4-methylphenyl) -1-methyl-1H-1,2,4-triazole (6.7 g), N-bromosuccinimide (4.3)
g) and azobisisobutyronitrile (50 mg) were added, and the mixture was heated under reflux for 1 hr with stirring. After cooling the reaction mixture, the insoluble material was filtered off, and the filtrate was concentrated under reduced pressure. The obtained concentrate was purified by silica gel column chromatography to obtain 5.0 g of the desired product (melting point: 124.0-126.0 ° C).

Reference Example 4 5- (4-acetoxymethyl-
Preparation of 3-chlorophenyl) -3- (2-chloro-6-fluorophenyl) -1-methyl-1H-1,2,4-triazole DMF (50 ml) in 5- (4-bromomethyl-3-chlorophenyl)- 3- (2-Chloro-6-fluorophenyl) -1-methyl-1H-1,2,4-triazole (4.9 g) and potassium acetate (5.8 g) were added, 13
Stirred at 0 ° C. for 3 hours. The reaction mixture was cooled to room temperature, poured into water and extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. This concentrate was purified by silica gel column chromatography to obtain 2.4 g of the desired product. NMR data (60 MHz, CD
Cl ₃ solvent, δ value: ppm) 2.13 (3H, s) 4.07 (3H, s) 5.24 (2H, S) 6.90 to 7.85 (6H, m)

Reference Example 5 Preparation of 3- (2-chloro-6-fluorophenyl) -5- (3-chloro-4-hydroxymethylphenyl) -1-methyl-1H-1,2,4-triazole 5- (4-acetoxymethyl-3-chlorophenyl)-
3- (2-chloro-6-fluorophenyl) -1-methyl-1H-1,2,4-triazole (2.2 g) was dissolved in a mixed solvent of ethanol (20 ml) and water (5 ml) and hydroxylated. Sodium (0.5 g) was added, and the mixture was heated under reflux for 1 hr with stirring. After cooling to room temperature, ethyl acetate was added to the reaction mixture and washed with water. Next, it was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to obtain crude crystals. The crude crystals were washed with a hexane-ethanol mixed solvent to obtain 1.3 g of the desired product (melting point: 111 to 113 ° C). NMR data (60 MHz, CDCl ₃ solvent, δ value: p
pm) 3.50 (1H, t) 4.05 (3H, s) 4.75 (2H, d) 6.95 to 7.70 (6H, m)

Reference Example 6 3- (2-chloro-6-fluorophenyl) -5- (4-hydroxyphenyl) -1-
Production of Methyl-1H-1,2,4-triazole o-Dichlorobenzene (200 ml) in 4-methoxybenzonitrile (31.9 g) and anhydrous ferric chloride (42.
2 g) was added and heated to 120 ° C. with stirring. N- dissolved in o-dichlorobenzene (300 ml) was added to this mixture.
Methyl-N- (p-toluenesulfonyl) -2-chloro-6-fluorobenzohydrazonoyl chloride (62.
9 g) was added dropwise with stirring at 120 ° C. over 30 minutes,
Furthermore, it stirred at 120 degreeC for 3 hours. After cooling to room temperature, the reaction mixture was poured into a large amount of water and extracted with chloroform. The obtained organic layer was mixed with 10% NaOH aqueous solution (200 ml) and 2
Aqueous 5% ammonia (200 ml) was added and the mixture was stirred at 50 ° C. for 1 hour. After cooling to room temperature, the organic layer was washed with water, dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give 3- (2-chloro-6-
Fluorophenyl) -5- (4-methoxyphenyl)-
63.7 g of a crude product of 1-methyl-1H-1,2,4-triazole was obtained. 3-to benzene (300 ml)
(2-Chloro-6-fluorophenyl) -5- (4-methoxyphenyl) -1-methyl-1H-1,2,4-triazole crude product (70.5 g), anhydrous aluminum chloride (80.0 g) ) Was added, and the mixture was stirred and heated under reflux for 3 hours. After cooling to room temperature, the reaction mixture was poured into ice water and extracted with toluene. The obtained organic layer was washed with water and then extracted with a 20% aqueous solution of NaOH. The aqueous layer was acidified by adding concentrated sulfuric acid little by little while cooling with ice and extracted with ethyl acetate. The obtained organic layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain 55.5 g of the desired product (melting point 236 to 240 ° C). NMR data (60 MHz, CDCl ₃ solvent, δ value: p
pm) 4.10 (3H, s) 7.00 to 7.90 (7H, m) 10.85 (1H, s) The insecticide and acaricide of the present invention is a triazole derivative represented by the general formula [I]. As an active ingredient.

When the compound of the present invention is used as an insecticidal or acaricidal agent, the compound of the present invention may be used as it is, but a carrier, a surfactant, a dispersant, an auxiliary agent or the like which is generally used for formulation may be used. It is also possible to mix them and formulate into powders, wettable powders, emulsions, fine granules or granules and the like for use. As the carrier used in the formulation, Sieglite, talc, bentonite, clay, kaolin, diatomaceous earth, white carbon, vermiculite, slaked lime, silica sand, ammonium sulfate,
Examples thereof include solid carriers such as urea and liquid carriers such as isopropyl alcohol, xylene, cyclohexanone and methylnaphthalene. 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 foliar application, 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 the environmental conditions, the dosage form used, etc., when used as it is for powders and granules, it is selected as appropriate from the range of 0.05 g to 5 kg, preferably 0.1 g to 1 kg per 10 are as an active ingredient. Is good. Also,
When it is used in a liquid state such as an emulsion and a wettable powder, it is 0.1 to 5,000 ppm, preferably 1 to 1,
It is preferable to appropriately select from the range of 000 ppm.

The insecticidal and acaricidal agents of the present invention are other insecticides,
A fungicide, a fertilizer, and a plant growth regulator can also be mixed and used.

Next, the formulation method will be specifically described with reference to typical formulation examples. The kinds 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 No. (111) 30%, cyclohexanone 20
%, Polyoxyethylene alkyl aryl ether 11
%, Calcium alkylbenzene sulfonate 4% and methylnaphthalene 35% were uniformly dissolved to obtain an emulsion.

Formulation Example 2 Wettable powder Compound No. (67) 40%, diatomaceous earth 15%, clay 15
%, White carbon 25%, sodium dinaphthylmethanedisulfonate 2% and sodium ligninsulfonate 3% were uniformly mixed and pulverized to obtain a wettable powder.

Formulation Example 3 Dust Compound No. (43) 2%, diatomaceous earth 5% and clay 93
% Were uniformly mixed and pulverized to obtain a powder.

Formulation Example 4 Granules Compound No. (335) 5%, lauryl alcohol sulfate sodium salt 2%, sodium lignin sulfonate 5%, carboxymethylcellulose 2% and clay 86% are uniformly mixed and ground. 20 parts by weight of water was added to 100 parts by weight of this mixture, and the mixture was kneaded, processed into granules of 14 to 32 mesh using an extrusion granulator, and then dried to obtain granules.

[0176]

INDUSTRIAL APPLICABILITY The triazole derivative of the present invention is a half-pest insect such as lepidopteran pests such as diamondback moth, white-spotted gall midge, corn borer, and white-spotted aphid, aphids such as cotton aphid, green peach aphid, aphid aphid, and whiteflies such as whitefly. Diptera pests such as house flies, house flies and mosquitoes, rice weevil,
It is effective for the control of Coleoptera insect pests such as Azuki bean weevils and urchin beetles, Orthoptera insect pests such as American cockroaches and German cockroaches, and spider mites such as Nami mites, Kanzawa mites and citrus mites. Especially, diamondback moth, white-spotted armyworm,
It shows an extremely excellent control effect against lepidopteran pests such as scabbard moth, Spodoptera litura, aphids such as cotton aphid, green peach aphid, aphid such as radish aphid, and 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. The comparative drugs a and b used are the compounds of [Example 1] and [Example 18] exemplified in the specification of JP-A-56-154464, and the comparative drug c is exemplified in RD278004 published technical report. [Compound No. 24]. These were formulated and used in the same manner as the compounds of the present invention.

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) -5- (2,4-dichlorophenyl) -1-methyl-1H-1, 2,4-triazole

Test Example 1 Diamondback moth insecticidal test A wettable powder prepared according to Formulation Example 2 was used as an active ingredient.
Diluted with water to a concentration of 0 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 2
It was placed in a constant temperature room at 5 ° C., and 6 days later, the number of dead insects was investigated and the mortality rate was calculated by the calculation formula of Equation 1. The mortality was evaluated according to the criteria shown in Table 27, and the results are shown in Table 28. The test is 2
I went on a cycle.

[0180]

[Equation 1]

[0181]

[Table 27]

[0182]

[Table 28]

Test Example 2 Insecticidal test of Spodoptera litura L., a wettable powder prepared according to Formulation Example 2 was used as an active ingredient.
Diluted with water to a concentration of 0 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. After that, it was placed in a constant temperature room at 25 ° C., and 6 days later, the number of dead insects was investigated and the mortality rate was calculated by the formula of number 1. The mortality was evaluated according to the criteria shown in Table 27, and the results are shown in Table 29.
The test was carried out in a two-series system.

[0184]

[Table 29] 3

Test Example 3 Insecticide test for Nicamoga 50 Wet powder prepared according to Formulation Example 2 was used as an active ingredient.
Diluted with water to a concentration of 0 ppm. Rice bud stock was soaked in the chemical solution and put in a vinyl chloride cup. Ten larvae of Nikameiga were released in it and the lid was closed. Then 25
The sample was placed in a constant temperature chamber at ℃, 6 days later, the number of dead insects was examined, and the dead insect rate was calculated by the formula of number 1. The mortality was evaluated according to the criteria shown in Table 27, and the results are shown in Table 30. The test was carried out in a two-series system.

[0186]

[Table 30]

Test Example 4 Cotton Aphid Insecticidal Test 10 Wet powder prepared according to Formulation Example 2 was used as an active ingredient.
Diluted with water to a concentration of 0 ppm. Soak the cucumber seedlings that had been inoculated with the cotton aphid nymphs in advance,
Air dried. The cucumber seedlings after the treatment were placed in a thermostatic chamber at 25 ° C., and the number of dead insects was examined 3 days later, the mortality rate was calculated using the formula of number 1, and the result was evaluated according to the criteria in Table 27.
It was shown to. The test was conducted in two consecutive cycles.

[0188]

[Table 31]

Test Example 5 Acaricidal Acaricidal Test 50 A wettable powder prepared according to Formulation Example 2 was used as an active ingredient.
Diluted with water to a concentration of 0 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., and after 14 days, the number of surviving insects was examined, and the control value was calculated by the mathematical formula of Equation 2. The control value was evaluated according to the criteria in Table 27, and the results are shown in Table 32. The test was conducted in two consecutive cycles.

[0190]

[Equation 2]

[0191]

[Table 32]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C07D 401/12 249 403/12 239 (72) Inventor Junko Suzuki Shiinata, Fukuda-cho, Iwata-gun, Shizuoka 1 at 408 Kei Research Institute, Inc. (72) Masao Nakatani, Masao Nakatani, Shiota, Fukuda-cho, Iwata-gun, Shizuoka Prefecture 1 at Ka Research Institute, Inc. (72) Nobuo Takefuji Iwata-gun, Shizuoka Prefecture 408 Shioshinda, Fukuda-cho 1 KA Institute Inc. (72) Inventor Yuyuki Yano 1809 Kamo, Kikugawa-cho, Ogasa-gun, Shizuoka Prefecture 72 Inventor Saegusa Asaoka 1809 Kamo, Kikugawa-cho, Ogasa-gun, Shizuoka Prefecture (72) ) Inventor Hiroshi Kurihara 1-6-4 Aobadai, Kikugawa-cho, Ogasa-gun, Shizuoka Prefecture (72) Tadami Hirano 3-9 Katsugaoka, Kakegawa-shi, Shizuoka Prefecture 2

Claims (2)

[Claims] 1. A general formula: {In the formula, R ¹ represents an alkyl group, X is a halogen atom,
It represents an alkyl group, an alkoxy group, an alkylthio group, a nitro group, a cyano group or a haloalkyl group, n is 0 or an integer of 1 to 5, and when n is 2 or more, X may be the same or different combination. Y is a halogen atom, a nitro group, a cyano group, an alkyl group, an alkoxy group,
It represents an alkylthio group, a haloalkyl group or a haloalkoxy group, m represents 0 or an integer of 1 to 4, and when m is 2 or more, Y may be the same or different combination. A is the formula (In the formula, R ³ represents a hydrogen atom, an alkyl group or a cycloalkyl group, and j and k each represent an integer of 0 or 1.). R ² is a hydrogen atom, an alkyl group or a compound of the formula (In the formula, Q and Q ′ represent a methine group or a nitrogen atom, and R ⁴ represents a halogen atom, a nitro group, a cyano group, an alkyl group, an alkoxy group, an alkylthio group, an alkylsulfinyl group, an alkylsulfonyl group, a haloalkyl group, a halo group. It represents an alkoxy group, a haloalkylthio group, a haloalkylsulfinyl group, a haloalkylsulfonyl group, an alkylamino group or a dialkylamino group, p represents an integer of 0 or 1 to 3, and when p is 2 or more, R ⁴ is the same or different. It may be a heterogeneous combination). } The triazole derivative represented by these. 2. An insecticide and acaricide containing the triazole derivative according to claim 1 as an active ingredient.