JP2003277362A - Pyrazolecarboxamide, intermediate of the same and pest- controlling agent with the same as active ingredient - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a compound having high bactericidal activity on various pathogenic bacteria and having high insecticidal/miticidal activity, thus useful for controlling pests, and to provide a pest-controlling agent comprising the compound as an active ingredient. <P>SOLUTION: The compound is a pyrazolecarboxamide of general formula (I) (wherein, R<SP>1</SP>is a 1-5C alkyl; R<SP>2</SP>is a 1-5C alkyl, 1-5C haloalkyl or 1-5C alkoxy; R<SP>3</SP>is H or a 1-3C alkyl; R<SP>4</SP>is a 1-5C alkyl, 1-5C haloalkyl or halogen atom; R<SP>5</SP>is an alkyl, haloalkyl, alkoxy, haloalkoxy or the like; m is an integer of 0-4; n is an integer of 1-5; p is 0 or 1; and X is H, a 1-3C alkyl, 1-3C alkoxy or halogen atom). Acid addition salts of the compound, and the pest-controlling agent with the compound as the active ingredient are also provided, respectively. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to novel pyrazole carboxamides and pest control agents containing these as active ingredients. The novel pyrazole carboxamides of the present invention are useful as agricultural and horticultural fungicides, insecticides and acaricides.

[0002]

2. Description of the Related Art In the field of agriculture and horticulture, various fungicides, insecticides and acaricides have been developed and put into practical use for the purpose of controlling various pests. However, conventional pesticides that have been generally used cannot be said to satisfy the requirements of efficacy, spectrum, residual effect, etc., or reduction in the number of times of application and the amount of application.

In addition, the appearance of pests that have acquired resistance to conventional pesticides has also been a problem. For example, in the cultivation of vegetables, fruit trees, flowers, tea, wheat, rice, etc., for example, resistance to various types of insecticides such as carbamate, pyrethroid, benzoylurea, organochlorine, organophosphorus, etc. Various pests acquired and various pathogens that have acquired resistance to various types of fungicides such as triazole, imidazole, pyrimidine, benzimidazole, dicarboximide, phenylamide, etc. It has become difficult to control various pests caused by these resistant pests every year.

[0004] A new pesticide that exhibits a sufficient control effect with a low dose even against various pathogenic bacteria and pests that have acquired resistance to conventional general-purpose agricultural and horticultural insecticides and fungicides, and has little adverse effect on the environment. Appearance is always desired. It has been found by the present inventors that the N-benzylpyrazole-5-carboxamide derivative has insecticidal and acaricidal activity (see, for example, Patent Document 1). The patent document discloses the following compounds having insecticidal and acaricidal activity.

[0005]

[Chemical 5] Further, it is known that the following compounds having a phenoxy group exhibit insecticidal and acaricidal activity (for example, refer to Patent Document 2).

[0006]

[Chemical 6]

On the other hand, it has a structure similar to that of the compound of the present invention.
As the N-pyridylmethylpyrazole-5-carboxamide derivative, a compound in which the substituent corresponding to R ⁵ of the compound of the present invention represented by the following general formula (I) according to the invention of the present inventors is an alkyl group is an insecticide. , Acaricide, epidemics, and downy mildew bacteria are disclosed (see, for example, Patent Document 3). (See the following structural formula (III), Compound No. 34 in the patent document.)

[0008]

[Chemical 7] And compounds having both bactericidal activity and insecticidal and acaricidal activity are very important in agricultural and horticultural applications.

[0009]

[Patent Document 1] Japanese Patent Laid-Open No. 64-25763

[Patent Document 2] Japanese Patent Laid-Open No. 3-81266

[Patent Document 3] Japanese Patent Application Laid-Open No. 2-62876

[0010]

An object of the present invention is to provide a new substance which exhibits a high control effect against various pathogenic bacteria and is effective in controlling pests such as insects and mites, In particular, it provides a highly safe substance that exhibits a high control effect against various insect pests that are resistant to conventional insecticides, is effective even at low doses, and has reduced problems such as residual toxicity and environmental pollution. To do.

[0011]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that novel pyrazole carboxamides having a phenylpyridine skeleton and having a certain combination of substituents are The inventors have found that they have excellent bactericidal, insecticidal, and acaricidal activities that satisfy the above requirements, and completed the present invention. That is, the gist of the present invention is the following general formula (I)

[0012]

[Chemical 8]

(Wherein R ¹ represents a C _{1 to} C ₅ alkyl group, R ² represents a C _{1 to} C ₅ alkyl group, a C _{1 to} C ₅ haloalkyl group, or a C _{1 to} C ₅ alkoxy group. R ³ represents a hydrogen atom or a C _{1 to} C ₃ alkyl group, and R ⁴ represents C ₁ to C ₃ .
C ₅ alkyl group, C ₁ -C ₅ haloalkyl group or halogen atom is shown, and R ⁵ is alkyl group, haloalkyl group, alkoxy group, alkoxyalkoxy group, haloalkoxy group, hydroxyl group, acyloxy group, halopropenyloxy group. , An alkylthio group, a formyl group,

[Chemical 9] (Wherein R ⁶ and R ⁷ represent a hydrogen atom or a C ₁ -C ₅ alkyl group) or two adjacent R ⁵ are joined together.

[Chemical 10] (Provided that when n is 1, R ⁵ is not an alkyl group). m is an integer of 0 to 4, n is 1
Represents an integer of 5 and p represents 0 or 1. X represents a hydrogen atom, C ₁ -C ₃ alkyl group, a C ₁ -C ₃ alkoxy group or a halogen atom. ) Pyrazolecarboxamides and acid addition salts thereof represented by the following general formula, which is a pest control agent containing the pyrazolecarboxamides and / or acid addition salts thereof as an active ingredient and an intermediate thereof
(II)

[0014]

[Chemical 11] (In the formula, R ³ , R ⁴ and m are as defined in the general formula (I), and R ⁸ represents a haloalkoxy group.)
Phenylpyridylmethylamines represented by and their acid addition salts.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
In the pyrazolecarboxamides of the present invention represented by the general formula (I), the substituent R ¹ is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-
Butyl group, isobutyl group, tert-butyl group, n-pentyl group, 2-methylbutyl group, 3-methylbutyl group, isopentyl group, 2-ethylpropyl group, neopentyl group, 2,2-dimethylpropyl group, 2-methylisobutyl group a linear or branched alkyl group of C ₁ -C ₅ group, or the like. Of these, a methyl group is preferred as the substituent R ¹ .

The substituent R ² is methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, n-pentyl group, 2-
Methylbutyl group, 3-methylbutyl group, isopentyl group,
2-ethylpropyl group, neopentyl group, 2,2-dimethylpropyl group, 2-linear C ₁ -C _5, such as methyl isobutyl group or a branched chain alkyl group; fluoromethyl group, chloromethyl group, bromomethyl group, difluoromethyl Methyl group, difluoroethyl group, trifluoromethyl group, trichloromethyl group, tribromomethyl group, 2-fluoroethyl group, 2,2,2-
Trifluoroethyl group, 1- (trifluoromethyl) ethyl group, 1,1,2,3,3,3-hexafluoropropyl group, 2,2,3,
3,3-pentafluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 2,2,3,3,4,4,4-heptafluorobutyl group, 2,2,3,3,4 C such as 4,4,5,5,5-nonafluoropentyl group
_{1 to} C ₅ linear or branched haloalkyl group; methoxy group, ethoxy group, n-propoxy group, isopropoxy group,
n-butoxy group, sec-butoxy group, isobutoxy group, tert
-Butoxy group, n-pentoxy group, 2-methylbutoxy group, 3
- showing methylbutoxy, isopentoxy, 2-ethyl-propoxy group, neopentoxy group, 2,2-dimethyl-propoxy group, a straight-chain or branched-chain alkoxy group of C ₁ -C _5, such as 2-methyl-isobutoxy group. Among them, the substituent R ² is preferably a C _{1 to} C ₃ linear alkyl group, and particularly preferably a methyl group or an ethyl group.

The substituent R ³ represents a hydrogen atom; a C ₁ -C ₃ linear or branched alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group or the like. Of these, the substituent R
³ is preferably a hydrogen atom. The substituent R ⁴ is methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, n
-Pentyl group, 2-methylbutyl group, 3-methylbutyl group,
C ₁ -C ₅ linear or branched alkyl groups such as isopentyl group, 2-ethylpropyl group, neopentyl group, 2,2-dimethylpropyl group, 2-methylisobutyl group; fluoromethyl group, chloromethyl group, bromomethyl Group, difluoromethyl group, difluoroethyl group, trifluoromethyl group, trichloromethyl group, tribromomethyl group, 2-fluoroethyl group, 2,2,2-trifluoroethyl group, 1- (trifluoromethyl) ethyl group , 1,1,2,3,3,3-hexafluoropropyl group, 2,2,3,3,3-pentafluoropropyl group,
2,2,3,3-tetrafluoropropyl group, 2,2,3,3,4,4,4-heptafluorobutyl group, 2,2,3,3,4,4,5,5,5- A C ₁ -C ₅ straight or branched chain haloalkyl group such as a nonafluoropentyl group; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom is shown. Of these, a hydrogen atom is preferable as the substituent R ⁴ .

The substituent R ⁵ is a methyl group, an ethyl group or n-
Propyl group, isopropyl group, n-butyl group, sec-
Butyl group, isobutyl group, tert-butyl group, n-pentyl group, 2-methylbutyl group, 3-methylbutyl group,
Isopentyl group, 2-ethylpropyl group, neopentyl group, 2,2-dimethylpropyl group, 2-methyl-straight or branched alkyl group C ₁ -C _5, such as isobutyl group, fluoromethyl group, chloromethyl group, bromomethyl Group, difluoromethyl group, difluoroethyl group, trifluoromethyl group, trichloromethyl group, tribromomethyl group, 2-
Fluoroethyl group, 2,2,2-trifluoroethyl group, 1-
(Trifluoromethyl) ethyl group, 1,2,3,3,3-hexafluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 2,2,3,3-tetrafluoropropyl group Base, 2,2,3,3,4,4,
4-heptafluorobutyl group, linear or branched haloalkyl group such as 2,2,3,3,4,4,5,5,5-nonafluoropentyl group; methoxy group, ethoxy group, n-propoxy group, Isopropoxy group, n-butoxy group, sec-butoxy group, isobutoxy group, tert-butoxy group, n-pentoxy group, 2-methylbutoxy group, 3-methylbutoxy group, isopentoxy group,
2-Ethylpropoxy group, neopentoxy group, 2,2-dimethylpropoxy group, 2-methylisobutoxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group and other straight or branched chain alkoxy groups A linear or branched alkoxyalkoxy group such as methoxymethoxy group or 2-ethoxyethoxy group; difluoromethoxy group, trifluoromethoxy group, fluoromethoxy group, trichloromethoxy group, tribromomethoxy group, 2-fluoroethoxy group, 2 1,2,2-trifluoroethoxy group, 2,2,2-trichloroethoxy group, 1- (trifluoromethyl) ethoxy group, 1,
1,2,3,3,3-hexafluoropropoxy group, 2,2,3,3,3-pentafluoropropoxy group, 2,2,3,3-tetrafluoropropoxy group, 2,2,3,3 Linear or branched haloalkoxy group such as 4,4,4,4-heptafluorobutoxy group; hydroxyl group: acyloxy group such as acetyloxy group, propionyloxy group, n-butyryloxy group, i-butynyloxy group, pivaloyloxy group; Fluoropropenyloxy group, chloropropenyloxy group, difluoropropenyloxy group, dichloropropenyloxy group and other halopropenyloxy groups; methylthio group, ethylthio group, propylthio group, isopropylthio group, butylthio group, sec-
Butylthio group, isobutylthio group, tert-butylthio group, pentylthio group, 2-methylbutylthio group, 3-
Linear or branched alkylthio groups such as methylbutylthio group, isopentylthio group, 2-ethylpropylthio group, neopentylthio group, 2,2-dimethylpropylthio group, 2-methylisobutylthio group; formyl group;

[0019]

[Chemical 12]

A group represented by the formula (wherein R ⁶ and R ⁷ are hydrogen atoms; or a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, tert-butyl group, n-pentyl group, 2-methylbutyl group, 3-methylbutyl group, isopentyl group, 2-ethylpropyl group, neopentyl group,
2,2-dimethylpropyl group, a straight or branched chain alkyl group of C ₁ -C _5, such as 2-methyl isobutyl group. ); Also, two adjacent R ⁵ are joined together

[0021]

[Chemical 13]

A group represented by The alkyl group, haloalkyl group, alkoxy group, haloalkoxy group and alkylthio group are preferably C _{1 to} C ₈ ,
As the alkoxyalkoxy group and the acyloxy group, those having C _{2 to} C ₈ are preferable. Of these, the substituent R ⁵
Is preferably a C _{1 to} C ₅ haloalkyl group or a C _{1 to} C ₅ haloalkoxy group, and particularly preferably a trifluoromethoxy group or a difluoromethoxy group. The substitution position is preferably 4-position.

The substituent X is a hydrogen atom; a C ₁ -C ₃ linear or branched alkyl group such as a methyl group, an ethyl group, an n-propyl group or an isopropyl group; a methoxy group, an ethoxy group, n-
A C _{1 to} C ₃ linear or branched alkoxy group such as a propoxy group or an isopropoxy group; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom is shown. this house,
As the substituent X, a hydrogen atom is preferable.

M is an integer of 0-4, of which 0-2
Is preferable, n is an integer of 1 to 5, preferably 1 or 2, and p is 0 or 1, and preferably 0. Examples of the acid added to the pyrazolecarboxamides of the present invention represented by the general formula (I) include acetic acid, propionic acid, butyric acid, oxalic acid, adipic acid, dodecanedioic acid, lauric acid, stearic acid, trifluoroacetic acid, Carboxylic acids such as fumaric acid, maleic acid, benzoic acid, and phthalic acid; sulfonic acids such as methanesulfonic acid, 1,3-propanedisulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid; hydrochloric acid, sulfuric acid, nitric acid, carbonic acid And other inorganic acids. The phenylpyridylmethylamines of the present invention represented by the general formula (II) and acid addition salts thereof are novel intermediates for producing the pyrazole carboxamides and acid addition salts thereof.

The acid to be added to the phenylpyridylmethylamines of the present invention represented by the general formula (II) is:
Carboxylic acids such as acetic acid, propionic acid, butyric acid, oxalic acid, adipic acid, dodecanedioic acid, lauric acid, stearic acid, trifluoroacetic acid, fumaric acid, maleic acid, benzoic acid and phthalic acid; methanesulfonic acid, 1,3 -Sulfonic acids such as propanedisulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid; hydrochloric acid, sulfuric acid, nitric acid,
Indicates an inorganic acid such as carbonic acid.

The compound of the present invention represented by the above general formula (I) is a novel compound and can be produced, for example, according to the following reaction formula. (1) Reaction of carboxylic acid chloride with phenylpyridylmethylamines

[0027]

[Chemical 14]

(In the above formulas (IV) and (V), R ¹ , R ² and R
³ , R ⁴ , R ⁵ , X, m and n are as defined in the above general formula (I). ) That is, carboxylic acid chlorides (IV) and phenylpyridylmethylamines (V) are added in the presence or absence of a base, preferably in a solvent, at -10 to 50 ° C, preferably 0 to 25 ° C.
React at ℃.

The solvent is not particularly limited as long as it does not directly participate in this reaction, and examples thereof include aromatic hydrocarbons such as benzene, toluene and xylene; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; chloroform and dichloromethane. Halogenated hydrocarbons such as; water; esters such as methyl acetate, ethyl acetate; or tetrahydrofuran, acetonitrile, dioxane,
Examples thereof include polar solvents such as N, N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide and pyridine.

Examples of the base include alkali metal hydrides such as sodium hydride; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; inorganic salts; pyridine, Examples thereof include amines such as triethylamine. After the reaction, in order to isolate the target compound of the general formula (I), when a solvent soluble in water is used, the solvent is distilled off under reduced pressure, water is added, and then the compound is insoluble in water. Aromatic hydrocarbons such as benzene, toluene and xylene; Halogenated hydrocarbons such as chloroform and dichloromethane; Extract with esters such as ethyl acetate, wash with saturated saline, and then dry agents such as anhydrous sodium sulfate and anhydrous magnesium sulfate Dried in
The solvent may be distilled off under reduced pressure. When a solvent insoluble in water is used, water is added to the reaction mixture and then the organic layer is separated, washed with a saturated saline solution, and then dried with a desiccant such as anhydrous sodium sulfate and anhydrous magnesium sulfate, and the mixture is decompressed. The solvent may be distilled off with. The residue obtained after evaporation of the solvent is purified by recrystallization, suspension washing, column chromatography or the like to obtain the target compound of the general formula (I). (2) Synthesis using Suzuki coupling

[0031]

[Chemical 15]

(In the above formulas (VI) and (VII), R ¹ , R ² ,
R ³ , R ⁴ , R ⁵ , X, m and n are as defined in the above general formula (I). W represents a leaving group. ) That is, carboxamides (VI) and phenylboronic acids (VI)
I) in the presence or absence of a base and a transition metal catalyst, preferably using a solvent, at 0 to 150 ° C., preferably room temperature to 1
React at 20 ° C.

The solvent is not particularly limited as long as it does not directly participate in the reaction, and examples thereof include alcohols such as methanol, ethanol and isopropanol; benzene,
Aromatic hydrocarbons such as toluene and xylene; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; halogenated hydrocarbons such as chloroform and dichloromethane; water; esters such as methyl acetate and ethyl acetate;
Or tetrahydrofuran, acetonitrile, dioxane, N, N-dimethylformamide, N-methylpyrrolidone,
Examples thereof include polar solvents such as dimethyl sulfoxide and pyridine.

Examples of the leaving group include chlorine atom, bromine atom, iodine atom, methylsulfonyloxy group, p-toluenesulfonyloxy group and trifluoromethylsulfonyloxy group. Examples of the base include alkali metal hydrides such as sodium hydride; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; inorganic salts; pyridine, triethylamine and the like. Examples thereof include amines.

As the transition metal catalyst, palladium acetate, dichlorobis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium and palladium compounds such as tris (dibenzylacetone) palladium, bis (triphenylphosphine) nickel chloride and Examples thereof include nickel compounds such as tetrakis (triphenylphosphine) nickel.

After the reaction, in order to isolate the desired compound of the general formula (I), when a solvent soluble in water is used, the solvent is distilled off under reduced pressure, water is added, and then water is added. Insoluble in benzene, toluene, xylene and other aromatic hydrocarbons; chloroform, dichloromethane and other halogenated hydrocarbons; extracted with ethyl acetate and other esters and washed with saturated saline, and then anhydrous sodium sulfate, anhydrous magnesium sulfate, etc. It may be dried with the above desiccant and the solvent may be distilled off under reduced pressure. When a solvent insoluble in water is used, water is added to the reaction mixture and then liquid separation is performed,
The organic layer may be washed with saturated saline and then dried with a desiccant such as anhydrous sodium sulfate or anhydrous magnesium sulfate, and the solvent may be distilled off under reduced pressure. The residue obtained after evaporation of the solvent is purified by recrystallization, suspension washing, column chromatography and the like to obtain the desired compound of the general formula (I).

The compound represented by the general formula (IV) as a raw material is
For example, it can be synthesized by the method described in JP-A-64-25763. Furthermore, the acid addition salt of the pyrazole carboxamides of the present invention can be produced by the following method.

[0038]

[Chemical 16]

(In the formula (I '), R ¹ , R ² , R ³ , R ⁴ ,
R ⁵ , m and n are as defined in general formula (I), and Y is an acid. ) The pyrazole carboxamides (I) and the acid are reacted preferably at -5 to 50 ° C, preferably 0 to 25 ° C using a solvent. As the acid, an organic acid or an inorganic acid can be used, and as the organic acid, acetic acid, propionic acid, butyric acid, oxalic acid, adipic acid, dodecanedioic acid, lauric acid, stearic acid, trifluoroacetic acid, fumaric acid, maleic acid. Carboxylic acids such as benzoic acid and phthalic acid; sulfonic acids such as methanesulfonic acid, 1,3-propanedisulfonic acid, p-toluenesulfonic acid and dodecylbenzenesulfonic acid. As the inorganic acid, hydrochloric acid, sulfuric acid,
Examples thereof include nitric acid and carbonic acid.

The solvent is not particularly limited as long as it does not directly participate in this reaction, and examples thereof include aromatic hydrocarbons such as benzene, toluene and xylene; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; chloroform and dichloromethane. Halogenated hydrocarbons such as; water; esters such as ethyl acetate and methyl acetate; or tetrahydrofuran, acetonitrile, dioxane,
Examples thereof include polar solvents such as N, N-dimethylformamide, N-methylpyrrolidone and dimethyl sulfoxide. After the reaction, the solvent is distilled off under reduced pressure, and the crystals are filtered to synthesize benzylamine inorganic acid salt and organic acid salt. Although it is sufficient as it is, if it is desired to further purify it, a high-purity pyrazolecarboxamic acid addition salt can be synthesized by washing with the organic solvent mentioned above. The compound represented by the general formula (V) as a raw material can be synthesized by the following method. (1) Catalytic hydrogen reduction of phenylcyanopyridines

[0041]

[Chemical 17]

(In the above formulas (VIII) and (Va), R ⁴ , R ⁵ , m
And n are as defined in the general formula (I). ) Phenyl cyanopyridines (VIII) and hydrogen in the presence of a metal catalyst and aqueous ammonia, preferably using a solvent, 0 to 100
The reaction is carried out at ℃, preferably 25 to 50 ℃. The solvent is not particularly limited as long as it does not directly participate in this reaction, and examples thereof include alcohols such as methanol, ethanol and isopropanol; aromatic hydrocarbons such as benzene, toluene and xylene; acetone, methyl ethyl ketone, methyl isobutyl ketone and the like. Ketones; halogenated hydrocarbons such as chloroform and dichloromethane; water; esters such as methyl acetate and ethyl acetate; or tetrahydrofuran, acetonitrile, dioxane, N, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, pyridine And other polar solvents.

Examples of the metal catalyst include Raney nickel, palladium carbon, platinum oxide and the like. After the reaction, in order to isolate the target compound of the general formula (Va), the metal catalyst may be filtered off from the reaction mixture, and then the solvent may be distilled off under reduced pressure to obtain the target general formula (Va). A compound represented by It may be a pure product as it is, but if necessary, a pure product can be obtained by purification by means of distillation, column chromatography or the like. (2) Reduction of phenylcyanopyridines with metal hydrogen compounds

[0044]

[Chemical 18]

The phenylcyanopyridines (VIII) are reacted with the metal hydrogen compound preferably in a solvent at -78 to 150 ° C, preferably -78 to 100 ° C. The solvent is not particularly limited as long as it does not directly participate in this reaction, and examples thereof include aromatic hydrocarbons such as benzene, toluene and xylene; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; halogens such as chloroform and dichloromethane. And hydrocarbons; esters such as methyl acetate and ethyl acetate; and polar solvents such as tetrahydrofuran, acetonitrile, dioxane, N, N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide and pyridine.

Examples of the metal hydrogen compound include sodium borohydride, lithium aluminum hydride and the like. After the reaction, the target compound of general formula (Va)
In order to isolate the compound (1), the residual metal hydrogen compound is post-treated and then the solvent is distilled off under reduced pressure to obtain the target compound of the general formula (Va). It may be a pure product as it is, but if necessary, a pure product can be obtained by purification by means of distillation, column chromatography or the like. (3) Reduction of oximes

[0047]

[Chemical 19]

(In the above formula (IX), R ³ , R ⁴ , R ⁵ , m and n are as defined in the above general formula (I).) The oxime (IX) and hydrogen are used as a metal catalyst and ammonia. In the presence of water, preferably using a solvent, 0 to 100 ° C, preferably 2
React at 5-50 ° C. The solvent is not particularly limited as long as it does not directly participate in this reaction, and examples thereof include alcohols such as methanol, ethanol and isopropanol;
Aromatic hydrocarbons such as benzene, toluene, xylene; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone; halogenated hydrocarbons such as chloroform, dichloromethane; water; esters such as methyl acetate, ethyl acetate; or tetrahydrofuran, Examples thereof include polar solvents such as acetonitrile, dioxane, N, N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide and pyridine. Examples of the metal catalyst include Raney nickel, palladium carbon, platinum oxide and the like. After the reaction, the general formula of the target
In order to isolate the compound of (V), the metal catalyst is filtered off from the reaction mixture, and then the solvent is distilled off under reduced pressure to obtain the desired compound of the general formula (V).

The phenylcyanopyridines (VIII) can be prepared by known methods, for example, Synthetic Communications, Vol. 11, p. 513 (19
By the method described in 81), it can be synthesized by reacting the corresponding haloarene and phenylboronic acid in the presence of a transition metal catalyst and a base. The oximes (IX) can be synthesized by reacting the corresponding acetophenones with hydroxylamines in the presence of potassium carbonate by a known method. The phenylpyridylmethylamine acid addition salt (X) can be synthesized by the following method.

[0050]

[Chemical 20]

(In the above formula, R ³ , R ⁴ , R ⁵ , m and n are as defined in the above general formula (I), and Y is an acid.) Phenylpyridylmethylamines (V) The acid is reacted, preferably with a solvent, at -5 to 50 ° C, preferably 0 to 25 ° C. As the acid, an organic acid or an inorganic acid can be used,
Organic acids include acetic acid, propionic acid, butyric acid, oxalic acid,
Carboxylic acids such as adipic acid, dodecanedioic acid, lauric acid, stearic acid, trifluoroacetic acid, fumaric acid, maleic acid, benzoic acid and phthalic acid; methanesulfonic acid,
Examples thereof include sulfonic acids such as 1,3-propanedisulfonic acid, p-toluenesulfonic acid and dodecylbenzenesulfonic acid. Examples of the inorganic acid include hydrochloric acid, sulfuric acid, nitric acid, carbonic acid and the like.

The solvent is not particularly limited as long as it does not directly participate in this reaction, and examples thereof include aromatic hydrocarbons such as benzene, toluene and xylene; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; chloroform and dichloromethane. Halogenated hydrocarbons such as; water; esters such as ethyl acetate and methyl acetate; or tetrahydrofuran, acetonitrile, dioxane,
Examples thereof include polar solvents such as N, N-dimethylformamide, N-methylpyrrolidone and dimethyl sulfoxide.

After the reaction, the solvent is distilled off under reduced pressure and the crystals are filtered to synthesize benzylamine inorganic acid salt and organic acid salt. Although it is sufficient as it is, if further purification is desired, a highly pure pyridylmethylamine acid adduct (X) can be synthesized by washing with the organic solvent mentioned above. The compound represented by the general formula (VI) as a raw material can be synthesized by the following method.

[0054]

[Chemical 21]

(In the above formula (XI), R ³ , R ⁴ , X, m and
W is as defined in the above general formulas (I) and (VI). ) That is, carboxylic acid chlorides (IV) and pyridylmethylamines (XI) are reacted in the presence or absence of a base, preferably with a solvent, at -10 to 50 ° C, preferably 0 to 25 ° C. Let

The solvent is not particularly limited as long as it does not directly participate in this reaction, and examples thereof include aromatic hydrocarbons such as benzene, toluene and xylene; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; chloroform and dichloromethane. Halogenated hydrocarbons such as; water; esters such as methyl acetate, ethyl acetate; or tetrahydrofuran, acetonitrile, dioxane,
Examples thereof include polar solvents such as N, N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide and pyridine.

Examples of the base include alkali metal hydrides such as sodium hydride; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; inorganic salts; pyridine, Examples thereof include amines such as triethylamine. After the reaction, in order to isolate the target compound of the general formula (VI), when a solvent that dissolves in water is used, the solvent is distilled off under reduced pressure, water is added, and then the compound is insoluble in water. Aromatic hydrocarbons such as benzene, toluene and xylene; Halogenated hydrocarbons such as chloroform and dichloromethane; Extract with esters such as ethyl acetate, wash with saturated saline, and then dry agents such as anhydrous sodium sulfate and anhydrous magnesium sulfate Dried in
The solvent may be distilled off under reduced pressure. When a solvent insoluble in water is used, water is added to the reaction mixture and then the organic layer is separated, washed with a saturated saline solution, and then dried with a desiccant such as anhydrous sodium sulfate and anhydrous magnesium sulfate, and the mixture is decompressed. The solvent may be distilled off with. The residue obtained after evaporation of the solvent is purified by recrystallization, suspension washing, column chromatography and the like to obtain the target compound of the general formula (VI). Compound
(XI) can be synthesized by the method described in JP-A-2-62876.

The compound of the present invention represented by the general formula (I) has a high bactericidal effect against plant pathogenic fungi such as blast fungus, powdery mildew, rust fungus and downy mildew, and is a fungicide for agricultural and horticultural use. It is useful as an active ingredient of. Further, the compound of the present invention is a planthopper such as a sedge brown planthopper, a brown planthopper, a brown leafhopper, a leafhopper such as a leafhopper, a leafhopper such as a leafhopper, an aphid such as a green peach aphid; ; Coleoptera such as azuki bean weevils;
Diptera such as housefly, Aedes aegypti and Culex pipiens; insecticides for agricultural and horticultural use, as they have high control activity against insects of the order Orthoptera and eggs and larvae of the order of the mites such as Nymphalid mite, Nicaria spp. It is also useful as an active ingredient of agents and acaricides. However, the phytopathogenic fungi, insects and mites to be controlled by the compound of the present invention are not limited to those exemplified above.

When the compound of the present invention represented by the general formula (I) is used as a fungicide, insecticide, and / or acaricide for agricultural and horticultural use, it may be used alone, but preferably in the art. The agricultural and horticultural fungicide in the form of a composition produced by using a pesticide adjuvant commonly used in, the insecticide, and / or the form of acaricide is not particularly limited, for example, emulsion, wettable powder,
It is preferable to use powders, flowables, fine granules, granules, tablets, oils, sprays, fumes and the like. One or more of the above compounds can be blended as an active ingredient.

The above-mentioned agricultural and horticultural fungicides, insecticides, and / or
Or the agricultural chemical auxiliary agent used for producing an acaricide is used for the purpose of, for example, improving the effect of the fungicide for agricultural and horticultural use, an insecticide, and / or an acaricide, stabilizing, dispersibility, etc. You can do it. For example, carriers (diluents), spreading agents, emulsifiers, wetting agents, dispersing agents, disintegrating agents and the like can be used.

Examples of the liquid carrier include water, aromatic hydrocarbons such as toluene and xylene, alcohols such as methanol, butanol and glycol, ketones such as acetone, amides such as dimethylformamide, sulfoxides such as dimethylsulfoxide, and the like. Methylnaphthalene, cyclohexane, animal and vegetable oils, fatty acids, etc. can be mentioned. Also,
As a solid carrier, clay, kaolin, talc, diatomaceous earth,
Silica, calcium carbonate, montmorillonite, bentonite, feldspar, quartz, alumina, sawdust, nitrocellulose,
Starch, gum arabic, etc. can be used.

Usual surfactants can be used as the emulsifier and dispersant. For example, anionic surfactants such as higher alcohol sodium sulfate, stearyl trimethyl ammonium chloride, polyoxyethylene alkyl phenyl ether, and lauryl betaine. , Cationic surfactants, nonionic surfactants, zwitterionic surfactants and the like can be used. Further, spreading agents such as polyoxyethylene nonyl phenyl ether and polyoxyethylene lauryl phenyl ether; wetting agents such as dialkyl sulfosuccinate; carboxymethyl cellulose,
A fixing agent such as polyvinyl alcohol; a disintegrating agent such as sodium ligninsulfonate and sodium lauryl sulfate can be used.

Agricultural and horticultural fungicides, insecticides, and / or
Or the content of the active ingredient in the acaricide is 0.1 to 99.5
%, And may be appropriately determined according to various conditions such as formulation form and application method.
5 to 20% by weight, preferably 1 to 10% by weight, wettable powder about 1 to 90% by weight, preferably 10 to 80% by weight, emulsion about 1 to 90% by weight, preferably 10 to 40% by weight. It is suitable to produce so as to contain the active ingredient by weight.

For example, in the case of an emulsion, a stock solution emulsion can be prepared by mixing a solvent, a surfactant and the like with the above-mentioned compound as an active ingredient, and further diluting the stock solution with water to a predetermined concentration at the time of use. Can be applied. In the case of a wettable powder, the above-mentioned compound as an active ingredient, a solid carrier, a surfactant and the like may be mixed to prepare a stock solution, which may be diluted with water to a predetermined concentration before use. In the case of powders, the above-mentioned compound of the active ingredient, solid carrier and the like can be mixed and applied as it is. In the case of granules, the above-mentioned compound of active ingredient, solid carrier, surfactant and the like can be mixed to prepare. It can be manufactured by granulating and applied as it is. However, the method for producing each of the above-mentioned preparation forms is not limited to the above, and can be appropriately selected by those skilled in the art according to the type of active ingredient, the purpose of application and the like.

Agro-horticultural germicide, insecticide, and / or
Or the acaricide, in addition to the compound of the present invention is an active ingredient, other active ingredients such as other fungicides, insecticides, acaricides, herbicides, insect growth regulators, fertilizers, soil conditioners, etc. You may mix. Agricultural and horticultural fungicides of the present invention, insecticides, and / or
The application method of the acaricide is not particularly limited, and it can be applied by any method such as foliage spraying, water surface application, soil treatment and seed treatment. For example, in the case of spraying foliage, a solution having a concentration range of 5 to 1000 ppm, preferably 10 to 500 ppm can be used at an application rate of about 100 to 200 liters per 10 ares. When applied to water, the application rate is usually 1 to 10 per 10 are for granules containing 5 to 15% of active ingredient.
It is kg. In the case of soil treatment, a solution having a concentration range of 5 to 1000 ppm can be used at an application rate of about 1 to 10 liters per m ² . For seed treatment, 10 to 1 per 1 kg seed weight
A solution having a concentration range of 000 ppm can be applied to about 10 to 100 ml. Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not limited to the following Examples.

[0066]

EXAMPLES The present invention will be described in more detail with reference to Examples, Formulation Examples and Test Examples, but the present invention is not limited to these examples as long as the gist thereof is not exceeded. Example 1 Synthesis of 3-ethyl-1-methyl-N- [6- (4-trifluoromethoxyphenyl) -3-pyridylmethyl] pyrazole-5-carboxamide 6- (4-trifluoromethoxyphenyl) -3- After cooling a mixture of pyridylmethylamine (5.00 g), triethylamine (5 ml) and dichloromethane (50 ml) to 0-4 ° C, 1-methyl
A solution of 3-ethylpyrazole-5-carboxylic acid chloride (3.21 g) in toluene (20 ml) was added, and the mixture was stirred for 30 minutes. The reaction mixture was poured into water (50 ml) and extracted with ethyl acetate. The organic layer was washed with dilute hydrochloric acid and saturated saline and then dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, the residue was purified by silica gel column chromatography, and the compound shown in Table-1 was used.
6.32 g of No. 4 was obtained. The melting point was 120-121 ° C.

Example 2 Synthesis of 1,3-dimethyl-N- [6- (4-trifluoromethoxyphenyl) -2-pyridylmethyl] pyrazole-5-carboxamide N- (6-chloro-2- Pyridylmethyl) -1,3-dimethylpyrazole-5-carboxamide (9.00 g), 4-trifluoromethoxybenzeneboronic acid (10.5 g), toluene (10
0 ml), dioxane (50 ml), 2M sodium carbonate aqueous solution
A mixture of (50 ml) and water (25 ml) was heated to 70 ° C., tetrakistriphenylphosphine palladium (3.93 g) was added, and the mixture was stirred under heating reflux for 2 hours. Water (100 m
l) was added, and the mixture was extracted with ethyl acetate. The organic layer is sodium bicarbonate water,
The extract was washed with saturated saline and dried over anhydrous sodium sulfate.
The solvent was distilled off under reduced pressure, the residue was purified by silica gel column chromatography, and Compound No. 31 shown in Table 1 was added to 11.8.
g got. The melting point was 123-124 ° C.

Example 3 1,3-Dimethyl-N- [6-
Synthesis of (4-trifluoromethoxyphenyl) -2-pyridylmethyl] pyrazole-5-carboxamide hydrochloride 1,3-dimethyl-N- [6- (4-trifluoromethoxyphenyl) -2-pyridylmethyl] pyrazole- 5
-Carboxamide (0.5 g) in methanol (10 m
l) 12N hydrochloric acid (1 ml) was added to the solution, and the mixture was stirred at room temperature for 2 hours. The solvent was distilled off under reduced pressure, the crystals were washed with methanol, and the compound No. 0.35 g of 60 was obtained. The melting point was 208-209 ° C (decomposition). The compounds shown in Table-1 and Table-2 were synthesized according to the methods of Examples 1 to 3.

[0069]

[Table 1]

[0070]

[Table 2]

[0071]

[Table 3]

[0072]

[Table 4]

[0073]

[Table 5]

[0074]

[Table 6]

[0075]

[Table 7]

[0076]

[Table 8]

Example 4 Synthesis of 6- (4-trifluoromethoxyphenyl) -3-pyridylmethylamine Under a hydrogen atmosphere, 3-cyano-6- (4-trifluoromethoxyphenyl) pyridine (10 g) and Raney nickel R- 100 (10 g)
And a mixture of 28% aqueous ammonia (10 ml) were shaken at 50 ° C. for 3 hours. After cooling to room temperature, Raney nickel was filtered off and the solvent was distilled off under reduced pressure to obtain 9.73 g of Compound No. 65 shown in Table-3. Similarly, No. 68 was synthesized.

Example 5 Synthesis of 6- (4-trifluoromethoxyphenyl) -3-pyridylmethylamine hydrochloride 6- (4-trifluoromethoxyphenyl) -3-pyridylmethylamine (9.25 g) in methanol (50 12N hydrochloric acid (6 ml) was added to the solution), and the mixture was stirred at room temperature for 2 hours. The solvent was distilled off under reduced pressure, and the crystals were washed with methanol to give the compounds shown in Table-3.
9.35 g of No. 66 was obtained. The melting point was 120-125 ° C. The compounds shown in Table 3 were synthesized according to the methods of Examples 4 and 5.

[0079]

[Table 9]

1) ¹ H NMR (CDCl ₃ ) δppm: 3.96 (2H, s), 7.3
1 (2H, d), 7.69 (1H, d), 7.77 (1H, dd), 8.02 (2H, d), 8.63 (1H,
d) 2) ¹ HNMR (CDCl ₃ ) δppm: 4.05 (2H, s), 7.33 (2H, d), 7.38
(1H, d), 7.59 (2H, dd), 7.82 (1H, dd), 8.77 (1H, d) or less, agricultural and horticultural insecticide containing the compound of the present invention as an active ingredient, showing a formulation example of an acaricide However, the use form of the present invention is not limited to the following.

Formulation Example 1: Wettable powder 20 parts by weight of the compound of the present invention, 20 parts by weight of Carplex # 80 (white carbon, Shionogi Pharmaceutical Co., Ltd., trade name), ST Kaolin clay (kaolinite, Tsuchiya Kaolin Co., Ltd., Brand name) 52 parts by weight, Solpol 9047K (anionic surfactant, Toho Chemical Co., Ltd., product name) 5 parts by weight, Lunox P65L (anionic surfactant, Toho Chemical Co., Ltd., product name) 3 parts by weight Then, the mixture was uniformly mixed and pulverized to obtain a wettable powder containing 20% by weight of the active ingredient.

Formulation Example 2: Dust 2 parts by weight of the compound of the present invention, clay (manufactured by Nippon Talc) 9
3 parts by weight, Carplex # 80 (white carbon,
Shionogi Seiyaku Co., Ltd., 5 parts by weight) were uniformly mixed and pulverized to produce a powder formulation containing 2% by weight of the active ingredient. Formulation Example 3: Emulsion 20 parts by weight of the compound of the present invention is dissolved in a mixed solvent consisting of 35 parts by weight of xylene and 30 parts by weight of dimethylformamide, and Solpol 3005X (a mixture of a nonionic surfactant and an anionic surfactant is added thereto. , Toho Chemical Co., Ltd., product name) 15 parts by weight, 20% by weight of active ingredient
An emulsion of was obtained.

Formulation Example 4: Flowable Agent 30 parts by weight of the compound of the present invention and Solpol 9047K 5
Parts by weight, sorbon T-20 (nonionic surfactant, Toho Chemical Co., Ltd., trade name) 3 parts by weight, 8 parts by weight of ethylene glycol and 44 parts by weight of water are wet-milled with Dynomill (manufactured by Shinmaru Enterprises Co., Ltd.). Then, 10 parts by weight of a 1% by weight xanthan gum (natural polymer) aqueous solution was added to this slurry mixture, and the mixture was thoroughly mixed and ground to prepare an active ingredient 20.
A weight percent flowable agent was obtained. Hereinafter, test examples of agricultural and horticultural fungicides, insecticides and acaricides containing the compound of the present invention as an active ingredient will be shown, but the use form of the present invention is not limited to the following.

Test Example 1 Bactericidal effect against wheat powdery mildew The compound (III) disclosed in the above-mentioned JP-A-64-62876 and various compounds of the present invention are each prepared in Formulation Example 3
Dilute the formulation prepared in the same manner as above with water to the specified concentration,
Wheat (cultivar: 1-2 leaves) grown in a pot with a diameter of 6 cm
Norin 61), the foliage was sprayed at a rate of 10 ml per pot. After air-drying the chemical solution, the powdery mildew of wheat (Erysophe gr
After spray-inoculating a spore suspension obtained from a wheat leaf infected with aminis), it was left in a greenhouse for 7 to 10 days. For the evaluation, the diseased area ratio was evaluated for each type, and the control value was calculated from the following formula. The results are shown in Table 4 (in the following table, compound numbers correspond to Nos in Tables 1 and 2). As a comparative compound,
Compounds (II) in which R ⁵ in formula (I) is an alkyl group
I) was shown.

[0085]

[Equation 1]

[0086]

[Table 10]

[0087]

[Table 11]

Test Example 2 Bactericidal effect against wheat leaf rust A formulation prepared by adjusting each compound of the present invention in the same manner as in Formulation Example 3 was diluted with water to a predetermined concentration, and seedlings were grown in pots having a diameter of 6 cm. Wheat (variety: Norin 61) at the leaf stage was sprayed with foliage at a rate of 10 ml per pot. After air-drying the chemical solution, after spray inoculation with a spore suspension obtained by grinding wheat leaves infected with wheat leaf rust (Puccinia recondita),
After keeping it in a humid chamber at 22 ° C for 15 hours, it was left in a greenhouse bath for 7 days. In the evaluation, the affected area ratio was evaluated for each type, and the control value was calculated by the same method as in Test Example 1 above. The results are shown in Table-5 (in the table below, the compound numbers are shown in Table-1 and Table-2).
Corresponds to No).

[0089]

[Table 12]

Test Example 3 Insecticidal effect of Spodoptera litura, cabbage cut leaves (diameter: 6 cm) were immersed in a water-diluted solution of the insecticide of the present invention (wettable powder) prepared according to the formulation of Formulation Example 1 for 1 minute. Soaked. After the immersion, it was air-dried and placed in a plastic cup (inner diameter 7 cm), and 5 third-instar insects of Spodoptera litura were released in the cup (1 concentration, 2 repetitions). The cells were kept in a thermostatic chamber at 25 ° C., and the life and death and agony of the larvae were examined 5 days after the release of the insects, and the insecticidal activity (%) was determined assuming that the agony insects were 1/2 dead. The results are shown in Table-6 (in the table below, the compound number corresponds to No. in Table-1).

[0091]

[Table 13]

Test Example 4 Acaricidal effect against adults of Nami-dani mite The stalk portion of the kidney bean seedling, which leaves one initial leaf, is inserted into a test tube (volume: 50 ml) containing water, and 15 female adults of Nami-dani mite are attached per leaf. I inoculated my head. One day after the inoculation, the mites parasitic leaves were treated with the compound (III) disclosed in JP-A-64-62876 and the various compounds of the present invention according to the formulation of Formulation Example 3, respectively. Immersion treatment (about 5 seconds) in a water-diluted solution (1 concentration, 2 repetitions). 25
It was kept in a thermostatic chamber at 0 ° C., and the number of adult female mites on the green leaves was examined 5 days after the treatment, and the mortality rate (%) was calculated based on the results. The results are shown in Table-7 (in the table below,
The compound number corresponds to No. in Tables 1-2.

[0093]

[Table 14]

[0094]

INDUSTRIAL APPLICABILITY The pyrazole carboxamides of the present invention have excellent control effects against strains, harmful insects and mites, and are excellent insecticides and acaricides for agriculture and forestry and epidemics. Furthermore, it is expected to be used as a pest control agent for various pests in terms of preservation of livestock, fisheries or various products, and public health.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Toshiki Fukuchi             1000 Kamoshida-cho, Aoba-ku, Yokohama-shi, Kanagawa             Within Mitsubishi Chemical Corporation F-term (reference) 4C055 AA01 BA02 BA08 BA15 BB07                       CA02 CA03 CA06 CA08 CA15                       CA25 CA27 CB07 DA01 DA06                       DA25                 4C063 AA01 AA03 BB01 BB09 CC22                       CC81 CC82 DD12 EE03                 4H011 AA01 AC01 AC04 BB09 DA02                       DA15 DA16 DD03

Claims (11)

[Claims] 1. The following general formula (I): (In the formula, R ¹ represents a C _{1 to} C ₅ alkyl group, and R ² represents C ₁
To C ₅ alkyl group, C _{1 to} C ₅ haloalkyl group or C _{1 to} C ₅ alkoxy group, R ³ represents a hydrogen atom or C _{1 to} C ₃ alkyl group, and R ⁴ represents C ₁ to alkyl C _5, shows a haloalkyl group or a halogen atom C ₁ ~C ^_5, R ₅ is an alkyl group, a haloalkyl group, an alkoxy group, alkoxyalkoxy group, haloalkoxy group, a hydroxyl group, an acyloxy group, haloprogin Bae oxy group , An alkylthio group, a formyl group, A group represented by the formula (wherein R ⁶ and R ⁷ represent a hydrogen atom or a C ₁ -C ₅ alkyl group), or two adjacent R ⁵ are joined together and (Provided that when n is 1, R ⁵ is not an alkyl group). m is an integer of 0 to 4, n is 1
Represents an integer of 5 and p represents 0 or 1. X represents a hydrogen atom, C ₁ -C ₃ alkyl group, a C ₁ -C ₃ alkoxy group or a halogen atom. ) Pyrazole carboxamides and acid addition salts thereof. 2. The pyrazole carboxamides and acid addition salts thereof according to claim 1, wherein in the general formula (I), R ¹ is a methyl group. 3. The pyrazole carboxamides and acid addition salts thereof according to claim 1, wherein in the general formula (I), R ² is a methyl group or an ethyl group. 4. In the general formula (I), R ⁵ is C _{1 to} C ₅
The pyrazole carboxamides and acid addition salts thereof according to any one of claims 1 to 3, wherein the haloalkyl group is a C _{1 to} C ₅ haloalkoxy group. 5. The pyrazole carboxamides and acid addition salts thereof according to claim 1, wherein in the general formula (I), R ³ is a hydrogen atom. 6. The pyrazole carboxamides and acid addition salts thereof according to claim 1, wherein X in the general formula (I) is a hydrogen atom. 7. The pyrazole carboxamides and acid addition salts thereof according to claim 1, wherein in the general formula (I), m is an integer of 0 to 2 and n is 1 or 2. 8. The following general formula (II): (In the formula, R ³ , R ⁴ and m are as defined in the general formula (I), and R ⁸ represents a haloalkoxy group.)
And phenylpyridylmethylamines and acid addition salts thereof. 9. A pest control agent containing the pyrazolecarboxamides according to any one of claims 1 to 7 and / or an acid addition salt thereof as an active ingredient. 10. A bactericide containing the pyrazole carboxamides according to any one of claims 1 to 7 and / or an acid addition salt thereof as an active ingredient. 11. An insecticide or acaricide containing the pyrazolecarboxamide according to any one of claims 1 to 7 and / or an acid addition salt thereof as an active ingredient.