JP2001089463A - Bis-isoxazole derivative and plant disease-controlling agent for agricultural and horticultural purposes - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel compound that has a new skeleton of the chemical structure different from that of conventional chemicals and manifests excellent plant disease-controlling activity. SOLUTION: A novel isoxazolecarboxylic derivative represented by the general formula (I) [R1 and R4 are identical to or different from each other a halogen atom; R2 and R3 are identical to or different from each other H or a halogen atom; X1 is carbonyl or methylene; Y1 and Y2 are identical to or different from each other an O atom or S atom or NRE, (R5 is H, a lower alkyl, a lower haloalkl or a lower alkoxy-lower-alkyl); and Z is an alkylene] has been synthesized. The compound of the general formula (I) has excellent controlling action against the plant diseases, for example, rice blast disease and the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel isoxazole carboxylic acid derivative useful in the field of agriculture and horticulture, particularly in the field of agrochemical production, and also relates to an agricultural and horticultural plant disease controlling agent containing the compound as an active ingredient. Therefore, the present invention is useful in the fields of the chemical industry and the agrochemical manufacturing industry.

[0002]

2. Description of the Related Art The following are known as isoxazole-5-carboxylic acid derivatives. EP-A-761654 discloses that compounds of the following general formula (A) have herbicidal activity. Y: hydrogen atom, halogen atom, substituted alkyl group, etc. W: substituted alkyl group, alkenyl group, etc. X: O, S Z: substituted C ₁ -C ₄ alkylene group R ₁ : substituted alkyl group, substituted acyl group, etc. R ₂ : Substituted aryl group, heteroaryl group, etc.

[0003] Japanese Patent Publication No. 2-500365 discloses the following general formula:
It is described that the compound (B) has a recognition assisting action. R: hydrogen atom, lower alkyl group, halogen atom, etc. R ₁ : hydroxyl group, alkoxy group, etc. n: an integer of 1 or 2.

JP-A-3-130270, JP-A-5-86039
JP-A-6-505228 and JP-A-8-41037 describe that a compound represented by the following formula (C) has herbicidal activity. R ₁ : hydrogen, halogen atom, lower alkyl group, etc. R ₂ : formyl group, lower alkoxycarbonyl group, etc. R ₃ : hydrogen atom, haloalkyl group, alkoxyalkyl group, etc. R ₄ : hydrogen atom, hydroxy group, lower alkoxy group, etc. X : Oxygen atom, sulfur atom.

[0005]

In the cultivation of agricultural or horticultural crops, various diseases that have a significant effect on production efficiency are known. For example, blast in rice cultivation can be mentioned as an important disease.

Various fungicides have been used for the diseases caused by the plant pathogens.
However, these known agricultural and horticultural fungicides are resistant to bacteria due to long-term use, and cannot be used because they do not have a sufficient bactericidal effect, or are combined with other agents to obtain a sufficient bactericidal effect. Had to be used. Therefore, in the field of cultivation of agricultural or horticultural crops,
There is a demand for the appearance of a novel compound having a plant disease controlling activity which has a different skeleton from conventional drugs and exhibits a sufficient controlling effect.

[0007] The present invention is intended to solve the problems associated with the prior art as described above, and an object of the present invention is to generate resistant bacteria due to the difference in the skeleton of the chemical structure from conventional drugs. It is an object of the present invention to provide a novel compound and a fungicide which exhibit a sufficient plant disease controlling activity without causing any problem.

[0008]

Means for Solving the Problems In order to achieve the above object, the present inventors have synthesized isoxazole carboxylic acid derivatives which are not known to have a plant disease controlling activity. Then, the plant disease controlling activity and the usefulness as a controlling agent were studied diligently. As a result, they have found that the isoxazole carboxylic acid derivative represented by the following general formula (I) has an excellent plant disease control effect without causing phytotoxicity to plants, and is particularly effective for controlling rice blast. .

Therefore, the gist of the first invention is that the general formula (I) Wherein R ₁ and R ₄ may be the same or different and each represent a halogen atom; R ₂ and R ₃ may be the same or different; each represents a hydrogen atom or a halogen atom;
₁ represents a carbonyl group C = O or a methylene group CH ₂ , and Y ₁
And Y ₂ may be the same or different and represent an oxygen atom or a sulfur atom, or a compound of the formula NR ₅ (where R ₅ is a hydrogen atom, a lower alkyl group, a lower haloalkyl group or a lower alkoxy lower alkyl group) Z represents the following formula (a) (Wherein, R ₆ , R ₇ , R ₈ , and R ₉ may be the same or different, and include a hydrogen atom, a hydroxy group, a lower alkyl group, a lower alkoxy group, a lower haloalkyl group, a lower alkoxy lower alkyl group, and a carboxy group. Represents a lower alkoxycarbonyl group, a lower alkoxycarbonyl lower alkyl group or an unsubstituted phenyl group, or a lower alkyl group, a lower alkoxy group, a lower haloalkyl group, a lower haloalkoxy group, a carboxy group, a lower alkoxycarbonyl group, a lower alkylthio group. A lower alkylsulfonyl group, a halogen atom, a phenyl group substituted with a cyano group, m represents an integer of 1 to 10, and when m = 1, R ₇ and R ₉ together represent 5 in cooperation with an alkylene group
Can form a 6-membered cycloalkyl ring, m ≧
In the case of 2, any one of R ₆ , R ₇ , R ₈ , and R ₉ is represented by the following formula (b) Wherein R ₁ , R ₂ and X ₁ may have the same meanings as described above, or Z represents the following formula (c) (Where b represents an integer of 1 to 2, and a represents a hydrogen atom, a halogen atom or a lower alkyl group)].

In the general formula (I), the lower alkyl group in the definition of R _{5 to} R ₉ is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. It may be shaped or branched. Such lower alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, se
Examples thereof include a c-butyl group, a t-butyl group, an n-pentyl group, an isoamyl group, and an n-hexyl group.

In the above formula (I), the lower alkoxy group in the definition of R _{6 to} R ₉ includes an alkoxy group having 1 to 6 carbon atoms, specifically, a methoxy group, an ethoxy group, an n-propoxy group, Examples include a propoxy group, an n-butoxy group, a sec-butoxy group, a t-butoxy group, an isoamyloxy group, and an n-hexyloxy group. The above general formula (I)
Wherein, as the lower haloalkyl group in the definition of R _{5 to} R ₉ , a haloalkyl group having 1 to 6 carbon atoms, specifically, a trifluoromethyl group, a difluoromethyl group, a trichloromethyl group, a dichloromethyl group, a fluoromethyl group, Chloromethyl group, iodomethyl group, bromomethyl group, difluorochloromethyl group, 2,2,2-trifluoroethyl group, 2,2,2-
Examples thereof include a trichloroethyl group, a pentafluoroethyl group, and a pentachloroethyl group.

The lower haloalkoxy group has 1 carbon atom.
To 6 haloalkoxy groups, specifically, trifluoromethoxy, difluoromethoxy, fluoromethoxy, trichloromethoxy, tribromomethoxy, 2,2
2,2-trifluoroethoxy group, 2,2,2-trichloroethoxy group, pentafluoroethoxy group, 2-fluoroethoxy group, 2-chloroethoxy group, 2-bromoethoxy group, 2-iodoethoxy group, 3- Examples thereof include a chloropropoxy group.

In the above general formula (I), the lower alkoxycarbonyl group in the definition of R _{6 to} R ₉ has 2 to 2 carbon atoms.
And 7-alkoxycarbonyl group, for example, methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, t-butoxycarbonyl group, sec-butoxycarbonyl group, isoamyloxycarbonyl group and the like. In the above general formula (I), R
The halogen atom in the definition of _{1 to} R ₉ represents a chlorine atom, a bromine atom, an iodine atom or a fluorine atom.

The first isoxazolecarboxylic acid derivative of the general formula (I) according to the present invention has, as an embodiment thereof,
Derivatives represented by the following general formulas (Ia), (Ib), (Ic) and (Id) are included. (1) General formula (Ia) [Wherein, R ₁ , R ₂ , R ₃ , R ₄ , Y ₁ , Y ₂ and Z have the same meaning as defined in the general formula (I), ie, R
₁ and R ₄ may be the same or different and represent a halogen atom, R ₂ and R ₃ may be the same or different, represent a hydrogen atom or a halogen atom, and Y ₁ and Y ₂ are the same or different Or an oxygen atom or a sulfur atom, or a group of the formula NR ₅ (where R ₅ is a hydrogen atom, a lower alkyl group, a lower haloalkyl group or a lower alkoxy lower alkyl group); (A) (Wherein, R ₆ , R ₇ , R ₈ , and R ₉ may be the same or different, and include a hydrogen atom, a hydroxy group, a lower alkyl group, a lower alkoxy group, a lower haloalkyl group, a lower alkoxy lower alkyl group, and a carboxy group. Represents a lower alkoxycarbonyl group, a lower alkoxycarbonyl lower alkyl group or an unsubstituted phenyl group, or a lower alkyl group, a lower alkoxy group, a lower haloalkyl group, a lower haloalkoxy group, a carboxy group, a lower alkoxycarbonyl group, a lower alkylthio group. A lower alkylsulfonyl group, a halogen atom, a phenyl group substituted with a cyano group, m represents an integer of 1 to 10, and when m = 1, R ₇ and R ₉ together represent 5 in cooperation with an alkylene group
Can form a 6-membered cycloalkyl ring, m ≧
In the case of 2, any one of R ₆ , R ₇ , R ₈ , and R ₉ is represented by the following formula (b) Wherein X ₁ represents a carbonyl group C = O or a methylene group CH ₂ , and R ₁ and R ₂ may have the same meanings as described above. (C) (Where b represents an integer of 1 to 2, and a represents a hydrogen atom, a halogen atom or a lower alkyl group).]

(2) General formula (Ib) [Wherein R ₁ , R ₂ , R ₃ , R ₄ , X ₁ , Y ₂ and Z have the same meaning as defined in the above general formula (I)].

(3) General formula (Ic) [Wherein R ₁ , R ₂ , R ₃ , R ₄ , X ₁ , Y ₂ and Z have the same meaning as defined in the above general formula (I)].

(4) General formula (Id) [Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , X ₁ , Y ₂ and Z have the same meaning as defined in the above general formula (I)] Acid derivatives.

Further, in the second aspect of the present invention, the derivatives of the above general formula (I), particularly the above general formulas (Ia) and (Ia)
The present invention provides an agricultural and horticultural plant disease control agent comprising a derivative of (b), (Ic) or (Id) as an active ingredient.

The second control agent according to the present invention is effective for controlling rice blast, rice sheath blight, barley powdery mildew, cucumber downy mildew and the like, and has the activity of a compound of the general formula (I). It can be in the form of a composition containing the carrier admixed with the components.

Next, specific examples of the compounds included in the general formula (I) of the present invention are shown in Table 1 below. However, the present invention is not limited to only these examples. In Table 1, Me represents a methyl group, Et represents an ethyl group, and Pr represents
Represents a propyl group, Bu represents a butyl group, and Ph represents a phenyl group.

[0021]

[0022]

[0023]

[0024]

[0025]

[0026]

[0027]

[0028]

Next, the method for producing the compound of the general formula (I) of the first invention will be described in detail. The isoxazole carboxylic acid derivative represented by the general formula (I) of the first invention can be produced, for example, by the following production method 1 and production method 2. The production method 1 is represented by the following reaction formula. (Where Halo represents a halogen atom, X ₁ ^a represents C = O, and R
_l , R ₂ , R ₃ , R ₄ , Y ₁ , Y ₂ , and Z represent the same meaning as described above).

That is, in the production method 1, the acid halide derivative represented by the general formula (II) and the compound represented by the general formula (III) are reacted in a suitable solvent in the presence of a deoxidizing agent. The isoxazolecarboxylic acid derivative represented by the general formula (I) can be produced.

Examples of the deoxidizing agent include organic tertiary amines such as triethylamine, tributylamine, diethylisopropylamine, pyridine, 4-dimethylaminopyridine, 2,6-dimethylpyridine, N-methylaniline and N-ethylaniline. Examples include amines, metal carbonates such as sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, and potassium carbonate, and alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, and barium hydroxide. The acid agent is preferably triethylamine, potassium hydrogen carbonate, potassium carbonate and the like.

The solvents used in the reaction include aromatic hydrocarbons such as benzene, toluene and xylene;
Halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, diethyl ether, dibutyl ether, 1,2-dimethoxyethane, 1,2
Ethers such as 2-diethoxyethane, tetrahydrofuran, and 1,4-dioxane; esters such as methyl acetate, ethyl acetate and butyl acetate; nitriles such as acetonitrile and propionitrile; acetone and methyl ethyl ketone Ketones, pyridine and the like can be used, or a mixed solvent thereof can also be used. Preferably, 1,2-dimethoxyethane, ethyl acetate, dichloromethane and the like can be mentioned.

The reaction temperature is usually from -80 to 150 ° C, preferably from 0 to 100 ° C. The reaction time varies depending on the reaction temperature and the reaction substrate, but is usually completed in 30 minutes to 24 hours. The compound of the general formula (I), which is the reaction target, is collected from the reaction mixture by a usual post-treatment. For example,
It is obtained by adding water to the reaction mixture, washing with water, and distilling off the solvent. The obtained target product can be purified, if necessary, by an operation such as column chromatography or recrystallization.

Production method 2 is represented by the following reaction formula. (Where Halo represents a halogen atom, R ₁ , R ₂ , R ₃ ,
R ₄ , X ₁ , Y ₁ , Y ₂ , Z and X ₁ are those of the above-mentioned general formula (I)
Has the same meaning as in).

In this production method 2, in the first reaction step, the halide derivative represented by the general formula (II) and the compound represented by the general formula (III) are dissolved in a suitable solvent in the presence of a deoxidizing agent. To produce an isoxazole derivative represented by the general formula (IV), and then, after isolating the compound (IV) or without isolation, it is converted to the compound represented by the general formula (V) in the second reaction step. The isoxazole carboxylic acid derivative represented by the general formula (I) can be produced by reacting the compound represented by the formula (I) with a deoxidizing agent.

The isoxazole derivative represented by the general formula (IV) can be produced, for example, by the following first reaction step. As the deoxidizing agent used in the first reaction step, triethylamine, tributylamine, diethylisopropylamine, pyridine, 4-dimethylaminopyridine, 2,6-dimethylpyridine, N-methylaniline, N-methylaniline,
Organic tertiary amines such as ethylaniline, metal carbonates such as sodium bicarbonate, potassium bicarbonate, sodium carbonate and potassium carbonate; alkali metal waters such as potassium hydroxide, sodium hydroxide and barium hydroxide Oxides can be mentioned, but the deoxidizing agent is preferably triethylamine, potassium hydrogen carbonate, potassium carbonate or the like.

Solvents used in the first reaction step include aromatic hydrocarbons such as benzene, toluene and xylene, and halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride and 1,2-dichloroethane. , Diethyl ether, dibutyl ether, 1,2-dimethoxyethane, 1,2-diethoxyethane, tetrahydrofuran, ethers such as 1,4-dioxane, methyl acetate,
Esters such as ethyl acetate and butyl acetate, nitriles such as acetonitrile and propionitrile, ketones such as acetone and methyl ethyl ketone, and pyridine can be used, or a mixed solvent thereof can also be used. Can be. Preferably, 1,2-dimethoxyethane, ethyl acetate, dichloromethane and the like can be mentioned.
The reaction temperature is usually from -80 to 150 ° C, preferably from 0 to 100 ° C.

The reaction time in the first reaction step varies depending on the reaction temperature and the reaction substrate, but is usually completed in 30 minutes to 24 hours. The compound of the general formula (IV) as the reaction target is collected from the reaction mixture by a usual post-treatment. For example, it can be obtained by adding water to the reaction mixture, washing with water, and then distilling off the solvent. The obtained target product can be purified, if necessary, by an operation such as column chromatography or recrystallization.

Next, in the second reaction step, a compound of the general formula (IV) is reacted with a carboxylic acid halide of the general formula (V) in the presence of a deoxidizing agent to give a compound of the general formula (I). The isoxazole derivative can be produced, for example, by the following method. Examples of the deoxidizing agent used in the second reaction step include triethylamine, tributylamine, diethylisopropylamine, pyridine, 4-dimethylaminopyridine, 2,6-dimethylpyridine, N-methylaniline, and N-methylaniline.
Organic tertiary amines such as ethylaniline, metal carbonates such as sodium bicarbonate, potassium bicarbonate, sodium carbonate and potassium carbonate; alkali metal waters such as potassium hydroxide, sodium hydroxide and barium hydroxide Oxides may be mentioned, and the deoxidizing agent is preferably triethylamine, potassium hydrogen carbonate, potassium carbonate or the like.

Solvents used for the reaction in the second reaction step include aromatic hydrocarbons such as benzene, toluene and xylene, and halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride and 1,2-dichloroethane. , Diethyl ether, dibutyl ether, 1,2-dimethoxyethane, 1,2-diethoxyethane, tetrahydrofuran, ethers such as 1,4-dioxane, methyl acetate,
Esters such as ethyl acetate and butyl acetate, nitriles such as acetonitrile and propionitrile, ketones such as acetone and methyl ethyl ketone, and pyridine can be used, or a mixed solvent thereof can also be used. Can be. Preferably, 1,2-dimethoxy methane, ethyl acetate, dichloromethane and the like are mentioned.
The reaction temperature is usually from -80 to 150 ° C, preferably from 0 to 100 ° C. The reaction time varies depending on the reaction temperature and the reaction substrate, but is usually completed in 30 minutes to 24 hours. The compound of the general formula (I), which is the reaction target, is collected from the reaction mixture by a usual post-treatment. For example, it can be obtained by adding water to the reaction mixture, washing with water, and then distilling off the solvent. The obtained target product can be purified, if necessary, by an operation such as column chromatography or recrystallization.

The compounds represented by the general formulas (II) and (V), which are the starting compounds of the above-mentioned production methods 1 and 2, can be produced, for example, by the following known production methods. it can. The isoxazole-5-carbonyl halide derivative represented by the general formula (V) can be obtained from Acta. Chem. Scand. S.
er. B), Volume B38, Page 815 (1984), Biochemical Pharmacology (B1ochem. Pharmacol) Volume 18,
P. 569 (1969), Pharmaco Edison Scientifica (Farmaco, Ed. Sci) Vol. 41, p. 440 (19
1986), Liebigs Ann.
Chem.) 8, 815 (1993), JP-A-62-501416
Bulletin, Journal of Heterocycl. Chem. 24 , p. 43 (1987)
Year), British Patent No. 1146448, 1st. Lombard Sci. P
t. I. ClasseSci. Mat. e Nat 94A , 729 (1960), Gazetta Kimica Italiana (Gazz. Chim. Ital) No. 91
Vol. 47, 1961, JP-A-2-292284, Journal of Medicinal Chemistry (J. Med. Che.
m.) 39, 2232 (1996), Synthesis (Synthe
sis), p. 69 (1986), Journal of Organic Chemistry (J. Org. Chem.) 26, 151
4 pages (1961), Journal of Industrial Science, 66 , 1831 (1963), Journal of Industrial Science, 66 , 1838 (1963), Berichte (Ber.) No. 106
Vol. 3345 (1973), Journal of American Palmerutical Association (J. Am. P.
harm. Assoc.), 42, 594 (1953), Gazza Chim. Ital. 8
1, page 117 (1951) and the like, or a method analogous thereto.

Further, as shown in the following reaction formula, the general formula (VI)
Can be oxidized with an oxidizing agent to produce a compound of the general formula (V). (Wherein R ₁ and R ₂ represent the same meaning as described above, and R ₁₀ represents a hydroxymethyl group or an aldehyde group).

That is, the carboxylic acid derivative of the general formula (V) can be synthesized by oxidizing the compound of the general formula (VI) in a solvent using an appropriate oxidizing agent. Oxidizing agents include inorganic peroxides such as potassium permanganate, potassium dichromate, and sodium perchlorate, and peroxides such as aqueous hydrogen peroxide, m-chloroperbenzoic acid, peracetic acid, and t-butyl hydroperoxide. Can be used. Or platinum,
Oxygen oxidation can also be carried out using a metal such as cobalt or ruthenium and a complex thereof as a catalyst. These reactions are performed in a usual solvent. Examples of the solvent that can be used include ketones such as acetone and methyl ethyl ketone, organic acids such as acetic acid and propionic acid, organic halogenated hydrocarbons such as dichloromethane, chloroform and chlorobenzene, and water, or a mixed solvent thereof. Preferably, water, acetic acid, acetone, chloroform and the like are used.

The compound of the general formula (VI) can be obtained from Pharmaco, Ed. Sci.
Vol. 1, p. 440 (1986), JP-A-62-501416, JP-A-59-137472, Bulletin of Chemical Society of Japan (Bu11. Chem. Soc. J
p.) Vol. 57, p. 2184, (1984) and the like, and can be easily produced according to them.

The isoxazole-5-halomethyl derivative contained in the general formula (II) is described in Synthesis Communication, vol. 18, (1).
0), pages 1171-1176 (1988) and the like, and can be easily produced according to them.

Next, several production examples of the compound of the formula (I) will be described with reference to examples. The compound numbers are shown in Table 1.
Refer to the above.

Example 1 (Production by Production Method 1) Production of Bis (3-chloroisoxazole-5-carboxylic acid) ethylene (Compound No. 1) 0.6 g of ethylene glycol was placed in a 50 ml four-necked flask.
(9.6 mmol) and 1.9 g (19.3 mmol) of triethylamine.
Dissolved in 20 ml of chloroform. 3.2 g (1.93 mmol) of 3-chloroisoxazole-5-carbonyl chloride was added dropwise to the mixture under ice-water cooling. After the addition, the mixture was stirred at room temperature for 3 hours to complete the reaction. The reaction solution was washed with 1 N hydrochloric acid, a 5% sodium hydrogen carbonate solution and then with saturated saline, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The residue was purified by silica gel chromatography (n-hexane: acetone = 7: 1), and 2.7 g of the title compound was obtained.
(87% yield).

Example 2 (Production by Production Method 2) 2- (3-chloroisoxazole-5-methyloxy) ethyl
Preparation of 3-chloroisoxazole-5-carboxylate (Compound No. 53) In a 50 ml four-necked flask, 0.3% of 60% sodium hydride was added.
g (6.8 mmol) in 20 ml ethylene glycol,
The mixture was stirred at room temperature for 10 minutes. 1.0 g (6.8 mm) of 3-chloroisoxazole-5-methyl chloride was added to this mixed solution under water cooling.
ol) was added dropwise. After the addition, the mixture was stirred at room temperature for 2 hours to complete the reaction. The reaction solution was poured into ethyl acetate, washed twice with a saturated saline solution, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. This residue was dissolved in 10 ml of tetrahydrofuran, and 0.9 g (8.4 mmol) of triethylamine was added. 1.1 g (6.8 mmol) of 3-chloroisoxazole-5-carbonyl chloride was added dropwise to the mixture under cooling with water. After the addition, the mixture was stirred at room temperature for 2 hours to complete the reaction. The reaction solution was poured into ethyl acetate, washed with 1 N hydrochloric acid, a 5% sodium hydrogen carbonate solution and then with a saturated saline solution, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The residue was purified by silica gel chromatography (n-hexane: acetone = 5: 1) to give the title compound (1.4 g, yield 67%).
I got

Example 3 (Production by Production Method 1) Production of N- [2- (3-chloroisoxazole-5-carbonyloxy) ethyl] -3-chloroisoxazole-5-carboxamide (Compound No. 89) 0.6 g aminoethanol in a 100 ml four-necked flask
(9.6 mmol) and 1.9 g (19.3 mmol) of triethylamine.
Dissolved in 50 ml of tetrahydrofuran. 3.2 g (19.3 mmol) of 3-chloroisoxazole-5-carbonyl chloride was added dropwise to the mixture under ice-water cooling. After the addition, the mixture was stirred at room temperature for 2 hours to complete the reaction. The reaction solution was poured into 50 ml of toluene, washed with 1N hydrochloric acid, a 5% sodium hydrogen carbonate solution and then with a saturated saline solution, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The residue was purified by silica gel chromatography (toluene: acetone: 15: 1) to give the title compound (1.7 g, yield 54%).

Example 4 (Production by Production Method 1) Production of N- (3-chloroisoxazole-5-carboxyl) -cysteineethyl ester 3-chloroisoxazole-5-carboxylate (Compound No. 122) 0.9 g (4.9 mmol) of cysteine ethyl ester hydrochloride and 1.6 g of triethylamine (1
5.7 mmol) was dissolved in 30 ml of dimethylformamide. To this mixture, add 3-chloroisoxazole under ice-water cooling.
2.0 g (11.8 mmol) of -5-carbonyl chloride was added dropwise. After the addition, the mixture was stirred at room temperature for 2 hours to complete the reaction. The reaction solution was washed with 1 N hydrochloric acid, a 5% sodium hydrogen carbonate solution and then with saturated saline, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The residue was purified by silica gel chromatography (n-hexane: ethyl acetate = 4: 1) to give the title compound (1.2 g, yield 60%).

Example 5 (Production by Production Method 1) Production of N, N'-1,2-ethylenediylbis (3-chloroisoxazole-5-carboxylic acid) (Compound No. 139) 0.3 g ethylenediamine in flask
(5.2 mmol) and 1.0 g (10.4 mmol) of triethylamine in 3
It was dissolved in 0 ml of chloroform. 3-chloroisoxazole-5-carbonyl chloride is added to the mixture under water cooling.
1.6 g (10.4 mmol) was added dropwise. After the addition, the mixture was stirred at room temperature for 3 hours to complete the reaction. The precipitated crystals were collected by filtration, washed successively with chloroform and then with water and air-dried to obtain 1.4 g (yield 82%) of the title compound.

Example 6 (Production by Production Method 1) Bis (3,4-dichloroisoxazole-5-carboxylic acid)
Preparation of ethylene (Compound No. 157) 1.2 g of ethylene glycol in a 100 ml four-necked flask
(19.3 mmol), 3.8 g (38.6 mmol) of triethylamine
Was dissolved in 50 ml of chloroform. Under cooling with ice water, 7.7 g (38.6 mmol) of 3,4-dichloroisoxazole-5-carbonyl chloride was added dropwise to the mixture. After the addition, the mixture was stirred at room temperature for 2 hours to complete the reaction. The reaction solution was washed with 1 N hydrochloric acid, a 5% sodium hydrogen carbonate solution and then with saturated saline, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The residue was purified by silica gel chromatography (n-hexane: acetone = 10: 1) to give the title compound 6.4.
g (85% yield).

Example 7 (Production by Production Method 1) N- [2- (3,4-dichloroisoxazole-5-carbonyloxy) ethyl] -3,4-dichloroisoxazole-5-carboxamide (Compound No. Preparation of 188) 0.6 g of aminoethanol in a 100 ml four-necked flask
(9.6 mmol) and 1.9 g (19.3 mmol) of triethylamine.
Dissolved in 50 ml of tetrahydrofuran. Under cooling with ice water, 3.9 g (19.3 mmol) of 3,4-dichloroisoxazole-5-carbonyl chloride was added dropwise to the mixture. After the addition, the mixture was stirred at room temperature for 2 hours to complete the reaction. The reaction solution was poured into 50 ml of toluene, washed with 1N hydrochloric acid, a 5% sodium hydrogen carbonate solution and then with a saturated saline solution, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. Silica gel chromatography of the residue (toluene: acetone = 20: 1)
Then, 2.8 g (yield: 75%) of the title compound was obtained.

Next, the case of formulating an agricultural and horticultural disease controlling agent, particularly a fungicide, in the second invention will be described.

When the compound of the present invention represented by the general formula (I) is used as an active ingredient in an agricultural and horticultural fungicide, it may be used alone, but depending on the purpose, it may be prepared by a conventional method in the art. It is preferable to use it by formulating it as a composition.
That is, the compound of the general formula (I) is mixed with a suitable carrier, and if necessary, a surfactant and other formulation auxiliaries are blended to obtain a formulation generally used as a formulation of an agricultural chemical. . For example, powders, fine granules, granules,
It can be formulated into tablets, wettable powders, concentrated emulsions, suspoemulsions, wettable powders, flowables, solutions, emulsions, oils, pastes, aerosols, microcapsules, coatings for seeds and the like. The dosage forms that can be formulated are not limited to those listed here. In addition, one or more compounds of the present invention according to the general formula (I) can be blended as an active ingredient.

As the liquid carrier used in the above-mentioned formulation, generally, aromatic hydrocarbons (eg, benzene, toluene, xylene, alkylnaphthalene, etc.), aliphatic hydrocarbons (eg, cyclohexane, paraffins, etc.), alcohols (Eg, ethylene glycol, isopropyl alcohol, butanol, etc.), ethers (eg,
Dioxane, tetrahydrofuran, etc.), esters (eg, glycerin esters of fatty acids, etc.), ketones (eg, acetone, methyl ethyl ketone, etc.), amides (eg, dimethylformamide, dimethylacetamide, etc.), sulfoxides (eg, dimethyl sulfoxide, etc.) ), Water and the like. As a solid carrier, kaolin, bentonite, clay, talc, attapull guide, montmorillonite, diatomaceous earth, silica sand, synthetic silicate, alumina, white carbon, calcium carbonate,
Calcium phosphate, starch, sawdust, soy flour, walnut shell flour,
Examples include tobacco stem powder, ammonium sulfate, urea, vermiculite and the like.

Examples of the surfactant include anionic surfactants such as alkyl sulfates, alkyl (aryl) sulfonates, dialkyl sulfosuccinates, and polyoxyethylene alkyl aryl ether phosphates; polyoxyethylene alkyl ethers; Non-ionic surfactants such as polyoxyethylene alkylaryl ether, sorbitan fatty acid ester and polyoxyethylene sorbitan acid ester can be exemplified. Examples of the formulation auxiliary include a physical property improver, a decomposition inhibitor, a binder and the like.

The compounding amount of the compound of the present invention in the composition preparation is as follows:
It can be appropriately adjusted depending on the dosage form of the preparation and the method of use, and it is generally desirable to use it in the range of 0.1 to 95% by weight.

The agricultural and horticultural disease controlling agent of the second invention includes:
In addition to the compound of the present invention, which is an active ingredient in the above various formulation forms, other known active compounds, for example, a bactericide,
An insecticide, an acaricide, a nematicide, an insect growth regulator, a herbicide, a bird repellent, a growth regulator, a fertilizer, a soil conditioner, and the like may be added.

The method for applying the agricultural and horticultural disease controlling agent of the second invention is not particularly limited, and is applied to foliage application, water application (paddy rice), nursery box application (paddy rice), soil application, and seed treatment. And the like. The active ingredient in actual application can be appropriately changed according to the type of compound, the target of application (eg, target disease, target crop, etc.), the timing of application, and the like. For example, in the case of foliar application, a wettable powder, a flowable, a formulation used in liquid form such as a wettable powder as an active ingredient amount of 5 to 1000 ppm, preferably 10 to 10 ppm
300-1000 liters per 10 ares when diluted with water etc. in a solution with a concentration range of ~ 500 ppm, usually 70-180 liters for paddy rice, 100-up for field crops depending on the type and fertility of the target crop
It can be used at an application rate of 300 liters or 300-800 liters for fruit trees.

When a solid preparation such as a powder is sprayed on foliage, it can be used at an application rate of 2 to 5 kg per 10 ares (active ingredient amount: 5 to 150 g / 10 ares).
In the case of paddy rice surface application, a solid preparation such as granules is applied in an amount of 0.3 to 5 kg per 10 ares (50 to 50 kg of active ingredient).
300 g / 10 ares).

In the case of applying the rice seedling raising box, the treatment time is from immediately after sowing the seeds to the seedling raising box until immediately before rice planting.
There is no particular limitation, and a solid preparation such as a granule is added to a seedling box (size: length x width x height 60 cm x 30 cm x 3 cm) in a range of 20 to 100.
g (active ingredient, 0.5-20 g / seedling box). Formulations such as wettable powders, flowables, wettable powders, etc. may be diluted with water, etc., as needed, 0.03
~ 1 liter application rate (0.5-20 g of active ingredient)
/ Seedling box).

In the case of soil application, the soil surface or in the soil
1m solid preparation such as granules²3 to 300 g per
Application rate (1 to 100 g / m as active ingredient amount)²Used in
Liquids such as wettable powders, flowables, wettable powders, etc.
1m after diluting the preparation to be used with water²0.1-1 per
0 liter application rate (1 to 100 g /
m ²) Can be used. In addition, these solid preparations
And the formulation used in liquid form, on the soil surface
Alternatively, it can also be applied to local treatments in soil (active ingredient content and
5 to 500 mg / strain).

In the case of treating seeds, liquid preparations such as wettable powders, flowables, wettable powders and the like may be diluted with water or the like, if necessary, to give an application rate of 1 to 5% of the seed weight ( It can be used in spraying or slurry treatment with an active ingredient amount of 0.5 to 20 g / seed weight 1 kg), and a solid preparation such as a wettable powder is applied in an amount of 0.1 to 2% of the seed weight (as an active ingredient amount). , 0.5-20 g / seed weight 1 kg).

Hereinafter, the second composition of the present invention will be described more specifically with reference to examples, but the scope of the present invention is not limited to the following examples. The compound No. indicates the one shown in Table 1. Example 8 (Powder) 2 parts of the compound of Compound No. 1, 0.3 part of PAP (physical property improver) and 97.7 parts of clay are uniformly mixed and pulverized to obtain a powder containing 2% of the active ingredient. Granules can be obtained in the same manner by using the compounds shown in Table 1 in place of the compound of Compound No. 1.

Example 9 (Wettable powder) 20 parts of compound No. 52, 3 parts of sodium alkylbenzenesulfonate, 5 parts of polyoxymethylene nonylphenyl ether, 5 parts of white carbon and 67 parts of clay were mixed uniformly, Grinding gives a wettable powder containing 20% of active ingredient. A wettable powder can be obtained in the same manner by using the compounds shown in Table 1 in place of the compound of Compound No. 52.

Example 10 (Emulsion) 30 parts of Compound No. 157, 55 parts of methyl ethyl ketone and 15 parts of polyoxyethylene nonylphenyl ether were mixed and dissolved to obtain an emulsion containing 30% of the active ingredient. Emulsions can be obtained in the same manner by using the compounds shown in Table 1 in place of the compound of Compound No. 157.

Example 11 (Sol) 40 parts of compound No. 172, lauryl sulfate 2
Parts, 2 parts of sodium alkylnaphthalenesulfonate, 1 part of methylcellulose and 55 parts of water are uniformly mixed to obtain a sol containing 40% of the active ingredient. A sol can be obtained in the same manner by using the compounds shown in Table 1 in place of the compound of Compound No. 172.

Example 12 (Granules) 10 parts of Compound No. 188, lauryl sulfate 1
Parts, calcium lignin sulfonate 5 parts, bentonite
30 parts and 54 parts of clay are mixed with 15 parts of water, kneaded with a kneader, granulated with a granulator, and dried with a fluidized drier to obtain granules containing 10% of active ingredient. Granules can be obtained in the same manner by using the compounds shown in Table 1 in place of the compound of Compound No. 188.

[0070]

The compound of the present invention of the general formula (I) has a high control effect on rice blast and is useful as an active ingredient of a fungicide for agricultural and horticultural use. It is also useful for diseases such as rice sheath blight, barley powdery mildew, and cucumber downy mildew. However, the plant diseases to be controlled by the compound of the present invention are not limited to those exemplified above.

Next, Tests 1 to 3 show specific examples of the usefulness of the compound of the present invention. Test Example 1 Rice blast control effect test Example 2 was carried out on the third leaf stage seedling (5 seedlings per pot) of paddy rice (cultivar: Asahi) cultivated in soil in a greenhouse in a plastic pot having a diameter of 6 cm. 10m / pot using an automatic spraying machine with a predetermined concentration diluted solution of wettable powder prepared according to
l Sprayed. Seven days after the chemical treatment, the rice blast fungus ( Pyriculari) previously formed on the oatmeal agar medium was used.
a oryzae : Pyroclaria oryzae conidiospores obtained by adjusting the spore concentration to 5 × 10 ⁵ spores (number) / ml with a 50 ppm aqueous solution of a spreading agent (polyoxyethylene alkyl ether) The suspension was sprayed using a spray gun to inoculate the rice bacterium. After being kept in an inoculation box at 24 ° C and 100% humidity overnight, they were transferred to a greenhouse at 24 ° C to promote disease. Six days after inoculation, the total number of rice blast lesions per pot of the third leaf was examined, and the control value (%) was calculated by the following formula.

This test was carried out in three repetitions per chemical concentration group, the average control value (%) was determined, and converted to an evaluation value according to the following criteria. In addition, phytotoxicity to rice was investigated according to the following criteria. Table 2 shows the results. In addition, the evaluation value of the control value and the investigation index of the chemical damage are the same in Test Examples 2 and 3 below.

[0073] Investigation index of phytotoxicity 5: Severe 4: Severe 3: Many 2: Slight 1: Slight 0: None

[0074]

Test Example 2 Effect of Rice Blast Water Surface Application The fifth leaf stage seedling of rice (cultivar: Asahi) cultivated in a greenhouse under a flooded condition (water depth: 3 cm) in a Wagner pot having a size of 1/10000 ares. Granules prepared according to Example 5 were sprayed onto 3 kg per 10 ares per plant (5 seedlings per pot).
Seven days after the drug treatment, conidia of rice blast ( Pyricularia oryzae ) previously formed on an oatmeal agar medium were condensed with a 50 ppm aqueous solution of a spreading agent (polyoxyethylene alkyl ether) at a spore concentration of 5 ×. The spore suspension obtained by adjusting the number of spores to 10 ⁵ cells / ml was sprayed using a spray gun to inoculate rice germs. After being kept in an inoculation box at 24 ° C and 100% humidity overnight, they were transferred to a greenhouse at 24 ° C to promote disease. Six days after inoculation, one of the fifth leaves
The total number of rice blast spots per pot was investigated, and Test Example 1 was used.
The control value (%) was calculated in the same manner as described above.

This test was performed in a three-repeat system for each drug, and the evaluation value of the control effect and the degree of chemical damage to rice were displayed in the same manner as in Test Example 1. Table 3 shows the results.

Test Example 3 Test of rice blast nursery box treatment effect test Nursery box for test (length × width × height: 15 cm × 12 cm ×
5 g of the granules prepared according to Example 5 were sprayed on the 2.5th leaf stage seedling of paddy rice (variety: Asahi) cultivated at 3 cm) per box. One day after the chemical treatment, 5 seedlings were transplanted per 5 pots into a Wagner pot having a size of 1/10000 are and cultivated under flooded conditions (water depth 3 cm). Thirty days after transplantation, conidia of rice blast ( Pyricularia oryzae : Pyricularia oryzae ) previously formed on oatmeal agar medium were dissolved in a 50 ppm aqueous solution of a spreading agent (polyoxyethylene alkyl ether) at a concentration of 5 × 10 5 A spore suspension obtained by adjusting the number of spores to ⁵ (number) / ml was spray-inoculated using a spray gun. After being kept in an inoculation box at 24 ° C and 100% humidity overnight, they were transferred to a greenhouse at 24 ° C to promote disease. Six days after the inoculation, the total number of rice blast spots per pot was investigated, the average total number of spots per pot at 5 hot spots was determined, and the control value (%) was calculated in the same manner as in Test Example 1. .

This test was performed in a three-repeat system for each drug, and the evaluation value of the control effect and the degree of phytotoxicity to rice were displayed in the same manner as in Test Example 1. Table 4 shows the results.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Shinji Onoue 2264-1, Toda, Atsugi-shi, Kanagawa Sun-Am Katamachi A-203 (72) Inventor Shinya Maehara 2385, Toda, Atsugi-shi, Kanagawa Hokuko Chemical Dormitory (72) Invention Person Masato Ando 317 Munegami, Tamano City, Okayama Prefecture (72) Inventor Hideki Ohno 21-21 Wakaba-cho, Okayama City, Okayama Prefecture Casa Wakaba B-102 (72) Inventor Hideyuki Murakami 4-272, Iriya, Zama City, Kanagawa Prefecture 98 (72) Inventor Seiichi Kutsuma 1-59-901, Tsumada-Higashi 1-chome, Atsugi-shi, Kanagawa Prefecture (72) Inventor Tomomi Tahara 5-11-29-105, Sagami-Ono, Sagamihara-shi, Kanagawa Prefecture (72) Inventor Yoshihisa Watanabe 1F term of 2352 Toda, Atsugi-shi, Kanagawa 4C056 AA01 AB01 AC01 AD01 AE03 FA02 FA16 FA17 FB03 FC01 4H011 AA01 BA01 BB10 BC05 BC07 BC19 BC20 DA02 DA15 DA16 DD01 DD03 DD04 DH03

Claims (7)

[Claims] 1. Formula (I) Wherein R ₁ and R ₄ may be the same or different and each represent a halogen atom; R ₂ and R ₃ may be the same or different; each represents a hydrogen atom or a halogen atom;
₁ represents a carbonyl group C = O or a methylene group CH ₂ , and Y ₁
And Y ₂ may be the same or different and represent an oxygen atom or a sulfur atom, or a compound of the formula NR ₅ (where R ₅ is a hydrogen atom, a lower alkyl group, a lower haloalkyl group or a lower alkoxy lower alkyl group) Z represents the following formula (a) (Wherein, R ₆ , R ₇ , R ₈ , and R ₉ may be the same or different, and include a hydrogen atom, a hydroxy group, a lower alkyl group, a lower alkoxy group, a lower haloalkyl group, a lower alkoxy lower alkyl group, and a carboxy group. Represents a lower alkoxycarbonyl group, a lower alkoxycarbonyl lower alkyl group or an unsubstituted phenyl group, or a lower alkyl group, a lower alkoxy group, a lower haloalkyl group, a lower haloalkoxy group, a carboxy group, a lower alkoxycarbonyl group, a lower alkylthio group. A lower alkylsulfonyl group, a halogen atom, a phenyl group substituted with a cyano group, m represents an integer of 1 to 10, and when m = 1, R ₇ and R ₉ together represent 5 in cooperation with an alkylene group
Can form a 6-membered cycloalkyl ring, m ≧
In the case of 2, any one of R ₆ , R ₇ , R ₈ , and R ₉ is represented by the following formula (b) Wherein R ₁ , R ₂ and X ₁ have the same meanings as described above, or Z represents the following formula (c) (Where b represents an integer of 1 to 2, and a represents a hydrogen atom, a halogen atom or a lower alkyl group).] 2. The derivative of the general formula (I) according to claim 1, wherein Wherein R ₁ , R ₂ , R ₃ , R ₄ , Y ₁ , Y ₂ and Z are
R ₁ and R ₄ may be the same or different and represent a halogen atom, R ₂ and R ₃ may be the same or different and represent a hydrogen atom or a halogen atom. , Y ₁ and Y ₂ may be the same or different and each represent an oxygen atom or a sulfur atom, or a group represented by the formula NR ₅ (where R ₅ is a hydrogen atom, a lower alkyl group, a lower haloalkyl group or a lower alkoxy lower alkyl group) A) and Z represents the following formula (a) (Wherein, R ₆ , R ₇ , R ₈ , and R ₉ may be the same or different, and include a hydrogen atom, a hydroxy group, a lower alkyl group, a lower alkoxy group, a lower haloalkyl group, a lower alkoxy lower alkyl group, and a carboxy group. Represents a lower alkoxycarbonyl group, a lower alkoxycarbonyl lower alkyl group or an unsubstituted phenyl group, or a lower alkyl group, a lower alkoxy group, a lower haloalkyl group, a lower haloalkoxy group, a carboxy group, a lower alkoxycarbonyl group, a lower alkylthio group. A lower alkylsulfonyl group, a halogen atom, a phenyl group substituted with a cyano group, m represents an integer of 1 to 10, and when m = 1, R ₇ and R ₉ together represent 5 in cooperation with an alkylene group
Can form a 6-membered cycloalkyl ring, m ≧
In the case of 2, any one of R ₆ , R ₇ , R ₈ , and R ₉ is represented by the following formula (b) Wherein X ₁ represents a carbonyl group C = O or a methylene group CH ₂ , and R ₁ and R ₂ can have the same meanings as described above. Equation (c) Wherein b represents an integer of 1 to 2, and a represents a hydrogen atom, a halogen atom or a lower alkyl group.] The isoxazole carboxylic acid derivative represented by the formula (1): Derivatives. 3. The derivative of the general formula (I) according to claim 1 has the following general formula (Ib): Wherein R ₁ , R ₂ , R ₃ , R ₄ , X ₁ , Y ₂ and Z are
R ₁ and R ₄ may be the same or different and represent a halogen atom, R ₂ and R ₃ may be the same or different and represent a hydrogen atom or a halogen atom. , X ₁ represents a carbonyl group C = O or a methylene group CH ₂ , Y ₂ represents an oxygen atom or a sulfur atom, or a compound represented by the formula NR ₅ (where R ₅ is a hydrogen atom, a lower alkyl group, a lower haloalkyl Z is a group represented by the following formula (a): (Wherein, R ₆ , R ₇ , R ₈ , and R ₉ may be the same or different, and include a hydrogen atom, a hydroxy group, a lower alkyl group, a lower alkoxy group, a lower haloalkyl group, a lower alkoxy lower alkyl group, and a carboxy group. Represents a lower alkoxycarbonyl group, a lower alkoxycarbonyl lower alkyl group or an unsubstituted phenyl group, or a lower alkyl group, a lower alkoxy group, a lower haloalkyl group, a lower haloalkoxy group, a carboxy group, a lower alkoxycarbonyl group, a lower alkylthio group. A lower alkylsulfonyl group, a halogen atom, a phenyl group substituted with a cyano group, m represents an integer of 1 to 10, and when m = 1, R ₇ and R ₉ together represent 5 in cooperation with an alkylene group
Can form a 6-membered cycloalkyl ring, m ≧
In the case of 2, any one of R ₆ , R ₇ , R ₈ , and R ₉ is represented by the following formula (b) Wherein R ₁ , R ₂ and X ₁ have the same meanings as described above, or Z represents the following formula (c) Wherein b represents an integer of 1 to 2, and a represents a hydrogen atom, a halogen atom or a lower alkyl group.] The isoxazole carboxylic acid derivative represented by the formula (1): Derivatives. 4. The derivative of the general formula (I) according to claim 1 has the following general formula (Ic): Wherein R ₁ , R ₂ , R ₃ , R ₄ , X ₁ , Y ₂ and Z are
R ₁ and R ₄ may be the same or different and represent a halogen atom, R ₂ and R ₃ may be the same or different and represent a hydrogen atom or a halogen atom. , X ₁ represents a carbonyl group C = O or a methylene group CH ₂ , Y ₂ represents an oxygen atom or a sulfur atom, or a group represented by the formula NR ₅ (where R ₅ is a hydrogen atom, a lower alkyl group, a lower haloalkyl group Or a lower alkoxy lower alkyl group), and Z represents the following formula (a) (Wherein, R ₆ , R ₇ , R ₈ , and R ₉ may be the same or different, and include a hydrogen atom, a hydroxy group, a lower alkyl group, a lower alkoxy group, a lower haloalkyl group, a lower alkoxy lower alkyl group, and a carboxy group. Represents a lower alkoxycarbonyl group, a lower alkoxycarbonyl lower alkyl group or an unsubstituted phenyl group, or a lower alkyl group, a lower alkoxy group, a lower haloalkyl group, a lower haloalkoxy group, a carboxy group, a lower alkoxycarbonyl group, a lower alkylthio group. A lower alkylsulfonyl group, a halogen atom, a phenyl group substituted with a cyano group, m represents an integer of 1 to 10, and when m = 1, R ₇ and R ₉ together represent 5 in cooperation with an alkylene group
Can form a 6-membered cycloalkyl ring, m ≧
In the case of 2, any one of R ₆ , R ₇ , R ₈ , and R ₉ is represented by the following formula (b) Wherein R ₁ , R ₂ and X ₁ may have the same meanings as described above, or Z represents the following formula (c) Wherein b represents an integer of 1 to 2, and a represents a hydrogen atom, a halogen atom or a lower alkyl group.] The isoxazole carboxylic acid derivative represented by the formula (1): Derivatives. 5. The derivative of the general formula (I) according to claim 1 is a compound represented by the following general formula (Id) Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , X ₁ , Y ₂ and Z have the same meaning as in claim 1, that is, R ₁ and R ₄ are the same or different. R ₂ and R ₃ may be the same or different, and represent a hydrogen atom or a halogen atom, and X ₁ represents a carbonyl group
C = O or a methylene group CH ₂ , Y ₂ represents an oxygen atom or a sulfur atom, or a compound represented by the formula NR ₅ (where R ₅ is a hydrogen atom, a lower alkyl group, a lower haloalkyl group or a lower alkoxy lower alkyl group) Wherein Z is the following formula (a) (Wherein, R ₆ , R ₇ , R ₈ , and R ₉ may be the same or different, and include a hydrogen atom, a hydroxy group, a lower alkyl group, a lower alkoxy group, a lower haloalkyl group, a lower alkoxy lower alkyl group, and a carboxy group. Represents a lower alkoxycarbonyl group, a lower alkoxycarbonyl lower alkyl group or an unsubstituted phenyl group, or a lower alkyl group, a lower alkoxy group, a lower haloalkyl group, a lower haloalkoxy group, a carboxy group, a lower alkoxycarbonyl group, a lower alkylthio group. A lower alkylsulfonyl group, a halogen atom, a phenyl group substituted with a cyano group, m represents an integer of 1 to 10, and when m = 1, R ₇ and R ₉ together represent 5 in cooperation with an alkylene group
Can form a 6-membered cycloalkyl ring, m ≧
In the case of 2, any one of R ₆ , R ₇ , R ₈ , and R ₉ is represented by the following formula (b) Wherein R ₁ , R ₂ and X ₁ have the same meanings as described above, or Z represents the following formula (c) Wherein b represents an integer of 1 to 2, and a represents a hydrogen atom, a halogen atom or a lower alkyl group.] The isoxazole carboxylic acid derivative represented by the formula (1): Derivatives. 6. An agricultural and horticultural plant disease controlling agent comprising the isoxazole carboxylic acid derivative according to claim 1 as an active ingredient. 7. The controlling agent according to claim 6, which is used for controlling rice blast.