JPH054969A - Pyrazolyl acrylate derivative, agricultural and horticultural fungicide containing the same derivative as active component and intermediate thereof - Google Patents

Abstract

PURPOSE:To provide new compounds excellent in fungicidal effect and penetrating force and useful as an agricultural and horticultural fungicide. CONSTITUTION:Compounds of formula I (R1 and R2 are H or 1-5C alkyl; W is 2-4C alkylene, 2-4C alkenylene, O, S, NH, etc.; q is 0 or 1; A is 3-7C cycloalkyl, 6-12C aryl, heteroaryl, etc.), e.g. (E)-methyl 2-[4-(2,4- dichlorobenzoyloxy)-1, 3-dimethylpyrazol-5-y]-3-methoxyacrylate. The compounds of formula I can be obtained by reacting a pyrazole derivative of formula II with a carboxylic acid of formula III in an inert solvent (e.g. ethyl acetate) at -701 biling temperature of solvent. The compound of formula III is used in an amount of 0.5-1.5 equivalent based on the compound of formula II. Useful for rice blast, rice sheath blight, wheat or barley rust, powdery mildew, grey mold, epidemics, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel pyrazolyl acrylic acid derivative, an agricultural and horticultural fungicide containing the same as an active ingredient, and an intermediate thereof.

[0002]

2. Description of the Related Art Conventionally, it is known that certain acrylic acid derivatives have biological activity such as bactericidal effect. For example, European Patent Publication No. 178826 discloses the following formula:

[0003]

[Chemical 4]

The compound represented by the formula: JP-A-61-27
No. 7652 discloses the following formula

[0005]

[Chemical 5]

The compound represented by the formula:
No. 254669 discloses the following formula

[0007]

[Chemical 6]

It is described that the compound represented by the formula (1) has bactericidal activity. However, as is clear from the test examples described below, none of these compounds can always be said to have sufficient bactericidal activity and penetrating activity as agricultural and horticultural germicides.

[0009]

Means for Solving the Problems The present inventors have paid attention to such an acrylic acid derivative, and as a result of intensive studies, the pyrazolyl acrylic acid derivative having a specific structure has excellent bactericidal activity, and The inventors have found that they have extremely excellent penetrability for plants, and have completed the present invention.

That is, the gist of the present invention is the following general formula (I):

[0011]

[Chemical 7]

(In the above formula, R ₁ and R ₂ each independently represent a hydrogen atom or a C ₁ -C ₅ alkyl group, and W may be substituted by a C ₁ -C ₄ alkyl group. C ₁ -C alkylene group _4, C ₁ -C ₄ alkyl group by an optionally substituted C ₂ -C ₄ alkenylene group, alkynylene group of _{C 2 ~C 4, -O -,} - S-
Or -NH-, q represents 0 or 1, and A
Each is an optionally substituted C ₃ -C ₇ cycloalkyl group, a C ₆ -C ₁₂ aryl group or an oxygen atom, a sulfur atom or a nitrogen atom having 1 to 3 total atoms of 5 to 14 A pyrazolyl acrylic acid derivative represented by (representing a heteroaryl group), an agricultural and horticultural fungicide containing this derivative as an active ingredient, and an intermediate thereof.

The present invention will be described in detail below. Starting
The bright compound is represented by the general formula (I). The general
In formula (I), R₁And R₂Each independently
Hydrogen atom or methyl group, ethyl group, n-propyl group,
iso-propyl group, n-butyl group, t-butyl group, n
-C such as pentyl group₁~ C_FiveRepresents an alkyl group. R
₁Is preferably a hydrogen atom or C ₁~ C_FourThe alkyl
Represents a group, particularly preferably a methyl group or an ethyl group.
Represent.

R ₂ is preferably a hydrogen atom or C _1-
Represents a C ₃ alkyl group, particularly preferably a methyl group,
Represents an ethyl group or a propyl group. W is a methylene group,
Vinylene group; methylmethylene group, dimethylmethylene group, an ethyl methylene group, an ethylene group, ethylethylene group, such as a trimethylene group, an alkylene group of C ₁ -C optionally substituted by alkyl groups of ₄ C ₁ -C ₄ , such as methylvinylene group or propenylene group, alkenylene group of C ₁ may be substituted by an alkyl group of ~C ₄ C ₂ ~C _4; ethynylene group, C ₂ -C such propynylene
₄ alkynylene group; or -O-, -S-, -NH-
Represents Preferably, it represents a methylene group, an ethylene group, a vinylene group, -O-, -S- or -NH-.

Q represents 0 or 1. A is a C _{6 to} C ₁₂ aryl group such as a phenyl group, a xylyl group and a naphthyl group; a thiazolyl group, a benzothiazolyl group, a pyridyl group,
A heteroaryl group having a total of 5 to 14 oxygen atoms such as a thienyl group, a furyl group, a pyrazolyl group and a pyrimidyl group, a sulfur atom or a nitrogen atom, and a total of 5 to 14 atoms; or a cyclopropyl group, a cyclobutyl group or a cyclohexyl group, etc. It represents a C ₃ -C ₇ cycloalkyl group, which may have a substituent. Preferably A is

[0016]

[Chemical 8]

Or the above-mentioned sikh having r substituents X
Represents an alkyl group, X is a methyl group, an ethyl group, n
-Propyl group, iso-propyl group, n-butyl group, i
so-butyl group, sec-butyl group, tert-butyl group
Group, n-pentyl group, n-hexyl group, n-heptyl
Group, n-octyl group, n-ninor group, n-decyl group, etc.
C₁~ C_TenAlkyl group; vinyl group, allyl group, 1-propyl group
Lopenenyl group, 2-butenyl group, 1,3-butadienyl group
Group, 2-pentenyl group, 2-hexenyl group, 2-heptene
Nyl group, 2-octenyl group, 2-nonenyl group, 2-decene
C such as nyl group and 2-undecenyl group₂~ C₁₁Archeni
Group; methoxy group, ethoxy group, n-propoxy group, i
so-propoxy group, n-butoxy group, iso-butoxy group
Si group, sec-butoxy group, tert-butoxy group, n
-Pentyloxy group, n-hexyloxy group, n-hep
Tyloxy group, n-octyloxy group, n-nonyloxy group
C such as Si group and n-decyloxy group₁~ C_TenThe alkoxy
Group; methylthio group, ethylthio group, n-propylthio group
Group, iso-propylthio group, n-butylthio group, is
o-butylthio group, sec-butylthio group, tert-
Butylthio group, n-pentylthio group, n-hexylthio group
Group, n-heptylthio group, n-octylthio group, n-no
C such as nylthio group and n-decylthio group₁~ C_TenThe archi
Ruthio group; vinyloxy group, allyloxy group, 1-pro
Penyloxy group, 2-butenyloxy group, 1,3-butane
Dienyloxy group, 2-pentenyloxy group, 2-hexyl
Cenyloxy group, 2-heptenyloxy group, 2-octe
Nyloxy group, 2-nonenyloxy group, 2-decenyloxy group
C such as xy group and 2-undecenyloxy group₂~ C ₁₁A
Lucenyloxy group; ethynyloxy group, propargylo
Xy, 1-propynyloxy, 2-butynyloxy
Group, 2-pentynyloxy group, 2-hexynyloxy
Group, 2-heptynyloxy group, 2-octynyloxy
Group, 2-nonynyloxy group, 2-decynyloxy group, 2
-C such as undecynyloxy group₂~ C₁₁Alkynillo
Xy group; acetyl group, propionyl group, butyryl group, a
Sobutyryl group, valeryl group, isovaleryl group, pivalloy
Group, hexanoyl group, heptanoyl group, octanoyl
Group, nonanoyl group, decanoyl group, undecanoyl group, etc.
C₂~ C₁₁Alkylcarbonyl group of acetoxy
Group, propionyloxy group, butyryloxy group, isobutane
Tyryloxy group, valeryloxy group, isovaleryl oki
Si group, pivaloyloxy group, hexanoyloxy group,
Putanoyloxy group, octanoyloxy group, nonanoi
Ruoxy group, decanoyloxy group, undecanoyloxy
C such as Si group₂~ C₁₁Alkylcarbonyloxy group of
C such as nzoyl group, toluoyl group and naphthoyl group₇~ C
₁₃Arylcarbonyl group of cyclobutylcarbonylo
Xy, cyclopentylcarbonyloxy, cyclohexyl
Xylcarbonyloxy group, cycloheptylcarbonyl
Oxy group, cyclooctylcarbonyloxy group, cyclo
C such as nonylcarbonyloxy group_Four~ C₉The cycloal
Kircarbonyloxy group; Benzoyloxy group, Truo
C such as yloxy group and naphthoyloxy group₇~ C₁₃A
Reel carbonyloxy group; phenyl group, tolyl group, key
C such as silyl group and naphthyl group₆~ C₁₂Aryl group of
Enoxy group, tolyloxy group, xylyloxy group, naphth
C such as tyloxy group₆~ C₁₂Aryloxy group of
Nyl group, benzothienyl group, thianthrenyl group, furyl
Group, isobenzofuryl group, benzofuryl group, phenoxa
Thiinyl group, pyrrolyl group, imidazolyl group, pyrazolyl
Group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyri
Dazinyl group, indolizinyl group, isoindolyl group, a
Group, isoquinolyl group, quinolyl group, phthalazini
Group, naphthyridinyl group, quinoxalinyl group, quinazoli
Nyl group, cinnolinyl group, carbazolyl group, phenance
Ridinyl group, acridinyl group, phenanthrolinyl group,
Phenazinyl group, isothiazolyl group, thiazolyl group, a
Soxazolyl group, oxazolyl group, flazanyl group, etc.
Total raw material with 1 to 3 oxygen, sulfur and nitrogen atoms
A heteroaryl group having 5 to 14 children; a thienyloxy group,
Benzothienyloxy group, thianthrenyloxy group, fluorine
Ryloxy group, isobenzofuryloxy group, benzofuri
Group, phenoxathinyloxy group, pyrrolyl group
Xy group, imidazolyloxy group, pyrazolyloxy group,
Pyridyloxy group, pyrazinyloxy group, pyrimidinyl
Oxy group, pyridazinyloxy group, indolizinyloxy
Si group, isoindolyloxy group, indolyloxy group,
Isoquinolyloxy group, quinolyloxy group, phthalazini
Ruoxy group, naphthyridinyloxy group, quinoxalinyl
Oxy group, quinazolinyloxy group, cinnolinyloxy
Group, carbazolyloxy group, phenanthridinyloxy
Group, acridinyloxy group, phenanthrolinyloxy
Group, phenazinyloxy group, isothiazolyloxy group,
Thiazolyloxy group, isoxazolyloxy group, oxy
1 to 3 groups such as sazolyloxy group and flazanyloxy group
Total number of atoms having oxygen atom, sulfur atom, nitrogen atom 5 to 1
4 heteroaryloxy group; benzyl group, phenethyl group
Group, phenylpropyl group, naphthylmethyl group, naphthyl
C such as ethyl group₇~ C₁₂Aralkyl group of benzyloxy
Si group, phenethyloxy group, phenylpropyloxy
Group, naphthylmethyloxy group, naphthylethyloxy group
Such as C₇~ C₁₂Aralkyloxy group; hydrogen atom;
Halogen such as elementary atom, chlorine atom, bromine atom, iodine atom
Represents an atom; a cyano group; or a nitro group. C above₁~
C_TenAlkyl group of C₂~ C₁₁Alkenyl group of C₁~
C_TenAlkoxy group of C₁~ C_TenAlkylthio group of C
₂~ C₁₁Alkenyloxy group, C₂~ C₁₁The alkini
Luoxy group, C₂~ C₁₁An alkylcarbonyl group of
C₂~ C₁₁The alkylcarbonyloxy groups of are
C₁~ C_FiveAlkoxy group, halogen atom, nitro group,
1 or more selected from a cyano group and a trifluoromethyl group
It may have the above substituents, and C₇~ C₁₃The ant
Carbonyl group, C_Four~ C₉Cycloalkyl carbo
Nyloxy group, C₇~ C₁₃Aryl carbonyloxy
Base, C₆~ C₁₂Aryl group of C₆~ C₁₂Aryl's
Xyl group, having 1-3 oxygen, sulfur and nitrogen atoms
A heteroaryl group having a total number of atoms of 5 to 14 of 1 to 3
Total number of atoms having oxygen atom, sulfur atom, nitrogen atom 5 to 1
4 heteroaryloxy groups, C₇~ C₁₂Aralkyl
Radical and C₇~ C₁₂The aralkyloxy groups of are each C
₁~ C _FiveAlkyl group of C₁~ C_FiveThe alkoxy group of
Rogen atom, nitro group, cyano group and trifluorome
It may have one or more substituents selected from chill groups.
Yes.

X is preferably substituted with a halogen atom.
May be C₁~ C_FourAlkyl group of; with a halogen atom
C which may be substituted₂~ C₃Alkenyl group; halo
C optionally substituted with a gen atom₁~ C₃The Archoki
Si group; C optionally substituted by a halogen atom₁~ C₃
Alkylthio group; may be substituted with halogen atom
I C₂~ C₃Alkenyloxy group; placed with a halogen atom
C that may be replaced ₂~ C₃An alkynyloxy group of
C optionally substituted with a halogen atom₂~ C _FiveThe al
Killcarbonyloxy group; hydrogen atom; halogen atom;
Ano group; nitro group; or each is C₁~ C_FourThe al
Kill group, C₁~ C_FourAlkoxy group, halogen atom,
Toro group, cyano group and trifluoromethyl group
A phenyl group which may have one or more substituents,
Phenoxy group, benzyl group, benzyloxy group, thiazo
Ryl group, thiazolyloxy group, pyridyloxy group, benzene
It represents a zoyl group or a benzothiazolyloxy group.

More preferably, X is an optionally substituted methyl group, an ethyl group, an i-propyl group, a t-butyl group; an optionally substituted methoxy group, an ethoxy group,
Optionally substituted propoxy group; optionally substituted methylthio group; optionally substituted vinyl group; optionally substituted phenyl group; optionally substituted phenoxy group; optionally substituted Good benzyl group; benzyloxy group; optionally substituted pyridyloxy group; hydrogen atom; fluorine atom, chlorine atom, bromine atom; cyano group; or nitro group, methyl group, methoxy group, propoxy group, methylthio group Examples of the substituent of the vinyl group include a fluorine atom and a chlorine atom, and examples of the substituents of the phenyl group, phenoxy group, benzyl group and pyridyloxy group include a methyl group, a butyl group; a methoxy group; a fluorine atom and a chlorine atom; And nitro group; cyano group; or trifluoromethyl group.

In X, adjacent substituents may combine together to form a condensed ring with the benzene ring, thiazole ring or the like of A. Examples of such a condensed ring include 2,3-dihydrobenzofuran residue, chroman residue, naphthalene residue, fluorene residue, anthraquinone residue, benzo-1,3-
Examples thereof include a dioxole residue and the like, and a 2,3-dihydrobenzofuran residue, a chroman residue and a naphthalene residue are preferable.

1 is 1 to 5, preferably 1 to 3, m is 1
2, n is 1 to 3, p is 1 to 4, preferably 1 to 3, r is 1
Represents an integer of ˜2, preferably 1 to 6. Specific examples of the compound of the present invention represented by the general formula (I) are shown in Tables 1 to 7 below, but the compound of the present invention is not limited thereto.

[0022]

[Table 1]

[0023]

[Table 2]

[0024]

[Table 3]

[0025]

[Table 4]

[0026]

[Table 5]

[0027]

[Table 6]

[0028]

[Table 7]

The compounds of the present invention are all novel compounds and are produced, for example, according to the following reaction scheme.

[0030]

[Chemical 9]

(In the above formula, R ₁ , R ₂ , W, q and A
Is as defined in the above general formula (I)) The compound represented by the above general formula (I) is
And a carboxylic acid represented by the general formula (III) or a reactive derivative thereof are reacted in the presence or absence of a solvent inert to the reaction.

The carboxylic acids represented by the general formula (III) used in the reaction or their reactive derivatives are represented by the general formula (II)
With respect to the pyrazole derivative represented by
It is used in the range of 1.5 equivalents, preferably 0.9 to 1.1 equivalents. This reaction can be carried out in the temperature range of -70 ° C to the boiling point of the solvent used, preferably -40 ° C to the boiling point of the solvent.

Examples of the carboxylic acids represented by the general formula (III) or their reactive derivatives include corresponding carboxylic acids, acid halides, acid halides such as acid chlorides, and carboxylic acid esters. be able to. Examples of the solvent used in the reaction include aromatic hydrocarbons such as benzene and toluene; halogenated hydrocarbons such as carbon tetrachloride and chloroform; aromatic halogenated hydrocarbons such as chlorobenzene; diethyl ether, tetrahydrofuran, Ethers such as dioxane; esters such as ethyl acetate; polar solvents such as dimethyl sulfoxide, dimethylformamide, water and the like.

In order to allow the present reaction to proceed smoothly, an appropriate reaction aid can be used depending on the kind of the carboxylic acid represented by the general formula (III) or its reactive derivative. As an example of the reaction aid, when a carboxylic acid is used as the compound represented by the general formula (III), a dehydrating agent such as ethoxyacetylene, dicyclohexylcarbodiimide, phosphorus pentoxide, or an acid anhydride is used. Is N
-Tertiary amines such as methylmorpholine and triethylamine; aromatic bases such as pyridine, picoline and N, N-diethylaniline; tertiary amines such as triethylamine when acid halides are used; pyridine and picoline Such as aromatic bases; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal hydrides such as sodium hydride; or alkali metal alcoholates such as sodium ethylate, and carboxylic acid esters In that case, an alkali metal alcoholate such as sodium ethylate can be used. These reaction auxiliaries are usually 0.01 to 2.0 with respect to the pyrazole derivative represented by the general formula (II).
The equivalent is used, preferably 0.9 to 1.1 equivalents.

The compound represented by the general formula (II), which serves as a starting material for the above reaction and serves as an important intermediate for the production of the compound of the present invention, is produced, for example, according to the following reaction formula.

[0036]

[Chemical 10]

(In the above reaction formula, R ₁ and R ₂ are as defined in the above general formula (I)) The compound represented by the general formula (IV) as a starting material for the above reaction is, for example, European Publication. It is produced by the method described in Japanese Patent Publication No. 433899 or a method similar thereto. The compound represented by the general formula (II) can be obtained by hydrogenating the compound represented by the general formula (IV) in the presence of a suitable solvent.

Examples of the solvent used in the reaction include aromatic hydrocarbons such as benzene and toluene; esters such as ethyl acetate; carboxylic acids such as acetic acid and formic acid; alcohols such as methanol and ethanol; tetrahydrofuran, dioxane and the like. Ethers; or polar solvents such as water. In order to allow this reaction to proceed smoothly, a catalyst such as palladium-carbon powder can be used.

The reaction temperature is selected from the range of 0 ° C. to the boiling point of the solvent used, and the reaction is preferably carried out at 10 to 70 ° C. The compounds of the present invention thus obtained are all novel and have excellent bactericidal activity. In particular, since it has an excellent control effect against disease fungi of various plants, it is useful as an agricultural and horticultural fungicide.

For example, rice blast ( Phricula)
ria oryzae ); rice blight ( Rhizoct)
nia solani ); various rust diseases of wheat ( Puc
Cinia recondita ); Powdery mildew of various crops ( Erysiphe graminis ) ;; Gray mold of vegetables and fruit trees ( Botrytis cin)
erea ); Diseases of various crops ( Phytophtho
It is useful as a fungicide for agricultural and horticultural use because it has a high activity against ra stance and the like and has extremely excellent permeability to plants.

The compounds of the present invention are also extremely useful for controlling plant diseases since they have low toxicity to humans and animals. In using the compound of the present invention as an agricultural and horticultural fungicide, this compound may be used as it is, but in order to effectively disperse the active ingredient in the application scene,
It is preferable to add an auxiliary agent according to a conventional method and use it in the form of an emulsion, a wettable powder, a powder or the like.

Examples of the solvent which is one of the auxiliary agents in the agricultural / horticultural germicide of the present invention include water, alcohols (methyl alcohol, ethyl alcohol, ethylene glycol, etc.), ketones (acetone, methyl ethyl ketone, cyclohexanone, etc.). ), Ethers (ethyl ether, dioxane, cellosolves, etc.), aliphatic hydrocarbons (kerosene, kerosene, fuel oil, etc.), aromatic hydrocarbons (benzene, toluene, xylene, solvent naphtha, methylnaphthalene, etc.), Halogenated hydrocarbons (dichloroethane, trichlorobenzene, carbon tetrachloride, etc.), acid amides (dimethylformamide, etc.), esters (ethyl acetate, butyl acetate, glycerin esters of fatty acids, etc.), nitriles (acetonitrile, etc.), etc. Suitable, one or more of these Mixture is used.

As the extender, clays such as kaolin and bentonite, talc such as talc and pyrophyllite, diatomaceous earth, mineral powder such as oxides such as white carbon and soybean powder, carboxymethyl cellulose (CMC). And the like are suitable, and one kind or a mixture of two or more kinds thereof is used. It may also be used as a surface active agent spreading agent, dispersant, emulsifier, or penetrant. Examples of the surfactant include nonionic surfactants (polyoxyethylene alkyl allyl ether, polyoxyethylene sorbitan monolaurate, etc.), cationic surfactants (alkyldimethylbenzyl ammonium chloride, alkylpyridinium chloride, etc.), Examples include anionic surfactants (alkylbenzene sulfonate, lignin sulfonate, higher alcohol sulfate), amphoteric surfactants (alkyl dimethyl betaine, dodecylaminoethylglycine, etc.). These surfactants are used as one kind or as a mixture of two or more kinds depending on the application.

When the agricultural or horticultural fungicide of the present invention is applied in the form of an emulsion, the compounds of the present invention 10 to 10 are used.
80 parts, preferably 10-70 parts, solvent 10-90 parts,
A mixture of 20 to 80 parts and a surfactant of 3 to 20 parts, preferably 5 to 15 parts, in an appropriate ratio is used as a raw material, which is diluted with water to a predetermined concentration at the time of use. Apply. When used in the form of a wettable powder, the compound of the present invention is 5 to 80 parts, preferably 10 to 70 parts and the extender 10 to 90 parts, preferably 20 to 80 parts and a surfactant 1 to 20 parts, preferably Is used by diluting 3 to 15 parts in an appropriate ratio and diluting the mixture with water or the like as in the case of the emulsion.

When used in the form of powder, 0.1 to 10 parts, preferably 1 to 5 parts, of the compound of the present invention is usually used as a bulking agent such as kaolin, bentonite and talc 90 to 99.9.
Parts, preferably 95 to 99 parts, uniformly mixed. The agricultural / horticultural germicide of the present invention can also be used as a mixture with other active ingredients that do not inhibit the germicidal effect of the present active ingredient, such as germicides, insecticides and acaricides.

The agricultural and horticultural germicide of the present invention can be suitably applied to both foliar application and water surface application. In the case of foliar application, it is usually diluted with water so as to contain 10 to 1000 ppm of emulsion or wettable powder, and 10 to 500 per 10 are.
Apply liters.

[0047]

EXAMPLES Next, the present invention will be explained more specifically with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist. In the following description, “part” means “part by weight”. The production of each of the compounds of the present invention synthesized in Production Examples was confirmed by elemental analysis, IR spectrum, NMR spectrum and the like.

Synthesis Example 1 [Synthesis of (E) -methyl 2- (1,3-dimethyl-4-hydroxypyrazol-5-yl) -3-methoxyacrylate] (E) -Methyl 2- (4-benzyloxy) To a solution of 56 g (17.7 mmol) of -1,3-dimethylpyrazol-5-yl) -3-methoxyacrylate in 560 ml of methanol, 5.3 g of 5% palladium-carbon powder was added and hydrogenated. After completion of the reaction, the mixture was filtered, and the filtrate was concentrated under reduced pressure.
The obtained residue was recrystallized in a system of methanol ethyl acetate-n-hexane to give pure (E) -methyl 2
-(1,3-Dimethyl-4-hydroxypyrazole-5
38 g of -yl) -3-methoxy acrylate was obtained. The yield was 94.8%. Melting point 172.7-173.4 ° C. NMR spectrum (300 MHz, CDCl ₃ , pp
m) 2.41 (3H, s), 3.77 (3H, s), 3.8
8 (3H, s), 4.0 (3H, s), 5.33 (H,
s), 7.78 (H, s)

Example 1 [(E) -Methyl 2- [4- (2,4-dichlorobenzoyloxy) -1,3-dimethylpyrazol-5-yl] -3-methoxyacrylate (Compound N in Table 9)
o. Synthesis of 7)] (E) -Methyl 2- (1,3-dimethyl-4-hydroxypyrazol-5-yl) 3-methoxyacrylate obtained in Synthesis Example 1 (0.6 g, 2.65 mmol), triethylamine. A solution of 32 g (3.17 mmol) in 10 ml of ethyl acetate was cooled with water to give 2,4-dichlorobenzoyl chloride (0.1 ml).
65 g (3.15 mmol) was added dropwise. After stirring at room temperature for 1 hour, the mixture was washed successively with water and saturated brine, dried over anhydrous sodium sulfate and concentrated. The residue was purified by silica gel chromatography (elution solvent; ethyl acetate / n-hexane = 1/1) and recrystallization (recrystallization solvent: ethyl acetate-n-hexane) to obtain (E) -methyl 2-.
[4- (2,4-dichlorobenzoyloxy) -1,3
1.04 g of -dimethylpyrazol-5-yl] -3-methoxyacrylate was obtained. The yield was 99%.

According to the method described in Example 1 above, Table 8
No. 18 to Compound No. 1-6,8-71 were manufactured.

[0051]

[Table 8]

[0052]

[Table 9]

[0053]

[Table 10]

[0054]

[Table 11]

[0055]

[Table 12]

[0056]

[Table 13]

[0057]

[Table 14]

[0058]

[Table 15]

[0059]

[Table 16]

[0060]

[Table 17]

[0061]

[Table 18]

Formulation Example 1 Compound Nos. Shown in Tables 8-12. 1 part 20 parts, diatomaceous earth 75
Parts and 5 parts of a surfactant containing alkylbenzene sulfonic acid as a main component were uniformly pulverized and mixed to obtain a wettable powder.

Formulation Example 2 Compound No. shown in Tables 8-12. 10 parts 40 parts, white carbon 10 parts, diatomaceous earth 47 parts, "Sorball" 503
3 parts of 9 (trademark of Toho Chemical Industry Co., Ltd., a surfactant containing polyoxyethylene alkylaryl ether sulfonate as a main component) was uniformly pulverized and mixed to obtain a wettable powder.

Formulation Example 3 Compound Nos. Shown in Tables 8-12. 5 to 30 parts, "Sorbol" 3005X (trademark of Toho Chemical Industry Co., Ltd., mixture of nonionic surfactant and anionic surfactant) 15
Parts, xylene 25 parts, and dimethylformamide 30 parts were mixed and dissolved to obtain an emulsion.

Formulation Example 4 Compound Nos. Shown in Tables 8-12. 2 parts of 1 and 98 parts of N, N-kaolin clay (manufactured by Tsuchiya Kaolin Co., Ltd.) were mixed and pulverized to obtain a powder.

Next, the usefulness of the compounds of the present invention as agricultural and horticultural fungicides will be clarified by giving test examples. The compounds of the present invention are shown by compound numbers in Tables 8 to 18, and the compounds used for comparison and control are shown in Table 19.

[0067]

[Table 19]

Test Example 1 Wheat Powdery Mildew Control Effect Test 1-2 leaf stages of seedlings grown in a pot with a diameter of 6 cm were cultivated in wheat (cultivar:
A water dispersible powder prepared in the same manner as in Formulation Example 1 was diluted with Norin 61) with water to a predetermined concentration and sprayed on foliage at a rate of 10 ml per pot. After air-drying the chemical solution, wheat powdery mildew ( Erysiphe gramin
After inoculation with a spore suspension obtained from a wheat leaf affected by is ), it was left in a greenhouse for 7 to 10 days.

For the evaluation, the diseased area ratio of each leaf was evaluated and the control value was calculated by the following formula. The results are shown in Tables 20-23.

[0070]

[Table 20]

[0071]

[Table 21]

[0072]

[Table 22]

[0073]

[Table 23]

Test Example 2 Effect on Tomato Phytophthora Three tomato plants (variety: red cherry) were grown in a resin pot having a diameter of 6 cm, and the wettable powder prepared in Formulation Example 1 at the 3 to 4 leaf stage. Was diluted to a prescribed concentration with water, and the resulting reagent was sprayed on the foliage at a rate of 10 ml per pot. After air-drying the sprayed chemical liquid, the tomato blight (Phytophthora i) was cultured on tomato cut leaves.
nfestans) spores were spray-inoculated, kept in a greenhouse at 20 ° C. for 24 hours, and then left in a water tank in the greenhouse for 2 days, and the lesion area in the emerging leaves was measured and shown by the disease index according to the following formula. The control value was calculated. The results are shown in Tables 24-27.

Disease occurrence index 0: No lesions 1: Lesion area 1/3 or less 3: Lesion area 1/3 to 2/3 5: Lesion area 2/3 or more n _x : the number of tomato leaves having the disease index of X per pot

[0076]

[Table 24]

[0077]

[Table 25]

[0078]

[Table 26]

[0079]

[Table 27]

[0080]

The compounds of the present invention thus obtained are all novel compounds and have excellent bactericidal activity. In particular, since it has an excellent control effect against disease fungi of various plants, it is useful as an agricultural and horticultural fungicide. For example, rice blast ( Phricularia oryza)
e ); Rice blight ( Rhizoctinia sola)
ni ); Various rust diseases of wheat ( Puccinia rec)
ondita ); powdery mildew of various crops ( Erysip
he graminis ); Botrytis cinerea ) such as vegetables and fruit trees; Phytophthora infestan of various crops
ce ) and the like, as well as having extremely high permeability to plants, they are useful as fungicides for agriculture and horticulture.

Further, the compound of the present invention has very little harmful effect on plants, and has low toxicity to human livestock or fish. Therefore, it is extremely useful for controlling plant diseases.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁵ Identification number Internal reference number for FI Technical indication C07D 409/12 231 8829-4C 417/12 231 9051-4C (72) Inventor Kazuhiko Kikutake Kanagawa Sanryo Kasei Co., Ltd., Ryōsei Kasei Co., Ltd. 1000, Kamoshida-cho, Midori-ku, Yokohama (72) Inventor Manami Sekine 1000, Kamoshita-cho, Midori-ku, Yokohama, Kanagawa

Claims (4)

[Claims] 1. The following general formula (I): (In the above formula, R ₁ and R ₂ each independently represent a hydrogen atom or a C ₁ -C ₅ alkyl group, and W is C ₁
~ C ₁ optionally substituted by a C ₄ alkyl group ~
A C ₄ alkylene group, a C _{2 to} C ₄ alkenylene group optionally substituted by a C _{1 to} C ₄ alkyl group, C ₂
To C ₄ alkynylene group, —O—, —S— or —NH
Represents-, q represents 0 or 1, and A is a C ₃ -C ₇ cycloalkyl group which may be optionally substituted, a C ₆ -C ₁₂ aryl group, or an oxygen atom, a sulfur atom or a nitrogen atom. Total number of atoms having 1 to 3 atoms 5 to 1
4 represents the heteroaryl group of 4). 2. A is the following: Or a C ₃ -C ₇ cycloalkyl group having r substituents X (X is a C ₁ -C ₅ alkoxy group,
A C _{1 to} C ₁₀ alkyl group which may have one or more substituents selected from a halogen atom, a nitro group, a cyano group and a trifluoromethyl group, a C _{2 to} C ₁₁ alkenyl group, and a C _{1 to} C group. ₁₀ alkoxy groups, C ₁ -C ₁₀ alkylthio groups, C ₂ -C ₁₁ alkenyloxy groups, C ₂ -C ₁₁
An alkynyloxy group, a C _{2 to} C ₁₁ alkylcarbonyl group or a C _{2 to} C ₁₁ alkylcarbonyloxy group; a C _{1 to} C ₅ alkyl group, a C _{1 to} C ₅ alkoxy group, a halogen atom, and nitro, respectively. group, one or more may have a substituent group C ₇ -C ₁₃ arylcarbonyl group selected from cyano group and a trifluoromethyl group,
Cycloalkylcarbonyl group of C ₄ ~C _9, C ₇
To C ₁₃ arylcarbonyloxy group, C _{6 to} C ₁₂ aryl group, C _{6 to} C ₁₂ aryloxy group, 1 to 3 oxygen atoms, sulfur atom, and nitrogen atom, and the total number of atoms is 5 to 1
4 of heteroaryl groups include 1 to 3 oxygen atoms, sulfur atoms, the heteroaryl group having a total atom number of 5 to 14 with a nitrogen atom, an aralkyl group or a C ₇ to C ₇ -C ₁₂ ~
C ₁₂ aralkyloxy group; hydrogen atom, halogen atom,
Represents a cyano group or a nitro group, 1 is 1 to 5 and m is 1
˜2, n is 1 to 3, p is 1 to 4, and r is an integer of 1 to 12. The two X's may together represent a condensed aromatic ring or a condensed heterocycle), and the compound according to claim 1. 3. A fungicide for agricultural and horticultural use containing the pyrazolyl acrylic acid derivative according to claim 1 as an active ingredient. 4. The following general formula (II): (In the above formula, R ₁ and R ₂ each independently represent a hydrogen atom or a C ₁ -C ₅ alkyl group).