JPH04217668A - Pyrazolylacrylic acid derivative, agricultural/ horticultural bactericide with the same as active ingredient and intermediate thereof - Google Patents

Abstract

PURPOSE:To provide the title novel, low toxic derivative having high bactericidal activity and plant penetrability in the form of an agricultural/horticultural bactericide. CONSTITUTION:The objective compound of formula I [R1 and R2 are each H or 1-5C alkyl; A is of formula II (X is 1-5C alkoxy, halogen, nitro, etc.), etc.; n is 1-5; B is methoxycarbonyl or cyano], for example, (E)-methyl 2-(4- benzyloxy-1,3-dimethyl pyrazole-5-yl)-3-methoxyacrylate. The present compound can be obtained by the following process: a compound of formula III as the starting material is reacted, in the presence of a base, with a compound of formula A-CH2hal (hal is halogen) into an important intermediate of formula IV, which is then reduced into an alcohol derivative followed by conversion, through an intermediate, into a compound of formula V. This compound is then reacted with a methylating reagent and a base.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel pyrazolylacrylic acid derivative, a fungicide for common use in farms containing the same as an active ingredient, and intermediates thereof.

[Prior art and problems to be solved by the invention] It has been known that certain acrylic acid derivatives have biological activities such as bactericidal effects.

For example, in European Patent Publication No. 178826,
A compound represented by the following formula is disclosed in JP-A-61-277652, and a compound represented by the following formula is also disclosed in JP-A-1-254669.
The publication describes that the compound represented by the following formula has bactericidal activity. However, as is clear from the test examples described later, none of these compounds has a bactericidal effect as an agricultural or horticultural fungicide. At present, its efficacy cannot always be said to be sufficient in terms of both activity and permeability.

[Means for solving problems]

The present inventors focused on such acrylic acid derivatives and, as a result of intensive studies, found that pyrazolyl acrylic acid derivatives having a specific structure have excellent fungicidal activity and excellent permeability to plants. This discovery led to the completion of the present invention.

That is, the gist of the present invention is the following general formula (I) [in the above formula,
R1 and R2 are each independently a hydrogen atom or C1
-C5 alkyl group (X is a C1-C10 alkyl group which may have one or more substituents selected from a C1-C5 alkoxy group, a halogen atom, a nitro group, a cyano group, and a trifluoromethyl group) alkyl group, C2-C11 alkenyl group, C1-C10 alkoxy group, C2-C
11 alkenyloxy group, C2-C11 alkynyloxy group, C2-C11 alkylcarbonyl group or C2-C11 alkylcarbonyloxy group; C1-
C7 which may have one or more substituents selected from C5 alkyl group, C1 to C5 alkoxy group, halogen atom, nitro group, cyano group and trifluoromethyl group
~C13 arylcarbonyl group, C4-C9 cycloalkylcarbonyloxy group, C7-C13 arylcarbonyloxy group, C6-C12 aryl group, C6
~C12 aryloxy group, a heteroaryl group having 5 to 14 total atoms having 1 to 3 oxygen atoms, sulfur atoms or nitrogen atoms, total atoms having 1 to 3 oxygen atoms, sulfur atoms or nitrogen atoms 5 to 14 heteroaryloxy groups, C7 to C12 aralkyl groups, or C7 to C12 aralkyl groups
C12 aralkyloxy group; represents a hydrogen atom, a halogen atom, a cyano group or a nitro group, n represents an integer of 1 to 5, and m represents an integer of 1 to 2. Note that two Xs may be combined to form a fused ring structure with a benzene ring or a thiazole ring. ), and B represents a methoxycarbonyl group or a cyano group. ), agricultural and horticultural fungicides containing this as an active ingredient, and intermediates thereof.

Hereinafter, the present invention will be explained in detail.

The compound of the present invention is represented by the above general formula (I). In the general formula (I), R1 and R2 each independently represent a hydrogen atom or a methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, t-butyl group, n-pentyl group, etc. represents a C1-C5 alkyl group. R1 preferably represents a hydrogen atom or a C1-C4 alkyl group, particularly preferably a methyl group or an ethyl group.

R2 preferably represents a hydrogen atom or a C1-C3 alkyl group, particularly preferably a methyl group, an ethyl group or a propyl group.

represent.

X is a methyl group, ethyl group, n-propyl group, iso-
C1-C10 alkyl groups such as propyl group, n-butyl group, t-butyl group, n-pentyl group; C2-C11 alkenyl groups such as vinyl group, allyl group, 1-propenyl group; methoxy group, ethoxy group , iso-propoxy group, n
- C1 to C10 alkoxy groups such as butoxy groups; C2 to C11 alkenyloxy groups such as vinyloxy, allyloxy, and 1-propenyloxy groups; C2 to C11 alkynyloxy groups such as propargyloxy groups; acetyl groups, propionyl group, C2-C11 alkylcarbonyl group such as butyryl group; benzoyl group, toluoyl group,
C7-C13 arylcarbonyl groups such as naphthol groups; C2-C11 alkylcarbonyloxy groups such as acetoxy groups, propionyloxy groups, butyryloxy groups;
C4-C9 cycloalkylcarbonyloxy groups such as cyclohexanecarbonyloxy groups; C7-C13 arylcarbonyloxy groups such as benzoyloxy and tolylcarbonyloxy groups; C6-C6 such as phenyl, tolyl, xylyl, and naphthyl groups C12 aryl group; C6 such as phenoxy group, tolyloxy group, naphthyloxy group
-C12 aryloxy group; heteroaryl group having 5 to 14 atoms in total having 1 to 3 oxygen atoms, sulfur atoms or nitrogen atoms such as thiazolyl group, benzothiazolyl group, pyridyl group, pyrazolyl group; pyridyloxy group, 1 to 3 of thiazolyloxy group, benzothiazolyloxy group, etc.
Heteroaryloxy group having a total number of atoms of 5 to 14 having 3 oxygen atoms, sulfur atoms or nitrogen atoms; benzyl group,
C7-C12 aralkyl group such as phenethyl group; C7-C12 aralkyloxy group such as benzyloxy group, phenethyloxy group; hydrogen atom; fluorine atom, chlorine atom,
Represents a halogen atom such as a bromine atom or an iodine atom; a cyano group; or a nitro group. The above alkyl group, alkenyl group, alkoxy group, alkenyloxy group, alkynyloxy group, alkylcarbonyl group, and alkylcarbonyloxy group are a C1 to C5 alkoxy group, a halogen atom, a nitro group, a cyano group, and a trifluoromethyl group, respectively. Optionally substituted with one or more substituents selected from arylcarbonyl group, cycloalkylcarbonyloxy group, arylcarbonyloxy group, aryl group, aryloxy group, heteroaryl group, heteroaryloxy group, aralkyl group, and an aralkyloxy group are a C1-C5 alkyl group and a C1-C5 alkyl group, respectively.
may be substituted with one or more substituents selected from an alkoxy group, a halogen atom, a nitro group, a cyano group, and a trifluoromethyl group.

X is preferably a C1-C4 alkyl group, which may have one or more substituents selected from a halogen atom, a nitro group, a cyano group, and a trifluoromethyl group;
3 alkenyl group, C1-C3 alkoxy group, C2-
C3 alkenyloxy group, C2-C7 alkynyloxy group, or C2-C5 alkylcarbonyloxy group; C1-C4 alkyl group, C1-C4 alkoxy group, halogen atom, nitro group, cyano group, and trifluoromethyl A phenyl group, a phenoxy group, a benzyl group, a benzyloxy group, a thiazolyl group, a thiazolyloxy group, a pyridyloxy group, a benzoyl group, or a benzothiazolyloxy group, which may have one or more substituents selected from the group ; Represents a hydrogen atom, a halogen atom, a cyano group or a nitro group.

More preferably, X is an optionally substituted methyl group or butyl group; an optionally substituted methoxy group, an ethoxy group, an optionally substituted propoxy group; an optionally substituted propenyloxy group; Propargyloxy group; butyryloxy group; optionally substituted phenyl group; optionally substituted phenoxy group; optionally substituted benzyl group; benzyloxy group; optionally substituted pyridyloxy group, thiazolyloxy group , benzothiazolyloxy group; benzoyl group; hydrogen atom; fluorine atom, chlorine atom, bromine atom: cyano group; substituents for phenyl, phenoxy, benzyl, and pyridyloxy groups include methyl, butyl, methoxy, fluorine, chlorine, nitro, cyano, and trifluoro. Examples include methyl group.

In addition, adjacent substituents of X may be combined to form a condensed ring with the benzene ring or thiazole ring of A. Such condensed rings include 2,3-dihydrobenzofuran, chroman, naphthalene, Preferred examples include fluorene, anthraquinone, and benzo-1,3-dioxole.

n represents an integer of 1 to 5, and m represents an integer of 1 to 2.

B represents a methoxycarbonyl group or a cyano group.

The compounds of the present invention are all new compounds, for example,
It is produced according to the following reaction scheme.

(In each of the above formulas, R1, R2, A and B are represented by the general formula (
As defined in I). ) The compound represented by the general formula (III) serving as the starting material for the above reaction is T
etrahedron Letters, No. 19,
1591-2 (1971) or a method similar thereto.

The general formula (IIa
) is prepared by adding the compound represented by the general formula (III) to the compound represented by the general formula A-CH2 in the presence of a base such as sodium hydride, potassium carbonate, or sodium ethylate.
-hal (where A is as defined above and h
al represents a halogen atom or a reactive leaving group such as toluenesulfonyloxy group or methanesulfonyloxy group. ) in a reaction-inert solvent such as dimethylformamide, dimethylsulfoxide, tetrahydrofuran, diisopropyl ether, etc.

The nitrile derivative (manufacturing intermediate) represented by the general formula (IIb) is obtained by converting the ester derivative represented by the general formula (IIa) into lithium aluminum hydride, sodium metal,
The alcohol derivative represented by the general formula (IV) is reduced by hydrogenation using sodium borohydride or various catalysts, and then halogenated using a halogenating agent such as hydrochloric acid, thionyl chloride, phosphorus oxychloride, or phosphorus tribromide. After making it into a derivative, it is manufactured using a cyanating agent such as sodium cyanide or potassium cyanide.

The reduction of the ester derivative represented by the above general formula (IIa) to the alcohol derivative represented by the above general formula (IV) is described in Organic Synthesis, Col.
Vol. II, p. 468; ibid, Col. Vol.
II, page 325; ibid, Col. Vol. IV, 8
This is carried out by the method described on page 34 or a method similar thereto.

The halogenation reaction of the alcohol derivative represented by the above general formula (IV) to the halogen derivative is carried out using Organic
Synthesis, Col. Vol. IV, page 576; ibid, Col. Vol. IV, page 169; Tet
rahadron Letters, No. 10, 9
01-904 (1978) or a method similar thereto.

The cyanation reaction to the nitrile derivative represented by the above general formula (IIb) is carried out by Organic Synthesis.
, Col. Vol. I, page 107;
o Ryoiki ZokanNo. 125, 155~
175 (1980) or a method similar thereto.

The nitrile derivative represented by the above general formula (IIb) is further reacted with methanol, water, etc. in the presence of hydrochloric acid or sulfuric acid, thereby leading to a methyl ester derivative also represented by the above general formula (IIb).

This reaction was described by J. Chem. Soc. 2417 (196
3);J. Org. Chem. , 23, 1225 (19
58); Ber. 105, 1778 (1972); Or
ganic Synthesis, Col. Vol. I
, (page 270) or a method similar thereto.

When the production intermediate represented by the above general formula (IIb) is reacted with methyl formate and a base in the presence or absence of a solvent inert to the reaction, a compound represented by the above general formula (V) or a salt thereof is obtained. is obtained. Then, when the compound represented by the above general formula (V) or a salt thereof is reacted with a methylating reagent and a base in the presence or absence of a solvent inert to the reaction, the desired general formula (I ) is obtained.

All reactions can be carried out at temperatures ranging from -78°C to the boiling point of the solvent used, but preferably from 0°C to 1°C.
React at 50°C.

Examples of solvents used include aromatic hydrocarbons such as benzene and toluene; halogenated hydrocarbons such as chlorobenzene; ethers such as diethyl ether and tetrahydrofuran; polar solvents such as dimethylformamide, dimethyl sulfoxide, and water; Examples include alcohols such as methanol, and mixed solvents thereof.

Examples of bases used in the reaction include tertiary amines such as N-methylmorpholine and triethylamine; aromatic bases such as pyridine, picoline, and N,N-diethylaniline; alkali metal hydroxides such as sodium hydroxide. Oxides; alkali metal hydrides such as sodium hydride; alkali metal alcoholades such as sodium methylate; alkali metal carbonates or alkali metal bicarbonates such as potassium carbonate and sodium hydrogen carbonate. Examples of the methylation reagent include methyl iodide and dimethyl sulfate.

The compound of the present invention can also be produced, for example, according to the following reaction formula.

(In the formula, R1, R2, A and B are as defined in the above general formula (I).) The compound of the above general formula (I) is a compound of the above general formula (VI), which corresponds to the compound of the above general formula (VI). It is obtained by reacting a Wittig reagent in a suitable solvent.

The Wittig reagent used in the reaction is obtained, for example, by reacting triphenylphosphonium halide obtained from methoxymethyl chloride with a base.

All reactions can be carried out at temperatures ranging from -78°C to the boiling point of the solvent used, but preferably at -20°C to 150°C.

Examples of bases used include alkali metal bases such as sodium hydride, sodium metal, sodium amide, sodium dimethylsulfone; alkali metal alcoholades such as sodium methylate; alkyllithiums such as butyllithium; tertiary bases such as triethylamine. Examples include amines.

Examples of the solvent used include ethers such as diethyl ether and tetrahydrofuran; polar solvents such as dimethylformamide and dimethyl sulfoxide.

The α-keto ester derivative represented by the above general formula (VI) is, for example, Synth. Commun. 11 943
(1981) or a method similar thereto.

That is, it can be obtained by reacting the corresponding pyrazolyl-magnesium halide derivative or pyrazolyl-lithium derivative with dimethyl oxalate.

Further, the α-ketoester derivative represented by the general formula (VI) is an acetate derivative represented by the general formula (IIb),
It can also be obtained by oxidation using a suitable oxidizing agent such as selenium dioxide.

The compounds of the present invention thus obtained are all novel compounds and have excellent bactericidal activity. In particular, it is useful as a fungicide for agriculture and horticulture because it has an excellent control effect against pathogens of various plants.

For example, rice blast disease (Phricularia or
yzae); rice sheath blight (Rhizoctonia s
olani); various rust diseases of wheat (Puccinia
powdery mildew of various crops (Ery recondita);
siphe graminis); Botrytis cinerea on vegetables, fruit trees, etc.; Phytophthora infes on various crops
It not only has high activity against
Because it has excellent permeability to plants, it is useful as a fungicide for agriculture and horticulture.

Furthermore, the compounds of the present invention have low toxicity to humans, livestock, and fish, and are therefore extremely useful for controlling plant diseases.

When using the compound of the present invention as a fungicide for agriculture and horticulture, the compound may be used as it is, but in order to effectively disperse the active ingredient at the time of application, an adjuvant may be added in accordance with a conventional method and an emulsion prepared. It is preferable to use it in the form of , wettable powder, powder, etc.

Examples of the solvent, which is one of the auxiliary agents in the agricultural and horticultural fungicide of the present invention, include water, alcohols (methyl alcohol, ethyl alcohol, ethylene glycol, etc.), ketones (acetone, methyl ethyl ketone, cyclohexanone, etc.), and ether. (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. are suitable, and one or two of these are suitable.
Mixtures of more than one species are used.

In addition, as fillers, mineral powders such as clays such as kaolin and bentonite, talcs such as talc and pyrophyllite, oxides such as diatomaceous earth and white carbon, and plants such as soybean powder and carboxymethyl cellulose (CMC) are used. suitable powders, and one or a mixture of two or more of these may be applied.

Additionally, surfactants may be used as spreading agents, dispersants, emulsifiers, and penetrants. Such surfactants include:
For example, nonionic surfactants (polyoxyethylene alkyl allyl ether, polyoxyethylene sorbitan monolaurate, etc.), cationic surfactants (alkyldimethylbenzylammonium chloride, alkylpyridinium chloride, etc.), anionic surfactants ( Examples include alkylbenzenesulfonates, ligninsulfonates, higher alcohol sulfates), amphoteric surfactants (alkyldimethylbetaine, dodecylaminoethylglycine, etc.).

These surfactants are used singly or as a mixture of two or more depending on the purpose.

When applying the agricultural and horticultural fungicide of the present invention in the form of an emulsion, 10 to 50 parts of the compound of the present invention, 10 to 80 parts of a solvent, and 3 to 20 parts of a surfactant are mixed in an appropriate ratio. The solution is made into a stock solution, which is diluted with water to a predetermined concentration before use, and applied by spraying or other methods.

In addition, when used in the form of a hydrating powder, the compounds of the present invention 5-
80 parts and 10-90 parts of filler and 1-20 parts of surfactant
The mixture is diluted with water or the like in the same manner as an emulsion and used.

When used in the form of a powder, it is usually a mixture of 1 to 5 parts of the compound of the present invention and 95 to 99 parts of a filler such as kaolin, petonite, and talc.

The agricultural and horticultural fungicide of the present invention can also be used in combination with other active ingredients that do not inhibit the fungicidal effect of the active ingredient, such as fungicides, insecticides, acaricides, etc.

The agricultural and horticultural fungicide of the present invention can be suitably applied to both foliar spraying and water surface application.In the case of foliar spraying, usually,
The emulsion or wettable powder may be diluted with water to contain 10 to 1000 ppm, and 10 to 500 liters of this may be applied per 10 ares.

〔Example〕

Next, the present invention will be explained in more detail by giving examples.
The present invention is not limited to the following examples unless it exceeds the gist thereof.

In the following description, "parts" indicate "parts by weight."

In addition, the production of all the compounds of the present invention synthesized in the production examples was confirmed by elemental analysis, IR spectrum, NMR spectrum, etc.

Synthesis Example 1 (E)-Methyl 2-(4-benzyloxy-1,3-
Synthesis of dimethyl-pyrazol-5-yl)-3-methoxyacrylate (Compound No. 1 listed in Table 1) 2 g (11.6 mmol) of ethyl 1,3-dimethyl-4-hydroxypyrazole-5-carboxylate (11.6 mmol) anhydrous Dimethylformamide (hereinafter abbreviated as "DMF") 5
0.47 g (11.8 mmol) of sodium hydride (60% dispersion in oil) was added to the ml solution under ice cooling. Then, 2 g (11.7 mmol) of benzyl bromide was added dropwise, and the mixture was stirred at room temperature for 1 hour. The reaction solution was poured into water and extracted with ethyl acetate. The extract was washed successively with water and saturated brine, and dried over anhydrous sodium sulfate. After concentration, the residue was purified by silica gel column chromatography (elution solvent: ethyl acetate/n-hexane = 1/4), ethyl 4
-benzyloxy-1,3-dimethylpyrazole-5-
2.5 g (9.1 mmol) of carboxylate was obtained.

(Yield 78%) NMR (90 MHz, CDCl3), 1
．． 35 (3H, t), 2.05 (3H, s), 4.05
(3H, s), 4.40 (2H, q), 5.0 (3H,
s), 7.45 (5H) Ethyl 4-benzyloxy-1,3-dimethylpyrazole-5-carboxylate 2.5 g (9.1 mmol)
anhydrous tetrahydrofuran (hereinafter abbreviated as "THF")
Add 0 lithium aluminum hydride to 15 ml solution under ice cooling.
．． 2 g (5.3 mmol) was added.

After stirring at room temperature for 1 hour, the reaction solution was poured into aqueous hydrochloric acid under cooling, extracted with ethyl acetate, and washed successively with water and saturated brine. After drying with anhydrous sodium sulfate, it was concentrated.

5 ml of toluene was added to 2 g of the residue, and 2 g of thionyl chloride was added. After heating under reflux for 1 hour, low-boiling substances were concentrated, ethyl acetate was added, and the mixture was washed successively with water, sodium hydrogen aqueous solution, water, and saturated brine.

It was dried over anhydrous sodium sulfate and then concentrated. The resulting residue was 1.9 g of dimethyl sulfoxide (hereinafter referred to as “DMSO
) 0.43g of sodium cyanide in 5ml solution
(8.8 mmol) was added, stirred at room temperature, and left overnight. The reaction solution was poured into water and extracted with ethyl acetate.

After sequentially washing with water and saturated brine, it was dried over anhydrous sodium sulfate.

The residue was purified by silica gel chromatography (elution solvent: ethyl acetate/n-hexane = 1/2),
(4-benzyloxy-1,3-dimethylpyrazole-
5-yl)acetonitrile 1.6g (6.6mmol)
I got it. (Yield 73%) NMR (90 MHz, CDCl
3), 2.2 (3H, s), 3.35 (3H, s), 3
．． 8 (3H, s), 4.9 (2H, s), 7.42 (5
H) Add (4-benzyloxy-1,
3-dimethylpyrazol-5-yl)acetonitrile 1
．． 6g (6.6mmol) was added. The mixture was heated under reflux for 6 hours, and low-boiling substances were distilled off. Ethyl acetate was added to the residue, and the mixture was washed successively with water, hydrogenated sodium chloride solution, water, and saturated brine. It was dried over anhydrous sodium sulfate and concentrated. The residue was purified by silica gel chromatography (elution solvent: ethyl acetate/n-hexane = 1/2) to obtain methyl (4-benzyloxy-
1,3-dimethylpyrazol-5-yl)acetate 0
．． 6 g (2.2 mmol) was obtained. (Yield 33%) NM
R (90MHz, CDCl3), 2.15 (3H, s)
, 3.5 (3H, s), 3.7 (3H, s), 4.88
(2H, s), 7.42 (5H) 0.5 Sodium hydride (60% dispersion in oil) suspended in 5 ml of anhydrous DMF
In 5 g (13.8 mmol), a solution of 2.5 g (9.1 mmol) of methyl (4-benzyloxy-1,3-dimethyl-pyrazol-5-yl) acetate and 15 g (250 mmol) of methyl formate in 10 ml of anhydrous DMF was added. It was added dropwise under ice cooling while keeping the temperature below 10°C. After stirring at room temperature for 2 hours, low-boiling substances were distilled off under reduced pressure, and the residue contained 2.5 g (18.1 mmol) of potassium carbonate and 2.3 g of dimethyl sulfate.
g (18.2 mmol) and 5 ml of DMF were added under water cooling. Stirred at room temperature for 3 hours. After distilling off low-boiling substances under reduced pressure, ethyl acetate was added to the residue, and the mixture was washed successively with water and saturated brine. After drying over anhydrous sodium sulfate, it was concentrated under reduced pressure, and the resulting residue was subjected to silica gel column chromatography (elution solvent: ethyl acetate/n-hexane = 1/
1), and 2.1 g of transparent oily substance was obtained (Table 1).
Compound No. 1) was obtained (yield 73%).

In the above reaction, the Z form (compound No. 2 listed in Table 1) is also obtained at the same time.

Compounds Nos. 3 to 8 and 12 to 115 shown in Table 1 were produced according to the method described in Synthesis Example 1 above.

Synthesis Example 2 (E)-Methyl 2-{1,3-dimethyl-4-[1-
Synthesis of (2-methylthiazol-4-yl)methyloxy]pyrazol-5-yl}-3-methoxyacrylate (compound No. 9 listed in Table 2) n-butyllithium 1.6 mol hexane solution under nitrogen atmosphere 3.5 ml was added to 2 g (5.84 mmol) of methoxymethyltriphenylphosphonium chloride in anhydrous TH.
F suspension solution. After stirring at room temperature for 30 minutes, methyl {1,3-dimethyl-4-[1-(2-methylthiazol-4-yl)methyloxy]pyrazole-5
-yl}glyoxalate 0.6g (1.95mmol
of anhydrous THF6mβ solution was added. After 2 hours, the reaction solution was poured into water and extracted with ethyl acetate. The extract was washed successively with water and saturated brine, and dried over magnesium sulfate.

After concentration, the residue was purified by silica gel column chromatography to obtain 0.25 g of the title compound (compound N listed in Table 1).
o. 9) was obtained as an oily substance. (Yield 38.1%) Compound N listed in Table 1 was prepared according to the method described in Synthesis Example 2 above.
o. 10 and 11 were produced.

In addition, by the method described in Synthesis Example 1 or Synthesis Example 2,
Compounds described in 2 can also be synthesized.

Table 4 shows intermediates of the compounds listed in Table 1 and their physical properties of sulfuric acid.

Among the compounds listed in Table-1, proton NMR spectrum data for specific compounds are shown in Table-3. Chemical shifts are given in ppm from tetramethylsilane.

The solvent is deuterated chloroform unless otherwise specified. The symbols in the table have the following meanings.

s = singlet d = goblet t = triplet q = quartet m = multiplet br = broad dd = double doublet Formulation Example 1 Compound No. 1 listed in Table-1. 20 parts of 1, diatomaceous earth for 75 minutes,
A hydrate was obtained by uniformly pulverizing and mixing 5 parts of a surfactant containing alkylbenzenesulfonic acid as a main component.

Formulation Example 2 Compound No. 2 listed in Table-1. 40 parts of 10, 10 parts of white carbon, 47 parts of diatomaceous earth, "Solbol" 5039 (
A hydrate was obtained by uniformly pulverizing and mixing 3 parts of a surfactant (trademark of Toho Chemical Industry Co., Ltd., surfactant whose main component is polyoxyethylene alkylaryl ether sulfonate).

Formulation Example 3 Compound No. 3 listed in Table-1. 30 parts of 15, 15 parts of "Solbol" 3005X (trademark of Toho Chemical Industry Co., Ltd., a mixture of nonionic surfactant and anionic surfactant),
An emulsion was obtained by mixing and dissolving 25 parts of xylene and 30 parts of dimethylformamide.

Production Example 4 Compound No. listed in Table-1. A powder was obtained by mixing and pulverizing 2 parts of 1 and 98 parts of N,N-kaolin clay (manufactured by Tsuchiya Kaolin Co., Ltd.).

Next, by giving test examples, the usefulness of the compound of the present invention as an agricultural and horticultural fungicide will be clarified.

The compounds of the present invention are indicated by the compound numbers in Table-1, and the compounds used for comparison are indicated by the compound symbols in Table-5.

Test Example 1 Wheat powdery mildew control effect test Seedlings of 1-2 leaf stage wheat (variety: Norin 61) were grown in pots with a diameter of 6 cm.
A hydrating powder prepared in the same manner as in Formulation Example 1 was diluted 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
After spray inoculation with a spore suspension obtained from wheat leaves infected with Erysiphe graminis,
It was left in the greenhouse for 7-10 days.

For evaluation, the diseased area ratio of each leaf was assessed and the control value was calculated using the following formula. The results are shown in Table-6.

Test Example 2 Wheat powdery mildew control effect test (penetration effect) Wheat seedlings at the 1-2 leaf stage grown in a greenhouse (variety: Norin 6)
No. 1) was immersed in a chemical solution prepared by diluting a wettable powder prepared in the same manner as in Formulation Example 1 with water to a predetermined concentration.

Two days later, wheat powdery mildew (Erysiphe graminis E.
After spray inoculation with a spore suspension obtained from wheat leaves infected with P. rysiphe graminis)
It was left for 10 days.

For evaluation, the lesion area ratio on each leaf was assessed, and the control value was calculated using the following formula. The results are shown in Table-7.

Test Example 3 Wheat rust control effect test Wheat seedlings at 1-2 leaf stage grown in pots with a diameter of 6 cm (variety: Norin No. 61)
Next, a hydrating powder prepared in the same manner as in Test Example 1 was diluted with water to a predetermined concentration and sprayed on foliage at a rate of 10 ml per pot.

After the chemical solution was air-dried, the leaves were sprayed with wheat red rust.

After the chemical solution was air-dried, a spore suspension obtained by grinding wheat infected with wheat rust (Puccinia recondita) was spray inoculated, and the mixture was incubated at 22°C.
After keeping it in a humid room for 15 hours, it was left in an aquarium in a greenhouse for 7 days.

For evaluation, the ratio of lesion area on each leaf was assessed and the control value was calculated using the following formula.

The results are shown in Table-8.

Test Example 4 Effect on Tomato Phytophthora fungi Three tomato plants (variety: Red Cherry) were grown per pot in resin pots with a diameter of 6 cm, and at the 3rd to 4th leaf stage, the hydrating agent prepared in Formulation Example 1 was added with water. The test chemical obtained by diluting it to a predetermined concentration was sprayed on foliage at a rate of 10 ml per pot. After air-drying the sprayed chemical solution, the tomato late blight fungus (Phytophthora blight) was cultured on cut tomato leaves.
Infestans) spores were spray inoculated, kept in a humid room at 20°C for 24 hours, and then left in a greenhouse aquarium for 2 days.The area of lesions that appeared on the leaves was measured and expressed as a disease index.
The control value was calculated using the following formula. The results are shown in Table-9.

Disease index: 0: No lesions 1: Lesion area 1/3 or less 3: 〃 1/3 to 2/3 5: 〃 2/3 or more nx: Tomato leaves with the above disease index of X per pot [Effects of the Invention] The compounds of the present invention thus obtained are all novel compounds and have excellent bactericidal activity. In particular, it is useful as a fungicide for agriculture and horticulture because it has an excellent control effect against pathogens of various plants.

For example, rice blast disease (Phricularia or
yzae); rice sheath blight (Rhizoctonia s
olani); various rust diseases of wheat (Puccinia
powdery mildew of various crops (Ery recondita);
siphe graminis); Botrytis sinerea on vegetables, fruit trees, etc.; Phytophthora infes on various crops
It is useful as an agricultural and horticultural fungicide because it not only has high activity against bacteria such as P. tance, but also has excellent permeability to plants.

Furthermore, the compounds of the present invention have low toxicity to humans, livestock, and fish, and are therefore extremely useful for controlling plant diseases.

Claims (3)

[Claims] Claim 1: The following general formula (I) [In the above formula, R1 and R2 each independently represent a hydrogen atom or a C1 to C5 alkyl group, (X is C
C1-C10 alkyl group which may have one or more substituents selected from 1-C5 alkoxy group, halogen atom, nitro group, cyano group and trifluoromethyl group, C2-C11 alkenyl group, C1 -C10 alkoxy group, C2-C11 alkenyloxy group, C2-C
11 alkynyloxy group, C2-C11 alkylcarbonyl group or C2-C11 alkylcarbonyloxy group; C1-C5 alkyl group, C1-C5 alkoxy group, halogen atom, nitro group, cyano group and trifluoromethyl group C7 to C13 arylcarbonyl group optionally having one or more substituents selected from C
4-C9 cycloalkylcarbonyloxy group, C7-
C13 arylcarbonyloxy group, C6-C12 aryl group, C6-C12 aryloxy group, 1-3
Total number of atoms with 5 oxygen atoms, sulfur atoms, and nitrogen atoms
~14 heteroaryl group, a heteroaryloxy group with a total of 5 to 14 atoms having 1 to 3 oxygen atoms, sulfur atoms, and nitrogen atoms, a C7 to C12 aralkyl group, or a C7 to C12 aralkyl group
7-C12 aralkyloxy group; represents a hydrogen atom, a halogen atom, a cyano group or a nitro group, n represents an integer of 1-5, and m represents an integer of 1-2. Note that two Xs may be combined to form a fused ring structure with a benzene ring or a thiazole ring. ), B
represents a methoxycarbonyl group or a cyano group. ] A pyrazolylacrylic acid derivative represented by 2. An agricultural and horticultural fungicide comprising the pyrazolylacrylic acid derivative according to claim (1) as an active ingredient. Claim 3: The following general formula (II) [In the above formula, R1, R2 and A are as defined in claim (1), and E is an ethoxycarbonyl group or -C
H2-B (B is as defined in claim (1))
represents. ] A pyrazole derivative represented by.