JP2000095778A - Pyrazole derivative, production thereof and horticultural bactericide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound useful as a horticultural bactericide. SOLUTION: This pyrazole derivative is a compound of formula I [R1 is H, a 1-6C alkyl or the like; R2 is H, a 1-4C alkyl or the like; R3 is OH, a (substituted)phenyl or the like; y is CH or N), e.g. 4-(imidazo-1-yl-3-(2,4- dichlorophenyl)pyrazole. The compound of the formula I is obtained by, as one of the preferable production methods, reacting (A) a compound of formula II [R3' is a (substituted)phenyl or the like] [e.g. 1-(2,4-dichlorophenyl)-2-(imidazo-1- yl)-3-(N,N-dimethylamino)-2-propen-1-one] with (B) a compound of the formula: R2-NHNH2 (e.g. hydrazine monohydrate) by preferably using 1.0-3 fold mole component B based on the component A in a solvent such as ethanol preferably at 10-110 deg.C, for usually 0.5-5 hr.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel pyrazole derivative which is useful as a fungicide for agricultural and horticultural use.

[0002]

2. Description of the Related Art As a compound similar to the present invention, a pyrazole derivative is described in JP-A-6-80665, but the 5-position is fixed to an alkylthio group, and a substituent such as the present invention is introduced. No disclosure of such pyrazole derivatives. Therefore, the pyrazole derivative of the present invention is a novel compound and is not known to have a fungicidal activity for agricultural and horticultural purposes.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel pyrazole derivative, a process for producing the same, and a fungicide for agricultural and horticultural use containing the same as an active ingredient.

[0004]

Means for Solving the Problems The present inventors have conducted studies to solve the above problems, and as a result, have found that a novel pyrazole derivative has a remarkable bactericidal activity for agricultural and horticultural use, and completed the present invention. did. That is, the present invention is as follows. According to a first aspect, the following formula (1):

[0005]

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[Wherein, R¹Is hydrogen atom, carbon atom number 1
Up to 6 alkyl groups, cycloalkyl having 3 to 8 carbon atoms
Represents a kill group or a haloalkyl group having 1 to 4 carbon atoms.
R ^TwoIs a hydrogen atom, an alkyl having 1 to 4 carbon atoms
Group, alkenyl group having 3 to 6 carbon atoms, 3 carbon atoms
Up to 6 alkynyl groups, haloalk having 1 to 4 carbon atoms
A kill group,-(CH_Two)_m-OR^Four,-(CH_Two)_m-O-
(CH_Two)_n-OR^Four, COR ^Four, COOR^Four, SO_TwoR^Five,
A substituted or unsubstituted phenyl group,-(CH_Two)_m−
R ⁶, A cycloalkyl group having 3 to 8 carbon atoms or carbon
Represents a haloalkenyl group having 3 to 6 atoms (here, R
^FourRepresents an alkyl group having 1 to 4 carbon atoms;
^FiveIs an alkyl group having 1 to 4 carbon atoms, 1 carbon atom
Up to 4 haloalkyl groups or substituted or unsubstituted
R represents a phenyl group;⁶Is a substituted or unsubstituted phenyl
And m and n represent an integer of 1 to 4. );
R^ThreeIs a hydroxyl group, a substituted or unsubstituted phenyl group,
Substituted or unsubstituted naphthyl group, -O- (CH_Two)_m-R
⁶, -O- (CH_Two)_m-OR⁶, 1 to 10 carbon atoms
An alkoxy group, a substituted or unsubstituted phenoxy group or
Represents a substituted or unsubstituted pyridyloxy group.
Contact, R^FourAnd m are as defined above. ); Y is CH
Or N. The pyrazole derivative represented by
Things. The second invention provides the following formula (2):

[0007]

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(Wherein R ^{3 ′} represents a substituted or unsubstituted phenyl group, naphthyl group or alkoxy group having 1 to 10 carbon atoms; y has the same meaning as described above). And the following equation (3):

[0009]

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The present invention relates to a process for producing a pyrazole derivative represented by the above formula (1), which comprises reacting a compound represented by the formula (wherein R ² has the same meaning as described above). A third invention provides the following equation (4):

[0011]

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(Wherein R ¹ , R ³ and y have the same meanings as described above) and the compound represented by the above formula (3) are reacted with each other. (1)
The present invention relates to a method for producing a pyrazole derivative represented by the formula: A fourth invention provides the following equation (5):

[0013]

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Wherein R ¹ , R ³ and y have the same meanings as defined above, and a compound represented by the above formula (3). (1)
The present invention relates to a method for producing a pyrazole derivative represented by the formula:

[0015] The fifth invention relates to a fungicide for agricultural and horticultural use containing the pyrazole derivative represented by the above formula (1) as an active ingredient.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. Compounds represented by the above formulas (1) to (5) [hereinafter, compounds corresponding to formulas (1) to (5) are referred to as compounds (1) to (5). ] And the like are as follows. [R ¹ ] R ¹ is a hydrogen atom,
Examples thereof include an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, and a haloalkyl group having 1 to 4 carbon atoms. (1) Examples of the alkyl group include linear or branched ones; preferably, the alkyl group has 1 to 1 carbon atoms.
Four; more preferably, CH ₃ , C
₂ H ₅ , t-Bu. (2) The cycloalkyl group preferably has 3 to 6 carbon atoms; more preferably, cyclopropyl. (3) The haloalkyl group, a chlorine atom, an iodine atom, a bromine atom, and a halogen atom such as a fluorine atom and a straight-chain or branched alkyl group having as substituents; preferably in CF ₃ is there.

[R ² ] R ² is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, an alkynyl group having 3 to 6 carbon atoms, a carbon atom The number 1 to 4 haloalkyl groups, — (CH ₂ ) _m —OR ⁴ ,
— (CH ₂ ) _m —O— (CH ₂ ) _n —OR ⁴ , COR ⁴ , CO
OR ⁴ , SO ₂ R ⁵ , phenyl group, — (CH ₂ ) _m —R ⁶ , cycloalkyl group having 3 to 8 carbon atoms, 3 to carbon atoms
Six haloalkenyl groups can be mentioned. (1) Examples of the alkyl group include linear or branched ones; preferably, the alkyl group has 1 to 1 carbon atoms.
Four; more preferably, CH ₃ , C
₂ H ₅ , n-Pr, iso-Pr. (2) Examples of the alkenyl group include linear or branched ones; preferably, the alkenyl group has 3 carbon atoms.
~ 6; more preferably, propenyl.

(3) Examples of the alkynyl group include straight-chain or branched ones; preferably those having 3 to 6 carbon atoms;
It is propynyl. (4) Examples of the haloalkyl group include linear or branched ones; preferably, CF ₃ , CH ₂
CF ₃ . (5) - in (CH _{2) m} -OR ^4, m is an integer from 1 to 4, but R ⁴ is alkyl group having 1 to 4 carbon atoms; preferably, m is 1 or 2 There, the alkyl group is CH _3. And the most preferred — (CH ₂ ) _m —O
R ⁴ is —CH ₂ —OCH ₃ .

(6)-(CH ₂ ) _m -O- (CH ₂ ) _n -O
In R ⁴ , m and n are integers from 1 to 4, and R ⁴ is an alkyl group having 1 to 4 carbon atoms; preferably, m is 1 or 2 and n is 1 to 3 And the alkyl group is CH ₃ . The most preferred - (CH _{2) m}
—O— (CH ₂ ) _n —OR ⁴ is —CH ₂ —O— (CH ₂ ) ₂
—OCH ₃ . (7) In COR ⁴ , R ⁴ is a linear or branched alkyl group having 1 to 4 carbon atoms;
OC ₂ H ₅ . (8) In COOR ⁴ , R ⁴ is a linear or branched alkyl group having 1 to 4 carbon atoms;
COOCH ₃ .

(9) In SO ₂ R ⁵ , R ⁵ represents an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms or a substituted or unsubstituted phenyl group. As the alkyl group, there may be mentioned a straight or branched; preferably, is CH _3. Examples of the haloalkyl group include a linear or branched alkyl group having a halogen atom such as a chlorine atom, an iodine atom, a bromine atom, and a fluorine atom as a substituent; preferably, CF ₃ . Examples of the phenyl group include those having no substituent or an alkyl group having 1 to 4 carbon atoms as a substituent. The position of the substitution is not particularly limited, but the substitution at the 4-position is preferable; as the alkyl group, CH ₃ is preferable. (10) Examples of the phenyl group include substituted and unsubstituted ones. Examples of the substituent include a halogen atom such as a chlorine atom, an iodine atom, a bromine atom and a fluorine atom; preferably, a chlorine atom.
And the substitution position is not particularly limited, but 4-position substitution is preferable.

(11) In-(CH ₂ ) _m -R ⁶ , m is an integer of 1 to 4, and R ⁶ represents a substituted or unsubstituted phenyl group; preferably, m is 1 to 3. is there. Examples of the substituent of the phenyl group include a halogen atom such as a chlorine atom, an iodine atom, a bromine atom and a fluorine atom; preferably a chlorine atom. And the substitution position is not particularly limited, but 4-position substitution is preferable. (12) The cycloalkyl group having 3 to 8 carbon atoms is preferably cyclopropyl, cyclobutyl or cyclohexyl. (13) Examples of the haloalkenyl group having 3 to 6 carbon atoms include those having a halogen atom such as a chlorine atom, an iodine atom, a bromine atom, and a fluorine atom as a substituent; The number is from 3 to 6; more preferably CF = CHI.

[R ³ ] As R ³ , a hydroxyl group, a phenyl group, a naphthyl group, —O— (CH ₂ ) _m —R ⁶ , —O— (C
H ₂ ) _m —O—R ⁶ , an alkoxy group having 1 to 10 carbon atoms, a phenoxy group, and a pyridyloxy group. (1) Examples of the phenyl group include substituted or unsubstituted ones. Examples of the substituent include a halogen atom, an alkyl group having 1 to 4 carbon atoms, and a 1 to 1 carbon atom.
Examples thereof include four alkoxy groups, haloalkyl groups having 1 to 4 carbon atoms, haloalkoxy groups having 1 to 4 carbon atoms, nitro groups, cyano groups, and phenyl groups. The substitution position is not particularly limited: 2- or / and 4-position substitution is preferred. Examples of the substituted halogen atom include a chlorine atom, an iodine atom, a bromine atom, a fluorine atom and the like; preferably, a chlorine atom and a fluorine atom. Examples of the substituted alkyl group include straight-chain or branched ones; preferably those having 1 to 4 carbon atoms; and more preferably CH ₃ .

The substituted alkoxy group may be straight-chain or branched.
A branch-like one; preferably carbon
Having 1 to 4 atoms; more preferably O
CH _ThreeIt is. As the substituted haloalkyl group, a straight-chain or
May be branched; preferably,
Having 1 to 4 carbon atoms; more preferred
Is CF _ThreeIt is. As the substituted haloalkoxy group,
Linear or branched; but preferred
At least one having 1 to 4 carbon atoms;
Or OCF_ThreeIt is. As the substituted phenyl group,
And substituted or unsubstituted phenyl groups.

(2) The naphthyl group may be substituted or
Unsubstituted ones can be mentioned. (3) -O- (CH_Two)_m-R⁶Wherein m is 1 to 4
An integer, R⁶Is a substituted or unsubstituted phenyl group
However, preferably, m is an integer from 1 to 3. Pheni
Substituents of the chlorine group, iodine atom, bromine atom
And halogen atoms such as fluorine atom
But preferably a chlorine atom. And its replacement
The position is not particularly limited, but 4-position substitution is preferred. (4) -O- (CH_Two)_m-OR⁶Where m is 1 or
Represents 2, R⁶Represents a substituted or unsubstituted phenyl group
Represents; preferably, m is 2. Substitution of phenyl group
Groups include chlorine, iodine, bromine and fluorine
Examples include halogen atoms such as atoms, nitro groups, and cyano groups.
Chlorine atoms are preferred as halogen atoms.
Good. (5) straight-chain or branched alkoxy groups
And preferably 5 carbon atoms.
And more preferably OC ₈H₁₇
It is.

(6) The phenoxy group may be substituted or unsubstituted. Examples of the substituent include a haloalkyl group having 1 to 4 carbon atoms and a nitro group. The substitution position is not particularly limited: 2- or / and 4-position substitution is preferred. The substituted haloalkyl group, there may be mentioned a straight or branched; preferably, is CF _3. (7) Examples of the pyridyloxy group include substituted and unsubstituted ones. Examples of the substituent include a nitro group. The substitution position is not particularly limited: 2- or / and 4-position substitution is preferred.

[R^{3 '}] R^{3 '}May have 1 to 1 carbon atoms
Zero alkoxy, phenyl, and naphthyl groups
be able to. (1) Linear or branched alkoxy groups
But preferably has 1 carbon atom.
OCH; more preferably OCH _Three, O
C_TwoH_Five, OC₈H₁₇It is. (2) Substituted or unsubstituted phenyl groups
Can be mentioned. As the substituent, one having 1 carbon atom
~ 4 alkoxy groups, C1-4 alkyl
Group, haloalkyl group having 1 to 4 carbon atoms, number of carbon atoms
1 to 4 haloalkoxy groups, phenyl groups, halogen atoms
And a nitro group and a cyano group. Substitution position
The position is not particularly limited: substitution at the 2- or / and 4-position is preferred.
Good. As the substituted alkoxy group, a linear or branched
But preferably a carbon atom
More preferably one to four;
_ThreeIt is. As the substituted alkyl group, linear or branched
But preferably a carbon atom
More preferably from 1 to 4; more preferably CH_Three
It is.

The substituted haloalkyl group may be straight-chain or
Branched ones can be mentioned; preferably, charcoal is used.
Having 1 to 4 elementary atoms; more preferably,
CF _ThreeIt is. As the substituted haloalkoxy group, a linear
Or a branched one; preferably
Is one having 1 to 4 carbon atoms; more preferred
Or OCF_ThreeIt is. As the substituted halogen atom, a salt
Including iodine, iodine, bromine, and fluorine
But preferably a chlorine atom and a fluorine atom.
I am a child. Substituted or unsubstituted phenyl groups
And a substituted phenyl group. (3) A substituted or unsubstituted naphthyl group
Can be mentioned.

[Y] y is CH, N; preferably CH. As the compound (1), compounds obtained by combining the above-mentioned various substituents can be mentioned, and preferable compounds from the viewpoint of drug efficacy are as follows.

(1) A compound wherein R ¹ is a hydrogen atom, R ² is an alkyl group having 1 to 4 carbon atoms, R ³ is a substituted or unsubstituted phenyl group, and y is CH. For example, compounds 1 to 5, 28 and the like can be mentioned. (2) R ¹ and R ² are an alkyl group having 1 to 4 carbon atoms, and R ³ is —O— (CH ₂ ) _m —R ⁶ (where R ⁶ is a substituted or unsubstituted phenyl group And y is CH
What is. For example, compounds 47, 48, 52, 54,
55, 60 and the like. (3) R ¹ and R ² are an alkyl group having 1 to 4 carbon atoms, and R ³ is —O— (CH ₂ ) _m —O—R ⁶ (where R ⁶ is as defined above). ) And y is CH. For example, compound 58 and the like can be mentioned.

(4) R ¹ is a hydrogen atom, R ² is an alkenyl group having 3 to 6 carbon atoms, R ³ is a phenyl group, and y is CH. For example, compound 6 and the like can be mentioned. (5) R ¹ is a hydrogen atom, R ² is an alkynyl group having 3 to 6 carbon atoms, R ³ is a phenyl group, and y is C
What is H. For example, compound 7 and the like can be mentioned. (6) R ¹ is a hydrogen atom, R ² is an alkyl group having 1 to 4 carbon atoms, and R ³ is —O— (CH ₂ ) _m —R ⁶ (where R ⁶ is substituted or unsubstituted) Represents a substituted phenyl group.)
And y is CH. For example, Compound 56 and the like can be mentioned.

(7) R ¹ is a hydrogen atom, R ² is a haloalkenyl group having 3 to 6 carbon atoms, R ³ is a phenyl group, and y is CH. For example, Compound 64 and the like can be mentioned. (8) R ¹ and R ² are an alkyl group having 1 to 4 carbon atoms, R ³ is an alkoxy group having 1 to 10 carbon atoms, and y is CH. For example, compound 50 and the like can be mentioned. R ¹ , R ² , R ³ ,
Preferred examples of y, m and n include those described above and more preferred.

[Synthesis of Compound (1)] The above formula (1)
As a preferable method for producing a pyrazole derivative represented by the following, in addition to the synthetic methods 1, 2, and 3 described as the second, third, and fourth inventions, the following two types of production methods (synthetic methods 4 and 5) Can be mentioned. (Synthesis method 4) The following formula (1-1):

[0033]

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(Wherein R ¹ , R ³ and y are as defined above) and the following formula (6):

[0035]

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Wherein X represents a halogen atom;
² has the same meaning as described above. ) Or the following equation (7):

[0037]

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(Wherein R ² has the same meaning as described above). A process for producing a pyrazole derivative represented by the above formula (1), characterized by reacting with a compound represented by the following formula (1). (Synthesis method 5)

[0039]

Embedded image The following formula (1-2):

(Wherein R ¹ , R ² and y are as defined above) and the following formula (7):

[0041]

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Wherein R ³ has the same meaning as defined above;
Represents a halogen atom. A method for producing a pyrazole derivative represented by the above formula (1), which comprises reacting a compound represented by the formula (1). The synthesis methods 1 to 5 of the compound (1) of the present invention will be described in more detail.

(Synthesis Method 1) Synthesis method 1 is a method of reacting compound (2) with compound (3) in a solvent to obtain compound (1). The type of the solvent is not particularly limited as long as it does not directly participate in the reaction.For example, benzene, toluene, xylene, methylnaphthalene, petroleum ether, ligroin, hexane, chlorobenzene, dichlorobenzene, chloroform, dichloroethane, Chlorinated or unchlorinated aromatic, aliphatic, cycloaliphatic hydrocarbons such as trichloroethylene; diethyl ether,
Ethers such as tetrahydrofuran and dioxane; alcohols such as methanol, ethanol and ethylene glycol; N, N-dimethylformamide, dimethylsulfoxide, N, N-dimethylimidazolidinone, N-methylpyrrolidone and the like Such aprotic polar solvents; and mixtures of the above solvents.

The amount of the solvent used is 5 to 80 for compound (2).
Weight percent can be used; however, 10
~ 70% by weight is preferred. The reaction temperature is not particularly limited, but is in the range of room temperature to the boiling point of the solvent used or lower; The reaction time varies depending on the concentration and temperature in the previous period; it is usually 0.5 to 5 hours. The compound (3) is used in an amount of 1.0 to 5 times the molar amount of the compound (2);
Double molar is preferred. Compound (2) used in the present invention is J
ownnal of the American Ch
electronic Society, 1980, 102
Vol., Page 2838.
As the compound (3), a commercially available product can be used. After completion of the reaction, the target compound (1) produced as described above is subjected to ordinary post-treatments such as extraction, concentration and filtration, and if necessary, by known means such as recrystallization and various types of chromatography. It can be refined appropriately.

(Synthesis method 2) In the synthesis method 2, the compound (4) and the compound (3) are reacted in a solvent to obtain the compound (1). Examples of the type of the solvent include the ethers described in Synthetic Method 1, chlorinated or non-aromatic, aliphatic, alicyclic hydrocarbons, alcohols, aprotic polar solvents, and Mixtures can be mentioned. The amount of the solvent to be used may be such that the amount of the compound (4) is 5 to 80% by weight; however, it is preferably 10 to 70% by weight. The reaction temperature is not particularly limited, but is within a temperature range from room temperature to the boiling point of the solvent used or less;
0-110 ° C is preferred. The reaction time varies depending on the concentration and temperature in the previous period; it is usually 0.5 to 5 hours. The amount of the starting compound used is 1.0 to 5 times mol of the compound (3) with respect to the compound (4); preferably 1.0 to 3 times mol. Compound (4) was prepared according to Czech. Che
m. Pap. , 1993, 47 (1), 41-44. After completion of the reaction, the target compound (1) produced as described above is extracted,
It can be subjected to ordinary post-treatments such as concentration and filtration, and if necessary, can be appropriately purified by known means such as recrystallization and various types of chromatography.

(Synthesis Method 3) Synthesis method 2 is a method of reacting compound (5) with compound (3) in a solvent to obtain compound (1). Examples of the type of the solvent include the ethers described in Synthetic Method 1, chlorinated or non-aromatic, aliphatic, alicyclic hydrocarbons, alcohols, aprotic polar solvents, and Mixtures can be mentioned. The amount of the solvent to be used may be such that the amount of the compound (5) is 5 to 80% by weight; however, it is preferably 10 to 70% by weight. The reaction temperature is not particularly limited, but is within a temperature range from room temperature to the boiling point of the solvent used or less;
0-110 ° C is preferred. The reaction time varies depending on the concentration and temperature in the previous period; it is usually 0.5 to 5 hours. The compound (3) is used in an amount of 1.0 to 5 moles, preferably 1.0 to 3 moles, based on the compound (5). Compound (5) was prepared according to Synth. Comm
un. , 1984, pp. 1045-1047. After completion of the reaction, the target compound (1) produced as described above is subjected to ordinary post-treatments such as extraction, concentration and filtration, and if necessary, by known means such as recrystallization and various types of chromatography. It can be refined appropriately.

(Synthesis Method 4) The synthesis method 4 comprises the compound (1-
1) and compound (6) or compound (7) in a solvent,
This is a method of reacting in the presence of a base to obtain compound (1). Examples of the type of the solvent include those described in Synthesis Method 1 and water. The amount of the solvent used depends on the amount of the compound (1-
1) can be used in an amount of 5 to 80% by weight; however, 10 to 70% by weight is preferable. The type of base is not particularly limited, and organic bases such as organic bases such as triethylamine, pyridine, 4- (N, N-dimethylamino) pyridine, N, N-dimethylaniline, and DBU; sodium methoxide; Potassium-t-
Alkali metal alkoxides such as butoxide;
Inorganic bases such as hydroxides, hydrides, carbonates and bicarbonates of alkali metals and alkaline earth metals can be mentioned. The amount of the base to be used is 1 to compound (1-1).
５5 moles, preferably 1.2 to 2.0 moles. The reaction temperature is not particularly limited, but is within a temperature range from room temperature to the boiling point of the solvent used or less;
C is preferred. The reaction time varies depending on the concentration and temperature in the previous period; it is usually 0.5 to 5 hours. The amount of the starting compound used is 1.0 to 5 times mol of the compound (5) or the compound (6) with respect to the compound (1-1);
It is preferably from 0 to 3 moles. As the compound (6) and the compound (7), commercially available products can be used. The target compound (1) produced as described above, after completion of the reaction,
It can be subjected to ordinary post-treatments such as extraction, concentration and filtration, and if necessary, can be appropriately purified by known means such as recrystallization and various types of chromatography.

(Synthesis Method 5) The synthesis method 5 comprises the compound (1-
In this method, compound (1) is obtained by reacting 2) with compound (8) in a solvent in the presence of a base. Examples of the type of the solvent include those described in Synthesis Method 1 and water. The amount of the solvent to be used may be such that the compound (1-2) is 5 to 80% by weight;
0% by weight is preferred. Examples of the type of the base include those described in Synthesis Method 3. The amount of the base to be used is 1 to 5 moles compared to Compound (1-2);
A 2- to 2.0-fold molar amount is preferred. The reaction temperature is not particularly limited, but is in the range of room temperature to the boiling point of the solvent used or lower; The reaction time varies depending on the concentration and temperature in the previous period; it is usually 0.5 to 5 hours. The compound (8) is used in an amount of 1.0 to 5 times the molar amount of the compound (1-2);
1.0 to 3 times mol is preferable. As the compound (8), a commercially available product can be used. After completion of the reaction, the target compound (1) produced as described above is subjected to ordinary post-treatments such as extraction, concentration and filtration, and if necessary, by known means such as recrystallization and various types of chromatography. It can be refined appropriately.

[Control effect] The pathogen for agricultural and horticultural use which is effective in controlling the compound (1) of the present invention includes, for example,
Wheat red rust fungus, barley powdery mildew, cucumber gray mold, cucumber downy mildew, rice blast fungus, tomato late blight fungus and the like. (Pest control agent) The fungicide for agricultural and horticultural use of the present invention contains at least one compound (1) as an active ingredient. Compound (1) can be used alone,
Usually, a carrier, a surfactant, a dispersant, an auxiliary agent, and the like are blended by a usual method (for example, a powder, an emulsion, a fine granule, a granule,
(Prepared as a composition such as a wettable powder, an oily suspension, or an aerosol).

Examples of the carrier include solid carriers such as talc, bentonite, clay, kaolin, diatomaceous earth, white carbon, vermiculite, slaked lime, silica sand, ammonium sulfate, and urea; hydrocarbons (kerosene, mineral oil, etc.); Hydrogen (benzene, toluene, xylene, etc.), chlorinated hydrocarbons (chloroform, carbon tetrachloride, etc.), ethers (dioxane, tetrahydrofuran, etc.), ketones (acetone, cyclohexanone, isophorone, etc.), esters (ethyl acetate, ethylene Liquid carriers such as glycol acetate, dibutyl maleate, etc.), alcohols (methanol, n-hexanol, ethylene glycol, etc.), polar solvents (dimethylformamide, dimethyl sulfoxide, etc.), water, etc .; air, nitrogen, carbon dioxide, freon, etc. Body carrier (in this case, can be mixed injection) out and the like.

Surfactants and dispersants which can be used to improve the performance of the agent, such as adhesion to animals and plants, improvement in absorption, and dispersion, emulsification and spreading of drugs, include, for example, alcohol sulfates, alkyl sulfates and the like. Sulfonate, lignin sulfonate, polyoxyethylene glycol ether and the like can be mentioned. And the properties of the formulation
For improvement, for example, carboxymethylcellulose, polyethylene glycol, gum arabic and the like can be used as adjuvants. In the production of the present agent, the above-mentioned carrier, surfactant, dispersant, and auxiliary can be used alone or in appropriate combination according to the respective purposes. When the compound (1) of the present invention is formulated, the concentration of the active ingredient is usually 1 to 50% by weight for emulsions, usually 0.3 to 25% by weight for powders, and usually 1 to 90% for wettable powders.
% By weight, usually 0.5 to 5% by weight for granules, 0.5 to 5% by weight for oils and 0.1 to 5% by weight for aerosols. These preparations can be diluted to an appropriate concentration and applied to various uses by spraying them on plant foliage, soil, or the water surface of paddy fields, or directly applying them, depending on the purpose.

[0052]

EXAMPLES The present invention will be specifically described below with reference examples and examples. Note that these do not limit the scope of the present invention. Reference Example 1 [Synthesis of α-imidazo-1-yl acetoacetic acid methyl ester] To a 200 ml ethanol solution of 54.5 g (0.88 mol) of imidazole was added 155 g (0.88 mol) of a 28% sodium methylate methanol solution, and the mixture was added for 20 minutes. After stirring at room temperature, the solvent was distilled off and the residue was thoroughly dried. The residue is treated with N, N-dimethylformamide 100
Then, a solution of methyl α-chloroacetoacetate in 50 ml of N, N-dimethylformamide was added dropwise over 1 hour while slowly generating heat, followed by stirring at room temperature for 5 hours. After the completion of the reaction, 200 ml of ethyl acetate was added, and the mixture was further stirred at room temperature for 20 minutes. The obtained residue was purified by silica gel chromatography to obtain 73 g of the desired product (yield 46%).

¹ H-NMR (CDCl ₃ , δ ppm) 1.86 (s, 3H), 3.75 (s, 3H), 6.80
(S, 1H), 7.12 (s, 1H), 7.41 (s, 1
H)

Example 1 [Synthesis of Compound (1)] (1) 4- (imidazo-1-yl) -3 (5)-(2
Synthesis of 4-dichlorophenyl) -1-n-propylpyrazole [compound 4] Potassium carbonate was added to a solution of 1.40 g (5 mmol) of 4- (imidazo-1-yl) -3- (2,4-dichlorophenyl) pyrazole in 10 ml of acetonitrile. .69g (5
mmol) and 1.02 g (6 mmol) of n-propyl iodide
l) was added and the mixture was refluxed under heating for 1 hour. After cooling to room temperature, water 20
Then, the mixture was extracted twice with 10 ml of ethyl acetate. The combined organic layer was washed with saturated saline, dried over sodium sulfate, and evaporated under reduced pressure. The obtained residue is purified by silica gel column chromatography to give 4- (imidazo-1-yl) -3- (2,4-dichlorophenyl).
0.27 g (yield 17%) of a mixture of -1-n-propylpyrazole and 4- (imidazo-1-yl) -5- (2,4-dichlorophenyl) -1-n-propylpyrazole in a ratio of 2: 1 was obtained. Obtained.

4- (imidazo-1-yl) -3- (2,
4-Dichlorophenyl) -1-n-propylpyrazole ¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm) 1.03 (t, 3H), 1.99 (m, 2H), 4.1
7 (t, 2H), 6.83 (s, 1H), 7.06
(S, 1H), 7.35 (m, 4H), 7.63 (s,
1H)

4- (imidazo-1-yl) -5- (2,
4-dichlorophenyl) -1-n-propylpyrazole ¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm) 0.84 (t, 3H), 1.80 (m, 2H), 3.8
8 (m, 2H), 6.86 (s, 1H), 7.03
(S, 1H), 7.35 (m, 4H), 7.69 (s,
1H)

(2) 1-methyl-3 (5)-(3,4-
Dichlorophenyl) -4- (1-imidazolyl) -3
Synthesis of (5) -methyl-pyrazole [compound 40] (3,4-dichlorophenacyl) -imidazole 2.0
g (7.8 mmol), 4.8 g of trimethyl orthoacetate
(0.04 mol), zinc chloride 0.16 g (1.2 mm
ol) in 8 g (0.08 mol) of acetic anhydride,
The mixture was stirred under reflux for an hour. After completion of the reaction, the solvent was distilled off under reduced pressure.
2- (1-imidazolyl) -3-methoxy- as residue
3 ', 4' Dichrocrotonofenone was obtained. 100 ml of methanol and 1 g of methylhydrazine (2 g
2 mmol), and the mixture was heated and stirred at about 60 ° C. for 4 hours.
After completion of the reaction, the solvent was evaporated under reduced pressure, and the residue was purified by silica gel chromatography to give 4- (imidazo-1-yl) -3- (2,4-dichlorophenyl) -1- as a pale brown viscous substance. 80 mg of a mixture of methyl-5-methyl-pyrazole and 4- (imidazo-1-yl) -5- (2,4-dichlorophenyl) -1-methyl-5-methyl-pyrazole in a ratio of 1: 1 was obtained.

4- (imidazo-1-yl) -3- (2,
4-Dichlorophenyl) -1-methyl-5-methyl-pyrazole ¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm) 2.27 (s, 3H), 3.91 (s, 3H), 6.8
4 (s, 1H), 7.08 (s, 1H), 7.35
(M, 3H), 7.51 (s, 1H)

4- (imidazo-1-yl) -5- (2,
4-Dichlorophenyl) -1-methyl-5-methyl-pyrazole ¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm) 2.23 (s, 3H), 3.67 (s, 3H), 6.8
1 (s, 1H), 7.05 (s, 1H), 7.35
(M, 3H), 7.52 (s, 1H)

(3) Synthesis of 3- (4-chlorobenzyl) oxy-4- (imidazo-1-yl) -5-methylpyrazole [compound 52] α-imidazo-1-yl acetoacetic acid methyl ester 7
3 g (0.40 mol) of an ethanol solution (200 m
l) was added to hydrazine monohydrate 40.1 g (0.80 mo)
l) was added and the mixture was stirred at room temperature for 3 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, and the residue was reconstituted with ethanol / ethyl acetate to give 3-oxo-4- (imidazo-1-yl).
42 g of -5-methylpyrazoline were obtained. 3-Okipo 4-
(Imidazo-1-yl) -5-methylpyrazoline 3.7
1.8 g (45 mmol) of sodium hydroxide were added to 20 ml of an aqueous solution of g- (23 mmol), and then di-n-
40 g (45 mmol) of propyl sulfuric acid was added dropwise, and the mixture was stirred at room temperature. After completion of the reaction, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel chromatography to give 3-hydroxy-4- (imidazo-1-yl)-.
1.5 g of 5-methylpyrazole were obtained. To a solution of 0.50 g (2.4 mmol) of 3-hydroxy-4- (imidazo-1-yl) -5-methylpyrazole in 10 ml of N, N-dimethylformamide was added potassium-t-butoxide 0.1 ml.
30 g (2.7 mmol) and 0.40 g (2.5 mmol) of 4-chlorobenzyl chloride were sequentially added, and the mixture was stirred at room temperature. After the completion of the reaction, toluene was added, washed with water,
The toluene layer was dried over sodium sulfate, the solvent was distilled off, and the residue was purified by silica gel column chromatography to obtain 0.30 g (yield 37%) of the desired product.

¹ H-NMR (CDCl ₃ , δ ppm) 0.94 (t, 3H), 1.84 (m, 2H), 2.15
(S, 3H), 3.88 (t, 2H), 5.19 (s, 2
H), 6.96 (s, 1H), 7.15 (s, 1H),
7.29 (s, 4H), 7.51 (s, 1H)

(4) 4- (imidazo-1-yl) -3-
(2,4-dichlorophenyl) pyrazole [compound 6
Synthesis of 3] A solution of 30.0 g (118 mmol) of α- (imidazo-1-yl) -2,4-dichloroacetophenone in 17 g (140 mmol) of DMF dimethylacetal was stirred at 60 ° C. for 1 hour. After cooling, 100 ml of water was added, and the mixture was extracted twice with 30 ml of ethyl acetate. The combined organic layer was washed with saturated saline, dried over sodium sulfate, and evaporated under reduced pressure.
The obtained 1- (2,4-dichlorophenyl) -2- (imidazo-1-yl) -3- (N, N-dimethylamino)
37 g of 2-propen-1-one was used for the next reaction without purification. Hydrazine monohydrate 9 was added to a solution of 20 g of 1- (2,4-dichlorophenyl) -2- (imidazo-1-yl) -3- (N, N-dimethylamino) -2-propen-1-one in 140 ml of ethanol. 0.7g
(194 mmol), and the mixture was stirred at room temperature for 30 minutes, and then heated under reflux for 2 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, and the residue was dissolved in ethyl acetate. The extract was washed successively with water and saturated saline, the organic layer was dried over sodium sulfate, and evaporated under reduced pressure. The obtained residue was purified by silica gel column chromatography to give 13.8 g of the desired product (yield 7).
6%).

¹ H-NMR (300 MHz, d6-DMS
O / CDCl ₃ ) δ (ppm) 6.89 (t, 1H), 7.04 (t, 1H), 7.3
0 (m, 2H), 7.43 (s, 1H), 7.43
(S, 1H), 7.76 (s, 1H)

(5) Other compounds (1) in Tables 1-4
According to the methods described in the above (1) to (4), other compounds (1) in Tables 1 to 4 were synthesized. Compound (1) synthesized as described above [These compounds (1) are referred to as compounds 1 to 66 as shown in these tables. For example,
Compound 1 has a compound A and compound B formation ratio of 1: 0.
R ¹ in the compound (1) is a hydrogen atom, R ²
Is a methyl group, R ³ is 2,4-dichlorophenyl, y is C
H. ] Are shown in Tables 1 to 6 together with the formation ratio and physical properties of compound A and compound B.

[0065]

[Table 1]

[0066]

[Table 2]

[0067]

[Table 3]

[0068]

[Table 4]

[0069]

[Table 5]

[0070]

[Table 6]

Example 2 [Preparation of preparation] (1) Preparation of granules 5 parts by weight of compound (1), 35 parts by weight of bentonite, 57 parts by weight of talc, Neorex powder (trade name; manufactured by Kao Corporation) 1 Parts by weight and sodium lignin sulfonate 2
The parts by weight were uniformly mixed, and then a small amount of water was added and kneaded, followed by granulation and drying to obtain granules.

(2) Preparation of wettable powder 10 parts by weight of compound (1), 70 parts by weight of kaolin, 18 parts by weight of white carbon, 1.5 parts by weight of Neorex powder (trade name, manufactured by Kao Corporation) and Demol 0.5 parts by weight (trade name, manufactured by Kao Corporation) were uniformly mixed and then pulverized to obtain a wettable powder.

(3) Preparation of emulsion 10 parts by weight of compound (1), N-methylpyrrolidone 30
To 10 parts by weight of xylene and 40 parts by weight of phenylxylylethane, 10 parts by weight of Solpol 3685 (trade name; manufactured by Toho Chemical Co., Ltd.) were added, mixed uniformly, and dissolved to obtain an emulsion.

(4) Preparation of Dust A powder was prepared by uniformly mixing 5 parts by weight of the compound (1), 50 parts by weight of talc and 45 parts by weight of kaolin.

Example 3 [Efficacy Test] ________ (1) Test for controlling efficacy against rice blast (preventive effect) Ten rice plants (variety: Nipponbare) were grown per pot in a plastic flowerpot having a diameter of 6 cm. A test compound was added to a young plant at the leaf stage in a 500 ppm chemical solution (surfactant 0. 1).
20% per pot). Cultivation was performed in a glass greenhouse until the inoculation after spraying the chemicals. The day after the application of the drug, the rice blast fungal conidia spore suspension (3 × 10 ⁵ spores /
ml) was prepared, and this was sprayed and inoculated uniformly on the plant body.
4 days after inoculation, 25 ° C, moist chamber (in the dark for the first 3 days,
One day later, the plants were cultivated under light) and the degree of rice blast lesions appeared on the leaves was examined. As a result, compounds 2, 3, 2
8, 54 and 60 showed 10% lesion area.

(2) Test for controlling efficacy against wheat leaf rust (prevention test) Wheat (cultivar: Kobushi wheat) was grown 10 plants per pot in a plastic flower pot having a diameter of 6 cm. A wettable powder of the test compound prepared according to Example 2 was mixed with water containing a surfactant (0.01%) in 500 parts.
It diluted to ppm and sprayed at 20 ml per pot. After spraying, the plants were cultivated in a glass greenhouse for 2 days, and then a spore suspension (7 × 10 ⁴ spores / ml) of wheat leaf rust was uniformly spray-inoculated on the plants. After inoculation, the plants were grown for one week in a glass greenhouse, and the degree of wheat leaf rust spots on the first leaves was examined. As a result, Compounds 1 to 7, 47, 50, 52,
54, 55 and 56 showed a lesion area of 10% or less.

(3) Barley powdery mildew control effect test (prevention test) Ten barleys (cultivar: chromium) are grown in plastic plant pots having a diameter of 6 cm per pot, and the seedlings are planted at the 1.5 leaf stage. The wettable powder of the test compound prepared according to Example 2 was mixed with water containing a surfactant (0.01%) by 500 p.
pm and sprayed at 20 ml per pot. After spraying, the plants were cultivated in a glass greenhouse for 2 days, and then the conidiospores of barley powdery mildew were collected from the diseased leaves, and sprinkled evenly over the plants sprayed with the drug and inoculated.
After inoculation, they were grown in a glass greenhouse for 10 days, and the degree of barley powdery mildew spots that appeared on the first leaf was examined. As a result, Compounds 1 to 7, 28, 47, 48, 50, 52, 5
4, 55, 56, 58 and 64 showed a lesion area of 10% or less.

[0078]

Industrial Applicability The novel pyrazole derivative of the present invention has an excellent agricultural and horticultural bactericidal effect.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Takehiko Asahara 5 in 1978 Kogushi, Oji, Ube City, Yamaguchi Prefecture Inside Ube Research Laboratories Co., Ltd. F-term in Ube Laboratory Co., Ltd. (reference) 4C063 AA01 BB02 CC25 CC41 DD22 EE03 4H011 AA01

Claims (5)

[Claims] (1) The following formula (1):[Wherein, R¹Is a hydrogen atom, an alkyl having 1 to 6 carbon atoms.
Kill group, cycloalkyl group having 3 to 8 carbon atoms or carbon
A haloalkyl group having 1 to 4 atoms; ^TwoIs
Hydrogen atom, alkyl group having 1 to 4 carbon atoms, carbon atom
An alkenyl group of 3 to 6 carbon atoms or an alkenyl group of 3 to 6 carbon atoms
Quinyl group, haloalkyl group having 1 to 4 carbon atoms,-
(CH_Two)_m-OR^Four,-(CH_Two)_m-O- (CH_Two)_n−
OR^Four, COR ^Four, COOR^Four, SO_TwoR^Five, Replace or
Unsubstituted phenyl group,-(CH_Two)_m-R ⁶, Number of carbon atoms
3 to 8 cycloalkyl groups or 3 to 6 carbon atoms
Represents a haloalkenyl group (note that R^FourIs the number of carbon atoms
R represents 1 to 4 alkyl groups;^FiveIs 1 carbon atom
Haloalkyl having 1 to 4 alkyl groups and 1 to 4 carbon atoms
R or a substituted or unsubstituted phenyl group;
⁶Represents a substituted or unsubstituted phenyl group;
And n represents an integer of 1 to 4. ); R^ThreeIs a hydroxyl group,
Substituted or unsubstituted phenyl group, substituted or unsubstituted
Naphthyl group, -O- (CH_Two)_m-R⁶, -O- (CH_Two)
_m-OR⁶, An alkoxy group having 1 to 10 carbon atoms,
Substituted or unsubstituted phenoxy group or substituted or unsubstituted
Represents a substituted pyridyloxy group (note that R^FourAnd m are
It is the same as the above. ); Y represents CH or N. ]
A pyrazole derivative represented by the formula: 2. The following formula (2): (Wherein, R ^{3 ′} represents a substituted or unsubstituted phenyl group, a naphthyl group, or an alkoxy group having 1 to 10 carbon atoms; y has the same meaning as in claim 1). Compound and the following formula (3): (Wherein, R ² has the same meaning as described in claim 1).
A method for producing a pyrazole derivative represented by the formula (1): 3. The following formula (4): (Wherein R ¹ , R ³ and y have the same meanings as in claim 1) and a compound represented by formula (3) in claim 2. A method for producing a pyrazole derivative represented by the formula (1) according to claim 1. 4. The following formula (5): (Wherein R ¹ , R ³ and y have the same meanings as in claim 1) and a compound represented by formula (3) in claim 2. A method for producing a pyrazole derivative represented by the formula (1) according to claim 1. 5. A fungicide for agricultural and horticultural use comprising the pyrazole derivative represented by the formula (1) according to claim 1 as an active ingredient.