JPH10168063A - Substituted pyrazole derivative, its production and antimicrobial agent containing the derivative as active ingredient and useful for agricultute and horticulture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new substituted pyrazole derivative exhibiting excellent control effects related to preventions, treatments and penetrative migration against wide plant diseases, expressing safety for crops and capable of being used as an agricultural antimicrobial agent showing excellent antimicrobial effects. SOLUTION: A substituted pyrazole derivative of formula I(R<1> is H, a halogen, an alkyl, an alkenyl, cyano, etc.; R<2> is H, an alkyl, phenyl, a cycloalkyl, a halolkyl, etc.; R<3> , R<4> are each independently an alkyl; Ar is phenyl, etc.; X is O atom, etc.; (n) is 0, 1, 2,), e.g. methyl-2-(3-(3-chlorophenyl)-5-methylpyrazol-1- yl)-3-methoxypropenoate. The compound of formula I is obtained by reacting an alkanoic acid ester derivative of formula II(R<4a> is H, an alkyl) with a formulating agent in the presence of a base and subsequently reacting the obtained compound formula III with an alkylating agent in the presence of a base.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel pyrazole derivative useful as an agricultural and horticultural fungicide, a method for producing the same, and an agricultural and horticultural fungicide containing the derivative as an active ingredient.

[0002]

2. Description of the Related Art Various fungicides have been developed so far, but their efficacy and appearance of resistant bacteria are not always satisfactory. Also, JP-A-61-291
No. 565 discloses that certain pyrazole derivatives have bactericidal activity.However, even the compounds described therein are not satisfactory in terms of efficacy, residual efficacy, phytotoxicity, etc. There is a need for the development of agricultural and horticultural fungicides that are more useful against plant diseases.

[0003]

Means for Solving the Problems In view of such circumstances, the present inventors have made various studies to develop compounds having excellent bactericidal activity, and as a result, they are represented by the following general formula (I). They have found that substituted pyrazole derivatives have excellent bactericidal activity, and have completed the present invention.

That is, the present invention provides: 1) a compound represented by the general formula (I):

Embedded image [Wherein, R ¹ represents a hydrogen atom, a halogen atom, an alkyl group,
Cycloalkyl, alkenyl, cyano, alkoxycarbonyl, nitro, alkylthio, alkylsulfinyl, alkylsulfonyl or

Embedded image (Wherein R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group), and R ² represents a hydrogen atom, an alkyl group, a phenyl group, a cycloalkyl group, a haloalkyl group, a halogen atom, an alkylthio group. A group, an alkylsulfinyl group or an alkylsulfonyl group,
R ³ and R ⁴ independently represent an alkyl group;
Is an unsubstituted or substituted phenyl group, or a compound of the formula (A)

Embedded image X represents an oxygen atom or

Embedded image (In the group, R ⁷ represents a hydrogen atom or an alkyl group.)
And n represents 0, 1 or 2. A substituted pyrazole derivative represented by the formula:

2) General formula (III)

Embedded image (Wherein R ^4a represents a hydrogen atom or an alkyl group;
¹ , R ² , Ar and n have the same meaning as described above. ) Is reacted with a formylating agent in the presence of a base to give a compound of the general formula (II)

Embedded image Wherein R ¹ , R ² , R ^4a , Ar and n have the same meanings as described above, and then reacting with an alkylating agent in the presence of a base. Formula (IA)

Embedded image (Wherein, R ^3a represents an alkyl group, and R ¹ , R ² ,
R ^4a , Ar and n have the same meaning as described above. A method for producing a substituted pyrazole derivative represented by

3) In the compound represented by formula (IA), alkylamine ((R ⁷ ) ₂ NH) (two R ^{7 s} may be the same or different and represent a hydrogen atom or a lower alkyl group). , Which do not represent a hydrogen atom at the same time).

Embedded image (The symbols in the formula have the same meanings as described above.)

4) A fungicide for agricultural and horticultural use containing the derivative represented by the general formula (I) as an active ingredient.

In the general formula (I), the halogen atoms represented by R ¹ and R ² are fluorine, chlorine, bromine and iodine atoms.

In the general formulas (I) and (IB), R
^{1, R 2, R 3,} R 4, R 5, alkyl groups R ⁶ and R ⁷ represent are those having 1 to 6 carbon atoms, may be branched be linear. Specific examples include methyl, ethyl, propyl, butyl, pentyl, hexyl and their isomeric groups.

In the general formula (I), the cycloalkyl group represented by R ¹ and R ² has 3 to 6 carbon atoms and includes, for example, cyclopropyl, cyclobutyl, cyclopentyl,
A cyclohexyl group is mentioned, and a cyclopropyl group is preferred.

In the general formula (I), the alkenyl group represented by R ¹ has 2 to 4 carbon atoms and may be linear or branched. For example, vinyl, propenyl and butenyl groups are mentioned, and a propenyl group is preferable.

In the general formula (I), the alkoxycarbonyl group represented by R ¹ has 2 to 5 carbon atoms, and the alkyl group in the alkoxy group may be linear or branched.
Examples include methoxycarbonyl, ethoxycarbonyl, with a methoxycarbonyl group being preferred.

In the general formula (I), the alkylthio group, alkylsulfinyl group and alkylsulfonyl group represented by R ¹ and R ² have an alkyl moiety having 1 to 4 carbon atoms, May be linear or branched. Examples of alkylthio groups include methylthio,
An ethylthio group is mentioned, and a methylthio group is preferred. Examples of the alkylsulfinyl group include a methylsulfinyl group and an ethylsulfinyl group, and a methylsulfinyl group is preferable. Examples of the alkylsulfonyl group include a methylsulfonyl group and a methylsulfonyl group, and a methylsulfonyl group is preferable.

In the general formula (I), the haloalkyl group represented by R ² corresponds to a group in which a hydrogen atom in the above-mentioned alkyl group has been substituted with 1 to 3 halogen atoms, such as a trifluoromethyl group. Can be

In the general formula (I), examples of the substituent of the substituted phenyl group represented by Ar include lower alkyl, lower haloalkyl, lower alkoxy, lower haloalkoxy, halogen (fluorine, chlorine, bromine, etc.), phenyl and phenoxy. , Di-lower alkylamino, cyano and the like. A plurality of the same or different substituents may be present.

Next, typical examples of the compound of the present invention represented by the general formula (I) are shown in Table 1. However, the compound of the present invention is not limited to these compounds (the compound number is also referred to in the following description). In the table, Me is a methyl group, Et is an ethyl group, Pr is a propyl group, Bu is a butyl group, Ph is a phenyl group, i is iso, t is tertiary,
c represents cyclo, respectively, (Y) in the column of _n (A) phrase is intended to represent a group represented by (Y) _n Formula as substituted phenyl group (A).

[0017]

[Table 1]

[0018]

[Table 2]

[0019]

[Table 3]

[0020]

[Table 4]

[0021]

[Table 5]

[0022]

[Table 6]

[0023]

[Table 7]

[0024]

[Table 8]

[0025]

[Table 9]

[0026]

[Table 10]

[0027]

[Table 11]

[0028]

[Table 12]

[0029]

[Table 13]

[0030]

[Table 14]

[0031]

[Table 15]

[0032]

[Table 16]

[0033]

[Table 17]

[0034]

[Table 18]

[0035]

[Table 19]

[0036]

[Table 20]

[0037]

[Table 21]

[0038]

[Table 22]

Next, a method for producing the compound of the present invention will be described. The compound of the present invention, as shown in the following reaction scheme,
For example, by reacting an alkanoic acid ester derivative (acetic acid ester, propionic acid ester derivative or butanoic acid ester derivative) represented by the general formula (III) with a formylating agent in the presence of a base and a solvent, the general formula (I
Compound (I) is obtained (step (a)) and then reacted with an alkylating agent in the presence of a base to give a compound of the general formula (IA) in which X represents an oxygen atom in the general formula (I)
Can be obtained (step (b)).

[0040]

Embedded image

In the above reaction scheme, R ^3a and R ^4a independently represent an alkyl group, and R ¹ , R ² , Ar, X and n have the same meaning as described above. First, in the reaction of an alkanoic ester represented by the general formula (III) (acetic acid ester derivative, propionate ester derivative, or butanoic acid ester derivative) with a formylating agent, the formylating agent is a formate such as methyl formate. And acid amides such as N, N-dimethylformamide. Also,
Examples of the base include alkyl lithiums such as sodium hydride and normal butyl lithium, and lithium amides such as N, N-diisopropyl lithium amide.

The amount of the reagent used for the reaction is determined by the general formula (II)
The amount of the formylating agent is about 1 to 10 equivalents and the amount of the base is 1 to 2 equivalents to 1 equivalent of the acetic acid ester derivative, propionic acid derivative or butanoic acid derivative represented by I). In the above reaction, the reaction temperature and reaction time are usually about 0 ° C to 1 ° C.
00 ° C, 10 minutes to 24 hours. A solvent is usually used for the above reaction. Examples of the solvent that can be used include ethers such as diethyl ether, 1,2-dimethoxyethane and tetrahydrofuran, and acid amides such as N, N-dimethylformamide.

Next, in the reaction of the compound represented by the general formula (II) with the alkylating agent in the step (b), the alkylating agent may be an alkyl halide such as methyl iodide or a sulfate such as dimethyl sulfate. Is used. As the base, tertiary amines such as pyridine, triethylamine and 4-N, N-dimethylaminopyridine, and inorganic bases such as sodium hydride, sodium carbonate and potassium carbonate are used.

The amount of the reagent used for the reaction is determined by the general formula (II)
The amount of the alkylating agent is usually about 1 to 2 equivalents, and the amount of the base is about 1 to 2 equivalents to 1 equivalent of the compound represented by In the above reaction, a solvent is usually used. Examples of the solvent that can be used include ethers such as diethyl ether, tetrahydrofuran, and 1,2-dimethoxyethane, acid amides such as N, N-dimethylformamide, and ketones such as acetone and methyl ethyl ketone. After completion of the reaction, a usual post-treatment is carried out, and if necessary, purification is carried out by an operation such as chromatography, recrystallization or the like to obtain the desired compound of the general formula (I
The compound of the present invention represented by A) can be obtained.

In the present invention, the compound of the general formula (IA) can be prepared in one pot without isolating the compound of the general formula (II) from the acetate, propionate or butanoate derivative of the general formula (III). Can also be produced. That is, the acetic acid ester of the general formula (III), the propionic acid ester derivative or the butanoic acid ester derivative is reacted with formate esters using the above-mentioned base and solvent to give a compound of the general formula (II) in the reaction system. And then adding an alkylating agent such as an alkyl halide or a sulfate ester to obtain a compound of the formula (IA)
Of the present invention can be produced.

In the acrylate derivative represented by the general formula (IA) thus obtained, alkylamine ((R ⁷ ) ₂ NH) (two R ^{7 s} may be the same or different, and may be a hydrogen atom or A lower alkyl group, but not a hydrogen atom at the same time) in an appropriate solvent such as an alcohol such as methanol or ethanol, or an ether such as diethyl ether or tetrahydrofuran. In the formula (I), X is

Embedded image (Wherein, R ⁷ has the same meaning as described above.)

Embedded image (Wherein, R ¹ , R ² , R ^3a , R ⁷ , Ar and n have the same meanings as described above).

The reaction temperature at this time is usually 0 ° C. to 100 ° C.,
Reaction times range from 1 hour to 24 hours. General formula (II
The acetate, propionate or butanoate derivative represented by I) is represented by the general formula (V)

Embedded image (Wherein, R ¹ , R ² , Ar and n have the same meanings as described above) and a general formula (I
V)

Embedded image Z-CH ₂ (CH ₂ ) _n CO ₂ R ^4a (IV) (wherein, Z represents a halogen atom, R ^4a represents an alkyl group, and n represents 0, 1 or 2) By reacting the compound with a haloacetic acid ester, a halopropionic acid ester, or a halobutanoic acid ester in the presence of a base.

In the above reaction, as the base, for example, tertiary amines such as pyridine, triethylamine, 4-N, N-dimethylaminopyridine, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydride, etc. And inorganic bases. The reaction solvent is not necessarily required, but usable solvents include ethers such as diethyl ether, tetrahydrofuran and 1,2-dimethoxyethane, acid amides such as N, N-dimethylformamide, acetone, methyl ethyl ketone and the like. Ketones, acetonitrile, N-methylpyrrolidone, and the like.

The reaction temperature and the reaction time are about 10 ° C. to 1
The objective can be achieved at 50 ° C. for about 10 minutes to 24 hours. The amount of the reagent used is about 1 equivalent of the pyrazole derivative represented by the general formula (V) and the haloacetic acid ester, the halopropionate ester, or the halobutanoate ester represented by the general formula (IV) is about 1 equivalent.
~ 2 equivalents, base is about 1-2 equivalents. After the completion of the reaction, normal post-treatment is performed, and if necessary, chromatography,
The desired product can be obtained by purification by an operation such as recrystallization. The pyrazole derivative represented by the general formula (V) can be produced, for example, according to the following reaction scheme. In the formula, B represents a base, and other symbols have the same meanings as described above.

[0050]

Embedded image

The compound (I) according to the present invention is applied to plants by treating the active ingredient by spraying, spraying, applying, or the like, or by sowing plant seeds or soil or seeds surrounding the plants. It can be carried out by treating the soil, paddy field, or water of hydroponics with an active ingredient. The application can be made before or after the plant is infected with the pathogen.
The compound is in the form of a conventional preparation, for example, a disinfectant for agricultural chemicals such as liquid, wettable powder, emulsifier, suspension, liquid concentrate, tablet, granule, aerosol, paste, powder, smoke and the like. It can be used as a suitable drug. Such embodiments include at least one compound of the present invention and suitable solid or liquid carriers and, if desired, suitable adjuvants (eg, surfactants) for improving the dispersibility or other properties of the active ingredient. Agents, spreading agents, dispersants, stabilizers).

Examples of solid carriers or diluents include:
Plant substances, fibrous substances, artificial plastic powders, clays (eg, kaolin, bentonite, clay), talc and minerals (pumice, sulfur powder), chemical fertilizers and the like. As liquid carriers and diluents, water, alcohols, ketones, ethers, aromatic hydrocarbons, aliphatic hydrocarbons,
Examples include esters, nitriles, amides (N, N-dimethylformamide, dimethyl sulfoxide), halogenated hydrocarbons, and the like.

Examples of the surfactant include an alkyl sulfate, an alkyl sulfonate, a polyethylene glycol ether and polyhydric alcohol esters. Examples of spreading or dispersing agents include casein, gelatin, starch, carboxymethylcellulose, acacia, alginic acid, lignin, bentonite, polyvinyl alcohol, pine oil, molasses and agar.

Examples of the stabilizer include isopropyl phosphate mixture, tricresyl phosphate, true oil, epoxy oil, surfactants, fatty acids and esters thereof. In addition to the above ingredients, the formulations of the present invention may contain other fungicides,
It can be used in admixture with pesticides, herbicides or fertilizers.

In general, the above-mentioned preparation contains at least one compound of the present invention (I) in an amount of 1 to 95% by weight, preferably 1 to 95% by weight.
Contains 50% by weight. These preparations can be used alone or in a diluted form, and the compound of the present invention is used in an amount of about 1 g to 5 kg.
/ Ha, preferably about 2 g to 100 g / ha, usually about 1 to 50,000 ppm, preferably about 50 to 10 ppm.
Used at a concentration of 00 ppm.

The plant diseases which the compound of the present invention exhibits excellent control effects include rice blast (Pyricularia oryzae),
Sesame leaf blight (Cochliobolus miyabeanus), sheath blight (Rhizo
ctonia solani), idiot disease (Gibberella fujikuroi), wheat powdery mildew (Erysiphegraminis f.sp.hordei, Er)
ysiphe graminis f.sp.tritici), rust (Puccinia s
triiformis, Puccinia graminis, Puccinia recondita
f.sp.tritici, Puccinia hordei), Fusarium head blight (Gibberel
la zeae), net spot (Pyrenophora teres), snow rot (Typh)
ula incarnata, Typhula ishikariensis, Sclerotinia
borealis, Micronectriell a nivalis), naked smut (Usti
lago nuda), Tilletia caries, Tille
tia toetida), eye spot disease (Tapesia yallundea), scald disease
(Phynchosporium secalis f.sp.hordei), leaf blight (Sep
toria tritici), Fusarium wilt (Lentosphaeria nodorum), Citrus black spot (Diaporthe citri), Scab (Elsinoe)
fawcettii), brown rot (Phytophthora citrophthor)
a), green mold (Penicilliumdigitatum), blue mold (Pe
nicillium italicum), Monilinia on apples (Monilinia)
mali), rot (Valsa ceratosperma), powdery mildew (P
odosphaera leucotricha), spot leaf spot (Alternaria al
ternata apple pathotype), scab (Venturia inaequal)
is), scab (Gymnosporangium yamadae), ring spot (Bot)
riophaeria berengeriana f.sp.piricola), soot spot disease
(Zygophiala jamaicensis), soot spot disease (Gloeodes pomige
na), black spot (Mycosphaerella pomi), anthracnose (Glomere)
lla cingulata), brown spot (Diplocarpon mali), pear scab (Venturia nashicola), black spot (Alternaria alte)
rnata japanese pear pathotype), ring spot disease (Physalospor)
a piricola), scab (Gymnosporangium asiaticum),
Peach ash (Moniliniafructicola), scab (Cladospo)
rium carpophilum), Phomopsis rot
p.), downy mildew of grape (Plasmopara viticola), brown spot
(Pseudocercospora vitis), ring spot disease (Marssonina vitico
la), black rot (Elsinoe ampelina), late rot (Glomerell)
a cingulata), powdery mildew (Uncinula necator), rust
(Phakopsora ampelopsidis), branch swelling (Phomopsis sp.)
, Oyster powdery mildew (Phyllactiniakakicola), Anthracnose
(Colletotrichum gloeosporioides), horn spot leaf disease (Cer
cospora kaki,), Maruboshi deciduous disease (Mycosphaerella n awae)
, Black scab of plum (Cladosporium carpophilum), Brown scab of sweet cherry (Monilinia fructicola), Powdery mildew of cucumber (Sphaerotheca fuliginea), Downy mildew (Pseudoperonospo)
ra cubensis), vine blight (Didymella bryoniae), anthracnose
(Colletotorichum legenarium), Seedling blight (Pythium cuc
urbitacearum, Pythium debaryanum, Rhizoctonia sola
ni), tomato ring spot (Alternaria solani), leaf mold (C
ladosporium fulvum), plague (Phytophthora infestan)
s), eggplant brown spot (Phomopsis vexans), powdery mildew (Ery
siphe cichoracearum), black spot of cruciferous vegetables (Alter
naria japonica, Alternaria bracicae, Alternaria br
assicicola), vitiligo (Cercosporella brassicae), spinach downy mildew (Peronospora spinaciae), plague (P
hytophthora sp.), downy mildew of onion (Peronospora des)
tructor), plague (Phytophthora nicotiana), gray rot
(Botrytis allii), green onion rust (Puccinia allii), ginger rhizome rot (Pyrhium ultimum, Pythium zigibe
ris), strawberry powdery mildew (Sphaerotheca humuli), anthracnose (Glomerella cingulata), soybean purpura (Cercosp
ora kikuchii), downy mildew (Peronospora manshurica), black rot (Elsinoe glycines), black spot (Diaporthe phaseol)
orum var. sojae), brown spot of adzuki bean (Cercospora canesc)
ens), rust (Uromyces phaseoli var.
rachidis), pea powdery mildew (Erysiphe pisi),
Potato summer plague (Alternaria solani), plague (Phyto
phthora infestans), tea net blast (Exobasidium re
ticulatum), scab (Elsinoe leucospila), ring spot (Pes
talotiopsis theae, Pestalotiopsis longiseta), tobacco scab (Alternaria longipes), powdery mildew (Erysi
phe cichoracearum), anthracnose (Colletotrichum gloeospo)
rioides), brown spot of sugar beet (Cercospora beticola),
Curvularia geniculata (Shiba)
Leaf blight (Rhizoctonia solani), pseudo blight (Ceratobasid
ium spp.), Pythium disease (Pythiumperiplocum, Pythium
graminicola, Pythium vanterpoolii), rose scab
(Diplocarpon rosae), powdery mildew (Shaerotheca panno
sa), chrysanthemum leaf spot (Septoria obesa), white rust (Pucci
nia horiana), gray mold on various crops (Botrytisciner
ea), sclerotium disease (Sclerotinia sclerotiorum) and the like.

[0057]

EXAMPLES Next, production examples and reference examples of the compound of the present invention, and test examples of the compound of the present invention as a fungicide for agricultural and horticultural use will be specifically described.

Production Example 1: In the general formula (I), R ¹ =
H, R ² = methyl, R ³ = methyl, R ⁴ = methyl, n =
Synthesis of Compound (Compound No. 40) of 0, X = Oxygen atom, Ar = 3-chlorophenyl Add 3.7 g of 60% sodium hydride to 100 ml of dry dimethylformamide, and stir under ice-cooling.
(3-chlorophenyl) -5-methylpyrazole-1-
A mixed solution of 15.0 g of methyl ylacetate and 34.0 g of methyl formate was added dropwise. After the completion of the foaming, the mixture was returned to room temperature and stirred for 4 hours. Thereafter, 10.7 g of dimethyl sulfate was added and stirred for 4 hours. After completion of the reaction, the reaction solution was poured into 100 ml of water and extracted three times with 50 ml of ether. The collected ether layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and the ether was distilled off under reduced pressure. The obtained oil was purified by silica gel column chromatography (solvent: n-hexane / ethyl acetate = 2/1) to give methyl-2- (3
-(3-chlorophenyl) -5-methylpyrazole-1
-Yl) -3-methoxypropenate (12.3 g) was obtained as white crystals (yield 71%). 112-113 ° C.

Production Example 2: In the general formula (I), R ¹ =
Synthesis of Compound (Compound No. 109) of chlorine atom, R ² = methyl, R ³ = methyl, R ⁴ = methyl, n = 0, X = oxygen atom, Ar = 3-chlorophenyl Methyl-2 in 80 ml of dry chloroform − (3- (3
2.6 g of sulfuryl chloride were slowly added dropwise to 4.0 g of -chlorophenyl) -5-methylpyrazol-1-yl) -3-methoxypropenate at room temperature, and the mixture was stirred for 2 hours. After completion of the reaction, the reaction solution was poured into 50 ml of water, neutralized with a saturated sodium hydrogen carbonate solution, and extracted three times with 30 ml of chloroform. The collected organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and ether was distilled off under reduced pressure. The obtained oil is subjected to silica gel column chromatography (solvent: n-hexane / ethyl acetate = 2).
/ 1) to give 3.3 g of methyl-2- (3- (3-chlorophenyl) -4-chloro-5-methylpyrazol-1-yl) -3-methoxypropenate as white crystals. Rate 74%). 96-97 ° C.

Production Example 3: In the general formula (I), R ¹ =
Synthesis of Compound (Compound No. 178) of bromine atom, R ² = methyl, R ³ = methyl, R ⁴ = methyl, n = 0, X = oxygen atom, Ar = 3-chlorophenyl Methyl-2- in 60 ml of acetic acid 1.9 g of sodium acetate was added to 3.0 g of (3- (3-chlorophenyl) -5-methylpyrazol-1-yl) -3-methoxypropenate, and a solution obtained by dissolving 1.8 g of bromine in 10 ml of acetic acid was stirred at room temperature. And slowly stirred for 2 hours. After the reaction is completed, the reaction solution is poured into 50 ml of water,
After neutralization with a saturated sodium hydrogen carbonate solution, the mixture was extracted three times with 30 ml of ether. The collected ether layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and the ether was distilled off under reduced pressure. The obtained oil is subjected to silica gel column chromatography (solvent: n-hexane / ethyl acetate =
2/1) to give methyl-2- (3- (3-chlorophenyl) -4-bromo-5-methylpyrazole-1-
2.9 g of yl) -3-methoxypropenate were obtained as white crystals (yield 77%). Melting point 101-102 [deg.] C.

Production Example 4: In the general formula (I), R ¹ =
Synthesis of compound of iodine atom, R ² = methyl, R ³ = methyl, R ⁴ = methyl, n = 0, X = oxygen atom, Ar = 3-chlorophenyl (Compound No.248) Methyl-2 in 25 ml of methylene chloride -(3- (3-chlorophenyl) -5-methylpyrazol-1-yl)-
1.2 g of iodine was added to 1.5 g of 3-methoxypropenate, and then 3 ml of concentrated nitric acid was slowly added dropwise at room temperature.
I stirred for two hours. After completion of the reaction, add 50 ml of the reaction solution.
And neutralized with saturated sodium bicarbonate solution, and extracted with 30 ml of methylene chloride three times. The collected organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The resulting oil was purified by silica gel column chromatography (solvent: n-hexane / ethyl acetate = 2/1) to give methyl-2- (3-
1.9 g of (3-chlorophenyl) -4-iodo-5-methylpyrazol-1-yl) -3-methoxypropenate
Was obtained as white crystals (yield 89%). Melting point 136-1
37 ° C.

The physical properties of the compound of the present invention obtained by such a production method are shown in Table 2 below. Table 3 shows the NMR data of the compound of the present invention.

[0063]

[Table 23]

[0064]

[Table 24]

[0065]

[Table 25]

[0066]

[Table 26]

[0067]

[Table 27]

[0068]

[Table 28]

[0069]

[Table 29]

Reference Example 1: 1- (3-chlorophenyl)-
Synthesis of 1,3-butanedione A solution of 119 g of 3'-chlorophenylacetophenone in 200 ml of tetrahydrofuran was added dropwise to 37.0 g of 60% sodium hydride in 150 ml of dry tetrahydrofuran under ice-cooling, and after the foaming was completed, the mixture was returned to room temperature and stirred for 1 hour. . The reaction solution was added dropwise to 300 ml of dry ethyl acetate at room temperature over 30 minutes and stirred for 4 hours. After the completion of the reaction, the reaction solution was poured into 300 ml of ice water, the solution was adjusted to pH 1 with 2N hydrochloric acid, and stirred at room temperature for 1 hour.
Thereafter, the solution was neutralized with sodium hydrogen carbonate and extracted three times with 200 ml of ethyl acetate. The combined organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. Diisopropyl ether was added to the obtained oil to crystallize it, followed by filtration and drying to obtain 140.0 g of 1- (3-chlorophenyl) -1,3-butanedione as white crystals (yield 87%).

Reference Example 2: 3- (3-chlorophenyl)-
Synthesis of 5-methylpyrazole 1- (3-chlorophenyl) -1, synthesized in Reference Example 1.
To a solution of 140.0 g of 3-butanedione in 500 ml of ethanol was slowly added 35.0 g of hydrazine monohydrate under ice-cooling, the mixture was stirred at room temperature for 1 hour, and then stirred at reflux temperature for 2 hours.
It was time stirring. After completion of the reaction, ethanol was distilled off under reduced pressure. The obtained crude crystals were washed with diisopropyl ether and n-hexane, filtered, and dried under reduced pressure to give white crystals of 3- (3-chlorophenyl)-.
103.0 g of 5-methylpyrazole was obtained (80% yield).

Reference Example 3: 3- (3-chlorophenyl)-
Synthesis of methyl 5-methylpyrazol-1-ylacetate 3- (3-chlorophenyl) -5-synthesized in Reference Example 2
19.6g of methylpyrazole in dry acetonitrile 200m
To this solution, 21.1 g of potassium carbonate was added, and the mixture was stirred at room temperature for 1 hour. To this solution was added 23.3 g of methyl bromoacetate, and the mixture was stirred at reflux temperature for 12 hours. After completion of the reaction, the solvent was distilled off under reduced pressure.
The mixture was extracted three times with 00 ml, and the combined organic layers were washed with saturated saline and dried over anhydrous sodium sulfate. The oily substance obtained by evaporating the solvent under reduced pressure was purified by silica gel column chromatography (solvent: n-hexane / ethyl acetate = 3/1) to obtain 3- (3-chlorophenyl) -5 as white crystals.
18.7 g of methyl-methylpyrazol-1-ylacetate was obtained (69% yield).

Test Examples Next, test examples of the compound of the present invention as a fungicide for agricultural and horticultural use will be described. The control effect was evaluated by visually observing the diseased area ratio, disease length and the number of lesions at the time of the investigation, and the control index was indicated in the following five stages.
The evaluation criteria were in accordance with the present evaluation criteria unless otherwise specified. Index 5: No lesions found Index 4: Diseased area rate, disease length, number of lesions 1 to 1 in untreated plot
Less than 10%, Index 3: Diseased area rate, disease length, number of lesions is 10 in the untreated plot
Index: less than 30%, index 2: disease area rate, disease length, number of lesions in untreated plots
<50%, Index 1: 50% of diseased area rate, disease length and number of lesions in untreated plot
未 満 <100%, Index 0: Diseased area rate, diseased length, and number of lesions are equivalent to the untreated plot.

Test Example 1: Test for Control of Powdery Mildew in Cucurbits Separation of powdery mildew fungus (Sphaerotheca fuliginea) on cucumber (variety: Hikari No. 3 P type) at the 3 leaf stage grown in a plastic pot with a diameter of 6 cm Spores were sprinkled and inoculated. Three days later, the active ingredient compound was diluted with water containing Tween 20 to prepare a drug solution of 200 ppm / 10
a was sprayed using a spray gun. Thereafter, the pot was kept in a greenhouse, and after 12 days from the inoculation, the lesion areas formed on the first and second true leaves were examined, and the control index was determined according to the evaluation criteria described above. As a result, the following compound was 500 ppm
Indicates an index of 5.

Compound No. 10 of the present invention showing an index of 5,
11, 23, 24, 36, 37, 39, 41, 45, 4
6, 55, 56, 61, 62, 63, 74, 77, 7
9,80,81,93,99,101,105,10
6, 108, 109, 112, 115, 117, 12
3, 125, 130, 131, 132, 143, 14
6, 147, 148, 149, 150, 162, 16
5, 168, 170, 171, 174, 175, 17
7, 178, 181, 183, 184, 186, 19
2,193,194,195,197,199,20
0, 201, 213, 216, 217, 248, 25
6, 262, 270, 282, 286, 287, 29
2,296,298,301,315,327,34
2, 357, 358, 359, 361, 362, 36
3, 365, 380, 382, 384, 385, 38
6, 388, 403, 405, 408, 414, 41
5, 417, 424, 425, 429, 467, 47
0.

Test Example 2: Rice Blast Control Test Tween 20 was used as an active ingredient compound for rice (cultivar: Koshihikari) at the 3 leaf stage grown in a plastic pot having a diameter of 9 cm.
200 diluted with water containing water and adjusted to 500 ppm
An amount equivalent to liter / 10a was sprayed using a spray gun.
The next day, a conidia suspension of rice blast (Pyricularia oryzae) was spray-inoculated. After the pot was kept in a humid chamber at 23 ° C. for 24 hours, and then kept in a greenhouse for 7 days, the number of lesions on the inoculated leaves was examined, and the control index was determined according to the evaluation criteria described above. As a result, the following compounds had an index of 5 at 500 ppm.
showed that.

Compound No. 4 of the present invention showing an index of 5,
6, 9, 10, 11, 21, 23, 24, 34, 41,
45, 46, 47, 48, 54, 56, 61, 62, 7
4, 77, 79, 80, 81, 99, 105, 106,
117, 123, 131, 143, 146, 148, 1
50, 168, 175, 178, 181, 183, 18
6, 200, 213, 248, 256, 270, 28
2, 287, 289, 292, 297, 298, 30
0, 301, 302, 306, 316, 322, 32
8, 334, 340, 342, 350, 357, 35
9, 361, 363, 365, 386, 388, 40
3, 405, 408, 409, 414, 417, 41
9, 420, 421, 422, 425, 428, 42
9,443,455,480.

Test Example 3: Test for controlling downy mildew of cucurbits An active compound was added to a cucumber (variety: Hikari No. 3 P type) at the 3 leaf stage grown in a plastic pot having a diameter of 6 cm.
Chemical solution 2 diluted to 500 ppm with water containing n20
An amount of 00 liter / 10a was sprayed using a spray gun. 20 ml of the drug solution adjusted to 500 ppm was sprayed using a spray gun. The next day cucumber downy mildew (Pseudopero
Nospora cubensis) zoospore suspension was spray inoculated. After the pot was kept in a humid room at 22 ° C. for 18 hours and then in a greenhouse for 5 days, the lesion length was examined, and the control index was determined according to the evaluation criteria described above. As a result, the following compound is 500
An index of 5 was shown in ppm.

Compound No. 27 of the present invention having an index of 5
30, 36, 37, 39, 54, 55, 56, 58, 5
9, 61, 62, 63, 74, 79, 80, 81, 9
3, 96, 99, 101, 104, 105, 106, 1
08, 109, 110, 112, 114, 115, 11
7, 123, 124, 125, 127, 128, 13
0, 131, 132, 143, 146, 147, 14
8, 149, 150, 162, 165, 168, 17
0, 171, 174, 175, 177, 178, 17
9, 181, 183, 184, 186, 192, 19
3, 194, 196, 197, 199, 200, 20
1, 213, 216, 217, 248, 256, 26
2,270,282,285,286,287,28
9,292,294,295,297,298,30
0, 310, 322, 327, 331, 334, 34
0, 342, 358, 359, 361, 362, 36
3, 365, 384, 385, 386, 404, 40
7, 408, 409, 414, 415, 416, 41
9, 420, 421, 424, 425, 427, 42
9,432.

Test Example 4: Rice Sheath Blight Control Test Tween 20 was used as an active ingredient compound for rice (cultivar: Koshihikari) at the 3 leaf stage grown in a plastic pot having a diameter of 9 cm.
200 diluted with water containing water and adjusted to 500 ppm
An amount equivalent to liter / 10a was sprayed using a spray gun.
20 ml of the drug solution adjusted to 500 ppm was sprayed using a spray gun. The next day, the fungus of Rhizoctonia solani grown on the PDA medium was punched out with a cork borer and inoculated on a leaf sheath. After the pot was kept in a humid room at 28 ° C. for 24 hours, and then kept in a greenhouse for 3 days, the lesion length was examined, and the control index was determined according to the evaluation criteria described above. As a result, the following compound is 50
An index of 5 was shown at 0 ppm.

Compound No. 11 of the present invention showing an index of 5,
12, 16, 24, 30, 41, 45, 46, 54, 5
5, 56, 61, 62, 63, 68, 78, 79, 8
0, 81, 89, 93, 96, 99, 104, 106,
108, 109, 110, 112, 114, 115, 1
17, 123, 124, 125, 127, 130, 13
1, 132, 143, 147, 148, 150, 15
8, 162, 165, 168, 173, 174, 17
5, 177, 178, 179, 181, 183, 18
4, 186, 192, 193, 194, 196, 19
7, 199, 200, 201, 213, 217, 22
6, 248, 256, 270, 282, 285, 28
9, 296, 297, 298, 301, 316, 32
2,328,342,347,357,359,36
1, 363, 365, 370, 373, 380, 38
1, 382, 384, 385, 386, 388, 39
3, 396, 403, 404, 405, 408, 40
9, 414, 415, 417, 424, 428, 44
1, 467, 470, 478, 480, 499.

Test Example 5: Control test of Chinese cabbage black spot disease The active ingredient compound was added to Twenty-five Chinese cabbage (variety: Nozaki No. 2) grown in a plastic pot having a diameter of 6 cm.
Drug solution 20 diluted to 500 ppm by dilution with water containing 20
0 liter / 10a equivalent amount was sprayed using a spray gun. The next day, a conidia suspension of Chinese cabbage black spot (Alternaria brassicae) was spray-inoculated. Place the pot in a 24 ° C moist chamber for 3
After keeping for 1 day and then for 1 day in a greenhouse, the diseased area ratio of the inoculated leaves was investigated, and the control index was determined according to the evaluation criteria described above. As a result, the following compounds showed an index of 5 at 500 ppm.

Compound No. 4 of the present invention showing an index of 5,
6, 10, 16, 23, 30, 36, 37, 39, 4,
0, 43, 45, 54, 61, 62, 63, 74, 8
0, 96, 104, 105, 106, 108, 115,
117, 131, 132, 143, 149, 165, 1
68, 174, 175, 177, 184, 186, 20
0, 201, 213, 248, 256, 262, 27
0, 282, 287, 292, 298, 300, 32
2, 334, 347, 350, 370, 373, 38
0, 393, 403, 415, 421, 437, 44
8.

Test Example 6: Control test of cucumber gray mold A cucumber (variety: Hikari No. 3 P type) at the cotyledon stage grown in a plastic pot having a diameter of 9 cm was treated with a Twee as an active ingredient.
Chemical solution 2 diluted with water containing n20 and adjusted to 500 ppm
An amount of 00 liter / 10a was sprayed using a spray gun. The next day, a conidia suspension of cucumber gray mold (Botrytis cinerea) was spray-inoculated. After keeping the pot in a humidity chamber at 22 ° C. for 24 hours, then in a greenhouse for 2 days,
The number of lesions on the inoculated leaves was investigated, and a control index was determined according to the evaluation criteria described above. As a result, the following compounds showed an index of 5 at 500 ppm.

Compound No. 11 of the present invention showing an index of 5,
12, 30, 32, 36, 37, 39, 46, 54, 5,
6, 61, 62, 63, 68, 74, 77, 79, 8
0, 93, 101, 105, 106, 108, 109,
112, 114, 115, 117, 130, 131, 1
32, 143, 146, 148, 149, 158, 17
4, 175, 177, 178, 181, 183, 18
4, 186, 194, 199, 200, 201, 21
3, 216, 248, 256, 262, 270, 28
2,285,286,287,289,292,29
8, 340, 342, 347, 357, 363, 37
0, 386, 388, 393, 409, 414, 41
5.

[0086]

INDUSTRIAL APPLICABILITY The novel substituted pyrazole derivative of the present invention exhibits excellent control effects on a wide range of plant diseases in terms of prevention, treatment and systemic transfer, while showing safety on crops and excellent sterilization. It is useful as a fungicide for agricultural and horticultural purposes.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Shigeyoshi Kanno 2-1-1 Midorigahara, Tsukuba, Ibaraki Pref. Inside SDS Biotech Tsukuba Research Laboratories Co., Ltd. (72) Takashi Sakakibara 2, Midorigahara, Tsukuba, Ibaraki No. 1 SDS Biotech Tsukuba Research Laboratories (72) Inventor Takuo Kimura 2-1-1 Midorigahara, Tsukuba-shi, Ibaraki Pref. SDS Biotech Tsukuba Research Laboratories

Claims (4)

[Claims] 1. A compound of the general formula (I) [Wherein, R ¹ represents a hydrogen atom, a halogen atom, an alkyl group,
Cycloalkyl, alkenyl, cyano, alkoxycarbonyl, nitro, alkylthio, alkylsulfinyl, alkylsulfonyl, or Wherein R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group. R ² represents a hydrogen atom, an alkyl group, a phenyl group, a cycloalkyl group, a haloalkyl group, a halogen atom, an alkylthio group. R ³ and R ⁴ independently represent an alkyl group; Ar represents an unsubstituted or substituted phenyl group, or a compound represented by the formula (A): And X represents an oxygen atom or (In the group, R ⁷ represents a hydrogen atom or an alkyl group.)
And n represents 0, 1 or 2. ] The substituted pyrazole derivative represented by these. 2. A compound of the general formula (III) (Wherein R ^4a represents a hydrogen atom or an alkyl group;
¹ , R ² , Ar and n have the same meaning as described in claim 1. ) Is reacted with a formylating agent in the presence of a base to give a compound of the general formula (II) Wherein R ¹ , R ² , R ^4a , Ar and n have the same meanings as described above, and then reacting with an alkylating agent in the presence of a base. Formula (IA) (Wherein, R ^3a represents an alkyl group, and R ¹ , R ² ,
R ^4a , Ar and n have the same meaning as described above. )). 3. A compound of the general formula (IA) (Wherein R ¹ , R ² , R ^3a , R ^4a , Ar and n have the same meanings as in claim 2). The compound represented by the formula (1) is obtained by adding an alkylamine ((R ⁷ ) ₂ NH) (two R ⁷ may be the same or different and represents a hydrogen atom or a lower alkyl group, provided that they do not represent a hydrogen atom at the same time.)
Reacting with a compound represented by the general formula (IB): (The symbols in the formula have the same meanings as described above.) 4. A fungicide for agricultural and horticultural use comprising one or more of the substituted pyrazole derivatives according to claim 1 as an active ingredient.