JP2985364B2 - Pyrazolecarboxamides, insecticides, acaricides and fungicides for agricultural and horticultural use containing the same as an active ingredient - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to pyrazolecarboxamides, insecticides, acaricides, and fungicides for agricultural and horticultural use containing the same as an active ingredient.

[0002]

BACKGROUND OF THE INVENTION In recent years, the long-term use of insecticides and acaricides has resulted in resistance to insect pests, making it difficult to control with conventional insecticides and acaricides. . For example, the occurrence of resistant pests has become a problem for the typical insecticides such as organophosphates and carbamates, and the development of resistance to synthetic pyrethroid insecticides has been reported. ing. on the other hand,
In the field of plant disease control, the occurrence of drug-resistant bacteria has reduced the control effect of conventional fungicides, and has become a serious problem. Under such circumstances, development of new insecticides, acaricides, and agricultural and horticultural fungicides is desired.

[0003]

Means for Solving the Problems The present inventors have conducted intensive studies in order to deal with such a situation, and as a result, have found novel pyrazolecarboxamides having excellent insecticidal, acaricidal and fungicidal activities, and The invention has been completed. That is, the gist of the present invention resides in novel pyrazolecarboxamides represented by the following general formula (I), insecticides, acaricides, and agricultural / horticultural fungicides containing the same as an active ingredient.

[0004]

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[In the above formula, R ¹ and R ² each independently represent a C ₁ -C ₃ alkyl group, and R ³ represents a hydrogen atom or a halogen atom, but R ² and R ³ together represent To form a C ₃ -C ₄ alkylene chain which may be substituted with a C ₁ -C ₃ alkyl group. R ⁴ is a C ₁ -C ₆ alkyl group, a benzyl group which may be substituted or —XR ⁵ (wherein X is an oxygen atom, a sulfur atom,
A sulfinyl group or a sulfonyl group, wherein R ⁵ is C ₁
Alkyl group -C _8, an alkenyl group of C ₂ ~C _6, C ₁
C ₃ -C ₇ which may be substituted with a C ₃ to C ₃ alkyl group
Represents a cycloalkyl group, a C ₁ -C ₅ haloalkyl group or a phenyl group which may be substituted).] Hereinafter, the present invention will be described in detail.

In the general formula (I), R ¹ and R
² each independently represents a C ₁ -C ₃ alkyl group such as a methyl group, an ethyl group, an n-propyl group, and an isopropyl group, and preferably represents a methyl group or an ethyl group. R ³
Represents a hydrogen atom or a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom, and preferably represents a hydrogen atom or a chlorine atom.

However, R ² and R ³ together may be substituted by a C ₁ -C ₃ alkyl group as described above,

[0008]

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A propylene chain which may be substituted with a C ₃ -C ₄ alkylene chain, preferably a C ₁ -C ₃ alkyl group, particularly preferably

[0010]

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May be formed. R ⁴ is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group,
n-pentyl group, isopentyl group, neopentyl group, t
-Pentyl, 1-methylbutyl, 2-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, n-hexyl, isohexyl, neohexyl, 1-methylpentyl, 2-methylpentyl , 3
-Methylpentyl group, 1-ethylbutyl group, 1,2,2
-Trimethylpropyl group, 1,1-dimethylbutyl group,
A C ₁ -C ₆ alkyl group such as a 1-ethyl-1-methylpropyl group (preferably a C ₁ -C ₄ alkyl group, particularly preferably a methyl group or an isobutyl group), an optionally substituted benzyl group A group or —XR ⁵ .

The substituent of the benzyl group is a fluorine atom,
Halogen atoms such as chlorine atom and bromine atom; methyl group, ethyl
Group, n-propyl group, isopropyl group, n-butyl
Group, isobutyl group, sec-butyl group, t-butyl group, etc.
C₁~ C_FourAlkyl group; fluoromethyl group, chloro
Methyl, bromomethyl, difluoromethyl, dic
Loromethyl group, dibromomethyl group, trifluoromethyl
Group, trichloromethyl group, tribromomethyl group, 2,
2,2-trifluoroethyl group, 2,2,2-trichloro
C such as roethyl group, 2,2,2-tribromoethyl group₁
~ C_FourHaloalkyl group; cyclopropyl group, cyclobut
C such as tyl, cyclopentyl, cyclohexyl, etc._Three
~ C₆Cycloalkyl group; hydroxyl group; methoxy
Group, ethoxy group, n-propoxy group, isopropoxy
Group, n-butoxy group, isobutoxy group, sec-butoxy
C, such as a di- or t-butoxy group₁~ C_FourAn alkoxy group of
Fluoromethoxy group, chloromethoxy group, bromomethoxy
Di group, difluoromethoxy group, dichloromethoxy group, di
Bromomethoxy group, trifluoromethoxy group, trichloro
Romethoxy group, tribromomethoxy group, 2,2,2-to
Trifluoroethoxy group, 2,2,2-trichloroethoxy
C, such as a di- or 2,2,2-tribromoethoxy group₁~ C
_FourA haloalkoxy group; a mercapto group; a methylthio group;
Ethylthio group, n-propylthio group, isopropylthio
Group, n-butylthio group, isobutylthio group, sec-butyl
C such as tylthio group and t-butylthio group₁~ C_FourArchi
Ruthio group; methylsulfinyl group, ethylsulfinyl
Group, n-propylsulfinyl group, isopropylsulfur
Ynyl group, n-butylsulfinyl group, isobutylsulfur
Finyl group, sec-butylsulfinyl group, t-butyl
C such as rusulfinyl group₁~ C_FourAlkylsulfini
A methylsulfonyl group, an ethylsulfonyl group, n-
Propylsulfonyl group, isopropylsulfonyl group, n
-Butylsulfonyl group, isobutylsulfonyl group, se
a c-butylsulfonyl group, a t-butylsulfonyl group, etc.
C₁~ C_FourAn alkylsulfonyl group; a carboxyl group;
Methoxycarbonyl group, ethoxycarbonyl group, n-propyl
Ropoxycarbonyl group, isopropoxycarbonyl group,
n-butoxycarbonyl group, isobutoxycarbonyl
Group, sec-butoxycarbonyl group, t-butoxycal
C such as bonyl group_Two~ C_FiveAn alkoxycarbonyl group;
Ano group; formyl group, acetyl group, propionyl group, n
-Butyryl group, isobutyryl group, n-valeryl group, iso-
C such as valeryl group and pivaloyl group ₁~ C_FiveAn acyl group of
Hydroxymethyl group; methoxymethyl group, ethoxymethyl
Group, n-propoxymethyl group, isopropoxymethyl
Group, n-butoxymethyl group, isobutoxymethyl group, etc.
C_Two~ C_FiveAlkoxyalkyl group; nitro group; amino
Group: methylamino group, ethylamino group, n-propyl group
Mino group, isopropylamino group, n-butylamino group,
Isobutylamino group, sec-butylamino group, t-butyl
C such as tylamino group₁~ C_FourAn alkylamino group of
Tylamino group, diethylamino group, di-n-propylpropyl
Mino group, diisopropylamino group, methylethylamino
Group, methyl-n-propylamino group, etc._Two~ C_FourNo
Alkylamino group, preferably C₁~ C_Fourof
It represents an alkyl group, particularly preferably a methyl group.

-XR^FiveWhere X is an oxygen atom, a sulfur atom,
A rufinyl group or a sulfonyl group, preferably an acid
Represents an elementary atom or a sulfur atom. Also, -XR^FiveMedium, R^Five
Are methyl, ethyl, n-propyl, isopropyl
Group, n-butyl group, isobutyl group, sec-butyl
Group, t-butyl group, n-pentyl group, isopentyl group,
Neopentyl group, t-pentyl group, 1-methylbutyl
Group, 2-methylbutyl group, 1-ethylpropyl group, 1,
2-dimethylpropyl group, n-hexyl group, isohexyl
Group, neohexyl group, 1-methylpentyl group,
Tylpentyl group, 3-methylpentyl group, 1-ethylbut
Tyl group, 1,2,2-trimethylpropyl group, 1,1-
Dimethylbutyl group, 1-ethyl-1-methylpropyl
Group, n-heptyl group, isoheptyl group, 1-methylhexyl
Sil group, 1-ethylpentyl group, 1-propylbutyl
Group, 1,3,3-trimethylbutyl group, 1,1-dimethyl
Rupentyl group, n-octyl group, 2-ethylhexyl
Group, 2-propylpentyl group, 1-methylheptyl group,
1-ethylhexyl group, 1,5-dimethylhexyl group,
1-ethyl-4-methylpentyl group, 1,1-dimethyl
Hexyl group, 1,1,4-trimethylpentyl group, 3-
C such as ethyl-3-methylpentyl group₁~ C₈Archi
Group (preferably C₁~ C₆Alkyl groups, especially preferred
Or C_Three~ C₆Alkyl group); vinyl group, 1-methyl
Butyl vinyl group, allyl group, 2-butenyl group, 3-butenyl
Group, 1-methylallyl group, 2-methylallyl group, 2-
Pentenyl group, 3-pentenyl group, 4-pentenyl group,
3-methyl-2-butenyl group, 2-methyl-3-butenyl
Group, 3-methyl-3-butenyl group, 1-methyl-2-
Butenyl group, 1-methyl-3-butenyl group, 2-hexene
Hexyl, 3-hexenyl, 4-hexenyl, 5-hexyl
C such as a xenyl group and a 4-methyl-3-pentenyl group_Two~
C₆Alkenyl group (preferably C_Two~ C_FourArche of
A cycloalkyl group, particularly preferably a 3-butenyl group);
Ropyl, cyclobutyl, cyclopentyl, cyclo
Hexyl group, cycloheptyl group, 2-methylcyclopro
Pill group, 1-methylcyclopentyl group, 2-methylcyclyl
Lopentyl group, 3-methylcyclopentyl group, 1-methyl
Rucyclohexyl group, 2-methylcyclohexyl group, 3
-Methylcyclohexyl group, 4-methylcyclohexyl
Group such as a group or a 4-ethylcyclohexyl group₁~ C_ThreeAl
C optionally substituted with a kill group _Three~ C₉The cycloal
A kill group (preferably C₁~ C_ThreeSubstituted with an alkyl group of
May be C_Three~ C₆Cycloalkyl groups, particularly preferred
Alternatively, the cyclopentyl group or the 4-position is C₁~ C_ThreeNo
A cyclohexyl group which may be substituted with an alkyl group);
Fluoromethyl group, chloromethyl group, bromomethyl group,
Difluoromethyl group, dichloromethyl group, dibromomethyl
Group, trifluoromethyl group, trichloromethyl group,
Libromomethyl group, 2-fluoroethyl group, 2-chloro
Ethyl group, 2-bromoethyl group, 2,2,2-trifur
Oloethyl group, 2,2,2-trichloroethyl group, 2,
2,2-tribromoethyl group, 3-fluoropropyl
Group, 3-chloropropyl group, 3-bromopropyl group,
3,3,3-trifluoropropyl group, 1-methyl-
2,2,2-trifluoroethyl group, 1- (trifluoro
Romethyl) -2,2,2-trifluoroethyl group, 2,
2,3,3-tetrafluoropropyl group, 2,2,3
3,3-pentafluoropropyl group, 2,2-dichloro
-3,3,3-trifluoropropyl group, 2,2,3
3,4,4,4-heptafluorobutyl group, 2,2
3,3,4,4,5,5-octafluoropentyl group, etc.
C₁~ C_FiveHaloalkyl group (preferably C₁~ C
_ThreeHaloalkyl group, particularly preferably a fluorine atom
Transformed C₁~ C_ThreeHaloalkyl group); or substituted
Represents a phenyl group which may be substituted.

The substituent of the phenyl group is a fluorine atom,
Halogen atoms such as chlorine atom and bromine atom; methyl group, ethyl
Group, n-propyl group, isopropyl group, n-butyl
Group, isobutyl group, sec-butyl group, t-butyl group, etc.
C₁~ C_FourAlkyl group; fluoromethyl group, chloro
Methyl, bromomethyl, difluoromethyl, dic
Loromethyl group, dibromomethyl group, trifluoromethyl
Group, trichloromethyl group, tribromomethyl group, 2,
2,2-trifluoroethyl group, 2,2,2-trichloro
C such as roethyl group, 2,2,2-tribromoethyl group₁
~ C_FourHaloalkyl group; cyclopropyl group, cyclobut
C such as tyl, cyclopentyl, cyclohexyl, etc._Three
~ C₆A cycloalkyl group; a hydroxyl group; methoxy
Group, ethoxy group, n-propoxy group, isopropoxy
Group, n-butoxy group, isobutoxy group, sec-butoxy
C, such as a di- or t-butoxy group₁~ C_FourAn alkoxy group of
Fluoromethoxy group, chloromethoxy group, bromomethoxy
Di group, difluoromethoxy group, dichloromethoxy group, di
Bromomethoxy group, trifluoromethoxy group, trichloro
Romethoxy group, tribromomethoxy group, 2,2,2-to
Trifluoroethoxy group, 2,2,2-trichloroethoxy
C, such as a di- or 2,2,2-tribromoethoxy group₁~ C
_FourA haloalkoxy group; a mercapto group; a methylthio group;
Ethylthio group, n-propylthio group, isopropylthio
Group, n-butylthio group, isobutylthio group, sec-butyl
C such as tylthio group and t-butylthio group₁~ C_FourArchi
Ruthio group; methylsulfinyl group, ethylsulfinyl
Group, n-propylsulfinyl group, isopropylsulfur
Ynyl group, n-butylsulfinyl group, isobutylsulfur
Finyl group, sec-butylsulfinyl group, t-butyl
C such as rusulfinyl group₁~ C _FourAlkylsulfini
A methylsulfonyl group, an ethylsulfonyl group, n-
Propylsulfonyl group, isopropylsulfonyl group, n
-Butylsulfonyl group, isobutylsulfonyl group, se
a c-butylsulfonyl group, a t-butylsulfonyl group, etc.
C₁~ C_FourAn alkylsulfonyl group; a carboxyl group;
Methoxycarbonyl group, ethoxycarbonyl group, n-propyl
Ropoxycarbonyl group, isopropoxycarbonyl group,
n-butoxycarbonyl group, isobutoxycarbonyl
Group, sec-butoxycarbonyl group, t-butoxycal
C such as bonyl group_Two~ C_FiveAn alkoxycarbonyl group;
Ano group; formyl group, acetyl group, propionyl group, n
-Butyryl group, isobutyryl group, n-valeryl group, iso-
C such as valeryl group and pivaloyl group₁~ C_FiveAn acyl group of
Hydroxymethyl group; methoxymethyl group, ethoxymethyl
Group, n-propoxymethyl group, isopropoxymethyl
Group, n-butoxymethyl group, isobutoxymethyl group, etc.
C_Two~ C_FiveAlkoxyalkyl group; nitro group; amino
Group: methylamino group, ethylamino group, n-propyl group
Mino group, isopropylamino group, n-butylamino group,
Isobutylamino group, sec-butylamino group, t-butyl
C such as tylamino group₁~ C_FourAn alkylamino group of
Tylamino group, diethylamino group, di-n-propylpropyl
Mino group, diisopropylamino group, methylethylamino
Group, methyl-n-propylamino group, etc._Two~ C_FourNo
Selected from alkylamino groups, preferably₁~ C_Four
An alkyl group of C₁~ C_FourAn alkylthio group of
₁~ C_FourRepresents an alkylsulfonyl group of
Or methyl, methylthio or methylsulfonyl
Represents a group.

R ⁴ is preferably the aforementioned alkyl group or -XR ⁵ (R ⁵ is as defined above), and more preferably -XR ⁵ . Next, the production method of the compound of the present invention will be described. The compound of the present invention represented by the above general formula (I) can be produced according to the following reaction formula (1) or (2).

[0016]

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(In the above reaction formula, R ¹ , R ² , R ³ and R ⁴ are as defined in the above formula (I), and Z is a chlorine atom, a bromine atom, a hydroxyl group, a methoxy group, an ethoxy group. Or a propoxy group.) The above general formula (I
In I), when Z represents a chlorine atom or a bromine atom, the compound represented by the general formula (II) and the compound represented by the general formula (III)
Water; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride and dichloroethane; ethers such as diethyl ether, tetrahydrofuran and dioxane; Ketones such as acetone and methyl ethyl ketone; esters such as methyl acetate and ethyl acetate or polar solvents such as N, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane and acetonitrile, preferably at -20 to 60 ° C. More preferably, the compound is reacted in a temperature range of 0 to 20 ° C. in the presence of a base to obtain a compound represented by the general formula (I). As the base used, inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate and pyridine;
Organic bases such as triethylamine are exemplified.

In the above general formula (II), when Z represents a hydroxyl group, a methoxy group, an ethoxy group or a propoxy group, the compound represented by the general formula (II) and the compound represented by the general formula (III) The compound is used without solvent or in a high boiling point solvent such as N, N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, sulfolane, etc., preferably at 150 to 250 ° C, more preferably at 20 ° C.
By reacting in a temperature range of 0 to 250 ° C., a compound represented by the general formula (I) is obtained.

The compounds represented by formulas (II) and (III) can be easily obtained by known methods.

[0020]

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(In the above reaction formula, R ¹ , R ² , R ³ and R ⁵ are as defined in the above general formula (I).) In the above general formula (I), a compound wherein X represents a sulfinyl group ( Hereinafter, “(I) (X = SO)” and a compound showing a sulfonyl group (hereinafter “(I) (X = SO ₂ )”)
Is a compound represented by the general formula (I) wherein X represents a sulfur atom (hereinafter referred to as "(I) (X = S)").
Water; acetic acid; aromatic hydrocarbons such as benzene, toluene and xylene; hydrogen peroxide, peracetic acid, and metachloroperbenzoic acid in solvents such as methylene chloride, chloroform, carbon tetrachloride, and halogenated hydrocarbons such as dichloroethane Of the present invention in the temperature range of usually -20 to 120 ° C, more preferably 0 to 80 ° C.

The compound represented by the general formula (I) (X = SO) and the compound represented by the formula (I) (X = SO ₂ ) can be selectively obtained by adjusting the amount of the oxidizing agent. In the production of the general formula (I) (X = SO), the oxidizing agent is 0.9 to 1.5 with respect to the general formula (I) (X = S).
Equivalent, _{2 in} the production of general formula (I) (X = SO ₂ )
It is preferred to use from 10 to 10 equivalents.

The compound represented by the general formula (I) (X = SO) can be easily obtained by the method (1). The compound of the present invention thus obtained, insecticide, miticide,
Or when used as an agricultural or horticultural fungicide, it may be used alone, but is usually formulated in the form of a wettable powder, a powder, an emulsion, etc.
Alternatively, dilute and use. As the adjuvant, those usually used for general pesticide preparations are used. For example,
Solid carriers such as kaolin, bentonite, talc, diatomaceous earth, white carbon, starch; water, alcohols (methanol, ethanol, propanol, butanol, ethylene glycol, etc.), ketones (acetone, methyl ethyl ketone, cyclohexanone, etc.), ethers (diethyl Ethers, dioxane, cellosolves, etc.), aliphatic hydrocarbons (kerosene, kerosene, 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, fatty acid glycerin esters, etc.),
Solvents such as nitriles (acetonitrile, etc.); nonionic surfactants (polyoxyethylene alkyl allyl ether, polyoxyethylene sorbitan monolaurate, etc.)
Cationic surfactants (alkyldimethylbenzylammonium chloride, alkylpyridinium chloride, etc.), anionic surfactants (alkylbenzenesulfonate, ligninsulfonate, higher alcohol sulfates, etc.), amphoteric surfactants (alkyldimethylbetaine) ,
And a surfactant such as dodecylaminoethylglycine). These solid carriers, solvents, surfactants,
Each is used as one kind or as a mixture of two or more kinds as necessary. The content of the compound of the present invention in the preparation is not particularly limited, but is usually preferably 1 to 90% by weight, more preferably 10 to 80% by weight in a wettable powder,
For powders, preferably 0.5 to 20% by weight, more preferably 1 to 10% by weight, for emulsions preferably 1 to 90% by weight,
It is more preferably used as a preparation containing 10 to 50% by weight of the active ingredient.

When the compound of the present invention is used as a fungicide for insecticidal, acaricidal, or agricultural and horticultural use, the active ingredient is usually preferably 1 to 1000 ppm, more preferably 5 to 50 ppm.
Use in a concentration range of 0 ppm. The compound of the present invention can be mixed or used in combination with other insecticides, acaricides, fungicides for agricultural and horticultural use, and plant growth regulators, if desired.

[0025]

The compound of the present invention represented by the general formula (I) has remarkable controlling activity against insects and mites such as the following Hemiptera, Lepidoptera, Coleoptera, Orthoptera and Diptera. However, it is needless to say that the present invention is not limited to these. DESCRIPTION OF SYMBOLS 1 Hemiptera; Planthoppers such as brown planthoppers, brown planthoppers, brown planthoppers, etc. Leafhoppers such as black leafhoppers, leafhoppers, etc. Aphids such as peach aphids 2 Lepidopteran; Pteryridae; house flies, Aedes aegypti, mosquitoes and the like. It has a high control activity against plant pathogens, but is not limited thereto.

1 Rice blast 2 Various rusts of barley 3 Powdery mildew of various crops 4 Diseases of various crops

[0027]

The present invention will be described in more detail with reference to Production Examples, Formulation Examples and Test Examples of the compound of the present invention. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Absent. Example 1 Preparation of N- (2-n-propoxythiazol-5-ylmethyl) -4-chloro-3-ethyl-1-methylpyrazole-5-carboxamide 2-n-propoxythiazol-5-ylmethylamine 52 g and 0.36 g of triethylamine were dissolved in 15 ml of ethyl acetate, cooled in an ice bath, and a solution of 0.62 g of 4-chloro-3-ethyl-1-methylpyrazole-5-carboxylic acid chloride in 10 ml of ethyl acetate was stirred. It was dropped. After completion of the dropwise addition, stirring was continued for 2 hours at room temperature, and then water was injected. The organic layer was washed with saturated aqueous sodium hydrogen carbonate and then with saturated saline,
It was dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (developing solvent: ethyl acetate / hexane = 1/2).
0.79 g of the compound (No. 5) described in Table 1 was obtained.

The NMR and IR spectra of this compound are as follows. ¹ H-NMR (δ, CDCl ₃ ): 7.04 (1H,
s), 4.63 (2H, d), 4.33 (2H, t),
4.13 (3H, s), 2.62 (2H, q), 1.8
8-1.74 (2H, m), 1.23 (3H, t),
1.01 (3H, t) IR (KBr) cm ^-1 : 3280, 1645, 1540,
1510, 1470, 1290, 1250, 1220,
1165,970 Similarly, the compound Nos. 1
-4, 6-19, 24-31. Example 2 N- [2- (isopropylsulfinyl) thiazole-
Preparation of 5-ylmethyl] -4-chloro-3-ethyl-1-methylpyrazole-5-carboxamide N- [2- (isopropylthio) thiazol-5-ylmethyl] -4-chloro-3-ethyl-1-methyl 0.65 g of pyrazole-5-carboxamide is added to chloroform 2
The mixture was dissolved in 0 ml, and 0.40 g of metachloroperbenzoic acid was added little by little, followed by stirring at room temperature overnight. The reaction mixture was washed with saturated aqueous sodium hydrogen carbonate and then with saturated saline, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was subjected to silica gel column chromatography (developing solvent: ethyl acetate /
Purification with hexane = 2/1) gave 0.46 g of the compound (No. 20) shown in Table 1.

The NMR and IR spectra of this compound are as follows. ¹ H-NMR (δ, CDCl ₃ ): 7.85 (1H,
s), 4.92-4.78 (2H, m), 4.13 (3
H, s), 3.21 (1H, sept), 2.62 (2
H, q), 1.37 (3H, d), 1.24 (3H,
d), 1.23 (3H, t) IR (KBr) cm ^-1 : 3380, 1650, 1530,
1505, 1285, 1270, 1050, 1030,
865,555 Similarly, Compound No. 21 were produced. Example 3 N- [2- (isopropylsulfonyl) thiazole-5
Preparation of -ylmethyl] -4-chloro-3-ethyl-1-methylpyrazole-5-carboxamide N- [2- (isopropylthio) thiazol-5-ylmethyl] -4-chloro-3-ethyl-1-methylpyrazole 0.65 g of -5-carboxamide in chloroform 2
The mixture was dissolved in 0 ml, and 0.78 g of metachloroperbenzoic acid was added little by little, followed by stirring at room temperature overnight. The reaction mixture was washed with saturated aqueous sodium hydrogen carbonate and then with saturated saline, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was subjected to silica gel column chromatography (developing solvent: ethyl acetate /
(Hexane = 3/2) to give 0.54 g of the compound (No. 22) shown in Table 1.

The NMR and IR spectra of this compound are as follows. ¹ H-NMR (δ, CDCl ₃ ): 7.95 (1H,
s), 4.87 (2H, d), 4.14 (3H, s),
3.58 (1H, sept), 2.63 (2H, q),
1.41 (6H, d), 1.24 (3H, t) IR (KBr) cm ^-1 : 3410, 1650, 1530,
1500, 1315, 1170, 1130, 875, 6
90 Similarly, compound No. 23 were produced.

[0031]

[Table 1]

[0032]

[Table 2]

[0033]

[Table 3]

[0034]

[Table 4]

[0035]

[Table 5]

Compound No. 1 described in Table 1 15 and N
o. Table 3 shows 29 IR spectra.

[0037]

[Table 6]

Next, preparation examples of the compound of the present invention will be shown. In addition,
Hereinafter, “parts” and “%” mean “parts by weight” and “% by weight”, respectively. Formulation Example 1 wettable powder The present compound No. 17 20 parts, Carplex # 80 (Shionogi Pharmaceutical Co., Ltd., trade name) 20 parts, Kunilite 201 (Kunimine Industry Co., Ltd., trade name) 55 parts, higher alcohol sulfate ester surfactant Solpol 8070
(Toho Chemical Co., Ltd., 5 parts) were mixed and uniformly mixed and pulverized to obtain a wettable powder containing 20% of the active ingredient.

Formulation Example 2 Powder Compound of the present invention No. 1 in Table 1 172 parts, clay (Nippon Talc) 92.8 parts, white carbon 5 parts, and isopropyl acid phosphate 0.2 parts were blended and uniformly mixed and pulverized to obtain a powder containing 2% of an active ingredient. Formulation Example 3 Emulsion Compound 1 of the present invention in Table 1 17 20 parts was dissolved in a mixed solvent consisting of 32.5 parts of Kawakazole (Kawasaki Kasei Corporation, trade name) and 32.5 parts of dimethylformamide,
In addition to this, polyoxyethylene surfactant Solpol 30
The emulsion containing 20% of the active ingredient was obtained by adding 15 parts of 05X (trade name of Toho Chemical Co., Ltd.).

Formulation Example 4 Flowable Agent Compound No. 1 of the present invention shown in Table 1. 17 30 parts, ethylene glycol 8 parts, Solpol AC3032 (Toho Chemical Co., Ltd.
5 parts of trade name and 0.1 part of xanthan gum were well mixed and dispersed in 56.9 parts of water. Next, this slurry-like mixture is
It was wet-pulverized with a Dynomill (Shinmaru Enterprises) to obtain a flowable agent containing 30% of the active ingredient.

Next, test examples of the compound of the present invention will be shown. In addition, the compound No. of Tables 4-9 shown below. Is the above Table-1
And the compound Nos. Corresponding to Test Example 1 Effect of Japanese moth on larvae The compound of the present invention formulated according to the formulation of Formulation Example 1 was applied to the spreading agent Solpol 3005X (trade name of Toho Chemical Co., Ltd.) 20
Diluted with water containing 0 ppm, the active ingredient concentration is 500pp
m. Cabbage cut leaves (5 cm × 5 cm) were immersed in this solution for 1 minute. After air-drying the chemical,
In a plastic cup (diameter: 7 cm), five third instar larvae of the Japanese moth were released and left in a thermostat at 25 ± 1 ° C. (2 repetitions).

Four days after the treatment, the larvae were examined for viability and the mortality was calculated by the following equation. The results are shown in Table-4.

[0043]

(Equation 1)

[0044]

[Table 7]

Test Example 2 Effect of brown planthopper on larvae The compound of the present invention prepared according to the formulation of Preparation Example 1 was applied to the spreading agent Solpol 3005X (trade name of Toho Chemical Co., Ltd.) 20
Diluted with water containing 0 ppm, the active ingredient concentration is 500pp
m. Put five larvae of brown planthopper and rice seedlings in a glass cylinder 2.5 cm in diameter and 18 cm in height.
The cap was covered with a mesh, and 0.5 ml of the above-mentioned drug solution was sprayed from above, and left in a constant temperature room at 25 ± 1 ° C. (2 repetitions).

Five days after the treatment, the life and death of the larvae in the cylinder were examined, and the insecticidal rate was calculated by the following equation. The results are shown in Table-5.

[0047]

(Equation 2)

[0048]

[Table 8]

Test Example 3 Effect of Azuki Beetle on Adult Insect Compound of the present invention prepared according to the formulation of Preparation Example 1 was applied to spreading agent Solpol 3005X (trade name of Toho Chemical Co., Ltd.) 20
Diluted with water containing 0 ppm, the active ingredient concentration is 500pp
m. Put 5 adults of Azuki weevil and 2 adzuki beans in a glass cylinder 2.5 cm in diameter and 18 cm in height, cover with a cap with a mesh attached, spray 0.5 ml of the above drug solution from the top, and apply 25 ± 1 ° C. It was left in a thermostatic chamber (2 repetitions).

Five days after the treatment, the life and death of the adults in the cylinder were examined, and the insecticidal rate was calculated by the following equation. The results are shown in Table-6.

[0051]

(Equation 3)

[0052]

[Table 9]

Test Example 4 Effect on the Larvae and Eggs of the Tetranychus spider mite The compound of the present invention prepared according to the formulation of Preparation Example 1 was applied to the spreading agent Solpol 3005X (trade name of Toho Chemical Co., Ltd.) 20
Diluted with water containing 0 ppm, the active ingredient concentration is 500pp
m. Ten adult female spider mites were inoculated into the primary leaves of kidney beans and allowed to stand in a room for 24 hours to lay eggs. The leaves holding the adult female spider mites and eggs were immersed in the above-mentioned chemical solution for 5 seconds, and then left in a constant temperature room at 25 ± 1 ° C. (2 repetitions).

Five days after the treatment, the life and death of the adult was investigated, and the insecticidal rate was calculated by the following equation.

[0055]

(Equation 4)

At the same time, the hatching state of eggs and the life and death of hatching larvae were examined. The effect on eggs was evaluated as ○ (survival insect rate 0
%), Δ (survival insect rate less than 20%), × (survival insect rate 20%)
Judgment was made based on the above three grades. The results are shown in Table-7.

[0057]

[Table 10] Test Example 5 Test for Control of Wheat Powdery Mildew The compound of the present invention prepared according to the formulation of Preparation Example 1 was diluted with water to prepare an active ingredient concentration of 200 ppm. The above aqueous solution was added to a 1-2 leaf stage wheat (cultivar: Norin 61) grown in a 6 cm diameter pot.
0 ml of foliage was sprayed. After air-drying with a chemical solution, a spore suspension obtained from wheat leaves infected with wheat powdery mildew ( Erysiphegraminis ) was sprayed and inoculated, and then placed in a greenhouse.
Leave for -10 days. The diseased area ratio of each leaf was evaluated, and the control value was calculated by the following formula. The results are shown in Table-8.

[0058]

(Equation 5)

[0059]

[Table 11]

Test Example 6 Wheat Leaf Rust Control Effect Test The compound of the present invention prepared according to the formulation of Preparation Example 1 was diluted with water to prepare an active ingredient concentration of 200 ppm. The above aqueous solution was added to a 1-2 leaf stage wheat (cultivar: Norin 61) grown in a 6 cm diameter pot.
0 ml of foliage was sprayed. After chemical drying, wheat leaf rust ( P
succinia recondita ) was sprayed and inoculated with a spore suspension obtained by grinding wheat, kept in a greenhouse at 22 ° C. for 15 hours, and then left in the greenhouse for 7 days. The diseased area ratio of each leaf was evaluated, and the control value was calculated by the following formula. The results are shown in Table-9.

[0061]

(Equation 6)

[0062]

[Table 12]

[0063]

As is clear from the above Test Examples, the compounds of the present invention are useful as insecticides, acaricides, and fungicides for agricultural and horticultural use.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Kazuhiko Kikutake 1000 Kamoshita-cho, Midori-ku, Yokohama-shi, Kanagawa Prefecture Inside Mitsubishi Chemical Research Institute (56) References JP-A-1-199963 (JP, A) (58) ) Surveyed field (Int. Cl. ⁶ , DB name) C07D 417/12 CA (STN) REGISTRY (STN)

Claims (6)

(57) [Claims] 1. A pyrazolecarboxamide represented by the following general formula (I). Embedded image [In the above formula, R ¹ and R ² are each independently C _1-
R ³ represents a hydrogen atom or a halogen atom, and R ² and R ³ together represent a C ₁ -C ₃ alkyl group;
Substituted with an alkyl group of C ₃ may form an alkylene chain of good C ₃ -C ₄ also. R ⁴ is a C ₁ -C ₆ alkyl group, an optionally substituted benzyl group or —X
R ⁵ (wherein, X represents an oxygen atom, a sulfur atom, a sulfinyl group or a sulfonyl group, R ⁵ is a C ₁ -C ₈ alkyl group, a C ₂ -C ₆ alkenyl group, a C ₁ -C ₃ alkyl A C ₃ -C ₇ cycloalkyl group, a C ₁ -C ₅ haloalkyl group or a phenyl group which may be substituted). 2. In the general formula (I), R^FourIs C₁~ C₆No
Alkyl group; halogen atom, C₁~ C_FourAn alkyl group of C
₁~ C_FourHaloalkyl group of C_Three~ C₆Cycloalkyl
Group, hydroxyl group, C₁~ C_FourAn alkoxy group of C
₁~ C_FourHaloalkoxy group, mercapto group, C₁~ C
_FourAn alkylthio group of C₁~ C_FourAlkylsulfini
Group, C₁~ C_FourAlkylsulfonyl group, carboxy
Group, C_Two~ C_FiveAn alkoxycarbonyl group, cyano
Group, C₁~ C_FiveAn acyl group, a hydroxymethyl group, C_Two
~ C_FiveAn alkoxyalkyl group, a nitro group, an amino group,
C ₁~ C_FourAlkylamino group and C_Two~ C_FourZia of
Having one or more substituents selected from alkylamino groups
A benzyl group which may be substituted; or -XR^Five(Where X is oxygen
Atom, sulfur atom, sulfinyl group or sulfonyl group
And R^FiveIs C₁~ C₈An alkyl group of C_Two~ C₆No
Lucenyl group; C₁~ C_ThreeSubstituted with an alkyl group of
Good C_Three~ C₇A cycloalkyl group of C;₁~ C_FiveNo ha
Loalkyl group or halogen atom, C₁~ C_FourArchi
Group, C₁~ C_FourHaloalkyl group of C_Three~ C₆No shiku
Loalkyl group, hydroxyl group, C₁~ C_FourAlcoqui
Si group, C₁~ C_FourHaloalkoxy group, mercapto group,
C₁~ C_FourAn alkylthio group of C₁~ C_FourThe alkyls of
Rufinyl group, C₁~ C_FourAlkylsulfonyl group,
Ruboxyl group, C_Two~ C_FiveAn alkoxycarbonyl group of
Cyano group, C₁~ C_FiveAcyl group, hydroxymethyl
Group, C_Two~ C_FiveAn alkoxyalkyl group, a nitro group,
Mino group, C₁~ C_FourAlkylamino group and C_Two~ C
_FourAt least one substituent selected from dialkylamino groups of
A phenyl group which may be substituted).
2. The pyrazolecarboxamides according to 1. 3. A compound of the formula (I)¹And R^TwoIs C₁~
C_TwoRepresents an alkyl group represented by^ThreeIs a hydrogen atom or chlorine atom
Show child, but R^TwoAnd R^ThreeIs C₁~ C_ThreeAlkyl group
May form a propylene chain which may be substituted
Well, R^FourIs C₁~ C_FourAn alkyl group of C₁~ C_FourNo
A benzyl group which may be substituted with a alkyl group or -X
R^Five(Where X is an oxygen atom, a sulfur atom, a sulfinyl group
Or a sulfonyl group;^FiveIs C₁~ C₆Archi
Group, C_Two~ C_FourAn alkenyl group of C₁~ C_ThreeArchi
C which may be substituted with_Three~ C₆Cycloalkyl
Group, C₁~ C _ThreeA haloalkyl group, or C₁~ C_Four
An alkyl group of C₁~ C_FourAlkylthio group or C
₁~ C_FourMay be substituted with an alkylsulfonyl group of
The pyrazole according to claim 1, which represents a phenyl group).
Lucarboxamides. 4. An insecticide and acaricide comprising the pyrazolecarboxamides according to claim 1 as an active ingredient. 5. A fungicide for agricultural and horticultural use comprising the pyrazolecarboxamides according to claim 1 as an active ingredient. 6. In the general formula (I), R ¹ and R ² are C ₁ to
An alkyl group of C _2, R ³ represents a hydrogen atom or a chlorine atom, R ⁴ is in -XR ⁵ (wherein, X represents an oxygen atom or a sulfur atom, R ⁵ is an alkyl group of C ₁ -C ₆ , C ₁
C _{3 to} C ₆ which may be substituted with a C ₃ to C ₃ alkyl group
A cycloalkyl group or a C ₁ -C ₃ haloalkyl group). The agricultural and horticultural fungicide comprising the pyrazolecarboxamides according to claim 5 as an active ingredient.