JPH1143480A - Pyrazole compound and herbicide and intermediate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound capable of being profitably synthesized and useful as a herbicide sure in the activity at a reduced dose, high in safety, and good in selectivity for crops. SOLUTION: A compound of formula I [R<1> , R<2> are each H, nitro, cyano, a halogen, etc.; R<3> , R<4> are each H, a 1-6C alkyl; R<5> , R<6> are each R<3> , a 2-6C (halo)alkenyl, etc., or R<5> and R<6> may together form a three to six-membered ring; R<7> , R<8> are each a 1-6C (halo)alkyl, a 2-6C alkenyl, a 2-6C alkynyl, etc.; Y is SO2 , a single bond, etc.; R<9> is H, a 3-8C cycloalky, etc.], e.g. 1-methyl-5- hydroxy-4-(2-chloro-3-acetoximemethyl-4-methanesulfonylbenzoyl)pyriazole. The compound of the formula I is obtained e.g. by reacting a compound of formula III with a compound of formula III to produce a compound of formula IV, reacting the compound of the formula III with a compound produced by allowing a halogenating agent to act on the compound of the formula II, and subsequently reacting the produced compound of formula V with the compound of the formula IV.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel 4-benzoylpyrazole compound, a herbicide containing the compound as an active ingredient, and a novel intermediate benzoic acid.

[0002]

2. Description of the Related Art In cultivating agricultural and horticultural crops, many herbicides have been used for weed control, which has required a great deal of labor. However, since it causes phytotoxicity to crops, remains in the environment, and contaminates, there is a demand for the development of a drug that can be used reliably and safely with a lower dose. JP-A-2-173 discloses a compound related to the compound of the present invention.

[0003]

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The compound represented by the general formula (B) is described in JP-A-7-309869.

[0005]

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[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a herbicide which can be synthesized industrially advantageously, is effective at a lower dose, has high safety, and has high selectivity to crops. And benzoic acids useful as intermediates for agricultural chemicals and medicines.

[0007]

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

[0008]

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[Wherein R ¹ and R ² each independently represent a hydrogen atom, a nitro group, a cyano group, a halogen atom,
_1-6 alkyl group, C _1-6 alkoxy group, C _1-6 haloalkyl group, C _1-6 haloalkoxy group, C _1-6 alkylthio group, C _1-6 alkylsulfinyl group or C _1-6 alkylsulfonyl group Represents R ³ and R ⁴ each independently represent a hydrogen atom or a C _1-6 alkyl group. R ⁵ , R
⁶ each independently represents a hydrogen atom, a C _1-6 alkyl group, a C _1-6 haloalkyl group, a C _2-6 alkenyl group,
_2-6 haloalkenyl, C _2-6 alkynyl, C _2-6 haloalkynyl group, C _3-8 cycloalkyl group, C _1-6 alkoxy C _1-6 alkyl group, C _1-6 alkylthio C _{1- 6 represents} an alkyl group, a phenyl group which may have a substituent, a benzyl group which may have a substituent, and a 3- to 6-membered heterocyclic group containing a nitrogen atom, an oxygen atom or a sulfur atom.
R ⁵ and R ⁶ may be combined to form a ring having 3 to 6 members. R ⁷ and R ⁸ are each independently
Hydrogen atom, C _1-6 alkyl group, C _1-6 haloalkyl group,
C _2-6 alkenyl group, C _2-6 alkynyl group or C _3-8
Represents a cycloalkyl group. Y is SO ₂ , (CH ₂ ) m
CO represents a methylene group or a single bond which may be substituted by an alkyl group. m represents 0, 1, 2, and 3. R ⁹ is a hydrogen atom, a C _1-6 alkyl group, a C _2-6 alkenyl group, a C _2-6
Represents an alkynyl group or a phenyl group which may be substituted. Or a salt thereof, and a herbicide containing one or more of these compounds. Further, the present invention provides a compound represented by the general formula (2):

[0010]

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Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ have the same meaning as described above, and Q represents a hydroxyl group, a halogen atom or a C _1-6 alkoxy group. ).

In the above general formulas (1) and (2), R
¹ and R ² are each independently a halogen atom such as fluorine, chlorine and bromine; a C _1-6 alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl and t-butyl; , Ethoxy, propoxy, isopropoxy, butoxy, t-butoxy and other C _1-6 alkoxy groups, fluoromethyl, 1-fluoroethyl, 2-fluoroethyl, difluoromethyl, trifluoromethyl, difluorochloromethyl, fluorochloromethyl, C _1-6 haloalkyl groups such as trichloromethyl, tribromomethyl, trifluoroethyl and pentafluoroethyl, trifluoromethoxy, 1,1,2,2
C _1-6 haloalkoxy groups such as tetrafluoroethoxy, trichloromethoxy, difluoromethoxy, methylthio, ethylthio, propylthio, isopropylthio,
C _1-6 alkylthio groups such as butylthio, methylsulfinyl, ethylsulfinyl, propylsulfinyl,
Isopropyl sulfinyl, butylsulfinyl C _1-6 alkylsulfinyl group such as Le, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, represent a C _1-6 alkylsulfonyl group such as butylsulfonyl.

R ³ and R ⁴ each independently represent a hydrogen atom or methyl, ethyl, propyl, isopropyl,
C such as butyl, isobutyl, s-butyl, t-butyl, etc.
Represents a _1-6 alkyl group.

R ⁵ and R ⁶ each independently represent a hydrogen atom, a C _1-6 alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, s-butyl, t-butyl,
C _1-6 haloalkyl groups such as fluoromethyl, 1-fluoroethyl, 2-fluoroethyl, difluoromethyl, trifluoromethyl, difluorochloromethyl, fluorochloromethyl, trichloromethyl, tribromomethyl, trifluoroethyl, and pentafluoroethyl , vinyl, 1-propenyl, allyl, crotyl, C _2-6 alkenyl group such as butadienyl, 1-chloro vinyl, 2-chlorovinyl, 3-chloroallyl, C _2-6 haloalkenyl group such as 2-Kurorokurochiru, ethynyl, C _2-6 alkynyl groups such as 1-propynyl and 2-propynyl, 2-chloroethynyl, 2-bromoethynyl, 3-chloro-2-
C _2-6 haloalkynyl groups such as propynyl, 3,3,3-trifluoro-1-propynyl, C _3-8 cycloalkyl groups such as cyclopropyl, cyclopentyl and cyclohexyl, methoxymethyl, ethoxymethyl, propoxymethyl, Isopropoxymethyl, butoxymethyl, t
-Butoxymethyl, methoxyethyl, ethoxyethyl,
C _1-6 alkoxy C _1-6 such as propoxyethyl, isopropoxyethyl, butoxyethyl, t-butoxyethyl, methoxypropyl, ethoxypropyl, propoxypropyl, isopropoxypropyl, butoxypropyl, etc.
C _1-6 alkylthio C such as alkyl, methylthiomethyl, methylthioethyl, ethylthiomethyl, propylthiomethyl, isopropylthiomethyl and butylthiomethyl
Represents _1-6 alkyl.

The substituent of the phenyl group which may be substituted includes a halogen atom such as fluorine, chlorine, bromine, methyl, ethyl, etc. at any position of the benzene ring.
Propyl, isopropyl, butyl, isobutyl, C _1-4 alkyl group such as t- butyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, C _1-4 alkoxy group such as t- butoxy, fluoromethyl, 1-fluoroethyl , 2-fluoroethyl, difluoromethyl, trifluoromethyl, difluorochloromethyl, fluorochloromethyl, trichloromethyl, tribromomethyl,
C such as trifluoroethyl and pentafluoroethyl
_1-4 haloalkyl group, trifluoromethoxy, 1,1,
C _1-4 haloalkoxy groups such as 2,2-tetrafluoroethoxy, trichloromethoxy, difluoromethoxy and the like can be mentioned. Examples of the substituent of the benzyl group which may be substituted include a halogen atom such as fluorine, chlorine and bromine, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and t at any position on the benzene ring.
- C _1-4 alkyl group such as butyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, C _1-4 alkoxy group such as t- butoxy, fluoromethyl, 1-
C _1-4 haloalkyl groups such as fluoroethyl, 2-fluoroethyl, difluoromethyl, trifluoromethyl, difluorochloromethyl, fluorochloromethyl, trichloromethyl, tribromomethyl, trifluoroethyl and pentafluoroethyl, trifluoromethoxy, 1,
And C _1-4 haloalkoxy groups such as 1,2,2-tetrafluoroethoxy, trichloromethoxy, difluoromethoxy and the like.

Further, R ⁵ and R ⁶ each independently represent a saturated heterocycle such as oxirane, aziridine, oxetane, azetidine, tetrahydrofuran, tetrahydrothiophene, dithiolane, oxathiolane, tetrahydropyran, tetrahydrothiopyran, pyrrolidine, piperidine, morpholine and the like. Ring, nitrogen atom and oxygen atom of unsaturated heterocycle such as thiophene, furan, pyrrole, pyrazole, imidazole, isoxazole, oxazole, isothiazole, thiazole, oxadiazole, triazole, tetrazole, pyridine, pyrazine, pyrimidine, pyridazine, etc. Alternatively, it represents a heterocyclic group containing a sulfur atom. Examples of the ring formed by R ⁵ and R ⁶ together include cyclopropane, cyclobutane, cyclopentane, and cyclohexane.

R ⁷ and R ⁸ are each independently a hydrogen atom, a C _1-6 alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, s-butyl, t-butyl,
C _1-6 haloalkyl groups such as fluoromethyl, 1-fluoroethyl, 2-fluoroethyl, difluoromethyl, trifluoromethyl, difluorochloromethyl, fluorochloromethyl, trichloromethyl, tribromomethyl, trifluoroethyl and pentafluoroethyl , vinyl, 1-propenyl, allyl, crotyl, C _2-6 alkenyl group such as butadienyl, ethynyl, 1-propynyl, C _2-6 alkynyl groups such as 2-propynyl, cyclopropyl, cyclopentyl, C, such as cyclohexyl
Represents a _3-8 cycloalkyl group.

Y represents SO ₂ , (CH ₂ ) mCO, a methylene group which may be substituted with an alkyl group such as a methyl group or an ethyl group, or a single bond.

R ⁹ represents a hydrogen atom, a C _1-6 alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, s-butyl and t-butyl; and a C _1-6 alkyl group such as vinyl, 1-propenyl, allyl, crotyl and butadienyl. A C _2-6 alkynyl group such as _2-6 alkenyl group, ethynyl, 1-propynyl and 2-propynyl; and a C _3-8 cycloalkyl group such as cyclopropyl, cyclopentyl and cyclohexyl. Further, as the phenyl group which may be substituted,
Halogen atoms such as fluorine, chlorine and bromine, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t
- C _1-4 alkyl group such as butyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, C _1-4 alkoxy group such as t- butoxy, fluoromethyl, 1-
C _1-4 haloalkyl groups such as fluoroethyl, 2-fluoroethyl, difluoromethyl, trifluoromethyl, difluorochloromethyl, fluorochloromethyl, trichloromethyl, tribromomethyl, trifluoroethyl, trifluoromethoxy, 1,1, And a phenyl group which may be substituted with a C _1-4 haloalkoxy group such as 2,2-tetrafluoroethoxy, trichloromethoxy, difluoromethoxy and the like. Examples of YR ⁹ include a hydrogen atom, a p-methylphenylsulfonyl group, a benzyl group, and a phenacyl group.

Some of the compounds of the present invention and the intermediate compounds described below have a substituent having 1 to 6 (C _1-6 ) or 2 to 6 (C _2-6 ) carbon atoms. Preferably, the carbon number is 1-4 (C _1-4 ) or 2-4 (C _2-4 ), respectively. The same applies to the following.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION The compound of the present invention can be produced by the following method. Production method (i) (when R ⁹ Y is a hydrogen atom)

[0022]

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(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ ,
R ⁶ , R ⁷ and R ⁸ have the same meaning as described above;
Represents a halogen. )

That is, by reacting compound (3) or compound (5) with hydroxypyrazole (4), intermediates (6a) and (6b) are obtained, and then the desired product (1a) is obtained. .

The compound (5) can be produced by a general synthetic chemistry method using the compound (3) with an inorganic halide such as thionyl chloride and phosphorus pentachloride.

Compound (6a) and compound (6b) are
It can be obtained by reacting compound (5) and compound (4) in the presence of 1 mol or an excess of a base, using 1 mol or one of each in excess.

The base used in this reaction is KO
Alkali metal hydroxides such as H and NaOH; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide; alkaline earth metal carbonates such as calcium carbonate And tertiary amines such as triethylamine and diisopropylethylamine, organic bases such as pyridine, sodium phosphate and the like.

As the solvent, water, methylene chloride,
Chloroform, toluene, ethyl acetate, dimethylformamide (DMF), tetrahydrofuran (THF), dimethoxyethane (DME), acetonitrile and the like are used.

The reaction mixture is stirred at a temperature between 0 ° C. and the boiling point of the solvent until the reaction is completed. The reaction can also be performed in a two-phase system using a phase transfer catalyst such as a quaternary ammonium salt.

Further, compounds (6a) and (6b)
Can also be obtained by reacting compound (3) with compound (4) in the presence of a dehydrating condensing agent such as dicyclohexylcarbodiimide (DCC). DCC
Solvents used in the reaction with, for example, methylene chloride, chloroform, toluene, ethyl acetate, DM
F, THF, DME, acetonitrile, t-amyl alcohol and the like are used. The reaction mixture is stirred at a temperature from −10 ° C. to the boiling point of the solvent until the reaction is completed, and the reaction mixture is worked up in a conventional manner.

Compounds (6a) and (6b) can be used as a mixture as they are in the next rearrangement reaction. The rearrangement reaction is performed in the presence of a cyano compound and a mild base. That is, the compounds (6a) and (6
1 mol of b) is replaced by 1-4 mol of base, preferably 1-2 mol
Compound (1a) can be obtained by reacting with a mole of a base and 0.01 to 1.0 mole, preferably 0.05 to 0.2 mole of a cyanide compound.

The base used in this reaction includes the above-mentioned bases, that is, alkali metal hydroxides such as KOH and NaOH, alkali metal carbonates such as sodium carbonate and potassium carbonate, calcium hydroxide, magnesium hydroxide and the like. Examples thereof include alkaline earth metal hydroxides, alkaline earth metal carbonates such as calcium carbonate, tertiary amines such as triethylamine and diisopropylethylamine, organic bases such as pyridine, and sodium phosphate. Examples of the cyan compound include potassium cyanide, sodium cyanide, acetone cyanohydrin, hydrogen cyanide, and a polymer holding potassium cyanide. It is preferable to add a small amount of a phase transfer catalyst such as crown ether to the reaction system because the reaction is completed in a shorter time. The reaction temperature is lower than 80 ° C, preferably from room temperature to 40 ° C. The solvents used are benzene, toluene, acetonitrile, 1,2
-Dichloroethane, methylene chloride, chloroform, ethyl acetate, DMF, methyl isobutyl ketone, THF, D
ME and the like.

This rearrangement reaction can also be carried out in an inert solvent in the presence of a base such as potassium carbonate, sodium carbonate, triethylamine, pyridine and the like. The amount of the base used is based on Compounds (6a) and (6b).
The solvent is 0.5 to 2.0 mol, and THF, dioxane, t-amyl alcohol, t-butyl alcohol and the like are used as the solvent. The reaction temperature is preferably from room temperature to the boiling point of the solvent used.

Further, the compound (1a) can be obtained by using a base together with a dehydrating condensing agent such as DCC without isolating the compounds (6a) and (6b). The base used is potassium carbonate, sodium carbonate, triethylamine, pyridine, etc.
The amount of the base used is 0.5 to 2.
0 mol. Examples of the solvent include THF, dioxane, t-amyl alcohol and t-butyl alcohol, and the reaction temperature is preferably from room temperature to the boiling point of the solvent used.

Production method (ii) (when R ⁹ Y is other than a hydrogen atom)

[0036]

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(Where R ¹ , R ² , R ³ , R ⁴ , R ⁵ ,
R ^6, R ⁷ and R ⁸ are as defined above, R ⁹
Y has the same meaning as described above except for a hydrogen atom. Also, Z
Represents a halogen atom. )

That is, compound (1a) and R ⁹ YZ
(Z represents the same meaning as described above) in the presence of a base to obtain the desired product (1b).

The base used in this reaction includes alkali metal hydroxides such as KOH and NaOH, alkali metal carbonates such as potassium carbonate and sodium carbonate, alkaline earth metal hydroxides such as calcium hydroxide, and calcium carbonate. Alkaline earth metal carbonates, tertiary amines such as triethylamine and diisopropylethylamine, organic bases such as pyridine, sodium phosphate, and the like. Solvents include methylene chloride, chloroform, toluene, ethyl acetate, DMF, THF, and the like. DME,
Acetonitrile and the like are used. The reaction is carried out at a temperature between 0 ° C. and the boiling point of the solvent until the reaction is completed. The reaction can also be carried out in a two-phase system of water and a solvent insoluble in water in the above-mentioned solvent, using a phase transfer catalyst such as a quaternary ammonium salt.

The compound represented by the general formula (2), which is an important synthetic intermediate for producing the compound of the present invention, is a novel compound and can be produced as follows.

[0041]

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(Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ have the same meaning as described above, Q ^′ represents an alkoxy group, and V and W each represent Independently represents a halogen atom.)

That is, compound (7) is used as a starting material for halogenation, or 3-acyl or 3-formylbenzoic acid ester (13) is used as a starting material for Grigg.
After a compound (14) is obtained by a nard reaction, a compound (8) is obtained by halogenation, and further condensed with a hydroxyphthalimide (9) to obtain a compound (10). The compound (11) obtained by reaction with hydrazine The desired product (2) can be obtained by dehydration condensation of
a) is obtained.

Compound (8) can be prepared by a known method from compound (7), for example, a simple halogen such as chlorine or bromine or a halogenated compound such as N-bromosuccinimide (NBS) or N-chlorosuccinimide (NCS). The agent can be obtained by reacting the agent in the presence of light or a radical initiator such as benzoyl peroxide.

The compound (8) can be obtained from the compound (13) according to, for example, Org. Synth. , III, 200
Compound (14) by the method based on the Grignard reaction described in (1955), and then a known method, for example,
Hydrogen halides such as hydrochloric acid and hydrobromic acid, phosphorus trichloride,
Phosphoric acid halides such as phosphorus tribromide, triphenylphosphine-carbon tetrachloride, triphenylphosphine-carbon tetrabromide, etc., triphenylphosphonic acid-alkyl halides, sulfonyl halides such as methanesulfonyl chloride, p-toluenesulfonyl chloride It can also be produced by reacting a halogenating agent such as a nitride or a thionyl halide such as thionyl chloride.

The compound (10) can be obtained by reacting the compound (8) and the compound (9) with each other in an amount of 1 mol or one of them in excess, in the presence of 1 mol or an excess of a base.

The base used in this reaction includes alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, sodium methoxide, sodium ethoxide, and the like.
Metal alkoxides such as potassium t-butoxide, carbonates such as sodium carbonate and potassium carbonate, hydrides such as sodium hydride, triethylamine, diisopropylethylamine, 1,8-diazabicyclo [5.4.
0] Unde-7-cene (DBU), pyridine and the like. Examples of the solvent used in the reaction include alcohols such as methanol and ethanol, ethers such as THF and DME, DMF, N,
Examples thereof include amides such as N-dimethylacetamide, aromatic hydrocarbons such as benzene, toluene, and xylene, dimethyl sulfoxide (DMSO), and acetonitrile. The reaction mixture is kept until the reaction is complete.
The mixture is stirred at a temperature from -10 ° C to the boiling point of the solvent, and treated in a conventional manner.

Compound (11) is different from compound (10)
Known methods, for example, Chem. Soc. , 192
6 , 2348 by the Ing-Manke method.

Further, compound (11) and compound (12)
Are used in a molar amount or one of them in excess, for example, O
rg. Synth. , I, 80 (1941) to produce compound (2a).

The solvent used in this reaction includes halogenated hydrocarbons such as methylene chloride and chloroform;
Aromatic hydrocarbons such as benzene and toluene, alcohols such as methanol and ethanol, ethers, THF
And the like. The reaction mixture is stirred at a temperature between −10 ° C. and the boiling point of the solvent until the reaction is completed.

The substituted benzoic acid ester thus obtained can be obtained by a general synthetic chemistry method using a substituted benzoic acid (Q = OH) or a substituted benzoic halide (Q = halogen).
Can be guided to

[0052]

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(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ ,
Q ^′ and X represent the same meaning as described above. )

The 5-hydroxypyrazoles represented by the general formula (4) can be produced, for example, according to the following method described in JP-A-62-234069 or JP-A-3-44375. Can be.

[0055]

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The compound (1) of the present invention can exist in many tautomeric forms, for example, as shown below. All of these compounds are included in the scope of the present invention.

[0057]

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In the compound (1) of the present invention and the intermediate compound (2), when R ⁵ is different from R ⁶ ,
There are geometric isomers of Z, which are also included in the scope of the present invention.

In the present invention, after completion of the reaction, the desired product can be obtained by performing ordinary post-treatment. The structure of the compound of the present invention was determined from IR, NMR, MS and the like.

(Herbicide) The compound of the present invention shows a high herbicidal activity under any conditions of upland crops in any of soil treatment and foliage treatment, and is effective for various field weeds such as Aquinoerocologsa, Oat, Onamimomi, Ichibai and Inubiyu. In addition, some compounds have selectivity for crops such as corn and wheat.

The compounds of the present invention also include compounds that exhibit a plant growth regulating effect such as a growth inhibiting effect on useful plants such as crops, ornamental plants and fruit trees.

Further, the compound of the present invention has excellent herbicidal activity against various paddy weeds such as paddy field weeds such as Nobie, Tamaya-tsuri, Omodaka and Firefly, and also includes a compound showing selectivity to rice. Furthermore, the compound of the present invention can also be applied to the control of weeds in orchards, lawns, track ends, vacant lots and the like. The compounds of the present invention also include those having a plant growth regulating action, a bactericidal activity, an insecticidal / miticidal activity.

The herbicide of the present invention contains one or more of the compounds of the present invention as an active ingredient. When the compound of the present invention is actually applied, it can be used in a pure form without adding other components, and can be in the form of a general pesticide for use as a pesticide, that is, wettable powder, granule, powder ,emulsion,
It can be used in the form of a water solvent, a suspending agent, a flowable or the like. When solid additives are used as additives and carriers, plant powders such as soybean flour and flour, diatomaceous earth,
Mineral fine powders such as apatite, gypsum, talc, bentonite, pyrophyllite, and clay, and organic and inorganic compounds such as sodium benzoate, urea, and sodium sulfate are used. For liquid dosage forms, petroleum fractions such as kerosene, xylene and solvent naphtha, cyclohexane,
Cyclohexanone, DMF, DMSO, alcohol, acetone, trichloroethylene, methyl isobutyl ketone, mineral oil, vegetable oil, water, etc. are used as solvents. In order to take a uniform and stable form in these formulations,
If necessary, a surfactant can be added. Examples of the surfactant include, but are not particularly limited to, alkyl phenyl ether to which polyoxyethylene is added, alkyl ether to which polyoxyethylene is added, higher fatty acid ester to which polyoxyethylene is added, and sorbitan to which polyoxyethylene is added. Nonionic surfactants such as higher fatty acid esters, tristyryl phenyl ether added with polyoxyethylene, sulfates of alkyl phenyl ethers added with polyoxyethylene, alkyl benzene sulfonates, sulfates of higher alcohols, alkyls Examples thereof include sulfates, alkylnaphthalene sulfonates, polycarboxylates, lignin sulfonates, formaldehyde condensates of alkylnaphthalene sulfonates, and copolymers of isobutylene-maleic anhydride.

The active ingredient concentration in the herbicide of the present invention varies depending on the form of the preparation described above. For example, in the case of a wettable powder, it is 5 to 90% by weight, preferably 10 to 85% by weight. : 3 to 70% by weight, preferably 5 to 60% by weight in emulsion: 0.
It is used in a concentration of from 01 to 50% by weight, preferably from 0.05 to 40% by weight.

The wettable powder and emulsion thus obtained are diluted with water to a predetermined concentration to form a suspension or emulsion.
The granules are sprayed or mixed before or after germination of the weeds. In actually applying the herbicide of the present invention, an appropriate amount of 0.1 g or more of the active ingredient per hectare is applied.

The herbicide of the present invention can be used in combination with known fungicides, insecticides, acaricides, herbicides, plant growth regulators, fertilizers and the like. In particular, it is possible to reduce the amount of the drug used by mixing and using the herbicide. In addition to not only saving labor, but also higher effects can be expected due to the synergistic action of the mixed drug. In that case, a combination with a plurality of known herbicides is also possible.

Suitable agents to be used in combination with the herbicide of the present invention include anilide herbicides such as diflufenican and propanil, chloroacetanilide herbicides such as arachlor and pretilachlor, and 2,4-D, 2,4.
-An aryloxyalkanoic acid herbicide such as DB; an aryloxyphenoxyalkanoic acid herbicide such as diclohop-methyl and fenoxaprop-ethyl; an arylcarboxylic acid herbicide such as dicamba and pyrithiobac; imidazo such as imazaquin and imazethapyr; Linone herbicides, urea herbicides such as diuron and isoproturon, carbamate herbicides such as chlorprofam and fenmedipham, thiocarbamate herbicides such as thiobencarb and EPTC, and dinitroaniline herbicides such as trifluralin and pendimethalin. Diphenyl ether herbicides, such as, ashifluorfen and fomesafen;
Sulfonylurea herbicides such as bensulfuron-methyl and nicosulfuron; triazinone herbicides such as metribuzin and metamitrone; triazine herbicides such as atrazine and cyanazine; triazopyrimidine herbicides such as flumeturum; and nitriles such as bromoxynil and diclobenil. -Based herbicides, phosphate-based herbicides such as glyphosate and glyphosinate, quaternary ammonium salt-based herbicides such as paraquat and difenzoquat, full microlac-
Cyclic imide herbicides such as pentyl and fluthiacet-methyl, and others such as isoxaben, etofumesate, oxadiazon, quinclorac, chromazone, sulcotrione, simmethillin, dithiopyr, pyrazolate, pyridate, flupoxam, bentazone, benflusate, and also cetoxydim, tralkoxydim. And cyclohexanedione-based herbicides. Vegetable oils and oil concentrates can also be added to these combinations.

[0068]

Next, the present invention will be described in further detail with reference to Reference Examples and Examples.

Reference Example 1 Production of 2,4-dichloro-3- (1-hydroxy) ethylbenzoic acid methyl ester

[0070]

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To 10 g (42.9 mmol) of 2,4-dichloro-3-formylbenzoic acid methyl ester was added 80 ml of dry THF, and at -70 ° C., 25 ml of a 3M methylmagnesium bromide ether solution was added dropwise. Thereafter, the reaction solution was naturally heated to room temperature and left at room temperature for 30 minutes. The reaction mixture was poured into cold dilute hydrochloric acid and extracted with ethyl acetate.
After washing with water and saturated saline and drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure to obtain 10.44 g of the desired product.

Reference Example 2 Production of 2-chloro-3-methoxycarbonyl-6-methanesulfonylbenzyl bromide

[0073]

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2-chloro-3-methoxycarbonyl-6
-Dissolve 26.1 g (99.7 mmol) of methanesulfonyltoluene in 250 ml of carbon tetrachloride, add 21.3 g (120 mmol) of N-bromosuccinimide and 0.96 g (4 mmol) of benzyl peroxide, and irradiate the lamp. The mixture was heated under reflux for 6 hours. Again, 1.7 g (9.5 mmol) of N-bromosuccinimide and 0.01 g (0.04 mmol) of benzoyl peroxide were added, and the mixture was refluxed for 3 hours. The reaction mixture was cooled, insolubles were filtered, and the filtrate was filtered for 10 minutes.
After washing with a sodium thiosulfate solution, washed with water and saturated saline and dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure to obtain 29.5 g of the desired product.

Reference Example 3 Production of 2,4-dichloro-3- (1-bromo) ethylbenzoic acid methyl ester

[0076]

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10 g (40.2 mmol) of 2,4-dichloro-3- (1-hydroxy) ethylbenzoic acid methyl ester are dissolved in 100 ml of methylene chloride, and triphenylphosphine is dissolved at room temperature at room temperature. 5g (47.
7 mmol), and further added with water-cooled 19.
9 g (59.5 mmol) were added. After standing at room temperature for 30 minutes, 3.2 g (12.2 mmol) of triphenylphosphine was further added, and the mixture was allowed to stand for 30 minutes. After adding water and chloroform to the reaction vessel and stirring for 10 minutes, the organic layer was washed with water, then with a saturated saline solution, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain 6.3 g of the desired product.

Reference Example 4 Production of N- (2-chloro-3-methoxycarbonyl-6-methanesulfonylbenzyloxy) phthalimide

[0079]

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7.16 g of N-hydroxyphthalimide
(43.9 mmol) was dissolved in 70 ml of DMF, 4.9 g (48.5 mmol) of triethylamine was added dropwise under cooling, and then 15 g of 2-chloro-3-methoxycarbonyl-6-methanesulfonylbenzyl bromide (43. 9 mmol) was added dropwise at 10 ° C. or lower, and after the completion of the addition, the temperature was raised to room temperature, left for 30 minutes, poured into water, and the crystallized product was collected by filtration.
After washing with water, the mixture was air-dried to obtain 20.2 g of the desired product as white crystals.

Reference Example 5 Production of 2-chloro-3-methoxycarbonyl-6-methanesulfonylbenzyloxyamine

[0082]

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N- (2-chloro-3-methoxycarbonyl-6-methanesulfonylbenzyloxy) phthalimide (14.9 g, 35.2 mmol) was added to ethanol (100 ml).
Suspended in ice-water, and hydrazine hydrate in it.
7 g (74 mmol) were added dropwise. After the completion of the dropwise addition, the reaction mixture was heated to room temperature and left for 2 hours. Then, insolubles were filtered, and the filtrate was concentrated to obtain a residue (1). Further, the insoluble matter was added to a mixed solvent of ethyl acetate and water, and 10
After stirring for minutes, the mixture was filtered. The ethyl acetate layer was washed with water, dried over anhydrous magnesium sulfate, and the residue obtained by evaporating the solvent under reduced pressure was combined with (1) to obtain 6.22 g of the desired product as crystals.

Example 1 Preparation of methyl 2-chloro-3-acetoximemethyl-4-methanesulfonylbenzoate

[0085]

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2-chloro-chloroform was added to 20 ml of acetone at room temperature.
3-methoxycarbonyl-6-methanesulfonylbenzyloxyamine (1.0 g, 3.4 mmol) was added, and after allowing to stand for 2 hours, the solvent was distilled off under reduced pressure. The obtained residue was dissolved in ethyl acetate, washed with water and saturated saline, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain 1.13 g of the desired product as white crystals.

Example 2 Preparation of methyl 2-chloro-3-ethyloximemethyl-4-methanesulfonylbenzoate

[0088]

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In 30 ml of ethyl alcohol, 3.0 g (10.2 mmol) of 2-chloro-3-methoxycarbonyl-6-methanesulfonylbenzyloxyamine was dissolved, and 0.63 g of a 90% acetaldehyde solution was dissolved therein.
(12.9 mmol) was added dropwise at room temperature, and after allowing to stand for 2 hours, the solvent was evaporated under reduced pressure. The obtained residue was dissolved in ethyl acetate,
After washing with water and saturated saline and drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure to obtain 3.21 g of the desired product.

Example 3 Preparation of 2,4-dichloro-3- (1-acetoxime) ethyl benzoate methyl ester

[0091]

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1.2 g (4.5 mmol) of 2,6-dichloro-3-methoxycarbonyl (1-methyl) benzyloxyamine was added to 20 ml of acetone and allowed to stand at room temperature for 2 hours. The solvent was distilled off under reduced pressure, the residue was dissolved in ethyl acetate, washed with water and washed with saturated saline. After drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure to obtain 1.31 g of the desired product.

Example 4 Preparation of 2,4-dichloro-3-acetoxime methylbenzoic acid methyl ester

[0094]

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In 30 ml of acetone, 2,6-dichloro-
2.0 g of 3-methoxycarbonylbenzyloxyamine
(8.0 mmol) was added at room temperature, and after standing for 2 hours, the solvent was distilled off under reduced pressure. The obtained residue was dissolved in ethyl acetate,
After washing with water and saturated saline and drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure to obtain 2.3 g of the desired product as white crystals.

Example 5 Preparation of 2-chloro-3-acetoximemethyl-4-methanesulfonylbenzoic acid [Compound No. (2b) -11]

[0097]

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2-chloro-3-acetoximemethyl-
4-methanesulfonylbenzoic acid methyl ester 1.09 g
(3.27 mmol) was dissolved in 10 ml of methyl alcohol, and 2.61 g (6.5%) of a 10% aqueous sodium hydroxide solution was added thereto.
(4 mmol) was added dropwise at room temperature and stirred overnight. The reaction solution was poured into iced water, and after acidification with hydrochloric acid, the crystallized product was collected by filtration and washed with water. The obtained crystallized product was dissolved in ethyl acetate, washed with water, washed with saturated saline, and dried over anhydrous magnesium sulfate.
The solvent was distilled off under reduced pressure to obtain 0.78 g of the desired product as white crystals. m. p. 185-186 ° C

Example 6 Preparation of 2-chloro-3-acetoximemethyl-4-methanesulfonylbenzoyl chloride

[0100]

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2-chloro-3-acetoximemethyl-
0.75 g (2.35 mmol) of 4-methanesulfonylbenzoic acid was suspended in 10 ml of benzene, 0.21 ml (2.82 mmol) of thionyl chloride and 1-2 drops of triethylamine were added thereto, and the mixture was heated for 2 hours. After refluxing, the mixture was concentrated under reduced pressure to obtain 0.79 g of the desired product.

Example 7 1-methyl-5-hydroxy-4- (2-chloro-3-
Production of acetoximemethyl-4-methanesulfonylbenzoyl) pyrazole [Compound No. (1) -21]

[0103]

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0.38 g (2.82 mmol) of 1-methyl-5-hydroxypyrazole hydrochloride, 0.38 g of triethylamine.
52 g (5.15 mmol) and molecular sieve 4
0.7 g of A was added to 10 ml of chloroform.
A chloroform solution of 0.79 g (2.35 mmol) of chloro-3-acetoximemethyl-4-methanesulfonylbenzoyl chloride was slowly added dropwise with cooling with ice water, and the mixture was stirred at room temperature for 1 hour. Furthermore, 0.3 g of triethylamine
(2.97 mmol) and 0.06 g of acetone cyanohydrin
(0.7 mmol) and stirred overnight at room temperature. The insoluble material was separated by filtration, and chloroform was added to the filtrate to carry out liquid separation. The chloroform layer was washed with cold diluted hydrochloric acid and then with water, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain 0.79 g of the desired product as a viscous oil.

Example 8 1-methyl-5-benzyloxy-4- (2-chloro-
Production of 3-acetoximemethyl-4-methanesulfonylbenzoyl) pyrazole [Compound No. (1) -29]

[0106]

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1-methyl-5-hydroxy-4- (2-
Dissolve 0.2 g (0.5 mmol) of chloro-3-acetoximemethyl-4-methanesulfonylbenzoyl) pyrazole in 2 ml of DMF and add anhydrous potassium carbonate 0.0 at room temperature.
8 g (0.55 mmol) and benzyl bromide 0.1
1 g (0.6 mmol) was added, and the mixture was stirred at room temperature overnight. The reaction solution was poured into ice water, extracted with ethyl acetate, and the residue was purified by silica gel column chromatography (benzene / ethyl acetate = 2/1) to obtain 0.2 g of the desired product as a transparent oil.

Including the above Examples, the compound (1) of the present invention
And representative examples of the intermediate compound (2b)
The results are shown in Table 2 and Table 2.

[0109]

[Table 101]

[0110]

[Table 102]

[0111]

[Table 103]

[0112]

[Table 104]

[0113]

[Table 105]

[0114]

[Table 106]

[0115]

[Table 107]

[0116]

[Table 108]

[0117]

[Table 109]

¹ H-NMR data (CDCl ₃ , δpp
m) Compound No. 1: 1.87 (6H, d) 3.71 (3H, s) 5.15 (1H, bs)
5.38 (2H, s) 7.34 (1H, d) 7.35 (1H, s)
7.44 (1H, d) Compound No. 2: 1.99 (3H, s) 3.73 (3H, s) 5.58 (2H, s)
5.86 (1H, bs) 7.36 (1H, s) 7.40 (1H, d) 7.49 (1H, d) 3: 1.45 (3H, t) 1.98 (3H, s) 4.06 (2H, q)
5.57 (2H, s) 7.36 (1H, s) 7.40 (1H, d) 7.46 (1H, d) 9.78 (1
H, bs) Compound No. 4: 1.06 (3H, m) 2.27 (2H, m) 3.71 (3H, s)
5.40,5.44 (2H, s) 6.68,7.43 (1H, t) 7.38 (4H, m) 5: 1.03 (3H, m) 1.43 (3H, m) 2.28 (2H, m)
4.05 (2H, m) 5.38,5.42 (2H, s) 6.66,7.38 (1H, t) 7.39 (3
H, m) 8.58 (1H, bs) Compound No. 6: 1.03 (6H, m) 2.48, 3.11 (1H, m) 3.71 (3
H, s) 5.38,5.42 (2H, s) 6.53,7.38 (1H, d) 7.39 (4H, m) 7: 1.01 (6H, m) 1.93 (3H, t) 2.46,3.09 (1
(H, m) 4.05 (2H, q) 5.38,5.40 (2H, s) 6.50,7.35 (1H, d) 7.
36 (3H, m) 9.33 (1H, bs) Compound No. 8: 1.03 (6H, m) 1.75 (3H, m) 2.46, 3.36 (1
H, m) 3.71 (3H, s) 5.36,5.40 (2H, s) 6.90 (1H, bs) 7.36 (3
H, m) Compound No. 9: 1.00 (6H, m) 1.42 (3H, t) 1.74 (3H, m)
2.45,3.34 (1H, m) 4.05 (2H, q) 5.34,5.38 (2H, s) 7.36 (3
H, m) 9.39 (1H, bs) Compound No. 10: 1.71 (4H, m) 2.38 (4H, m) 3.70 (3H, s)
5.40 (2H, s) 6.58 (1H, bs) 7.38 (3H, m) Compound No. 11: 1.42 (3H, t) 1.70 (4H, m) 2.36 (4H, m)
4.05 (2H, q) 5.37 (2H, s) 7.37 (3H, m) 9.13 (1H, bs) Compound No. 12: 1.65 (4H, m) 2.48,3.13 (1H, m) 3.45 (2
H, m) 3.72 (3H, s) 3.96 (2H, m) 5.27 (1H, bs) 5.38,5.42 (2
H, s) 6.55,7.37 (1H, d) 7.38 (3H, m) Compound No. 13: 1.45 (3H, t) 1.63 (4H, m) 2.38,3.12 (1
(H, m) 3.44 (2H, m) 3.95 (2H, m) 4.08 (2H, q) 5.32 (1H, bs)
5.39,5.43 (2H, s) 6.55,7.38 (1H, d) 7.39 (3H, m) 14: 1.84,1.86 (3H, d) 3.49,3.71 (3H, s) 5.
39,5.46 (2H, s) 6.63 (1H, bs) 6.80,7.39 (1H, q) 7.40 (4H,
m) Compound No. 15: 1.43 (3H, t) 1.82,1.83 (3H, d) 4.05 (2
(H, q) 5.38,5.45 (2H, s) 6.78,7.38 (1H, q) 7.39 (3H, m) 9.4
5 (1H, bs) Compound No. 16: 3.71 (3H, s) 5.55 (2H, s) 7.42 (7H, m)
8.04 (1H, s) 8.06 (1H, bs) Compound No. 17: 1.45 (3H, t) 4.06 (2H, q) 5.54 (2H, s)
7.04 (7H, m) 8.03 (1H, s) 9.30 (1H, bs) Compound No. 18: 2.20 (3H, s) 3.71 (3H, s) 5.56 (2H, s)
7.45 (8H, m) Compound No. 23: 0.85, 1.24 (1H, m) 1.59 (4H, m) 2.44, 3.
09 (1H, m) 3.30 (3H, s) 3.40 (2H, m) 3.71 (3H, s) 3.94 (2H, m
m) 5.77 (2H, s) 7.31 (3H, m) 7.52 (1H, d) 8.17 (1H, d) Compound no. 24: 1.64 (3H, d) 1.80 (3H, s) 1.95 (3H, s)
3.70 (3H, s) 6.20 (1H, q) 7.22 (1H, d) 7.30 (1H, s) 7.37 (1
H, d) 9.30 (1H, bs) Compound No. 25: 1.65 (3H, d) 1.72 (4H, m) 2.30 (2H, t)
2.50 (2H, t) 3.70 (3H, s) 6.03 (1H, q) 7.22 (1H, d) 7.32 (1
H, s) 7.37 (1H, d) 8.55 (1H, bs) Compound No. 26: 1.63,1.68 (3H, d) 1.78,1.91 (3H, d) 3.
70 (3H, s) 6.02,6.09 (1H, m) 6.73,7.47 (1H, m) 7.31 (3H, m
m) 8.73 (1H, bs) Compound No. 27: 1.79,1.83 (3H, d) 3.32 (3H, s) 3.52 (3
(H, s) 5.59 (2H, s) 5.74,5.81 (2H, s) 6.77,7.42 (1H, q) 7.
22 (1H, s) 7.36 (5H, m) 7.48 (1H, d) 8.16 (1H, d) 28: 1.20 (3H, m) 1.79,1.82 (3H, d) 3.31 (3
(H, s) 3.87 (2H, q) 5.59 (2H, s) 5.74,5.80 (2H, s) 6.77,7.
37 (1H, q) 7.23 (1H, s) 7.37 (5H, m) 7.49 (1H, d) 8.16 (1H,
d) Compound No. 29: 1.82 (3H, s) 1.83 (3H, s) 3.36 (3H, s)
3.53 (3H, s) 5.60 (2H, s) 5.74 (2H, s) 7.23 (1H, s) 7.36 (5
(H, m) 7.48 (1H, d) 8.17 (1H, d)

[0119]

[Table 201]

[0120]

[Table 202]

[0121]

[Table 203]

[0122]

[Table 204]

[0123]

[Table 205]

[0124]

[Table 206]

¹ H-NMR data (CDCl ₃ , δpp
m) Compound No. 1: 1.88 (6H, d) 5.41 (2H, s) 7.43 (2H, s) 9: 3.60 (3H, s) 5.22 (2H, s) 7.35 (6H, m)

[0126]

EXAMPLES (Herbicide) Next, some formulation examples of the herbicide of the present invention will be described. It is. Parts in Formulation Examples are parts by weight.

Example 9 Wetting agent 20 parts of the compound of the present invention 20 parts White carbon 20 parts Diatomaceous earth 52 parts Sodium alkyl sulfate 8 parts The above components are uniformly mixed and finely pulverized to obtain a wetting agent having an active ingredient of 20%.

Example 10 Emulsion 20 parts of the compound of the present invention 55 parts of xylene 15 parts of dimethylformamide 10 parts of polyoxyethylene phenyl ether 10 parts of the above were mixed and dissolved to obtain an emulsion having an active ingredient of 20%.

Example 11 Granules Compound of the present invention 5 parts Talc 40 parts Clay 38 parts Bentonite 10 parts Sodium alkyl sulfate 7 parts After uniformly mixing and finely pulverizing, the diameter is 0.5 to 1.0 m.
m to obtain granules having an active ingredient of 5%.

[0130]

Next, test examples relating to the effect of the herbicide of the present invention will be shown. The herbicidal effect was investigated according to the following criteria and expressed as a weed kill index.

Survey criteria Weed kill ratio Weed kill index 0% 0 20-29% 240-49% 4 60-69% 680-89% 8 100% 10 Also, 1, 3, 5, 7, 9 The numerical values indicate intermediate values between 0 and 2, 2 and 4, 4 and 6, 6 and 8, and 8 and 10, respectively.

[0132]

(Equation 1)

Test Example 1 Foliage application treatment A 200 cm ² pot was filled with soil, and the surface layer was filled with soil,
Inubiyu, Onamimomi, Akinoenokorogusa, Oat,
Various seeds of wheat and corn were sown, lightly covered with soil, and grown in a greenhouse. When each plant has grown to a plant height of 5 to 25 cm, a water dilution of the emulsion shown in Example 10 is added at 1000 l / h so that the active ingredient has a predetermined dose.
(a) Sprayed on the foliage with a small sprayer in an amount equivalent to the spraying amount.
Three weeks later, the chemical damage of the crops and the herbicidal effect of the weeds were examined in accordance with the above-mentioned criteria, and the results are shown in Table 3.

[0134]

[Table 3]

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Masami Furuguchi 345 Takada, Odawara-shi, Kanagawa Japan Soda Co., Ltd. Odawara Research Laboratories (72) Inventor Takashi Kawana 62-1 Sakabe, Harihara-cho, Haibara-gun, Shizuoka Nippon Soda Odawara Research Co., Ltd. (72) Inventor Akihiro Takahashi 345 Takada, Odawara City, Kanagawa Prefecture Nippon Soda Co., Ltd.

Claims (3)

[Claims] 1. A compound of the general formula (1) [Wherein, R ¹ and R ² each independently represent a hydrogen atom,
Nitro group, cyano group, halogen atom, C _1-6 alkyl group, C _1-6 alkoxy group, C _1-6 haloalkyl group, C
_1-6 haloalkoxy group, C _1-6 alkylthio group, C _1-6
Represents an alkylsulfinyl group or a C _1-6 alkylsulfonyl group. R ³ and R ⁴ each independently represent a hydrogen atom or a C _1-6 alkyl group. R ⁵ and R ⁶ are each independently a hydrogen atom, a C _1-6 alkyl group, a C _1-6 haloalkyl group, a C _2-6 alkenyl group, a C _2-6 haloalkenyl group, a C _2-6 alkynyl group. , C _2-6 haloalkynyl group, C _3-8 cycloalkyl group, C _1-6 alkoxy C _1-6
An alkyl group, a C _1-6 alkylthio C _1-6 alkyl group, an optionally substituted phenyl group, an optionally substituted benzyl group, or a 3-6 membered hetero atom containing a nitrogen atom, an oxygen atom or a sulfur atom Represents a ring group. Also, R ⁵ , R
⁶ together may form a ring having 3 to 6 carbon atoms. R ⁷ and R ⁸ are each independently a hydrogen atom, C
Represents a _1-6 alkyl group, a C _1-6 haloalkyl group, a C _2-6 alkenyl group, a C _2-6 alkynyl group, or a C _3-8 cycloalkyl group. Y represents SO ₂ , (CH ₂ ) mCO, a methylene group which may be substituted with an alkyl group, or a single bond. m represents 0, 1, 2, and 3. R ⁹ is a hydrogen atom, C
Represents a _1-6 alkyl group, a C _2-6 alkenyl group, a C _2-6 alkynyl group, a C _3-8 cycloalkyl group or a phenyl group which may be substituted. Or a salt thereof. 2. A compound of the general formula (1) (Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ ,
R ⁸ , R ⁹ , Y and m represent the same meaning as described above. )
Or a salt thereof as an active ingredient. 3. A compound of the general formula (2) (Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are
Q has the same meaning as described above, and Q represents a hydroxyl group, a halogen atom or a C _1-6 alkoxy group. Benzoic acids represented by).