JPH0774214B2 - Sulfonamide compounds and salts thereof, herbicidal compositions containing them, and methods for producing the same - Google Patents

Description

The present invention relates to a sulfonamide compound represented by the following general formula (I) and a salt thereof, a herbicidal composition containing them as an active ingredient, and a method for producing them. Regarding

General formula (I): (In the formula, R is a hydrogen atom, a methyl group or a mono-, di- or trihalogenomethyl group, Y ₁ and Y ₂ are halogen atoms, and Z is a methyl group or a methoxy group).

[Conventional technology]

It is conceptually known that the isothiazole sulfonamide compound is useful as a herbicide because the compound is widely represented by the general formula in JP-A-58-219179. However, the compound of the present invention is not specifically disclosed in this publication, and the applicability of the sulfonamide compound as a herbicide for paddy rice is not specified. Further, the utility of the sulfonamide compounds as herbicides is also known from JP-A-59-1480 and JP-A-60-48988, but those disclosed from these publications are particularly The present invention compound is that the former does not have any substituent at the 5-position of the isothiazole nucleus of the sulfonamide compound, and the latter is different from the corresponding substituent of the present invention in its kind. And clearly different chemical structure.

[Object of the Invention]

An object of the present invention is to provide a novel sulfonamide compound and a salt thereof, a herbicidal composition containing them as an active ingredient, and a method for producing them.

[Structure of Invention]

The present invention is a sulfonamide compound represented by the following general formula (I) and a salt thereof, a herbicidal composition containing them as an active ingredient, and a method for producing them.

General (I): (In the formula, R is a hydrogen atom, a methyl group or a mono-, di- or trihalogenomethyl group, Y ₁ and Y ₂ are halogen atoms, and Z is a methyl group or a methoxy group).

The present inventors focused their attention on the sulfonamide compound and conducted various studies on the relationship between its chemical structure and physiological activity against plants. As a result, a methyl group was present at the 3-position of the isothiazole ring, and , A specific sulfonamide compound having a halogenoethoxy group or a halogenopropoxy group at the 5-position and further having a specific pyrimidinyl group at the 4-position sulfonylurea chain exhibits an extremely excellent herbicidal effect, The present inventors have found that harmful weeds that grow in paddy fields can be controlled selectively and at a low dose without giving any phytotoxicity to paddy rice, and completed the present invention.

Examples of the halogen atom of the halogenomethyl group of R or the halogen atom of Y ₁ and Y ₂ in the compound of the present invention represented by the above general formula include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. May be the same as or different from each other. The halogen atom is preferably a chlorine atom or a fluorine atom. Examples of the halogenoethoxy group or halogenopropoxy group include -OC
_{H 2 CF 2 H, -OCH 2} CFClH, -OCH 2 CF 2 CF 2 H, -OCH 2 CF 2 C
F _3, etc. -OCH ₂ CF ₂ CH ₃ and the like.

The salt of the sulfonamide compound is a salt of the compound of the general formula (I) and a basic salt-forming substance, and specifically,
Examples thereof include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as magnesium and calcium, and substituted or unsubstituted amines such as methylamine, dimethylamine and triethylamine.

The sulfonamide compound represented by the general formula (I) can be produced, for example, by the following method.

The above reaction is carried out in the presence of a solvent, if necessary. As the solvent, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene: chloroform,
Carbon tetrachloride, dichloromethane, dichloroethane, trichloroethane, hexane, cyclohexane and other cyclic or acyclic aliphatic hydrocarbons: diethyl ether, dioxane, tetrahydrofuran and other ethers, acetone,
Ketones such as methyl ethyl ketone and methyl isobutyl ketone: nitriles such as acetonitrile, propionitrile and acrylonitrile: aprotic polar solvents such as dimethyl sulfoxide and sulfolane: esters such as ethyl acetate. In the above reaction, 1,8-diazabicyclo [5.4.0] -7-undecene may be added to accelerate the reaction, if necessary.

The starting compound represented by the general formula (II) in the above reaction formula is shown to be produced, for example, by the following method.

[In the formula, R ₁ is a —CH ₂ CY ₁ Y ₂ R group (R, Y ₁ and Y ₂ are as described above)].

Next, a synthesis example of the compound of the present invention will be described below.

Synthesis Example 1. N-[(4,6-dimethoxypyrimidine-2-
Aryl) aminocarbonyl] -3-methyl-5- (2,2,3,
Synthesis of 3-Tetrafluoropropoxy) -4-isothiazolesulfonamide (Compound No. 1) [I] 3-Methyl-5- (2,2,3,3-tetrafluoropropoxy) -4-isothiazolesulfonamide Synthesis of (1) 5-bromo-3-methyl-4-nitroisothiazole 5.0 g, 2,2,3,3-tetrafluoropropanol 4.4
While a mixed solution of g and 100 ml of anhydrous tetrahydrofuran was cooled with ice water, 0.98 g of 60% sodium hydride was added little by little, and the mixture was reacted at room temperature for 4 hours with stirring.

After the reaction was completed, the reaction product was poured into 300 ml of water, and ethyl acetate 1
It was extracted with 00 ml, the extract layer was washed with water and dried, and then the solvent was distilled off under reduced pressure. The obtained residue was crystallized from a mixed solvent of ether / hexane to give 3-methyl-4-nitro-mp having a melting point of 38.5-40 ° C.
5.28 g of 5- (2,2,3,3-tetrafluoropropoxy) isothiazole was obtained.

(2) 5.08 g of 3-methyl-4-nitro-5- (2,2,3,3-tetrafluoropropoxy) isothiazole obtained in the above step (1) was dissolved in 50 ml of acetic acid, and reduced iron was added at room temperature.
4.12 g was gradually added little by little, and the mixture was reacted for 23 hours with stirring.

After the reaction was completed, the reaction product was poured into 300 ml of water, and ethyl acetate 1
It was extracted with 00 ml, and the extract layer was washed with an aqueous potassium carbonate solution and then with water, and then dried, and the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (developing solvent, hexane: ethyl acetate = 2: 1) to give an oily 4
3.9 g of -amino-3-methyl-5- (2,2,3,3-tetrafluoropropoxy) isothiazole were obtained.

(3) To 3.9 g of 4-amino-3-methyl-5- (2,2,3,3-tetrafluoropropoxy) isothiazole obtained in the above step (2), 8.9 ml of acetic acid, 11 ml of 85% phosphoric acid and Concentrated hydrochloric acid (6.7 ml) was added, and sodium sulfite (1.19 g) was added thereto at 0 ° C.
3 ml of an aqueous solution was added dropwise, and the mixture was stirred at 0-5 ° C for 2.5 hours to be reacted. Then, 47 ml of acetic acid saturated with sulfurous acid gas containing 0.47 g of cuprous chloride was added little by little while keeping the temperature at 0 ° C. The reaction was carried out at 0 ° C. for 1 hour with stirring.

After the reaction was completed, the reaction product was poured into 200 ml of ice water, and ethyl acetate 100 was added.
extracted with ml. The extract was thoroughly washed with water, dried and the solvent was distilled off under reduced pressure. Then, the obtained residue is purified by silica gel column chromatography (developing solvent, dichloromethane: hexane = 1: 1) to give oily 3-methyl-5- (2,
0.74 g of 2,3,3-tetrafluoropropoxy) -4-isothiazole sulfonyl chloride was obtained.

(4) 3-Methyl-5-obtained in the step (3)
0.74 g of (2,2,3,3-tetrafluoropropoxy) -4-isothiazole sulfonyl chloride was dissolved in 10 ml of acetone, and 0.19 g of sodium hydrogen carbonate was added thereto. The above mixture was cooled to −20 ° C., 0.5 ml of 28% aqueous ammonia was added, the temperature was gradually returned to room temperature, and the mixture was reacted with stirring for 2 hours.

After the reaction was completed, the reaction product was poured into 200 ml of water, and ethyl acetate 1
It was extracted with 00 ml, the extract layer was washed with water and dried, and the solvent was distilled off under reduced pressure. The obtained residue was crystallized from a mixed solvent of ether / hexane to give 3-methyl-5- (2,2,3,3, mp 102-103 ° C.
0.56 g of -tetrafluoropropoxy) -4-isothiazole sulfonamide was obtained.

[II] Synthesis of Target Product (Compound No. 1) 3-Methyl-5- (2, obtained in the above step [I] (4)
200 mg of 2,3,3-tetrafluoropropoxy) -4-isothiazolesulfonamide and 188 mg of phenyl N- (4,6-dimethoxypyrimidin-2-yl) carbamate were dissolved in 20 ml of acetonitrile, and 1,8-diazabicyclo was dissolved at room temperature. [5.4.0] -7-Undecene (104 mg) was added, and the mixture was reacted for 16 hours with stirring.

After the reaction was completed, 100 ml of water was added to the reaction product, and concentrated hydrochloric acid was added dropwise to make it acidic (pH = 3). Filter the precipitated white crystals,
It was dried under reduced pressure to obtain 293 mg of the desired product having a melting point of 166-168 ° C.

Synthesis Example 2. N- (4,6-dimethoxypyrimidin-2-ylaminocarbonyl) -3-methyl-5- (2,2,3,3,3
-Pentafluoropropoxy) -4-isothiazole sulfonamide (Compound No. 2) [I] 3-methyl-5- (2,2,3,3,3-pentafluoropropoxy) -4-isothiazole sulfone Synthesis of amide (1) 5-bromo-3-methyl-4-nitroisothiazole 5.0 g, 2,2,3,3,3-pentafluoropropanol
While cooling a mixed solution of 5.0 g and 100 ml of anhydrous tetrahydrofuran with ice water, 0.98 g of 60% sodium hydride was added little by little, and the mixture was reacted at room temperature for 30 minutes with stirring.

After the reaction was completed, the reaction product was poured into 300 ml of water, and ethyl acetate 1
It was extracted with 00 ml, the extract layer was washed with water and dried, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (developing solvent, hexane: ethyl acetate = 9: 1), and 3-methyl-4-nitro-5- (2,
2,3,3,3-Pentafluoropropoxy) isothiazole
Obtained 5.37 g.

(2) 3-Methyl-4-nitro-5- (2,2,3,3,3-pentafluoropropoxy) obtained in the step (1)
5.27 g of isothiazole was dissolved in 100 ml of acetic acid, 4.0 g of reduced iron was added little by little at room temperature, and the mixture was reacted under stirring for 24 hours.

After the reaction was completed, the reaction product was poured into 300 ml of water, and ethyl acetate 1
It was extracted with 00 ml, and the extract layer was washed with an aqueous potassium carbonate solution and then with water, and then dried, and the solvent was distilled off under reduced pressure. The obtained residue is subjected to silica gel column chromatography (developing solvent, dichloromethane: hexane: ethyl acetate = 8: 1: 1).
Oily 4-amino-3-methyl-5- (2,2,
3,3,3-Pentafluoropropoxy) isothiazole 4.2
I got 4g.

(3) 4-amino-3-methyl-5- (2,2,3,3,3-pentafluoropropoxy) obtained in the step (2)
8 g of acetic acid, 10 ml of 85% phosphoric acid and 6 ml of concentrated hydrochloric acid were added to 4.0 g of isothiazole, and a 3 l aqueous solution of 1.1 g of sodium nitrite was added dropwise at -10 to -5 ° C under stirring at 0 to 5 ° C for 3 hours. Then, it was added little by little to 50 ml of acetic acid saturated with sulfurous acid gas containing 0.5 g of cuprous chloride while keeping at 0 ° C little by little, and reacted at 0 ° C for 2 hours with stirring.

After the reaction was completed, the reaction product was poured into 200 ml of ice water, and ethyl acetate 1
It was extracted with 00 ml. Thoroughly wash the extract layer with water, and after drying,
The solvent was distilled off under reduced pressure. The resulting residue is then purified by silica gel column chromatography (developing solvent, dichloromethane) to give oily 3-methyl-5- (2,2,3,3,3-
1.5 g of pentafluoropropoxy) -4-isothiazolesulfonyl chloride was obtained.

(4) 3-Methyl-5-obtained in the step (3)
(2,2,3,3,3-pentafluoropropoxy) -4-isothiazolesulfonyl chloride 1.49 g in acetone 10 ml
Was dissolved in, and 0.36 g of sodium hydrogen carbonate was added thereto. The above mixture was cooled to -60 ° C and 28% ammonium water was added.
After adding 1 ml, the temperature was gradually returned to room temperature and the reaction was performed for 1.5 hours with stirring.

After the reaction was completed, the reaction product was poured into 200 ml of water, and ethyl acetate 1
It was extracted with 00 ml, the extract layer was washed with water and dried, and the solvent was distilled off under reduced pressure. The obtained residue was crystallized from a mixed solvent of hexane / ether to give 3-methyl-5- (2,2,3,3,3) having a melting point of 101-103 ° C.
0.96 g of 3-pentafluoropropoxy) -4-isothiazolesulfonamide was obtained.

[II] Synthesis of Target Product (Compound No. 2) 3-Methyl-5- (2,2,3,3,3-pentafluoropropoxy) obtained in Step [I] (4) of Synthesis Example 2 above -4
-200 mg of isothiazole sulfonamide and phenyl N
177 mg of-(4,6-dimethoxypyrimidin-2-yl) carbamate was dissolved in 10 ml of acetonitrile, and 1,8-
98 mg of diazabicyclo [5.4.0] -7-undecene was added, and the mixture was reacted under stirring for 15 hours.

After the reaction was completed, 100 ml of water was added to the reaction product, and concentrated hydrochloric acid was added dropwise to make it acidic (pH = 3). Filter the precipitated white crystals,
It was dried under reduced pressure to obtain 224 mg of the desired product having a melting point of 182-185 ° C.

Synthesis Example 3 Synthesis of N- (4,6-dimethoxypyrimidin-2-ylaminocarbonyl) -3-methyl-5- (2-chloro-2-fluoroethoxy) 4-isothiazolesulfonamide (Compound No. 8) [I] Synthesis of 3-methyl-5- (2-chloro-2-fluoroethoxy) -4-isothiazolesulfonamide (1) 5-Bromo-3-methyl-4-nitroisothiazole 5.0 g, 2,2 -While cooling a mixed solution of 4.6 g of a mixture of dichloro-2-fluoroethanol and 2-chloro-2-fluoroethanol (4: 1) and 20 ml of anhydrous tetrahydrofuran with ice water, add 1.35 g of 60% sodium hydride little by little. After that, the mixture was reacted at room temperature for 1 hour with stirring.

After the reaction was completed, the reaction product was poured into 300 ml of water, and ethyl acetate 1
It was extracted with 00 ml, the extract layer was washed with water, dried and the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (developing solvent, hexane: ethyl acetate = 9: 1) to give 3-methyl-4-nitro-5- (2-melting point 65-67 ° C.
Chloro-2-fluoroethoxy) isothiazole 1.02 g
Got

(2) 3.42 g of 3-methyl-4-nitro-5- (2-chloro-2-fluoroethoxy) isothiazole obtained by the same method as in the step (1) was dissolved in 40 ml of acetic acid,
After gradually adding 3.97 g of reduced iron at room temperature little by little, the mixture was reacted for 4 hours with stirring.

After the reaction was completed, the reaction product was poured into 300 ml of water, and ethyl acetate 1
The mixture was extracted with 00 ml, the extract layer was washed with an aqueous solution of potassium carbonate and then with water, and dried, and the solvent was distilled off under reduced pressure. The obtained residue is subjected to silica gel column chromatography (developing solvent,
Purified with hexane: ethyl acetate = 3: 1), melting point 30-31 ℃
2.62 g of 4-amino-3-methyl-5- (2-chloro-2-fluoroethoxy) isothiazole was obtained.

(3) To 2.35 g of 4-amino-3-methyl-5- (2-chloro-2-fluoroethoxy) isothiazole obtained in the above step (2) was added 5.7 ml of acetic acid, 7.6 ml of 85% phosphoric acid and concentrated hydrochloric acid. 4.0 ml was added, and a 3.6 ml aqueous solution of 0.83 g of sodium nitrite was added dropwise thereto at -20 to -10 ° C, and the mixture was reacted at -10 ° C for 2.5 hours with stirring. Then, it was added little by little to 30 ml of acetic acid saturated with sulfurous acid gas containing 0.33 g of cuprous chloride while maintaining the temperature at 0 ° C., and the mixture was reacted at 0 ° C. for 1 hour with stirring.

After the reaction was completed, the reaction product was poured into 200 ml of ice water, and ethyl acetate 100 was added.
extracted with ml. The extract layer was thoroughly washed with water, dried and the solvent was distilled off under reduced pressure. Then, the obtained residue is purified by silica gel column chromatography (developing solvent, hexane: ethyl acetate = 9: 1), and has a melting point of 51-53 ° C., 3-methyl-5-.
1.30 g of (2-chloro-2-fluoroethoxy) -4-isothiazolesulfonyl chloride was obtained.

(4) 3-Methyl-5-obtained in the step (3)
1.0 g of (2-chloro-2-fluoroethoxy) -4-isothiazolesulfonyl chloride was dissolved in 4.5 ml of acetone, and 0.29 g of sodium hydrogen carbonate was added thereto. The above mixture was cooled to −20 ° C., 0.37 ml of 28% ammonia water was added, and then gradually returned to room temperature and reacted for 2 hours with stirring.

After the reaction was completed, the reaction product was poured into 200 ml of water, and ethyl acetate 1
It was extracted with 00 ml, the extract layer was washed with water and dried, and the solvent was distilled off under reduced pressure. The obtained residue was crystallized with an ether / hexane mixed solvent to obtain 0.80 g of 3-methyl-5- (2-chloro-2-fluoroethoxy) -4-isothiazolesulfonamide having a melting point of 111 to 112 ° C.

[II] Synthesis of Target Product (Compound No. 8) 3-Methyl-5- (2-chloro-2-fluoroethoxy) -4-isothiazole obtained in Step [I] (4) of Synthesis Example 3 above Sulfonamide 200 mg and phenyl N-
210 mg of (4,6-dimethoxypyrimidin-2-yl) carbamate was dissolved in 20 ml of acetonitrile, and 1,8-
122 mg of diazabicyclo [5.4.0] -7-undecene was added, and the mixture was reacted under stirring for 16 hours.

After the reaction was completed, 100 ml of water was added to the reaction product, and concentrated hydrochloric acid was added dropwise to make it acidic (pH = 3). Filter the precipitated white crystals,
After drying under reduced pressure, 312 mg of the desired product having a melting point of 169 to 170 ° C. was obtained.

Representative examples of the compound of the present invention included in the general formula (I) are shown below.

Compound No. 1 N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -3-methyl-5- (2,2,3,3-tetrafluoropropoxy) -4-isothiazolesulfonamide Melting point 166-168 ° C. Compound No. 2 N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -3-methyl-5- (2,2,3,3,3-pentafluoropropoxy) -4 -Isothiazole sulfonamide Melting point 182-185 ° C Compound No. 3 N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -3-methyl-5- (2,2-difluoropropoxy) -4- Isothiazole sulfonamide Melting point 160-162 ° C Compound No. 4 N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -3-methyl-5- (2,2,3,3-tetrafluoropropoxy ) -4-isothiazolesulfonami Compound No. 5 N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -3-methyl-5- (2,2,3,3,3-pentafluoropropoxy) -4 -Calcium salt of isothiazole sulfonamide Compound No. 6 N-[(4-methoxy-6-methylpyrimidin-2-yl) aminocarbonyl] -3-methyl-5- (2,2,3,3,
3-Pentafluoropropoxy) -4-isothiazolesulfonamide Melting point 158.5-159 ° C Compound No. 7 N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -3-methyl-5- (2, 2-Difluoroethoxy) -4-isothiazolesulfonamide Melting point 170-172 ° C Compound No. 8 N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -3-methyl-5- (2-chloro -2-
Fluoroethoxy) -4-isothiazolesulfonamide Melting point 169-170 ° C Compound No. 9 N-[(4-methoxy-6-methylpyrimidin-2-yl) aminocarbonyl] -3-methyl-5- (2,2 -Difluoroethoxy) -4-isothiazolesulfonamide Compound No. 10 N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -3-methyl-5- (2,2-dichloropropoxy) -4 -Isothiazole sulfonamide Melting point 168 to 169 [deg.] C. The sulfonamide compounds and salts thereof of the present invention show an excellent herbicidal effect when used as an active ingredient of a herbicidal composition, as will be seen in the test examples below. Especially harmful weeds that grow in paddy fields, such as firefly, Cyperus cylindrica, Cyperus japonicus, Pinus sylvestris, Cyperaceae, such as Kurowai, Urikawa,
Selective and low dose without damaging paddy rice with weeds such as Omodaka and Heraomodaka, Oedaceae such as Konagi, Sesameaceae such as Azena, Misohagidae such as Cicada, and Gramineae such as Mussel. Can be controlled with. Moreover, since these harmful weeds can be controlled even if they are relatively advanced, they are suitable as a herbicidal composition for paddy fields. Furthermore, it is preferable because it can control harmful weeds in upland fields.

In addition to the above-mentioned agricultural land, the herbicidal composition of the present invention can be applied in various fields such as orchards, mulberry fields, forests, farm roads, grounds, and factory sites, and the application method can be appropriately selected from soil treatment and foliage treatment.

When the control composition of the present invention is applied, it is usually a carrier, optionally mixed with a diluent, a solvent, an emulsifier, a spreading agent, various auxiliary agents such as a surfactant, granules, wettable powders, It is used by formulating it in an emulsion, liquid agent, water solvent, etc.

As an auxiliary agent used in the preparation, a solid carrier such as diatomaceous earth, slaked lime, calcium carbonate, talc, white carbon, talc, kaolin, bentonite, sigleite, clay, starch; water, toluene, xylene, solvent naphtha, dioxane, acetone. , Isophorone, methyl isobutyl ketone, chlorobenzene, cyclohexane, dimethyl sulfoxide, dimethylformamide, N-methyl-
Solvents such as 2-pyrrolidone and alcohol; sodium alkyl sulfate, sodium alkylbenzene sulfonate, sodium lignin sulfonate, polyoxyethylene alkylaryl ether sulfate, polyoxyethylene glycol alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene alkylaryl ether ,
Examples thereof include spreading agents such as polyoxyethylene fatty acid ester and polyoxyethylene sorbitan fatty acid ester, surfactants, etc., but are not limited thereto.

A suitable compounding weight ratio of the active ingredient compound and the agricultural chemical auxiliary is generally 0.02: 99.98 to 90:10, preferably 0.03: 99.97 to 60:
40. The appropriate amount of the active ingredient compound cannot be generally defined due to differences in weather conditions, soil conditions, drug formulation, target weed types, application time, etc., but generally, the amount of active ingredient applied per ares is 0.05 to 50 g, Preferably
It is 0.1 to 30 g. The herbicide of the present invention can be mixed or used in combination with other pesticides, fertilizers, soil, phytotoxicity-reducing agents, etc.
In this case, more excellent effect and action may be exhibited.
When mixed or used in combination with other herbicides, examples of the active ingredient of the mixed partner herbicide include the following.

2,4-dichlorophenyl-3'-methoxy-4'-nitrophenyl ether, 2,4-dichlorophenyl-3'-
Methoxycarbonyl-4'-nitrophenyl ether,
2-chloro-2 ', 6'-diethyl-N- (butoxymethyl) acetanilide, 2-chloro-2', 6'-diethyl-N- (propoxyethyl) acetanilide, S-
[(2-Methyl-1-piperidyl) -carbonylmethyl] -0,0-di-n-propyldithiophosphate, S
-(4-chlorobenzyl) -N, N-diethylthiol carbamate, S-ethyl-hexahydro-1H-azepine-1-carbothioate, S- (1-methyl-1-phenethyl) piperidine-1-carbothioate , S-benzyl-N-ethyl-N- (1,2-dimethylpropyl) thiocarbamate, 2-naphthyl-N-methyl-N- (2
-Methoxy-6-pyridyl) thiocarbamate, O-
(Metatertiary butylphenyl) -N-methyl-
N- (6-methoxypyridin-2-yl) -thiocarbamate, 5-tert-butyl-3- (2,4-dichloro-5-isopropoxyphenyl) -1,3,4-oxadiazoline-2- On, 2-benzthiazol-2-yloxyacetic acid, N-methylanilide, 4- (2,4-dichlorobenzoyl) -1,3-dimethyl-5-phenacyloxypyrazole, 4- (2,4-dichlorobenzoyl) ) -1,3
-Dimethylpyrazol-5-yl-p-toluenesulfonate, 4- (2,4-dichloro-3-methylbenzoyl) -1,3-dimethyl-5- (4-methylphenacyloxy) pyrazole, 3,7- Dichloro-8-quinolinecarboxylic acid.

When mixed or used in combination with the herbicidal compound of the present invention and another herbicidal compound, the compounding ratio cannot be unconditionally defined due to differences in meteorological conditions, soil conditions, drug formulation, application timing, application method, etc. The mixing partner herbicidal compound 0.1 per part by weight of the isothiazole compound of (I) and a salt thereof.
To 200 parts by weight, preferably 0.5 to 100 parts by weight, and a suitable application amount is 1 to 10 as the total amount of the active ingredient compounds per are.
It is 0 g, preferably 2 to 50 g.

Further, in that case, the appropriate drug application time is usually from before the weed emergence to the 3 to 4 leaf stage, and in the case of transplanted paddy fields, it is generally from before the transplanting of paddy rice to around 20 days after the transplanting. In addition, upon application, the active ingredient compound is blended with various auxiliary agents as described above in accordance with ordinary pesticide formulation methods, for example, emulsions, wettable powders,
It is prepared in the form of granules or the like, but the active ingredient compounds may be mixed and prepared together, or separately prepared and further mixed.

Next, test examples of the herbicidal composition of the present invention will be described.

Test Example 1. A paddy field soil was filled in a 1 / 10,000 are pot, seeds of firefly were sown, and about 0.5 cm of soil was covered and then flooded to 3 cm. Tuber of Urikawa was planted at the time of germination of firefly, and when the firefly grew in the 0.5 leaf stage, a wettable powder of the given compound was diluted with water,
A predetermined amount was dropped with bipet. After 16 to 26 days from the drug treatment, the growth state was visually observed, and the degree of growth inhibition was evaluated based on the following criteria (5-point method of 1 to 5), and the results shown in Table 1 below were obtained.

Degree of growth suppression 5: Complete withered state ~ 1: Growth equivalent to untreated plots Test example 2. Paddy soil was filled in 1 / 10,000 are pots, seeds of fly were sown, lightly covered with soil, and flooded to 3 cm . When the fly was germinated, a wettable powder of the given compound was diluted with water, and a given amount of the wettable powder was added dropwise with a pipette. After 24-26 days of drug treatment, the growth state is visually observed and evaluated based on the criteria of Test Example 1,
The results shown in Table 1 below were obtained.

Test Example 3 Paddy field soil was filled in 1 / 10,000 are pots, and after the water was filled, scratching was performed, and the next day, 2.5 leaf stage paddy rice (variety: Nihonbare) was transplanted one per pot. On the 4th day after transplantation, a wettable powder of a predetermined compound was diluted with water, and a predetermined amount was dropped by a pipette. After 26 to 38 days from the chemical treatment, the growth state was visually observed and evaluated based on the criteria of Test Example 1, and the results shown in Table 1 below were obtained.

Next, formulation examples of the herbicidal composition of the present invention will be described.

Formulation example 1. (1) 78 parts by weight of dikelite (2) 2 parts by weight of laberin S (trade name: manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) (3) 5 parts by weight of Solpol 5039 (trade name: manufactured by Toho Chemical Industry) (4) Carplex 15 parts by weight (trade name: manufactured by Shionogi Pharmaceutical Co., Ltd.) A mixture of the components (1) to (4) and the compound No. 1 of the present invention.
And 9 are mixed in a weight ratio of 9: 1 to obtain a wettable powder.

Formulation Example 2. (1) 0.5 part by weight of the compound of the present invention (2) 6 parts by weight of Solpol 5146 (trade name: manufactured by Toho Chemical Industry) (3) 2 parts by weight of Neugen EA-112 (trade name: Daiichi Kogyo) (4) Dikelite 25 parts by weight (5) Bentonite 66.5 parts by weight The above (1) to (5) are kneaded with a small amount of water, extruded into granules, and dried to obtain granules.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Tsunezo Yoshida 2-3-1, Nishi-Shibukawa, Kusatsu City, Shiga Ishihara Sangyo Co., Ltd. Central Research Institute (72) Inventor Masahiko Ikeguchi 2-3, Nishi-Shibukawa, Kusatsu City, Shiga Prefecture No. 1 Seiko Tamura, Examiner, Central Research Laboratory, Ishihara Sangyo Co., Ltd. (56) Reference JP 63-270670 (JP, A) JP 63-264508 (JP, A) JP 63-190887 (JP, A) JP 58-219179 (JP, A) JP 60-48988 (JP, A) JP 59-1480 (JP, A)

Claims (3)

[Claims] 1. A general formula: (Wherein R is a hydrogen atom, a methyl group or a mono-, di- or trihalogenomethyl group, Y ₁ and Y ₂ are halogen atoms, and Z is a methyl group or a methoxy group). Compounds and salts thereof. 2. A general formula: (Wherein R is a hydrogen atom, a methyl group or a mono-, di- or trihalogenomethyl group, Y ₁ and Y ₂ are halogen atoms, and Z is a methyl group or a methoxy group). A herbicidal composition comprising a base compound or a salt thereof as an active ingredient. 3. A general formula: (Wherein R is a hydrogen atom, a methyl group or a mono-, di- or trihalogenomethyl group, and Y ₁ and Y ₂ are halogen atoms), and a phenyl N- (4, 6-dimethoxypyrimidin-2-yl) carbamate or phenyl N- (4-methoxy-6-methylpyrimidin-2-yl) carbamate and then optionally treated with a basic salt-forming substance. General formula: (In the formula, Z is a methyl group or a methoxy group, and R, Y ₁ and Y ₂ are as described above.) A method for producing a sulfonamide compound and a salt thereof.