JPH0660180B2 - Sulfonylurea derivative, process for producing the same, and herbicide containing the derivative - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel sulfonylurea derivative, a process for producing the compound, and a selective herbicide containing the compound as an active ingredient.

JP-A-55-102577 and JP-A-56-139.
No. 466 discloses a pyridinesulfonylurea derivative,
JP-A-56-169688 describes that pyrrolesulfonylurea derivatives are useful as herbicides.

It is indispensable to use herbicides to protect important crops such as rice, wheat and corn from weed damage and increase their yield. Particularly in recent years, in arable land where these useful crops and weeds are mixed, a selective herbicide capable of selectively killing only the weeds without showing phytotoxicity to the crops even when the foliage of the crops and the weeds are simultaneously treated is desired. It is rare. Also, to prevent environmental pollution,
From the viewpoint of reducing the economic cost of transportation and spraying, research and exploration of compounds that show high herbicidal effects with the lowest possible dose has been continued for many years. Although some of the compounds with such properties are currently used as selective herbicides, there is still a need for new compounds with these properties.

The present inventors have continued to study for many years to develop a herbicide that is selective for important crops, and to produce a compound having higher herbicidal activity and selectivity, the herbicidal activity of many compounds was determined. I have examined the characteristics. As a result, the compound of the present invention represented by the general formula (I) is remarkably superior to many known weeds in both soil treatment and foliage treatment, even when compared with known pyridinesulfonylurea derivatives and pyrrolesulfonylurea derivatives. The present invention has been completed by discovering that it has strong herbicidal activity and high safety against important crops such as rice, wheat and corn. On the other hand, since the compound of the present invention exhibits a high herbicidal activity with a very low dose as compared with conventional herbicides, it is also useful as a herbicide for other orchards and non-arable land.

The compound of the present invention represented by the general formula (I) is a novel compound and can be easily produced by selecting one of the following reaction formulas 1 to 3.

Reaction formula 1 [In the formula, A, B, W, X, Y and Z have the same meanings as described above. That is, a sulfonyl isocyanate derivative is dissolved in a sufficiently dried inert solvent such as dioxane or acetonitrile, and the pyrimidine or triazine derivative represented by the formula (III) is added thereto and stirred to generally rapidly To give the compound (I) of the present invention. When the reaction is difficult to proceed, the reaction easily proceeds by adding an appropriate base, for example, triethylamine, triethylenediamine, pyridine, sodium alkoxide, sodium hydride and the like in minute amounts.

Reaction formula 2 [In the formula, A, B, W, X, Y and Z have the same meanings as described above. R ¹ represents an alkyl group or a phenyl group. ] That is, the sulfonamide derivative (V)
Compound (IV) is obtained by reacting with chloroformic acid ester or carbonic acid ester in the presence of a base such as potassium carbonate in a solvent such as methyl ethyl ketone and treating with an acidic substance such as hydrochloric acid after the reaction. Then, the compound (I) of the present invention can be obtained by heating the compound (III) in a solvent such as toluene.

Reaction formula 3 [In the formula, A, B and W have the same meanings as described above. E and F represent a halogen atom, R ² represents a lower alkyl group, and G represents a nitrogen atom or a = CH-group.
Compound (VII), which is a part of the compound of the present invention, is synthesized by reacting sulfonamide derivative (V) with pyrimidine or triazine isocyanate (VI) with reference to JP-A No. 1, and then reacted with sodium alcoholate. By doing so, compound (VIII), which is also a part of the compound of the present invention, can be synthesized. Part of the raw material sulfonyl isocyanate used in Reaction Scheme 1 is J. Che.
m.Soc., 7283 (1965) and Gazz.chim.ital., 70 11-18 (19
40) to synthesize isothiazole or isoxazole sulfonamide.
It can be synthesized with reference to the method described in Japanese Patent Publication No. 66. Many of the intermediate sulfonamides are novel compounds, but their synthesis can be achieved by appropriately selecting some of the synthetic routes described below.

Reaction formula 4 [In the formula, A, B and W have the same meanings as described above. Specific examples of the compounds of the present invention are shown in Table 1, Table 2 and Table 3, but the present invention is not limited thereto.

Compound No. is referred to in the description below.

A synthesis example of the intermediate sulfonamide used in the present invention is described below as a reference example.

Reference Example 1 4-Ethoxycarbonyl-3-methylisothiazole-
Synthesis of 5-sulfonamide 5-amino-4-ethoxycarbonyl-3-methylisothiazole 12 g, concentrated hydrochloric acid 20 m, phosphoric acid 40 m and acetic acid 30 m were mixed with an aqueous solution of sodium nitrite 4.8 g at -20 ° C to -10 ° C. It was added at ° C. This solution was stirred at -5 ° C for 30 minutes, and then added little by little to 200 m of a sulfurous acid gas-saturated acetic acid solution containing 2.0 g of cuprous chloride at -10 to -5 ° C. After dropping, the mixture was stirred at 0 to 5 ° C for 1 hour, poured into ice water, and extracted with chloroform. The extract was thoroughly washed with water, dried and the solvent was distilled off to obtain 13 g of crude sulfonyl chloride. The sulfonyl chloride obtained here was dissolved in 50 m of tetrahydrofuran, and this was added to 80 m of 28% aqueous ammonia at a temperature of 10 ° C or lower under ice cooling. After stirring for 3 hours at room temperature, the solid obtained by concentration under reduced pressure was filtered, washed with water and hexane, and dried to give the desired product.
6.3 g was obtained.

Melting point 109-110 ° C. Reference Example 2 Synthesis of 3,5-diethoxycarbonylisothiazole-4-sulfonamide According to the above-mentioned Reference Example, 10 g of 4-amino-3,5-diethoxycarbonylisothiazole was added to give 3,5- Diethoxycarbonylisothiazole-4-sulfonyl chloride
10.3 g was obtained. This was dissolved in 20 m of acetone and 2.6 g of sodium hydrogen carbonate was added. After cooling to -20 ° C, 2.7 g of 28% ammonia water was added dropwise. After the dropwise addition, the mixture was stirred at room temperature for 1 hour, water was added, the mixture was extracted with ethyl acetate, dried, and the solvent was distilled off to obtain 10.5 g of a crude target product. When ether was added and left standing, 6.0 g of the target crystal was precipitated.

Melting point 119 to 120 ° C. Reference Example 3 Synthesis of 5-phenylisothiazole-3-sulfonamide It was synthesized from 3-amino-5-phenylisothiazole according to the above Reference Examples 1 and 2.

Melting point 145 to 147 ° C. Reference Example 4 Synthesis of 3,5-dimethoxycarbonylisothiazole-4-sulfonamide Obtained from 4-amino-3,5-dimethoxycarbonylisothiazole according to the method of Reference Example 2.

Melting point 129 to 131 ° C. Reference Example 5 Synthesis of 5-ethoxycarbonyl-3-methoxycarbonylisothiazole-4-sulfonamide According to the method of Reference Example 2, 4-amino-5-ethoxycarbonyl-3-methoxycarbonylisothiazole ( Melting point
100.6-102.6 ° C).

Melting point 139.0-141.6 ° C. Reference example 6 Synthesis of 3-ethoxycarbonyl-5-methoxycarbonylisothiazole-4-sulfonamide According to the method of Reference example 2, 4-amino-3-ethoxycarbonyl-5-methoxycarbonylisothiazole ( Melting point
94.7-97.5 ° C).

Melting point 132.4-137.8 ° C Reference Example 7 Synthesis of 3-methylisothiazole-5-sulfonamide Obtained as a solid substance from 5-amino-3-methylisothiazole according to the method of Reference Example 1.

Specific synthetic examples of the compound of the present invention using the sulfonamides obtained in Reference Examples 1 to 3 will be described below, but the present invention is not limited thereto.

Example 1 N-[(4-Methoxy-6-methylpyrimidin-2-yl) aminocarbonyl] -3-methylisothiazole-
Synthesis of 4-sulfonamide (Compound No. 2) 5.0 g of 3-methylisothiazole-4-sulfonamide
Is dissolved in 50 m of acetone and 5.0 g of dry potassium carbonate, n
-Butyl isocyanate (3.3 g) was added, the mixture was reacted at room temperature for 1 hour, and then heated under reflux for 3 hours. After the reaction, the solvent was removed under reduced pressure, water was added to the residue to dissolve it, and the insoluble matter was filtered.
The filtrate was acid-precipitated with dilute hydrochloric acid, and the precipitated crystals were filtered, washed with water,
After drying, 7.2 g of N- (n-butylaminocarbonyl) -3-methylisothiazole-4-sulfonamide was obtained.

Melting point 120-122 ° C. Add the above compound to 80 m of dry toluene and heat to reflux.
7.1 g of phosgene was blown in, and the mixture was heated under reflux for another 3 hours. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain a crude sulfonyl isocyanate. This crude sulfonyl isocyanate 1.
0 g was added to a solution of 0.4 g of 2-amino-4-methoxy-6-methorpyrimidine in 20 m of dry acetonitrile, and the mixture was stirred at room temperature. The precipitated crystals were filtered, washed and dried to obtain 0.8 g of the desired product.

Melting point 175 to 176 ° C Example 2 Synthesis of N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl) aminocarbonyl] -3,5-dimethylisoxazole-4-sulfonamide (Compound No. 116) According to the above-mentioned example, N- (n-butylaminocarbonyl) -3,5-dimethylisoxazole-4-sulfonamide was obtained from 3,5-dimethylisoxazole-4-sulfonamide. It was

Mp 163-169 ° C., followed by phosgene, then 2-amino-4-methoxy-6
The target compound was obtained by reacting with -methyl-1,3,5-triazine.

Melting point 177 to 179 ° C. Example 3 Synthesis of N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -4-ethoxycarbonyl-3-methylisothiazol-5-sulfonamide (Compound No. 170) Using the sulfonamide obtained in Reference Example 1 and in accordance with Example 1 above, N- (n-butylaminocarbonyl) -4
-Ethoxycarbonyl-3-methylisothiazole-5
-The sulfonamide was obtained.

Melting point 143-145 ° C. This was reacted with phosgene and then 2-amino-4,6-dimethoxypyrimidine to obtain the desired product.

Melting point 145 to 146 [deg.] C. Then, the compound specifically synthesized according to the above Examples 1, 2, and 3 together with the compounds synthesized in Examples 1, 2, and 3 (Compound No. 2, 116, 170). The results are shown in Table 4 below.

In applying the compound of the present invention as a herbicide, generally, a suitable carrier, such as clay, talc, bentonite, a solid carrier such as diatomaceous earth or water, alcohols (methanol, ethanol, etc.), aromatic hydrocarbons (benzene, Toluene, xylene, etc.), chlorinated hydrocarbons, ethers, ketones, esters (ethyl acetate, etc.), acid amides (dimethylformamide, etc.), etc. By adding an emulsifier, a dispersant, a suspending agent, a penetrating agent, a spreading agent, a stabilizer and the like, it can be put into practical use in any dosage form such as liquid, emulsion, wettable powder, powder and granules.

Next, formulation examples of a herbicide containing the compound of the present invention as an active ingredient will be shown, but the invention is not limited thereto. In the following formulation examples, "part" means part by weight.

Formulation Example 1 Wettable powder Compound No. 1 of the present invention ...... 50 parts Diquelite A ...... 46 parts (Kaolin clay: product name of Sikelite Co., Ltd.) Sorpol 5039 ...... 2 parts (Nonionic surfactant And anionic surfactant: Toho Chemical Co., Ltd. trade name Carplex (anti-caking agent) 2 parts (white carbon: Shionogi Seiyaku Co., Ltd. trade name) To make wettable powder. Upon use, the wettable powder is diluted 50 to 50,000 times and sprayed so that the amount of the active ingredient is 0.005 kg to 10 kg per hectare.

Formulation Example 2 Wettable powder Compound No. 2 of the present invention ...... 75 parts Diquelite A …… 19 parts (Kaolin-based clay: product name of Siglite Industrial Co., Ltd.) Solpol 5039 …… 2 parts (Nonionic surfactant And anionic surfactant: Toho Chemical Co., Ltd. trade name Carplex (anti-caking agent) …… 4 parts (white carbon: Shionogi Seiyaku Co., Ltd. trade name) To make wettable powder.

Formulation Example 3 Wettable powder Compound No. 98 of the present invention: 50 parts Diquelite A: 46 parts (Kaolin-based clay: product name of Sikelite Industry Co., Ltd.) Solpol 5039: 2 parts (Nonionic surfactant And anionic surfactant: Toho Chemical Co., Ltd. trade name Carplex (anti-caking agent) 2 parts (white carbon: Shionogi Seiyaku Co., Ltd. trade name) To make wettable powder.

Formulation Example 4 Wettable powder Compound No. 169 of the present invention ...... 25 parts Diquelite A ...... 71 parts (Kaolin clay: Sikhlite Industry Co., Ltd. trade name) Solpol 5039 ...... 2 parts (Nonionic surfactant And anionic surfactant: Toho Chemical Co., Ltd. trade name Carplex (anti-caking agent) 2 parts (white carbon: Shionogi Seiyaku Co., Ltd. trade name) To make wettable powder.

Formulation Example 5 Emulsion Compound No. 99 …… 2 parts Xylene …… 78 parts Dimethylformamide …… 15 parts Solpol 2680 …… 5 parts (Mixture of nonionic surfactant and anionic surfactant: Toho Kagaku) Brand name) The above is uniformly mixed to form an emulsion. At the time of use, the above emulsion is diluted 10 to 10,000 times and sprayed so that the amount of the active ingredient is 0.005 kg to 10 kg per hectare.

Formulation Example 6 Flowable compound of the present invention No. 3 ... 25 parts Agrisol S-710 ... 10 parts (Nonionic surfactant: Kao Atlas Co., Ltd. trade name) Lunox 1000C ... 0.5 part (anionic interface Activator: Toho Kagaku Co., Ltd. product name) 1% Rhodopol water ...... 20 parts (Thickener: Lone Poulean company product name) Water ...... 44.5 parts

Formulation Example 7 Granules Compound of the present invention No. 1 ...... 0.5 part Bentonite ...... 55.0 parts Talc ...... 44.5 parts After uniformly mixing and pulverizing the above, add a small amount of water, knead with stirring, and knead with extrusion type. Granulate with a granulator and dry to granules.

Compounding Example 8 Granules Compound of the present invention No. 7 ...... 0.7 parts Bentonite ...... 55.0 parts Talc ...... 44.3 parts After uniformly mixing and pulverizing the above, a small amount of water is added and the mixture is kneaded with stirring, and extrusion molding is performed. Granulate with a granulator and dry to give granules.

Further, the compound of the present invention may be mixed and applied with other kinds of herbicides, various insecticides, fungicides, synergists and the like at the time of preparation or spraying, if necessary.

Examples of the above-mentioned other types of herbicides include, for example, Farm Chemicals. Handbook (Farm Chemicals Handbook) 6
8th edition (1982) and the like.

The compound of the present invention can be applied to the control of various weeds in non-agricultural fields such as fields, paddy fields, orchards in fields other than agricultural and horticultural fields such as orchards, and its application dosage is Although there are differences depending on the time of application, application method, target grass species, cultivated product, etc., generally, the amount of active ingredient is preferably about 0.005 to 10 kg per hectare.

Next, the usefulness of the compound of the present invention as a herbicide will be specifically described in the following test examples.

Test Example-1 Herbicidal effect test by soil treatment Put sterilized diluvial soil in a plastic box having a length of 15 cm, a width of 22 cm, and a depth of 6 cm, and sowing rice, novier, crabgrass, cyperaceae, koa kaza, purslane, syringa, and Capsicum in a mixed manner. After covering the soil with about 1.5 cm, it was uniformly sprayed on the soil surface so that the amount of the active ingredient was a predetermined ratio.

The chemical solution for spraying was prepared by diluting the wettable powder of the above formulation example with water and spraying it over the entire surface with a small spray. Four weeks after spraying the chemical solution, the herbicidal effect on rice and various weeds was investigated according to the following criteria.

The results are shown in Table 5.

Some of the compounds of this invention are selective for certain crops.

Criteria 5 ... Herbicide rate 90% or more (almost complete death) 4 ... Herbicide rate 70-90% 3 ... Herbicide rate 40-70% 2 ... Herbicide rate 20-40% 1 ... Herbicide rate 5-20% 0 ... Herbicide rate 5% or less (almost no effect) However, the above-mentioned herbicidal rate is obtained by measuring the above-ground vegetation weight of the chemical treatment area and the above-ground vegetation weight of the non-treatment area by the following formula.

Test Example-2 Herbicidal effect test by foliar treatment 15 cm long, 22 cm wide, 6 cm deep in a plastic box containing sterilized diluvial soil, rice, crabgrass, cyperaceae,
Koa kaza, leaf-shaped sage, dog pepper, corn,
Soybean, wheat, and tomato seeds were sown in spots and covered with about 1.5 cm of soil. When various plants reached the 2-3 leaf stage, the active ingredients were sprayed evenly on the foliage so that the amount of the active ingredient became a predetermined ratio.

The chemical solution for spraying was prepared by diluting the wettable powder of the above formulation example with water and spraying it over the entire surface of the foliage of various weeds with a small spray. Four weeks after spraying the chemical solution, the herbicidal effect on rice and various weeds was investigated according to the criteria of Test Example-1.

The results are shown in Tables 6 and 7.

Front page continued (72) Inventor Toshihiko Oguchi 1470 Shiraoka, Shiraoka-cho, Minami-Saitama-gun, Saitama Nissan Biochemical Laboratory Co., Ltd. (72) Inventor Tsutomu Namaki 1470 Shiraoka, Shirooka-cho, Minami-Saitama-gun, Saitama Nissan Chemical Industry Co., Ltd. Misao Takanashi, Examiner, Institute for Biochemistry, Japan (56) References JP-A-58-219179 (JP, A) JP-A-59-1480 (JP, A)

Claims (3)

[Claims] 1. General formula (I): [Wherein Q is (In the formula, A ¹ represents a lower alkyl group or COOR (R represents a lower alkyl group), A ² represents a lower alkyl group,
A ³ represents a hydrogen atom, B ¹ is a lower alkyl group or COOR
(R represents a lower alkyl group) and B ² represents COOR (R
Represents a lower alkyl group. ), B ³ represents a phenyl group, W ¹ represents a sulfur atom or an oxygen atom, and W ² and W ³
Are each independently a sulfur atom. ), X and Y each independently represent a lower alkyl group or a lower alkoxy group, and Z represents a nitrogen atom or a CH group. However, Q is Represents a CH group. ] A sulfonylurea derivative represented by: 2. A general formula (II): Q-SO ₂ NCO (II) [wherein Q is (In the formula, A ¹ represents a lower alkyl group or COOR (R represents a lower alkyl group), A ² represents a lower alkyl group,
A ³ represents a hydrogen atom, B ¹ is a lower alkyl group or COOR
(R represents a lower alkyl group) and B ² represents COOR (R
Represents a lower alkyl group. ), B ³ represents a phenyl group, W ¹ represents a sulfur atom or an oxygen atom, and W ² and W ³
Are each independently a sulfur atom. ) Is shown. ] And a sulfonyl isocyanate derivative represented by the following formula (III): [In the formula, X and Y each independently represent a lower alkyl group or a lower alkoxy group, and Z is a nitrogen atom or CH.
Indicates a group. However, Q is Represents a CH group. ] An aminopyrimidine or aminotriazine derivative represented by the following formula is reacted in an inert solvent, represented by the general formula (I): A method for producing a sulfonylurea derivative represented by: 3. General formula (I): [Wherein Q is (In the formula, A ¹ represents a lower alkyl group or COOR (R represents a lower alkyl group), A ² represents a lower alkyl group,
A ³ represents a hydrogen atom, B ¹ is a lower alkyl group or COOR
(R represents a lower alkyl group) and B ² represents COOR (R
Represents a lower alkyl group. ), B ³ represents a phenyl group, W ¹ represents a sulfur atom or an oxygen atom, and W ² and W ³
Are each independently a sulfur atom. ), X and Y each independently represent a lower alkyl group or a lower alkoxy group, and Z represents a nitrogen atom or a CH group. However, Q is Represents a CH group. ] The herbicide which contains 1 type, or 2 or more types of the sulfonylurea derivative represented by these as an active ingredient.