JPH06329642A - Sulfonylurea derivative and herbicide containing the same as an active ingredient - Google Patents

Abstract

PURPOSE:To obtain a new sulfonylurea derivative having board herbicidal spectrum, high herbicidal effect and excellent safety to crop plants. CONSTITUTION:A compound of formula I (R is lower alkyl; X, R are halogen, lower alkyl, lower alkoxy; n is 0, 1), for example, 2-[3-(4,6-dimethoxypyrimidin-2- yl)ureidosulfonyloxy]-1-fluorocyclopentanecarboxylic acid ethyl ester. This compound is obtained by reaction of an alkoxysulfonyl isocyanate of formula III with a compound of formula IV, preferably in a solvent at -10 deg.C to the boiling point of the solvent for 1 to 20 hours. The herbicides containing the compound can be applied to rice paddies and crop fields against weeds before their germination to their growing stage for expelling as well as prevention.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel sulfonylurea derivative not described in the literature, and a herbicide containing the derivative as an active ingredient.

[0002]

2. Description of the Related Art JP-A-2-279677 describes a phenoxysulfonylurea derivative represented by the following general formula (II) and a herbicide containing the same.

[0003]

[Chemical 3]

[Wherein R ₁ is C ₁ -C ₄ alkyl,
R ₂ is halogen, methoxy, ethyl or propyl, R ₃ is hydrogen or methyl, E is CH or N
And R ₄ and R ₅ independently of _one another are C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄ alkylthio, the group bearing said alkyl group being unsubstituted or A compound represented by: or a salt thereof, which is substituted with one or more halogen atoms or one or more C ₁ -C ₄ alkylthio groups. ]

[0005]

However, the compounds described in the above documents still have points to be improved in terms of herbicidal spectrum, amount of dropped drug, selectivity for crops and the like.
An object of the present invention is to develop a compound having a broad herbicidal spectrum, a high herbicidal effect, and excellent safety for crops.

[0006]

[Means for Solving the Problems] As a result of intensive studies to achieve the above object, the present inventors succeeded in creating a new sulfonylurea derivative, and this compound was excellent not only for annual but also for perennial weeds. The present invention has been completed by finding that it has a herbicidal effect and is highly safe for certain crops. That is, according to the present invention, the following general formula:

[0007]

[Chemical 4]

[Wherein R represents a lower alkyl group, X
And Y each independently represent a halogen atom, a lower alkyl group or a lower alkoxy group, and n is 0 or 1. ] The sulfonylurea derivative represented by these, and the herbicide which makes it an active ingredient are provided.

[0009]

DETAILED DESCRIPTION OF THE INVENTION In the definitions of the substituents R, X and Y in the general formula (I), specific examples of each group are shown below. Halogen atom : Examples include fluorine, chlorine and bromine. Lower alkyl group : for example, methyl, ethyl, normal propyl, isopropyl, normal butyl, isobutyl,
Examples thereof include lower alkyl groups having 4 or less carbon atoms such as secondary butyl and tertiary butyl groups. Lower alkoxy group : For example, a lower alkoxy group having 4 or less carbon atoms such as methoxy, ethoxy, normal propoxy, isopropyloxy, normal butoxy, isobutoxy, secondary butoxy, tertiary butoxy and the like can be mentioned. The groups not specifically shown above can be selected in any combination from the above groups and atoms, or according to commonly known common sense.

Among the compounds represented by the above general formula (I), particularly preferable one is R is a methyl group or an ethyl group, X is a methoxy group, Y is a methoxy group, a methyl group or chlorine. , X is methyl, and Y is chlorine. Specific examples of the compound of the present invention represented by the general formula (I) are shown in Table 1. In Table 1, Me means a methyl group, Et means an ethyl group, n-Pr means a normal propyl group, and i-Pr means an isopropyl group. In addition, a compound in which the alkoxycarbonyl group and the pyrimidinylureidosulfonyloxy group have a cis configuration is
A compound that is in the trans configuration is is.

[0011]

[Table 1]

[0012]

[Table 2]

[0013]

[Table 3]

[0014]

[Table 4]

[0015]

[Table 5]

[0016]

[Table 6]

[0017]

[Table 7]

[0018]

[Table 8]

[0019]

[Table 9]

[0020]

[Table 10]

[0021]

[Table 11]

[0022]

[Table 12]

[0023]

[Table 13]

The compound of the present invention can be produced, for example, by the following methods (method A, method B and method C).

[0025]

[Chemical 5]

[In the formula, R, X, Y and n have the same meanings as described above. In the reaction formula of the above Method A, the compound of the present invention represented by the formula (I) is a compound represented by the formula (III) and a compound represented by the formula (IV), preferably methylene chloride and chloroform. Halogenated hydrocarbon solvents such as; ether ether solvents such as diethyl ether, tetrahydrofuran, 1,4-dioxane, dimethoxyethane; benzene, toluene,
It can be produced by reacting in a hydrocarbon solvent such as xylene or chlorobenzene; a solvent such as acetonitrile at a temperature range of -10 ° C to the boiling point of the solvent for 1 to 24 hours. The alkoxysulfonyl isocyanate represented by the formula (III) is obtained by combining the corresponding cycloalkanol and chlorosulfonyl isocyanate of the following formula (V) with
For example, it can be easily produced by reacting in a hydrocarbon solvent such as benzene, toluene, xylene, and chlorobenzene. The compounds of formula (IV) are known compounds or can be obtained, for example, by cyclizing the corresponding guadinine derivatives with the correspondingly substituted 1,3-diketone derivatives.

[0027]

[Chemical 6]

[In the formula, R, X, Y and n have the same meanings as described above. In this method, the compound represented by the formula (V) and the chlorosulfonylurea derivative represented by the formula (VI) are treated with a halogenated hydrocarbon solvent such as methylene chloride or chloroform; diethyl ether, tetrahydrofuran, 1, 4-
By reacting in an ether solvent such as dioxane or dimethoxyethane in the presence of a base in the temperature range of −10 ° C. to the boiling point of the solvent in the presence of a base for 0.5 to 24 hours, the formula ( The compound of I) is produced. As the base, carbonates such as sodium carbonate and potassium carbonate,
Examples thereof include tertiary amines such as triethylamine and pyridine. Cycloalkanols of formula (V) can be prepared, for example, by the method described in EP-A-46867, chlorosulfonylurea derivatives of formula (VI) are described, for example, in EP-A-1.
It can be prepared from the amine of formula (IV) and chlorosulfonyl isocyanate by the method described in 41199.

[0029]

[Chemical 7]

[In the formula, R, X, Y and n have the same meanings as described above, and Z represents a phenyl group or an alkyl group having 1 to 6 carbon atoms. In this method, the compound of the formula (VII) and the carbamate derivative of the formula (VIII) are prepared, for example, in an ether solvent such as diethyl ether, tetrahydrofuran, 1,4-dioxane or dimethoxyethane, or a solvent such as acetonitrile. , Diazabicyclo- [5,4,0] -undecene (7) and the like in the presence of a tertiary amine at a temperature range of 0 to the boiling point of the solvent for 0.5 to 24 hours to give a compound of formula ( The compound of I) is produced. The compound of formula (VII) can be prepared from the corresponding cycloalkanol (V), for example as described in Chemiche Berichte 2791 105 (1972), and the carbamate of formula (VIII) is described, for example, in European Patent Publication No. It can be produced by a method described in a known document such as the specification of 70804.

The compound represented by the above general formula (I) of the present invention has activity as a herbicide. When the compound of the present invention is used as a herbicide, the compound is mixed with a carrier or diluent, an additive, an auxiliary agent and the like by a method known per se, and a formulation form usually used as an agricultural chemical, for example, a powder, It is used after being prepared into granules, wettable powders, emulsions, liquids, flowables and the like. Also other pesticides, such as fungicides, insecticides, acaricides, other herbicides, plant growth regulators,
It can be used as a mixture or in combination with a fertilizer, a soil conditioner or the like. In particular, when used in combination with other herbicides, it not only reduces the amount of the drug used and saves labor, but it is also expected that the synergistic action of both drugs will broaden the herbicidal spectrum and further enhance the synergistic effect. .

As the carrier or diluent used in the preparation, a solid or liquid carrier generally used in agriculture is used. Examples of solid carriers include clays and talc represented by kaolinite group, montmorillonite group, illite group, apatargite group, and the like;
Other inorganic substances such as diatomaceous earth, magnesium lime, apatite, zeolite, anhydrous silicic acid, synthetic calcium silicate; soy flour, tobacco flour, walnut flour, wheat flour, wood flour, starch, crystalline cellulose and other plant organic substances Substances: coumarone resin, petroleum resin, alkyd resin, polyvinyl chloride, polyalkylene glycol, ketone resin, ester gum,
Examples thereof include synthetic or natural polymer compounds such as cobal gum and dammal gum; and waxes such as carnauba wax and beeswax and urea.

Suitable liquid carriers include, for example, paraffinic or naphthenic hydrocarbons such as kerosene, mineral oil, spindle oil and white oil; aromatic hydrocarbons such as toluene, xylene, ethylbenzene, cumene and methylnaphthalene; dioxane, Ethers such as tetrahydrofuran; methyl ethyl ketone, diisobutyl ketone,
Ketones such as cyclohexanone, acetophenone, and isophorone; esters such as ethyl acetate, amyl acetate, ethylene glycol acetate, diethylene glycol acetate, dibutyl maleate, diethyl succinate; methanol, n-hexanol, ethylene glycol, diethylene glycol, cyclohexanol, benzyl Examples thereof include alcohols such as alcohols, ether alcohols such as ethylene glycol ethyl ether, ethylene glycol phenyl ether, diethylene glycol ethyl ether, and diethylene glycol butyl ether; polar solvents such as dimethylformamide and dimethyl sulfoxide, and water. In addition, surfactants and other auxiliary agents may be used for the purpose of emulsification, dispersion, wetting, spreading, binding, disintegration control, stabilization of active ingredient, improvement of fluidity, rust prevention, etc. of the compound of the present invention. . Examples of surfactants used may be nonionic, anionic, cationic and zwitterionic, but are usually nonionic and / or anionic. A compound is used.

Suitable nonionic surfactants include, for example, compounds obtained by polymerizing addition of ethylene oxide to higher alcohols such as lauryl alcohol, stearyl alcohol and oleyl alcohol; isooctylphenol,
Compounds obtained by polymerizing addition of ethylene oxide to alkylphenols such as nonylphenol; Compounds obtained by polymerizing addition of ethylene oxide to alkylnaphthols such as butylnaphthol and octylnaphthol; Polymerization addition of ethylene oxide to higher fatty acids such as palmitic acid, stearic acid and oleic acid Examples thereof include compounds; higher fatty acid esters of polyhydric alcohols such as sorbitan, compounds obtained by polymerizing addition of ethylene oxide, and compounds obtained by block-polymerizing addition of ethylene oxide and propylene oxide.

Suitable anionic surfactants include, for example, alkyl sulphate ester salts such as sodium lauryl sulphate, oleyl alcohol sulphate ester amine salts; alkyl succinate dioctyl ester sodium, 2-ethylhexene sulphonate sodium and the like. Sulfonates; aryl sulfonates such as sodium isopropylnaphthalenesulfonate, sodium methylenebisnaphthalenesulfonate, sodium ligninsulfonate, sodium dodecylbenzenesulfonate, and the like.

Further, in the herbicide of the present invention, polymers such as casein, gelatin, albumin, glue, sodium alginate, carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose and polyvinyl alcohol are used for the purpose of improving the properties of the preparation and enhancing the herbicidal effect. Compounds and other auxiliary agents can be used in combination. The above carriers and various auxiliary agents are appropriately used alone or in combination depending on the purpose, taking into consideration the dosage form of the preparation, the application scene and the like.

The content of the compound (active ingredient) of the present invention in the various dosage forms thus obtained varies depending on the dosage form, but is usually 0.1 to 99% by weight, and particularly preferably Most preferred is 1-80% by weight. In the case of a wettable powder, for example, the active ingredient compound is usually 25 to 9
The rest is a solid carrier and a dispersion wetting agent, and a protective colloid agent, a defoaming agent and the like are added if necessary. In the case of granules, for example, the active ingredient compound is usually contained in an amount of 1 to 35% by weight, and the balance is mostly solid carriers and surfactants. The active ingredient compound is either uniformly mixed with the solid carrier or is uniformly fixed or adsorbed on the surface of the solid carrier, and the particle diameter is about 0.2 to 1.5 mm. In the case of emulsions, for example, the active ingredient compound is usually 5
˜60% by weight, which contains about 5 to 20% by weight of emulsifier, the balance being a liquid carrier, optionally with a rust inhibitor. In the case of a flowable agent, for example, it usually contains 5 to 50% by weight of the active ingredient compound, and this contains 3 to 10% by weight of a dispersion wetting agent.
The balance is water, and a protective colloid agent, a preservative, an antifoaming agent and the like are added if necessary. The sulfonylurea derivative of the present invention can be applied as it is to the compound of general formula (I) or in any of the preparation forms as described above. The herbicide of the present invention can be applied to the control or control of various weeds growing in paddy fields and upland fields from the time of outbreak to the growing season. The application amount is about 0.1 to 10,000 g, preferably about 1 to 5,000 g per 1 ha as the amount of the compound represented by the general formula (I) (the amount of the active ingredient), and the kind of the weed of interest. It can be appropriately selected and changed depending on the growth stage, application place, application time, weather and the like.

[0038]

EXAMPLES Next, the present invention will be described more specifically with reference to examples. Example 1 2- [3- (4,6-dimethoxypyrimidin-2-i
Le) Ureidosulfonyloxy] -1-fluorocyclo
Pentanecarboxylic acid ethyl ester (cis form) (Compound
No. 115) synthesis : 2-amino-4,6-dimethoxypyrimidine 0.78 g was dissolved in methylene chloride 25 ml,
Chlorosulfonyl isocyanate 0.44 ml under ice temperature
Was dripped. After stirring for 1 hour at room temperature, 1.14 ml of triethylamine and 0.88 of 1-ethoxycarbonyl-1-fluorocyclopentanol (cis form) were added to this solution.
A solution of g in methylene chloride 10 ml was slowly added dropwise under ice temperature. The reaction solution was stirred overnight at room temperature, poured into diluted hydrochloric acid, and extracted with methylene chloride. The methylene chloride layer was washed with saturated brine, dried over magnesium sulfate, and the solvent was evaporated under reduced pressure. The concentrated residue was purified by silica gel chromatography to give 0.50 g of the desired compound.
Got

Example 2 2- [3- (4,6-dimethoxypyrimidin-2-i
Le) Ureidosulfonyloxy] -1-fluorocyclo
Pentanecarboxylic acid ethyl ester (trans form)
Compound No. 160) Synthesis : 1- Ethoxycarbonyl -1-
Fluorocyclopentanol (trans form) 0.88g
Was dissolved in 5 ml of xylene, and 0.52 ml of chlorosulfonyl isocyanate was added dropwise at room temperature. After completion of the dropping, the mixture was stirred at room temperature for 30 minutes and then under reflux for 3 hours. After cooling the reaction solution, the solvent was distilled off under reduced pressure. The concentrated residue was dissolved in 5 ml of methylene chloride, and 2-amino-4,6-
0.78 g of dimethoxypyrimidine is added to 13 m of methylene chloride.
The solution dissolved in 1 was added dropwise under ice temperature. The reaction solution was stirred overnight at room temperature, poured into diluted hydrochloric acid, and extracted with methylene chloride. The methylene chloride layer was washed with saturated brine, dried over magnesium sulfate, and the solvent was evaporated under reduced pressure. The concentrated residue was purified by silica gel chromatography to obtain 1.05 g of the target compound.

Example 3 2- [3- (4,6-dimethoxypyrimidin-2-i]
Le) Ureidosulfonyloxy] -1-fluorocyclo
Hexanecarboxylic acid ethyl ester (trans form)
Compound No. 340) : 1-ethoxycarbonyl-1-
Fluorocyclohexanol (trans form) 1.90 g
Was dissolved in 10 ml of xylene, and 1.04 ml of chlorosulfonyl isocyanate was added dropwise at room temperature. After completion of the dropping, the mixture was stirred at room temperature for 30 minutes and then under reflux for 3 hours. After cooling the reaction solution, the solvent was distilled off under reduced pressure. The concentrated residue was dissolved in 5 ml of methylene chloride, and 2-amino-4,6-
1.55 g of dimethoxypyrimidine in 25 m of methylene chloride
The solution dissolved in 1 was added dropwise under ice temperature. The reaction solution was stirred overnight at room temperature, poured into diluted hydrochloric acid, and extracted with methylene chloride. The methylene chloride layer was washed with saturated brine, dried over magnesium sulfate, and the solvent was evaporated under reduced pressure. The concentrated residue was purified by silica gel chromatography to obtain 3.34 g of the desired compound.

Physical property data of the compound of the present invention synthesized by the same method are shown in Table 2. In addition, NMR represents a nuclear magnetic resonance spectrum of protons, and the unit is ppm and the unit of melting point is ° C.

[0042]

[Table 14]

Next, several embodiments of formulation examples using the compound of the present invention will be shown. "Parts" in the following formulation examples are based on weight. Formulation Example 1 (Wettable powder) Compound No. 340 20 parts Clay 70 parts Sodium lignin sulfonate 7 parts Alkylnaphthalene sulfonate formalin condensate 3 parts The above components are mixed and uniformly pulverized by a jet mill to obtain wettable powder 100. I got a part.

Formulation Example 2 (Emulsion) Compound No. 344 20 parts Xylene 50 parts Cyclohexanone 20 parts Calcium dodecylbenzene sulfonate 5 parts Polyoxyethylene styryl phenyl ether 5 parts The above components were uniformly mixed and dissolved to obtain 100 parts of an emulsion. . A drug using the compound of the present invention could be prepared according to the above-mentioned preparation examples.

Formulation Example 3 (Flowable) Compound NO.340 20 parts Sulfosuccinic acid di-ethylhexyl ester sodium salt 2 parts Polyoxyethylene nonylphenyl ether 2 parts Defoamer 0.5 parts Propylene glycol 5 parts Water 70.5 parts or more Were uniformly pulverized and mixed with a wet ball mill to obtain 100 parts of a flowable agent. Herbicides using the compounds of the present invention can be prepared according to the above-mentioned formulation examples.

Next, the herbicidal effect will be described with reference to test examples. Test Example 1 (paddy soil treatment) A 130 cm ² plastic pot was filled with paddy soil,
A proper amount of water and a chemical fertilizer were added and kneaded to form a paddy field. Rice seedlings (cultivar: Koshihikari), which had been grown in a greenhouse so that the number of leaves was 2 in advance, were transplanted to each plant as 1 strain per pot, and 1 plant / pot was further transplanted. A certain amount of pups were sowed and submerged at a depth of 3 cm. The next day, a wettable powder was prepared according to Formulation Example 1 and the active ingredient was added for 1 h.
It was diluted with an appropriate amount of water so that the amount per a was 1 kg, and the solution was dropped with a pipette. Twenty-one days after the chemical treatment, the herbicidal effect on each weed and the degree of chemical damage to paddy rice were determined according to the following criteria. The results are shown in Table 3.

[0047]

[Table 15]

[0048]

[Table 16]

Test Example 2 (Paddy field foliage treatment) A 130 cm ² plastic pot was filled with paddy soil,
A proper amount of water and a chemical fertilizer were added and kneaded to form a paddy field. Rice seedlings (cultivar: Koshihikari), which had been grown in a greenhouse so that the number of leaves was 2 in advance, were transplanted to each plant as 1 strain per pot, and 1 plant / pot was further transplanted. A certain amount of pups were sowed and submerged at a depth of 3 cm. After growing Nobie in the greenhouse until the 1.5 leaf stage, prepare a wettable powder according to Formulation Example 1, dilute with an appropriate amount of water to 5 kg per ha, and pipette. It was dropped. Twenty-one days after the chemical treatment, the herbicidal effect on each weed and the degree of chemical damage to paddy rice were determined according to the following criteria. The results are shown in Table 4.

[0050]

[Table 17]

Test Example 3 (Treatment of Upland Soil) A 130 cm ² plastic pot was filled with upland soil,
A certain amount of each variety of Novier, Crabgrass, Ekologsa, velvetleaf, Onami fir, Tedda and P. persicae was sown and then covered with 1 cm of soil. The day after seeding, Formulation Example 1
A wettable powder is prepared in accordance with
It was diluted with an appropriate amount of water so as to be g and sprayed evenly on the soil surface. Twenty-one days after the chemical treatment, the herbicidal effect on each weed was determined according to the criteria of Test Example 1. The results are shown in Table 5.

[0052]

[Table 18]

Test Example 4 (Treatment of Upland Field and Leaves) 130 cm ² plastic pot was filled with upland soil,
A certain amount of each variety of Novier, Crabgrass, Ekologsa, velvetleaf, Onami fir, Tedda and P. persicae was sown and then covered with 1 cm of soil. After seeding, the pot was placed in a glass greenhouse and each plant was grown to have 2 to 4 leaves, and then a wettable powder was prepared according to Formulation Example 1, and the active ingredient was used for 1 h.
It was diluted with an appropriate amount of water so as to be 5 kg per a and sprayed evenly on the leaf surface of the plant. Twenty-one days after the chemical treatment, the herbicidal effect on each weed was determined according to the criteria of Test Example 1. The results are shown in Table 6.

[0054]

[Table 19]

[0055]

Industrial Applicability The sulfonylurea derivative represented by the general formula (I) of the present invention is an annual weed that occurs in paddy fields such as barnyardgrass, pearl oyster, konjac, yellow cypress, azena, and aphid, and firefly, matsubai, heraomodaka, mizugayatsuri, etc. It has an excellent herbicidal effect with a very low dose over a wide range of germination and growing season of perennial weeds, and at the same time has high safety against transplanted paddy rice, directly flooded paddy rice and direct paddy rice. is there. Further, various weeds that are also problematic in the field, such as, for example, broadleaf weeds such as Japanese radish, Ayuubi, and Shiloza, perennial and annual perennial Cyperaceae weeds such as Hamanasu, Yellow hemlock, Himekugu, Cyperus edulis, Kogomegayatsu, etc. It shows high herbicidal effect by soil treatment or foliage treatment against grass weeds such as bluegrass, Johnsongrass, wild oats, and bluegrass, as well as soybean, cotton, sugar beet, rapeseed, sunflower, corn, upland rice, wheat, etc. Has a feature of showing high safety. Furthermore, it can be used not only in paddy fields and upland fields but also in orchards, mulberry fields, lawns, and non-agricultural fields.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Mitsuru Hikido 8-3-1 Chuo, Ami-cho, Inashiki-gun, Ibaraki Mitsubishi Petrochemical Co., Ltd. Tsukuba Research Institute (72) Inventor Miki Komine, Ami-cho, Inashiki-gun, Ibaraki Chuo 8-3-1, Mitsubishi Petrochemical Co., Ltd. Tsukuba Research Institute

Claims (2)

[Claims] 1. The following general formula: [Wherein, R represents a lower alkyl group, X and Y each independently represent a halogen atom, a lower alkyl group or a lower alkoxy group, and n is 0 or 1. ] The sulfonylurea derivative represented by these. 2. The following general formula: [Wherein, R represents a lower alkyl group, X and Y each independently represent a halogen atom, a lower alkyl group or a lower alkoxy group, and n is 0 or 1. ] A herbicide containing the sulfonylurea derivative represented by these as an active ingredient.