JPS6160070B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to novel substituted phenylsulfonylurea derivatives and methods for producing the derivatives. More specifically, the novel substituted phenylsulfonylurea derivatives of the present invention have the formula: It is expressed as In addition, substituted phenylsulfonylurea derivatives of the above general formula (), namely N-2-biphenylylsulfonyl, N'-(4,6-dimethoxy-1,3,
5-triazin-2-yl)urea can be produced by the following method, and the present invention also relates to the production method. That is, Eq. 2-biphenylylsulfonyl isocyanate represented by the formula: 2-amino-4,6-dimethoxy-
N-2-biphenylylsulfonyl, N'-(4,6-dimethoxy-1,3,5-triazine) represented by the above formula (), characterized by reacting with 1,3,5-triazine -2-yl)urea production method. U.S. Patent No. 4127405, U.S. Patent No. 4169719, and Japanese Patent Application Publication No. 122384 of 1972, which were known before the filing of the present invention, have the formula (Here,

[expression] or

[Formula]; R ₁ is

【formula】

【formula】

[expression] or

[Formula]; R ₃ and R ₆ are independently hydrogen, fluorine, bromine,
Iodine, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, nitro, trifluoromethyl,
Cyano, CH ₃ S(O) _o − or CH ₃ CH ₂ S(O) _o −
R ₄ is hydrogen, fluorine, chlorine, bromine or methyl; R ₅ is hydrogen, fluorine, chlorine, bromine, methyl or methoxy; R ₇ is hydrogen, fluorine, bromine, 1-2 is alkyl of carbon atoms or alkoxy of 1 to 2 carbon atoms; R ₈ is hydrogen, methyl, chlorine or bromine; R ₉ and R ₁₀ are independently hydrogen, methyl, chlorine or bromine; W and Q are independently oxygen or sulfur; n is 0, 1 or 2; X is hydrogen, chlorine, bromine, methyl, ethyl, 1-
3 carbon atom alkoxy, trifluoromethyl,
CH ₃ S- or CH ₃ OCH ₂ -; and Z is methyl or methoxy; provided that: a When R ₅ is other than hydrogen, R ₃ ,
At least one of R ₄ , R ₆ and R ₇ must be other than hydrogen, and at least 2 of R ₃ , R ₄ , R ₆ and R ₇ must be hydrogen; b R ₅ is hydrogen; and when R ₃ , R ₄ , R ₆ and R ₇ are all other than hydrogen, R ₃ ,
R ₄ , R ₆ and R ₇ must all be either chlorine or methyl; and when c R ₃ and R ₇ are both hydrogen, R ₄ ,
At least one of R ₅ or R ₆ must be hydrogen;) It is stated that a compound or a salt thereof suitable as an agricultural chemical has herbicidal activity. The inventors of the present invention have repeatedly conducted experimental research on substituted phenylsulfonylurea derivatives in order to find new derivatives having superior herbicidal activity, and as a result, they have discovered a novel substituted phenylsulfonylurea represented by the above formula (). It has been found that the derivative has excellent selective herbicidal activity that is not seen at all in the compound of the above general formula (). In other words, the substituted phenylsulfonylurea derivatives of the present invention exhibit herbicidal effects at considerably lower doses than conventional herbicides, while also causing considerable phytotoxicity to rice. In contrast, it does not cause any phytotoxicity to rice plants, and exhibits an accurate and excellent selective herbicidal effect at a low dose. In particular, when the compound of the present invention is used as a pre-emergence soil treatment agent for paddy field weeds or as a foliage and soil treatment agent,
Shows excellent selective control efficacy. The compound of the present invention is excellent in safety, exhibits outstanding herbicidal activity, and has a wide herbicidal spectrum. For example, as paddy field weeds,

【table】

[Table] Herbicidal activity is observed in the following, and it has the characteristic that it has no harmful effect on paddy rice. In addition, as upland weeds, for example,

[Table] It has a characteristic that it has herbicidal activity on the following crops, and has no harmful effects on the following crops. For example, dicotyledonous plants include mustard, mustard, cotton, carrot, legumes, potato, beet, and citrus. Examples of monocotyledonous plants include corn, rice, oats, barley, wheat, millet, and sugarcane. However, the above-mentioned plant types should be considered to be representative examples of the genus given by its Latin name. However, the adaptability of the active compound of the present invention is not limited only to weeds in paddy fields and upland fields, but is also effective against weeds harmful to rushes, etc., and weeds in fallow land, etc. be. The word weed here means in its broadest sense any plant that grows in undesirable locations. The substituted phenylsulfonylurea derivative of the present invention represented by the above formula () is synthesized by the following general method. In the method for producing a compound of formula () of the present invention shown in the above reaction formula, the compound of formula () as a raw material represents 2-biphenylylsulfonyl isocyanate. Similarly, the compound of formula (), which is also a raw material, is
2-Amino-4,6-dimethoxy-1,3,5-
Indicates triazine. The above manufacturing method of the present invention is preferably carried out using a solvent or diluent. All inert solvents and diluents can be used for this purpose. Such solvents or diluents include aliphatic, cycloaliphatic and aromatic hydrocarbons (which may optionally be chlorinated) such as hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, methylene chloride,
Chloroform, carbon tetrachloride, ethylene chloride and tri-chloroethylene, chlorobenzene;
Other ethers such as diethyl ether, methyl ethyl ether, di-iso-propyl ether, dibutyl ether, propylene oxide,
Dioxane, tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, methyl-iso
-Propyl ketone, methyl-iso-butyl ketone; Nitriles such as acetonitrile, propionitrile, acrylonitrile; Esters such as ethyl acetate, amyl acetate; Acid amides such as dimethylformamide, dimethylacetamide; Sulfones, sulfoxides such as dimethyl Sulfoxides, sulfolanes; and bases, e.g.
Examples include pyridine. Furthermore, the above method can be carried out efficiently in the presence of a catalyst, such as 1,4-diazabicyclo[2,2,2]octane. The above method can be carried out within a wide temperature range. It is generally carried out between -20°C and the boiling point of the mixture, preferably between 0 and 100°C. Further, although it is preferable to carry out the reaction under normal pressure, it is also possible to operate under increased pressure or reduced pressure. When the compound of the present invention is used as a herbicide, it can be used directly as it is after being diluted with water, or it can be made into various formulations using a pesticide auxiliary by a method commonly used in the field of pesticide manufacturing. can be used. In actual use, these various formulations can be used directly or diluted with water to a desired concentration. The pesticide adjuvants mentioned here are, for example,
Mention may be made of diluents (solvents, fillers, carriers), surfactants (solubilizers, emulsifiers, dispersants, wetting agents), stabilizers, sticking agents, propellants for aerosols, and synergists. Solvents include water: organic solvent; hydrocarbons [e.g., n-hexane, petroleum ether, naphtha, petroleum fractions (paraffin wax, kerosene, light oil, medium oil, heavy oil), benzene, toluene, xylenes], halogenated Hydrocarbons [e.g., chlormethylene, carbon tetrachloride, trichlorethylene, ethylene chloride, ethylene dibromide, chlorobenzene, chloroform], alcohols [e.g., methyl alcohol, ethyl alcohol, propyl alcohol, ethylene glycol], ethers, [e.g. ethyl ether, ethylene oxide, dioxane],
Alcohol ethers [e.g. ethylene glycol monomethyl ether], ketones [e.g.
acetone, isophorone], esters, [e.g.
Ethyl acetate, amyl acetate], amides, [e.g.
dimethylformamide, dimethylacetamide], sulfoxides [for example, dimethyl sulfoxide]. Inorganic powder and granules as fillers or carriers: sulfur, slaked lime, magnesium lime, gypsum, calcium carbonate, silica, perlite, pumice, calcite, diatomaceous earth, amorphous silicon oxide, alumina, zeolite,
Clay minerals (e.g. pyrophyllite, talcum, montmorillonite, beidellite, vermiculite, kaolinite, mica): Vegetable granules; Grain flour, starch, modified starch, sugar, glucose, crushed plant stems: Synthetic resins Powder; phenolic resin,
Examples include urea resin and vinyl chloride resin. Examples of the surfactant include anionic surfactants; alkyl sulfate esters, [e.g. sodium lauryl sulfate], arylsulfonic acids, [e.g. alkylaryl sulfonate, sodium alkylnaphthalene sulfonate], succinates, Polyethylene glycol alkylaryl ether sulfate salts: cationic surfactants; alkylamines, [e.g., laurylamine, stearyltrimethylammonium chloride, alkyldimethylbenzylammonium chloride], polyoxyethylene alkylamines: nonionic interface Activator; polyoxyethylene glycol ethers, [e.g.
polyoxyethylene alkylaryl ether,
and condensates thereof], polyoxyethylene glycol esters, [e.g. polyoxyethylene fatty acid esters], polyhydric alcohol esters,
[For example, polyoxyethylene sorbitan monolaurate]: Ampholytic surfactant, etc. can be mentioned. In addition, stabilizers, fixing agents [e.g., agricultural soap, casein lime, sodium alginate, polyvinyl alcohol (PVA), vinyl acetate adhesives, acrylic adhesives], potency extenders, dispersion stabilizers [e.g., casein, tragacanth, carboxymethylcellulose (CMC), polyvinyl alcohol (PVA)], synergists, etc. The compound of the present invention can be manufactured into various formulations by methods generally practiced in the agricultural chemical manufacturing field. Examples of formulation forms include emulsions, oils, wettable powders, aqueous solutions, suspensions, powders, granules, powders, capsules, and the like. When using the compounds of the invention as herbicides,
0.001 to 100% by weight of said active ingredient, preferably
It can contain from 0.005 to 95% by weight. In actual use, the various formulations and spray preparations described above (ready-to-use)
The active compound content in the preparation is generally
A range of 0.01 to 95% by weight, preferably 0.05 to 60% by weight is suitable. The content of these active ingredients is
It can be changed as appropriate depending on the form of the preparation, the method of application, purpose, timing, location, weed growth situation, etc. The compounds of the present invention may also be used, if necessary, with other agricultural chemicals such as insecticides, fungicides, acaricides, nematicides,
Antiviral agents, herbicides, plant growth regulators, attractants [e.g., organophosphate compounds, carbamate compounds, dithio (or thiol) carbamate compounds, organochlorine compounds, dinitro compounds, organic sulfur or metal compounds] compounds, antibiotics, substituted diphenyl ether compounds, urea compounds, triazine compounds] or/and fertilizers, etc. may also be present. Also, in particular, other active ingredients, such as 2-chloro-2',6'-diethyl-N-(butoxymethyl)-acetanilide, N-(O,O-dipropyl-diethylphosphorylacetyl)-2-methylpiperidine , S-(4-chlorobenzyl)-N,N-diethylthiol carbamate S-ethyl-N,N-hexamethylenethiol carbamate, O-methyl-O-(2-nitro-p-tolyl)-
N-isopropylphosphoramidothioate, O-ethyl-O-(2-nitro-5-methylphenyl)-N-sec-butylphosphoramidothioate, 3,4-dimethyl-2,6-dinitro-N- 1
-ethylpropylanilide, α,α,α-trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidine, 2-chloro-2',6'-diethyl-N-(n-propoxyethyl)acetanilide , 4,5-dichloro-1,3-thiazole-2-
yloxyacetic acid N-isopropyl-N-ethoxyethoxyamide, 5-ethyl-1,3,4-thiadiazole-2
-yloxyacetic acid 1',2',3',4'-tetrahydroquinolide, benzothiazol-2-yloxyacetic acid N,N
-Diallylamide, benzoxazol-2-yloxyacetic acid N-
sec-butyl-N-methylamide, benzoxazol-2-yloxyacetic acid N-
Cyclohexyl-N-methylamide, Benzothiazol-2-yloxyacetic acid N-methyl-N-(1-methylpropargyl)amide, Benzoxazol-2-yloxyacetic acid N-
Benzyl-N-propargylamide, Benzothiazol-2-yloxyacetic acid 2'-ethylpiperidide, Benzothiazol-2-yloxyacetic acid 2',
4'-dimethylpiperidide, benzoxazol-2-yloxyacetic acid 2',
4',6'-trimethylpiperidide, benzoxazol-2-yloxyacetic acid hexamethyleneimide, benzothiazol-2-yloxyacetic acid perhydroindolide, benzoxazol-2-yloxyacetic acid perhydroindolide, benzothiazole-2 -yloxyacetic acid 1′,
2′,3′,4′-tetrahydroquinolide, benzoxazol-2-yloxaacetic acid 2′-
Methyl-1',2',3',4'-tetrahydroquinolide, benzoxazol-2-yloxyacetic acid N-
Methylanilide, Benzothiazol-2-yloxyacetic acid N-methylanilide, Benzoxazol-2-yloxyacetic acid N-
Ethylanilide, benzoxazol-2-yloxyacetic acid N-
Propylanilide, benzoxazol-2-yloxyacetic acid N-
Isopropylanilide, Benzothiazol-2-yloxyacetic acid N-methyl-N-2'-methoxyanilide, Benzoxazol-2-yloxyacetic acid N-
Methyl-N-2'-methoxyanilide, benzoxazol-2-yloxyacetic acid N-
Methyl-N-2'-trifluoromethylanilide, Benzothiazol-2-yloxyacetic acid N-methyl-N-2'-chloroanilide, Benzoxazol-2-yloxyacetic acid N-
Methyl-N-2'-chloroanilide, Benzothiazol-2-yloxyacetic acid N-methyl-N-2'-fluoroanilide, Benzoxazol-2-yloxyacetic acid N-
Methyl-N-2'-fluoroanilide, Benzothiazol-2-yloxyacetic acid N-methyl-N-3'-methylanilide, Benzoxazol-2-yloxyacetic acid N-
Methyl-N-3'-methylanilide, Benzothiazol-2-yloxyacetic acid N-methyl-N-3'-methoxyanilide, Benzoxazol-2-yloxyacetic acid N-
Methyl-N-3'-methoxyanilide, Benzothiazol-2-yloxyacetic acid N-methyl-N-3'-isopropoxyanilide, Benzoxazol-2-yloxyacetic acid N-
Methyl-N-3'-isopropoxyanilide, Benzothiazol-2-yloxyacetic acid N-methyl-N-3'-trifluoromethylanilide, Benzoxazol-2-yloxyacetic acid N-
Methyl-N-3'-trifluoromethylanilide, Benzothiazol-2-yloxyacetic acid N-methyl-N-3'-chloroanilide, Benzoxazol-2-yloxyacetic acid N-
Methyl-N-3'-chloroanilide, Benzothiazol-2-yloxyacetic acid N-methyl-N-3'-fluoroanilide, Benzoxazol-2-yloxyacetic acid N-
Methyl-N-3'-fluoroanilide, Benzothiazol-2-yloxyacetic acid N-methyl-N-3'-bromoanilide, Benzoxazol-2-yloxyacetic acid N-
Methyl-N-3'-bromoanilide, benzoxazol-2-yloxyacetic acid N-
Methyl-N-4'-methylanilide, benzoxazol-2-yloxyacetic acid N-
Methyl-4'-methoxyanilide, benzoxazol-2-yloxyacetic acid N-
Methyl-N-4'-fluoroanilide, benzoxazol-2-yloxyacetic acid N-
Methyl-N-2',3'-dimethylanilide, benzoxazol-2-yloxyacetic acid N-
Methyl-N-2',3'-dichloroanilide, benzoxazol-2-yloxyacetic acid N-
Methyl-N-4'-chloro-2'-methylanilide, Benzothiazol-2-yloxyacetic acid N-methyl-N-2',5'-dichloroanilide, Benzoxazol-2-yloxyacetic acid N-
Methyl-N-2',5'-dichloroanilide, Benzothiazol-2-yloxyacetic acid N-methyl-N-3',5'-dimethylanilide, Benzoxazol-2-yloxyacetic acid N-
Methyl-N-3',5'-dimethylanilide, benzoxazol-2-yloxyacetic acid N-
Methyl-N-3',5'-di-trifluoromethylanilide, benzoxazol-2-yloxyacetic acid N-
Methyl-N-5'-indanilamide, Benzothiazol-2-yloxyacetic acid N-methyl-N-3'-ethylanilide, Benzoxazol-2-yloxyacetic acid N-
By adding appropriate amounts of methyl-N-3'-ethylanilide, benzothiazol-2-yloxyacetic acid N-isopropylanilide, etc., a broader herbicidal spectrum and more accurate control effect can be obtained, as well as a synergistic effect by mixing these. is also expected. Various formulations or ready-to-use preparations containing the active ingredients of the invention are available.
Preparation) refers to the application methods commonly used in the field of agrochemical manufacturing, such as spraying, misting, atomizing, dusting, powdering, water surface application, and pouring. ]: Can be carried out by soil application [for example, soil mixing, sprinkling], etc. It can also be used by what is called an ultra-low-volume spraying method. In this method, the active ingredient
It is possible to contain 100%. The application rate per unit area is approximately 0.1 to 3 kg of active compound per hectare, preferably 0.2 to 1 kg.
Kg is used. However, in special cases,
Exceeding or falling below these ranges is possible, and sometimes even necessary. The present invention comprises a compound of the above formula () as an active ingredient, and further contains diluents (solvents and/or fillers and/or carriers) and/or surfactants, if necessary, e.g. A herbicidal composition comprising a herbicidal agent is provided. Furthermore, the present invention applies the compound of formula () to weeds and/or their growth sites alone or in the presence of diluents (solvents and/or fillers and/or carriers) and/or surfactants and, if necessary, A weed control method is provided in which a mixture of a stabilizer, a fixing agent, and a synergist is applied. EXAMPLES Next, the content of the present invention will be specifically explained with reference to Examples, but the present invention should not be limited thereto. Example 1 (Wettable powder) Compound of the above formula (), 15 parts, mixture of powdered silica earth and powdered clay (1:5), 80 parts, sodium alkylbenzenesulfonate, 2 parts, sodium alkylnaphthalenesulfonate Three parts of the formalin condensate were ground and mixed to form a wettable powder. This is diluted with water and applied dropwise to weeds and/or their growing areas. Example 2 (emulsion) Compound of the above formula (), 30 parts, xylene, 55
1 part, polyoxyethylene alkyl phenyl ether, 8 parts, and calcium alkylbenzenesulfonate, 7 parts, were mixed and stirred to prepare an emulsion. This is diluted with water and dripped onto weeds and/or their growing areas. Example 3 (powder) Compound of the above formula (), 2 parts, powdered clay, 98
Pulverize and mix to make a powder. Sprinkle this on weeds and/or their growing areas. Example 4 (Powder) 15 parts of the compound of the formula (), 0.5 parts of isopropyl hydrogen phosphate (PAP), and 98 parts of powdered clay are ground and mixed to make a powder, and applied to weeds and/or their growing areas. Sprinkle with powder. Example 5 (granules) Compound of the above formula (), 10 parts, bentonite (montmorillonite), 30 parts, talc (talc), 58
1 part, lignin sulfonate, in a mixture of 2 parts,
Add 25 parts of water, mix well, and use an extrusion granulator to form 10 to 40 mesh granules at 40 to 50℃.
Dry to make granules. Sprinkle this on weeds and/or their growing areas. Example 6 (granules) Granular soil mineral particles having a particle size distribution of 0.2 to 2 mm, 95
1 part was placed in a rotary mixer, and while rotating, 5 parts of the compound of formula (2) dissolved in an organic solvent was sprayed onto the mixer to evenly coat the mixture, and then dried at 40 to 50 DEG C. to form granules.
This is sprinkled on weeds and/or their growing areas. When compared with active compounds of similar structure and of similar active form already known from the literature, the novel compounds according to the invention show a substantially improved efficacy and a very low toxicity for warm-blooded animals. This compound is characterized by a low oxidation rate, and therefore has very high utility value. The unexpected superiority and remarkable efficacy of the active compounds according to the invention can be seen from the following test results when used against various weeds. Test Example 1 Submerged foliage and soil treatment test on paddy field weeds (pot test) Preparation of active compound Carrier: 5 parts by weight of acetone Emulsifier: 1 part by weight of benzyloxypolyglycol ether The preparation of the active compound contains 1 part by weight of active compound. mixing the compound with the above-mentioned amounts of carrier and emulsifier;
Obtained as an emulsion. The prescribed dosage of the preparation,
Prepare by diluting with water. Test method A 1/5000 are Wagner pot was filled with paddy soil, and two paddy rice seedlings (variety: Kinnanfu) at the 2- to 3-leaf stage (plant height approximately 10 cm) were transplanted to each pot. In addition, wild grass, cyperus, cyperus, firefly,
Seeds of broad-leaved weeds and small pieces of Pinus vulgaris and tubers of Cyperus japonica and Uricula were inoculated and kept moist. After the wildflowers grew to around the two-leaf stage (about 7 to 9 days after inoculation), they were submerged in water to a depth of about 6 cm, and treated with a predetermined amount of the compound of the present invention in the form of an emulsion using a pipette. After treatment, water leakage was treated for 2 days at a rate of 2 to 3 cm per day, and after that, water was maintained at approximately 3 cm per day, and the herbicidal effect and degree of chemical damage were evaluated from 0 to 0 according to the following criteria after 4 weeks of chemical treatment.
The evaluation was graded into 5 stages. Evaluation of effectiveness is as follows when compared to untreated area: 5: Weed killing rate 95% or more (death) compared to untreated area 4: 80% or more but less than 95% 3: 50% or more but less than 80% 2: 30% or more Less than 50% 1: 〃 10% or more but less than 30% 0: 〃 Less than 10%
(No effect) Evaluation of chemical damage to paddy rice compared to untreated area: 5: Weed killing rate over 90% compared to untreated area
(Fatal damage) 4: 〃 50% or more and less than 90% 3: 〃 30% or more and less than 50% 2: 〃 10% or more and less than 30% 1: 〃 More than 0 and less than 10% 0: 〃 0% (no chemical damage) did. The test results are shown in Table 1.

[Table] Next, a synthesis example of the compound of the above formula () of the present invention is shown below. Synthesis example 2-Amino-4,6-dimethoxy-1,3,5
- 15.6g of triazine in 100ml of dry acetonitrile
and further suspended in 1,4-diazabicyclo[2,
2,2] Add 0.1g of octane. Add 2-biphenylylsulfonyl isocyanate to this mixture.
A solution of 28.5 g in 30 ml of xylene is added dropwise over 1 hour.
During the addition, the reaction occurs with a slight exotherm, so cool if necessary. After the completion of dropping, continue at room temperature for 5 hours.
React at 40°C for 5 hours. After cooling the contents to room temperature, filter the precipitated colorless crystals, wash with ether, and dry to obtain the target product, N-2-biphenylylsulfonyl, N'-(4,6-dimethoxy- 1,3,5-triazin-2-yl)urea
35.3g is obtained. mp.175-180℃.

Claims (1)

[Claims] 1 Formula: N-2-biphenylylsulfonyl represented by
N'-(4,6-dimethoxy-1,3,5-triazin-2-yl)urea. 2 formula: 2-biphenylylsulfonyl isocyanate represented by the formula: 2-amino-4,6-dimethoxy-
1,3,5-triazine, characterized in that the formula: N-2-biphenylylsulfonyl represented by
A method for producing N'-(4,6-dimethoxy-1,3,5-triazin-2-yl)urea.