JPH0372635B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention has the following features: (1) General formula () [In the formula, R represents a lower alkyl group having 1 to 4 carbon atoms or a propargyl group, X represents a chlorine atom or a bromine atom, and n represents an integer of 0 or 2. A phenylhydantoin derivative represented by (2) General formula () [In the formula, X is as described above, and R _U1 represents a lower alkyl group having 1 to 4 carbon atoms. ] A phenyl isocyanate derivative represented by
General formula () characterized by reacting with methoxycarbonylthiomorpholine [In the formula, R _U1 and X are as described above.] ] A method for producing a substituted phenylhydantoin derivative represented by (3) General formula () [In the formula, X and n are as described above.] ] A substituted phenylhydantoin derivative represented by the general formula () RX () [wherein R and X are as described above. ] A method for producing a substituted phenylhydantoin derivative represented by the general formula (), which comprises reacting the substituted phenylhydantoin derivative with an alkyl halide represented by the formula (). (4) General formula () characterized by oxidizing a substituted phenylhydantoin derivative represented by general formula () [In the formula, X and R _U1 are as described above.] ] A method for producing a substituted phenylhydantoin derivative represented by (5) A herbicide characterized by containing a substituted phenylhydantoin derivative represented by the general formula () as an active ingredient. The compound of the present invention is a novel compound, and is characterized by having extremely high herbicidal activity against upland weeds and paddy field weeds at low doses in pre- or post-emergence treatments. Its herbicidal activity is much stronger than that of conventionally known hydantoin related compounds, and it can kill a wide range of weeds. Moreover, as is clear from the examples described later, some of the compounds of the present invention have a specific structure due to changes in It has the excellent feature of being selective for several crops. The compound of the present invention is included in the general formula described in U.S. Pat. 1,2-(4-chloro-2-fluorophenyl)-5,6,8,8a-tetrahydro-1H-imidazo[5,1-C][1,4] -thiazine-1,3-(2H)-dione (comparison compound (a) described below and 1,2-(4-chloro-2-fluorophenyl)-5,6,8,8a-tetrahydro-1H
-imidazo[5,1-C][1,4]-thiazine-
The Examples described below demonstrate that the compounds of the present invention exhibit superior herbicidal activity at lower doses than 1,3(2H)-dione-7,7 dioxide (comparative control compound (b) described below). ing. Next, the method for producing substituted phenylhydantoin derivatives according to the present invention will be explained in detail. The phenylhydantoin derivative represented by the general formula (1) can be synthesized, for example, according to the following reaction formulas () and (2). [In the formula, R, R _U1 , X and n are as described above.] ] A phenyl isocyanate derivative represented by the general formula () and 2-carbomethoxythiomorpholine are reacted at room temperature in an inert solvent such as hexane or benzene, using an appropriate base such as triethylamine if necessary. By this, the general formula ()
A phenylhydantoin derivative represented by is synthesized. This compound is further oxidized using a peracid such as m-chloroperbenzoic acid in the presence of a halogenated solvent such as methylene chloride at a temperature of -10°C to 10°C to obtain the general formula (). [In the formula, R _U1 and X are as described above.] ] A substituted phenylhydantoin derivative represented by the following is synthesized. In addition, the substituted phenylhydantoin derivative represented by the general formula () and the alkyl halide represented by the general formula () may be combined in an inert solvent such as dimethylformamide, acetonitrile, or dimethyl sulfoxide, if necessary, with potassium carbonate or carbonate. A substituted phenylhydantoin derivative represented by the general formula () can be synthesized by using a suitable dehydrohalogenating agent such as sodium or caustic soda and reacting at room temperature or under heating. The substituted phenylhydantoin derivative represented by general formula () is synthesized from 2-fluoro-4-halo-5-hydroxyphenyl isocyanate and 2-carbomethoxythiomorpholine in the same manner as in reaction formula (1). be able to. Next, the present invention will be explained in more detail with reference to Examples. Example 1 (Compound No. (1)) 2-methoxycarbonyl- in 60 ml of n-hexane
Dissolve 6 g of 4-thiomorpholine, add a catalytic amount of triethylamine, and prepare 4-chloro-2-fluoro-5-methoxyphenyl isocyanate at room temperature.
Add 6.9g little by little. An insoluble oil forms which solidifies. The n-hexane was removed by decantation, and 60 ml of methanol and a catalytic amount of sodium methoxide were added thereto, followed by refluxing for 1 hour. Methanol was distilled off, water was added, extracted with ether, washed with water,
Dry over anhydrous magnesium sulfate, concentrate, and purify the residue by silica gel chromatography.
2.6 g of 1,2-(4-chloro-2-fluoro-5
-methoxyphenyl)-5,6,8,8a-tetrahydro-1H-imidazo[5,1-C][1,4]
-thiazine-1,3-(2H)-dione was obtained. mp 121-123℃ IRνV _Ucn-1/nax 1780, 1720 Example 2 (Compound No. (2)) 1,2-(4-chloro-2-fluoro-5-methoxyph) prepared according to Example 1 enyl)-5,
6,8,8a-tetrahydro-1H-imidazo[5,
1-C][1,4]-thiazine-1,3-(2H)-
Dissolve 1.6 g of dione in 30 ml of methylene chloride, add 2.2 g of 70% m-chloroperbenzoic acid, and -10 to
The reaction was carried out at 0°C for 6 hours. After confirming that no peracid remained using iodostarch paper, the reaction solution was washed with aqueous sodium bicarbonate to remove m-chlorobenzoic acid, and the organic layer was dried over anhydrous sodium sulfate and concentrated. The residue was crystallized and recrystallized from ether and petroleum ether to give 0.9 g of 1,2-(2-fluoro-4-chloro-5-methoxyphenyl)-5,6,8,8a-
Tetrahydro-1H-imidazo[5,1-C]
[1,4]-thiazine-1,3-(2H)-dione-
7,7-oxide was obtained. mp 195-196°C Example 3 (Compound No. (3)) 1,2-(2-fluoro-4-chloro-5-hydroxyphenyl)-5,6,8,8a-tetrahydro-1H-imidazo [ 5,1-C] [1,4]-
1.3 g of thiazine-1,3-(2H)-dione-7,7-oxide was stirred with 0.28 g of potassium carbonate, 20 ml of dimethylformamide and 0.5 g of propargyl bromide for 2.5 hours at 50-61°C. After cooling,
After extraction with ethyl acetate, washing with water, drying over anhydrous sodium sulfate, and concentration under reduced pressure, the residue was purified using silica gel column chromatography to obtain 1,2-(2-fluoro-4-chloro-5-
Propargyloxyphenyl)-5,6,8,8a
-tetrahydro-1H-imidazo[5,1-C]
[1,4]-thiazine-1,3-(2H)-dione-
1.0 g of 7,7-oxide was obtained. mp 178-181°C Example 4 (Compound No. 8) 3.2 g of 3-carboethoxythiomorpholine was added to n
- Dissolved in 10 ml of hexane and added a few drops of triethylamine. To this, 4 g of 4-chloro-2-fluorophenyl isocyanate was added little by little. n-
The hexane was decanted off, dissolved in 10 ml of methanol, 0.05 g of sodium methoxide was added, and the mixture was refluxed for 1.5 hours. After cooling, ether extraction,
After washing with water, drying, and concentrating, the residue was purified by silica gel column chromatography to obtain 1.7 g of 1,2
-(2-Fluoro-4-chloro-5-isopropoxyphenyl)-5,6,8,8a-tetrahydro-1H-imidazo[5,1-C][1,4]-4-
Thiazine-1,3-(2H)-dione was obtained. Glassy substance IRνV ^cm-1 _nax 1780, 1720 Examples of the compounds of the present invention represented by the general formula () are as follows, but the compounds of the present invention are not limited to these. Note that the compound numbers shown here are commonly used in the following formulation examples and examples.

[Table] When actually applying the compound of the present invention obtained as described above, the raw material of the compound of the present invention () may be sprayed as it is, but in general, powders, granules,
Spread in formulations such as wettable powders and emulsions. The active ingredient content in the preparation is usually 0.1 to 80
% range, but depending on the purpose, the formulation can be 0.1% or less or 80% or more. In preparing these pharmaceutical products, solid carriers such as mineral powders (kaolin, bentonite, clay, montmorillonite, talc, diatomaceous earth, mica, vermiculite, gypsum,
calcium carbonate, apatite, etc.), vegetable powders (soybean flour, wheat flour, wood flour, tobacco flour, starch,
crystalline cellulose, etc.), polymer compounds (petroleum resin,
Polyvinyl chloride, dammar gum, ketone resin, etc.), alumina, waxes, etc. Examples of liquid carriers include alcohols (methyl alcohol, ethyl alcohol, ethylene glycol, benzene alcohol, etc.), aromatic hydrocarbons (toluene, benzene, xylene, methylnaphthalene, etc.), chlorinated hydrocarbons (chloroform, carbon tetrachloride, monochlorobenzene, etc.), ethers (dioxane, tetrahydrofuran, etc.), ketones (acetone, methyl ethyl ketone, cyclohexanone, etc.), esters (ethyl acetate, butyl acetate, ethylene glycol acetate, etc.), acid amides (dimethylformamide, etc.) ), nitriles (such as acetonitrile), ether alcohols (such as ethylene glycol ethyl ether), and water. The surfactant used for the purpose of emulsification, dispersion, spreading, etc. may be nonionic, anionic, cationic, or amphoteric. Examples of surfactants used include polyoxyethylene alkyl ether, polyoxyethylene alkyl allurether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, oxyethylene oxypropylene polymer, polyoxy Ethylene alkyl phosphate ester, fatty acid salt,
These include alkyl sulfate salts, alkyl sulfonate salts, alkylaryl sulfone salts, alkyl phosphate salts, polyoxyethylene alkyl sulfate esters, quaternary ammonium salts, and the like, but are not limited to these. Furthermore, for these purposes, gelatin, casein, sodium alginate, starch, agar, polyvinyl alcohol, and the like may be used as adjuvants, if necessary. Examples of formulations of the herbicide of the present invention are shown below. In addition, the compound name is indicated by the above-mentioned compound number. Formulation Example 1 80 parts by weight of compound (1), 3 parts by weight of alkyl sulfate, 2 parts by weight of lignin sulfonate and 15 parts by weight of white carbon are thoroughly ground and mixed to obtain a wettable powder. Formulation Example 2 10 parts by weight of compound (9), 10 parts by weight of the emulsifier Sonpol 2680 (registered trademark of Toho Chemical), 60 parts by weight of cyclohexanone and 20 parts by weight of xylene are thoroughly mixed to obtain an emulsion. Formulation example 3 Compound (4) 0.1 part by weight, white carbon 1 part by weight, bentonite 35 parts by weight, and clay 63.9
Parts by weight are thoroughly ground and mixed, water is added and the mixture is thoroughly kneaded, followed by granulation and drying to obtain granules. Formulation Example 4 3 parts by weight of compound (5), 0.3 parts by weight of isopropyl phosphate, 66.7 parts by weight of clay and 30 parts by weight of talc are thoroughly ground and mixed to obtain a powder. Formulation Example 5 20 parts by weight of compound (3) was mixed with 60 parts by weight of an aqueous solution containing 3% by weight of polyoxyethylene sorbitan monolactate, wet-pulverized until the particle size of the active ingredient became 3μ or less, and alginic acid was added as a dispersion stabilizer. 100 parts by weight of a suspension preparation is obtained by mixing 20 parts by weight of an aqueous solution containing 3% by weight of sodium. When using the compounds of the invention by pre-emergence and post-emergence application methods, the application rates can be varied over a fairly wide range. Generally the amount of active compound is from 0.05 g to 50 g per are, preferably from 0.1 g to 20 g. Furthermore, the compound of the present invention can be used in combination with other herbicides in order to improve its effectiveness as a herbicide, and in some cases, a synergistic effect can be expected. Examples include phenoxy herbicides such as 2,4-dichlorophenoneoxyacetic acid; 2-methyl-4-chlorophenoxybutyric acid; 2-methyl-4-chlorophenoxyacetic acid (including esters and salts); -dichlorophenyl-4'-nitrophenyl ether; 2,4,6-trichlorophenyl-4'-nitrophenyl ether; 2-chloro-4
-trifluoromethylphenyl-3'-ethoxy-
Diphenyl such as 4'-nitrophenyl ether; 2,4-dichlorophenyl-4'-nitro-3'-methoxyphenyl ether; 2,4-dichlorophenyl-3'-methoxycarbonyl-4'-nitrophenyl ether Ether herbicide, 2-chloro-4,
6-bisethylamino-1,3,5-triazine; 2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine; 2-methylthio-4,6-bisethylamino-1, 3,
5-triazine; 2-methylthio-4,6-bisisopropylamino-1,3,5-triazine;
Triazine herbicides such as 4-amino-6-tert-butyl-3-methylthio-1,2,4-triazin-5-one, 3-(3,4-dichlorophenyl)-1,1-dimethylurea; 3 -(3,4
-dichlorophenyl)-1-methoxy-1-methylurea; 1-(2,2-dimethylbenzyl)-3
-p-tolylurea; 1,1-dimethyl-3-
Urea herbicides such as (3-trifluoromethylphenyl)urea, isopropyl N-(3-chlorophenyl)carbamate; methyl N-(3,4
Carbamate herbicides such as -dichlorophenyl)carbamate, S-(4-chlorobenzyl)-N,
N-diethylthio-carbamate; S-ethyl-N,N-hexamethylenethiol-carbamate; S-ethyl-N,N-diisobutylthio-carbamate; S-ethyl-N,N-dinormalpropyl Thiol carbamate herbicides such as S-normal propylo-N,N-di-normal propyl thio-carbamate;
3,4-dichloropropionanilide; N-methoxymethyl-2,6-diethyl-α-chloroacetanilide; 2-chloro-2',6'-diethyl-N
-(Butoxymethyl)-acetanilide; 2-chloro-2',6'-diethyl-N-(n-propoxyethyl)-acetanilide; N-chloroacetyl-
N-(2,6-diethylphenyl)-glycine ethyl ester; 2-chloro-N-(2-ethyl-6
Acid anilide herbicides such as -methylphenyl)-N-(2-methoxy-1-methyl)acetamide, 5
-bromo-3-secondary-butyl-6-methyluracil; uracil herbicides such as 3-cyclohexyl-5,6-trimethyleneuracil, 1,1'-
Pyridinium chlorine herbicides such as dimethyl-4,4-bispyridinium chloride, N,N-bis(phosphonomethyl)-glycine, O-ethyl-O-
(2-nitro-5-methylphenyl)-N-secondary-butylphosphoroamidothioate, S-
(2-methyl-1-piperidylcarbonylmethyl)
O,O-di-n-propyldithiophosphate;
Phosphorus herbicides such as S-(2-methyl-1-piperidylcarbonylmethyl)O,O-diphenyldithiophosphate, α,α,α-trifluoro-
Toluidine herbicides such as 2,6-dinitro-N,N-dipropyl-p-toluidine, 5-tert-butyl-3-(2,4-dichloro-5-isopropoxyphenyl)-1,3,4 -Oxadiazolin-2-one; 3-isopropyl-1H-2,
1,3-Benzothiadiazin-(4)-3H-one-
2,2-dioxide, α-(β-naphthoxy)-propionanilide, 4-(2,4-dichlorobenzoyl)-1,3-dimethylpyrazole-5-
yl p-toluenesulfonate; 4'-phenylsulfonyl-1,1,1-trifluorosulfono-
o-Toluidide; 4-chloro-5-methylamino-2-(3-trifluoromethylphenyl)pyridazin-3(2H)-one, 1-methyl-3-phenyl-5-(3-trifluoromethylphenyl) enil)
Pyridin-4(1H)-one, 2-methyl-4-phenylsulfonyltrifluoromethylsulfoanilide, 2-(3,4-dichlorophenyl)-4-methyltetrahydro-1,2,4-oxadiazo-
-3,5-dione; 4-chloro-5-methylamino-2-(3-trifluoromethylphenyl)
Examples include pyridazin-3(2H)-one,
It is not limited to these. Furthermore, the compound of the present invention may be used as an insecticide, nematocide, fungicide, or
Mixed use with plant growth regulators, fertilizers, etc. is also possible. Next, the present invention will be explained in more detail with reference to Examples, but it goes without saying that the present invention is not limited to these Examples. In each of the following Examples as a herbicide, the evaluation of phytotoxicity to cultivated plants and efficacy against weeds was all expressed as an evaluation value using an integer from 0 to 5 in accordance with the criteria described below. Measure the fresh weight of the above-ground parts of the plants that remained withered at the time of the survey, and compare it to the fresh weight of the plants in the untreated area (%)
Calculate. Cultivated plants and weeds were evaluated for chemical damage and herbicidal efficacy on a scale from 0 to 5 based on the criteria shown in the table below. An evaluation value of 0 or 1 for cultivated plants or an evaluation value of 5 or 4 for weeds is generally considered to be an appropriate cultivated plant protection effect or weed control effect.

[Table] In order to further clarify the properties of the compounds of the present invention, the following compounds were used as comparative compounds. Comparison compound Example 5 Comparative test on the efficacy of pre-germination soil treatment in upland fields A cylindrical plastic beaker with a diameter of 10 cm and a height of 10 cm was filled with upland soil, and weed seeds of Japanese barnyard grass, oat, mulva morning glory, and Japanese crocodile were sown. After covering with soil, a predetermined amount of the raw material was made into an emulsion, diluted with water, and the soil was treated with a hand sprayer. Thereafter, the plants were grown in a greenhouse, and the herbicidal efficacy was observed 20 days after treatment. The results are shown in Table 3.

【table】

[Table] Example 6 Post-germination foliar treatment efficacy comparative test A cylindrical plastic beaker with a diameter of 10 cm and a height of 10 cm was filled with field soil, and weed seeds of Japanese barnyard grass, oat, wild mustard, and Japanese grass were sown. After covering the plants with soil and growing them in a greenhouse for two weeks, a predetermined amount of the chemical was applied to the entire stems and leaves from above using a hand sprayer. After the chemical treatment, each plant was grown in a greenhouse for an additional three weeks, and then its herbicidal efficacy was investigated. The results are shown in Table 4. The processing agent was formulated into an emulsion, a predetermined amount of which was dispersed in water (including a spreading agent), and the test was conducted at a rate of 5 liters per are.

【table】

[Table] Example 7 Weeding test on corn and wheat (post-emergence treatment) Field soil was packed into plastic trays measuring 35 cm in height, 25 cm in width, and 10 cm in height, and corn, wheat, Japanese crocodile, Japanese fir tree, Japanese mulberry morning glory, white locust, Japanese brilliance, After sowing chickweed and foxtail grass and growing them in a greenhouse for 2 to 3 weeks,
Arrange two of these trays in a frame measuring 50 cm, width 100 cm, and height 40 cm, and use a small sprayer from above the plants.
A predetermined amount of each drug was applied to the entire area within the frame. After being grown in a greenhouse for an additional three weeks after spraying the chemicals, each plant was examined for chemical damage or herbicidal efficacy. The results are shown in Table 5. In addition, the processing agent is formulation example 2.
An emulsion prepared according to the recipe was used and emulsified in 25 ml of water to which a spreading agent was added. The size of the plants at the time of drug administration varied depending on the species, but they were approximately 1-4 true leaves and 1.5-2.0 cm tall.

[Table] Example 8 Corn weeding test (post-emergence treatment) The field was divided into 1 section of 3 m ² , and seeds of Japanese chinese fir, purslane, common morning glory, Japanese morning glory, Ebisugusa, and Japanese crocodile were mixed within 4 cm of the soil surface layer, and then corn was grown. (variety Golden Cross Bantamuber) was sown. After 18 days, when the corn had grown to a 6-leaf stage and a plant height of 40 cm, and the weeds had grown to a 2- to 4-leaf stage and a plant height of 5 to 15 cm, they were treated with the chemical. In this case, the compound of the present invention (9) was prepared using an emulsion prepared according to the formulation of Formulation Example 2, and the control drug atrazine was prepared using a commercially available hydrating powder, and the predetermined amount was 150 ml per section.
The mixture was diluted with water (containing a spreading agent) and treated with a hand sprayer over the entire area. The treatment was repeated three times. On the 18th day after chemical treatment, chemical damage and herbicidal efficacy were investigated. The results are shown in Table 6.

[Table] Example 9 Cyperus rotundus stem and foliage treatment test A plastic pot with a diameter of 10 cm was filled with field soil, tubers of Cyperus rotundus were planted at a depth of 2 cm from the soil surface, grown in a greenhouse for 4 weeks, and leaves were tested. I obtained about 7 individuals of the common lizard. A predetermined amount of the raw material was made into an emulsion, diluted with water, and treated with a hand sprayer from above the plants. After the chemical treatment, the soil was grown in a greenhouse for another 8 weeks, and the soil was washed with water to observe the above-ground parts (stem leaves) and the underground regenerated parts (rhizomes and tubers), and the herbicidal efficacy was evaluated as a number from 0 to 5. It was expressed as The results are shown in Table 7.

【table】 /
H.O.
Example 10 Paddy-like soil treatment test A 1/5000a Wagner pot was filled with Takarazuka paddy soil, seeds of annual weeds were mixed in at a depth of 2 to 3 cm from the soil surface layer, and the pot was flooded with water. After flooding, tubers and overwintering buds of perennial weeds were planted. Five days later, when each weed started to germinate, a predetermined amount of the chemical was dropped onto the water surface using an emulsion. The herbicidal efficacy was investigated 4 weeks after the treatment, and the results are shown in Table 8.

【table】

Claims (1)

[Claims] 1. General formula [In the formula, R represents a lower alkyl group having 1 to 4 carbon atoms or a propargyl group, X represents a chlorine atom or a bromine atom, and n represents an integer of 0 or 2. ] A substituted phenylhydantoin derivative represented by 2 General formula [In the formula, R represents a lower alkyl group having 1 to 4 carbon atoms or a propargyl group, X represents a chlorine atom or a bromine atom, and n represents an integer of 0 or 2. ] A herbicide characterized by containing a substituted phenylhydantoin derivative represented by the following as an active ingredient.