JPH039911B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel imidazolidin-2-one derivative, a method for producing the same, and a herbicide containing the derivative as an active ingredient. The imidazolidin-2-one derivative of the present invention is a new compound that has not been described in any literature, and has the following general formula []
It is indicated by. [In the formula, R represents a lower alkyl group. X represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a benzyloxy group, or a lower haloalkyl group. n represents an integer from 1 to 3. ] In this specification, examples of lower alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, and tert-butyl group. Examples of halogen atoms include fluorine, chlorine,
Examples include bromine and iodine atoms. Examples of lower alkoxy groups include methoxy, ethoxy, n-propyloxy, isopropyloxy, and n-butoxy groups. Examples of lower haloalkyl groups include monochloromethyl group, monochloroethyl group, monochloropropyl group, dichloroethyl group, monobromomethyl group, monobromoethyl group, monobromopropyl group, monofluoromethyl group, trifluoromethyl group, and trifluoroethyl group. etc. can be mentioned. The compound of the present invention represented by the above general formula [] can be produced by various methods, but one preferred example thereof is produced according to the following reaction formula-1. Reaction formula-1 [In the formula, R, X and n are the same as above. ) In the above reaction formula-1, the imidazolidine represented by the general formula () used as a starting material -
The 2-one derivative is a new compound, and can be obtained, for example, by reducing a known compound, a hydantoin derivative (), according to Reaction Formula-2 below. Reaction formula-2 [In the formula, X and n are the same as above. ] The reaction of reducing the compound represented by the general formula [] to obtain the compound represented by the general formula [] can be carried out in an appropriate solvent. Examples of the solvent used include water, alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, and butyl alcohol, or mixed solvents of the above-mentioned alcohols and ethers such as diethyl ether, dibutyl ether, tetrahydrofuran, and dioxane. be able to. For example, sodium borohydride is used as a reducing agent in the reaction of reducing the compound represented by the general formula [] to obtain the compound represented by the general formula []. The ratio of the compound represented by the general formula [] and sodium borohydride is not particularly limited and can be appropriately selected from a wide range, but usually the latter is 0.1% of the former.
It is preferable to use about 5 to 5 times the mole, preferably about 0.25 to about the same mole. The reaction temperature for this reaction is not particularly limited, but the reaction normally proceeds suitably at about -50 to 100°C, preferably about 0 to 50°C, and is generally completed in about 1 to 5 hours. The other starting material, the isocyanate represented by the general formula [], is a known compound, such as methyl isocyanate, ethyl isocyanate,
Examples include n-propylisocyanate, isopropylisocyanate, n-butyl isocyanate, isobutyl isocyanate, sec-butyl isocyanate, and the like. The reaction between the compound of general formula [] and the compound of general formula [] is carried out without a solvent or in a solvent.
When carrying out the reaction without a solvent, it is preferable to carry out the reaction under pressure in an autoclave in order to prevent the compound represented by the general formula [] from volatilizing. When carrying out the process in a solvent, any solvent that does not adversely affect the raw materials can be used, such as diethyl ether,
Ethers such as dipropyl ether, dibutyl ether, tetrahydrofuran and dioxane, halogenated hydrocarbons such as methylene chloride and chloroform, aromatic solvents such as benzene, toluene, xylene and chlorobenzene, pyridine, acetonitrile, N,N- Dimethylformamide and the like can be used. The usage ratio of the compound represented by the general formula [] and the compound represented by the general formula [] is not particularly limited and can be appropriately selected from a wide range, but the latter is usually equivalent to 5 times the molar amount of the former. It is preferable to use about the same mole to about 2 times the mole. Compounds represented by general formula [] and general formula []
When the reaction with the compound represented by is carried out without a solvent, a catalyst may or may not be used, but when the reaction is carried out in a solvent, it is preferable to use a catalyst. Examples of the catalyst used include tertiary amines, specifically triethylamine, tributylamine, N,N-dimethylaniline, hexamethylenetetramine, and the like. The amount of the catalyst to be used may be a normal catalyst amount, for example, it is usually about 0.01 to 0.5 mole based on the compound represented by the general formula []. The reaction temperature for this reaction is not particularly limited, but the reaction usually proceeds at about 0 to 150°C, and generally at about 3 to 150°C.
The reaction is completed in about 15 hours. The compound of the present invention having the general formula [] thus obtained can be easily purified by conventional methods such as recrystallization, solvent extraction, column chromatography, etc. Examples of the compounds of the present invention obtained by the above method are as follows. Γ3-Methyl-4-methylcarbamoyloxyimidazolidin-2-one-1-carboxyanilide Γ3-methyl-4-ethoxycarbamoyloxyimidazolidin-2-one-1-carboxyanilide Γ3-methyl-4-isopropylcarbamoyloxyimidazo Lysin-2-one-1-carboxyanilide Γ2',3'-dimethyl-4-methylcarbamoyloxyimidazolidin-2-one-1-carboxyanilide Γ3,3'-dimethyl-4-methylcarbamoyloxyimidazolidine-2 -one-1-carboxyanilide Γ2'-chloro-3-methyl-4-methylcarbamoyloxyimidazolidin-2-one-1-carboxyanilide Γ2'-chloro-3-methyl-4-isopropylcarbamoyloxyimidazolidine-2 -on-
1-carboxyanilide Γ2',4'-dichloro-3-methyl-4-methylcarbamoyloxyimidazolidin-2-one-
1-carboxyanilide Γ3'-chloro-3-methyl-4-methylcarbamoyloxyimidazolidin-2-one-1-carboxyanilide Γ 3-methyl-4'-methoxy-4-methylcarbamoyloxyimidazolidin-2-one -1
-carboxyanilide Γ3-methyl-4'-trifluoromethyl-4-methylcarbamoyloxyimidazolidine-2-
imidazolidin-2-one-1-carboxyanilide Γ3-methyl-4'-benzyloxy-4-methylcarbamoyloxyimidazolidin-2-one-1-carboxyanilide The present invention also provides imidazolidin-2-one represented by the general formula [] This invention relates to a herbicide containing a derivative as an active ingredient. The compounds of the present invention include Takasaburou, Aobiyu,
It exhibits a strong herbicidal effect against weeds such as Japanese grasshopper, Japanese knotweed, artemisia, Japanese mugwort, Japanese aphrodisiac, Japanese aphrodisiac, Japanese azalea, Japanese bush grass, Japanese wild grass, Japanese aphrodisiac, Japanese cyperus, and other weeds.
It is useful for the production of agricultural crops such as soybean, corn, mulberry, tea, and paddy rice, and for controlling weeds that are harmful to the landscape. When applying the compound of the present invention as a herbicide, the compound of the present invention may be used as it is, but in general, it may be mixed with an adjuvant commonly used in the formulation of agricultural chemicals and used in any dosage form. Can be done. Among these, emulsion, wettable powder, and granule forms are preferably used. At this time, examples of auxiliary agents to improve stability and effectiveness include fillers such as diatomaceous earth, kaolin, clay, bentonite, white carbon, and talc, polyoxyethylene alkyl ether, and polyoxyethylene alkyl ether. Nonionic or anionic surfactants such as phenyl ether, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene fatty acid ester, sodium alkylbenzene sulfonate, sodium lignin sulfonate, sodium alkyl sulfate, sodium polyoxyethylene alkyl sulfate, Organic solvents such as xylol, acetone, methanol, ethanol, isopropanol, dioxane, dimethylformamide, dimethyl sulfoxide, and carbon tetrachloride are used. The herbicidal composition of the present invention is formulated so that the active ingredient is about 1 to 90% by weight, preferably about 5 to 70% by weight.
It is formulated by adding adjuvants to achieve the desired results. The appropriate amount to be applied depends on the drug formulation form, application method,
The amount of active ingredient varies depending on the time of application, the type of target weed, and the weather conditions and soil conditions that tend to affect the herbicidal effect, and is selected appropriately from a wide range, but in general, the amount of active ingredient is approximately About 5 to 400 g/a, preferably about 10 to 100 g/a
The degree is scattered. The present invention will be explained in more detail by referring to Reference Examples, Examples, Prescription Examples, and Test Examples below. Note that the test compound numbers in the test examples correspond to the numbers in the examples. Reference Example 1 Production of 3,3'-dimethyl-4-hydroxyimidazolidin-2-one-1-carboxyanilide 7.4 g (0.03 mol) of 3,3'-dimethylimidazolidine-2,5-dione-1-carboxyanilide )
was suspended in 50 ml of methanol. After cooling to 10°C, add 1.2 g (0.03 mol) of sodium borohydride under stirring.
added. After stirring for 30 minutes, the mixture was returned to room temperature and further stirred for 2 hours. After the reaction was completed, the reaction solution was concentrated, and water was added to the residue to precipitate crystals. After filtering the crystals, recrystallization from ethanol yielded 6.7 g of colorless crystals (yield 90%).
I got it. Melting point 164-164.5°C Example 1 Production of 3,3'-dimethyl-5-methylcarbamoyloxyimidazolidin-2-one-1-carboxanilide 3,3'-dimethyl-5-hydroxyimidazolidin-2-one- 1-carboxyanilide 5.0g
(0.02 mol) was dissolved in 50 ml of chloroform, and 0.5 ml of triethylamine was added. After cooling to 5℃,
1.7 g (0.03 mol) of methyl isocyanate under stirring
was dripped. After stirring for 30 minutes, the mixture was returned to room temperature and further stirred for 5 hours. After the reaction is completed, the reaction solution is concentrated under reduced pressure.
A crystalline residue was obtained. This was recrystallized from ethanol to obtain 5.2 g of colorless crystals (yield: 85%). Melting point: 130-131°C NMR of the crystal in deuterated chloroform showed the following. δ 2.30ppm (3H), δ 2.77ppm (3H) δ 2.80ppm (3H), δ 3.30ppm (1H) δ 5.17ppm (1H), δ 6.75ppm (1H) δ 6.80-7.50ppm (4H) Elemental analysis value (C ₁₄ H ₁₈ N ₄ O ₄ = 306.32) Analytical value % C54.85 H5.93 N18.31 Theoretical value % C54.89 H5.92 N18.29 From the above results It was confirmed. Example 2 Preparation of 4'-chloro-3-methyl-5-ethylcarbamoyloxyimidazolidin-2-one-1-carboxyanilide 4'-chloro-3-methyl-5-hydroxyimidazolidin-2-one-1 -carboxyanilide
Dissolve 2.7g (0.01mol) in 40ml of chloroform,
0.4 ml of triethylamine was added. After cooling to 5° C., 1.1 g (0.015 mol) of ethyl isocyanate was added dropwise while stirring. After stirring for 30 minutes, return to room temperature, and then
Stirred for 12 hours. After the reaction was completed, the reaction solution was concentrated under reduced pressure to obtain a crystalline residue. This was recrystallized from ethanol to obtain 2.6 g of colorless crystals (yield 77%). Melting point: 156-157°C NMR of the crystal in deuterated chloroform showed the following. δ 1.12ppm (3H), δ 2.82ppm (3H) δ 3.10~3.50ppm (3H) δ 3.70ppm (1H), δ 5.20ppm (1H) δ 6.70ppm (1H), δ 7.28ppm (2H) 7.53ppm ( 2H) Elemental analysis value (C ₁₄ H ₁₇ N ₄ O ₄ Cl = 340.77) Analysis value % C49.30 H5.05 N16.45 Theoretical value % C49.35 H5.03 N16.44 From the above results It was confirmed. Examples 3 to 17 Performing the same operations as in Examples 1 and 2, Examples 3 to 17
17 compounds were obtained. Melting point and NMR data first
Shown in the table.

【table】

【table】

[Table] Formulation example 1 (30% emulsion) (parts by weight) Compound of Example 1 30 Polyoxyethylene nonyl 10 Phenyl ether dimethylformamide 20 Xylene 40 Formulation example 2 (50% hydrating agent) Compound of Example 2 50 Sodium ligninsulfonate 1 Sodium dodecylbenzenesulfonate 4 Clay 45 Formulation example 3 (10% granules) Compound of Example 3 10 Sodium ligninsulfonate 0.5 Sodium dodecylbenzenesulfonate 2 Diatomaceous earth 27.5 Bentonite 60 In the case of emulsion They can be obtained by uniformly mixing and dissolving each component, and in the case of a wettable powder, by uniformly mixing and pulverizing each component. In the case of granules, the ingredients are uniformly mixed, water is added and thoroughly kneaded, and then granulated, then finely cut into granules and dried. Test Example 1 (Stem and Leaf Treatment Test) Sterilized alluvial soil was placed in a 1/2000a Wagner pot, and seeds of the test plants shown in Table 2 were sown.
When each plant reaches an approximately certain size (approximately 2 to 3 leaf stage), an emulsion containing the compound obtained by the method shown in the example as an active ingredient is formulated according to Formulation Example 1, and each of the active ingredients is A solution diluted with water to a concentration of 100 g/a was sprayed so that the entire surface of the stems and leaves of the plant was thoroughly and uniformly wetted. Three weeks after spraying, the herbicidal activity on each plant was examined. The results are shown in Table 2.
The herbicidal activity was evaluated by visual observation using an index in comparison with that of no treatment according to the following criteria. (Index) (Herbicidal activity) 0 No change 1 1-24% inhibition 2 25-49% inhibition 3 50-74% inhibition 4 75-90% inhibition 5 Complete death

[Table] In the above table, test plants A to H are the following plants. A... Blueberry B... Kusanemu C... Wildflower D... Radish E... Buckwheat F... Morning glory G... Wheat H... Takasaburou test example 2 (Soil treatment test) Alluvial soil sterilized in a 1/2000a Wagner pot The seeds of the test plants shown in Table 3 were sown and covered with soil to a depth of about 0.5 to 1.0 cm. Next, wettable powders containing the compound obtained by the method shown in the example as an active ingredient were prepared according to Formulation Example 2, and each powder contained 100% of the active ingredient.
It was diluted with water to give a ratio of g/a, and was sprayed so that the soil surface was evenly wetted. Three weeks after spraying, the herbicidal activity on each plant was examined. The results are shown in Table 3. The evaluation criteria were the same as in Test Example 1.

[Table] The control compounds are the same as in Table 2. Moreover, the test plants A to G are the same as those in Table 2. Test example 3 (flooding treatment test) Paddy soil was placed in a 1/5000a Wagner pot.
Furthermore, soil mixed with seeds of Japanese wildflower, Japanese cypress, Japanese azalea, and Kikashigusa seeds was added to the surface layer, and the water depth was maintained at 3 cm. Next, granules containing the compound obtained by the method shown in the example as an active ingredient were prepared according to Formulation Example 3, and the active ingredient was uniformly dispersed at 50 g/a. Three weeks after application, Herbicidal activity against each plant was examined.
The results are shown in Table 4. The evaluation criteria were the same as in Test Example 1.

【table】

[Table] The control compounds are the same as in Table 2. The test plants C, I to K are as follows. C...Novie I...Tamagayatsuri J...Azena K...Kikashigusa

Claims (1)

[Claims] 1. General formula [In the formula, R represents a lower alkyl group. X represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a benzyloxy group, or a lower haloalkyl group. n represents an integer from 1 to 3. ] An imidazolidin-2-one derivative represented by: 2 General formula [In the formula, X represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a benzyloxy group, or a lower haloalkyl group. n represents an integer from 1 to 3. ] An imidazolidin-2-one derivative represented by the general formula RNCO [wherein R represents a lower alkyl group]. ] The isocyanate represented by is reacted to form the general formula [In the formula, R, X and n are the same as above. ] A method for producing an imidazolidin-2-one derivative, which comprises obtaining an imidazolidin-2-one derivative represented by the following. 3 General formula [In the formula, R represents a lower alkyl group. X represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a benzyloxy group, or a lower haloalkyl group. n represents an integer from 1 to 3. ] A herbicide containing an imidazolidin-2-one derivative as an active ingredient.