JPH039909B2 - - 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 hydrogen atom, a lower alkyl group, a lower alkoxy lower alkyl group, a benzyl group, or a lower alkoxycarbonyl lower alkyl group. Ar
represents a phenyl group, a phenoxyphenyl group, or an aralkyloxyphenyl group, and each of these groups may be substituted with a halogen atom, a lower alkyl group, a lower alkoxy group, or a haloalkyl group. ] 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 the lower alkoxy lower alkyl group include a methoxymethyl group, a methoxyethyl group, a methoxypropyl group, and a butoxymethyl group. Examples of the lower alkoxycarbonyl lower alkyl group include a methoxycarbonylmethyl group, an ethoxycarbonylmethyl group, a propyloxycarbonylmethyl group, a methoxycarbonylethyl group, an ethoxycarbonylethyl group, and a propyloxycarbonylethyl group. Examples of the aralkyloxyphenyl group include benzyloxyphenyl group and phenethyloxyphenyl group. Examples of the halogen atom include fluorine, chlorine, bromine, and iodine atoms. Examples of lower alkoxy groups include methoxy, ethoxy, n-propyloxy, isopropyloxy, and n-butoxy groups. Examples of haloalkyl groups include monochloromethyl group, monochloroethyl group, monochloropropyl group, dichloroethyl group,
Examples include monobromomethyl group, monobromoethyl group, monobromopropyl group, monofluoromethyl group, trifluoromethyl group, and trifluoroethyl group. Examples of the phenyl group having a halogen atom, lower alkyl group, lower alkoxy group, or haloalkyl group as a substituent include 2-chlorophenyl group, 3-chlorophenyl group, 3,4
-dichlorophenyl group, 2-fluorophenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 3,4-dimethylphenyl group, 2-isopropylphenyl group, 2-methoxyphenyl group, 3 -methoxyphenyl group, 2
Examples include -n-propyloxyphenyl group, 2-isopropyloxyphenyl group, and 3-trifluoromethylphenyl group. Examples of the phenoxyphenyl group having a halogen atom, lower alkyl group, lower alkoxy group, or haloalkyl group as a substituent include 2-chlorophenoxyphenyl group, 3-chlorophenoxyphenyl group, 2-chlorophenoxyphenyl group,
Examples include methylphenoxyphenyl group, 4-methylphenoxyphenyl group, 3-trifluoromethylphenoxyphenyl group, 2-methoxyphenoxyphenyl group, 4-methoxyphenoxyphenyl group, etc. . Examples of the aralkyloxyphenyl group having a halogen atom, lower alkyl group, lower alkoxy group, or haloalkyl group as a substituent include 2-chlorobenzyloxyphenyl group, 4-chlorobenzyloxyphenyl group, 4-chlorobenzyloxyphenyl group,
Methylbenzyloxyphenyl group, 2-methylbenzyloxyphenyl group, 4-methoxybenzyloxyphenyl group, 3-trifluoromethylbenzyloxyphenyl group, 2-chlorophenethyloxyphenyl group, 4-methyl Examples include phenethyloxyphenyl group, 4-methoxyphenethyloxyphenyl group, and 3-trifluoromethylphenethyloxyphenyl group. 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. [In the formula, R' represents a lower alkyl group, a lower alkoxy lower alkyl group, a benzyl group, or a lower alkoxycarbonyl lower alkyl group. X represents a halogen atom. Ar is the same as above. ] In the above reaction formula, the hydantoin derivative represented by the general formula [ ] used as a raw material is a known compound, and can be obtained, for example, from N-methylglycine and allyl isocyanate by a conventional method. The reaction of reducing the compound represented by the general formula [] to obtain the compound represented by the general formula [a] can be carried out in a 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 [a]. The ratio of the compound represented by the general formula [] to sodium borohydride is not particularly limited and can be selected from a wide range, but the ratio of the former to the latter is usually 0.1 to 1.
It is preferable to use about 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 reaction between the compound represented by the general formula [a] and the alkyl halide represented by the general formula [] is
This can be carried out without a solvent or in a suitable solvent. Examples of the solvent include water, alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, and butyl alcohol, diethyl ether, dipropyl ether, dibutyl ether,
Ethers such as tetrahydrofuran and dioxane, halogenated hydrocarbons such as methylene chloride and chloroform, aromatic solvents such as benzene, toluene, xylene, chlorobenzene and nitrobenzene, pyridine, ethyl acetate, acetonitrile, dimethylformamide, etc. Can be done. The ratio of the compound represented by the general formula [a] 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 former. It is preferable to use about a molar amount, preferably about 1 molar to 2 times the molar amount. In the reaction between the compound represented by the general formula [a] and the compound represented by the general formula [], a base is used to collect the hydrogen halide that is released. Examples of the base used include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate,
Examples include tertiary amines such as triethylamine and tributylamine, pyridines such as pyridine, picoline, and lutidine, metallic sodium, sodium hydride, and sodium alcoholate.
The ratio of the compound represented by the general formula [a] and the hydrogen halide scavenger is not particularly limited and can be appropriately selected from a wide range, but usually the latter is about 5 times the molar equivalent of the former. It is preferable to use about equimolar to twice the molar amount. The reaction temperature for this reaction is not particularly limited, but is usually 0 to 0.
The reaction proceeds suitably at about 100°C, and generally
The reaction is completed in about 10 hours. The obtained compound can be processed by conventional means such as recrystallization,
It is purified by solvent extraction, column chromatography, etc. Examples of the compounds of the present invention obtained by the above method are as follows. 1-Methyl-3-phenyl-4-hydroxyimidazolidin-2-one 1-methyl-3-(2-chlorophenyl)-4-hydroxyimidazolidin-2-one 1-methyl-3-(3,4-dichlorophenyl )−
4-hydroxyimidazolidin-2-one 1-methyl-3-(3-methylphenyl)-4-hydroxyimidazolidin-2-one 1-methyl-3-(4-methoxyphenyl)-4-
Hydroxyimidazolidin-2-one 1-methyl-3-(4-benzyloxyphenyl)
-4-hydroxyimidazolidin-2-one 1-methyl-3-(4-phenoxyphenyl)-4
-Hydroxyimidazolidin-2-one 1-methyl-3-(3,4-dichlorophenyl)-
4-methoxyimidazolidin-2-one 1-methyl-3-(3,4-dichlorophenyl)-
4-benzyloxyimidazolidin-2-one 1-methyl-3-(3,4-dichlorophenyl)-
4-ethoxycarbonylmethyloxyimidazolidin-2-one 1-methyl-3-(3,4-dichlorophenyl)-
4-methoxymethyloxyimidazolidine-2-
The present invention also relates to a herbicide containing an imidazolidin-2-one derivative represented by the general formula [] as an active ingredient. The compounds of the present invention include Takasaburou, Aobiyu,
Kusanem, sparrow gnome, polygonum, mugwort, oarechingi, japonica, azaena, japonica,
It has a strong herbicidal effect on weeds such as wild grass, crabgrass, cyperus, and cyperus, so it can be used in the production and landscape of agricultural crops such as tangerines, apples, soybeans, corn, mulberries, tea, and paddy rice, where the growth of these weeds is harmful. It is useful for controlling harmful weeds. 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 alkyl bezene sulfonate, sodium lignin sulfonate, sodium alkyl sulfate, sodium polyoxyethylene alkyl sulfate, etc. organic solvents such as xylol, acetone, methanol, ethanol, isopropanol, dioxane, dimethylformamide, dimethyl sulfoxide, carbon tetrachloride, etc. 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, 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 giving Examples, Prescription Examples, and Test Examples below. Note that the test compound numbers in the test examples correspond to the numbers in the examples. Example 1 1-Methyl-3-(3,4-dichlorophenyl)
-Production of 4-hydroxyimidazolidin-2-one 1-methyl-3-(3,4-dichlorophenyl)
Hydantoin 10.4g/(0.04mol) in methanol
Suspended in 80ml. After cooling to 10° C., 1.5 g of sodium borohydride was added under stirring. After stirring for 30 minutes,
The mixture was returned to room temperature and further stirred for 2 hours. After the reaction is complete,
The reaction solution was concentrated, and water was added to the residue to precipitate crystals. The crystals were filtered and recrystallized from ethanol to obtain 9.2 g of white crystals (yield: 88%). Melting point: 185-186°C NMR of the crystal in DMSO- _d6 was shown as follows. δ2.85ppm (3H), δ3.28ppm (1H) δ3.65ppm (1H), δ5.57ppm (1H) δ6.45ppm (1H), δ7.36ppm (1H) δ7.68ppm (1H), δ7.97ppm ( 1H) Elemental analysis value (as C ₁₀ H ₁₀ N ₂ O ₂ Cl ₂ ) Analysis value % C46.04, H3.77, N10.69 Theoretical value % C46.00, H3.86, N10.73 Based on the above results It was confirmed. Example 2 1-methyl-3-(3,4-dichlorophenyl)
-Production of 4-ethoxyimidazolidin-2-one 1-methyl-3-(3,4-dichlorophenyl)
-4-hydroxyimidazolidin-2-one 10.4
g (0.04 mol) was dissolved in 100 ml of dimethylformamide. After cooling to 10° C., 2 g (0.04 mol) of sodium hydride was added under stirring. After stirring for 30 minutes, 4.4 g of ethyl bromide was added dropwise. After stirring at room temperature for 2 hours,
Water was added to the reaction solution, and the mixture was extracted with chloroform. The chloroform extract was concentrated to obtain an oil. yield
9.5 g (yield 82.1%) The oil was purified by silica gel column chromatography (solvent benzene:ethyl acetate = 1:1) to obtain an oil. MMR of the obtained oil in deuterated chloroform
was shown as follows. δ1.19ppm (3H), δ2.90ppm (3H) δ3.30-3.72ppm (4H) δ5.43ppm (1H), δ7.38ppm (1H) δ7.60ppm (1H), δ7.90ppm (1H) Elemental analysis Value (as C ₁₂ H ₁₄ N ₂ O ₂ Cl ₂ ) Analytical value % C49.79, H4.81 N9.72 Theoretical value % C49.84, H4.88, N9.69 Based on the above results It was confirmed. Examples 3 to 16 Examples 3 to 16 were prepared in the same manner as in Example 1 or 2.
Sixteen compounds were synthesized. Physical properties and NMR data are shown in Table 1.

【table】

[Table] Formulation example 1 (50% hydrating powder) (parts by weight) Compound of Example 1 50 Sodium ligninsulfonate 1 Dodecylbenzenesulfonic acid 4 Sodium clay 45 Formulation example 2 (30% emulsion) Compound of Example 2 30 Polyoxyethylene nonyl 10 Phenyl ether dimethylformamide 20 Xylene 40 Formulation example 3 (10% granules) Compound of Example 3 10 Sodium ligninsulfonate 0.5 Dodecylbenzenesulfonic acid 2 Sodium diatomaceous earth 27.5 Bentonite 60 In the case of an emulsion, the components can be uniformly mixed and ground, and in the case of an emulsion, the components can be uniformly mixed and dissolved. 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 (Soil Treatment Test) Sterilized alluvial soil was placed in a 1/2000a Wagner pot, seeds of test plants shown in Table 2 were sown, and the pot was covered with soil to a depth of approximately 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 1, 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 2. In addition, the herbicidal activity was evaluated by visual observation using an index compared to 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 G are the following plants. A... Blueberry B... Kusanemu C... Wildflower D... Japanese radish E... Buckwheat F... Morning glory G... Wheat test example 2 (stem and leaf treatment test) Sterilized alluvial soil was placed in a 1/2000a Wagner pot, and the Seeds of the test plants shown in Table 3 were sown, and when each plant reached an approximately certain size (approximately 2-3 leaf stage), an emulsion containing the compound obtained by the method shown in the example as an active ingredient was applied. Each product was prepared according to Formulation Example 2, diluted with water to contain 100 g/a of the active ingredient, and 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 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. H is Takasaburou. Test Example 3 (Flooding treatment test) Paddy soil was placed in a 1/5000a Wagner pot, and soil containing seeds of Japanese wildflower, Japanese cypress, Japanese azalea, and Kikashigusa seeds was added to the surface layer, and Urikawa tubers were placed on the bed. 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 formulated according to Formulation Example 3, and after transplanting paddy rice, the active ingredient was 50g/
The herbicidal activity on each plant was examined 3 weeks after application. The results are shown in Table 4. 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 C, I to L are as follows. C...Novie I...Kikashigusa J...Azena K...Kayatsuri L...Urikawa

Claims (1)

[Claims] 1. General formula [In the formula, R represents a hydrogen atom, a lower alkyl group, a lower alkoxy lower alkyl group, a benzyl group, or a lower alkoxycarbonyl lower alkyl group. Ar
represents a phenyl group, a phenoxyphenyl group, or an aralkyloxyphenyl group, and each of these groups may be substituted with a halogen atom, a lower alkyl group, a lower alkoxy group, or a haloalkyl group. ] An imidazolidin-2-one derivative represented by: 2 General formula [In the formula, Ar represents a phenyl group, a phenoxyphenyl group, or an aralkyloxyphenyl group, and each of these groups may be substituted with a halogen atom, a lower alkyl group, a lower alkoxy group, or a haloalkyl group. ] By reducing the hydantoin derivative represented by the general formula [In the formula, Ar is 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, Ar represents a phenyl group, a phenoxyphenyl group, or an aralkyloxyphenyl group, and each of these groups may be substituted with a halogen atom, a lower alkyl group, a lower alkoxy group, or a haloalkyl group. ] An imidazolidin-2-one derivative represented by the general formula R′X [wherein R′ represents a lower alkyl group, a lower alkoxy lower alkyl group, a benzyl group or a lower alkoxycarbonyl lower alkyl group]. X represents a halogen atom. ] by reacting with an alkyl halide represented by the general formula [In the formula, R' and Ar 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. 4 General formula [In the formula, R represents a hydrogen atom, a lower alkyl group, a lower alkoxy lower alkyl group, a benzyl group, or a lower alkoxycarbonyl lower alkyl group. Ar
represents a phenyl group, a phenoxyphenyl group, or an aralkyloxyphenyl group, and each of these groups may be substituted with a halogen atom, a lower alkyl group, a lower alkoxy group, or a haloalkyl group. ] A herbicide characterized by containing an imidazolidin-2-one derivative represented by the following as an active ingredient.