JPH039908B2 - - 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. Many imidazolidin-2-one derivatives have been known so far, and among them, Japanese Patent Publication No. 47-5840, No. 47-
No. 32064 and No. 50-11452 disclose imidazolidin-2-one-1-carboxyamide derivatives, and it is known that these compounds have herbicidal activity. However, these compounds cannot be said to be sufficient as herbicides.
On the other hand, as seen in these documents, many compounds in which the 4th or 5th position of the imidazolidine ring is a hydrogen atom have already been synthesized and used for various purposes. As a result of various studies on compounds with strong herbicidal activity and practical use, the present inventors found that
Imidazolidine having a methyl group at position or 5-
A compound in which a methyl group is introduced into the 3-position nitrogen atom of a 2-one-1-carboxyanilide derivative, that is,
3,4-dimethylimidazolidin-2-one-1
-Carboxanilide derivatives and 3,5-dimethylimidazolidin-2-one-1-carboxanilide derivatives have been found to have excellent herbicidal activity. The imidazolidin-2-one derivative of the present invention is
This is a new compound that has not been described in any literature and is represented by the general formula [ ]. [In the formula, Ar represents a phenyl group with or without a substituent or a pyridyl group with or without a substituent. Here, the substituent is a halogen atom,
A lower alkyl group, a lower haloalkyl group, a lower alkoxy group, a hydroxyl group, a nitro group, a carboxyl group, a lower alkoxycarbonyl group, an amino group, or a lower alkyl-substituted amino group. ] The compound of the present invention represented by the general formula [ ] can be produced by various methods, for example, synthesized by the following formula. [In the formula, Ar is the same as above] In the above reaction formula, the imidazolidin-2-one derivative represented by the general formula [ ] used as a raw material is a new compound, for example, 4-methylimidazolidin-2-one. [] is reacted with an isocyanic acid derivative [] or a carbamic acid derivative [], or 4-methylimidazolidine-2
It is obtained by reacting -one [] with phosgene to produce 4-methylimidazolidin-2-one-1-carbonyl chloride [], and then reacting it with an amine derivative []. When the methyl group of the imidazolidine ring is a 4-position derivative, the above reaction is carried out directly, but in the case of a 5-position derivative, the above reaction is carried out after protecting the nitrogen atom at the 3-position with an acetyl group, and then the acetyl group is further hydrolyzed. [See reference example below]. The above reaction and reaction formula are as follows. [In the formula, Ar is the same as above] 4-Methylimidazolidin-2-one [] used as a raw material here is obtained by a conventional method using propylene diamine and urea or carbonate ester. The reaction between the compound [] and the compound [] or [] and the reaction between the compound [] and the compound [] or [] can be carried out without a solvent or in a solvent. The solvent used may be any solvent that does not interact with the isocyanate or N-allyl ethyl carbamate, but generally diethyl ether, dipropyl ether, dibutyl ether,
Examples include ethers such as tetrahydrofuran, halogenated hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride, and aromatic hydrocarbons such as benzene, toluene, and xylene. The ratio of the compound [] or [] and the compound [] or [] is not limited and can be used within a wide range, but generally the latter is used in a molar amount of 1 to 10 times the former, preferably 1 to 5 times the molar amount of the latter. Used in twice the molar amount. A catalyst may be used in the reaction between compound [] or [] and compound []. Examples of the catalyst include tertiary amines such as triethylamine and tributylamine, and the amount used is usually 0.01 to the compound [] or [].
~0.5 molar amount is sufficient. The reaction temperature is usually 50 to 200°C, preferably 70 to 150°C, and the reaction is completed in 3 to 5 hours. To obtain the compound [] or [] by reacting the compound [] or [] with phosgene, for example,
The method shown in J.Org.Chem. 29 , 2401-2404 (1964) may be followed. The reaction between compound [] or [] and compound [] is carried out without a solvent or in a solvent. Examples of solvents used include ethers such as diethyl ether, dipropyl ether, dibutyl ether, and tetrahydrofuran, halogenated hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride, and aromatic carbons such as benzene, toluene, and xylene. Examples include hydrogens, ethyl acetate, acetonitrile, water and the like. The ratio of compound [ ] or [ ] to compound [ ] is not limited and can be used within a wide range, but in general, the former should be used in proportion to the latter.
~10 times the molar amount, preferably 1 to 5 times the molar amount. In this reaction, a base is used as a scavenger for the hydrochloric acid that is eliminated. The base used may be the amines [] used as raw materials, or tertiary amines such as triethylamine, tributylamine, and ethylmorpholine, pyridines, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, etc. Can be mentioned. The amount of such a base to be used is 1 to 1 for the compound [] or [].
It is preferable to use 10 times the molar amount, preferably 1 to 5 times the molar amount. The reaction temperature may be generally 50 to 150°C, and the reaction is generally completed in about 3 to 5 hours. Acetylation by reaction of compound [] with acetyl chloride or acetic anhydride is carried out by a conventional method. The reaction is carried out in a solvent, and examples of the solvent used include ethers such as diethyl ether, dipropyl ether, and dibutyl ether, halogenated hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride, benzene, and toluene. , xylene, and other aromatic hydrocarbons.
The ratio of compound [] and acetyl chloride or acetic anhydride to be used is not limited and can be varied within a wide range, but the latter is usually used in an amount of 1 to 5 times, preferably 1 to 2 times, by molar amount relative to the former. . In the reaction of the compound [] with acetyl chloride or acetic anhydride, a base is used as a scavenger for the hydrochloric acid that is eliminated. The base used is triethylamine,
Examples include tertiary amines such as tributylamine and ethylmorpholine, and pyridines. The amount of base used is equivalent to the amount of acetyl chloride or acetic anhydride used. The reaction temperature for this reaction is -10 to 50°C and the reaction time is about 2 to 10 hours. In the present invention, compound [b] can be obtained by further hydrolyzing compound []. An alkaline aqueous solution is used for hydrolysis. Examples of the alkali used include sodium hydroxide and potassium hydroxide. The concentration of the alkaline aqueous solution may be 5 to 20%, and the hydrolysis is preferably carried out under reflux. The reaction time is about 1 to 3 hours. The compound of the present invention can be obtained by methylating the compound represented by the general formula [] with dimethyl sulfate or methyl iodide. The methylation reaction is carried out in dimethylformamide in the presence of a base agent. Examples of the base agent used include sodium metal, sodium hydride, and sodium alcoholate. The ratio of the compound represented by the general formula [] and dimethyl sulfate or methyl iodide is not particularly limited, but the latter is usually used in an amount of 1 to 10 times, preferably 1 to 5 times, by molar amount relative to the former. . Reaction temperature is usually 0
The temperature is ~100°C, and the reaction time is about 5 to 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. Γ3,4-dimethylimidazolidin-2-one-
1-carboxyanilide Γ3,4-dimethylimidazolidin-2-one-
1-Carboxy-(2'-chloranilide) Γ3,4-dimethylimidazolidin-2-one-
1-Carboxy-(3'-chloranilide) Γ3,4-dimethylimidazolidin-2-one-
1-Carboxy-(4'-chloranilide) Γ3,4-dimethylimidazolidin-2-one-
1-Carboxy-(2',4'-dichloroanilide) Γ3,4-dimethylimidazolidin-2-one-
1-Carboxy-(2'-methylanilide) Γ3,4-dimethylimidazolidin-2-one-
1-Carboxy-(3'-methylanilide) Γ3,4-dimethylimidazolidin-2-one-
1-Carboxy(4'-nitroanilide) Γ3,4-dimethylimidazolidin-2-one-
1-Carboxy-(2'-methoxyanilide) Γ3,4-dimethylimidazolidin-2-one-
1-Carboxy-(4'-methoxyanilide) Γ3,4-dimethylimidazolidin-2-one-
1-Carboxy-(4'-dimethylaminoanilide) Γ3,5-dimethylimidazolidin-2-one-
1-carboxyanilide Γ3,5-dimethylimidazolidin-2-one-
1-Carboxy-(2'-chloranilide) Γ3,5-dimethylimidazolidin-2-one-
1-Carboxy-(3'-methylanilide) Γ3,5-dimethylimidazolidin-2-one-
1-Carboxy-(4'-methoxyanilide) Γ3,5-dimethylimidazolidin-2-one-
1-Carboxy-(3'-nitroanilide) Γ3,5-dimethylimidazolidin-2-one-
1-Carboxy-(2'-pyridylamide) Γ3,5-dimethylimidazolidin-2-one-
1-Carboxy-(4'-pyridylamide) The present invention also relates to a herbicide containing an imidazolidin-2-one derivative represented by the above general formula [] as an active ingredient. The compounds of the present invention include Takasaburou, Aobiyu, Kusanemu, Sparrow gnome, Japanese knotweed, Artemisia annua, Porphyra spp.
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 mandarin oranges, 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 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, application method,
It 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 as appropriate, but in general, the amount of active ingredient is about 5 to 400 g /
a, preferably about 10 to 100 g/a. The present invention will be explained in more detail below with reference to Reference Examples, Examples, Prescription Examples, and Test Examples. Reference Example 1 Production of 4-methylimidazolidin-2-one-1-carboxyanilide 10 g of 4-methylimidazolidin-2-one
(0.1 mol) and 11.9 g (0.1 mol) of phenyl isocyanate were combined and melted at 150°C for 2 hours. The crystalline melt was recrystallized from ethanol to obtain 20 g of white crystals. Reference Example 2 Production of 5-methylimidazolidin-2-one-1-carboxy-(2'-chloroanilide) 20 g of 4-methylimidazolidin-2-one
(0.2 mol) was dissolved in 200 ml of chloroform, and 15.8 g (0.2 mol) of pyridine was added. 15.7 g (0.2 mol) of acetyl chloride was added dropwise under ice-cooling and stirring. After stirring at room temperature for 5 hours, the reaction solution was washed with water, dried, and concentrated.
Obtained crystals. The obtained crystals were recrystallized from toluene to obtain 16.5 g of white crystals. 14.2 g (0.1 mol) of the crystals obtained here and 15.4 g (0.1 mol) of 2-chlorophenyl isocyanate.
were combined and melted at 150°C for 2 hours. into a crystalline melt
85 ml of 10% sodium hydroxide was added and the mixture was refluxed for 30 minutes. After the reaction, the reaction solution was extracted with chloroform, washed with water, dried, and concentrated to obtain crystals. The obtained crystals were recrystallized from ethanol to obtain 20.7 g of white crystals. Example 1 3,4-dimethylimidazolidin-2-one-
Production of 1-carboxyanilide 4-methylimidazolidine-2 obtained in Reference Example 1
11 g (0.05 mol) of -one-1-carboxyanilide was dissolved in 100 ml of DMF, and 2.4 g (oily 50%, 0.05 mol) of sodium hydride was added under ice-cooling and stirring. After stirring for 1 hour, 7.1 g (0.05 mol) of methyl iodide
was added dropwise, and the mixture was stirred at room temperature for 5 hours. After the reaction, water was added to the reaction solution to precipitate crystals. The crystals were filtered, washed with water, and recrystallized from ethanol to yield 8.2 g of white crystals.
(yield 70%). Melting point: 62-63°C NMR of this crystal in deuterated chloroform was shown as follows. δ (ppm) 1.26 (3H), 2.80 (3H), 3.35~4.20
(3H), 7.00-7.70 (5H) Elemental analysis Actual value (%) C: 67.77 H: 6.50 N: 17.98 Calculated value (%) C: 61.79 H: 6.48 N: 18.01 From the above results It was confirmed. Experimental example 2 3,5-dimethylimidazolidin-2-one-
Production of 1-carboxy-(2'-chloroanilide) 5-methylimidazolidine-2 obtained in Reference Example 2
-one-1-carboxy-(2'-chloranilide)
Dissolve 12.7g (0.05mol) in 100ml of DMF and add 2.4g of sodium hydride (50% oily, 0.05mol) under ice cooling.
added. 6.3g of dimethyl sulfate after stirring for 1 hour
(0.05 mol) was added dropwise and stirred at room temperature for 5 hours. After the reaction, water was added to the reaction solution to precipitate crystals. After filtering and washing the crystals with water, recrystallize them from ethanol to obtain white crystals.
9.3g (yield 70%) was obtained. Melting point: 91-92°C NMR of this crystal in deuterated chloroform was shown as follows. δ (ppm) 1.45 (3H), 2.90 (3H), 2.95 (1H),
3.60 (1H), 4.50 (1H), 6.85~7.55 (3H), 8.40
(1H) Elemental analysis analysis value (%) C: 53.81 H: 5.28 N: 15.69 Calculated value (%) C: 53.84 H: 5.27 N: 15.70 From the above results It was confirmed. Examples 3 to 29 Compounds of Examples 3 to 29 were produced in the same manner as in Reference Examples 1 and 2 and Examples 1 and 2. The physical properties and NMR data of the compound are shown in Table 1.

【table】

【table】

【table】

【table】

[Table] Formulation example 1 (30% emulsion) (parts by weight) Compound of Example 1 30 Polyoxyethylene nonyl phenyl ether
10 Dimethylformamide 20 Xylene 40 Formulation example 2 (50% hydrating powder) 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 an emulsion, the components can be uniformly mixed and dissolved, and in the case of a wettable powder, they can be obtained by uniformly mixing and pulverizing. In the case of granules, each component is mixed uniformly, water is added and kneaded thoroughly, and then granulated.
It is 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 the seeds of the test plants shown in the table were sown until each plant had an approximately constant size (approximately 2-3 leaf stage). When this is achieved, an emulsion containing the compound obtained by the method shown in the example as an active ingredient is formulated according to Formulation Example 1,
Each of the active ingredients was diluted with water to a concentration of 100 g/a 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 against each plant was examined. The results are shown in Table 1.
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] Test Example 2 (Soil treatment test) Sterilized alluvial soil was placed in a 1/2000a Wagner pot, seeds of the test plants shown in Table 1 were sown, and the soil 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 2, and each powder contained 100 g/a of the active ingredient.
It was diluted with water so that the soil surface was evenly wetted. Three weeks after spraying, the herbicidal activity against each plant was examined. The results are shown in Table 1. The evaluation criteria were the same as in Test Example 1.

[Table] * Same as table
Test Example 3 (Irrigation treatment test) Paddy soil was put into a 1/5000a Wagner pot, and soil mixed with seeds of Japanese wildflower, Japanese cypress, azalea, and Kikashigusa were added to the surface layer, and then Urikawa tubers were placed on the bed. ,
The water depth was kept 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, granules containing 50 g/g of each active ingredient were prepared.
The herbicidal activity on each plant was examined three weeks after application. The results are shown in Table 1. The evaluation criteria were the same as in Test Example 1.

【table】

[Table] * Same as table

Claims (1)

[Claims] 1. General formula [In the formula, Ar represents a phenyl group with or without a substituent or a pyridyl group with or without a substituent. Here, the substituent is a halogen atom,
A lower alkyl group, a lower haloalkyl group, a lower alkoxy group, a hydroxyl group, a nitro group, a carboxyl group, a lower alkoxycarbonyl group, an amino group, or a lower alkyl-substituted amino group. ] An imidazolidin-2-one derivative represented by: 2 General formula [In the formula, Ar represents a phenyl group with or without a substituent or a pyridyl group with or without a substituent. Here, the substituent is a halogen atom,
A lower alkyl group, a lower haloalkyl group, a lower alkoxy group, a hydroxyl group, a nitro group, a carboxyl group, a lower alkoxycarbonyl group, an amino group, or a lower alkyl-substituted amino group. ] A general formula characterized by reacting the imidazolidin-2-one derivative represented by with dimethyl sulfate or methyl iodide. [In the formula, Ar is the same as above. ] A method for producing an imidazolidin-2-one derivative represented by the following. 3 General formula [In the formula, Ar represents a phenyl group with or without a substituent or a pyridyl group with or without a substituent. Here, the substituent is a halogen atom,
A lower alkyl group, a lower haloalkyl group, a lower alkoxy group, a hydroxyl group, a nitro group, a carboxyl group, a lower alkoxycarbonyl group, an amino group, or a lower alkyl-substituted amino group. ] A herbicide characterized by containing an imidazolidin-2-one derivative represented by the following as an active ingredient.