JPH03176475A - Cyclic urea derivative and herbicide - Google Patents

Abstract

NEW MATERIAL:A compound of formula I (X is H, halogen, alkyl or alkoxy; Y is halogen, alkoxy, alkyl, halogenated alkyl or phenyl); Z is O or S; (m) is 0 or 1; (n) is 0, 1, 2 or 3). EXAMPLE:3-Phenyl-1-(3,4,5-trichloro-alpha-alpha-dimethylbenzyl)-2-perh ydroxypyrimidinone. USE:A herbicide. PREPARATION:An aminoalkanoic acid amide derivative of formula II is reduced with a suitable reducing agent (e.g. lithium aluminum hydride) and the prepared intermediate of formula III is made to react with phosgene or thiophosgene of formula IV in the presence of a base (e.g. triethylamine, pyridine or NaOH), in a suitable solvent to provide the compound of formula I.

Description

[Detailed description of the invention] (Industrial application field) The present invention relates to novel cyclic urea derivatives.

More specifically, the present invention relates to a novel cyclic urea derivative represented by the general formula [Natsu] and herbicides containing the derivative.

(Prior Art) Several cyclic urea derivatives having herbicidal activity have been known,9 for example, l-aryl-3-aminoalkanoyl-2-imidazolidinones, described in US Pat. No. 3,334. No. 098 and Swiss Patent No. 430,324 describe that 1-phenyl-2-imidazolidinones have herbicidal effects, respectively.

Substituted tetrahydro-2-pyrimidinone derivatives and the like are also disclosed in JP-A-49-132,073, JP-A-57-E-39.069 and JP-A-58-140゜07.
It is described in Specification No. 8 as a selective herbicide.

(Problems to be Solved by the Invention) The minimum conditions that herbicides must meet include weed control effects and high safety for humans and animals. recent years,
In addition, from the user's perspective, there is a strong demand for expanded selective action that kills only weeds without harming crops, as well as moderate residual efficacy that can reduce the number of chemical treatments. From this point of view, it is desired to develop a drug that has a high herbicidal effect at a low dose and causes less environmental pollution.

However, although the conventionally known cyclic urea derivatives described above have a certain degree of activity and selectivity as herbicides, these are not always satisfactory.

The purpose of the present invention is to meet these demands and solve problems in the field of herbicides. The present invention provides highly cyclic urea derivatives as well as herbicides.

(Means for Solving the Problems) In order to achieve the above object, the present inventors synthesized various cyclic urea derivatives and conducted extensive research on their usefulness. As a result, α, α expressed by the following general formula [+]
It was discovered that a novel cyclic urea derivative having a -dimethyl (substituted) benzyl group has higher herbicidal activity and selectivity than conventional cyclic urea derivatives, leading to the present invention.

That is, 1 the present invention is based on the general formula (wherein, 1m indicates oxygen or sulfur atom
represents O or 1, and n represents O or an integer from 1 to 3), and a herbicide containing the same as an active ingredient.

Next, typical specific examples of the compounds of the present invention represented by the general formula [11] are shown in Table 1, and the compound numbers are referred to in the following description.

(The following is a blank space) Table 1 Table 1 continued The compound of the present invention represented by general formula (11) can be produced by Production Method 1 and Production Method 2 shown below.

Production method 1 (X, Y, Z, m and n in the formula have the same meanings as above) An aminoalkanoic acid amide derivative represented by general formula (II) is reduced with an appropriate reducing agent, One reaction which can give intermediate Cm) can be carried out at room temperature or heated or cooled as required. Preferably, the temperature range is from 0°C to the boiling point of the solvent.

After the completion of the reaction, the intermediate (m) can be taken out from the reaction mixture according to a conventional method.6For example, the reaction mixture is poured into ice water, made alkaline with sodium hydroxide, extracted with a water-immiscible organic solvent, and the solvent is removed. It can be obtained by distillation. Examples of the reducing agent used in the O-reaction, which can be further purified by distillation or column chromatography if necessary, include lithium aluminum hydride. Examples of solvents that can be used in the reaction include benzene and toluene.

Examples include hydrocarbons such as xylene, ethers such as diethyl ether, tetrahydrofuran, and dimethoxyethane.

Next, the obtained intermediate (m) was added in the presence of a base.

By reacting with phosgene or thiophosgene represented by the general formula (IV) in a suitable solvent, the compound of the present invention represented by -Momonen (1) can be obtained in good yield. Further, the reaction in which diphosgene or triphosgene can be used instead of phosgene can be carried out under water cooling or at room temperature. After completion of the reaction, which is preferably carried out at 0°C to 50°C, the compound of the present invention can be taken out according to a conventional method. After dissolving in water or alkali, the solvent can be removed by distillation.

Examples of bases that can be used in one reaction that can be further purified by column chromatography if necessary include organic amines such as triethylamine and pyridine, and inorganic bases such as sodium hydroxide and potassium hydroxide. It will be done. Inorganic bases can also be used as aqueous solutions 0 Reaction solvents include 1 Hydrocarbons such as benzene, toluene, etc., ethers such as diethyl ether, tetrahydrofuran, etc., halogenated carbons such as dichloromethane, chloroform, etc. Hydrogens, acetone, ketones such as methyl ethyl ketone, etc. can be mentioned.

Here, regarding the manufacturing method of the aminoalkanoic acid amide derivative represented by the general formula (11) used as the starting material in the above manufacturing method of the compound of the present invention, the following (1) case of m=1 (V) (Vl ) [■-1] (X, Y and n in the formula have the same meanings as above.) When m = 1, the compound represented by -Mongan (11-13 is represented by the general formula (V)) It can be obtained by reacting the compound represented by the general formula (VI) with the compound represented by the general formula (VI). That is, the compound represented by the -monana [■] and the general formula (
It can be obtained in good yield by reacting the compound represented by Vl) without a solvent or in a suitable solvent at room temperature or under heating conditions. Preferably from 20°C to 150°C
After the completion of the zero reaction carried out at 0.degree. C., the used solvent can be distilled off and taken out. Solvents that can be used in the 6 reactions, which can be purified by recrystallization or column chromatography if necessary, include, for example, hydrocarbons such as benzene and toluene, ethers such as diethyl ether and dioxane, dichloromethane, Examples include halogenated hydrocarbons such as chloroform and alcohols such as methanol and ethanol.

(2) When m=o [V] (■) [■-2] (X, Y, and n in the formula have the same meanings as above) When m=o, -Monken (II- The compound represented by 2) is a compound represented by the general formula (V), the general formula is the general formula [■]
It can be obtained by reacting with a compound represented by That is, it can be obtained by reacting a compound represented by -Momonana (Vl) and a compound represented by the general formula [■] in the presence of a base, without a solvent or in an appropriate solvent at room temperature or by heating. Preferably, after completion of the reaction, which is carried out at a temperature ranging from 20°C to the boiling point of the solvent.

For example, the reaction mixture is poured into water and extracted with a water-immiscible organic solvent.

After washing with water, the solvent is distilled off.

Bases that can be used in one reaction, which can be purified by recrystallization or column chromatography if necessary, include organic amines such as triethylamine and pyridine, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc. Reaction solvents that can be used include hydrocarbons such as benzene and toluene, ethers such as diethyl ether and tetrahydrofuran, and protic polar solvents such as acetonitrile, dimethylformamide and dimethylacetamide. can be used.

Production method 2 When m=1 and Z=O, the general formula (
The compound of the present invention represented by 1) can be produced.

(X, Y and n in the formula have the same meanings as above) By reacting the compound represented by the general formula (V) with 1-bromo-3-chloropropane, the compound represented by the general formula [■] For example, -Momonana (
0 obtained by reacting a mixture of the compound represented by V) and 1-bromo-3-chloropropane at 30°C to 150°C without a solvent. After the reaction is complete, dissolve in a water-immiscible organic solvent as necessary. After washing with water or alkali, the solvent can be distilled off. If necessary, it can also be purified by distillation or column chromatography.

Next, the compound represented by -monana [■] is expressed by the general formula (IX)
React with a phenyl isocyanate derivative represented by
- One reaction capable of obtaining the compound represented by Monka (X) is carried out in cooling or at room temperature, but it can also be heated if necessary.

After completion of the 6 reactions, which are preferably carried out at 0°C to 60°C, the target product can be taken out according to a conventional method.

For example, it can be obtained by distilling off the solvent used, or by dissolving in a water-immiscible organic solvent, washing with water, and then distilling off the solvent. Examples of solvents that can be used in the 6 reactions, which can be purified by recrystallization or column chromatography as necessary, include hydrocarbons such as benzene and toluene, ethers such as diethyl ether and tetrahydrofuran, Halogenated hydrocarbons such as dichloromethane, chloroform, etc., ketones such as acetone, methyl ethyl ketone, etc., aprotic polar solvents such as acetonitrile, dimethylformamide, etc. can be used.

Next, in the presence of a base, the compound represented by -Momonana (X),
By cyclization, general formula (1) (m=1.Z=O
) The reaction capable of obtaining the compound of the present invention represented by 0 is carried out at room temperature or by heating. Preferably, the reaction is carried out within the range from room temperature to the boiling point temperature of the solvent. After the reaction is completed, it can be taken out according to a conventional method. It can be taken out by dissolving it in a solvent, washing it with water, and distilling off the solvent.

If necessary, the base that can be used in the reaction may be purified by recrystallization or column chromatography, such as sodium hydroxide.

Inorganic bases such as potassium hydroxide, sodium carbonate, potassium carbonate, organic bases such as triethylamine, pyridine, etc., sodium methylate.

Examples include metal alcoholades such as sodium ethylate, metal hydrides such as sodium hydride, potassium hydride, and the like. Hydrocarbons such as benzene, toluene, etc. can also be used as solvents in the reaction.

Examples include ethers such as diethyl ether and tetrahydrofuran, alcohols such as methanol and ethanol, and aprotic polar solvents such as dimethylformamide, trimethylacetamide, and pyridine.

Next, the method for producing the compound of the present invention and its intermediate will be specifically explained with reference to Reference Examples and Examples.

Reference M1 Production of 3-(3,4,5-trichloro-α,α-dimethylbenzylamino)propionanilide 1.8 g (12.6 mmol) of acrylanilide and 3.
4.5-hlichloroα,α-dimethylbenzylamine3. After stirring a mixture of Qg (12.6 mmol) at 120°C for 1 day, the obtained crude product was crystallized with isopropyl ether to obtain 3.4 g of the target compound (yield 70%).
) was obtained.

Reference Example 2 Production of N-(3,4,5-trichloro-α,α-dimethylbenzylaminopropane 3-(3,4,5-trichloro-α,α-dimethylbenzylaminopropane) ) 3.4 g (8.8 mmol) of propionanilide was dissolved in 20 mfl of tetrahydrofuran, and this was added dropwise to 150 mQ of diethyl ether in which 0.5 g of lithium aluminum hydride was suspended with stirring.After refluxing for 5 hours, the mixture was poured into ice water. After stirring and making alkaline with sodium hydroxide, an oil was extracted with diethyl ether. After drying the extract over anhydrous magnesium sulfate, the solvent was distilled off to obtain 2.9 g of the target compound (
A yield of 89% was obtained.

Example 1 3-phenyl-1-(3,4,5-trichloro-α,α
-dimethylbenzyl)-2-berhydropyrimidinone (
Production of Compound 7) N-(3,4,5-trichloro-α,α-dimethylbenzyl〉-N゛-)l produced by the method of Reference Example 2; Ru 1
, 3-diaminopropane 1.2. (3.2 mmol),
To a mixture of 1.4 g (14.2 mmol) of triethylamine and 100 mA of dichloromethane was added 3.7 mL of a 1.93 mol solution of phosgene in toluene (7,
1 mmol) was added dropwise under water cooling. - After stirring at room temperature overnight, the solvent was distilled off, the resulting residue was partitioned with ethyl acetate and an aqueous sodium hydroxide solution, and the organic layer was washed with water and then dried over anhydrous magnesium sulfate. After distilling off the solvent, the residue was recrystallized from ethanol-isopropyl ether to obtain 0.4 g (yield: 33%) of the target compound.

Reference Example 3 Production of 3-(3,5-dichloro-α α-dimethylbenzylamino)-N-(2-fluorophenyl)propionamide N-(2-fluorophenyl)acrylamide 4, Og
(24,5 mmol) and 3,5-dichloro-α,α-
Dimethylbenzylamine 5.0g (245 mmol)
After stirring the mixture at 120° C. for 1 day, the obtained crude product was crystallized from isopropyl ether to obtain 7.6 g (yield: 84%) of the target compound.

Reference example 4 N-(3,5-dichloro-α,α-dimethylbenzyl)
-N'-(2-fluorophenyl)-1,3-diaminopropane 3-(3,5-dichloro-α produced by the method of Reference Example 3)
7.6 g (20.6 mmol) of α-dimethylbenzylamino)-N-(2-fluorophenyl)propionamide was dissolved in 30 mg of tetrahydrofuran, and 1.2 g of lithium aluminum hydride (3Q, 73
The mixture was poured into 200 mg of diethyl ether in which Millimorun was suspended while stirring. After refluxing for 4 hours, the mixture was poured into water, made alkaline by adding sodium hydroxide, and extracted with diethyl ether. The extract was washed with water, dried over anhydrous magnesium sulfate, and the solvent was distilled off. The resulting residue was purified using silica gel column chromatography to obtain 5.2 g (yield: 71%) of the target compound.

Example 2 l-(35-dichloro-α,α-dimethylbenzyl)-
Production of 3-(2-fluorophenyl)-2-perhydro,pyrimidinone (Compound 12) N-(3,5-dichloro-α produced by the method of Reference Example 4)
, α-dimethylbenzyl)-N'-(2-fluorophenyl)-1,3-diaminopropane 2.0 g (5,
6 mmol), triethylamine 2-3 g (22,
A 1°93 molar solution of phosgene in toluene was added with stirring to a mixture of 100 ml dichloromethane (6 mmol) and 5 ml of dichloromethane.
．． 8mQ (11.2 mmol) was added dropwise under water cooling. - After stirring at room temperature overnight, the solvent was distilled off, the residue was separated between ethyl acetate and an aqueous sodium hydroxide solution, the organic layer was washed with water, and then dried over anhydrous magnesium sulfate. After distilling off the solvent, the obtained residue was recrystallized from ethanol-isopropyl ether to obtain 0.8 g of the target compound (yield 37%).
I got it.

Reference Example 5 Production of 3-(3,5-dichloro-α,α-dimethylbenzylamino)propionanilide Acrylanilide 1
．． 8 g (12,2 mmol) and 3,5-dichloro-α
A mixture of 2.5 g (12.3 mmol) of α-dimethylbenzylamine was stirred at 120°C for 1 day, and the resulting crude product was purified using silica gel column chromatography to obtain 3.5 g (yield) of the target compound. 81%).

Reference example 6 N-(3,5-dichloro-α,α-dimethylbenzyl)
-N'-phenyl-1,3-diaminopropane 3-(3,5-dichloro-α produced by the method of Reference Example 5)
, α-dimethylbenzylamino)propionanilide
3.5 g (10 mmol) was dissolved in 20 rnfl of tetrahydrofuran, and the solution was diluted with diethyl ether 150 ml.
Lithium aluminum hydride suspended in mA 0
．． 6 g (15.0 mmol) was added dropwise with stirring. After refluxing this mixture for 2 hours, it was poured into ice water, made alkaline by adding sodium hydroxide, and extracted with diethyl ether. After drying this extract over anhydrous magnesium sulfate, the solvent was distilled off, and the resulting residue was purified using silica gel column chromatography to obtain the target compound 0.
．． 9 g (yield 27%) was obtained.

Example 3 l-(3,5-dichloro-α,α-dimethylbenzyl)
-3-Phenyl-2-berhydropyrimidinethione (compound 38) N-(3,5-dichloro-α produced by the method of Reference Example 6)
, α-dimethylbenzyl)-N'-phenyl-1,3-
0.9 g (2.7 mmol) of diaminopropane and 0.6 g (5.9 mmol) of triethylamine were dissolved in 50 mA of dichloromethane, and 0.0 g of thiophosgene was added to this solution.
．． 3 g (2.8 mmol) was added dropwise under water cooling while stirring. - After continuing to stir at room temperature overnight, the solvent was distilled off, and the resulting residue was separated between ethyl acetate and an aqueous sodium hydroxide solution.

The organic layer was washed with water and then dried over anhydrous magnesium sulfate. After distilling off the solvent, the residue was purified by silica gel column chromatography to obtain 0.4 g (yield: 39%) of the target compound.

Reference example 7 3-(3,5-dichloro-4-fluoro-α.

Preparation of α-dimethylbenzylamino)propionanilide 3.0 g (20.0 mmol) of acrylanilide and 3
, 5-dichloro-4-fluoro-α α-dimethylbenzylamine (4.5 g (20.0 mmol)) was heated at 120°C for 24 hours with stirring.The resulting solid was washed with hexane to obtain the desired product. Compound 6.8g (yield 9
3%).

Reference example 8 N-(3,5-dichloro-4-fluoro-α.

Production of α-dimethylbenzyl)-N'-phenyl-1,3-diaminopropane Lithium aluminum hydride 0.4 g (10,
0 mmol) in diethyl ether suspension.
A solution of 3.7 g (10.0 mmol) of 5-dichloro-4-fluoro-α,α-dimethylbenzylamino)propionanilide in diethyl ether was gradually added dropwise with stirring.After one drop was completed.

After the completion of one reaction in which stirring was continued for 1 hour, the solution was gradually poured into ice water and extracted with diethyl ether. After drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure to obtain 2.6 g (yield: 74%) of the target compound.

Example 4 l-(3,5-dichloro-4-fluoro-α.

Preparation of α-dimethylbenzyl)-3-phenyl-2-berhydropyrimidinone (compound 16) N-(3,5-dichloro-4-fluoro-α,α-dimethylbenzyl)-N'-phenyl-1 To a toluene solution of 1.8 g (5.0 mmol) of ,3-diaminopropane and 1.1 g (10.0 mmol) of triethylamino was added dropwise a solution of 1.93 mol of phosgene in toluene at 3 mA under water cooling. After finishing under Wl, stirring was continued at room temperature for 3 hours. The solution was poured into water, extracted with ethyl acetate, and then dried over anhydrous magnesium sulfate. After distilling off the solvent under reduced pressure, silica gel column chromatography (hexane:
Purification with ethyl acetate = 6:1) yields the target compound. −
8 g (yield 50%) was obtained.

Reference Example 9 N-(3-chloropropyl)-3,4-difluoro-α
, Preparation of α-dimethylbenzylamine A mixture of 5.2 g (30,0 mmol) of 3,4-difluoro-α,α-dimethylbenzylamine, 4.8 g (30,0 mmol) of 1-bromo-3-chloropropane The target compound 7. was reacted for 3 days with stirring at 50°C.
2 g (yield 97%) was obtained.

Reference Example 1O Production of N-(3-chloropropyl)-N-(3,4-difluoro-α1α-dimethylbenzyl)-N”-phenylurea N-(3-chloropropyl)-3,4-difluoro-α
, α-dimethylbenzylamine 5.0 g (20.0 mmol) toluene [to phenyl isocyanate 2.4
g (20.0 mmol) was added at room temperature and stirring was continued for 4 hours. The solution was poured into water and extracted with ethyl acetate. After drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure to obtain 6.4 g (yield: 88%) of the target compound.

Example 5 Preparation of l-(3,4-difluoro-α,α-dimethylbenzyl)-3-phenyl-2-berhydropyrimidinone (compound 11) N-(3-chloropropyl)-N-(3 , 4-difluoro-α,α-dimethylbenzyl)-N'-phenylurea 0.5 g (8.0 mmol) was added to an ethanol solution of 3.7 g (10.0 mmol) and stirred. While heating under reflux for 10 minutes, the solvent was distilled off under reduced pressure, water was added and extracted with ethyl acetate.Furthermore, after drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure.Silica gel Purification was performed using column chromatography (hexane:ethyl acetate = 7:1) to obtain 1.8 g (55%) of the target compound.

Reference Example 11 N-(3-chloropropyl)-α,α-dimethyl-3-
Production of trifluoromethylbenzylamine 6.1 g (30.0 mmol) of α,α-dimethyl-3-trifluoromethylbenzylamine and 4-7 g of l-bromo-3-chloropropane (
The reaction solution was stirred at 50° C. for about 30 hours, then extracted with toluene, and thoroughly stirred with 5% sodium hydroxide solution. Furthermore, after washing with water, the toluene layer was dried with anhydrous magnesium sulfate. After distilling off the solvent, the residue was purified by silica gel column chromatography to obtain 1.8 g (yield 21%) of the target compound.

Reference Example 12 Production of N-(3-chloropropyl)-N-(α,α-dimethyl-3-trifluoromethylbenzyl)-N゛-phenylurea N-(3-chloropropyl)-α,α-dimethyl-3 −
1.8 g (6.4 mmol) of triple-omethylbenzylamine was dissolved in 30 mQ of acetone, 0.8 g (6.4 mmol) of phenyl isocyanate was added, and the mixture was stirred at room temperature overnight. Acetone was distilled off and the residual solid was
- Washed with hexane to obtain 2.6 g of the target compound (yield: 10
0%) was obtained.

Example 6 1-(α,α-dimethyl-3-trifluoromethylbenzyl)-3-phenyl-2-berhydropyrimidinone (
Preparation of compound 17) N-(3-chloropropyl)-N-
Dissolve 2.6 g (6.4 mmol) of (α,α-dimethyl-3-trifluoromethylbenzyl)-N-phenylurea in 30 mA of ethanol, and add 0.5 g (7.0 mmol) of 85% potassium hydroxide powder. ) in addition.

Stirred at 40-50°C for 1 hour. After distilling off the ethanol, add water, extract with ethyl acetate, and wash thoroughly with water.
It was dried over anhydrous magnesium sulfate.

The solvent was distilled off, and the resulting residue was recrystallized from ethanol to obtain 1.5 g (yield: 65%) of the target compound.

Reference Example 13 2-(3-chloro-α,α-dimethylbenzylamino)
-Preparation of acetanilide 5.0 g (29.5 mmol) of 2-chloroacetanilide was dissolved in 50 mA of dimethylacetamide, and 5.0 g of 3-chloro-α,α-dimethylbenzylamine was added to the solution.
(29.5 mmol) and 3.5 g of triethylamine
(35.0 mmol) was added and stirred at 80° C. for 14 hours. After completion of the reaction, the reaction solution was poured into ice water and extracted with ethyl acetate. After thoroughly washing with water, it was dried over anhydrous magnesium sulfate, and the Ts medium was distilled off. The obtained residue was purified by silica gel column chromatography to obtain the target compound 5.
3 g (yield 60%) was obtained.

Reference example 14 N-(3-chloro-α,α-dimethylbenzyl)-No
-Production of phenylethylenediamine 2-(3-chloro-α,α-dimethylbenzylamino)
3.5 g (11.6 mmol) of acetanilide was dissolved in 50 mQ of tetrahydrofuran, and 0.48 g (12 mmol) of lithium aluminum hydride was gradually added dropwise at room temperature. The reaction mixture was stirred at room temperature overnight, poured into ice water, added with 10% sodium hydroxide, and extracted with ether. After thoroughly washing with water, it was dried over anhydrous magnesium sulfate, and the solvent was distilled off. The obtained residue was purified by silica gel column chromatography.

1.8 g (yield 55%) of the target compound was obtained.

Example 7 l-(3-chloro-α,α-dimethylbenzyl)-3-
Preparation of phenyl-2-imidazolidinone (compound 4) N-(3-chloro-α,α-dimethylbenzyl)-N'
-1.8 g (6.2 mmol) of phenylethylenediamine was dissolved in 30 mQ of dichloromethane, and 1.3 g (13.0 mmol) of triethylamine was added thereto. Under water cooling, triphosgene 0.6 g (2.1 mmol)
was added dropwise and stirred day and night.

The reaction solution was extracted with dichloromethane, thoroughly washed with water, and dried.
The solvent was distilled off. The residue was purified by silica gel column chromatography to obtain 1.5 g of the target compound (yield 77%).
I got it.

The herbicide of the present invention contains a cyclic urea derivative represented by general formula (1) as an active ingredient.

When the compound of the present invention is used as a herbicide in rice fields, fields, orchards, non-agricultural lands, etc., the active ingredient can be used in a suitable dosage form depending on the purpose.

In normal cases, the active ingredient is diluted with an inert liquid or solid carrier, and if necessary, surfactants, dispersants, adjuvants, etc. are added to form powders, wettable powders, emulsions, granules, etc. It can be formulated and used in various forms. Examples of carriers used in formulation include solid carriers such as dicrite, talc, bentonite, clay, kaolin, diatomaceous earth, white carbon, vermiculite, slaked lime, silica sand, ammonium sulfate, and urea, isopropyl alcohol, xylene, cyclohexanone, and methyl. Examples include liquid carriers such as naphthalene. Examples of surfactants and dispersants include alcohol sulfate ester salts, alkylaryl sulfonates, lignin sulfonates, polyoxyethylene glycol ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene sorbitan monoalkylates, and the like. It will be done. Examples of the adjuvant include carboxymethyl cellulose, polyethylene glycol, gum arabic, and the like. When used, it can be diluted to an appropriate concentration and sprayed, or applied directly.

The amount of application varies depending on the occasion and timing of application, application method, cultivated crops, etc., but in general, 0.1 g to IKg of the active ingredient of the compound of the present invention is applied per 10 ares.

The compound of the present invention may also be used as an insecticide if necessary.

It may be used in combination with fungicides, other herbicides, plant growth regulators, fertilizers, etc.

Next, the formulation method will be specifically explained using typical formulation examples. In the following description, "1 part" means part by weight.

Formulation Example 1 Wettable powder compound (10) 10 parts, Emulgen 81O (registered trademark of Kao Corporation) 0.5 parts, Demol N (registered trademark of Kao Corporation) 0.5 parts, Kunilite 210 (Kunimine Industries Co., Ltd.) (registered trademark) 20 copies, Zeeklite CA (registered trademark)
A wettable powder was prepared by uniformly mixing and pulverizing 41:69 parts of a WD commercial product manufactured by Kreit Co., Ltd.

Formulation v42 Wettable powder Compound (11) 10 parts, Emuldan 8100.5 parts, Demol N 0.5 parts, Kunilite 20120 parts.

Carplex 80 (registered trademark of Shionogi & Co., Ltd.)
A wettable powder was prepared by uniformly mixing and pulverizing 64 parts of 5M and Zeekrite CA.

Formulation Example 3 Emulsion compound (12) 30 parts, xylene 30 parts, isophorone 3
0 parts and 10 parts of the surfactant Tsurupol 800A (registered trademark 411t of Toho Chemical Industry Co., Ltd.) were thoroughly stirred to prepare an emulsion.

Formulation example 4 Granule compound (13) 10 parts, talc 20 parts, bentonite 6
0 parts, white carbon 5 parts, surfactant Tsurupol 8
A paste was prepared by mixing 5 parts of 00A and 10 parts of water and extruding it through a sieve hole with a diameter of 0.7 mm. After drying, the paste was cut into a length of 1 part of 05 to form a single granule.

(Effects of the Invention) The compound of the present invention represented by the general formula [■] can be applied to annual weeds such as Japanese barnyard grass, Japanese cypress, Japanese cypress, Japanese cypress, azalea, and Japanese aphrodisiac, which occur in rice fields, and perennial weeds such as bulrush, Japanese cypress, Japanese cypress, and Japanese cypress. It exhibits excellent herbicidal effects at extremely low dosages over a wide range from the time of weed germination to the growing season, and at the same time is highly safe for paddy rice. In addition, various weeds, such as knotweed, Japanese knotweed, and whiteweed, can also cause problems in fields.
Soil treatment or foliage treatment is applied to perennial and annual Cyperaceae weeds such as m-grass, Cyperus japonica, Cyperus japonica, Cyperus japonica, Poaceae weeds such as Japanese barnyard grass, Japanese grasshopper, Japanese foxtail grass, Poaceae weeds, Johnson grass, and Japanese grasshopper. At the same time, it shows high herbicidal effect when treated with soybeans, cotton, sugar radish,
It is characterized by high safety against upland rice, wheat, etc.

Furthermore, since the compound of the present invention has excellent residual efficacy, it exhibits stable effects over a long period of time even in the field.

Also, orchards, meadows, and lawns.

It can also be used for non-agricultural land.

Next, the effects of the compounds of the present invention will be explained by giving test examples.

Test example 1 (herbicidal effect test by paddy soil treatment) 100
am'' plastic pots were filled with paddy soil, and after raking for the first generation, seeds of Japanese millet, Japanese cabbage, and firefly were sown.
The garden was flooded at a depth of 3C. the next day.

A wettable powder prepared according to Formulation Example 1 was diluted with water.

It was treated by dripping on the water surface. The application amount was 100 g of active ingredient per 10 ares. After that, it was grown in a greenhouse and processed 21
On day 0, the herbicidal effect was investigated according to the standards in Table 2. The results are shown in Table 3.

Table 3 Table 3 continued Test example 2 (#herbicidal effect test by soil treatment) 120C
-Plastic bottle 1- was filled with field soil, and seeds of Japanese barnyard grass, Japanese grasshopper, and Kogomegayari were sown and covered with soil.

A wettable powder prepared according to Formulation Example 1 was diluted with water, and 1 ooQ per 10 are was uniformly sprayed on the soil surface using a small sprayer III so that the active ingredient was 400 g per 10 are. Thereafter, the plants were grown in a greenhouse, and the herbicidal effect was investigated blindly on the 21st day of treatment according to the criteria in Table 2. The results are shown in Table 4.

Table 4 Table 4 continued Test example 3 (herbicidal effect test by field soil foliage treatment) 120
c++'' plastic pots were filled with field soil, and seeds of Japanese barnyard grass, Japanese grasshopper, and Japanese grasshopper were sown and grown in a greenhouse until the Japanese barnyard grass reached the 3-leaf stage. Prepared according to Formulation Example 1 at the 3-leaf stage of the Japanese barnyard grass. The wettable powder was diluted with water, and 10012 per IO were sprayed on the foliage from the top of the plant using a small sprayer so that the active ingredient was 400 g per 10 are.Then, the plant was grown in an i-room, The herbicidal effect was investigated on the 21st day of treatment according to the criteria in Table 2.

The results are shown in Table 5.

Table 5 Test Example 4 (Medical efficacy and phytotoxicity test by paddy soil treatment) 100
c1 Fill the plastic pot with paddy soil, add water,
After puddling, seeds of Japanese millet and bulrush were sown, and one individual of paddy rice at the 2.5-leaf stage was transplanted to a transplant depth of 2c11, and then flooded to a water depth of 3c+s. The next day, a predetermined amount of the active ingredient of a wettable powder prepared according to Formulation Example 1 was diluted with water and dropped onto the water surface. Thereafter, the plants were grown in a greenhouse and 30 days after treatment, the herbicidal effect and phytotoxicity were investigated according to the criteria in Table 2. The results are shown in Table 6.

Table 6 Table 6 continued Test example 5 (crop selectivity test in field soil treatment) 60
0 cm" plastic pots were each filled with upland soil and sown with soybeans, persimmons, Japanese barnyard grass, Japanese foxtail grass, foxtail grass, and johnson grass. After water was absorbed from the bottom of the pots,
The predetermined amount of active ingredient in the hydrating powder prepared according to Formulation Example 1 was 1
It was diluted with 100 a/are of water and sprayed onto the soil surface using a small sprayer. After the treatment, the plants were grown again in the greenhouse, and on day 21 of the treatment, the herbicidal effect and phytotoxicity were investigated according to the criteria in Table 2. The results are shown in Table 7.

Test Example 6 (Crop selectivity test in field soil treatment) 12
0 cm" plastic pots were each filled with soil and sown with rice, wheat, barnyard grass, crabgrass, foxtail grass, and sagebrush. After water was absorbed from the bottom of the pot,
According to II agent fs1! The specified amount of active ingredient of the wettable powder prepared by Li is diluted with 100 parts of water per 10 ares, and
It was sprayed on the soil surface using a II vessel. After the treatment, the plants were grown again in the greenhouse, and on day 21 of the treatment, the grass effect and phytotoxicity were investigated according to the criteria in Table 2. The results are shown in Table 8.

Claims (2)

[Claims] (1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [ I ] (In the formula, X represents a hydrogen atom, halogen atom, alkyl group, or alkoxy group, and Y represents a halogen atom, alkoxy group, alkyl group, or halogen represents a substituted alkyl group or phenoxy group, Z represents an oxygen atom or a sulfur atom, m
represents 0 or 1, and n represents 0 or an integer of 1 to 3. ) is a cyclic urea derivative represented by (2) General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼[I] (In the formula, represents a substituted alkyl group or phenoxy group, Z represents an oxygen atom or a sulfur atom, m
represents 0 or 1, and n represents 0 or an integer of 1 to 3. ) A herbicide containing a cyclic urea derivative represented by the following as an active ingredient.