JPH0931060A - Production of cyclic urea compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a cyclic urea compound having a structure in which a nitrogen atom constituting urea structure is substituted with an isolactic acid derivative and useful as a herbicide or its intermediate by using specific hydantoins as raw material compounds. SOLUTION: This urea compound of formula II [e.g. 2-(3-phenyl-tetrahydro-2- pyrimidon-1-yl)isolactic acid] is obtained from a hydantoin derivative of formula I [Q<2> is a (substituted) phenyl or a (substituted) thienyl; R<1> is a 1-4C alkyl; R<2> is H or a 1-4C alkyl; (n) is 1 or 2; W is a halogen, OH or OR<3> (R<3> is a 1-4C alkylsulfonyl, a 1-4C haloalkylsulfonyl, benzenesulfonyl, a (substituted) phenylsulfonyl or benzylsulfonyl)] [e.g. 1-(3-chloropropyl)-5,5-dimethyl-3- phenylhydantoin]. Furthermore, the reaction is preferably carried out in the presence of a base such as potassium hydroxide in a solvent such as ethanol at 0 deg.C to a reflux temperature for 10min to 24hr.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a cyclic urea compound useful as a herbicide or an intermediate thereof (Japanese Patent Application No. 7-24).
No. 788).

[0002]

2. Description of the Related Art A method for producing a cyclic urea compound is
JP-A-49-132073, JP-A-57-13906
No. 9, JP-A-58-140078 and JP-A-3-1.
No. 76475 and the like. However, it is not known that a cyclic urea compound in which a nitrogen atom forming a urea structure is substituted with an isobutyric acid derivative is produced from hydantoins.

[0003]

[Means for Solving the Problems]

 Formula (1a):

[0004]

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[In the formula, Q ² represents an optionally substituted phenyl group or an optionally substituted thienyl group,
R ¹ represents a C ₁ -C ₄ alkyl group, R ² represents a hydrogen atom or a C ₁ -C ₄ alkyl group, n represents 1 or 2, and W
Is a halogen atom, a hydroxyl group or OR ³ (R ³ is a C ₁ -C ₄ alkylsulfonyl group, a C ₁ haloalkylsulfonyl group,
It represents a benzenesulfonyl group, a phenylsulfonyl group or a benzylsulfonyl group substituted with 1 to 3 methyl groups. ) Represents. ] From the hydantoin derivative represented by the formula (1)

[0006]

[Chemical 6]

A method for producing a cyclic urea compound represented by (hereinafter referred to as the method of the present invention).

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The method of the present invention will be described in detail below. The scheme is as follows, and in scheme 1, Q
² , R ¹ , R ² , n and W have the same meanings as described above.

[0009]

[Chemical 7]

Scheme 1 is a hydantoin derivative (1a)
Represents a method for producing a cyclic urea compound (1) by reacting with a base in the presence of a base. The base is usually used in an amount of 0.2 to 10 mol, preferably 0.8 to 3 mol, based on (1a). A base may be used as a solvent. Pyridine, triethylamine, N, N-dimethylaniline, N, N-diethylaniline, 4- (N, N) as a base
-Dimethylamino) pyridine, nitrogen-containing organic bases such as 1,4-diazabicyclo [2,2,2] octane, sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, carbonic acid Inorganic bases such as sodium hydrogen, sodium methoxide,
Examples thereof include metal alcoholates such as sodium ethoxide, and preferably the above-mentioned inorganic bases and metal alcoholates.

The reaction usually requires a solvent, and as the solvent, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, halogenated hydrocarbons such as chloroform and methylene chloride, alcohols such as methanol, ethanol and propanol, Diethyl ether, dioxane,
Ethers such as tetrahydrofuran, ketones such as acetone and methyl ethyl ketone, nitriles such as acetonitrile and isobutyronitrile, tertiary amines such as pyridine and N, N-diethylaniline, N, N-dimethylacetamide, N, Examples thereof include acid amides such as N-dimethylformamide and N-methylpyrrolidone, sulfur-containing compounds such as dimethylsulfoxide and sulfolane, and mixtures thereof, preferably the above-mentioned aromatic hydrocarbons, alcohols, ethers and ketones. And acid amides and mixtures.

The reaction temperature is generally -10 to 180 ° C, preferably 0 ° C to the reflux temperature. The reaction time is usually 3 minutes to 36 hours, preferably 10 minutes to 24 hours. Preferred as the leaving group W of the starting material hydantoin derivative (1a) are fluorine atom, chlorine atom, bromine atom, iodine atom, hydroxyl group, methylsulfonyloxy group, ethylsulfonyloxy group, normal propylsulfonyloxy group, isopropylsulfonyl group. Oxy group, normal butyl sulfonyloxy group, isobutyl sulfonyloxy group,
Secondary butylsulfonyloxy group, tertiary butylsulfonyloxy group, trifluorosulfonyloxy group, benzenesulfonyloxy group, paratoluenesulfonyloxy group, orthotoluenesulfonyloxy group, paraxylenesulfonyloxy group, mesitylsulfonyloxy group and benzylsulfonyl group. The group is raised.

The hydantoin derivative (1a) can be produced, for example, according to the following scheme 2 or scheme 3.

[0014]

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(In Scheme 2, Q ² , R ¹ , R ² , R ³ and n
And W have the same meanings as described above, R is a hydrogen atom, C
₁ -C ₆ alkyl group, a phenyl group or a benzyl group, Hal represents a halogen atom. ) Scheme 2 is a hydantoin derivative (1a) by reacting an α-amino acid derivative (A) with an isocyanic acid ester (B), and further, when W represents a hydroxyl group, a sulfonyl halide or a sulfonic anhydride. By reacting (C), a hydantoin derivative (1
It represents a method for producing a-1).

[0016]

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(In the scheme 3, Q ² , R ¹ , R ² , n and W have the same meanings as described above, and Hal represents a halogen atom.) In the scheme 3, compound (D) has halogenated alkyls ( By reacting E) with the hydantoin derivative (1
3 represents a method for producing a).

[0018]

EXAMPLES The method of the present invention will be specifically described below as examples, but the method of the present invention is not limited thereto. Further, as reference examples, production examples of the starting materials hydantoin derivatives (1a) and (1a-1) and herbicides derived from the cyclic urea compound produced by the method of the present invention will be specifically described.

Example 1 Preparation of 2- (3-phenyl-tetrahydro-2-pyrimidone-1-yl) isobutyric acid (Compound No. 1)

[0020]

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5.1 g of 1- (3-chloropropyl) -5,5-dimethyl-3-phenylhydantoin was dissolved in 35 ml of ethanol, 1.0 g of potassium hydroxide powder was added, and the mixture was refluxed for 2 hours. Ethanol was distilled off under reduced pressure, water was added, the aqueous layer was washed with diethyl ether, and the aqueous layer was acidified with hydrochloric acid and extracted with ethyl acetate. The organic layer was washed with water and saturated brine, dried over anhydrous sodium sulfate, and ethyl acetate was evaporated under reduced pressure. The obtained crystals were washed with diisopropyl ether to give the target compound (1.9 g) as white crystals. Melting point 218-220 ° C

Example 2 Preparation of 2- [3- (2-fluorophenyl) -tetrahydro-2-pyrimidone-1-yl] isobutyric acid (Compound No. 2)

[0023]

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6.5 g of 1- (3-chloropropyl) -5,5-dimethyl-3- (2-fluorophenyl) hydantoin was dissolved in 35 ml of ethanol, 1.1 g of potassium hydroxide powder was added, and the mixture was refluxed for 2 hours. did. Ethanol was distilled off under reduced pressure, water was added, the aqueous layer was washed with diethyl ether, and the aqueous layer was acidified with hydrochloric acid and extracted with ethyl acetate. The organic layer was washed with water and saturated brine, dried over anhydrous sodium sulfate, and ethyl acetate was evaporated under reduced pressure. The crystals obtained were washed with diisopropyl ether to give 2.1 g of the target compound as white crystals. Melting point 2
09 ~ 211 ℃

Example 3 Production of 2- (4-methyl-3-phenyl-2-imidazolidinone-1-yl) isobutyric acid (Compound No. 3)

[0026]

[Chemical 12]

A mixture of 1.5 g of 5,5-dimethyl-1- (2-methanesulfonyloxypropyl) -3-phenylhydantoin and 60 ml of ethanol was heated to 50 ° C. and 0.5 g of powdered potassium hydroxide was added, Then, it heated and refluxed for 20 minutes. After concentrating under reduced pressure, ether was added to the reaction mixture and it was extracted with water. Concentrated hydrochloric acid was added to the aqueous layer to make it acidic, and it was extracted with ethyl acetate. The organic layer was washed with water and dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. Diisopropyl ether was added to the obtained crude product to crystallize and wash the desired compound 0.4.
8 g was obtained. Melting point 192-194 ° C

[Reference Example 1] Production of 5,5-dimethyl-3-phenyl-1- (2-hydroxypropyl) hydantoin

[0029]

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A solution of 6.9 g of ethyl 2- (2-hydroxypropylamino) isobutyrate in 50 ml of methylene chloride was added to 0.
It was cooled to 0 ° C., and 3.6 g of phenyl isocyanate was added dropwise thereto. After the dropping, the mixture was stirred at room temperature for 1 hour, and then the solvent was distilled off under reduced pressure. Ethanol was added to the obtained crude product.
ml and 10% aqueous sodium hydroxide solution 0.5 ml were added, and the mixture was stirred at room temperature for 20 minutes. The solvent is distilled off under reduced pressure,
Water was added thereto and extracted with chloroform. After the organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure. The obtained crude product was washed with diisopropyl ether to obtain 3.3 g of the desired product. 93-95 ° C

Reference Example 2 5,5-Dimethyl-3-phenyl-1- (2-methanesulfonyloxypropyl)
Hydantoin manufacturing

[0032]

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5,5-dimethyl-3-phenyl-1-
A solution of 0.5 g of (2-hydroxypropyl) hydantoin in 10 ml of methylene chloride was cooled to 0 ° C., 0.3 g of triethylamine was added, and then 0.23 g of methanesulfonyl chloride was added dropwise. After the dropping, the mixture was stirred at room temperature for 1 hour. Saturated sodium hydrogen carbonate aqueous solution was added to the reaction solution,
Extracted with chloroform. The organic layer was dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain 0.6 g of the desired product. Glassy

¹ HNMR [CDCl ₃ ]: 1.45 (3
H, d, J = 6 Hz), 1.50 (6H, s), 2.9
9 (3H, s), 3.47 (2H, d, J = 6Hz),
5.00 to 5.35 (1H, m), 7.46 (5H,
s)

Reference Example 3 5,5-Dimethyl-3-
Production of (2-fluorophenyl) -1- (3-chloropropyl) hydantoin

[0036]

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A solution of 17 g of ethyl 2- (3-chloropropylamino) isobutyrate in 50 ml of toluene was cooled to 0 ° C., and 9 g of 2-fluorophenyl isocyanate was added dropwise. After the dropping, the mixture was stirred overnight at room temperature. The solvent was distilled off under reduced pressure, and the obtained crude product was purified by column chromatography (ethyl acetate / n-hexane = 1/2) to obtain 22 g of the target product. Viscous oil ¹ H NMR [CDCl ₃ ]: 1.44 (6 H, s),
1.95 to 2.30 (2H, m), 3.29 to 3.66
(4H, m), 7.15 to 7.40 (4H, m)

Reference Example 4 Production of 5,5-dimethyl-3-phenyl-1- (2-chloroethyl) hydantoin

[0039]

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A solution of 0.5 g of 5,5-dimethyl-3-phenylhydantoin in 15 ml of dimethylformamide was added to 0.
Cool to 0 ° C, add 100 mg of sodium hydride, and add 0 ° C.
For 30 minutes. Then add 1-bromo-2-to the solution.
0.4 g of chloroethane was added dropwise, and after the addition, the mixture was stirred at room temperature for 30 minutes. Water was added to the reaction solution, and the mixture was extracted with ethyl acetate. After the organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure. The obtained crude product was purified by thin layer chromatography (ethyl acetate / n-hexane = 1/2),
0.13 g of the desired product was obtained. 114-115 ° C

Reference Example 5 Production of ethyl 2- [3- (2-fluorophenyl) -tetrahydro-2-pyrimidon-1-yl] isobutyrate (Compound No. B-147)

[0042]

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2- [3- (2-fluorophenyl) -tetrahydro-2-pyrimidon-1-yl] isobutyric acid.
To a suspension of 4 g of methylene chloride in 15 ml, 50 mg of N, N-dimethylaminopyridine and 0.4 g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride were added, and the mixture was stirred at room temperature for 10 minutes. Next, 0.5 ml of ethanol was added to the solution, and the mixture was stirred at room temperature for 1 hour. A 0.5% aqueous hydrochloric acid solution was added to the reaction solution, and the mixture was extracted with chloroform. The organic layer was dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained crude product was washed with diisopropyl ether to obtain 0.3 g of the desired product. Melting point 92-9
4 ℃

Reference Example 6 Production of N- (3,5-dichlorophenyl) 2- (4-methyl-3-phenylimidazolidin-2-on-1-yl) isobutyric acid amide (Compound No. 151)

[0045]

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A suspension of 0.5 g of 2- (4-methyl-3-phenylimidazolidin-2-one-1-yl) isobutyric acid in 8 ml of toluene was cooled to 0 ° C. and 3 ml of thionyl chloride was added.
Was added. After stirring at 0 ° C. for 20 minutes and at room temperature for 40 minutes, the solvent was distilled off under reduced pressure to obtain 2- (4-methyl-3-phenylimidazolidin-2-on-1-yl) isobutyric acid chloride. .

Next, 0.35 of 3,5-dichloroaniline
A solution of 10 g of methylene chloride in 10 ml was cooled to 0 ° C., 0.8 g of triethylamine was added, and the obtained 2-
(4-Methyl-3-phenylimidazolidin-2-on-1-yl) isobutyric acid chloride methylene chloride 5 ml
The solution was added dropwise. After dropping, the mixture was stirred at room temperature for 2 hours, saturated aqueous sodium hydrogen carbonate solution was added to the reaction solution, and the mixture was extracted with chloroform. The organic layer is dried over anhydrous sodium sulfate,
The solvent was distilled off under reduced pressure. The obtained crude product was subjected to thin layer chromatography (ethyl acetate / n-hexane = 1/2).
The desired crystals (0.31 g) were obtained by washing the resulting crystals with diisopropyl ether. Melting point 170-
173 ° C

As shown in the above schemes or Examples, Table 1 shows the structural formulas and physical properties of the cyclic urea compounds produced by the method of the present invention, including the compounds produced in the above Examples. Further, the structural formula of the herbicide produced according to Reference Example 5 or Reference Example 6 is shown in Table 2, and the physical properties thereof are shown in Table 3. However, in Table 1 and Table 2, Me is a methyl group,
Et is an ethyl group, Pr is a normal propyl group, i-Pr
Represents an isopropyl group and Ph represents a phenyl group.

[Table 1]

[0050]

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[0051]

[Table 1] ──────────────────────────────────── Compound No. R ² n Q ² Melting point (° C.) ──────────────────────────────────── 1 H 2 Ph 218 -220 2 H 2 2-F-Ph 209-211 3 Me 1 Ph 192-194 4 H 2 2-Cl-Ph 231-233 5 H 2 2-CF ₃ -Ph 213-214 6 Me 2 Ph 199-201 7 Me 2 2-F-Ph 205-207 8 H 1 Ph 215-216 9 H 2 2,6-F ₂ -Ph 255-257 10 Me 1 2-F-Ph 198-200 ──────── ─────────────────────────────

[Table 2]

[0053]

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[0054]

[Table 2] Compound No. Q ¹ X R ² n Q ² ───────────────────────────────────── B-118 4-CF ₃ -5-Cl-Q-24 NH H 2 2-F-Ph B-119 4-CF ₃ -5-Br-Q-24 NH H 2 2-F-Ph B-120 4-CF ₃ -Q- 24 NH H 2 2-F-Ph B-121 3-Cl-5-OMe-Ph NH H 2 Ph B-122 3-Cl-5-F-Ph NH H 2 Ph B-123 3-F-4- CF ₃ -Ph NH H 2 Ph B-124 2-Me-5-Cl-Ph NH H 2 Ph B-125 2-F-5-CN-Ph NH H 2 Ph B-126 2-F-5-CN -Ph NH H 2 2-F-Ph B-127 3-OEt-Ph NH H 2 Ph B-128 3,5-F ₂ -Ph NH Me 1 Ph B-129 3-Cl-Ph NH Me 1 Ph B -130 4-Me-Q-39 NH H 2 Ph B-131 CH (i-Pr) CO ₂ Me NH H 2 Ph B-132 3-Cl-Ph NMe H 2 Ph B-133 Q-59 NH H 2 2-F-Ph B-134 CH ₂ (2-Cl-Ph) NH H 2 Ph B-135 CH ₂ (3-Cl-Ph) NH H 2 Ph B-136 CH ₂ (4-Cl-Ph) NH H 2 Ph B-137 Et OH 2 Ph B-138 3,5-F ₂ -Ph NH Me 1 2-F-Ph B-139 3-Cl-Ph NH Me 1 2-F-Ph B-140 5- Cl-Q-24 NH Me 1 2-F-Ph ─────────────────────────────────────

[0055]

[Table 3] [Continued Table 2] ──────────────────────────────────── Compound No. Q ¹ X R ² n Q ² ──────────────────────────────────── B-141 5-Cl -Q-24 NH Me 1 Ph B-142 3-Cl-Q-34 NH H 2 2-F-Ph B-143 3-Cl-Q-34 NH Me 1 Ph B-144 3-Cl-Q-34 NH Me 1 2-F-Ph B-145 2,5-F ₂ -Ph NH Me 1 Ph B-146 2,5-F ₂ -Ph NH Me 1 2-F-Ph B-147 Et OH 2 2- F-Ph B-148 Pr OH 2 2-F-Ph B-149 CH ₂ CF ₃ OH 2 2-F-Ph B-150 CH ₂ Ph OH 2 Ph B-151 3,5-Cl ₂ -Ph NH Me 1 Ph B-152 3,5-Cl ₂ -Ph NH Me 1 2-F-Ph B-153 4-CF ₃ -Q-17 NH H 2 Ph B-154 CH ₂ (4-Cl-Ph) OH 2 Ph B-155 CH ₂ (2-Cl-Ph) OH 2 Ph B-156 CH ₂ Q-2 NH H 2 Ph B-157 4-OMe-6-CF ₃ -Q-44 NH H 2 Ph B-158 CH ₂ (3-Cl-Ph) OH 2 Ph ─────────────────────────────────────

[0056]

[Table 4] [Table 3] ─────────────────────────────────── Compound No. Melting point (° C.) Compound No. Melting point (° C) ──────────────────────────────────── B-118 210-212 B-139 169- 170 B-119 206-209 B-140 163-165 B-120 173-174 B-141 155-156 B-121 Glassy B-142 257-260 (decomposition) B-122 162-165 B-143 210-210 215 (decomposition) B-123 220-221 B-144 231-235 (decomposition) B-124 178-180 B-145 160-162 B-125 172-174 B-146 91-92 B-126 194-196 B -147 92-94 B-127 113-115 B-148 Viscous liquid B-128 168-170 B-149 Viscous liquid B-129 88-91 B-15 0 95-96 B-130 144-145 B-151 170-173 B-131 Glassy B-152 199-200 B-132 95-100 B-153 194-195.5 B-133 180-184 B-154 131-134 B-134 194-196 B-155 Viscous liquid B-135 168-170 B-156 134-135 B-136 172-175 B-157 Viscous liquid B-137 101-102 B-158 555- 59 B-138 151-153 ────────────────────────────────────

However, in Table 2, Q-2, Q-17, Q-2
4, Q-34, Q-39, Q-44 and Q-59 represent the following.

[0058]

[Chemical 21]

In applying the compounds shown in Table 2 as herbicides, generally, a suitable carrier, for example, solid carrier such as clay, talc, bentonite, diatomaceous earth, white carbon or water, alcohols (isopropanol, butanol, Benzyl alcohol, furfuryl alcohol, etc.), aromatic hydrocarbons (toluene, xylene, etc.), ethers (anisoles), ketones (cyclohexanone, isophorone), esters (butyl acetate, etc.), acid amides (N -Methylpyrrolidone etc.) or halogenated hydrocarbons (chlorobenzene etc.) and the like can be mixed and applied, and if desired, surfactants, emulsifiers, dispersants, penetrants, spreading agents, thickeners Agents, antifreeze agents, anti-caking agents, stabilizers, etc.
It can be put to practical use in any dosage form such as wettable powders, dry flowables, flowables, powders, granules and the like.

If desired, they may be used in combination with other types of herbicides, various insecticides, bactericides, plant growth regulators, synergists and the like during formulation or spraying. The application amount of the herbicides shown in Table 2 varies depending on the application scene, application time, application method, cultivated crop, etc., but generally the amount of active ingredient is about 0.0001 to 10 kg per hectare (ha), preferably About 0.001 to 5 kg is suitable.

Next, specific formulation examples of the preparations using these herbicides will be shown. However, the compounding examples are not limited to these. In the following formulation examples, "part" means part by weight.

[Wettable powder] Compound in Table 2 5 to 80 parts Solid carrier 10 to 85 parts Surfactant 1 to 10 parts Others 1 to 5 parts Other examples include anticaking agents. [Emulsion] Compound in Table 2 1 to 30 parts Liquid carrier 30 to 95 parts Surfactant 5 to 15 parts

[Flowable Agent] Compound in Table 2 5-70 parts Liquid carrier 15-65 parts Surfactant 5-12 parts Others 5-30 parts Others include, for example, antifreezing agents, thickeners and the like. [Granular wettable powder (dry flowable agent)] Compound in Table 2 20 to 90 parts Solid carrier 9 to 60 parts Surfactant 1 to 20 parts [Granular] Compound in table 2 0.01 to 10 parts Solid carrier 90-99.9 parts Others 0-5 parts

[Formulation Example 1] Wettable powder Compound No. B-129 50 parts Di-Klyte PFP 43 parts (Kaolin-based clay: Di-Kryte Industry Co., Ltd. trade name) Sorpol 5050 2 parts (Anionic surfactant: Toho Chemical Industry Co., Ltd. trade name) Lunox 1000C 3 parts (Anionic surfactant: Toho Chemical Industry Co., Ltd. trade name) Carplex # 80 (anti-caking agent) 2 parts (White carbon: Shionogi Seiyaku Co., Ltd. trade name) Use as a Japanese medicine.

[Formulation Example 2] Emulsion Compound No. B-120 3 parts Xylene 76 parts Isophorone 15 parts Sorpol 3005X 6 parts (mixture of nonionic surfactant and anionic surfactant: trade name of Toho Chemical Industry Co., Ltd.) To do.

[Formulation Example 3] Flowable agent Compound No. B-138 35 parts Agrisol S-711 8 parts (Nonionic surfactant: Kao Corporation trade name) Lunox 1000C 0.5 parts (Anionic surfactant: Toho Chemical Industry Co., Ltd. trade name) 1% Rhodopol water 20 parts (Thickener: Trade name of Lorne Poulin Co., Ltd.) Ethylene glycol (antifreezing agent) 8 parts Water 28.5 parts The above ingredients are uniformly mixed to obtain a flowable agent.

[Formulation Example 4] Granular wettable powder (dry flowable agent) Compound No. B-152 75 parts Isoban No. 1 10 parts (anionic surfactant: Kuraray Isoprene Chemical Co., Ltd. trade name) Vanilex N 5 parts (anionic surfactant: Sanyo Kokusaku Pulp Co., Ltd. trade name) Carplex # 80 10 parts (white carbon: Shiono Gyosei Co., Ltd. trade name) The above is uniformly mixed and pulverized to obtain a dry flowable agent.

[Formulation Example 5] Granules Compound No. B-196 0.1 part Bentonite 55.0 parts Talc 44.9 parts After uniformly mixing and pulverizing the above, a small amount of water was added and the mixture was kneaded with stirring, granulated with an extrusion granulator, and dried. To make granules.

In use, the above-mentioned wettable powder, emulsion, flowable agent and granular wettable powder are diluted 50 to 1000 times with water to contain 1 to 10,000 ppm of active ingredient or 1 hectare (ha) of active ingredient. Per 0.0001-10
Disperse so that it becomes kg. Next, the usefulness of the compounds in Table 2 as herbicides will be specifically described in the following reference test examples. [Reference Test Example 1] Herbicidal effect test by soil treatment Put sterilized diluvial soil in a plastic box having a length of 21 cm, a width of 13 cm, and a depth of 7 cm.
Soybean seeds, cotton seeds, and corn seeds were sown in spots, covered with soil for about 1.5 cm, and then sprayed uniformly on the soil surface with a small spray so that the amount of the active ingredient was a predetermined ratio. As a chemical solution for spraying, a wettable powder appropriately prepared according to the above-mentioned formulation example etc. was diluted with water and used, and this was sprayed on the entire surface. Three weeks after spraying the chemical solution, the herbicidal effect on the plants was investigated according to the following criteria. The degree of suppression was determined by visual observation. The results are shown in Table 4.

Criteria 5: Complete death or 90% or more inhibition 4: 70-90% inhibition 3: 40-70% inhibition 2: 20-40% inhibition 1: 5-20% inhibition 0: 5 Suppression of% or less The symbols in Table 4 have the following meanings.

A (Novier), B (Enocologsa), a
(Soybean), b (cotton), c (corn)

[0072]

[Table 5] [Table 4] ──────────────────────────────────── Compound No. Amount kg / ha A B a b c ──────────────────────────────────── B-118 0 .63 5 5 0 0 3 B-119 0.63 5 5 0 0 B-120 0.63 5 5 3 0 5 B-121 0.63 5 5 0 0 2 B-122 0.63 5 5 2 0 5 B-124 0.63 5 5 0 0 1 B-125 0.63 5 5 2 0 2 B-126 0.63 5 5 0 0 4 B-128 0.63 5 5 3 0 5 B-129 0. 63 5 5 0 0 4 B-138 0.63 5 5 2 0 5 B-139 0.63 5 5 0 0 3 B-141 0.63 5 5 0 0 2 B-142 0.63 5 5 5 0 0 2 B-145 0.63 5 5 0 0 3 B-146 0.63 5 5 0 0 4 B-150 0.63 5 5 0 0 0 B-152 0.6 3 5 5 0 0 ─────────────────────────────────────

[Reference Test Example 2] Herbicidal effect test by foliar treatment: A sterilized diluvial soil was placed in a plastic box having a length of 21 cm, a width of 13 cm, and a depth of 7 cm.
Seeds of velvetleaf, Onami fir, Aoyu, and morning glory were sown in spots, and the soil was covered by about 1.5 cm. When each plant reached the 2-3 leaf stage, it was sprayed uniformly with a small spray to the foliage so that the amount of the active ingredient became a predetermined ratio. As a chemical solution for spraying, a wettable powder appropriately prepared according to the above-mentioned formulation example etc. was diluted with water and used, and this was sprayed on the entire surface. Reference Test Example 1 for the herbicidal effect on plants 3 weeks after spraying the chemical solution
The investigation was carried out according to the criteria. The results are shown in Table 5.

The symbols in Table 5 have the following meanings. A (Novier), B (Enokurokakuza), C (Ichibi), D
(Onamomi), E (Aobiyu), F (Morning glory)

[0075]

[Table 6] [Table 5] ──────────────────────────────────── Compound No. Amount kg / ha A B C D E F ──────────────────────────────────── B-118 2.5 5 5 2 5 2 0 B-120 2.5 5 5 5 4 4 2 0 B-121 2.5 5 5 2 4 2 0 B-122 2.5 5 5 5 4 4 2 0 B-125 2. 5 5 5 4 5 0 0 B-126 2.5 5 5 5 3 0 0 0 B-127 2.5 5 5 5 3 4 2 0 B-128 2.5 5 5 5 5 5 4 0 B-129 2.5 5 5 4 5 20 B-132 2.5 5 5 4 5 2 2 B-138 2.5 5 5 5 4 4 2 0 B-139 2.5 5 5 4 4 3 0 B-140 2.5 5 5 5 4 40 0 B-145 2.5 5 5 5 3 4 5 0 B-151 2.5 5 5 5 0 4 2 0 B-152 2.5 5 5 5 4 0 2 0 ──────────── ─────── ──────────────────

[Reference Test Example 3] Herbicidal effect test under waterlogging condition After alluvial soil was put in a Wagner pot of 1 / 10,000 are, water was added and mixed to make a waterlogging condition with a water depth of 4 cm. After seeds of Nobie and Firefly were sown in the above pot, rice seedlings at the 2.5 leaf stage were transplanted. One day after seeding, the drug diluent was dropped onto the water surface with a measuring pipette so that a predetermined amount of the drug was obtained. The pots were placed in a greenhouse at 25 to 30 ° C. to grow the plants, and the herbicidal effect on the plants was investigated 3 weeks after dropping the drug according to the criteria of Reference Test Example 1. The results are shown in Table 6.

The symbols in Table 6 have the following meanings. A (Novier), G (Firefly), d (Transplanted rice)

[0078]

[Table 7] [Table 6] ──────────────────────────────────── Compound No. Dosage kg / ha AG d ──────────────────────────────────── B-118 0.25 5 5 1 B-119 0.25 5 5 0 B-120 0.25 5 5 0 B-121 0.25 5 5 0 B-122 0.25 5 5 2 B-123 0.25 5 5 0 B- 124 0.25 5 5 0 B-125 0.25 5 5 5 3 B-126 0.25 5 5 0 B-127 0.25 5 5 5 0 B-128 0.25 5 5 0 B-129 0.25 5 5 0 B-130 0.25 5 5 0 B-132 0.25 5 5 0 B-133 0.25 5 5 0 B-134 0.25 5 5 0 B-135 0.25 5 5 0 B-136 0.25 5 5 0 B-138 0.25 5 5 0 B-139 0.25 5 5 0 B-140 0.25 5 5 0 B 141 0.25 5 5 0 ────────────────────────────────────

[0079]

[Table 8] [Continued Table 6] ──────────────────────────────────── Compound No. Dosage kg / ha AG d ──────────────────────────────────── B-142 0.25 5 5 0 B-143 0.25 5 5 0 B-144 0.25 5 5 0 B-145 0.25 5 5 0 B-146 0.25 5 5 0 B-151 0.25 5 5 5 0 B- 152 0.25 5 5 0 ─────────────────────────────────────

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location A01N 43/54 A01N 43/54 C C07D 401/04 C07D 401/04 403/04 403/04 405 / 04 405/04 413/04 413/04 417/04 417/04 (72) Inventor Kanji Sawada 1 722 Tsuboi-cho, Funabashi City, Chiba Prefecture, Central Research Laboratory, Nissan Chemical Industries, Ltd. (72) Inventor, Kajo Tamada, Chiba 1 722, Tsuboi-cho, Funabashi, Fukushima Pref., Central Research Laboratory, Nissan Chemical Industry Co., Ltd. (72) Tsutomu Namaki, 1470, Shiraoka, Shirooka-cho, Minamisaitama-gun, Saitama Nissan Chemical Industry Co., Ltd.

Claims (5)

[Claims] 1. Formula (1a): [In the formula, Q ² represents an optionally substituted phenyl group or an optionally substituted thienyl group, and R ¹ is C ₁ -C
₄ alkyl group, R ² represents a hydrogen atom or a C _{1 to} C ₄ alkyl group, n represents 1 or 2, W is a halogen atom, a hydroxyl group or OR ³ (R ³ is a C _{1 to} C ₄ alkylsulfonyl group. Group, a C ₁ haloalkylsulfonyl group, a benzenesulfonyl group, a phenylsulfonyl group substituted with a methyl group of 1 to 3 or a benzylsulfonyl group). ] From the hydantoin derivative represented by the formula (1) A method for producing a cyclic urea compound represented by: 2. Q ² is Wherein, Z is a halogen atom, C ₁ -C ₄ alkyl group, C ₁
To C ₄ alkoxy group, C _{1 to} C ₄ haloalkyl group or C ₁
To C ₄ haloalkoxy group, e represents an integer of 0 to 3, and when e represents 2 or 3, Z may be the same or different. ] The method according to claim 1, which represents 3. R ¹ represents a methyl group, R ² represents a hydrogen atom,
Represents a methyl group or an ethyl group, and Q ² is The method of claim 2, wherein 4. The method according to claim 3, wherein n represents 1. 5. The method according to claim 3, wherein n represents 2.