JPS6135990B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel substance, and more specifically, the present invention relates to a novel compound represented by the following formula. That is, the expression (In the formula, X is hydrogen or halogen; R ¹ is C ₁ - C ₃ alkyl or C ₁ - C ₃ haloalkyl; Q is hydroxyl group, or

A compound represented by the formula: (wherein R ² is hydrogen, a C ₁ -C ₃ alkyl group or a C ₂ -C ₅ alkoxyalkyl group). The compounds of the present invention are useful as herbicides and can be formulated using suitable carriers in a conventional manner. Q is

The compound of the present invention having the formula (wherein, X and R ¹ have the same meanings as above), a compound represented by the formula (In the formula, R ² has the same meaning as above.) It can be produced by reacting with an amine represented by the following formula. This reaction involves mixing a compound of formula () with an approximately equimolar amount or an excess molar amount of an amine of formula () in an inert reaction medium such as heptane or toluene, and then bringing the reaction mixture under stirring to its reflux. This can be carried out by heating to a certain temperature and azeotropically removing the water of reaction. Thereafter, the reaction mixture can be cooled and the desired product can be recovered by filtration if it forms as a precipitate or by evaporating it if it is dissolved in the organic reaction medium. The product can then be purified by conventional methods such as recrystallization and the like. The compounds of the present invention can also be prepared by converting a compound of formula () in the presence of a catalytic amount of p-toluenesulfonic acid. (In the formula, R ² has the same meaning as above.) It can also be produced by reacting with an acid anhydride represented by the following formula. The reaction is carried out by mixing the reactants and catalyst at room temperature in an inert organic reaction medium and then heating the reaction mixture in a steam bath with stirring for 1/2 to 4 hours. Thereafter, the reaction mixture can be cooled and the desired product can be recovered by filtration if it forms as a precipitate or by evaporating it if it is dissolved in the organic reaction medium. In some cases, acid anhydrides can be used as solvents for compounds of formula (), avoiding the use of inert solvents as reaction media. When a lower alkanoic anhydride is used, after the reaction is complete, water can be added to the reaction mixture to precipitate the desired product. The product can then be purified by conventional methods such as recrystallization. In some cases, the above reaction may be carried out with the desired compound of the invention and the formula A mixture of products consisting of the dehydrated starting materials of the formula (wherein X and R ¹ have the same meanings as above) may be obtained. In such cases, the desired product can be isolated by fractional precipitation. The compound represented by the formula () is the formula (wherein X and R ¹ have the same meanings as above) can be easily produced by heating the compound represented by the formula in a dilute acidic reaction medium for about 10 to 60 minutes. Temperatures from about 60° C. to the reflux temperature of the reaction mixture can be used. The reaction medium can contain a dilute aqueous solution of an inorganic acid, such as hydrochloric acid, at a concentration of about 0.5-10%.
Additionally, a water-soluble lower alkanol can preferably be added to the reaction medium to aid in dissolving the starting materials. After the reaction is complete, the desired product can be recovered by evaporation if it is dissolved in the solvent used or by filtration if it forms as a precipitate. This product can then be used as is or further purified by standard methods such as grinding, recrystallization, washing, etc. The compound represented by the formula () is the formula (In the formula, X has the same meaning as above.) 1 molar amount of the isocyanate dimer represented by the formula (In the formula, R ¹ has the same meaning as above.) It can be produced by reacting with about 2 molar amount of dimethyl acetal represented by the following formula. This reaction is carried out using the formula () dissolved in an inert organic solvent such as benzene.
isocyanate of formula () at room temperature and stirring the reaction mixture for about 1/2 to 4 hours. The reaction mixture is then filtered and the solvent is distilled off to yield the desired product. This product can be used as is or can be further purified by standard methods if desired. The formula () isocyanate dimer is the formula It can be produced by reacting benzothiazole represented by the formula (wherein, X has the same meaning as above) with phosgene. This reaction can be accomplished by adding a slurry or solution of benzothiazole dispersed or dissolved in a suitable organic solvent such as ethyl acetate to a solution of phosgene in a similar solvent. Then the reaction mixture is 1/2 to 2
Can be heated under reflux for hours. The desired product can then be recovered by filtration if it forms as a precipitate or by evaporation of the solvent if it is dissolved in an organic solvent. Formula () suitable for preparing compounds of the invention
Examples of the compounds are dimethyl acetal of 2-methylaminoacetaldehyde, dimethyl acetal of 2-ethylaminoacetaldehyde, dimethyl acetal of 2-propylaminoacetaldehyde, dimethyl acetal of 2-allylaminoacetaldehyde, and dimethyl acetal of 2-chloromethylaminoacetal. , dimethyl acetal of 2-β-bromoethylaminoacetaldehyde,
Dimethyl acetal of 2-propargylaminoacetaldehyde, etc. Formula () suitable for preparing compounds of the invention
Examples of compounds include 2-aminobenzothiazole, 2
-Amino-5-methylbenzothiazole, 2-amino-6-chlorobenzothiazole, 2-amino-4,5-dimethylbenzothiazole, 2-amino-7-bromobenzothiazole, 2-amino-
6-methoxybenzothiazole, 2-amino-6
-Fluorobenzothiazole, 2-amino-4-
Methyl-6-chlorobenzothiazole, 2-amino-4-chloromethylbenzothiazole, 2-amino-5-β-bromoethylbenzothiazole,
2-amino-6-trifluoromethylbenzothiazole and the like. Formula () suitable for preparing compounds of the invention
Examples of compounds of and () are acid chlorides or acid anhydrides of the following acids. Acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, octanoic acid,
Dodecanoic acid, octadecanoic acid, acrylic acid, butenoic acid, pentenoic acid, chloroacetic acid, bromoacetic acid, β
-Chlorbutanoic acid, chlorhexylcarboxylic acid,
Cyclopropylcarboxylic acid, benzoic acid, toluic acid, 4-chlorobenzoic acid, 3-bromobenzoic acid,
4-fluorobenzoic acid, 4-methoxybenzoic acid,
4-Ethoxybenzoic acid, 4-chloromethylbenzoic acid, 4-trifluoromethylbenzoic acid, 3.4.
5-Trichlorobenzoic acid, 3-methylthiobenzoic acid, 3-ethylthiobenzoic acid, 4-butylthiobenzoic acid, phenyl acetic acid, β-phenylpropionic acid, 4-methylphenylacetic acid, propic acid, butic acid, methoxyacetic acid, β- Methoxypropionic acid, γ-ethoxybutanoic acid, etc. The method for producing the compounds of the present invention will be explained in more detail with reference to the following examples. Example 1 Preparation of benzothiazol-2-yl isocyanate dimer A saturated solution of phosgene in ethyl acetate (1200 ml) was charged to a glass reactor equipped with a mechanical stirrer, a thermometer and a reflux condenser. Then 2-aminobenzothiazole (100.0 g; 067 mole) was added under stirring. After the addition was complete, the reaction mixture was heated to reflux for about 1 hour. Thereafter, the reaction mixture was evaporated to dryness to obtain the desired product, benzothiazol-2-yl isocyanate dimer, as a yellow solid with a melting point of 250-252°C. Example 2 2-(1-methyl-3-benzothiazole-2
-Production of dimethyl acetal of ylureido)acetaldohyde Benzothiazole produced in Example 1-
2-yl isocyanate dimer, benzene,
(300 ml) and the dimethyl acetal of 2-methylaminoacetaldehyde (80 g; 0.67 mole) were charged to a glass reaction vessel equipped with a mechanical stirrer and a thermometer. The reaction mixture was stirred at room temperature for about 1 hour. Thereafter, the mixture was filtered to remove the produced yellow solid. Next, the desired product 2 is obtained by removing the solvent from the liquid under reduced pressure.
-(1-Methyl-3-(benzothiazol-2-ylureto)acetaldehyde dimethyl acetal was obtained as an oil. Example 3 1-benzothiazol-2-yl-3-methyl-
5-hydroxy-1,3-imidazolidine-2
Production of -one 2-(1-methyl-3-benzothiazol-2-
dimethyl acetal of acetaldehyde (150g), methanol (750ml), water (750ml)
ml) and concentrated hydrochloric acid (75 ml) were charged into a glass reactor equipped with a mechanical stirrer, a thermometer and a reflux condenser. Surround the reaction mixture with a nitrogen gas atmosphere for approximately 15 min.
Heat to reflux for minutes. Thereafter, most of the solvent was distilled off from the mixture, and the residue was mixed with aqueous sodium hydrogen carbonate solution (500 ml). The mixture was then extracted with methyl acetate, and the resulting solution was dried over anhydrous magnesium sulfate. The desired product, 1, is then obtained by distilling off the solvent from this dry solution.
-benzothiazol-2-yl-3-methyl-5-
Hydroxy-1,3-imidazolidin-2-one was obtained as a yellow solid with a melting point of 168-170°C. Example 4 1-benzothiazol-2-yl-3-methyl-
5-ethylamino-1,3-imidazolidine-
Preparation of 2-one 1-benzothiazol-2-yl-3-methyl-
5-hydroxy-1,3-imidazolidine-2-
(0.1 mole) and heptane (100 ml) using a mechanical stirrer, thermometer, Dean Stark
-Stark) into a glass reaction vessel equipped with a collector and a reflux condenser. Ethylamine (0.1 mole) was added to the reaction vessel and the mixture was heated to reflux. The water produced during that time was removed. After the evolution of water has stopped, the desired product, 1-benzothiazol-2-yl-3-methyl-5-ethylamino-1,3-imidazolidine-, is obtained by removing the solvent from the reaction mixture under reduced pressure. 2-one was obtained as a residue. (Melting point 157-158°C) Example 5 1-benzothiazol-2-yl-3-methyl-
Production of 5-acetyloxy-1,3-imidazolidin-2-one 1-benzothiazol-2-yl-3-methyl-
5-hydroxy-1,3-imidazolidine-2-
(0.1 mole), acetyl chloride (0.11 mole), and pyridine (0.11 mole) were charged to a glass reaction vessel equipped with a mechanical stirrer and a thermometer. The reaction mixture was stirred for about 15 minutes and then left for about 2 hours. Then water (100ml) and hexane (30ml)
was added to the mixture. The organic phase was then separated from the aqueous phase and dried over anhydrous magnesium sulfate. The desired product, 1-benzothiazole-, was then obtained by filtering the dry solution and removing the solvent under reduced pressure.
2-yl-3-methyl-5-acetyloxy-
1,3-imidazolidin-2-one was obtained as a residue. Example 6 Preparation of 5-methylbenzothiazol-2-yl isocyanate dimer A saturated solution of phosgene in ethyl acetate (200 ml) was
A glass reaction vessel equipped with a mechanical stirrer, thermometer and reflux condenser was charged. 2-amino-5-methylbenzothiazole (0.1 mole) was added under stirring. After the addition was complete, the reaction mixture was heated to reflux for about 1 hour. Thereafter, the mixture was cooled and the solid product formed was collected. Next, the desired product, 5-methylbenzothiazol-2-yl isocyanate dimer, was obtained by drying this solid. Example 7 Preparation of dimethyl acetal of 2-[1-methyl-3-(5-methylbenzothiazol-2-yl)ureido]acetaldehyde 5-methylbenzothiazol-2-yl isocyanate dimer (0.1 mole ), dimethyl acetal of 2-methylaminoacetaldehyde (0.2 mole) and benzene (100 ml) were charged to a glass reaction vessel equipped with a mechanical stirrer and a thermometer. The reaction mixture was stirred at ambient temperature for about 1 hour. Thereafter, the reaction mixture is filtered and the solvent is distilled off to obtain the desired product, 2-
[1-Methyl-3-(5-methylbenzothiazole-
Dimethyl acetal of 2-yl)ureido]acetaldehyde was obtained as a residue. (Melting point 214-215
℃) Example 8 1-(5-methylbenzothiazol-2-yl)-
Production of 3-methyl-5-hydroxy-1,3-imidazolidin-2-one Dimethyl acetal of 2-[1-methyl-3-(5-methylbenzothiazol-2-yl-)ureido]acetaldehyde (15 g ), water (200 ml), methanol (200 ml) and concentrated hydrochloric acid (10 ml) were charged into a glass reaction vessel equipped with a mechanical stirrer, thermometer and reflux condenser. The reaction mixture was heated to reflux for approximately 15 minutes. Thereafter, the solvent was distilled off from the reaction mixture under reduced pressure to obtain a residue. By recrystallizing this residue, the desired product 1-(5-
Methylbenzothiazol-2-yl)-3-methyl-5-hydroxy-1,3-imidazolidine-2
- Got on. Example 9 1-(5-methylbenzothiazol-2-yl)-
3-Methyl-5- t -butylamino-1,3-
Production of imidazolidin-2-one 1-(5-methylbenzothiazol-2-yl)-
3-Methyl-5-hydroxy-1,3-imidazolidin-2-one (0.1 mole) and heptane (100
ml) was charged to a glass reaction vessel equipped with a mechanical stirrer, thermometer, Dean-Stark collector, and reflux condenser. t-Butylamine (0.1 mole) was added to the reaction vessel and the mixture was heated to reflux. The water produced during that time was removed. After water evolution has stopped, the desired product 1-(5
-methylbenzothiazol-2-yl)-3-methyl-5-t-butylamino-1,3-imidazolidin-2-one was obtained as a residue. Example 10 1-(5-methylbenzothiazol-2-yl)-
3-methyl-5-acryloyloxy-1,3
-Production of imidazolidin-2-one 1-(5-methylbenzothiazol-2-yl)-
3-Methyl-5-hydroxy-1,3-imidazolidin-2-one (0.1 mole), acryloyl chloride (0.11 mole) and pyridine (0.11 mole) were mixed in a glass reactor equipped with a mechanical stirrer and a thermometer. I put it in a container. The reaction mixture was stirred for about 15 minutes and then left for about 2 hours. Water (100ml) and hexane (30ml) were then added to the mixture. The organic phase was then separated from the aqueous phase and dried over anhydrous magnesium sulfate. The desired product, 1-
(5-Methylbenzothiazol-2-yl)-3-methyl-5-acryloyloxy-1,3-imidazolidin-2-one was obtained as a residue. Example 11 Preparation of 6-chlorobenzothiazol-2-yl isocyanate dimer A saturated solution of phosgene in ethyl acetate (200 ml) was added to a glass reaction vessel equipped with a mechanical stirrer, a thermometer and a reflux condenser. I prepared it in. 2-amino-6
- Chlorbenzothiazole (0.1 mole) was added under stirring. After the addition was complete, the reaction mixture was heated to reflux for about 1 hour. Thereafter, the mixture was cooled and the solid product formed was collected. The solid was then dried to obtain the desired product, 6-chlorobenzothiazol-2-yl isocyanate dimer. Example 12 Preparation of dimethyl acetal of 2-[1-allyl-3-(6-chlorobenzothiazol-2-yl)ureido]acetaldehyde 6-chlorobenzothiazol-2-yl isocyanate dimer (0.1 mole ), dimethyl acetal of 2-allylaminoacetaldehyde (0.2 mole) and benzene (100 ml) were charged to a glass reaction vessel equipped with a mechanical stirrer and a thermometer. The reaction mixture was stirred at ambient temperature for about 1 hour. Thereafter, the reaction mixture is filtered and the solvent is distilled off to obtain the desired product, 2-
[1-allyl-3-(6-chlorobenzothiazole-
Dimethyl acetal of 2-yl)ureido]acetaldehyde was obtained as a residue. Example 13 1-(6-chlorobenzothiazol-2-yl)-
Production of 3-allyl-5-hydroxy-1,3-imidazolidin-2-one Dimethyl acetal of 2-[1-allyl-3-(6-chlorobenzothiazol-2-yl)ureido]acetaldehyde (15 g) , water (200 ml), methanol (200 ml) and concentrated hydrochloric acid (10 ml) were charged into a glass reaction vessel equipped with a mechanical stirrer, thermometer and reflux condenser. The reaction mixture was heated to reflux for approximately 15 minutes. Thereafter, the solvent was distilled off from the reaction mixture under reduced pressure to obtain a residue. By recrystallizing this residue, the desired product 1-(6-chlorobenzothiazol-2-yl)-3-allyl-
5-hydroxy-1,3-imidazolidine-2-
Got it on. Example 14 1-(6-chlorobenzothiazol-2-yl)-
Production of 3-allyl-5-allylamimino-1,3-imidazolidin-2-one 1-(6-chlorobenzothiazol-2-yl)-
3-allyl-5-hydroxy-1,3-imidazolidin-2-one (0.1 mole) and heptane (100
ml) was charged to a glass reaction vessel equipped with a mechanical stirrer, thermometer, Dean-Stark collector, and reflux condenser. Allylamine (0.1 mole) was added to the reaction vessel and the mixture was heated to reflux. The water produced during that time was removed. After the evolution of water has stopped, the desired product, 1-(6-chlorobenzothiazol-2-yl)-3-allyl-5, is obtained by removing the solvent from the reaction mixture under reduced pressure.
-Alylamino-1,3-imidazolidine-2-
On was obtained as a residue. Example 15 1-(6-chlorobenzothiazol-2-yl)-
3-allyl-5-α-chloroacetyloxy-
Production of 1,3-imidazolidin-2-one 1-(6-chlorobenzothiazol-2-yl)-
3-allyl-5-hydroxy-1,3-imidazolidin-2-one (0.1 mole), α-chloroacetyl chloride (0.11 mole) and pyridine (0.11 mole) were added to a glass plate equipped with a mechanical stirrer and a thermometer. It was placed in a prepared reaction vessel. The reaction mixture was stirred for approximately 15 minutes and then left for 2 hours. Water (100ml) and hexane (30ml) were then added to the mixture. Then,
The organic phase was separated from the aqueous phase and dried over anhydrous magnesium sulfate. The desired product 1-(6-
Chlorobenzothiazol-2-yl)-3-allyl-5-α-chloroacetyloxy-1,3-imidazolidin-2-one was obtained as a residue. Example 16 Preparation of 7-bromobenzothiazol-2-yl isocyanate dimer A saturated solution of phosgene in ethyl acetate (200 ml) was
A glass reaction vessel equipped with a mechanical stirrer, thermometer and reflux condenser was charged. 2-Amino-7-bromobenzothiazole (0.1 mole) was added under stirring. Thereafter, the mixture was cooled and the solid product formed was collected. The solid was then dried to obtain the desired product, 7-bromobenzothiazol-2-yl isocyanate dimer. Example 17 Preparation of dimethyl acetal of 2-[1-propargyl-3-(7-bromobenzothiazol-2-yl)ureido]acetaldehyde 7-bromobenzothiazol-2-yl isocyanate dimer (0.1 mole ), dimethyl acetal of 2-propargylaminoacetaldehyde (0.2 mole) and benzene (100 ml) were charged to a glass reaction vessel equipped with a mechanical stirrer and a thermometer. The reaction mixture was stirred at ambient temperature for about 1 hour. Thereafter, the reaction mixture is filtered and the solvent is distilled off to obtain the desired product, 2-
Dimethyl acetal of [1-propargyl-3-(7-bromobenzothiazol-2-yl)ureido]acetaldehyde was obtained as a residue. Example 18 1-(7-brombenzothiazol-2-yl)-
3-propargyl-5-hydroxy-1,3-
Production of imidazolidin-2-one 2-[1-propargyl-3-(7-bromobenzothiazol-2-yl)ureido]acetaldehyde (15g), water (200ml), methanol (200ml)
and concentrated hydrochloric acid (10 ml) were charged to a glass reaction vessel equipped with a mechanical stirrer, thermometer and reflux condenser. The reaction mixture was heated to reflux for approximately 15 minutes. Thereafter, the solvent was distilled off from the reaction mixture under reduced pressure to obtain a residue. The desired product, 1-(7-brombenzothiazol-2-yl)-3-propargyl-5-hydroxy-1,3-imidazolidin-2-one, was obtained by recrystallizing this residue. . Example 19 1-(7-brombenzothiazol-2-yl)-
Production of 3-propargyl-5-β-chloroethylamino-1,3-imidazolidin-2-one 1-(7-brombenzothiazol-2-yl)-
3-propargyl-5-hydroxy-1,3-imidazolidin-2-one (0.1 mole) and heptane (100 ml) were mixed with a mechanical stirrer, thermometer, Dean-Stark collector and reflux. A glass reaction vessel equipped with a condenser was charged. β-
Chlorethylamine (0.1 mole) was added to the reaction vessel and the mixture was heated to reflux. The water produced during this time was removed. After the evolution of water has stopped, the desired product, 1-(7-bromobenzothiazole-2-
yl)-3-propargyl-5-β-chloroethylamino-1,3-imidazolidin-2-one was obtained as a residue. Example 20 1-(7-brombenzothiazol-2-yl)-
3-propargyl-5-propinoyloxy-
Production of 1,3-imidazolidin-2-one 1-(7-bromobenzothiazol-2-yl)-
3-propargyl-5-hydroxy-1,3-imidazolidin-2-one (0.1 mole), propinoyl chloride (0.11 mole) and pyridine (0.11 mole)
was charged into a glass reaction vessel equipped with a mechanical stirrer and a thermometer. The reaction mixture was stirred for about 15 minutes and then left for about 2 hours. Then water (100
ml) and hexane (30 ml) were added to the mixture.
The organic phase was then separated from the aqueous phase and dried over anhydrous magnesium sulfate. The dry solution was then filtered and the solvent was removed under reduced pressure to obtain the desired product, 1-(7-bromobenzothiazol-2-yl)-3.
-propargyl-5-propinoyloxy-1.
3-imidazolidin-2-one was obtained as a residue. Example 21 Preparation of 4-methoxybenzothiazol-2-yl isocyanate dimer A saturated solution of phosgene in ethyl acetate (200 ml) was charged to a glass reaction vessel equipped with a mechanical stirrer, thermometer and reflux condenser. is. 2-amino-4-methoxybenzothiazole (0.1 mole) was added with stirring. After the addition was complete, the reaction mixture was heated to reflux for about 1 hour. Thereafter, the mixture was cooled and the solid product formed was collected. The desired product, 4-methoxybenzothiazol-2-yl isocyanate dimer, was then obtained by drying the solid. Example 22 Preparation of dimethyl acetal of 2-[1-ethyl-3-(4-methoxybenzothiazol-2-yl)ureido]acetaldehyde 4-methoxybenzothiazol-2-yl isocyanate dimer (0.1 mole ), dimethyl acetal of 2-ethylaminoacetaldehyde (0.2 mole), and benzene (100 ml) were charged to a glass reaction vessel equipped with a mechanical stirrer and a thermometer. The reaction mixture was stirred for about 1 hour at ambient temperature. Thereafter, the reaction mixture is taken and the solvent is distilled off from the solution to obtain the desired product 2-
Dimethyl acetal of [1-ethyl-3-(4-methoxybenzothiazol-2-yl)ureido]acetaldehyde was obtained as a residue. Example 23 1-(4-methoxybenzothiazol-2-yl)-3-ethyl-5-hydroxy-1,3-
Preparation of imidazolidin-2-one Dimethyl acetal of 2-[1-ethyl-3-(4-methoxybenzothiazol-2-yl)ureido]acetaldehyde (15 g), water (200 ml), methanol (200 ml) and concentrated Hydrochloric acid (10 ml) was charged to a glass reaction vessel equipped with a mechanical stirrer, thermometer and reflux condenser. The reaction mixture was heated to reflux for approximately 15 minutes. Thereafter, the solvent was distilled off from the reaction mixture under reduced pressure to obtain a residue. By recrystallizing this residue, the desired product 1-(4-
Methoxybenzothiazol-2-yl)-3-ethyl-5-hydroxy-1,3-imidazolidine-
2-on was obtained. Example 24 Preparation of 1-(4-methoxybenzothiazol-2-yl)-2-ethyl-5-β-hydroxyethylamino-1,3-imidazolidin-2-one 1-(4-methoxybenzothiazol-2-yl) Sol-2-yl)-3-ethyl-5-hydroxy-1,3-imidazolidin-2-one (0.1 mole) and heptane (100 ml) were mixed with a mechanical stirrer, a thermometer, and a Dean Stark mixture. Stark) was placed in a glass reaction vessel equipped with a collector and a reflux condenser. β-
Hydroxyethylamine (0.1 mole) was added to the reaction vessel and the mixture was heated to reflux. Water was removed as it formed during that time. After the evolution of water has stopped, the desired product, 1-(4-methoxybenzothiazol-2-yl)-3-ethyl-5-β-hydroxyethyl, is obtained by removing the solvent from the reaction mixture under reduced pressure. Amino-1,3-imidazolidin-2-one was obtained as a residue. Example 25 Production of 1-(4-methoxybenzothiazol-2-yl)-3-ethyl-5-α-methoxyacetyloxy-1,3-imidazolidin-2-one 1-(4-methoxybenzothiazol-2-yl)-3-ethyl-5-α-methoxyacetyloxy-1,3-imidazolidin-2-one Sol-2-yl)-3-ethyl-5-hydroxy-1,3-imidazolidin-2-one (0.1 mole), α-methoxyacetyl chloride (0.11 mole) and pyridine (0.11 mole) were mixed with mechanical stirring. The mixture was placed in a glass reaction vessel equipped with a thermometer and a thermometer. The reaction mixture is approx.
Stir for 15 minutes and leave for about 2 hours. Water (100ml) and hexane (30ml) were then added to the mixture. The organic phase was then separated from the aqueous phase and dried over anhydrous magnesium sulfate. The desired product, 1-(4-methoxybenzothiazole-2), was then obtained by filtering the dry solution and removing the solvent under reduced pressure.
-yl)-3-ethyl-5-α-methoxyacetyloxy-1,3-imidazolidin-2-one was obtained as a residue. Example 26 Preparation of 5-fluorobenzothiazol-2-yl isocyanate dimer A saturated solution of phosgene in ethyl acetate (200 ml) was
A glass reaction vessel equipped with a mechanical stirrer, thermometer and reflux condenser was charged. 2-amino-5-fluorobenzothiazole (0.1 mole) was added under stirring. After the addition was complete, the reaction mixture was heated to reflux for about 1 hour. Thereafter, the mixture was cooled and the solid product formed was collected. The desired product, 5-fluorobenzothiazol-2-yl isocyanate dimer, was then obtained by drying the solid. Example 27 Preparation of dimethyl acetal of 2-[1-chloromethyl-3-(5-fluorobenzothiazol-2-yl)ureido]acetaldehyde 5-fluorobenzothiazol-2-yl isocyanate dimer ( 0.1 mole), dimethyl acetal of 2-chloromethylaminoacetaldehyde (0.2 mole), and benzene (100 ml) were charged to a glass reaction vessel equipped with a mechanical stirrer and a thermometer. The reaction mixture was stirred for about 1 hour at ambient temperature. Thereafter, the reaction mixture is filtered and the solvent is distilled off to obtain the desired product, 2-
Dimethyl acetal of [1-chloromethyl-3-(5-fluorobenzothiazol-2-yl)ureido]acetaldehyde was obtained as a residue. Example 28 1-(5-fluorobenzothiazol-2-yl)-3-chloromethyl-5-hydroxy-
Production of 1,3-imidazolidin-2-one 2-[1-chloromethyl-3-(5-fluorobenzothiazol-2-yl)ureido] dimethyl acetal of acetaldehyde (15 g), water (200 g)
ml), methanol (200ml) and concentrated hydrochloric acid (10ml)
was charged to a glass reaction vessel equipped with a mechanical stirrer, thermometer and reflux condenser. The reaction mixture is approx.
Heated at reflux for 15 minutes. Thereafter, the solvent was distilled off from the reaction mixture under reduced pressure to obtain a residue. Recrystallization of this residue yields the desired product 1
-(5-fluorobenzothiazol-2-yl)-3
-Chloromethyl-5-hydroxy-1,3-imidazolidin-2-one was obtained. Example 29 Preparation of 1-(5-fluorobenzothiazol-2-yl)-3-chloromethyl-5-methoxymethylamino-1,3-imidazolidin-2-one 1-(5-fluorobenzothiazol-2-yl) sol-2-yl)-3-chloromethyl-5-hydroxy-1.
3-imidazolidin-2-one (0.1 mole) and heptane (100 ml) were mixed with a mechanical stirrer, a thermometer,
A glass reaction vessel equipped with a Dean-Stark collector and reflux condenser was charged. Methoxymethylamine (0.1 mole) was added to the reaction vessel and the mixture was heated to reflux. The water produced during that time was removed. After the aqueous nature of the water has stopped, the desired product, 1-(5-fluorobenzothiazol-2-yl)-3-chloromethyl-5-methoxymethylamino, is obtained by evaporating the solvent from the reaction mixture under reduced pressure. -1,3-imidazolidin-2-one was obtained. (Melting point 125°C) Example 30 1-(5-fluorobenzothiazol-2-yl)-3-chloromethyl-5-cyclopropylcarbonyloxy-1,3-imidazolidine-
Preparation of 2-one 1-(5-fluorobenzothiazol-2-yl)-3-chloromethyl-5-hydroxy-1.
3-imidazolidin-2-one (0.1 mole), cyclopropylcarboxylic acid chloride (0.11 mole) and pyridine (0.11 mole) were charged to a glass reaction vessel equipped with a mechanical stirrer and a thermometer. The reaction mixture was stirred for about 15 minutes and left for about 2 hours. Water (100ml) and hexane (30ml) were then added to the mixture. The organic phase is then separated from the aqueous phase,
It was dried with anhydrous magnesium sulfate. The desired product, 1-(5-fluorobenzothiazol-2-yl)-3-chloromethyl-5, is then obtained by filtering the dry solution and removing the solvent from the liquid under reduced pressure.
-Cyclopropylcarbonyloxy-1,3-imidazolidin-2-one was obtained as a residue. Example 31 5-trifluoromethylbenzothiazole-2-
Preparation of isocyanate dimer A saturated solution of phosgene in ethyl acetate (200 ml) was
A glass reaction vessel equipped with a mechanical stirrer, thermometer and reflux condenser was charged. 2-Amino-5-trifluoromethylbenzothiazole (0.1mole)
was added under stirring. After the addition was complete, the reaction mixture was heated to reflux for about 1 hour. Thereafter, the mixture was cooled and the solid product formed was collected. Next, the solid was dried to obtain 5-trifluoromethylbenzothiazol-2-yl isocyanate dimer. Example 32 Preparation of dimethyl acetal of 2-[1-β-bromoethyl-3-(5-trifluoromethylbenzothiazol-2-yl)ureido]acetaldehyde 5-trifluoromethylbenzothiazol-2-
isocyanate dimer (0.1mole), 2-β
- Dimethyl acetal of bromoethylaluminoacetaldehyde (0.2 mole) and benzene (100
ml) was charged into a glass reaction vessel equipped with a mechanical stirrer and a thermometer. The reaction mixture was stirred for about 1 hour at ambient temperature. Thereafter, the reaction mixture was filtered and the solvent was distilled off to obtain the desired product, 2-[1-β-bromoethyl-3-(5
-trifluoromethylbenzothiazol-2-yl)ureido] dimethyl acetal of acetaldehyde was obtained as a residue. Example 33 Preparation of 1-(5-trifluoromethylbenzothiazol-2-yl)-3-bromoethyl-5-hydroxy-1,3-imidazolidin-2-one 2-[1-β-bromoethyl-3 Dimethyl acetal of -(5-trifluoromethylbenzothiazol-2-yl)ureido)acetaldehyde (15
g), water (200 ml), methanol (200 ml) and concentrated hydrochloric acid (10 ml) were charged into a glass reaction vessel equipped with a mechanical stirrer, a thermometer and a reflux condenser. The reaction mixture was heated to reflux for approximately 15 minutes. Thereafter, the solvent was distilled off from the reaction mixture under reduced pressure to obtain a residue. By recrystallizing this residue, the desired product 1-(5-trifluoromethylbenzothiozol-2-yl)-3-β-bromoethyl-5
-Hydroxy-1,3-imidazolidin-2-one was obtained. Example 34 Preparation of 1-(5-trifluoromethylbenzothiazol-2-yl)-3-β-bromoethyl-5-cyclopropylamino-1,3-imidazolidin-2-one methylbenzothiazol-2-yl)-3-β-bromoethyl-5-hydroxy-1,3-imidazolidin-2-one (0.1 mole) and heptane (100 ml) using a mechanical stirrer, a thermometer, Dean Stark
Stark) was placed in a glass reaction vessel equipped with a collector and a reflux condenser. Cyclopropylamine (0.1 mole) was added to the reaction vessel and the mixture was heated to reflux. The water produced during that time was removed. After the evolution of water has stopped, the desired product 1-(5-trifluoromethylbenzothiazol-2-yl)-3 is obtained by removing the solvent from the reaction mixture under reduced pressure.
-β-bromoethyl-5-cyclopropylamino-1,3-imidazolidin-2-one was obtained as a residue. Example 35 1-(5-trifluoromethylbenzothiazol-2-yl)-3-β-bromoethyl-5-benzoyloxy-1,3-imidazolidine-2
Production of -one 1-(5-trifluoromethylbenzothiazol-2-yl)-3-β-bromoethyl-5-hydroxy-1,3-imidazolidin-2-one (0.1 mole), benzoyl chloride (0.11 mole) mole) and pyridine (0.11 mole) were charged to a glass reaction vessel equipped with a mechanical stirrer and a thermometer. The reaction mixture was stirred for about 15 minutes and left for about 2 hours. Water (100ml) and hexane (30ml) were then added to the mixture. The organic phase is then separated from the aqueous phase,
It was dried with anhydrous magnesium sulfate. Then, by filtering the dry solution and distilling off the solvent under reduced pressure,
The desired product 1-(5-trifluoromethylbenzothiazol-2-yl)-3-β-bromoethyl-5-benzoyloxy-1,3-imidazolidin-2-one was obtained as a residue. Example 36 1-benzothiazol-2-yl-3-methyl-
5-anilino-1,3-imidazolidine-2-
Preparation of 1-benzothiazol-2-yl-3-methyl-
5-hydroxy-1,3-imidazolidine-2-
(0.1 mole) and heptane (100 ml) with a mechanical stirrer, Dean-Stark
A glass reaction vessel equipped with a collector and a reflux condenser was charged. Aniline (0.1 mole) was added to the reaction vessel and the mixture was heated to reflux. The water produced during that time was removed. After the evolution of water has stopped, the desired product, 1-benzothiazol-2-yl-3-methyl-5-anilino-1,3-imidazolidine-, is obtained by evaporating the solvent from the reaction mixture under reduced pressure.
2-one was obtained as a residue. Example 37 1-benzothiazol-2-yl-3-methyl-
Production of 5-dimethylamino-1,3-imidazolidin-2-one 1-benzothiazol-2-yl-3-methyl-
5-hydroxy-1,3-imidazolidine-2-
(0.1 mole) and heptane (100 ml) with a mechanical stirrer, Dean-Stark
A glass reaction vessel equipped with a collector and a reflux condenser was charged. Dimethylamine (0.1 mole) was added to the reaction vessel and the mixture was heated to reflux. The water produced during that time was removed. After the evolution of water has stopped, the desired product, 1-benzothiazol-2-yl-
3-Methyl-5-dimethylamino-1.3-imidazolidin-2-one was obtained as a residue. The novel compounds of this invention are of particular value for weed control because, while relatively non-toxic to many useful plants, they are toxic to many species and groups of weeds. The exact amount of compound required will depend on a variety of factors, including the infestation of particular weed species, weather, soil quality, method of application, types of useful plants in the same area, and the like. Therefore, a mild infestation of weeds growing under adverse conditions requires only 28.4 or 56.8 grams per acre.
Applications of less than 284 g (10 oz.) per acre are sufficient for good control of heavy perennial weeds that grow under favorable conditions. )
Application of the above compounds may be necessary. The weed toxicity of the novel compounds of the present invention can be demonstrated by established methods known in the art, pre-emergence and post-emergence tests, such as those described below. The weed activity of the compounds of the present invention can be demonstrated by tests conducted for pre-emergence control of various weeds. In these tests, seeds of various weeds are sown in small plastic greenhouse pots filled with dry soil. Within 24 hours after sowing, the pots are watered until the soil is wet and the test compound, formulated as an aqueous emulsion in acetone solution containing an emulsifier, is sprayed onto the soil surface at the desired concentration. After spraying, the soil container is placed in a greenhouse and provided with the necessary supplemental heat and once or more frequent watering daily. The plants are kept under these conditions for 15-21 days, at which point the condition of the plants and the degree of damage to the plants are evaluated according to the scale described below. 0 = no damage, 1, 2 = slight damage, 3, 4
= moderate damage, 5, 6 = moderate damage, 7,
8, 9=severe damage, 10=death The weed activity of the compounds of the invention can also be demonstrated by tests conducted on post-emergence control of various weeds. In these tests, the test compound is formulated as an aqueous emulsion and sprayed at the desired application rate onto the leaves of weeds that have reached a predetermined size. After spraying, the plants are placed in a greenhouse and watered once daily or more frequently. Do not apply water to the leaves of treated plants. 10-15 after processing
After a few days, determine the extent of the damage and rate it on the 0-10 scale described above.

[Table] The weed activity of the compounds of the present invention was also demonstrated by tests conducted on post-emergence control of various weeds. In these tests, the product of Example 3 was formulated as an aqueous emulsion and sprayed at the indicated application rate onto the leaves of weeds that had reached a predetermined size. After spraying, the plants were placed in a greenhouse and watered once daily or more frequently.
No water was applied to the leaves of the treated plants. The extent of damage was determined 14 days after treatment and rated according to the 0-10 scale described above. The effectiveness of these compounds is evidenced by the data in Table 2.

【table】

[Table] Tsuetsuji

Claims (1)

[Claims] 1 formula _{( wherein} ^, _{_ _} ^_ _{_ _} or a _C2 - _C5 alkoxyalkyl group). 2 1-benzothiazol-2-yl-3-methyl-5-hydroxy-1,3-imidazolidine-2
The compound according to claim 1, which is -one. 3 1-benzothiazol-2-yl-3-methyl-5-ethylamino-1,3-imidazolidine-
A compound according to claim 1 which is a 2-one. 4 1-(5-fluorobenzothiazol-2-yl)-3-chloromethyl-5-methoxymethyl-
The compound according to claim 1, which is 1,3-imidazolidin-2-one. 5 formula A herbicidal composition containing a compound represented by the following formula (wherein X is hydrogen or halogen; ^R1 is _C1 - _C3 alkyl or _C1 - _C3 haloalkyl) as an active ingredient.