JPH07196654A - Chloroethoxythiazolidine derivative and herbicide - Google Patents

Abstract

PURPOSE:To obtain a chloroethoxythiazolidine derivative of specific formula useful as a selective herbicide, having extremely strong fungicidal power on weeds in a paddy field, especially barnyard grass and high safety to rice plants. CONSTITUTION:The derivative of formula I. The derivative is preferably produced by reacting a pyrimidine derivative of formula II with chlorosulfonyl isocyanate in a solvent such as tetrahydrofuran and then successively with 2-imino-3-chloroethoxythiazolidine of formula III or the compound of formula IV in the presence of a base such as triethylamine.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel chloroethoxy thiazolidine derivative and a herbicide for paddy fields containing the same as an active ingredient.

[0002]

2. Description of the Related Art It is indispensable to use herbicides to protect important crops such as rice, wheat, corn, soybean, cotton and beet from weed damage and increase yields. In particular, in recent years, a selective herbicide capable of selectively killing only weeds without phytotoxicity to the crops even when simultaneously treating the foliage of the crops and weeds in arable land where these useful crops and weeds are mixed is desired. ing. In addition, from the viewpoint of prevention of environmental pollution, reduction of economic costs in transportation and spraying, research and exploration of compounds that show high herbicidal effect with the lowest possible dose has been continued for many years. Although some of the compounds with such properties are currently used as selective herbicides, there is still a need for better new compounds with these properties.

As a prior art similar to the compound of the present invention, substituted thiazolidines are disclosed in JP-A-5-501236.
Although disclosed in the publication, there is no description of specific physical properties of the thiazolidine derivative substituted with a haloalkoxy group containing the compound of the present invention, and the compound of the present invention is a novel compound. Further, in the patent, specific utility of the compound of the present invention,
That is, there is no description about the property as a highly active and highly selective herbicide for paddy fields (fly control agent).

[0004]

[Means for Solving the Problems] The present inventors have continued to study for many years to develop a herbicide having selectivity for important crops, and produce compounds having higher herbicidal activity and selectivity. Therefore, the herbicidal properties of many compounds have been investigated. As a result, formula (1):

[0005]

[Chemical 2]

A chloroethoxy thiazolidine derivative represented by the following formula and its agriculturally suitable salts (hereinafter referred to as the compound of the present invention) are used for paddy field weeds in both soil treatment and foliage treatment under flooded conditions. In particular, the inventors have found that the present invention has a remarkably strong herbicidal activity against fly and high safety against rice, which is an important crop, and completed the present invention. The compound of the present invention can be easily produced by selecting one of the following reaction formulas 1 to 6. [Reaction formula 1]

[0007]

[Chemical 3]

[In the formula, Z represents a halogen atom. That is, the pyrimidine derivative (2) is reacted with chlorosulfonyl isocyanate in a solvent such as tetrahydrofuran, dimethoxyethane, acetonitrile, propionitrile, dimethylformamide, dichloromethane, ethylene dichloride, benzene and toluene, and then triethylamine and pyridine are added. , In the presence of a base such as sodium hydride, sodium methoxide, sodium ethoxide, sodium hydroxide, potassium hydroxide, potassium carbonate,
2-Imino-3-chloroethoxythiazolidines (3)
Alternatively, the compound (1) of the present invention can be obtained by reacting with (4).

Chlorsulfonyl isocyanate is used in an amount of 0.7 to 1.3 mol per 1 mol of the pyrimidine derivative (2). The reaction temperature can be arbitrarily selected from the range of -50 ° C to 80 ° C. 2-imino-3-chloroethoxythiazolidines (3) or (4) is used in an amount of 0.7 to 1.3 mol, based on 1 mol of the pyrimidine derivative (2), and
The base is used in an amount of 0.5 to 4.0 mol per 1 mol of 2-imino-3-chloroethoxythiazolidines (3) or (4).

The reaction temperature can be arbitrarily selected from the range of -50 ° C to 100 ° C. [Reaction formula 2]

[0011]

[Chemical 4]

[Wherein Z represents the same meaning as described above, and Y represents
Represents a lower alkyl group having 1 to 6 carbon atoms or a phenyl group. ] That is, 2-imino-3-chloroethoxythiazolidines (3) or (4) and phenyl N-chlorosulfonylcarbamate (5: Y = phenyl group) or alkyl N-chlorosulfonylcarbamate (5: Y = lower alkyl group) The reaction with is carried out using 0.5 to 3.0 mol amount of the carbamate derivative (5) per 1 mol of 2-imino-3-chloroethoxythiazolidines (3) or (4), but preferably A range of 0.9 to 1.2 molar is suitable.

The reaction temperature can be arbitrarily selected from the range of -50 ° C to 100 ° C, but is preferably -20 ° C to 30 ° C.
The range is appropriate. This reaction is carried out using various bases. The amount of the base is 0.5 per 1 mol of 2-imino-3-chloroethoxythiazolidine (3) or (4).
To 4.0 molar amount.

Suitable bases include, for example, organic bases such as triethylamine and pyridine, metal hydrides such as sodium hydride, sodium hydroxide, potassium hydroxide,
Inorganic bases such as potassium carbonate, sodium methoxide,
Metal alkoxides such as sodium ethoxide are used. Suitable solvents for this reaction include solvents inert to this reaction, for example, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as dichloromethane, chloroform and ethylene dichloride, ethyl ether and isopropyl ether. , Ethers such as dioxane and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, hydrocarbons such as petroleum ether, petroleum benzine and heptane, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate, dimethylformamide, Amides such as dimethylacetamide and hexamethylphosphoric triamide. These solvents may be used alone or as a mixture. Particularly preferred is the case where ethers or amides are used.

Then, phenyl 3-chloroethoxy thiazolidine-2-iminosulfonyl carbamate (6: Y
= Phenyl group) or alkyl 3-chloroethoxythiazolidine-2-iminosulfonylcarbamate (6:
The compound (1) of the present invention can be obtained by heating (Y = lower alkyl group) and the pyrimidine derivative (2) in various solvents such as benzene, toluene, xylene and dioxane. [Reaction formula 3]

[0016]

[Chemical 5]

[Wherein Y represents the same meaning as described above. That is, 3-chloroethoxythiazolidine-2-iminosulfonamide (7) is added to an inorganic base such as potassium carbonate or triethylamine or 1,8-diazabicyclo [5.4.0] in a solvent such as acetone, acetonitrile or dioxane. ] The compound (1) of the present invention can be obtained by reacting with the carbamate derivative (8) in the presence of an organic base such as -7-undecene (DBU). [Reaction formula 4]

[0018]

[Chemical 6]

[In the formula, Y represents the same meaning as described above. ] That is, 3-chloroethoxythiazolidine-2-iminosulfonamide (7) was added to a solvent such as acetone, methyl ethyl ketone, acetonitrile, tetrahydrofuran, dimethylformamide, dioxane, potassium carbonate,
Phenyl 3-chloroethoxythiazolidine-2-iminosulfonylcarbamate (6: Y = phenyl group) or alkyl 3-chloroethoxythiazolidine-2-imino by reacting with chloroformic acid ester or carbonic acid ester in the presence of a base such as triethylamine. A sulfonyl carbamate (6: Y = lower alkyl group) is obtained. Then, the compound (1) of the present invention can be obtained by heating the pyrimidine derivative (2) in a solvent such as benzene, toluene, xylene, or dioxane. [Reaction formula 5]

[0020]

[Chemical 7]

That is, the reaction of 2-imino-3-chloroethoxythiazolidine (3) with chlorosulfonylisocyanate is carried out by reacting 1 mol of 2-imino-3-chloroethoxythiazolidine (3) with chlorosulfonylisocyanate. It is carried out in an amount of 7 to 2.0 moles, preferably 0.9 to 1.5 moles. In this reaction, the intermediate 1- [3- (2-chloroethoxy) thiazolidine-2-iminosulfonyl] -3-chlorosulfonylurea was synthesized at a reaction temperature of −50 ° C. to 50 ° C.
It is carried out in the range of ° C. Next, the reaction temperature is set within the range of 60 ° C. to 150 ° C. to a temperature suitable for the rearrangement reaction and the accompanying removal of hydrogen chloride produced, and the mixture is heated to give 3-chloroethoxythiazolidine-2-iminosulfonyl isocyanate ( You can lead to 9).

Suitable solvents for this reaction include solvents inert to this reaction, for example, aromatic hydrocarbons such as benzene, toluene and xylene, aromatic halides such as chlorobenzene and dichlorobenzene, and nitrobenzene. Etc., aromatic nitrates such as ethylene dichloride, halogenated hydrocarbons such as ethylene dichloride, ethers such as dioxane and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, hydrocarbons such as petroleum ether, petroleum benzine and heptane, methyl ethyl ketone And the like, and esters such as ethyl acetate. These solvents may be used alone or as a mixture. Particularly preferred is the case where aromatic halides or aromatic hydrocarbons are used.

Then, 3-chloroethoxythiazolidine-2-iminosulfonyl isocyanate (9) and pyrimidine derivative (2) were added to dichloromethane, chloroform and
The compound (1) of the present invention can be obtained by reacting in a solvent such as ethylene dichloride, ethyl ether, dioxane, acetonitrile, acetone, methyl ethyl ketone, benzene, toluene, xylene, chlorobenzene or dichlorobenzene. [Reaction formula 6]

[0024]

[Chemical 8]

That is, the reaction of 3-chloroethoxythiazolidine-2-iminosulfonyl chloride (10) with the pyrimidine derivative (2) and sodium cyanate is
Pyrimidines (2) per mol of 3-chloroethoxythiazolidine-2-iminosulfonyl chloride (10)
In an amount of 0.5 to 1.5 mol and sodium cyanate in an amount of 1 to 3 mol. Reaction temperature is -20 ° C to 5
The temperature can be arbitrarily selected from the range of 0 ° C, but the range of 5 ° C to 30 ° C is preferable.

This reaction is carried out using various bases.
The amount of the base is 1 to 3 with respect to 1 mol of 3-chloroethoxythiazolidine-2-iminosulfonyl chloride (10).
Used in molar amounts. Suitable bases include organic bases such as triethylamine and pyridine, metal alkoxides such as sodium methoxide and sodium ethoxide, metal hydrides such as sodium hydride, sodium hydroxide, potassium hydroxide, potassium carbonate and the like. Inorganic bases are used, but organic bases are particularly preferable.

Suitable solvents for this reaction include solvents inert to this reaction, for example, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as dichloromethane, chloroform and ethylene dichloride, dioxane, and the like. Ethers such as tetrahydrofuran, nitriles such as acetonitrile and propionitrile, ketones such as acetone and methyl ethyl ketone, dimethylformamide,
Amides such as dimethylacetamide and hexamethylphosphoric triamide. These solvents may be used alone or as a mixture. Particularly preferred is the case where nitriles or amides are used.

3-Chloroethoxythiazolidine-2-iminosulfonyl chloride (10) can be synthesized from 2-imino-3-chloroethoxythiazolidines (3) or (4) using the method of the following reaction formula 7 and the like. You can [Reaction formula 7]

[0029]

[Chemical 9]

[In the formula, Z represents the same meaning as described above. In Reaction Scheme 7, the amount of sulfuryl chloride can be arbitrarily selected from the equimolar amount to the excess amount. This reaction is carried out using various bases. The amount of base is 2-imino-3-
Chlorethoxythiazolidines (3) or (4) are used in an amount of 0.8 to 5 mol per 1 mol.

Suitable bases include triethylamine,
Organic bases such as pyridine, metal alkoxides such as sodium methoxide and sodium ethoxide, metal hydrides such as sodium hydride, and inorganic bases such as sodium hydroxide, potassium hydroxide and potassium carbonate are used. Particularly preferred is the case where organic bases are used.
Suitable solvents for this reaction include solvents inert to this reaction,
For example, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as dichloromethane, chloroform and ethylene dichloride, ethers such as dioxane and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, acetone and methyl ethyl ketone. Amides such as dimethylformamide, dimethylacetamide, and hexamethylphosphoric triamide.

These solvents may be used alone or as a mixture. The reaction temperature can be arbitrarily selected from the range of -50 ° C to 100 ° C, but the range of -20 ° C to 50 ° C is preferable. 3-chloroethoxy thiazolidine-2
-Iminosulfonamide (7) can be synthesized using the methods of Reaction Schemes 8 and 9 below. [Reaction formula 8]

[0033]

[Chemical 10]

[In the formula, Z represents the same meaning as described above. In Reaction Scheme 8, the reaction of tert-butanol with chlorosulfonyl isocyanate can be carried out by a method known per se, for example, by referring to JP-A No. 50-101323. The reaction of 2-imino-3-chloroethoxythiazolidines (3) or (4) with tert-butylsulfamoyl chloride is 2-imino-3.
-Chloroethoxythiazolidines (3) or (4) 1
It is carried out using 0.5 to 3.0 molar amount of tert-butylsulfamoyl chloride per mol, preferably 0.9 to 1.2 molar amount is suitable.

The reaction temperature can be arbitrarily selected from the range of -50 ° C to 100 ° C, but is preferably -20 ° C to 30 ° C.
The range is appropriate. This reaction is carried out using various bases. The amount of the base used is 0.5 to 4.0 mols, preferably 0.8 to 2.5 mols, per 1 mol of the 2-imino-3-chloroethoxythiazolidine (3) or (4). The range is appropriate. Suitable bases include, for example, metal hydrides such as sodium hydride, organic bases such as triethylamine and pyridine, inorganic bases such as sodium hydroxide, potassium hydroxide and potassium carbonate,
Although metal alkoxides such as sodium methoxide and sodium ethoxide are used, the case where organic bases are used is particularly preferable.

Suitable solvents for this reaction include solvents inert to this reaction, for example, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as dichloromethane, chloroform and ethylene dichloride, ethyl ether. , Ethers such as isopropyl ether, dioxane and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, hydrocarbons such as petroleum ether, petroleum benzine and heptane, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate, Amides such as dimethylformamide, dimethylacetamide, and hexamethylphosphoric triamide. These solvents may be used alone or as a mixture. Particularly preferred is when ethers or amides are used.

In reaction scheme 8, the tert-butyl group is removed by using trifluoroacetic acid. The amount of trifluoroacetic acid can be arbitrarily selected from equimolar amount to excess amount. There is no problem even if trifluoroacetic acid is used as a solvent. The reaction temperature can be arbitrarily selected from the range of -50 ° C to 80 ° C. A range of -20 ° C to 30 ° C is preferable.

When a solvent is used in this reaction, a solvent inert to this reaction, for example, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as dichloromethane, chloroform and ethylene dichloride, Ethers such as ethyl ether, isopropyl ether, dioxane and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, hydrocarbons such as petroleum ether, petroleum benzine and heptane, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate Kind,
Amides such as dimethylformamide, dimethylacetamide, and hexamethylphosphoric triamide. You may use these solvent individually or in mixture. [Reaction formula 9]

[0039]

[Chemical 11]

In reaction formula 9, the amount of ammonia is 3-
It can be optionally selected from 2 mol to an excess amount with respect to 1 mol of chloroethoxythiazolidine-2-iminosulfonyl chloride (10). As ammonia, there is no problem even if liquid, gaseous or aqueous ammonia is used. The reaction temperature can be arbitrarily selected from the range of -76 ° C to 80 ° C.

Suitable solvents for this reaction include solvents inert to this reaction, for example, aromatic hydrocarbons such as benzene, toluene and xylene, dichloromethane, chloroform,
Halogenated hydrocarbons such as ethylene dichloride, ethers such as ethyl ether, isopropyl ether, dioxane and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, hydrocarbons such as petroleum ether, petroleum benzene and heptane, acetone and methyl ethyl ketone. And the like, esters such as ethyl acetate, amides such as dimethylformamide, dimethylacetamide and hexamethylphosphoric triamide, and alcohols such as methanol and ethanol. These solvents may be used alone or as a mixture. Also, the optimum solvent differs depending on the properties of the ammonia used.

The intermediate phenyl 3- used in the present invention
Chlorethoxythiazolidine-2-iminosulfonylcarbamate (6: Y = phenyl group), alkyl 3-chloroethoxythiazolidine-2-iminosulfonylcarbamate (6: Y = lower alkyl group), 3-chloroethoxythiazolidine-2-iminosulfone Amide (7), 3
-Chloroethoxythiazolidine-2-iminosulfonyl isocyanate (9) and 3-chloroethoxythiazolidine-2-iminosulfonyl chloride (10) are also novel compounds.

In Reaction Scheme 2, phenyl N-chlorosulfonylcarbamate (5: Y = phenyl group) and alkyl N-chlorosulfonylcarbamate (5: Y = lower alkyl group) can be prepared by a method known per se, for example, Chemiche-Berichte. (Chemische Bericht
e), 96, page 56 (1963).

2-used as a starting material for the above reaction
Imino-3-chloroethoxythiazolidines (3) or (4) can be obtained, for example, from Journal of Organics.
Chemistry (Journal of Organic)
Chemistry, Vol. 30, p. 4298 (19).
1965) and the like can be used for the synthesis. Reaction scheme 10 shows a synthetic scheme of 2-imino-3-chloroethoxythiazolidine hydrobromide. [Reaction formula 10]

[0045]

[Chemical 12]

The synthetic examples of the compounds of the present invention will be specifically described below as Reference Examples and Examples, but the present invention is not limited thereto. [Reference Example 1] Synthesis of 2-chloroethoxyamine hydrochloride

[0047]

[Chemical 13]

Hydroxyphthalimide 56.8 g (34
8 mmol) was dissolved in 500 ml of DMF, and 50 g (348 mmol) of 1-bromo-2-chloroethane was added. 56.6 g (410 mmol) of potassium carbonate at room temperature
Was added in several times, and the mixture was subsequently stirred at 85 ° C. for 3 hours.
After allowing to cool to room temperature, it was poured into 1 liter of ice water. Benzene 400
The mixture was extracted 3 times with ml, the benzene layer was washed with water and saturated saline, and then dried over anhydrous sodium sulfate. After distilling off the solvent under reduced pressure, a small amount of ethyl ether was added to the residue, and the crystals were collected by filtration to obtain 44.5 g of N- (2-chloroethoxy) phthalimide. Melting point 83-86 ° C. N- (2-chloroethoxy) phthalimide 44 g (19
(5 mmol) was dissolved in 500 ml of ethanol, 11.7 g (234 mmol) of hydrazine monohydrate was added dropwise at room temperature, the temperature was gradually raised, and the mixture was heated under reflux for 5 minutes. After allowing to cool to room temperature, 20.3 g (195 mmol) of 35% hydrochloric acid was added dropwise, and then the temperature was gradually raised and heated under reflux for 5 minutes. After allowing to cool to room temperature, it was further cooled with ice water, the insoluble matter was removed by filtration, and the solvent was evaporated under reduced pressure. A small amount of ethanol and water were added to the residue, the insoluble matter was filtered off, and the solvent was distilled off again under reduced pressure. Ethyl ether was added to the residue for crystallization, and the crystals were collected by filtration to give 2-chloroethoxyamine hydrochloride (18.6 g).
Melting point 140-144 ° C. [Reference Example 2] Synthesis of ethyl N- (2-chloroethoxy) carbamate

[0049]

[Chemical 14]

2-Chloroethoxyamine hydrochloride 18.6
g (141 mmol) was dissolved in 100 ml of water, and 200 ml of ethylene dichloride was added. Under cooling, 39 g (283 mmol) of potassium carbonate was added in several portions, and then 15.3 g (141 mmol) of ethyl chloroformate was added to 10 times.
It was added dropwise at a temperature of not higher than 0 ° C. After warming to room temperature, the mixture was stirred at the same temperature for 4 hours. After separating the ethylene dichloride layer, the aqueous layer was extracted twice with 100 ml of chloroform. The ethylene dichloride layer and the chloroform layer were combined, washed with saturated saline and then dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. Distillation under reduced pressure gave 16.8 g of ethyl N- (2-chloroethoxy) carbamate. Boiling point 78 ° C /
0.3 mmHg [Reference Example 3] Synthesis of ethyl N- (2-bromoethyl) -N- (2-chloroethoxy) carbamate

[0051]

[Chemical 15]

2.80 g (70%) of 60% sodium hydride
mmol) was suspended in 60 ml of dry tetrahydrofuran, and a solution of 10.6 g (63 mmol) of ethyl N- (2-chloroethoxy) carbamate in 15 ml of dry tetrahydrofuran was added dropwise at 10 ° C or lower under ice cooling. 10 mg
18-crown-6 and 10 mg of tetra-n-butylammonium bromide were added, and the mixture was warmed to room temperature, stirred at the same temperature for 30 minutes, and ice-cooled again. Then 1,2-
34.8 g (185 mmol) of dibromoethane was added all at once, the temperature was gradually raised, and the mixture was heated under reflux for 3 hours. After allowing to cool to room temperature, the reaction mixture was poured into 100 ml of ice water. The mixture was extracted 3 times with 100 ml of chloroform, the chloroform layer was washed with saturated saline and then dried over anhydrous sodium sulfate. After evaporating the solvent under reduced pressure, the residue was purified by silica gel column chromatography (chloroform), and oily ethyl N- (2
7.25 g of -bromoethyl) -N- (2-chloroethoxy) carbamate was obtained. [Reference Example 4] Synthesis of S- [2- (N- (2-chloroethoxy) -N-ethoxycarbonyl) aminoethyl] isothiuronium hydrobromide

[0053]

[Chemical 16]

Ethyl N- (2-bromoethyl) -N-
(2-chloroethoxy) carbamate 6.69 g (2
4.4 mmol), thiourea 1.84 g (24.2 mm)
ol) and 20 ml of ethanol were heated under reflux for 16 hours. After cooling, the solvent was distilled off under reduced pressure, 100 ml of chloroform was added to the residue, and the mixture was stirred at room temperature for 10 minutes. After removing the insoluble matter by filtration, chloroform was distilled off under reduced pressure. 200 ml of ethyl ether was added to the residue, and the mixture was kept at room temperature for 3
Stir for 0 minutes. The ethyl ether was removed by decantation, and the residue was dried using a vacuum pump to give oily S- [2- (N- (2-chloroethoxy)-].
N-ethoxycarbonyl) aminoethyl] isothiuronium hydrobromide salt (8.43 g) was obtained. [Reference Example 5] Synthesis of S- [2- (N- (2-chloroethoxy)) aminoethyl] isothiuronium hydrobromide

[0055]

[Chemical 17]

S- [2- (N- (2-chloroethoxy)]
8.43 g (24.1 mmol) of -N-ethoxycarbonyl) aminoethyl] isothiuronium hydrobromide and 0.9 ml of water were added to 54 ml of 30% hydrogen bromide / acetic acid solution, and the mixture was heated with stirring at 60 ° C for 4 hours. After cooling, acetic acid was distilled off under reduced pressure, ethyl ether and a small amount of ethanol were added to the residue for crystallization, and the crystals were collected by filtration to give S- [2-
6.71 g of (N- (2-chloroethoxy)) aminoethyl] isothiuronium hydrobromide was obtained. Melting point 112-
115 ° C. [Reference Example 6] Synthesis of 2-imino-3- (2-chloroethoxy) thiazolidine hydrobromide (4: Z = Br)

[0057]

[Chemical 18]

S- [2- (N- (2-chloroethoxy)) aminoethyl] isothiuronium hydrobromide 6.
71 g (24.1 mmol) was added to 40 ml of ethanol, and the mixture was heated under reflux for 3 hours. After allowing to cool, ethanol was distilled off under reduced pressure, ethanol was added to the residue, and the mixture was stirred at room temperature for 10 minutes. After removing the insoluble matter by filtration, ethanol was distilled off under reduced pressure. Ethyl ether and a small amount of ethanol were added to the residue for crystallization, and the crystals were collected by filtration to give 2-imino-3-.
(2-chloroethoxy) thiazolidine hydrobromide (4:
2.0 g of Z = Br) was obtained. Melting point 118-120 ° C

[0059]

【Example】

[Example 1] 1- [3- (2-chloroethoxy) thiazolidine-2-
Synthesis of iminosulfonyl] -3- (4-methoxy-6-methylpyrimidin-2-yl) urea (1)

[0060]

[Chemical 19]

209 mg (1.50 mmol) of 2-amino-4-methyl-6-methoxypyrimidine was dissolved in 10 ml of dry tetrahydrofuran, and -50 ° C to -40 ° C.
Within the range of chlorosulfonyl isocyanate 213m
g (1.51 mmol) was added dropwise. The reaction temperature was raised to 0 ° C and then cooled to -50 ° C again, and then 2-imino-3 was used.
-(2-Chloroethoxy) thiazolidine hydrobromide 36
8 mg (1.41 mmol), triethylamine 333
mg (3.30 mmol) and tetrahydrofuran 1
0 ml of the mixture was added. Raise the reaction temperature to room temperature,
The mixture was continuously stirred at the same temperature for 1 hour. Next, the solvent was distilled off under reduced pressure, 20 ml of water was added to the obtained residue, and the mixture was extracted 3 times with 50 ml of chloroform. Chloroform layer is water 50
After washing with ml, it was dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, ethyl ether and acetonitrile were added to the residue for crystallization, and the crystals were collected by filtration to give the desired 1- [3- (2-chloroethoxy) thiazolidine-2.
300 mg of -iminosulfonyl] -3- (4-methoxy-6-methylpyrimidin-2-yl) urea (1) was obtained. Melting point 146 to 148 ° C. The application dose of the compound of the present invention varies depending on the application scene, application time, application method, target weeds, cultivated crops, etc., but is generally 0.00 per hectare (ha) as the active ingredient amount.
01 to 1 kg, preferably 0.001 to 0.5 kg
The degree is appropriate.

If desired, the compound of the present invention may be mixed with other herbicides, various insecticides, fungicides, plant growth regulators, safeners, synergists and the like at the time of formulation or spraying. Especially when mixed with other herbicides,
It is expected that the cost will be reduced by reducing the applied amount, the herbicidal spectrum will be expanded by the synergistic action of the mixed agents, and a higher herbicidal effect will be obtained. At this time, it is possible to combine a plurality of known herbicides at the same time. Examples of the type of herbicide used in combination with the compound of the present invention include, for example, Form Chemicals Handbook (Farm Chemicals Hand).
(book) Compounds described in 1990 edition.

When the compound of the present invention is applied as a herbicide, generally, a suitable carrier, for example, solid carrier such as clay, talc, bentonite, diatomaceous earth, white carbon or the like, water, alcohols (isopropanol, butanol, benzine alcohol, flue alcohol) Furyl alcohol etc.), aromatic hydrocarbons (toluene, xylene etc.), ethers (anisole), ketones (cyclohexanone, isophorone etc.), esters (butyl acetate etc.), acid amides (N-methylpyrrolidone etc.) ) Or halogenated hydrocarbons (chlorobenzene, etc.) and other liquid carriers can be mixed and applied, and if desired, surfactants, emulsifiers, dispersants, penetrants, spreading agents, thickeners, antifreeze. Agents, anti-caking agents, stabilizers, etc., liquids, emulsions, wettable powders,
It can be put into practical use in any dosage form such as a dry flowable agent, a flowable agent, a powder agent, and a granule agent.

Next, specific examples of formulation of the preparation when the compound of the present invention is used will be shown. However, the compounding examples of the present invention are not limited to these. In the following formulation examples, "part" means part by weight. [Wettable powder] Compound of the present invention 5 to 80 parts Solid carrier 10 to 85 parts Surfactant 1 to 10 parts Others 1 to 5 parts Other examples include anti-caking agents.

[Emulsion] Compound of the present invention 1 to 30 parts Liquid carrier 30 to 95 parts Surfactant 5 to 15 parts [Flowable agent] Compound of the present invention 5 to 70 parts Liquid carrier 15 to 65 parts Surfactant 5 to 12 parts Others 5 to 30 parts Other examples include antifreezing agents and thickeners.

[Granular wettable powder (dry flowable agent)] Compound of the present invention 20 to 90 parts Solid carrier 10 to 60 parts Surfactant 1 to 20 parts [Granule] Compound of the present invention 0.1 to 10 parts Solid carrier 90 -99.9 parts Others 1-5 parts [Formulation Example 1] Wettable powder Compound of the present invention 20 parts Diquelite A 76 parts (Kaolin-based clay: product name of Sikhlite Industrial Co., Ltd.) Solpol 5039 2 parts (nonionic) Mixture of surfactant and anionic surfactant: Toho Chemical Industry Co., Ltd. trade name Carplex (anti-caking agent) 2 parts (white carbon: Shionogi Seiyaku Co., Ltd. trade name) Crush into wettable powder.

[Compounding Example 2] Wettable powder Compound of the present invention 40 parts Dikelite A 54 parts (Kaolin clay: trade name of Sikhlite Industry Co., Ltd.) Sorpol 5039 2 parts (Nonionic surfactant and anionic interface Mixture with activator: Toho Chemical Industry Co., Ltd. trade name Carplex (anti-caking agent) 4 parts (white carbon: Shionogi Seiyaku Co., Ltd. trade name) To do.

[Formulation Example 3] Emulsion Compound of the present invention 5 parts Xylene 75 parts Dimethylformamide 15 parts Sorpol 2680 5 parts (Mixture of nonionic surfactant and anionic surfactant: Toho Chemical Industry Co., Ltd.) ) Mix the above uniformly to make an emulsion.

[Formulation Example 4] Flowable agent Compound of the present invention 25 parts Aglycol S-710 10 parts (Nonionic surfactant: Kao Corporation trade name) Lunox 1000C 0.5 part (Anionic surfactant: Toho) Chemical Industry Co., Ltd. product name) 1% Rhodopol water 20 parts (Thickener: Lone Poulean Company product name) water 44.5 parts The above ingredients are uniformly mixed to obtain a flowable agent.

[Formulation Example 5] Flowable agent Compound of the present invention 40 parts Aglycol S-710 10 parts (Nonionic surfactant: Kao Corporation trade name) Lunox 1000C 0.5 part (Anionic surfactant: Toho) Chemical Industry Co., Ltd. product name) 1% Rhodopol water 20 parts (Thickener: Lone Poulean Company product name) water 29.5 parts The above ingredients are uniformly mixed to obtain a flowable agent.

[Formulation Example 6] Granular wettable powder (dry flowable agent) Compound of the present invention 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 7] Granules Compound of the present invention 1 part Bentonite 55 parts Talc 44 parts After uniformly mixing and pulverizing the above, a small amount of water was added and the mixture was kneaded with stirring, and granulated with an extrusion granulator. And dry to make granules.

In use, the wettable powder, emulsion, flowable powder and granular wettable powder are diluted 50 to 1000 times with water to prepare an active ingredient of 0.000 per hectare (ha).
Sprinkle so that it is 1 to 1 kg. The compound of the present invention can be used as a herbicide for paddy fields in any treatment method such as soil treatment under flooded water and foliar treatment. Paddy weed (Pa
Examples of ddy weeds include, for example, gramineae weeds typified by Echinochloa crus-galli and the like, Alisma canaliculatu.
m ), Japanese sardine ( Sagittaria trifol
ia ), Urikawa ( Sagittaria pygma )
ea ) etc.
eae) Weeds, Cyperus dif
formis ), Cyperus se ( Cyperus se )
rotinus ), firefly ( Sirrpus jun )
Coides ), Kurogui ( Eleocharis )
Kuroguwai ) and other weeds, Cyperaceae weeds, Adena ( Lindem )
nia pyxidaria) and the weeding mallow family (Schothularia aceae) weeds, and the pearl oyster family ( Monochoria vaginalis ).
e) Weeds, Potamogetondis
tinctus ) and other representatives of the family Amphiaceae (Pot
amogetonaceae) weed, yellow cypress ( Ro
and the weeds of the Lythraceae family represented by Tala indica ).

Next, the usefulness of the compound of the present invention as a herbicide will be specifically described in the following test examples. [Test Example-1] Herbicidal effect test by waterlogging treatment After alluvial soil was put in a 1/5000 are Wagner pot, water was added to mix it to obtain a waterlogging condition with a water depth of 4 cm. After sowing the seeds of Novier in the above pot, 2.5
Leaf stage rice seedlings were transplanted. The pot was placed in a greenhouse at 25 to 30 ° C. to grow a plant, and on the third day after sowing, the drug diluent was added dropwise to the water surface with a measuring pipette so that a predetermined drug amount was obtained. Three weeks after the dropping of the drug, the herbicidal effect on rice and millet was visually examined according to the following criteria.
The results are shown in Table 1. The compound of the present invention has selectivity for rice.

Criteria 5 ... Herbicide rate 90% or more (almost complete death) 4 ... Herbicide rate 70-90% 3 ... Herbicide rate 40-70% 2 ... Herbicide rate 20-40% 1 ... Herbicide rate 5 to 20% 0 ... Herbicidal rate 5% or less (almost no effect) [Test example-2] Test of herbicidal effect on growing season by flooding treatment After putting alluvial soil in a 1/5000 ares Wagner pot, water was added. The mixture was put in and mixed, and the water was submerged at a depth of 4 cm. After sowing the seeds of Novier in the above pot, 2.5
Leaf stage rice seedlings were transplanted. The pot is placed in a greenhouse at 25 to 30 ° C. to grow plants, and when the Nobye reaches the 1 to 2 leaf stage and the rice reaches the 4 leaf stage, the prescribed amount of water is given,
The drug diluted solution was dropped by a measuring pipette. Test Example 1 for herbicidal effect on rice and millet 3 weeks after dropping the medicine
According to the judgment standard of No. 1, it was visually inspected. The results are shown in Table 2. However, Comparative Compound A and Comparative Compound D in the table
Is the same compound as in Test Example 1.

[Table 1]

[Table 1] ────────────────────────────── Compounds Treatment amount Novie Transplanted rice g / a ─────── ──────────────────────── Present Invention 0.01 5 0 Compound 0.04 5 0 0.16 5 0 ───────── ────────────────────── Comparison 0.01 0 0 Compound A 0.04 2 0 0.16 4 0 ───────── ───────────────────── Comparison 0.01 0 0 Compound B 0.04 2 0 0.16 4 0 ────────── ──────────────────── Comparative comparison 0.01 0 0 Compound C 0.04 2 0 0.16 4 0 ─────────── ─────────────────── Comparison 0.01 0 Compound D 0. 42 0 0.16 40 0 ────────────────────────────── Comparative Compounds A to D; Published Japanese Patent Application No. 5-501236 Compounds described in the publication

[0077]

[Chemical 20]

[Table 2]

[Table 2] ────────────────────────────── Compounds Treatment dosage Novie Transplanted rice g / a ────── ──────────────────────── 0.01 40 The present invention 0.04 50 Compound 0.16 5 0 0.64 50 ─── ─────────────────────────── 0.01 0 0 Comparison 0.04 1 0 Compound A 0.16 3 0 0.64 5 2 ────────────────────────────── 0.01 0 0 Ratio comparison 0.04 0 0 Compound D 0.16 4 0 0.64 5 2 ──────────────────────────────

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Takeshi Nagaoka 1 722 Tsuboi-cho, Funabashi-shi, Chiba Central Research Laboratory, Nissan Chemical Industries, Ltd. (72) Toshio Niki 722 Tsuboi-cho, Funabashi, Chiba 1 Nissan Chemical Kogyo Co., Ltd. Central Research Institute (72) Inventor Koichi Suzuki 1470 Shiraoka, Shiraoka-cho, Minami-Saitama-gun, Saitama Nissan Chemical Industry Co., Ltd. Bioscience Research Institute (72) Inventor Namaki, Shirooka, Shirooka-cho, Minami-Saitama-gun, Saitama 1470 Nissan Kagaku Kogyo Co., Ltd.Biological Sciences Research Institute (72) Inventor Shigeomi Watanabe Large Shiraoka 1470, Shiraoka-cho, Minami Saitama-gun, Saitama Prefecture Nissan Kagaku Kogyo Co. Ltd. Bioscience Research (72) Inventor, Kimihiro Ishikawa 1470 Shiraoka Nissan Kagaku Kogyo Co., Ltd.

Claims (2)

[Claims] 1. Formula (1): A chloroethoxy thiazolidine derivative represented by or a salt thereof. 2. A selective herbicide containing the compound according to claim 1 as an active ingredient.