JP2003096059A - Thiazole compound and herbicidal composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thiazole compound and a herbicidal composition containing said thiazole compound as the effective ingredient. SOLUTION: The thiazole compound is represented by formula (I), [wherein, R<1> is a halogen atom; R<2> and R<3> are each the same or different from each other, and is hydrogen atom, a 1-4C alkyl group or a benzyl group; X represents a halogen atom, a 1-4C alkyl group, a 1-4C haloalkyl group, a 1-4C alkoxycarbonyl group or a nitro group; m represents an integer of 0 to 3; Xs are the same or different from each other; n represents an integer of 0 to 2], and the herbicidal composition contains said thiazole compound as the effective ingredient.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a thiazole compound and a herbicidal composition containing the thiazole compound as an active ingredient.

[0002]

Many herbicides have been found and used to date. In paddy fields, weed control is mainly performed with a herbicide that is a mixture of a fly mill and a sulfonylurea herbicide.

[0003]

However, it has been recognized that there are many cases where the firefly is left over. Therefore, in order to control difficult-to-control weeds such as firefly, an additional mixture of scallops has come to be used. Although the effect is expected by mixing various kinds of drugs, the cost is increased and the user is economically burdened. Therefore, it has been earnestly desired to develop a compound which has an effect on all annual weeds in paddy fields and has a controlling effect on Cyperaceae weeds such as firefly as well as on the fly.

By the way, many compounds having a thiazole ring are known. For example, Pesticide Sc
ience, 31, 65 (1991), a 5-cyanothiazole compound represented by the following formula (A) is described as a photo-involved herbicide.

[0005]

[Chemical 4]

However, there is no description of the 5-cyanothiazole compound (A) as a herbicide for paddy fields. The object of the present invention is, particularly for paddy weeds, a compound having a wide herbicidal spectrum with a low dosage, and having sufficient herbicidal activity even for all annual weeds including fireflies and firefly, and the thiazole compound is effective. To provide a herbicide composition as an ingredient.

[0007]

The present invention relates to a thiazole compound represented by the formula (1) and a herbicidal composition containing the thiazole compound as an active ingredient.

[0008]

[Chemical 5]

[In the formula, R ¹ represents a halogen atom. R ²
And R ³ are the same or different and each represents a hydrogen atom, a C _1-4 alkyl group or a benzyl group. X is a halogen atom, C _1-4
An alkyl group, a C _1-4 haloalkyl group, a C _1-4 alkoxycarbonyl group and a nitro group are shown. m represents an integer of 0 to 3. The m Xs may be the same or different. n represents an integer of 0 or 2. According to the present invention, it is possible to obtain an excellent herbicidal effect with low dosage on agricultural and horticultural weeds, especially paddy weeds.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The thiazole compound represented by the above formula (1) includes the following compound (2) in which n in the formula (1) is 0.

[0011]

[Chemical 6]

[In the formula, R ¹ represents a halogen atom. R ²
And R ³ are the same or different and each represents a hydrogen atom, a C _1-4 alkyl group or a benzyl group. X is a halogen atom, C _1-4
An alkyl group, a C _1-4 haloalkyl group, a C _1-4 alkoxycarbonyl group and a nitro group are shown. m represents an integer of 0 to 3. The m Xs may be the same or different. ]

The thiazole compound represented by the formula (1) has the following compound (3) in which n in the formula (1) is 2.
Includes.

[0014]

[Chemical 7]

[In the formula, R ¹ represents a halogen atom. R ²
And R ³ are the same or different and each represents a hydrogen atom, a C _1-4 alkyl group or a benzyl group. X is a halogen atom, C _1-4
An alkyl group, a C _1-4 haloalkyl group, a C _1-4 alkoxycarbonyl group and a nitro group are shown. m represents an integer of 0 to 3. The m Xs may be the same or different. ]

Specific examples of the groups shown in the present specification include the following. As a halogen atom,
For example, fluorine atom, chlorine atom, bromine atom, iodine atom and the like can be mentioned.

The C _1-4 alkyl group includes, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n
-Butyl group, sec-butyl group, tert-butyl group and the like can be mentioned. Examples of the C _1-4 haloalkyl group include a fluoromethyl group, a chloromethyl group, a bromomethyl group, an iodomethyl group, a difluoromethyl group, a trifluoromethyl group, a 2-fluoroethyl group, a 2-chloroethyl group, a 1-fluoroethyl group, 1-fluoropropyl group,
2-chloropropyl group, 3-fluoropropyl group, 3-
Examples thereof include a chloropropyl group, a 1-fluorobutyl group, a 1-chlorobutyl group and a 4-fluorobutyl group.

Examples of the C _1-4 alkoxycarbonyl group include alkoxy groups such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, isobutoxycarbonyl group and tert-butoxycarbonyl group. Examples thereof include an alkoxycarbonyl group having 1 to 4 carbon atoms.

Among the compounds of the present invention represented by the above formula (1)
But R¹Is a chlorine atom, R^TwoAnd R ^ThreeIs a hydrogen atom, X is
Halogen atom or haloalkyl group, n is 2, m is 1 to 3
Are preferred. This is represented by the above formula (1)
R among the bright compounds¹Is a chlorine atom, R^TwoAnd R ^ThreeBut water
Elementary atom, X is chlorine atom, n is 2, m is 2 to 3
Compounds are particularly preferred.

The thiazole compound represented by the formula (1) of the present invention can be produced by various methods. For example, the thiazole compound represented by the formula (2) has the following reaction formula-
It is manufactured by the method shown by 1.

[0021]

[Chemical 8] [In the formula, R ¹ , X and m are the same as defined above. ]

According to reaction formula-1, the thiazole compound of the present invention represented by the formula (2) [2a] is obtained by reacting the thiazole compound of the formula (6) with a halogenating agent in a suitable solvent. A compound in which n in the thiazole compound represented by the formula (1) is 0 and R ² and R ³ are hydrogen atoms] is produced.

As the solvent used in this reaction, a solvent inert to the reaction can be used. For example, hydrocarbons such as hexane, cyclohexane and heptane, aromatic carbons such as benzene, chlorobenzene, toluene and xylene. Hydrogen, methylene chloride, dichloroethane, chloroform, carbon tetrachloride and other halogenated hydrocarbons, ethyl acetate, methyl acetate and other esters, diethyl ether, tetrahydrofuran, dioxane and other ethers, acetonitrile, propionitrile and other nitriles Examples thereof include alcohols such as methanol, ethanol and isopropyl alcohol, amides such as N, N-dimethylformamide and N, N-diethylformamide, and sulfoxides such as dimethylsulfoxide. Also, a mixed solvent of these may be used.

As the halogenating agent, chlorine gas, bromine,
Sulfuryl chloride, N-chlorosuccinimide, N-
Examples thereof include bromosuccinimide. In this reaction, the compound of the formula (6) and the halogenating agent can be used in arbitrary ratios, but it is preferable that the latter is 0.8 to 1.5 mol with respect to 1 mol of the former. . This reaction is -20 ℃
To the boiling temperature of the solvent used, and it is usually completed in about 0.5 to 24 hours.

The thiazole compound represented by the formula (6) used in the reaction formula-1 can be produced, for example, by the method shown in the reaction formula-2 below.

[0026]

[Chemical 9] [In the formula, X and m are the same as above. ]

According to Reaction formula-2, 2-aminothiazole (4) is represented by formula (6) by reacting 2-aminothiazole (4) with a diazotizing agent and a benzyl disulfide compound represented by formula (5). Thiazole compounds can be prepared.

As the solvent used in this reaction, a solvent inert to the reaction can be used. For example,
Hydrocarbons such as hexane, cyclohexane, heptane,
Aromatic hydrocarbons such as benzene, chlorobenzene, toluene and xylene, halogenated hydrocarbons such as methylene chloride, dichloroethane, chloroform and carbon tetrachloride, esters such as ethyl acetate and methyl acetate, diethyl ether, tetrahydrofuran, dioxane, etc. Ethers,
Examples thereof include nitriles such as acetonitrile and propionitrile, alcohols such as methanol, ethanol and isopropyl alcohol, amides such as N, N-dimethylformamide and N, N-diethylformamide, and sulfoxides such as dimethylsulfoxide. Moreover, these mixed solvents and the mixed solvent of these and water can also be used. The amount of these solvents used may be about 0.05 to 500 liters, preferably about 0.5 to 20 liters, per kg of the compound represented by the formula (6).

As the diazotizing agent, nitrites such as isoamyl nitrite and nitrites such as sodium nitrite can be used. In this reaction, 2-aminothiazole (4), the benzyl disulfide compound represented by the formula (5) and the diazotizing agent can be used in any proportions, but preferably 2-aminothiazole (4) 1 It is preferable that the benzyl disulfide compound represented by the formula (5) is 0.8 to 3 mol and the diazotizing agent is 0.8 to 4 mol per mol. The reaction is preferably carried out in the temperature range from -20 ° C to the boiling temperature of the solvent used, and usually 0.1 to
It will be completed in about 40 hours.

The starting material 2-aminothiazole (4) is a known compound, and a commercially available product can be used. The benzyl disulfide compound (5) is also a known compound, and can be easily prepared according to the method described in the literature, for example, Tetrahed.
The method described in ron 35, 2329 (1979) can be used. The thiazole compound represented by the formula (6) produced by this reaction had no control effect on paddy weeds or was far inferior to the compounds of the present invention.

The thiazole compound represented by the formula (3) can be produced by the reaction represented by the following reaction formula-4.

[0032]

[Chemical 10] [In the formula, R ¹ , X and m are the same as defined above. ]

According to the reaction formula-3, the thiazole compound represented by the formula (2a) prepared by the reaction represented by the reaction formula-1 is oxidized in a solvent to obtain the compound represented by the formula (3). The thiazole compound of the present invention represented [3a:
N in the thiazole compound represented by the formula (1) is 2,
A compound in which R ² and R ³ are hydrogen atoms is produced.

As the solvent used in this reaction, a solvent inert to the reaction can be used. For example,
Hydrocarbons such as hexane, cyclohexane, heptane,
Aromatic hydrocarbons such as benzene, chlorobenzene, toluene and xylene, halogenated hydrocarbons such as methylene chloride, dichloroethane, chloroform and carbon tetrachloride, esters such as ethyl acetate and methyl acetate, diethyl ether, tetrahydrofuran, dioxane, etc. Ethers,
Nitriles such as acetonitrile and propionitrile, alcohols such as methanol, ethanol and isopropyl alcohol, amides such as N, N-dimethylformamide and N, N-diethylformamide, sulfoxides such as dimethylsulfoxide, and carvone such as acetic acid. Acids and water are mentioned. Also, a mixed solvent of these may be used. The amount of these solvents used may be about 0.05 to 500 liters, preferably about 0.5 to 20 liters per kg of the compound represented by the formula (2a).

In this reaction, a generally used oxidation reaction from sulfide to sulfoxide can be used. Examples of the oxidizing agent used in this reaction include metachloroperbenzoic acid, hydrogen peroxide, peracetic acid, permanganate, hydroperoxide, potassium peroxysulfate, sodium perborate, sodium metaperiodate, osmium oxide, ruthenium oxide. , Nitric acid, chromic acid, sodium dichromate,
Examples thereof include halogen, sodium hypochlorite, iodobenzene dichloride, ozone and singlet oxygen.

The oxidizing agent may be used in a stoichiometric amount or in excess of the thiazole compound represented by the formula (2a), but is preferably a stoichiometric amount or 2 to 5 times. It is better to use an excessive amount. This reaction is usually carried out preferably in the temperature range from -20 ° C to the boiling temperature of the solvent used, and is usually completed in about 0.5 to 24 hours. Furthermore, the thiazole compound represented by the formula (3) is produced by the method represented by the following reaction formula-4.

[0037]

[Chemical 11] [In the formula, R¹, X and m are the same as above. R²¹And R
³¹Are the same or different and are C _1-4Alkyl group or benzyl
Represents a radical. ]

According to the reaction formula-4, the thiazole compound of the present invention represented by the formula (3a) prepared by the reaction represented by the reaction formula-3 is added to the alkylating agent in the presence of a base in a solvent. Or by reacting with a benzylating agent,
Thiazole compound represented by formula (3) [3b: formula (1)
In the thiazole compound represented by, n is 2 and R ² is R
²¹ , a compound in which R ³ is a hydrogen atom, 3c: n in the thiazole compound represented by the formula (1) is 2, R
² is R ²¹ and R ³ is R ³¹ ] is obtained.

The reaction for producing the thiazole compound represented by the formula (3b) from the thiazole compound of the present invention represented by the formula (3a) is preferably carried out as follows. As the solvent used, for example, hexane, heptane, aliphatic hydrocarbons such as pentane, alicyclic hydrocarbons such as cyclohexane, benzene, toluene, aromatic hydrocarbons such as xylene, dichloromethane, chloroform,
1,2-dichloroethane, 1,1,1-trichloroethane, tetrachloroethylene, trichloroethylene, carbon tetrachloride, chlorobenzene, halogenated hydrocarbons such as o-dichlorobenzene, alcohols such as methanol, ethanol and isopropanol, diethyl ether, Isopropyl ether, tetrahydrofuran, dioxane,
Ethers such as monoglyme, esters such as methyl formate, methyl acetate, ethyl acetate, butyl acetate and methyl propionate, N, N-dimethylformamide, N, N-dimethylacetamide, 1,3-dimethylimidazolidinone, etc. Examples thereof include amides, nitriles such as acetonitrile, sulfoxides such as dimethyl sulfoxide, water, and a mixed solvent thereof.

The amount of these solvents used may be about 0.05 to 500 liters, preferably about 0.5 to 20 liters, per kg of the compound represented by the formula (3a). Examples of the alkylating agent used in this reaction include alkyl halides such as methyl iodide, methyl bromide and ethyl bromide, and sulfuric acid esters such as dimethylsulfate and ethyl methanesulfonate. Examples of the benzylating agent used in this reaction include benzyl chloride and benzyl bromide. The alkylating agent or benzylating agent is used in an amount of 0.8 to 1.6 equivalents, preferably 1 to 1.1 equivalents, based on the thiazole compound represented by the formula (3a).

This reaction is preferably carried out in the presence of a base. Examples of the base used include alkali metal alkoxides such as sodium methoxide, sodium ethoxide and potassium tert-butoxide, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal salts such as sodium carbonate and potassium carbonate. Examples thereof include carbonates, alkali metal hydrides such as sodium hydride, organic bases such as triethylamine, pyridine and DBU, and lithium salts such as butyllithium, lithium diisopropylamide and lithium bistrimethylsilylamide. These bases can be used alone or in combination of two or more, and the amount thereof used is 0.8 to 5 equivalents, preferably 1 to 1.1 equivalents to the thiazole compound represented by the formula (3a). Is good. This reaction can be arbitrarily set within the range of -100 ° C to the boiling temperature of the solvent used. Although the reaction time is not particularly limited, about 10 minutes to 24 hours is usually sufficient.

In the reaction for producing the thiazole compound represented by the formula (3c) from the thiazole compound represented by the formula (3b) produced in the above reaction, the kind and amount of the solvent used and the alkyl used. The thiazole compound represented by the formula (3b) from the thiazole compound represented by the above formula (3a) in terms of the type and amount of the oxidizer or benzylating agent, the type and amount of the base used, the reaction temperature and the reaction time. The reaction may be the same as the reaction for producing the compound.

The reaction for producing the thiazole compound represented by the formula (3b) from the thiazole compound represented by the formula (3a) and then the thiazole compound represented by the formula (3c) is performed by the reaction of the formula (3c). It is particularly effective when R ²¹ and R ³¹ of the thiazole compound represented by are different.

Formula (3c) in which R ²¹ and R ³¹ are the same
In the case of producing the thiazole compound represented by the formula (3), the thiazole compound represented by the formula (3a) can be directly produced by adjusting the amounts of the alkylating agent or the benzylating agent and the base used. In this case, the amount of the alkylating agent or benzylating agent used is 1.8 to 10 equivalents, preferably 2 to 3 equivalents based on the thiazole compound represented by the formula (3a). The amount of the base used is 1.8 with respect to the thiazole compound represented by the formula (3a).
It is good to use 10 to 10 equivalents, preferably 2 to 3 equivalents.

The type and amount of the solvent used, the type of alkylating agent or benzylating agent used, the type of base used, the reaction temperature and the reaction time can be calculated from the thiazole compound represented by the formula (3a). The reaction may be similar to the reaction for producing the thiazole compound represented by (3b). Each compound obtained in each of the above reactions can be separated by an ordinary separation means, for example,
It is easily isolated and purified from the reaction mixture by a conventional isolation and purification means such as an organic solvent extraction method, a chromatography method and a recrystallization method.

The compound of the present invention and a herbicidal composition containing the compound as an active ingredient act effectively on a wide variety of weeds, which are a major agricultural and horticultural problem. It shows excellent herbicidal activity against paddy field weeds.

Further, the herbicidal composition containing the compound of the present invention as an active ingredient is effective in foliar treatment and soil treatment, but exhibits a particularly excellent herbicidal effect in flooded treatment. Although the mechanism of action of the compound of the present invention is unknown,
It is considered that this is a completely different action, because no rapid onset of effects peculiar to light-involved herbicides and browning of the drug contact part were observed.

When the compound of the present invention is used as a herbicide, it may be used as it is without adding other components, but it is usually mixed with various carriers such as liquid, solid and gas, and further if necessary. Depending on the addition of surfactants and other formulation aids, emulsions, wettable powders, dry flowables, flowables, water solutions, granules, fine granules, granules, powders, coatings, spray formulations, It can be used by formulating it into various formulation forms such as an aerosol formulation, a microcapsule formulation, a fumigation formulation and a fumigation formulation.

In these preparations, the content of the compound of the present invention as an active ingredient can be appropriately selected from a wide range according to various conditions such as the form of the preparation and the place of use, but is usually 0.01.
˜95% by weight, preferably 0.1 to 50% by weight. Examples of solid carriers used in preparing these formulations include kaolin clay, diatomaceous earth, bentonite, fubasami clay, clay such as acid clay, talc, ceramics, celite, quartz, sulfur, activated carbon, silica carbonate, hydrated silica. Inorganic minerals such as, fine powders of chemical fertilizers, granules and the like.

Examples of the liquid carrier include water, alcohols, ketones such as acetone and methyl ethyl ketone, hydrocarbons such as hexane, cyclohexane, kerosene and light oil, aromatic hydrocarbons such as benzene, toluene, xylene and naphthalene, Esters such as ethyl acetate and butyl acetate, nitriles such as acetonitrile and isobutyronitrile, ethers such as diisopropyl ether and dioxane,
Examples thereof include acid amides such as N, N-dimethylformamide and N, N-dimethylacetamide, halogenated hydrocarbons such as dichloromethane, trichloroethane and carbon tetrachloride, and vegetable oils such as dimethyl sulfoxide, soybean oil and cottonseed oil.

The gaseous carrier is one generally used as a propellant, and examples thereof include butane gas, liquefied petroleum gas, dimethyl ether, carbon dioxide gas and the like. Specific examples of the surfactant include, for example, polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyethylene sorbitan alkyl ester and the like as the nonionic surfactant, and alkylbenzene sulfonate and alkyl sulfo as the anionic surfactant. Examples thereof include succinate, alkyl sulfate, polyoxyethylene alkyl sulfate, allyl sulfonate, and lignin sulfite.

Examples of the auxiliaries for the formulation include a sticking agent,
Examples thereof include dispersants and stabilizers. Examples of fixing agents and dispersants include casein, gelatin, polysaccharides (starch, gum arabic, cellulose derivatives, alginic acid, etc.), lignin derivatives, bentonite, saccharides, synthetic water-soluble polymers (polyvinyl alcohol, polyvinylpyrrolidone, polyacryl). Acids, etc.) and the like. As the stabilizer, for example, PAP (isopropyl acid phosphate), BHT (2,
6-di-tert-butyl-4-methylphenol).
Examples thereof include BHA (mixture of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol), vegetable oil, mineral oil, surfactant, fatty acid or its ester. These formulations may be colored with organic and inorganic dyes.

The preparation thus obtained can be used as it is or after diluted with water or the like. However, granules,
Dust and the like are usually used as they are without dilution. When an emulsion, wettable powder, flowable agent or the like is diluted with water or the like, the active ingredient concentration is usually 0.0001 to 1
The amount may be about 00% by weight, preferably about 0.001 to 10% by weight.

Further, the compounds of the present invention are used as other herbicides, insecticides, nematicides, acaricides, fungicides, plant growth regulators,
You may formulate by mixing with a synergist (for example, piperonyl butoxide), a soil conditioner, etc. beforehand. Alternatively, the formulation of the present invention and each of the above agents may be used together when used.

When the compound of the present invention is used as a herbicide, its application amount is not particularly limited, and various types such as formulation form, application method, application time, application site, type of applied crop, type of weeds to be weeded, etc. It is appropriately selected from a wide range according to the conditions. For example, when a foliage treatment method, a soil treatment method, or a waterlogging treatment method is performed, the amount of active ingredient is 10,000 m ²
Usually about 1 to 4000 g, preferably 10 to 10 g
It may be about 00 g.

[0056]

EXAMPLES The production examples of the starting materials for producing the compound of the present invention will be given below as reference examples, and the production examples of the compound of the present invention will be given below as examples. In the following, simply "parts" means "parts by weight".

Reference Example 1 Synthesis of compound (6) Synthesis of 2- (2,6-dichlorobenzylthio) thiazole (1) Synthesis of bis (2,6-dichlorobenzyl) disulfide Sodium sulfide nonahydrate 17.2 g (71.4 mmol)
And 2.3 g (71.4 mmol) of sulfur in ethanol 10
It was suspended in 0 ml and heated to reflux with stirring for 10 minutes.
After cooling to room temperature, an ethanol solution 4 of 18.5 g (95 mmol) of 2,6-dichlorobenzyl chloride 4
0 ml was added dropwise over 5 minutes. Heated reflux was performed with stirring for 2 hours. The reaction solution was returned to room temperature, concentrated under reduced pressure, 200 ml of water was added to the obtained residue, and the mixture was extracted 3 times with 50 ml of diethyl ether. The obtained diethyl ether extract was dried over anhydrous magnesium sulfate, concentrated and dried under reduced pressure to give bis (2,6-dichlorobenzyl) disulfide as a white solid. Yield 19 g Yield 100% ¹ H-NMR (300 MHz, CDCl ₃ , δpp
m): 7.35-7.25 (4H, m), 7.20-7.1
0 (2H, m), 4.28 (4H, s)

(2) Synthesis of 2- (2,6-dichlorobenzylthio) thiazole Under a nitrogen atmosphere, 19 g (50 mmol) of bis (2,6-dichlorobenzyl) disulfide obtained above and 5.0 g of 2-aminothiazole were obtained. While stirring 120 ml of a dichloromethane solution of (50 mmol) at room temperature, tert-nitrite was added.
-A mixed solution of 12 ml (100 mmol) of butyl and 10 ml of dichloromethane was added dropwise over 10 minutes. The mixture was stirred at room temperature for 18 hours, concentrated under reduced pressure, and the obtained crude product was purified by silica gel column chromatography (hexane: ethyl acetate = 15: 1) to give 2- (2,6-dichlorobenzylthio). The thiazole was obtained as an orange liquid. Yield 2.7 g Yield 19.6% ¹ H-NMR (300 MHz, CDCl ₃ , δpp
m): 7.76 (1H, d, J = 3.3Hz), 7.33
-7.24 (3H, m), 7.20-7.10 (1H,
m), 4.74 (2H, m)

Example 1 Synthesis of 2- (2,6-dichlorobenzylthio) -5-chlorothiazole (Compound No. 7) 2- (2,6-dichlorobenzylthio) under nitrogen atmosphere
2.2 g (6.44 mmol) of thiazole was dissolved in 15 ml of dimethylformamide and heated to 45 ° C. With stirring, 0.58 ml of sulfuryl chloride (6.44 mmo
A mixed solution of 1) and 5 ml of chloroform was added dropwise over 1.5 hours. After stirring for 2.5 hours as it was, a mixed solution of 0.01 ml (0.06 mmol) of sulfuryl chloride and 1 ml of chloroform was added dropwise over 0.5 hour.
After stirring for 6 hours, the temperature was returned to room temperature, and the reaction solution was poured into 100 ml of water. The resulting solution is 25 ml of hexane
The resulting hexane solution was dried over anhydrous magnesium sulfate and then dried under reduced pressure. The obtained crude product was purified by silica gel column chromatography (hexane: ethyl acetate = 15: 1) to obtain 2- (2,6-dichlorobenzylthio) -5-chlorothiazole as a yellow liquid. Yield 1.96 g Yield 79.2% ¹ H-NMR (300 MHz, CDCl ₃ , δpp
m): 7.63 (1H, s), 7.34-7.29 (2
H, m), 7.18-7.14 (1H, m), 4.69
(2H, s)

Example 2 2- (2,6-dichlorobenzylsulfonyl) -5-
Synthesis of chlorothiazole (Compound No. 28) 1.8 g (5.22 mmol) of 2- (2,6-dichlorobenzylthio) -5-chlorothiazole and 2.7 g (15.7 mmol) of metachloroperbenzoic acid were added to chloroform 30.
It was dissolved in ml and stirred as it was at room temperature for 2 hours. The reaction mixture was washed with 10% aqueous sodium hydroxide solution, magnesium sulfate was added, and the mixture was dried. After removing magnesium sulfate by filtration, the chloroform solution was dried under reduced pressure, and the obtained crude product was purified by silica gel column chromatography (hexane: ethyl acetate = 4: 1) to give 2-
(2,6-Dichlorobenzylsulfonyl) -5-chlorothiazole was obtained as a white solid. Yield 1.42 g Yield 71.5% ¹ H-NMR (300 MHz, CDCl ₃ , δpp
m): 7.88 (1H, s), 7.39-7.25 (3
H, m), 5.12 (2H, s)

Example 3 Synthesis of 2- (2,6-dichloro-α-methylbenzylsulfonyl) -5-chlorothiazole (Compound No. 40) 2- (2,6-dichlorobenzylsulfonyl) -5 under nitrogen atmosphere -Chlorothiazole 0.2 g (0.584 m
mol) and methyl iodide 0.1 g (0.642 mmol)
Was dissolved in 20 ml of dehydrated dimethylformamide. 0 ° C
60% oily substance of sodium hydride under stirring at 0.03 g
(0.642 mmol) was added. After stirring as it was at room temperature overnight, the reaction solution was added to 200 ml of water, and the mixture was extracted 3 times with 30 ml of diethyl ether. The obtained diethyl ether solution was washed with water and dried over anhydrous magnesium sulfate,
It was concentrated to dryness under reduced pressure. The obtained crude product was subjected to silica gel column chromatography (hexane: ethyl acetate = 4:
Purification in 1) gave 2- (2,6-dichloro-α-methylbenzylsulfonyl) -5-chlorothiazole as a white solid. Yield 0.26 g Yield 100% ¹ H-NMR (300 MHz, CDCl ₃ , δpp
m): 7.85 (1H, s), 7.39-7.35 (2
H, m), 7.27-7.20 (1H, m), 5.82
(1H, q, J = 7.27Hz), 2.0 (3H, d, J
= 7.27Hz)

Example 4 2- (2,6-Dichloro-α, α-dimethylbenzylsulfonyl) -5-chlorothiazole (Compound No. 44)
Synthesis of 2- (2,6-dichloro-α-methylbenzylsulfonyl) -5-chlorothiazole 0.2 g (0.561 mm
ol) and methyl iodide 0.088 g (0.617 mmo)
l) was dissolved in 20 ml of dehydrated dimethylformamide. Under stirring at 0 ° C., 0.1 g (0.617 mmol) of a 60% oily substance of sodium hydride was added. After stirring as it was at room temperature overnight, the reaction solution was added to 200 ml of water, and the mixture was extracted 3 times with 30 ml of diethyl ether. The obtained diethyl ether solution was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to dryness. The obtained crude product was purified by silica gel column chromatography (hexane: ethyl acetate = 4: 1) to give 2- (2,6-dichloro-α, α).
-Dimethylbenzylsulfonyl) -5-chlorothiazole was obtained as a pale yellow solid. Yield 0.18 g Yield 86.6% ¹ H-NMR (300 MHz, CDCl ₃ , δppm):
7.84 (1H, s), 7.37-7.30 (2H, m), 7.
17-7.10 (1H, m), 2.43 (6H, s) The compounds of the present invention shown in Tables 1 and 2 below were produced according to any of the methods in the above Production Examples. In addition, Tables 3 to 6 show physical properties and the like of each compound. The ¹ H-NMR spectrum was measured using tetramethylsilane (TMS) as a standard substance.

[0063]

[Table 1]

[0064]

[Table 2]

[0065]

[Table 3]

[0066]

[Table 4]

[0067]

[Table 5]

[0068]

[Table 6]

Formulation examples are shown below.

Formulation Example 1 (Emulsion) 10 parts of each of the compounds of the present invention were added to 45 parts of Solvesso 150.
Parts and 35 parts of N-methylpyrrolidone, 10 parts of an emulsifier (trade name: Solpol 3005X, manufactured by Toho Kagaku Co., Ltd.) were added, and mixed by stirring to obtain 10% emulsions of each.

Formulation Example 2 (wettable powder) 20 parts of each of the compounds of the present invention were mixed with 2 parts of sodium lauryl sulfate, 4 parts of sodium ligninsulfonate, 20 parts of synthetic silicon oxide hydroxide fine powder and 54 parts of clay. In addition, 20% wettable powder was obtained by stirring and mixing with a juice mixer.

Production Example 3 (Granule) 5 parts of each of the compounds of the present invention, 2 parts of sodium dodecylbenzenesulfonate, 10 parts of bentonite and 8 parts of clay.
3 parts were added and mixed thoroughly with stirring. An appropriate amount of water was added, and the mixture was further stirred, granulated with a granulator, and dried under ventilation to obtain 5% granules.

Production Example 4 (powder) 1 part of each of the compounds of the present invention was dissolved in an appropriate amount of acetone,
To this, 5 parts of synthetic hydrous silicon oxide fine powder, 0.3 part of PAP (isopropyl acid phosphate) and 93.7 parts of clay were added, stirred and mixed with a juice mixer, and acetone was removed by evaporation to obtain a 1% powder. .

Formulation Example 5 (flowable agent) 20 parts of each of the compounds of the present invention, 3 parts of polyoxyethylene tristyrylphenyl ether phosphate triethanolamine, a silicone antifoaming agent [trade name: RHODO
RSIL 426R, RHODIA CH
20 parts of water containing 0.2 parts of IMIE Co., Ltd. was mixed and wet-milled using a mill (Dynomill, Willy A. Bachofen Co.), then 8 parts of propylene glycol,
20 parts by mixing with 60 parts water containing 0.32 parts xanthan gum
% Suspension in water was obtained.

Next, it will be shown that the compound of the present invention is useful as an active ingredient of a herbicide. The compounds of the present invention are shown by the compound numbers shown in Table 1.

Test Example 1 Test for herbicidal effect of waterlogging Styrene cups having a diameter of 8 cm (about 52 cm ² ) were filled with sieved (2 mm) soil (45 ml), and water (about 1) was added.
(15 ml) and mixed to make a submerged state. After leaving the bed for one day,
Seeds of eel, cypress tree, tadpole, and firefly were sown. Each of the compounds of the present invention was dissolved in acetone, and a chemical solution diluted with water containing Tween 80 was added dropwise to the front surface in the treatment section in an amount of 1 ml per section (amount of 2 kg / ha). After the treatment, the plants were grown in a glass room, and the herbicidal activity was visually examined on the 21st day and evaluated according to the following criteria. The results are shown in Table 7. 0: The growth suppression effect is less than 10%. 1: The growth suppression effect is 10% or more and less than 30%. 2: The growth suppression effect is 30% or more and less than 50%. 3: The growth suppression effect is 50% or more and less than 70%. 4: The growth suppression effect is 70% or more and less than 90%. 5: Growth inhibitory effect is 90% or more, or complete killing.

[0077]

[Table 7]

Test Example 2 Tests were conducted in the same manner as in Test Example 1 except that the compounds shown in Table 8 were selected from the compounds of the present invention produced in the above Production Example and the dosage was adjusted to 0.2 kg / ha. did. The results are shown in Table 8
Shown in.

[0079]

[Table 8]

[0080]

According to the present invention, especially against paddy weeds,
It is possible to obtain a compound having a wide herbicidal spectrum with a low dose and having sufficient herbicidal activity against all annual weeds including millet and firefly, and a herbicide composition containing the thiazole compound as an active ingredient. it can.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Tatsuya Akasaka             615 Hana, Satoura, Satoura-machi, Naruto City, Tokushima Prefecture             Otsuka Chemical Co., Ltd. Naruto Laboratory F-term (reference) 4C033 AD10 AD12 AD17                 4H011 AB02 BB10 DA02 DA15 DA16                       DD01

Claims (5)

[Claims] 1. A thiazole compound represented by the formula (1). [Chemical 1] [In the formula, R ¹ represents a halogen atom. R ² and R ³ are the same or different and each represents a hydrogen atom, a C _1-4 alkyl group or a benzyl group. X is a halogen atom, a C _1-4 alkyl group,
A _C1-4 haloalkyl group, a _C1-4 alkoxycarbonyl group, and a nitro group are shown. m represents an integer of 0 to 3. The m Xs may be the same or different. n represents an integer of 0 or 2. ] 2. A thiazole compound represented by the formula (2). [Chemical 2] [In the formula, R ¹ represents a halogen atom. R ² and R ³ are the same or different and each represents a hydrogen atom, a C _1-4 alkyl group or a benzyl group. X is a halogen atom, a C _1-4 alkyl group,
A _C1-4 haloalkyl group, a _C1-4 alkoxycarbonyl group, and a nitro group are shown. m represents an integer of 0 to 3. The m Xs may be the same or different. ] 3. A thiazole compound represented by the formula (3). [Chemical 3] [In the formula, R ¹ represents a halogen atom. R ² and R ³ are the same or different and each represents a hydrogen atom, a C _1-4 alkyl group or a benzyl group. X is a halogen atom, a C _1-4 alkyl group,
A _C1-4 haloalkyl group, a _C1-4 alkoxycarbonyl group, and a nitro group are shown. m represents an integer of 0 to 3. The m Xs may be the same or different. ] 4. A herbicidal composition comprising the thiazole compound according to claim 1 as an active ingredient. 5. A herbicide composition for paddy fields, which comprises the thiazole compound according to any one of claims 1 to 3 as an active ingredient.