JP4561068B2 - 2-Chloro-1,3-thiazole-5-methanol derivative, process for producing the same and agricultural and horticultural disease control agent - Google Patents

Description

  The present invention relates to a novel 2-chloro-1,3-thiazole-5-methanol derivative derivative and an agrochemical containing the compound as an active ingredient, particularly a plant disease control agent.

Regarding 1,3-thiazole-5-methanol derivatives, its use is known as a disinfectant.
JP-A-5-255268

In addition, regarding 1,3-thiazole-5-methyl derivatives, use as a bactericidal agent is also known.
JP 62-59276 A

  On the other hand, the 2-chloro-1,3-thiazole-5-methanol derivative according to the present invention undergoes a reduction reaction using, for example, 2-chloro-1,3-thiazole-5-carboxylic acid or an ester thereof as a starting material. Can be synthesized. However, the 2-chloro-1,3-thiazole-5-methanol derivatives of the present invention and 2-chloro-1,3-thiazole-5-methanol and 2-chloro-1,3-thiazole-5-methanol derivatives The use as an agricultural fungicide has never been known.

  An object of the present invention is to provide a novel compound having an excellent effect in controlling various plant diseases, a method for synthesizing the compound, and an agrochemical comprising a 2-chloro-1,3-thiazole-5-methanol derivative as an active ingredient, particularly It is to provide a plant disease control agent.

  The present inventors have eagerly created a novel agricultural and horticultural disease control agent that has low toxicity to human livestock, is highly safe in handling, and exhibits an excellent control effect on a wide range of plant diseases. As a result of repeated research, the 2-chloro-1,3-thiazole-5-methanol derivative represented by the general formula (I) of the present invention is a novel compound not described in the literature, and is useful as an agricultural and horticultural disease control agent. Thus, the present invention has been completed.

  The present invention has been completed based on the above findings, and the first gist of the present invention is a 2-chloro-1,3-thiazole-5-methanol derivative represented by the following formula (I). Exist.

Wherein, R represents a hydrogen _atom; C 1 -C ₄ alkyl group; (unsubstituted or _C 1 -C ₄ alkyl _groups, the same or different are selected from the group of C 1 -C ₄ alkoxy group and a halogen atom It is substituted with 1-5 groups _phenyl) C 1 -C ₄ alkyl group; C ₃ -C ₆ alkenyl group; _(cyano) C 1 -C ₄ alkyl group; (unsubstituted or _C 1 -C ₄ alkyl group, C ₁ -C ₄ alkoxy and the same or different are selected from the group of halogen atoms is substituted with may also be one to five groups) tetrahydropyranyl group; C ₁ -C ₄ alkylcarbonyl group ; (unsubstituted or _C 1 -C ₄ alkyl _group, C 1 -C ₄ alkoxy group and the same or different substituted with may also be one to five groups phenyl is selected from the group of halogen atom) (C _{2 ~C 4} A Kenyir) carbonyl _group; C 1 -C ₄ haloalkylcarbonyl group; (unsubstituted or _C 1 -C ₄ alkyl _group, C 1 -C ₄ same or different and may 1 is selected from the group of alkoxy group and a halogen atom A phenyl group (substituted by 5 groups); (unsubstituted or C ₁ -C ₄ alkyl group, C ₁ -C ₄ alkoxy group and the same or different 1 to 4 selected from the group of halogen atoms) Thiazolyl substituted with ₁ group) C ₁ -C ₄ alkyl group; (unsubstituted or identical or different selected from the group of C ₁ -C ₄ alkyl group, C ₁ -C ₄ alkoxy group and halogen atom) _{isothiazolyl)} C 1 -C ₄ alkyl group substituted with may also be 1-4 groups; (unsubstituted or _C 1 -C ₄ alkyl _group, C 1 -C ₄ alkoxy and C Identical or different substituted with also good 1-4 groups pyridyl) carbonyl group is selected from the group of plasminogen atoms; (unsubstituted or C ₁ -C ₄ alkyl group, C ₁ -C ₄ alkoxy and A thiazolyl substituted with 1 to 4 groups which may be the same or different and selected from the group of halogen atoms; a carbonyl group; (unsubstituted or a C ₁ -C ₄ alkyl group, a C ₁ -C ₄ alkoxy group and Phenyl substituted with 1 to 5 groups, which may be the same or different, selected from the group of halogen atoms) C ₁ -C ₄ alkylsulfonyl group; or (unsubstituted or C ₁ -C ₄ alkyl group, C _{1 to} C4 represents a phenyl) sulfonyl group substituted with ₁ to ₄ alkoxy groups and 1 to 5 groups which may be the same or different and selected from the group of halogen atoms.

  A second gist of the present invention is a compound represented by the formula (I), characterized by reacting a compound represented by the following formula (II) with a compound represented by the following formula (III): -It exists in the manufacturing method of a chloro- 1, 3- thiazole-5-methanol derivative.

  In the formula, X and Y represent a leaving group or a hydroxyl group. R is the same as defined above.

  The third gist of the present invention resides in an agricultural and horticultural plant disease control agent comprising the 2-chloro-1,3-thiazole-5-methanol derivative described in the first gist as an active ingredient. .

Hereinafter, the present invention will be described in detail. Among the definitions of the substituents of the 2-chloro-1,3-thiazole-5-methanol derivative (hereinafter sometimes abbreviated as “the compound of the present invention”) represented by the above formula (I), The substituents shown include the following preferred substituents. C ₁ -C ₄ alkyl includes methyl, ethyl, 1-methylethyl, 1,1-dimethylethyl, propyl and 2-methylpropyl. The C ₁ -C ₄ alkoxy, methoxy, ethoxy, 1-methylethyl-oxy, 1,1-dimethylethyl oxy, propyloxy and 2-methyl-propyloxy and the like. And as a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom is mentioned.

  In preferred combinations of substituents, the compounds of the following Table 1 can be exemplified as the compounds of the present invention represented by the formula (I).

  The following can be illustrated as a diluent used with the manufacturing method of this invention. Water, organic acids such as formic acid, acetic acid and propionic acid, hydrocarbons such as benzene, toluene, xylene, petroleum ether, pentane, hexane and heptane, halogenated hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride, methanol , Ethanol, isopropanol, alcohols such as t-butanol, diethyl ether, dimethoxyethane, diisopropyl ether, ethers such as tetrahydrofuran, diglyme, dioxane, carbon disulfide, acetonitrile, acetone, ethyl acetate, acetic anhydride, pyridine, dimethylformamide Dimethylacetamide, 1-methyl-2-pyrrolidinone, dimethyl sulfoxide, hexamethylphosphoric amide and the like.

  The following can be illustrated as a base. Alkaline metal carbonates such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, alkaline earth metal carbonates such as calcium carbonate, barium carbonate, alkali metal such as sodium acetate, potassium acetate, sodium propionate Alkali metal hydroxides such as carboxylates, sodium hydroxide and potassium hydroxide, alkaline earth metal oxides such as magnesium oxide and calcium oxide, alkali metals such as lithium, sodium and potassium, alkaline earth such as magnesium Alkali metals, sodium methoxide, sodium ethoxide, alkali metal alkoxides such as potassium t-butoxide, alkali metal hydrides such as sodium hydride and potassium hydride, methyl lithium, ethyl lithium, n-butyl lithium, phenyl lithium Organic metal compounds of alkali metals, organic Grignard reagents such as methylmagnesium iodide, ethylmagnesium bromide, n-butylmagnesium bromide, etc., organometallic compounds of alkali metals, and organic copper compounds that can be prepared from Grignard reagents and copper (I) salts , Alkali metal amides such as lithium diisopropylamide, aqueous ammonia, ammonium hydroxides such as benzyltrimethylammonium hydroxide, tetramethylammonium hydroxide, methylamine, ethylamine, n-propylamine, benzylamine, ethanolamine, dimethylamine, Organic amines such as benzylmethylamine, dibenzylamine, triethylamine, triethanolamine and pyridine.

  The compound represented by the general formula (I) of the present invention can be advantageously produced, for example, by formula (II) and formula (III) in a diluent in the presence of a base. In order to carry out the production method of the present invention, for example, the formula (III) is dissolved in the above-mentioned diluent, and, if necessary, the formula (III) Add 1.5 equivalents, or conversely, add Formula (II) and a base to a solution of Formula (III) dissolved in a diluent. As the reaction temperature at this time, any temperature from the freezing point to the boiling point of the diluent as the solvent can be applied, but in practice, the reaction is preferably performed at a temperature in the range of 0 to 100 ° C. The reaction time is in the range of 1 to 10 hours, and it is desirable to carry out the reaction with stirring. After completion of the above reaction, the reaction mixture obtained by the reaction is cooled, extracted with an organic solvent such as ethyl acetate, chloroform, benzene, etc. to separate the organic layer, and then the organic layer is washed with water and dried. A 2-chloro-1,3-thiazole-5-methanol derivative (I) can be obtained by distilling off the solvent under reduced pressure and purifying the resulting residue. The purification treatment can be performed by recrystallization or silica gel column chromatography.

  Next, the usefulness of the 2-chloro-1,3-thiazole-5-methanol derivative of the formula (I) according to the present invention as an active ingredient of an agricultural and horticultural disease control agent will be described. The 2-chloro-1,3-thiazole-5-methanol derivative (I) of the present invention exhibits a controlling effect against the following wide range of plant diseases. For example, rice blast (Pyricularia oryzae), rice sesame leaf blight fungus (Cochliobolus miyabeanus), rice blast fungus (Gibberella fujikuroi), rice black rot fungus (Helminthosporium sigmoideum), rice blight fungus (Rhizoctonia solani) Botrytis cinerea, Sclerotinia sclerotiorum, watermelon vine split fungus (Fusarium oxysporum f.sp.niveum), cucumber vine split fungus (Fusarium oxysporum f.sp.cucumerinum), cucurbits Colletotrichum lagenarium, sugar beet brown fungus (Cercospora beticola), soybean purpura fungus (Cercospora kikuchii), peach blight fungus (Sclerotinia cinerea), apple leaf spot fungus (Alternaria alternata (mali)), pear black spot fungus (Alternaria alternata (kikuchiana)), grape rot fungus (Glomerella cingulata), cucumber downy mildew (Pseudoperonosora cubensis), tomato plague (Phytophthra infestans), cucumber ash Phytophthora (Phytophthora capsici), rice seedling blight (Pythium aphanidermatum), and the like.

  In order to apply the 2-chloro-1,3-thiazole-5-methanol derivative (I) of the present invention as an agricultural and horticultural disease control agent as described above, the compound can be used as it is, but usually a formulation aid. Along with the preparation, it is formulated into various forms such as powders, wettable powders, granules and emulsions. At this time, in the preparation, one or more 2-chloro-1,3-thiazole-5-methanol derivatives (I) are 0.1 to 95% by weight, preferably 0.5 to 90% by weight, More preferably, it is formulated so as to contain 2 to 70% by weight. Examples of carriers, diluents and surfactants used as formulation aids include solid carriers such as talc, kaolin, bennite, diatomaceous earth, white carbon, clay, etc., and liquid diluents such as water, xylene , Toluene, chlorobenzene, cyclohexane, cyclohexanone, dimethyl sulfoxide, dimethylformamide, alcohol, etc., surfactants should be used properly depending on their effects, and as emulsifiers, polyoxyethylene alkyl aryl ether, polyoxyethylene sorbitan monolaurate Examples of the dispersant include lignin sulfonate and dibutyl naphthalene sulfonate, and examples of the wetting agent include alkyl sulfonate and alkylphenyl sulfonate. The above preparations include those that are used as they are and those that are diluted to a predetermined concentration with a diluent such as water. The concentration of the compound of the present invention when diluted is preferably in the range of 0.001 to 1.0%. Moreover, the usage-amount of this invention compound is 20-5000g normally, preferably 50-1000g per 1 ha of agricultural and horticultural lands such as a field, a rice field, an orchard, and a greenhouse. Since these use concentrations and amounts vary depending on the dosage form, use time, use method, use place, target crop, etc., it is of course possible to increase or decrease without sticking to the above range. Furthermore, the compound of the present invention can be used in combination with other active ingredients such as fungicides, insecticides, acaricides and herbicides. Incidentally, since this compound contains a carboxylic acid, it can be used in the form of inorganic salts, organic salts or metal complex salts.

  According to the present invention, the 2-chloro-1,3-thiazole-5-methanol derivative of the formula (I) can be used as an active ingredient of an agricultural and horticultural disease control agent.

  Hereinafter, the present invention will be described in more detail with reference to production examples, formulation examples, and test examples. However, the present invention is not limited to the following production examples as long as the gist thereof is not exceeded. The NMR spectrum was measured using TMS as an internal standard, and indicated by the following symbol or a combination thereof. s: single line, d: double line, t: triple line, m: multiple line, b: broad line, dd: double double line, qq: quadruple line

(Production Example 1)
<Production of 2-chloro-5-hydroxymethylthiazole (Compound No. 1)>
1.05 g of 2-chloro-5-chloromethylthiazole was dissolved in a 50% aqueous acetone solution, and 1.28 g of silver nitrate was added. After stirring at room temperature for 4 hours and at 55 ° C. for 5 hours, a gray precipitate (silver chloride) was filtered off and washed with chloroform. The filtrate was extracted with chloroform, and the organic layer was washed with saturated brine and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the resulting residue was separated and purified by silica gel column chromatography (Wakogel C-300 hexane / ethyl acetate = 1/1) to obtain 0.774 g of the desired compound. The physical properties of this compound are shown in Table 2.

(Production Example 2)
<Production of (2-chlorothiazol-5-yl) methyl benzyl sulfonate (Compound No. 19)>
Under an argon atmosphere, 0.160 g of 2-chloro-5-hydroxymethylthiazole was dissolved in 4.8 ml of anhydrous tetrahydrofuran, 0.028 g of sodium hydride was added with ice cooling, and the mixture was stirred for 30 minutes. 244g was added and it stirred for further 4 hours. After completion of the reaction, 10 ml of water was added to stop the reaction, and this was separated with ethyl acetate and then dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the resulting residue was separated and purified by silica gel column chromatography (hexane / ethyl acetate = 2/1) to obtain 0.155 g of the objective compound. Table 3 shows the physical properties of this compound.

(Production Example 3)
<Production of (2-chlorothiazol-5-yl) methyl 3-phenyl-2-propenate (Compound No. 9)>
Under an argon atmosphere, 0.226 g of 2-chloro-5-hydroxymethylthiazole was dissolved in 6.8 ml of dichloromethane, 0.302 g of cinnamoyl chloride and 0.314 ml of triethylamine were added, and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, 5 ml of water was added for liquid separation, and the organic layer was distilled off under reduced pressure. The obtained residue was separated and purified by silica gel column chromatography to obtain 0.449 g of the target compound. Table 4 shows the physical properties of this compound.

  The compounds shown in Table 5 below were synthesized by operations according to the above Production Examples 1 to 3. Table 5 shows melting points and NMR data of these compounds.

(Formulation example 1)
<Dust>
3 parts by weight of the compound of the present invention (Compound No. 3), 40 parts by weight of clay and 57 parts by weight of talc are pulverized and mixed and used as dust.

(Formulation example 2)
<Wettable powder>
50 parts by weight of the compound of the present invention (Compound No. 10), 5 parts by weight of lignin sulfonate, 3 parts by weight of alkyl sulfonate and 42 parts by weight of diatomaceous earth are pulverized and mixed to obtain a wettable powder and diluted with water for use. .

(Formulation example 3)
<Granule>
The compound of the present invention (Compound No. 18), 5 parts by weight of Bennite, 43 parts by weight of Bennite, 45 parts by weight of clay and 7 parts by weight of lignin sulfonate are mixed uniformly and further kneaded with water, and granulated with an extrusion granulator. Process dry to form granules.

(Formulation example 4)
<Emulsion>
20 parts by weight of the compound of the present invention (Compound No. 20), 10 parts by weight of polyoxyethylene alkylaryl ether, 3 parts by weight of polyoxyethylene sorbitan monolaurate and 67 parts by weight of xylene are uniformly mixed and dissolved to prepare an emulsion.

(Test Example 1)
<Rice blast control effect test (water surface application)>
Grains prepared in accordance with Formulation Example 3 to have a predetermined concentration (500 g / 10a) after transplanting rice (variety: Koshihikari) at the third leaf stage into a 1 / 10000a Wagner pot filled with paddy soil. Applied to the water surface. 10 to 20 days after the drug treatment, a spore suspension of rice blast fungus formed on rice disease was spray-inoculated and kept under high humidity in a vinyl tunnel in a glass greenhouse. 10-20 days after the inoculation, the disease incidence rate (%) was investigated objectively, and the disease incidence was investigated for all seedlings per test area according to the survey criteria shown in Table 6 below (Chinese agricultural leaf potato survey criteria). The control value (%) was calculated from the average disease degree per pot by the following formula: control value = (1−treatment disease degree / non-treatment disease occurrence degree) × 100. The results are shown in Table 7.

(Test Example 2)
<Wheat powdery mildew control effect (stem and leaf spray)>
Using a square-shaped pot (1.5 cm × 2.0 cm), a wet concentration prepared in accordance with Formulation Example 2 was added to wheat (cultivar: Norin 61) grown in a tillering greenhouse. 125 g / ha) was diluted with water and suspended at a rate of 1000 L / ha. 10 to 20 days after the drug treatment, spores were inoculated with spores of wheat powdery mildew. After that, she was sick in a glass greenhouse. On the 10th to 20th day after the inoculation, the disease incidence rate (%) was investigated objectively, and calculated from the average disease severity per pot according to the survey criteria shown in Table 8 below: control value = (1−treatment disease severity / The control value (%) was calculated by (non-treated morbidity) × 100. The results are shown in Table 9.

Claims (3)

A 2-chloro-1,3-thiazole-5-methanol derivative represented by the following formula (I).

[Wherein, R is a C ₂ -C ₄ alkyl group; (unsubstituted or C ₁ -C ₄ alkyl group, C ₁ -C ₄ alkoxy group and the same or different 1 selected from the group of halogen atoms 1 to five-phenyl is substituted with a _group) C 1 -C ₄ alkyl group; C ₃ -C ₆ alkenyl group; _(cyano) C 1 -C ₄ alkyl group; (unsubstituted or _C 1 -C ₄ alkyl group A tetrahydropyranyl group substituted with 1 to 5 groups which may be the same or different and selected from the group consisting of a C _{1 to} C ₄ alkoxy group and a halogen atom; a C _{2 to} C ₄ alkylcarbonyl group; Unsubstituted or substituted with ₁ to ₅ groups which may be the same or different and selected from the group consisting of a C _{1 to} C ₄ alkyl group, a C _{1 to} C ₄ alkoxy group and a halogen atom (C ₂ to C ₄ alkenyl Carbonyl _group; C 1 -C ₄ haloalkylcarbonyl group; (unsubstituted or _C 1 -C ₄ alkyl _groups, 1-5 which may be the same or different are selected from the group of C 1 -C ₄ alkoxy group and a halogen atom A phenyl group (which is substituted with a group of the following): (an unsubstituted or a C ₁ -C ₄ alkyl group, a C ₁ -C ₄ alkoxy group and ₁ to ₄ groups which may be the same or different and are selected from the group of halogen atoms) Thiazolyl substituted with a group) C ₁ -C ₄ alkyl group; (unsubstituted or C ₁ -C ₄ alkyl group, C ₁ -C ₄ alkoxy group and may be the same or different selected from the group of halogen atoms) 1-4 isothiazolyl substituted with _group) C 1 -C ₄ alkyl group; (unsubstituted or _C 1 -C ₄ alkyl _group, C 1 -C ₄ alkoxy groups and halogen atoms Identical or different substituted with also good 1-4 groups pyridyl) carbonyl group is selected from the group of; (unsubstituted or C ₁ -C ₄ alkyl group, C ₁ -C ₄ alkoxy group and a halogen atom identical or different substituted with also good 1-4 groups thiazolyl) carbonyl group is selected from the group; or (unsubstituted or C ₁ -C ₄ alkyl group, C ₁ -C ₄ alkoxy groups and halogen represent the same or different substituted with may also be one to five groups phenyl) C ₂ -C ₄ alkylsulfonyl group is selected from the group of atoms. ] 2-chloro-1,3-thiazole- represented by the formula (I), characterized by reacting a compound represented by the following formula (II) with a compound represented by the following formula (III) A method for producing a 5-methanol derivative.

[Wherein, X and Y represent a leaving group or a hydroxyl group. R is the same as defined in claim 1 . ] A plant disease control agent for agricultural and horticultural use comprising a 2-chloro-1,3-thiazole-5-methanol derivative represented by the following formula (I) as an active ingredient.

[Wherein, R represents a hydrogen _atom; the same or different and is selected from (unsubstituted or _C 1 -C ₄ alkyl _group, the group of C 1 -C ₄ alkoxy group and a halogen atom; C 1 -C ₄ alkyl group _phenyl) C 1 -C ₄ alkyl group substituted with may also be one to five groups; C ₃ -C ₆ alkenyl group; _(cyano) C 1 -C ₄ alkyl group; (unsubstituted or _C 1 -C ₄ alkyl group, C ₁ -C ₄ alkoxy and the same or different are selected from the group of halogen atoms are substituted with 1-5 groups may be) a tetrahydropyranyl group; C ₁ -C ₄ alkylcarbonyl group; (unsubstituted or C ₁ -C ₄ alkyl group, C ₁ -C ₄ alkoxy group and the same or different substituted with may also be one to five groups phenyl is selected from the group of halogen atom) ( C ₂ ~C ₄ Alkenyl) carbonyl _group; C 1 -C ₄ haloalkylcarbonyl group; (unsubstituted or _C 1 -C ₄ alkyl _group, C 1 -C ₄ same or different and may 1 is selected from the group of alkoxy group and a halogen atom A phenyl group (substituted by 5 groups); (unsubstituted or C ₁ -C ₄ alkyl group, C ₁ -C ₄ alkoxy group and the same or different 1 to 4 selected from the group of halogen atoms) Thiazolyl substituted with ₁ group) C ₁ -C ₄ alkyl group; (unsubstituted or identical or different selected from the group of C ₁ -C ₄ alkyl group, C ₁ -C ₄ alkoxy group and halogen atom) _{isothiazolyl)} C 1 -C ₄ alkyl group substituted with may also be 1-4 groups; (unsubstituted or _C 1 -C ₄ alkyl _group, C 1 -C ₄ alkoxy and Identical or different substituted with also good 1-4 groups pyridyl) carbonyl group is selected from the group of androgenic atoms; (unsubstituted or C ₁ -C ₄ alkyl group, C ₁ -C ₄ alkoxy and A thiazolyl substituted with 1 to 4 groups which may be the same or different and selected from the group of halogen atoms; a carbonyl group; (unsubstituted or a C ₁ -C ₄ alkyl group, a C ₁ -C ₄ alkoxy group and Phenyl substituted with 1 to 5 groups, which may be the same or different, selected from the group of halogen atoms) C ₁ -C ₄ alkylsulfonyl group; or (unsubstituted or C ₁ -C ₄ alkyl group, C _{1 to} C4 represents a phenyl) sulfonyl group substituted with ₁ to ₄ alkoxy groups and 1 to 5 groups which may be the same or different and selected from the group of halogen atoms. ]