KR830000377B1 - Preparation method of perhydroimidazo thiazole derivative - Google Patents

Abstract

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Description

Preparation method of perhydroimidazo thiazole derivative

The present invention relates to the preparation of novel perhydroimidazo thiazole derivatives. More specifically, 6- (3,5-dichlorophenyl) perhydroimidazo [5,1-b] thiazole-5,7-dione or 6- (3,5-dichlorophenyl) perhydro which is a hydantoin derivative The present invention relates to the preparation of imidazo [5,1-b] thiazole-5-thione-7-ones, which is a compound exhibiting excellent bactericidal activity.

As for the 3-substituted hydantoin derivatives, it has been reported that some compounds have biological activities such as bactericidal effect and manufacturing effect. (OLS 2604989)

MEANS TO SOLVE THE PROBLEM The present inventors are the 6- (3,5-dichlorophenyl) perhydro imidazo [5,1-b] thiazole-5,7-dione or 6 which are the new hydantoin derivative represented by following General formula (I). It was found that-(3,5-dichlorophenyl) perhydroimidazo [5,1-b] thiazole-5-thione-7- warm is an extremely useful substance with potent bactericidal effects against plant diseases. That is, this invention relates to the manufacturing method of a compound represented by following General formula (I),

General formula

Wherein R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, X represents an oxygen atom or a sulfur atom, and n represents 0, 1 or 2, and is represented by 6- (3,5- It is intended to prepare dichlorophenyl) perhydro imidazo [5,1-b] thiazole derivatives. Specific examples of the alkyl group are methyl, ethyl, fluoropropyl, and butyl groups.

None of the compounds of the present invention represented by the above general formula (I) are novel compounds, and have a strong bactericidal effect against plant diseases, and furthermore, harmful effects on plants are hardly seen, Low toxicity In particular, the compound of the present invention exhibits excellent effects on vegetables, fruit trees, gray mold disease, army nucleus disease, pear plaque, apple spot deciduous disease, onion gray rot, etc. Indicates. In addition, the compound of the present invention exhibits excellent bactericidal effect against bacteria that have developed resistance to a drug which has conventionally been widely used. Among the compounds represented by the general formula (I), in view of bactericidal effect, X is oxygen, R is hydrogen or an alkyl group having 1 to 3 carbon atoms, n is preferably 0, X is an oxygen atom, R is hydrogen, Methyl group and ethyl group are more preferable. Particularly, among them, 6- (3,5-dichlorophenyl) perhydroimidazo [5,1-b] thiazole-5,7-dione and 7a-methyl-6- (3, Most preferred is 5-dichlorophenyl) perhydroimidazo [5,1-b] thiazole-5,7-dione.

The compound of the present invention is represented by the following general formula (II)

Thiazori represented by (wherein R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, X represents an oxygen atom or a sulfur atom and R 'represents a hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms) It is prepared by condensation cyclization of a din-2-carboxylic acid derivative.

This raw material compound (II) is thiazolidine-2-carboxylic acid or its lower alkyl ester which may be substituted with a C1-C4 alkyl group at 2nd position, and 3, 5- dichlorophenyl isocyanic acid or 3, 5- dichloro It can manufacture using phenyl isothiocyanic acid as a raw material. If this is expressed as a reaction scheme, it is as follows.

(Wherein R and X have the same meaning as defined in the general formula (I), R 'represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and m represents 1 or 2)

That is, when using the lower alkyl ester of thiazolidine-2-carboxylic acid as a raw material, this ester, 3, 5- dichlorophenyl isocyanic acid, or 3, 5- dichlorophenyl isothiocyanic acid, is selected from benzene, toluene, 3- (3,5-dichlorophenyl carbamoyl) thiazolidine-2-carboxylic acid ester or 3- (3,5-dichlorophenyl thiocarba by reacting in a solvent such as ether or dimethylformamide Moyl) thiazoridin-2-carboxylic acid ester (R '= lower alkyl group in the said General formula (II)) is obtained. In this reaction, depending on the reaction conditions, the reaction is continued as it is after passing through the 3-substituted thiazolidine-2-carboxylic acid esters (R '= lower alkyl group in the general formula (II)), 6- (3,5-dichlorophenyl) perhydroimidazo [5,1-b] thiazole-5,7-diones or 6- (3,5- condensed with cyclization and represented by the general formula (Ia) Dichlorophenyl) perhydro imidazo [5,1-b] thiazole-5,7-thione-7-ones can be obtained. In the case of using thiazoridin-2-carboxylic acid as a raw material, it is suspended or dissolved in a mixed solvent of organic solvents such as benzene, chlorobenzene, ether, dimethyl formamide and water, for example. After reacting with 3,5-dichlorophenyl isocyanic acid or 3,5-dichlorophenyl thioisocyanic acid in the presence of an alkali such as Oda and caustic caustic, and neutralizing with an acid such as hydrochloric acid or sulfuric acid, 3- (3, 5-dichlorophenyl carbamoyl) thiazolidine-2-carboxylic acids or 3- (3,5-dichlorophenyl thiocarbamoyl) thiazolidine-2-carboxylic acids (in the general formula (II) , R '= hydrogen atom).

The condensation cyclization reaction may be carried out by heating this compound (II) in the presence of a mineral acid such as hydrochloric acid or sulfuric acid, or in acetic anhydride in the presence of an alkali metal salt of acetic acid such as sodium acetate, or, moreover, sodium alkoxide potassium It is carried out by reacting in a lower alkanol in the presence of alkali metal alcocoxides such as alcocoxides. Thus, 6- (3,5-dichlorophenyl) perhydroimidazo [5,1-b] thiazole-5,7-diones or 6- (3,5-dichlorophenyl) perhydroimidazo [5 , 1-b] thiazole-5-thione-7-ones (Ia) are obtained.

These compounds are purified according to conventional methods such as recrystallization and chromatography. 6- (3,5-dichlorophenyl) perhydroimidazo [5,1-b] thiazole-5,7-dione-1-oxide or 1,1-dioxides or 6- (3,5- Dichlorophenyl) perhydro imidazo [5,1-b] thiazole-5-thione-7-one-1-oxide or 1,1-dioxide (Ib) is said compound (Ia), such as methylene chloride It is obtained by dissolving in a solvent and oxidizing with oxidizing agents, such as m-chloro perbenzoic acid and peracetic acid.

In using the compound of the present invention as an agricultural or horticultural germicide, the compound may be used as it is, but in order to effect dispersion in the use scene of the active ingredient, an auxiliary agent is added according to a conventional method, and an emulsion, a hydrating agent, a powder, etc. It is preferable to use it as a mold.

Examples of the main agent in the agricultural and horticultural fungicide of the present invention include water, alcohols (methyl alcohol, ethyl alcohol, ethylene glycol, etc.), ketones (acetone, methyl ethiketone, cyclohexanone, etc.). , Ethers (ethyl ether, dioxane, cellosolves, etc.), aliphatic hydrocarbons (kerosene, kerosene fuel oil, etc.), aromatic hydrocarbons (benzene, toluene, xylene, solvent naphtha, methylnaphthalene, etc.), halogenated hydrocarbons Acids (dichloroethane, trichlorobenzene, oxygen tetrachloride, etc.) acid amides (dimethylformamide, etc.), esters (ethyl acetate, butyl acetate, fatty acid glyceline esters, etc.), nitriles (acetnitriles), etc. This is suitable, and 1 type, or 2 or more types thereof is used. As the weighting agent, clays such as kaolin and bentonite, talc, talc and talc, talc, mineral powder such as oxides such as white carbon and vegetable powder such as soy flour and CMC are suitable. One or a mixture of two or more of them is used.

Moreover, surfactant is used as an electrodeposition agent, a dispersing agent, an emulsifier, and a penetrant. As this surfactant, For example, nonionic surfactant (polyoxyethylene alkylaryl ether, polyoxyethylene sorbitan monolaurate etc.), cationic surfactant (alkyldimethyl benzyl ammonium chloride, alkylpyridinium chloride, etc.), Anionic crab surfactant (alkylbenzene sulfonate, lignin sulfonate, higher alcohol sulfate), an amphoteric surfactant (alkyldimethyl betaine, dodecylamino ethyl glycine etc.) etc. are mentioned. These surfactants are used as 1 type, or 2 or more types of mixtures according to a use.

In the case of using the agricultural and horticultural fungicide of the present invention, when using in the form of an emulsion, a mixture of 10 to 15 parts of the compound of the present invention, 10 to 80 parts of the solvent and 3 to 20 parts of the surfactant at an appropriate ratio is used as a stock solution. The solution is diluted with water to a predetermined concentration and used by spraying or the like.

In the case of using in the form of a hydrating agent, 5 to 80 parts of the compound of the present invention, 10 to 90 parts of the weight agent and 1 to 20 parts of the surfactant are mixed in an appropriate ratio, and the mixture is diluted with water or the like as in the case of the emulsion. use.

Moreover, when using in the form of powder, the thing mix | blended uniformly with 95-99 parts of weight agents, such as kaolin, bent nito, talc, and the like of 1-5 parts of this compound is used normally.

Moreover, the agricultural / horticultural germicide of this invention can also be mixed and mixed with another active ingredient which does not impair the bactericidal effect of this active ingredient, for example, a fungicide, an insecticide, acaricide.

In the case of the foliage treatment, the amount of the fungicide for farming of the present invention is about 50 to 500 L per 10α of the solution of 250 to 1500 ppm.

Next, the preparation of the compound of the present invention will be described in more detail with reference to preparation examples of agricultural fungicides containing the same and control tests by the present fungicides, but the present invention is limited to those exemplified in these specific examples. It is not. In addition, a part represents a weight part.

[Production Example 1]

56.6 g of cysteamine hydrochloride was dissolved in 500 ml of ethanol, and 148.1 g of a 25% aqueous solution of glyoxylic acid was added thereto. The mixture was heated and refluxed for 1.5 hours to cool, and the precipitated crystals were filtered out to obtain 41.6 g (yield 62.5%) of thiazolidine-2-carboxylic acid. Melting Point: 187 ~ 9 ° (Decomposition)

6.66 g of the obtained thiazolidine-2-carboxylic acid and 2.0 g of sodium hydroxide were dissolved in 100 ml of water, and a solution of 9.40 g of 3,5-dichlorophenyl isocyanic acid and 50 ml of chlorobenzene was added thereto at room temperature. The reaction was carried out by stirring for 2 hours. After the reaction, ether was extracted and the aqueous phase was neutralized with concentrated hydrochloric acid. The precipitated crystals were filtered, washed with water, and dried to obtain 14.4 g (yield 89.5%) of dml 3- (3,5-dichlorophenyl carbamoyl) diazolidine-2-carboxylic acid.

Melting Point: 175.5 ~ 7.0 ℃, Elemental Analysis Value (Calculated Value in Brackets)

C 40.88% (41.14%), H 3.11% (3.14%), N 8.86% * 8.72%), Cl 22.24% (22.08%)

13.0 g of obtained 3- (3,5-dichlorophenyl carbamoyl) thiazolidine-2-carboxylic acid was added to 50 ml of concentrated hydrochloric acid, and it heated and stirred at 120 degreeC for 2 hours, and reacted. After the reaction, the mixture was cooled, and the precipitated crystals were filtered out and recrystallized in an ethyl acetate-n-hexane mixed solvent to obtain 10.7 g (86.9% of yield) of 1,1-dioxides or 6- (3,5-dichlorophenyl). Perhydro imidazo [5,1-b] thiazole 5,7-dione (Compound No. 1) was obtained. Melting point 141-2 degrees Celsius, elemental analysis value (calculated value in parenthesis)

C 43.40% (43.58%), H 2.73% (2.66%), N 9.18% (9.24%), Cl 23.25% (23.39%)

[Production Example 2]

20.0 g of thiazolidine-2-carboxylic acid obtained in Preparation Example 1 was added to 200 ml of 20% ethanol hydrochloride solution, and after heating under reflux for 2 hours, the solvent was distilled off under reduced pressure, and neutralized with saturated sodium bicarbonate water. After extracting with ethyl acetate, the extract was vacuum distilled to obtain 19.1 g (yield 79.8%) of thiazolidine-2-carboxylic acid ethyl ester. Boiling point 104 ~ 5 ° C / 5.5mmHg. 1.61 g of obtained thiazolidine-2-carboxylic acid ethyl ester and 2.04 g of 3,5-dichlorophenyl isothiocyanic acid were added to 20 ml of toluene, and it heated at 90 degreeC for 1 hour, and reacted. After the reaction, the mixture was cooled and the precipitated crystals were filtered out to obtain 3.11 g (yield 85.1%) of 3- (3,5-dichlorophenyl thiocarbamoyl) thiazolidine-2-carboxylic acid ethyl ester. Melting point: 170.5 ~ 1.5 ° C, elemental analysis value (calculated value in parentheses).

C 42.68% (42.74%), H 3.93% (3.86%), N 7.70% (7.67%), Cl 19.32% (19.41%)

2.19 g of obtained 3- (3,5-dichlorophenyl carbamoyl) thiazolidine-2-carboxylic acid ethyl ester was added to 20 ml of concentrated hydrochloric acid, and the mixture was heated and stirred at 120 ° C. for 1.5 hours to carry out the reaction. After the reaction, the mixture was cooled and the precipitate was filtered and then recrystallized in an ethyl acetate-n-hexane mixed solvent to yield 1.43 g (yield 74.7%) of 6- (3,5-dichlorophenyl) perhydroimidazo [5,1- d] thiazole-5-thione-7-one (compound No. 2) was obtained.

Melting Point: 149.5 ~ 50.5 ℃ Elemental Analysis Value (Calculated Value in Parenthesis)

C 41.33% (41.39%), H 2.59% (2.53%), N 8.60% (8.78%), Cl 22.51% (22.21%)

[Manufacture example 3]

36.6 g of cysteamine hydrochloride, 32.6 g of triethylamine and 32.9 g of pyruvic acid methyl ester were added to 500 ml of ethanol, and the mixture was heated and refluxed for 2 hours to carry out the reaction. After the reaction, the solvent was distilled off under reduced pressure, water was added, and then acetate ester was extracted. The extract was vacuum distilled to give 36.6 g (70.4% of yield) of 2-methylthiazolidine-2-carboxylic acid methyl ester. Boiling point: 76 ° C./2 mmHg.

3.22 g of the obtained 2-methylthiazolidine-2-carboxylic acid methyl ester was added to a solution of 0.80 g of caustic sodium and 20 ml of water, and stirred at room temperature to give an aqueous sodium salt solution of 2-methylthiazolidine-2-carboxylic acid. After that, a solution of 3.76 g of 3,5-dichloro isocyanic acid and 20 ml of chlorobenzene was added, followed by stirring at room temperature for 1.5 hours. After the reaction, the mixture was collected with ether, and the aqueous phase was neutralized with concentrated hydrochloric acid. The precipitated crystals were collected by filtration, washed with water and dried to obtain 5.22 g (77.9% of child yield) of 5.0 g of 2-methyl-3- (3,5-dichlorophenyl carbamoyl) thiazolidine-2-carboxylic acid and acetic acid. 5 mg of Oda was added to 30 ml of acetic anhydride, and heated at 90 ° C. for 2 hours to conduct a reaction. After the reaction, the mixture was concentrated under reduced pressure and poured into water. The precipitated crystals were recrystallized from a mixed solvent of ethyl acetate-n-hexane to give 3.92 g of 7a-methyl-6- (3,5-dichlorophenyl) perhydroimidazo [5,1-b] thiazole-5,7-dione. (Compound No. 3) was obtained.

Melting point: 110 ~ 2 ℃, elemental analysis value (calculated value in parentheses).

C 45.56% (45.44%), H 3.09% (3.18%), N 8.72% (8.83%), Cl 22.20% (22.35%)

[Production Example 4]

1.61 g of 2-methylthiazolidine-2-carboxylic acid methyl ester obtained in Production Example 3 and 2.04 g of 3,5-dichlorophenyl isothiocyanic acid were added to 30 ml of toluene, followed by heating and stirring at 90 ° C. for 2 hours. It was done. After the reaction, the mixture was concentrated under reduced pressure, recrystallized from a toluene-n-hexane mixed solvent, and 2.50 g (yield 75.0%) of 7a-methyl-6- (3,5-dichlorophenyl) perhydroimidazo [5,1- b] Thiazol-5-thione-7-one (compound No. 4) was obtained.

Melting point 160 ~ 1 ℃, elemental analysis value (calculated value in parentheses)

C 43.36% (43.25%), H 2.95% (3.02%), N 8.36% (8.41%), Cl 21.41% (21.28%)

Production Example 5

1.52 g of compound No. 1 obtained in Production Example 1 was dissolved in 10 ml of methylene chloride, and 1.04 g of m-chloroperbenzoic acid and 12.5 ml of methylene chloride were added thereto under ice cooling, and the mixture was heated to reflux for 1 hour. Subsequently, a solution of 1.04 g of m-chloro-benzoic acid and 12.5 ml of methylene chloride was added thereto, and the mixture was heated to reflux for 1 hour to complete the reaction. After the reaction, the mixture was washed with dilute sodium hydroxide, concentrated and purified by column chromatography using ethyl acetate as a developing solvent, and 0.50 g (yield 29.8%) of 6- (3,5-dichlorophenyl) perhydroimidazo. [5,1-b] thiazole-5,7-dione-1,1-dioxide (Compound No. 5) was obtained. Melting point: 176 ~ 8 ℃, elemental analysis value (calculated value in parentheses).

C 40.01% (39.42%), H 2.36% (2.41%), C 8.27% (8.36%), Cl 21.35% (21.16%)

[Manufacture example 6]

Instead of compound No. 1, 1.52 g of compound No. 3 obtained in Production Example 3 was used, and the others were reacted in the same manner as in Production Example 5. After the reaction, the mixture was washed with a dilute sodium hydroxide solution, concentrated, and then recrystallized from a mixed solvent of ethyl acetate-n-hexane to yield 1.18 g (yield 67.6%) of 7a-methyl-6- (3,5-dichlorophenyl) per Hydroimidazo [5,1-b] thiazole-5,7-dione-1,1-dioxide (Compound No. 6) was obtained.

Melting Point: 190 ~ 1 ℃, Elemental Analysis Value (Calculated Values in Parentheses)

C 41.35% (41.28%), H 2.95% (2.89%), N 7.89% (8.02%), Cl 20.13% (20.31%)

[Manufacture example 7]

11.4 g of cysteamine hydrochloride and 10.1 g of triethylamine were dissolved in 100 ml of ethanol, and 10.2 g of 2-ketonoxane was added thereto. The reaction was carried out by refluxing for 30 minutes. After cooling, the precipitated crystals were filtered to obtain 10.6 g (yield 65.7%) of 2-ethylthiazolidine-2-carboxylic acid. Melting Point 235 ~ 8 ℃ (Decomposition)

10.0 g of 2-ethyl-thiazolidine-2-carboxylic acid obtained was added to 200 ml of a 20% hydrogen chloride-methanol solution, and after heating to reflux for 30 minutes, the solvent was distilled off under reduced pressure. Water was added and neutralized with saturated sodium bicarbonate water. After extraction with ethyl acetate, the extract was purified by silica gel column chromatography to obtain 2.0 g (yield 18.4%) of 2-ethylthiazolidine-2-carboxylic acid methyl ester.

0.62 g of 2-ethylthiazolidine-2-carboxylic acid methyl ester and 0.66 g of 3,5-dichlorophenyl isocyanic acid were added to 10 ml of toluene and stirred at room temperature for 1 hour. The precipitated crystals were filtered to obtain 1.00 g (77.8% yield) of 2-ethyl-3- (3,5-dichlorophenyl carbamoyl) thiazolidine-2-carboxylic acid methyl ester.

Melting Point: 187 ~ 8 ℃, Elemental Analysis Value (Calculated Value in Brackets)

C 46.48% (46.29%), H 4.35% (4.44%), C 7.50% (7.71%), Cl 19.86% (19.52%)

0.70 g of the obtained 2-ethyl-3- (3,5-dichlorophenyl carbamoyl) thiazolidine-2-carboxylic acid methyl ester was added to 20 ml 0.1 N sodium methite methanol solution, and heated to 50 DEG C for 20 minutes. The reaction was carried out. After the reaction, the mixture was cooled, and the precipitated crystals were filtered to obtain 0.16 g (25% yield) of 7a-ethyl-6- (3,5-dichlorophenyl) perhydroimidazo [5,1-b] thiazole-5,7 -Dione (compound No. 7) was obtained.

Melting point: 138 ~ 9 ℃ Elemental analysis (calculated values in parentheses).

C 46.99% (47.14%), H 3.87% (3.65%), N 8.22% (8.46%), Cl 21.41% (21.41%)

[Manufacture example 8]

The reaction was carried out in the same manner as in Production Example 7 using 2-ketogilic acid in place of 2-ketobutyric acid, followed by post-treatment to give 2-n-furofilthiazolidine-2-carboxylic acid (melting point: 222 to 3 ° C (decomposition)). , 2-n-furophilthiazoridine-2-carboxylic acid methyl ester (melting point: 39-40 degreeC), 2-n-furophyl-3- (3,5-dichlorophenyl carbamoyl) thiazolidine- 2-carboxylic acid methyl ester melting point: 187 ~ 9 ℃, elemental analysis value (calculated values in parentheses)

C 47.36% (47.75%), H 4.95% (4.81%), N 7.61% (7.42%), Cl 18.53% (18.79%)

And 7a-n-furophil-6- (3,5-dichlorophenyl) perhydroimidazo [5,1-b] thiazole-3,7-dione Compound No. 8, melting point: 145.5 to 6.5 ° C., element Analysis (calculated values in brackets)

C 48.34% (48.70%), H 4.08% (4.09%), N 7.83% (8.11%), Cl 20.28% (20.54%)

[Manufacture example 9]

0.33 g of 2-ethylthiazolidine-2-carboxylic acid methyl ester obtained in Production Example 7 and 0.38 g of 3,5-dichlorophenyl isothiocyanic acid were added to 5 ml of toluene and heated at 90 ° C. for 2 hours to carry out a reaction. . Purified by silica gel column chromatography, 0.15 g of 7a-ethyl-6- (3,5-dichlorophenyl) perhydroimidazo [5,1-b] thiazol-5-thione-7-one (Compound No. 9) was obtained. Melting Point: 139 ~ 40 ℃, Elemental Analysis Value (Calculated Values in Parentheses)

C 44.70% (44.96%), H 3.55% (3.48%), N 8.16% (8.07%), Cl 20.12% (20.42%)

[Production Example 10]

The reaction was carried out in the same manner as in Preparation Example 9, using 3-n-furophyl thiazolidine-2-carboxylic acid methyl ester obtained in Preparation Example 8 instead of 2-ethyltaazoridine-2-carboxylic acid methyl ester. 7a-n-furophil-6- (3,5-dichlorophenyl) perhydroimidazo [5,1-b] thiazole-5-thione-7-one (Compound No. 10) was obtained.

Melting Point: 153 ~ 3.5 ℃, Elemental Analysis Value (Calculated Values in Parentheses)

C 46.81% (46.54%), H 3.90% (3.91%), N 7.91% (7.75%), Cl 19.78% (19.62%)

TABLE 1

Formulation Example 1

50 parts of compound No. 1, 45 parts of talc, and 5 parts of solfool 8070 *** (surfactant mainly containing a higher alcohol sulfate ester) were uniformly ground and mixed to obtain a disinfectant (hydrating agent).

Formulation Example 2

(폴리옥시에틸렌 알킬아틸에테르 솔포네이트를 주성분으로 하는 계면 활성제) 3부를 균일하게 분쇄 혼합하여 살균제(수화제)를 얻었다.Compound No. 3 40 parts, white carbon 10 parts, diatomaceous earth 47 parts, solfool 5039

(Surfactant which has a polyoxyethylene alkyl aryl ether sorbonate as a main component) 3 parts was uniformly ground and mixed, and the sterilizing agent (hydrating agent) was obtained.

Formulation Example 3

(비이온 계면활성제와 음이온 계면활성제와의 혼합물) 15부, 크실렌 25부, 디메틸포름아미드 30부를 혼합용해하여 살균제(유제)를 얻었다.Compound No. 2 30 parts, Solfool 3005

(Mixture of nonionic surfactant and anionic surfactant) 15 parts, 25 parts of xylene, and 30 parts of dimethylformamide were mixed and dissolved to obtain a disinfectant (emulsion agent).

Formulation Example 4

2 parts of compound No. 4 and 98 parts of N, N-kaolin crayfish (manufactured by Tsuchiya Kaolin) were mixed and ground to obtain a disinfectant (emulsion agent).

Test Example 1 Cucumber gray mold control effect test

Cucumber at the time of the first column cultivated in a vinyl pot having a diameter of 15 cm (variety: Satsuki Midori hydrating agent (Compound No. As a hydrating agent having 2 to 10 as an active ingredient and a comparator, a tetrachloroisophthalonitrile obtained as an active ingredient as an active ingredient) was diluted with water, sprayed 10 ml per pot, and air dried for 5 hours. Subsequently, the fungus was inoculated with gray fungal bacteria (Portritic cinerea) shaken in yeast glucose liquid medium, and maintained in a humidified environment at 23 ° C. for 4 days after inoculation. In other words, the incidence is obtained by calculating the incidence area ratio of irradiated leaves, and classifying them according to the degree into the indices of 0,1,2,3,4,5, and the leaves corresponding to each incidence index. The subject to be _{n 0, n 1, n 2} , n 3, n 4, n 5 irradiation was calculated from the following equation.

(n is the number of leaves examined)

The control value was calculated by the following equation.

The results are shown in the second table.

TABLE 2

Test Example 2 Rice horseshoe leaf disease control effect test

Hydrating agent to 3-4 leaf rice seedlings (variety: nannan hoo) grown in earthenware pots with a diameter of 10 cm [Hydrating agent which uses compound No. 1 obtained in preparation 1 as an active ingredient and compound no. Wetting agent containing bis (dimethyl thiocarbamoim) disulfide as an active ingredient obtained in the same manner as in Formulation Example 1 using a hydrating agent containing 2 to No. 10 as an active ingredient and diluting with water, and spraying 10 ml per pot. After 5 hours of air drying, a spore suspension of cochliobolus miyabeanus (cultivated at 25 ° C. for 5 days in a rice hull medium) was spray-inoculated in a wet room (temperature of 27 ° C. and humidity of 100%). After leaving it in the wet room again for 48 hours, the onset was investigated and the control effect was computed.

The results are shown in Table 3.

TABLE 3

* Pharmaceutical: Bis (dimethylthiocarbamoyl) disulfide

Experimental Example 3 Control effect test

10 ml per pot is diluted by diluting the hydrated co-agents and the control agent in water, which are obtained in the same manner as in Preparation Example 1 and Preparation Example 1, in Gangnam beans (variety: ginto), grown in plastic pots with a diameter of 15 cm. After sparging and air drying for 5 hours, Sclerotinia Sclorotionum was inoculated with shaking culture in yeast glucose liquid medium, and maintained for 4 days after the inoculation, and kept in a humidified room at 23 ° C. The investigation method is the same as Test Example 1. The results are shown in Table 4. (Comparative agent is 2,6-dichloro-4-nitroaniline)

TABLE 4

Test Example 4 Antibacterial Test

Each chemical solution is mixed to a predetermined concentration in PDA medium, and poured into an experimental container having a diameter of 9 cm and solidified.

Thereafter, various pathogens were inoculated at the center of the agar plate and incubated at 25 ° C for 4 days. In the judgment, the concentration at which growth was not seen at all by the naked eye was defined as the minimum growth inhibition concentration (MIC). The results are shown in Table 5.

[Table 5] Antibacterial test results [MIC (ppm)]

Claims (1)

Condensation of a thiazolidine-2-carboxylic acid derivative of the following general formula (II) to 6- (3,5-dichlorophenyl) perhydroimidazo [5,1-b] thiazole of the following general formula (I) Method of Making Derivatives.

In the above formula, R is hydrogen or an alkyl group having 1 to 4 carbon atoms, X is an oxygen or sulfur atom, and R 'is hydrogen or a lower alkyl group.