KR970006246B1 - 2-imino-4-thiazolidinone derivatives and process for preparing thereof - Google Patents

Abstract

2-imino-4-thiazolidinone derivative of general formula(I) is prepared by reacting a compound of general formula(II) with a compound of general formula(III) in a solvent under alkali presence. The produced thiazolidinone derivative is effective as agri & horticultural bactericide. At the above formula, R1 is phenyl group or phenyl group including 1 or 2 halogen atom or trifluoromethyl group. R2 is hydrogen, alkyl or cycloalkyl group with 1-3 carbon number and R3 is cyano, fulfuryl, replaced cyclohexyl, naphthylmethyl group and like.

Description

2-imino-4-thiazolidinone derivatives and preparation method thereof

The present invention relates to a novel compound 2-imino-4-thiazolidinone derivative represented by the following general formula (I).

[Formula 1]

In Formula (I), R ¹ represents a phenyl group or a phenyl group including one or two halogen or trifluoromethyl groups, R ² represents hydrogen or an alkyl group having 1 to 3 carbon atoms or a cycloalkyl group, and R ³ is A cyano, fulfuryl, substituted cyclohexyl, naphthylmethyl group or the following formula is shown.

(Wherein R ⁴ , R ⁵ independently represent hydrogen, methyl group, halogen, nitro or methoxycarbonyl and n is 0 to 2).

The present invention also relates to a method for producing these 2-imino-4-thiazolidinone derivatives and a fungicide containing these derivatives as an active ingredient.

2. Description of the Prior Art Many studies have been conducted on 2-imino-4-thiazolidinone derivatives in connection with photosensitive substances and pharmaceutical activity. However, there are relatively few studies related to pesticide activity, and very few studies related to practical use are described in the Federal Republic of Germany Patent No. 3,505,435.

Meanwhile, as a horticultural fungicide, synthetic compounds having various chemical structures have been used to play a huge role in controlling food diseases. As a result, they have greatly contributed to the development of agriculture. However, since many of the compounds have problems such as toxicity to the environment and to the human body, the development of a new low-toxic fungicide that is stable to both the environment and the human body is required.

In order to meet these demands, the inventors of the present invention have excellent bactericidal powers of 2-imino-4-thiazolidinone compounds represented by the above general formula (I), which are different from the known structures while carrying out research and development of new low-toxic bactericides. The present invention was completed.

That is, it is an object of the present invention to provide a fungicide and a method for producing the same as a fungicide without having harmful toxicity to both humans and animals as an agricultural horticultural fungicide.

In order to achieve the object of the present invention as described above, the 2-imino-4-thiazolidinone derivative of the following general formula (I) according to the present invention is a compound of the general formula (II) and a compound of the general formula (III) Is prepared by reacting in the presence of a base in a solvent.

[Formula 1]

[Formula 2]

[Formula 3]

Formulas R ¹ , R ² and R ³ are as described above, X is a halogen atom, and Y represents a lower alkoxy group or halogen atom having 1 to 4 carbon atoms.

Looking at the present invention in more detail as follows.

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

[Formula 2]

(In Formula (II), R ¹ is the same as described above, X is a halogen atom, Y is a halogen atom or a lower alkoxy group having 1 to 4 carbon atoms.) In the presence of a base, represented by the following general formula (III) It can be easily synthesized by reacting with thiourea.

[Formula 3]

(In Formula (III), R ² and R ³ are the same as described above.)

When R ² is hydrogen in the compound, the compound of general formula (I) may exist in the form of tautomer of general formula (I ′) and (II) as shown in the following formula.

[Formula 1 ']

[Formula 1]

It is preferable to carry out in a solvent that does not significantly hinder the progress of the reaction of the present invention. Suitable solvents for this purpose include aliphatic hydrocarbons such as hexane and cyclohexane, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, acetone and cyclohexane. Silver, ketones such as methyl ethyl ketone, ethyl ethers such as ethyl ether, dioxane, tetrahydrofuran, halogenated hydrocarbons such as methylene chloride, chloroform, hydrogen tetrachloride, dichloroethane, aliphatic esters such as ethyl acetate, aceto Nitrile, nitromethane, nitropropane and the like, aliphatic amides such as dimethylformamide and dimethylacetimide, alcohols such as ethanol, isopropanol and t-butanol, dimethyl sulfoxide and the reaction of the present invention are not severely affected. Other solvents or mixtures thereof. These solvents can also be used in admixture with water.

Examples of bases that can be used in the reaction of the present invention include inorganic hydroxides such as potassium hydroxide, sodium hydroxide, aqueous ammonia solution, potassium carbonate, sodium carbonate, sodium hydrogen carbonate, sodium phosphate, sodium hydrogen phosphate, boric acid, calcium hydroxide, calcium oxide, and the like. And organic bases such as ethylamine and pyridine.

In most cases these bases are used in powder form and can also be used in solution form.

The present invention is reacted in the temperature range between -10 ° C and 150 ° C. However, in the compound of general formula (II), when is a halogen atom, 10 degreeC-50 degreeC is preferable, and when Y is an alkoxy group, 50 degreeC-110 degreeC is preferable.

The reactants may be reacted in a 1: 1 molar ratio in stoichiometric amounts, but one of the reactants may be used in an excessive amount, that is, 1 to 20%.

After completion of the reaction, the product 4-thiazolidinone derivative is separated and economical according to the method commonly performed in the art such as type, crystallization, chromatography according to the physical properties of each compound, the identification of the compound is IR, NMR This is done using a mass spectrometer.

Representative examples of the general formula (I) are as shown in Table 1 below.

2 = imino-4-thiazolidinone derivatives according to the present invention prepared as described above are prepared as fungicides by conventional methods.

Conventionally, 2-imino-4-thiozolidinone compounds in which 5-position carbon is connected to a substituent by a double bond have been mainly known, and 2-position carbon by compounds in which 5-position carbon is connected to a substituent by a single bond is known. Compounds linked by a single substituent with a single bond are also most of the compounds substituted in 2-position nitrogen and 3-position nitrogen are alkyl or aryl groups, so the bactericidal effect was not excellent. Thus, the compounds represented by the general formula (I) having excellent sterilization efficacy were completed.

Hereinafter, the present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following compounds.

Example 1

Synthesis of 2-benzylimino-3-isopropyl-5-phenyl-4-thiazolidinone (Compound No. 1)

1.8 g of methyl alpha-chlorophenylacetate was dissolved in 30 ml of acetonitrile, 2.0 g of N-benzyl-N'isopropyl thiourea was added thereto, and then dissolved. After the reaction was completed, the mixture was lowered to room temperature, filtered, and the solvent was removed. The oil was dissolved in 30 ml of ethyl acetate and washed three times with 30 ml of water.

After drying with forget-me-not and removing the solvent, the oily residue was chromatographed on a silica gel column using hexane and ethyl acetate solvent to obtain 2.0 g of an oily target product.

Example 2

Synthesis of 2-benzylinomy-3-methyl-5-phenyl-4-thiazolidinone (Compound No. 2)

2.0 g of methyl alpha-chlorophenyl acetate was dissolved in 30 ml of dichloroethane, and 1.8 g of N-benzyl-N'-methyl thiourea was added thereto to dissolve. 3.0 g of calcium hydroxide was added thereto, and the mixture was warmed and stirred at 80 ° C. for 8 hours. After the reaction was completed, the mixture was cooled to room temperature, filtered, and the solvent was removed, followed by crystallization with isopropyl alcohol to obtain 2.5 g of the target substance.

M.P. : 84 to 86 ° C

Example 3

Synthesis of 2- (4-fluorobenzyl) imino-3-isopropyl-5-phenyl-4-thiazolidinone (Compound No. 3)

1.8 g of methyl alpha-chlorophenyl acetate and 2.2 g of N- (4-fluoro) benzyl-N'-isopropyl thiourea were used in the same manner as in Example 1 to obtain 2.1 g of an oily target product.

Example 4

Synthesis of 2- (2,6-difluorobenzyl) imino-3-isopropyl-5-phenyl-4-thiazolidinone (Compound No. 4)

1.8 g of methyl alpha-chlorophenyl acetate and 2.4 g of N- (2,6-difluoro) benzyl-N'-isopropyl thiourea were used in the same manner as in Example 1 to obtain 1.9 g of an oily target product.

Example 5

Synthesis of 2- (cyano) imino-3-methyl-5-phenyl-4-thiazolidinone (Compound No. 5)

1.7 g of the target product was obtained by using 2.0 g of ethyl alpha-chlorophenyl acetate and 1.2 g of N-cyano-N'-methyl thiourea in the same manner as in Example 1.

M.P. : 146-149 degreeC

Example 6

Synthesis of 2- (4-chlorobenzyl) imino-3-methyl-5-phenyl-4-thiazolidinone (Compound No. 6)

2.1 g of the target product was obtained by using 2.9 g of ethyl alpha-chlorophenyl acetate and 2.1 g of N- (4-chloro) phenyl-N'-methylthiourea in the same manner as in Example 1.

M.P. : 85 to 87 ° C

Example 7

Synthesis of 2- (4-fluorobenzyl) imino-3-methyl-5-phenyl-4-thiazolidinone (Compound No. 7)

0.7 g of methyl alpha-bromophenyl acetate was dissolved in 20 ml of acetonitrile, and 0.6 g of N- (4-fluoro) benzyl-N'-methyl thiourea was added to dissolve it. Stir for 10 hours. After the reaction was completed, the mixture was lowered to room temperature, filtered, and the solvent was removed. The oil was dissolved in 30 ml of ethyl acetate and washed three times with 20 ml of water. After drying with forget-me-not and removing the solvent, the residue was crystallized in hexane and ethyl acetate solution to obtain the target product 0.8g.

M.P. : 96 to 98 ° C

Example 8

Synthesis of 2- (4-chlorophenyl) imino-3-methyl-5-phenyl-4-thiazolidinone (Compound No. 8)

2.2 g of n-butyl alpha-chloroniphenyl acetate and 1.8 g of N- (4-chloro) phenyl-N'-methyl thiourea were used in the same manner as in Example 1 to obtain 1.8 g of the target product.

M.P. : 89-91 degreeC

Example 9

Synthesis of 2- (3-fluorobenzyl) imino-3-isopropyl-5-phenyl-4-thiazolidinone (Compound No. 9)

In the same manner as in Example 1, 1.8 g of methyl alpha-chlorophenylacetate and 2.2 g of N- (3-fluoro) benzyl-N'-isopropyl thiourea were used to obtain 1.9 g of an oily target product.

Example 10

Synthesis of 2- (4-fluorobenzyl) imino-5-phenyl-4-thiazolidinone (Compound No. 10)

1.8 g of methyl alpha-chlorophenyl acetate and 1.7 g of l- (4-fluoro) phenyl-2-thiourea were used in the same manner as in Example 1 to obtain 1.8 g of the target product.

M.P. : 189 to 190 ° C

Example 11

Synthesis of 3-methyl-2- (4-nitrophenyl) imino-5-phenyl-4-thiazolidinone (Compound No. 11)

In the same manner as in Example 1, 1.8 g of methyl alpha-chlorophenyl acetate and 1.7 g of N- (4-nitro) phenyl-N'-methylthiourea were used to obtain 1.9 g of the target product.

M.P. : 149 to 151 ° C

Example 12

Synthesis of 2-fulfurylimino-3-isopropyl-5-phenyl-4-thiazolidinone (Compound No. 12)

1.8 g of methyl alpha-chlorophenyl acetate and 1.9 g of N-fulfuryl-N'-isopropylthiourea were used in the same manner as in Example 1 to obtain 2.0 g of an oily target product.

Example 13

Synthesis of 2- (4-fluorophenyl) imino-3-phenyl-4-thiazolidinone (Compound No. 13)

1.8 g of methyl alpha-chlorophenyl acetate and 2.2 g of N- (4-fluoro) phenyl-N'-methylthiourea were used in the same manner as in Example 1 to obtain 1.9 g of an oily target product.

Example 14

Synthesis of 2- (2-chlorophenyl) imino-3-methyl-5-phenyl-4-thiazolidinone (Compound No. 14)

1.8 g of methyl alpha-chlorophenyl acetate and 2.0 g of N- (2-chloro) phenyl-N'-methylthiourea were used in the same manner as in Example 1 to obtain 1.8 g of an oily target product.

Example 15

Synthesis of 2- (2-fluorophenyl) imino-5-phenyl-4-thiazolidinone (Compound No. 15)

1.8 g of methyl alpha-chlorophenyl acetate and 1.7 g of 1- (2-fluoro) phenyl-2-thiourea were used in the same manner as in Example 1 to obtain 1.5 g of the target product.

M.P. : 159 to 162 ° C

Example 16

Synthesis of 2- (3,4-difluorobenzyl) imino-3-methyl-5-phenyl-4-thiazolidinone (Compound No. 16)

0.6 g of methyl alpha-chlorophenyl acetate was dissolved in 30 ml of acetonitrile, and 0.6 g of N- (3,4-difluorobenzyl) -N'-methyl thiourea was added to dissolve it. Stir at 15 ° C. for 15 hours. After the reaction was completed, the mixture was lowered to room temperature, filtered, and the solvent was removed. The oil was dissolved in 30 ml of ethyl acetate and washed three times with 30 ml of water. After drying with forget-me-not and removing the solvent, the oily residue was chromatographed on a silica gel column. The column was eluted with hexane and ethyl acetate to give 0.5 g of the desired product.

M.P. : 106 to 108 ° C

Example 17

Synthesis of 2- (2,4-difluorobenzyl) imino-3-methyl-5-phenyl-4-thiazolidinone (Compound No. 17)

0.6 g of methyl alpha-chlorophenyl acetate and 0.6 g of N- (2,4-difluorobenzyl) -N'-methyl thiourea were used in the same manner as in Example 16 to obtain 0.4 g of the target substance.

M.P. : 88-91 degreeC

Example 18

Synthesis of 2- (2,5-difluorobenzyl) imino-3-methyl-5-phenyl-4-thiazolidinone (Compound No. 18)

0.6 g of methyl alpha-chlorophenyl acetate and 0.6 g of N- (2,5-difluorobenzyl) N'-methylthiourea were used in the same manner as in Example 16 to obtain 0.4 g of the target substance.

M.P. : 82 to 85 ° C

Example 19

Synthesis of 2- (2,6-difluorobenzyl) imino-3-methyl-5-phenyl-4-thiazolidinone (Compound No. 19)

0.3 g of the target product was obtained by using 0.6 g of methyl alpha-chlorophenyl acetate and 0.6 g of N- (2,6-difluorobenzyl) N'-methylthiourea in the same manner as in Example 16.

M.P. : 98-101 degreeC

Example 20

Synthesis of 2- (2-bromophenyl) imino-3-methyl-5-phenyl-4-thiazolidinone (Compound No. 20)

1.8 g of methyl alpha-chlorophenyl acetate and 2.4 g of N- (2-bromo) N'-methylthiourea were used in the same manner as in Example 1 to obtain 2.2 g of an oily target product.

Example 21

Synthesis of 2- (2-bromophenyl) imino-5-phenyl-4-thiazolidinone (Compound No. 21)

0.6 g of methyl alpha-bromophenyl acetate was dissolved in 30 ml of acetonitrile, and 0.6 g of 1- (2-bromophenyl) -2-thiourea was added to dissolve it. Then, 2.0 g of calcium hydroxide was added thereto and warmed. Stir for hours. After the reaction was completed, the mixture was cooled to room temperature, filtered, and the solvent was removed, and then the oily residue was chromatographed on a silica gel column. The column was eluted with hexane and ethyl acetate to give the desired product 0.6g.

M.P. : 140 to 143 ° C

Example 22

Synthesis of 3-methyl-2- (2-phenylethyl) imino-5-phenyl-4-thiazolidinone (Compound No. 22)

0.7 g of methyl alpha-bromophenyl acetate was dissolved in 30 ml of acetone, 0.5 g of N-methyl-N '-(2-phenyl) ethyl thiourea was added to dissolve it, 0.4 g of triethylamine was added thereto, and warmed at 56 ° C for 15 hours. Was stirred. After the reaction was completed, the mixture was lowered to room temperature, filtered, and the solvent was removed. The oil was dissolved in 30 ml of dichloroethane and washed three times with 30 ml of water. After drying with forget-me-not and removing the solvent, the oily residue was chromatographed on a silica gel column. The column was eluted with hexane and ethyl acetate to give 0.6 g of the desired product in the oil phase.

Example 23

Synthesis of 2- (2-phenylethyl) imino-5-phenyl-4-thiazolidinone (Compound No. 23)

In the same manner as in Example 1, 1.8 g of methyl alpha-chlorophenyl acetate and 1.8 g of 1- (2-phenylethyl) 2-thiourea were used to obtain 1.9 g of the target substance.

M.P. : 167 to 170 ° C

Example 24

Synthesis of 3-cyclopropyl-2- (2,6-difluorobenzyl) imino-5-phenyl-4-thiazolidinone (Compound No. 24)

1.8 g of methyl alpha-chlorophenyl acetate and 2.4 g of N-cyclopropyl-N '-(2,6-difluorobenzyl) phenyl thiourea were used in the same manner as in Example 16 to obtain 1.2 g of an oily target product.

Example 25

Synthesis of 2- (3-fluorobenzyl) imino-3-methyl-5-phenyl-4-thiazolidinone (Compound No. 25)

1.8 g of methyl alpha-chlorophenyl acetate and 2.0 g of N- (3-fluoro) phenyl-N'-methyl thiourea were used in the same manner as in Example 1 to obtain 1.8 g of the target product.

M.P. : 87-88 degreeC

Example 26

Synthesis of 2- (2-chlorobenzyl) imino-3-methyl-5-phenyl-4-thiazolidinone (Compound No. 26)

1.8 g of methyl alpha-chlorophenyl acetate and 2.1 g of N- (2-chloro) phenyl-N'-methyl thiourea were used in the same manner as in Example 1 to obtain 2.0 g of the target product.

M.P. : 81 to 84 ° C

Example 27

Synthesis of 2- (2-fluorobenzyl) imino-3-methyl-5-phenyl-4-thiazolidinone (Compound No. 27)

2.3 g of alpha-bromophenylacetyl chloride was dissolved in 30 ml of acetonitrile, and 1.9 g of N- (2-fluoro) benzyl-N'-methyl thiourea was added to dissolve it. Stir for 2 hours. 30 ml of water was added to the reaction mixture, followed by extraction with 40 ml of ether. The diethyl ether layer was washed three times with 20 ml of water, dried over forget-me-not and the solvent was removed. The oily residue was chromatographed on a silica gel column. The column was eluted with hexane and ethyl acetate to give 2.0 g of the desired product.

M.P. : 91 to 94 ° C

Example 28

Synthesis of 2- (3-chlorobenzyl) imino-3-methyl-5-phenyl-4-thiazolidinone (Compound No. 28)

1.8 g of methyl alpha-chlorophenyl acetate and 2.1 g of N- (3-chloro) benzyl-N'-methyl thiourea were used in the same manner as in Example 1 to obtain 1.9 g of the target product.

M.P. : 74 to 77 ° C

Example 29

Synthesis of 2- (4-methylbenzyl) imino-3-methyl-5-phenyl-4-thiazolidinone (Compound No. 29)

After dissolving in 2.3 g of alpha-bromophenylacetyl chloride and 30 ml of toluene, 1.9 g of N- (4-methyl) benzyl-N'-methyl thiourea was added, followed by stirring at room temperature for 2 hours. 2.2 g of triethylamine was added to the reaction mixture, followed by further stirring at room temperature for 30 minutes. The mixture was filtered and washed three times with 30 ml of water, then dried over forget-me-not and the solvent was removed. The oily residue was chromatographed on a silica gel column. The column was eluted with hexane and ethyl acetate to give 1.3 g of the desired product.

M.P. : 74 to 77 ° C

Example 30

Synthesis of 2- [4- (methoxycarbonyl) phenyl] imino-3-methyl-5-phenyl-4-thiazolidinone (Compound No. 30)

1.8 g of methyl alpha-chlorophenyl acetate and 2.2 g of N- (4-methoxycarbonyl) phenyl-N'-methyl thiourea were used in the same manner as in Example 1 to obtain 2.2 g of the target product.

M.P. : 162 to 164 ° C

Example 31

Synthesis of 2- (4-methylcyclohexyl) imino-3-methyl-5-phenyl-4-thiazolidinone (Compound No. 31)

1.8 g of methyl alpha-chlorophenylacetate was dissolved in 30 ml of acetonitrile and dissolved by adding 2.2 g of N- (4-methyl) cyclohexyl-N'-methyl thiourea. Then, 2.0 g of triethylamine was added and warmed. Was stirred. After the reaction was completed, the mixture was lowered to room temperature, filtered, and the solvent was removed. The oil was dissolved in 30 ml of diethyl ether, and washed three times with 30 ml of water. After drying with forget-me-not and removing the solvent, the oily residue was chromatographed on a silica gel column. The column was eluted with hexane and ethyl acetate to give 1.9 g of the desired product.

M.P. : 91 to 93 ° C

Example 32

Synthesis of 2-fulfurylimino-3-methyl-5-phenyl-4-thiazolidinone (Compound No. 32)

1.8 g of methyl alpha-chlorophenyl acetate and 1.7 g of N-fulfuryl-N'-methyl thiourea were used in the same manner as in Example 1 to obtain 2.2 g of the target product.

M.P. : 96-99 degreeC

Example 33

Synthesis of 5- (2,4-dichloro) phenyl-2- (4-fluorobenzyl) imino-3-methyl-4-phenyl-thiazolidinone (Compound No. 33)

3.0 g of alpha-bromo (2,4-dichloro) phenylacetyl chloride was dissolved in 30 ml of acetonitrile, 2.0 g of N- (4-fluoro) benzyl-N'-methyl thiourea was added, followed by stirring at room temperature for 2 hours. It was. 2.2 g of triethyl amine was added to the reaction mixture, followed by further stirring at room temperature for 30 minutes. After removing the solvent, the oil was dissolved with 30 ml of ethyl acetate and washed three times with 30 ml of water. After drying with forget-me-not and removing the solvent, the oily residue was chromatographed on a silica gel column using hexane and ethyl acetate solvent to obtain 2.0 g of the desired product.

M.P. : 110 to 112 ° C

Example 34

Synthesis of 2-benzylimino-5- (2,4-dichloro) phenyl-3-methyl-4-thiazolidinone (Compound No. 34)

3.0 g of alpha-bromo (2,4-dichloro) phenyl acetyl chloride and 2.0 g of N-benzyl-N'-methyl thiourea were used in the same manner as in Example 33 to obtain 2.2 g of the target substance.

M.P. : 104 to 105 ° C

Example 35

Synthesis of 3-methyl-2- (1-naphthylmethyl) imino-5-phenyl-4-thiazolidinone (Compound No. 35)

1.8 g of methyl alpha-chlorophenyl acetate and 2.3 g of N-methyl-N '-(1-naphthyl) methyl thiourea were used in the same manner as in Example 1 to obtain 2.4 g of an oily target product.

M. P.: 81-84 ° C

Example 36

Synthesis of 2-benzylimino-5- (4-chloro) phenyl-3-4-thiazolidinone (Compound No. 36)

1.8 g of methyl alpha-chloro-4-chlorophenyl acetate and 1.8 g of N-benzyl-N'-methyl thiourea were used in Example 1 to obtain 2.1 g of the target product in oil form.

Example 37

Synthesis of 2- (4-chloro) phenyl-2- (4-fluorobenzyl) amino-3-methyl-4-thiazolidinone (Compound No. 37)

1.8 g of methyl alpha-chloro-4-chlorophenyl acetate and 2.0 g of N- (4-fluoro) benzyl-N'-methyl thiourea were used in the same manner as in Example 1 to obtain 2.0 g of the target substance.

M.P. : 95 to 96 ° C

Example 38

Synthesis of 2-benzylimino-3-methyl-5- (4-trifluoromethyl) phenyl-4-thiazolidinone (Compound No. 38)

1.3 g of alpha-bromo-4-trifluoromethylphenylacetyl chloride and 0.9 g of N-benzyl-N'-methyl thiourea were used in the same manner as in Example 33 to obtain 0.9 g of the target substance.

M.P. : 84 to 86 ° C

Example 39

Synthesis of 2- (4-fluorobenzyl) imino-3-methyl-5- (4-trifluoromethyl) phenyl-4-thiazolidinone (Compound No. 39)

1.3 g of alpha-bromo-4-trifluoromethylphenylacetyl chloride and 1.0 g of N- (4-fluoro) benzyl-N'-methyl thiourea were used in the same manner as in Example 33 to obtain 1.1 g of the target substance.

M.P. : 76 to 79 ° C

Example 40

Synthesis of 2- (4-methylcyclohexyl) imino-3-methyl-5- (4-trifluoromethyl) phenyl-4-thiazolidinone (Compound No. 40)

1.3 g of alpha-bromo-4-trifluoromethylphenylacetyl chloride and 0.9 g of N-methyl-N '(4-methyl) cyclohexyl thiourea were used in the same manner as in Example 33 to obtain 0.8 g of the target substance.

M.P. : 130 to 132 ° C

[Test Example 1]

Wheat rust disease test

8 seed seeds were sown in a disposable pot (5 cm in diameter) and grown in a greenhouse for 7 days to grow single-leafed wheat. The compound to be tested described in Table 2 was dissolved in acetone, and then diluted with Tween 20 solution to prepare a drug at 250 ppm concentration. This diluent was sprayed evenly on wheat, air-dried in a greenhouse for 1 day, and then inoculated with wheat rust spores. The inoculated wheat was stored for one day in the dark at 20 ° C. with 100% relative humidity, and then transferred to a 20 ± 1 ° C. humidity chamber with a relative humidity of 79% for 10 days.

The lesion formation temperature of the leaves was investigated, and the same test was repeated three times, and the results are shown in Table 2. Abbreviation evaluation criteria are as follows.

5: 95% or more control 100%

4: Control is 80% or more but less than 95%

3: Control is 50% or more but less than 80%

2: Control is more than 30% and less than 50%

1: 10% or more and less than 30%

0: Control is less than 10%

* As a control agent, the results were described in the same manner as in Test Example 1 using the fungicide 4-thiazolidinone reported in the Indian magazine Bokin Bobai, 1982, 10 (4), 155-8.

[Test Example 2]

Cucumber gray mold disease control test

Cucumber plants were grown until reaching one leaf level in the pot in the greenhouse. Next, the compound to be tested described in Table 3 was dissolved in acetone, and then diluted with Tween20 solution to prepare a drug at 250 ppm concentration. After spraying the diluted solution of this drug on one side of the cucumber leaf, a 5 × 10 ⁶ concentration of spore suspension was prepared from the white fungus grown in a greenhouse and incubated in a medium, and then sprayed and inoculated in a wet room at 20 ° C. for 5 days. It was treated and developed. The degree of lesion formation of the oil leaf was examined, and the same test was repeated three times, and the results are shown in Table 3. The symbol evaluation criteria were the same as in Test Example 1.

* As a control agent, the results were described in the same manner as in Test Example 2 using the fungicide 4-thiazolidinone reported in the Indian magazine Bokin Bobai, 1982, 10 (4), 155-8.

[Test Example 3]

Barley flour control test

8 seeds of barley seeds were sown in a disposable pot (5 cm in diameter) and grown in a greenhouse for 7 days to grow single-leafed barley. Next, as shown in Table 4, the compound to be tested was dissolved in acetone and diluted with Tween 20 solution to prepare a drug at 250 ppm concentration. The diluted solution of this drug was sprayed evenly over barley, air-dried in a greenhouse for 1 day, and inoculated with powdery mildew spores.

The inoculated barley was developed for 7 days in 22 ± 1 ° C. cultivation, and the degree of disease formation of the leaves was examined. The results of statistical treatment by repeating the same test three times are shown in Table 4. Drug evaluation criteria were the same as in Test Example 1.

* The control agent was described in the same manner as in Test Example 3 using the fungicide 4-thiazolidinone reported in the Indian magazine Bokin Bobai, 1982, 10 (4), 155-8.

By the test example as described above, it was proved that the 2-imino-4-thiozolidinone derivative prepared according to the present invention showed excellent control effects against wheat red rust, cucumber gray fungus, and barley powdery mildew.

Claims (6)

2-imino-4-thiozolidinone derivative represented by the following structural formula (I). [Formula 1] In Formula (I), R ¹ represents a phenyl group or a phenyl group including one or two halogen or trifluoromethyl groups, R ² represents hydrogen or an alkyl group having 1 to 3 carbon atoms or a cycloalkyl group, and R ³ is Cyano, fulfuryl, substituted cyclohexyl, naphthylmethyl group or the following formula. (In the formula, R ⁴ and R ⁵ independently represent hydrogen, methyl group or halogen, n is 0 to 2.) The compound of claim 1, wherein in formula (I), R ¹ represents a phenyl group or a phenyl group substituted with one or two halogen or trifluoromethyl groups, R ² is a lower alkyl group having 1 to 3 carbon atoms, and R ³ 2-amino-4-thiazolidinone derivative characterized by the following formula. (In the formula, R ⁴ and R ⁵ independently represent hydrogen, methyl group or halogen, n is 0 to 2.) 2-imino-4-thiae represented by the following general formula (I) characterized by reacting the compound represented by the following general formula (II) and the compound represented by the following general formula (III) in the presence of a base in a solvent. Method for preparing zolidinones derivatives. [Formula 1] [Formula 2] [Formula 3] Wherein R ¹ represents a phenyl group or a phenyl group comprising one or two halogen or trifluoromethyl groups, X represents a halogen group, Y represents a C1-4 lower alkoxy or halogen atom, and R ² represents hydrogen or C1 It represents ^-3 alkyl groups or a cycloalkyl group, R <^3> is represented by a cyano and a fupu by the methylcyclohexyl, a naphthylmethyl group, or the following formula. (In the formula, R ⁴ and R ⁵ independently represent hydrogen, methyl group or halogen, n is 0 to 2.) According to claim 3, wherein the reaction is a method for producing a 2-imino-4-thiazolidinone derivative, characterized in that the reaction within a temperature range of -10 ~ 150 ℃. The 2-imino-4-thia according to claim 3 or 4, wherein the reaction is carried out at 10 to 50 DEG C when Y is a halogen atom and at 50 to 110 DEG C when Y is an alkoxy group. Method for preparing zolidinones derivatives. A bactericide containing at least one compound selected from the 2-imino-4-thiazolidinone derivatives according to claim 1.