KR830002009B1 - Method for preparing substituted 1-thia-3-aza-4-one - Google Patents

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Description

Method for preparing substituted 1-thia-3-aza-4-one

The present invention relates to a process for the preparation of substituted 1-thia-3-aza-4-one, which is an organic heterocycle compound, and more particularly to a process for preparing the 4-thiazolidinone compound of the general formula (VII).

In the above formula,

R is C ₃ to C ₁₀ alkyl, C ₃ to C ₈ cyclo-alkyl, metaryl, phenyl, halophenyl, tri-fluoromethylphenyl, benzyl, methoxybenzyl, methylbenzyl, halobenzyl, dimethylaminoethyl, methylcyclo Hexyl, C ₃ to C ₈ cyclo-alkyl (C ₁ to C ₃ ) alkyl, α-methylbenzyl, 2-thiazolyl, nitrophenyl, phenoxyphenyl, (tetrahydro-2-furanyl) methyl, haloaniyl , Trifluoromethylthiophenyl, methylthiophenyl, 2-norbornyl, furfuryl, 2- (1-methoxypropyl), methoxyphenyl, fluoro (C ₁ to C ₂ ) alkoxy-phenyl, 3, 4 -(Methylenedioxy) phenyl, xylyl, biphenylyl, tolyl or halotolyl,

R ¹ is hydrogen, methyl or —S (C ₁ to C ₆ alkyl);

R ² is hydrogen, C ₁ to C ₆ alkyl or —S (C ₁ to C ₆ alkyl).

In the prior art, Surrey described in J. Chem. Am. Chem. Soc. 69. 2911-2912 (1947) describes the preparation of 4-thiazolidone by reaction of thioglycolic acid with a Schiffbase. However, no mention is made of the usefulness of the compounds prepared in this document.

Also in the prior art, Troutman et al. Am. Chem. Soc. 70. 3436-3439 (1948)] describes the synthesis of 2-aryl-3-alkyl- or 2-hetero-3-alkyl-4-thiazolidone exhibiting mycelial action.

Another prior art document [J. Am. Chem. Soc. 75. 109-114 (1953) described Pennington et al. Preparing a 2-substituted-4-thiazolidone that exhibits anti-tuberculosis activity in vitro.

Surrey et al. Also describe J. Am. Chem. Soc. 76. 578-580 (1954), for the preparation of 2-aryl-4-thiazolidone, which exhibits excellent livemeba function (for Endamoeba criceti) in experiments with hamsters. Described.

See also Singh's [J. Indian Chem. Soc., 595-597 (1976), discloses various 5-methyl-3-aryl-2-arylimino-4-thiazolidinones that exhibit fungicidal activity against the test strain, Alternaria Solani. And the synthesis ratio of the acetoxy mercury derivative thereof is described.

In addition, Japanese Patent No. 48-17276 relates to a method for preparing a 2-pyridyl substituted thiazolidinone derivative in a molecular structure, and these compounds have been demonstrated to have a central nervous inhibitory effect.

In addition, US Pat. No. 4,017,628 (April 12, 1977) relates to a method of improving (ohm) treatment of animals using a 2-pyridyl substituted thiazolidinone compound.

See also Jadhab et al., J. Indian Chem. Soc., 424-426 (1978), discloses 2-methyl-2- (2-hydroxy-4, 5-dimethylphenyl) -3, which exhibits fungicidal activity against Helmynthosporium appatarnae. A process for preparing aryl-4-thiazolidinone is described.

The present invention relates to a process for the preparation of novel 1-thia-3-aza-4-one useful as plant fungicides, terrestrial and aquatic plant growth regulators.

According to the present invention, the 4-thiazolidinone compound of the following general formula (VII) is reacted with 3-pyridylcarboxaldehyde of the following general formula (VIII) with a substituted amine of the following general formula (IX), followed by thioglycol Prepared by reaction with acid or thioractic acid.

In the above formula,

R is C ₃ to C ₁₀ alkyl, C ₃ to C ₈ -C ₃ cycloalkyl, metaryl, phenyl, halophenyl, trifluoromethylphenyl, benzyl, methoxybenzyl, methylbenzyl, halobenzyl, dimethylaminoethyl, methyl Cyclohexyl, C ₃ to C ₈ cyclo-alkyl (C ₁ to C ₃ ) alkyl, α-methylbenzyl, 2-thiazolyl, nitrophenyl, phenoxyphenyl, (tetrahydro-2-furanyl) methyl, haloaniyl Reel, trifluoromethylthiophenyl, methylthiophenyl, 2-norbornyl, furfuryl, 2- (1-methoxypropyl), methoxyphenyl, fluoro (C ₁ to C ₂ ) alkoxyphenyl, 3, 4 -(Methylenedioxy) phenyl, xylyl, biphenylyl, tolyl or halotolyl;

R ¹ is hydrogen, methyl or —S (C ₁ to C ₆ alkyl);

R ² is hydrogen, C ₁ to C ₆ alkyl or —S (C ₁ to C ₆ alkyl).

When R ¹ or R ² in the compound of formula (VII) is hydrogen, the compound is mono- or di-alkylated such that R ¹ is methyl or —S (C ₁ to C ₆ alkyl) or R ² is C ₁ to It is possible to produce compounds of formula (VII) which are C ₆ alkyl or -S (C ₁ to C ₆ alkyl). The 4-keto group of formula (VII) also reacts further with P ₂ S ₅ to produce the corresponding thions. When the R group of the amine is a steric hindrance group, pulmonary ring agents such as N, N'-dicyclohexylcarbodiimide or N-ethoxy-carbonyl-2-ethoxy-1, 2-dihydroquinoline Use to complete the ring closure.

The present invention relates to fungicidal compositions characterized by containing the following general formula (IV) compounds as active ingredients and fungicidally acceptable excipients.

In the above formula

R ¹¹ is C ₃ to C ₁₀ alkyl, phenyl, halophenyl, metaryl, C ₃ to C ₈ cycloalkyl, nitrophenyl, methylcyclohexyl, fluoro- (C ₁ to C ₂ ) alkoxyphenyl, tolyl, xylyl Methoxyphenyl, trifluoromethylphenyl, halotolyl, habenzyl, 3, 4- (methylenedioxy) phenyl or biphenylyl;

R ¹² is hydrogen or methyl;

R ¹³ is hydrogen or C ₁ to C ₆ alkyl.

The present invention also relates to an aquatic plant growth regulator composition, which comprises the following general formula (VI) compound as an active ingredient and aquaculture acceptable excipients.

In the above formula

R ¹⁶ is C ₃ to C ₁₀ alkyl, C ₃ to C ₈ -cycloalkyl, metaryl, phenyl, halophenyl, trifluoromethylphenyl, methoxybenzyl, methyl-benzyl, halobenzyl, benzyl, dimethylaminoethyl, C ₃ to C ₈ cycloalkyl (C ₁ to C ₃ ) -alkyl, methylcyclohexyl, 2-thiazolyl, α-methylbenzyl, phenoxyphenyl, (tetrahydro-2-furanyl) methyl, haloaniyl, Silyl, trifluoromethylthiophenyl, methylthiophenyl, methoxyphenyl, fluoro (C ₁ to C ₂ ) alkoxyphenyl, 3, 4- (methylenedioxy) phenyl, biphenylyl, 2-norbornyl, green Furyl, 2- (1-methoxypropyl), halotolyl or tolyl;

X is oxygen or sulfur;

이며 ;Z is

And;

R ¹ is hydrogen, methyl or —S (C ₁ to C ₆ alkyl);

R ² is hydrogen, C ₁ to C ₆ alkyl or —S (C ₁ to C ₆ alkyl).

The present invention also relates to a method of protecting a plant from phytopathogenic fungi by contacting the following general formula (IV) compound with fungi in an amount that is fungicidally effective but without herbicidal effect.

In the above formula

R ¹¹ is C ₃ to C ₁₀ alkyl, phenyl, halophenyl, metaryl, C ₃ to C ₈ cycloalkyl, nitrophenyl, methylcyclohexyl, fluoro- (C ₁ to C ₂ ) alkoxyphenyl, tolyl, xylyl Methoxyphenyl, trifluoromethylphenyl, halotolyl, habenzyl, 3, 4- (methylenedioxy) phenyl or biphenylyl;

R ¹² is hydrogen or methyl;

R ¹³ is hydrogen or C ₁ to C ₆ alkyl.

The present invention is also characterized in that the following general formula (VI) compound is added to the growing water in water and floating aquatic weeds in an amount sufficient to provide a concentration that regulates plant growth but does not exhibit herbicidal effects. A method of controlling the growth of aquatic weeds.

In the above formula

R ¹⁶ is C ₃ to C ₁₀ alkyl, C ₃ to C ₈ -cycloalkyl, metaryl, phenyl, halophenyl, trifluoromethylphenyl, methoxybenzyl, methylbenzyl, halobenzyl, benzyl, dimethylaminoethyl, C ₃ To C ₈ -cycloalkyl (C ₁ to C ₃ ) alkyl, methylcyclohexyl, 2-thiazolyl, α-methylbenzyl, phenoxyphenyl, (tetrahydro-2-furanyl) methyl, haloaniyl, xylyl , Trifluoromethylthiophenyl, methylthiophenyl, methoxyphenyl, fluoro (C ₁ to C ₂ ) alkoxyphenyl, 3, 4- (methylenedioxy) phenyl, biphenylyl, 2-norbornyl, furfuryl , 2- (1-methoxypropyl), halotolyl or tolyl;

X is oxygen or sulfur;

이며 ;Z is

And;

R ¹ is hydrogen, methyl or —S (C ₁ to C ₆ alkyl);

R ² is hydrogen, C ₁ to C ₆ alkyl or —S (C ₁ to C ₆ alkyl).

The compound of formula (VI) may also be used as a terrestrial plant growth regulator.

In the above formula, C ₃ to C ₁₀ alkyl is n-propyl, isopropyl, n-butyl, secondary butyl, isobutyl, t-butyl, n-pentyl, isopentyl, secondary-pentyl, t-pentyl, n -Hexyl, secondary-hexyl, isohexyl, t-hexyl, n-heptyl, isoheptyl, secondary-heptyl, n-octyl, secondary-octyl, isooctyl, n-nonyl, secondary-nonyl, isononyl , n-decyl, secondary-decyl and the like.

In addition, C ₁ to C ₆ alkyl are methyl, ethyl, n-propyl, isopropyl, n-butyl, secondary-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, secondary-pentyl, t- Pentyl, n-hexyl, secondary-hexyl, isohexyl, t-hexyl and the like.

The term -s (C ₁ to C ₆ alkyl) refers to methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, secondary-butylthio, t-butylthio, n-amyl Alkylthios such as thio, isoamylthio, secondary-amylthio, n-hexylthio, secondary-hexylthio, isohexylthio and the like.

C ₃ to C ₈ cycloalkyl denote saturated monocyclic cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.

Halophenyls are o-chlorophenyl, p-chlorophenyl, p-fluorophenyl, p-bromophenyl, p-iodophenyl, m-chlorophenyl, o-bromophenyl, o-fluorophenyl, 2, 4-difluorophenyl, 2, 5-dichlorophenyl, 2, 5-dibromophenyl, 2, 4-dichlorophenyl, 2-bromo-4-chlorophenyl, 2, 4-dibromophenyl, 3 , 4-difluorophenyl, 4-bromo-2-chlorophenyl, 4-bromo-3-fluorophenyl, 3, 4-dichlorophenyl, 3, 4-dibromophenyl, 4-chloro-3 -Fluorophenyl, 3, 5-difluorophenyl, 3, 5-dichlorophenyl, 3, 5-dibromophenyl, 2, 3, 4-trichlorophenyl, 2, 4, 5-trichlorophenyl, 2, 3, 4, 5-tetrachlorophenyl, etc. are shown.

Halobenzyl is o-chlorobenzyl, p-chlorobenzyl, p-fluorobenzyl, p-bromobenzyl, p-iodobenzyl, m-chlorobenzyl, m-bromobenzyl, m-fluorobenzyl, 2, 4-dichlorobenzyl, 2-bromo-4-chlorobenzyl, 3, 4-dibromobenzyl, 2, 5-dichlorobenzyl, 3, 5-dibromobenzyl, 4-chloro-3-fluorobenzyl, 2, 5-difluorobenzyl, etc. are shown.

Haloanilyl refers to p-chloroanilyl, o-chloroanilyl, m-chloroanilyl, 2, 6-dichloroanilyl, p-bromoanilyl, o-bromoanilyl and the like.

Fluoro (C ₁ to C ₂ ) alkoxyphenyl represents trifluoromethoxyphenyl, 1, 1, 2, 2-tetrafluoroethoxyphenyl and pentafluoroethoxyphenyl.

C ₃ to C ₈ cycloalkyl (C ₁ to C ₃ ) alkyl is cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyclopropylethyl, cyclobutylethyl, cyclopentylethyl, cyclohexylethyl, cycloheptyl Ethyl, cyclooctylethyl, cycloheptylmethyl, cyclooctylmethyl, cyclopropylpropyl, cyclobutylpropyl, cyclopentylpropyl, cycloheptylpropyl, cyclooctylpropyl, 1- (2-cyclopentyl-1-methyl) ethyl, 1- Cyclohexylpropyl, and the like.

Methoxyphenyl represents 4-methoxyphenyl, 3, 4-dimethoxyphenyl, 3-methoxyphenyl and 3, 5-dimethoxyphenyl.

Halo or halogen is chlorine, bromine, iodine or fluorine.

Xylyl represents 3, 4-dimethylphenyl, 2, 3-dimethylphenyl, 3, 5-dimethylphenyl, 2, 4-dimethylphenyl and 2, 5-dimethylphenyl.

Tolyl refers to o-, m- and p-tolyl.

Compounds of formula (VI) have been found to have an effect of regulating aquatic weed growth when applied to the weed's habitat in a concentration range of about 0.25 to about 10 ppm, suitably about 0.25 to about 2 ppm.

Preferred compounds of general formula (VI) for use as aquatic plant growth regulators

R is cyclopentyl, cyclohexyl, 1-methylhexyl, n-hexyl, o-tolyl, 2-chlorophenyl, 2-fluorophenyl, 2-4-difluorophenyl, 4-chlorophenyl, and 2, 4 -Dichlorophenyl;

이고 ;Z is

ego ;

R ¹ is hydrogen or methyl;

R ² is hydrogen, methyl, n-propyl or n-butyl.

Another aspect of the present invention is that the fungal but not herbicidal effect of the compound of general formula (IV) may inhabit the part of the plant in which the fungus inhabits, ie, leaves, stems, flowers or roots or fungi. The present invention relates to a method of protecting a plant from phytopathogenic fungi, characterized by contact with soil. The application amount may vary depending on the method of protecting the plant from phytopathogenic fungi in the greenhouse or outdoors and the degree of infection of the fungi. For example, when used in a greenhouse, the fungicidal compound is applied by the soil trench method using a composition containing the active ingredient at a concentration of about 1 to about 200 ppm, preferably at a concentration of about 5 to about 100 ppm. . As will be well understood by those skilled in the art, outdoor treatments generally use higher amounts than those used in greenhouses, i.e., from about 25 to about 1000 ppm.

The novel compounds of general formula (IV) are Erysiphe graminis tritici, the homogeneous cause of powdery mildew in wheat by suitable tests; Erysiphe cicoracearum, the causative agent of cucumber powdery mildew; Erysiphe polygoni, the causative agent of soybean flour; Helminthosporium sativum, the causative agent of Helminthosporium leaf spot; Venturia inaequalis, the causative agent of apple black spots; Plasmopara viticola, the causative agent of Staphylococcus aureus; Cercospora beticola, a causative agent of cercospora leaf spots; It has been shown to inhibit various fungi, including septoria tritici, the causative agent of septoria leaf blatch, and Rhizoctonia solani, the causative agent of Rhizoctonia damping-off.

Preferred compounds of the general formula (IV) for use in the method of protecting plants from phytopathogenic fungi are R halophenyl, cyclohexyl or tolyl;

이고 ;Z is

ego ;

R ¹ is hydrogen or methyl,

R ² is hydrogen, methyl or propyl.

The novel compounds of formula (VII) are prepared by the process described below, and this fixation is slightly different depending on whether the specific compound to be produced is thiazolidinone or thiazinone. Substituted 1-thia-3-aza-4-, represented by the substituted 4-thiazolidinone compound, is prepared according to the following general reaction sequence;

In which R has the same meaning as described above.

In carrying out the present reaction, an appropriately substituted aniline or alkyneamine is dissolved in a water-immiscible solvent which is inert to the conditions under which the reaction is carried out, and 3-pyridylcarboxaldehyde is added to this solution.

Suitable solvents include benzene, toluene, xylene and the like. The mixture is refluxed for a period of time and the reaction byproduct water in the transfer is collected in a suitable water collector, for example a Dean-Stark trap. The intermediate formed, 3-[(substituted phenylimino) methyl] pyridine, is generally not isolated. After the calculated amount of water generated from the reaction mixture has been collected, the reaction mixture is cooled to approximately room temperature and excess thioglycolic acid (α-mercaptoacetic acid) or thioractic acid (2-mercaptopropionic acid) is added, and Dean-Starktrap The reaction mixture is refluxed again until no more water is collected. This reaction takes about 4 hours. The reaction mixture is then cooled and concentrated to dryness in vacuo and the residue is recrystallized from a suitable solvent or purified by column chromatography. By this general process, 4-thiazolidinone containing a 5-membered heterocycle nucleus is produced.

이고 R¹및/또는 R²가 함께 동일한 수소인 일반식(VI)의 화합물은 본 분야의 전문가에게 알겨진 방법에 의해 용이하게 알킬화시킬 수 있다. 알킬화는 4-티아졸리디논환의 카보닐관능기에 대한 α-위치에서 일어난다. 그러므로 예를 들어, 테트라하이드로푸란에 용해된 3-(4-클로로페닐)-5-메틸-2-(3-피리딜)-4-티아졸리디논을 교반하면서 n-부틸리튬의 헥산용액 및 테트라하이드로푸란의 혼합물에 가하고, 건조 질소대기하에서 유지시킨 후 약 -50℃ 내지 약 -70℃의 온도로 냉각시킨다. 반응 혼합물을 약 -70℃에서 약 1/2시간 동안 교반한 후에, 메틸요오다이드를 교반하면서 적가한 다음, 반응혼합물을 약 12시간 교반하고, 실온까지 서서히 가온한다. 반응생성물의 혼합물에 물을 가한 후 에테르로 추출한다. 에테르추출물을 건조시켜 진공하에 농축시키고, 잔사는 적절한 용매, 예를 들면 석유에테르(비점 60 내지 70℃) 및 에틸에테르의 혼합물로부터 재결정시켜 융점 약 140 내지 141℃의 생성물을 수득하며, 이 생성물은 3-(4-클로로페닐)-5, 5-디메틸-2-(3-피리딜)-4-티아졸리디논으로 확인된다.Z is

And wherein R ¹ and / or R ² together are the same hydrogen, compounds of formula (VI) can be readily alkylated by methods known to those skilled in the art. Alkylation occurs at the α-position to the carbonyl functional group of the 4-thiazolidinone ring. Thus, for example, hexane solution of n-butyllithium and tetra while stirring 3- (4-chlorophenyl) -5-methyl-2- (3-pyridyl) -4-thiazolidinone dissolved in tetrahydrofuran It is added to a mixture of hydrofuran and maintained under dry nitrogen atmosphere and then cooled to a temperature of about -50 ° C to about -70 ° C. The reaction mixture is stirred at about −70 ° C. for about 1/2 hour, then methyl iodide is added dropwise with stirring, then the reaction mixture is stirred for about 12 hours and slowly warmed to room temperature. Water is added to the mixture of reaction products and extracted with ether. The ether extract is dried and concentrated in vacuo and the residue is recrystallized from a mixture of a suitable solvent such as petroleum ether (boiling point 60-70 ° C.) and ethyl ether to give a product having a melting point of about 140-141 ° C., which product 3- (4-chlorophenyl) -5, 5-dimethyl-2- (3-pyridyl) -4-thiazolidinone.

The process for the preparation of the compound of general formula (VII) in which 4-carbonyloxygen is substituted with sulfur is performed by the process of preparing the carbonyloxygen compound in a suitable solvent, preferably anhydrous pyridine (P) for about 18 hours. ₂ S ₅ ) and then the product is separated.

Suitable acid addition salts of the general formula (VII) compounds can be readily prepared by conventional processes well known to those skilled in the art, using acids selected from the group consisting of hydrochloric acid, hydrobromic acid, sulfuric acid, p-toluenesulfonic acid, and the like. Can be.

(여기에서, R¹과 R²는 같지 않다)인 경우에 입체이성체로 존재한다. 이러한 입체이성체는 본 분야의 전문가에게 잘 알려진 방법으로, 적합한 단리제를 사용하거나 크로마토그라피 방법에 의해 분리될 수 있다.Compound of formula (VII) is Z

Where R ¹ and R ² are not the same. Such stereoisomers are well known to those skilled in the art and can be separated using suitable isolators or by chromatographic methods.

Synthesis of the compound of formula (VII) is described in more detail in the following examples in accordance with the general procedure above, which examples do not limit the scope of the invention.

Example 1

3- (4-chlorophenyl) -5-methyl-2- (3-pyridyl) -4-thiazolidinone

25.4 g (0.27 mole) of 4-chloroaniline and 250 ml of toluene were placed in a round bottom three-necked flask equipped with a condenser, Dean-Stark trap and a mechanical stirrer. 21.4 g (0.27 mol) of 3-pyridylcarbaldehyde is added to this solution while stirring and the reaction mixture is refluxed until a calculated amount of water (about 3.6 mL) is collected in the Dean-Stark trap.

After the thermal reaction mixture is cooled to room temperature, excess thiolactic acid (30 g in total) is added and the reaction mixture is heated to reflux again until no more water is collected in the Dean-Stark trap. In this case, about 4 hours of heating is required. The reaction mixture is then cooled and concentrated to dryness in vacuo. The solid residue is recrystallized from a mixture of hot ethyl ether and acetone to give a product having a melting point of about 120 to 122 ° C., which is obtained by infrared and NMR spectroscopy and elemental analysis by 3- (4-chlorophenyl) -5-methyl-. It is identified as 2- (3-pyridyl) -4-thiazolidinone.

Yield: 7 g

Elemental Analysis: C ₁₅ H ₁₃ ClN ₂ OS

Additional compounds are prepared and identified according to the general preparation of Example 1. The following examples describe the main starting materials used in the preparation and the compounds produced along with their weights.

Example 2

3- (2,4-difluorophenyl) -2- (3-pyri) having a melting point of about 125 to 127 ° C. from 13 g of 2, 4-difluoroaniline, 10 g of 3-pyridyl carboxaldehyde and 13 g of thioglycolic acid 15 g of dill) -4-thiazolidinone is obtained.

Elemental analysis ‥ C ₁₄ H ₁₀ F ₂ N ₂ OS

Example 3

3- (2-fluorophenyl) -2- (3-pyridyl) -4-thiane having a melting point of about 142 to 143 ° C from 15 g of 2-fluoroaniline, 15 g of 3-pyridyl carboxaldehyde and 13 g of thioglycolic acid 8 g of zolidinones are obtained.

Elemental Analysis: C ₁₄ H ₁₁ FN ₂ OS

Example 4

From 2.3 g of N-nonylamine, 15 g of 3-pyridylcarboxaldehyde and 13 g of thioglycolic acid, 2.3 g of 3-nonyl-2- (3-pyridyl) -4-thiazolidinone having a melting point of about 82 to 83 ° C is obtained. .

Elemental Analysis: C ₁₇ H ₂₆ N ₂ OS

Example 5

20 g of 3- (4-chlorobenzyl) -2- (3-pyridyl) -4-thiazolidinone at a melting point of about 134 DEG C from 15 g of 4-chlorobenzylamine, 15 g of 3-pyridyl carboxaldehyde and 13 g of thioglycolic acid To obtain.

Elemental Analysis: C ₁₅ H ₁₃ ClN ₂ OS

Example 6

6.5 g of 3-cyclopentyl-2- (3-pyridyl) -4-thiazolidinone having a melting point of about 118 to 119 ° C. are obtained from 12 g of cyclopentylamine, 15 g of 3-pyridyl carboxaldehyde and 13 g of thioglycolic acid. .

Elemental Analysis: C ₁₃ H ₁₆ N ₂ OS

Example 7

From 9 g of aniline, 15 g of 3-pyridylcarboxaldehyde and 13 g of thioglycolic acid, 9 g of 3-phenyl-2- (3-pyridyl) -4-thiazolidinone having a melting point of about 177 to 178 ° C is obtained.

Elemental Analysis: C ₁₄ H ₁₂ N ₂ OS

Example 8

From 23 g of 2-methallyl aniline, 20 g of 3-pyridylcarboxaldehyde and 20 g of thioglycolic acid, 23 g of 3- (2-methallyl) -2- (3-pyridyl) -4-thiazolidinone having a melting point of 84 ° C. were obtained. do.

Elemental Analysis: C ₁₂ H ₁₃ N ₂ OS

Example 9

3 g of 3- (1-methylhexyl) -2- (3-pyridyl) -4-thiazolidinone having a melting point of about 67 ° C. was obtained from 16 g of 2-aminoheptane, 15 g of 3-pyridylcarboxaldehyde and 13 g of thioglycolic acid. do.

Elemental Analysis: C ₁₅ H ₂₂ N ₂ OS

Example 10

13 g of 3- (3-chlorophenyl) -2- (3-pyridyl) -4-thiazolidinone having a melting point of about 154 to 155 DEG C from 13 g of 3-chloroaniline, 10 g of 3-pyridylcarboxaldehyde and 10 g of thioglycolic acid To obtain.

Elemental Analysis: C ₁₄ H ₁₁ ClN ₂ OS

Example 11

2- (3-pyridyl) -3- (α, α, α-trifluoro-m-tolyl) in oil form from 16 g of 3-trifluoromethylaniline, 15 g of 3-pyridylcarboxaldehyde and 13 g of thioglycolic acid 8 g of 4-thiazolidinone is obtained.

NMR (CDCl ₃ ) (S)

Elemental Analysis: C ₁₅ H ₁₁ F ₃ N ₂ OS

Example 12

3- (4-fluorophenyl) -2- (3-pyridyl) -4-thiazoli having a melting point of about 161 DEG C from 55.5 g of 4-fluoroaniline, 53.5 g of 3-pyridylcarboxaldehyde and 46 g of thioglycolic acid 70 g of dinon are obtained.

Elemental Analysis: C ₁₄ H ₁₁ FN ₂ OS

Example 13

15 g of 3- (cyclohexylmethyl) -2- (3-pyridyl) -4-thiazolidinone at a melting point of about 70 ° C. are obtained from 11.3 g of cyclohexanemethaneamine, 10 g of 3-pyridylcarboxaldehyde and 10 g of thioglycolic acid. do.

Confirm by NMR spectrum.

Example 14

3- (3,5-dichlorophenyl) -2- (3-pyridyl) having a melting point of about 160 ° C. to 161 ° C. from 16.2 g of 3, 5-dichloroaniline, 11 g of 3-pyridyl carboxaldehyde and 10 g of thioglycolic acid 11 g of 4-thiazolidinone is obtained.

NMR (CDCl ₃ ) (δ)

Example 15

(2-fluorobenzyl) -2- (3-pyridyl) -4-thia at a melting point of about 103 ° C. from 12.5 g of 2-fluorobenzylamine, 10.7 g of 3-pyridyl carboxaldehyde, and 10 g of thioglycolic acid 6 g of zolidinones are obtained.

NMR (CDCl ₃ ) (δ)

Example 16

3- (3,4-methylenedioxybenzyl) -2- (3-pyridyl) -4 at a melting point of about 121-122 ° C. from 15.1 g of piperonyl amine, 11 g of 3-pyridylcarboxaldehyde and 14 g of thioglycolic acid 4 g of thiazolidinone is obtained.

Elemental Analysis: C ₁₆ H ₁₄ N ₂ O ₃ S

Example 17

3- (3,4-dichlorophenyl) -2- (3-pyridyl) -4 at a melting point of about 160 to 162 ° C. from 16.2 g of 3, 4-dichloroaniline, 11 g of 3-pyridylcarboxaldehyde and 14 g of thioglycolic acid 14 g of thiazolidinone is obtained.

Elemental Analysis: C ₁₄ H ₁₀ Cl ₂ N ₂ OS

Example 18

3- (2,4-dichlorophenyl) -2- (3-pyridyl) -4 at a melting point of about 170-171 ° C. from 16.2 g of 2, 4-dichloroaniline, 12 g of 3-pyridylcarboxaldehyde and 12 g of thioglycolic acid 4 g of thiazolidinone is obtained.

Elemental Analysis: C ₁₄ H ₁₀ Cl ₂ N ₂ OS

Example 19

3- (4-chlorophenyl) -2- (3-pyridyl) -4-thiazolidinone at a melting point of about 149-151 ° C. from 9 g of 4-chloroaniline, 7.5 g of 3-pyridylcarboxaldehyde and 15 g of thioglycolic acid 9 g are obtained.

Elemental Analysis: C ₁₄ H ₁₁ ClN ₂ OS

Example 20

2- (3-pyridyl) -3- [3- (1, 1, 2, 2-tetrafluoro) in oil phase from 21 g of 3-tetrafluoroethoxyaniline, 11 g of 3-pyridylcarboxaldehyde and 14 g of thioglycolic acid 4 g of roethoxy) phenyl] -4-thiazolidinone is obtained.

NMR (CDCl ₃ ) (δ)

Elemental analysis: C ₁₆ H ₁₂ F ₄ N ₂ O ₂ S

Example 21

From 10 g of cyclohexylamine, 15 g of 3-pyridylcarboxaldehyde and 13 g of thioglycolic acid, 4.6 g of 3-cyclohexyl-2- (3-pyridyl) -4-thiazolidinone having a melting point of about 110 to 111 ° C is obtained.

Elemental Analysis: C ₁₄ H ₁₈ N ₂ OS

Example 22

16 g of 3-cyclopropyl-2- (3-pyridyl) -4-thiazolidinone having a melting point of about 112 to 113 ° C. are obtained from 8 g of cyclopropylamine, 15 g of 3-pyridylcarboxaldehyde and 13 g of thioglycolic acid.

Elemental Analysis: C ₁₁ H ₁₂ N ₂ OS

Example 23

3- (3-chlorophenyl) -5-methyl-2- (3-pyridyl) -4-thiazolidinone at a melting point of about 133 ° C. from 18 g of 3-chloroaniline, 15 g of 3-pyridylcarboxaldehyde and 13 g of thiolactic acid 9.5 g are obtained.

Elemental Analysis: C ₁₅ H ₁₃ ClN ₂ OS

Example 24

4.6 g of 3- (2-chlorophenyl) -2- (3-pyridyl) -4-thiazolidinone at a melting point of about 134 ° C. was obtained from 18 g of 2-chloroaniline, 15 g of 3-pyridylcarboxaldehyde and 13 g of thioglycolic acid. To obtain.

Elemental Analysis: C ₁₄ H ₁₁ ClN ₂ OS

Example 25

From 16 g of p-toluidine, 15 g of 3-pyridylcarboxaldehyde and 13 g of thioglycolic acid, 16 g of 2- (3-pyridyl) -3- (4-tolyl) -4-thiazolidinone at a melting point of about 187 ° C are obtained.

Elemental Analysis: C ₁₅ H ₁₄ N ₂ OS

Example 26

3- (4-methoxyphenyl) -2- (3-pyridyl) -4-thiazoli having a melting point of about 144 to 145 DEG C from 17 g of 4-methoxyaniline, 15 g of 3-pyridylcarboxaldehyde and 13 g of thioglycolic acid 5 g of dinon is obtained.

Elemental Analysis: C ₁₅ H ₁₄ N ₂ O ₂ S

Example 27

16 g of 4-aminobenzotrifluoride, 15 g of 3-pyridylcarboxaldehyde and 13 g of thioglycolic acid, 2- (3-pyridyl) -3- (α, α, α-trifluoro-p having a melting point of about 148 ° C 8 g of -tolyl) -4-thiazolidinone is obtained.

Elemental Analysis: C ₁₅ H ₁₁ F ₃ N ₂ OS

Example 28

From 21 g of n-hexylamine, 11 g of 3-pyridylcarboxaldehyde and 10 g of thioglycolic acid, 21 g of 3-hexyl-2- (3-pyridyl) -4-thiazolidinone having a melting point of about 78 ° C are obtained.

Elemental Analysis: C ₁₄ H ₂₀ N ₂ OS

Example 29

13 g of 3-cyclohexyl-5-methyl-2- (3-pyridyl) -4-thiazolidinone having a melting point of about 106 ° C. were obtained from 10 g of cyclohexylamine, 10.7 g of 3-pyridylcarboxaldehyde and 10.6 g of thiolactic acid. do.

Elemental Analysis: C ₁₅ H ₂₀ N ₂ OS

Example 30

5-methyl-3- (4-tolyl) -2- (3-pyridyl) -4-thiazoli having a melting point of about 170 ° C. from 10.7 g of p-toluidine, 10.7 g of 3-pyridylcarboxaldehyde and 10.6 g of thiolactic acid 18 g of dinon is obtained.

Elemental Analysis: C ₁₆ H ₁₆ N ₂ OS

Example 31

3- (4-chlorobenzyl) -5-methyl-2- (3-pyridyl) -4-thiazolidinone in oil form from 14 g of 4-chlorobenzylamine, 10.7 g of 3-pyridylcarboxaldehyde and 10.6 g of thiolactic acid 7.9 g is obtained.

Elemental Analysis: C ₁₆ H ₁₅ ClN ₂ OS

Example 32

3- (2-chlorophenyl) -5-methyl-2- (3-pyridyl)-having a melting point of about 104 to 105 ° C. from 12.7 g of 2-chloroaniline, 10.7 g of 3-pyridylcarboxaldehyde and 10.6 g of thiolactic acid 600 mg of 4-thiazolidinone is obtained.

Elemental Analysis: C ₁₅ H ₁₃ ClN ₂ OS

Example 33

5-methyl-3- (1-methylhexyl) -2- (3-pyridyl) -4-thiazolidinone in oil form from 11.5 g of 2-aminoheptane, 10.7 g of 3-pyridylcarboxaldehyde and 10.6 g of thiolactic acid 14 g are obtained.

NMR (CDCl ₃ ) (δ)

Elemental Analysis: C ₁₆ H ₂₄ N ₂ OS

Example 34

3-hexyl-5-methyl-2- (3-pyridyl) -4-thiazolidinone having a melting point of about 67 to 68 ° C. from 10.1 g of n-hexylamine, 10.7 g of 3-pyridylcarboxaldehyde and 10.6 g of thiolactic acid 5.7 g are obtained.

Elemental Analysis: C ₁₅ H ₂₂ N ₂ OS

Example 35

3- (2-fluorophenyl) -5-methyl-2- (3-pyridyl) -4 at a melting point of about 105 ° C. from 11 g of 2-fluoroaniline, 10.7 g of 3-pyridylcarboxaldehyde and 10.6 g of thiolactic acid 16 g of thiazolidinone is obtained.

Elemental Analysis: C ₁₅ H ₁₃ FN ₂ OS

Example 36

3- (4-fluorophenyl) -5-methyl-2- (3-pyridyl) -4 at a melting point of about 148 ° C. from 22.2 g of 4-fluoroaniline, 21.4 g of 3-pyridylcarboxaldehyde and 24 g of thiolactic acid 36 g of thiazolidinones are obtained.

Elemental Analysis: C ₁₅ H ₁₃ FN ₂ OS

Example 37

3- (3-nitrophenyl) -2- (3-pyridyl) -4-thiazolidinone having a melting point of about 114 to 115 DEG C from 13.8 g of 3-nitroaniline, 11 g of 3-pyridylcarboxaldehyde and 9 g of thioglycolic acid 1.5 g are obtained.

Elemental Analysis: C ₁₄ H ₁₁ N ₃ OS

Example 38

3- (4-phenoxyphenyl) -2- (3-pyridyl) -4-thiazoli having a melting point of about 168 to 170 ° C from 26 g of 4-phenoxyaniline, 15 g of 3-pyridylcarboxaldehyde and 13 g of thioglycolic acid Obtain 26 g of dinone.

Elemental analysis: C ₂₀ H ₁₆ N ₂ O ₂ S

Example 39

3- [1- (2-cyclopentyl-1-methyl) -ethyl-5-methyl--2 having a melting point of about 102 ° C. from 26 g of α-methylcyclopentaneethylamine, 22 g of 3-pyridylcarboxaldehyde and 25 g of thiolactic acid 2 g of-(3-pyridyl) -4-thiazolidinone is obtained.

NMR (CDCl ₃ ) (δ)

Example 40

5-methyl-3- (α-methylbenzyl) -2- (3-pyridyl) -4- at a melting point of about 89 ° C. from 12 g of α-methylbenzylamine, 10.7 g of 3-pyridylcarboxaldehyde and 10.7 g of thiolactic acid 1.8 g of thiazolidinone is obtained.

Elemental Analysis: C ₁₇ H ₁₈ N ₂ OS

Example 41

3-isopropyl-5-methyl-2- (3-pyridyl) -4-thiazolidinone having a melting point of about 110 to 111 DEG C from 11.8 g of isopropylamine, 20.0 g of 3-pyridylcarboxaldehyde and 22.0 g of thiolactic acid 21 g is obtained.

Elemental Analysis: C ₁₂ H ₁₆ N ₂ OS

Example 42

3- (3,5-xylyl) -5-methyl-2- (3-pyridyl) having a melting point of about 140 to 142 ° C. from 25 g of 3, 5-dimethylaniline, 22 g of 3-pyridylcarboxaldehyde and 12 g of thiolactic acid 12 g of 4-thiazolidinone are obtained.

NMR (CDCl ₃ ) (δ)

Elemental Analysis: C ₁₆ H ₁₈ N ₂ OS

Example 43

2- (3-pyridyl) -3- (2-thiazolyl) -4- having a melting point of about 164 to 165 ° C. from 14.0 g of 2-aminothiazole, 15.0 g of 3-pyridylcarboxaldehyde and 13.0 g of thioglycolic acid 2.0 g of thiazolidinone is obtained.

Elemental Analysis: C ₁₁ H ₉ N ₃ OS ₂

Example 44

3- (3,4-xylyl) -5-methyl-2- (3-pyridyl) having a melting point of about 189 ° C. from 12.1 g of 3, 4-dimethylaniline, 10.7 g of 3-pyridylcarboxaldehyde and 12 g of thiolactic acid 16 g of 4-thiazolidinone are obtained.

NMR (CDCl ₃ ) (δ)

Elemental Analysis: C ₁₇ H ₁₈ N ₂ OS

Example 45

3- [2- (1-Metoxypropyl)]-2- (3 at a melting point of about 111-112 ° from 8.9 g of 2-amino-1-methoxypropane, 10.7 g of 3-pyridylcarboxaldehyde and 15 g of thiolactic acid 6.9 g of -pyridyl) -5-methyl-4-thiazolidinone is obtained.

NMR (CDCl ₃ ) (δ)

Example 47

12 g of 3- (isopropyl-2- (3-pyridyl) -4-thiazolidinone having a melting point of about 119 to 120 ° C. is obtained from 7 g of isopropylamine, 15 g of 3-pyridylcarboxaldehyde and 13 g of thioglycolic acid.

Elemental Analysis: C ₁₁ H ₁₄ N ₂ OS

Example 48

3- (cyclohexylmethyl) -5-methyl-2- (3-pyridyl) -4 at a melting point of about 73 to 74 ° C. from 11.3 g of cyclohexanemethaneamine, 10.7 g of 3-pyridylcarboxaldehyde and 10.8 g of thiolactic acid 11 g of thiazolidinone is obtained.

Elemental Analysis: C ₁₆ H ₂₂ N ₂ OS

Example 49

3-cyclooctyl-5-methyl-2- (3-pyridyl) -4-thiazolidinone having a melting point of about 58 to 61 DEG C from 12.7 g of cyclooctylamine, 10.7 g of 3-pyridylcarboxaldehyde and 10.6 g of thiolactic acid 11.2 g is obtained.

Elemental Analysis: C ₁₇ H ₂₄ N ₂ OS

Example 50

From 18.6 g of aniline, 21.4 g of 3-pyridylcarboxaldehyde and 21.2 of thiolactic acid, 15 g of 5-methyl-3-phenyl-2- (3-pyridyl) -4-thiazolidinone having a melting point of about 159 to 161 ° C are obtained. .

Elemental Analysis: C ₁₅ H ₁₄ N ₂ OS

Example 51

6 g of 5-methyl-3- (2-tolyl) -2- (3-pyridyl) -4-thiazolidinone in oil form are obtained from 21.4 g of 2-toluidine, 21.4 g of 3-pyridylcarboxaldehyde and 25 g of thioractic acid. do.

NMR (CDCl ₃ ) (δ)

1.6 (q, -CH ₃ ); 2.1 (s, -CH ₃ );

Elemental Analysis: C ₁₆ H ₁₆ N ₂ OS

Example 52

5-methyl-3- (4-methylthiophenyl) -2- (3-pyridyl) at about 147 to 148 ° C. from 17.5 g of 4-methylthioaniline hydrochloride, 10.7 g of 3-pyridylcarboxaldehyde and 12 g of thiolactic acid 23 g of 4-thiazolidinone is obtained.

Elemental Analysis: C ₁₆ H ₁₆ N ₂ OS ₂

Example 53

5-methyl-3- [2- (1-methoxypropyl)]-at a melting point of about 111-112 ° C. from 8.9 g of 2-amino-1-methoxypropane, 10.7 g of 3-pyridylcarboxaldehyde and 15 g of thiolactic acid 2.1 g of 2- (3-pyridyl) -4-thiazolidinone are obtained.

Confirm by NMR spectrum.

Example 54

3- (4-nitrophenyl) -2- (3-pyridyl) -4-thiazolidinone having a melting point of about 142 to 143 ° C from 13.8 g of 4-nitroaniline, 11 g of 3-pyridylcarboxaldehyde and 9 g of thioglycolic acid Yield 4.0 g.

Elemental Analysis: C ₁₄ H ₁₁ N ₃ O ₃ S

Example 55

7.5 g of 2- (3-pyridyl)-(2-norbornyl) -4-thiazolidinone at a melting point of about 143 ° C. are obtained from 14 g of norbornylamine, 15 g of 3-pyridylcarboxy aldehyde and 13 g of thioglycolic acid.

Elemental Analysis: C ₁₄ H ₁₈ N ₂ OS

Example 56

3- (2,4-difluorophenyl) -5-methyl-2- (3-pyrid) having a melting point of about 102 ° C. from 6 g of 2, 4-difluoroaniline, 6 g of 3-pyridylcarboxaldehyde and 8 g of thiolactic acid 3.2 g of dill) -4-thiazolidinone is obtained.

Elemental Analysis: C ₁₅ H ₁₂ F ₂ N ₂ OS

Example 57

3- (4-iodophenyl) -5-methyl-2- (3-pyridyl)-at a melting point of about 149-150 ° C. from 21.9 g of 4-iodoaniline, 11 g of 3-pyridylcarboxaldehyde and 12 g of thioractic acid 12 g of 4-thiazolidinone are obtained.

Elemental Analysis: C ₁₅ H ₁₃ IN ₂ OS

Example 58

5-methyl-3- (4-methylbenzyl) -2- (3-pyridyl) -4- at a melting point of about 96 ° C. from 12 g of 4-methylbenzylamine, 10.7 g of 3-pyridylcarboxaldehyde and 10.7 g of thiolactic acid 4.9 g of thiazolidinones are obtained.

Elemental Analysis: C ₁₇ H ₁₈ N ₂ OS

Example 59

5-methyl-3- (4-methylcyclohexyl) -2- (3-pyridyl having a melting point of about 1088 to 109 DEG C from 11.5 g of 4-methylcyclohexylamine, 10.5 g of 3-pyridylcarboxaldehyde and 11 g of thiolactic acid 500 mg))-4-dithiazolidinone is obtained.

Elemental Analysis: C ₁₆ H ₂₂ N ₂ OS

Example 60

3- (2,4-dichlorobenzyl) -2- (3-pyridyl)-having a melting point of about 125 to 126 ° C. from 17.6 g of 2, 4-dichlorobenzylamine, 10.7 g of 3-pyridylcarboxaldehyde and 12 g of thiolactic acid 15 g of 5-methyl-4-thiazolidinone is obtained.

Elemental Analysis: C ₁₆ H ₁₄ Cl ₂ N ₂ OS

Example 61

3- (2-methoxybenzyl) -5-methyl-2- (3-pyridyl) -4- in oil form from 13.7 g of 2-methoxybenzylamine, 10.5 g of 3-pyridylcarboxaldehyde and 10.7 g of thiolactic acid 2 g of thiazolidinone is obtained.

NMR (CDCl ₃ ) (δ)

1.7 (q, -CH ₃ ); 3.7 (s, -OCH ₃ );

Elemental Analysis: C ₁₇ H ₁₈ N ₂ O ₂ S

Example 62

3- (2-furfuryl) -5-methyl-2- (3-pyridyl) -4-dithiazolidi having a melting point of about 74 ° C. from 19.4 g of furfurylamine, 22 g of 3-pyridylcarboxaldehyde and 25 g of thiolactic acid 6 g of paddy rice is obtained.

Elemental Analysis: C ₁₄ H ₁₄ N ₂ O ₂ S

Example 63

5-methyl-2- (3-pyridyl) -3-[(tetra) having a melting point of about 86 to 87 DEG C from 10.6 g of 3-pyridylcarboxaldehyde, 10.1 g of tetrahydro-2-furanmethaneamine and 10.7 g of thiolactic acid. 5.5 g of hydro-2-furinyl) methyl] -4-thiazolidinone are obtained.

Elemental Analysis: C ₁₄ H ₁₈ N ₂ O ₂ S

Example 64

3- [2- (dimethylamino) ethyl] -5-methyl-2- (3-pyridyl)-solid from 10.7 g of 3-pyridylcarboxaldehyde, 8.8 g of 2-dimethylaminoethylamine and 12 g of thioglycolic acid 12 g of 4-thiazolidinone are obtained.

NMR (CDCl ₃ ) (δ)

1.6 (d, -CH ₃ ); 2.1 (s, -N (CH ₃ ) ₂ );

2.6 (m, -CH _2- ); 3.9 (m, -CH ₂ ); 5.9

Elemental Analysis: C ₁₃ H ₁₉ N ₃ OS

Example 64A

3-[(2,6-dichlorophenyl) amino] -5-methyl-2- (3) having a melting point of 198 to 200 ° C. from 11 g of 3-pyridylcarboxaldehyde, 21.3 g of 2.6-dichlorophenylhydrazine hydrochloride and 7 g of thiolactic acid. 2 g of -pyridyl) -4-thiazolidinone is obtained.

Elemental Analysis: C ₁₅ H ₁ Cl ₂ N ₃ OS

Example 64B

3-[(3-chloro-4-methylphenyl) amino] -5-methyl- having a melting point of 150 to 160 ° C. from 6.43 g of 3-pyridylcarboxaldehyde, 8.5 g of 3-chloro-4-methylaniline and 6.7 g of thioractic acid 10.5 g of 2- (3-pyridyl) -4-thiazolidinone is obtained.

Elemental Analysis: C ₁₆ H ₁₅ ClN ₂ OS

Example 64C

3- (2,4-dimethylphenyl) -5-methyl-2- (3-pyridyl)-having a melting point of 121 to 123 ° C. from 25 g of 2,4-dimethylaniline, 22 g of 3-pyridylcarboxaldehyde and 24 g of thiolactic acid 14 g of 4-thiazolidinone is obtained.

NMR (CDCl ₃ ) (δ)

1.7 (d, -CH ₃ ); 2.2 (d, -CH ₃ ); 4.2

Example 64D

3- (2-trifluoromethyl-phenyl) -5-methyl-2- (3-pyridyl having a melting point of about 87 ° C. from 24 g of 2-trifluoromethylaniline, 16 g of 3-pyridylcarboxaldehyde and 18 g of thiolactic acid 4.0 g of 4-thiazolidinone is obtained.

Elemental Analysis: C ₁₆ H ₁₃ N ₂ F ₃ SO

Example 64E

3- (4-bromo-3-methylphenyl) -5-methyl- having a melting point of about 127 to 129 ° C. from 11.2 g of 4-bromo-3-methylaniline, 6.4 g of 3-pyridylcarboxaldehyde and 6.7 g of thioractic acid 12.2 g of 2- (3-pyridyl) -4-thiazolidinone are obtained.

Elemental Analysis: C ₁₅ H ₁₄ BrN ₂ OS

Example 65

3- (4-chlorophenyl) -5, 5-dimethyl-2- (3-pyridyl) -4-thiazolidinone

To 150 ml of anhydrous tetrahydrofuran cooled to −70 ° C. under dry nitrogen atmosphere, 25 ml of a hexane solution of n-butyllithium are added all at once. The mixture was again cooled to -70 ° C and 3- (4-chlorophenyl) -5-methyl-2- (3-pyridyl) -4-thiazolidinone in 100 ml of anhydrous tetrahydrofuran (the method of Example 1 above) 15 g of solution was added dropwise while stirring. Approximately 0.5 hours after the addition is completed, 14 g of methyl iodide is added dropwise to the mixture while stirring is continued, and the reaction mixture is stirred overnight to slowly warm to room temperature.

Water is added and extraction with ether completes the reaction. The ether layer is dried over anhydrous magnesium sulfate and the drying agent is filtered off, and the filtrate is concentrated in vacuo to give a residual oil. The resulting oil is crystallized using a mixture of petroleum ether (boiling point 60-70 ° C.) and ethyl ether. The product obtained is identified as 3- (4-chlorophenyl) -5, 5-dimethyl-2- (3-pyridyl) -4-thiazolidinone at a melting point of about 140 to 141 ° C.

Yield: 4.8 g

NMR (CDCl ₃ / DMSO) (δ)

Elemental Analysis: C ₁₆ H ₁₅ ClN ₂ OS

By the same general process as in Example 65, the following additional compounds were prepared and identified. The following examples describe the main starting materials used in the manufacturing process and the compounds produced along with their weights.

Example 66

Melting point about 76 to 15 g of 3- (4-chlorophenyl) -5-methyl-2- (3-pyridyl) -4-thiazolidinone, 25 ml of hexane solution of n-butyllithium and 9 g of n-butyl iodide 2 g of 5-butyl-3- (4-chlorophenyl) -5-methyl-2- (3-pyridyl) -4-thiazolidinone at 77 ° C. are obtained.

Elemental Analysis: C ₁₉ H ₂₁ ClN ₂ OS

Example 67

3- (4-chlorophenyl) -5-methyl-2- (3-pyridyl) -4-thiazolidinone (prepared by the method of Example 1 above) 15.2 g, n-propyl iodide 8.5 g and n 1.6 g of 3- (4-chlorophenyl) -5-methyl-5-propyl-2- (3-pyridyl) -4-thiazolidinone having a melting point of 81 to 83 ° C. is obtained from 23 ml of a hexane solution of -butyllithium. .

Elemental Analysis: C ₁₈ H ₁₉ ClN ₂ OS

Example 68

15.2 g of 3- (4-chlorophenyl) -5-methyl-2- (3-pyridyl) -4-thiazolidinone (prepared by the method of Example 1 above), 10.5 g of n-hexyl iodide and n 1.5 g of 3- (4-chlorophenyl) -5-hexyl-5-methyl-2- (3-pyridyl) -4-thiazolidi at a melting point of 82 to 83 ° C. was obtained from 23 ml of a hexane solution of butyllithium. do.

Elemental Analysis: C ₂₁ H ₂₅ ClN ₂ OS

Example 69

3- (4- (chlorophenyl) -2- (3-pyridyl) -4-thiazolidinone (prepared by the method of Example 19), 13 g, 9.2 g n-butyl iodide and n-butyl lithium 700 mg of 5-butyl-3- (4-chlorophenyl) -2- (3-pyridyl) -4-thiazolidi having a melting point of 93 to 94 DEG C from 25 ml of a hexane solution was obtained.

Elemental Analysis: C ₁₈ H ₁₉ ClN ₂ OS

Example 70

3- (2-methoxyphenyl) -2- (3-pyridyl) -4-thiazolidinone

This compound is prepared in the following steps.

Step 1

A mixture of 17 g of 0-anisidine, 15 g of 3-pyridylcarboxaldehyde and 13 g of thioglycolic acid in toluene is refluxed for several hours. The mixture of reaction products is cooled and the precipitated material is collected by filtration. 20 g of product at a melting point of about 118-120 ° C. are obtained, which is identified as [[(0-methoxyanilino)-(3-pyridyl) methyl] thio] acetic acid by NMR and IR spectra.

Step 2

[[(0-Methyldilanilino) (3-pyridyl) methyl] thio] A mixture of 5 g of acetic acid, 3.4 g of N, N'-dicyclohexylcarbo-diimide and 300 ml of toluene was refluxed for several hours. Toluene is then removed in vacuo. The residue thus obtained is chromatographed on silica gel / toluene column and eluted with acetone / toluene mixture. The desired fractions are concentrated and the residue is recrystallized from a mixture of ether and pentane to give a product having a melting point of about 104-105 ° C., which is 3- (2-methoxyphenyl) -2- (3-pyridyl) -4- It is identified as thiazolidinone. Yield 1.5 g

Elemental Analysis: C ₁₅ H ₁₄ N ₂ O ₂ S

Example 71

5-methyl-2- (3-pyridyl) -3- (3-trifluoromethylthiophenyl) -4-thiazolidinone

This compound is prepared in the following steps.

Step 1

A mixture of 15 g of trifluoro-methylthio-3-nitrobenzene in 100 ml of anhydrous methanol is hydrogenated using a Parr hydrogenation apparatus in the presence of a Ranikel catalyst. When the uptake of hydrogen stops, the reaction is stopped to filter off the catalyst and the filtrate is concentrated to give 12 g of product, which is identified as trifluoro-methylthio-3-aminobenzene.

Step 2

A mixture of 11 g of trifluoromethylthio-3-aminobenzene, 7.7 g of 3-pyridylcarboxaldehyde and 20 ml of toluene is refluxed for about 2 hours using a Dean-Stark trap to capture the water produced in the reaction. A total of 1.2 ml of water are separated. The mixture of reaction products is cooled and concentrated in vacuo. Residual oil is dissolved in toluene and chromatographed on silica column. This material is eluted with toluene-5% acetone eluent and the contents from the column are examined by thinning chromatography. The appropriate fractions are then combined and concentrated to give the bottoms oil. The separated material (15 g, yellow oil) is identified as 3- (3-trifluoromethylthio) -N- (3-pyridylmethylene) benzeneamine by NMR spectrum. This material is used for the next step reaction without further purification.

Step 3

A mixture of 14 g of 3- (3-trifluorotomethylthio) -N- (3-pyridylmethylene) benzeneamine, 8 g of thiolactic acid and 200 ml of toluene was used a Dean-Stark trap to capture the water produced in the reaction. Reflux for about 6 hours. Thereafter, the mixture of reaction products is concentrated in vacuo, and the residue thus obtained is dissolved in toluene and chromatographed on silica column. The product is eluted from the column with 5% acetone-toluene and the fractions are concentrated to give 6 g of yellow oil. The product is identified as 5-methyl-2- (3-pyridyl) -3- (3-trifluoromethylthiophenyl)-4-thiazolidinone.

Example 72

3- (4-chlorophenyl) -2- (3-pyridyl) -4-thiazolidinone hydrochloride

3- (4-chlorophenyl) -2- (3-pyridyl) -4-thiazolidi in ethyl ether (Example 19 above) prepared 1.5 g of solution, cooled and saturated with anhydrous hydrogen chloride. The precipitated solid material was filtered to confirm that it is 3- (4-chlorophenyl) -2- (3-pyridyl) -4-thiazolidinone hydrochloride.

Example 73A

3- (4-chlorophenyl) -5- (methylthio) -2- (3-pyridyl) -4-thiazolidinone and

Example 73B

3- (4-chlorophenyl) -5, 5-bis (methylthio) -2- (3-pyridyl) -4-thiazolidinone

A mixture of 10.1 g of diisopropylamine and 500 ml of tetrahydrobutane is cooled to about 0 ° C. under nitrogen atmosphere. 45 ml of hexane solution of n-butyllithium was added dropwise to the mixture with stirring, and stirring was continued for about 30 minutes after the addition was completed. The mixture was then cooled to about −70 ° C. and a solution of 14.5 g of 3- (4-chlorophenyl) -2- (3-pyridyl) -4-thiazolidinone (Example 19 above) in 100 ml of tetrahydrofuran was added. Add it down. 30 minutes after the end of the addition, 9.4 g of methyl-disulfide are added. The reaction mixture is stirred overnight and slowly warmed to room temperature. The reaction mixture is treated by dropwise addition of water at approximately room temperature. The organic phase is then extracted with methylene chloride and the methylene chloride layer is washed with dilute hydrochloric acid solution. The methylene chloride layer is separated and dried over anhydrous sodium sulfate. The desiccant is filtered off and the filtrate is concentrated in vacuo to give a residual oil. The oil is dissolved in toluene and chromatographed on silica gel. Toluene: eluted with 10% acetone, and the separated fractions were concentrated to give 1 g of a product having a melting point of about 104 to 106 DEG C, which was 3- (4-chlorophenyl) -5- (methylthio) -2- (3- Pyridyl) -4-thiazolidinone.

Elemental Analysis: C ₁₅ H ₁₃ ClN ₂ OS ₂

In the same manner, 400 mg of a second product having a melting point of about 133 to 135 ° C., which is 3- (4-chlorophenyl-5, 5-bis (methylthio) -2- (3-pyridyl) -4-thiazolidinone Is confirmed.

Elemental Analysis: C ₁₆ H ₁₅ ClN ₂ OS ₃

Growth control of aquatic plants is carried out by adding active-substituted 1-thia-3-aza-4-one compounds of formula (VI) to water containing aquatic or floating aquatic weeds. This compound can be applied to water as a powder by mixing it with powdered high carriers such as bentonite, Fuller's earth, diatomaceous earth, or various mineral silicates (eg mica, larks, pyrophyllite and clay). The compound may also be mixed with a surfactant dispersant to form a concentrate to promote dispersion in water and to improve wettability when used as a spray. If desired, the compound may be mixed with the powdery solid carrier and the surfactant dispersing agent to obtain a wetting acid agent which may be applied directly or by shaking with water to apply in the form of an aqueous acid powder. The compound may be dissolved in an oil such as a hydrocarbon or chlorinated hydrocarbon oil, and the oil solution of the compound may be dispersed in water with the aid of an interfacial-active dispersing agent to form a spraying water dispersion. Such surfactant dispersants include anionic, nonionic or cationic surfactants. Such surfactants are well known and detailed examples are described in Hoffman et al. US Pat. Nos. 2, 614, 916 (2-4 stages). Compounds of formula (VI) can also be used by the aerosol method. Solutions for use in the aerosol method are either directly dissolved in an aerosol carrier which is a liquid under pressure and a gas at room temperature (eg 20 ° C.) and atmospheric pressure, or the compound is first dissolved in a less volatile solvent and then the solution is volatile. It can be prepared by mixing with this large liquid aerosol carrier.

The compound of general formula (VI) is added to the water with water and floating weeds in an amount which shows growth regulation activity but not herbicidal activity, that is, the concentration of the active compound is about 0.25 to about 10 ppm.

The optimal concentration of the active compound to control a particular aquatic weed in question depends on the temperature, the type of weeds to be inhibited and the type of water to be treated. When the water temperature is high, generally, the amount of the compound required to exhibit a predetermined degree of inhibition is small in comparison with the case where the temperature is low.

In the treatment for suppressing the plant group fixed in the flowing water, the active compound used in the treatment passes through the treatment zone, and the concentration of the compound during the contact period depends on the flow rate of the water, the rate of addition of the chemical, and the duration of the addition. Particular consideration should be given to this.

The novel aquatic plant growth control method according to the invention and the composition used for this is described by the following experiment.

[Exam 1]

In order to evaluate the aquatic plant growth control activity when the compound of the present invention is used at a concentration of 10ppm for representative submerged aquatic weeds, a laboratory experiment is performed as follows.

The compound of formula (VI) used in this test is prepared by the following method. 20 mg of compound is placed in a 12 ml disposable vial. To the vial containing compound 1 ml of acetone and 9 ml of 0.1% aqueous polyoxyethylene sorbitan monooleate (Tween 80) are added. 4.00 ml of this stock solution is added to 785 ml of water in a plastic container to obtain a test concentration of 10 ppm. The plastic container used is a pot-shaped container having a lower diameter of 9 cm, an upper diameter of 11.5 cm, and a height of 13.5 cm.

For the test, 10 cm long end pieces without side branches of Florida elodea, Hydrilla verticillata (L.F) (hereinafter referred to as hydilla) are used. Three cut pieces are placed in each plastic container containing 785 ml of water, and the test compound prepared as described above is added together with 3 ml of Hogland nutrient solution. Into several control vessels containing water, add three 10 cm cut pieces of Hydila. Water in each control vessel is also added to the amount of solvent used in the preparation of the test compound.

After 2-3 weeks the total length of each plant is measured. The average total growth is obtained by dividing the total length by the number of test subjects. Subtracting 10 cm from the average length gives the average growth increase. This difference is divided by the average increase in plant length in the solvent control group (SC) and multiplied by 100 to obtain an inhibition rate (%).

Average length-10 cm = average growth increase

Each compound used in this experiment is indicated by its preparation example number described above.

The results of the test measured after 3 weeks of testing at a compound concentration of 10ppm are shown in Table 1 below. The numbers in the first column in the table represent test compounds, and the second column represents the growth inhibition rate of the measured hydila.

TABLE 1

Substituted 1-thia-3-aza-4-one derivatives

[Exam 2]

Repeat the general procedure of Test 1 for Hydila Verticillara (L.F.) using various other compounds of formula (VI). At this time, test compound concentration is 1, 0.5 and 0.25ppm.

The test compound is prepared by the following method: 20 mg of compound is placed in a 12 ml disposable vial. To the vial containing the compound 1 ml of acetone and 0.1% aqueous polyoxyethylene sorbitan monooleate are added. This solution is referred to as stock solution A.

A test concentration of 1 ppm is obtained as follows: 4 ml of Stock A is diluted with 36 ml of 0.1% aqueous polyoxyethylene sorbitan monooleate to obtain Stock B. 4 ml of stock B is added to 785 ml of water in a plastic test container to make the test compound 1 ppm. Plastic test containers are the same as those used in Test 1.

A test compound at 0.5 ppm concentration is prepared as follows: Dilute 20 ml of Stock Solution B with 20 ml of 0.1% aqueous polyoxyethylene sorbitan monooleate and label this stock as Stock Solution C. 4 ml of Stock Solution C is added to 785 ml of water in a plastic test vessel to bring the concentration to 0.5 ppm.

A test compound at 0.25 ppm concentration is obtained as follows: Dilute 20 ml of Stock Solution C with 20 ml of 0.1% aqueous polyoxyethylene sorbirane monooleate to obtain Stock D. 4 ml of the stock solution D is added to 785 ml of water in a plastic test container to make the concentration of the test compound 0.25 ppm.

Three weeks after the application of the test compound, the totality of each plant is measured as described in Test 1 and the percent inhibition is calculated using the formula described in Test 1 above. The results are reported in Table 2. Each test compound is indicated by the number of the preparation example described above.

TABLE 2

Substituted 1-thia-3-aza-4-one derivatives

Another aspect of the invention is practiced by applying a fungicidally effective amount of one or more general formula (IV) compounds to the habitat of phytopathogenic fungi. The effective amount in the application of the compound varies somewhat depending on other factors such as the extent of fungal infection and the treatment environment.

The composition comprises one or more additives, including water, polyhydroxy compounds, petroleum distillates and other dispersion media, surfactant dispersants, emulsifiers and fine inert solids, in addition to substituted 1-thia-3-aza-4-silver antifungal agents. It is preferable to contain. The concentration of substituted 1-thia-3-aza-4-silver, an antifungal agent in such a composition, may be applied directly to the plant or subsequently diluted with an additional inert carrier such as water to produce a final treatment composition. It may vary depending on whether you use it.

It is most convenient to prepare a composition for treatment by diluting a liquid or solid concentrate and continuing diluting to the concentration necessary for use. Emulsifying liquid concentrates can be prepared by mixing about 1 to about 10 weight percent of the active ingredient and an emulsifier in a suitable water-immiscible organic liquid. This concentrate may be further diluted with water to form a spray mixture in the form of an oil-in-water emulsion. Such spray compositions consist of the active ingredient, a water-immiscible solvent, an emulsifier and water. Suitable emulsifiers are in nonionic or ionic form or mixtures thereof, including condensation products of alkylene oxides with phenols and organic acids, polyoxyethylene derivatives of sorbitan esters, ether alcohol complexes and arylalkyl sulfonates Compounds and the like. Suitable water-immiscible organic liquids used include mixtures thereof, such as aromatic hydrocarbons, aliphatic hydrocarbons, cycloaliphatic hydrocarbons and petroleum distillates.

The solid concentrate mixture is about 10 to about 50% by weight of 1-thia-3-aza-4-silver compound substituted in fine solid carriers such as bentonite, fullerto, diatomaceous earth, hydrated silica, diatom silica, expanded mica, talc, chalk It can be prepared by mixing. Such concentrates are optionally formulated into powder compositions for direct use, or optionally diluted with additional insoluble solid carriers to replace 1-thia-3-aza-4- about 0.05-1% by weight. Powder for powder containing can be obtained. Or a surfactant, i.e. a dispersant and / or a wetting agent, is mixed with substituted 1-thia-3-aza-4-one in the solid carrier to form a wetting acid concentrate at a concentration of about 10 to about 25% by weight, and then It may be dispersed in water or other hydroxylated carrier to form a spray composition. Suitable surfactants include condensed arylsulfonic acids and their sodium salts, sodium lignosulfates, sulfonate-oxide condensate mixtures, alkylaryl polyetheralcohols, sulfonates, nonionic mixtures, anionic wetting agents and the like.

In addition, the active substance, substituted 1-thia--3-aza-4-one, can be mixed with solutions, simple dispersants, aerosol formulations, and other media that can be used for plant or soil treatment.

Antifungal compositions are applied to plant surfaces that are infected or susceptible by conventional methods such as spraying, scattering, dipping or drenching. Spraying methods are preferred, particularly when treating a large number of plants in view of the speed and uniformity of the treatment. Upon spraying, it is usually sufficient to wet the infected or susceptible surface completely with the liquid dispersant used. Good results have been obtained when the spray composition is an emulsion or an aqueous dispersion of a solid concentrate.

If the fungus to be inhibited is present in the soil, the antifungal compound may be applied directly to the soil or diluted with various insoluble solid or liquid diluents as described above and then applied to the fungal-invasive area. One method of application to soil is to spray the soil surface with a liquid dispersant or emulsion of the active ingredient. Applicable materials may be encapsulated on the surface of the soil or incorporated into the soil by disking, hoeing or other methods well known to those skilled in the art. Another application method is to use the active ingredient by drenching the soil with a liquid dispersant or emulsion. The application rate of the active ingredient for suppressing fungi inhabiting soil at room temperature is about 5 to 200 ppm. When acid addition salts of 1-thia-3-aza-4-one bases are used, the rate of application depends, of course, on the amount of base present. Salts are mainly used because of their ease of handling and formulation.

The fungicidally active compound of formula (IV) has also been found to be effective when used as a seeding agent before seeding. When a fungicide compound is applied as a fungicide, a fungicide composition containing the fungicide compound and other excipients such as ethanol-acetone mixtures, polyoxyethylene sorbitan monooleate and the like is prepared. When the general formula (IV) compound is used as an invading agent, the fungicide substituted 1-thia-3-aza-4- is a compound, and a satisfactory inhibitory effect is obtained at an application rate of about 50 to about 400 ppm. Seeds are sown after about 4 hours soaking in the composition.

The effect of the general formula (IV) compound and its acid addition salt as a plant fungicide is explained by the following test method.

[Exam 3]

The effect of the soil drenching method of the compound of formula (IV) on the erythropoie cichoracearum, the causative agent of cucumber powdery mildew, was evaluated in the greenhouse by the following method.

The compound of formula (VI) was dissolved in a 1: 1 mixture of ethanol: acetone containing polyoxyethylene sorbitan monolaurate (Tween 20) and deionized water so that the final concentration was 1% solvent and 0.1% surfactant. Dilution with to prepare a fungicidal composition. Firstly, the most concentrated fungicidal composition is prepared, ie a composition containing the highest concentration of active ingredient. Other fungicidal compositions containing lower concentrations of the active ingredient are prepared from the highest concentration compositions by serial dilution methods. Solvent-surfactant blanks are used for control.

Five cucumber seeds (Cucumis sativus L., variance "Green Prolific") are sown and sanded in 4-inch square plastic pots with soil. After seed germination, the plants are squeezed to two per pot. 15 days after seed sowing, the soil is drenched with 50 ml of the test compound formulated for one pot for each concentration of each test compound. After that, the pots in which the plants are planted are transferred to a greenhouse and inoculated by spraying conidia of cucumber plants infected with the leaves of the plants. Occurrence of cucumber powdery mildew on cucumber plants after 23 days of sowing

TABLE 3

Measure The results of this test are reported in Table 3 below. In the table, 0 percent indicates that powdery mildew did not develop (infection). The compound is indicated by the number of the preparation example described above.

[Exam 4]

In order to determine the inhibitory effect of selected generic formula (IV) compounds as fungicides on the erythropoie graminis tritice, the causative agent of wheat powdery mildew disease, the test is carried out in a greenhouse as follows.

Fungicidal compositions are prepared in the same manner as described in Test 3.

30 to 40 wheat seeds (Nonon) are sown in a 4-inch square plastic pot with soil and covered with sand. If seedlings grow to 4 to 6 inches after about 6 to 8 days, the soil in one pot is drenched with the formulated test compound. Next, the plants are transferred to a greenhouse and inoculated by dispersing conidia obtained from wheat plants invaded by the leaves of the plants. About 14 to 16 days after sowing, plants are observed to determine the incidence of wheat flour in wheat plants. The results are reported in Table 4 below.

0 percent in the table means that powdery mildew has not occurred (infection). The compound is indicated by the number of the preparation example described above.

TABLE 4

[Exam 5]

The efficacy of the general formula (IV) compound against Erysiphe graminis hordei, the causative agent of barley white powdery disease, is evaluated in the greenhouse in the same manner as described in Test 4. The results are reported in Table 5 below, and the compounds are indicated by the numbers of the preparation examples described above.

TABLE 5

[Exam 6]

The efficacy of the general formula (IV) compound against barley white powder bottle is evaluated by further testing in the greenhouse as follows.

Fungicidal compositions are prepared by dissolving the test compound in 0.1% polyoxyethylene sorbitan monolaurate in 2% ethanol: acetone (1: 1) and deionized water. Each test compound is prepared at concentrations of 200, 400 and 800 ppm. 5 ml of each concentration of test compound is sprayed into 3 cups of soil in a tumbler to ensure complete incorporation of the compound. This should contain 1, 2 and 3 mg of test compound per 3 cups of soil, respectively. Place 5 cups of untreated greenhouse soil in a plastic pot 20.32 cm in diameter and 25.4 cm deep. The upper 6 cm of each pot is filled using 3 cups of treated soil. 20 seeds of Lacker varieties of barley are sown to the treated soil 1 cm deep. If necessary, wet the top of the pot with water. After 6 days, powdery mildew spores from all infected plants are inoculated.

Begin with 12 days after sowing (DAP) and observe the incidence of powdery mildew in plants. The observed results are reported in Table 6 below. 0% in the table means that no white powdery disease has occurred, ie 100% suppressed. The compound is indicated by the number of the preparation example described above.

TABLE 6

[Exam 7]

This test was conducted to further evaluate the efficacy of the formula (IV) compound as a fungicide that inhibits the causative agents of wheat and barley powdery mildew.

500 mg of test compound is dissolved in 10 ml of acetone and sprayed into 50 g of rotating Florex 30/60 granules for air drying. The sprayed granules thus contain 1.0% of the active ingredient. Three test specimens prepare 800, 400 and 200 mg of 1% granules containing 8, 4 and 2 mg of test compounds, respectively. Three untreated granules are also prepared for control. Granules are added and mixed thoroughly using 3 cups of rotating soil each time per treatment.

Three cups of soil containing granules are placed on top of the untreated soil in the pot as in Test 6. Twenty seeds of lacquer bark, Proctor barley or Logan wheat are sown each 1 cm deep into the treated soil per pot. If necessary, wet the top of the pot with water. Six days after sowing, each powdery mildew conidia obtained from wheat and barley plants already infected with the plant is inoculated.

Beginning 12 days after sowing (DAP), the incidence of powdery mildew is measured. The results are reported in the following Table 7, and the compounds are indicated by the numbers of the above-described preparation examples.

TABLE 7

^* Mg in 1% granules per pot.

[Exam 8]

The effect of the formula (IV) compound on the causative agent of four fungal diseases of wheat is measured in the greenhouse by drenching the test compound in leaves and soil according to the following method.

Seeds of monaural varieties are seeded in a 6.25 cm diameter round plastic pot containing sandy soil. Prepare two test ports and four control ports per disease (24 ports total). When the seedlings grew about 4 to 5 inches, that is, about 5 to 7 days after sowing, depending on the season in which the test was carried out, spray the test compound formulated (approximately 400 ppm) on each plant of the two test ports, In soil treatment, 10 ml of the same formulated test compound (application rate 12.32 kg / ha) is drenched the soil of each of the two test ports. This procedure is performed for each of the formulated test compounds. For each test compound per disease, two methods of spray application and soil trench application are performed in each of two ports. Using a total of four control ports for each disease for control, the plants in the two control ports were sprayed with a solvent-emulsifier solution diluted with water and the soil in the other two control ports with a solvent-emulsifier solution diluted with water. Drenched.

Within 24 hours of application of the formulated test compound and solvent-surfactant solution as described above, all pots are transferred into the greenhouse and inoculated with conidia of test fungi respectively. After moving the plant into the greenhouse, observe the symptoms of the disease for 4 to 8 days and record the extent.

Depending on the severity of the disease it is indicated as follows:

1-Severe (Helmintosporium Sativaum)

2-Slightly Severe Red Rust (LR)

3-Normal (Pushonia Recondita Tritish)

4-weak powdery mildew (PM)

5-No disease (100% inhibition) (Ericifer Graminis Tritici)

Test microorganisms are as follows: Leaf blight (S)

Spotted Pattern Disease (H) (Septoria Tritici)

The results are shown in the following Table 8, wherein the compound is indicated by the preparation example number thereof.

TABLE 8

Disease suppression

[Exam 9]

In accordance with the same general test method as the method described in Test 8, further test for the efficacy of the compound used in Test 8 at the same application rate as well as at a lower application rate. The results are reported in Table 9.

TABLE 9

Disease suppression

[Exam 10]

Activity of compound (VI) as a plant growth regulator is tested in a greenhouse according to the following method.

The plants used in this test include Chippewa varieties of soybeans, Lacquer varieties of barley, Manhattan varieties of barley and green prolypic varieties. All plants grow in soil in a 10 cm plastic pot. After sowing, half of the pots are covered with vermiculite and used for foliar spray application of the test compound. Soil in the remaining half of the pot is sown with seeds and covered with soil for use in the soil drenching of the test compound. Until the end of the test, fertilize every other week with a solution containing 6.7 g of Rapid-Gro (commercial fertilizer) per gallon. After the plant grows and before the start of the test, the plants in each port are squeezed to include the number of plants per each pot. Two soybean plants per pot, five soybean plants, about 100 barley and one cucumber. The barley is cut to 2.5 cm in length the day before treatment.

Plants in half the pots are treated with soil drenching at a rate of 5.6 kg / ha of the test compound. Plants in the other half of the pot are sprayed with foliar at an application rate of 2000 ppm. Foliar spray application is carried out using a Devilbis sprayer under a pressure of 10 to 12 psi and sprayed to wet all leaves of the plant.

Test compounds are formulated in the following manner. 50 mg of the test compound was dissolved in 3 ml of a mixture of ethanol and acetone (1: 1 in a volume ratio), and Toximul R and S water (300 ppm of methoxymal R in deionized water and 400 ppm of methoxymal S) were added to a total volume of 25 ml. Dilute as much as possible. [Toxymal R and Toxymal S are pairs of emulsifiers formulated for general purposes and are liquid sulfonate / nonionic mixtures produced by Stepan Chemical Company (Northfield, Illinois, U. S. A.). 14 ml of solution is used for foliar application. When trenching the soil, dilute 11 ml of the solution to 100 ml and pour an aliquot of 20 ml into each pot. The age of the plant at the time of treatment differs as follows:

Soybean-16 days

Barley-7 days

Red barley-10 days

Cucumber-17 days

After treatment, soybeans and barley are left in the greenhouse for 15 days. Thereafter, the growth control effect and the degree of damage are visually evaluated. Evaluators of 0, 1, 2, and 3 are used. 0 is invalid and 3 is obvious or significant. "+" Indicates growth promotion and "-" indicates growth inhibition or inhibition. The results are reported in Table 10. The compound is indicated by the number of the preparation example described above.

TABLE 10

Plant growth regulation effect

/H=키 ; BR=분지 ; I=손상 ; F=개화 ; T=번식 ; M=형태학적 효과

/ H = key; BR = branch; I = damage; F = flowering; T = propagation; M = morphological effect

B = image; C = Sulfide

The results obtained in the experiments described above show that the newly substituted 1-thia-3-aza-4 silver derivatives of the general formula according to the present invention are grown in aquatic and floating aquatic plants according to the methods described and claimed herein. It has been shown to be effective in regulating, protecting plants from phytopathogenic fungi, and regulating growth of carnivorous plants such as wheat and barley.

Claims (1)

3-pyridylcarbox aldehyde of the following structural formula (III) is reacted with a substituted amine of the following general formula (III) and subsequently reacted with thioglycolic acid or thioractic acid, thereby To prepare a thiazolidinone compound.

Wherein R is C ₃ to C ₁₀ alkyl, C ₃ to C ₈ -cycloalkyl, metallyl, phenyl, halophenyl, trifluoromethylphenyl, benzyl, methoxybenzyl, methylbenzyl, halobenzyl, dimethylaminoethyl, Methylcyclohexyl, C ₃ to C ₈ cycloalkyl (C ₁ to C ₃ ) alkyl, α-methylbellyl, 2-thiazolyl, nitrophenyl, phenoxyphenyl, (tetrahydro-2-furanyl) methyl, haloaniyl Reel, trifluoromethylthiophenyl, methylthiophenyl, 2-norbornyl, furfuryl, 2- (1-methuxipropyl), methoxyphenyl, fluoro (C ₁ to C ₂ ) alkoxyphenyl, 3, 4 -(Methylenedioxy) phenyl, xylyl, biphenylyl, tolyl or halotolyl; R ¹ is hydrogen, methyl or —S (C ₁ to C ₆ alkyl); R ² is hydrogen, C ₁ to C ₆ alkyl or —S (C ₁ to C ₆ alkyl).