KR100329808B1 - An efficient method for preparing 2-phenacylidene-3,5-dialkylsubstituted-1,3-thiazolidine-4-ones - Google Patents
An efficient method for preparing 2-phenacylidene-3,5-dialkylsubstituted-1,3-thiazolidine-4-ones Download PDFInfo
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Abstract
본 발명은 화학식 1을 갖는 2-펜아실리덴-3,5-알킬치환된-1,3-티아졸리딘-4-온을 효율적으로 제조하는 방법에 관한 것으로서, 그 반응은 반응식 1과 같다.The present invention relates to a method for efficiently preparing 2-phenacylidene-3,5-alkylsubstituted-1,3-thiazolidin-4-one having the formula (1), wherein the reaction is shown in Scheme 1.
본 발명의 제조방법에 따르면, 상기 화학식 1의 화합물을 한 반응 용기 내에서, 그리고 보다 용이한 반응 조건 하에서 얻을 수 있다.According to the preparation method of the present invention, the compound of formula 1 can be obtained in one reaction vessel and under easier reaction conditions.
Description
본 발명은 하기 화학식 1로 표시되는 2-펜아실리덴-3,5-알킬치환된-1,3-티아졸리딘-4-온의 제조 방법에 관한 것이다.The present invention relates to a process for preparing 2-phenacylidene-3,5-alkyl substituted-1,3-thiazolidin-4-one represented by the following formula (1).
[화학식 1][Formula 1]
상기 화학식 1에서 R1은 탄소수 1∼6의 알킬기, 탄소수 7∼8의 아릴알킬기, 방향족고리내에 탄소수 1∼3의 알킬기, 탄소수 1∼3의 알콕시기 및 할로겐으로 구성되는 군에서 선택되는 하나 이상에 의해 치환된 탄소수 7∼8의 아릴알킬기, 탄소수 5∼7의 시클로알킬기를 의미하며; R2는 수소 또는 탄소수 1∼3의 저급 알킬기를 의미한다.In Formula 1, R 1 is one or more selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an arylalkyl group having 7 to 8 carbon atoms, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, and a halogen in an aromatic ring An arylalkyl group having 7 to 8 carbon atoms and a cycloalkyl group having 5 to 7 carbon atoms substituted with; R 2 means hydrogen or a lower alkyl group having 1 to 3 carbon atoms.
상기 화학식 1의 화합물은 Justis Liebigs Ann. Chem. 150∼165 (1963)에서기술된 바와 같이 2-(알킬아미노아실리덴)-3-메틸-1,3-티아졸리딘-4-온 화합물 및 이의 유사 화합물들은 Na+통로에 작용하여 신경보호제로 쓰일 수 있으며, 독일특허 제1,150,985호에 기술되어 있는 바와 같이 진통제, 진정제 등으로 사용될 수 있는 화합물이다.The compound of Formula 1 is Justis Liebigs Ann. Chem. As described in 150-165 (1963), 2- (alkylaminoacylidene) -3-methyl-1,3-thiazolidin-4-one compounds and their analogous compounds act on the Na + channel to protect neurons It is a compound which can be used as a zero and can be used as analgesics, sedatives and the like as described in German Patent No. 1,150,985.
하지만 본 화합물은 지금까지 그 합성법이 크게 제한되어 있어 그 약리적 효능에도 불구하고 많이 발전하지 못하였다.However, the present compound has not been developed much in spite of its pharmacological efficacy since its synthesis is greatly limited.
지금까지 알려진 합성방법은 상기 독일특허 제1,150,985호에 도식 및 기술되어 있는 방법이 대표적이며, 구체적으로는 말로니트릴 및 그 유도체와 에틸 티오아세트에스테르를 산소가 없는 무수 조건에서 고온 반응시켜 2-에틸리덴-1,3-티아졸리딘-4-온 화합물을 얻고, 얻어진 화합물을 다시 알킬화 시약과 반응시켜 2-에틸리덴-3-알킬-1,3-티오졸리딘-4-온 화합물을 얻는 극히 제한적 방법이 사용되어졌다. 이때 사용되는 에틸 티오아세트산 에스테르는 공기 중에서 쉽게 산화되어 S-S결합, 즉 디설파이드 결합를 형성하므로 반응시 산소를 제거해야 하는 어려움이 따르고, 또한 첫 번째 단계에서 고온조건이 필요하며 알킬화 과정이 요구되는 2단계의 공정이 필요하다.Synthesis methods known to date are represented by the method described and described in the German Patent No. 1,150,985, specifically, 2-ethylidene by high-temperature reaction of malonitrile and its derivatives with ethyl thioacetester under anhydrous conditions without oxygen Extremely limited to obtain a -1,3-thiazolidin-4-one compound and react the compound again with an alkylating reagent to give a 2-ethylidene-3-alkyl-1,3-thiozolidin-4-one compound The method was used. At this time, the ethyl thioacetic acid ester is easily oxidized in air to form an SS bond, that is, a disulfide bond, and thus it is difficult to remove oxygen during the reaction, and in the first step, a high temperature condition is required and an alkylation process is required. The process is necessary.
본 발명의 목적은 2-펜아실리덴-3,5-알킬치환된-1,3-티아졸리딘-4-온을 보다 효과적으로 제조하는 방법을 제공하는 것이다. 즉, 상기 독일 특허에 비해 한단계로 이루어지며, 반응조건도 까다롭지 아니한 조건하에서 2-펜아실리덴-3,5-알킬치환된-1,3-티아졸리딘-4-온을 고수율로 제공하는 것을 그 목적으로 한다.It is an object of the present invention to provide a process for producing 2-phenacylidene-3,5-alkylsubstituted-1,3-thiazolidin-4-one more effectively. That is, it is made in one step compared to the German patent, and provides a 2-phenacylidene-3,5-alkyl-substituted-1,3-thiazolidin-4-one in high yield under conditions that are not demanding. It is for that purpose.
본 발명자들은 티오펜아실 케텐 S,N-아세탈을 이용하여 한 단계의 공정을 거치며 반응 조건도 상온에서 비교적 쉽게 하기 화학식 1을 갖는 2-펜아실리덴-3,5-알킬치환된-1,3-티아졸리딘-4-온을 합성하는 방법을 개발하였다. 하기 반응식 1에서 알 수 있듯이, 화학식 2의 티오펜아실 케텐 S,N-아세탈을 상온에서 화학식 3의 α-할로아실 할로겐 화합물과 반응시켜 2-펜아실리덴-3,5-알킬치환된-1,3-티아졸리딘-4-온을 보다 효과적으로 제조하는 방법을 개발하였다.The present inventors go through a one-step process using thiophenacyl ketene S, N-acetal, and the reaction conditions are also relatively easy at room temperature, 2-phenacylidene-3,5-alkylsubstituted-1,3 A method of synthesizing thiazolidin-4-ones has been developed. As can be seen in Scheme 1, 2-phenacylidene-3,5-alkylsubstituted-1 is reacted with an thiophenacyl ketene S, N-acetal of Formula 2 with an α-haloacyl halogen compound of Formula 3 at room temperature. A method for more effectively preparing, 3-thiazolidin-4-one has been developed.
[화학식 1][Formula 1]
[반응식 1]Scheme 1
상기 화학식 1, 2, 3 및 반응식 1에서 R1은 탄소수 1∼6의 알킬기, 탄소수 7∼8의 아릴알킬기, 방향족고리내에 탄소수 1∼3의 알킬기, 탄소수 1∼3의 알콕시기 및 할로겐으로 구성되는 군에서 선택되는 하나 이상에 의해 치환된 탄소수 7∼8의 아릴알킬기, 탄소수 5∼7의 시클로알킬기를 의미하며; R2는 수소 또는 탄소수 1∼3의 저급 알킬기를 의미하며; R3는 탄소수 1∼6의 알킬기, 벤질, 방향족고리내에 탄소수 1∼3의 알킬기, 탄소수 1∼3의 알콕시기, 할로겐, 디알킬아미노기 등에 의해 하나 이상 치환된 벤질기 등을 의미하며; X는 불소, 염소, 브롬 또는 요오드를 의미하며, 그 중에서 염소 또는 브롬이 보다 바람직하다.In Formulas 1, 2, 3 and Scheme 1, R 1 is an alkyl group having 1 to 6 carbon atoms, an arylalkyl group having 7 to 8 carbon atoms, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, and a halogen in an aromatic ring. An arylalkyl group having 7 to 8 carbon atoms and a cycloalkyl group having 5 to 7 carbon atoms substituted by one or more selected from the group consisting of; R 2 means hydrogen or a lower alkyl group having 1 to 3 carbon atoms; R 3 means an alkyl group having 1 to 6 carbon atoms, benzyl, a benzyl group substituted with one or more substituents by an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a halogen, a dialkylamino group, or the like; X means fluorine, chlorine, bromine or iodine, of which chlorine or bromine is more preferable.
탄소수 1∼6의 알킬기의 바람직한 예로는 메틸, 에틸, 프로필, 이소프로필, 부틸, 이소부틸, sec-부틸, t-부틸, 펜틸, 헥실 등이 있으며, 그 중에서 메틸, 예틸, 프로필 등의 저급알킬기가 보다 바람직하다.Preferred examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, t-butyl, pentyl, hexyl, and the like, and lower alkyl groups such as methyl, ethyl, propyl, etc. Is more preferable.
탄소수 7∼8의 아릴알킬기의 예로는 벤질, 펜에틸 등이 있다.Examples of the arylalkyl group having 7 to 8 carbon atoms include benzyl and phenethyl.
탄소수 1∼3의 알킬기에 의해 치환된 탄소수 7∼8의 아릴알킬기의 바람직한 예로는 4-메틸벤질, 2-메틸벤질, 3-메틸벤질, 4-에틸벤질, 3-에틸벤질, 4-프로필벤질, 2-프로필벤질, 4-메틸펜에틸, 2-메틸펜에틸, 3-메틸펜에틸, 에틸펜에틸, 프로필펜에틸 등이 있다.Preferred examples of the arylalkyl group having 7 to 8 carbon atoms substituted by an alkyl group having 1 to 3 carbon atoms include 4-methylbenzyl, 2-methylbenzyl, 3-methylbenzyl, 4-ethylbenzyl, 3-ethylbenzyl, 4-propylbenzyl , 2-propylbenzyl, 4-methylphenethyl, 2-methylphenethyl, 3-methylphenethyl, ethylphenethyl, propylphenethyl and the like.
탄소수 1∼3의 알콕시에 의해 치환된 탄소수 7∼8의 아릴알킬기의 바람직한 예로는 4-메톡시벤질, 2-메톡시벤질, 3-메톡시벤질, 4-에톡시벤질, 3-에톡시벤질, 2-에톡시벤질, 4-프로폭시벤질, 3-프로폭시벤질, 2-프로폭시벤질, 그리고 각각에대응되는 펜에틸 등이 있다.Preferred examples of the arylalkyl group having 7 to 8 carbon atoms substituted by alkoxy having 1 to 3 carbon atoms include 4-methoxybenzyl, 2-methoxybenzyl, 3-methoxybenzyl, 4-ethoxybenzyl and 3-ethoxybenzyl , 2-ethoxybenzyl, 4-propoxybenzyl, 3-propoxybenzyl, 2-propoxybenzyl, and the corresponding phenethyl, respectively.
할로겐에 의해 치환된 탄소수 7∼8의 아릴알킬기의 바람직한 예로는 4-클로로벤질, 2-클로로벤질, 3-클로로벤질, 4-브로모벤질, 3-브로모벤질, 2-브로모벤질, 4-플루오로벤질, 3-플루오로벤질, 2-플루오로벤질, 4-요오도벤질, 3-요오도벤질, 2-요오도벤질, 4-클로로-3-브로모벤질, 4-브로모-3-클로로벤질 및 각각에 대응되는 펜에틸 등이 있다.Preferred examples of the arylalkyl group having 7 to 8 carbon atoms substituted by halogen include 4-chlorobenzyl, 2-chlorobenzyl, 3-chlorobenzyl, 4-bromobenzyl, 3-bromobenzyl, 2-bromobenzyl, 4 -Fluorobenzyl, 3-fluorobenzyl, 2-fluorobenzyl, 4-iodobenzyl, 3-iodobenzyl, 2-iodobenzyl, 4-chloro-3-bromobenzyl, 4-bromo- 3-chlorobenzyl and the corresponding phenethyl each.
상기 탄소수 7∼8의 아릴알킬기는 탄소수 1∼3의 알킬기, 탄소수 1∼3의 알콕시기 및 할로겐으로 구성되는 군에서 선택되는 하나 이상의 치환기를 가질 수 있으며, 그 바람직한 예로는 4-메톡시-3-메틸벤질, 2-에톡시-4-메틸벤질, 4-클로로-3-에틸벤질, 3-브로모-4-메톡시벤질, 그리고 대응되는 펜에틸 등이 있다.The arylalkyl group having 7 to 8 carbon atoms may have one or more substituents selected from the group consisting of an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, and a halogen, and a preferred example thereof is 4-methoxy-3. -Methylbenzyl, 2-ethoxy-4-methylbenzyl, 4-chloro-3-ethylbenzyl, 3-bromo-4-methoxybenzyl, and the corresponding phenethyl.
시클로알킬기의 바람직한 예로는 시클로펜틸, 시클로헥실, 시클로헥실 등이 있으며, 시클로헥실이 보다 바람직하다.Preferred examples of the cycloalkyl group include cyclopentyl, cyclohexyl, cyclohexyl and the like, with cyclohexyl being more preferred.
본 발명의 화합물을 합성하기 위한 출발물질인 티오펜아실 케텐 S,N-아세탈은 주지의 화합물로서Bull. Korean Chem. Soc. 1994. 15(4), 273에 그 제조 방법이 명시되어 있으며, 티오펜아실 케텐 S,N-아세탈의 효용가치는J. Heterocyclic Chem.,1994,31, 1361,Heteroatom Chemistry1995, 6(4), 387 - 390 등에 기술되어 있듯이 헤테로고리 화합물을 합성하는 중간체로서 유용한 화합물이다.Thiophenacyl ketene S, N-acetal, a starting material for synthesizing the compound of the present invention, is known as Bull. Korean Chem. Soc. 1994. 15 (4), 273 describes the preparation method, and the utility value of thiophenacyl ketene S, N-acetal is J. Heterocyclic Chem., 1994, 31 , 1361, Heteroatom Chemistry 1995, 6 (4) 387-390, etc., are useful compounds as intermediates for the synthesis of heterocyclic compounds.
상기 반응의 반응온도는 0∼50℃가 적당하나, 15∼25℃ 로 조절하는 것이 보다 바람직하다. 반응용매는 특별히 제한되지 아니하며, 무극성 용매 및 극성 용매 모두를 사용할 수 있다. 그 예로는 클로로포름, 디클로로메탄, 클로로벤젠, 1,2-디클로로에탄, 1,1,2,2-테트라클로로에탄, 사염화탄소, 브로모포름, 디브로모메탄, 1,2-디브로모에탄, 브로모벤젠 등의 할로겐화 용매, 아세토니트릴, 프로피오니트릴, 벤조니트릴등 니트릴화 용매, 에틸아세테이트, 메틸아세테이트, 에틸프로피오네이트, 메틸프로피오네이트 등의 에스테르 용매, 아세톤, 메틸에틸케톤, 메틸프로필케톤, 시클로펜타논, 시클로헥사논, 시클로헵타논 등의 케톤류, N,N-디메틸포름아미드, 디메틸설폭시드 등 극성 비양자성용매, 니트로메탄, 니트로벤젠 등의 니트로화 용매, 디에틸 에테르, 디글라임, 모노글라임, 디페닐에테르 등의 에테르류가 있다. 용매의 조건은 무수일 필요가 없는 장점을 갖고 있으며, 오히려 적당량의 물을 함유하는 것이 반응에 도움을 줄 수 있는 등의 장점을 갖고 있다. 또한 이 제조방법은 질소 및 아르곤등의 무활성 대기 조건이 필요하지 않기 때문에, 일반적 실험 초보자도 쉽게 제조할 수 있는 이점을 갖고 있다.Although 0-50 degreeC is suitable for the reaction temperature of the said reaction, it is more preferable to adjust to 15-25 degreeC. The reaction solvent is not particularly limited, and both nonpolar and polar solvents can be used. Examples include chloroform, dichloromethane, chlorobenzene, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, carbon tetrachloride, bromoform, dibromomethane, 1,2-dibromoethane, Halogenated solvents such as bromobenzene, nitrile solvents such as acetonitrile, propionitrile and benzonitrile, ester solvents such as ethyl acetate, methyl acetate, ethyl propionate and methyl propionate, acetone, methyl ethyl ketone and methyl propyl Ketones such as ketones, cyclopentanone, cyclohexanone and cycloheptanone, polar aprotic solvents such as N, N-dimethylformamide and dimethyl sulfoxide, nitration solvents such as nitromethane and nitrobenzene, diethyl ether and digles Ethers such as lime, monoglyme and diphenyl ether. The condition of the solvent has the advantage that it does not need to be anhydrous, but rather has the advantage that containing an appropriate amount of water can help the reaction. In addition, this production method does not require inert atmospheric conditions such as nitrogen and argon, and thus has an advantage that it can be easily manufactured even by a beginner of a general experiment.
본 발명의 제조 방법에 의해 제조된 화학식 1의 화합물에 대한 분리 정제는 유기 화학 분야의 통상의 분리 정제 방법, 예를 들면 크로마토그라피법이나 재결정 방법을 사용하여 행할 수 있다.Separation and purification of the compound of formula (1) produced by the production method of the present invention can be carried out using a conventional separation and purification method in the field of organic chemistry, for example, chromatography or recrystallization.
본 발명의 범위가 그 메카니즘에 의존하지는 아니하나, 본 발명의 제조방법은 하기 반응식 2로 표현되는 메카니즘을 갖는 것으로 판단된다.Although the scope of the present invention does not depend on the mechanism, it is determined that the production method of the present invention has a mechanism represented by the following Scheme 2.
상기 반응식 2에서 R1, R2및 R3의 정의는 전술한 바와 같다.In Scheme 2, the definitions of R 1 , R 2, and R 3 are as described above.
상기 반응식 2에서 알 수 있는 바와 같이, 본 발명의 제조 방법에 대한 메카니즘은 먼저 티오펜아실 케텐 S,N-아세탈과 α-할로아실 할로겐 화합물이 반응하여 반응초기에 반응식 2의 괄호 안에 표기된 중간 염이 형성되고, 이 염은 따로 분리가능하나 반응 용매 중에 함유된 물, 또는 첨가되는 물에 의하여 고리가 풀어지고 고리 재배치 반응에 의하여 화학식 1의 화합물이 제조되는 것으로 구성된다.As can be seen in Scheme 2, the mechanism for the preparation method of the present invention is the intermediate salt indicated in the parentheses of Scheme 2 at the beginning of the reaction by first reacting thiophenacyl ketene S, N-acetal and α-haloacyl halogen compound These salts are formed separately, but the salts are separated, but consist of being released by the water contained in the reaction solvent or by the added water, and the compound of formula (1) being prepared by the ring rearrangement reaction.
실시예Example
본 발명의 제조방법은 아래의 실시예에 의해 보다 자세히 설명될 것이나, 본 발명의 범위가 아래의 실시예에 국한되는 것은 아니다.The manufacturing method of the present invention will be described in more detail by the following examples, but the scope of the present invention is not limited to the following examples.
실시예 1Example 1
2-펜아실리덴-3-에틸-1,3-티아졸리딘-4-온의 제조Preparation of 2-phenacylidene-3-ethyl-1,3-thiazolidin-4-one
1-에틸아미노-1-메틸티오-3-페닐프로펜-3-티온(12 mg, 0.13 mmol)을 톨루엔 (2 ml)에 용해시킨 후, 클로로아세틸 클로라이드(25 mg, 0.13 mmol)를 20℃에서 천천히 가한 후 10분간 교반하여 노란색의 고체를 석출시켰다. 이 반응계에 소량의 H2O를 가한 후 5분간 교반하였다. 반응의 종결을 TLC로 확인한 후, 10 ml 에테로로 추출하고, 얻어진 유기층을 10 ml H2O 및 10 ml 5% 탄산나트륨 수용액으로 씻었다. 유기층을 황산 나트륨으로 건조한 다음, 감압하에서 용매를 제거한 후 크로마토그래피(EA/HEX = 1/2)로 분리 정제하여 연갈색 고체인 목적 화합물 (25 mg, 0.10 mmol)을 얻었다.1-ethylamino-1-methylthio-3-phenylpropene-3-thione (12 mg, 0.13 mmol) was dissolved in toluene (2 ml), followed by chloroacetyl chloride (25 mg, 0.13 mmol) at 20 ° C. The solution was slowly added to and stirred for 10 minutes to precipitate a yellow solid. A small amount of H 2 O was added to the reaction system, followed by stirring for 5 minutes. After completion of the reaction was confirmed by TLC, extracted with 10 ml ether, and the obtained organic layer was washed with 10 ml H 2 O and 10 ml 5% sodium carbonate aqueous solution. The organic layer was dried over sodium sulfate, and the solvent was removed under reduced pressure, and then purified by chromatography (EA / HEX = 1/2) to obtain the target compound (25 mg, 0.10 mmol) as a light brown solid.
수득률: 92%Yield: 92%
mp 135℃mp 135 ℃
1H NMR (CDCl3): δ 1.32 (t, 3H, J = 7.2 Hz, CH2 CH 3), 3.72 (s, 2H, SCH2), 3.88 (q, 2H, J = 7.2 Hz,CH 2CH3), 6.72 (s, 1H, =CH), 7.50∼7.95 (m, 5H Ar); IR (KBr): 2970, 1704, 1628, 1516, 1326, 1216, 764 cm-1; MS: m/z 247 (M+, 12), 230 (72), 204 (20), 170 (37), 142 (23), 105 (100), 77 (71) 1 H NMR (CDCl 3 ): δ 1.32 (t, 3H, J = 7.2 Hz, CH 2 CH 3 ), 3.72 (s, 2H, SCH 2 ), 3.88 (q, 2H, J = 7.2 Hz, CH 2 CH 3 ), 6.72 (s, 1H, = CH), 7.50 to 7.95 (m, 5H Ar); IR (KBr): 2970, 1704, 1628, 1516, 1326, 1216, 764 cm −1 ; MS: m / z 247 (M + , 12), 230 (72), 204 (20), 170 (37), 142 (23), 105 (100), 77 (71)
실시예 2Example 2
2-펜아실리덴-3-메틸-1,3-티아졸리딘-4-온의 제조Preparation of 2-phenacylidene-3-methyl-1,3-thiazolidin-4-one
실시예 1과 같은 방법으로 1-메틸아미노-1-메틸티오-3-페닐프로펜-3-티온과 클로로아세틸 클로라이드를 반응시켜 노란색 고체인 목적 화합물을 얻었다.In the same manner as in Example 1, 1-methylamino-1-methylthio-3-phenylpropene-3-thione and chloroacetyl chloride were reacted to obtain the target compound as a yellow solid.
수득률: 89%Yield: 89%
mp 140℃mp 140 ℃
1H NMR (CDCl3): δ 3.24 (s, 3H, CH3), 3.66 (s, 2H, SCH2), 6.62 (s, 1H, =CH), 7.40∼7.89 (m, 5H Ar); IR (KBr): 2976, 1726, 1641, 1586, 1526, 1391, 1217, 1117, 1062, 923, 763 cm-1; MS: m/z 233 (M+, 100), 216 (39), 156 (88), 105 (64), 82 (19), 77 (67). 1 H NMR (CDCl 3 ): δ 3.24 (s, 3H, CH 3 ), 3.66 (s, 2H, SCH 2 ), 6.62 (s, 1H, = CH), 7.40 to 7.89 (m, 5H Ar); IR (KBr): 2976, 1726, 1641, 1586, 1526, 1391, 1217, 1117, 1062, 923, 763 cm −1 ; MS: m / z 233 (M + , 100), 216 (39), 156 (88), 105 (64), 82 (19), 77 (67).
실시예 3Example 3
2-펜아실리덴-3-(4-메틸벤질)-1,3-티아졸리딘-4-온의 제조Preparation of 2-phenacylidene-3- (4-methylbenzyl) -1,3-thiazolidin-4-one
실시예 1과 같은 방법으로 1-(4-메틸벤질아미노)-1-메틸티오-3-페닐프로펜-3-티온과 클로로아세틸 클로라이드를 반응시켜 연갈색 고체인 목적화합물을 얻었다.In the same manner as in Example 1, 1- (4-methylbenzylamino) -1-methylthio-3-phenylpropene-3-thione was reacted with chloroacetyl chloride to obtain a target compound as a light brown solid.
수득률: 91%Yield: 91%
mp 129-130℃mp 129-130 ℃
1H NMR (CDCl3): δ 2.24 (s, 3H, CH3), 3.74 (s, 2H, SCH2), 4.90 (s, 2H, NCH2), 6.62 (s, 1H, =CH), 7.11-7.71 (m, 9H Ar); IR (KBr): 2996, 1724, 1628, 1512, 1332, 1172, 1067, 903, 760 cm-1; MS: m/z 323 (M+, 10), 218 (9), 105 (100), 77 (29) 1 H NMR (CDCl 3 ): δ 2.24 (s, 3H, CH 3 ), 3.74 (s, 2H, SCH 2 ), 4.90 (s, 2H, NCH 2 ), 6.62 (s, 1H, = CH), 7.11 -7.71 (m, 9H Ar); IR (KBr): 2996, 1724, 1628, 1512, 1332, 1172, 1067, 903, 760 cm -1 ; MS: m / z 323 (M + , 10), 218 (9), 105 (100), 77 (29)
실시예 4Example 4
2-펜아실리덴-3-(4-메톡시벤질)-1,3-티아졸리딘-4-온의 제조Preparation of 2-phenacylidene-3- (4-methoxybenzyl) -1,3-thiazolidin-4-one
실시예1과 같은 방법으로 1-(4-메톡시벤질아미노)-1-메틸티오-3-페닐프로펜-3-티온과 클로로아세틸 클로라이드를 반응시켜 연갈색 고체인 목적화합물을 얻었다.In the same manner as in Example 1, 1- (4-methoxybenzylamino) -1-methylthio-3-phenylpropene-3-thione was reacted with chloroacetyl chloride to obtain a target compound as a light brown solid.
수득률: 83%Yield: 83%
mp 138-139℃mp 138-139 ℃
1H NMR (CDCl3): δ 3.80 (s, 3H, OCH3), 3.81 (s, 2H, SCH2), 4.96 (s, 2H, NCH2), 6.73 (s, 1H, =CH), 6.90-7.24 (m, 4H Ar), 7.45 - 7.80 (m, 5H Ar); IR (KBr): 2957, 1714, 1626, 1512, 1176, 1053, 898, 763 cm-1; MS: m/z 339 (M+, 16), 234 (2), 121 (100), 91 (4), 77 (13) 1 H NMR (CDCl 3 ): δ 3.80 (s, 3H, OCH 3 ), 3.81 (s, 2H, SCH 2 ), 4.96 (s, 2H, NCH 2 ), 6.73 (s, 1H, = CH), 6.90 -7.24 (m, 4H Ar), 7.45-7.80 (m, 5H Ar); IR (KBr): 2957, 1714, 1626, 1512, 1176, 1053, 898, 763 cm −1 ; MS: m / z 339 (M + , 16), 234 (2), 121 (100), 91 (4), 77 (13)
실시예 5Example 5
2-펜아실리덴-3-(2-펜에틸)-1,3-티아졸리딘-4-온의 제조Preparation of 2-phenacylidene-3- (2-phenethyl) -1,3-thiazolidin-4-one
실시예 1과 같은 방법으로 1-(2-펜에틸아미노)-1-메틸티오-3-페닐프로펜-3-티온과 클로로아세틸 클로라이드를 반응시켜 연갈색 고체인 목적화합물을 얻었다.In the same manner as in Example 1, 1- (2-phenethylamino) -1-methylthio-3-phenylpropene-3-thione was reacted with chloroacetyl chloride to obtain a target compound as a light brown solid.
수득률: 94%Yield: 94%
mp 121-122℃mp 121-122 ℃
1H NMR (CDCl3): δ 2.99 (t, 2H, J = 7.5 Hz, NCH2), 3.66 (s, 2H, SCH2),4.04 (t, 2H, J = 7.5 Hz, NCH2 CH 2), 6.69 (s, 1H, =CH), 7.34-7.89 (m, 10H, Ar); IR (KBr): 2957, 1712, 1624, 1508, 1352, 12172 1154, 1053, 928, 748 cm-1; MS: m/z 323 (M+, 28), 238 (12), 219 (37), 203 (45), 190 (16), 177 (46), 147 (23), 104 (100), 91 (29), 77 (16) 1 H NMR (CDCl 3 ): δ 2.99 (t, 2H, J = 7.5 Hz, NCH 2 ), 3.66 (s, 2H, SCH 2 ), 4.04 (t, 2H, J = 7.5 Hz, NCH 2 CH 2 ) , 6.69 (s, 1H, = CH), 7.34-7.89 (m, 10H, Ar); IR (KBr): 2957, 1712, 1624, 1508, 1352, 12172 1154, 1053, 928, 748 cm −1 ; MS: m / z 323 (M + , 28), 238 (12), 219 (37), 203 (45), 190 (16), 177 (46), 147 (23), 104 (100), 91 ( 29), 77 (16)
실시예 6Example 6
2-펜아실리덴-3-시클로헥실-1,3-티아졸리딘-4-온의 제조Preparation of 2-phenacylidene-3-cyclohexyl-1,3-thiazolidin-4-one
실시예 1과 같은 방법으로 1-시클로헥실아미노-1-에틸티오-3-페닐프로펜-3-티온과 클로로아세틸 클로라이드를 반응시켜 연노란색 고체인 목적화합물을 얻었다.In the same manner as in Example 1, 1-cyclohexylamino-1-ethylthio-3-phenylpropene-3-thione was reacted with chloroacetyl chloride to obtain a target compound as a pale yellow solid.
수득률: 88%Yield: 88%
mp 115 - 117℃mp 115-117 ℃
1H NMR (CDCl3): δ 1.25-2.35 (m, 10H), 3.66 (S, 2H, SCH2), 4.19 (m, 1H, NCH), 6.87 (s, 1H, =CH), 7.33-7.92 (m, 5H, Ar); MS: m/z 301 (M+, 6), 220 (40), 196 (8), 142 (8) , 105 (100), 77 (17) 1 H NMR (CDCl 3 ): δ 1.25-2.35 (m, 10H), 3.66 (S, 2H, SCH 2 ), 4.19 (m, 1H, NCH), 6.87 (s, 1H, = CH), 7.33-7.92 (m, 5H, Ar); MS: m / z 301 (M + , 6), 220 (40), 196 (8), 142 (8), 105 (100), 77 (17)
실시예 7Example 7
2-펜아실리덴-3-(4-벤질)-1,3-티아졸리딘-4-온의 제조Preparation of 2-phenacylidene-3- (4-benzyl) -1,3-thiazolidin-4-one
실시예 1과 같은 방법으로 1-(4-벤질아미노)-1-프로필티오-3-페닐프로펜-3-티온과 클로로아세틸 클로라이드를 반응시켜 연노란색의 고체인 목적화합물을 얻었다.In the same manner as in Example 1, 1- (4-benzylamino) -1-propylthio-3-phenylpropene-3-thione was reacted with chloroacetyl chloride to obtain a target compound as a pale yellow solid.
수득률: 87%Yield: 87%
mp 151-152℃mp 151-152 ℃
1H NMR (CDCl3): δ 3.83 (s, 2H, SCH2), 5.02 (s, 2H, NCH2), 6.67 (s, 1H, =CH), 7.29 -7.76 (m, 10H, Ar); IR (KBr): 2927, 1720, 1626, 1510, 1322, 1177, 1067, 923, 888, 762, 709 cm-1; MS: m/z 309 (M+, 58), 292 (12), 234 (7), 131 (13), 105 (36), 91 (100), 77 (21) 1 H NMR (CDCl 3 ): δ 3.83 (s, 2H, SCH 2 ), 5.02 (s, 2H, NCH 2 ), 6.67 (s, 1H, = CH), 7.29 -7.76 (m, 10H, Ar); IR (KBr): 2927, 1720, 1626, 1510, 1322, 1177, 1067, 923, 888, 762, 709 cm −1 ; MS: m / z 309 (M + , 58), 292 (12), 234 (7), 131 (13), 105 (36), 91 (100), 77 (21)
실시예 8Example 8
2-펜아실리덴-3-(4-클로로벤질)-1,3-티아졸리딘-4-온의 제조Preparation of 2-phenacylidene-3- (4-chlorobenzyl) -1,3-thiazolidin-4-one
실시예1과 같은 방법으로 1-(4-클로로벤질아미노)-1-메틸티오-3-페닐프로펜-3-티온과 클로로아세틸 클로라이드를 반응시켜 연갈색 고체인 목적화합물을 얻었다.In the same manner as in Example 1, 1- (4-chlorobenzylamino) -1-methylthio-3-phenylpropene-3-thione was reacted with chloroacetyl chloride to obtain a target compound as a light brown solid.
수득률: 90%Yield: 90%
mp 182-183℃mp 182-183 ℃
1H NMR (CDCl3): δ 3.86 (s, 2H, SCH2), 5.16 (s, 2H, NCH2), 6.62 (s, 1H, =CH), 7.10 -7.81 (m, 9H, Ar); IR (KBr): 2964, 1716, 1628, 1812, 1366, 1324, 1178, 1062, 894, 756 cm-1; MS: m/z 343 (M+, 3), 308 (29), 266 (10), 125 (48), 105 (100), 89 (14), 77(24) 1 H NMR (CDCl 3 ): δ 3.86 (s, 2H, SCH 2 ), 5.16 (s, 2H, NCH 2 ), 6.62 (s, 1H, = CH), 7.10 -7.81 (m, 9H, Ar); IR (KBr): 2964, 1716, 1628, 1812, 1366, 1324, 1178, 1062, 894, 756 cm -1 ; MS: m / z 343 (M + , 3), 308 (29), 266 (10), 125 (48), 105 (100), 89 (14), 77 (24)
실시예 9Example 9
2-펜아실리덴-3-(3-클로로벤질)-1,3-티아졸리딘-4-온의 제조Preparation of 2-phenacylidene-3- (3-chlorobenzyl) -1,3-thiazolidin-4-one
실시예1과 같은 방법으로 1-(3-클로로벤질아미노)-1-에틸티오-3-페닐프로펜-3-티온과 클로로아세틸 클로라이드를 반응시켜 노란색 고체인 목적화합물을 얻었다.In the same manner as in Example 1, 1- (3-chlorobenzylamino) -1-ethylthio-3-phenylpropene-3-thione was reacted with chloroacetyl chloride to obtain a target compound as a yellow solid.
수득률: 95%Yield: 95%
mp 151℃mp 151 ℃
1H NMR (CDCl3): δ 3.84 (s, 2H, SCH2), 4.98 (s, 2H, NCH2), 6.63 (s, 1H, =CH), 7.19 -7.78 (m, 9H, Ar); IR (KBr): 2986, 1728, 1626, 1504, 1360, 1172, 1062, 903, 756, 709 cm-1; MS: m/z 343 (M+, 38), 304 (15), 300 (6), 268 (11), 238 (2), 164 (9), 164 (2), 131 (26), 125 (75), 105 (100), 77 (46) 1 H NMR (CDCl 3 ): δ 3.84 (s, 2H, SCH 2 ), 4.98 (s, 2H, NCH 2 ), 6.63 (s, 1H, = CH), 7.19 -7.78 (m, 9H, Ar); IR (KBr): 2986, 1728, 1626, 1504, 1360, 1172, 1062, 903, 756, 709 cm -1 ; MS: m / z 343 (M + , 38), 304 (15), 300 (6), 268 (11), 238 (2), 164 (9), 164 (2), 131 (26), 125 ( 75), 105 (100), 77 (46)
실시예 10Example 10
2-펜아실리덴-3-에틸-5-메틸-1,3-티아졸리딘-4-온의 제조Preparation of 2-phenacylidene-3-ethyl-5-methyl-1,3-thiazolidin-4-one
실시예1과 같은 방법으로1-(4-에틸아미노)-1-메틸티오-3-페닐프로펜-3-티온과 2-브로모프로피오닐 브로마이드를 반응시켜 연갈색 고체인 목적화합물을 얻었다.In the same manner as in Example 1, 1- (4-ethylamino) -1-methylthio-3-phenylpropene-3-thione was reacted with 2-bromopropionyl bromide to obtain the target compound as a light brown solid.
수득률: 92 %Yield: 92%
mp 150-150.5℃mp 150-150.5 ℃
1H NMR (CDCl3): δ 1.24 (t, 3H, J = 7.2 Hz, CH2 CH 3), 1.57 (d, 3H, J = 7.2 Hz, CH3), 3.80 (q, 3H, J = 7.2 Hz, SCH, NCH2), 6.62 (s, 1H, =CH), 7.40-7.80 (m, 5H, Ar); IR (KBr): 2970, 1704, 1628, 1516, 1326, 1216, 764 cm-1; MS: m/z 261 (M+, 76), 244 (100), 204 (23), 184 (39), 156 (21), 131 (29), 105 (92), 77 (62) 1 H NMR (CDCl 3 ): δ 1.24 (t, 3H, J = 7.2 Hz, CH 2 CH 3 ), 1.57 (d, 3H, J = 7.2 Hz, CH 3 ), 3.80 (q, 3H, J = 7.2 Hz, SCH, NCH 2 ), 6.62 (s, 1H, = CH), 7.40-7.80 (m, 5H, Ar); IR (KBr): 2970, 1704, 1628, 1516, 1326, 1216, 764 cm −1 ; MS: m / z 261 (M + , 76), 244 (100), 204 (23), 184 (39), 156 (21), 131 (29), 105 (92), 77 (62)
실시예 11Example 11
2-펜아실리덴-3-메틸-5-메틸-1,3-티아졸리딘-4-온의 제조Preparation of 2-phenacylidene-3-methyl-5-methyl-1,3-thiazolidin-4-one
실시예 1과 같은 방법으로 1-(4-메틸아미노)-1-프로필티오-3-페닐프로펜-3-티온과 2-브로모프로피오닐 브로마이드를 반응시켜 연갈색의 고체인 목적화합물을 얻었다.1- (4-methylamino) -1-propylthio-3-phenylpropene-3-thione and 2-bromopropionyl bromide were reacted in the same manner as in Example 1 to obtain a target compound as a light brown solid.
수득률: 90%Yield: 90%
mp 131-132Cmp 131-132C
1H NMR (CDCl3): δ 1.57 (d, 3H, J = 7.2 Hz, CH3), 3.24 (s, 3H, NCH3), 3.82 (q, 1H, J = 7.2 Hz, SCH), 6.59 (s, 1H, =CH), 7.40-7.80 (m, 5H, Ar); IR (KBr): 2937, 1710, 1622, 1514, 1357, 1232, 1062, 758 cm-1; MS: m/z 247 (M+, 100), 230 (42), 170 (82), 142 (16), 114 (15), 105 (56), 77 (56). 1 H NMR (CDCl 3 ): δ 1.57 (d, 3H, J = 7.2 Hz, CH 3 ), 3.24 (s, 3H, NCH 3 ), 3.82 (q, 1H, J = 7.2 Hz, SCH), 6.59 ( s, 1H, = CH), 7.40-7.80 (m, 5H, Ar); IR (KBr): 2937, 1710, 1622, 1514, 1357, 1232, 1062, 758 cm -1 ; MS: m / z 247 (M + , 100), 230 (42), 170 (82), 142 (16), 114 (15), 105 (56), 77 (56).
실시예 12Example 12
2-펜아실리덴-3-(4-메틸벤질)-5-메틸-1,3-티아졸리딘-4-온의 제조.Preparation of 2-phenacylidene-3- (4-methylbenzyl) -5-methyl-1,3-thiazolidin-4-one.
실시예 1과 같은 방법으로 1-(4-메틸벤질아미노)-1-에틸티오-3-페닐프로펜-3-티온과 2-브로모프로피오닐 브로마이드를 반응시켜 연갈색 고체인 목적화합물을 얻었다.In the same manner as in Example 1, 1- (4-methylbenzylamino) -1-ethylthio-3-phenylpropene-3-thione was reacted with 2-bromopropionyl bromide to obtain the target compound as a light brown solid.
수득률: 78%;Yield: 78%;
mp 167-168℃mp 167-168 ℃
1H NMR (CDCl3): δ 1.70 (d, 3H, J = 7.2 Hz, CH3), 2.34 (s, 3H, Ph-CH3), 4.00 (q, 1H, J = 7.2 Hz, SCH), 4.97 (s, 2H, NCH2), 6.67 (s, 1H, =CH), 7.23-7.77 (m, 9H, Ar); IR (KBr): 2927, 1716, 1622, 1494, 1328, 1170, 1053, 898, 748 cm-1; MS: m/z 337 (M+, 8), 105 (100), 77 (26). 1 H NMR (CDCl 3 ): δ 1.70 (d, 3H, J = 7.2 Hz, CH 3 ), 2.34 (s, 3H, Ph-CH 3 ), 4.00 (q, 1H, J = 7.2 Hz, SCH), 4.97 (s, 2H, NCH 2 ), 6.67 (s, 1H, = CH), 7.23-7.77 (m, 9H, Ar); IR (KBr): 2927, 1716, 1622, 1494, 1328, 1170, 1053, 898, 748 cm −1 ; MS: m / z 337 (M + , 8), 105 (100), 77 (26).
실시예 13Example 13
2-펜아실리덴-3-(4-메톡시벤질)-5-메틸-1,3-티아졸리딘-4-온의 제조.Preparation of 2-phenacylidene-3- (4-methoxybenzyl) -5-methyl-1,3-thiazolidin-4-one.
실시예1과 같은 방법으로 1-(4-메톡시벤질아미노)-1-에틸티오-3-페닐프로펜-3-티온과 2-브로모프로피오닐 브로마이드를 반응시켜 연갈색 고체인 목적화합물을 얻었다.In the same manner as in Example 1, 1- (4-methoxybenzylamino) -1-ethylthio-3-phenylpropene-3-thione was reacted with 2-bromopropionyl bromide to obtain the target compound as a light brown solid. .
수득률: 88%Yield: 88%
mp 151-152℃mp 151-152 ℃
1H NMR (CDCl3): δ 1.69 (d, 3H, J = 7.2 Hz, CH3), 3.79 (s, 3H, OCH3),3.96 (q, 1H, J = 7.2 Hz, SCH), 4.95 (s, 2H, NCH2), 6.69 (s, 1H, =CH), 6.89-7.21 (m, 4H, Ar), 7.45- 7.78 (m, 5H, Ar); IR (KBr): 2928, 1712, 1622, 1502, 1322, 1248, 1170, 1067, 893, 746 cm-1; MS: m/z 353 (M+, 22), 248 (3), 121 (100), 91 (4), 77 (13) 1 H NMR (CDCl 3 ): δ 1.69 (d, 3H, J = 7.2 Hz, CH 3 ), 3.79 (s, 3H, OCH 3 ), 3.96 (q, 1H, J = 7.2 Hz, SCH), 4.95 ( s, 2H, NCH 2 ), 6.69 (s, 1H, = CH), 6.89-7.21 (m, 4H, Ar), 7.45-7.78 (m, 5H, Ar); IR (KBr): 2928, 1712, 1622, 1502, 1322, 1248, 1170, 1067, 893, 746 cm −1 ; MS: m / z 353 (M + , 22), 248 (3), 121 (100), 91 (4), 77 (13)
실시예 14Example 14
2-펜아실리덴-3-(2-페닐에틸)-5-메틸-1,3-티아졸리딘-4-온의 제조.Preparation of 2-phenacylidene-3- (2-phenylethyl) -5-methyl-1,3-thiazolidin-4-one.
실시예 1과 같은 방법으로 1-(2-페닐에틸아미노)-1-메틸티오-3-페닐프로펜-3-티온과 2-브로모프로피오닐 브로마이드를 반응시켜 연갈색 고체인 목적화합물을 얻었다.In the same manner as in Example 1, 1- (2-phenylethylamino) -1-methylthio-3-phenylpropene-3-thione was reacted with 2-bromopropionyl bromide to obtain the target compound as a light brown solid.
수득률: 83%Yield: 83%
1H NMR (CDCl3): δ 1.64 (s, 3H, CH3), 3.01 (t, 2H, J = 7.2 Hz, NCH2), 3.80 (q, 1H , J = 7.2 Hz, SCH), 4.05 (m, 2H, NCH2 CH 2), 6.68 (s, 1H, =CH), 7.20-7.89 (m, 10H, Ar); 1 H NMR (CDCl 3 ): δ 1.64 (s, 3H, CH 3 ), 3.01 (t, 2H, J = 7.2 Hz, NCH 2 ), 3.80 (q, 1H, J = 7.2 Hz, SCH), 4.05 ( m, 2H, NCH 2 CH 2 ), 6.68 (s, 1H, = CH), 7.20-7.89 (m, 10H, Ar);
MS: m/z 337 (M+, 9), 233 (8), 104 (100), 91 (4), 77 (22)MS: m / z 337 (M + , 9), 233 (8), 104 (100), 91 (4), 77 (22)
실시예 15Example 15
2-펜아실리덴-3-시클로헥실-5-메틸-1,3-티아졸리딘-4-온의 제조.Preparation of 2-phenacylidene-3-cyclohexyl-5-methyl-1,3-thiazolidin-4-one.
실시예 1과 같은 방법으로 1-(4-시클로헥실아미노)-1-에틸티오-3-페닐프로펜-3-티온과 2-브로모프로피오닐 브로마이드를 반응시켜 노란색 고체인 목적화합물을 얻었다.In the same manner as in Example 1, 1- (4-cyclohexylamino) -1-ethylthio-3-phenylpropene-3-thione was reacted with 2-bromopropionyl bromide to obtain the target compound as a yellow solid.
수득률: 73%Yield: 73%
mp 173-174℃mp 173-174 ℃
1H NMR (CDCl3): δ 1.25 - 2.32 (m, 10H), 1.61 (d, 3H, J = 7.2 Hz, CH3), 3.79 (q, 1H, J = 7.2 Hz, SCH), 4.14 (m, 1H, NCH), 6.85 (s, 1H, =CH), 7.26-7.92 (m, 5H, Ar); IR (KBr): 2914, 1714, 1628, 1500, 1327, 1207, 1062, 758 cm-1; MS: m/z 315 (M+, 4), 234 (26), 210 (6), 156 (4), 105 (100), 77 (16) 1 H NMR (CDCl 3 ): δ 1.25-2.32 (m, 10H), 1.61 (d, 3H, J = 7.2 Hz, CH 3 ), 3.79 (q, 1H, J = 7.2 Hz, SCH), 4.14 (m , 1H, NCH), 6.85 (s, 1H, = CH), 7.26-7.92 (m, 5H, Ar); IR (KBr): 2914, 1714, 1628, 1500, 1327, 1207, 1062, 758 cm -1 ; MS: m / z 315 (M + , 4), 234 (26), 210 (6), 156 (4), 105 (100), 77 (16)
실시예 16Example 16
2-펜아실리덴-3-벤질-5-메틸-1,3-티아졸리딘-4-온의 제조.Preparation of 2-phenacylidene-3-benzyl-5-methyl-1,3-thiazolidin-4-one.
실시예 1과 같은 방법으로 1-벤질아미노-1-메틸티오-3-페닐프로펜-3-티온과 2-브로모프로피오닐 브로마이드를 반응시켜 연갈색 고체인 목적화합물을 얻었다.In the same manner as in Example 1, 1-benzylamino-1-methylthio-3-phenylpropene-3-thione and 2-bromopropionyl bromide were reacted to obtain the target compound as a light brown solid.
수득률: 88%Yield: 88%
mp 154℃mp 154 ℃
1H NMR (CDCl3): δ 1.71 (d, 3H, J = 7.2 Hz, CH3), 3.99 (q, 1H, J = 7.2 Hz, SCH), 5.01 (s, 2H, NCH2), 6.64 (s, 1H, =CH), 7.29-7.75 (m, 10H, Ar); IR (KBr): 2937, 1712, 1628, 1520, 1327, 1217, 1182, 1062, 763, 704 cm-1; MS: m/z 323 (M+, 57), 306 (15), 266 (7), 235 (15), 163 (8), 131 (18), 105 (39), 91(100), 77 (28). 1 H NMR (CDCl 3 ): δ 1.71 (d, 3H, J = 7.2 Hz, CH 3 ), 3.99 (q, 1H, J = 7.2 Hz, SCH), 5.01 (s, 2H, NCH 2 ), 6.64 ( s, 1H, = CH), 7.29-7.75 (m, 10H, Ar); IR (KBr): 2937, 1712, 1628, 1520, 1327, 1217, 1182, 1062, 763, 704 cm −1 ; MS: m / z 323 (M + , 57), 306 (15), 266 (7), 235 (15), 163 (8), 131 (18), 105 (39), 91 (100), 77 ( 28).
실시예 17Example 17
2-펜아실리덴-3-(2-클로로벤질)-5-메틸-1,3-티아졸리딘-4-온의 제조.Preparation of 2-phenacylidene-3- (2-chlorobenzyl) -5-methyl-1,3-thiazolidin-4-one.
실시예1과 같은 방법으로 1-(2-클로로벤질아미노)-1-메틸티오-3-페닐프로펜-3-티온과 2-브로모프로피오닐 브로마이드를 반응시켜 연갈색 고체인 목적화합물을 얻었다.In the same manner as in Example 1, 1- (2-chlorobenzylamino) -1-methylthio-3-phenylpropene-3-thione was reacted with 2-bromopropionyl bromide to obtain the target compound as a light brown solid.
수득률: 70%Yield: 70%
mp 154℃mp 154 ℃
1H NMR (CDCl3): δ 1.73 (d, 3H, J = 7.2 Hz, CH3), 4.02 (q, 1H, J = 7.2 Hz, SCH), 5.15 (s, 2H, NCH2), 6.59 (s, 1H, =CH), 7.05-7.80 (m, 9H, Ar); IR (KBr): 2624, 1716, 1628, 1512, 1366, 1324, 1178, 1062, 894, 754 cm-1; MS: m/z 343 (M+, 3), 308 (29), 266 (10), 125 (48), 105 (100), 89 (14), 77 (24). 1 H NMR (CDCl 3 ): δ 1.73 (d, 3H, J = 7.2 Hz, CH 3 ), 4.02 (q, 1H, J = 7.2 Hz, SCH), 5.15 (s, 2H, NCH 2 ), 6.59 ( s, 1H, = CH), 7.05-7.80 (m, 9H, Ar); IR (KBr): 2624, 1716, 1628, 1512, 1366, 1324, 1178, 1062, 894, 754 cm -1 ; MS: m / z 343 (M + , 3), 308 (29), 266 (10), 125 (48), 105 (100), 89 (14), 77 (24).
실시예 18Example 18
2-펜아실리덴-3-(3-클로로벤질)-5-메틸-1,3-티아졸리딘-4-온의 제조.Preparation of 2-phenacylidene-3- (3-chlorobenzyl) -5-methyl-1,3-thiazolidin-4-one.
실시예1과 같은 방법으로 1-(3-클로로벤질아미노)-1-메틸티오-3-페닐프로펜-3-티온과 2-브로모프로피오닐 브로마이드를 반응시켜 연갈색 고체인 목적화합물을 얻었다.In the same manner as in Example 1, 1- (3-chlorobenzylamino) -1-methylthio-3-phenylpropene-3-thione was reacted with 2-bromopropionyl bromide to obtain the target compound as a light brown solid.
수득률: 78%Yield: 78%
1H NMR (CDCl3): δ 1.68 (d, 3H, J = 7.2 Hz, CH3), 4.01 (q, 1H, J = 7.2 Hz, SCH), 4.98 (s, 2H, NCH2), 6.60 (s, 1H, =CH), 7.14-7.76 (m, 9H, Ar); MS: m/z 357 (M+, 38), 340 (15), 300 (6), 269 (14), 252 (9), 164 (2), 131 (26), 125 (75), 105 (100), 77 (46). 1 H NMR (CDCl 3 ): δ 1.68 (d, 3H, J = 7.2 Hz, CH 3 ), 4.01 (q, 1H, J = 7.2 Hz, SCH), 4.98 (s, 2H, NCH 2 ), 6.60 ( s, 1H, = CH), 7.14-7.76 (m, 9H, Ar); MS: m / z 357 (M + , 38), 340 (15), 300 (6), 269 (14), 252 (9), 164 (2), 131 (26), 125 (75), 105 ( 100), 77 (46).
실시예 19Example 19
2-펜아실리덴-3-(4-클로로벤질)-5-메틸-1,3-티아졸리딘-4-온의 제조.Preparation of 2-phenacylidene-3- (4-chlorobenzyl) -5-methyl-1,3-thiazolidin-4-one.
실시예1과 같은 방법으로 1-(4-클로로벤질아미노)-1-메틸티오-3-페닐프로펜-3-티온과 2-브로모프로피오닐 브로마이드를 반응시켜 연갈색 고체인 목적화합물을 얻었다.In the same manner as in Example 1, 1- (4-chlorobenzylamino) -1-methylthio-3-phenylpropene-3-thione was reacted with 2-bromopropionyl bromide to obtain the target compound as a light brown solid.
수득률: 87%Yield: 87%
mp 166℃mp 166 ℃
1H NMR (CDCl3): δ 1.70 (d, 3H, J =7.2 Hz, CH3), 3.98 (q, 1H, J = 7.2 Hz, SCH), 4.97 (s, 2H, NCH2), 6.60 (s, 1H, =CH), 7.20-7.77 (m, 9H, Ar); IR (KBr): 3066, 1716, 1624, 1498, 1375, 1324, 1212, 1172, 1062, 803, 748 cm-1; MS: m/z 357 (M+, 49), 340 (14), 300 (6), 269 (16), 252 (11), 163 (10), 131 (26), 125 (100), 105 (65), 77 (35). 1 H NMR (CDCl 3 ): δ 1.70 (d, 3H, J = 7.2 Hz, CH 3 ), 3.98 (q, 1H, J = 7.2 Hz, SCH), 4.97 (s, 2H, NCH 2 ), 6.60 ( s, 1H, = CH), 7.20-7.77 (m, 9H, Ar); IR (KBr): 3066, 1716, 1624, 1498, 1375, 1324, 1212, 1172, 1062, 803, 748 cm −1 ; MS: m / z 357 (M + , 49), 340 (14), 300 (6), 269 (16), 252 (11), 163 (10), 131 (26), 125 (100), 105 ( 65), 77 (35).
본 발명의 제조 방법은 기존의 제조방법과 달리 화학식 1의 2-펜아실리덴-3,5-알킬치환된-1,3-티아졸리딘-4-온을 한 반응용기, 즉 1단계 반응에 의해 제조 할 수 있는 장점이 있다. 그리고 반응 온도도 고온을 요하지 않고 상온 근처에서 수행할 수 있으며, 반응환경 역시 질소 또는 아르곤 등의 특이한 환경을 요하지 않는 일반적 반응환경에서 수행할 수 있다는 장점이 있다.Unlike the conventional production method, the production method of the present invention uses a 2-phenacylidene-3,5-alkyl-substituted-1,3-thiazolidin-4-one of formula (1), that is, a one-step reaction There is an advantage that can be manufactured by. In addition, the reaction temperature may be performed near room temperature without requiring a high temperature, and the reaction environment may also be performed in a general reaction environment that does not require a specific environment such as nitrogen or argon.
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|---|---|
| KR (1) | KR100329808B1 (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56164174A (en) * | 1980-05-23 | 1981-12-17 | Kureha Chem Ind Co Ltd | Novel thiazolidone derivative, its preparation and antipeptic ulcer agent containing the same |
| US4563471A (en) * | 1983-05-10 | 1986-01-07 | Warner-Lambert Company | 4-Oxothiazolidin-2-ylidene-acetamide derivatives as CNS agents |
| JPH04117371A (en) * | 1990-09-05 | 1992-04-17 | Otsuka Pharmaceut Factory Inc | Thiazole derivative |
| JPH07242645A (en) * | 1994-01-14 | 1995-09-19 | Taisho Pharmaceut Co Ltd | 3-arylthiazoline derivative |
-
2000
- 2000-01-14 KR KR1020000001703A patent/KR100329808B1/en not_active IP Right Cessation
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56164174A (en) * | 1980-05-23 | 1981-12-17 | Kureha Chem Ind Co Ltd | Novel thiazolidone derivative, its preparation and antipeptic ulcer agent containing the same |
| US4563471A (en) * | 1983-05-10 | 1986-01-07 | Warner-Lambert Company | 4-Oxothiazolidin-2-ylidene-acetamide derivatives as CNS agents |
| JPH04117371A (en) * | 1990-09-05 | 1992-04-17 | Otsuka Pharmaceut Factory Inc | Thiazole derivative |
| JPH07242645A (en) * | 1994-01-14 | 1995-09-19 | Taisho Pharmaceut Co Ltd | 3-arylthiazoline derivative |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20010073360A (en) | 2001-08-01 |
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