• Archives of Pharmacal Research
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• 제23권4호
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• pp.315-323
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• 2000

Syntheses of new analogues of oxathiin carboxanilide (UC84) and their antiviral activities were described. The heterocyclic carboxylic acids including oxathiins (4), thiazines (9) and dithiins (13) in which the methyl was replaced either by lipophilic trifluoromethyl- or bulky phenylgroup were synthesized starting from $\beta$-keto esters (5). Reaction of 4, 9 and 13 with thionyl chloride followed by treatment of the substituted aniline 22 gave the corresponding carboxanilides (24a~24f). The carboxanilides were subjected to Laweson's reagent the corresponding thiocarboxanilides (24g~24k). The antiviral activities of the synthesized compounds against human immunodeficiency virus type 1 (HIV-1), poliovirus type 1 (PV-1 ), coxsackie B virus type 3 (CoxB-3), vesicular stomatitis virus (VSV) and herpes simplex virus type 1 (HSV-1) were presented. The antiviral activity against HIV-1 of dithiin carboxanilide (24e) was similar with that of UC84 (24a). The corresponding thiocarboxanilides (24g~24k) showed higher inhibitory activity against HIV-1 than the carboxanilides (24a, 24b, 24d, 24e). The compounds in which ether the lipophilic trifluorormethyl substituents (24d, 24f, 24i ,24k) or bulky phenyl substituent is present in the heterocyclic compounds showed lower inhibitory activity than that of the methyl substituents is present in the compounds against the HIV-1. But the trifluoromethylated dithiin (24f) showed higher inhibitory activity against PV-1 and CoxB-3 virus than commercial antiviral agents, ribavirin (RV).

• Bulletin of the Korean Chemical Society
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• 제13권1호
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• pp.83-87
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• 1992

The ring expansion of 1,3-thiazolidines 4 derived from ${\beta}$-ketoacid derivatives to the corresponding dihydro-1,4-thiazines 1 by using the action of chlorine on 4 has been achieved. In the chlorinolysis unisolable sulfenyl chlorides 5 may be formed from chlorosulfonium ions 11 by ${\beta}$-elimination involving carbonyl activated methylene hydrogens. Addition of sulfenyl chloride to the internal double bond appears to form probable thiiranium ions 14, which in turn gave 1 with loss of acidic proton. Imminium ions 15 could be hydrolyzed easily to give enol 8. As a side reaction, dihydrothiazine that was formed was further chlorinated to produce dichlorides 16 which were rearranged readily to the chloromethyl compounds 10.

• 대한화학회지
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• 제33권2호
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• pp.247-256
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• 1989

4-아세틸-5,6-디히드로-2-메틸-1,4-티아진-3-카르복실산 유도체 24를 상응하는 티아졸리딘 술폭시드의 고리확대에 의하여 제조하였다. 2-메틸-1,3-티아졸라딘-2-아세트산 유도체 12를 산화하여 시스와 트랜스 술폭시드, 14 및 15를 얻었으며 이들의 구조는 수소핵자기 공명스펙트럼, 적외선 흡수스펙트럼, 그리고 중수소 치환반응에 의한 regioselectivity에 근거하여 결정하였다. 산촉매 존재하에서 시스와트랜스 술폭시드, 14 및 15는 중간체 술페닌산 18을 거쳐 디히드로-1,4-티아진 24로 전환되었다. 그러나 중성조건($100^{\circ}C$의 DMF)에서 트랜스 술폭시드 15는 중간체 술페닌산 21을 거쳐 isomeric 디히드로-1,4-티아진 27로 전환하였다. 화합물 24와 27의 생성반응기전도 논의하였다.