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Journal of the Korean Chemical Society (JKCS)

ISSN 1017-2548(Print)
ISSN 2234-8530(Online)
Volume 37, Number 1
JKCSEZ 37(1)
February 20, 1993 

A Study on the Stereochemistry of 1,3-Thiazolidine

1,3-티아졸리딘 술폭시드의 입체구조에 관한 연구
He-Duck Mah, Shin-Ja Park, Hoh-Gyu Hahn

마혜덕, 박신자, 한호규
한 분자 내에 3개의 chiral 중심이 있는 1,3-티아졸리딘 술록시드 1의 입체화학을 중수소치환반응 및 trapping 반응을 통해 밝혔다. 3-아세틸-1,3-티아졸리딘 5의 부분이성질체를 분리한 다음 6과 8을 각각 술록시드로 산화시켜 상응하는 α-시스 10, α-트랜스 11과 β-시스 12, β-트랜스이성체 13을 얻었다. 술폭시드 10은 중성 조건하의 환류하는 벤젠 또는 톨루엔 용액 중에서 열역학적으로 보다 안정한 13으로 이성질화하였다. 중수소치환반응에 의해서 술폭시드 13과 술폭시드 11의 2-메틸기의 수소원자는 중수소로 치환되었다. 술폭시드 10과 12로부터 sigmatropic 전위에 의해서 생성된 중간체 슬페닌산 25 및 26은 2-머캡토벤조티아졸(2-MBT)에 의하여 trap되어 디술피드 27 및 28로 전환되었으나 동일한 반응조건하에서 술폭시드 11 및 13은 환팽창 생성물 디히드로-1,4-티아진 29로 전환되었다. 산촉매 존재하에서 술폭시드 10, 11, 12는 술폭시드 13을 통해서 디히드로-1,4-티아진 29로 정량적으로 전환되었다. 술폭시드들의 이성질화 및 29의 생성메카니즘도 기술하였다.

The stereochemistry of 1,3-thiazolidine sulfoxides 1 in which 3 chiral centres are present in a molecule was elucidated by deuterium exchange and trapping reactions. 3-Acetoxy-1,3-thiazolidines 5 was oxidized to 6 and 8, corresponding α-cis 10, α-trans 11, β-cis 12, and β-trans 13 isomers were separated from their diasteromeric mixtures. Sulfoxide 10 was isomerized to more thermodynamically stable isomer 13 under neutral conditions in refluxing benzene or toluene. The methyl hydrogens of 2-methyl group in the sulfoxide 13 and those of the sulfoxide 11 were deuterated by the deuterium incorporation reactions. The intermediate sulfenic acids 25 and 26 derived from the sulfoxides 10 and 12 via sigmatropic rearrangement were trapped by 2-mercaptobenzothiazole (2-MBT) to give disufides 27 and 28 respectively. However, the sulfoxides 11 and 13 were transformed to ring expansion product dihydro-1,4-thiazine 29 under the same reaction conditions. In the presence of acid catalyst, the sulfoxides 10, 11, and 12 were converted to dihydro-1,4-thiazine 29 through the sulfoxide 13 quantitatively. The mechanisms of isomerization of sulfoxides and the formation of 29 were also discussed.

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