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Journal of the Korean Chemical Society (JKCS)

ISSN 1017-2548(Print)
ISSN 2234-8530(Online)
Volume 16, Number 6
JKCSEZ 16(6)
December 20, 1972 

Nucleophilic Substitution at a Carbonyl Carbon Atom. Part Ⅱ. CNDO / 2 Studies on Conformation and Reactivity of the Thio-Analogues of the Thio-Analogues of Methyl Chloroformate

카보닐 탄소원자 친핵 치환반응. 제2보. Methyl chloroformate의 티오 치환제들의 구조와 반응성에 관한 CNDO / 2 계산
Ikchoon Lee

메틸 클로로 티올, 메틸클로로 티오노 및 메틸 클로로 디티오 훠메이트에 대하여 CNDO/2 계산을 실시하였다. 결과로 이들 화합물은 trans형이 안정한 것임을 밝혔다. 또 유황 원자는 산소원자에 비하여 그 고립쌍 전자들을 π-결합 형성에 사용하려는 경향이 적고 티올 훠메이트의 경우는 메틸기의 hyperconjugation에 의하여 안정화됨을 알았다. 가용매 반응성의 순서는 양이온의 안정도와 일치하며 이것은 알려진 Sn1형 반응 메카니즘과 부합된다.

CNDO/2 calculations have been carried out on methyl chloro-thiol-, methyl chloro-thiono-, and methyl chloro-dithio-formates. Results show that the trans is the stable configuration for these compounds. It was found that sulfur atom has much less tendency to use its lone pair electrons for π bond formation compared with oxygen, and that thiolformates are stabilized by hyperconjugation of methyl hydrogens. The order of solvolytic reactivity was found to follow the order of cation stability, which is consistent with the SN1 mechanism proposed for these compounds.

334 - 340
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