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Journal of the Korean Chemical Society (JKCS)

ISSN 1017-2548(Print)
ISSN 2234-8530(Online)
Volume 26, Number 2
JKCSEZ 26(2)
April 20, 1982 

Mechanistic Studies on the Reaction of Thioxanthylium Ion with Dimedone

티오크잔틸이움 이온과 디메돈의 반응메카니즘에 관한 연구
Kwang Hyun Ahn, Kyongtae Kim

안광현, 김경태
티안트렌양이온 자유라디칼의 아세토니트릴 용액에 의해 티오크잔틴이 산화되어 생성된 티오크잔틸이움 이온에 디메돈을 넣어주면 9-(4,4-dimethylcyclohexane-2,6-dionyl)thioxanthylium 과염소산염(2)이 생성되나 순서를 바꾸어 넣어주면 초기에 9-(4,4-dimethylcyclohexane-2,6-dionyl)thioxanthene (1)이 생성되며 이것은 계속 반응하여 2를 만든다. 화합물 2는 물이 섞인 아세톤에서 쉽게 탈 수소화되어 9-(4,4-dimethylcyclohexane-2,6-dionylidene)thioxanthene (3)이 된다. 그러나 물이 섞인 아세토니트릴용액중에서 관찰된 219, 289, 348 nm의 isobestic point는 3이 2와 평형상태로 존재함을 말한다. 3의 380nm 근처에 있는 흡수띠의 위치와 강도는 용매에 따라 변하는데 이것은 용매-용질 사이의 상호작용으로 설명한다.

Addition of dimedone to thioxanthylium ion generated from the oxidation of thioxanthene by thianthrene cation radical perchlorate in acetonitrile gave 9-(4,4-dimethylcyclohexane-2,6-dionyl)thioxanthylium perchlorate (2), whereas from the reverse addition between two reactants was obtained initially 9-(4,4-dimethylcyclohexane-2,6-dionyl)thioxanthene (1), which then underwent further reaction to give 2. The compound 2 was readily deprotonated in aq acetone to give 9-(4,4-dimethylcyclohexane-2,6-dionylidene)thioxanthene (3). However, 3 turned out to be in equilibrium with 2 in which three isosbestic points at 219, 289, and 348 nm were recorded in aq acetonitrile. The intensity and the position of the maximum absorption of 3 near 380 nm vary depending on the solvents which has been explained in terms of the solvent-solute interactions.

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