Thiol oxidation by 1,2,3-oxadiazolinium ions, presumed carcinogens.
Thiol oxidation by 1,2,3-oxadiazolinium ions, presumed carcinogens.
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硫醇被 1,2,3-恶二唑啉鎓离子氧化，被认为是致癌物质。
DOI：
10.1021/tx00048a001
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发表时间：
1995
影响因子：
4.1
通讯作者：
Srinivasan,A
中科院分区：
文献类型：
--
作者：
Loeppky,RN;Srinivasan,A
3-Alkyl-1, 2, 3-oxadiazolinium ions 1 have been proposed as reactive intermediates in the activation of (2-hydroxyethyl) nitrosamines. The reaction of 3-methyl-l, 2, 3-oxadiazolinium tosylate (la), 2-ethyl-l-methoxy-2-phenyldiazenium tetrafluoroborate (3), and 3-phenyl-l, 2, 3-oxadiazolinium triflate (lb) with thiols was investigated to determine the behavior of these compounds toward typical “cellular nucleophiles”. Each of these substances oxidizes ben-zenethiol to diphenyl disulfide. The reaction in aqueous buffer at pH 7.4 is rapid. Reaction of lb with benzenethiol gives, in addition to the disulfide, benzene, biphenyl, azobenzene, diphenyl sulfide, aniline, and glycolaldehyde. Similar products are obtained from 3. Phenyldiazene is postulated as an intermediate in this process, and its generation from phenyldiazoformate in the presence of benzenethiolgives similar products. Diazenes are presumed to arise by proton abstraction from the CH adjacent to N. The kinetics of reaction of la with N-acetylcysteine to give the corresponding disulfide show first order dependence on each reactant and base catalysis. The data from these model chemical experiments suggest that 1, 2, 3-oxadiazolinium ions could react with abundant thiols in cells to lead to either their detoxification or radical processes emanating from diazenes. The occurrence of thiol-oxadiazolinium ion redox transformations could modulate the alkylation chemistry of these substances as well.
