Reactive sulfur species: hydrolysis of hypothiocyanite to give thiocarbamate-S-oxide.
Reactive sulfur species: hydrolysis of hypothiocyanite to give thiocarbamate-S-oxide.
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DOI：
10.1021/ja0770532
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发表时间：
2007-12
影响因子：
15
通讯作者：
P. Nagy;Xiaoguang Wang;K. Lemma;M. Ashby
中科院分区：
文献类型：
--
作者：
P. Nagy;Xiaoguang Wang;K. Lemma;M. Ashby
次硫氰酸盐（OSCN-）在碱性条件下水解生成硫代氨基甲酸盐-S-氧化物（H2 NC（=O）SO-，氨基硫代过氧酸的共轭碱），其机理涉及OH-对OSCN-的限速亲核攻击，然后快速质子化（在pH 11.7时没有H+/OH-的净消耗）。硫代氨基甲酸酯-S-氧化物已通过13 C NMR、15 N NMR、UV光谱和离子色谱法表征。它也是通过硫代氨基甲酸酯（H2 NC（=O）S-）和次氯酸盐（OCl-）反应独立合成的。由OSCN-水解和H2 NC（=O）S-氧化生成的硫代氨基甲酸酯-S-氧化物的性质相同。硫代氨基甲酸盐-S-氧化物在人类过氧化物酶防御机制中的可能相关性仍有待探索。
Hypothiocyanite (OSCN-) hydrolyzes under alkaline conditions to give thiocarbamate-S-oxide (H2NC(=O)SO-, the conjugate base of carbamothioperoxoic acid) via a mechanism that involves rate-limiting nucleophilic attack of OH- on OSCN-, followed by fast protonation (with no net consumption of H+/OH- at pH 11.7). Thiocarbamate-S-oxide has been characterized by 13C NMR, 15N NMR, UV spectroscopy, and ion chromatography. It has also been independently synthesized by the reaction of thiocarbamate (H2NC(=O)S-) and hypochlorite (OCl-). The properties of thiocarbamate-S-oxide that is produced by hydrolysis of OSCN- and by oxidation of H2NC(=O)S- are the same. The possible relevance of thiocarbamate-S-oxide in human peroxidase defense mechanisms remains to be explored.