A GENERAL STRATEGY FOR ELABORATION OF THE DITHIOCARBONYL FUNCTIONALITY, -(C=O)SS- - APPLICATION TO THE SYNTHESIS OF BIS(CHLOROCARBONYL)DISULFANE AND RELATED DERIVATIVES OF THIOCARBONIC ACIDS
A GENERAL STRATEGY FOR ELABORATION OF THE DITHIOCARBONYL FUNCTIONALITY, -(C=O)SS- - APPLICATION TO THE SYNTHESIS OF BIS(CHLOROCARBONYL)DISULFANE AND RELATED DERIVATIVES OF THIOCARBONIC ACIDS
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DOI：
10.1021/jo00172a056
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发表时间：
1983-01-01
影响因子：
3.6
通讯作者：
HALSRUD, DA
中科院分区：
文献类型：
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作者：
BARANY, G;SCHROLL, AL;HALSRUD, DA
各种亚硫酰氯与各种烷氧基硫代羰基化合物反应生成加合物，然后这些加合物(自发地、热分解或在Lewis酸催化剂存在的情况下)失去烷基氯，以很好到很好的产率提供各种二硫代甲酰化合物。优化了双(氯甲酰基)二硫代烷(1)、(三氯甲基二硫代)甲酰氯(2)、(烷氧基)二硫代甲酰氯(3和4)和((烷基硫代)羰基)二硫代甲酰氯(5和6)的制备方法，得到了较为稳定的产物，如R0CC12SS(C=0)C1(10)和R0CC12SS(C=0)0R‘(54)。所有新化合物均经分析数据、13CNMR、ER、UV和MS以及与醇或TV-甲基苯胺的高产率衍生化进行了表征。与IV-甲基苯胺的反应也适用于含有酰氯和/或亚磺酰氯官能团的化合物混合物的快速、方便和精确的分析规模分析。讨论了二硫代甲酰基合成的动力学、机理和立体化学。作为开发在温和还原条件下可移除的氨基保护基团的计划的一部分，1，2我们寻找了一种方便地进入各种二硫代甲基氯化物的途径。这些化合物包括二(氯甲酰基)二硫代烷(L)，1，3，可与伯胺反应连接二硫代琥珀酰基官能团，以及(三氯甲基)二硫代甲酰氯(2)，1 23，伯胺和仲胺的氨甲酰二硫代衍生物的合成前体，以及新的化合物3至6。
A variety of sulfenyl chlorides have been reacted with a variety of alkoxythiocarbonyl compounds to give adducts which then lose (spontaneously, or upon thermolysis, or in the presence of a Lewis acid catalyst) the alkyl chloride to provide an assortment of dithiocarbonyl compounds in good toexcellent yields. The preparations of bis-(chlorocarbonyl) disulfane (1),((trichloromethyl) dithio) carbonyl chloride (2),((alkoxycarbonyl) dithio) carbonyl chlorides (3 and 4), and (((alkylthio) carbonyl) dithio) carbonyl chlorides (5 and 6) by this methodology were optimized; some of the (alkoxydichloromethyl) disulfanyl adducts, eg, R0CC12SS (C= 0) C1 (10) and R0CC12SS (C= 0) 0R'(54), were reasonably stable and could be isolated. All new compounds were characterized by analytical data, and 13C NMR, ER, UV, and mass spectrometry, and high-yield derivatizations with alcohols or TV-methylaniline. The reaction with IV-methylaniline was also adapted to a rapid, convenient, andprecise analytical-scale assay of mixtures of compounds containing acid chloride and/or sulfenyl chloride functionalities. The kinetics, mechanism, and stereochemistry of the dithiocarbonyl synthesis are discussed.As part of a program to develop amino protecting groups removable under mild reductive conditions, 1, 2 we sought a convenient entry to a variety of dithiocarbonyl chlorides. These include bis (chlorocarbonyl) disulfane (l), 1, 3 which might be expected1 to react with primary amines to attach a dithiasuccinoyl function, and ((trichloromethyl) di-thio) carbonyl chloride (2), 1 23 which is a synthetic precursor of carbamoyl disulfide derivatives of primary and sec-ondary amines, as well as the novel compounds 3 to 6.