CONVERSION OF PHENOLS TO THIOPHENOLS VIA DIALKYLTHIOCARBAMATES
CONVERSION OF PHENOLS TO THIOPHENOLS VIA DIALKYLTHIOCARBAMATES
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DOI：
10.1021/jo01350a023
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发表时间：
1966-01-01
影响因子：
3.6
通讯作者：
KARNES, HA
中科院分区：
文献类型：
--
作者：
NEWMAN, MS;KARNES, HA
许多酚类和羟基杂环化合物已通过以下途径转化为相应的硫醇化合物：苯酚转化为O-芳基二烷基硫代氨基甲酸酯，S-芳基二烷基硫代氨基甲酸酯，苯硫酚。描述了高产率地完成每个步骤的方法。由于所形成的硫醇化合物易于通过与阮内镍一起加热而脱硫，因此用氢取代芳族羟基的有用方法是现成的。在本文报道的工作之前，这种转化已经通过将二-O-芳基硫代碳酸酯（I）热解成O-芳基S-芳基硫代碳酸酯（II）来实现。2进一步的研究表明，在此范围内，总转化率为纯物质的20-28%。[3]该路线的一个明显限制是，就苯酚转化为相应苯硫酚而言，可能的最大产率为50%。
A number of phenols and hydroxyheterocyclic compounds have been converted to the corresponding thiol compounds by the route, phenol to O-aryl dialkylthiocarbamate to S-aryldialkylthiocarbamate to thiophenol. Methods for accomplishing each stepin high yield are described. Since the thiol compounds formed are readily desulfurized by heating with Raney nickel, a useful way of replacing aromatic hydroxyl groups by hydrogen is at hand.The conversion of a phenol to the corresponding thiophenol represents a transformation for which there has been developed no good general method to date. Prior to the work herein reported this conversion had been effected by pyrolysis of di-O-aryl thiocarbonates (I), to O-aryl S-aryl thiocarbonates (II). 2 Further work showed that over-allconversion in theregion of 20-28% of pure materials were obtained. 3 An obvious limitation of this route is that the maximum yield possible is 50% with respect to conversion of a phenol to the corresponding thiophenol.