VAPOR PHASE REARRANGEMENT OF THIONCARBONATES AND THIONCARBAMATES
VAPOR PHASE REARRANGEMENT OF THIONCARBONATES AND THIONCARBAMATES
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DOI：
10.1021/jo01340a015
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发表时间：
1966-01-01
影响因子：
3.6
通讯作者：
EVANS, ER
中科院分区：
文献类型：
--
作者：
KWART, H;EVANS, ER
在气相热解中对芳基碳酸亚硫酯进行了Schonberg重排，收率得到了显著提高。这些结果与Powers和Tarbell提出的环四元过渡态相一致，并扩展到硫氨基甲酸酯的气相重排，作为制备某些难以获得的取代芳基硫醇的有效和简单的方法。涉及这些气相重排步骤的程序被认为是某些取代酚的脱氧最普遍有效的途径，否则这些取代酚不易被还原或氢解（用兰尼镍）。首先由Schonberg和Vargha2描述的二芳基碳酸亚硫酯的重排，后来在很大程度上通过Tarbell及其同事的努力被证明，在取代硫酚的制备中具有重要的合成意义。这种重排显然适用于对称和不对称二芳基碳酸亚硫酯。最初的
The Schonberg rearrangement of aryl thioncarbonates has been carried out in a vapor phase pyrolysis with considerable improvement in yield. These results have been reconciled with the cyclic four-membered transi-tion state proposed by Powers and Tarbell and extended to the vapor phase rearrangementof thioncarbamates as an efficient and simple method of preparing certain difficultly available substituted aryl thiols. A pro-cedure involving the steps of these vapor phase rearrangements is conceived as the most generally effective route for deoxygenation of certain substituted phenols which are otherwise not readily subject to reduction or hydrogenolysis (with Raney nickel).The rearrangement ofdiaryl thioncarbonates, first described by Schonberg and Vargha2 has later been shown, largely through the efforts of Tarbell and co-workers, 3· 4 to be of synthetic importance in the prepa-ration of substituted thiophenols. The rearrangement is apparently applicable to both symmetricaland un-symmetrical diaryl thioncarbonates. The original