Development of a new Synthetic Method of Thiol Esters by Using Carbon Monoxide-Disulfide System

开发一种方便、高效的合成s -烷基和s -芳基碳硫酸盐的方法已引起合成界和工业化学界的广泛关注。到目前为止，虽然已经有许多合成s -烷基和s -芳基碳硫酸盐的方法，但这些方法都是由多个步骤组成的：(i)通过硫与一氧化碳反应制备SCO， （ii）亲核加成醇或硫醇，以及（iii）随后的烷基化。现在，我们发现了一种一锅合成s -烷基和s -芳基碳硫酸盐的方法，该方法是在催化量的硒存在下，用醇与二硫化物和一氧化碳反应。例如，当用二苯基二硫化物处理乙醇时，在一氧化碳加压的气氛下，有催化量的硒存在，s -苯基- o -乙基碳硫酸盐几乎定量生成。同样，二硫代二芳基取代的各种官能团在一氧化碳的压力下与乙醇反应，得到相应的s -芳基- o -乙基碳硫酸盐，收率中等至较高。在此反应中，脂肪族醇也可用作醇，以中等产率生成相应的硫醇酯。另一方面，在二烷基二硫化物的情况下，得到了S-烷基- O-烷基碳硫酸盐和S， S-二烷基碳硫酸盐的混合物。

The development of a convenient and efficient method for the synthesis of S-alkyl and S-arylcarbonothiolates has attracted considerable attention in synthetic and industrial chemistry. Hitherto, although many synthetic methods of S-alkyl- and S-arylcarbonothiolates have been shown, these methods consisted on a multi-step procedures: (i) the preparation of SCO by the reaction of sulfur with carbon monoxide, (ii) the nucleophilic addition of alcohol or thiol and (iii) subsequent alkylation.Now we found a one-pot synthetic method of S-alkyl- and S-arylcarbonothiolates by the reaition of alcohol with disulfide and carbon monoxide in the presence of a catalytic amount of selenium. For example, when ethanol was treated with diphenyl disulfide in the presence of a catalytic amount of selenium under an atmosphere pressurized of carbon monoxide, S-phenyl-O-ethylcarboncpthiolate was formed in almost quantitative yield. Similarly, diaryl disulfide substituted various functional groups were reacted with ethanol under the pressure of carbon monoxide to give the corresponding S-aryl-O-ethylcarbonothiolates in moderate to good yields. In this reaction, aliphatic alcohols can also be used as an alcohol, the corresponding thiol esters were formed in moderate yields. On the other hand, in the case of dialkyl disulfide, the mixture of S- alkyl- O- alkylcarbonothiolates and S, S- dialkylcarbonothiolates were obtained.