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

开发一种简便有效的合成S-烷基和S-芳基硫代碳酸酯的方法已引起合成化学界和工业化学界的广泛关注。到目前为止，虽然已经提出了许多合成S-烷基和S-芳基硫代碳酸酯的方法，但这些方法包括以下几个步骤：(I)硫与一氧化碳反应制备SCO；(Ii)醇或硫醇的亲核加成；(Iii)随后的烷基化。现在，我们找到了醇与二硫化物和一氧化碳在催化量硒存在下一锅合成S-烷基和S-芳基硫代碳酸酯的方法。例如，当乙醇在一氧化碳加压的气氛中与二苯二硫醚在催化量的硒存在下处理时，S-苯基-O-乙基碳硫酸酯几乎定量地生成。同样，二芳基二硫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-乙基硫代碳酸酯，产率中等到很好。在该反应中，脂肪醇也可以作为醇使用，生成相应的硫醇酯，产率适中。另一方面，对于二烷基二硫化物，得到了S-烷基-O-烷基硫代碳酸酯与S、S-二烷基硫代碳酸酯的混合物。

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.