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-芳基硫代羧酸酯的方法已引起合成化学和工业化学的极大关注。目前，虽然已经显示了许多S-烷基-和S-芳基硫代羰基酯的合成方法，但是这些方法由多步程序组成：（i）通过硫与一氧化碳的反应制备SCO，（ii）醇或硫醇的亲核加成和（iii）随后的烷基化反应，我们找到了一种一锅法合成S-烷基-和S-在催化量的硒存在下，通过醇与二硫化物和一氧化碳的反应制备芳基硫代羰基化合物。例如，当乙醇在催化量的硒存在下在一氧化碳加压的气氛下用二苯基二硫化物处理时，以几乎定量的产率形成S-苯基-O-乙基硫代甲酸酯。类似地，二芳基二硫化物取代的各种官能团与乙醇在一氧化碳压力下反应，以中等至良好的产率得到相应的S-芳基-O-乙基硫代甲酸酯。在该反应中，脂肪醇也可以用作醇，以中等产率形成相应的硫羟酸酯。另一方面，在二烷基二硫化物的情况下，得到S-烷基- O-烷基硫代碳酸酯和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.