Development of New Carbonylation Method by Carbon Monoxide and the Synthesis of Thiocarbonates

证实了硒对二烷基二硫化物与一氧化碳反应具有独特的催化作用。二丁基二硫与一氧化碳在二丁基二硫代甲酸二丁酯的催化下与一氧化碳在二丁基二硫代铜的存在下进行羰化反应生成相应的二烷基二硫代碳酸酯，在80℃的条件下，二丁基二硫代硫醚与一氧化碳反应6h，产率为92%。叔胺作为碱对二硫代碳酸酯的产率有影响。二烷基二硫化物如二丙基、二己基和十二烷基二硫化物在硒催化剂存在下的羰基化反应也进展顺利，以较高的产率得到相应的二烷基二硫代碳酸酯。对于含二次烷基链的二硫化物的反应，基于反应的二硫化物的产率较高，但二硫化物的转化率低于伯二硫化物。在叔二烷基二硫化物的情况下，未确认形成二烷基二硫代碳酸酯，并回收了二硫化物。相反，在二苯二硫醚的情况下，根本没有得到碳化产物，并且以中等产率生成了硫醇。

It was confirmed a unique catalytic ability of selenium on the reaction of dialkyl disulfides with carbon monoxide. The carbonylation of dialkyl disulfide with carbon monoxide was promoted by the selenium catalyst in the presence of DBU to give the corresponding dialkyl dithiocarbonates.When dibutyl disulfide was allowed to react with carbon monoxide in the presence of selenium catalyst and DBU as a base at 80℃ for 6h, dibutyl dithiocarbonate, which was the carbonylated product of disulfide, was obtained in 92% yield. The yield of the dithiocarbonate was influenced by the tertiary amine used as a base. The carbonylation of dialkyl disulfides such as dipropyl, dihexyl, and didecyl disulfide also proceeded smoothly in the presence of selenium catalyst to give the corresponding dialkyl dithiocarbonates in good yields. For the reaction of disulfide bearing secondary alkyl chain, the yield of the product based on reacted disulfide was high ; however, the conversion of disulfide was lower that that of primary one. In the case of tertiary dialkyl disulfide, the formation of dialkyl dithiocarbonate was not confirmed and disulfide was recovered. On the contrast, in the case of diphenyl disulfide, the carbonylated product was not obtained at all and thiol was formed in moderate yield.