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

一氧化碳羰基化新方法的开发及硫代碳酸酯的合成

基本信息

批准号：
15550096
负责人：
NISHIYAMA Yutaka
金额：
$ 2.37万
依托单位：
Kansai University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2003
资助国家：
日本
起止时间：
2003 至 2005
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-15550096/
关键词：
selenium carbon monoxide carbonylation organosulfur compound 触媒チオカーボネート

项目摘要

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.

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。在DBU存在下，硒催化剂促进了二烷基二硫醚与一氧化碳的羰基化反应，得到了相应的二烷基二硫代碳酸盐。二硫化二丁酯在硒催化剂存在下，以DBU为碱，与一氧化碳在80℃下反应6h，得到二硫化二丁酯羰基化产物二硫代碳酸二丁酯，产率为92%。叔胺作为碱对二硫代碳酸盐的收率有影响。在硒催化剂的作用下，二烷基二硫化物如二丙基、二己基和二癸基二硫化物的羰基化反应也顺利进行，得到相应的二烷基二硫代碳酸盐，收率较高。在含二硫仲烷基链反应中，以二硫为原料的反应产物收率高；二硫化物的转化率低于原硫化物的转化率。在叔二烷基二硫化的情况下，二烷基二硫碳酸盐的形成未被证实，二硫被回收。而二苯基二硫化物则完全没有羰基化产物，并以中等产率生成硫醇。