2005 Fiscal Year Final Research Report Summary
Development of New Carbonylation Method by Carbon Monoxide and the Synthesis of Thiocarbonates
| Project/Area Number |
15550096
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Synthetic chemistry
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| Research Institution | Kansai University |
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Principal Investigator |
NISHIYAMA Yutaka Kansai University, Faculty of Engineering, Assistant Professor, 工学部, 助教授 (30180665)
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| Project Period (FY) |
2003 – 2005
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| Keywords | selenium / carbon monoxide / carbonylation / organosulfur compound |
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| Research Abstract |
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.
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