由邻糠基二硫代碳酸酯生成糠基硫醚的机理：芳香族[3,3] - 西格玛重排的密度泛函理论研究
Formation mechanism of furfuryl sulfides from o-furfuryl dithiocarbonates: density functional theory study for aromatic [3,3]-sigmatropic rearrangement.
作者信息
Eto Masashi, Yamaguchi Koki, Yoshitake Yasuyuki, Harano Kazunobu
机构信息
Liberal Arts Education Center, Aso Campus, Tokai University, 5435 Kawayo, Minami-Aso, Kumamoto, Japan.
出版信息
Chem Pharm Bull (Tokyo). 2011;59(6):681-5. doi: 10.1248/cpb.59.681.
Density functional theory (DFT) calculations at the B3LYP/6-31G(d) and B3LYP/6-31G+(d) levels demonstrated that O-furfuryl S-alkyl dithiocarbonate (1) undergoes aromatic [3,3]-sigmatropic rearrangement to the energetically unfavorable S-(2-methylene-2,3-dihydrofuran-3-yl) S-alkyl dithiocarbonate (2'), which then rearranges to furfuryl alkyl sulfide (3) with COS extrusion to regain the aromaticity lost in the first step.
在B3LYP/6 - 31G(d)和B3LYP/6 - 31G+(d)水平上进行的密度泛函理论(DFT)计算表明，糠基O - 烷基二硫代碳酸酯(1)发生芳香族[3,3] - 西格玛重排，生成能量上不利的S - (2 - 亚甲基 - 2,3 - 二氢呋喃 - 3 - 基)S - 烷基二硫代碳酸酯(2')，然后该产物通过挤出COS重排为糠基烷基硫醚(3)，以恢复第一步中失去的芳香性。
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