一些富勒烯C60双加成物稳定性的理论研究

Ｃ6 0 具有 30个等同的可参与化学反应的活泼双键 ,制备并表征富勒烯多加成产物是富勒烯化学中最前沿的课题之一 .Ｈｉｒｓｃｈ等[15 ]通过研究Ｃ6 0 亚甲基加成反应 ,提出了双加成物立体选择性的一般规律 .我们在Ｃ6 0 氧加成方面做了类似的研究工作[6 8].本文选取几类富勒烯环双加成衍生物即富勒烯氧化产物Ｃ6 0 Ｏ2 [6 ]( 1 )、富勒烯含氮衍生物Ｃ6 0 (ＮＨ) 2 [5 ]( 2 )、富勒烯含吡咯环衍生物Ｃ6 0 (ＣＨ2 ＮＨＣＨ2 ) 2 [9]( 3)和富勒醇前体Ｃ6 0 (ＳＯ4) 2 [10 ]( 4)作为模型分子进行理论研究 ,以探寻富勒烯多加成反应的一般性规律 .…     

Unexpected selective monoadduct formation from 2-methyl-3-butyn-2-ol and α,ω-diiodoperfluorobutane

Radical chain addition of α,ω-diiodoperfluorobutane to 2-methyl-3-buten-2-ol and 2-methyl-3-butyn-2-ol has been studied. The Huang sulfinatodehalogenation system, used as initiator, gave satisfactory conversion yields of the starting diiodide when compared to more classical initiators (AIBN, Fe, triethylborane). Addition to the alkenol yields classically the bis-adduct with variable amounts of the monoadduct. On the contrary the alkynol leads exclusively to the monoadduct formation, in high yield. Some considerations are proposed for interpreting this result. The monoadduct selectively obtained constitutes a powerful intermediate for synthesis.