Study of Fragmentation Reactions of Highly Sterically Hindered Organosilicon Compounds with Alcoholic Sodium Alkoxides
作者:Kazem D. Safa、Mirzaagha Babazadeh、Aiub Haghnia、Nahid Soleimani
DOI:10.1080/104265090968532
日期:2006.1.1
The compounds (Me3Si)3CSiXX′X″ [X = Me, X′ = (C6H4Me-p), X″ = I; X = Et, X′ = X″ = Cl; X = Bu, X′ = X″ = Cl)] reacted with boiling RONa/ROH [R = Pr, iso-Pr, Bu, Et, Benzyl, iso-Amyl] to give the fragmentation products of the type (Me3Si)2CHSiXX′(OR) and Me3SiCH2SiXX′(OR) [X = Me, X′ = (C6H4Me-p] or (Me3Si)2CHSiX(OR)2 [X = Et or Bu]. Study of the products showed that alkoxides as nucleophile cannot
化合物 (Me3Si)3CSiXX'X" [X = Me, X' = (C6H4Me-p), X" = I; X = Et,X′ = X″ = Cl;X = Bu, X' = X″ = Cl)] 与沸腾的 RONa/ROH [R = Pr, iso-Pr, Bu, Et, Benzyl, iso-Amyl] 反应得到 (Me3Si)2CHSiXX 类型的裂解产物'(OR) 和 Me3SiCH2SiXX'(OR) [X = Me, X' = (C6H4Me-p] 或 (Me3Si)2CHSiX(OR)2 [X = Et 或 Bu]。产物的研究表明,醇盐作为亲核试剂不能由于空间位阻,攻击带有 (Me3Si)3C- 基团的硅中心。这表明反应通过消除进行,类似于烷基卤化物的 E2 消除,涉及 RO− 在 Me3Si 基团上的同步攻击, X- 的释放,以及 (Me3Si)2C=SiXX' 的形成。