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早在1870年马尔可夫尼可夫〔1〕就提出了烯烃与卤化氢加成时的定位规则-氢原子加成到烯烃的连接氢原子较多的不饱和碳原子上,卤原子加到连接氢原子较少的不饱和碳原子上.随着烯烃加成机理研究的深入和有机化学电子理论的发展,人们对这一加成定位规则的认识也逐步深入. 1933年Kharasch等〔2〕发现,烯烃与HBr加成时,常常不遵守马氏规则.他指出,马氏规则只适用于烯烃亲电加成反应.在过氧
As early as 1870 Markovnikov [1] proposed the rules for the addition of alkenes to hydrogen halides - the addition of hydrogen atoms to the more unsaturated carbon atoms of the alkene to which hydrogen is attached, the addition of halogen atoms to Linking less hydrogen atoms on the unsaturated carbon atoms with the deepening of the research on the mechanism of olefin addition and the development of organic electronic chemistry theory, people’s understanding of this addition positioning rules are gradually deepening .1933 Kharasch et al [2] It was found that the addition of olefins to HBr often failed to comply with the Markov rule, and he pointed out that the Markov rule applies only to the olefinic electrophilic addition reaction.