双烷基α-烯烃的制备及与溴化氢的反应

SYNTHESES OF DI-SUBSTITUTED α-OLEFIN AND ITS REACTION WITH HYDROGEN BROMIDE

以短链α-烯烃为原料制备了高纯度的、结构明确的具有双烷基结构的α-烯烃，并研究双烷基α-烯烃与HBr加成制备1-溴代烷烃的反应。考察了反应温度、反应时间、溶剂类型和过氧化物对α-烯烃的转化率和1-溴代烷烃选择性的影响。结果表明，在-6～75℃范围，温度α-烯烃的转化率没有明显的影响，但1-溴代烷烃的选择性随温度的降低而升高；溶剂对1-溴代烷烃的选择性也产生显著的影响，非极性溶剂有利于1-溴代烷烃选择性的提高；双烷基α-烯烃与HBr进行加成反应过程中发生了重排反应，生成了既不同于马式加成也不同于反马式加成产物的新化合物。

A di-substituted α-olefin with high purity and definitive structure was prepared by short chain α-olefin as starting material, and the preparation of 1-bromo-hydrocarbon through the reaction of di-substituted α-olefin with gaseous hydrogen bromide was carried out. The effects of reaction variables, such as solution type, reaction temperature and initiator, upon conversion of α-olefin and the selectivity of 1-bromo-hydrocarbon were investigated. The results indicated that at reaction temperature in the range of -6 75℃, the conversion of α-olefin was not affected by the temperature while the selectivity of 1-bromo-hydrocarbon was markedly affected, which increased with the temperature decreasing. The solution type also had significant effect on the selectivity of 1- bromo-hydrocarbon, the no polar solution was favorable for the selectivity. It was found that a new compound, neither the product of Markovnikon addition nor the product of anti-Markovnikov addition, was produced by rearrangement reaction occurred during the addition reaction of di-substituted α-olefin with gaseous hydrogen bromide.