双烷基α-烯烃的制备及与溴化氢的反应.pdf

石油学报(石油加工
2010年2月
ACTA PETROLEI SINICA (PETROLEUM PROCESSING SECTION)
第26卷第1期
文章编号:1001-8719(2010)01-0110-05
双烷基α-烯烃的制备及与溴化氢的反应
徐志成,周朝辉,斬志强,赵濉,俞稼鏞
(中国科学院理化技术研究所,北京100190)
摘要:以短链α烯烃为原料备了高纯度的、结构明确的具有双烷基结构的α烯烃,并研究双烷基￠烯烃与HBr
加成制备1-溴代烷烃的反。考察了反应温度、反应时间、溶剂类型和过氧化物对烯烃的转化率和1-溴代烷烃
选择性的影响。结果表明,在-6~75℃范围,温度对@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
关键词:α-烯烃;HIBr;加成反应;溴代烷烃
中图分类号:062;0621.3文献标识码:
SYNTHESES OF DI-SUBSTITUTED A-OLEFIN AND ITS REACTION WITH
HYDROGEN BROMIDE
XU Zhicheng, ZIOU Zhaohui, JIN Zhiqiang, ZHAO Sui, YU Jiayong
Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190, China)
Abstract: A di-substituted a-olefin with high purity and definitive structure was prepared by short
hain a-olefin as starting material, and the preparation of 1-bromo-hydrocarbon through the reaction
of di-substituted a-olefin with gaseous hydrogen bromide was carried out. The effects of reaction
variables, such as solution type, reaction temperature and initiator, upon conversion of a-olefin and
the selectivity of l-bromo-hydrocarbon were investigated. The results indicated that at reaction
temperature in the range of-675c, the conversion of a-olefin was not affected by th
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
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 a-olefin with gaseous hydrogen bromide.
Key words: a-olefin; hydrogen bromide; addition reaction; alkyl bromide
-溴代烷烃是一种非常重要的有机化合物中间1-溴代烷烃的制备主要采用伯醇与氢溴酸反应的工
体,它可以用来制备表面活性剂、染料、油品添加艺,而伯醇通常多来源于烯烃,成本相对较高。若
剂、医药品、脂肪伯醇和伯胺等。目前,国内外能直接由烯烃与HBr反应制备1-溴代烷烃,则既可
收稿日期:2008-11-21
基金项目:国家基础研究重大项目前期专项研究基金项目(20082X05011)资助
通讯联系人:徐志成,Tel:01082543589; E-mail: zhchxu(@ mail. ipc,ac,cn