钯-膦-酸催化剂体系催化烯烃的氢羧基化反应

Catalytic Hydrocarboxylation of Olefins Using Palladium phosphine acid Catalyst System

烯烃的氢羧基化反应是制备有机羧酸的重要途径之一．我们用Ｐｄ（ＯＡｃ）２、三苯基膦（ＰＰｈ３）和对甲基苯磺酸（ｐ－Ｔｓ）催化剂体系，研究了在相转移试剂的存在下，烯烃的氢羧基化反应．对影响反应的各种因素如反应温度、压力、相转移试剂的加入量、不同相转移试剂等作了考察．实验结果表明，较适宜的条件为温度１３０℃、压力４．０ＭＰａ、反应时间为２４ｈ．在此两相反应中，相转移试剂是不可少的，较理想的相转移试剂是十二烷基苯磺酸钠；而当使用β－环糊精作为反应相的转移试剂时，得到的产物基本上是正构物．并将此催化体系用于不同结构烯烃的氢羧基化反应，发现有如下的活性顺序：苯乙烯＞庚烯＞环己烯．

Alkenes were converted to the corresponding carboxylic acids in the presence of Pd(OAc) 2 PPh 3 p Ts catalyst system and a surface active agent. The effects of reaction parameters, such as temperature, pressure, different phase transfer agents and the amount of phase transfer agent, on the hydrocarboxylation of 1 heptene have been investigated. It was found that good results were obtained at T =130 ℃ and p (CO)=4. 0 MPa for 24 h. The phase transfer agent is necessary for this biphasic reaction, and the best transfer agent is sodium salt of dodecylbenzene sulfonic acid. In addition, almost linear product was obtained when the β cyclodextrin is used as inverse phase transfer agent. It was also found that the catalytic activity is strongly influenced by the structure of the alkene in the following order: styrene>heptene>cyclohexene.