水溶性钯膦络合物催化1-辛烯的氢羧基化反应

Hydrocarboxylation of 1-Octene in Water-Soluble Palladium Phosphine Complexes Catalyst System

利用水溶性配体TPPTS与Pd(OAc)2在水相中催化1-辛烯的氢羧基化反应,能实现有机相产物与水相催化剂的清洁分离和催化剂的循环利用.分别考察了钯浓度、表面活性剂(CTAB)、酸助剂、反应时间、CO压力以及温度对该反应的影响.在H2O=16 mL,c(Pd)=2.0 mmol/L,c(TPPTS)/c(Pd)=25,c(p-TsOH)=33.8mmol/L,c(CTAB)=79.4 mmol/L,反应时间5.5 h,CO压力为4 MPa,反应温度150℃时,烯烃转化率可达到90.8%,生成壬酸的选择性为76.8%,正异构壬酸的摩尔比为3.96,催化剂循环3次都保持较高的催化活性.最后,通过对钯膦络合物的31P NMR分析,推测出反应过程中可能的反应机理.

Hydroearboxylation of 1-octene with carbon monoxide has been carried out using a catalytic aqueous phase consisting of Pd（OAc） 2, TPPTS I P（ C6H4-m-SO3 Na）31, surfactant and acid. The organic products and the catalyst aqueous phase could be easily separated by extraction. The effects of concentrations of palladium, CTAB （eetyltrimethylammonium bromide） , acid promoter, as well as the reaction temperature and the CO pressure on the conversion of olefin were investigated. Under the conditions of H20 16 mL, c （Pd） = 2.0 retool/L, c （TPFFS）/c （Pd（OAe）2 =25, c（p-TsOH） （p-toluenesulfonie acid） = 33.8 retool/L, c（CTAB） = 79.4 retool/L, reaction time 5.5 h, CO pressure 4 MPa and reaction temperature 150℃ , the conversion of 1-octene reached 90.8% and the selectivity towards nonanoic acid was found to be 76.8% and n/i （molar ratio） 3.96. The catalyst system was reused 3 times without obvious loss of activity. 31p NMR was also used to invesffgate the active species arisen from the coordination of Pd （OAc） 2 with TPFFS under reaction conditions.