摘要
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.
出处
《分子催化》
EI
CAS
CSCD
北大核心
2011年第5期406-414,共9页
Journal of Molecular Catalysis(China)