| 何珍红,侯震山,王永垒,刘远凤,刘红来,吾满江·艾力.水溶性钯膦络合物催化1-辛烯的氢羧基化反应[J].分子催化,2011,(5):406-414 |
| 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 |
| 投稿时间：2011-06-25 修订日期：2011-08-19 |
| DOI： |
| 中文关键词: 1-辛烯，氢羧基化反应，钯膦络合物，两相催化体系，31P NMR |
| 英文关键词:1-octene, hydrocarboxylation, Pd-P complex, biphasic catalysis system, 31P NMR |
| 基金项目:中国科学院百人计划项目 |
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| 摘要点击次数: 1994 |
| 全文下载次数: 2475 |
| 中文摘要: |
| 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、酸助剂、表面活性剂 (CTAB)、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) = 33.8 mmol/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。 |
| 英文摘要: |
| Hydrocarboxylation of 1-octene with carbon monoxide has been carried out using a catalytic aqueous phase consisting of Pd(OAc)2, TPPTS, surfactant and acid. The organic products and the catalytic aqueous phase could be easily separated by extraction. The effects of concentrations of palladium, CTAB (cetyltrimethylammonium bromide), acid promoter, as well as the reaction temperature and the CO pressure on the conversion of olefin were investigated. Under the conditions of H2O 16 mL, c(Pd)=2.0 mmol/L, c(TPPTS)/c(Pd(OAc)2)=25, c(p-TsOH) (p-toluenesulfonic acid)= 33.8 mmol/L，c(CTAB) = 79.4 mmol/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 investigate the active species arisen from the coordination of Pd(OAc)2 with TPPTS [P(C6H4-m-SO3Na)3] under reaction conditions. |
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