催化学报

催化学报 ›› 2009, Vol. 30 ›› Issue (12): 1192-1196.

• 研究论文 • 上一篇    下一篇

水/有机两相体系 1-癸烯氢氨甲基化反应中 TPPTS 和TPPDS 的协同效应

毛卉, 付海燕, 陈华, 李瑞祥, 李贤均   

  1. 四川大学化学学院有机金属络合催化研究所绿色化学与技术教育部重点实验室, 四川成都 610064
  • 收稿日期:2009-12-25 出版日期:2009-12-25 发布日期:2013-09-29

Synergistic Effect of TPPTS and TPPDS on the Regioselectivity for 1-Decene Hydroaminomethylation in a Two-Phase Catalytic System

MAO Hui, FU Haiyan*, CHEN Hua*, LI Ruixiang, LI Xianjun   

  1. Key Laboratory of Green Chemistry and Technology of the Ministry of Education, Institute of Homogeneous Catalysis, College of Chemistry, Sichuan University, Chengdu 610064, Sichuan, China
  • Received:2009-12-25 Online:2009-12-25 Published:2013-09-29

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943

被引次数

12

摘要： 在 RhCl(CO)(TPPTS)2-TPPTS[P(m-C6H4SO3Na)3]/TPPDS[C6H5P(m-C6H4 SO3Na)2]-CTAB (十六烷基三甲基溴化铵) 水-有机两相催化体系中, 系统考察了 TPPTS/TPPDS 摩尔比、反应压力、阳离子表面活性剂结构及其浓度对 1-癸烯氢氨甲基化反应区域选择性的影响. 结果表明, TPPDS 的加入对生成胺的区域选择性的影响非常大. 当 TPPTS/TPPDS 摩尔比为 4 时, 直链胺和支链胺之比由不加 TPPDS 时的 8.2 增加到 21.0. 可见, TPPTS 和 TPPDS 存在着明显的协同效应. 阳离子表面活性剂的结构对生成胺的区域选择性影响也很大, 加入双长链阳离子表面活性剂时区域选择性远低于单长链阳离子表面活性剂, 且形成的聚集体越紧密, 越有利于提高产物正/异比.

关键词: 1-癸烯, 氢氨甲基化, 区域选择性, 协同效应, 阳离子表面活性剂

Abstract: The hydroaminomethylation of 1-decene in the RhCl(CO)(TPPTS)2-TPPTS[P(m-C6H4SO3Na)3]/TPPDS[C6H5P(m-C6H4SO3Na)2]- CTAB aqueous/organic biphasic system was studied under different conditions of molar ratios of TPPTS to TPPDS, reaction pressures, and concentrations and structures of cationic surfactants. The synergistic effect of TPPTS and TPPDS on the regioselectivity was observed. The results showed that the ratio of linear/branched amine rose from 8.2 (without TPPDS) to 21.0 ([TPPTS]/[TPPDS] = 4:1). The structure of cationic surfactants exhibited an important influence on the regioselectivity. The ratio of linear/branched amine decreased when using dou-ble-chain cationic surfactants instead of single-chain cationic surfactants. The cationic surfactant that could form compact aggregate favored the formation of linear amine.

Key words: 1-decene, hydroaminomethylation, regioselectivity, synergistic effect, cationic surfactant