在RhCl(CO)(TPPTS)_2-TPPTS[P(m-C_6H_4S0_3Na)_3]/TPPDS[C_6HsP(m-C_6H_4 S0_3Na)_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,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-癸烯氧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.阳离子表而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.
The hydroaminomethylation of 1-decene in the RhCl(CO)(TPPTS)_2-TPPTS[P(m-C_6H_4SO_3Na_3)]/TPPDS[C_6HsP(m-C_6H_4SO_3Na)_2]-CTAB aqueous/organic biphasic system was studied under different conditions of molar ratios of TPPTS to TPPDS,reaction pressures,and concentrations and structuers 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 double-chain cationic suffactants instead of single-chain cationic surfaetants.The cationic surfactant that could form compact aggregate favored the formation of linear amine.
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