两相体系中钌膦配合物催化4-苯基-3-丁烯-2-酮加氢反应的研究  

Benzylideneacetone Hydrogenation with WaterSoluble RuTPPTS Complexes in the Biphasic Catalytic System

作　　者：胡家元[1] 陈华[1] 李贤均[1] 田金忠[2] 黄宁表[2] 

机构地区：[1]四川大学化学系 [2]香港城市大学

出　　处：《分子催化》1999年第3期169-175,共7页Journal of Molecular Catalysis(China)

摘　　要：研究了水和有机物组成的两相催化体系中，由ＲｕＣｌ３－ＴＰＰＴＳ（ＴＰＰＴＳ：Ｐ（ｍ－Ｃ６Ｈ４ＳＯ３Ｎａ）３）原位反应生成的催化活性物种对４－苯基－３－丁烯－２－酮（又名苄叉丙酮）的催化加氢反应．考察了钌浓度（１．０×１０－３～６．０×１０－３ｍｏｌ／Ｌ）、氢压（１．０～６．０ＭＰａ）、反应温度（３０～７０℃）、配体浓度（１．２～７．２×１０－２ｍｏｌ／Ｌ）、阳离子表面活性剂（ＣＴＡＢ：十六烷基三甲基溴化铵）及反应时间等对加氢反应活性和选择性的影响，并与以配合物ＲｕＣｌ２（ＴＰＰＴＳ）３为催化剂前体生成的催化活性物种对加氢反应的活性及选择性进行了比较．结果表明，分别由配合物ＲｕＣｌ２（ＴＰＰＴＳ）３及ＲｕＣｌ３－ＴＰＰＴＳ原位反应生成的催化活性物种，都只催化４－苯基－３－丁烯－２－酮的Ｃ＝Ｃ键选择加氢．由配合物ＲｕＣｌ２（ＴＰＰＴＳ）３形成的催化体系的加氢活性及选择性均优于ＲｕＣｌ３－ＴＰＰＴＳ原位反应生成的催化活性物种．阳离子表面活性剂的加入，使加氢反应活性下降。The catalytic performance of two catalyst precursors, RuCl3TPPTS and RuCl2\|(TPPTS)3 (TPPTS: P(mC6H4SO3Na)3) for selective hydrogenation of carboncarbon double bond in benzylideneacetone were studied in biphasic catalytic system(aqueous/organic phase). The results show that the activity and selectivity of the catalytic species derived from ruthenium complex RuCl2 (TPPTS)3 is higher than that formed in situ from RuCl3 and TPPTS. The addition of surfactant CTAB (cetyltrimethylammonium bromide) decreases the hydrogenation activity of catalyst in the biphasic catalytic system, but the selectivity for \{carboncarbon\} double bond hydrogenation increases to 98%. This is attributed to the steric effect of micelle formation, because the hydrogenated position is in the middle of the substrate molecule. In the absence of CTAB conversion of substrate and selectivity for benzylacetone are 70% and 94%, respectively. The change of / (molar ratio) has an obvious influence on the catalytic activity. The maxim um activity is obtained at / =3, while Ru is reduced sufficiently to RuI by TPPTS, which was favorable for the formation of catalytic active species. When the ]/ ratio increases further, the competitive coordination of TPPTS with substrate molecule on Ru complex causes the decrease of hydrogenation rate.

关 键 词：选择加氢 催化剂 钌 膦 苯基丁烯酮 苄叉丙酮 

分 类 号：O625.42[理学—有机化学] O643.38[理学—化学]