RhCl(PPh3)3的制备及其催化松节油加氢反应

doi:10.3969/j.issn.0253-2417.2020.04.017

摘要/Abstract

摘要：

使用可溶性铑盐和三苯基膦乙醇溶液制备了催化剂RhCl（PPh₃）₃，并将其用作α-蒎烯加氢反应的催化剂。以α-蒎烯的转化率和顺式蒎烷选择性作为RhCl（PPh₃）₃催化性能的评价指标，考察了制备条件对RhCl（PPh₃）₃催化性能的影响，同时，探讨了RhCl（PPh₃）₃催化α-蒎烯加氢反应的较优条件和RhCl（PPh₃）₃的使用寿命及反应机理。研究结果显示：较适宜的催化剂制备条件为膦与铑物质的量比4：1，加热温度75℃，回流时间4 h。将该条件下制备的RhCl（PPh₃）₃用于α-蒎烯加氢反应，在较优的加氢反应条件下，即α-蒎烯4 g，以离子液体[BMIM]PF₆为加氢反应介质，离子液体用量4 mL，反应温度120℃，反应压力1 MPa，转速800 r/min，催化剂RhCl（PPh₃）₃用量5%，反应时间3 h，α-蒎烯的平均转化率达到99.49%，顺式蒎烷的平均对映选择性为96.73%。离子液体催化剂体系与产物分离容易，可循环使用，使用2次，转化率仍能达到91.19%。离子液体为介质，RhCl（PPh₃）₃的催化反应机理为“离子介质-中心金属-底物”的相互作用，带电荷的离子液体与中心金属Rh的相互作用，使得其他配位体如Cl^-等的配位能力减弱，从而有利于烯烃的配位活化。

关键词: α-蒎烯, 不对称加氢, 离子液体, RhCl(PPh₃)₃, 顺式蒎烷

Abstract:

The catalyst RhCl(PPh₃)₃ was prepared from soluble rhodium salt and triphenylphosphine ethanol solution and used in the hydrogenation of α-pinene. Taking the conversion rate of α-pinene and the enantioselectivity of cis-pinene as the evaluation indexes, the effect of catalyst preparation conditions on the catalytic performance was investigated. The optimal conditions of catalytic preparation, catalyst life and reaction mechanism were also studied. The results showed that the most suitable catalyst preparation conditions were the ratio of phosphine to rhodium 4:1, the heating temperature 75 ℃, and the reflux time 4 h. The RhCl(PPh₃)₃ prepared under these conditions was used in the hydrogenation reaction of α-pinene. Under the optimal hydrogenation reaction conditions, namely α-pinene 4 g, the ionic liquid [BMIM] PF₆ 4 mL as reaction medium, reaction temperature 120 ℃, reaction pressure 1 MPa, speed 800 r/min, catalyst RhCl(PPh₃)₃ 5%, and reaction time 3 h, the average conversion rate of α-pinene reached 99.49%, and the average enantioselectivity of cis-pinane was 96.73%. The ionic liquid catalyst system was easy to separate from the product, and could be reused. The conversion rate could reach 91.19% at the second use. The ionic liquid was the medium, and the catalytic reaction mechanism of RhCl(PPh₃)₃ was the interaction of "ionic medium-center metal-substrate". The interaction of the charged ionic liquid with the center metal Rh made the coordination ability other ligands such as Cl^- weak, which was beneficial to the coordination activation of olefins.

Key words: α-pinene, asymmetric hydrogenation, ionic liquid, RhCl(PPh₃)₃, cis-pinane

中图分类号:

TQ231

刘壁莹,蒋丽红,王亚明,郑燕娥,郭炜,朱桂华. RhCl(PPh₃)₃的制备及其催化松节油加氢反应[J]. 林产化学与工业, 2020, 40(4): 123-128.

Biying LIU,Lihong JIANG,Yaming WANG,Yan'e ZHENG,Wei GUO,Guihua ZHU. Preparation of Phosphine and Rhodium Complexes and Its Catalytic Performance for Turpentine Hydrogenation[J]. Chemistry and Industry of Forest Products, 2020, 40(4): 123-128.

图/表 4

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次数times	转化率conversion/%	选择性selectivity/%
1	99.51	95.44
2	91.19	50.47
3	46.35	49.61

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RhCl(PPh₃)₃的制备及其催化松节油加氢反应

Preparation of Phosphine and Rhodium Complexes and Its Catalytic Performance for Turpentine Hydrogenation

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