[Rh(COD) Cl]2催化剂的制备及催化α-蒎烯不对称加氢反应

doi:10.16085/j.issn.1000-6613.2017.01.025

摘要/Abstract

摘要： 以RhCl₃·3H₂O和1，5-环辛二烯为原料制备了[Rh（COD）Cl]₂催化剂，并利用傅里叶变换红外光谱仪（FTIR）和X射线光电子能谱（XPS）对其进行了表征。以α-蒎烯加氢为探针反应，考察了COD/Rh摩尔比、回流温度及回流时间对催化剂催化性能的影响，并通过正交试验确定了催化剂适宜的制备条件：COD/Rh摩尔比（1，5-环辛二烯与三水合氯化铑摩尔比）3.5：1，回流温度75℃，回流时间3.5h。将该条件下制备的[Rh（COD）Cl]₂催化剂用于α-蒎烯加氢反应，α-蒎烯转化率达97.3%以上，顺式蒎烷对映选择性高于97.5%，顺式蒎烷收率达95.0%以上。与文献报道的其他工艺相比，该工艺特点是加氢条件比较温和，选择性高，催化效率高，能耗低。

关键词: α-蒎烯, 催化作用, 加氢, 铑催化剂, 选择性

Abstract: [Rh(COD)Cl]₂ catalyst was prepared by using RhCl₃·3H₂O and 1,5-cyclooctadiene as raw materials and characterized by Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. Taking α-pinene hydrogenation as a probe reaction,we investigated the effects of COD/Rh molar ratio,reflux temperature and reflux time on the catalytic properties. The suitable conditions for preparing the catalysts were proposed through orthogonal experiment,which were COD/Rh molar ratio of 3.5:1,reflux temperature of 75℃ and reflux time of 3.5h. Then the conversion of α-pinene was above 97.3%,the enantioselective of cis-pinane was above 97.5% and the yield of cis-pinane was above 95.0%. Compared with other processes reported in the literature,the proposed process had features of mild hydrogenation conditions,high enantioselective,high catalytic efficiency and low energy consumption.

Key words: α-pinene, catalysis, hydrogenation, rhodium catalyst, selectivity

中图分类号:

TQ54

王红琴, 王亚明, 蒋丽红, 张家华, 鞠江月. [Rh(COD) Cl]₂催化剂的制备及催化α-蒎烯不对称加氢反应[J]. 化工进展, 2017, 36(01): 196-202.

WANG Hongqin, WANG Yaming, JIANG Lihong, ZHANG Jiahua, JU Jiangyue. Preparation of [Rh(COD)Cl]₂ catalyst and its activity for asymmetric hydrogenation of α-pinene[J]. Chemical Industry and Engineering Progree, 2017, 36(01): 196-202.

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[Rh(COD) Cl]₂催化剂的制备及催化α-蒎烯不对称加氢反应

Preparation of [Rh(COD)Cl]₂ catalyst and its activity for asymmetric hydrogenation of α-pinene

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