高等学校化学学报

高等学校化学学报 ›› 1993, Vol. 14 ›› Issue (9): 1265.

• 研究论文 • 上一篇    下一篇

铑螯合物对苯乙烯氢甲酰化的催化作用

陈万之1, 徐筠2, 廖世健2   

  1. 1. 山东大学新材料研究所, 济南 250100;
    2. 中国科学院大连化学物理研究所
  • 收稿日期:1992-10-27 修回日期:1993-03-22 出版日期:1993-09-24 发布日期:1993-09-24
  • 通讯作者: 陈万之.
  • 作者简介:第一作者:男, 28岁, 博士, 副教授.
  • 基金资助:

    国家自然科学基金

Hydroformylation of Styrene Catalyzed by Chelate Rhodium Complexes

CHEN Wan-Zhi1, XU Yun2, LIAO Shi-Jian2   

  1. 1. Institute of New Materials, Shandong University, Jinan, 250100;
    2. Dalian Institute of Chemical Physics, Academia Sinica, Dalian
  • Received:1992-10-27 Revised:1993-03-22 Online:1993-09-24 Published:1993-09-24

PDF (PC)

被引次数

5

摘要： 合成了螯合物二羰基邻氨基苯酚铑、二羰基(8-羟基喹啉)铑和二羰基亮氨酸铑,在常压、60℃下研究了其对苯乙烯氢甲酰化的催化作用.催化活性及选择性与氮氧螯合配体和外加膦配体结构有关,在双齿膦配体存在下,催化活性和选择性较高,膦铑比增大一般可使初活性降低,但转化率提高,而膦铑比对区域选择性影响很小.二羰基亮氨酸铑既表现出较好的活性和选择性,又可作为苯乙烯氢甲酰化手性催化剂,旋光产率9.5％.苯乙烯氢甲酰化的化学选择性均达100％.

关键词: 铑螯合物, 苯乙烯, 氢甲酰化, 催化

Abstract: Rhodium(Ⅰ) complexes prepared from the reaction between Rh2(CO)4Cl2 and the salts of aminophenol, 8-hydroxyquinoline and leucine respectively can catalyze the hydroformylation of styrene at 0.1 MPa and 60℃.The results show that the kind of phosphine ligands plays a crucial role in determining the catalyst activity and regioselectivity.Diphosphine ligands can induce a higher catalyst activity and regioselectivity to the branched aldehyde than PPh3.Triph-enylphosphite promotes the formation of normal aldehyde.Increasing the P/Rh ratio leads to a decrease of initial activity, nevertheless, the higher conversion can be obtained in the case of higher P/Rh ratio.The variation of P/Rh ratio does not affect the regioselectivity apparently.Dicarbonyl leucinatorhodium combined with diphosphines offers a high selectivity to 2-phenyl-propanal, furthermore, it can also be used as an asymmetric catalyst for the hydroformylation of styrene.The optical yield is 9.5% in the presence of Ph2P(CH2)3PPh2 at a P/Rh ratio of 5.

Key words: Chelate rhodium complexes, Styrene, Hydroformylation, Catalysis

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