Study of the reactivity of ClCo(PPh3)3

Q4 Chemical Engineering

分子催化 Pub Date : 1994-08-12 DOI:10.1016/0304-5102(94)85005-4

Hae-Youn Rhyoo, Bun Yeoul Lee, Hye Kyung Bae Yu, Young Keun Chung

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引用次数: 20

Abstract

The catalytic activity of ClCo(PPh₃)₃ in oligomerization of alkynes and reduction of carbonyl compounds has been investigated. Monosubstituted alkynes with an electron withdrawing group give quantitative yields of arene derivatives when reacted with 5 mol% of ClCo(PPh₃)₃. Cyclotrimerization of disubstituted alkynes with at least one electron withdrawing group requires the addition of NaBPh₄. In the oligomerization of phenylacetylene, cyclotrimerization and linear dimerization are in competition. However, when the reaction is run in the presence of 1.2 equiv. of NaOMe at room temperature, only linear dimerization is observed. Diethyl allylpropargylmalonate also cyclodimerizes or codimerizes with diphenylacetylene by catalytic amount of ClCo(PPh₃)₃ in the presence of NaOEt. Reaction of a variety of carbonyl compounds with 5 mol% of ClCo(PPh₃)₃ in i-propanol leads to the reduction of the compounds to the corresponding alcohols. The reaction requires the addition of NaH which produces (i-PrO)Na in situ. The role of alkoxides or NaBPh₄ in ClCo(PPh₃)₃ catalyzed oligomerization of alkynes or reduction of carbonyl compounds is discussed.

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ClCo(PPh3)3的反应性研究

研究了ClCo(PPh3)3在炔烃低聚反应和羰基化合物还原反应中的催化活性。带吸电子基团的单取代炔与5mol %的ClCo(PPh3)3反应时，给出了芳烃衍生物的定量产率。具有至少一个吸电子基团的二取代炔的环三聚化需要NaBPh4的加成。在苯乙炔的低聚反应中，环三聚反应和线性二聚反应是相互竞争的。然而，当反应在室温下在1.2等量的NaOMe存在下进行时，只观察到线性二聚化。在NaOEt的存在下，二乙基烯丙基丙二酸二乙酯也可与二苯乙炔环二聚或共二聚。在i-丙醇中，多种羰基化合物与5mol %的ClCo(PPh3)3反应，使化合物还原为相应的醇。该反应需要添加Na，从而原位生成(i-PrO)Na。讨论了烷基氧化物或NaBPh4在ClCo(PPh3)3催化炔烃低聚反应或羰基化合物还原中的作用。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

分子催化 Chemical Engineering-Catalysis

CiteScore

1.50

自引率

0.00%

发文量

2959

期刊介绍： Journal of Molecular Catalysis (China) is a bimonthly journal, founded in 1987. It is a bimonthly journal, founded in 1987, sponsored by Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, under the supervision of Chinese Academy of Sciences, and published by Science Publishing House, which is a scholarly journal openly circulated both at home and abroad. The journal mainly reports the latest progress and research results on molecular catalysis. It contains academic papers, research briefs, research reports and progress reviews. The content focuses on coordination catalysis, enzyme catalysis, light-ribbed catalysis, stereochemistry in catalysis, catalytic reaction mechanism and kinetics, the study of catalyst surface states and the application of quantum chemistry in catalysis. We also provide contributions on the activation, deactivation and regeneration of homogeneous catalysts, solidified homogeneous catalysts and solidified enzyme catalysts in industrial catalytic processes, as well as on the optimisation and characterisation of catalysts for new catalytic processes. The main target readers are scientists and postgraduates working in catalysis in research institutes, industrial and mining enterprises, as well as teachers and students of chemistry and chemical engineering departments in colleges and universities. Contributions from related professionals are welcome.