The cyanation of aromatic halides catalyzed by nickel(0) complexes generated in situ. I. General scope and limitations.
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概要
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The cyanation of chlorobenzene catalyzed by Ni(PPh<SUB>3</SUB>)<I><SUB>n</SUB></I>, which was generated in situ from NiBr<SUB>2</SUB>(PPh<SUB>3</SUB>)<SUB>2</SUB>–Zn–PPh<SUB>3</SUB>(Ni : Zn : P=1 : 3 : 2 molar ratio), was at first examined with various MCN (M=K, Na)–solvent systems by three procedures in order to clarify the conditions under which the reaction occurs. The effects of the systems and the procedures on the reaction were remarkable. It was observed that the cyanide ion has an inhibitory action on both the reduction of Ni(II) and the oxidative addition of the halide to Ni(0). However, when such MCN–dipolar aprotic solvent systems as KCN–HMPA, KCN or NaCN–MeCN, which give low cyanide concentrations, were used, the reaction readily took place at 50–60 °C without reducing Ni(II) prior to the addition of MCN and adding MCN slowly. Various Y-substituted chlorobenzenes, except for those with Y=<I>o</I>-Cl, <I>o</I>-CN, and <I>m</I>-NO<SUB>2</SUB>, were cyanated to give the corresponding nitriles in fair to good yields. NiBr<SUB>2</SUB>–PPh<SUB>3</SUB> can be used in place of NiBr<SUB>2</SUB>(PPh<SUB>3</SUB>)<SUB>2</SUB> if MCN is added after reduction. In addition, less reactive halides, such as <I>o</I>-dichlorobenzene and <I>o</I>-chlorobenzonitrile, were fairly smoothly cyanated by the use of NiBr<SUB>2</SUB>–1,1′-bis(diphenylphosphino)ferrocene.
- 公益社団法人 日本化学会の論文
著者
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Sakai Mutsuji
Department Of Polymer Science And Engineering Kyoto Institute Of Technology
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Sakakibara Yasumasa
Department Of Polymer Science And Engineering Kyoto Institute Of Technology
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Takagi Kentaro
College Of Liberal Arts And Science Okayama University
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Okuda Fumio
Department of Hydrocarbon Chemistry, Faculty of Engineering, Kyoto University
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Uchino Norito
Department of Fiber Chemistry, Kyoto Technical University
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Shimobayashi Akira
Department of Polymer Science and Engineering, Kyoto Institute of Technology
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Kirino Kunihiko
Department of Polymer Science and Engineering, Kyoto Institute of Technology
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Sakakibara Yasumasa
Department of Fiber Chemistry, Kyoto Technical University
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