• Search Research Projects
  • Search Researchers
  • How to Use
  1. Back to previous page

Reactions of Highly Nucleophilic Triphenylphosphines

Research Project

Project/Area Number 60550611
Research Category

Grant-in-Aid for General Scientific Research (C)

Allocation TypeSingle-year Grants
Research Field Synthetic chemistry
Research InstitutionTottori University (1986)
Osaka University (1985)

Principal Investigator

WADA Masanori  Tottori University, Faculty of Engineering, 工学部, 教授 (30029053)

Co-Investigator(Kenkyū-buntansha) KAWASAKI Yosikane  Osaka University, Faculty of Engineering, 工学部, 助教授 (50029055)
ERABI Tatsuo  Tottori University, Faculty of Engineering, 工学部, 助手 (60032025)
Project Period (FY) 1985 – 1986
Project Status Completed (Fiscal Year 1986)
Budget Amount *help
¥2,000,000 (Direct Cost: ¥2,000,000)
Fiscal Year 1986: ¥600,000 (Direct Cost: ¥600,000)
Fiscal Year 1985: ¥1,400,000 (Direct Cost: ¥1,400,000)
KeywordsNucleophile / Tertiary phosphine / Quarternary phosphonium salt / Alkyl chloride / Epoxide / Michael addition / ニトロアルカン
Research Abstract

Triphenylphosphines bearing methoxy substituents at the 2,6-positions of the phenyl groups, (2,4,6) <_3P> and (2,6) <_3P> [abbr. (2,4,6)= 2,4,6- <MeO_3> <C_6> <H_2> and (2,6)= 2,6- <MeO_2> <C_6> <H_3> ], exhibit unusually high nucleophilicity. Thus, they reacted under mild conditions with a variety of alkyl halides including butyl chloride and 2-propyl chloride to give the corresponding quarternary phosphonium salts. Treatment of (2,6) <_3P> with epoxides <CH_2> <CR^1> <R^2> O in alcohol at room temperature readily gave the [(2,6) <_3P> - <CH_2> <CR^1> <R^2> OH] <^+> species. Thermolysis of these salts in the presence of the ethoxide anion gave the [(2,6) <_3P> -Me] <^+> salt and ketone <R^1> <R^2> CO [ <R^1> <R^2> = Me,Me; Me,Ph; Ph,Ph, <(CH_2CH_2)_2> CH <Bu^t> ], the [(2,6) <_3P> - <CH_2> CH <R^1> OEt] <^+> salt ( <R^1> <R^2> = Me,H; H,H), the [(2,6) <_3P> -CH=CH=CHMe] <^+> salt ( <R^1> <R^2> =Et,H), or the [(2,6) <_3P> -CH=CHPh] <^+> salt ( <R^1> <R^2> = Ph,H); however, no phosphorus-carbon bond cleavage product was obtained. (2,4,6) <_3P> was found to work as a convenient and excellent catalyst (initiator) for the Michael addition of <CH_2> =CHCN, <CH_2> CHCOOEt, and <CH_2> =CHC(O)Me with some nitroalkanes.

Report

(1 results)
  • 1986 Final Research Report Summary
  • Research Products

    (6 results)

All Other

All Publications (6 results)

  • [Publications] 和田正徳: 有機合成化学協会誌. 44. 957-960 (1986)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1986 Final Research Report Summary
  • [Publications] Masanori Wada: J.Chem.Soc.,Perkin Trans.I. (1987)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1986 Final Research Report Summary
  • [Publications] 和田正徳: 日本化学会誌. 39. (1987)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1986 Final Research Report Summary
  • [Publications] Masanori Wada: "Highly Nucleophilic Triphenylphosphines" Journal of Synthetic Organic Chemistry, Japan. 44. 957-960 (1986)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1986 Final Research Report Summary
  • [Publications] Masanori Wada: "Reactions of Tris(2,6-dimethoxyphenyl)phosphine with Epoxides" Journal of Chemical Society, Perkin Transaction <I> . (1987)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1986 Final Research Report Summary
  • [Publications] Masanori Wada: "Michael Addition of Nitroalkanes Catalysed by Highly Nucloephilic Triarylphosphine, [2,4,6-( <CH_3> O) <_3> <C_6> <H_2> ] <_3P> " Journal of Japan Chemical Society (Nippon Kagaku Kaisi). 39. (1987)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1986 Final Research Report Summary

URL: 

Published: 1987-03-31   Modified: 2016-04-21  

Information User Guide FAQ News Terms of Use Attribution of KAKENHI

Powered by NII kakenhi