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Synthetic Communications
An International Journal for Rapid Communication of Synthetic Organic Chemistry
Volume 27, 1997 - Issue 10
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Original Articles

Triphenylphosphine-Catalyzed Isomerisation of Propargyl Bromide to 1-Bromopropadiene

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Pages 1685-1688 | Received 13 Dec 1996, Published online: 22 Aug 2006

References and Notes

  • Brandsma , L. and Verkruijsse , H. D. 1991 . Synth. Commun. , 21 : 69 – 72 .
  • Brandsma , L. and Verkruijsse , H. D. 1981 . Synthesis of Acetylenes, Allenes and Cumulenes , 178 – 179 . Amsterdam : Elsevier .
  • Jacobs , T. L. and Brill , W. F. 1953 . J. Am. Chem. Soc. , 75 : 1314 – 1317 .
  • For other examples of triphenylphosphine-catalyzed isomerisations see: a) Trost B. M. Li C.-J. J. Am. Chem. Soc. 1994 116 3167 3168
  • Rychnovsky , S. and Kim , J. 1994 . J. Org. Chem. , 59 : 2659 – 2660 . for the formation of propargyl phosphonium salts see
  • Hann , M. M. , Sammes , P. G. , Kennewell , P. D. and Taylor , J. B. 1982 . J. Chem. Soc., Perkin Trans. , 1 : 307 – 314 .
  • Ahmed , M. , Barley , M. T. W. , Jones , E. R. H. , Thaller , V. and Yates , J. A. 1974 . J. Chem. Soc., Perkin Trans. , 1 : 1981 – 1987 .
  • Yield relating to the conversion of propargyl bromide.
  • No isomerisation was observed in CDCl3. Treatment of 2 with triphenyl-phosphine in benzene under the given conditions did not result in the formation of 1.
  • Isomerisation of 1 to 2 was also observed with tricyclohexylphosphine. Without added phosphine no isomerisation was detected if a benzene solution of 1 was heated for 48 h.
  • a) 3-Bromo-3-phenyl-l-propyne and 3-bromo-hex-1-yne show a sluggish reaction with triphenylphosphine. No defined products could be isolated
  • All investigated propargylic compounds have been prepared according to procedures in: Brandsma L. Preparative Acetylenic Chemistry Elsevier Amserdam 1988
  • Aidhen , I. S. and Braslau , R. 1994 . Synth. Commun. , 24 : 789 – 797 . For a recent example of SN2′ reaction in allene formation see:
  • the restriction of the reaction to non-polar solvents indicates the importance of a contact ion pair for the isomerisation process;
  • for the reaction of triphenyl(prop-2-ynyl)phosphonium bromide with nucleophiles see: Schweizer E. E. DeVoe Goff S. J. Org. Chem. 1978 43 2972 2976

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