Triphenylphosphine-catalyzed isomerisation of propargyl bromide to 1-bromopropadiene

Synthetic Communications

Volumn 27, Issue 10, 1997, Pages 1685-1688

  König, Burkhard ^a   Eilers, Beate ^a  

^a TECHNICAL UNIVERSITY OF BRAUNSCHWEIG   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

ORGANOBROMINE DERIVATIVE;

ARTICLE; DRUG SYNTHESIS; IN VITRO STUDY; REACTION ANALYSIS;

EID: 1842291553     PISSN: 00397911     EISSN: None     Source Type: Journal    
DOI: 10.1080/00397919708004078     Document Type: Article

References (15)

1. a) Brandsma, L. and Verkruijsse, H. D. Synth. Commun. 1991, 21, 69-72;
2. b) Brandsma, L. and Verkruijsse, H. D. "Synthesis of Acetylenes, Allenes and Cumulenes" Elsevier, Amsterdam, 1981, pp. 178-179;
3. c) Jacobs, T. L. and Brill, W. F. J. Am. Chem. Soc. 1953, 75, 1314-1317.
4. For other examples of triphenylphosphine-catalyzed isomerisations see: a) Trost, B. M. and Li, C.-J. J. Am. Chem. Soc. 1994, 116, 3167-3168;
5. b) Rychnovsky, S. and Kim, J. J. Org. Chem. 1994, 59, 2659-2660; for the formation of propargyl phosphonium salts see:
6. c) Hann, M. M., Sammes, P. G., Kennewell, P. D. and Taylor, J. B. J. Chem. Soc., Perkin Trans. 1, 1982, 307-314;
7. d) Ahmed, M., Barley, M. T. W., Jones, E. R. H., Thaller, V. and Yates, J. A. J. Chem. Soc., Perkin Trans. 1, 1974, 1981-1987.
8. Yield relating to the conversion of propargyl bromide.
9. 3. Treatment of 2 with triphenylphosphine in benzene under the given conditions did not result in the formation of 1.
10. 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.
11. a) 3-Bromo-3-phenyl-1-propyne and 3-bromo-hex-1-yne show a sluggish reaction with triphenylphosphine. No defined products could be isolated;
12. b) All investigated propargylic compounds have been prepared according to procedures in: Brandsma, L. 'Preparative Acetylenic Chemistry'', Elsevier, Amserdam, 1988.
13. N2′ reaction in allene formation see: Aidhen, I. S. and Braslau, R. Synth. Commun. 1994, 24, 789-797;
14. b) the restriction of the reaction to non-polar solvents indicates the importance of a contact ion pair for the isomerisation process;
15. for the reaction of triphenyl(prop-2-ynyl)phosphonium bromide with nucleophiles see: Schweizer, E. E. and DeVoe Goff, S. J. Org. Chem. 1978, 43, 2972-2976.