Alkynylhalocarbenes 1. Generation of alkynylchloro- and alkynylbromocarbenes from alkynylchlorobromo- and alkynyldibromomethanes, their multiplicity and philicity

  • K. N. Shavrin
  • I. B. Shvedova
  • O. M. Nefedov
Organic Chemistry
  • 28 Downloads

Abstract

The action of t-BuOK on alkynyldihalomethanes RC≡CCHBrX (I, R=Me, t-Bu, Ph; X= Br, Cl) in pentane at −20 to 0°C generates the corresponding alkynylhalocarbenes RC≡C\(\ddot C\)X (II; X=Br, Cl) which in the presence of olefins give alkynylhalocyclo-propanes (V) in 26–70% yield. It has been shown for the example of the reaction of (methylethynyl-) and (tert-butylethynyl)bromocarbenes with cis-butene-2 that the cycloaddition is fully stereospecific. The selectivity index for (methyl-ethynyl)bromocarbene was experimentally determined as 0.48 which is evident for electrophilic character in this carbene.

Keywords

Pentane Carbene Selectivity Index Electrophilic Character 

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Copyright information

© Plenum Publishing Corporation 1992

Authors and Affiliations

  • K. N. Shavrin
    • 1
  • I. B. Shvedova
    • 1
  • O. M. Nefedov
    • 1
  1. 1.N. D. Zelinskii Institute of Organic ChemistryAcademy of Sciences of the USSRMoscow

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