Reactions of Allenyltri-n-butylstannane with Halides of Phosphorus, Arsenic, Antimony, Germanium, Tin, and Boron. Preparation of Propargylic and/or Allenic Derivatives

Abstract

The reaction of allenyltri-n-butylstannane with a phosphorus or arsenic trihalide and with germanium tetrachloride gave the corresponding propargylic halophosphine, arsine, or germane. When they were heated, the propargylic products partially (P, Ge) or completely (As) rearranged into the corresponding allenyl derivatives, the thermodynamic products. The allenic or propargylic stannane reacted with stronger Lewis acidic halides such as a boron halide, antimony trichloride, or tin tetrachloride to give only the allenic product, even when the reaction was performed and analyzed at low temperature (−80 °C). The propargylic intermediate was observed with the antimony and tin compounds when a substituted derivative (e. g. Vi2SbCl, ViSnCl3) was used. The reduction of the propargylic halide products prior to their isomerization gave the corresponding primary propargylic phosphine, arsine, germane, and stannane.