Reactions of allenyltri-n-butylstannane with halides of phosphorus, arsenic, antimony, germanium, tin, and boron. Preparation of propargylic and/or allenic derivatives

The reaction of allenyltri-n-butylstannane with a phosphorus or arsenic tri halide and with germanium tetrachloride gave the corresponding propargylic halophosphine, arsine, or germane. When they were heated, the propargylic p roducts partially (P, Ge) or completely (As) rearranged into the correspond ing allenyl derivatives, the thermodynamic products. The allenic or proparg ylic stannane reacted with stronger Lewis acidic halides such as a boron ha lide, antimony trichloride, or tin tetrachloride to give only the allenic p roduct, even when the reaction was performed and analyzed at low temperatur e (-80 degrees C). The propargylic intermediate was observed with the antim ony and tin compounds when a substituted derivative (e.g. Vi(2)SbCl, ViSnCl (3)) was used. The reduction of the propargylic halide products prior to th eir isomerization gave the corresponding primary propargylic phosphine, ars ine, germane, and stannane.