Flash Communication: Gram-Scale Synthesis of White Phosphorus, P4

A convenient chemical vapor transport approach is reported for the preparation of white phosphorus, P₄, on a gram scale. The activation of P₄ has long fascinated main group and transition metal chemists, who have sought a greener route to directly convert this allotrope of phosphorus to organophosphorus compounds. However, the absence of a commercial supplier of P₄ has hindered the thorough exploration of this small molecule’s activation and functionalization. Although methods for the generation of P₄ from red phosphorus have been reported, safety considerations associated with these methods necessitated the development of a safer alternative synthetic route. Herein, we report a method for the preparation of pure white phosphorus, P₄, by heating its readily available red phosphorus allotrope in a sealed quartz tube across a large temperature gradient.