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.