Organophosphorus Synthesis Without Phosphorus Trichloride: The Case for the Hypophosphorous Pathway

Abstract

The vast majority of organophosphorus compounds is currently synthesized from phosphorus trichloride (PCl₃), even though the final consumer products do not contain reactive phosphorus–chlorine bonds. In order to bypass phosphorus trichloride, significant interest has been devoted to functionalizing elemental phosphorus (P₄, the precursor to PCl₃), red phosphorus (P_red), or phosphine (PH₃). Yet, other industrial-scale precursors are hypophosphorous derivatives (H₃PO₂ and its alkali salts), but their use as phosphorus trichloride replacements has been completely overlooked. Here, the case is made for an alternative approach to the industrial synthesis of organophosphorus compounds based on hypophosphites.

GRAPHICAL ABSTRACT

Keywords:

• Hypophosphite
• H-phosphinic acid
• phosphonic acid
• phosphorus trichloride
• elemental phosphorus
• phosphine

Acknowledgments

This material is based, in part, upon work supported by the National Science Foundation under Grant No. 0953368. Support from the Robert A. Welch Foundation (Grant P-1666) is also acknowledged. The author would also like to thank all coworkers, past and present, who have contributed/are contributing so much to the development of hypophosphorous chemistry.