Convenient and Scalable Synthesis of Aryldichlorophosphines and Primary Arylphosphines via Perthiophosphonic Anhydrides

Abstract

A scalable synthetic route to both primary arylphosphines ArPH₂ and aryldichlorophosphines ArPCl₂ is reported. The C–P bond formation was performed in a highly regiospecific manner through electrophilic substitution of selected aromatic hydrocarbons (ArH) with phosphorus pentasulfide. The resultant perthiophosphonic anhydrides Ar₂P₂S₄ were then reacted with LiAlH₄ to give primary phosphines ArPH₂. Subsequent reaction of ArPH₂ with phosgene solution gives dichlorophosphines ArPCl₂. Each reaction step requires minimum purification and uses commercially available and economical precursors. The scope of the reaction was shown to include alkoxy and phenoxy substituted benzenes as well as naphthalene and fluorene as starting materials.

Key Words

primary phosphine - chlorophosphine - organophosphorus synthesis - ³¹P NMR

Publication History

Received: 12 September 2022

Accepted after revision: 07 December 2022

Accepted Manuscript online:
07 December 2022

Article published online:
09 January 2023

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