CC BY 4.0 · Synthesis 2023; 55(06): 919-926
DOI: 10.1055/a-1994-2301
special topic
Synthetic Advancements Enabled by Phosphorus Redox Chemistry

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

Daniel Picthall
a   EaStChem School of Chemistry, University of St. Andrews, St. Andrews, Fife, KY16 9ST, UK
,
Brian A. Surgenor
b   Treatt Plc, Bury St Edmunds, IP32 7FR, UK
,
Petr Kilian
a   EaStChem School of Chemistry, University of St. Andrews, St. Andrews, Fife, KY16 9ST, UK
› Author Affiliations
The authors acknowledge EastChem School of Chemistry for funding.


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.

Supporting Information



Publication History

Received: 12 September 2022

Accepted after revision: 07 December 2022

Accepted Manuscript online:
07 December 2022

Article published online:
09 January 2023

© 2022. The Author(s). This is an open access article published by Thieme under the terms of the Creative Commons Attribution License, permitting copying and reproduction so long as the original work is given appropriate credit. Contents may not be used for commercial purposes or adapted, remixed, transformed or built upon. (https://creativecommons.org/licenses/by/4.0/)

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