Convenient and scalable synthesis of aryldichlorophosphines and primary arylphosphines via perthiophosphonic anhydrides

Daniel Picthall; Brian Surgenor; Petr Kilian

doi:10.1055/a-1994-2301

Convenient and scalable synthesis of aryldichlorophosphines and primary arylphosphines via perthiophosphonic anhydrides

Daniel Picthall, Brian Surgenor, Petr Kilian^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

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.

Original language	English
Pages (from-to)	A-H
Number of pages	8
Journal	Synthesis
Volume	eFirst
DOIs	https://doi.org/10.1055/a-1994-2301
Publication status	Published - 9 Jan 2023

Keywords

Primary phosphine
Chlorophosphine
Organophosphorus synthesis
31P NMR

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10.1055/a-1994-2301Licence: CC BY

Picthall_2023_Synthesis_Convenient-scalable_CC
Copyright © 2023. The Author(s). This is an open access article published by Thieme under the terms of the Creative Commons Attribution License, permitting unrestricted use, distribution and reproduction, so long as the original work is properly cited (https://creativecommons.org/licenses/by/4.0/).
Final published version, 718 KBLicence: CC BY

Convenient and Scalable Synthesis of Aryldichlorophosphines and Primary Arylphosphines via Perthiophosphonic Anhydrides (dataset)
Kilian, P. (Owner), Picthall, D. (Creator) & Surgenor, B. (Contributor), University of St Andrews, 20 Dec 2022
DOI: 10.17630/29cff64a-cb08-48ab-b2fd-edd2284d9df5
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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.",

keywords = "Primary phosphine, Chlorophosphine, Organophosphorus synthesis, 31P NMR",

author = "Daniel Picthall and Brian Surgenor and Petr Kilian",

note = "Funding: The authors acknowledge EastChem School of Chemistry for funding.",

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doi = "10.1055/a-1994-2301",

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TY - JOUR

T1 - Convenient and scalable synthesis of aryldichlorophosphines and primary arylphosphines via perthiophosphonic anhydrides

AU - Picthall, Daniel

AU - Surgenor, Brian

AU - Kilian, Petr

N1 - Funding: The authors acknowledge EastChem School of Chemistry for funding.

PY - 2023/1/9

Y1 - 2023/1/9

N2 - 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.

AB - 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.

KW - Primary phosphine

KW - Chlorophosphine

KW - Organophosphorus synthesis

KW - 31P NMR

U2 - 10.1055/a-1994-2301

DO - 10.1055/a-1994-2301

M3 - Article

SN - 0039-7881

VL - eFirst

SP - A-H

JO - Synthesis

JF - Synthesis

ER -

Convenient and scalable synthesis of aryldichlorophosphines and primary arylphosphines via perthiophosphonic anhydrides

Abstract

Keywords

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Convenient and Scalable Synthesis of Aryldichlorophosphines and Primary Arylphosphines via Perthiophosphonic Anhydrides (dataset)

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