Chlorodiphenylphosphine

Chlorodiphenylphosphine
Names
	Preferred IUPAC name Diphenylphosphinous chloride
	Other names chlorodiphenylphosphine; p-chlorodiphenylphosphine; diphenyl phosphine chloride; diphenylchlorophosphine
Identifiers
CAS Number	1079-66-9 ;
3D model (JSmol)	Interactive image;
ChemSpider	59567 ;
ECHA InfoCard	100.012.813
EC Number	214-093-2;
PubChem CID	66180;
UNII	WO975PJK1Y ;
CompTox Dashboard (EPA)	DTXSID7038789 ;
	InChI InChI=1S/C12H10ClP/c13-14(11-7-3-1-4-8-11)12-9-5-2-6-10-12/h1-10H Key: XGRJZXREYAXTGV-UHFFFAOYSA-N ; InChI=1/C12H10ClP/c13-14(11-7-3-1-4-8-11)12-9-5-2-6-10-12/h1-10H Key: XGRJZXREYAXTGV-UHFFFAOYAM;
	SMILES ClP(c1ccccc1)c2ccccc2;
Properties
Chemical formula	C12H10ClP
Molar mass	220.63776 g mol−1
Appearance	clear to light yellow liquid
Density	1.229 g cm−3
Boiling point	320 ˚C
Solubility in water	Reacts
Solubility	Reacts with alcohols; highly soluble in benzene, THF, and ethers
Hazards
GHS pictograms
GHS Signal word	Danger
GHS hazard statements	H290, H302, H314, H318, H412
GHS precautionary statements	P234, P260, P264, P270, P273, P280, P301+312, P301+330+331, P303+361+353, P304+340, P305+351+338, P310, P321, P330, P363, P390, P404, P405, P501
	Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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	Infobox references

Chlorodiphenylphosphine is an organophosphorus compound with the formula (C₆H₅)₂PCl, abbreviated Ph₂PCl. It is a colourless oily liquid with a pungent odor that is often described as being garlic-like and detectable even in the ppb range. It is useful reagent for introducing the Ph₂P group into molecules, which includes many ligands.[1] Like other halophosphines, Ph₂PCl is reactive with many nucleophiles such as water and easily oxidized even by air.

Synthesis and reactions

Chlorodiphenylphosphine is produced on a commercial scale from benzene and phosphorus trichloride (PCl₃). Benzene reacts with phosphorus trichloride at extreme temperatures around 600 °C to give dichlorophenylphosphine (PhPCl₂) and HCl. Redistribution of PhPCl₂ in the gas phase at high temperatures results in chlorodiphenylphosphine.[1][2]

2 PhPCl₂ → Ph₂PCl + PCl₃

Alternatively such compounds are prepared by redistribution reactions starting with triphenylphosphine and phosphorus trichloride.

PCl₃ + 2 PPh₃ → 2 Ph₂PCl

Chlorodiphenylphosphine hydrolyzes to give diphenylphosphine oxide. Reduction with sodium affords tetraphenyldiphosphine:

2 Ph₂PCl + 2 Na → [Ph₂P]₂ + 2 NaCl

Uses

Chlorodiphenylphosphine, along with other chlorophosphines, is used in the synthesis of various phosphines. A typical route uses Grignard reagents:[2]

Ph₂PCl + MgRX → Ph₂PR + MgClX

The phosphines produced from reactions with Ph₂PCl are further developed and used as pesticides (such as EPN), stabilizers for plastics (Sandostab P-EPQ), various halogen compound catalysts, flame retardants (cyclic phosphinocarboxylic anhydride), as well as UV-hardening paint systems (used in dental materials) making Ph₂PCl an important intermediate in the industrial world.[1][2]

Precursor to diphenylphosphido derivatives

Chlorodiphenylphosphine is used in the synthesis of sodium diphenylphosphide via its reaction with sodium metal in refluxing dioxane.[3]

Ph₂PCl + 2 Na → Ph₂PNa + NaCl

Diphenylphosphine can be synthesized in the reaction of Ph₂PCl and LiAlH₄, the latter usually used in excess.[4]

4 Ph₂PCl + LiAlH₄ → 4 Ph₂PH + LiCl + AlCl₃

Both Ph₂PNa and Ph₂PH are also used in the synthesis of organophosphine ligands.

Characterization

The quality of chlorodiphenylphosphine is often checked by 31P NMR spectroscopy.[5]

Compound	³¹P chemical shift (ppm vs 85% H₃PO₄)
PPh₃	-6
PPh₂Cl	81.5
PPhCl₂	165
PCl₃	218

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References

Quin, L. D. A Guide to Organophosphorus Chemistry; Wiley IEEE: New York, 2000; pp 44-69. ISBN 0-471-31824-8
Svara, J.; Weferling, N.; Hofmann, T. "Phosphorus Compounds, Organic," In 'Ullmann's Encyclopedia of Industrial Chemistry, 7th ed.; Wiley-VCH: 2008; doi:10.1002/14356007.a19_545.pub2; Accessed: February 18, 2008.
Roy, Jackson W; Thomson, RJ; MacKay.m.f, . (1985). "The Stereochemistry of Organometallic Compounds. XXV. The Stereochemistry of Displacements of Secondary Methanesulfonate and p-Toluene-sulfonate esters by Diphenylphosphide Ions. X-ray Crystal Structure of (5α-Cholestan-3α-yl)diphenylphosphine Oxide". Australian Journal of Chemistry. 38 (1): 111–18. doi:10.1071/CH9850111.CS1 maint: numeric names: authors list (link)
Stepanova, Valeria A.; Dunina, Valery V.; Smoliakova, Irina P. (2009). "Reactions of Cyclopalladated Complexes with Lithium Diphenylphosphide". Organometallics. 28 (22): 6546–6558. doi:10.1021/om9005615.
O. Kühl "Phosphorus-31 NMR Spectroscopy" Springer, Berlin, 2008. ISBN 978-3-540-79118-8

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[Quin-1] Quin, L. D. A Guide to Organophosphorus Chemistry; Wiley IEEE: New York, 2000; pp 44-69. ISBN 0-471-31824-8

[Svara-2] Svara, J.; Weferling, N.; Hofmann, T. "Phosphorus Compounds, Organic," In 'Ullmann's Encyclopedia of Industrial Chemistry, 7th ed.; Wiley-VCH: 2008; doi:10.1002/14356007.a19_545.pub2; Accessed: February 18, 2008.

[3] Roy, Jackson W; Thomson, RJ; MacKay.m.f, . (1985). "The Stereochemistry of Organometallic Compounds. XXV. The Stereochemistry of Displacements of Secondary Methanesulfonate and p-Toluene-sulfonate esters by Diphenylphosphide Ions. X-ray Crystal Structure of (5α-Cholestan-3α-yl)diphenylphosphine Oxide". Australian Journal of Chemistry. 38 (1): 111–18. doi:10.1071/CH9850111.CS1 maint: numeric names: authors list (link)

[4] Stepanova, Valeria A.; Dunina, Valery V.; Smoliakova, Irina P. (2009). "Reactions of Cyclopalladated Complexes with Lithium Diphenylphosphide". Organometallics. 28 (22): 6546–6558. doi:10.1021/om9005615.

[5] O. Kühl "Phosphorus-31 NMR Spectroscopy" Springer, Berlin, 2008. ISBN 978-3-540-79118-8