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 labelling:
Pictograms
Signal word	Danger
Hazard statements	H290, H302, H314, H412
Precautionary statements	P234, P260, P264, P270, P273, P280, P301+P312, P301+P330+P331, P303+P361+P353, P304+P340, P305+P351+P338, 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). verify (what is ?) 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.^[2] 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.^[2]^[3]

2 PhPCl₂ → Ph₂PCl + PCl₃

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

PCl₃ + 2 PPh₃ → 3 Ph₂PCl

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

2 Ph₂PCl + 2 Na → [Ph₂P]₂ + 2 NaCl

With ammonia and elemental sulfur, it converts to the thiophosphorylamide:^[4]

Ph₂PCl + 2 NH₃ + S → Ph₂P(S)NH₂ + NH₄Cl

Uses

Chlorodiphenylphosphine, along with other chlorophosphines, is used in the synthesis of various phosphines. A typical route uses Grignard reagents:^[3]

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.^[2]^[3]

Precursor to diphenylphosphido derivatives

Chlorodiphenylphosphine is used in the synthesis of sodium diphenylphosphide via its reaction with sodium metal in refluxing dioxane.^[5]

Ph₂PCl + 2 Na → Ph₂PNa + NaCl

Diphenylphosphine can be synthesized in the reaction of Ph₂PCl and LiAlH₄, the latter usually used in excess.^[6]

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.^[7]

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

References

^ International Union of Pure and Applied Chemistry (2014). Nomenclature of Organic Chemistry: IUPAC Recommendations and Preferred Names 2013. The Royal Society of Chemistry. p. 926. doi:10.1039/9781849733069. ISBN 978-0-85404-182-4.
^ ^a ^b ^c Quin, L. D. A Guide to Organophosphorus Chemistry; Wiley IEEE: New York, 2000; pp 44-69. ISBN 0-471-31824-8
^ ^a ^b ^c 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.
^ Lin, Shaoquan; Otsuka, Yasunari; Yin, Liang; Kumagai, Naoya; Shibasaki, Masakatsu (2017). "Catalytic Enantioselective Addition of Diethyl Phosphite to N-Thiophosphinoyl Ketimines: Preparation of (R)-Diethyl (1-Amino-1-phenylethyl)phosphonate". Organic Syntheses. 94: 313–331. doi:10.15227/orgsyn.094.0313.
^ 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.
^ 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

[1] International Union of Pure and Applied Chemistry (2014). Nomenclature of Organic Chemistry: IUPAC Recommendations and Preferred Names 2013. The Royal Society of Chemistry. p. 926. doi:10.1039/9781849733069. ISBN 978-0-85404-182-4.

[Quin-2] Quin, L. D. A Guide to Organophosphorus Chemistry; Wiley IEEE: New York, 2000; pp 44-69. ISBN 0-471-31824-8

[Svara-3] 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.

[4] Lin, Shaoquan; Otsuka, Yasunari; Yin, Liang; Kumagai, Naoya; Shibasaki, Masakatsu (2017). "Catalytic Enantioselective Addition of Diethyl Phosphite to N-Thiophosphinoyl Ketimines: Preparation of (R)-Diethyl (1-Amino-1-phenylethyl)phosphonate". Organic Syntheses. 94: 313–331. doi:10.15227/orgsyn.094.0313.

[5] 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.

[6] 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.

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

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