Chlorodiphenylphosphine

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{{nbsp}}PhPCl₂ → Ph₂PCl + PCl₃

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

:PCl₃ + 2{{nbsp}}PPh₃ → 3{{nbsp}}Ph₂PCl

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

:2{{nbsp}}Ph₂PCl + 2{{nbsp}}Na → [Ph₂P]₂ + 2{{nbsp}}NaCl

With ammonia and elemental sulfur, it converts to the thiophosphorylamide:{{cite journal |doi=10.15227/orgsyn.094.0313|title=Catalytic Enantioselective Addition of Diethyl Phosphite to N-Thiophosphinoyl Ketimines: Preparation of (R)-Diethyl (1-Amino-1-phenylethyl)phosphonate|year=2017|last1=Lin|first1=Shaoquan|first2=Yasunari|last2=Otsuka|first3=Liang|last3=Yin|first4=Naoya|last4=Kumagai|first5=Masakatsu|last5=Shibasaki|journal=Organic Syntheses|volume=94|pages=313–331|doi-access=free}}

:Ph₂PCl + 2{{nbsp}}NH₃ + S → Ph₂P(S)NH₂ + NH₄Cl

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

: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.

Chlorodiphenylphosphine is used in the synthesis of sodium diphenylphosphide via its reaction with sodium metal in refluxing dioxane.{{cite journal | doi = 10.1071/CH9850111 | last1 = Roy | first1 = Jackson W | last2 = Thomson | first2 = RJ | last3 = MacKay | first3 = M.F. | title = 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 | journal = Australian Journal of Chemistry | year = 1985 | volume = 38 | issue = 1 | pages = 111–18}}

:Ph₂PCl + 2 Na → Ph₂PNa + NaCl

Diphenylphosphine can be synthesized in the reaction of Ph₂PCl and LiAlH₄, the latter usually used in excess.{{cite journal | doi = 10.1021/om9005615 | last1 = Stepanova | first1 = Valeria A. | last2 = Dunina | first2 = Valery V. | last3 = Smoliakova | first3 = Irina P. | title = Reactions of Cyclopalladated Complexes with Lithium Diphenylphosphide | journal = Organometallics | year = 2009 | volume = 28 | issue = 22 | pages = 6546–6558}}

:4 Ph₂PCl + LiAlH₄ → 4 Ph₂PH + LiCl + AlCl₃

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

The quality of chlorodiphenylphosphine is often checked by 31P NMR spectroscopy.O. Kühl "Phosphorus-31 NMR Spectroscopy" Springer, Berlin, 2008. {{ISBN|978-3-540-79118-8}}

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Category:Phenyl compounds

Category:Chlorophosphine