Phenylphosphine

Phenylphosphine
Names
	Other names Monophenylphosphine
Identifiers
CAS Number	638-21-1 ;
3D model (JSmol)	Interactive image;
ChemSpider	12002 ;
ECHA InfoCard	100.010.297
EC Number	211-325-4;
PubChem CID	12519;
CompTox Dashboard (EPA)	DTXSID7073224 ;
	InChI InChI=1S/C6H7P/c7-6-4-2-1-3-5-6/h1-5H,7H2 Key: RPGWZZNNEUHDAQ-UHFFFAOYSA-N ; InChI=1/C6H7P/c7-6-4-2-1-3-5-6/h1-5H,7H2 Key: RPGWZZNNEUHDAQ-UHFFFAOYAH;
	SMILES C1=CC=C(C=C1)P;
Properties
Chemical formula	C6H5PH2
Molar mass	110.09 g/mol
Appearance	Colorless liquid
Odor	foul
Density	1.001 g/cm3
Boiling point	160 °C (320 °F; 433 K)
Hazards
	NIOSH (US health exposure limits):
PEL (Permissible)	none
REL (Recommended)	C 0.05 ppm (0.25 mg/m3)
IDLH (Immediate danger)	N.D.
	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

Phenylphosphine is an organophosphorus compound with the chemical formula C₆H₅PH₂. It is the phosphorus analog of aniline. Like other primary phosphines, phenylphosphine has an intense penetrating odor and is highly oxidizable. It is mainly used as a precursor to other organophosphorus compounds. It can function as a ligand in coordination chemistry.^[2]

Synthesis

Phenylphosphine can be produced by reducing dichlorophenylphosphine with lithium aluminum hydride in ether:

LiAlH₄ + 2C₆H₅PCl₂ → 2C₆H₅PH₂ + Li⁺ + Al³⁺ + 4Cl⁻

This reaction is performed under a nitrogen atmosphere to prevent side reactions involving oxygen.^[3]

Reactions

Oxidation of phenylphosphine with air affords the oxide.^[3]

C₆H₅PH₂ + O₂ → C₆H₅P(OH)₂

Bis(2-cyanoethylphenyl)phosphine, which is of interest as a synthetic intermediate, can be made from phenylphosphine by base-catalyzed allylic addition to acrylonitrile.

C₆H₅PH₂ + 2CH₂=CHCN → C₆H₅P(CH₂CH₂CN)₂

Bis(2-cyanoethylphenyl)phosphine is a useful precursor to 1-phenyl-4-phosphorinanone by base-induced cyclization followed by hydrolysis. Phosphorinanones can be used to prepare alkenes, amines, indoles, and secondary and tertiary alcohols by reduction, Grignard, and Reformatsky reagents. ^[4]

Phenylphosphine reacts with many metal complexes to give complexes and clusters.^[5] It is the precursor to the bridging phosphinidene ligand in certain clusters.

2 (C₆H₅)₂MCl + C₆H₅PH₂ + 3 (C₂H₅)₃N → ((C₆H₅)₂M)₂PC₆H₅ + 3 (C₂H₅)₃N•HCl

Phenylphosphine also have uses in polymer synthesis. Using radical initiations or UV irradiation, polyaddition of phenylphosphine to 1,4-divinylbenzene or 1,4-diisopropenylbenzene will form phosphorus-containing polymers, which have self-extinguishing properties. When mixed with flammable polymers such as polystyrene and polyethylene, the mixed polymer exhibits flame resistant properties.^[6]

References

^ ^a ^b ^c NIOSH Pocket Guide to Chemical Hazards. "#0501". National Institute for Occupational Safety and Health (NIOSH).
^ Svara, Jürgen; Weferling, Norbert ; Hofmann, Thomas "Phosphorus Compounds, Organic" in Ullmann's Encyclopedia of Industrial Chemistry. John Wiley & Sons, Inc, 2008. doi:10.1002/14356007
^ ^a ^b Freedman, Leon D.; Doak, G. O. (1952). "The Reduction of Benzenephosphonyl Dichloride". Journal of the American Chemical Society. 74 (13): 3414–3415. doi:10.1021/ja01133a504.
^ Snider, Theodore E.; Morris, Don L.; Srivastava, K. C.; and Berlin, K. D. (1988). "1-Phenyl-4-Phosphorinanone". Organic Syntheses{{cite journal}}: CS1 maint: multiple names: authors list (link); Collected Volumes, vol. 6, p. 932.
^ Schumann, Herbert; Schwabe, Peter; Stelzer, Othmar (1969). "Organogermyl, stannyl und plumbylphosphine". Chemische Berichte. 102 (9): 2900–2913. doi:10.1002/cber.19691020904.{{cite journal}}: CS1 maint: multiple names: authors list (link)
^ Obata, Takatsugu; Kobayashi, Eiichi; Aoshima, Sadahito; Furukawa, Junji (1994). "Synthesis of new linear polymers containing phosphorus atom in the main chain by the radical polyaddition: Addition polymers of phenylphosphine with 1,4-divinylbenzene or 1,4-diisopropenylbenzene and their properties". Journal of Polymer Science Part A: Polymer Chemistry. 32 (3): 475–483. doi:10.1002/pola.1994.080320309.{{cite journal}}: CS1 maint: multiple names: authors list (link)

[PGCH-1] NIOSH Pocket Guide to Chemical Hazards. "#0501". National Institute for Occupational Safety and Health (NIOSH).

[2] Svara, Jürgen; Weferling, Norbert ; Hofmann, Thomas "Phosphorus Compounds, Organic" in Ullmann's Encyclopedia of Industrial Chemistry. John Wiley & Sons, Inc, 2008. doi:10.1002/14356007

[freedman-3] Freedman, Leon D.; Doak, G. O. (1952). "The Reduction of Benzenephosphonyl Dichloride". Journal of the American Chemical Society. 74 (13): 3414–3415. doi:10.1021/ja01133a504.

[4] Snider, Theodore E.; Morris, Don L.; Srivastava, K. C.; and Berlin, K. D. (1988). "1-Phenyl-4-Phosphorinanone". Organic Syntheses{{cite journal}}: CS1 maint: multiple names: authors list (link); Collected Volumes, vol. 6, p. 932.

[5] Schumann, Herbert; Schwabe, Peter; Stelzer, Othmar (1969). "Organogermyl, stannyl und plumbylphosphine". Chemische Berichte. 102 (9): 2900–2913. doi:10.1002/cber.19691020904.{{cite journal}}: CS1 maint: multiple names: authors list (link)

[6] Obata, Takatsugu; Kobayashi, Eiichi; Aoshima, Sadahito; Furukawa, Junji (1994). "Synthesis of new linear polymers containing phosphorus atom in the main chain by the radical polyaddition: Addition polymers of phenylphosphine with 1,4-divinylbenzene or 1,4-diisopropenylbenzene and their properties". Journal of Polymer Science Part A: Polymer Chemistry. 32 (3): 475–483. doi:10.1002/pola.1994.080320309.{{cite journal}}: CS1 maint: multiple names: authors list (link)

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