Bis(diethylamino)chlorophosphine

Bis(diethylamino)chlorophosphine
Names
	Other names N,N,N',N'-tetraethylphosphorodiamidous chloride
Identifiers
CAS Number	685-83-6;
3D model (JSmol)	Interactive image;
ChemSpider	2015150;
ECHA InfoCard	100.155.896
PubChem CID	3316562;
CompTox Dashboard (EPA)	DTXSID10391390;
	InChI InChI=1S/C6H4Cl4P2/c7-11(8)5-3-1-2-4-6(5)12(9)10/h1-4H Key: IGYHSFVSIYJSML-UHFFFAOYSA-N;
	SMILES C1=CC=C(C(=C1)P(Cl)Cl)P(Cl)Cl;
Properties
Chemical formula	C8H20Cl4N2P
Molar mass	210,687
Appearance	colorless liquid
Boiling point	87–90 °C (189–194 °F; 360–363 K) 2 torr
Hazards
	GHS labelling:
Pictograms
Signal word	Danger
Hazard statements	H314
Precautionary statements	P260, P264, P280, P301+P330+P331, P303+P361+P353, P304+P340, P305+P351+P338, P310, P321, P363, P405, P501
	Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). Infobox references

Bis(diethylamino)chlorophosphine is an organophosphorus compound with the formula (Et₂N)₂PCl (Et = ethyl). This colorless liquid serves as a masked source of PCl₂⁺.

Synthesis and reactions

The compound is prepared by treatment of phosphorus trichloride with diethylamine:

4 Et₂NH + PCl₃ → (Et₂N)₂PCl + 2 Et₂NH₂Cl

Illustrative of its utility is the synthesis of 1,2-bis(dichlorophosphino)benzene. The synthesis involves sequential lithiation of 1,2-dibromobenzene followed by treatment with (Et₂N)₂PCl:^[1]

C₆H₄Br₂ + BuLi → C₆H₄(Br)Li + BuBr

C₆H₄(Br)Li + (Et₂N)₂PCl → C₆H₄(Br)(P(NEt₂)₂) + LiCl

C₆H₄(Br)(P(NEt₂)₂) + BuLi → C₆H₄(Li)(P(NEt₂)₂) + BuBr

C₆H₄(Li)(P(NEt₂)₂) + (Et₂N)₂PCl → C₆H₄[P(NEt₂)₂]₂ + LiCl

Finally, the amino substituents are removed using hydrogen chloride:

C₆H₄[P(NEt₂)₂]₂ + 8 HCl → C₆H₄(PCl₂)₂ + 4 Et₂NH₂Cl

References

^ Reetz, Manfred T.; Moulin, Dominique; Gosberg, Andreas (2001). "BINOL-Based Diphosphonites as Ligands in the Asymmetric Rh-Catalyzed Conjugate Addition of Arylboronic Acids". Organic Letters. 3 (25): 4083–4085. doi:10.1021/ol010219y. PMID 11735590.

[1] Reetz, Manfred T.; Moulin, Dominique; Gosberg, Andreas (2001). "BINOL-Based Diphosphonites as Ligands in the Asymmetric Rh-Catalyzed Conjugate Addition of Arylboronic Acids". Organic Letters. 3 (25): 4083–4085. doi:10.1021/ol010219y. PMID 11735590.

[1]