Dimethylphosphine oxide explained

Dimethylphosphine oxide is an organophosphorus compound with the formula (CH3)2P(O)H. It is a colorless liquid that soluble in polar organic solvents. It exists as the phosphine oxide, not the hydroxy tautomer. A related compound is diphenylphosphine oxide. Both are sometimes called secondary phosphine oxides.

Preparation

The compound arises by the hydrolysis of chlorodimethylphosphine:[1]

Me2PCl + H2O → Me2P(O)H + HClMethanol, but not ethanol, can also be used in place of water, the co-product being methyl chloride.

Since chlorodimethylphosphine is dangerous to handle, alternative routes to dimethylphosphine oxide have been developed. A popular method starts with diethylphosphite, according to the following idealized equations:[2]

(C2H5O)2P(O)H + 3 CH3MgBr → (CH3)2P(O)MgBr + 2 MgBr(OC2H5) + CH4

(CH3)2P(O)MgBr + H2O → (CH3)2P(O)H + 2 MgBr(OH)

Reactions

Chlorination gives dimethylphosphoryl chloride. It undergoes hydroxymethylation with formaldehyde.

Me2P(O)H + CH2O → Me2P(O)CH2OHMany aldehydes effect a similar reaction.

References

  1. Kleiner, H. J.. Herstellung und Umsetzungen von Dimethylphosphinoxid (Preparation and Reactions of Dimethylphosphine Oxide). Justus Liebigs Ann. Chem.. 1974. 751-764. 10.1002/jlac.197419740507.
  2. Hays, H. R.. Reaction of diethyl phosphonate with methyl and ethyl Grignard reagents. J. Org. Chem.. 1968. 33. 3690-3694. 10.1021/jo01274a003.