Diallylphenylphosphine oxide

The mode of reaction of alkyl- or arylphosphonic halides with Grignard reagents in ether is most often unpredictable. Bis(p-tolyl)phenyl-phosphine oxide is reported as the major product from phenylphos-phonic dichloride and the required quantity of Grignard reagent (148). Attempted synthesis of diallylphenylphosphine oxide under similar circumstances gave only undistillable black oils and tars (13). Equimolar quantities of reactants furnished diphenylphosphinic acid in good yield plus a small quantity of triphenylphosphine oxide (45). 

Ozonized oxygen passed at -78° through a soln. of diallylphenylphosphine oxide in methanol until after ca. 4 hrs. a blue color appears, the solvent evaporated, the residue treated at -78° with 97%-formic acid and 30%-H2O2, stirred at room temp, overnight, finally refluxed 2 hrs. -> 2,2 -(phenylphosphinylidene)diacetic acid. Y 83%. J. L. Eichelberger and J. K. Stille, J. Org. Chem. 36, 1840 (1971). 

The formation of a strong intramolecular dative P—B bond in the hydro-borylation reaction of diallylphenylphosphine with triethylaminophenyl-borane results in a bicyclic product, l-borata-5-phosphoniabi-cyclo[3,3,0]octane (204) [Eq. (145)] (64JA5045). The presence of the dative bond in this compound is indicated by an NMR study and by its stability to hydrolysis and oxidation. 

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