Wiley InterScience Backfile Collection 1832-2000
Chemistry and Pharmacology
The rate of alkylation of (2-N,N-dimethylaminophenyl)diphenylphosphine with benzyl bromide in chloroform is faster than that of the corresponding reaction of (4-N,N-dimethylaminophenyl)diphenylphosphine. This result is discussed in terms of a through-space N2p-P(IV) interaction for the former.The rate of alkaline cleavage of benzyl(4-N,N-dimethylaminophenyl)diphenylphosphonium bromide, which gives toluene, is slower than the rate of alkaline cleavage of benzyl(2-N,N-dimethylaminophenyl)diphenylphosphonium bromide, which gives dimethylaniline. This result is also discussed in terms of the through-space N2p-P(IV) interaction.The 31P NMR spectra of a series of ortho-dimethylamino-substituted triarylphosphines and benzyltriarylphosphonium halides show that the phosphorus atom is more shielded than in the corresponding para-dimethylamino compounds, as anticipated on the basis of an N2p-P(IV) interaction for the former.
Type of Medium: