REACTIVITY OF THE ACIDS OF TRIVALENT PHOSPHORUS AND THEIR DERIVATIVES. PART VIII.∗ REACTIVITY OF THE >P-O⁻ NUCLEOPHILES TOWARD ARYLMETHYLBROMIDE SYSTEMS. FURTHER EVIDENCE FOR THE X-PHILIC SUBSTITUTION/SET TANDEM MECHANISM

Abstract

The reaction of sodium dimethyl and diisopropyl phosphite, as well as dibenzylphosphinite with bromodiphenylmethane. 9-bromofluorene and triphenylmethyl bromide was studied in detail by (1) isolating and identification of all products, (2) studying the effects of the solvents, as well as light on product distribution. The results of the experiments carried out are compatible with the proposed X-philic substitution/SET tandem mechanism. It was demonstrated that the triphenylmethyl radical can couple with the diethyl phosphite anion producing diethyl triphenylmethylphosphonate in the chain process.

Key Words:

• bromodiphenylmethane
• triphenylmethyl bromide
• 9-bromofluorene
• Michaelis-Becker reaction
• X-philic substitution/SET tandem mechanism