REACTIVITY OF THE ACIDS OF TRIVALENT PHOSPHORUS AND THEIR DERIVATIVES. PART IX. THE >P-0⁻ AND >P-S⁻ NUCLEOPHILES IN THE REACTIONS OF HALOPHILIC SUBSTITUTION

Abstract

The reaction of the > P-Y⁻ (Y = O; S) nucleophiles with the compounds possessing a C-Br bond and electron-withdrawing groups is described. The isolation of the products derived from dialkyl bromophosphates, the results of the ³¹P NMR studies, as well as the isolation of bromothiophosphate from the reaction mixture of > P-S⁻ nucleophile and methyl α-bromocarboxylate, are further evidence for halophilic substitution as the principal process in the X-philic substitution/SET tandem mechanism operating in the reaction of these phosphorus nucleophiles with the bromederivatives possessing electron-withdrawing groups.

Key Words:

• ³¹P NMR studies
• >P-Y⁻ nucleophiles
• Michaelis—Becker reaction
• X-philic substitution/SET tandem mechanism
• Faculty of Chemistry is gratefully acknowledged