Dihydrophenophosphazine ring system

Abstract

The reaction of diarylamines with phosphorus trichloride followed by treatment of the reaction mixtures with water has been employed to synthesize the secondary phosphine oxides 1, 3, 5, and 7 and the spirophosphonium chlorides 2, 4, 6, and 8. A mechanism for the formation of the oxides has been proposed. Phosphinic acids have been prepared by oxidation of the oxides. The JV-methyl derivative 12 has been obtained by a variant of the Friedel-Crafts reaction in which (V-methyl-di-p-tolylamine and phosphorus trichloride were heated together in the presence of aluminum chloride and the reaction mixture was then hydrolyzed and oxidized.

Polycyclic carbon-phosphorus heterocycles

“…Most aspects of the stereochemistry of these systems have already been treated.112•227 Later, a more rapid method for the preparation of diphenyldiphosphanthrene (83b) was de-vised230 which involved the interaction of phenyldilithiophosphine (prepared from lithium and diphenylphosphonous dichloride or n-butyllithium and phenylphosphine in THF) with o-dihalobenzenes at low temperature. The diphosphanthrene 83b (isolated as the dibenzyl salt 85b) was, however, obtained in a much lower yield compared to the earlier method, but the reaction afforded additionally the novel 1,2,3-triphenyl-1,2,3-triphosphaindane (86d), mp [184][185][186]…”