REACTION DES CETONES ACETYLENIQUES AVEC LES PHOSPHITES ET LES AMINOPHOSPHITES EN PRESENCE DE REACTIFS DE PIEGEAGE PROTIQUES. SYNTHESE, MECANISME DE FORMATION ET STEREOCHIMIE D'YLURES DE PHOSPHORANES MONOCYCLIQUES ET DE SPIROPHOSPHORANES.

Article abstract of DOI:10.1016/0040-4020(86)80007-2

Cyclic and acyclic trivalent phosphorus compounds (1, 2, 3, 4) were reacted with activated carbonyl acetylenic compounds as 1-4-diphenyl-2 butyne-1,4-dione; 1-Methoxy-phenyl-4-Phenyl-2-Butyne-1,4-dione; 4-oxo-4-phenyl-Methyl-2-butynoate and 1,3-diphenyl-1-propyne-2-one.All these reaction were performed in presence of protic trapping reagents ZH such as methanol a, phenol b or phtalimid c.All these reactions lead to a very unstable 1,3 dipolar species like which is not detected even at low temperature.This species is protonated instantaneously with the protic trapping reagent ZH giving the following intermediate .Further, Z^- may attack the phosphorus atom with formation of a vinylic phosphorane: compounds series A and C, or Z^- may attack the electrophilic center of the keto group leading either to ylid formation i.e. compounds serie B or to spirophosphoranes formation i.e. compounds serie D.Mechanisms involved in these reactions are studied.