1474-93-7Relevant academic research and scientific papers
Reaction of Triphenylphosphine Radical Cation with 1,3-Dicarbonyl Compounds: Electrochemical One-Step Preparation of Dioxomethylenetriphenylphosphoranes
Ohmori, Hidenobu,Maeda, Hatsuo,Tamaoka, Mie,Masui, Masaichiro
, p. 613 - 620 (2007/10/02)
Electrochemical oxidation of Ph3P (1) in MeCN in the presence of 1,3-dicarbonyl compounds, R1COCH2COR2 (3), with HClO4 as the supporting electrolyte resulted in the formation of the phosphonium salts, Ph3P+ -CH(COR1)COR2 ClO4- (4), provided that R1 and/or R2 is a phenyl group.On the other hand, electrolysis in CH2Cl2 with 2,6-lutidinium perchlorate gave the phosphoranes, Ph3P=C(COR1)COR2 (5), directly from 1 and 3 in fair to excellent yields: in this case, R1 or R2 need not necessarily be a phenyl group.Thus, the electrolysis is shown to be a convenient method to prepare 5 in a single step.Plausible processes for the formation of 4 and 5 are proposed, involving the reaction of electrochemically generated Ph3P+. with the enol form of 3 as the keystep.Keywords - triphenylphosphine; 1,3-dicarbonyl compound; dioxomethyltriphenylphosphonium perchlorate; dioxomethylenetriphenylphosphorane; electrochemical oxidation; constant current electrolysis
