56351-16-7Relevant articles and documents
SYNTHESE ET REDUCTION CHIMIQUE DE SELS DE VINYLENE-1,2 ET BUTADIENYLENE-1,4 BIPHOPHONIUMS
Cristau, Henri-Jean,Labaudiniere, Lydie,Christol, Henri
, p. 359 - 372 (2007/10/02)
1,2-vinylene- and 1,4-butadienylene-biphosphonium salts with labile groups on phosphorus (e.g. benzyl, 2-cyanoethyl, allyl or benzyl) are synthetized in the reaction of the corresponding tertiary phosphines with acetyl- or vinylacetyl bromide.When the salts are reacted with lithium aluminium hydride and with alkaline alcoholates or cyanides, the unsaturated bridge between the two phosphorus atoms is selectively cleaved to afford one or several tertiary phosphines.For each kind of cleavage a mechanism is proposed and discussed: with alcoholate or cyanide ions, the reaction gives rise to an ethynylphosphonium intermediate which accounts for the formation of the reaction products.