57057-06-4Relevant academic research and scientific papers
Mechanism of the Reaction of Trialkyl Phosphites with α-Halogenoacetophenones in Alcoholic Solvents
Petnehazy, Imre,Keglevich, Gyoergy,Toeke, Laszlo,Hudson, Harry R.
, p. 127 - 132 (2007/10/02)
Second-order rate constants and activation parameters have been determined for the reactions of trialkyl phosphites in alcoholic media with α-chloro- or α-bromo-acetophenones having various substituents in the benzene ring (3,4-Me2, 4-Me, H, 4-Cl, and 4-I).Linear Hammett plots are consistent with the involvement of a common first intermediate in the rate-determining stage, leading to the formation of vinyl phosphate, α-hydroxyphosphonate, and acetophenone.The results provide the first kinetic evidence in support of the initial formation of the previously suggested betaine as a common intermediate in alcoholic solution.Further reaction then involves rearrangement to give the vinyloxyphosphonium species (and hence the Perkow product) or protonation followed by dealkylation to give the α-hydroxyphosphonate.Evidence for the possible formation of dehalogenated ketone via solvolysis of the α-hydroxyphosphonium intermediate is also presented.
Novel Synthetic Aspects of the Phosphonate-Phosphate-Rearrangement. II. Synthesis of Enolphosphates from 1-Oxoalkanphosphonates and Sulfur-Ylides
Hammerschmidt, Friedrich,Zbiral, Erich
, p. 1015 - 1024 (2007/10/02)
Acylphosphonates 1 react with Sulfur-ylides 2 to give enolphosphates 3 and phosphonophosphates 4.The product ratio of 3 and 4 is determined by the substituent R3.If R3 is not electronwithdrawing the phosphonophosphate 4 is the sole reaction product. - Keywords: Acylphosphonates, behaviour towards S-ylides; Rearrangement of α-hydroxyphosphonates
