On the Facile P-C Bond Break

Theoretical Studies on the Mechanism of C−P Bond Cleavage of a Model α-Aminophosphonate in Acidic Condition

“…Three different reaction paths could be suggested for the P−C bond cleavage of DMABP in acidic conditions (Schemes −4). All of them were suggested before using the available experimental evidence. ,, The first mechanism (Scheme ) is the decomposition of the P−C bond due to the protonation of oxygen. While the second probable mechanism (Scheme ) involves hydrogen transfer from protonated anilino-nitrogen to the phosphorus atom, the third one (Scheme ) assumes the cleavage of the neutral molecule into cations.…”

“…The analysis of concentrations of components in solution indicates that at least a large part of phosphonic acid originates from the direct decomposition of diester. Additionally, as indicated by Deron et al the initiation of the reaction takes place through the protonation of oxygen of the phosphonic group. The amino group of the aniline part is a competitive site for such a protonation, and experimental studies indicated a correlation between the acidity of amino group and the kinetics of the reaction .…”

“…Additionally, as indicated by Deron et al the initiation of the reaction takes place through the protonation of oxygen of the phosphonic group. The amino group of the aniline part is a competitive site for such a protonation, and experimental studies indicated a correlation between the acidity of amino group and the kinetics of the reaction . On the basis of the available experimental evidence, the mechanism of P−C bond decomposition is assumed to proceed through three consecutive steps, namely, protonation of phosphonates, P−C bond cleavage, and conversion of transition products into final derivatives of phosphonic acid.…”

“…It was shown that the P−C bond cleavage of diethyl esters of (α-anilinobenzyl)phosphonates takes place in acidic environment. , Time dependent NMR (nuclear magnetic resonance) studies of these compounds in aqueous acidic media and at a high temperature indicated the presence of diester, monoester, (α-anilinobenzyl)phosphonates, and phosphonic acid (Figure 1s, Supporting Information). The analysis of concentrations of components in solution indicates that at least a large part of phosphonic acid originates from the direct decomposition of diester.…”