76095-09-5Relevant academic research and scientific papers
Hewitt reaction revisited
Afarinkia, Kamyar,Yu, Hiu-Wan
, p. 781 - 783 (2007/10/03)
A range of alkyl phenylphosphonites are prepared from the reaction of phenylphosphinic acid with the corresponding alkyl chloroformates. A mechanism for this reaction is proposed.
SILICON-PHOSPHORUS ANALOGIES. NUCLEOPHILIC CATALYSIS IN THE ALCOHOLYSIS OF CHLOROPHOSPHORUS DERIVATIVES
Corriu, Robert J. P.,Lanneau, Gerard F.,Leclercq, Dominique
, p. 1959 - 1974 (2007/10/02)
The mechanism of the alcoholysis of chlorophosphonates and chlorophosphates in presence of nucleophilic catalysts like hexamethylphosphotriamide, pyridine and N-methylimidazole is discussed on the basis of kinetic and stereochemical results.We have proposed a mechanism for the reaction, which is governed by entropy, involving reaction of the alcohol with a pentacoordinated intermediate.This accounts for the differences in the stereochemical outcome and the rate equation which can be derived for the reaction with a variety of substrates in addition to the absence of common ion + solvent effects observed.
SILICON-PHOSPHORUS ANALOGIES. PARTICIPATION OF EXTERNAL NUCLEOPHILES TO ACTIVATED PROCESSES OF RACEMIZATION AND HYDROLYSIS OF CHLOROPHOSPHONO DERIVATIVES
Corriu, R. J. P.,Lanneau, G. F.,Leclercq, D.
, p. 1617 - 1626 (2007/10/02)
Kinetic and stereochemical studies show nucleophilic assistance by dimethylformamide (DMF), dimethylacetamide (DMA), hexamethylphosphotriamide (HMPT) and N-methylimidazole (NMI) in racemization and solvolysis of menthylchloro(phenyl)phosphonate, 1a, and O-ethylchloro(phenyl)thiophosphonate, 2.Similar orders of nucleophilic reactivity (Nu = NMI >> HMPT > DMF> DMA), and identical rate laws (vrac = k 2 and vH2O = k') are consistent with a common mechanism, governed by entropy (-60 u.e/= -40 u.e.).Analogies between reaction mechanisms at silicon and phosphorus are clearly evidenced.A two step process, involving rate-determining attack on a pentacoordinate complex is discussed.
