110823-07-9Relevant articles and documents
Volumes of Reaction for the Formation of Some Analogues of Tetrahedral Intermediates
Isaacs, Neil S.,Rzepa, Henry S.,Sheppard, Richard N.,Lobo, Ana M.,Prabhakar, Sundaresan,Merbach, A. E.
, p. 1477 - 1482 (2007/10/02)
Two reactions which comprise equilibrium addition of a protic species to a carbonyl group, the hydroxyketone-hemiacetal interconversion (1a) = (1b), and the thiol addition of acetyl cyanide (2a) = (2b), have been studied by n.m.r. and their spectra thoroughly analysed.Equilibrium constants have been measured as a function of pressure to obtain volumes of reaction which relate to the formation of the 'tetrahedral intermediate' of ester hydrolysis.The intramolecular reaction is shown to have a much less negative volume change than the intermolecular analogue, pointing to the important contribution to ΔV and to ΔV(excit.) of molecular bond formation.
