29877-01-8Relevant articles and documents
Reestimation of the Taft's substituent constant of the pentafluorophenyl group
Korenaga, Toshinobu,Kadowaki, Koichi,Ema, Tadashi,Sakai, Takashi
, p. 7340 - 7343 (2007/10/03)
The Taft's substituent constant of the pentafluorophenyl group (σ*C6F5)) was reestimated to be 1.50 by correlation between IR spectral data (vC=O) and σ* constants for a series of esters (involving the pentafluorobenzyl group) of 3-phenylpropanoic acid and butanoic acid. The possibility of the disturbance of the correlation by the intramolecular π-π interaction between C 6F5 and C6H5 groups in pentafluorobenzyl 3-phenylpropanoate was excluded by ab initio and DFT calculations of the stable conformations and their carbonyl frequencies. The reestimated σ* (C6F5) value was used for calculation of the pKa value of pentafluorobenzyl alcohol [14.5 (or 14.3)].
Alkyl Group Effects on the Rate Constants and Equilibrium Constants for Formation of Cyclic Tetrahedral Intermediates
Santry, Linda J.,Azer, Salwa,McClelland, Robert A.
, p. 2909 - 2914 (2007/10/02)
2-Hydroxy-2-alkyl-1,3-dioxolanes T are the cyclic intermediates of the degenerate intramolecular ester interchange reactions of ethylene glycol monoalkanoates A, in which alkanoyl groups transfer from one end of ethylene glycol to the other.This study reports equilibrium constants for the cyclization AT to the tetrahedral intermediate stage with 10 alkanoate derivatives.These equiilibrium constants, which when written as / are all large (1 E7-1 E9) in favor of the ring opened form, were obtained as the ratio of rate constants for equilibration occuring with H+ catalysis.Rate constants for the ring opening of T were directly measured through a study of kinetics of the hydrolysis of 2-methoxy-2-alkyl-1,3-dioxolane ortho esters.These hydrolysis proceed via T, and under acid conditions the breakdown of this intermediate is rate-limiting.Rate constants in the ring-closing direction were obtained by preparing HOCH2CD2OOCR and, with the use of 1H NMR spectroscopy, measuring the kinetics of isomerization to an equilibrium mixture with RCOOCH2CD2OH.The reaction under investigation is an intramolecular analogue of H+-catalyzed alkanoate ester hydrolysis, whose rate constant define the steric substituent parameter Es.The ring-closure rate constant for A -> T do show an excellent correlation with Es.However, the rate constants for ring-opening T -> A and the overall equilibrium constant are badly correlated, showing quite different behavior for series with α and β branching in the alkyl group.Thus, for this system the Es parameter does not correlate free energy differencies between the acyl derivative and tetrahedral intermediate.It is only the free energy differences between the acyl form and the transition state leading to the intermediate that fit Es.