M. Oki et al., Dimensiosolvatic effects. VI. Rates of ionization of 2-fluoro-4,4,5,5-tetramethyl-1,3-dioxolane: Dimensiosolvatic vs. hydrogen-bond effects, B CHEM S J, 72(6), 1999, pp. 1343-1349
The title compound was prepared by treating 4,4,5,5-tetramethyl-1,3-dioxola
n-2-yl acetate with cesium fluoride. Rates of ionization of this compound w
ere determined in various solvents by the dynamic NMR technique. While effe
cts due to polarity as well as solvent molecular size were observed in many
solvents examined, the rates in solutions of which the solvent is capable
of being an acceptor in hydrogen-bond formation with the substrate were unu
sually small, and this effect is diminished in bulky solvents. Such results
are attributed to stabilization of the original state due to hydrogen-bond
formation with the acidic C(2) - H group of the substrate in those solvent
s. The hydrogen-bond formation is hindered by the steric effects in bulkier
solvents than in smaller solvents. The rates of contact ion pair and solve
nt-separated ion pair formations should be independently determined in 2-fl
uoro-4,4,5,5-tetramethyl-1,3-dioxolane, but so far no clear example which s
hows that the rate-limiting step is the solvent intervention has been found
, even though various bulky solvents were examined.