The specific rates of solvolysis of n-octyl fluoroformate have been measured at 24.2 °C in 28 pure and binary solvents. For the 23 solvents for which both NT (solvent nucleophilicity) and YCl (solvent ionizing power) values are known, a correlation using the two-term Grunwald–Winstein equation leads to sensitivities towards changes in the two scales of 1.80 ± 0.13 (l value) and 0.79 ± 0.06 (m value), respectively. For seven solvents, a parallel study was made of n-octyl chloroformate solvolysis and F : Cl specific rate ratios were, in most instances, above unity, consistent with the association step of an association–dissociation (addition–elimination) pathway being rate-determining.
Journal of the Chemical Society, Perkin Transactions 2
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