Interpretation of Dispersion Phenomena in Grunwald-Winstein Correlation for Solvolyses of Naphthoyl Chloride

Solvolyses rate constant of 1- and 2- naphthoyl chlorides ( 1 and 2) are reported for aqueous binary mixtures with methanol, ethanol, fluorinated alcohol, acetonitrile and dioxane. Kinetic solvent isotope effects (KISE) in methanol and product selectivities (S) of 2-naphthoyl chloride ( 2) in alcohol-water are also reported. Dispersions in Grunwald-Winstein correlations (r 0.901) are discussed by multiple regression analysis incorporating ionizing power (YCl) scale and rate-rate profiles. Major causes for these phenomena are investigated as an aromatic ring solvation effects, in conjunction with weakly nucleophilic solvation effects (SN2 character), for solvolyses of 1 and for solvolyses of 2, as dual reaction channels, described as S N1-SN2 and SAN-SN2 processes. Distinct border lines between the two pathways are derived from solvolyses rates of 2 in 18 solvent using the results of log(k/ko) = mYCl + lNT + hI plot with values of 1.13 for m, 0.37 for l and 0.15 for h value in 5 aqueous fluorinated alcohol mixtures. Using rate-product correlation, the validity of a third order model based on a general base catalyzed by solvent and contribution from these rate constants, kaa, kaw and kwa, are investigated for S AN/SN2 solvolyses of 2 favored in more rich alcohol media and gradual addition of water to alcohol solvent shows a great shift away from stoichiometric solvation to predominantly medium effects. Rate-rate correlation between solvolyses of 2 and trimethyl acetylchloride ( 5) with alkyl group in the 29 aqueous solvent mixtures shows appreciable linearity (slope = 0.84, r = 0.987), caused by the same pathway (SN1-SN2 process), even if this correlation coincides with appreciable dispersion (different solvation effect).

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