K. Okamoto, H. Kushiro, I. Nitta
Aug 1, 1967
Citations
0
Influential Citations
5
Citations
Journal
Bulletin of the Chemical Society of Japan
Abstract
The rates of the bimolecular nucleophilic substitution (SN2 reactions) of phenacyl bromide with sodium para-substituted phenoxides, sodium para-substituted benzoates, and sodium aliphatic carboxylates have been measured in 50% aqueous acetone at 10–70°C. Linear free-energy relationships between the nucleophilic reactivities and basicites (expressed in terms of the pKa’s of the conjugate acids) have been observed in the reactions of para-substituted aromatic nucleophiles, whereas no linear relationships have been seen in the reactions of aliphatic carboxylates except in the cases of sodium acetate, sodium formate, and sodium monochloracetate. An equation, logk2=αpKa+const., has been applied to these reaction series and to the 30 literally-known series of SN2 reactions. The correlation coefficients have then been calculated as a measure of the precision of these linear relationships. Hammett’s ρ values for the reactions of para-substituted aromatic nucleophiles have also been calculated, and the several fac...