| Abstract
| - A series of N-4-R-benzylpivalamides (R = MeO, Me, H, CF3, and NO2) was nitrosated using astandardized solution of N2O4 in CDCl3 at −40 °C. The reactions, which produced the correspondingN-4-R-benzyl-N-nitrosopivalamides, were followed by 1H NMR spectroscopy. The rate of nitrosationwas found to vary in a systematic way with the nature of the 4-R-group on the aromatic ring.Thus, electron-releasing groups increased the rate of the reaction, whereas electron-withdrawingones decelerated N-nitrosation. In a similar fashion, the nitrosations were accelerated in polarsolvents but were slower in solvents of low polarity. The sensitivities of N-nitrosation to theseintra- and intermolecular electronic effects are compared to those from a previous study examiningthe dependence of the kinetics of nitrosoamide thermolyses on the same factors.
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