The quaternisation reaction of phosphines and amines in aliphatic alcohols. A similarity analysis using the isokinetic, isosolvent and isoselective relationships

摘要: Accurate second-order rate constants were measured at 5 K intervals in the temperature range 298.15–328.15 for quaternisation reaction of triethylphosphine with iodoethane methanol, ethanol, propan-1-ol and butan-1-ol. These data are complemented previously reported triethylamine same solvents similar temperatures. Each these two series is analysed terms isokinetic relationship (IKR) respect to solvent variation isosolvent (ISoR) variation, using latter case five different empirical scales. Statistically validated IKR ISoR have been found both series. The resulting temperatures 347 (phosphine series) 730 (amine discussed Linert's theory relationship. best correlation obtained Dimroth–Reichardt ETN scale phosphine Kamlet–Taft αKT amine It demonstrated that no real can be envisaged as having characteristics an solvent. selectivity nucleophiles attack on examined by treating together isoselective (ISeR). 289 K, which close value 302 predicted Exner Giese's formula basis individual A novel ISeR analysis performed. reveals most appropriate describing this series, it feasible find new equation developed predicting parameter from parameters shown yield realistic values. present similarity shows there significant differences between courses reactions. On experimentally determined isoparameter values, liquid alcohols proposed follows a classic bimolecular nucleophilic substitution pathway, whereas desolvation molecules has taken into account describe mechanism original Menshutkin reaction.