the more basic the amine—the more favorable is the reaction.

European Journal of Mass Spectrometry

The reactions of various amines (RNH2: R = H, CH3, C2H5 and i-C3H7) with the methoxy methyl cation (CH2OCH3) have been investigated using a Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer, and the experimental results are complemented with ab initio calculations. The amines show clear trends in their reactivities with variable degree of: (1) nucleophilic substitution, (2) addition-elimination and (3) hydride abstraction. In all cases, addition–elimination dominates over nucleophilic substitution, and for R ≠ H the observed reactions occur at the collisional limit. The potential energy profiles for all three reaction types correlate with the basicities of the amines: i.e. the more basic the amine—the more favorable is the reaction. In other words, nucleophilicity follows basicity in the gas phase.

the more basic the amine—the more favorable is the reaction.

Trends in Alkyl Substituent Effects on Nucleophilic Reactions of Carbonyl Compounds: Gas-Phase Reactions between Amines and the Methoxy Methyl Cation