| 15103101 |
Bache-Andreassen L, Uggerud E: Trends in alkyl substituent effects on nucleophilic reactions of carbonyl compounds: gas phase reactions between amines and the methoxy methyl cation. Eur J Mass Spectrom (Chichester
The reactions of various amines (RNH (2); R = H, CH (3), C (2) H (5) and i-C (3) H (7)) with the methoxy methyl cation (CH (2) OCH (3)(+)) have been investigated using an FT-ICR mass spectrometer, and the experimental results are supplied 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 not equal 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; the more basic amine-the more favourable is the reaction; in other words: nucleophilicity follows basicity in the gas phase. |
6(0,0,1,1) |