Trans-N-alkylation Covalent Exchanges on 1,3,4-Trisubstituted 1,2,3-Triazolium Iodides

1,3,4-Trisubstituted 1,2,3-triazolium salts having either aliphatic or benzylic substituents at the N-1 and N-3 positions were synthesized in two steps involving: i) copper(I) catalyzed azide-alkyne 1,3-dipolar cycloaddition (CuAAC), and ii) N-alkylation of the 1,2,3-triazole intermediates. Trans-N-alkylation reactions in bulk and in the presence of excess methyl iodide were monitored by 1H NMR spectroscopy for each 1,2,3-triazolium molecular model. By assigning the different formed species and their respective evolution with time, it was possible to conclude that trans-N-alkylation exchange reactions are significantly faster for benzylic substituents than for aliphatic ones. Furthermore, the exchange reactions are noticeably faster at the N-3 position than at the N-1 position most likely due to the steric hindrance induced by the neighboring C-4 substituent. The kinetics of trans-N-alkylation reactions are thus influenced by both the chemical nature of the N-1 and N-3 substituents and the regiochemistry of the 1,2,3-triazolium group. This provides important structural design rules to improve the properties of thermosetting covalent adaptable networks involving trans-N-alkylation of 1,2,3-triazolium salts.