Acetaldehyde–Ammonia Interaction: A DFT Study of Reaction Mechanism and Product Identification

Abstract

The product of acetaldehyde and ammonia reaction, namely, 2,4,6-trimethyl-1,3,5-hexahydrotriazine trihydrate, was synthesized and identified using a combination of experimental (NMR spectroscopy, IR spectroscopy, melting point determination) and DFT-based theoretical approaches. A reaction mechanism was proposed. The reaction was shown to proceed via the formation of aminoalcohol, imine, and geminal diamine intermediates accompanied by cyclization of these species. The calculation results allowed us to build a potential energy surface of the acetaldehyde and ammonia interaction and determine the most energetically favorable pathway to yield acetaldehyde ammonia trimer. The reaction product was found in an energy minimum (-53.5 kcal/mol).

Catalytic Non-redox Carbon Dioxide Fixation in Cyclic Carbonates

“…In particular, we examined a commonly reported procedure to form an aldehyde ammonia trimer. 37,38 We speculated that the one-pot reaction of terephthalaldehyde and ammonium chloride salt would form a new porous material containing cyclic amines.…”

Metal-Ion- and Hydrogen-Bond-Mediated Interstellar Prebiotic Chemistry: The First Step in the Formose Reaction

“…In this context of using NH 3 as the small molecule, it should be mentioned that there are several computational and experimental studies on the interaction of carbonyl compounds and ammonia both in solution and in ISM. − It is very much possible that with NH 3 the more thermodynamically advantageous interaction due to the formation of C–N bonds can render NH 3 useless in the formose reaction.…”

The reaction of acetaldehyde, glyoxal, and ammonia to yield 2-methylimidazole: thermodynamic and kinetic analyses of the mechanism

“…In our previous works we presented the results of the studies separately for the acetaldehyde and ammonia reaction leading to the formation of THT, 19 and the glyoxal and ammonia reaction with the formation of the C–N oligomers. 20 Namely, the mechanisms of formation of THT and C–N oligomers were determined.…”

“…Thus, our research purpose was to determine the most thermodynamically and kinetically favorable reaction pathways and intermediate products in the reaction of glyoxal, acetaldehyde, and ammonia with the formation of 2-methylimidazole in aqueous solution by performing electronic structure calculations. This work was partially based on the results of our previous studies to determine the favorable routes of the reaction of acetaldehyde with ammonia leading to the formation of 2,4,6-trimethyl-1,3,5-hexahydrotriazine (THT), 19 and the reaction of glyoxal with ammonia with the formation of imidazole C-N oligomers. 20…”