In solution, formaldehyde and ammonia co-oligomerize into a wide array of products. The observed product distribution is dependent on the reaction conditions such as relative concentration, pH, and temperature. In order to understand how different conditions influence the product distribution, we use quantum chemical calculations to map the thermodynamic and kinetic landscape of the myriad chemical reactions that can take place. This allows us to identify low barrier pathways, key intermediates, kinetic traps, and therefore enable us to design the necessary reaction conditions to favor a desired suite of products. In particular we have outlined the most likely pathways to the formation of hexamethylenetetramine (HMT), one of the main observed products in the reaction. Our computational results also suggest the identity and reaction pathway of products and intermediates observed by mass spectrometry. The chemistry of these reactions is pertinent to industrial chemists synthesizing chemical feedstock compounds such as HMT, atmospheric chemists studying organic aerosol formation and origin-of-life research chemists studying prebiotic reaction mechanisms.

Mapping the energy landscape of formaldehyde and ammonia co-oligomerization

248th National Meeting (2014)

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