Synthesis of Pyrimidines and Triazines in Ice: Implications for the Prebiotic Chemistry of Nucleobases

Abstract: From urea to nucleobases: Freeze–thaw cycles in urea (1) solutions under methane/nitrogen atmospheres lead, with application of an energy source, to the synthesis of pyrimidines (mainly cytosine (2) and uracil (3)), triazines (such as cyanuric acid (4)), and adenine. This synthesis appears to be dependent on the atmosphere and the freezing conditions. At room temperature, hydantoin (5) is obtained. However, a freezing urea/water system subjected to an energy source under an inert atmosphere generates s-triazines.

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Herein, we report the efficient synthesis of RNA bases and functionalized s-triazines from 0.1 M urea solutions in water after subjection to freeze–thaw cycles for three weeks. The icy solution was under a reductive, methane-based atmosphere, which was subjected to spark discharges as an energy source for the first 72 h of the experiment. Analysis of the products indicates the synthesis of the s-triazines cyanuric acid, ammeline, ammelide, and melamine, the pyrimidines cytosine, uracil, and 2,4-diaminopyrimidine, and the purine adenine. An experiment performed as a control at room temperature, with the urea solution in the liquid phase and with the same atmosphere and energy source, led to the synthesis of hydantoins and insoluble tholin, but there was no evidence of the synthesis of pyrimidines or triazines. The synthesis of pyrimidines from urea is possible under a methane/nitrogen atmosphere only at low temperature, in the solid phase. The generation of both pyrimidines and triazines in comparable yields from urea, together with a possible role for triazines as alternative nucleobases, opens new perspectives on the prebiotic chemistry of informational polymers.

Menor-Salvan, C., Ruiz-Bermejo, D.M., Guzman, M., Osuna-Esteban, S. and Veintemillas-Verdaguer, S. (2009), Synthesis of Pyrimidines and Triazines in Ice: Implications for the Prebiotic Chemistry of Nucleobases. Chemistry – A European Journal, 15: 4411-4418. https://doi.org/10.1002/chem.200802656

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