De. Woon, Ab initio, quantum chemical studies of reactions in astrophysical ices 3. Reactions of HOCH2NH2 formed in H2CO/NH3/H2O ices, J PHYS CH A, 105(41), 2001, pp. 9478-9481
Prior experimental and theoretical studies have demonstrated that reactions
involving H2CO and NH3 Can occur in water ice mixtures even at temperature
s below 100 K. The key reaction between H2CO and NH3 generates monohydroxym
ethylamine, HOCH2NH2. The present study examines further reactions between
this product and H2CO in ices. Quantum-chemical calculations at the MP2/6-3
1+G** level indicate that while H2CO may add across the OH bond in HOCH2NH2
to yield the amine-terminated polyoxymethylene species HOCH2OCH2NH2, it. i
s much more favorable to add across one of the two remaining NH bonds of th
e original ammonia molecule to yield (HOCH2)(2)NH. In fact, another H2CO ma
y add across the final NH to form the tertiary amine (HOCH2)(3)N. On the ba
sis of the favorable energetics of these reactions, it is suggested that on
e or both of these products. may be an, intermediate in the pathway to the
formation of hexamethylenetetramine (C6H12N4), which is produced when ices
containing methanol, ammonia, and water are subjected to UV irradiation and
heated to room temperature.