The first steps in the mechanism for the formation of hexamethylenetriperoxidediamine (HMTD) from hexamine and hydrogen peroxide with acid catalyst were investigated using ab initio quantum chemical methods. Determining the possible intermediates involved in the synthesis of this peroxide explosive may lead to the development of better detection methods. Preliminary results using the MP2/cc-pVTZ method indicate an exergonic process for the net reaction of -26 and -32 kJ/mol for the C<sub>2</sub> and D<sub>3</sub> HMTD conformers, respectively. The first step in the mechanism is presumed to be proton addition to a basic nitrogen site in a nearly barrier-less process. Then steps consisting of alternating C-N bond scission, peroxide addition, and ring formation continue until all three peroxides are added; during which one of the two product ammonias is formed. Intramolecular rearrangement then leads to the loss of a second ammonia and final ring closure. Possible alternate pathways will also be discussed.

Computational study on the formation of hexamethylene triperoxide diamine

249th National Meeting (2015)

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