NITROLYSIS OF HEXAMETHYLENETETRAMINE: II. NITROLYSIS OF l,5-ENDOMETHYLENE-3,7-DINITRO-1,3,5,7-TETRAZA-CYCLOÖCTANE (DPT)

Abstract

When 1,5-enedomethylene-3,7-dinitro-1,3,5,7-tetrazacycloöctane (DPT) is nitrolyzed with nitric acid – ammonium nitrate mixture the products are cyclic trimeric and tetrameric methylenenitramines (RDX and HMX). When the ammonium nitrate in this nitrolysis mixture is replaced by anhydrides such as nitrogen pentoxide or acetic anhydride then terminally esterified linear poly-methylenenitramines such as 1,9-dinitroxy-2,4,6,8-tetranitro-2,4,6,8-tetrazanonane and the 1,9-diacetoxy analogue respectively are obtained. Replacement of this nitric acid – anhydride mixture by acetyl nitrate does not produce the same type of nitrolysis. It is therefore concluded that nitric acid and an anhydride act independently, the former as a nitrolyzing agent and the latter as an esterifying agent. Alternatively the presence of ammonium nitrate serves to promote esterification and/or promote demethylolation.

Theoretical Investigation on the Mechanism and Design of Catalysts for Nitrolysis of Hexamine

“…Considering the importance of NO ＋ judged by some experimental and theoretical results. 5 It was reported that HA could be converted to DPT by AcONO 2 in the presence of HOAc, but hardly reacted to form DPT (1,5-endomethylene-3,7-dinitro-1,3,5,7-tetrazacyclooctane) when only AcONO 2 was used, 6 so the acidic reagents, Ac 2 O and HOAc, are the key factors for the nitrolysis of HA. Other acidic mixing reagents, e.g., HNO 3 -Ac 2 O, HNO 3 -HOAc, and HNO 3 -NH 4 NO 3 -Ac 2 O, are also often used in the nitration or nitrolysis reaction.…”

Increasing the Efficiency of the Production of 1,3,5,7-Tetranitro-1,3,5,7-tetrazocane (HMX)

“…DPT, acetic anhydride, ammonium nitrate, and nitric acid 65 [18,39] DPT, hexamine, acetic anhydride, ammonium nitrate, nitric acid, and paraformaldehyde 70 [31] Acetic acid, acetic anhydride, paraformaldehyde, hexamine, nitric acid, and ammonium nitrate 95 [31] TAT, nitric acid and phosphorous pentoxide 80 [ [7] Hexamine, acetic acid, acetic anhydride, boron tri-fluoride, diethyl ether, ammonium nitrate 90 [39] 2…”

A Groundbreaking Stepwise Protocol to Prepare HMX from DPT: New Mechanism Hypothesis and Corresponding Process Study

“…Although DPT is considered as the intermediate of Bachmann process, the smallmolecule route using urea as starting material to prepare HMX via DPT is figured as a promising method for scale-up [6][7][8][9]. The nitrolysis mechanism of DPT has two main disputable opinions in early studies: gradual degradation path and small-molecule recombination path [10][11][12][13].…”