15973-99-6Relevant academic research and scientific papers
An Alternate Synthesis of Cyclic 1,3-Dinitramines
Willer, Rodney L.,Atkins, Ronald L.
, p. 5147 - 5150 (1984)
An alternate synthesis for cyclic 1,3-dinitramines has been developed.The new method involves the trapping of an in situ generated cyclic aminal with nitrous acid to generate a cyclic 1,3-dinitrosamine, which is subsequently converted to the cyclic 1,3-dinitramine by treatment with 100percent nitric acid or solutions of N2O5 in 100percent nitric acid.This alternate synthesis is superior for the synthesis of 5- and some 6-membered cyclic 1,3-dinitramines but not for 7-membered compounds.
Mechanisms of Nitramine Thermolysis
Oxley, J. C.,Kooh, A. B.,Szekeres, R.,Zheng, W.
, p. 7004 - 7008 (2007/10/02)
The thermal decomposition of a number of nitramines was studied in dilute solution and in the melt.The nitramines included acyclic mononitramines , cyclic mononitramines , cyclic dinitramines , and 1,3,5-trinitro-1,3,5-triazocyclohexane (RDX), octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), hexanitrohexaazaisowurtzitane (HNIW), and 1,3,3-trinitroazetidine (TNAZ).For the acyclic and cyclic mono- and dinitramines, the corresponding nitrosamines were the only or major condensed-phase product.Kinetics and activation parameters were determined for the thermolysis of dilute solutions (0.01-1.0 wtpercent) over the range 200-300 deg C.The thermolyses were found to be first-order with the rate constants unaffected by the use of deuterated solvent.As the nitramines became more complex than dimethylnitramine (DMN), the rate of decomposition increased and the product distribution became more complex.As the length of the aliphatic chain increased (DMN DEN DPN), the rate of thermolysis increased, yet nitrosamine remained the only observed condensed-phase product.When a secondary carbon was attached to the N-nitramine (DIPN) rather than the primary (DPN), the rate of decomposition increased and a new condensed-phase product was observed.Among the cyclic nitramines, the rate of decomposition increased as the number of NNO2 groups increased (NPIP pDNP; NPyr DNI; mDMP RDX).The position of the nitramine groups affected the decomposition: meta NNO2 groups (mDNP) decomposed faster than para (pDNP).Ring strain decreased stability: mDNP DNI; HMX RDX.In complex nitramines, the increase in decomposition rate, the appearance of new products, and the change in the relative importance of nitrosamine and of N2 and N2O are attributed to new decomposition routes available to them.However, since complex nitramines (e.g.RDX) maintain first-order kinetics and since most have activation energies in the range of 40-50 kcal/mol, it is belived that the triggering mechanism remains N-NO2 homolysis.Intramolecular hydrogen transfer is also considered an important mode of nitramine decomposition.
