ABSTRACT
Thermal decomposition of secondary nitramines always starts from N — N 0 2 bond breaking. Note that the most important explosives such as hexogen ( R D X ) and octogen ( H M X ) belong to the secondary nitramines. However, from time to time other mechanisms o f the first decomposition stage are proposed. Thus, for the simplest substance o f this class, dimethylnitramine ( D M N A ) , based on the composition o f the products o f laser-induced pyrolysis ( C H 2 0 , N O , N 0 2 ) in a molecular beam at 900 K , it was concluded [5.1] that nitro-nitrite rearrangement occurs together with N — N bond breaking:
These data were not later confirmed experimentally in [5.2]. Apparently, in [5.1], photolysis products were observed. In addition, this rearrangement is not in agreement with quantum-chemical calculations [5.3], which also confirm the primary N — N bond breaking. Many different mechanisms of the first stage of decomposition were proposed for cyclic nitramines (see review [5.4]): cycle expansion to eliminate N 2 0 and C H 2 0
( C H 3 ) 2 N N 0 2 ( C H 3 ) 2 N O N O .
