Approaches to Synthesis of Caged Nitramine Explosives

Two of the most important military explosives are RDX (13.5-UinitH -U,5-hexahydrotriazine (3) and HMX (1) (Refs. 10-17). 

Both RDX and HMX are prepared by the first method. Reactant hexamethylenetetramine (hexamine, 4) may be directly nitrated with nitric add to produce a mixture of RDX and HMX (principally RDX) (Refe. 10,12). Another nitration procedure that employs nitric acid, ammonium nitrate, and acetic anhydride is used to prepare HMX (Refe. 11,17). 

The second approach to cyclic nitramines may be illustrated in the reaction of ethylenedinitramine (5) with formaldehyde to produce l,3-dinitro-l,3-diazacyclopentane (6) (Refe. 18-20). This approach has limitations when applied to more complex cyclic nitramines (Ref. 20). 

the preferred approach to caged nitramines is usually the fifit method, which departs from a caged polyamine containing the required number of amino groups in the desired positions. 

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