SYNTHESIS OF 2-NITROIMINO-5-NITROHEXAHYDRO-1,3,5-TRIAZINE VIA CHLORIDE-ASSISTED NITROLYSIS OF A TERTIARY AMINE

An alternative synthesis of the insensitive energetic nitramine 2-nitr oimino-5-nitrohexahydro-1,3,5-triazine (1) via nitrolysis of a tertiar y amine is presented. Nitration of the tertiary amine precursor (2) is effected by chloride-assisted elimination of the tert-butyl moiety, w ith the chloramine presumably formed as an intermediate. The reaction fails to proceed in the absence of chloride at 0 degrees C, however, i ts inclusion in the reaction system leads to a smooth conversion to (1 ) under mild nitrating conditions, which can be scaled up to yield mul tigram quantities. This is the first known example of a chloride-assis ted nitrolysis of a tertiary amine to appear in the open literature.