Dense compounds of C, H, N, and O atoms: II [1]. Nitramine and nitrosamine derivatives of 2-oxo- and 2-iminooctahydroimidazo-[4,5-d]imidazole

The 4,6‐dinitroso derivative 11 was obtained (83%) by the nitrosation of 2‐oxooctahydroimidazo[4,5‐d]‐imidazole 1 as the dihydrochloride and was converted to the 4,6‐dinitro derivative 12 [66%] by treatment with nitric acid (100%, ‐40°C) and to the 1,4,6‐trinitro derivative 13 (66%) and the 1,3,4,6‐tetranitro derivative 2 (86%) by treatment with nitric acid (100%) in acetic anhydride at 0–5°C and 10–25°C respectively. Similar treatment with nitric acid (100%) in either acetic or trifluoroacetic anhydride at 0–25°C converted the trinitro compound 13 to the tetranitro compound 2 (86%). The dinitramine 12 was also obtained (43%) from the diamine 1 by nitration with nitric acid (100%, ‐40°C). A reaction between 2‐nitrimino‐5‐iminooctahydroimidazo[4,5‐d]imidazole 7 as a hydrochloride salt (from an acid catalyzed condensation between 4,5‐dihydroxy‐2‐nitriminoimidazolidine 6 and guanidine) and nitric acid (100%, ‐40°C) gave the 2,5‐dinitrimino derivative 14 (85%) isolated as a monohydrate. The nitrate salt 7 · HNO3, isomeric with 14 · H2O, was obtained from the corresponding hydrochloride 7 · HCl and silver nitrate. Both nitrimines 7 and 14 gave 1,3,4,6‐tetranitro‐2,5‐dioxooctahydroimidazo[4,5‐d]imidazole 15 (66% and 59%) by treatment with nitric acid (100%) in acetic anhydride.