A reaction between 2, 8‐dichloro‐4, 10‐dinitro‐5, 11‐dehydro‐5H, 11H‐benzotriazolo[2, 1‐a]‐benzotriazole 8 and sodium azide in dimethyl sulfoxide produced 3, 9‐diazido‐4, 10‐dinitro‐5, 11‐dehydro‐5H, 11H‐benzotriazolo [2, 1‐a]benzotriazole 10 rather than the 2.8‐diazido isomer 9 expected by direct displacement. Thermolytic elimination of nitrogen (2 moles) converted the dinitro diazide 10 to 3,4,9,10‐bisfuroxano‐5, 11‐dehydro‐5H, 11H‐benzotriazolo[2, 1‐a]benzotriazole 11 that was subsequently nitrated to give the 2,8‐dinitro derivative 12. Similar nitration converted the dinitro diazide 9 to the trinitro 15 and tetranitro 14 derivatives: thermolysis of the latter gave 1,2,7,8‐bisfuroxano‐4, 10‐dinitro‐5, 11‐dehydro‐5H, 11H‐benzotriazolo[2, 1‐a]‐benzotriazole 16. Nitration (100% HNO3, CF3SO3H) converted compound 16 to the 3,4,10‐trinitro derivative 17, whereas a similar nitration (100% HNO3, FSO3H) gave the title compound BTBB, an insensitive high‐energy, high‐density (d 2.03 g/cc) molecule. © 1995 John Wiley & Sons, Inc.