Attempts to prepare 5-chloro-6-nitrobenzodifuroxan from the reaction of 5,7-dichloro-4,6-dinitrobenzofuroxan with sodium azide have failed and, surprisingly, the formation of the powerful hydrogen-free explosive benzotrifuroxan (BTF) through spontaneous cyclization at 0?degrees C was observed (yield: 75?%). Importantly, BTF was synthesized avoiding the isolation and the heating of the hazardous intermediate trinitro-triazidobenzene. The structure of BTF was confirmed by IR spectroscopy, elemental analysis, and melting point measurement.