New synthesis of TATB using inexpensive starting materials and mild reaction conditions

摘要

TATB is currently manufactured in US by nitration of the expensive TCB to give 2,4,6-trichloro- 1,3,5-trinitrobenzene which is then aminated to yield TATB. Elevated temperatures (150 C) are required for both reactions. There is a need for a more economical synthesis of TATB that also addresses current environmental issues. We have recently found that 1,1,1-trimethylhydrazinium iodide (TMHI) allows the amination of nitroarenes at ambient temperature via Vicarious Nucleophilic Substitution of hydrogen. TMHI reacts with picramide in presence of strong base (NaOMe or t-BuOK) to give TATB in over 95% yield. TMHI and picramide can be obtained from either inexpensive starting materials or surplus energetic materials from demilitarization activities, such as the 30,000 metric tons of UDMH (surplus rocket propellant) from the former Soviet Union.