Novel Reagents for N-NO2 Scission.
Abstract
Two novel approaches to N-NO2 bond scission in military nitramines under gentle, environmentally benign conditions were proposed for the Phase I program and have been successfully demonstrated. These approaches to N-denitration were based on mechanisms of: electron transfer hydrogenolysis by certain dihydropyridine derivatives, which was demonstrated on both tetryl and HMX as model aromatic and heterocyclic nitramines, respectively; and catalytic transfer hydrogenolysis, which employed hydrazine as a gentle reagent which denitrated HMX as a model nitramine. In the first system, N-NO2 bond scisssion in tetryl was demonstrated as the predominant transformation in its reaction with 1-benzyl-1,4-dihydronicotinamide (BNAH), a commercial dihydropyridine derivative, resulting in N-methylpicramide as the major product. In the HMX-BNAH system, HMX was definitively shown to be denitrated, and spectroscopic evidence was obtained for its conversion to hexamethylenetetramine, the expected product of its denitration. Similarly, in palladium-catalyzed reactions between HMX and hydrazine, HMX was unequivocally denitrated. The products produced depended on reaction conditions. The initial intermediate is the reactive species formaldazine; under oxidizing conditions with catalyst, this reacts further to form 4-amino-4H-1,2,4-triazole as a final product.
Document Details
- Document Type
- Technical Report
- Publication Date
- Feb 01, 1997
- Accession Number
- ADA328022
Entities
People
- Paul A. Kondracki
- Richard A. O'brien
- Robert D. Chapman