Accession Number : ADA328022

Title :   Novel Reagents for N-NO2 Scission.

Descriptive Note : Final rept. Jun 94-Apr 95,

Corporate Author : TPL INC ALBUQUERQUE NM

Personal Author(s) : Chapman, Robert D. ; O'Brien, Richard A. ; Kondracki, Paul A.

PDF Url : ADA328022

Report Date : FEB 1997

Pagination or Media Count : 55

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.

Descriptors :   *DEMILITARIZATION, *NITRAMINES, NUCLEAR MAGNETIC RESONANCE, DEGRADATION, HYDRAZINES, CHEMICAL BONDS, AROMATIC COMPOUNDS, METHYLENES, NITRATION, HETEROCYCLIC COMPOUNDS, TETRYL, HMX, HEXAMINES.

Subject Categories : Industrial Chemistry and Chemical Processing
      Ammunition and Explosives
      Solid Wastes Pollution and Control

Distribution Statement : APPROVED FOR PUBLIC RELEASE