Thermal rearrangement of 1,4-dinitroimidazole to 2,4-dinitroimidazole. Characterization and investigation of the mechanism by mass spectrometry and isotope labeling
- Army Armaments Research, Development and Engineering Center, Picatinny Arsenal, NJ (United States)
- Sandia National Lab., Livermore, CA (United States)
- Geo Centers, Inc., Picatinny Arsenal, NJ (United States)
- City College of the City Univ., New York, NY (United States)
The thermal rearrangement of 1,4-dinitroimidazole to 2,4-dinitroimidazole has been investigated by differential scanning calorimetry and mass spectrometry techniques. When mixtures of independently prepared deuterium-and {sup 15}N-labeled samples of the 1,4-isomer were subjected to thermal rearrangement, the resulting 2,4-dinitroimidazole failed to show isotope-scrambled molecular ions in its mass spectrum, suggesting that the reaction was intramolecular in nature. This was interpreted to mean that the mechanism was of the (1,5)-sigmatropic type rearrangement. Extensive NMR measurements were used to obtain unequivocal evidence for the identity of the assumed structures of the isomeric dinitroimidazoles. Two byproducts (4-nitroimidazole and a trinitroimidazole), formed during the rearrangement reaction, have also been identified. Plausible mechanisms for their formation are discussed. 15 refs., 3 figs., 3 tabs.
- Research Organization:
- Sandia National Laboratories (SNL), Albuquerque, NM, and Livermore, CA (United States)
- DOE Contract Number:
- AC04-94AL85000
- OSTI ID:
- 41636
- Journal Information:
- Journal of Physical Chemistry, Vol. 99, Issue 14; Other Information: PBD: 6 Apr 1995
- Country of Publication:
- United States
- Language:
- English
Similar Records
Solid-phase thermal decomposition of 2,4-dinitroimidazole (2,4-DNI)
Solid-phase thermal decomposition of 2,4-dinitroimidazole (2,4-DNI)