The effect of pressure on the thermal decomposition of nitroalkanes catalyzed by amines |
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| Authors: | Darren L. Naud Kay R. Brower |
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| Affiliation: | 1. Department of Chemistry , New Mexico Institute of Mining and Technology , Socorro, New Mexico, 87801, U.S.A.;2. Lockheed-NASA, White Sands Testing Facility , P.O. Drawer MM, Las Cruces, NM, 88004;3. Department of Chemistry , New Mexico Institute of Mining and Technology , Socorro, New Mexico, 87801, U.S.A. |
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| Abstract: | Abstract Solutions of 1° and 2° nitroalkanes were thermolyzed in the presence of amines at hydrostatic pressures up to 1.5 GPa, and their rates of decomposition were measured. The probable mechanism of base catalyzed decomposition involves a bimolecular reaction of the aci-nitroalkane with the nitronate ion to yield a carbonyl compound, its corresponding oxime, and nitrite ion as the early rate determining steps. In the case of nitroethane, the products react further to give 3,4,5-trimethylisoxazole as a major product above 0.4 GPa. The effects of pressure on the rates of decomposition of nonacidic nitroalkanes, 2,2-dinitropropane and 2-methyl-2-nitropropane, were measured and used to infer the rate-controlling steps. 2,2-Dini-tropropane appears to undergo rearrangement to a nitrite, followed by homolysis to give acetone, NO and NO2. 2-Methyl-2-nitropropane gives mostly isobutylene and HONO, probably via a 5-membered cyclic transition state. |
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| Keywords: | Pressure activation volume thermolysis nitroalkanes nitromethane nitroethane 2-nitropropane |
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