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Novel strategies for the synthesis of vincinal dinitro cage compounds

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Description: Two $N,N\sp\prime$-dinitroimidazolinones were prepared as potential energetic materials and their single crystal X-ray structures were determined. 2,4-Diaza-1,5-dimethyl-2,4-dinitrobicyclo(3.1.0) hexan-3-one and 2,4-diaza-1,5-dimethyl-2,4-dinitrobicyclo(3.2.0) heptan-3-one were successfully synthesized in 33% and 26% yield via nitration of cis-2,4-diaza-1,5-dimethylbicyclo (3.1.0) hexan-3-one and cis-2,4-diaza-1,5-dimethylbicyclo- (3. 2.0) heptan-3-one, respectively. The synthesis of two cyclobutyl vicinal diamines; cis-1,2-diamino-1,2-dimethylcyclobutane and cis-2,3-diamino-2,3-dimethylbicyclo (4.2.0) -octane was achieved from a common precursor, 1,3-diacetyl-4,5-dimethyl-4-imidazolin-3-one. An attempted preparation of cis-1,2-diamino-1,2-dimethylcyclopropane from the hydrolysis of cis-2,4-diaza-1,5-dimethyl-bicyclo (3.1.0) hexan-3-one resulted in the isolation of 2,5-dihydro-2,2,3,5,5,6-hexamethylpyrazine. Dimethyldioxirane (DMDO) oxidation of several vicinal diamines and vicinal diamine derivatives was performed. 4-Nitro-5-carbomethoxy-pentacyclo (4.3.0.0$\sp{2,4}$.0.$\sp{3,8}$.0$\sp{5,7}$) nonane was prepared from the corresponding amine in 61% yield via a DMDO oxidation. 1,2-Dinitro-benzene (80%) was obtained upon DMDO oxidation of o-phenylenediamine. The dioxirane oxidation of 2,3-diamino-2,3-dimethylbutane produced a mixture of 3,3,4,4-tetramethyl-1,2-diazetine-1,2-dioxide (49%) and 2,3-di-methyl-2,3-dinitrobutane (13%). $\sp1$H NMR indicated the mixture consisted of a 1.0: 2.9 ratio of nitroso dimer to dinitrobutane. Dimethyldioxirane oxidation of 1,2-diamino-1,2-dimethylcyclobutane did not provide the corresponding dinitro product; rather, acetonylacetone, the ring fragmentation product, was obtained (86%). Dimethyldioxirane oxidation of $N,N\sp\prime$-dibenzylidene-2,3-diamino-2,3-dimethylbutane produced a blue solid having severely broadened resonances in the $\sp1$H and $\sp{13}$C NMR spectra. Subsequent ozonation of this product gave 2,3-dimethyl-2,3-dinitrobutane (32%). The DMDO oxidation of 4,4,5,5-tetramethyl-2-phenylimidazolidine also resulted in the isolation of a blue intermediate which exhibited severely broadened resonances in the NMR spectra. Dimethyldioxirane oxidation and subsequent ozonation of 4,4,5,5-tetramethyl-2-phenylimidazolidine resulted in the isolation of 2,3-dimethyl-2,3-dinitrobutane (49%).
Language: English
Format: Degree Work