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DC Field | Value | Language |
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dc.contributor.advisor | Coombes, RG | - |
dc.contributor.author | Philbin, Simon Patrick | - |
dc.date.accessioned | 2008-05-09T13:45:44Z | - |
dc.date.available | 2008-05-09T13:45:44Z | - |
dc.date.issued | 2001 | - |
dc.identifier.uri | http://bura.brunel.ac.uk/handle/2438/2165 | - |
dc.description | This thesis was submitted for the degree of Doctor of Philosophy and awarded by Brunel University. | - |
dc.description.abstract | The novel candidate high energy insensitive explosive; 2,5-diamino-3,6-dinitropyrazine (ANPZ-i) has been prepared in acceptable overall yield. ANPZ-i was synthesised by the nitration of 2,5-diethoxypyrazine using nitronium tetrafluoroborate (NO2+BF4-) in sulfolane and the subsequent amination of 2,5-diethoxy-3,6-dinitropyrazine, under autoclave conditions. Oxidation studies towards the dioxide derivative of ANPZ-i, 2,5-diamino-3,6-dinitropyrazine-1,4-dioxide (PZDO), were unsuccessful. The synthesis of existing high explosives; 2,6-diamino-3,5-dintropyrazine (ANPZ) and 2,6-diamino-3,5-dinitropyrazine-1-oxide (PZO) has been scaled up to produce approximately 25 g batches of material. A number of novel nitrations using NO2+BF4- have been carried out on a range of chloro-, methyl- and hydroxy-functionalised quinoxalines and quinazolines. A range of novel functionalisations have also been carried out on the platform molecule; 2,4-diamino-6,8-dinitroquinazoline giving rise to 2,4-diamino-6,8-dinitroquinazoline-1,3-dioxide (di-N-oxidation product), 2,4,7-triamino-6,8-dinitroquinazoline (monoamination product) and 2,4,6,8-tetra-aminoquinazoline (dihydrogenation product). Detonics molecular modelling was carried out on the following target molecules: 2,5-diamino-3,6-dinitropyrazine-1,4-dioxide (PZDO), 2,5,8-triamino-3,6,7-trinitroquinoxaline-1-oxide and 2,5,7-triamino-4,6,8-trinitroquinazoline-1-oxide. The detonation velocity of the new explosive molecule; 2,5-diamino-3,6-dinitropyrazine (ANPZ-i) was calculated and it was found to be a similar value to that obtained experimentally for the existing high explosive RDX. Calculation by molecular modelling of the steric energies of ANPZ, PZO, ANPZ-i and PZDO gave a quantitative assessment of the difficulty in oxidising ANPZ-i to give PZDO. Extensive analysis of carbon-13 NMR spectroscopy shift values was carried out for approximately twenty nitrogen heterocyclic compounds. Comparison of shift values indicated consistency in the interpretations. On-line literature searches have shown that the following compounds prepared in this project are new: 2,3,6-trichloro-5-nitroquinoxaline, 2,3-dimethoxy-6,7-dinitroquinoxaline, 2,3,6-trichloroquinoxaline-1-oxide, 2,4-diamino-6,8-dinitroquinazoline-1,3-dioxide, 2,4,7-triamino-6,8-dinitroquinazoline and 2,5-diamino-3,6-dinitropyrazine (ANPZ-i). Furthermore, new synthetic routes have been used in the preparation of the following compounds: 2,3-dichloro-5-nitroquinoxaline, 2,3,6,7-tetrachloro-5-nitroquinoxaline, 2-hydroxy-6-nitroquinoxaline, 2-hydroxy-3-methyl-6-nitroquinoxaline and 2,5-diethoxy-3,6-dinitropyrazine. | en |
dc.format.extent | 10854912 bytes | - |
dc.format.mimetype | application/pdf | - |
dc.language.iso | en | - |
dc.publisher | Brunel University Institute for the Environment PhD Theses | en |
dc.relation.uri | http://bura.brunel.ac.uk/bitstream/2438/2165/3/FulltextThesis.pdf | - |
dc.subject.other | Nitration of heterocyclic compounds | en |
dc.subject.other | Energetic materials | en |
dc.title | Studies of novel nitro-substituted nitrogen heterocyclic compounds | en |
dc.type | Thesis | - |
dc.contributor.sponsor | Ministry of Defence | en |
Appears in Collections: | Environment Institute for the Environment |
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File | Description | Size | Format | |
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FulltextThesis.pdf | 20.43 MB | Adobe PDF | View/Open |
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