Synthesis of the hexanitrohexaazaisowurtzitane( HNIW)
| Autor: | Tzu-Hao Ting, 丁自豪 |
|---|---|
| Rok vydání: | 2000 |
| Druh dokumentu: | 學位論文 ; thesis |
| Popis: | 88 A high enrgy material hexanitrohexaazaisowurtzitane (HNIW) is synthesized in this research via hexabenzylhexaazaisowurtzitane (HBIW) as starting material and tetraacetyldibenzylhexazaisowurtzitane (TADB) as intermediate. In the presence of a catalytic amount of formic acid, treatment of benzylamine with glyoxal in acetonitrile achieves high yield of hexabenzylhexaazaisowurtzitane (HBIW). Substituted benzylamines such as piperonyl- benzylamine, 3,5-dimethoxylbenzylamine, (3-trifluoromethylbenzylamine) and 2 - chlorobenzylamine also react with glyoxal to form 2,4,6,8,10,12- hexapiperonyl-2,4,6,8,10,12-hexaaza- tetracyclo[5,5,0,05,9,03,11]dodecane (HPIW), 2,4,6,8,10,12-Hexa (3,5- dimethoxylbenzyl)2,4,6,8,10,12-hexaazatetracyclo[5,5,0,0,5,9,03,11]dodecane (HDIW), 2,4,6,8,10,12-hexa-(3-trifluoromethoxylbenzyl) - 2, 4, 6, 8, 10, 12-hexaazatetracyclo[5,5,0,0,5,903,11 ] dodecane (HTIW) and 2, 4, 6, 8, 10, 12 - hexa- 4 - chlorobenzyl -2, 4, 6, 8, 10, 12- hexaazatetracyclo [ 5, 5, 0, 0 5,9, 0 3,11 ] dodecane (HCIW) compounds, respectively. Some methods are tried for the synthesis of hexanitrohexaazaisowurtzitane (HNIW). First, all attempts to synthesize hexanitrohexaazaisowurtzitane (HNIW) directly via the nitrolysis of hexabenzylhexaazaisowurtzitane (HBIW) are failed. The methods involve (1) 100 % nitric acid, (2) nitric acid / sulfuric acid, and (3) nitric acid / acetic acid. But these reactions lead to the skeleton-breaking of caged ring and no hexanitrohexaazaisowurtzitane (HNIW) compound is observed. Next, all attempts to synthesize hexaazaisowurtzitane (HIW) as precursor for hexanitrohexaazaisowurtzitane (HNIW) via the debenzylation of hexabenzylhexaazaisowurtzitane (HBIW) are also failed. The attempts to prepare HIW uses three methods including (1) 4.4 % formic acid / methanol with Pd / C, (2) ammonium formate / methanol with Pd / C and (3) 1-chloroethylchloroformate / dichloroethane. But no HIW compound is observed on 1H NMR spectrum. Finally, an improved reduction - debenzylation reaction is successfully carried out in acetic anhydride at the room temperature and normal pressure in the presence of a catalytic amount of Pd / C to produce tetraacetyldibenzylhexaazaisowurtzitane (TADB) in high yield. The nitrosonation of tetraacetyldibenzylhexaazaisowurtzitane (TADB) with nitrosonium tetrafluoroborate (NOBF4) followed by subsequent nitration of the nitrosonated compound with nitronium tetrafluoroborate (NO2BF4) in sulfolane affords hexanitrohexaaza- isowurtzitane (HNIW) in high yield. |
| Databáze: | Networked Digital Library of Theses & Dissertations |
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