Study On The Synthesis Of Tetranitroadamantanes

Polynitroadamantanes and polyazaadamantanes contain high energy density and have good stability which can be widely used as the insensitive energetic materials. In this dissertation, the synthesis of2,2,4,4-tetranitroadamantane,2,2,6,6-tetranitroadamantane and3,5,7-triamino-l-azaadamantane were studied. The structure of all the products were identified and thermal stability of the final products were studied.2,2,4,4-Tetranitroadamantane was synthesized from adamantan-2-one via a nine-step process including Baeyer-Villiger oxidation, lactone rearrangement, oximation, oxidation and nitration. The synthesis of key intermediate4,4-(ethylenedioxy)adamantan-2-one was improved dramatically. The oxidative nitration of oxime was intensively investigated and afforded gem-dinitro derivative when the reaction was carried out with dinitrogen pentoxide. The overall yield was14.2%, which is2.9times higher than that reported.2,2,6,6-Tetranitroadamantane was synthesized from adamantine-2,6-dione via a two-step process including oximation and nitration. The synthesis of adamantine-2,6-dioxime was improved dramatically. The yield of oximation was86.4%and10%higher than that reported. The oxidative nitration of adamantine-2,6-dioxime afforded the product in a yield of44.9%when the reaction was carried out with dinitrogen pentoxide. The yield is4.1times higher than that reported and this method is more simple than the three-step method which was reported.3,5,7-Triamino-l-azaadamantane was synthesized from1,3-dinitrobenzene via a four-step process including nitration, reduction, Henry reaction and condensation.1,3,5-tri-hydroxymethyl-1,3,5-trinitrocyelohexane was synthesized by "fractional step" or "one-pot" processes. The reaction time of Henry reaction was shortened and the yield was improved by elevating reaction temperature. The final step of the reaction was intensively investigated. The reaction time was shortened and the energy consumption was reduced.The synthesis of three comprounds was improved dramatically in this dissertation and the yields were higher than that reported before. The oxidative nitration of oxime afforded gem-dinitro derivatives in a higher yield when the reaction was carried out with dinitrogen pentoxide, at the same time this method is more simple and convenient.