| Polynitrocyclic compounds are widely used in many fields including energy material, medicine, fuel, antirust, etc. The introduction of nitrogen atom on the skeleton would further improve the energy density.In this thesis,9-azabicyclo[3.3.1]nonane motif was constructed through cyclization. Based on this motif, a series of derivatives were synthesized. 9-Azabicyclo[3.3.1]nonane-2,6-diol was prepared via epoxidation and aminative cyclization from cycloocta-1,5-diene. A new energetic compound 9-nitro-9-azabicyclo[3.3.1] nonane-2,6-diyl dinitrate was synthesized by further nitration. The thermal stability was studied by thermogravimetry (TG) and differential scanning calorimetry (DSC). The results show that 9-nitro-9-azabicyclo[3.3.1]nonane-2,6-diyl dinitrate has a melting point of 120℃, furthermore, it decomposes from 150℃ and the decomposition peak temperature is 192℃. The nitration reaction and epoxidation reaction were emphasized studied. Under the optimized reaction conditions, the total yield was achieved as high as 55.7%.With the successful method for the construction of 9-azabicyclo[3.3.1]nonane motif in hand, we designed the synthetic route of 2,6-diazaadamantane motif. 9-Benzyl-9-azabicyclo[3.3.1]nonane-2,6-diol and 9-benzyl-9-azabicyclo[3.3.1]nonane-2,6-dione were synthesized from cycloocta-1,5-diene through epoxidation, aminative cyclization and oxidation. The effort to prepare 9-azabicyclo[3.3.1]nonane-2,6-diene via elimination of bromine, acetic acid and tosic acid all failed. Bromination and ammonolysis were carried out with 9-benzyl-9-azabicyclo[3.3.1]nonane-2,6-dione and the product was no 2,6-diazaadamantane skeleton but 3-amino-9-benzyl-9-azabicyclo[3.3.1]nonane-2,6-dione.’In conclusion,9-azabicyclo[3.3.1]nonane skeleton was constructed through epoxidation and amination from cycloocta-1,5-diene. Based on this motif, a series of derivatives were synthesized. This protocol is valuable to construct other azapolycyclic structures. |
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