由四乙酰基二苄基六氮杂异伍兹烷合成六硝基六氮杂异伍兹烷

以四乙酰基二苄基六氮杂异伍兹烷为基质,经亚硝解脱苄合成了四乙酰基二亚硝基六氮杂异伍兹烷(TADNSIW);用纯硝酸氧化TADNSIW制备四乙酰基二硝基六氮杂异伍兹烷(TADNIW),收率93.0%,以上两步反应均在室温下完成。在85℃条件下,TADNIW经硝硫混酸硝解合成了六硝基六氮杂异伍兹烷(HNIW),反应时间50 m in,收率95.1%,质量分数98.80%。用硝硫混酸对TADNSIW进行硝解合成了HNIW,并优化了反应条件,反应温度90℃,反应时间60 m in,硝解剂必须大于14 mL(底物TADNSIW 1.2 g),收率为96.1%,质量分数98.87%。分别用FTIR,1HNMR和元素分析对目标化合物进行了表征。前体TADNSIW和TADNIW分子中只有乙酰基和亚硝基,它们的硝解反应体系较简单,反应时间短、反应条件温和,母液中只含有乙酸和硝解剂,产物易分离。

Synthesis of HNIW from Tetraacetyldibenzylhexaazaisowurtzitane

Nitrosolysis with debenzylation of tetraacetyldibenzylhexaazaisowurtzitane(Ⅰ) gave tetraacetyldinitrosohexaazaisowurtzitane(Ⅱ),which was then oxidized by 100% nitric acid to give tetraacetyldinitrohexaazaisowurtzitane(Ⅲ) in 93.0% yield.Both reactions were achieved at room temperature.Ⅲ was nitrated at 85 ℃ with a mixture of conc.sulfuric acid and fuming nitric acid for 50 min to give hexanitrohexaazaisowurtzitane(Ⅳ) in 95.1% yield and of 98.80% purity.Ⅳ was also prepared directly from Ⅱ under the optimized reaction conditions of 90 ℃,60 min and 14 mL nitrating agent for 1.2 g Ⅱ with the yield of 96.1% and purity of 98.87%.The synthesized compounds were characterized by FTIR,~1HNMR and elementary analysis.The precursors Ⅱ and Ⅲ contain only nitroso and acetyl group,therefore they are easily nitrated to form the target compound Ⅳ under mild conditions in short time,and it is easy to separate the product from acetic acid and nitrating agents in the mother solution.