【摘要】 以金刚烷酮为原料,经Baeyer-Villiger氧化、内酯重排、缩酮化、氧化和偕硝化等单元反应合成了2,2,4,4-四硝基金刚烷。优化了重要中间体4,4-乙撑二氧基金刚烷-2-酮的合成方法。使用绿色硝化剂五氧化二氮对酮肟进行偕硝化反应,考察了溶剂、温度、反应时间、物料配比对第一步偕硝化反应的影响,确定了最佳反应条件:溶剂为二氯甲烷,n(4,4-乙撑二氧基-2-金刚烷酮肟)∶n(五氧化二氮)=1∶3,反应温度为45℃,反应时间为30 min,收率为52.3%。本路线总收率为14.2%,是文献报道的2.9倍。更多还原

【Abstract】 2,2,4,4-Tetranitroadamantane was synthesized via Baeyer-Villiger oxidation,lactone rearrangement,ketalization,oxidation and gem-nitration etc unit reaction using adamantan-2-one as raw material. The synthesis condition of an important intermediate 4,4-( ethylenedioxy) adamantan-2-one w as optimized. The gem-nitration reaction of 4,4-( ethylenedioxy) adamantan-2-one oxime w as performed using green nitration agent dinitrogen pentoxide( N2O5). The effectsof solvent,temperature,reaction time and ratio of material on the first-step gem-nitration reaction w ere investigated. R esults show that the optimum reaction conditions of the reaction are determined as: methylene chloride as solvent,the molar ratio of 4,4-( ethylenedioxy) adamantan-2-one oxime to N2O5 is 1∶ 3,reaction temperature 45 ℃ and reaction time 30 min w ith yield of 52. 3%. The overall yield of 2,2,4,4-tetranitroadamantane is 14. 2%,w hich is 1. 9 times higher than that reported in reference.更多还原