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以二氨基氧化偶氮呋咱(DAOAF)和2,2-二甲基-5-硝基-5-亚硝基-1,3-二氧环己烷(DMNNDO)为原料,通过氧化偶联、水解、溴化、还原、硝化、成盐、氟化等7步反应,合成了含能化合物3,3’-双(氟二硝甲基-ONN-氧化偶氮基)氧化偶氮呋咱(FDNAF),并采用IR、~1H NMR、~(13)C NMR、~(15)N NMR、~(19)F NMR和元素分析等手段对中间体及目标化合物进行了结构表征.改进了水解反应条件,采用HCl/CH_3CH_2OH代替AcCl/CH_3OH水解体系,反应时间由18 h缩短为2 h,粗品纯度提高至93%.研究了溴化反应的最佳条件,在20℃反应30 min获得溴化产物,收率最高为51.5%.基于量子化学密度泛函理的B3LYP方法,对FDNAF的~(13)C NMR,~(15)N NMR的化学位移和IR吸收频率进行理论研究,实验结果和理论结果具有较好的一致性.开展了单硝基甲基-ONN-氧化偶氮化合物(BNMAF)、二硝基甲基-ONN-氧化偶氮化合物(BDNAF)和氟二硝甲基-ONN-氧化偶氮化合物(FDNAF)三种含能化合物的物化、爆轰性能和热性能研究,含能化合物FDNAF理论密度2.02 g·cm~(-3)、热分解峰温233.4℃、氧平衡6.72%、爆速9735 m·s~(-1)、爆压44.9 GPa、特性落高36 cm,表明FDNAF是一种性能突出的高能量密度含能化合物.
Using DAOAF and 2,2-dimethyl-5-nitro-5-nitroso-1,3-dioxetane (DMNNDO) as starting materials, , 7-step reaction of hydrolysis, bromination, reduction, nitration, salt formation, and fluorination was carried out to synthesize a compound of 3,3’-bis (fluoronitr dinitrophenyl-ONN- azoxy) (FDNAF) were synthesized and characterized by IR, ~ 1H NMR, ~ (13) C NMR, ~ (15) N NMR, ~ (19) F NMR and elemental analysis. The reaction conditions were as follows: HCl / CH 3 CH 2 OH instead of AcCl / CH 3 OH hydrolysis system, the reaction time was shortened from 18 h to 2 h and the purity of the crude product was increased to 93% .The optimum conditions of bromination reaction were studied and reacted at 20 ℃ for 30 min to obtain bromine The yield of the product was 51.5% .The theoretical calculations of ~ (13) C NMR and ~ (15) N NMR chemical shifts and IR absorption of FDNAF were carried out based on the B3LYP method of quantum chemical density functional theory. The experimental results And the theoretical results are in good agreement.Mononitro methyl-ONN-azo compounds (BNMAF), dinitro methyl-ONN-azo compounds (BDNAF) ONN-Oxazo compounds (FDN AF). The theoretical density of FDNAF was 2.02 g · cm ~ (-3), the peak temperature of thermal decomposition was 233.4 ℃, the oxygen balance was 6.72%, and the detonation velocity was 9735 m · s ~ (-1), burst pressure 44.9 GPa, characteristic drop height 36 cm, indicating that FDNAF is a kind of high performance energy density compound with high energy density.