吡啶类含能化合物的合成、表征和性能初步研究

发布时间：2018-04-22 18:03

本文选题：有机化学 + 合成　；参考：《南京理工大学》2015年博士论文

【摘要】：本文以吡啶类含能衍生物为研究对象,主要进行了[1,2,5]VA二唑并[3,4-e]四唑并[1,5-a]吡啶-3-氧化物,2-氨基-3,5-二硝基-6-取代吡啶衍生物,2-取代-4-氨基-3,5-二硝基吡啶衍生物,2,6-二取代-4-氨基-3,5-二硝基吡啶衍生物,吡啶或苯并环脲硝胺硝基衍生物的合成路线设计与合成,并对它们的爆炸性能进行了理论计算与初步预测。以2,6-二氯吡啶为原料合成出[1,2,5]VA二唑并[3,4-e]四唑并[1,5-a]吡啶-3-氧化物(88b),并对其结构进行了研究,发现该化合物结构中的氧化呋咱环在强酸性、强碱性及弱碱性条件下能稳定存在,而吡啶环上由叠氮基形成的四唑环结构则不稳定,易被羟基、甲氧基和甲胺基等供电性基团所取代。设计了2-氨基-3,5-二硝基-6-氯吡啶及其衍生物的合成新方法,以廉价易得的2,6-二氯吡啶为起始原料,通过硝化、氨化、硝化反应步骤得到中间体2-氨基-3,5-二硝基-6-氯吡啶,再与氨、叠氮化钠等亲核试剂反应得到2-氨基-3,5-二硝基-6-取代吡啶含能衍生物：2,6-二氨基-3,5-二硝基吡啶(20)、2,6-二氨基-3,5-二硝基吡啶-1-氧化物(21)、5-氨基-6,8-二硝基四唑并[4,5-a]吡啶(102b)、5-氨基-6-硝基-[1,2,5]VA二唑并[3,4-b]吡啶-1-氧化物(103)、N2-(6,8-二硝基四唑基[1,5-a]吡啶-5-基)-2,6-二氨基-3,5-二硝基吡啶(106)。研究结果表明该方法具有原料便宜易得、后处理操作简单和产品纯度高等优点。研究了2-氯-4-氨基-3,5-二硝基吡啶及其衍生物的合成,设计以2-氯-4-氨基吡啶为原料,经一步二硝化反应得到2-氯-4-氨基-3,5-二硝基吡啶(111)及副产物(E)-1,2-双(2-氯-3-硝基吡啶基-4-基)二氮烯(112)。将2-氯-4-氨基-3,5-二硝基吡啶与亲核试剂叠氮化钠、氟化钾、氨气、甲胺、4-硝基咪唑等反应可生成2-取代-4-氨基-3,5-二硝基吡啶系列含能衍生物：(E)-1,2-双(2-氨基-3-硝基吡啶-4-基)二氮烯(113)、2,4-二氨基-3,5-二硝基吡啶(114)、7-氨基-6-硝基-[1,2,5]VA二唑并[3,4-b]吡啶-1-氧化物(115)、7-氨基-6,8-二硝基四唑基[1,,5-a]吡啶(116b)。研究结果表明：所有的亲核取代反应条件温和,后处理过程简单。设计了2,4,6-三氨基-3,5-二硝基吡啶-1-氧化物的新法合成,以2,6-二氯吡啶为原料,经氮氧化、硝化、还原、再硝化四步反应制备出中间体2,6-二氯-3,5-二硝基-4-氨基吡啶(129),并经氨化和氮氧化步骤得到目标化合物。研究了吡啶或苯并环脲硝胺结构含能化合物的合成,采用2,3-二氨基吡啶为原料,经闭环、硝化反应得到化合物1,3,5-三硝基-1,3-二氢-2H-咪唑并[4,5-b]吡啶-2-酮(155);并进一步拓展使用5-氨基-1,3-二氢-2H-苯并咪唑-2-酮为原料,采用直接硝化法及通过氨基保护、硝化、脱保护、再硝化的间接合成法制备出5-氨基-1,3,6-三硝基-1,3-二氢-2H-苯并咪唑-2-酮(160),其中直接硝化法产率仅为11%,而间接合成法总产率48%。
[Abstract]:In this paper, pyridine derivatives with energy as the research object, In this paper, the derivatives of [1] -2-Amino-3-nitro-6-substituted pyridine derivatives, 2-substituted -4-diamino-5-dinitropyridine derivatives, have been prepared by [1] VAZO4-e] tetrazolido [1O5-a] pyridine 2-amino-3-oxide-5-dinitro-6-substituted pyridine derivatives, the derivatives of which are 2-substituted -4-amino-5-dinitropyridine, and the derivatives of pyridine are 2-substituted -4-amino-3-nitro-5-dinitropyridine, a derivative of pyridine. The synthetic route of pyridine or benzocyclic nitroamine derivatives was designed and synthesized, and their explosive properties were theoretically calculated and preliminarily predicted. In this paper, a new method for synthesizing [1 (2) (2) (2) -diazobenzo [(3) (4-e)] [1 (5) -a] pyridine (3) -3-oxide (8 8) b ~ (2 +) with 2'-6 '-dichloropyridine as raw material was prepared. It was found that the furoxan ring in the structure of the compound could exist stably under strong acidity, strong alkalinity and weak alkalinity, and its structure was studied. On the other hand, the structure of tetrazolium ring formed by azide on pyridine ring is unstable and easy to be replaced by hydroxyl, methoxy and methylamino groups. A new method for the synthesis of 2-amino-3-pyridyl 5-dinitro-6-chloropyridine and its derivatives was designed. The intermediate 2-amino-3-dinitro-5-dinitro-6-chloropyridine was synthesized by nitration, ammoniation and nitration of 2-amino-3-dinitro-6-chloropyridine. And then with ammonia, Synthesis of 2-Amino-3N-5-Dinitro-6- substituted pyridine derivative: 2-Amino-6-diamino-3-Amino-5-dinitropyridine 20 ~ (20) -dinitropyridine ~ (5) -5-dinitropyridinitridinitropyridine 5-oxide-1-oxide ~ (21) Amino -68-dinitro-tetrazolium [45-a] pyridine 102b ~ (-1) -Amino 6-nitro-6-nitro- [1-diazolyl] VA diazobenzo [34-b] pyridine -1-oxide-103Ox N2-O2-N2-DNTAZO _ 2-DINITROtetrazolyl [1-NITRO-5-A] pyridine -5- (5-pyridyl) pyridinitropyridyl (106-) -5-pyridinitropyridine. The results show that the method has the advantages of cheap raw material, simple post-treatment and high purity. The synthesis of 2-chloro-4-amino-5-dinitropyridine and its derivatives were studied. 2-Chloro-4-amino-5-dinitropyridine (111) and its by-product, E ~ (2 +) -1 ~ (- 1) -diazo _ 2-chloro-3-nitropyridyl _ (4-yl) diazene were obtained by one-step and two-step nitration. 2-chloro-4-amino-5-dinitropyridine and nucleophilic reagent sodium azide, potassium fluoride, ammonia, A series of energetic derivatives of 2-substituted -4-amino-3-nitro-5-dinitropyridine can be synthesized by the reaction of methylamine 4-nitroimidazole and so on. A series of energetic derivatives of 2-Bis 2-Amino-3-nitropyridyl 4-yl) Diazene (113Amino-3Amino-5-dinitropyridine 114- amino-6nitropyridine) can be obtained by the reaction of 2-substituted -4-amino-3-nitro-5-dinitropyridine and [34-b] pyridine [34-b] pyridine [34-b]. Pyridine -1-oxide-1-oxide-115Amino-6-pyridinitrotetrazolyl [1-pyridyl 5-a] pyridine 116b ~ (-1). The results showed that all the nucleophilic substitution reaction conditions were mild and the post-treatment process was simple. A new method was designed for the synthesis of 2'4'4'6'- triamino-5'5 'dinitropyridine 1' oxide, which was oxidized, nitrified and reduced by nitrogen with 2'6 'dichloropyridine as raw material. The intermediate 2o 6-dichloro-3-trichloro-5-dinitro-4-aminopyridine was synthesized by four steps of nitrification, and the target compound was obtained by ammoniation and nitrogen oxidation. The synthesis of pyridine or benzocyclourea nitramine structure energetic compounds was studied. The compound 1: 3N 5- trinitro-1H 2 H imidazolido [4N 5 b] pyridine 2 ketone was synthesized by nitration reaction, and further expanded the use of 5 amino-1o 3 H 2 H benzimidazole-2-one as raw material, using direct nitration and amino protection, nitration and deprotection, The indirect synthesis of 5-amino-1-aniline, 6-trinitro-1n, 3-dihydro-2H-benzimidazole-2-one, 160%, in which the yield of direct nitration is only 11%, and the total yield of indirect synthesis is 48%.
【学位授予单位】：南京理工大学
【学位级别】：博士
【学位授予年份】：2015
【分类号】：TQ560.1

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