本文選題：有機化學(xué) + 合成　； 參考：《南京理工大學(xué)》2015年博士論文

【摘要】：本文以吡啶類含能衍生物為研究對象,主要進行了[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,吡啶或苯并環(huán)脲硝胺硝基衍生物的合成路線設(shè)計與合成,并對它們的爆炸性能進行了理論計算與初步預(yù)測。以2,6-二氯吡啶為原料合成出[1,2,5]VA二唑并[3,4-e]四唑并[1,5-a]吡啶-3-氧化物(88b),并對其結(jié)構(gòu)進行了研究,發(fā)現(xiàn)該化合物結(jié)構(gòu)中的氧化呋咱環(huán)在強酸性、強堿性及弱堿性條件下能穩(wěn)定存在,而吡啶環(huán)上由疊氮基形成的四唑環(huán)結(jié)構(gòu)則不穩(wěn)定,易被羥基、甲氧基和甲胺基等供電性基團所取代。設(shè)計了2-氨基-3,5-二硝基-6-氯吡啶及其衍生物的合成新方法,以廉價易得的2,6-二氯吡啶為起始原料,通過硝化、氨化、硝化反應(yīng)步驟得到中間體2-氨基-3,5-二硝基-6-氯吡啶,再與氨、疊氮化鈉等親核試劑反應(yīng)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)。研究結(jié)果表明該方法具有原料便宜易得、后處理操作簡單和產(chǎn)品純度高等優(yōu)點。研究了2-氯-4-氨基-3,5-二硝基吡啶及其衍生物的合成,設(shè)計以2-氯-4-氨基吡啶為原料,經(jīng)一步二硝化反應(yīng)得到2-氯-4-氨基-3,5-二硝基吡啶(111)及副產(chǎn)物(E)-1,2-雙(2-氯-3-硝基吡啶基-4-基)二氮烯(112)。將2-氯-4-氨基-3,5-二硝基吡啶與親核試劑疊氮化鈉、氟化鉀、氨氣、甲胺、4-硝基咪唑等反應(yīng)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-雙(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)。研究結(jié)果表明：所有的親核取代反應(yīng)條件溫和,后處理過程簡單。設(shè)計了2,4,6-三氨基-3,5-二硝基吡啶-1-氧化物的新法合成,以2,6-二氯吡啶為原料,經(jīng)氮氧化、硝化、還原、再硝化四步反應(yīng)制備出中間體2,6-二氯-3,5-二硝基-4-氨基吡啶(129),并經(jīng)氨化和氮氧化步驟得到目標(biāo)化合物。研究了吡啶或苯并環(huán)脲硝胺結(jié)構(gòu)含能化合物的合成,采用2,3-二氨基吡啶為原料,經(jīng)閉環(huán)、硝化反應(yīng)得到化合物1,3,5-三硝基-1,3-二氫-2H-咪唑并[4,5-b]吡啶-2-酮(155);并進一步拓展使用5-氨基-1,3-二氫-2H-苯并咪唑-2-酮為原料,采用直接硝化法及通過氨基保護、硝化、脫保護、再硝化的間接合成法制備出5-氨基-1,3,6-三硝基-1,3-二氫-2H-苯并咪唑-2-酮(160),其中直接硝化法產(chǎn)率僅為11%,而間接合成法總產(chǎn)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%.
【學(xué)位授予單位】：南京理工大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2015
【分類號】：TQ560.1

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