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1.
综述了六苄基六氮杂异伍兹烷(HBIW)五种氢解脱苄化合物的合成条件和工业制备工艺。这五种化合物是:四乙酰基二苄基六氮杂异伍兹烷(TADBIW)、四乙酰基二甲酰基六氮杂异伍兹烷(TADFIW)、四乙酰基六氮杂异伍兹烷(TAIW)、四乙酰基二乙基六氮杂异伍兹烷(TADEIW)和六乙酰基六氮杂异伍兹烷(HAIW)。其中的TADBIW系由HBIW经一次氢解合成,其它四种都系由HBIW经两次氢解合成。HBIW的这五种氢解脱苄化合物均可经硝解合成六硝基六氮杂异伍兹烷(HNIW)。另外,本文总结了HBIW及其五种氢解脱苄产物的红外、核磁和质谱数据及它们的基本性能参数。 相似文献
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综述了六苄基六氮杂异伍兹烷(HBIW)五种氢解脱苄化合物的合成条件和工业制备工艺。这五种化合物是:四乙酰基二苄基六氮杂异伍兹烷(TADBIW)、四乙酰基二甲酰基六氮杂异伍兹烷(TADFIW)、四乙酰基六氮杂异伍兹烷(TAIW)、四乙酰基二乙基六氮杂异伍兹烷(TADEIW)和六乙酰基六氮杂异伍兹烷(HAIW)。其中的TADBIW系由HBIW经一次氢解合成,其它四种都系由HBIW经两次氢解合成。HBIW的这五种氢解脱苄化合物均可经硝解合成六硝基六氮杂异伍兹烷(HNIW)。另外,本文总结了HBIW及其五种氢解脱苄产物的红外、核磁和质谱数据及它们的基本性能参数。 相似文献
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高张力笼形氮杂环化合物的合成 总被引:9,自引:0,他引:9
以六苄基六氮杂异伍兹烷(HBIW)为母体,Pd(OH)2/C为催化剂,在温和条件下,通过选择性催化氢解脱苄,使部分或全部苄基被其它官能团(如CH3O-,C2H5-,CHO-)取代,合成了4种N-取代六氮杂异伍兹烷,并鉴定了它们的结构.这些化合物都是高张力的笼形氮杂环化合物,且均可作为合成六硝基六氮杂异伍兹烷(HNIW)的前体,而HNIW是当今最引人注目和最有军用前景的高能量密度化合物(HEDC). 相似文献
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以CN, NC, ONO2, N3, NH2, N2H, NHNH2, N4H和N4H3 9种含氮高能基团为取代基, 分别取代2,4,6,8,10,12-六氮杂异伍兹烷(IW)中亚氨基的6个H原子所形成的9种六氮杂异伍兹烷衍生物作为研究目标分子. 运用密度泛函理论, 在B3LYP/6-31G**水平上求得了它们的分子几何构型、电子结构、解离能(BDE)及IR谱等信息, 并设计等键反应计算了生成热( ). 基于统计热力学原理计算拟合了100~1200 K温度范围内体系的热力学函数, 利用Kamlet-Jacobs方程估算了它们的爆轰性能. 研究结果表明, 9种六氮杂异伍兹烷衍生物存在两种可能的热解引发类型. 在衍生物HNiIW, HBDAIW和HBAIW中, 可能的热解引发键是取代基内部的化学键, 而其余衍生物的热解引发键则可能是骨架N与取代基R之间N—R键. 另外, 硝酸酯基(ONO2)取代所得化合物HNiIW的密度ρ、爆速D及爆压p分别为1.998 g8226;cm-3, 9.71 km8226;s-1和44.47 GPa, 完全达到高能量密度化合物(HEDC)的基本要求, 且优于已应用的HNIW, 有望成为新型的HEDC. 相似文献
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β-六硝基六氮杂异伍兹烷的合成及晶体结构 总被引:2,自引:1,他引:2
从苄胺和乙二醛出发 ,通过缩合、氢解脱苄及硝解三步合成了高张力多环笼形化合物———六硝基六氮杂异伍兹烷 (HNIW) ,它是迄今为止密度及能量水平最高的高能量密度化合物 .β HNIW的晶体结构表明 ,它是由 2个五元环及 1个六元环构成的笼形结构 ,每个桥氮原子上各连有 1个硝基 ,—NO2 基本位于一平面内 ,C—C键长为 0 1 5 6~ 0 .1 5 9nm ,比标准的sp3 C—C键长 0 0 0 2~ 0 .0 0 5nm .晶体学数据为 :正交晶系 ,空间群Pca2 1,a =0 .96 70 ( 2 )nm ,b =1 .1 6 1 6 ( 2 )nm ,c =1 .30 32 ( 3)nm ;V =1 .46 38( 5 )nm3 ,Z =4,Dc=1 .989g·cm-3 (Dm=1 .982 g·cm-3 ) . 相似文献
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通过控制六苄基六氮杂异伍兹烷(HBIW)的氢解程度,成功制备了其氢解反应过程中一个重要的中间体三乙酰基三苄基六氮杂异伍兹烷(TATBIW),并对其单晶结构(TATBIW·0.5H2O)进行了测定,它属三斜晶系,空间群为P-1,a=0.9893(2)nm,b=1.2624(3)nm,c=1.3396(3)nm;V=1.5963(6)nm3,z=2,Dc=1.194 g·cm-3,该化合物的单晶数据未见文献报道.TATBIW的制备有助于我们进一步了解HBIW的氢解反应机理,提高氢解产品得率. 相似文献
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Reduction of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane with a sub-stoichiometric amount of SnCl2 afforded a mixture of isomeric 2,4,6,8,10- and 2,4,6,8,12-pentanitro-2,4,6,8,10,12-hexaazaisowurtzitanes, their ratio depending on the solvent used. Treatment of these compounds with NOBF4 gave rise to isomeric pentanitronitroso-2,4,6,8,10,12-hexaazaisowurtzitanes, which can be transformed into the starting NH products by treating with HCl. 相似文献
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Zhang Shijie Zhang Jiaoqiang Kou Kaichang Jia Qian Xu Yunlong Zerraza Sofiane Liu Ning Hu Rongzu 《Journal of Thermal Analysis and Calorimetry》2019,135(6):3363-3373
Journal of Thermal Analysis and Calorimetry - 2,4,6,8,10,12-Hexanitro-2,4,6,8,10,12-hexazisowurtzitane (HNIW)·1,3,5,7-tetranitro-1,3,5,7-tetrazocane (HMX) co-crystal in a 2:1 molar ratio was... 相似文献
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Multi‐functionality compound 2,4,6,8,10,12‐hexa(p‐bromo)‐benzyl‐2,4,6,8,10,12‐hexaazaiso‐wurtzitane (Br‐HBIW) was synthesized and used for the core of star‐like polymers. Star‐like polyfluorene based on 2,4,6,8,10,12‐hexabenzyl‐2,4,6,8,10,12‐hexaazaisowurtzitane (HBIW) caged‐core was synthesized by Suzuki coupling method. The comparative studies between the star‐like polyfluorene and the linear polyfluorene based on UV–Vis and photoluminescence (PL) spectra revealed that the bulky HBIW cage could reduce the chain aggregation and π–π interaction, so brought about improved PL quantum efficiency and annealing PL stability. Such results could be owed to the successful suppression of excimers formation, which originated from the incorporation of the HBIW cage and star‐like architecture. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
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Reductive debenzylation of hexabenzylhexaazaisowurtzitane — the key step of the synthesis of polycyclic nitramine hexanitrohexaazaisowurtzitane 总被引:1,自引:0,他引:1
Main features of the reductive debenzylation of 2,4,6,8,10,12-hexabenzyl-2,4,6,8,10,12-hexaazaisowurtzitane were studied.
This process is the key step of the synthesis of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazatetracyclo[5.5.0.03,11.05,9]dodecane (hexanitrohexaazaisowurtzitane, CL-20), a compound with unique energetic and explosive characteristics. The use
of the latter is restricted so far by the high cost of the two-step process of debenzylation during which the compound is
rapidly deactivated. The expensive Pd/C catalyst is deactivated in the first step of the process, which limits the use of
this polycyclic nitramine. The influence of the solvent nature; loadings of the reactants, catalyst, and cocatalyst; the hydrogen
pressure and reaction temperature on the general features of the process and the yield of the target precursor of CL-20 was
studied.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2290–2295, December, 2007. 相似文献
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Anton P. Koskin Irina L. Simakova Valentin N. Parmon 《Reaction Kinetics and Catalysis Letters》2007,92(2):293-302
Polycyclic nitramine hexanitrohexaazaisowurtzitane (HNIW, CL-20) is synthesized via hydrodebenzylation of a precursor over
palladium-based catalyst. In the present work, we studied the influence of the synthesis method of the palladium-based catalyst
on the catalyst behavior during the hydrodebenzylation reaction of 2,4,6,8,10,12-hexabenzyl-2,4,6,8,10,12-hexaazatetracyclo[5.5.0.03,11.05,9] dodecane. 相似文献
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S. M. Aldoshin Z. G. Aliev T. K. Goncharov A. I. Kazakov Yu. M. Milekhin N. A. Plishkin N. I. Shishov 《Russian Chemical Bulletin》2013,62(6):1354-1360
Crystals containing 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane and trinitrotoluene molecules in a 1: 1 ratio were obtained. The crystal structure was determined, and DSC thermograms, thermal stability, and the standard enthalpy of formation were investigated. An analysis of the crystal structure shows that interactions between the oxygen and nitrogen atoms of the nitro groups ON=O…NO2 of adjacent molecules are among the structure-forming intermolecular interactions in the crystals of polynitroamine compounds. 相似文献
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A sulfobutyl ether-beta-cyclodextrin-assisted electrokinetic chromatographic method was developed to rapidly resolve and detect the cyclic nitramine explosives 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaaza-isowurtzitane (CL-20), octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and their related degradation intermediates in environmental samples. Development of the electrophoretic method required the measurement of the aqueous solubility of CL-20 which was determined to be 3.59 +/- 0.74 mg/l at 25 degrees C (95% confidence interval, n=3). The performance of the method was then compared to results obtained from existing high-performance liquid chromatography methods including US Environmental Protection Agency method 8330. 相似文献
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Kalashnikov A. I. Sysolyatin S. V. Sakovich G. V. Dubkov A. S. Kulagina D. A. 《Russian Chemical Bulletin》2017,66(3):531-536
Russian Chemical Bulletin - Nitrolysis of 2,6,8,12-tetraacetyl-4,10-dibenzyl-2,4,6,8,10,12-hexaazatetracyclo-[5.5.0.03,11.05,9]dodecane results in the substitution of benzyl groups by the nitro... 相似文献
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The mechanism of unimolecular decomposition of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane. A computational DFT study 总被引:2,自引:0,他引:2
Okovytyy S Kholod Y Qasim M Fredrickson H Leszczynski J 《The journal of physical chemistry. A》2005,109(12):2964-2970
By using the B3LYP level of density functional theory, possible decomposition reaction pathways of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20) in the gas phase have been investigated. We have found several types of reactions for this process: homolytic cleavage of an N-N bond to form the NO2* group; HONO elimination; C-C and C-N bonds breaking leading to ring opening; and H-migration. On the basis of the results of computation scanning of the potential energy surface, the most favorite pathway of CL-20 unimolecular decomposition that results in the formation of the stable aromatic compound 1,5-dihydrodiimidazo[4,5-b:4',5'-e]pyrazine has been proposed. 相似文献
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Saint Martin S Marre S Guionneau P Cansell F Renouard J Marchetto V Aymonier C 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(45):13473-13478
HNIW or CL20 (2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane) is a nitramine, which is considered as the highest energetic molecular compound known to date, therefore, attracting increasing interest in propulsion applications. Additionally, CL20 is an interesting system for fundamental studies, exhibiting several polymorphs, which can behave as host lattices for trapping guest molecules. Herein, a new CL20 structure that contains inserted CO(2) molecules is reported. A combination of Fourier transform infra red (FTIR) spectroscopy, scanning electron microscopy (SEM), single-crystal X-ray diffraction, and thermal analyses (thermogravimetric analysis coupled with mass spectrometry and differential scanning calorimetry) was used to characterize this new material. 相似文献