以4-硝基咪唑为原料,用HNO3/KI/AcO H作为硝化体系,通过一锅法制备了2,4,5-三硝基咪唑,用1H N M R,IR,M S以及元素分析对其结构进行了表征。优化了反应路线,结果表明,在反应时间4 h,反应温度为120℃,n(4-硝基咪唑)∶n(65%HN O3)∶n(AcO ...以4-硝基咪唑为原料,用HNO3/KI/AcO H作为硝化体系,通过一锅法制备了2,4,5-三硝基咪唑,用1H N M R,IR,M S以及元素分析对其结构进行了表征。优化了反应路线,结果表明,在反应时间4 h,反应温度为120℃,n(4-硝基咪唑)∶n(65%HN O3)∶n(AcO H)=1∶30∶30条件下,目标化合物产率高达80.6%。展开更多
In this paper,the solubility of 4-nitroimidazole in twelve pure solvents(toluene,benzene,1,4-dioxane,acetonitrile,ethyl acetate,acetone,GBL,ethanol,methanol,n-butanol,DMF and NMP)were determined by using the laser mon...In this paper,the solubility of 4-nitroimidazole in twelve pure solvents(toluene,benzene,1,4-dioxane,acetonitrile,ethyl acetate,acetone,GBL,ethanol,methanol,n-butanol,DMF and NMP)were determined by using the laser monitoring system from 278.15 K to 323.15 K under 101.1 k Pa,which are 0.00018–0.00070,0.00021–0.00073,0.00034–0.00092,0.00038–0.00142,0.00047–0.00120,0.00126–0.00303,0.00225–0.00517,0.00310–0.00724,0.00467–0.00982,0.00453–0.01940,0.01947–0.04652,and 0.04670–0.07452,respectively.At constant temperature,the mole fraction solubility of 4-nitroimidazole were increased as the following order:toluene<benzene<1,4-dioxane<(ethyl acetate or acetonitrile)<acetone<GBL<ethanol<(methanol or nbutanol)<DMF<NMP,and the solubility of 4-nitroimidazole in(ethyl acetate,acetonitrile)and(methanol,n-butanol)had an intersection point at 297.55 K and 281.85 K,respectively.The solubility of 4-nitroimidazole could be increased with increasing temperature in twelve pure solvents.The ideal model,modified Apelblat equation,polynomial empirical equation,andλh equation were used to correlate the experimental values.The experimental solubility values were employed to calculate the standard dissolution enthalpy,standard dissolution entropy and Gibbs energy.The dissolution of 4-nitroimidazole could be an endothermic process in twelve pure solvents.The determination and fitting solubility of 4-nitroimidazole have important guiding significance for the purification and crystallization of its preparation process.展开更多
以4-硝基咪唑为原料,通过与2-氨基-3,5-二硝基-6-氯吡啶、2,6-二氯-3-硝基吡啶缩合,合成出未见文献报道的化合物6-（4-硝基-咪唑-1-基）-2-氨基-3,5-二硝基吡啶（1#）及6-氯-3-硝基-2-（4-硝基-咪唑-1-基）-吡啶（3#）,收率分别为65%、5...以4-硝基咪唑为原料,通过与2-氨基-3,5-二硝基-6-氯吡啶、2,6-二氯-3-硝基吡啶缩合,合成出未见文献报道的化合物6-（4-硝基-咪唑-1-基）-2-氨基-3,5-二硝基吡啶（1#）及6-氯-3-硝基-2-（4-硝基-咪唑-1-基）-吡啶（3#）,收率分别为65%、52%;并采用此种方法优化了3-硝基-2-（4-硝基-咪唑-1-基）-吡啶（2#）的合成,收率为85%。进一步尝试了化合物3#的叠氮化反应,得到5-叠氮基-6-硝基四唑基[1,5-a]吡啶（4#）。采用核磁共振、质谱、红外光谱、元素分析等方法对相关化合物的结构进行了表征。利用TG和DSC分析法研究了化合物1#的热行为,结果表明：化合物1#的初始分解温度为221.83℃,分解放热总量为302.65 k J/mol,热失重温度范围为209.17~398.67℃,累计热失重71.84%。展开更多
A novel histidine derivative containing 4-nitroimidazole,(S)-2-(4-((4-nitro-1H-imidazol-1-yl) methyl) benzamido)-3-(1H-imidazol-4-yl)propanoic acid (His-NI),was synthesized and labeled with [99mTc(CO)3(H2O)3]+.The tri...A novel histidine derivative containing 4-nitroimidazole,(S)-2-(4-((4-nitro-1H-imidazol-1-yl) methyl) benzamido)-3-(1H-imidazol-4-yl)propanoic acid (His-NI),was synthesized and labeled with [99mTc(CO)3(H2O)3]+.The tricarbonyl technetium complex,the 99mTc(CO)3-His-NI,showed a 99% yield under mild conditions at a low His-NI ligand concentration of 10-4 molL-1,and its biodistribution in mice bearing S180 tumor had a selective accumulation in tumor (2.01±0.40%ID/g at 1 h postinjection) and a slow clearance.The tumor/muscle ratio was 1.64 at 1 h,3.10 at 4 h,and 3.88 at 24 h,indicating that the 99mTc(CO)3-His-NI has a potential to image tumor hypoxia.展开更多
2-Azido-4-nitroimidazole and its derivatives have been synthesized for energetic material applications. The synthesized compounds were fully characterized by 1H, 13C NMR spectroscopy and elemental analysis. Most of th...2-Azido-4-nitroimidazole and its derivatives have been synthesized for energetic material applications. The synthesized compounds were fully characterized by 1H, 13C NMR spectroscopy and elemental analysis. Most of them were determined by single crystal X-ray diffraction. The calculated densities of the compounds range between 1.71 and 1.92 g,cm-3. The calculated detonation pressures （P） for these derivatives fall in the range of 25.17 to 32.62 GPa and the detonation velocities （D） are distributed from 7.65 to 8.55 km·s-1.展开更多
The 2-azido-4-nitroimidazole-based energetic salts were synthesized in a simple and straightforward manner. The structures of these new salts were determined by IR, 1H NMR and 13C NMR spectroscopy and elemental analys...The 2-azido-4-nitroimidazole-based energetic salts were synthesized in a simple and straightforward manner. The structures of these new salts were determined by IR, 1H NMR and 13C NMR spectroscopy and elemental analysis. These salts also exhibited high positive enthalpies of formation, high nitrogen content, and moderate detonation properties.展开更多
A new method for synthesizing 5-chloro-1-methyl-4-nitroimidazole had been devoloped with diethyl oxalate,aqueous methylamine formate,phosphorus pentachloride,mixed acid etc as starting materials.Target molecule was ob...A new method for synthesizing 5-chloro-1-methyl-4-nitroimidazole had been devoloped with diethyl oxalate,aqueous methylamine formate,phosphorus pentachloride,mixed acid etc as starting materials.Target molecule was obtained through aminolysis reaction,semi-ring reaction and nitration reaction.The process provided an energy saving,high yield synthetic methodology.The yield of producing 5-chloro-1-methyl-4-nitroimidazole was up to 64%.All products were determined by MS,NMR and FT-IR.展开更多
基金National Natural Science Foundation of China and the China Academy of Engineering Physics(Grant No.11076017)the National Defense Advanced Research Projects(No.JKY-2012-1317)the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)
文摘以4-硝基咪唑为原料,用HNO3/KI/AcO H作为硝化体系,通过一锅法制备了2,4,5-三硝基咪唑,用1H N M R,IR,M S以及元素分析对其结构进行了表征。优化了反应路线,结果表明,在反应时间4 h,反应温度为120℃,n(4-硝基咪唑)∶n(65%HN O3)∶n(AcO H)=1∶30∶30条件下,目标化合物产率高达80.6%。
基金supported by the Military Chemistry and Pyrotechnics National Defense Specialty Fund for North University of China。
文摘In this paper,the solubility of 4-nitroimidazole in twelve pure solvents(toluene,benzene,1,4-dioxane,acetonitrile,ethyl acetate,acetone,GBL,ethanol,methanol,n-butanol,DMF and NMP)were determined by using the laser monitoring system from 278.15 K to 323.15 K under 101.1 k Pa,which are 0.00018–0.00070,0.00021–0.00073,0.00034–0.00092,0.00038–0.00142,0.00047–0.00120,0.00126–0.00303,0.00225–0.00517,0.00310–0.00724,0.00467–0.00982,0.00453–0.01940,0.01947–0.04652,and 0.04670–0.07452,respectively.At constant temperature,the mole fraction solubility of 4-nitroimidazole were increased as the following order:toluene<benzene<1,4-dioxane<(ethyl acetate or acetonitrile)<acetone<GBL<ethanol<(methanol or nbutanol)<DMF<NMP,and the solubility of 4-nitroimidazole in(ethyl acetate,acetonitrile)and(methanol,n-butanol)had an intersection point at 297.55 K and 281.85 K,respectively.The solubility of 4-nitroimidazole could be increased with increasing temperature in twelve pure solvents.The ideal model,modified Apelblat equation,polynomial empirical equation,andλh equation were used to correlate the experimental values.The experimental solubility values were employed to calculate the standard dissolution enthalpy,standard dissolution entropy and Gibbs energy.The dissolution of 4-nitroimidazole could be an endothermic process in twelve pure solvents.The determination and fitting solubility of 4-nitroimidazole have important guiding significance for the purification and crystallization of its preparation process.
文摘以4-硝基咪唑为原料,通过与2-氨基-3,5-二硝基-6-氯吡啶、2,6-二氯-3-硝基吡啶缩合,合成出未见文献报道的化合物6-（4-硝基-咪唑-1-基）-2-氨基-3,5-二硝基吡啶（1#）及6-氯-3-硝基-2-（4-硝基-咪唑-1-基）-吡啶（3#）,收率分别为65%、52%;并采用此种方法优化了3-硝基-2-（4-硝基-咪唑-1-基）-吡啶（2#）的合成,收率为85%。进一步尝试了化合物3#的叠氮化反应,得到5-叠氮基-6-硝基四唑基[1,5-a]吡啶（4#）。采用核磁共振、质谱、红外光谱、元素分析等方法对相关化合物的结构进行了表征。利用TG和DSC分析法研究了化合物1#的热行为,结果表明：化合物1#的初始分解温度为221.83℃,分解放热总量为302.65 k J/mol,热失重温度范围为209.17~398.67℃,累计热失重71.84%。
基金Supported by the National Natural Science Foundation of China(Grant No.20771011and21071010)
文摘A novel histidine derivative containing 4-nitroimidazole,(S)-2-(4-((4-nitro-1H-imidazol-1-yl) methyl) benzamido)-3-(1H-imidazol-4-yl)propanoic acid (His-NI),was synthesized and labeled with [99mTc(CO)3(H2O)3]+.The tricarbonyl technetium complex,the 99mTc(CO)3-His-NI,showed a 99% yield under mild conditions at a low His-NI ligand concentration of 10-4 molL-1,and its biodistribution in mice bearing S180 tumor had a selective accumulation in tumor (2.01±0.40%ID/g at 1 h postinjection) and a slow clearance.The tumor/muscle ratio was 1.64 at 1 h,3.10 at 4 h,and 3.88 at 24 h,indicating that the 99mTc(CO)3-His-NI has a potential to image tumor hypoxia.
文摘2-Azido-4-nitroimidazole and its derivatives have been synthesized for energetic material applications. The synthesized compounds were fully characterized by 1H, 13C NMR spectroscopy and elemental analysis. Most of them were determined by single crystal X-ray diffraction. The calculated densities of the compounds range between 1.71 and 1.92 g,cm-3. The calculated detonation pressures （P） for these derivatives fall in the range of 25.17 to 32.62 GPa and the detonation velocities （D） are distributed from 7.65 to 8.55 km·s-1.
文摘The 2-azido-4-nitroimidazole-based energetic salts were synthesized in a simple and straightforward manner. The structures of these new salts were determined by IR, 1H NMR and 13C NMR spectroscopy and elemental analysis. These salts also exhibited high positive enthalpies of formation, high nitrogen content, and moderate detonation properties.
文摘A new method for synthesizing 5-chloro-1-methyl-4-nitroimidazole had been devoloped with diethyl oxalate,aqueous methylamine formate,phosphorus pentachloride,mixed acid etc as starting materials.Target molecule was obtained through aminolysis reaction,semi-ring reaction and nitration reaction.The process provided an energy saving,high yield synthetic methodology.The yield of producing 5-chloro-1-methyl-4-nitroimidazole was up to 64%.All products were determined by MS,NMR and FT-IR.
