Recyclable CuO nanoparticles were successfully employed to catalyze the microwave‐assisted(3+2)cycloaddition reaction between nitriles and NaN3to efficiently synthesize5‐substituted1H‐tetrazoles.The salient feature...Recyclable CuO nanoparticles were successfully employed to catalyze the microwave‐assisted(3+2)cycloaddition reaction between nitriles and NaN3to efficiently synthesize5‐substituted1H‐tetrazoles.The salient features associated with this protocol are its cost effectiveness,rapid synthesis,stability,reusability,mild reaction conditions without any additives,high tolerance to various functional groups,and excellent yields under microwave irradiation.This environmentally friendly,microwave‐assisted,nanoparticle‐catalyzed synthetic methodology is seen as an alternative to conventional procedures that involve Lewis acid catalysts and a simple operation to the privileged scaffold.展开更多
An efficient route for the synthesis of 5-substituted 1H-tetrazole via[2＋3]cycloaddition of nitriles and sodium azide is reported usingγ-Fe2O3 nanoparticles as a magnetic separable catalyst.Under optimized condition...An efficient route for the synthesis of 5-substituted 1H-tetrazole via[2＋3]cycloaddition of nitriles and sodium azide is reported usingγ-Fe2O3 nanoparticles as a magnetic separable catalyst.Under optimized conditions,the moderate to good yields（71-95%） can be obtained.The catalyst can be easily separated by a magnet and reused for several circles.展开更多
Two 5-substituted tetrazoles, 5-(2-thienyl)-1,2,3,4-tetrazole (2-THTT) and 5-(4-pyridyl)-1,2,3,4-tetrazole (4-PYTT), as copper corrosion inhibitors in aerated 0.5 M H2SO4 solution were studied by using potentiodynamic...Two 5-substituted tetrazoles, 5-(2-thienyl)-1,2,3,4-tetrazole (2-THTT) and 5-(4-pyridyl)-1,2,3,4-tetrazole (4-PYTT), as copper corrosion inhibitors in aerated 0.5 M H2SO4 solution were studied by using potentiodynamic polarization, electrochemical impedance spectroscopy (EIS) and quantum chemical calculation. Polarization curves indicate that inhibition efficiencies of tetrazoles increase with increasing inhibitors concentration. The electrochemical results show that the inhibition efficiency of 2-THTT is higher than that of 4-PYTT. Inhibition efficiency of 2-THTT reached 98.9% at very low concentrations (0.25 mM) by EIS, which makes 2-THTT an efficient inhibitor in aerated 0.5 M H2SO4 solution. The adsorption of 5-substituted tetrazoles on copper surface obeys the Langmuir isotherm. All the computed quantum chemical parameters are found to correlate well with experimental inhibition efficiencies of inhibitors.展开更多
A practical and metal-flee oxidative amidation of aldehydes with tetrazoles into 1,3,4-oxadiazoles has been de- veloped by employing tetrabutylammonium iodide （TBAI） as catalyst and tert-butyl hydroperoxide （TBHP）...A practical and metal-flee oxidative amidation of aldehydes with tetrazoles into 1,3,4-oxadiazoles has been de- veloped by employing tetrabutylammonium iodide （TBAI） as catalyst and tert-butyl hydroperoxide （TBHP） as oxidant. A wide range of 2,5-disubstituted 1,3,4-oxadiazoles can be conveniently generated in moderate to good yields. Gram-scale reaction was also realized in this catalytic system.展开更多
Based on the parent tetrazole 2N-oxide, six series of novel carbon-linked ditetrazole 2N- oxides with different energetic substituent groups （-NH2, -Na, -NO2, NF2, -NHNO2） and energetic bridge groups （-CH2-, -CH2-C...Based on the parent tetrazole 2N-oxide, six series of novel carbon-linked ditetrazole 2N- oxides with different energetic substituent groups （-NH2, -Na, -NO2, NF2, -NHNO2） and energetic bridge groups （-CH2-, -CH2-CH2-, -NH-, -N=N-, -NH-NH-） were designed. The overall performance and the effects of different energetic substituent groups and energetic bridge groups on the performance were investigated by density functional theory and electrostatic potential methods. The results showed that most of designed compounds have oxygen balance around zero, high heats of formation, high density, high energy, and acceptable sensitivity, indicating that tetrazole N-oxide is a useful parent energetic compound employed for obtaining high energy compounds, even only combined with some very common energetic substituent groups and bridge groups. Comprehensively considering the effects on energy and sensitivity, the -NO2, -NF2, -NH- and-NH-NH- are appropriate substituent groups for combining tetrozale N-oxide to design new energetic compounds, while -NH2, -Na, -CH2-CH2-, and -N=N- are inappropriate.展开更多
A combination of tetrachlorosilane（TCS） and phenol in dichloromethane was found to be an efficient reagent for hydro-chlorination ofα,β-unsaturated ketones to afford the correspondingβ-chloroketones in good yield...A combination of tetrachlorosilane（TCS） and phenol in dichloromethane was found to be an efficient reagent for hydro-chlorination ofα,β-unsaturated ketones to afford the correspondingβ-chloroketones in good yield at ambient temperature. Reactions of the titled compounds with TCS-NaN_3 as well as with nitriles utilizing TCS-ZnCl_2 to give 1,5-disubstituted tetrazole derivatives orβ-amido ketones respectively are also described.展开更多
A series of 1,3-bis（2-alkyltetrazol-5-yl）triazenes have been synthesized in high yields by treatment of sodium nitrite and hydrochloric acid with substituted-5-aminotetrazoles. All compounds were fully characterized...A series of 1,3-bis（2-alkyltetrazol-5-yl）triazenes have been synthesized in high yields by treatment of sodium nitrite and hydrochloric acid with substituted-5-aminotetrazoles. All compounds were fully characterized using IR spectroscopy,~1H NMR and^（13） C NMR spectroscopy and high resolution mass spectrometer（HRMS）. Most of these triazenes exhibit good detonation performance comparable with TNT and low melting points ranging from 81°C to 106°C, which are suitable for melt-cast explosives.Among these compounds, 1,3-bis（2-azidoethyltetrazol-5-yl）triazene（2g） displays a low melting point（106°C）, moderate onset decomposition temperature（183°C） and good detonation performance（D：7087 m/s; P： 17.6 GPa）.展开更多
The reaction of picoline derivatives 3-6 with hydrazonoylhalide 1a produced imidazo[1,2-a]pyridines 7-10, while the reaction of the same picoline derivatives with hydrazonoylhalide 1b afforded imidazo[1,2-a]pyridine-2...The reaction of picoline derivatives 3-6 with hydrazonoylhalide 1a produced imidazo[1,2-a]pyridines 7-10, while the reaction of the same picoline derivatives with hydrazonoylhalide 1b afforded imidazo[1,2-a]pyridine-2-ones 11-13. The reaction of 1b, c with 3-amino-1,2,4-triazole 14 produced the acyclic adducts 18 and 19, respectively. Reaction of 1b, 1c with 5-aminotetrazole 20 produced the acyclic products 23 and 24, respectively. Finally, the reaction of 1b with 4, 6-dimethyl-2-aminopyrimidine 27 afforded compound 29 rather than its isomeric structure 28. The structure of the products was confirmed by the different spectroscopic analytical methods including IR, MS, 1HNMR and 13CNMR.展开更多
Heterocyclic skeleton(Azoles)and different energetic groups containing high performing explosives are highly emerged in recent years to meet the challenging requirements of energetic materials in both military and civ...Heterocyclic skeleton(Azoles)and different energetic groups containing high performing explosives are highly emerged in recent years to meet the challenging requirements of energetic materials in both military and civilian applications with improved performance.For this purpose tetrazole(Azole)is identified as an attractive heterocyclic backbone with energetic functional groups nitro(-NO_(2)),nitrato(-ONO_(2)),nitrimino(-NNO_(2)),and nitramino(eNHeNO_(2))to replace the traditionally used high performing explosives.The tetrazole based compounds having these energetic functional groups demonstrated advanced energetic performance(detonation velocity and pressure),densities,and heat of formation(HOF)and became a potential replacement of traditional energetic compounds such as RDX.This review presents a summary of the recently reported nitro-tetrazole energetic compounds containing poly-nitro,di/mono-nitro,nitrato/nitramino/nitrimino,bridged/bis/di tetrazole and nitro functional groups,describing their preparation methods,advance energetic properties,and further applications as highperforming explosives,especially those reported in the last decade.This review aims to provide a fresh concept for designing nitro-tetrazole based high performing explosives together with major challenges and perspectives.展开更多
Photosensitive peptide hydrogels(PPHs) which allow photo-modulation on the self-assembly of peptides were broadly developed over the recent decades. The real-time and spatial modulation of hydrogel properties upon non...Photosensitive peptide hydrogels(PPHs) which allow photo-modulation on the self-assembly of peptides were broadly developed over the recent decades. The real-time and spatial modulation of hydrogel properties upon non-contact light illumination, allow the PPHs serving as super "smart" soft materials.Herein, we briefly summarized the PPHs preparing from the integration of diverse photosensitive moieties with peptides through gelation abilities, "smart" manner and applications. Moreover, a novel type of PPHs based on intramolecular biorthogonal photo-click reaction developed by our group has been demonstrated with relative mechanism and applications.展开更多
This review covers recent advances in the synthesis and energetic performance of nitrogen-rich 1,2,4-oxadiazole-azoles-based energetic materials.These materials comprise of 1,2,4-oxadiazole subunit as a key structural...This review covers recent advances in the synthesis and energetic performance of nitrogen-rich 1,2,4-oxadiazole-azoles-based energetic materials.These materials comprise of 1,2,4-oxadiazole subunit as a key structural motif linked to different nitrogen-rich or nitrogen-oxygen azoles:tetrazole,furazan,furoxan,1,3,4-oxadiazole,pyrazole,and triazole.Particular attention is devoted to the introduction of various energetic groups including nitro,nitramino,azo,azoxy,dinitromethyl,trinitroethyl moieties,and their combination.The physicochemical and available performance parameters including density,decomposition temperature,heat of formation,detonation pressure,detonation velocity,impact sensitivity,and friction sensitivity of typical energetic compounds are also provided and analyzed.Eventually,it was obtained that several screened compounds exhibit superior detonation properties and outstanding insensitivities,which can be classified as a new family of high-performance energetic materials.Additionally,1,2,4-oxadiazole-azoles-based energetic materials still have many thorough works to further exploited and studied,expecting to get very promising insensitive high explosives for practical application and industrialization.展开更多
Potassium 5,5＇-azobis（1-nitraminotetrazolate）,（K2ABNAT）, a new green primary explosive, was synthesized via a safe and convenient synthetic procedure based on methylcarbazate and cyanogen azide. The compound was ...Potassium 5,5＇-azobis（1-nitraminotetrazolate）,（K2ABNAT）, a new green primary explosive, was synthesized via a safe and convenient synthetic procedure based on methylcarbazate and cyanogen azide. The compound was characterized by single-crystal X-ray diffraction, IR spectroscopy, Raman spectroscopy, multinuclear NMR spectroscopy, elemental analysis, and differential scanning calorimetry（DSC）. With the calculated（CBS-4M） heat of formation（617.0 kJ/mol） and the room temperature X-ray density（2.11 g/cm^3）, impressive values for the detonation parameters such as detonation velocity（8367 m/s） and pressure（31.5 GPa） were computed using the EXPLO5 program. The superior calculated energetic performance show it could serve as a green replacement for the widely used primary explosive,lead（II） azide, which contains toxic ingredient.展开更多
A series of novel tetrazole containing 1,2,3-thiadiazole derivatives were designed and synthesized via Ugi reaction. Their structures were confirmed by melting points, IR, 1H NMR, and HRMS （ESI）. Preliminary bioassa...A series of novel tetrazole containing 1,2,3-thiadiazole derivatives were designed and synthesized via Ugi reaction. Their structures were confirmed by melting points, IR, 1H NMR, and HRMS （ESI）. Preliminary bioassay indicated that most target compounds exhibited very good direct anti-TMV activity at 100 μg/mL, which was equal to or higher than that of ribavirin. Among them, compounds 4b, 4c and 4i also showed equivalent protection effect to ribavirin in vivo at 100 μg/mL.展开更多
Three bench-stable difluoromethylene phosphonate hydrazones were prepared from simple diethyl(difluoromethyl)phosphonate within two steps in good yields. The [3 + 2] cycloaddition reaction of these diazo precursors wi...Three bench-stable difluoromethylene phosphonate hydrazones were prepared from simple diethyl(difluoromethyl)phosphonate within two steps in good yields. The [3 + 2] cycloaddition reaction of these diazo precursors with aryl diazonium salts has been accomplished under metal-free conditions with exclusive regioselectivity. This transformation provides practical access to a broad panel of 2-aryl-2 H-tetrazol-5-yl difluoromethylene phosphonates, including the corresponding derivatives of amino acid(phenylalanine) and drug cores(Pomalidomide and Lapatinib fragment).展开更多
A clean and saIe synthesis method of 5-（4＇-methylbiphenyl-2-yl）-1H-tetrazole was round： under hydrothermal conditions, 1.2 equiv, of 4＇-methylbiphenyl-2-carbonitrile react with 1 equiv, of sodium azide in a mixed...A clean and saIe synthesis method of 5-（4＇-methylbiphenyl-2-yl）-1H-tetrazole was round： under hydrothermal conditions, 1.2 equiv, of 4＇-methylbiphenyl-2-carbonitrile react with 1 equiv, of sodium azide in a mixed solvent of propane-1,2-diol/H2O, with 1.5 equiv, of ammonium chloride and 0.2 equiv. of ammonium fluoride as catalyst. After simple post-processing, the yield can be improved to 95%, and the purity of the product is 99% without further recrystaUization.展开更多
In this research,a promising class of insensitive and high-energy dense biopolymers,which contain nitrogen-rich 1H-tetrazol-1-yl acetate and nitrate ester functional groups,was successfully synthesized through tetrazo...In this research,a promising class of insensitive and high-energy dense biopolymers,which contain nitrogen-rich 1H-tetrazol-1-yl acetate and nitrate ester functional groups,was successfully synthesized through tetrazole derivatization and nitration of cellulose and its micro-sized derivative(TNCN and TCMCN).Their molecular structures,physicochemical properties,thermal behaviors,mechanical sensitivities and detonation performances were studied and compared to those of the corresponding nitrocellulose and nitrated micro-sized cellulose(NCN and CMCN).The developed energetic TNCN and TCMCN exhibited insensitive character with excellent features such as density of 1.710 g/cm3and 1.726 g/cm3,nitrogen content of 20.95%and 22.59%,and detonation velocity of 7552 m/s and 7786 m/s,respectively,and thereby demonstrate their potential applications as new generation of energetic biopolymers to substitute the common NCN.Furthermore,thermal results showed that the designed nitrated and chemical modified cellulosic biopolymers displayed good thermal stability with multistep decomposition mechanism.These results enrich future prospects for the design of promising insensitive and high-energy dense cellulose-rich materials and commence a new chapter in this field.展开更多
The title compound N-（（1-cyclohexyl-lH-tetrazol-5-yl）（5-methyl-l,2,3-thiadia- zol-4-yl） methyl）-4-nitrobenzenamine （C17H20N8O2S, Mr = 400.47） was synthesized via Ugi four- components condensation reaction （U-...The title compound N-（（1-cyclohexyl-lH-tetrazol-5-yl）（5-methyl-l,2,3-thiadia- zol-4-yl） methyl）-4-nitrobenzenamine （C17H20N8O2S, Mr = 400.47） was synthesized via Ugi four- components condensation reaction （U-4CR）, and its structure was characterized by IR, aH NMR, high-resolution mass spectrometry and single-crystal X-ray diffraction. The crystal belongs to orthorhombic, space group Pna21 with a = 20.390（2）, b = 12.9660（14）, c = 6.9399（8） A,β = 90.00°, Z = 4, V= 1834.7（3）A3, Mr = 400.47, Dc = 1.450 g/cm3, μ= 0.210 mm-1, F（000） = 840, R = 0.0348 and wR = 0.0717. X-ray analysis reveals that the dihedral angles formed between the thiadiazole and tetrazole rings, the benzene and tetrazole rings and the thiadiazole and benzene rings are 62.59, 86.73 and 70.07°, respectively. Three intermolecular hydrogen bonds N（1）-H（2）...N（6）, C（4）-H（4B）...O（2） and C（17）-H（17）...N（3） are observed. Bioassay shows that the title compound has antifungal and antivirus activities against tobacco mosaic virus.展开更多
Tetrazole monomers （Ⅰ, Ⅱ） and all of their possible stable dimers （1, 2, 3, 4, 5, 6, 7 and 8） were fully optimized by DFT method at the B3LYP/6-311＋＋G^＊＊ level. Among the eight dimers, there were two 1H-tetr...Tetrazole monomers （Ⅰ, Ⅱ） and all of their possible stable dimers （1, 2, 3, 4, 5, 6, 7 and 8） were fully optimized by DFT method at the B3LYP/6-311＋＋G^＊＊ level. Among the eight dimers, there were two 1H-tetrazole dimers, three 2H-tetrazole dimers and three hetero dimers of 1H-tetrazole and 2H-tetrazole. Vibrational frequencies were calculated to ascertain that each structure was stable （no imaginary frequencies）. The basis set superposition errors （BSSE） are 2.78, 2.28, 2.97, 2.75, 2.74, 2.18, 1.23 and 3.10 kJ/mol, and the zero point energy （ZPE） corrections for the interaction energies are 4.88, 4.18, 3.87, 3.65, 3.54, 3.22, 2.87 and 4.34 kJ/mol for 1, 2, 3, 4, 5, 6, 7 and 8, respectively. After BSSE and ZPE corrections, the greatest corrected intermolecular interaction energy of the dimers is -43.71 kJ/mol. The charge redistribution mainly occurs on the adjacent N-H…N atoms between submolecules. The charge transfer between two subsystems is very small. Natural bond orbital （NBO） analysis was performed to reveal the origin of the interaction. Based on the statistical thermodynamic method, the standard thermodynamic functions, heat capacities （C^0P）, entropies （S^0T） and thermal corrections to enthalpy （H^0T）, and the changes of thermodynamic properties from monomer to dimer in the temperature range of 200.00 K to 700 K have been obtained. 1H-tetrazole monomer can spontaneously turn into two stable dimers at 298.15 K.展开更多
基金CSIR-Govt of India for funding through Grant No. 01(2913)/17/EMR-II
文摘Recyclable CuO nanoparticles were successfully employed to catalyze the microwave‐assisted(3+2)cycloaddition reaction between nitriles and NaN3to efficiently synthesize5‐substituted1H‐tetrazoles.The salient features associated with this protocol are its cost effectiveness,rapid synthesis,stability,reusability,mild reaction conditions without any additives,high tolerance to various functional groups,and excellent yields under microwave irradiation.This environmentally friendly,microwave‐assisted,nanoparticle‐catalyzed synthetic methodology is seen as an alternative to conventional procedures that involve Lewis acid catalysts and a simple operation to the privileged scaffold.
基金the Jiangsu Province Foundation of Natural Science(No.BK2009678) for the financial support
文摘An efficient route for the synthesis of 5-substituted 1H-tetrazole via[2＋3]cycloaddition of nitriles and sodium azide is reported usingγ-Fe2O3 nanoparticles as a magnetic separable catalyst.Under optimized conditions,the moderate to good yields（71-95%） can be obtained.The catalyst can be easily separated by a magnet and reused for several circles.
文摘Two 5-substituted tetrazoles, 5-(2-thienyl)-1,2,3,4-tetrazole (2-THTT) and 5-(4-pyridyl)-1,2,3,4-tetrazole (4-PYTT), as copper corrosion inhibitors in aerated 0.5 M H2SO4 solution were studied by using potentiodynamic polarization, electrochemical impedance spectroscopy (EIS) and quantum chemical calculation. Polarization curves indicate that inhibition efficiencies of tetrazoles increase with increasing inhibitors concentration. The electrochemical results show that the inhibition efficiency of 2-THTT is higher than that of 4-PYTT. Inhibition efficiency of 2-THTT reached 98.9% at very low concentrations (0.25 mM) by EIS, which makes 2-THTT an efficient inhibitor in aerated 0.5 M H2SO4 solution. The adsorption of 5-substituted tetrazoles on copper surface obeys the Langmuir isotherm. All the computed quantum chemical parameters are found to correlate well with experimental inhibition efficiencies of inhibitors.
基金This project was financially supported by the National Natural Science Foundation of China （No. 21302014） and the Natural Science Foundation for Colleges and Universities of Jiangsu Province （No. 13KJB 150002）.
文摘A practical and metal-flee oxidative amidation of aldehydes with tetrazoles into 1,3,4-oxadiazoles has been de- veloped by employing tetrabutylammonium iodide （TBAI） as catalyst and tert-butyl hydroperoxide （TBHP） as oxidant. A wide range of 2,5-disubstituted 1,3,4-oxadiazoles can be conveniently generated in moderate to good yields. Gram-scale reaction was also realized in this catalytic system.
基金This work was supported by the Natural Science Foundation of Nanjing Institute of Technology （YKJ201507, CKJA201603） and the Youth Natural Sci- ence Foundation of Jiangsu Province （BK20160774）, and Outstanding Scientific and Technological Innovation Team in Colleges and Universities of Jiangsu Province.
文摘Based on the parent tetrazole 2N-oxide, six series of novel carbon-linked ditetrazole 2N- oxides with different energetic substituent groups （-NH2, -Na, -NO2, NF2, -NHNO2） and energetic bridge groups （-CH2-, -CH2-CH2-, -NH-, -N=N-, -NH-NH-） were designed. The overall performance and the effects of different energetic substituent groups and energetic bridge groups on the performance were investigated by density functional theory and electrostatic potential methods. The results showed that most of designed compounds have oxygen balance around zero, high heats of formation, high density, high energy, and acceptable sensitivity, indicating that tetrazole N-oxide is a useful parent energetic compound employed for obtaining high energy compounds, even only combined with some very common energetic substituent groups and bridge groups. Comprehensively considering the effects on energy and sensitivity, the -NO2, -NF2, -NH- and-NH-NH- are appropriate substituent groups for combining tetrozale N-oxide to design new energetic compounds, while -NH2, -Na, -CH2-CH2-, and -N=N- are inappropriate.
文摘A combination of tetrachlorosilane（TCS） and phenol in dichloromethane was found to be an efficient reagent for hydro-chlorination ofα,β-unsaturated ketones to afford the correspondingβ-chloroketones in good yield at ambient temperature. Reactions of the titled compounds with TCS-NaN_3 as well as with nitriles utilizing TCS-ZnCl_2 to give 1,5-disubstituted tetrazole derivatives orβ-amido ketones respectively are also described.
基金Financial support of this work from the National Natural Science Foundation of China(No.21372027)
文摘A series of 1,3-bis（2-alkyltetrazol-5-yl）triazenes have been synthesized in high yields by treatment of sodium nitrite and hydrochloric acid with substituted-5-aminotetrazoles. All compounds were fully characterized using IR spectroscopy,~1H NMR and^（13） C NMR spectroscopy and high resolution mass spectrometer（HRMS）. Most of these triazenes exhibit good detonation performance comparable with TNT and low melting points ranging from 81°C to 106°C, which are suitable for melt-cast explosives.Among these compounds, 1,3-bis（2-azidoethyltetrazol-5-yl）triazene（2g） displays a low melting point（106°C）, moderate onset decomposition temperature（183°C） and good detonation performance（D：7087 m/s; P： 17.6 GPa）.
文摘The reaction of picoline derivatives 3-6 with hydrazonoylhalide 1a produced imidazo[1,2-a]pyridines 7-10, while the reaction of the same picoline derivatives with hydrazonoylhalide 1b afforded imidazo[1,2-a]pyridine-2-ones 11-13. The reaction of 1b, c with 3-amino-1,2,4-triazole 14 produced the acyclic adducts 18 and 19, respectively. Reaction of 1b, 1c with 5-aminotetrazole 20 produced the acyclic products 23 and 24, respectively. Finally, the reaction of 1b with 4, 6-dimethyl-2-aminopyrimidine 27 afforded compound 29 rather than its isomeric structure 28. The structure of the products was confirmed by the different spectroscopic analytical methods including IR, MS, 1HNMR and 13CNMR.
基金We are thankful to the NSAF(U1830134),NSFC(21905023 and 21911530096)for their generous financial support.
文摘Heterocyclic skeleton(Azoles)and different energetic groups containing high performing explosives are highly emerged in recent years to meet the challenging requirements of energetic materials in both military and civilian applications with improved performance.For this purpose tetrazole(Azole)is identified as an attractive heterocyclic backbone with energetic functional groups nitro(-NO_(2)),nitrato(-ONO_(2)),nitrimino(-NNO_(2)),and nitramino(eNHeNO_(2))to replace the traditionally used high performing explosives.The tetrazole based compounds having these energetic functional groups demonstrated advanced energetic performance(detonation velocity and pressure),densities,and heat of formation(HOF)and became a potential replacement of traditional energetic compounds such as RDX.This review presents a summary of the recently reported nitro-tetrazole energetic compounds containing poly-nitro,di/mono-nitro,nitrato/nitramino/nitrimino,bridged/bis/di tetrazole and nitro functional groups,describing their preparation methods,advance energetic properties,and further applications as highperforming explosives,especially those reported in the last decade.This review aims to provide a fresh concept for designing nitro-tetrazole based high performing explosives together with major challenges and perspectives.
基金the financial support from the National Natural Science Foundation of China(Nos. 21572102, 21672103,21302093)the International Scientific Partnership Program ISPP at King Saud University for funding the research work through ISPP#0101
文摘Photosensitive peptide hydrogels(PPHs) which allow photo-modulation on the self-assembly of peptides were broadly developed over the recent decades. The real-time and spatial modulation of hydrogel properties upon non-contact light illumination, allow the PPHs serving as super "smart" soft materials.Herein, we briefly summarized the PPHs preparing from the integration of diverse photosensitive moieties with peptides through gelation abilities, "smart" manner and applications. Moreover, a novel type of PPHs based on intramolecular biorthogonal photo-click reaction developed by our group has been demonstrated with relative mechanism and applications.
基金We are thankful to the NSAF(No.U1830134)NSFC(No.21905023 and 22175025)+1 种基金State Key Laboratory of Explosion Science and Technology(No.YBKT21-02)Open Research Fund Program of CAS Key Laboratory of Energy Regulation Materials(No.ORFP2020-01)for their generous financial support.
文摘This review covers recent advances in the synthesis and energetic performance of nitrogen-rich 1,2,4-oxadiazole-azoles-based energetic materials.These materials comprise of 1,2,4-oxadiazole subunit as a key structural motif linked to different nitrogen-rich or nitrogen-oxygen azoles:tetrazole,furazan,furoxan,1,3,4-oxadiazole,pyrazole,and triazole.Particular attention is devoted to the introduction of various energetic groups including nitro,nitramino,azo,azoxy,dinitromethyl,trinitroethyl moieties,and their combination.The physicochemical and available performance parameters including density,decomposition temperature,heat of formation,detonation pressure,detonation velocity,impact sensitivity,and friction sensitivity of typical energetic compounds are also provided and analyzed.Eventually,it was obtained that several screened compounds exhibit superior detonation properties and outstanding insensitivities,which can be classified as a new family of high-performance energetic materials.Additionally,1,2,4-oxadiazole-azoles-based energetic materials still have many thorough works to further exploited and studied,expecting to get very promising insensitive high explosives for practical application and industrialization.
基金the National Natural Science Foundation of China (No. 21373157)
文摘Potassium 5,5＇-azobis（1-nitraminotetrazolate）,（K2ABNAT）, a new green primary explosive, was synthesized via a safe and convenient synthetic procedure based on methylcarbazate and cyanogen azide. The compound was characterized by single-crystal X-ray diffraction, IR spectroscopy, Raman spectroscopy, multinuclear NMR spectroscopy, elemental analysis, and differential scanning calorimetry（DSC）. With the calculated（CBS-4M） heat of formation（617.0 kJ/mol） and the room temperature X-ray density（2.11 g/cm^3）, impressive values for the detonation parameters such as detonation velocity（8367 m/s） and pressure（31.5 GPa） were computed using the EXPLO5 program. The superior calculated energetic performance show it could serve as a green replacement for the widely used primary explosive,lead（II） azide, which contains toxic ingredient.
基金funded in part by the NSF of Tianjin (No. 10JCZDJC17500)the National Key Project for Basic Research (No. 2010CB126105)+3 种基金National Key Technology Research and Development Program (No. 2011BAE06B02)the Foundation of Achievements Transformation and Application of Tianjin Agricultural Science and Technology (No. 201002250)Tianjin Key Technology Research and Development Program (No. 11ZCGYNC00100)The Commonweal Specialized Research Fund of China Agriculture (Nos. nyhyzx3-21, 201103016 and 201003029)
文摘A series of novel tetrazole containing 1,2,3-thiadiazole derivatives were designed and synthesized via Ugi reaction. Their structures were confirmed by melting points, IR, 1H NMR, and HRMS （ESI）. Preliminary bioassay indicated that most target compounds exhibited very good direct anti-TMV activity at 100 μg/mL, which was equal to or higher than that of ribavirin. Among them, compounds 4b, 4c and 4i also showed equivalent protection effect to ribavirin in vivo at 100 μg/mL.
基金supported by the National Natural Science Foundation of China (Nos.21772142,21901181 and 21961142015)the National Key Research and Development Program of China (No.2019YFA0905100)+1 种基金Tianjin Municipal Science & Technology Commission (No.19JCQNJC04700)the CNRS in France。
文摘Three bench-stable difluoromethylene phosphonate hydrazones were prepared from simple diethyl(difluoromethyl)phosphonate within two steps in good yields. The [3 + 2] cycloaddition reaction of these diazo precursors with aryl diazonium salts has been accomplished under metal-free conditions with exclusive regioselectivity. This transformation provides practical access to a broad panel of 2-aryl-2 H-tetrazol-5-yl difluoromethylene phosphonates, including the corresponding derivatives of amino acid(phenylalanine) and drug cores(Pomalidomide and Lapatinib fragment).
基金supported by the National Natural Science Foundations of China(Nos.21101026,20931002,20921004,90922005 and 91022003)
文摘A clean and saIe synthesis method of 5-（4＇-methylbiphenyl-2-yl）-1H-tetrazole was round： under hydrothermal conditions, 1.2 equiv, of 4＇-methylbiphenyl-2-carbonitrile react with 1 equiv, of sodium azide in a mixed solvent of propane-1,2-diol/H2O, with 1.5 equiv, of ammonium chloride and 0.2 equiv. of ammonium fluoride as catalyst. After simple post-processing, the yield can be improved to 95%, and the purity of the product is 99% without further recrystaUization.
基金financial support and the necessary facilities for this study by the Ecole Militaire polytechnique and the Ludwig-Maximilian University of Munich(LMU)。
文摘In this research,a promising class of insensitive and high-energy dense biopolymers,which contain nitrogen-rich 1H-tetrazol-1-yl acetate and nitrate ester functional groups,was successfully synthesized through tetrazole derivatization and nitration of cellulose and its micro-sized derivative(TNCN and TCMCN).Their molecular structures,physicochemical properties,thermal behaviors,mechanical sensitivities and detonation performances were studied and compared to those of the corresponding nitrocellulose and nitrated micro-sized cellulose(NCN and CMCN).The developed energetic TNCN and TCMCN exhibited insensitive character with excellent features such as density of 1.710 g/cm3and 1.726 g/cm3,nitrogen content of 20.95%and 22.59%,and detonation velocity of 7552 m/s and 7786 m/s,respectively,and thereby demonstrate their potential applications as new generation of energetic biopolymers to substitute the common NCN.Furthermore,thermal results showed that the designed nitrated and chemical modified cellulosic biopolymers displayed good thermal stability with multistep decomposition mechanism.These results enrich future prospects for the design of promising insensitive and high-energy dense cellulose-rich materials and commence a new chapter in this field.
基金funded in part by the NNSFC(20872071)the NSF of Tianjin(10JCZDJC17500)+3 种基金the National Key Project for Basic Research(2010CB126105)National Key Technology Research and Development Program(2011BAE06B02 and 2011BAE06B05)the Foundation of Achievements Transformation and Spreading of Tianjin Agricultural Science and Technology(201002250)the Common Wealth Specialized Research Fund of China Agriculture (nyhyzx3-21,201103016and201003029)
文摘The title compound N-（（1-cyclohexyl-lH-tetrazol-5-yl）（5-methyl-l,2,3-thiadia- zol-4-yl） methyl）-4-nitrobenzenamine （C17H20N8O2S, Mr = 400.47） was synthesized via Ugi four- components condensation reaction （U-4CR）, and its structure was characterized by IR, aH NMR, high-resolution mass spectrometry and single-crystal X-ray diffraction. The crystal belongs to orthorhombic, space group Pna21 with a = 20.390（2）, b = 12.9660（14）, c = 6.9399（8） A,β = 90.00°, Z = 4, V= 1834.7（3）A3, Mr = 400.47, Dc = 1.450 g/cm3, μ= 0.210 mm-1, F（000） = 840, R = 0.0348 and wR = 0.0717. X-ray analysis reveals that the dihedral angles formed between the thiadiazole and tetrazole rings, the benzene and tetrazole rings and the thiadiazole and benzene rings are 62.59, 86.73 and 70.07°, respectively. Three intermolecular hydrogen bonds N（1）-H（2）...N（6）, C（4）-H（4B）...O（2） and C（17）-H（17）...N（3） are observed. Bioassay shows that the title compound has antifungal and antivirus activities against tobacco mosaic virus.
文摘Tetrazole monomers （Ⅰ, Ⅱ） and all of their possible stable dimers （1, 2, 3, 4, 5, 6, 7 and 8） were fully optimized by DFT method at the B3LYP/6-311＋＋G^＊＊ level. Among the eight dimers, there were two 1H-tetrazole dimers, three 2H-tetrazole dimers and three hetero dimers of 1H-tetrazole and 2H-tetrazole. Vibrational frequencies were calculated to ascertain that each structure was stable （no imaginary frequencies）. The basis set superposition errors （BSSE） are 2.78, 2.28, 2.97, 2.75, 2.74, 2.18, 1.23 and 3.10 kJ/mol, and the zero point energy （ZPE） corrections for the interaction energies are 4.88, 4.18, 3.87, 3.65, 3.54, 3.22, 2.87 and 4.34 kJ/mol for 1, 2, 3, 4, 5, 6, 7 and 8, respectively. After BSSE and ZPE corrections, the greatest corrected intermolecular interaction energy of the dimers is -43.71 kJ/mol. The charge redistribution mainly occurs on the adjacent N-H…N atoms between submolecules. The charge transfer between two subsystems is very small. Natural bond orbital （NBO） analysis was performed to reveal the origin of the interaction. Based on the statistical thermodynamic method, the standard thermodynamic functions, heat capacities （C^0P）, entropies （S^0T） and thermal corrections to enthalpy （H^0T）, and the changes of thermodynamic properties from monomer to dimer in the temperature range of 200.00 K to 700 K have been obtained. 1H-tetrazole monomer can spontaneously turn into two stable dimers at 298.15 K.
