Heterocyclic ketene aminals 1 react with aryl azides 2 to give the titled compounds 3,and in some cases also with the formation of fused heterocycles 4.
A visible-light-enabled method for the synthesis ofα-azidoketones has been developed via oxo-azidation of alkenyl silanes with trimethylsilylazide and molecular oxygen under mild conditions.The reaction could be carr...A visible-light-enabled method for the synthesis ofα-azidoketones has been developed via oxo-azidation of alkenyl silanes with trimethylsilylazide and molecular oxygen under mild conditions.The reaction could be carried out in gram scale.Various radical sources,including trifluoromethyl radical,thiocyanate radical,bromide radical,chlorine radical could partici-pate effectively instead of azide radical in the reaction.展开更多
Isothiocyanates(ITCs)are an important class of organic compounds characterized by the functional group R-N=C=S.These functional groups are widely found in multiple natural products and pharmaceutical important drugs.M...Isothiocyanates(ITCs)are an important class of organic compounds characterized by the functional group R-N=C=S.These functional groups are widely found in multiple natural products and pharmaceutical important drugs.Moreover,due to their high and versatile reactivity,they are widely used as an intermediate in organic synthesis.Keeping in view ITCs importance,this review summarizes their synthesis from nitrogen rich raw materials like amines,isocyanides,azides and some other compounds like oximes.Besides their synthesis,their application in organic compound synthesis as an intermediate will also be covered.Future research will likely focus on optimizing the synthesis of multifunctional isothiocyanates,understanding their complex biological mechanisms,exploring new applications,and highlighting the continued importance of isothiocyanates in modern chemistry and biotechnology.展开更多
Gold-catalyzed amination reactions based on azides viaα-imino gold carbene intermediates have attracted extensive attention in the past decades because this methodology leads to the facile and efficient construction ...Gold-catalyzed amination reactions based on azides viaα-imino gold carbene intermediates have attracted extensive attention in the past decades because this methodology leads to the facile and efficient construction of synthetically useful N-containing molecules,especially valuable N-heterocycles.However,successful examples of intermolecular generation ofα-imino gold carbenes by using azides as amination reagents are rarely explored probably due to the weak nucleophilicity of azides.Herein,we disclose an efficient gold-catalyzed intermolecular aminative cyclopropanation of ynamides with the allyl azides,enabling flexible synthesis of a wide range of valuable 3-azabicyclo[3.1.0]hex-2-ene derivatives in good to excellent yields with excellent diastereoselectivities.Importantly,this protocol represents the first use of allyl azide as an efficient amination reagent in gold-catalyzed alkyne amination reactions.展开更多
The high-pressure structure and elastic properties of calcium azide(Ca(N_(3))_(2))were investigated using in-situ highpressure x-ray diffraction and Raman scattering up to 54 GPa and 19 GPa,respectively.The compressib...The high-pressure structure and elastic properties of calcium azide(Ca(N_(3))_(2))were investigated using in-situ highpressure x-ray diffraction and Raman scattering up to 54 GPa and 19 GPa,respectively.The compressibility of Ca(N_(3))_(2)changed as the pressure increased,and no phase transition occurred within the pressure from ambient pressure up to 54 GPa.The measured zero-pressure bulk modulus of Ca(N_(3))_(2)is higher than that of other alkali metal azides,due to differences in the ionic character of their metal-azide bonds.Using CASTEP,all vibration modes of Ca(N_(3))_(2)were accurately identified in the vibrational spectrum at ambient pressure.In the high-pressure vibration study,several external modes(ext.)and internal bending modes(ν_(2))of azide anions(N_(3)^(-))softened up to~7 GPa and then hardened beyond that pressure.This evidence is consistent with the variation observed in the F_(E)–f_(E)data analyzed from the XRD result,where the slope of the curve changes at 7.1 GPa.The main behaviors under pressure are the alternating compression,rotation,and bending of N_(3)^(-)ions.The bending behavior makes the structure of Ca(N_(3))_(2)more stable under pressure.展开更多
Copper-based azide(Cu(N_(3))2 or CuN_(3),CA)chips synthesized by in-situ azide reaction and utilized in miniaturized explosive systems has become a hot research topic in recent years.However,the advantages of in-situ ...Copper-based azide(Cu(N_(3))2 or CuN_(3),CA)chips synthesized by in-situ azide reaction and utilized in miniaturized explosive systems has become a hot research topic in recent years.However,the advantages of in-situ synthesis method,including small size and low dosage,bring about difficulties in quantitative analysis and differences in ignition capabilities of CA chips.The aim of present work is to develop a simplified quantitative analysis method for accurate and safe analysis of components in CA chips to evaluate and investigate the corresponding ignition ability.In this work,Cu(N_(3))2 and CuN_(3)components in CA chips were separated through dissolution and distillation by utilizing the difference in solubility and corresponding content was obtained by measuring N_(3)-concentration through spectrophotometry.The spectrophotometry method was optimized by studying influencing factors and the recovery rate of different separation methods was studied,ensuring the accuracy and reproducibility of test results.The optimized method is linear in range from 1.0-25.0 mg/L,with a correlation coefficient R^(2)=0.9998,which meets the requirements of CA chips with a milligram-level content test.Compared with the existing ICP method,component analysis results of CA chips obtained by spectrophotometry are closer to real component content in samples and have satisfactory accuracy.Moreover,as its application in miniaturized explosive systems,the ignition ability of CA chips with different component contents for direct ink writing CL-20 and the corresponding mechanism was studied.This study provided a basis and idea for the design and performance evaluation of CA chips in miniaturized explosive systems.展开更多
The long sought cubic gauche polymeric nitrogen(cg-N)consisting of N-N single bonds has been synthesized by one pot route using sodium azide as a precursor at ambient conditions.The recrystallization process was desig...The long sought cubic gauche polymeric nitrogen(cg-N)consisting of N-N single bonds has been synthesized by one pot route using sodium azide as a precursor at ambient conditions.The recrystallization process was designed to expose crystal faces with low activation energy that facilitates initiating the polymeric reaction at ambient conditions.The azide was considered as a precursor due to the low energy barrier in transforming double bonded N=N to single bonded cg-N.Raman spectrum measurements detected the emerging vibron peaks at 635 cm^(−1) for the polymerized sodium azide samples,demonstrating the formation of cg-N with N-N single bonds.Different from traditional high-pressure technique and recently developed plasma enhanced chemical vapor deposition method,the route achieves the quantitative synthesis of cg-N at ambient conditions.The one pot synthesis of cg-N offers potential for further scaling up production as well as practical applications of polymeric nitrogen based materials as high energy density materials.展开更多
An efficient visible-light-induced radical cascade azidation/cyclization of 2-aryl indoles with trimethylsilyl azide(TMSN3)has been developed using organic dye Rose Bengal as the photocatalyst.This method did not requ...An efficient visible-light-induced radical cascade azidation/cyclization of 2-aryl indoles with trimethylsilyl azide(TMSN3)has been developed using organic dye Rose Bengal as the photocatalyst.This method did not require metal catalysts and additives,and used air as the oxidant to obtain diverse indolo[2,1-a]isoquinolin-6(5H)-ones in moderate to good yields.Mechanistic studies demonstrated that the reaction proceeded via a radical pathway.展开更多
In the pursuit of advancing imidazolium-based energetic ionic liquids (EILs),the current study is devoted to the synthesis and characterization of 1,3-dibutyl-imidazolium azide ([BBIm][N_(3)]),as a novel member in thi...In the pursuit of advancing imidazolium-based energetic ionic liquids (EILs),the current study is devoted to the synthesis and characterization of 1,3-dibutyl-imidazolium azide ([BBIm][N_(3)]),as a novel member in this ionic liquids class.The chemical structure of this EIL was rigorously characterized and confirmed using FTIR spectroscopy,1D,and 2D-NMR analyses.The thermal behavior assessment was conducted through DSC and TGA experiments.DSC analysis revealed an endothermic glass transition at T_(g)=-61℃,followed by an exothermic degradation event at T_(onset)=311℃.Similarly,TGA thermograms exhibited a one-stage decomposition process resulting in 100% mass loss of the sample.Furthermore,the short-term thermal stability of the azide EIL was investigated by combining the non-isothermal TGA data with the TAS,it-KAS,and VYA/CE isoconversional kinetic approaches.Consequently,the Arrhenius parameters(E_(a)=154 kJ·mol^(-1),Log(A/s^(-1))=11.8) and the most probable reaction model g(a) were determined.The observed high decomposition temperatures and the significantly elevated activation energy affirm the enhanced thermal stability of the modified EIL.These findings revealed that[BBIm][N_(3)]EIL can be a promising candidate for advanced energetic material application.展开更多
bis(azidomethyl) 3,3′ bis(1,2,4 oxadiazole)(Ⅰ) and bis(azidoacetamino) oxazofurazan(Ⅱ) were synthesized. The structures of these two compounds have been identified by IR, 1H NMR, MS and elemental analy...bis(azidomethyl) 3,3′ bis(1,2,4 oxadiazole)(Ⅰ) and bis(azidoacetamino) oxazofurazan(Ⅱ) were synthesized. The structures of these two compounds have been identified by IR, 1H NMR, MS and elemental analysis. Azido groups were introduced into furazan derivatives and energetic materials of high nitrogen content and high enthalpy of formation can be obtained. The densities of compound Ⅰ and Ⅱ are relatively high. Compound Ⅰ is an azide of lower melting point, it is hopeful to be applied as energetic plastic additives.展开更多
Tazobactam,β lactamase inhibitor, was synthesized from 6 aminopenicillanic acid through eleven steps, including diazotization, bromination, oxidation, chlorization, cyclization, deprotection and so on. The designed...Tazobactam,β lactamase inhibitor, was synthesized from 6 aminopenicillanic acid through eleven steps, including diazotization, bromination, oxidation, chlorization, cyclization, deprotection and so on. The designed route was examined, particularly the azide substitution and cyclization. In the latter reaction, vinyl acetic ester was employed in place of acetylene.展开更多
The photocatalytic activity of cobalt octakis（butylthio） porphyrazine（CoPz（BuS）8） was assessed through photodegradation of the dye rhodamine B（RhB） in water under irradiation with a Xe lamp and aerated conditi...The photocatalytic activity of cobalt octakis（butylthio） porphyrazine（CoPz（BuS）8） was assessed through photodegradation of the dye rhodamine B（RhB） in water under irradiation with a Xe lamp and aerated conditions.The photocatalytic activity of CoPz（BuS）8 loaded on Al2O3 or SiO2@Fe3O4nanoparticles or coordinated with an axial azide ligand was also investigated.The results demonstrated that the photocatalytic activity of CoPz（BuS）8 loaded on Al2O3 was higher than that loaded on SiO2@Fe3O4.The kinetic curves of RhB degradation in aqueous solutions at different pH indicated the pseudo first-order kinetics of the reaction.The highest degradation rate for CoPz（BuS）8 loaded Al2O3 at pH = 4 after 160 min was 84.6%.However,the advantages of easier separation and recycling as well as the ability to terminate the reaction at any time for the CoPz（BuS）8 loaded SiO2@Fe3O4 cannot be ignored.When electron-rich NaN3 was coordinated with CoPz（BuS）8 as an axial ligand and loaded on Al2O3,the resulting catalyst produced more active oxygen species such as O2^- and HO· to promote the quicker degradation of RhB than that by the other catalysts.For the N3-coordinated CoPz（BuS）8 loaded on Al2O3,the reactions at pH = 4 and 7 distinctly deviated from first-order kinetics,and the degradation rate reached 77.6%after 80 min at pH = 4.展开更多
A core trisaccharide of laminin, β-D-Gal-（1→4）-β-D-GlcpNAc-（1→6）-α-D-Manp-OMe, with potential anti-rumor metastatic activity was designed and prepared. 2-Iodoglactosyl azide was used as the donor to construct...A core trisaccharide of laminin, β-D-Gal-（1→4）-β-D-GlcpNAc-（1→6）-α-D-Manp-OMe, with potential anti-rumor metastatic activity was designed and prepared. 2-Iodoglactosyl azide was used as the donor to construct 2-N-acetamido-2-deoxylactosyl moiety through an azidoiodo-glycosylation reaction. Simultaneously, 1, 2-trans-β-glycosic bond was formed stereoselectively in one step with a moderate yield. This novel procedure avoided the use of 2-amino-2-deoxyglucose as both donor and acceptor.展开更多
The great achievements of click chemistry have encouraged polymer scientists to use this reaction in their field. This review assembles an update of the advances of using azide-alkyne click polymerization to prepare f...The great achievements of click chemistry have encouraged polymer scientists to use this reaction in their field. This review assembles an update of the advances of using azide-alkyne click polymerization to prepare functional polytriazoles（PTAs） with linear and hyperbranched structures.The Cu（I）-mediated click polymerization furnishes 1,4-regioregular PTAs,whereas,the metal-free click polymerization of propiolates and azides produces PTAs with 1,4-regioisomer contents up to 90%.The PTAs display advanced functions,such as aggregation-induced emission,thermal stability,biocompatibility and optical nonlinearity.展开更多
Wide potential windows were found at carbon nanotube film electrodes in neutral solutions after being treated with nitric acid and mixed acid. Electrochemical reversibility was investigated at carbon nanotube films wi...Wide potential windows were found at carbon nanotube film electrodes in neutral solutions after being treated with nitric acid and mixed acid. Electrochemical reversibility was investigated at carbon nanotube films with different pretreatments for ferri/ferrocyanide and quinone /hydroquinone. Carbon nanotube film electrodes presented quasi-reversible electrochemical behavior for both electrolytes. In the range of scan rate, carbon nanotube film electrodes treated with acids showed heterogeneous electron-transfer properties, which was mainly controlled by its electron state density on the surface of the film. On the whole, the carbon nanotube electrode with nitric acid treatment presented the best electrochemical behaviors, so we chose it as an analytical electrode to determine the trace compound in dilute solution. The results demonstrated that this new electrode material exhibits superior performance characteristics for the detection of azide anion.展开更多
Aluminum(Al) particles are good fuel additives to improve the energy output performances of explosives. Under detonation environment, reaction delay of Al particles plays a key role in the energy release efficiency. U...Aluminum(Al) particles are good fuel additives to improve the energy output performances of explosives. Under detonation environment, reaction delay of Al particles plays a key role in the energy release efficiency. Up to date, reaction delay of Al particles is still limited by the efficiency of mass and heat transfer from oxidizers to Al particles. To address this issue, a homogeneous fuel-oxidizer assembly has recently become a promising strategy. In this work, oxidizer-activated Al fuel particles(ALG) were prepared with glycidyl azide polymer(GAP) as the oxidizer. The ALG was in uniform spherical shape and core-shell structure with shell layer of around 5 nm which was observed by scanning electron microscope and transmission electron microscope. The localized nanoscale mid-IR measurement detected the uniform distribution of characteristic absorption bond of GAP in the shell layer which confirmed the homogenous fuel-oxidizer structure of ALG. A thermal gravimetric analysis of ALG at ultrafast heating rate of 1000℃/min under argon atmosphere was conducted. The decomposition of GAP finished much earlier than that of GAP at heating rate of 10℃/min. Under ultrafast high laser fluence, the reaction response of ALG was characterized and compared with that of micro-sized Al(μAl). With the increase of laser energy, the propagation distance of the shock wave increased. However, the velocity histories were nearly the same when energies were lower than 299 mJ or higher than 706 mJ. The propagation distance of the shock wave for ALG was 0.5 mm larger than that for μAl at 2.1 μs. The underwater explosion showed the peak pressure and the shock wave energy of the ALG-based explosive were both higher than those of the μAl-based explosive at 2.5 m. This study shows the feasibility to improve the energy release of Al-based explosives via using the oxidizer-activated Al fuel particles with energetic polymer as the oxidizer.展开更多
A new method for the synthesis of 4,4′,6,6′-tetra(azido)azo-1,3,5-triazine (TAAT) is described. The key intermediate 4,4′,6,6′-tetra(azido)hydrazo-1,3,5-triazine (TAHT) was synthesized by nucleophilic substitution...A new method for the synthesis of 4,4′,6,6′-tetra(azido)azo-1,3,5-triazine (TAAT) is described. The key intermediate 4,4′,6,6′-tetra(azido)hydrazo-1,3,5-triazine (TAHT) was synthesized by nucleophilic substitution in the case of sodium azide as nucleophile. N-Bromosuccinide (NBS) was used as oxidant to oxidize TAHT by a tractable operation under mild reaction condition. The target compound TAAT was obtained with a facile process and high overall yield of 81%. The structures of TAAT and its intermediates were identified by spectroscopic methods.展开更多
Field and pot experiments were conducted using indica rice varieties with differential chalkiness. There were significant differences in root activity among the varieties. The percentages of chalky grains and chalky a...Field and pot experiments were conducted using indica rice varieties with differential chalkiness. There were significant differences in root activity among the varieties. The percentages of chalky grains and chalky area were both negatively correlated with root activity expressed as α-naphthylamine oxidation ability （RA） per gram of fresh root （RAfw） , RA per spikelet （RAgrn）, or RA per sink capacity （RAsink）. The RAsink was more closely related to chalkiness than RAt, and RAgrn when varieties differed greatly in panicle size and grain weight. Application of NO3^--N fertilizer at heading resulted in higher root activity and reduced chalkiness. Application of 30 mg/L NaN3 （respiration inhibitor） resulted in reduced root activity and increased chalkiness for one variety ＇GD9501＇, but for the other variety ＇Qinluai＇ was in reverse. The percentages of chalky grains and chalky area were negatively correlated with root activity at 10 days after heading under different chemical treatments （r=-0.8567^＊ and r=-0.9211^＊＊, respectively）.展开更多
An efficient and mild protocol for bromination of aryl azides with N-bromosuccinimide（NBS） under FeCl_3 catalysis in 1,2- dichloroethane was developed.It is proved to be an efficient method for obtaining brominated ...An efficient and mild protocol for bromination of aryl azides with N-bromosuccinimide（NBS） under FeCl_3 catalysis in 1,2- dichloroethane was developed.It is proved to be an efficient method for obtaining brominated aryl azides.展开更多
The excited state structural dynamics of phenyl absorbing S2（A＇）, S3（A＇）, and S6（A＇） states were troseopy and complete active space self-consistent and the UV absorption bands were assigned on azide （PhN3） ...The excited state structural dynamics of phenyl absorbing S2（A＇）, S3（A＇）, and S6（A＇） states were troseopy and complete active space self-consistent and the UV absorption bands were assigned on azide （PhN3） after excitation to the light studied using the resonance Raman specfield calculations. The vibrational spectra the basis of the Fourier transform （FT）- Raman, FT-infrared measurements, the density-functional theory computations and the normal mode analysis. The A-, B-, and C-bands resonance Raman spectra in cyclohex- ane, acetonitrile, and methanol solvents were, respectively, obtained at 273.9, 252.7, 245.9, 228.7, 223.1, and 208.8 nm excitation wavelengths to probe the corresponding structural dynamics of PhN3. The results indicated that the structural dynamics in the S2 （A＇）, S3（A＇）, and S6（A＇） states were significantly different. The crossing points of the potential energy surfaces, S2S1（1） and S2S1（2）, were predicted to play a key role in the low-lying excited state decay dynamics, in accordance with Kasha＇s rule, and NT=N8 dissociation. Two decay channels initiated from the Franck-Condon region of the S2（A＇） state were predicted： the radiative S2,min→S0 radiative decay and the S2→S1 internal conversion through the crossing points S2S1 （1）/S2S1（2）.展开更多
文摘Heterocyclic ketene aminals 1 react with aryl azides 2 to give the titled compounds 3,and in some cases also with the formation of fused heterocycles 4.
文摘A visible-light-enabled method for the synthesis ofα-azidoketones has been developed via oxo-azidation of alkenyl silanes with trimethylsilylazide and molecular oxygen under mild conditions.The reaction could be carried out in gram scale.Various radical sources,including trifluoromethyl radical,thiocyanate radical,bromide radical,chlorine radical could partici-pate effectively instead of azide radical in the reaction.
文摘Isothiocyanates(ITCs)are an important class of organic compounds characterized by the functional group R-N=C=S.These functional groups are widely found in multiple natural products and pharmaceutical important drugs.Moreover,due to their high and versatile reactivity,they are widely used as an intermediate in organic synthesis.Keeping in view ITCs importance,this review summarizes their synthesis from nitrogen rich raw materials like amines,isocyanides,azides and some other compounds like oximes.Besides their synthesis,their application in organic compound synthesis as an intermediate will also be covered.Future research will likely focus on optimizing the synthesis of multifunctional isothiocyanates,understanding their complex biological mechanisms,exploring new applications,and highlighting the continued importance of isothiocyanates in modern chemistry and biotechnology.
基金financial support from the National Natural Science Foundation of China(Nos.22125108,22331004 and 22121001)Yunnan Normal University,Applied Basic Research Projects of Yunnan Province(No.202101AT070217)+1 种基金the Jiangxi Provincial Natural Science Foundation(No.20224BAB213013)the Jiangxi Provincial Department of Education in Science and Technology Program Project(No.GJJ210906)。
文摘Gold-catalyzed amination reactions based on azides viaα-imino gold carbene intermediates have attracted extensive attention in the past decades because this methodology leads to the facile and efficient construction of synthetically useful N-containing molecules,especially valuable N-heterocycles.However,successful examples of intermolecular generation ofα-imino gold carbenes by using azides as amination reagents are rarely explored probably due to the weak nucleophilicity of azides.Herein,we disclose an efficient gold-catalyzed intermolecular aminative cyclopropanation of ynamides with the allyl azides,enabling flexible synthesis of a wide range of valuable 3-azabicyclo[3.1.0]hex-2-ene derivatives in good to excellent yields with excellent diastereoselectivities.Importantly,this protocol represents the first use of allyl azide as an efficient amination reagent in gold-catalyzed alkyne amination reactions.
基金Project supported financially by the Program for the Development of Science and Technology of Jilin Province,China(Grant Nos.YDZJ202301ZYTS382,YDZJ202201ZYTS316,and 20230101285JC)the National Natural Science Foundation of China(Grant No.11904128)+1 种基金the Program for Science and Technology of Education Department of Jilin Province,China(Grant Nos.JJKH20220438KJ and JJKH20220423KJ)the Program for the Jilin Provincial Development and Reform Commission Project(Grant No.2022C040-6)。
文摘The high-pressure structure and elastic properties of calcium azide(Ca(N_(3))_(2))were investigated using in-situ highpressure x-ray diffraction and Raman scattering up to 54 GPa and 19 GPa,respectively.The compressibility of Ca(N_(3))_(2)changed as the pressure increased,and no phase transition occurred within the pressure from ambient pressure up to 54 GPa.The measured zero-pressure bulk modulus of Ca(N_(3))_(2)is higher than that of other alkali metal azides,due to differences in the ionic character of their metal-azide bonds.Using CASTEP,all vibration modes of Ca(N_(3))_(2)were accurately identified in the vibrational spectrum at ambient pressure.In the high-pressure vibration study,several external modes(ext.)and internal bending modes(ν_(2))of azide anions(N_(3)^(-))softened up to~7 GPa and then hardened beyond that pressure.This evidence is consistent with the variation observed in the F_(E)–f_(E)data analyzed from the XRD result,where the slope of the curve changes at 7.1 GPa.The main behaviors under pressure are the alternating compression,rotation,and bending of N_(3)^(-)ions.The bending behavior makes the structure of Ca(N_(3))_(2)more stable under pressure.
基金the financial support provided by the National Natural Science Foundation of China(Grant No.11872013).
文摘Copper-based azide(Cu(N_(3))2 or CuN_(3),CA)chips synthesized by in-situ azide reaction and utilized in miniaturized explosive systems has become a hot research topic in recent years.However,the advantages of in-situ synthesis method,including small size and low dosage,bring about difficulties in quantitative analysis and differences in ignition capabilities of CA chips.The aim of present work is to develop a simplified quantitative analysis method for accurate and safe analysis of components in CA chips to evaluate and investigate the corresponding ignition ability.In this work,Cu(N_(3))2 and CuN_(3)components in CA chips were separated through dissolution and distillation by utilizing the difference in solubility and corresponding content was obtained by measuring N_(3)-concentration through spectrophotometry.The spectrophotometry method was optimized by studying influencing factors and the recovery rate of different separation methods was studied,ensuring the accuracy and reproducibility of test results.The optimized method is linear in range from 1.0-25.0 mg/L,with a correlation coefficient R^(2)=0.9998,which meets the requirements of CA chips with a milligram-level content test.Compared with the existing ICP method,component analysis results of CA chips obtained by spectrophotometry are closer to real component content in samples and have satisfactory accuracy.Moreover,as its application in miniaturized explosive systems,the ignition ability of CA chips with different component contents for direct ink writing CL-20 and the corresponding mechanism was studied.This study provided a basis and idea for the design and performance evaluation of CA chips in miniaturized explosive systems.
文摘The long sought cubic gauche polymeric nitrogen(cg-N)consisting of N-N single bonds has been synthesized by one pot route using sodium azide as a precursor at ambient conditions.The recrystallization process was designed to expose crystal faces with low activation energy that facilitates initiating the polymeric reaction at ambient conditions.The azide was considered as a precursor due to the low energy barrier in transforming double bonded N=N to single bonded cg-N.Raman spectrum measurements detected the emerging vibron peaks at 635 cm^(−1) for the polymerized sodium azide samples,demonstrating the formation of cg-N with N-N single bonds.Different from traditional high-pressure technique and recently developed plasma enhanced chemical vapor deposition method,the route achieves the quantitative synthesis of cg-N at ambient conditions.The one pot synthesis of cg-N offers potential for further scaling up production as well as practical applications of polymeric nitrogen based materials as high energy density materials.
基金Project supported by the Scientific Research Foundation of Hunan Provincial Education Department(No.23B0650)the Natural Science Foundation of Hunan Province(No.2022JJ30418)+1 种基金the Key Scientific Research Foundation of Hunan University of Arts and Science(No.22ZD04)the Innovation and Entrepreneurship Training Program for College Students of Hunan University of Arts and Science(No.XDC202318)。
文摘An efficient visible-light-induced radical cascade azidation/cyclization of 2-aryl indoles with trimethylsilyl azide(TMSN3)has been developed using organic dye Rose Bengal as the photocatalyst.This method did not require metal catalysts and additives,and used air as the oxidant to obtain diverse indolo[2,1-a]isoquinolin-6(5H)-ones in moderate to good yields.Mechanistic studies demonstrated that the reaction proceeded via a radical pathway.
文摘In the pursuit of advancing imidazolium-based energetic ionic liquids (EILs),the current study is devoted to the synthesis and characterization of 1,3-dibutyl-imidazolium azide ([BBIm][N_(3)]),as a novel member in this ionic liquids class.The chemical structure of this EIL was rigorously characterized and confirmed using FTIR spectroscopy,1D,and 2D-NMR analyses.The thermal behavior assessment was conducted through DSC and TGA experiments.DSC analysis revealed an endothermic glass transition at T_(g)=-61℃,followed by an exothermic degradation event at T_(onset)=311℃.Similarly,TGA thermograms exhibited a one-stage decomposition process resulting in 100% mass loss of the sample.Furthermore,the short-term thermal stability of the azide EIL was investigated by combining the non-isothermal TGA data with the TAS,it-KAS,and VYA/CE isoconversional kinetic approaches.Consequently,the Arrhenius parameters(E_(a)=154 kJ·mol^(-1),Log(A/s^(-1))=11.8) and the most probable reaction model g(a) were determined.The observed high decomposition temperatures and the significantly elevated activation energy affirm the enhanced thermal stability of the modified EIL.These findings revealed that[BBIm][N_(3)]EIL can be a promising candidate for advanced energetic material application.
文摘bis(azidomethyl) 3,3′ bis(1,2,4 oxadiazole)(Ⅰ) and bis(azidoacetamino) oxazofurazan(Ⅱ) were synthesized. The structures of these two compounds have been identified by IR, 1H NMR, MS and elemental analysis. Azido groups were introduced into furazan derivatives and energetic materials of high nitrogen content and high enthalpy of formation can be obtained. The densities of compound Ⅰ and Ⅱ are relatively high. Compound Ⅰ is an azide of lower melting point, it is hopeful to be applied as energetic plastic additives.
文摘Tazobactam,β lactamase inhibitor, was synthesized from 6 aminopenicillanic acid through eleven steps, including diazotization, bromination, oxidation, chlorization, cyclization, deprotection and so on. The designed route was examined, particularly the azide substitution and cyclization. In the latter reaction, vinyl acetic ester was employed in place of acetylene.
基金supported by National Natural Science Foundation of China (20977115, 21272281)Natural Science Foundation of Hubei Province (2014CFB919)the Science and Technology Plan Innovation Team of Wuhan City (2015070504020220)~~
文摘The photocatalytic activity of cobalt octakis（butylthio） porphyrazine（CoPz（BuS）8） was assessed through photodegradation of the dye rhodamine B（RhB） in water under irradiation with a Xe lamp and aerated conditions.The photocatalytic activity of CoPz（BuS）8 loaded on Al2O3 or SiO2@Fe3O4nanoparticles or coordinated with an axial azide ligand was also investigated.The results demonstrated that the photocatalytic activity of CoPz（BuS）8 loaded on Al2O3 was higher than that loaded on SiO2@Fe3O4.The kinetic curves of RhB degradation in aqueous solutions at different pH indicated the pseudo first-order kinetics of the reaction.The highest degradation rate for CoPz（BuS）8 loaded Al2O3 at pH = 4 after 160 min was 84.6%.However,the advantages of easier separation and recycling as well as the ability to terminate the reaction at any time for the CoPz（BuS）8 loaded SiO2@Fe3O4 cannot be ignored.When electron-rich NaN3 was coordinated with CoPz（BuS）8 as an axial ligand and loaded on Al2O3,the resulting catalyst produced more active oxygen species such as O2^- and HO· to promote the quicker degradation of RhB than that by the other catalysts.For the N3-coordinated CoPz（BuS）8 loaded on Al2O3,the reactions at pH = 4 and 7 distinctly deviated from first-order kinetics,and the degradation rate reached 77.6%after 80 min at pH = 4.
基金National Science Foundation of China (Grant No.20732001 and 90713004).
文摘A core trisaccharide of laminin, β-D-Gal-（1→4）-β-D-GlcpNAc-（1→6）-α-D-Manp-OMe, with potential anti-rumor metastatic activity was designed and prepared. 2-Iodoglactosyl azide was used as the donor to construct 2-N-acetamido-2-deoxylactosyl moiety through an azidoiodo-glycosylation reaction. Simultaneously, 1, 2-trans-β-glycosic bond was formed stereoselectively in one step with a moderate yield. This novel procedure avoided the use of 2-amino-2-deoxyglucose as both donor and acceptor.
基金partially supported by the National Natural Science Foundation of China(Nos.50703033,20974098 and 20974028)the Ministry of Science and Technology of China(2009CB623605)+1 种基金the Research Grants Council of Hong Kong (603509,HKUST2/CRF/10)the University Grants Committee of Hong Kong(AoE/P-03/08)
文摘The great achievements of click chemistry have encouraged polymer scientists to use this reaction in their field. This review assembles an update of the advances of using azide-alkyne click polymerization to prepare functional polytriazoles（PTAs） with linear and hyperbranched structures.The Cu（I）-mediated click polymerization furnishes 1,4-regioregular PTAs,whereas,the metal-free click polymerization of propiolates and azides produces PTAs with 1,4-regioisomer contents up to 90%.The PTAs display advanced functions,such as aggregation-induced emission,thermal stability,biocompatibility and optical nonlinearity.
文摘Wide potential windows were found at carbon nanotube film electrodes in neutral solutions after being treated with nitric acid and mixed acid. Electrochemical reversibility was investigated at carbon nanotube films with different pretreatments for ferri/ferrocyanide and quinone /hydroquinone. Carbon nanotube film electrodes presented quasi-reversible electrochemical behavior for both electrolytes. In the range of scan rate, carbon nanotube film electrodes treated with acids showed heterogeneous electron-transfer properties, which was mainly controlled by its electron state density on the surface of the film. On the whole, the carbon nanotube electrode with nitric acid treatment presented the best electrochemical behaviors, so we chose it as an analytical electrode to determine the trace compound in dilute solution. The results demonstrated that this new electrode material exhibits superior performance characteristics for the detection of azide anion.
基金National Natural Science Foundation of China(Grant No.11832006,U1530262,21975024).
文摘Aluminum(Al) particles are good fuel additives to improve the energy output performances of explosives. Under detonation environment, reaction delay of Al particles plays a key role in the energy release efficiency. Up to date, reaction delay of Al particles is still limited by the efficiency of mass and heat transfer from oxidizers to Al particles. To address this issue, a homogeneous fuel-oxidizer assembly has recently become a promising strategy. In this work, oxidizer-activated Al fuel particles(ALG) were prepared with glycidyl azide polymer(GAP) as the oxidizer. The ALG was in uniform spherical shape and core-shell structure with shell layer of around 5 nm which was observed by scanning electron microscope and transmission electron microscope. The localized nanoscale mid-IR measurement detected the uniform distribution of characteristic absorption bond of GAP in the shell layer which confirmed the homogenous fuel-oxidizer structure of ALG. A thermal gravimetric analysis of ALG at ultrafast heating rate of 1000℃/min under argon atmosphere was conducted. The decomposition of GAP finished much earlier than that of GAP at heating rate of 10℃/min. Under ultrafast high laser fluence, the reaction response of ALG was characterized and compared with that of micro-sized Al(μAl). With the increase of laser energy, the propagation distance of the shock wave increased. However, the velocity histories were nearly the same when energies were lower than 299 mJ or higher than 706 mJ. The propagation distance of the shock wave for ALG was 0.5 mm larger than that for μAl at 2.1 μs. The underwater explosion showed the peak pressure and the shock wave energy of the ALG-based explosive were both higher than those of the μAl-based explosive at 2.5 m. This study shows the feasibility to improve the energy release of Al-based explosives via using the oxidizer-activated Al fuel particles with energetic polymer as the oxidizer.
文摘A new method for the synthesis of 4,4′,6,6′-tetra(azido)azo-1,3,5-triazine (TAAT) is described. The key intermediate 4,4′,6,6′-tetra(azido)hydrazo-1,3,5-triazine (TAHT) was synthesized by nucleophilic substitution in the case of sodium azide as nucleophile. N-Bromosuccinide (NBS) was used as oxidant to oxidize TAHT by a tractable operation under mild reaction condition. The target compound TAAT was obtained with a facile process and high overall yield of 81%. The structures of TAAT and its intermediates were identified by spectroscopic methods.
基金Guangdong Provincial Natural Science Foundation(20010102)the PhD-Degree-Bearer's Startup Foundation of Guangdong Academy of Agricultural Sciences(00-Boshi-05).
文摘Field and pot experiments were conducted using indica rice varieties with differential chalkiness. There were significant differences in root activity among the varieties. The percentages of chalky grains and chalky area were both negatively correlated with root activity expressed as α-naphthylamine oxidation ability （RA） per gram of fresh root （RAfw） , RA per spikelet （RAgrn）, or RA per sink capacity （RAsink）. The RAsink was more closely related to chalkiness than RAt, and RAgrn when varieties differed greatly in panicle size and grain weight. Application of NO3^--N fertilizer at heading resulted in higher root activity and reduced chalkiness. Application of 30 mg/L NaN3 （respiration inhibitor） resulted in reduced root activity and increased chalkiness for one variety ＇GD9501＇, but for the other variety ＇Qinluai＇ was in reverse. The percentages of chalky grains and chalky area were negatively correlated with root activity at 10 days after heading under different chemical treatments （r=-0.8567^＊ and r=-0.9211^＊＊, respectively）.
基金supported by National Natural Science Foundation of China(No30873153)the Key Projects of Shanghai in Biomedical(No08431902700)the Scientific Research Foundation of State Education Ministry for the Returned Overseas Chinese Scholars
文摘An efficient and mild protocol for bromination of aryl azides with N-bromosuccinimide（NBS） under FeCl_3 catalysis in 1,2- dichloroethane was developed.It is proved to be an efficient method for obtaining brominated aryl azides.
基金This work is supported by the National Natural Science Foundation of China （No.21473163, No.21033002, No.21202032） and the National Basic Research Program of China （No.2013CB834604）.
文摘The excited state structural dynamics of phenyl absorbing S2（A＇）, S3（A＇）, and S6（A＇） states were troseopy and complete active space self-consistent and the UV absorption bands were assigned on azide （PhN3） after excitation to the light studied using the resonance Raman specfield calculations. The vibrational spectra the basis of the Fourier transform （FT）- Raman, FT-infrared measurements, the density-functional theory computations and the normal mode analysis. The A-, B-, and C-bands resonance Raman spectra in cyclohex- ane, acetonitrile, and methanol solvents were, respectively, obtained at 273.9, 252.7, 245.9, 228.7, 223.1, and 208.8 nm excitation wavelengths to probe the corresponding structural dynamics of PhN3. The results indicated that the structural dynamics in the S2 （A＇）, S3（A＇）, and S6（A＇） states were significantly different. The crossing points of the potential energy surfaces, S2S1（1） and S2S1（2）, were predicted to play a key role in the low-lying excited state decay dynamics, in accordance with Kasha＇s rule, and NT=N8 dissociation. Two decay channels initiated from the Franck-Condon region of the S2（A＇） state were predicted： the radiative S2,min→S0 radiative decay and the S2→S1 internal conversion through the crossing points S2S1 （1）/S2S1（2）.
