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1.
Synthesis and Characteristics of Bis(2, 2‐dinitroethyl‐N‐nitro)ethylenediamine‐Based Energetic Salts
Jinhong Song Prof. Dr. Zhiming Zhou Haifeng Huang Dan Cao Lixuan Liang Kai Wang Jun Zhang Fen‐Qui Zhao 《无机化学与普通化学杂志》2012,638(6):957-964
New energetic bis(2, 2‐dinitroethyl‐N‐nitro)ethylenediamine‐based salts exhibiting moderate physical properties, good detonation properties, and relatively low impact sensitivities were synthesized in high yield by direct reactions of bis(2, 2‐dinitroethyl‐N‐nitro)ethylenediamine with organic bases. The resulting salts were fully characterized by multinuclear NMR spectroscopy (1H and 13C), vibrational spectroscopy (IR), differential scanning calorimetry (DSC), and elemental analysis. Solid‐state 15N NMR spectroscopy was used as an effective technique to further determine the structure of some products. Thermal decomposition kinetics and several thermodynamic parameters of some salts were obtained under non‐isothermal conditions by DSC. The densities of the energetic salts paired with organic cations were in the range 1.60–1.89 g · cm–3 as measured with a gas pycnometer. Based on the measured densities and calculated heats of formation, detonation pressures and velocities were calculated using Explo 5.05 and found to be 23.6–44.8 GPa and 7790–9583 m · s–1, respectively, which make them potentially useful as energetic materials. 相似文献
2.
3.
Haifeng Huang Prof. Dr. Zhiming Zhou Lixuan Liang Jinhong Song Kai Wang Dan Cao Chengming Bian Wenwen Sun Min Xue 《无机化学与普通化学杂志》2012,638(2):392-400
Nitrogen‐rich 3, 4‐bis(1H‐tetrazol‐5‐yl)furoxan (H2BTF, 2 ) and its energetic salts with excellent thermal stability were successfully synthesized and fully characterized by 1H, and 13C NMR, and IR spectroscopy, differential scanning calorimetry (DSC), and elemental analyses. Additionally, the structures of barium ( 3 ) and 1‐methyl‐3, 4, 5‐triamino‐triazolium ( 10 ) salts were confirmed by single‐crystal X‐ray diffraction. The densities of the energetic salts paired with organic cations range between 1.56 and 1.85 g · cm–3 as measured by a gas pycnometer. Based on the measured densities and calculated heats of formation, the detonation pressures and velocities are calculated to be in the range 23.4–32.0 GPa and 7939–8915 m · s–1, which make them competitive energetic materials. 相似文献
4.
Kangzhen Xu Xiaolei Ren Jirong Song Fengqi Zhao Li Ding Jianhua Yi Yaoyu Wang 《中国化学》2009,27(10):1907-1913
A new compound, 2‐(dinitromethylene)‐1,3‐diazacyclopentane (DNDZ), was prepared by the reaction of 1,1‐diamino‐2,2‐dinitroethylene (FOX‐7) with 1,2‐diaminoethane in N‐methylpyrrolidone (NMP). Thermal decomposition of DNDZ was studied under non‐isothermal conditions by DSC, TG/DTG methods, and the enthalpy, apparent activation energy and pre‐exponential factor of the exothermic decomposition reaction were obtained as 317.13 kJ·mol?1, 269.7 kJ·mol?1 and 1024.51 s?1, respectively. The critical temperature of thermal explosion was 261.04°C. Specific heat capacity of DNDZ was determined with a micro‐DSC method and a theoretical calculation method, and the molar heat capacity was 205.41 J·mol?1·K?1 at 298.15 K. Adiabatic time‐to‐explosion was calculated to be a certain value between 263–289 s. DNDZ has higher thermal stability than FOX‐7. 相似文献
5.
David Bevk Uro Groelj Anton Meden Jurij Svete Branko Stanovnik 《Helvetica chimica acta》2006,89(11):2774-2782
A simple and efficient synthesis of novel 2‐heteroaryl‐substituted 1H‐indole‐2‐carboxylates and γ‐carbolines, compounds 1 – 3 , from methyl 2‐(2‐methoxy‐2‐oxoethyl)‐1‐methyl‐1H‐indole‐3‐carboxylate ( 4 ) by the enaminone methodology is presented. 相似文献
6.
Equilibrium geometries, bond dissociation energies and relative energies of axial and equatorial iron tetracarbonyl complexes of the general type Fe(CO)4L (L = CO, CS, N2, NO+, CN–, NC–, η2‐C2H4, η2‐C2H2, CCH2, CH2, CF2, NH3, NF3, PH3, PF3, η2‐H2) are calculated in order to investigate whether or not the ligand site preference of these ligands correlates with the ratio of their σ‐donor/π‐acceptor capabilities. Using density functional theory and effective‐core potentials with a valence basis set of DZP quality for iron and a 6‐31G(d) all‐electron basis set for the other elements gives theoretically predicted structural parameters that are in very good agreement with previous results and available experimental data. Improved estimates for the (CO)4Fe–L bond dissociation energies (D0) are obtained using the CCSD(T)/II//B3LYP/II combination of theoretical methods. The strongest Fe–L bonds are found for complexes involving NO+, CN–, CH2 and CCH2 with bond dissociation energies of 105.1, 96.5, 87.4 and 83.8 kcal mol–1, respectively. These values decrease to 78.6, 64.3 and 64.2 kcal mol–1, respectively, for NC–, CF2 and CS. The Fe(CO)4L complexes with L = CO, η2‐C2H4, η2‐C2H2, NH3, PH3 and PF3 have even smaller bond dissociation energies ranging from 45.2 to 37.3 kcal mol–1. Finally, the smallest bond dissociation energies of 23.5, 22.9 and 18.5 kcal mol–1, respectively are found for the ligands NF3, N2 and η2‐H2. A detailed examination of the (CO)4Fe–L bond in terms of a semi‐quantitative Dewar‐Chatt‐Duncanson (DCD) model is presented on the basis of the CDA and NBO approach. The comparison of the relative energies between axial and equatorial isomers of the various Fe(CO)4L complexes with the σ‐donor/π‐acceptor ratio of their respective ligands L thus does not generally support the classical picture of π‐accepting ligands preferring equatorial coordination sites and σ‐donors tending to coordinate in axial positions. In particular, this is shown by iron tetracarbonyl complexes with L = η2‐C2H2, η2‐C2H4, η2‐H2. Although these ligands are predicted by the CDA to be stronger σ‐donors than π‐acceptors, the equatorial isomers of these complexes are more stable than their axial pendants. 相似文献
7.
2‐(1‐Aryl‐2‐methoxyethenyl)benzaldehydes 2 , obtained by successive treatment of 1‐(1‐aryl‐2‐methoxyethenyl)‐2‐bromobenzenes 1 with BuLi and 1‐formylpiperidine, were transformed to the corresponding phenylhydrazones 3 on treatment with PhNHNH2. When these hydrazones were allowed to react with conc. HBr, cyclization, followed by dehydrogenation with air occurred, furnished 3‐aryl‐2‐methoxyinden‐1‐one (Z)‐phenylhydrazones 4 . 相似文献
8.
Jing Shang Jianguo Zhang Tonglai Zhang Huisheng Huang Shaowen Zhang Yuanjie Shu 《中国化学》2012,30(7):1624-1630
The geometric conformation and electronic structure of bis‐(5‐nitro‐2H‐tetrazolato‐N2)tetraammine cobalt(III) perchlorate and its Ni/Fe/Cu/Zn analogues are studied under the TPSS (Tao‐Perdew‐Staroverov‐Scuseria) levels of density functional theory in order to throw light on the relationship between their energy gaps and impact sensitivity. While the perchlorate ions are coordinated with the copper cation, which is different from the other four compounds. NBO (Natural bond orbital) analyses indicated that the metal‐ligand interaction in the Co complex is covalent, while the others are ionic. The analysis of the electrostatic potential demonstrated that the O atoms from the nitro‐tetrazole ring and perchlorate were primarily negative, while the other atoms were positive. The study was also conducted to gain a better understanding of the correlation of the energy gap and impact sensitivity. 相似文献
9.
A Facile Synthesis of 1‐Substituted 3‐Alkoxy‐1H‐isoindoles Based on the Reaction of 2‐(Dialkoxymethyl)phenyllithiums with Nitriles,Followed by Acid‐Catalyzed Cyclization 下载免费PDF全文
A two‐step synthesis of 1‐substituted 3‐alkoxy‐1H‐isoindoles 4 has been developed. Thus, the reaction of 2‐(dialkoxymethyl)phenyllithium compounds, which are easily generated in situ by Br/Li exchange between 1‐bromo‐2‐(dialkoxymethyl)benzenes 1 and BuLi in THF at ?78°, with nitriles afforded [2‐(dialkoxymethyl)phenyl]methanimines 2 , which were treated with a catalytic amount of TsOH?H2O in refluxing CHCl3 to give the desired products in reasonable yields. Similarly, 3‐aryl‐1‐ethoxy‐1‐methyl‐1H‐isoindoles 7 have been prepared starting from 1‐bromo‐2‐(1,1‐diethoxyethyl)benzenes 5 . 相似文献
10.
A series of novel 3‐((4‐(t‐butyl)‐2‐(2‐benzylidenehydrazinyl)thiazol‐5‐yl)methyl)quinolin‐2(1H)‐ones ( 7a – 7z ) were designed, synthesized and evaluated for their ability of inhibiting neuraminidase (NA) of in?uenza H1N1 virus. Some compounds displayed moderate influenza NA inhibitory activity. Compound 7l with the scaffold of 2‐(2‐(2‐methoxybenzylidene)hydrazinyl)thiazole was the best one, exhibiting moderate NA inhibitory activity with IC50 of 44.66 µmol/L. Structure‐activity relationship showed that compounds with methoxy or hydroxy groups at the ortho position, fluorine and nitro groups at the meta position and chlorine and bromine groups at the para position of phenyl ring were more active. Docking study indicated that compound 7l has important interactions with some key residues (including Asp151, Glu119, Arg292, Tyr406, and Asn347) and binds to 430‐cavity adjacent to NA active site. 相似文献
11.
Synthesis of 2‐Substituted 3‐Alkylidene‐2,3‐dihydro‐1H‐isoindol‐1‐imines through Cyclization of [1‐(2‐Cyanophenyl)alkylidene]aminide Intermediates Generated from the Reaction of 2‐(1‐Azidoalkyl)benzonitriles with NaH 下载免费PDF全文
A convenient sequence for the preparation of 3‐alkylidene‐2,3‐dihydro‐1H‐isoindol‐1‐imine derivatives 6 has been developed. Thus, 2‐(1‐azidoalkyl)benzonitriles 2 , readily accessible from 2‐alkylbenzonitriles, are allowed to react with NaH in DMF at 0° to room temperature to generate [1‐(2‐cyanophenyl)alkylidene]aminide intermediates 3 , of which cyclization and the subsequent rearrangement, followed by alkylation with alkyl halides, affords 2‐substituted 1‐alkylidene‐2,3‐dihydro‐1H‐isoindol‐2‐imines 6 in generally moderate yields. 相似文献
12.
1D Structure Sodium Coordination Anion based on [5‐(Dinitromethylene)‐4,5‐dihydro‐1H‐tetrazole]: Syntheses,Structures, and Thermal Behavior 下载免费PDF全文
The ten‐coordinate complex, (HATr)[Na(DNMz)] · H2O ( 1 ) was synthesized by reaction of 5‐(dinitromethylene)‐4,5‐dihydro‐1H‐tetrazole (DNMz), sodium hydroxide, and 3‐hydrazinium‐4‐amino‐1,2,4‐1H‐triazolium dichloride (HATr) in aqueous solution and characterized by various physico‐chemical techniques. Complex 1 is an energetic material with a nitrogen content of 51.2 % and a decomposition temperature of 128.9 °C. The molecular structure of complex 1 crystallizes in the monoclinic system with P2(1)/c group and shows an infinite 1D chain structure. The heat of formation was determined as –122.27 kJ · mol–1 by using bomb calorimetry. In addition, the kinetic parameters were studied by Kissinger's and Ozawa‐Doyle's methods. 相似文献
13.
Tamara I. Vakulskaya Lyudmila I. Larina Nadezhda I. Protsuk Valentin A. Lopyrev 《Magnetic resonance in chemistry : MRC》2009,47(9):716-719
The non‐degenerate tautomers of 3‐nitro‐1,2,4‐triazole‐5‐one (NTO) radical anions were investigated for the first time by an ESR method during electrochemical reduction of NTO in an aprotic medium. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
14.
Synthesis of 3‐(ω‐Hydroxyalkoxy)isobenzofuran‐1(3H)‐ones by Trifluoroacetic Acid‐Mediated Lactonization of tert‐Butyl 2‐(1,3‐Dioxol‐2‐yl)‐ or 2‐(1,3‐Dioxan‐2‐yl)benzoates 下载免费PDF全文
An efficient two‐step method for the preparation of 3‐(2‐hydroxyethoxy)‐ or 3‐(3‐hydroxypropoxy)isobenzofuran‐1(3H)‐ones 3 has been developed. Thus, the reaction of 1‐(1,3‐dioxol‐2‐yl)‐ or 1‐(1,3‐dioxan‐2‐yl)‐2‐lithiobenzenes, generated in situ by the treatment of 1‐bromo‐2‐(1,3‐dioxol‐2‐yl)‐ or 1‐bromo‐2‐(1,3‐dioxan‐2‐yl)benzenes 1 with BuLi in THF at ?78°, with (Boc)2O afforded tert‐butyl 2‐(1,3‐dioxol‐2‐yl)‐ or 2‐(1,3‐dioxan‐2‐yl)benzoates 2 , which can subsequently undergo facile lactonization on treatment with CF3COOH (TFA) in CH2Cl2 at 0° to give the desired products in reasonable yields. 相似文献
15.
Irradiation (350 nm) of the newly synthesized 3‐(alk‐1‐ynyl)cyclohept‐2‐en‐1‐ones 1 and 2 leads to the selective formation of tricyclic head‐to‐head dimers. In the presence of 2,3‐dimethylbuta‐1,3‐diene, the (monocyclic) enone 1 affords trans‐fused 7‐alkynyl‐bicyclo[5.2.0]nonan‐2‐ones as major photoproducts, whereas photocycloaddition of benzocyclohept‐5‐en‐7‐one 2 to the same diene gives preferentially the eight‐membered cyclic allene 16 via ‘end‐to‐end’ cyclization of the intermediate allyl‐propargyl biradical 22 . On contact with acid, cycloocta‐1,2,5‐triene 16 isomerizes to cycloocta‐1,3,5‐triene 18 . 相似文献
16.
Yong Guo Dr. Guo‐Hong Tao Dr. Zhuo Zeng Dr. Haixiang Gao Dr. Damon A. Parrish Dr. Jean'ne M. Shreeve Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(12):3753-3762
High‐density energetic salts that contain nitrogen‐rich cations and the 5‐(tetrazol‐5‐ylamino)tetrazolate (HBTA?) or the 5‐(tetrazol‐5‐yl)tetrazolate (HBT?) anion were readily synthesized by the metathesis reactions of sulfate salts with barium compounds, such as bis[5‐(tetrazol‐5‐ylamino)tetrazolate] (Ba(HBTA)2), barium iminobis(5‐tetrazolate) (BaBTA), or barium 5,5′‐bis(tetrazolate) (BaBT) in aqueous solution. All salts were fully characterized by IR spectroscopy, multinuclear (1H, 13C, 15N) NMR spectroscopy, elemental analyses, density, differential scanning calorimetry (DSC), and impact sensitivity. Ba(HBTA)2 ? 4 H2O crystallizes in the triclinic space group P$\bar 1$ , as determined by single‐crystal X‐ray diffraction, with a density of 2.177 g cm?3. The densities of the other organic energetic salts range between 1.55 and 1.75 g cm?3 as measured by a gas pycnometer. The detonation pressure (P) values calculated for these salts range from 19.4 to 33.6 GPa, and the detonation velocities (νD) range from 7677 to 9487 m s?1, which make them competitive energetic materials. Solid‐state 13C NMR spectroscopy was used as an effective technique to determine the structure of the products that were obtained from the metathesis reactions of biguanidinium sulfate with barium iminobis(5‐tetrazolate) (BaBTA). Thus, the structure was determined as an HBTA salt by the comparison of its solid‐state 13C NMR spectroscopy with those of ammonium 5‐(tetrazol‐5‐ylamino)tetrazolate (AHBTA) and diammonium iminobis(5‐tetrazolate) (A2BTA). 相似文献
17.
Mayra Cortés‐Hernández Susana Rojas‐Lima Marcos Hernández‐Rodríguez Julián Cruz‐Borbolla Heraclio López‐Ruiz 《Helvetica chimica acta》2016,99(6):416-424
An efficient, simple protocol for the synthesis of a new family of chiral ureas 1 – 4 is described. The binding properties of 1 – 4 toward different anion (acetate, benzoate, fluoride, and chloride) have been studied by 1H‐NMR titration and have been observed in the case of 4 is a selective receptor for acetate. The theoretical calculation M06/6‐311+G(d,p) helped us explain the binding properties observed. The most interesting observation is that this calculated structure is consistent with expected, based on the concept of allylic 1,3‐strain (A1,3 strain). When chiral caboxylates were studied, urea 1 was the best in discriminating between enantiomers. 相似文献
18.
Abdolali Alizadeh Hamid Reza Esmaili zand Vahid Saberi Javad Mokhtari 《Helvetica chimica acta》2013,96(12):2240-2244
An efficient approach for the preparation of functionalized 5‐aryl‐3‐(methylsulfanyl)‐1H‐pyrazoles 2 is described. This three‐component reaction between benzaldehydes 1 , NH2NH2?H2O, and 1,1‐bis(methylsulfanyl)‐2‐nitroethene proceeds in EtOH under reflux conditions in good‐to‐excellent yields. The structures of 2 were corroborated spectroscopically (IR, 1H‐ and 13C‐NMR, and EI‐MS). A plausible mechanism for this type of reaction is proposed (Scheme 2). 相似文献
19.
Using the ligands N‐methylimidazole ( MeIm ), N‐ethylimidazole ( EtIm ), N‐propylimidazole ( PrIm ), and 1‐methyl‐1H‐1, 2, 4‐triazole ( MeTz ) three series with a total of 13 iron(II) complexes were isolated. The series comprise of the following complexes: (a) [Fe( MeIm )6](ClO4)2 ( 1 ), [Fe( EtIm )6](ClO4)2 ( 2 ), [Fe( PrIm )6](ClO4)2( 3 ), [Fe( MeTz )6](ClO4)2 ( 4 ), [Fe( MeIm )6](MeSO3)2 ( 5 ), [Fe( EtIm )6](MeSO3)2 ( 6 ), and [Fe( MeTz )6](BF4)2 ( 10 ); (b) [Fe( MeIm )4(MeSO3)2]( 7 ), [Fe( EtIm )4(MeSO3)2] ( 8 ), and [Fe( PrIm )4(MeSO3)2] ( 9 ); (c) [Fe( MeIm )4(NCS)2] ( 15 ), [Fe( EtIm )4(NCS)2] ( 16 ), and [Fe( MeTz )4(NCS)2] ( 17 ). Single crystal X‐ray diffraction studies were performed on 7 – 10 and 15 – 17 . Temperature dependent magnetic susceptibility measurements were performed on selective examples of all series, and confirmed them to be in the HS state over the range 6–300 K. DFT calculations were performed at BP86/def‐SV(P) and TPSSh/def2‐TZVPP level on all [Fe L 6]2+ complex cations and the neutral complexes 7 – 9 and 15 – 17 . Additionally the four homoleptic nickel(II) complexes [Ni L 6](ClO4)2 ( 11 : L = MeIm ; 12 : L = EtIm ; 13 : L = PrIm ; 14 : L = MeTz ) were synthesized and compounds 11 – 13 structurally characterized. UV/Vis/NIR spectroscopic measurements were carried out on all homoleptic iron(II) and nickel(II) complexes. The 10Dq values were determined to be in the range of 11547–11574 and 10471–10834 cm–1 for the iron(II) and nickel(II) complexes, respectively. 相似文献
20.
4‐Arylisocoumarins (=4‐aryl‐1H‐2‐benzopyran‐1‐ones) 6 were prepared from 2‐(1‐aryl‐2‐methoxyethenyl)‐1‐bromobenzenes 1 . Successive treatment of these bromo styrenes with BuLi and 1‐formylpiperidine gave a mixture of (E)‐ and (Z)‐2‐(1‐aryl‐2‐methoxyethenyl)benzaldehydes 2 . Hydrolysis of (Z)‐isomers with conc. HBr, followed by pyridinium chlorochromate (PCC) oxidation of the resulting 1H‐2‐benzopyran‐1‐ol derivatives 4 (and 5 ), afforded the desired products. 相似文献