The energetic material, 3‐nitro‐1,5‐bis(4,4′‐dimethyl azide)‐1,2,3‐triazolyl‐3‐azapentane (NDTAP), was firstly synthesized by means of Click Chemistry using 1,5‐diazido‐3‐nitrazapentane as main material. The structure of NDTAP was confirmed by IR, 1H NMR, and 13C NMR spectroscopy; mass spectrometry, and elemental analysis. The crystal structure of NDTAP was determined by X‐ray diffraction. It belongs to monoclinic system, space group C2/c with crystal parameters a=1.7285(8) nm, b=0.6061(3) nm, c=1.6712(8) nm, β=104.846(8)°, V=1.6924(13) nm3, Z=8, μ=0.109 mm−1, F(000)=752, and Dc=1.422 g cm−3. The thermal behavior and non‐isothermal decomposition kinetics of NDTAP were studied with DSC and TG‐DTG methods. The self‐accelerating decomposition temperature and critical temperature of thermal explosion are 195.5 and 208.2 °C, respectively. NDTAP presents good thermal stability and is insensitive. 相似文献
In order to evaluate 2,4,6‐trinitro‐1,3,5‐triazine (TNTAz), 3,6‐dinitro‐1,2,4,5‐tetrazine (DNTAz), and 2,5,8‐trinitro‐tri‐s‐triazine (TNTsTAz), the geometries of these compounds have been fully optimized employing the B3LYP density functional method and the AUG‐cc‐pVDZ basis set. The accurate gas phase enthalpies of formation have been obtained by using the atomization procedure and designing isodesmic reactions in which the parent rings are not destroyed. Based on B3LYP/AUG‐cc‐pVDZ calculated geometries and natural charges, the crystal structures have been predicted using the Karfunkel–Gdanitz method. Computed results show that there exists extended conjugation over the parent rings of these compounds. More energy content is reserved in DNTAz than in both TNTAz and TNTsTAz. The title compounds are much more sensitive than 1,3,5‐trinitrobenzene. The calculated detonation velocity of DNTAz reaches 9.73–9.88 km s−1, being larger than those of CL‐20 and TNTAz. TNTsTAz has no advantage over the widely used energetic compounds such as RDX and HMX. 相似文献
Ten 5‐(substituted phenylazo)‐3‐cyano‐1‐ethyl‐6‐hydroxy‐4‐methyl‐2‐pyridones were studied (five new compounds) to provide insight into the electronic effects of diverse substituents located at different positions in their phenyl moieties. The structural features of these dyes were examined by combining experimental and theoretical approaches. The crystal structures of two derivatives were revealed by X‐ray crystallography and diverse packing modes owing to different intermolecular interactions (π–π stacking and lone pair–π interactions, as well as hydrogen bonds) were found. A study on lattice energy and energy related to the molecular pairs obtained from their crystal packing was performed. The tautomerism and ionisation of the dyes in ethanol or N,N ‐dimethylformamide solution were rationalised in terms of diazo component substitution pattern. 相似文献
In accordance with a novel strategy for generating the 2‐benzazepine scaffold by connecting C6–C1 and C3–N building blocks, a set of 5‐phenylsulfanyl‐ and 5‐benzyl‐substituted tetrahydro‐2‐benzazepines was synthesized and pharmacologically evaluated. Key steps of the synthesis were the Heck reaction, the Stetter reaction, a reductive cyclization, and the introduction of diverse N substituents at the end of the synthesis. High σ1 affinity was achieved for 2‐benzazepines with linear or branched alk(en)yl residues containing at least an n‐butyl substructure. The butyl‐ and 4‐fluorobenzyl‐substituted derivatives, (±)‐5‐benzyl‐2‐butyl‐2,3,4,5‐tetrahydro‐1H‐2‐benzazepine ( 19 b ) and (±)‐5‐benzyl‐2‐(4‐fluorobenzyl)‐2,3,4,5‐tetrahydro‐1H‐2‐benzazepine ( 19 m ), show high selectivity over more than 50 other relevant targets, including the σ2 subtype and various binding sites of the N‐methyl‐D ‐aspartate (NMDA) receptor. In the Irwin screen, 19 b and 19 m showed clean profiles without inducing considerable side effects. Compounds 19 b and 19 m did not reveal significant analgesic and cognition‐enhancing activity. Compound 19 m did not have any antidepressant‐like effects in mice. 相似文献
hMTH1 (8‐oxo‐2′‐deoxyguanine triphosphatase) hydrolyzes oxidized nucleoside triphosphates; its presence is non‐essential for survival of normal cells but is required for survival of cancer cells. In this study, 8‐halogenated‐7‐deaza‐2′‐deoxyguanosine triphosphate (8‐halogenated‐7‐deazadGTP) derivatives were synthesized. Interestingly, these triphosphates were poor substrates for hMTH1, but exhibited strong competitive inhibition against hMTH1 at nanomolar levels. This inhibitory effect is attributed to slower rate of hydrolysis, possibly arising from enzyme structural changes, specifically different stacking interactions with 8‐halogenated‐7‐deazadGTP. This is the first example of using nucleotide derivatives to inhibit hMTH1, thus demonstrating their potential as antitumor agents. 相似文献
Analysis of the recently solved X‐ray crystal structures of Saccharomyces cerevisiae ribonucleotide reductase I (ScRnr1) in complex with effectors and substrates led to the discovery of a conserved water molecule located at the active site that interacted with the 2′‐hydroxy group of the nucleoside ribose. In this study 2′‐(2‐hydroxyethyl)‐2′‐deoxyadenosine 1 and the 5′‐diphosphate derivative 2 were designed and synthesized to see if the conserved water molecule could be displaced by a hydroxymethylene group, to generate novel RNR inhibitors as potential antitumor agents. Herein we report the synthesis of analogues 1 and 2 , and the co‐crystal structure of adenosine diphosphate analogue 2 bound to ScRnr1, which shows the conserved water molecule is displaced as hypothesized.相似文献
The energetic material 3‐(4‐aminofurazan‐3‐yl)‐4‐(4‐nitrofurazan‐3‐yl)furazan (ANTF) with low melting‐point was synthesized by means of an improved oxidation reaction from 3,4‐bis(4′‐aminofurazano‐3′‐yl)furazan. The structure of ANTF was confirmed by 13C NMR spectroscopy, mass spectrometry, and the crystal structure was determined by X‐ray diffraction. ANTF crystallized in monoclinic system P21/c, with a crystal density of 1.785 g cm−3 and crystal parameters a=6.6226(9) Å, b=26.294(2) Å, c=6.5394(8) Å, β=119.545(17)°, V=0.9907(2) nm3, Z=4, μ=0.157 mm−1, F(000)=536. The thermal stability and non‐isothermal kinetics of ANTF were studied by differential scanning calorimetry (DSC) with heating rates of 2.5, 5, 10, and 20 K min−1. The apparent activation energy (Ea) of ANTF calculated by Kissinger's equation and Ozawa's equation were 115.9 kJ mol−1 and 112.6 kJ mol−1, respectively, with the pre‐exponential factor lnA=21.7 s−1. ANTF is a potential candidate for the melt‐cast explosive with good thermal stability and detonation performance. 相似文献
1‐Azido‐2‐nitro‐2‐azapropane ( 1 ) was synthesized in high yield from 1‐chloro‐2‐nitro‐2‐azapropane and sodium azide. 1‐Nitrotetrazolato‐2‐nitro‐2‐azapropane ( 2 ) was synthesized in high yield from 1‐chloro‐2‐nitro‐2‐azapropane and silver nitrotetrazolate. The highly energetic new compounds ( 1 and 2 ) were characterized using vibrational (IR and Raman) and multinuclear NMR spectroscopy (1H, 13C, 14N), elemental analysis and low‐temperature single crystal X‐ray diffraction. 1‐Azido‐2‐nitro‐2‐azapropane ( 1 ) represents a covalently bound liquid energetic material which contains both a nitramine unit and an azide group in the molecule. 1‐Nitrotetrazolato‐2‐nitro‐2‐azapropane ( 2 ) is a covalently bound room‐temperature stable solid which contains a nitramine group and a nitrotetrazolate ring unit in the molecule. Compounds 1 and 2 are hydrolytically stable at ambient conditions. The impact sensitivity of compound 1 is very high (<1 J) whereas compound 2 is less sensitive (<6 J). 相似文献
6‐Amino‐6‐deoxy‐5,6‐di‐ N ‐( N ′‐octyliminomethylidene)nojirimycin , a reducing analogue of N‐nonyl‐1‐deoxynojirimycin, proved to be a potent and very selective inhibitor of β‐glucosidases, including human acid β‐glucosidase. Structural studies of the enzyme–inhibitor complex showed a binding mode in which the anomeric hydroxy group is accommodated in the “wrong” α configuration.