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A comprehensive study of the solvent effects on the cycloaddition reaction of diethyl azodicarboxylate and ethyl vinyl ether: Efficient implementation of QM and TD‐DFT study 下载免费PDF全文
In this work, quantum chemistry calculations performed to study the kinetics and thermodynamic parameters of [2+2] cycloaddition reaction of diethyl azodicarboxylate and ethyl vinyl ether in eighty‐three solvents and gas phase. The solvent effect on the reaction path and electron density of the C2? N6 critical bond as the reaction coordinate at the TS was investigated. Calculated rate constants in various solvents showed that increase in the activation dipole moment accelerates the reaction. Based on the time‐dependent studies, using a conductor like polarizable continuum model solvation model, the solvent effects on the excitation energies of the reactants and transition states (TSs) and the corresponding chemical shifts were analyzed. Finally, some correlations between the rate constant and quantum reactivity indices such as electrophilicity index, chemical hardness, and electronic chemical potential were investigated. © 2014 Wiley Periodicals, Inc. 相似文献
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Yan Liu Hongchen Du Guixiang Wang Xuedong Gong Lianjun Wang Heming Xiao 《International journal of quantum chemistry》2011,111(5):1115-1126
The density functional theory has been used to study the tautomeric equilibrium of 2‐diazo‐4,6‐dinitrophenol(DDNP) in the gas phase and in 14 solvents at the B3LYP/6‐31G* level. The solvent effects on the tautomeric equilibria were investigated by the self‐consistent reaction field theory (SCRF) based on conductor polarized continuum model (CPCM) in apolar and polar solvents and by the hybrid continuum‐discrete model in protic solvent, respectively. Solvent effects on the computed molecular properties, such as molecular geometries, dipole moments, ELUMO, EHOMO, total energies for DDNP tautomers and transition state, tautomerization energies and solvation energies have been found to be evident. The tautomeric equilibrium of DDNP is solvent‐dependent to a certain extent. The tautomer I (cyclic azoxy form) is preferred in the gas phase, while in nonpolar solvents tautomer I and II (quinold form) exist in comparable amounts, and in highly polar solvents, the tautomeric equilibrium is shifted in favor of the more polar tautomer II . © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011 相似文献
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Lingping Cheng Jianfeng Cai Qing Fu Yanxiong Ke 《Journal of separation science》2019,42(15):2482-2490
6‐(4‐Aminophenyl)‐5‐methyl‐4,5‐dihydro‐3(2H)‐pyridazinone is a key synthetic intermediate for cardiotonic agent levosimendan. Very few studies address the use of chiral stationary phases in chromatography for the enantioseparation of this intermediate. This study presents two efficient preparative methods for the isolation of (R)(?)‐6‐(4‐aminophenyl)‐5‐methyl‐4,5‐dihydro‐3(2H)‐pyridazinone in polar organic solvent chromatography and supercritical fluid chromatography using polysaccharide‐based chiral stationary phases and volatile organic mobile phases without additives in isocratic mode. Under optimum conditions, Chiralcel OJ column showed the best performance (α = 1.71, Rs = 5.47) in polar organic solvent chromatography, while Chiralpak AS column exhibited remarkable separations (α = 1.81 and Rs = 6.51) in supercritical fluid chromatography with an opposite enantiomer elution order. Considering the sample solubility, runtime and solvent cost, the preparations were carried out on Chiralcel OJ column and Chiralpak AS column (250 × 20 mm i.d.; 10 µm) in polar organic mode and supercritical fluid chromatography mode with methanol and CO2/methanol as mobile phases, respectively. By utilizing the advantages of chromatographic techniques and polysaccharide‐based chiral stationary phases, this work provides two methods for the fast and economic preparation of (R)(?)‐6‐(4‐aminophenyl)‐5‐methyl‐4,5‐dihydro‐3(2H)‐pyridazinone, which are suitable for the pharmaceutical industry. 相似文献
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The molecule of the title compound, C18H18O2, is a substituted cyclopropane ring. The electron density in this molecule has been determined by refining single‐crystal X‐ray data using scattering factors derived from quantum mechanical calculations. Topological analysis of the electron densities in the three cyclopropane C—C bonds was carried out. The results show the effects of this substitution on these C—C bonds. 相似文献
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The molecular structures of 1, 8‐naphthalimide derivatives were investigated at density functional theory level within framework of PBE1PBE/6‐31G*. The vertical ionization potential and their delocalization energy of the X‐ray solid structure and gas‐phase optimized structure were explored. The configuration difference between them was attributed to the π‐π interaction of the solid effect, which has negligible effect on their absorption spectra. Solid effect also weakens the intramolecular interaction. Their absorption and luminescent spectra in gas and solvent phase were calculated by time‐dependent density functional theory (TDDFT) and conductor polarizable continuum models (CPCM)‐TDDFT approaches. Obvious red shifts from the solvent effect were found. Substituents on the imides will not improve their spectra properties a lot, whereas substituents on the naphthalene of naphthalimide would modify their properties to emit different spectra. Systematical deviation of vertical excitation energy from absorption and emission spectra, obtained by CPCM‐PBEPBE/6‐31G* and CIS‐CPCM‐PBEPBE/6‐31G* models, were about 0.05 eV and 0.02 eV compared with the experimental values. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011 相似文献
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The 2H‐1‐benzo/naphthopyran‐2‐one‐4‐yl (un)substituted phenyl‐1,3,4‐oxadiazoles has been synthesized by the oxidative cyclization of benzoic acid hydrazides formed in situ by the condensation of the respective 2H‐1‐benzo/naphthopyran‐2‐one‐4‐carboxaldehyde and (un)substituted monobenzoyl hydrazide in moderate yields. Also, spiro[indoline‐thiozolidine]‐2,4′‐diones has been syhthesized in a similar way from 3‐phenyl‐spiro[3H‐indoline‐3,2′‐thiozolidine]‐2,4′‐(1 H)dione monohydrazide and (un)substituted benzaldehydes. 相似文献
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Density functional theory calculations have been carried out on nonconjugated D‐π‐A chromophores to investigate the different electron donors and conjugated bridges effects on the molecular nonlinear optical response. The results show that the large second‐order polarizability values can be achieved through careful combination of available electron donors, conjugated bridges for our studied nonconjugated D‐π‐A chromophores. The calculations also provide a clear explanation for the second‐order polarizability changes from the standpoint of transition energies, oscillator strengths, electron density difference, and bond length alternation. Solvent effect has great influence on the second‐order polarizability and electronic absorption spectrum. It is hoped that the results presented in this article will give some hints to the interrelated studies. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2009 相似文献
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Ali GUNDOGDU Volkan N. BULUT Celal DURAN Baris KEMER Olcay BEKIRCAN Mustafa SOYLAK 《中国化学》2008,26(1):143-145
2‐Phenyl‐5‐p‐tolyl‐1‐salicylideneamino‐1,3,4‐triazole (PTST) was studied among 2,5‐diaryl‐1‐salicylidene amino‐1,3,4‐triazole derivatives as a novel potential pH indicator. In terms of absorption intensity coming from the acid‐base reactions, PTST showed strong yellow‐green colour with high extinction coefficient in the pH range 7.0–9.5. In addition, the corresponding colour development at the transition point can be attributed to the resonance structures of PTST, which were caused by the hydrogen ion dissociation from the acidic form of the compound in the presence of alkali. The full geometric optimization and achievement of the electronic structure of the molecule were performed by an AM1 semiempirical method. The triazole compound was compared with phenolphthalein (PT), which is widely used as an acid‐base indicator in titrimetry, for accuracy test. 相似文献
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《国际化学动力学杂志》2018,50(9):651-658
The data on temperature, solvent, and high hydrostatic pressure influence on the rate of the ene reactions of 4‐phenyl‐1,2,4‐triazoline‐3,5‐dione ( 1 ) with 2‐carene ( 2 ), and β‐pinene ( 4 ) have been obtained. Ene reactions 1 + 2 and 1 + 4 have high heat effects: ∆Hr‐n ( 1 + 2 ) −158.4, ∆Hr‐n( 1 + 4 ) −159.2 kJ mol−1, 25°C, 1,2‐dichloroethane. The comparison of the activation volume (∆V≠( 1 + 2 ) −29.9 cm3 mol−1, toluene; ∆V≠( 1 + 4 ) −36.0 cm3 mol−1, ethyl acetate) and reaction volume values (∆Vr‐n( 1 + 2 ) −24.0 cm3 mol−1, toluene; ∆Vr‐n( 1 + 4 ) −30.4 cm3 mol−1, ethyl acetate) reveals more compact cyclic transition states in comparison with the acyclic reaction products 3 and 5 . In the series of nine solvents, the reaction rate of 1+2 increases 260‐fold and 1+4 increases 200‐fold, respectively, but not due to the solvent polarity. 相似文献
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Hasan Tanak Ayşen Ağar Metin Yavuz 《International journal of quantum chemistry》2011,111(9):2123-2136
The Schiff base compound, 4‐[(2‐hydroxy‐3‐methylbenzylidene)amino]‐1,5‐dimethyl‐2‐phenyl‐1,2‐dihydro‐3H‐pyrazol‐3‐one, has been synthesized and characterized by IR, UV–vis, and X‐ray single‐crystal determination. Molecular geometry from X‐ray experiment of the title compound in the ground state have been compared using the density functional method (B3LYP) with 6‐31G(d,p) basis set. Calculated results show that density functional theory (DFT) can well reproduce the structure of the title compound. The energetic behavior of the title compound in solvent media has been examined using B3LYP method with the 6‐31G(d,p) basis set by applying the Onsager and the polarizable continuum model (PCM). The results obtained with these methods reveal that the PCM method provided more stable structure than Onsager's method. By using TD‐DFT method, electronic absorption spectra of the title compound have been predicted and a good agreement with the TD‐DFT method and the experimental one is determined. The predicted nonlinear optical properties of the title compound are much greater than ones of urea. In addition, DFT calculations of the title compound, molecular electrostatic potential and NBO analysis were performed at B3LYP/6‐31G(d,p) level of theory. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011 相似文献
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Tautomeric equilibria of 2‐ and 4‐thiouracil in gas phase and in solvent: A density functional study
T. Marino N. Russo E. Sicilia M. Toscano 《International journal of quantum chemistry》2001,82(1):44-52
The relative stabilities of the five favored tautomers of 2‐ and 4‐thiouracil in gas phase and in water solution were determined by density functional theory employing the Becke, Lee, Yang, and Parr (B3LYP) exchange–correlation potential and the three 6‐31G(d,p), 6‐311++G(d,p), and triple‐zeta valence (TZVP) basis sets. Zero‐point vibrational corrections were also computed. Bulk solvent effects were studied in the framework of the self‐consistent reaction field approach by the polarizable continuum model. All calculations indicate that the most stable tautomer for both species, in the gas phase as well as in solution, has the oxo‐thione form, in full agreement with the previous ab initio and experimental studies. The tautomeric stability orders obtained in the aqueous solution are sensibly different from that in the gas phase. At B3LYP/6‐311++G(d,p) level in the gas phase, the following orders of stability for 2‐ and 4‐thiouracil tautomers were observed, respectively: S2U1>S2U2>S2U4>S2U5>S2U3 and S4U1>S4U2>S4U3>S4U4>S4U5. The corresponding trends in the aqueous phase are S2U1>S2U3>S2U2>S2U5>S2U4 and S4U1>S4U2>S4U3>S4U5>S4U4. On the basis of the computed energy differences we can hypothesize that only the oxo‐thione forms of 2‐ and 4‐thiouracil should exist in the gas phase and in water solution. © 2001 John Wiley & Sons, Inc. Int J Quant Chem 82: 44–52, 2001 相似文献
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Tsuneyuki Sato Shin‐Ichi Tada Makiko Seno Tomohiro Hirano 《Journal of polymer science. Part A, Polymer chemistry》2000,38(22):4137-4146
The polymerization of α‐N‐(α′‐methylbenzyl) β‐ethyl itaconamate derived from racemic α‐methylbenzylamine (RS‐MBEI) by initiation with dimethyl 2,2′‐azobisisobutyrate (MAIB) was studied in methanol kinetically and with ESR spectroscopy. The overall activation energy of polymerization was calculated to be 47 kJ/mol, a very low value. The polymerization rate (Rp ) at 60 °C was expressed by Rp = k[MAIB]0.5±0.05[RS‐MBEI]2.9±0.1. The rate constants of propagation (kp ) and termination (kt ) were determined by ESR. kp was very low, ranging from 0.3 to 0.8 L/mol s, and increased with the monomer concentration, whereas kt (4–17 × l04 L/mol s) decreased with the monomer concentration. Such behaviors of kp and kt were responsible for the high dependence of Rp on the monomer concentration. Rp depended considerably on the solvent used. S‐MBEI, derived from (S)‐α‐methylbenzylamine, showed somewhat lower homopolymerizability than RS‐MBEI. The kp value of RS‐MBEI at 60 °C in benzene was 1.5 times that of S‐MBEI. This was explicable in terms of the different molecular associations of RS‐MBEI and S‐MBEI, as analyzed by 1H NMR. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 4137–4146, 2000 相似文献
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Eun Young Chung Sung Mook Choi Hyun Bo Sim Kwang Kyu Kim Dong Suck Kim Kyung Jun Kim Mi Hye Yi 《先进技术聚合物》2005,16(1):19-23
A negative type photosensitive polyimide with alicyclic moiety (NPI) was synthesized from 5‐(2,5‐dioxotetrahydrofuryl)‐3‐methyl‐3‐cyclohexene‐1,2‐dicarboxylic anhydride and 4,4‐diaminobenzophenone by one‐step polymerization in m‐cresol. Properties of the polyimides were characterized and a photo‐crosslinking mechanism was investigated using DEPT 13C‐NMR and FT‐IR spectroscopy. The negative polyimide showed good photosensitivity on exposure to UV light from a mercury xenon lamp. The polyimide showed remarkable solubility difference after photo‐ irradiation with an exposure dose of 500 mJ/cm2. The resulting negative pattern of the photo‐cured NPI exhibited 10 μm resolution. Glass transition temperature of the photo‐crosslinked polyimide was about 307°C, which increased by 10°C compared to that of the polyimide before UV exposure. Transmittance of NPI after photo‐irradiation was about 87% at 500 nm. Copyright © 2004 John Wiley & Sons, Ltd. 相似文献
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《International journal of quantum chemistry》2018,118(14)
The role of nitrous oxide (N2O) in stratospheric ozone depletion and as a greenhouse gas has inspired the scientific community across the globe in understanding the capture, activation, and decomposition of it. Very recently people have started fixing N2O using frustrated Lewis pairs. In this study, we have tried to analyze the fixation of N2O by 1,4,2,5‐diazadiborinine by applying various computational tools and techniques associated with density functional theory. 1,4,2,5‐Diazadiborinine is taken as the fixing agent because of the ambiphilic nature of the two boron centers within it as reported by Wang et al. There are three possible ways of binding of N2O within it as observed in this study. A free energy surface is also generated for the three possible paths representing their thermochemical as well as kinetic stability. The fixation of N2O may become possible using this species as demonstrated by the current results. The nature of bonding between them is also explored through NBO, EDA, and electron density analyses. 相似文献
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Tsuneyuki Sato Masahiko Hashimoto Makiko Seno Tomohiro Hirano 《Journal of polymer science. Part A, Polymer chemistry》2003,41(12):1819-1830
The polymerizations of α‐ethyl β‐N‐(α′‐methylbenzyl)itaconamates carrying (RS)‐ and (S)‐α‐methylbenzylaminocarbonyl groups (RS‐EMBI and S‐EMBI) with dimethyl 2,2′‐azobisisobutyrate (MAIB) were studied in methanol (MeOH) and in benzene kinetically and with electron spin resonance (ESR) spectroscopy. The initial polymerization rate (Rp) at 60 °C was given by Rp = k[MAIB]0.58 ± 0.05[RS‐EMBI]2.4 ± 0.l and Rp = k[MAIB]0.61 ± 0.05[S‐EMBI]2.3 ± 0.l in MeOH and Rp = k[MAIB]0.54 ± 0.05[RS‐EMBI]1.7 ± 0.l in benzene. The rate constants of initiation (kdf), propagation (kp), and termination (kt) as elementary reactions were estimated by ESR, where kd is the rate constant of MAIB decomposition and f is the initiator efficiency. The kp values of RS‐EMBI (0.50–1.27 L/mol s) and S‐EMBI (0.42–1.32 L/mol s) in MeOH increased with increasing monomer concentrations, whereas the kt values (0.20?7.78 × 105 L/mol s for RS‐EMBI and 0.18?6.27 × 105 L/mol s for S‐EMBI) decreased with increasing monomer concentrations. Such relations of Rp with kp and kt were responsible for the unusually high dependence of Rp on the monomer concentration. The activation energies of the elementary reactions were also determined from the values of kdf, kp, and kt at different temperatures. Rp and kp of RS‐EMBI and S‐EMBI in benzene were considerably higher than those in MeOH. Rp of RS‐EMBI was somewhat higher than that of S‐EMBI in both MeOH and benzene. Such effects of the kinds of solvents and monomers on Rp were explicable in terms of the different monomer associations, as analyzed by 1H NMR. The copolymerization of RS‐EMBI with styrene was examined at 60 °C in benzene. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1819–1830, 2003 相似文献
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Theoretical study of molecular and electronic structure of 2‐Se‐(2‐methyl‐2‐propenyl)‐1‐benzoic acid
Ali Jameel Hameed Abraham F. Jalbout Bartosz Trzaskowski 《International journal of quantum chemistry》2007,107(1):152-158
A theoretical study of 2‐Se‐(2‐methyl‐2‐propenyl)‐1‐benzoic acid was carried out to investigate the molecular and electronic structure of this molecule, using the B3LYP density functional theory (DFT) method with the 6‐311+G** basis set. The optimized geometry of the molecule was obtained for the ortho, meta, and para isomers of the complex. In addition, the theoretical vibrational spectrum is presented, and thermal corrections in the limit of 100–1,000 K are discussed using the Shomate thermodynamic equations. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 相似文献