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991.
The study of the energetics of phenolic compounds has a considerable practical interest since this family of compounds includes numerous synthetic and naturally occurring antioxidants. In this work, density functional theory (DFT) has been used to investigate gas-phase thermochemical properties of the following tri-substituted phenols: 2,4,6-trimethylphenol, 2,6-dimethyl-4-tert-butylphenol, 2,6-dimethyl-4-methoxyphenol, 2,4,6-tri-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-methoxyphenol, 2,4,6-trimethoxyphenol, 2,6-dimethoxy-4-methylphenol and 2,6-dimethoxy-4-tert-butylphenol. Molecular structures were computed with the B3LYP and the ωB97X-D functionals and the 6-31G(d) basis set. More accurate energies were obtained from single-point energy calculations with both functionals and the 6-311++G(2df,2pd) basis set. Standard enthalpies of formation of the phenolic molecules and phenoxyl radicals were derived using an appropriate homodesmotic reaction. The OH homolytic bond dissociation enthalpies, gas-phase acidities and adiabatic ionization enthalpies were also calculated. The general good agreement found between the calculated and the few existent experimental gas-phase thermochemical parameters gives confidence to the estimates concerning the phenolic compounds which were not yet experimentally studied. 相似文献
992.
Experimentally determined volumetric properties of the liquid binary mixture of {water (1) + glycerol (2)} were processed to calculate the changes of the following thermodynamic parameters with pressure: excess molar Gibbs free energy, , excess molar entropy, , excess molar enthalpy, , as well as the enthalpy of mixing of water and glycerol, , at 100 MPa. The mixing enthalpies of water and glycerol, , became more exothermic with pressure increasing at all temperatures studied. 相似文献
993.
In this work, speed of sound for n-decane, n-hexadecane and tetralin, as well as for binary mixtures involving these hydrocarbons, were determined at pressures of (0.1, 5, 10, 15, 20 and 25) MPa at temperatures of (313.15, 323.15 and 333.15) K at different compositions. Density data at atmospheric pressure for these same systems were measured experimentally at temperatures of (313.15, 323.15 and 333.15) K. From these results and thermodynamic definitions, the following properties were calculated: density at high pressures, excess molar volume and excess isentropic compressibility. Tetralin, n-decane and n-hexadecane are chemicals asymmetrical in shape, length and chemical nature that can be found in naphtha and kerosene fractions. The influence of these differences on the physical properties of these mixtures was then evaluated. Density and speed of sound data were correlated with Prigogine–Flory–Patterson (PFP) equation of state. The PFP model correlated well experimental densities for pure components but did not correlate so well the speed of sound dependency with pressure. The model calculated well excess properties, with correct signs, magnitudes, and the qualitative effect of pressure and temperature on these properties. 相似文献
994.
Diorganotin(IV) Complexes with Monohydrate Disodium Salt of Iminodiacetic Acid: Synthesis,Characterization, Crystal Structure and Biological Activities 下载免费PDF全文
Shabbir Hussain Saqib Ali Saira Shahzadi Corrado Rizzoli Muhammad Shahid 《中国化学会会志》2015,62(9):793-802
Diorganotin(IV) derivatives have been synthesized by the reaction of R2SnL2 (R=n‐Bu 1 , Ph 2 ) with monohydrate disodium salt of iminodiacetic acid ( Na2L ) in 1 : 1 M/L ratio under reflux conditions. The compounds have been characterized by FT‐IR, NMR (1H and 13C) spectoscopy, electron ionization mass spectrometry (EIMS), thermogravimetric analyses (TGA) and single crystal XRD. FTIR data indicates a mono‐dentate binding mode of the carboxylic acid group as well as participation of the amino nitrogen and aqua oxygen in coordination with organotin(IV) moieties. NMR data demonstrates a tetra‐coordinated environment around tin(IV) in solution. Mass spectrometric and thermogravimetric analyses verify the close similarities between the molecular structures of both complexes. The thermal stability of diphenyltin(IV) derivative ( 2 ) was found slightly higher than that of the free ligand ( Na2L ). Single crystal X‐ray analysis of the complex 1 have shown a hexa‐coordinated geometry around Sn(IV) with trans configuration. There are evidences for the existence of intermolecular hydrogen bonding in the structure of the complexes. The products displayed significant antibacterial and antifungal activities in contrast to the biologically inactive ligand precursor. However, the hemolytic cytoxicity of the complexes was comparatively high than the free ligand. 相似文献
995.
Stimulated by the recent experimental success in production and characterization of YCN@Cs(6)‐C82, the possibility of encapsulating YCN cluster in the C78 fullerene has been performed using density functional theory. Six isomers of YCN@C78 are considered based on six lowest energy C782? isomers. The results reveal that YCN@D3h(24109)‐C78 and YCN@C2v(24107)‐C78, both of which satisfy the isolated‐pentagon rule, present excellent thermodynamic stability with very small energy differences. Moreover, the large HOMO‐LUMO gaps (1.55 and 1.47 eV for YCN@D3h(24109)‐C78 and YCN@C2v(24107)‐C78, respectively) indicate their high kinetic stabilities. Significantly, in both the structures, the encapsulated YCN cluster is triangular, similar to the cases of YCN@Cs(6)‐C82 and TbCN@C2(5)‐C82. In addition, electronic absorption spectra, infrared spectra, and 13C nuclear magnetic resonance spectra of two stable structures have also been explored to further disclose the molecular structures and properties. © 2015 Wiley Periodicals, Inc. 相似文献
996.
Novel and Stereospecific Synthesis of (2S)‐3‐(2,4,5‐Trifluorophenyl)propane‐1,2‐diol from D‐Mannitol 下载免费PDF全文
Derya Aktaş Meryem Fıstıkçı Özlem Gündoğdu Hasan Seçen M. Fethi Şahin Ramazan Altundaş Yunus Kara 《Helvetica chimica acta》2015,98(8):1127-1131
A stereospecific synthesis of (2S)‐3‐(2,4,5‐trifluorophenyl)propane‐1,2‐diol from D ‐mannitol has been developed. The reaction of 2,3‐O‐isopropylidene‐D ‐glyceraldehyde with 2,4,5‐trifluorophenylmagnesium bromide gave [(4R)‐2,2‐dimethyl‐1,3‐dioxolan‐4‐yl](2,4,5‐trifluorophenyl)methanol in 65% yield as a mixture of diastereoisomers (1 : 1). The Ph3P catalyzed reaction of the latter with C2Cl6 followed by reduction with Pd/C‐catalyzed hydrogenation gave (2S)‐3‐(2,4,5‐trifluorophenyl)propane‐1,2‐diol with >99% ee and 65% yield. 相似文献
997.
Heat capacities and phase-transition properties for xanthone (IUPAC name 9H-xanthen-9-one and Chemical Abstracts registry number [90-47-1]) are reported for the temperature range 5 < T/K < 524. Statistical calculations were performed and thermodynamic properties for the ideal gas were derived based on molecular geometry optimization and vibrational frequencies calculated at the B3LYP/6-31+G(d,p) level of theory. These results are combined with sublimation pressures from the literature to allow critical evaluation of inconsistent enthalpies of sublimation for xanthone, also reported in the literature. Literature values for the enthalpy of combustion of xanthone are re-assessed, a revision is recommended for one result, and a new value for the enthalpy of formation of the ideal gas is derived. Comparisons with thermophysical properties reported in the literature are made for all other reported and derived properties, where possible. 相似文献
998.
Base‐Catalyzed Formation of Isoxazoles from Dialkyl Acetylenedicarboxylates and 2‐Nitroacetophenones 下载免费PDF全文
The reaction of dialkyl acetylenedicarboxylates with 1‐aryl‐2‐nitroethanones in the presence of pyridine leads to dialkyl 5‐aryloyl‐isoxazole‐3,4‐dicarboxylates through a novel mechanism, which involves a [2+2] cycloaddition/ring opening/cyclization sequence. 相似文献
999.
Novel 1,2,3,4‐Tetrahydroquinazolinones via Reaction of 2‐Amino‐N‐substituted Benzamides and Dimethyl Acetylenedicarboxylate 下载免费PDF全文
Semiramis Nahavandian Sadegh Allameh Mina Saeedi Shirin Ansari Mohammad Mahdavi Alireza Foroumadi Abbas Shafiee 《Helvetica chimica acta》2015,98(7):1028-1033
Reaction of 2‐amino‐N‐substituted benzamides and dimethyl acetylenedicarboxylate (DMAD) in the presence of 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU) in H2O at room temperature led to the formation of novel 1,2,3,4‐tetrahydroquinazolinones. 相似文献
1000.
Reaction of 3‐Hydroxyquinoline‐2,4‐diones with Inorganic Thiocyanates in the Presence of Ammonium or Alkylammonium Ions: the Unexpected Replacement of a Hydroxy Group by an Amino Group 下载免费PDF全文
Antonín Klásek Ondřej Rudolf Michal Rouchal Antonín Lyčka 《Helvetica chimica acta》2015,98(3):318-335
3‐Hydroxyquinoline‐2,4‐diones react with KSCN in the presence of the NH$\rm{{_{4}^{+}}}$ ions to generate 2,3‐dihydro‐3‐thioxoimidazo[1,5‐c]quinazolin‐5(6H)‐ones, 2,3‐dihydro‐2‐thioxo‐1H‐imidazo[4,5‐c]quinolin‐4(5H)‐ones, and products of molecular rearrangement of the 3‐aminoquinolinedione intermediates. Starting compounds with a benzyl (Bn) group at C(3) afford 3‐aminoquinolinediones, even when only AcONH4 is used. The results of the reaction between 3‐hydroxyquinoline‐2,4‐diones and KSCN in the presence of BuNH2 show that replacing a OH group with a secondary NH2 group is also possible. 相似文献