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1.
The nature of the 1,3 hydrogen rearrangement of formamidine (H2N-CH=NH) and the solvent effects on that reaction are studied with ab initio molecular orbital calculations on the basis of the supermolecule model. The reaction path and the motion of the migrating hydrogen atom are traced by using the concept of the intrinsic reaction coordinate (IRC). Four types of orientation of one water molecule to formamidine at the transition state of reaction are examined and the results are discussed from the standpoint of the orbital interactions. 相似文献
2.
A simple electrostatic analysis is given of the virtual charge (solvaton) model to represent the environment effect on the electronic wave function of a solute immersed in a polarizable surrounding. New features of this model are found. The classical aspects are discussed and secondly the quantal implications are considered. A correct Hartree-Fock-like operator is derived which represents an electron in a molecular orbital subjected to the average effect of the other electrons and to the reaction field produced by the virtual charges on the atomic centers.A general formalism based on the preceding model is presented in appendix. The final equations have a form similar to Newton's equation to represent a solvated electron. Unlike some other theories in this field, there is no cut-off involved in the evaluation of the molecular integrals. 相似文献
3.
A. B. Remizov D. I. Kamalova R. A. Skochilov I. A. Suvorova N. N. Batyrshin Kh. E. Kharlampidi 《Journal of Molecular Structure》2004,700(1-3):73-79
Self-association of cumyl, tertiary butyl and 3-phenylmethyl hydroperoxides in solutions of n-decane, carbon tetrachloride and chlorobenzene were studied by IR spectroscopy (3100–3700 cm−1, 293–353 K). The experimental data were interpreted by factor analysis and band contour resolution. The di- and trimerization constants and thermodynamic parameters of self-associates were determined. Intramolecular hydrogen bond of cumyl hydroperoxide was investigated. The conformations of tertiary butyl and cumyl hydroperoxides were studied. The solvent influence on the thermodynamic parameters of hydrogen bond was found. 相似文献
4.
B.A. Shainyan N.N. Chipanina T.N. Aksamentova L.P. Oznobikhina G.N. Rosentsveig I.B. Rosentsveig 《Tetrahedron》2010,66(44):8551-8556
The hydrogen bonding in [(1-arylsulfonylamino-2,2,2-trichloro)ethyl]biuret 1, [(1-arylsulfonylamino-2,2,2-trichloro)ethyl]oxamide 2, and [(1-arylsulfonylamino-2,2,2-trichloro)ethyl]dithiooxamide 3, the sulfonamide derivatives of biuret 4, oxamide 5, and dithiooxamide 6, has been studied by molecular spectroscopy and DFT theoretical calculations including frequency calculations, at the B3LYP/6-311+G(d,p) level of theory. The analysis of the CO?HN and CS?HN intramolecular hydrogen bonds closing the five- and six-membered rings employing the atoms-in-molecules (AIM) method using the MP2(full)/6-311++G(d,p) wave functions has shown that their stability is increased in comparison to the original molecules and is much higher in the thiocarbonyl compounds. The results of the AIM and the NBO analysis of donor-acceptor interactions are in good agreement with each other and with the experimental FT-IR spectroscopy data. 相似文献
5.
Infrared vibrational spectroscopy of 3-methylbutanone [Me(CO)iPr] leads to two conclusions: (1) The conformational identity is different in the gas phase and in various solvents. (2) In the gas phase, type B rovibrational structures are observed. Thus, the molecular symmetry isC
5. The following interpretation is based upon a model which implicitly takes the solvent into account in the framework of an empirical calculation. The solvent increases the interconversion barrier between two enantiomers. As a consequence, the molecule changes conformation, moving from the stable conformation with bisected carbonyl seen in the gas phase, to a conformation with an eclipsed carbonyl in solutions. 相似文献
6.
Frieder Birnstock Hans -Jörg Hofmann Hans -Joachim Köhler 《Theoretical chemistry accounts》1976,42(4):311-323
Based on Sinanolu's solvent theory in connection with a method for the calculation of the molecular volume given by Beveridge a modified continuum model is suggested. The model is tested by the determination of the conformational structure of the title compounds. The predictions obtained by this model are in good agreement with the experimentally determined data. 相似文献
7.
8.
Heinz Falk Norbert Müller Helmut Wöss 《Monatshefte für Chemie / Chemical Monthly》1987,118(11):1301-1315
10-(2-Pyridyl)-, 10-(2-pyrrolyl)-, and 10-(2-imidazolyl)-bilatrienes-abc were prepared and their configurations and conformations in several solvents were investigated using UV-VIS-spectroscopy and NMR-techniques. Whereas the pyridyl and the pyrrolyl derivatives adopt the common circular helical arrangement of the bilin chromophor in a variety of solvents like chloroform, methanol, and dimethylsulfoxid, the imidazolyl derivative exhibits a dramatic solvent dependence of its geometry. It is of circular helical form in methanol; in chloroform, however, it adopts a stretched arrangement at the 10-methine position with an intermediate exchange (NMR-timescale) between the two identical tautomers at room temperature. In dimethylsulfoxide the population of the two diastereomers is comparable and exchange at room temperature is slow enough to allow their characterisation by1H-NMR. A variable temperature study allowed a determination of thermodynamic and kinetic parameters for this isomerising system. 相似文献
9.
Bin Tu Brahmananda Ghosh David A. Lightner 《Monatshefte für Chemie / Chemical Monthly》2004,135(5):519-541
Summary. Bilirubin congeners with dipyrrinones conjoined to a diaceteylene unit (–CC–CC–) rather than to –CH2– were synthesized and examined spectroscopically. This new class of rubrified linear tetrapyrroles cannot easily fold or bend in the middle, but the dipyrrinones can rotate independently about the diacetylene unit. Thus, unlike bilirubin, which is bent in the middle and has a ridge-tile shape, the diacetylene unit orients the attached dipyrrinones along a linear path, and intramolecular hydrogen bonding between the dipyrrinones and opposing carboxylic acids preserves a twisted linear molecular shape when the usual propionic acids are replaced by hexanoic. In a bis-hexanoic acid rubin, the extended planes of the dipyrrinones intersect along the –(CC)2– axis at an angle of 102° for the conformation stabilized by intramolecular hydrogen bonding. With propionic acid chains, however, neither CO2H can engage an opposing dipyrrinone in intramolecular hydrogen bonding, and the energy-minimum conformation of this linear pigment, shows nearly co-planar dipyrrinones, with an intersection of an angle of 180° of the extended planes of the dipyrrinones. Spectroscopic evidence for such linearized and twisted (bis-hexanoic) and planar (bis-propionic) structures comes from the pigments NMR spectral data and their exciton UV-Vis and induced circular dichroism spectra. 相似文献
10.
Giorgio Tosi Paolo BalerciaCarla Conti Paolo FerrarisElisabetta Giorgini Lorenzo Lo MuzioSimona Sabbatini Daniela StramazzottiCorrado Rubini 《Vibrational Spectroscopy》2011,57(1):140-147
This study has been undertaken to investigate spectral features of cystic lesions of the jaw with the aim to understand their tumoral progression and to evidence initial signals of neoplastic changes.Three important groups (according to the World Health Organization classification) representing inflammatory (radicular) and developmental (orthokeratinized odontogenic, OOC) cysts as well as keratocystic odontogenic tumor (KCOT) of the jaw have been studied by microimaging infrared spectroscopy. From the spectral data analysed with the multivariate pattern recognition procedure, representative spectra were isolated and used to build correlation maps to localize the biochemical components in the tissue.The procedure enabled to better understand spectral features of these classes of cysts and to discriminate tumoral from non-tumoral spectra through the analysis of ‘vibrational markers’. In KCOT, the correlation of calcium derivatives (in metaplastic or displastic bones) with the tumor has been highlighted, too. The distribution of various biochemical components in the tissues, achieved through correlation maps of representative spectra, resulted in satisfactory agreement with the histopathological analysis. ‘Spectral isolation’ of micro tumorigenic zones in some normal OOC cysts, demonstrated the potentiality of infrared spectroscopy to evidence the early stage of a hidden lesion. 相似文献
11.
The intrachain and interchain hydrogen bonding of poly(N-isopropylacrylamide) (PNIPA) and intermolecular hydrogen bonding between PNIPA chains and the solvent molecules in the mixed solvent of methanol and water have been quantitatively investigated by using Fourier transform infrared (FTIR) spectroscopy at 25 °C. In this spectroscopic system with curve fitting program, we found that in the C-H stretching region, both the N-isopropyl group and the backbone underwent conformational change upon the solvent composition. An analysis of the amide I band suggested that the amide groups of PNIPA were mainly involved in intermolecular hydrogen bonding with water molecules, and the polymer chains were flexible and disordered in the mixed solvent when the methanol volume fraction (χv) was lower than 15%. While χv was in the range of 15-65%, about 30% of these intermolecular hydrogen bonding between the polymer and water were replaced by intrachain and interchain hydrogen bonding, consequently, PNIPA shrinked as aggregates. If χv was above 65%, the interchain hydrogen bonding became predominant due to the solubility characteristics of amphiphilic methanol, and the PNIPA system was homogeneous solution again. We believe that the reentrant transition is related to the weaker interaction between PNIPA molecules and methanol-water complexes, (H2O)m(CH3OH)n (m/n = 5/1, 5/2, 5/3, 5/4, 5/5) as compared to that between PNIPA and free water or free methanol. 相似文献
12.
The intrinsic viscosities of methylene blue, glucose and dextran were determined in various solvents. They are linear againstY Winstein-Grunwald solvent parameters. The relation observed offers an alternative route of the evaluation of the solvent effects by means of viscosimetric measurements.
Viskosimetrische Auswertung von Lösungsmittel-Effekten
Zusammenfassung Die Grenzviskositäten von Methylenblau, Glukose und Dextran wurden in verschiedenen Lösungsmitteln bestimmt. Sie sind gegen denWinstein-Grunwald-LösungsmittelparameterY linear. Die festgestellte Beziehung bietet einen alternativen Weg zur Bestimmung von Lösungsmitteleffekten mittels viskosimetrischer Messungen.相似文献
13.
13C NMR spectroscopic studies were performed for carbonyl compounds having a hydroxyl group, a carboalkoxy group, an acetoxy group, or a carboxyl group in various solvents with different polarities for observation of their behaviors of 13C NMR chemical shifts of carbonyl carbons in solutions. It was found that the chemical shifts of the carbonyl carbons in 13C NMR have good correlation with the empirical parameter for solvent polarities, ETN, depending on the structures. Inter- or intramolecular hydrogen bonding and dipolar-dipolar interactions appear to play a key role in this observation. 相似文献
14.
Conformational analysis of famotidine (FAMO) and some analogues have been performed using AM1 calculations. In addition, Conformational analysis were done on the 2-guanidinylthiazole moiety in order to see the effect of the N-sulfamoyl fragment and the methylthioethyl chain of FAMO on the thiazole ring. The results revealed that the N6H form (the guanidinium cation) was the most stable and might therefore be the best candidate for interacting with the histamine H2-receptor. The calculations for the N6H forms of FAMO and analogues showed a strong hydrogen bond anchoring the guanidine chain in the same plane as the thiazole ring, in agreement with X-ray diffraction and 1H NMR studies. 相似文献
15.
M. Tommasini C. Castiglioni G. Zerbi P. Toniolo R. Picozzi C. Tonelli 《Journal of fluorine chemistry》2006,127(3):320-329
A new partially halogenated ether (ClCF2CF(CF3)OCF2CH3) has been synthesized and characterized using DSC, GC, 1H and 19F NMR, IR. The experimental infrared spectra of this “flexible” molecule have been successfully interpreted on the basis of reliable Density Functional Theory calculations. An efficient method useful for the identification of the many stable conformers has been developed and applied. Infrared spectra of the stable conformers have been simulated after full geometry optimization. The results obtained allow detection of conformation-sensitive bands, making possible the interpretation of fine details in the spectra. 相似文献
16.
Toshio Fuchigami 《Journal of fluorine chemistry》2007,128(4):311-316
Recent studies on solvent effects on electrochemical partial fluorination are reviewed. At first, the historical background and some problems of electrochemical fluorination in organic solvents like acetonitrile (MeCN) are briefly mentioned. Ethereal solvents like dimethoxyethane (DME) and a mixture of DME and MeCN were found to improve both the yield and current efficiency for electrochemical fluorination since these solvent systems effectively suppress anode passivation and overoxidation of fluorinated products once formed during the electrolysis. It was also found that DME stabilizes radical cationic intermediates of 4-arylthio-1,3-dioxolan-2-ones and 3-phenylthiophthalide leading to α-fluorination while dichloromethane (CH2Cl2) destabilizes them leading to fluorodesulfurization. On the other hand, imidazolium ionic liquids and liquid fluoride salts like Et4NF·4HF and Et3N·5HF exhibited similar effects to CH2Cl2. Selective fluorination of hardly oxidizable phthalide was also achieved using a combination of two kinds of ionic liquids (imidazolium triflate and liquid fluoride salts). 相似文献
17.
One of two fundamental types of solute–solvent intermolecular interactions are the specific interactions, such as hydrogen bonding complexation between solute and solvent. The Gibbs energy of specific interactions is an important quantity that determines rate and equilibrium constants in solutions, but it is difficult to obtain by direct measurement. We proposed equations allowing to determine the contribution of specific interactions to the Gibbs energy of solvation in nonelectrolyte solutions. Applying it for the case of proton donating solutes with one acidic hydrogen atom dissolved in basic solvents, we obtained the values of the Gibbs energies of 1:1 complexation in pure base. These values have been compared with the Gibbs energies of 1:1 complexation in tetrachloromethane. Most of the hydrogen bonds are found to have the same energy in pure base and in CCl4, however, some weakly bound complexes seem to become even more weakened in pure base medium. Suggested method is applicable in a general situation when multiple associates of different stoichiometry and structure are formed. 相似文献
18.
Tetramethylurea was hydrolyzed in aqueous hydrochloric acid at temperatures of 80, 90, and 100°C. All reactions were carried out in an excess of both tetramethylurea and water, with first-order dependence on acid concentration being observed. As the concentration of water was increased, the rate of hydrolysis decreased until equimolar amounts of water and tetramethylurea were present. Subsequent addition of water had no effect on the observed rate. 相似文献
19.
Mariza N. Alberti 《Tetrahedron》2006,62(46):10660-10675
The factors that control the stereochemistry of sensitized photooxygenation of alkenes via singlet oxygen (ene reaction) are selectively reported. We also introduce our most recent stereoelectronic effects on the singlet oxygen-ene reaction. The origin of site selectivity and solvent-dependent stereoselectivity in this classical ene reaction with simple as well as functionalized alkenes is highlighted. These studies and other similar studies have enhanced substantially the utility of singlet oxygen in the synthesis of natural and non-natural products. 相似文献
20.
A detailed analysis of the bands appearing in the OH stretching region of the infrared spectrum of ethyl phenol solutions is presented. In cyclohexane solutions, the band due to “free” (non-hydrogen-bonded groups) contains overlapping contributions from both monomeric and end-group species. Other assignments are made on the basis of whether the proton and oxygen in a particular OH group are both involved in hydrogen bonds (as “donors” and “acceptors”, respectively), or if only the proton is acting as a donor. The strongest band in the spectra obtained at the highest concentration of ethyl phenol is due to OH groups present in linear chains of hydrogen-bonded OH groups (as recognized in numerous other studies), but a band due to cyclic trimers has also been identified. The assignment of other modes is more uncertain and various possibilities are discussed. In toluene solutions, assignments are more complicated, because bands due to OH–π hydrogen bonds are observed instead of free groups. Finally, the data from cyclohexane solutions was used to calculate equilibrium constants capable of describing the distribution of species present. A new methodology for determining the equilibrium constant describing association in the form of dimers is described. 相似文献