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21.
The energy of a disubstituted molecule has often been approximated by simple electrostatic formulas that represent the substituents as poles or dipoles. Herein, we test this approach on a new model system that is more direct and more efficient than testing on acid-base properties. The energies of 27 1,4-derivatives of bicyclo[2.2.2]octane were calculated within the framework of the density functional theory at the B3LYP/6-311+G(d,p) level; interaction of the two substituents was evaluated in terms of isodesmic homodesmotic reactions. This interaction energy, checked previously on some experimental gas-phase acidities, was considered to be accurate and served as reference to test the electrostatic approximation. This approximation works well in the qualitative sense as far as the sign and the order of magnitude are concerned: beginning with the strongest interaction between two poles, a weaker interaction between pole and dipole, and the weakest between two dipoles. However, all the electrostatic calculations yield energies that are too small, particularly for weak interaction, and this fundamental defect is not remedied by some possible improvements. In particular, variation of the effective permittivity would require a physically impossible value less than unity. The explanation must lie in a more complex distribution of electron density than anticipated in the electrostatic model. It also follows that possible conclusions about the transmission of substituent effects "through space" have little validity. 相似文献
22.
V. V. Shaposhnikova D. S. Sharapov I. A. Kaibova V. V. Gorlov S. N. Salazkin L. V. Dubrovina T. P. Bragina V. V. Kazantseva K. A. Bychko A. A. Askadskii A. S. Tkachenko G. G. Nikiforova P. V. Petrovskii A. S. Peregudov 《Polymer Science Series A》2007,49(10):1071-1078
Exchange reactions that may proceed in the course of polycondensation during formation of a polymer from 4,4′-difluorobenzophenone and 4,4′-(isopropylidene)diphenol have been studied. It has been shown that the molecular mass of the polymer decreases under the action of 4,4′-(isopropylidene)diphenol diphenolate. The nucleophilic substitution of the activated aryl halide in DMAA in the presence of potassium carbonate yields high-molecular-mass block copoly(arylene ether ketones) based on 4,4′-difluorobenzophenone and a number of bisphenols. It was demonstrated the synthetic procedure and the chemical structure of block copoly(arylene ether ketones) strongly affect the onset temperature of softening and the mechanical characteristics of the films based on these polymers. 相似文献
23.
A. I. Kovalev Yu. I. Lyakhovetskli M. M. Teplyakov A. L. Rusanov P. V. Petrovskii S. O. Yakushin 《Russian Chemical Bulletin》1993,42(9):1529-1535
The chemical heterogeneity of polyphenylenes obtained by trimerization poiycycio-condensation of acetylaromatic compounds has been investigated by GLC-MS analysis of the products of trimerization cyclocondensation of acetophenone. The mechanism for the formation of side products of the reaction is discussed. The presence of dypnone fragments in the polyphenylene structure results in a decrease in the thermal stability of these polymers.Deceased March, 1993.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1595–1601, September, 1993. 相似文献
24.
25.
E. G. Ter-Gabriélyan N. P. Gambaryan É. P. Lur'e P. V. Petrovskii 《Russian Chemical Bulletin》1979,28(5):992-995
Conclusions Perfluoro-(2-isobutenyl-1,1,4,4-tetramethyl-1,3-butadiene) yields 1,4 addition products both in nucleophilic addition and in radical chlorination.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1061–1064, May, 1979. 相似文献
26.
27.
S. D. Sokolov T. N. Egorova P. V. Petrovskii 《Chemistry of Heterocyclic Compounds》1974,10(5):516-520
The 4-nitro derivative is formed in the nitration of 3,5-diphenylisoxazole (I) in acetic anhydride. Mononitration of isoxazole I in concentrated H2SO4 gave 3-phenyl-5-(p-nitrophenyl)isoxazole, while polynitration gave a mixture of dinitro derivatives, among which 3- (m-nitro-phenyl)-5-(p-nitrophenyl)isoxazole was identified. The structures of the isolated products were established by means of the spectra, by reaction-chromatography methods, and gasliquid chromatography, as well as by a comparison with genuine samples of the two mononitro and four dinitro derivatives of isoxazole I. 相似文献
28.
ValeryN. Kalinin IgorV. Shishkov SergeyK. Moiseev ElviraE. Shults GenrikhA. Tolstikov NataliaI. Sosnina PavelV. Petrovskii KonstantinA. Lyssenko Helmut Schmidhammer 《Helvetica chimica acta》2006,89(5):861-869
In a search for starting materials for the preparation of 7,8‐fused morphine alkaloid derivatives, 8‐[(1E‐2‐phenylethenyl]codeinone dimethyl ketal ( 4 ) and 8‐[(1E‐2‐phenylethenyl]codeine ( 5 ) were prepared. These dienes were used as substrates in the Diels–Alder reactions. Compound 5 formed the ‘normal’ adduct 12 with N‐phenylmaleimide, while compound 4 behaved in reactions with dienophiles as the ‘masked’ diene 11 , a 8‐[(1E)‐2‐phenylethenyl]‐substituted thebaine, yielding the corresponding 19‐substituted 6,14‐endo‐etheno‐6,7,8,14‐tetrahydrothebaines. Specifically, reaction of 4 with methyl vinyl ketone gave rise to 19‐[(1E)‐phenylethenyl]thevinone ( 14 ) whose structure was elucidated by an X‐ray diffraction analysis. The thebaine derivative 11 was also prepared from 4 . 相似文献
29.
A many-body diagrammatic perturbation theory of rotation–vibration spectra is elaborated. The present approach is based on two many-body techniques, namely on the second quantization formalism (a rotating–vibrating molecule is formally treated here as a system of interacting vibrons, obeying the Bose–Einstein statistics) and the many-body diagrammatic theory of a model Hamiltonian, initially suggested in the microscopic theory of nuclei and in the last decade very frequently exploited in the accounting for the correlation effects in many electron systems. In the framework of this theory, the rotation–vibration energies are determined as the eigenvalues of a finite-dimensional model eigenproblem. 相似文献
30.
A.N. Nesmeyanov V.V. Krivykh P.V. Petrovskii V.S. Kaganovich M.I. Rybinskaya 《Journal of organometallic chemistry》1978,162(3):323-342
Irradiation of alkenylarene tricarbonyl-chromium, -molybdenum, and -tungsten compounds in which the double bond is separated from the arene moiety by a two- or three-atom bridge results in intramolecular cyclization to give stable chelate alkenylarenedicarbonylmetal complexes. Chelate complexes containing four-atom bridges have low stabilities, and those with monoatomic bridges were not formed at all. Irradiation of styrenetricarbonyl-chromium and -molybdenum leads to dinuclear tricarbonylmetal—dicarbonylmetal complexes. The chelate complexes obtained have been studied by IR, proton NMR, and 13C NMR spectroscopy. The electron density distributions and the stereochemistry of the complexes are discussed. With nonsymmetric arenes, diastereoisomers are formed; the predominant isomers have been isolated in the pure form. According to the proton NMR data the double bond in alkenylarenechromium chelates is parallel of nearly parallel to the arene ring plane. 相似文献