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S. A. Kirillov A. Morresi M. Paolantoni P. Sassi 《Journal of Physical Organic Chemistry》2007,20(8):568-573
The most obvious consequence of the concept of aromaticity is the common confidence that in aromatic compounds, bond lengths do not alternate and are between typical to the single and double ones. However, in 1994, performing crystal structure investigations of substituted pyridines and their salts, Krygowski and co‐workers have discovered a very surprising angular group induced bond alteration (AGIBA) effect: It appears that some angular substituents, like methoxy or nitrozo groups, can induce bond alternation in aromatic rings. Crystal studies do not allow one to operate with liquids that are more common in organic chemistry. This paper presents the first possible evidence of spectroscopic manifestations of the AGIBA effect. Raman spectra of the liquid toluene are analyzed. It is found that instead of being single, the line corresponding to the ring breathing vibrations is clearly split by 1.0–1.4 cm?1, thus indicating the presence of two (cis‐ and trans‐) AGIBA isomers. The energy difference between these isomers estimated in temperature dependent Raman studies is found equal to 6.68 kJ mol?1. The low‐wavenumber line therefore corresponds to the cis‐AGIBA isomer and the high‐wavenumber line to the trans‐AGIBA isomer stabilized by the AGIBA effect. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
3.
For any finite Coxeter system (W,S) we construct a certain noncommutative algebra, the so-called bracket algebra, together with a family of commuting elements, the so-called Dunkl elements. The Dunkl elements conjecturally generate an algebra which is canonically isomorphic to the coinvariant algebra of the Coxeter group W. We prove this conjecture for classical Coxeter groups and I2(m). We define a “quantization” and a multiparameter deformation of our construction and show that for Lie groups of classical type and G2, the algebra generated by Dunkl’s elements in the quantized bracket algebra is canonically isomorphic to the small quantum cohomology ring of the corresponding flag variety, as described by B. Kim. For crystallographic Coxeter systems we define the so-called quantum Bruhat representation of the corresponding bracket algebra. We study in more detail the structure of the relations in Bn-, Dn- and G2-bracket algebras, and as an application, discover a Pieri-type formula in the Bn-bracket algebra. As a corollary, we obtain a Pieri-type formula for multiplication of an arbitrary Bn-Schubert class by some special ones. Our Pieri-type formula is a generalization of Pieri’s formulas obtained by A. Lascoux and M.-P. Schützenberger for flag varieties of type A. We also introduce a super-version of the bracket algebra together with a family of pairwise anticommutative elements, the so-called flat connections with constant coefficients, which describes “a noncommutative differential geometry on a finite Coxeter group” in the sense of S. Majid. 相似文献
4.
N. F. Kirillov V. V. Shchepin V. S. Melekhin 《Russian Journal of Organic Chemistry》2007,43(11):1628-1631
Methyl 1-(2-bromo-2-methyl-1-oxopropyl)-, 1-(1-bromocyclopentylcarbonyl)-, and 1-(1-bromocyclohexylcarbonyl) cyclobutanecarboxylates reacted with zinc and aromatic aldehydes to give, respectively, 7-aryl-2,2-dimethyl-6-oxaspiro[3.5]nonane-5,9-diones, 11-aryl-12-oxadispiro[3.1.4.3]tridecane-5,13-diones, and 12-aryl-13-oxadispiro[3.1.5.3]tetradecane-5,14-diones. 相似文献
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A generalization of the Heisenberg XXZ model to the case of arbitrary spin with anisotropy of light-plane type is investigated. The base state of the system, the spectrum of excitations over it, and their scattering matrix are found. The magnetic susceptibility of the model for small magnetic fields and the low-temperature heat capacity are computed.Translated from Zapiski Nauchnykh Seminarov Leningradskogo Otdeleniya Matematicheskogo Instituta im. V. A. Steklova AN SSSR, Vol. 145, pp. 109–133, 1985. 相似文献
7.
A continuum model describing highly excited (Rydberg) electronic states in clusters composed of polar molecules was proposed. On the basis of this model, the wave functions of Rydberg electronic states of clusters were calculated for a wide range of characteristic cluster parameters. These states are not hydrogen-like and can be described using the quantum defect theory. This fact indicates that radiative transitions can be forbidden within certain ranges of cluster parameters. The quantum defects in clusters and the lifetimes of different states were calculated. The possibility of formation of metastable Rydberg states and anomalous spectral characteristics of Rydberg clusters was shown. 相似文献
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V. V. Shchepin N. F. Kirillov V. S. Melekhin 《Russian Journal of Organic Chemistry》2006,42(10):1486-1489
Reformatsky reagents obtained from methyl 1-bromocyclohexane-and 1-bromocyclopentane-1-carboxylates reacted with aromatic aldehyde phenyl-and benzoylhydrazones to give 3-aryl-2-phenylamino-2-azaspiro[3.5]nonan-, 3-aryl-2-phenylamino-2-azaspiro[3.4]octan-, 3-aryl-2-benzoylamino-2-azaspiro[3.5]-nonan-, and 3-aryl-2-benzoylamino-2-azaspiro[3.4]octan-1-ones, respectively. The reaction of furan-2-carbaldehyde phenylhydrazone with methyl 1-bromocyclohexane-1-carboxylate and zinc led to the formation of 4-(2-furyl)-2-phenyl-2,3-diazaspiro[4.5]decan-1-one. 相似文献
10.
Shchepin V. V. Kirillov N. F. Nedugov A. N. 《Russian Journal of General Chemistry》2003,73(8):1264-1266
Methyl esters of 1-(-bromoisobutyryl)cyclohexanecarboxylic or 3-(1-bromocyclohexyl)-2,2-dimethyl-3-oxopropanoic acids react with zinc and arylglyoxals to form 3-aroyl-4,4-dimethyl-2-oxaspiro[5.5]undecane-1,5-diones or 1-aroyl-4,4-dimethyl-2-oxaspiro[5.5]undecane-3,5-diones, respectively. The former products react with phenylhydrazine, yielding 3-[aryl(2-phenylhydrazono)methyl]-4,4-dimethyl-2-oxaspiro[5.5]undecane-1,5-diones. 相似文献