2-[6-Alkyl-3-hetaryl-4-oxo-9,10-dihydro-4H,8H-chromeno-[8,7-<Emphasis Type="Italic">e</Emphasis>][1,3]oxazin-9-yl]acetic acids

The interaction has been studied of a series of substituted 3-hetaryl-7-hydroxychromones with amino acids and formaldehyde (reactants ratio 1: 1: 2 respectively). In the case of glycine and Het = 3-isoxazolyl the product of aminomethylation at position 8 of the chromone was obtained, and with other Het (including Het = 4-phenyl-1,2,4-triazol-3-yl) 2-[6-alkyl-3-hetaryl-4-oxo-9,10-dihydro-4H,8H-chromeno[8,7-e][1,3]-oxazin-9-yl]acetic acids were formed. With β-alanine and Het = 4-phenyl-1,2,4-triazol-3-yl the corresponding β-substituted propionic acid was synthesized, but proline did not participate in the reaction, leading to bis(6-ethyl-3-hetaryl-7-hydroxychromon-8-yl)methane. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 683–689, May, 2007.     

AES investigations on starting powders for high performance ceramics

AES depth profiles on ceramic powders (untreated/hydrolyzed/oxidized/ (Al, Y)₂O₃ coated Si₃N₄, [BaO, SiO₂] coated Al₂O₃) are feasible on thin, homogeneous layers or m sized agglomerations prepared on an Au foil. By means of the depth profiles one can qualitatively characterize the coating around the particles. Factor analysis of the depth profiles on the differently treated Si₃N₄ powders suggests the existence of an Si₂N₂O phase on the oxidized sample.Dedicated to Professor Günther Tölg on the occasion of his 60th birthday     

Photochemical synthesis of 2-amino-1-hydroxy-9,10-anthraquinone-9-alkyl(aryl)imines

Irradiation of a mixture of 1-aryloxy-2-amino-9,10-anthraquinone and amines in benzene results in formation of the derivatives of 2-amino-1-hydroxy-9,10-anthraquinone-9-alkyl(aryl)imines in a high yield. 2-Amino-1-hydroxy-9,10-anthraquinone-9-aikylimines were shown by¹³C and¹⁵N NMR to exist predominantly in the enaminoquinoid form whereas 2-amino-1-hydroxy-9,10-anthraquinone-9-arylimines exist in the oxyimine form. Sunlight irradiation of the derivatives of 2-benzoylamino-9,10-anthraqumone-9-alkylimines results in formation of the photocyclization products — 4-benzoylaminoanthra-[9,1-d,e]-1,3-oxasinones-7.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 940–944, May, 1993.     

The reaction of phenylarsenazo with chromium(III)

The conditions for the reaction between phenylarsenazo (PAA) (2-[(2-arsonophenyl)azoj-7-(phenylazo)-1, 8-dihydroxynaphthalene-3,6-disulphonic acid) and chromium(III) have been studied. A blue 1:1 complex is formed at pH 2.2 on heating the reactants at 100 degrees for 15 min. It has maximum absorption at 635 nm and is stable for at least 24 hr. The molar absorptivity is 3.3 x 10(4) 1.mole(-1).cm(-1). Beer's law is obeyed in the chromium concentration range 0-1.4 mug ml . The reaction has been successfully applied to determination of chromium in alloy steel.     

Effect of 1,1,2,2-tetrachloroethane on IR spectra of HCl complexes withN,N-dimethylformamide and 1-methyl-2-pyrrolidone formed by a strong quasi-symmetric hydrogen bond

The effect of 1,1,2,2-tetrachloroethane (TCE) on the IR spectra of HCl complexes withN,N-dimethylformamide (DMF) and 1-methyl-2-pyrrolidone (N-MP) with strong quasisymmetric hydrogen bonds was studied using Multiple Attenuated Total Reflection (MATR) IR spectroscopy. The addition of TCE does not change the background absorption spectra, but results in a change in the extinction coefficients of some bands of these complexes. The analysis of the spectra shows that the HCl−DMF complexes interact only with one molecule of TCE, and the HCl−N-MP complexes interact with two molecules of TCE. It is shown that the neutral component of the system (TCE) has no effect on the parameters of the strong quasi-symmetric H-bond in the complexes studied. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 956–960, May, 1997.     

Interaction of vinylpyridines with 1,3-dienes catalyzed by transition metal complexes

The linear and cyclic cooligomerization of 2-vinyl-, 2-methyl-5-vinyl-, and 4-vinylpyridines with 1,3-dienes and trienes catalyzed by complexes of transition metals (Fe, Co, Ni, Mn, Cr, Pd, Ru, Rh, and Zr) was carried out to give unsaturated pyridines containing alkenyl and cycloalkenyl substituents.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 916–921, May, 1993.     

The electronic structure of molecules by a many-body approach

The vertical valence ionization potentials of cyclopropane, ethylene oxide and ethylene imine are calculated by a many-body Green's function method. For C₃H₆ the ordering of the ionization potentials is 2e(), 1e(), 2a₁(), 1a₂(), 1e(). The assignment of the 2a₁ and the 1a₂ ionization potentials which has been controversial is thus clarified. The ordering is in agreement with the result obtained via Koopmans' theorem. For ethylene oxide and ethylene imine Koopmans' theorem fails in predicting the correct order of ionic states. For C₂H₄O the ordering of the ionization potentials is 2b ₁(), 4a ₁, 1a ₂(), 2b ₂,3a ₁, 1b ₁(), 1b ₂, 2a ₁ and for C₂H₅N 6a, 5a, 3a, 2a, 4a, 3a, 1a, 2a. The agreement of the computed ionization potentials with the experimental values is very satisfactory.     

Porous ceramic bed supports for fused silica packed capillary columns used in liquid chromatography

Porous ceramic bed supports for fused silica packed capillary columns utilized in liquid chromatography were prepared by polymerizing solutions containing potassium silicate in-situ within a column to create a mechanically stable, rugged, and easily constructed termination. The effect of the bed support length on efficiency, and comparisons to glass wool bed supports, were considered in terms of column efficiencies and hydrodynamic variables. Results obtained indicate better performance for the ceramic bed support.     

CEPA calculations on open-shell molecules. V. The vibration frequencies of SF and SCl

Ab initio calculations for the ² ground states of SF and SCl have been performed on Hartree-Fock level and with inclusion of valence shell correlation effects by means of the CI and CEPA approaches. The calculated properties are: Equilibrium distances, vibration frequencies, and dipole moment curves in the vicinity of the respective equilibrium geometries. Our best estimates for the 0 1 infrared absorption frequencies _o for SF and SCl are 786 cm^–1 and 520 cm^–1, respectively, both with an uncertainty of about 10 cm^–1. This confirms a recent experimental value obtained by Willner for SF (791 cm^–1), but indicates that for SCl both experimental values reported previously in the literature (617 cm^–1 and 574 cm^–1) are wrong. The S—F and S—Cl bonds in SF and SCl are very similar to the ones in SF₂ and SCl₂, being essentially single p-bonds in either case. In the analogous oxygen-halogen molecules the situation is different, the O—F and O—Cl bonds in the diatomic radicals OF and OCl have partial double bond character and are much stronger than those in OF₂ and OCl₂ or in HOF and HOCl.     

Note on the ab initio PUHF treatment of open-shell systems

Ab initio projected-unrestricted Hartree-Fock calculations have been carried out on a number of excited and ionic states of the water molecule. Results have been compared with large-scale CI calculations, with IVO calculations, and with those of Mrozek and Golebiewski obtained by the 2 × 2 rotation method applied to orbitals. It is concluded that the PUHF method may provide the most useful alternative to large-scale CI for calculating properties of open-shell systems. But it will not be generally useful for calculating spectral transition energies.