Intramolecular hydrogen bond in substituted 3-hydroxypyridines

To explain the character of the intramolecular hydrogen bond in substituted 3-hydroxypyridines, the chemical shifts in the NMR spectra of the hydroxyl group and the IR spectra were studied. It was established that the stability of the intramolecular hydrogen bond of the O-HNR₂ type in substituted 3-hydroxypyridines increases when compared with the corresponding phenols, while an opposite pattern is observed for bonds of the O-H0₂ N type. An approximate evaluation of the energy of the intramolecular hydrogen bond in substituted 3-hydroxypyridines was achieved. When reacting with bases of the same strength, 3-hydroxypyridine forms more stable complexes than phenol.     

Form of the dihedral angle dependence of the spin-spin coupling constant JHNNH

Cyclic hydrazides (derivatives of phtalhydrazide,pyrozolidone-3, indazolone, cyclic hydrazide camphoric acid) are studied by the NMR¹H method. The size of the dihedral HNNH angle of several model compounds (pyrozolidone-3, cyclic hydrazide norcamphoric acid) are calculated by the MINDO/3 SSF MO LCAO method. It is shown that in the hydrazides with HNNH dihedral angle 0–70° the magnitude of the HNNH spin-spin interaction constant does not exceed 1 Hz. The form of its dependence on the dihedral angle is determined.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 25, No. 3, pp. 363–366, 1989.     

Dissociative Excitation Processes upon Collisions of Slow Electrons with MgBr2 Molecules

Dissociative excitation of MgI, MgII, and MgBr upon e–MgBr₂ collisions was experimentally studied. The excitation cross sections of the spectral lines of MgI and MgII, as well as two sets of bands of the MgBr molecule were measured at an incident electron energy of 100 eV. In the electron energy range from the excitation threshold to 100 eV, ten optical excitation functions with a complex structure were recorded. The principal pathways of dissociative excitation of MgI, MgII, and MgBr by slow electrons are discussed.     

Heterocyclic bioantioxidants 4. Chlorolysis of 3-nitro-4-s-benzylcoumarin

3-Nitro-4-S-benzylcoumarin reacts with sulfuryl chloride to give an unstable compound, which in turn reacts with p-toluidine to give 3-nitro-4-p-tolylaminocoumarin.For Communication 3, see [1].Translated from Khimiya Geterotsiklicheskikh Soednenii, No. 7, 888–889, July, 1992.     

Basicity and structure of 5-hydroxybenzimidazoles in nitromethane

Examination of the acid-base properties of 5-hydroxybenzimidazoles has shown them to exist in nitromethane as the 5-hydroxy-tautomers. Substituents in the 2-position have a predominantly inductive effect on the basicity of the 3-nitrogen, rationalized as in other nitrogen heterocycles by the proximity of the substituents to the reaction center.N. N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, 117977 Moscow. The Research Institute for Intermediates and Dyes, 103787 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 2, pp. 421–425, February, 1992.     

Structure of Aqueous Gallium(III) Bromide Solutions Over a Temperature Range 80–333 K by Raman Spectroscopy, X-ray Absorption Fine Structure, and X-ray Diffraction

The structure and complex formation of concentrated aqueous gallium(III) bromide (GaBr₃) solutions have been investigated over a temperature range 80–333 K by Raman spectroscopy, X-ray absorption fine structure (XAFS), and X-ray diffraction. The Raman spectra obtained at various [Br^?]/[Ga³⁺] molar ratios and temperatures have shown that complex formation between Ga³⁺ and Br^? occurs as a predominant species, with [GaBr₄]^? at [Ga³⁺] as high as 1～2 M (M = mol?dm ^?3) and [Br^?]/[Ga³⁺] ratios > ～2, and that cooling of the solutions favors the formation of the aqua Ga³⁺. The intermediate species were not seen in the Raman spectra. The XAFS data have revealed that the aqua complex has a sixfold coordination as [Ga(H₂O)₆]³⁺ with a Ga³⁺–H₂O distance of (1.96 ± 0.02) Å, whereas the [GaBr₄]^? complex has a Ga³⁺–Br^? distance of (2.33± 0.02) Å, and that vitrification of the aqueous GaBr₃ solution at liquid nitrogen temperature shifts the equilibrium toward the aqua complex. The X-ray diffraction data at different subzero temperatures have shown a tendency of decreasing Ga³⁺–Br^? and increasing Ga³⁺–H₂O interactions with lowering temperature, confirming the preference of aqua Ga³⁺ in the supercooled liquid state as well as in the glassy state. The Ga³⁺–H₂O distance of ～1.8 Å for the tetrahedral coordination was found in a 2.01 M gallium(III) bromide solution with a [Br^?]/[Ga³⁺] ratio of 3.7 and gradually increased to a value of 1.92 Å for octahedral geometry with decreasing temperature, suggesting that equilibrium shifts from [GaBr₄]^? to [Ga(H₂O)₆]³⁺ through intermediate species, [GaBr _n ]^(3?n)+ (n = 2 and 3). The Ga³⁺–Br^? and Br^?–Br^? distances within [GaBr₄]^? with an almost tetrahedral symmetry are (2.35± 0.02) and (3.82± 0.03) Å, respectively. The Ga³⁺ has the second hydration shell at (4.03± 0.03) Å and the hydration of Br^? is characterized with a Br^?–H₂O distance of (3.35± 0.02) Å at all temperatures investigated.     

Approximation of enthalpy of formation by Fourier series

A possible approximation of the enthalpy of formation of C,H,N,O-containing compounds by trigonometric Fourier series has been shown.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1389–1390, August, 1994.     

Polynuclear nonfused bis(1,3,4-oxadiazole)-containing systems

Nonfused bis-1,3,4-oxadiazoles were synthesized by reaction of 5-substituted mono-and bis-tetrazoles with mono-and dicarboxylic acid chlorides. The results of kinetic studies showed that the transformation of tetrazoles into 1,3,4-oxadiazoles is accelerated by 1 to 2 orders of magnitude on addition of a catalytic amount of dimethylformamide, triethylamine, or pyridine.     

The mechanism of 2-methylbutene-2 hydrohalogenation in solid phase

Complexes and reactions of 2-methylbutene-2 with hydrohalogen (HCl, HBr) have been studied in solid phase at 80–150 K. It has been found that 2-methylbutene-2 forms with HX complexes of 1:1 and 1:2 composition. Hydrohalogenation proceeds via the rearrangement of complex 2HX·C₅H₁₀ into complex of the addition product with HX. Kinetic equation depends on the reagents ratio. In excess of HX (1< HX:C₅H₁₀< 10) reaction can be described by the first order kinetic equation. If the ratio HX:C₅H₁₀ is more than 10, reaction is described by polychronous kinetic law. The effective activation energy of solid phase hydrohalogenation does not exceed 20 kJ/mole. The molecular mechanism of hydrohalogenation in solid phase has been proposed.     

Two wavelength-CARS thermometry of hydrogen

In this work, we present the results of two-wavelength (2)-CARS thermometry of hydrogen at temperatures from 300–1200 K. The choice of the pair of spectral lines for the 2-CARS thermometer with respect to optimal temperature sensitivity within a given temperature range was analysed. Software was developed to process the experimental data and calculate the temperature. In the experiments, temperature and density were measured in a heated cell using single-shot and averaged CARS intensities in the pure rotationalS branch. The accuracy achieved and its dependence on measured temperature values and on the number of averaged shots was analysed.The sponsoring of this work by the Stabsabteilung Internationale Beziehungen at the Kernforschungszentrum Karlsruhe under project number RUS 222.12 is gratefully acknowledged