Structures of 2-hydroxypyridine and its vinyl derivatives

The PMR, Raman, and UV absorption spectra of 2-hydroxypyridine and its vinyl derivatives were investigated. Their electrochemical reduction was studied, and a quantum-chemical analysis of them was performed. It was concluded that the structure of 2-hydroxypyridine in proton-donor solvents is mesomeric, and its wave function, to a first approximation, is a linear combination of the wave functions of the 2-pyridone and zwitterion models. The contribution of the wave functions of each of the models depends substantially on the concentration of the solution and the nature of the solvent. An assumption was made regarding the presence of dynamic conjugation between the vinyl group and the ring in vinyl derivatives of 2-hydroxypyridine.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 95–102 January, 1972.     

Researches on benzodiazines

2-R-Quinazolones have been synthesized (R=Me, Ph,-pyridyl,-furyl), and subsequently the 4-chlorides and the corresponding 2-R-4-hydrazinoquinazolines were obtained. By the reaction of orthoformic ester and nitric acid on the hydrazines, 5-R- [3, 4-c]-s-triazoloquinazolines and 5-R- [1, 5-c] tetrazoloquinazolines were prepared, respectively. The compounds in which R=Me differ considerably from compounds with other groups, both in color and stability of intermediate reaction products. 5-R- [1, 5-c] tetrazoloquinazolines are hydrolyzed by HCl into quinazol-4-ones.For Part IV see [1].     

Spectral study of the conversion of porphyrins during interaction with molecular negative ions

In the interaction of ethioporphyrin and of several of its metal derivatives with negative ions of pyridine and anthracene in tetrahydrofuran solutions, an electron transfer takes place which results in the conversion of the pyridine and anthracene ions into neutral molecules, whereas the molecules of the pigment are first transformed into monovalent anions and subsequently into the di-, tri-, tetra-, and sometimes even into the hexavalent anions. In the first stage of this interaction, ferriethioporphyrin is reduced to ferro-ethioporphyrin, whereas the unmetallized pigment and its copper complex are transformed into the disodium derivative of ethioporphyrin. When the temperature is lowered, the rate of the electron transfer from pyridine ions to zinc-ethioporphyrin is decreased, and illumination leads to a substantial rate increase. The photochemical sensitivity of this system is possibly linked to the formation of stable complexes between pigment molecules and pyridine ions.     

Preparation of block copolymers by use of peroxide-terminated prepolymer

Block copolymers containing poly(tetramethylene oxide) and poly(methyl methacrylate) segments were prepared. A commercially available poly(tetramethylene oxide) terminated with tolylene diisocyanate was capped with tert-butyl hydroxymethyl peroxide and the resulting prepolymer peroxide was used as a free-radical initiator of vinyl polymerization. Block copolymers formed in temperature-programmed vinyl polymerizations possessed improved impact strengths over poly(methyl methacrylate) from 0.35 to 1.18 for a fixed (nonoptimized) block length of poly(tetramethylene oxide).     

Metal coordination polymers. II. Molecular weight studies of beryllium phosphinate polymers in toluene

The number-average molecular weights of beryllium 4-biphenyl(phenyl)phosphinate, di-n-pentylphosphinate, di-n-heptylphosphinate, and trifluoromethyl(phenyl)phosphinate are degraded by the presence of water in toluene. It is proposed that easily hydrolyzable P? O? P bonds contribute, in part, to the bonding of these polymers.     

Reactions of Vanillin and Vanillal Esters with 6-Quinolylamine and Phenidone

Previously unknown 2-methoxy(or ethoxy)-4-(11-oxo-9-phenyl-7,8,9,10,11,12-hexahydrobenzo[b][4,7]phenanthrolin-12-yl)phenyl esters of carboxylic acids were prepared by ternary condensation of vanillin or vanillal alkanoates with 6-quinolylamine and Phenidone. According to the ¹H NMR spectra, the target products are formed as mixtures of diastereomers.     

New Method of Analysis of Intermolecular Contacts in the Crystal Structure: π-Complexes

A new method for analysis of intermolecular contacts in the crystal structure based on characteristics of the Voronoi-Dirichlet polyhedra (VDP) is considered using metal π-complexes as examples. The crystal data of the compounds were used to determine the surface area of the VDP faces corresponding to all intermolecular contacts in one π-complex, the total volume of the pyramids with VDP faces as bases and the nuclei of atoms involved in the intermolecular contacts at the vertices, and the total solid angle at which the “intermolecular” VDP faces are seen from the corresponding nuclei of the molecule. A common linear correlation between the enthalpy of sublimation of π-complexes and saturated or unsaturated hydrocarbons and the molecular VDP characteristics was elucidated. On the basis of the results, the enthalpies of sublimation were calculated for some iron π-complexes (for which data on the crystal structure were available) and C₆₀ and C₇₀ fullerenes.__________Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 7, 2005, pp. 495–505.Original Russian Text Copyright © 2005 by Serezhkin, Shevchenko, Serezhkina.     

High-performance anion-exchange chromatographic study of desialylated human alpha 1-acid glycoprotein variants. Development of a fractionation method for the protein slow variants

The three main desialylated variants (F1, S and A) of human alpha 1-acid glycoprotein (AAG), a serum acute-phase reactant, were analysed by high-performance anion-exchange chromatography in order to determine their optimum separation conditions. The analysis consisted of three steps, as follows: (1) A desialylated commercial AAG was separated into one "fast"- and one "slow"-migrating fraction by preparative isoelectrofocusing. The "fast" and "slow" fractions were shown to contain the F1 variant and a mixture of the S and A variants, respectively. (2) The pH titration curves of these two fractions were then measured by strong anion-exchange chromatography with several buffer systems of increasing pH. From the data obtained, it was not possible to select the optimum conditions to separate the "fast" variant F1 from the "slow" variants A and S. However, the S and A variants were shown to ionize very differently. (3) The specific fractionation of the S and A variants was therefore carried out by anion-exchange chromatography under operating conditions based on the data obtained from the study of their pH titration curves. This was performed both with the "slow"-migrating fraction obtained by preparative isoelectrofocusing of commercial AAG and with an AAG (containing only variants S and A) purified from an individual serum on immobilized Cibacron Blue F3G-A. Identification of the fractionated proteins was achieved by analytical isoelectrofocusing.     

Mass spectrometric study of the pyrolysis of perfluorinated compounds of composition C6F12-C9F20, containing perfluoroisopropyl groups

The primary and final products arising from the pyrolysis of perfluoro-2,4-dimethyl-3-ethylpentane, perfluoro-3-isopropyl-4-methyl-2-pentene, perfluoro-2-methyl-3-isopropyl-2-pentene, perfluoro-2,4-dimethyl-3-heptene, and perfluoro-4-methyl-2-pentene have been studied using low-energy mass spectrometry and chromatography-mass spectrometry. Thermal decomposition of hexafluoropropene oligomers, containing perfluoroisopropyl groups attached to a double bond, occurs via loss of a radical pair to form perfluorodienes, as well as via abstraction of a hexafluoropropene molecule from the iso-C₃F₇ group. A correlation between the principal fragmentation pathway observed under electron impact and the primary process in the main thermolysis pathway was detected only in the case of perfluoro-4-methyl-2-pentene and perfluoro-2,4-dimethyl-3-heptene, which are capable of cleavage of^.CF₃ and^.C₂F₅ radicals, respectively, to give a single possible allyl radical structure.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1037–1041, May, 1990.