Halomethanes in tri-n-octylamine and squalane mixtures at infinite dilution

The retention behavior of eight halomethanes and four saturated hydrocarbons was measured in gas chromatographic stationary phases consisting in tri-n-octylamine (TOA), squalane (SQ) and six TOA+SQ mixtures, at 55.0, 58.5, 62.5 and 65.0°C. Equlibrium constants for complex formation were extracted from experimental data by using a lattice model developed by Martire. The results may be interpreted in terms of the formation of weak hydrogen-bonded complexes, with sociation constants of about 0.13 L-mol^–1 for haloforms and 0.07 L-mol^–1 for dihalomethanes at 60°C.     

Influence of the sulfonate countercation on the thermal stability of nafion perfluorosulfonate membranes

We report a strong dependence of the thermal stability of Nafion® perfluorosulfonate ionomer on the nature of the counterion associated with the fixed sulfonate site. These results were obtained using thermal gravimetric analysis on a series of alkali metal and alkyl ammonium cation-exchanged Nafion films. We have found that the temperature of decomposition of Nafion is inversely dependent on the size of the exchanged cation; i.e., Nafion films show improved thermal stability as the size of the counter cation decreases. We attribute this inverse relationship of thermal stability with counterion size to an initial decomposition reaction which is strongly influenced by the strength of the sulfonate-coun-terion interaction. © 1993 John Wiley & Sons, Inc.     

Increasing the accuracy of eigenvalue computation in the spectral problem

A simple method is proposed for increasing the accuracy of computation of the eigenvalues of elliptic operators, which does not require high-order accurate schemes.Translated from Vychislitel'naya i Prikladnaya Matematika, No. 63, pp. 63–68, 1987.     

2-Carbethoxymethyl-4H-3,1-benzoxazin-4-one. 4. Reaction with anilines

In a solution of DMF, 2-carbethoxymethyl-4H-3,1-benzoxazin-4-one reacts with primarily aromatic amines basically with the formation of the corresponding 2-carbethoxymetlzyl-3-arylquinazolin-4(3H)-ones. Possible mechanisms of these chemical transformations are reported and discussed.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 225–228, February, 1994. Original article submitted June 28, 1993.     

Porphyrins 34. Mass spectrometric study of ethane- and ethylene-bis-porphyrins

The mass spectral behavior of 1, 2-di (mesoetioporphyr inyl-1)- and 1, 2-di (mesooctaethylporphyrlnyl) ethanes and ethylenes, their Cu and Ni complexes, as well as Ni Schiff bases of 1, 2-di (mesooctaethylporphyrinyl)ethane complexes, under ionization by electron impact and bombardment by accelerated atoms, was studied. Peaks of molecular ions, for which the basic decomposition pathways were established on the basis of an analysis of the parent and daughter ions, were observed in the electron impact mass spectra of all these compounds.For Communication 29, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 24–29, January, 1994.     

Interaction of 4-aminobenzofurazan with aryldiazonium salts

The reaction of 4-aminobenzofurazan with aryldiazonium salts leads to the formation of 4-amino-5-aryl-azobenzofurazans and 5-amino-2-aryl-4-nitroso-2H-benzotriazoles, products of the rearrangement of the initially formed 4-amino-7-(arylazo)benzofurazans. Oxidation of the benzofurazan as well as of the triazole derivatives gives 7-aryl-1,2,3-triazol[4,5-e]benzofurazans. The chemical properties of some of the compounds obtained have been investigated.Novosibirsk Institute of Organic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk 630090. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1432–1438, October, 1994. Original article submitted July 25, 1994.     

Use of ultrasound in heterocyclic chemistry (review)

We review literature data on synthesis and conversions of heterocyclic compounds using ultrasonic treatment.We analyze the effect of ultrasound on organic reactions involving participation of heterocyclic compounds.A. N. Kosygin State Technical Academy, Moscow 117918. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 723–755, June 1994. Original article submitted December 22, 1993.     

Synthesis,structure, and chemical properties of some N-(3-chloro-2-quinoxalyl)arylsulfonamides

We have developed a method for synthesis of N-(3-clzloro-2-quinoxalyl)sulfonamides by reaction of 2,3-dichloroquinoxaline with substituted arylsufonamides. Based on the IR spectra, we have established that in the solid state, the synthesized compounds exist in the form of amide tautomers. Alkylation of these compounds leads to N-metliyl-N-(3-chloro-2-quinoxalyl)arylsulfonamides. We demonstrate the possibility of nucleophilic substitution of the halogen upon treatment with O- and N-nucleophiles. The use of bifunctional nucleophiles leads to condensed quinoxalines.Translated from Khimiya Geterotsiklicheskikh Soedinenii, Vol. 30, No. 3, pp. 387–392, March, 1994.     

Synthesis and ring-chain isomerism of acid chlorides and amides of 2-(2-pyridyl and 2-quinolylcarbonyl) benzoic acids

The reaction of 2-(2 pyridytcarbonyl)benzoic acid with thionyl chloride affords an unexpected product of the intramolecular acylation of the pyridine nitrogen atom, namely, 6,11-dioxo-6,11-dihydrobenzo[blquinotizinium chloride. At the same time, 2-(2-quinotylcarbonyl)benzoic acid forms the expected cyclic acid chloride, namely, 3-(2-gitinotyl)-3-chlorophthalide in this reaction. Both compounds acylate ammonia and primary amines, including those with bulky alkyl groups (tert-butyl, 1-adamantyl, and 1,1,3,3-tetramethylbutyl) with the formation of 2-R-3-hydroxy-3-(2pyridyl- or 2-quinolyl)isoindolines. The protonation of the pyridine nitrogen atom of N-(1,1,3,3-tetramethylbutyl)-2-(2pyridylcarbonyl)benzamide, obtained in the open amide form, is accompanied by the closing of the isoindotinone ring; the deprotonation is accompanied by ring opening.Riga Technical University, Riga LV-1048. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 499–504, April, 1994. Original article submitted March 17, 1994.