Partial molal heat capacities of aqueous tetraalkylammonium bromides as functions of temperature

Enthalpies of solution have been measured from 5 to 85°C for aqueous tetraethyl- and tetrapropylammonium bromides, and the integral heat method is employed to evaluate for these electrolytes over a wide temperature range. Data taken from the literature have been used to evaluate for aqueous Bu₄NBr over a similar temperature range. These data, along with similar data for Me₄NBr, previously reported, have been used to evaluate absolute ionic heat capacities. While the absolute values agree only qualitatively with two other methods of division, the temperature dependences of the three methods essentially agree up to 65°C. Heat capacities due to structural effects on the solvent, obtained by subtracting the inherent heat capacities of the ions, are extraordinarily positive for all four tetraalkylammonium ions and have negative temperature coefficients, indicating that all four ions, including the tetramethylammonium ion, are structure-making ions.     

The lipids of microalgae II. Lipids of the dry biomass ofMonochrysis lutheri

Institute of the Chemistry of Plant Substances, Uzbekistan Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 899–900, November–December, 1993.     

Copper precipitation from sulfate solutions with calcium carbonates

Mechanism of interaction of copper sulfate with natural calcium carbonates, responsible for low residual copper concentrations in solutions and for the behavior of open and closed systems in storage is considered.     

Electronic properties of polyoxometalates: a DFT study of alpha/beta-[XM(12)O(40)](n-) relative stability (M=W, Mo and X a main group element)

Keggin heteropolyanions [XM(12)O(40)](n-) have various isomeric structures, alpha and beta being the most common. Conventionally, the alpha structure appears to be the most stable, but calculations carried out at the DFT level for X = P(V), Si(IV), Al(III), As(V), Ge(IV), and Ga(III) and M = W(VI) and Mo(VI) show that this stability depends on several factors, particularly on the nature of the heteroatom (X) and the total charge of the cluster. In this paper, we apply the clathrate model to the Keggin molecule to carry out a fragment-interaction study to elucidate when and why the traditional relative stability of various isomers can be inverted. The fully oxidized anions that have inverted the traditional stability trend in this series are [AlW(12)O(40)](5-) and [GaW(12)O(40)](5-), both of which contain a third-group heteroatom and an overall charge of -5. beta-isomers are always more easily reduced than alpha-isomers. This experimental observation suggests that reduction favors the stability of beta-isomers and one of the most important results of this study is that the alpha/beta inversion is achieved in most cases after the second reduction. The alpha- and beta-isomers may have different properties because the energy of the LUMO, a symmetry-adapted d(xy)-metal orbital, is different.     

Effect of hydrothermal treatment on catalytic properties of superhigh-silica zeolites

The effect of hydrothermal treatment of decationized superhigh-silica zeolite on the mechanism of n-hexane conversion has been studied. It has been established that thermosteam modification sharply decreases the cracking activity and increases the selectivity to aromatization reactions. Zeolite acidity markedly decreases, but its crystal structure does not become amorphous.

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Synthesen von Heterocyclen, 122. Mitt.: Über die Reaktion des Perimidons mit aktiven Malonestern

Zusammenfassung Perimidon (1) reagiert mit monosubstit. Malonsäure-trichlorphenylestern (2) bei 250° zu 9-Hydroxy-5,7-dioxo-4,5-dihydro-7H-pyrido[1,2,3-cd]perimidinen (3), die durch saure Hydrolyse zu 10-Amino-4-hydroxy-benzo[h]carbostyrilen (4) gespalten werden.

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Syntheses of heterocycles, CXXII: Reaction of perimidone with reactive malonates

Perimidone (1) reacts with monosubstituted 2.4.6-trichlorophenyl malonates at 250° to 9-hydroxy-5.7-dioxo-4.5-dihydro-7H-pyrido[1.2.3-cd]perimidines (3), which are cleaved by acid yielding 10-amino-4-hydroxy-benzo[h]quinolin-2-ones (4).

     

Synthesis and conversions of metallocycles. 7. A novel approach to the synthesis of 3,4-dialkyl-substituted aluminacyclopentanes in the presence of Cp2ZrCl2

A novel approach was developed for the stereoselective synthesis of trans-3,4-dialkyl-substituted aluminacyclopentanes from -olefins, metallic magnesium, and EtAlCl₂ in the presence of catalytic amounts of Cp₂ZrCl₂. The hydrolysis and deuterolysis products of the 3,4-dialkyl-substituted aluminacyclopentanes obtained are only in the trans configuration.For previous communication, see [1].Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1607–1609, July, 1991.     

2,3-Diphenylthiazolo[3,2-a]pyrimidinium salts

The corresponding 2,3-diphenyl[3,2-a]pyrimidinium salts were obtained by the condensation of 4,5-diphenyl-2-aminothiazole perchlorate with -diketones, -chlorovinyl ketones, -chlorovinyl aldehydes, and 1,1,3,3-tetraethoxypropane. The PMR spectra were used to prove the structures of the compounds obtained, particularly to select the structures of the isomeric salts obtained in the condensation with unsymmetrical -diketones, -chlorovinyl ketones, and -chlorovinyl aldehydes. As a rule, the latter give one isomer — the -unsubstituted (relative to the bridge nitrogen atom) derivative.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 629–631, May, 1972.     

Preparation and characterization of dealuminated metakaolin and its use in the transformation of waste plastics to aromatic hydrocarbons

Acid activated metakaolins (AAMKs) have been prepared by calcination of the natural clay at 600 degrees C to provide a metakolin which was then leached at 80 degrees C for 3 h using 1M, 2M, 3M, and 6M HCl. These materials were characterized and their ability to transform the off gases from HDPE decomposition into useful aromatic species was evaluated. The amount of adsorbed water and the number of acid sites increased with the severity of acid treatment. Variable temperature DRIFTS spectroscopy of pyridine treated samples revealed that both Br?nsted and Lewis acid centers were present until 425 degrees C. Pyridine bonded to the Lewis acid centers was more thermally stable. The AAMKs were all selective to the production of toluene with respectable, but lesser, amounts of xylenes and trimethylbenzenes. This selectivity contrasts with that of acid leached and pillared smectites which are selective toward trimethylbenzene.