Cis- undtrans-α,β-dialkylsubstituierte Phenylazo-alkene

Zusammenfassung Bei der Umsetzung aliphatischer Keto-phenylhydrazone (1) mit J₂ in Pyridin wird ein H-Atom einer -ständigen Methyloder Methylengruppe durch den Pyridinium-Substituenten ersetzt, so daß die -Phenylhydrazonoalkyl-pyridiniumjodide2 bzw.3 entstehen. Aus3 werden durch Alkalieinwirkung unter 1,4-Eliminierung von Pyridin·HJ die orangefarbenen s-trans-(E, E)-Phenylazo-alkene5 und—in der offenkettigen Reihe—die s-trans(E,Z)-Phenylazo-alkene6 erhalten. Die Strukturen von5 und6 werden durch spektroskopische Daten (EA,¹H-NMR) gestützt.

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Cis- and trans-,-dialkylated Phenylazo-alkenes

Phenylhydrazones of aliphatic ketones1 react with I₂ in pyridine replacing one hydrogen atom of a methyl or methylene group at the -position of the functional group by the N-pyridinium substituent to give1-(2-phenylhydrazonoalkyl)-pyridinium iodides2 and3 respectively. Upon alkali induced 1.4-elimination of pyridine·HI from3 the orange s-trans(E, E)-phenylazo-alkenes5 and—in the acyclic series—s-trans(E,Z)-phenylazo-alkenes6 are obtained. Their structures are derived from their spectroscopic properties (ea and¹H-nmr).

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Oxidationsprodukte von Arylhydrazon-Verbindungen, 7. Mitt. (6. Mitt.)     

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).

     

Titrimetrische Bestimmung von Zink mit Äthylendiamintetraessigsäure in Gegenwart von Palladium(II)

Zusammenfassung Komplexometrische Methoden zur Bestimmung von Zink in Gegenwart von Palladium(II) wurden ausgearbeitet. Dabei wird Palladium(II) mit Kaliumcyanid getarnt und der Zinkgehalt entweder bei p_H 5,8 oder nach Demaskierung mit Chloralhydrat bei p_H 10 mit ÄDTA gegen Methylthymolblau titriert. Diese Zinkbestimmung läßt sich auch in Anwesenheit einer Mischung von Palladium(II), Kupfer(II), Nickel und Kobalt(II) durchführen.

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Summary Complexometric methods have been developed for determining zinc in the presence of palladium(II). In these procedures, Pa(II) is masked with potassium cyanide and the zinc content is titrated either at p_H 5.8 or after demasking with chloralhydrate is titrated with EDTA at p_H 10 in the presence of methylthymol blue. This zinc determination may also be conducted in the presence of a mixture of palladium(II), copper(II), nickel(II),and cobalt(II).

     

The electrocapillarity of polyacrylates

Summary The electrocapillary properties of polyacrylic acid have been studied by two methods. Exploratory measurements have been made of the effect of the polymer on the differential capacity of a mercury drop in 0.1 m sodium perchlorate. They showed that the polymer was strongly adsorbed over a wide range of potentials but that it did not appear to form a monolayer. The surface excess of polymer obtained from drop weight data showed a maximum at very low concentrations and then a decline at higher concentrations. The bulk of the work was carried out by making surface tension measurements, using a sessile mercury drop, in solutions of a fraction of polyacrylic acid (mol. wt. 7.02×10⁴) in potassium chloride at 0.01, 0.1, 0.2, and 0.5 m at 25°C.The data have been used to evaluate the surface excesses of the polymer and of the inorganic ions. The distribution of K⁺ and Cl^– in the electrical double layer and the contact adsorption of Cl^– on the mercury were very little affected by the presence of the polymer. The surface excess of polymer was always found to be greatest at low concentrations, to decrease steeply at first as the concentration was increased and then to decrease more slowly at higher concentrations.Possible explanations of this behaviour are discussed and it is concluded that the rapid decrease is a consequence of molecular weight dispersion and the stronger adsorption of high molecular weight polymer. The slow decrease in surface excess at higher concentrations may be a result of configurational changes of the polymer molecules.Surface pressure data show that, despite this decrease in the surface excess, the surface coverage reaches a high level at very low polymer concentrations and then continues to increase slowly as the concentration of polymer is increased. This apparent contradiction is due to changes in configuration of the adsorbed polymer molecules. At higher bulk concentrations the chain configurations are more compact and each adsorbed molecule makes more contacts with and so occupies a greater area of the mercury surface than at low concentrations.The conclusion is reached that the surface excess of polymer is mostly contained in a layer probably more than 1000 Å thick. It consists of a concentrated and entangled mass of polymer chains. Relatively few of these chains are in contact with the mercury at any istant. The concentration in this surface layer decreases steadily with increasing distance from the mercury surface and it merges without discontinuity into the bulk solution.With 10 figures in 22 details     

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.     

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.     

Structure of the products of the cyclization in acetic anhydride of β-(2-carboxy-5-chlorophenylamino) propionic acid and its nitrile

-(2-Carboxy-5-chlorophenylamino)propionic acid cyclizes in acetic anhydride to form 4-chloro-2-(2,4-dioxopiperidino)benzoic acid, which subsequently undergoes conversion into its lactone. Under the same conditions, -[acetyl(2-carboxy-5-chlorophenyl)amino]-propionitrile forms 7-chloro-1--cyanoethyl-1,2,3,4-tetrahydroquinoline-2,4-dione. The structures of the compounds obtained were confirmed by their IR, UV, and PMR spectra. An evaluation of the stability of the ketonic and enolic forms of the compounds obtained on the basis of calculations by Hückel's method has been made.Translated from Khimiya Geterotsiklicheskikh Soedinenii, Vol. 6, No. 7, pp. 879–884, July, 1970.     

Application of a nickel hexacyanoferrate(II) composite ion exchanger to fast separation of Ra from Fr and Ba from Cs

Sorption studies of Ra, Ba, Fr and Cs on nickel hexacyanoferrate(II) composite ion exchanger from hydrochloric acid and EDTA solutions are presented.