Homolytic reactions of polyfluoroaromatic compounds V. The reaction of pentafluorophenyl radicals with fluorobenzene

The arylation of fluorobenzene with pentafluorophenyl radicals obtained by the reaction of the corresponding aniline with pentyl nitrite is described. The reaction involves attact at the 2t?-,3t?-and 4t?-positions. The composition of the mixture and the nature of its components were determined by ¹⁹F NMR spectroscopy and were confirmed by gas-liquid chromatography.     

A new solid-phase polymerization—metal phthalocyanine sheet polymers

The thermal reactions of pure metal(11) 4,4′,4″,4′″-phthalocyanine-tetracarboxylic acids of copper, cobalt, and nickel at 350–400°C in vacuum have been studied using Fourier transform infrared spectrometry, gas chromatography, and mass spectrometry. Based on these observations, novel in situ reactions for the synthesis of heat-resistant phthalocyanine “sheet” polymers are described. The poly(metal phthalocyanine) polymers of copper, cobalt, and nickel so synthesized have been characterized by elemental analysis, infrared spectroscopy, and dynamic thermogravimetric analysis. The most noteworthy property of these polymers is their extreme resistance to heat in an anaerobic atmosphere and their high char yields (89–93%) at 800°C in a nitrogen atmosphere.     

Ring cleavage and ring expansion of indoles by superoxide ion

The reaction of indoles ($\text{1}$) with superoxide ion resulted in ring cleavage to give $\text{o}$-formyl and $\text{o}$-acylaminoketones ($\text{6}$) or N-acylanthranilic acid ($\text{8}$) and ring expansion yielding 2-quinolones ($\text{7}$). All reactions are chemiluminescent except that of 2-methylindole ($\text{lh}$), which gave a coupled product ($\text{9}$).     

Gitoxigenin glycosides

Summary Three cardiac glycosides have been synthesized from gitoxigenin and D-glucose: gitoxigenin 3-O--D-glucopyranoside, gitoxigenin 16 -O- -D-glucopyranoside, and gitoxigenin 3, 16-di-O- -D-glucoside. The first glycoside, obtained with a yield of 49% on the weight of the initial aglycone, possesses a fairly high biological activity (0.25 mg/kg), while the other two, formed in a yield of about 0.3%, do not possess the action on the heart that is specific for the cardenolides.Khar'kov Chemical and Pharmaceutical Scientific-Research Institute. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 45–49, January, 1971.     

Preparation and chain extension of C100dicarboxylic acid

The selective degradation of polyethylene crystals with fuming nitric acid has been used to prepare a C₁₀₀ chain with terminal functional groups. After treating this product with concentrated sulphuric acid, it is shown by average molecular weight, titration and infra-red spectroscopy measurements that each molecule contains two carboxylic acid groups. This C₁₀₀ dicarboxylic acid is chain extended with several low molecular weight difunctional coupling agents. Block copolymers of this acid and poly(propylene glycol) have been prepared.     

Elektrische Leitfähigkeiten geschmolzener Salzmischungen aus Strontiumchlorid und Alkalimetallchloriden

Electrical Conductivity of Molten Strontium Chloride-Alkali Chloride Salt Mixtures The temperature and concentration dependence of the specific electrical conductivity is measured for binary fused mixtures SrCl₂–MeCl (Me = Li, Na, K, Rb, Cs). Minima of the conductivity are found at the concentration x · 0.5 in the systems SrCl₂–(KCl, RbCl, CsCl).     

Bemerkungen zur chemischen Bestimmung von zweiwertigem Eisen und dreiwertigem Mangan in manganhaltigen Ferriten

Zusammenfassung Die Methode von Bonsels u. Linnemann [1] zur Bestimmung von Fe^II und Mn^III lieferte bei der Überprüfung falsche Ergebnisse. Die Ursache liegt darin, daß sich der Blindwert des Azides in Gegenwart von Mn^2ü-Ionen erheblich erhöht und in der Siedehitze eine Reaktion zwischen Mn^III und Cr^III abläuft. Da eine Auflösung selbst fein pulverisierter Ferrite in dem mitgeteilten Lösungsgemisch nur in der Siedehitze erfolgt, ist eine Bestimmung von Fe^II und Mn^III in Ferriten nach dieser Methode nicht möglich.

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Summary The method for the determination of Fe^II and Mn^III in manganese ferrites by Bonsels and Linnemann [1] was examined. It was found that the consumption of NaN₃, used for the reduction of Mn^III and effecting in a second (not wanted) reaction the reduction of Cr₂O₇ ^2–, is essentially increased by the presence of Mn^II and causes an error in the determination of Fe^II. The second error is the reaction between Mn^III and Cr^III at boiling temperature. On account of the necessity to dissolve the ferrites with the acid mixture at boiling temperature the determination of Mn^III and Fe^II is not possible.

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Herrn Dr. P. Kleinert vom Institut für Magnetische Werkstoffe danken wir an dieser Stelle für wertvolle Diskussionsbeiträge und das bei der Durchführung der Arbeit gezeigte Interesse.     

Analyse de la fraction monophénolique des condensats de fumée de cigarettes par association de méthodes chromatographiques

Résumé Les monophénols sont isolés des condensats de fumées de cigarette par chromatographie sur couche mince de Kieselgel G avec un mélange (31) de cyclohexane et d'acétate d'éthyle extraits du support, puis séparé et dosés par chromatographie en phase gazeuse sur colonne capillaire. Le rendement de l;opération est de 80±2% pour le triméthyl 3,4,5 phénol, de 65% pour le triméthyl 2,3,5 phénol. Les teneurs obtenues sont de 8g de phénol, 3g de (para + méta) crésol et 0,5 g de diméthyl 2,6 phénol par mg de condensat. De nombreux autres alkylphénols ont été identifiés.

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Analysis of the monophenolic fraction of tobacco smoke condensates by a combination of chromatographic methods

Summary Monophenols are separated from tobacco smoke condensates by thin-layer chromatography on Kieselgel G using a 31 mixture of cyclohexane and ethylacetate. The monophenolic fraction is recovered from the support and analyzed by GC on a capillary column. The yield is 80±2% for 3,4,5 trimethylphenol and 65% for 2,3,5 trimethylphenol. The concentration determined for phenol, (para+meta) cresol and 2,6 dimethylphenol are 8,3 and 0.5 g per mg of condensate respectively. Numerous other alkyl phenols have been identified.

     

Addition of mercaptans to acetylenic γ-hydroxy ketones

Conclusions Both the nucleophilic and the free radical addition of n-butyl mercaptan to acetylenic-hydroxy ketones (1,1-disubstituted derivatives of 2-pentyn-1-ol-4-one) lead to the formation of the corresponding 1,1-disubstituted derivatives of 2-butylthio-2-penten-1-ol-4-one in 41–65% yield.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1669–1670, July, 1973.     

Ionotropic reactions of β-sultones

The reaction mechanism of-sultones are discussed; a scheme for the reactivity is proposed. Polyfluoro--sultones can undergo anionotropic reactions of the type Hydrogeneous-sultones under prototropic reactions: