Chemo- and regioselectivity in the reactions between highly electrophilic fluorine containing dicarbonyl compounds and amines. Improved synthesis of the corresponding imines/enamines

Chemo- and regioselectivity in the reactions between highly electrophilic fluorine containing dicarbonyl compounds (ethyl 4,4,4-trifluoroacetoacetate, 3,3,3-trifluoropyruvate and 1,1,1,5,5,5-hexafluoropentane-2,4-dione) and various benzylamines were systematically studied. The results obtained lead to the development of a generalized and practical method for large-scale synthesis of the corresponding imines/enamines, useful starting materials for preparation fluorinated amines and amino acid.     

Investigations of synthetic dyes. XLV. Styryls from N-arylquinaldine salts

Condensation of N-arylquinaldine salts with benzaldehyde and its o- and p-derivatives gives a series of styryl compounds. The absorption maxima of the hydroxystyryls are bathochromically shifted by 12–34 m, as compared with the unsubstituted analogs. Transformation of hydroxystyryl salts to the bases is linked with deepening of the color by 90–130 m.The other styryls were prepare similarly.     

Synthesis of organometallic compounds from trialkylaluminums and metal salts

Summary Reaction between trialkylaluminums and salts of antimony, bismuth, mercury, thallium, tin, and lead gives alkyl derivatives of these metals.     

Analysis and classification of individual outdoor aerosol particles with SIMS time-of-flight mass spectrometry

Individual aerosol particles sampled in the north of the city Karlsruhe were analysed with a TOF-SIMS instrument. The results confirmed the integral analysis of many particles [1]. In order to employ a signal pattern analysis of the negative secondary ions for the classification of organic compounds an earlier classification scheme for 5 keV Ar⁺ bombardment was found to be generally also applicable for the TOF-SIMS conditions. Two main classes of particles were distinguished, which consist of submicron mainly organic particles of vehicle traffic provenance on one side and coarse particles of geogenic sources on the other side. Additionally, the geogenic class could be devided into a fraction consisting of lime soil and a fraction with alumo-silicate soil. A quantification of the class population was performed by counting the particles of different type.     

Theoretical aspects of a preparative continuous chromatograph

Summary Equipment which has been used or suggested for preparative scale chromatography is reviewed. Particular attention is paid to one form of equipment for continuous counter-current chromatography which employs a moving mechanical seal. The theoretical effects of practical operating conditions and the mode of operation of this equipment are discussed. The influence of these effects on polymer fractionation is also considered. A theoretical model, based on the equilibrium stage concept, is proposed for the simulation of continuous gel permeation chromatography of a binary feed on such an apparatus. Examples of the results obtained from the computer simulation are given.     

Silanization and non-aqueous electrochemistry of two oxide states on platinum electrodes

When the surface of a Pt electrode is oxidized in aqueous 1 M H₂SO₄ at +0.8 to +2.0 V vs. SSCE for a few seconds to 10 min, disconnected, washed and dried, and placed in CH₃CN solvent, a negative potential scan shows that the surface oxide is reduced in two waves at potentials between?1.2 and?1.6 V vs. SSCE. The combined charge of the two waves amounts to 0.3–2.5 layers of oxide, depending on anodization potential and time. The more easily reduced oxide becomes non-reducible after reaction of the electrode with methyltrichlorosilane. The two oxide waves are interpreted as surface and subsurface oxide layers.     

Cyclisierungsreaktionen zu Pyrano[3,2-c]pyridinen und pyrano[3,2-c]chinolinen unter Verwendung von Ethoxymethylen-malodinitril bzw.-cyanessigester Synthesen mit Nitrilen, 50. Mitt. pyrano[3,2-c]quinolines with ethoxymethylene-malonitrile and-ethyl cyanoacetate,resp.

Reaction of ethoxymethylene-malonitrile and ethoxymethyleneethyl cyanoacetate, resp., with 4-hydroxy-2-pyridones (1a–b) and 4-hydroxy-2-quinolones (3a–b) leads to 2,5-dioxo-5,6-dihydro-2 H-pyrano[3,2-c]pyridine-(2a–d) and 2,5-dioxo-5,6-dihydro-pyrano[3.2-c]quinoline-derivatives (4a–d), resp.2a–d and4a–d exhibit remarkable visible fluorescence. Absorption- and emmission-data in different solvents are reported.     

Thianaphthenoyltrifluoroacetone as an analytical reagent: The keto-enol tautomerism of the 2- and 3-isomers of thianaphthenoyltrifluoroacetone

Summary The keto-enol tautomerism of the 2- and 3-isomers of thianaphthenoyltrifluoroacetone has been studied and the results explained by considering the relative negativities of the 2- and 3-position of thianaphthene. The results of the comparison of the keto-enol tautomerism of 3-thianaphthenoyltrifluoroacetone to that of 2-thenoyltrifluoroacetone in 80% benzene-20% ethanol may explain in part the greater sensitivity of the former in trace metal analysis.

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Zusammenfassung Die Keto-Enol-Tautomerie der 2- und 3-Isomeren des Thianaphthenoyltrifluoracetons wurde untersucht und mit der relativen Negativität der 2- und 3-Stellung des Thianaphtens zu erklären versucht. Der Vergleich der Keto-Enol-Tautomerie von II mit der des 2-Thenoyltrifluoracetons in BenzolÄthanol (80+20) könnte eine Erklärung für die größere Sensitivität von II bei der Spurenmetallanalyse bieten.

     

The Role of Active Oxygen Transfer through the Gas Phase in Propylene Oxidation over a Bismuth–Molybdenum Catalyst

The transfer of atomic oxygen from the surface of bismuth oxide onto molybdenum oxide through the gas phase, including the case when ozone was fed to the catalyst bed, is experimentally studied. It is found that the transfer of atomic oxygen through the gas phase only leads to the formation of the products of complete oxidation of propylene under conditions of heterogeneous propylene oxidation on the mixture of molybdenum and bismuth oxides. No new sites are formed on the surface of molybdenum oxide.