Trennung und Identifizierung von Bactericiden auf der Basis von halogenierten Aromaten durch Dünnschicht-Chromatographie

Plates coated with silica gel with addition of fluorescence indicator are used for thin-layer chromatography with a solvent mixture of benzene and acetone (8∶2). The substances are made visible with UV-light and by spraying with solutions of 2,6-dibromoquinonechloroimide and sodium carbonate. The R_f-values, the fluorescence, and the colour of the spots allow to detect and to identify the bactericides rapidly and without further chemical techniques.     

Isolierung von 10′-Apo-β-carotin-10′-ol und (3R)-10′-Apo-β-carotin-3,10′-diol (Galloxanthin) aus Rosenblüten. 5. Mitteilung über Rosenfarbstoffe

Isolation of 10′-Apo-β-carotene-10′-ol and (3R)-10′-Apo-β-carotene-3,10′-diol (Galloxanthin) from Rose Flowers The novel (all-E)-10′-apol-β-carotene-10′-ol ( 2 ) and (all-E,3R)-10′-apo-β-carotene-3,10′-diol ( 5 ) have been isolated from petals of one yellow species and various whitish or yellow blend varieties of rose cultivars. Each (all-E)-compound is accompanied by a (Z)-isomer, probably the (9Z)-isomer. Diol 5 proved to be identical with galloxanthin, an apo-10′-carotenol previously isolated from the retina of chicken.     

Studies of the reactions between indole-2,3-diones (isatins) and 2-aminobenzylamine

Reflux of equimolecular amounts 2-aminobenzylamine and isatins in acetic acid produced indolo[3,2-c]quinolin-6-ones in good yields. A proposed mechanism involving initial formation of a spiro compound is given. This isolable intermediate subsequently rearranges via a sequential isocyanate ring opening and a cyclisation process to a urea derivative which finally cyclized to the indolo[3,2-c]quinolin-6-ones. The urea derivative could be prepared separately and cyclized selectively to indolo[3,2-c]quinolin-6-one. Reaction of N-acetylisatin with 2-aminobenzylamine at room temperature yielded the 1,4-benzodiazepinone 3-(2-acetamidophenyl)-1,5-dihydro-1,4-benzodiazepin-2-one whereas its isomer 2(2-acetamidophenyl)-4,5-dihydro-1,4-benzodiazepin-3-one was obtained from 2-(2-acetylaminophenyl)-N-(2-aminobenzyl)-2-oxoacetamide in acetic acid at room temperature.The previously unknown linear isomer of indolo[3,2-c]quinolin-6-one, i.e. indolo[2,3-b]quinolin-11-one, has been prepared by thermal (260°C) cyclization of methyl 2-phenylamino indole-3-carboxylate, which in turn was prepared in two steps from methyl indole-3-carboxylate.     

Übergangsmetallphosphidokomplexe. VIII. Strukturuntersuchungen an Übergangsmetallphosphor-Vier- und Sechsringkomplexen. Die Strukturen von [(CO)4MnPH2]2, [(CO)4MnPH2]3 und [cpNiPH2]3

Transition Metal Phosphido Complexes. VIII. X-Ray Diffraction Studies of Transition Metal Phosphorus Four- and Six-Membered Ring Complexes. Structures of [(CO)₄MnPH₂]₂, [(CO)₄MnPH₂]₃, and [cpNiPH₂]₃ [(CO)₄MnPH₂]₂ 1 crystallizes triclinic in the space group P1 with a = 680.4 pm, b = 706.4 pm, c = 919.1 pm, α 110.5°, β = 91.92°, γ 115.65°, and Z = 1 formula unit. The molecule exhibits a centrosymmetrical structure. The bond angles within the planar four-membered (Mn? P)₂-ring are 76.1° at the Mn atoms and 103.9° at the P atoms, respectively. The average Mn? P bond distance is found to be 235.1 pm. [(CO)₄MnPH₂]₃ 2 crystallizes monoclinic in the space group P2/n with a = 905.2 pm, b = 974.8 pm, c = 1264.2 pm, β = 109.1°, and Z = 2 formula units. The framework of the six-membered (Mn? P)₃-ring can be described as having a twist boat conformation. The average endocyclic bond angles are with 89.1° at the Mn atoms and 130.1° at the P atoms, respectively, largely widened compared to 1 . The average Mn? P bond distance, which is found to be 238.5 pm, is also slightly increased compared to 1 . [cpNiPH₂]₃ 3 crystallizes rhombohedral in the space group R3. The cell constants (hexagonal setting) are a = b = 1686.1 pm, c = 561.1 pm and Z = 3 formula units. The six-membered (Ni? P)₃-ring exhibits a chair conformation. The endocyclic bond angles are with 92.3° at the Ni atoms and 124.3° at the P atoms, respectively, comparable with those of the six-membered ring compound 2 . The Ni? P bond distance is found to be 215.2 pm. The eyclopentadienyl ligands are disordered and have been refined as rigid groups.     

R?ntgenspektrometrische Goldbestimmung in sulfidischen Erzen nach chemischer Anreicherung

Zusammenfassung Es wird eine Goldbestimmung an sulfidischen Erzen für den Bereich von 0,05–5 ppm bei 20 g Einwaage beschrieben. Das Gold wird durch Salpetersäurebehandlung von den übrigen Metallen getrennt, mit Salzsäure/ Salpetersäure gelöst und mit Selen als innerem Standard und Tellur als Spurenfänger mittels Zinn(II)-chlorid gefällt. Der Niederschlag wird auf ein Membranfilter aufgezogen. Die Goldbestimmung erfolgt über den Impulsratenquotienten der Gold L- und Selen K-Linien. Die störende Molybdän K-Strahlung und die Comptonstreuung werden durch ein Zirkoniumblech auf dem Röhrenfenster unterdrückt. Der Variationskoeffizient beträgt 20% für 0,2–5 ppm und 53,6% für 0,05 ppm.

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Summary A method is described for the determination of gold in sulphide ores within the concentration range of 0.05–5 ppm with sample weights of 20 g. Gold is separated from the other metals by treatment with nitric acid, dissolved by hydrochloric acid, containing some nitric acid, and is finally precipitated by stannous chloride applying selenium as internal standard and tellurium as collecting agent. The precipitate is mounted on a diaphragm filter and the determination of gold is carried out by X-ray analysis suppressing the disturbing Mo _K radiation and compton scattering by a zirconium sheet-metal on the X-ray tube. The pulse rate quotient of the lines Au _L /Se _K is a function of the concentration of gold. The variation coefficient is 20% for 0.2–5 ppm and 53.6% for 0.05 ppm.

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Herrn Prof. Dr.-Ing. habil. J. Hesemann zum 65. Geburtstag gewidmet.     

Über eine Klasse von nichtlinearen Randwertproblemen: Änderung des kritischen Parameters bei Symmetrisierungen

Zusammenfassung Seif(t) positiv und wachsend. Es wird gezeigt, dass die Stabilität kleiner wird für die nichtlinearen Randwertprobleme (1) bzw. (1) bei Steiner-bzw. Schwarz-Symmetrisierung.

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Summary We show, forf(t) positive and increasing, that stability of (1) resp. (1) is diminished by Steiner's symmetrization resp. Schwarz's symmetrization.

     

Struktur von S-9,10-Dimethyl-1,3,5,7-tetraarsa-2,4,6,8-tetraoxaadamantan und 9,10-Diethyl-1,3,5,7-tetraarsa-2,4,6,8-tetraoxaadamantan

Structure of S-9,10-Dimethyl-1,3,5,7-tetraarsa-2,4,6,8-tetraoxaadamantane and 9,10-Diethyl-1,3,5,7-tetraarsa-2,4,6,8-tetraoxaadamantane S-9,10-Dimethyl-1,3,5,7-tetraarsa-2,4,6,8-tetraoxaadamantane ( 1 ) and 9,10-diethyl-1,3,5,7-tetraarsa-2,4,6,8-tetraoxaadamantane ( 2 ) have been prepared by the reaction of propionic acid, propionic anhydride and butyric acid, butyric anhydride, respectively, with arsenic(III)-oxide. The crystals of 1 are rhombic, a = 6.902(4), b = 11.121(5), c = 13.988(8), space group P2₁2₁2₁. The crystals of 2 are monoclinic, a = 11.757(10), b = 11.255(10), c = 18.631 (18), β = 91.78(7), space group P2₁/n. The mean bond lengths and angles in 1 are AsO = 1.790 Å, AsC = 1.959 Å, OAsO = 100.60°, CAsO = 99.65°, AsOAs = 128.77°, AsCAs = 118.73°, and in 2 they are AsO = 1.780 Å, AsC = 1.978 Å, OAsO = 101.45°, CAsO = 99.55°, AsOAs = 129.64°, AsCAs = 117.72°.     

Strukturchemische Untersuchungen von Monammin-Kupfer(I)-Komplexen: [CuNH3]2[Pt(CN)6], [CuNH3]2[Pt(CN)4] und Cu3[Co(CN)6]-2 NH3

Structurally Chemical Investigation of Monoammin Copper (I) Complexes : [CuNH₃]₂[Pt(CN)₆], [CuNH₃]₂[Pt(CN)₄] and Cu₃[Co(CN)₆] · 2NH₃ The preparation and the properties of [CuNH₃]₂[Pt(CN)₆], [CuNH₃]₂[Pt(CN)₄] and Cu₃[Co(CN)₆] · 2NH₃ are described. I.R. and Raman spectra have been recorded and assigned. According to X-ray powder diagrams, [CuNH₃]₂[Pt(CN)₆] crystallizes in the trigonal space group D–P3 ml, a = 7.771, c = 5.988 Å, Z = 1. According to the spectroscopic and crystallographic data, it is concluded that the Cu_I ion is coordinated with one NH₃ group and with the N atoms of the cyanometallate anions. The coordination number of the Cu⁺ is 4 in [CuNH₃]₂[Pt(CN)₆] and 3 in [CuNH₃]₂[Pt(CN)₄]. In the Cu₃[Co(CN)₆] · 2 NH₃ complex two Cu atoms have the coordination number 2, the third Cu atom 4.     

13 C 183W-Kopplungen als sonde für metall—carbin-, —carbenund—alkyl-bindungen

Carbon-13 NMR data are reported for trimethyltin derivatives containing ER_n groups where E  C, Si, Ge, Sn, N, O and S including a series of cyclic amines with ring sizes from three to seven. Coupling constant values for the homologous series of fourth group derivatives give goood correlations with the electronegativity of E. The observation of the two-bond, ¦ ²J(¹¹⁹SnE¹³C) ¦ couplings only in the derivatives containing bulky R groups is rationalized by a bimolecular exchange of ER_n groups in the concentrated solutions studied.     

Zur Ermittlung der Äthylen-Sequenzlängenverteilung und der chemischen Uneinheitlichkeit in Copolymeren mit Propylen durch Pyrolyse-Gas-Chromatographie

Pyrolysis coupled with gas chromatography has been applied to investigate the sequence distribution in copolymers of ethylene and propylene. The copolymers analyzed have been prepared with soluble Ziegler-Natta-catalysts and show different degrees of crystallinity. In one series of samples the methyl group of the propylene units has been labeled with tritium. It was then possible to detect carbons by flame ionization detector and simultaneously the methyl groups by the radio-detector in parallel. Within the errors of these methods the results from both detectors are consistent with the calculations from kinetics. The accuracy of the data is best in copolymers with long ethylene sequences. By GPC fractionation a heterogeneity in the chemical composition can be observed. One component of the copolymers is of high molecular weight, while the other has a molecular weight of less than 1000 and is very rich in ethylene. The influence of chemical heterogeneity on sequence distribution derived from kinetics and pyrolysis has been discussed. A mechanism in which chains with different chemical composition are growing from different species of the catalyst has been proposed. The experimental results show that the heterogeneity is not critical for the sequence analysis by kinetics and pyrolysis.