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991.
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.
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).


Oxidationsprodukte von Arylhydrazon-Verbindungen, 7. Mitt. (6. Mitt.)  相似文献   
992.
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 pH 5,8 oder nach Demaskierung mit Chloralhydrat bei pH 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.
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 pH 5.8 or after demasking with chloralhydrate is titrated with EDTA at pH 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).
  相似文献   
993.
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  相似文献   
994.
995.
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.  相似文献   
996.
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.  相似文献   
997.
Conclusions The high catalytic activity of (CH2=CHSiR3)·Fe(CO)4 complexes was demonstrated in the reaction of vinylsilanes with polyhalomethanes and hydrosilanes.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 914–920, April, 1982.  相似文献   
998.
When the cations bound to purple membrane are removed it turns blue, and when this blue membrane is irradiated its color changes to pink. Irradiation of pink membrane leads to the reformation of blue membrane. We have determined that the quantum efficiency for the formation of pink membrane from deionized blue membrane is 1.6 ± 0.6 ± 10 4 at 0oC, pH 5.0. We also found that the quantum efficiency for the back photoconversion, i.e. the formation of blue membrane from pink membrane, is 8.8 ± 1.6 ± 10-3 at 0oC, 55 times greater than that of the forward photoconversion reaction. The extinction coefficients of the pink membrane and blue membrane were determined to be 44 500 ± 670 cm-1 M-1 at 491 nm and 54 760 ± 830 cm-1 M -1 at 603 nm, respectively, assuming light-adapted purple membrane is 63 000 cm-1 M -1 at 568 nm. The quantum efficiency for forming pink membrane from blue membrane is much lower than that for forming the photointermediate of the blue membrane's photocycle. Their relationship is similar to that of light-adaptation and photocycle of the dark-adapted purple membrane.  相似文献   
999.
1000.
Abstract From April 1982 to April 1986 we used photodynamic therapy to treat 192 patients with various malignancies. In all, 172 injections of hematoporphyrin derivative and 135 injections of dihematoporphyrin ether were made intravenously to sensitize the tumors; 684 photodynamic treatments were given using a tunable dye argon laser system for the light source. The technical problems of the light source and delivery systems are presented and the efficacy of therapy is analyzed.  相似文献   
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