Alkylation de l'acetylacetate de methyle par le α(p-nitrophenyl)-ethanol chiral par deshydratation intermoleculaire

Mitsunobu's method of acetoacetic ester alkylation by $\text{p}$-nitrophenyl-ethanol avoid the S_RN1 reaction and is well appropriate for the correlation of absolute configuration and $\text{ee}$ of the O and C alkylation products.     

Synthesis of 1-alkyl(aralkyl)-4-acyl-2-piperazinones

1-Alkyl(aralkyl)-4-acyl-2-piperazinones are formed in high yields during selective acylation of N-monosubstituted ethylenediamines by benzoyl and cyclohexylcarbonyl chlorides in the presence of pyridine hydrochloride and treatment of the reaction products with chloroacetyl chloride in the presence of potassium tert-butylate.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 514–517, April, 1986.     

Polarographic microdetermination of sulphur in organic compounds after oxygen flask combustion

Summary Three polarographic micro-methods are described for the determination of sulphur in organic compounds after oxygen-flask combustion. The products are converted into sulphuric acid by oxidation with hydrogen peroxide, the excess of which is expelled through boiling. The methods are based upon allowing the sulphuric acid to react with an excess of barium iodate or bromate, then recording polarographically the cathodic reduction wave of the iodate or bromate ion. The bromate methods are superior to the iodate method being simpler and more rapid, and the results are correct to within ca. ±0.5%.

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Zusammenfassung Drei polarographische Mikromethoden zur Bestimmung von Schwefel in organischen Verbindungen nach deren Verbrennung im Sauerstoffkolben wurden beschrieben. Die Verbrennungsprodukte werden durch Oxydation mit Wasserstoffperoxid in Schwefelsäure umgesetzt. Der Überschuß des Oxydationsmittels wird durch Kochen zerstört. Die Schwefelsäure läßt man mit überschüssigem Bariumjodat oder -bromat reagieren und mißt dann polarographisch die kathodische Reduktionswelle des Jodats oder Bromats. Die Bromatmethode ist der Jodatmethode überlegen, da sie einfacher und rascher zu Resultaten führt, die innerhalb ±0,5% korrekt sind.

     

Mass-spectrometer investigation of 3, 6-dialkyl-2, 5-diketopiperazines

Analysis of mass-spectra of various 2, 5-diketopiperazines gives the basic fragmentation rules for their molecular ions, and the effects of nature and positions of substituents on the process.Mass-spectrometry Laboratory of the Institute of the Chemistry of Natural Compounds.Antibiotics Chemistry Laboratory of the Institute of the Chemistry of Natural Compounds.     

Kinetics of the γ-radiation-induced polymerization of methyl methacrylate in the solid state

Studies have been made of the γ-radiation-induced polymerization of methyl methacrylate in bulk, in the solid state at a temperature of ?65°C. and a radiation intensity of 346,000 rad/hr. The reaction was found to have an extremely long induction period (～50 hr.) when pure monomer was used, and to be first-order with respect to polymer concentration. This first-order dependency was confirmed by a series of irradiations in which 0.6% poly(methyl methacrylate) was dissolved in the monomer before irradiation. These irradiations showed no induction period. Nuclear magnetic resonance spectroscopy indicated a much more heterotactic polymer than that obtained in the liquid state at ?49°C.     

Synthesis and bromination of 8-methylquinoline-5-carboxylic acid

8-Methylquinoline-5-carboxylic acid was obtained by the Skraup reaction from 3-amino-p-toluic acid or by hydrolysis of 5-cyano-8-methylquinoline. The latter was synthesized by the Rosenmund-von Braun reaction from 5-bromo-8-methylquinoline, which was obtained by bromination of 8-methylquinoline in the presence of silver sulfate. Bromination in the side chain of 8-methylquinoline-5-carboxylic acid and its nitrile was studied. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 366–368, March, 1980.     

Synthesis and Structure of Triphenylbismuth Bis(Fluorobenzoates)

The reaction between triphenylbismuth, hydrogen peroxide, and 3,4,5-trifluorobenzoic or pentafluorobenzoic acid (molar ratio 1 : 1 : 2, respectively) in ether gave triphenylbismuth bis(3,4,5-trifluorobenzoate) (I) and triphenylbismuth bis(pentafluorobenzoate) (II) in 74 and 89% yields, respectively. The structures of compounds I and II were established by X-ray diffraction. The Bi atoms have a distorted trigonal-bipyramidal coordination with acylate groups in the axial positions. The OBiO angles are 170.2(2)° and 171.5(2)° in I and II, respectively. The Bi–C(Ph)_eq bond lengths vary in the range of 2.187(6)–2.204(5) Å, the Bi–O(acyl) lengths are 2.256(5) Å in I, and 2.281(5) and 2.318(5) Å in II. In the crystals I and II, the Bi and carbonyl O atoms are involved in intramolecular interactions (Bi···O(=C) 2.926(5)–3.176(5) Å), which increase the equatorial CBiC angles on the side of these contacts to 136.2(3)° and 138.6(2)° in I and II, respectively.     

Kinetics of solid-state synthesis and properties of lead-containing niobate pyrochlores

The main features of the synthesis of (Pb_1-x Sr_x)₂Nb₂O₇ and (Pb_1-x Ba_x)₂Nb₂O₇ pyrochlore solid solutions were determined using isothermal thermogravimetry in tandem with formal-kinetic analysis. The stability and electron-transport properties of the triple niobates were studied, which allowed us to test them as electrode-active materials for membranes in ion-selective electrodes (ISEs).