Ion-Molecular Reactions of Diethylsilylium Ions with Alcohols in the Gas Phase

Radiochemistry was used to study reaction of tritium-labeled diethylsilylium ions with alcohols in the gas phase. The reaction involves both rearrangement of the diethylsilylium ions and isomerization of the substituent in the substrate. The hydroxyl hydrogen of the alcohol and the tritium atom of the diethyl-silylium ion undergo exchange which, however, is less vigorous that in the case of the monoethylsilylium ion. A possible reaction mechanism is proposed.     

Cycloaddition of fluorinated oxazoles

Cycloaddition reactions of polyfluorinated 1,3-oxazoles with cyclic and acyclic alkenes were studied. The results of these reactions were interpreted using quantum chemical calculations. An unusual product, viz., fluorine-containing acylpyrrole, was studied by X-ray diffraction. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1630–1635, July, 2005.     

Isolation of fusicoccin from a culture filtrate ofFusicoccum amygdali

Fusicoccin A has been isolated from a culture filtrate of the filtrate of the fungusFusicoccum amygdali Del., and it has been characterized as an -glycoside of a tricyclic diterpenoid. The trimethylsilyl derivative of fusicoccin A has been investigated by combined GLC and mass spectrometry.All-Union Scientific-Research Institute of Applied Biology and Genetics, VASKhNIL, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 792–796, November–December, 1980.     

Halogenated 3-pyridylketones

The oxidation of 2,6-dichloro-3-benzylpyridines and bis(2,6-dichloro-3-pyridyl)methanes, respectively, was accomplished using chromic trioxide in a highly acidic medium. The synthesis of several phenyl-3-(2,6-dichloropyridyl)ketones and of bis(2,6-dichloro-3-pyridyl)ketone are reported.     

Dialkylindiumacetate R2InOOCCH3 (R = CH3, C2H5) Darstellung,Eigenschaften und Struktur

Dialkylindium Acetates R₂InOOCCH₃ (R = CH₃, C₂H₅). Preparation, Properties, and Structure. Dimethyl- and diethylindium acetate were prepared and the vibrational spectra (IR and RAMAN ) discussed. The X-ray structure determination shows that diethylindium acetate belongs to the orthorhombic space group Pnma. The unit cell with lattice constants a = 8.40, b = 7.41, c = 15.13 Å contains four molecules. Each indium atom forms with an acetate group a planar four-membered ring. The indium-oxygen distance within such a ring is only a little shorter than the distance of this oxygen to the indium of the next neighboured ring. Indium has therefore the coordination number six.     

Synthese von 8-Alkylamino-8-aryl-1,2,3,4,5,6-hexathiocan-7-thionen

Zusammenfassung Durch gemeinsame Einwirkung von primären aliphat. Aminen und Schwefel auf Methylarylketone in Methanol bei Raumtemp. erhält man in meist guten Ausbeuten 8-Alkylamino-8-aryl-1,2,3,4,5,6-hexathiocan-7-thione (1a-h). Die Umsetzung von 1,4-Diacetylbenzol mit n-Propyl-bzw. n-Butylamin und Schwefel liefert Phenylen-1,4-di-hexathiocanderivate (3 a, b).Bei der Reaktion von Acetophenon mit 3-N,N-Diäthylaminopropylamin und Schwefel entstehen neben dem 8-(3-N,N-Diäthylaminopropylamino)-8-phenyl-1,2,3,4,5,6-hexathiocan-7-thion (1e) 51% einer Verbindung der Summenformel C₁₅H₂₂N₂S₂ (2), der die Struktur der (3-N,N-Diäthylaminopropylimino)-phenyldithioglyoxylsäure zugeordnet wird.1 e läßt sich durch Behandlung mit wäßr. Natriumsulfit-Lösung zu2 abbauen,2 durch Reaktion mit Schwefel wieder in1 e überführen.

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Synthesis of 8-alkylamino-8-aryl-1,2,3,4,5,6-hexathiocan-7-thiones (Joint action of elemental sulfur and gaseous ammonia upon ketones, LXXVIII: Action of sulfur and amines on acetophenone, IX)

8-Alkylamino-8-aryl-1,2,3,4,5,6-hexathiocan-7-thiones (1a toh) are obtained mostly in good yields by the concomitant action of primary aliphatic amines and sulfur upon methyl aryl ketones in methanol at room temperature. Reaction of 1,4-diacetyl benzene and sulfur with n-propylamine or n-butylamine respectively leads to phenylene-1,4-dihexathiocane derivatives (3 a, b).Besides 8-(3-N,N-diethylaminopropylamino)-8-phenyl-1,2,3,4,5,6-hexathiocan-7-thione (1 e), which is obtained by reaction of acetophenone with 3-N,N-diethylaminopropylamine and sulfur, a product with the formula C₁₅H₂₂N₂S₂ (2) is isolated in 51% yield, to which the structure (3-N,N-diethylaminopropylimino)phenyl dithioglyoxylic acid is assigned. By treatment of1 e with aqueous sodium sulfite solution2 is obtained, which can be transformed back into1 e by reaction with sulfur.

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77. Mitt.:F. Asinger, A. Saus, H. Offermanns undP. Scherberich, Ann. Chem.753, 151 (1971).

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8. Mitt.:F. Asinger, A. Saus, H. Offermanns undF. Abo Dagga, Ann. Chem.723, 119 (1969).

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Teil der DiplomarbeitJ. Hartig, Techn. Hochschule Aachen, 1969.     

Zur komplexchemie von 4-zentren-π-systemen : XII. Glyoxaldiiminkomplexe: 1H-nmr-spektren und long range-kopplungen

Glyoxaldiimines (I) RN=CHCH=NR show in the NMR a downfield shift of glyoxalic protons (H_gly) when complexed to

(II: M = Mo, W), but increasing high field shifts when going to

(III) and

complexes (IV). In the tungsten complexes II H_glyW coupling satellites are resolved (J(WH) ≈4–6 Hz); in the phosphine compounds III, IV long range PH_gly coupling is clearly visible. Mechanisms of spinspin interaction are briefly discussed in connection with the EPR results on monoanionic radicals of II–IV.     

Effect of Gamma Irradiation on Strength Properties of Basalt Composites

Mechanics of Composite Materials - The problem of improving the strength properties of polymer composite materials based of roving made of basalt complex filaments and epoxy resin as a binder was...