Über Verbindungen der Siliciumtetrahalogenide mit aromatischen N-Heterocyclen: Bestätigung und Berichtigung

Zusammenfassung Von den früher⁶ beschriebenen Additionsverbindungen zwischen Siliciumtetrahalogeniden und Pyridin bzw. seinen Homologen konnten J₄Sipy ₄ ⁷ und HSiCl₃ py ₂ eindeutig bestätigt und in ihren Eigenschaften wie einigen chemischen Reaktionen näher festgelegt werden. Nicht dagegen existieren Verbindungen zwischen SiJ₄ und Chinolin, -Picolin, Acridin oder Collidin. SiF₄ bildet bei direktem Einleiten in Chinolin eine bereits kurz oberhalb Raumtemperatur zersetzliche Additionsverbindung F₄Si(chin)₂.

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From addition compounds of silicon tetrahalogenides and pyridine, published⁶ in 1954, the somewhat doubtful J₄Sipy ₄ ⁷ and HSiCl₃ py ₂ could be confirmed and fixed in their properties as well as in some chemical reactions. On the contrary compounds between SiJ₄ and quinoline, -picoline, acridine and collidine do not exist. On passing SiF₄ directly into quinoline, an addition compound F₄Si(chin)₂ is formed which decomposes already at temperatures somewhat higher than room temperature.

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64. Mitt.:H. Bürger, M. Schulze undU. Wannagat, Inorg. Nucl. Chem. Letters3, 43 (1967).

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Zugleich 4. Mitt. über Verbindungen von Nichtmetallhalogeniden mit Pyridin und seinen Homologen; 3. Mitt.:U. Wannagat undG. Schindler, Angew. Chem.69, 784 (1957).

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Mit Auszügen aus der DissertationK. Hensen, Techn. Hochschule Aachen 1962.

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Mit Auszügen aus der DiplomarbeitP. Petesch, T. H. Aachen 1958.     

Alkylamino- und Dialkylamino-phenoxy-methylsilane

Zusammenfassung Alkyl-und Dialkylamino-phenoxy-methylsilane ließen sich sowohl durch Umsetzung von Phenoxy-methyl-chlorsilanen mit primären und sekundären Aminen unter Cl/NRR-Austausch als auch durch Reaktion von Phenoxymethylsilanen mit substituierten Alkaliamiden unter C₆H₅O/NRR-Austausch gemäß den Gl. (1) bis (6) darstellen. Ihre Eigenschaften sind aus Tab. 1 zu ersehen.

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We succeeded in preparing alkyl- and dialkylamino-phenoxymethylsilanes by reaction of phenoxy-methyl-chlorosilanes with primary and secondary amines (Cl/NRR-exchange) as well as by reaction of phenoxymethylsilanes with substituted alkaliamides (C₆H₅O/NRR-exchange)according equations (1) to (6). Their properties are to be seen in table 1.

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53. Mitt.:U. Wannagat undG. Schreiner, Mh. Chem.96, 1902 (1965).

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Mit Auszügen aus der DissertationG. Schreiner und der DiplomarbeitJ. Pohl, Techn. Hochsch. Graz, 1964.     

Reducing waste contamination from animal-processing plants by anaerobic thermophilic fermentation and by flesh fly digestion

There is currently no market in Israel for the large amounts of waste from fish- and poultry-processing plants. Therefore, this waste is incinerated, as part of the measures to prevent the spread of pathogens. Anaerobic methanogenic thermophilic fermentation (AMTF) of wastes from the cattle-slaughtering industry was examined previously, as an effective system to treat pathogenic bacteria, and in this article, we discuss a combined method of digestion by thermophilic anaerobic bacteria and by flesh flies, as a means of waste treatment. The AMTF process was applied to the wastes on a laboratory scale, and digestion by rearing of flesh fly (Phaenicia sericata) and housefly (Musca domestica) larvae on the untreated raw material was done on a small scale and showed remarkable weight conversion to larvae. The yield from degradation of poultry waste by flesh fly was 22.47% (SD = 3.89) and that from fish waste degradation was 35.34% (SD = 12.42), which is significantly higher than that from rearing houseflies on a regular rearing medium. Bacterial contents before and after thermophilic anaerobic digestion, as well as the changes in the chemical composition of the components during the rearing of larvae, were also examined.     

Synthesis of Cyclopropyl Ethers and Cyclopropanols by Carbene Transfer – Acetolysis of Cyclopropyl p-Toluenesulfonates

The reaction of chloromethyl phenyl ether with butyllithium in olefins yields phenoxy-cyclopropanes. 1-Chloro-1-phenoxycyclopropanes can be prepared in a similar manner, though the yields are poor. Alkoxycyclopropanes are formed when dichloromethyl alkyl ethers are treated with methyllithium/lithium iodide in the presence of olefins. Cyclopropanols can be obtained in good yields by reaction of (β-chloroethoxy)cyclopropanes either with butyl- or ethyllithium or with bases. – As was shown by acetolysis experiments with cyclopropyl p-toluenesulfonates having a known steric configuration, the rearrangement of a cyclopropyl derivative into an allyl cation proceeds in accordance with the Woodward-Hoffmann-DePuy rule. The solvolysis of exo-bicyclo[n.1.0]alkyl p-toluene-sulfonates is assumed to proceed via “semi-open” intermediates, which are somewhere between an allyl cation and a cyclopropyl cation.     

Verwendung von Carboxylpapier in der Papierchromatographie

Zusammenfassung Bei der Chromatographie auf Carboxylpapier herrschen definierte Ionenaustauschvorgänge vor, die sich theoretisch näherungsweise ableiten lassen. Durch Variation von Carboxylgehalt und austauschfähigem Kation im Papier, sowie vonph-Wert, Pufferkapazität und Kationenstärke in der entwickelnden Lösung ist es möglich, die für die chromatographische Trennung der drei basischen Aminosäuren günstigsten Bedingungen festzustellen. Es ist zu erwarten, daß sich auf Carboxylpapier weitere, kationenbildende Stoffe trennen lassen, die sich entweder in ihrer Affinität zur Oxycellulose oder in ihrer Basizität oder in beidem voneinander unterscheiden.Die Arbeit wurde durch wertvolle Kritik von Herrn Professor Dr. Th. Wieland gefördert. Wesentliche Anregungen stammen auch von Herrn Dr. W. Vollmer. Im Labor wurden die Chromatogramme sämtlich von Frau E. v. Dungen ausgeführt.     

A 13C endor study on Copper(II)/Zinc(II) bis-(diethyl-dithiocarbamate) Cu/Zn(et2dtc)2

¹³C ENDOR spectra of Cu(et₂dtc)₂ substituted into a single crystals of Zn(et₂dtc)₂ are reported. The symmetry of the incorporated guest molecule appears to be considerably influenced by the Zn(et₂dtc)₂ host lattice. The unexpectedly large isotropic ¹³C hfs coupling can be understood assuming a “transannular overlap” mechanism.     

Use of S-matrix approach to develop a theory of perturbations in 1/Z

On the basis of the S-matrix approach, a theory of perturbations in 1/Z is developed; the energy of a multielectron system is written in the form of a double series in powers of andZ and a method of determining the coefficients of this series in a j-j coupling scheme is given. The method is applied to configurations of the type , and numerical results are given for the wavelength of transitions between several states of the isoelectronic as sequence of carbon, illustrating the good agreement between experiment and theory.Translated from Izvestiya Vysshikh Uchebnikh Zavedenii, Fizika, No. 8, pp. 59–63, August, 1978.     

Structure, activity and selectivity of V2O5-TiO2 catalysts for o-xylene conversion

The formation of needle shaped crystallites of V₆O₁₃ at low V concentrations on V₂O₅-anatase coated catalysts explains the low selectivity for phthalic anhydride during o-xylene oxidation. The (010) plane of V-oxide, most active for selective oxidation of o-xylene, is not accessible and the contact of this plane with the anatase faces promotes the anatase-rutile transformation and the incorporation and blocking of V⁴⁺ ions.

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V₆O₁₃ V , V₂O₅-, -. (010) , -, , - V⁺⁴.