Ein Dreikomponenten-Zweiphasensystem für die schnelle Flüssigkeits-Chromatographie

Zusammenfassung Für die Hochdruck-Flüssigkeits-Chromatographie wird ein Dreikomponenten-Zweiphasensystem beschrieben. Die Mischungslücke besteht zwischen dem wenig polaren Methylenchlorid und dem stark polaren Wasser und kann durch Zugabe von Äthanol als Lösungsvermittler geschlossen werden. Durch den Anteil der stark polaren Komponente in den jeweils koexistenten Phasen ist die Polarität von stationärer und mobiler Phase als stationäre gebunden und aus der mobilen immer wieder regeneriert. Durch Verteilungs-Chromatographie in der Mischungslücke ist eine Vielzahl von Stoffklassen der Trennung zugänglich, so z.B. Corticosteroide, Östrogene, Phenole, Phenolcarbonsäuren usw.

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A three-component two-phase system for high speed liquid chromatography

Summary High pressure liquid chromatography with a three-component two-phase system is described. For the less polar methylenechloride and the highly polar water a wide range of incomplete miscibility exists which can be decreased with ethanol. The water content of the coexistent phases determines the polarity of the stationary and the mobile phases. The more polar phase is adsorbed on silicagel as the column support material and serves as the stationary phase. Numerous compounds can be separated by partition chromatography between the coexistent phases, for instance; corticosteroids, estrogens, phenols, phenol-carboxylic acids and so on

     

Strukturaufklärung gemischter Komplexe von Eisen(II), Kobalt(II) und Nickel

Iron(II), cobalt(II) and nickel form complexes of the formula [Me(TTA)₂B¹] with 1-(2′-thenoyl)-3,3,3-trifluoroacetone (HTTA) and 2-pyridinalphenylimines (B¹) or bis-(2-pyridinal-R-diimines) (B²) and — in dependence of the -R group in the B² compounds — complexes of the formula [Me₂(TTA)₄B₂] and [Me₂(TTA)₂B²]. The octahedral geometry of the complexes can be unequivocally proven by means of electron spectra, IR spectra and from magnetic measurements. The labelling of solid [Ni(TTA)₂B¹] complexes with the nickel isotopes⁵⁸Ni or⁶²Ni permits an allocation of the Me-O- and Me-N-valency oscillations in the FIR.     

Theory of chirality functions,generalized for molecules with chiral ligands

The theory of chirality functions described in a previous publication is generalized to allow for chiral ligands. In the earlier theory, all symmetry operations of the molecular frame could be thought of as permutations of the ligands among the sites; in the present work, improper rotations not only permute the ligands, but convert them into mirror images. The group that generates all isomers from a given ordered molecule belonging to a frame with n sites is now the hyperoctahedral group of order 2ⁿ n! consisting of all possible combinations of permutations and site reflections. The representation theory of these groups is described, and applied to the problem of constructing qualitatively complete chirality functions, and of deciding which ligand partitions, and which isomer mixtures, are chiral. It is found useful to classify chiral representations of the covering group as ligand specific and class specific. The ligand specific representations describe chiral properties which are common to all frames and arise purely from the chirality of the ligands, while the class specific representations describe the chiral properties of the frame. A number of examples are explicitly worked out.     

Über die Cyclisierung von Histidinderivaten

Cyclisierung vonl-Histidin-methylester und Histamin über die (nicht isolierten) N-Phenylthiocarbonyl-derivate (Ia) führt durch intramolekulare Harnstoffbildung zu Derivaten des neuartigen bicyclischen Ringsystems Imidazo(1,5-c)tetrahydrooxopyrimidin (II, III).Dieses ist relativ beständig gegen saure Hydrolyse; Einwirkung von basischen Reagenzien (Alkali und Amine) und von Lithiumaluminiumhydrid führt unter Öffnung des Pyrimidinringes (zwischen 4 und 5) zur Bildung von 4(5)-substituierten Imidazolderivaten, wobei mit Aminen N-Carbonsäure-amide (V bis IX) und mit LAH in der Seitenkette N-methylierte Produkte (X, XI) entstehen.Untersuchungen an offenkettigen Modellsubstanzen mit ähnlicher Struktur (XVI, XVII) führten zu ähnlichen Ergebnissen — Abspaltung von Imidazol und entsprechender Substitution der zweiten Komponente, die in manchen Fällen primär als Isocyanat abgespalten wird. Für diese Reaktionen wird ein möglicher Mechanismus diskutiert.DieR _F-Werte einiger Imidazolderivate wurden bestimmt.     

Determination of isotopic composition of lithium by neutron activation analysis; comparison with mass spectrometry

An activation analysis method is described for routine determination of⁶Li-abundances in various lithium compounds on the basis of the reaction sequence⁶Li(n,α)T and¹⁶O(t, n)¹⁸F and the measurement of¹⁸F. Irradiations of diluted equeous solutions of samples containing CrO₃ as internal flux monitor were carried out at a thermal neutron flux density of ϕ≤10¹¹ n·cm⁻²·sec⁻¹. Interferences from variations in neutron self-shielding oxygen concentration and triton range do not exceed 0.5% when using the dilution technique. The results for⁶Li abundances from 3.52 to 7.60% with standard deviations of 1 to 2.5% were confirmed by mass spectrometric measurements.     

Schnelle Trennung von Rückstoßprodukten in der Gasphase

Experiments are described in which recoil products are separated fast and selectively. The aim of these investigations is an identification of short-lived nuclides, either for the study of nuclear reactions or for the study of decay properties of new products. The recoil products were provided by a Cf-252 source. The transportation zone and the identification zone could be heated to different temperatures. Using N₂ as carrier gas it was possible to separate Te selectively under certain experimental conditions. When Cl₂ was added, Sb, Tc, Nb, Mo, Zr, Ru and Sn were transported. Transport output was determined in dependence of temperature and composition of the gas.     

The catalytic hydrogenolysis of 1-phenylbicyclo[4.1.0]heptane and the corresponding azidirine and epoxide

The hydrogenolysisof 1-phenylbicyclo[4.1.0]heptane (1a), cis-1-phenyl-2-methylbicyclo[4.1.0]heptane (1b), 1-phenyl-7-azabicyclo[4.1.0]heptane (2) and 1-phenyl-7-oxabicyclo[4.1.0]heptane (3) was studied using Ni, Pd, Rh and Pt as catalysts. The hydrogenolysis of the C₁C₇ bond of 1a and 1b led to the selective formation of trans-1-phenyl-2-methylcyclohexane (4a) with retention of configuration. Compound 1a gave not only 4a but also phenylcycloheptane (6a), which is the product of C₁C₆ bond fission, and the ratio of 6a to 4a increased in the sequence: Ni ? Pd, Rh < Pt. No C₁C₆ bond fission was observed in the hydrogenolysis of 1b. These results can be explained by a mechanism involving the formation of the π-benzyl complex.trans-2-Phenylcyclohexylamine (8) was obtained stereoselectively in the hydrogenolysis of 2 over Raney Ni. This selective formation can be ascribed to the competition of “SN i” and “radical” processes. The Pd catalysed hydrogenolysis gave cis-2-phenylcyclohexylamine (9) as the main product, while the presence of sodium hydroxide promoted the formation of 8.Raney Ni catalysed hydrogenolysis of 3 yielded a mixture of phenylcyclohexane (13) and 2-phenylcyclohexanols (10 and 11). trans-2-Phenylcyclohexanol (10) was the dominant isomer; the hydrogenolysis resulted in the predominant configurational retention. Compound 13 was confirmed to be produced via 1-phenylcyclohexene (12). This deoxygenation may be explained by a mechanism involving the radical cleavage reaction of 3. The presence of sodium hydroxide led to the formation of cis-2-phenylcyclohexanol (11). The Pd catalysed hydrogenolysis also gave mainly 11.The difference in behaviour of cyclopropane, azidirine and epoxide we ascribe to the differences in the affinity for the catalyst and differences in the electronegativity between C, N and O atoms.     

Synthesis,spectroscopic characterization and redox reactivity of the copper(II) salicylaldiminates containing sterically hindered 2,6-diphenylphenol

New bidentate N-(2,6-di-phenyl-1-hydroxyphenyl) salicylaldimines bearing X = H and 3,5-di-t-butyl substituents on the salicylaldehyde ring, L ^x H, and their copper(II) complexes, Cu(L ^x )₂, have been synthesized and characterized by i.r., u.v./vis., ¹H-n.m.r., ¹³C-n.m.r., e.s.r. spectroscopy and magnetic susceptibility measurements. E.s.r. study has shown that chemical oxidation of Cu(L ^x )₂ with PbO₂ produces ligand-centered Cu^II-phenoxyl radical species. The complexes are easily reduced with PPh₃ via intramolecular electron transfer from ligand to copper(II) to give unstable radical intermediates, which in time are converted to another stable secondary radical species. The analysis of e.s.r. spectra of Cu(L ^x )₂ and generated radical intermediates are presented.     

Eine neuc Umlagerung an einem Metathebainon-Derivat mit Cyclohexa-2,5-dienon-Struktur

Zusammenfassung 4-O-Methyl-7,8-dehydro-metathebainon-methin (1) geht in alkalischer Lösung in das Naphthalin-Derivat3 über, das unter Abspaltung von Formiat7 liefert. Das Auftreten von3 kann durch Isolierung von13a nach Reduktion mit NaBH₄ nachgewiesen werden. Die aus3 und7 durch Reduktion erhaltenen Alkohole8a und13a werden in saurer Lösung unter Methanol-Abspaltung zu den 2,3-Dihydro-naphtho[1,8-bc]pyranen9 und14 cyclisiert.

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A new rearrangement of a metathebainone derivative with a cyclohexa-2,5-dienone groupment

4-O-Methyl-7.8-dehydrometathebainonemethine (1) in alkaline solution rearranges to the naphthalene derivative3, which eliminates formiate to give7. The occurrence of3 was confirmed by isolation of13a after reduction with NaBH₄. The hydroxy compounds8a and13a, obtained by reduction, eliminate methanol and cyclize to the 2.3-dihydronaphtho[1.8-bc]pyrans9 and14.

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Mit 2 Abbildungen     

Zur Ermittlung und rechnerischen Überprüfung thermodynamischer Daten aus experimentell gefundenen Werten, 11. Mitt.1: Ein Beitrag zur Berechnung der molaren Exzeßenthalpie und der molaren Exzeßentropie aus Dampfdruckdaten unter Verwendung der Ansätze vonRedlich-Kister undMusil-Breitenhuber

Zusammenfassung Für das binäre System n-Hexan(1)/Methylamin(2) werden die molare Exzeßenthalpie, die molare Exzeßentropie und die freie molare Zusatzenthalpie aus Dampfdruckdaten berechnet. Für die Berechnung der beiden ersten Größen wird sowohl die Ableitung der Parameter der verwendeten Ansätze als auch die Ableitung der freien molaren Zusatzenthalpie verwendet, die beiden Methoden werden verglichen. Zur Glättung der Ergebnisse werden die Parameter bzw. die freie Zusatzenthalpie durch Parabeln verschiedener Ordnung angenähert. Die Berechnung der vorliegenden Arbeit wurde auf der UNIVAC-490-Anlage des Rechen-Zentrums Graz durchgeführt^*.

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Determination and verification by calculation of thermodynamic data from experimentally obtained values, XI.: Contribution to the calculation of molar excess enthalpies from vapour pressure data using the treatments of Redlich-Kister and Musil-Breitenhuber

The molar heat of mixing and the molar excess entropy and the excessGibbs energy of the binary system n-hexane(1)/methylamine(2) are calculated using vapor-pressure data. As method the authors use differentiation of parameters of the statements as well as differentiation of the free molar excess enthalpy; both methods are compared. For smoothening the results the parameters resp. the free molar excess enthalpyG ^E are approximated by polynomals of different degree. The programm is written in FORTRAN IV and the UNIVAC-490-computer of the Graz Computer Centre has been used^*.

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Mit 5 Abbildungen

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1. bis 6. Mitt.:F. Gölles, Mh. Chem.92, 981 (1961);93, 191, 201 (1962);94, 1108 (1963);95, 1656 (1964);96, 1366 (1965); 7. bis 9. Mitt.:F. Gölles undA. Höpfner, Mh. Chem.97, 368, 911 (1966);99, 230 (1968); 10. Mitt.:F. Gölles undO. Wolfbauer, Mh. Chem.99, 1814 (1968).