Thermisches Verhalten von Cyclopropa[c]chromenen

The Cyclopropa[c]chromenes 14 , trans-and cis- 15 , trans-and cis- 16 and 17 rearrange on heating > 200° in N, N-diethylaniline to give 2-alkyl-2H-chromenes 7, 8, 21, 22. The rate determining step of this rearrangement is the ‘homoelectrocyclic’ ring opening of the cyclopro-pa[c]chromenes to give ω-allyl-quinomethanes of type 4. These intermediates show fast [1,5s] and [1,7a] H-shifts, followed by electrocyclic ring closure. Deuterium labelling experiments are in agreement with this mechanism. The remarkable dependence of the rates of rearrangement with respect to the stereochemistry of the cyclopropa[c]chromenes (cf. table 2) suggests that in the first step only one of the two possible disrotatory modes of ring opening is involved.     

Synthesis of enantiomerically enriched allenes by (-)-sparteine-mediated lithiation of alkynyl carbamates

[reaction: see text]. The alpha-deprotonation of alkynyl carbamates 3 with the chiral base (-)-sparteine (4)/n-butyllithium, transmetalation with ClTi(O(i)()Pr)3, and subsequent substitution with an aldehyde results in the formation of enantioenriched 4-hydroxyallenyl carbamates 11. Stereoselection is determined by dynamic resolution of the lithium/(-)-sparteine complexes by selective crystallization.     

Über die Polymerisation des Phosphornitrilchlorids II

Zusammenfassung Die Polymerisation des Phosphornitrilchlorids in Substanz erweist sich als thermisch gestartete Radikalpolymerisation, die mit gleicher Geschwindigkeit und gleicher Temperaturabhängigkeit wie die durch Sauerstoff aktivierte Polymerisation in Lösung verläuft. Schon geringer Lösungsmittelzusatz bringt die thermische Polymerisation zum Erliegen. Ein Reaktionsschema mit Start-Kette-Abbruch wird diskutiert, das sowohl die Substanz- wie die Lösungspolymerisation wiedergibt. Der seinerzeit beschriebene Einfluß von Sauerstoff auf den Ablauf der Polymerisation erfährt dadurch eine wesentliche Korrektur.Die Depolymerisation von polymerem Phosphornitrilchlorid wird von 350 bis 600° C verfolgt und als gegenläufige Reaktionsfolge zur Polymerisation gefunden. Für das aus Polymerisation und Depolymerisation resultierende Gleichgewicht werden Druck- und Temperaturabhängigkeit festgestellt.Mit 8 Abbildungen.Herrn Prof. Dr.A. Klemenc zu seinem 70. Geburtstage gewidmet.Als I soll die ArbeitPatat-Kollinsky ¹ Über die Polymerisation des Phosphornitrilchlorids¹ gelten, die im folgenden Text auch mit (I) bezeichnet wird.— Eine Literaturzusammenstellung Phosphornitrilchlorid findet sich in der Monographie vonL. F. Audrieth, R. Steinmann undA. O. F. Toy, Chem. Rev.32, 109 (1943).     

Doppler-free laserspectroscopic investigations of hyperfine structure in the atomic cobalt spectrum

Performing Doppler-free laserspectroscopic investigations in the red wavelength region (640–670 nm) we were able to determine 10A-factors and 9B-factors of atomic cobalt levels. Now precise values of 18A-factors and 16B-factors of levels belonging to the configurations (3d+4s)⁹ are known. Fitting of the one-electron radial parameters to introduce agreement between experimental and theoretical hfs constants allows the prediction of hfs constants of not yet investigated fine structure levels. Values of the electric quadrupole moment of the Co⁵⁹ nucleus are determined in two electron configurations. The resulting mean value of the spectroscopic quadrupole moment isQ=0.35(3) barn.     

Mechanisms for the solvolytic decompositions of nucleoside analogues—I: Acidic hydrolysis of 2-substituted 1-(1-ethoxyethyl)benzimidazoles

A few 2-substituted 1-(1-ethoxyethyl)benzimidazoles have been prepared and the rate constants for their hydrolysis measured at various temperatures and oxonium ion concentrations. The formal kinetics followed and the effect of varying the 2-substitution on the hydrolysis rate suggest that the acid-catalyzed cleavage of these compounds involves a rapid initial protonation of the benzimidazole ring and a subsequent rate-limiting heterolysis of the protonated substrate to form a free nitrogen base and an ocarbenium ion derived from the ethoxyethyl group. The values obtained for the entropy of activation are consistent with the assumed unimolecular nature of the rate-limiting step. The effects of 2-substituents on the acidities of the protonated substrates and their heterolysis rates have been compared. The latter partial reaction has been suggested to be the subject of steric acceleration.     

L X-ray production cross sections, average L shell fluorescence yield and intensity ratios in heavy elements

L X-ray fluorescence cross sections, and intensity ratios were measured for elements in the 70￡Z￡92 atomic range at the excitation energy 59.5 keV using a Si(Li) detector. Furthermore, L X-ray fluorescence cross sections and intensity ratios were calculated for elements in the same range. The average L shell fluorescence yields were derived using experimental L X-ray fluorescence cross sections and theoretical photoionization cross sections. The obtained results were compared with other experimental and theoretical values. This revised version was published online in August 2006 with corrections to the Cover Date.     

Thermische Zersetzung von CuInSe2, LiInSe2 und LiInTe2

The thermal decompositions of CuInSe₂, LiInSe₂ and LiInTe₂ in vacuum at high temperatures were studied by using TG/DTG coupled with mass spectrometry. For CuInSe₂, two steps were found to be significant. Up to 1000 °C Se₂ and In₂Se evaporate, followed later by Cu₂Se. The Li-containing compounds show similar behaviour. However, Li⁺ was already detected during the first step. Obviously, Li₂Se dissociates more readily than Cu₂Se. No Cu⁺ species were detected up to the complete evaporation of CuInSe₂.     

Oxepinamides A-C and fumiquinazolines H--I: bioactive metabolites from a marine isolate of a fungus of the genus Acremonium

Three new oxepin-containing natural products (1-3) and two new fumiquinazoline metabolites (4-5) have been isolated from organic extracts of the culture broth and mycelia of an Acremonium sp., a fungus obtained from the surface of the Caribbean tunicate Ecteinascidia turbinata. The structures of the five compounds were determined through extensive analysis of 1D- and 2D-NMR data, and mass spectrometry. Compound 1 exhibited good anti-inflammatory activity in a topical RTX-induced mouse ear edema assay. Compounds 4 and 5 exhibited weak antifungal activity toward Candida albicans in a broth microdilution assay.     

Substituenteneffekte auf azido-tetrazolo-gleichgewichte elektronische und sterische effekte bei s-triazolo[4,3-c]tetrazolo[1,5-a]pyrimidinen1

The azido tetrazolo valence isomerism of twenty 9-methyl-s-triazolo[4,3-c]tetrazolo[1,5-a]pyrimidines with different substituents at position 5 has been studied by means of ¹H NMR spectroscopy. All the compounds have been found to be tetrazoles in the solid state and in (CD₃)₂SO solution; in CF₃COOH azido and tetrazolo isomers are in equilibrium. From equilibrium constants K and thermodynamic data determined it is concluded that in this series K depends on both electronic effects and steric requirements of the 5-substituents. A linear relation between K and σ was found for 5-arylderivatives because ΔS° keeps approximately constant and the substituent mainly operates on ΔH°.     

über Katalysatoren- und Fermentmodelle (1)

Ohne Zusammenfassung Die Arbeit wurde aus Mitteln des Marshall-Planes (ERP-Mittel) und mit Spenden aus dem „Fonds Chemie“ ausgeführt. Wir sprechen den zust?ndigen Stellen für die Gew?hrung der Beihilfe unseren verbindlichsten Dank aus. Der Deutschen Forschungsgemeinschaft danken wir für die überlassung einer Ultrazentrifuge, den Behring-Werken für die uns zur Verfügung gestellten Serumalbumin- und -globulin-Pr?parate.