Kinetik und Mechanismus der α/β-Umwandlung von Li2ZnGe

Kinetics and Mechanism of the α/βαTransformation of Li₂ZnGe The α/β-transformation of Li₂ZnGe was investigated by differential thermal analysis under nearly isothermal conditions. The possible mechanisms of solid state reactions are represented using the integrated and differentiated kinetic equations. For the investigation of DTA curves soft ware is developed to calculate the activation parameters and to find an adequate kinetic equation. A mechanism for the α/β-transformation of Li₂ZnGe is proposed and discussed.     

Sythese von α und β-Sinensal

β-Sinensal (2,6-dimethyl-10-methylene-dodeca-2,6,11-trienal) was synthesized from the diene-aldehyde 5 . This was converted into the trans- and cis-triene-aldehydes 16 and 17 , which were condensed with the phosphorane 18 to give the corresponding two geometrical isomers ( 3 and 19 ) of β-sinensal.     

Synthese von diastereo- und enantio-selektiv deuterierten β,ε-, β,β-, β,γ- und γ,γ-Carotinen

Synthesis of Diastereo- and Enantioselectively Deuterated β,ε-, β,β-, β,γ- and γ,γ-Carotenes We describe the synthesis of (1′R, 6′S)-[16′, 16′, 16′-²H₃]-β, εcarotene, (1R, 1′R)-[16, 16, 16, 16′, 16′, 16′-²H₆]-β, β-carotene, (1′R, 6′S)-[16′, 16′, 16′-²H₃]-γ, γ-carotene and (1R, 1′R, 6S, 6′S)-[16, 16, 16, 16′, 16′, 16′-²H₆]-γ, γ-carotene by a multistep degradation of (4R, 5S, 10S)-[18, 18, 18-²H₃]-didehydroabietane to optically active deuterated β-, ε- and γ-C₁₁-endgroups and subsequent building up according to schemes \documentclass{article}\pagestyle{empty}\begin{document}${\rm C}_{11} \to {\rm C}_{14}^{C_{\mathop {26}\limits_ \to }} \to {\rm C}_{40} $\end{document} and C₁₁ → C₁₄; C₁₄+C₁₂+C₁₄→C₄₀. NMR.- and chiroptical data allow the identification of the geminal methyl groups in all these compounds. The optical activity of all-(E)-[²H₆]-β,β-carotene, which is solely due to the isotopically different substituent not directly attached to the chiral centres, is demonstrated by a significant CD.-effect at low temperature. Therefore, if an enzymatic cyclization of [17, 17, 17, 17′, 17′, 17′-²H₆]lycopine can be achieved, the steric course of the cyclization step would be derivable from NMR.- and CD.-spectra with very small samples of the isolated cyclic carotenes. A general scheme for the possible course of the cyclization steps is presented.