172ChemInform Abstract The new catalytic system consisting of dicyclopentadienyltitanium dichloride and trisisobutylaluminum catalyzes the rearrangement of cis,trans,trans-dodecatriene (I) to give the tricyclododecenes (V) and (VI), together with (VII), whereas with polyphosphoric acid a mixture of the octahydroacenaphthenes (II) and (III) is obtained. Both mixtures are hydrogenated and the resulting hydrocarbons (IV), (VII) and (VIII), or (VIII) and (IX) rearrange in the presence of aluminum tribromide, producing 1,3-dimethyladamantane (X). (NMR-, MS-data).
Kondensationen des Cyclododecanon‐enamins (I) mit Methylacrylat bzw. ‐methacrylat liefern bei nachfolgender Hydridreduktion, hydrolytischer Spaltung der Enamin‐Gruppierung und schließlich Cyclisierung der anfallenden Ketoalkohole die Dihydropyrane (III) (b: Ausb. bezogen auf Id).
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