Der aus dem Adamantylacetylchlorid (I) mit Äthoxy‐Mg‐malonsäurediäthyl‐ ester in siedendem Benzol dargestellte Acylmalonsäureester (II) geht unter der Einwirkung von H2SO4 in wäßriger Essigsäure bei Erwärmung glatt in das Adamantylaceton (IV) über.
Beim Erhitzen des Adamantylalkanols (I)′mit HBr in Eisessig entsteht an Stelle des zu erwartenden Adamantylbromalkans ein Gemisch des Bromadamantans (III) mit den Isopropenyladamantanen (IV) und (V).
123ChemInform Abstract The title compound (I) contains a carbon-carbon double bond activated by the conjugated carbonyl function. Activated carbon-carbon double bonds of this type are known to react stereospecifically with Grignard reagents. Thus, the reaction of (I) with MeMgI stereospecifically yields the exo-derivative (II), whose structure is elucidated by 1H NMR, using shift reagent. Reduction of the ketone (II) according to Wolff and Kishner affords the hydrocarbon (III). The Michael addition of bulky substituents to the title compound (I) proceeds highly stereoselectively and predominantly yields the exo-derivatives. This is shown by the Michael addition of diethyl malonate to (I) and subsequent structure elucidation of the adduct (IV) using the 1H NMR shift technique. Starting from the adduct (IV), the 4-exo-substituted bicyclononanones (V) and (VI) and the 4-exo-bicyclononanes (VII) and (VIII) are prepared. The latter can be converted to the hydrocarbon (III) mentioned above. This again confirms the results of the structure elucidation.
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