Derivate des 5, 9‐Methano‐6, 7,8, 9‐tetrahydro‐5 H‐benzocycloheptens und Umlagerungen zum 1, 4‐Äthano‐1,2,3,4‐tetrahydronaphtalin‐System

Derivatives of 5,9‐Methano,7,8,9‐tetrahydro‐5 H ‐benzocycloheptene and Rearrangements to the 1,4‐Ethano‐I,2,3,4‐tetrahydronaphthalene System Reduction of the oxime 2 with Raney alloy gives the amine 3a , with AlH 3 a mixture of the isomeric amines 3a and 3b , whilst LiAlH 4 yields the aziridines 4a and 4b . The bicyclo[3.2.1]octane 4b rearranges under acidic conditions to the bicyclo[2.2.2]octane 5 . The olefin 7 can be converted to the aminoalcohol 9 via the epoxide 8 and to the amine 13 using iodine isocyanate: the carbon skeleto. remains intact. However, treatment of the olefin 17 with iodine isocyanate leads to the bicyclo[2.2.2]octanes 21 and 24 in which a skeletal rearrangement has taken place. The configuration was determined by NMR. and X‐ray analysis.