Bromination and Iodination of 6 H ,12 H ‐5,11‐Methanodibenzo[ b , f ][1,5]diazocine: A Convenient Entry to Unsymmetrical Analogs of Tröger's Base

6 H ,12 H ‐5,11‐Methanodibenzo[ b , f ][1,5]diazocine can easily be prepared from aniline and paraformaldehyde. Its reactions with either N ‐bromosuccinimide (NBS) or with iodine monochloride (ICl) in the presence of a suitable activator smoothly afford 2‐bromo‐ and 2‐iodo‐ derivatives, respectively. The combination of these halogenation methods provides access to the 8‐bromo‐2‐iodo derivative, which is an interesting and otherwise inaccessible intermediate for the synthesis of unsymmetrical analogs of Tröger's base. The reported halogenations represent the first examples of electrophilic substitution in 6 H ,12 H ‐5,11‐methanodibenzo[ b , f ][1,5]diazocine. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)