Synthesis of Dihalo‐Substituted Analogues of Tröger’s Base from <i>ortho</i>‐ and <i>meta</i>‐Substituted Anilines

Abstract

Abstract For the first time, ortho ‐ and meta ‐halo‐substituted anilines were successfully condensed with formaldehyde to dihalo‐substituted analogues of Tröger’s base. By using paraformaldehyde and TFA, yields of 2−85% of these potential supramolecular building blocks were obtained. Even the inconceivable achievement of condensing anilines unsubstituted in para ‐position to analogues of Tröger’s base was successful. Adding our present results to our previous, makes it now possible to synthesize analogues of Tröger’s base halo‐substituted in almost any desired position in each of its two aromatic rings. In addition the first X‐ray structure of a dihalo‐substituted analogue of Tröger’s base, 3,9‐dibromo‐4,10‐dimethyl‐6 H ,12 H ‐5,11‐methanodibenzo[ b , f ][1,5]diazocine ( 17 ), is presented. (© Wiley‐VCH Verlag GmbH &amp; Co. KGaA, 69451 Weinheim, Germany, 2003)