SYNTHESIS OF CYCLOPHANES WITH INTRA-ANNULAR FUNCTIONALITY AND CAGE STRUCTURE

Cyclophanes of the type 1 and 2, with large cavity sizes, have been sy nthesized from the corresponding dichloride 8 or 8a and o-xylene-alpha ,alpha'-dithiol (9), p-xylene-alpha,alpha'-dithiol (10), or m-terpheny ldithiol (11). Similarly, cyclophanes of the type 3 with intra-annular functionality have been obtained by the coupling of the corresponding dithiol 15 or 19 and m-terphenyl dibromide 5, 5a, 5b, or 5c. With the aim of introducing multifunctionality, cyclophanes of the type 21 and 23 were prepared from 3,5-bis(mercaptomethyl)anisole or 3,5-bis(merca ptomethyl)phenol and the corresponding substituted m-terphenyl dibromi de Bb or 5c. Cyclophanes 24, 24a, 24b, and 32, with a new type of cage structure, have been obtained by the coupling of the corresponding te trathiol as with 2 equiv of the dibromides 5c, 5a, and 5b or 1 equiv o f the tetrabromide 31, respectively. Further, the sodium salts of the cyclophanes 3c, 21, and 24b were completely characterized by H-1 NMR s pectroscopy. XRD analysis of the cyclophane 21 revealed the presence o f an ethanol molecule inside the cavity, indicating the facile formati on of a host-guest complex.