Macrocyclic hydrocarbons with rigid and flexible building blocks

We report the synthesis of a series of new hydrocarbon macrocycles. Followi ng the dithia-phane route, four large rings 3-6 of the cyclophane type cont aining different numbers of ring atoms were prepared confirming the general applicability of this route compared to alternative macrocyclizations. Cyc le 3 is the hydrocarbon analogue to the tetralactam and the sulfone amide m acrocycles 1 and 2 used in many rotaxane syntheses. The macrocycles synthes ized here are supposed to be useful as wheels in the slipping approach to r otaxanes to further establish a reference system for the cavity size of cyc lic compounds by comparing them to certain complementary blocking groups. T he x-ray data obtained of the macrocycles 3, 5, and 6 reveal the cavity sha pe and size in solid state.