Conformationally Selective Synthesis of Mononitrocalix[4]arene in Cone or Partial Cone

Nitro‐substituted calixarenes in a cone and a partial cone conformation were prepared selectively using distinct synthetic routes. The selective nitration of tris‐ or penta‐substituted phenols of calix4]arene or calix6]arene provided mononitrocalixn ]arenes (n  =  4, 6). Subsequent addition of ethylene glycol (EG) moieties to mononitrocalix4]arene provided tetraEGylcalix4]arene in locked partial cone conformation. By an alternative route – initial addition of EG moieties to the non‐derivatized calix4]arene followed by the uncontrolled nitration – provided mononitro‐ and dinitro‐tetraEGylcalix4]arenes locked in the cone conformation. These nitrocalix4]arenes with locked cone or partial cone conformation are useful building blocks for further assembly of supramolecular systems, especially in the area of material sciences.