The Synthesis And The Properties Of Fluorine-containing Calix[4]arene Derivatives

Calixarenes are cavity-containing macrocyclic compounds with two distinct hydrophobic (upper rim) and hydrophilic (lower rim) regions in their molecular architecture. Based upon the detailed research on the supramolecular chemistry of calixarenes and the long research on the fluorine materials, we prepared for novel fluorine-containing calix[4]arene derivatives via esterification reaction and a novel bis(benzoyloxy)calix[4]arene derivative via the Fries rearrangement. The consequences are shown below:1. In accordance with the principal of molecular design and the technique of chemical synthesis, 25-[perfluoro-(3-oxo-2-methyl)-hexanoyl]-26,27,28-trihydroxy calix[4]arene was obtained from a series procedures. The novel fluorine-containing calix[4]arene was characterized by IR, ESI-MS, ¹H NMR, ¹⁹F NMR and elemental analysis. The ESI-MS spectrogram showed the existence of the dimmer of this compound. The optimal reaction conditions were achieved by use of K2CO3 as a catalyst, in acetonitrile, at 50℃ in six hours. The yield reached up to 32.8 % .2. In accordance with the principal of the technique of chemical synthesis, 25-[Perfluoro-(3,6-dioxo-2,5-dimethyl)nonoyl]-26,27,28- trihydroxycalix[4]arene was obtained from a series procedures. It was characterized by ¹H NMR, ¹⁹F NMR and IR. The optimal reaction conditions were achieved by use of K₂CO₃ as a catalyst, in acetonitrile, at 80℃ in ten hours. The yield reached up to 20.1 %3. 5,17-dibenzoyl-25,26,27,28-tetrahydroxycalix[4]arene was prepared via the Fries rearrangement. The single crystal of the compound was obtained. It possesses crystallographic twofold rotation symmetry and displays the calixarene cone conformation. The crystal is Monoclinic, C2/c, a=18.615(4) A, b=15.609(4) A, c=12.220(3) A, p=116.187(4)°, V=3186.1(13) (?)³, Dx=1.319 Mg/m³.4. The TGA and DSC analysis showed that the fluorine-containing calix[4]arene derivatives were stable below 350℃ and had good thermal stability.