Polyfluorinated oxacalixarenes. Interaction of perfluoro- m -xylene with resorcinol and tetrafluororesorcinol

Synthesis of Polyfluorinated Thia- and Oxathiacalixarenes Based on Perfluoro-m-xylene

“…We have previously observed a noticeable upfield shift of the inner-rim hydrogen and fluorine atoms of the resorcinol fragments in the 1 H and 19 F NMR spectra of polyfluorinated tetraoxacalixarenes, which is characteristic for this class of compounds [16][17][18][19]. The value of this upfield shift is solvent dependent, which may be due to implementation of some equilibrium 1,3-alternate conformations characterized by different degrees of magnetic shielding of the inner-rim protons and fluorines of the resorcinol fragments by the neighboring aromatic rings [19].…”

“…Therefore, based on studies of the reactivity of polyfluorinated arenthiols [23], for deprotection of the thiobenzyl group in compound 5, it was proposed to use chlorination by SO 2 Cl 2 , hydrolysis and subsequent reduction by Zn of the resulting product mixture. We have previously shown that the reaction of perfluoro-m-xylene with resorcinol under mild conditions led to the formation of a mixture of polyphenyl ethers with a predominant content of triphenyl ether [17]. Further heating of this mixture with resorcinol or tetrafluororesorcinol gave polyfluorinated oxacalixarenes of the ABAB or ABAC type.…”

“…Intramolecular cyclization of isothiouronium derivative 10 with the formation of dioxatiacalix [3]arene is unlikely, which can be explained in terms of strain of the intended cycle. We have previously shown that the reaction of perfluoro-m-xylene with resorcinol under mild conditions led to the formation of a mixture of polyphenyl ethers with a predominant content of triphenyl ether [17]. Further heating of this mixture with resorcinol or tetrafluororesorcinol gave polyfluorinated oxacalixarenes of the ABAB or ABAC type.…”

“…Thus, the interaction of two equivalents of perfluoro-m-xylene with the equivalent of resorcinol or orcinol under mild conditions and subsequent heating of the reaction mixtures with the equivalent of dithioresorcinol 4 leads to the formation of polyfluorinated dioxadithiacalix [4]arenes 8, 9 with a good yield (Scheme 3). We have previously shown that the reaction of perfluoro-m-xylene with resorcinol under mild conditions led to the formation of a mixture of polyphenyl ethers with a predominant content of triphenyl ether [17]. Further heating of this mixture with resorcinol or tetrafluororesorcinol gave polyfluorinated oxacalixarenes of the ABAB or ABAC type.…”

“…We have previously shown that the interaction of polyfluoroaromatic compounds (perfluoro-m-xylene, pentafluorobenzonitrile and pentafluoronitrobenzene) with various resorcins and bisphenols leads to the formation of polyfluorinated tetraoxacalixarenes with a good yield [16][17][18][19]. Interest in fluorinated tetraoxacalixarenes is associated with a fairly high electron-deficiency of polyfluorinated aromatic nuclei in these compounds, which may increase their ability with regard to host-guest intermolecular interactions.…”