Polyfluorinated tetraoxacalixarenes and bicyclooxacalixarenes. Interaction of pentafluorobenzonitrile with resorcinol, orcinol 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].…”

“…Further heating of this mixture with resorcinol or tetrafluororesorcinol gave polyfluorinated oxacalixarenes of the ABAB or ABAC type. The same approach was used in the reactions of pentafluorobenzonitrile and pentafluoronitrobenzene with various resorcinoles [18,19], and the synthesis was also performed without intermediate isolation of triphenyl ethers. We used this approach for the synthesis of dioxadithiacalix [4]arenes.…”

“…By column chromatography on silica gel using CCl 4 and CHCl 3 as eluents, 0.68 g of the solid product containing (GC-MS) 93% tetrathiacalixarene 1 was isolated. 5,11,17,23,25,26,27,6,10,12,16,18,22,24-octakis(trifluoromethyl)-2,8,14, 20-tetrathiapentacyclo[19.3.1.1 3,7 .1 9,13 .1 15,19 ]octacosa-1(25),3 (28),4,6,9(27),10,12,15(26),16,18, 21,23-dodecaene 1:…”

“…mp 304.6-304.9 • C. 19 F NMR ((CD 3 ) 2 CO): δ −112.1 (septet d, 4F, J F(5)-2CF3(4,6) = 33 Hz, J F(5)-F(28) = 15 Hz, F-5,11,17,23), −91.6 (m, 4F, F-25,26,27,28), −53.5 (dd, 24F, J CF3(4)-F(5) = 33 Hz, J CF3(4)-F(28) = 7 Hz, CF 3 (4,6,10,12,16,18,22,24)). 13 10)-F(11) = 28 Hz, CF 3 (10,24)), −55.3 (dd, 6F, J CF3(12)-F(11) = 36 Hz, J CF3(12)-F(27) = 6 Hz, CF 3 (12,22)), −55.1 (dd, 6F, J CF3(16)-F(17) = 36 Hz, J CF3(16)-F(26) = 4 Hz, CF 3 (16,18)). 19…”

“…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.…”