Synthesis of Polyfluorinated Tetraoxacalix[4]arenes by Reaction of Pentafluoronitrobenzene with Resorcinol, Orcinol, and
- PDF / 254,407 Bytes
- 7 Pages / 612 x 792 pts (letter) Page_size
- 83 Downloads / 152 Views
hesis of Polyfluorinated Tetraoxacalix[4]arenes by Reaction of Pentafluoronitrobenzene with Resorcinol, Orcinol, and Tetrafluororesorcinol V. N. Kovtonyuka,*, H. Hana,b, and Yu. V. Gatilova a
Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, 630090 Russia b
Novosibirsk National Research State University, Novosibirsk, 630090 Russia *e-mail: [email protected] Received February 28, 2020; revised March 27, 2020; accepted April 13, 2020
Abstract—Successive reactions of pentafluoronitrobenzene with resorcinol, orcinol, and tetrafluororesorcinol in acetonitrile in the presence of triethylamine afforded polyfluorinated ABAB and ABAC tetraoxacalix[4]arenes. Analysis of the 1H and 19F NMR spectra of the synthesized oxacalixarenes indicated high conformational mobility of the resorcinol and tetrafluororesorcinol fragments of their molecules due to interaction with the solvent. Keywords: polyfluorinated tetraoxacalixarenes, pentafluoronitrobenzene, resorcinol, orcinol, tetrafluororesorcinol, conformational behavior
DOI: 10.1134/S1070428020070052 Tetraoxacalixarenes are among scaffolds used in supramolecular chemistry to study host–guest intermolecular interactions [1]. A number of chemosensors for neutral organic compounds [2–4], cations [5–7], and anions [8–11] have been obtained on the basis of tetraoxacalixarenes. The possibility of using oxacalixarenes as ion pair transporters through cell membranes has been demonstrated [12–15]. Some oxacalixarenes have been found to exhibit physiological activity [16].
Likewise, successive reactions of pentafluoronitrobenzene with resorcinol and tetrafluororesorcinol in acetonitrile in the presence of triethylamine gave triphenyl ethers 1a and 3a and tetraoxacalixarenes 4a–8a containing an impurity of the corresponding isomers (Scheme 1). Diether 3a was synthesized previously in a moderate yield (37%) by heating pentafluoronitrobenzene with tetrafluororesorcinol in acetonitrile in the presence of potassium carbonate [23].
Fluorinated tetraoxacalixarenes were synthesized previously via [3 + 1] two-step fragment coupling approach by reaction of 4-substituted tetrafluoropyridines with resorcinol and orcinol [17, 18], as well as by reaction of dichlorotriazines with perfluorinated dihydroxybenzenes [19].
The synthesis of tetraoxacalixarenes 4a–8a can be performed both with intermediate isolation of triphenyl ethers 1a, 1b, 3a, and 3b and via reaction of orcinol with 2 equiv of pentafluoronitrobenzene under mild conditions, followed by heating of the resulting mixture of triphenyl ethers 2a and 2b with 1 equiv of orcinol or tetrafluororesorcinol.
In this work we examined a fragment coupling approach to the synthesis of polyfluorinated tetraoxacalixarenes via reaction of pentafluoronitrobenzene with resorcinol, orcinol, and tetrafluororesorcinol. This approach has been utilized by us in the synthesis of A3B perfluorinated tetraoxacalixarenes [20]. Recently, we have also shown that polyfluorinated ABAC tetraoxacalixarenes
Data Loading...
