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Synthesis of monocrown-substituted p-tert-butyl(thia)calix[4]arenes
A.A. Muravev, S.E. Solovieva, S.K. Latipov, I.S. Antipin, A.I. Konovalov
A.E. Arbuzov Institute of Organic and Physical Chemistry KazCS RAS, Russia
420088, Kazan, Arbuzov str. 8. E-mail: anton_muravyov@rambler.ru
One of the extensively developing fields of organic chemistry is the design,
synthesis, and study of the properties of nanosized molecular systems, which
incorporate some structural blocks performing various functions, such as receptor and
signal (sensor). For example, the combination of calixarenes and crown-ether fragments
in one molecule gave rise to the formation of novel class of receptors, calixcrown
ethers, which have an outstanding selectivity of recognition of alkali metal cations.
For this reason, in this work, the synthetic route to the preparation of
thiacalixmonocrown-ethers in 1,3-alternate conformation was given., which have
bromo- 1, thioaceto- 2 (4), and mercapto- 3 groups. With an aim to prevent the
formation of biscrown-ethers, we performed the distal substitution of two phenolic
groups of calixarene by ω-haloalcohols.
Currently new bromoderivatives of thiacalix[4]arene 1 and 5 have been
synthesized under Mitsunobu protocol and the methods of preparation of known
derivatives were improved. Bromo-substituents were substituted for thioaceto-groups
and, then, mercapto-groups with high yields. Structures of compounds were elucidated
by 1D and 2D NMR spectroscopy (HSQC, HMBC, COSY, NOESY), MALDI TOF
MS, IR spectra, and elemental analysis.
The work was supported by the Russian Foundation for Basic Research (grant
no. 11-03-00985).