International Summer School PROGRAM - Laboratoire d'Infochimie ...

Synthesis of disubstituted by mercapto groups (thia)calix[4]arenes
T.A. Rovnova, A.A. Muravev, S.K. Latipov, S.E. Solovieva, 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: leksa330@list.ru, svsol@iopc.knc.ru
Thiacalix[4]arenes (TCA) are next member of calixarene family. Special interest
has focused on using TCAs as suitable building blocks, multidentate preorganized
macrocyclic type ligands, precursors for creation of supramolecular architectures and
many other applications in nanotechnology and chemistry.
(Thia)calixarenes with narrow rim mercapto-substituents are potential precursors
for further modification with various functional groups and can be immobilized on a
solid surface, giving rise to sensors for heavy metal ions.
In this report, the synthesis of terminal disubstituted allyl- 3, 5; thioaceto-5, 6, 9;
and mercapto-7 (thia)calixarenes will be discussed. Interesting behavior of TCA
counterparts unsubstituted by upper rim was confirmed by MALDI TOF spectrometry
and 1 H NMR spectroscopy.
During the disubstitution of allyl-4 and bromoalkyl-8 thiacalix[4]arenes for
thioaceto-groups, the partial dealkylation of the lower rim was observed, when there
was an excess of potassium thioacetate or thioacetic acid, thus resulting in the mixture
of mono- and disubstituted products. Disubstitution was observed only when
stoichiometric amount of reagent was used.
The work was supported by RFBR grant № 11-03-00985.