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Published on: May 26, 2019
Synthesis of Thiacalix[4]arene Skeleton by the Conjugate Addition of Benzoquinone
Kamil Mamleev1, Nicolai Nikishkin1, Jan Čejka2
1Department of Organic Chemistry, University of Chemistry and Technology Prague (UCTP), Technická 5, 166 28 Prague 6, Czech Republic.
Abstract:
Macrocyclic systems having a thiacalix[4]arene-like structure with four bridging sulfur atoms can be easily constructed using benzoquinone and dithiol-based building blocks. The conjugate addition of benzene-1,3-dithiol with two equivalents of 2,6-dimethylbenzoquinone afforded the corresponding hydroquinone trimer, which, after oxidation to benzoquinone, undergoes a final macrocyclization with another benzene-1,3-dithiol molecule. The whole sequence represents a new strategy for the synthesis of macrocycles based on thiacalix[4]arenes. The conformational behavior of these macrocycles was studied using nuclear magnetic resonance and X-ray analyses, and their basic redox properties were investigated with electrochemical methods.
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