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The synthesis of thiamacrocycles and the study of their properties
Nejedlý, Jindřich ; Kroutil, Jiří (referee) ; Starý, Ivo (advisor)
The aim of this work is the study of a simple method of preparing macrocyclic ligands for complexation of fullerenes. Necessary attribute of those ligands is their construction of electron-rich building blocks, which are prerequisite for π-π interactions with electron- deficiency fullerene spherical systems. Tetrathiafulvalene (TTF) is a known electron-rich system and for this reason, 2,3-bis(butylthio)-6,7-bis(2-kyanoethylthio)- tetrathiafulvalene was chosen as a basic building block. The protecting cyanoethyl group in this derivative can be removed by the acting of a base and thus generated thiolate function group is used in alkylation reactions of bis(bromomethyl)aryls. In reactions of these two components of bifunctional alkylation reactions was produced (in addition to the prevalent oligomeric products) a mixture of macrocycles with different sizes, the number of included building units was marked as [2 +2], [3 +3] and [4 +4] macrocycles. Reactions of TTF derivative with 4,4'- bis(bromomethyl)biphenyl and 4,4'-bis(bromomethyl)diphenylether have been performed. Column chromatography fractions of cyclic products were in both cases analyzed by gel permeation chromatography, NMR spectroscopy. The performed study has shown, that an equipoise to the simplicity of the synthetic protocol are low yields of...
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Synthesis of selectively disubstituted derivatives of alpha-cyclodextrin for chemosensoric applications
Diviš, Martin ; Kroutil, Jiří (referee) ; Jindřich, Jindřich (advisor)
Tato diplomová práce se zabývá problematikou vhodné selektivní derivatizace - cyklodextrinu pro jeho následné použití jako stacionárního chemosenzoru s fluorescenční skupinou. Byla vyvinuta a vypracována metodika pro přípravu selektivně disubstituovaného -CD. Dále byla vyvinuta metodika pro přípravu knihovny linkerů s fluoroforem a jejich navázání na CD. Také byly připraveny linkery pro připojení CD na pevnou fázi. Byla vyvinuta metodika pro připojení jednotlivých linkerů na CD za pomoci "click" reakcí, jmenovitě 1,3-dipolární cykloadice a reduktivní aminace. Nebyla připravena cílová série látek.
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On Azahelicenes: Synthesis, Resolution, Properties and Applications
Míšek, Jiří ; Starý, Ivo (advisor) ; Kroutil, Jiří (referee) ; Macháček, Vladimír (referee) ; Závada, Jiří (referee)
1 Abstract A novel and modular approach to azahelicenes has been developed. Using 12+2+2) cyclotrimerisation of appropriate triyne as a key step, azahelicenes 83, 84 and 85 have been prepared (Scheme 1). &83 84 Scheme 1. Aza[6]he|icenes 84 and 85 have shown to be sufÍicienl|y conÍigurationa||y stable and have been resolve inlo individual enantiomers by the diastereoisomeric sa|t crysta|isation and chira| HPLC. This a||owed to determine exact Va|ues oÍ racemisation barriers Íorboth aza[6]he|icenes 84 and 85. In general' both hexacyclic derivatives 84 and 85 are stable enough to be used in asymmetric transÍormations or chira| sensing. The abi|ity oÍ aza[6]he|icenes 84 and 85 to serve as chira| ligands íortransition meta|s has been proven by the preparation and X. ray analysis ol corresponding si|ver comp|exes. lnteresting chira| selÍ.recogniton properties oÍaza[6]he|icenes 84 in gas phase have been described using mass spectrometry techniques. |n order to comp|ement inÍormation about azahelicenes basicilies, gas phase proton afÍinities oÍ derivatives 84 and 85 and so|ution phase dissociation constants oÍ azahe|icenes 83. 84 and 85 have been determined. Eventua||y, the Íirst uti|ization oÍ azahe|icene in asymmetric catalysis has been demonstrated by the successÍu| use oÍ optical|y pure aza[6]he|icene...
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