|
|
The synthesis of thiamacrocycles and the study of their properties
Nejedlý, Jindřich ; Starý, Ivo (advisor) ; Kroutil, Jiří (referee)
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...
|
|
|
The tetrathiofulvalene derivatives: Their synthesis and properties
Nejedlý, Jindřich ; Starý, Ivo (advisor) ; Hocek, Michal (referee)
The goal of the diploma thesis was to prepare a spectrum of electron-rich macrocyclic derivatives of tetrathiafulvalene (TTF), which should serve as electron donors in interactions with electron-deficient acceptor molecules. A two-step synthesis was used for their preparation. First, a non-cyclic three-segment precursor was prepared by a reaction of a thiolate TTF construction block with a bis(bromomethyl)aromate. Then, a reaction of this precursor with another molecule of bis(bromomethyl)derivative closed the macrocycle. The latter reaction produced mainly [2+2] macrocycles containing two TTF and two aromatic units. In most cases, larger [4+4] macrocycles were also isolated from the reaction mixture. Besides thiolate TTF unit two other thiolate units, one with extended TTF core and other with smaller trithiafulvene ring, were used analogically in synthesis. By a combination of three thiolate blocks and five bis(bromomethyl)aromates 11 three-segment components were prepared and these were converted to 11 structural types of macrocycles with [2+2] and 7 macrocycles with [4+4] stoichiometry. The resulting macrocycles were characterized by 1 H a 13 C NMR spectroscopy and analyzed by a gel permeation chromatography. Their structures were also confirmed by high-resolution mass spectroscopy. Interaction...
|
|
|
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...
|
guest ::
