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Synthesis and properties of complex π-electron systems with helical chirality
Houska, Václav ; Stará, Irena (advisor) ; Machara, Aleš (referee)
Planar shape-persistent macrocycles have been known for a long time and are routinely synthesized today. Non-planar 3D structures, however, still remain challenging synthetic targets in many cases. The objective of this Thesis was to develop a synthetic route to shape-persistent macrocycles containing dibenzo[5]helicene or its derivatives as structural units employing alkene and alkyne metathesis. The Introduction focuses on various methods of the macrocycle synthesis, on alkyne metathesis, and synthesis of helicenes is shortly reviewed as well. Then, the first part of Results and discussion describes the synthesis of 3,16-dichlorodibenzo[5]helicene and its derivatives. In the second part, the macrocycle synthesis from these dibenzohelicenes is discussed. The Experimental part provides a detailed description of performed experiments along with characterization of all new compounds prepared.
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Preparation and properties of building blocks of specialty polymers
Šichová, Kristýna
This Diploma Thesis presents results obtained by solution of two partial projects: a) Preparation of monomers from renewable sources using metathesis and tandem hydrogenation catalyzed with ruthenium compounds - project solved during my Erasmus stay at the Université de Rennes 1 in France; b) Preparation and properties of ,-bis(tpy)quarterthiophene oligomers carrying ionic side groups as oligomonomers for polyelectrolyte conjugated dynamers - project solved at the Department of Physical and Macromolecular Chemistry, Faculty of Science, Charles University in Prague. Project a): Self-metathesis of 1,2-epoxyhex-5-ene (but-3-enyloxirane) and its cross-metathesis with methyl acrylate and acrylonitrile catalyzed with ruthenium compounds as well as tandem design of these metatheses and consecutive hydrogenation of their products by gaseous hydrogen have been optimized. The following influences have been studied and tuned: (i) type of the catalyst (Grubbs, Hoveyda, Zhan) and its concentration and method of dosing, (ii) concentration of reactants and additives, (iii) type of solvent, and (iv) reaction temperature. Reactions were monitored by the GC, GC and MS methods and the products were characterized by the NMR method. Methyl 6,7-epoxyheptanoate (methyl 5-oxiranylpentanoate) obtained by the tandem...
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Synthesis of 1,2-disubstituted cyclopentadienes and their application in syntheses of metallocenes
Vician, Marek ; Kotora, Martin (advisor) ; Míšek, Jiří (referee)
In this master thesis 1,2-disubstituted cyclopentadienes were prepared by method composed of three transition metal catalysed reactions. Then, the cyclopentadienes were converted into cyclopentadienyl manganese, rhenium and iron complexes. A one-pot synthesis of the cyclopentadienyl metal complexes was developed without isolation of the intermediate cyclopentadienes. The second goal of this thesis was preparation of vinyl-substituted cyclopentadienes using ring closing enyne metathesis. The last part of thesis dealt with synthesis of a chiral cyclopentadiene and preparation of the corresponding metal complexes. The important part of this work was preparation of starting materials using palladium catalysed cross-coupling reactions. Key words: cyclopentadienes, carbometallation, cross-coupling, metathesis, metallocenes.
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Preparation and properties of building blocks of specialty polymers
Šichová, Kristýna
This Diploma Thesis presents results obtained by solution of two partial projects: a) Preparation of monomers from renewable sources using metathesis and tandem hydrogenation catalyzed with ruthenium compounds - project solved during my Erasmus stay at the Université de Rennes 1 in France; b) Preparation and properties of ,-bis(tpy)quarterthiophene oligomers carrying ionic side groups as oligomonomers for polyelectrolyte conjugated dynamers - project solved at the Department of Physical and Macromolecular Chemistry, Faculty of Science, Charles University in Prague. Project a): Self-metathesis of 1,2-epoxyhex-5-ene (but-3-enyloxirane) and its cross-metathesis with methyl acrylate and acrylonitrile catalyzed with ruthenium compounds as well as tandem design of these metatheses and consecutive hydrogenation of their products by gaseous hydrogen have been optimized. The following influences have been studied and tuned: (i) type of the catalyst (Grubbs, Hoveyda, Zhan) and its concentration and method of dosing, (ii) concentration of reactants and additives, (iii) type of solvent, and (iv) reaction temperature. Reactions were monitored by the GC, GC and MS methods and the products were characterized by the NMR method. Methyl 6,7-epoxyheptanoate (methyl 5-oxiranylpentanoate) obtained by the tandem...
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Preparation and properties of building blocks of specialty polymers
Šichová, Kristýna ; Svoboda, Jan (advisor) ; Sedláček, Jan (referee)
This Diploma Thesis presents results obtained by solution of two partial projects: a) Preparation of monomers from renewable sources using metathesis and tandem hydrogenation catalyzed with ruthenium compounds - project solved during my Erasmus stay at the Université de Rennes 1 in France; b) Preparation and properties of ,-bis(tpy)quarterthiophene oligomers carrying ionic side groups as oligomonomers for polyelectrolyte conjugated dynamers - project solved at the Department of Physical and Macromolecular Chemistry, Faculty of Science, Charles University in Prague. Project a): Self-metathesis of 1,2-epoxyhex-5-ene (but-3-enyloxirane) and its cross-metathesis with methyl acrylate and acrylonitrile catalyzed with ruthenium compounds as well as tandem design of these metatheses and consecutive hydrogenation of their products by gaseous hydrogen have been optimized. The following influences have been studied and tuned: (i) type of the catalyst (Grubbs, Hoveyda, Zhan) and its concentration and method of dosing, (ii) concentration of reactants and additives, (iii) type of solvent, and (iv) reaction temperature. Reactions were monitored by the GC, GC and MS methods and the products were characterized by the NMR method. Methyl 6,7-epoxyheptanoate (methyl 5-oxiranylpentanoate) obtained by the tandem...
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Synthesis and properties of complex π-electron systems with helical chirality
Houska, Václav ; Stará, Irena (advisor) ; Machara, Aleš (referee)
Planar shape-persistent macrocycles have been known for a long time and are routinely synthesized today. Non-planar 3D structures, however, still remain challenging synthetic targets in many cases. The objective of this Thesis was to develop a synthetic route to shape-persistent macrocycles containing dibenzo[5]helicene or its derivatives as structural units employing alkene and alkyne metathesis. The Introduction focuses on various methods of the macrocycle synthesis, on alkyne metathesis, and synthesis of helicenes is shortly reviewed as well. Then, the first part of Results and discussion describes the synthesis of 3,16-dichlorodibenzo[5]helicene and its derivatives. In the second part, the macrocycle synthesis from these dibenzohelicenes is discussed. The Experimental part provides a detailed description of performed experiments along with characterization of all new compounds prepared.
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