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Orgonophosphorus analogues of triphosphate
Šrein, Jakub ; Kubíček, Vojtěch (advisor) ; Štěpnička, Petr (referee)
Two substances were prepared in this work, both with PCPCP structure motif. The motif is similar to ATP molecule, although the oxygen bridges are replaced with methylene groups. Both compounds were characterized by mass spectrometry and NMR spectroscopy. Since bis(methylenephosphonato)phosphinate is soluble in water, four pKa values were determined. Both prepared compounds have potential to serve as chelating ligands. Powered by TCPDF (www.tcpdf.org)
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Aminophosphinic acids
Kruliš, Tomáš ; Kubíček, Vojtěch (advisor) ; Gyepes, Róbert (referee)
Two phosphinic acids were prepared: 1-hydroxy-ethan-1,1-bis[N,N- bis(karboxymethyl)aminomethyl]phosphinic acid; H6L1 and methylenebis[N,N- bis(karboxymethyl)aminomethyl]phosphinic acid; H6L2 . Acid-base and complexation properties were studied by potenciometric titrations. Complexes of both ligands with Cu2+ ions were studied in detail using UV/VIS spectrometry. Keywords: Organophosphorus synthesis, bisphosphinic acids, coordination properties
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Symmetrical aminophosphinates
Procházková, Soňa ; Kubíček, Vojtěch (advisor) ; Vojtíšek, Pavel (referee)
Title: Symmetrical aminophosphinates Author: Bc. Soňa Procházková Department of Inorganic Chemistry, Faculty of Science, Charles University Supervisor: RNDr. Vojtěch Kubíček, Ph.D. Supervisor's email address: kubicek@natur.cuni.cz ABSTRACT Two types of α-aminophosphinates were prepared and studied: phosphinate analogues of iminodiacetic acid − aminobis(methyl(hydroxymethyl)phosphinic acid) (IDPhm ) and aminobis(methyl(2-carboxyethyl)phosphinic acid) (IDPce ), and bis(aminomethyl- phosphinates) − (hydroxy(fenyl)methylen)bis(aminomethylphosphinic acid) (PheOHABPin) and (methylen)bis(aminomethylphosphinic acid) (ABPin). All prepared compounds were fully characterized (by NMR, MS, elemental analysis). One crystal structure was determined by X-ray singlecrystal analysis. The diphosphinates were synthesized by Mannich type reaction, whereas the bis(aminomethylphosphinates) were prepared by multistep synthesis including reactive silylesters. Compounds were prepared in moderate or good yields Acid-base and coordination properties of ligands were investigated and compared by potentiometric and NMR titrations. The values of protonation constants of aminogroups, which determine stability of complexes, showed surprising results. An extremely low basicity of nitrogen atom was found in diphosphinates. So, these compounds...
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Reactivity and properties of triphosphate analogues
Šrein, Jakub ; Kubíček, Vojtěch (advisor) ; Vojtíšek, Pavel (referee)
Reactions leading to cyclization on methylene bridges in PCPCP structure motif were investigated. It was found, that these reactions result in number of various isomers. Some of these isomers were characterized by NMR and MS spectroscopy, but none was isolated. Further, acid-base properties of bis(methylenephosphonato)phosphineic acid were investigated. Formation of complexes was studied with lithium(I), calcium(II), copper(II) and zinc(II) cations. Furthermore, interaction between bis(methylenephosphonato)phosphinic acid and ethylenediamine was investigated by NMR and potentiometric titration. The results show formation of H-bond-based adducts.
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Complexes of aminoalkylphosphineoxides
Mészáros, Bence ; Kubíček, Vojtěch (advisor) ; Mosinger, Jiří (referee)
Title: Comlpexes of aminoalkylphosphineoxides Author: Bence Mészáros Department: Department of Inorganic Chemistry, Faculty of Science UK Supervisor: doc. RNDr. Vojt ch Kubí ek, Ph.D. Supervisor's e-mail address: kubicek@natur.cuni.cz Three selected aminoalkylphosphine oxides were synthesized: Aminomethyl(diphenyl)phosphine oxide, N-piperidylmethyl(diphenyl)phosphine oxide, N,N-diethylaminomethylbis(hydroxomethyl)phosphine oxide. All prepared substances were characterized by NMR spectroscopy and mass spectrometry. The aminomethyl(diphenyl)phosphine oxide and N-piperidylmethyl(diphenyl)phosphine oxide were obtained in the solid state as single crystals and their structure was determined by X-ray analysis. Acid-base and complexing properties of the studied compounds were studied by potentiometric titration and NMR titration. Protonation constants of all three compounds were obtained, stability constants were not determined because of the low solubility of the complexes in water or low stability of the complexes. The structure of the aminomethyl(diphenyl)phosphine oxide complex with Cu2+ was determined by X-ray analysis. Keywords: complexes, organophosphorus synthesis, phosphine oxides, acid-base and complexation properties
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Aminophosphinic acids
Kruliš, Tomáš ; Kubíček, Vojtěch (advisor) ; Gyepes, Róbert (referee)
Two phosphinic acids were prepared: 1-hydroxy-ethan-1,1-bis[N,N- bis(karboxymethyl)aminomethyl]phosphinic acid; H6L1 and methylenebis[N,N- bis(karboxymethyl)aminomethyl]phosphinic acid; H6L2 . Acid-base and complexation properties were studied by potenciometric titrations. Complexes of both ligands with Cu2+ ions were studied in detail using UV/VIS spectrometry. Keywords: Organophosphorus synthesis, bisphosphinic acids, coordination properties
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Geminal bis(phosphinates)
David, Tomáš ; Lukeš, Ivan (advisor) ; Grüner, Bohumír (referee) ; Růžička, Aleš (referee)
Slow complexation is one of the major limitations of current macrocyclic chela- tors utilized in nuclear medicine for complexation of metal radionuclides. This property can be improved by ligand design. Among metal radioisotopes, the copper ones (e.g. 60Cu, 61Cu, 62Cu, 64Cu and 67Cu) have become commonly available in recent years and cyclam-derived ligands are the most suitable ligands for Cu2+ complexation. To alter the complexation rate, bis(phosphinic acid) group is promising unit as it is able to complex metal ions in acidic solu- tions. However, geminal bis(phosphinates) represent poorly studied group of compounds and, thus, it is challenging to uncover their properties. Several simple amino-bis(phosphinates) were synthesized and its acid-base and coordi- nation properties were studied. Unlike structurally similar geminal bis(phosphonates), the title compounds showed negligible adsorption onto hydroxyapatite (commonly used model of bone tissue). The obtained knowledge dealing with geminal bis(phosphinates) was utilized in synthe- sis of two novel cyclam derivatives. The ligands (bearing either one geminal bis(phosphinate) or one geminal phosphino-phosphonate pendant arm) were synthesized by highly efficient procedure. The corresponding Cu2+ complexes are formed with very high rates and show...
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Orgonophosphorus analogues of triphosphate
Šrein, Jakub ; Kubíček, Vojtěch (advisor) ; Štěpnička, Petr (referee)
Two substances were prepared in this work, both with PCPCP structure motif. The motif is similar to ATP molecule, although the oxygen bridges are replaced with methylene groups. Both compounds were characterized by mass spectrometry and NMR spectroscopy. Since bis(methylenephosphonato)phosphinate is soluble in water, four pKa values were determined. Both prepared compounds have potential to serve as chelating ligands. Powered by TCPDF (www.tcpdf.org)
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Synthesis of phosphinic acids
Kruliš, Tomáš ; Kubíček, Vojtěch (advisor) ; Schulz, Jiří (referee)
Two types of phosphinic acids were prepared: N,N-bis(carboxymethyl)aminomethyl phosphinic acid and carboxyethylphosphinic acid. Afterwards they were used to synthesize bisphosphinic acids: 1-hydroxy-ethan-1,1-bis[N,N-bis(carboxymethyl)aminomethyl phosphinic] acid and 1-hydroxy-ethan-1,1-bis(carboxyethyl)phosphinic acid. All compounds were characterized by NMR and mass spectroscopy. N,N-bis(carboxymethyl)aminomethylphosphinic acid was synthesized by Mannich type reaction. Carboxyethylphosphinic acid was prepared by alkylation of bis(trimethylsilyloxy)phosphine. Both bisphosphinic acids were prepared by reaction of silylesters of phosphinic acids with acetylchloride. All compounds were prepared in moderate or good yields. Keywords: Organophosphorus synthesis, phosphinic acids, bisphosphinic acids
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