Oxidation and reduction processes for 1,10-phenanthroline derivatives and their analogs

Rozprawa doktorska podzielona jest na trzy części: wstęp teoretyczny, badania własne oraz część eksperymentalną. Wstęp teoretyczny podzielony jest na poszczególne rozdziały, w których opisano: otrzymywanie, zastosowanie i funkcjonalizacje pochodnych 1,10-fenantroliny, chinoliny oraz właściwości elektrochemiczne wybranych N-heterocykli. W badaniach własnych opisano syntezy wybranych symetrycznych i niesymetrycznych pochodnych 1,10-fenantroliny oraz ich funkcjonalizację a także reakcje utleniania i hydrolizy ww. związków. Poza tym przedstawiono badania elektrochemiczne, w których zaproponowano mechanizmy utlenienia i redukcji badanych związków. Dodatkowo przedstawiono syntezy i funkcjonalizacje pochodnych chinoliny i benzo[h]chinoliny oraz reakcje VNS dla wybranych pochodnych nitrochinoliny. Część eksperymentalna zawiera procedury otrzymywania związków, analizę spektralną produktów oraz spis instrumentów, z których korzystano podczas realizacji tej pracy

Synthesis and Electrochemical and Spectroscopic Characterization of 4,7-diamino- 1,10-phenanthrolines and Their Precursors

New approaches to the synthesis of 4,7-dichloro-1,10-phenanthrolines and their corresponding 9H-carbazol-9-yl-, 10H-phenothiazin-10-yl- and pyrrolidin-1-yl derivatives were developed. Their properties have been characterized by a combination of several techniques: MS, HRMS, GC-MS, electronic absorption spectroscopy and multinuclear NMR in both solution and solid state including 15N CP/MAS NMR. The structures of 5-fluoro-2,9-dimethyl-4,7-di(pyrrolidin- 1-yl)-1,10-phenanthroline (5d), 4,7-di(9H-carbazol-9-yl)-9-oxo-9,10-dihydro-1,10-phenanthroline-5- carbonitrile (6a) and 4,7-di(10H-phenothiazin-10-yl)-1,10-phenanthroline-5-carbonitrile (6b) were determined by single-crystal X-ray diffraction measurements. The nucleophilic substitutions of hydrogen followed by oxidation produced compounds 6a and 6b. The electrochemical properties of selected 1,10-phenanthrolines were investigated using cyclic voltammetry and compared with commercially available reference 1,10-phenanthrolin-5-amine (5l). The spatial distribution of frontier molecular orbitals of the selected compounds has been calculated by density functional theory (DFT). It was shown that potentials of reduction and oxidation were in consistence with the level of HOMO and LUMO energies

Synthesis, electrochemical and spectroscopic characterization of selected quinolinecarbaldehydes and their Schiff base derivatives

A new approach to the synthesis of selected quinolinecarbaldehydes with carbonyl groups located at C5 and/or in C7 positions is presented in this paper in conjunction with spectroscopic characterization of the products. The classical Reimer-Tiemann, Vilsmeier-Haack and Duff aldehyde synthesis methods were compared due to their importance. Computational studies were carried out to explain the preferred selectivity of the presented formylation transformations. A carbene insertion reaction based on Reimer-Tiemann methodology is presented for making 7-bromo-8-hydroxyquinoline-5-carbaldehyde. Additionally, Duff and Vilsmeier-Haack reactions were used in the double formylation of quinoline derivatives and their analogues benzo[h]quinolin-10-ol, 8-hydroxy-2-methylquinoline-5,7-dicarbaldehyde, 8-(dimethylamino) quinoline-5,7-dicarbaldehyde and 10-hydroxybenzo[h]quinoline-7,9-dicarbaldehyde. Four Schiff base derivatives of 2,6-diisopropylbenzenamine were prepared from selected quinoline-5-carbaldehydes and quinoline-7-carbaldehyde by an efficient synthesis protocol. Their properties have been characterized by a combination of several techniques: MS, HRMS, GC-MS, FTIR, electronic absorption spectroscopy and multinuclear NMR. The electrochemical properties of 8-hydroxy-quinoline-5-carbaldehyde, 6-(dimethylamino)quinoline-5-carbaldehyde and its methylated derivative were investigated, and a strong correlation between the chemical structure and obtained reduction and oxidation potentials was found. The presence of a methyl group facilitates oxidation. In contrast, the reduction potential of methylated compounds was more negative comparing to non-methylated structure. Calculations of frontier molecular orbitals supported the finding. The structures of 8-hydroxy-2-methylquinoline-5,7-dicarbaldehyde and four Schiff bases were determined by single-crystal X-ray diffraction measurements

Spectroelectrochemical properties of 1,10- phenanthroline substituted by phenothiazine and carbazole redox-active units

Complexes of 1,10-phenanthrolines with cations of transition metals have broad range of applications. This work aims at designing and investigating phenothiazine and carbazole substituted 1,10-phenanthrolines as ligands for future complexes with transient metal cations. The combined electrochemical, spectroelectrochemical and DFT studies were employed to demonstrate the effect of broken symmetry in substituted 4,7-di(phenothiazine)-1,10-phenanthrolines on their spectroelectrochemical properties. A reversible color change (new absorption band around 500 nm) due to phenothiazine radical cation was observed in the first oxidation step. Results further indicate that phenothiazine substituents behave as two equivalent but almost electronically isolated redox centres. The work additionally presents a comprehensive reaction mechanistic study of oxidation and reduction processes complemented by HPLC-MS/MS identification

Direct amination of nitroquinoline derivatives via nucleophilic displacement of aromatic hydrogen

The vicarious nucleophilic substitution of hydrogen (VNS) reaction in electron-deficient nitroquinolines was studied. Properties of all new products have been characterized by several techniques: MS, HRMS, FTIR, GC-MS, electronic absorption spectroscopy, and multinuclear NMR. The structures of 4-chloro-8-nitroquinoline, 8-(tert-butyl)-2-methyl-5-nitroquinoline, 9-(8-nitroquinolin-7-yl)-9H-carbazole and (Z)-7-(9H-carbazol-9-yl)-8-(hydroxyimino)quinolin-5(8H)-one were determined by single-crystal X-ray diffraction measurements. The 9-(8-nitroquinolin-7-yl)-9H-carbazole and (Z)-7-(9H-carbazol-9-yl)-8-(hydroxyimino)quinolin-5(8H)-one illustrate the nitro/nitroso conversion within VNS reaction. Additionally, 9-(8-isopropyl-2-((8-isopropyl-2-methyl-5-nitroquinolin-6-yl)methyl)-5-nitrosoquinolin-6-yl)-9H-carbazole is presented as a double VNS product. It is postulated that the potassium counterion interacts with the oxygen on the nitro group, which could influence nucleophile attack in that way