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1
Millan, Barrios Enrique Jose. "Synthesis and electrochemistry of pyrrole derivatives." Thesis, University of Southampton, 1996. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.242418.
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Armitage, Georgina Kate. "The Zav'yalov pyrrole synthesis revisited : some derivatives of 3-hydroxy- and 3-amino-pyrroles." Thesis, University of Huddersfield, 2017. http://eprints.hud.ac.uk/id/eprint/34175/.
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The objective of this study was to investigate the acylative-cyclisation-decarboxylation reactions of enamino acids derived from 1,3-difunctional compounds. Remarkably little is known regarding the generality of these variants of the Zav’yalov pyrrole synthesis, despite their considerable scope for the synthesis of functionalised pyrroles. The cyclisation of diethyl 2-(1-carboxyalkylaminomethylene)malonates provided access to a range of 5-(un)substituted-4-acetoxypyrrole-3-carboxylates. However, in some instances the corresponding 4-ethoxypyrrole-3-carboxylates also accounted for up to 20% of the reaction product. 1-Acetyl-4-ethoxy-5-ethylpyrrole-3-carboxylate was characterised by X-ray crystallography. Some of the (aminomethylene)malonates from bifunctional α-amino acids provided anomalous products. For example, the glutamine-derived enamino malonate gave a 5-acetylpyrrolidin-2-one via a Dakin-West-type reaction. The asparagine-enamino malonate cyclised to 4-acetoxy-1-acetyl-5-cyanomethylpyrrole-3-carboxylate probably via an isosuccinimide intermediate. Several mechanisms for the formation of the pyrrole products have been discussed. A 13C-labelling experiment confirmed that the carboxyl function in the starting material is not incorporated in the product. Evidence for the involvement of a 1,3-oxazolium-5-olate (münchnone) accrued from cyclisation of diethyl 2-(1-carboxymethylaminomethylene)malonate with Ac2O in the presence of dimethyl acetylenedicarboxylate which provided a novel 1-alkenylpyrrole, characterised by X-ray crystallography. An alternative pathway supervenes in the Zav’yalov reaction when α,α-disubstitution of the amino acid prevents münchnone and thus pyrrole formation to afford an N-alkenyloxazolidin-5-one. Novel ethyl 4-(di)acetamido-5-(un)substituted-pyrrole-3-carboxylates and the corresponding 3-carbonitriles have been obtained in good yields via the cyclisation of ethyl 2-(1-carboxyalkylaminomethylene)cyanoacetates and (1-carboxyalkylaminomethylene)malononitriles respectively. Evidence for a different cyclisation pathway, in the former, involving intramolecular acylation of the enaminonitrile moiety was observed. Thus, ethyl (2R*,3S*)-1-acetyl-3-cyano-2,4-diacetoxy-5-methyl-2,3-dihydropyrrole-3-carboxylate was characterised by X-ray crystallography. A wide range of novel 2-alkanoyl- and 2-aroyl-3-(1-carboxyalkylamino)acrylonitriles has been obtained via aminomethylenation of β-ketonitriles. The products from their cyclisations (Ac2O-NEt3) were largely independent of the nature of the acyl group but determined by the substituent in the α-amino acid moiety. The 3-(1-carboxy-1-phenylmethylamino)acrylonitriles provided mixtures of 3-acyl-4-(di)acetamido-5-phenylpyrroles in which the 4-acetamido- derivatives predominated. Contrasting behaviour was displayed by the 3-(1-carboxyalkylamino)acrylonitriles derived from alanine, 2-aminobutyric acid and valine in which the cyclisation followed an unexpected course, via enaminone acylation, to the novel 4-acetoxy-1-acetyl-5-alkylpyrrole-3-carbonitriles in high yields. The acylative cyclisation of the 2-acyl-3-(1-carboxymethylamino)acrylonitriles furnished mixtures of pyrroles. In two cases, 3-acetamido-6-aryl-5-cyanopyran-2-ones, generated by a unique cyclisation pathway were isolated. The structure of the 6-phenyl- derivative was confirmed by unambiguous synthesis. The synthesis and acylative cyclisation of (Z)-2-benzoyl-3-(1-carboxyalkylamino)crotononitriles was investigated. Whereas the 3-(1-carboxyethylamino)- derivative provided 4-acetoxy-1-acetyl-2,5-dimethylpyrrole-3-carbonitrile exclusively, the 3-(1-carboxy-1-phenylmethylamino)crotononitrile afforded a mixture of pyrroles. A remarkable minor component was characterised as 4-acetoxy-1-benzoyl-2-methyl-5-phenylpyrrole-3-carbonitrile, the result of sequential [1,5]-benzoyl migrations of a 3H-pyrrole intermediate. The acylative cyclisation of 3-(1-carboxyalkylamino)-2-tosylacrylonitriles provides access to hitherto unknown 3-diacetamido-4-tosyl- and 3-acetamido-4-tosylpyrroles. Cyclisation of 2-(1-carboxyalkylaminomethylene)dibenzoylmethanes offers an excellent, complementary approach to access 5-(un)substituted-3-benzoyl-4-phenylpyrroles, to the existing tosylmethyl isocyanide-based protocols.
3
Ngwerume, Simbarashe. "Gold-multifaceted catalysis approach to pyrrole synthesis." Thesis, University of Nottingham, 2013. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.604293.
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The work presented in this thesis is concerned with the development of novel approaches to the regioselective synthesis of highly substituted pyrroles from simple starting materials. The work detailed herein covers three main research areas: i) A nucleophilic catalysis method for the concise synthesis of substituted NH- or N-Boc-pyrroles, directly from oximes and alkynes; ii) The development of a novel gold-multifaceted catalysis (gold-MFC) method for the regioselective synthesis NH-pyrroles directly from oximes and alkynes, together with a detailed mechanistic investigation which provides an insight into the mechanistic pathway; iii) studies towards an intramolecular macrocyclisation approach towards the synthesis of substituted pyrroles from oximes and alkynes. i) A novel nucleophilic catalysis / microwave irradiation protocol that provides a succinct synthesis of di-, tri, and tetrasubstituted pyrroles in a single operation will be discussed. This one-pot method relies on the use of a nucleophilic catalyst to regioselectively promote the in situ formation of O-vinyloximes from the reaction of oximes and electron deficient alkynes, which after subjection to microwave irradiation afforded the desired pyrroles as single regioisomers. ii) The main body of work in this thesis concerns the development of a novel gold(I)-catalysed method for the regioselective synthesis of highly substituted pyrroles directly from oximes and electron deficient alkynes. This one-pot method was developed via optimisation of two key gold(I)catalysed steps: the formation of O-vinyloximes and rearrangement of preformed O-vinyloximes into the corresponding pyrrole. The cationic gold species was shown to activate multiple mechanistically distinct steps along the reaction pathway and therefore act as a multifaceted catalyst. Notably, this method provides a concise synthesis of di-, tri- and tetrasubstituted pyrroles which contain a functional group handle in the form of an ester at the 3/4-position for further exploitation. The proposed mechanistic pathway is supported by a novel application of the Huisgen cycloaddition click reaction, which was used to probe the relative stability of substituted O-vinyloximes. Further support for the proposed mechanism was provided by high-temperature lH, 2H{lH}, and 13C{lH} NMR experiments. X-ray crystallographic evidence was used to further support the mechanistic hypothesis by confirming the absolute configuration of the oximes, 0- vinyloximes and pyrroles. iii) Preliminary studies into an unprecedented intramolecular pyrrole formation via the direct addition of an oxime to an alkyne are described. ii
4
鍾惠玲 and Chung Wai-ling Margaret Chiu. "The synthesis and reactions of 3, 5-diaryl-2, 2-bis(ethoxycarbonyl)-2H-pyrroles." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 1986. http://hub.hku.hk/bib/B31230829.
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李思明 and Sze-ming Lee. "An investigation into novel synthetic routes for 3h-pyrroles." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 1989. http://hub.hku.hk/bib/B31209257.
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Maeda, Rina. "Synthesis and Evaluation of the Pyrrole-Imidazole Polyamides for Cancer Treatment." Doctoral thesis, Kyoto University, 2021. http://hdl.handle.net/2433/263806.
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付記する学位プログラム名: 京都大学大学院思修館京都大学
新制・課程博士
博士(総合学術)
甲第23345号
総総博第18号
京都大学大学院総合生存学館総合生存学専攻
(主査)教授 山敷 庸亮, 教授 杉山 弘, 教授 積山 薫
学位規則第4条第1項該当
Doctor of Philosophy
Kyoto University
DGAM
7
Mezlova, Marie. "Benzofused thieno[3,2-b]pyrroles-synthesis, electrochemical and spectral behaviour." Paris 7, 2005. http://www.theses.fr/2005PA077212.
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This thesis deals with the synthesis of novel 1,4-diheteropentalene compounds, especially 4H-thieno[3,2-b]indoles and 1H-benzothieno[3,2-b]pyrrole, and the investigation of their electropolymerization. The aim was to prepare new conducting polymers and to determine how the structure of the monomer influences their electrochemical and spectral properties. The investigation can be subdivided into four parts. 1. In the context of the research on 1,4-diheteropentalenes performed in our laboratory in recent years, I have designed and prepared a series of novel thienoindoles and the isomeric benzothienopyrrole. The known synthetic procedure was extended to the preparation of thienoindoles with various electron-donating substituents in the benzene ring. After several unsuccessful synthetic approaches I found a new synthetic route to the thienoindole core. 2. The compounds synthesized are ideal candidates for the preparation of new conducting polymers which can be obtained by their electropolymerization. This hypotesis has already been proved by the polymerization of structurally related thieno[3,2-b]benzomiophenes. Thus, the second part of my research work has been focused on the electrochemical behaviour of the compounds prepared and on the electrosynthesis of polymers. This research work represents the first attempt to polymerize these 1,4-diheteropentalenes. 3. As a consequence with my research on polymer preparation, I have been also engaged in the investigation of their physicochemical and spectral properties. After the appropriate analyses I found that most of the polymers, obtained as films, are electroactive or conducting and consist of an oligomer mixture. Moreover, several exhibit very interesting spectral properties which designate them for applications in electrochromic devices or polymer-based light-emitting diodes. 4. I have also focused on the relationship between the structure of the monomer and the properties of the polymer. Electron-donating groups introduced into the thienoindole core, as well as the order of the pentalenes in the fused heterocycle, change basically the monomer reactivity towards polymerization, and determine the electroactivity and structure of the products. In addition, electron-donating substituents in the benzene ring of thienoindole have an essential influence on the spectral properties of the polymers.
8
Lee, BoRa. "The Synthesis of Chemically Well-defined and Biocompatible Oligopyrroles for Tissue Engineering Applications." Phd thesis, Canberra, ACT : The Australian National University, 2016. http://hdl.handle.net/1885/102346.
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The studies described in this Thesis involve the development of syntheses of a wide range of chemically well-defined oligopyrroles for tissue engineering applications. In particular, the outcomes of a detailed investigation into the preparation of certain types of such oligopyrroles are presented using Suzuki-Miyaura cross-coupling reactions as a means for linking pyrrole-based building blocks.
9
楊小雯 and Siu-man Yeung. "The synthesis and reactions of 3H-pyrroles bearing methyl and aryl groups." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 1991. http://hub.hku.hk/bib/B31210119.
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Sandrin, Franco. "Lewis acid catalyzed reactions of 1-benzyl-2, 5-bis (trimethylsiloxy) pyrrole." Thesis, McGill University, 1985. http://digitool.Library.McGill.CA:80/R/?func=dbin-jump-full&object_id=66047.
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Cai, Xuediao. "Synthesis and Characterization of Pyrrole Based Adhesion Promoter Systems on Oxide Substrates." Doctoral thesis, Saechsische Landesbibliothek- Staats- und Universitaetsbibliothek Dresden, 2005. http://nbn-resolving.de/urn:nbn:de:swb:14-1109334028224-37122.
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For grafting polypyrrole on oxidized surfaces, 3-substituted pyrrole alkyl phosphonic acids, 11-(pyrrol-3-yl undecyl) trimethoxysilanes and 1-substituted pyrrole alkyl organosilanes with different chain length were designed and successfully synthesized as adhesion promoters. These new derivatives were studied for their adsorption behavior on oxide substrates and chemical or electrochemical deposition of polypyrrole over modified oxide surface or electrodes. Several analytical techniques such as contact angle measurement, surface plasmon resonance spectroscopy (SPR), UV-VIS Spectroscopy, grazing incident FTIR, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and atomic force microscopy (AFM) were employed to characterize the adsorbed layers on different substrates. Contact angle measurement and ellipsometry data showed that high concentrations in apolar hydrocarbon solvent and long reaction times are sufficient to form tightly packed monolayer of 1-substituted pyrrole alkyl monochlorosilanes (PMCS) on substrates. Adsorption kinetics were studied by SPR and showed that the adsorption took place within a few seconds, then continuously increased and reached a plateau. The orientation of these synthesized monomers is investigated to be well-suited for use as adhesion promoter. CV-measurements showed that 3-substrated pyrrole derivatives had lower oxidation potential, whereas 1-substituted pyrrole derivatives had higher oxidation potential compared with pyrrole. Surface deposition of polypyrrole on the adhesion promoter modified (silane-modified and phosphonic acid-modified) substrates by chemical and electrochemical polymerization were investigated. PPy films formed on the modified surfaces by surface chemical polymerization showed a better adhesion compared to those on the unmodified surfaces. The morphology of PPy films was influenced by the alkyl chain length of the adhesion promoter and the deposition condition, such as choice of oxidant and solvent. The thickness of the resulting PPy films were controlled by the polymerization conditions, such as choice of solvent, deposition time, pyrrole to oxidant ratio and monomer concentration. The thickness of the deposited PPy film was estimated in the range of 10-400 nm by AFM and ellipsometry. The electrical properties were studied by current-voltage (j-V) measurement. Temperature dependence of j-V characteristics of Si/SiO2/PPy/PMCS-16/Al films revealed that the current increases with temperature, the film shows a typical semiconductor behavior. The use of these adhesion promoters modified electrode for electrochemical polymerization resulted in adhesive polypyrrole films.Also the 3-substituted pyrrole phosphonic acids were found to be homo-and co-polymerizable (with pyrrole) under chemical methods. TGA showed that homopolymers are less stable than polypyrrole due to the 3-substitution. he homopolymer of 3-substituted phosphonic acid derivatives of pyrrole is soluble. Films coated from the MeOH solution of homopolymer could be successfully used as humidity sensors. It is observed that the resistivity of the 3-substituted homopolypyrrole sensors increases and capacitance decreases during exposure to humid air. The polypyrrole films obtained by surface chemical polymerization was also used as humidity sensors.
12
Cai, Xuediao. "Synthesis and Characterization of Pyrrole Based Adhesion Promoter Systems on Oxide Substrates." Doctoral thesis, Technische Universität Dresden, 2004. https://tud.qucosa.de/id/qucosa%3A24463.
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For grafting polypyrrole on oxidized surfaces, 3-substituted pyrrole alkyl phosphonic acids, 11-(pyrrol-3-yl undecyl) trimethoxysilanes and 1-substituted pyrrole alkyl organosilanes with different chain length were designed and successfully synthesized as adhesion promoters. These new derivatives were studied for their adsorption behavior on oxide substrates and chemical or electrochemical deposition of polypyrrole over modified oxide surface or electrodes. Several analytical techniques such as contact angle measurement, surface plasmon resonance spectroscopy (SPR), UV-VIS Spectroscopy, grazing incident FTIR, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and atomic force microscopy (AFM) were employed to characterize the adsorbed layers on different substrates. Contact angle measurement and ellipsometry data showed that high concentrations in apolar hydrocarbon solvent and long reaction times are sufficient to form tightly packed monolayer of 1-substituted pyrrole alkyl monochlorosilanes (PMCS) on substrates. Adsorption kinetics were studied by SPR and showed that the adsorption took place within a few seconds, then continuously increased and reached a plateau. The orientation of these synthesized monomers is investigated to be well-suited for use as adhesion promoter. CV-measurements showed that 3-substrated pyrrole derivatives had lower oxidation potential, whereas 1-substituted pyrrole derivatives had higher oxidation potential compared with pyrrole. Surface deposition of polypyrrole on the adhesion promoter modified (silane-modified and phosphonic acid-modified) substrates by chemical and electrochemical polymerization were investigated. PPy films formed on the modified surfaces by surface chemical polymerization showed a better adhesion compared to those on the unmodified surfaces. The morphology of PPy films was influenced by the alkyl chain length of the adhesion promoter and the deposition condition, such as choice of oxidant and solvent. The thickness of the resulting PPy films were controlled by the polymerization conditions, such as choice of solvent, deposition time, pyrrole to oxidant ratio and monomer concentration. The thickness of the deposited PPy film was estimated in the range of 10-400 nm by AFM and ellipsometry. The electrical properties were studied by current-voltage (j-V) measurement. Temperature dependence of j-V characteristics of Si/SiO2/PPy/PMCS-16/Al films revealed that the current increases with temperature, the film shows a typical semiconductor behavior. The use of these adhesion promoters modified electrode for electrochemical polymerization resulted in adhesive polypyrrole films.Also the 3-substituted pyrrole phosphonic acids were found to be homo-and co-polymerizable (with pyrrole) under chemical methods. TGA showed that homopolymers are less stable than polypyrrole due to the 3-substitution. he homopolymer of 3-substituted phosphonic acid derivatives of pyrrole is soluble. Films coated from the MeOH solution of homopolymer could be successfully used as humidity sensors. It is observed that the resistivity of the 3-substituted homopolypyrrole sensors increases and capacitance decreases during exposure to humid air. The polypyrrole films obtained by surface chemical polymerization was also used as humidity sensors.
13
趙百勤 and Pak-kan Chiu. "Isolation of hydroxypyrrolines in the Paal-Knorr reaction; and the synthesis and properties of 3H-phrroles carrying an ester or nitrilegroup at C-3." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 1988. http://hub.hku.hk/bib/B31231524.
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Subasi, Nuriye Tuna. "Novel Synthetic Methodologies For Heeocycles As Building Blocks In Drug Synthesis." Phd thesis, METU, 2011. http://etd.lib.metu.edu.tr/upload/12613028/index.pdf.
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Nitrogen containing heterocycles have always constituted a subject of great interest due to their wide presence in biologically important compounds so the development of efficient methods for the preparation of pyrrole derivatives and formation of new pyrrole-based heterocyclic compounds are an attractive goal in heterocyclic chemistry. In this study, starting from dimethoxytetrahydrofurane and amino acid esters, unsubstituted pyrrole derivatives, and treatment of amino acid esters with convenient chloroenones 1,2-disubstituted and 1,2,4-trisubstituted pyrrole derivatives were synthesized without racemization. Reaction of unsubstituted pyrrole derivatives with norephedrine toward inter- and intramolecular cyclizations give new interesting heteropolycylic compounds with oxazole-pyrrole-pyrazine structures. Study continued with cyclization reaction of these synthesized substituted and unsubstituted pyrrole derivatives with BBr3 and new bicyclic pyrrole derivatives were obtained in moderate yield.
15
Kawamoto, Yusuke. "Synthesis and Biological Evaluation of Pyrrole-Imidazole Polyamide Probes for Visualization of Telomeres." Kyoto University, 2018. http://hdl.handle.net/2433/232264.
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Roth, Steven Daniel. "Synthesis and investigations of di-, tri-, and tetra-pyrrole analogs of bilirubin IXa /." abstract and full text PDF (UNR users only), 2007. http://0-gateway.proquest.com.innopac.library.unr.edu/openurl?url_ver=Z39.88-2004&rft_val_fmt=info:ofi/fmt:kev:mtx:dissertation&res_dat=xri:pqdiss&rft_dat=xri:pqdiss:3294914.
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Thesis (Ph. D.)--University of Nevada, Reno, 2007."December, 2007." Includes bibliographical references (leaves 125-129). Library also has microfilm. Ann Arbor, Mich. : ProQuest Information and Learning Company, [2008]. 1 microfilm reel ; 35 mm. Online version available on the World Wide Web.
17
Jackson, Delwin S. "Synthesis and evaluation of peptidyl and non-peptidyl diphenyl phosphonate esters and a mechanistic study of hydroxy pyrrole and 4-nitroanlide substrates with serine proteases." Diss., Georgia Institute of Technology, 1996. http://hdl.handle.net/1853/27142.
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Bérubé, Christian Denis. "Delving into the rare-earth metal chemistry of pyrrole-based ligands: Synthesis and analysis of divalent samarium and ytterbium pyrrolide complexes." Thesis, University of Ottawa (Canada), 2001. http://hdl.handle.net/10393/9097.
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The reaction of YbI2(THF)2 with diphenylmethyldipyrrolide leads to a complex reaction from which is obtained an octameric divalent Yb macrocycle (Diphenyldipyrromethanedi-yl-Yb)8 2.1 as a major product, but from which is also isolated a tetrameric cyclic Yb(II)-oxo complex [(diphenyldipyrrolyl-methanedi-yl)Yb]4[(K2)(THF) 6](mu-O)•2(THF) 2.2•2(THF) and a monomeric Yb(III) complex, Yb(diphenyldipyrrolylmethane-di-yl)3(K 3THF3) 2.3, as minor products. Complex 2.1 is analogous to the Sm(II) dipyrrolide octameric clusters obtained under an argon atmosphere, which are thought to represent the intermediate species in the formation of dinitrogen complexes. The reactions of SmI2(THF)2 and YbI2(THF) 2 with the alkali salts of 2,5-dimethylpyrrole, or the reaction of SMCl 3(THF)3 and YbCl3(TBF)3 with the same ligands followed by reduction with the appropriate alkali metals, led to the formation of divalent mono- and polynuclear complexes. (Abstract shortened by UMI.)
19
Connolly, Emma Anne. "Macrocycles as platforms for mono-and dinuclear calcium chemistry." Thesis, University of Edinburgh, 2017. http://hdl.handle.net/1842/25879.
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This thesis presents the design and structure of a number of Schiff-base pyrrole macrocycles, their use in the formation of mono- and dinuclear calcium complexes, and reactions with various alkali- and transition metals to form mixed-metal clusters. Chapter One introduces the range of Schiff-base macrocycles with tuneable properties for various synthetic applications. Previously reported complexes of various s-, d- and f-block metals in these macrocyclic frameworks are also discussed. Research into calcium chemistry is reviewed, both in catalysis of synthetic organic processes, and in synthetic modelling of reaction clusters found in protein structures. Chapter Two details the synthesis of three monometallic calcium complexes utilising Schiff base macrocycles H4LEt and H4LA, and dipyrrin ligand HLD. Reactions of Ca(THF)2(H2LEt) with transition metal halides and amines is outlined, leading to the formation of M2(LEt) (M = Fe, Co, Cu). Deprotonation of Ca(THF)2(H2LEt) with alkali metal amines forms calcium-alkali metal complexes; further reactivity of these with transition metal halides demonstrates unusual stoichiometry in the synthesis of mixed-metal clusters. Some of these complexes were assessed for catalytic activity in the hydroamination of isocyanates. Chapter Three describes the synthesis and characterisation of bimetallic calcium complexes of the ligands H4LEt, H4LA and H4LS5. Reactions of Ca2(THF)2(μ- THF)(LEt) with a range of small molecules - including H2O, LiOH and KOH - is outlined. In particular, reactivity of Ca2(THF)2(μ-THF)(LEt) with NaOH yielded calcium-alkali metal clusters Ca2(THF)2(μ-OH)(Na{THF}2)(LEt) and Ca2(THF)2(μ- OH)2(Na{THF})2(LEt), which displayed alternate wedged and bowl-shaped conformations of the macrocycle ligand. Further homobimetallic complex syntheses of M2(LEt) (M = Sn, Mn, Sr) are also outlined for comparison to calcium complexes. Chapter Four presents a summary of the work presented in this thesis, and Chapter Five outlines the full experimental procedures and analytical data for all described complexes.
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Yeisley, Christopher R. "Synthesis of Early Transition Metal Complexes Supported by Pyrrolyl and Indolyl Based Ligands." University of Toledo / OhioLINK, 2013. http://rave.ohiolink.edu/etdc/view?acc_num=toledo1363282845.
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Kim, Jisu. "Acetylene coupling chemistry on copper surfaces : towards a new route for the heterogeneous synthesis of pyrrole." Thesis, University of Cambridge, 2004. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.615691.
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Mikhedkina, E. I., I. I. Melnik, A. V. Tsygankov, D. T. Kozhich, and M. V. Vasyleiko. "Synthesis of ethyl 3,5-dimethyl-4-(aryliminomethyl)-1h-pyrrole-2-carboxylates and their reactions with thioglycolic acid." Thesis, Ekskluziv Publ, 2018. http://repository.kpi.kharkov.ua/handle/KhPI-Press/45015.
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Kayalar, Metin. "Synthesis Of 1,2,3,5-tetrasubstituted Pyrrole Derivatives Via 5-exo-dig Type Cyclization And Stereoselective Functionalisation Of Ferrocene Derivatives." Master's thesis, METU, 2005. http://etd.lib.metu.edu.tr/upload/12605757/index.pdf.
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ABSTRACT
SYNTHESIS OF 1,2,3,5-TETRASUBSTITUTED PYRROLE DERIVATIVES VIA 5-EXO-DIG TYPE CYCLIZATION AND STEREOSELECTIVE FUNCTIONALISATION OF FERROCENE DERIVATIVES
Metin Kayalar
M.S., Department of Chemistry
Supervisor: Prof. Dr. Ayhan S. Demir
January 2005, 102 pages
A convenient and new method for the synthesis of 1,2,3,5-tetrasubstituted pyrrole derivatives starting from 1,3,-dicarbonyl compounds through acid catalyzed cyclization reaction is described. Alkylation of 1,3-dicarbonyl compound with propargyl bromide followed by one step cyclization with the introduction of primary amines in the presence of catalytic amount of triflouroacetic acid (TFA) affords the corresponding pyrrole derivatives in high yields.
The investigations on the studies of developing a new method for catalytic and stereoselective functionalisation of ferrocene derivatives were summarized. Functionalisation studies were carried out in three main strategy the first one of which is carboxylation, second one is arylation and the last one is oxidative cross-coupling with α
, &
#946
-unsaturated carbonyl compounds.
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François, Benjamin. "Utilisation d’organoboranes fonctionnalisés pour la construction de structures polycycliques." Thesis, Rennes 1, 2018. http://www.theses.fr/2018REN1S114.
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Les composés organoborés constituent des outils remarquables en synthèse organique de par leur chimie très diversifiée. Les travaux présentés dans ce mémoire abordent de nouveaux aspects de leur réactivité. Une méthode de synthèse rapide et efficace de 9-hydroxyfluorènes est décrite via une séquence tandem Suzuki/ aldolisation phénolique. Ce processus a été ensuite étendu aux 9-aminofluorènes en ajoutant simplement comme troisième partenaire diverses amines au milieu réactionnel. Des hypothèses mécanistiques sont proposées pour rationaliser ces résultats expérimentaux. Dans une deuxième partie, est présentée une étude articulée autour de la mise en œuvre de réactions ène sur des diènes borylés 1,3. Les produits ainsi obtenus sont ensuite utilisés comme intermédiaires clé de structures polycycliques plus complexes. Enfin, le troisième chapitre est consacré à une nouvelle voie d'accès aux pyrroles C-fusionnés à partir de diènes cycliques borylés, ces derniers étant préparés par hydroboration d'énynes, bora-Wittig ou métathèse. Une grande diversité structurale est alors accessible à partir de ces précurseurs d'accès aiséOrganoboron compounds are remarkable tools in organic synthesis due to their very diversified chemistry. The work presented in this thesis addresses new aspects of their reactivity. A rapid and efficient synthesis of 9-hydroxyfluorenes is described via a tandem Suzuki/phenol aldolisation sequence. This process was then extended to 9-aminofluorenes by simply adding various amines to the reaction medium as the third partner. Mechanistic hypotheses are proposed to rationalize these experimental results. In a second part, was presented a study articulated around the implementation of ene reactions on borylated 1,3-dienes. The products thus obtained are then used as key intermediates of more complex polycyclic scaffolds. Finally, the third chapter is dedicated to a new access to C-fused pyrroles from borylated cyclic dienes, the latter being prepared by hydroboration of enynes, boron-Wittig or metathesis reactions. A great structural diversity is then accessible from these easily prepared precursors
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Bulut, Umut. "Synthesis And Characterization Of Conducting Copolymers Of Carboxylic Acid Multithiophene Functionalized Monomers." Master's thesis, METU, 2003. http://etd.lib.metu.edu.tr/upload/1108018/index.pdf.
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Synthesis of 2-[(3-thienylcarbonyl)oxy]ethyl 3-thiophene carboxylate
(TOET), 2,3-bis-[(3-thienylcarbonyl)oxy]propyl 3-thiophene carboxylate (TOPT),
and 3-[(3-thienylcarbonyl)oxy]-2,2-bis{[(3-thienylcarbonyl)oxy]}propyl 3-
thiophene carboxylate (TOTPT), and their copolymerization either with
thiophene or pyrrole were achieved. The chemical structures of the monomers
were investigated by Nuclear Magnetic Resonance Spectroscopy (NMR) and
Fourier Transform Infrared Spectroscopy (FTIR). Electrochemical behavior of
the monomers and copolymers were studied by cyclic voltammetry (CV). The
resultant conducting copolymers were characterized via FTIR, Thermal Gravimetry Analysis (TGA), Differential Scanning Calorimetry (DSC), and
morphologies of the films were inspected by Scanning Electron Microscope
(SEM). Conductivities of the samples were measured by using four-probe
technique. The electrochromic and spectroelectrochemical properties of the
copolymers were investigated.
26
Epik, Bugra. "The Synthesis Of Donor-acceptor Type Electroactive Monomers Bearing Pyrrole And Selenophene As The Donor Moieties And Their Polymers." Master's thesis, METU, 2010. http://etd.lib.metu.edu.tr/upload/2/12611341/index.pdf.
Full textAbstract:
Synthesis of new electroactive monomers are highly desired since these compounds can be utilized as active layers in many device applications such as ECDs, LEDs and solar cells. Pyrrole and selenophene bearing polymers were also proven to be excellent candidates as electrochromic materials. Benzothiodiazole can be coupled to to pyrrole and selenophene yield materials that can be polymerized to give donor acceptor type polymers. These donor-acceptor type materialsPoly(4,7-di(1H-pyrrol-2-yl)benzo[c][1,2,5]thiadiazole P(PYBTPY) and poly(4,7-di(selenophen-2-yl)benzo[c][1,2,5]thiadiazole P(SEBTSE) were synthesized via bromination, stannylation and Stille coupling reactions. Electrochemical and electrochromic properties of the polymers were examined in detail.
27
Berg, Keimpe Jan van den. "Heterocyclic analogs of o-xylylene a study of the synthesis and reactivity of dimethylene derivatives of thiophene and pyrrole /." [S.l. : [Groningen : s.n.] ; University Library Groningen] [Host], 1990. http://irs.ub.rug.nl/ppn/292990278.
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Turkarslan, Ozlem. "Synthesis, Characterization And Electrochromic Properties Of Conducting Copolymers Of Terephthalic Acid Bis-(thiophen-3-ylmethyl)thioester With Thiophene And Pyrrole And Conducting Polymer Of 1-(4-fluorophenyl)-2,5-di(thiophen-2-yl)-1h-pyrrole." Master's thesis, METU, 2006. http://etd.lib.metu.edu.tr/upload/12607169/index.pdf.
Full textAbstract:
Terephthalic acid bis-(thiophen-3-ylmethyl)thioester (TTMT) was synthesized via the reaction of thiophen-3-ylmethanethiol with terephthaloyl dichloride. Nuclear magnetic resonance (1H-NMR) and Fourier transform infrared (FTIR) spectroscopies were utilized for the characterization of the monomer. This 3-functionalized thiophene monomer was polymerized in the presence of thiophene (Th) and pyrrole (Py) upon constant potential application in acetonitrile/tetrabutylammonium tetrafluoroborate (TBAFB). The resulting copolymers were characterized via cyclic voltammetry (CV), FTIR, differential scanning calorimetry (DSC), scanning electron microscopy (SEM), four-probe technique conductivity measurement and UV-Vis spectroscopy. Spectroelectrochemical analysis of P(TTMT-co-Th) revealed π
to &
#960
* transition at 476 nm with a band gap of 2.0 eV whereas, &
#955
max and Eg were found as 375 nm and 2.4 eV for P(TTMT-co-Py), respectively. Dual type electrochromic devices (ECDs) of P(TTMT-co-Th) and P(TTMT-co-Py) with poly(3,4-ethylenedioxythiophene) (PEDOT) were constructed. Spectroelectrochemistry, switching ability, open circuit memory and stability of the devices were examined by UV-Vis spectroscopy and cyclic voltammetry. The device P(TTMT-co-Th)/PEDOT switches between brown and blue upon application of 0.0 V and +2.6 V, respectively with 11% optical contrast and 1.1 s as the switching time. On the other hand, P(TTMT-co-Py)/PEDOT ECD exhibits greenish yellow, grayish red and blue colors with the application of -2.4 V, 0.0 V and +0.8 V, respectively and the contrast between extreme potentials was 17.5% with a switching time of 1.6 s. 1-(4-Fluorophenyl)-2,5-di(thiophen-2-yl)-1H-pyrrole (FPTP) was synthesized and polymerized both chemically and electrochemically. Several analytical techniques, such as NMR, FTIR, CV, gel permeation chromatography (GPC), four-probe conductivity measurement, SEM were utilized when applicable. Spectroelectrochemistry experiments reflected a &
#960
to &
#960
* transition at 398 nm with a band gap energy of 1.94 eV for the polymer. A dual type electrochromic device (ECD) of PFPTP and poly(3,4-ethylenedioxythiophene) (PEDOT) was constructed. The device switches between yellowish brown and blue upon application of &
#8211
0.8 V and +1.1 V, respectively. Optical contrast was calculated as 19.4% with a switching time of 1.4 s at maximum contrast point.
29
Zhang, Yu. "SYNTHESIS OF FLUORINATED AND IODINATED CARBOXYETHYLPYRROLE RECEPTOR LIGANDS." Case Western Reserve University School of Graduate Studies / OhioLINK, 2014. http://rave.ohiolink.edu/etdc/view?acc_num=case1380551750.
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30
Park, Saerom [Verfasser], and Oliver [Akademischer Betreuer] Reiser. "Studies on Reactions of Cyclopropanated Pyrrole: Synthesis of Bis-β-homoproline, Tropane- and Pyrrolidinone-derivatives / Saerom Park ; Betreuer: Oliver Reiser." Regensburg : Universitätsbibliothek Regensburg, 2020. http://d-nb.info/1211556581/34.
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31
Ak, Metin. "Synthesis Of Polythiophene And Polypyrrole Derivatives And Their Application In Electrochromic Devices." Phd thesis, METU, 2006. http://etd.lib.metu.edu.tr/upload/12608070/index.pdf.
Full textAbstract:
Different substituted thiophene and pyrrole monomers namely hexamethylene (bis-3-thiopheneacetamide) (HMTA), N-(4-(3-thienylmethylene)-oxycarbonylphenyl)maleimide (MBThi), 2,4,6-Tris-(4-pyrrol-1-yl-phenoxy)-[1,3,5]triazine (TriaPy), 2,4,6-Tris-(thiophen-3-ylmethoxy)-[1,3,5] triazine (TriaTh), and N-(2-(thiophen-3-yl)methylcarbonyloxyethyl) maleimide (NMT) were synthesized. The chemical structures of the monomers were characterized by Nuclear Magnetic Resonance (1H-NMR and 13C-NMR) and Fourier Transform Infrared (FTIR) Spectroscopies. Electrochemical behavior of the monomers in the presence and absence of comonomers were studied by cyclic voltammetry. Subsequently, monomers were homopolymerized and copolymerized via electrochemical methods and the resultant polymers were characterized by FTIR, Scanning Electron Microscopy (SEM) and conductivity measurements.
Second part of the study was devoted to investigate one of most interesting property of conducting polymers, the ability to switch reversibly between the two states of different optical properties, &ldquoelectrochromism&rdquo
. In recent years there has been a growing interest in application of conducting polymers in electrochromic devices. Thus, electrochromic properties of the synthesized conducting polymers were investigated by several methods like spectroelectrochemistry, kinetic and colorimetry studies. Spectroelectrochemistry experiments were performed in order to investigate key properties of conjugated polymers such as band gap, maximum absorption wavelength, the intergap states that appear upon doping and evolution of polaron and bipolaron bands. Switching time and optical contrast of the homopolymers and copolymers were evaluated via kinetic studies. Results implied the possible use of these materials in electrochromic devices due to their good electrochromic properties.
32
Kerman, Ipek. "Synthesis And Characterization Of Poly(oxalic Acid Dithiophen-3-yl Methyl Ester) And Thiophene Ended Poly-&." Master's thesis, METU, 2004. http://etd.lib.metu.edu.tr/upload/2/12605014/index.pdf.
Full textAbstract:
Synthesis and characterization of thiophene ended poly-ε
-caprolactone (PCL) and oxalic acid dithiophen-3-yl methyl ester (ODME) and their copolymers with both pyrrole and thiophene were achieved. Chemical structure of the precursor polymer and monomer were investigated Redox behavior of polymer and monomers were determined by Cyclic Voltammetry (CV). Structural characterization of samples were carried out by 1H, 13C Nuclear Magnetic Resonance (NMR) and Fourier Transform Infrared Spectroscopy (FTIR). Conductivities of the films were measured by using four probe technique. Thermal analyses of conducting copolymers were investigated via Differential Scanning Calorimetry (DSC) and Thermal Gravimetry Analysis (TGA). The morphologies of the copolymer films were examined by Scanning Electron Microscopy (SEM). Electrochromic and spectroelectrochemical behavior of the copolymers were investigated, and their ability of employment in device construction has been examined.
33
Martin, René. "Neuartige Myosin ATPase-Inhibitoren auf der Basis polyhalogenierter Pyrrolalkaloide und stereoselektive Synthese hormonell aktiver Steroide." Doctoral thesis, Saechsische Landesbibliothek- Staats- und Universitaetsbibliothek Dresden, 2009. http://nbn-resolving.de/urn:nbn:de:bsz:14-ds-1231328688848-12720.
Full textAbstract:
Während meiner Dissertation beschäftigte ich mich mit der Synthese von polyhalogenierten Pyrrolalkaloiden. Im Zentrum der Darstellung dieser Verbindungen stand die von mir in meiner Diplomarbeit erfolgreich zur Synthese von Pentabrompseudilin angewandte silber-katalysierte Cyclisierung von N-tosylsubstituierten Homopropargylaminen. So konnte das Pentachlorpseudilin in der zweiten Totalsynthese überhaupt sowie mehrere gemischt halogenierte synthetische Derivate aufgebaut werden. Diese Verbindungen konnten in einer Kooperation mit Herrn Prof. Gutzeit aus der Fachrichtung Biologie der TU Dresden und Herrn Prof. Manstein von der Medizinischen Hochschule Hannover, als hochwirksame Myosin ATPase-Inhibitoren identifiziert werden. Bei den verschieden halogenierten Verbindungen ließen sich deutliche Unterschiede in der inhibitorischen Aktivität feststellen. Ein zum Pentabrompseudilin benzologes Indolderivat, welches in einer kurzen Synthese aufgebaut werden konnte, war hingegen nicht aktiv. Im zweiten Teil der Promotion beschäftigte ich mich in einer Kooperation mit Dr. Kurzchalia vom Max-Planck-Institut für Molekulare Zellbiologie und Genetik (Dresden) mit der Synthese von hormonell aktiven Steroiden, speziell den Cholesten-26-säuren, welche Liganden für den hormonellen Rezeptor DAF-12 des Nematoden Caenorhabditis elegans repräsentieren. Die an C-25 R-konfigurierten Säuren waren in der Literatur mit einer deutlich geringeren Aktivität als die 25S-Säuren beschrieben. Die 25R-Steroide waren synthetisch leicht aus kommerziell erhältlichem Diosgenin zugänglich. So konnten alle drei 25R-Säuren in kurzen Synthesen dargestellt werden. In deren Verlauf wurden verschiedene Oxidations- und Schutzgruppenreaktionen eindrucksvoll angewendet. Für die Einführung der 25S-Konfiguration in der Seitenkette sollte eine EVANS-Aldolreaktion an geeignetem Startmaterial angewandt werden. In der Tat führte die Verwendung eines chiralen Oxazolidinons stereoselektiv zum gewünschten Enantiomer in sehr guten Ausbeuten, selbst bei großen Ansätzen. Zur weiteren Transformation musste die durch die Aldolreaktion eingeführte Hydroxygruppe an C-24 entfernt werden. Dies gelang in exzellenter Ausbeute mit Hilfe einer radikalischen Deoxygenierung nach BARTON und MCCOMBIE. So konnte in acht Stufen ein zentrales Syntheseintermediat gewonnen werden, dass in alle drei Naturstoffe überführt werden konnte. Damit waren ausreichende Mengen für biologische Untersuchungen hergestellt worden. Mit der gesättigten (25S)-Dafachronic Acid konnte ein neuer Ligand für DAF-12 synthetisiert werden. Gleichzeitig konnte gezeigt werden, dass die Existenz einer Doppelbindung in den Cholesten-26-säuren für die biologische Aktivität unerheblich ist. Für weitere biologische Tests konnten neue Normethylderivate des Cholesterols gewonnen werden. Diese zeigten zum Teil ungewöhnliche biologische Aktivität. Außerdem wurden Versuche zu an verschiedenen Positionen bromierten Cholesterolderivaten unternommen. Im letzten Teil meiner Dissertation konnten neue hoch hydroxylierte Steroide dargestellt werden, die in einer Kooperation mit Prof. Franzblau vom Institute for Tuberculosis Research (Chicago, USA) auf ihre Aktivität gegen Mycobacterium tuberculosis getestet werden sollten. Dabei konnte eine ungewöhnliche 1,2-anti-Hydroborierung beoachtet werden, deren Mechanismus noch genauer untersucht werden muss.
34
Varis, Serhat. "Synthesis And Electrochromic Properties Of Conducting Polymers Of 1-(4-nitrophenyl)-2,5-di(2-thienyl)-1h-pyrrole And Their Use In Electrochromic Devices." Master's thesis, METU, 2007. http://etd.lib.metu.edu.tr/upload/12607926/index.pdf.
Full textAbstract:
A new monomer1-(4-Nitrophenyl)-2,5-di-2-thienyl-1H-pyrrole SNSNO2 was synthesized through the Knorr-Paal condensation reaction of 1,4-di-2-thienyl-1,4-butanedione and p-nitroaniline. The chemical structure of monomer and polymer were characterized via Nuclear Magnetic Resonance Spectroscopy (NMR) and Fourier Transform Infrared Spectroscopy (FTIR). Chemical polymerization produced a polymer which was completely soluble in organic solvents. Electrochemical behaviors of SNSNO2 and SNSNO2 in the presence of EDOT were studied by cyclic voltammetry (CV). The synthesis of homopolymer and copolymer were achieved via constant potential electrolysis. Both homopolymer P(SNSNO2) and copolymer P(SNSNO2-co-EDOT) were characterized by various techniques including cyclic voltammetry, FTIR, Scanning Electron Microscopy (SEM) and UV-VIS Spectrophotometer. Conductivities of samples were measured by four probe technique. The electrochromic properties of the polymers were investigated via spectroelectrochemistry, colorimetry and switching studies. In addition, dual type electrochromic devices (ECDs) composed of P(SNSNO2), P(SNSNO2-co-EDOT) and poly(3,4-ethylenedioxythiophene) (PEDOT) were constructed and evaluated. Spectroelectrochemistry, switching ability and stability of the devices were investigated by UV-Vis Spectrophotometer and Cyclic Voltammetry. They have shown to possess good switching times, reasonable contrasts and high stabilities.
35
Weller, Tina [Verfasser], and Mukundan [Akademischer Betreuer] Thelakkat. "Synthesis, structure formation, charge transport and applications of semiconducting copolymers based on thieno[3,4-c]pyrrole-4,6-dione / Tina Weller ; Betreuer: Mukundan Thelakkat." Bayreuth : Universität Bayreuth, 2019. http://d-nb.info/1177142376/34.
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36
Tamgho, Ingrid-Suzy. "Synthesis of Ligands and Macrocycles Based on 1,3-Diiminoisoindoline and Study of New Highly Fluorescent and Symmetric Pyrrole-BF2 Chromophores." University of Akron / OhioLINK, 2014. http://rave.ohiolink.edu/etdc/view?acc_num=akron1412163224.
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37
Ogunrombi, Modupe Olufunmilayo. "The synthesis and evaluation of 1-methyl-3-pyrrolines and 1-methylpyrroles as substrates and inhibitors of monoamine oxidase B / Modupe O. Ogunrombi." Thesis, North-West University, 2007. http://hdl.handle.net/10394/1837.
Full textAbstract:
Very little is known about why and how the Parkinson's disease (PD) neurodegenerative process begins and progresses. In the course of developments for treatment of PD, the discovery of the inhibition of monoamine oxidase (MAO B) was a conceptual breakthrough, and has now been firmly established. MAO B has also been implicated in the neurodegenerative processes resulting from exposure to xenobiotic amines. For example, MAO B catalyzes the first step of the bioactivation of the parkinsonian inducing pro-neurotoxin, 1-methyl-4-phenyl-1,2,3,6-tetrahydropyridine (MPTP). Additional insight into the mechanism of catalysis of MAO B and the mechanism of neurotoxicity by MPTP is therefore very valuable in the pursuit of the treatment of PD.Thesis (Ph.D. (Pharmaceutical Chemistry))--North-West University, Potchefstroom Campus, 2008.
38
Ciardi, Moira. "Design, synthesis and binding studies of calix(4)pyrrole based receptors suitable for ion-pair complexation and n-oxide recognition. Synthesis of resorcin(4) arene derivatives as potential ligands for supramolecular catalysis." Doctoral thesis, Universitat Rovira i Virgili, 2012. http://hdl.handle.net/10803/90244.
Full textAbstract:
El trabajo de tesis doctoral ha consistido en el diseño y síntesis de diferentes receptores moleculares. En particular, de nuevos derivados calix[4]pirrolaril-extendidos con dos y cuatro grupos fosfonatocomo receptores ditópicos para la complejación de pares iónicos,importantes para la extracción de sales y para el transporte de iones a través de las membranas celulares. Asimismo, derivados de calix[4]pirrol han sido preparados para la inclusión de N-óxidos en conformación de alta energía.La importancia de la inclusiónha sido demostrada en la modificación dela reactividad químicatípica delN-óxidoenreacciones en las queel mismo seutilizacomo co-oxidante. Porúltimo, se presentan derivados de resorcin[4]areno con grupos etilo en la parte inferior y una pared móvil en la parte superior como potenciales ligandos para catálisis supramolecular.The work developed during the PhD thesis deals mainly with the design and synthesis ofSupramolecular Hosts. In particular, we present new aryl-extended calix[4]pyrroleswith two or four phosphonate groups as heteroditopic receptors for the complexation of ion-pairs and that result important for the extraction of salts and for the transportof ions through membranes. Likewise, derivativesofcalix[4]pyrroles have been prepared for the selective inclusionofN-oxides in high energy conformation.The importance of the inclusion has been demonstrated by the change of the reactivity of the N-oxide in reactions in which it is commonly used as co-catalyst. Finally, we present derivatives ofresorcin[4]arenes with ethyl groups at the lower rim of thereceptor and a mobile wall in the upper rim as potential ligands for Supramolecular catalysis.
39
Barber, David M. "The development of nitro-Mannich/hydroamination cascades for the synthesis of substituted N-heterocycles." Thesis, University of Oxford, 2013. http://ora.ox.ac.uk/objects/uuid:18e7c533-3789-4800-9813-1d5c7bb4e4ea.
Full textAbstract:
This thesis describes the development of nitro-Mannich/hydroamination cascade reactions for the synthesis of N-heterocycles, which are important motifs found in a variety of biologically active natural products and pharmaceuticals, such as atorvastatin (Lipitor®). Chapter 2 outlines the development of an efficient synthesis of 2,5-disubstituted pyrroles using a nitro-Mannich/hydroamination cascade. Starting from easily prepared N-protected imines and nitroalkyne substrates, a compatible combination of KOtBu (10 mol%) and AuCl3 (5 mol%) was used to afford the desired pyrrole products, after an alkene isomerisation/HNO2 elimination reaction sequence. Chapter 3 describes the extension of this methodology to the diastereo- and enantioselective synthesis of 1,2,3,4-tetrahydropyridine derivatives using a nitroalkyne substrate with an extended carbon chain. The sequential addition of a bifunctional Brønsted base/H-bond donor organocatalyst and a gold complex was found to facilitate the desired cascade reaction affording substituted 1,2,3,4-tetrahydropyridine products. We then established that highly substituted pyrrolidine compounds could be prepared by replacing the nitroalkyne substrate with a nitroallene substrate (Chapter 4). The combination of KOtBu (5 mol%) and a gold catalyst derived from Au(PPh3)Cl (10 mol%) and AgSbF6 (20 mol%) was found to give an efficient diastereoselective synthesis of pyrrolidine derivatives after an additional nitro group epimerisation step. In addition, the nitro-Mannich/hydroamination cascade using nitroallene substrates was developed into an enantioselective variant using the previously employed bifunctional Brønsted base/H-bond donor organocatalyst. This afforded enantioenriched pyrrolidine derivatives.
40
Igdir, A. Cigdem. "Reinvestigation Of The Synthetic And Mechanistic Aspects Of Manganese(iii) Acetate Mediated Reactions Synthesis Of 1,2,4-trisubstituted Pyrroles Via Amination / Annulation Reactions Of Chloroenones With Chiral Amine Compounds." Phd thesis, METU, 2006. http://etd.lib.metu.edu.tr/upload/12607643/index.pdf.
Full textAbstract:
The first part of the thesis presents the reinvestigation of the synthetic and mechanistic aspects of manganese (III) acetate mediated reactions. The main concern about this subject was to perform a ¢- acetoxylation reactions of enones and saturated systems in shorter reactions times and higher yields than the ones known in literature reproducibly. Although successful a ¢
-acetoxylation of a great variety of substrates have been reported so far, there are some problems associated with the use of Mn(OAc)3. Considering that there are not many simple methods for the direct acetoxylation of enones, optimization of Mn(OAc)3 mediated a ¢
-acetoxylation of enones and reaching its maximum potential has a great importance from a synthetic and economical point of view. In the second part of the thesis, 1,2,4-trisubstituted pyrrole derivatives were the target molecules to be synthesized. Although there are quite a number of methods available for the synthesis of pyrroles, most of them involve multistep synthetic operations which lower the overall yield. There are limited reports on the preparation of the enantiomers of pyrrole derivatives having 1-N directly linked to the stereogenic center. Thus, developing a new synthetic method for the efficient preparation of polysubstituted pyrroles without racemization still remains an attractive goal.
41
Martin, René. "Neuartige Myosin ATPase-Inhibitoren auf der Basis polyhalogenierter Pyrrolalkaloide und stereoselektive Synthese hormonell aktiver Steroide." Doctoral thesis, Technische Universität Dresden, 2008. https://tud.qucosa.de/id/qucosa%3A23861.
Full textAbstract:
Während meiner Dissertation beschäftigte ich mich mit der Synthese von polyhalogenierten Pyrrolalkaloiden. Im Zentrum der Darstellung dieser Verbindungen stand die von mir in meiner Diplomarbeit erfolgreich zur Synthese von Pentabrompseudilin angewandte silber-katalysierte Cyclisierung von N-tosylsubstituierten Homopropargylaminen. So konnte das Pentachlorpseudilin in der zweiten Totalsynthese überhaupt sowie mehrere gemischt halogenierte synthetische Derivate aufgebaut werden. Diese Verbindungen konnten in einer Kooperation mit Herrn Prof. Gutzeit aus der Fachrichtung Biologie der TU Dresden und Herrn Prof. Manstein von der Medizinischen Hochschule Hannover, als hochwirksame Myosin ATPase-Inhibitoren identifiziert werden. Bei den verschieden halogenierten Verbindungen ließen sich deutliche Unterschiede in der inhibitorischen Aktivität feststellen. Ein zum Pentabrompseudilin benzologes Indolderivat, welches in einer kurzen Synthese aufgebaut werden konnte, war hingegen nicht aktiv. Im zweiten Teil der Promotion beschäftigte ich mich in einer Kooperation mit Dr. Kurzchalia vom Max-Planck-Institut für Molekulare Zellbiologie und Genetik (Dresden) mit der Synthese von hormonell aktiven Steroiden, speziell den Cholesten-26-säuren, welche Liganden für den hormonellen Rezeptor DAF-12 des Nematoden Caenorhabditis elegans repräsentieren. Die an C-25 R-konfigurierten Säuren waren in der Literatur mit einer deutlich geringeren Aktivität als die 25S-Säuren beschrieben. Die 25R-Steroide waren synthetisch leicht aus kommerziell erhältlichem Diosgenin zugänglich. So konnten alle drei 25R-Säuren in kurzen Synthesen dargestellt werden. In deren Verlauf wurden verschiedene Oxidations- und Schutzgruppenreaktionen eindrucksvoll angewendet. Für die Einführung der 25S-Konfiguration in der Seitenkette sollte eine EVANS-Aldolreaktion an geeignetem Startmaterial angewandt werden. In der Tat führte die Verwendung eines chiralen Oxazolidinons stereoselektiv zum gewünschten Enantiomer in sehr guten Ausbeuten, selbst bei großen Ansätzen. Zur weiteren Transformation musste die durch die Aldolreaktion eingeführte Hydroxygruppe an C-24 entfernt werden. Dies gelang in exzellenter Ausbeute mit Hilfe einer radikalischen Deoxygenierung nach BARTON und MCCOMBIE. So konnte in acht Stufen ein zentrales Syntheseintermediat gewonnen werden, dass in alle drei Naturstoffe überführt werden konnte. Damit waren ausreichende Mengen für biologische Untersuchungen hergestellt worden. Mit der gesättigten (25S)-Dafachronic Acid konnte ein neuer Ligand für DAF-12 synthetisiert werden. Gleichzeitig konnte gezeigt werden, dass die Existenz einer Doppelbindung in den Cholesten-26-säuren für die biologische Aktivität unerheblich ist. Für weitere biologische Tests konnten neue Normethylderivate des Cholesterols gewonnen werden. Diese zeigten zum Teil ungewöhnliche biologische Aktivität. Außerdem wurden Versuche zu an verschiedenen Positionen bromierten Cholesterolderivaten unternommen. Im letzten Teil meiner Dissertation konnten neue hoch hydroxylierte Steroide dargestellt werden, die in einer Kooperation mit Prof. Franzblau vom Institute for Tuberculosis Research (Chicago, USA) auf ihre Aktivität gegen Mycobacterium tuberculosis getestet werden sollten. Dabei konnte eine ungewöhnliche 1,2-anti-Hydroborierung beoachtet werden, deren Mechanismus noch genauer untersucht werden muss.
42
AlHaddad, Nancy. "Synthèse de nouvelles entités complexantes à base de calix[4]pyrrole pour la décontamination des milieux aquatiques en radionucléides naturels." Thesis, Littoral, 2020. https://documents.univ-littoral.fr/access/content/group/50b76a52-4e4b-4ade-a198-f84bc4e1bc3c/BULCO/Th%C3%A8ses/Toxicologie/Version_finale_These_Nancy_AlHaddad.pdf.
Full textAbstract:
Les radionucléides se retrouvent naturellement dans l'air, le sol, et l'eau et génère une radioactivité de l'environnement. Suite aux activités anthropiques récentes telle que l'extraction d'uranium ou la production de pétrole et de gaz naturel, des quantités plus importantes de radionucléides naturels ont été émises et induisent un risque pour la santé humaine. L'une des voies les plus importantes de contamination humaine aux radionucléides, en dehors de l'inhalation, passe par une contamination de l'eau résultant de l'hydrosolubilité importante de certains sels de radionucléides. De fait, des niveaux maximums de contamination en radionucléides, notamment dans les approvisionnements publics en eau, ont été internationalement réglementés. Afin de se conformer à ces exigences, des méthodes de décontamination en radionucléides de l'eau ont été développées et parmi elles, des extractants macrocycliques tels que les calixpyrroles. De structure cyclique préorganisée, ces macrocycles présentent des propriétés de chélation que l'on retrouve également chez leurs homologues de type phénoxycalix[4]pyrrole (PCP). Cependant, ce dernier présente un potentiel accru de fonctionnalisation chimique permettant l'introduction de sites supplémentaires de chélation de par la présence de quatre entités phénoliques. Dans ce contexte, la synthèse des dérivés de PCP ainsi que la capacité à complexer et extraire des éléments stables ou radioactifs ont été étudiées. Pour cela, la fonctionnalisation du PCP a été réalisée par des groupements tels que : acide carboxylique, acide hydroxamique, azide, amine et dérivés de type hétéroaryle. A l'issue de ces synthèses, l'étude des capacités de chélation du dérivé 2-pyridino-1,2,3-triazolo-PCP a été réalisée et l'existence d'une complexation sélective du fer ferreux et ferrique dans le DMSO a été mise en évidence par fluorescence moléculaire. L'étude des capacités de chélation des halogénures ont, quant à elles, étaient étudiées par titrage RMN ¹H ainsi que par fluorescence moléculaire et a montré une sélectivité pour le fluorure, habituelle pour ce type de structure. Une seconde partie de ce travail a été consacrée à la synthèse et l'étude des propriétés d'un nouveau polymère de phénoxycalix[4]pyrrole par l'épichlorohydrine (PCP-EP), ceci en vue de la décontamination des effluents aqueux chargés en radionucléides par extraction solide/liquide. Premier polymère référencé de la littérature dans cette série, sa structure a été déterminée par RMN, IRTF et ATG puis sa capacité de chélation envers les halogénures a été testée par chromatographie ionique. Les résultats ont démontré que ce polymère, contrairement à sa structure monomérique, possède une affinité supérieure pour l'iodure. Les capacités d'extraction solide/liquide des radionucléides par le PCP-EP ont été ensuite étudiées par spectromètre gamma couplé à un détecteur germanium de haute pureté, à l'aide de solutions aqueuses contenant des radionucléides et a abouti à un taux d'extraction de 22% en Ra-226. Le développement d'un plan d'expérience Doehlert a été par la suite mené afin d'optimiser les conditions d'extraction expérimentale. Lors de cette étape, l'étude du BA²⁺, métal stable et de comportement chimique similaire au RA²⁺, a été priorisée afin de réduire la production de déchets radioactifs. Les résultats de ce plan d'expérience ont abouti à des conditions d'extraction optimales de pH, température et de durée, qui translatée à une solution aqueuse radioactive, ont montré une capacité du PCP-EP à extraire 89% de Ra-226Radionuclides are found naturally in air, soil and water and generate radioactivity in the environment. As a result of recent anthropogenic activities such as uranium mining or the production of oil and natural gaz, larger quantities of natural radionucleides have been released and induce a risk to Human Health. One of the most important routes for Human contamination with radionucleides, other than inhalation, is water contamination that results from the high hydro-solubility of certain radionuclide salts. In fact, maximum contaminant levels for radionuclides contamination, especially in public water supplies, have been internationally regulated. In order to comply with these requirements, methods for decontaminating water from radionuclides have been developes, among which macrocyclic extractants such as calixpyrroles. With a preorganized cyclic structure, these macrocycles exhibit chelating properties that are also found in their phenoxycalix[4]pyrrole (PCP) homologs. However, the latter has an increased potential for chemical functionalization allowing the introduction of additional chelation sites due to the presence of four phenolic entities. In this context, the synthesis of PCP derivatives and the study of their ability to complex and extract stable or radioactive elements have been studied. For this, the functionalization of the PCP was carried out by functional groups such as : carboxylic acid, hydroxamic acid, azide, amine and heteroaryl-extended derivatives. At the end of these syntheses, the study of the chelation capacities of the derivative 2-pyridino-1,2,3-triazolo-PCP was carried out and the existence of a selective complexation of ferrous and ferric iron in DMSO was demonstrated by molecular fluorescence. As for the chelation capacities for halides, they were studied by ¹H NMR and molecular fluorescence titrations and showed a selectivity for fluoride. A second part of this work was devoted to the synthesis and study of the properties of a new polymerof PCP crosslinked by epichlorohydrin (PCP-EP), in the aim of engaging it into solid/liquid extractions, applied for the decontamination of aqueous effluents containing radionuclides. In this series of polymers, PCP-EP is the first to be reported in literature. Accordingly, its structure was determined by NMR, FTIR and TGA, then its chelation capacities towards halides was tested by ion chromatography after solid/liquid extractions. The results demonstrated that this polymer, unlike its monomeric structure, has a higher affinity for iodide. The solid/liquid extraction capacities of radionuclides by PCP-EP were then studied by a gamma spectrometer coupled to a High Purity Germanium detector, using aqueous solutions containing radionuclides and resulted in an extraction rate of 22% for Ra-226. The development of a Doehlert experimental design was then carried out in order to optimize the experimental extraction conditions. During this step, the study of BA²⁺, a stable metal with a chemical behavior similar to RA²⁺, was prioritized in order to reduce the production of radioactive waste. The results of this experimental design led to optimal extraction conditions of pH, temperature and time, which translated to an aqueous radionuclides-containing solution, showed the ability of PCP-EP to extract 89% Ra-226
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Semyonov, Alexander N. "Design, Synthesis and Characterization of Fluorescent Dyes and Liquid Crystal Semiconductors." Kent State University / OhioLINK, 2006. http://rave.ohiolink.edu/etdc/view?acc_num=kent1153556141.
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Leroux, Marcel Rainer [Verfasser], and Paul [Akademischer Betreuer] Knochel. "Late-stage functionalization of peptides and cyclopeptides using organozinc reagents and pyrrole protected 2-Aminoalkylzinc reagents for the enantioselective synthesis of amino derivatives / Marcel Rainer Leroux ; Betreuer: Paul Knochel." München : Universitätsbibliothek der Ludwig-Maximilians-Universität, 2020. http://d-nb.info/1208150057/34.
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Sirindil, Fatih. "Développement de réactions catalysées à l'or et au palladium : synthèse totale d'alcaloïdes de la famille du Rhazinilam." Thesis, Strasbourg, 2019. http://www.theses.fr/2019STRAF001/document.
Full textAbstract:
Ce travail de thèse s’articule autour de la synthèse totale des alcaloïdes de la famille Rhazinilam, potentiels agents anticancéreux. Dans ce contexte, deux méthodologies clés ont été développées. Premièrement, une réaction de cyclisation-migration de groupements sulfonyles catalysée à l'or (I) conduisant à des sulfonates de pyrroles a été optimisée et le champ d'application a été largement étendu. En tirant profit de la carbophilie des catalyseurs d’or (I), une réaction en cascade comprenant une séquence de cyclisation-migration-hydrocarbonation a été mise en place, permettant la synthèse d’indolizines ou de pyrroloazépines dans un procédé en un seul pot. Deuxièmement, des conditions réactionnelles sans précèdent par catalyse au palladium ont été développées pour le couplage de Suzuki-Miyaura impliquant des substrats de types sulfonates de pyrroles. Ces conditions ont été appliquées de façon efficace sur divers types de partenaires (aryle, hétéroaryle, vinyle sulfonates ou analogues halogénés) mais également utilisées dans différents types de couplages (Sonogashira, Buchwald). Ces méthodologies ont ensuite été appliquées à la synthèse totale du Rhazinilam et permis d’ouvrir la voie à la synthèse des Kopsiyunnanines et du Leuconolam. En parallèle, de nouveaux complexes associant des polyoxométallates et des carbènes d'or (I) ont été synthétisés, caractérisés et utilisés en catalyse hétérogèneThis PhD work was articulated around the total synthesis of the Rhazinilam family alkaloids, potential anticancer agents. In this context, two key methodologies have been developed. Firstly, a gold(I)-catalyzed cyclization-sulfonyl migration reaction leading to pyrrole sulfonates has been optimized and the scope was largely extended. By taking advantage of the carbophilicity of gold(I) catalysts, a cascade reaction including a sequence of cyclization-migration-hydrocarbonation has been implemented, allowing the synthesis of indolizidines or pyrroloazepines in a one pot process. Secondly, unprecedented reaction conditions were developed for palladium-catalyzed Suzuki−Miyaura cross-coupling using pyrrole sulfonates as substrates. These conditions have been applied efficiently on various types of partners (aryl, heteroaryl, vinyl sulfonates or halogenated analogues) but also used in different types of cross-coupling (Sonogashira, Buchwald). These methodologies were then applied to the total synthesis of Rhazinilam and to open the way to the synthesis of Kopsiyunnanines and Leuconolam natural products. In parallel, new complexes combining polyoxometalates and gold(I) carbenes have been synthesized, characterized and used in heterogeneous catalysis
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Ottaway, Carol Jean. "Synthesis of carbapenams from pyrroles." Thesis, University of Liverpool, 1995. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.283487.
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Addie, Matthew Stuart. "Synthetic strategies towards pyrrole marine alkaloids." Thesis, University of East Anglia, 1998. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.267273.
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VanNess, Brandon G. "Synthetic approach to epibatidine from 1-(phenylsulfonyl)pyrrole." Wright State University / OhioLINK, 2007. http://rave.ohiolink.edu/etdc/view?acc_num=wright1183494979.
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Agarwal, Sameer. "Transition Metal-Mediated Syntheses of Yohimbane and Indolizidine Alkaloids." Doctoral thesis, Saechsische Landesbibliothek- Staats- und Universitaetsbibliothek Dresden, 2005. http://nbn-resolving.de/urn:nbn:de:swb:14-1119360417222-39155.
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Polycyclic nitrogen containing heterocycles form the basic skeleton of numerous alkaloids and physiologically active drugs. Alloyohimbane was obtained from 3,4-dihydro-â-carboline using an iron-mediated [2+2+1] cycloaddition as the key-step. The bis-TMS-diyne was conveniently obtained by the C-alkylation of 3,4-dihydro-â-carboline followed by N-alkylation. Demetalation of the iron-complex followed by hydrogenation, E-ring expansion, and reduction provided alloyohimbane, a structurally and biologically interesting substance, via a linear eight-step sequence in 7% overall yield based on 3,4-dihydro-â-carboline. Another sequence provided (±)-alloyohimbane and (±)-3-epi-alloyohimbane in nine steps. The pyrrole unit occurs in a variety of naturally occurring compounds, pharmaceutical products and polymers. A novel two-step procedure for the synthesis of pyrroles by addition of a propargyl Grignard reagent to a Schiff base and subsequent silver(I)-promoted oxidative cyclization of the resulting homopropargylamine has been developed. The generality of this reaction was proven by the synthesis of a broad variety of substituted pyrroles using silver(I)-promoted cyclization. A three-step synthesis of (±)-harmicine, a natural product isolated from the Malaysian plant Kopsia griffithii having strong anti-leishmania activity, from 3,4-dihydro-â-carboline is achieved by addition of 3-trimethylsilylpropargyl Grignard reagent, Ag(I)-promoted oxidative cyclization to a pyrrole, and chemoselective hydrogenation of pyrrole ring. Total synthesis of anti-tumor active crispine A and biologically active 1,2,3,5,6,10b-hexahydropyrrolo[2,1-a]isoquinoline have been achieved in three steps using silver(I)-promoted oxidative cyclization as key step.
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Voro, Tevita N. "Synthesis of potentially biologically active indoles and pyrroles." Thesis, University of East Anglia, 1990. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.254485.
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