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MORIN, ISABELLE. "3-aryl as-triazines : bioisosterie avec les 6-aryl pyridazines." Université Louis Pasteur (Strasbourg) (1971-2008), 1991. http://www.theses.fr/1991STR13021.
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Un examen comparatif de bioisosteres potentiels de derives pyridaziniques (pyrazines, pyrimidines, 1,3,4-thiadiazoles, et 1,2,4-triazines) a ete realise. Les structures etablies par diffraction aux rayons x suivies de calculs semi-empiriques ont mis en evidence l'importance du moment dipolaire comme critere de differenciation entre ces differents systemes heterocycliques. Le systeme as-triazinique, predit comme devant etre bioequivalent des pyridazines a ete plus particulierement etudie. Sur le plan chimique, des ameliorations ont ete apportees a leur synthese au depart de derives d'hippurate d'ethyle. La reactivite du systeme a egalement ete etudiee, en particulier par la mise au point d'aminoalkyltriazines et de triazolotriazines. Une vingtaine d'aminoalkyltriazinones ont ete etudiees pour leurs proprietes analgesiques. Les affinites micromolaires de ces derives envers les recepteurs opiaces sigma et kappa concordent avec les valeurs moderees observees sur des tests d'analgesie chez l'animal. Des predictions d'activite inhibitrice de l'acetylcholinesterase pour des alkylaminotriazines se sont averees verifiees et demontrent a nouveau la bioequivalence entre les triazines et les pyridazines et l'absence de bioequivalence entre la pyrazine et les pyridazines. Au depart d'une dizaine de molecules synthetisees, plusieurs se sont revelees interessantes comme inhibiteur competitif et reversible de l'acetylcholinesterase; la plus puissante montrant une ic#5#0 de 3. 10#-#7 m
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Barman, Gopa. "Synthetic studies on N - Aryl Y - Lactam & N - Aryl Y - Thio - Lactam : chemoselective Transformation to N-Aryl-Pyrrolidine, N-Aryl Succinimide and Other Bioactive Compounds." Thesis, University of North Bengal, 2009. http://hdl.handle.net/123456789/1379.
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Zhou, Edouard. "Nouveaux systèmes catalytiques appliqués aux formations de liaisons C—C par couplage croisé catalysé par des sels de fer : applications, mécanismes." Thesis, Paris Sciences et Lettres (ComUE), 2018. http://www.theses.fr/2018PSLEC008.
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Gramberg, Joachim. "Synthese von threo-3-Aryl-glutaminsäurediethylestern und cis-3-Aryl-prolinen /." [S.l. : s.n.], 1996. http://www.gbv.de/dms/bs/toc/225111152.pdf.
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Leyva-Ramos, Elisa. "The temperature dependent photochemistry of aryl azides and aryl diazo compounds /." The Ohio State University, 1986. http://rave.ohiolink.edu/etdc/view?acc_num=osu1487267024997622.
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Sun, Qingqing. "Aryl and Super Aryl-Extended Calix[4]pyrroles: Synthesis and Applications." Doctoral thesis, Universitat Rovira i Virgili, 2021. http://hdl.handle.net/10803/672268.
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Aquesta tesi doctoral descriu el disseny i la síntesi d’una sèrie de receptors supramoleculars que presenten cavitats aromàtiques polars. Els receptors preparats inclouen receptors organometàl·lics, contenidors moleculars solubles en aigua, caixes moleculars basades en enllaços de coordinació i metal·lo-cavitands. S’han seleccionat unitats de calix[4]pirrole aril i super-aril estesos (AEC[4]P i SAE-C[4]P) com a components principals. S’han estudiat les propietats de reconeixement molecular dels receptors sintètics amb sals de clorur de tetraalquilamoni, així com de molècules polars neutres, en dissolvents orgànics i en aigua. Concretament, s’ha preparat un calix[4]pirrole super aril estès substituït amb una fosfina mono-Au(I) i s’han estudiat les seves propietats de reconeixement davant diferents sals de clorur de tetraalquilamoni en diclorometà i acetona. Els complexos organometàl·lics d'inclusió amb aquestes sals presenten una estabilitat termodinàmica reduïda respecte al seu anàleg no organometàlic simètric "de dues parets". Molt probablement això és degut a que les interaccions repulsives anió-π són més fortes al complex de clorur del receptor organometàl·lic. S’ha explorat l'aplicació d'un receptor SAE-C[4]P soluble en aigua en la hidròlisi de bis-isonitrils alifàtics catalitzada per àcids. El receptor SAE-C[4]P forma complexos 1:1 termodinàmicament estables amb els bis-isonitrils, mono-isonitrils-mono-formamides i bis-formamides. Els compostos mono reaccionats units presenten el grup formamida exclusivament en la conformació cis. Aquesta disposició protegeix el grup isonitril i provoca millores en el rendiment dels compostos mono-reaccionats. També s’ha dut a terme l’auto assemblatge d’una caixa metàl·lica soluble en aigua amb dos llocs d’unió polar endoèdrics. S’ha demostrat que l’assemblatge eficient de la caixa metàl·lica requereix l’encapsulació de molècules polars mono i ditòpiques neutres. La caixa metàl·lica mostra selectivitat conformacional per la unió de bis-formamides alifàtiques amb diferents longituds del espaiadors (grups metilè). Finalment, es descriu la síntesi d'un lligand tetra-oxazolo [4,5-b]pirazinil SAE-C[4]P sense precedents. Es descriu l’auto assemblatge d’un bis-metal·lo-cavitand basat en el lligand SAE-C[4]P i Pt(II) com a precursors. De la mateixa manera, es demostra que la incEsta tesis doctoral describe el diseño y la síntesis de una serie de receptores supramoleculares que presentan cavidades aromáticas polares. Los receptores preparados incluyen receptores organometálicos, contenedores moleculares solubles en agua, cajas moleculares basadas en enlaces de coordinación y metalo-cavitandos. Se han seleccionado unidades de calix[4]pirrol aril- y super-aril extendidos (AEC[4]P y SAE-C[4]P) como componentes principales. Se han estudiado las propiedades de reconocimiento molecular de los receptores sintéticos con sales de cloruro de tetraalquilamoni, así como de moléculas polares neutras, en disolventes orgánicos y en agua. Concretamente, se ha preparado un calix[4]pirrol super-aril extendido sustituido con una fosfina mono-Au(I) y se han estudiado sus propiedades de reconocimiento molecular ante diferentes sales de cloruro de tetraalquilamonio en diclorometano y acetona. Los complejos organometálicos de inclusión con estas sales presentan una estabilidad termodinámica reducida respecto a su análogo no organometálico simétrico "de dos paredes". Muy probablemente esto se debe a que las interacciones repulsivas anión-π son más fuertes en el complejo de cloruro del receptor organometálico. Se ha explorado la aplicación de un receptor SAE-C[4]P soluble en agua en la hidrólisis de bis-isonitrilos alifáticos catalizada por ácidos. El receptor SAE-C[4]P forma complejos 1: 1 termodinámicamente estables con los bis-isonitrilos, mono-isonitrilos-mono-formamida y bis-formamida. Los compuestos mono-reaccionados unidos presentan el grupo formamida exclusivamente en la conformación cis. Esta disposición protege el grupo isonitrilo y produce mejoras en el rendimiento de los compuestos mono-reaccionados. También se ha llevado a cabo el auto ensamblaje de una caja metálica soluble en agua con dos sitios de unión polar endoèdricos. Se ha demostrado que el ensamblaje eficiente de la caja metálica requiere la encapsulación de moléculas polares mono y di-tópicas neutras. La caja metálica muestra selectividad conformacional para la unión de bis-formamida alifáticas con diferentes longitudes de espaciadores (número de grupos metileno). Finalmente, se describe la síntesis de un ligando tetra-oxazolo [4,5-b] pirazinil SAE-C[4]P sin precedentes. Se describe el auto ensamblaje de un bis-metalo-cavitando basado
This PhD Thesis describes the design and synthesis of a series of supramolecular receptors featuring polar aromatic clefts and cavities. The prepared receptors include organometallic receptors, water-soluble containers, metallocages and metallocavitands. We selected aryl and super aryl-extended calix[4]pyrrole scaffolds (AE-C[4]P and SAE-C[4]P) as their main building blocks. We studied the molecular recognition properties of the synthetic receptors with tetraalkylammonium chloride salts, as well as neutral polar guests, in organic solvents and in water. Specifically, we prepared a mono-gold(I) phosphine substituted AE-C[4]P and studied its binding properties towards tetraalkylammonium chloride salts in dichloromethane and acetone solutions. The inclusion organometallic complexes featured a reduced thermodynamic stability with respect to its parent symmetrical “two-wall” counterpart. These results were explained considering the stronger repulsive anion-π interactions present in the chloride complex of the organometallic receptor. Next, we explored the application of a water-soluble SAE-C[4]P in the acid-catalyzed hydrolysis of aliphatic bis-isonitriles. The SAE-C[4]P receptor formed thermodynamically stable 1:1 complexes with the bis-isonitriles, mono-isonitrile-mono-formamides and bis-formamides. The bound mono-reacted compounds featured the formamide group in exclusive cis-conformation. This arrangement protected the unreacted isonitrile group from water solvation and induced yield enhancements for the mono-reacted compounds. We also reported the self-assembly of water-soluble metallocage featuring two endohedral polar binding sites. We showed that the efficient assembly of the metallcage requires the encapsulation of neutral mono-and ditopic polar guests. The assembled metallocage displayed conformational selectivity in the binding of aliphatic bis-formamides having different methylene spacers. Finally, we described the synthesis of an unprecedented tetra-oxazolo[4,5-b]pyrazinyl SAE-C[4]P ligand. We reported the self-assembly of a bis-metallocavitand based on the SAE-C[4]P ligand and Pt(II) precursors. Similarly, we showed that the inclusion of suitable polar guest was mandatory for the metallocavitand formation. The SAE-C[4]P ligand chelated only two Pt(II) metals between its adjacent substituents affordin
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Payton, John L. PhD. "The Photophysical Behavior of Aryl-diphosphenes and Aryl-phosphaalkenes: A Theoretical Study." Cleveland, Ohio : Case Western Reserve University, 2010. http://rave.ohiolink.edu/etdc/view?acc_num=case1270488297.
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Thesis (Doctor of Philosophy)--Case Western Reserve University, 2010Department of Chemistry Title from PDF (viewed on 2010-05-25) Includes abstract Includes bibliographical references and appendices Available online via the OhioLINK ETD Center
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Chamoin, Sylvie. "Aryl-aryl Stille and Suzuzi-Miyaura cross-coupling reactions on solid support." Thesis, National Library of Canada = Bibliothèque nationale du Canada, 2000. http://www.collectionscanada.ca/obj/s4/f2/dsk1/tape3/PQDD_0022/NQ51184.pdf.
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Rydfjord, Jonas. "Palladium(II)-Catalyzed Addition Reactions : Synthesis of Aryl Amidines and Aryl Ketones." Doctoral thesis, Uppsala universitet, Avdelningen för organisk farmaceutisk kemi, 2017. http://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-326816.
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Palladium-catalyzed reactions have become one of the most important tools in modern organic chemistry due to its ability to catalyze the formation of new carbon-carbon bonds. The aim of the work presented in this thesis was to develop new palladium(II)-catalyzed addition reactions. In this work, cyanamides were investigated as a new substrate to give aryl amidines as products. The first protocol developed employed aryltrifluoroborates as the aryl partner, and the insertion of the aryl group into un-, mono-, and di-substituted cyanamides was successful for a wide variety of aryltrifluoroborates. An alternative method of generating the necessary intermediate for insertion into the cyanamide is the decarboxylative formation of aryl-palladium from aryl carboxylic acids. A protocol was developed for this reaction, but was unfortunately limited to a small number of ortho-substituted electron-rich aryl carboxylic acids. The mechanism was investigated by the means of DFT calculations and ESI-MS studies, and the rate-determining step was suggested to be the 1,2-carbopalladation based upon those results. A translation of the batch protocol to continuous-flow conditions was also demonstrated. The ideal method of generating the aryl-palladium species is by C-H bond activation, and this approach was demonstrated with indoles, giving a variety of 3-amidinoindoles as products. The mechanism was investigated by DFT calculations and a plausible catalytic cycle was proposed. A continuous-flow application of a desulfitative palladium(II)-catalyzed addition to nitriles to give ketones was developed. In addition, different reactor materials were evaluated in the microwave heated reactor cavity. Thus the reaction was shown to proceed with microwave heating in a borosilicate glass and an aluminum oxide reactor, and also in conditions mimicking conventional heating in a silicon carbide reactor. Finally, a protocol was developed for the convenient synthesis of sodium aryl sulfinates from Grignard and lithium reagents using a solid sulfur dioxide source as a safe alternative to the gas. The products of this protocol can be used as aryl-palladium precursors by a desulfitative process.
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Mei, Hua. "Perfluoroalkyl (aryl) sulfonimide zwitterions." Connect to this title online, 2006. http://etd.lib.clemson.edu/documents/1175185494/.
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Truong, Phong Minh. "Hexa-aryl/alkylsubstituted Cyclopropanes." Digital Archive @ GSU, 2006. http://digitalarchive.gsu.edu/chemistry_theses/2.
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A series of penta-aryl/alkyl-1-(toluene-4-sulfonyl)-4,5-dihydro-1H-pyrazole 5a-c was synthesized by addition of methyllithium or phenylllithium followed by trapping the nitrogen anion intermediate with tosyl-fluoride to cyclic azines 2a,b. Addition of methyllithium or phenyllithium to 5a-c generated a series of hexa-aryl/alkylsubstituted-4,5-dihydro-3H-pyrazoles 6a-c. Neat thermolysis of hexa-aryl/alkylsubstituted-4,5-dihydro-3H-pyrazoles 6a-c at 200◦C produced hexa-aryl/alkylsubstituted cyclopropanes 7a-c in high yield.
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Steinberg, Brian David. "Examining the Boundaries of Strained Aryl-Aryl Coupling Reactions in Polycyclic Aromatic Hydrocarbons." Thesis, Boston College, 2009. http://hdl.handle.net/2345/993.
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Thesis advisor: Lawrence T. ScottChapter 1. The impact and growth of carbon nanotubes within the framework of nanotechnology is presented. Methods to produce single chirality nanotubes from template-mediated sources are evaluated. The concept of a nanotube endcap is introduced as a potential synthetic target toward the selective synthesis and growth of a single chirality carbon nanotube. Chapter 2. A modified synthesis of corannulene is presented, highlighting a selective imine based reaction protocol for the fuctionalization 4,7-dimethylacenaphthenequinone. Also reviewed is a cascade coupling approach toward the synthesis of corannulene, followed by an analysis of the thermochemistry of the two-component disconnection. Chapter 3. The synthesis of 6 different indenoannulated corannulene congeners derived from a single flash vacuum pyrolysis (FVP) is described. X-ray crystal structures for each indenoannulated corannulene are presented along with computational modeling. Spectroscopic comparison between observed and theoretical 1H NMR provides one of the largest complete and comparative data sets for a collection of PAHs. Chapter 4. The application of a palladium based indenoannulation reaction is presented as an alternative synthetic method to FVP. Heteroatom based derivatives of both tetraindenocorannulene and pentaindenocorannulene were both developed as potential solubilizing factors. The thermochemistry for each successive indenoannulation of 1,3,5,7,9-pentaphenylcorannulene leading to pentaindenocorannnulene has been calculated, providing an approximated energy landscape for the total transformation. Chapter 5. Several routes for the synthesis of 1,3,5,7,9-pentakis(2,6-dichlorophenyl)-corannulene are presented. The yield for this reaction has been improved through the use of a palladium based precatalyst. During this time we studied a five-fold palladium catalyzed borylation of corannulene using B2pin2. Finally development of a cascade coupling reaction towards a [5,5] SWNT endcap is highlighted by a 12 bond coupling reaction. Chapter 6. A nickel-promoted homo-coupling between the proximally situated aryl halides of 1,2,5,6-tetrakis(2-chlorophenyl)corannulene is used to complete the synthesis of diphenanthro[9,10-a:9′,10′-g]corannulene. X-ray quality crystal were grown of diphenanthro[9,10-a:9′,10′-g]corannulene, and the structure was solved. The crystals forms highly ordered arrays in a columnar fashion with each phenanthro segment aligned through a series of π - π stacking interactions
Thesis (PhD) — Boston College, 2009
Submitted to: Boston College. Graduate School of Arts and Sciences
Discipline: Chemistry
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CRESPI, STEFANO. "New Intermediates from Photogenerated Phenyl Cations." Doctoral thesis, Università degli studi di Pavia, 2017. http://hdl.handle.net/11571/1203367.
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La tesi presenta uno studio sulla fotoreattività di composti aromatici volta ad ampliare la classe di substrati in grado di fotogenerare alfa,n-dideidrotolueni a partire da aril cationi nel loro stato di tripletto. Viene riportato inoltre lo studio fotochimico di arilazo mesilati come nuovi prescursori di aril cationi e radicali. In aggiunta viene presentato un approccio fotocatalitico per la generazione di intermedi reattivi svoltosi presso l’Università di Ratisbona. Il lavoro è corredato dallo studio computazionale e meccanicistico sulle reazioni fotochimiche studiate sperimentalmente.This thesis is devoted to the study of the aromatic compounds photoreactivity and in particular to widen the number of alfa,n didehydrotoluenes precursors from photogenerated triplet aryl cations. The photochemical investigation on arylazo mesylates photoreactivity as novel aryl radicals and cations generators is also presented. Moreover, all reactions experimentally studied are analysed on the basis of computational chemistry.
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Fuglseth, Erik. "Synthesis of 1-aryl-2-fluoroethanones and their use in the preparation of enantioenriched 1-aryl-2-fluoroethanols and 1-aryl-2-fluoroethylamines." Doctoral thesis, Norges teknisk-naturvitenskapelige universitet, Institutt for kjemi, 2010. http://urn.kb.se/resolve?urn=urn:nbn:no:ntnu:diva-11631.
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Jones, D. "The synthesis of aryl ethers." Thesis, Swansea University, 1994. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.637726.
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The synthesis of biaryl ethers is a process of importance in many fields within the chemical industry. Generally, the Ullmann ether synthesis is employed, though improvements in the general method have not been commonplace since the inception of the process at the turn of the century. By reinvestigating the parameters present, it was found that the use of cuprous iodide in a solventless reaction led to high yields of diaryl ethers. Further improvements were developed by the implementation of ultrasound in conjunction with lower reaction temperatures, with similarly high yields being afforded. Study was then undertaken to investigate the applicability of electrophilic bromination of various aromatic moieties. Thus, phenol, 2-methoxyphenol and aniline were examined in relation to the amount of ortho-bromination occurring with reagents such as 1,3-dibromo-5,5-dimethylhydantoin and N-bromosuccinimide in the presence of solid supports. These studies indicated that the use of solid supports, especially Amberlyst 15 and XN1010 and Montmorillonite K10 realised high degrees of bromination, though in the case of aniline the natural tendency to realise bromination in the para-position reduced the observed effectiveness of the process. By the implementation of acetyl hypobromite and N,N-dibromourethane, good para selectivity was found for the bromination of toluene in the presence of solid supports, though when applied to nitrobenzene, bromination of the straight chain alkane present at the internal standard present for gas chromatography analysis occurred. The use of molecular bromine in conjunction with solid supports such as Montmorillonite K10 led to high yields of 1-bromonaphthalene.
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Singh, Sacha U. N. "Aryl hydrocarbon-mediated inhibition of osteogenesis, reversal by resveratrol, a novel aryl hydrocarbon receptor antagonist." Thesis, National Library of Canada = Bibliothèque nationale du Canada, 1999. http://www.collectionscanada.ca/obj/s4/f2/dsk2/ftp01/MQ45976.pdf.
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Hofmann, Josefa [Verfasser], and Markus [Gutachter] Heinrich. "Entwicklung radikalischer Aryl-Aryl-Kupplungsreaktionen mit Anwendungen in der pharmazeutischen Chemie / Josefa Hofmann ; Gutachter: Markus Heinrich." Erlangen : Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), 2017. http://d-nb.info/1145293093/34.
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Monzón, Díaz Gabriel Andrés. "Zincation of heterocycles and aryl nonaflates." Diss., lmu, 2012. http://nbn-resolving.de/urn:nbn:de:bvb:19-147520.
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Ferguson, Douglas. "Selectivity of aryl and benzylic bromination." Thesis, University of Glasgow, 1997. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.340755.
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Brunton, Shirley Ann. "An aryl radical approach to mitomycins." Thesis, King's College London (University of London), 1998. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.313989.
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Tate, Joseph Andrew. "O-aryl imidates, isoureas and thiocarbamates." Thesis, University of Edinburgh, 2016. http://hdl.handle.net/1842/20976.
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Phenols are some of the most readily available and easily elaborated aromatic compounds, but the strength of the CAr-O bond hampers their conversion to highly sought CAr-N, CAr-S and CAr-C analogues. Attempts have therefore been made to establish new protocols for achieving such transformations by derivatising phenols with suitable CAr-O bond activating groups. In particular, investigations have focussed on the development of reactions with the potential to enable phenols to be conveniently converted to anilines. Towards this goal, the synthesis of O-aryl trihaloacetimidates was investigated with a view to probing their ability to rearrange to N-aryl trihaloacetamides via transition metal catalysis (Scheme 1). It was found that O-aryl trichloroacetimidates could be obtained from the base-catalysed reactions of phenols with trichloroacetonitrile, but only when electron-rich phenols were applied. In contrast, N-(4-methylphenyl)-O-aryl trifluoroacetimidates were generated in good yields from electron-rich and electron-poor phenols by their condensation with N-(4-methylphenyl)trifluoroacetimidoyl chloride. With these substrates in hand, a number of transition metal catalysts were screened for activity in the proposed rearrangement reactions, but the desired transformations were not achieved. As part of this screen, a novel mono-NHC palladium(II) precatalyst with the potential to be thermally activated was developed. Scheme 1 The proposed strategy for converting phenols to anilines. The hydroxide-catalysed rearrangement of O-aryl-N,N’-diisopropyl isoureas to N-aryl- N,N’-diisopropyl ureas was reported in 1983, but there have been no reported applications of this reaction to date. The reaction was therefore revisited with the intention of realising its unexplored synthetic potential. The reported hydroxide-catalysed rearrangement of O-phenyl-N,N’-diisopropyl isourea to N-phenyl-N,N’- diisopropyl urea was, however, discredited on the basis of 1H NMR and UV spectrometric analyses (Scheme 2). This isourea was instead, found to be converted to phenoxide and diisopropyl urea under the reported conditions. A detailed kinetic study revealed that the isourea was not directly hydrolysed, but underwent hydroxide-mediated elimination to produce phenoxide and diisopropyl carbodiimide. The hydrolysis of diisopropyl carbodiimide to diisopropyl urea then occurred in a slower, second step which was catalysed by hydroxide. Attempts to identify and synthesise N-heterocylcic isourea structures which were more disposed towards rearrangement were unsuccessful. Scheme 2 The reported and observed reactivity of O-phenyl-N,N’-diisopropyl isourea in aqueous base. Early attempts to use O-aryl-N,N’-dimethyl thiocarbamates as phenol-derived pseudohalides in palladium(0)-catalysed, CAr-C bond-forming cross-coupling reactions showed little promise due to the onset of their base-induced decomposition. However, the formation of a diaryl thioether side product was observed during these studies, leading to a preliminary investigation into the use of aryl thiocarbamates as hydrogen sulfide surrogates and thiophenol precursors in palladium(0)-catalysed C-S coupling reactions (Scheme 3). The promise of this approach was demonstrated by the synthesis of both symmetrical and unsymmetrical diaryl thioethers in the palladium(0)-catalysed couplings of O- and S-(4-trifluoromethyl)-N,N-dimethyl thiocarbamate with 1-bromo-4- fluorobenzene. Scheme 3 The preparation of diaryl thioethers from O-aryl thiocarbamates and aryl bromides via palladium(0) catalysis.
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Tsurumaki, Eiji. "Chemistry of meso-Aryl-Substituted Subporphyrins." 京都大学 (Kyoto University), 2013. http://hdl.handle.net/2433/180636.
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Burtin, Guillaume. "Synthèse totale de 13β-aryl stéroides." Aix-Marseille 3, 1997. http://www.theses.fr/1997AIX30004.
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Nos travaux concernent la preparation de 13-aryl steroides a partir d'aryl-divinylcyclopentanes issus de la condensation du 1,8-bis(trimethylsilyl)-2,6-octadiene (bistro) sur des derives de l'acide 3-benzoyl-propanoique. Nos strategies de synthese mettent en jeu une reaction de diels-alder intramoleculaire impliquant un systeme o-quinodimethane, issu de l'ouverture thermique de benzocyclobutene. La premiere sequence reactionnelle conduit, en seulement cinq etapes a partir du butadiene, a des 13-aryl steroides avec des rendements globaux de 9% ou 19%. La modification de la nature de la chaine hydrocarbonee portant le groupement benzocyclobutene a permis d'acceder en sept etapes a trois 13-phenyl-1,3,5(10)-gonatrienes, avec un rendement global de 7% a partir du butadiene. L'un d'eux possede la stereochimie de jonction de cycles trans-anti-trans des steroides naturels. La transformation selective, par une reaction d'iodolactonisation, du groupement vinylique syn du precurseur divinylcyclopentane a permis d'acceder a un nouvel intermediaire clef vinylcyclopentanique. La thermolyse de ce dernier conduit, en treize etapes a partir du butadiene et avec un rendement global de 4%, majoritairement a deux epimeres de jonction de cycles trans-anti-trans
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Vuoti, S. (Sauli). "Syntheses and catalytic properties of palladium (II) complexes of various new aryl and aryl alkyl phosphane ligands." Doctoral thesis, University of Oulu, 2007. http://urn.fi/urn:isbn:9789514286483.
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Thirty three aryl and aryl alkyl phosphane ligands were prepared and characterized for catalytic purposes. The aryl groups in both types of ligands were modified with alkyl substituents (methyl, ethyl, isopropyl, cyclohexyl, phenyl) or hetero substituents (methoxy, N,N-dimethylaniline, thiomethyl). The alkyl groups directly attached to the phosphorous atom were ethyl, isopropyl or cyclohexyl. Mono- and in some cases also dinuclear palladium (II) complexes of the ligands were prepared and characterized. The syntheses of the palladium complexes are solvent-dependent and afford either mono- or dinuclear complexes depending on the choice of the solvent. Additionally, two 2-mercaptobenzothiazole palladium complexes were synthesized and characterized. A rare distorted lantern-type structure was presented for the first time.
The ligands were characterized by 1H, 13C, 31P NMR spectroscopy and mass spectrometry. The palladium complexes were characterized by 31P NMR spectroscopy, X-ray crystallography and elemental analysis. Links between the NMR data of the palladium complexes and ligands and their catalytic activity was screened and correlation found. The crystal structures of the palladium complexes were studied for possible attractive interactions between two ligands. Such interactions were found from two examples. There is an attractive interaction between the phenyl and quinolinyl moieties of 2-quinolinyldiphenyl phosphane. A similar interaction was found between the methyl substitute and phenyl ring of o-tolylphosphane.
The ligands and palladium complexes presented in this thesis were prepared in hope of finding suitable catalysts for Suzuki coupling reactions of various bulky aryl halides and phenyl boronic acids to prepare sterically hindered bi- and triaryls under microwave irradiation. A selection of aryl alkyl phosphane ligands catalyzed the couplings of bulky aryl bromides and even unactivated aryl chlorides efficiently and produced high yields. The reaction conditions of a new catalyst system were optimized, and it was noticed that the addition of a small amount of water enhanced the purity and yield of the coupling products further.
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Kabdulov, Mikhail [Verfasser], and Martin [Akademischer Betreuer] Jansen. "Fluorine-promoted intramolecular aryl-aryl coupling : toward the isomer-specific fullerene synthesis / Mikhail Kabdulov. Betreuer: Martin Jansen." Stuttgart : Universitätsbibliothek der Universität Stuttgart, 2013. http://d-nb.info/1034074148/34.
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Crepy, Karen Viviane Lucile. "A new asymmetric aryl-aryl coupling reaction and its application to the synthesis of novel liquid crystals." Thesis, University of East Anglia, 2001. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.327498.
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Tai, Guoying. "Structural determinants of CYP2C9's genetic variability, substrate specificity and dioxygen cleavage /." Thesis, Connect to this title online; UW restricted, 2006. http://hdl.handle.net/1773/8185.
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Mridha, Niranjan Kumar. "Studies on solid phase hetero cross-coupling reactions leading to systhesis of aryl amines and their applications." Thesis, University of North Bengal, 2004. http://hdl.handle.net/123456789/774.
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Lipp, Alexander [Verfasser]. "Totalsynthese von (–)-Thebain und (–)-Oxycodon durch intramolekulare anodische Aryl–Aryl-Kupplung 3’,4’,5’-trioxygenierter Laudanosinderivate / Alexander Lipp." Mainz : Universitätsbibliothek Mainz, 2019. http://d-nb.info/1197618236/34.
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Zwiener, Matthias. "Aryl-Aryl-Kopplungen, Decarbonylierungen und Decarboxylierungen von aromatischen Anhydriden und Carbonsäuren durch das Cu(0)/Cu(I)-Paar." Diss., Ludwig-Maximilians-Universität München, 2014. http://nbn-resolving.de/urn:nbn:de:bvb:19-177937.
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Das, Purak. "Aryl azene oxides : synthesis, structure and mesogenic behaviour." Thesis, University of North Bengal, 2006. http://hdl.handle.net/123456789/870.
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Drumright, Ray E. "Radical anion rearrangements. aryl cyclopropyl ketyl anions." Diss., This resource online, 1991. http://scholar.lib.vt.edu/theses/available/etd-07282008-134853/.
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Fruteau, de Laclos Anne-Marie F. (Anne-Marie François). "Cleavage of benzyl aryl ethers by chlorine." Thesis, McGill University, 1991. http://digitool.Library.McGill.CA:80/R/?func=dbin-jump-full&object_id=70291.
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In order to extend application of the gel-degradation mechanism of delignification, model compounds of the general structure (3,4-dimethoxyphenyl)-CH(OR)R$ sp prime$ were treated at room temperature with increasing charges of molecular Cl$ sb2$ in glacial HOAc.Catalytic amounts of Cl$ sb2$ cleaved benzyl aryl ether bonds (OR=2-methoxy-4-methylphenoxy) before any ring chlorination occurred. Yields of cleavage decreased in the order: R$ sp prime$=H; R$ sp prime$=$-$CH$ sb2$-2-methoxyphenoxy; R$ sp prime$=$-$CH(CH$ sb2$OH)-2-methoxyphenoxy. These results support the concept that the delignification of wood pulp by chlorine results from benzyl aryl ether cleavage. The conditions of the reaction, as well as control reactions with hydrochloric acid, suggest that the cleavage is due to conventional acid hydrolysis induced by chlorine. The experimental evidence does not rule out another possible mechanism in which the cleavage is initiated by molecular chlorine.
Benzyl ether links were generally stable in models of the benzyl alkyl type, whose primary reactions were ring chlorination. A large excess of chlorine caused side-chain displacement, hitherto considered the primary reaction in the solubilization of lignin.
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Leary, Edmund. "Single Molecule Conductance of Dithiahexyl-Aryl Compounds." Thesis, University of Liverpool, 2008. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.507724.
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Shaikh-Omar, Osama. "Recombinant expression of the aryl hydrocarbon receptor." Thesis, University of Nottingham, 2007. http://eprints.nottingham.ac.uk/10398/.
Full textAbstract:
Aryl Hydrocarbon Receptor (AhR) mediates drug and toxin action. The AhR proteins have been characterised in several mammalian species, and are soluble proteins found in various tissues. The AhR is normally found in the cytoplasm in a complex with 90 KDa heat shock protein (hsp90) and cellular chaperones such as ARA9 (AIP or XAP2) and p23. However, there has not been a systematic analysis of the proteins which chaperone the AhR ligand-binding domain (LBD). This work investigates the interaction between ligands and the AhR, the protein composition of the AhR ligand-binding domain (LBD) complex, by establishing translation of AhR LBD in reticulocyte lysate, which contains molecular chaperones such as hsp90, and p23 that stabilise the ligand binding form of AhR. EGFP (Enhanced Green Fluorescent Protein) has been coupled to the mouse AhR b-1 LBD, to enable fluorescence analytical techniques of ligand-binding to the AhR. The Glutathione S-Transferase (GST) affinity tag was fused to EGFP (GST-EGFP), then fused to AhR.LBD with one or two EGFP (GST-EGFP-AhR.LBD and GST-EGFP-AhR.LBD-EGFP) to enable rapid one-step purification of AhR fusion proteins, and associated chaperone proteins. Proteins were expressed in E.coli (BL21(DE3)plysS). The GST protein is soluble, and not fluorescent, and GST-EGFP and GST-EGFP-AhR.LBD-EGFP was soluble and fluoresecent. The GST-EGFP-AhR.LBD was an insoluble fluorescent protein. Thus, the AhR proteins were purified from bacteria to test the specificity of the pulldown system under conditions which do not yield functional Ah Receptor. The tagged AhR constructs were translated with [35S]-methionine in reticulocyte lysate and translation products were ~36, 66, 84 and 109 kDa on SDS-PAGE. Reticulocyte lysate programmed with GST-EGFP-AhR.LBD and GST-EGFP-AhR.LBD-EGFP both bound ~800 d.p.m 2,3,7,8-[1,6-3H]tetrachlorodibenzo-p-dioxin (a ligand for the AhR), while lysate programmed with GST.EGFP showed binding of ~15 d.p.m, indistinguishable from unprogrammed lysate. The AhR proteins were purified from reticulocyte lysate and subsequent pulldown experiments will enable proteomic analysis of the proteins associated with the AhR LBD.
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Ross, Jennifer Nicola. "Alkoxy- substituted aryl- and benzyl- organotin compounds." Thesis, University of Aberdeen, 1995. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.324880.
Full textAbstract:
New organotin compounds containing alkoxy- functionalities have been prepared. The methods of preparation of the tetraorganotin species have involved three routes. Hydrostannation reactions using triphenyltin hydride have resulted in the synthesis of triphenyltin derivatives of a series of alkoxy- substituted allyl ethers. The addition of tin IV chloride, diphenyltin dichloride and phenyltin trichloride to alkoxy- substituted aryl- and benzyl- Grignard reagents have also been successful. Alkoxy- substituted benzyltin compounds have been prepared by following an alternative preparation of benzylmagnesium halides from that commonly used to prepare Grignard reagents. Nucleophilic substitution of (iodomethyl)triphenyltin by a novel ligand has been effective. The structures of the products have been investigated by 1H, 13C and 119Sn nmr. Single crystal X-ray diffraction studies have led to the determination of the crystal structures of tetra-2-anisyltin, tetrakis-(2-methoxybenzyl)tin and N,N'-bis(5-triphenylstannoxymethyl-2-phenyl-1,3-dioxan-5-yl)ethanediamide. Selective tin-carbon bond cleavage has been effected by the use of iodine and bromine to give rise to mono- and dihalo- organotin compounds and the crystal structures of tri-2-anisyltin iodide and di-2-anisyltin dibromide have been elucidated by X-ray crystallography. Chloro(3-ethoxypropyl)diphenyltin has been synthesised directly from diphenyltin dichloride and has been found to contain a penta-co-ordinate tin centre with a four membered chelate ring as a result of intramolecular tin-oxygen co-ordination. Other tin-carbon bond cleavage reactions by halogens have been studied by 1H and 119Sn nmr and GLC and the results discussed.
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Williams, Anthony. "The crisscross cycloaddition reactions of aryl azines." Thesis, Open University, 1992. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.259488.
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Khashoqji, Moayad. "Structural characterisation of novel poly-aryl compounds." Thesis, University of Manchester, 2016. https://www.research.manchester.ac.uk/portal/en/theses/structural-characterisation-of-novel-polyaryl-compounds(3fb1fac6-548a-4afc-8ac2-5a14885b0ba4).html.
Full textAbstract:
Poly-aryl, also known as polyphenylene compounds are a class of dendrimer, which contain a large number of aromatic rings. They are of interest because they display restricted rotation of their stearically congested aromatic rings. These extended structures have the potential to act as precursors for even larger aromatic systems and have many applications including electronic devices, drug delivery and catalysis. A total of 23 novel poly-aryl compounds have been examined using single crystal X-ray diffraction and a number of structural patterns have emerged. Six of the compounds contain alkynes and it has been observed that their conformation is governed by a combination of conjugation between the alkyne and aryl groups and inter-molecular interactions. In the more extended poly-aryl compounds steric congestion rules out any possibility of conjugation between the rings and their conformation is governed by intra-molecular non-bonded interactions in the core of the molecules and by inter-molecular interactions in their periphery. Where possible, solution NMR measurements were carried out on the poly-aryl compounds and confirmed that the solution structures are in agreement with those obtained from individual crystal.
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Prime, Jeremy Charles. "Some consequences of aryl substitution of porphyrins." Thesis, University of Cambridge, 1997. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.627053.
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Arrica, Maria A. "Synthesis and reactivity of aryl iodo difluorides." Thesis, Cardiff University, 2005. http://orca.cf.ac.uk/55973/.
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Organofluorine substrates are molecules of increasing demand in both academic and industrial settings. Organofluorine compounds are very rare in nature and therefore several approaches to their synthesis have been developed. In the work performed during this research tenure, the approach towards the synthesis of organofluorine substrates is based on the use of hypervalent iodine reagents. The structure of the research program can be summarized into three main sections: Synthesis of aryl iodo difluorides; Reactivity of aryl iodo difluorides towards organoselenium substrates; Approach toward stereoselective fluorinations with the synthesis of chiral iodo difluorides. Aryl iodo difluorides reagents have been known for more than a century but they have not been extensively used mainly due to their difficulty of synthesis, which require harmful and hazardous reagents. We have developed an alternative method for their preparation involving three synthetic steps: perborate oxidation of an aryl iodide, followed by basic hydrolysis and subsequent treatment with hydrofluoric acid. A number of aryl iodo difluorides were synthesized using this procedure and each of them is characterized by high purity and high yield. The reactivity of (difluoroiodo)toluene (DFIT) as a fluorinating agent was tested on organoselenium substrates. a-Seleno esters, amide and nitriles undergo a-fluorination when treated with 2 equivalents of DFIT. Under these conditions, the monofluoro derivatives were obtained with yields ranging from 20% to 65%. Additionally, (difluoroiodo)toluene can be employed in oxidative fluorinations. The exploitation of its oxidative nature produced tetraethyl ammonium iodo difluoride, and preliminary results indicate that it can be used as fluorinating agent, as well. The third aspect of the research dealt with stereoselective fluorination reactions. The synthesis of an opportune chiral iodo difluoride can provide the further development of hypervalent iodine reagents as fluorinating reagents. Different substrates were used to reach this goal and the study conducted in this direction brought about the synthesis of a difluoride with the iodine atom in oxidation state V, which can be use as chiral fluorine transfer after a simple modification of its structure.
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Mahoney, Peter M. J. "Potential routes to 11-aryl[10]annulenes." Thesis, Keele University, 1988. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.280905.
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Pintaric, Christine. "Electrosynthèse d'esters aryl- et benzylboroniques : aspects mécanistiques." Nice, 2007. http://www.theses.fr/2007NICE4091.
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L’utilisation du procédé à anode soluble pour l’élaboration d’halogénures d’aryle polyhalogénés ou fonctionnalisés par des groupements nitrile ou ester carboxylique a été développée en présence de pinacolborane et a permis d’obtenir les esters arylboroniques correspondants avec de bonnes sélectivités. La mise au point d’une nouvelle voie d’électrosynthèse d’acides et d’esters benzylboroniques basée sur l’utilisation de méthodes électrochiliques a permis la boration de substrats benzyliques par divers agents boratants (comme les trialkyl borates ou encore les dialkoxyboranes). Une approche mécanistique de la réaction d’électrosynthèse a permis de proposer une réduction des composés organoborés et l’évolution vers un produit de couplage par transfert électroniques. Les études mécanistiques ont permis de développer une nouvelle synthèse d’acides et d’esters aryl- et benzylboroniques par voie conventionnelle mettant en jeu me dérivé halogéné benzylique, le pinacolborane et la triéthylamine dans un système catalytique en magnésium (0). Nous proposons un cycle catalytique pour cette réactionFunctionalized aryl halides using sacrificial process allows the access to the corresponding arylboronic esters with good selectivity. A novel strategy for the one-step synthesis of benzylboronic acids and esters by using and electrochemical methodology is presented. The electrochemical functionalization of benzyl halides by several borating agents has been developed. Mechanistic studies on the elaboration in the presence of trialkyl borates reveal the possibility of the electroreduction of the borating agent followed by an electronic transfer. The studies of the electrolysis of benzyl halides in the presence of pinacolborane consider the electroreduction of benzyl halides to generate in situ organometallic species. These mechanistic considerations led us to develop a new preparation of aryl- and benzylboronic esters involving the halogenated derivative, pinacolborane and triethylamine in a new catalytic system using 10 mol% of magnesium(0). A catalytic cycle is proposed to understand the mechanism
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Rowland, Keith E. (Keith Edward). "An NMR Investigation of Aryl Mercury Compounds." Thesis, North Texas State University, 1987. https://digital.library.unt.edu/ark:/67531/metadc500453/.
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A variable temperature ^13 C and ^199 Hg NMR study has been conducted for diphenyl-, bis(o-tolyl)-, bis(m-tolyl)-, and bis(2, 6-xylyl)mercury in dimethyl sulfoxide and 1,1,2,2 tetrachloroethane; ^13 C T1 relaxation times are reported as a function of temperature. Barriers to rotation of the aryl rings are obtained. Chemical shifts and couplings in CDCl_3 are given for bis(p-tolyl)-, bis(2, 5-xylyl)-, bis(mesityl)-,phenyl(o-tolyl)-, phenyl(m-tolyl)mercury, and the compounds listed above. The steric interactions of these aryl mercury compounds are discussed.
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Suzuki, Masaaki. "Chemistry of meso-aryl substituted hexaphyrins(1.1.1.1.1.1)." 京都大学 (Kyoto University), 2007. http://hdl.handle.net/2433/136786.
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Chamberlin, Rachel Alexandra. "Some substitution reactions of aryl sulfides and aryl ethers with aliphatic amines in DMSO : the mechanism of base catalysis." Thesis, Durham University, 1995. http://etheses.dur.ac.uk/5213/.
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The reactions of several nitro-aromatic substrates with the aliphatic amines, n- butylamine, pyrrolidine and piperidine in DMSO have been studied. Reaction of the amines with trinitroaromatic compounds, such as ethyl thiopicrate, phenyl thiopicrate and phenyl 2,4,6-trinitrophenyl ether, was shown to occur in two well separated processes. A rapid reaction, occuring at an unsubstituted ring position, resulted in the formation of a a-adduct; this was followed by a slower substitution reaction, resulting in the displacement of the 1-substituent to give the amino-substituted compound. Kinetic results show that in the formation of the σ-adduct, the rate determining step changes from nucleophilic attack by amine with n-butylamine to proton transfer from the zwitterionic intermediate with piperidine; with pyrrolidine the proton transfer step is partially rate limiting. The substitution reaction involving n-butylamine is not base catalysed indicating nucleophilic attack, the k(_1) step, is rate determining. However, the reactions with pyrrolidine and piperidine are subject to general base catalysis showing proton transfer is involved in the slow step. The rate limiting step is thought to be the proton transfer from the zwitterionic intermediate to base. A single substitution reaction was seen for the reaction of the less activated 1-substituted 2,4-dinitrophenyl and 1-substituted 2,4-dinitronaphthyl compounds. The rate limiting step again changes from nucleophilic attack with n-butylamine to proton transfer with pyrrolidine and piperidine. The uncatalysed, k(_2), pathway was detected during the reaction of the 1-substituted 2,4-dinitrophenyl compounds. Those were the least activated substrates studied and as the effectiveness of the base catalysed step relative to the uncatalysed decomposition of the intermediate decreases with decreasing activation of the substrate, detection of the uncatalysed step became possible. Kinetic and equilibrium studies were also made on the reaction of morpholine with several phenyl ethers. Results were compared with those for piperidine with the same substrates, the values of the kinetic and equilibrium constants were as expected considering morpholine has the same steric requirements as piperidine but is considerably less basic.
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White, David Charles. "Synthesis of 3-Aryl-2-(2-aryl-2-oxoethyl)pyrido[2,3-d]-4(3H)pyrimidones and 3-Aryl-2-(2-arylethenyl)pyrido[2,3-d]-4(3H)pyrimidones as Potential Antiepileptic Drugs." Thesis, Virginia Tech, 1997. http://hdl.handle.net/10919/46506.
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A series of 2-alkyl-3-arylpyrido[2,3-d]pyrimidones were synthesized for testing as
potential antiepileptic drugs. The goal was to achieve better neurological activity and/or
lower toxicity than displayed by a series of 2-alkyl-3-aryl-4(3H)-quinazolinones prepared
previously in our research group. From the pharmacological testing data of these target
compounds, we have found that the additional nitrogen at the C-8 position of the quinazolinone
framework increased the anticonvulsant activity. However, the neurological toxicity increased
as well. The anticonvulsant and neurotoxic activity seen in the variuos 2-alkyl side chains
and 3-aryl substituents incorporated into these new pyridopyrimidones was consistent with the
activity observed with the same substituents on the 4(3H)-quinazolinones. The 3-aryl group
consists of various ortho-substituted phenyl rings, while the 2-alkyl chain consists of a
2-(2-aryl-2-oxo)ethyl or 2-arylethenyl group.Master of Science
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Richter, Catherine Ann. "Regulation of subcellular localization of the aryl hydrocarbon receptor (AHR)." free to MU campus, to others for purchase, 2000. http://wwwlib.umi.com/cr/mo/fullcitt?p9988694.
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Rosenzweig, Ella. "Exploring the role and the function of Aryl Hydrocarbon Receptor (AhR) and Aryl Hydrocarbon Nuclear Translocator (ARNT) in T cells." Thesis, University of Dundee, 2012. https://discovery.dundee.ac.uk/en/studentTheses/1d8657f4-b7b1-4508-a93f-76f21fa8d605.
Full textAbstract:
The Aryl Hydrocarbon Receptor (AhR) and the Aryl Hydrocarbon Nuclear Translocator (ARNT) play a role in mediating transcriptional responses to environmental pollutants, including the highly toxic compound 2,3,7,8-tetrachlorodibenzo -p-dioxin (TCDD) but also endogenous physiological ligands. More recent studies have also indicated that the AhR plays a role in the immune system notably in effector Th17 cells where it seems to be critical for the production of the IL-22 cytokine. It is known that AhR ligands such as dioxins can suppress CD8 T cell mediated antiviral immune responses but it is not known whether this reflects a direct role of the AhR in CD8 T cells.Accordingly, one objective of the present study was to explore AhR and ARNT expression in CD8 T cells. The initial strategy was to probe AhR and ARNT expression by western blot analysis. A second approach was to develop a mouse model that would fate mark single lymphocytes that have activated AhR signaling pathways. A third strategy was to examine the impact of deletion of AhR and ARNT on CD8 T-cell function.The data show that AhR and ARNT expression in CD8 T cells is limited to immune activated effector cells and these transcription factors are not expressed in naïve CD8 T cells. There are only low levels of AhR complexes in conventional CD8 positive cytotoxic T cells. To investigate AhR function at the single cell level we developed a mouse model to fate mark cells that have activated AhR signaling. In this model a mouse expressing Cre recombinase ‘knocked in’ to the CYP1A locus (CYP1A1Cre+/-) was backcrossed to the R26REYFP reporter mouse. In R26REYFP mice, a gene encoding EYFP is knocked into the ubiquitously expressed Rosa26 locus preceded by a loxP flanked stop sequence. CYP1A1 expression is controlled by AhR/ARNT complexes and the concept of our model was that cells that express AhR and ARNT complexes and are triggered with AhR ligands will express Cre recombinase and delete the loxP flanked stop sequence in the R26REYFP reporter locus and hence begin to express YFP.In vitro experiments demonstrated the validity of this AhR reporter model. The in vitro data reveal that expression of functional AhR/ARNT complexes occurs during Th17 and Tc17 cell differentiation but only a very low frequency of cytotoxic T cells activates the AhR. In vivo data found no evidence for AhR activation during T cell development in the thymus but show strong evidence for activation of AhR/ARNT signaling in innate lymphocytes in the gut. The ARNT transcription factor is highly expressed in cytotoxic T cells. These cells do not express functional AhR complexes, yet we considered that ARNT might play a role in CD8 T cell biology because of its ability to dimerise with the transcription factor Hif-1a. Our studies of T cells lacking ARNT expression revealed that in CD4 T cells the ARNT transcription factor regulates IL-17 and IL-22 production. In CD8 T cells we discovered that Hif-1a/ARNT signaling controls glycolysis in immune activated cells by sustaining expression of glucose transporters and multiple rate limiting glycolytic enzymes. ARNT was not required for CD8 T cell proliferation but was required for immune activated CD8 T cells to normally differentiate to express perforin and granzymes and to acquire the migratory program of effector T cells. Importantly, we discovered that Hif-1a/ARNT signaling is regulated by mTOR (mammalian target of rapamycin) thus revealing a fundamental mechanism linking nutrient sensing and transcriptional control of CD8 T-cell differentiation.
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Gil, Ramírez Guzmán. "Supramolecular chemistry of aryl extended calix [4] pyrroles." Doctoral thesis, Universitat Rovira i Virgili, 2009. http://hdl.handle.net/10803/9038.
Full textAbstract:
La presente tesis consta de dos vertientes interrelacionadas. La primera se centra en intentar cuantificar experimentalmente la contribución energética en disolución de la interacción anión-, mediante el uso de calix[4]pirroles aril substituidos en las posiciones meso- como moléculas modelo. El trabajo realizado muestra que la interacción anión- es repulsiva para anillos con valores de ESP negativos y a medida que el efecto electrón atrayente de los sustituyentes aumenta la interacción se vuelve menos repulsiva, hasta que, cuando el valor de ESP en el centro del anillo aromático es positivo la interacción se vuelve ligeramente atractiva. La segunda en el uso de estos receptores simples para obtener arquitecturas supramoleculares más complejas, y su autoensamblaje en capsulas. Los estudios muestran que calix[4]pirroles sustituidos con grupos urea en sus anillos aromáticos se autoemsamblan en capsulas diméricas en presencia de un huesped adecuado como los N-óxidos de alquil aminas y piridinas en disolventes apolares.This thesis consists of two interrelated aspects. The first one pretends to quantify experimentally the energetic contribution in solution of the anion- interaction, using aryl extended calix[4] pyrroles substituted in their meso- positions as a model system. The work performed shows that the anion- interaction is repulsive for aromatic rings with negative ESP values, as the electron withdrawing character of the substituent increases the interaction becomes less repulsive, until eventually, when the ESP value in the center of the aromatic ring is positive the interaction turns into slightly attractive.
The second one is based on the use of these simple receptors as scaffolds to obtain complex structures and their self-assembly into capsules. The studies performed show that aryl extended calix[4]pyrroles substituted with urea functions on their upper rim self-assemble into dimeric capsules in the presence of a suitable guest like the N-oxides of alkyl amines and pyridines in non-polar solvents.
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Rousseau, Cyril. "Synthèse de C-aryl glycosides par voie intramoléculaire." Phd thesis, Université d'Orléans, 2002. http://tel.archives-ouvertes.fr/tel-00168483.
Full textAbstract:
De par leurs propriétés biologiques et leur structure remarquables, les C-aryl glycosidesont suscité l'intérêt de nombreuses équipes de recherche. La création de la liaison Cglycosidique
de façon régio- et stéréocontrôlée constitue la principale difficulté de la synthèse
de ces composés.
L'objectif de ce travail est la mise au point d'une synthèse de C-aryl glycosides par voie
intramoléculaire. Nous avons développé une méthode de C-arylation intramoléculaire efficace
et stéréocontrôlée basée sur l'activation d'un glycoside de pentényle. Cette méthode a été
appliquée à la synthèse de dérivés de la Bergénine et a conduit à des produits de cyclisation
inattendus en série mannopyranose.
Pour généraliser la méthode, nous avons exploré plusieurs liens temporaires entre
l'aglycone et la copule glucidique : les agrafes de type arylsilyle nous ont permis de mettre au
point la première méthode de synthèse d'αlpha-C-aryl glucosides avec un stéréocontrôle total et de
bons rendements.