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Dissertations / Theses on the topic 'Nucleophilic substitution reaction mechanisms'

Author: Grafiati

Published: 4 June 2021

Last updated: 6 February 2022

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1

Parker, David J. "Modelling nucleophilic substitution at main group elements by NMR spectroscopy and X-ray crystallography." Thesis, Open University, 1997. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.363493.

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2

Dolliver, Debra D. "Mechanisms of Methoxide Ion Substitution and Acid- Catalyzed Z/E Isomerization of N-Methoxyimines." Thesis, University of North Texas, 2001. https://digital.library.unt.edu/ark:/67531/metadc3017/.

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The second order rate constants for nucleophilic substitution by methoxide of (Z)- and (E)-O-methylbenzohydroximoyl fluorides [C6H4C(F)=NOCH3] with various substituents on the phenyl ring [p-OCH3 (1h, 2h), p-CH3 (1g, 2g), p-Cl (1f, 2f), p-H (1e, 2e), (3,5)-bis-CF3 (1i, 2i)] in 90:10 DMSO:MeOH have been measured. A Hammett plot of these rate constants vs σ values gave positive ρ values of 2.95 (Z isomer) and 3.29 (E isomer). Comparison of these rates with methoxide substitution rates for Omethylbenzohydroximoyl bromide [C6H4C(Br)=NOCH3] and Omethylbenzohydroximoyl chloride [C6H4C(Cl)=NOCH3] r

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3

Moagi, Kgotso Herbet. "Reaction Mechanism of 2-monosubstituted Quinoxalines with Organolithium Compounds : a Theoretical Study." Diss., University of Pretoria, 2020. http://hdl.handle.net/2263/75182.

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This dissertation describes the density functional theory (DFT) computational modelling of reactions between organolithium nucleophiles and various substituted quinoxalines. These reactions result in the functionalisation of the C (sp2)–H bond, thus substituting the sigma-hydrogen. The reactions are known as nucleophilic substitution of hydrogen (SNH) and are used by experimental chemists to form new C–C bonds. The SNH reactions are very important in various industries, e.g. in designing and manufacturing of pharmaceuticals. Quinoxaline is widely used in medicinal chemistry due to its various

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4

Brammer, Larry E. "The elucidation of single electron transfer (SET) mechanisms in the reactions of nucleophiles with carbonyl compounds." Diss., This resource online, 1996. http://scholar.lib.vt.edu/theses/available/etd-06062008-151247/.

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5

MacMillar, Susanna. "Isotopes as Mechanism Spies : Nucleophilic Bimolecular Substitution and Monoamine Oxidase B Catalysed Amine Oxidation Probed with Heavy Atom Kinetic Isotope Effects." Doctoral thesis, Uppsala : Acta Universitatis Upsaliensis (AUU), 2006. http://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-7441.

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6

Chamseddine, Yssam. "Sondes mecanistiques chirales et/ou regioselectivement deuteriees : application a l'etude de quelques processus de substitution nucleophile." Paris 6, 1988. http://www.theses.fr/1988PA066133.

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7

Belknap, Ethan M. "Computational Model of the Nucleophilic Acyl Substitution Pathway." Wittenberg University Honors Theses / OhioLINK, 2021. http://rave.ohiolink.edu/etdc/view?acc_num=wuhonors1623251026132848.

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8

Curry, Omadee S. "Reaction of o-Nitrobenzenesulfonyl Azide/n-Butyl Lithium with Hindered Alcohols." Youngstown State University / OhioLINK, 2013. http://rave.ohiolink.edu/etdc/view?acc_num=ysu1379945812.

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9

Buquoi, John Quentin III. "Exploration Using Reaction Temperature to Tailor the Degree of Order in Micro-Block Copolymer Proton Exchange Membranes." Wright State University / OhioLINK, 2010. http://rave.ohiolink.edu/etdc/view?acc_num=wright1274493418.

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10

Kahef, Lana el. "Oxydation des mesotetraphenyl porphyrines : beta-substitution par voie electrochimique directe." Université Louis Pasteur (Strasbourg) (1971-2008), 1987. http://www.theses.fr/1987STR13221.

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11

Shough, Anne Marie. "Quantum chemistry studies of catalytic and photocatalytic materials transition metal substitution, active sites, thermodynamics and reaction mechanisms /." Access to citation, abstract and download form provided by ProQuest Information and Learning Company; downloadable PDF file, 260 p, 2008. http://proquest.umi.com/pqdweb?did=1597619031&sid=2&Fmt=2&clientId=8331&RQT=309&VName=PQD.

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12

Goy, Aytunc. "Axial Ligand Substitution Reaction Kinetics Of Pyrimidine-2-thionato Bridged Binuclear Platinum(iii) Complexes." Master's thesis, METU, 2007. http://etd.lib.metu.edu.tr/upload/2/12608684/index.pdf.

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ABSTRACT AXIAL LIGAND SUBSTITUTION REACTION KINETICS OF PYRIMIDINE-2-THIONATO BRIDGED BINUCLEAR PLATINUM(III) COMPLEXES G&ouml<br>y, Aytun&ccedil<br>M. S. Department of Chemistry Supervisor: Prof. Dr. H&uuml<br>seyin iS&ccedil<br>i Co-supervisor: Assoc. Prof.Dr. Seniz &Ouml<br>zalp Yaman September 2007, 89 pages The kinetics of the ligand substitution reactions, which is represented by the equation, [Pt2(C4H3N2S)4X2] + 2Y- Pt2(C4H3N2S)4Y2 + 2X- where X- = Cl-, Br-, I- and Y- = Cl-, Br-, I- are studied in acetonitrile in the presence of excess Y-

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13

Machover, Sarah B. "Understanding the Solvent-free Nucleophilic Substitution Reaction Performed in the High Speed Ball Mill (HSBM): Reactions of Secondary Alkyl Halides and Alkali Metal-Halogen Salts." University of Cincinnati / OhioLINK, 2011. http://rave.ohiolink.edu/etdc/view?acc_num=ucin1307043848.

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14

Chan, Mary S. W. "Factors influencing the regiochemistry of nucleophilic addition to the radical cation of alkenes and dienes studied in the context of the photochemical nucleophile-olefin combination, aromatic substitution (photo-NOCAS) reaction." Thesis, National Library of Canada = Bibliothèque nationale du Canada, 1998. http://www.collectionscanada.ca/obj/s4/f2/dsk2/ftp02/NQ36574.pdf.

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15

Kulchat, Sirinan. "Dynamic covalent chemistry of C=N, C=C and quaternary ammonium constituents." Thesis, Strasbourg, 2015. http://www.theses.fr/2015STRAF018/document.

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Cette thèse décrit la Chimie Covalente Dynamique (CCD) des échanges imine/imine, Knoevenagel/imine et Knoevenagel/Knoevenagel. La L-proline est un excellent organocatalyseur pour la formation de Bibliothèques Covalentes Dynamiques (BCDs). Cependant, l’interconversion entre des dérivées Knoevenagel de l’acide diméthylbarbiturique et des imines se déroule rapidement sans catalyseur. Une nouvelle classe de CCD basée sur des échanges par substitutions nucléophiles (SN2/SN2’) entre des sels d’ammonium quaternaires et des amines tertiaires est développée, impliquant la catalyse par l’iodure. Les réa

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16

Xie, Sheng. "Perfluroaryl azides : Reactivities, Unique Reactions and their Applications in the Synthesis of Theranostic Agents." Doctoral thesis, KTH, Organisk kemi, 2015. http://urn.kb.se/resolve?urn=urn:nbn:se:kth:diva-172950.

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The work centersaround perfluoroaryl azides (PFAAs), and theirability to undergo certain fast and robusttransformations. The chemistry was furtherappliedfor biomedical applications. The first section focuses on the azide-aldehyde-amine cycloaddition using PFAAs. Experimental and computational investigations uncovered a fast azide-enamine cycloaddition to form triazolines, which spontaneously rearrange into stable amidine products. In addition, this transformation was explored in the formulation of pure nanodrugs. Because this reaction can introduce a phenyl and a perfluoroaryl moiety enabling

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17

Dlubala, Alain. "Etude de la reactivite de dianions formes par double deprotonation de dithioesters beta-thiosubstitues." Caen, 1987. http://www.theses.fr/1987CAEN2010.

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18

CAPET, MARC. "Synthese d'amines allyliques : oxydation de sulfones." Paris 6, 1986. http://www.theses.fr/1986PA066547.

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L'amination allylique des olefines est catalysee par le cuivre ; application a la synthese de la gabaculine en 4 etapes. Les regio- et stereoselectivite de cette reaction sont comparees a celles de l'acetoxylation de kharasch et de sosnovsky. Des sulfones sont oxydees par des complexes peroxydique du molybdene en hydroxysulfones a squelette carbone symetrique

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19

Bielawski, Marcin. "Diaryliodonium Salts : Development of Synthetic Methodologies and α-Arylation of Enolates". Doctoral thesis, Stockholms universitet, Institutionen för organisk kemi, 2011. http://urn.kb.se/resolve?urn=urn:nbn:se:su:diva-54738.

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This thesis describes novel reaction protocols for the synthesis of diaryliodonium salts and also provides an insight to the mechanism of α-arylation of carbonyl compounds with diaryliodonium salts. The first chapter gives a general introduction to the field of hypervalent iodine chemistry, mainly focusing on recent developments and applications of diaryliodonium salts. Chapter two describes the synthesis of electron-rich to electron-poor diaryliodonium triflates, in moderate to excellent yields from a range of arenes and iodoarenes. In chapter three, it is described that molecular iodine can

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20

Vázquez, Valero Marta. "Estudio cinético de la interacción de complejos de metales de transición con moléculas biológicamente relevantes." Doctoral thesis, Universitat de Barcelona, 2016. http://hdl.handle.net/10803/390954.

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El uso de complejos inertes de metales de transición en procesos en los que se involucran moléculas biológicamente relevantes es un sistema ampliamente estudiado en la actualidad. El ejemplo a destacar de estos estudios se basa en la interacción del cisplatino, cis-[Pt(NH3)2Cl2], con polinucleótidos. La existencia de dos posiciones substitucionalmente activas en cis es crucial para los efectos observados. A partir de estas consideraciones, el objetivo propuesto para esta Tesis se basa en el estudio de reacciones de substitución sobre sistemas equivalentes con un esqueleto de coordinación inert

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21

Alvarez, Gonzalez Eleuterio. "Substitution d'ethers et d'alcools allyliques par differents nucleophiles en presence de complexes de nickel(0) : synthese stereoselective des dienes-1,4 a partir des sulfones dieniques avec le chlorure d'isopropylmagnesium en presence de sels de." Paris 6, 1987. http://www.theses.fr/1987PA066064.

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22

Jund, Rodolphe. "Electrochimie de clusters mixtes tetrametalliques." Université Louis Pasteur (Strasbourg) (1971-2008), 1987. http://www.theses.fr/1987STR13175.

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23

Chen, Yan-Ming, and 陳彥銘. "Organocatalysts in Asymmertic Nucleophilic Substitution Reaction and their Applications in Kinetic Resolution." Thesis, 2011. http://ndltd.ncl.edu.tw/handle/44674579345714916325.

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碩士<br>國立臺灣師範大學<br>化學系<br>100<br>This dessertation deals with the organocatalytic kinetic resolution of activated nitroallylic acetates 56a-h and 2-methylcyclopentane-1,3-dione 55 via SN2 reaction to produce chiral products 65a-h with a high enantiomeric excess (up to 90% ee) and a moderate chemical yield (41%) and acetates 56a-h was recovered obtained with high chemical yield (46%) ，but with a low enantiomeric excess (20% ee). Exclusive screening of various organocatalyst in our laboratory led to the conclusion that pyrrolidinyl-camphor based bifunctional organocatalyst catalyses the reaction

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24

LIN, LIN-BIN, and 林稟彬. "ynthesis of new azulenoid compounds(Nucleophilic substitution reaction, diazotization, and synthesis of new azulenopyran derivatives)." Thesis, 1993. http://ndltd.ncl.edu.tw/handle/00434585983519959643.

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25

Chu, Hon-Bein, and 朱宏彬. "The solvent effects and the structural effects of anions(Y) on the reactivity of the nucleophilic substitution reaction BzCl + Bu4NY→BzBr + Bu4NCl." Thesis, 2002. http://ndltd.ncl.edu.tw/handle/13540826365353545725.

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碩士<br>國立中央大學<br>化學工程與材料工程研究所<br>90<br>The reactivities (kf,kb) depend on the structures of the nucleophiles (Bu4NY), the solvent used. For the structural effects of Bu4NY, Y = Cl, Br, I, AcO, OH, ClO4, HSO4 were studied. And for the solvent effect, the relations between the reactivity and solvent properties (solubility parameter) has found for the various types of solvents (aprotic aliphatics, aprotic aromatics). And the effect of water on kf and kb were studies as well.

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26

Hardee, David James. "Part 1: Lanthanum(III) Triflate-Catalyzed Cyclopropanation via Intramolecular Methylene Transfer. Part 2: Reaction Design with Aromatic Ions - Nucleophilic Acyl Substitution and Organophotoredox Catalysts." Thesis, 2011. https://doi.org/10.7916/D8RX9K2H.

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This thesis describes the development of novel synthetic methods in the areas of methylene transfer cyclopropanation and reaction design with aromatic cations. The first chapter presents a new cyclopropanation method involving intramolecular methylene transfer from an epoxide to an olefin. The lanthanum(III) triflate-catalyzed process proceeds with high stereoselectivity and a range of examples are presented to illustrate the reaction scope. An asymmetric cyclopropane synthesis combining enantioselective epoxidation and the methylene transfer protocol is also presented. The second chapter desc

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27

Dubland, Joshua. "Studies towards Developing Diastereoselective SN1 Reactions of α-Keto Carbocations". Thesis, 2010. http://hdl.handle.net/1807/24246.

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Although α-keto carbocations have been demonstrated to be viable intermediates in solvolysis reactions, their applications in synthesis are scarce. These species can be considered to be equivalent to “reversed polarity” enolates and, as such, could be useful for the asymmetric formation of carbon-carbon and carbon-heteroatom bonds. In principle, facial selectivity in additions to α-keto carbocations may be induced using easily removed ester, amide, or imide chiral auxiliaries. Efforts to achieve such diastereoselective SN1 reactions of α-keto carbocations are described herein.

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