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1
Lassahn, Paul-Gerhard. "Neue Katalysatorsysteme für die Vinyl-Polymerisation von Norbornen." [S.l. : s.n.], 2003. http://www.freidok.uni-freiburg.de/volltexte/711.
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Gosmann, Mattis. "Norbornenhomo- und Copolymerisation durch Katalysatoren auf Basis der späten Übergangsmetalle." [S.l. : s.n.], 2000. http://deposit.ddb.de/cgi-bin/dokserv?idn=960263012.
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Kirsten, André. "Chemisches Recycling von PVC-haltigen gemischten Polyolefinabfällen sowie COC-Materialien durch Pyrolyse und Optimierung von Versuchsparametern mittels Pyrolyse-GC-MS." [S.l. : s.n.], 2003. http://deposit.ddb.de/cgi-bin/dokserv?idn=96907364X.
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Tran, Phu-Dennis. "Ethen-Norbornen-Copolymerisation durch Single-site-Katalysatoren-MAO." [S.l. : s.n.], 2003. http://deposit.ddb.de/cgi-bin/dokserv?idn=968875459.
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Donner, Matthias. "Synthese und Pyrolyse von metallocen-katalysierten Ethen-Norbornen-Copolymeren." [S.l.] : [s.n.], 2006. http://deposit.ddb.de/cgi-bin/dokserv?idn=980197465.
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Müller, Julia Maria. "Metatheseabbau von Butadien-Acrylnitril-Copolymeren und neue Pfropfcopolymere aus Norbornen-terminierten Poly(ferrocenyldimethylsilan)en." kostenfrei, 2008. http://mediatum2.ub.tum.de/doc/646547/646547.pdf.
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Stöhr, Torsten. "Oberflächenmodifizierungen von Siliciumoxid und Poly(ethylen-stat-norbornen) durch Blockcopolymere und an Plasmaschichten gebundene Homopolymere." [S.l. : s.n.], 2000. http://ArchiMeD.uni-mainz.de/pub/2000/0107/diss.pdf.
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Júnior, Valdemiro Pereira de Carvalho. "Reatividade de complexos do tipo [RuCl2(S-dmso)2(NIII)2 para ROMP de norborneno." Universidade de São Paulo, 2008. http://www.teses.usp.br/teses/disponiveis/75/75132/tde-20062008-165939/.
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Este trabalho reporta sínteses e caracterizações de complexos do tipo [RuCl2(S-dmso)2(N)III)2], onde NIII = piridina, isonicotinamida e nicotinamida. Os complexos foram aplicados em ROMP de norborneno de modo investigar os efeitos cooperativos entre os ligantes ancilares dmso e aminasneste tipo de reação. O complexo com nicotinamida apresentou a maior atividade catalítica em 60 min a 50 ºC (20% de rendimento; Mw / Mn = 1,98). Os outros complexos derivados foram praticamente inertes para ROMP. Usando uma solução envelhecida por 140 min a 50 ºC do complexo com isonicotinamida, não foi observada mudanças significativas na atividade catalítica por 60 min a 50 ºC (17% de rendimento; Mw / Mn = 4,24). Experimentos com uma solução do complexo com isonicotinamida na presença do sal NBu4ClO4, o rendimento foi de 19% (Mw / Mn = 1,78) mediante as mesmas condições. Usando soluções irradiadas com luz branca (5-10 min) à temperatura ambiente, os complexos com piridina e isonicotinamida mostraram rendimentos de 36% (Mw / Mn = 1,8) e 26% (Mw / Mn = 1,7) por 60 min a 50 ºC, respectivamente. O complexo [RuCl3 (Ph2SO) 3] foi também isolado e sua atividade em ROMP para norborneno foi de 33% (Mw / Mn = 1,32) à temperatura ambiente por 5 min. O rendimento aumentou para 58% (Mw / Mn = 1,41) a 50 ºC por 30 min. Na presença do sal NBu4ClO4, o rendimento de reação não apresentou mudanças significativas. Dos resultados obtidos, conclui-se que os ligantes dmso e as aminas estudadas podem ser empregados como ligantes ancilares em complexos de Ru(II) para as reações de ROMP, considerando um efeito cooperativo de sintonia eletrônica.This work reports the synthesis and characterizations of [RuCl2(S-dmso)2(N)III)2] complexes, where NIII = pyridine, isonicotinamide and nicotinamide. The complexes were applied in ROMP of norbornene in order to investigate the cooperative effects among the dmso and amines as ancillary ligands in this kind of reaction. The complex with nicotinamide showed the highest catalytic activity for 60 min at 50 ºC (20% yield; Mw / Mn = 1,98). The other derivatives were roughing inert for ROMP. Using an aged solution for 140 min at 50 ºC of the isonicotinamide complex, it was observed a significant change in their catalytic activity for 60 min at 50 ºC (17% yield; Mw / Mn = 4,24). Experiments using isonicotinamide complex solution in presence of the salt NBu4ClO4, the yield was 19% (Mw / Mn = 1,78) under similar conditions. When using irradiated solution with white lamp (5-10 min) at room temperature, the pyridine (for 10 min) and isonicotinamide (for 5 min) complexes showed yields of 36% (Mw / Mn = 1,8) and 26% (Mw / Mn = 1,7) for 60 min at 50 ºC respectively. The complex [RuCl3 (Ph2SO) 3] was also isolated and the ROMP active for norbornene was 33% (Mw / Mn = 1,32) at room temperature for 5 min. The yield increased to 58% (Mw / Mn = 1,41) at 50 ºC for 30 min. In the presence of the salt NBu4ClO4, the yield showed no significant changes. It is concluded that the ligands dmso and the studied amines can be selectively used as ancillary ligands in Ru(II) complexes for ROMP reactions inside of an electronic tuning cooperative effect.
9
Ferreira, Daniele Marcondes. "Coordenação a centros de rutênio e polimerização via metátese de um novo monômero-ligante do tipo norborneno-piridina." Universidade de São Paulo, 2012. http://www.teses.usp.br/teses/disponiveis/75/75135/tde-17042012-170048/.
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O monômero-ligante (3amdpy)2NBE foi sintetizado e caracterizado por análise elementar (CHN), infravermelho e RMN (1H e 13C), tratando-se de um novo ligante quelante que apresenta duas piridinas conectadas ao monômero norborneno via grupos amidas. Esse monômero-ligante foi ligado a um centro de Ru(II)-polipiridínico e o complexo resultante foi caracterizado por análise elementar (CHN), infravermelho, RMN (1H e 13C) e espectrometria de massa como sendo cis-[Ru(bpy)2((3amdpy)2NBE)](PF6)2. O espectro eletrônico do novo complexo apresentou absorção no visível em 460 e 480 nm. Essa bandas são típicas de MLCT com valores de ε na ordem de 104 L cm-1 mol-1. O voltamograma cíclico em CH3CN apresentou um processo redox com potencial de meia-onda de 0,89 V vs Ag/AgCl que é de 60 unidades mais positivo do que o complexo precursor cis- [RuCl2(bpy) 2]. O novo metalo-monômero foi submetido à irradiação a λ= 480 nm, demonstrando ser fotoquimicamente inerte em DMSO, CH3CN, acetona e DMF. A emissão do complexo obtido variou em função do solvente e apresentou maior intensidade de emissão em acetonitrila (λem= 720 nm). A variação do solvente não levou ao deslocamento do máximo de emissão do complexo. O monômero-ligante foi polimerizado via metátese catalisada por catalisador de Grubbs, com 23% de rendimento a 50 °C por 5 min. O polímero foi caracterizado por IV e RMN de 1H. Foi solúvel em água e apresentou um ponto de fusão de 288ºC.The monomer-ligand (3amdpy)2NBE was synthesized and characterized by elemental analysis (CHN), infrared and NMR (1H and 13C) as a new chelate ligand that features two pyridines connected to the monomer norbornene via amide groups. This monomer-ligand was coordinated to a Ru(II)-polypyridinic center and the resulting complex como sendo cis- [Ru(bpy) 2 ((3amdpy) 2NBE)](PF6)2 was characterized by elemental analysis (CHN), IR, NMR (1H and 13C) and mass spectrometry. The electronic spectrum of the new complex showed absorptions in the visible with bands at 460 and 480 nm. These bands are typical of MLCT with ε values in the order of magnitude of 104 L cm-1 mol-1. The cyclic voltammetry in CH3CN showed a redox process with half-wave potential of 0,89 V vs Ag/AgCl which is ca. 60 units higher than the halfwave potential for the cis-[RuCl2(bpy)2] precursor complex. The new complex was photochemically inert when irradiated at 480 nm either in DMSO, CH3CN, acetone or DMF. The emission of the complex depends on the solvent and presented large emission intensity in acetonitrile (λem = 720 nm). The variation of the solvent does not shift the emission maximum. Ring opening metathesis polymerization of the monomer-ligand (3amdpy)2NBE was carried out at 50 °C for 5 min with 23% of yield using Grubbs type catalyst. The resulting polymer was characterized by IR and NMR-1H. It was water-soluble and showed a melting point of 288°C.
10
Henkel, Michael Max Franz Klaus [Verfasser], Thorsten [Akademischer Betreuer] Bach, Thorsten [Gutachter] Bach, and Wolfgang [Gutachter] Eisenreich. "Palladium-katalysierte CH-Aktivierung von Indolen mit 1,n-Dibromiden und chiralen Norbornen-Derivaten / Michael Max Franz Klaus Henkel ; Gutachter: Thorsten Bach, Wolfgang Eisenreich ; Betreuer: Thorsten Bach." München : Universitätsbibliothek der TU München, 2020. http://d-nb.info/1225480035/34.
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11
Han, Bo. "Deuteriohalogenation of norbornene via organoborane /." Online version of thesis, 1991. http://hdl.handle.net/1850/11307.
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12
Banti, Donatella. "Ene-Yne metathesis of norbornene derivatives." Thesis, King's College London (University of London), 2003. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.411341.
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13
Tomazett, Vinicius Kalil. "Síntese de monômeros luminescentes com norborneno e suas polimerizações via metátese." Universidade de São Paulo, 2016. http://www.teses.usp.br/teses/disponiveis/75/75135/tde-30032017-094650/.
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As reações de metatese assim como o desenvolvimento de complexos metal-carbeno (W, Mo, Ru) se tornaram amplamente conhecidos na química graças aos avanços que trouxeram. Na química orgânica, possibilitou a síntese de macrocíclos por meio da RCM e na química de polímeros a ROMP permitiu um alto grau de controle da polimerização além da alta reatividade dos catalisadores. Isso fez desta reação uma poderosa ferramenta no desenvolvimento de novos materias. A tentativa de combinar a processabilidade dos polímeros com as propriedades luminescentes de determinandos compostos tem sido tema de muitas pesquisas.O objetivo deste trabalho é derivatizar compostos luminescentes , como o complexo metálico [Ru(bpy)3] (PF6)2e a porfirina tetrakis-(pentafluorfenil)porfirina (TPPF20), com o monômero norborneno (NBE) para obtenção de monômeros lumiscentes passíveis de serem polimerizados via ROMP. Aqui será apresentado e discutido a síntese e a caracterização desses compostos partindo-se dos reagentes: ácido-5-norborneno-2carboxílico; etilenodiamina e o ácido-2,2\'-bipiridina-4,4\'-dicarboxílico, cis-[RuCl2(bpy)2] e a porfirina TPPF20. Os compostos foram sintetizados com rendimentos superiores a 60%, com exceção da obtenção da porfirina, e caracterizados por RMN - 1H e 13C; FTIR; UV-vis. Os estudos de copolimerização entre NEN (norborneno-etilenodiamina-norborneno), NBE-TPPF e [Ru(bpy)2(NBbpy)](PF6)2 foram feitos usando o catalisador de Grubbs segunda gereação. Os polímeros gerados foram caracterizados usando TG-FTIR e RMN-1H, as massas moleculares não puderam ser calculadas por GPC porém os estudos indicam obtenção de baixo peso molelcular. O material obtido foi testado como sensibilizador em vidro condutor ITO, porém não houve adsorção do composto necessitam algumas modificações no metalomonômero.The metathesis reactions as well as the development of metal-carbene complexes (W, Mo, Ru) became widely known in chemistry thanks to advancements brought. In organic chemistry, it enabled the synthesis of macrocycle by RCM. Useful for the synthesis of natural products. In polymer chemistry, ROMP, allow a high degree of polymerization control. This made the ROMP reaction a powerful tool in the development of new materials. In attempt to combine the processability of polymers with luminescent properties of such compounds has been the subject of several researchs. The aim of this work is to synthesize luminescent compounds based on [Ru(bpy)3] (PF6)2 metal complex and on the porphyrin tetrakis-(pentafluorphenyl)porphyrin (TPPF20), funcionalized with pendant norbornene monomer (NBE) to obtain lumiscentes monomers which can undergo ROMP polymerization. Here will be discussed the synthesis and characterization of these compounds using as starting materials: 5-norbornene-2-carboxylic acid; ethylenediamine; 2,2\'-bipyridine-4,4\'dicarboxylic acid, cis-[RuCl2(bpy)2] and the porphyrin TPPF20. The compounds were synthesized with yields higher than 60%, with the exception of the porphyrin, and characterized by 1H and 13C-NMR; FTIR; UV-vis. Copolymerization reaction between NEN (Norbornene-Ethylenediamine-Norbornene), NBE-TPPFe [Ru(bpy)2(NBbpy)] (PF6)2 were performed using Grubbs second generation catalyst. Resultinf polymers were characterized by TG-FTIR and 1H-NMR, molecular weight could not be measured by GPC, since polymers were insoluble, but studies indicate low molelcular weight. The material obtained was tested as sensitizer in conductive glass ITO. The polymer didn\'t adsorb in to the ITO surface. Some changes in the compound molecular structure are required to improve adsorption.
14
Hansell, Claire F. "Tetrazine-norbornene cycloadditions in macromolecular synthesis and functionalisation." Thesis, University of Warwick, 2013. http://wrap.warwick.ac.uk/58244/.
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This thesis explores the use of the tetrazine–norbornene inverse electron demand Diels-Alder cycloaddition reaction in polymer and materials science. Chapter 1 gives an introduction to the main concepts and techniques used throughout the thesis. Chapter 2 applies the tetrazine–norbornene reaction to polymer endfunctionalisation and polymer–polymer coupling, in both organic media and water, and establishes the methods (UV/vis and 1H NMR spectroscopies) for monitoring the coupling reaction. Chapter 3 applies the reaction to the modification of a self-assembled polymer micelle and demonstrates its use in tandem with the coppercatalysed azide–alkyne click reaction. The synthesis of an amphiphile bearing both norbornene and alkyne groups is described, the amphiphile is self-assembled and a one-pot dual functionalisation of both the core and shell carried out. Chapter 4 describes the formation and analysis by a variety of methods of sub-20 nm sized polystyrene nanoparticles through the single chain collapse of a norbornene-decorated polymer, ligated with a bisfunctional tetrazine. Chapter 5 discusses attempts to further expand the use of the reaction of tetrazines to polymers bearing pendent alkene groups. The synthesis and characterisation of such polymers is detailed, and attempts to functionalise with a variety of tetrazines described.
15
Al-Hajaji, Abdullah Mosed Ahmed. "Ring opening metathesis polymerisation of some imido norbornene derivatives." Thesis, Durham University, 1995. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.294661.
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Jones, Iwan Gwynedd. "Desymmetrization of meso-anhydrides by proline esters." Thesis, Bangor University, 1998. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.265515.
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Blanco, Jiménez Carolina. "Norbornene functionalization through asymmetric pd- and rh-catalyzed carbonylation processes." Doctoral thesis, Universitat Rovira i Virgili, 2010. http://hdl.handle.net/10803/9109.
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Esta tesis se ha centrado en el estudio de las reacciones de carbonilación de norborneno catalizada por metales. Este sustrato puede ser funcionalizado a través de este proceso, empleando sistemas catalíticos y condiciones de reacción adecuadas, en productos intermedios con aplicación en la industria de perfumes y química fina. En este trabajo se han llevado a cabo estudios en la reacción de metoxicarbonilación de norborneno catalizada por paladio empleando ligandos monofosfina y difosfina logrando un importante control de la selectividad hacia la formación del producto deseado. Algunos aspectos mecanísticos de esta reacción han sido desarrollados empleando métodos de resonancia magnética nuclear que incluyen experimentos de alta presión. Finalmente, se ha estudiado la reacción de hidroformilación asimétrica de norborneno catalizada por complejos de rodio usando ligandos difosfito derivados de carbohidrato. Estos sistemas catalíticos han mostrado alta actividad y selectividad con excesos enantioméricos moderados.This thesis focuses on the study of the metal-catalyzed carbonylation of norbornene. The transformation of this substrate in esters and aldehydes offers potential applications for the production of valuable compounds in fine chemistry and perfumery industry. In this work we have performed studies on the palladium-catalyzed methoxycarbonylation of norbornene bearing monodentate and bidentate phosphine ligands achieving an important control of the selectivity towards the formation of the desired product. Mechanistic aspects of this reaction have been developed using nuclear magnetic resonance methods, including High-Pressure techniques. Finally, we have studied the asymmetric rhodium-catalyzed hydroformylation of norbornene using chiral 1,3-diphosphites ligands derived from carbohydrates. These catalytic systems have shown high activities with excellent stereoselectivities and moderate enantioselectivities.
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Egunlusi, Ayodeji Olatunde. "Novel norbornane derivatives as potential neuroprotective agents." University of Western Cape, 2020. http://hdl.handle.net/11394/7339.
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Philosophiae Doctor - PhDNeurodegenerative disorders are characterised by progressive loss of the brain’s physiological functions as a result of gradual degeneration of neurons in the central nervous system. Even though they are classified as diseases of the elderly, occurrence earlier in life is possible, but that would suggest the influence of genetic and/or environmental factors. Due to the continuous rise in modernisation and industrialisation over the years, there has been an increase in incidence and prevalence of neurodegenerative disorders. With the advances in technology and life expectancy, the rates of the common forms (Alzheimer’s disease and Parkinson’s disease), are expected to increase exponentially by 2050. Unfortunately, there is still no clinically approved treatment or therapy to slow down or halt the degenerative process as most registered drugs only offer symptomatic relief. Confounding this issue is the lack of definite mechanism of neurodegeneration, which is still poorly defined and not completely understood. Nonetheless, the pathology of most neurodegenerative disorders is believed to be a combination of interrelated processes that eventually leads to neuronal cell death. Among the postulated processes, the impact of excitotoxicity mediated by NMDA receptor over-activation is prominent and it is implicated in virtually all neurodegenerative disorders. With this basic insight, it is believed that molecules capable of inhibiting NMDA receptors and associated calcium channels, without affecting the normal physiological functions of the brain, could potentially serve as good neuroprotective drugs. Competitive and uncompetitive blockers (MK-801 and ketamine) have been explored, but none were clinically accepted due to undesirable side effects such as hallucinations, sedation and depression. However, NGP1-01, a polycyclic cage molecule, has been shown to be neuroprotective through modulation of NMDA receptors and voltage gated calcium channels and attenuation of MPP+ -induced toxicity. A similar approach could be useful in the design and development of new neuroprotective drugs. The aim of this study was to synthesise a series of open and rearranged cage-like molecules and explore their neuroprotective potential in neuroblastoma SH-SY5Y cells. The proposed structures, with norbornane scaffolds that contained different moieties, were designed to structurally resemble NGP1-01 and MK-801. Once synthesised, the compounds were purified and characterised, and were evaluated for their biological activities. Compounds were first screened for cytotoxicity at different concentrations. Thereafter, they were evaluated for neuroprotective effects against MPP+ -induced excitotoxicity and for calcium flux modulatory effects on NMDA receptor and voltage gated calcium channels. The norbornane derivatives were synthesised and characterised, and all final products were afforded in sufficient yields. All compounds with the exception of two compounds displayed good cytotoxic profiles towards the SH-SY5Y neuroblastoma cells at 10 µM, 50 µM and 100 µM concentrations as they demonstrated percentage cell viabilities close to 100% (control treated cells). Only two compounds showed percentage cell viability of 51% and 59% at 100 µM. Utilising the same cell line, all compounds, tested at 10 µM, attenuated MPP+ -induced toxicity after 24 hours of exposure to a neurotoxin. This was evident in the 23% to 53% enhancement (significant with p < 0.05) in cell viability when compared to the MPP+ only treated cells. In comparison to known NMDA receptor and/or voltage gated calcium channel blockers (MK-801, NGP1-01 or nimodipine), the synthesised compounds demonstrated mono or dual inhibition of calcium channels as they effectively attenuated calcium influx by blocking NMDA receptors and/or voltage gated calcium channels expressed in neuroblastoma SHSY5Y cells. This group of compounds were found to be more potent NMDA receptor inhibitors, probably due to similarities with MK-801 and memantine, than voltage gated calcium channel inhibitors. All compounds demonstrated moderate to good calcium inhibitory effects at NMDA receptors in the range of 23% to 70% while a selected few displayed very little or no activity at the voltage gated calcium channels. In conclusion, 27 compounds with norbornane scaffolds were successfully synthesised and evaluated for cytotoxicity and neuroprotection. The abilities of the synthesised compounds to protect neurons from the neurotoxin MPP+ and reduce calcium flux into neuronal cells were successfully demonstrated. These characteristics are essential in neuroprotection as they may prove significant in halting or slowing down the disease progression. The compounds showing a good cytotoxicity profile, neuroprotective effects and ability to reduce calcium overload, could potentially act as neuroprotective agents with good safety profiles or contribute as lead structures to the development and design of structurally related molecules that could clinically benefit people with neurodegenerative disorders.
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Laird, Darin Wiley. "Theoretical and experimental investigations of norbornyne and cyclohexyne /." Full text (PDF) from UMI/Dissertation Abstracts International, 2001. http://wwwlib.umi.com/cr/utexas/fullcit?p3008374.
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Gumus, Aysegul. "Stereoselective Synthesis Of Cyclopentanoids And Cyclitol Derivatives Originated From Polychlorinated Norbornene Systems." Phd thesis, METU, 2009. http://etd.lib.metu.edu.tr/upload/3/12611020/index.pdf.
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Optically active polychlorinated norbornene systems are important starting compounds for the synthesis of many complex molecules. The synthetic strategy of this study mainly depends upon the enzymatic resolution of hydroxymethyl-substituted polychlorinated norbornene structures. The enantiomerically enriched acetoxymethyl derivatives were synthesized in high ee values by several lipases. The absolute configuration of tetrachlorinated norbornene system was determined by X-ray analysis.
The second part of the thesis involves the ruthenium and cerium-catalyzed oxidation reactions of various polychlorinated norbornene derivatives to afford α
-diketones. The regioselectivity of ruthenium catalyst was tested in polychlorinated norbornadiene systems. In the third part of the study, cyclopentanoid derivatives were synthesized in high chemical yield starting from enantio-enriched both tetra- and hexa-chlorinated norbornene derivatives. In the last part of the study, stereo- and regioselective synthesis of carbasugar systems which are potential glycosidase inhibitors were performed. Starting from enantio-enriched acetoxymethyl substituted tetrachloro norbornene system both carbasugar by cleavage of C1-C7 bond and &lsquo
confused&rsquo
carbasugar by cleavage of C4-C7 bond were synthesized.
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Mainville-Dale, Rachel M. E. "Theoretical prediction and spectroscopic characterization of novel norbornene and norbornadiene polymer structures." Thesis, University of Ottawa (Canada), 2002. http://hdl.handle.net/10393/6134.
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This thesis describes efforts in theoretical prediction of the macrostructures of poly(norbornadienes) and poly(norbornenes). In contrast to existing synthetic helical polymers such as poly(isocyanides) and poly(methacrylates), the helical parameters of norbornene and norbornadiene polymers may be tunable by judicious choice of substituents. Computer modelling surveys were carried out to qualitatively compare effects from tacticity, steric bulk, pi-stacking and hydrogen-bonding on polymer topology. Models capable of pi-stacking and hydrogen-bonding displayed interactions between substituents on neighbouring repeat units. These modelling studies suggest that helical turns will collapse to form and enforce a tube-like structure. Polymers of functionalized norbornenes and norbornadienes were produced using different achiral and racemic catalysts. Microstructural characterization was conducted by 1H, 1H-1H COSY and 13C{1H} NMR spectroscopy. The tacticities of poly(norbornadienes) agreed well with literature reported values of the catalyst used. However, all three poly(norbornenes) had the same tacticity. Macrostructural characterization was accomplished by GPC, LS, polarimetry and CD spectroscopy. All polymers had a spherical conformation in solution. Polymers made of optically active monomers were optically active whereas polymers made of non-optically active monomers were not.
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Carlise, Joseph Raymond. "Poly(norbornene) supported side-chain coordination complexes : an efficient route to functionalized polymers /." Diss., Available online, Georgia Institute of Technology, 2006, 2006. http://etd.gatech.edu/theses/available/etd-04072006-111344/.
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Thesis (Ph. D.)--Chemistry and Biochemistry, Georgia Institute of Technology, 2006.Prof. Will Rees, Committee Member ; Prof. Charles Liotta, Committee Member ; Prof. David Collard, Committee Member ; Prof. Marcus Weck, Committee Chair ; Prof. Kent Barefield, Committee Member.
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Giles, Matthew Robert. "The ring opening metathesis polymerisation of norbornene monomers containing amino acid/ester functionalities." Thesis, Imperial College London, 1998. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.301002.
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Gillan, Eileen Marie Danielle. "The mechanism of initiation and propagation of ring-opening metathesis polymerization of norbornene." Thesis, Queen's University Belfast, 1988. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.335961.
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Lago, Wowro Rosine Sonia. "Etude du vieillissement des copolymères d'éthylène et de norbornène." Thesis, Université Paris-Saclay (ComUE), 2018. http://www.theses.fr/2018SACLS556/document.
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Ce travail de thèse avait pour objectif d’étudier différents vieillissements des copolymères d’éthylène et de norbornène (ENC), utilisés comme conditionnement de produits pharmaceutiques. Grâce à la stratégie analytique adoptée qui a fait appel à différentes techniques de caractérisation, telles que les techniques séparatives comme la chromatographie d’exclusion stérique, la chromatographie liquide haute performance à polarité de phases inversée, les techniques spectrales dont la spectroscopie infra rouge à transformée de Fourier et la spectroscopie UV, les techniques d’analyse thermique à travers l’analyse thermogravimétrie et la calorimétrie différentielle à balayage, puis d’une étude de toxicité des produits de dégradations, nous avons pu mettre en évidence différents types de modifications dans le volume du matériau après vieillissement. La modification principale dans la masse du matériau, observée à la dose réglementaire de stérilisation (25 kGy), est la scission des chaînes du polymère qui s’accompagne de la création de composés de basses masses molaires, donc de migrants potentiels risquant d’influencer la sécurité d’emploi des ENC. Puis pour des doses élevées de rayonnement (150 kGy) et pendant 500h d’exposition UV, on a la réticulation des chaînes.La présence de l’additif (l’antioxydant phénolique l’Irganox 1010®) empêche la création des CBMM après vieillissements. Cependant, en absence d’additif, les vieillissements génèrent de nouveaux CBMM.Toutefois, l’étude de toxicité montre une certaine toxicité à 150 kGy du grade ENCThe aim of this thesis work was to study different ages of copolymers of ethylene and norbornene (ENC), used as packaging of pharmaceutical products. Thanks to the analytical strategy adopted using different characterization techniques, such as separation techniques such as size exclusion chromatography, reverse phase high performance liquid chromatography, spectral techniques including infrared spectroscopy transforming of Fourier and UV spectroscopy, thermal analysis techniques through thermogravimetric analysis and differential scanning calorimetry, and then a toxicity study of degradation products, we were able to highlight different types of modifications in the volume of the material after aging. The main modification in the bulk of the material, observed at the prescribed sterilization dose (25 kGy), is the cleavage of the polymer chains, which is accompanied by the creation of compounds with low molar masses, and therefore potential migrants, which are likely to influence ENC job security. Then for high doses of radiation (150 kGy) and for 500h UV exposure, there is the crosslinking of the chains. The presence of the additive (the phenolic antioxidant Irganox 1010®) prevents the creation of MBMM after aging. However, in the absence of an additive, aging generates new CBMMs. However, the toxicity study shows some toxicity at 150 kGy of the ENC
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Sunbul, Murat. "Asymmetric Synthesis Of Norbornene Based 1,4-amino Alcohol Derivatives And Applications In Asymmetric Transformations." Master's thesis, METU, 2005. http://etd.lib.metu.edu.tr/upload/12606174/index.pdf.
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The asymmetric synthesis of cis-1,4-aminoalcohols with norbornene backbone was performed starting with simple and cheap anhydride 30. Quinine-mediated desymmetrization of anhydride 30 with methanol resulted in (2S,3R)-(-)-cis-hemiester 31 (98% e.e.). Chemoselective amination with HMPTA and NH4OH followed by LAH reduction afforded (2S,3R)-(+)-36 and (2S,3R)-(-)-37, respectively. The amidoester (2S,3R)-(-)-32 was transformed into chiral ligand (2S,3R)-(-)-35 with Grignard reaction followed by LAH reduction.
The chiral ligands (2S,3R)-(-)-35, (2S,3R)-(+)-36 and (2S,3R)-(-)-37 were subjected to asymmetric diethylzinc addition reaction to examine their effectiveness as chiral catalyst. Among these, chiral ligand 36 exhibited the highest enantioselectivity (88% e.e.)
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Erdem, Mine. "Asymmetric Synthesis Of Norbornene Based 1,4-aminoalcohol Derivatives And Applications In Asymmetric Diethylzinc Reactions." Master's thesis, METU, 2007. http://etd.lib.metu.edu.tr/upload/12608318/index.pdf.
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The asymmetric synthesis of chiral norbornene based 1,4-aminoalcohols and their applications in asymmetric diethylzinc addition reactions was perfomed starting from meso-anhydride 50. The desymmetrization of this meso-anhydride 50 was done by the usage of quinine or quinidine cinchona alkaloids with very high enantiomeric excess values (up to 98% ee) and chemical yields. The Quinidine-mediated desymmetrization of meso-anhydride 50 with methanol gave (2R,3S)-(+)-cis-monoester 51. The amination of this resulting compound with HMPTA was performed and by keeping the amine group constant, the amidoester was transformed into chiral ligands with Grignard reaction followed by LAH reduction.
The effectiveness of 1,4-aminoalcohol type ligands, (2R,3S)-(-)-57, (2R,3S)-(-)-58, (2R,3S)-(-)-59 and (2S,3R)-(+)-60 as chiral catalysts in asymmetric diethylzinc addition reaction to benzaldehyde were examined and the ligand 60 gave the highest enantioselectivity (69% e.e.)
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Chung, Won Jae. "Molecular modeling of structure-property relationship for palladium catalyzed poly(norbornene) and it derivatives." Diss., Georgia Institute of Technology, 2003. http://hdl.handle.net/1853/11318.
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Atter, Kieran Timothy. "Syntheses and ROMP of norbornene-functionalised polyesters and polyurethanes and evaluation of their products." Thesis, Durham University, 2018. http://etheses.dur.ac.uk/12612/.
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The aim of this project is to develop a polymer system which: 1) incorporates one or more norbornene rings in the pre-polymer; 2) can be polymerised using ROMP to yield linear or cross-linked polymers; 3) utilises little, or no, styrene; 4) produces products with comparable properties to current unsaturated polyester resins; 5) can polymerise in solvent, or in the presence of a reactive diluent; 6) is as environmentally friendly as possible; and 7) is as cost-effective as possible. Chapter 1 contains a history of olefin metathesis, ROMP, and ROMP catalysts. Using ROMP to polymerise norbornene-containing monomers is also included, as well as the synthesis of random and block-copolymers using ROMP. In Chapter 2, norbornene-containing polyesters – synthesised at Scott Bader – are characterised using 1H and 13C NMR spectroscopy, and SEC. The syntheses of hexamethylene-1,6-bis(5-norbornene-2-methoxy tetraethylene glycol carbamate) (DFM1); 2-hydroxyethyl-5-norbornene-2-carboxylate (HE-NBE-CO2); hexamethylene-1,6-bis(5-norbornene-2-carboxylate-2-ethoxy carbamate) (DFM2); and 2-hydroxyethyl-5-norbornene-2-carboxylate butyl carbamate (MFM) are all reported, and confirmed by characterisation using 1H and 13C NMR spectroscopy and ASAP mass spectrometry. Chapter 3 details the polymerisation of N-2-ethylhexyl norbornene dicarboximide (EHNBEDC) using Grubbs 1st generation (G1); 2nd generation (G2); and modified 2nd generation (MG2) catalysts; and analyses thereof. As well as this, Polyesters 1 and 2 are shown to undergo ROMP with all three catalysts and cross-link to form a gelled polymer. The gel contents and gel time of which was measured. Finally, Polyesters 1 and 2 are copolymerised with EHNEBDC using the three catalysts and shown to increase the gel contents with increasing concentration of the polyester. In Chapter 4, styrene is added to the reaction mixture for the ROMP of Polyesters 1 and 2. Increasing the level of styrene up to 2 equivalents with respect to the initiator is shown to have no effect on the gel contents with any of G1, G2 or MG2. However, the gel time can be increased by increasing the styrene up to 5 equivalents with respect to G1 or G2; though there is no increase in gel time observed when using styrene with MG2. Chapter 5 shows that MFM, DFM1 and DFM2 can be polymerised using ROMP with G1, G2 and MG2. The ROMP of MFM produces a linear polymer which can be characterised using 1H and 13C NMR spectroscopy, as well as SEC. DFM1 and DFM2 produce cross-linked polymers when they undergo ROMP. MFM can produce a block copolymer with EHNBEDC when using G1 as the initiator. Random and block copolymers of HE-NBE-CO2 and MFM are also formed using varying levels of each monomer. Some of the copolymer systems are tested using Dynamic Mechanical and Thermal Analysis (DMTA): measuring their Tg’s and storage moduli. In-mould bulk copolymers, using MG2 as the initiator, are achievable in several copolymer systems. Any trends in the Tg, or storage modulus, are investigated for each system. Finally, Chapter 6 offers conclusions to the work undertaken and some possible future work to further understand the polyesters and polyurethanes and their ROMP products, as well as the possibility of increasing the library of polyesters and polyurethanes using differing starting materials.
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Cramail, Henri. "Oligomérisation fonctionnelle du norbornène : application à la synthèse de réseaux." Bordeaux 1, 1990. http://www.theses.fr/1990BOR10511.
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La polymerisation metalla-carbenique (par reaction de metathese) du norbornene en presence de diesters insatures a permis d'obtenir des oligomeres du norbornene porteurs de fonctions ester aux extremites des chaines. Les diesters derives d'acides ethyleniques se sont averes les meilleurs agents de transfert et conduisent a des oligomeres de fonctionnalite proche de deux. Une etude cinetique du processus a ete realisee et a permis de proposer un mecanisme de la reaction. Ces oligomeres ont ete ensuite transformes en prepolymeres hydroxy-telecheliques lesquels peuvent etre utilises comme precurseurs de reseaux polyurethane. Les proprietes physico-chimiques et thermo-mecaniques de ces resequx ont ete evaluees
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Leymet-Digelmann, Isabelle. "Etude de l'activation de la polymérisation du norbornene, amorcée par un complexe carbénique du tungstène." Paris 13, 1987. http://www.theses.fr/1987PA132013.
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Cinétique, mécanisme faisant intervenir le coordination du monomère au tungstene préalablement à son insertion dans la double liaison carbenique. Système à très haute activité faisant intervenir alcl::(3) comme activateur
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Thompson, Ian. "Synthesis, characterisation and property evaluation of methyl methacrylate functionalised poly(norbornenes)." Thesis, Imperial College London, 2002. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.252262.
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Bordes, Romain. "Synthèse, physicochimie et polymérisation de tensioactifs paires d'ions dérivés du norbornène." Toulouse 3, 2007. http://thesesups.ups-tlse.fr/60/.
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L'introduction d'une fonction polymérisable par voie radicalaire au niveau d'un tensioactif permet de figer les morphologies des agrégats, et contourner ainsi le problème de la réversibilité dynamique des objets formés dans l'eau. Grâce à une stratégie de synthèse polyvalente, des tensioactifs paires d'ions polymérisables par voie organométallique de type alkylcarboxylate-norbornène méthylèneammonium ou alkylammonium-norbornène carboxylate ont été préparés. Ces tensioactifs, d'un comportement proche d'amphiphiles zwittérioniques, forment spontanément dans l'eau des vésicules stables, ce qui traduit une organisation en bicouche avec une forte cohésion des ions de la paire. L'étude de ces systèmes paires d'ions en fonction de la concentration a également mis en évidence, pour certains dérivés, une transition micelle-vésicule, qui dépend principalement de la structure du contre-ion. Les tests de polymérisation par voie vinylique et par métathèse ont montré le maintien de la structure vésiculaire des agrégats lors de la polymérisation. Ces tensioactifs peuvent aussi stabiliser des émulsions, ce qui permet d'envisager la préparation de latex stables par voie organométallique. Cette étude a également conduit à la mise au point d'un nouveau tensioactif polymérisable, basé sur l'association entre un dérivé acide du norbornène et l'hydroxyde de cétyltriméthylammonium (CTAOH)A polymerizable function via a radical route, for a rapid lock’ in of the morphologies, is generally introduced in order to overcome the reversibility of the dynamical aggregation of surfactants in water. Ion paired surfactants polymerizable via an organometallic route, as norbornene methyleneamonium alkylcarboxylate or alkylammonium norbornene carboxylate, were prepared via a versatile synthesis way. These ion-paired systems exhibit a physico-chemical behaviour close to zwitterionic surfactants. They form spontaneous vesicles in water as the result of a bilayer organization with a strong cohesion of the pair. Moreover a lyotropic micelle-vesicle transition that depends on the counterion structure was observed and demonstrated. Preliminary vinylic or metathetic polymerization tests show the conservation of the vesicular morphology during the reaction. Also we involve these ion paired surfactants in stabilizing emulsions, allowing the preparation of stable latex via an organometallic polymerization. Finally, the study also presents a new polymerizable surfactant based on the association between cethyltrimethylammonium hydroxide (CTAOH) and a norbornene acid derivative
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Schröder, Michael. "Neue C2-symmetrische Liganden mit Norbornan-Rückgrat Synthese und Anwendung in asymmetrisch katalysierten C-C-Verknüpfungsreaktionen." Köln Blunk, 2005. http://deposit.ddb.de/cgi-bin/dokserv?id=2789547&prov=M&dok_var=1&dok_ext=htm.
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Schröder, Michael. "Neue C2-symmetrische Liganden mit Norbornan-Rückgrat : Synthese und Anwendung in asymmetrisch katalysierten C-C-Verknüpfungsreaktionen /." Köln : Blunk, 2006. http://deposit.ddb.de/cgi-bin/dokserv?id=2789547&prov=M&dok_var=1&dok_ext=htm.
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Greene, Tanja L. "Modular crosslinking of gelatin based thiol-norbornene hydrogels for in vitro 3D culture of hepatic cells." Thesis, ACS Biomaterials Science and Engineering, 2015. http://hdl.handle.net/1805/9929.
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Indiana University-Purdue University Indianapolis (IUPUI)As liver disease becomes more prevalent, the development of an in vitro culture system to study disease progression and its repair mechanisms is essential. Typically, 2D cultures are used to investigate liver cell (e.g., hepatocyte) function in vitro; however, hepatocytes lose function rapidly when they were isolated from the liver. This has promoted researchers to develop 3D scaffolds to recreate the natural microenvironment of hepatic cells. For example, gelatin-based hydrogels have been increasingly used to promote cell fate processes in 3D. Most gelatin-based systems require the use of physical gelation or non-specific chemical crosslinking. Both of these methods yield gelatin hydrogels with highly interdependent material properties (e.g., bioactivity and matrix stiffness). The purpose of this thesis research was to prepare modularly crosslinked gelatin-based hydrogels for studying the influence of independent matrix properties on hepatic cell fate in 3D. The first objective was to establish tunable gelatin-based thiol-norbornene hydrogels and to demonstrate that the mechanical and biological properties of gelatin hydrogels can be independently adjusted. Furthermore, norbornene and heparin dual-functionalized gelatin (i.e., GelNB-Hep) was prepared and used to sequester and slowly release hepatocyte growth factor (HGF). The second objective was to investigate the viability and functions of hepatocytes encapsulated in gelatin-based hydrogels. Hepatocellular carcinoma cells, Huh7, were used as a model cell type to demonstrate the cytocompatibility of the system. The properties of GelNB hydrogels were modularly tuned to systematically evaluate the effects of matrix properties on cell viability and functions, including CYP3A4 activity and urea secretion. The last objective was to examine the effect of heparin immobilization on hepatocyte viability and functions. The conjugation of heparin onto GelNB led to suppressed Huh7 cell metabolic activity and improved hepatocellular functions. This hybrid hydrogel system should provide a promising 3D cell culture platform for studying cell fate processes.
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Puech, Laurence. "Preparation de nouveaux latex par polymerisation vinylique du norbornene et de ses derives en milieu disperse." Toulouse 3, 1997. http://www.theses.fr/1997TOU30264.
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Nous avons mis au point une nouvelle voie de preparation de latex par oligomerisation du bicyclo2. 2. 1hept-2-ene ou norbornene, en emulsion aqueuse au sds, catalysee par pdcl#2. Cette technique originale permet d'obtenir des latex tres stables, de repartition granulometrique monodisperse a 10 nm. A l'aide de differentes techniques analytiques, nous avons propose un modele de mecanisme reactionnel a la polymerisation. Lors de l'etude du mecanisme reactionnel, il est mis en lumiere l'intervention de l'eau ainsi que le role des protons du milieu reactionnel dans le processus de polymerisation. Ainsi nous montrons qu'ils sont directement impliques dans le processus de terminaison de chaine en permettant de controler les masses des oligomeres obtenus. Ce procede a ete etendu a la synthese de particules de latex fonctionnalises. Les monomeres fonctionnalises choisis sont le 5-hydroxymethyl bicyclo2. 2. 1hept-2-ene ainsi que des norbornenes substitues par des fonctions sucres derives du glucose et du lactose. En ce qui concerne le 5-hydroxymethyl bicyclo2. 2. 1hept-2-ene, la polymerisation en suspension dans l'eau, catalysee par pdcl#2(tppts)#2, permet l'obtention de latex fonctionnalises. Leur repartition granulometrique est monodisperse a 316 nm. Les polymeres formes sont constitues d'environ 149 motifs. Ils presentent des proprietes physiques interessantes : temperature de decomposition elevee (superieure a 200c), fort compactage des chaines de polymere. . . Enfin, dans le cas des neoglycopolymeres prepares a partir de norbornenes derives de sucres, nous avons developpe leur polymerisation vinylique dans l'eau, sans protection prealable de la fonction sucre, et catalysee par pdcl#2(tppts)#2. Ce procede permet l'obtention d'agregats plurimoleculaires d'une taille allant de 10 a 350 nm et de repartition granulometrique plus ou moins monodisperse. Leur tendance a s'agreger fortement peut s'expliquer par l'etablissement de liaisons hydrogene entre motifs sucres.
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SUTTHASUPA, Sutthira. "Ring-Opening Metathesis Polymerization of Amino Acid Functionalized Norbornene Monomers, and Properties of the Formed Polymers." 京都大学 (Kyoto University), 2010. http://hdl.handle.net/2433/97971.
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Cuny, Nathalie. "Synthèse et caractérisation de copolymères à base de styrène et de norbornène." Bordeaux 1, 1993. http://www.theses.fr/1993BOR10655.
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L’étude concerne la tentative de copolymérisation radicalaire du styrène avec le norbornene, dans l'objectif d'obtenir un copolymère styrenique de température de transition vitreuse élevée. En raison du caractère agent de transfert du norbornene, seuls des copolymères de faible degré de polymérisation ont été obtenus par copolymérisation directe. Par contre, la terpolymérisation des 2 co monomères précédents avec le n-cyclohexylmaleimide, conduit à des matériaux dont les propriétés thermomécaniques sont nettement supérieures à celles du polystyrène. La détermination ou l'évaluation des différents rapports de réactivité, la caractérisation structurale des terpolymères et l'évaluation de leurs propriétés thermomécaniques, font l'objet d'une discussion approfondie qui fait apparaitre l'intérêt économique de ces nouveaux matériaux polymères
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Singh, Alicia. "Physical organic studies of substituted norbornyl systems: aspects of mechanisms and chirality." Thesis, Rhodes University, 2017. http://hdl.handle.net/10962/50558.
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Fenchone and camphor are essential natural products that are available optically pure and contribute to the chiral pool in asymmetric synthesis. Further, they are both derivatives of norbornane, a structure that undergoes a remarkable diversity of rearrangements in acidic conditions. This work explores two aspects of the camphor/fenchone derived systems. Firstly an attempt to clarify rearrangement mechanisms on a camphor system successfully via deuterium labelling and unsuccessfully via derivatization of fenchone (with rearrangement) to produce other 13C-labelled camphor substitutions, has resulted in confirmation of a theoretically proposed, highly concerted Wagner-Meerwein, 6,2 - hydride shift, Wagner-Meerwein rearrangement in competition with an associated 2,3-methide shift. Kinetics and activation parameters for many steps have been resolved in this rearrangement of the deuterium labelled camphor-derived tosylate system to two pairs of isotopomers. Further, the kinetics and formation of an unexpected pair of dimers encountered during the scheme for 13C labelling are investigated in detail. These dimers (forming during the initial stages of the synthetic scheme) are unusual in that they are not expected rotamers of each other, but diastereomers resulting from chirality of a sulfur atom in a sulfite moiety. A feasible mechanism of formation that matches the kinetics has been proposed in this unexpectedly complex system, and thermodynamic parameters have been determined. The second aspect of substituted norbornyl systems pertains to their chirality, and the influence of this chirality on reaction mixtures, with an aim to identify novel chiral micellar catalysts for use in heterogeneous reaction mixtures. Headway has been made towards the synthesis of the appropriate surfactants to be used in the construction of these micelles, but extensive molecular dynamics simulations have illustrated the feasibility of forming the stable chiral micelles in a dual-solvent system, and detail precisely the influence of chirality on surrounding media. These studies add important physical organic data as well as show the immense possibilities pertaining to substituted norbornane systems.
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Le, Meur Anne-Claire. "Développement de vecteurs pharmaceutiques pour le relargage contrôlé de principes actifs." Phd thesis, Université Sciences et Technologies - Bordeaux I, 2009. http://tel.archives-ouvertes.fr/tel-00627907.
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La délivrance contrôlée de médicaments constitue un enjeu thérapeutique de première importance pour le milieu médical. Elle doit, en effet, permettre de diminuer la toxicité du médicament en limitant sa concentration dans l'organisme et en ciblant son lieu de délivrance. Ce projet de recherche a conduit à la réalisation de nouveaux nano-vecteurs particulaires utilisables pour la délivrance de médicaments par hyperthermie locale. Ces objets sont constitués d'un cœur de polynorbornène et d'une écorce de poly (oxyde d'éthylène) et sont synthétisés par polymérisation par ouverture de cycle de type métathèse (ROMP) en dispersion. L'acide salicylique est encapsulé dans ces particules en tant que molécule modèle. L'originalité de ce sujet pluridisciplinaire réside : dans la nature de la particule, qui permet une libération du principe actif à partir de 35-45°C et dans la technique d'imprégnation des particules par la voie fluide supercritique.
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Donlon, Lynn. "Synthesis and kinetic studies on palladium hydride-initiated vinyl polymerisation of functionalised norbornenes." Thesis, Durham University, 2011. http://etheses.dur.ac.uk/678/.
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Chapter I provides a summary of the vinyl polymerisation of norbornenes and their functionalised derivatives, using palladium-based initiators. The concept of photolithography is introduced along with discussion of hexafluoropropanol-(HFP) functionalised norbornene derivatives that provide the basis for the work described in this thesis. In Chapter II, the synthesis of a series of HFP-functionalised monomers of the type NB(CH2)nC(CF3)2OH (n = 1-2) and NB(CH2)nOCH2C(CF3)2OH (n = 0-6) is described. The monomers prepared differ in the number of methylene units (n) separating the HFP-functionality from the norbornene skeleton, which has previously been shown to have an influence upon polymerisation rate. The series of palladium hydride initiator complexes [Pd(H)(MeCN)(PCy3)2][X] (anion X = BF4, PF6, SbF6, I and B(C6F5)4) were also prepared with a view to determining the effect of the anion on polymerisation rate. The in-depth study of the stability and reactivity of the discrete complex [PdH(MeCN)(PCy3)2][B(C6F5)4] (Pd1388) is examined in Chapter III. The complex Pd1388 is shown to decompose in chlorinated solvents at 70 °C to form PdCl2(PCy3)2 and two further species, b and c that, despite extensive efforts, could not be identified. Both Pd1388 itself and Pd1388 in its decomposed form (i.e. the mixture of PdCl2(PCy3)2, b and c) are able to act as pro-initiator systems in the polymerisation of exo-NBCH2OCH2C(CF3)2OH (SX1). The kinetics of these polymerisation reactions are explored in detail and a kinetic model is proposed, which accurately describes the overall observed polymerisation rate. In Chapter IV the kinetic model was extended to the study of pure exo- and pure endo-HFP-functionalised norbornenes, with the model proving to be an excellent fit to experimental data for monomer consumption. An increase in the value of n is shown to produce a corresponding enhancement of polymerisation rate. An examination of the polymerisation of HFP-functionalised norbornenes using GPC as function of time is also described. High molecular weight material is formed at low conversion (<35%) with a reduction in molecular weight observed during the first 30 minutes of the reaction to yield a polymer of peak average molecular weight ~20,000 Daltons and low PDI (<1.4). In Chapter V, the kinetic model is further extended to the study of mixtures of endo- and exo-HFP-functionalised norbornenes (n = 0-6). As in the case of pure isomers, an increase in the value of n leads to an enhancement in overall polymerisation rate. Finally, the polymerisation of endo-/exo-NBCH2C(CF3)2OH (SXN4) is explored using initiators containing different counter anions (prepared in Chapter II) in order to determine the effect of the anion on polymerisation rate.
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Nguyen, Duc Anh. "Cycloalkenyl macromonomers from new multifunctional inimers : a platform for graft, bottle-brush and mikto-arm star copolymers." Thesis, Le Mans, 2016. http://www.theses.fr/2016LEMA1001/document.
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Le sujet de cette thèse concerne l'élaboration de macromonomères, de copolymères greffés et de polymères étoiles de type 'mikto-arm'. De telles architectures macromoléculaires ont été synthétisées par la combinaison de techniques de polymérisation contrôlées/vivantes telles que la polymérisation par ouverture de cycle (par métathèse) (RO(M)P) etde chimie 'click' orthogonales : cycloaddition 1,3-dipolaireazoturealcyne catalysée au cuivre (CuAAC) et thiol-ène.Dans un premier temps, des macromonomères originaux à fonctionnalité polymérisable (oxa)norbornène portant deux chaînes macromoléculaires poly(e-caprolactone) (PCL) et/ou poly(oxyde d'éthylène) (POE) ont été synthétisés par combinaison ROP/CuAAC. Les macromonomères à fonctionnalité (oxa)norbornène avec deux chaînes PCL de masse molaire moyenne en nombre (Mn) compris entre 1400 et 5000 g/mol ont été obtenus par ROP organocatalysée. La synthèse des macromonomères POE44-b-PCLn à fonctionnalité norbornène avec un bloc PCL de longueur variable (1100 g/mol The objective of the present thesis was the preparation of complex macromolecules by the combination of controlled/livingpolymerization methods such as ring-opening (metathesis) polymerization (RO(M)P) and highly efficient orthogonal chemistries: copper-catalyzed azide-alkyne coupling (CuAAC) and thiol-ene reactions.In the first part of this work, a series of well-defined structural (co)polymers containing a cycloolefin (norbornene (NB) oroxanorbornene (ONB)) functionality bearing two polymer chains including poly(ε-caprolactone) (PCL) and/or poly(ethylene oxide) (PEO) have been successfully prepared using the combination of ring-opening polymerization (ROP) and CuAAC ‘click’ chemistry. Well-defined (oxa)norbornenyl-functionalized bis-PCL polymers with PCL chain ranging from 1400 to 5000 g/mol were obtained by organocatalyst-mediated ROP. Norbornenyl-functionalized PEO-b-PCL block copolymers with PCL block in the range 1100 to 4100 g/mol were synthesized from commercially available PEO 2000 g/mol by CuAAC followed by ROP of CL. The presence of a hydrophilic PEO chain and a hydrophobic PCL chain in norbornenylfunctionalizedPEO-b-PCL copolymers gives rise to self-assembling properties in water solution. Critical micellar concentrations (CMC)are in the range of 0.08 – 0.006 g/L for copolymers with PCL chain length ranging from 10 to 36 CL units, respectively. Thecorresponding micelles show hydrodynamic diameters in range of 10 – 23 nm with low polydispersities.In the second part of this work, well-defined copolymers were used to prepare bottle-brush and (mikto-arm) star copolymersthrough reactions involving the cycloolefin functionality. On the one hand, high density grafting bottle-brush copolymerspoly(oxa)norbornene-g-bisPCL, polynorbornene-g-PEO/PCL (PNB-g-(PEO/PCL)) and PNB-b-(PNB-g-(PEO/PCL)) were achieved by ROMP according to the ‘grafting through’ strategy using Grubbs’ catalysts. On the other hand, PCL, PEO, PNIPAM-based 3-arms star, 4-arms star copolymers were obtained via radical thiol-ene reactions as demonstrated by 1H NMR, SEC and MALDI-ToF MS analysis.The high reactivity of these copolymers toward ROMP and thiol-ene reactions makes them interesting candidates in order toprepare new well-defined copolymers with controlled structures and properties through highly efficient synthetic strategies
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Olcay, Elmali. "Asymmetric Syntheses Of Various Novel Chiral Ligands With Norbornene Backbone: The Use Of Chiral Catalyst In Asymmetric Reactions." Phd thesis, METU, 2005. http://etd.lib.metu.edu.tr/upload/2/12606192/index.pdf.
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The synthetic strategy of this study mainly depends upon the asymmetric desymmetrization of meso norbornene type an anhydride. Asymmetric desymmetrization was achieved by using chinchona alkaloids under kinetically controlled conditions. The resultant mono ester carboxylic acid was epimerized to trans configuration. Subsequent esterification followed by lithium aluminum hydride reduction afforded the first chiral diol ligand with 98 % ee. Transformation of diol to corresponding trans diamine was achieved via Mitsunobu-Gabriel combination. The resultant diamine was first transformed into salen type ligand with 3,5-di-tert-butyl-2-hydroxybenzaldehyde. Throughout this process, no racemization was observed and all the ligands tested in asymmetric reactions have 98 % ee value.
The second part of the thesis involves the asymmetric test reactions of the chiral ligands to check the effectiveness of them. The first testing method was diethylzinc addition to benzaldehyde. The ligands showed moderate effectiveness. The salen type ligand was tested in asymmetric epoxidation and aziridination reactions and it showed good effectiveness. Another applied method was desymmetrization of meso 2-cyclohexene-3,4-diol in which 2-(diphenylphosphino)benzoic acid attached trans-diol and trans-diamine type ligands were tested. Since norbornene type strained bicyclic systems are available in ring opening methathesis polymerization (ROMP) reactions, trans-diamine was subjected to ROMP to get an enlarged macromolecular system
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Ferraz, Camila Palombo. "Efeito da acidez-π de ligantes ancilares na atividade de complexos carbonílicos de rutênio em ROMP de norborneno." Universidade de São Paulo, 2010. http://www.teses.usp.br/teses/disponiveis/75/75132/tde-04052010-085850/.
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Os complexos [RuCl2(PPh3)3], cct-[RuCl2(CO)2(PPh3)2], ttt-[RuCl2(CO)2(PPh3)2], [RuCl2(CO)2(PPh3)(pip)] e [RuCl2(CO)(PPh3)2(DMF)] foram investigados em ROMP de norborneno. O objetivo foi observar a influência eletrônica das moléculas CO, PPh3, piperidina e dimetilformamida como ligantes ancilares na reatividade dos complexos. Experimentos realizados por 1 h à 50°C na razão [NBE]/[Ru] = 5000 mostraram que o complexo [RuCl2(CO)2(PPh3)(pip)] é inerte para ROMP, o complexo cct-[RuCl2(CO)2(PPh3)2] apresentou valores não maiores que 1% e o complexo ttt-[RuCl2(CO)2(PPh3)2] formou 3,75% de poliNBE. Sugere-se que a reação ocorra pela liberação de uma molécula de CO para a formação do complexo carbeno, o que explica a reatividade dos diferentes complexos. O complexo [RuCl2(CO)(PPh3)2(DMF)] foi ativo tanto a 50 como a 25 °C, com 25,0 and 12,2% de rendimento, respectivamente, com a razão [NBE]/[Ru] = 5000 por 1 h. A atividade desse complexo está associada à liberação da molécula DMF, como observado nos espectros de RMN de 31P e UV-visível. Os valores de IPD e Mn foram 1,7-1,8 e na ordem de 104 g/mol, respectivamente. A outra espécie presente em solução foi observada por RMN de 31P na razão de 2/3 o qual foi inerte para ROMP. Assim, considerando apenas 1/3 de espécie ativa, o rendimento de poliNBE pode ser aceito como cerca de 75 e 36% à 50 e 25 °C, respectivamente. O valor à 50 °C é similar àquele obtido com o precursor [RuCl2(PPh3)3] (70% de rendimento em 5 min) e melhor que à 25 °C, no qual o precursor é inerte. Os resultados obtidos mostraram que os complexos contendo CO ácido-π como ligante ancilar podem ser ativos para ROMP de norborneno quando uma posição lábil no complexo ocorra.The complexes [RuCl2(PPh3)3], cct-[RuCl2(CO)2(PPh3)2], ttt-[RuCl2(CO)2(PPh3)2], [RuCl2(CO)2(PPh3)(pip)] and [RuCl2(CO)(PPh3)2(DMF)] were investigated for ROMP of norbornene. The aim is to observe the electronic influence of the CO, PPh3, piperidine and dimethylformamide molecules as ancillary ligands in the reactivity of the complexes. Experiments performed for 1 h at 50 °C with the ratio [NBE]/[Ru] = 5000 showed that the complex [RuCl2(CO)2(PPh3)(pip)] is inert for ROMP, the complex cct-[RuCl2(CO)2(PPh3)2] yielded values not higher than 1% and the complex ttt-[RuCl2(CO)2(PPh3)2] provided 3.75% of polyNBE. It is suggested that the reactions occur via release of a CO molecule for the formation of the carbene complex, thus explains the reactivity of the different complexes. The complex [RuCl2(CO)(PPh3)2(DMF)] was active either at 50 or 25 °C, with 25.0 and 12.2% yield, respectively, with the ratio [NBE]/[Ru] = 5000 for 1 h. The activity of this complex is associated to the release of the DMF molecule, as observed in the 31P NMR and UV-visible spectra. The IPD and Mn values were 1.7-1.8 and 104 g/mol in magnitude. Other specie present in solution was observed in the 31P NMR spectra in a ratio of 2/3 which is inert for ROMP. Thus, considering just 1/3 of active specie, the yield of polyNBE can be acceptable as c.a. 75 and 36% at 50 or 25 °C, respectively. The value at 50 °C is similar to that obtained with the precursor [RuCl2(PPh3)3] (70% yield for 5 min) and better at 25 °C, where the precursor is inert. The obtained results showed that the complexes containing π-acid CO as ancillary ligand can be active for ROMP of norbornene when a labile position in the complex occurs.
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Laschewsky, André, and Wolfgang Schulz-Hanke. "Ring-opening metathesis polymerization of amphiphilic norbornenes functionalized with non-linear optical (NLO) chromophores." Universität Potsdam, 1993. http://opus.kobv.de/ubp/volltexte/2008/2691/.
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Contents:
Potential of amphiphilic NLO polymers
Ring-opening metathesis polymerization (ROMP)
Properties of the polymers
Monolayer properties
Experimental part
- Methods
- Materials
- Analytical data
- General polymerization procedure
Conclusions
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Santos, Francisco Paulo dos. "Determinação e analise das constantes de acoplamento nJch (n=2,3,4) em derivados do norbornano." [s.n.], 2009. http://repositorio.unicamp.br/jspui/handle/REPOSIP/250095.
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Orientador: Claudio Francisco TormenaTese (doutorado) - Universidade Estadual de Campinas, Instituto de Quimica
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Resumo: A tese está estruturada da seguinte forma. Primeiro uma parte introdutória relatando o efeito das interações hiperconjugativas na constante de acoplamento JXY e uma discussao sobre a as principais metodologias para a determinação de constantes de acoplamento a JXY a longa distância. Nesta primeira parte o leitor e introduzido nos tópicos básicos desta tese. Seguindo o corpo da tese contém os resultados e discussão. Primeiro apresentamos as metodologias para determinação das constantes de acoplamento JCH com enfase para o experimento de HSQMBC e para os experimentos de estado de spin seletivo (HSQC-TOCSY-IPAP e HSQC-TOCSY-IPAP-triplamente editado). Posteriormente apresentamos uma racionalização para a diferença entre os acoplamentos JC4H1 e JC1H4 da 3-exo-2-norbornanona (X = Cl, Br, SCH3). Mostramos que ambos os acoplamentos JC1H e JC4H14 deveriam apresentar uma redução de seus valores, devido as interações hiperconjugativas sC1-C7p*C2=O e sC1-C7s*C2=O que retiram densidade eletrônica do caminho a três ligações.Entretanto, observamos que a existência de uma terceira interação sC3-C4s*C2-O recupera parte da densidade eletrônica do acoplamento JC4H1 através de um caminho adicional a quatro ligações fazendo com que o acoplamento JC4H1 seja maior. Este caminho a quatro ligações é similar ao observado em sistemas homoalílicos, sendo que a principal diferença é a natureza do orbital antiligante, que para nossos sistemas é um orbital do tipo s, enquanto para os homoalílicos é do tipo p.
Abstract: In the introduction, it is presented a discussion about the effect of hyperconjugative interactions on coupling constants and a discussion about some methodologies for the measurement of long range heteronuclear coupling constants. JCH, with special emphasis on HSQMBC experiments and the spin state selective methodologies (HSQC-TOCSY-IPAP and HSQC-TOCSY-IPAP-triple editing). After that, a rationalization of the known difference between the JC4H1 and JC1H4 coupling constant transmitted mainly through the 7-bridge in norbornanone is presented in terms of the effects of hyperconjugative interactions involving the carbonyl group. Theoretical and experimental JC4H couplings were carried out for 3-endo- and 3-exo-X-2-norbornanone (X = Cl, Br, SCH3) and for exo- and endo-2- norbornanes derivatives. The hyperconjugative interactions were studied with the Natural Bond Orbital (NBO) analyses. It was observed that interactions involving the carbonyl p*C2=O and s*C2=O antibonding orbitals produce a decrease of threebond contribution for o both JC4H1 and JC1H4 couplings.However, the latter antibonding orbital also undergoes a strong sC3-C4s*C2=O interaction, which defines an additional coupling pathway for JC4H1 but not for JC1H4 .This pathway is similar to that known for homoallylic couplings, being the only difference the nature of the intermediate antibonding orbital, i.e. for JC4H1 is of s-type, while in homoallylic couplings is of p-type.
Doutorado
Quimica Organica
Doutor em Ciências
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Talukdar, Pinaki. "Synthesis Of Carbasugars And Other Related Structural Motifs." Thesis, Indian Institute of Science, 2001. http://hdl.handle.net/2005/247.
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Recent years have witnessed a great deal of interest in the design and synthesis of small molecules, which can mimic complex carbohydrates of vital importance in various life processes. Carbasugars constitute one such class of molecules among several others, in which ring oxygen of sugar is replaced by a methylene unit. Several approaches have been reported in the literature for the synthesis of carbasugars emanating both from carbohydrate and non-carbohydrate sources. While the carbohydrate-based approaches require extensive prote'ction-deprotection maneuver, the non-carbohydrate-based approaches generally have problems of diastereoselection and introduction of chirality.
In the context of synthesis of carbasugars, we envisaged that a suitable derivative of i bicyclo[2.2.1]heptane (norbornyl system), could serve as a carbasugar equivalent provided the
inherent cyclohexane ring could be disengaged through a tactical cleavage of C1-C7 or C4-C7 bonds. In the present thesis entitled "Synthesis of carbasugars and other structurally related
motifs", we have established the carbasugar-norbornyl system equivalence by using 7-* oxobicyclo[2.2.1]hept~5-en-2~yl acetate as precursor . While the tactical cleavage of C1-C7 bond was employed in the synthesis of carbasugars, the C4-G7 bond cleavage provided access to a new class of carbasugars i.e. "confused" carbasugars* The quest for stronger and specific inhibitors of glycosidases led us to synthesize a diverse array of polyoxygenated compounds in this new family of carbasugars.
The thesis has been organized under five main sections: I. Introduction, II. Results & Discussion, III. Experimental, IV. Spectra, and V. References where we have narrated our I synthetic efforts with suitable literature citations.
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Edel, Andrea L. "Synthesis and ring-opening metathesis polymerization of norbornenes containing pendent aromatic and aliphatic side chains." Thesis, National Library of Canada = Bibliothèque nationale du Canada, 1999. http://www.collectionscanada.ca/obj/s4/f2/dsk1/tape7/PQDD_0020/MQ56122.pdf.
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McClary, LaKeisha Michelle. "Synthesis and characterization of norbornene-functionalized side-chain monomers for potential use as transport materials in organic light-emitting diodes." Thesis, Atlanta, Ga. : Georgia Institute of Technology, 2007. http://hdl.handle.net/1853/26696.
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Thesis (M.S.)--Chemistry and Biochemistry, Georgia Institute of Technology, 2008.Committee Chair: Marder, Seth; Committee Member: Bredas, Jean-Luc; Committee Member: Tolber, Laren. Part of the SMARTech Electronic Thesis and Dissertation Collection.