Dissertations / Theses on the topic 'Diels-Alder Reaction'
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Göstl, Robert. "Photocontrolling the Diels-Alder reaction." Doctoral thesis, Humboldt-Universität zu Berlin, Mathematisch-Naturwissenschaftliche Fakultät, 2014. http://dx.doi.org/10.18452/17060.
Full textThe synthetic chemist’s profession is devoted to the formation of chemical bonds to create new molecules, building blocks, or drugs from basic starting materials. However, the growing complexity of these synthetic products necessitates that the development of the tools to fulfill this task must also keep pace. Light as a stimulus with its superior spatial, temporal, as well as energetic resolution in combination with its non-invasive character outperforms the traditional means to control a chemical reaction, such as heat, pressure, or pH, clearly. In this work, the unprecedented reversible photocontrol over a dynamic covalent reaction was established by the combination of a molecular photoswitch and the well-known Diels-Alder reaction. The outcome of the reaction of a furyl-substituted diarylethene and maleimide could be determined exclusively by illumination with differently colored light. This prototypical system was then advanced for the application under physiological conditions while retaining its superior photochemical properties. The release of therapeutically effective concentrations of different antitumor agents could be photoreversibly triggered in buffered, aqueous solution at body temperature employing bioorthogonal visible light. It is shown how the release properties of these photoswitchable prodrugs can be fine-tuned and a thorough investigation of the release dynamics is presented promoting this system to a level where in vivo application can be considered. Furthermore, the foundations for the implementation of the photocontrollable Diels-Alder reaction in the reversible covalent functionalization of carbon nanotubes have been laid. Despite the fact that a successful functionalization has not yet been achieved, the basic principles were investigated and have paved the way for the application of more advanced techniques to effectively modulate the physicochemical properties of sp2-carbon allotropes.
Yamamoto, Yuhei. "Catalytic asymmetric nitroso Diels-Alder reaction." 京都大学 (Kyoto University), 2006. http://hdl.handle.net/2433/143962.
Full textHo, David Gai. "Adventures in Lewis acid catalyzed highly hindered Diels-Alder reactions; Novel non-Diels-Alder Diels-Alder reaction and its utility for the synthesis of haterumaimide E." Diss., Restricted to subscribing institutions, 2007. http://proquest.umi.com/pqdweb?did=1495960681&sid=1&Fmt=2&clientId=1564&RQT=309&VName=PQD.
Full textBirkinshaw, Timothy Nicholas. "Diels-Alder routes to Prosopis alkaloids." Thesis, University of Cambridge, 1987. https://www.repository.cam.ac.uk/handle/1810/270418.
Full textCernak, Timothy Andrew. "A Diels-Alder approach to palau'amine /." Thesis, McGill University, 2007. http://digitool.Library.McGill.CA:80/R/?func=dbin-jump-full&object_id=103369.
Full textFour families of dienophiles---oxazolones, dehydroalanines, hydantoins and thiohydantoins---were investigated. The hydantoins and thiohydantoins react with cyclopentadiene with up to 13:1 exo-selectivity while the dehydroalanines are modestly selective and the oxazolones are unselective. The exo-selectivity of the hydantoin and thiohydantoin dienophiles is attributed to a novel stabilizing interaction whereby the lone pair of electrons on nitrogen interacts with a developing positive charge on the diene in the transition state. In terms of reactivity, the oxazolones are the superior dienophiles. The reactivity of the thiohydantoins is greater than that of analogous hydantoins and approaches that of the oxazolones. The bolstered reactivity of the thiohydantoins is attributed to the increased donation of the nitrogen lone-pair into the thiocarbonyl bond. This phenomenon was recognized first in DFT predictions and then proven experimentally. Synthetic access to the requisite beta-(chloromethylene)thiohydantoins necessitated the development of a reaction between dilithium diamides and thiophosgene.
2-silyloxy-5-(silyloxymethyl)cyclopentadienes were studied experimentally and computationally and found to be much more stable than conventional 5-substituted cyclopentadienes towards thermal decomposition by 1,5 hydride shift. The new dienes undergo Diels-Alder reaction with oxazolone and thiohydantoin dienophiles with exoselectivities as high as 6:1 for nonchlorinated dienophiles. Fully functionalized chlorinated exo-cycloadducts were prepared with up to 1.5:1 selectivity and subjected to oxidative ring-opening to reveal the persubstituted core of palau'amine.
Grossmith-Hague, Catharine. "New catalysts for the hetero Diels-Alder reaction." Thesis, University of Bath, 2002. https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.760796.
Full textWarmus, Joseph Scott Warmus. "Synthetic studies of the intramolecular Diels-Alder reaction." Thesis, Massachusetts Institute of Technology, 1990. http://hdl.handle.net/1721.1/13718.
Full textTan, Siu Min. "Multicomponent Diels-Alder Sequences of 1-Aminodendralenes." Phd thesis, Canberra, ACT : The Australian National University, 2017. http://hdl.handle.net/1885/143040.
Full textGomes, Maria Goretti. "Diels-alder reactions of a cyclopentadienone derivative." Diss., Columbia, Mo. : University of Missouri-Columbia, 2007. http://hdl.handle.net/10355/4670.
Full textThe entire dissertation/thesis text is included in the research.pdf file; the official abstract appears in the short.pdf file (which also appears in the research.pdf); a non-technical general description, or public abstract, appears in the public.pdf file. Title from title screen of research.pdf file (viewed on February 13, 2008) Vita. Includes bibliographical references.
Pettersson, Max. "Computational Design of an Enzyme-catalyzed Diels-Alder reaction." Thesis, KTH, Skolan för kemivetenskap (CHE), 2016. http://urn.kb.se/resolve?urn=urn:nbn:se:kth:diva-207576.
Full textDiels-Alder är en viktig reaktion då den är ett redskap för att syntetisera cykliska kolstrukturer, samtidigt som uppemot fyra stereocentra introduceras i den resulterande produkten. Reaktionen används inte enbart inom organisk kemi, utan är även ett viktigt redskap inom industriella sammanhang för att ta fram nya preparat som direkt kan tillämpas inom farmakologi. En återstående problematik är faktumet att introduktionen av nya stereogena kol bidrar till att drastiskt minska möjligheten att bibehålla en stereoselektiv kontroll. En vanlig lösning för att undvika oönskade stereoisomerer är att nyttja kirala hjälpmolekyler och ligander för att öka utbytet av en specifik stereoisomer. Dock innebär införandet av dessa hjälpmolekyler i strävan att erhålla en enantiomeriskt ren produkt ett ökat antal syntes-steg att hantera, vilket antyder att ett eller flera reningssteg är nödvändiga för att uppnå önskat resultat. Ur en miljösynpunkt är detta värt att ha i åtanke, då principerna för grön kemi är viktiga. Detta arbete utforskar möjligheterna att konstruera ett enzym som kan katalysera en asymmetrisk Diels-Alder-reaktion, med hjälp av molekylär modellering. Baserat på tidigare arbeten har enzymet ketosteroid isomeras valts ut som en potential kandidat till ett Diels-Alderase. För att noggrant evaluera enzymet så screenades ett set av substrat mot dess aktiva säte, där de bästa träffarna gentemot vildtypen sparades och återevaluerades allteftersom rationella mutationer kontinuerligt introducerades. Trots avsaknaden av klara indikationer på att en optimal design har kunnat tas fram vid slutet av detta arbete, så erhölls värdefull insikt på möjliga design-strategier, vilket skulle kunna bistå sökandet av det första katalytiskt effektiva Diels-Alderase.
Thomas, Jermaine D. O. "Highly regio and stereoselective hydroxy-directed Diels-Alder reaction." Thesis, University of Ottawa (Canada), 2002. http://hdl.handle.net/10393/6123.
Full textThompson, Robert Lee. "Supercritical fluid solvent effects on a diels-alder reaction." Thesis, Georgia Institute of Technology, 1996. http://hdl.handle.net/1853/10021.
Full textBeligny, Samuel Daniel Charles. "Stereoselective synthesis of tetrahydropyridines using the Diels-Alder reaction." Thesis, Imperial College London, 2005. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.414751.
Full textAhmed, K. M. "Diels-Alder reaction of quinones carrying electron-withdrawing groups." Thesis, University of Manchester, 1988. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.234154.
Full textSmith, David F. "Applications of the imino Diels-Alder reaction in synthesis." Thesis, University of Cambridge, 1992. https://www.repository.cam.ac.uk/handle/1810/272878.
Full textTabti, Boufeldja. "Preparation de synthons lactoniques par reaction de diels-alder." Le Mans, 1987. http://www.theses.fr/1987LEMA1019.
Full textTAHRI, ABDELLAH. "Synthese de dodecahydrophenanthrenone par reaction de diels-alder intramoleculaire." Paris 6, 1994. http://www.theses.fr/1994PA066267.
Full textBuckle, Ronald Neil. "Asymmetric Diels-Alder studies involving chiral acetylenic diesters and investigations of an intramolecular Diels-Alder approach to the pentalenolactones." Thesis, National Library of Canada = Bibliothèque nationale du Canada, 1998. http://www.collectionscanada.ca/obj/s4/f2/dsk2/ftp03/NQ36199.pdf.
Full textEvans, Jessica. "Synthesis of Highly Fluorinated Diels-Alder Polyphenylenes." Diss., Virginia Tech, 2010. http://hdl.handle.net/10919/39179.
Full textPh. D.
Xidos, James Dimitrios. "A theoretical study of stereoselectivity in the Diels-Alder reaction." Thesis, National Library of Canada = Bibliothèque nationale du Canada, 1999. http://www.collectionscanada.ca/obj/s4/f2/dsk1/tape7/PQDD_0015/NQ47505.pdf.
Full textBushby, Nicholas. "The synthesis of bipyridines by double intramolecular Diels-Alder reaction." Thesis, University of Exeter, 2000. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.324066.
Full textWu, Kitty Kit Ying. "The Diels-Alder reaction in the synthesis of qinghaosu analogues /." View Abstract or Full-Text, 2002. http://library.ust.hk/cgi/db/thesis.pl?CHEM%202002%20WU.
Full textIncludes bibliographical references (leaves 152-169). Also available in electronic version. Access restricted to campus users.
Chumachenko, Natasha. "[Beta]-acryloyloxysulfonyl tethers for intramolecular Diels-Alder cycloaddition reactions." [Kent, Ohio] : Kent State University, 2005. http://rave.ohiolink.edu/etdc/view?acc%5Fnum=kent1135392557.
Full textTitle from PDF t.p. (viewed July 28, 2005). Author's first name appears on the abstract page as: Nataliya. Advisor: Paul Sampson. Keywords: b-hydroxysulfones; [beta]-hydroxysulfones; epoxide opening; intramolecular Diels-Alder reaction; vinylsulfones. Includes bibliographical references (p.194- 202).
Herring, Laura Elizabeth. "The steroelectivity of chiral allenes in the dielsalder reaction." Thesis, Georgia Institute of Technology, 1991. http://hdl.handle.net/1853/27311.
Full textBarbosa, Jader da Silva. "Estudo sobre a síntese de furanoliangolidos pela Reação de Diels-Alder." Universidade de São Paulo, 2010. http://www.teses.usp.br/teses/disponiveis/59/59138/tde-08062010-185911/.
Full textOur research group has been studying, for some years, new methods for the synthesis of the core structure of the furanoheliangolides, more specifically of goyazensolide. The basic structure of this compound is a 7-oxabicyclo [6.2.1] undecane system, and it shows biological activities such as schistosomicidal, cytotoxic and anti-inflammatory. In this work, we have used the Diels-Alder reaction as a key step, since it is usually fast and efficient for the synthesis of polycyclic structures. As a last step, we proposed that the cleavage of the internal bond of the rings should furnish the desired macrocycle.
Wang, Bing. "A self replicating reaction and a new approach to ionophore selection." Thesis, University of Liverpool, 1996. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.337144.
Full textWozniak, John C. "Preparation and reactions of Diels-Alder adducts of lignin-derived quinones." Diss., Georgia Institute of Technology, 1988. http://hdl.handle.net/1853/5515.
Full textChumachenko, Nataliya. "b-Acryloyloxysulfonyl Tethers for Intramolecular Diels-Alder Cycloaddition Reactions." Kent State University / OhioLINK, 2005. http://rave.ohiolink.edu/etdc/view?acc_num=kent1135392557.
Full textWee, Chorng Shin. "Theoretical studies of Diels-Alder reactions in natural product biosynthesis /." View abstract or full-text, 2008. http://library.ust.hk/cgi/db/thesis.pl?CHEM%202008%20WEE.
Full textSteizer, Lindsay S. "Synthesis of polysubstituted pyridines : Diels-Alder addition of 1-AZA-1, 3-dienes with acetylenic and ethylenic dienophil." Virtual Press, 1986. http://liblink.bsu.edu/uhtbin/catkey/452401.
Full textDepartment of Chemistry
Bainbridge, Jeremy D. E. "Synthetic studies towards gelsemine." Thesis, University of East Anglia, 1997. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.389255.
Full textJiang, La Sheng. "The chemistry of 1-propene-1,3-sultone and related homochiral sultams : their preparation, chemical transformations and applications in asymmetric Diels-Alder reactions." HKBU Institutional Repository, 1998. http://repository.hkbu.edu.hk/etd_ra/141.
Full textChan, Tin-yau. "A synthetic approach to Yuehchukene analogues /." [Hong Kong : University of Hong Kong], 1987. http://sunzi.lib.hku.hk/hkuto/record.jsp?B12266280.
Full textSnelgrove, Jennifer L. "The intramolecular Diels-Alder reaction of diene-tethered 1-alkenesulfinate esters." Thesis, National Library of Canada = Bibliothèque nationale du Canada, 1999. http://www.collectionscanada.ca/obj/s4/f2/dsk2/ftp01/MQ35934.pdf.
Full textYuyitung, Gay M. "Studies towards a catalytic antibody for an intramolecular Diels-Alder reaction." Thesis, National Library of Canada = Bibliothèque nationale du Canada, 1999. http://www.collectionscanada.ca/obj/s4/f2/dsk1/tape7/PQDD_0007/NQ39011.pdf.
Full textClapham, Gary. "New Lewis acid promoted Diels-Alder reaction and transition catalysed hydrocarbons." Thesis, University of Exeter, 1998. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.284618.
Full textClarke, Philip John. "Synthesis and Diels-Alder reaction of novel Câ‚‚-symmetric chiral dienes." Thesis, University of Southampton, 2005. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.419400.
Full textBatchelor, M. J. "The application of the intramolecular Diels-Alder reaction to lactone synthesis." Thesis, University of Southampton, 1986. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.375071.
Full textCoelho, Dora Salomé Correia. "Novel furan polymer materials based on the reversible Diels-Alder reaction." Doctoral thesis, Universidade de Aveiro, 2011. http://hdl.handle.net/10773/3841.
Full textA futura e inevitável escassez dos recursos fósseis, juntamente com o aumento imprevisível dos seus preços, levou, nas últimas décadas, a um aumento impressionante de iniciativas dedicadas não só à procura de fontes alternativas de fornecedores de energia, mas também de produtos químicos e polímeros a partir de fontes renováveis, em particular da biomassa vegetal. Entre estes, os polímeros derivados de monómeros furânicos constituem uma classe única de materiais cujas estruturas podem, em princípio, simular virtualmente os seus homólogos actualmente derivados de recursos fósseis. O anel furânico é uma estrutura heterocíclica com um carácter diénico pronunciado, o que torna-o um dieno particularmente apropriado para a reacção de Diels-Alder (DA) com dienófilos como a maleimida. Um dos aspectos mais relevantes da reacção de DA é a sua reversibilidade em função da temperatura, a qual permite que os aductos sejam facilmente revertidos nos seus precursores por aumento da temperatura (reacção de retro-DA). No caso específico da combinação furano-maleimida, a formação do aducto predomina até cerca de 60ºC, enquanto a reacção inversa é dominante acima de 100ºC. A combinação desta característica da reacção de DA com a química de compostos furânicos pode abrir um novo caminho para a preparação de materiais macromoleculares funcionais com base em fontes renováveis e com aplicações promissoras como auto-reparação e reciclabilidade. O principal objectivo desta Tese, é a síntese e caracterização de novos materiais poliméricos termo-reversíveis, aplicando a reacção de DA a monómeros complementares com estruturas dos tipos furânico (o dieno, designado por A) e de maleimida (o dienófilo, designado por B). A primeira etapa neste trabalho envolveu a síntese, purificação e caracterização de novos monómeros furânicos e de maleimida do tipo AA, A3, BB, B3, AB, AB2, cada um com diferentes grupos separadores das funções reactivas. Posteriormente, estes monómeros foram polimerizados e despolimerizados por ciclos de DA/retro-DA utilizando diferentes combinações. A formação e dissociação de todos os aductos de DA foram seguidas por ambas espectroscopias de UV e RMN de 1H. O primeiro sistema de DA estudado foi uma combinação modelo entre reagentes mono-funcionais (-A+-B), nomeadamente o acetato furfurílico (FA) e a N-metilmaleimida (MM), ambos comercialmente disponíveis. O objectivo desta abordagem foi estudar a cinética e o equilíbrio da formação/dissociação dos aductos de DA e obter indicações sobre as condições mais adequadas a serem usadas na preparação dos correspondentes novos materiais macromoleculares. Além disso, pretendia-se verificar a presença ou ausência de reacções secundárias que poderiam intervir em ambas as vias directa e inversa das reacções, mesmo após vários ciclos. A espectroscopia de UV forneceu informação quantitativa sobre a cinética de formação do aducto através da diminuição progressiva da absorvência máxima a 293 nm correspondente ao grupo maleimida, a diferentes temperaturas (35, 50, 65 ºC) Reciprocamente, a correspondente reacção de retro-DA foi seguida a 90 ºC através do aumento do mesmo pico. A reversibilidade destes sistemas foi verificada com sucesso após uma sequência de ciclos de DA/retro-DA. Adicionalmente, verificou-se que os espectros originaram um ponto isosbéstico, provando que estes sistemas não envolvem quaisquer reacções secundárias. Uma vez que foi usado um excesso de FA, as reacções de DA modelo apresentaram um comportamento cinético de pseudo-primeira ordem, com a constante de velocidade k mais alta (2.1x10-5 dm3mol-1s-1) para T=65 ºC. A correspondente energia de activação foi de 39.0 kJ.mol-1. A reacção de retro-DA seguiu um comportamento de primeira ordem, com constante de velocidade de 1.6x10-6 s-1. A evolução deste sistema por RMN de 1H a 65ºC deu-nos informações mais detalhadas sobre a sua evolução estrutural, ou seja, à medida que a intensidade dos picos atribuídos à formação do aducto aumentaram progressivamente ao longo do tempo, os pertencentes aos reagentes iniciais diminuiram proporcionalmente. O “rendimento final”, calculado após 20 dias à temperatura ambiente, foi de aproximadamente 70%. A reacção de retro-DA foi depois seguida a 90ºC, observando-se tal como na espectroscopia de UV, o deslocamento da reacção no sentido da regeneração dos reagentes de partida. A viabilidade de múltiplos ciclos de DA/retro-DA estabelecidos pela espectroscopia de UV foi igualmente confirmada por RMN de 1H. O passo seguinte envolveu o estudo de um sistema de policondensação linear baseado no crescimento gradual por reacção de DA entre um monómero bisfurânico A-A e um do tipo bismaleimida B-B, seguindo a mesma abordagem que no sistema modelo. O poliaducto linear foi obtido a partir de soluções equimolares dos monómeros, por reacção de DA a 65ºC. O progresso desta polimerização foi seguido por espectroscopia de UV e RMN de 1H e, mais qualitativamente, pelo aumento da viscosidade do meio. A reacção seguiu um comportamento de segunda ordem, com uma constante de velocidade de 9.4x10-6 dm3mol-1s-1, e observou-se novamente um ponto isosbéstico nos dados de UV. Os espectros de RMN apresentaram o padrão esperado, nomeadamente o aumento progressivo dos sinais associados ao aducto e a correspondente diminuição dos grupos furano e maleimida livres. A despolimerização do poliaducto através da reacção de retro-DA foi seguida a 110ºC usando as mesmas técnicas. Os dados de UV mostraram o retorno progressivo da absorção dos grupos de maleimida, seguindo um comportamento cinético de primeira ordem, com constante de velocidade de 2.5x10-6 s-1, até à completa regeneração de ambos os monómeros. Os espectros de RMN providenciaram mais uma vez informação estrutural sobre o progresso da despolimerização, a qual foi acompanhada por uma diminuição progressiva da viscosidade. Adicionalmente, para seguir a retro- DA, adicionou-se um excesso de composto furânico monofuncional, nomeadamente o 2,5-dimetilfurano (DMFu), ao sistema de modo a bloquear as funções maleimida complementares, evitando assim a repolimerização após arrefecimento. Os productos isolados foram então o monómero bisfurânico AA, DMFu que não reagiu e o bisaducto não-polimerizável de BB com DMFu. Este resultado indicou claramente que o polímero foi de facto revertido nos seus monómeros durante a reacção de retro-DA. O terceiro sistema estudado foi outra polimerização linear, seguindo as mesmas condições experimentais que os anteriores, mas com uma estratégia diferente de modo a contornar o problema clássico de assegurar a estequiometria exacta dos monómeros. As estruturas dos monómeros utilizados incorporam ambos os grupos reactivos, i.e, moléculas do tipo A-B. A polimerização prematura destes monómeros intrinsecamente reactivos foi evitada com a protecção do grupo maleimida na forma de um aducto de DA com furano, até a incorporação do substituinte furânico na outra extremidade. Portanto, a policondensação destes monómeros foi iniciada após a desprotecção in situ deste composto mediante aquecimento, seguido de arrefecimento até à temperatura adequada para polimerizar. Os resultados obtidos por UV e RMN sugerem que de facto o uso de monómeros do tipo A-B oferece um melhor sistema linear. Em seguida, foram estudados sistemas de policondensação não-linear por reacção de DA, entre monómeros (um ou ambos) com funcionalidade superior a dois, nomeadamente sistemas do tipo A3+B-B ou A-A+B3, seguindo mais uma vez as mesmas condições experimentais. Uma vez que utilizam monómeros complementares contendo, em média, mais de duas funcionalidades, estes sistemas conduzem a materiais reticulados. Nestes estudos, foram usadas três razões molares de [maleimida]/[furano], nomeadamente 1.0, 0.75 e 0.5, de modo a estudar ambas as situações de não-gelificação e reticulação. Ambos sistemas apresentaram um comportamento regular e boa reciclabilidade quer para gerar situações que possam conduzir à formação de redes a diferentes graus de conversão, ou que possam parar antes da sua obtenção, conforme previsto pela equação de Flory-Stockmayer. Como esperado, a utilização de grupos complementares em quantidades estequiométricas produziu o espessamento mais rápido e a reticulação quase completa; à medida que a quantidade relativa de monómero trifuncional decresceu, as reacções pararam antes da reticulação, ou seja, originaram meios altamente viscosos contendo polímeros solúveis altamente ramificados. As reacções de retro-DA a 110 ºC conduziram à gradual dissolução das partículas de gel (quando presentes), tendo sido comprovado pelos espectros de UV e de RMN de 1H, evidenciado a regeneração dos monómeros. Tal como no sistema do tipo A-A+B-B, a reacção de retro-DA foi seguida adicionando um excesso de DMFu ao sistema reaccional. Como esperado, os produtos finais foram os monómeros furânicos, o DMFu em excesso e o trisaducto ou o bisaducto maleimida-DMFu, o que confirma a eficiência da despolimerização com regeneração dos monómeros iniciais. O último sistema de policondensação por reacção de DA envolveu um monómero assimetricamente substituído do tipo AB2, capaz de originar estruturas macromoleculares hiper-ramificadas que não reticulam. Este estudo preliminar deste sistema foi seguido nas mesmas condições experimentais que os anteriores, apresentando um comportamento com as características esperadas.
The inevitable future scarcity of fossil resources, together with their skyrocketting prices, has led in the last decades to a dramatic increase of initiatives devoted not only to the search for alternative sources of energy providers, but also to the search for chemical commodities and polymers from renewable resources, namely the vegetable biomass. Among these, polymers from furan monomers constitute a unique class of materials whose structures can in principle simulate virtually all their current fossil-derived counterparts. The furan heterocycle displays a pronounced dienic character, which makes it highly suitable as diene in the Diels-Alder (DA) reaction, with dienophiles like maleimide. One of the most relevant aspects of the DA reaction is its thermal reversibility, which allows the adducts to be readily reverted to their precursors as the temperature is raised (retro-DA reaction). In the specific case of the furan-maleimide combination, the adduct formation dominates up to ca. 60ºC, whereas the reverse reaction is overwhelming above ca. 100ºC. The coupling of this DA feature with the furan chemistry can open a new way to prepare functional macromolecular materials based on renewable resources with novel properties and promising applications like mendability and recyclability. In this Thesis, the main goal is the synthesis and characterisation of novel thermoreversible polymer materials by means of the DA reaction, using complementary monomers bearing furan (the diene, assigned as A) and maleimide (the dienophile, assigned as B) moieties. The first step in this study was the synthesis, purification and characterization of new furan and maleimide monomers, viz. AA, A3, BB, B3, AB, AB2, each bearing different spacing moieties separating the reactive functions. They were then polymerized and depolymerised using different modes of DA/retro-DA cycles. The formation and decoupling of all the DA adducts were followed by both UV and 1H NMR spectroscopy. The first DA system investigated was on a model combination of monofunctional reagents (-A+-B), namely the commercially available furfuryl acetate (FA) and N-methylmaleimide (MM). The purpose of this approach was to study the kinetics and the equilibrium of the formation/decoupling of the DA adducts and to provide clear indications about the most appropriate conditions to be applied in the preparation of the corresponding novel macromolecular materials. Additionally, it aimed at verifying that no detectable side reactions intervened in both forward and backward pathways, even after several cycles. The UV spectroscopy provided quantitative information on the kinetics of the DA adduct formation by monitoring the progressive decrease in the maximum absorbance at 293 nm related to the maleimide moiety, at different temperatures (35, 50, 65ºC). Conversely, the corresponding retro-DA reaction was followed at 90ºC through the increase of the same peak. The reversibility of these systems was successfully checked over a couple of cycles. Additionally, all set of spectra gave rise to an isosbestic point, which proved that these systems did not involve any side reactions.Since an excess of FA was used here, these model DA reactions displayed a pseudo-first order behaviour, with the highest rate constant k (2.1x10-5 M-1.s-1) for T= 65ºC. The corresponding activation energy was found to be 39.0 kJ.mol-1. The retro-DA reaction followed a first order behaviour, with a rate constant of 1.6x10-6s-1.The evolution of the same system followed by 1H NMR spectroscopy at 65ºC gave a detailed insight into its structural evolution, viz. as the intensity of the peaks assigned to the adduct formation progressively increased with time, those belonging to the initial reagents decreased correspondingly. The “final yield” taken after 20 days at room temperature, was approximately 70%. The retro- DA reaction was then carried out at 90ºC, and showed the same features as its UV counterparts, namely the displacement of the reaction towards the regeneration of the initial reagents. The feasibility of multiple DA/retro-DA cycles established by UV spectroscopy was confirmed here. The subsequent stage involved the study of a linear polycondensation system based on the stepwise DA growth between a difuran monomer A-A and a complementary bismaleimide B-B, following the same approach as the model system. The formation of the linear DA polyadduct was achieved by letting equimolar solutions evolve at 65 ºC. The progress of this polymerization was followed by UV and 1H NMR spectroscopy and, more qualitatively, by the increase in the viscosity of the medium. The reaction followed a second order behaviour, with a rate constant of 9.4x10-6 M-1.s-1, and again, a characteristic isosbestic point was observed in the UV data. The NMR spectra gave the expected pattern, namely the progressive increase in the signals associated with the adduct and the corresponding decrease of those attributed to the unreacted furan and maleimide cycles. The depolymerization of the polyadduct through the retro-DA reaction was followed at 110ºC by the same techniques. The UV time scans showed the progressive return of the absorption due to maleimide moieties following a first-order kinetic pattern, with a rate constant of 2.5x10-6 s-1, until both monomers were fully regenerated. The 1H NMR spectra provided once more structural information about the course of this depolymerization, which was accompanied by a progressive decrease in viscosity. Additionally to follow the retro-DA, an excess of a monofunctional furan compound, namely 2,5-dimethylfurfural (DMFu), was added to the system in order to block the complementary maleimide functions, thus avoiding the repolymerisation after cooling. The isolated products were then the difuran monomer AA, the unreacted DMFu and the non-polymerizable bisadduct of BB with DMFu. This result clearly indicated that the polymer had indeed reverted to its monomers during the retro-DA. The third system studied was another linear polymerization, following the same experimental conditions as the previous, but with a different strategy, in order to avoid the classical problem of ensuring the exact monomer stoichiometry. Here, the monomers incorporated both reactive moieties in their structures, i.e. A-B molecules. Here, the premature polymerization of these intrinsically reactive monomers was avoided by protecting the maleimide group in the form of a furan-DA adduct, until the incorporation of the furan moiety. Therefore, the polycondensation of these monomers was initiated after the in situ deprotection of this compound through heating, followed by the cooling to appropriate temperature for polymerization. The results obtained by both UV and NMR spectroscopy suggested that indeed the use of an A-B monomer provides a better linear system. Non-linear DA polycondensations between monomers (one or both) with functionality higher than two, viz. A-A+B3 or A3+B-B systems, were then studied, following once more the same experimental conditions. The use of complementary monomers bearing on average more than two functionalities lead to crosslinked materials. In these systems, three [maleimide]/[furan] molar ratios, viz. 1.0, 0.75 and 0.50, were applied in order to examine both nongelling and crosslinking situations. Both types of systems displayed a clean-cut behaviour and good recyclability to generate situations either leading to the formation of a network at different degrees of conversions, or ending before its attainment, as predicted by the Flory-Stockmayer equation. As expected, the use of complementary moiety stoichiometry produced the most rapid thickening and near-complete crosslinking, whereas as the relative amount of trifunctional monomer was decreased, the reactions stopped short of crosslinking, i.e. gave highly viscous media containing soluble highly branched polymers. The retro-DA reactions at 110ºC revealed the gradual dissolution of the gel particles (when present), while the UV and 1H NMR spectra gave, once more, the details of the depolymerization processes leading the systems steadily back to the monomers. As in A-A+B-B depolymerization, to follow the retro-DA, an excess of DMFu DA trap, was added to the systems under the same conditions. As expected, the final products were the furan monomers, the unreacted DMFu and the non-polymerizable trisadduct or the bisadduct of maleimide-DMFu, confirming the efficiency of the retro-DA depolymerisation in the regeneration of the starting monomers. The last DA polycondensation system involved an assymmetrically substituted monomer of the AB2 type, capable of generating hyperbranched macromolecular structures that do not crosslink. This preliminary study was followed by the experimental approach applied above and the behaviour of the system displayed the expected features.
POCTI; FCT; FSE - SFRH/BD/28271/2006
Durrant, Steven. "Electronic effects in the Diels-Alder reaction : towards catalytic chiral auxiliaries." Thesis, University of Bath, 2002. https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.393873.
Full textD’Aurizio, Antonio <1978>. "Microwave-Mediated Hetero Diels-Alder reaction: Synthesis of biologically active compounds." Doctoral thesis, Alma Mater Studiorum - Università di Bologna, 2009. http://amsdottorato.unibo.it/1641/1/D%27Aurizio_Antonio_Tesi.pdf.
Full textD’Aurizio, Antonio <1978>. "Microwave-Mediated Hetero Diels-Alder reaction: Synthesis of biologically active compounds." Doctoral thesis, Alma Mater Studiorum - Università di Bologna, 2009. http://amsdottorato.unibo.it/1641/.
Full textZhao, Dalian. "Syntheses and the Structures of Polymethylpolycyclic and Polycyclic "Cage" Molecules." Thesis, University of North Texas, 1989. https://digital.library.unt.edu/ark:/67531/metadc500344/.
Full textMacNevin, Christopher J. "Reactivity of substituted 4-Pyridones in normal and inverse demand Diels-Alder cycloaddition /." Electronic version (PDF), 2003. http://dl.uncw.edu/etd/2003/macnevinc/christophermacnevin.pdf.
Full textEberlin, Ludovic. "Novel applications of polyfunctionalised organoboron and nitroso compounds." Thesis, Rennes 1, 2016. http://www.theses.fr/2016REN1S078/document.
Full textThis thesis presents the reactivity of dienylboronated compounds towards arylnitroso and carbonylnitroso derivatives and its use in the synthesis of heterocyclic and polycyclics compounds. The first study focused on the reactivity of dienylboronate compounds with arylnitroso derivatives resulting in pyrrole or furan products. The outcome and efficiency of the reaction is related to the boron on the dienyl moiety and the solvent used. Using the certain conditions, pyrroles, boronated MIDA ester oxazines or nitrones could be obtained. A one-pot strategy was then applied to synthesise oxazoline derivatives using nitrones as an intermediate. Theoretical, as well as experimental, work has supported that the formation of the pyrrole was obtained by a regioselective nitroso Diels-Alder reaction/rearrangement/borate elimination cascade process. Details on the nitrone formation have not been clarified, but further investigations are on-going. Secondly, attention was focused on the reactivity of dienylboronate compounds with carbonylnitroso derivatives. Contrary to the arylnitroso species, the nature of the carbonylnitroso had a dramatic impact on reactivity. On the one hand, similar reactivity towards the formation of pyrroles and boronated MIDA ester oxazines was observed, however, by employing a higher electron-deficient carbonylnitroso species, the product resulting from a nitroso-ene reaction was obtained. Ene-product was used as the key intermediate for the synthesis of different polycyclic compounds. A multicomponent, one-pot, Diels-Alder/allylboration procedure was optimised to yield various structures depending on the nature of the dienophile and the aldehyde. To diversify the chemistry of the ene-product another sequence was designed using the pyrrole synthesis. A multi-step pathway was optimised to afford novel fused bicylic oxazine-pyrrole products
Jump, Joseph M. "Synthesis and use of chiral dienes in the asymmetric diels-alder reaction." Diss., Georgia Institute of Technology, 1990. http://hdl.handle.net/1853/30292.
Full textCoisson, David. "Application of the hetero diels-alder reaction for synthesis of carbohydrate analogues." Thesis, University of Reading, 2009. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.515689.
Full textBollans, Lee. "The acylnitroso diels-alder reaction : Application to Amino Acids and their glycoconjugates." Thesis, University of Liverpool, 2009. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.511092.
Full textPoumaroux, Ambroise. "Réaction d'hétéro Diels-Alder entre des carbazole-1,4-diones et des 1- ou 2-azadiènes : application à la synthèse régiospécifique de pyridocarbazole-5,11-diones." Lyon 1, 1997. http://www.theses.fr/1997LYO1T125.
Full textFriesen, Richard William. "Annulations leading to bicyclic dienes : Diels-Alder reactions of (some of) the dienes and dolastane diterpenoid syntheses." Thesis, University of British Columbia, 1988. http://hdl.handle.net/2429/28781.
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