To see the other types of publications on this topic, follow the link: Amine.
Dissertations / Theses on the topic 'Amine'
Create a spot-on reference in APA, MLA, Chicago, Harvard, and other styles
Consult the top 50 dissertations / theses for your research on the topic 'Amine.'
Next to every source in the list of references, there is an 'Add to bibliography' button. Press on it, and we will generate automatically the bibliographic reference to the chosen work in the citation style you need: APA, MLA, Harvard, Chicago, Vancouver, etc.
You can also download the full text of the academic publication as pdf and read online its abstract whenever available in the metadata.
Browse dissertations / theses on a wide variety of disciplines and organise your bibliography correctly.
1
Sandford, Graham. "Some amine hydrofluorides and amines in organofluorine chemistry." Thesis, Durham University, 1991. http://etheses.dur.ac.uk/6209/.
Full text
2
Abrahamson, Michael J. "Development of an amine dehydrogenase." Diss., Georgia Institute of Technology, 2012. http://hdl.handle.net/1853/50138.
Full textAbstract:
Biocatalysts are increasingly prevalent in the large-scale synthesis of enantiomerically pure compounds. However, many sought-after reactions lack a suitable enzymatic production route. This work describes the development of a novel amine dehydrogenase through the application of directed evolution altering the substrate specificity of an existing leucine dehydrogenase scaffold. Eleven rounds of directed evolution completely altered the enzyme’s specificity and successfully created amination activity. The resulting amine dehydrogenase asymmetrically catalyzes methyl isobutyl ketone and free ammonia to 1, 3-dimethyl butyl amine. The enantioselectivity of the wild-type enzyme was maintained despite the drastic changes to the binding pocket and yielded (R)-1,3-DMBA with nearly complete conversion making it an attractive catalyst in the synthesis of chiral amines. This was the first example of a cofactor-dependent amine dehydrogenase capable of selectively synthesizing chiral amines from a prochiral ketone and free ammonia. Additionally, knowledge gained altering the specificity of the leucine dehydrogenase scaffold was applied to an analogous phenylalanine dehydrogenase scaffold allowing for rapid evolution of novel activity. A single mutational library resulted in a second amine dehydrogenase with enhanced activity toward significantly different substrates, while maintaining comparable conversion and enantioselectivity. These two scaffolds provide examples of the broad applicability of the identified mutations in creating amine dehydrogenase activity.
3
Pieper, Matthias [Verfasser]. "Nachhaltige Synthese pharmazeutisch aktiver Amine und Amide / Matthias Pieper." Bielefeld : Universitätsbibliothek Bielefeld, 2019. http://d-nb.info/1196640637/34.
Full text
4
Silva, Alexandre Vieira. "Síntese de organo-seleno aminas e sua resolução cinética via reação de acetilação enantiosseletiva mediada por lipases." Universidade de São Paulo, 2008. http://www.teses.usp.br/teses/disponiveis/46/46135/tde-02072008-125408/.
Full textAbstract:
Nesse trabalho foi desenvolvido um método de síntese quimioenzimática de organo-seleno aminas (1-((2, 3 ou 4 selenocianato)fenil)etanonas) e amidas (N-(1-(2, 3 ou 4-(etilseleno)fenil)etil)acetamida) enantiomericamente enriquecidas. Inicialmente, as organo-seleno aminas, na forma racêmica, foram sintetizadas a partir das orto-, meta- e para- aminoacetofenonas. A incorporação do átomo de selênio nas cetonas aromáticas foi realizada através da reação de selenocianato de potássio com sais de diazônio, preparados a partir das aminoacetofenonas, para levar as o, m ou p-selenocianato acetofenonas (28-65 %). Reações desses compostos com NaBH4, formaram os intermediários organo-selenoboro, que foram posteriormente alquilados com haletos de alquila de modo a formar as organo-seleno acetofenonas (1-(2, 3 ou 4-(etilseleno)fenil)etanona) (63-78 %). As Organo-seleno aminas racêmicas foram preparadas por aminação redutiva das cetonas correspondentes (39-73 %). Após desenvolvido o protocolo de síntese das organo-seleno aminas, nós estudamos a resolução cinética desses compostos através de reação de acetilação mediada por lipases. Um estudo inicial foi conduzido com a amina para substituído, como substrato modelo, de modo a buscar a lipase, solvente, temperatura, razão lipase/substrato e acilante apropriados para a resolução cinética. De acordo com os resultados obtidos, as condições ideais para se conduzir a resolução cinética foi CAL-B como biocatalisador, hexano como solvente e acetato de etila ou metóxi-acetato de etila como acilante a 30°C. Utilizando esse protocolo, as organo-seleno amidas foram preparadas com excelentes excessos enantioméricos (99 %).In this work, we have developed a chemoenzymatic method to enantiomerically synthesize enriched organoselenium amines (1-(2, 3 or 4 -(ethylselanyl)phenyl)ethanamine) and amides (N-(1-(2, 3 or 4-(ethylselanyl)phenyl)ethyl)acetamide). Initially, the organoselenium amines, in the racemic form, were synthesized from ortho-, meta- and para- aminoacetophenones. The incorporation of the selenium atom into the aromatic ketones was achieved by the use of reaction of potassium selenocyanate and diazonium salts, prepared from aminoacetophenones, to afford selenocyanate acetophenones (28-65 %). These compounds were alkylated with alkyl halide to yield the organoselenium acetophenones (1-(2, 3 or 4-(ethylselanyl)phenyl)ethanone) (63-78 %) which were converted into their corresponding racemic organoselenium amines by reductive amination (39-73 %). After developing the protocol for the synthesis of racemic organoselenium amines, we studied the kinetic resolution of these compounds by their acetylation mediated by lipases. An initial study was carried out with the organoselenium amine para substituted, as a model substrate, in order to screen for appropriate lipase, solvent, temperature, lipase/substrate ratio and acylant. This study showed that the ideal condition to conduct the kinetic resolution was CAL-B as biocatalyst, hexane as solvent and ethyl acetate or ethyl methoxyacetate as acylant at 30°C. By using this protocol, the organoselenium amides were prepared in excellent enantiomeric excess (99 %).
5
Ghislieri, Diego. "Application of engineered amine oxidases for the synthesis of chiral amines." Thesis, University of Manchester, 2013. https://www.research.manchester.ac.uk/portal/en/theses/application-of-engineered-amine-oxidases-for-the-synthesis-of-chiral-amines(de93d851-97f8-4422-8dc4-0f7402488021).html.
Full textAbstract:
The development of cost-effective and sustainable catalytic methods for the production of enantiomerically pure chiral amines is a key challenge facing the pharmaceutical and fine chemical industries. There is an increasing demand for broadly applicable synthetic methods which deliver the desired amine product in high yield and enantiomeric excess (e.e.). Previously we have described the development of variants of monoamine oxidase from Aspergillus niger (MAO-N) which are able to mediate the complete conversion of racemic amines to the corresponding enantiomerically pure products in a single step. In this thesis we report a panel of MAO-N variants (D5, D9 and D11) developed in our laboratory, which are able to mediate the deracemisation of primary, secondary and tertiary amines with broad structural features. In particular, we have synthesized and subjected to deracemisation a broad range of tetrahydroisoquinolines and tetrahydro-β-carbolines checking enantioselectivity and enantiopreference of our biocatalysts. A relation between lipophilicity of the substituents and enantiopreference of the enzyme has been identified. We have also engineered a new MAO-N variant (D11) with a greatly increased substrate scope and enhanced tolerance for bulky substrates. Application of this engineered biocatalyst is highlighted by the asymmetric synthesis of the generic drugs Solifenacin and Levocetirizine as well as a number of important classes of biologically active alkaloid natural products. We also report a novel MAO-N mediated asymmetric oxidative Pictet-Spengler approach to the synthesis of (R)-harmicine.Another challenge facing the chemist in the new millennium is the development of cleaner and more efficient chemical processes. To this aim the combination of two or more catalytic systems to complete a series of cascade reactions is considered particularly appealing. We have reported a concurrent redox cascade for the deracemisation of pyrrolidines and tetrahydroisoquinolines using our monoamine oxidase-N with a biotinylated Ir-complex within streptavidin (SAV). To achieve the final goal it is necessary to shield the metal inside a host to avoid the mutual inactivation of the two catalysts. We have also described the combination of MAO-N with berberine bridge enzyme (BBE) for the synthesis of berbines (tetrahydroprotoberberines), which represent a sub-class of tetrahydro-isoquinoline alkaloids found in various plants. This bi-enzymatic cascade allows the synthesis of these structures achieving a theoretical 100% yield instead of the 50% given by the kinetic resolution using BBE itself.
6
Parkinson, Andrew. "DNA-amine interactions." Thesis, University of Warwick, 1998. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.302652.
Full text
7
Dawood, Ayad [Verfasser], Uwe [Gutachter] Bornscheuer, and Florian [Gutachter] Rudroff. "Application of Amine Transaminases in the Chemoenzymatic Synthesis of Chiral Amines using Isopropylamine as Amine Donor / Ayad Dawood ; Gutachter: Uwe Bornscheuer, Florian Rudroff." Greifswald : Universität Greifswald, 2019. http://d-nb.info/1182536417/34.
Full text
8
Dawood, Ayad Verfasser], Uwe Theo [Gutachter] [Bornscheuer, and Florian [Gutachter] Rudroff. "Application of Amine Transaminases in the Chemoenzymatic Synthesis of Chiral Amines using Isopropylamine as Amine Donor / Ayad Dawood ; Gutachter: Uwe Bornscheuer, Florian Rudroff." Greifswald : Universität Greifswald, 2019. http://nbn-resolving.de/urn:nbn:de:gbv:9-opus-25574.
Full text
9
Cherif, Mohamed Amine. "Sur l'approximation rationnelle pour le semi-groupe de transport." Poitiers, 2010. http://theses.edel.univ-poitiers.fr/2010/Cherif-Mohamed-Amine/2010-Cherif-Mohamed-Amine-These.pdf.
Full textAbstract:
La notion de l'approximation rationnelle est normalement conçue pour la discrétisation en temps. Dans cette thèse nous mélangeons cette notion avec la notion de la convergence au sens de Kato qui découle d'une discrétisation en espace pour l'équation de transport neutronique. Nous appliquons cette procedure aux schémas d'Euler explicite et implicite, Crank-Nicolson et Prédicateur-Correcteur qui ont le degré de convergence 1,2 et 3 au sens de l'approximation rationnelle. Pour démontrer la convergence nous utiliserons le théorème de Cherno et nous donnons aussi des illustrations numérique pour justifier ces degrés de convergence. Dans le dernier chapitre nous donnons quelques nouvelles généralisations des théorèmes de point fixe de type Schauder et de type Krasnoselskii qui se basent sur la notion de la compacité faible sur des espaces Fréchet ayant la propriété de Dunford- Pettis et sur la notion de la U-équicontractionIn this thesis we mix the rational approximation procedure, which is a time approximation with approximation in the sense of Kato, which is a space approximation for neutron transport equation. We apply this procedure for explicit and implicit Euler, Crank-Nicolson and Predictor-Corrector schemes which have the rate 1,2 and 3 in the sense of rational approximation. By using Cherno's Theorem, we prove the convergence and we construct also the numerical illustration for justifying the above rate of convergence. In the last chapter, we give some generalization of Schauder and Krasnoselskii fixed point theorems in Dunford-Pettis Frechet spaces and which based on the notion of weakly compactness and U-equicontraction
10
Constantinou, Constantinos Petrou. "The nitromethane - amine interaction." Thesis, University of Cambridge, 1992. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.386675.
Full text
11
Rowley, Julian H. "Imidazolidinones in amine catalysis." Thesis, University of Strathclyde, 2014. http://oleg.lib.strath.ac.uk:80/R/?func=dbin-jump-full&object_id=25637.
Full text
12
Pullin, Robert David Charles. "Amine-promoted alkene aziridination." Thesis, Imperial College London, 2011. http://hdl.handle.net/10044/1/6939.
Full textAbstract:
Aziridines, the smallest saturated aza-heterocycle, are not only prevalent in several natural products, but also represent a versatile synthetic tool for the chemist via exploitation of the strained ring system. Research described in this thesis concerns the chemistry of N-N ylides (aminimines), which were utilised in a novel tertiary amine-promoted organocatalytic approach to the aziridination of α,β-unsaturated carbonyl compounds. Through the use of modified conditions two important classes of substrates, dienones and alpha-enolizable enones, both of which had previously shown poor reactivity with the system, can now be aziridinated in good yields. Studies have also focused on the development of an asymmetric variant of the methodology using chiral tertiary amine promoters. A variety of novel chiral six-membered 1,4-heterocycles and cinchona alkaloid derivatives have been synthesised and their utility towards asymmetric alkene aziridination has been assessed, aiding the understanding of the proposed transition state model for the reaction.
13
Steele, David Fraser. "Amine/microcrystalline cellulose interactions." Thesis, University of Bath, 2002. https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.275882.
Full text
14
Brotzel, Frank. "Nucleophilicities of Amines, Amino Acids and Pyridines." München : Verl. Dr. Hut, 2008. http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&doc_number=017069126&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA.
Full text
15
Cullum, Neil Richard. "New photoinitiators and amine synergists." Thesis, University of Kent, 1997. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.270528.
Full text
16
McKnight, Michael Vincent. "Heterocycles as amine protecting groups." Thesis, University of Liverpool, 1987. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.328176.
Full text
17
Strutt, Ian. "New axially chiral amine organocatalysts." Thesis, University of East Anglia, 2014. https://ueaeprints.uea.ac.uk/53435/.
Full textAbstract:
Organocatalysis has become one of the most popular areas of research within organic chemistry over the past 15 years. This is due to the fact that, usually under mild conditions, it is possible to access either highly functionalized or previously inaccessible structural motifs using this relatively new type of catalysis. Firstly, methodology is reported for the synthesis and use of tertiary amine organocatalysts based on the now ubiquitous binaphthyl backbone. The tertiary amines synthesized were shown to be effective nitrogen transfer reagents in the asymmetric aziridination of chalcone substrates, with enantiomeric excesses of up to 37% seen. The first example of an isolated chiral hydrazinium salt being used as a nitrogen transfer reagent for the aziridination of enones is also described. Secondly, a range of α-substituted secondary amines based on the binaphthyl backbone has been synthesized from easily accessible iminium salts. Preliminary catalyst testing showed them to be interesting alternatives to the more commonly seen proline-derived catalysts for asymmetric conjugate additions reactions between cyclic enones and malonates, with enantiomeric excesses of 24% seen using optimized conditions.
18
FEREY, VINCENT. "Utilisation de complexes amine-borane dans la synthese stereoselective de derives d'acides alpha-amines." Paris 11, 1996. http://www.theses.fr/1996PA112084.
Full textAbstract:
Ce memoire concerne l'etude de nouvelles methodes stereoselectives d'acces a des derives d'acides alpha-amines, precurseurs d'acides alpha-amines non proteinogeniques. Dans la premiere partie, nous decrivons des tentatives d'utilisation d'heterocycles comportant une fonction amidine ou iminoester. Cependant, ces composes, utilises comme substrats dans des reactions d'alkylation pouvant nous mener aux derives desires, se sont reveles inertes vis-a-vis de bases fortes. Ainsi, malgre de nombreuses variantes synthetiques explorees, cette etude n'a pas donne les resultats escomptes. Une approche plus generale utilisant comme substrats des complexes amine-borane a ensuite ete mise au point. Nous presentons successivement: - dans la deuxieme partie, une revue bibliographique sur la synthese de ces complexes et leur utilisation en synthese organique. - dans la troisieme partie, une etude de l'influence de la complexation par le borane d'un aminoester sur sa reactivite dans la reaction d'aldolisation: elle nous permet, suivant les conditions, de preparer selectivement des alpha-amino-beta-hydroxyesters de configuration syn ou anti. - dans la quatrieme partie, une methode enantioselective d'acces a des acides alpha-amines alpha-substitues, derives de l'alanine et de la proline. Cette methode repose sur une preparation efficace et diastereoselective de complexes amine-borane chiraux, et sur une procedure d'alkylation conduisant a des composes enantiomeriquement enrichis (purete enantiomerique: jusqu'a 92%)
19
Panchanan, Subrata. "Studies on coordination compounds of dioxouranium(VI) and molybdenum with ligands derived from amino acids especially with emidazole, amine and amide r groups." Thesis, University of North Bengal, 1993. http://hdl.handle.net/123456789/739.
Full text
20
Bode, Matthias. "Benzo[c][2,7]naphthyridin-5-yl-amine und Benzo[h][1,6]naphthyridin-5-yl-amine." [S.l.] : [s.n.], 2006. http://deposit.ddb.de/cgi-bin/dokserv?idn=979241499.
Full text
21
Jie, Yuanping Livant Peter D. "Tris(1,3-dihydroxy-2-propyl)amine, a planar trialkylamine synthesis, structure, and properties ; a potential precursor to hypervalent nitrogen /." Auburn, Ala., 2006. http://repo.lib.auburn.edu/2006%20Spring/doctoral/JIE_YUANPING_0.pdf.
Full text
22
Zhong, Bo. "Mechanism-based Inhibitors for Copper Amine Oxidases: Synthesis, Mechanism, and Enzymology." Cleveland, Ohio : Case Western Reserve University, 2010. http://rave.ohiolink.edu/etdc/view?acc_num=case1259013895.
Full textAbstract:
Thesis(Ph.D.)--Case Western Reserve University, 2010Title from PDF (viewed on 2009-12-30) Department of Chemistry Includes abstract Includes bibliographical references and appendices Available online via the OhioLINK ETD Center
23
Fujieda, Nobutaka. "Enzymes in bacterial amine degradation : biochemical and electrochemical characterization of quinohemoprotein amine dehydrogenase and histamine dehydrogenase." Kyoto University, 2006. http://hdl.handle.net/2433/78169.
Full textAbstract:
Kyoto University (京都大学)0048
新制・課程博士
博士(農学)
甲第12376号
農博第1557号
新制||農||926(附属図書館)
学位論文||H18||N4134(農学部図書室)
UT51-2006-J368
京都大学大学院農学研究科応用生命科学専攻
(主査)教授 加納 健司, 教授 宮川 恒, 教授 井上 國世
学位規則第4条第1項該当
24
Cooper, Cindy L. "Neuropeptides, amines and amine receptors in the human spinal cord : the effects of Parkinson's disease." Thesis, University of Nottingham, 1989. http://eprints.nottingham.ac.uk/13218/.
Full textAbstract:
The aims of this study were to investigate (i) the levels of catecholamines, indoleamines, substance P and thyrotrophin-releasing hormone (TRH) in the post-mortem spinal cord of subjects who had died with Parkinson's disease and to compare them with those of control subjects (ii) adrenergic and serotonergic receptors in the post-mortem Parkinsonian and control spinal cord and (iii) the effects of subject age and sex and the interval between death and post-mortem (PMI) on the levels of neurotransmitters and neuropeptides and on receptor binding in post-mortem tissue. To perform these investigations (i) a sensitive radioimmunoassay which is specific for substance P and has low cross-reactivity with other similar peptides and (ii) a common extraction medium for the concomitant extraction of catecholamines, indoleamines, substance P and TRH from CNS tissue were developed. The main findings were: There were significant correlations between the levels of 5HT, TRH and α2-adrenoceptor binding and both subject age and the PMI. In Parkinson's disease compared with control subjects: (i) the levels of noradrenaline were significantly reduced in the thoracic ventral region of the spinal cord,(ii) dopamine levels were higher in the thoracic ventral and dorsal spinal cord,(iii) in the lumbar spinal cord 5HT levels were significantly reduced in the dorsal horn with an increase in the ratio of 5HIAA/5HT, (iv) noradrenaline levels were reduced in both dorsal and ventral horns of the lumbar spinal cord and (v) there were no differences between the levels of substance P and TRH in any spinal cord region. There were no measurable 5HT1A or 5HT2 binding sites in the human spinal cord under the conditions used. However, specific α2-adrenoceptor binding was defined in terms of binding affinity and number of receptors in the spinal cord.
25
Karlsson, Anna. "Exploring amino acid metabolism in Saccharomyces cerevisiae for improved eco-efficient production of chiral amine." Thesis, Malmö universitet, Fakulteten för hälsa och samhälle (HS), 2019. http://urn.kb.se/resolve?urn=urn:nbn:se:mau:diva-25085.
Full textAbstract:
Kirala aminer används idag både som aktiva substanser och som bindningsmedel i flertalet läkemedel, dock är dagens produktion med kinetic resolution ineffektiv vilket gör att mer effektiva och miljövänliga produktionssätt eftersträvas. Biotransformation har visat sig både vara miljövänligt och en effektiv metod för att producera kirala aminer. Aminosyror kan användas som aminodonatorer för att producera den kirala aminen 1-methyl-3-phenylpropylamine (MPPA) från prokirala ketonen bensylaceton (BA) med hjälp av aminetransaminas. I denna studie användes metaboliskt konstruerad Saccharomyces cerevisiae med enzymet CV-ωTA för att identifiera vilka aminosyror som var bäst lämpade för MPPA produktion. MPPA produktion kunde detekteras för alla testade aminosyror. Aminosyrans koncentration hade ingen tydlig påverkan på produktionen av MPPA. Alanin vara den aminosyra som gav högst produktionsutbyte följt av lysin. Ingen tydlig relation mellan produktion av MPPA och aminosyrornas koncentrationer kunde ses. Produktionen av MPPA var snabbare än förväntat och var klar redan dag tre för flera av aminosyrorna. Det fanns en antydan att BA kunde vara toxiskt för cellerna i högre koncentrationer och därmed påverka produktionen av MPPA.Chiral amines are used in several types of pharmaceuticals as both active substrates and building blocks, and there is an endeavor to find new and more eco-efficient ways to produce them than today’s production with kinetic resolution. Biotransformation in yeast has shown great potential for production and is also seen as an eco-friendly way to produce chiral amines. Amino acids can be used as an amino donor for the production of chiral amines, e.g. 1-methyl-3-phenylpropylamine (MPPA) from prochiral ketones, e.g. benzylacetone (BA) with aminotransaminase. In this study the production was done with metabolically engineered Saccharomyces cerevisiae, with the gene for the enzyme CV-ωTA transformed. Ten different amino acids were screened in up to three different concentrations for each amino acid. Production of MPPA was observed for all amino acids, with alanine as the most efficient followed by lysine. No clear relationship was seen between amino acid concentration and MPPA production. The production of MPPA for several amino acids were quicker than expected and was completed at day three. Our data indicated a cytotoxic effect of BA at higher concentrations, that negatively affected the production of MPPA.
26
Günler, Zeynep Inci. "Primary amine thioureas in asymmetric organocatalysis." Doctoral thesis, Universitat Rovira i Virgili, 2016. http://hdl.handle.net/10803/396191.
Full textAbstract:
Aquesta tesi es centra en organocatalitzadors de tipus tiourea amina primària (PAT). L’addició de Michael d’acetona a nitroestiré catalitzada per tiourees amina primària va ser estudiada en detall. Els efectes sinergístics de múltiples additius (aigua i àcid acètic) en aquesta reacció varen ser determinats mitjançant anàlisi espectroscòpica de 1H NMR. Els nostres estudis mecanístics van mostrar que l’àcid acètic facilita la hidròlisi dels intermedis d’imina, donant lloc a la catàlisi, i minimitza la formació del subproducte de doble addició. Per la seva banda, l’aigua alenteix la reacció però minimitza la desactivació del catalitzador per nitroestiré, fornint finalment rendiment més elevats. A més a més, vam explorar efectes de concentració en la mateixa reacció: en diluir la reacció, l’enantioselectivitat del producte augmentava de forma significativa, mentres que els rendiments aïllats es mantenien elevats. D’aquesta manera, l’estereoselectivitat de varis organocatalitzadors PAT va poder ser millorada fàcilment.
Finalment, la immobilització d’organocatalitzadors quirals PAT ha estat duta a terme sobre resines poliestirèniques per primera vegada a tarvés d’usa estratègia “click” que forneix el grup tiourea i la unió a la resina simultàniament. Els polímers catalítics obtinguts han estat aplicats a les reaccions asimétriques d’addicó de Michael i de Mannich de cetones. Es van obtenir elevades enantioselectivitats en la reacció de Mannich, mentres que van ser moderades per l’addició de Michael.Esta tesis se centra en organocatalizadores de tipo tiourea amina primaria. La adición de Michael de acetona a nitroestireno catalizada por tioureas amina primaria (PAT) fue estudiada en detalle. Los efectos sinergísticos de múltiples aditivos (agua y ácido acético) en esta reacción fueron determinados por análisis espectroscópico de 1H NMR. Nuestros estudios mecanísticos mostraron que el ácido acético facilita la hidrólisis de los intermedios de imina, conduciendo a la catálisis, y minimiza la formación del subproducto de doble adición. El agua, por su parte, ralentiza la reacción pero minimiza la desactivación del catalizador por nitroestireno, conduciendo finalmente a rendimientos más elevados. Además, exploramos efectos de concentración en la misma reacción: al diluir la reacción, la enantioselectividad del producto se incrementa significativamente. Atribuímos este comportamiento a la minimización de la desactivación del catalizador durante la dilución. De esta manera, la estereoselectividad de varios organocatalizadores PAT pudo ser fácilmente mejorada. Finalmente, la immobilización de organocatalizadores quirales PAT ha sido llevada a cabo sobre resinas poliestirénicas por primera vez a través de una estrategia “click” que permite la formación del grupo tiourea y su sunión a la resina simultáneamente. Los polímeros catalíticos así obtenidos han sido aplicados a las reacciones asimétricas de adición de Micheal y de Mannich de cetonas. Se obtuvieron elevadas enantioselectividades en la reacción de Mannich, mientras que los resultados fueron moderados para las adiciones de Michael.
This thesis focuses on primary amine thiourea organocatalysis. The Michael addition reaction of acetone to nitrostyrene catalyzed by primary amine thioureas (PAT) was studied in detail. The synergistic effects of multiple additives (water and acetic acid) in this reaction were determined by 1H NMR spectroscopic analysis. Our mechanistic studies showed that acetic acid facilitates hydrolysis of the imine intermediates, thus leading to catalysis, and minimizes the formation of the double addition side product. Water on the other hand, slows down the reaction but minimizes catalyst deactivation by nitrostyrene leading to higher yields. Moreover, we explored the concentration effects on the same reaction: upon reaction dilution, product enantioselectivity increases significantly whereas isolated yield can be kept high. We attribute this behavior to the minimization of catalyst deactivation upon dilution. In this way, the stereoselectivity of several PAT organocatalysts could be easily improved. Finally, the immobilization of chiral PAT organocatalysts has been performed on polystyrene-based resins for the first time through a “click” strategy that renders the thiourea group and the linkage simultaneously. The as-synthesized catalytic polymers have been applied to the asymmetric Michael addition and Mannich reaction of ketones. High enantioselectivities were recorded for the Mannich reaction, whereas moderate ee’s were obtained for the Michael addition reaction.
27
Elnan, Jørund. "Screening of Inhibitors for Amine Degradation." Thesis, Norges teknisk-naturvitenskapelige universitet, Institutt for kjemi, 2012. http://urn.kb.se/resolve?urn=urn:nbn:no:ntnu:diva-18867.
Full textAbstract:
Hindering the degradation of amines in the CO2-capturing process is important both for economical purposes when it comes to loss of solvent and impacts on the process, and to prevent emissions of volatile degradation compounds such as ammonia, nitrosamines and formaldehyde. To prevent the absorbent from degrading, either a non-degrading absorbent can be developed or a degradation inhibitor can be added to minimize the degradation. The degradation inhibitors tested in this thesis are meant to inhibit the oxidative degradation that mainly occurs in the absorber. The carbamate polymerization degradation due to CO2 and temperature has to be addressed on its own. The inhibitor screening apparatus was new, and a part of the assignment was testing this setup. The first experiment conducted on the inhibitor screening apparatus used a gas blend of 6% O2/2 % CO2 (N2 balance). This did not give enough degradation, which caused the need for rebuilding the rig. In the other experiments on the screening apparatus, a gas composition of 98 % O2/2 % CO2 was used to get sufficient amount of degradation for inhibitor screening. Inhibitor screening experiments were done using 150 mL of a 30 weight% (wt%) 2-aminoethanol (MEA) solution loaded with 0,4 mol CO2/mol MEA, at 55 °C with a gas flow of 10 mL/min. To test the stability of the inhibitors at higher temperature, thermal experiments with inhibitors were conducted. 7 mL solution was filled in stainless steel cylinders and heated at 135 °C, for a period of five weeks. The solution was 30 wt% MEA loaded with 0,5 mol CO2/mol MEA. Hydrazine was screened for inhibitory effect using a circulative closed loop apparatus because of the hazards related to this compound. The experiment was run with air, using a 30 wt% MEA solution loaded with 0,4 mol CO2/mol MEA, at 55 °C. Since experiments with both 6 % and 98 % oxygen were conducted, it was natural to compare the impact of oxygen concentration on the degradation products. Results indicated that 2-oxazolidinone (OZD) was preferred at the conditions with high oxygen, while N-(2-hydroxyethyl) glycine (HeGly) concentrations increased with decreasing oxygen content. The effect of metals on product composition was also investigated. The degradation compound N-(2-hydroxyethyl) imidazole (HEI) seems to be dependent on the metal concentrations, increasing in the presence of metals. For the inhibitors screened, the inhibition ranged from 23,59-67,81 %. Two compounds gave an increase in degradation. 1-hydroxyethane 1,1-diphosphonic acid (HEDP) was the only chelating agent stable at thermal conditions. The inhibitors did not appear to have a substantial effect on the carbamate polymerization. Quantification of degradation compounds in the samples was done using liquid chromatography-mass spectrometry (LC-MS) and anion chromatography-electrochemical detector (IC-EC). Amine loss and CO2-loading were determined using titration methods. Metal concentrations were determined using inductively coupled plasma-mass spectrometry (ICP-MS). Some analyses were done gravimetrically while others were done volumetrically. For comparison purposes, simple density measurements were done, and the data converted according to the amine loss in the sample.The initial intention was to use gas chromatography - mass spectrometry (GC-MS) to analyze the samples from the thermal experiments. The system was however not operable during the time available. ICP-MS analysis was not done in time for the last experiment. Ammonia analyses were not conducted in time for this thesis.
28
Ernault, Estève. "Thermo-oxydation de résines époxy/amine." Thesis, Paris, ENSAM, 2016. http://www.theses.fr/2016ENAM0060/document.
Full textAbstract:
Les résines époxy/amine obtenues grâce au mélange d’un prépolymère époxy et d’un durcisseur amine, sont utilisées dans divers domaines d’applications : peinture, potting de composés électroniques... L’objectif de cette thèse est la prédiction de la durée de vie de trois résines : DGEBA ou DGEBU/cycloalipahtique diamine, DGEBA/aliphatique diamine, soumises à un vieillissement thermo-oxydant. Pour cela, une étude multi échelle de l’oxydation est réalisée à différentes conditions de température (de 110°C à 200°C) et de pression d’oxygène (0,2 bars et 50 bars). A l’échelle moléculaire, la spectroscopie IRTF a montré la formation d’amides et de carbonyles. A l’échelle macromoléculaire, les coupures de chaînes semblent prédominantes lorsque le durcisseur est une diamine cycloaliphatique. En revanche, lorsque le système contient des séquences méthylènes portées par des segments flexibles, elles peuvent induire un mécanisme de réticulation qui peut prédominer. Ces résultats gouvernent l’évolution des propriétés fonctionnelles : la fragilisation mécanique et la dégradation des propriétés diélectriques de DGEBA/cycloaliphatique diamine se produit pour des temps d’exposition inférieurs à ceux observés pour DGEBA/aliphatique diamine. L’extrapolation des durées de vie est réalisée grâce à une modélisation cinétique basée sur un schéma mécanistique de l’oxydation des trois résines. La résolution de ce schéma cinétique permet la modélisation de l’ensemble des résultats expérimentaux (concentration en produits d’oxydation, coupures de chaînes et réticulation) pour une oxydation homogène ou bien sur des échantillons épais présentant un gradient d’oxydation. Les contraintes mécaniques engendrées lors de l’oxydation d’un échantillon épais (3 mm) de DGEBA/cycloaliphatique diamine ont été simulées afin de prédire la fissuration spontanéeEpoxy/amine resins are thermoset materials made of epoxy prepolymer and amine hardener. Those materials are used in several industrial applications, such as paint or to encapsulate electronics. The main goal of this work is to predict lifetime of three resins: DGEBA or DGEBU/cycloaliphatic diamine, DGEBA/aliphatic diamine, in thermo-oxidative environment. In order to achieve this, a multi scale study of the oxidation is done, at several temperatures (from 110°C to 200°C) and oxygen partial pressures (0,2 bars et 50 bars). At molecular scale, the formation of amides and carbonyls has been noticed. At macromolecular scale, chain scission has been observed in epoxy/cycloaliphatic diamine but in DGEBA/aliphatic diamine cross linking seems to be predominant. Those properties are directly related to functional properties: mechanical and dielectric break down appear later in DGEBA/aliphatic diamine than in epoxy/cycloaliphatic diamine. The extrapolation of life is possible thank to kinetic modelling, based on chemical mechanistic scheme. The resolution of this kinetic scheme allowed us to model all experimental data (concentration of oxidation products, chain scission and cross linking), either in homogenous oxidation and in thick samples (3 mm). Stresses induced by oxidation in a thick sample of DGEBA/cycloaliphatic diamine have been simulated thanks to Matlab ® and finite elements by Abaqus ®
29
Jiang, Xiao. "Fixation chemistry of amine-copper preservatives." Thesis, National Library of Canada = Bibliothèque nationale du Canada, 2001. http://www.collectionscanada.ca/obj/s4/f2/dsk3/ftp04/NQ61121.pdf.
Full text
30
Armstrong, S. K. "Homoallylic amine synthesis using phosphine oxides." Thesis, University of Cambridge, 1992. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.596156.
Full textAbstract:
This thesis will describe the development of a new route to homoallylic amines 9, in four steps from alcohols 1, or acetals 2, which may themselves have to be synthesised. The synthesis is stereoselective, and generates E-9 and Z-9 quite separately, thereby avoiding the sometimes difficult separation of these isomers. Alkenes 3, readily available from alcohols 1 or acetals 2, undergo regio- and stereo-selective 1,3-dipolar cycloadditions with nitrile oxides 4 or nitrones 6. The resulting heterocycles 5 and 7 are reductively cleaved to give β-hydroxy-δ-aminoalkyldiphenylphosphine oxides 8. These alcohols undergo Horner-Emmons-type elimination of sodium diphenylphosphinite to give homallylic amines 9, stereospecifically. Isoxazolines 5, resulting from nitrile oxide cycloadditions, undergo stereoselective reduction, and give rise to primary amines 9, R3 = H. Isoxazolines 7, resulting from nitrone cycloadditions, give rise to secondary amines 9, R3 = alkyl or aryl. When the alkoxy substituted alkenes 3, R1 = OR are used, protected enol ethers 9, R1 = OR, R3 = Ac are the final products. The vital cycloaddition and reduction steps are both high yielding, although the elimination is often less so.
31
Challinor, Lee. "Allylic amine synthesis via sulfimide rearrangement." Thesis, Imperial College London, 2008. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.485415.
Full textAbstract:
This thesis reports the development of a novel asymmetric route towards a variety of NBoc protected allylic amines. This was achieved by creating an organocatalytic asymmetric transformation of aldehydes into a diverse range of allylic sulfides, and then applying a [2,3]-sigmatropic rearrangement with chirality transfer to afford five target motifs that will be discussed in individual chapters. Chapter One. introduces the general topi:along with supporting references. Chapter Two focuses on allylic amines and a [2,3]-sigmatropic rearrangement as a method ofasymmetric C-N bond construction via sulfimidation. The use of an oxaziridine reagent as an electrophilic source ofNBoc to induce rearrangement of prochiral allylic sulfides is then discussed prior to optimisation of a chemoselective version utilising chiral substrates..The chirality transfer is addressed in light of contradictory evidence, and confirmed as complete with simple aliphatic allylic sulfides and several unexplored substrates. Chapter Three highlights vinyl glycines and the development of an organocatalytic preparation of chiral substrates which had previously only been available from a limited chiral pool. Both (E) and (2) allylic sulfides were selectively prepared and the creation of a one-pot amination-rearrangement/N-S- bond cleavage sequence afforded both optical isomers of the target compounds with a variety of y-substituents. Chapter Four focuses on quaternary substituted vinyl glycines which were prepared with an array of a- and y-substituents by optimising the asymmetric organocatalytic preparation of geometrically enriched tri-substituted allylic sulfides through variation ofthe aldehyde and olefinating reagent respectively. Chapter Five discuses allylic afluoro aminoacids and their inherent instability. Chapter Six covers allylic a-aminophosphonates where the organocatalytic preparation of chiral vinylic phosphonates was achieved along with their amination-rearrangement, but the chirality transfer remains to be examined. Chapter Seven concludes our findings and outlines future research. Chapter Eight provides experimental details with spectroscopic and physical data for new compounds.
32
Lu, Jinni, and 陆今妮. "Amine functionalized polymeric catalysts and reagents." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2011. http://hub.hku.hk/bib/B4775252X.
Full textAbstract:
Polymer-supported reagents and catalysts, which allow for simple product
separation and easy recycling, have been widely studied in the context of organic
synthesis. The past decade has witnessed a number of new variations of
polymeric materials, and among the most frequently immobilized functionalities
are amines that possess versatile synthetic utilities.
Polymers with new structures and improved properties for use in synthesis
have been continuously developed since the support may impact the chemical
reactions in which they are used in various ways. A new heterogeneous
polystyrene-based amine, rasta resin-DMAP, has been synthesized and used in
addition reactions of carbon dioxide to epoxides to afford cyclic carbonate
products. This new material was found to be a more efficient catalyst than
divinylbenzene cross-linked polystyrene supported DMAP, and was readily
recycled without significant loss of catalytic activity.
Compared to polymers bearing a single functionality, polymers possessing
multiple different functional groups attached to a single polymer backbone would
have greater potential utility, especially in reactions requiring multiple catalysts or
reagents. As an example of this concept, a bifunctional polystyrene bearing both
DMAP and piperazine groups has been prepared and applied as an organocatalyst
for decarboxylative Doebner-Knoevenagel reactions of arylaldehydes and
mono-ethyl malonate to produce (E)-,-unsaturated esters in high yields.
Additionally, both non-cross-linked and cross-linked bifunctional polystyrenes
featuring amine and thiourea groups have been developed, and their catalytic
performance were evaluated in reactions of nitroalkenes with either nitroalkanes
or sulfur ylides. Both polymers proved to be efficient catalysts in these reactions
and the insoluble polymer demonstrated high recyclability. Control experiments
using monofunctional polymers indicated that both catalytic groups of these
bifunctional polymers are essential and they could work cooperatively to achieve
efficient catalysis.
Finally, a second generation bifunctional phosphine-amine polymer, rasta
resin-PPh3-NBniPr2, was prepared and examined in tandem Wittig-reductive aldol
reactions. In these reaction cascades, the phosphine oxide groups generated
from the Wittig reaction served as the catalyst for the reductive aldol reaction, and
moderate yields of structurally diverse -hydroxy ketones could be obtained from
one-pot processes involving 5 sequential reactions.published_or_final_version
Chemistry
Doctoral
Doctor of Philosophy
33
Johnson, Steven A. "Spectroscopic studies of copper amine oxidase." Thesis, University of Salford, 1998. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.300884.
Full text
34
Miller, Andrew Philip. "Homochiral amine oxides in organic synthesis." Thesis, University of Liverpool, 1998. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.365894.
Full text
35
Fu, Tiantian. "Quaternary amine metabolism in gut microbiota." Thesis, University of Warwick, 2017. http://wrap.warwick.ac.uk/95877/.
Full textAbstract:
Quaternary amines such as choline and carnitine are essential nutrients for humans supplied from daily food; however, quaternary amines metabolism by gut microbiota can lead to the development of various diseases, including non-alcoholic fatty liver disease and cardiovascular disease. It is hypothesized that both diseases are promoted by microbial catabolism of choline and carnitine to trimethylamine (TMA). Proteus mirabilis is a Gram-negative gut proteobacterium, which can metabolize choline anaerobically to form TMA. I demonstrated that the identified cutC gene is essential for choline degradation and subsequent TMA production in this bacterium. Using P. mirabilis as the model, I investigated the physiological role of quaternary amine metabolism from the bacterial perspective and demonstrated that P. mirabilis can rapidly uptake and degrade choline to enhance growth rate, cell yield and swarming speed under anaerobic and microaerophilic conditions. I also provide the first evidence of a novel choline-metabolizing microcompartment, which is present in both vegetative and swarming cells supplemented with choline. Another important dietary source of TMA in human gut is carnitine. I used two model proteobacteria Acinetobacter baumannii and Escherichia coli in this project to investigate the role of carnitine metabolism to TMA in health and disease. A. baumannii and E. coli can use carnitine as a growth substrate to produce TMA. To better understand the role of quaternary amine metabolism in host health and disease, I used Caenorhabditis elegans model to investigate carnitine metabolism on the life span of the worm. My data suggest that malate, the degradation product of carnitine, extends the life span of C. elegans fed on A. baumannii or E. coli. Together, my study reveals that choline and carnitine metabolism as an adaptation strategy for gut proteobacteria and contributes to better understand the ecology of these TMA-forming gut bacteria in health and disease.
36
Malet, Federic Louis Gino. "Aqueous ATRP of amine-based methacrylates." Thesis, University of Sussex, 2001. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.367786.
Full text
37
Armstrong, Susan Katherine. "Phosphine oxides in homoallyic amine synthesis." Thesis, University of Cambridge, 1991. https://www.repository.cam.ac.uk/handle/1810/272612.
Full text
38
Meyer, Holger. "Pyrido[3,2-b]indol-4-yl-amine, [1]Benzofuro[3,2-b]pyridin-4-yl-amine und [1]Benzothieno[3,2-b]pyridin-4-yl-amine : Darstellung von Antimalariamitteln /." [S.l. : s.n.], 2003. http://www.gbv.de/dms/bs/toc/374105367.pdf.
Full text
39
麥成達 and Shing-tat Mak. "Synthesis and reactivities of cobalt and rhodium complexes with macrocyclic tertiary amine and multianionic amide ligands." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 1988. http://hub.hku.hk/bib/B31231305.
Full text
40
鄭永堅 and Wing-kin Cheng. "Synthesis, reactivities, and electrochemistry of osmium complexes withmacrocyclic tertiary amine and multianionic amide and schiff-baseligands." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 1989. http://hub.hku.hk/bib/B31231512.
Full text
41
Taylor, Morgan James. "Chemistry of β-diketiminate Group 14 and Group 2 complexes and macrocyclic amines and amine ethers." Thesis, University of Sussex, 2012. http://sro.sussex.ac.uk/id/eprint/39640/.
Full textAbstract:
Group 14 metal(II) alkyl complexes are very rare, with few examples being studied in great detail. To this end, a series of β-diketiminate lead(II) alkyl and aryl complexes, [{(2,6-iPr2C6H3)NC(CH3)}2CH]PbR (R = Me, iPr, sBu, Np, Bn, tBu and Ph) were synthesised and a number of computational studies were performed on them to increase the understanding of the nature of these compounds. Reactivity studies on both the lead, and the analogous tin systems, showed that they could be used as precursors to generate examples of very rare two-coordinate group 14 metal cation complexes, including the first example of a β-diketiminate two-coordinate lead(II) cation, and an analogous example of a rare low-coordinate tin(II) system. These were studied in detail by computational methods, including the stabilising effects of a coordinated solvent molecule on the metal centre. β-Diketiminate magnesium alkyl complexes were generated to investigate the +2 oxidation state metal environment without the presence of a stereochemically active lone pair, as present in the group 14 metal(II) complexes. A carbodiimide was successfully inserted into the magnesium-carbon bond, and novel magnesium phosphides were generated from the alkyl complexes. Solvent stabilisation effects on these phosphides were also studied by computational methods. A series of macrocyclic amines and amine ethers were synthesised to investigate the hydrolysis of a phosphate diester model RNA system by lead(II) salts, monitored by UV-visible kinetics. The reaction kinetics gave no reproducible results, but the syntheses of the macrocycles are presented in detail for further citation.
42
Mak, Shing-tat. "Synthesis and reactivities of cobalt and rhodium complexes with macrocyclic tertiary amine and multianionic amide ligands /." [Hong Kong : University of Hong Kong], 1988. http://sunzi.lib.hku.hk/hkuto/record.jsp?B12349823.
Full text
43
Jachmann, Nicole. "Flüssigchromatographische Bestimmung aliphatischer und aromatischer Amine mit 4-Chloro-7-nitrobenzo-2-oxa1,3-diazol." [S.l. : s.n.], 2001. http://deposit.ddb.de/cgi-bin/dokserv?idn=967326168.
Full text
44
Ethier, Amy Lynn. "Applications of reversible and sustainable amine-based chemistries: carbon dioxide capture, in situ amine protection and nanoparticle synthesis." Diss., Georgia Institute of Technology, 2013. http://hdl.handle.net/1853/52913.
Full textAbstract:
A multidisciplinary approach has been applied to the development of sustainable technologies for three industrially relevant projects. Reversible ionic liquids are novel carbon dioxide capture solvents. These non-aqueous silylamines efficiently capture carbon dioxide through chemical and physical absorption and release carbon dioxide with minimal addition of heat. The development of these capture agents aims to eliminate the need for a co-solvent, while minimizing energy loss and achieving solvent recyclability. Also presented is the use of carbon dioxide for amine protection during chemical syntheses. Amine protection is widely used in almost all sectors of chemical and pharmaceutical industries. The use of carbon dioxide as a reversible protecting group reduces solvent waste during protection and deprotection and improves the atom economy of existing processes. Sustainable chemistry has also been applied to the use of reversible ionic liquids as switchable surfactants for nanoparticle synthesis. The reversible ionic liquid system offers two significant advantages toward a more efficient synthesis and deposition of nanoparticles in that an additional surfactant is not required, and due to the reversible nature of the ionic liquids, a facile and waste-reduced deposition method exists.
45
Wilfong, Walter Christopher. "In Situ FTIR and Tubular Reactor Studies for CO2 Capture of Immobilized Amine Sorbents and Liquid Amine Films." University of Akron / OhioLINK, 2014. http://rave.ohiolink.edu/etdc/view?acc_num=akron1403704363.
Full text
46
Blain, Marine. "Substitution des isocyanates dans les polyuréthanes pour des revêtements transparents de forte épaisseur." Thesis, Lyon, 2016. http://www.theses.fr/2016LYSE1058.
Full textAbstract:
L'entreprise Juxta produit des résines pour des revêtements transparents de fortes épaisseurs en polyuréthane. Ces revêtements sont fabriqués à partir de deux produits dangereux : les isocyanates et un catalyseur à base de mercure. Pour protéger ses employés et consommateurs, l'entreprise Juxta a lancé un projet de substitution des isocyanates dans les polyuréthanes. Pour ce faire, trois nouvelles voies de synthèse ont été envisagées :La voie cyclocarbonate/amine est la plus novatrice. Dans un premier temps, la réactivité de cyclocarbonates et d'amines modèles a été étudiée ainsi que l'effet de différents catalyseurs. Les meilleurs catalyseurs sont de la famille des thiourées, urées et guanidines. Puis une voie d'accès à des cyclocarbonates incolores a été mise au point. Enfin, une étude a permis de mettre en évidence que les liaisons hydrogènes étaient responsables du faible avancement de la réaction lors de la synthèse de polyhydroxyuréthanes linéaires.La voie époxy/amine a permis de développer une gamme de matériaux transparents avec des Tg allant de 18 à 47°C. Une étude IR a été réalisée, permettant de mieux appréhender le phénomène de carbonatation de l'amine, récurent lors de la synthèse de résines époxys à température ambiante. L'utilisation de prépolymères aminotéléchéliques permet de contourner ce phénomène.La voie acrylate/amine a permis de développer un matériau transparent de basse Tg, -12°C. L'étude de la réactivité des acrylates avec les amines a été réalisée par DSC et RMN. Des tests de formulation ont été effectués dans le but d'augmenter la TgJuxta company produces thick transparent polyurethane coatings. These coatings are made from hazardous compounds, isocyanates and a mercury based catalyst. In order to protect its employees and consumers Juxta company wants to get rid of the isocyanates in its formulations. Therefore, three new synthesis pathways have been considered.The carbonate/amine pathway is the more innovative one. First, the reactivity and catalysis of model cyclocarbonates and amines were studied. The thioureas, ureas and guanidines proved to be very efficient catalyst families for the cyclocarbonate aminolysis. Then a synthesis was developed to obtain transparent cyclocarbonates. To conclude, a study conducted on linear polyurethanes demonstrated that hydrogen bondings are responsible for the low conversions observed with this reaction.Transparent materials with Tg ranging from 18°C to 47°C were synthesized using the epoxy/amine pathway. An IR study was performed to better understand the amine carbonation phenomenon. It is a frequent phenomenon when the epoxy resins are synthesized at room temperature. Aminotelechelic prepolymers can be used to circumvent it.A low Tg (-12°C) transparent material was synthesized using acrylate/amine synthesis. The couple reactivity was studied by DSC and NMR. Then several formulations were performed in order to increase the Tg
47
Coldham, Iain. "Stereocontrolled cyclic amine synthesis by phenylthio migration." Thesis, University of Cambridge, 1989. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.315736.
Full text
48
Marsh, Sarah Margaret Beatrice. "New amine-substituted cyclopentadienyl and indenyl ligands." Thesis, Durham University, 1997. http://etheses.dur.ac.uk/5012/.
Full textAbstract:
This thesis concerns the new amine-substituted cyclopentadiene and indene ligands C(_5)H(_5)(CH(_2))(_3)N((^t)Bu)H and C(_9)H(_7)(CH(_2))(_3)N((^t)Bu)H which can co-ordinate to a metal through all five carbon atoms of the five-membered ring (η(^5)) and/ or through the nitrogen (σ). Chapter 1 reviews the recent literature concerning Lewis-base functionalised cyclopentadienyl and indenyl ligands and their compounds with s-, p-, d- and f-block metals. Chapter 2 contains a brief review of possible synthetic routes to amine-substituted cyclopentadienyl and indenyl ligands with some examples from the recent literature, and a detailed account of the synthesis of C(_5)H(_5)(CH(_2))(_3)N((^t)Bu)H and C(_9)H(_7)(CH(_2))(_3)N((^t)Bu)H. The amino alcohol (^t)BuNH(CH(_2))(_3) OH was synthesised by the conjugate addition of (^t)BuNH(_2) to ethyl acrylate and reduction of the product ester (^t)BuNH(CH(_2))(_2)C0(_2)Et using LiAIH(_4). (^t)BuNH(CH(_2))(_3)OH was converted into (^t)BuNH(CH(_2))(_3)Br.HBr and (^t)BuNH(CH(_2)(_3)Cl.HCl by reaction with HBr or SOCI(_2). Reaction between (^t)BuNH(CH(_2))(_3)C1.HC1 and two equivalents of Na(C(_5)H(_5)) gave C(_5)H(_5)(CH(_2))(_3)N((^t)Bu)H in good yield. Treatment of (^1)BuNH(CH(_2))(_3)C1.HC1 with excess NaOH followed by reaction with Li(C(_9)H(_7)) gave C(_9)H(_7)(CH(_2))(_3)N((^t)Bu)H, also in good yield. Chapter 3 describes the synthesis of various main group and iron compounds of C(_5)H(_5)(CH(_2))(_3)N((^t)Bu)H and C(_9)H(_7)(CH(_2))(_3)N((^t)Bu)H. Lithium salts Li[C(_5)H(_4)(CH(_2))(_3)N((^t)Bu)H], Li[C(_5)H(_4)(CH(_2))(_3)N((^t)Bu)]Li, Li[C(_9)H(_6)(CH(_2))(_3)N((^t)Bu)H] and Li[C(_9)H(_6)(CH(_2))(_3)N((^t)Bu)]Li were prepared for use as reactive intermediates and Li[C(_5)H(_4)(CH(_2))(_3)N((^t)Bu)H] was characterised as its THF-adduct by (^t)H NMR spectroscopy. The silyl derivatives (Me(_3)Si)C(_5)H(_4)(CH(_2))(_3)NH(^t)Bu and (Me(_3)Si)C(_5)H(_4)(CH(_2))(_3)N((^t)Bu)SiMe(_3) were synthesised and characterised by NMR spectroscopy, and (Me(_3)Si)C(_9)H(_6)(CH(_6))(_3)N((^t)Bu)H and (Me(_3)Si)C(_9)H(_6)(CH(_2))(_3)N((^t)Bu)(SiMe(_3)) were also synthesised. The anune-substituted ferrocene Fe{η(^5)-C(_5)H(_4)(CH(_2))(_3)N((^t)Bu)H}(_2) was synthesised and oxidised to the corresponding ferricenium ion which was isolated as its PF(_6)(^-) salt. Exploratory work was carried out into the preparation of heterobimetallic species by reaction between Fe{η(^5)-C(_5)H(_4)(CH(_2))(_3)N((^t)Bu)H}(_2) and MX(_2) (M = Co, Ni, X = CI, M = Mn, X = Br). The substituted bis(indenyl) iron(II) complex Fe{η(^5)-C(_9)H(_6)(CH(_2))(_3)N((^t)Bu)H}(_2) was also synthesised. Chapter 4 is an account of the chemistry of {η(^5) :σ-C(_5)H(_4) (CH(_2))(_3)N(^t)Bu}Ti(NMe(-2))(_2) which was synthesised by an aminolysis reaction between C(_5)H(_5)(CH(_2))(_3)NH(^t)Bu and Ti(NMe(_2))(_4) Reaction between this compound and various weak acids gave a range of new compounds including{η(^5):σ-C(_5)H(_4)(CH(_2))(-3)N(^t)Bu} Ti(O(^t)Pr)(_2), {η(^5):σ-C(_5)H(_4)(CH(_2))(_3)N(^t)Bu)(_2), {η(^5):σC, {η(^5):σ-C(_5)H(_4)(CH(_2))(_3)N(^t)Bu}Ti(C(_5)H(_5))(NMe(_2)) , {η(^5):σ-C(_5)H(_4)(CH(_2))(_3)N(^t)Bu}Ti(SnBu(_3))(_z) and the imido-bridged dimer [{η(^5):σ-C(_5)H(_4)(CH(_2))(_3)N(^t)Bu}Ti(NHPh)](_2)(µ-NPh)2, the X-ray structure of which is reported. Chapter 5 describes the experimental procedures used, and chapter 6 gives lists of characterising data for each compound. Appendix A gives details of the methods used for magnetic susceptibility determinations; appendix B lists X-ray crystallographic data for [ {η(^5):σ-C(_5)H(_4)(CH(_2))(_3)N(^t)Bu}Ti(NHPh)](_2)(µ-NPh)(_2) and appendix C lists departmental colloquia attended.
49
Snowden, David John. "Stereoselective bicyclic amine synthesis by anionic cyclisation." Thesis, University of Exeter, 1999. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.264609.
Full text
50
Lo, David. "Photostability and photostabilisation of amine acrylated monomers." Thesis, Manchester Metropolitan University, 1994. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.359825.
Full text