L’acylation de Friedel-Crafts est parmi les réactions les plus fondamentales et les plus utiles pour former des cétones aromatiques. Bien que la mise en oeuvre de ces réactions soit habituellement pénalisante en termes de sous produits formés, de rendement atomique et de quantité de catalyseur utilisée, cette voie est encore largement utilisée dans l’industrie de la chimie fine. Ces dernières années, la prise de conscience de l’impact des activités industrielles sur l’environnement a mené les chimistes à travailler sur de nouvelles voies, moins dangereuses et plus respectueuses de l’environnement.Nous avons considéré ici l’acylation d’un dérivé du benzofurane par un chlorure d’acyle, correspondant à une étape intermédiaire pour la fabrication d’un principe actif pharmaceutique. Dans cette étude, la première proposition a consisté à remplacer les catalyseurs classiques (FeCl3 ou AlCl3) par des catalyseurs solides réutilisables. Dans ce travail, plusieurs catalyseurs (zéolites, résines échangeuses d’ions...) ont d’abord été testés dans des conditions « conventionnelles » , c’est-à-dire en utilisant un solvant organique, afin de déterminer le plus performant, en termes de réactivité, de durée de vie et de réutilisabilité. Une zéolite Y s’est avéré la plus adaptée. Cependant, l’utilisation d’un solvant organique (ici le 1,2-dichlorobenzène) reste discutable et l’utilisation du CO2 supercritique comme solvant a donc été envisagée. Pour cela, nous avons imaginé et dimensionné un réacteur tubulaire à lit fixe de catalyseur fonctionnant sous pression et en continu. Les résultats présentés montrent la faisabilité d’un tel procédé et pose les jalons pour arriver à une ou des solutions pour une meilleure mise en oeuvre industrielle des réactions de Friedel-Crafts. / Friedel-Crafts acylation is among the most fundamental and useful reactions to yield aromatic ketones, but it is one of the less acceptable in terms of unwanted polluting by-products or atom economy because of overconsumption of catalyst which is used in stoichiometric quantities in the conventional process. This route is nevertheless still widely used in the fine chemicals industry. In recent years, awareness of the impact of industrial activities on the environment has lead chemists to work on new chemical routes, less dangerous and more environmentally friendly. We considered here the acylation of a benzofurane derivative by an acid chloride, as an intermediary step for a pharmaceutical product. In this study, one of the first alternative was to replace conventional catalysts (FeCl3 or AlCl3), by reusable solid catalysts. In this work, different catalysts (zeolites, ion-exchange resins...) were first tested in "conventional" conditions, i.e., using an organic solvent (1,2-dichlorobenzene in our case), to determine the best one, in terms of reactivity, lifetime and reusability. The zeolite Y was found the most appropriate. However, the use of an organic solvent still remains questionable and the use of supercritical carbon dioxide as the solvent was also considered. Its inherent properties include non-flammability, mild critical conditions, tuneable solubility near to the critical point and very low environmental impact. The reaction was operated using a specifically designed continuous high pressure fixed bed and results concerning yield and selectivity are presented. These results demonstrate the feasibility of such an approach, which would ultimately yield to better industrial operation of Friedel-Crafts reactions.

Submitted by (lucia.rodrigues@ufrpe.br) on 2016-06-17T13:16:44Z No. of bitstreams: 1 Wendell Rodrigues Costa.pdf: 1893651 bytes, checksum: 0200c0289e0f82e9f533f37a96edc663 (MD5) / Made available in DSpace on 2016-06-17T13:16:44Z (GMT). No. of bitstreams: 1 Wendell Rodrigues Costa.pdf: 1893651 bytes, checksum: 0200c0289e0f82e9f533f37a96edc663 (MD5) Previous issue date: 2013-05-27 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / This work aims to understand why and how the Society of Mechanical Artists and Liberals sought to promote the development of the teaching of crafts in Pernambuco. To do so, we proceeded to an analysis of the Society of the Artists, from its formation to its commitment to manage the School of Arts and Crafts (Liceu de Artes e Ofícios). The analytical course proved to be the Society of Artists not only the beneficiary of the public funds to finance the activities of the School, but also left some visible conflicts arising from the relationship of Society with the government - in the person of the inspector - and with some partners and students. The first question was to know how the leaders of the Society took care of the public funds to manage the School. Then, we tried to understand why, in many situations, the officers asked the government to extinguish the post of inspector of the School of Arts and Crafts. This present research approaches the theoretical perspective proposed by the French philosopher Michel Foucault, due to his large study on biopower and the effect on the discipline. With the foucauldian concept of biopower, it was possible to understand the position of the Brazilian State as manager of the society. The dissertation was drawn from the analysis of sources such as documents of the Society of the Mechanical Artists and Liberals and reports relating to the supervision of the School of Arts and Crafts. The clipping researched is between 1880 to 1908, covering the period since the inauguration of the School of Arts and Crafts till the end of the inspection of the inspector Francisco Augusto Pereira da Costa. With the survey, we could understand that the inspection directed to the Society of the Artists had the intention to make the School provide to the working classes a vocational training that would meet the labor market. From the research procedures and the results obtained, it is evident that despite the conflicts in which they became involved, the Society of Artists bequeathed to Brazil from the First Republic, through the School of Arts and Crafts, an educational establishment that resting in the pedagogy of work, produced a workforce able to meet the sectors of industry and commerce. / Este trabalho objetiva compreender por que e de que forma a Sociedade dos Artistas Mecânicos e Liberais procurou promover o desenvolvimento do ensino de ofícios em Pernambuco. Para isso, procedeu-se a uma análise da Sociedade dos Artistas, desde a sua formação até o seu empenho em administrar o Liceu de Artes e Ofícios. O percurso analítico revelou ser a Sociedade dos Artistas não só beneficiária de verbas públicas para financiamento das atividades do Liceu, mas também deixou visíveis alguns conflitos surgidos do relacionamento da Sociedade com o governo – na pessoa do fiscal – e com alguns sócios e alunos. A primeira questão foi saber como os dirigentes da Sociedade cuidavam das verbas públicas para administrar o Liceu. Em seguida, procurou-se entender por que, em diversas situações, os diretores pediam ao governo que extinguisse o cargo de fiscal do Liceu de Artes e Ofícios. A presente pesquisa aproxima-se da perspectiva teórica proposta pelo filósofo francês Michel Foucault, em virtude de seu largo estudo sobre o biopoder e, por efeito, sobre a disciplina. Com o conceito foucaultiano de biopoder, foi possível entender a posição do Estado brasileiro como gestor da sociedade. A dissertação foi elaborada a partir da análise de fontes como os documentos da Sociedade dos Artistas Mecânicos e Liberais e os relatórios referentes à fiscalização do Liceu de Artes e Ofícios. O recorte pesquisado se dá entre 1880 a 1908, porquanto abrange o período da inauguração do Liceu de Artes e Ofícios até o final da inspeção do fiscal Francisco Augusto Pereira da Costa. Com a pesquisa realizada, pôde-se compreender que a fiscalização dirigida à Sociedade dos Artistas intencionava fazer com que o Liceu proporcionasse às classes operárias uma formação profissional que atendesse ao mercado de trabalho. A partir dos procedimentos de pesquisa e dos resultados obtidos, fica evidente que, apesar dos conflitos nos quais se viu envolvida, a Sociedade dos Artistas legou ao Brasil da Primeira República, por meio do Liceu de Artes e Ofícios, um estabelecimento educacional que, repousando na pedagogia do trabalho, produziu uma mão de obra capaz de atender aos setores da indústria e do comércio.

Triquentrinas A são produtos naturais marinhos com atividade biológica e alta complexidade estrutural. Estes fatores tornam estes alcaloides e compostos análogos, como os herbindóis, alvos para a síntese total e plataforma para o desenvolvimento de novas metodologias sintéticas. Nesta Dissertação de Mestrado, procurou-se completar a síntese estereosseletiva da (+)-cis-triquentrina A empregando-se intermediários sintéticos protegidos com o grupo benzila que poderão ser usados para a futura prospecção de novos compostos com atividade biológica. A rota proposta baseia-se na obtenção do ácido (S)-3-(1-benzil-4-etil-1H-indol-7-il)butanóico, um intermediário-chave já descrito por Silva e colaboradores no percurso da síntese total da (+)-trans-triquentrina A, e da finalização da síntese de acordo com a abordagem proposta pelo grupo de RajanBabu para conversão do análogo protegido com grupo tosila à (+)-cis-triquentrina A. A resolução enzimática do intermediário-chave com lipase de Pseudomonas cepacia imobilizada em terra diatomácea foi otimizada, resultando em rendimentos de 32% e 99% ee na metade do tempo descrito anteriormente. Na etapa-chave da síntese, o (S)-ácido foi submetido a uma acilação de Friedel-Crafts intramolecular na presença de anidrido trifluoroacético que produziu o produto de ciclização desejado com 40% de rendimento. Na etapa final da síntese, o intermediário sintético protegido com grupo benzila não pode ser convertido à (+)-cis-triquentrina A, empregando-se a metodologia desenvolvida para a redução do composto análogo tosilado, dada a diferença de reatividade imposta pela troca do grupo protetor. As etapas realizadas até o penúltimo intermediário sintético (S)-8, consta com 10 etapas e rendimento global de 1,3%. viii As diferenças eletrônicas e estruturais relacionadas a diferentes grupos protetores poderão ser refletidas em variações na atividade antiproliferativa de indóis relacionados a triquentrinas. Ainda no interesse de preparar moléculas para envio à análises de atividade antiproliferativa preparou-se um composto relacionado à síntese da trans-triquentrina A tendo como etapa-chave uma contração de anel mediada por I(III) em 21% de rendimento, cujo trabalho foi incluído nos anexos. / Trikentrins A are marine natural products with biological activity and high structural complexity. These factors make these alkaloids and analogous compounds, such as herbidoles, targets for total synthesis and platform for the development of new synthetic methodologies. In this Master\'s Dissertation, we attempted to complete the stereoselective synthesis of (+)-cis-trikentrin A using synthetic intermediates protected with the benzyl group that could be used for the future prospection of new compounds with biological activity. The proposed route is based on the preparation of (S)-3-(1-benzyl-4-ethyl-1H-indol-7-yl) butanoic acid, a key intermediate already described by Silva et al., in the course of total synthesis (+)-trans-triquentrin A, and the final part of the synthesis according to the approach proposed by the RajanBabus group for conversion of the protected analogue with tosyl group to (+)-cis-trikentrin A. The enzymatic resolution of the key intermediate with Pseudomonas cepacia lipase immobilized on diatomaceous earth was optimized, resulting in 32% yield and 99% ee in half the time described above. In the key step of the synthesis, the (S)-acid was subjected to an intramolecular Friedel-Crafts acylation in the presence of trifluoroacetic anhydride which yielded the desired cyclization product in 40% yield. In the final step of the synthesis, the synthetic intermediate protected with benzyl group couldnt be converted to (+)-cis-trikentrin A, employing the methodology developed for the reduction of the tosylated analogous compound, given the difference of reactivity imposed by exchange of the protective group. The steps carried out up to the synthetic intermediate (S)-8, consists of 10 steps and overall yield of 1.3%. Electronic and structural differences related to different protective groups may be reflected in variations in the antiproliferative activity of indoles related to trikentrins. A compound related to the synthesis of trans-triquentrin A having as its key step an I(III) mediated ring contraction in 21% yield was also prepared in the interest of preparing molecules for antiproliferative activity analysis, whose work was included in the appendix.

O objetivo desta pesquisa é o estudo da arquitetura residencial que se desenvolveu na cidade de São Paulo nos anos 1920, e das influências que ajudaram a moldá-la. Entre estas, a do movimento Arts and Crafts, que revolucionou a arquitetura doméstica britânica no final do século XIX e teve repercussão internacional. Tais ressonâncias ocorreram de forma direta e também através de uma triangulação com os Estados Unidos. Ali, haverá certa popularização do movimento inglês na figura do bangalô, juntamente com o aprimoramento da cultura burguesa da habitação do Arts and Crafts. Esta nova cultura da habitação chegará ao Brasil principalmente através das revistas de decoração, trazendo uma nova maneira de morar para a classe média, que se estabelecerá principalmente nos novos subúrbios que se constituem em São Paulo nas primeiras décadas do século XX, particularmente o Jardim América, executado pela Companhia City. / The subject of this work is the domestic architecture that arises in the city of São Paulo, Brazil, in the 1920\'s decade and the influences it has suffered. Among them, there is the resonance from the Arts and Crafts movement, which changed the course of the british domestic architecture in the 1890\'s and acquired international reputation. The influences on brazilian architecture probably came by two ways; straight from britain and also through the United States. In this country, there will be a mass production of a new kind of dwelling, the bungalow, which embodies the spirit of the british movement, in a more democratic way. This bourgeois housing culture, inherited from England, will arrive in Brazil mainly through domestic interior magazines. These domestic life-styles will settle in the suburbs that arise in São Paulo in the first decades of twentieth century, mainly in Jardim America from the Companhia City.

Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(工学) / 甲第17584号 / 工博第3743号 / 新制||工||1570(附属図書館) / 30350 / 京都大学大学院工学研究科物質エネルギー化学専攻 / (主査)教授 中村 正治, 教授 大江 浩一, 教授 村田 靖次郎 / 学位規則第4条第1項該当

L’élaboration de synthèses rapides et efficaces de molécules complexes à partir de substrats de départ simples en utilisant un minimum d’étapes constitue un véritable enjeu de la chimie organique contemporaine. Dans ce contexte, les réactions multicomposant, grâce à leur capacité à créer plusieurs liaisons en une étape, offrent une grande efficacité pour synthétiser des structures d’une grande complexité moléculaire. Par ailleurs, la catalyse organométallique s’est considérablement développée ces dernières années, pour devenir un outil de choix pour la formation de liaisons carbone-carbone. La réaction de Tsuji-Trost est notamment un des plus connues dans ce domaineDans le cadre de cette thèse, la découverte de post-condensations originales à partir d’adduits obtenus par les réactions multicomposant impliquant un isonitrile est l’axe majeur de nos recherches. Ces réactions permettent un accès efficace à un large éventail de composés hétérocycliques.Tout d’abord, nous avons développé une nouvelle voie efficace de synthèse des indolylacétamides via une cascade Passerini/Friedel-Crafts à partir d’adduits de Passerini et d’indoles en présence d’un acide de Lewis. Une version monotope de cette cascade a été ainsi développée.Par ailleurs, nous avons exploité la réactivité des hydrazones N-monosubstitués en tant que bis-nucléophile 1,3 en vue de préparer divers dérivés de 2-pyrazolines via une cascade Tsuji-Trost/Cyclisation pallado-catalysée à partir des adduits de Passerini ou de phosphonates. Dans le but de préparer des 2-pyrazolines énantiosélectivement enrichis, une version énantiosélective de cette cascade a été également réalisée à partir d’adduits de Passerini.Enfin, la mise au point d’une nouvelle cascade Tsuji-Trost/Cyclisation exploitant l’allyle méthyle carbonate a permis l’accès rapide à des motifs hétérocycliques de type oxazolidine-2,4-diones en exploitant le dioxyde de carbone généré in situ. / The development of rapid and efficient syntheses of complex molecules from simple starting substrates using a minimum of steps is a real challenge of contemporary organic chemistry. In this context, multicomponent reactions, thanks to their ability to create several one-step bonds, offer a high efficiency in synthesizing structures of great molecular complexity. Moreover, organometallic catalysis has developed considerably in recent years, becoming a tool of choice for the formation of carbon-carbon bonds. The Tsuji-Trost reaction is specially well known in this field.In this thesis, the discovery of the original post-condensations from the adducts obtained by multicomponent reactions involving isonitrile is the major axis of our research. These reactions allow efficient access to a wide range of heterocyclic compounds.First, we have developed a new efficient pathway for the synthesis of indolylacetamides via the Passerini/Friedel-Crafts cascade from the Passerini adducts and indole in the presence of a Lewis acid. A one-pot version of this cascade has been also developed.Furthermore, we have exploited the reactivity of N-monosubstituted hydrazones as 1,3-bis-nucleophile in order to prepare various 2-pyrazoline derivatives via a pallado-catalyzed Tsuji-Trost/Cyclisation cascade from the Passerini adducts or Phosphonates. In order to prepare enantioselectively enriched 2-pyrazolines, the enantioselective version of this cascade was also realized from the Passerini adduct.Finally, the development of a new Tsuji-Trost/Cyclization cascade from the Passerini adducts and the allyl methyl carbonate provide straight fast and efficient access to oxazolidine-2,4-diones heterocyclic units by exploiting the carbon dioxide generated in situ.

This study analyzes the reactivity and selectivity of Friedel-Crafts alkylations using benzylic alcohols and phenols in the presence of a Lewis acid, to synthesize methoxylated bisphenols as a benign alternative to BPA. The degree of methoxylation on the electrophile appears to affect the yield of the reaction while the degree of methoxylation on the nucleophile appears to affect the selectivity. A more methoxylated electrophile results in a lower yield whereas a more methoxylated nucleophile results in a change in ratio between the bisphenol isomers and/or causes other isomers to form. Neither the yield nor the selectivity appears to be affected significantly by the temperature.

Carbon nano-onions (CNOs) discovered by Ugarte in 1992 are multi-layered fullerenes that are spherical analogs of multi-walled carbon nanotubes with diameters varying from 6 nm to 30 nm. Among the various methods of synthesis, CNOs prepared by graphitization of nanodiamonds (N-CNOs) and underwater electric arc of graphite rods (A-CNOs) are the subject of our research. N-CNOs are considered as more reactive than A-CNOs due to their smaller size, high curvature and surface defects. This dissertation focuses on structural analysis and surface functionalization of N- CNOs with diameters ranging from 6—10 nm. Synthetic approaches such as oleum- assisted oxidation, Freidel-Crafts acylation and Billups reductive alkylation were used to functionalize N-CNOs to improve their dispersion properties in aqueous and organic solvents. Functionalized N-CNOs were characterized using various techniques such as TGA, TG-MS, Raman spectroscopy and pH-titrimetry. We designed an experimental method to isolate polycyclic aromatic adsorbates formed on the surface of oleum oxidized N-CNOs (ON-CNOs) and characterized them. A-CNOs, on the other hand are bigger than N-CNOs with diameters ranging from 20—40 nm. In this dissertation, we discuss the preparation of graphene structures by unzipping of A-CNOs using KMnO4 as oxidizing agent. These graphene structures were characterized using powder X-ray diffraction, TGA, BET nitrogen adsorption/desorption studies and compressed powder conductivity. This dissertation also focuses on lithiation/delithiation studies of N-CNOs, A- CNOs and A-CNO-derived graphene structures to use them as negative electrode materials in lithium-ion batteries. The cycling performances of these materials at a charge/discharge rate of C/10 were discussed. The cycling performance of N-CNOs was tested at faster charge/discharge rate of C.

Syftet med detta arbete är att öka insikten i hur fördelningen mellan hantverk och uttryck ser ut på trumsetslektioner inom genrerna rock/pop/jazz och hur olika lärare arbetar kring/med begreppen personligt uttryck och hantverk. Jag har intervjuat fyra pedagoger – tre från musikskolan och en från gymnasiet – och använt mig av kvalitativ intervju som metod. Följande forskningsfrågor ligger som grund för arbetet: Finns det en tydlig uppdelning mellan moment som fokuserar på hantverk och personligt uttryck under trumsetslektioner på gymnasieskolan och kulturskolan - och i så fall, hur ser fördelningen mellan dessa inslag ut? Hur hanterar trumsetslärare dessa två begrepp i sin undervisning?   Resultatet visar att samtliga informanter inkluderar moment som kretsar kring både hantverk och personligt uttryck i trumsetsundervisningen. De kombinerar ibland dessa två områden men resultaten visar även att användandet kan bero på undervisningens natur snarare än aktiva val gjorda av informanterna. De deltagande trumsetslärarna definierar personligt uttryck som något som har med det musikaliska att göra till skillnad från hantverket, som har att göra med tekniskt kunnande. Fokus på lektionen tenderar att väga över åt det personliga uttrycket, så länge eleven har kommit till en viss grundläggande hantverksmässig nivå. Gemensamt för alla informanter är att fokus har flyttats från ett mer tekniskt/hantverksmässigt fokus till ett mer individinriktat med betoning på uttryck, i takt med ökad arbetslivserfarenhet. De informanter som har arbetat på både gymnasium och kulturskola menar att betygen kan verka hämmande i valet av fokus, eftersom personligt uttryck kan te sig mera svårbedömt än teknisk färdighet. / The aim of this work is to increase an understanding of how the division between a technical and personal expression in teaching the drums in the genres of rock, pop and jazz, and how teachers work around or with the concepts of personal expression and technique. I have interviewed four teachers and used the qualitative interview method. The following research questions are the basis of the work: Is there a clear division between the elements that focus on a technical and personal expression in teaching the drums in high school and school of music and arts - and if so, what is the relationship between those elements? How do drum teachers handle these two concepts in their teaching? The results indicate that all the informants include elements that revolve around both a technical and personal expression in drum lessons. They sometimes combine these two, but the results also show that the use may depend on the nature of teaching rather than an active choice made by the informants. The participating teachers define self-expression as anything that relates to the musical side of playing as opposed to the technical, which has to do with technical expertise. Focus on the lesson tends to lean more to the personal expression, as long as the student has reached a certain basic level of technique. Common to all informants is that the focus has shifted from a more technical and craft-oriented focus to a more individual emphasis with a focus on expression, with an increase in work experience. The informants who have worked at both the high school and school of music and arts level believe that grades may constrain the choice of focus, as self-expression may seem more difficult to assess than technical skills.

Founded on the premise that the existing literature on Gabrielle ‘Coco’ Chanel does not give a comprehensive, balanced and objective survey of the dress designs produced by the house from 1916-1929, the thesis ‘Reviewing Chanel’ provides a catalogue raisonné of the designs shown in British and French Vogue during this period. This representative sample of Chanel’s work facilitates the very necessary and overdue re-assessment of Chanel’s early career and contribution to twentieth century fashion. Part One of the Introduction includes a review of the existing literature on Chanel and explains the rationale behind the production of a catalogue of the dress designs reproduced in British and French Vogue. Part Two serves as the introduction to the twenty-eight essays which outline the principal developments in each of the dress design collections presented by the house between 1916-1929. Each essay provides an analytical summary of the key themes and developments of the collection and relates Chanel’s work to that of the other leading houses in Paris during this period.