Les travaux présentés dans ce mémoire décrivent une nouvelle voie de synthèse d'aminoalcools 1,2 à partir de γ-bromo-β-cétosulfoxydes, dans lesquels seul le centre stéréogène du soufre est défini. Cette synthèse s'appuie sur deux processus hautement stéréocontrôlés dirigés par le groupement sulfoxyde : le dédoublement cinétique dynamique lors de la substitution nucléophile du brome par la dibenzylamine et la réduction diastéréosélective du carbonyle. Les syn-γ-N,N-dibenzylamino-β-hydroxysulfoxydes correspondants ont été obtenus avec des excès diastéréoisomériques supérieurs à 95%. Les syn-γ-N,N-dibenzylamino-β-hydroxysulfoxydes se sont avérés être des intermédiaires très intéressants pour la synthèse de produits comportant le motif aminoalcool 1,2. Ainsi, nous avons décrit la préparation d'un 3-N,N-dibenzylamino-1,2-diol et son utilisation dans une nouvelle stratégie de déprotection régiodivergente d'acétals cycliques. Nous avons également décrit un nouvel accès aux cis-2-méthyl-6-alkylpipéridin-3-ols, via l'ouverture de cycle d'un 3-N,N-dibenzylamino-1,2-époxyde par l'azaénolate dérivé d'une hydrazone, et l'avons appliqué à la synthèse d'un alcaloïde, la (+)-déoxocassine. Parallèlement, nous avons débuté une étude de synthèse d'aminoalcools 1,3 par la réduction diastéréosélective d'une oxime dérivée d'un δ-céto-β-hydroxysulfoxyde. / In this thesis manuscript, we report on a new pathway to 1,2-aminoalcohols starting from chiral nonracemic γ-bromo-β-ketosulfoxides. This two-step approach, where the stereo control is provided by the sulfoxide group, relies on a highly stereocontrolled nucleophilic substitution of the bromine by dibenzylamine, combined with a dynamic kinetic resolution process, and the reduction of the carbonyl group. The corresponding syn-γ-N,N-dibenzylamino-β-hydroxysulfoxides were obtained with more than 95% diasteroisomeric excess. These syn-γ-N,N-dibenzylamino-β-hydroxysulfoxides turned out to be very useful intermediates for the synthesis of aminoalcohol containing products. Thus, we described the preparation of a 3-N,N-dibenzylamino-1,2-diol, and its use in an original strategy of regiodivergent cyclic acetals deprotection. We also developed a new access to "all cis"-2-methyl-6-alkylpiperidin-3-ols, by the mean of a 3-N,N-dibenzylamino-1,2-epoxide ring opening reaction with the azaenolate derived from an hydrazone. We applied this methodology to the synthesis of an alkaloid, (+)-deoxocassine. In addition, we studied a synthesis of 1,3-aminoalcohols using a diasteroselective reduction of a δ-keto-β-hydroxysulfoxyde-derived oxime.

Submitted by PPG Comunica??o Social (famecos-pg@pucrs.br) on 2018-01-22T12:17:05Z No. of bitstreams: 1 CARLOS_ROBERTO_GASPAR_TEIXEIRA_DIS.pdf: 5062808 bytes, checksum: 3f481299c8472816e21d1520b7145d7d (MD5) / Approved for entry into archive by Caroline Xavier (caroline.xavier@pucrs.br) on 2018-01-29T12:43:25Z (GMT) No. of bitstreams: 1 CARLOS_ROBERTO_GASPAR_TEIXEIRA_DIS.pdf: 5062808 bytes, checksum: 3f481299c8472816e21d1520b7145d7d (MD5) / Made available in DSpace on 2018-01-29T12:47:33Z (GMT). No. of bitstreams: 1 CARLOS_ROBERTO_GASPAR_TEIXEIRA_DIS.pdf: 5062808 bytes, checksum: 3f481299c8472816e21d1520b7145d7d (MD5) Previous issue date: 2017-12-08 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior - CAPES / This research has sought to analyze how the evolution and the development of the number of followers in the Olympic athletes? profiles in the social media Facebook, Twitter and Instagram, was influenced by their participation and performance in Rio 2016. For this purpose, was developed a methodology based on the grounded theory, having as proposal a graphical and statistical analysis of the evolution of the followers in the social media of eight Olympic athletes, divided among gold, silver and bronze medalists, besides not medalists. From the results obtained, was developed a theoretical discussion that has allowed to establish some inferences based on the data and concepts explored by other authors. After all the analyzes it was possible to perceive that the participation and performance of the athletes in Rio 2016 had a significant impact on the growth of their social media. However, it was verified the existence of other influential factors besides the presence and success in the Olympic Games, such as economic, mediatic, aesthetic aspects and even the structure of social media platforms analyzed. Instagram was the platform that presented the greatest growth potential, which reinforced the significance of the visual and aesthetic character that sports practice denotes. It has been realized that the Olympic Games, mass media networks, digital social media and athletes are related in such a peculiar and intense way that they can be observed and analyzed as a unique system, where the construction of an image in the digital environment by every athlete characterizes itself as an important asset for the development of their career. / Esta disserta??o buscou analisar de que forma a evolu??o e o desenvolvimento do n?mero de seguidores nos perfis dos atletas ol?mpicos nas redes sociais, Facebook, Twitter e Instagram, foi influenciada pelas suas participa??es e desempenhos nos Jogos Rio 2016. Para isso, foi desenvolvida uma metodologia pr?pria, baseada na teoria fundamentada, tendo como proposta uma an?lise gr?fica e estat?stica da evolu??o dos seguidores nas redes sociais de oito atletas ol?mpicos, divididos entre medalhistas de ouro, prata e bronze, al?m de n?o vencedores. A partir dos resultados obtidos, foi desenvolvida uma discuss?o te?rica que permitiu estabelecer algumas infer?ncias, fundamentadas nos dados e em conceitos explorados por outros autores. Ao final de todas as an?lises, foi poss?vel perceber que a participa??o e o desempenho dos atletas nos Jogos Ol?mpicos Rio 2016 teve impacto no crescimento de suas redes sociais. Entretanto, foi constatada a exist?ncia de outros fatores influentes, al?m da presen?a e sucesso nos jogos, como aspectos econ?micos, midi?ticos, est?ticos e at? mesmo de estrutura??o dos sites de redes sociais analisados. O Instagram foi a plataforma que apresentou maior potencial de crescimento, o que refor?ou a signific?ncia do car?ter visual e est?tico que a pr?tica esportiva denota. Percebeu-se que os Jogos Ol?mpicos, meios de comunica??o de massa, m?dias sociais digitais e atletas se relacionam de modo t?o peculiar e intenso que podem ser observados e analisados como um sistema ?nico retroalimentado, onde a constru??o de uma imagem no ambiente digital por parte do atleta, dentro desse contexto, se caracteriza como um ativo importante para o desenvolvimento de sua carreira.

Facultad de Filosof?a y Humanidades / Informe de Seminario para optar al grado de Licenciado en Lengua y Literatura Hisp?nica, menci?n Ling??stica / La presente investigaci?n tiene por objetivo analizar la funci?n pragm?tico-discursiva y la estratificaci?n socioling??stica del empleo de los marcadores argumentativos en el habla de Santiago de Chile. En este estudio partimos del supuesto de que las variables sociales influyen en el empleo de los marcadores argumentativos. Esta investigaci?n se enmarca en la corriente de la socioling??stica variacionista, espec?ficamente, en el nivel sint?ctico discursivo. En la actualidad, los estudios en torno a los marcadores discursivos han experimentado un gran incremento, raz?n por la que disciplinas tales como la pragm?tica ling??stica y el an?lisis del discurso han publicado diversos trabajos en relaci?n con el tema. A pesar de esto, uno de los ?mbitos menos considerados en el estudio y an?lisis de los marcadores discursivos es su dimensi?n social, hecho por el cual esta investigaci?n intenta ser un aporte al estudio socioling??stico de dichas part?culas.

Des travaux de recherche en fermentation liquide ont montré que P. canescens est une souche hyperproductrice de xylanases non contaminées par des activités cellulolytiques et amylolytiques. Selon les scientifiques, lintérêt de lutilisation industrielle de ces hémicellulases dans différents secteurs (particulièrement dans la formulation daliments pour le bétail, en industries des jus de fruits et brassicoles, en amidonnerie, en industrie du papier, en pharmacie, dans les textiles et dans la production du bioéthanol) va croître significativement. Mais le développement de ces enzymes est fréquemment limité par le coût de production. Ce travail sest intéressé à loptimisation de la production des xylanases de P. canescens à partir de matières premières peu coûteuses telles les résidus agro-industriels par fermentation solide, une technique traditionnellement utilisée dans la fermentation des aliments en Asie. Létude a démontré que le tourteau de soja est un bon inducteur de la production des xylanases. La teneur initiale en eau, le pH initial, la température de la culture et laération active influencent la synthèse de l'enzyme. Compte tenu des résultats obtenus à léchelle du laboratoire, la transposition à léchelle industrielle serait facilitée naturellement par de fines épaisseurs de cultures statiques, ce qui réduit de moitié le coût de production comparativement à la fermentation liquide. Les expérimentations ont confirmé que la production de xylanases par P. canescens répondait à des phénomènes dinduction et de répression dépendant du substrat et des conditions physico-chimiques de croissance, et non pas à des phénomènes de régulation de type quorum sensing. Lenzyme sous forme liquide concentrée présente une bonne stabilité pendant six mois sans protection préalable (stérilisation, stabilisation ou inhibition de protéases).

As organizações, assim como as pessoas, precisam desenvolver a capacidade de se modificarem, adaptando-se e criando alternativas para solução dos problemas com os quais se defrontam a cada dia. Nesse sentido, a Aprendizagem Organizacional (AO) por meio do compartilhamento e da construção coletiva de novos conhecimentos, é um dos fatores determinantes para produzir novas situações e novos desafios. E para Organizações Sem Fins Lucrativos (NPOs), a AO torna-se imperativo, pois como afirma Drucker (1999), este tipo de organização precisa aprender a medir e avaliar desempenho principalmente em torno de sua missão. Assim, se em qualquer organização o fator humano é fundamental, nas instituições sem fins lucrativos, este, se torna decisivo para avaliar desempenho. Porém, antes de tudo, as organizações precisam avaliar onde elas “estão”, para planejar o próximo caminho. Nesse contexto, os modelos de níveis de maturidade podem contribuir como uma ferramenta de avaliação do estágio de desenvolvimento de uma organização em relação a um determinado interesse organizacional. Dessa forma, o interesse organizacional desse trabalho foi inicialmente a proposição de cinco dimensões da AO das NPOs, e em especial, das entidades de classe, as Câmara de Dirigentes Lojistas (CDL´s), as quais foram: (1) Clima para Questionamentos, (2) Tomada de Decisões, (3) Programas de Capacitação, (4) Comprometimento e Desempenho, e (5) Memória Organizacional. Após, tais dimensões foram associadas com os níveis de maturidade preconizados pela proposta de um modelo de maturidade, a partir dos critérios estruturais utilizados no CMM (Capability Maturity Model) para aferir maturidade. Isso propiciou a criação de um instrumento de pesquisa, com 27 (vinte e sete) perguntas do tipo fechadas, que foi aplicado, por meio de uma survey, a um grupo de 41 (quarenta e uma) CDL´s em atuação no Rio Grande do Sul. Como resultado obteve-se um panorama do estado do RS, identificando como as CDL´s consideram os aspectos da AO, dentro das categorias de estudo definidas nessa pesquisa. Também foi identificado o grau de importância atribuído a cada dimensão e categoria. Assim, considerando a associação com os critérios dos níveis de maturidade propostos, o estudo mostrou que as CDL´s atingiram na média geral o grau de 1,96 (em um máximo de 5,00) nos aspectos mensurados da AO. Este grau, que está muito próximo do chamado nível Controlado (2,00 a 2,99), mas ainda pertencente ao nível considerado Imprevisível (até 1,99), demonstra que as CDL´s sinalizam estar em um processo de início de utilização de práticas repetidas, ou seja, iniciando a utilização de processos planejados, executados e controlados, de acordo com os critérios do CMM e às dimensões propostas. O estudo também revelou que as dimensões propostas da AO para aferição, atingiram um grau de importância elevado, de 4,43 (em um máximo de 5,00), o que demonstrou a relevância destas dimensões atribuídas pelas CDL´s. / Submitted by Marcelo Teixeira (mvteixeira@ucs.br) on 2014-06-17T11:34:13Z No. of bitstreams: 1 Dissertacao Zilio Sartori Junior.pdf: 8500913 bytes, checksum: afbfa2909ac830606e29100d3aa8bf3d (MD5) / Made available in DSpace on 2014-06-17T11:34:13Z (GMT). No. of bitstreams: 1 Dissertacao Zilio Sartori Junior.pdf: 8500913 bytes, checksum: afbfa2909ac830606e29100d3aa8bf3d (MD5) / Organizations, like people, need to develop the capacity of modifying, adapting and creating alternatives to solve the problems that they face every day. In this sense, organizational learning (OL) through the sharing and collective construction of new knowledge, is one of the determining factors to produce new situations and new challenges. And for Nonprofit Organizations (NPOs), OL becomes imperative because as it claims Drucker (1999), this type of organization must learn to measure and evaluate performance particularly around its mission. Thus, in any organization the human factor is essential in nonprofits, it becomes decisive for evaluate performance. However first of all, organizations need to evaluate where they "are", to plan the next path. In this context, models of maturity levels could serve as a tool for assessing the stage of development of an organization in relation to a particular organizational interest. Thus, the organizational interest of this work was first to propose five dimensions of OL of NPOs, in particular, the associations, the Shop Manager Chamber (CDL's), which were: (1) Climate for Questions, (2) Decision Making, (3) Training Programs (4), Compromise and Performance, and (5) Organizational Memory. After such dimensions were associated with the maturity levels recommended by proposing a maturity model, based on structural criteria used in the CMM (Capability Maturity Model) to assess maturity. This caused the creation of a research instrument, with 27 (twenty-seven) closed type questions, which was applied by means of a survey, a group of 41 (forty-one) CDL's acting on the Rio Grande do Sul. As a result it was obtained an overview of the state of RS, identifying as CDL's consider aspects of OL within the categories defined in this research study. Also was identified the degree of importance given to each dimension and category. Thus, considering the association with the criteria proposed maturity levels, the study showed that the CDL's reach general average the level of 1.96 (at a maximum of 5.00) in the measured aspects of the OL. This degree, which is very close to the level called Controlled (2.00 to 2.99), but still belonging to the level considered Unpredictable (up to 1.99), shows that the CDL's signal to be in a process of start of use repeated practice, namely starting the use of procedures planned, executed and controlled in accordance with the criteria of the CMM and the proposed dimensions. The study also found that the proposed dimensions of the OL to measure, attained a high degree of importance, of 4.43 (for a maximum of 5.00), demonstrating the relevance of these dimensions given by CDL's.

As organizações, assim como as pessoas, precisam desenvolver a capacidade de se modificarem, adaptando-se e criando alternativas para solução dos problemas com os quais se defrontam a cada dia. Nesse sentido, a Aprendizagem Organizacional (AO) por meio do compartilhamento e da construção coletiva de novos conhecimentos, é um dos fatores determinantes para produzir novas situações e novos desafios. E para Organizações Sem Fins Lucrativos (NPOs), a AO torna-se imperativo, pois como afirma Drucker (1999), este tipo de organização precisa aprender a medir e avaliar desempenho principalmente em torno de sua missão. Assim, se em qualquer organização o fator humano é fundamental, nas instituições sem fins lucrativos, este, se torna decisivo para avaliar desempenho. Porém, antes de tudo, as organizações precisam avaliar onde elas “estão”, para planejar o próximo caminho. Nesse contexto, os modelos de níveis de maturidade podem contribuir como uma ferramenta de avaliação do estágio de desenvolvimento de uma organização em relação a um determinado interesse organizacional. Dessa forma, o interesse organizacional desse trabalho foi inicialmente a proposição de cinco dimensões da AO das NPOs, e em especial, das entidades de classe, as Câmara de Dirigentes Lojistas (CDL´s), as quais foram: (1) Clima para Questionamentos, (2) Tomada de Decisões, (3) Programas de Capacitação, (4) Comprometimento e Desempenho, e (5) Memória Organizacional. Após, tais dimensões foram associadas com os níveis de maturidade preconizados pela proposta de um modelo de maturidade, a partir dos critérios estruturais utilizados no CMM (Capability Maturity Model) para aferir maturidade. Isso propiciou a criação de um instrumento de pesquisa, com 27 (vinte e sete) perguntas do tipo fechadas, que foi aplicado, por meio de uma survey, a um grupo de 41 (quarenta e uma) CDL´s em atuação no Rio Grande do Sul. Como resultado obteve-se um panorama do estado do RS, identificando como as CDL´s consideram os aspectos da AO, dentro das categorias de estudo definidas nessa pesquisa. Também foi identificado o grau de importância atribuído a cada dimensão e categoria. Assim, considerando a associação com os critérios dos níveis de maturidade propostos, o estudo mostrou que as CDL´s atingiram na média geral o grau de 1,96 (em um máximo de 5,00) nos aspectos mensurados da AO. Este grau, que está muito próximo do chamado nível Controlado (2,00 a 2,99), mas ainda pertencente ao nível considerado Imprevisível (até 1,99), demonstra que as CDL´s sinalizam estar em um processo de início de utilização de práticas repetidas, ou seja, iniciando a utilização de processos planejados, executados e controlados, de acordo com os critérios do CMM e às dimensões propostas. O estudo também revelou que as dimensões propostas da AO para aferição, atingiram um grau de importância elevado, de 4,43 (em um máximo de 5,00), o que demonstrou a relevância destas dimensões atribuídas pelas CDL´s. / Organizations, like people, need to develop the capacity of modifying, adapting and creating alternatives to solve the problems that they face every day. In this sense, organizational learning (OL) through the sharing and collective construction of new knowledge, is one of the determining factors to produce new situations and new challenges. And for Nonprofit Organizations (NPOs), OL becomes imperative because as it claims Drucker (1999), this type of organization must learn to measure and evaluate performance particularly around its mission. Thus, in any organization the human factor is essential in nonprofits, it becomes decisive for evaluate performance. However first of all, organizations need to evaluate where they "are", to plan the next path. In this context, models of maturity levels could serve as a tool for assessing the stage of development of an organization in relation to a particular organizational interest. Thus, the organizational interest of this work was first to propose five dimensions of OL of NPOs, in particular, the associations, the Shop Manager Chamber (CDL's), which were: (1) Climate for Questions, (2) Decision Making, (3) Training Programs (4), Compromise and Performance, and (5) Organizational Memory. After such dimensions were associated with the maturity levels recommended by proposing a maturity model, based on structural criteria used in the CMM (Capability Maturity Model) to assess maturity. This caused the creation of a research instrument, with 27 (twenty-seven) closed type questions, which was applied by means of a survey, a group of 41 (forty-one) CDL's acting on the Rio Grande do Sul. As a result it was obtained an overview of the state of RS, identifying as CDL's consider aspects of OL within the categories defined in this research study. Also was identified the degree of importance given to each dimension and category. Thus, considering the association with the criteria proposed maturity levels, the study showed that the CDL's reach general average the level of 1.96 (at a maximum of 5.00) in the measured aspects of the OL. This degree, which is very close to the level called Controlled (2.00 to 2.99), but still belonging to the level considered Unpredictable (up to 1.99), shows that the CDL's signal to be in a process of start of use repeated practice, namely starting the use of procedures planned, executed and controlled in accordance with the criteria of the CMM and the proposed dimensions. The study also found that the proposed dimensions of the OL to measure, attained a high degree of importance, of 4.43 (for a maximum of 5.00), demonstrating the relevance of these dimensions given by CDL's.

The importance of knowledge transfer inside organizations is an undisputable fact, which got the attention of managers in recent decades. One of the most important reasons that make the knowledge transfer a compulsory task is the danger of its loss. Storytelling in any of its forms, including movie script writing, facilitates knowledge transfer by the use of its potency in representing different information’s component and interrelationships between them. But using movies and movie-scripts in organizations as a knowledge management tool is not as easy as it sounds. There are some issues that should be considered, otherwise the result will not be as good as expected or can even have negative effects on the audience. Based on a search that we have done, we noticed the lack of a comprehensive research which tackles these issues from both knowledge management and scriptwriting perspectives, and provides practical solutions for them. In this thesis we introduce a set of guidelines to inspire knowledge managers or screenwriters who are supposed to write a movie script for transferring knowledge inside organizations. These guidelines may facilitate this process by guiding them to foresee and prevent the issues and solve the problems which may occur. For achieving this goal, we first did a comprehensive literature review and developed a set of guidelines. Then we applied the resulted guidelines on a case. Finally, we evaluated them by utilizing method triangulation. We asked experts' opinions about the applicability and efficiency of the guidelines, tested the clarity and understandability of them, and tested the performance of a movie script which we wrote for the case. The result of the evaluations was pretty satisfying. The knowledge management and screenwriting experts gave us positive comments about efficiency of the guidelines. The managers, who we consulted, found this set of guidelines applicable in real situations. The clarity and understandability test returned an average of 75.58% positive results, which shows that the user of the set of guidelines can read and understand it easily. Finally the test of the movie-script, which we wrote for a real case according to the guidelines, resulted in an average of 85% correct answers. It shows that we were successful in transferring the knowledge, which was embedded in the movie-script, to the recipients. The experts’ opinion and test results indicate that these guidelines are clear, understandable, applicable, and may efficiently facilitate the process of screenwriting for transferring knowledge inside organizations. It can increase the benefits that organizations make from investing in film production by the purpose of transferring knowledge internally.

The importance of knowledge transfer inside organizations is an undisputable fact, which got the attention of managers in recent decades. One of the most important reasons that make the knowledge transfer a compulsory task is the danger of its loss. Storytelling in any of its forms, including movie script writing, facilitates knowledge transfer by the use of its potency in representing different information’s component and interrelationships between them. But using movies and movie-scripts in organizations as a knowledge management tool is not as easy as it sounds. There are some issues that should be considered, otherwise the result will not be as good as expected or can even have negative effects on the audience. Based on a search that we have done, we noticed the lack of a comprehensive research which tackles these issues from both knowledge management and scriptwriting perspectives, and provides practical solutions for them. In this thesis we introduce a set of guidelines to inspire knowledge managers or screenwriters who are supposed to write a movie script for transferring knowledge inside organizations. These guidelines may facilitate this process by guiding them to foresee and prevent the issues and solve the problems which may occur.For achieving this goal, we first did a comprehensive literature review and developed a set of guidelines. Then we applied the resulted guidelines on a case. Finally, we evaluated them by utilizing method triangulation. We asked experts' opinions about the applicability and efficiency of the guidelines, tested the clarity and understandability of them, and tested the performance of a movie script which we wrote for the case. The result of the evaluations was pretty satisfying. The knowledge management and screenwriting experts gave us positive comments about efficiency of the guidelines. The managers, who we consulted, found this set of guidelines applicable in real situations. The clarity and understandability test returned an average of 75.58% positive results, which shows that the user of the set of guidelines can read and understand it easily. Finally the test of the movie-script, which we wrote for a real case according to the guidelines, resulted in an average of 85% correct answers. It shows that we were successful in transferring the knowledge, which was embedded in the movie-script, to the recipients. The experts’ opinion and test results indicate that these guidelines are clear, understandable, applicable, and may efficiently facilitate the process of screenwriting for transferring knowledge inside organizations. It can increase the benefits that organizations make from investing in film production by the purpose of transferring knowledge internally.

The need for renewable and cleaner sources of energy has made biofuels an interesting alternative to fossil fuels, especially in the case of butanol isomers, with their favorable blend properties and low hygroscopicity. Although C4 alcohols are prospective fuels, some key reactions governing their pyrolysis and combustion have not been adequately studied, leading to incomplete kinetic models. Butanol reactions kinetics is poorly understood. Specifically, the unimolecular and H-assisted tautomerism of propen-2-ol to acetone, which are included in butanol combustion kinetic models, are assigned rate parameters based on the analogous unimolecular tautomerism vinyl alcohol ↔ acetaldehyde and H addition to the double bound of iso-butene, respectively. In an attempt to update current kinetic models for tert- and 2-butanol, a theoretical kinetic study of the unimolecular and H-assisted tautomerism, i-C3H5OH⟺CH3COCH3 and i-C3H5OH+Ḣ⟺CH3COCH3+Ḣ, was carried out by means of CCSD(T,FULL)/aug-cc-pVTZ//CCSD(T)/6-31+G(d,p) and CCSD(T)/aug-cc-pVTZ//M062X/cc-pVTZ ab initio calculations, respectively. For H-assisted tautomerism, the reaction takes place in two consecutive steps: i-C3H5OH+Ḣ⟺CH3ĊOHCH3 and CH3ĊOHCH3⟺CH3COCH3+Ḣ. Multistructural torsional anharmonicity and variational transition state theory were considered in a wide temperature and pressure range (200 K – 3000 K, 0.1 kPa – 108 kPa). It was observed that decreasing pressure leads to a decrease in rate constants, describing the expected falloff behavior for both isomerizations. Results for unimolecular tautomerism differ from vinyl alcohol ↔ acetaldehyde analogue reactions, which shows lower rate constant values. Tunneling turned out to be important, especially at low temperatures. Accordingly, pyrolysis simulations in a batch reactor for tert- and 2-butanol with computed unimolecular rate constants showed important differences in comparison with previous results, such as larger acetone yield and quicker propen-2-ol consumption. In the combustion and pyrolysis batch reactor simulations, using all the rate constants computed in this work, H-assisted reactions are limited because H radicals become abundant once the propen-2-ol has been consumed by other reactions, such as the non-catalyzed tautomerism i-C3H5OH⟺CH3COCH3, which becomes one of the main source of acetone. The intermediate radical (CH3ĊOHCH3) is formed exclusively from tert-butanol, with its concentration in 2-butanol oxidation being smaller because the secondary alcohol is unable to produce the radical directly. In all cases, the intermediate is converted effectively to acetone.

The acetate of 6,6-dimethyl-2-cyclohexen-l-ol was thermally decomposed and the pyrolysis products were characterized. This allylic ester decomposed with difficulty. Under conditions which led to complete decomposition of 3-acetoxcyclo-hexene, 6,6-dimethy-2-cyclohexene-l-ol acetate was virtually unreacted. Complete decomposition of the allylic acetate was achieved at about 600°C. The pyrolysis products consisted mainly of o-xylene, toluene, 5,5-dimethyl-l,3-cyclohexadiene and acetic acid. The aromatic compounds are thought to be formed from the less stable diene. Partial decomposition of ester enriched with deuterium in the 4-position, permitted estimation of the isotope effect, Ku/kD, for the pyrolytic elimination. The value obtained was about 2. Together with other experimental evidence, it indicates that the main mode of decomposition is 1,4-conjugate elimination and that allylic rearrangement, if it occurs at all, is unimportant. / Thesis / Master of Science (MS)