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Recent advances in ketenedithioacetal chemistryBrowne, Rory January 1996 (has links)
No description available.
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DESIGN, SYNTHESIS, AND CHARACTERIZATION OF INDANE 2,5-DIKETOPIPERAZINES FOR LIQUID CRYSTAL APPLICATIONSMurigi, Francis January 2011 (has links)
Non-covalent interactions are of great importance in biology, chemistry, and material sciences. Although much information about different types of non-covalent interactions is available, incorporating them in a molecular design to generate a molecule that can undergo association to form a molecular assembly with bulk properties of interest is a challenge. To understand and harness intermolecular interactions, we have designed an indane 2,5-diketopiperazine (DKP) scaffold. Crystal engineering studies with this scaffold show that the molecules assemble into one dimensional tapes via reciprocal amide hydrogen bonds, tapes assemble into two dimensional sheets via arene-arene interactions, and sheets assemble into three dimensional solids via van der Waals contacts. A series of tetraalkoxy-substituted DKPs previously investigated exhibited liquid crystalline behavior. A new class of DKPs with one alkoxy substituent, rather than two, on each benzene ring has been synthesized. Thermochemical studies of the new DKPs by differential scanning calorimetry and polarized optical microscopy show that they are not liquid crystalline as expected. However, in the process of making the DKPs, conformationally constrained tyrosine analogues, (R)- and (S)-5-hydroxy-2-aminoindan- 2-carboxylic acids, were prepared by chromatographic separation of diastereomeric dipeptide derivatives formed from N-Boc-L-phenylalanine. Absolute configurations were assigned by X-ray crystallographic analysis. The series of tetraalkoxy-substituted DKPs showed a remarkable trend in freezing point. The freezing point for the series decreases with an increase in alkyl chain length. To understand the relationship between the crystal packing interactions and the freezing point trend, a study of the association of DKPs in solution by NMR was initiated. An Nmethylated 2,5-diketopiperazine was previously synthesized and studied by NMR using chloroform as solvent to obtain equilibrium constants for self association. Attempted multi-step syntheses of a more lipophilic N-3,7-dimethyloctyl 2,5-diketopiperazine, which was expected to have solubility in non-interfering solvents such as carbon disulfide, benzene, and carbon tetrachloride, failed. In response, a direct and concise method for accessing N-alkyl DKPs was developed, and an N-decyl 2,5-diketopiperazine was synthesized. X-ray crystallographic analysis of the N-decyl 2,5-diketopiperazine reveals formation of dimers via hydrogen bonding in the solid state.
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Aplicação de trinitrato de tálio na preparação de indanos e na síntese total do mutisiantol / Thallium trinitrate application in the preparation of indanes and in the total synthesis of mutisiantholAguilar, Andréa Maria 08 May 2003 (has links)
Esta tese apresenta a primeira aplicação sintética da metodologia desenvolvida em nosso grupo de pesquisa, que se trata da contração de anel de 1,2-diidronaftalenos promovida por trinitrato de tálio (TTN) para fornecer derivados indânicos. A molécula-alvo da abordagem sintética é o Mutisiantol, um sesquiterpeno fenólico, que foi isolado da Mutisia homoeantha em 1979, e que possui substituintes nas posições 1 e 3 do anel ciclopentânico, com uma relação estereoquímica trans entre os mesmos. A rota proposta foi otimizada primeiramente na síntese de um composto modelo e depois aplicada na síntese total do Mutisiantol. O material de partida escolhido para a síntese do Mutisiantol foi o 2-metil-anisol, que é um composto comercial e bastante acessível economicamente. A etapa chave da seqüência envolveu a contração de anel do 1,6-dimetil-7-metóxi-1,2-diidronaftaleno promovida por TTN, que forneceu um derivado indânico com bom rendimento e elevada diastereosseletividade. Três etapas posteriores completaram a seqüência sintética, fornecendo o Mutisiantol em um total de 12 etapas. Descrevemos também o estudo de contração de anel de uma série de 1- tetralonas e 1,2-diidronaftalenos promovida por TTN, visando à obtenção de outros indanos e à complementação de estudos iniciados anteriormente. / This thesis presents the first synthetic application of the methodology developed in our research group, which involves the ring contraction of 1,2- dihydronaphthalenes promoted by thallium trinitrate (TTN) to afford indane derivatives. The target molecule of the synthetic approach is Mutisianthol, a phenolic sesquiterpene, isolated from Mutisia homoeantha in 1979, which embodies a trans-1,3-disubstituted cyclopentyl unit. The proposed route was first optimized in the synthesis of a model compound and then applied to the total synthesis of Mutisianthol. The starting material chosen for the Mutisianthol synthesis was the commercially available and cheap 2-methyl-anisol. The key step of the sequence involved the ring contraction of the 1,6-dimethyl-7-methoxy-1,2-dihydronaphthalene promoted by TTN, which furnished a functionalized indan with good yield and with high diastereoselectivity. The indan derivative was transformed into the final product in 3 steps. Overall, the total synthesis of Mutisianthol was accomplished in 12 steps. The TTN- promoted ring contraction of a series of 1-tetralones and of 1,2- dihydronaphthalenes was also studied in this thesis, with the aim to prepare other indanes and to extend earlier studies.
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Aplicação de trinitrato de tálio na preparação de indanos e na síntese total do mutisiantol / Thallium trinitrate application in the preparation of indanes and in the total synthesis of mutisiantholAndréa Maria Aguilar 08 May 2003 (has links)
Esta tese apresenta a primeira aplicação sintética da metodologia desenvolvida em nosso grupo de pesquisa, que se trata da contração de anel de 1,2-diidronaftalenos promovida por trinitrato de tálio (TTN) para fornecer derivados indânicos. A molécula-alvo da abordagem sintética é o Mutisiantol, um sesquiterpeno fenólico, que foi isolado da Mutisia homoeantha em 1979, e que possui substituintes nas posições 1 e 3 do anel ciclopentânico, com uma relação estereoquímica trans entre os mesmos. A rota proposta foi otimizada primeiramente na síntese de um composto modelo e depois aplicada na síntese total do Mutisiantol. O material de partida escolhido para a síntese do Mutisiantol foi o 2-metil-anisol, que é um composto comercial e bastante acessível economicamente. A etapa chave da seqüência envolveu a contração de anel do 1,6-dimetil-7-metóxi-1,2-diidronaftaleno promovida por TTN, que forneceu um derivado indânico com bom rendimento e elevada diastereosseletividade. Três etapas posteriores completaram a seqüência sintética, fornecendo o Mutisiantol em um total de 12 etapas. Descrevemos também o estudo de contração de anel de uma série de 1- tetralonas e 1,2-diidronaftalenos promovida por TTN, visando à obtenção de outros indanos e à complementação de estudos iniciados anteriormente. / This thesis presents the first synthetic application of the methodology developed in our research group, which involves the ring contraction of 1,2- dihydronaphthalenes promoted by thallium trinitrate (TTN) to afford indane derivatives. The target molecule of the synthetic approach is Mutisianthol, a phenolic sesquiterpene, isolated from Mutisia homoeantha in 1979, which embodies a trans-1,3-disubstituted cyclopentyl unit. The proposed route was first optimized in the synthesis of a model compound and then applied to the total synthesis of Mutisianthol. The starting material chosen for the Mutisianthol synthesis was the commercially available and cheap 2-methyl-anisol. The key step of the sequence involved the ring contraction of the 1,6-dimethyl-7-methoxy-1,2-dihydronaphthalene promoted by TTN, which furnished a functionalized indan with good yield and with high diastereoselectivity. The indan derivative was transformed into the final product in 3 steps. Overall, the total synthesis of Mutisianthol was accomplished in 12 steps. The TTN- promoted ring contraction of a series of 1-tetralones and of 1,2- dihydronaphthalenes was also studied in this thesis, with the aim to prepare other indanes and to extend earlier studies.
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Étude cinétique de la combustion en flamme prémélangée de molécules modèles présentes dans les gazoles / Kinetic combustion studies of surrogate diesel fuel molecules in premixed flamesPousse, Émir 08 January 2009 (has links)
Le moteur HCCI pourrait être une alternative intéressante aux procédés de combustion conventionnels. Néanmoins, le contrôle de la combustion reste difficile dans ce moteur car, contrairement au moteur essence et Diesel, celui-ci est directement contrôlé par la chimie d’oxydation du combustible. Une connaissance très précise des modèles cinétiques détaillés de l’oxydation du carburant est donc indispensable pour pouvoir contrôler ce mode de combustion. L’objectif de cette thèse était de développer et valider expérimentalement des modèles cinétiques d’oxydation à haute température de 3 molécules modèles du gazole en utilisant un brûleur à flamme plate laminaire comme dispositif expérimental. Cette étude présente de nouveaux résultats expérimentaux obtenus sur une flamme laminaire pauvre pré mélangée de méthane ensemencée respectivement avec du n butylbenzène, du n propylcyclohexane et de l’indane. Un modèle cinétique d’oxydation a été développé et validé à haute température pour le n butylbenzène et un autre a été validé en flamme pour le n propylcyclohexane. Dans l’ensemble, ces modèles ont permis de simuler correctement les profils de la plupart des produits mesurés en flamme. Par ailleurs, un modèle cinétique qualitatif d’oxydation pour l’indane a été proposé / The HCCI engine could be an interesting alternative to conventional combustion processes. However, the control of the combustion remains difficult in this engine because, unlike the gasoline and diesel engine, it is directly related to the chemical oxidation of fuel. The development of accurate detailed kinetic models of the oxidation of fuel is therefore essential to control this mode of combustion. The aim of this PhD was to develop and experimentally validate high temperature kinetic oxidation models for 3 molecules representative of diesel fuel by using a flat flame burner experimental device. This study presents new experimental results obtained in a lean laminar premixed methane flame seeded respectively with n butylbenzene, n propylcyclohexane and indane. A kinetic oxidation model was developed and validated at high temperature for n-butylbenzene and another one was validated in flame for n propylcyclohexane. Overall, the models correctly simulated the profiles of most products measured in the flames. Moreover, a qualitative kinetic model for the oxidation of indane has been proposed
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Formation de composés polycycliques par activation de doubles liaisons : approche catalytique intra et intermoléculaire de réactions de type Friedel-Crafts : applications au domaine des arômes et parfums / Non disponibleCacciuttolo, Bastien 14 February 2013 (has links)
L’utilisation de méthodologies de synthèse toujours plus performantes et respectueuses de l’environnement est un axe de recherche majeur de la chimie moderne. L’apport de la catalyse, avec l’utilisation de superacides de Lewis, a permis d’améliorer de nombreux processus synthétiques. Nous avons pu développer dans ce manuscrit des réactions de cycloisomérisation de type réaction de Friedel-Crafts qui donnent accès à un ensemble de structures polycycliques intéressantes avec de bons rendements et sélectivités. L’utilisation d’une quantité catalytique, entre 1 et 10 mol% de Bi(OTf)3, permet l’activation d’oléfines et d’allènes non activés ainsi que de systèmes 1,3-diéniques. Ce type de méthodologie, à économie d’atomes maximale, a permis de limiter la formation de sous-produits, le catalyseur pouvant être recyclé et réutilisé sans perte d’activité. Des approches intra- et intermoléculaires, des réactions cascades et tandems ainsi qu’une étude mécanistique ont été effectuées afin de mieux comprendre la réactivité et ses limitations, et ainsi atteindre une plus large gamme de structures. Les méthodologies développées ont été appliquées au domaine des arômes et parfums pour la synthèse d’analogues de la Calone 1951®, de chromanes, d’indanes et de tétralines fonctionnalisés, posant les bases de travaux futurs pour une meilleur compréhension des relations structures-odeurs / Efficient and ecofriendly synthetic methodologies have always constituted an important area of research in modern organic chemistry. Lewis superacid catalysis has contributed in the improvement of many synthetic processes. We have developed some cycloisomerization reactions including Friedel-Crafts type reaction, giving access to a set of interesting polycyclic structures with good yields and selectivities. The use of a catalytic amount of Bi(OTf)3 (1 to 10 mol%), has allowed the activation of olefins, non-activated allenes and of 1,3-dienic systems. This atom economy methodology can prevent the formation of by-products and the catalyst can be recycled without loss of activity. Intra- and intermolecular approaches, tandem and cascades reactions, as well as mechanistic studies were conducted to enable a better understanding of the reactivity and its limitations to reach a wider range of structures. The developed methodologies were applied to the field of flavors and fragrances in the synthesis of Calone 1951® analogues, and for the preparation of chromans, indanes and tetralins type functionalized structures, for a better understanding of the structure/odor relationship.
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Exploring the iodine(III)-mediated ring contraction: new substrates, novel conditions and asymmetric reactions / Explorando a contração de anel mediada por iodo(III): novos substratos, novas condições e reações assimétricasAhmad, Anees 28 August 2015 (has links)
In the first section this thesis includes the reactivity of various oxygen-containing benzofused cyclic alkenes with HTIB (Hydroxy(tosyloxy)iodobenzene). Instead of getting ring contraction products, 2H-chromene resulted in 4H-chromenes together with trans-addition products. Only cis-addition products were isolated from 4-methyl-2H-chromene. Ring contraction was observed in dihydrobenzoxepines and 2,2-dimethyl-2H-chromenes giving functionalized chromanes and benzofurans, respectively. In the second part, the ring contraction of 1,2-dihydronaphthalenes using HTIB was expanded to substrates bearing oxygen and nitrogen substituents in the aromatic ring. The N-protecting groups Fmoc and Bz are stable under the reaction conditions giving indanes in 64-77% yield. The Ts-protected substrate gave only addition products. Acetoxy and benzoyloxy alkenes afforded indanes in 60-71% yield. A new and efficient method for the oxidative rearrangement (ring contraction and expansion) of alkenes using in situ generated iodine(III) is described in the third section. The protocol uses inexpensive and stable chemicals (PhI, mCPBA and TsOH) furnishing rearrangement products in yields comparable to those obtained using commercially available iodine(III). Additionally, a new route for the one step transformation of 4-methyl-1,2-dihydronaphthalene into 1-methyl-2-tetralone using mCPBA and TsOH was developed. In the last section is presented the reactivity of chiral iodine(III) with 1,2-dihydronaphthalenes. The hypervalent iodine species is generated in situ from chiral aryl iodide, which is prepared in one high yield step from inexpensive starting materials. Protected (Ac, Bz and Fmoc) amine alkenes gave indanes in 60-75% and 58-64% ee. In the same way, oxygenated substrates afforded acetal in 41-61% yield and 54-78% ee. Ring contraction products were obtained in 77-88% yield and 34-40% ee when 1-methyl and aryl substituted alkenes were utilized. / A primeira parte desta tese inclui a reatividade de vários alquenos benzofundidos cíclicos contendo oxigênio com HTIB (Hidróxi(tosilóxi)iodobenzeno). Em vez de obter os produtos de contração de anel, 2H-cromeno resultou em 4H-cromenos, juntamente com produtos trans-adição. Apenas produtos de adição de cis foram isolados a partir de 4-metil-2H-cromeno. Contração do anel foi observada em di-hidrobenzoxepinas e 2,2-dimetil-2H-cromenos dando cromanos funcionalizados e benzofuranos, respectivamente. Na segunda parte, a contração de anel de 1,2-di-hidronaftalenos usando HTIB foi expandida para substratos contendo substituintes de oxigênio e de nitrogênio no anel aromático. Os grupos N-protetores Fmoc e Bz são estáveis sob as condições de reação fornecendo indanos em 64-77% de rendimento. O substrato protegido com Ts deu apenas os produtos de adição. Acetóxi e benzoilóxi alquenos geraram indanos em 60-71% de rendimento. Um método novo e eficiente para o rearranjo oxidativo (contração e expansão do anel) de alquenos utilizando iodo(III) gerado in situ é descrito na terceira parte. O protocolo utiliza reagentes baratos e estáveis (PhI, mCPBA e TsOH) fornecendo produtos de rearranjo com rendimentos comparáveis aos obtidos utilizando iodo(III) disponível comercialmente. Além disso, um método para a transformação em uma etapa de 4-metil-1,2-di-hidronaftaleno em 1-metil-2-tetralona utilizando mCPBA e TsOH foi desenvolvido. Na última parte é apresentada a reatividade de iodo(III) quiral com 1,2-di-hidronaftalenos. A espécie de iodo hipervalente é gerada in situ a partir de iodeto de arila quiral, o qual é preparado em uma etapa em rendimento elevado a partir de materiais de partida baratos. Amino alquenos protegidos (Ac, Bz e Fmoc) deram indanos em 60-75% de rendimento e 58-64% ee. Da mesma forma, os substratos oxigenados proporcionram acetais em 41-61% de rendimento e 54-78% de ee. Produtos de contração de anel foram obtidos em 77-88% de rendimento e 34-40% de ee quando alquenos 1-metil e aril substituídos foram utilizados.
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Formation de composés polycycliques par activation de doubles liaisons : approche catalytique intra et intermoléculaire de réactions de type Friedel-Crafts : applications au domaine des arômes et parfumsCacciuttolo, Bastien 14 February 2013 (has links) (PDF)
L'utilisation de méthodologies de synthèse toujours plus performantes et respectueuses de l'environnement est un axe de recherche majeur de la chimie moderne. L'apport de la catalyse, avec l'utilisation de superacides de Lewis, a permis d'améliorer de nombreux processus synthétiques. Nous avons pu développer dans ce manuscrit des réactions de cycloisomérisation de type réaction de Friedel-Crafts qui donnent accès à un ensemble de structures polycycliques intéressantes avec de bons rendements et sélectivités. L'utilisation d'une quantité catalytique, entre 1 et 10 mol% de Bi(OTf)3, permet l'activation d'oléfines et d'allènes non activés ainsi que de systèmes 1,3-diéniques. Ce type de méthodologie, à économie d'atomes maximale, a permis de limiter la formation de sous-produits, le catalyseur pouvant être recyclé et réutilisé sans perte d'activité. Des approches intra- et intermoléculaires, des réactions cascades et tandems ainsi qu'une étude mécanistique ont été effectuées afin de mieux comprendre la réactivité et ses limitations, et ainsi atteindre une plus large gamme de structures. Les méthodologies développées ont été appliquées au domaine des arômes et parfums pour la synthèse d'analogues de la Calone 1951®, de chromanes, d'indanes et de tétralines fonctionnalisés, posant les bases de travaux futurs pour une meilleur compréhension des relations structures-odeurs
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Exploring the iodine(III)-mediated ring contraction: new substrates, novel conditions and asymmetric reactions / Explorando a contração de anel mediada por iodo(III): novos substratos, novas condições e reações assimétricasAnees Ahmad 28 August 2015 (has links)
In the first section this thesis includes the reactivity of various oxygen-containing benzofused cyclic alkenes with HTIB (Hydroxy(tosyloxy)iodobenzene). Instead of getting ring contraction products, 2H-chromene resulted in 4H-chromenes together with trans-addition products. Only cis-addition products were isolated from 4-methyl-2H-chromene. Ring contraction was observed in dihydrobenzoxepines and 2,2-dimethyl-2H-chromenes giving functionalized chromanes and benzofurans, respectively. In the second part, the ring contraction of 1,2-dihydronaphthalenes using HTIB was expanded to substrates bearing oxygen and nitrogen substituents in the aromatic ring. The N-protecting groups Fmoc and Bz are stable under the reaction conditions giving indanes in 64-77% yield. The Ts-protected substrate gave only addition products. Acetoxy and benzoyloxy alkenes afforded indanes in 60-71% yield. A new and efficient method for the oxidative rearrangement (ring contraction and expansion) of alkenes using in situ generated iodine(III) is described in the third section. The protocol uses inexpensive and stable chemicals (PhI, mCPBA and TsOH) furnishing rearrangement products in yields comparable to those obtained using commercially available iodine(III). Additionally, a new route for the one step transformation of 4-methyl-1,2-dihydronaphthalene into 1-methyl-2-tetralone using mCPBA and TsOH was developed. In the last section is presented the reactivity of chiral iodine(III) with 1,2-dihydronaphthalenes. The hypervalent iodine species is generated in situ from chiral aryl iodide, which is prepared in one high yield step from inexpensive starting materials. Protected (Ac, Bz and Fmoc) amine alkenes gave indanes in 60-75% and 58-64% ee. In the same way, oxygenated substrates afforded acetal in 41-61% yield and 54-78% ee. Ring contraction products were obtained in 77-88% yield and 34-40% ee when 1-methyl and aryl substituted alkenes were utilized. / A primeira parte desta tese inclui a reatividade de vários alquenos benzofundidos cíclicos contendo oxigênio com HTIB (Hidróxi(tosilóxi)iodobenzeno). Em vez de obter os produtos de contração de anel, 2H-cromeno resultou em 4H-cromenos, juntamente com produtos trans-adição. Apenas produtos de adição de cis foram isolados a partir de 4-metil-2H-cromeno. Contração do anel foi observada em di-hidrobenzoxepinas e 2,2-dimetil-2H-cromenos dando cromanos funcionalizados e benzofuranos, respectivamente. Na segunda parte, a contração de anel de 1,2-di-hidronaftalenos usando HTIB foi expandida para substratos contendo substituintes de oxigênio e de nitrogênio no anel aromático. Os grupos N-protetores Fmoc e Bz são estáveis sob as condições de reação fornecendo indanos em 64-77% de rendimento. O substrato protegido com Ts deu apenas os produtos de adição. Acetóxi e benzoilóxi alquenos geraram indanos em 60-71% de rendimento. Um método novo e eficiente para o rearranjo oxidativo (contração e expansão do anel) de alquenos utilizando iodo(III) gerado in situ é descrito na terceira parte. O protocolo utiliza reagentes baratos e estáveis (PhI, mCPBA e TsOH) fornecendo produtos de rearranjo com rendimentos comparáveis aos obtidos utilizando iodo(III) disponível comercialmente. Além disso, um método para a transformação em uma etapa de 4-metil-1,2-di-hidronaftaleno em 1-metil-2-tetralona utilizando mCPBA e TsOH foi desenvolvido. Na última parte é apresentada a reatividade de iodo(III) quiral com 1,2-di-hidronaftalenos. A espécie de iodo hipervalente é gerada in situ a partir de iodeto de arila quiral, o qual é preparado em uma etapa em rendimento elevado a partir de materiais de partida baratos. Amino alquenos protegidos (Ac, Bz e Fmoc) deram indanos em 60-75% de rendimento e 58-64% ee. Da mesma forma, os substratos oxigenados proporcionram acetais em 41-61% de rendimento e 54-78% de ee. Produtos de contração de anel foram obtidos em 77-88% de rendimento e 34-40% de ee quando alquenos 1-metil e aril substituídos foram utilizados.
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Structure and Exciton Coupling in Jet-Cooled BichromophoresHamza, Abdulhamid 23 March 2008 (has links)
No description available.
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