The major aim of this thesis has been to contribute to the understanding of the CH$ sb2$/OH/NH$ sb2$ group interactions by means of studies of alcohol-amine mixtures in the gas and liquid phases. / To study these interactions in the gas phase a Burnett type equipment was designed, built and operated at low pressure, obtaining experimental pressure-temperature (P-T) data for various systems including alcohol-amylamine mixtures. The P-T data were reduced by a method developed in this work to give values of second virial coefficients. Measurements on known systems were in excellent agreement with values reported in the literature. A group contribution method for predicting pure compounds and interaction second virial coefficients is presented. This method is equal, or superior to methods already available. / To study the CH$ sb2$/OH/NH$ sb2$ group interactions in the liquid phase, vapor-liquid-equilibrium (VLE) experiments with alcohol-amylamine mixtures were carried out in a Van Ness type apparatus. The raw data were reduced by a novel model free method using the second virial coefficients obtained previously for these mixtures. A group contribution method for predicting vapor-liquid-equilibria of multicomponent multigroup mixtures is proposed. Excellent predictions are obtained with this method. / Finally, computer experiments of Lennard-Jones fluid mixtures were carried out to help in the understanding of the local composition concept. This concept is of fundamental importance not only in the models used in this work but also in numerous other solution models.

Thesis (Ph.D.)--University of Tulsa, 1990. / Bibliography: leaves 123-126.

Thesis (M.Sc. (Organic Chemistry))--Mahidol University, 1984.

Thesis (Ph. D.)--University of Missouri-Columbia, 1997. / Typescript. Vita. Includes bibliographical references (leaves 362-370). Also available on the Internet.

Thesis (Ph. D.)--University of Missouri-Columbia, 1997. / Typescript. Vita. Includes bibliographical references (leaves 362-370). Also available on the Internet.

Thesis (M.S.)--University of Wisconsin--Madison, 1961. / Typescript. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references (leaf 27).

Thesis (M. S.)--Chemical Engineering, Georgia Institute of Technology, 2009. / Committee Chair: Realff, Matthew; Committee Member: DeMartini, Nikolai; Committee Member: Muzzy, John; Committee Member: Sievers, Carsten.

Thesis (M.S.)--University of North Carolina at Wilmington, 2005. / Includes bibliographical references (leaf: [36] )

Orientador: Luiz Carlos Dias / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-10T02:46:17Z (GMT). No. of bitstreams: 1 Fattori_Juliana_M.pdf: 2240885 bytes, checksum: 9db38d985e4bc4fb6668aeb311352757 (MD5) Previous issue date: 2007 / Resumo: A unidade aminodiol está presente em esfingolipídeos que são uma importante classe de biomoléculas. Os esfingolipídeos são componentes das membranas celulares e estão relacionados a processos de crescimento, diferenciação celular e apoptose. Alguns esfingolipídeos como a esfingosina e compostos análogos apresentam atividade antitumoral, por isso metodologias para a obtenção de compostos deste tipo têm despertado a atenção dos químicos orgânicos sintéticos. Assim, neste trabalho foi desenvolvida uma metodologia curta e eficiente para a preparacao de derivados de 2-amino-3,5-diois, com o intuito de fornecer material para testes biologicos. A sintese aqui apresentada envolveu o acoplamento de uma aliltricloroestanana aquiral com a-aminoaldeidos fornecendo alcoois homoalilicos em bons rendimentos e com alta diastereosseletividade. Em seguida a clivagem oxidativa da dupla ligação presente nos álcoois homoalilicos levou a formacao de b-hidroxicetonas inéditas na literatura. E, por fim, a reducao das b-hidroxicetonas sob diferentes condições conduziu aos 2-amino-3,5-diois 1,3-syn e 1,3-anti em bons rendimentos e excelente diastereosseletividade / Abstract: The aminodiol moiety is present in sphingolipids which are an important class of biologically active compounds. These compounds play an important role in the chemistry of cellular membranes, cell growth differentiation and apoptosis. Some of them, like sphingosine and analogues have showed anticancer activity. Therefore procedures to prepare this kind of compounds have been developed by the organic chemists. In this work we have developed a short and efficient route for the synthesis of 2- amino-3,5-diol derivatives, in order to provide material for further biological studies. Our approach to the 2-amino-3,5-diols involved the coupling of an achiral alilthriclorostannane with a-aminoaldehydes to give the corresponding homoallylic alcohols in good yields and with high levels of diastereoslectivity. Double bond oxidation gave the corresponding b-hydroxyketones in excellent yields. Finally, reduction of the b-hydroxyketones under different conditions gave the desired 2- amino-3,5-diols 1,3-syn and 1,3-anti in good yields and high diastereoselectivities / Mestrado / Quimica Organica / Mestre em Química

Submitted by Fabio Sobreira Campos da Costa (fabio.sobreira@ufpe.br) on 2016-08-31T13:18:33Z No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) Tese-Jucleiton-5.pdf: 12633477 bytes, checksum: a9581d3a8bca6762bb7a3d370f0ca74d (MD5) / Made available in DSpace on 2016-08-31T13:18:33Z (GMT). No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) Tese-Jucleiton-5.pdf: 12633477 bytes, checksum: a9581d3a8bca6762bb7a3d370f0ca74d (MD5) Previous issue date: 2016-02-15 / CNPq / Neste trabalho quatro diferentes métodos para a síntese de álcoois homopropargílicos obtidos a partir de aldeídos e compostos de boro foram desenvolvidos. A primeiro método foi baseado na utilização da resina Amberlyst A-31 como promotora. Os melhores rendimentos (70-95%) foram obtidos quando foi empregado uma quantidade de 200% m/m da Amberlyst A-31 em CH2Cl2, sob atmosfera aberta, com tempos reacionais que variaram de 1,5-7,0 horas. A resina pôde ser recuperada e reutilizada até três vezes em outras reações de propargilação sem perdas no rendimento. O segundo método desenvolvido baseou-se na utilização da argila Tonsil como promotora. Neste caso, os compostos desejados foram obtidos em bons rendimentos (60-96%) quando uma quantidade de 150% m/m de Tonsil em CH2Cl2, sob atmosfera aberta e temperatura ambiente foi utilizada. Quando os dois métodos usando promotores heterogêneos foram comparados frente a reações de propargilação de aldeídos contendo grupos protetores sensíveis em meio ácido, o melhor resultado foi obtido utilizando Tonsil onde o produto desejado foi obtido em bom rendimento juntamente com uma pequena quantidade do produto de desproteção. O terceiro método desenvolvido foi baseado na utilização do BF3•Et2O como promotor. Novamente, os produtos foram obtidos em bons rendimentos (75-91%) após um tempo reacional de 30 minutos. A melhor condição reacional foi observada quando uma quantidade de 4 equivalentes de BF3•Et2O em THF, sob atmosfera de argônio e temperatura ambiente foi utilizada. As tentativas de reação de propargilação assimétrica de aldeídos empregando-se BF3Et2O e diferentes ligantes quirais levaram aos álcoois homoalílicos desejados em bom rendimento, no entanto, em nenhuma das reações testadas foi observado excesso enantiomérico. Por fim, quando foi empregado a irradiação de micro-ondas, a melhor condição encontrada para a propargilação de aldeídos pelo ácido alenilborônico pinacol éster foi utilizando a temperatura de 100ºC e uma potência de 300 W. Os álcoois homopropargílicos correspondentes foram obtidos em bons rendimentos (51-98%) após 20 minutos. Através dos quatros métodos os produtos foram obtidos em rendimentos elevados de maneira regio- e quimiosseletivo. Foram obtidos vinte sete álcoois homopropargílicos e todos os compostos foram caracterizados por RMN de 1H e 13C. / In this work, four different methods for the synthesis of homopropargylic alcohols from aldehydes and boron compounds were developed. The first method was based on the use of the Amberlyst A-31 resin as the promoter. Best yields (70- 95%) were observed when an amount of 200% m/m of Amberlyst A-31 was used in CH2Cl2 under open atmosphere after 1,5 to 7,0 hours. The resin could be recovered and reused for three times in other reactions without looses in the yield. The second method was based on the use of tonsil clay as promoter. In this case, the desired compounds were obtained in good yields (60-96%) when an amount of 150% m/m of tonsil in CH2Cl2 under open atmosphere at room temperature was used. When the two methods using heterogeneous promoters were compared using aldehydes containing protecting groups sensitives to acidic medium, the best result was observed when tonsil was used, where the desired product was obtained in good yield together with a small amount of deprotected product. The third method was based on the use of BF3•Et2O as promoter. Again, the products were obtained in good yields (75-91%) after 30 minutes. The best condition was observed when 4 equivalents of BF3•Et2O in THF under argon atmosphere at room temperature was used. Attempts for the asymmetric propargylation reaction using BF3Et2O and different chiral ligands gave the corresponding products in good yields without any enantiomeric excess. Finally, when microwave irradiation was used to promote the propargylation of aldehydes, the best condition was found when allenylboronic acid pinacol ester was used at 100ºC using a 300 W potency. The homopropargylic alcohols were obtained in good yields (51-98%) after 20 minutes. Using the four developed methods, the products were obtained in high yields in a regio- and chemoselective way. Twenty seven homopropargylic alcohols were synthesized and all compounds were characterized by 1H and 13C NMR.