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ReaÃÃes de reduÃÃo, hidrÃlise e resoluÃÃo de racematos, usando como biocatalisador cÃlulas Ãntegras de sementes de gergelim Sesamum indicum L / Reduction reactions, hydrolysis and resolution of racemates, using as whole cell biocatalys SESAME SEED (Sesamum indicum L.)

nÃo hà / O presente trabalho relata a utilizaÃÃo de sementes de gergelim secas e germinadas como fonte de enzimas em reaÃÃes de reduÃÃo, hidrÃlise e esterificaÃÃo. Uma sÃrie de reaÃÃes de reduÃÃo utilizando como biocatalisador sementes de gergelim quimiotipo negra (SGN) foram realizadas, tendo como substratos: acetofenona e derivados halogenados de acetofenona: 2-bromo-acetofenona, 3-bromo-acetofenona, 4-bromo-acetofenona, 2-cloro-acetofenona, 3-cloro-acetofenona, 4-cloro-acetofenona, 2-fluor-acetofenona, 3-fluor-acetofenona, 4-fluor-acetofenona, 2,4-dicloro-acetofenona, 2,4-dibromo-acetofenona e 2,2,2-trifluor-acetofenona. TambÃm foram submetidos à anÃlise derivados de acetofenona substituÃdas com grupos retiradores como, 2-metoxi-acetofenona, 3-metoxi-acetofenona e 4-metoxi-acetofenona e por nitro compostos. TambÃm foram empregadas acetofenonas substituÃdas por grupo amina nas posiÃÃes 2, 3 e 4 do anel aromÃtico. Para vÃrios dos compostos citados, os alcoÃis foram obtidos com bons e excelentes conversÃes (43â99%), a SGN foi enantio e quimiosseletiva, apresentando exelentes excessos enantiomÃricos (80-99%). A segunda parte do trabalho consistiu na utilizaÃÃo do sistema enzimÃtico do gergelim com sementes germinadas (SGG) em reaÃÃes de esterificaÃÃo e na hidrÃlise de Ãsteres. A 1,2-difenil-α-hidroxi-etanona, foi selecionada como substrato padrÃo, em mistura com o agente acilante acetato de vinila, observando como produto o composto identificado como α-acetato de 1,2-difenil-etanona, com um excelente ee ˃99% e conversÃo de 50%. Todos os produtos foram analisados atravÃs de CCD, CLAE, CG-EM e RMN1H e nas determinaÃÃes dos excessos enantiomÃricos utilizou-se CLAE em colunas quirais. / ABSTRACT

The present work reports the use of enzyme present in the sesame seeds in the in reduction, hydrolysis and esterification reactions. A series of reactions using as seeds black chemotype extract (SBS) were performed, using selected substrates such as acetophenone and halogenated acetophenones: 2-bromo-acetophenone, 3-bromo-acetophenone, 4-bromo-acetophenone, 2-chloro-acetophenone, 3-chloro-acetophenone, 4-chloro-acetophenone, 2-fluoro-acetophenone, 3-fluoro-acetophenone, 4-fluoro-acetophenone, 2,4-dichloro-acetophenone, 2,4-dibromo-acetophenone and 2,2,2-trifluoro-acetophenone. Experiments were also performed with substituted acetophenone such as 2-methoxy-acetophenone, 3-methoxy-acetophenone and 4-methoxy-acetophenone as well as acetophenones having amine group at C-2, C-3 and C-4 of the aromatic ring. Chiral alcohols were obtained vary from good to excellent yields, in some cases reactions proceeded with chemoselectivity, in others, with enantioselectivity. The second part of research involved the use of the enzyme system of sesame seeds in the esterification and esters hydrolysis. In these reactions were used germinated seeds (GSS) using methodology adapted from the literature. The compound 1,2-diphenyl-α-hydroxy-ethanone were selected as a standard substrate in acetylation reactions. The reactions using vinyl acetate as acylation agent and germinated seeds (GSS) yielded the product identified as α-ethyl- 1,2-diphenyl-ethanone. Optimized parameters were obtained including: amount of seed and substrate, reaction time, solvent, speed and temperature. All products were analyzed by TLC, HPLC, GC-MS and 1H NMR and enantiomeric excess were determined using chiral columns using HPLC.

Identiferoai:union.ndltd.org:IBICT/oai:www.teses.ufc.br:5866
Date24 September 2012
CreatorsLeila Lima Parente
ContributorsTelma Leda Gomes de Lemos, Ãngela Martha Campos Arriaga, Marcos Carlos de Mattos, Jorge Mauricio David, Luciana Lucas Machado
PublisherUniversidade Federal do CearÃ, Programa de PÃs-GraduaÃÃo em QuÃmica, UFC, BR
Source SetsIBICT Brazilian ETDs
LanguagePortuguese
Detected LanguageEnglish
Typeinfo:eu-repo/semantics/publishedVersion, info:eu-repo/semantics/doctoralThesis
Formatapplication/pdf
Sourcereponame:Biblioteca Digital de Teses e Dissertações da UFC, instname:Universidade Federal do Ceará, instacron:UFC
Rightsinfo:eu-repo/semantics/openAccess

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