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Please use this identifier to cite or link to this item: https://tede.ufrrj.br/jspui/handle/jspui/3530
???metadata.dc.type???: Tese
Title: Síntese de derivados das quinonas lapachol, α- e β-lapachona. Explorando o sistema quinônico
Other Titles: Synthesis of quinone derivatives of lapachol, α- and β-lapachone. Exploring the system quinone
???metadata.dc.creator???: Bernardes, Bauer de Oliveira 
???metadata.dc.contributor.advisor1???: Ferreira, Aurelio Baird Buarque
???metadata.dc.contributor.referee1???: Silva, Francisco de Assis da
???metadata.dc.contributor.referee2???: Mello, Heloísa de
???metadata.dc.contributor.referee3???: Ferreira, José Carlos Netto
???metadata.dc.contributor.referee4???: Garden, Simon John
???metadata.dc.description.resumo???: Neste trabalho exploramos a síntese de dioxolanos, dioxinas, ésteres, éteres e fenazinas a partir das quinonas lapachol, -lapachona, 2-metóxi-lapachol e, principalmente, - lapachona. Verificamos que a -lapachona pode formar dioxolano a partir de diazompostos ou nitroalcanos. Estudamos reações fotoquímicas entre o-quinonas e diferentes sistemas olefínicos, onde observamos cicloadições do tipo [4+2], formação de um aldeído inédito na reação com 2,3-di-hidro-1,4-dioxina, e a característica da - lapachona em transferir energia através da dimerização do acenaftileno. Além disso, fotólise por pulso de laser das quinonas -, -, nor-- e 3-sulfo--lapachona foi usada para caracterizar e estudar a reatividade e propriedades do estado excitado triplete destas quinonas. Reações de redução seguidas de acetilação ou alquilação foram realizadas com lapachol, -, -lapachona e 2-metóxi-lapachol, e o uso de piridina nesta última quinona forneceu principalmente a -xiloidona. A -lapachona submetida ao NaBH4 ou LiAlH4 seguido de brometo de benzila forneceu um álcool terciário, só obtido anteriormente por nosso grupo, através de reação de Grignard. Novas fenazinas e quinoxalinas foram formadas por reações com diaminas vicinais. Aplicamos metodologias distintas na tentativa de nitração dos ésteres, éteres, dioxina ou dioxolano formados a partir das quinonas, mas em quase todos os casos houve retorno a forma quinônica; Nas condições de Laszlo uma dioxina formou um acetal inédito. Os compostos obtidos foram analisados por espectrometria de massa, espectroscopia de ressonância magnética nuclear de carbono-13 e hidrogênio-1, infravermelho e/ou difração de raio-X.
Abstract: In this work we investigated the reactivity of the quinones lapachol, -lapachone, 2- methoxy-lapachol and mainly -lapachone. It was found that diazocompounds react with -lapachone with formation of dioxolanes, but with diazomethane an oxirane and an aldehyde were also formed, depending on the reaction conditions. Dioxolanes were also made from nitroalkanes by reaction with -lapachone, but nitromethane was unreactive. We have made theoretical calculations to compare the reactivity of different nitroalkanes and Grignard compounds with this quinone. Reactions with vicinal diamines led to different phenazines and quinoxalines, some unpublished. Photochemical reactions with different systems olefinic were observed in type cycloaddition [4 +2], notably the reaction with 5,6-diphenyl-2,3-dihydro-1,4-dioxin product which provided a yield of 96% and we not isolate products by cycloaddition [2 +2]. We observed the characteristic of -lapachone in transferring energy through the dimerization of acenaphthylene and also isolated a novel aldehyde in the reaction with 2,3-dihydro-1 ,4-dioxin. Laser flash photolysis of quinones -, -, nor-- and 3-sulfo-- lapachone was used to characterize and study the properties and reactivity of the triplet excited state of these quinones. Different vicinal diamines reacted with -lapachone to form new quinoxalines and phenazines. Reduction reactions followed by acetylation or alkylation were performed with lapachol, -, -lapachone and 2-methoxy-lapachol, and the use of pyridine latter quinone provided mainly -xiloidona. The -lapachone subjected to LiAlH4 or NaBH4 followed by benzoyl bromide gave a tertiary alcohol, previously only obtained via Grignard reaction by our group. Distinct methodologies were used in attempting the nitration products obtained, such as esters, ethers or dioxin or dioxolane ring, but in almost all cases there was a return to quinone form. Under the conditions of Laszlo dioxin DXBL formed a novel acetal. The compounds obtained were analyzed by mass spectrometry, nuclear magnetic resonance spectroscopy of carbon-13 and hydrogen-1, infrared and / or X-ray diffraction.
Keywords: B-lapachona
naftoquinonas
cicloadições
B-lapachone
naphthoquinones
cycloaddition
???metadata.dc.subject.cnpq???: Química
Language: por
???metadata.dc.publisher.country???: Brasil
Publisher: Universidade Federal Rural do Rio de Janeiro
???metadata.dc.publisher.initials???: UFRRJ
???metadata.dc.publisher.department???: Instituto de Ciências Exatas
???metadata.dc.publisher.program???: Programa de Pós-Graduação em Química
Citation: BERNARDES, Bauer de Oliveira. Síntese de derivados das quinonas lapachol, α- e β-lapachona. Explorando o sistema quinônico. 2012. 348 f. Tese (Doutorado em Química) - Instituto de Ciências Exatas, Universidade Federal Rural do Rio de Janeiro, Seropédica - RJ, 2012.
???metadata.dc.rights???: Acesso Aberto
URI: https://tede.ufrrj.br/jspui/handle/jspui/3530
Issue Date: 21-Nov-2012
Appears in Collections:DOUTORADO EM QUÍMICA

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