Synthesis of quinone derivatives of lapachol, ?- and ?-lapachone. Exploring the system quinone

Autor: Bernardes, Bauer de Oliveira
Přispěvatelé: Ferreira, Aur?lio Baird Buarque, Silva, Francisco de Assis da, Mello, Helo?sa de, Ferreira, Jos? Carlos Netto, Garden, Simon John
Jazyk: portugalština
Rok vydání: 2012
Předmět:
Zdroj: Biblioteca Digital de Teses e Dissertações da UFRRJ
Universidade Federal Rural do Rio de Janeiro (UFRRJ)
instacron:UFRRJ
Popis: Submitted by Sandra Pereira (srpereira@ufrrj.br) on 2020-05-18T14:30:42Z No. of bitstreams: 1 2012 - Bauer de Oliveira Bernardes.pdf: 26455317 bytes, checksum: 00a0134e16b9ac8c75310f952830c6af (MD5) Made available in DSpace on 2020-05-18T14:30:42Z (GMT). No. of bitstreams: 1 2012 - Bauer de Oliveira Bernardes.pdf: 26455317 bytes, checksum: 00a0134e16b9ac8c75310f952830c6af (MD5) Previous issue date: 2012-11-21 Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico, CNPq, Brasil. 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 Reactions with vicinal diamines led to different phenazines and quinoxalines, some unpublished.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. Neste trabalho exploramos a s?ntese de dioxolanos, dioxinas, ?steres, ?teres e fenazinas a partir das quinonas lapachol, ?-lapachona, 2-met?xi-lapachol e, principalmente, ?-lapachona. Verificamos que a ?-lapachona pode formar dioxolano a partir de diazompostos ou nitroalcanos. Estudamos rea??es fotoqu?micas entre o-quinonas e diferentes sistemas olef?nicos, onde observamos cicloadi??es do tipo [4+2], forma??o de um alde?do in?dito na rea??o com 2,3-di-hidro-1,4-dioxina, e a caracter?stica da ?-lapachona em transferir energia atrav?s da dimeriza??o do acenaftileno. Al?m disso, fot?lise 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. Rea??es de redu??o seguidas de acetila??o ou alquila??o foram realizadas com lapachol, ?-, ?-lapachona e 2-met?xi-lapachol, e o uso de piridina nesta ?ltima quinona forneceu principalmente a ?-xiloidona. A ?-lapachona submetida ao NaBH4 ou LiAlH4 seguido de brometo de benzila forneceu um ?lcool terci?rio, s? obtido anteriormente por nosso grupo, atrav?s de rea??o de Grignard. Novas fenazinas e quinoxalinas foram formadas por rea??es com diaminas vicinais. Aplicamos metodologias distintas na tentativa de nitra??o dos ?steres, ?teres, dioxina ou dioxolano formados a partir das quinonas, mas em quase todos os casos houve retorno a forma quin?nica; Nas condi??es de Laszlo uma dioxina formou um acetal in?dito. Os compostos obtidos foram analisados por espectrometria de massa, espectroscopia de resson?ncia magn?tica nuclear de carbono-13 e hidrog?nio-1, infravermelho e/ou difra??o de raio-X.
Databáze: OpenAIRE
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