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Doctoral Thesis
DOI
10.11606/T.46.2008.tde-10122009-092843
Document
Author
Full name
Luís Rogerio Ferreira Santos
E-mail
Institute/School/College
Knowledge Area
Date of Defense
Published
São Paulo, 2008
Supervisor
Committee
Viertler, Hans (President)
Brocksom, Ursula
Comninos, Francisco Carlos Mikula
Di Vitta, Claudio
Gruber, Jonas
Title in Portuguese
Reduções e oxidações eletroquímicas de cinamatos de metila ariltio e etiltio substituídos nas posições vinílicas
Keywords in Portuguese
Ariltio
Cinamato
Eletrólises
Etiltio substituídos
Abstract in Portuguese
Este trabalho apresenta o estudo do comportamento eletroquímico de cinamatos de metila sulfenilados: o 3-feniltio-3-fenil-propenoato de metila, 2-feniltio-3-fenil-propenoato de metila, 3-fenil-3-etiltio-propenoato de metila e 2-etiltio-3-fenil-proenoato de metila. Está incluído a síntese dos substratos, a voltametria e as eletrólises preparativas, abrangendo oxidações e reduções eletroquímicas. As sínteses de três dos quatro ésteres selecionados partiram de um mesmo intermediário, o 3-fenil-propinato de metila, através de reações de Michael e radicalares com etanotiol e tiofenol. O 2-etiltio-3-fenil-propenoato de metila foi obtido a partir do ácido 2-etiltio-acético. As reduções catódicas foram feitas usando-se cela dividida, acetonitrila ou DMF anidros como solventes, mercúrio como eletrodo de trabalho, atmosfera inerte e potencial fixo. Em alguns casos foi utilizado uma mistura de acetonitrila com metanol como solvente, e também cela de compartimento único. Houve uma distinção entre os produtos obtidos das eletrólises dos cinamatos α e β-sulfenilados. Para os primeiros, predominou a saída do grupo do enxofre, formando cinamato de metla, ácidos cinâmico, éster de partida hidrogenado, ciclopentanonas e adipatos de metila acíclicos. Os outros dois α-isômeros não mostraram a mesma facilidade de quebra da ligação carbono-enxofre, levando a produtos de hidrólise, ciclopentanonas e derivados de hexanoatos que mantiveram os grupos sulfenilados As oxidações anódicas foram feitas em celas de compartimento único e separados, usando platina como eletrodo de trabalho, atmosfera inerte e corrente controlada. A maior parte dos experimentos ocorreu em meio reacional prótico (acetonitrila/metanol), fornecendo ésteres di e trimetoxilados, α e β-ésteres e tioacetais (com etiltio e feniltio)
Title in English
Electrochemicals reductions and oxidations of methyl cinnamate esters phenylthio and ethylthio substituted in vinylics positions
Keywords in English
Arylthio substituteds
Cinnamates
Electrolysis
Ethylthio
Abstract in English
This work presents the studing of electrochemical behavior of sulfenyl cinnamates: the 3-phenyl-3-phenylthio-propenoic methyl ester, 2-phenyl-3-phenyl-propenoic methyl-ester, 3-phenyl-3-ethylthio-propenoic methyl ester, 2-ethylthio-3-phenyl-propenoic methyl ester. The overall plane includes the synthesis of substrates, the cyclic voltammetry and the preparative eletrolysis, enclosing the reductions and oxidations. The synthesis of the three among the four chosen esters came from the same compound, the 3-phenyl-propenoic methyl ester, by Michael and radicals reactions with ethanethyol and thiophenol. The 2-ethylthio-propenoic methyl ester was achieved from the 2-ethylthio-acetic acid. The cathodic reductions werw carried out in divided glass cells, dry acetonitrile or DMF as solvents, mercury as work electrode, inert atmosphere and controlled potential. In some cases, was used a mixture of acetonitrile and methanol and only one experiment was performed in undivided cell. The products formed in β and α-sulfenyl substrates were not equal, because to the first the main role was the cleavage of the sulfur-carbon bond, giving methyl cinnamate ester, cinnamic acid, starting materials hydrogenateds, cyclopentanone and adipates derivatives. The others two isomers not exhibit the loss of sulfur group, forming hydrolisis products, cyclopentanones and hexanoates derivatives what keeping the sulfenyl groups. The anodic oxidations was carried out in divided and undivided glass cells, with platine as work electrode, inert atmosphere and controlled current Most of the electrochemicals reactions were run in protic reactional middle (acetonitrile/methanol), to furhter di and trimethoxylateds esters, β-keto-esters and thioketals (both ethyl and phenylthio).
 
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Publishing Date
2010-01-28
 
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