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Master's Dissertation
DOI
10.11606/D.46.2006.tde-04092006-193506
Document
Author
Full name
Ricardo Curilazo
E-mail
Institute/School/College
Knowledge Area
Date of Defense
Published
São Paulo, 2006
Supervisor
Committee
Viertler, Hans (President)
Baader, Josef Wilhelm
Romero, Jose Ricardo
Title in Portuguese
Redução eletroquímica de 3,3' - (1,X - fenileno) - bis - (2 - propenoatos de etila)
Keywords in Portuguese
esteres alfa beta insaturados
hidrodímero cíclico
redução eletroquímica
Abstract in Portuguese
A redução eletroquímica de 3,3'-(1,3- e 1,4-fenileno)-bis-(2-propenoatos de etila), sistemas diolefínicos cujas duplas ligações estão separadas por um anel benzênico, foi investigada em N,N-dimetilformamida (DMF) e acetonitrila (MeCN) e metanol/acetonitrila (MeOH/MeCN) (7:3) (v/v). As eletrólises a potencial controlado em DMF e MeCN conduziram a hidrodímeros cíclicos derivados da ciclopentanona com elevada estereosseletividade, análogos aos produtos formados a partir de ésteres do ácido cinâmico nas mesmas condições experimentais. Ao lado dos hidrodímeros, quantidades variáveis de produtos de polimerização e de hidrogenação das duplas ligações dos grupos etoxicarbonilvinila eram formados. Foram examinados a influência do pH, concentração inicial dos substratos e presença de doadores de prótons (MeOH/MeCN) sobre o curso da redução eletroquímica. A maior complexidade dos produtos de eletrólise no substrato 1,4-substituído quando comparada as produtos do 1,3-substituído pode ser explicada, em parte, pela maior interação eletrônica dos grupos etoxicarbonilvinila através do anel aromático no primeiro.
Title in English
Electrochemical Reduction of Ethyl 3,3' - (1,X - phenylene) - bis - (2- propenoates)
Keywords in English
alpha beta-unsaturated esters
cyclic hydrodimer
electrochemical reduction
Abstract in English
The electrochemical reduction of ethyl 3,3' -(1,3 and 1,4-phenylene)-bis-(2-propenoates), diolefinic systems whose double bonds are separated by a benzene ring, was investigated in N,N-dimethylformamide (DMF), acetonitrile (MeCN) and methanol/acetonitrile (MeOH/MeCN) (7:3) (v/v). Controlled potential electrolyses in DMF and MeCN afforded cyclic hydrodimers derivatives of cyclopentanone with high stereoselectivity as are the products formed from cinnamic acid esters under similar experimental conditions. Besides the hydrodimers variable amounts of polymerization and side chain carbon-carbon double bond hydrogenation products were formed. The influence of pH, initial concentration of substrates and the presence of proton donors (MeOH/MeCN) upon the electrochemical reduction was examined. The formation of more complex reaction mixtures in the case of the 1,4-substituted substrate when compared with the 1,3-substituted may be explained, at the least partially, due to a larger electronic interaction between the ethoxycarbonylvinyl groups through the aromatic ring in former.
 
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Publishing Date
2006-11-24
 
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