Redução eletroquímica de cinamatos de metila orto-substituídos / Electrochemical reduction of ortho-substituted methyl cinnamates

AUTOR(ES)

Camila dos Santos Gonçalves

DATA DE PUBLICAÇÃO

2004

RESUMO

The synthesis and electrochemical reduction in DMF of some ring substituted cinnamic esters are described. The main objective if this work is to verify the influence of the substituents on the electrohydrodimerization (EHD). The substrates studied were the methyl esters of o-methyl- (1), o-chloro- (2), o-nitro- (3), m,p-dichloro- (4), m-chloro- (5), p-chloro- (6), m-nitro- (7) and o-methoxycarbonyl- (8) cinnamic acids. Their electrochemistry was investigated employing cyclic voltammetry (determination of the reduction potentials) and preparative electrolysis at controlled potential. When substrate 1 was electrolyzed, a mixture of two stereoisomers of methyl 4,5-bis-(o-methylphenyl)-2-oxo-cyclopentane-carboxylate, not yet described in literature, was obtained, a result which differs from the usual EHD of cinnamates, which lead to only one stereoisomer with high diastereoselectivity. Methyl o-chlorocinnamate (2) electrolysed at –1,25 V vs Ag/AgI was dehalogenated and afforded methyl cinnamate. When the electrolysis was performed at –1,45 V, the main product was the cyclic expected hydrodimer of methyl cinnamate. In the case of substrates 4 and 6 a competition of dehalogenation and cimerization was observed whereas for 5 only the EHD occurred. A mechanism for the dehalogenation is suggested. Several electrolysis at different potentials, of the nitro-derivatives 3 and 7 yielded mixtures of starting material and the corresponding carboxylic acids. In this no EHD products were observed. The electrochemical reduction of methyl o methoxycarbonyl-cinnamate (8) did not lead to the expected EHD dimer, but new polycyclic compounds were isolated. Their formation is conventiently explained by Dieckmann cyclization which involve the methoxycarbonyl group of the aromatic ring.

ASSUNTO(S)

organic electrosynthesis eletrodimerização síntese eletroquímica cinamato de metila electrodimerization dimerização organic electrochemistry eletrossíntese orgânica methyl cinnamate electrochemical synthesis eletroquímica orgânica

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