Síntese de ácidos 3-alcóxi-3-cianopropanóicos, ácidos 2-ciano tetraidrofuran(2h-piran)-3-óicos e sua aplicação na obtenção dos respectivos ácidos succinâmicos e succínicos

• Ano de defesa: 2007
• Autor(a) principal: Silva, Fabio Machado da
• Orientador(a): Zanatta, Nilo
• Banca de defesa: Martins, Marcos Antonio Pinto , Flores, Alex Fabiani Claro
• Tipo de documento: Dissertação
• Tipo de acesso: Acesso aberto
• Idioma: por
• Instituição de defesa: Universidade Federal de Santa Maria
• Programa de Pós-Graduação: Programa de Pós-Graduação em Química
• Departamento: Química
• País: BR
• Palavras-chave em Português: β-Alcoxivinil triclorometil cetonas; Cianeto de sódio; Ácidos β-cianocarboxílicos; Ácidos 3-alcóxi-3-cianopropanóicos; Ácidos succinâmicos; Ácidos succínicos
• Palavras-chave em Inglês: β-Alkoxyvinyl trichloromethyl ketones; Sodium cyanide; β-cyanocarboxylic acids; Succinamic acids; Succinic acids; 3-alkoxy-3-cyanopropanoic acids
• Área do conhecimento CNPq: CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA
• Link de acesso: http://repositorio.ufsm.br/handle/1/10407

This work presents the synthesis of a series of 3-alkoxy-3-cyanopropanoic acids and 2-cyanotetrahydrofuran(2H-pyran)-3-carboxylic acids of general formula HO2CCH(R2)CR1(OR)CN, where R/R2= Et/H, Et/Me, -(CH2)2-, -(CH2)3-, iso-Pr/H, sec- Bu/H, iso-Pr/Me, sec-Bu/Me and R1= H, obtained through the reaction of β-alkoxyvinyl trichloromethyl ketones [Cl3CCOC(R2)=CR1(OR)] with sodium cyanide. The methodology used in the synthesis provided high selectivity to the reaction, being observed only the formation of the expected products, through a conjugated addition the cyanide to the β-carbon of the enones and substitution of the CCl3 group by the hydroxyl ion originated from the basic medium used in the reaction. The β-alkoxyvinyl trichloromethyl ketones where R/R2= Et/H, R1= OEt and R/R2= Et/Br, R1=H, when submitted the same reaction conditions, furnished the succinimide 3,3-diethoxypyrrolidine-2,5-dione and the maleimide 3-ethoxy-1H-pyrrole-2,5-dione, respectively. In a second reaction, the synthesized 3-alkoxy-3-cyanopropanoic acids and 2- cyanotetrahydrofuran(2H-pyran)-3-carboxylic acids were used to obtain succinamic acids and succinic acids of general formula HO2CCH(R2)CR1(OR)CONH2 and HO2CCH(R2)CR1(OR)CO2H, respectively. The succinamic acids were formed by the spontaneous conversion of the cyano group to amide (partial hydrolysis) and the succinic acids were obtained by the total hydrolysis of the cyano group to carboxylic acid, under reflux and acid medium.