38615-92-8Relevant academic research and scientific papers
CINETIQUE ET MECANISME DE LA REACTION DE KNOEVENAGEL DANS LE BENZENE-2 REACTION DU MALONITRILE ET DE LA (+) METHYL-3 CYCLOHEXANONE EN PRESENCE D'UNE AMINE PRIMARIE PURE ET DE SON MELANGE AVEC L'ACIDE ACETIQUE
Guyot, J.,Kergomard, A.
, p. 1167 - 1179 (2007/10/02)
The kinetics of the reaction of (+)-3-methyl cyclohexanone with malonitrile were studied in benzene at 25 deg C, in the presence of hexylamine-acetic acid mixtures.Hexylamine gives an imine with cyclohexanone in an acid-catalyzed step.This imine then reacts quickly with malononitrile.A rate law of zero order in malononitrile is observed.Separate kinetic results obtained for the formation of the imine and for the imine-malonitrile reaction support this mechanism.Without acetic acid, a complex rate law is observed; hexylamine acts mainly as a basic catalyst.Primary amine-carboxylic acid was used as a catalyst in Knoevenagel reaction, often giving an increase in yield and a diminution in the reaction time compared with the more commonly used catalysts: piperidine, β-alanine, AcOH-AcONH4.
CINETIQUE ET MECHANISME DE LA REACTION DE KNOVENAGEL DANS LE BENZENE-1 REACTION DU MALONITRILE ET DE LA (+) METHYL-3 CYCLOHEXANONE EN PRESENCE D'AMINES TERTIAIRE ET SECONDAIRE PURES OU EN MELANGE AVEC DES ACIDES CARBOXYLIQUES
Guyot, J.,Kergomard, A.
, p. 1161 - 1166 (2007/10/02)
The kinetics of the reaction of malonitrile with (+) 3-methyl-cyclohexanone were studied in benzene at 25 deg C in the presence of triethylamine or piperidine, either alone or together with acetic acid or benzoic acid.The rate law of the reaction was found to be: v=k (Amine)(Ketone)(Nitrile).It is interpreted in terms of a basic catalysis by the amine.When amine-acid mixtures were used, a general acid catalysis was observed but its effect on the overall rate of the reaction was slight, since the acid also lowered the concentration of free amine.
