28738-15-0Relevant academic research and scientific papers
THERMODYNAMIC DISSECTION OF SOLVENT EFFECTS IN THE SCHIFF REACTION
Arcoria, Antonino,Cipria, Antonio,Longo, Maria Luisa,Maccarone, Emanuele,Tomaselli, Gaetano Andrea
, p. 723 - 730 (2007/10/02)
Rate constants for the reactions of p-substituted benzaldehydes with aniline and some 2-alkyl- and 2,6-dialkylanilines to give imines have been measured in acetonitrile and N,N-dimethylformamide at 25 and 75 deg C.The contributions of solvation energies to the free energy of activation have been measured at 25 deg C in cyclohexane, carbon tetrachloride, methanol, N,N-dimethylformamide, acetonitrile, ethylene glycol, dimethyl sulphoxide and N-methylformamide for the reaction of benzaldehyde and aniline.The observed reactivity depends on both polar and steric effects of the alkyl groups.Thermodynamic dissection of solvent effects points out that acidic or basic properties of solvents are important features in determining the rate of the process.However, the changeover of the rate-limiting step from the formation of the intermediate α-amino alcohol (with electron-donating groups) to its dehydration (with electron-withdrawing substituents) seems scarcely affected by solvent variations. 1H NMR measurements in dimethyl sulphoxide allowed the detection of the intermediate α-amino alcohol.
