Effect of Neighboring Groups on the Methylolation of Acid Amides

Abstract

Methylolation of acid amides containing various electron-releasing and electron-withdrawing substituents has been carried out with formaldehyde in the presence of sodium hydroxide at pH 10 and at 55°C. The methylolation relative rates and extents of these acid amides have been studied. The results indicate that a number of factors, such as inductive effect, hyperconjugation, stereochemistry, and solvation, govern the rate and extent of methylolation. It was observed that methylol derivatives of acid amides with electron-withdrawing substituents tend to polymerize during methylolation. Methylolation of acid amides containing electron-releasing substituents proceeds better in the presence of triethylamine as compared to sodium hydroxide.

Keywords

Synthesis acid amides. Methylolation halogen hydrolysis NaOH triethylamine methylolation rate methylotation extent. Nucleophilic substitution nucleophilicity proton abstraction. Electron-releasing substituent electron- attracting substituent inductive effect hyperconjugation steric effect solvation effect. Polymerization.

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