Metal nitrate-catalyzed one-pot oxidative esterification of benzaldehyde with hydrogen peroxide in alcoholic solutions at room temperature

• Published in: New journal of chemistry Vol. 45; no. 7; pp. 3683 - 3691
• Main Authors: da Silva, Márcio José, de Oliveira, Cesar Macedo
• Format: Journal Article
• Language: English
• Published: Cambridge Royal Society of Chemistry 22.02.2021
• Subjects: Additives; Benzaldehyde; Benzoates; Benzoic acid; Catalysts; Catalytic activity; Esterification; Ethanol; Hydrogen peroxide; Iron; Metal nitrates; Methanol; Molecular chains; Nitrates; Oxidizing agents; Room temperature; Selectivity; Steric hindrance; Stoichiometry; Transition metals
• ISSN: 1144-0546; 1369-9261
• DOI: 10.1039/d0nj05671e

The activity of metal nitrate catalysts was investigated in the oxidative esterification reactions of benzaldehyde with hydrogen peroxide. Several types of metal nitrates (alkaline, alkaline earth, and transition metals) were evaluated as catalysts. Among the assessed salts, Fe(NO 3 ) 3 was the most efficient catalyst toward the formation of the target product ( i.e. , benzoic alkyl ester). In methyl alcohol, benzaldehyde was selectively oxidized to benzoic acid and then esterified to methyl benzoate. The efficiency of the catalyst was correlated with its higher Lewis acidity character, which was established through the pH measurements of methanolic solutions of the soluble metal nitrate salts. The influence of main variables of the reaction, such as catalyst load, temperature, and reactant stoichiometry, was investigated. The size of the carbon chain and steric hindrance played an essential role in the reaction selectivity. While methyl and ethyl alcohols selectively provided ester as the main product ( ca. 70-75%) and acetal as the subproduct, the other alcohols gave ester, hemiacetal, and benzoic acid, which was formed in the least amount. The use of an inexpensive catalyst, a green oxidant, mild conditions, and short reaction times were the positive aspects of this one-pot process. The high TON ( ca. 900) is evidence of the high catalytic activity of Fe(NO 3 ) 3 . It is noteworthy that this methodology does not rely upon ligands and other additives. The ferric nitrate was the most active and selective metal nitrate catalyst in the one-pot synthesis of alkyl esters from benzaldehyde with hydrogen peroxide at room temperature.