Study of Selectivity of Metal Phosphates and Phosphonates in Baeyer-Villiger Oxidations

• Published in: Catalysis letters Vol. 141; no. 1; pp. 100 - 110
• Main Authors: Rocha, Graça M. S. R. O, Santos, Teresa M, Bispo, Cláudia S. S
• Format: Journal Article
• Language: English
• Published: Boston Boston : Springer US 2011; Springer US; Springer
• Subjects: Acetic acid; Aluminum; Baeyer-Villiger oxidation; Catalysis; Chemical properties; Chemistry; Chemistry and Materials Science; Exact sciences and technology; General and physical chemistry; Hydrogen peroxide; Industrial Chemistry/Chemical Engineering; Metal phosphates and phosphonates; Organic acids; Organometallic Chemistry; Phosphates; Phosphonates; Physical Chemistry; Selectivity; Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry; Zirconium; Baeyer–Villiger oxidation; Metal phosphates and phosphonates; Selectivity; Phosphates; Baeyer-Villiger oxidation; Hydrogen peroxide; Transition metal; Aluminium; Zirconium phosphate; Baeyer Villiger reaction; Heterogeneous catalysis; Potassium phosphate; Zirconium; Sodium phosphate; Carboxylic acid; Oxidation; Acetic acid; Structure; Catalyst
• ISSN: 1011-372X; 1572-879X
• DOI: 10.1007/s10562-010-0481-2

Layered materials including metal phosphates and phosphonates have been widely investigated in several fields acting as good selective catalysts in a great number of oxidative reactions. Zirconium phosphate amorphous [Zr(HPO₄)₂·H₂O; ZrPA], sodium exchanged zirconium phosphate amorphous [Zr(NaPO₄)₂; NaZrPA], potassium exchanged zirconium phosphate amorphous [Zr(KPO₄)₂; KZrPA], zirconium phenylphosphonate amorphous [Zr(O₃PC₆H₅)₂; ZrPPA], zirconium carboxyethylphosphonate [Zr(O₃PCH₂CH₂COOH)₂; ZrCEP] and aluminium carboxyethylphosphonate [Al₃(OH)₃(O₃PCH₂CH₂CO₂)₂·3H₂O; AlCEP] were prepared, characterized and evaluated as selective catalysts in the Baeyer-Villiger oxidation of cyclopentanone, p-methoxybenzaldehyde and 2,4,6-trimethylbenzaldehyde by hydrogen peroxide, in acetic acid. The selectivity of δ-valerolactone, p-methoxyphenol and 2,4,6-trimethylphenol have been found to be strongly related with the properties and structure of each catalyst. Graphical Abstract The selectivity of zirconium phosphate amorphous [Zr(HPO₄)₂·H₂O; ZrPA], sodium exchanged zirconium phosphate amorphous [Zr(NaPO₄)₂; NaZrPA], potassium exchanged zirconium phosphate amorphous [Zr(KPO₄)₂; KZrPA], zirconium phenylphosphonate amorphous [Zr(O₃PC₆H₅)₂; ZrPPA], zirconium carboxyethylphosphonate [Zr(O₃PCH₂CH₂COOH)₂; ZrCEP] and aluminium carboxyethylphosphonate [Al₃(OH)₃(O₃PCH₂CH₂CO₂)₂·3H₂O; AlCEP] was evaluated in the Baeyer-Villiger oxidation of cyclopentanone, p-methoxybenzaldehyde and 2,4,6-trimethylbenzaldehyde by hydrogen peroxide, in acetic acid. Different selectivities have been found which were correlated with the properties and structure of each compound.