Kinetic study of α-pinene allylic oxidation over FePcCl16-NH2-SiO2 catalyst

Thermodynamic Analysis of α‐Pinene and Limonene Allylic Oxidation over a FePcCl16‐NH2‐SiO2 Catalyst

“…Baker were used for catalyst synthesis. The hexadecachlorinated iron phthalocyanine complex FePcCl 16 was synthesized following the method reported by Metz [20] and immobilized over the amino-modified silica support NH 2 -SiO 2 according to the Sorokin procedure [21]; catalyst characterization was reported in previous works [18,19].…”

“…The reaction mixtures were analyzed by gas chromatography (under the heterogeneous conditions the catalyst was removed by filtration) in a GC Agilent 7890A equipped with FID, TCD, MS Agilent 5975C detectors and an HP5 column (ID 0.20 mm, length 50 m, film 0.5 μm), in n-decane as internal standard. TBHP was quantified by iodometric titration with Na 2 S 2 O 3 in an aqueous solution of KI + H 2 SO 4 [18,19].…”

“…1), under mild reaction conditions (313 K, 1 atm, acetone as solvent). The kinetic study of a-pinene oxidation under homogeneous and heterogeneous conditions considering the contribution of free radicals formed during the reaction, the catalytic TBHP decomposition, and the verbenol oxidation to verbenone over FePcCl 16 -NH 2 -SiO 2 were previously reported, in the absence of external and internal mass transfer limitations [18].…”

“…The evaluation of the catalytic activity of the metallophthalocyanine-based catalysts in the oxidation of a-pinene, limonene, and cyclohexene has been carried out with different oxidizing agents including TBHP, H 2 O 2 , and O 2 in previous works [18,19]; however, the use of TBHP favors the formation of the ketone (verbenone, carvone, and cyclohexanone) that is the main interest product from this research. When H 2 O 2 was employed as oxidant for a-pinene and limonene oxidation, diols or epoxides were the main products.…”

“…The main products from a-pinene oxidation are verbenone, a-pinene epoxide, and verbenol, whereas TBHP decomposition leads to the formation of oxygen, tert-butanol and di-tert-butyl peroxide [18]. The activity of FePcCl 16 -NH 2 -SiO 2 has been already evaluated in the limonene oxidation with TBHP, with carvone, limonene 1,2-epoxide, and carveol as the main terpene-derived products, as well as in the oxidation of carveol to carvone [19].…”