CYCLIZATION AND HYDROGENATION OF (+)-CITRONELLAL TO MENTHOLS OVER ZnBr2 AND Ni CATALYSTS SUPPORTED ON γ-Al2O3

https://doi.org/10.22146/ijc.21461

Elvina Dhiaul Iftitah(1*), M. Muchalal(2), Wega Trisunaryanti(3), Ria Armunanto(4)

(1) Department of Chemistry, University of Brawijaya, Jl. Veteran, Malang
(2) Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Gadjah Mada, Jl. Sekip Utara, Jogjakarta
(3) Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Gadjah Mada, Jl. Sekip Utara, Jogjakarta
(4) Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Gadjah Mada, Jl. Sekip Utara, Jogjakarta
(*) Corresponding Author

Abstract


Two steps transformation of (+)-citronellal, cyclization and hydrogenation, on ZnBr2/γ-Al2O3 and Ni/γ-Al2O3 catalyst have been realized with the selectivity to cyclization products (isopulegols) was very high (yield up to ~92.58%) over ZnBr2/γ-Al2O3 under mild condition (90 °C and 1 atm nitrogen atmosphere) with high Brønsted acid concentration, while at the same time very low cyclization rates were achieved over Ni/γ-Al2O3 with low or no Brønsted acidity, respectively. The highest cyclization rates were observed over Ni/ZnBr2/γ-Al2O3 under mild condition (90 °C and 1 atm hydrogen atmosphere). The second step transformation towards cyclization products, hydrogenation to menthols, was performed with Ni/γ-Al2O3 under hydrogen atmosphere. Surprisingly the one-step transformation of (+)-citronellal into menthols was investigated over Ni/γ-Al2O3 with yield ~84% under hydrogen atmosphere (90 °C, 1 atm) by exploiting the presence of acidic and hydrogenation sites on the catalyst surface. On the Ni/γ-Al2O3 catalyst it was found that the cyclization of (+)-citronellal to isopulegols occurs on the surface of the support. In the presence of the noble metal, the isopulegols are further hydrogenated to the menthols.


Keywords


cyclization; hydrogenation; citronellal; isopulegol; menthol

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DOI: https://doi.org/10.22146/ijc.21461

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