Edy Cahyono(1*), Muchalal Muchalal(2), Triyono Triyono(3), Harno Dwi Pranowo(4)

(1) Student of Doctorate Program Department of Chemistry, Universitas Gadjah Mada; Department of Chemistry, Universitas Negeri Semarang, Jln. Sekaran, Gunungpati, Semarang
(2) Department of Chemistry, Universitas Gadjah Mada, Jln. Sekip Utara, Yogyakarta
(3) Department of Chemistry, Universitas Gadjah Mada, Jln. Sekip Utara, Yogyakarta
(4) Department of Chemistry, Universitas Gadjah Mada, Jln. Sekip Utara, Yogyakarta
(*) Corresponding Author


Kinetic in cyclisation-acetylation of (R)-(+)-citronellal with acetic anhydride was investigated over Zn2+-Natural zeolite (Zn2+-Natzeo) as a catalyst. (R)-(+)-citronellal has been isolated from citronella oil by fractional distillation under reducing pressure. Enantioselective capillary GC on a Supelco β-DEX 225 column has been used for analysis the enantiomers ratio of citronellal. Catalyst Zn2+-Natzeo has prepared through acid activation of natural zeolite from Malang using HF 1% and HCl 6 M, followed by ion-exchange with 3 M NH4Cl and calcination at 450 °C for 1 h under nitrogen to obtained H-natural zeolite (H-Natzeo). H-Natzeo was modified to Zn2+-Natzeo by ion exchange with 0.1 M ZnCl2. Cyclisation-acetylation reaction was carried out by heating (R)-(+)-citronellal (CIT), acetic anhydride (AA), and 1 g catalyst in glass batch reactor with vigorous stirring at 80 °C. Molar ratio CIT/AA that used, i.e. 0.25; 0.5; 1.0; 1.2 and 1.5. As the reaction proceeded, 1 mL sample was taken off at 10; 20; 30; 60; 120; 180 min and extracted using n-hexane for every molar ratio. Structure analysis of product was conducted by GC-MS. Kinetic of the cyclisation-acetylation reaction was analyzed according to the Langmuir-Hinshelwood mechanism. Increasing molar ratio of CIT/AA will decrease the isopulegyl acetate (IPA) and neo-isopulegyl acetate (NIPA) formation. Rate constant of cyclisation-acetylation reaction catalyzed by Zn2+-Natzeo was 30.964-47.619 mmol(min. g cat)-1 at 80 °C, 30 min and the ratio  adsorption equilibrium constant KCIT/KAA was 7.09.


Cyclisation-acetylation; (R)-(+)-citronellal; Zn2+-natural zeolite; kinetic

Full Text:

Full Text PDF


[1] Andrade, C.K.Z., Vercillo, O.E., Rodrigues, O.E., and Silviera, D.P., 2004, J. Braz. Chem. Soc., 15, 6, 813–817.

[2] Chuah, G.K., Liu, S.H., Jaenicke, S, and Harrison, L.J., 2001, J. Catal., 200, 2, 352–359.

[3] Chuah, G.K., Nie, Y., and Jaenicke, S., 2006, Chem. Commun., 1, 790–792.

[4] Arvela, P.M, Narendra, K., Ville, N., Rainer, S., Tapio, S., and Yu, M.D., 2004, J. Catal., 225, 155–169.

[5] Yongshong, Z., Yuntong, N., Jaenicke, S., and Chuah, G.K., 2005, J. Catal., 229, 2, 404–413.

[6] Kikukawa, Y., Yamaguchi, S., Nakagawa, Y., and Uehara, K., 2008, J. Am. Chem. Soc., 130, 47, 15872–15878.

[7] Sheldon, R.A., and Bekkum, H.V., 2000, Fine Chemicals through Heterogeneous Catalysis, Wiley–VCH, Weinheim.

[8] Cahyono, E., Muchalal, Triyono, and Pranowo, H. D., 2009, Analysis of the Enantiomers Ratio of Citronellal Using Enantioselective Gas Chromatography, Proceedings of XIX International Chemistry Seminar 2009 (XIX ICS), Chemistry Department-Universitas Gadjah Mada, Yogyakarta, Indonesia.

[9] Cahyono, E., Muchalal, Triyono, and Pranowo, H. D., 2009, Cyclisation-acetylation of (R)-(+)-Citronellal by Modified Natural Zeolite Catalysts, Proceeding of International Seminar ICORAFSS II, UTM, Johor Bahru.

[10] Cahyono, E. and Kadarwati, S., 2007, The Selectivity of Lewis Acid in the Cyclisation-Acetylation of Citronellal, Proceedings of International Conferences on Chemical Sciences 2007 (ICCS’07), Chemistry Department-Universitas Gadjah Mada, Yogyakarta, Indonesia.

[11] Derouane, E.G., Andre, J.M., and Lucas, A.A., 1988, J. Catal., 110, 29-45.

[12] Derouane, E.G., Crehan, G., Dillon, C.J., Bethell, H., He, H., and Hamid, S. B., 2000, J. Catal., 194, 410–423.

[13] Derouane, E.G., 1998, in A Molecular View of Heterogeneous Catalysis”, E.G. Derouane, Ed., De Boeck Universit´e, Brusselles.

[14] Derouane, E.G., 1998, J. Mol. Cat. A, 134, 29.

[15] Derouane, E.G., Dillon, C., Bethell, D., and Hamid, S.B., 1999, J. Catal., 187, 209.

[16] Freese, U., Heinrich F., and Roessner, F., 1999, Catal. Today, 49, 237.

[17] Smith, K., Zenhua, Z., and Hodgson, P.K.G., 1998, J. Mol. Cat. A, 134, 121.


Article Metrics

Abstract views : 1482 | views : 1296

Copyright (c) 2010 Indonesian Journal of Chemistry

Creative Commons License
This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.


Indonesian Journal of Chemistry (ISSN 1411-9420 /e-ISSN 2460-1578) - Chemistry Department, Universitas Gadjah Mada, Indonesia.

Analytics View The Statistics of Indones. J. Chem.