IJOC  Vol.3 No.3 , September 2013
Green Synthesis of Carvenone by Montmorillonite-Catalyzed Isomerization of 1,2-Limonene Oxide
Montmorillonite was considered as a good heterogeneous catalyst for the isomerization of 1,2-limonene oxide into car-venone under solvent-free condition. Both conventional heating and green activations were tested in this research. The microwave-assisted isomerization afforded carvenone in high yield within only 6 minutes.

Cite this paper
T. Nguyen, D. Chau, F. Duus and T. Le, "Green Synthesis of Carvenone by Montmorillonite-Catalyzed Isomerization of 1,2-Limonene Oxide," International Journal of Organic Chemistry, Vol. 3 No. 3, 2013, pp. 206-209. doi: 10.4236/ijoc.2013.33027.
[1]   J. Verghese, “Carvenone,” Indian Perfumer, Vol. 24, No. 1, 1980, pp. 1-8.

[2]   F. Yoshito, N. Masato and I. Kazunari, “Production of Carvenone,” Japanese Patent No. 62-114926, 1987.

[3]   G. Büchi and R. E. Erickson, “Terpenes. II. The Reactions of Carvone and Dihydrocarvone with Methanol in the Presence of Sulfuric Acid,” Journal of the American Chemical Society, Vol. 76, No. 13, 1954, pp. 3493-3495. doi:10.1021/ja01642a039

[4]   E. E. Royals and L. L. Harrell, “Oxygenated Derivatives of d-α-Pinene and d-Limonene. Preparation and Use of Monoperphthalic Acid,” Journal of the American Chemical Society, Vol. 77, No. 12, 1955, pp. 3405-3408. doi:10.1021/ja01617a085

[5]   D. Mandelli, M. C. A. Van Vliet, R. A. Sheldon and U. Schuchardt, “Alumina-Catalyzed Alkene Epoxidation with Hydrogen Peroxide,” Applied Catalysis A: General, Vol. 219, No. 1-2, 2001, pp. 209-213. doi:10.1016/S0926-860X(01)00693-7

[6]   H. Kropf and M. R. Yazdanbakhch, “Oxirane Durch Cooxidation Von Alkenen und Aldehyden Mit Sauerstoff,” Synthesis, Vol. 10, 1977, pp. 711-713. doi:10.1055/s-1977-24546

[7]   M. C. A. Van Vliet, D. Mandelli, I. W. C. E. Arends, U. Schuchardt and R. A. Sheldon, “Alumina: A Cheap, Active and Selective Catalyst for Epoxidations with (Aqueous) Hydrogen Peroxide,” Green Chemistry, Vol. 3, No. 5, 2001, pp. 243-246. doi:10.1039/B103952K

[8]   R. Buffon and U. Schuchardt, “Heterogenization of Alkene Epoxidation Catalysts,” Journal of the Brazilian Chemistry Society, Vol. 14, No. 3, 2003, pp. 347-353. doi:10.1590/S0103-50532003000300002

[9]   R. Saladino, A. Andreoni, V. Neri and C. Crestini, “A Novel and Efficient Catalytic Epoxidation of Olefins and Monoterpenes with Microencapsulated Lewis Base Adducts of Methyltrioxorhenium,” Tetrahedron, Vol. 61, No. 5, 2005, pp. 1069-1075. doi:10.1016/j.tet.2004.11.065

[10]   H. Ziyat, M. Y. A. Itto, M. A. Ali, A. Riahi, A. Karim and J.-C. Daran, “Convenient Synthesis of New Functionalized Cyclopropanes from Monoterpenic Olefins,” Arkivoc, Vol. 12, No. 12, 2006, pp. 152-160. doi:10.3998/ark.5550190.0007.c18

[11]   P. Buranaprasertsuk, Y. Tangsakol and W. Chavasiri, “Epoxidation of Alkenes Catalyzed by Cobalt (II) Calix[4]pyrrole,” Catalysis Communications, Vol. 8, No. 3, 2007, pp. 310-314. doi:10.1016/j.catcom.2006.06.022

[12]   N. Fdil, M. Y. A. Itto, M. A. Ali, A. Karim and J.-C. Daran, “Epoxydation Aerobique des Terpens Naturels: Etude de l’Activité Catalytique des Nouveaux Comlexes Ru-1,2,4-triazepines,” Tetrahedron Letters, Vol. 43, No. 48, 2002, pp. 8769-8771. doi:10.1016/S0040-4039(02)02072-5

[13]   M. Aitali, M. Y. A. Itto, A. Hasnaoui, A. Riahi, A. Karim and J.-C. Daran, “A New Class of Triazepine—Ruthenium(II) Complexes: Synthesis, Crystal Structure and NMR Spectroscopic Properties,” Journal of Organometallic Chemistry, Vol. 619, No. 1-2, 2001, pp. 265-270. doi:10.1016/S0022-328X(00)00680-X

[14]   K. A. D. Swift, “Catalytic Transformations of the Major Terpene Feedstocks,” Topics in Catalysis, Vol. 27, No. 1-4, 2004, pp. 143-155. doi:10.1023/B:TOCA.0000013549.60930.da

[15]   I. C. Nigam and L. Levi, “Essential Oils and Their Constituents. XLII. Isomerization of Epoxides on Active Alumina,” Canadian Journal of Chemistry, Vol. 46, No. 21, 1968, pp. 1944-1947. doi:10.1139/v68-565

[16]   K. Arata, S. Akutagawa and K. Tanabe, “Isomerization of d-Limonene Oxide over Solid Acids and Bases,” Journal of Catalysis, Vol. 41, No. 1, 1976, pp. 173-179. doi:10.1016/0021-9517(76)90213-X

[17]   K. Arata and K. Tanabe, “Isomerization of d-Limonene Oxide over Aluminas,” Chemistry Letters, Vol. 5, No. 4, 1976, pp. 321-322. doi:10.1246/cl.1976.321

[18]   K. Arata, H. Takahashi and K. Tanabe, “Isomerization of d-Limonene Oxide Catalyzed by NiSO4, FeSO4 and TiO2-ZrO2,” Roczniki Chemii (Polish Journal of Chemistry), Vol. 50, No. 12, 1976, pp. 2101-2106.

[19]   T. Kurata, H. Takao, N. Kawashima and M. Hiroshi, “Isomerization of d-Limonene-1,2-Epoxide with Activated Carbon Catalyst,” Yukagaku, Vol. 34, No. 12, 1985, pp. 1032-1304.

[20]   B. M. Choudary and Y. Sudha, “Fe3+-Montmorillonite: An Efficient Heterogeneous Catalyst for Highly Regioselective Alcoholysis of Epoxides,” Synthetic Communications, Vol. 26, No. 16, 1996, pp. 2989-2992. doi:10.1080/00397919608004602

[21]   N. Ravasio, F. Zaccheria, M. Guidotti and R. Psaro, “Mono and Bifunctional Heterogeneous Catalytic Transformation of Terpens and Terpenoids,” Topics in Catalysis, Vol. 27, No. 1-4, 2004, pp. 157-168. doi:10.1023/B:TOCA.0000013550.28170.6a

[22]   J. M. S. Silva, F. S. Vinhado, D. Mandelli, U. Schuchardt and R. Rinaldi, “The Chemical Reactivity of Some Terpenes Investigated by Alumina Catalyzed Epoxidation with Hydrogen Peroxide and by DFT Calculations,” Journal of Molecular Catalysis A: Chemical, Vol. 252, No. 1-2, 2006, pp. 186-193. doi:10.1016/j.molcata.2006.02.042

[23]   T. W. Del Pesco, “Modified Montmorillonite Clay Catalyst,” US Patent, No. 4235751, 1980.