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  • 1 Laboratorio de Fisicoquímica de Superficies, DETEMA, Fac. de Química, Universidad de la República, Gral. Flores 2124, Montevideo, Uruguay
  • | 2 Laboratorio de Productos Naturales, Departamento de Química Orgánica, Fac. de Química, Universidad de la República, Gral. Flores 2124, Montevideo, Uruguay
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Abstract

Liquid-phase oxidation of limonene was performed with molecular oxygen as the sole oxidizing agent under non-solvent conditions. The oxidation took place under atmospheric pressure and temperatures between 70 and 90 °C in the presence of three different nickel–aluminium hydrotalcites. The final limonene conversion at 80 °C and 6 h of reaction time was comprised between 40 and 50 %. Several oxygenated limonene derivatives such as endo- and exo-epoxides, carveol and carvone represent 45–60 % of the whole amount of products. In the absence of a catalyst, a higher initial content of peroxides in limonene lead to a higher reaction rate with no significant changes in product selectivities. Thermal decomposition of limonene peroxides took place as the initiation path of an autooxidation mechanism leading to the different products. The catalyst played an important role in the initial paths involving activation of both reactants as well as in the decomposition of limonene peroxide to form radicals.

  • 1. Hobbs, CC 1995 Hydrocarbon oxidation J Kroschwitz eds. Kirk-Othmer encyclopedia of chemical technology, vol 13. 4 Wiley New York.

  • 2. Brégeault JM (2003) Dalton Trans 32893302.

  • 3. Oyama ST (ed) (2008) In: Mechanisms in homogeneous and heterogeneous epoxydation catalysis, Elsevier, Amsterdam.

  • 4. Sheldon RA , Kochi JK (1976) Metal catalyzed oxidation of organic compound: a mechanistic approaches, in advances in catalysis, vol 25, Academic Press, New York.

    • Search Google Scholar
    • Export Citation
  • 5. Monteiro, JLF, Veloso, CO 2004 Top Catal 27 1–4 169180 .

  • 6. Santa, AM, Vergara, JC, Palacio, LA, Echavarría, A 2008 Catal Today 133–135:8086 .

  • 7. Cagnoli, MV, Casuscelli, SG, Alvarez, AM, Bengoa, JF, Gallegos, NG, Samaniego, NM, Crivello, ME, Ghione, GE, Pérez, CF, Herrero, ER, Marchetti, SG 2005 Appl Catal A Gen 287:227235 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 8. Villa, AL, Taborda, F, Montes de Correa, C 2002 J Mol Catal A Chem 185:269277 .

  • 9. Kala Raj, NK, Puranik, VG, Gopinathan, C, Ramaswamy, AV 2003 Appl Catal A Gen 256:265273 .

  • 10. Goncalves, JA, Bueno, AC, Gusevskaya, EV 2006 J Mol Catal A Chem 252:511 .

  • 11. Lima, LF, Corraza, ML, Cardozo-Filho, L, Márquez-Alvarez, H, Antunes, OAC 2006 Braz J Chem Eng 23:8392 .

  • 12. Oliveira, P, Rojas-Cervantes, ML, Ramos, AM, Fonseca, IM, Botelho do Rego, AM, Vital, J 2006 Catal Today 118:307314 .

  • 13. Martin-Luengo, MA, Yates, M, Diaz, M, Saez Rojo, E, Gonzalez Gil, L 2011 Appl Catal B Environ 106:488493 .

  • 14. Saikia, L, Srinivas, D, Ratnasamy, P 2006 Appl Catal A Gen 309:144154 .

  • 15. Szczepanik, A, Sobkowiak, A 2008 Catal Lett 126:261267 .

  • 16. Robles-Dutenhefner, PA MJ da Silva Sales, LS, Sousa, EMB, Gusevskaya, EV 2004 J Mol Catal A Chem 217:139144 .

  • 17. Bussi, J, López, A, Peña, F, Timbal, P, Paz, D, Lorenzo, D, Dellacassa, E 2003 Appl Catal A Gen 253:177189 .

  • 18. Naróg, D, Szczepanik, A, Sobkowiak, A 2008 Catal Lett 120:320325 .

  • 19. Gómez-Hortiguela, L, Corà, F, Catlow, CRA 2011 ACS Catal 1:1828 .

  • 20. Porter NA (1992) In: Ando W (ed) Organic peroxides. Wiley, Chichester.

  • 21. Ziegler, M, Brandauer, H, Ziegler, E, Ziegler, G 1991 J Essent Oil Res 3:209220 .

  • 22. Ancel, JE, Maksimchuk, NV, Simakova, IL, Semikolenov, VA 2004 Appl Catal A Gen 272:109114 .

  • 23. Lajunen, MK, Maunula, T, Koskinen, AMP 2000 Tetrahedron 56:81678171 .

  • 24. Jana, SK, Wu, P, Tatsumi, T 2006 J Catal 240:268274 .

  • 25. Zăvoianu, R, Cruceanu, A, Pavel, OD, Angelescu, E, Soares Dias, AP, Bîrjega, R 2012 Reac Kinet Mech Cat 105:145162 .

  • 26. Choudary, BM, Bhuma, V, Narender, N 1997 Indian J Chem 36B:278280.

  • 27. Frizzo, CD, Lorenzo, D, Dellacassa, E 2004 J Agric Food Chem 52:30363041 .

  • 28. Lajunen, MK, Koskinen, AMP 1994 Tetrahedron Lett 35:44614464 .

  • 29. Chakrabarty, R, Das, BK 2004 J Mol Catal A Chem 223:3944 .

  • 30. Lajunen, MK 2001 J Mol Catal A Chem 169:3340 .

  • 31. Hermans, I, Peeters, J, Jacobs, PA 2008 Top Catal 50:124132 .

  • 32. Kehrer, JP 2000 Toxicology 149:4350 .

  • 33. KA da Silva Rocha Hoehne, JL, Gusevskaya, EV 2008 Chem Eur J 14:61666172 .