Actividad catalítica de complejos p-R-cinamato de Ce(III), Nd(III) y Sm(III) en la oxidación de β-pineno y canfeno
Palabras clave:
cinamato, lantánidos, actividad catalítica, canfeno, β-pineno
Resumen
Se realizó la síntesis de nueve complejos lantánidos de cerio, neodimio y samario con ligandos trans-cinamato (L1), trans-p-clorocinamato (L2) y trans-p-metoxicinamato (L3). La caracterización se realizó mediante espectroscopia FT-IR, análisis térmicos (TGA y DSC) y análisis elemental. Los compuestos obtenidos se utilizaron como catalizadores para la oxidación de canfeno y β-pineno, usando peróxido de hidrógeno (30 %) y ácido peracético (12 %) como agentes oxidantes. En la oxidación de canfeno, el complejo [Nd(L2)3] presentó la conversión más alta (97.99 %) con una selectividad del 84.05 % hacia el ácido 3-canfenilocarboxílico, mientras que en la oxidación de β-pineno, el complejo [Ce(L3)3 . 2H2O] presentó la conversión más alta (82.62 %) con una selectividad hacia la nopinona del 70.52 %.
Referencias bibliográficas
Aragón-Muriel, A., Camprubi, M., Gonzalez, E., Salinas, A., Rodriguez, A., Gomez, S., y Polo- Cerón, D. (2014). Dual investigation of lanthanide complexes with cinnamate and phen- ylacetate ligands: study of the cytotoxic properties and the catalytic oxidation of styrene. Polyhedron, 80, 117-128.
Aragón-Muriel, A., y Polo-Cerón, D. (2013). Synthesis, characterization, thermal behavior, and antifungal activity of La(III) complexes with cinnamates and 4-methoxyphenylacetate. Journal of Rare Earths, 31(11), 1106-1113.
Aragón-Muriel, A., Upegui, Y., Muñoz, J., Robledo, S., y Polo-Cerón, D. (2016). Synthesis, characterization and biological evaluation of rare earth complexes against tropical diseases Leishmaniasis, malaria and trypanosomiasis. Avances en Química, 11(2), 53-61.
Belanger, J. (1998). Perillyl alcohol: applications in oncology. Alternative Medicine Review, 3(6), 448-457.
Blaz, E., y Pielichowski, J. (2006). Polymer-Supported Cobalt (II) Catalysts for the Oxidation of Alkenes. Molecules, 11(1), 115-120.
Caovilla, M., Caovilla, A., Pergher, S., Esmelindro, M., Fernandes, C., Dariva, C., Bernardo-Gus- mao, K., Oestreicher, E., y Antunes, O. (2008). Catalytic oxidation of limonene, α-pinene and β-pinene by the complex [Fem(BPMP)Cl( μ-O)FeinCl3] biomimetic to MMO enzyme. Catalysis Today, 133-135, 695-698.
Carvalho, M., Fernandes, N., Fertonani, F. y Ionashiro, M. (2003). A thermal behaviour study of solid-state cinnamates of the latter trivalent lanthanides and yttrium(III). Thermochimica Acta, 398(1), 93-99.
Casuscelli, S., Eimer, G., Canepa, A., Heredia, A., Poncio, C., Crivello, M., Perez, C., Aguilar, A., y Herrero, E. (2008). Ti-MCM-41 as catalyst for a-pinene oxidation. Study of the effect of Ti content and H2O2 addition on activity and selectivity. Catalysis Today, 133-135, 678-683
Cejka, J., Corma, A., y Zones, S. (Eds). (2010). Zeolites and Catalysis: Synthesis, Reactions and Applications. Alemania: John Wiley & Sons.
Corma, A., Renz, M., y Susarte, M. (2009). Transformation of biomass products into fine chemicals catalyzed by solid Lewis- and Bransted-acids. Topics in Catalysis, 52(9), 1182-1189.
da Silva, M., Vieira, L., Oliveira, A., y Ribeiro, M. (2013). Novel effect of palladium catalysts on chemoselective oxidation of β-pinene by hydrogen peroxide. Monatshefte für Chemie- Chemical Monthly, 144(3), 321-326.
de Oliveira, A., Lopes, M., da Silva, M. (2009). Palladium-Catalysed Oxidation of Bicycle Monoterpenes by Hydrogen Peroxide in Acetonitrile Solutions: A Metal Reoxidant-Free and Environmentally Benign Oxidative Process. Catalysis Letters, 130, 424-431.
Deacon, G., Huber, F., y Phillips R. (1980) Relationships between the carbon-oxygen stretching frequencies of carboxylato complexes and the type of carboxylate coordination. Coordination Chemistry Reviews, 33(3), 227-250.
Kalinowska, M., Lewandowski, W., Swislocka, R., y Regulska, E. (2010). The FT-IR, FT-Raman, 1H and 13C NMR study on molecular structure of sodium(I), calcium(II), lanthanum(III) and thorium(IV) cinnamates. Journal of Spectroscopy, 24(3-4), 277-281.
Mercandante, A., Ionashiro, M., de Oliveira, L., Ribeiro, C., y Moscardini, L. (1993). Preparation and thermal decomposition of solid state lanthanide(III) and yttrium(III) chelates of ethylenediaminetetraacetic acid. Thermochimica Acta, 216, 267-277.
Nalone, L., Cardoso, T., Guimarães, R., do Ó Pessoa, C., Odorico, M., Marques, B., Gomes, L., Andrade, A., y Pergentino, D. (2015). Evaluation of the cytotoxicity of structurally correlated p-menthane derivatives. Molecules, 20(7), 13264-13280.
Pakdel, H., Sarron, S., y Roy, C. (2001). α-Terpineol from hydration of crude sulfate turpentine oil. Journal of Agricultural and Food Chemistry, 49(9), 4337-4341.
Patel, A. (Ed.). (2013). Environmentally benign catalysts: for clean organic reactions. India: Springer Science & Business Media.
Silva, M., Robles-Dutenhefner, P., Menini, L., y Gusevskaya, E. (2003). Cobalt catalyzed autoxi- dation of monoterpenes in acetic acid and acetonitrile solutions. Journal of Molecular Catalysis A: Chemical, 201(1), 71-77.
Stolle, A. (2013). Synthesis of Nopinone from P-Pinene-A Journey Revisiting Methods for Oxidative Cleavage of C=C Bonds in Terpenoid Chemistry. European Journal of Organic Chemistry, 2013(12), 2265—2278.
Suh, Y., Kim, N., Ahn, W., y Rhee, H. K. (2003) One-pot synthesis of campholenic aldehyde from a-pinene over Ti-HMS catalyst II: effects of reaction conditions. Journal of Molecular Catalysis A: Chemical, 198(1), 309-316.
Aragón-Muriel, A., y Polo-Cerón, D. (2013). Synthesis, characterization, thermal behavior, and antifungal activity of La(III) complexes with cinnamates and 4-methoxyphenylacetate. Journal of Rare Earths, 31(11), 1106-1113.
Aragón-Muriel, A., Upegui, Y., Muñoz, J., Robledo, S., y Polo-Cerón, D. (2016). Synthesis, characterization and biological evaluation of rare earth complexes against tropical diseases Leishmaniasis, malaria and trypanosomiasis. Avances en Química, 11(2), 53-61.
Belanger, J. (1998). Perillyl alcohol: applications in oncology. Alternative Medicine Review, 3(6), 448-457.
Blaz, E., y Pielichowski, J. (2006). Polymer-Supported Cobalt (II) Catalysts for the Oxidation of Alkenes. Molecules, 11(1), 115-120.
Caovilla, M., Caovilla, A., Pergher, S., Esmelindro, M., Fernandes, C., Dariva, C., Bernardo-Gus- mao, K., Oestreicher, E., y Antunes, O. (2008). Catalytic oxidation of limonene, α-pinene and β-pinene by the complex [Fem(BPMP)Cl( μ-O)FeinCl3] biomimetic to MMO enzyme. Catalysis Today, 133-135, 695-698.
Carvalho, M., Fernandes, N., Fertonani, F. y Ionashiro, M. (2003). A thermal behaviour study of solid-state cinnamates of the latter trivalent lanthanides and yttrium(III). Thermochimica Acta, 398(1), 93-99.
Casuscelli, S., Eimer, G., Canepa, A., Heredia, A., Poncio, C., Crivello, M., Perez, C., Aguilar, A., y Herrero, E. (2008). Ti-MCM-41 as catalyst for a-pinene oxidation. Study of the effect of Ti content and H2O2 addition on activity and selectivity. Catalysis Today, 133-135, 678-683
Cejka, J., Corma, A., y Zones, S. (Eds). (2010). Zeolites and Catalysis: Synthesis, Reactions and Applications. Alemania: John Wiley & Sons.
Corma, A., Renz, M., y Susarte, M. (2009). Transformation of biomass products into fine chemicals catalyzed by solid Lewis- and Bransted-acids. Topics in Catalysis, 52(9), 1182-1189.
da Silva, M., Vieira, L., Oliveira, A., y Ribeiro, M. (2013). Novel effect of palladium catalysts on chemoselective oxidation of β-pinene by hydrogen peroxide. Monatshefte für Chemie- Chemical Monthly, 144(3), 321-326.
de Oliveira, A., Lopes, M., da Silva, M. (2009). Palladium-Catalysed Oxidation of Bicycle Monoterpenes by Hydrogen Peroxide in Acetonitrile Solutions: A Metal Reoxidant-Free and Environmentally Benign Oxidative Process. Catalysis Letters, 130, 424-431.
Deacon, G., Huber, F., y Phillips R. (1980) Relationships between the carbon-oxygen stretching frequencies of carboxylato complexes and the type of carboxylate coordination. Coordination Chemistry Reviews, 33(3), 227-250.
Kalinowska, M., Lewandowski, W., Swislocka, R., y Regulska, E. (2010). The FT-IR, FT-Raman, 1H and 13C NMR study on molecular structure of sodium(I), calcium(II), lanthanum(III) and thorium(IV) cinnamates. Journal of Spectroscopy, 24(3-4), 277-281.
Mercandante, A., Ionashiro, M., de Oliveira, L., Ribeiro, C., y Moscardini, L. (1993). Preparation and thermal decomposition of solid state lanthanide(III) and yttrium(III) chelates of ethylenediaminetetraacetic acid. Thermochimica Acta, 216, 267-277.
Nalone, L., Cardoso, T., Guimarães, R., do Ó Pessoa, C., Odorico, M., Marques, B., Gomes, L., Andrade, A., y Pergentino, D. (2015). Evaluation of the cytotoxicity of structurally correlated p-menthane derivatives. Molecules, 20(7), 13264-13280.
Pakdel, H., Sarron, S., y Roy, C. (2001). α-Terpineol from hydration of crude sulfate turpentine oil. Journal of Agricultural and Food Chemistry, 49(9), 4337-4341.
Patel, A. (Ed.). (2013). Environmentally benign catalysts: for clean organic reactions. India: Springer Science & Business Media.
Silva, M., Robles-Dutenhefner, P., Menini, L., y Gusevskaya, E. (2003). Cobalt catalyzed autoxi- dation of monoterpenes in acetic acid and acetonitrile solutions. Journal of Molecular Catalysis A: Chemical, 201(1), 71-77.
Stolle, A. (2013). Synthesis of Nopinone from P-Pinene-A Journey Revisiting Methods for Oxidative Cleavage of C=C Bonds in Terpenoid Chemistry. European Journal of Organic Chemistry, 2013(12), 2265—2278.
Suh, Y., Kim, N., Ahn, W., y Rhee, H. K. (2003) One-pot synthesis of campholenic aldehyde from a-pinene over Ti-HMS catalyst II: effects of reaction conditions. Journal of Molecular Catalysis A: Chemical, 198(1), 309-316.
Cómo citar
Mazuera-Méndez, J., Aragón-Muriel, A., & Polo-Cerón, D. (2017). Actividad catalítica de complejos p-R-cinamato de Ce(III), Nd(III) y Sm(III) en la oxidación de β-pineno y canfeno. Revista De Investigación, 10(2), 23–48. https://doi.org/10.29097/2011-639X.79
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