Abstract
A study of the Knoevenagel condensation of p-substituted benzaldehydes with malononitrile or ethyl cyanoacetate over potassium, calcium and lanthanum modified MgO was carried out under thermal and microwave activation. The catalysts were fully characterized to determine their textural, structural and surface acid–base properties. The whole set of catalysts were essayed in propan-2-ol test reaction in order to gain a better understanding of their acid–base properties. As for the surface basic properties of the catalysts, the modification of MgO with Ca and K led to solids with enhanced basicity while La modification slightly reduced the basicity of bare MgO. Inductive and mesomeric effects of the substituent in p-substituted benzaldehydes were coherent with a reaction mechanism in which a nucleophilic attack to the carbon atom of the carbonyl group takes place. Malononitrile or ethyl cyanoacetate were used as the active methylene reagent and the reaction was faster in the case of malononitrile as compared to ethyl cyanoacetate, indicating that the nucleophile formation (carbanion) on the catalyst basic sites is an important issue in this reaction. As for the catalysts, the overall reactivity order in thermal Knoevenagel condensation was \({\text{MgO}}-{\text{K}}\left( {\text{I}} \right)>{\text{MgO}}-{\text{K}}\left( {\text{II}} \right)>{\text{MgO}}-{\text{Ca}}\left( {\text{I}} \right) \approx {\text{MgO}}{-}{\text{La}}\left( {\text{II}} \right) \approx {\text{MgO}}>{\text{MgO}}{-}{\text{La}}\left( {\text{I}} \right)\), which completely agrees with the catalyst basicity extracted from the propan-2-ol test reaction (yield to acetone). The above correlation confirmed that, in Knoevenagel condensation, the carbanion formation on the surface basic sites of the catalysts is a key step in the reaction mechanism. The microwave-activated Knoevenagel reaction was much faster than the conventional, thermally activated reaction. The results indicate that the nucleophilic character of the Knoevenagel condensation also prevails under microwave activation.
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Marinas A, Marinas JM, Aramendia MA, Urbano FJ (2005) New developments in catalysis research, New York
Corma A, Iborra S (2006) Adv Catal 49(49):239–302
Wei Y, Zhang S, Yin S, Zhao C, Luo S, Au C-T (2011) Catal Commun 12:1333–1338
Gawande MB, Jayaram RV (2006) Catal Commun 7:931–935
Yuzhakova T, Rakic V, Guimon C, Auroux A (2007) Chem Mater 19:2970–2981
Ivanova AS (2005) Kinet Catal 46:620–633
Ivanova AS, Moroz BL, Moroz EM, Larichev YV, Paukshtis EA, Bukhtiyarov VI (2005) J Solid State Chem 178:3265–3274
Sun LB, Yang J, Kou JH, Gu FN, Chun Y, Wang Y, Zhu JH, Zou ZG (2008) Angewandte Chemie Int Ed 47:3418–3421
Wang Y, Huang WY, Chun Y, Xia JR, Zhu JH (2001) Chem Mater 13:670–677
Sun Y-H, Sun L-B, Li T-T, Liu X-Q (2010) J Phys Chem C 114:18988–18995
Yin SF, Xu BQ, Wang SJ, Au CT (2006) Appl Catal 301:202–210
Tsuji H, Kabashima H, Kita H, Hattori H (1995) React Kinet Catal Lett 56:363–369
Wang Y, Zhu JH, Huang WY (2001) Phys Chem Chem Phys 3:2537–2543
Ikeue K, Miyoshi N, Tanaka T, Machida M (2011) Catal Lett 141:877–881
Peng YQ, Song GH (2003) Indian journal of chemistry. Org Chem Incl Med Chem 42:924–926
Angelescu E, Pavel OD, Birjega R, Zavoianu R, Costentin G, Che M (2006) Appl Catal 308:13–18
Calvino-Casilda V, Martin-Aranda RM, Lopez-Peinado AJ, Sobczak I, Ziolek M (2009) Catal Today 142:278–282
Hasegawa T, Krishnan CK, Ogura M (2010) Microporous Mesoporous Mater 132:290–295
Ruiz JR, Jimenez-Sanchidrian C, Hidalgo JM (2007) Catal Commun 8:1036–1040
Aramendia MA, Borau V, Garcia IM, Jimenez C, Marinas A, Marinas JM, Urbano FJ (2003) Applied Catalysis 43:71–79
Manriquez-Ramirez M, Gomez R, Hernandez-Cortez JG, Zuniga-Moreno A, Reza-San CM (2013) German, S.O. flores-valle. Catal Today 212:23–30
Ardizzone S, Bianchi CL, Vercelli B (1998) Coll Surf A 144:9–17
Cho YB, Seo G, Chang DR (2009) Fuel Process Technol 90:1252–1258
Taufiq-Yap YH, Lee HV, Hussein MZ, Yunus R (2011) Biomass Bioenerg 35:827–834
Alarcon N, Garcia X, Centeno MA, Ruiz P, Gordon A (2004) Appl Catal 267:251–265
Jimenez R, Garcia X, Cellier C, Ruiz P, Gordon AL (2006) Appl Catal 314:81–88
Natile MM, Ugel E, Maccato C, Glisenti A (2007) Appl Catal 72:351–362
Gonzalez-Cortes SL, Aray I, Rodulfo-Baechler SMA, Lugo CA, Del Castillo HL, Loaiza-Gil A, Imbert FE, Figueroa H, Pernia W, Rodriguez A, Delgado O, Casanova R, Mendialdua J, Rueda F (2007) J Mater Sci 42:6532–6540
Aramendia MA, Borau V, Jimenez C, Marinas JM, Porras A, Urbano FJ (1997) J Chem Soc Faraday Trans 93:1431–1438
Aramendia MA, Borau V, Jimenez C, Marinas JM, Porras A, Urbano FJ (1999) J Mater Chem 9:819–825
Dewick PM (2006) Essentials of organic chemistry. Wiley, Chichester, pp 125–135
Climent MJ, Corma A, Iborra S, Velty A (2002) J Mol Catal A 182–183:327–342
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The authors are thankful to the staff at the Central Service for Research Support (SCAI) of the University of Córdoba for their assistance in ICP-MS measurements. Supported by Spanish MICINN and MEC (CTQ2008-01330, CTQ2010-18126) and Junta de Andalucía (P08-FQM-3931 and P09-FQM-4781 projects), co-financed by FEDER funds.
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Álvarez, L., Hidalgo-Carrillo, J., Marinas, A. et al. Sustainable C–C bond formation through Knoevenagel reaction catalyzed by MgO-based catalysts. Reac Kinet Mech Cat 118, 247–265 (2016). https://doi.org/10.1007/s11144-016-1003-z
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DOI: https://doi.org/10.1007/s11144-016-1003-z