Volume 2, Issue 6-1, December 2014, Page: 1-8
Synergism of Metal and Organocatalysis in Condensation Reactions of Aromatic Aldehydes with Anilines Affording Imines: Effect of Catalysts on the Base of a Supported Cerium(III) and Proline
Eva Havránková, Centre for Syntheses at Sustainable Conditions and their Management, Chemistry Department, Masaryk University, Kamenice 5, CZ-625 00 Brno, Czech Republic
Patrik Pospíšil, Gymnázium Brno, Kpt. Jaroše 14, CZ-658 70, Brno 2, Czech Republic
Pavel Pazdera, Centre for Syntheses at Sustainable Conditions and their Management, Chemistry Department, Masaryk University, Kamenice 5, CZ-625 00 Brno, Czech Republic
Received: Aug. 26, 2014;       Accepted: Sep. 6, 2014;       Published: Sep. 17, 2014
DOI: 10.11648/j.sjc.s.2014020601.11      View  4924      Downloads  265
Condensation reactions between 4-X-benzaldehydes (X = NO2, H, OCH3) and 4-Y-anilines (X = NO2, H, OCH3) catalyzed by new catalyst, i.e. Ce (III) supported on weakly acidic cation-exchanger resin of polyacrylate type and/or by proline as organocatalyst giving 4-Y-N-[(E)-(4-X-phenyl)methylidene]anilines, were studied. It was found that the both of the used catalysts, i.e. metal and organocatalyst, shortened reaction time, thus contributing to higher yields of products. The synergism between catalytic action of polymer supported Ce (III) and proline was found. It was observed that simultaneous application of metal and organocatalyst led to shorter reaction times. On the other hand, it was found that the synergic efficiency of the both applied catalysts depends on electron influence of the substituents X, Y present in 4-X-benzaldehyde and 4-Y-aniline, as well. Imines were prepared under catalysis by Ce (III), proline or by simultaneous use of both catalysts in the yields 97-99% and identified. For comparison, the above mentioned condensation reactions were carried out under classical catalysis by mineral acid with different, usually poor, results.
Imines, Metal Catalysis, Organocatalysis, Synergism, Polymer Supported Ce(III)
To cite this article
Eva Havránková, Patrik Pospíšil, Pavel Pazdera, Synergism of Metal and Organocatalysis in Condensation Reactions of Aromatic Aldehydes with Anilines Affording Imines: Effect of Catalysts on the Base of a Supported Cerium(III) and Proline, Science Journal of Chemistry. Special Issue: Green Chemistry: Synthesis and Its Uses. Vol. 2, No. 6-1, 2014, pp. 1-8. doi: 10.11648/j.sjc.s.2014020601.11
P. Pazdera, “Emerging Ubiquity of Green Chemistry in Engineering and Technology,” in Handbook on Applications of Ultrasound - Sonochemistry for Sustainability, D. Chen, S. K. Sharma, A. Mudhoo, Eds. Boca Raton FL USA: CRC Press/Taylor & Francis Group, 2011, pp. 1-22.
A. Choplin, and F. Quignard, “From supported homogeneous catalysts to heterogeneous molecular catalysts,” Coordination Chem. Rev., vol. 178, pp. 1679-1702, 1988.
V. K. Ahluwalia, and R. Aggarwal, “Organic Synthesis: special Techniques,” 2nd, Alpha Science International, Oxford, 2006.
S. F. Martin, “Recent applications of imines as key intermediates in the synthesis of alkaloids and novel nitrogen heterocycles,” Pure and Applied Chemistry, vol. 81, pp. 195-204, 2009.
L.-X. Dai, Y.-R. Lin, X.-L. Hou, and Y.-G. Zhou, “Stereoselective reactions with imines,” Pure and Applied Chemistry, vol. 71, pp. 1033-1040, 1999.
CH. S. Rajput, and S. Singhal, “Synthesis, characterization, and anti-inflammatory activity of newer quinazolinone analogs,” Journal of Pharmaceutics, vol. 2013, pp. 1-7, 2013.
M. A. Fox, and J. K. Whitesell, “Organic chemistry,” 2nd, Mass.: Jones and Bartlett, Sudbury, 1977.
T. Imamoto, “Chapter 1.8,” in: B. M. Trost, I. Fleming, Eds., Comprehensive Organic Synthesis, Pergamon: Oxford, vol. 1, 1991, pp. 231-250.
G. A. Molander, “Application of Lanthanide Reagents in Organic Synthesis,” Chem. Rev., vol. 92, pp. 29-68, 1992.
T. Imamoto, “Lanthanides in Organic Synthesis,” 1st, Academic Press, London, 1994.
G. Bartoli, M. Bosco, E. Marcantoni, M. Petrini, L. Sambri, and E. Torregiani, “Conjugate addition of amines to α,β-enones promoted by CeCl3.7H2O-NaI system supported in silica gel,” J. Org. Chem., vol. 66, pp. 9052-9055, 2001.
G. Bartoli, M. Bartolacci, M. Bosco, G. Foglia, A. Giuliani, E. Marcantoni, L. Sambri, and E. Torregiani, ”The Michael additon of indoles to α,β-unsaturated ketones catalyzed by CeCl3.7H2O-NaI combination supported on silica gel,” J. Org. Chem., vol. 68, pp. 4594-4597, 2003.
E. Havránková, and P. Pazdera, “Comparative studies of catalytic application of cerium(III) chloride and resin supported cerium(III) in domino syntheses of 1,5-benzodiazepine and 1,3-diazine skeletons,” Journal of Chemical Engineering and Chemistry Research, in press.
M. T. Reetz, B. List, S. Jaroch, and H. Weinmann, “Organocatalysis,” 1st, Springer-Verlag, Berlin, 2008, pp. 5.
A. V. Rama Rao, K. Laxma Reddy, and M. Machender Reddy, “A concise route to biaryls: formal synthesys of biaryl diamino diacid (AB segment) of vancomycin,” Tetrahedron Letters, vol. 35, pp. 5039-5042, 1994.
U. K. Roy, and S. Roy, “Pd0/SnII promoted Barbier-type allylation and crotylation of sulfonimines,” Tetrahedron Letters, vol. 48, pp. 7177-7180, 2007.
L. Da Silva-Filho, V. Lacerda  Júnior, M. Constantino, and G. Da Silva, “Fast and efficient synthesis of pyrano[3,2-c]quinolines catalyzed by niobium(V) chloride,” Synthesis, vol. 2008, pp. 2527-2536, 2008.
K. P. Guzen, A. S. Guarezemini, A. T. G. Órfão, R. Cella, C. M. P. Pereira, and H. A. Stefani, “Eco-friendly synthesis of imines by ultrasound irradiation,” Tetrahedron Letters, vol. 48, pp. 1845-1848, 2007.
D. Blanco-Ania, P. H. H. Hermkens, L. A. J. M. Sliedregt, H. W. Scheeren, F. P. J. T. Rutjes, and H. A. Stefani, “Synthesis of cucurbitine derivatives: Facile straightforward approach to methyl 3-amino-4-aryl-1-methylpyrrolidine- 3-carboxylates,” Tetrahedron, vol. 65, pp. 5393-5401, 2009.
X.-F. Lin, J. Zhang, S.-L. Cui, and Y.-G. Wang, “Poly(ethylene glycol) supported liquid-phase synthesis of 1,2,4-oxadiazolines,” Synthesis, vol. 65, pp. 1569-1573, 2003.
M. Hirano S. Yakabe, H. Chikamori, J. H. Clark, and T. Morimoto, “Oxidation by chemical manganese dioxide. Part 3. Oxidation of benzylic and allylic alcohols, hydroxyarenes and aminoarenes,” Journal of Chemical Research, vol. 65, pp. 770-771, 1988.
Y. Yamane, X. Liu, A. Hamasaki, T. Ishida, M. Haruta, T. Yokoyama, and M. Tokunaga, “One-pot synthesis of indoles and aniline derivatives from nitroarenes under hydrogenation condition with supported gold nanoparticles,” Organic Letters, vol. 11, pp. 5162-5165, 2009.
M. Akazome, T. Kondo, Y. Watanabe, T. Ishida, M. Haruta, T. Yokoyama, and M. Tokunaga, “Novel synthesis of indoles via palladium-catalyzed reductive N-heterocyclization of o-nitrostyrene derivatives,” Chemistry Letters, vol. 5, pp. 769-772, 1992.
M. Akazome, T. Kondo, Y. Watanabe, T. Ishida, M. Haruta, T. Yokoyama, and M. Tokunaga, “Palladium complex-catalyzed reductive n-heterocyclization of nitroarenes - novel synthesis of indole and 2H-indazole derivatives,” The Journal of Organic Chemistry, vol. 59, pp. 3375-3376, 1994.
J. M. Pérez, R. Cano, M. Yus, and D. J. Ramón, “Straightforward synthesis of aromatic imines from alcohols and amines or nitroarenes using an impregnated copper catalyst,” European Journal of Organic Chemistry, vol. 2012, pp. 4548-4554, 2012.
R. Cano, D. J. Ramón, and M. Yus, “Impregnated ruthenium on magnetite as a recyclable catalyst for the N–alkylation of amines, sulfonamides, sulfinamides, and nitroarenes using alcohols as electrophiles by a hydrogen autotransfer process,” The Journal of Organic Chemistry, vol. 76, pp. 5547-5557, 2011.
D. Mahajan, B. A. Ganai, R. L. Sharma, and K. K. Kapoor, “Antimony chloride doped on hydroxyapatite catalyzed stereoselective one-pot synthesis of pyrano[3,2- c]quinolones,” Tetrahedron Letters, vol. 47, pp. 7919-7921, 2006.
A. Grirrane, A. Corma, H. Garcia, and K. K. Kapoor, “Highly active and selective gold catalysts for the aerobic oxidative condensation of benzylamines to imines and one-pot, two-step synthesis of secondary benzylamines,” Journal of Catalysis, vol. 264, pp. 138-144, 2009.
P. Pazdera, B. Zberovská, D. Němečková, and V. Datinská, “Catalyst based on metal complex for chemical syntheses and process for preparing thereof (Masaryk Univerzity)”, Patent CZ20110799 (A3).
F. Bolognese, and O. Mazzoni, “Cycloadition of chloroketene to imines: synthesis of cis and trans 3-chloro-2-azetidines,” Tetrahedron, vol. 47, pp.7417-7428, 1991.
S. Margerum, “Spectroscopic studies of substituted benzalanilines,” Applied Spectroscopy, vol. 19, pp. 91-97, 1965.
S. Prot, Chem. Abstr., vol. 73, pp. 119 947, 1970.
H. Neuvonen, K. Neuvonen, and F. Fueloep, “Substituent cross-interaction effects on the electronic character of the CN bridging group in substituted benzylidene anilines − models for molecular cores of mesogenic compounds. A 13C NMR study and comparison with theoretical results,” Journal of Organic Chemistry, vol. 71, pp. 3141-3148, 2006.
C. Baldoli, P. Del Buttero, G. Molteni, and T. Pilati, “Stereoselective synthesis of a new enantiopure tricyclic β-lactam derivative via a tricarbonyl(η6-arene)chromium(0) complex,” Tetrahedron Asymmetry, vol. 11, pp. 1927-1941, 2000.
A. G. M. Barrett, and P. Quayle, “Synthesis of β-lactams from imines and 1-lithio-oxy-2-phenylacetylene,” Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry, vol. 9, pp. 2193-2196, 1982.
M. Carr, M. J. , Meegen, N. M. O´Boyle, L. M. Greene, S. M. Nathwani, D. M. Zisterer, O. Bergin, T. McCabe, and D. G. Lloyd, “Synthesis and evaluation of azetidinone analogues of combretastatin A-4 as tubulin targeting agents,” Journal of Medicinal Chemistry, vol. 53, pp. 8569-8584, 2010.
J. Emsermann, T. Opatz, and A. Arduengo, “Synthesis of highly substituted 2-13C-imidazolium salts and metal NHC ­complexes for the investigation of electronic unsymmetry by NMR,” Synthesis (Germany), vol. 45, pp. 2251-2264, 2013.
Y. Ikegami, and S.-i. Yamada, “Chemistry of sodium borohydride and diborane. II. Reduction of Schiff bases with diborane in tetrahydrofuran,” Chemical and Pharmaceutical Bulletin, vol. 14, pp. 1389-1399, 1966.
Browse journals by subject