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International Journal of Chemistry

Vol. 2, No. 2; August 2010

One-pot Preparation of β–amino Carbonyl Compounds by Mannich Reaction Using MgO/ZrO2 as Effective and Reusable Catalyst
Deepak.M. Nagrik (Corresponding author) Department of Chemistry, PLIT and MS Buldana-443001, M.S., India E-mail: dmnagrik@rediffmail.com D.M.Ambhore P.G.Department of Chemistry, Jijamata Mahavidyalaya Buldana-443001, M.S., India Manoj.B. Gawande (Corresponding author) Departamento de Química, Faculdade de Ciências and Tecnologia Quinta da Torre, 2829-516 Caparica, Portugal E-mail: mbgawande@yahoo.co.in, m.gawande@fct.unl.pt Abstract A new one-pot and efficient three-component condensation of aldehydes, ketones, and amines in the presence of MgO/ZrO2 as an inexpensive and effective catalyst for the synthesis of β-amino carbonyl compounds by Mannich reaction is described. The present methodology offers several advantages, such as good yields, short reaction times and a recyclable catalyst with a very easy work up. Keywords: Multi-component reaction, MgO/ZrO2, heterogeneous catalyst, β-amino Carbonyl compounds 1. Introduction The synthesis of natural molecules, pharmaceuticals and other nitrogenous biologically active compounds has long been a significant branch of organic synthesis. (B. List, 2002; 2000; R. O. Duthaler, 2003) The Mannich reaction provides one of the most basic and useful methods for the synthesis of such compounds. Multi-component reactions (MCRs) are important for the achievement of high levels of brevity and diversity. They allow more than two simple and flexible building blocks to be combined in practical, time-saving one-pot operations, giving rise to complex structures by simultaneous formation of two or more bonds, according to the domino principle. (Zhu, J., 2005) MCRs contribute to the requirements of an environmentally friendly process by reducing the number of synthetic steps, energy consumption and waste production. Researchers have transformed this powerful technology into one of the most efficient and economic tools for combinatorial and parallel synthesis. (Zhu, J., 2005; Beck, B., 2000) Due to their inherent simple experimental procedures and their one-pot character, they are perfectly suited for automated synthesis. An amine, two carbonyl compounds and catalysts are used to produce β-amino carbonyl compounds (Scheme1) β -amino carbonyl compounds are very useful in pharmaceutical and other biologically related areas of chemistry. One of the many synthetic routes to these compounds is the Mannich reaction which brings together three compounds under appropriate catalytic conditions. These simplified reaction systems fulfill several of the principles of green chemistry including the use of recyclable catalysts and reduced auxiliaries. Mannich reaction is one of the most important C-C bond forming reactions in organic synthesis for the preparation of secondary and tertiary amine derivatives (M. Arend, 1998). These amines are further used for the synthesis of many intermediates, biologically active and natural products such as alkaloids and polyketides. The products of Mannich reaction are mainly β -amino carbonyl compounds and its derivatives that are used for the synthesis of amino alcohols, peptides, and lactams and as precursors to optically active amino acids. The conventional catalysts for classical Mannich reaction of aldehydes, ketones and amines involve mainly organic and mineral acids like proline (B. List, 2002; 2000; R.O. Duthaler, 2003), acetic acid (K. Mogilaiah, 2002),


ISSN 1916-9698

E-ISSN 1916-9701

10 mmol ketone. an appropriate amount of magnesium nitrate[MgO(NO3)2. They often suffer from the drawbacks of long reaction times and harsh reaction conditions. and ketones.65.D. 2. 2-nitroaniline (2b) and 4-bromoaniline (3b) and the ketones were acetophenone (1c) and p-hydroxy acetophenone (2c). The reaction mixture turned turbid after a certain reaction time and at last became very viscous and close to solid. Dilute ammonia solution was added dropwise with vigorous stirring until the precipitation was complete (PH=10). Tao Jiang et. which limit its use in the synthesis of complex molecules. we have investigated heterogeneous basic catalyst MgO/ZrO2 for the Knovenagel condensation reaction (Gawande M. Experimental 2. In continuation of our study for the development of heterogeneous catalysis (Gawande M. 3-chloro-benzaldehyde (4a) and benzaldehyde (5a). amines. The amines included aniline (1b). After reaction.1 Chemicals All the aldehydes.0. acetophenone. Manabe. 2007. (3) the catalyst can be easily recycled and reused. toxicity and difficulty in product separation. First. % of catalyst in acetonitrile were loaded into a magnetically stirred glass reactor under reflux condition at 80 °C.al (Hamid Reza Shaterian. ketones and amines in presence of MgO/ZrO2 (0. The reusability of the catalyst was checked by the reaction of benzaldehyde. 3-chloro-benzaldehyde (3a).86).56.25:0. p-methoxy benzaldehyde (2a).44:0. The resultant solution was filtered and washed with distilled water till free from chloride ions. the mixture was washed with distilled water (15 mL) and filtered.35:065) has been successfully used as catalyst for Mannich reactions using aldehydes. 298-313) have synthesized β–amido ketones and esters in four-component condensation reaction using ferric hydrogensulfate as effective and reusable catalyst.35:0. P.35/0.2 General procedure for the synthesis of catalyst In a typical experiment for the preparation of MgO/ZrO2 with varying mole compositions(0.al (Suman Sahoo.35:065) under reflux condition at 80 °C.8H2O] were dissolved separately in deionised water and mixed together. The mole ratio of MgO/ZrO2 was chosen to be 0. 2006) and applications in organic synthesis. Mumbai. we optimized the mole ratio of MgO/ZrO2 for the reaction benzaldehyde. Fine Chemicals. 2. Utilization of this catalyst has several advantages: (1) high yield and high reaction rate can be achieved. The residue was dried for 24 hours at 383K in an oven and further calcined at 873 K for 6 hours. Recently. in a muffle furnace in air. amines. The results indicate that the catalyst can be used five times without any loss of its activity.65 wt. The % and mole composition of MgO/ZrO2 are given in following Table 1. The solid product was re-crystallized using ethanol or a mixture of ethanol and benzene and then dried at 50 °C under vacuum until constant weight. 4.35/0. and 0. 10 mmol amine. 2006) have synthesized β-amino carbonyl compounds by using Bronsted ionic liquids as a solvent and catalyst. To best of our knowledge. the aldehydes used were Piperonal (1a).75.Yarahmadi et. Kobayashi.3 Procedures for Mannich reaction In a typical experiment.al (2004) has carried out Mannich reaction by using ionic liquids as a solvent and catalyst. For Mannich reactions. No. which shows a balance between recyclisation and activity for the Mannich reaction. we are present application of MgO/ZrO2 for synthesis of β-amino carbonyl compounds. 2001) and some Lewis acids (S. 2006). 2005. were obtained from S. 2. and used without further purification. 10 mmol aldehyde.65 Wt. this is first report for the synthesis of β-amino carbonyl compounds over MgO/ZrO2. The main contribution of this work is synthesizing MgO/ZrO2(0. Conclusions MgO/ZrO2 (0. Desai. Results and discussion In this article.www. % (Table 3). Published by Canadian Center of Science and Education 99 . ketones. The most efficient reaction went to completion in 8 hours at 80oC The Mannich reactions of aldehydes. 2000). convenient and efficient protocol for the synthesis of β-amino carbonyl compounds by Mannich reaction using MgO/ZrO2 as a novel catalyst. and aniline. (Table 2) 3.ccsenet. Herewith. aniline and acetophenone in the presence of acetonitrile using MgO/ZrO2 (0.0. 2002.35:065) successfully. 2.Trissa Joseph et. (2) the preparation of catalyst is simple.0. 2. August 2010 p-dodecylbenzenesulfonic acid (K.35:065) to be fashioned for specific chemical applications. (4) this protocol provides further examples of the capacity of MgO/ZrO2 (0. Guoying Zhao.6H2O] and zirconium oxy chloride[ZrOCl2.35:065) catalyst were carried under reflux condition at 80 °C and are summarized in Table 4.14:0.org/ijc International Journal of Chemistry Vol. we wish to report a mild.

Mori. Green Chem. G. Jayaram. M. References B. 11. Gawande. C. 7. (2002).56 O + NH2 + CHO MgO/ZrO2 (0.. M. Huang. S. M. Med. Chem. 23. Of Chemistry. 10. O HN 100 ISSN 1916-9698 E-ISSN 1916-9701 . B. J. August 2010 Acknowledgements We are thankful to The Principal. (2006).V. Dept.L. Res. Jijamata Mahavidyalaya. Catal. List. Gawande.. Jayaram. Wiley. Kobayashi. Soc.179. Hamada. B. Heterocycl. B. Commun. Bioorg.14/0. 10. J. R. Buldana (M. V. J. Biller and H.. 122. T. Mixed oxides of MgO/ZrO2 Entry 1 2 3 4 Mixed oxides of MgO/ZrO2 MgO Wt% 5 10 15 20 ZrO2 Wt.86 0. P. Kankaiah. A 241. Catalysis Commun. Zhao. Desai. Han. Sahoo. 283. Westermann. (2000). B.65 0.44/0. B. Am.75 0. (2000). Chem. G. Ed. S. (2007). Soc. Manabe. (1998). Chem. 80 oC Scheme 1. R. J. (2002). K. 931.) India. 576.35:065) CH3CN. R. Deshpande. Dömling.Beck. ARKIVOC (xvi) 298.35/0. J. Mol.. (2004).G. S. Halligudi. 244 . Bienayme. (2006).B. P. Duthaler.ccsenet. 93. R. Engl. List..B.S. Jayaram. Soc. Chem. Journal of Molecular Catalysis A Chemical..25/0.. 2537. 7226. (2005). Arend. 122. Jiang. (2001).. Buldana (M. India. Int. Gawande. The Head.V. 124. 8170. Agrios..org/ijc International Journal of Chemistry Vol. D. for providing necessary laboratory facilities. 2. S.Aube. K. Manabe. Tetrahedron. R. Indian J. Multicomponent Reactions. 57. Risch. S. 975.). T. J. Gawande. T. and Environ. Chem. 8. DMN is thankful to his mother for her inspiration and moral support. (2002). Chem.www. Jayaram. 37. T. Am. K. Table 1. Soc. S.B. H. 48. H.. Am. (2007). J.151 M. Ed.S. J. B. 5640. Mini-Review green cluster. Polshettiwar. Lett. Murkute. M. 2. M. Angew. 1701. 827. Joseph. Sun. 1044. Gao. Martin. 42. Angew.V. Kobayashi. J. Chem.A. K. S. Tetrahedron Lett. (2000). K. G. (2003). A. J. Schildknegt. Milligan. R. S. Chem.Gawande. B. Mogilaiah. Zhu. (2006). J. Int.. Hess. Am. S. Ghashang. Pojarliev. Shaterian. P. Mossman.Sonavane. and Environ. V. R. B. No. Y. (2006). H. V. M. Jijamata Mahavidyalaya. S. Yarahmadi. Chem. 9336. W. 124. Catal. N. Gawande. 75 H. 10.. Varma. Chem. R. O. U. 6. Jayaram. Res. (2005). R.% 95 90 85 80 MgO/ZrO2 0. M.

2.14/0. Run no.14/0.44/0. 1 2 3 4 5 Yield (%) 91 90 89 87 87 Table 3. Recyclability of the catalyst in the reaction of benzaldehyde. 2.86 0. acetophenone and aniline using various ratio of MgO/ZrO2 under reflux condition at 80 oC Entry 1 2 3 4 5 MgO/ZrO2 (Wt.%) 0.56 0. Three-component Mannich reactions of aldehydes. amines. No.86 Time/h 12 16 8 12 13 Yield% 77 85 91 81 79 Table 4.www.35:065) catalyst at 80 oC Entry Aldehyde Ketone Amine Time/h Yield (%) 91 66 62 31 89 67 54 87 81 83 0 1 2 3 4 5 6 7 8 9 10 11 1a 2a 3a 4a 5a 1a 2a 3a 4a 5a 1a 1c 1c 1c 1c 1c 1c 1c 1c 1c 1c 1c 1b 1b 1b 1b 1b 2b 2b 2b 2b 2b 3b 08 08 05 04 12 12 12 12 12 12 12 Published by Canadian Center of Science and Education 101 .65 0.86 0. August 2010 Table 2. and ketones in the presence of MgO/ZrO2 (0.14/0.35/0. aniline and acetophenone in the presence of acetonitrile using MgO/ZrO2 (0.35:065) under reflux condition at 80 oC.org/ijc International Journal of Chemistry Vol. Reaction of benzaldehyde.ccsenet.

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