CuO nanoparticles as an efficient and reusable catalyst for the one-pot friedlander quinoline synthesis

Full text of DOI:10.5012/bkcs.2011.32.11.3853

Communications to the Editor
Bull. Korean Chem. Soc. 2011, Vol. 32, No. 11 3853
http://dx.doi.org/10.5012/bkcs.2011.32.11.3853
CuO Nanoparticles as an Efficient and Reusable Catalyst for the
One-pot Friedlander Quinoline Synthesis
†,*
Jafar Mohammad nezhad, Jafar Akbari, Akbar Heydari, and Behrooz Alirezapour
‡
§,‡
Chemistry Department, Shahre Ghods Branch, Islamic Azad University, Shahre Ghods, Iran
†
Chemistry Department, Buinzahra Branch, Islamic Azad University, Buinzahra, Iran. P.O. Box: 3451686799
*
E-mail: j_akbari@modares.ac.ir
‡
Research Center for Organic Chemical Synthesis, No.10. First-Kosar St., Tohid St, Tehran, Iran
§
Nuclear Medicine Research Group, Agricultural, Medical and Industrial Research School (AMIRS),
Nuclear Science and Technology Institute, Karaj, Iran
Received August 23, 2011, Accepted September 21, 2011
Key Words : Quinoline, Nano CuO, Heterogeneous, Solvent free
1
The quinoline ring system is presents in a number of
2
area about 214 m /g. The prepared Cuo nanoparticles were
2
natural and synthetic products often endowed with inter-
characterized by XRD and SEM.
3
esting pharmacological or physical properties. Quinoline
Model reaction was carried out by taking the mixture of 2-
aminobenzophenone, ethyl acetoacetate and 5 mol % of
catalyst in solvent free condition at 60 °C. TiO2, SiO2,
Al2O3, ZnO, MgO, CuO bulk and nano CuO have been used.
In our screening CuO nano was the best. This would be a
novel application of CuO nano catalyst for the Friedlander
quinoline synthesis.
4 5
derivatives are utilized as antimalarial, antitumor, and
6,7
antibacterial agents. Due to their importance, the synthesis
of quinolines attracted widespread attention. Despite quino-
line usage in pharmaceutical and other industries, com-
paratively few methods for their preparation have been
reported. The Friedlander annulation is one of the simplest
and most straightforward methods for the synthesis of poly
Various reaction parameters are optimized for this reac-
tion. The reaction was carried out with and without solvents
keeping the catalyst amount constant. It is observed that
solvent-free condition gave the excellent yield of product
than that in the presence of solvents.
10
substituted quinolines. Modified methods employing acid
catalysts such as lewis acids, brønsted acids and ionic liquid
11
have been reported for the quinoline synthesis. Although
these approaches are satisfactory for a one-pot synthesis of
quinolines, they suffer from at least one of the following
drawbacks such as long reaction times, low yields of the
products requiring stoichiometric amounts of catalysts,
excess amounts of diketone compounds or use of additives.
Such reactions under solvent-free condition have received
more attention in comparison with their homogeneous
counterparts, due to economical and environmental demands.
Metal oxide nanoparticles are known to generate a very
Subsequently, we applied the optimized conditions to a
variety of 2-aminoaryl ketones, active methylene compounds
and simple cyclic ketones which furnished diversely sub-
stituted quinoline derivatives (Table 1). The solid products
could be easily separate by using organic solvent and
heterogeneous catalyst was separated by simple filtration. To
determine the applicability of catalyst recovery, catalyst was
washed with diethyl ether to remove residual product, dried,
and reused over five successive cycles without any pretreat-
ment of the catalyst.
high catalytic activity toward a wide range of catalytic-
12,13
based applications.
In recent years, methods have been
developed for the preparation of novel nanostructures of
In summary, the advantages of performing the Friedlander
reaction in the presence of CuO nano as catalyst can be
summarized as follows: (1) use of a safe, nonvolatile, non-
corrosive catalyst; (2) high yields of recovering of catalyst at
the end of the reactions by simple filtration; (3) the target
products are obtained generally in excellent yields under
easy and mild reaction conditions; and (4) the reactions are
carried out under solvent free conditions with economic
benefits.
14
oxides. They can be generated by a number of preparation
methods that typically are described as physical and
15
chemical methods. Recently, nano ctystalline Al2O3 and γ-
Fe2O3 nanoparticles have been used for Freindlander reac-
16
tion. In another hand, CuO nanoparticles have been
previously used as heterogeneous and recyclable catalyst for
α-aminophosphonate synthesis and cross coupling reac-
17
tions. The solvent-less protocol has an added advantage in
the green context. The major benefits of the CuO nano as a
heterogeneous catalytic process are the fast reactions, solv-
ent-free environment, and improved yields. The catalytical
activity of CuO is well known. The CuO catalyst is prepared
General Procedure for One-Pot Synthesis of Quino-
lines: To a mixture of 2-aminoaryl ketones (2 mmol) and
β-ketoester/1,3-diketone/cyclic ketone (2 mmol) was added
CuO nanoparticles (5 mol %). The mixture was stirred at 60
18
by PEG assisted method with a few modification. The size
o
C until completion of the reaction, as indicated by TLC.
of the prepared catalyst is found to be 25-27 nm and surface
The nanocatalyst was separated from the reaction mixture by

3854 Bull. Korean Chem. Soc. 2011, Vol. 32, No. 11
Communications to the Editor
a
Acknowledgments. This research is supported by the
Table 1. Synthesis of Quinoline derivatives catalyzed by CuO nano
Islamic Azad University, Shahre-Gods branch.
Time Yield
Entry Compound 1 Compound 2
Product
(h)
(%)
References
a
1
98
1. Jones, G. In Comprehensive Heterocyclic Chemistry II; Katritzky,
A. R., Rees, C. W., Scriven, E. F. V., Eds.; Pergamon: New York,
1996; Vol. 5, Chapter 5.05, pp 167-243. (b) Gilchrist, T. L.
Heterocyclic Chemistry; Longman: London, 1997.
b
1
96
2. (a) Deng, X. Q.; Wei, C. X.; Song, M. X.; Chai, K. Y.; Sun, Z. G.;
Quan, Z. S. Bull. Korean Chem. Soc. 2011, 31, 447. (b) Chen, Y.;
Lee, Y. R. Bull. Korean Chem. Soc. 2011, 32, 2485.
3. Marjani, A. P.; Khalafy, J.; Molla Ebrahimlo, A. R.; Prager, R. H.
Bull. Korean Chem. Soc. 2011, 32, 2183.
c
3
1
94
98
4. (a) Samosorn, S.; Bremner, J. B.; Ball, A.; Lewis, K. Bioorg. Med.
Chem. 2006, 14, 857.
d
5. (a) Myers, A. G.; Tom, N. J.; Fraley, M. E.; Cohen, S. B.; Madar,
D. J. J. Am. Chem. Soc. 1997, 119, 6072.
6. (a) Singh, S.; Kumar, V.; Kumar, A.; Sharma, S.; Dua, P. Bull.
Korean Chem. Soc. 2010, 31, 3605.
e
5
5
90
88
7. (a) Aggarwal, A. K.; Jenekhe, S. A. Macromolecules 1991, 24, 6806.
8. (a) Friedlander, P. Chem. Ber. 1882, 15, 2572. (b) Lee, W. J.;
Chea, J. M.; Jahng, Y. Bull. Korean Chem. Soc. 2011, 30, 3061. (i)
Cheng, C.-C.; Yan, S.-J. Org. React. 1982, 28, 37.
f
9. (a) SMansake, R. H.; Kulka, M. Org. React. 1953, 7, 59. (c)
Linderman, R. J.; Kirollos, S. K. Tetrahedron Lett. 1990, 31, 2689.
10. Contelles, H. M.; Mayoral, E.; Samadi, A.; Carreiras, M.; Soriano,
E. Chem. Rev. 2009, 109, 2652.
b
85
g
h
i
8
8
1
1
11. (a) Strekowski, L.; Czamy, A. J. Fluoresc. Chem. 2000, 104, 281.
(b) Hu, Y. Z.; Zang, G.; Thummel, R. P. Org. Lett. 2003, 5, 2251.
(c) Arcadi, A.; Chiarini, M.; Di Giuseppe, S.; Marinelli, F. Synlett.
2003, 203. (d) Akbari, J. Heydari, A.; Kalhor, H. R.; Azizian
Kohan, S. J. Comb. Chem. 2009, 12, 137.
b
85
12. Cho, Y. S.; Huh, Y. D. Bull. Korean Chem. Soc. 2009, 30, 1410.
13. (a) Choudary, B. M.; Mulukutla, R. S.; Klabunde, K. J. J. Am.
Chem. Soc. 2003, 125, 2020. (b) Choudary, B. M.; Kantam, M. L.;
Ranganath, K. V. S.; Mahendar, K.; Sreedhar, B. J. Am. Chem.
Soc. 2004, 126, 3396. (c) Cho, Y. S.; Huh, Y. D. Bull. Korean
Chem. Soc. 2008, 29, 2525.
96
94
j
14. (a) Gleiter, H. Nanostructured Mater. 1995, 6, 3. (b) Valden, M.;
Lai, X.; Goodman, D. W. Science 1998, 281, 1647. (c) Prasetyanto,
E. A.; Sujandi, Lee, S. C.; Park, S. E. Bull. Korean Chem. Soc
2007, 28, 2359.
k
3
2
88
94
15. Khaleel, A.; Richards, R. M. in Nanoscale Materials in Chemistry;
Kladunde, K. J., Ed.; Wiley: New York, 2001; Chapter 4. Page 1-
50.
l
16. (a) Sheykhan, M.; Mámani, L.; Ebrahimi, A.; Heydari, A. J. Mol.
Catal. A: Chem. 2011, 335, 253. (b) Sadjadi, S.; Shiri, S.; Hekmatshoar,
R.; Beheshtiha, Y. S. Monatsh. Chem. 2009, 140, 343.
17. (a) Karmakar, B.; Paul, S.; Banerji, J. Arkivoc. 2011, ii, 61. (b)
Ahmadi, S. J.; Sadjadi, S.; Hosseinpour, M. Monatsh. Chem.
2011, 142, 841.
a
Reaction condition: 2 mmol 1, 2 mmol 2 and 5 mol % CuFe2O4 at 60
o
b
C. 5 mol % catalyst, 80 C; 1.5 eq of 2 was used.
o
simple filtration. The products being soluble in CH2Cl2 and
could be separated by filtration.
18. Jiang, Z.; Niu, Q.; Dang, W. Nanoscience 2007, 12, 40.