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Journal of Chemistry
Volume 2013 (2013), Article ID 834656, 6 pages
http://dx.doi.org/10.1155/2013/834656
Research Article

1-Methyl-3-(2-(sulfooxy)ethyl)-1H-imidazol-3-ium Chloride as a New and Green Ionic Liquid Catalyst for One-Pot Synthesis of Dihydropyrimidinones under Solvent-Free Condition

Department of Chemistry, Payame Noor University, P.O. Box 19395-4697, Tehran, Iran

Received 8 June 2012; Revised 11 September 2012; Accepted 15 September 2012

Academic Editor: Francisco José Hernández Fernández

Copyright © 2013 Sami Sajjadifar et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

Abstract

An efficient and simple method for the preparation of 1-methyl-3-(2-(sulfooxy)ethyl)-1H-imidazol-3-ium chloride as an acidic ionic liquid is described. One-pot multicomponent condensation of 1,3-dicarbonyl compounds, urea/thiourea and aldehydes at 80C affords the corresponding compounds in high yields and in short reaction times by using (MSEI)Cl.

1. Introduction

First reported for multicomponent reaction involves a three-component, one-pot condensation of an aldehyde, α,β-ketoester, and urea under strongly acidic conditions discovered by Biginelli in 1893 [10]. In the past few decades, interest in this reaction has increased dramatically since dihydropyrimidinones have a wide range of biological activities, acting as calcium channel antagonists, anti-hypertensive, anti-bacterial and anti-inflammatory agents, while also possessing cytotoxic activity [1117]. In order to improve the efficiency of Biginelli reaction, a variety of catalysts have been reported which of them H4PMo11VO40, [18], Dowex-50W [19], H3PW12O40/SiO2 [20], MgBr2 [21], polymer-supported 4-aminoformoyldiphenylammonium triflate [22], NaHSO4/SiO2 [23], FeCl3 [24], ZrCl4 [25], Cu(OTf)2 [26], Bi(OTf)3 [27], yutterbium triflate [28], NH2SO3H [29], 12-Molybdopho sphoric acid [30], natural HEU type zeolite [31], Sr(OTf)2 [32], covalently anchored sulfonic acid onto silica [33], ZrOCl2·8H2O [34], silica triflate [35], Fe(HSO4)3 [36], TCICA [37], PPh3 [38], CaF2 [39], [bmim]BF4-immobilized Cu(II) acetylacetonate [40], [bmim][FeCl4] [7], ionic liquidsunder ultrasound irradiation [41], and melamine trisulfonic acid [42] are examples. Ionic liquids (ILs), which have been widely promoted as green solvents, are attracting much attention for applications in many fields of chemistry and industry due to their chemical and thermal stability, low vapor pressure, and high-ionic-conductivity properties. Over the last few years, ILs have been popularly used as solvents for organic synthesis, catalysis,and also been used as media for extraction processes [43, 44]. But some of the mentioned methods encounter drawbacks such as the requiring expensive reagents, long reaction times, low yields of the products and tedious workup. The advantages of the present procedure are simplicity of operation, short reaction times, inexpensive reagents, green condition, and the high yields of products.

We synthesized the bronsted acidic ionic liquid 1-methyl-3-(2-(sulfooxy)ethyl)-1H-imidazol-3-ium chloride [45] as an efficient and reusable catalyst for the synthesis of DHPMs derivatives.

2. Experimental

IR spectra of the compounds were obtained on a PerkinElmer spectrometer version 10.03.06 using a KBr disk. The 1H nuclear magnetic resonance (1H NMR) spectra were recorded on a Bruker AQS 400 Avance instrument at 400 MHz in dimethyl sulfoxide (DMSO-d6) using tetramethylsilane as an internal standard. The progress of reaction was followed with thin-layer chromatography (TLC) using silica gel SILG/UV 254 and 365 plates. All the products are known compounds and were characterized by comparing the IR, 1H NMR, and 13C NMR spectroscopic data and their melting points with the literature values.

2.1. Preparation of Bronsted Acidic Ionic Liquid

1-Methylimidazole 1 (4.1 g, 50 mmol) and 2-chloroethanol 2 (4.02 g, 50 mmol) were added in a flask containing 10 mL of CHCl3, and the mixture was refluxed for 8 h and removed CHCl3 under vacuum. Unreacted 1-methylimidazole or 2-chloroehanol was extracted with ether (3 × 10 mL) to give 1-methyl-3-(2-hydroxylethyl) imidazolium chloride (yield 95%). IR spectrum of compound 3: OH (3200–3600 cm−1), C=C (1450, 1575 cm−1), and C=N (1643 cm−1) (Figure 2).

A stoichiometric amount of 97% chlorosulfonic acid (3.4 mL, 50 mmol) in CCl4 (10 mL) was added dropwise to compound 3 over a period of 45–60 min at 0°C, and HCl gas was evolved in an alkali trap immediately (Scheme 1). The mixture was washed with CCl4 (3 × 10 mL) to remove the unreacted chlorosulfonic acid (yield 92%). IR spectrum of compound 4: OH (3200–3600 cm−1), C=C (1440, 1579 cm−1), C=N (1648 cm−1), S=O (1019 cm−1), and S–O (623 cm−1) (Figures 1 and 2) [44].

834656.sch.001
Scheme 1: Synthesis of 1-methyl-3-(2-(sulfooxy)ethyl)-1H-imidazol-3-ium chloride.
834656.sch.002
Scheme 2: Synthesis of 3,4-dihydropyrimidin-2(1H)-ones and -thiones.
834656.fig.001
Figure 1
834656.fig.002
Figure 2: Comparison IR spectrum of ionic liquid 3, bronsted acidic ionic liquid 4.
2.2. General Procedure for the Preparation of DHPMs

A mixture of an aromatic aldehyde (1 mmol), β-dicarbonyl (1 mmol), urea/thiourea (1.5 mmol), and catalyst (50 mg) was finely mixed together in a test tube at 80°C for the times reported in (Table 2). During the reaction process, a solid product spontaneously formed. The completion of the reaction was monitored by TLC. The reaction mixture was cooled to room temperature and then cold water (20 mL) was added to the reaction mixture and stirred for 10–15 min. During this time, crystals of the product formed which were collected by filtration and dried and then recrystallized from ethanol to afford the pure product. The results are summarized in Table 2. The aqueous layer (including BAIL) was separated, and its solvent was evaporated to obtain pure BAIL. The recycled catalyst was used for the next run under identical reaction conditions.

3. Results and Discussion

The one-pot synthesis of 3,4-dihydropyrimidin-2(1H)-ones and -thiones was achieved by the three-component condensation of aldehydes, dicarbonyl, and urea or thiourea in presence of bronsted acidic ionic liquid is conducted at 80°C, and the results are summarized in Table 1. The procedure gives products in good yields, short reaction times and avoids the use of organic solvents (handling, cost, safety, pollution) (Table 4). Environmental friendly ionic liquid afforded a valuable alternative to promote a numerous efficient catalytic systems that have already been proposed for the achievement of DHPMs. As long as, the reaction rate and the yields are depending on electron donating/withdrawing effect of the groups on the benzene ring in benzaldehydes. Aryl aldehydes containing electron-donating substituent gave excellent yields of the products in a shorter reaction time. The mechanism of the Biginelli reaction established by Kappe [6] proposed that the key step in this cyclocondensation process should involve the formation of N-acyliminium ion intermediate (Scheme 3).

tab1
Table 1: Temperature and time effect on dihydropyrimidinones synthesis.
tab2
Table 2: Dihydropyrimidinones synthesis catalyzed by BrØnsted acidic ionic liquid (BAIL).
834656.sch.003
Scheme 3: Mechanism of synthesis of 3,4-dihydropyrimidin-2(1H)-ones and -thiones.

According at Table 2 the using of thiourea and ethylacetoacetate increased reaction time, and also the using of thiourea reduces the efficiency of Biginelli reaction. Thiourea stability of negatively charged than urea and low nucleophiles property of thiourea than urea at intermediate State. The catalyst is reusable and can be applied several times without any decrease in the yield of the reaction. As it can be seen from Table 3, (MSEI)Cl as a catalyst afforded the good results with respect to the another ionic liquid catalysts.

tab3
Table 3: Comparison of catalytic ability of catalysts.
tab4
Table 4: Formation of DHMP in different solvents and comparison with solvent-free condition.

4. Conclusions

In summary, we have developed the use of bronsted acidic ionic liquid 1-methyl-3-(2-(sulfooxy)ethyl)-1H-imidazol-3-ium chloride as an inexpensive, easy to handle, noncorrosive and environmentally benign catalyst for the Biginelli reaction from an aldehyde, a β-dicarbonyl, and urea or thiourea. The advantages of the present procedure are simplicity of operation, very short reaction times compared with other procedures for the preparation of dihydropyrimidinones derivatives, and the high yields of products. In this reaction the catalyst can be were easily recyclable after removing starting materials and water (Table 5).

tab5
Table 5: Recovery of catalyst.

Acknowledgments

The authors gratefully acknowledge partial support of this work by Payame Noor University (PNU) of Ilam.

References

  1. X. Jing, Z. Li, X. Pan, Y. Shi, and C. Yan, “NaIO4-catalyzed one-pot synthesis of dihydropyrimidinones at room temperature under solvent-free conditions,” Journal of the Iranian Chemical Society, vol. 6, no. 3, pp. 514–518, 2009. View at Publisher · View at Google Scholar
  2. M. Dabiri, P. Salehi, M. Baghbanzadeh et al., “Efficient and eco-friendly synthesis of dihydropyrimidinones, bis(indolyl)methanes, and N-alkyl and N-arylimides in ionic liquids,” Journal of the Iranian Chemical Society, vol. 4, no. 4, pp. 393–401, 2007. View at Google Scholar · View at Scopus
  3. R. Zheng, X. Wang, H. Xu, and J. Du, “Brønsted acidic ionic liquid: An efficient and reusable catalyst for the synthesis of 3,4-dihydropyrimidin-2(1H)-ones,” Synthetic Communications, vol. 36, p. 1503, 2006. View at Google Scholar
  4. S. Ghassamipour and A. R. Sardarian, “One-Pot synthesis of dihydropyrimidinones by dodecylphosphonic acid as solid Bronsted Acid Catalyst under Solvent-Free Conditions via Biginelli condensation,” Journal of the Iranian Chemical Society, vol. 7, no. 1, pp. 237–242, 2010. View at Publisher · View at Google Scholar
  5. S. Besoluk, M. Kucukislamoglu, M. Nebioglu, M. Zengin, and M. Arslan, “Solvent-free synthesis of dihydropyrimidinones catalyzed by alumina sulfuric acid at room temperature,” Journal of the Iranian Chemical Society, vol. 5, no. 1, pp. 62–66, 2008. View at Google Scholar · View at Scopus
  6. H. W. Zhan, J. X. Wang, and X. T. Wang, “Solvent- and catalyst-free synthesis of dihydropyrimidinthiones in one-pot under focused microwave irradiation conditions,” Chinese Chemical Letters, vol. 19, no. 10, pp. 1183–1185, 2008. View at Publisher · View at Google Scholar
  7. X. Chen and Y. Peng, “Chloroferrate(III) ionic liquid: efficient and recyclable catalyst for solvent-free synthesis of 3,4-dihydropyrimidin-2(1H)-ones,” Catalysis Letters, vol. 122, no. 3-4, pp. 310–313, 2008. View at Publisher · View at Google Scholar
  8. J. Peng and Y. Deng, “Ionic liquids catalyzed Biginelli reaction under solvent-free conditions,” Tetrahedron Letters, vol. 42, no. 34, pp. 5917–5919, 2001. View at Publisher · View at Google Scholar · View at Scopus
  9. Garima, V. P. Srivastava, and L. D. S. Yadav, “Biginelli reaction starting directly from alcohols,” Tetrahedron Letters, vol. 51, no. 49, pp. 6436–6438, 2010. View at Publisher · View at Google Scholar · View at Scopus
  10. P. Biginelli, “Derivati aldeiduredici degli eteri acetile dossal-acetico,” Gazzetta Chimica Italiana, vol. 23, pp. 360–413, 1893. View at Google Scholar
  11. C. Oliver Kappe, W. M. F. Fabian, and M. A. Semones, “Conformational analysis of 4-aryl-dihydropyrimidine calcium channel modulators. A comparison of ab initio, semiempirical and X-ray crystallographic studies,” Tetrahedron, vol. 53, no. 8, pp. 2803–2816, 1997. View at Publisher · View at Google Scholar · View at Scopus
  12. C. O. Kappe, “100 years of the Biginelli dihydropyrimidine synthesis,” Tetrahedron, vol. 49, no. 32, pp. 6937–6963, 1993. View at Publisher · View at Google Scholar · View at Scopus
  13. K. S. Atwal, G. C. Rovnyak, B. C. O'Reilly, and J. Schwartz, “Substituted 1,4-dihydropyrimidines. 3. Synthesis of selectively functionalized 2-hetero-1,4-dihydropyrimidines,” Journal of Organic Chemistry, vol. 54, no. 25, pp. 5898–5907, 1989. View at Google Scholar · View at Scopus
  14. M. M. Amini, A. Shaabani, and A. Bazgir, “Tangstophosphoric acid (H3PW12O40): an efficient and eco-friendly catalyst for the one-pot synthesis of dihydropyrimidin-2(1H)-ones,” Catalysis Communications, vol. 7, no. 11, pp. 843–847, 2006. View at Publisher · View at Google Scholar · View at Scopus
  15. B. Jauk, T. Pernat, and C. O. Kappe, “Design and synthesis of a conformationally rigid mimic of the dihydropyrimidine calcium channel modulator SQ 32,926,” Molecules, vol. 5, no. 3, pp. 227–239, 2000. View at Google Scholar · View at Scopus
  16. J. Azizian, M. K. Mohammadi, O. Firuzi, B. Mirza, and R. Miri, “Microwave-assisted solvent-free synthesis of bis(dihydropyrimidinone) benzenes and evaluation of their cytotoxic activity: research article,” Chemical Biology and Drug Design, vol. 75, no. 4, pp. 375–380, 2010. View at Publisher · View at Google Scholar · View at Scopus
  17. M. B. Deshmukh, S. M. Salunkhe, D. R. Patil, and P. V. Anbhule, “A novel and efficient one step synthesis of 2-amino-5-cyano-6-hydroxy-4-aryl pyrimidines and their anti-bacterial activity,” European Journal of Medicinal Chemistry, vol. 44, no. 6, pp. 2651–2654, 2009. View at Publisher · View at Google Scholar · View at Scopus
  18. S. P. Maradur and G. S. Gokavi, “Heteropoly acid catalyzed synthesis of 3,4-dihydropyrimidin-2(1H)-ones,” Catalysis Communications, vol. 8, no. 3, pp. 279–284, 2007. View at Publisher · View at Google Scholar · View at Scopus
  19. K. Singh, D. Arora, and S. Singh, “Dowex-promoted general synthesis of N,N′-disubstituted-4-aryl-3,4-dihydropyrimidinones using a solvent-free Biginelli condensation protocol,” Tetrahedron Letters, vol. 47, no. 25, pp. 4205–4207, 2006. View at Publisher · View at Google Scholar · View at Scopus
  20. E. Rafiee and F. Shahbazi, “One-pot synthesis of dihydropyrimidones using silica-supported heteropoly acid as an efficient and reusable catalyst: improved protocol conditions for the Biginelli reaction,” Journal of Molecular Catalysis A, vol. 250, no. 1-2, pp. 57–61, 2006. View at Publisher · View at Google Scholar
  21. H. Salehi and Q. X. Guo, “A facile and efficient onepot synthesis of dihydropyrimidinones catalyzed by magnesium bromide under solventfree conditions,” Synthetic Communications, vol. 34, no. 1, pp. 171–179, 2004. View at Publisher · View at Google Scholar
  22. M. Lei, D. D. Wu, H. G. Wei, and Y. Wang, “Polymer-supported 4-aminoformoyldiphenylammonium triflate (PS-AFDPAT): an effective and recyclable catalyst for the Biginelli reaction,” Synthetic Communications, vol. 39, no. 3, pp. 475–483, 2009. View at Publisher · View at Google Scholar
  23. M. A. Chari and K. Syamasundar, “Silicagel supported sodium hydrogensulfate as a heterogenous catalyst for high yield synthesis of 3,4-dihydropyrimidin-2 (1H)-ones,” Journal of Molecular Catalysis A, vol. 221, no. 1-2, pp. 137–139, 2004. View at Publisher · View at Google Scholar
  24. J. Lu and Y. Bai, “Catalysis of the Biginelli reaction by ferric and nickel chloride hexahydrates. One-pot synthesis of 3,4-dihydropyrimidin-2(1H)-ones,” Synthesis, vol. 4, pp. 466–470, 2002. View at Publisher · View at Google Scholar
  25. C. V. Reddy, M. Mahesh, P. V. K. Raju, T. R. Babu, and V. V. N. Reddy, “Zirconium(IV) chloride catalyzed one-pot synthesis of 3,4-dihydropyrimidin-2(1H)-ones,” Tetrahedron Letters, vol. 43, no. 14, pp. 2657–2659, 2002. View at Publisher · View at Google Scholar · View at Scopus
  26. A. S. Paraskar, G. K. Dewkar, and A. Sudalai, “Cu(OTf)2: a reusable catalyst for high-yield synthesis of 3,4-dihydropyrimidin-2(1H)-ones,” Tetrahedron Letters, vol. 44, no. 16, pp. 3305–3308, 2003. View at Publisher · View at Google Scholar · View at Scopus
  27. R. Varala, M. M. Alam, and S. R. Adapa, “Bismuth triflate catalyzed one-pot synthesis of 3,4-dihydropyrimidin-2 (1H)-ones: an improved protocol for the Biginelli reaction,” Synlett, no. 1, pp. 67–70, 2003. View at Google Scholar · View at Scopus
  28. Y. Ma, C. Qian, and M. Yang, “Lanthanide triflate catalyzed Biginelli reaction. One-pot synthesis of dihydropyrimidinones under solvent-free conditions,” The Journal of Organic Chemistry, vol. 65, no. 12, pp. 3864–3868, 2000. View at Publisher · View at Google Scholar
  29. S. A. Kotharkar, M. R. Jadhav, R. R. Nagawade, S. S. Bahekar, and D. B. Shinde, “Sulphamic acid (H2NSO3H) catalysed one pot synthesis of 3,4-dihydropyrimidin-2(1H)-ones and their thione analogues,” Letters in Organic Chemistry, vol. 2, p. 662, 2005. View at Publisher · View at Google Scholar
  30. M. M. Heravi, K. Bakhtiari, and F. F. Bamoharram, “12-Molybdophosphoric acid: a recyclable catalyst for the synthesis of Biginelli-type 3,4-dihydropyrimidine-2(1H)-ones,” Catalysis Communications, vol. 7, no. 6, pp. 373–376, 2006. View at Publisher · View at Google Scholar · View at Scopus
  31. M. Tajbakhsh, B. Mohajerani, M. M. Heravi, and A. N. Ahmadi, “Natural HEU type zeolite catalyzed Biginelli reaction for the synthesis of 3,4-dihydropyrimidin-2(1H) one derivatives,” Journal of Molecular Catalysis A, vol. 236, no. 1-2, pp. 216–219, 2005. View at Publisher · View at Google Scholar · View at Scopus
  32. W. Su, J. Li, Z. Zheng, and Y. Shen, “One-pot synthesis of dihydropyrimidiones catalyzed by strontium(II) triflate under solvent-free conditions,” Tetrahedron Letters, vol. 46, no. 36, pp. 6037–6040, 2005. View at Publisher · View at Google Scholar
  33. R. Gupta and S. Paul, “Covalently anchored sulfonic acid onto silica as an efficient and recoverable interphase catalyst for the synthesis of 3,4-dihydropyrimidinones/thiones,” Journal of Molecular Catalysis A, vol. 266, no. 1-2, pp. 50–54, 2006. View at Publisher · View at Google Scholar
  34. F. Shirini, M. A. Zolfigol, and E. Mollarazi, “ZrOCl2·8H2O as an efficient reagent for the solvent-free synthesis of 3,4-dihydropyrimidin-2-(1H)-ones,” Synthetic Communications, vol. 36, no. 16, pp. 2307–2310, 2006. View at Publisher · View at Google Scholar · View at Scopus
  35. F. Shirini, K. Marjani, and H. T. Nahzomi, “Silica triflate as an efficient catalyst for the solvent-free synthesis of 3,4-dihydropyrimidin-2(1H)-ones,” Arkivoc, vol. 2007, no. 1, pp. 51–57, 2007. View at Google Scholar · View at Scopus
  36. F. Shirini, M. A. Zolfigol, and A. R. Abri, “Fe(HSO4)3 as an efficient catalyst for the preparation of 3,4-dihydropyrimidin-2(1H)-ones in solution and under solvent-free conditions,” Journal of the Iranian Chemical Society, vol. 5, no. 1, pp. 96–99, 2008. View at Publisher · View at Google Scholar
  37. F. Shirini, M. A. Zolfigol, and E. Mollarazi, “Solvent-free synthesis of 3,4-dihydropyrimidin-2(1H)-ones using trichloroisocyanuric acid,” Letters in Organic Chemistry, vol. 2, no. 8, pp. 718–720, 2005. View at Publisher · View at Google Scholar · View at Scopus
  38. A. Debache, M. Amimour, A. Belfaitah, S. Rhouati, and B. Carboni, “A one-pot Biginelli synthesis of 3,4-dihydropyrimidin-2-(1H)-ones/thiones catalyzed by triphenylphosphine as Lewis base,” Tetrahedron Letters, vol. 49, no. 42, pp. 6119–6121, 2008. View at Publisher · View at Google Scholar · View at Scopus
  39. S. Chitra and K. Pandiarajan, “Calcium fluoride: an efficient and reusable catalyst for the synthesis of 3,4-dihydropyrimidin-2(1H)-ones and their corresponding 2(1H)thione: an improved high yielding protocol for the Biginelli reaction,” Tetrahedron Letters, vol. 50, no. 19, pp. 2222–2224, 2009. View at Publisher · View at Google Scholar · View at Scopus
  40. S. L. Jain, J. K. Joseph, and B. Sain, “Ionic liquid promoted an improved synthesis of 3,4-dihydropyrimidinones using [bmim]BF4 immobilized Cu (II) acetylacetonate as recyclable catalytic system,” Catalysis Letters, vol. 115, no. 1-2, pp. 52–55, 2007. View at Publisher · View at Google Scholar
  41. A. N. Dadhania, V. K. Patel, and D. K. Raval, “A convenient and efficient protocol for the one pot synthesis of 3,4-Dihydropyrimidin-2-(1H)-ones catalyzed by ionic liquids under ultrasound irradiation,” The Journal of the Brazilian Chemical Society, vol. 22, no. 3, p. 511, 2011. View at Publisher · View at Google Scholar
  42. F. Shirini, M. A. Zolfigol, and J. Albadi, “Melamine trisulfonic acid: a new, efficient and recyclable catalyst for the synthesis of 3,4-dihydropyrimidin-2(1H)-ones/thiones in the absence of solvent,” Chinese Chemical Letters, vol. 22, no. 3, pp. 318–321, 2011. View at Publisher · View at Google Scholar · View at Scopus
  43. H. Shi, W. Zhu, H. Li et al., “Microwave-accelerated esterification of salicylic acid using Brönsted acidic ionic liquids as catalysts,” Catalysis Communications, vol. 11, no. 7, pp. 588–591, 2010. View at Publisher · View at Google Scholar
  44. J. S. Wilkes, “Properties of ionic liquid solvents for catalysis,” Journal of Molecular Catalysis A, vol. 214, no. 1, pp. 11–17, 2004. View at Publisher · View at Google Scholar
  45. H. Wu, Y. Wan, X. M. Chen et al., “Synthesis of 2,4,5-triaryl-5H-chromeno[4,3-b]pyridines under microwave radiation,” Journal of Heterocyclic Chemistry, vol. 46, no. 4, pp. 702–707, 2009. View at Publisher · View at Google Scholar · View at Scopus