About this Journal Submit a Manuscript Table of Contents
Journal of Chemistry
Volume 2013 (2013), Article ID 179013, 5 pages
http://dx.doi.org/10.1155/2013/179013
Research Article

A Fast, Highly Efficient, and Green Protocol for Synthesis of Biscoumarins Catalyzed by Silica Sulfuric Acid Nanoparticles as a Reusable Catalyst

Department of Chemistry, Yazd Branch, Islamic Azad University, P.O. Box 89195-155, Yazd 8916871967, Iran

Received 13 May 2013; Accepted 11 July 2013

Academic Editor: Christophe Len

Copyright © 2013 Bahareh Sadeghi and Tayebe Ziya. 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

Silica sulfuric acid nanoparticles have been prepared and shown to efficiently catalyse the reaction between an aromatic aldehyde or phenylglyoxal and a 4-hydroxycoumarin at reflux in EtOH to afford the biscoumarin derivatives in high yield.

1. Introduction

A variety of biological activities are associated with coumarins and biscoumarins, for example, anticoagulants and antianthelmintic and antifungal activities [13]. Furthermore, these compounds can be complexed with rare earth metals as anti-HIV agents [4]. The synthesis of biscoumarins has been reported in the presence of piperidine [5], molecular iodine [6], tetrabutylammonium bromide [7], [bmim]BF4 [8], sodium dodecyl sulfate [9], SO3H-functionalized ionic liquid [10], and [MIM(CH2)4SO3H][HSO4] [11].

In this paper, we report a simple and efficient method for synthesis of biscoumarin derivatives using different aromatic aldehydes and phenylglyoxals and 4-hydroxycoumarin in the presence of silica sulfuric acid nanoparticles under reflux in ethanol. The catalyst is recyclable with reproducible results without any loss of its activity. The morphology of the silica sulfuric acid nanoparticles was observed using a scanning electron microscope (SEM).

2. Experimental

2.1. General

IR spectra were recorded on a Shimadzu IR-470 spectrometer in KBr discs. The NMR spectra were obtained on a Bruker Avance DRX-500 FT spectrometer (1H NMR at 500 Hz, 13C NMR at 125 Hz) using CDCl3 as solvent with TMS as internal standard. Melting points were determined with an Electrothermal 9100 apparatus. Elemental analyses were performed using a Costech ECS 4010 CHNS-O analyzer at Analytical Laboratory of Science and Researches Unit of Islamic Azad University. The morphology of the catalyst was observed using an SEM model VEGA//TESCAN with an accelerating voltage of 15 kV. The chemicals used in this work were purchased from Sigma Aldrich and Fluka (Buchs, Switzerland) and were used without further purification.

2.2. Synthesis of  Silica Sulfuric Acid Nanoparticles

The reagent was prepared by combination of chlorosulfonic acid (23.3 g) drop by drop over 10 min via a syringe to nanosilica gel powder (60 g) in a 100 mL flask at 0°C. The reaction mixture was then stirred, and then after 30 min, the white powder was separated. The dimensions of nanoparticles were observed with SEM (Figure 1). The size of particles is between 28 and 32 nm.

179013.fig.001
Figure 1: The SEM images of SiO2-OSO3H NPs.
2.3. General Procedure for the Synthesis of Biscoumarin

A mixture of 4-hydroxycoumarin (2 mmol), aromatic aldehyde or arylglyoxal (1 mmol), SiO2-OSO3H NPs (0.003 g), and EtOH (5 mL) was placed in a round bottom flask. The materials were mixed and refluxed for 20 min. The progress of the reaction was followed by TLC (n-hexane:ethylacetate). After completion of the reaction, the mixture was filtered to remove the catalyst. By evaporation of the solvent, the crude product was recrystallized from hot ethanol to obtain the pure compound.

2.4. Selected Spectral Data

3,3′-Bis (4-hydroxy coumarin-3yl) (3-nitro-4-chlorophenyl) methane (4m). IR (KBr) : 3450, 3015, 1664, 1603, 1561, 1348, 761 cm−1. 1H NMR (500 MHz, CDCl3): δ 6.3 ( , 1H, CH), 7.27 ( , 2H,  Hz, aromatic), 7.34 ( , 2H,  Hz, aromatic), 7.48 ( , 1H,  Hz, aromatic), 7.55–7.59 ( , 3H, aromatic), 7.79 ( , 1H, aromatic), 7.88 ( , 2H,  Hz, aromatic), 12.3 (broad , 2H, OH) ppm. 13C NMR (125 MHz, CDCl3): δ 36.9, 104.1, 116.8, 118.9, 122.6, 124.6, 131.7, 132.7, 133.3, 143.4, 148.5, 153.2, 165.2, 166.6 ppm. Anal. Calcd. For C25H14ClNO8: C, 61.03; H, 2.83; N, 2.83 Found: C, 61.02; H, 2.87; N, 2.85.

3,3′-Bis (4-hydroxy coumarin-3yl) (2,4-dichlorophenyl) methane (4n). IR (KBr) : 3485, 3085, 1664, 1603, 766 cm−1. 1H NMR (500 MHz, CDCl3): δ 6.1 ( , 1H, CH), 7.26 ( , 2H,  Hz,  Hz, aromatic), 7.39 ( , 2H, .1 Hz,  Hz, aromatic), 7.41 ( , 2H, Hz, aromatic), 7.43 ( , 1H, aromatic), 7.66 ( , 2H,  Hz,  Hz, aromatic), 8.05 ( , 2H, Hz, aromatic), 11.68 (broad , 2H, OH) ppm. 13C NMR (125 MHz, CDCl3): δ 31.9, 102.1, 114.2, 119.1, 121.4, 123.7, 130.3, 132.9, 133.3, 135.8, 143.5, 152.1, 165.9, 167.1 ppm. Anal. Calcd. For C25H14Cl2O6: C, 62.38; H, 2.93 Found: C, 62.32; H, 2.79.

3,3′-Bis (4-hydroxy coumarin-3yl) (4-nitrophenyl) ethanon (5a). IR (KBr) : 3355, 3015, 1696, 1664, 1547, 1357, 754 cm−1. 1H NMR (500 MHz, CDCl3): δ 6.4 ( , 1H, CH), 7.34 ( , 2H,  Hz,  Hz, aromatic), 7.36 ( , 2H, aromatic), 7.58 ( , 2H,  Hz,  Hz, aromatic), 7.78 ( , 2H, aromatic), 7.91 ( , 2H,  Hz, aromatic), 8.29 ( , 2H,  Hz, aromatic), 11.3 (broad , 2H, OH) ppm. 13C NMR (125 MHz, CDCl3): δ 80.2, 104.1, 115.7, 119.2, 121.7, 124.2, 128.4, 130.2, 132.9, 142.1, 153.7, 158.2, 162.9, 167.2, 198.0 ppm. Anal. Calcd. For C26H15NO9: C, 64.33; H, 3.11; N, 2.88 Found: C, 64.21; H, 3.04; N, 2.85.

3,3′-Bis (4-hydroxy coumarin-3yl) (4-bromophenyl) ethanon (5b). IR (KBr) : 3335, 3085, 1696, 1648, 759 cm−1. 1H NMR (500 MHz, CDCl3): δ 6.31 ( , 1H, CH), 7.24 ( , 2H,  Hz, aromatic), 7.27 ( , 2H,  Hz, aromatic), 7.5 ( , 2H,  Hz, aromatic), 7.58 ( , 2H,  Hz, aromatic), 7.71 ( , 2H,  Hz, aromatic), 7.84 ( , 2H,  Hz, aromatic), 10.41 (broad , 2H, OH) ppm. 13C NMR (125 MHz, CDCl3): δ 80.0, 102.5, 116.7, 119.0, 121.6, 124.2, 124.7, 130.2, 132.0, 132.4, 153.1, 164.3, 167.2, 165.2, 196.5 ppm. Anal. Calcd. For C26H15BrO7: C, 60.13; H, 2.91 Found: C, 60.08; H, 2.89.

3,3′-Bis (4-hydroxy coumarin-3yl) (phenyl) ethanon (5c). IR (KBr) : 3405, 3015, 1692, 1637, 764 cm−1. 1H NMR (500 MHz, CDCl3): δ 6.35 ( , 1H, CH), 7.29 ( , 2H,  Hz,  Hz, aromatic), 7.35 ( , 3H, aromatic), 7.47 ( , 2H,  Hz, aromatic), 7.57 ( , 2H, aromatic), 7.71 ( , 2H, aromatic), 7.82 ( , 2H,  Hz, aromatic), 10.41 (broad , 2H, OH) ppm. 13C NMR (125 MHz, CDCl3): δ 80.3, 101.9, 115.5, 118.7, 121.0, 124.3, 129.7, 130.1, 131.8, 133.2, 136.2, 151.3, 161.8, 167.4, 194.2 ppm. Anal. Calcd. For C26H16O7: C, 70.9; H, 3.66 Found: C, 70.7; H, 3.59.

3. Results and Discussion

In continuation of our investigations of the application of solid acids in organic synthesis [1216], we have investigated the synthesis of biscoumarin derivatives by condensation of  a 4-hydroxycoumarin 1 and an aromatic aldehyde 2 or phenylglyoxals 3 in the presence of 0.003 g SiO2-OSO3H NPs catalyst.

The stable silica gel nanoparticles are easily prepared [17] and used for preparation of catalyst (SiO2-OSO3H NPs).

To optimize the reaction conditions, the reaction of benzaldehyde and 4-hydroxycoumarin was used as a model reaction. Initially, the catalytic activity of SiO2-OSO3H NPs has been compared with other catalysts, according to the obtained data, and this catalyst afforded good yields; however, it has limitations of long reaction time, harsh reaction conditions, and often expensive catalysts (Table 1, entry 1–6). In order to determine the optimum quantity of SiO2-OSO3H NPs, model reaction was carried out at reflux in ethanol condition (Table 1, entry 7–9). SiO2-OSO3H NPs (0.003 g) gave an excellent yield in 20 min (Table 1, entry 8). The previous reaction was also examined in various solvents. The best results were obtained when EtOH was used as a solvent at reflux (Table 1, entry 8). An interesting feature of this method is that the reagent can be regenerated at the end of the reaction and can be used several times without losing its activity. To recover the catalyst, after completion of the reaction, the mixture was filtered, and catalyst was washed with CHCl3, and then the solid residue dries. This process was repeated for two cycles, and the yield of product 4a did not change significantly (Table 1, entry 12, 13).

tab1
Table 1: Synthesis of 4a under various conditions.

To study the scope of the reaction, a series of aromatic aldehydes or phenylglyoxals and 4-hydroxycoumarin catalysed by SiO2-OSO3H NPs were examined (Scheme 1). The results are shown in Table 2. In all cases, aromatic aldehyde or phenylglyoxals substituted with either electron-donating or electron-withdrawing groups underwent the reaction smoothly and gave products in excellent yields.

tab2
Table 2: SiO2-OSO3H NPs catalyzed the synthesis of biscoumarin derivatives.
179013.sch.001
Scheme 1: Synthesis of biscoumarins by condensation of 4-hydroxycoumarin with an aromatic aldehyde or phenylglyoxals using SiO2-OSO3H NPs as catalyst.

The compounds 4a–l were characterised by their 1H-NMR and IR spectroscopies and elemental analyses. Spectral data were compared with the literature data [5, 9, 11].

Compounds 4m, n and 5a–c were new, and their structures were deduced by elemental and spectral analysis. The 1H-NMR spectrum of compound 5a exhibited proton of methine at 6.4 ppm, and OH proton is observed at 11.3 ppm which disappears after addition of some D2O to the CDCl3 solution of 5a. There are observed multiplets between 7.34 and 8.29 ppm which are related to aromatic protons. The 13C-NMR spectrum of compound 5a showed 15 signals in agreement with the proposed structure. The IR spectrum of compound 5a also supported the suggested structure.

4. Conclusion

In summary, we have reported an easy and efficient protocol for the synthesis of biscoumarins in the easily accessible SiO2-OSO3H nanoparticles. The method offers marked improvement with its operational simplicity and short reaction time and affords excellent yield. The solid phase acidic catalyst was reusable for a number of times without appreciable loss of activity. The present method does not involve any hazardous organic solvent. Therefore, this procedure could be classified as green chemistry.

Acknowledgment

The authors gratefully acknowledge the financial support from the Research Council of Islamic Azad University of Yazd.

References

  1. J. H. Lee, H. B. Bang, S. Y. Han, and J.-G. Jun, “An efficient synthesis of (+)-decursinol from umbelliferone,” Tetrahedron Letters, vol. 48, no. 16, pp. 2889–2892, 2007. View at Publisher · View at Google Scholar · View at Scopus
  2. R. D. R. S. Manian, J. Jayashankaran, and R. Raghunathan, “A rapid access to indolo[2,1-a]pyrrolo[4′,3′:4,5]pyrano[5,6-c]coumarin/[6,5-c]chromone derivatives by domino Knoevenagal intramolecular hetero Diels-Alder reactions,” Tetrahedron Letters, vol. 48, no. 8, pp. 1385–1389, 2007. View at Publisher · View at Google Scholar · View at Scopus
  3. H. Zhao, N. Neamati, H. Hong et al., “Coumarin-based inhibitors of HIV integrase,” Journal of Medicinal Chemistry, vol. 40, no. 2, pp. 242–249, 1997. View at Publisher · View at Google Scholar · View at Scopus
  4. I. Manolov, S. Raleva, P. Genova et al., “Antihuman immunodeficiency virus type 1 (HIV-1) activity of rare earth metal complexes of 4-hydroxycoumarins in cell culture,” Bioinorganic Chemistry and Applications, vol. 2006, Article ID 71938, 7 pages, 2006. View at Publisher · View at Google Scholar · View at Scopus
  5. K. M. Khan, S. Iqbal, M. A. Lodhi et al., “Biscoumarin: new class of urease inhibitors; Economical synthesis and activity,” Bioorganic and Medicinal Chemistry, vol. 12, no. 8, pp. 1963–1968, 2004. View at Publisher · View at Google Scholar · View at Scopus
  6. M. Kidwai, V. Bansal, P. Mothsra et al., “Molecular iodine: a versatile catalyst for the synthesis of bis(4-hydroxycoumarin) methanes in water,” Journal of Molecular Catalysis A, vol. 268, no. 1-2, pp. 76–81, 2007. View at Publisher · View at Google Scholar · View at Scopus
  7. J. M. Khurana and S. Kumar, “Tetrabutylammonium bromide (TBAB): a neutral and efficient catalyst for the synthesis of biscoumarin and 3,4-dihydropyrano[c]chromene derivatives in water and solvent-free conditions,” Tetrahedron Letters, vol. 50, no. 28, pp. 4125–4127, 2009. View at Publisher · View at Google Scholar · View at Scopus
  8. J. M. Khurana and S. Kumar, “Ionic liquid: an efficient and recyclable medium for the synthesis of octahydroquinazolinone and biscoumarin derivatives,” Monatshefte fur Chemie, vol. 141, no. 5, pp. 561–564, 2010. View at Publisher · View at Google Scholar · View at Scopus
  9. H. Mehrabi and H. Abusaidi, “Synthesis of biscoumarin and 3,4-dihydropyrano[c]chromene derivatives catalysed by sodium dodecyl sulfate (SDS) in neat water,” Journal of the Iranian Chemical Society, vol. 7, no. 4, pp. 890–894, 2010. View at Scopus
  10. W. Li, Y. Wang, Z. Wang, L. Dai, and Y. Wang, “Novel SO3H-functionalized ionic liquids based on benzimidazolium cation: efficient and recyclable catalysts for one-pot synthesis of biscoumarin derivatives,” Catalysis Letters, vol. 141, no. 11, pp. 1651–1658, 2011. View at Publisher · View at Google Scholar · View at Scopus
  11. N. Tavakoli-Hoseini, M. M. Heravi, F. F. Bamoharram, A. Davoodnia, and M. Ghassemzadeh, “An unexpected tetracyclic product isolated during the synthesis of biscoumarins catalyzed by [MIM(CH2)4SO3H] [HSO4]: characterization and X-ray crystal structure of 7-(2-hydroxy-4-oxo-4H-chromen-3-yl)-6H,7H-chromeno[4,3-b]chromen-6-one,” Journal of Molecular Liquids, vol. 163, no. 3, pp. 122–127, 2011. View at Publisher · View at Google Scholar · View at Scopus
  12. B. Sadeghi, A. Hassanabadi, and S. Bidaki, “Synthesis of nanoparticles silica supported sulfuric acid (NPs SiO2-H2SO4): a solid phase acidic catalyst for one-pot synthesis of 4H-chromene derivatives,” Journal of Chemical Research, vol. 35, no. 11, pp. 666–668, 2011. View at Publisher · View at Google Scholar · View at Scopus
  13. M. Khazaei, M. Anary-Abbasinejad, A. Hassanabadi, and B. Sadeghi, “ZnO nanoparticles: an efficient reagent, simple and one-pot procedure for synthesis of highly functionalized dihydropyridine derivatives,” E-Journal of Chemistry, vol. 9, no. 2, pp. 615–620, 2012. View at Publisher · View at Google Scholar · View at Scopus
  14. B. Sadeghi, A. Namakkoubi, and A. Hassanabadi, “BF3.SiO2 nanoparticles: a solid phase acidic catalyst for efficient one-pot Hantzsch synthesis of 1,4-dihydropyridines,” Journal of Chemical Research, vol. 37, pp. 11–13, 2013.
  15. B. Sadeghi, S. Zavar, and A. Hassanabadi, “Monolayer-protected silver nanoparticles: an efficient and versatile reagent for the synthesis of 3,4-dihydropyrimidine-2-(1H)-ones (thiones),” Journal of Chemical Research, vol. 36, pp. 343–346, 2012.
  16. B. Sadeghi and M. Ghasemi Nejad, “Silica sulfuric acid: an eco-friendly and reusable catalyst for synthesis of benzimidazole derivatives,” Journal of Chemistry, vol. 2013, Article ID 581465, 5 pages, 2013. View at Publisher · View at Google Scholar
  17. K. Lee, A. N. Sathyagal, and A. V. McCormick, “A closer look at an aggregation model of the Stober process,” Colloids and Surfaces A, vol. 144, no. 1–3, pp. 115–125, 1998. View at Publisher · View at Google Scholar · View at Scopus