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Synlett 2012; 23(9): 1379-1383
DOI: 10.1055/s-0031-1290955
letter
© Georg Thieme Verlag Stuttgart · New York

A New Three-Component Reaction Catalyzed by Silica Sulfuric Acid: Synthesis of Tetrasubstituted Pyrroles

Fatemeh Tamaddon*
Department of Chemistry, Yazd University, Yazd, 89195-741, Iran, Fax: +98(351)8210664   Email: ftamaddon@yazduni.ac.ir
,
Mahnaz Farahi
Department of Chemistry, Yazd University, Yazd, 89195-741, Iran, Fax: +98(351)8210664   Email: ftamaddon@yazduni.ac.ir
› Author Affiliations
Further Information

Publication History

Received: 19 November 2011

Accepted after revision: 23 March 2012

Publication Date:
10 May 2012 (online)

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Abstract

A novel, convenient, and efficient three-component reaction of benzoin derivatives, 1,3-dicarbonyls, and ammonium acetate in the presence of silica sulfuric acid (SSA) is described for the synthesis of 2,3,4,5-tetrasubstituted pyrroles under solvent-free conditions.

Key words

three-component reaction - silica sulfuric acid (SSA) - benzoin - 2,3,4,5-tetrasubstituted pyrroles - 1,3-dicarbonyls

Supporting Information

    for this article is available online at http://www.thieme-connect.com/ejournals/toc/synlett.
  • Supporting Information
 

  • References and Notes

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  • 28 Chemicals were purchased from Aldrich, Fluka, and Merck chemical companies and freshly used without purification. The products were isolated and identified by their physical and spectral data. IR spectra were recorded on FT-IR JASCO-680 using KBr disks. The 1H NMR spectra were recorded on a Bruker instrument 400 MHz ultrashield model as CDCl3 and DMSO-d 6 solutions. Preparation of Silica Sulfuric Acid21 A 500 mL suction flask equipped with a constant-pressure dropping funnel and a gas inlet tube for conducting HCl gas over an adsorbing solution (i.e., H2O) was used. It was charged with silica gel (60.0 g). Chlorosulfonic acid (23.3 g, 0.2 mol) was added dropwise over a period of 30 min at r.t. HCl gas evolved from the reaction vessel immediately. After the addition was completed the mixture was shaken for 30 min. A white solid (SSA) 76.0 g was obtained
  • 29 General Experimental Procedure for the Synthesis of Tetrasubstituted Pyrroles A mixture of benzoin derivative (1 mmol), 1,3-dicarbonyl compound (1 mmol), NH4OAc (2 mmol), and SSA (0.02 g) was stirred at 80 °C under solvent-free conditions. The progress of the reaction was monitored by TLC (hexane–EtOAc = 8:2). After completion of the reaction, the obtained mixture was diluted with EtOAc (10 mL) and filtered to remove the catalyst. The filtrate was washed with aq 5% NaHCO3, dried over Na2SO4, and evaporated. The resulting product was purified in some cases by crystallization from H2O–EtOH (30:70) to afford pure product
  • 30 Selected Characterization Data 1-(2-Methyl-4,5-diphenyl-1H-pyrrol-3-yl)ethanone (Table 3, Entry 1) Pale yellow needles; mp 170–171 °C. IR (KBr): νmax = 3177, 1635, 1602, 1579, 767, 698 cm–1. 1H NMR (400 MHz, DMSO-d 6): δ = 1.72 (s, 3 H, CH3), 2.46 (s, 3 H, CH3), 7.10–7.36 (m, 10 H), 11.61 (s, 1 H, NH) ppm. 13C NMR (100 MHz, DMSO-d 6): δ = 14.32, 30.96, 79.64, 122.53, 122.58, 126.53, 127.03, 127.33, 128.61, 128.76, 131.22, 132.65, 135.74, 137.57, 194.95 ppm. Anal. Calcd (%) for C19H17NO: C, 82.88; H, 6.22; N, 5.09. Found: C, 82.74; H, 6.19. Ethyl 2-Methyl-4,5-diphenyl-1H-pyrrole-3-carboxylate (Table 3, Entry 2) Pale yellow solid; mp 205–206 °C. IR (KBr): νmax = 3310, 1676, 1599, 766, 697 cm–1. 1H NMR (400 MHz, DMSO-d 6): δ = 0.93 (t, J = 6.4 Hz, 3 H, OCH2CH3), 2.49 (s, 3 H, CH3), 3.91 (q, J = 6.4 Hz, 2 H, OCH2CH3), 7.11–7.24 (m, 10 H), 11.56 (s, 1 H, NH) ppm. 13C NMR (100 MHz, DMSO-d 6): δ = 13.69, 14.27, 58.76, 111.91, 123.02, 126.48, 127.18, 127.33, 127.88, 128.58, 131.12, 132.71, 136.26, 137.14, 165.11 ppm. Anal. Calcd (%) for C20H19NO3: C, 74.75; H, 5.96; N, 4.36; O, 14.94. Found: C, 74.50; H, 5.90. Methyl 2-Methyl-4,5-diphenyl-1H-pyrrole-3-carboxylate (Table 3, Entry 3) Pale yellow needles; mp 177–179 °C. IR (KBr): νmax = 3340, 1681, 1598, 1522, 756, 696 cm–1. 1H NMR (400 MHz, DMSO-d 6): δ = 2.47 (s, 3 H, CH3), 3.45 (s, 3 H, OCH3), 7.07–7.24 (m, 10 H), 11.58 (s, 1 H, NH) ppm. 13C NMR (100 MHz, DMSO-d 6): δ = 13.81, 50.48, 111.57, 123.02, 126.56, 127.32, 127.57, 127.95, 128.59, 130.08, 131.08, 132.67, 136.30, 136.89, 165.53 ppm. Anal. Calcd (%) for C19H17NO2: C, 78.33; H, 5.88; N, 4.81; O, 10.98. Found: C, 78.25; H, 5.82. (2-Methyl-4,5-diphenyl-1H-pyrrol-3yl)(phenyl)-methanone (Table 3, Entry 4) Yellow needles; mp 221–223 °C. IR (KBr): νmax = 3289, 1610, 1576, 1522, 740, 696 cm–1. 1H NMR (400 MHz, DMSO-d 6): δ = 2.24 (s, 3 H, CH3), 6.94–7.48 (m, 15 H), 11.65 (s, 1 H, NH) ppm. 13C NMR (100 MHz, DMSO-d 6): δ = 11.11, 121.49, 122.52, 126.16, 126.80, 127.31, 127.65, 128.10, 128.19, 128.70, 129.37, 130.74, 131.79, 132.73, 134.55, 136.08, 140.27, 193.27 ppm. Anal. Calcd (%) for C24H19NO: C, 85.43; H, 5.68; N, 4.15; O, 4.74. Found: C, 85.22; H, 5.59. 1-[4,5-Bis(4-chlorophenyl)-2-methyl-1H-pyrrol-3-yl]ethanone (Table 3, Entry 7) White crystals; mp 234–235 °C. IR (KBr): νmax = 3195, 1631, 1576, 1523, 1445, 829, 798 cm–1. 1H NMR (400 MHz, DMSO-d 6): δ = 1.82 (s, 3 H, CH3), 3.33 (s, 3 H, CH3), 7.08–7.40 (m, 8 H), 11.73 (s, 1 H, NH) ppm. 13C NMR (100 MHz, DMSO-d 6): δ = 14.35, 31.10, 121.61, 122.45, 126.21, 128.80, 128.82, 131.17, 131.39, 132.14, 132.93, 136.06, 136.16, 194.50 ppm. Anal. Calcd (%) for C19H15Cl2NO: C, 66.29; H, 4.39; Cl, 20.60; N, 4.07; O, 4.65. Found: C, 66.05; H, 4.25. Ethyl 4,5-Bis(4-chlorophenyl)-2-methyl-1H-pyrrole-3-carboxylate (Table 3, Entry 8) Pale yellow needles; mp 155–156 °C. IR (KBr): νmax = 3286, 1672, 1498, 1481, 831, 732 cm–1. 1H NMR (400 MHz, CDCl3): δ = 1.09 (t, J = 7.2 Hz, 3 H, OCH2CH3), 2.58 (s, 3 H, CH3), 4.09 (q, J = 7.2 Hz, 2 H, OCH2CH3), 6.99–7.26 (m, 8 H), 8.66 (s, 1 H, NH) ppm. 13C NMR (100 MHz, CDCl3): δ = 13.89, 14.04, 59.45, 112.36, 122.46, 126.50, 127.92, 128.11, 128.73, 130.38, 132.08, 132.47, 134.28, 136.15, 165.50 ppm. Anal. Calcd (%) for C20H17Cl2NO2: C, 64.18; H, 4.58; Cl, 18.95; N, 3.74; O, 8.55. Found: C, 63.96; H, 4.31. Methyl 4,5-Bis(4-chlorophenyl)-2-methyl-1H-pyrrole-3-carboxylate (Table 3, Entry 9) White crystals; mp 212–213 °C. IR (KBr): νmax = 3330, 1685, 1524, 1499 cm–1. 1H NMR (400 MHz, DMSO-d 6): δ = 3.33 (s, 3 H, CH3), 3.49 (s, 3 H, OCH3), 7.07–7.31 (m, 8 H), 11.80 (s, 1 H, NH) ppm. 13C NMR (100 MHz, DMSO-d 6): δ = 13.79, 50.66, 111.53, 122.04, 126.63, 128.15, 128.83, 129.01, 131.13, 131.46, 131.87, 132.81, 135.38, 136.82, 165.26 ppm. Anal. Calcd (%) for C19H15Cl2NO2: C, 63.35; H, 4.20; Cl, 19.68; N, 3.89; O, 8.88. Found: C, 63.22; H, 4.38. [4,5-Bis(4-chlorophenyl)-2-methyl-1H-pyrrol-3-yl](phenyl)methanone (Table 3, Entry 10) Yellow solid; mp 247–249 °C. IR (KBr): νmax = 3304, 1617, 1595, 1498, 831, 699 cm–1. 1H NMR (400 MHz, DMSO-d 6): δ = 2.21 (s, 3 H, CH3), 7.18–7.48 (m, 13 H), 11.85 (s, 1 H, NH) ppm. 13C NMR (100 MHz, DMSO-d 6): δ = 13.21, 121.67, 126.42, 128.28, 128.36, 128.92, 129.31, 131.05, 131.58, 131.97, 132.36, 134.71, 135.11, 140.15, 192.98 ppm. Anal. Calcd (%) for C24H17Cl2NO: C, 70.95; H, 4.22; Cl, 17.45; N, 3.45; O, 3.94. Found: C, 70.78; H, 4.37