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Synlett 2014; 25(08): 1127-1131
DOI: 10.1055/s-0033-1340986
letter
© Georg Thieme Verlag Stuttgart · New York

Amberlyst A26 OH as a Recyclable Catalyst for Hydration of Nitriles and ­Water-Based Synthesis of 4(1H)-Quinazolinones from 2-Aminobenzonitrile and Carbonyl Compounds

Fatemeh Tamaddon*
Department of Chemistry, Faculty of Science, Yazd University, Yazd 89195-741, Iran   Fax: +98(351)8210644   eMail: ftamaddon@yazduni.ac.ir
,
Farzaneh Pouramini
Department of Chemistry, Faculty of Science, Yazd University, Yazd 89195-741, Iran   Fax: +98(351)8210644   eMail: ftamaddon@yazduni.ac.ir
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Publikationsverlauf

Received: 22. Dezember 2013

Accepted after revision: 19. Februar 2014

Publikationsdatum:
18. März 2014 (online)

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Abstract

Selective hydration of nitriles to primary amides as well the base-catalyzed synthesis of 2-substituted 4(1H)-quinazolinones via reaction of 2-aminobenzonitrile with carbonyl compounds using macroporous Amberlyst A26 OH in H2O–EtOH is described. The latter reaction proceeds via tandem hydration of 2-aminobenzonitrile, condensation of the in situ generated 2-aminobenzamide with carbonyl compounds, and cyclization of the imine intermediate to give the quinazolinone derivatives.

Key words

hydration - nitriles - amides - quinazolinones - Amberlyst A26 OH - recyclable catalyst
 

  • References and Notes

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  • 23 General Procedure for the Synthesis of 2-Substituted 2,3-dihydro-4(1H)-quinazolinones Amberlyst A26 OH (0.11 g) was added to a solution of 2-aminobenzonitrile (1 mmol) and the requisite benzaldehyde (1 mmol) in EtOH–H2O (0.5 mL). The reaction mixture was stirred at 50–60 °C for the specified period of time as indicated in Table 2, and the progress of the reaction was followed by TLC. After the completion reaction, the mixture was diluted with hot EtOH and filtered to remove the catalyst. The desired products were isolated by addition of H2O and filtration of the precipitate. To check the regenerability of Amberlyst A26 OH from the model reaction of 2-aminobenzonitrile with benzaldehyde, Amberlyst was removed after reaction completion by dispersing the reaction mixture in warm EtOH or EtOAc and filtering the reaction mixture. To remove impurities and regeneration of the filtered resin, it was washed with EtOAc, distilled H2O, and 0.1 M NaOH and dried at r.t.
  • 24 General Procedure for Synthesis of Primary Amides Amberlyst A26 OH (0.11 g) was added to a suspension of the nitrile (1 mmol) in EtOH–H2O (0.5 mL). The reaction mixture was stirred at 50–60 °C, and the progress of the reaction was followed by TLC. After the completion of reaction, the mixture was diluted with acetone or EtOAc and filtered to remove the catalyst. The desired products were isolated by evaporation of the EtOAc or addition of H2O and filtration of the precipitate. Selected Spectroanalytical Data for Products 2-(Phenyl)-2,3-dihydro-4(1H)-quinazolinone (Table 3, Entry 1) White solid; mp 219–222 °C; yield: 93%. FTIR (KBr): νmax = 3302 (NH), 3055 (CH), 1655 (C=O) cm–1. 1H NMR (500 MHz, CDCl3): δ = 4.40 (br s, 1 H, NH), 5.85 (br s, 1 H, CH), 6.60–6.70 (m, 2 H, Harom), 6.95–7.10 (m, 1 H, Harom), 7.20–7.38 (m, 4 H, Harom), 7.58–7.78 (m, 2 H, Harom), and 7.94 (d, J = 10 Hz, 1 H, NH) ppm. 13C NMR (125 MHz, CDCl3): δ = 72.5, 119.5, 119.8, 122.6, 132.1, 132.5, 132.6, 132.8, 138.5, 145.8, 152.9, 169.6 ppm. 2-(Pyridin-3′-yl)-2,3-dihydroquinazolin-4(1H)-one (Table 3, Entry 11) White solid; mp 189–192 °C (lit.3a 190–192 °C); yield: 92%. FTIR (KBr): νmax = 3310 (NH), 3065 (CH), 1660 (C=O), 1612 cm–1. 1H NMR (500 MHz, CDCl3): δ = 5.90 (s, 1 H, NH), 6.65 (d, J = 8.0 Hz, 1 H, CH), 6.81 (t, J = 7.9 Hz, 1 H, Harom), 7.23–7.38 (m, 3 H, Harom), 7.77 (dd, J 1 = 7.8 Hz, J 2 = 1.5 Hz, 1 H), 7.93–7.99 (m, 1 H, NH), 8.53 (dd, J 1 = 4.8 Hz, J 2 = 1.5 Hz, 1 H), 8.6 (s, 1 H) ppm. 13C NMR (125 MHz, CDCl3): δ = 69.5, 117.5, 118.7, 119.8, 122.6, 128.5, 131.6, 138.2, 139.5, 140.8, 151.5, 151.9, 153.9, 169.6 ppm. 1′H-Spiro[cyclohexane-1,2′-quinazolin]-4′(3′H)-one White solid; mp 225–227 °C; yield: 90%. FTIR (KBr): νmax = 3305 (NH), 3065 (CH), 1665 (C=O) cm–1. 1H NMR (500 MHz, CDCl3): δ = 1.48–1.68 (m, 6 H), 1.85 (br s, 4 H), 4.40 (br s, 1 H, NH), 6.43 (s, 1 H, NH), 6.66 (d, J = 5.2 Hz, 1 H), 6.82 (t, J = 5.2 Hz, 1 H), 7.28–7.35 (m, 1 H), 7.87 (dd, J 1 = 7.5 Hz, J 2 = 1.0 Hz, 1 H) ppm. 13C NMR (125 MHz, CDCl3): δ = 24.0, 26.8, 39.7, 70.5, 117.0, 119.0, 120.8, 130.4, 136.2, 148, 167.0 ppm. Benzamide (Table 4, Entry 3) White crystals; mp 129–131 °C (lit.25a 129 °C); yield: 91%. FTIR (neat): νmax = 3369, 3171, 1657 cm–1. 1H NMR (250 MHz, CDCl3): δ = 6.15 (s, NH2, 2 H), 7.46 (t, J = 6.0 Hz, 1 H), 7.55 (t, J = 6.0 Hz, 2 H), 7.83 (d, J = 6.0 Hz, 2 H, Ph) ppm. Nicotinamide (Table 4, Entry 6) White crystals; mp 129–131 °C (lit.25b 131 °C); yield: 94%. FTIR (neat): νmax = 3275, 3410, 1601 cm–1; 1H NMR (250 MHz, DMSO-d 6): δ = 7.47 (t, J = 5.0 Hz, 1H), 7.59 (s, 2 H, NH2), 8.18 (d, J = 5.0 Hz, 1 H), 8.67 (d, J = 5.0 Hz, 2 H, Ph), 9.00 (s, 1 H) ppm. 13C NMR (62.5 MHz, DMSO-d 6): δ = 123.9, 130.1, 135.6, 149.1, 152.3, 166.9 ppm.