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Synlett 2012; 23(15): 2209-2214
DOI: 10.1055/s-0032-1317014
letter
© Georg Thieme Verlag Stuttgart · New York

A Greener Protocol for Accessing 2,3-Dihydro/spiroquinazolin-4(1H)-ones: Natural Acid-SDS Catalyzed Three-Component Reaction

Rashmi Sharma
Division of Medicinal and Process Chemistry, CSIR Central Drug Research Institute, Lucknow 226001, India, Fax: +91(522)2623405   Email: prem_chauhan_2000@yahoo.com   Email: premsc58@hotmail.com
,
Anand Kumar Pandey
Division of Medicinal and Process Chemistry, CSIR Central Drug Research Institute, Lucknow 226001, India, Fax: +91(522)2623405   Email: prem_chauhan_2000@yahoo.com   Email: premsc58@hotmail.com
,
Prem M. S. Chauhan*
Division of Medicinal and Process Chemistry, CSIR Central Drug Research Institute, Lucknow 226001, India, Fax: +91(522)2623405   Email: prem_chauhan_2000@yahoo.com   Email: premsc58@hotmail.com
› Author Affiliations
Further Information

Publication History

Received: 13 April 2012

Accepted after revision: 09 July 2012

Publication Date:
14 August 2012 (online)

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Abstract

A novel green and energy-efficient synthesis of 2,3-dihydro/spiroquinazolin-4(1H)-ones via three-component cyclo­condensation reaction involving isatoic anhydride, amines and aldehydes/ketones utilizing recyclable tartaric acid–SDS catalyst system has been achieved. With simple requirements of mechanical stirring or mechanochemical activation at room temperature and one of the shortest reported times as of yet, it is a significant improvement on previously described methods for the synthesis of such compounds. Moreover the catalyst system can also be efficiently applied in large-scale reactions which indicates the potential for applications in industry.

Key words

2,3-dihydroquinazolin-4(1H)-one - mechanochemical activation - multicomponent reaction - sodium dodecyl sulfate (SDS) - tartaric acid
 

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  • 10 Representative Procedure: Method A: In a round-bottom flask, isatoic anhydride (0.1 g, 0.61 mmol) and amine (0.61 mmol) were dissolved in micellar solution of H2O–EtOH (3:1; 4 mL) sensitized with SDS (20 mol%). Tartaric acid (0.92 g, 0.61 mmol) and aldehyde/ketone (0.61 mmol) were then successively added and the reaction was allowed to stir at r.t. for an appropriate time indicated in Tables 2–4. The solid precipitate was filtered, washed with H2O, dried and could be used without further purification, however in case of 4r, 4s and 4t recrystallization with EtOH–ice was required. Method B: isatoic anhydride (0.1 g, 0.61 mmol) and amine (0.61 mmol) were mixed with a few drops of the solvent system (H2O–EtOH, 3:1) in a mortar. Tartaric acid (0.92 g, 0.61 mmol), SDS (20 mol%) and aldehyde/ketone (0.61 mmol) were then successively added and ground together with a pestle until completion of the reaction (Tables 2–4). In most of the cases the product was washed with H2O, however in case of 4r–t recrystallization with EtOH–ice was required. 3-Butyl-2-phenyl-2,3-dihydroquinazolin-4(1H)-one (4a): colorless solid; yield: 0.15 g (87%); mp 132–135 °C. 1H (300 MHz, CDCl3): δ = 7.88 (d, 1 H, J = 6.9 Hz), 7.21 (br s, 4 H), 7.13–7.19 (m, 2 H), 6.76 (t, 1 H, J = 7.3 Hz), 6.44 (d, 1 H, J = 8.0 Hz), 5.76 (s, 1 H), 3.85–3.94 (m, 1 H), 2.64–2.74 (m, 1 H), 1.45–1.49 (m, 2 H), 1.20–1.27 (m, 2 H), 0.80 (t, 3 H, J = 7.3 Hz).13C (50 MHz, CDCl3): δ = 163.2, 145.2, 140.0, 133.4, 129.2, 128.9, 128.4, 126.5, 119.1, 116.2, 114.4, 72.1, 44.6, 29.8, 20.2, 13.8. IR (KBr): 3360, 1634 cm–1. MS (ES+): m/z = 281.1 [M+ + 1]. HRMS (DART): m/z calcd for [C18H20N2O + H+]: 281.1654; found: 281.1647. 3-Butyl-2-ferrocenyl-2,3-dihydroquinazolin-4(1H)-one (4q): yellow solid; yield: 0.17 g (72%); mp 137–140 °C. 1H NMR (300 MHz, CDCl3): δ = 7.83 (d, 1 H, J = 7.4 Hz), 7.19–7.27 (m, 1 H), 6.79 (t, 1 H, J = 7.4 Hz), 6.64 (d, 1 H, J = 6.9 Hz), 5.40 (s, 1 H), 4.08–4.21 (m, 10 H), 3.75–3.79 (m, 1 H), 2.88–2.92 (m, 1 H), 1.42–1.50 (m, 2 H), 1.19–1.28 (m, 2 H), 0.82 (t, 3 H, J = 7.5 Hz). 13C NMR (50 MHz, CDCl3): δ = 162.7, 146.4, 133.3, 128.7, 119.3, 116.5, 113.9, 88.6, 73.3, 69.1, 68.81, 68.76, 68.6, 68.2, 66.3, 44.0, 30.1, 20.3, 14.0. IR (KBr): 3285, 1631 cm–1. MS (ES+) m/z = 389.0 [M+ + 1]. HRMS (DART): m/z calcd for [C22H24FeN2O + H+]: 389.1316; found: 389.1318. 2,3-Diphenyl-2,3-dihydroquinazolin-4(1H)-one (4t): colorless solid; yield: 0.14 g (74%); mp 212–214 ºC. 1H NMR (300 MHz, CDCl3): δ = 8.04 (d, 1 H, J = 7.8 Hz), 7.19–7.38 (m, 11 H), 6.92 (t, 1 H, J = 7.5 Hz), 6.65 (d, 1 H, J = 7.8 Hz), 6.11 (s, 1 H). 13C NMR (75 MHz, CDCl3 + CD3OD): δ = 165.6, 147.8, 142.1, 141.6, 135.8, 130.6, 130.5, 130.2, 128.7, 128.4, 120.5, 117.5, 116.5, 76.2. IR (KBr): 3327, 1649 cm–1. MS (ES+): m/z = 301.1 [M+ + 1]. HRMS (DART): m/z calcd for [C20H16N2O + H+]: 301.1335; found: 301.1333. 2-Phenyl-2,3-dihydroquinazolin-4(1H)-one (4u): colorless solid; yield: 0.12 g (89%); mp 218–220 ºC. 1H NMR (200 MHz, CDCl3): δ = 7.96 (d, 1 H, J = 8.1 Hz), 7.26–7.58 (m, 6 H), 6.94 (t, 1 H, J = 7.2 Hz), 6.69 (d, 1 H, J = 8.0 Hz), 5.90 (s, 1 H), 5.82 (s, 1 H, NH), 4.41 (s, 1 H, NH). 13C NMR (75 MHz, CDCl3): δ = 169.5, 152.9, 145.8, 138.4, 133.8, 133.3, 132.6, 132.0, 122.6, 119.8, 119.5, 72.5. IR (KBr): 3296, 3190, 1656 cm–1. MS (ES+): m/z = 225.0 [M+ + 1]. HRMS (DART): m/z calcd for [C14H12N2O + H+]: 225.1022; found: 225.1017. 1′H-Spiro[cyclohexane-1,2′-quinazolin]-4′(3′H)-one (4v): colorless solid; yield: 0.09 g (71%); mp 217–219 °C.1H NMR (200 MHz, CDCl3): δ = 7.89 (dd, 1 H, J 1 = 7.8 Hz, J 2 = 1.2 Hz), 7.28–7.33 (m, 1 H), 6.84 (t, 1 H, J = 7.5 Hz), 6.67 (d, 1 H, J = 7.8 Hz), 6.43 (s, 1 H, NH), 4.40 (s, 1 H, NH), 1.84 (br s, 4 H), 1.47–1.68 (m, 6 H). 13C NMR (75 MHz, CDCl3 + CD3OD): δ = 167.0, 148.0, 136.2, 130.3, 120.7, 117.0, 70.5, 39.7, 26.8, 24.0. IR (KBr): 3362, 3179, 1647 cm–1. MS (ES+): m/z = 217.0 [M+ + 1]. HRMS (DART): m/z calcd for [C13H16N2O + H+]: 217.1335; found: 217.1326. 1-Ethyl-1′H-spiro[indoline-3,2′-quinazoline]-2,4′(3′H)-dione (4x): tan solid; yield: 0.15 g (85%); mp 227–230 °C. 1H NMR (300 MHz, DMSO-d 6): δ = 8.29 (s, 1 H, NH), 7.62 (d, 1 H, J = 7.1 Hz), 7.52 (d, 1 H, J = 7.2 Hz), 7.42 (t, 1 H, J = 7.6 Hz), 7.18–7.25 (m, 2 H), 7.00–7.16 (m, 2 H), 6.69 (t, 1 H, J = 7.3 Hz), 6.61 (d, 1 H, J = 4.0 Hz), 3.57–3.68 (m, 2 H), 1.16 (t, 3 H, J = 6.9 Hz). 13C NMR (75 MHz, DMSO-d 6): δ = 173.8, 163.9, 146.7, 142.6, 133.3, 130.9, 129.0, 126.8, 125.1, 122.7, 117.2, 114.2, 113.9, 109.0, 70.7, 34.0, 12.3. IR (KBr): 3368, 3227, 1638, 1613 cm–1. MS (ES+): m/z = 294.0 [M+ + 1]. HRMS (DART): m/z calcd for [C17H15N3O2 + H+]: 294.1164; found: 294.1156
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