Synlett 2010(19): 2847-2852  
DOI: 10.1055/s-0030-1259035
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Organic Reactions in Water: An Efficient Synthesis of Pyranocoumarin Derivatives

Rupam Sarma, Manas M. Sarmah, Kushal C. Lekhok, Dipak Prajapati*
Medicinal Chemistry Division, North East Institute of Science & Technology (CSIR), Jorhat, Assam 785006, India
Fax: +91(376)2370011; e-Mail: [email protected];
Further Information

Publication History

Received 21 July 2010
Publication Date:
10 November 2010 (online)

Abstract

A mild and efficient protocol for the synthesis of pyrano[3,2-c]coumarins from 4-hydroxycoumarin through a one-pot ­reaction in water under phase-transfer conditions has been developed.

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  • 13a

    Typical procedure for the synthesis of 4a-l:
    A mixture of alkyl isocyanide (1 mmol), dialkyl acetylene-dicarboxylate (1 mmol) and 1,3-dicarbonyl compound (1 mmol) in H2O (5 mL), in the presence of TBAB (10 mol%) was stirred at 80 ˚C until the reaction was complete as indicated by TLC. The crude solid product was filtered, washed with H2O, dried and purified by column chromatography (EtOAc-hexane, 3:7). The products thus obtained were characterized by their IR, NMR spectroscopic and mass spectrometric data. Dimethyl 2-(cyclohexyl-amino)-5-oxo-4H,5H-pyrano[3,2-c]chromene-3,4-dicarboxylate (4a): White solid; mp 198-200 ˚C; IR (CHCl3): 3264.9 (N-H), 1732.6, 1686.3, 1659.4 (C=O) cm. ¹H NMR (300 MHz, CDCl3): δ = 1.37-2.09 (m, 10 H, 5 × CH2), 3.71 (s, 3 H, OCH3), 3.74 (s, 3 H, OCH3), 3.78-3.87 (m, 1 H, NCH), 4.73 (s, 1 H, CH), 7.30-7.72 (m, 4 H, ArH), 8.70 (s, 1 H, NH); ¹³C NMR (75 MHz, CDCl3): δ = 24.41, 24.46, 25.3, 33.4, 33.7, 36.3, 50.6, 51.2, 52.7, 72.1, 102.9, 113.5, 117.1, 121.9, 124.6, 132.7, 152.7, 154.9, 158.2, 160.7, 169.3, 173.1. GC/MS: m/z = 413 [M+]

  • 13b

    Typical procedure for the synthesis of 9: An equimolar mixture of ylidine malononitrile 8 (1 mmol) and 4-hydroxycoumarin (1 mmol) in H2O (5 mL), in the presence of TBAB (10 mol%) was stirred at 80 ˚C until the reaction was complete as indicated by TLC. The solid product was filtered, washed with water, dried and purified by recrystallization (EtOH-CHCl3, 1:1). The products thus obtained were characterized by their IR, NMR spectroscopic and mass spectrometric data (9a): Yellow crystal; mp 240-243 ˚C; IR (KBr): 3430, 3340 (NH2), 1714 (CO), 2181 (CN) cm. ¹H NMR (300 MHz, CDCl3): δ = 1.16 (t, 3 H), 4.08 (q, 2 H), 5.03 (s, CH, 1 H), 6.56 (br s, NH2, 2 H), 7.33-8.13 (m, 8 H, ArH); ¹³C NMR (75 MHz, CDCl3): δ = 14.2, 35.8, 60.2, 106.4, 113.1, 117.0, 122.3, 123.4, 124.3, 124.6, 129.5, 132.7, 146.7, 151.7, 152.7, 153.6, 158.0, 160.5, 168.2; LCMS (ESI): m/z = 408 [M+].

12

CCDC-784897 contains the supplementary crystallographic data for compound 10a. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.