Efficient Synthesis of 7,8-Dihydro-6H-benzo[c]chromen-6-one Derivatives by Base-Mediated Chemoselective Annulation of Alkylidene Malononitriles with α,β-Unsaturated Coumarins

Abdolali Alizadeh; Behnaz Farajpour; Mojtaba Khanpour

doi:10.1055/s-0040-1706012

Synlett, Table of Contents

Synlett 2021; 32(07): 697-700
DOI: 10.1055/s-0040-1706012

letter

Efficient Synthesis of 7,8-Dihydro-6H-benzo[c]chromen-6-one Derivatives by Base-Mediated Chemoselective Annulation of Alkylidene Malononitriles with α,β-Unsaturated Coumarins

Authors

Abdolali Alizadeh∗

^aDepartment of Chemistry, Tarbiat Modares University, P. O. Box 14115-175, Tehran, Iran
Behnaz Farajpour

^aDepartment of Chemistry, Tarbiat Modares University, P. O. Box 14115-175, Tehran, Iran
Mojtaba Khanpour

^bState Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, 350002, Fujian, P. R. of China

Abstract

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Abstract

An efficient and chemoselective synthesis of biologically valuable 7,8-dihydro-6H-benzo[c]chromen-6-ones is described. In this method, neither a metal catalyst nor expensive starting materials are needed, and the products can be purified by simple filtration and washing with EtOH. Readily available starting materials, green and mild conditions, synthetically useful yields, and operational simplicity are some highlighted advantages of this unprecedented transformation.

Key words

alkylidenemalononitriles - coumarins - benzochromenones - 6π-electrocyclic ring closure - hydride shift

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References

References and Notes

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21 7,8-Dihydro-6H-benzo[c]chromen-6-ones 3a–i; General Procedure Et₃N (0.5 mmol) was added to a mixture of the appropriate alkylidene malononitrile derivative 1 (0.5 mmol) and 4-chloro-3-(3-oxo-3-phenylprop-1-en-1-yl)-2H-chromen-2-one 2 (0.5 mmol) in anhyd EtOH (1 mL), and the mixture was stirred at 80 °C for 10 h until the reaction was complete (TLC). The resulting solid was isolated by simple filtration and washed twice with 96% EtOH. 6-Oxo-7-(2-oxo-2-phenylethyl)-9-phenyl-6H-benzo[c]chromene-8,8(7H)-dicarbonitrile (3a) White powder; yield: 0.34 g (77%); mp 284–286 °C. IR (KBr): 2229 (C≡N), 1732 (C=O), 1687 (COO), 1600, 1580, and 1500 (Ar), 1159, and 1085 (C–O) cm^–1. ¹H NMR (500 MHz, CDCl₃): δ = 3.25 (dd, ² J _HH = 16.0 Hz, ³ J _HH = 6.5 Hz, 1 H, CH¹), 3.83 (dd, ² J _HH = 16.0 Hz, ³ J _HH = 5.7 Hz, 1 H, CH¹), 4.77 (t, ³ J _HH = 6.0 Hz, 1 H, CH⁷), 7.27 (d, ³ J _HH = 8.3 Hz, 2 H, 2CH _ortho of Ph), 7.37 (t, ³ J _HH = 7.5 Hz, 1 H, CH² of coumarin), 7.43 (d, ³ J _HH = 8.4 Hz, 1 H, CH⁴ of coumarin), 7.45 (t, ³ J _HH = 7.6 Hz, 2 H, 2CH _meta of Ph), 7.54–7.57 (m, 3 H, 3CH of Ph), 7.63 (s, 1 H, CH¹⁰), 7.63 (t, ³ J _HH = 7.6 Hz, 1 H, CH³ of coumarin), 7.64 (t, ³ J _HH = 7.9 Hz, 1 H, CH _para of Ph), 7.73 (d, ³J_HH = 8.0 Hz, 1 H, CH¹ of coumarin), 7.92 (d, ³ J _HH = 7.7 Hz, 2 H, 2CH _ortho of Ph). ¹³C NMR (125 MHz, CDCl₃): δ = 37.3 (CH⁸), 37.3 (CH⁷), 37.8 (CH₂), 112.6 (CN), 113.4 (CN), 116.0 (C^10b), 116.8 (C^6a), 117.7 (CH⁴ of coumarin), 121.8 (CH¹⁰), 123.4 (CH² of coumarin), 124.8 (CH¹ of coumarin), 127.0 (2CH _meta of Ph), 128.3 (2CH _meta of Ph), 128.7 (2CH _ortho of Ph), 129.2 (2CH _ortho of Ph), 130.9 (CH _para of Ph), 132.6 (CH³ of coumarin), 133.6 (CH _para of Ph), 135.2 (C⁹), 136.1 (C of Ph), 137.8 (C of Ph), 139.8 (C^10a), 153.5 (C^4a), 159.4 (CO of coumarin), 194.9 (CO). MS (EI, 70 eV): m/z (%) = 442 (M⁺, 20), 416 (28), 297 (26), 105 (100), 77 (24). Anal. Calcd for C₂₉H₁₈N₂O₃ (442.46): C, 78.72; H, 4.10, N, 6.33. Found: C, 78.73; H, 4.12, N, 6.32.
22 CCDC 1955482 contains the supplementary crystallographic data for compound 3c. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/structures.

Supplementary Material

Supporting Information (PDF)