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Synlett 2017; 28(07): 825-830
DOI: 10.1055/s-0036-1588941
DOI: 10.1055/s-0036-1588941
letter
Ph3P/I2-Mediated Synthesis of 3-Aryl-Substituted and 3,4-Disubstituted Coumarins
Further Information
Publication History
Received: 15 December 2016
Accepted after revision: 30 December 2016
Publication Date:
02 February 2017 (online)
![](https://www.thieme-connect.de/media/synlett/201707/lookinside/thumbnails/st-2016-d0845-l_10-1055_s-0036-1588941-1.jpg)
Abstract
Ph3P/I2–Et3N-mediated one-pot two-step esterification–cyclization toward 3-aryl coumarins and 3-aryl-4-methylcoumarins is reported. The reaction of a variety of aryl acetic acids containing steric or reactive group with 2-hydroxybenzaldehydes or 2′-hydroxyacetophenone proceeded smoothly at room temperature to afford the corresponding products in good to excellent yields using inexpensive and readily available reactants and reagents.
Supporting Information
- Supporting information for this article is available online at http://dx.doi.org/10.1055/s-0036-1588941.
- Supporting Information
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References and Notes
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- 22 General Procedure To a solution of Ph3P (0.62 mmol) in CH2Cl2 (4 mL) was added I2 (0.62 mmol) at 0 °C. The resulting solution was sequentially added with aryl acetic acid (0.41 mmol) and hydroxybenzaldehyde (0.45 mmol) at 0 °C, followed by Et3N (2.05 mmol). After that, the solution was allowed to warm up to r.t. and stirred until the completion of reaction. The crude material was purified by column chromatography using EtOAc–hexanes as the eluent to afford pure product. 3-(4-Methoxyphenyl)-2H-chromen-2-one (Table 2, Entry 4) White solid (0.1013 g, 98% yield); mp 140–141 °C (lit.2 mp 140 °C); Rf = 0.38 (30% EtOAc–hexanes). 1H NMR (400 MHz, CDCl3): δ = 7.75 (s, 1 H), 7.68 (d, J = 8.8 Hz, 2 H), 7.53–7.48 (m, 2 H), 7.34 (d, J = 7.6 Hz, 1 H), 7.28 (t, J = 7.6 Hz, 1 H), 6.97 (d, J = 8.8 Hz, 2 H), 3.85 (s, 3 H). 13C NMR (100 MHz, CDCl3): δ = 160.8, 160.2, 153.3, 138.5, 131.0, 129.9, 127.8, 127.1, 124.5, 119.9, 116.3, 113.9, 55.4. 6-Nitro-3-(2-nitrophenyl)-2H-chromen-2-one (Table 2, Entry 6) Yellow solid (0.0912 g, 71% yield); mp 217–218 °C; Rf = 0.41 (40% EtOAc–hexanes). 1H NMR (400 MHz, CDCl3 + TFA): δ = 8.55 (d, J = 2.4 Hz, 1 H), 8.47 (dd, J = 9.2, 2.4 Hz, 1 H), 8.22 (d, J = 7.6 Hz, 1 H), 7.94 (s, 1 H), 7.80 (t, J = 7.6 Hz, 1 H), 7.70 (t, J = 7.6 Hz, 1 H), 7.58 (d, J = 9.2 Hz, 1 H), 7.51 (d, J = 7.6 Hz, 1 H). 13C NMR (100 MHz, CDCl3+TFA): δ = 160.4, 156.8, 148.2, 144.8, 139.3, 134.6, 132.1, 131.2, 130.1, 129.0, 127.1, 125.5, 124.2, 119.5, 118.5. HRMS (ESI-TOF): m/z calcd for C15H9N2O6 [M + H]+: 313.0461; found. 313.0467. 6-Chloro-3-(2-nitrophenyl)-2H-chromen-2-one (Table 2, Entry 8) White solid (0.0832 g, 67% yield); mp 214–215 °C; Rf = 0.46 (30% EtOAc–hexanes). 1H NMR (400 MHz, CDCl3 + TFA): δ = 8.20 (d, J = 8.0 Hz, 1 H), 7.85 (s, 1 H), 7.77 (td, J = 8.0, 1.2 Hz, 2 H), 7.67 (td, J = 8.0, 1.2 Hz, 1 H), 7.62 (s, 1 H), 7.60 (dd, J = 8.8, 2.4 Hz, 1 H), 7.49 (dd, J = 8.0, 1.2 Hz, 1 H), 7.41 (d, J = 8.8 Hz, 1 H). 13C NMR (100 MHz, CDCl3 + TFA): δ = 162.6, 151.6, 148.2, 140.6, 134.5, 132.9, 132.2, 131.4, 130.9, 129.3, 127.7, 125.4, 118.6, 110.3. HRMS (ESI-TOF): m/z calcd for C15H9ClNO4 [M + H]+: 302.0220; found: 302.0226. 3-(4-Fluorophenyl)-4-methyl-2H-chromen-2-one (Table 2, Entry 18) White solid (0.0921 g, 88% yield); mp 183–184 °C; Rf = 0.30 (20% EtOAc–hexanes). 1H NMR (400 MHz, CDCl3): δ = 7.68 (dd, J = 8.0, 1.2 Hz, 1 H), 7.55 (td, J = 8.0, 1.2 Hz, 1 H), 7.36 (t, J = 8.8 Hz, 2 H), 7.31–7.26 (m, 2 H), 7.14 (td, J = 8.8, 2.0 Hz, 2 H), 2.32 (s, 3 H). 13C NMR (100 MHz, CDCl3): δ = 163.9, 161.4, 161.0, 152.7, 148.1, 132.07, 131.99, 131.6, 130.4 (d, J = 14.4 Hz), 126.4, 125.3, 124.5, 120.5, 117.0, 115.70, 115.5, 16.7. HRMS (ESI-TOF): m/z calcd for C16H12FO2 [M + H]+: 255.0821; found: 255.0824. 3-(3,4-Dichlorophenyl)-4-methyl-2H-chromen-2-one (Table 2, Entry 19) White solid (0.0901 g, 72% yield); mp 209–210 °C; Rf = 0.31 (20% EtOAc–hexanes). 1H NMR (400 MHz, CDCl3 + TFA): δ = 7.76 (dd, J = 8.4, 1.6 Hz, 1 H), 7.64 (td, J = 8.4, 1.6 Hz, 1 H), 7.55 (d, J = 8.4 Hz, 1 H), 7.45–7.41 (m, 2 H), 7.41 (d, J = 2.0 Hz, 1 H), 7.15 (dd, J = 8.4, 2.0 Hz, 1 H), 2.39 (s, 3 H). 13C NMR (100 MHz, CDCl3 + TFA): δ = 163.2, 152.3, 151.4, 133.7, 133.2, 133.0, 132.7, 132.1, 130.9, 129.6, 125.6, 125.5, 124.6, 120.3, 117.3, 113.3, 16.9. HRMS (ESI-TOF): m/z calcd for C16H11ClO2 [M + H]+: 305.0136; found: 305.0129. 4-Methyl-3-(2-nitrophenyl)-2H-chromen-2-one (Table 2, Entry 20) White solid (0.0957 g, 83% yield); mp 167–168 °C; Rf = 0.37 (30% EtOAc–hexanes). 1H NMR (400 MHz, CDCl3): δ = 8.21 (d, J = 8.0 Hz, 1 H), 7.72 (td, J = 7.6, 1.2 Hz, 1 H), 7.67 (dd, J = 8.0, 1.6 Hz, 1 H), 7.62–7.55 (m, 2 H), 7.40–7.32 (m, 3 H), 2.27 (s, 3 H). 13C NMR (100 MHz, CDCl3): δ = 159.9, 152.8, 148.8, 147.2, 133.8, 132.7, 131.9, 130.2, 129.8, 125.19, 125.17, 125.0, 124.6, 120.2, 117.2, 16.6. HRMS (ESI-TOF): m/z calcd for C16H12NO4 [M + H]+: 282.0766; found: 282.0767.
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