Copper(II) Acetate Catalyzed Ullmann-Type C–O Coupling Reaction of 
Phenols with 4-Tosylcoumarin

Abdolali Alizadeh; Rashid Ghanbaripour

doi:10.1055/s-0034-1379231

Synlett, Inhaltsverzeichnis

Synlett 2014; 25(19): 2777-2780
DOI: 10.1055/s-0034-1379231

letter

Copper(II) Acetate Catalyzed Ullmann-Type C–O Coupling Reaction of Phenols with 4-Tosylcoumarin

Abdolali Alizadeh*

Department of Chemistry, Tarbiat Modares University, P.O. Box 14115-175, Tehran, Iran Fax: +98(21)88006544 eMail: abdol_alizad@yahoo.com eMail: aalizadeh@modares.ac.ir

,

Rashid Ghanbaripour

Department of Chemistry, Tarbiat Modares University, P.O. Box 14115-175, Tehran, Iran Fax: +98(21)88006544 eMail: abdol_alizad@yahoo.com eMail: aalizadeh@modares.ac.ir

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Abstract

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Abstract

A copper(II) acetate mediated Ullmann-type reaction of phenols with 4-tosylcoumarin for the synthesis of 4-aryloxycoumarins is reported. The method has some attractive features such as operational simplicity, moderate to good yields, and the use of ligand-free copper(II) acetate as a green and stable catalyst.

Key words

coumarins - ligand free - phenols - synthetic methods - Ullmann coupling

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Referenzen

References and Notes
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25 General Procedure: A solution of 4-toluenesulfonyloxycoumarin (1 mmol), phenol (1 mmol), K₂CO₃ (1.5 mmol), and Cu(OAc)₂ (0.1 mmol) in DMF (6 mL), was stirred for 3 h at 80 °C. Upon completion, as monitored by TLC, the reaction mixture was cooled to room temperature and water (20 mL) was added. The mixture was extracted with CH₂Cl₂ (3 × 10 mL) and dried over anhydrous Na₂SO₄. The solution was filtered, concentrated, and the residue was purified by column chromatography (EtOAc–hexane, 1:10 v/v) to afford the product 2a–f. 4-Phenoxy-2H-chromene-2-one (2a): Yield: 0.154 g (65%); white powder; mp 99–101 °C. IR (KBr): 1714 (C=O), 1614, 1561 and 1483 (Ar), 1223 and 1183 (C–O) cm^–1. ¹H NMR (400 MHz, DMSO-d ₆): δ = 5.18 (s, 1 H, CH³), 7.39 (d, ³ J _H–H = 7.6 Hz, 2 H, CH _ortho of Ph), 7.43–7.51 (m, 2 H, ArH), 7.58 (d, ³ J _H–H = 7.6 Hz, 2 H, ArH), 7.59 (t, ³ J _H–H = 8.0 Hz, 1 H, ArH), 7.77 (td, ³ J _H–H = 8.0 Hz, ⁴ J _H–H = 1.6 Hz, 1 H, ArH), 8.07 (dd, ³ J _H–H = 8.0 Hz, ⁴ J _H–H = 1.6 Hz, 1 H, ArH). ¹³C NMR (100 MHz, DMSO-d ₆): δ = 92.83 (CH³), 115.18 (C^4a), 116.59 (ArH), 121.28 (2 × CH _meta of Ph), 123.01 (ArH), 124.52 (CH _para of Ph), 126.90 (ArH), 130.60 (2 × CH _ortho of Ph), 133.41 (ArH), 152.08 (C^8a), 153.08 (C _ipso -O), 161.10 (C⁴), 165.80 (CO₂). MS: m/z = 238 [M⁺], 221, 210, 197, 181, 145, 118, 101, 89, 77, 63. Anal. Calcd for C₁₅H₁₀O₃: C, 75.62; H, 4.23. Found: C, 75.69; H, 4.12. 4-(4-Ethylphenoxy)-2H-chromene-2-one (2b): Yield: 0.162 g (61%); yellow powder; mp 100–104 °C. IR (KBr): 1722 (C=O), 1619 and 1491 (Ar), 1179 (C-O) cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 1.19 (t, ³ J _H–H = 7.6 Hz, 3 H, CH₃), 2.62 (q, ³ J _H–H = 7.6 Hz, 2 H, CH₂), 5.35 (s, 1 H, CH³), 6.99 (d, ³ J _H–H = 8.4 Hz, 2 H, ArH), 7.21 (d, ³ J _H–H = 8.4 Hz, 2 H, ArH), 7.26 (t, ³ J _H–H = 8.0 Hz, 1 H, ArH), 7.28 (d, ³ J _H–H = 8.0 Hz, 1 H, ArH), 7.52 (td, ³ J _H–H = 7.2 Hz, ⁴ J _H–H = 1.2 Hz, 1 H, ArH), 7.94 (d, ³ J _H–H = 7.6 Hz, 1 H, ArH). ¹³C NMR (100 MHz, CDCl₃): δ = 15.59 (CH₃), 28.32 (CH₂), 93.46 (CH³), 115.55 (C^4a), 116.82 (ArH), 121.00 (2 × ArH), 123.09 (CH of Ar), 124.03 (ArH), 129.68 (2 × ArH), 132.70 (ArH), 142.97 (C _ipso -Et), 150.38 (C^8a), 153.71 (C _ipso -O), 162.62 (C⁴), 166.55 (CO₂). MS: m/z = 266 [M⁺], 238, 181, 165, 155, 146, 131, 121, 101, 89, 77, 63. Anal. Calcd for C₁₇H₁₄O₃: C, 76.68; H, 5.30. Found: C, 76.72; H, 5.38. 4-(3,5-Dimethylphenoxy)-2H-chromene-2-one (2c): Yield: 0.196 g (74%); yellow powder; mp 109–113 °C. IR (KBr): 1716 (C=O), 1621, 1565 and 1487 (Ar), 1273 and 1223 (C–O) cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 2.28 (s, 6 H, CH₃), 5.38 (s, 1 H, CH³), 6.70 (s, 2 H, ArH), 6.88 (s, 1 H, ArH), 7.26 (t, ³ J _H–H = 7.6 Hz, 1 H, ArH), 7.26 (d, ³ J _H–H = 7.2 Hz, 1 H, ArH), 7.53 (td, ³ J _H–H = 8.0 Hz, ⁴ J _H–H = 1.6 Hz, 1 H, ArH), 7.93 (dd, ³ J _H–H = 7.2 Hz, ⁴ J _H–H = 1.6 Hz, 1 H, ArH). ¹³C NMR (100 MHz, CDCl₃): δ = 21.21 (2 × CH₃), 93.54 (CH³), 115.59 (C^4a), 116.82 (ArH), 118.67 (2 × ArH), 123.05 (ArH), 124.02 (ArH), 128.33 (ArH), 132.65 (ArH), 140.43 (2 × C _ipso -Me), 152.45 (C^8a), 153.71 (C _ipso -O), 162.73 (C⁴), 166.42 (CO₂). MS: m/z = 266 [M⁺], 249, 238, 195, 155, 145, 121, 105, 91, 77. Anal. Calcd for C₁₇H₁₄O₃: C, 76.68; H, 5.30. Found: C, 76.59; H, 5.35. 4-(3-Methylphenoxy)-2H-chromene-2-one (2d): Yield: 0.181 g (72%); beige powder; mp 118–120 °C. IR (KBr): 1715 (C=O), 1621, 1567 and 1484 (Ar), 1240 (C–O) cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 2.43 (s, 6 H, CH₃), 5.46 (s, 1 H, CH³), 6.99 (d, ³ J _H–H = 7.6 Hz, 1 H, ArH), 7.00 (s, 1 H, ArH), 7.17 (d, ³ J _H–H = 7.6 Hz, 1 H, ArH), 7.38 (t, ³ J _H–H = 7.6 Hz, 1 H, ArH), 7.39 (d, ³ J _H–H = 8.0 Hz, 1 H, ArH), 7.64 (t, ³ J _H–H = 8.0 Hz, 1 H, ArH), 8.05 (d, ³ J _H–H = 8.0 Hz, 1 H, ArH). ¹³C NMR (100 MHz, CDCl₃): δ = 21.29 (CH₃), 93.58 (CH³), 115.51 (C^4a), 116.85 (ArH), 118.13 (ArH), 121.76 (ArH), 123.07 (ArH), 124.05 (ArH), 127.52 (ArH), 130.09 (ArH), 124.05 (ArH), 132.71 (ArH), 140.85 (C _ipso -Me), 152.45 (C^8a), 153.71 (C _ipso -O), 162.66 (C⁴), 166.37 (CO₂). MS: m/z = 252 [M⁺], 235, 224, 211, 195, 181, 145, 132, 121, 101, 89, 77, 63. Anal. Calcd for C₁₆H₁₂O₃: C, 76.18; H, 4.79. Found: C, 76.30; H, 4.75. 4-(4-Fluorophenoxy)-2H-chromene-2-one (2e): Yield: 0.174 g (68%); yellow powder; mp 118–121 °C. IR (KBr): 1722 (C=O), 1621 and 1495 (Ar), 1182 (C-O) cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 5.31 (s, 1 H, CH³), 7.08–7.17 (m, 2 H, ArH), 7.17–7.19 (m, 2 H, ArH), 7.22–7.31 (m, 2 H, ArH), 7.52-7.57 (m, 1 H, ArH), 7.92–7.95 (m, 1 H, ArH). ¹³C NMR (100 MHz, CDCl₃): δ = 93.61 (CH³), 115.28 (C^4a), 117.00 (d, ² J _C–F = 169.0 Hz, 2 × ArH), 117.31 (ArH), 122.84 (d, ³ J _C–F = 85.0 Hz, 2 × ArH), 123.00 (ArH), 124.14 (ArH), 132.91 (ArH), 148.28 (C^8a), 153.71 (C _ipso -O), 160.75 (d, ¹ J _C–F = 244.0 Hz, C _ipso -F), 162.33 (C⁴), 166.35 (CO₂). MS: m/z = 256 [M⁺], 215, 199, 145, 136, 121, 101, 89, 75, 63. Anal. Calcd for C₁₅H₉FO₃: C, 70.31; H, 3.54. Found: C, 70.26; H, 3.47. 4-(4-Methoxyphenoxy)-2H-chromene-2-one (2f): Yield: 0.209 g (78%); yellow oil. IR (KBr): 1685 (C=O), 1629, 1509 and 1455 (Ar), 1224 (C–O) cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 3.78 (s, 3 H, OMe), 5.35 (s, 1 H, CH³), 6.90 (d, ³ J _H–H = 9.2 Hz, 2 H, ArH), 7.02 (d, ³ J _H–H = 9.2 Hz, 2 H, ArH), 7.27 (t, ³ J _H–H = 8.0 Hz, 1 H, ArH), 7.29 (d, ³ J _H–H = 8.0 Hz, 1 H, ArH), 7.54 (td, ³ J _H–H = 7.6 Hz, ⁴ J _H–H = 0.9 Hz, 1 H, ArH), 7.95 (d, ³ J _H–H = 7.6 Hz, 1 H, ArH). ¹³C NMR (100 MHz, CDCl₃): δ = 55.73 (OMe), 93.35 (CH³), 114.49 (C^4a), 115.39 (2 × ArH), 116.84 (ArH), 122.10 (2 × ArH), 123.07 (ArH), 124.04 (ArH), 132.06 (ArH), 151.86 (C^8a), 152.50 (C _ipso -O), 153.70 (C _ipso -OMe), 162.68 (C⁴), 163.31 (CO₂). MS: m/z = 268 [M⁺], 184, 145, 133, 121, 109, 101, 89, 77, 63. Anal. Calcd for C₁₆H₁₂O₄: C, 71.64; H, 4.51. Found: C, 71.85; H, 4.37.