Solvent-Free Condensation of Phenols with Aldehydes and Amides Using 3-Methyl-1-sulfonic Acid Imidazolium Chloride

Abstract

One-pot, three-component condensation of phenols, aromatic aldehydes, and amides in the presence of 3-methyl-1-sulfonic acid imidazolium chloride {[Msim]Cl} as ionic liquid and catalyst under solvent-free condition to prepare a new category of compounds, namely amido-alkyl-phenols has been described. In the presented work, all products have been reported for the first time.

Key words

amidoalkyl phenol - ionic liquid - sulfonic acid functionalized imidazolium salts - SAFIS - phenol - aldehyde - solvent-free

• References and Notes

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• 22 Experimental Materials: All chemicals were purchased from Fluka or Merck Chemical Companies. Progress of the reactions was monitored by TLC using silica gel SIL G/UV 254 plates. The ¹H NMR (400 MHz) and ¹³C NMR (100 MHz) were recorded on a Bruker AVANCE- DRX FT–NMR spectrometer (δ in ppm). Melting points were determined on a Büchi B-545 apparatus in open capillary tubes. IR spectra were recorded on a Perkin–Elmer PE-1600-FTIR instrument. Mass spectra were run on Agilent Technology (HP) Network Mass Selective Detector 5973 (70 eV) apparatus. Optical rotations were studied in spectral grade solvents using a Perkin–Elmer 341 polarimeter. General Procedure for the Synthesis of Amidoalkyl Phenols Using [Msim]Cl: To a well-ground mixture of phenolic compound (1 mmol), aldehyde (1 mmol) and amide derivative (1.2 mmol) in a 10-mL round-bottomed flask connected to a reflux condenser, was added the catalyst (15 mol%), and the resulting mixture was stirred in an oil bath at 110 °C. After completion of the reaction, as monitored by TLC, the reaction mixture was cooled to r.t., extracted with warm EtOAc (20 mL) to separate the catalyst (the product is soluble in warm EtOAc; however, the catalyst is not soluble in this solvent). Then, EtOAc was evaporated and the solid residue (crude product) was purified by plate chromat-ography on silica gel with n-hexane–EtOAc (6:4) as an eluent to give the desired amidoalkyl phenols. The recovered catalyst was washed with EtOAc (2 × 15 mL), dried at 90 °C under vacuum condition, and reused for the preparation of amidoalkyl phenols according to the mentioned procedure. Spectral Data of the New Compounds: N-[(5-Benzyl-2-hydroxyphenyl)(phenyl)methyl]-acetamide (1): R_f = 0.057 (EtOAc–n-hexane, 1:1); mp 174–176 °C. IR (KBr): 3410, 3179, 3024, 1644, 1611 cm^–1. ¹H NMR (400 MHz, DMSO-d ₆): δ = 1.96 (s, 3 H), 3.85 (s, 2 H), 6.48 (d, J = 8.4 Hz, 1 H), 6.77 (d, J = 8.0 Hz, 1 H), 6.99 (d, J = 8.0 Hz, 1 H), 7.15–7.28 (m, 7 H), 7.37–7.72 (m, 2 H), 8.09 (d, J = 8.0 Hz, 2 H), 8.76 (d, J = 8.0 Hz, 1 H), 9.56 (s, 1 H). ¹³C NMR (100 MHz, DMSO-d ₆): δ = 23.09, 40.98, 50.61, 115.89, 121.83, 122.14, 126.28, 127.82, 128.79, 129.26, 130.17, 132.10, 134.41, 142.21, 145.25, 148.17, 153.08, 169.28. MS: m/z = 331 [M⁺]. N-[(5-Benzyl-2-hydroxyphenyl)(p-tolyl)methyl]-acetamide (2): R_f = 0.057 (EtOAc–n-hexane, 1:1); mp 183–184 °C. IR (KBr): 3412, 3246, 3025, 1648, 1610 cm^–1. ¹H NMR (400 MHz, DMSO-d ₆): δ = 1.90 (s, 3 H), 2.25 (s, 3 H), 3.81 (s, 2 H), 6.31 (d, J = 6.0 Hz, 1 H), 6.71 (d, J = 5.5 Hz, 1 H), 6.87 (dd, J = 4.0, 1.4 Hz, 1 H), 7.07–7.28 (m, 10 H), 8.47 (d, J = 6.0 Hz, 1 H), 9.56 (s, 1 H). ¹³C NMR (100 MHz, DMSO-d ₆): δ = 21.04, 23.10, 41.03, 50.47, 115.63, 126.23, 127.44, 128.45, 128.53, 128.76, 128.93, 129.01, 129.19, 131.66, 135.96, 140.29, 142.30, 153.04, 168.84. MS: m/z = 345 [M⁺]. N-[(5-Benzyl-2-hydroxyphenyl)(3-nitrophenyl)methyl]-acetamide (3): R_f = 0.042 (EtOAc–n-hexane, 1:1); mp 210–215 °C. IR (KBr): 3381, 3025, 2733, 1635, 1606 cm^–1. ¹H NMR (400 MHz, DMSO-d ₆): δ = 1.88 (s, 3 H), 3.79 (s, 2 H), 6.44 (d, J = 7.6 Hz, 1 H), 6.74 (d, J = 8.0 Hz, 1 H), 6.81 (s, 1 H), 6.92 (d, J = 8.0 Hz, 1 H), 7.13–7.58 (m, 8 H), 7.59 (d, J = 4.8 Hz, 1 H (, 8.41 (s, 1 H), 9.39 (s, 1 H). ¹³C NMR (100 MHz, DMSO-d ₆): δ = 22.89, 40.97, 51.48, 115.58, 124.14, 126.26, 127.38, 127.83, 128.76, 128.82, 128.93, 128.98, 129.25, 129.58, 131.25, 133.13, 141.85, 142.15, 153.72, 168.78. MS: m/z = 376 [M⁺]. N-[(5-Benzyl-2-hydroxyphenyl)(2-nitrophenyl)methyl]-acetamide (4): R_f = 0.05 (EtOAc–n-hexane, 1:1); mp 226–228 °C. IR (KBr): 3403, 3271, 3027, 1656, 1614 cm^–1. ¹H NMR (400 MHz, DMSO-d ₆): δ = 1.79 (s, 3 H), 3.68 (s, 2 H), 6.60–6.70 (m, 3 H), 6.82 (dd, J = 6.2, 2.0 Hz, 1 H), 7.01–7.18 (m, 3 H), 7.32–7.34 (m, 2 H), 7.34–7.41 (m, 1 H), 7.75 (s, 1 H), 7.77 (s, 1 H), 7.78 (d, J = 7.4 Hz, 1 H), 8.43 (d, J = 8.0 Hz, 1 H), 9.36 (s, 1 H). ¹³C NMR (100 MHz, DMSO-d ₆): δ = 22.28, 46.91, 56.00, 115.01, 124.06, 125.73, 126.80, 127.65, 128.10, 128.43, 128.48, 128.63, 129.54, 130.89, 132.63, 135.98, 141.53, 148.81, 153.00, 168.41. MS: m/z = 376 [M⁺]. N-[(5-Benzyl-2-hydroxyphenyl)(phenyl)methyl]-benzamide (5): R_f = 0.11 (EtOAc–n-hexane, 1:1); mp 204–206 °C. IR (KBr): 3403, 3062, 3028, 1630, 1603 cm^–1. ¹H NMR (400 MHz, DMSO-d ₆): δ = 3.78 (s, 2 H), 6.46 (d, J = 8.4 Hz, 1 H), 6.67–6.92 (m, 11 H), 7.13–7.27 (m, 7 H), 8.23 (d, J = 8.4 Hz, 1 H), 9.25 (s, 1 H). ¹³C NMR (100 MHz, DMSO-d ₆): δ = 41.04, 56.45, 111.91, 112.47, 115.41, 115.55, 126.21, 128.44, 128.56, 128.74, 128.87, 128.93, 131.14, 132.07, 142.39, 151.31, 153.50, 153.58, 168.59. MS: m/z = 393 [M⁺]. N-[(5-Bromo-2-hydroxyphenyl)(4-chlorophenyl)-methyl]acetamide (6): R_f = 0.028 (EtOAc–n-hexane, 1:1); mp 220–225 °C. IR (KBr): 3309, 3074, 2980, 2739, 1649, 1631 cm^–1. ¹H NMR (400 MHz, DMSO-d ₆): δ = 1.85 (s, 3 H), 5.95 (d, J = 8.4 Hz, 1 H), 6.68 (s, 2 H), 6.99 (d, J = 8.0 Hz, 2 H), 7.23–7.35 (m, 3 H), 8.66 (s, 1 H), 9.35 (s, 1 H). ¹³C NMR (100 MHz, DMSO-d ₆): δ = 24.19, 56.36, 116.70, 129.78, 130.14, 130.50, 132.84, 133.97, 143.90, 158.02, 169.99. MS: m/z = 354 [M⁺]. N-[(2,4-Dichlorophenyl)(2-hydroxyphenyl)methyl]-acetamide (7): R_f = 0.028 (EtOAc–n-hexane, 1:1); mp 228–230 °C. IR (KBr): 3301, 3065, 2808, 1634, 1613 cm^–1. ¹H NMR (400 MHz, DMSO-d ₆): δ = 1.85 (s, 3 H), 6.33 (d, J = 8.0 Hz, 1 H), 6.47 (d, J = 8.0 Hz, 1 H), 6.71 (d, J = 8.0 Hz, 1 H), 6.91 (d, J = 7.6 Hz, 1 H), 7.14–7.81 (m, J = 8.0 Hz, 4 H), 7.96 (s, 1 H), 8.69 (s, 1 H). ¹³C NMR (100 MHz, DMSO-d ₆): δ = 24.08, 58.14, 117.91, 124.91, 125.23, 127.41, 129.90, 130.08, 130.48, 133.03, 133.9, 134.12, 143.26, 154.17, 170.50. MS: m/z = 310 [M⁺]. N-[(5-Bromo-2-hydroxyphenyl)(2-bromophenyl)-methyl]acetamide (8): R_f = 0.08 (EtOAc–n-hexane, 1:1); mp 197–200 °C. IR (KBr): 3300, 3064, 2808, 1634, 1613 cm^–1. ¹H NMR (400 MHz, DMSO-d ₆): δ = 1.21 (s, 3 H), 6.45 (s, 1 H), 6.61 (s, 1 H), 6.98 (s, 1 H), 7.06–7.32 (m, 5 H), 7.55 (d, J = 6.8 Hz, 1 H), 8.69 (s, 1 H). ¹³C NMR (100 MHz, DMSO-d ₆): δ = 22.82, 51.72, 126.26, 127.17, 127.86, 128.09, 128.67, 128.86, 129.10, 129.34, 133.25, 141.20, 141.42, 169.66. MS: m/z = 399 [M⁺]. N-[(5-Bromo-2-hydroxyphenyl)(2,5-dimethoxyphenyl)-methyl]acetamide (9): R_f = 0.08 (EtOAc–n-hexane, 1:1); mp 215–217 °C. IR (KBr): 3372, 3267, 2854, 1652 cm^–1. ¹H NMR (400 MHz, DMSO-d ₆): δ = 1.82 (s, 3 H), 3.31 (s, 3 H), 3.76 (s, 3 H), 6.30 (d, J = 6.0 Hz, 1 H), 6.69 (d, J = 8.4 Hz, 1 H), 6.87 (d, J = 6.4 Hz, 1 H), 7.09–7.28 (m, 4 H), 8.50 (d, J = 9.2 Hz, 1 H), 9.35 (s, 1 H). ¹³C NMR (100 MHz, DMSO-d ₆): δ = 23.12, 41.05, 50.46, 115.68, 126.26, 127.32, 128.33, 128.48, 128.79, 128.96, 129.05, 131.78, 141.55, 142.32, 152.94, 168.75. MS: m/z = 380 [M⁺]. N,N′-{1,4-Phenylenebis[(5-benzyl-2-hydroxyphenyl)-methylene]}diacetamide (10): R_f = 0.084 (EtOAc–n-hexane, 1:1); mp 257–259 °C. IR (KBr): 3402, 3026, 1639, 1604 cm^–1. ¹H NMR (400 MHz, DMSO-d ₆): δ = 1.88 (s, 6 H), 3.85 (s, 4 H), 6.72 (d, J = 8.8 Hz, 1 H), 6.81 (d, J = 8.0 Hz, 1 H), 6.96 (d, J = 8.0 Hz, 1 H), 7.15–7.57 (m, 17 H), 7.92 (d, J = 6.8 Hz, 2 H), 9.11 (d, J = 9.2 Hz, 2 H), 9.55 (s, 2 H). ¹³C NMR (100 MHz, DMSO-d ₆): δ = 18.98, 41.17, 51.54, 115.17, 126.28, 127.12, 127.83, 128.02, 128.23, 128.58, 128.73, 128.75, 128.80, 129.02, 129.18, 131.70, 131.97, 135.17, 142.35, 143.02, 153.35, 166.37. MS: m/z = 584 [M⁺].