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Synlett 2014; 25(11): 1611-1615
DOI: 10.1055/s-0033-1341270
DOI: 10.1055/s-0033-1341270
letter
Base-Mediated Synthesis of Imines and Amines from N-Phenylureas and Alcohols
Authors
Further Information
Publication History
Received: 14 March 2014
Accepted after revision: 27 March 2014
Publication Date:
30 April 2014 (online)
Abstract
A new base-mediated protocol has been developed for the synthesis of imines and amines from N-phenylureas and alcohols under normal air. From the synthetic point of view, the protocol can be considered as an efficient alternative to conventional methods for the synthesis of imines and amines in moderate to excellent yields.
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References and Notes
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- 21 Imines 3a–s; General Procedure A mixture of the appropriate N-arylurea (1 mmol), arylmethanol (3 mmol), and KOH (1.5 mmol) was stirred at 135 °C under a normal air atmosphere in a sealed 20-mL Schlenk tube for 24 h. When the reaction was complete (GC), EtOAc (3 mL) and H2O (3 mL) were added and the mixture was stirred vigorously. The organic layer was separated, and the aqueous layer was extracted with EtOAc (2 × 3 mL). The organic layers were combined, dried (Na2SO4), and concentrated under reduced pressure. The crude product was purified by column chromatography (basic alumina saturated with Et3N, PE). The identity of the compound was confirmed by various spectroscopic techniques, and its purity was determined by GC-MS analysis. N-Benzylideneaniline (3a) 18 Brown oil; yield: 172 mg (95%). 1H NMR (400 MHz, CDCl3): δ = 8.45 (s, 1 H), 7.91–7.88 (m, 2 H), 7.47–7.37 (m, 5 H), 7.24–7.20 (m, 3 H). 13C NMR (100 MHz, CDCl3): δ = 160.4, 152.1, 136.2, 131.4, 129.1, 128.8, 128.7, 125.9, 120.9. GC-MS (EI, 70 eV): m/z (%) = 181 (90) [M]+, 180 (100), 152 (5), 104 (10), 77 (60), 51 (15), 39 (5). N-(4-Methoxybenzylidene)aniline (3c) 28 White solid; yield: 198 mg (94%); mp 63–67 °C. 1H NMR (400 MHz, CDCl3): δ = 8.37 (s, 1 H), 7.84 (d, J = 8.8 Hz, 2 H), 7.37 (t, J = 7.5 Hz, 2 H), 7.20–7.12 (m, 3 H), 6.97 (d, J = 8.8 Hz, 2 H), 3.85 (s, 3 H). 13C NMR (100 MHz, CDCl3): δ = 162.2, 159.7, 152.4, 130.5, 129.1, 125.5, 120.9, 114.2, 55.4. GC–MS (EI, 70 eV): m/z (%) = 211 (20) [M]+, 210 (100), 195 (6), 167 (10), 77 (42), 51 (15). N-(2-Chlorobenzylidene)aniline (3f) 18 Brown oil; yield: 148 mg (69%). 1H NMR (400 MHz, CDCl3): δ = 8.91 (s, 1 H), 8.25–8.23 (m, 1 H), 7.42–7.32 (m, 5 H), 7.27–7.23 (m, 3 H). 13C NMR (100 MHz, CDCl3): δ = 156.9, 151.8, 136.1, 133.6, 132.4, 129.9, 129.3, 128.6, 127.2, 126.4, 121.1. GC–MS (EI, 70 eV): m/z (%) = 217 (26) [M + 2]+, 215 (80) [M]+, 180 (37), 152 (7), 112 (7), 104 (24), 89 (7), 77 (100), 63 (8), 51 (41). N-(3-Chlorobenzylidene)aniline (3g) 18 Brown oil; yield: 172 mg (80%). 1H NMR (400 MHz, CDCl3): δ = 8.39 (s, 1 H), 7.93 (s, 1 H), 7.73 (d, J = 7.6 Hz, 1 H), 7.45–7.37 (m, 4 H), 7.25–7.20 (m, 3 H). 13C NMR (100 MHz, CDCl3): δ = 158.6, 151.5, 137.9, 134.9, 131.2, 130.4, 129.2, 128.3, 127.1, 126.3, 120.8. GC–MS (EI, 70 eV): m/z (%) = 217 (26) [M + 2]+, 215 (78) [M]+, 180 (4), 151 (5), 112 (4), 104 (30), 89 (13), 77 (100), 63 (8), 51 (38). N-(4-Chlorobenzylidene)aniline (3h) 18 White solid; yield: 187 mg (87%); mp 75–77 °C. 1H NMR (400 MHz, CDCl3): δ = 8.40 (s, 1 H), 7.83 (d, J = 8.4 Hz, 2 H), 7.43 (d, J = 8.4 Hz, 2 H), 7.41–7.37 (m, 2 H), 7.26–7.19 (m, 3 H). 13C NMR (100 MHz, CDCl3): δ = 158.8, 151.7, 137.3, 134.7, 130.0, 129.2, 129.0, 126.2, 120.8. GC–MS (EI, 70 eV): m/z (%) = 217 (28) [M + 2]+, 215 (40) [M]+, 178 (4), 152 (5), 138 (2), 104 (17), 89 (13), 77 (100), 63 (8), 51 (38). N-(4-Fluorobenzylidene)aniline (3i) 18 Brown oil; yield: 163 mg (82%). 1H NMR (400 MHz, CDCl3): δ = 8.40 (s, 1 H), 7.91–7.87 (m, 2 H), 7.40–7.37 (m, 2 H), 7.25–7.12 (m, 5 H). 13C NMR (100 MHz, CDCl3): δ = 164.7 (d, J C–F = 251 Hz), 158.8, 151.8, 132.6 (d, J C–F = 3 Hz), 130.8 (d, J C–F = 8 Hz), 129.2, 126.1, 120.8, 115.9 (d, J C–F = 22 Hz). GC–MS (EI, 70 eV): m/z (%) = 199 (93) [M]+, 198 (100), 169 (1), 107 (6), 104 (13), 99 (3), 96 (6), 95 (3), 89 (7), 85 (3), 78 (7), 77 (79), 51 (27), 50 (5).
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