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DOI: 10.1055/s-2003-36798
A New Green Approach to the Friedländer Synthesis of Quinolines
Publikationsverlauf
Publikationsdatum:
22. Januar 2003 (online)
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Abstract
A new approach to the Friedländer synthesis of quinolines is described. Polysubstituted quinolines are readily prepared under milder conditions than in other existing methods through a gold(III)-catalysed sequential condensation/annulation reaction of o-amino aromatic carbonyls and ketones containing active methylene groups.
Key words
quinolines - gold catalysis - annulations - o-amino aromatic carbonyls - domino reactions
- 1
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References
Arcadi, A.; Bianchi, G.; Di Giuseppe, S.; Marinelli, F. Green Chemistry, in press.
12A typical procedure for quinoline 3 is as follows: to a solution of 2-amino-5-chlorobenzophenone 2c (0.2 g, 0.86 mmol) and 2,4-pentanedione 1b (0.13 g, 1.29 mmol) in EtOH (3 mL) NaAuCl4·2H2O was added at r.t. under nitrogen atmosphere. The reaction mixture was stirred for 48 h. The solvent was then evaporated under reduced pressure. The residue, purified by flash chromatography (silica gel, 95/5 v/v n-hexane/ethyl acetate), afforded 1-(6-chloro-2-methyl-4-phenyl-quinolin-3-yl)-ethanone 3f (0.23 g, 89% yield); mp 153-155 °C. IR (KBr): 1715 cm-1. 1H NMR (CDCl3): δ = 2.00 (s, 3 H), 2.68 (s, 3 H), 7.33-7.96 (m, 8 H). 13C NMR (CDCl3): δ = 23.8, 31.7, 124.8, 125.7, 128.9, 129.2, 129.8, 130.5, 130.8, 132.3, 134.4, 135.4, 142.9, 145.8, 153.8, 205.1. EI-MS: m/z (relative intensity) = 295 (39) [M+], 281 (100), 252 (22).
13Selected data for 3g, 3i, 3j, 3g: Mp 80-81 °C. IR (KBr): 1750 cm-1. 1H NMR (CDCl3): δ = 2.71 (s, 3 H), 7.34-7.67 (m, 9 H). 13C NMR (CDCl3): δ = 23.8, 115,4 (q, J = 308 Hz), 126.3, 127.1, 127.6, 128.2, 129.1, 129.4, 130.3, 131.3, 131.6, 147.5, 148.3, 153.3, 189.4 (q, J = 38 Hz). EI-MS: m/z (relative intensity) = 315(68) [M+], 247 (100), 218 (27). 3i: Mp 118-120 °C. 1H NMR (CDCl3): δ = 1.33-1.47 (m, 6 H), 1.90-1.95 (m, 2 H), 2.73 (t, J = 5.6 Hz, 2 H), 3.21 (t, J = 6.1 Hz, 2 H), 7.18-7.26 (m, 4 H), 7.42-7.47 (m, 3 H), 7.52-7.60 (m, 1 H), 8.05-8.09 (m, 1 H). 13C NMR (CDCl3): δ = 25.6, 26.5, 27.9, 31.0, 31.1, 36.2, 125.2, 125.9, 127.0, 127.4, 128.0, 128.1, 128.4, 129.1, 131.6, 137.4, 146.2, 146.3, 163.2. EI-MS: m/z (relative intensity) = 287 (100) [M+], 258 (27). 3j: Mp 194-196 °C. 1H NMR (CDCl3): δ = 2.02-2.06 (m, 2 H), 2.38 (t, J = 6.7 Hz, 2 H), 2.57 (t, J = 6.9 Hz, 2 H), 7.07-8.22 (m, 12 H). 13C NMR (CDCl3): δ = 25.1, 29.6, 31.9, 115.8 (d, J = 22.2 Hz), 126.2, 126.3, 127.2, 127.9, 128.4, 128.6, 129.4, 129.5, 129.7, 130.4, 161.9 (d, J = 244.2 Hz). EI-MS: m/z (relative intensity) = 339 (100) [M+].
19Selected data for 4:
IR(neat): 3460, 3350, 1720, 1665 cm-1. 1H
NMR (CDCl3): δ = 2.05 (s, 3 H), 5.43
(s, 1 H), 7.27-7.66 (m, 9 H). 13C
NMR (CDCl3): δ = 20.3, 91.5, 114.4
(q, J = 218
Hz), 126.9, 127.3, 128.5, 129.4, 129.9, 130.7, 131.7, 133.5, 134.4,
137.6, 176.6 (q, J = 33
Hz), 195.3. EI-MS:
m/z (relative
intensity) = 324 (100) [M + 1+],
265 (21), 220 (94), 105 (67).