One-Pot Four Component Synthesis
Letters in Organic Chemistry, 2010, Vol. 7, No. 5
409
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for providing necessary facilities. SVB and SVN are
thankful to DST, New Delhi, for the financial assistance
under Fast Track Scheme for Young Scientists [Sanction
Letter No. SR/FTP/CS-82/2007].
EXPERIMENTAL SECTION
Melting points were uncorrected and IR Spectra were
recorded using Nujol for solids on a Perkin-Elmer-1710
1
spectrophotometer. H NMR spectra were recorded at 200
MHz and 300 MHz in CDCl3 and DMSO-d6 using TMS as
an internal standard. Mass spectra were recorded under ESI
mode, on Thermo Finnigan (Model-LCQ Advantage MAX)
mass spectrometer.
[15]
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Li, W.; Chen, Y.; Lam, Y. A facile solid-phase synthesis of 3, 4, 6-
trisubstituted-2-pyridones using sodium benzenesulfinate as
a
traceless linker. Tetrahedron Lett., 2004, 45, 6545.
Rong, L.; Han, H.; Jiang, H.; Shi, D.; Tu, S. One-Pot synthesis of 4,
6-diaryl-2-oxo-1, 2-dihydropyridine-3-carbonitriles via three-
component cyclocondensation under solvent-free conditions. Synth.
Commun., 2008, 38, 217.
General Procedure for the Preparation of Substituted 2-
Pyridones
[17]
Spectral data for selected compound:
A mixture of aromatic ketone I (1mmol), aldehydes II
(1mmol), ethyl cyanoacetate III (1mmol), and ammonium
acetate IV (8mmol), in PEG-600(5-6ml) was stirred at 1100C
for appropriate time (mentioned in Tables 1, 2). After
completion of the reaction (monitored by TLC), the reaction
mass poured in to cold water. The solid 2-pyridone product,
which separated out, was filtered washed with water and
dried. The crude products were recrystallized from
ethanol/DMF mixture provided substituted 2-pyridone
(Scheme 1) with 60-80% yield.
1,2-dihydro-2-oxo-4,6-diphenylpyridine-3-carbonitrile
[Va]:
Yield - 80%, M.p.: >3000C. IR(Nujol): (NH) 3382, (CN) 2218,
(C=O) 1647 cm-1. 1H NMR (200 MHz,CDCl3+ DMSO-d6 )
ꢀ=12.60 (br, s, 1H, N-H), 7.53(m, 2H), 7.40 (m, 3H), 7.10-7.29 (m,
5H),6.80 ( s, 1H, pyridone C-H), MS (m/z): 273 (M+H) +, 272(M+).
1,2-dihydro-4-(3,4-dimethoxyphenyl)-2-oxo-6-phenylpyridine-
3-carbonitrile [Vb]: Yield- 71%, M.p.: 276-2770 C, IR(Nujol):
(NH) 3355, (CN) 2219, (C=O) 1651 cm-1 , 1H NMR (300 MHz,
DMSO-d6): ꢀ = 12.75 (br, s, 1H, NH), 7.88 (d, 2H), 7.53-7.55 (m,
3H), 7.34-7.36 (m, 2H), 7.12 (d, 1H), 6.83 (s, 1H, pyridone H),
3.83 (s, 6H, -OCH3), MS (m/z): 332 (M+).
6-(4-chlorophenyl)-1,2-dihydro-4-(3,4-dimethoxyphenyl)-2-oxo-
pyridine-3-Carbonitrile [Vc]: Yield
-
68%, M.p.: >3000C,
IR(Nujol): (N-H) 3305, (CN) 2221, (C=O) 1633 cm-1. 1H NMR
(300 MHz, DMSO-d6) ꢀ = 12.51 (br, s, 1H, NH), 7.92 (d, 2H), 7.60
(d, 2H), 7.33-7.36 (m, 2H), 7.12 (d, 1H), 6.89 (s, 1H), 3.83 (s, 6H, -
OCH3), MS (m/z): 366 (M+ ).
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6-(4-bromophenyl)-1,2-dihydro-4-(3,4-dimethoxyphenyl)-2-oxo-
pyridine-3-carbonitrile [Vd]: Yield- 67%, M.p.: 300 0C,
IR(Nujol): (N-H) 3431, (CN) 2222, (C=O) 1635 cm-1. 1H NMR
(300 MHz, DMSO-d6): ꢀ= 12.74 (br, s, 1H, NH), 7.84 (d, 2H),
7.73-7.76 (m, 2H), 7.34-7.37 (m, 2H), 7.13 (d, 1H), 6.90 (s, 1H,
pyridone H), 3.84 (s, 6H, -OCH3), MS (m/z): 411 (M+ ).
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1,2-dihydro-4-(3,4-dimethoxyphenyl)-6-(4-methoxyphenyl)-2-
oxopyridine-3-carbonitrile [Vf]: Yield-65%, M.p.: 2660C,
IR(Nujol): (N-H) 3350, (CN) 2222, (C=O) 1652 cm-1 1H NMR
.
(300 MHz , CDCl3+ DMSO-d6): ꢀ= 12.58 (br, s, 1H, NH), 7.88 (d,
2H), 7.32-7.34 (m, 2H), 7.12 (d, 1H), 7.07 (d, 2H), 6.78 (s, 1H,
pyridone H), 3.83 (s, 9H, -OCH3), MS (m/z): 363 (M++H),
362(M+).
6-(4-bromophenyl)-1,2-dihydro-2-oxo-4-phenylpyridine-3-car-
bonitrile6 [Vg]: Yield-68%, M.p: 2900C, IR(Nujol): (N-H) 3300,
(CN) 2223, (C=O) 1652 cm-1, 1H NMR (200 MHz, CDCl3+ DMSO-
d6): ꢀ= 12.75 (br, s, 1H, NH), 8.00-8.14 (m, 2H), 7.82 (m, 2H),
7.61-7.63 (m, 2H), 7.30-7.47 (m, 3H), 6.54 (s, 1H, pyridone H),
MS (m/z): 351 (M+ ).
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1, 2-dihydro-6-(naphthalen-3-yl)-2-oxo-4-phenylpyridine-3-car-
bonitrile [Vj]: Yield-70%, M.p.: >3000C, IR (Nujol): (N-H) 3320,
(CN) 2226, (C=O) 1639 cm-1, 1H NMR (300 MHz, DMSO-d6): ꢀ=
12.83 (br, s, 1H, NH), 8.55 (s, 1H), 7.98-8.06 (m, 4H), 7.75-7.78
(m, 2H), 7.58-7.63 (m, 5H), 7.01 (s, 1H), MS (m/z): 322 (M+).
4-hexyl-1,2-dihydro-2-oxo-6-phenylpyridine-3-carbonitrile [Vk]:
Yield- 68%, M.p.: 156-1580C, IR (Nujol): (N-H) 3400, (CN) 2217,
(C=O) 1653 cm-1, 1H NMR (300 MHz DMSO-d6): ꢀ=12.52 (br, s,
1H, N-H), 7.79 (d, 2H), 7.52-7.54 (m, 3H), 6.75 (s, 1H), 2.67 (t,
2H), 1.63 (t, 2H), 1.30 (m, 6H), 0.85 (t, 3H) MS (m/z): 281 (M+).
1,2-dihydro-4-isobutyl-2-oxo-6-phenylpyridine-3-carbonitrile
[Vl]: Yield-60%, M.p.: 188-1900C, IR (Nujol): (N-H) 3390, (CN)
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1
2216, (C=O)1646 cm-1, H NMR (300 MHz DMSO-d6): ꢀ= 12.5
(br, s, 1H, N-H), 7.80 (d, 2H), 7.52-7.54 (m, 3H), 6.72 (s, 1H), 2.57
(d, 2H), 2.02-2.07 (m, 1H), 0.94 (d, 6H), MS (m/z): 253 (M+).
4-butyl-1,2-dihydro-2-oxo-6-phenylpyridine-3-carbonitrile [Vm]:
Yield-72%, M.p.: 142-1440C, IR (Nujol): (N-H) 3400, (CN) 2219,
(C=O)1629 cm-1, 1H NMR (300 MHz DMSO-d6): ꢀ= 12.52 (br, s,