ꢂꢁꢁꢁ
O. Gómez-García et al.: Formamidines microwave reaction with methyl vinyl ketoneꢀ
ꢀ23
148.9, 151.2, 162.1, 206.8. Anal. Calcd for C11H14N2O2: C, 64.06; H, 6.84.
Found: C, 63.64; H, 7.29.
J ꢀ= ꢀ 7.5 Hz), 7.07 (1H, d, J ꢀ= ꢀ 8.5 Hz), 7.11 (1H, dq, J ꢀ= ꢀ 8.5 Hz, J ꢀ= ꢀ 2.5 Hz,
J ꢀ= ꢀ 1 Hz), 7.7 (1H, dt, J ꢀ= ꢀ 8.5 Hz, J ꢀ= ꢀ 1 Hz), 8.38 (d, 1H, J ꢀ= ꢀ 8.5 Hz), 9.06
(s, 1H); 13C NMR (125 MHz): δ 29.9, 37.6, 41.4, 112.6, 120.5, 138.5, 148.8,
153.3, 162.1, 206.7. Anal. Calcd for C10H12N2O2: C, 62.48; H, 6.29. Found:
C, 62.02; H, 6.53.
N-Formyl-6-methyl-N-(3-oxobutyl)-2-pyridylamine (4e)ꢀThis
compound was obtained afer 22 min of mw irradiation as brown
1
oil; yield 82%; H NMR (300 MHz): δ 2.03 (3H, s), 2.36 (3H, s), 2.71
(2H, t, J ꢀ= ꢀ 7.5 Hz), 4.04 (2H, t, J ꢀ= ꢀ 7.5 Hz), 6.76 (1H, d, J ꢀ= ꢀ 8.5 Hz),
6.87 (1H, d, J ꢀ= ꢀ 8.5 Hz), 7.49 (1H, t, J ꢀ= ꢀ 8.5 Hz), 8.93 (1H, s); 13C NMR
(75 MHz): δ 24.2, 30, 37.5, 41.4, 109.4, 119.9, 138.6, 152.4, 158.1, 162.2,
206.9. Anal. Calcd for C11H14N2O2: C, 64.06; H, 6.84. Found: C, 64.50;
H, 7.21.
5-Bromo-N-Formyl-N-(3-oxobutyl)-2-pyridylamine
(4b)ꢀThis
compound was obtained afer 60 min of mw irradiation as yellow
crystals; yield 83%; mp 102–103°C; 1H NMR (300 MHz): δ 2.09 (3H, s),
2.83 (2H, t, J ꢀ= ꢀ 7.5 Hz), 4.16 (2H, t, J ꢀ= ꢀ 7.5 Hz), 7 (1H, d, J ꢀ= ꢀ 8.5 Hz), 7.82
(1H, dd, J ꢀ= ꢀ 8.5 Hz, J ꢀ= ꢀ 2.5 Hz), 8.43 (1H, d, J ꢀ= ꢀ 2.5 Hz), 9,07 (1H, s); 13
C
NMR (75 MHz): δ 29.8, 37.4, 41.1, 113.4, 115.9, 140.8, 149, 151.7, 161.5, 206.3.
5-Methyl-N-(3-oxobutyl)-2-pyridylamine (5)ꢀ[10] This compound
was obtained as reported previously by the reaction of 2-amino-
5-methylpyridine (1.08 g, 10 mmol) with MVK (0.77 g, 11 mmol); yield
Anal. Calcd for C10H11N2BrO2: C, 44.3; H, 4.08. Found: C, 44.19; H, 3.98.
5-Chloro-N-Formyl-N-(3-oxobutyl)-2-pyridylamine
(4c)ꢀThis
1
80% of yellow crystals; mp 124–125.5°C; H NMR (300 MHz): δ 2.13
compound was obtained afer 55 min of mw irradiation as dark
1
(6H, s), 2.73 (2H, t, J ꢀ= ꢀ 6.0 Hz), 3.54 (2H, t, J ꢀ= ꢀ 6.0 Hz), 6.29 (1H, d, J ꢀ= ꢀ
8.4 Hz), 7.19 (1H, dd, J ꢀ= ꢀ 8.4 Hz, J ꢀ= ꢀ 2.4 Hz), 7.85 (1H, dd, J ꢀ= ꢀ 2.4 Hz, J ꢀ= ꢀ
0.9 Hz); 13C NMR (75 MHz): δ 17.3, 30.26, 36.4, 43, 107.4, 121.5, 138.4,
147.2, 156.4, 208.4.
yellow crystals; yield 81%; mp 92–93°C; H NMR (500 MHz): δ 2.09
(1H, s), 2.77 (2H, t, J ꢀ= ꢀ 7.5 Hz), 4.09 (2H, t, J ꢀ= ꢀ 7.5 Hz), 7.02 (1H, d, J ꢀ= ꢀ
8.5 Hz), 7.63 (1H, dd, J ꢀ= ꢀ 8.5 Hz, J ꢀ= ꢀ 2.5 Hz), 8.26 (1H, d, J ꢀ= ꢀ 2.5 Hz),
8.98 (1H, s); 13C NMR (125 MHz): δ 29.9, 37.5, 41.1, 113.1, 128, 138.1,
147.1, 151.4, 161.7, 206.6. Anal. Calcd for C10H11N2ClO2: C, 52.99; H, 4.89.
Found: C, 52.77; H, 5.04.
N1,N1-Dimethyl-N2-(5-methyl-2-pyridyl)formamidine
Dark yellow crystals; yield 90%; mp 68–70°C; H NMR (300 MHz): δ
2.14 (3H, s), 2.96 (6H, s), 6.77 (1H, d, J ꢀ= ꢀ 8.1 Hz), 7.25 (1H, dq, J ꢀ= ꢀ 8.1 Hz,
J ꢀ= ꢀ 3 Hz, J ꢀ= ꢀ 0.9 Hz), 7.96 (1H, dd, J ꢀ= ꢀ 3 Hz, J ꢀ= ꢀ 0.9 Hz), 8.26 (1H, s); 13C
(1f)ꢀ[6]
1
N-Formyl-5-methyl-N-(3-oxobutyl)-2-pyridylamine
(4d)ꢀThis
compound was obtained afer 20 min of mw irradiation as clear yel-
1
low oil; yield 88%; H NMR (300 MHz): δ 2.13 (3H, s), 2.28 (3 H, s),
NMR (75 MHz): δ 17.4, 17.5, 34.3, 117, 126.5, 138.3, 148, 155, 159.6.
2.57 (2H, t, J ꢀ= ꢀ 7.5 Hz), 4.15 (3H, t, J ꢀ= ꢀ 7.5 Hz), 6.95 (1H, d, J ꢀ= ꢀ 8.5 Hz),
7.51 (1H, dt, J ꢀ= ꢀ 8.5 Hz, J ꢀ= ꢀ 1.0 Hz), 8.20 (1H, dd, J ꢀ= ꢀ 2.5 Hz, J ꢀ= ꢀ 1.0 Hz),
8.94 (1H, s); 13C NMR (75 MHz): δ 17.7, 29.7, 37.9, 41.6, 112.63, 130.8, 139.1,
Received October 21, 2013; accepted November 19, 2013; previously
published online January 18, 2014
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