(C-4, C6H5); 128.88 (C-2, C-6, C6H5); 129.45 (C-3, C-5, C6H5); 133.73 (C-1, C6H5); 155.07 (=C–N); 170.69
(NHCO); 199.55 (COMe). Found, %: C 71.94; H 6.95; N 6.40. C13H15NO2. Calculated, %: C 71.87; H 6.96; N 6.45.
N-(1-Methyl-3-oxobut-1-en-1-yl)-2-[(4-methylphenyl)sulfonyl]acetamide (1c).
A
mixture of
chloroacetamide 1a (0.176 g,1.0 mmol) sodium p-toluenesulfinate monohydrate (0.294 g, 1.5 mmol), and KI
(0.017 g) in absolute DMF (3 ml) was stirred for 38 h, then poured into water (12 ml) and cooled. The
precipitated solid was filtered off, and recrystallized from ethanol. Compound 1c (0.265 g, 90%) was obtained
with mp 160-161oC. IR spectrum, ν, cm-1: 1601 (NC=O), 1704 (C=O), 3250-3400 (NH). 1H NMR spectrum, δ,
4
ppm (J, Hz): 2.16 (3H, s, COCH3); 2.30 (3H, d, J = 0.7, =C–CH3); 2.45 (3H, s, C6H4CH3); 4.08 (2H, s, CH2);
3
3
5.41 (1H, s, =CH); 7.36 (2H, d, J = 8.1, Ar); 7.82 (2H, d, J = 8.1, Ar); 12.60 (1H, br. s, NH). 13C NMR
spectrum, δ, ppm: 21.64 (C6H4CH3); 21.71 (=C–CH3); 30.53 (COCH3); 64.49 (CH2); 107.23 (=CH-); 128.45,
129.98, 135.52, 145.54 (Ar); 153.42 (=C–N); 160.34 (NHCO); 199.82 (C=O). Found, %: C 55.55; H 5.42;
N 4.94. C13H15NO4S. Calculated, %: C 55.50; H 5.37; N 4.98.
4,6-Dimethyl-3-phenylpyridin-2(1H)-one (4). Potassium tert-butylate (0.084 g, 0.75 mmol) was added
with ice-cooling and stirring to a solution of phenylacetamide 1b (0.109 g, 0.5 mmol) in absolute THF (4 ml).
After 2.5 h the solvent was evaporated, the residue triturated with water, the compound was filtered off, and
recrystallized from ethanol. Compound 4 (0.053 g, 53%) was obtained with mp 212-213oC. IR spectrum, ν, cm-1:
1
1628 (NC=O), 3300-3400 (NH). H NMR spectrum, δ, ppm (J, Hz): 2.02 (3H, s, 4-CH3); 2.22 (3H, s, 6-CH3);
13
5.96 (1H, s, H-5); 7.19-7.50 (5H, m, C6H5); 12.87 (1H, br. s, NH). C NMR spectrum, δ, ppm: 18.74 (4-CH3);
20.67 (6-CH3); 109.10 (C-5); 126.95 (C-4, Ph); 127.16 (C-3); 128.03 (C-3, C-5, C6H5); 130.32 (C-2, C-6, C6H5);
135.97 (C-1, C6H5); 143.14 (C-4); 149.45 (C-6); 164.44 (C-2). Mass spectrum, m/z, 199 [M]+·. Found, %:
C 78.40; H 6.53; N 6.98. C13H13NO. Calculated, %: C 78.36; H 6.58; N 7.03.
4,6-Dimethyl-3-[(4-methylphenyl)sulfonyl]pyridin-2-one (5). A mixture of compound 1a (0.176 g,
1.0 mmol), K2CO3 (0.207 g, 1.5 mmol), sodium p-toluenesulfinate monohydrate (0.294 g, 1.5 mmol), 0.017g KI,
and absolute DMF (3 ml) was stirred for 3 days, after which the mixture was poured into water (12 ml), and
cooled. The solid was filtered off, and recrystallized from ethanol. Compound 5 (0.196 g, 71%) was obtained.
Compound 5 (0.177 g, 64%) was also obtained having mp 268-270oC (decomp.) analogously, from compound 1c
(0.295 g, 1.0 mmol) and K2CO3 (0.207 g) in absolute DMF (3 ml) with stirring for 24 h. IR spectrum, ν, cm-1: 1623
1
(NC=O), 3200-3400 (NH). H NMR spectrum (DMSO-d6), δ, ppm (J, Hz): 2.16 (3H, s, 4-CH3); 2.36 (3H, s,
6-CH3); 2.62 (3H, s, C6H4CH3); 6.07 (1H, s, H-5); 7.33 (2H, d, 3J = 8.1, Ar); 7.80 (2H, d, 3J = 8.1, Ar); 12.01 (1H,
br. s, NH). 13C NMR spectrum (DMSO-d6), δ, ppm: 18.37 (6-CH3); 20.91 (4-CH3); 21.14 (C6H4CH3); 109.15
(C-5); 122.70 (C-3); 127.55, 128.68, 139.46, 142.95 (Ar); 151.29 (C-6); 156.33 (C-4); 158.29 (NCO). Found, %:
C 60.72; H 5.50; N 4.99. C13H13NO3S. Calculated, %: C 60.63; H 5.45; N 5.05.
REFERENCES
1.
2.
3.
K. Gewald, M. Rehwald, H. Müller, and P. Bellman, Liebigs Ann. Chem., 787 (1995).
P. G. Baraldi, D. Simoni, and S. Manfredini, Synthesis, 902 (1983).
R. Shabana, J. B. Rasmussen, and S.-O. Lawesson, Tetrahedron, 37, 1819 (1981).
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