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H. Schirok et al.
PAPER
6-(Cyclobutylamino)-5-(4-fluorobenzoyl)-1-(2-methoxyeth-
yl)pyridin-2(1H)-one (3l)
5-(4-Fluorobenzoyl)-6-[(trans-4-hydroxycyclohexyl)amino]-1-
phenylpyridin-2(1H)-one (3q)
1H NMR (400 MHz, DMSO-d6): d = 1.50–1.61 (m, 1 H), 1.62–1.70
(m, 1 H), 1.92–2.02 (m, 2 H), 2.15–2.23 (m, 2 H), 3.28 (s, 3 H), 3.62
(t, J = 5.0 Hz, 2 H), 3.99 (m, 1 H), 4.23 (t, J = 5.0 Hz, 2 H), 5.71 (d,
J = 9.5 Hz, 1 H), 7.29–7.35 (m, 3 H), 7.64 (dd, J = 7.4, 6.0 Hz, 2 H),
9.19 (d, J = 5.0 Hz, 1 H).
1H NMR (500 MHz, DMSO-d6): d = 0.57–0.64 (m, 2 H), 1.05–1.12
(m, 2 H), 1.55–1.63 (m, 4 H), 1.86–1.96 (m, 1 H), 3.21–3.28 (m, 1
H), 4.48 (d, J = 3.9 Hz, 1 H), 5.75 (d, J = 9.7 Hz, 1 H), 7.34 (t,
J = 8.7 Hz, 2 H), 7.43–7.48 (m, 3 H), 7.54–7.61 (m, 5 H), 11.16 (d,
J = 8.8 Hz, 1 H).
13C NMR (125 MHz, DMSO-d6): d = 13.9, 31.0, 42.8, 51.0, 58.4,
13C NMR (125 MHz, DMSO-d6): d = 31.1, 33.2, 52.5, 67.1, 99.1,
2
3
2
69.3, 100.3, 104.8, 115.4 (d, JC,F = 21.8 Hz), 131.4 (d, JC,F = 8.9
104.6, 115.4 (d, JC,F = 21.7 Hz), 128.8, 129.1, 129.5, 130.6 (d,
4
Hz), 135.5 (d, JC,F = 3.0 Hz), 142.9, 155.6, 162.0, 163.6 (d,
3JC,F = 8.7 Hz), 136.4 (d, 4JC,F = 3.1 Hz), 137.8, 144.3, 157.2, 161.7,
1JC,F = 249 Hz), 190.5.
163.1 (d, 1JC,F = 248 Hz), 191.6.
HRMS: m/z [M+] calcd for C19H21FN2O3: 344.1536; found:
HRMS: m/z [M+] calcd for C24H23FN2O3: 406.1693; found:
344.1533.
406.1704.
5-Benzoyl-6-(isobutylamino)-1-phenylpyridin-2(1H)-one (3m)
1H NMR (500 MHz, DMSO-d6): d = 0.71 (d, J = 6.6 Hz, 6 H), 1.57
(tsept, J = 6.6, 6.2 Hz, 1 H), 2.16 (dd, J = 6.2, 5.5 Hz, 2 H), 5.71 (d,
J = 9.6 Hz, 1 H), 7.42–7.57 (m, 11 H), 11.29 (t, J = 5.5 Hz, 1 H).
13C NMR (125 MHz, DMSO-d6): d = 19.5, 28.3, 52.0, 98.8, 104.1,
127.9, 128.3, 129.0, 129.1, 129.6, 130.2, 137.5, 139.9, 144.3, 157.8,
161.7, 192.8.
5-Benzoyl-6-(ethylsulfinyl)-1-phenylpyridin-2(1H)-one (11a)
5-Benzoyl-6-(ethylthio)-1-phenylpyridin-2(1H)-one 5i (600 mg,
1.79 mmol) was dissolved in CH2Cl2 (8 mL) and cooled to 0 °C.
MCPBA (77%, 420 mg, 1.88 mmol) was added and the mixture was
warmed to r.t. After stirring for 3 h the reaction was cooled to 0 °C
and filtered. The filtrate was extracted twice with a sat. solution of
NaHCO3 (2 × 10 mL) and brine (10 mL). The organic layer was
dried (Na2SO4) and the solvent was evaporated. The crude product
was purified by column chromatography on silica gel (EtOAc–pe-
troleum ether, 2:1) to yield 614 mg (93%) of a slightly yellow solid.
HRMS: m/z [M+] calcd for C22H22N2O2: 346.1681; found:
346.1676.
1H NMR (500 MHz, DMSO-d6): d = 0.95 (t, J = 7.5 Hz, 3 H), 2.90–
3.05 (m, 2 H), 6.67 (d, J = 9.4 Hz, 1 H), 7.47 (d, J = 9.4 Hz, 1 H),
7.49–7.61 (m, 6 H), 7.62–7.68 (m, 2 H), 7.84–7.87 (m, 2 H).
13C NMR (125 MHz, DMSO-d6): d = 7.6, 47.7, 119.1, 121.1, 128.4,
128.8, 129.2, 129.4, 129.5, 129.6, 129.8, 133.2, 135.7, 137.0, 139.0,
151.9, 160.8, 192.5.
5-Benzoyl-1-phenyl-6-[(2-thienylmethyl)amino]pyridin-2(1H)-
one (3n)
1H NMR (500 MHz, DMSO-d6): d = 3.77 (d, J = 4.6 Hz, 2 H), 5.78
(d, J = 9.7 Hz, 1 H), 6.84 (br s, 1 H), 6.93 (t, J = 3.5 Hz, 1 H), 7.44–
7.61 (m, 12 H), 10.59 (t, J = 4.6 Hz, 1 H).
13C NMR (125 MHz, DMSO-d6): d = 43.1, 99.6, 105.0, 126.4,
126.7, 127.1, 128.1, 128.4, 129.4, 129.5, 129.6, 130.6, 137.1, 139.3,
139.7, 144.2, 156.9, 161.7, 193.0.
HRMS: m/z [M+] calcd for C20H17NO3S: 351.0929; found:
351.0930.
HRMS: m/z [M+] calcd for C23H18N2O2S: 386.1089; found:
386.1087.
5-Benzoyl-6-(cyclohexylamino)-1-phenylpyridin-2(1H)-one (3s)
1H NMR (500 MHz, DMSO-d6): d = 0.65–0.77 (m, 2 H), 0.97–1.11
(m, 3 H), 1.29–1.36 (m, 1 H), 1.46–1.57 (m, 4 H), 1.93–2.03 (m, 1
H), 5.73 (d, J = 9.7 Hz, 1 H), 7.44–7.61 (m, 11 H), 11.26 (d, J = 9.0
Hz, 1 H).
13C NMR (125 MHz, DMSO-d6): d = 23.8, 24.3, 33.1, 52.5, 99.0,
104.3, 127.8, 128.2, 128.7, 129.0, 129.3, 130.1, 137.7, 139.8, 144.2,
156.9, 161.6, 192.8.
5-(4-Fluorobenzoyl)-1-(4-fluorophenyl)-6-[(3-furylmethyl)ami-
no]pyridin-2(1H)-one (3o)
1H NMR (500 MHz, DMSO-d6): d = 3.51 (d, J = 4.4 Hz, 2 H), 5.76
(d, J = 9.6 Hz, 1 H), 6.35 (s, 1 H), 7.33 (t, J = 8.7 Hz, 2 H), 7.40 (t,
J = 8.6 Hz, 2 H), 7.47 (d, J = 9.6 Hz, 1 H), 7.50–7.56 (m, 5 H), 7.61
(s, 1 H), 10.76 (t, J = 4.4 Hz, 1 H).
13C NMR (125 MHz, DMSO-d6): d = 39.8, 99.1, 104.4, 109.8,
HRMS: m/z [M+] calcd for C24H24N2O2: 372.1838; found:
372.1827.
2
2
115.2 (d, JC,F = 21.7 Hz), 116.1 (d, JC,F = 22.9 Hz), 120.9, 130.6
3
3
4
(d, JC,F = 8.8 Hz), 131.8 (d, JC,F = 8.9 Hz), 133.1 (d, JC,F = 3.0
Hz), 136.0 (d, 4JC,F = 3.1 Hz), 140.5, 143.96, 144.02, 156.9, 161.5
(d, 1JC,F = 152 Hz), 161.6, 163.5 (d, 1JC,F = 153 Hz), 191.2.
5-Benzoyl-6-[(2-hydroxy-1-phenylethyl)amino]-1-phenylpyri-
din-2(1H)-one (3t)
1H NMR (500 MHz, DMSO-d6): d = 3.23–3.30 (m, 1 H), 3.39–3.46
(m, 1 H), 3.53–3.60 (m, 1 H), 5.13 (t, J = 5.0 Hz, 1 H), 5.74 (d,
J = 9.7 Hz, 1 H), 6.82 (dd, J = 7.8, 1.8 Hz, 2 H), 6.89 (d, J = 7.8 Hz,
1 H), 7.20–7.28 (m, 3 H), 7.36 (t, J = 7.6 Hz, 1 H), 7.47 (d, J = 9.7
Hz, 1 H), 7.46–7.63 (m, 8 H), 11.25 (br s, 1 H).
HRMS: m/z [M+] calcd for C23H16F2N2O3: 406.1129; found:
406.1120.
5-(4-Fluorobenzoyl)-1-(4-fluorophenyl)-6-[(2-hydroxyeth-
yl)amino]pyridin-2(1H)-one (3p)
1H NMR (500 MHz, DMSO-d6): d = 2.47 (dt, J = 7.0, 4.9 Hz, 2 H),
3.33 (2 H, under water peak), 4.88 (t, J = 4.7 Hz, 1 H), 5.70 (d,
J = 9.6 Hz, 1 H), 7.34 (t, J = 8.8 Hz, 2 H), 7.38 (t, J = 8.5 Hz, 2 H),
7.46 (d, J = 9.6 Hz, 1 H), 7.49 (dd, J = 8.7, 4.9 Hz, 2 H), 7.57 (dd,
J = 8.2, 5.7 Hz, 2 H), 11.04 (br s, 1 H).
13C NMR (125 MHz, DMSO-d6): d = 59.9, 65.6, 100.1, 104.7,
126.4, 127.3, 128.0, 128.2, 128.3, 128.7, 128.9, 129.0, 129.2, 129.5,
130.4, 136.9, 138.8, 139.7, 144.2, 157.5, 161.5, 193.1.
HRMS: m/z [M+] calcd for C26H22N2O3: 410.1630; found:
410.1633.
13C NMR (125 MHz, DMSO-d6): d = 47.5, 59.2, 98.7, 103.6, 115.2
(d, 2JC,F = 21.7 Hz), 116.0 (d, 2JC,F = 22.8 Hz), 130.5 (d, 3JC,F = 8.8
5-Benzoyl-6-(tert-butylamino)-1-phenylpyridin-2(1H)-one (3u)
1H NMR (500 MHz, DMSO-d6): d = 0.80 (s, 9 H), 5.99 (d, J = 9.6
Hz, 1 H), 7.43–7.48 (m, 4 H), 7.50–7.56 (m, 4 H), 7.58–7.64 (m, 3
H), 8.46 (s, 1 H).
3
4
Hz), 131.8 (d, JC,F = 8.8 Hz), 133.5 (d, JC,F = 3.1 Hz), 136.3 (d,
4JC,F = 3.1 Hz), 144.2, 157.5, 161.4 (d, 1JC,F = 154 Hz), 161.7, 163.3
(d, 1JC,F = 155 Hz), 191.0.
HRMS: m/z [M+] calcd for C20H16F2N2O3: 370.1129; found:
370.1124.
Synthesis 2005, No. 18, 3085–3094 © Thieme Stuttgart · New York