Halogen-Containing 4H-Pyrido[e][1,3]oxazin-4-ones
H), 8.87 (s, 1 H), 8.06 (dd, J = 8.3, 1.5 Hz, 1 H), 7.60 (td, J = 7.5, 693, 671, 639, 620 cm–1. HRMS (ESI+): calcd. for C14H10BrN2O2
1.0 Hz, 1 H), 7.45 (d, J = 5.2 Hz, 1 H), 7.44 (d, J = 7.0 Hz, 1 H), [M + H] 316.9920; found 316.9925, m.p. 208–210 °C.
2.68 (s, 3 H) ppm. J-MOD 13C NMR (125 MHz, [D6]DMSO): δ =
Sodium (3,5-Dibromoisonicotinoyl)(2-fluorobenzoyl)amide (7e):
163.7, 162.6, 151.2, 149.7, 140.2, 139.6, 133.0, 132.0, 130.7, 128.7,
Compound 7e was obtained (97%, 0.586 g) as a pale yellow powder
126.2, 121.5, 116.3, 21.4 ppm. IR (film): ν = 3444, 3058, 2962, 2924,
˜
from 3,5-dibromoisonicotinamide (2; 0.4 g) according to general
procedure A. H NMR (400 MHz, [D6]DMSO): δ = 8.52 (s, 2 H),
1695, 1610, 1592, 1658, 1538, 1491, 1457, 1406, 1378, 1333, 1309,
1287, 1272, 1246, 1209, 1201, 1169, 1146, 1099, 1060, 1033, 1026,
930, 890, 807, 784, 731, 695, 643, 635, 608, 556 cm–1. HRMS
(ESI+): calcd. for C14H10BrN2O2 [M + H] 316.9920; found
316.9921, m.p. 172–174 °C.
1
7.80 (td, J = 7.7, 1.8 Hz, 1 H), 7.34 (m, 1 H), 7.10 (qd, J = 7.5,
1.0 Hz, 1 H), 7.05 (dd, J = 8.3, 0.8 Hz, 1 H) ppm. J-MOD 13C
NMR (100 MHz, [D6]DMSO): δ = 172.9, 170.9, 160.4 (d, J =
250 Hz, 1 C), 153.9, 149.1 (2 C), 131.4 (d, J = 2.9 Hz, 1 C), 130.6
(d, J = 8.3 Hz, 1 C), 129.1 (d, J = 11.1 Hz, 1 C), 123.1 (d, J =
3.6 Hz, 1 C), 117.0 (2 C); 115.8 (d, J = 22.5 Hz, 1 C) ppm. 19F
Sodium (3,5-Dibromoisonicotinoyl)(3-methylbenzoyl)amide (7c):
Compound 7c was obtained (96%, 0.574 g) as a white powder from
3,5-dibromoisonicotinamide (2; 0.4 g) according to general pro-
cedure A. 1H NMR (500 MHz, [D6]DMSO): δ = 8.51 (s, 2 H), 7.84
(s, 1 H), 7.79 (d, J = 6.3 Hz, 1 H), 7.21 (t, J = 7.3 Hz, 1 H), 7.19
(m, 1 H), 2.31 (s, 3 H) ppm. J-MOD 13C NMR (125 MHz, [D6]
DMSO): δ = 174.2, 171.3, 154.4, 149.1 (2 C), 139.5, 136.2, 130.6,
NMR (188 MHz, [D ]DMSO): δ = –113.7 ppm. IR (film): ν =
˜
6
3431, 3072, 2303, 1629, 1611, 1575, 1517, 1482, 1445, 1388, 1295,
1263, 1211, 1156, 1139, 1113, 1083, 1043, 913, 888, 843, 813, 800,
759, 695, 680, 631, 593, 561, 526, 498 cm–1. HRMS (only the free
imide-NH could be detected; ESI+): calcd. for C13H8Br2FN2O2
[M – Na + 2] 400.8936; found 400.8947, m.p. 272–274 °C.
129.6, 127.2, 126.0, 117.0 (2 C), 21.0 ppm. IR (film): ν = 3445,
˜
3057, 2918, 1811, 1613, 1596, 1577, 1518, 1476, 1441, 1402, 1299,
1217, 1180, 1163, 1126, 1084, 1051, 883, 810, 783, 760, 746, 715,
691, 679, 636, 592, 538, 506 cm–1. HRMS (only the free imide-NH
could be detected; ESI+): calcd. for C14H11Br2N2O2 [M – Na + 2]
396.9182; found 396.9178, m.p. 275–277 °C.
5-Bromo-2-(2-fluorophenyl)-4H-pyrido[4,3-e][1,3]oxazin-4-one (8e):
Compound 8e was obtained (47%, 0.107 g) as a brown powder
from sodium (3,5-dibromoisonicotinoyl)(2-fluorobenzoyl)amide
(7e; 0.300 g) according to general procedure D, using DMSO
1
(14 mL). H NMR (400 MHz, [D6]DMSO): δ = 9.04 (s, 1 H), 8.90
(s, 1 H), 8.21 (t, J = 7.4 Hz, 1 H), 7.82 (d, J = 5.0 Hz, 1 H), 7.49
(t, J = 10.3 Hz, 1 H), 7.47 (t, J = 7.2 Hz, 1 H) ppm. J-MOD 13C
NMR (100 MHz, [D6]DMSO): δ = 162.5, 160.5 (d, J = 4.0 Hz, 1
C), 160.2 (d, J = 255.6 Hz, 1 C), 151.2, 150.0, 140.2, 136.5 (d, J =
9.2 Hz, 1 C), 132.0, 125.1 (d, J = 3.5 Hz, 1 C), 121.8, 117.5 (d, J
= 21.7 Hz, 1 C), 117.4, 116.4 ppm. 19F NMR (188 MHz, [D6]-
5-Bromo-2-(m-tolyl)-4H-pyrido[4,3-e][1,3]oxazin-4-one (8c): Com-
pound 8c was obtained (71%, 0.160 g) as a white powder from
sodium (3,5-dibromoisonicotinoyl)(3-methylbenzoyl)amide (7c;
0.3 g) according to general procedure D, using DMSO (14 mL). 1H
NMR (400 MHz, [D6]DMSO): δ = 9.12 (s, 1 H), 8.87 (s, 1 H), 8.14
(s, 1 H), 8.12 (d, J = 8.0 Hz, 1 H), 7.59 (d, J = 7.5 Hz, 1 H), 7.54
(t, J = 7.5 Hz, 1 H), 2.45 (s, 3 H) ppm. J-MOD 13C NMR
(100 MHz, [D6]DMSO): δ = 162.9, 162.3, 151.2, 149.8, 140.3,
138.7, 135.3, 129.4, 129.1, 128.9, 126.4, 121.8, 116.4, 20.8 ppm. IR
DMSO): δ = –107.8 ppm. IR (CH Cl ): ν = 3390, 3063, 3047, 1707,
˜
2
2
1613, 1604, 1578, 1541, 1486, 1459, 1449, 1403, 1328, 1241, 1230,
1201, 1157, 1136, 1126, 1112, 1096, 1025, 935, 897, 885, 821, 808,
775, 685, 668, 639, 631 cm–1. HRMS (ESI+): calcd. for
C13H7BrFN2O2 [M + H] 320.9675; found 320.9681, m.p. 169–
170 °C.
(CH Cl ): ν = 3685, 3061, 3048, 2984, 2926, 1705, 1602, 1582, 1539,
˜
2
2
1480, 1449, 1403, 1383, 1319, 1289, 1243, 1216, 1203, 1175, 1137,
1125, 1088, 1047, 998, 939, 918, 912, 884, 802, 789, 677, 668,
641 cm–1. HRMS (ESI+): calcd. for C14H10BrN2O2 [M + H]
316.9920; found 316.9920, m.p. 200–202 °C.
Sodium (3,5-Dibromoisonicotinoyl)(3-fluorobenzoyl)amide (7f):
Compound 7f was obtained (99%, 0.600 g) as a white powder from
3,5-dibromoisonicotinamide (2; 0.4 g) according to general pro-
cedure A. 1H NMR (500 MHz, [D6]DMSO): δ = 8.52 (s, 2 H), 7.83
(d, J = 7.7 Hz, 1 H), 7.70 (dq, J = 10.4, 1.4 Hz, 1 H), 7.37 (td, J
= 8.0, 5.9 Hz, 1 H), 7.20 (tdd, J = 8.4, 2.7, 0.8 Hz, 1 H) ppm. J-
MOD 13C NMR (125 MHz, [D6]DMSO): δ = 172.5 (d, J = 2.1 Hz,
1 C), 171.7, 161.8 (d, J = 240.7 Hz, 1 C), 154.3, 149.1 (2 C), 142.5
(d, J = 6.2 Hz, 1 C), 129.3 (d, J = 7.8 Hz, 1 C), 124.7 (d, J =
2.3 Hz, 1 C), 116.9 (2 C), 116.7 (d, J = 21.3 Hz, 1 C), 115.1 (d, J
Sodium (3,5-Dibromoisonicotinoyl)(4-methylbenzoyl)amide (7d):
Compound 7d was obtained (89%, 0.535 g) as a white powder from
3,5-dibromoisonicotinamide (2; 0.4 g) according to general pro-
cedure A. 1H NMR (400 MHz, [D6]DMSO): δ = 8.52 (s, 2 H), 7.91
(d, J = 7.9 Hz, 2 H), 7.13 (d, J = 7.9 Hz, 2 H), 2.31 (s, 3 H) ppm.
J-MOD 13C NMR (100 MHz, [D6]DMSO): δ = 174.2, 171.3, 154.2,
149.1 (2 C), 139.6, 136.8, 129.0 (2 C), 128.0 (2 C), 117.1 (2 C),
21.0 ppm. IR (film): ν = 3627, 3432, 3066, 3030, 2920, 1622, 1609,
˜
= 21.6 Hz, 1 C) ppm. IR (film): ν = 3440, 3068, 1950, 1883, 1837,
˜
1572, 1549, 1506, 1441, 1406, 1306, 1293, 1279, 1211, 1170, 1139,
1116, 1091, 1051, 1018, 901, 847, 794, 771, 759, 730, 691, 656, 637,
621, 607, 590 cm–1. HRMS (only the free imide-NH could be de-
tected; ESI+): calcd. for C14H11Br2N2O2 [M – Na + 2] 396.9187;
found 396.9173, m.p. 290–291 °C.
1624, 1583, 1550, 1508, 1446, 1406, 1284, 1272, 1244, 1210, 1179,
1153, 1123, 1099, 1090, 1069, 1053, 1002, 976, 947, 910, 896, 829,
808, 782, 772, 758, 734, 678, 669, 654, 603, 555, 524 cm–1. HRMS
(only the free imide-NH could be detected; ESI+): calcd. for
C13H8Br2FN2O2 [M – Na + 2] 400.8931; found 400.8929, m.p. 291–
294 °C.
5-Bromo-2-(p-tolyl)-4H-pyrido[4,3-e][1,3]oxazin-4-one (8d): Com-
pound 8d was obtained (72%, 0.134 g) as a yellow powder from
sodium (3,5-dibromoisonicotinoyl)(4-methylbenzoyl)amide (7d;
0.247 g) according to general procedure D, using DMSO (12 mL).
1H NMR (400 MHz, [D6]DMSO): δ = 9.10 (s, 1 H), 8.86 (s, 1 H),
5-Bromo-2-(3-fluorophenyl)-4H-pyrido[4,3-e][1,3]oxazin-4-one (8f):
Compound 8f was obtained (44%, 0.101 g) as a yellow powder
from sodium (3,5-dibromoisonicotinoyl)(3-fluorobenzoyl)amide
(7f; 0.300 g) according to general procedure D, using DMSO
1
8.21 (d, J = 8.3 Hz, 2 H), 7.47 (d, J = 8.1 Hz, 2 H), 2.45 (s, 3 H) (20 mL). H NMR (500 MHz, [D6]DMSO): δ = 9.15 (s, 1 H), 8.89
ppm. J-MOD 13C NMR (100 MHz, [D6]DMSO): δ = 162.8, 162.3,
(s, 1 H), 8.17 (dt, J = 7.8, 1.2 Hz, 1 H), 8.09 (ddd, J = 9.7, 2.3,
151.2, 149.7, 145.5, 140.3, 129.8 (2 C), 129.2 (2 C), 126.2, 121.8, 1.8 Hz, 1 H), 7.72 (td, J = 8.1, 5.8 Hz, 1 H), 7.65 (tdd, J = 8.3, 2.7,
116.4, 21.3 ppm. IR (CH Cl ): ν = 3052, 2980, 2917, 1703, 1653,
1603, 1585, 1571, 1539, 1507, 1449, 1404, 1317, 1256, 1241, 1208,
1182, 1137, 1127, 1119, 1036, 1018, 930, 894, 884, 833, 808, 788,
0.9 Hz, 1 H) ppm. J-MOD 13C NMR (125 MHz, [D6]DMSO): δ =
162.7, 162.1 (d, J = 244 Hz, 1 C), 161.0 (d, J = 3.5 Hz, 1 C), 151.0,
149.9, 140.3, 131.4 (d, J = 8.0 Hz, 1 C), 131.3 (d, J = 8.2 Hz, 1 C),
˜
2
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Eur. J. Org. Chem. 2015, 3830–3840
© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
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