The Journal of Organic Chemistry
Article
126.7 (d, J = 9.3 Hz), 125.4, 123.3, 115.1, 111.1 (d, J = 22.3 Hz), 99.8
(
1
d, J = 27.9 Hz), 63.2, 21.3; IR (KBr) ν = 2954, 2916, 2848, 1660, 1617,
̃
−
1
593, 1482, 1426, 1328, 1266, 1171, 1037, 1010, 941, 836 cm ; HR-
+
MS (ESI-TOF) m/z calcd for C H FNO [M + H] 258.0925, found
1
5
13
2
258.0936.
5
3
3
-Chloro-5-methoxyphenanthridin-6(5H)-one (2f): R = 0.45
f
1
(
(
(
(
3
1
1
2
hexane/ethyl acetate 4:1); white solid; yield 89% (71 mg); H NMR
400 MHz, CDCl + DMSO-d ) δ 8.63 (dd, J = 8.0, 1.2 Hz, 1H), 8.32
3
6
d, J = 8.0 Hz, 1H), 8.29 (d, J = 8.4 Hz, 1H), 7.93−7.87 (m, 1H), 7.77
d, J = 2.0 Hz. 1H), 7.75−7.69 (m, 1H), 7.44−7.39 (m, 1H), 4.25 (s,
H); 13C{ H} NMR (100 MHz, CDCl + DMSO-d ) δ 157.3, 136.7,
1
3
6
36.1, 132.9, 132.3, 128.6, 128.4, 126.1, 124.6, 123.5, 122.0, 117.1,
3-Ethyl-5-methoxy-8-methylphenanthridin-6(5H)-one (2k): R =
f
+
12.6, 62.9; HR-MS (ESI-TOF) m/z calcd for C H ClNO [M + H]
0.45 (hexane/ethyl acetate 4:1); white solid; yield 86% (68 mg); mp
1
4
11
2
1
60.0473, found 260.0474.
116−118 °C; H NMR (400 MHz, CDCl ) δ 8.34 (s, 1H), 8.13 (d, J =
3
3
.6 Hz, 1H), 8.11 (d, J = 3.6 Hz, 1H), 7.56 (dd, J = 8.4, 1.6 Hz, 1H), 7.48
(
s, 1H), 7.18 (dd, J = 8.4, 1.2 Hz, 1H), 4.13 (d, J = 4.4 Hz, 3H), 2.81 (q,
1
3
1
J = 7.6 Hz, 2H), 2.51 (s, 3H), 1.33 (t, J = 7.6 Hz, 3H); C{ H} NMR
100 MHz, CDCl ) δ 157.7, 146.5, 137.9, 135.6, 134.0, 130.8, 128.3,
(
3
125.9, 123.3, 123.1, 121.9, 116.7, 111.7, 62.7, 29.3, 21.4, 15.7; IR (KBr)
5
8
ν = 2922, 2852, 1707, 1646, 1613, 1482, 1458, 1327, 1284, 1159, 1097,
̃
5
-Methoxy-3-(trifluoromethyl)phenanthridin-6(5H)-one (2g):
−
1
1
065, 984, 862 cm ; HR-MS (ESI-TOF) m/z calcd for C H NO
17 18 2
R = 0.50 (hexane/ethyl acetate 4:1); white solid; yield 93% (55.5
mg); H NMR (700 MHz, CDCl ) δ 8.59 (dd, J = 8.4, 0.7 Hz, 1H), 8.38
f
+
1
3
(
(
(
d, J = 8.4 Hz, 1H), 8.31 (d, J = 8.4 Hz, 1H), 7.93 (s, 1H), 7.87−7.82
m, 1H), 7.69 (dd, J = 11.2, 3.5 Hz, 1H), 7.59 (d, J = 8.4 Hz, 1H), 4.18
s, 3H); 13C{ H} NMR (175 MHz, CDCl ) δ 157.3, 136.1, 133.2,
1
3
1
2
31.9, 131.9 (q, J = 33.0 Hz), 129.4, 128.9, 127.1, 124.2, 123.9 (q, J =
72.5 Hz), 122.6, 121.4, 119.8 (q, J = 3.3 Hz), 63.2; HR-MS (ESI-
TOF) m/z calcd for C H F NO [M + H]+ 294.0736, found
1
5
11
3
2
3
-Chloro-5-methoxy-8-methylphenanthridin-6(5H)-one (2l): R =
f
0
1
8
.50 (hexane/ethyl acetate 4:1); white solid; yield 83% (66 mg); mp
91−193 °C; H NMR (400 MHz, CDCl + DMSO-d ) δ 8.17 (s, 1H),
.02 (d, J = 8.4 Hz, 1H), 7.98 (d, J = 8.4 Hz, 1H), 7.51 (d, J = 2.0 Hz,
1
3
6
1
H), 7.48 (d, J = 8.4 Hz, 1H), 7.17 (dt, J = 8.4, 2.0 Hz, 1H), 4.01 (s,
1
3
1
3H), 2.40 (s, 3H); C{ H} NMR (100 MHz, CDCl + DMSO-d ) δ
3 6
1
57.1, 138.6, 136.0, 135.2, 134.1, 129.6, 128.0, 125.6, 124.2, 123.3,
5
8
121.9, 116.9, 112.3, 62.7, 21.2; IR (KBr) ν = 2915, 2847, 1659, 1618,
̃
1537, 1425, 1312, 1137, 1091, 1039, 827 cm ; HR-MS (ESI-TOF) m/
5
-Methoxy-8-methylphenanthridin-6(5H)-one (2h): R = 0.50
f
1
−1
(
(
1
2
hexane/ethyl acetate 4:1); white solid; yield 88% (87 mg); H NMR
400 MHz, DMSO-d ) δ 8.47 (d, J = 8.0 Hz, 1H), 8.43 (d, J = 8.4 Hz,
+
6
H), 8.16 (s, 1H), 7.69 (dd, J = 8.4, 1.6 Hz, 1H), 7.64 (d, J = 4.0 Hz,
1
3
1
H), 7.42−7.30 (m, 1H), 4.02 (s, 3H), 2.49 (s, 3H); C{ H} NMR
(
100 MHz, DMSO-d ) δ 156.1, 138.2, 135.1, 134.2, 130.2, 129.9, 127.3,
6
1
25.6, 123.6, 123.3, 122.8, 117.9, 112.2, 62.5, 20.9; HR-MS (ESI-TOF)
+
15
14
2
-Chloro-5-methoxy-8-methylphenanthridin-6(5H)-one (2m): Rf
=
0.50 (hexane/ethyl acetate 4:1); white solid; yield 78% (62 mg); mp
1
1
=
82−184 °C; H NMR (400 MHz, DMSO-d ) δ 8.49 (s, 1H), 8.43 (d, J
6
8.4 Hz, 1H), 8.13 (s, 1H), 7.67 (dd, J = 8.4, 1.6 Hz, 1H), 7.62 (s, 2H),
1
3
1
4
1
1
1
.02 (s, 3H), 2.48 (s, 3H); C{ H} NMR (100 MHz, DMSO-d ) δ
56.3, 139.4, 134.7, 134.4, 129.9, 129.6, 128.3, 127.8, 126.4, 123.7,
23.6, 120.1, 114.7, 63.2, 21.3; IR (KBr) ν
583, 1477, 1404, 1332, 1227, 1132, 1038, 848 cm ; HR-MS (ESI-
5
3
6
5
-Methoxy-3,8-dimethylphenanthridin-6(5H)-one (2i): Rf = 0.50
1
(
(
(
2
1
1
hexane/ethyl acetate 4:1); white solid; yield 89% (88 mg); H NMR
̃
= 2975, 2927, 1663, 1613,
400 MHz, CDCl ) δ 8.33 (s, 1H), 8.09 (dd, J = 8.0, 5.2 Hz, 2H), 7.56
−1
3
d, J = 8.0 Hz, 1H), 7.45 (s, 1H), 7.15 (d, J = 8.0 Hz, 1H), 4.14 (s, 3H),
+
1
3
1
H12ClNaNO [M + Na] 296.0449, found
2
.51 (s, 3H), 2.49 (s, 3H); C{ H} NMR (100 MHz, CDCl ) δ 157.7,
3
296.0478.
40.1, 137.9, 135.4, 134.1, 130.8, 128.3, 1258, 124.5, 123.0, 121.8,
16.4, 112.8, 62.8, 21.9, 21.4; HR-MS (ESI-TOF) m/z calcd for
+
16
15
2
5
-Methoxy-2-nitrophenanthridin-6(5H)-one (2o): R = 0.50
f
(
2
8
hexane/ethyl acetate 4:1); white solid; yield 88% (70 mg); mp
3
-Fluoro-5-methoxy-8-methylphenanthridin-6(5H)-one (2j): R =
f
1
46−247 °C; H NMR (400 MHz, CDCl ) δ 9.18 (s, 1H), 8.58 (d, J =
0
1
.45 (hexane/ethyl acetate 4:1); white solid; yield 84% (67 mg); mp
90−192 °C; H NMR (400 MHz, DMSO-d ) δ 8.48 (dd, J = 8.4, 6.0
Hz, 1H), 8.34 (d, J = 8.4 Hz, 1H), 8.10 (s, 1H), 7.66 (d, J = 8.0 Hz, 1H),
3
1
.0 Hz, 1H), 8.44 (d, J = 9.2 Hz, 1H), 8.37 (d, J = 8.0 Hz, 1H), 7.89 (d, J
6
= 8.0 Hz, 1H), 7.79 (d, J = 9.2 Hz, 1H), 7.73 (d, J = 7.6 Hz, 1H), 4.18 (s,
3H); C{ H} NMR (100 MHz, CDCl
131.8, 129.6, 128.9, 126.5, 124.9, 122.5, 119.6, 118.7, 113.4, 63.3; IR
1
3
1
7
3
.42 (dd, J = 10.2, 1.6 Hz, 1H), 7.21 (dd, J = 12.0, 5.2 Hz, 1H), 4.03 (s,
3
) δ 157.3, 143.3, 140.1, 133.6,
H), 2.46 (s, 3H); 1 C{ H} NMR (100 MHz, DMSO-d ) δ 163.4 (d, J
3
1
6
=
245.6 Hz), 156.8, 138.5, 137.1 (d, J = 11.0 Hz), 134.8, 130.2, 127.8,
(KBr) ν
̃
= 3072, 2946, 1658, 1517, 1488, 1332, 1299, 1284, 1136, 1033,
M
J. Org. Chem. XXXX, XXX, XXX−XXX