Page 7 of 9
The Journal of Organic Chemistry
(d, J = 8.8 Hz, 1H), 4.11 (s, 3H), 4.04 (s, 3H); 13C NMR (100
63.0, 62.9. HRMS (ESI): Exact mass calcd for C14H11ClNO2
[M+H]+ 260.0473, found 260.0468; Exact mass calcd for
C14H10Cl2NO2 [M+H]+ 294.0083, found 294.0090.
1
2
3
4
MHz, CDCl3): δ 161.5, 156.1, 136.3, 135.9, 133.2, 130.2,
123.8, 122.7, 117.8, 115.4, 114.1, 123.8, 112.2, 110.3, 62.5,
56.5.
2,3ꢀDibromoꢀ5ꢀmethoxyphenanthridinꢀ6(5H)ꢀone
(2s).11a,11c
5ꢀMethoxyꢀ[1,3]dioxolo[4,5ꢀJ]phenanthridinꢀ6(5H)ꢀone (2l).36
and 2,3ꢀdibromoꢀ5ꢀmethoxyphenanthridinꢀ6(5H)ꢀone (2s’).
o
1
White solid, 46.5 mg, 86% yield, mp 235ꢀ237 C; 1H NMR
(4:1) White solid, 41mg 68% yield, H NMR (400 MHz,
5
6
7
8
9
(400 MHz, CDCl3): δ 8.05 (d, J = 8.0 Hz, 1H), 7.89 (s, 1H),
7.64 (d, J = 8.0 Hz, 1H), 7.59 (s, 1H), 7.54 (t, J = 8.0 Hz, 1H),
7.31 (t, J = 8.0 Hz, 1H), 6.13 (s, 2H), 4.12 (s, 3H); 13C NMR
(100 MHz, CDCl3): δ 156.6, 152.4, 148.5, 135.0, 129.8, 129.2,
123.0, 122.8, 121.8, 118.3, 112.5, 106.5, 102.1, 100.7, 62.7.
CDCl3): 8.53 (d, J = 8.0 Hz, 1H), 8.20 (d, J = 8.0 Hz, 1H),
8.08 (d, J = 8.4 Hz, 1H), 7.90ꢀ7.76(m, 2H), 7.62(t, J = 7.2 Hz,
1H), 7.44 (dd, J = 1.6 Hz, J = 8.4 Hz, 1H), 4.14 (s, 3H); 13C
NMR (100 MHz, CDCl3): 157.1, 136.6, 133.1, 132.9, 132.3,
129.0, 128.7, 128.6, 128.4, 127.8, 126.3, 126.1, 124.6, 124.0,
122.0, 121.9, 117.4, 115.5, 63.0, 62.9; HRMS (ESI): Exact
mass calcd for C14H11BrNO2 [M+H]+ 303.9968, found
303.9976; Exact mass calcd for C14H10Br2NO2 [M+H]+
381.9073, found 381.9074.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
5ꢀMethoxyꢀ10ꢀmethylphenanthridinꢀ6(5H)ꢀone (2m). White
solid, 35 mg, 73% yield, mp 120ꢀ122 oC; 1H NMR (400 MHz,
CDCl3): δ 8.54 (d, J = 7.6 Hz, 1H), 8.47 (d, J = 8.8 Hz, 1H),
7.75 (d, J = 8.4 Hz, 1H), 7.63ꢀ7.56 (m, 2H), 7.49 (t, J = 8.0 Hz,
1H), 7.34 (t, J = 7.6 Hz, 1H), 4.13 (s, 3H), 2.96 (s, 3H); 13C
NMR (100 MHz, CDCl3): δ 157.5, 137.1, 135.9, 134.9, 132.4,
129.1, 127.8, 127.3, 127.0, 122.4, 120.0, 112.4, 62.6, 26.2;
HRMS (ESI): Exact mass calcd for C15H14NO2 [M+H]+
240.1019, found 240.1025.
3,5ꢀDimethoxyphenanthridinꢀ6(5H)ꢀone (2t).11a White solid, 11
o
mg, 22% yield, mp 145ꢀ148 C; 1H NMR (400 MHz, CDCl3):
δ 8.51 (d, J = 8.0 Hz, 1H), 8.16 (d, J = 7.6 Hz, 1H), 7.74 (t, J =
8.8 Hz, 1H), 7.53 (t, J = 7.6 Hz, 1H), 7.16 (d, J = 2.0 Hz, 1H),
6.93 (dd, J = 8.4 Hz, J = 2.4 Hz, 1H), 4.14 (s, 3H), 3.96 (s,
3H); 13C NMR (100 MHz, CDCl3): δ 161.3, 157.7, 137.2,
133.2, 132.7, 128.5, 126.9, 125.0, 124.7, 121.3, 111.9, 110.7,
96.7, 62.6, 55.7.
5ꢀMethoxyꢀ3ꢀmethylphenanthridinꢀ6(5H)ꢀone
(2n).11a 11c,11d
,
White solid, 41 mg, 86% yield, mp 146ꢀ148 oC; 1H NMR (400
MHz, CDCl3): δ 8.53 (d, J = 7.6 Hz, 1H), 8.22 (d, J = 7.6 Hz,
1H), 8.13 (d, J = 7.6 Hz, 1H), 7.75 (t, J = 8.0 Hz, 1H), 7.56 (t,
J = 8.0 Hz, 1H), 7.47 (s, 1H), 7.16 (d, J = 8.4 Hz, 1H), 4.14 (s,
3H), 2.52 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 152.7,
135.8, 131.0, 128.3, 127.8, 123.7, 122.8, 121.1, 119.6, 118.3,
116.9, 111.4, 107.9, 57.9, 17.1.
2'ꢀMethoxyspiro[cyclohexaneꢀ1,1'ꢀisoindoline]ꢀ2,5ꢀdieneꢀ3',4ꢀ
dione (2r’’). Yellowishꢀbrown solid, 27 mg, 56% yield, mp
198ꢀ200 oC; 1H NMR (400 MHz, CDCl3): δ 7.91 (d, J = 7.6 Hz,
1H), 7.63ꢀ7.54 (m, 2H), 7.19 (d, J = 7.6 Hz, 1H), 6.64 (d, J =
10.0 Hz, 2H), 6.51 (d, J = 10.0 Hz, 2H), 3.96 (s, 3H); 13C
NMR (100 MHz, CDCl3): δ 184.6, 165.4, 145.6, 139.3, 133.5,
131.6, 130.2, 129.3, 125.0, 122.8, 66.1, 65.1; HRMS (ESI):
Exact mass calcd for C14H12NO3 [M+H]+ 242.0812, found
242.0824.
5ꢀMethoxyꢀ3ꢀ(trifluoromethyl)phenanthridinꢀ6(5H)ꢀone (2o).
White solid, 58 mg, 99% yield, mp 184ꢀ187 oC; 1H NMR (400
MHz, CDCl3): δ 8.59 (d, J = 8.0 Hz, 1H), 8.38 (d, J = 8.4 Hz,
1H), 7.93 (s, 1H), 7.85 (t, J = 8.0 Hz, 1H), 7.69 (t, J = 8.0 Hz,
1H), 7.59 (d, J = 8.4 Hz, 1H), 4.18 (s, 3H); 13C NMR (125
MHz, CDCl3): δ 157.1, 135.9, 133.0, 131.9, 131.8, 131.6,
129.3, 128.7, 126.9, 125.1, 124.0, 122.4, 121.2, 119.6, 109.94,
109.89, 63.0. HRMS (ESI): Exact mass calcd for C15H11F3NO2
[M+H]+ 294.0736, found 294.0740.
5ꢀMethoxyꢀ2ꢀmethylphenanthridinꢀ6(5H)ꢀone (2u). and 5ꢀ
methoxyꢀ4ꢀmethyl
phenanthridinꢀ6(5H)ꢀone
(2u’).35
Yellowishꢀbrown solid, 47 mg, 98% yield, 1H NMR (400 MHz,
CDCl3): δ 8.54 (t, J = 8.0 Hz, 2H), 8.26 (d, J = 8.4 Hz, 2H),
8.15 (d, J = 8.0 Hz, 1H), 8.05 (s, 1H), 7.76 (d, J = 8.0 Hz, 2H),
7.61ꢀ7.55 (m, 3H), 7.41ꢀ7.35 (m, 2H), 7.23 (t, J = 8.0 Hz, 1H),
4.12 (s, 3H), 3.97 (s, 3H), 2.79 (s, 3H), 2.50 (s, 3H); 13C NMR
(100 MHz, CDCl3): δ 158.5, 157.1, 134.9, 134.6, 133.6, 133.4,
132.9, 132.8, 132.7, 132.5, 131.0, 128.5, 128.3, 128.0, 127.9,
126.3, 125.9, 124.4, 123.3, 122.3, 121.9, 119.9, 118.5, 112.6,
63.0, 62.6, 23.4, 21.1; HRMS (ESI): Exact mass calcd for
C15H14NO2 [M+H]+ 240.1019, found 240.1027.
Methyl
5ꢀmethoxyꢀ6ꢀoxoꢀ5,6ꢀdihydrophenanthridineꢀ3ꢀ
carboxylate (2p).11a White solid, 54 mg, 96% yield, mp 195ꢀ
o
196 C; 1H NMR (400 MHz, CDCl3): δ 8.58 (d, J = 7.6 Hz,
1H),8.34ꢀ8.30 (m, 3H), 7.99 (d, J = 8.0 Hz, 1H), 7.82 (t, J =
8.0 Hz, 1H), 7.67 (d, J = 8.0 Hz, 1H), 4.18 (s, 3H), 4.01 (s,
3H); 13C NMR (100 MHz, CDCl3): δ 166.3, 157.1, 135.7,
132.9, 132.0, 131.2, 129.2, 128.7, 127.0, 123.9, 122.6, 122.2,
114.0, 63.0, 52.6.
3ꢀFluoroꢀ5ꢀmethoxyphenanthridinꢀ6(5H)ꢀone (2q).11d White
solid, 33 mg, 68% yield, mp 148ꢀ150 oC; 1H NMR (400 MHz,
CDCl3): δ 8.54 (d, J = 8.0 Hz, 1H), 8.24ꢀ8.17 (m, 2H), 7.78 (t,
J = 7.2 Hz, 1H), 7.59 (t, J = 8.0 Hz, 1H), 7.38ꢀ7.26 (m, 1H),
7.08ꢀ7.04 (m, 1H), 4.14 (s, 3H); 13C NMR (100 MHz, CDCl3):
δ 163.8 (J = 247 Hz), 157.4, 137.3 (J = 10.5 Hz), 132.9, 132.5,
128.6, 127.9, 125.6, 125.3 (J = 10.4 Hz), 121.7, 114.9, 110.8
(J = 23.8 Hz), 99.8 (J = 26.8 Hz), 62.8.
Methyl
5ꢀmethoxyꢀ6ꢀoxoꢀ5,6ꢀdihydrophenanthridineꢀ2ꢀ
carboxylate (2v). and methyl 5ꢀmethoxyꢀ6ꢀoxoꢀ5,6ꢀ
dihydrophenanthridineꢀ4ꢀcarboxylate (2v’). White solid, 55
1
mg, 97% yield, H NMR (400 MHz, CDCl3): δ 8.99 (s, 1H),
8.50ꢀ8.47 (m, 2H), 8.32 (d, J = 8.0 Hz, 1H), 8.27 (d, J = 8.0 Hz,
1H), 8.21 (d, J = 8.0 Hz, 1H), 8.17 (dd, J = 1.6 Hz, J = 8.4 Hz
1H), 7.79ꢀ7.73 (m, 2H), 7.65 (d, J = 8.8 Hz, 1H), 7.61ꢀ7.56 (m,
2H), 7.46 (d, J = 6.4 Hz, 1H), 7.31 (t, J = 8.0 Hz, 1H), 4.16 (s,
3H), 4.00 (s, 3H), 3.98 (s, 3H), 3.93 (s, 3H); 13C NMR (100
MHz, CDCl3): δ 169.7, 166.4, 157.4, 138.8, 133.0, 132.9,
132.6, 132.5, 130.8, 128.9, 128.5, 128.4, 126.2, 126.1, 125.4,
124.9, 124.5, 122.9, 122.2, 122.1, 120.7, 119.4, 118.2, 112.6,
63.9, 63.0, 52.7, 52.4. HRMS (ESI): Exact mass calcd for
C16H14NO4 [M+H]+ 284.0917, found 284.0920.
3ꢀChloroꢀ5ꢀmethoxyphenanthridinꢀ6(5H)ꢀone (2r).11a and 2,3ꢀ
dichloroꢀ5ꢀmethoxy phenanthridinꢀ6(5H)ꢀone (2r’). (4:1)
1
White solid, 39 mg, 75% yield, H NMR (400 MHz, CDCl3):
8.52 (d, J = 8.0 Hz, 1H), 8.19ꢀ8.12 (m, 2H), 7.78 (t, J = 7.6 Hz,
1H), 7.65ꢀ7.58 (m, 2H), 7.29 (m, 1H); 13C NMR (100 MHz,
CDCl3): 157.2, 156.9, 136.6, 136.0, 135.0, 134.0, 133.1, 132.9,
132.2, 131.2, 129.0, 128.7, 128.6, 128.3, 127.2, 126.4, 126.0,
124.8, 124.5, 123.5, 122.0, 121.9, 118.3, 117.0, 114.3, 112.6,
5ꢀMethoxyꢀ1ꢀ(trifluoromethyl)phenanthridinꢀ6(5H)ꢀone (2w).
o
1
White solid, 41.6 mg, 71% yield, mp 126ꢀ128 C; H NMR
(400 MHz, CDCl3): δ 8.09 (d, J = 8.0 Hz, 1H), 8.03 (d, J = 8.0
Hz, 2H), 7.77ꢀ7.74 (m, 3H), 7.56ꢀ7.51 (m, 4H), 7.50ꢀ7.43 (m,
ACS Paragon Plus Environment