Zhou et al.
JOCArticle
100 MHz) δ 172.3, 162.5, 141.4, 137.1, 134.3, 133.2, 133.1, 132.6,
130.0, 128.7, 127.4, 125.7, 120.2, 119.1, 104.3, 62.1, 34.1, 30.2, 27.5;
LRMS (EI) m/z 384 (Mþ); HRMS (EI) m/z calcd C20H14Cl2N2O2
(Mþ) 384.0432, found 384.0427.
127.1, 119.7 (d, J = 9.0 Hz), 112.8 (d, J = 23.8 Hz), 106.3, 105.9 (d,
J = 23.8 Hz), 62.4, 42.0, 40.5, 31.5, 30.7, 28.8, 28.7, 27.6, 22.5, 14.0;
LRMS (EI) m/z 418 (Mþ); HRMS (EI) m/z calcd C26H27FN2O2
(Mþ) 418.2057, found 418.2058.
7-Fluoro-15b-methyl-1H-benzo[e]indolo[1,2-a]pyrrolo[2,1-c]-
[1,4]diazepine-3,9(2H,15bH)-dione (3Qa): 1H NMR (CDCl3,
300 MHz) δ 8.55 (d, J = 8.1 Hz, 1H), 8.29 (dd, J = 10.2 Hz,
3.0 Hz, 1H), 7.60-7.65 (m, 1H), 7.54 (d, J = 7.2 Hz, 1H), 7.29-
7.42 (m, 3H), 6.61 (s, 1H), 2.93-2.96 (m, 1H), 2.64-2.71 (m, 2H),
2.29-2.34 (m, 1H), 1.51 (s, 3H); 13C NMR (CDCl3, 100 MHz) δ
172.3, 162.7, 160.6 (d, J = 245.5 Hz), 140.2, 138.8, 130.6, 129.2
(d, J = 7.8 Hz), 128.8, 128.4, 125.6, 124.6, 121.5 (d, J = 22.8
Hz), 120.6, 119.6 (d, J = 25.1 Hz), 118.1, 105.3, 62.2, 34.3, 30.3,
27.6; LRMS (EI) m/z 334 (Mþ); HRMS (EI) m/z calcd
C20H15FN2O2 (Mþ) 334.1118, found 334.1123.
7-Fluoro-13-chloro-15b-methyl-1H-benzo[e]indolo[1,2-a]pyrrolo-
[2,1-c][1,4]diazepine-3,9(2H,15bH)-dione (3Ra): 1H NMR (CDCl3,
300 MHz) δ 8.47 (d, J = 9.0 Hz, 1H), 8.25 (dd, J = 10.2 Hz, 3.3
Hz, 1H), 7.59-7.65 (q, 1H), 7.49 (s, 1H), 7.36-7.43 (m, 1H), 7.31
(dd, J = 9.0 Hz, 2.4 Hz, 1H), 6.54 (s, 1H), 2.90-2.97 (m, 1H),
2.63-2.69 (m, 2H), 2.29-2.36 (m, 1H), 1.50 (s, 3H); 13C NMR
(CDCl3, 100 MHz) δ 172.3, 162.5, 160.6 (d, J = 245.5 Hz), 141.6,
137.1, 130.6, 130.1, 130.0, 129.3 (d, J = 8.2 Hz), 128.1 (d, J = 6.9
Hz), 125.6, 121.8 (d, J = 22.8 Hz), 120.2, 119.6 (d, J = 25.1 Hz),
119.1, 104.4, 62.1, 34.3, 30.2, 27.5; LRMS (EI) m/z 368 (Mþ);
HRMS (EI) m/z calcd C20H14ClFN2O2 (Mþ) 368.0728, found
368.0730.
15,16b-Dimethyl-1H-benzo[e]indolo[1,2-a]pyrido[2,1-c][1,4]-
diazepine-4,10(2H,16bH)-dione (3Ac):1HNMR(CDCl3, 300MHz)
δ 8.57 (d, J = 8.7 Hz, 1H), 8.19 (d, J = 7.8 Hz, 1H), 7.60 (t, 1H),
7.46 (t, 1H), 7.28-7.32 (m, 2H), 7.12 (d, J = 7.2 Hz, 1H), 6.52 (s,
1H), 2.76-2.81(m, 1H), 2.55-2.64 (m, 2H), 2.52 (s, 3H), 2.10-2.28
(m, 2H), 1.91-1.96 (m, 1H), 1.35 (s, 3H); 13C NMR (CDCl3, 100
MHz) δ 169.9, 165.3, 142.6, 138.1, 137.1, 132.9, 132.4, 131.5, 129.9,
129.6, 128.5, 127.8, 125.5, 125.0, 116.3, 105.1, 60.9, 37.7, 31.8, 31.7,
18.3, 17.1; LRMS (EI) m/z 344 (Mþ); HRMS (EI) m/z calcd
C22H20N2O2 (Mþ) 344.1525, found 344.1527.
16b-Methyl-1H-benzo[e]indolo[1,2-a]pyrido[2,1-c][1,4]diazepine-
4,10(2H,16bH)-dione (3Bc): 1H NMR (CDCl3, 300 MHz) δ 8.75
(d, J = 8.7 Hz, 1H), 8.23 (d, J = 8.1 Hz, 1H), 7.62 (t, 1H),
7.45-7.55 (m, 2H), 7.31-7.42 (m, 3H), 6.52 (s, 1H), 2.75-2.80
(m, 1H), 2.57-2.66 (m, 2H), 2.19-2.29 (m, 1H), 2.11-2.14 (m,
1H), 1.92-1.97 (m, 1H), 1.36 (s, 3H); 13C NMR (CDCl3, 100
MHz) δ 169.9, 165.3, 143.1, 138.3, 137.1, 133.0, 132.5, 131.3,
130.0, 129.1, 127.8, 125.5, 124.5, 120.3, 118.8, 106.8, 60.8, 37.6,
31.9, 31.6, 17.0; LRMS (EI) m/z 330 (Mþ); HRMS (EI) m/z
calcd C21H18N2O2 (Mþ) 330.1368, found 330.1369.
14,16b-Dimethyl-1H-benzo[e]indolo[1,2-a]pyrido[2,1-c][1,4]-
diazepine-4,10(2H,16bH)-dione (3Cc):1HNMR(CDCl3, 300MHz)
δ 8.60 (d, J = 8.4 Hz, 1H), 8.21 (d, J = 8.1 Hz, 1H), 7.60 (t, 1H),
7.46 (t, 1H), 7.29-7.31 (m, 2H), 7.18 (d, J = 9.0 Hz, 1H), 6.42 (s,
1H), 2.71-2.76(m, 1H), 2.54-2.63 (m, 2H), 2.45 (s, 3H), 2.16-2.25
(m, 1H), 1.91-2.11 (s, 2H), 1.33 (s, 3H); 13C NMR (CDCl3, 100
MHz) δ 169.9, 165.0, 143.1, 137.1, 136.5, 134.2, 132.9, 132.5, 131.4,
130.0, 129.3, 127.8, 126.7, 120.2, 118.5, 106.7, 60.8, 37.6, 31.8, 31.5,
21.3, 17.0; LRMS (EI) m/z 344 (Mþ); HRMS (EI) m/z calcd
C22H20N2O2 (Mþ) 344.1525, found 344.1521.
13,16b-Dimethyl-1H-benzo[e]indolo[1,2-a]pyrido[2,1-c][1,4]-
diazepine-4,10(2H,16bH)-dione (3Dc):1HNMR(CDCl3,300MHz)
δ 8.60 (s, 1H), 8.20 (d, J = 7.8 Hz, 1H), 7.60 (t, 1H), 7.47 (t, 1H),
7.39 (d, J = 7.5, 1H), 7.29 (d, J = 7.8, 1H), 7.15 (d, J = 8.1, 1H),
6.45 (s, 1H), 2.54-2.75 (m, 3H), 2.52(s, 3H), 2.15-2.26 (m, 1H),
2.08-2.11 (m, 1H), 1.89-1.94 (m, 1H), 1.33 (s, 3H); 13C NMR
(CDCl3, 100 MHz) δ 169.9, 165.3, 142.4, 138.7, 137.1, 135.5, 132.9,
132.4, 131.4, 129.9, 127.8, 126.7, 125.8, 119.8, 119.1, 106.8, 60.8, 37.6,
31.8, 31.6, 22.1, 17.0; LRMS (EI) m/z 344 (Mþ); HRMS (EI) m/z
calcd C22H20N2O2 (Mþ) 344.1525, found 344.1529.
14-Methoxyl-16b-methyl-1H-benzo[e]indolo[1,2-a]pyrido[2,1-c]-
[1,4]diazepine-4,10(2H,16bH)-dione (3Ec): 1H NMR (CDCl3,
300 MHz) δ 8.64 (d, J = 8.1 Hz, 1H), 8.21 (d, J = 7.8 Hz,
1H), 7.60 (t, 1H), 7.46 (t, 1H), 7.29 (d, J = 7.8 Hz, 1H), 6.95-
6.99 (m, 2H), 6.43 (s, 1H), 3.87 (s, 3H), 2.56-2.76 (m, 3H),
1.91-2.26 (m, 3H), 1.33 (s, 3H); 13C NMR (CDCl3, 100 MHz) δ
169.9, 156.9, 143.7, 137.1, 132.9, 132.5, 131.3, 130.1, 130.0,
127.8, 119.7, 113.2, 106.7, 103.4, 60.7, 55.6, 37.5, 31.8, 31.5,
17.0; LRMS (EI) m/z 360 (Mþ); HRMS (EI) m/z calcd C22H20-
N2O3 (Mþ) 360.1474, found 360.1478.
14-Cyano-16b-methyl-1H-benzo[e]indolo[1,2-a]pyrido[2,1-c]-
[1,4]diazepine-4,10(2H,16bH)-dione (3Fc): 1H NMR (CDCl3,
300 MHz) δ 8.84 (d, J = 9.0 Hz, 1H), 8.19 (d, J = 8.1 Hz,
1H), 7.85 (s, 1H), 7.64 (d, J = 9.3 Hz, 2H), 7.51 (t, 1H), 7.32 (d,
J = 8.1 Hz, 1H), 6.55 (s, 1H), 2.74-2.76 (m, 1H), 2.57-2.66 (m,
2H), 2.20-2.24 (m, 1H), 1.96-2.00 (m, 2H), 1.31 (s, 3H); 13C
NMR (CDCl3, 100 MHz) δ 169.8, 165.4, 145.7, 140.2, 137.3,
133.6, 132.7, 130.7, 130.2, 129.2, 128.5, 128.1, 124.8, 119.6,
119.4, 107.8, 105.9, 60.7, 37.5, 31.8, 31.4, 17.0; LRMS (EI)
m/z 355 (Mþ); HRMS (EI) m/z calcd C22H17N3O2 (Mþ) 355.1321,
found 355.1316.
2-Hexyl-15b-methyl-1H-benzo[e]indolo[1,2-a]pyrrolo[2,1-c]-
[1,4]diazepine-3,9(2H,15bH)-dione (3Ab-1): H NMR (CDCl3,
1
300 MHz) δ 8.59 (t, 2H), 7.60-7.67 (m, 2H), 7.54 (d, J = 6.6 Hz,
1H), 7.42-7.48 (m, 1H), 7.27-7.39 (m, 1H), 6.58 (s, 1H), 3.10
(q, 1H), 2.67-2.70 (m, 2H), 2.05-2.07 (m, 1H), 1.94 (t, 1H),
1.25-1.55 (m, 12H), 0.92 (t, 3H); 13C NMR (CDCl3, 100 MHz)
δ 174.1, 164.0, 140.7, 138.8, 134.8, 134.0, 133.7, 128.9, 127.3,
126.6, 126.5, 125.3, 124.4, 120.5, 118.1, 104.8, 60.1, 41.2, 40.8,
31.7, 30.3, 29.3, 27.7, 27.2, 22.6, 14.1; LRMS (EI) m/z 400 (Mþ);
HRMS (EI) m/z calcd C26H28N2O2 (Mþ) 400.2151, found
400.2143.
2-Hexyl-15b-methyl-1H-benzo[e]indolo[1,2-a]pyrrolo[2,1-c]-
[1,4]diazepine-3,9(2H,15bH)-dione (3Ab-2): H NMR (CDCl3,
1
300 MHz) δ 8.67 (d, J = 8.4 Hz, 1H), 8.41 (d, J = 7.8 Hz, 1H),
7.64-7.67 (m, 2H), 7.54 (d, J = 7.5 Hz, 1H), 7.42-7.48 (m, 1H),
7.32-7.40 (m, 2H), 6.61 (s, 1H), 2.73-2.78 (m, 2H), 2.53-2.59
(m, 1H), 1.72-1.76 (m, 1H), 1.51 (s, 3H), 1.39-1.45 (m, 3H),
1.24-1.30 (m, 6H), 0.86 (t, 3H); 13C NMR (CDCl3, 100 MHz) δ
175.7, 164.7, 143.7, 138.4, 134.3, 133.7, 133.2, 128.9, 128.3,
127.2, 127.0, 125.3, 124.4, 120.3, 118.4, 106.7, 62.4, 42.0, 40.4,
31.5, 30.6, 28.8, 28.7, 27.6, 22.5, 14.0; LRMS (EI) m/z 400 (Mþ);
HRMS (EI) m/z calcd C26H28N2O2 (Mþ) 400.2151, found
400.2143.
2-Hexyl-13-fluoro-15b-methyl-1H-benzo[e]indolo[1,2-a]pyrrolo-
[2,1-c][1,4]diazepine-3,9(2H,15bH)-dione (3Gb-1):1HNMR(CDCl3,
300 MHz) δ 8.51-8.60 (m, 2H), 7.60-7.68 (m, 2H), 7.45 (t, 1H),
7.18 (dd, J = 8.4, 2.4 Hz, 1H), 7.04-7.17 (m, 1H), 6.55 (s, 1H),
3.05-3.12 (q, 1H), 2.68-2.70 (m, 1H), 1.89-2.26 (m, 2H), 1.48 (s,
3H), 1.25-1.44 (m, 9H), 0.86-0.93 (m, 3H);13CNMR (CDCl3, 100
MHz) δ 174.1, 163.8, 159.9 (d, J = 240.3 Hz), 148.9, 142.3, 135.0,
134.8, 134.2, 133.7, 130.0, 127.4, 126.7, 126.3, 119.4 (d, J = 9.0 Hz),
112.8 (d, J = 24.5 Hz), 106.0 (d, J = 23.8 Hz), 104.4, 60.1, 41.2, 40.8,
31.7, 30.3, 29.3, 27.7, 27.2, 22.6; LRMS (EI) m/z 418 (Mþ); HRMS
(EI) m/z calcd C26H27FN2O2 (Mþ) 418.2057, found 418.2058.
2-Hexyl-13-fluoro-15b-methyl-1H-benzo[e]indolo[1,2-a]pyrrolo-
[2,1-c][1,4]diazepine-3,9(2H,15bH)-dione (3Gb-2):1HNMR(CDCl3,
300 MHz) δ8.59-8.61 (m, 1H), 8.39 (d, J = 7.5 Hz, 1H), 7.63-7.67
(m, 2H), 7.45 (t, 1H), 7.07-7.19 (m, 2H), 6.56 (s, 1H), 2.69-2.75(m,
2H), 2.52-2.58 (m, 1H), 1.69 (m, 1H), 1.49 (s, 3H), 1.21-1.45 (m,
9H), 0.81-0.88 (m, 3H); 13C NMR (CDCl3, 100 MHz) δ 175.7,
164.5, 160.0, 145.4, 134.7, 134.4, 133.9, 133.3, 130.0, 128.1, 127.3,
14-Fluoro-16b-methyl-1H-benzo[e]indolo[1,2-a]pyrido[2,1-c]-
[1,4]diazepine-4,10(2H,16bH)-dione (3Gc): 1H NMR (CDCl3,
300 MHz) δ 8.68-8.73 (q, 1H), 8.20 (d, J = 7.8 Hz, 1H), 7.62
J. Org. Chem. Vol. 76, No. 5, 2011 1247