1094
M. A. Ponce and R. Erra-Balsells
Vol. 38
8-Bromoharmine (3b).
13
(s, 1H, 8-H), 2.67 ppm (s, 3H, CH ); C-nmr (deuteriochloro-
3
form/methanol-d ): δ 154.2 (7-C), 141.7 (1-C), 140.7 (9a-C),
136.5 (3-C), 130.8 (8a-C), 128.0 (4b-C), 125.2 (5-C), 115.7
1
4
Compound 3b has mp 206-208°; H-nmr (deuteriochloro-
form): δ 11.70 (s, 1H, NH), 8.37 (d, 1H, 3-H, J = 5.5 Hz), 7.99 (d,
(4a-C), 111.9 (4-C), 103.4 (6-C), 97.4 (8-C), 18.5 ppm (CH );
3
1H, 5-H, J = 8.4 Hz), 7.73 (d, 1H, 4-H, J = 5.5 Hz), 6.96 (d, 1H,
6-H, J = 8.4), 4.04 (s, 3H, CH O), 2.85 ppm (s, 3H, CH ); C-
81
+
79
+
ms: m/z 278 ( Br, M , 85 ), 276 ( Br, M , 100 ), 249 (4), 198
(40), 196 (33), 170 (23), 169 (25), 152 (4), 140 (16), 127 (7), 115
(12), 99 (29), 84 (41), 77 (13).
13
3
3
nmr (deuteriochloroform/methanol-d ): δ 156.3 (7-C), 141.7
4
(1-C), 138.4 (3-C), 130.9 (9a-C), 129.3 (8a-C), 128.7 (4b-C),
121.3 (5-C), 117.0 (4a-C), 112.6 (4-C), 105.8 (6-C), 93.0 (8-C),
56.9 (CH O), 19.5 ppm (CH ); ms: m/z 292 ( Br, M , 85), 290
Br, M , 100 ), 277 (32), 275 (35), 249 (44), 247 (51), 211 (1),
210 (2), 196 (6), 181 (13), 168 (20), 152 (6), 140 (17).
Anal. Calcd. For C H N OBr: C, 53.63; H, 3.81; N, 9.62;
Anal. Calcd. For C
H N OBr: C, 51.82; H, 3.62; N, 10.07;
12 10 2
Br, 28.73. Founds: C, 51.85; H, 3.61; N, 10.06; Br, 28.76.
81
+
3
3
79
+
(
8-Bromoharmol (4b).
1
Compound 4b has mp 193-195° (d); H-nmr (deuteriochloro-
13 11
2
form/methanol-d ): δ 11.60 (s, 1H, NH), 8.18 (d, 1H, 4-H, J =
4
Br, 27.44. Founds: C, 53.64; H, 3.80; N, 9.63; Br, 27.47.
5.5 Hz), 7.84 (d, 1H, 5-H, J = 8.4 Hz), 7.70 (d, 1H, 3-H, J = 5.5
Hz), 7.21 (sa, 1H, OH), 6.91 (d, 1H, 6-H, J = 8.4 Hz), 2.83 ppm
6,8-Dibromoharmine (3c).
13
(s, 3H, CH ); C-nmr (dimethylsulfoxide-d ): δ 154.6 (7-C),
1
3
6
Compound 3c has mp 208-210° (d); H-nmr (deuteriochloro-
form): δ 11.90 (s, 1H, NH), 8.20 (d, 1H, 3-H, J = 5.5 Hz), 8.16
(s, 1H, 5-H), 7.65 (d, 1H, 4-H, J = 5.5 Hz), 3.93 (s, 3H, CH O),
2.78 ppm (s, 3H, CH ); C-nmr (dimethylsulfoxide): δ 152.6
(7-C), 143.2 (9a-C), 139.6 (1-C), 138.6 (3-C), 135.1 (8a-C),
126.7 (4b-C), 124.8 (5-C), 119.9 (4a-C), 112.8 (4-C), 107.8
(6-C), 100.1 (8-C), 60.8 (CH O), 20.8 ppm (CH ); ms: m/z 372
142.1 (1-C), 141.0 (9a-C), 138.2 (3-C), 134.4 (8a-C), 128.5
(4b-C), 121.1 (5-C), 115.1 (4a-C), 111.8 (4-C), 109.7 (6-C), 90.8
3
81
+
13
(8-C), 20.6 ppm (CH ); ms: m/z 278 ( Br, M , 75 ), 276
(
3
3
79
+
Br, M , 100 ), 249 (5), 198 (46), 196 (53), 170 (23), 169 (18),
152 (5), 140 (17).
Anal. Calcd. For C
H N OBr: C, 51.82; H, 3.62; N, 10.07;
12 10 2
3
3
81
81
+
81
79
+
79
79
Br, 28.73. Founds: C, 51.80; H, 3.61; N, 10.05; Br, 28.76.
(
Br/ Br, M , 12), 370 ( Br/ Br, M , 25), 368 ( Br/ Br,
+
M , 13), 357 (6), 355 (11), 353 (5), 326 (17), 324 (7), 292 (1),
290 (1), 276 (11), 275 (5), 261 (4), 260 (4), 248 (7), 246 (8), 210
(5), 180 (33), 167 (19), 166 (18), 152 (5), 140 (26).
6-Bromo-7-acetylharmol (5a).
1
Compound 5a has mp 276-278°; H-nmr (deuteriochloro-
form/methanol-d ): δ 11.60 (s, 1H, NH), 8.19 (d, 1H, 3-H, J =
Anal. Calcd. For C
Br, 43.19. Founds: C, 42.21; H, 2.71; N, 7.58; Br, 43.22.
H N OBr : C, 42.20; H, 2.72; N, 7.57;
4
13 10 2 2
5.4), 8.15 (s, 1H, 5-H), 7.58 (d, 1H, 4-H, J = 5.4 Hz), 7.24 (s, 1H,
13
8-H), 2.72 (s, 3H, CH ), 2.59 ppm (s, 3H, CH CO); C-nmr
3
3
3,6-Dibromoharmine (3d).
(deuteriochloroform/methanol-d ): δ 169.8 (CO), 147.4 (7-C),
4
1
142.1 (1-C), 139.8 (9a-C), 137.8 (3-C), 137.4 (8a-C), 126.7
(4b-C), 125.6 (5-C), 120.9 (4a-C), 112.6 (4-C), 106.8 (6-C),
Compound 3d has mp 278-280° (d); H-nmr (deuteriochloro-
form): δ 11.40 (s, 1H, NH), 8.08 (s, 1H, 5-H), 7.72 (s, 1H, 4-H),
6.94 (s, 1H, 8-H), 3.92 (s, 3H, CH O), 2.64 ppm (s, 3H, CH );
C-nmr (dimethylsulfoxide): δ 155.9 (7-C), 142.1 (9a-C), 141.7
81
106.6 (8-C), 20.9 (CH ), 19.5 ppm (CH CO); ms: m/z 320 ( Br,
3
3
3
3
+
79
+
13
M , 85 ), 318 ( Br, M , 100 ), 275 (45), 273 (23), 194 (35), 179
(15).
(1-C), 134.3 (8a-C), 129.9 (3-C), 127.9 (4b-C), 126.2 (5-C),
Anal. Calcd. For C H N O Br: C, 52.69; H, 3.47; N, 8.78;
Br, 25.04. Founds: C, 52.66; H, 3.48; N, 8.80; Br, 25.08.
115.4 (4-C), 114.7 (4a-C), 103.6 (6-C), 94.7 (8-C), 56.3 (CH O),
14 11
2 2
3
81
81
+
19.8 ppm (CH ); ms: m/z 372 ( Br/ Br, M , 12), 370
3
81
79
+
79
79
+
(
Br/ Br, M , 24), 368 ( Br/ Br, M , 13), 357 (1), 355 (2),
8-Bromo-7-acetylharmol (5b).
353 (1), 326 (9), 324 (4), 292 (2), 291 (6), 276 (1), 275 (5), 261
(4), 260 (4), 248 (5), 246 (5), 210 (2), 195 (10), 194 (3), 180 (9),
167 (14), 166 (12), 152 (8), 140 (17).
1
Compound 5b has mp 220-222°; H-nmr (deuteriochloro-
form/methanol-d ): δ 8.42 (s, 1H, NH), 8.39 (d, 1H, 3-H, J = 5.5
4
Anal. Calcd. For C
H N OBr : C, 42.20; H, 2.72; N, 7.57;
Hz), 7.88 (d, 1H, 5-H, J = 8.4 Hz), 7.68 (d, 1H, 4-H, J = 5.5 Hz),
13 10 2 2
Br, 43.19. Founds: C, 42.19; H, 2.71; N, 7.58; Br, 43.21.
7.03 (d, 1H, 6-H, J = 8.4 Hz), 2.84 (s, 3H, CH ), 2.45 ppm (s, 3H,
3
13
CH CO); C-nmr (deuteriochloroform/methanol-d ): δ 168.9
3
4
3,6,8-Tribromoharmine (3e).
(CO), 148.0 (7-C), 142.4 (1-C), 139.9 (9a-C), 139.6 (3-C), 134.7
(8a-C), 128.5 (4b-C), 120.8 (4a-C), 121.1 (5-C), 115.8 (6-C),
113.0 (4-C), 98.9 (8-C), 20.8 (CH ), 20.3 ppm (CH CO); ms: m/z
1
Compound 3e has mp 248-250° (d); H-nmr (deuteriochloro-
form): δ 9.48 (bs, 1H, NH), 8.15 (s, 1H, 5-H), 7.48 (s, 1H, 4-H),
3
3
81
+
79
+
13
320 ( Br, M , 80 ), 318 ( Br, M , 100 ), 275 (40), 273 (25), 194
(15), 179 (10).
3.96 (s, 3H, CH O), 2.79 ppm (s, 3H, CH ); C-nmr (deuterio-
3
3
chloroform): δ 154.2 (7-C), 143.4 (1-C), 140.0 (9a-C), 136.5
Anal. Calcd. For C H N O Br: C, 52.69; H, 3.47; N, 8.78;
(8a-C), 130.1 (4b-C), 129.4 (3-C), 124.9 (5-C), 119.1 (4a-C),
14 11
2 2
116.3 (4-C), 109.7 (6-C), 100.5 (8-C), 61.2 (CH O); 19.9 ppm
Br, 25.04. Founds: C, 52.68; H, 3.46; N, 8.80; Br, 25.07.
3
81
81
81
+
(CH ); ms: m/z 452 ( Br/ Br/ Br, M , 23), 450
3
3,6-Dibromo-7-acetylharmol (5d).
81
79
81
79
+
81
79
79
+
(
(
Br/ Br/ Br, M , 15), 448 ( Br/ Br/ Br, M , 53), 446
Br/ Br/ Br, M , 100), 437 (29), 406 (54), 371 (75).
79
79
+
1
Compound 5d was obtained as a syrup; H-nmr (deuterio-
Anal. Calcd. For C H N OBr : C, 34.78; H, 2.02; N, 6.24; Br,
chloroform): δ 8.54 (s, 1H, NH), 7.83 (s, 1H, 5-H), 7.53
13
9
2
3
53.40. Founds: C, 34.76; H, 2.01; N, 6.25; Br, 53.43.
(s, 1H, 4-H), 7.06 (s, 1H, 8-H), 2.69 (s, 3H, CH ), 2.51 ppm
3
81
81
+
(s, 3H, CH CO); ms: m/z 400 ( Br/ Br, M , 12), 398
3
6-Bromoharmol (4a).
81
79
+
79
79
+
(
Br/ Br, M , 26), 396 ( Br/ Br, M , 18), 353 (15), 338
(22), 257 (18), 176 (10),
Anal. Calcd. For C
1
Compound 4a has mp 236-238°; H-nmr (deuteriochloro-
form/methanol-d ): δ 11.60 (s, 1H, NH), 8.08 (s, 1H, 5-H), 8.06
H
N O Br : C, 42.24; H, 2.53; N, 7.04;
2 2 2
4
14 10
(d, 1H, 3-H, J = 5.5 Hz), 7.58 (d, 1H, 4-H, J = 5.5 Hz), 6.97
Br, 40.15. Founds: C, 42.26; H, 2.52; N, 7.06; Br, 40.19.