K.-J. Fodor et al.
H-70, H-90), 7.03 (t, J = 7.7 Hz, 1H, H-7), 7.07 (s, 1H, H-10),
7.09 (dd, 1H, J = 7.7 Hz, 1.9 Hz, H-60), 7.24 and 7.25
(overlapping t and d, J = 7.7 Hz, 2H, H-80 and H-8), 7.45 (d,
J = 7.7 Hz, 1H, H-5), 10.46 (s, 1H, NH) ppm (protons H-1,
H-3–H-8 belong to the b-carboline skeleton, whereas protons
H-10, H-40, H-60, H-90 are attached to the phenothiazine ring);
13C NMR (125 MHz, DMSO-d6): d = 23.0, 36.2, 41.9, 53.5,
110.1, 112.1, 115.8, 116.1, 118.5, 119.2, 121.6, 121.7, 122.4,
123.8, 127.6, 127.8, 128.4, 128.9, 133.5, 134.7, 135.0, 136.8,
145.5, 146.4 ppm.
3-(2,3,4,9-Tetrahydro-1H-pyrido[3,4-b]indol-2-ium-1-yl)-
1H-indole-4-carboxylate (6, C20H17N3O2)
ꢀ
Yellowish powder; m.p.: 296–300 °C; IR (ATR): m = 3,133,
*3,100–2,500 br, 1,580, 1,552, 1,492, 1,411, 1,378, 1,340,
1
1,302, 1,295, 1,231, 1,197, 1,165, 1,042, 480, 404 cm-1; H
NMR (500 MHz, DMSO-d6): d = 2.98 (m, 1H, H-4A), 3.08
(m, 1H, H-4B), 3.32-3.40 (m, 2H, H-3A,B), 6.01 (s, 1H, H-1),
6.96 (br s, 1H, H-20), 7.04 (t, J = 7.7 Hz, 1H, H-6), 7.10
(exactly overlapping t’s, 2H, J = 7.7 Hz, H-7 and H-70), 7.33
(d, J = 7.7 Hz 1H, H-8), 7.42 (d, J = 7.7 Hz, 1H, H-70), 7.44
(d, J = 7.7 Hz, 1H, H-50), 7.50 (d, J = 7.7 Hz, 1H, H-5),
10.80 (s, 1H, NH, 5-carboxyindole), 11.17 (s, 1H, NH,
b-carboline) ppm (protons H-1, H-3–H-8 belong to the
b-carboline skeleton, whereas protons H-20, H-50–H-70 are
attached to the 5-carboxyindole ring); 13C NMR (125 MHz,
DMSO-d6): d = 19.8, 39.7, 50.0, 108.2, 111.7, 112.0, 113.0,
118.5, 118.9, 119.5, 121.9 (three coalesced lines), 122.8,
127.2, 128.3, 131.8, 134.8, 173.4 ppm.
8-Chloro-10-methyl-3-(2,3,4,9-tetrahydro-1H-pyrido[3,4-
b]indol-1-yl)-10H-phenothiazine (3i, C24H20ClN3S)
Light orange powder; m.p.: 208–211 °C; IR (ATR):
ꢀ
m = *3,200 br, 1,571, 1,495, 1,460, 1,426, 1,395, 1,318,
1,305, 1,267, 1,246, 1,225, 1,139, 881, 847, 805, 750,
1
720 cm-1; H NMR (500 MHz, DMSO-d6): d = 2.67 (m,
1H, H-4A), 2.75 (m, 1H, H-4B), 2.93 (m, 1H, H-3A), 3.04
(m, 1H, H-3B), 3.33 (s, 3H, NCH3), 5.02 (s, 1H, H-1),
6.96–6.98 (overlapping m’s, 4H, H-6, H-7, H-10, H-90),
7.00 (br s, 1H, H-90), 7.07 (br s, 1H, H-40), 7.15 (exactly
overlapping d’s, 2H, J = 7.7 Hz, H-20 and H-80), 7.23 (d,
J = 7.7 Hz, 1H, H-8), 7.42 (d, J = 7.7 Hz, 1H, H-5),
10.36 (s, 1H, NH) ppm (protons H-1, H-3–H-8 belong to
the b-carboline skeleton, whereas protons H-10, H-20, H-40,
H-60, H-80, H-90 are attached to the phenothiazine ring); 13C
NMR (125 MHz, DMSO-d6): d = 23.0, 36.2, 42.3, 56.6,
109.1, 111.9, 115.3, 115.6, 118.4, 119.1, 121.4, 121.9,
122.2, 122.9, 127.6, 127.7, 128.6, 128.9, 133.5, 136.2,
136.9, 138.9, 144.6, 147.7 ppm.
4-(2,3,4,9-Tetrahydro-1H-pyrido[3,4-b]indol-2-ium-1-yl)-
1H-pyrazole-5-carboxylate (7, C15H14N4O2)
ꢀ
White powder; m.p.: 320–323 °C; IR (ATR): m = *3,400–
2,400 br, 1,580, 1,560, 1,442, 1,416, 1,391, 1,365, 1,302,
1
1,237, 1,110, 945, 863, 803, 770, 736, 703 cm-1; H NMR
(500 MHz, DMSO-d6): d = 2.80–3.00 (m, 2H, H-4A,B),
3.37–3.45 (m, 2H, H-3A,B), 5.73 (s, 1H, H-1), 7.03 (t,
J = 7.7 Hz, 1H, H-6), 7.12 (t, J = 7.7 Hz, 1H, H-7), 7.35
(d, J = 7.7 Hz, 1H, H-8), 7.46 (s, 1H, H-50, pyrazole), 7.49
(d, J = 7.7 Hz, 1H, H-5), 10.89 (s, 1H, NH, b-carboline),
13.31 (s, 1H, NH, pyrazole) ppm; 13C NMR (125 MHz,
DMSO-d6): d = 19.7, 41.2, 48.7, 106.6, 112.4, 116.4, 119.0,
119.8, 126.8, 131.1, 137.1, 139.2, 140.3, 123.3, 127.58,
127.64, 127.7, 128.6, 128.7, 136.3, 136.8, 162.9 ppm.
5-Methyl-2-(2,3,4,9-tetrahydro-1H-pyrido[3,4-b]indol-2-
ium-1-yl)-1H-indole-3-carboxylate (5, C21H19N3O2)
ꢀ
White powder; m.p.: 196–199 °C; IR (ATR): m = 3,453,
2-[2-(1H-Indol-3-yl)ethyl]isoindolin-1-one
(13, C18H16N2O)
3,314, 3,045, 1,637, 1,622, 1,537, 1,446, 1,348, 1,257,
1,230, 1,155, 802, 755, 732, 625, 544, 490 cm-1; 1H NMR
(500 MHz, DMSO-d6): d = 2.42 (s, 3H, 50-CH3), 2.97 (dd,
J = 15.7, 3.8 Hz, 1H, H-4 eq), 3.09 (ddd, J = 15.7, 12.3,
4.5 Hz, 1H, H-4ax), 3.39 (m, 1H, H-3ax, partly overlapped
by the HDO signal of the solvent), 3.70 (dd, J = 11.7,
4.5 Hz, 1H, H-3eq), 6.15 (s, 1H, H-1), 7.00 (t, J = 7.7 Hz,
1H, H-6), 7.03 (t, J = 7.7 Hz, 1H, H-7), 7.07 (d,
J = 7.7 Hz, 1H, H-60), 7.25 (d, 1H, J = 7.7 Hz, H-8),
7.38 (d, J = 7.7 Hz, 1H, H-70), 7.46 (d, J = 7.7 Hz, 1H,
H-5), 7.49 (br s, 1H, H-40), 10.23 (s, 1H, NH, b-carboline),
11.40 (s, 1H, NH, 3-carboxy-5-methylindole) ppm (protons
H-1, H-3–H-8 belong to the b-carboline skeleton, whereas
protons H-40, H-50 and H-60 are attached to the 3-carboxy-
5-methylindole unit); 13C NMR (125 MHz, DMSO-d6):
d = 19.7, 22.7, 42.2, 49.1, 106.4, 110.1, 112.5, 113.0,
118.7, 119.4, 119.6, 122.0, 125.6, 126.9, 128.5, 128.9,
132.3, 133.7, 134.4, 137.3, 165.6 ppm.
ꢀ
White powder; m.p.: 186–187 °C; IR (ATR): m = 3,174 br,
1,659, 1,452, 1,421, 1,328, 1,285, 1,245, 1,228, 1,212, 1,011,
;
885, 745, 732 cm-1 1H NMR (500 MHz, DMSO-d6):
d = 3.06 (t, J = 6.8 Hz, 2H, CCH2), 3.85 (t, J = 6.8 Hz,
2H, NCH2), 4.47 (s, 2H, H-30), 7.00 (t, J = 7.5 Hz, 1H,
H-5), 7.09 (t, J = 7.5 Hz, 1H, H-6), 7.19 (br s, 1H, H-2),
7.36 (d, J = 7.5 Hz, 1H, H-7), 7.49 (t, J = 7.5 Hz, 1H,
H-60), 7.54–7.61 (overlapping m’s, 3H, H-4, H-40, H-50),
7.69 (d, J = 7.5 Hz, 1H, H-70), 10.82 (s, 1H, NH) ppm
(protons H-2, H-4–H-7 belong to the indole skeleton,
whereas protons H-30–H-70 are attached to the isoindolone
unit); 13C NMR (125 MHz, DMSO-d6): d = 24.8, 43.2,
50.5, 112.2, 112.3, 119.1, 119.2, 121.9, 123.52, 123.57,
124.2, 128.0, 128.6, 132.0, 133.5, 137.1, 142.7, 168.0 ppm.
Acknowledgments This work was financially supported by the
Hungarian Scientific Research Fund (OTKA K-83,874) and the
123