Month 2015
Tetrazole Containing Quinoline and -1H-β-Carboline Derivatives
114.6, 125.5, 126.8, 127.6, 127.8, 128.1, 130.3, 130.7, 131.1,
(CH CH N), 57.2 (CH of cyclohexyl), 57.7 (CH), 106.3,
2 2
1
36.9, 137.9, 143.4, 146.5, 149.1, 153.6 (C―Ar); ms: m/z (%)
110.9, 117.4, 118.4, 120.5, 126.5, 126.8, 127.4, 127.7,
128.6, 128.8, 131.4, 131.9, 135.8, 139.7, 146.5, 149.1,
+
35
+ 37
476 (56, M [ Cl]), 478 (19, M [ Cl]), 364 (100), 320 (14),
+
35
306 (18), 295 (97), 259 (45). Anal. Calcd for C H ClN : C,
152.4 (C―Ar); ms: m/z (%) 497 (1, M [ Cl]), 499
27
33
6
+
37
67.98; H, 6.97; N, 17.62%. Found: C, 68.16; H, 7.11; N, 17.54%.
(0.33, M [ Cl]), 292 (22), 215 (35), 171 (100), 143
(74), 115 (20). Anal. Calcd for C28 : C, 67.53; H,
N-((2-chloro-6-methylquinolin-3-yl)(1-(2,4,4-trimethylpentan-2-yl)-
H-tetrazol-5-yl)methyl)-4-methylaniline (6k).
H28ClN
7
1
White solid;
5.67; N, 19.69%. Found: C, 67.59; H, 5.75; N, 19.81%.
Yield: 78%; mp 222–225°C; IR (KBr) 3296 (NH), 1596,
2-((2-chloroquinolin-3-yl)(1-(2,4,4-trimethylpentan-2-yl)-1H-tetrazol-
À1
1
1387, 1339cm ; H NMR (500 MHz, DMSO): δ 0.77 (9H,
5-yl)methyl)-2,3,4,9-tetrahydro-1H-pyrido[3–23]indole (7b).
White
s, CMe ), 1.84 and 1.88 (6H, 2s, CMe ), 2.02 (1H, d, J
solid; Yield: 70%; mp 205–207°C; IR (KBr) 3278 (NH), 1619,
1399, 1325cm ; H NMR (500MHz, DMSO): δ 0.50 (9H, s,
3
2
À1 1
1
4.9 Hz, CCHC), 2.09 (3H, s, Me), 2.26 (1H, d, J 14.9 Hz,
CCHC), 2.45 (3H, s, Me), 6.41 (1H, d, J 9.4 Hz, CHNH),
.64 (2H, d, J 8.1Hz, Ar), 6.91 (2H, d, J 8.0 Hz, Ar), 7.09
1H, d, J 9.4 Hz, CHNH), 7.64 (1H, d, J 7.8 Hz, Ar), 7.75
CMe ), 1.77–2.01 (8H, m, CMe , CCH C), 2.63 (2H, br s,
3
2
2
6
CH CH N), 3.05 (1H, br s, CH CHN), 3.24 (1H, br s,
2 2 2
CH CHN), 4.00 (2H, AB-q, J 13.9Hz, CH N), 6.42 (1H, s,
2 2
(
13
(
1H, s, Ar), 7.87 (1H, d, J 8.5Hz, Ar), 8.43 (1H, s, Ar);
NMR (125MHz, DMSO): δ 20.0 (Me), 21.0 (Me), 28.8
CMe ), 29.3 (CMe ), 30.5 (CMe ), 31.2 (CMe ), 50.0
C
CH), 6.89–6.97 (2H, m, Ar), 7.22 (1H, d, J 6.7Hz, Ar), 7.30
(1H, d, J 6.4Hz, Ar), 7.67 (1H, br s, Ar), 7.85 (1H, br s, Ar),
7.99 (1H, d, J 7.4 Hz, Ar), 8.16 (1H, d, J 7.1 Hz, Ar), 8.65 (1H,
(
2
2
3
3
13
(
CHNH), 52.7 (CCH C), 66.2 (CMe ), 113.0 (2C), 126.5,
s, Ar), 10.66 (1H, s, NH); C NMR (125 MHz, DMSO): δ
2
2
1
26.8, 127.3, 127.6, 129.8 (2C), 130.4, 133.1, 137.3, 137.6,
21.9 (CH CH N), 29.1 (CMe ), 30.0 (CMe ), 31.0 (CMe ),
46.4 (CH N), 47.0 (CH CH N), 52.5 (CCH C), 58.8 (CH),
2 2 2 2
2
2
2
3
3
+
1
43.1, 145.1, 148.2, 153.6 (C―Ar); ms: m/z (%) 476 (30, M
3
5
+ 37
[
Cl]), 478 (10, M [ Cl]), 462 (19), 364 (70), 350 (44),
65.6 (CMe ), 106.3, 110.8, 117.3, 118.3, 120.4, 126.3, 126.5,
2
2
95 (100), 281 (60). Anal. Calcd for C H ClN : C, 67.98;
126.9, 127.5, 127.9, 128.7, 131.7, 132.0, 135.8, 140.9, 146.4,
27
33
6
+
35
H, 6.97; N, 17.62%. Found: C, 68.16; H, 7.11; N, 17.54%.
Representative procedure for the synthesis of 7a–d. To a
stirring solution of 2-chloroquinoline-3-carbaldehyde
149.9, 152.7 (C―Ar); ms: m/z (%) 527 (1, M [ Cl]), 529
+
37
(0.33, M [ Cl]), 345 (5), 245 (8), 187 (49), 171 (100), 143
(83). Anal. Calcd for C30 : C, 68.23; H, 6.49; N,
H
34ClN
7
(
(
(
1.0 mmol) in MeOH (5 mL) was added tryptamine
0.160 g, 1.0mmol), isocyanide (1.0 mmol), and TMIS
0.115 g, 1.0mmol) and the mixture stirred for 6h at
18.57%. Found: C, 68.15; H, 6.61; N, 18.53%.
2-((2-chloro-6-methylquinolin-3-yl)(1-cyclohexyl-1H-tetrazol-5-yl)met
hyl)-2,3,4,9-tetrahydro-1H-pyrido[3–23]indole (7c).
White solid;
room temperature. Formaldehyde solution (0.122 cc,
7.0% in MeOH, 1.5 mmol) and TFA (0.228 g, 2.0 mmol)
Yield: 72%; mp 196–198°C; IR (KBr) 3296 (NH), 1592, 1339,
1307cm ; H NMR (500 MHz, DMSO): δ 1.15–1.97 (10H,
À1
1
3
were then added and the mixture stirred for 15 min. After
completion as indicated by TLC, the solvent was
evaporated under reduced pressure. The crude was then
dissolved in DCM (20 mL) and washed with saturated
NaHCO3 (10 mL) and brine (10mL) solutions,
respectively. The organic layer was dried over anhydrous
Na SO . After evaporation of the solvent under reduced
m, 5CH of cyclohexyl), 2.47 (3H, s, Me), 2.74 (2H, br s,
2
CH CH N), 2.92–3.05 (2H, m, CH CH N), 3.80 (2H, AB-q, J
2
2
2
2
14.3Hz, CH N), 4.81 (1H, br s, CH of cyclohexyl), 6.10 (1H,
2
s, CH), 6.93 (1H, t, J 7.3Hz, Ar), 7.00 (1H, t, J 7.3Hz, Ar),
7.25 (1H, d, J 7.8 Hz, Ar), 7.36 (1H, d, J 7.5 Hz, Ar), 7.67 (1H,
d, J 8.5Hz, Ar), 7.86 (1H, d, J 8.5Hz, Ar), 7.95 (1H, s, Ar),
13
8.74 (1H, s, Ar), 10.66 (1H, s, NH); C NMR (125 MHz,
2
4
pressure, the crude product was purified by column
chromatography on silica gel using a mixture of Hex-
AcOEt (3:1 V/V) as eluent to afford compounds 7a–d.
DMSO): δ 21.1 (Me), 21.5 (CH CH N), 24.4 (CH ), 24.6
2
2
2
(CH ), 24.7 (CH ), 32.7 (CH ), 32.9 (CH ), 47.4 (CH N), 47.9
2
2
2
2
2
(CH CH N), 57.2 (CH of cyclohexyl), 57.6 (CH), 106.4, 110.9,
2
2
2
-((2-chloroquinolin-3-yl)(1-cyclohexyl-1H-tetrazol-5-yl)met
117.4, 118.4, 120.5, 126.5, 126.8, 127.2, 127.3, 128.7, 131.9,
hyl)-2,3,4,9-tetrahydro-1H-pyrido[3–23]indole (7a).
White
solid; Yield: 68%; mp 209–211°C; IR (KBr) 3280 (NH),
133.6, 135.8, 137.5, 138.9, 145.1, 148.2, 152.5 (C―Ar); ms:
m/z (%) 511 (1, M [ Cl]), 513 (0.33, M [ Cl]), 295 (8), 259
(8), 217 (9), 190 (17), 171 (100). Anal. Calcd for C29H30ClN :
7
+
35
+ 37
À1
1
1
619, 1392, 1330cm ; H NMR (500MHz, DMSO): δ
1
.15–1.97 (10H, m, 5CH of cyclohexyl), 2.74 (2H, br s,
C, 68.02; H, 5.91; N, 19.15%. Found: C, 67.93; H, 6.07; N,
19.27%.
2
CH CH N), 2.97–3.05 (2H, m, CH CH N), 3.81 (2H,
2
2
2
2
AB-q, J 13.9Hz, CH N), 4.83 (1H, br s, CH of
cyclohexyl), 6.13 (1H, s, CH), 6.90–7.02 (2H, m, Ar),
2-((2-chloro-6-methylquinolin-3-yl)(1-(2,4,4-trimethylpentan-2-
yl)-1H-tetrazol-5-yl)methyl)-2,3,4,9-tetrahydro-1H-pyrido[3,4-b]in
dole (7d). White solid; Yield: 79%; mp 231–234°C; IR
2
7
7
.25 (1H, d, J 7.7 Hz, Ar), 7.36 (1H, d, J 7.5 Hz, Ar),
.67 (1H, t, J 7.2 Hz, Ar), 7.84 (1H, t, J 7.3 Hz, Ar), 7.98
À1
1
(KBr) 3296 (NH), 1630, 1375, 1340cm ; H NMR
(
(
1H, d, J 8.2Hz, Ar), 8.21 (1H, d, J 7.4Hz, Ar), 8.88
1H, s, Ar), 10.66 (1H, s, NH); C NMR (125MHz,
(500MHz, DMSO): δ 0.50 (9H, s, CMe ), 1.77 and 1.85
3
1
3
(6H, 2s, CMe ), 1.92 (2H, AB-q, J 15.1Hz, CCH C), 2.46
2
2
DMSO): δ 21.4 (CH CH N), 24.4 (CH ), 24.5 (CH ),
(3H, s, Me), 2.60–2.63 (2H, m, CH CH N), 3.00–3.04 (1H,
2 2
2
2
2
2
2
4.7 (CH ), 32.8 (CH ), 32.9 (CH ), 47.4 (CH N), 47.9
m, CH CH N), 3.22–3.26 (1H, m, CH CH N), 3.99 (2H,
2 2 2 2
2
2
2
2
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet