Chemistry of Heterocyclic Compounds 2017, 53(2), 196–206
10-Chloro-6,7-dihydro-5Н-benzо[e]pyrido[2,3-b]indole
mp 172–173°С (hexane), Rf 0.4 (CHCl3). IR spectrum, ν, cm−1:
(4g). Yield 0.631 g (62%), yellow-brown powder, mp 220–
221°C (benzene). Rf 0.4 (CHCl3). IR spectrum, ν, cm−1:
3106, 3035, 2938, 2831, 1507, 1479, 1415, 1271, 977, 892,
757. 1H NMR spectrum (DMSO-d6), δ, ppm (J, Hz): 2.97–
3.03 (4H, m, 5,6-CH2); 7.08 (1H, t, J = 7.4, H-3); 7.24–
7.28 (2H, m, H-2,4); 7.76 (1H, d, J = 7.3, H-1); 8.18 (1H,
d, J = 2.2, H-11); 8.41 (1H, d, J = 2.2, H-9); 12.12 (1H,
br. s, NH). 13C NMR spectrum (DMSO-d6), δ, ppm: 21.5;
28.2; 107.3; 117.5; 122.1; 123.1; 124.6; 125.6; 127.0;
128.1; 132.1; 132.9; 139.5; 141.0; 147.1. Mass spectrum,
m/z (Irel, %): 256 [М(37Cl)]+ (29), 255 (30), 254 [М(35Cl)]+
(100), 253 (50), 218 (49), 190 (18), 163 (9), 127 (9), 109
(8), 28 (17). Found, %: C 70.84; H 4.24; N 10.96.
C15H11ClN2. Calculated, %: C 70.73; H 4.35; N 11.00.
3-Chloro-5,10-dihydroindeno[2',1':4,5]pyrrolo[2,3-b]-
pyridine (4h). Yield 0.433 g (45%), dark-gray crystals, mp
194–195°С (benzene). Rf 0.5 (EtOAc). IR spectrum,
ν, cm−1: 3108, 3055, 2929, 1569, 1453, 1279, 1073, 944,
3136, 3040, 2959, 2926, 2866, 2751, 1570, 1491, 1466,
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1407, 1387, 1279, 1069, 950, 869, 748. H NMR spectrum
(CDCl3), δ, ppm (J, Hz): 1.38 (6H, d, J = 7.1, CH(CH3)2);
2.46 (3H, s, 2-CH3); 3.14 (1H, sept, J = 7.1, CH(CH3)2);
8.12 (1H, d, J = 2.1, H-4); 8.13 (1H, d, J = 2.1, H-6); 10.55
(1H, br. s, NH). 13C NMR spectrum (CDCl3), δ, ppm: 12.3;
23.2 (2C); 25.8; 103.4; 121.1; 122.6; 126.6; 132.8; 138.7;
146.7. Mass spectrum, m/z (Irel, %): 210 [М(37Cl)]+ (8),
208 [М(35Cl)]+ (26), 195 (31), 193 (100), 178 (6), 158 (14), 27
(10). Found, %: C 63.25; H 6.43; N 13.32. C11H13ClN2.
Calculated, %: C 63.31; H 6.28; N 13.42.
3-Benzyl-5-chloro-2-methyl-1Н-pyrrolo[2,3-b]pyridine
(4l). Yield 0.421 g (41%), beige powder, mp 194–195°С
(MeOH). Rf 0.65 (EtOAc). IR spectrum, ν, cm−1: 3133,
3019, 2921, 2861, 1577, 1483, 1388, 1277, 914, 877, 698.
1H NMR spectrum (DMSO-d6), δ, ppm (J, Hz): 2.40 (3H,
s, CH3); 3.98 (2H, s, CH2); 7.12–7.16 (1H, m, H-4 Ph);
7.21–7.27 (4H, m, H-2,3,5,6 Ph); 7.76 (1H, d, J = 2.1,
H-4); 8.05 (1H, d, J = 2.1, H-6); 11.62 (1H, br. s, NH).
13C NMR spectrum (DMSO-d6), δ, ppm: 11.4; 29.1; 108.3;
121.5; 121.7; 124.4; 125.7; 128.1 (2C); 128.3 (2C); 135.6;
138.9; 141.3; 146.2. Mass spectrum, m/z (Irel, %): 258
[М(37Cl)]+ (33), 256 [М(35Cl)]+ (100), 243 (11), 241 (41),
181 (25), 179 (85), 151 (6), 102 (6), 77 (11), 51 (14).
Found, %: C 70.26; H 5.15; N 10.80. C15H13ClN2.
Calculated, %: C 70.18; H 5.10; N 10.91.
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759, 721. H NMR spectrum (DMSO-d6), δ, ppm (J, Hz):
3.75 (2H, s, 5-СН2); 7.30 (1H, d, J = 7.2, H-7); 7.40 (1H, d,
J = 7.2, H-8); 7.61 (1H, d, J = 7.2, H-6); 7.67 (1H, d,
J = 7.2, H-9); 8.09 (1Н, s, Н-4); 8.16 (1Н, s, Н-2); 12.43
(1Н, br. s, NH). 13C NMR spectrum (DMSO-d6), δ, ppm: 30.8;
117.5; 118.4; 119.2; 123.2; 125.7; 126.0; 126.3; 127.3;
134.6; 139.8; 146.1; 147.6; 151.1. Mass spectrum, m/z (Irel, %):
242 [М(37Cl)]+ (349), 241 (33), 240 [М(35Cl)]+ (100), 239
(53), 205 (39), 177 (17), 151 (11), 128 (10), 102 (15), 75
(14). Found, %: C 70.01; H 3.62; N 11.57. C14H9ClN2.
Calculated, %: C 69.86; H 3.77; N 11.64.
5-Chloro-2-ethyl-3-methyl-1Н-pyrrolo[2,3-b]pyridine
(4m). Yield 0.483 g (62%), light-cream colored crystals,
mp 154–155°С (hexane). Rf 0.8 (EtOAc). IR spectrum, ν, cm−1:
3159, 3060, 2970, 2857, 1577, 1495, 1410, 1280, 1092,
5-Chloro-2,3-dimethyl-1Н-pyrrolo[2,3-b]pyridine (4i).
Yield 0.462 g (64%), gray crystals, mp 204–205°С (MeOH).
Rf 0.7 (EtOAc). IR spectrum, ν, cm−1: 3138, 3039, 2928,
2855, 1578, 1492, 1401, 1286, 921, 874. 1H NMR
spectrum (DMSO-d6), δ, ppm (J, Hz): 2.14 (3H, s, 3-CH3);
2.33 (3H, s, 2-CH3); 7.86 (1H, d, J = 1.8, H-4); 8.04 (1H, d,
J = 1.8, H-6); 11.43 (1H, br. s, NH). 13C NMR spectrum
(DMSO-d6), δ, ppm: 7.7; 11.0; 103.7; 121.6; 122.0; 123.6;
134.2; 138.6; 146.0. Mass spectrum, m/z (Irel, %): 182
[М(37Cl)]+ (32), 181 (45), 180 [М(35Cl)]+ (98), 179 (100),
167 (19), 165 (2), 144 (7), 138 (6), 102 (8), 51 (7), 28 (13).
Found, %: C 59.93; H 4.89; N 15.47. C9H9ClN2.
Calculated, %: C 59.84; H 5.02; N 15.51.
5-Chloro-2-methyl-3-propyl-1Н-pyrrolo[2,3-b]pyridine
(4j). Yield 0.559 g (67%), beige crystals, mp 124–125°С
(hexane). Rf 0.55 (EtOAc). IR spectrum, ν, cm−1: 3146,
3050, 2956, 2930, 2866, 1576, 1494, 1409, 1388, 1289,
1078, 954, 874. 1H NMR spectrum (CDCl3), δ, ppm
(J, Hz): 0.94 (3H, t, J = 7.3, 3-CH3); 1.63 (2H, sext, J = 7.3,
CH2CH3); 2.45 (3H, s, 2-CH3); 2.63 (2H, t, J = 7.3,
CH2CH2CH3); 7.76 (1H, d, J = 2.1, H-4); 8.13 (1H, d, J = 2.1,
H-6); 10.55 (1H, br. s, NH). 13C NMR spectrum (CDCl3),
δ, ppm: 12.0; 14.0; 23.9; 25.9; 110.4; 122.7; 122.9; 125.5;
134.3; 138.9; 146.6. Mass spectrum, m/z (Irel, %): 210
[М(37Cl)]+ (7), 208 [М(35Cl)]+ (21), 181 (32), 179 (100),
144 (10), 102 (4). Found, %: C 63.40; H 6.15; N 13.39.
C11H13ClN2. Calculated, %: C 63.31; H 6.28; N 13.42.
5-Chloro-3-isopropyl-2-methyl-1Н-pyrrolo[2,3-b]py-
ridine (4k). Yield 0.302 g (36%), cream colored crystals;
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925, 874. H NMR spectrum (DMSO-d6), δ, ppm (J, Hz):
1.22 (3H, t, J = 7.6, CH2CH3); 2.15 (3H, s, 3-CH3); 2.70
(2H, q, J = 7.6, CH2CH3); 7.90 (1H, d, J = 2.2, H-4); 8.06
(1H, d, J = 2.2, H-6); 11.47 (1H, br. s, NH). 13C NMR
spectrum (DMSO-d6), δ, ppm: 7.8; 13.8; 18.9; 103.2; 121.6;
122.2; 124.4; 138.9; 140.6; 146.3. Mass spectrum, m/z (Irel, %):
196 [М(37Cl)]+ (17), 194 [М(35Cl)]+ (57), 181 (32), 179
(100), 165 (14), 144 (13), 102 (10), 89 (7), 75 (9), 26 (22).
Found, %: C 61.62; H 5.77; N 14.37. C10H11ClN2.
Calculated, %: C 61.70; H 5.70; N 14.39.
5-Chloro-2-ethyl-3-phenyl-1Н-pyrrolo[2,3-b]pyridine
(4n). Yield 0.893 g (87%), yellowish crystals, mp 194–195°С
(MeOH). Rf 0.55 (CHCl3). IR spectrum, ν, cm−1: 3139,
3033, 2974, 2934, 2874, 1600, 1504, 1452, 1407, 1280,
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1082, 972, 940, 879, 760, 706, 682. H NMR spectrum
(DMSO-d6), δ, ppm (J, Hz): 1.30 (3H, t, J = 7.4, CH3); 2.85
(2H, q, J = 7.4, CH2); 7.33 (1H, t, J = 7.6, H-4 Ph); 7.36–
7.50 (4H, m, H-2,3,5,6 Ph); 7.86 (1H, d, J = 1.7, H-4); 8.18
(1H, d, J = 1.7, H-6); 12.01 (1H, br. s, NH). 13C NMR
spectrum (DMSO-d6), δ, ppm: 14.1; 19.4; 110.4; 120.3;
122.7; 124.8; 126.2; 128.3 (2С); 128.9 (2С); 133.7; 139.9;
141.2; 146.4. Mass spectrum, m/z (Irel, %): 258 [М(37Cl)]+
(35), 256 [М(35Cl)]+ (100), 243 (22), 241 (74), 206 (65),
205 (44), 179 (11), 164 (8), 151 (8), 102 (7), 77 (8). Found,
%: C 70.27; H 4.99; N 10.88. C15H13ClN2. Calculated, %:
C 70.18; H 5.10; N 10.91.
5-Chloro-3-ethyl-2-propyl-1Н-pyrrolo[2,3-b]pyridine (4o).
Yield 0.642 g (72%), light-yellow crystals, mp 109–110°С
201