Medicinal Chemistry Research (2021) 30:940–951
949
(
1H, s, H-12′), 7.51–7.49 (1H, m, H-18′), 7.28–7.23 (3H,
m, H-16′, H-17′, H-10′ or H-11′), 5.14 (1H, br s, H-12),
.49-4.47 (2H, m, Н-4′), 4.24-4.22 (1H, m, Н-3), 4.06-4.01
N-{4-[(3β-acetoxyolean-12-en-28-oyl)-butyl]-(E)-4-[2-(1H-
indol-3-yl)-vinyl]}pyridinium bromide (17)
4
(
(
(
2H, m, Н-1′), 2.23 (1H, d, J = 11.0 Hz, Н-18), 2.06–0.82
Brown powder. Yield: 85%; mp 162–164 °C (EtOH); [α]
2
1
26H, m, CH, CH in pentacyclic skeleton, H-2′, H-3′), 1.93
+ 23.3 (с 0.03, СН ОН); IR (film) ν
1722 (C = O),
2
D
3
max
−
1
1
3H, s, Me), 1.06, 0.97, 0.89, 0.76, 0.73, 0.69, and 0.59 (3H
3443 (NH) сm ; H NMR (500 MHz, MeOD): δ = 8.60
(2H, d, J = 6.5 Hz, H-5′, H-9′), 8.21 (1H, d, J = 16.0 Hz, H-
10′ or H-11′), 8.09–8.08 (1H, m, H-15′), 8.02 (2H, d, J =
6.5 Hz, H-6′, H-8′), 7.89 (1H, s, H-12′), 7.50-7.49 (1H, m,
H-18′), 7.29–7.21 (3H, m, H-16′, H-17′, H-10′ or H-11′),
5.17 (1H, br s, H-12), 4.52-4.43 (2H, m, Н-4′), 4.26–4.23
(1H, m, Н-3), 4.09–4.02 (2H, m, Н-1′), 2.86 (1H, d, J =
13
each, all s, H-23–H-27, H-29 and H-30) ppm; C NMR
(
(
125 MHz, MeOD): δ = 180.5 (C-28), 172.9 (С = О), 157.4
C-7′), 144.3 (C-5′, C-9′), 140.1 (C-19′), 139.6 (C-13),
1
1
1
8
4
1
3
2
39.3 (C-10′ or C-11′), 134.1 (C-12′), 126.7 (C-12, C-14′),
24.6 (C-16′), 123.5 (C-6′, C-8′), 122.9 (C-17′), 121.8 (C-
5′), 117.9 (C-10′ or C-11′), 115.9 (C-13′), 113.6 (C-18′),
2.4 (C-3), 65.1 (C-1′), 60.8 (C-4′), 56.6 (C-5), 54.4 (C-18),
9.3 (C-17), 48.6 (C-9), 43.3 (C-14), 40.9 (C-8), 40.5 (C-
9, C-20), 39.3 (C-1), 38.6 (C-4), 38.1 (C-22), 38.0 (C-10),
4.2 (C-7), 31.8 (С-21), 30.2 (С-2′), 29.1 (C-15), 28.6 (C-
3), 26.5 (C-3′), 25.4 (C-16), 24.5 (C-2), 24.3 (C-11), 24.2
11.0 Hz, Н-18), 2.07-0.71 (26H, m, CH, CH in pentacyclic
2
skeleton, H-2′, H-3′), 1.95 (3H, s, Me), 1.11, 0.95, 0.91,
0.75, 0.72, 0.69, and 0.56 (3H each, all s, H-23–H-27, H-29
1
3
and H-30) ppm; C NMR (125 MHz, MeOD): δ = 179.4
(C-28), 172.8 (С = О), 157.3 (C-7′), 145.4 (C-13), 144.2
(C-5′, C-9′), 139.6 (C-19′), 139.2 (C-10′ or C-11′), 134.1
(C-12′), 126.7 (C-14′), 124.6 (C-16′), 123.6 (C-12), 123.4
(C-6′, C-8′), 122.9 (C-17′), 121.7 (C-15′), 117.9 (C-10′ or
C-11′), 115.9 (C-13′), 113.6 (C-18′), 82.4 (C-3), 64.9 (C-
1′), 60.7 (C-4′), 56.6 (C-5), 48.6 (C-19), 48.2 (C-9), 47.1
(
C-27), 21.7 (СН ), 21.3 (C-30), 19.3 (C-6), 18.1 (C-29),
3
1
7.8 (C-26), 17.2 (C-24), and 16.2 (C-25) ppm; MS (APCI):
+
m/z [M-Br] : 773.6 C H N O (calcd. 773.5); Anal.
Calcd. for C H BrN O : С 71.73; Н 8.14. Found: 71.68;
Н 8.11.
51
69
2
4
5
1
69
2
4
(C-17), 42.9 (C-14, C-18), 40.7 (C-8), 39.2 (C-1), 38.6 (C-
N-{4-[(3β-hydroxyolean-12-en-28-oyl)-butyl]-(E)-4-[2-(1H-
indol-3-yl)-vinyl]}pyridinium bromide (16)
4), 38.1 (C-10), 34.9 (C-22), 33.9 (C-7), 33.8 (С-21), 33.7
(C-30), 31.7 (C-20), 30.2 (C-2′), 28.8 (C-15), 28.6 (C-23),
26.5 (С-3′, C-29), 24.6 (C-2), 24.3 (C-11), 24.2 (C-27,
Orange powder. Yield: 83%; mp 184–186 °C (EtOH); [α]
C-16), 21.3 (CH ), 19.4 (C-6), 17.9 (C-26), 17.2
(C-24), and 16.2 (C-25) ppm; MS (APCI): m/z [M-Br] :
3
2
1
+
+
15 (с 0.04, DMSO); IR (film) ν
1716 (C = O),
D
max
−
1 1
2
928 (OH), 3437 (NH) cm ; H NMR (400 MHz, DMSO-
773.6 C H N O (calcd. 773.5); Anal. Calcd. for
5
1
69
2
4
d6): δ = 11.99 (1H, s, NH), 8.84 (2H, d, J = 6.5 Hz, H-5′,
H-9′), 8.31 (1H, d, J = 16.0 Hz, H-10′ or H-11′), 8.19–8.15
C H BrN O : С 71.73; Н 8.14. Found: С 71.69; Н 8.11.
51 69 2 4
(
3H, m, H-15′, H-6′, H-8′), 7.98 (1H, s, H-12′), 7.53–7.51
N-{4-[(3β-hydroxy-11-oxo-18β,20β-olean-12-en-29-oyl)-
butyl]-(E)-4-[2-(1H-indol-3-yl)-vinyl]}pyridinium bromide
(18)
(
1H, m, H-18′), 7.33–7.21 (3H, m, H-16′, H-17′, H-10′ or
H-11′), 5.11 (1H, br s, H-12), 4.51–4.47 (2H, m, Н-4′),
.04–3.93 (2H, m, Н-1′), 2.91–2.88 (1H, m, Н-3), 2.75 (1H,
4
d, J = 11.0 Hz, Н-18), 2.01–0.71 (26H, m, CH, CH in
pentacyclic skeleton, H-2′, H-3′), 1.05, 0.88, 0.87, 0.78,
Orange powder. Yield: 81%; mp 154–156 °C (EtOH); [α]
2
2
1
+ 75 (с 0.04, DMSO); IR (film) ν
1721 (C = O),
D
max
−
1 1
0
.72, 0.56, and 0.52 (3H each, all s, H-23–H-27, H-29 and
2927 (OH), 3440 (NH) cm ; H NMR (400 MHz, DMSO-
d6): δ = 11.99 (1H, s, NH), 8.81 (2H, d, J = 6.5 Hz, H-5′,
H-9′), 8.27 (1H, d, J = 16.0 Hz, H-10′ or H-11′), 8.16–8.14
(3H, m, H-15′, H-6′, H-8′), 7.98 (1H, s, H-12′), 7.53–7.52
(1H, m, H-18′), 7.32–7.22 (3H, m, H-16′, H-17′, H-10′ or
H-11′), 5.37 (1H, br s, H-12), 4.51–4.48 (2H, m, Н-4′),
4.15–4.06 (2H, m, Н-1′), 3.02–2.99 (1H, m, Н-3), 2.59-2.56
(1H, m, Н-18), 2.31 (1H, s, Н-9), 2.11–0.68 (23H, m, CH,
1
3
H-30) ppm; C NMR (100 MHz, DMSO-d ): δ = 177.1 (C-
6
2
(
1
(
8), 155.3 (C-7′), 143.9 (C-13), 143.7 (C-5′, C-9′), 138.1
C-19′), 137.3 (C-10′ or C-11′), 133.1 (C-12′), 125.4 (C-
4′), 123.4 (C-16′), 122.4 (C-6′, C-8′), 122.3 (C-12), 121.6
C-17′), 120.9 (C-15′), 117.2 (C-10′ or C-11′), 114.2 (C-
13′), 113.1 (C-18′), 77.2 (C-3), 63.6 (C-1′), 58.9 (C-4′),
55.2 (C-5), 47.4 (C-9), 46.5 (C-17), 45.8 (C-19), 42.9 (C-
14), 41.7 (C-18), 40.2 (C-8), 39.6 (C-1), 38.7 (C-4), 36.9
CH in pentacyclic skeleton, H-2′, H-3′), 1.33, 1.11, 0.99,
2
(
3
3
(
C-10), 33.6 (C-22), 33.2 (C-30), 32.8 (C-7), 32.6 (С-21),
0.8 (C-20), 29.5 (C-2′), 28.6 (C-23), 28.3 (C-15), 27.2 (С-
′), 26.1 (C-29), 25.3 (C-16), 23.9 (C-27), 23.3 (C-11), 23.1
0.98, 0.89, 0.73, and 0.66 (3H each, all s, H-23–H-28 and
1
3
H-30) ppm; C NMR (100 MHz, DMSO-d ): δ = 199.5 (C-
6
11), 176.2 (C-29), 169.9 (C-13), 155.1 (C-7′), 143.7 (C-5′,
C-9′), 138.1 (C-19′), 137.2 (C-10′ or C-11′), 132.9 (C-12′),
127.8 (C-12), 125.4 (C-14′), 123.4 (C-16′), 122.4 (C-6′, C-
8′), 121.6 (C-17′), 120.9 (C-15′), 117.3 (C-10′ or C-11′),
114.1 (C-13′), 113.1 (C-18′), 77.1 (C-3), 63.6 (C-1′), 61.6
C-2), 18.4 (C-6), 17.2 (C-26), and 16.4 (C-24), 15.5 (C-25)
+
ppm; MS (APCI): m/z [M-Br] : 731.6 C H N O (calcd.
7
Found: С 72.51; Н 8.27.
49
67
2
3
31.5); Anal. Calcd. for C H BrN O : 72.48; Н 8.32.
49 67 2 3