Molecules 2019, 24, 948
12 of 16
(3
β)-N-(2-Pyrrolidin-1-ylethyl)-3-hydroxy-olean-12-en-28-amide (37), Compound 37 was prepared
from 32 according to general procedure C. Column chromatography (SiO , CHCl /MeOH 95:5) gave
2
3
◦
◦
3
7
(yield: 76%); m.p. 189–192 C; [
α
] = +40.8 (c 0.325, MeOH); R = 0.28 (CHCl /MeOH 9:1); IR
= 3386br w, 2941m, 1631m, 1527m, 1320s, 1031m, 996m, 823m, 752m cm ; H-NMR (500
D
f
3
−
1 1
(ATR):
ν
MHz, CDCl ):
δ
= 6.94 (t, J = 5.6 Hz, 1H, NH), 5.42 (t, J = 3.7 Hz, 1H, 12-H), 3.88–3.78 (m, 2H, 33-H
a
,
3
0
0
33 -H
a
), 3.73–3.62 (m, 1H, 31-H
a
), 3.51–3.41 (m, 1H, 31-H ), 3.35–3.22 (m, 2H, 33-H , 33 -H ), 3.20
b
b
b
(
(
dd, J = 11.5, 4.4 Hz, 1H, 3-H), 2.99–2.88 (m, 2H, 32-H), 2.66 (dd, J = 12.9, 3.7 Hz, 1H, 18-H), 2.19–2.05
0
m, 4H, 34-H, 34 -H), 2.01 (ddd, J = 13.9, 13.8, 3.9 Hz, 1H, 16-H
a
a
), 1.97–1.84 (m, 2H, 11-H , 11-Hb),
1
1
1
2
2
.70 (t, J = 13.4 Hz, 1H, 19-H
5-H , 7-H , 6-H , 21-H ), 1.28–1.23 (m, 1H, 7-H ), 1.21–1.15 (m, 2H, 19-H , 21-H ), 1.14 (s, 3H, 27-H),
.04 (ddd, J = 14.4, 3.5, 3.4 Hz, 1H, 15-H ), 0.98 (s, 3H, 23-H), 0.97–0.92 (m, 1H, 1-H ), 0.91 (s, 3H,
a
), 1.65–1.29 (m, 12H, 1-H
a
, 16-H , 2-H , 2-H , 22-H , 22-H , 9-H, 6-H ,
a
a
a
b
b
b
a
a
b
a
b
b
b
b
b
9-H), 0.90 (s, 3H, 25-H), 0.89 (s, 3H, 30-H), 0.77 (s, 3H, 24-H), 0.74–0.70 (m, 1H, 5-H), 0.71 (s, 3H,
6-H) ppm; 13C-NMR (126 MHz, CDCl ):
δ = 180.1 (C-28), 143.8 (C-13), 123.4 (C-12), 79.1 (C-3), 55.3
3
0
(
C-5), 55.1 (C-33, C-33 ), 54.9 (C-32), 47.7 (C-9), 46.5 (C-17, C-19), 41.9 (C-14), 41.5 (C-18), 39.6 (C-8), 38.9
(
2
1
C-4), 38.6 (C-1), 37.1 (C-10), 36.4 (C-31), 34.3 (C-21), 33.2 (C-30), 32.9 (C-22), 32.6 (C-7), 30.8 (C-20),
0
8.2 (C-23), 27.5 (C-15), 27.3 (C-2), 26.0 (C-27), 23.7 (C-29), 23.6 (C-16), 23.5 (C-11), 23.4 (C-34, C-34 ),
+
8.5 (C-6), 17.2 (C-26), 15.7 (C-24), 15.5 (C-25) ppm; MS (ESI, MeOH): m/z = 553.5 (100%, [M + H] );
analysis calcd. for C H N O (552.89): C 78.21, H 10.94, N 5.07; found: C 78.01, H 11.13, N 4.83.
36
60
2
2
(2α β)-N-(2-Pyrrolidin-1-ylethyl)-2,3-dihydroxy-olean-12-en-28-amide (38), Compound 38 was prepared
,3
from 33 according to general procedure C. Column chromatography (SiO , CHCl /MeOH 9:1) gave
2
3
◦
◦
α] = +44.3 (c 0.330, CHCl ); R = 0.10 (CHCl /MeOH
f
D 3 3
3
8
(yield: 67%); m.p. 153–156 C (decomp.); [
9
5:5); IR (KBr): = 3406br s, 2946s, 2878s, 2808m, 1636s, 1522m, 1462m, 1386m, 1364m, 1268w, 1194w,
ν
−
150w, 1050m cm ; H-NMR (400 MHz, CDCl ): δ = 6.72 (t, J = 5.1 Hz, 1H, NH), 5.34 (t, J = 3.6 Hz,
3
1 1
1
1
H, 12-H), 3.67 (ddd, J = 11.3, 9.4, 4.4 Hz, 1H, 2-H), 3.53–3.43 (m, 1H, 31-H
a
), 3.31–3.22 (m, 1H, 31-Hb),
0
2
2
2
.99 (d, J = 9.5 Hz, 1H, 3-H), 2.80–2.63 (m, 6H, 32-H, 33-H, 33 -H), 2.56 (dd, J = 13.4, 4.3 Hz, 1H, 18-H),
.02–1.89 (m, 4H, 1-H
2-H , 16-H , 9-H, 22-H , 6-H
0
a
, 11-H
a
, 11-H , 16-H
b
a
), 1.89–1.83 (m, 4H, 34-H, 34 -H), 1.79–1.24 (m, 11H, 19-H
a
,
a
b
b
a
, 15-H
a
, 7-H
a
, 6-H , 21-H , 7-H ), 1.23–1.11 (m, 2H, 21-H , 19-H ), 1.14
b
a
b
b
b
(
s, 3H, 27-H), 1.08–0.99 (m, 1H, 15-H ), 1.02 (s, 3H, 23-H), 0.97 (s, 3H, 25-H), 0.94–0.87 (m, 1H, 1-H ),
b
b
0
.90 (s, 3H, 29-H), 0.89 (s, 3H, 30-H), 0.85–0.79 (m, 1H, 5-H), 0.81 (s, 3H, 24-H), 0.75 (s, 3H, 26-H) ppm;
13
C-NMR (101 MHz, CDCl3):
δ
= 178.6 (C-28), 144.5 (C-13), 122.8 (C-12), 84.0 (C-3), 68.9 (C-2), 55.3
0
(
(
(
(
C-5), 54.6 (C-32), 54.2 (C-33, C-33 ), 47.7 (C-9), 46.8 (C-19), 46.5 (C-1), 46.5 (C-17), 42.2 (C-18), 42.1
C-14), 39.6 (C-8), 39.3 (C-4), 38.3 (C-10), 37.6 (C-31), 34.3 (C-21), 33.2 (C-30), 32.8 (C-22), 32.5 (C-7), 30.8
C-20), 28.8 (C-23), 27.5 (C-15), 25.9 (C-27), 23.8 (C-11), 23.7 (C-29), 23.7 (C-34, C-34 ), 23.6 (C-16), 18.5
C-6), 17.1 (C-26), 16.9 (C-24), 16.8 (C-25) ppm; MS (ESI, MeOH): m/z = 569 (100%, [M + H] ); analysis
0
+
calcd. for C H N O (568.89): C 76.01, H 10.63, N 4.92; found: C 75.86, H 10.90, N 4.77.
36
60
2
3
(
3
β)-N-(2-Piperidin-1-ylethyl)-3-acetyloxy-olean-12-en-28-amide (42), Compound 42 was prepared
from
7
according to general procedure B using 1-(2-aminoethyl)-piperidine as amino compound.
◦
Column chromatography (SiO , CHCl /MeOH 9:1) gave 42 (yield: 76%); m.p. = 163–166 C (decomp.);
2
3
◦
[
α
] = +47.5 (c 0.305, CHCl ); R = 0.55 (silica gel, CHCl /MeOH 9:1); IR (ATR):
D
ν
= 2943m, 2864w,
3
f
3
1
9
732m, 1642w, 1523w, 1432m, 1388m, 1365s, 1330m, 1244vs, 1214m, 1149w, 1097w, 1027m, 1007m,
1
86m, 751m; H-NMR (500 MHz, CDCl ): δ = 6.93 (t, J = 5.3 Hz, 1H, NH), 5.42 (dd, J = 3.3 Hz, 3.3 Hz,
3
1
1
2
a
H, 12-H), 4.51–4.44 (m, 1H, 3-H), 3.71 (dq, J = 11.9, 5.9 Hz, 1H, 31-H ), 3.46 (dq, J = 12.2, 6.0 Hz,
H, 31-H ), 3.13 (s, 2H, 32-H), 2.64 (dd, J = 12.9, 3.3 Hz, 1H, 18-H), 2.03 (s, 3H, Ac), 2.02–1.84 (m, 8H,
b
0
-H
a
, 2-H , 16-H
a
, 16-H . 33-H, 33 -H), 1.70 (m, 1H, 19-H
a
), 1.66–1.40 (m, 15H, 1-H
a
, 11-H
a a
, 22-H ,
b
b
0
1
1
2
1-H , 9-H, 22-H , 6-H
a
, 15-H
a
, 7-H
a
, 34-H, 34 -H, 35-H), 1.40–1.30 (m, 2H, 6-H , 21-H
a
), 1.24 (m,
b
b
b
H, 7-H ), 1.22–1.14 (m, 2H, 19-H , 21-H ), 1.13 (s, 3H, 27-H), 1.04 (m, 2H, 1-H , 15-H ), 0.92 (s, 3H,
b
b
b
b
b
9-H) 0.92 (s, 3H, 26-H), 0.89 (s, 3H, 30-H), 0.85 (s, 3H, 23-H), 0.84 (s, 3H, 25-H), 0.81 (s, 1H, 5-H), 0.71
(
(
s, 3H, 24-H); 13C-NMR (126 MHz, CDCl3):
δ
= 179.9 (C-28), 171.1 (Ac), 143.9 (C-13), 123.3 (C-12), 81.0
0
C-3), 56.9 (C-32), 55.3 (C-5), 54.5 (C-33 + C-33 ), 47.6 (C-9), 46.5 (C-19), 46.5 (C-17), 41.9 (C-14), 41.5