Derivatives of Oleanolic Acid and Their Biological Activity
3β-Acetoxyolean-12-en-28-oic acid morpholide 4a: C36H57NO4; mol. mass: 567.85; yield:
549 mg (96.6%); m.p.: 238–239°C; IR (KBr, ν, cm-1): 1720 (C = O, CH3COO), 1630 (C = O,
amide); 1H NMR (CHCl3, δ, ppm): 5.27 (1H, t, J = 3.4 Hz, C12-H), 4.49 (1H, dd, J = 7.0 and 8.9
Hz, C3-Hα), 3.70–3.57 (8H, m, morpholine ring), 2.05 (3H, s, CH3COO), 1.14, 0.93, 0.92, 0.90,
0.86, 0.85 and 0.74 (21 H, 7 x s, 7 x CH3); 13C NMR (CHCl3, δ, ppm): 175.1 (Cq, C-28), 171.0
(Cq, CH3COO), 144.6 (Cq, C-13), 121.5 (CH, C-12), 80.9 (CH, C-3), 2 x 66.9, 46.3 and 46.0 (4 x
CH2, morpholine ring), 47.4 (Cq, C-17), 21.3 (CH3, CH3COO); DEPT: 8 x CH3, 14 x CH2, 5 x
CH (36 x C atoms); MS (m/z, %): 567.4 (68.8, M+•); HR MS: calcd. for C36H57NO4: 567.4287,
found: 567.4285.
3β-Acetoxyolean-12-en-28-oic acid N-methylpiperazide 4b: C37H60N2O3; mol. mass:
580.90; yield: 541 mg (93.2%); m.p.: 218–220°C; IR (KBr, ν, cm-1): 1710 (C = O, CH3COO),
1600 (C = O, amide); 1H NMR (CHCl3, δ, ppm): 5.26 (1H, t, J = 3.5 Hz, C12-H), 4.49 (1H, dd,
J = 7.0 and 8.8 Hz, C3-Hα), 3.70–3.59 and 2.41–2.31 (2 x 4H, 2 x m, piperazine ring), 2.29 (3H,
s, >N–CH3), 2.05 (3H, s, CH3COO), 1.13, 0.93, 0.92, 0.90, 0.86, 0.85 and 0.74 (21 H, 7 x s, 7 x
CH3); 13C NMR (CHCl3, δ, ppm): 174.9 (Cq, C-28), 170.9 (Cq, CH3COO), 144.8 (Cq, C-13),
121.3 (CH, C-12), 80.9 (CH, C-3), 55.2 x 2 and 38.0 x 2 (4 x CH2, piperazine ring), 47.6 (Cq, C-
17), 46.0 (CH3, >N–CH3), 21.3 (CH3, CH3COO); DEPT: 9 x CH3, 14 x CH2, 5 x CH (37 x C
atoms); MS (m/z, %): 580.7 (3.6, M+•); HR MS: calcd. for C37H60N2O3: 580.4604, found:
580.4600.
3β-Acetoxyolean-12-en-28-oic acid pyrrolidide 4c: C36H57NO3; mol. mass: 551.85; yield:
507 mg (91.9%); m.p.: 212–213°C; IR (ν, cm-1): 1720 (C = O, CH3COO), 1710 (C = O, amide);
1H NMR (CHCl3, δ, ppm): 5.26 (1H, t, J = 3.5 Hz, C12-H), 4.49 (1H, dd, J = 7.0 and 8.9 Hz, C3-
Hα), 3.55–3.44 and 1.73–1.54 (2 x 4H, 2 x m, pyrrolidine ring), 2.04 (3H, s, CH3COO), 1.14,
0.94, 0.92, 0.90, 0.86, 0.85 and 0.72 (21 H, 7 x s, 7 x CH3); 13C NMR (CHCl3, δ, ppm): 175.1
(Cq, C-28), 170.9 (Cq, CH3COO), 144.8 (Cq, C-13), 121.6 (CH, C-12), 80.9 (CH, C-3), 47.3 (Cq,
C-17), 46.1 x 2 and 27.5 x 2 (4 x CH2, pyrrolidine ring), 21.2 (CH3, CH3COO); DEPT: 8 x CH3,
14 x CH2, 5 x CH (36 x C atoms); MS (m/z, %): 551.6 (99.9, M+•); HR MS: calcd. for
C36H57NO3: 551.4338, found: 551.4340.
3β-Acetoxyolean-12-en-28-oic acid N,N-diethylamide 4d: C36H59NO3; mol. mass: 553.87;
yield: 512 mg (92.5%); m.p.: 224–226°C; IR (KBr, ν, cm-1): 1720 (C = O, CH3COO), 1705
(C = O, amide); 1H NMR (CHCl3, δ, ppm): 5.26 (1H, t, J = 3.6 Hz, C12-H), 4.49 (1H, dd, J = 7.0
and 8.9 Hz, C3-Hα), 3.49–3.26 and 1.99–1.81 (2 x 2H, 2 x m,—N< (CH2–CH3)2), 2.04 (3H, s,
CH3COO), 1.14 (6H, s,—N<(CH2–CH3)2), 1.12, 0.93, 0.92, 0.89, 0.86, 0.85 and 0.78 (21 H, 7 x
s, 7 x CH3); 13C NMR (CHCl3, δ, ppm): 174.9 (Cq, C-28), 170.9 (Cq, CH3COO), 145.0 (Cq, C-
13), 121.1 (CH, C-12), 80.9 (CH, C-3), 47.7 (Cq, C-17), 46.7 x 2 (CH2 x 2,—N<(CH2–CH3)2),
21.3 (CH3, CH3COO), 16.6 x 2 (CH3 x 2,—N<(CH2–CH3)2); DEPT: 10 x CH3, 12 x CH2, 5 x
CH (36 x C atoms); MS (m/z, %): 553.7 (34.7, M+•); HR MS: calcd. for C36H59NO3: 553.4492,
found: 553.4490.
3β-Acetoxyolean-12-en-28-oic acid N’,N’-dimethylaminoethylamide 4f: C36H60N2O3;
mol. mass: 568.88; yield: 535 mg (94.1%); m.p.: 163–165°C; IR (KBr, ν, cm-1): 3400 (N–H),
1720 (C = O, CH3COO), 1630 (C = O, amide); 1H NMR (DMSO, δ, ppm): 7.71 (1H, t, J = 5.2
Hz, N–H), 5.23 (1H, s, C12-H), 4.49 (1H, dd, J = 4.6 and 11.1 Hz, C3-Hα), 2.72 (6H, s,—NH–
CH2–CH2–N<(CH3)2), 2.02 (3H, s, CH3COO), 1.62–1.44 (4H, m,—NH–CH2–CH2–N<
(CH3)2), 1.11, 0.89, 0.88, 0.87, 0.81, 0.80, 0.67 (21 H, 7 x s, 7 x CH3); 13C NMR (DMSO,
δ, ppm): 177.1 (Cq, C-28), 170.9 (Cq, CH3COO), 143.9 (Cq, C-13), 121.5 (CH, C-12), 79.9 (CH,
C-3), 56.0 x 2 (2 x CH2,—NH–CH2–CH2–N<(CH3)2), 45.4 (Cq, C-17), 42.5 x 2 (2 x CH3,—
NH–CH2–CH2–N<(CH3)2), 21.0 (CH3, CH3COO); DEPT: 10 x CH3, 12 x CH2, 5 x CH (36 x
C atoms); MS (m/z, %): 568.4 (6.01, M+•); HR MS: calcd. for C36H60N2O3: 568.4603, found:
568.4606.
PLOS ONE | DOI:10.1371/journal.pone.0122857 May 26, 2015
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