310 J ournal of Natural Products, 1999, Vol. 62, No. 2
Notes
EIMS, FABMS, UV, and specific rotations were taken on a
J EOL J MS-HX 300, a J EOL J MS-HX 110, a Hitachi S-3200
spectrometer, and a J ASCO DIP-180 digital polarimeter,
respectively. Extracts were chromatographed on Si gel (Merck
3374, 70-230 mesh).
P la n t Ma ter ia l. The stems of Diospyros maritima Blume
were collected in Lin-Ko, Taiwan, in 1993. The plant material
was identified by Mr. Muh-Tsuen Gun, formerly a technician
of the Department of Botany, National Taiwan University. A
voucher specimen has been deposited at the National Research
Institute of Chinese Medicine, Taipei, Taiwan, Republic of
China.
(1H, d, J ) 2.0 Hz, H-29), 1.70 (3H, s, H-30), 7.41 (2H, d, J )
8.8 Hz, H-2′, 6′), 6.81 (2H, d, J ) 8.8 Hz, H-3′, 5′), 7.58 (1H, d,
J ) 16.0 Hz, H-7′), 6.27 (1H, d, J ) 16.0 Hz, H-8′), 2.32 (2H,
t, J ) 7.5 Hz, H-2′′), 1.20-1.30 (26H, br s, H-3′′-15′′), 0.87 (3H,
m, H-16′′); 13C NMR (CDCl3, 75 MHz) δ 38.4 (t, C-1), 23.8 (t,
C-2), 80.8 (d, C-3), 38.0 (s, C-4), 55.4 (d, C-5), 18.1 (t, C-6),
34.1 (t, C-7), 40.9 (s, C-8), 50.3 (d, C-9), 37.1 (s, C-10), 21.0 (t,
C-11), 25.2 (t, C-12), 37.6 (d, C-13), 42.7 (s, C-14), 27.1 (t, C-15),
29.6 (t, C-16), 46.4 (s, C-17), 48.8 (d, C-18), 47.7 (d, C-19), 150.1
(s, C-20), 29.7 (t, C-21), 34.5 (t, C-22), 28.0 (q, C-23), 16.0 (q,
C-24), 16.2 (q, C-25), 16.7 (q, C-26), 14.7 (q, C-27), 63.0 (t, C-28),
109.9 (t, C-29), 19.1 (q, C-30), 127.2 (s, C-1′), 130.2 (d, C-2′),
115.9 (d, C-3′), 157.8 (s, C-4′), 115.9 (d, C-5′), 130.2 (d, C-6′),
144.0 (d, C-7′), 116.2 (d, C-8′), 167.3 (s, C-9′), 174.6 (s, C-1′′),
33.9 (t, C-2′′), 25.1 (t, C-3′′), 29.1-29.7 (t, C-4′′-13′′), 31.9 (t,
C-14′′), 22.7 (t, C-15′′), 14.1 (q, C-16′′); EIMS (70 eV) m/z 662
[M - C9H8O3]+ (38), 619 (15), 424 (24), 203 (76), 189 (100),
147 (40); HREIMS m/z 662.5977 [M - C9H8O3]+ (calcd for
E xt r a ct ion a n d Isola t ion . Dried pieces of stems of D.
maritima (16 kg) were extracted three times with EtOH (160
L) at 60 °C (10 h for each time). The EtOH extract was
evaporated in vacuo, yielding a black residue, which was
suspended in H2O (12 L), and then partitioned (5 ×) with 1 L
of n-hexane. The aqueous layer was partitioned again with (4
× 1 L) n-BuOH. The combined n-BuOH extract (180 g) was
chromatographed on Si gel using n-hexane and EtOAc of
increasing polarity as eluent and further purified by HPLC,
eluting with EtOAc-n-hexane (3:7). Two components, 3-(E)-
coumaroylbetulinaldehyde (1) (10 mg) and 3-(E)-coumaroyl-
28-palmitoylbetulin (2) (15 mg), were obtained in pure state.
3-(E)-Cou m a r oylbetu lin a ld eh yd e (1): amorphous solid;
[R]20D +20.2° (c 0.4, CHCl3); UV (MeOH) λmax (log ꢀ) 312 (4.60)
nm; IR (dry film) νmax 3360, 3045, 1715, 1684, 1660, 1610, 1595,
1585, 1510, 970, 880 cm-1; 1H NMR (CDCl3, 300 MHz) δ 4.57
(1H, m, H-3), 2.85 (1H, m, H-19), 0.88 (3H, s, H-23), 0.83 (3H,
s, H-24), 0.85 (3H, s, H-25), 0.90 (3H, s, H-26), 0.96 (3H, s,
H-27), 9.66 (3H, s, H-28), 4.61 (1H, d, J ) 2.0 Hz, H-29), 4.73
(1H, d, J ) 2.0 Hz, H-29), 1.68 (3H, s, H-30), 7.41 (2H, d, J )
8.8 Hz, H-2′, 6′), 6.81 (2H, d, J ) 8.8 Hz, H-3′, 5′), 7.57 (1H, d,
J ) 16.7 Hz, H-7′), 6.27 (1H, d, J ) 16.7 Hz, H-8′); 13C NMR
(CDCl3, 75 MHz) δ 38.0 (t, C-1), 23.8 (t, C-2), 80.8 (d, C-3),
38.7 (s, C-4), 55.4 (d, C-5), 18.2 (t, C-6), 34.3 (t, C-7), 40.8 (s,
C-8), 50.4 (d, C-9), 37.1 (s, C-10), 20.8 (t, C-11), 25.5 (t, C-12),
38.4 (d, C-13), 42.6 (s, C-14), 29.2 (t, C-15), 28.8 (t, C-16), 59.3
(s, C-17), 48.0 (d, C-18), 47.5 (d, C-19), 149.7 (s, C-20), 29.8 (t,
C-21), 33.2 (t, C-22), 28.0 (q, C-23), 15.9 (q, C-24), 16.2 (q, C-25),
16.6 (q, C-26), 14.2 (q, C-27), 206.8 (d, C-28), 110.2 (t, C-29),
19.0 (q, C-30), 127.4 (s, C-1′), 129.9 (d, C-2′), 115.8 (d, C-3′),
157.5 (s, C-4′), 115.8 (d, C-5′), 129.9 (d, C-6′), 143.9 (d, C-7′),
116.4 (d, C-8′), 167.2 (s, C-9′); EIMS (70 eV) m/z 586 [M]+ (21)
558 (8), 422 (26), 394 (14), 189 (39), 147 (100); HREIMS m/z
586.4047 (calcd for C39H54O4, 586.4024).
C
46H78O2: 662.6005).
P a r t ia l Hyd r olysis of 2 w it h 5% Met h a n olic HCl.
o
Compound 2 (8 mg) was heated at 60 C in 5% methanolic
HCl (1.5 mL) for 4 h. The reaction was quenched with 20 mL
of H2O; the products were extracted with 10 mL of EtOAc and
purified by HPLC, eluting with EtOAc-n-hexane (2.5:7.5), to
yield 3-(E)-coumaroyllbetulin (3.0 mg)15 and methyl palmitate
(1.5 mg).16
Ack n ow led gm en t. This research was supported by the
National Science Council of the Republic of China.
Refer en ces a n d Notes
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233.
(4) Chen, C. C.; Yu, H. J .; Ou, J . C.; Pan, T. M. J . Chin. Chem. Soc. 1994,
41, 195-198.
(5) Lee, T. J .; Shih, T. S.; Lin, Y. M.; Chen, F. C. Formosan Sci. 1984,
38, 147-151.
(6) Chen, H. C.; Lin, Y. M.; Shih, T. S.; Chen, F. C. Formosan Sci.
1987,41, 46-52.
(7) Chen, H. K.; Chen, K. J .; Lin Y. S.; Chen, F. C. Formosan Sci. 1991,
44, 63-71.
(8) Kan, W. S. Pharmaceutical Botany, National Research Institute of
Chinese Medicine: Taipei, 1997; p 440.
(9) Kuo, Y. H.; Chang, C. I.; Kuo, Y. H. J . Chin. Chem. Soc. 1996, 43,
511-514.
(10) Kuo, Y. H.; Chang, C. I.; Kuo, Y. H. Phytochemistry 1997, 46, 1135-
1137.
(11) Kuo, Y. H.; Chang, C. I.; Kuo, Y. H. Chem. Pharm. Bull. 1997, 45,
1221-1222.
(12) Kuo, Y. H.; Chang, C. I.; Kuo, Y. H. Planta Med. 1997, 63, 363-365.
(13) Monaco, P.; Previtera, L. J . Nat. Prod. 1984, 47, 463-468.
(14) Tinto, W. F.; Blair, L. C.; Ali, A.; Reynolds, W. F.; McLean S. J . Nat.
Prod. 1992, 55, 395-398.
(15) Rashid, M. A.; Gray, A. I.; Waterman, P. G. J . Nat. Prod. 1992, 55,
851-859.
(16) Kuo, Y. H.; Yeh, M. H. J . Chin Chem. Soc. 1997, 44, 379-383.
3-(E)-Cou m a r oyl-28-p a lm itoylbetu lin (2): amorphous
solid; [R]20 +32.1° (c 0.6, CHCl3); UV (MeOH) λmax (log ꢀ) 309
D
(4.70) nm; IR (dry film) νmax 3400, 3040, 1730, 1680, 1670,
1
1640, 1600, 1595, 1507, 960, 877 cm-1; H NMR (CDCl3, 300
MHz) δ 4.55 (1H, m, H-3), 2.39 (1H, m, H-19), 0.86 (3H, s,
H-23), 1.00 (3H, s, H-24), 0.85 (3H, s, H-25), 0.88 (3H, s, H-26),
0.95 (3H, s, H-27), 3.81 (1H, d, J ) 10.8 Hz, H-28), 4.27 (1H,
d, J ) 10.8 Hz, H-28), 4.57 (1H, d, J ) 2.0 Hz, H-29), 4.66
NP980217V