T.-C. Lin et al. / Phytochemistry 51 (1999) 793±801
799
(C-1), 27.8 (C-3), 35.4 (C-7), 38.9 (C-5), 41.8 (C-18),
50.4 (C-20), 55.5 (OMe), 58.4 (C-10), 68.9 (C-19), 70.3
(C-4), 114.2 (C-11), 126.5 (C-14), 133.0 (C-8), 135.6
(C-13), 135.7 (C-9), 155.0 (C-12). EI-MS (70 eV) m/z
(rel. int.): 332 [M]+ (8), 314 (3), 190 (100), 175 (28),
161 (15), 149 (20), 133 (18), 81 (22), 69 (25), 55 (40).
HR-MS for C21H32O3 requires 332.2343; found
332.2340.
44.8 (C-7), 55.9 (OMe), 56.7 (C-5), 61.7 (C-9), 66.8 (C-
19), 74.0 (C-8), 109.5, 113.5, 114.7, 115.6, 122.9, 126.9,
138.7, 144.6 (2 C), 146.8, 147.3, 147.9, 167.5. UV
MeOH
l
nm (e): 220 (13 200). EI-MS (70 eV) m/z (rel.
max
int.): 482 [M]+ (1), 384 (0.5), 288 (1), 271 (2), 202 (2),
177 (100). HR-MS for C30H42O5 requires 482.3021;
found 482.3025.
3.12. 8a-Acetoxylabda-12,14-dien-19-oic acid (56a)
3.10. 8a-Hydroxylabda-13(16),14-dien-19-yl (Z )-4-
hydroxycinnamate (52)
neat
Gum, TLC (40% EtOAc in hexane) Rf 0.34. IR n
max
1
1
cm : 3500±2500, 1760, 1600, 887. H NMR (CDCl3,
400 MHz): d 0.72 (3 H, s, H-20), 1.01 (3 H, s, H-18),
1.24 (3 H, s, H-17), 1.24±1.62 (8 H, m), 1.63±1.85 (2
H, m), 1.89 (1 H, m), 1.72 (3 H, s, H-16), 1.91 (3 H, s,
OAc), 1.98±2.08 (2 H, m), 2.24 (1 H, m), 4.85 (1 H, t,
J=6.4 Hz, H-12), 4.87 (1 H, dd, J=10.4, 4.4 Hz, H-
15), 5.16 (1 H, dd, J=17.2, 4.4 Hz, H-15), 5.73 (1 H,
dd, J=10.4, 17.2 Hz, H-14). 13C NMR (CDCl3, 75
MHz): d 11.8 (C-16), 15.1 (C-20), 18.7 (C-2), 21.0 (C-
17), 23.5 (C-11), 26.9 (C-6), 28.5 (C-18), 29.0 (OAc),
35.1 (C-3), 36.4 (C-7), 37.5 (C-1, C-4), 40.6 (C-10),
49.8 (C-5), 50.2 (C-9), 51.9 (C-8), 110.3 (C-15), 129.7
(C-12), 135.8 (C-13), 148.6 (C-14), 170.3 (OAc), 181.8
(C-19). EI-MS (70 eV) m/z (rel. int.): 362 [M]+ (78),
302 (100), 287 (34), 257 (18), 175 (65), 121 (70), 81
(80).
Solid, m.p. 206±2088C, [a]2D5 +6.5 (MeOH; c 1.65).
neat
1
TLC (35% EtOAc in hexane) Rf 0.30. IR n
cm :
max
3483, 3300, 1680, 1620, 1590, 1500, 1260, 1175. 1H
NMR (CDCl3, 300 MHz): d 0.79 (3 H, s, H-20), 0.92
(3 H, s, H-18), 0.97±1.08 (3 H, m), 1.12 (3 H, s, H-17),
1.22±1.26 (1 H, m), 1.32±1.45 (4 H, m), 1.53±1.58 (1
H, m), 1.63±1.75 (4 H, m), 1.86 (1 H, dd, J=9.0, 2.7
Hz, H-9), 2.26 (1 H, td, J=10.8, 7.1 Hz, H-12), 2.31
(1 H, td, J=11.8, 7.1 Hz, H-12), 3.92(1 H, d, J=11.1
Hz, H-19), 4.18 (1 H, d, J=11.1 Hz, H-19), 4.99 (2 H,
br s, H-16), 5.04 (1 H, d, J=10.7 Hz, H-15), 5.27(1 H,
d, J=17.6 Hz, H-15), 5.79 (1 H, d, J=12.8 Hz, H-8'),
6.33 (1 H, dd, J=10.7, 17.6 Hz, H-14), 6.76 (2 H, d,
J=8.6 Hz), 6.81 (1 H, d, J=12.8 Hz, H-7'), 7.56 (2 H,
d, J=8.6 Hz). 13C NMR (CDCl3, 75 MHz): d 15.9 (C-
20), 18.0 (C-2), 36.2 (C-3), 36.9 (C-4), 21.0 (C-6), 23.8
(C-17), 24.6 (C-11), 27.4 (C-18), 34.9 (C-12), 38.9 (C-
10), 39.5 (C-1), 44.5 (C-7), 56.6 (C-5), 61.6 (C-9), 66.9
(C-19), 74.5 (C-8), 113.5 (C-15), 115.1 (2 C), 115.7 (C-
16), 116.7, 126.9, 132.2 (2 C), 138.7 (C-14), 143.8,
147.2 (C-13), 157.3, 167.2. EI-MS (70 eV) m/z (rel.
int.): 452 [M]+ (0.5), 434 (1), 288 (2.5), 270 (4), 189
(20), 147 (100). HR-MS for C29H40O4 requires
452.2916; found 452.2920.
3.13. (7R,8R )-9'-(b-Rhamnopyranosyl)-3-methoxy-
3':7,4':8-diepoxyneolignan-4,9-diol pentaacetate (73a)
Gum, [a]2D5 25 (CHCl3; c 4.0). TLC (35% Me2CO
in hexane) Rf 0.3. CD (MeOH, nm): [y]368.2 346,
[y]326.8 +45, [y]306.8 79, [y]272.1 26, [y ]256.4 61,
neat
1
[y]244.4 3, [y]236.0 +31, [y ]218.0 36. IR n
cm :
max
1
2939, 1747, 1607, 1594, 1507, 1452. H NMR (CDCl3,
300 MHz): d 1.17 (3 H, d, J=6.1 Hz, H-60), 1.86 (2
H, m, H-8'), 1.94 (3 H, s), 1.99 (6 H, s, 2 Ac), 2.09 (3
H, s), 2.26 (3 H, s), 2.59 (2 H, t, J=6.8 Hz, H-7'),
3.40 (1 H, m, H-9'), 3.62 (1 H, m, H-9'), 3.82 (1 H, m,
H-50), 3.83 (3 H, s, OMe), 3.94 (1 H, dd, J=4.4, 12
Hz, H-9), 4.17 (1 H, m, H-8), 4.29 (1 H, dd, J=3.3, 12
Hz, H-9), 4.66 (1 H, d, J=1.4 Hz, H-10), 4.87 (1 H, d,
J=7.8 Hz, H-7), 5.01 (1 H, dd, J=9.9, 9.9, Hz, H-40),
5.20 (1 H, dd, J=1.4, 3.5 Hz, H-20), 5.29 (1 H, dd,
J=3.5, 9.9 Hz, H-30), 6.69 (1 H, dd, J=1.9, 8.2 Hz,
H-6'), 6.76 (1 H, d, J=1.9 Hz, H-2'), 6.85 (1 H, d,
J=8.2 Hz, H-5'), 6.92 (1 H, br d, J=8.0 Hz, H-5),
6.95 (1 H, br s, H-2), 7.02 (1 H, d, J=8.0 Hz, H-6).
13C NMR (CDCl3, 75 MHz): d 17.2 (C-60), 20.4 (Ac),
20.5 (Ac), 20.6 (3 Ac), 30.7 (C-8'), 31.3 (C-7'), 55.8
(OMe), 62.7 (C-9), 66.1 (C-50), 67.1 (C-9'), 69.0 (C-30),
69.8 (C-20), 70.9 (C-40), 75.2 (C-8), 76.2 (C-7), 97.3 (C-
10), 110.9 (C-2), 116.7 (C-2'), 116.8 (C-5'), 119.7 (C-5),
121.7 (C-6'), 122.9 (C-6), 134.7 (C-1), 134.9 (C-1'),
140.2 (C-4), 140.9 (C-4'), 142.9 (C-3'), 151.4 (C-3),
3.11. 8a-Hydroxylabda-13(16),14-dien-19-yl (E )-4-
hydroxy-3-methoxycinnamate (53)
Solid, m.p. 110±1128C, [a ]2D5 +6.2 (MeOH; c 0.7).
neat
1
cm :
TLC (35% EtOAc in hexane) Rf 0.32. IR n
max
1
3490, 3310, 1675. H NMR (CDCl3, 300 MHz): d 0.82
(3 H, s, H-20), 1.01 (3 H, s, H-18), 0.97±1.08 (3 H, m),
1.13 (3 H, s, H-17), 1.22±1.26 (1 H, m), 1.35±1.50 (4
H, m), 1.53±1.65 (2 H, m), 1.70±1.92 (4 H, m), 2.20±
2.42 (2 H, m), 3.90 (3 H, s, OMe), 3.98 (1 H, d, J=11
Hz, H-19), 4.27 (1 H, d, J=11 Hz, H-19), 4.99 (2 H,
br s, H-16), 5.04 (1 H, d, J=10.7 Hz, H-15), 5.27 (1
H, d, J=17.6 Hz, H-15), 6.25 (1 H, d, J=15.9 Hz),
6.33 (1 H, dd, J=10.7, 17.6 Hz, H-14), 6.89 (1 H, d,
J=8.1 Hz), 7.00 (1 H, d, J=1.7 Hz), 7.05 (1 H, dd,
J=1.7, 8.1 Hz), 7.56 (1 H, d, J=15.9 Hz, H-7'). 13C
NMR (CDCl3, 75 MHz): d 15.9 (C-20), 18.0 (C-2),
20.8 (C-6), 23.7 (C-17), 24.7 (C-11), 27.5 (C-18), 35.0
(C-12), 36.4 (C-3), 37.2 (C-4), 38.9 (C-10), 39.6 (C-1),