3
34
S. Schulz et al. / Phytochemistry 54 (2000) 325±336
3
.3.8. 4,6-Pentacosanedione (6f)
1
3.3.11. 1-Phenyl-1,3-hexadecanedione (7a)
1
H-NMR (400 MHz, CDCl ): d 0:88 (3H, t, J =
H-NMR (400 MHz, CDCl ): d 0:88 (3H, t, J =
3
3
7
1
.1 Hz, CH ), 0.95 (3H, t, J = 7.1 Hz, CH ), 1.21±
3
.32 (30H, m, H-9±H-24), 1.53±1.69 (4H, m, H-2 and
6.9 Hz, H-16), 1.20±1.42 (20H, m, H-6±H-15), 1.64±
1.72 (2H, m, H-5), 2.42 (2H, t, J = 7.6 Hz, H-4), 2.57
(2H, t, J = 7.6 Hz, H-4 enol), 4.08 (2H, s, H-2), 6.18
(1H, s, H-2 enol), 7.4±7.9 (5H, m, ar), 15.54 (1H, br s,
3
H-8), 2.25 (2H, t, J = 7.6 Hz, H-7), 2.27 (2H, t, J =
.6 Hz, H-3), 2.49 (2H, t, J = 7.6 Hz, H-7 enol), 2.50
2H, t, J = 7.6 Hz, H-3 enol), 3.55 (2H, s, H-5), 5.48
7
13
(
(
(
OH enol). C-NMR (100.6 MHz, CDCl ), only the
3
13
1H, s, H-5 enol), 15.5 (1H, br s, OH enol). C-NMR
100.6 MHz, CDCl ): d 13:7 (q, C-1), 14.1 (q, C-25),
enol form could be observed: d 14:1 (q, C-16), 22.7
(t, C-15), 25.9 (t, C-5), 29.3±29.7 (t, C-6±C-13), 31.9 (t,
C-14), 39.3 (t, C-4), 96.1 (d, C-2), 127.0 (2d, ar), 128.6
(2d, ar), 132.2 (d, ar), 135.1 (s, ar), 183.5 (s, C-1),
3
16.8 (t, C-2), 19.1 (t, C-2 enol), 22.7 (t, C-24), 23.4 (t,
C-8), 25.7 (t, C-8 enol), 28.6 (t ), 29.0±29.7 (t, C-9±C-
+
2
2), 31.9 (t, C-23), 38.5 (t, C-7 enol), 40.2 (t, C-3 enol),
3.8 (t, C-7), 45.6 (t, C-3), 57.2 (t, C-5), 99.1 (d, C-5
197.0 (s, C-3). EIMS 70 eV (rel. int.): 330 [M] (0.4),
+
312 [M±H O] (0.8), 175 (3), 162 (29), 147 (22), 120
(11), 105 (100), 77 (24).
4
enol), 194.1 (s, C-4 enol), 194.8 (s, C-6 enol), 204.1 (s,
2
+
C-4), 204.4 (s, C-6). EIMS 70 eV (rel. int.): 380 [M]
(
+
0.8), 362 [M±H O] (3), 337 (8), 295 (2), 141 (19),
3.3.12. 1-Phenyl-1,3-octadecanedione (7b)
1
2
128 (75), 113 (70), 100 (41), 85 (42), 71 (100), 43 (67).
H-NMR (400 MHz, CDCl ): d 0:88 (3H, t, J =
3
6
.9 Hz, H-18), 1.20±1.34 (24H, m, H-6±H-17), 1.64±
3
.3.9. 6,8-Pentacosanedione (6g)
1
1.72 (2H, m, H-5), 2.42 (2H, t, J = 7.6 Hz, H-4), 2.57
(2H, t, J = 7.6 Hz, H-4), 4.10 (2H, s, H-2), 6.16 (2H,
s, H-2 enol), 7.4±7.9 (5H, m, ar), 15.54 (1H, br s, OH
H-NMR (400 MHz, CDCl ): d 0:88 (3H, t, J =
3
7
1
.1 Hz, CH ), 0.90 (3H, t, J = 7.1 Hz, CH ), 1.21±
3
.30 (32H, m, H-2 and H-3, H-11±H-24), 1.52±1.67
3
enol). 13 C-NMR (100.6 MHz, CDCl ), only the enol
3
(
4H, m, H-4 and H-10), 2.26 (4H, 2t, J = 7.6 Hz, H-5
form could be observed: d 14:1 (q, C-18), 22.7 (t, C-
17), 25.9 (t, C-5 enol), 29.3±29.7 (t, C-6±C-15), 31.9 (t,
C-16), 39.3 (t, C-4 enol), 96.1 (d, C-2 enol), 127.0 (2d,
ar), 128.6 (2d, ar), 132.2 (d, ar), 135.1 (s, ar), 183.5 (s,
C-1 enol), 197.0 (s, C-3). EIMS 70 eV (rel. int.): 358
and H-9), 2.49 (4H, 2t, J = 7.6 Hz, H-5 and H-9
enol), 3.54 (2H, s, H-7), 5.49 (1H, s, H-7 enol), 15.53
13
(
1H, br s, OH enol). C-NMR (100.6 MHz, CDCl3):
d 13:9 (q, C-1), 14.1 (q, C-25), 22.4 (t, C-2), 22.7 (t,
+
+
C-24), 23.1 (t, C-4), 23.4 (t, C-10), 25.4 (t, C-4 enol),
[M] (1), 340 [M±H O] (3), 175 (4), 162 (34), 147
2
2
3
5.7 (t, C-10 enol), 29.0±29.7 (t, C-11-C22), 31.3 (t, C-
), 31.4 (t, C-3 enol), 31.9 (t, C-23), 38.4 (2t ), C-5 and
(27), 120 (10), 105 (100), 77 (21).
C-9 enol), 43.8 (2t, C-5 and C-9), 57.2 (t, C-7), 99.0 (d,
C-7 enol), 194.5 (2s, C-6 and C-8 enol), 204.3 (2s, C-6
3.3.13. 14,16-dioxopentacosanoic acid (15a)
This acid was synthesized according to the general
procedure by condensation of methyl 3-oxododecano-
ate with the acid chloride of monomethyl tetradecan-
dioate. The methyl ester group was partially saponi®ed
during decarbmethoxylation, leading to a mixture of
the free acid and the methyl ester, which was separated
+
and C-8). EIMS 70 eV (rel. int.): 380 [M] (0.5), 362
+
[
M±H O] (0.7), 309 (2), 267 (1), 169 (5), 156 (16),
2
1
3
2
41 (27), 113 (13), 100 (78), 99 (100), 71 (46), 43 (49).
.3.10. 10,12-Nonacosanedione (6h)
1
1
H-NMR (400 MHz, CDCl ): d = 0.88±0.93 (6H,
by column chromatography on silica. H-NMR (400
3
t, J = 7 Hz, H-1 and H-29), 1.2±1.31 (40H, m, H-2±
MHz, CDCl ): d 0:88 (3H, t, J = 7 Hz, H-25), 1.2±
3
H-7, H-15±H-28), 1.52±1.64 (4H, m, H-8 and H-14),
1.31 (28H, m, H-4±H-11, H-19±H-24), 1.52±1.68 (6H,
m, H-3, H-12, and H-18), 2.27 (4H, t, J = 7.6 Hz,
12.H-13 and H-17 enol), 2.34 (2H, t, J = 7.6 Hz, H-
2), 2.49 (4H, t, J = 7.6 Hz, H-13 and H-17), 3.55 (2H,
s, H-15), 5.47 (1H, s, H-15 enol), 10.0 (1H, br s,
2
2
.24±2.29 (4H, 2t, J = 7.6 Hz, H-9 and H-13 enol),
.49 (4H, 2t, J = 7.6 Hz, H-9 and H-13), 3.55 (2H, s,
H-11), 5.47 (1H, s, H-11 enol), 15.54 (1H, br s, OH
1
3
enol). C-NMR (100.6 MHz, CDCl ): d 14:1 (2q,
3
13
C-1 and C-29), 22.7 (2t, C-2 and C-28), 23.5 (2t, C-8
and C-14), 25.8 (2t, C-8 and C-14 enol), 28.9±29.8 (t,
C-4±C-7 and C-15ÐC-26), 31.9 (2t, C-3 and C-27),
COOH), 15.54 (1H, br s, OH enol). C-NMR (100.6
MHz, CDCl ): d 14:1 (q, C-25), 22.6 (t, C-24), 23.4
3
(2t, C-12 and C-18), 24.7 (t, C-3), 25.7 (t, C-12 and C-
18 enol), 29.0±29.5 (t, C-4±C-11 and C-19±C-22), 31.8
(t, C-23), 33.9 (t, C-2), 38.4 (2t, C-13 and C-17 enol),
43.8 (2t, C-13 and C-17), 57.2 (t, C-15), 99.0 (d, C-15
enol), 179.4 (s, C-1), 194.6 (2s, C-14 and C-16 enol),
204.5 (2s, C-14 and C-16). EIMS 70 eV (rel. int.) of
3
8.4 (2t ), C-9 and C-13 enol), 43.8 (2t, C-9 and C-13),
7.3 (t, C-11), 99.0 (d, C-11 enol), 194.5 (2s, C-10 and
5
C-12 enol), 204.3 (2s, C-10 and C-12). EIMS 70 eV
+
+
(
rel. int.): 436 [M] (3), 418 [M±H O] (9), 337 (4),
2
3
2
1
1
4
09 (12), 306 (10), 281 (8), 278 (7), 267 (10), 252 (4),
48 (9), 239 (9), 225 (17), 222 (6), 212 (8), 197 (22),
94 (10), 183 (16), 164 (7), 155 (42), 142 (9), 138 (19),
24 (10), 113 (19), 100 (100), 97 (21), 85 (33), 71 (46),
3 (42).
+
methyl ester: 424 [M] (2), 406 (8), 351 (6), 312 (6),
297 (9), 294 (10), 265 (20), 255 (42), 239 (41), 225 (22),
212 (11), 197 (66), 155 (60), 100 (100), 87 (11), 85 (39),
84 (15), 83 (27), 74 (18), 71 (45), 69 (51), 59 (10).