1
8
MALYKHINA et al.
–
1
in size with a sorbent layer 2 mm thick; compounds 5
IR (KBr, ν, cm ): 766, 945, 971, 1036, 1081, 1126,
i
and 8 were eluted with a Pr OH–Et O mixture (4 : 96 v/v), 1179, 1271, 1367, 1450, 1637, 1713 (C=O), 2820,
2
and compound 11 was eluted with a hexane–Et O mix-
2
2928, 3511 (OH). UV (EtOH, λmax, nm (logε )): 225
4.31), 269 (4.15).
ture (4 : 1 v/v).
(
Analytical TLC was accomplished on 7.5 × 7.5 cm
2
Ethyl
3-{2-[(7,8-methylenedioxy-20-ethyl-
glass plates with a sorbent layer (0.04 g/cm ), neutral
1
a,6b,14a,16b-tetramethoxy-4-aconitylmethyle-
Al O , 5/40 µm (Chemapol, Czech Republic), contain-
2
3
ing 1 wt % of K-35 fluorescent indicator (TU 6-09-458- neoxy)carbonyl]phenyl}-2E-propenoate (8). Yield,
2
0
7
6, Russia) and 1% Na CO prepared as described previ- 0.559 g (82%). Amorphous powder, [α] = +15.8 (c 2,
2 3
ously [8]. Alkaloid spots were detected on a dried plate CHCl ). Found by mass spectrometry (m/z): 650.3310
3
in UV light and also by development with iodine vapors.
(
fragment ion). C H NO – CH O = C H NO . Cal-
38 51 10 3 37 48 9
1
N-Deacetyllappaconitine 3 and anthranoylelatidine 6 culated: M = 650.3329. H NMR (δ, ppm, J, Hz): 1.03
used had the physicochemical and spectral characteris- (t, 3H, NCH CH , J = 7); 1.30 (t, 3H, OCH CH , J = 7);
.23 (s, 3H), 3.30 (s, 6H), and 3.39 (s, 3H) (1-, 6-, 14-,
and 16-OCH ); 4.23 (q, 2H, OCH CH , J = 7); 5.03 (s,
pounds 5, 8, and 11. Ethyl acrylate (0.200 g, 2 mmol) 2H, OCH O); 6.27 (d, 1H, 2"-H, J = 16); 7.36–7.61 (m,
and Pd(dba) (0.029 g, 0.05 mmol) were added to a 3H, 4'-, 5'-, and 6'-H); 7.90 (dd, 1H, 3'-H, J = 7.5 and
2
3
2
3
tics reported in [5] and [6], respectively.
3
General procedure for the synthesis of com-
3
2
3
2
2
solution of 1 mmol of compound 3, 6, or 9 in 3 mL of
glacial acetic acid, the mixture was heated on a water
bath to 50°C, and a solution of 0.113 g (1.10 mmol) of
t-BuONO in 1.0 mL of glacial acetic acid was added
dropwise under stirring. The mixture was kept for
13
J = 1.5); 8.36 (d, 1H, 3"-H, J = 16). C NMR (δ, ppm,
J, Hz): 83.3 (C-1), 26.3 (C-2), 31.7 (C-3), 36.9 (C-4),
5
2.3 (C-5), 89.2 (C-6), 92.0 (C-7), 83.2 (C-8), 39.8
(
C-9), 48.2 (C-10), 49.9 (C-11), 27.8 (C-12), 38.6
C-13), 81.5 (C-14), 34.7 (C-15), 81.1 (C-16), 63.9
C-17), 70.2 (C-18), 52.8 (C-19), 50.2 (C-21), 13.7
C-22), 55.0 (1-OCH ), 57.6 (6-OCH ), 58.7 (14-OCH ),
(
3
0 min at 50°C and then cooled to 20°C. To neutralize
(
acetic acid, the resulting solution was carefully poured
(
3
3
3
with stirring into 15 mL of saturated Na CO solution.
2
3
5
1
1
6.0 (16-OCH ), 136.4 (C-1'), 130.6 (C-2'), 128.8 (C-3'),
29.7 (C-4'), 132.3 (C-5'), 128.0 (C-6'), 121.2 (C-2"),
43.6 (C-3"), 14.2 (OCH CH ), 60.4 (OCH CH ), 93.4
3
The mixture was extracted with chloroform (4 × 5 mL).
The chloroform was removed from the extract in vac-
uum, and the residue was dried at 50°C (3 torr), dis-
2
3
2
3
1
1
solved in 3 mL of chloroform, and subjected to prepar- (OCH O), 166.2 (COOC-4), 166.6 (COOEt).
2
ative TLC on Al O containing a K-35 fluorescent indi-
2
3
–
1
cator. UV-absorbing sorbent layers with R 0.64, 0.78,
IR (KBr, ν, cm ): 755, 964, 1047, 1089, 1123,
and 0.19, corresponding to target compounds 5, 8, and 1180, 1262, 1314, 1368, 1450, 1597, 1638, 1716
f
1
1, respectively, were collected, and the compounds
(
(
C=O), 2821, 2933. UV (EtOH, λmax, nm (logε )): 226
4.10), 270 (3.88).
were eluted with methanol.
Ethyl 3-{2-[(8,9-dihydroxy-1a,14a,16b-trimethoxy-
Ethyl 3-[(2-methoxycarbonyl)phenyl]-2E-prope-
noate (11). After molecular distillation (3 torr, bath
temperature 160°C), 0.199 g (85%) of compound 11
2
0-ethyl-4-aconityloxy)carbonyl]phenyl}-2E-prope-
noate (5). Yield, 0.507 g (81%). Amorphous powder,
20
[
α] = +18.4 (c 5, CHCl ). Found by mass spectrome-
3
2
0
try (m/z): 625.3251. C H NO . Calculated: M = was obtained as a yellowish liquid, n 1.5545. Found
25.3268. H NMR (δ, ppm, J, Hz): 1.09 (t, 3H, by mass spectrometry (m/z): 234.0892. C H O . Cal-
3
5
47
9
D
1
6
13 14 4
NCH CH , J = 7); 1.31 (t, 3H, OCH CH , J = 7); 3.27,
1
2
3
2
3
culated: M = 234.0892. H NMR (δ, ppm, J, Hz): 1.26
t, 3H, OCH CH , J = 7); 3.84 (s, 3H, OMe); 4.20 (q,
H, OCH CH , J = 7); 6.23 (d, 1H, 2"-H, J = 16); 7.33
2 3
and 7.44 (both td, 1H each, J = 7.5 and J = 1.5, 5'- and
'-H, respectively); 7.51 and 7.93 (both dd, 1H each,
J = 7.5 and J = 1.5, 6'- and 3'-H, respectively); 8.41 (d, 1H,
3
4
1
3
.28, and 3.38 (all s, 3H each, 1-, 14-, and 16-OMe);
(
3
2 3
.25 (q, 3H, OCH CH , J = 7); 6.24 (d, 1H, 2"-H, J =
2
3
6); 7.32–7.53 (m, 3H, 4'-, 5'-, and 6'-H); 7.84 (dd, 1H,
'-H, J = 7.5 and J = 1.5); 8.33 (d, 1H, 3"-H, J = 16).
C NMR (δ, ppm, J, Hz): 84.2 (C-1), 26.7 (C-2), 31.8
C-3), 84.3 (C-4), 49.8 (C-5), 24.0 (C-6), 47.6 (C-7),
4
1
3
(
13
3
1
1
"-H, J = 16). C NMR (δ, ppm, J, Hz): 136.2 (C-1'),
30.6 (C-2'), 129.1 (C-3'), 129.7 (C-4'), 132.1 (C-5'),
27.7 (C-6'), 121.0 (C-2"), 143.4 (C-3"), 52.1
1
7
5.5 (C-8), 78.4 (C-9), 48.3 (C-10), 50.9 (C-11), 26.2
(
(
(
(
C-12), 36.3 (C-13), 90.1 (C-14), 44.6 (C-15), 82.8
C-16), 61.4 (C-17), 55.4 (C-19), 48.8 (C-21), 13.4
C-22), 56.3 (1-OCH ), 57.7 (14-OCH ), 55.9 (COOCH ), 14.1 (OCH CH ), 60.4 (OCH CH), 166.4
3
3
3 2 3 2
1
16-OCH ), 136.1 (C-1'), 131.1 (C-2'), 129.1 (C-3'),
3
(COOMe), 167.0 (COOEt).
1
30.5 (C-4'), 131.8 (C-5'), 127.8 (C-6'), 120.7 (C-2"),
–
1
1
43.9 (C-3"), 14.2 (OCH CH ), 60.3 (OCH CH ),
IR (KBr, ν, cm ): 766, 978, 1039, 1079, 1132,
1180, 1263, 1315, 1367, 1435, 1484, 1572, 1597, 1637
C=O), 1719. UV (EtOH, λmax, nm (logε )): 225 (4.30),
2
3
2
3
1
1
1
65.6 (COOC-4), 166.4 (COOEt).
(
1
The assignments may be swapped.
271 (4.17).
DOKLADY CHEMISTRY Vol. 394 Part 1 2004