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18
11,12-Seco-11,12-epoxi-11,12-dioxo-8,13-abietadien-20,7β-olide(3):
Mp: 226-228 °C; UV (EtOH):
207, 258 nm. IR (CHCl3): 3440, 2962, 1744, 1725, 1290,
1112, 1046, 757 cm-1. 1H
NMR (300 MHz, CDCl3): δ = 0.86 (3 H,
s, Me-19), 0.90 (3 H, s, Me-18), 1.19 (3 H, d, J = 7.0
Hz, Me-16), 1.20 (3 H, d, J = 7.0
Hz, Me-17), 1.28 (1 H, dd, J
1
= 3.2
Hz, J
2
= 13.1 Hz,
H-3), 1.60 (3 H, overlapping signal, H-2, H-3′, H-5), 1.87
(3 H, overlapping signal, H-1α, H-2′, H-6), 2.15 (1
H, m, H-6′), 2.68 (1 H, bd, J = 13.3
Hz, H-1β), 2.97 (1 H, hept, J = 7.0
Hz, H-15), 5.15 (1 H, dd, J
1
= 1.5
Hz, J
2
= 4.0 Hz,
H-7), 6.37 (1 H, s, H-14). 13C NMR
(75 MHz, CDCl3): δ = 18.1 (t, C-2),
19.2 (q, C-18), 21.0 (q, C-16), 21.4 (q, C-17), 25.7 (t, C-6), 31.8
(q, C-19), 33.0 (d, C-15), 34.5 (s, C-4), 40.3 (t, C-3), 44.8 (d,
C-5), 47.9 (s, C-10), 76.6 (d, C-7), 124.0 (d, C-14), 134.6 (s,
C-9), 144.6 (s, C-8), 147.4 (s, C-13), 155.6 (s, C-11), 160.7 (s,
C-12), 172.7 (s, C-20). MS-FAB: m/z (%) = 345
(14) [M+], 317 (6), 299 (20),
289 (11), 139 (13), 133 (41), 89 (24), 77 (11). HRMS-FAB: m/z = 345.1690 (calcd
for C20H25O5: 345.1702).
19 A. L. Spek, PLATON. A multipurpose
crystallographic tool, Utrecht University, Utrecht, Netherlands(2001). Crystallographic Data for (3): Colourless
irregular shaped crystals, C20H48O5,
Mw = 344.4, monoclinic system,
space group P21, Z = 2, a = 6.530(2) Å, b = 11.034(3) Å, c = 12.705(3) Å, β = 103.76(2)º,
V = 889.1(4) Å3,
Dc = 1.29 gcm-3,
F(000) = 368, µ (MoKα) = 0.09
mm-1. The intensity data of all unique
reflections within the θ range 2.5-26.3º were
collected at r.t. on an Enraf-Nonius CAD4 diffractometer, using
MoKα radiation and graphite monochromador. Three standard
reflections monitored every 2 h of X-ray exposure showed no significant
decay of the intensity. A total of 1260 unique reflections were recorded
of which 592 were considered as observed under F0>4σ (F0).
The intensities were corrected for Lorentz and polarization factors,
but no absorption correction was made. The structure was solved
by direct methods using SHELXS86, refinement was performed with
SHELXL93, using full-matrix least squares with anisotropic thermal parameters
for all the non-H atoms. The H-atoms were placed in idealized positions
and added in the last steps of the refinement as a fixed isotropic
contribution. The refinement converged at R1 = 6.06% and wR2 = 18.23%,
with a goodness of fit for F
[2]
of
1.01, the largest peak on the final difference map was 0.22 e/Å
[3]
. Crystallographic data
of(3), including atomic coordinates, have
been deposited with the Cambridge Crystallographic Data Centre as
supplementary publication nº CCDC 188402. Copies of the
data can be obtained free of charge on applications to the Director, CCDC,
12 Union Road, Cambridge CB2 1EZ, U.K. (Fax: +44(1223)336033,
e-mail: deposit@ccdc.cam.ac.uk).
20
11,12-Seco-8,13-abietadien-20,7β-lacton-11,12-dioic Acid
Dimethyl Ester (4): UV (EtOH): 246 nm. IR (CHCl3): 2924,
1754, 1722, 1242, 1091, 1031 cm-1. 1H
NMR (300 MHz, CDCl3): δ = 0.83 (3 H,
s, Me-19), 0.88 (3 H, s, Me-18), 1.08 (3 H, d, J = 7.0
Hz, Me-16), 1.09 (3 H, d, J = 7.0
Hz, Me-17), 2.47 (1 H, bd, J = 14.2
Hz, H-1β), 2.74 (1 H, hept, J = 6.8
Hz, H-15), 3.75 (3 H, s, -OCH3), 3.77 (3 H,
s,
-OCH3), 5.00 (1 H, s, H-7), 6.22
(1 H, s, H-14). 13C NMR (75 MHz, CDCl3): δ = 18.3
(t, C-2), 19.2 (q, C-18), 21.4 (q, C-16), 21.5 (q, C-17), 26.9 (t,
C-1), 28.0 (t, C-6), 31.8 (q, C-19), 32.6 (d, C-15), 34.2 (s, C-4),
40.5 (t, C-3), 45.4 (d, C-5), 47.2 (s, C-10), 52.0 (t, 2 × -OCH3),
75.9 (d, C-7), 123.8 (d, C-14), 136.8 (s, C-9), 142.0 (s, C-8),
144.0 (s, C-13), 165.1 (s, C-11), 168.8 (s, C-12), 174.2 (s, C-20).
MS (EI): m/z (%) = 390
(11) [M+], 347 (24), 331 (100),
299 (29), 255 (44), 211 (10), 69 (15). HRMS (EI): m/z = 390.2041
(calcd for C22H30O6: 390.2042).
21
11,12-
O
-Didehydrocarnosol
(5): UV (EtOH): 207 nm. IR (CHCl3): 2960, 1750,
1665, 1462, 1109, 1029, 755 cm-1. 1H NMR
(300 MHz, CDCl3): δ = 0.87 (3 H, s,
Me-19), 0.89 (3 H, s, Me-18), 1.12 (6 H, d, J = 7.0
Hz, Me-16, Me-17), 1.23 (1 H, m, H-3), 1.53 (1 H, bd, J = 13.3 Hz,
H-3′), 1.65 (2 H, overlapping signal, H-2, H-5), 1.87 (1
H, dt, H-2′), 1.97 (1 H, m, H-6), 2.20 (1 H, m, H-6′),
2.30 (1 H, td, J
1
= 4.6 Hz, J
2
= 14.0 Hz,
H-1α), 2.68 (1 H, bd, J = 14.4
Hz, H-1β), 2.97 (1 H, hept, J = 7.0
Hz, H-15), 5.19, 5.20 (1 H, dd, J
1
= 1.4 Hz, J
2
= 4.0 Hz,
H-7), 6.67 (1 H, s, H-14). 13C NMR
(75 MHz, CDCl3): δ = 18.2 (t, C-2),
19.3 (q, C-18), 21.3 (q, C-16), 21.3 (q, C-17), 27.0 (t, C-1), 27.8
(t, C-6), 27.8 (d, C-15), 32.0 (q, C-19), 34.4 (s, C-4) 40.5 (t,
C-3), 44.8 (d, C-5), 48.7 (s, C-10), 76.4 (d, C-7), 129.6 (d, C-14),
135.6 (s, C-9), 151.1 (s, C-13), 173.3 (s, C-20), 176.2 (s, C-11),
179.2 (s, C-12). MS (EI): m/z (%) = 328
(5) [M+], 284 (43), 215 (100),
204 (17), 165 (14), 141 (14), 55(20). HRMS (EI): m/z = 328.1696
(calcd for C20H24O4: 328.1675).
