Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807045126/is2209sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807045126/is2209Isup2.hkl |
CCDC reference: 663802
The dried herb of Lobelia chinensis (18 kg) was extracted with refluxing 95% ethanol (3 × 20 L), after removal of the solvent under reduced pressure, the extract was suspended in water and then partitioned with light petroleum, EtOAc and n-BuOH successively. The EtOAc-soluble part (150 g) was chromatographed on a silica gel column, using a gradient mixture of light petroleum-EtOAc as eluent. The fraction eluted with petrol-EtOAc (9: 2, v/v) was further purified by sephadex LH-20 column chromatography using CHCl3—CH3OH (1:1 v/v) as eluent, to yield the title compound (10 mg). IR (KBr) cm-1: 3450, 3310, 1740, 1698, 1459, 1375, 1248, 1100, 1053. 1H NMR (500 MHz, DMSO-d6) δ: 2.47 (1H, m, H-1a), 2.32 (1H, m, H-1 b), 2.87 (1H, m, H-2a), 2.44 (1H, m, H-2 b), 2.25 (1H, dd, J = 11.0, 5.1 Hz, H-5),1.41 (1H, m, H-6a), 1.98 (1H, m, H-7a), 1.26 (2H, m, H-6 b, 7 b), 1.95 (1H, d, J = 11.0 Hz, H-9), 4.0 4 (1H, m, H-11), 2.91 (1H, dd, J = 13.0, 5.8 Hz, H-12a), 2.39 (1H, dd, J = 13.0, 12.8 Hz, H-12b), 2.28 (1H, dd, J = 13.8, 6.5 Hz, H-15a), 1.40 (1H, dd, J = 13.8, 5.5 Hz, H-15b), 4.58 (1H, dd, J=9.1, 7.1 Hz, H-16), 1.01 (3H, s, H-18), 1.38 (3H, s, H-19), 2.84 (1H, m, H-20), 1.14 (3H, d, J = 7.1 Hz, H-21), 1.88 (1H, m, H-22a), 1.51 (1H, m, H-22b), 4.48 (1H, m, H-23), 5.21 (1H, d, J = 2.6 Hz, H-24), 1.56 (3H, s, H-26), 1.60 (3H, s, H-27), 1.11 (3H, s, H-28), 1.18 (3H, s, H-29), 1.19 (3H, s, H-30), 2.10 (3H, s, 24-OAc); 13C NMR (125 MHz, in DMSO-d6) δ: 30.9 (C-1), 34.4 (C-2), 219.1 (C-3), 47.1 (C-4), 48.4 (C-5), 20.2 (C-6), 34.0 (C-7), 40.9 (C-8), 49.8 (C-9), 37.5 (C-10), 69.8 (C-11), 34.2 (C-12), 137.6 (C-13), 55.5 (C-14), 39.8 (C-15), 80.9 (C-16), 133.1 (C-17), 23.8 (C-18), 25.6 (C-19), 26.9 (C-20), 18.4 (C-21), 35.6 (C-22), 72.0 (C-23), 79.9 (C-24), 72.3 (C-25), 28.4 (C-26), 27.3 (C-27), 29.4 (C-28), 20.9 (C-29), 24.4 (C-30), 171.0 (24-OAc). Crystals suitable for X-ray structure analysis were obtained by slow evaporation of a methanol solution at room temperature.
H atoms were positioned geometrically, with O—H = 0.82 and C—H = 0.98 (methine H), 0.97 (methylene H) or 0.96 Å (methyl H), and constrained to ride on their parent atoms, with Uiso(H) = xUeq(C,O), where x = 1.2 for methine and methylene H and x = 1.5 for all other H. The acetyl group was restrained to keep their atomic displacement parameters close to those of the spatially adjacent atoms. In the absence of significant anomalous scattering effects, Friedel pairs were merged, and the absolute configuration is assigned arbitrarily.
The title compound, C32H50O6, a known protostane-type triterpene, named alisol F 24-acetate [systematic name: 16β, 23β-epoxy-11β, 25-dihydroxy-24(R)-acetoxy-protost-13 (17)-en-3-one], was isolated from the Chinese herbal medicine Lobelia chinensis Lour firstly obtained by Peng & Lou (2001) and found to possess activity for inhibiting formation of urinary oxalate calcium calculi. Its structure was elucidated on the basis of spectroscopic methods such as 1H NMR, 13C NMR, two-dimensional NMR and chemical correlation (Peng & Lou, 2001; Zhou et al., 2005).
The molecule contains a five-fused ring system including four six-membered rings, A(C1—C5/C10), B(C5—C10), C(C8—C14) and E(O3/C16—C20) and a five-membered ring D(C13—C17) (Fig. 1). The junctions of the three fused six-membered rings A, B and C, two of which, A and B, adopt slightly distorted boat conformations and the C exhibits a perfect chair conformation, are all trans. The five-membered ring D is almost planar. Ring E adopts a chair conformation. A chain running along the b axis was formed via the classic intermolecular O—H···O hydrogen bonds as shown in Fig. 2.
For related literature, see: Peng & Lou (2001); Zhou et al. (2005).
Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL (Bruker, 2001).
C32H50O6 | F(000) = 580 |
Mr = 530.72 | Dx = 1.201 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 1829 reflections |
a = 6.525 (4) Å | θ = 2.5–20.9° |
b = 15.885 (10) Å | µ = 0.08 mm−1 |
c = 14.401 (9) Å | T = 298 K |
β = 100.475 (10)° | Prism, colourless |
V = 1467.8 (16) Å3 | 0.50 × 0.47 × 0.40 mm |
Z = 2 |
Bruker SMART 1000 CCD area-detector diffractometer | 2697 independent reflections |
Radiation source: fine-focus sealed tube | 1811 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.072 |
φ and ω scans | θmax = 25.0°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | h = −7→7 |
Tmin = 0.959, Tmax = 0.968 | k = −16→18 |
7306 measured reflections | l = −17→16 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.089 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.236 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.1619P)2] where P = (Fo2 + 2Fc2)/3 |
2697 reflections | (Δ/σ)max < 0.001 |
343 parameters | Δρmax = 0.48 e Å−3 |
37 restraints | Δρmin = −0.26 e Å−3 |
C32H50O6 | V = 1467.8 (16) Å3 |
Mr = 530.72 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 6.525 (4) Å | µ = 0.08 mm−1 |
b = 15.885 (10) Å | T = 298 K |
c = 14.401 (9) Å | 0.50 × 0.47 × 0.40 mm |
β = 100.475 (10)° |
Bruker SMART 1000 CCD area-detector diffractometer | 2697 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | 1811 reflections with I > 2σ(I) |
Tmin = 0.959, Tmax = 0.968 | Rint = 0.072 |
7306 measured reflections |
R[F2 > 2σ(F2)] = 0.089 | 37 restraints |
wR(F2) = 0.236 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.48 e Å−3 |
2697 reflections | Δρmin = −0.26 e Å−3 |
343 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.5063 (9) | 1.1516 (4) | 0.2720 (4) | 0.0555 (15) | |
O2 | 0.2109 (9) | 0.8135 (3) | 0.4045 (3) | 0.0460 (14) | |
H2 | 0.2120 | 0.7918 | 0.4562 | 0.069* | |
O3 | 0.7078 (9) | 0.4694 (3) | 0.2211 (3) | 0.0371 (13) | |
O4 | 1.0287 (8) | 0.3572 (3) | 0.2271 (4) | 0.0428 (13) | |
O5 | 0.8746 (14) | 0.2837 (6) | 0.1019 (4) | 0.085 (2) | |
O6 | 0.7817 (9) | 0.2528 (3) | 0.4048 (4) | 0.0444 (13) | |
H6 | 0.6889 | 0.2314 | 0.3659 | 0.067* | |
C1 | 0.5384 (12) | 0.9359 (5) | 0.3534 (5) | 0.0383 (18) | |
H1A | 0.4649 | 0.9368 | 0.4062 | 0.046* | |
H1B | 0.6501 | 0.8949 | 0.3675 | 0.046* | |
C2 | 0.6326 (15) | 1.0232 (5) | 0.3431 (6) | 0.052 (2) | |
H2A | 0.6314 | 1.0541 | 0.4010 | 0.062* | |
H2B | 0.7773 | 1.0155 | 0.3374 | 0.062* | |
C3 | 0.5303 (11) | 1.0768 (5) | 0.2622 (5) | 0.0349 (17) | |
C4 | 0.4809 (12) | 1.0350 (5) | 0.1647 (5) | 0.0383 (18) | |
C5 | 0.4810 (11) | 0.9379 (5) | 0.1782 (5) | 0.0331 (16) | |
H5 | 0.6285 | 0.9222 | 0.1935 | 0.040* | |
C6 | 0.3929 (13) | 0.8873 (5) | 0.0909 (5) | 0.0389 (18) | |
H6A | 0.4321 | 0.9132 | 0.0357 | 0.047* | |
H6B | 0.2420 | 0.8864 | 0.0822 | 0.047* | |
C7 | 0.4770 (14) | 0.7981 (5) | 0.1020 (5) | 0.0410 (19) | |
H7A | 0.6161 | 0.7979 | 0.0871 | 0.049* | |
H7B | 0.3903 | 0.7627 | 0.0559 | 0.049* | |
C8 | 0.4879 (10) | 0.7578 (5) | 0.2008 (5) | 0.0314 (15) | |
C9 | 0.3477 (11) | 0.8093 (5) | 0.2591 (4) | 0.0301 (16) | |
H9 | 0.2051 | 0.8026 | 0.2242 | 0.036* | |
C10 | 0.3867 (11) | 0.9081 (5) | 0.2639 (5) | 0.0317 (16) | |
C11 | 0.3472 (12) | 0.7679 (5) | 0.3552 (5) | 0.0331 (16) | |
H11 | 0.4887 | 0.7704 | 0.3923 | 0.040* | |
C12 | 0.2799 (12) | 0.6763 (5) | 0.3456 (5) | 0.0385 (18) | |
H12A | 0.2947 | 0.6509 | 0.4077 | 0.046* | |
H12B | 0.1343 | 0.6730 | 0.3158 | 0.046* | |
C13 | 0.4099 (12) | 0.6295 (4) | 0.2876 (5) | 0.0335 (17) | |
C14 | 0.4086 (11) | 0.6647 (5) | 0.1904 (5) | 0.0327 (16) | |
C15 | 0.5620 (13) | 0.6021 (5) | 0.1531 (5) | 0.0394 (18) | |
H15A | 0.4849 | 0.5622 | 0.1090 | 0.047* | |
H15B | 0.6580 | 0.6326 | 0.1214 | 0.047* | |
C16 | 0.6790 (12) | 0.5568 (5) | 0.2389 (5) | 0.0351 (17) | |
H16 | 0.8152 | 0.5836 | 0.2591 | 0.042* | |
C17 | 0.5477 (12) | 0.5702 (4) | 0.3132 (5) | 0.0345 (17) | |
C18 | 0.5973 (14) | 0.5198 (5) | 0.4025 (5) | 0.0396 (19) | |
H18 | 0.4731 | 0.5186 | 0.4319 | 0.047* | |
C19 | 0.6453 (12) | 0.4289 (5) | 0.3749 (5) | 0.0361 (17) | |
H19A | 0.7017 | 0.3974 | 0.4315 | 0.043* | |
H19B | 0.5168 | 0.4018 | 0.3451 | 0.043* | |
C20 | 0.7985 (12) | 0.4269 (4) | 0.3083 (5) | 0.0333 (16) | |
H20 | 0.9246 | 0.4572 | 0.3375 | 0.040* | |
C21 | 0.8607 (11) | 0.3405 (5) | 0.2789 (5) | 0.0356 (17) | |
H21 | 0.7430 | 0.3145 | 0.2366 | 0.043* | |
C22 | 0.9502 (11) | 0.2777 (5) | 0.3590 (5) | 0.0343 (17) | |
C23 | 1.0319 (14) | 0.2005 (5) | 0.3158 (6) | 0.050 (2) | |
H23A | 0.9253 | 0.1784 | 0.2671 | 0.075* | |
H23B | 1.0709 | 0.1585 | 0.3637 | 0.075* | |
H23C | 1.1514 | 0.2157 | 0.2891 | 0.075* | |
C24 | 1.1135 (13) | 0.3150 (6) | 0.4342 (6) | 0.052 (2) | |
H24A | 1.0593 | 0.3647 | 0.4591 | 0.079* | |
H24B | 1.2336 | 0.3296 | 0.4078 | 0.079* | |
H24C | 1.1524 | 0.2748 | 0.4841 | 0.079* | |
C25 | 0.2861 (14) | 1.0721 (5) | 0.1050 (6) | 0.053 (2) | |
H25A | 0.2588 | 1.0445 | 0.0447 | 0.080* | |
H25B | 0.3064 | 1.1312 | 0.0962 | 0.080* | |
H25C | 0.1698 | 1.0640 | 0.1365 | 0.080* | |
C26 | 0.6698 (13) | 1.0584 (6) | 0.1182 (6) | 0.050 (2) | |
H26A | 0.6526 | 1.0337 | 0.0565 | 0.075* | |
H26B | 0.7955 | 1.0375 | 0.1564 | 0.075* | |
H26C | 0.6782 | 1.1185 | 0.1131 | 0.075* | |
C27 | 0.1778 (13) | 0.9489 (6) | 0.2643 (5) | 0.045 (2) | |
H27A | 0.1942 | 1.0090 | 0.2670 | 0.068* | |
H27B | 0.1237 | 0.9300 | 0.3183 | 0.068* | |
H27C | 0.0828 | 0.9338 | 0.2077 | 0.068* | |
C28 | 0.7171 (11) | 0.7592 (5) | 0.2526 (6) | 0.0403 (18) | |
H28A | 0.7263 | 0.7351 | 0.3143 | 0.060* | |
H28B | 0.7663 | 0.8162 | 0.2582 | 0.060* | |
H28C | 0.8012 | 0.7270 | 0.2173 | 0.060* | |
C29 | 0.1928 (12) | 0.6566 (6) | 0.1275 (5) | 0.0452 (19) | |
H29A | 0.1967 | 0.6800 | 0.0664 | 0.068* | |
H29B | 0.0921 | 0.6865 | 0.1559 | 0.068* | |
H29C | 0.1545 | 0.5983 | 0.1210 | 0.068* | |
C30 | 0.7728 (18) | 0.5592 (6) | 0.4713 (5) | 0.067 (3) | |
H30A | 0.7997 | 0.5264 | 0.5281 | 0.100* | |
H30B | 0.7346 | 0.6154 | 0.4859 | 0.100* | |
H30C | 0.8960 | 0.5611 | 0.4436 | 0.100* | |
C31 | 1.0144 (18) | 0.3278 (7) | 0.1390 (6) | 0.060 (2) | |
C32 | 1.193 (2) | 0.3555 (10) | 0.0980 (8) | 0.102 (4) | |
H32A | 1.2844 | 0.3889 | 0.1434 | 0.153* | |
H32B | 1.1447 | 0.3885 | 0.0425 | 0.153* | |
H32C | 1.2671 | 0.3071 | 0.0814 | 0.153* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.056 (4) | 0.039 (4) | 0.072 (4) | 0.002 (3) | 0.015 (3) | 0.002 (3) |
O2 | 0.064 (4) | 0.040 (3) | 0.040 (3) | 0.006 (3) | 0.025 (3) | −0.004 (2) |
O3 | 0.059 (4) | 0.028 (3) | 0.027 (2) | 0.008 (2) | 0.015 (2) | −0.001 (2) |
O4 | 0.046 (3) | 0.043 (3) | 0.045 (3) | 0.007 (2) | 0.023 (2) | −0.005 (2) |
O5 | 0.121 (7) | 0.095 (6) | 0.037 (3) | 0.004 (5) | 0.007 (4) | −0.010 (4) |
O6 | 0.053 (3) | 0.039 (3) | 0.047 (3) | −0.006 (3) | 0.023 (3) | −0.012 (2) |
C1 | 0.042 (5) | 0.040 (4) | 0.031 (4) | 0.000 (4) | 0.003 (3) | 0.001 (3) |
C2 | 0.068 (6) | 0.044 (5) | 0.037 (4) | −0.016 (4) | −0.004 (4) | −0.008 (4) |
C3 | 0.033 (4) | 0.035 (5) | 0.039 (4) | −0.004 (3) | 0.012 (3) | 0.003 (3) |
C4 | 0.028 (4) | 0.039 (4) | 0.049 (4) | 0.005 (3) | 0.010 (3) | 0.002 (3) |
C5 | 0.033 (4) | 0.034 (4) | 0.032 (4) | 0.007 (3) | 0.007 (3) | 0.001 (3) |
C6 | 0.049 (5) | 0.034 (4) | 0.033 (4) | −0.005 (4) | 0.007 (3) | −0.004 (3) |
C7 | 0.050 (5) | 0.045 (5) | 0.030 (4) | 0.004 (4) | 0.012 (3) | −0.004 (3) |
C8 | 0.021 (4) | 0.029 (4) | 0.044 (4) | 0.004 (3) | 0.004 (3) | 0.004 (3) |
C9 | 0.023 (4) | 0.038 (4) | 0.029 (3) | 0.000 (3) | 0.006 (3) | 0.001 (3) |
C10 | 0.025 (4) | 0.038 (4) | 0.033 (3) | 0.002 (3) | 0.008 (3) | −0.004 (3) |
C11 | 0.039 (4) | 0.029 (4) | 0.033 (4) | 0.001 (3) | 0.010 (3) | −0.004 (3) |
C12 | 0.041 (5) | 0.037 (4) | 0.043 (4) | −0.002 (3) | 0.021 (3) | −0.001 (3) |
C13 | 0.039 (4) | 0.030 (4) | 0.036 (4) | −0.001 (3) | 0.018 (3) | 0.002 (3) |
C14 | 0.035 (4) | 0.037 (4) | 0.026 (3) | 0.004 (3) | 0.005 (3) | 0.004 (3) |
C15 | 0.050 (5) | 0.037 (4) | 0.035 (4) | 0.003 (4) | 0.017 (4) | 0.001 (3) |
C16 | 0.044 (5) | 0.034 (4) | 0.029 (3) | −0.002 (3) | 0.013 (3) | −0.004 (3) |
C17 | 0.052 (5) | 0.026 (4) | 0.029 (3) | −0.001 (3) | 0.016 (3) | −0.001 (3) |
C18 | 0.067 (6) | 0.029 (4) | 0.026 (3) | 0.006 (3) | 0.017 (4) | 0.003 (3) |
C19 | 0.045 (5) | 0.033 (4) | 0.034 (4) | 0.003 (3) | 0.017 (3) | 0.003 (3) |
C20 | 0.042 (4) | 0.019 (3) | 0.039 (4) | 0.003 (3) | 0.008 (3) | 0.000 (3) |
C21 | 0.031 (4) | 0.038 (4) | 0.038 (4) | 0.005 (3) | 0.006 (3) | −0.008 (3) |
C22 | 0.027 (4) | 0.031 (4) | 0.044 (4) | 0.000 (3) | 0.007 (3) | −0.002 (3) |
C23 | 0.055 (6) | 0.044 (5) | 0.051 (5) | 0.018 (4) | 0.011 (4) | 0.010 (4) |
C24 | 0.044 (5) | 0.062 (6) | 0.048 (5) | −0.003 (4) | −0.001 (4) | 0.008 (4) |
C25 | 0.053 (6) | 0.045 (5) | 0.059 (5) | 0.010 (4) | 0.003 (4) | 0.015 (4) |
C26 | 0.048 (5) | 0.046 (5) | 0.060 (5) | 0.005 (4) | 0.020 (4) | −0.002 (4) |
C27 | 0.041 (5) | 0.053 (5) | 0.042 (4) | 0.006 (4) | 0.007 (4) | 0.003 (4) |
C28 | 0.031 (4) | 0.038 (4) | 0.055 (4) | 0.010 (3) | 0.020 (3) | 0.006 (4) |
C29 | 0.040 (5) | 0.049 (5) | 0.046 (4) | 0.000 (4) | 0.007 (4) | −0.006 (4) |
C30 | 0.131 (9) | 0.039 (5) | 0.026 (4) | 0.010 (5) | 0.005 (5) | −0.008 (3) |
C31 | 0.080 (7) | 0.065 (6) | 0.040 (5) | 0.016 (5) | 0.026 (5) | 0.003 (4) |
C32 | 0.118 (10) | 0.134 (11) | 0.070 (7) | −0.007 (9) | 0.061 (7) | −0.006 (7) |
O1—C3 | 1.210 (9) | C15—C16 | 1.511 (11) |
O2—C11 | 1.432 (8) | C15—H15A | 0.9700 |
O2—H2 | 0.8200 | C15—H15B | 0.9700 |
O3—C16 | 1.430 (9) | C16—C17 | 1.502 (9) |
O3—C20 | 1.455 (8) | C16—H16 | 0.9800 |
O4—C31 | 1.340 (11) | C17—C18 | 1.499 (10) |
O4—C21 | 1.458 (9) | C18—C30 | 1.507 (13) |
O5—C31 | 1.196 (13) | C18—C19 | 1.546 (10) |
O6—C22 | 1.435 (9) | C18—H18 | 0.9800 |
O6—H6 | 0.8200 | C19—C20 | 1.505 (10) |
C1—C2 | 1.535 (12) | C19—H19A | 0.9700 |
C1—C10 | 1.540 (10) | C19—H19B | 0.9700 |
C1—H1A | 0.9700 | C20—C21 | 1.513 (10) |
C1—H1B | 0.9700 | C20—H20 | 0.9800 |
C2—C3 | 1.499 (11) | C21—C22 | 1.557 (10) |
C2—H2A | 0.9700 | C21—H21 | 0.9800 |
C2—H2B | 0.9700 | C22—C24 | 1.497 (11) |
C3—C4 | 1.533 (11) | C22—C23 | 1.515 (11) |
C4—C25 | 1.518 (11) | C23—H23A | 0.9600 |
C4—C26 | 1.551 (10) | C23—H23B | 0.9600 |
C4—C5 | 1.554 (11) | C23—H23C | 0.9600 |
C5—C6 | 1.515 (10) | C24—H24A | 0.9600 |
C5—C10 | 1.550 (10) | C24—H24B | 0.9600 |
C5—H5 | 0.9800 | C24—H24C | 0.9600 |
C6—C7 | 1.518 (11) | C25—H25A | 0.9600 |
C6—H6A | 0.9700 | C25—H25B | 0.9600 |
C6—H6B | 0.9700 | C25—H25C | 0.9600 |
C7—C8 | 1.549 (10) | C26—H26A | 0.9600 |
C7—H7A | 0.9700 | C26—H26B | 0.9600 |
C7—H7B | 0.9700 | C26—H26C | 0.9600 |
C8—C28 | 1.545 (10) | C27—H27A | 0.9600 |
C8—C14 | 1.564 (10) | C27—H27B | 0.9600 |
C8—C9 | 1.579 (10) | C27—H27C | 0.9600 |
C9—C11 | 1.533 (9) | C28—H28A | 0.9600 |
C9—C10 | 1.589 (10) | C28—H28B | 0.9600 |
C9—H9 | 0.9800 | C28—H28C | 0.9600 |
C10—C27 | 1.511 (10) | C29—H29A | 0.9600 |
C11—C12 | 1.518 (10) | C29—H29B | 0.9600 |
C11—H11 | 0.9800 | C29—H29C | 0.9600 |
C12—C13 | 1.492 (10) | C30—H30A | 0.9600 |
C12—H12A | 0.9700 | C30—H30B | 0.9600 |
C12—H12B | 0.9700 | C30—H30C | 0.9600 |
C13—C17 | 1.308 (10) | C31—C32 | 1.466 (15) |
C13—C14 | 1.507 (9) | C32—H32A | 0.9600 |
C14—C29 | 1.535 (11) | C32—H32B | 0.9600 |
C14—C15 | 1.573 (10) | C32—H32C | 0.9600 |
C11—O2—H2 | 109.5 | C17—C16—H16 | 109.4 |
C16—O3—C20 | 110.0 (5) | C15—C16—H16 | 109.4 |
C31—O4—C21 | 119.4 (7) | C13—C17—C18 | 131.0 (7) |
C22—O6—H6 | 109.5 | C13—C17—C16 | 110.7 (6) |
C2—C1—C10 | 112.7 (6) | C18—C17—C16 | 118.2 (6) |
C2—C1—H1A | 109.1 | C17—C18—C30 | 111.2 (7) |
C10—C1—H1A | 109.1 | C17—C18—C19 | 107.5 (6) |
C2—C1—H1B | 109.1 | C30—C18—C19 | 113.1 (7) |
C10—C1—H1B | 109.1 | C17—C18—H18 | 108.3 |
H1A—C1—H1B | 107.8 | C30—C18—H18 | 108.3 |
C3—C2—C1 | 117.3 (7) | C19—C18—H18 | 108.3 |
C3—C2—H2A | 108.0 | C20—C19—C18 | 111.9 (6) |
C1—C2—H2A | 108.0 | C20—C19—H19A | 109.2 |
C3—C2—H2B | 108.0 | C18—C19—H19A | 109.2 |
C1—C2—H2B | 108.0 | C20—C19—H19B | 109.2 |
H2A—C2—H2B | 107.2 | C18—C19—H19B | 109.2 |
O1—C3—C2 | 121.0 (7) | H19A—C19—H19B | 107.9 |
O1—C3—C4 | 121.5 (7) | O3—C20—C19 | 109.1 (6) |
C2—C3—C4 | 117.1 (7) | O3—C20—C21 | 105.5 (5) |
C25—C4—C3 | 111.4 (6) | C19—C20—C21 | 116.1 (6) |
C25—C4—C26 | 108.2 (7) | O3—C20—H20 | 108.6 |
C3—C4—C26 | 103.9 (6) | C19—C20—H20 | 108.6 |
C25—C4—C5 | 115.9 (7) | C21—C20—H20 | 108.6 |
C3—C4—C5 | 108.6 (6) | O4—C21—C20 | 104.0 (6) |
C26—C4—C5 | 108.0 (6) | O4—C21—C22 | 106.3 (5) |
C6—C5—C10 | 110.7 (6) | C20—C21—C22 | 117.2 (6) |
C6—C5—C4 | 115.5 (6) | O4—C21—H21 | 109.7 |
C10—C5—C4 | 114.4 (6) | C20—C21—H21 | 109.7 |
C6—C5—H5 | 105.0 | C22—C21—H21 | 109.7 |
C10—C5—H5 | 105.0 | O6—C22—C24 | 106.3 (6) |
C4—C5—H5 | 105.0 | O6—C22—C23 | 108.8 (6) |
C5—C6—C7 | 109.4 (6) | C24—C22—C23 | 111.1 (7) |
C5—C6—H6A | 109.8 | O6—C22—C21 | 107.5 (5) |
C7—C6—H6A | 109.8 | C24—C22—C21 | 113.8 (6) |
C5—C6—H6B | 109.8 | C23—C22—C21 | 109.0 (6) |
C7—C6—H6B | 109.8 | C22—C23—H23A | 109.5 |
H6A—C6—H6B | 108.2 | C22—C23—H23B | 109.5 |
C6—C7—C8 | 116.0 (6) | H23A—C23—H23B | 109.5 |
C6—C7—H7A | 108.3 | C22—C23—H23C | 109.5 |
C8—C7—H7A | 108.3 | H23A—C23—H23C | 109.5 |
C6—C7—H7B | 108.3 | H23B—C23—H23C | 109.5 |
C8—C7—H7B | 108.3 | C22—C24—H24A | 109.5 |
H7A—C7—H7B | 107.4 | C22—C24—H24B | 109.5 |
C28—C8—C7 | 108.4 (6) | H24A—C24—H24B | 109.5 |
C28—C8—C14 | 109.5 (6) | C22—C24—H24C | 109.5 |
C7—C8—C14 | 110.1 (6) | H24A—C24—H24C | 109.5 |
C28—C8—C9 | 109.8 (6) | H24B—C24—H24C | 109.5 |
C7—C8—C9 | 109.9 (6) | C4—C25—H25A | 109.5 |
C14—C8—C9 | 109.1 (5) | C4—C25—H25B | 109.5 |
C11—C9—C8 | 110.8 (6) | H25A—C25—H25B | 109.5 |
C11—C9—C10 | 114.3 (5) | C4—C25—H25C | 109.5 |
C8—C9—C10 | 115.5 (5) | H25A—C25—H25C | 109.5 |
C11—C9—H9 | 105.0 | H25B—C25—H25C | 109.5 |
C8—C9—H9 | 105.0 | C4—C26—H26A | 109.5 |
C10—C9—H9 | 105.0 | C4—C26—H26B | 109.5 |
C27—C10—C1 | 108.5 (6) | H26A—C26—H26B | 109.5 |
C27—C10—C5 | 111.1 (6) | C4—C26—H26C | 109.5 |
C1—C10—C5 | 106.9 (6) | H26A—C26—H26C | 109.5 |
C27—C10—C9 | 106.7 (6) | H26B—C26—H26C | 109.5 |
C1—C10—C9 | 113.1 (6) | C10—C27—H27A | 109.5 |
C5—C10—C9 | 110.6 (5) | C10—C27—H27B | 109.5 |
O2—C11—C12 | 109.6 (6) | H27A—C27—H27B | 109.5 |
O2—C11—C9 | 109.5 (6) | C10—C27—H27C | 109.5 |
C12—C11—C9 | 112.1 (6) | H27A—C27—H27C | 109.5 |
O2—C11—H11 | 108.5 | H27B—C27—H27C | 109.5 |
C12—C11—H11 | 108.5 | C8—C28—H28A | 109.5 |
C9—C11—H11 | 108.5 | C8—C28—H28B | 109.5 |
C13—C12—C11 | 110.1 (6) | H28A—C28—H28B | 109.5 |
C13—C12—H12A | 109.6 | C8—C28—H28C | 109.5 |
C11—C12—H12A | 109.6 | H28A—C28—H28C | 109.5 |
C13—C12—H12B | 109.6 | H28B—C28—H28C | 109.5 |
C11—C12—H12B | 109.6 | C14—C29—H29A | 109.5 |
H12A—C12—H12B | 108.2 | C14—C29—H29B | 109.5 |
C17—C13—C12 | 129.3 (7) | H29A—C29—H29B | 109.5 |
C17—C13—C14 | 114.6 (6) | C14—C29—H29C | 109.5 |
C12—C13—C14 | 115.3 (6) | H29A—C29—H29C | 109.5 |
C13—C14—C29 | 111.5 (6) | H29B—C29—H29C | 109.5 |
C13—C14—C8 | 108.4 (6) | C18—C30—H30A | 109.5 |
C29—C14—C8 | 112.8 (6) | C18—C30—H30B | 109.5 |
C13—C14—C15 | 100.7 (6) | H30A—C30—H30B | 109.5 |
C29—C14—C15 | 108.5 (6) | C18—C30—H30C | 109.5 |
C8—C14—C15 | 114.3 (6) | H30A—C30—H30C | 109.5 |
C16—C15—C14 | 106.3 (5) | H30B—C30—H30C | 109.5 |
C16—C15—H15A | 110.5 | O5—C31—O4 | 122.9 (9) |
C14—C15—H15A | 110.5 | O5—C31—C32 | 126.4 (10) |
C16—C15—H15B | 110.5 | O4—C31—C32 | 110.6 (10) |
C14—C15—H15B | 110.5 | C31—C32—H32A | 109.5 |
H15A—C15—H15B | 108.7 | C31—C32—H32B | 109.5 |
O3—C16—C17 | 112.1 (6) | H32A—C32—H32B | 109.5 |
O3—C16—C15 | 112.2 (6) | C31—C32—H32C | 109.5 |
C17—C16—C15 | 104.2 (6) | H32A—C32—H32C | 109.5 |
O3—C16—H16 | 109.4 | H32B—C32—H32C | 109.5 |
C10—C1—C2—C3 | 14.8 (10) | C17—C13—C14—C8 | −112.1 (7) |
C1—C2—C3—O1 | 139.2 (8) | C12—C13—C14—C8 | 58.6 (8) |
C1—C2—C3—C4 | −47.6 (10) | C17—C13—C14—C15 | 8.2 (9) |
O1—C3—C4—C25 | −38.8 (10) | C12—C13—C14—C15 | 178.8 (6) |
C2—C3—C4—C25 | 148.1 (7) | C28—C8—C14—C13 | 64.1 (7) |
O1—C3—C4—C26 | 77.4 (9) | C7—C8—C14—C13 | −176.7 (6) |
C2—C3—C4—C26 | −95.7 (8) | C9—C8—C14—C13 | −56.1 (7) |
O1—C3—C4—C5 | −167.7 (7) | C28—C8—C14—C29 | −171.9 (6) |
C2—C3—C4—C5 | 19.1 (9) | C7—C8—C14—C29 | −52.8 (8) |
C25—C4—C5—C6 | 41.8 (9) | C9—C8—C14—C29 | 67.9 (7) |
C3—C4—C5—C6 | 168.2 (6) | C28—C8—C14—C15 | −47.2 (7) |
C26—C4—C5—C6 | −79.7 (8) | C7—C8—C14—C15 | 71.9 (7) |
C25—C4—C5—C10 | −88.3 (8) | C9—C8—C14—C15 | −167.5 (5) |
C3—C4—C5—C10 | 38.0 (8) | C13—C14—C15—C16 | −16.3 (8) |
C26—C4—C5—C10 | 150.1 (6) | C29—C14—C15—C16 | −133.5 (7) |
C10—C5—C6—C7 | −70.2 (8) | C8—C14—C15—C16 | 99.7 (7) |
C4—C5—C6—C7 | 157.9 (6) | C20—O3—C16—C17 | −56.3 (8) |
C5—C6—C7—C8 | 41.4 (9) | C20—O3—C16—C15 | −173.2 (6) |
C6—C7—C8—C28 | −103.5 (8) | C14—C15—C16—O3 | 140.1 (6) |
C6—C7—C8—C14 | 136.8 (7) | C14—C15—C16—C17 | 18.6 (8) |
C6—C7—C8—C9 | 16.6 (9) | C12—C13—C17—C18 | 11.1 (14) |
C28—C8—C9—C11 | −63.7 (8) | C14—C13—C17—C18 | −179.8 (7) |
C7—C8—C9—C11 | 177.1 (6) | C12—C13—C17—C16 | −165.5 (7) |
C14—C8—C9—C11 | 56.3 (7) | C14—C13—C17—C16 | 3.6 (9) |
C28—C8—C9—C10 | 68.2 (7) | O3—C16—C17—C13 | −135.9 (7) |
C7—C8—C9—C10 | −51.0 (8) | C15—C16—C17—C13 | −14.3 (9) |
C14—C8—C9—C10 | −171.7 (6) | O3—C16—C17—C18 | 47.0 (9) |
C2—C1—C10—C27 | −81.3 (8) | C15—C16—C17—C18 | 168.6 (7) |
C2—C1—C10—C5 | 38.6 (8) | C13—C17—C18—C30 | −94.0 (11) |
C2—C1—C10—C9 | 160.6 (6) | C16—C17—C18—C30 | 82.4 (8) |
C6—C5—C10—C27 | −83.3 (8) | C13—C17—C18—C19 | 141.7 (8) |
C4—C5—C10—C27 | 49.3 (8) | C16—C17—C18—C19 | −41.9 (9) |
C6—C5—C10—C1 | 158.6 (6) | C17—C18—C19—C20 | 48.9 (9) |
C4—C5—C10—C1 | −68.9 (8) | C30—C18—C19—C20 | −74.2 (8) |
C6—C5—C10—C9 | 35.0 (8) | C16—O3—C20—C19 | 65.3 (7) |
C4—C5—C10—C9 | 167.5 (6) | C16—O3—C20—C21 | −169.3 (6) |
C11—C9—C10—C27 | −84.3 (7) | C18—C19—C20—O3 | −62.6 (8) |
C8—C9—C10—C27 | 145.4 (6) | C18—C19—C20—C21 | 178.4 (6) |
C11—C9—C10—C1 | 34.9 (8) | C31—O4—C21—C20 | −125.2 (7) |
C8—C9—C10—C1 | −95.4 (7) | C31—O4—C21—C22 | 110.5 (8) |
C11—C9—C10—C5 | 154.8 (6) | O3—C20—C21—O4 | 66.9 (7) |
C8—C9—C10—C5 | 24.5 (8) | C19—C20—C21—O4 | −172.1 (6) |
C8—C9—C11—O2 | −177.1 (5) | O3—C20—C21—C22 | −176.1 (6) |
C10—C9—C11—O2 | 50.3 (8) | C19—C20—C21—C22 | −55.1 (9) |
C8—C9—C11—C12 | −55.3 (8) | O4—C21—C22—O6 | −173.8 (5) |
C10—C9—C11—C12 | 172.1 (6) | C20—C21—C22—O6 | 70.5 (8) |
O2—C11—C12—C13 | 175.4 (6) | O4—C21—C22—C24 | 68.7 (7) |
C9—C11—C12—C13 | 53.7 (8) | C20—C21—C22—C24 | −47.0 (9) |
C11—C12—C13—C17 | 112.2 (9) | O4—C21—C22—C23 | −56.0 (8) |
C11—C12—C13—C14 | −56.8 (9) | C20—C21—C22—C23 | −171.7 (7) |
C17—C13—C14—C29 | 123.1 (8) | C21—O4—C31—O5 | −4.5 (13) |
C12—C13—C14—C29 | −66.2 (9) | C21—O4—C31—C32 | 176.9 (8) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O6i | 0.82 | 2.09 | 2.904 (7) | 172 |
O6—H6···O1ii | 0.82 | 2.07 | 2.867 (8) | 165 |
Symmetry codes: (i) −x+1, y+1/2, −z+1; (ii) x, y−1, z. |
Experimental details
Crystal data | |
Chemical formula | C32H50O6 |
Mr | 530.72 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 298 |
a, b, c (Å) | 6.525 (4), 15.885 (10), 14.401 (9) |
β (°) | 100.475 (10) |
V (Å3) | 1467.8 (16) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.50 × 0.47 × 0.40 |
Data collection | |
Diffractometer | Bruker SMART 1000 CCD area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2001) |
Tmin, Tmax | 0.959, 0.968 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7306, 2697, 1811 |
Rint | 0.072 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.089, 0.236, 1.00 |
No. of reflections | 2697 |
No. of parameters | 343 |
No. of restraints | 37 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.48, −0.26 |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2001).
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O6i | 0.82 | 2.09 | 2.904 (7) | 172.3 |
O6—H6···O1ii | 0.82 | 2.07 | 2.867 (8) | 165.3 |
Symmetry codes: (i) −x+1, y+1/2, −z+1; (ii) x, y−1, z. |
The title compound, C32H50O6, a known protostane-type triterpene, named alisol F 24-acetate [systematic name: 16β, 23β-epoxy-11β, 25-dihydroxy-24(R)-acetoxy-protost-13 (17)-en-3-one], was isolated from the Chinese herbal medicine Lobelia chinensis Lour firstly obtained by Peng & Lou (2001) and found to possess activity for inhibiting formation of urinary oxalate calcium calculi. Its structure was elucidated on the basis of spectroscopic methods such as 1H NMR, 13C NMR, two-dimensional NMR and chemical correlation (Peng & Lou, 2001; Zhou et al., 2005).
The molecule contains a five-fused ring system including four six-membered rings, A(C1—C5/C10), B(C5—C10), C(C8—C14) and E(O3/C16—C20) and a five-membered ring D(C13—C17) (Fig. 1). The junctions of the three fused six-membered rings A, B and C, two of which, A and B, adopt slightly distorted boat conformations and the C exhibits a perfect chair conformation, are all trans. The five-membered ring D is almost planar. Ring E adopts a chair conformation. A chain running along the b axis was formed via the classic intermolecular O—H···O hydrogen bonds as shown in Fig. 2.