organic compounds
Ethoxycarbonylmethyl ursolate
aCollege of Chemistry, Sichuan University, Chengdu 610064, People's Republic of China
*Correspondence e-mail: chuandayouji217@163.com
The title compound, C34H54O5, was synthesized by the reaction of ursolic acid with ethyl chloroacetate in the presence of DMA. All six-membered rings of the pentacyclic triterpene skeleton adopt chair conformations. In the molecules are linked by intermolecular O—H⋯O hydrogen-bond interactions, forming zigzag chains along the c axis.
Related literature
For the pharmacological activity of ursolic acid, see: Es-saady et al. (1996); Kashiwada et al. (2000). For the of ursolic acid, see: Simon et al. (1992). For the synthesis and characterization of the title compound and other ursolic acid derivatives, see: Yang et al. (2008); Liu et al. (2007).
Experimental
Crystal data
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Data collection
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Refinement
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Data collection: DIFRAC (Gabe & White, 1993); cell DIFRAC; data reduction: NRCVAX (Gabe et al., 1989); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
Supporting information
10.1107/S1600536808039706/rz2269sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536808039706/rz2269Isup2.hkl
To a solution of ursolid acid (456 mg, 1 mmol) in DMF (10 ml) was added K2CO3 (300 mg, 2.2 mmol), KI (50 mg, 0.3 mmol) and NEt3 (0.5 ml). After stirring at room temperature for 10 minutes, a solution of ethyl chlorocetate (0.4 ml, 3 mmol) in DMF was added dropwise, and the reaction monitored by TLC. After completion of the reaction, satured brines and ehtyl acetate were added. The organic layer was separated, washed with water until neutral, dried with Na2SO4, filtered and evaporated in vacuo to get the solid title compound. Colourless crystals suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution at room temperature.
H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93–0.98 Å, O—H = 0.82 Å and with Uiso(H) = 1.2Ueq(C) or 1.5 Ueq(C, O) for hydroxy and methyl H atoms. In the absence of significant
effects, Friedel pairs were merged.Data collection: DIFRAC (Gabe & White, 1993); cell
DIFRAC (Gabe & White, 1993); data reduction: NRCVAX (Gabe et al., 1989); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level. |
C34H54O5 | F(000) = 1192 |
Mr = 542.77 | Dx = 1.158 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 14 reflections |
a = 11.624 (3) Å | θ = 4.3–5.6° |
b = 12.465 (4) Å | µ = 0.08 mm−1 |
c = 21.478 (3) Å | T = 292 K |
V = 3112.0 (14) Å3 | Block, colourless |
Z = 4 | 0.60 × 0.56 × 0.44 mm |
Enraf–Nonius CAD-4 diffractometer | Rint = 0.009 |
Radiation source: fine-focus sealed tube | θmax = 25.2°, θmin = 1.9° |
Graphite monochromator | h = −2→13 |
ω/2θ scans | k = −6→14 |
3435 measured reflections | l = −3→25 |
3116 independent reflections | 3 standard reflections every 200 reflections |
1818 reflections with I > 2σ(I) | intensity decay: 0.9% |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.047 | H-atom parameters constrained |
wR(F2) = 0.125 | w = 1/[σ2(Fo2) + (0.0695P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.97 | (Δ/σ)max < 0.001 |
3116 reflections | Δρmax = 0.19 e Å−3 |
362 parameters | Δρmin = −0.17 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0090 (12) |
C34H54O5 | V = 3112.0 (14) Å3 |
Mr = 542.77 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 11.624 (3) Å | µ = 0.08 mm−1 |
b = 12.465 (4) Å | T = 292 K |
c = 21.478 (3) Å | 0.60 × 0.56 × 0.44 mm |
Enraf–Nonius CAD-4 diffractometer | Rint = 0.009 |
3435 measured reflections | 3 standard reflections every 200 reflections |
3116 independent reflections | intensity decay: 0.9% |
1818 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.125 | H-atom parameters constrained |
S = 0.97 | Δρmax = 0.19 e Å−3 |
3116 reflections | Δρmin = −0.17 e Å−3 |
362 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 > 2σ(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 | 0.3112 (2) | −0.0655 (2) | 0.43876 (11) | 0.0676 (8) | |
H1 | 0.2632 | −0.1128 | 0.4442 | 0.101* | |
O2 | 0.5639 (2) | 0.28015 (19) | −0.04823 (12) | 0.0593 (7) | |
O3 | 0.3922 (2) | 0.20169 (19) | −0.04048 (12) | 0.0554 (7) | |
O4 | 0.4470 (3) | 0.4876 (2) | −0.14161 (14) | 0.0785 (9) | |
O5 | 0.4757 (3) | 0.3145 (2) | −0.16352 (13) | 0.0855 (10) | |
C1 | 0.3267 (3) | 0.0359 (3) | 0.24624 (16) | 0.0457 (9) | |
C2 | 0.4278 (3) | 0.0554 (3) | 0.29194 (16) | 0.0465 (9) | |
H2 | 0.4800 | −0.0049 | 0.2841 | 0.056* | |
C3 | 0.4019 (3) | 0.0475 (3) | 0.36250 (16) | 0.0495 (10) | |
C4 | 0.3383 (3) | −0.0584 (3) | 0.37360 (17) | 0.0516 (10) | |
H4 | 0.3922 | −0.1166 | 0.3641 | 0.062* | |
C5 | 0.2331 (4) | −0.0748 (3) | 0.33319 (18) | 0.0597 (11) | |
H5A | 0.1764 | −0.0201 | 0.3425 | 0.072* | |
H5B | 0.1993 | −0.1443 | 0.3421 | 0.072* | |
C6 | 0.2661 (3) | −0.0687 (3) | 0.26447 (16) | 0.0527 (10) | |
H6A | 0.1970 | −0.0764 | 0.2395 | 0.063* | |
H6B | 0.3164 | −0.1285 | 0.2547 | 0.063* | |
C7 | 0.3321 (4) | 0.1428 (3) | 0.38858 (18) | 0.0654 (11) | |
H7A | 0.2538 | 0.1374 | 0.3749 | 0.098* | |
H7B | 0.3647 | 0.2089 | 0.3738 | 0.098* | |
H7C | 0.3346 | 0.1414 | 0.4333 | 0.098* | |
C8 | 0.5167 (4) | 0.0419 (3) | 0.39817 (19) | 0.0649 (12) | |
H8A | 0.5018 | 0.0303 | 0.4416 | 0.097* | |
H8B | 0.5578 | 0.1081 | 0.3929 | 0.097* | |
H8C | 0.5622 | −0.0163 | 0.3822 | 0.097* | |
C9 | 0.2352 (4) | 0.1256 (3) | 0.24777 (19) | 0.0648 (12) | |
H9A | 0.1847 | 0.1145 | 0.2825 | 0.097* | |
H9B | 0.1915 | 0.1242 | 0.2099 | 0.097* | |
H9C | 0.2726 | 0.1939 | 0.2519 | 0.097* | |
C10 | 0.4969 (4) | 0.1536 (3) | 0.27172 (17) | 0.0579 (11) | |
H10A | 0.5552 | 0.1693 | 0.3027 | 0.069* | |
H10B | 0.4461 | 0.2152 | 0.2688 | 0.069* | |
C11 | 0.5544 (3) | 0.1341 (3) | 0.20874 (16) | 0.0537 (10) | |
H11A | 0.6105 | 0.0770 | 0.2132 | 0.064* | |
H11B | 0.5955 | 0.1985 | 0.1966 | 0.064* | |
C12 | 0.4692 (3) | 0.1036 (3) | 0.15636 (17) | 0.0478 (9) | |
C13 | 0.3811 (3) | 0.0197 (3) | 0.18028 (16) | 0.0472 (9) | |
H13 | 0.4251 | −0.0471 | 0.1837 | 0.057* | |
C14 | 0.4064 (4) | 0.2061 (3) | 0.13466 (18) | 0.0583 (11) | |
H14A | 0.3572 | 0.1892 | 0.1001 | 0.087* | |
H14B | 0.4620 | 0.2588 | 0.1221 | 0.087* | |
H14C | 0.3610 | 0.2341 | 0.1683 | 0.087* | |
C15 | 0.5377 (3) | 0.0506 (3) | 0.10000 (17) | 0.0472 (9) | |
C16 | 0.4504 (3) | 0.0129 (2) | 0.05037 (16) | 0.0450 (9) | |
C17 | 0.3432 (3) | −0.0089 (3) | 0.06576 (17) | 0.0521 (10) | |
H17 | 0.2946 | −0.0305 | 0.0337 | 0.063* | |
C18 | 0.2915 (3) | −0.0026 (3) | 0.12919 (18) | 0.0597 (11) | |
H18A | 0.2528 | −0.0697 | 0.1383 | 0.072* | |
H18B | 0.2342 | 0.0540 | 0.1297 | 0.072* | |
C19 | 0.6073 (4) | −0.0486 (3) | 0.12069 (19) | 0.0615 (11) | |
H19A | 0.5554 | −0.1046 | 0.1332 | 0.092* | |
H19B | 0.6559 | −0.0297 | 0.1551 | 0.092* | |
H19C | 0.6538 | −0.0734 | 0.0867 | 0.092* | |
C20 | 0.6231 (3) | 0.1324 (3) | 0.07259 (18) | 0.0599 (11) | |
H20A | 0.5860 | 0.2021 | 0.0712 | 0.072* | |
H20B | 0.6886 | 0.1381 | 0.1004 | 0.072* | |
C21 | 0.6667 (3) | 0.1052 (3) | 0.00753 (17) | 0.0597 (11) | |
H21A | 0.7111 | 0.0394 | 0.0091 | 0.072* | |
H21B | 0.7168 | 0.1621 | −0.0071 | 0.072* | |
C22 | 0.5655 (3) | 0.0913 (3) | −0.03835 (17) | 0.0495 (10) | |
C23 | 0.4897 (3) | −0.0026 (3) | −0.01690 (16) | 0.0482 (9) | |
H23 | 0.4199 | 0.0008 | −0.0424 | 0.058* | |
C24 | 0.5438 (4) | −0.1142 (3) | −0.02978 (18) | 0.0640 (12) | |
H24 | 0.6126 | −0.1207 | −0.0037 | 0.077* | |
C25 | 0.5818 (4) | −0.1250 (3) | −0.0978 (2) | 0.0719 (13) | |
H25 | 0.5131 | −0.1206 | −0.1241 | 0.086* | |
C26 | 0.6616 (4) | −0.0351 (4) | −0.1159 (2) | 0.0772 (14) | |
H26A | 0.6821 | −0.0427 | −0.1595 | 0.093* | |
H26B | 0.7317 | −0.0403 | −0.0916 | 0.093* | |
C27 | 0.6083 (4) | 0.0742 (3) | −0.10584 (18) | 0.0615 (11) | |
H27A | 0.5440 | 0.0829 | −0.1342 | 0.074* | |
H27B | 0.6647 | 0.1290 | −0.1157 | 0.074* | |
C28 | 0.6415 (5) | −0.2339 (4) | −0.1107 (2) | 0.114 (2) | |
H28A | 0.6680 | −0.2357 | −0.1530 | 0.171* | |
H28B | 0.5878 | −0.2912 | −0.1040 | 0.171* | |
H28C | 0.7058 | −0.2422 | −0.0830 | 0.171* | |
C29 | 0.4606 (4) | −0.2040 (3) | −0.0109 (2) | 0.0799 (14) | |
H29A | 0.3923 | −0.1998 | −0.0359 | 0.120* | |
H29B | 0.4406 | −0.1962 | 0.0322 | 0.120* | |
H29C | 0.4969 | −0.2724 | −0.0173 | 0.120* | |
C30 | 0.4959 (4) | 0.1934 (3) | −0.04108 (16) | 0.0479 (9) | |
C31 | 0.5087 (4) | 0.3793 (3) | −0.06002 (19) | 0.0600 (11) | |
H31A | 0.5601 | 0.4377 | −0.0491 | 0.072* | |
H31B | 0.4404 | 0.3851 | −0.0343 | 0.072* | |
C32 | 0.4757 (4) | 0.3882 (4) | −0.1274 (2) | 0.0605 (11) | |
C33 | 0.4120 (5) | 0.5073 (4) | −0.2062 (2) | 0.0857 (15) | |
H33A | 0.4706 | 0.4813 | −0.2346 | 0.103* | |
H33B | 0.3407 | 0.4698 | −0.2151 | 0.103* | |
C34 | 0.3961 (6) | 0.6224 (4) | −0.2142 (2) | 0.1113 (19) | |
H34A | 0.3488 | 0.6497 | −0.1812 | 0.167* | |
H34B | 0.3593 | 0.6359 | −0.2535 | 0.167* | |
H34C | 0.4696 | 0.6575 | −0.2134 | 0.167* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.076 (2) | 0.083 (2) | 0.0439 (16) | −0.0207 (18) | 0.0043 (15) | 0.0021 (13) |
O2 | 0.0541 (16) | 0.0551 (16) | 0.0687 (18) | −0.0096 (14) | 0.0000 (15) | 0.0092 (13) |
O3 | 0.0504 (17) | 0.0527 (15) | 0.0631 (18) | −0.0007 (14) | 0.0040 (15) | 0.0057 (13) |
O4 | 0.100 (2) | 0.0616 (18) | 0.074 (2) | 0.0112 (19) | −0.0051 (18) | 0.0084 (15) |
O5 | 0.124 (3) | 0.073 (2) | 0.0590 (18) | 0.004 (2) | 0.009 (2) | 0.0028 (16) |
C1 | 0.044 (2) | 0.043 (2) | 0.050 (2) | −0.0025 (19) | −0.0064 (19) | −0.0030 (16) |
C2 | 0.049 (2) | 0.0384 (19) | 0.052 (2) | −0.0028 (19) | −0.002 (2) | −0.0017 (16) |
C3 | 0.051 (2) | 0.054 (2) | 0.044 (2) | 0.000 (2) | 0.002 (2) | −0.0035 (17) |
C4 | 0.053 (2) | 0.053 (2) | 0.049 (2) | −0.004 (2) | −0.001 (2) | 0.0001 (18) |
C5 | 0.060 (3) | 0.061 (3) | 0.057 (2) | −0.019 (2) | 0.007 (2) | −0.004 (2) |
C6 | 0.052 (2) | 0.057 (2) | 0.048 (2) | −0.015 (2) | −0.001 (2) | −0.0026 (18) |
C7 | 0.073 (3) | 0.062 (2) | 0.062 (3) | −0.008 (2) | 0.008 (2) | −0.013 (2) |
C8 | 0.064 (3) | 0.079 (3) | 0.051 (2) | −0.012 (2) | −0.008 (2) | 0.000 (2) |
C9 | 0.066 (3) | 0.063 (3) | 0.065 (3) | 0.010 (2) | −0.012 (2) | −0.004 (2) |
C10 | 0.064 (3) | 0.054 (2) | 0.056 (2) | −0.014 (2) | −0.003 (2) | −0.0048 (19) |
C11 | 0.049 (2) | 0.058 (2) | 0.054 (2) | −0.015 (2) | 0.000 (2) | −0.0023 (18) |
C12 | 0.048 (2) | 0.046 (2) | 0.049 (2) | −0.0072 (19) | −0.0035 (19) | 0.0031 (17) |
C13 | 0.041 (2) | 0.046 (2) | 0.055 (2) | −0.0082 (18) | −0.0107 (18) | −0.0003 (18) |
C14 | 0.065 (3) | 0.050 (2) | 0.060 (2) | −0.005 (2) | 0.002 (2) | 0.0080 (19) |
C15 | 0.043 (2) | 0.045 (2) | 0.053 (2) | −0.0041 (19) | −0.0038 (19) | 0.0013 (18) |
C16 | 0.050 (2) | 0.0393 (19) | 0.046 (2) | −0.0048 (19) | −0.0056 (19) | 0.0028 (17) |
C17 | 0.051 (3) | 0.055 (2) | 0.050 (2) | −0.013 (2) | −0.010 (2) | 0.0068 (18) |
C18 | 0.052 (2) | 0.073 (3) | 0.054 (3) | −0.016 (2) | −0.004 (2) | 0.004 (2) |
C19 | 0.059 (3) | 0.067 (3) | 0.058 (3) | 0.006 (2) | −0.011 (2) | 0.003 (2) |
C20 | 0.049 (2) | 0.078 (3) | 0.053 (3) | −0.010 (2) | −0.009 (2) | −0.002 (2) |
C21 | 0.046 (2) | 0.069 (3) | 0.064 (3) | −0.005 (2) | −0.001 (2) | 0.003 (2) |
C22 | 0.049 (2) | 0.053 (2) | 0.047 (2) | 0.000 (2) | −0.004 (2) | 0.0011 (17) |
C23 | 0.045 (2) | 0.052 (2) | 0.048 (2) | 0.0040 (19) | −0.0065 (19) | 0.0016 (17) |
C24 | 0.073 (3) | 0.058 (2) | 0.062 (3) | 0.020 (2) | −0.017 (2) | −0.0056 (19) |
C25 | 0.067 (3) | 0.067 (3) | 0.081 (3) | 0.022 (3) | −0.015 (3) | −0.018 (2) |
C26 | 0.064 (3) | 0.100 (4) | 0.068 (3) | 0.014 (3) | 0.008 (3) | −0.020 (3) |
C27 | 0.051 (2) | 0.076 (3) | 0.057 (3) | 0.001 (2) | 0.006 (2) | −0.001 (2) |
C28 | 0.129 (5) | 0.093 (3) | 0.121 (5) | 0.045 (4) | 0.004 (4) | −0.029 (3) |
C29 | 0.103 (4) | 0.050 (2) | 0.087 (3) | 0.002 (3) | −0.017 (3) | 0.001 (2) |
C30 | 0.049 (3) | 0.059 (2) | 0.035 (2) | −0.008 (2) | 0.003 (2) | 0.0008 (18) |
C31 | 0.073 (3) | 0.047 (2) | 0.060 (3) | −0.008 (2) | 0.003 (2) | 0.0049 (19) |
C32 | 0.062 (3) | 0.055 (3) | 0.064 (3) | −0.007 (2) | 0.010 (2) | 0.006 (2) |
C33 | 0.090 (4) | 0.105 (4) | 0.063 (3) | 0.018 (3) | −0.001 (3) | 0.021 (3) |
C34 | 0.142 (5) | 0.093 (4) | 0.100 (4) | 0.030 (4) | 0.009 (4) | 0.036 (3) |
O1—C4 | 1.437 (4) | C15—C19 | 1.543 (5) |
O1—H1 | 0.8200 | C15—C16 | 1.545 (5) |
O2—C30 | 1.348 (4) | C16—C17 | 1.317 (5) |
O2—C31 | 1.415 (4) | C16—C23 | 1.528 (5) |
O3—C30 | 1.210 (4) | C17—C18 | 1.491 (5) |
O4—C32 | 1.319 (5) | C17—H17 | 0.9300 |
O4—C33 | 1.466 (5) | C18—H18A | 0.9700 |
O5—C32 | 1.203 (5) | C18—H18B | 0.9700 |
C1—C6 | 1.533 (5) | C19—H19A | 0.9600 |
C1—C9 | 1.543 (5) | C19—H19B | 0.9600 |
C1—C2 | 1.551 (5) | C19—H19C | 0.9600 |
C1—C13 | 1.565 (5) | C20—C21 | 1.525 (5) |
C2—C10 | 1.527 (5) | C20—H20A | 0.9700 |
C2—C3 | 1.548 (5) | C20—H20B | 0.9700 |
C2—H2 | 0.9800 | C21—C22 | 1.544 (5) |
C3—C4 | 1.531 (5) | C21—H21A | 0.9700 |
C3—C8 | 1.540 (5) | C21—H21B | 0.9700 |
C3—C7 | 1.544 (5) | C22—C30 | 1.510 (5) |
C4—C5 | 1.513 (5) | C22—C23 | 1.535 (5) |
C4—H4 | 0.9800 | C22—C27 | 1.547 (5) |
C5—C6 | 1.527 (5) | C23—C24 | 1.552 (5) |
C5—H5A | 0.9700 | C23—H23 | 0.9800 |
C5—H5B | 0.9700 | C24—C25 | 1.531 (6) |
C6—H6A | 0.9700 | C24—C29 | 1.534 (6) |
C6—H6B | 0.9700 | C24—H24 | 0.9800 |
C7—H7A | 0.9600 | C25—C26 | 1.506 (6) |
C7—H7B | 0.9600 | C25—C28 | 1.550 (5) |
C7—H7C | 0.9600 | C25—H25 | 0.9800 |
C8—H8A | 0.9600 | C26—C27 | 1.512 (5) |
C8—H8B | 0.9600 | C26—H26A | 0.9700 |
C8—H8C | 0.9600 | C26—H26B | 0.9700 |
C9—H9A | 0.9600 | C27—H27A | 0.9700 |
C9—H9B | 0.9600 | C27—H27B | 0.9700 |
C9—H9C | 0.9600 | C28—H28A | 0.9600 |
C10—C11 | 1.528 (5) | C28—H28B | 0.9600 |
C10—H10A | 0.9700 | C28—H28C | 0.9600 |
C10—H10B | 0.9700 | C29—H29A | 0.9600 |
C11—C12 | 1.546 (5) | C29—H29B | 0.9600 |
C11—H11A | 0.9700 | C29—H29C | 0.9600 |
C11—H11B | 0.9700 | C31—C32 | 1.501 (6) |
C12—C14 | 1.544 (5) | C31—H31A | 0.9700 |
C12—C13 | 1.551 (5) | C31—H31B | 0.9700 |
C12—C15 | 1.592 (5) | C33—C34 | 1.457 (6) |
C13—C18 | 1.538 (5) | C33—H33A | 0.9700 |
C13—H13 | 0.9800 | C33—H33B | 0.9700 |
C14—H14A | 0.9600 | C34—H34A | 0.9600 |
C14—H14B | 0.9600 | C34—H34B | 0.9600 |
C14—H14C | 0.9600 | C34—H34C | 0.9600 |
C15—C20 | 1.541 (5) | ||
C4—O1—H1 | 109.5 | C18—C17—H17 | 116.6 |
C30—O2—C31 | 117.1 (3) | C17—C18—C13 | 112.9 (3) |
C32—O4—C33 | 116.5 (4) | C17—C18—H18A | 109.0 |
C6—C1—C9 | 107.1 (3) | C13—C18—H18A | 109.0 |
C6—C1—C2 | 108.6 (3) | C17—C18—H18B | 109.0 |
C9—C1—C2 | 113.3 (3) | C13—C18—H18B | 109.0 |
C6—C1—C13 | 107.9 (3) | H18A—C18—H18B | 107.8 |
C9—C1—C13 | 113.1 (3) | C15—C19—H19A | 109.5 |
C2—C1—C13 | 106.7 (3) | C15—C19—H19B | 109.5 |
C10—C2—C3 | 115.6 (3) | H19A—C19—H19B | 109.5 |
C10—C2—C1 | 110.1 (3) | C15—C19—H19C | 109.5 |
C3—C2—C1 | 117.5 (3) | H19A—C19—H19C | 109.5 |
C10—C2—H2 | 103.9 | H19B—C19—H19C | 109.5 |
C3—C2—H2 | 103.9 | C21—C20—C15 | 114.7 (3) |
C1—C2—H2 | 103.9 | C21—C20—H20A | 108.6 |
C4—C3—C8 | 107.6 (3) | C15—C20—H20A | 108.6 |
C4—C3—C7 | 110.7 (3) | C21—C20—H20B | 108.6 |
C8—C3—C7 | 108.0 (3) | C15—C20—H20B | 108.6 |
C4—C3—C2 | 107.5 (3) | H20A—C20—H20B | 107.6 |
C8—C3—C2 | 108.7 (3) | C20—C21—C22 | 110.9 (3) |
C7—C3—C2 | 114.1 (3) | C20—C21—H21A | 109.5 |
O1—C4—C5 | 111.9 (3) | C22—C21—H21A | 109.5 |
O1—C4—C3 | 108.1 (3) | C20—C21—H21B | 109.5 |
C5—C4—C3 | 114.7 (3) | C22—C21—H21B | 109.5 |
O1—C4—H4 | 107.3 | H21A—C21—H21B | 108.1 |
C5—C4—H4 | 107.3 | C30—C22—C23 | 110.3 (3) |
C3—C4—H4 | 107.3 | C30—C22—C21 | 109.8 (3) |
C4—C5—C6 | 110.2 (3) | C23—C22—C21 | 109.3 (3) |
C4—C5—H5A | 109.6 | C30—C22—C27 | 104.6 (3) |
C6—C5—H5A | 109.6 | C23—C22—C27 | 111.1 (3) |
C4—C5—H5B | 109.6 | C21—C22—C27 | 111.6 (3) |
C6—C5—H5B | 109.6 | C16—C23—C22 | 111.1 (3) |
H5A—C5—H5B | 108.1 | C16—C23—C24 | 113.8 (3) |
C5—C6—C1 | 113.9 (3) | C22—C23—C24 | 113.4 (3) |
C5—C6—H6A | 108.8 | C16—C23—H23 | 105.9 |
C1—C6—H6A | 108.8 | C22—C23—H23 | 105.9 |
C5—C6—H6B | 108.8 | C24—C23—H23 | 105.9 |
C1—C6—H6B | 108.8 | C25—C24—C29 | 111.7 (3) |
H6A—C6—H6B | 107.7 | C25—C24—C23 | 111.4 (3) |
C3—C7—H7A | 109.5 | C29—C24—C23 | 110.6 (3) |
C3—C7—H7B | 109.5 | C25—C24—H24 | 107.6 |
H7A—C7—H7B | 109.5 | C29—C24—H24 | 107.6 |
C3—C7—H7C | 109.5 | C23—C24—H24 | 107.6 |
H7A—C7—H7C | 109.5 | C26—C25—C24 | 111.1 (3) |
H7B—C7—H7C | 109.5 | C26—C25—C28 | 109.3 (4) |
C3—C8—H8A | 109.5 | C24—C25—C28 | 112.1 (4) |
C3—C8—H8B | 109.5 | C26—C25—H25 | 108.1 |
H8A—C8—H8B | 109.5 | C24—C25—H25 | 108.1 |
C3—C8—H8C | 109.5 | C28—C25—H25 | 108.1 |
H8A—C8—H8C | 109.5 | C25—C26—C27 | 112.4 (3) |
H8B—C8—H8C | 109.5 | C25—C26—H26A | 109.1 |
C1—C9—H9A | 109.5 | C27—C26—H26A | 109.1 |
C1—C9—H9B | 109.5 | C25—C26—H26B | 109.1 |
H9A—C9—H9B | 109.5 | C27—C26—H26B | 109.1 |
C1—C9—H9C | 109.5 | H26A—C26—H26B | 107.9 |
H9A—C9—H9C | 109.5 | C26—C27—C22 | 113.0 (3) |
H9B—C9—H9C | 109.5 | C26—C27—H27A | 109.0 |
C2—C10—C11 | 110.7 (3) | C22—C27—H27A | 109.0 |
C2—C10—H10A | 109.5 | C26—C27—H27B | 109.0 |
C11—C10—H10A | 109.5 | C22—C27—H27B | 109.0 |
C2—C10—H10B | 109.5 | H27A—C27—H27B | 107.8 |
C11—C10—H10B | 109.5 | C25—C28—H28A | 109.5 |
H10A—C10—H10B | 108.1 | C25—C28—H28B | 109.5 |
C10—C11—C12 | 113.7 (3) | H28A—C28—H28B | 109.5 |
C10—C11—H11A | 108.8 | C25—C28—H28C | 109.5 |
C12—C11—H11A | 108.8 | H28A—C28—H28C | 109.5 |
C10—C11—H11B | 108.8 | H28B—C28—H28C | 109.5 |
C12—C11—H11B | 108.8 | C24—C29—H29A | 109.5 |
H11A—C11—H11B | 107.7 | C24—C29—H29B | 109.5 |
C14—C12—C11 | 108.6 (3) | H29A—C29—H29B | 109.5 |
C14—C12—C13 | 110.3 (3) | C24—C29—H29C | 109.5 |
C11—C12—C13 | 110.3 (3) | H29A—C29—H29C | 109.5 |
C14—C12—C15 | 110.5 (3) | H29B—C29—H29C | 109.5 |
C11—C12—C15 | 109.6 (3) | O3—C30—O2 | 121.2 (4) |
C13—C12—C15 | 107.6 (3) | O3—C30—C22 | 127.2 (4) |
C18—C13—C12 | 109.4 (3) | O2—C30—C22 | 111.5 (3) |
C18—C13—C1 | 113.3 (3) | O2—C31—C32 | 110.7 (3) |
C12—C13—C1 | 118.7 (3) | O2—C31—H31A | 109.5 |
C18—C13—H13 | 104.7 | C32—C31—H31A | 109.5 |
C12—C13—H13 | 104.7 | O2—C31—H31B | 109.5 |
C1—C13—H13 | 104.7 | C32—C31—H31B | 109.5 |
C12—C14—H14A | 109.5 | H31A—C31—H31B | 108.1 |
C12—C14—H14B | 109.5 | O5—C32—O4 | 124.6 (4) |
H14A—C14—H14B | 109.5 | O5—C32—C31 | 124.5 (4) |
C12—C14—H14C | 109.5 | O4—C32—C31 | 110.9 (4) |
H14A—C14—H14C | 109.5 | C34—C33—O4 | 108.2 (4) |
H14B—C14—H14C | 109.5 | C34—C33—H33A | 110.1 |
C20—C15—C19 | 107.6 (3) | O4—C33—H33A | 110.1 |
C20—C15—C16 | 111.2 (3) | C34—C33—H33B | 110.1 |
C19—C15—C16 | 107.4 (3) | O4—C33—H33B | 110.1 |
C20—C15—C12 | 109.7 (3) | H33A—C33—H33B | 108.4 |
C19—C15—C12 | 112.1 (3) | C33—C34—H34A | 109.5 |
C16—C15—C12 | 108.8 (3) | C33—C34—H34B | 109.5 |
C17—C16—C23 | 119.7 (3) | H34A—C34—H34B | 109.5 |
C17—C16—C15 | 120.7 (3) | C33—C34—H34C | 109.5 |
C23—C16—C15 | 119.6 (3) | H34A—C34—H34C | 109.5 |
C16—C17—C18 | 126.8 (4) | H34B—C34—H34C | 109.5 |
C16—C17—H17 | 116.6 | ||
C6—C1—C2—C10 | 174.9 (3) | C20—C15—C16—C23 | 36.8 (4) |
C9—C1—C2—C10 | −66.1 (4) | C19—C15—C16—C23 | −80.7 (4) |
C13—C1—C2—C10 | 58.9 (3) | C12—C15—C16—C23 | 157.7 (3) |
C6—C1—C2—C3 | −49.9 (4) | C23—C16—C17—C18 | 177.5 (3) |
C9—C1—C2—C3 | 69.0 (4) | C15—C16—C17—C18 | −0.7 (6) |
C13—C1—C2—C3 | −165.9 (3) | C16—C17—C18—C13 | −7.3 (6) |
C10—C2—C3—C4 | −177.0 (3) | C12—C13—C18—C17 | 40.4 (4) |
C1—C2—C3—C4 | 50.2 (4) | C1—C13—C18—C17 | 175.2 (3) |
C10—C2—C3—C8 | −60.8 (4) | C19—C15—C20—C21 | 75.6 (4) |
C1—C2—C3—C8 | 166.4 (3) | C16—C15—C20—C21 | −41.8 (4) |
C10—C2—C3—C7 | 59.8 (4) | C12—C15—C20—C21 | −162.2 (3) |
C1—C2—C3—C7 | −73.0 (4) | C15—C20—C21—C22 | 56.4 (4) |
C8—C3—C4—O1 | 64.5 (4) | C20—C21—C22—C30 | 59.1 (4) |
C7—C3—C4—O1 | −53.3 (4) | C20—C21—C22—C23 | −62.0 (4) |
C2—C3—C4—O1 | −178.6 (3) | C20—C21—C22—C27 | 174.6 (3) |
C8—C3—C4—C5 | −170.0 (3) | C17—C16—C23—C22 | 137.4 (4) |
C7—C3—C4—C5 | 72.2 (4) | C15—C16—C23—C22 | −44.5 (4) |
C2—C3—C4—C5 | −53.0 (4) | C17—C16—C23—C24 | −93.2 (4) |
O1—C4—C5—C6 | −179.0 (3) | C15—C16—C23—C24 | 85.0 (4) |
C3—C4—C5—C6 | 57.5 (4) | C30—C22—C23—C16 | −66.1 (4) |
C4—C5—C6—C1 | −56.1 (4) | C21—C22—C23—C16 | 54.8 (4) |
C9—C1—C6—C5 | −71.5 (4) | C27—C22—C23—C16 | 178.4 (3) |
C2—C1—C6—C5 | 51.2 (4) | C30—C22—C23—C24 | 164.3 (3) |
C13—C1—C6—C5 | 166.4 (3) | C21—C22—C23—C24 | −74.9 (4) |
C3—C2—C10—C11 | 159.2 (3) | C27—C22—C23—C24 | 48.8 (4) |
C1—C2—C10—C11 | −64.7 (4) | C16—C23—C24—C25 | −179.9 (4) |
C2—C10—C11—C12 | 56.7 (4) | C22—C23—C24—C25 | −51.7 (4) |
C10—C11—C12—C14 | 76.7 (4) | C16—C23—C24—C29 | 55.2 (4) |
C10—C11—C12—C13 | −44.3 (4) | C22—C23—C24—C29 | −176.5 (3) |
C10—C11—C12—C15 | −162.5 (3) | C29—C24—C25—C26 | 178.9 (3) |
C14—C12—C13—C18 | 55.5 (4) | C23—C24—C25—C26 | 54.6 (5) |
C11—C12—C13—C18 | 175.4 (3) | C29—C24—C25—C28 | −58.6 (5) |
C15—C12—C13—C18 | −65.1 (4) | C23—C24—C25—C28 | 177.2 (4) |
C14—C12—C13—C1 | −76.6 (4) | C24—C25—C26—C27 | −56.9 (5) |
C11—C12—C13—C1 | 43.4 (4) | C28—C25—C26—C27 | 178.9 (4) |
C15—C12—C13—C1 | 162.9 (3) | C25—C26—C27—C22 | 55.1 (5) |
C6—C1—C13—C18 | 62.5 (4) | C30—C22—C27—C26 | −169.3 (3) |
C9—C1—C13—C18 | −55.8 (4) | C23—C22—C27—C26 | −50.2 (5) |
C2—C1—C13—C18 | 179.1 (3) | C21—C22—C27—C26 | 72.1 (4) |
C6—C1—C13—C12 | −167.1 (3) | C31—O2—C30—O3 | −5.0 (5) |
C9—C1—C13—C12 | 74.6 (4) | C31—O2—C30—C22 | 171.6 (3) |
C2—C1—C13—C12 | −50.6 (4) | C23—C22—C30—O3 | −15.3 (5) |
C14—C12—C15—C20 | 57.2 (4) | C21—C22—C30—O3 | −135.9 (4) |
C11—C12—C15—C20 | −62.4 (4) | C27—C22—C30—O3 | 104.2 (4) |
C13—C12—C15—C20 | 177.6 (3) | C23—C22—C30—O2 | 168.3 (3) |
C14—C12—C15—C19 | 176.7 (3) | C21—C22—C30—O2 | 47.8 (4) |
C11—C12—C15—C19 | 57.1 (4) | C27—C22—C30—O2 | −72.1 (4) |
C13—C12—C15—C19 | −62.8 (4) | C30—O2—C31—C32 | −80.2 (4) |
C14—C12—C15—C16 | −64.7 (3) | C33—O4—C32—O5 | 0.6 (7) |
C11—C12—C15—C16 | 175.7 (3) | C33—O4—C32—C31 | −179.6 (4) |
C13—C12—C15—C16 | 55.8 (3) | O2—C31—C32—O5 | 13.2 (6) |
C20—C15—C16—C17 | −145.1 (4) | O2—C31—C32—O4 | −166.6 (3) |
C19—C15—C16—C17 | 97.4 (4) | C32—O4—C33—C34 | −173.9 (4) |
C12—C15—C16—C17 | −24.1 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O3i | 0.82 | 2.14 | 2.944 (4) | 165 |
Symmetry code: (i) −x+1/2, −y, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C34H54O5 |
Mr | 542.77 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 292 |
a, b, c (Å) | 11.624 (3), 12.465 (4), 21.478 (3) |
V (Å3) | 3112.0 (14) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.60 × 0.56 × 0.44 |
Data collection | |
Diffractometer | Enraf–Nonius CAD-4 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3435, 3116, 1818 |
Rint | 0.009 |
(sin θ/λ)max (Å−1) | 0.600 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.125, 0.97 |
No. of reflections | 3116 |
No. of parameters | 362 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.19, −0.17 |
Computer programs: DIFRAC (Gabe & White, 1993), NRCVAX (Gabe et al., 1989), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997).
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O3i | 0.82 | 2.14 | 2.944 (4) | 165.1 |
Symmetry code: (i) −x+1/2, −y, z+1/2. |
Acknowledgements
The authors thank Mr Zhi-Hua Mao of Sichuan University for the X-ray data collection.
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Ursolic acid, a pentacyclic triterpene existing abundantly in the plant kingdom, has been reported to possess pharmacological activities, such as anti-tumor, anti-inflammatory and anti-HIV activities (Es-saady et al., 1996; Kashiwada et al., 2000). The synthesis and characterization of some derivatives of this compound have been recently reported (Liu et al., 2007). We report herein the crystal structure of the title compound, whose synthetic method has been already reported elsewhere (Yang et al., 2008).
In the molecule of the title compound (Fig.1) bond lengths and angles within the six-membered rings are very similar to those given in the literature for ursolic acid (Simon et al., 1992). The C(sp2)—C(sp2) bond distance (C16—C17) is 1.317 (5) Å, the C(sp3)—C(sp3) bond lengths range from 1.506 (6) Å to 1.592 (5) Å, and the three C(sp3)—C(sp2) bond distances (C17—C18, C16—C23 and C16—C15) are 1.491 (5), 1.528 (5) and 1.545 (5) Å, respectively. The five six-membered rings adopt a chair conformation. The carboxy group at C22 and the methyl groups C7, C9, C14 and C19 are axially oriented, while the hydroxy groups and the methyl groups C8, C28 and C29 are in equatorial positions. The O2–C30–C22–C27 and C2–C30–C22–C21 torsion angles are -72.1 (4) Å and 47.8 Å, respectively. In the crystal packing, intermolecular O—H···O hydrogen bonds (Table 1) link molecules to form zig-zag chains extending along the c axis.