Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102001002/av1099sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102001002/av1099IIsup2.hkl |
CCDC reference: 164256
Compound (II) was synthesized according to the method described by Egorov, Grinenko et al. (2001). Is this the correct reference? Colourless crystals of (II) suitable for diffraction analysis were obtained from hexane-ethyl acetate solution by slow evaporation at room temperature.
H atoms were treated as riding, with O—H = 0.82 Å and C—H = 0.93–0.98 Å, and Uiso(H) = 1.5Ueq of the parent atom. Are these the correct restraints?
Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SHELXTL (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Please provide missing details.
Fig. 1. The asymmetric unit of (II) with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. |
C20H30O2 | F(000) = 664 |
Mr = 302.44 | Dx = 1.203 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 6.957 (2) Å | Cell parameters from 612 reflections |
b = 12.035 (3) Å | θ = 2.5–23.1° |
c = 19.950 (6) Å | µ = 0.08 mm−1 |
β = 90.100 (6)° | T = 293 K |
V = 1670.4 (8) Å3 | Plate, colourless |
Z = 4 | 0.4 × 0.3 × 0.1 mm |
Bruker SMART 1000 CCD area-detector diffractometer | 1587 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.047 |
Graphite monochromator | θmax = 25.0°, θmin = 2.0° |
ϕ and ω scans | h = −8→7 |
7713 measured reflections | k = −13→14 |
2925 independent reflections | l = −23→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)] = 0.061 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.164 | H-atom parameters constrained |
S = 0.91 | w = 1/[σ2(Fo2) + (0.0886P)2] where P = (Fo2 + 2Fc2)/3 |
2925 reflections | (Δ/σ)max < 0.001 |
199 parameters | Δρmax = 0.34 e Å−3 |
0 restraints | Δρmin = −0.21 e Å−3 |
C20H30O2 | V = 1670.4 (8) Å3 |
Mr = 302.44 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 6.957 (2) Å | µ = 0.08 mm−1 |
b = 12.035 (3) Å | T = 293 K |
c = 19.950 (6) Å | 0.4 × 0.3 × 0.1 mm |
β = 90.100 (6)° |
Bruker SMART 1000 CCD area-detector diffractometer | 1587 reflections with I > 2σ(I) |
7713 measured reflections | Rint = 0.047 |
2925 independent reflections |
R[F2 > 2σ(F2)] = 0.061 | 0 restraints |
wR(F2) = 0.164 | H-atom parameters constrained |
S = 0.91 | Δρmax = 0.34 e Å−3 |
2925 reflections | Δρmin = −0.21 e Å−3 |
199 parameters |
Experimental. Egorov, M. S., Starova, G. L. & Shavva, A. G. (2001). Collected Abstacts of the Third National Conference of X-ray Synchrotron Radiation of Neutrons and Electrons to the Investigation of Materials. Rne, Moscow, p.69. (In Russian). |
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 | 0.0185 (3) | 0.20907 (15) | 1.07510 (9) | 0.0388 (5) | |
O2 | 0.1301 (3) | 0.22146 (14) | 0.57850 (9) | 0.0388 (5) | |
HO2 | 0.2469 | 0.2298 | 0.5806 | 0.058* | |
C1 | 0.3486 (4) | 0.1225 (2) | 0.94397 (12) | 0.0329 (7) | |
H1A | 0.3620 | 0.1981 | 0.9277 | 0.049* | |
H1B | 0.4738 | 0.0871 | 0.9421 | 0.049* | |
C2 | 0.2766 (4) | 0.1240 (2) | 1.01619 (13) | 0.0326 (7) | |
H2A | 0.2806 | 0.0491 | 1.0341 | 0.049* | |
H2B | 0.3620 | 0.1697 | 1.0431 | 0.049* | |
C3 | 0.0762 (4) | 0.1681 (2) | 1.02202 (14) | 0.0310 (7) | |
C4 | −0.0510 (4) | 0.1559 (2) | 0.96449 (13) | 0.0322 (7) | |
H4 | −0.1747 | 0.1849 | 0.9665 | 0.048* | |
C5 | 0.0069 (4) | 0.1035 (2) | 0.90854 (13) | 0.0309 (6) | |
C6 | −0.1073 (4) | 0.0827 (2) | 0.84564 (13) | 0.0355 (7) | |
H6A | −0.1497 | 0.1520 | 0.8258 | 0.053* | |
H6B | −0.2188 | 0.0368 | 0.8549 | 0.053* | |
C8 | 0.0353 (4) | 0.0214 (2) | 0.79882 (13) | 0.0310 (7) | |
H8 | 0.0245 | −0.0579 | 0.8092 | 0.046* | |
C9 | 0.2347 (4) | 0.0588 (2) | 0.82350 (12) | 0.0305 (6) | |
H9 | 0.3311 | 0.0031 | 0.8112 | 0.046* | |
C10 | 0.2081 (4) | 0.0596 (2) | 0.90007 (13) | 0.0310 (7) | |
H10 | 0.2080 | −0.0179 | 0.9151 | 0.047* | |
C11 | 0.2908 (4) | 0.1718 (2) | 0.79422 (12) | 0.0333 (7) | |
H11A | 0.2084 | 0.2289 | 0.8130 | 0.050* | |
H11B | 0.4223 | 0.1888 | 0.8068 | 0.050* | |
C12 | 0.2729 (4) | 0.1729 (2) | 0.71805 (13) | 0.0333 (7) | |
H12A | 0.3631 | 0.1197 | 0.6996 | 0.050* | |
H12B | 0.3089 | 0.2459 | 0.7017 | 0.050* | |
C13 | 0.0705 (4) | 0.1451 (2) | 0.69203 (13) | 0.0296 (6) | |
C14 | 0.0092 (4) | 0.0327 (2) | 0.72298 (13) | 0.0303 (6) | |
H14 | 0.0984 | −0.0217 | 0.7038 | 0.045* | |
C15 | −0.1887 (4) | −0.0039 (2) | 0.69833 (13) | 0.0321 (7) | |
H15A | −0.2833 | 0.0505 | 0.7122 | 0.048* | |
H15B | −0.2215 | −0.0741 | 0.7193 | 0.048* | |
C16 | −0.1988 (4) | −0.0175 (2) | 0.62205 (13) | 0.0322 (7) | |
C16A | −0.0871 (4) | −0.1202 (2) | 0.59997 (13) | 0.0377 (7) | |
H161 | 0.0452 | −0.1125 | 0.6130 | 0.056* | |
H162 | −0.0954 | −0.1277 | 0.5521 | 0.056* | |
H163 | −0.1407 | −0.1849 | 0.6209 | 0.056* | |
C16B | −0.4065 (4) | −0.0335 (2) | 0.59954 (14) | 0.0380 (7) | |
H164 | −0.4099 | −0.0474 | 0.5522 | 0.057* | |
H165 | −0.4790 | 0.0324 | 0.6094 | 0.057* | |
H166 | −0.4615 | −0.0956 | 0.6229 | 0.057* | |
C17 | −0.1173 (4) | 0.0879 (2) | 0.58883 (13) | 0.0322 (7) | |
H17A | −0.1052 | 0.0745 | 0.5411 | 0.048* | |
H17B | −0.2087 | 0.1480 | 0.5948 | 0.048* | |
C17A | 0.0763 (4) | 0.1249 (2) | 0.61589 (13) | 0.0308 (6) | |
H171 | 0.1702 | 0.0661 | 0.6068 | 0.046* | |
C18 | −0.0627 (4) | 0.2438 (2) | 0.70704 (14) | 0.0365 (7) | |
H181 | −0.1937 | 0.2225 | 0.6990 | 0.055* | |
H182 | −0.0297 | 0.3051 | 0.6784 | 0.055* | |
H183 | −0.0478 | 0.2656 | 0.7531 | 0.055* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0342 (12) | 0.0441 (12) | 0.0380 (12) | −0.0042 (9) | 0.0043 (9) | −0.0072 (9) |
O2 | 0.0315 (11) | 0.0428 (12) | 0.0420 (12) | −0.0037 (9) | 0.0012 (9) | 0.0122 (9) |
C1 | 0.0276 (16) | 0.0337 (15) | 0.0375 (17) | −0.0005 (12) | 0.0005 (12) | 0.0022 (12) |
C2 | 0.0315 (17) | 0.0316 (15) | 0.0348 (16) | −0.0017 (12) | 0.0009 (13) | −0.0003 (12) |
C3 | 0.0320 (17) | 0.0257 (14) | 0.0352 (16) | −0.0073 (12) | 0.0019 (13) | −0.0018 (12) |
C4 | 0.0267 (16) | 0.0311 (15) | 0.0389 (17) | −0.0015 (12) | 0.0003 (12) | 0.0006 (12) |
C5 | 0.0303 (16) | 0.0295 (15) | 0.0328 (16) | −0.0063 (12) | −0.0005 (12) | 0.0027 (12) |
C6 | 0.0279 (16) | 0.0445 (17) | 0.0342 (16) | −0.0048 (13) | 0.0012 (12) | 0.0002 (13) |
C8 | 0.0311 (16) | 0.0281 (15) | 0.0338 (16) | −0.0037 (11) | 0.0029 (12) | −0.0003 (11) |
C9 | 0.0270 (15) | 0.0316 (15) | 0.0329 (16) | 0.0028 (12) | 0.0036 (12) | −0.0036 (11) |
C10 | 0.0293 (16) | 0.0296 (14) | 0.0342 (16) | −0.0015 (12) | 0.0037 (12) | 0.0028 (11) |
C11 | 0.0246 (16) | 0.0379 (16) | 0.0375 (17) | −0.0006 (12) | 0.0028 (12) | −0.0013 (12) |
C12 | 0.0305 (16) | 0.0355 (15) | 0.0338 (16) | −0.0041 (12) | 0.0022 (12) | 0.0032 (12) |
C13 | 0.0240 (15) | 0.0313 (15) | 0.0336 (16) | 0.0008 (11) | 0.0006 (12) | −0.0001 (11) |
C14 | 0.0285 (15) | 0.0285 (14) | 0.0338 (16) | 0.0004 (11) | 0.0006 (12) | −0.0009 (11) |
C15 | 0.0291 (16) | 0.0303 (15) | 0.0369 (17) | −0.0042 (12) | 0.0052 (13) | 0.0012 (11) |
C16 | 0.0269 (16) | 0.0370 (16) | 0.0328 (16) | 0.0005 (12) | 0.0018 (12) | −0.0004 (12) |
C16A | 0.0390 (18) | 0.0367 (16) | 0.0373 (17) | 0.0007 (13) | −0.0009 (13) | −0.0024 (12) |
C16B | 0.0331 (17) | 0.0441 (17) | 0.0368 (17) | −0.0005 (13) | 0.0024 (13) | −0.0036 (13) |
C17 | 0.0277 (16) | 0.0349 (16) | 0.0341 (16) | 0.0041 (12) | 0.0013 (12) | −0.0011 (12) |
C17A | 0.0285 (16) | 0.0293 (15) | 0.0347 (16) | 0.0007 (12) | 0.0046 (12) | 0.0054 (12) |
C18 | 0.0379 (18) | 0.0317 (15) | 0.0400 (17) | 0.0030 (13) | −0.0016 (13) | −0.0024 (12) |
O1—C3 | 1.236 (3) | C12—C13 | 1.536 (4) |
O2—C17A | 1.432 (3) | C12—H12A | 0.9700 |
O2—HO2 | 0.8200 | C12—H12B | 0.9700 |
C1—C10 | 1.515 (4) | C13—C18 | 1.537 (3) |
C1—C2 | 1.526 (4) | C13—C17A | 1.539 (4) |
C1—H1A | 0.9700 | C13—C14 | 1.547 (3) |
C1—H1B | 0.9700 | C14—C15 | 1.526 (3) |
C2—C3 | 1.496 (4) | C14—H14 | 0.9800 |
C2—H2A | 0.9700 | C15—C16 | 1.532 (3) |
C2—H2B | 0.9700 | C15—H15A | 0.9700 |
C3—C4 | 1.455 (4) | C15—H15B | 0.9700 |
C4—C5 | 1.344 (4) | C16—C16B | 1.525 (4) |
C4—H4 | 0.9300 | C16—C16A | 1.525 (4) |
C5—C6 | 1.505 (4) | C16—C17 | 1.539 (4) |
C5—C10 | 1.506 (4) | C16A—H161 | 0.9600 |
C6—C8 | 1.550 (4) | C16A—H162 | 0.9600 |
C6—H6A | 0.9700 | C16A—H163 | 0.9600 |
C6—H6B | 0.9700 | C16B—H164 | 0.9600 |
C8—C14 | 1.530 (4) | C16B—H165 | 0.9600 |
C8—C9 | 1.538 (4) | C16B—H166 | 0.9600 |
C8—H8 | 0.9800 | C17—C17A | 1.517 (4) |
C9—C11 | 1.530 (3) | C17—H17A | 0.9700 |
C9—C10 | 1.539 (3) | C17—H17B | 0.9700 |
C9—H9 | 0.9800 | C17A—H171 | 0.9800 |
C10—H10 | 0.9800 | C18—H181 | 0.9600 |
C11—C12 | 1.525 (3) | C18—H182 | 0.9600 |
C11—H11A | 0.9700 | C18—H183 | 0.9600 |
C11—H11B | 0.9700 | ||
C17A—O2—HO2 | 109.5 | C13—C12—H12B | 108.7 |
C10—C1—C2 | 109.8 (2) | H12A—C12—H12B | 107.6 |
C10—C1—H1A | 109.7 | C12—C13—C18 | 108.6 (2) |
C2—C1—H1A | 109.7 | C12—C13—C17A | 110.0 (2) |
C10—C1—H1B | 109.7 | C18—C13—C17A | 109.3 (2) |
C2—C1—H1B | 109.7 | C12—C13—C14 | 108.0 (2) |
H1A—C1—H1B | 108.2 | C18—C13—C14 | 115.6 (2) |
C3—C2—C1 | 112.6 (2) | C17A—C13—C14 | 105.3 (2) |
C3—C2—H2A | 109.1 | C15—C14—C8 | 113.5 (2) |
C1—C2—H2A | 109.1 | C15—C14—C13 | 111.9 (2) |
C3—C2—H2B | 109.1 | C8—C14—C13 | 116.1 (2) |
C1—C2—H2B | 109.1 | C15—C14—H14 | 104.6 |
H2A—C2—H2B | 107.8 | C8—C14—H14 | 104.6 |
O1—C3—C4 | 121.2 (3) | C13—C14—H14 | 104.6 |
O1—C3—C2 | 120.8 (2) | C14—C15—C16 | 113.0 (2) |
C4—C3—C2 | 117.9 (2) | C14—C15—H15A | 109.0 |
C5—C4—C3 | 121.3 (3) | C16—C15—H15A | 109.0 |
C5—C4—H4 | 119.3 | C14—C15—H15B | 109.0 |
C3—C4—H4 | 119.3 | C16—C15—H15B | 109.0 |
C4—C5—C6 | 127.7 (3) | H15A—C15—H15B | 107.8 |
C4—C5—C10 | 122.5 (2) | C16B—C16—C16A | 107.2 (2) |
C6—C5—C10 | 109.7 (2) | C16B—C16—C15 | 110.4 (2) |
C5—C6—C8 | 104.1 (2) | C16A—C16—C15 | 110.5 (2) |
C5—C6—H6A | 110.9 | C16B—C16—C17 | 109.1 (2) |
C8—C6—H6A | 110.9 | C16A—C16—C17 | 110.8 (2) |
C5—C6—H6B | 110.9 | C15—C16—C17 | 108.9 (2) |
C8—C6—H6B | 110.9 | C16—C16A—H161 | 109.5 |
H6A—C6—H6B | 108.9 | C16—C16A—H162 | 109.5 |
C14—C8—C9 | 113.3 (2) | H161—C16A—H162 | 109.5 |
C14—C8—C6 | 118.6 (2) | C16—C16A—H163 | 109.5 |
C9—C8—C6 | 104.2 (2) | H161—C16A—H163 | 109.5 |
C14—C8—H8 | 106.6 | H162—C16A—H163 | 109.5 |
C9—C8—H8 | 106.6 | C16—C16B—H164 | 109.5 |
C6—C8—H8 | 106.6 | C16—C16B—H165 | 109.5 |
C11—C9—C8 | 111.6 (2) | H164—C16B—H165 | 109.5 |
C11—C9—C10 | 113.9 (2) | C16—C16B—H166 | 109.5 |
C8—C9—C10 | 102.1 (2) | H164—C16B—H166 | 109.5 |
C11—C9—H9 | 109.7 | H165—C16B—H166 | 109.5 |
C8—C9—H9 | 109.7 | C17A—C17—C16 | 114.6 (2) |
C10—C9—H9 | 109.7 | C17A—C17—H17A | 108.6 |
C5—C10—C1 | 111.0 (2) | C16—C17—H17A | 108.6 |
C5—C10—C9 | 103.1 (2) | C17A—C17—H17B | 108.6 |
C1—C10—C9 | 119.9 (2) | C16—C17—H17B | 108.6 |
C5—C10—H10 | 107.4 | H17A—C17—H17B | 107.6 |
C1—C10—H10 | 107.4 | O2—C17A—C17 | 106.6 (2) |
C9—C10—H10 | 107.4 | O2—C17A—C13 | 113.2 (2) |
C12—C11—C9 | 111.6 (2) | C17—C17A—C13 | 111.9 (2) |
C12—C11—H11A | 109.3 | O2—C17A—H171 | 108.3 |
C9—C11—H11A | 109.3 | C17—C17A—H171 | 108.3 |
C12—C11—H11B | 109.3 | C13—C17A—H171 | 108.3 |
C9—C11—H11B | 109.3 | C13—C18—H181 | 109.5 |
H11A—C11—H11B | 108.0 | C13—C18—H182 | 109.5 |
C11—C12—C13 | 114.1 (2) | H181—C18—H182 | 109.5 |
C11—C12—H12A | 108.7 | C13—C18—H183 | 109.5 |
C13—C12—H12A | 108.7 | H181—C18—H183 | 109.5 |
C11—C12—H12B | 108.7 | H182—C18—H183 | 109.5 |
C10—C1—C2—C3 | −54.1 (3) | C11—C12—C13—C17A | −168.5 (2) |
C1—C2—C3—O1 | −156.0 (2) | C11—C12—C13—C14 | −54.1 (3) |
C1—C2—C3—C4 | 27.1 (3) | C9—C8—C14—C15 | −179.8 (2) |
O1—C3—C4—C5 | −174.7 (2) | C6—C8—C14—C15 | −57.1 (3) |
C2—C3—C4—C5 | 2.2 (4) | C9—C8—C14—C13 | −48.0 (3) |
C3—C4—C5—C6 | 179.0 (2) | C6—C8—C14—C13 | 74.7 (3) |
C3—C4—C5—C10 | −3.3 (4) | C12—C13—C14—C15 | −178.3 (2) |
C4—C5—C6—C8 | 179.0 (2) | C18—C13—C14—C15 | 60.0 (3) |
C10—C5—C6—C8 | 1.0 (3) | C17A—C13—C14—C15 | −60.8 (3) |
C5—C6—C8—C14 | −152.4 (2) | C12—C13—C14—C8 | 49.2 (3) |
C5—C6—C8—C9 | −25.3 (3) | C18—C13—C14—C8 | −72.5 (3) |
C14—C8—C9—C11 | 47.9 (3) | C17A—C13—C14—C8 | 166.8 (2) |
C6—C8—C9—C11 | −82.4 (2) | C8—C14—C15—C16 | −167.0 (2) |
C14—C8—C9—C10 | 170.0 (2) | C13—C14—C15—C16 | 59.2 (3) |
C6—C8—C9—C10 | 39.6 (2) | C14—C15—C16—C16B | −169.8 (2) |
C4—C5—C10—C1 | −25.0 (3) | C14—C15—C16—C16A | 71.8 (3) |
C6—C5—C10—C1 | 153.1 (2) | C14—C15—C16—C17 | −50.1 (3) |
C4—C5—C10—C9 | −154.6 (2) | C16B—C16—C17—C17A | 170.0 (2) |
C6—C5—C10—C9 | 23.5 (3) | C16A—C16—C17—C17A | −72.2 (3) |
C2—C1—C10—C5 | 52.2 (3) | C15—C16—C17—C17A | 49.5 (3) |
C2—C1—C10—C9 | 172.2 (2) | C16—C17—C17A—O2 | 178.8 (2) |
C11—C9—C10—C5 | 82.1 (3) | C16—C17—C17A—C13 | −56.9 (3) |
C8—C9—C10—C5 | −38.4 (2) | C12—C13—C17A—O2 | −64.2 (3) |
C11—C9—C10—C1 | −41.9 (3) | C18—C13—C17A—O2 | 54.9 (3) |
C8—C9—C10—C1 | −162.3 (2) | C14—C13—C17A—O2 | 179.7 (2) |
C8—C9—C11—C12 | −52.7 (3) | C12—C13—C17A—C17 | 175.3 (2) |
C10—C9—C11—C12 | −167.6 (2) | C18—C13—C17A—C17 | −65.5 (3) |
C9—C11—C12—C13 | 58.1 (3) | C14—C13—C17A—C17 | 59.2 (3) |
C11—C12—C13—C18 | 71.9 (3) |
Experimental details
Crystal data | |
Chemical formula | C20H30O2 |
Mr | 302.44 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 6.957 (2), 12.035 (3), 19.950 (6) |
β (°) | 90.100 (6) |
V (Å3) | 1670.4 (8) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.4 × 0.3 × 0.1 |
Data collection | |
Diffractometer | Bruker SMART 1000 CCD area-detector diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7713, 2925, 1587 |
Rint | 0.047 |
(sin θ/λ)max (Å−1) | 0.596 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.061, 0.164, 0.91 |
No. of reflections | 2925 |
No. of parameters | 199 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.34, −0.21 |
Computer programs: SMART (Bruker, 1997), SMART, SHELXTL (Bruker, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), Please provide missing details.
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Steroid estrogen B-nor-8-isoanalogues are known to have more favourable biological properties than the natural hormones (Name et al., 1970). Similar androgen steroids have remained practically uninvestigated. The Birch reduction of 17β-hydroxy-18-methyl-3-methoxy-B-nor-8-isoestra-1,3,5(10)-triene and subsequent acid hydrolysis were reported to give only 16,16-dimethyl-D-homo-19,B-dinor-8-isotestosterone, (II), whose structure has been reported previously by Rao et al. (1977) but which has not been strictly established. The object of the present investigation is the determination of the configuration at C10, since this is critical for revealing structure-activity relationships.
We decided to carry out the Birch reduction (see Scheme) of 17aβ-acetoxy-16,16-dimethyl-3-methoxy-D-homo-B-nor-8-isoestra-1,3,5(10)- triene, (I), because, according to our data, it does not have any uterotropic activity at doses up to 100 mg kg-1 of body weight per day. The oestrogen- and androgen-receptor hormone-binding domains being similar (Ekena et al., 1998), we expect that the final androgen analogue, (II), will not have hormonal activity, and it will be possible to evaluate the convenience of such compounds for the realisation of nongenomic mechanisms of action. \sch
The synthesis of (II) has been described earlier by Egorov, Grinenko et al. (2001). Is this the correct reference? By means of the present X-ray analysis, the conformation of (II) in the solid state has now been determined (Fig. 1).
Ring B is a 9β-envelope, and the angle between the C5/C6/C8/C10 and C8/C9/C10 planes is 39.7°. Ring C is a half-chair, and the angle between the C2/C3/C4/C5/C10 and C1/C2/C10 planes is 48.4°. Atoms H1β and H2α are pseudo-axial. All chiral centres have the S-configuration. Rings B and C possess a cis-junction which causes the rings to be folded; this is usual for 8-isoanalogue molecules. The angle between the planes containing rings A and B (the angle between the C2/C3/C4/C5/C10 and C5/C6/C8/C10 planes is 0.8°), and C and D (the angle between planes C9/C11/C13/C14 and C13/C14/C16/C17 is 7.7°) is 91.1°.
In the crystal structure of (II), two molecules are joined by O2—HO2···O1 hydrogen bonds, with O1···O2 2.829 Å, HO2···O1 2.030 Å and O2—HO2···O1 164.58°. Positional parameters, bond lengths and angles, and torsion angles have been deposited in the Cambridge Crystallographic Database, No. 164256. Using correlation NMR spectroscopy, we also found that (II) in chloroform solution has the same structure as that reported by Egorov, Grinenko et al. (2001). Is this the correct reference?
As we have stated, H10 has an α orientation, contrary to the assumption of Rao et al. (1977), who synthesized a similar 19,B-dinoranalogue with a five-membered D ring and a methyl group at C18. We reproduced their synthesis and proved by correlation NMR spectroscopy that the orientation of H10 was α (Egorov, Starova & Shavva, 2001). Is this the correct reference? Our results are in agreement with data published by Banerjee et al. (1969), concerning an analogous synthesis and X-ray structure determination of a six-membered B-ring analogue of (II).
In the light of these results, we can conclude that the Birch reduction of 3-methoxy-B-nor-8-isoestra-1,3,5(10)-trienes followed by acid hydrolysis produces steroid androgen 19,B-dinor-8,10-isoanalogues, irrespective of the size and substitutions of ring D.
There are two different Egorov et al. (2001) references. Please make sure that each citation above is correct.