3-Meth­oxy­methyl-16β,17β-epiestriol-16β,17β-diyl sulfate

Jian-Jun Chen; Hai-Dong Wang; Cheng Yao

doi:10.1107/S1600536811039213

. 2011 Oct 12;67(Pt 11):o2910. doi: 10.1107/S1600536811039213

3-Methoxymethyl-16β,17β-epiestriol-16β,17β-diyl sulfate

Jian-Jun Chen ^a, Hai-Dong Wang ^a, Cheng Yao ^a,^*

PMCID: PMC3247325 PMID: 22219943

Abstract

The title compound, C₂₀H₂₆O₆S, synthesized by the reaction of 3-O-methoxymethyl-16β-epiestriol and sulfonyldiimidazole, is composed of a 3-methoxymethyl group connected via two O atoms to a 16,17-O-sulfuryl-16-epiestriol group. In the crystal, weak intermolecular C—H⋯O hydrogen bonds link the molecules into [001] chains.

Related literature

We have used the title compound as a substrate for the production of F-18 16α-fluoroestradiol via nucleophilic fluorination, see: Romer et al. (1996 ▶). Fluorine-18 16α-fluoroestradiol is a valuable radiopharmaceutical for the investigation of the estrogen receptor status of primary and metastatic breast cancer, see: Lim et al. (1996 ▶); Romer et al. (1996 ▶). For bond-length data, see: Allen et al. (2002 ▶).

Experimental

Crystal data

C₂₀H₂₆O₆S
M _r = 394.47
Orthorhombic,
a = 10.296 (2) Å
b = 23.503 (5) Å
c = 7.9060 (16) Å
V = 1913.1 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.20 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ▶) T _min = 0.942, T _max = 0.980
3875 measured reflections
3530 independent reflections
2174 reflections with I > 2σ(I)
R _int = 0.060
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F ² > 2σ(F ²)] = 0.064
wR(F ²) = 0.182
S = 1.00
3530 reflections
244 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.17 e Å⁻³
Absolute structure: Flack (1983 ▶), 1483 Friedel pairs
Flack parameter: 0.00 (18)

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ▶); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo,1995 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811039213/bq2303sup1.cif

e-67-o2910-sup1.cif^{(22.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811039213/bq2303Isup2.hkl

e-67-o2910-Isup2.hkl^{(173.1KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C20—H20A⋯O3ⁱ	0.96	2.50	3.338 (5)	146

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors would like to thank Professor Hua-qin Wang of Nanjing University for carrying out the X-ray crystallographic analysis.

supplementary crystallographic information

Comment

Fluorine-18 16alpha-fluoroestradiol has proven to be a valuable radiopharmaceuticalfor the investigation of the estrogen receptor status of primary and metastatic breast cancer. (Lim et al.,1996; Romer et al.,1996). We have prepared 3-methoxymethyl-16β,17β-epiestriol-O-cyclic sulfone and used it as a substrate for the production of F-18 16alpha-fluoroestradiol, via nucleophilic fluorination with fluoride ion. (Romer et al.,1996).

We report here the crystal structure of the titled compound, (I). The molecular strucutre of (I) is shown in Fig. 1. In this structure, ring A (S/O2/C3/C2/O1) and ring B (C1-C5) adopt twist conformation, the mean deviation from plane are 0.1171 Å and 0.1817 Å, respectively. Ring C (C4-C9) and ring D (C8-C13) are two twisty six-mermbered rings, the dihedral angles between the C7/C8/C9 and C5/C4/C6, C10/C11/C12 and C8/C9/C13 are 1.1 (1) ° and 43.3 (2) °, respectively. So it can be found that the ring C is a six-membered ring in its chair form. Ring E (C10/C11/C14-C17) is a planar six-mermbered ring and the mean deviation from plane is 0.0170 Å. In the crystal structure, intermolecular weak C—H···O hydrogen bond (Table 1) links the molecules to form a dimeric unit (Fig. 2), in which it may be effective in the stabilization of the structure.

Experimental

A mixture of 3-O-Methoxymethyl-l6β-Epiestriol (0.9 mmol) and sodium hydride (3.5 mmol) in anhydrous THF (10 ml) was stirred for 15 min. Added a solution of sulfonyldiimidazole (0.9 mmol) in THF slowly, then stirred for 1 h, filtered through celite and washed with EtOAc to give pure compound (I) (m.p. 425–426 K).(Lim et al.,1996). Crystals of (I) suitable for X-ray diffraction were obtained by slow evaporation of an ethanol solution.