Patent application title: Crystallization of 1alpha-Hydroxy-2-Methylene-18,19-Dinor-Homopregnacalciferol
Inventors:
Hector F. Deluca (Deerfield, WI, US)
Wisconsin Alumni Research Foundation (Madison, WI, US)
Rafal Barycki (Madison, WI, US)
Rafal Barycki (Madison, WI, US)
James B. Thoden (Madison, WI, US)
James B. Thoden (Madison, WI, US)
Hazel M. Holden (Fitchburg, WI, US)
Hazel M. Holden (Fitchburg, WI, US)
Assignees:
Wisconsin Alumni Research Foundation
IPC8 Class: AC07C40100FI
USPC Class:
552653
Class name: Organic compounds -- part of the class 532-570 series organic compounds (class 532, subclass 1) 9,10-seco-cyclopentanohydrophenanthrene ring system or 9,10-seco cyclopentanohydrophenanthrene ring system having a bond between the 3- and 5-positions (e.g., vitamin d compounds, cholecalciferols, activated 7-dehydrocholesterols, dihydrotachysterols, 3,5 cyclovitamin d compounds, etc.)
Publication date: 2013-04-11
Patent application number: 20130090486
Abstract:
A method of purifying
1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol to obtain
1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol in
crystalline form using precipitation with hexane from ethyl acetate. A
method of preparing
1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol crystals
acceptable for X-ray experiment using precipitation with hexane from
benzene by diffusive exchange of the solvents is also described.Claims:
1. 1.alpha.-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol in
crystalline form.
2. The crystalline form of 1.alpha.-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol having molecular packing arrangement defined by space group P2 and unit cell dimensions a=4.8 Å, b=22.9 Å, c=36.1 Å, α=90.degree., β=90.degree. and γ=90.degree..
3. A three dimensional structure for 1.alpha.-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol as defined by the molecular packing arrangement set forth in claim 2.
4. A method of purifying 1.alpha.-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol, comprising the steps of: (a) dissolving a product containing 1.alpha.-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol to be purified in a solvent comprising ethyl acetate; (b) adding hexane to said solvent and dissolved product to form a mixture; (c) cooling said mixture containing said dissolved product below ambient temperature for a sufficient amount of time to form a precipitate of 1.alpha.-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol crystals; and (d) separating the 1.alpha.-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol crystals from the mixture.
5. The method of claim 4 wherein the step of separating comprises filtering the mixture and precipitate to obtain the crystals.
6. The method of claim 4 including a further step (d) comprising repeating steps (a) through (c) using the recovered crystals from step (c) as the product of step (a).
7. The method of claim 4 wherein a ratio of ethyl acetate and hexane is about 1:99, by volume.
8. A method of preparing 1.alpha.-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol crystals by diffusive exchange of solvents, comprising the steps of: (a) dissolving a product containing 1.alpha.-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol in a first solvent comprising benzene; (b) providing a second solvent comprising hexane; (c) allowing said first solvent with dissolved product and said second solvent to diffuse together for a sufficient amount of time to form a precipitate of 1.alpha.-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol crystals; and (d) recovering the 1.alpha.-hydroxy-2-methyelene-18,19-dinor-homopregnacalciferol crystals.
9. The method of claim 8 wherein a ratio of benzene and hexane is about 13:87, by volume.
10. The method of claim 8 wherein the step of recovering comprises filtering to obtain the crystals.
11. The method of claim 8 wherein the step of allowing said first solvent with dissolved product and said second solvent to diffuse together takes place in a closed system purged with argon.
12. The method of claim 8 wherein the step of allowing said first solvent with dissolved product and said second solvent to diffuse together takes place at room temperature.
Description:
BACKGROUND OF THE INVENTION
[0002] The present invention relates to purification of organic compounds, and more particularly to the purification of 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol (referred to herein as "051810") by preparing it in crystalline form.
[0003] Purification of organic compounds, especially those designated for pharmaceutical use, is of considerable importance for chemists synthesizing such compounds. Preparation of the compound usually requires many synthetic steps and, therefore, the final product can be contaminated not only with side-products derived from the last synthetic step of the procedure but also with compounds that were formed in previous steps. Even chromatographic purification, which is a very efficient but relatively time-consuming process, does not usually provide compounds which are sufficiently pure to be used as drugs.
[0004] Depending on the method used to synthesize 1α-hydroxyvitamin D compounds, different minor undesirable compounds can accompany the final product. Thus, for example, if direct C-1 hydroxylation of 5,6-trans geometric isomer of vitamin D is performed, followed by SeO2/NMO oxidation and photochemical irradiation [see Andrews et al., J. Org. Chem. 51, 1635 (1986); Calverley et al., Tetrahedron 43, 4609 (1987); Choudry et al, J. Org. Chem. 58, 1496 (1993)], the final 1α-hydroxyvitamin D product can be contaminated with 1β-hydroxy- as well as 5,6-trans isomers. If the method consists of C-1 allylic oxidation of the 4-phenyl-1,2,4-triazoline-3,5-dione adduct of the previtamin D compound, followed by cycloreversion of the modified adduct under basic conditions [Nevinckx et al., Tetrahedron 47, 9419 (1991); Vanmaele et al, Tetrahedron 41, 141 (1985) and 40, 1179 (1994); Vanmaele et al., Tetrahedron Lett. 23. 995 (1982)], one can expect that the desired 1α-hydroxyvitamin can be contaminated with the previtamin 5(10), 6,8-triene and 1β-hydroxy isomer. One of the most useful C-1 hydroxylation methods, of very broad scope and numerous applications, is the experimentally simple procedure elaborated by Paaren et al. [see J. Org. Chem. 45, 3253 (1980) and Proc. Natl. Acad. Sci. U.S.A. 75, 2080 (1978)]. This method consists of allylic oxidation of 3,5-cyclovitamin D derivatives, readily obtained from the buffered solvolysis of vitamin D tosylates, with SeO2/t-BuOOH and subsequent acid-catalyzed cycloreversion to the desired 1α-hydroxy compounds. Taking into account this synthetic path it is reasonable to assume that the final product can be contaminated with 1α-hydroxy epimer, 5,6-trans isomer and the previtamin D form. 1α-hydroxyvitamin D4 is another undesirable contaminant found in 1α-hydroxyvitamin D compounds synthesized from vitamin D2 or from ergosterol. 1α-hydroxyvitamin D4 results from C-1 oxidation of vitamin D4, which in turn is derived from contamination of the commercial ergosterol material. Typically, the final product may contain up to about 1.5% by weight 1α-hydroxyvitamin D4. Thus, a purification technique that would eliminate or substantially reduce the amount of 1α-hydroxyvitamin D4 in the final product to less than about 0.1-0.2% would be highly desirable.
[0005] The vitamin D conjugated triene system is not only heat- and light-sensitive but it is also prone to oxidation, leading to the complex mixture of very polar compounds. Oxidation usually happens when a vitamin D compound has been stored for a prolonged time. Other types of processes that can lead to a partial decomposition of vitamin D compounds consist of some water-elimination reactions; their driving force is allylic (1α-) and homoallylic (3β-) position of the hydroxy groups. The presence of such above-mentioned oxidation and elimination products can be easily detected by thin-layer chromatography.
[0006] Usually, all 1α-hydroxylation procedures require at least one chromatographic purification. However, even chromatographically purified 1α-hydroxyvitamin D compounds, although showing consistent spectroscopic data, suggesting homogeneity, do not meet the purity criteria required for therapeutic agents that can be orally, parenterally or transdermally administered. Therefore, it was evident that a suitable method of purification of the 1α-hydroxylated vitamin D compound 051810 is required.
SUMMARY OF THE INVENTION
[0007] The present invention relates to a method of purifying 051810 by means of crystallization to obtain 051810 in crystalline form. The solvent plays a crucial role in the crystallization process, and is typically an individual liquid substance or a suitable mixture of different liquids. For crystallizing 051810, the most appropriate solvent and/or solvent system is characterized by the following factors:
[0008] (1) low toxicity;
[0009] (2) low boiling point;
[0010] (3) significant dependence of solubility properties with regard to temperature (condition necessary for providing satisfactory crystallization yield); and
[0011] (4) relatively low cost.
[0012] Interestingly, hexane, so frequently used for crystallization purposes, was found less suitable as the sole solvent for crystallization of 051810. However, it was found that a mixture of ethyl acetate and hexane, was most useful for the crystallization of 051810. In particular, it was determined that a mixture of about 1% ethyl acetate with about 99% hexane (by volume) performed well. The ethyl acetate/hexane solvent mixture was also easy to remove by evaporation or other well known methods. In all cases the crystallization process occurred easily and efficiently; and the precipitated crystals were sufficiently large to assure their recovery by filtration or other means.
[0013] Accordingly, there is obtained 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol in crystalline form. The crystalline form and three dimensional structure of 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol has a molecular packing arrangement defined by space group P2 and unit cell dimensions a=4.8 Å, b=22.9 Å, c=36.1 Å, α=90°, β=90° and γ=9°.
[0014] In one embodiment, there is described a method of purifying 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol, comprising the steps of:
[0015] (a) dissolving a product containing 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol to be purified in a solvent comprising ethyl acetate;
[0016] (b) adding hexane to said solvent and dissolved product to form a mixture;
[0017] (c) cooling said mixture containing said dissolved product below ambient temperature for a sufficient amount of time to form a precipitate of 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol crystals; and
[0018] (d) separating the 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol crystals from the mixture.
[0019] In another embodiment, there is described a method of preparing 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol crystals by diffusive exchange of solvents, comprising the steps of:
[0020] (a) dissolving a product containing 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol in a first solvent comprising benzene;
[0021] (b) providing a second solvent comprising hexane;
[0022] (c) allowing said first solvent with dissolved product and said second solvent to diffuse together for a sufficient amount of time to form a precipitate of 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol crystals; and
[0023] (d) recovering the 1α-hydroxy-2-methyelene-18,19-dinor-homopregnacalciferol crystals.
BRIEF DESCRIPTION OF THE DRAWINGS
[0024] FIG. 1 is an illustration of the three dimensional structure of the first crystallographic asymmetric molecule for 051810 as defined by the atomic positional parameters discovered and set forth herein;
[0025] FIG. 2a is an illustration of the three dimensional structure of the second crystallographic asymmetric molecule for 051810 in the absence of the benzene molecule and as defined by the atomic positional parameters discovered and set forth herein;
[0026] FIG. 2b is an illustration of the three dimensional structure of the second asymmetric molecule for 051810 in the presence of the benzene molecule and as defined by the atomic positional parameters discovered and set forth herein; and
[0027] FIG. 3 is an illustration of a ball-and-stick representation of the entire asymmetric unit for 051810.
DETAILED DESCRIPTION OF THE INVENTION
[0028] The present invention provides 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol (051810) in crystalline form, a pharmacologically important compound, characterized by the formula I shown below:
##STR00001##
[0029] The present invention also provides a valuable method of purification of 051810. The purification technique involves obtaining the 051810 product in crystalline form by utilizing a crystallization procedure wherein the 051810 material to be purified is dissolved using ethyl acetate as the solvent and further precipitation with hexane. Preferably a ratio of ethyl acetate and hexane is about 1:99 (by volume). Thereafter, the solvent can be removed by evaporation, with or without vacuum, or other means as is well known, or the resultant crystals may be filtered from the mother liquor. The technique can be used to purify a wide range of final products containing 051810 obtained from any known synthesis thereof, and in varying concentrations, i.e. from microgram amounts to kilogram amounts. As is well known to those skilled in this art, the amount of solvent utilized should be minimized and/or adjusted according to the amount of 051810 to be purified.
[0030] The usefulness and advantages of the present crystallization procedure is shown in the following specific Example 1. After crystallization, the precipitated material was observed under a microscope to confirm its crystalline form. Yields of crystals were relatively high and the obtained crystals showed a relatively sharp melting point of 140-145° C.
[0031] The described crystallization process of the synthetic 051810 product represents a valuable purification method, which can remove most side products derived from the synthetic path. Such impurity is the result of the contamination of starting raw materials. The crystallization process occurred easily and efficiently; and the precipitated crystals were sufficiently large to assure their recovery by filtration, or other means.
Crystallization of 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol (051810)
Example 1
Crystallization from Ethyl Acetate/Hexane
[0032] 1.25 g of prepurified (see U.S. Pat. No. 7,238,681) crude 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol was dissolved in ethyl acetate (3 ml) at room temperature and hexane (300 ml) was poured into the vigorously shaken solution. The mixture was kept in a refrigerator (at 4° C.) overnight and the resulted crystals were filtered off, washed with one portion (30 ml) of cooled (4° C.) hexane and dried under reduced pressure for 3 h giving 1.10 g of a pure product.
[0033] In order to obtain crystals acceptable for the X-ray experiment, 1α-Hydroxy-2-methylene-18,19-dinor-homopregnacalciferol (12 mg) was placed in an inner tube of a vessel and dissolved in 300 μl of benzene. To an outer tube of the vessel hexane (2 ml) was poured so that a benzene to hexane ratio of about 13:87, by volume, is obtained, and the whole system was carefully purged with argon, and then maintained as a closed system. The vessel was kept tightly closed for 4 days at room temperature. Crystals were grown employing diffusive exchange of the two solvents.
[0034] A colorless rod-shaped crystal of dimensions 0.73×0.08×0.02 mm was selected for structural analysis. Intensity data were collected using a Bruker AXS Platinum 135 CCD detector controlled with the PROTEUM software suite (Bruker AXS Inc., Madison, Wis.). The x-ray source was CuKα radiation (1.54178 Å) from a Rigaku RU200 x-ray generator equipped with Montel optics, operated at 50 kV and 90 mA. The x-ray data were processed with SAINT version 7.06 Å (Bruker AXS Inc.) and internally scaled with SADABS version 2005/1 (Bruker AXS Inc.). The sample was mounted on a glass fiber using vacuum grease and cooled to 100 K. The intensity data were measured as a series of phi and omega oscillation frames each of 10 for 60-120 sec/frame. The detector was operated in 1024×1024 mode and was positioned 5.0 cm from the sample. Cell parameters were determined from a non-linear least squares fit of 9999 peaks in the range of 3.0<theta<50.80. The data were merged to form a set of 4693 independent data with R(int)=0.0884.
[0035] The orthorhombic space group P2(1)2(1)2(1) was determined by systematic absences and statistical tests and verified by subsequent refinement. The structure was solved by direct methods and refined by full-matrix least-squares methods on F2, (a) G. M. Sheldrick (1994), SHELXTL Version 5 Reference Manual, Bruker AXS Inc.; (b) International Tables for Crystallography, Vol. C, Kluwer: Boston (1995). The asymmetric unit is comprised of two molecules of 051810 and a benzene molecule. Molecule "A" is shown in FIG. 1, with thermal ellipsoids drawn at the 40% probability level. Based on lattice packing, the benzene molecule could not be present at full occupancy, and refinement of its occupancy led to a value of approximately 0.5. The presence of the benzene molecule lead to a disorder in a portion of molecule "B". Refinement of the occupancies of the two disordered configurations independently of the occupancy of the benzene converged also at a value of about 0.5 for each. FIG. 2a shows molecule B in its configuration in the absence of the benzene molecule, and FIG. 2b shows its configuration in the presence of the benzene molecule; both figures are drawn with thermal ellipsoids at the 40% probability level. FIG. 3 shows a ball-and-stick representation of the entire asymmetric unit, with the hollow bonds showing the conformation in the presence of the benzene molecule. Hydrogen atom positions were refined by a riding model with idealized geometry. Non-hydrogen atoms were refined with anisotropic displacement parameters. The benzene molecule was refined with idealized geometry. A total of 559 parameters were refined against 26 restraints and 4693 data to give wR2=0.2524 and S=0.951 for weights of w=1/[s2(F2)+(0.1719P)2], where P=[Fo2+2Fc2]/3. The final R(F) was 0.0910 for the 6781 observed data. The largest shift/s.u. was 0.001 in the final refinement cycle and the final difference map had maxima and minima of 0.366 and -0.305 e/Å3, respectively. The absolute structure was determined by refinement of the Flack parameter, H. D. Flack, Acta Cryst. A, vol. 39, 876-881 (1983).
[0036] The three dimensional structure of 051810 as defined by the following physical data and atomic positional parameters described and calculated herein is illustrated in FIGS. 1, 2a, 2b and 3.
TABLE-US-00001 TABLE 1 Crystal data and structure refinement for 051810. Identification Code 051810 Empirical formula C45 H67 O4 Formula weight 671.99 Temperature 100(1) K Wavelength 1.54178 Å Crystal system Orthorhombic Space group P2(1)2(1)2(1) Unit cell dimensions a = 4.8020(10) Å α = 90° b = 22.940(5) Å β = 90° c = 36.124(7) Å γ = 90° Volume 3979.3(14) Å3 Z 4 Density (calculated) 1.122 Mg/m3 Absorption coefficient 0.533 mm-1 F(000) 1476 Crystal 0.73 × 0.08 × 0.02 mm Theta range for data collection 2.28 to 54.17° Limiting indices -4 < h < 4, -24 < k < 23, -37 < 1 < 37 Reflections collected 12592 Independent reflections 4693 [R(int) = 0.0884] Completeness to Theta = 54.17° 98.2% Refinement method Full-matrix least-squares on F2 Data/restraints/parameters 4693/26/559 Goodness-of-fit on F2 0.951 Final R indices [I > 2σ(I)] R1 = 0.0910, wR2 = 0.2214 R indices (all data) R1 = 0.1268, wR2 = 0.2524 Extinction coefficient 0.0124(12) Largest diff. peak and hole 0.366 and -0.305 e/A3 Melting Point 140-145° C.
TABLE-US-00002 TABLE 2 Atomic coordinates (× 104) and equivalent isotropic displacement parameters (Å × 103] for 051810. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. X y z U(eq) O(1A) -322(12) 7615(2) 6913(2) 59(2) O(3A) -2739(11) 9404(2) 7179(1) 51(1) C(10A) -165(18) 8424(3) 6486(2) 47(2) C(1A) -994(17) 8232(3) 6868(2) 46(2) C(3A) 148(16) 9249(3) 7108(2) 49(2) C(14A) -7331(19) 8940(3) 5377(2) 48(2) C(4A) 864(18) 9437(3) 6719(2) 49(2) C(13A) -6378(17) 9119(3) 4990(2) 42(2) C(7A) -4130(18) 9025(3) 5916(2) 50(2) C(17A) -7691(17) 8673(3) 4726(2) 47(2) C(2A) 472(16) 8595(3) 7156(2) 47(2) C(15A) -7129(18) 8276(3) 5360(2) 49(2) C(8A) -5795(16) 9274(3) 5667(2) 43(2) C(9A) -6387(19) 9924(3) 5624(2) 52(2) C(12A) -7120(18) 9770(3) 4931(2) 46(2) C(5A) -649(16) 9072(3) 6439(2) 43(2) C(16A) -8423(18) 8158(3) 4986(2) 50(2) C(21A) -4792(18) 9008(3) 4177(2) 48(2) C(20A) -5793(17) 8486(3) 4408(2) 45(2) C(11A) -5708(19) 10137(3) 5234(2) 51(2) C(6A) -2416(17) 9326(3) 6193(2) 47(2) C(22A) -7262(18) 8050(3) 4144(2) 55(2) C(2A') 1940(20) 8381(4) 7432(2) 76(3) O(3B) -3150(11) 10326(2) 7677(1) 48(1) O(1B) -4693(10) 12069(2) 8071(1) 40(1) C(1B) -4362(16) 11592(3) 7816(2) 39(2) C(2B) -6068(16) 11074(3) 7930(2) 40(2) C(10B) -5147(19) 11778(3) 7423(2) 49(2) C(3B) -5950(17) 10575(3) 7667(2) 46(2) C(4B) -6576(18) 10759(3) 7270(2) 48(2) C(6B) -3204(17) 11254(3) 6861(2) 51(2) C(5B) -4833(17) 11275(3) 7155(2) 44(2) C(7B) -1376(17) 11745(4) 6734(2) 58(2) C(2B) -7707(19) 11071(3) 8221(2) 56(2) C(8B) 259(18) 11713(5) 6435(3) 75(3) C(12B) 2040(50) 12137(10) 5703(5) 105(13) C(9B) 720(60) 11337(11) 6171(5) 65(7) C(14B) 1730(40) 12297(7) 6369(5) 66(5) C(13B) 1580(50) 12609(9) 5997(5) 86(8) C(11B) 420(50) 11584(11) 5782(5) 96(11) C(15B) 1870(60) 12851(8) 6602(7) 111(14) C(17B) 3160(40) 13190(9) 5995(8) 109(12) C(16B) 3350(40) 13356(9) 6404(7) 101(9) C(20B) 2050(50) 13662(10) 5735(7) 151(15) C(22B) 3890(50) 14206(10) 5741(8) 185(18) C(21B) 1610(120) 13442(14) 5339(8) 230(30) C(12') 1350(40) 11726(7) 5609(6) 45(6) C(9') 160(70) 11067(10) 6145(6) 46(8) C(14') 2290(40) 12120(8) 6246(4) 45(8) C(13') 1240(50) 12265(7) 5860(4) 36(6) C(11') -560(50) 11251(8) 5752(5) 39(6) C(15') 2350(40) 12687(8) 6459(5) 33(5) C(17') 2980(40) 12809(6) 5789(4) 38(5) C(16') 3750(40) 13067(7) 6167(4) 35(6) C(20') 1650(50) 13270(7) 5543(5) 72(8) C(22') 3670(70) 13750(10) 5428(8) 78(9) C(21') 80(60) 13041(10) 5206(6) 76(9) C(1) 1350(20) 14678(5) 6378(3) 67(5) C(2) 1060(20) 14340(5) 6695(4) 64(5) C(3) 3410(30) 14137(4) 6879(2) 69(5) C(4) 6050(20) 14270(4) 6746(3) 58(5) C(5) 6340(20) 14608(4) 6429(3) 62(5) C(6) 3990(30) 14811(4) 6245(3) 74(6)
TABLE-US-00003 TABLE 3 Bond lengths [Å] for 051810. O(1A)--C(1A) 1.460(8) O(1A)--H(1AA) 0.8200 O(3A)--C(3A) 1.454(9) O(3A)--H(3AA) 0.8200 C(10A)--C(1A) 1.502(9) C(10A)--C(5A) 1.513(10) C(10A)--H(10A) 0.9700 C(10A)--H(10B) 0.9700 C(1A)--C(2A) 1.508(11) C(1A)--H(1AB) 0.9800 C(3A)--C(4A) 1.507(10) C(3A)--C(2A) 1.518(10) C(3A)--H(3AB) 0.9800 C(14A)--C(8A) 1.492(10) C(14A)--C(13A) 1.527(10) C(14A)--C(15A) 1.529(9) C(14A)--H(14A) 0.9800 C(4A)--C(5A) 1.501(10) C(4A)--H(4AA) 0.9700 C(4A)--H(4AB) 0.9700 C(13A)--C(17A) 1.534(10) C(13A)--C(12A) 1.550(9) C(13A)--H(13A) 0.9800 C(7A)--C(8A) 1.332(10) C(7A)--C(6A) 1.469(10) C(7A)--H(7AA) 0.9300 C(17A)--C(20A) 1.529(10) C(17A)--C(16A) 1.548(10) C(17A)--H(17A) 0.9800 C(2A)--C(2A') 1.314(11) C(15A)--C(16A) 1.511(10) C(15A)--H(15A) 0.9700 C(15A)--H(15B) 0.9700 C(8A)--C(9A) 1.526(10) C(9A)--C(11A) 1.528(9) C(9A)--H(9AA) 0.9700 C(9A)--H(9AB) 0.9700 C(12A)--C(11A) 1.538(10) C(12A)--H(12A) 0.9700 C(12A)--H(12B) 0.9700 C(5A)--C(6A) 1.359(10) C(16A)--H(16A) 0.9700 C(16A)--H(16B) 0.9700 C(21A)--C(20A) 1.536(10) C(21A)--H(21A) 0.9600 C(21A)--H(21B) 0.9600 C(21A)--H(21C) 0.9600 C(20A)--C(22A) 1.552(10) C(20A)--H(20A) 0.9800 C(11A)--H(11A) 0.9700 C(11A)--H(118) 0.9700 C(6A)--H(6AA) 0.9300 C(22A)--H(22A) 0.9600 C(22A)--H(22B) 0.9600 C(22A)--H(22C) 0.9600 C(2A')--H(1A') 0.9300 C(2A')--H(2A') 0.9300 O(3B)--C(3B) 1.461(10) O(3B)--H(3BA) 0.8200 O(1B)--C(1B) 1.439(8) O(1B)--H(1BA) 0.8200 C(1B)--C(2B) 1.501(10) C(1B)--C(10B) 1.532(9) C(1B)--H(1BB) 0.9800 C(2B)--C(2B') 1.313(10) C(2B)--C(3B) 1.488(10) C(10B)--C(5B) 1.514(9) C(10B)--H(10C) 0.9700 C(10B)--H(10D) 0.9700 C(3B)--C(4B) 1.526(7) C(3B)--H(3BB) 0.9800 C(4B)--C(5B) 1.506(10) C(4B)--H(4BA) 0.9700 C(4B)--H(4BB) 0.9700 C(6B)--C(5B) 1.321(10) C(6B)--C(7B) 1.499(8) C(6B)--H(6BA) 0.9300 C(7B)--C(8B) 1.338(12) C(7B)--H(7BA) 0.9300 C(2B')--H(1B') 0.9300 C(2B')--H(2B') 0.9300 C(8B)--C(9B) 1.50(2) C(8B)--C(14') 1.514(10) C(8B)--C(14B) 1.534(10) C(8B)--C(9') 1.52(2) C(12B)--C(11B) 1.516(10) C(12B)--C(13B) 1.534(10) C(12B)--H(12C) 0.9700 C(12B)--H(12D) 0.9700 C(9B)--C(11B) 1.522(10) C(9B)--H(9BA) 0.9700 C(9B)--H(9BB) 0.9700 C(14B)--C(15B) 1.527(10) C(14B)--C(13B) 1.524(10) C(14B)--H(14B) 0.9800 C(13B)--C(17B) 1.532(10) C(13B)--H(13B) 0.9800 C(11B)--H(11C) 0.9700 C(11B)--H(11D) 0.9700 C(15B)--C(16B) 1.535(10) C(15B)--H(15C) 0.9700 C(15B)--H(15D) 0.9700 C(17B)--C(16B) 1.528(10) C(17B)--C(20B) 1.528(10) C(17B)--H(17B) 0.9800 C(16B)--H(16C) 0.9700 C(16B)--H(16D) 0.9700 C(20B)--C(22B) 1.528(10) C(20B)--C(21B) 1.532(11) C(20B)--H(20B) 0.9800 C(22B)--H(22D) 0.9600 C(22B)--H(22E) 0.9600 C(22B)--H(22F) 0.9600 C(21B)--H(21D) 0.9600 C(21B)--H(21E) 0.9600 C(21B)--H(21F) 0.9600 C(12')--C(11') 1.513(10) C(12')--C(13') 1.534(10) C(12')--H(12E) 0.9700 C(12')--H(12F) 0.9700 C(9')--C(11') 1.519(10) C(9')--H(9BC) 0.9700 C(9')--H(9BD) 0.9700 C(14')--C(15') 1.512(10) C(14')--C(13') 1.517(10) C(14')--H(14') 0.9800 C(13')--C(17') 1.523(10) C(13')--H(13') 0.9800 C(11')--H(11E) 0.9700 C(11')--H(11F) 0.9700 C(15')--C(16') 1.524(10) C(15')--H(15E) 0.9700 C(15')--H(15F) 0.9700 C(17')--C(20') 1.523(10) C(17')--C(16') 1.533(10) C(17')--H(17') 0.9800 C(16')--H(16E) 0.9700 C(16')--H(16F) 0.9700 C(20')--C(21') 1.525(10) C(20')--C(22') 1.528(10) C(20')--H(20C) 0.9800 C(22')--H(22G) 0.9600 C(22')--H(22H) 0.9600 C(22')--H(22I) 0.9600 C(21')--H(21G) 0.9600 C(21')--H(21H) 0.9600 C(21')--H(21I) 0.9600 C(1)--C(2) 1.3900 C(1)--C(6) 1.3900 C(1)--H(1A) 0.9300 C(2)--C(3) 1.3900 C(2)--H(2A) 0.9300 C(3)--C(4) 1.3900 C(3)--H(3A) 0.9300 C(4)--C(5) 1.3900 C(4)--H(4A) 0.9300 C(5)--C(6) 1.3900 C(5)--H(5A) 0.9300 C(6)--H6A) 0.9300
TABLE-US-00004 TABLE 4 Bond angles [°] for 051810. C(1A)--O(1A)--H(1AA) 109.5 C(3A)--O(3A)--H(3AA) 109.5 C(1A)--C(10A)--C(5A) 110.6(6) C(1A)--C(10A)--H(10A) 109.7 C(5A)--C(10A)--H(10A) 109.6 C(1A)--C(10A)--H(10B) 109.4 C(5A)--C(10A)--H(10B) 109.4 H(10A)--C(10A)--H(10B) 108.1 O(1A)--C(1A)--C(10A) 109.1(6) O(1A)--C(1A)--C(2A) 110.9(6) C(10A)--C(1A)--C(2A) 110.4(6) O(1A)--C(1A)--H(1AB) 108.8 C(10A)--C(1A)--H(1AB) 108.8 C(2A)--C(1A)--H(1AB) 108.8 O(3A)--C(3A)--C(4A) 108.2(6) O(3A)--C(3A)--C(2A) 108.6(6) C(4A)--C(3A)--C(2A) 111.5(6) O(3A)--C(3A)--H(3AB) 109.5 C(4A)--C(3A)--H(3AB) 109.5 C(2A)--C(3A)--H(3AB) 109.5 C(8A)--C(14A)--C(13A) 110.9(7) C(8A)--C(14A)--C(15A) 120.6(7) C(13A)--C(14A)--C(15A) 102.2(6) C(8A)--C(14A)--H(14A) 107.5 C(13A)--C(14A)--H(14A) 107.5 C(15A)--C(14A)--H(14A) 107.6 C(5A)--C(4A)--C(3A) 111.0(6) C(5A)--C(4A)--H(4AA) 109.4 C(3A)--C(4A)--H(4AA) 109.4 C(5A)--C(4A)--H(4AB) 109.4 C(3A)--C(4A)--H(4AB) 109.5 H(4AA)--C(4A)--H(4AB) 108.0 C(14A)--C(13A)--C(17A) 105.5(6) C(14A)--C(13A)--C(12A) 108.4(6) C(17A)--C(13A)--C(12A) 117.6(6) C(14A)--C(13A)--H(13A) 108.4 C(17A)--C(13A)--H(13A) 108.3 C(12A)--C(13A)--H(13A) 108.4 C(8A)--C(7A)--C(6A) 126.6(7) C(8A)--C(7A)--H(7AA) 116.8 C(6A)--C(7A)--H(7AA) 116.6 C(20A)--C(17A)--C(13A) 114.2(7) C(20A)--C(17A)--C(16A) 112.1(6) C(13A)--C(17A)--C(16A) 103.1(5) C(20A)--C(17A)--H(17A) 109.1 C(13A)--C(17A)--H(17A) 109.1 C(16A)--C(17A)--H(17A) 109.1 C(2A')--C(2A)--C(1A) 124.4(7) C(2A')--C(2A)--C(3A) 120.9(8) C(1A)--C(2A)--C(3A) 114.7(6) C(16A)--C(15A)--C(14A) 100.9(6) C(16A)--C(15A)--H(15A) 111.6 C(14A)--C(15A)--H(15A) 111.6 C(16A)--C(15A)--H(15B) 111.6 C(14A)--C(15A)--H(15B) 111.5 H(15A)--C(15A)--H(15B) 109.4 C(7A)--C(8A)--C(14A) 123.4(6) C(7A)--C(8A)--C(9A) 126.8(7) C(14A)--C(8A)--C(9A) 109.8(6) C(11A)--C(9A)--C(8A) 111.5(6) C(11A)--C(9A)--H(9AA) 109.3 C(8A)--C(9A)--H(9AA) 109.4 C(11A)--C(9A)--H(9AB) 109.3 C(8A)--C(9A)--H(9AB) 109.4 H(9AA)--C(9A)--H(9AB) 108.0 C(11A)--C(12A)--C(13A) 109.2(6) C(11A)--C(12A)--H(12A) 109.8 C(13A)--C(12A)--H(12A) 109.8 C(11A)--C(12A)--H(12B) 109.9 C(13A)--C(12A)--H(12B) 109.8 H(12A)--C(12A)--H(12B) 108.3 C(6A)--C(5A)--C(4A) 120.2(6) C(6A)--C(5A)--C(10A) 126.2(7) C(4A)--C(5A)--C(10A) 113.4(6) C(15A)--C(16A)--C(17A) 108.1(6) C(15A)--C(16A)--H(16A) 110.1 C(17A)--C(16A)--H(16A) 110.1 C(15A)--C(16A)--H(16B) 110.0 C(17A)--C(16A)--H(16B) 110.1 H(16A)--C(16A)--H(16B) 108.4 C(20A)--C(21A)--H(21A) 109.6 C(20A)--C(21A)--H(21B) 109.4 H(21A)--C(21A)--H(21B) 109.5 C(20A)--C(21A)--H(21C) 109.4 H(21A)--C(21A)--H(21C) 109.5 H(21B)--C(21A)--H(21C) 109.5 C(17A)--C(20A)--C(21A) 112.2(6) C(17A)--C(20A)--C(22A) 111.9(7) C(21A)--C(20A)--C(22A) 108.1(6) C(17A)--C(20A)--H(20A) 108.2 C(21A)--C(20A)--H(20A) 108.2 C(22A)--C(20A)--H(20A) 108.2 C(9A)--C(11A)--C(12A) 112.8(7) C(9A)--C(11A)--H(11A) 109.0 C(12A)--C(11A)--H(11A) 109.0 C(9A)--C(11A)--H(11B) 109.1 C(12A)--C(11A)--H(11B) 109.0 H(11A)--C(11A)--H(11B) 107.8 C(5A)--C(6A)--C(7A) 126.5(7) C(5A)--C(6A)--H(6AA) 116.8 C(7A)--C(6A)--H(6AA) 116.7 C(20A)--C(22A)--H(22A) 109.4 C(20A)--C(22A)--H(22B) 109.5 H(22A)--C(22A)--H(22B) 109.5 C(20A)--C(22A)--H(22C) 109.5 H(22A)--C(22A)--H(22C) 109.5 H(22B)--C(22A)--H(22C) 109.5 C(2A)--C(2A')--H(1A') 120.0 C(2A)--C(2A')--H(2A') 120.0 H(1A')--C(2A')--H(2A') 120.0 C(3B)--O(3B)--H(3BA) 109.4 C(1B)--O(1B)--H(1BA) 109.4 O(1B)--C(1B)--C(2B) 111.5(5) O(1B)--C(1B)--C(10B) 110.7(5) C(2B)--C(1B)--C(10B) 110.0(6) O(1B)--C(1B)--H(1BB) 108.2 C(2B)--C(1B)--H(1BB) 108.2 C(10B)--C(1B)--H(1BB) 108.2 C(2B')--C(2B)--C(3B) 122.1(7) C(2B')--C(2B)--C(1B) 123.4(7) C(3B)--C(2B)--C(1B) 114.4(6) C(5B)--C(10B)--C(1B) 110.8(6) C(5B)--C(10B)--H(10C) 109.6 C(1B)--C(10B)--H(10C) 109.5 C(5B)--C(10B)--H(10D) 109.4 C(1B)--C(10B)--H(10D) 109.5 H(10C)--C(10B)--H(10D) 108.1 O(3B)--C(3B)--C(2B) 108.7(6) O(3B)--C(3B)--C(4B) 108.2(6) C(2B)--C(3B)--C(4B) 112.4(6) O(3B)--C(3B)--H(3BB) 109.1 C(2B)--C(3B)--H(3BB) 109.2 C(4B)--C(3B)--H(3BB) 109.2 C(5B)--C(4B)--C(3B) 111.5(6) C(5B)--C(4B)--H(4BA) 109.3 C(3B)--C(4B)--H(4BA) 109.2 C(5B)--C(4B)--H(4BB) 109.4 C(3B)--C(4B)--H(4BB) 109.4 H(4BA)--C(4B)--H(4BB) 108.0 C(5B)--C(6B)--C(7B) 124.5(7) C(5B)--C(6B)--H(6BA) 117.8 C(7B)--C(6B)--H(6BA) 117.7 C(6B)--C(5B)--C(4B) 121.5(6) C(6B)--C(5B)--C(10B) 126.9(7) C(4B)--C(5B)--C(10B) 111.6(6) C(8B)--C(7B)--C(6B) 123.3(8) C(8B)--C(7B)--H(7BA) 118.3 C(6B)--C(7B)--H(7BA) 118.4 C(2B)--C(2B')--H(1B') 120.1 C(2B)--C(2B')--H(2B') 119.9 H(1B')--C(2B')--H(2B') 120.0 C(9B)--C(8B)--C(7B) 136.7(13) C(9B)--C(8B)--C(14') 88.1(14) C(7B)--C(8B)--C(14') 135.1(12) C(9B)--C(8B)--C(14B) 112.6(15) C(7B)--C(8B)--C(14B) 110.4(11) C(14')--C(8B)--C(14B) 24.9(8) C(9B)--C(8B)--C(9') 16.9(16) C(7B)--C(8B)--C(9') 119.8(12) C(14')--C(8B)--C(9') 105.0(13) C(14B)--C(8B)--C(9') 129.4(13) C(11B)--C(12B)--C(13B) 112.7(18) C(11B)--C(12B)--H(12C) 108.9 C(13B)--C(12B)--H(12C) 108.6 C(11B)--C(12B)--H(12D) 109.3 C(13B)--C(12B)--H(12D) 109.5 H(12C)--C(12B)--H(12D) 107.8 C(8B)--C(9B)--C(11B) 114.4(19) C(8B)--C(9B)--H(9BA) 109.1 C(11B)--C(9B)--H(9BA) 108.4 C(8B)--C(9B)--H(9BB) 108.6 C(11B)--C(9B)--H(9BB) 108.6 H(9BA)--C(9B)--H(9BB) 107.6 C(15B)--C(14B)--C(13B) 95.5(15) C(15B)--C(14B)--C(8B) 131.5(13) C(13B)--C(14B)--C(8B) 121.8(14) C(15B)--C(14B)--H(14B) 100.6 C(13B)--C(14B)--H(14B) 101.3 C(8B)--C(14B)--H(14B) 101.0 C(14B)--C(13B)--C(17B) 113.0(14) C(14B)--C(13B)--C(12B) 105.8(15) C(17B)--C(13B)--C(12B) 122.6(18) C(14B)--C(13B)--H(13B) 104.3 C(17B)--C(13B)--H(13B) 104.4 C(12B)--C(13B)--H(13B) 105.0 C(12B)--C(11B)--C(9B) 115.9(19) C(12B)--C(11B)--H(11C) 108.0 C(9B)--C(11B)--H(11C) 108.5 C(12B)--C(11B)--H(11D) 108.5 C(9B)--C(11B)--H(11D) 108.3 H(11)--C(11B)--H(11D) 107.4 C(14B)--C(15B)--C(16B) 113.1(17) C(14B)--C(15B)--H(15C) 109.4 C(16B)--C(15B)--H(15C) 109.8 C(14B)--C(15B)--H(15D) 107.9 C(16B)--C(15B)--H(15D) 108.7 H(15C)--C(15B)--H(15D) 107.6 C(16B)--C(17B)--C(20B) 115.9(19) C(16B)--C(17B)--C(13B) 104.0(16) C(20B)--C(17B)--C(13B) 116.6(16) C(16B)--C(17B)--H(17B) 106.2 C(20B)--C(17B)--H(17B) 106.6 C(13B)--C(17B)--H(17B) 106.7 C(17B)--C(16B)--C(15B) 103.5(18) C(17B)--C(16B)--H(16C) 111.1 C(15B)--C(16B)--H(16C) 110.8 C(17B)--C(16B)--H(16D) 111.7 C(15B)--C(16B)--H(16D) 110.5 H(16C)--C(16B)--H(16D) 109.2 C(22B)--C(20B)--C(17B) 111.7(17) C(22B)--C(20B)--C(21B) 111(2) C(17B)--C(20B)--C(21B) 113(2) C(22B)--C(20B)--H(20B) 107.2 C(17B)--C(20B)--H(20B) 107.2 C(21B)--C(20B)--H(20B) 106.3 C(20B)--C(22B)--H(22D) 109.5 C(20B)--C(22B)--H(22E) 109.5 H(22D)--C(22B)--H(22E) 109.5 C(20B)--C(22B)--H(22F) 109.3 H(22D)--C(22B)--H(22F) 109.5 H(22E)--C(22B)--H(22F) 109.5 C(20B)--C(21B)--H(21D) 110.2 C(20B)--C(21B)--H(21E) 109.4 H(21D)--C(21B)--H(21E) 109.5 C(20B)--C(21B)--H(21F) 108.8 H(21D)--C(21B)--H(21F) 109.5 H(21E)--C(21B)--H(21F) 109.5 C(11')--C(12')--C(13') 111.0(13) C(11')--C(12')--H(12E) 109.4 C(13')--C(12')--H(12E) 109.7 C(11')--C(12')--H(12F) 109.8 C(13')--C(12')--H(12F) 108.9 H(12E)--C(12')--H(12F) 108.0 C(11')--C(9')--C(8B) 108.5(15) C(11')--C(9')--H(9BC) 110.2 C(8B)--C(9')--H(9BC) 109.7 C(11')--C(9')--H(9BD) 109.9 C(8B)--C(9')--H(9BD) 110.3 H(9BC)--C(9')--H(9BD) 108.3 C(8B)--C(14')--C(15') 108.3(13) C(8B)--C(14')--C(13') 109.7(13) C(15')--C(14')--C(13') 106.5(15) C(8B)--C(14')--H(14') 111.1 C(15')--C(14')--H(14') 110.6 C(13')--C(14')--H(14') 110.5
C(14')--C(13')--C(17') 98.8(11) C(14')--C(13')--C(12') 110.8(17) C(17')--C(13')--C(12') 122.8(15) C(14')--C(13')--H(13') 107.9 C(17')--C(13')--H(13') 107.7 C(12')--C(13')--H(13') 107.8 C(12')--C(11')--C(9') 112.5(18) C(12')--C(11')--H(11E) 108.6 C(9')--C(11')--H(11E) 108.7 C(12')--C(11')--H(11F) 109.6 C(9')--C(11')--H(11F) 109.5 H(11E)--C(11')--H(11F) 107.9 C(14')--C(15')--C(16') 98.5(12) C(14')--C(15')--H(15E) 112.0 C(16')--C(15')--H(15E) 112.7 C(14')--C(15')--H(15F) 111.7 C(16')--C(15')--H(15F) 111.9 H(15E)--C(15')--H(15F) 109.7 C(20')--C(17')--C(13') 115.8(13) C(20')--C(17')--C(16') 110.6(13) C(13')--C(17')--C(16') 107.3(13) C(20')--C(17')--H(17') 107.9 C(13')--C(17')--H(17') 107.4 C(16')--C(17')--H(17') 107.5 C(15')--C(16')--C(17') 106.8(14) C(15')--C(16')--H(16E) 109.9 C(17')--C(16')--H(16E) 110.7 C(15')--C(16')--H(16F) 110.1 C(17')--C(16')--H(16F) 110.8 H(16E)--C(16')--H(16F) 108.6 C(17')--C(20')--C(21') 115.7(14) C(17')--C(20')--C(22') 112.9(18) C(21')--C(20')--C(22') 110(2) C(17')--C(20')--H(20C) 105.6 C(21')--C(20')--H(20C) 105.5 C(22')--C(20')--H(20C) 105.8 C(20')--C(22')--H(22G) 109.6 C(20')--C(22')--H(22H) 109.7 H(22G)--C(22')--H(22H) 109.5 C(20')--C(22')--H(22I) 109.1 H(22G)--C(22')--H(22I) 109.5 H(22H)--C(22')--H(22I) 109.5 C(20')--C(21')--H(21G) 109.3 C(20')--C(21')--H(21H) 109.7 H(21G)--C(21')--H(21H) 109.5 C(20')--C(21')--H(21I) 109.5 H(21G)--C(21')--H(21I) 109.5 H(21H)--C(21')--H(21I) 109.5 C(2)--C(1)--C(6) 120.0 C(2)--C(1)--H(1A) 120.0 C(6)--C(1)--H(1A) 120.0 C(1)--C(2)--C(3) 120.0 C(1)--C(2)--H(2A) 120.0 C(3)--C(2)--H(2A) 120.0 C(2)--C(3)--C(4) 120.0 C(2)--C(3)--H(3A) 120.0 C(4)--C(3)--H(3A) 120.0 C(5)--C(4)--C(3) 120.0 C(5)--C(4)--H(4A) 120.0 C(3)--C(4)--H(4A) 120.0 C(4)--C(5)--C(6) 120.00(5) C(4)--C(5)--H(5A) 120.0 C(6)--C(5)--H(5A) 120.0 C(5)--C(6)--C(1) 120.0 C(5)--C(6)--H(6A) 120.0 C(1)--C(6)--H(6A) 120.0
TABLE-US-00005 TABLE 5 Anisotropic displacement parameters [Å2 × 103] for 051810. The anisotropic displacement factor exponent takes the form: -2π2 [h2a*2U11 + . . . + 2hka*b*U12] U11 U22 U33 U23 U13 U12 O (1A) 50 (4) 34 (3) 93 (4) 21 (3) 2 (3) 9 (3) O (3A) 41 (4) 48 (3) 64 (3) -2 (3) 7 (3) 6 (3) C (10A) 53 (6) 33 (4) 54 (5) -5 (3) -2 (4) -4 (4) C (1A) 35 (5) 27 (4) 76 (5) 12 (4) 3 (4) 5 (3) C (3A) 37 (5) 36 (4) 75 (5) -2 (4) -6 (4) 4 (4) C (14A) 53 (6) 36 (4) 56 (5) 3 (4) 0 (4) 6 (4) C (4A) 50 (6) 36 (4) 61 (5) 7 (4) 0 (4) -6 (4) C (13A) 42 (5) 35 (4) 50 (4) 8 (3) 4 (4) 9 (4) C (7A) 60 (6) 35 (4) 55 (5) -8 (4) 13 (4) -9 (4) C (17A) 42 (5) 45 (4) 52 (5) 7 (4) -3 (4) 3 (4) C (2A) 41 (5) 50 (5) 50 (4) 12 (4) 8 (4) 4 (4) C (15A) 52 (6) 39 (4) 58 (5) 8 (4) 6 (4) 0 (4) C (8A) 44 (5) 35 (4) 50 (5) 8 (4) 4 (4) 6 (4) C (9A) 53 (6) 47 (5) 56 (5) 2 (4) 10 (4) 1 (4) C (12A) 54 (6) 36 (4) 46 (4) 6 (3) 2 (4) 9 (4) C (5A) 36 (5) 39 (4) 55 (4) 0 (4) 4 (4) 1 (4) C (16A) 43 (5) 44 (5) 62 (5) 4 (4) -3 (4) 2 (4) C (21A) 48 (6) 43 (4) 53 (4) 1 (4) 2 (4) 10 (4) C (20A) 39 (5) 38 (4) 57 (5) 1 (4) -1 (4) 4 (4) C (11A) 59 (6) 40 (4) 53 (5) 4 (4) 3 (4) 5 (4) C (6A) 50 (5) 33 (4) 60 (5) 2 (4) 8 (4) -3 (4) C (22A) 59 (6) 47 (5) 59 (5) 0 (4) -12 (4) -1 (4) C (2A') 77 (8) 78 (6) 74 (6) -4 (5) -5 (5) 33 (6) O (3B) 49 (4) 34 (3) 60 (3) -1 (2) -3 (3) 4 (2) O (1B) 48 (3) 31 (3) 41 (3) -5 (2) -3 (2) 4 (2) C (1B) 44 (5) 28 (4) 45 (4) -2 (3) -1 (3) -4 (3) C (2B) 37 (5) 42 (4) 41 (4) -3 (3) 0 (3) -4 (3) C (10B) 54 (6) 38 (4) 56 (5) -3 (4) 3 (4) -3 (4) C (3B) 49 (5) 32 (4) 57 (5) -6 (4) 0 (4) -3 (4) C (4B) 49 (5) 39 (4) 55 (5) -10 (4) 3 (4) -2 (4) C (6B) 49 (6) 55 (5) 48 (5) -6 (4) -4 (4) 10 (4) C (5B) 45 (5) 36 (4) 51 (4) -10 (3) -3 (4) 10 (4) C (7B) 38 (5) 79 (6) 57 (5) 15 (4) 1 (4) 12 (5) C (2B') 59 (6) 42 (5) 66 (5) -1 (4) 1 (5) 4 (4) C (8B) 33 (6) 124 (9) 68 (6) 37 (7) 6 (5) 28 (6) C (12B) 83 (18) 190 (30) 43 (14) 64 (16) 31 (12) 80 (20) C (9B) 43 (13) 100 (20) 48 (13) 5 (13) -7 (9) 8 (16) C (14B) 16 (11) 118 (13) 63 (11) 38 (10) 26 (8) 27 (10) C (13B) 74 (16) 109 (19) 74 (15) 40 (15) 38 (13) 44 (15) C (11B) 32 (16) 170 (40) 89 (19) 40 (20) 22 (12) 20 (17) C (15B) 44 (14) 140 (30) 150 (30) 110 (20) 30 (20) 20 (20) C (17B) 9 (12) 87 (19) 230 (30) 70 (20) -3 (15) 13 (11) C (16B) 50 (13) 84 (15) 170 (20) 66 (17) 0 (13) -1 (11) C (20B) 110 (20) 140 (30) 200 (30) 120 (30) 70 (20) 90 (20) C (22B) 120 (20) 140 (20) 300 (40) 140 (30) 130 (30) 51 (19) C (21B) 410 (90) 170 (50) 120 (30) 100 (40) 100 (50) 100 (50) C (12') 44 (15) 10 (9) 82 (17) -11 (11) 3 (11) 0 (9) C (9' ) 38 (17) 23 (13) 77 (17) -8 (11) -5 (11) -1 (10) C (14') 18 (16) 64 (14) 53 (16) 17 (12) 35 (12) 35 (12) C (13') 50 (16) 34 (14) 26 (13) -8 (9) 2 (11) 0 (12) C (11') 34 (14) 42 (12) 41 (11) -8 (9) 0 (9) -22 (9) C (15') 15 (13) 44 (9) 39 (10) 12 (7) 5 (7) -3 (8) C (17') 44 (13) 13 (11) 56 (12) 2 (9) -7 (10) -4 (9) C (16') 37 (14) 14 (10) 56 (13) -22 (10) -7 (11) 12 (9) C (20') 130 (20) 48 (17) 42 (14) -7 (13) -1 (15) -9 (16) C (22') 160 (30) 31 (13) 46 (14) 5 (11) 35 (15) -24 (14) C (21') 120 (20) 49 (15) 56 (14) 18 (11) -35 (14) 9 (14) C (1) 55 (14) 51 (11) 95 (14) -8 (10) 2 (10) 11 (9) C (2) 62 (14) 50 (10) 80 (13) -31 (10) 15 (10) 9 (10) C (3) 83 (16) 53 (10) 71 (12) -10 (9) 12 (12) -1 (11) C (4) 63 (13) 36 (9) 74 (12) -12 (8) 3 (9) 4 (9) C (5) 91 (15) 30 (9) 67 (12) 7 (8) 7 (11) 3 (9) C (6) 87 (17) 49 (11) 85 (13) -1 (10) 7 (13) 11 (11)
TABLE-US-00006 TABLE 6 Hydrogen coordinates (× 104) and isotropic displacement parameters (Å2 × 103) for 051810. x y z U(eq) H(1AA) -772 7508 7121 88 H(3AA) -3165 9304 7389 76 H(10A) -1247 8212 6304 56 H(10B) 1787 8337 6445 56 H(1AB) -3008 8283 6896 55 H(3AB) 1358 9452 7284 59 H(14A) -9307 9042 5399 58 H(4AA) 363 9843 6686 59 H(4AB) 2855 9400 6681 59 H(13A) -4349 9078 4977 51 H(7AA) -4044 8620 5914 60 H(17A) -9414 8836 4624 56 H(15A) -5210 8145 5369 59 H(15B) -8177 8093 5557 59 H(9AA) -8336 9998 5677 62 H(9AB) -5281 10140 5802 62 H(12A) -6487 9896 4689 55 H(12B) -9123 9821 4943 55 H(16A) -10428 8123 5010 60 H(16B) -7704 7797 4884 60 H(21A) -3850 9281 4334 72 H(21B) -6364 9194 4063 72 H(21C) -3535 8874 3988 72 H(20A) -4155 8293 4514 53 H(11A) -3707 10126 5198 61 H(11B) -6304 10539 5209 61 H(6AA) -2553 9730 6201 57 H(22A) -5981 7928 3955 82 H(22B) -8841 8235 4031 82 H(22C) -7870 7716 4282 82 H(1A') 2123 7979 7458 114 H(2A') 2789 8630 7600 114 H(3BA) -2777 10226 7889 72 H(1BA) -4248 11964 8280 60 H(1BB) -2397 11477 7816 47 H(10C) -7059 11915 7420 59 H(10D) -3958 12098 7346 59 H(3BB) -7298 10278 7744 55 H(4BA) -6208 10435 7105 57 H(4BB) -8532 10859 7249 57 H(6BA) -3190 10912 6723 61 H(7BA) -1379 12089 6870 69 H(1B') -8841 10751 8268 84 H(2B') -7733 11389 8381 84 H(12C) 1489 12288 5463 126 H(12D) 4012 12045 5691 126 H(9BA) -563 11014 6199 78 H(9BB) 2594 11184 6199 78 H(14B) 3687 12175 6372 79 H(13B) -381 12719 5970 103 H(11C) 1004 11288 5606 115 H(11D) -1538 11661 5737 155 H(15C) 2846 12767 6831 134 H(15D) -5 12972 6664 134 H(17B) 5058 13104 5913 131 H(16C) 2418 13724 6451 121 H(16D) 5278 13387 6482 121 H(20B) 220 13778 5830 181 H(22D) 3864 14386 5502 277 H(22E) 5760 14097 5804 277 H(22F) 3189 14475 5922 277 H(21D) -117 13593 5245 349 H(21E) 1547 13024 5339 349 H(21F) 3116 13572 5186 349 H(12E) 785 11834 5360 54 H(12F) 3241 11581 5598 54 H(9BC) 1963 10874 6148 55 H(9BD) -1223 10796 6237 55 H(14') 4150 11946 6235 54 H(13') -708 12386 5882 44 H(11E) -427 10915 5590 47 H(11F) -2464 11390 5746 47 H(15E) 3449 12658 6683 39 H(15F) 490 12824 6519 39 H(17') 4716 12684 5669 45 H(16E) 5753 13064 6201 42 H(16F) 3094 13466 6185 42 H(20C) 240 13461 5697 87 H(22G) 2711 14036 5282 118 H(22H) 5163 13584 5286 118 H(22I) 4425 13933 5646 118 H(21G) -707 13362 5071 114 H(21H) -1382 12784 5285 114 H(21I) 1345 12832 5048 114 H(1A) -219 14814 6255 81 H(2A) -706 14251 6784 77 H(3A) 3213 13911 7091 83 H(4A) 7619 14134 6869 69 H(5A) 8105 14697 6340 75 H(6A) 4186 15037 6032 89
TABLE-US-00007 TABLE 7 Observed and calculated structure factors for 051810. h k l 10Fo 10Fc 10s 2 0 0 42 37 16 4 0 0 138 11 0 15 1 1 0 437 450 11 2 1 0 362 322 16 3 1 0 252 218 24 0 2 0 271 282 8 1 2 0 426 437 14 2 2 0 277 256 13 3 2 0 352 250 29 4 2 0 158 155 27 1 3 0 177 158 10 2 3 0 400 366 25 3 3 0 502 441 19 4 3 0 108 115 41 0 4 0 2471 1827 86 1 4 0 364 399 10 2 4 0 337 336 22 3 4 0 262 232 10 4 4 0 121 91 37 1 5 0 76 86 7 2 5 0 79 85 29 3 5 0 117 101 12 4 5 0 175 222 27 0 6 0 296 309 14 1 6 0 589 676 20 2 6 0 86 46 29 3 6 0 199 199 14 1 7 0 111 130 6 2 7 0 99 12 27 3 7 0 164 132 10 0 8 0 833 923 65 1 8 0 272 335 26 2 8 0 75 86 41 3 8 0 158 156 23 1 9 0 300 305 18 2 9 0 293 277 14 3 9 0 306 302 16 0 10 0 259 184 39 1 10 0 259 210 11 2 10 0 77 5 43 3 10 0 97 83 21 1 11 0 348 359 13 2 11 0 86 11 31 3 11 0 236 225 17 4 11 0 288 303 23 0 12 0 585 527 37 1 12 0 283 234 12 2 12 0 344 321 15 3 12 0 88 37 25 4 12 0 169 156 21 1 13 0 38 9 37 2 13 0 97 124 22 3 13 0 168 188 18 4 13 0 88 4 40 0 14 0 105 104 19 1 14 0 164 161 11 2 14 0 123 93 11 3 14 0 89 139 27 4 14 0 0 50 1 1 15 0 83 60 30 2 15 0 248 227 10 3 15 0 283 273 15 0 16 0 77 26 25 1 16 0 40 24 40 2 16 0 63 39 23 3 16 0 62 93 61 1 17 0 50 8 50 2 17 0 58 46 57 3 17 0 114 143 14 0 18 0 100 100 25 1 18 0 122 122 27 2 18 0 65 44 29 3 18 0 67 21 37 1 19 0 67 82 34 2 19 0 86 77 15 3 19 0 44 9 43 0 20 0 188 199 19 1 20 0 0 42 1 3 0 1 336 325 28 4 0 1 0 25 1 -3 1 1 201 154 25 -2 1 1 116 114 8 -1 1 1 1143 962 30 0 1 1 134 157 3 1 1 1 1115 961 54 2 1 1 125 114 9 3 1 1 212 154 23 4 1 1 159 141 16 -3 2 1 441 430 24 -2 2 1 436 399 19 -1 2 1 1871 1484 56 0 2 1 142 155 3 1 2 1 1819 1485 117 2 2 1 432 400 28 3 2 1 453 431 34 4 2 1 117 84 36 -3 3 1 95 101 19 -2 3 1 356 355 23 -1 3 1 861 840 26 0 3 1 1901 1442 47 1 3 1 857 839 30 2 3 1 358 354 23 3 3 1 139 100 15 4 3 1 89 72 57 -4 4 1 146 157 30 -3 4 1 294 284 11 -2 4 1 334 364 20 -1 4 1 415 464 11 0 4 1 961 903 26 1 4 1 415 464 10 2 4 1 308 364 22 3 4 1 292 283 12 4 4 1 154 156 28 -3 5 1 218 162 21 -2 5 1 251 211 16 -1 5 1 621 673 26 0 5 1 143 120 6 1 5 1 624 673 16 2 5 1 214 212 19 3 5 1 193 163 11 4 5 1 97 32 53 -3 6 1 286 246 11 -2 6 1 179 174 25 -1 6 1 187 202 12 0 6 1 478 526 14 1 6 1 170 202 6 2 6 1 172 175 18 3 6 1 284 246 15 -3 7 1 122 113 11 -2 7 1 399 369 17 -1 7 1 317 373 10 0 7 1 185 170 7 1 7 1 313 372 9 2 7 1 368 369 28 3 7 1 128 112 17 4 7 1 146 100 24 -3 8 1 116 91 14 -2 8 1 104 93 13 -1 8 1 196 223 11 0 8 1 115 77 14 1 8 1 194 222 13 2 8 1 107 92 12 3 8 1 135 91 12 4 8 1 101 62 36 -3 9 1 114 91 17 -2 9 1 122 115 16 -1 9 1 522 569 22 0 9 1 556 610 16 1 9 1 513 570 22 2 9 1 126 116 11 3 9 1 79 92 30 -4 10 1 132 78 27 -3 10 1 195 194 19 -2 10 1 262 248 10 -1 10 1 375 400 14 0 10 1 690 690 21 2 11 1 322 300 23 3 11 1 63 25 49 -4 12 1 194 205 21 -3 12 1 232 275 22 -2 12 1 284 258 14 -1 12 1 522 526 18 0 12 1 680 694 30 1 12 1 509 525 23 2 12 1 260 268 9 3 12 1 285 275 14 4 12 1 198 205 20 -4 13 1 80 79 45 -2 13 1 91 91 13 -1 13 1 164 146 11 0 13 1 365 339 38 1 13 1 152 147 10 2 13 1 69 92 17 3 13 1 292 333 16 4 13 1 80 79 19 -4 14 1 132 123 26 -3 14 1 56 95 55 -2 14 1 247 228 11 -1 14 1 83 79 16 0 14 1 324 311 11 1 14 1 65 79 30 2 14 1 261 227 9 3 14 1 77 94 31 4 14 1 116 123 14 -3 15 1 11 72 11 -2 15 1 164 167 10 -1 15 1 119 102 13 0 15 1 62 54 23 1 15 1 88 103 19 2 15 1 166 167 10 3 15 1 0 72 1 -3 16 1 106 124 20 -2 16 1 98 95 14 -1 16 1 79 59 29 0 16 1 40 1 40 1 16 1 87 59 25 2 16 1 88 94 17 3 16 1 111 124 18 -3 17 1 85 71 25 -2 17 1 272 247 10 -1 17 1 162 152 15 0 17 1 76 18 18 1 17 1 159 153 15 2 17 1 280 248 10 3 17 1 85 71 18 -3 18 1 96 80 16 -2 18 1 103 83 13 -1 18 1 147 118 15 0 18 1 236 218 10 1 18 1 119 118 24 2 18 1 66 83 22 3 18 1 46 80 46 -3 19 1 75 77 21 -2 19 1 115 124 11 -1 19 1 103 120 19 0 19 1 175 179 11 1 19 1 75 120 28 2 19 1 118 124 11 3 19 1 49 77 48 -2 20 1 215 209 11 -1 20 1 64 54 32 0 20 1 69 84 27 1 20 1 0 54 1 2 20 1 207 209 14 -2 21 1 0 24 1 -1 21 1 77 97 21 0 21 1 155 180 11 1 21 1 83 97 19 2 21 1 42 25 42 -1 22 1 72 95 22 0 22 1 130 155 15 1 22 1 64 95 54 2 22 1 0 55 1 -1 23 1 120 133 12 -3 1 2 263 203 23 -2 1 2 315 296 10 -1 1 2 1086 934 28 0 1 2 752 671 17 1 1 2 1040 934 33 2 1 2 338 296 14 3 1 2 241 203 26 4 1 2 147 115 13 -4 2 2 0 44 1 -3 2 2 297 289 26
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-2 3 31 165 165 18 -1 3 31 71 87 32 0 3 31 103 113 20 1 3 31 88 86 31 2 3 31 117 166 19 -2 4 31 126 122 13 -1 4 31 69 68 36 0 4 31 103 87 18 1 4 31 100 69 20 2 4 31 110 122 19 -2 5 31 109 93 15 -1 5 31 159 179 32 0 5 31 0 25 1 1 5 31 167 178 14 2 5 31 0 93 1 -2 6 31 140 145 13 -1 6 31 80 33 21 0 6 31 167 181 12 1 6 31 42 33 41 2 6 31 151 145 34 -2 7 31 78 57 22 -1 7 31 77 100 48 0 7 31 142 140 12 1 7 31 86 99 34 2 7 31 0 57 1 -2 8 31 0 37 1 -1 8 31 88 88 20 0 8 31 74 23 27 1 8 31 100 88 70 2 8 31 0 37 1 -2 9 31 83 71 22 -2 1 32 128 126 12 -1 1 32 92 124 21 0 1 32 105 106 17 1 1 32 98 124 21 2 1 32 125 126 24 -2 2 32 77 79 25 -1 2 32 63 50 39 0 2 32 93 84 19 1 2 32 69 50 36 2 2 32 62 79 61 -2 3 32 181 163 11 -1 3 32 66 70 36 0 3 32 34 39 34 1 3 32 77 70 30 2 3 32 121 163 30 -2 4 32 81 70 21 -1 4 32 225 263 11 0 4 32 96 98 20 1 4 32 219 263 14 2 4 32 89 71 24 -2 5 32 42 55 41 -1 5 32 96 113 19 0 5 32 138 131 14 1 5 32 104 113 45 2 5 32 0 55 1 -2 6 32 61 30 32 -1 6 32 134 146 12 0 6 32 96 116 17 1 6 32 145 146 15 2 6 32 0 30 1 -2 7 32 49 23 49 -1 7 32 99 115 18 0 7 32 106 82 52 1 7 32 115 115 17 2 7 32 0 23 1 -2 8 32 50 83 49 -1 8 32 81 91 21 0 8 32 70 38 28 1 8 32 82 90 28 2 8 32 112 83 33 -1 9 32 36 39 35 0 9 32 50 68 50 1 9 32 65 39 42 -1 10 32 60 63 29 0 10 32 25 31 24 1 10 32 63 63 63 -1 11 32 80 66 19 0 11 32 0 42 1 1 11 32 19 66 19 -1 12 32 0 42 1 0 12 32 55 87 54 -1 4 33 112 140 14 0 4 33 78 75 24 1 4 33 148 139 23 2 4 33 27 74 26 -2 5 33 82 76 19 -1 5 33 120 120 17 0 5 33 80 57 23 1 5 33 133 121 17 2 5 33 77 76 77 -2 6 33 20 19 19 -1 6 33 0 42 1 0 6 33 65 61 32 1 6 33 55 42 54 2 6 33 0 20 1 -1 7 33 111 112 14 0 7 33 69 44 29 1 7 33 137 111 18 -1 8 33 62 73 33 0 8 33 6 18 5 1 8 33 82 74 27 -1 9 33 69 70 27 0 9 33 63 27 63 1 9 33 0 70 1 -1 10 33 8 50 8 0 10 33 48 11 48 1 10 33 46 50 45 0 11 33 132 125 13 0 0 34 254 258 25 1 0 34 57 41 56 2 0 34 0 45 1 -2 1 34 51 20 50 -1 1 34 120 141 17 0 1 34 150 131 13 1 1 34 131 141 17 2 1 34 33 20 32 -2 2 34 84 76 26 -1 2 34 92 103 21 0 2 34 123 120 15 1 2 34 103 103 20 2 2 34 0 76 1 -2 3 34 51 39 50 -1 3 34 95 103 17 0 3 34 161 176 24 1 3 34 101 103 21 2 3 34 0 39 1 -2 4 34 42 45 42 -1 4 34 107 135 15 0 4 34 75 89 37 1 4 34 130 135 34 -1 5 34 115 116 14 0 5 34 0 4 1 -1 2 35 75 63 74 0 2 35 0 71 1 1 2 35 106 63 21 -1 3 35 0 30 1 0 3 35 96 80 20 1 3 35 0 30 1 -1 4 35 89 93 19 0 4 35 0 18 1 1 4 35 109 93 21 -1 5 35 46 50 45 0 5 35 0 6 1 1 5 35 27 49 26 -1 6 35 107 115 16 0 6 35 70 54 27 1 6 35 126 115 17 -1 7 35 0 56 1 0 7 35 77 84 24 1 7 35 48 56 48 -1 8 35 80 26 38 0 8 35 46 50 46 0 9 35 0 7 1 0 0 36 97 106 35 1 0 36 55 1 55 -1 1 36 23 76 22 0 1 36 28 24 28 1 1 36 0 76 1 -1 2 36 0 26 1 0 2 36 49 87 48 1 2 36 41 25 40 -1 3 36 56 32 47 0 3 36 84 38 25 1 3 36 0 32 1 -1 4 36 78 49 29 0 4 36 23 16 23 1 4 36 0 49 1 -1 5 36 55 40 55 0 5 36 44 40 43 1 5 36 51 40 51 0 6 36 85 58 23 0 7 36 88 105 22 1 0 37 87 62 26 -1 1 37 75 69 62 0 1 37 68 67 37 1 1 37 82 69 35 -1 2 37 24 56 24 0 2 37 13 29 12 0 3 37 121 103 17 0 4 37 167 153 13 0 5 37 48 60 47
Example 2
Synthesis of 051810
[0037] The preparation of 051810 having the basic structure I can be accomplished by a common general method, i.e. the condensation of a bicyclic Windaus-Grundmann type ketone II with the allylic phosphine oxide III to the corresponding 2-methylene-19-nor-vitamin D analog IV followed by deprotection at C-1 and C-3 in the latter compound IV to obtain compound I, i.e. 051810.
##STR00002##
[0038] In phosphine oxide III, Y1 and Y2 are preferably hydroxy-protecting groups such as silyl protecting groups. The t-butyldimethylsilyl (TMDMS) group is an example of a particularly useful hydroxy-protecting group. The process described above represents an application of the convergent synthesis concept, which has been applied effectively to the preparation of numerous vitamin D compounds (see Lythgoe et al., J. Chem. Soc. Perkin Trans. I, 590 (1978); Lythgoe, Chem. Soc. Rev. 9, 449 (1983); Toh et al., J. Org. Chem. 48, 1414 (1983); Baggiolini et al., J. Org. Chem. 51, 3098 (1986); Sardina et al., J. Org. Chem. 51, 1264 (1986); J. Org. Chem. 51, 1269 (1986); DeLuca et al., U.S. Pat. No. 5,086,191; DeLuca et al., U.S. Pat. No. 5,536,713; and DeLuca et al, U.S. Pat. No. 5,843,928 all of which are hereby incorporated by reference in their entirety and for all purposes as if fully set forth herein.
[0039] Phosphine oxide III is a convenient reagent that can be used to prepare a large number of 19-nor-vitamin D compounds and is prepared according to the procedures described by Sicinski et al., J. Med. Che., 41, 4662 (1998), DeLuca et al., U.S. Pat. No. 5,843,928; Perlman et al., Tetrahedron Let. 32, 7663 (1991); and DeLuca et al., U.S. Pat. No. 5,086,191 which are hereby incorporated by reference in their entirety as if fully set forth herein.
[0040] The overall process of the synthesis of compound I is illustrated and described more completely in U.S. Pat. No. 5,843,928 entitled "2-Alkylidene-19-Nor-Vitamin D Compounds" and in U.S. Pat. No. 7,238,681, entitled "2-Methylene-18,19-Dinor-1α-Hydroxy-Homopregnacalciferol and Its Uses" the specifications of which are specifically incorporated herein by reference.
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