24-Methyl-25,26-dihydroxy-steroids

The mercury plus aqueous phase was separated, after partitioning, from the ether the latter may be further washed with water, with 0.5 N sodium hydroxide, and again with water to purify the alpha glycol. Evaporation of the ethereal phase yielded a crystalline residue of the isomeric transoid (16( 3),17(0i)-dihydroxy-steroid-3-methyl ether and cisoid 16(0 ),17(0 )-di-hydroxy-steroid-3-methyl ether. 

To approximately 1.3 g of hydrogen fluoride contained in a polyethylene bottle and maintained at -60°C was added 2.3 ml of tetrahydrofuran and then a solution of 500 mg (0.0012 mol) of 6a-fluoro-9p,lip-epoxy-16a-methyl-17a,21-dihydroxy-l,4-pregnadiene-3,20-dione-21-acetate in 2 ml of methylenechloride. The steroid solution was rinsed in with an additional 1 ml of methylene chloride. The light red colored solution was then kept at approximately -30°C for 1 hour and at -10°C for 2 hours. At the end of this... 

The situation is similar with cyclic boronates, which are prepared by the following procedure. Steroid (10 pmol) and the respective substituted boric acid (10 jumol) are dissolved in ethyl acetate (1 ml) and the mixture is allowed to stand for 5 min at room temperature. Under these conditions, 17,20-diols, 20,21-diols and 17,20,21-triols are converted completely into boronates. Cyclic boronate was mainly produced from 17,21-dihydroxy-20-ketone, but side-products also appeared, the formation of which could be suppressed by adding a 10% excess of the reagent [387—389]. Different substituents on the boron atom, such as methyl, n-butyl, tert.-butyl, cyclohexyl and phenyl, are interesting from the viewpoint of GC—MS application. They are further suitable for converting isolated hydroxyl groups into TMS or acetyl derivatives. 

The Leukart reaction has also been used in the conversion of dehydroepiandro-sterone into 17/3-formylamino-3/3-formyloxyandrost-5-ene, which on reduction with lithium aluminium hydride afforded 3/3-hydroxy-17/3-me thylaminoandrost-5-ene. Acylation with isocaproyl chloride then furnished the N-methyl-N-isocaproyl steroid (197), after selective ester hydrolysis of the initially formed ON-diacyl derivative. The amide (197) was further converted into its 3,5-cyclo-6-ketone via the 3,5-cyclo-6/3-alcohol and thence by reaction with hydrogen bromide into the corresponding 3/3-bromo-5a-6-ketone which upon dehydrobromination furnished a A2-5a-6-ketone and ultimately the 2-monoacetate of the 2/3,3/3-diol (198) after reaction with silver acetate and iodine. Hydrolysis to the 2/3,3/3-diol (198) gave a separable mixture of the 2/3,3/8-dihydroxy-5a- and -5/3-ketones.88... 

Reaction of steroidal tosylates with KNO2 in DMSO or DMF gave reasonable yields of alcohols with inverted configuration. The previously reported epi-merization at C-3 during Raney nickel-catalysed hydrogenation of methyl 3, 1 a-dihydroxy-12-oxo-5/8-cholanate was incorporated in a report of the synthesis of 3/3,7a,12j8-trihydroxy-5/3-cholanic acid and the 3a,7a,12/3-trihydroxy-analogue. Conversion of mestranol into epimestranol was achieved by treatment of the 17-mesylate with silver nitrate in aqueous THF. ... 

Ap-68 Sax, K. J., Holmlund, C. E, Feldman, L. I., Evans, R. H., Jr., Blank, R. H., Shay, A. J., Schultz, J. S., and Dann, M., Steroids 5, 345 (1965). la,2a-Di-hydroxylation of 17a-ethynyl-170-hydroxy-4-androsten-3-one, 9a-fluoro-110,170-dihydroxy-17a-methyl-4-androsten-3-one, and 110,21-dihydro Qr-16a,17a-isopro-pylidenedioxy-4-pregnene-3,20-dione by inducible enzyme from Nocardla corallina. Same reaction with a A -substrate, proposed as intermediate In this process. 

Kallner (66) studied the stereospecific formation of 5a steroids by the reduction of 3-keto- -derivatives with Li in liquid ammonia (Fig. 7). Oppenauer oxidation of methyl cholate provided the 3-dehydro derivative IX which was hydrolyzed to the free acid (X) and the product dehydrogenated with Se02 to the dihydroxy-3-ketochol-4-enoic acid (XI). The unsaturated acid (XI) was reduced with Li in liquid ammonia, and the product methylated to provide a mixture from which XII was separated from the desired ketone... 

The method of Chakravarti, Chakravarti, and Mitra (84) for the transformation,of 3-hydroxy-5 steroids to 3-keto-5a steroids has been utilized by Danielsson et al. (34) for the preparation of methyl 12a-hydroxy-3-keto-5a-cholanoate from the corresponding 5 3 derivative, and by Anderson and Haslewood (69) for the preparation of ethyl 3 3,7 ,r2 -trihydroxy-5a-chol-anoate from ethyl 7a,12a-dihydroxy-3-keto-5a-cholanoate in boiling cymene. The latter authors have commented on the poor and capricious yields obtained by this procedure (25). 

Estradiol is the actual ovarian follicular hormone. It is a colourless steroid, slightly soluble in water, but freely soluble in organic solvents. Chemically, it is the 3 4-dihydroxy derivative of oestrane, or 13-methyl cydo-pentano phenanthrene, the mono-methylated steroid nucleus which occurs in all the natural oestrogens (p. 172). (Estrone and oestiiol represent various oxidation... 

Steroids. A soln. of 21-acetoxy-20-ethylenedioxy-5a,17a-dihydroxy-6) -methyl-pregnane-3,ll-dione in 50%-aq.-methanolic 0.05 N NaOH allowed to stand 17 hrs. at room temp, under N2-> 20-ethylenedioxy-17 ,21-dihydroxy-6a-methyl-4-pregnene-3,ll-dione. Y ca. 100%.— The 6-methyl group is epimerized to the equatorial a-configuration. S. Bernstein and R. Littell, Am. Soc. 82, 1235 (1960). 

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