Androstane-3,17-diol

C21H28O3 2398-63-2) see Estrone (3p,5a,l 7P)-androstane-3,17-diol 17-benzoate (C24H3,j03 6242-26-8) see Mesterolone 3,17-androstanedione... 

Topical androgen posing oil" sterile solution 100MG free l,4-androstane-3,17 diol,. This is the product re-labelled as both Drive, and as Boldenone 50MG/ML. I have to admit results did seem similar. Those utilizing 2-4ML daily had compared Protest II to 200-400MG of Equipoise per week. 

Other compounds, such as ketols (1 l-keto-3-ol), as well as 11-monoketo, characterized by this p stereochemistry (for C-14), have a similar behavior concerning the formation of these ions. In addition to the interest in distinguishing ring junction geometries, Gaskell and co-workers [206a,b] studied the behavior of a and p stereochemistry of the di-OTBDMS (t-butyldimethylsilyl) groups in derivatives of androstane-3,17-diol (Fig. 56). 

The stereoselectivity of the hydride reduction of conjugated cyclohexenones has also been subjected to close examination from both experimental and theoretical viewpoints. Much of the work has involved polycyclic systems, e.g.. steroids which have little conformational flexibility and in which axial and equatorial directions of approach can be clearly defined. With small" hydride donors, these substrates show an even clearer preference for axial attack than the corresponding cyclohexanones. For examples involving reductions with lithium aluminum hydride and sodium borohydride, see Table 10. 3/(-Acetylcholest-5-en-7-one and cholest-2-en-l-one are notable in that the analogous saturated substrates are attacked from the equatorial direction115 l16. The reduction of 17/i-hydroxy-4-androsten-3-one (testosterone) to 4-androstene-3/1,17/j-diol with d.r. 90 10 can be compared with the sodium borohydride reduction of 17/i-hy-droxyandrostan-3-one (dihydrotestosterone) to androstane-3/ ,17/ -diol with d.r. 81 19 (see p 4030). 

Allopregnane -3(J,17 -diol -20-one. 3B, 17-D, hydr-oxy-Sa-presnan-20-one 30, 17-dihydroxy-20-oxo -5a-preg-nane 17-111-ketoethyl)androstane-3,17-diol Reichstein s subetance L winlcrsteiner s compound G. C2 HMOj mol... 

HjjJ mol wi 260.45, C 87.62%, H 12.37%. From androst -ane 3,17-dione fiutenandt Tscherning, Z, FhysjoJ, Chem-229, [85 (1934). From androstane-3,17-diol Steiger ... 

Scheme 6-17 Regio-selective hydroxylation of androstane-3,17-diol (37) catalyzed by the Mn -porphyrin 39 in the presence of iodoso-benzene.

The liquid-crystalline mesophases of cholesteryl benzoate and p-phenylbenzoate provide useful stationary phases for the gas chromatography of steroids, giving separations largely on the basis of molecular shape. These steroidal materials have distinct advantages over the more conventional stationary phases for certain applications, including separations of the isomeric androstane-3,17-diols or pregnane-3,20-diols, and of cholest-4-ene from the 5-ene. The dicho-lesteryl esters of some dicarboxylic acids are reported to exhibit liquid-crystalline properties. The temperature-dependence of the Kerr effect has been measured for a series of liquid-crystalline esters of cholesterol. 

Androstane Androstane-17-carboxylic acid, (5(3,17(3) Androstane-3,17-diol, (3a,5a,17(3)... 

Kidney Various 5a-androstane-diols 5a-Reductase and dehydrogenases Induction of enzymes Some induced proteins have yet to have a prescribed function... 

A number of steroids have been regioselectively acylated ia a similar manner (99,104). Chromobactenum viscosum hpase esterifies 5a-androstane-3P,17P-diol [571-20-0] (75) with 2,2,2-triduoroethyl butyrate ia acetone with high selectivity. The hpase acylates exclusively the hydroxy group ia the 3-position giving the 3P-(monobutyryl ester) of (75) ia 83% yield. In contrast, bacillus subtilis protease (subtihsia) displays a marked preference for the C-17 hydroxyl. Candida iylindracea]i 2Lse (CCL) suspended ia anhydrous benzene regioselectively acylates the 3a-hydroxyl group of several bile acid derivatives (104). 

Estr-5(10)-ene-3a,17 -diol (10 g, 36.2 mmoles) is added over a period of 1 hr to a refluxing mixture consisting of 60 g (0.92 moles) of zinc-copper couple, 350 ml of dry ether and 180 g (54 ml, 0.67 moles) of methylene iodide. After the addition is complete, half of the solvent is removed by distillation and 200 ml dry ether is added. The reaction mixture is then transferred to a sealed stainless steel tube and maintained for 3 hr at 92° before being cooled in an ice bath and poured into 500 ml of saturated aqueous sodium bicarbonate solution. The resultant mixture is extracted with ether and the extracts are dried over anhydrous sodium sulfate and concentrated to yield a solid residue which gives 8.4 g (80%) 5,19-cyclo-5a,10a-androstane-3a,17) -diol mp 161-163° [aJo 40° (CHCI3), on crystallization from acetone. 

Vinyllithium Reaction To a cooled solution of 80 g of 3y -hydroxy-5a-androstan-17-one in 1.5 liters of tetrahydrofuran is added 400 ml of 2 4/ vinyllithium in tetrahydrofuran. The solution is stirred at 0° for 0.5 hr, allowed to warm to room temperature, and stirred an additional hr. Cone ammonium chloride solution is added, and the mixture is concentrated under reduced pressure until a precipitate begins to form. The slurry is poured into water, and the precipitate is filtered and recrystallized twice from methanol, affording 52.2 g (60%) of 17a-vinyl-5a-androstane-3, 17i -diol mp 205-207.5°. 

Tiffeneau ring enlargement is a route to D-homosteroids. Goldberg and Monnier" treated the 17i5-hydroxy-20-amine (91) prepared by hydrogenation of 17a-cyano-5a-androstane-3)3,17j5-diol (90a) with nitrous acid and obtained 3i5-hydroxy-5a-D-homo-androstan-17a-one (92). 

Goldberg and Wydler have shown that the 17a-ketone is not the only product of the Tiffeneau ring enlargement sequence. Careful examination of the products derived from nitrous acid deamination of 17a-aminomethyl-5a-androstane-3/l,17j6-diol 3-acetate (91) showed the presence of a minor amount of isomeric D-homo-17-one (98). 

Similarly, androstane-5a,6a,17)S-triol 6-tosylate 17-benzoate (115b) is converted to 17)S-hydroxy-6)S-methyl-10(5 6)SH)flZ)en-androstan-5-one benzoate (116b) on treatment with calcium carbonate in dimethylformamide. Similar treatment of 10-methyldecalin-l,9-diol 1-tosylate (121) gives 10-methylbicyclo[5.3.0]decan-l-one (122). 

A-norsteroids (59) of the cholestane, androstane, pregnane and hydrocortisone series have been prepared from the diols (61)." However, preparation of these 1,2-diols is complicated by concomitant formation of isomeric 4,5-diols, which are usually difficult to separate. The sequence (58) -> (59) appears to be the most practical route to A-norsteroids (59), provided that diosphenol (58) is readily available. 

Acetylenedimagnesium bromide, 66, 84, 137 Acyl-alkyl diradical disproportionations, 299 Acyl-alkyl diradical recombination, 296 Alkaline hydrogen peroxide, 10, 12, 20 Alkylation of formyl ketones, 93 Alkylation via enolate anions, 86 17a-Alkynyl steroids from 17-ketones, 67 2a-Al]yl-17jS-hydroxy-5a-androstan-3 -one, 9 5 Allylic acetoxylation, 242 Allylmagnesium bromide, 64 17 -Aminoandrost-5-en-3 -ol, 145 17 a-Aminomethy 1-5 a-androstane-3, 1718-diol, 387... 

Cy ano-17- (2 -tetr ahydropyr anyloxy) -androst-5-en-3 -ol acetate, 134 5,19-Cyclo-5a, 10a-androstane-3a, 17/3-diol, 113... 

Vibrational relaxation, 293, 295 17 a-Vinyl-5a-androstane-3 /3,17 /3-diol, 164 Vinyllithium, 64, 163 Vinylmagnesium chloride, 58 4-Vinyltestosterone, 89... 

A solution of sodium borohydride (8 grams) in water (16 ml) was added to a stirred solution of 2(3,16(3-bis-piperidino-5a-androstan-3a-ol-17-one (17 grams) in tetrahydrofuran (70 ml) and methanol (30 ml) and the solution stirred at room temperature for 16 hours. The product was precipitated by the addition of water, filtered off, dried, and crystallized from acetone to give the diol (14.9 grams). 

C7H5NO4 499-83-2) see Pyridinol carbamate 2p,16p-diplperidino-5a-androstane-3a,17p diol... 

C7H,jOS 98-91-9) see Stepronin 3a-thiocyanato-5a-androstane-2f),l 7P-diol 17-acetate (C22H33NO3S 2469-96-7) see Epitiostanol thiocyanic acid... 

A-Nor-5.alpha.-androstan-3-one, 17.b. -hydr oxy-5-vinyl-, acetate (8CI) P ocarpa-8,11, 13-triene-3.beta.,12-diol, 13-isopropyl-, diacetate (8CI)... 

Hydroxy ketones and hydroxy-a,/3-unsaturated ketones in the steroids such as estrone and testosterone, respectively, can be reduced to diols biochemically. Estrone acetate gave 68% yield of a-estradiol on incubation with baker s yeast at room temperature after five days [909]. Testosterone was reduced by bacteria to the saturated hydroxy ketones, etiocholan-17-ol-3-one and androstan-17-ol-3-one, and further to the diols, ep/-etiocholane-3,17-diol and the epimeric isoandrostane-3,17-diol, both in low yields [329]. 

This enzyme [EC 1.1.1.53] catalyzes the reaction of an-drostane-3a,17j8-diol with NAD+ to produce 17/3-hydro-xyandrostan-3-one and NADH. The 3a-hydroxyl group or the 20/3-hydroxyl group of pregnane and androstane steroids can act as the substrate. 

Figu re 6.3 Complementary biocatalyzed regioselective acylation of the steroid model 5a-androstan-3P,17 3-diol (10). 

An enzyme reactor with immobilized 3 -hydroxysteroid dehydrogenase has been successfully used for the analysis of residues of 17 -methyltestosterone in trout by high-performance liquid chromatography (HPLC) (269). Following their separation by reversed-phase chromatography, the major tissue metabolites of 17 -methyltestosterone, namely 5 -androstane-17 -methyl-3, 17 -diol, and 5 -androstane-17 -methyl-3, 17 -diol, were enzymatically modified in the presence of a coreactant, nicotinamide-adenine dinucleotide (NAD), to the corresponding ketone. The position at 3 was enzymatically oxidized, and NADH, the reduced form of NAD, was produced as a coproduct and subjected to fluorescence detection. Reoxidation of NADH to NAD provides the possibility for electrochemical detection. 

Pancuronium bromide (2P,16P-dipiperidino-5a-androstan-3a,17p —diol diacetate... 

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