3a-Hydroxy-5a-androstan-17-one

Force-field calculations have given the atomic co-ordinates for 3a-hydroxy-5a-androstan-17-one ( androsterone ) with about the same accuracy as X-ray measurements, the errors being no greater than 0.1 A. The value of this method lies partly in its speed (10 minutes of IBM 360 computer time) and partly in the fact that no crystal is required. Variations of energy with conformation can also be computed. The authors stress the likely dangers in using Dreiding models, which may differ markedly in shape from actual molecules because they fail to simulate torsional and van der Waals effects. 

Ingenious application of remote oxidation has opened the way to a novel and potentially useful degradation of 5a-cholestan-3a-ol to 3a-hydroxy-5a-androstan-17-one ( androsterone ). The radical relay process, whereby photolysis of an iodoaryl ester with iodobenzene dichloride introduces a chlorine atom or unsaturation into the steroid nucleus, has been adapted by use of the 3a-(4 -iodobiphenyl-3-carboxylate) (301). The size of this ester grouping allows the iodine atom to come... 

As an example of a clear improvement in separation we can cite the data on the retention of steroids on a non-polar silicone stationary phase, SE-30, as presented by Heftmann [54]. Two monohydroxy-steroids, 5a-cholestan-3 3-ol and 5-cholesten-3 3-ol, have the same relative retention (2.85) on a column containing a non-polar stationary phase (internal standard cholestane), but the relative retentions of their trimethylsilyl derivatives are 2.60 and 2.55 and those of their chlorodichloroacetates are 3.79 and 3.62, respectively. The relative retention times of 3a-hydroxy-5a-androstan-17-one and 3j3-hydroxy-5a-androstan-17-one are similar at 0.96 and 1.00, respectively, whereas those of their TMS ethers are 0.46 and 0.61, respectively. 

Ap-54 Noguchi, S., and Fukushima, D. K., J. Org. Chem. 30, 3552 (1965). Penicillium sp. with 3a-hydroxy-5a-androstan-17-one gave 12 -hydroxy product. The same organism with 3/S-hydroxy-5o-androstan-17-one gave the la-hydroxy product and with 3/3-hydroxy-50-androstan-17-one gave the 7 -hydroxy product and 7/ -hydroxy-5/3-androstane-3,17-dione. 

Maltais, R., Luu-The, V., and Poirier, D., Parallel solid-phase synthesis of 3 3-peptido-3a-hydroxy-5a-androstan-17-one derivatives for inhibition of type 3 17 3-hydroxysteroid dehydrogenase, Bioorg. Med. Chem., 9, 3101, 2001. 

The marked influence of solvent and temperature on product composition is illustrated by results obtained with 3 5-hydroxy-5a-androstan-17-one (5), which yields in addition to the 3a-fluoro derivative (6) the elimination... 

The equatorial allylic alcohol 3)S-hydroxyandrost-4-ene is oxidised by Cr(Vl) 310 times faster than the saturated 3)3-hydroxy-5a-androstan-17-one, 5.7 times faster than the axial 3a-hydroxyandrost-4-ene and 6.9 times faster than its 3-deuterated analogue . The greater speed of oxidation of the equatorial isomer is in contrast to the pattern observed for saturated alcohols and probably arises from resonance between the double bond and the incipient carbonyl group. 

A solution of 70% perchloric acid (60 ml) in water (280 ml) was added to a stirred solution of 5a-androst-2-en-17-one (200.0 g) in ether (1.15 I) at 15°C followed by portionwise addition of N-bromacetamide (112.0 g) over 10 min. After stirring for 1 h the precipitated white crystalline solid was filtered off, washed neutral with ether and water and crystallised to give 2p-hydroxy-3a-bromo-5a-androstan-17-one (172.0 g). The ether layer of the filtrate was washed neutral, dried (Na2S04) and concentrated to give a second crop (28.0 g). The two crops (200.0 g) were suspended in methanol (1 L), 10 N aqueous potassium hydroxide solution (100 ml) added and the mixture slowly distilled over 45 min. Addition of water precipitated the product as a white solid which... 

A solution of the 2p,3[3-epoxy-5a-androstan-17-one (30.0 g) in ethanol (130 ml), water (15 ml) and liquid ammonia was heated in an autoclave at 150°C for 6 h and the resultant crystalline suspension evaporated to dryness. Water (35 ml) and acetic acid (36 ml) were added and the solution kept at 90°C for 1 h, cooled and excess water added. The precipitated material was filtered off and the filtrate made alkaline with aqueous 10 N potassium hydroxide solution to precipitate a white solid which was filtered off, washed neutral with water, dissolved in methylene chloride, the solution dried (Na2S04) concentrated and ether added to give 2p-hydroxy-3a-amino-5a-androstan-17-one (14.3 g), melting point I92°-195°C. 

Dihydroxy-5-androsten-16-one Sa-Hydroxy-o/S-androslan-lT-one 3a-Hydroxy-5a-aiidrostatt-17-one 3j3-HydrOxy-oa-androstan-17-onc... 

C32H37NO4 76811-98-8) see Fexofenadine hydrochloride 4-[4-[4-(hydroxydiphenylmethyl)-l-piperidinyl]-l-oxo-butyl]-a,a-dimcthylbenzeneacetic acid ethyl ester (C34H4[N04 76812-02-7) see Fexofenadine hydrochloride 3a-hydroxy-2p,16p-dipiperidino-5a-androstan-17-one (C2cjH4jN202 13522-14-0) see Pancuronium bromide Vecuronium bromide 9-hydroxyellipticine... 

List of abbreviations and trivial names. Dehydroepiandrosterone (DHA, D), 3/J-hydroxyandrost-5-en-17-one androstenediol (A°-diol, A ), androsta-5-en-3/S, 17 -diol androstenetriol (triol), androsta-5-en-3, 16o, 17 -triol androsterone (A), 3ot-hy-droxy-5a-androstan-17-one 5/S-androsterone (5fiA), 3a-hydroxy-5/3-androstan-17-one epiandrosterone, 3/3-hydroKy-5o-androstan-17-one androstanediol (Adiol), 5a-and-rostan-3a, 17/S-diol 3/S-androstanediol, 5a-androstan-3/9, 17/3-diol 5/3-androstanediol (5 Adiol), 5/S-androstan-3a, 17 -diol androstenedione (A ), androsta-4-en-3, 17,... 

Hydroxy-l7a-methyl-2-oxa-5a-androstan-3-one, 41B, 592 2,4-Dioxa-5a-androstan-17/3-ol acetate, 41B, 593 14p-Azido-5a-androstane, 40B, 486 3a, 17/J-Dihydroxy-5a-androstane, 38B, 531 5/3-Androstane-3a, 1 7 -diol, 37B, 295 17/3-Hydroxyandrostan-3-one monohydrate, 38B, 532 3/3,17/3-Dihydroxy-5a-androstane monohydrate, 39B, 382... 

Pregnene-17a,21-diol-3,20-dione, 38B, 539 39B, 386 Aldosterone monohydrate, 38B, 540, 17/3-Bromoacetoxy-5a-androstan-3-one, 44B, 482, 2/3-Bromo-3a-hydroxy-5a-pregnane-l 1, 20-dione, 46B, 528, 2a-Bromo-17p-acetoxy-9-methyl-5a,9P,1Oa-estran-3-one,... 

Androsten-3,16,17-trione 3a-Hydroxy-5 aiidrt tane-ll, 17-rKone 3tt-Hydr xy-5a-aiidrostane-11,17-dione 3a, 1 lp-Dihydroxy-5 androstan-17-one 3 , 11 )S-1 )ihydro -5a-androstan-l 7-one 3-Oxo-A-aiidrosten-17 yl-sulfatc l7 -Hydioxy-5-androsten-3/3-yl-sulfate l7-Oxo-5a-androstan-3a-yl-sulfate... 

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