5-Androstene

Bacterial removal of sterol side chains is carried out by a stepwise P-oxidation, whereas the degradation of the perhydrocyclopentanophenanthrene nucleus is prevented by metaboHc inhibitors (54), chemical modification of the nucleus (55), or the use of bacterial mutants (11,56). P-Sitosterol [83-46-5] (10), a plant sterol, has been used as a raw material for the preparation of 4-androstene-3,17-dione [63-05-8] (13) and related compounds using selected mutants of the P-sitosterol-degrading bacteria (57) (Fig. 2). 

DHEA(23) 4-Androstene-3,17-dione —> Estrone (26) Estrogens Cortisone (31)... 

Ammonium sulfate triolein, oleic acid, androsten-3,17-dione, xanthanonic acid, cholesterol-propionate, N-methy Ipheny lalanine, D-glucose fluorescence after heating to 150 — 180 °C, exposure to tert-butyl hypochlorite [203]... 

Treatment of 16a-mesyloxy or tosyloxy-20-hydroxypregnanes with base provides A -androstenes in ca. 30% yield... 

The 10l -acetoxy group can be red actively removed with zinc and acetic acid or chromous chloride to give I9-norsteroids in high yield. Thermal elimination (boiling tetralin) of acetic acid from the crude 10)5-acetoxy-A -3-ketone or treatment with methanolic alkali leads to aromatization of ring A. Estrone alkyl ethers are formed from 10)5-acetoxy-19-nor-A -androstene-3,17-dione by treatment with alcohols and perchloric acid. Similar aromatizations are observed with 5,10-oxido, 5,10-dihydroxy, 5,10-halohydrins or 5,10-dihalo-3-ketones. ... 

Selective conversion of l,4-androstadiene-3,l7-dione to 4-androsten-3,17-dione was achieved with (Ph Pi RuClj (SI), prepared by refluxing ruthenium... 

As described in U.S. Patent 3,029,263, one possibility is a multistep synthesis starting from 3/3,17/3-dihydroxy-l 7a-methyl-5-androstene. 

Dana2ol was prepared from 4.32 grams of 17a-ethynyl-2-hydroxymethylene-4-androsten-17(3-ol-3-one, 1.00 gram of hydroxylamine hydrochloride, 1.12 grams of fused sodium acetate and 135 ml of acetic acid. To a 500 ml, 3-necked flask, equipped with a sealed Hershberg-type stirrer, a reflux condenser and a stopper, was added the above androstenone derivative in 300 ml of 95% ethanol. Stirring was commenced and a slurry of fused sodium acetate and hydroxylamine hydrochloride in glacial acetic acid was added. 

The crude product is distributed between equal parts of petroleum ether and 70% methanol. From the petroleum ether layer 5.6 grams of A -17a-ethyl-17(3-hydroxy-19-nor-androstene with a melting point of about 50°C are obtained. 

The starting material for the purposes of this discussion is 3-cycloethylenedioxy-10-cyano-17a-ethynyl-19-nor-A -androstene-17/3-ol (I). 

Androstene-3,l 7-dione and other androstane and testosterone-related steroids are often also produced. 

The strains described in Table 9.4 are all of commerdal value since they produce compounds which are either pharmacologically active or can be converted to pharmacologically important compounds. For example, the production of 1,4-androstadiene-3,17-dione from (5-sitosterol provides material which can be readily converted to estrone, while 4-androstene-3,l 7-dione can be converted to testosterone. 

Acetophenone, 4 methoxy 2 (p-methoxyphenyl)-, 40,16 30 Acetoxy-5 androstene 170-car-boxylic acid, 42, 4 30-Acetoxyetienic acid, 42, 4 3/8-Acetoxy-S pregnen-20 one, conversion to 3/3-acetoxyetienic acid, 42, 5... 

Nitro-3/ -acetoxy-androsten-(5)4 Zu einer Suspension von 39,2 g (0,22 Mol) fein gepulvertem N-... 

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