ANDROSTAN-3-ONE, 17-HYDROXY

NX - 5-alpha 17-bata-ANDROSTAN-3-ONE 17-HYDROXY-2-1HYDROXYMETHYLENE)-17-METHYL-... 

Androstan-3-one, 17-hydroxy-2-(hydroxymethylene)-17-methyl-2,6-Pyridinediamine, 3-(phenylazo)-, monohydrochloride 3,3-Bis(4-hydroxyphenyl)-l(3A7)-isobenzofuranone Benzenemethanamine, A -(2-chloroethyl)-Ai-(l-methyl-2-phenoxyethyl)-, hydrochloride Styrene-7,8-oxide... 

Androstan-3-one, 17-hydroxy-2-(hydroxymethylene)-17-methyl-2,6-Pyridinediamine, 3-(phenylazo)-, monohydrochloride... 

N1 - 5-alpha-ANDROSTAN-3-ONE, 17-beta-HYDROXY-, 0-[Pg.58]

Ether formation often leads to enhanced oral activity. 17/8-Hydroxy-5a-androstan-3-one 17-(rmethoxy)cyclopentyl ether (D-130), 17)3-hydroxy-5a-androstan-3-one 17-(l -ethoxy)cyclopentyI ether (D-132), 17j3-hydroxy-5a-androst-l-en-3-one 17-(r-ethoxy)cyclopentyl ether (A-163), and 17j3-hydroxy-5a-androst-l-en-3-one 17-cyclopent-r-enyl ether (A-164) are all reported to possess favorable anabolic-androgenic ratios with increased anabolic and androgenic properties. The enhancement of oral activity is interesting in view of the fact that the ether bond of these compounds is easily broken, as manifested by the strongly enhanced excretion of 17-ketosteroids in humans treated with the ether derivatives [144]. 

Hydroxy-7a,l 7-dimethyl-4-androsten-3-one 17 /3-Hydroxyestr-4-en-3-one /3-phenylpropionate 17 /3-Hydroxy-l 7-ethyl-estr-4-en-3-one 17 /3-Hydroxy-l 7-methyl-2-oxa-5[Pg.214]

The N-oxyl-4, 4 -dimethyloxazolidine derivative (685) of 17)3-hydroxy-5a-androstan-3-one 17-methylphosphonofluoridate has been used as a spin label... 

The preparation of various heterocyclic androstanes has been reported. Condensation of 17jS-hydroxy-l-oxo-l,2-secoandrostan-2-oic acid (170a) with ammonia in the presence of hydrogen and Raney nickel led to 2-aza-17 8-hydroxy-5a-androstan-3-one (17 la). The synthesis of the -analogues was accomplished... 

The reaction of 6-amino-5-(l,2-diethoxycarbonylhydrazino)pyrimidines with enamines represents another convenient method for the preparation of pteridines. Fusion of 5-(l,2-diethoxycarbonylhydrazino)-2,4,6-triaminopyrimidine (281) with an excess of mor-pholinocyclohexene leads to 2,4-diaminotetrahydrobenzo[g]pteridine, and with the morpholinoenamine (282) from 17/3-hydroxy-5a-androstan-3-one regioselective condensation to the fused pteridine (283) takes place in almost quantitative yield (equation 101) (71CC83). 6-Amino-5-nitroso- and 6-amino-5-phenylazo-pyrimidines react similarly, imitating the Timmis-type reaction (72CPB1428). 

The presence of an a-bromo substituent may cause anomalies. With NaBH4, 2a-bromo-5a-cholestan-3-one gives a mixture of epimers, in which the 3p-o predominates. 4 -Bromo-17)5-hydroxy-5)5-androstan-3-one acetate gives 25% of the 315,4 -bromohydrin and 34% of the 3a,4)5-compound. Reduction of 7a-bromo-3)5,5a-diacetoxycholestan-6-one gives exclusively 7a-bromocholestane-3)5,5a,6a-triol 3,5-diacetate,whereas reduc-... 

A total of 3 g (0.13 moles) of sodium hydride is added to a solution consisting of 10 g of 17 -hydroxy-5a-androstan-3-one (36 mmoles) in 200 ml of benzene and 10 ml of ethyl formate. The reaction mixture is allowed to stand under nitrogen for 3 days followed by dropwise addition of 10 ml of methanol to decompose the excess of sodium hydride. The solution is then diluted with 300 ml water and the layers are separated. The basic aqueous solution is extracted with ether to remove neutral material. The aqueous layer is acidified with 80 ml of 3 A hydrochloric acid and the hydroxymethylene steroid is extracted with benzene and ether. The combined organic extracts are washed with water and saturated sodium chloride solution and then dried over magnesium sulfate and concentrated. The residue, a reddish-yellow oil, crystallized from 10 ml of ether to yield 9.12 g (83%) of 17 -hydroxy-2-hydroxymethylene-5a-androstan-3-one mp 162-162.5°. Recrystallization from chloroform-ether gives an analytical sample mp 165-165.5° [a]o 53° (ethanol) 2 ° 252 mjj. (g 11,500), 307 m u (e 5,800). 

A mixture of 3.18 g (10 mmoles) of 17 -hydroxy-2-hydroxymethylene-5a-androstan-3-one, 20 ml dry dimethyl formamide and 0.3 g (13 mmoles) of sodium hydride is stirred for 0.5 hr at room temperature under nitrogen. A total of 1.51 g (12.5 mmoles) of redistilled allyl bromide is added and the mixture is stirred for 1 hr on the steam bath. Aqueous potassium hydroxide (2 g in 5 ml of water) is added and stirring is continued for 1 hr on the steam bath. The reaction mixture is diluted with 50 ml of methylene dichloride followed by careful addition of 300 ml of water. The organic phase is separated and the aqueous phase is again extracted with 50 ml of methylene dichloride. The combined extracts are washed with water, dried over sodium sulfate, filtered and chromatographed on 200 g of silica gel. Elution with pentane-ether (4 1) provides 2a-allyl-17j -hydroxy-5a-androstan-3-one 0.85 g (26%) mp 118-119° [aj 14° (CHCI3), after crystallization from ether-hexane. 

Treatment of 4-methyltestosterone under the same conditions affords 17 -hydroxy-4,4-dimethyl-5a-androstan-3 One in about 60% yield while 17jS-hydroxyandrosta-4,6-dien-3-one gives only a low yield of 17 -hydroxy-4,4-dimethylandrost-5-en-3-one. ... 

Jones and Price"" therefore concluded that diazomethane ring enlargement of 17j5-hydroxy-5a-androstan-3-one (Ic) proceeds with predominately C3—C4. migration, in contrast to the 5a-cholestane series which differs from (Ic) only in the 17-substituent. 

Ring enlargement of 17jS-hydroxy-5jff-androstan-3-one (12) with diazomethane gives 17j8-hydroxy-A-homo-5j8-androstan-3-one (13) and 17)8-hydroxy-A-homo-5j8-androstan-4-one (14) in a total yield of 72%. 

B-Homosteroids were first reported by Ringold in the course of an investigation of the relationship of structural changes to biological activity of anabolic agents. The Tiffeneau rearrangement sequence described earlier for the preparation of A-homosteroids was used to synthesize 17/ -hydroxy-B-homo-5a-androstan-3-one (56a). 

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... 

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