19-Hydroxyandrost-4-ene-3,17-dione

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Following essentially the same procedure and substituting 19-hydroxy-4-methyl-4-androstene-3,17-dione, 17β,19-dihydroxy-17α-methyl-4-androsten-3-one and 17β,19-dihydroxy-17α-propinyl-4-androsten-3-one for the 19-hydroxy-4-androstene-3,17-dione above results in the preparation of 4-methyl-4,6-androstadiene-3,17,19-trione, 17β-hydroxy-17α-methyl-4,6-androstadiene-3,19-dione and 17β-hydroxy-17α-propinyl-4,6-androstadiene-3,19-dione.

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 19-Hydroxy-4-androstene-3,17-dione and chloranil are dissolved in t-butanol and rapidly brought to reflux. The t-butanol is removed by distillation at atmospheric pressure at such a rate so that the total reflux and distillation time equals one hour. The dark pasty residue is triturated with hot chloroform and cooled. The solid which remains is removed by filtration and the filtrate successively extracted with water, a 2% sodium hydroxide solution and again with water. The organic layer is dried over magnesium sulfate and the solvent removed under vacuum to yield 19-hydroxy-4,6-androstadiene-3,17-dione. The diene so prepared is dissolved in acetone and chilled in an ice bath. Jones reagent is added over a period of about 10 minutes and stirring continued for an additional 45 minutes. The mixture is poured onto water. The solid which forms is filtered and recrystallized from benzene to yield 4,6-androstadiene-3,17,19-trione. to reflux The t-butanol is removed by distillation at atmospheric pressure at such a rate so that the total reflux distillation time equals one hour The dark pasty residue is triturated with hot chloroform cooled The solid which remains is removed by filtration the filtrate successively extracted with water The organic layer is dried over magnesium sulfate the solvent removed under vacuum

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 19-Hydroxy-4-androstene-3,17-dione, t-butyldimethylsilylchloride and pyridine are mixed in dry dimethylformamide and heated on a steam bath overnight. The reaction mixture is poured onto water and stirred well for 15 minutes. The resulting solid is filtered and dissolved in methylenechloride, dried over magnesium sulfate and the solvent removed. The residue is crystallized from an acetone-hexane solution to yield 19-t-butyldimethylsiloxy-4-androstene-3,17-dione. heated on a steam bath overnight The reaction mixture is poured onto water The resulting solid is filtered dissolved in methylenechloride dried over magnesium sulfate the solvent removed The residue is crystallized from an acetone-hexane solution

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 19-Hydroxyandrost-4-ene-3,17-dione is dissolved in methylenechloride and trimethyloxonium fluoroborate added. After stirring at room temperature for a period of two hours, water is added to the reaction mixture, the organic layer is separated, dried over magnesium sulfate and the solvent removed under vacuum. The residue is crystallized from an acetone-hexane solution to yield the desired 19-methoxyandrost-4-ene-3,17-dione. the organic layer is separated dried over magnesium sulfate the solvent removed under vacuum The residue is crystallized from an acetone-hexane solution

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of 9.0 gm (0.03 mole) of 19-hydroxy-4-androstene-3,17-dione, 11.8 gm (0.04 mole) of triphenylchlorosilane and 9.6 gm (0.12 mole) of pyridine contained in 100 ml of benzene is refluxed for a period of 18 hours. The resulting suspension is filtered and concentrated in vacuo to a yellow oil. The oil is placed on a silica gel chromatographic column packed in chloroform which is further eluted with chloroform. The chloroform eluant is evaporated to dryness in vacuo and recrystallized from methanol to yield 19-(triphenylsiloxy)-4-androstene-3,17-dione methanolate having a m.p. of 100°-2° C., uv max (MeOH) 223 nm (ε30,430), 242 nm (ε17,300). is refluxed for a period of 18 hours The resulting suspension is filtered concentrated in vacuo to a yellow oil is further eluted with chloroform The chloroform eluant is evaporated to dryness in vacuo recrystallized from methanol

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 9.0 gm (0.03 mole) of 19-hydroxy-4-androstene-3,17-dione, 4.3 gm (0.04 mole) of trimethylchlorosilane and 3.2 gm (0.04 mole) of pyridine is refluxed in 100 ml of benzene for a period of 18 hours. The resulting suspension is filtered, the volatiles removed in vacuo and concentrated to a yellow oil. The oil is placed upon a silica gel chromatographic column packed in chloroform and eluted with chloroform. The chloroform eluate is evaporated to dryness in vacuo and the residue is recrystallized twice from hexane to yield the desired 19-(trimethylsiloxy)-4-androstene-3,17-dione having a m.p. of 87°-9° C., uv max (MeOH) 242 nm (ε14,700). The resulting suspension is filtered the volatiles removed in vacuo concentrated to a yellow oil eluted with chloroform The chloroform eluate is evaporated to dryness in vacuo the residue is recrystallized twice from hexane

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Androst-4-en-19-ol-3,17-dione (11) is treated with acetic anhydride (Ac2O, b) in pyridine. Aqueous work-up is followed by extraction and purification to yield the acetate (14). Aqueous work-up is followed by extraction and purification

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Also known as 19-Hydroxytestosterone, this compound is commercially available from Steraloids, Inc. Alternatively, 19-hydroxyandrost-4-en-3,17-dione (11) is treated with potassium borohydride (KBH4, a) in ethanol at -10° to 0° C. Aqueous work up is followed by extraction and purification to yield 19-hydroxytestosterone (12). at -10° to 0° C Aqueous work up is followed by extraction and purification

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 30 g of 19-hydroxyandrost-4-ene-3,17-dione in 3 liters of acetone cooled in an ice bath is added 28 ml of Jones reagent over a 1 hour period. The reaction mixture is stirred for an additional 15 minutes, filtered and the solvent removed under reduced pressure at 35° C. The residue is taken up in a large volume of ether and 1.5 liters of water. The ether layer is collected, dried over magnesium sulfate, filtered and the solvent removed. The residue is crystallized from acetone-hexane to give 3,17-dioxoandrost-4-en-19-al, M.P. 126°-129° C. filtered the solvent removed under reduced pressure at 35° C The ether layer is collected dried over magnesium sulfate filtered the solvent removed The residue is crystallized from acetone-hexane

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of 19-hydroxyandrost-4-ene-3,17-dione in acetic anhydride and pyridine is allowed to stand overnight after which the reaction mixture is poured into ice water. The resulting solid is collected, dried and recrystallized from hexane to give 19-acetoxyandrost-4-ene-3,17-dione. The resulting solid is collected dried recrystallized from hexane

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 30 g. of 19-hydroxyandrost-4-ene-3,17-dione in 3 liters of acetone cooled in an ice bath is added 28 ml of Jones reagent over a one hour period. The reaction mixture is stirred for an additional fifteen minutes, filtered and the solvent removed under reduced pressure at 35° C. The residue is taken up in a large volume of ether and 1.5 liters of water. The ether layer is collected, dried over magnesium sulfate, filtered and the solvent removed. The residue is crystallized from acetone-hexane to give 3,17-dioxoandrost-4en-19-al, M.P. 126°-129° C. filtered the solvent removed under reduced pressure at 35° C The ether layer is collected dried over magnesium sulfate filtered the solvent removed The residue is crystallized from acetone-hexane

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of 22 g of 19-hydroxyandrost-4-ene-3,17 -dione, 18 g of 1-adamantanecarboxylic acid chloride, and 29 ml of pyridine in 2.2 liters of toluene is refluxed overnight. The reaction mixture is cooled, and the toluene layer is washed with water, dried over magnesium sulfate and filtered then the solvent is removed. The resulting residue is crystallized from methanol to give 19-(1 -adamantanylcarbonyloxy)androst-4-ene-3,17-dione, M.P. 161°-163° C. The reaction mixture is cooled the toluene layer is washed with water dried over magnesium sulfate filtered the solvent is removed The resulting residue is crystallized from methanol