897-06-3

Basic information

• Product Name: Androsta-1,4-diene-3,17-dione
• Synonyms: delta-1,4-androstadiene-3,17-dione;ANDROSTADIENDIONE;ANDROSTADIENEDIONE;ANDROSTA-1,4-DIENE-3,17-DIONE;(8R,9S,10R,13S,14S)-10,13-DIMETHYL-7,8,9,10,11,12,13,14,15,16-DECAHYDRO-6H-CYCLOPENTA[A]PHENANTHRENE-3,17-DIONE;1-DEHYDROANDROSTENEDIONE;1,4-ANDROSTADIEN-3,17-DIONE;1,4-ANDROSTADIENE-3,17-DIONE
• CAS NO: 897-06-3
• Molecular Formula: C₁₉H₂₄O₂
• Molecular Weight: 284.39
• EINECS: 212-977-2
• Product Categories: Pharmaceutical Intermediates;Intermediates & Fine Chemicals;Pharmaceuticals;Steroids
• Mol File: 897-06-3.mol
• Article Data: 41

Chemical Properties

• Melting Point: 138-139 °C(lit.)
• Boiling Point: 434.2 °C at 760 mmHg
• Flash Point: 162.1 °C
• Appearance: White crystalline powder
• Density: 1.14 g/cm³
• Vapor Pressure: 9.62E-08mmHg at 25°C
• Refractive Index: 1.568
• Storage Temp.: Refrigerator
• Water Solubility: 430mg/L at 20℃
• CAS DataBase Reference: Androsta-1,4-diene-3,17-dione(CAS DataBase Reference)
• NIST Chemistry Reference: Androsta-1,4-diene-3,17-dione(897-06-3)
• EPA Substance Registry System: Androsta-1,4-diene-3,17-dione(897-06-3)

Safety Data

• Hazard Codes: Xn
• Statements: 20/21/22-36/37/38
• Safety Statements: 26-36
• WGK Germany: 3
• RTECS: BV7988000
• Hazardous Substances Data: 897-06-3(Hazardous Substances Data)

Usage

Description

Androsta-1,4-diene-3,17-dione (Item No. 24081) is an analytical reference standard categorized as an anabolic androgenic steroid. Androsta-1,4-diene-3,17-dione is a precursor in the synthesis of boldenone and has been used to enhance athletic performance. Androsta-1,4-diene-3,17-dione is regulated as a Schedule III compound in the United States. This product is intended for research and forensic applications.

Chemical Properties

White Crystalline Powder

Uses

Boldenone related steroid; anabolic androgenic steroid

Definition

ChEBI: A steroid that consists of androstane having double bonds at positions 1 and 4 and two keto groups at positions 3 and 17.

Flammability and Explosibility

Notclassified

InChI:InChI=1/C19H24O2/c1-18-9-7-13(20)11-12(18)3-4-14-15-5-6-17(21)19(15,2)10-8-16(14)18/h7,9,11,14-16H,3-6,8,10H2,1-2H3/t14?,15?,16?,18-,19-/m0/s1

Synthetic route

2-phenylseleno-4-androstene-3,17-dione → Androsta-1,4-diene-3,17-dione (897-06-3)

Conditions	Yield
With dihydrogen peroxide In dichloromethane for 4h;	90%

2α-phenylseleno-4-androstene-3,17-dione → Androsta-1,4-diene-3,17-dione (897-06-3)

Conditions	Yield
With dihydrogen peroxide In dichloromethane	90%

androstanedione (846-46-8) → Androsta-1,4-diene-3,17-dione (897-06-3) + 5α-androst-1-ene-3,17-dione (571-40-4)

Conditions	Yield
With 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione In fluorobenzene; dimethyl sulfoxide at 70℃; for 24h;	A 4% B 84%
With 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione In fluorobenzene; dimethyl sulfoxide at 70℃; for 24h; Dehydrogenation;	A 4% B 84%

Androstenedione (63-05-8) → Androsta-1,4-diene-3,17-dione (897-06-3)

Conditions	Yield
With iodoxybenzene; benzeneseleninic anhydride In benzene for 12h; Heating;	72%
With diphenyl diselenide; iodosylbenzene In benzene for 12h; Heating;	72%
With periodic acid

3-thioxo-androst-1,4-dien-17-on (57334-04-0) → Androsta-1,4-diene-3,17-dione (897-06-3)

Conditions	Yield
With sodium hydroxide; tetra(n-butyl)ammonium hydrogensulfate In dichloromethane for 8h; Ambient temperature;	72%

androstanedione (846-46-8) → Androsta-1,4-diene-3,17-dione (897-06-3)

Conditions	Yield
With 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione In fluorobenzene; dimethyl sulfoxide at 85℃; for 48h;	72%
With 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione In fluorobenzene; dimethyl sulfoxide at 85℃; for 48h; Dehydrogenation;	72%
Multi-step reaction with 2 steps 1: HBr; acetic acid; bromine / anschliessend Erwaermen auf 50grad View Scheme
Multi-step reaction with 2 steps 1: 3-ketosteroid Δ4-(5α)-dehydrogenase / Enzymatic reaction 2: 3-ketosteroid Δ1-dehydrogenase / Enzymatic reaction View Scheme

cholesterol (57-88-5) → Androstenedione (63-05-8) + Androsta-1,4-diene-3,17-dione (897-06-3) + (20S)-20-hydroxymethylpregn-4-en-3-one (40736-33-2) + 24-norchol-4-ene-3,22-dione (80981-37-9) + 24-norchola-1,4-diene-3,22-dione (80981-38-0) + (20S)-20-(hydroxymethyl)pregna-1,4-dien-3-one (35525-27-0)

Conditions	Yield
Product distribution; degradation by the Mycobacterium mutant CCM 3528;	A n/a B 0.20 g C n/a D 0.36 g E 1.21 g F 71%

1-dehydrotestosterone (846-48-0) → Androsta-1,4-diene-3,17-dione (897-06-3)

Conditions	Yield
for 336h; Rhodotorula mucilaginosa;	54%

Progesterone (57-83-0) → testosterone (58-22-0) + Androstenedione (63-05-8) + Androsta-1,4-diene-3,17-dione (897-06-3) + testololactone (4416-57-3)

Conditions	Yield
With Fusarium dimerum In water at 30℃; for 36h; pH=7; Product distribution; Further Variations:; Reagents; pH-values; var. times;	A 17.4% B 52.6% C 12.4% D 6.2%

cholesterol (57-88-5) → testosterone (58-22-0) + Androstenedione (63-05-8) + Androsta-1,4-diene-3,17-dione (897-06-3) + 1-dehydrotestosterone (846-48-0) + 2-[(8S,9S,10R,13S,14S)-10,13-Dimethyl-3-oxo-3,6,7,8,9,10,11,12,13,14,15,16-dodecahydro-cyclopenta[a]phenanthren-(17Z)-ylidene]-propionic acid methyl ester (79694-52-3) + 22-hydroxy-23,24-bisnor-1,4-choladien-3-one (71658-22-5)

Conditions	Yield
With Mycobacterium sp. CCM 3529 Product distribution;	A 0.01 g B 0.03 g C 51% D 0.06 g E n/a F 0.38 g

β-sitosterol (83-46-5) → Androsta-1,4-diene-3,17-dione (897-06-3) + 23,24-Bisnorchola-1,4-dien-3-one-22-carboxylic acid (3614-61-7, 5327-60-6, 66512-12-7, 96686-97-4, 14508-05-5)

Conditions	Yield
With 8-quinolinol In water; N,N-dimethyl-formamide for 96h; Myc. lacticola 114;	A 5% B 47%

β-sitosterol (83-46-5) → Androstenedione (63-05-8) + Androsta-1,4-diene-3,17-dione (897-06-3) + 23,24-Bisnorchola-1,4-dien-3-one-22-carboxylic acid (3614-61-7, 5327-60-6, 66512-12-7, 96686-97-4, 14508-05-5) + stigmast-4-en-3-one (1058-61-3)

Conditions	Yield
With 8-quinolinol In water; N,N-dimethyl-formamide at 27℃; for 72h; Product distribution; Myc. mucosum 3-AP, pH = 7.2 - 7.7; other strains of bacteria, other pH, other temperatures, other inhibitors, other time, different age of bacteria culture, different concentration of substrate;	A 0% B 12% C 44.1% D 22%

β-sitosterol (83-46-5) → Androsta-1,4-diene-3,17-dione (897-06-3) + 23,24-Bisnorchola-1,4-dien-3-one-22-carboxylic acid (3614-61-7, 5327-60-6, 66512-12-7, 96686-97-4, 14508-05-5) + stigmast-4-en-3-one (1058-61-3)

Conditions	Yield
With 8-quinolinol In water; N,N-dimethyl-formamide for 72h; Myc. mucosum 3-AP;	A 12% B 44.1% C 22%

dehydroepiandrosterone (53-43-0) → androst-4,6-diene-3,17-dione (633-34-1) + 5-androstenedione (571-36-8) + Androsta-1,4-diene-3,17-dione (897-06-3)

Conditions	Yield
With 2,2'-bipyridylchromium peroxide In benzene for 3h; Product distribution; Heating; effect of various chromium(VI) based oxidants;	A 40% B 10% C 8%
With 2,2'-bipyridylchromium peroxide In benzene for 3h; Heating;	A 40% B 10% C 8%

β-sitosterol (83-46-5) → Androstenedione (63-05-8) + Androsta-1,4-diene-3,17-dione (897-06-3)

Conditions	Yield
With [2,2]bipyridinyl In water; N,N-dimethyl-formamide for 72h; Myc. flavum var. methanicum B5;	A 4% B 35%

Epiandrosterone (481-29-8) → testosterone (58-22-0) + 3β,11α-dihydroxy-5α-androstan-17-one (25848-75-3) + 3beta-7alpha-Dihydroxy-5alpha-androstane-17-one (25848-68-4) + 3beta-7beta-Dihydroxy-5alpha-androstane-17-one (25848-69-5) + 1α,3β-dihydroxy-5α-androstan-17-one (2260-01-7) + Androsta-1,4-diene-3,17-dione (897-06-3) + 1-dehydrotestosterone (846-48-0) + 6β-hydroxytestosterone (62-99-7, 2944-87-8, 34096-63-4, 34442-08-5, 145772-79-8) + 5α-androst-1-ene-3,17-dione (571-40-4) + 6β-hydroxy-4-androstene-3,17-dione (63-00-3)

Conditions	Yield
With malt extract; disodium hydrogenphosphate; calcium(II) chloride dihydrate; magnesium(II) chloride hexahydrate; strontium (III) chloride hexahydrate; potassium chloride; boric acid; sodium hydrogencarbonate; sodium sulfate; sodium chloride; potassium bromide; potassium hydroxide In water; N,N-dimethyl-formamide at 32℃; for 168h; pH=8; Enzymatic reaction;	A 2% B 2% C 2% D 3% E 5% F 5% G 3% H 2% I 2% J 32%

...Expand

Dithiocarbonic acid O-((8S,9S,10R,11R,13S,14S,17S)-17-acetyl-10,13-dimethyl-3-oxo-6,7,8,9,10,11,12,13,14,15,16,17-dodecahydro-3H-cyclopenta[a]phenanthren-11-yl) ester S-methyl ester → Androsta-1,4-diene-3,17-dione (897-06-3) + 1-{(1S,3aS,4R,7aS)-4-[2-(5-Hydroxy-2-methyl-phenyl)-ethyl]-7a-methyl-2,3,3a,4,7,7a-hexahydro-1H-inden-1-yl}-ethanone (83568-64-3)

Conditions	Yield
With 2,2'-azobis(isobutyronitrile); tri-n-butyl-tin hydride In toluene for 40h; Heating;	A 25% B 25%

cholesterol (57-88-5) → Androstenedione (63-05-8) + Cholest-4-en-3-one (601-57-0) + Androsta-1,4-diene-3,17-dione (897-06-3)

Conditions	Yield
With [2,2]bipyridinyl; Moraxella sp at 28℃; for 72h;	A 23% B n/a C 7%

cholesterol (57-88-5) → Androstenedione (63-05-8) + Androsta-1,4-diene-3,17-dione (897-06-3)

Conditions	Yield
With [2,2]bipyridinyl; Moraxella sp at 28℃; for 72h;	A 23% B 7%

3-thioxo-androst-1,4-dien-17-on (57334-04-0) → Androsta-1,4-diene-3,17-dione (897-06-3) + 1-Mercapto-4-methylestra-1,3,5(10)-trien-17-on (167956-32-3)

Conditions	Yield
With hydrogen bromide for 240h; Ambient temperature;	A 5% B 10%

pyridine (110-86-1) + 5α-androstan-2α,4α-dibromo-3,17-dione (42453-26-9) → Androsta-1,4-diene-3,17-dione (897-06-3)

2,4,6-trimethyl-pyridine (108-75-8) + 5α-androstan-2α,4α-dibromo-3,17-dione (42453-26-9) → Androsta-1,4-diene-3,17-dione (897-06-3)

progesterone (57-83-0, 851-22-9, 2000-66-0, 2755-10-4, 3562-13-8, 3795-19-5, 5750-05-0, 14546-13-5, 36027-73-3, 36027-74-4, 55122-80-0, 56271-98-8, 59952-90-8, 73889-98-2, 137940-28-4) → Androsta-1,4-diene-3,17-dione (897-06-3)

Conditions	Yield
With fusarium solani

5-androstenediol (521-17-5, 1963-03-7, 4593-57-1, 4593-58-2, 14504-94-0, 16895-59-3, 47122-33-8, 64162-67-0, 75767-22-5, 139973-51-6, 151284-19-4) → Androsta-1,4-diene-3,17-dione (897-06-3)

Conditions	Yield
With corynebacterium simplex

1α,3β-dihydroxy-androst-5-en-17-one (20998-18-9) → Androsta-1,4-diene-3,17-dione (897-06-3)

Conditions	Yield
With cyclohexanone; aluminum isopropoxide; toluene

1-dehydrotestosterone (846-48-0) + cyclohexanone (108-94-1) → Androsta-1,4-diene-3,17-dione (897-06-3)

Conditions	Yield
With aluminum isopropoxide; toluene

androstane-3,17-dione (1229-12-5) → Androstenedione (63-05-8) + Androsta-1,4-diene-3,17-dione (897-06-3) + 5β-Androst-1-ene-3,17-dione (571-39-1)

Conditions	Yield
With Phenylselenyl chloride; dihydrogen peroxide Yield given. Multistep reaction. Yields of byproduct given;

androstanedione (846-46-8) → Androstenedione (63-05-8) + Androsta-1,4-diene-3,17-dione (897-06-3) + 5α-androst-1-ene-3,17-dione (571-40-4)

Conditions	Yield
With Phenylselenyl chloride; dihydrogen peroxide Yield given. Multistep reaction. Yields of byproduct given;

β-sitosterol (5779-62-4, 83-46-5, 83-47-6, 19044-06-5, 31793-83-6, 125636-84-2, 130062-49-6) → Androsta-1,4-diene-3,17-dione (897-06-3) + 23,24-Bisnorchola-1,4-dien-3-on-22-oic acid (71154-85-3)

Conditions	Yield
With 8-quinolinol; Myc. mucosum 3-AP In N,N-dimethyl-formamide for 72h; Product distribution; other mycobacteria, various media for cultivation of mycobacteria;

bis-(3α,17β-dihydroxyandrost-5-en-1α-yl) disulphide (138430-08-7) → Androsta-1,4-diene-3,17-dione (897-06-3)

Conditions	Yield
Yield given. Multistep reaction;

Androsta-1,4-diene-3,17-dione (897-06-3) → 4α,5α-Epoxy-1-androstene-3,17-dione

Conditions	Yield
With C16H16F6FeN4O6S2; dihydrogen peroxide; acetic acid In acetonitrile at 20℃; for 0.166667h; stereoselective reaction;	100%

Androsta-1,4-diene-3,17-dione (897-06-3) + 2-hydroxy-2-methylpropanenitrile (75-86-5) → 17α-cyano-17β-hydroxyandrost-1,4-dien-3-one

Conditions	Yield
With sodium carbonate In water at 20 - 50℃; Temperature; Solvent; Reagent/catalyst;	98.6%
With sodium carbonate In water at 20 - 45℃; Solvent; Reagent/catalyst;	98.6%

Androsta-1,4-diene-3,17-dione (897-06-3) → (E)-(8R,9S,10R,13S,14S,8'R,9'S,10'R,13'S,14'S)-10,13,10',13'-Tetramethyl-7,8,9,10,11,12,13,14,15,16,7',8',9',10',11',12',13',14',15',16'-icosahydro-6H,6'H-[3,3']bi[cyclopenta[a]phenanthrenylidene]-17,17'-dione (143613-55-2, 143679-02-1)

Conditions	Yield
With zinc In tetrahydrofuran for 10h; Heating; other substrates;	97%
With zinc In tetrahydrofuran for 10h; Heating;	97%
With titanium; chloro-trimethyl-silane In 1,2-dimethoxyethane for 1h; Heating;	84%

Androsta-1,4-diene-3,17-dione (897-06-3) → 3-thioxo-androst-1,4-dien-17-on (57334-04-0)

Conditions	Yield
With Lawessons reagent In tetrahydrofuran for 1h; Ambient temperature;	96%
With Lawessons reagent In tetrahydrofuran for 1h; Ambient temperature; various steroides;	96%
With tetraphosphorus decasulfide

Androsta-1,4-diene-3,17-dione (897-06-3) → Androsta-1,4-dien-3,17-dion-17-hydrazon

Conditions	Yield
With sodium acetate; hydrazinium sulfate In ethanol for 72h; Ambient temperature;	95%

methyl bromide (74-83-9) + Androsta-1,4-diene-3,17-dione (897-06-3) → metandienone (72-63-9)

Conditions	Yield
Stage #1: methyl bromide With magnesium In tetrahydrofuran at 40 - 45℃; Stage #2: Androsta-1,4-diene-3,17-dione In toluene at 50 - 55℃;	94.6%
Stage #1: methyl bromide With magnesium In tetrahydrofuran at 40 - 45℃; Stage #2: Androsta-1,4-diene-3,17-dione In toluene at 50 - 55℃;	94.6%
Stage #1: methyl bromide With magnesium In tetrahydrofuran at 40 - 45℃; Stage #2: Androsta-1,4-diene-3,17-dione In toluene at 50 - 55℃; Stage #3: With hydrogenchloride In water at 50 - 55℃; pH=2 - 3;	93.8%

Androsta-1,4-diene-3,17-dione (897-06-3) + trimethylaluminum (75-24-1) → 5β-methylandrost-1-ene-3,17-dione (51503-64-1) + 1α-methyl-androst-4-ene-3,17-dione (4136-62-3)

Conditions	Yield
With chloro-trimethyl-silane; copper(I) bromide In tetrahydrofuran; toluene for 2h; Ambient temperature;	A 2.6% B 93%

methylene chloride (74-87-3) + Androsta-1,4-diene-3,17-dione (897-06-3) → metandienone (72-63-9)

Conditions	Yield
Stage #1: methylene chloride With magnesium In tetrahydrofuran at 30 - 35℃; Stage #2: Androsta-1,4-diene-3,17-dione In tetrahydrofuran at 50 - 55℃;	92.5%
Stage #1: methylene chloride With magnesium In tetrahydrofuran at 30 - 35℃; Stage #2: Androsta-1,4-diene-3,17-dione In tetrahydrofuran at 50 - 55℃;	92.5%
Stage #1: methylene chloride With magnesium In tetrahydrofuran at 30 - 35℃; Stage #2: Androsta-1,4-diene-3,17-dione In tetrahydrofuran at 50 - 55℃; Stage #3: With hydrogenchloride In water at 50 - 55℃; pH=2 - 3;	92.5%

Androsta-1,4-diene-3,17-dione (897-06-3) + Benzeneselenol (645-96-5) → (1S,8S,9S,10R,13S,14S)-10,13-dimethyl-1-(phenylselanyl)-7,8,9,10,11,12,13,14,15,16-decahydro-1H-cyclopenta[a]-phenanthrene-3,17(2H,6H)-dione

Conditions	Yield
With γ-cyclodextrin; sodium hydride In water; acetone at 20℃; for 6h;	92%

Androsta-1,4-diene-3,17-dione (897-06-3) + methyl iodide (74-88-4) → metandienone (72-63-9)

Conditions	Yield
Stage #1: methyl iodide With magnesium In diethyl ether at 30 - 35℃; Stage #2: Androsta-1,4-diene-3,17-dione In benzene at 50 - 55℃;	90.8%
Stage #1: methyl iodide With magnesium In diethyl ether at 30 - 35℃; Stage #2: Androsta-1,4-diene-3,17-dione In benzene at 50 - 55℃;	90.8%
Stage #1: methyl iodide With magnesium In diethyl ether at 30 - 35℃; Stage #2: Androsta-1,4-diene-3,17-dione In benzene at 50 - 55℃; Stage #3: With hydrogenchloride In water at 50 - 55℃; pH=2 - 3;	90.8%

Androsta-1,4-diene-3,17-dione (897-06-3) → [1α,2α-2H2]androst-4-ene-3,17-dione (79037-28-8)

Conditions	Yield
With water-d2; Wilkinson's catalyst In benzene-d6 at 20℃; for 1h;	90.2%

Androsta-1,4-diene-3,17-dione (897-06-3) + triethylaluminum (97-93-8) → 1α-ethylandrost-4-ene-3,17-dione (148928-50-1) + 5β-ethylandrost-1-ene-3,17-dione

Conditions	Yield
With chloro-trimethyl-silane; copper(I) bromide In tetrahydrofuran; toluene for 2h; Ambient temperature;	A 90% B n/a

Androsta-1,4-diene-3,17-dione (897-06-3) → 16α,16β-dideuterium-1,4-androstenedione

Conditions	Yield
With water-d2; potassium carbonate In tetrahydrofuran for 24h; Reflux;	90%

Androsta-1,4-diene-3,17-dione (897-06-3) + trimethylaluminum (75-24-1) → 1α-methyl-androst-4-ene-3,17-dione (4136-62-3)

Conditions	Yield
With chloro-trimethyl-silane; copper(I) bromide In tetrahydrofuran for 2h; Ambient temperature;	89%
copper(I) bromide In 1,4-dioxane; water; toluene
copper(I) bromide In 1,4-dioxane; water; toluene
With chloro-trimethyl-silane; copper(I) bromide In tetrahydrofuran; water; toluene

Androsta-1,4-diene-3,17-dione (897-06-3) + triethylaluminum (97-93-8) → 1α-ethylandrost-4-ene-3,17-dione (148928-50-1)

Conditions	Yield
With chloro-trimethyl-silane; copper(I) bromide In tetrahydrofuran; water; toluene	89%
With chloro-trimethyl-silane; copper(I) bromide In tetrahydrofuran for 1h; Ambient temperature;	87%
copper(I) bromide In 1,4-dioxane; hexane; water	85%
copper(I) bromide In 1,4-dioxane; hexane; water	85%

Androsta-1,4-diene-3,17-dione (897-06-3) + thioacetic acid (507-09-5) → S-((1S,8S,9S,10R,13S,14S)-10,13-dmethyl-3,17-dioxo-2,3,6,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta-[a]phenanthren-1-yl) ethanethioate (111611-76-8)

Conditions	Yield
In tetrahydrofuran; methanol; water at 20℃; for 12h; Inert atmosphere;	89%

trifluoromethylsulfonic anhydride (358-23-6) + Androsta-1,4-diene-3,17-dione (897-06-3) → androsten-3,5-dienyl-17-one 3-triflate (95667-41-7)

Conditions	Yield
With 2,6-di-tert-butyl-4-methylpyridine In dichloromethane for 4h; Ambient temperature;	88%

O-Methylhydroxylamin (67-62-9) + Androsta-1,4-diene-3,17-dione (897-06-3) → Androsta-1,4-dien-3,17-dion-17-(O-methyloxim)

Conditions	Yield
With sodium acetate In ethanol for 120h; Ambient temperature;	85%

Androsta-1,4-diene-3,17-dione (897-06-3) → Androstenedione (63-05-8)

Conditions	Yield
With sodium hydroxide; iron pentacarbonyl In methanol; water at 50 - 60℃; for 16h;	85%
With thallium(III) nitrate trihydrate In diethylene glycol dimethyl ether for 24h; Ambient temperature;	29%
With hydrogen; silica gel; copper In toluene at 60℃; under 760 Torr; for 5h;

Androsta-1,4-diene-3,17-dione (897-06-3) → testolactone (968-93-4)

Conditions	Yield
With sodium hydrogencarbonate; 3-chloro-benzenecarboperoxoic acid In dichloromethane at 20℃; Baeyer-Villiger Ketone Oxidation;	85%
With Fusarium oxysporum SC1301 In dimethyl sulfoxide at 30℃; for 15h;	82%

Androsta-1,4-diene-3,17-dione (897-06-3) → (10R,13S)-17-(hydroxyimino)-10,13-dimethyl-6,7,8,9,10,11,12,13,14,15,16,17-dodecahydro-3H-cyclopenta[a]phenanthren-3-one

Conditions	Yield
With hydroxylamine hydrochloride; sodium acetate In ethanol; water for 6h; Inert atmosphere; Reflux;	84.4%
With hydroxylamine hydrochloride; sodium hydroxide In ethanol; water for 1.5h; Reflux;

Androsta-1,4-diene-3,17-dione (897-06-3) + 2-(methylamino)benzenethiol (21749-63-3) → 3'-Methylspiro-17-on

Conditions	Yield
With boron trifluoride diethyl etherate In chloroform 1) RT, 2h, 2) 50 deg C, 32 h;	84%

Androsta-1,4-diene-3,17-dione (897-06-3) + sodium thiophenolate (930-69-8) + thiophenol (108-98-5) → (1S,8S,9S,10R,13S,14S)-10,13-Dimethyl-1-(phenylthio)-7,8,9,10,11,12,13,14,15,16-decahydro-1H-cyclopenta[a]-phenanthrene-3,17(2H,6H)-dione

Conditions	Yield
In tetrahydrofuran at 20℃; for 48h; Inert atmosphere;	83%

Androsta-1,4-diene-3,17-dione (897-06-3) → 1β,2β-Epoxy-4-androstene-3,17-dione (97455-05-5) + 4α,5α-Epoxy-1-androstene-3,17-dione + 4β,5β-Epoxy-1-androstene-3,17-dione + 1α,2α-Epoxy-4-androstene-3,17-dione

Conditions	Yield
With 3,3-dimethyldioxirane In dichloromethane; acetone at 20℃; for 28h; Title compound not separated from byproducts;	A 1.2 % Spectr. B 12 % Spectr. C 81% D 5.8 % Spectr.
With 3,3-dimethyldioxirane In dichloromethane; acetone at 20℃; for 28h;	A 1.2 % Spectr. B 12 % Spectr. C 81% D 5.8 % Spectr.

Androsta-1,4-diene-3,17-dione (897-06-3) + 3,3-dimethyldioxirane (74087-85-7) → 4β,5β-Epoxy-1-androstene-3,17-dione

Conditions	Yield
In acetone at 23℃; Kinetics;	81%

2-phenylazlactone (1199-01-5) + Androsta-1,4-diene-3,17-dione (897-06-3) → 3-<5-Oxo-2-phenyl-1,3-oxazol-4(5H)-yliden>-1,4-androstadien-17-on (106193-55-9)

Conditions	Yield
With pyridine; titanium tetrachloride In tetrahydrofuran; tetrachloromethane 1.) 0-5 deg C, 20 min.; 2.) 2 h, room temp.;	80%

Androsta-1,4-diene-3,17-dione (897-06-3) + semicarbazide hydrochloride (563-41-7) → Androsta-1,4-dien-3,17-dion-17-semicarbazon

Conditions	Yield
With sodium acetate In ethanol for 120h; Ambient temperature;	80%

Upstream product

• 110-86-1 pyridine 
• 42453-26-9 5α-androstan-2α,4α-dibromo-3,17-dione 
• 108-75-8 2,4,6-trimethyl-pyridine 
• 521-17-5 5-androstenediol 
• 846-48-0 1-dehydrotestosterone 
• 108-94-1 cyclohexanone 
• 53-43-0 dehydroepiandrosterone 
• 57334-04-0 3-thioxo-androst-1,4-dien-17-on 
• 109-92-2 ethyl vinyl ether 
• 83-46-5 β-sitosterol 
• 57-87-4 Ergosterol 
• 1108-03-8 ergosterol acetate 
• 481-29-8 Epiandrosterone 
• 57-88-5 cholesterol 

Downstream Products

• 106193-55-9 3-<5-Oxo-2-phenyl-1,3-oxazol-4(5H)-yliden>-1,4-androstadien-17-on 
• 1229-12-5 5β-androstane-3,17-dione 
• 110325-37-6 7α-(4'-amino)phenylthio-1,4-androstadiene-3,17-dione 
• 110325-38-7 (1S,8S,9S,10R,13S,14S)-1-(4-Amino-phenylsulfanyl)-10,13-dimethyl-1,8,9,10,11,12,13,14,15,16-decahydro-2H-cyclopenta[a]phenanthrene-3,17-dione 
• 63-05-8 Androstenedione 
• 1229-12-5 androstane-3,17-dione 
• 571-40-4 5α-androst-1-ene-3,17-dione 
• 571-39-1 5β-Androst-1-ene-3,17-dione 
• 58-22-0 testosterone 
• 481-30-1 epitestosterone 
• 968-93-4 testolactone 
• 481-29-8 Epiandrosterone 
• 53-42-9 Etiocholanolone 
• 150634-79-0 16-(4'-methoxybenzal)androsta-1,4-diene-3,17-dione 

Relevant articles and documents

Preparation of androsta-1,4-diene-3,17-dione from sterols using Mycobacterium neoaurum VKPM Ac-1656 strain

A product of microbiological cleavage of the sterols side chain, androsta-1,4-diene-3,17-dione, is toxic for bacteria, in particular, actinobacteria of the genera Mycobacterium and Arthrobacter. Sterols were transformed into androsta-1,4-diene-3,17-dione by culturing the M. neoaurum VKPM Ac-1656 strain in a high yield, provided that a sorbent was used for elimination of contact between the bacterial cells and the product. Unlike the cholesterol side chain, the more branched chains of phytosterols were cleaved in the presence of M. neoaurum at a high rate only under turbulent stirring of the culture medium, which intensified the formation of hydrocarbonate ion from NaNI3 in situ. Nauka/Interperiodica 2007.

Bioconversion of 4-androstene-3,17-dione to androst-1,4-diene-3,17-dione by recombinant Bacillus subtilis expressing ksdd gene encoding 3-ketosteroid-Δ1-dehydrogenase from Mycobacterium neoaurum JC-12

The enzyme 3-ketosteroid-Δ1-dehydrogenase (KSDD), involved in steroid metabolism, catalyzes the transformation of 4-androstene-3,17-dione (AD) to androst-1,4-diene-3,17-dione (ADD) specifically. Its coding gene was obtained from Mycobacterium neoaurum JC-12 and expressed on the plasmid pMA5 in Bacillus subtilis 168. The successfully expressed KSDD was analyzed by native-PAGE. The activities of the recombinant enzyme in B. subtilis were 1.75 U/mg, which was about 5-fold that of the wild type in M. neoaurum. When using the whole-cells as catalysts, the products were analyzed by tin-layer chromatography and high-performance liquid chromatography. The recombinant B. subtilis catalyzed the biotransformation of AD to ADD in a percent conversion of 65.7% and showed about 18 folds higher than M. neoaurum JC-12. The time required for transformation of AD to ADD was about 10 h by the recombinant B. subtilis, much shorter than that of the wild-type strain and other reported strains. Thus, the efficiency of ADD production could be improved immensely. For industrial applications, the recombinant B. subtilis containing KSDD provides a new pathway of producing steroid medicines.

Synthesis of 3β-methyl ether of dehydroepiandrosterone by biotransformation of 3β-methyl ether of cholesterol with cells of mycobacteria Mycobacterium sp.

3p-Methyl ether of dehydroepiandrosterone was obtained by microbiological transformation of 3?-methyl ether of cholesterol with Mycobacterium sp. Androstane-3,17-dione, androst-4-ene-3,17-dione, and androsta-1,4-diene-3,17-dione were minor transformation products.

Hemisynthesis of 2,3,4-13C3-1,4-androstadien-3,17-dione: A key precursor for the synthesis of 13C3-androstanes and 13C3-estranes

In this contribution, we describe two simple and efficient routes for the preparation of keto-aldehyde 1, a key intermediate for the synthesis of 13C3-androstanes and 13C3-estranes. In the first route, the targeted aldehyde 1 was obtained in 40% overall yield from 1,4-androstadien-3,17-dione (3 mmol scale) via a two-step sequence involving a one-pot, abnormal ozonolysis/sulfur oxidation/retro-Michael/ozonolysis process. Alternatively, a second route from 4-androsten-3,17-dione, using a six-step sequence, was optimized to produce 40 mmol batches of the key intermediate 1 in 42% overall yield. At the final stage, the A-ring was reconstructed through a Wittig reaction with the 1-triphenylphosphoranylidene-13C3-2-propanone 2, followed by an intramolecular condensation assisted by thioacetic acid via a Michael addition/retro-Michael reaction sequence to provide 2,3,4-13C3-1,4-androstadien-3,17-dione.