633-35-2

Basic information

• Product Name: ANDROSTA-1,4,6-TRIENE-3,17-DIONE
• Synonyms: androsta-1,4,6-triene-3,17-dione;Δ1,4,6-androgen;1,4,6-Andorstatriene-3,17-dione
• CAS NO: 633-35-2
• Molecular Formula: C₁₉H₂₂O₂
• Molecular Weight: 282.37678
• EINECS: 1806241-263-5
• Product Categories: Various Metabolites and Impurities;Metabolites & Impurities;Steroids
• Mol File: 633-35-2.mol
• Article Data: 6

Chemical Properties

• Melting Point: 164-1650C
• Boiling Point: 452.8 °C at 760 mmHg
• Flash Point: 168.7 °C
• Appearance: /powder
• Density: 1.16 g/cm³
• Vapor Pressure: 2.17E-08mmHg at 25°C
• Refractive Index: 1.587
• Storage Temp.: -20°C Freezer
• Solubility: methanol: 50 mg/mL, soluble
• CAS DataBase Reference: ANDROSTA-1,4,6-TRIENE-3,17-DIONE(CAS DataBase Reference)
• NIST Chemistry Reference: ANDROSTA-1,4,6-TRIENE-3,17-DIONE(633-35-2)
• EPA Substance Registry System: ANDROSTA-1,4,6-TRIENE-3,17-DIONE(633-35-2)

Safety Data

• Safety Statements: 22-24/25
• WGK Germany: 3
• RTECS: BV8082250
• Hazardous Substances Data: 633-35-2(Hazardous Substances Data)

Usage

Chemical Properties

Brownish Yellow Solid

Definition

ChEBI: An androstanoid that is androsta-1,4,6-triene substituted by oxo groups at positions 3 and 17.

InChI:InChI=1/C19H22O2/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/h3-4,7,9,11,14-16H,5-6,8,10H2,1-2H3/t14-,15-,16-,18-,19-/m0/s1

Synthetic route

dehydroepiandrosterone (53-43-0) → 1,4,6-androstatriene-3,17-dione (633-35-2)

Conditions	Yield
With 2,3-dicyano-5,6-dichloro-p-benzoquinone In 1,4-dioxane for 24h; Heating;	61%
With 2,3-dicyano-5,6-dichloro-p-benzoquinone In 1,4-dioxane for 24h; Heating;	45%

androst-4,6-diene-3,17-dione (633-34-1) → 1,4,6-androstatriene-3,17-dione (633-35-2)

Conditions	Yield
With sodium periodate

6β-bromo-androsta-1,4-diene-3,17-dione (27759-21-3) → 1,4,6-androstatriene-3,17-dione (633-35-2)

Conditions	Yield
With 2,4,6-trimethyl-pyridine

2α,6β-dibromo-androst-4-ene-3,17-dione → 1,4,6-androstatriene-3,17-dione (633-35-2)

Conditions	Yield
With 2,4,6-trimethyl-pyridine

Androsta-1,4-diene-3,17-dione (897-06-3) → 1,4,6-androstatriene-3,17-dione (633-35-2)

Conditions	Yield
Multi-step reaction with 2 steps 1: dibenzoyl peroxide; CCl4; N-bromo-succinimide 2: 2,4,6-trimethyl-pyridine View Scheme

1,4,6-androstatriene-3,17-dione (633-35-2) + trimethylaluminum (75-24-1) → 1α-methyl-androsta-4,6-diene-3,17-dione

Conditions	Yield
copper(I) bromide In 1,4-dioxane; water; toluene	99%
With copper(I) bromide In tetrahydrofuran for 1h; Ambient temperature;	89%

1,4,6-androstatriene-3,17-dione (633-35-2) + 2-hydroxy-2-methylpropanenitrile (75-86-5) → C20H23NO2

Conditions	Yield
With sodium carbonate In methanol; water at 20 - 45℃; Reagent/catalyst; Solvent;	98.6%
With sodium carbonate In water at 20 - 45℃; Reagent/catalyst; Solvent;	98.6%
With sodium carbonate In water at 40 - 45℃; Solvent; Reagent/catalyst;	98.6%

1,4,6-androstatriene-3,17-dione (633-35-2) → 1α,2α-epoxy-4,6-androstadiene-3,17-dione (5902-32-9)

Conditions	Yield
With dihydrogen peroxide; sodium hydroxide In methanol at 20℃; for 12h;	86%
With sodium hydroxide; dihydrogen peroxide In methanol at 20℃; for 22h;	78%

1,4,6-androstatriene-3,17-dione (633-35-2) → 1,4,6-androstatrien-3β,17β-diol (34195-01-2)

Conditions	Yield
With sodium tetrahydroborate In ethanol at 20℃; for 24h;	83%
With sodium tetrahydroborate In ethanol at 20℃;	63%

sodium metabisulfite + oxone + 1,4,6-androstatriene-3,17-dione (633-35-2) → 6,7α-epoxyandrosta-1,4-diene-3,17-dione

Conditions	Yield
With sodium hydroxide In water; acetone	73%

1,4,6-androstatriene-3,17-dione (633-35-2) → (E)-6-hydroxyiminoandrosta-1,4-diene-3,17-dione (140421-66-5)

Conditions	Yield
With triethylsilane; tert.-butylnitrite; cobalt(II) 5,10,15,20-tetraphenylporphyrin In dichloromethane; isopropyl alcohol for 48h; Ambient temperature;	68%

1,4,6-androstatriene-3,17-dione (633-35-2) → 6-dehydrotestosterone (3591-23-9, 3593-33-7, 4030-88-0, 4223-57-8, 2484-30-2) + 1,4,6-Androstatrien-17beta-ol-3-one (4075-12-1)

Conditions	Yield
With lithium triethylborohydride In tetrahydrofuran at 20℃; for 2h;	A 65% B 13%
With lithium aluminium tetrahydride In tetrahydrofuran at 20℃; for 1h;	A 16% B 53%

1,4,6-androstatriene-3,17-dione (633-35-2) → 6α,7α-epoxy-4,6-androstadiene-3,17-dione (55651-50-8)

Conditions	Yield
With 3-chloro-benzenecarboperoxoic acid In chloroform at 20℃;	64%
With 3-chloro-benzenecarboperoxoic acid In chloroform at 60℃; for 6h; Inert atmosphere;	61%

1,4,6-androstatriene-3,17-dione (633-35-2) → 1,4,6-androstatrien-3α,17β-diol

Conditions	Yield
With L-Selectride In tetrahydrofuran at 20℃; for 18h;	63%

1-Naphthalenethiol (529-36-2) + 1,4,6-androstatriene-3,17-dione (633-35-2) → 7α-(1'-naphthyl)thioandrosta-1,4-diene-3,17-dione + (1S,7R,8S,9S,10R,13S,14S)-10,13-Dimethyl-1,7-bis-(naphthalen-1-ylsulfanyl)-1,6,7,8,9,10,11,12,13,14,15,16-dodecahydro-2H-cyclopenta[a]phenanthrene-3,17-dione

Conditions	Yield
With hydrogenchloride; acetic acid for 20h; Ambient temperature;	A 20% B 45%

1,4,6-androstatriene-3,17-dione (633-35-2) + 2-Naphthalenethiol (91-60-1) → 7α-(2'-naphthyl)thioandrosta-1,4-diene-3,17-dione + (1S,8S,9S,10R,13S,14S)-10,13-Dimethyl-1-(naphthalen-2-ylsulfanyl)-1,8,9,10,11,12,13,14,15,16-decahydro-2H-cyclopenta[a]phenanthrene-3,17-dione + (1S,7R,8S,9S,10R,13S,14S)-10,13-Dimethyl-1,7-bis-(naphthalen-2-ylsulfanyl)-1,6,7,8,9,10,11,12,13,14,15,16-dodecahydro-2H-cyclopenta[a]phenanthrene-3,17-dione

Conditions	Yield
With sodium In 1,4-dioxane at 80℃; for 18h;	A 25% B 35% C 10%

hypofluorous acid trifluoromethyl ester (373-91-1) + 1,4,6-androstatriene-3,17-dione (633-35-2) → 6α,7α-difluoroandrosta-1,4-diene-3,17-dione (82423-37-8) + 7α-fluoro-6α-trifluoromethoxyandrosta-1,4-diene-3,17-dione (82423-38-9)

Conditions	Yield
With calcium oxide In dichloromethane at -20℃;	A 15% B 30%

1,4,6-androstatriene-3,17-dione (633-35-2) → 6α,7α-difluoroandrosta-1,4-diene-3,17-dione (82423-37-8) + 7α-fluoro-6α-trifluoromethoxyandrosta-1,4-diene-3,17-dione (82423-38-9)

Conditions	Yield
With trichlorofluoromethane; calcium oxide In dichloromethane at -20℃;	A 15% B 30%

1,4,6-androstatriene-3,17-dione (633-35-2) + 4-aminotiophenol (1193-02-8) → 7α-(4'-amino)phenylthio-1,4-androstadiene-3,17-dione (110325-37-6) + (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 (110325-38-7)

Conditions	Yield
With hydrogenchloride; acetic acid for 24h; Ambient temperature;	A 15% B 30%

1,4,6-androstatriene-3,17-dione (633-35-2) + thiophenol (108-98-5) → 7α-phenylthioandrosta-1,4-diene-3,17-dione

Conditions	Yield
With hydrogenchloride; acetic acid for 24h; Ambient temperature;	27%

1,4,6-androstatriene-3,17-dione (633-35-2) + para-bromobenzenethiol (106-53-6) → 7α-(4'-bromo)phenylthioandrosta-1,4-diene-3,17-dione

Conditions	Yield
With hydrogenchloride; acetic acid for 15h; Ambient temperature;	15%

thioacetic acid (507-09-5) + 1,4,6-androstatriene-3,17-dione (633-35-2) → 1α-acetylsulfanyl-androsta-4,6-diene-3,17-dione (102472-23-1)

Conditions	Yield
Einwirkung von UV-Licht;
im UV-Licht;

1,4,6-androstatriene-3,17-dione (633-35-2) → 6-dehydroestrone (2208-12-0)

Conditions	Yield
With glass at 600℃;

1,4,6-androstatriene-3,17-dione (633-35-2) + acetic anhydride (108-24-7) → 3-acetoxy-1-methyl-estra-1,3,5(10),6-tetraen-17-one (53-55-4)

Conditions	Yield
With toluene-4-sulfonic acid
With toluene-4-sulfonic acid; acetic acid

1,4,6-androstatriene-3,17-dione (633-35-2) + acetic anhydride (108-24-7) → 1-Methyl-3-acetoxy-7-acetyl-Δ1.3.5(10).6-oestratetraen-17-on (18012-02-7)

Conditions	Yield
With toluene-4-sulfonic acid; acetic acid

1,4,6-androstatriene-3,17-dione (633-35-2) → (13S,14R)-1-Hydroxy-4,13-dimethyl-6,7,11,12,13,14,15,16-octahydro-cyclopenta[a]phenanthren-17-one

Conditions	Yield
With hydrogen fluoride; antimony pentafluoride at -50℃;

1,4,6-androstatriene-3,17-dione (633-35-2) → 2-ethoxy-1,4,6-androstatrien-3β,17β-dione

Conditions	Yield
Multi-step reaction with 2 steps 1: 78 percent / NaOH; H2O2 / methanol / 22 h / 20 °C 2: 73 percent / lithium / 18 h / 20 °C View Scheme

1,4,6-androstatriene-3,17-dione (633-35-2) → 1α,2α-epoxy-1,4-androstadien-3β,17β-diol

Conditions	Yield
Multi-step reaction with 2 steps 1: 78 percent / NaOH; H2O2 / methanol / 22 h / 20 °C 2: 69 percent / NaBH4 / ethanol / 20 °C View Scheme

1,4,6-androstatriene-3,17-dione (633-35-2) → 4β,5β-epoxyandrost-6-en-3β,17β-diol

Conditions	Yield
Multi-step reaction with 2 steps 1: 63 percent / NaBH4 / ethanol / 20 °C 2: 64 percent / m-chloroperoxybenzoic acid / CHCl3 / 20 °C View Scheme

Upstream product

• 897-06-3 Androsta-1,4-diene-3,17-dione 
• 53-43-0 dehydroepiandrosterone 
• 27759-21-3 6β-bromo-androsta-1,4-diene-3,17-dione 
• 633-34-1 androst-4,6-diene-3,17-dione 

Downstream Products

• 13698-49-2 6-chloro-17a-acetoxy-pregnane-1,4,6-,triene-3,20-dione 
• 15262-77-8 delmadinone 
• 66212-25-7 1,4,6-triene-3,20-dione-17α-hydroxyprogesterone 
• 3597-38-4 1-Methyl-estradiol 
• 116031-38-0 3-benzoyloxy-1-methyl-estra-1,3,5(10),6-tetraen-17β-ol 
• 10506-68-0 1-methyl-estra-1,3,5(10),6-tetraene-3,17β-diol 
• 3129-08-6 1-Methyl-6-dehydro-oestron 
• 152953-22-5 7α-<4'-(3'',3''-dimethylazido)phenyl>thioandrosta-1,4-diene-3,17-dione 
• 3591-23-9 6-dehydrotestosterone 
• 4075-12-1 1,4,6-Androstatrien-17beta-ol-3-one 
• 2208-12-0 6-dehydroestrone 
• 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 

Relevant articles and documents

NOVEL COMPOSITION TO INCREASE LIBIDO

The present invention relates to a composition for increasing testosterone physiological levels comprising a sufficient amount of at least two ketosteroid derivatives of testosterone metabolism in association with a liposomal carrier bound to a saliva-absorbing carrier, wherein said increase in testosterone levels increases libido.

Epoxidation and Reduction of DHEA, 1,4,6-Androstatrien-3-one and 4,6-Androstadien-3β,17β-diol

Dehydroepiandrosterone (DHEA) reacted with m-chloroperoxybenzoic acid (m-CPBA) to form 3β-hydroxy-5α,6α-epoxyandrostan-17-one (1), but it did not react with 30 percent H2O2. 1,4,6-Androstatrien-3,17-dione (2) was obtained from DHEA and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone in dioxane. Compound 2 was reacted with 30 percent H2O2 and 5 percent NaOH in methanol to give 1α,2α-epoxy-4,6-androstadien-3,17-dione (3), which was stereoselectively reduced with NaBH4 to form 1α,2α-epoxy-4,6-androstadien-3β,17β-diol (7) and reacted with Li metal in absolute ethanol-tetrahydrofuran mixture to give 2-ethoxy-1,4,6-androstatrien-3,17-dione (8). Compound 2 was also epoxidized with m-CPBA in dichloromethane to afford 6α,7α-epoxy-1,4- androstadien-3,17-dione (4), which was reacted with NaBH4 to synthesize 6α,7α-epoxy-4-androsten-3β,17β-diol (9). Compound 4 was reduced with Li metal in absolute ethanol-tetrahydrofuran mixture to form 7β-ethoxy-6α-hydroxy-1,4-androstadien-3,17-dione (10). Compound 2 was reduced with NaBH4 in absolute ethanol to form 4,6-androstadien-3β,17β-diol (5), which was reacted with 30 percent H2O2 to give the original compound, but which reacted with m-CPBA to give 4β,5β-epoxy-6-androsten-3β,17β-diol (6).

Electrophilic Fluorination of Some Steroidal α,β-Unsaturated Ketones

3β-Acetoxy-5α,6β-dichloropregn-16-en-20-one (1), on treatment with elemental fluorine at low temperature, gave the 16α,17α-difluoro-adduct (2) and, by rearrangement, the 13α,16α-difluoro-17β-methyl derivative (3).The adduct (2) was subsequently converted via a short, efficient synthetic sequence into 16α,17α-difluoroprogesterone (5).In contrast, fluorination of 21-acetoxypregna-1,4,16-triene-3,11,20-trione (6) afforded the corresponding 16α,17α-difluoro-adduct (8) in low yield.Similarly, androsta-1,4,6-triene-3,17-dione (9) was converted into the 6α,7α-difluoro-adduct (11).Fluorination with CF3OF led to an increased yield of the adduct (11) and also afforded the 6α-trifluoromethoxy-7α-fluoro-adduct (12).Dehydrofluorination of the latter gave 6-trifluoromethoxyandrosta-1,4,6-triene-3,17-dione (13). 21-Acetoxy-11β,17α-dihydroxypregna-1,4,6-triene-3,20-dione (5) was prepared by stepwise dehydrogenation of cortisol acetate (14).Subsequent low temperature treatment with CF3OF resulted in two major products, formulated as the adducts (17) and (18).