5173-46-6

Basic information

• Product Name: Estra-4,9-diene-3,17-dione
• Synonyms: 19-norandrosta-4,9-diene-3,17-dione;4,9-ESTRADIEN-3,17-DIONE;4,9-ESTRADIENE-3,17-DIONE;ESTRA-4,9-DIENE-3,17-DIONE;METHYLDIENEDIONE;ESTRA-4,9-DIENE-3,17-DIONE ENTERPRISE STANDARD;ESTRA-4,9-DIENE-3,17-DIONE 99%;Estra-4,9-diene-3
• CAS NO: 5173-46-6
• Molecular Formula: C₁₈H₂₂O₂
• Molecular Weight: 270.37
• EINECS: 1592732-453-0
• Product Categories: Pharmaceutical Intermediates;Amino Acids;Intermediates & Fine Chemicals;Metabolites & Impurities;Pharmaceuticals;Steroids;API;Metabolites & Impurities, Pharmaceuticals, Intermediates & Fine Chemicals, Steroids
• Mol File: 5173-46-6.mol
• Article Data: 14

Chemical Properties

• Melting Point: 131-134°C
• Boiling Point: 466.5 °C at 760 mmHg
• Flash Point: 173.4 °C
• Appearance: white or almost white crystalline powder
• Density: 1.16 g/cm³
• Vapor Pressure: 7.03E-09mmHg at 25°C
• Refractive Index: 1.575
• Storage Temp.: Refrigerator
• CAS DataBase Reference: Estra-4,9-diene-3,17-dione(CAS DataBase Reference)
• NIST Chemistry Reference: Estra-4,9-diene-3,17-dione(5173-46-6)
• EPA Substance Registry System: Estra-4,9-diene-3,17-dione(5173-46-6)

Safety Data

• Hazardous Substances Data: 5173-46-6(Hazardous Substances Data)

Usage

Chemical Properties

Light Beige Solid

Uses

Different sources of media describe the Uses of 5173-46-6 differently. You can refer to the following data:
1. A potential metabolite of STS 557 (Dienogest)(D441870). A steroid
2. A potential metabolitie of STS 557 (Dienogest). A steroid with antiglucocorticoid activity

InChI:InChI=1/C18H22O2/c1-18-9-8-14-13-5-3-12(19)10-11(13)2-4-15(14)16(18)6-7-17(18)20/h10,15-16H,2-9H2,1H3

Synthetic route

17β-hydroxyestra-4,9-dien-3-one (6218-29-7) → 4,9-Androstadiene-3,17-dione (5173-46-6)

Conditions	Yield
With tetrapropylammonium perruthennate for 3h;	98%
With Jones reagent In acetone at 0℃; Jones Oxidation;	97%
With tert.-butylhydroperoxide; 3 A molecular sieve; zircornium(IV) n-propoxide In dichloromethane for 17h;	90%

estra-4,9-diene-3,17-dione (2503-06-2) → 4,9-Androstadiene-3,17-dione (5173-46-6)

Conditions	Yield
With toluene-4-sulfonic acid In toluene for 0.75h; Reflux;	61%
With toluene-4-sulfonic acid
With phosphoric acid In dichloromethane; water

C17H24O4 → 4,9-Androstadiene-3,17-dione (5173-46-6) + estra-4,9-diene-3,17-dione (2503-06-2)

Conditions	Yield
With piperdinium acetate In toluene for 16h; Reflux;	A 36.4% B 36.6%

(3aS,7aS)-4-(3,7-Dioxo-octyl)-7a-methyl-hexahydro-indene-1,5-dione (33383-89-0, 40013-34-1, 40013-38-5, 65166-16-7) → 4,9-Androstadiene-3,17-dione (5173-46-6)

Conditions	Yield
With piperdinium acetate
Multi-step reaction with 2 steps 1: piperidine*AcOH 2: TsOH View Scheme

3S,6aS,3-(4-oxo-1-pentyl)-6a-methyl-1,2,3,5,6,6a-hexahydrocyclopenta[f][1]benzopyran-7(8H)-one (36668-14-1) → 4,9-Androstadiene-3,17-dione (5173-46-6)

Conditions	Yield
Multi-step reaction with 2 steps 2: piperidine*AcOH View Scheme
Multi-step reaction with 3 steps 2: piperidine*AcOH 3: TsOH View Scheme

10β-hydroxy-19-norandrost-4-ene-3,17-dione (5189-96-8) → 4,9-Androstadiene-3,17-dione (5173-46-6)

Conditions	Yield
With phosphoric acid; sulfuric acid In dichloromethane; isopropyl alcohol

(+)-3,3-dimethylpropylenedioxy-4,5-seco-estr-9-ene-5,17-dione + (+)-4,5-seco-estr-9-ene-3,5,17-trione (10582-53-3) + potassium tert-butylate (865-47-4) → 4,9-Androstadiene-3,17-dione (5173-46-6)

Conditions	Yield
With sodium chloride; sodium acetate; acetic acid In hexane; water; acetone; toluene; tert-butyl alcohol

3-(tert-butyldimethylsilyloxy)-3a-methyl-6-(3-oxobutyl)-3,3a,4,5,8,9,9a,9b-octaammon-1H-cyclopentadiene[a]naphthalene-7(2Η)-one → 4,9-Androstadiene-3,17-dione (5173-46-6)

Conditions	Yield
Multi-step reaction with 3 steps 1: potassium tert-butylate / toluene; tert-butyl alcohol / 5 h / 20 °C 2: tetrabutyl ammonium fluoride / tetrahydrofuran / 0.5 h / 20 °C 3: Jones reagent / acetone / 0 °C View Scheme

C24H38O2Si → 4,9-Androstadiene-3,17-dione (5173-46-6)

Conditions	Yield
Multi-step reaction with 2 steps 1: tetrabutyl ammonium fluoride / tetrahydrofuran / 0.5 h / 20 °C 2: Jones reagent / acetone / 0 °C View Scheme

(S)-Halos-Parish ketone (17553-86-5) → 4,9-Androstadiene-3,17-dione (5173-46-6)

Conditions	Yield
Multi-step reaction with 11 steps 1.1: sodium tetrahydroborate / ethanol / 4 h / -15 °C 2.1: 1H-imidazole / N,N-dimethyl-formamide / 18 h / 0 - 20 °C 3.1: sodium hydride / mineral oil; dimethyl sulfoxide / 3 h / 50 °C 3.2: 2 h 4.1: sodium tetrahydroborate; nickel(II) chloride hexahydrate / methanol / 1 h / -90 - -70 °C 5.1: pyridinium p-toluenesulfonate / acetone; water / 5 h / 60 °C 6.1: sodium methylate / methanol / 1.5 h / Reflux 7.1: sodium hydride / mineral oil; dimethyl sulfoxide / 4 h / 20 °C 7.2: 17 h / 20 °C 8.1: pyridinium p-toluenesulfonate / acetone; water / 5 h / 60 °C 9.1: potassium tert-butylate / toluene; tert-butyl alcohol / 5 h / 20 °C 10.1: tetrabutyl ammonium fluoride / tetrahydrofuran / 0.5 h / 20 °C 11.1: Jones reagent / acetone / 0 °C View Scheme
Multi-step reaction with 11 steps 1.1: sodium tetrahydroborate / ethanol / 4 h / -15 °C 2.1: 1H-imidazole / N,N-dimethyl-formamide / 18 h / 0 - 20 °C 3.1: sodium hydride / mineral oil; dimethyl sulfoxide / 4 h / 20 °C 3.2: 17 h / 20 °C 4.1: sodium tetrahydroborate; nickel(II) chloride hexahydrate / methanol / 1 h / -90 - -70 °C 5.1: pyridinium p-toluenesulfonate / acetone; water / 5 h / 60 °C 6.1: sodium methylate / methanol / 1.5 h / Reflux 7.1: sodium hydride / mineral oil; dimethyl sulfoxide / 4 h / 20 °C 7.2: 17 h / 20 °C 8.1: pyridinium p-toluenesulfonate / acetone; water / 5 h / 60 °C 9.1: potassium tert-butylate / toluene; tert-butyl alcohol / 5 h / 20 °C 10.1: tetrabutyl ammonium fluoride / tetrahydrofuran / 0.5 h / 20 °C 11.1: Jones reagent / acetone / 0 °C View Scheme

(1S,7aS)-1-hydroxy-7a-methyl-2,3,7,7a-tetrahydro-1H-inden-5(6H)-one (16271-49-1) → 4,9-Androstadiene-3,17-dione (5173-46-6)

Conditions	Yield
Multi-step reaction with 10 steps 1.1: 1H-imidazole / N,N-dimethyl-formamide / 18 h / 0 - 20 °C 2.1: sodium hydride / mineral oil; dimethyl sulfoxide / 3 h / 50 °C 2.2: 2 h 3.1: sodium tetrahydroborate; nickel(II) chloride hexahydrate / methanol / 1 h / -90 - -70 °C 4.1: pyridinium p-toluenesulfonate / acetone; water / 5 h / 60 °C 5.1: sodium methylate / methanol / 1.5 h / Reflux 6.1: sodium hydride / mineral oil; dimethyl sulfoxide / 4 h / 20 °C 6.2: 17 h / 20 °C 7.1: pyridinium p-toluenesulfonate / acetone; water / 5 h / 60 °C 8.1: potassium tert-butylate / toluene; tert-butyl alcohol / 5 h / 20 °C 9.1: tetrabutyl ammonium fluoride / tetrahydrofuran / 0.5 h / 20 °C 10.1: Jones reagent / acetone / 0 °C View Scheme
Multi-step reaction with 10 steps 1.1: 1H-imidazole / N,N-dimethyl-formamide / 18 h / 0 - 20 °C 2.1: sodium hydride / mineral oil; dimethyl sulfoxide / 4 h / 20 °C 2.2: 17 h / 20 °C 3.1: sodium tetrahydroborate; nickel(II) chloride hexahydrate / methanol / 1 h / -90 - -70 °C 4.1: pyridinium p-toluenesulfonate / acetone; water / 5 h / 60 °C 5.1: sodium methylate / methanol / 1.5 h / Reflux 6.1: sodium hydride / mineral oil; dimethyl sulfoxide / 4 h / 20 °C 6.2: 17 h / 20 °C 7.1: pyridinium p-toluenesulfonate / acetone; water / 5 h / 60 °C 8.1: potassium tert-butylate / toluene; tert-butyl alcohol / 5 h / 20 °C 9.1: tetrabutyl ammonium fluoride / tetrahydrofuran / 0.5 h / 20 °C 10.1: Jones reagent / acetone / 0 °C View Scheme

(1S,7aS)-1-((tert-butyldimethylsilyl)oxy)-7a-methyl-1,2,3,6,7,7a-hexahydro-5H-inden-5-one (149789-99-1, 126541-53-5) → 4,9-Androstadiene-3,17-dione (5173-46-6)

Conditions	Yield
Multi-step reaction with 9 steps 1.1: sodium hydride / mineral oil; dimethyl sulfoxide / 3 h / 50 °C 1.2: 2 h 2.1: sodium tetrahydroborate; nickel(II) chloride hexahydrate / methanol / 1 h / -90 - -70 °C 3.1: pyridinium p-toluenesulfonate / acetone; water / 5 h / 60 °C 4.1: sodium methylate / methanol / 1.5 h / Reflux 5.1: sodium hydride / mineral oil; dimethyl sulfoxide / 4 h / 20 °C 5.2: 17 h / 20 °C 6.1: pyridinium p-toluenesulfonate / acetone; water / 5 h / 60 °C 7.1: potassium tert-butylate / toluene; tert-butyl alcohol / 5 h / 20 °C 8.1: tetrabutyl ammonium fluoride / tetrahydrofuran / 0.5 h / 20 °C 9.1: Jones reagent / acetone / 0 °C View Scheme
Multi-step reaction with 9 steps 1.1: sodium hydride / mineral oil; dimethyl sulfoxide / 4 h / 20 °C 1.2: 17 h / 20 °C 2.1: sodium tetrahydroborate; nickel(II) chloride hexahydrate / methanol / 1 h / -90 - -70 °C 3.1: pyridinium p-toluenesulfonate / acetone; water / 5 h / 60 °C 4.1: sodium methylate / methanol / 1.5 h / Reflux 5.1: sodium hydride / mineral oil; dimethyl sulfoxide / 4 h / 20 °C 5.2: 17 h / 20 °C 6.1: pyridinium p-toluenesulfonate / acetone; water / 5 h / 60 °C 7.1: potassium tert-butylate / toluene; tert-butyl alcohol / 5 h / 20 °C 8.1: tetrabutyl ammonium fluoride / tetrahydrofuran / 0.5 h / 20 °C 9.1: Jones reagent / acetone / 0 °C View Scheme

1-(tert-butyldimethylsilyloxy)-7a-methyl-4-(2-(2-methyl-1,3-dioxolane-2-yl)ethyl)-2,3,5,6,7,7a-tetrahydro-1H-inden-5(6H)-one (1092775-41-1) → 4,9-Androstadiene-3,17-dione (5173-46-6)

Conditions

Yield

Multi-step reaction with 8 steps 1.1: sodium tetrahydroborate; nickel(II) chloride hexahydrate / methanol / 1 h / -90 - -70 °C 2.1: pyridinium p-toluenesulfonate / acetone; water / 5 h / 60 °C 3.1: sodium methylate / methanol / 1.5 h / Reflux 4.1: sodium hydride / mineral oil; dimethyl sulfoxide / 4 h / 20 °C 4.2: 17 h / 20 °C 5.1: pyridinium p-toluenesulfonate / acetone; water / 5 h / 60 °C 6.1: potassium tert-butylate / toluene; tert-butyl alcohol / 5 h / 20 °C 7.1: tetrabutyl ammonium fluoride / tetrahydrofuran / 0.5 h / 20 °C 8.1: Jones reagent / acetone / 0 °C View Scheme

1-(tert-butyldimethylsilyloxy)-7a-methyl-4-(2-(2-methyl-1,3-dioxolan-2-yl)ethyl)hexahydro-1H-inden-5(6)-one → 4,9-Androstadiene-3,17-dione (5173-46-6)

Conditions

Yield

Multi-step reaction with 7 steps 1.1: pyridinium p-toluenesulfonate / acetone; water / 5 h / 60 °C 2.1: sodium methylate / methanol / 1.5 h / Reflux 3.1: sodium hydride / mineral oil; dimethyl sulfoxide / 4 h / 20 °C 3.2: 17 h / 20 °C 4.1: pyridinium p-toluenesulfonate / acetone; water / 5 h / 60 °C 5.1: potassium tert-butylate / toluene; tert-butyl alcohol / 5 h / 20 °C 6.1: tetrabutyl ammonium fluoride / tetrahydrofuran / 0.5 h / 20 °C 7.1: Jones reagent / acetone / 0 °C View Scheme

1-(tert-butyldimethylsilyloxy)-7a-methyl-4-(3-oxobutyl)hexahydro-1H-inden-5(6)-one → 4,9-Androstadiene-3,17-dione (5173-46-6)

Conditions

Yield

Multi-step reaction with 6 steps 1.1: sodium methylate / methanol / 1.5 h / Reflux 2.1: sodium hydride / mineral oil; dimethyl sulfoxide / 4 h / 20 °C 2.2: 17 h / 20 °C 3.1: pyridinium p-toluenesulfonate / acetone; water / 5 h / 60 °C 4.1: potassium tert-butylate / toluene; tert-butyl alcohol / 5 h / 20 °C 5.1: tetrabutyl ammonium fluoride / tetrahydrofuran / 0.5 h / 20 °C 6.1: Jones reagent / acetone / 0 °C View Scheme

3-(tert-butyldimethylsilyloxy)-3a-methyl-3,3a,4,5,8,9,9a,9b-octahydro-1H-cyclopenta[a]naphthalene-7(2H)-one → 4,9-Androstadiene-3,17-dione (5173-46-6)

Conditions	Yield
Multi-step reaction with 5 steps 1.1: sodium hydride / mineral oil; dimethyl sulfoxide / 4 h / 20 °C 1.2: 17 h / 20 °C 2.1: pyridinium p-toluenesulfonate / acetone; water / 5 h / 60 °C 3.1: potassium tert-butylate / toluene; tert-butyl alcohol / 5 h / 20 °C 4.1: tetrabutyl ammonium fluoride / tetrahydrofuran / 0.5 h / 20 °C 5.1: Jones reagent / acetone / 0 °C View Scheme

<3aS-(3aα,9aα,9bβ)>-3β-((tert-butyldimethylsilyl)oxy)-3aβ-methyl-6-<2-(2-methyl-1,3-dioxolan-2-yl)ethyl>-1,2,3,3a,4,5,8,9,9a,9b-decahydro-7H-benzinden-7-one (95935-96-9) → 4,9-Androstadiene-3,17-dione (5173-46-6)

Conditions	Yield
Multi-step reaction with 4 steps 1: pyridinium p-toluenesulfonate / acetone; water / 5 h / 60 °C 2: potassium tert-butylate / toluene; tert-butyl alcohol / 5 h / 20 °C 3: tetrabutyl ammonium fluoride / tetrahydrofuran / 0.5 h / 20 °C 4: Jones reagent / acetone / 0 °C View Scheme

C12H16O3 → 4,9-Androstadiene-3,17-dione (5173-46-6)

Conditions	Yield
Multi-step reaction with 3 steps 1.1: magnesium / ethylene dibromide; tetrahydrofuran / 2 h / Reflux 1.2: 1.5 h / Cooling with ice 2.1: Jones reagent / acetone / 0.5 h / 0 - 20 °C 3.1: piperdinium acetate / toluene / 16 h / Reflux View Scheme
Multi-step reaction with 4 steps 1.1: magnesium / ethylene dibromide; tetrahydrofuran / 2 h / Reflux 1.2: 1.5 h / Cooling with ice 2.1: Jones reagent / acetone / 0.5 h / 0 - 20 °C 3.1: piperdinium acetate / toluene / 16 h / Reflux 4.1: toluene-4-sulfonic acid / toluene / 0.75 h / Reflux View Scheme

1-chloro-4-(1,3-dioxolane)-n-pentane (5978-08-5) → 4,9-Androstadiene-3,17-dione (5173-46-6) + estra-4,9-diene-3,17-dione (2503-06-2)

Conditions	Yield
Multi-step reaction with 3 steps 1.1: magnesium / ethylene dibromide; tetrahydrofuran / 2 h / Reflux 1.2: 1.5 h / Cooling with ice 2.1: Jones reagent / acetone / 0.5 h / 0 - 20 °C 3.1: piperdinium acetate / toluene / 16 h / Reflux View Scheme

C19H30O5 → 4,9-Androstadiene-3,17-dione (5173-46-6)

Conditions	Yield
Multi-step reaction with 2 steps 1: Jones reagent / acetone / 0.5 h / 0 - 20 °C 2: piperdinium acetate / toluene / 16 h / Reflux View Scheme
Multi-step reaction with 3 steps 1: Jones reagent / acetone / 0.5 h / 0 - 20 °C 2: piperdinium acetate / toluene / 16 h / Reflux 3: toluene-4-sulfonic acid / toluene / 0.75 h / Reflux View Scheme

C23H34O4 → 4,9-Androstadiene-3,17-dione (5173-46-6)

Conditions	Yield
Stage #1: C23H34O4 With hydrogenchloride In water; acetone for 3h; Reflux; Stage #2: With potassium tert-butylate In isopropyl alcohol; toluene for 2h; Reagent/catalyst; Solvent; Reflux;	67.1 g

methanol (67-56-1) + 4,9-Androstadiene-3,17-dione (5173-46-6) → 3,3-dimethoxy-estra-5(10),9(11)-diene-17-one (10109-76-9)

Conditions	Yield
With acetyl chloride at -20℃; for 2h;	97.5%
With tetrachlorosilane In hexane at 2 - 10℃; Product distribution / selectivity; Industry scale;
With acetyl chloride In hexane at 5 - 20℃; Product distribution / selectivity; Industry scale;
tetrachlorosilane In hexane at 2 - 15℃; for 1 - 1.5h; Product distribution / selectivity;
acetyl chloride In hexane at 5 - 20℃; for 1.35h; Product distribution / selectivity;

4,9-Androstadiene-3,17-dione (5173-46-6) + 2-hydroxy-2-methylpropanenitrile (75-86-5) → C19H23NO2

Conditions	Yield
With triethylamine In ethyl acetate at 30 - 35℃; for 20h; Reagent/catalyst; Time; Solvent;	95.1%

chloro-trimethyl-silane (75-77-4) + 4,9-Androstadiene-3,17-dione (5173-46-6) → C21H30O2Si

Conditions	Yield
With lithium diisopropyl amide In tetrahydrofuran at -40 - 20℃; for 0.666667h; Reagent/catalyst; Temperature; Industrial scale;	87.5%

4,9-Androstadiene-3,17-dione (5173-46-6) → 17β-hydroxyestra-4,9-dien-3-one (6218-29-7)

Conditions	Yield
With methanol; sodium tetrahydroborate In dichloromethane at -78℃; for 5h;	87%
With zygowilliopsis sp. WY7905 In aq. phosphate buffer at 30℃; for 24h; pH=8; Enzymatic reaction; stereoselective reaction;	61%
With sodium borohydrid; acetic acid In tetrahydrofuran; methanol
With sodium borohydrid; acetic acid In tetrahydrofuran; methanol

4,9-Androstadiene-3,17-dione (5173-46-6) + ethylene glycol (107-21-1) → C20H26O3

Conditions	Yield
With hydrogenchloride In water for 1h; Reflux; Green chemistry;	80%

methanol (67-56-1) + 4,9-Androstadiene-3,17-dione (5173-46-6) → C20H28O3

Conditions	Yield
With hydrogenchloride In water for 1h; Reagent/catalyst; Solvent; Reflux; Green chemistry;	77%

4,9-Androstadiene-3,17-dione (5173-46-6) + ethylene glycol (107-21-1) → 3,3:17,17-bis(ethylenedioxy)-estra-5(10),9(11)-diene (57905-07-4)

Conditions	Yield
With pyridine hydrochloride; sodium 1.) heptane, reflux, 2.) MeOH, 15 min; Yield given. Multistep reaction;

4,9-Androstadiene-3,17-dione (5173-46-6) → 17-hydroxy-estra-4,9-dien-3-one

Conditions	Yield
With sodium tetrahydroborate In tetrahydrofuran; methanol at -10℃;
With sodium tetrahydroborate In methanol; water for 0.5h; Cooling with ice;

4,9-Androstadiene-3,17-dione (5173-46-6) → ethylene deltenone (5571-36-8)

Conditions	Yield
Multi-step reaction with 2 steps 1: NaBH4 / tetrahydrofuran; methanol / -10 °C 2: 1.) (EtO)3CH, pTsOH, 2.) pyridinium chlorochromate / 2.) CH2Cl2 View Scheme

4,9-Androstadiene-3,17-dione (5173-46-6) → (8S,13S,14S,17R)-17-ethynyl-13-methyl-1,2,4,6,7,8,12,13,14,15,16,17-dodecahydrospiro[cyclopenta[a]phenanthrene-3,2’-[1,3]dioxolan]-17-ol (5490-76-6)

Conditions	Yield
Multi-step reaction with 3 steps 1: NaBH4 / tetrahydrofuran; methanol / -10 °C 2: 1.) (EtO)3CH, pTsOH, 2.) pyridinium chlorochromate / 2.) CH2Cl2 3: KOtBu / tetrahydrofuran View Scheme

4,9-Androstadiene-3,17-dione (5173-46-6) → 3-(ethylenedioxy)estra-5α,10α-epoxy-17α-ethynyl-17β-hydroxy-9(11)-ene (137532-55-9)

Conditions	Yield
Multi-step reaction with 4 steps 1: NaBH4 / tetrahydrofuran; methanol / -10 °C 2: 1.) (EtO)3CH, pTsOH, 2.) pyridinium chlorochromate / 2.) CH2Cl2 3: KOtBu / tetrahydrofuran 4: H2O2, trifluoroacetophenone, Py / CH2Cl2 View Scheme

4,9-Androstadiene-3,17-dione (5173-46-6) → 3,3-ethylenedioxy-5α,17β-dihydroxy-11β-[4-(N,N-dimethylamino)phenyl]-19-nor-17α-pregn-9-ene-21-ethyne (91934-95-1)

Conditions	Yield
Multi-step reaction with 5 steps 1: NaBH4 / tetrahydrofuran; methanol / -10 °C 2: 1.) (EtO)3CH, pTsOH, 2.) pyridinium chlorochromate / 2.) CH2Cl2 3: KOtBu / tetrahydrofuran 4: H2O2, trifluoroacetophenone, Py / CH2Cl2 5: Mg, CuCl View Scheme

4,9-Androstadiene-3,17-dione (5173-46-6) → (8S,11R,13S,14S,17S)-11-(4-Dimethylamino-phenyl)-17-hydroxy-13-methyl-17-phenylethynyl-1,2,6,7,8,11,12,13,14,15,16,17-dodecahydro-cyclopenta[a]phenanthren-3-one

Conditions	Yield
Multi-step reaction with 7 steps 1: NaBH4 / tetrahydrofuran; methanol / -10 °C 2: 1.) (EtO)3CH, pTsOH, 2.) pyridinium chlorochromate / 2.) CH2Cl2 3: KOtBu / tetrahydrofuran 4: H2O2, trifluoroacetophenone, Py / CH2Cl2 5: Mg, CuCl 6: CuI, Pd(OAc)2, PPh3 / various solvent(s) / Heating 7: H2SO4 / acetone View Scheme

4,9-Androstadiene-3,17-dione (5173-46-6) → (8S,11R,13S,14S,17R)-11-(4-Dimethylamino-phenyl)-17-[2-(4-dimethylamino-phenyl)-ethyl]-17-hydroxy-13-methyl-1,2,6,7,8,11,12,13,14,15,16,17-dodecahydro-cyclopenta[a]phenanthren-3-one

Conditions	Yield
Multi-step reaction with 7 steps 1: NaBH4 / tetrahydrofuran; methanol / -10 °C 2: 1.) (EtO)3CH, pTsOH, 2.) pyridinium chlorochromate / 2.) CH2Cl2 3: KOtBu / tetrahydrofuran 4: H2O2, trifluoroacetophenone, Py / CH2Cl2 5: Mg, CuCl 6: CuI, Pd(OAc)2, PPh3 / various solvent(s) / Heating 7: 1.) H2, 2.) H2SO4 / 1.) Pd/C / 1.) DMF, 2.) acetone View Scheme

4,9-Androstadiene-3,17-dione (5173-46-6) → C29H34O6 (173387-69-4)

Conditions	Yield
Multi-step reaction with 5 steps 1: NaBH4 / tetrahydrofuran; methanol / -10 °C 2: 1.) (EtO)3CH, pTsOH, 2.) pyridinium chlorochromate / 2.) CH2Cl2 3: KOtBu / tetrahydrofuran 4: H2O2, trifluoroacetophenone, Py / CH2Cl2 5: Mg, CuCl View Scheme

4,9-Androstadiene-3,17-dione (5173-46-6) → C30H36O6 (173387-77-4)

Conditions	Yield
Multi-step reaction with 5 steps 1: NaBH4 / tetrahydrofuran; methanol / -10 °C 2: 1.) (EtO)3CH, pTsOH, 2.) pyridinium chlorochromate / 2.) CH2Cl2 3: KOtBu / tetrahydrofuran 4: H2O2, trifluoroacetophenone, Py / CH2Cl2 5: Mg, CuCl View Scheme

4,9-Androstadiene-3,17-dione (5173-46-6) → (11β,17α)-11,21-bis[4-(dimethylamino)phenyl]-17-hydroxy-19-norpregna-4,9-dien-20-yn-3-one

Conditions	Yield
Multi-step reaction with 7 steps 1: NaBH4 / tetrahydrofuran; methanol / -10 °C 2: 1.) (EtO)3CH, pTsOH, 2.) pyridinium chlorochromate / 2.) CH2Cl2 3: KOtBu / tetrahydrofuran 4: H2O2, trifluoroacetophenone, Py / CH2Cl2 5: Mg, CuCl 6: CuI, Pd(OAc)2, PPh3 / various solvent(s) / Heating 7: H2SO4 / acetone View Scheme

4,9-Androstadiene-3,17-dione (5173-46-6) → C36H43NO4 (91934-88-2)

Conditions	Yield
Multi-step reaction with 6 steps 1: NaBH4 / tetrahydrofuran; methanol / -10 °C 2: 1.) (EtO)3CH, pTsOH, 2.) pyridinium chlorochromate / 2.) CH2Cl2 3: KOtBu / tetrahydrofuran 4: H2O2, trifluoroacetophenone, Py / CH2Cl2 5: Mg, CuCl 6: CuI, Pd(OAc)2, PPh3 / various solvent(s) / Heating View Scheme

4,9-Androstadiene-3,17-dione (5173-46-6) → (11β,17α)-11-[4-(dimethylamino)phenyl]-17-hydroxy-21-[4-(methylsulfonyl)phenyl]-19-norpregna-4,9-dien-20-yn-3-one

Conditions	Yield
Multi-step reaction with 7 steps 1: NaBH4 / tetrahydrofuran; methanol / -10 °C 2: 1.) (EtO)3CH, pTsOH, 2.) pyridinium chlorochromate / 2.) CH2Cl2 3: KOtBu / tetrahydrofuran 4: H2O2, trifluoroacetophenone, Py / CH2Cl2 5: Mg, CuCl 6: CuI, Pd(OAc)2, PPh3 / various solvent(s) / Heating 7: H2SO4 / acetone View Scheme

4,9-Androstadiene-3,17-dione (5173-46-6) → C38H48N2O4 (162607-85-4)

Conditions	Yield
Multi-step reaction with 6 steps 1: NaBH4 / tetrahydrofuran; methanol / -10 °C 2: 1.) (EtO)3CH, pTsOH, 2.) pyridinium chlorochromate / 2.) CH2Cl2 3: KOtBu / tetrahydrofuran 4: H2O2, trifluoroacetophenone, Py / CH2Cl2 5: Mg, CuCl 6: CuI, Pd(OAc)2, PPh3 / various solvent(s) / Heating View Scheme

4,9-Androstadiene-3,17-dione (5173-46-6) → (11β,17α)-11-(1,3-benzodioxol-5-yl)-21-[4-(methylsulfonyl)phenyl]-17-hydroxy-19-norpregna-4,9-dien-20-yn-3-one

Conditions	Yield
Multi-step reaction with 7 steps 1: NaBH4 / tetrahydrofuran; methanol / -10 °C 2: 1.) (EtO)3CH, pTsOH, 2.) pyridinium chlorochromate / 2.) CH2Cl2 3: KOtBu / tetrahydrofuran 4: H2O2, trifluoroacetophenone, Py / CH2Cl2 5: Mg, CuCl 6: CuI, Pd(OAc)2, PPh3 / various solvent(s) / Heating 7: H2SO4 / acetone View Scheme

4,9-Androstadiene-3,17-dione (5173-46-6) → 1-[4-[(11β,17α)-11-(2,3-dihydro-1,4-benzodioxin-6-yl)-17-hydroxy-3-oxo-19-nor-pregna-4,9-dien-20-yn-21-yl)phenyl]-2 pyrrolidinone

Conditions	Yield
Multi-step reaction with 7 steps 1: NaBH4 / tetrahydrofuran; methanol / -10 °C 2: 1.) (EtO)3CH, pTsOH, 2.) pyridinium chlorochromate / 2.) CH2Cl2 3: KOtBu / tetrahydrofuran 4: H2O2, trifluoroacetophenone, Py / CH2Cl2 5: Mg, CuCl 6: CuI, Pd(OAc)2, PPh3 / various solvent(s) / Heating 7: H2SO4 / acetone View Scheme

4,9-Androstadiene-3,17-dione (5173-46-6) → C37H45NO6S (196881-37-5)

Conditions	Yield
Multi-step reaction with 6 steps 1: NaBH4 / tetrahydrofuran; methanol / -10 °C 2: 1.) (EtO)3CH, pTsOH, 2.) pyridinium chlorochromate / 2.) CH2Cl2 3: KOtBu / tetrahydrofuran 4: H2O2, trifluoroacetophenone, Py / CH2Cl2 5: Mg, CuCl 6: CuI, Pd(OAc)2, PPh3 / various solvent(s) / Heating View Scheme

4,9-Androstadiene-3,17-dione (5173-46-6) → C36H40O8S (196881-38-6)

Conditions	Yield
Multi-step reaction with 6 steps 1: NaBH4 / tetrahydrofuran; methanol / -10 °C 2: 1.) (EtO)3CH, pTsOH, 2.) pyridinium chlorochromate / 2.) CH2Cl2 3: KOtBu / tetrahydrofuran 4: H2O2, trifluoroacetophenone, Py / CH2Cl2 5: Mg, CuCl 6: CuI, Pd(OAc)2, PPh3 / various solvent(s) / Heating View Scheme

Upstream product

• 6218-29-7 17β-hydroxyestra-4,9-dien-3-one 
• 17553-86-5 (S)-Halos-Parish ketone 
• 16271-49-1 (1S,7aS)-1-hydroxy-7a-methyl-2,3,7,7a-tetrahydro-1H-inden-5(6H)-one 
• 149789-99-1 (1S,7aS)-1-((tert-butyldimethylsilyl)oxy)-7a-methyl-1,2,3,6,7,7a-hexahydro-5H-inden-5-one 
• 1092775-41-1 1-(tert-butyldimethylsilyloxy)-7a-methyl-4-(2-(2-methyl-1,3-dioxolane-2-yl)ethyl)-2,3,5,6,7,7a-tetrahydro-1H-inden-5(6H)-one 
• 95935-96-9 <3aS-(3aα,9aα,9bβ)>-3β-((tert-butyldimethylsilyl)oxy)-3aβ-methyl-6-<2-(2-methyl-1,3-dioxolan-2-yl)ethyl>-1,2,3,3a,4,5,8,9,9a,9b-decahydro-7H-benzinden-7-one 
• 5978-08-5 1-chloro-4-(1,3-dioxolane)-n-pentane 
• 100981-86-0 5-(1,2-dihydro-4-methoxybenzocyclobuten-1-yl)-2-methyl-pent-1-en-3-one 
• 119804-91-0 3-(1,2-dihydro-4-methoxybenzocyclobutenyl)-1,1-ethylenedioxy-1-isopropenyl-propane 
• 119830-71-6 C₁₇H₂₂O₃ 
• 14776-96-6 (+/-)-Des-A-Δ⁹⁽¹⁰⁾-oestrendion-5,17 
• 26791-56-0 (3aS,9aS,9bS)-3a-Methyl-7-pyrrolidin-1-yl-1,2,3a,4,8,9,9a,9b-octahydro-cyclopenta[a]naphthalen-3-one 
• 13885-66-0 (+/-)-3-Chlor-4,5-secoestra-2,9-dien-5,17-dion 
• 10582-53-3 (+/-)-Δ⁹-4.5-seco-Oestrentrion-(3.5.17) 

Downstream Products

• 4019-90-3 (+/-)-17-Hydroxy-Δ^4,9-oestradienon-3 
• 901-93-9 Oestron-3-acetat 
• 10109-76-9 3,3-dimethoxy-estra-5⁽¹⁰⁾,9⁽¹¹⁾-diene-17-one 
• 49707-37-1 trenbolone acetate 
• 10161-33-8 trenbolone 
• 196881-39-7 C₄₀H₄₅NO₇ 
• 196881-38-6 C₃₆H₄₀O₈S 
• 196881-37-5 C₃₇H₄₅NO₆S 
• 162607-85-4 C₃₈H₄₈N₂O₄ 
• 91934-88-2 C₃₆H₄₃NO₄ 
• 91934-95-1 3,3-ethylenedioxy-5α,17β-dihydroxy-11β-[4-(N,N-dimethylamino)phenyl]-19-nor-17α-pregn-9-ene-21-ethyne 
• 5571-36-8 ethylene deltenone 
• 4019-90-3 (8R,13R,14R)-17-Hydroxy-13-methyl-1,2,6,7,8,11,12,13,14,15,16,17-dodecahydro-cyclopenta[a]phenanthren-3-one 
• 4019-90-3 (8S,14S)-17-Hydroxy-13-methyl-1,2,6,7,8,11,12,13,14,15,16,17-dodecahydro-cyclopenta[a]phenanthren-3-one 

Relevant articles and documents

- 4, 9 - Diene - 3, 17 - dione female ol the preparation method of the (by machine translation)

The invention provides a female neurosteroidogenesis - 4, 9 - diene - 3, 17 - dione of preparation method, the method comprising: in order to have the general formula I compound as the reaction raw material, to said reaction raw materials are mixed anhydride, Grignard reaction, ring-closing reaction, hydrolysis and ring-closing reaction, to obtain the compound having the structural formula V of; the compound has the formula V of the synthetic route of the are as follows: The embodiment of the invention provides a female steroid - 4, 9 - diene - 3, 17 - dione has the simple operation steps in the synthesis process, the raw materials, organic solvent consumption is small, after treatment is easy and easy to enlarge production and the like. (by machine translation)

Preparation method of estra-4,9-diene-3,17-dione

The present invention belongs to the field of synthesis of estra-4,9-diene-3,17-dione and discloses a preparation method of estra-4,9-diene-3,17-dione. The preparation method comprises preparation ofGrignard reagent, Grignard reaction, oxidation and hydrolysis reaction, and tandem cyclization reaction. The synthesis route designed in the present invention is characterized in that delta-lactone isused as the starting material and can be transformed to estra-4,9-diene-3,17-dione through three steps, namely, Grignard reaction, oxidation and hydrolysis reaction, and tandem cyclization reaction.The preparation method of estra-4,9-diene-3,17-dione is low in cost, low in environmental pollution, low in water consumption, easy to control, and high in yield with no need for highly toxic chemicals.

METHOD FOR PREPARING 4-[17β-METHOXY-17α-METHOXYMETHYL-3-OXOESTRA-4,9-DIEN-11β-YL]BENZALDEHYDE (E)-OXIME (ASOPRISNIL)

The present invention relates to a method for the reliable and reproducible preparation of 4-[17β-methoxy-17α-methoxymethyl-3-oxoestra-4,9-dien-llβ- yl]benzaldehyde (E)-oxime (asoprisnil) on the pilot and manufacturing scale. Asoprisnil, which is prepared by this method, is distinguished by a very good physical stability and is therefore particularly suitable for the manufacture of solid pharmaceutical forms (tablets, coated tablets, etc.).