4472-02-0

Basic information

• Product Name: 3α-Acetyloxy-12-oxo-5β-chol-9(11)-en-24-oic acid methyl ester
• Synonyms: 3α-Acetyloxy-12-oxo-5β-chol-9(11)-en-24-oic acid methyl ester
• CAS NO: 4472-02-0
• Molecular Formula: C₂₇H₄₀O₅
• Molecular Weight: 444.6035
• Mol File: 4472-02-0.mol
• Article Data: 8

Chemical Properties

• Boiling Point: 531°Cat760mmHg
• Flash Point: 224.6°C
• Appearance: /
• Density: 1.12g/cm³
• Vapor Pressure: 2.34E-11mmHg at 25°C
• Refractive Index: 1.529
• CAS DataBase Reference: 3α-Acetyloxy-12-oxo-5β-chol-9(11)-en-24-oic acid methyl ester(CAS DataBase Reference)
• NIST Chemistry Reference: 3α-Acetyloxy-12-oxo-5β-chol-9(11)-en-24-oic acid methyl ester(4472-02-0)
• EPA Substance Registry System: 3α-Acetyloxy-12-oxo-5β-chol-9(11)-en-24-oic acid methyl ester(4472-02-0)

Safety Data

• Hazardous Substances Data: 4472-02-0(Hazardous Substances Data)

Usage

General Description

3α-Acetyloxy-12-oxo-5β-chol-9(11)-en-24-oic acid methyl ester is a chemical compound that belongs to the steroid class of organic compounds. It is a methyl ester derivative of a bile acid and is involved in the regulation of cholesterol metabolism. 3α-Acetyloxy-12-oxo-5β-chol-9(11)-en-24-oic acid methyl ester has potential applications in the pharmaceutical industry, particularly in the development of cholesterol-lowering drugs. Additionally, it may have implications in research related to the treatment of liver and gallbladder diseases. The compound's structure and properties make it a subject of interest for further investigation and potential therapeutic development.

InChI:InChI=1/C27H40O5/c1-16(6-11-25(30)31-5)21-9-10-22-20-8-7-18-14-19(32-17(2)28)12-13-26(18,3)23(20)15-24(29)27(21,22)4/h15-16,18-22H,6-14H2,1-5H3/t16-,18-,19-,20+,21-,22+,26+,27-/m1/s1

Synthetic route

methyl 3α-acetoxy-12-oxo-5β-cholan-24-oate (5143-55-5) → methyl 3α-acetoxy-12-oxo-5β-chol-9(11)-en-24-oate (4472-02-0)

Conditions	Yield
With 3-iodosylbenzoic acid; diphenyl diselenide In toluene for 96h; Heating;	89%
With selenium(IV) oxide; acetic acid for 18h; Reflux;	78%
With selenium(IV) oxide; acetic acid
With selenium(IV) oxide; acetic acid at 180℃; for 0.5h; Temperature; Microwave irradiation;

methyl 3α-acetoxy-5β-chol-9(11)-en-24-oate (30365-63-0) → C31H50O6 (1311972-67-4) + methyl 3α-acetoxy-12-oxo-5β-chol-9(11)-en-24-oate (4472-02-0)

Conditions	Yield
Stage #1: methyl 3α-acetoxy-5β-chol-9(11)-en-24-oate With tert.-butylhydroperoxide; sodium hypochlorite In water; ethyl acetate at 0 - 5℃; for 7h; Stage #2: With sodium sulfite In ethyl acetate Stage #3: With pyridinium chlorochromate In ethyl acetate Product distribution / selectivity;	A n/a B 63%

methyl 3α-acetoxy-5β-chol-9(11)-en-24-oate (30365-63-0) → methyl 3α-acetoxy-12-oxo-5β-chol-9(11)-en-24-oate (4472-02-0)

Conditions	Yield
Stage #1: methyl 3α-acetoxy-5β-chol-9(11)-en-24-oate With tert.-butylhydroperoxide; sodium hypochlorite In water; ethyl acetate at 0℃; for 8 - 10h; Stage #2: With sodium sulfite In water; ethyl acetate at 50 - 55℃; for 2h; Stage #3: With pyridinium chlorochromate In ethyl acetate at 25 - 30℃; for 6 - 8h; Product distribution / selectivity;	62%
Stage #1: methyl 3α-acetoxy-5β-chol-9(11)-en-24-oate With tert.-butylhydroperoxide; sodium hypochlorite In water; ethyl acetate at 0 - 5℃; Stage #2: With pyridinium chlorochromate In ethyl acetate Solvent; Reagent/catalyst; Temperature;	60.6%
Multi-step reaction with 2 steps 1: tert.-butylhydroperoxide; sodium hypochlorite / ethyl acetate; water / 7 h / 0 - 5 °C 2: potassium carbonate; hydrogen / palladium on activated charcoal / dichloromethane / 24 h / 20 °C View Scheme
Stage #1: methyl 3α-acetoxy-5β-chol-9(11)-en-24-oate With tert.-butylhydroperoxide; sodium hypochlorite In water; ethyl acetate at 0 - 5℃; Stage #2: With pyridinium chlorochromate In ethyl acetate at 25 - 30℃; Reagent/catalyst; Solvent; Time; Temperature;	13 g
With chromium(VI) oxide In acetic acid at 50℃;

C31H50O6 (1311972-67-4) → methyl 3α-acetoxy-12-oxo-5β-chol-9(11)-en-24-oate (4472-02-0)

Conditions	Yield
With tert.-butylhydroperoxide; palladium on activated charcoal; potassium carbonate In dichloromethane at 20℃; for 24h;	11%
With hydrogen; potassium carbonate; palladium on activated charcoal In dichloromethane at 20℃; for 24h;	11 %Chromat.

pyridine (110-86-1) + 3α-acetoxy-11β-bromo-12-oxo-5β-cholan-24-oic acid methyl ester (88128-14-7) → methyl 3α-acetoxy-12-oxo-5β-chol-9(11)-en-24-oate (4472-02-0)

2,4,6-trimethyl-pyridine (108-75-8) + 3α-acetoxy-11α-bromo-12-oxo-5β-cholan-24-oic acid methyl ester (17550-22-0) → methyl 3α-acetoxy-12-oxo-5β-chol-9(11)-en-24-oate (4472-02-0)

methyl 3α-acetoxy-5β-chol-9(11)-en-24-oate (30365-63-0) → methyl 3α-acetoxy-12-oxo-5β-chol-9(11)-en-24-oate (4472-02-0) + 3α-acetoxy-9,11β-epoxy-5β,9β-cholan-24-oic acid methyl ester (107329-63-5)

Conditions	Yield
With potassium permanganate; acetic acid

12α-hydroxy-3α-acetoxy-5β-cholen-(9(11))-oic acid-(24)-methyl ester (24637-48-7) → methyl 3α-acetoxy-12-oxo-5β-chol-9(11)-en-24-oate (4472-02-0)

Conditions	Yield
With chromium(VI) oxide; acetic acid

3α-acetoxy-11β-bromo-12-oxo-5β-cholan-24-oic acid methyl ester (88128-14-7) → methyl 3α-acetoxy-12-oxo-5β-chol-9(11)-en-24-oate (4472-02-0)

Conditions	Yield
With pyridine

methyl 3α-hydroxy-12-oxo-5β-chol-9(11)-en-24-oate (65065-56-7) + acetic anhydride (108-24-7) → methyl 3α-acetoxy-12-oxo-5β-chol-9(11)-en-24-oate (4472-02-0)

Conditions	Yield
With pyridine

methyl 3α-acetoxy-5β-chol-11-ene-24-oate (2242-12-8) + N-bromoacetamide (79-15-2) → methyl 3α-acetoxy-12-oxo-5β-chol-9(11)-en-24-oate (4472-02-0) + methyl 3α-acetoxy-11-oxo-5β-cholan-24-oate (4651-66-5)

Conditions	Yield
With water; acetone Behandeln einer Loesung des Reaktionsprodukts in Chloroform und Essigsaeure mit Chrom(VI)-oxid und Erwaermen des danach isolierten Reaktionsprodukts mit Zink, Natriumacetat und Essigsaeure;
With water; tert-butyl alcohol Behandeln einer Loesung des Reaktionsprodukts in Chloroform und Essigsaeure mit Chrom(VI)-oxid und Erwaermen des danach isolierten Reaktionsprodukts mit Zink, Natriumacetat und Essigsaeure;

methyl 3α-acetoxy-5β-chol-9(11)-en-24-oate (30365-63-0) + acetic acid (64-19-7) + chromium (VI)-oxide → methyl 3α-acetoxy-12-oxo-5β-chol-9(11)-en-24-oate (4472-02-0)

methyl 3α-acetoxy-5β-chol-9(11)-en-24-oate (30365-63-0) + water containing acetic acid + aqueous potassium permanganate solution → methyl 3α-acetoxy-12-oxo-5β-chol-9(11)-en-24-oate (4472-02-0) + 3α-acetoxy-9.11β-epoxy-5β.9β-cholanoic acid (24)-methyl ester

methyl 3α-acetoxy-5β-chol-11-ene-24-oate (2242-12-8) + water (7732-18-5) + sodium acetate (127-09-3) + acetone (67-64-1) + N-bromoacetamide (79-15-2) → 11β.12α-dibromo-3α-acetoxy-5β-cholanoic acid-(24)-methyl ester + methyl 3α-acetoxy-12-oxo-5β-chol-9(11)-en-24-oate (4472-02-0) + 3α-acetoxy-11β.12β-epoxy-5β-cholanoic acid (24)-methyl ester

Conditions	Yield
Chromatographieren des Reaktionsprodukts an alkalihaltigem Aluminiumoxid;

methyl 3α-acetoxy-5β-chol-11-ene-24-oate (2242-12-8) + water (7732-18-5) + acetone (67-64-1) + N-bromoacetamide (79-15-2) → methyl 3α-acetoxy-12-oxo-5β-chol-9(11)-en-24-oate (4472-02-0) + methyl 3α-acetoxy-11-oxo-5β-cholan-24-oate (4651-66-5)

Conditions	Yield
Reaktion ueber mehrere Stufen;

methyl 3α-acetoxy-5β-chol-11-ene-24-oate (2242-12-8) + water (7732-18-5) + tert-butyl alcohol (75-65-0) + N-bromoacetamide (79-15-2) → methyl 3α-acetoxy-12-oxo-5β-chol-9(11)-en-24-oate (4472-02-0) + methyl 3α-acetoxy-11-oxo-5β-cholan-24-oate (4651-66-5)

Conditions	Yield
Reaktion ueber mehrere Stufen;

9(11),(5β)-cholenic acid-3α-ol-12-one (6874-18-6) → methyl 3α-acetoxy-12-oxo-5β-chol-9(11)-en-24-oate (4472-02-0)

Conditions	Yield
Multi-step reaction with 2 steps 1: diazomethane; diethyl ether 2: pyridine View Scheme

12-oxolithocholic acid (5130-29-0) → methyl 3α-acetoxy-12-oxo-5β-chol-9(11)-en-24-oate (4472-02-0)

Conditions	Yield
Multi-step reaction with 4 steps 1: acetic acid 2: hydrogen bromide; acetic acid; bromine 3: diazomethane; diethyl ether 4: pyridine View Scheme

3α-hydroxy-12-oxo-5β-cholan-24-oic acid methyl ester (28050-47-7) → methyl 3α-acetoxy-12-oxo-5β-chol-9(11)-en-24-oate (4472-02-0)

Conditions	Yield
Multi-step reaction with 4 steps 1: benzene; pyridine 2: bromine; acetic acid / Erwaermen des Reaktionsprodukts mit aethanol. Natriumaethylat 3: diazomethane; diethyl ether 4: pyridine View Scheme

3α-acetoxy-12-oxo-5β-cholanoic acid-(24) (66874-05-3) → methyl 3α-acetoxy-12-oxo-5β-chol-9(11)-en-24-oate (4472-02-0)

Conditions	Yield
Multi-step reaction with 3 steps 1: hydrogen bromide; acetic acid; bromine 2: diazomethane; diethyl ether 3: pyridine View Scheme
Multi-step reaction with 3 steps 1: bromine; acetic acid / Erwaermen des Reaktionsprodukts mit aethanol. Natriumaethylat 2: diazomethane; diethyl ether 3: pyridine View Scheme

3α-acetoxy-11β-bromo-12α-hydroxy-5β-cholan-24-oic acid methyl ester (117863-38-4) → methyl 3α-acetoxy-12-oxo-5β-chol-9(11)-en-24-oate (4472-02-0)

Conditions	Yield
Multi-step reaction with 2 steps 1: silver acetate; acetic acid 2: chromium (VI)-oxide; acetic acid View Scheme
Multi-step reaction with 2 steps 1: chromium (VI)-oxide; acetic acid 2: pyridine View Scheme

11β-bromo-3α-acetoxy-12-oxo-5β-cholanoic acid-(24) → methyl 3α-acetoxy-12-oxo-5β-chol-9(11)-en-24-oate (4472-02-0)

Conditions	Yield
Multi-step reaction with 2 steps 1: diazomethane; diethyl ether 2: pyridine View Scheme

3α-benzoyloxy-12-oxo-5β-cholanoic acid-(24)-methyl ester (17225-41-1, 89887-44-5) → methyl 3α-acetoxy-12-oxo-5β-chol-9(11)-en-24-oate (4472-02-0)

Conditions	Yield
Multi-step reaction with 3 steps 1: bromine; acetic acid / Erwaermen des Reaktionsprodukts mit aethanol. Natriumaethylat 2: diazomethane; diethyl ether 3: pyridine View Scheme

12α-chloro-3α-acetoxy-5β-cholen-(9(11))-oic acid-(24)-methyl ester (107159-90-0) → methyl 3α-acetoxy-12-oxo-5β-chol-9(11)-en-24-oate (4472-02-0)

Conditions	Yield
Multi-step reaction with 2 steps 1: silver carbonate; aqueous acetone 2: chromium (VI)-oxide; acetic acid View Scheme

12α-methoxy-3α-acetoxy-5β-cholen-(9(11))-oic acid-(24)-methyl ester (107177-54-8) → methyl 3α-acetoxy-12-oxo-5β-chol-9(11)-en-24-oate (4472-02-0)

Conditions	Yield
Multi-step reaction with 3 steps 1: chloroform; hydrogen chloride 2: silver carbonate; aqueous acetone 3: chromium (VI)-oxide; acetic acid View Scheme

9-alpha-hydroxyandrost-4-ene-3,17-dione (560-62-3, 23015-99-8) → methyl 3α-acetoxy-12-oxo-5β-chol-9(11)-en-24-oate (4472-02-0)

Conditions	Yield
Multi-step reaction with 9 steps 1.1: hydrogen / palladium 10% on activated carbon / N,N-dimethyl-formamide / 3 h / 25 - 35 °C / 3102.97 Torr 2.1: sulfuric acid / dichloromethane / 2.15 h / 10 - 35 °C 3.1: lithium tri-t-butoxyaluminum hydride / tetrahydrofuran / 2 h / -45 - -40 °C / Inert atmosphere 4.1: potassium tert-butylate / tetrahydrofuran / 1.33 h / 25 - 35 °C / Inert atmosphere 4.2: 3 - 5 h / 25 - 35 °C / Inert atmosphere 4.3: Cooling 5.1: triethylamine / dmap / tert-butyl methyl ether / 2 h / 25 - 35 °C / Inert atmosphere 6.1: ethylaluminum dichloride / dichloromethane; toluene / 20 h / 0 - 35 °C / Inert atmosphere 6.2: Cooling 7.1: hydrogen / palladium on activated charcoal / ethyl acetate / 16 h / 25 - 35 °C / 3620.13 Torr 8.1: tert.-butylhydroperoxide; sodium hypochlorite / ethyl acetate; water / 7 h / 0 - 5 °C 9.1: potassium carbonate; hydrogen / palladium on activated charcoal / dichloromethane / 24 h / 20 °C View Scheme
Multi-step reaction with 8 steps 1.1: hydrogen / palladium 10% on activated carbon / N,N-dimethyl-formamide / 3 h / 25 - 35 °C / 3102.97 Torr 2.1: sulfuric acid / dichloromethane / 2.15 h / 10 - 35 °C 3.1: lithium tri-t-butoxyaluminum hydride / tetrahydrofuran / 2 h / -45 - -40 °C / Inert atmosphere 4.1: potassium tert-butylate / tetrahydrofuran / 1.33 h / 25 - 35 °C / Inert atmosphere 4.2: 3 - 5 h / 25 - 35 °C / Inert atmosphere 4.3: Cooling 5.1: triethylamine / dmap / tert-butyl methyl ether / 2 h / 25 - 35 °C / Inert atmosphere 6.1: ethylaluminum dichloride / dichloromethane; toluene / 20 h / 0 - 35 °C / Inert atmosphere 6.2: Cooling 7.1: hydrogen / palladium on activated charcoal / ethyl acetate / 16 h / 25 - 35 °C / 3620.13 Torr 8.1: tert.-butylhydroperoxide; sodium hypochlorite / ethyl acetate; water / 7 h / 0 - 5 °C View Scheme
Multi-step reaction with 8 steps 1.1: hydrogen / palladium 10% on activated carbon / N,N-dimethyl-formamide / 3 h / 25 - 35 °C / 3102.97 Torr 2.1: sulfuric acid / dichloromethane / 2.15 h / 10 - 35 °C 3.1: lithium tri-t-butoxyaluminum hydride / tetrahydrofuran / 2 h / -45 - -40 °C / Inert atmosphere 4.1: potassium tert-butylate / tetrahydrofuran / 1.33 h / 25 - 35 °C / Inert atmosphere 4.2: 3 - 5 h / 25 - 35 °C / Inert atmosphere 4.3: Cooling 5.1: triethylamine / dmap / tert-butyl methyl ether / 2 h / 25 - 35 °C / Inert atmosphere 6.1: ethylaluminum dichloride / dichloromethane; toluene / 20 h / 0 - 35 °C / Inert atmosphere 6.2: Cooling 7.1: hydrogen / palladium on activated charcoal / ethyl acetate / 16 h / 25 - 35 °C / 3620.13 Torr 8.1: tert.-butylhydroperoxide; sodium hypochlorite / ethyl acetate; water / 8 - 10 h / 0 °C 8.2: 2 h / 50 - 55 °C 8.3: 6 - 8 h / 25 - 30 °C View Scheme

9α-hydroxy-5β-androstan-3,17-dione (1093397-61-5) → methyl 3α-acetoxy-12-oxo-5β-chol-9(11)-en-24-oate (4472-02-0)

Conditions	Yield
Multi-step reaction with 8 steps 1.1: sulfuric acid / dichloromethane / 2.15 h / 10 - 35 °C 2.1: lithium tri-t-butoxyaluminum hydride / tetrahydrofuran / 2 h / -45 - -40 °C / Inert atmosphere 3.1: potassium tert-butylate / tetrahydrofuran / 1.33 h / 25 - 35 °C / Inert atmosphere 3.2: 3 - 5 h / 25 - 35 °C / Inert atmosphere 3.3: Cooling 4.1: triethylamine / dmap / tert-butyl methyl ether / 2 h / 25 - 35 °C / Inert atmosphere 5.1: ethylaluminum dichloride / dichloromethane; toluene / 20 h / 0 - 35 °C / Inert atmosphere 5.2: Cooling 6.1: hydrogen / palladium on activated charcoal / ethyl acetate / 16 h / 25 - 35 °C / 3620.13 Torr 7.1: tert.-butylhydroperoxide; sodium hypochlorite / ethyl acetate; water / 7 h / 0 - 5 °C 8.1: potassium carbonate; hydrogen / palladium on activated charcoal / dichloromethane / 24 h / 20 °C View Scheme
Multi-step reaction with 7 steps 1.1: sulfuric acid / dichloromethane / 2.15 h / 10 - 35 °C 2.1: lithium tri-t-butoxyaluminum hydride / tetrahydrofuran / 2 h / -45 - -40 °C / Inert atmosphere 3.1: potassium tert-butylate / tetrahydrofuran / 1.33 h / 25 - 35 °C / Inert atmosphere 3.2: 3 - 5 h / 25 - 35 °C / Inert atmosphere 3.3: Cooling 4.1: triethylamine / dmap / tert-butyl methyl ether / 2 h / 25 - 35 °C / Inert atmosphere 5.1: ethylaluminum dichloride / dichloromethane; toluene / 20 h / 0 - 35 °C / Inert atmosphere 5.2: Cooling 6.1: hydrogen / palladium on activated charcoal / ethyl acetate / 16 h / 25 - 35 °C / 3620.13 Torr 7.1: tert.-butylhydroperoxide; sodium hypochlorite / ethyl acetate; water / 7 h / 0 - 5 °C View Scheme
Multi-step reaction with 7 steps 1.1: sulfuric acid / dichloromethane / 2.15 h / 10 - 35 °C 2.1: lithium tri-t-butoxyaluminum hydride / tetrahydrofuran / 2 h / -45 - -40 °C / Inert atmosphere 3.1: potassium tert-butylate / tetrahydrofuran / 1.33 h / 25 - 35 °C / Inert atmosphere 3.2: 3 - 5 h / 25 - 35 °C / Inert atmosphere 3.3: Cooling 4.1: triethylamine / dmap / tert-butyl methyl ether / 2 h / 25 - 35 °C / Inert atmosphere 5.1: ethylaluminum dichloride / dichloromethane; toluene / 20 h / 0 - 35 °C / Inert atmosphere 5.2: Cooling 6.1: hydrogen / palladium on activated charcoal / ethyl acetate / 16 h / 25 - 35 °C / 3620.13 Torr 7.1: tert.-butylhydroperoxide; sodium hypochlorite / ethyl acetate; water / 8 - 10 h / 0 °C 7.2: 2 h / 50 - 55 °C 7.3: 6 - 8 h / 25 - 30 °C View Scheme

(5β)-androst-9(11)-ene-3,17-dione (1093397-63-7) → methyl 3α-acetoxy-12-oxo-5β-chol-9(11)-en-24-oate (4472-02-0)

Conditions	Yield
Multi-step reaction with 7 steps 1.1: lithium tri-t-butoxyaluminum hydride / tetrahydrofuran / 2 h / -45 - -40 °C / Inert atmosphere 2.1: potassium tert-butylate / tetrahydrofuran / 1.33 h / 25 - 35 °C / Inert atmosphere 2.2: 3 - 5 h / 25 - 35 °C / Inert atmosphere 2.3: Cooling 3.1: triethylamine / dmap / tert-butyl methyl ether / 2 h / 25 - 35 °C / Inert atmosphere 4.1: ethylaluminum dichloride / dichloromethane; toluene / 20 h / 0 - 35 °C / Inert atmosphere 4.2: Cooling 5.1: hydrogen / palladium on activated charcoal / ethyl acetate / 16 h / 25 - 35 °C / 3620.13 Torr 6.1: tert.-butylhydroperoxide; sodium hypochlorite / ethyl acetate; water / 7 h / 0 - 5 °C 7.1: potassium carbonate; hydrogen / palladium on activated charcoal / dichloromethane / 24 h / 20 °C View Scheme
Multi-step reaction with 6 steps 1.1: lithium tri-t-butoxyaluminum hydride / tetrahydrofuran / 2 h / -45 - -40 °C / Inert atmosphere 2.1: potassium tert-butylate / tetrahydrofuran / 1.33 h / 25 - 35 °C / Inert atmosphere 2.2: 3 - 5 h / 25 - 35 °C / Inert atmosphere 2.3: Cooling 3.1: triethylamine / dmap / tert-butyl methyl ether / 2 h / 25 - 35 °C / Inert atmosphere 4.1: ethylaluminum dichloride / dichloromethane; toluene / 20 h / 0 - 35 °C / Inert atmosphere 4.2: Cooling 5.1: hydrogen / palladium on activated charcoal / ethyl acetate / 16 h / 25 - 35 °C / 3620.13 Torr 6.1: tert.-butylhydroperoxide; sodium hypochlorite / ethyl acetate; water / 7 h / 0 - 5 °C View Scheme
Multi-step reaction with 6 steps 1.1: lithium tri-t-butoxyaluminum hydride / tetrahydrofuran / 2 h / -45 - -40 °C / Inert atmosphere 2.1: potassium tert-butylate / tetrahydrofuran / 1.33 h / 25 - 35 °C / Inert atmosphere 2.2: 3 - 5 h / 25 - 35 °C / Inert atmosphere 2.3: Cooling 3.1: triethylamine / dmap / tert-butyl methyl ether / 2 h / 25 - 35 °C / Inert atmosphere 4.1: ethylaluminum dichloride / dichloromethane; toluene / 20 h / 0 - 35 °C / Inert atmosphere 4.2: Cooling 5.1: hydrogen / palladium on activated charcoal / ethyl acetate / 16 h / 25 - 35 °C / 3620.13 Torr 6.1: tert.-butylhydroperoxide; sodium hypochlorite / ethyl acetate; water / 8 - 10 h / 0 °C 6.2: 2 h / 50 - 55 °C 6.3: 6 - 8 h / 25 - 30 °C View Scheme

3α-hydroxy-5β-androst-9(11)-en-17-one (571-49-3) → methyl 3α-acetoxy-12-oxo-5β-chol-9(11)-en-24-oate (4472-02-0)

Conditions	Yield
Multi-step reaction with 6 steps 1.1: potassium tert-butylate / tetrahydrofuran / 1.33 h / 25 - 35 °C / Inert atmosphere 1.2: 3 - 5 h / 25 - 35 °C / Inert atmosphere 1.3: Cooling 2.1: triethylamine / dmap / tert-butyl methyl ether / 2 h / 25 - 35 °C / Inert atmosphere 3.1: ethylaluminum dichloride / dichloromethane; toluene / 20 h / 0 - 35 °C / Inert atmosphere 3.2: Cooling 4.1: hydrogen / palladium on activated charcoal / ethyl acetate / 16 h / 25 - 35 °C / 3620.13 Torr 5.1: tert.-butylhydroperoxide; sodium hypochlorite / ethyl acetate; water / 7 h / 0 - 5 °C 6.1: potassium carbonate; hydrogen / palladium on activated charcoal / dichloromethane / 24 h / 20 °C View Scheme
Multi-step reaction with 5 steps 1.1: potassium tert-butylate / tetrahydrofuran / 1.33 h / 25 - 35 °C / Inert atmosphere 1.2: 3 - 5 h / 25 - 35 °C / Inert atmosphere 1.3: Cooling 2.1: triethylamine / dmap / tert-butyl methyl ether / 2 h / 25 - 35 °C / Inert atmosphere 3.1: ethylaluminum dichloride / dichloromethane; toluene / 20 h / 0 - 35 °C / Inert atmosphere 3.2: Cooling 4.1: hydrogen / palladium on activated charcoal / ethyl acetate / 16 h / 25 - 35 °C / 3620.13 Torr 5.1: tert.-butylhydroperoxide; sodium hypochlorite / ethyl acetate; water / 7 h / 0 - 5 °C View Scheme
Multi-step reaction with 5 steps 1.1: potassium tert-butylate / tetrahydrofuran / 1.33 h / 25 - 35 °C / Inert atmosphere 1.2: 3 - 5 h / 25 - 35 °C / Inert atmosphere 1.3: Cooling 2.1: triethylamine / dmap / tert-butyl methyl ether / 2 h / 25 - 35 °C / Inert atmosphere 3.1: ethylaluminum dichloride / dichloromethane; toluene / 20 h / 0 - 35 °C / Inert atmosphere 3.2: Cooling 4.1: hydrogen / palladium on activated charcoal / ethyl acetate / 16 h / 25 - 35 °C / 3620.13 Torr 5.1: tert.-butylhydroperoxide; sodium hypochlorite / ethyl acetate; water / 8 - 10 h / 0 °C 5.2: 2 h / 50 - 55 °C 5.3: 6 - 8 h / 25 - 30 °C View Scheme

(Z)-3α-hydroxy-5β-pregna-9(11),17(20)-diene (1093397-66-0) → methyl 3α-acetoxy-12-oxo-5β-chol-9(11)-en-24-oate (4472-02-0)

Conditions	Yield
Multi-step reaction with 5 steps 1.1: triethylamine / dmap / tert-butyl methyl ether / 2 h / 25 - 35 °C / Inert atmosphere 2.1: ethylaluminum dichloride / dichloromethane; toluene / 20 h / 0 - 35 °C / Inert atmosphere 2.2: Cooling 3.1: hydrogen / palladium on activated charcoal / ethyl acetate / 16 h / 25 - 35 °C / 3620.13 Torr 4.1: tert.-butylhydroperoxide; sodium hypochlorite / ethyl acetate; water / 7 h / 0 - 5 °C 5.1: potassium carbonate; hydrogen / palladium on activated charcoal / dichloromethane / 24 h / 20 °C View Scheme
Multi-step reaction with 4 steps 1.1: triethylamine / dmap / tert-butyl methyl ether / 2 h / 25 - 35 °C / Inert atmosphere 2.1: ethylaluminum dichloride / dichloromethane; toluene / 20 h / 0 - 35 °C / Inert atmosphere 2.2: Cooling 3.1: hydrogen / palladium on activated charcoal / ethyl acetate / 16 h / 25 - 35 °C / 3620.13 Torr 4.1: tert.-butylhydroperoxide; sodium hypochlorite / ethyl acetate; water / 7 h / 0 - 5 °C View Scheme
Multi-step reaction with 4 steps 1.1: triethylamine / dmap / tert-butyl methyl ether / 2 h / 25 - 35 °C / Inert atmosphere 2.1: ethylaluminum dichloride / dichloromethane; toluene / 20 h / 0 - 35 °C / Inert atmosphere 2.2: Cooling 3.1: hydrogen / palladium on activated charcoal / ethyl acetate / 16 h / 25 - 35 °C / 3620.13 Torr 4.1: tert.-butylhydroperoxide; sodium hypochlorite / ethyl acetate; water / 8 - 10 h / 0 °C 4.2: 2 h / 50 - 55 °C 4.3: 6 - 8 h / 25 - 30 °C View Scheme

methyl 3α-acetoxy-12-oxo-5β-chol-9(11)-en-24-oate (4472-02-0) → methyl 3α-acetoxy-12-oxo-5β-cholan-24-oate (5143-55-5)

Conditions	Yield
Stage #1: methyl 3α-acetoxy-12-oxo-5β-chol-9(11)-en-24-oate With hydrogen; palladium 10% on activated carbon In ethyl acetate at 45 - 50℃; for 18h; Stage #2: With pyridinium chlorochromate In ethyl acetate at 20℃; for 2h; Stage #3: With hydrogen; palladium on activated charcoal In ethyl acetate at 45 - 50℃; under 2585.81 Torr; for 18h;	95%
With hydrogen; palladium 10% on activated carbon In ethyl acetate at 45 - 50℃; under 2585.81 Torr; for 16h; Product distribution / selectivity;	83.1%
Stage #1: methyl 3α-acetoxy-12-oxo-5β-chol-9(11)-en-24-oate With hydrogen; palladium-on-charcoal In ethyl acetate at 45 - 50℃; under 2585.81 Torr; for 16h; Autoclave; Stage #2: With pyridinium chlorochromate In ethyl acetate at 25 - 35℃; for 2h; Product distribution / selectivity;	83.1%
Stage #1: methyl 3α-acetoxy-12-oxo-5β-chol-9(11)-en-24-oate With palladium 10% on activated carbon; hydrogen In ethyl acetate at 45 - 50℃; under 2585.81 Torr; for 16h; Stage #2: With pyridinium chlorochromate In ethyl acetate at 25 - 35℃; for 2h; Concentration; Reagent/catalyst; Temperature;	83.1%
With palladium 10% on activated carbon; hydrogen In ethyl acetate at 50℃; under 2585.81 Torr; for 16h; Autoclave;	80%

methyl 3α-acetoxy-12-oxo-5β-chol-9(11)-en-24-oate (4472-02-0) → 5β-chol-9(11)-en-3α,24-diol (13002-74-9)

Conditions	Yield
With aluminum (III) chloride; lithium aluminium tetrahydride In tetrahydrofuran for 4h; Reflux;	64%
With lithium aluminium tetrahydride; aluminium trichloride

methyl 3α-acetoxy-12-oxo-5β-chol-9(11)-en-24-oate (4472-02-0) → 3α-hydroxy-5β-chol-9(11)-en-24-oic acid (62797-60-8)

Conditions	Yield
With sodium ethanolate; hydrazine hydrate at 170℃;

methyl 3α-acetoxy-12-oxo-5β-chol-9(11)-en-24-oate (4472-02-0) → 9(11),(5β)-cholenic acid-3α-ol-12-one (6874-18-6)

Conditions	Yield
With potassium hydroxide
Multi-step reaction with 2 steps 1: hydrogen chloride; methanol 2: methanol. KOH-solution View Scheme

methyl 3α-acetoxy-12-oxo-5β-chol-9(11)-en-24-oate (4472-02-0) → methyl 3α-hydroxy-12-oxo-5β-chol-9(11)-en-24-oate (65065-56-7)

Conditions	Yield
With hydrogenchloride; methanol
With methanol; potassium hydroxide at 20℃; for 1.5h;

methyl 3α-acetoxy-12-oxo-5β-chol-9(11)-en-24-oate (4472-02-0) → 12β-hydroxy-3α-acetoxy-5β-cholen-(9(11))-oic acid-(24)-methyl ester (24637-47-6) + 12α-hydroxy-3α-acetoxy-5β-cholen-(9(11))-oic acid-(24)-methyl ester (24637-48-7)

Conditions	Yield
With ethanol; acetic acid; platinum Hydrogenation;

methyl 3α-acetoxy-12-oxo-5β-chol-9(11)-en-24-oate (4472-02-0) → methyl 3α-acetoxy-12-hydroxy-9(11)-cholenate (24637-47-6, 24637-48-7)

Conditions	Yield
With sodium tetrahydroborate; cerium(III) chloride In methanol for 0.5h; Ambient temperature;	1.28 g

ethanol (64-17-5) + methyl 3α-acetoxy-12-oxo-5β-chol-9(11)-en-24-oate (4472-02-0) + acetic acid (64-19-7) + platinum → methyl 3α-acetoxy-5β-chol-9(11)-en-24-oate (30365-63-0)

Conditions	Yield
Hydrogenation;

methyl 3α-acetoxy-12-oxo-5β-chol-9(11)-en-24-oate (4472-02-0) + sodium ethanolate (141-52-6) + hydrazine hydrate (7803-57-8) → methyl 3α-acetoxy-5β-chol-9(11)-en-24-oate (30365-63-0) + methyl 3α-acetoxy-5β-chol-11-ene-24-oate (2242-12-8)

Conditions	Yield
at 170℃; Behandeln des Reaktionsprodukts mit Diazomethan in Aether und Behandeln des danach isolierten Reaktionsprodukts mit Acetanhydrid und Pyridin;

ethanol (64-17-5) + methyl 3α-acetoxy-12-oxo-5β-chol-9(11)-en-24-oate (4472-02-0) + acetic acid (64-19-7) + platinum → 12β-hydroxy-3α-acetoxy-5β-cholen-(9(11))-oic acid-(24)-methyl ester (24637-47-6) + 12α-hydroxy-3α-acetoxy-5β-cholen-(9(11))-oic acid-(24)-methyl ester (24637-48-7)

Conditions	Yield
Hydrogenation;

methyl 3α-acetoxy-12-oxo-5β-chol-9(11)-en-24-oate (4472-02-0) → methyl 3α,12β-diacetoxy-9(11)-cholenate (24637-51-2)

Conditions	Yield
Multi-step reaction with 2 steps 1: 1.28 g / NaBH4, CeCl3*6H2O / methanol / 0.5 h / Ambient temperature 2: toluene; pyridine / 6 h / 100 °C View Scheme

methyl 3α-acetoxy-12-oxo-5β-chol-9(11)-en-24-oate (4472-02-0) → methyl 3α,12α-diacetoxy-9(11)-cholenate (24637-34-1)

Conditions	Yield
Multi-step reaction with 2 steps 1: 1.28 g / NaBH4, CeCl3*6H2O / methanol / 0.5 h / Ambient temperature 2: toluene; pyridine / 6 h / 100 °C View Scheme

Upstream product

• 110-86-1 pyridine 
• 88128-14-7 3α-acetoxy-11β-bromo-12-oxo-5β-cholan-24-oic acid methyl ester 
• 108-75-8 2,4,6-trimethyl-pyridine 
• 17550-22-0 3α-acetoxy-11α-bromo-12-oxo-5β-cholan-24-oic acid methyl ester 
• 2242-12-8 methyl 3α-acetoxy-5β-chol-11-ene-24-oate 
• 79-15-2 N-bromoacetamide 
• 6874-18-6 9(11),(5β)-cholenic acid-3α-ol-12-one 
• 5130-29-0 12-oxolithocholic acid 
• 2242-12-8 3β-acetoxy-5β-cholen-(11)-oic acid-(24)-methyl ester 
• 881023-82-1 methyl 3β-hydroxy-5β-chol-9(11)-ene-24-oate acetate 
• 7732-18-5 water 
• 75-65-0 tert-butyl alcohol 
• 67-64-1 acetone 
• 27240-83-1 methyl 3α-acetoxy-12α-hydroxy-5β-cholan-24-oate 

Downstream Products

• 62797-60-8 3α-hydroxy-5β-chol-9(11)-en-24-oic acid 
• 65065-56-7 methyl 3α-hydroxy-12-oxo-5β-chol-9(11)-en-24-oate 
• 30365-63-0 methyl 3α-acetoxy-5β-chol-9(11)-en-24-oate 
• 2242-12-8 methyl 3α-acetoxy-5β-chol-11-ene-24-oate 
• 83-44-3 Deoxycholic acid 
• 5143-55-5 methyl 3α-acetoxy-12-oxo-5β-cholan-24-oate 
• 27240-83-1 methyl 3α-acetoxy-12α-hydroxy-5β-cholan-24-oate 
• 4560-58-1 3β-hydroxy-12-oxo-5β-cholanoic acid-(24) 
• 24637-47-6 12β-hydroxy-3α-acetoxy-5β-cholen-(9(11))-oic acid-(24)-methyl ester 

Relevant articles and documents

Synthesis and biological activity of novel deoxycholic acid derivatives

We report the synthesis and biological activity of new semi-synthetic derivatives of naturally occurring deoxycholic acid (DCA) bearing 2-cyano-3-oxo-1-ene, 3-oxo-1(2)-ene or 3-oxo-4(5)-ene moieties in ring A and 12-oxo or 12-oxo-9(11)-ene moieties in ring C. Bioassays using murine macrophage-like cells and tumour cells show that the presence of the 9(11)-double bond associated with the increased polarity of ring A or with isoxazole ring joined to ring A, improves the ability of the compounds to inhibit cancer cell growth.

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Bile acids and related compositions and methods of synthesis and use. More specifically, deoxycholic acid and related compositions, said compositions being free of all moieties of animal origin and free of pyrogenic moieties.