3730-84-5

Basic information

• Product Name: (25R)-spirost-4-en-3,6-dione
• CAS NO: 3730-84-5
• Molecular Formula: C₂₇H₃₈O₄
• Molecular Weight: 426.5882
• Mol File: 3730-84-5.mol
• Article Data: 4

Chemical Properties

• Boiling Point: 553°C at 760 mmHg
• Flash Point: 236.6°C
• Density: 1.17g/cm³
• Vapor Pressure: 2.83E-12mmHg at 25°C
• Refractive Index: 1.564
• CAS DataBase Reference: (25R)-spirost-4-en-3,6-dione(CAS DataBase Reference)
• NIST Chemistry Reference: (25R)-spirost-4-en-3,6-dione(3730-84-5)
• EPA Substance Registry System: (25R)-spirost-4-en-3,6-dione(3730-84-5)

Safety Data

• Hazardous Substances Data: 3730-84-5(Hazardous Substances Data)

Usage

General Description

(25R)-Spirost-4-en-3,6-dione, also known as diosgenin, is a naturally occurring steroid sapogenin found in various plants such as fenugreek and wild yam. It is a precursor for the synthesis of several other steroid hormones, including progesterone and corticosteroids. Diosgenin has been studied for its potential medicinal properties, including anti-inflammatory, anti-cancer, and cholesterol-lowering effects. It has also been investigated for its role in improving insulin sensitivity and treating menopausal symptoms. Additionally, diosgenin has been used as a starting material for the semi-synthesis of various steroid medications.

Synthetic route

diosgenin (512-04-9) → (22S,25R)-spirost-4-en-3,6-dione (3730-84-5)

Conditions	Yield
With jones reagent In acetone at 15℃; for 0.5h;	95%
With Jones reagent In acetone at 10 - 20℃; Jones oxidation;	95%
With Jones reagent In dichloromethane; acetone at -10 - 10℃;	85%
With pyridinium chlorochromate In dichloromethane at 20℃; for 5h;	55%
Multi-step reaction with 3 steps 1: acetic acid; aqueous hydrogen peroxide / Erwaermen des Reaktionsprodukts mit aethanol. Kalilauge 2: chromium (VI)-oxide; acetic acid 3: 280 °C / unter vermindertem Druck View Scheme

(25R)-6β-hydroxy-spirost-4-en-3-one (6877-76-5) → (22S,25R)-spirost-4-en-3,6-dione (3730-84-5)

Conditions	Yield
With chromium(VI) oxide; acetic acid

(25R)-5α-hydroxy-5α-spirosta-3,6-dione (74395-54-3) → (22S,25R)-spirost-4-en-3,6-dione (3730-84-5)

Conditions	Yield
at 280℃; unter vermindertem Druck;

(25R)-spirost-4-en-3β-ol → (22S,25R)-spirost-4-en-3,6-dione (3730-84-5)

Conditions	Yield
With chromium(VI) oxide; acetic acid

acetic acid (64-19-7) + (25R)-6β-hydroxy-spirost-4-en-3-one (6877-76-5) + chromium (VI)-oxide → (22S,25R)-spirost-4-en-3,6-dione (3730-84-5)

water (7732-18-5) + acetic acid (64-19-7) + diosgenin (512-04-9) + chromium (VI)-oxide → (22S,25R)-spirost-4-en-3,6-dione (3730-84-5)

(25R)-spirostan-22α-O-3β,5α,6β-triol (56816-69-4) → (22S,25R)-spirost-4-en-3,6-dione (3730-84-5)

Conditions	Yield
Multi-step reaction with 2 steps 1: chromium (VI)-oxide; acetic acid 2: 280 °C / unter vermindertem Druck View Scheme
Multi-step reaction with 5 steps 1: pyridine 2: thionyl chloride; pyridine 3: aqueous methanol. KOH-solution 4: manganese (IV)-oxide; chloroform 5: aqueous acetic acid; chromium (VI)-oxide View Scheme

(25R)-5α,6α-epoxyspirostan-22α-O-3β-ol (3514-60-1) → (22S,25R)-spirost-4-en-3,6-dione (3730-84-5)

Conditions	Yield
Multi-step reaction with 3 steps 1: hydrogen chloride; ethanol 2: chromium (VI)-oxide; acetic acid 3: 280 °C / unter vermindertem Druck View Scheme

(25R)-spirost-4-ene-3β,6β-diol → (22S,25R)-spirost-4-en-3,6-dione (3730-84-5)

Conditions	Yield
Multi-step reaction with 2 steps 1: manganese (IV)-oxide; chloroform 2: aqueous acetic acid; chromium (VI)-oxide View Scheme

(25R)-3-acetoxy-spirosta-3,5-diene (6877-75-4) → (22S,25R)-spirost-4-en-3,6-dione (3730-84-5)

Conditions	Yield
Multi-step reaction with 2 steps 1: monoperoxyphthalic acid; diethyl ether / Lichtausschluss 2: aqueous acetic acid; chromium (VI)-oxide View Scheme

(25R)-3β,6β-diacetoxy-spirost-4-ene → (22S,25R)-spirost-4-en-3,6-dione (3730-84-5)

Conditions	Yield
Multi-step reaction with 3 steps 1: aqueous methanol. KOH-solution 2: manganese (IV)-oxide; chloroform 3: aqueous acetic acid; chromium (VI)-oxide View Scheme

(25R)-5α-spirostan-3β,5,6β-triol 3,6-diacetate (74395-53-2) → (22S,25R)-spirost-4-en-3,6-dione (3730-84-5)

Conditions	Yield
Multi-step reaction with 4 steps 1: thionyl chloride; pyridine 2: aqueous methanol. KOH-solution 3: manganese (IV)-oxide; chloroform 4: aqueous acetic acid; chromium (VI)-oxide View Scheme

(25R)-spirost-4-ene-3-one (6870-79-7) → (22S,25R)-spirost-4-en-3,6-dione (3730-84-5)

Conditions	Yield
Multi-step reaction with 3 steps 1: benzene; isopropenyl acetate; toluene-4-sulfonic acid 2: monoperoxyphthalic acid; diethyl ether / Lichtausschluss 3: aqueous acetic acid; chromium (VI)-oxide View Scheme

(22S,25R)-spirost-4-en-3,6-dione (3730-84-5) → (25R)-5α-spirostan-3,6-dione (3514-59-8)

Conditions	Yield
With hydrogen; palladium on activated charcoal In ethyl acetate at 40℃; for 48h;	80%

(22S,25R)-spirost-4-en-3,6-dione (3730-84-5) → C27H40N2O4

Conditions	Yield
With pyridine; hydroxylamine hydrochloride In ethanol for 1h; Reflux;	77%

2,3,4,6-tetra-O-benzoyl-α,b-D-mannopyranosyl trichloroacetimidate (934492-05-4) + (22S,25R)-spirost-4-en-3,6-dione (3730-84-5) → C61H64O13

Conditions	Yield
With trimethylsilyl trifluoromethanesulfonate In dichloromethane at 0℃; for 1h; Inert atmosphere; Molecular sieve;	68%

(22S,25R)-spirost-4-en-3,6-dione (3730-84-5) → (25R)-4-en-2α-bromo-spirosta-3,6-dione

Conditions	Yield
With phenyl trimethylammonium perbromide In tetrahydrofuran at 20℃; for 0.166667h;	67%

(22S,25R)-spirost-4-en-3,6-dione (3730-84-5) → (25R)-4,5α-epoxy-5α-spirosta-3,6-dione (1268164-20-0)

Conditions	Yield
With dihydrogen peroxide; sodium hydroxide In methanol; water at 15℃; for 1h;	63%

acetic acid (64-19-7) + (22S,25R)-spirost-4-en-3,6-dione (3730-84-5) + zinc-powder → (25R)-5α-spirostan-3,6-dione

(22S,25R)-spirost-4-en-3,6-dione (3730-84-5) → (25R)-2α-bromo-4,5α-epoxy-5α-spirosta-3,6-dione (1268164-21-1)

Conditions	Yield
Multi-step reaction with 2 steps 1: dihydrogen peroxide; sodium hydroxide / methanol; water / 1 h / 15 °C 2: phenyltrimethylammonium tribromide / tetrahydrofuran / 0.17 h / 20 °C View Scheme

(22S,25R)-spirost-4-en-3,6-dione (3730-84-5) → C27H37N3O5

Conditions	Yield
Multi-step reaction with 3 steps 1: dihydrogen peroxide; sodium hydroxide / methanol; water / 1 h / 15 °C 2: phenyltrimethylammonium tribromide / tetrahydrofuran / 0.17 h / 20 °C 3: sodium azide; potassium iodide / N,N-dimethyl-formamide / 4 h / 50 °C View Scheme

(22S,25R)-spirost-4-en-3,6-dione (3730-84-5) → C27H39NO5

Conditions	Yield
Multi-step reaction with 4 steps 1: dihydrogen peroxide; sodium hydroxide / methanol; water / 1 h / 15 °C 2: phenyltrimethylammonium tribromide / tetrahydrofuran / 0.17 h / 20 °C 3: sodium azide; potassium iodide / N,N-dimethyl-formamide / 4 h / 50 °C 4: triphenylphosphine / tetrahydrofuran / Inert atmosphere View Scheme

(22S,25R)-spirost-4-en-3,6-dione (3730-84-5) → di(25R-6-oxo-4,5α-epoxy-5α-spirostano[2,3-b:2',3'-e])pyrazine (1268164-22-2)

Conditions	Yield
Multi-step reaction with 5 steps 1: dihydrogen peroxide; sodium hydroxide / methanol; water / 1 h / 15 °C 2: phenyltrimethylammonium tribromide / tetrahydrofuran / 0.17 h / 20 °C 3: sodium azide; potassium iodide / N,N-dimethyl-formamide / 4 h / 50 °C 4: triphenylphosphine / tetrahydrofuran / Inert atmosphere 5: toluene-4-sulfonic acid / ethanol / 20 °C / 760.05 Torr View Scheme

Upstream product

• 6877-76-5 (25R)-6β-hydroxy-spirost-4-en-3-one 
• 64-19-7 acetic acid 
• 7732-18-5 water 
• 512-04-9 diosgenin 
• 512-06-1 yamogenin 
• 74395-53-2 (25R)-5α-spirostan-3β,5,6β-triol 3,6-diacetate 
• 6877-75-4 (25R)-3-acetoxy-spirosta-3,5-diene 
• 3514-60-1 (25R)-5α,6α-epoxyspirostan-22α-O-3β-ol 
• 56816-69-4 (25R)-spirostan-22α-O-3β,5α,6β-triol 
• 74395-54-3 (25R)-5α-hydroxy-5α-spirosta-3,6-dione 
• 6870-79-7 (25R)-spirost-4-ene-3-one 

Relevant articles and documents

Synthesis of new symmetrical bis-steroidal pyrazine analogues from diosgenin

New symmetrical bis-steroidal pyrazine dimers that are cephalostatins/ ritterazines analogues have been prepared easily from a cheap, readily available natural steroid (diosgenin). These dimers were obtained by classical, condensation of α-amino ketones in order to construct the pyrazine rings. The three dimers differ in the functionalized diosgenin: (25R)-5α,6β- dihydroxy-5α-spirosta-3-one, (25R)-4,5α-epoxy-5β-spirosta-3,6- dione and (25R)-5α-hydroxy-5α-spirosta-3,6-dione respectively.

Synthesis of bis-diosgenin pyrazine dimers: New cephalostatin analogs

A convenient synthesis for bis-diosgenin pyrazine dimers, cephalostatin analogues is reported. These symmetrical dimeric steroid-pyrazines were obtained by the classical condensation of α-amino ketones, the most efficient method for pyrazine ring construction.