CN1077894C - Process for preparing dieneketonol acetate - Google Patents
Process for preparing dieneketonol acetate Download PDFInfo
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- CN1077894C CN1077894C CN99118692A CN99118692A CN1077894C CN 1077894 C CN1077894 C CN 1077894C CN 99118692 A CN99118692 A CN 99118692A CN 99118692 A CN99118692 A CN 99118692A CN 1077894 C CN1077894 C CN 1077894C
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- hour
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- diosgenin
- hydrogen peroxide
- acetic acid
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Steroid Compounds (AREA)
Abstract
The present invention provides a method for preparing dehydropregnenolone acetate by using hydrogen peroxide as an oxidizing agent and using diosgenin as raw material. The method has the advantages of mild reaction condition, easy control of reaction products, easy treatment of industrial wastewater, no pollution to environment and low cost.
Description
The invention belongs to the production method technical field of steroid drugs intermediate, particularly, relate to a kind of method of producing dehydropregnenolone acetate.
The commercial run that with the diosgenin is the raw material production dehydropregnenolone acetate at present all is to adopt chromic anhydride (chromium trioxide) as oxygenant, not only reaction conditions is violent, and need special equipment, the corrosion that reaction solution causes equipment and the industrial pollution of chromic anhydride never are well solved, and are greatly restricting the development of steroid drugs.
At the above-mentioned shortcoming that present technology exists, the invention provides a kind of is that the oxygenant diosgenin is the method for raw material production dehydropregnenolone acetate with the hydrogen peroxide, this method reaction conditions gentleness, reaction product is easy to control, trade effluent is easy to handle, and environmentally safe is with low cost.
In order to realize purpose of the present invention, the invention provides following technical proposals:
Get diosgenin and be dissolved in aceticanhydride and the glacial acetic acid solution, reflux 1-2 hour, when being cooled to 40 ℃, add hydrogen peroxide, reacted 1-2 hour, and added ferrous sulfate or iron protochloride or S-WAT or Sulfothiorine then, add the entry heating and be hydrolyzed 1-2 hour until removing excessive hydrogen peroxide, reaction solution extracts with hexanaphthene, extract ethanol heating for dissolving is placed, and separates out crystallization, centrifuging, dry dehydropregnenolone acetate crystallization.
Getting diosgenin is dissolved in aceticanhydride and the glacial acetic acid solution, reflux 1-2 hour, when being cooled to 40 ℃, add the hydrogen peroxide of equivalent, reacted 1-2 hour, add the entry heating and be hydrolyzed 1-2 hour, reaction solution extracts with hexanaphthene, extract ethanol heating for dissolving, place, separate out crystallization, centrifuging, dry dehydropregnenolone acetate crystallization.
With the present invention is that the oxygenant diosgenin is the method for raw material production dehydropregnenolone acetate with the hydrogen peroxide, replace existing known technology to use chromic anhydride (chromium trioxide) owing to use hydrogen peroxide as oxygenant, therefore bring direct excellent beneficial effect to be: the reaction conditions gentleness, reaction product is easy to control, trade effluent is easy to handle, environmentally safe, with low cost.
Further specify essentiality content of the present invention below in conjunction with embodiment, but content of the present invention is not limited thereto.
Embodiment 1:
Get diosgenin 10g and place three mouthfuls of reaction flasks of 250ml, add 100ml aceticanhydride and 20ml Glacial acetic acid, heated and stirred dissolving on electric mantle, continue reflux 1 hour, and stopped heating, be cooled to 40 ℃, stir the hydrogen peroxide that adds 5ml30% down, insulated and stirred reaction 1 hour adds the 2g ferrous sulfate, eliminates excessive hydrogen peroxide, add 20ml water, be heated to 80 ℃ and stir hydrolysis 1 hour, reaction solution is poured out and is put in the 500ml separating funnel, adds hexanaphthene 150ml and shakes extraction, tell the hexanaphthene layer, the reclaim under reduced pressure hexanaphthene, residue cools off and places with ethanol 50ml heating for dissolving, separate out white, needle-shaped crystals, filter, 120 ℃ of dryings 1 hour, dehydropregnenolone acetate 6.4g.Water layer can reclaim acetic acid and ferric sulfate.
Embodiment 2:
Get diosgenin 10g and place three mouthfuls of reaction flasks of 250ml, add 100ml aceticanhydride and 20ml Glacial acetic acid, heated and stirred dissolving on electric mantle, continue reflux 1 hour, and stopped heating, be cooled to 40 ℃, stir the hydrogen peroxide that adds 5ml50% down, insulated and stirred reaction 1 hour adds 5g Sulfothiorine, eliminates excessive hydrogen peroxide, add 20ml water, be heated to 80 ℃ and stir hydrolysis 1 hour, reaction solution is poured out and is put in the 500ml separating funnel, adds hexanaphthene 150ml and shakes extraction, tell the hexanaphthene layer, the reclaim under reduced pressure hexanaphthene, residue cools off and places with ethanol 50ml heating for dissolving, separate out white, needle-shaped crystals, filter, 120 ℃ of dryings 1 hour, dehydropregnenolone acetate 6.8g.
Embodiment 3:
Get diosgenin 10g and place three mouthfuls of reaction flasks of 250ml, add 100ml aceticanhydride and 20ml Glacial acetic acid, heated and stirred dissolving on electric mantle, continue reflux 2 hours, and stopped heating, be cooled to 40 ℃, stir the hydrogen peroxide that adds 5ml30% down, insulated and stirred reaction 1 hour adds 3 gram iron protochlorides, eliminates excessive hydrogen peroxide, add 20ml water, be heated to 80 ℃ and stir hydrolysis 1 hour, reaction solution is poured out and is put in the 500ml separating funnel, adds hexanaphthene 150ml and shakes extraction, tell the hexanaphthene layer, the reclaim under reduced pressure hexanaphthene, residue cools off and places with ethanol 50ml heating for dissolving, separate out white, needle-shaped crystals, filter, 120 ℃ of dryings 1 hour, dehydropregnenolone acetate 6.5g.
Embodiment 4:
Get diosgenin 10g and place three mouthfuls of reaction flasks of 250ml, add 100ml aceticanhydride and 20ml Glacial acetic acid, heated and stirred dissolving on electric mantle, continue reflux 1 hour, and stopped heating, be cooled to 40 ℃, stir the hydrogen peroxide that adds 5ml50% down, insulated and stirred reaction 1 hour adds the 4g S-WAT, eliminates excessive hydrogen peroxide, add 20ml water, be heated to 80 ℃ and stir hydrolysis 1 hour, reaction solution is poured out and is put in the 500ml separating funnel, adds hexanaphthene 150ml and shakes extraction, tell the hexanaphthene layer, the reclaim under reduced pressure hexanaphthene, residue cools off and places with ethanol 50ml heating for dissolving, separate out white, needle-shaped crystals, filter, 120 ℃ of dryings 1 hour, dehydropregnenolone acetate 6.7g.
Embodiment 5:
Get diosgenin 10g and place three mouthfuls of reaction flasks of 250ml, add 100ml aceticanhydride and 20ml Glacial acetic acid, heated and stirred dissolving on electric mantle, continue reflux 2 hours, and stopped heating, be cooled to 40 ℃, stir the hydrogen peroxide that adds 5ml30% down, insulated and stirred reaction 2 hours adds the 3g ferrous sulfate, eliminates excessive hydrogen peroxide, add 20ml water, be heated to 80 ℃ and stir hydrolysis 2 hours, reaction solution is poured out and is put in the 500ml separating funnel, adds hexanaphthene 150ml and shakes extraction, tell the hexanaphthene layer, the reclaim under reduced pressure hexanaphthene, residue cools off and places with ethanol 50ml heating for dissolving, separate out white, needle-shaped crystals, filter, 120 ℃ of dryings 1 hour, dehydropregnenolone acetate 6.8g.
Embodiment 6:
Get diosgenin 10g and place three mouthfuls of reaction flasks of 250ml, add 100ml aceticanhydride and 20ml Glacial acetic acid, heated and stirred dissolving on electric mantle, continue reflux 2 hours, and stopped heating, be cooled to 40 ℃, stir the hydrogen peroxide that adds 5ml50% down, insulated and stirred reaction 2 hours adds 5g Sulfothiorine, eliminates excessive hydrogen peroxide, add 20ml water, be heated to 80 ℃ and stir hydrolysis 2 hours, reaction solution is poured out and is put in the 500ml separating funnel, adds hexanaphthene 150ml and shakes extraction, tell the hexanaphthene layer, the reclaim under reduced pressure hexanaphthene, residue cools off and places with ethanol 50ml heating for dissolving, separate out white, needle-shaped crystals, filter, 120 ℃ of dryings 2 hours, dehydropregnenolone acetate 6.8g.Water layer can reclaim acetic acid and Sulfothiorine.
Claims (2)
1, produce the method for dehydropregnenolone acetate, with the diosgenin is the acetic acid synthesized diene alcohol ketone of raw material, it is characterized in that getting diosgenin is dissolved in aceticanhydride and the glacial acetic acid solution, reflux 1-2 hour, when being cooled to 40 ℃, add hydrogen peroxide, reacted 1-2 hour, and added ferrous sulfate or iron protochloride or S-WAT or Sulfothiorine then, add the entry heating and be hydrolyzed 1-2 hour until removing excessive hydrogen peroxide, reaction solution extracts with hexanaphthene, extract ethanol heating for dissolving is placed, and separates out crystallization, centrifuging, dry dehydropregnenolone acetate crystallization.
2, producing the method for dehydropregnenolone acetate, is the acetic acid synthesized diene alcohol ketone of raw material with the diosgenin, it is characterized in that getting diosgenin and is dissolved in aceticanhydride and the glacial acetic acid solution, reflux 1-2 hour, when being cooled to 40 ℃, add the hydrogen peroxide of equivalent, reacted 1-2 hour, add the entry heating and be hydrolyzed 1-2 hour, reaction solution extracts with hexanaphthene, extract ethanol heating for dissolving, place, separate out crystallization, centrifuging, dry dehydropregnenolone acetate crystallization.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99118692A CN1077894C (en) | 1999-09-03 | 1999-09-03 | Process for preparing dieneketonol acetate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99118692A CN1077894C (en) | 1999-09-03 | 1999-09-03 | Process for preparing dieneketonol acetate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1247187A CN1247187A (en) | 2000-03-15 |
| CN1077894C true CN1077894C (en) | 2002-01-16 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99118692A Expired - Fee Related CN1077894C (en) | 1999-09-03 | 1999-09-03 | Process for preparing dieneketonol acetate |
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| Country | Link |
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| CN (1) | CN1077894C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102516066B (en) * | 2011-12-22 | 2016-05-04 | 东北师范大学 | Ostopanic acid analog and Preparation method and use |
| CN103242421B (en) * | 2013-05-09 | 2015-04-15 | 北京化工大学 | Process method for co-producing diosgenin, glucose, xylose and arabinose by hydrolyzing yellow ginger by utilizing volatile acid |
| CN104045676A (en) * | 2013-12-13 | 2014-09-17 | 成都丽璟科技有限公司 | Method for producing 16-dehydropregnenolone acetate |
| CN112608363A (en) * | 2020-12-18 | 2021-04-06 | 湖北民生生物医药有限公司 | Process for extracting dehydropregnenolone acetate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1026181C (en) * | 1987-07-26 | 1994-10-12 | 湖北制药厂 | Cracking of disgenin and new art of mother liquor recovery therefrom |
| US5808117A (en) * | 1996-01-22 | 1998-09-15 | Chowdhury; Pritish Kumar | Process for the production of 16-Dehydropregenolone acetate form diosgenin |
-
1999
- 1999-09-03 CN CN99118692A patent/CN1077894C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1026181C (en) * | 1987-07-26 | 1994-10-12 | 湖北制药厂 | Cracking of disgenin and new art of mother liquor recovery therefrom |
| US5808117A (en) * | 1996-01-22 | 1998-09-15 | Chowdhury; Pritish Kumar | Process for the production of 16-Dehydropregenolone acetate form diosgenin |
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| Publication number | Publication date |
|---|---|
| CN1247187A (en) | 2000-03-15 |
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