CN87105226A - Novel process for cracking dehydropregnenolone acetate and recovering mother liquor - Google Patents
Novel process for cracking dehydropregnenolone acetate and recovering mother liquor Download PDFInfo
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- CN87105226A CN87105226A CN87105226.1A CN87105226A CN87105226A CN 87105226 A CN87105226 A CN 87105226A CN 87105226 A CN87105226 A CN 87105226A CN 87105226 A CN87105226 A CN 87105226A
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- mother liquor
- diosgenin
- cracking
- temperature
- heating
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- 239000012452 mother liquor Substances 0.000 title claims abstract description 35
- 238000005336 cracking Methods 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title abstract description 18
- MZWRIOUCMXPLKV-RFOVXIPZSA-N 16-Dehydropregnenolone acetate Chemical compound C([C@@H]12)C[C@]3(C)C(C(C)=O)=CC[C@H]3[C@@H]1CC=C1[C@]2(C)CC[C@H](OC(=O)C)C1 MZWRIOUCMXPLKV-RFOVXIPZSA-N 0.000 title abstract 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 238000011084 recovery Methods 0.000 claims abstract description 9
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 65
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 31
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 26
- DWCSNWXARWMZTG-UHFFFAOYSA-N Trigonegenin A Natural products CC1C(C2(CCC3C4(C)CCC(O)C=C4CCC3C2C2)C)C2OC11CCC(C)CO1 DWCSNWXARWMZTG-UHFFFAOYSA-N 0.000 claims description 24
- WQLVFSAGQJTQCK-VKROHFNGSA-N diosgenin Chemical compound O([C@@H]1[C@@H]([C@]2(CC[C@@H]3[C@@]4(C)CC[C@H](O)CC4=CC[C@H]3[C@@H]2C1)C)[C@@H]1C)[C@]11CC[C@@H](C)CO1 WQLVFSAGQJTQCK-VKROHFNGSA-N 0.000 claims description 24
- WQLVFSAGQJTQCK-UHFFFAOYSA-N diosgenin Natural products CC1C(C2(CCC3C4(C)CCC(O)CC4=CCC3C2C2)C)C2OC11CCC(C)CO1 WQLVFSAGQJTQCK-UHFFFAOYSA-N 0.000 claims description 24
- 235000019439 ethyl acetate Nutrition 0.000 claims description 22
- 150000001993 dienes Chemical class 0.000 claims description 20
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 18
- 150000002576 ketones Chemical class 0.000 claims description 17
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 13
- 229960000583 acetic acid Drugs 0.000 claims description 12
- 238000005516 engineering process Methods 0.000 claims description 12
- 239000012362 glacial acetic acid Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 4
- GMBQZIIUCVWOCD-WWASVFFGSA-N Sarsapogenine Chemical compound O([C@@H]1[C@@H]([C@]2(CC[C@@H]3[C@@]4(C)CC[C@H](O)C[C@H]4CC[C@H]3[C@@H]2C1)C)[C@@H]1C)[C@]11CC[C@H](C)CO1 GMBQZIIUCVWOCD-WWASVFFGSA-N 0.000 claims description 2
- RTMWIZOXNKJHRE-UHFFFAOYSA-N Tigogenin Natural products CC1COC2CC(C)(OC12)C3CCC4C5CCC6CC(O)CCC6(C)C5CCC34C RTMWIZOXNKJHRE-UHFFFAOYSA-N 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims description 2
- 239000000284 extract Substances 0.000 abstract description 4
- 239000001397 quillaja saponaria molina bark Substances 0.000 abstract description 4
- 229930182490 saponin Natural products 0.000 abstract description 4
- 150000007949 saponins Chemical class 0.000 abstract description 4
- 238000004090 dissolution Methods 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- VZRAKVPDZIQRGT-WZBAXQLOSA-N (8r,9s,10s,13r,14s,17r)-17-ethenyl-10,13-dimethyl-2,3,4,5,6,7,8,9,11,12,14,15,16,17-tetradecahydro-1h-cyclopenta[a]phenanthrene Chemical compound C1CCC[C@]2(C)[C@H]3CC[C@](C)([C@H](CC4)C=C)[C@@H]4[C@@H]3CCC21 VZRAKVPDZIQRGT-WZBAXQLOSA-N 0.000 abstract 1
- 238000002844 melting Methods 0.000 abstract 1
- 230000008018 melting Effects 0.000 abstract 1
- 239000012046 mixed solvent Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 11
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- FGKJLKRYENPLQH-UHFFFAOYSA-N isocaproic acid Chemical compound CC(C)CCC(O)=O FGKJLKRYENPLQH-UHFFFAOYSA-N 0.000 description 7
- 230000007017 scission Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 4
- 238000010504 bond cleavage reaction Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 229910052728 basic metal Inorganic materials 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- -1 steroid diene Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000003818 basic metals Chemical class 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 229960004249 sodium acetate Drugs 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 241001253206 Andrias Species 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000006166 lysate Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229940063767 oxygen 95 % Drugs 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Abstract
The invention improves the cracking and mother liquor recovery process in the preparation of 5.16 pregnene diene-3 beta-alcohol-20-ketone acetate (abbreviated as dehydropregnenolone acetate) from yam saponin, adopts a heating method of heating the bottom of a reaction tank and rapidly raising the temperature in the cracking process, increases the temperature rise speed, controls the dissolution and reaction temperature well, firstly saponifies the mother liquor by alkali metal hydroxide in the mother liquor treatment and recovery, then extracts by a mixed solvent of methanol and cyclohexane, and recycles all the mother liquor after layering and concentration treatment. By adopting new cracking and mother liquor recovery processes, the product yield is improved by 4.5 percent and reaches 66.5 percent, and the melting point is improved by 1 ℃ and reaches 166 ℃.
Description
The invention belongs to the compound synthesis technology relevant, be applicable to that diosgenin prepares the pregnant steroid diene of 5.16--3 β-alcohol-20-ketone acetic ester (abbreviation diene alcohol ketone acetic ester) and the synthetic enol ketone acetic ester of tigogenin with chemical synthetic drug.
At present, the traditional technology of our factory and domestic other manufacturer production diene alcohol ketone acetic ester, be be raw material with the diosgenin, through operations such as pressurization cracking, oxidation, hydrolysis (eliminations), extractions, refining, mother liquor processing and recyclings, accompanying drawing 1 is seen in its technical process.
Chemical equation is as follows:
For many years, each producer of the whole nation utilizes above-mentioned technology to produce diene alcohol ketone acetic ester from the raw material diosgenin, product yield is about 60～62%, in order to improve yield and quality product, someone proposes from different perspectives and carried out process modification, but so far, product yield does not surpass 60～62%, and quality product still can not be satisfactory, and it is on the low side that this master need show as the first fusing point of product.(seeing medicine industry, the fifth phase, P15,1979).
How improving the yield and the quality product (raising fusing point) of diene alcohol ketone acetic ester, is the problem that domestic units concerned pay close attention to very much, and many units are all in research, but all obtains satisfied result.
Through research and production practice for many years, we find that the cracking of diosgenin and the processing of mother liquor are to improve the yield of diene alcohol ketone acetic ester and the important procedure of quality with reclaiming.In order to improve product yield and quality product, the present invention has reformed both at home and abroad from the synthetic diene alcohol ketone acetic ester technology of diosgenin, pressurization cracking and mother liquor separating technology, the diene alcohol ketone acetic ester yield has been improved about 4.5% than advanced international level 62%, yield has been reached about 66.5%, and fusing point improves 1 ℃.
In order to illustrate the main points of process modification, cracking and mother liquid recovery process comparative illustration are as follows before and after will improving below:
One, improve preceding cracking technology:
1. type of heating and intensification situation: when diosgenin is pressurizeed cracking, employing be the oil bath heating, ceaselessly be heated to 203 ± 3 ℃ of the best (thinking now) cracking temperatures continuously;
2. begun to reach 203 ± 3 ℃ of cracking temperatures to temperature by heat temperature raising, required time was wanted 2.5～3 hours.
Use above-mentioned heating means, the situation that temperature is risen is seen the relation curve 1 that accompanying drawing 2-heat-up time and temperature rise.
The state that this type of heating, temperature do not rise with stopping, and the time that reaches required 2.5～3 hours length of cracking temperature are very disadvantageous for scission reaction, and reason is:
(1) diosgenin, below 160 ℃, in Glacial acetic acid and aceticanhydride, rare scission reaction, just a dissolution process; More than 160 ℃, diosgenin begins cracking, along with temperature raises, cracking aggravation, but diosgenin dissolves in Glacial acetic acid a process will be arranged, if diosgenin is below 160 ℃, dissolving is incomplete as yet, temperature has just surpassed 160 ℃, has promptly entered the temperature cracking zone, undissolved diosgenin, can not react, this is very disadvantageous to yield, and former technology temperature-rise period ceaselessly continuously is very easy to produce this situation.
(2) heating-up time longly promptly rises to best cracking temperature by starting temperature, needs 2.5～3 hours, cause cracking easily diosgenin, further destroyed, produce yield and quality that side reaction influences product.
Made following process modification at the problems referred to above:
1, on type of heating, employing can be heated the type of heating that is rapidly heated in the retort bottom, as adopts efficient power frequency well heater.(seeing China Patent No. 86203184)
2, diosgenin is fine to be dissolved in Glacial acetic acid and the aceticanhydride in order to make, when temperature is raised to 140～160 ℃ (promptly enter cracking zone before), keep for some time, as guarantee in 20～45 minutes, after treating that diosgenin all dissolves, be rapidly heated again, as in 20～45 minutes, temperature is raised to 205 ± 5 ℃ of best cracking temperatures, kept 25～50 minutes.Temperature rising situation is seen the relation curve 2 that accompanying drawing 2-heat-up time and temperature rise.
When changing reaction conditions, composition of raw materials is adjusted.Better prescription is as follows:
Material name specification proportioning remarks
Diosgenin m.p 〉=195 ℃ 1 water content 0.5%
Acetic acid 95% 1.5～1.6
Glacial acetic acid 98% 0.5～0.6
Batch production 0.3～0.4 on the diene mother liquor
And make
(liquid: liter, solid: kilogram)
Two, improving preceding mother liquor handles and recovery technology:
Reclaim ethanol mother liquor afterwards, directly backspace cracking operation is used, because mother liquor is too many, and the material imbalance, so can not all utilize, about 1/3～1/2 mother liquor will give up, and this has not only caused waste, and pollutes the environment, by product isocaproic acid acetic ester in the mother liquor is more simultaneously, it is not separated, directly return the cracking operation and use, influence quality product.Fig. 2 is seen in technical process.
Made following process modification at the problems referred to above:
Handle mother liquor with alkali metal hydroxide, potassium hydroxide (KOH) preferably makes the by product isocaproic acid acetic ester saponification in the mother liquor:
The isocaproic acid acetic ester
M is a basic metal, is preferably potassium (K).
Reclaim after the ethanol, mixed extractant solvent with methyl alcohol and hexanaphthene, difference according to different substances solubility property in different solvents, isocaproic acid acetic ester basic metal saponification thing mostly is dissolved in the potassium alcohol, and diene alcohol ketone acetic ester and unreacted saponin mostly are dissolved in the hexanaphthene, again through sedimentation, and layering, concentrate, the diene alcohol ketone acetic ester in the mother liquor and unreacted diosgenin all can be recycled pressurization cracking operation in next batch.Fig. 3 is seen in technical process:
Handle the raw material and the proportioning (liquid: liter of mother liquor; Solid: kilogram):
Material name specification proportioning charging capacity remarks
1 batch of scission reaction of diene alcohol ketone vinegar is used
Acid esters mother liquor diosgenin weight is 1
Basic metal hydrogen-oxygen 95% 0.02
Change thing
Hexanaphthene industrial goods 3
Methyl alcohol 96% 0.16
Our factory is handled and is reclaimed after two step process improve the cracking of diene alcohol ketone acetic ester and mother liquor, and product yield is by the 62%(advanced international level) about bring up to 66.5%, produced tangible economic benefit.
See attached list:
Diene alcohol ketone acetic ester economic target contrast table.
Annotate: the popular technology of domestic current is called for short old technology, and the present invention is called for short novel process.The reform of novel process cleavage method can improve yield 1.5～2%, and the reform of mother liquor yield can improve yield 3.0～3.5%, and this table improves 4.5% by total recovery.
As can be seen from the above table, after " cracking " and " mother liquor handle with recovery " two step process of preparation diene alcohol ketone acetic ester were carried out, the output value increased to 786.695/ yuan/year by 733.46 ten thousand yuan/year, profit is increased to 155.0 ten thousand yuan/year by 104.78 ten thousand yuan/year, and economic benefit is very considerable.
Embodiment:
One, scission reaction
(1) raw material specification, proportioning (liquid: liter; Solid: kg)
Material name specification proportioning charging capacity remarks
145 ℃ 1 100 of saponin m.p
Moisture content 0.5%
Aceticanhydride industry content 98% 1.55 155
Glacial acetic acid industry content 98% 0.5 50
The present invention of diene mother liquor separating obtained 0.38 38
(2) technological operation:
With saponin, diene mother liquor input crack tank, sealed tank cap with efficient power frequency heater heats; Add aceticanhydride, Glacial acetic acid, the sealing charging valve; Open the power frequency well heater, simultaneously to vacuumizing in the jar, extremely jar interior vacuum tightness is more than the 600mmHg, to close vacuum; In temperature rose to 150 ℃ ± 5 ℃ in 30 minutes, closes the power frequency well heater and under this temperature, kept 20～45 minutes, and then heating makes a jar interior temperature rise to 205 ± 5 ℃ rapidly, interior pressure 5.0kg-6kg/cm
2Stop heating, insulation is 30 minutes in this temperature range, and self pressure in relying on then jar is pressed into and has 200 liter Glacial acetic acid, and is cooled to below 20 ℃ in the oxidation tank, treats oxidation.
Two, oxidation
(1) specifications of raw materials, proportioning (liquid: liter; Solid: kilogram)
Material name specification proportioning charging capacity remarks
Glacial acetic acid industrial goods content 98% 2 200
Chromic anhydride industrial goods content 98% 0.42 42 is made into oxidation liquid
Sodium-acetate industrial goods 0.3 30 are made into oxidation liquid
Water tap water 0.8 80 is made into oxidation liquid
(2) technological operation:
Chromic anhydride, sodium-acetate, water are added the oxygenant preparing tank, stir, be cooled to behind the CL 5 ℃ standby.
Lysate is stirred, be cooled to 8 ℃, add the interior temperature of oxidation hydraulic control system, kept 20 minutes at 92 ± 6 ℃.
Three, hydrolysis
Oxidation liquid was heated to the first atmospheric pressure reflux of boiling after 30 minutes, reclaim under reduced pressure acetic acid 200 liters.
Four, extract
In extractor, add hexanaphthene 1000 liters, stir, hydrolyzed solution is pressed into extractor, stirred 15 minutes; Add 60 ℃ of hot water 500 liters, left standstill 50 minutes, divide the sub-cloud acid solution, with 60 ℃ of hot water agitator treatings of 400 liters, left standstill 30 minutes, branch vibration layer with 60 ℃ of washings of 400 liters once, left standstill branch vibration layer 30 minutes again.
Five, refining
Cyclohexane extract liquid is evaporated near doing, adding 10 liter ethanol reconcentration does near, so triplicate adds 82 liter ethanol (content is more than 94%), atmospheric pressure reflux 1.5 hours after near the doing, be cooled to 6 ± 2 ℃, it is centrifugal to put into whizzer, gets rid of near doing and washs several times with 5 ℃ of ethanol of 60 liters, and getting fusing point after the drying is 166 ℃ of diene alcohol ketone acetic ester elaboration, oven dry, control moisture content 0.5%.
Six, the processing of mother liquor and recovery
With a collection of whole suction mother liquor of centrifugal gained ethanol mother liquor treatment tank when refining, stir and add 2kg potassium hydroxide down, chuck is with 1.5kg/cm
2Steam-heated cal(l)andria, normal pressure reclaimed ethanol 30 minutes, was evaporated near doing, and was cooled to 50 ℃, respectively 300 liter hexanaphthenes, 15 liter methyl alcohol was added the mother liquor treatment tank, with 0.5kg/cm
2Be steam heated to backflow, atmospheric pressure reflux 30 minutes is cooled to 30 ℃, leaves standstill 3 hours, divides the sub-cloud methanol mother liquor, and upper strata cyclohexane extract liquid concentrating under reduced pressure reclaims hexanaphthene near dried, adds 5 liter methyl alcohol reconcentration and does near, is discharged in the dish standby after the cooling while hot.
166 ℃ of the first fusing points of gained diene alcohol ketone acetic ester, moisture content 0.5%, color and luster yellowish white, yield 66.5%(are benchmark with the diosgenin).
Claims (2)
1, a kind of improvement technology by the synthetic diene alcohol ketone acetic ester of diosgenin, this technology also are suitable for the synthetic diene alcohol ketone acetic ester of tigogenin, it is characterized in that:
(1) on type of heating, a reacting by heating pot bottom is not around the reacting by heating jar (wall);
(2) (in the reaction) heats up in diosgenin heating pyrolyze operation, and the Control essentials of insulation is:
A, the solvent temperature of diosgenin in acetic anhydride and Glacial acetic acid are controlled at 140～160 ℃, and keep under this temperature 20～45 minutes.
B, diosgenin are rapidly heated after all dissolving, and in 20～45 minutes temperature are risen to 205 ± 5 ℃;
C, at 205 ± 5 ℃, interior pressure is 5～6kg/cm
2(with the temperature is standard, is reference with pressure) keeps reaction 25～50 minutes;
The raw material of d, cracking operation and prescription: (liquid: liter; Solid: kilogram; )
The material name proportioning
Diosgenin 1
Acetic anhydride 1.5～1.6
Glacial acetic acid 0.5～0.6
Diene mother liquor 0.3～0.4.
2, in mother liquor processing and recovery process, use alkali metal hydroxide, preferably KOH handles mother liquor, uses the mixed extractant solvent mother liquor of methyl alcohol and hexanaphthene then, and proportioning is (liquid liter, solid: kilogram)
The material name proportioning
Mother liquor 1(refers to the diosgenin that feeds intake)
Alkali metal hydroxide 0.01～0.04
(being preferably potassium hydroxide)
Methyl alcohol 0.10～0.5
Hexanaphthene 2.0～4
Alkali metal hydroxide 0.01～0.04
(being preferably potassium hydroxide)
Methyl alcohol 0.10～0.5
Hexanaphthene 2.0～4
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 87105226 CN1026181C (en) | 1987-07-26 | 1987-07-26 | Cracking of disgenin and new art of mother liquor recovery therefrom |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 87105226 CN1026181C (en) | 1987-07-26 | 1987-07-26 | Cracking of disgenin and new art of mother liquor recovery therefrom |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN87105226A true CN87105226A (en) | 1988-08-24 |
| CN1026181C CN1026181C (en) | 1994-10-12 |
Family
ID=4815245
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 87105226 Expired - Fee Related CN1026181C (en) | 1987-07-26 | 1987-07-26 | Cracking of disgenin and new art of mother liquor recovery therefrom |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1026181C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101942004A (en) * | 2010-05-22 | 2011-01-12 | 竹溪县华驰医药化工有限责任公司 | New process method for improving quality of diene by secondary saponification |
| CN103113448A (en) * | 2013-02-04 | 2013-05-22 | 湖北民生生物医药有限公司 | Production method for synthesizing pregnenolone acetate from ticogenin |
| CN112279767A (en) * | 2020-10-29 | 2021-01-29 | 陕西嘉禾生物科技股份有限公司 | Preparation method of diacerein |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5808117A (en) * | 1996-01-22 | 1998-09-15 | Chowdhury; Pritish Kumar | Process for the production of 16-Dehydropregenolone acetate form diosgenin |
| CN1077894C (en) * | 1999-09-03 | 2002-01-16 | 中国科学院昆明植物研究所 | Process for preparing dieneketonol acetate |
-
1987
- 1987-07-26 CN CN 87105226 patent/CN1026181C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101942004A (en) * | 2010-05-22 | 2011-01-12 | 竹溪县华驰医药化工有限责任公司 | New process method for improving quality of diene by secondary saponification |
| CN103113448A (en) * | 2013-02-04 | 2013-05-22 | 湖北民生生物医药有限公司 | Production method for synthesizing pregnenolone acetate from ticogenin |
| CN103113448B (en) * | 2013-02-04 | 2016-05-11 | 湖北民生生物医药有限公司 | A kind of production method by the synthetic pregnenolone acetate of tigogenin |
| CN112279767A (en) * | 2020-10-29 | 2021-01-29 | 陕西嘉禾生物科技股份有限公司 | Preparation method of diacerein |
| CN112279767B (en) * | 2020-10-29 | 2023-02-03 | 陕西嘉禾生物科技股份有限公司 | Preparation method of diacerein |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1026181C (en) | 1994-10-12 |
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