CN102060901A - Process for synthesizing progesterone by using dehydropregnenolone acetate - Google Patents
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- RJKFOVLPORLFTN-LEKSSAKUSA-N Progesterone Chemical compound C1CC2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H](C(=O)C)[C@@]1(C)CC2 RJKFOVLPORLFTN-LEKSSAKUSA-N 0.000 title claims abstract description 68
- 229960003387 progesterone Drugs 0.000 title claims abstract description 30
- 239000000186 progesterone Substances 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title abstract description 19
- 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
- 230000002194 synthesizing effect Effects 0.000 title abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 64
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 15
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 14
- 239000012043 crude product Substances 0.000 claims abstract description 9
- 238000010992 reflux Methods 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- 230000007062 hydrolysis Effects 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 42
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- 150000001993 dienes Chemical class 0.000 claims description 14
- 235000019439 ethyl acetate Nutrition 0.000 claims description 14
- 150000002576 ketones Chemical class 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 7
- 238000007670 refining Methods 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000012141 concentrate Substances 0.000 claims description 6
- 230000018044 dehydration Effects 0.000 claims description 6
- 238000006297 dehydration reaction Methods 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 239000012047 saturated solution Substances 0.000 claims description 5
- 238000003457 Shi epoxidation reaction Methods 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 238000003672 processing method Methods 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 229960000583 acetic acid Drugs 0.000 claims description 3
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 3
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 238000006073 displacement reaction Methods 0.000 claims description 3
- 239000012362 glacial acetic acid Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 238000004062 sedimentation Methods 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000001117 sulphuric acid Substances 0.000 claims description 3
- 235000011149 sulphuric acid Nutrition 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 13
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 239000012535 impurity Substances 0.000 abstract description 4
- 230000035484 reaction time Effects 0.000 abstract description 4
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 3
- 238000001914 filtration Methods 0.000 abstract description 2
- 239000000706 filtrate Substances 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 6
- 150000004678 hydrides Chemical class 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 3
- 238000002203 pretreatment Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 235000015320 potassium carbonate Nutrition 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- -1 methyl alcohol hydride Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012453 solvate Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Abstract
The invention discloses a process for synthesizing progesterone by using dehydropregnenolone acetate. The method comprises the following steps of: 1, performing low-temperature hydrogenation in a hydrogenation reaction process, wherein the temperature in the hydrogenation reaction process is controlled at a temperature of 10 to 15 DEG C, and the hydrogenation reaction time is 2 to 3 hours; 2, hydrolyzing the hydrogenation solution at a low temperature by directly adopting sodium hydroxide, wherein the hydrolysis temperature is controlled at 15 to 20 DEG C, and the hydrolysis reaction time is 1.5 to 2 hours; and 3, after Wolfowitz oxide is distilled completely, performing centrifugal throw drying to obtain a crude progesterone product, dissolving the crude product into warm ethanol, adding active alumina and active argil, heating and refluxing, filtering, cooling the filtrate, and then performing throw drying and drying to obtain a fine progesterone product, wherein the content of the product reaches over 99.3 percent. after the process is improved, the yield of the progesterone is improved by 4 percent compared with the domestic advanced level (65 percent), the yield reaches 69 percent, the content of the main impurities is less than 0.3 percent, and the production cost is greatly reduced.
Description
The ㈠ technical field: the present invention relates to the synthetic method of chemicals, specifically is the processing method by the synthetic Progesterone of diene alcohol ketone acetic ester.
The ㈡ prior art: at present, producing the traditional technology of Progesterone, is to be raw material with the diene alcohol ketone acetic ester, through hydrogenation, concentrate, hydrolysis, condensing crystal, filtration, washing, drying, promptly get Vitarrine; Carry out the Wo Shi oxidation again, dash and heat up in a steamer, dry, soak with sherwood oil again and carry out pre-treatment, dry once more, get the Progesterone crude product, at first carry out making with extra care the first time and use dissolve with ethanol, use activated carbon decolorizing, filter, concentrate, cooling, filter is got rid of in crystallization, carries out the second time then and makes with extra care, with ethanol filter cake is carried out heating for dissolving, filter, concentrate, cooling, filter is got rid of in crystallization, gets the Progesterone elaboration, carry out analyzing and testing,, then can directly put in storage if qualified; If defective, then need carry out making with extra care for the third time, be heated dissolving with ethanol once more, crystallisation by cooling can get the Progesterone elaboration.When diene alcohol ketone acetic ester is carried out hydrogenation, adopt ethanol as solvent in the above-mentioned technology, utilize active nickel as catalyzer, reaction is 3.5 hours under 34-36 ℃ of temperature condition; The manufacturer that had afterwards brings up to 50 ± 3 ℃ with temperature, reacts 5 hours; When hydrolyzing process, the ethanol in the hydride is concentrated near doing, add methyl alcohol hydride is dissolved, add solution of potassium carbonate, be hydrolyzed at reflux state, temperature is approximately 60-65 ℃, promptly adopts the pyritous mode to be hydrolyzed; This hydrogenation hydrolysis reaction condition can produce many unfavorable results, and promptly hydrogenation temperature height, long reaction time easily produce side reaction, and also hydrogenation is saturated with two keys of No. 5 positions in the diene alcohol ketone acetic ester, thereby forms impurity, influences product quality; In hydrolyzing process, need to change solvent, ethanol distillation used in the hydrogenation is concentrated dried, add methyl alcohol then as solvent, the schedule of operation complexity, solvent-oil ratio is big, and uses the higher alkali (salt of wormwood) of price to be hydrolyzed, and the intermediate Vitarrine yield of production is low, the cost height, thus cause the yield of Progesterone low-cost high.Need carry out pre-treatment to the Progesterone crude product earlier in the treating process, pass through secondary then or make with extra care for three times to obtain qualified Progesterone product, and program is loaded down with trivial details, and product yield is low, and solvent consumption is big.
For many years, each manufacturer utilizes above-mentioned technology to produce Progesterone from the raw material diene alcohol ketone acetic ester, product yield is always at 60-65%, for yield and the quality product that improves Progesterone, someone proposes from different perspectives and carried out process modification, but product yield does not surpass 65% so far, and quality product still can not be satisfactory, and it is higher that this mainly shows as main impurity.
How improving the yield and the quality product of Progesterone, 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.
The ㈢ summary of the invention: purpose of the present invention just provides a kind of through improved processing method by the synthetic Progesterone of diene alcohol ketone acetic ester; Present method makes Progesterone yield ratio by associated process conditions in hydrogenation hydrolysis reaction, oxidizing reaction, the several committed steps of refining step is improved
Advanced international level 65% has improved 4 percentage points, makes yield reach 69%, and main impurity is below 0.3%, and production cost descends significantly.
The processing step of the inventive method is as follows:
A, hydrogenation hydrolysis
The ethanolic soln that in the hydrogenation jar, adds ethanol total amount 2/9 earlier, under nitrogen protection, drop into active nickel, again diene alcohol ketone acetic ester is mixed with the ethanol of surplus in the back suction hydrogenation jar, temperature in the jar is risen to 60 ± 5 ℃, dissolving is more than 30 minutes, with hydrogen that air displacement in the jar is clean, cooling again, controlled temperature led to H-H reaction 2-3 hour between 10-15 ℃, sedimentation, with supernatant liquor suction hydrolysis reaction jar, temperature is controlled between 15-20 ℃ the saturated solution of dropping sodium, dropwise, insulation pulled back to PH=7.0 at 1.5-2 hour with Glacial acetic acid, carried out concentrating under reduced pressure, reclaim ethanol, until ethanol being concentrated near doing, discharging is cooled to centrifuge dripping below 5 ℃, with Warm Wash to there not being obvious Pao Droplets, centrifuge dripping is sent into oven for drying again, promptly gets Vitarrine; Weight part ratio between the above-mentioned raw materials is a diene alcohol ketone acetic ester: ethanol: active nickel: sodium hydroxide saturated solution=1:30:2:0.2;
B, Wo Shi oxidation
Put into toluene earlier in Wo Shi oxidizing reaction jar, thermal dehydration is cooled to 95-105 ℃, add pimelinketone and Vitarrine again, dehydration once more is cooled to below 90 ℃ after the stirring and dissolving, drop into aluminum isopropylate,, be cooled to 80 ℃ in 110-115 ℃ of reaction 2 hours, add 2.5% cold dilute sulphuric acid, standing demix, branch vibration layer, toluene layer washes with water to neutrality, carries out steam then towards heating up in a steamer, and toluene is steamed, the residuum centrifuge dripping promptly gets the Progesterone crude product;
C, refining
In ethanol suction bleacher, drop into the Progesterone crude product again, the reflux dissolving, drop into activated alumina and atlapulgite again, reflux 60 minutes, filtered while hot concentrates in crystallizer, be cooled to below 5 ℃, centrifuge dripping 70-75 ℃ of oven dry, promptly gets content and reaches Progesterone elaboration more than 99.3%.
The present invention compared with prior art has following characteristics by the critical process condition in hydrogenation hydrolysis in the existing technology, oxidation, the step such as refining is improved:
1. the hydrogenation temperature is reduced to 10-15 ℃, adopts cryogenic method to carry out hydrogenation.Low temperature hydrogenation can strengthen the selectivity of hydrogenation, makes two keys of No. 16 positions in the saturated diene alcohol ketone acetic ester of its hydrogenation, and the generation that reduces side reaction falls in two keys of No. 5 positions of not hydrogenation, improves the content of product; According to the PV=nRT formula, reduce temperature T, increase n, promptly can improve the concentration of hydrogen in the retort, help improving speed of response, according to our production experience, react and can finish in 2-2.5 hour.Reaction times of high temperature hydrogen metallization processes than other shortens dramatically, and has improved production efficiency;
2. in hydrolysis reaction, directly dripping saturated aqueous sodium hydroxide solution under 15-20 ℃ of condition in hydride is hydrolyzed, not needing that the ethanol in the hydride is concentrated distillation cements out, need not to add methanol solvate,, directly in hydride, be hydrolyzed owing to need not the replacement solvent kind, thereby simplified schedule of operation, shorten the production time, improved production efficiency, reduced solvent consumption.Adopt cheap sodium hydroxide (2300 yuan/ton) to substitute the higher salt of wormwood (10400 yuan/ton) of price, adopt the method for low temperature hydrolysis, reduced energy consumption, reduced the loss through volatilization of solvent; Production cost is significantly lowered; 3. it is refining in the process for refining an original pre-treatment to be added secondary or three times, is reduced to once refiningly, is reduced to the consumption of solvent greatly, has simplified production process, has improved product yield, has also reduced production cost.
(4) embodiment:
Embodiment 1
A, hydrogenation hydrolysis
In the hydrogenation jar, add earlier 200L ethanol, under nitrogen protection, drop into active nickel 60kg, again with the mixed solution suction hydrogenation jar of diene alcohol ketone acetic ester 30kg and ethanol 700L, temperature in the jar is risen to 60 ± 5 ℃, dissolving is more than 30 minutes, and is with hydrogen that air displacement in the jar is clean, again cooling, controlled temperature led to H-H reaction 2-2.5 hour between 10-15 ℃, sedimentation, supernatant liquor suction hydrolysis reaction jar is controlled at temperature between 15-20 ℃, the saturated solution 6kg of dropping sodium, dropwise, be incubated 1.5-2 hour, pull back to PH=7.0 with Glacial acetic acid, carry out concentrating under reduced pressure, reclaim ethanol, near dried until ethanol is concentrated, discharging, be cooled to below 5 ℃, centrifuge dripping, with Warm Wash to not having obvious Pao Droplets, centrifuge dripping again, send into oven for drying, promptly get the about 25.5kg of Vitarrine;
B, Wo Shi oxidation
In Wo Shi oxidizing reaction jar, put into toluene 14L earlier, thermal dehydration, be cooled to 95-105 ℃, add pimelinketone 125L and Vitarrine 50kg (two crowdes merge oxidation) again, dehydration once more is cooled to below 90 ℃ after the stirring and dissolving, drops into aluminum isopropylate 10kg, in 110-115 ℃ of reaction 2 hours, be cooled to 80 ℃, add 2.5% cold dilute sulphuric acid 3.75L, standing demix, branch vibration layer, toluene layer washes with water to neutrality, carries out steam then towards heating up in a steamer, and toluene is steamed, the residuum centrifuge dripping promptly gets Progesterone crude product 98kg;
C, refining
In ethanol 300L suction bleacher, drop into Progesterone crude product 98kg again, the reflux dissolving, drop into each 5kg of activated alumina and atlapulgite again, reflux 60 minutes, filtered while hot concentrates in crystallizer, be cooled to below 5 ℃, centrifuge dripping 70-75 ℃ of oven dry, promptly gets content and reaches the about 83kg of Progesterone elaboration more than 99.3%.
Table 1 is to produce Progesterone major economic indicators control case before and after the process modification
Table 2 is raw material specification used among the present invention
In the technology of the present invention in improved several correlation step related raw material and consumption do the adaptation, all the other each step and processing condition, the raw material of use and proportioning are all identical with existing technology.
Claims (1)
1. by the processing method of the synthetic Progesterone of diene alcohol ketone acetic ester, it is characterized in that comprising following processing step:
A, hydrogenation hydrolysis
The ethanolic soln that in the hydrogenation jar, adds ethanol total amount 2/9 earlier, under nitrogen protection, drop into active nickel, again diene alcohol ketone acetic ester is mixed with the ethanol of surplus in the back suction hydrogenation jar, temperature in the jar is risen to 60 ± 5 ℃, dissolving is more than 30 minutes, with hydrogen that air displacement in the jar is clean, cooling again, controlled temperature led to H-H reaction 2-3 hour between 10-15 ℃, sedimentation, with supernatant liquor suction hydrolysis reaction jar, temperature is controlled between 15-20 ℃ the saturated solution of dropping sodium, dropwise, insulation pulled back to PH=7.0 at 1.5-2 hour with Glacial acetic acid, carried out concentrating under reduced pressure, reclaim ethanol, until ethanol being concentrated near doing, discharging is cooled to centrifuge dripping below 5 ℃, with Warm Wash to there not being obvious Pao Droplets, centrifuge dripping is sent into oven for drying again, promptly gets Vitarrine; Weight part ratio between the above-mentioned raw materials is a diene alcohol ketone acetic ester: ethanol: active nickel: sodium hydroxide saturated solution=1:30:2:0.2;
B, Wo Shi oxidation
Put into toluene earlier in Wo Shi oxidizing reaction jar, thermal dehydration is cooled to 95-105 ℃, add pimelinketone and Vitarrine again, dehydration once more is cooled to below 90 ℃ after the stirring and dissolving, drop into aluminum isopropylate,, be cooled to 80 ℃ in 110-115 ℃ of reaction 2 hours, add 2.5% cold dilute sulphuric acid, standing demix, branch vibration layer, toluene layer washes with water to neutrality, carries out steam then towards heating up in a steamer, and toluene is steamed, the residuum centrifuge dripping promptly gets the Progesterone crude product;
C, refining
In ethanol suction bleacher, drop into the Progesterone crude product again, the reflux dissolving, drop into activated alumina and atlapulgite again, reflux 60 minutes, filtered while hot concentrates in crystallizer, be cooled to below 5 ℃, centrifuge dripping 70-75 ℃ of oven dry, promptly gets content and reaches Progesterone elaboration more than 99.3%.
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| CN201110007898A CN102060901B (en) | 2011-01-14 | 2011-01-14 | Process for synthesizing progesterone by using dehydropregnenolone acetate |
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| CN201110007898A CN102060901B (en) | 2011-01-14 | 2011-01-14 | Process for synthesizing progesterone by using dehydropregnenolone acetate |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102911232A (en) * | 2012-11-02 | 2013-02-06 | 湖北丹江口丹澳医药化工有限公司 | Progesterone preparation method |
| CN103087136A (en) * | 2012-11-06 | 2013-05-08 | 湖南科源生物制品有限公司 | Novel process for preparing progesterone |
| CN103113453A (en) * | 2013-02-04 | 2013-05-22 | 湖北民生生物医药有限公司 | Technique for producing 16,17-epoxyprogesterone by vacuum concentration instead of flush distillation |
| CN103524588A (en) * | 2013-11-04 | 2014-01-22 | 浙江神洲药业有限公司 | Method for preparing progesterone |
| CN103641880A (en) * | 2013-11-18 | 2014-03-19 | 陕西汉江药业集团股份有限公司 | Method for recovering progesterone from progesterone production mother liquor |
| CN104130305A (en) * | 2014-07-15 | 2014-11-05 | 湖北葛店人福药业有限责任公司 | Method for synthesizing progesterone intermediate, namely, pregnenolone acetate |
| CN105732757A (en) * | 2016-03-02 | 2016-07-06 | 湖南科瑞生物制药股份有限公司 | Progesterone preparation method |
| CN106589036A (en) * | 2016-12-11 | 2017-04-26 | 湖北竹溪人福药业有限责任公司 | Method for separating progesterone and isomer of progesterone |
| CN113956318A (en) * | 2021-09-10 | 2022-01-21 | 丽江映华生物药业有限公司 | Progesterone refining method |
| CN113999275A (en) * | 2021-11-30 | 2022-02-01 | 陕西众和振华生物科技有限公司 | Carbon neutralization process for comprehensive recovery treatment of progesterone mother liquor |
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| CN102911232B (en) * | 2012-11-02 | 2015-03-11 | 湖北丹澳药业有限公司 | Progesterone preparation method |
| CN102911232A (en) * | 2012-11-02 | 2013-02-06 | 湖北丹江口丹澳医药化工有限公司 | Progesterone preparation method |
| CN103087136A (en) * | 2012-11-06 | 2013-05-08 | 湖南科源生物制品有限公司 | Novel process for preparing progesterone |
| CN103113453B (en) * | 2013-02-04 | 2016-03-16 | 湖北民生生物医药有限公司 | A kind of concentrating under reduced pressure substitutes punching and heats up in a steamer the processing method of producing 16ALPHA,17ALPHA-epoxyprogesterone |
| CN103113453A (en) * | 2013-02-04 | 2013-05-22 | 湖北民生生物医药有限公司 | Technique for producing 16,17-epoxyprogesterone by vacuum concentration instead of flush distillation |
| CN103524588A (en) * | 2013-11-04 | 2014-01-22 | 浙江神洲药业有限公司 | Method for preparing progesterone |
| CN103524588B (en) * | 2013-11-04 | 2015-09-23 | 浙江神洲药业有限公司 | A kind of method preparing Progesterone |
| CN103641880A (en) * | 2013-11-18 | 2014-03-19 | 陕西汉江药业集团股份有限公司 | Method for recovering progesterone from progesterone production mother liquor |
| CN103641880B (en) * | 2013-11-18 | 2015-09-09 | 陕西汉江药业集团股份有限公司 | A kind of method reclaiming Progesterone from progesterone production mother liquor |
| CN104130305A (en) * | 2014-07-15 | 2014-11-05 | 湖北葛店人福药业有限责任公司 | Method for synthesizing progesterone intermediate, namely, pregnenolone acetate |
| CN105732757A (en) * | 2016-03-02 | 2016-07-06 | 湖南科瑞生物制药股份有限公司 | Progesterone preparation method |
| CN106589036A (en) * | 2016-12-11 | 2017-04-26 | 湖北竹溪人福药业有限责任公司 | Method for separating progesterone and isomer of progesterone |
| CN106589036B (en) * | 2016-12-11 | 2018-07-24 | 湖北竹溪人福药业有限责任公司 | A kind of separation method of progesterone and its isomers |
| CN113956318A (en) * | 2021-09-10 | 2022-01-21 | 丽江映华生物药业有限公司 | Progesterone refining method |
| CN113999275A (en) * | 2021-11-30 | 2022-02-01 | 陕西众和振华生物科技有限公司 | Carbon neutralization process for comprehensive recovery treatment of progesterone mother liquor |
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