CN1814615A - 7-keto deoxy epiandrosterone and its acetate synthesizing method - Google Patents
7-keto deoxy epiandrosterone and its acetate synthesizing method Download PDFInfo
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Abstract
The invention relates to 7-keto-dehydroepiandrosterone and its acetate synthetic method. It belongs to organic synthesis technique field. It uses dehydroepiandrosterone and its acetate as raw material, and uses CrO<SUB>3</SUB>/NHPI carrier CH<SUB>2</SUB>Cl<SUB>2</SUB> carrier reagent system to do selectivity allyl place oxidizing reaction to compose at 18-40 centigrade degree. The carrier reagent preparation method includes the following steps: using water as medium; forming CrO<SUB>3</SUB> and NHPI homogeneous phase solution; adsorbing to carrier; vaporizing to remove moisture content. The mol ratio of NHPI and Cr03 is 1:3.3-5.5. The weight ratio of CrO<SUB>3</SUB> and carrier is 1:4-6. The carrier is activated clay, silica gel or diatomaceous earth. In reaction system, the mol ratio of substrate and CrO<SUB>3</SUB> and NHPI is 1:2-5.5:1-2.7. The reaction medium is dichloromethane. The carrier reagent can be reclaimed after reacting. The invention has the advantages that the reaction condition is moderate; the dosage of the CrO<SUB>3</SUB> is less; the operation is simple; the product is easy to separate and purify; the yield is good; the carrier reagent is easy to reclaim or treat to reduce environmental pollution.
Description
Technical field
The invention belongs to technical field of organic synthesis.
Background technology
7-ketone group dehydroepiandros-sterone (7-keto-dehydroepiandrosterone, write a Chinese character in simplified form 7-Keto DHEA,) and 7-ketone group trans-Dehydrorosterone acetate (7-keto-dehydroepiandrosterone acetate, write a Chinese character in simplified form 7-Keto DHEAAc,) all are the dehydroepiandros-sterone (dehydroepiandrosterone that exist in the human body, write a Chinese character in simplified form DHEA,) meta-bolites, their structural formula and trans-Dehydrorosterone acetate (dehydroepiandrosterone acetate, write a Chinese character in simplified form DHEAAc) structural formula as follows:
1，R＝H，DHEA 3，R＝H，7-KetoDHEA
2，
DHEAAc 4，
，7-Keto?DHEAAc
Dehydroepiandros-sterone (DHEA), be by human acth excretory product, it is hormone the abundantest in the blood of human body, also be that other many wholesome hormones of human body (comprise sexual hormoue, as testosterone and oestrogenic hormon etc.) precursor, therefore be called as " mother's hormone " (" The Mother Hormone ").It plays an important role in human body: comprise and construct immunity system, regulate hormonal equilibrium, keep normal physiological function, particularly anti-ageing, nervus centralis is spiritual, unique effect is arranged aspect the adjusting of immune, metabolism, bone, cardiovascular systems and blood fat etc.But its content descends with the increase at age in human body.Therefore, it is useful that the elderly suitably replenishes DHEA, and in many countries, DHEA uses as the anti-ageing composition of food or medicine.
Though DHEA generally is safe,, may bring certain hidden danger to health if take for a long time also because it can be the male sex and women's sexual hormoue the human body metabolism.
Over surplus in the of nearly ten year, through studies show that in a large number, 7-Keto DHEA, or 7-Keto DHEAAc has the physiologically active stronger than DHEA, particularly at anti-ageing, strengthening immunity, improve hypermnesia brain function, prevention senile dementia and diabetes, there is stronger effect the aspects such as vigor that reduce heart trouble danger, fat-reducing, bone density improving and muscle, and not metabolism is sexual hormoue (comprising the male sex and women's sexual hormoue) in human body, have no side effect more effective and safety than DHEA.7-Keto DHEAAc has been a food supplement by drugs approved by FDA.
7-Keto DHEAAc easily is transformed into 7-Keto DHEA in human body, so both activity are the same, and just, 7-Keto DHEA not only is used for food supplement, also is used for the activeconstituents of cosmetics, treatment tetter etc.
About synthesizing of 7-Keto DHEA and 7-Keto DHEAAc, available following formula is summarized:
Generally speaking, need earlier DHEA to be carried out acetylize, with protection 3-position hydroxyl, if directly use CrO
3Or chromium reagent such as PPC carries out oxidation, will obtain corresponding 4-alkene-3-ketone and 4-alkene-3, the 6-derovatives.Therefore, the most frequently used is to carry out allylic oxidation by DHEAAc to get 7-Keto DHEAAc (in case of necessity, solving 7-Keto DHEA through alkaline water again, as shown above).Used oxygenant kind is also more, chromium reagent commonly, for example: CrO
3-Ac
2O-AcOH, sodium dichromate 99, Collins reagent (CrO
32Py), CrO
3-DMP (3,5-dimethylpyrazole), PCC (pyridinium chlorochromate and PDC (pyridinium dichromate) etc.Also can adopt the catalyst system and the t-BuO of tertbutyl peroxide and copper, cobalt, ruthenium, chromic salts etc.
2H-NaOCl, t-BuO
2H-HIO
4Deng the co-oxidation system.But used chromium reagent dosage excessive (general excessive 10-20 doubly reach more than) needs strict control reaction conditions, and environment is had bigger pollution.Use the tertbutyl peroxide oxidation system, relatively good, take place but also often be attended by the epoxidation side reaction.
Recently, bibliographical information (Marwah, P.et al., U.S. Pat, 6384251) is arranged, adopt CrO
3/ NHPI (N-hydroxyphthalimide)/acetone oxidation system can effectively realize the allylic oxidation of 5-en steroids, CrO
3Consumption can significantly reduce (excessive 2-5 doubly), and reaction conditions is also relatively gentleer.But the separation of product and chromic oxide is difficulty relatively, and operation also bothers, and environment is still had certain pollution.
Summary of the invention
The objective of the invention is to overcome the shortcoming of prior art, the synthetic method of a kind of 7-ketone group dehydroepiandros-sterone and acetic ester thereof is provided, not only its reaction conditions gentleness, CrO
3Consumption is less, and easy and simple to handle, and product is easy to separation and purification, and environmental pollution is little.
The object of the present invention is achieved like this: with dehydroepiandros-sterone or its acetic ester is raw material, uses CrO
3/ NHPI/ carrier/CH
2Cl
2The support agent system is carried out the directly synthetic corresponding 7-ketone group dehydroepiandros-sterone of selectivity allylic oxidation reaction or its acetic ester under 18～40 ℃.
Preparation is a medium with water during support agent, makes CrO earlier
3With the homogeneous phase solution of NHPI, be adsorbed in again on the carrier, evaporate the branch that anhydrates, NHPI and CrO then
3Mol ratio be: 1: 3.3-5.5, CrO
3With the weight ratio of carrier be: 1: 4-6.
Said carrier is atlapulgite or 100-200 purpose silica gel or the chemical pure diatomite of diameter less than 75 μ m.
In the reaction system, substrate: CrO
3: the mol ratio of NHPI is 1: 2～5.5: 1～2.7, and reaction medium is a methylene dichloride.Preferred substrate: CrO
3: the mol ratio of NHPI is 1: 2.5～4: 1.2～1.5.
Can be with reacted support agent filtered and recycled.
Beneficial effect of the present invention: reaction conditions gentleness, CrO
3Consumption is less, and is easy and simple to handle, and product is easy to separation and purification, and yield is good, and support agent is easy to reclaim to be used or processing, thereby has reduced environmental pollution.
Below the present invention is described further by embodiment, but scope of the present invention is not subjected to the limitation of illustrated embodiment.
Embodiment
See following examples:
Embodiment 1.Preparation is the reagent of carrier with the atlapulgite: 10.0g (0.1mol) chromium trioxide is dissolved in the deionized water of 10mL, in 40 ℃ of waters bath with thermostatic control, dissolve, the NHPI that adds 5g (0.03mol) again, stirred about 20 minutes, use the deionized water dissolving of 10mL again, adding the 45g diameter is the atlapulgite of 75 μ m, after mixture is fully stirred, vacuum-drying no longer reduces to weighing, levigate with milling, obtain the powder carrier reagent 70g of red black, i.e. the 7g support agent, be equivalent to 1g chromium trioxide (0.01mol), in loft drier, preserve.
Embodiment 2.Preparation is the reagent of carrier with silica gel: 10.0g (0.1mol) chromium trioxide is dissolved in the deionized water of 10mL, in 40 ℃ of waters bath with thermostatic control, dissolve, the NHPI that adds 5g (0.03mol) again, stirred about 20 minutes, use the deionized water dissolving of 10mL again, add 50g 150 purpose silica gel, after mixture is fully stirred, vacuum-drying no longer reduces to weighing, levigate with milling, obtain the powder carrier reagent 97.2g of red black, i.e. the 9.7g support agent, be equivalent to 1g chromium trioxide (0.01mol), in loft drier, preserve.
Embodiment 3.Preparation is that the reagent of carrier: 20.0g (0.2mol) chromium trioxide is dissolved in the deionized water of 20mL with diatomite, dissolves in 40 ℃ of waters bath with thermostatic control, and the NHPI that adds 10g (0.06mol) again stirred about 20 minutes, used the deionized water dissolving of 20mL again.Add 100g chemical pure diatomite, mixture is fully stirred after, 90 ℃ of freeze-day with constant temperature no longer reduce to weighing, levigate with milling, obtain the powder carrier reagent 132g of dark red black, i.e. the 6.6g support agent, be equivalent to 1g chromium trioxide (0.01mol), in loft drier, preserve.
Embodiment 4.Synthetic 7-ketone group trans-Dehydrorosterone acetate (7-Keto DHEAAc): take by weighing DHEAAc1.00g (0.003mol), adding 0.50gNHPI (0.003mol) again is dissolved in the methylene dichloride of 100mL, after stirring 10min, the support agent that adds the 3.5g atlapulgite (is equivalent to 0.50g, 0.005mol chromium trioxide) normal temperature stirs after 4 hours down, the atlapulgite support agent that adds 3.5g is again finished (thin layer detection) (42 hours) until reaction.Mixture is filtered,, reclaim support agent with the washed with dichloromethane filter cake twice of 20mL.Filtrate is used saturated NaHCO
3Twice of solution washing, remove water layer, organic layer adds the 5g atlapulgite, filter, remove methylene dichloride, get the 0.94g crude product with Rotary Evaporators, again through column chromatography for separation (20g silica gel, sherwood oil: ethyl acetate: 3: 1), obtain the pure product of 0.66g 7-keto-DHEAAc. productive rate: 63%, 181-183 ℃ of fusing point (mp).
FAB
+-MS：m/z345(M
+，26)，
1HNMR(CDCl
3，500MHz)：5.72(s，1H，H-6)，4.69(m，1H，H-3)，2.02(s，3H，-O-CO-CH
3)，1.21(s，3H，H-19)，0.86(s，3H，H-18)，
13CNMR(CDCl
3，500MHz)219.3(C-17)，199.8(C-7)，169.3(COOEt)，163.9(C-5)，125.5(C-6)，71.0(C-3)，49.0，46.9，44.8，43.4，37.5，36.9，35.0，34.7，29.7，26.3，23.2，20.3，19.6，16.4(C-19)，12.8(C-18).
Embodiment 5.Synthetic 7-ketone group trans-Dehydrorosterone acetate (7-Keto DHEAAc): take by weighing DHEAAc 1.00g (0.003mol), adding 0.50gNHPI (0.003mol) again is dissolved in the methylene dichloride of 100mL, after stirring 10min, the support agent that adds the 5.3g atlapulgite (is equivalent to 0.75g, 0.0075mol chromium trioxide) normal temperature stirs after 4 hours down, the atlapulgite support agent that adds 5.3g is again finished (thin layer detection) (22 hours) until reaction, mixture is filtered, with twice of the washed with dichloromethane filter cake of 20mL, filter cake reclaims drying and deposits, and filtrate is used saturated NaHCO
3Solution washing twice is removed water layer, and organic layer adds the 5g atlapulgite, filter, remove methylene dichloride, get the 1.12g crude product with Rotary Evaporators, through column chromatography for separation (20g silica gel, sherwood oil: ethyl acetate: 3: 1), obtain the pure product of 0.78g7-keto-DHEAAc again. productive rate: 75%
Embodiment 6.Synthetic 7-ketone group trans-Dehydrorosterone acetate (7-Keto DHEAAc): take by weighing DHEAAc3.3g (0.01mol), adding 1gNHPI (0.006mol) again is dissolved in the methylene dichloride of 150mL, after stirring 10min, the support agent that adds 9.0g silica gel (is equivalent to 1g, 0.01mol chromium trioxide) normal temperature stirs after 4 hours down, the support agent that adds the silica gel of 9.0g again, the support agent that adds 9.0g silica gel after 24 hours is again finished (thin layer detection) (52 hours) until reaction, mixture is filtered, with twice of washed with dichloromethane filter cake and the recovery of 30mL, filtrate is used saturated NaHCO
3Solution washing twice is removed water layer, and organic layer adds the 10g atlapulgite, filter, remove methylene dichloride, get the 3.4g crude product with Rotary Evaporators, through column chromatography for separation (60g silica gel, sherwood oil: ethyl acetate: 3: 1), obtain the pure product of 2.4g7-keto-DHEAAc again. productive rate: 70%
Embodiment 7.Synthetic 7-ketone group trans-Dehydrorosterone acetate (7-Keto DHEAAc): take by weighing DHEAAc1.00g (0.003mol), adding 0.5gNHPI (0.003mol) again is dissolved in the methylene dichloride of 100mL, after stirring 10min, add the diatomaceous support agent of 5.5g and (be equivalent to 0.83g, 0.0083mol chromium trioxide) normal temperature stirs after 4 hours down, the diatomaceous support agent that adds 5.5g is again finished (thin layer detection) (24 hours) until reaction.Mixture is filtered, and with twice of washed with dichloromethane filter cake and the recovery of 20mL, filtrate is used saturated NaHCO
3Solution washing twice is removed water layer, and organic layer adds the 5g atlapulgite, filter, remove methylene dichloride, get the 1.00g crude product with Rotary Evaporators, through column chromatography for separation (20g silica gel, sherwood oil: ethyl acetate: 3: 1), obtain the pure product of 0.71g7-keto-DHEAAc again. productive rate: 67%
Embodiment 8.Synthetic 7-ketone group dehydroepiandros-sterone (keto DHEA): take by weighing DHEA2.8g (0.01mol), adding 0.6gNHPI (0.0036mol) again is dissolved in the methylene dichloride of 150mL, after stirring 10min, the support agent that adds 9.0g silica gel (is equivalent to 1g, 0.01mol chromium trioxide) normal temperature stirs after 4 hours down, the support agent that adds the silica gel of 9.0g again, the support agent that adds 9.0g silica gel after 24 hours is again finished (thin layer detection) (50 hours) until reaction.Mixture is filtered, and with twice of washed with dichloromethane filter cake and the recovery of 20mL, filtrate is used saturated NaHCO
3Solution washing twice is removed water layer, and organic layer adds the 5g atlapulgite, filter, remove methylene dichloride, get the 2.4g crude product with Rotary Evaporators, through column chromatography for separation (60g silica gel, sherwood oil: ethyl acetate: 3: 1), obtain the pure product of 1.8g7-keto-DHEA again. productive rate: 61%
Fusing point (mp): 236-238 ℃.
EI-MS(70ev，％)：m/z302(M
+，94)，
1HNMR(CDCl
3，500MHz)：5.71(s，1H，H-6)，3.66(m，1H，H-3)，1.23(s，3H，H-19)，0.88(s，3H，H-18)，
13CNMR(CDCl
3，500MHz)219.7(C-17)，200.3(C-7)，165.7(C-5)，124.8(C-6)，69.2(C-3)，49.1，47.0，44.8，43.3，41.0，37.5，35.3，34.7，30.1，29.74，23.2，19.6，16.5(C-19)，12.8(C-18).
Embodiment 9.Use the allylic oxidation that reclaims support agent: take by weighing DHEAAc0.50g (0.0015mol), adding 0.3gNHPI (0.0018mol) again is dissolved in the methylene dichloride of 60mL, after stirring 10min, the support agent (support agent of the atlapulgite that embodiment 5 reclaims) that adds the atlapulgite of 2.7g recovery, normal temperature stirs after 4 hours down, add the support agent of atlapulgite of the recovery of 2.7g again, finish (thin layer detection) (40 hours) until reaction.Mixture is filtered, and with the washed with dichloromethane filter cake twice of 20mL, filtrate is used saturated NaHCO
3Solution washing twice is removed water layer, and organic layer adds the 5g atlapulgite, filter, remove methylene dichloride, get the 0.44g crude product with Rotary Evaporators, through column chromatography for separation (10g silica gel, sherwood oil: ethyl acetate: 3: 1), obtain the pure product of 0.71g7-keto-DHEAAc again. productive rate: 61%
Claims (7)
1, the synthetic method of a kind of 7-ketone group dehydroepiandros-sterone and acetic ester thereof is characterized in that: with dehydroepiandros-sterone or its acetic ester is raw material, uses CrO
3/ NHPI/ carrier/CH
2Cl
2The support agent system is carried out the directly synthetic corresponding 7-ketone group dehydroepiandros-sterone of selectivity allylic oxidation reaction or its acetic ester under 18～40 ℃.
2, as the said synthetic method of claim 1, it is characterized in that: preparation is a medium with water during support agent, makes CrO earlier
3With the homogeneous phase solution of NHPI, be adsorbed in again on the carrier, evaporate the branch that anhydrates, NHPI and CrO then
3Mol ratio be: 1: 3.3～5.5, CrO
3With the weight ratio of carrier be: 1: 4～6.
3, as the said synthetic method of claim 2, it is characterized in that: said carrier is atlapulgite or 100-200 purpose silica gel or the chemical pure diatomite of diameter less than 75 μ m.
4, as the said synthetic method of claim 3, it is characterized in that: in the reaction system, substrate: CrO
3: the mol ratio of NHPI is 1: 2～5.5: 1～2.7, and reaction medium is a methylene dichloride.
5, as the said synthetic method of claim 4, it is characterized in that: in the reaction system, substrate: CrO
3: the mol ratio of NHPI is 1: 2.5～4: 1.2～1.5.
6,, it is characterized in that reacted support agent filtered and recycled as the said synthetic method of claim 1.
7,, it is characterized in that carrying out according to the following steps as the said synthetic method of claim 5:
(1) preparation support agent: chromium trioxide is dissolved in the deionized water, in 38～42 ℃ of waters bath with thermostatic control, dissolves, add NHPI again, stirred 15～25 minutes, use deionized water dissolving again, add carrier, mixture is fully stirred after, being dried to weighs no longer reduces, levigate, obtains support agent;
(2) obtain product: take by weighing dehydroepiandros-sterone or its acetic ester, add NHPI again, be dissolved in the methylene dichloride, after stirring 8～12min, add support agent, normal temperature stirs after 3～5 hours down, add support agent again and finish until reaction, mixture is filtered, filtrate is used saturated NaHCO
3Solution washing is removed water layer, and organic layer adds atlapulgite, filters, and methylene dichloride is removed in evaporation, gets crude product, again through column chromatography for separation, obtains pure product.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100434175C (en) * | 2006-10-17 | 2008-11-19 | 郑州大学 | Catalyst and its use for synthesizing 4-nitro-3-methyl benzoic acid |
| CN102703560A (en) * | 2011-05-03 | 2012-10-03 | 四川师范大学 | Method for preparing testolactone by microbial transformation |
| CN105669813A (en) * | 2015-12-31 | 2016-06-15 | 厦门金达威维生素有限公司 | Synthesis method of vitamin D3 intermediate 7-ketocholesteryl acetate |
| CN108484710A (en) * | 2018-03-20 | 2018-09-04 | 江阴技源药业有限公司 | A kind of content of beary metal control method of 7-Keto DHEAAc |
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|---|---|---|---|---|
| US4006172A (en) * | 1976-04-26 | 1977-02-01 | The Upjohn Company | Process for 7-keto-Δ5 -steroids |
| US6686486B1 (en) * | 1997-05-07 | 2004-02-03 | Padma Marwah | Process for effecting allylic oxidation |
| US6384251B1 (en) * | 1998-03-18 | 2002-05-07 | Humanetics Corporation | Process for effecting allylic oxidation using dicarboxylic acid imides and chromium reagents |
| EP1615944A4 (en) * | 2003-04-01 | 2010-08-11 | Harbor Biosciences Inc | Antiandrogens with marginal agonist activity and methods of use |
-
2006
- 2006-03-02 CN CNB2006100107146A patent/CN100422204C/en active Active
Cited By (7)
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| CN100434175C (en) * | 2006-10-17 | 2008-11-19 | 郑州大学 | Catalyst and its use for synthesizing 4-nitro-3-methyl benzoic acid |
| CN102703560A (en) * | 2011-05-03 | 2012-10-03 | 四川师范大学 | Method for preparing testolactone by microbial transformation |
| CN105669813A (en) * | 2015-12-31 | 2016-06-15 | 厦门金达威维生素有限公司 | Synthesis method of vitamin D3 intermediate 7-ketocholesteryl acetate |
| CN105669813B (en) * | 2015-12-31 | 2017-11-07 | 厦门金达威维生素有限公司 | A kind of synthetic method of the ketone cholesterol acetate of intermediates of vitamin D_3 7 |
| CN108484710A (en) * | 2018-03-20 | 2018-09-04 | 江阴技源药业有限公司 | A kind of content of beary metal control method of 7-Keto DHEAAc |
| CN111253461A (en) * | 2020-01-15 | 2020-06-09 | 江西青峰药业有限公司 | Synthesis method of 7-oxoacetic acid abiraterone |
| CN111253461B (en) * | 2020-01-15 | 2022-07-01 | 江西山香药业有限公司 | Synthesis method of 7-oxoacetic acid abiraterone |
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Effective date of registration: 20170120 Address after: 224352 Jiangsu province Yancheng City Sheyang County Zhen bin Dong Cun Chiaki Patentee after: Yancheng Ciyt Chunzhu Aroma Co., Ltd. Address before: 653100 high tech Development Zone, Yunnan, Yuxi Patentee before: Yunnan Tianhong Essence and Spice Co., Ltd. |