CN109456379A - A kind of preparation method of danabol product - Google Patents
A kind of preparation method of danabol product Download PDFInfo
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- CN109456379A CN109456379A CN201811555281.1A CN201811555281A CN109456379A CN 109456379 A CN109456379 A CN 109456379A CN 201811555281 A CN201811555281 A CN 201811555281A CN 109456379 A CN109456379 A CN 109456379A
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- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J1/00—Normal steroids containing carbon, hydrogen, halogen or oxygen, not substituted in position 17 beta by a carbon atom, e.g. estrane, androstane
- C07J1/0003—Androstane derivatives
- C07J1/0033—Androstane derivatives substituted in position 17 alfa and 17 beta
- C07J1/0037—Androstane derivatives substituted in position 17 alfa and 17 beta the substituent in position 17 alfa being a saturated hydrocarbon group
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Abstract
The present invention provides a kind of preparation method of danabol product, the method includes using Isosorbide-5-Nitrae-androsadiendione i.e. IDD for raw material, in the presence of methyl-magnesium-halide, organic solvent and acid, in 17 introducing α-CH3With β-OH, the danabol is prepared, then obtained danabol is heated to reflux decoloration in acetone or C4 or less low-carbon alcohols with active carbon and is recrystallized, obtains danabol product.The present invention prepares danabol by raw material of IDD, and the opposite conventional method for making raw material with Chinese yam saponin, raw material sources are extensive, and process economics environmental protection, production cost declines to a great extent.For the method for the present invention compared with conventional production methods, synthetic route is short, and simple process environmental protection, product yield is high, high-quality, and with the calculating of the current prices of raw materials, raw materials for production cost reduces 40-45%.
Description
Technical field
The invention belongs to the fabricating technologies of steroid hormone drug, and in particular to go to a kind of protein anabolic hormone drug
The preparation method of hydrogen methyl testosterone product.
Background technique
Danabol is a kind of protein anabolic hormone drug, has both androgenic effect, is clinically mainly used for burning
Wound, wound and aftertreatment, the treatment etc. of childhood dystrophy are also used for treatment alpastic anemia, chronic debilitating disease
The convalescence of disease and patient etc. that is long-term or widely applying cortex hormone of aadrenaline, market tool are big.
The conventional production methods of danabol are to extract Chinese yam saponin from Chinese yam plant, through protection, oxidation,
Cracking is eliminated, and the key intermediate acetic acid gestation diene alcohol ketone (abbreviation diene) of acquisition is raw material, through oximate, Beckmann rearrangement,
3 step such as sour water solution, which is reacted, is made Dehydroepiandrosterone Acetate, then by dehydroepiandros-sterone again through grignard reaction, basic hydrolysis, Ovshinsky oxygen
4 steps such as 1 change, DDQ dehydrogenation, which are reacted, is made danabol, and synthetic route is shown in attached drawing 1.Wherein Chinese yam saponin mentions
It takes, oxicracking, Beckmann rearrangement, acid, basic hydrolysis, the techniques such as DDQ dehydrogenation reaction, it is more to generate waste water, and it is not easy to handle, it is easily dirty
Contaminate environment；The Ovshinsky oxidation technology used in production need to use steam distillation, and water consume, energy consumption is high.Importantly, with open country
Raw Chinese yam plant resources are increasingly depleted, and artificial growth Chinese yam plant, also because of the increasingly rising of the planting costs such as artificial, chemical fertilizer,
Cause the production cost of saponin, diene to be doubled and redoubled, the production cost of danabol is caused substantially to increase with the market price
It is long, significant impact was produced to global danabol pharmaceutical market already.
According to the design feature of product danabol, particularly, there are three the preparations of danabol
Key point, first point is to convert α-CH for the 17th in raw material ketone group3With β-OH；Second point is double in the 4th upper introducing
Key；It is thirdly in the 1st upper introducing double bond.The method of most traditional production danabol is using double bond at 5
On Dehydroepiandrosterone Acetate be raw material, first upper introduce α-CH at 173With β-OH, then at 4 while 3 introducing ketone groups
Double bond is introduced, finally obtains danabol in 1 upper double bond that introduces, i.e. the scheme as shown in Fig. 1 of the present invention.In the application
The preparation method of another danabol is disclosed in the first invention CN201710754305 of people, specifically uses 17
α-CH is had been incorporated on position3Mestanlone with β-OH is raw material, double bromine Mestanlones is first formed at 1 and 4, then at 1
Danabol is obtained with 4 formation double bonds.
But this field still needs the preparation method of more excellent danabol.
Summary of the invention
And it is raw material that the solution of the present invention, which is the IDD for directly having formed double bond using 1 and 4, up at 17
Fall ketone group and introduces α-CH3With β-OH, a step obtains danabol.
Therefore, the present invention provides a kind of preparation method of danabol product, and the method includes using Isosorbide-5-Nitrae-
Androsadiendione, that is, IDD is raw material, in the presence of methyl-magnesium-halide, organic solvent and acid, in 17 introducing α-CH3With β-OH,
The danabol is prepared, then by obtained danabol in acetone or C4 or less low-carbon alcohols with work
Property charcoal is heated to reflux decoloration and recrystallizes, and obtains danabol product.
In a kind of specific embodiment, the methyl-magnesium-halide is methyl-magnesium-chloride, methyl-magnesium-bromide or methyl iodide
Change magnesium.
In a kind of specific embodiment, the organic solvent is toluene, benzene, chloroform, tetrahydrofuran and dioxane
One or more of, preferred tetrahydrofuran.
In a kind of specific embodiment, it is described acid be organic acid or inorganic acid, and preferably acetic acid, to toluene sulphur
One of acid, hydrochloric acid and sulfuric acid, more preferable hydrochloric acid.
In a kind of specific embodiment, reaction temperature is 30~100 DEG C, and includes first to organic molten in reaction process
Methyl-magnesium-halide generation grignard addition reaction is added in agent and IDD, then adds the grignard object water that acid obtains grignard addition reaction
Then solution is recovered under reduced pressure organic solvent and obtains the danabol after adding water to carry out elutriation.
In a kind of specific embodiment, the method also includes first phytosterol being used to prepare after microbial fermentation
Obtain the IDD.
In a kind of specific embodiment, the method also includes first the deodorization in soybean oil production process being used to distillate
The isolated phytosterol of object.
IDD is dissolved in organic solvent in the present invention, grignard addition reaction one occurs with the solution of methyl-magnesium-halide reagent
Step synthesis danabol；
Further, the concrete operations synthesized are as follows:
A: the preparation of Grignard Reagent
Magnesium powder, organic solvent are added into reactor, stirred, temperature control to 25-55 degree is slowly passed through methyl halogenated alkane,
It is spare to obtain Grignard Reagent until magnesium powder completely disappears for reaction 4-6 hours；
B: the preparation of danabol
Starting material IDD is dissolved in organic solvent, is stirred, temperature control to 30-100 degree, above-mentioned get ready is slowly added dropwise
Grignard Reagent, about 1-1.5 hour drip off, then keep the temperature and react 2~3 hours in 30~100 DEG C, TLC (thin-layer chromatographic analysis) confirmation
Reaction end after having reacted, then is slowly added dropwise acid, hydrolyzes 2-3 hours, after having hydrolyzed, divide water, washes, and organic layer is concentrated under reduced pressure
Organic solvent is recycled, then tap water elutriation is crystallized with alcohol water blend, obtain danabol crude product, HPLC content
98.0% or more, weight yield 90~95%.
C: the purification of danabol
Danabol crude product is dissolved in organic solvent, active carbon is added, reflux decoloration 1-1.5 hours is taken advantage of
Heat filtering washes charcoal with the solvent for being equivalent to 1 times of volume of crude product weight, and filter cake send producer to recycle, and filtrate and washing lotion merge, and depressurizes dense
Contracting solvent is subsequently cooled to -5~0 degree of crystallization 3-4 hours to there is crystal precipitation, filters, and washs, and drying obtains dehydrogenation methyl testis
Plain product, 165~168 DEG C of fusing point, HPLC content 99.0-99.5%, disposing mother liquor is applied, this step weight total recovery 90-95%,
Synthesize total recovery 84-88%.
Organic solvent described in above-mentioned Grignard Reagent synthesis, can be one of methylene chloride, toluene, ether, THF etc.
Or it is several；Methyl halogenated alkane used in synthesis can be chloromethanes, bromomethane or iodomethane；Above-mentioned Grignard reagent synthesis reaction
20~50 DEG C of temperature；Weight proportion between reactant is: magnesium: alkyl halide=1g:2.5~4.0g；Matching between reactant and solvent
Than being: magnesium: organic solvent=1g:2~12ml.
The organic solvent of grignard reaction, can be toluene, benzene, chloroform, tetrahydro furan in above-mentioned danabol synthesis
It mutters, one or more of dioxane etc.；Hydrolysis acid used can be organic acid such as acetic acid, p-methyl benzenesulfonic acid etc., can also
Select inorganic acid such as hydrochloric acid, sulfuric acid etc.；The reaction temperature of grignard reaction and hydrolysis is 30~100 DEG C；Weight between reactant
Proportion is: IDD: grignard reagent solution=1g:5~15ml；Proportion between reactant and solvent is: IDD: react organic solvent=
1g:2~10ml.
Above-mentioned danabol refines organic solvent used, can be toluene, acetone, C4 or less low-carbon alcohols such as first
One or more of alcohol, ethyl alcohol, isopropanol, tert-butyl alcohol etc.；40~100 DEG C of temperature of purification control；The weight of each storeroom is matched
Than being: crude product: active carbon=1g:0.03~0.10g；Proportion between crude product and solvent is crude product: organic solvent=1g:3-
10ml。
Particularly, most preferred process of the present invention is described as follows:
Organic solvent, preferably THF described in above-mentioned Grignard Reagent synthesis, safety and environmental protection facilitate recycling；Used in synthesis
Methyl halogenated alkane, preferably chloromethanes, it is economic and environment-friendly；Preferably 20~30 DEG C of above-mentioned Grignard reagent synthesis reaction temperature；Between reactant
Weight proportion it is preferred: magnesium: chloromethanes=1:2.8；Proportion between reactant and solvent is preferred: magnesium: THF=1g:6ml.
The organic solvent of grignard reaction, preferably THF, convenient post-treatment in above-mentioned danabol synthesis.Hydrolysis institute
The preferred hydrochloric acid of acid is quality-high and inexpensive；Preferably 50~55 DEG C of the reaction temperature of grignard reaction and hydrolysis；Weight between reactant
Amount proportion is preferred: IDD: grignard reagent solution=1g:8ml；Proportion between reactant and solvent is preferred: IDD: reacting organic solvent
=1g:5ml.
Above-mentioned danabol refines organic solvent used, and preferably ethanol, refining effect is good, safety and environmental protection, convenient
Recycling；Extraction temperature preferably ethanol reflux temperature；The weight proportion of each storeroom is preferred: crude product: active carbon=1g:0.05g；Slightly
Proportion between product and solvent is preferred, crude product: organic solvent=1g:5ml.
The beneficial effect comprise that
1, the present invention prepares danabol by raw material of IDD, the opposite conventional method for making raw material with Chinese yam saponin,
Raw material sources are extensive, and process economics environmental protection, production cost declines to a great extent.The method of the present invention is compared with conventional production methods, synthesis
Route is short, and simple process environmental protection, product yield is high, high-quality, and with the calculating of the current prices of raw materials, raw materials for production cost is reduced
40-45%；Recycled can be recycled in solvent used in technique, not only economical, but also environmental protection, is very beneficial to industrialized production.
2, the danabol product that the present invention obtains, 165~168 DEG C of fusing point, HPLC content 99.0-99.5%,
Synthesize total recovery 84-88%.
Detailed description of the invention
Fig. 1 is traditional production danabol synthetic route chart.
Fig. 2 is that dehydrogenation Methyltestosterone synthetic route chart is produced in the present invention.
Specific embodiment
In order to which main points and spirit of the invention are described in more detail, name several embodiments and be explained.
In the following example, the method includes first included using the deodorization distillate in soybean oil production process
The step of Crystallization Separation, obtains phytosterol, specifically for example with prior art CN200680047150.1,
Method described in CN200710014171.X or CN101074258B is prepared from the deodorization distillate in soybean oil production process
Obtain phytosterol.Then using the method microbial fermentation in the prior art as described in CN1250709C phytosterol is turned
Turn to Isosorbide-5-Nitrae-androsadiendione i.e. IDD.It and then further include following steps.
Embodiment 1
A, the preparation of Grignard Reagent
In a 1000ml there-necked flask, 35g magnesium powder, 800ml tetrahydrofuran, stirring is added, heat preservation is passed through in 30-35 DEG C
98g chloromethanes after having led to, continues to be stirred to react 4~6 hours, until magnesium powder disappears substantially, it is spare to obtain Grignard Reagent；
B, the preparation of danabol
In a 1000ml there-necked flask, 100gIDD, 500mlTHF is added, stirring is warming up to 50~55 DEG C, is slowly added dropwise
The above-mentioned about 800ml grignard reagent solution got ready, drips off for about 1-1.5 hours, is further continued for insulated and stirred and reacts 2~3 hours, TLC
Reaction end is detected, after having reacted, slowly dropwise addition 2N hydrochloric acid is small in 50~55 DEG C of continuation hydrolysis 2-3 after dripping off to PH2-3
When, completely, after having reacted, about 90-95%THF is concentrated under reduced pressure out, the THF processing of recycling is applied in TLC detection hydrolysis.Again above-mentioned
600ml tap water is added in raffinate, and system is cooled to 5~10 DEG C, stirring and crystallizing 2~3 hours, filtering, filter cake was with originally
Water washing to neutrality, 70 DEG C or less drying obtain danabol crude product 94.6g, HPLC content 98.2%, weight yield
94.6%.
C, the purification of danabol
In a 1000ml there-necked flask, the danabol crude product of the above-mentioned B step preparation of 100g, 500ml wine is added
Essence is stirred at 30-35 DEG C and is made it completely dissolved, and 5g active carbon is then added, and is heated reflux 1.5-2 hours, is then dropped
Temperature filters, filter cake about 100ml alcohol foam washing, filter cake send producer to recycle, and filtrate is normal after merging with washing lotion while hot to 55-60 degree
Pressure is concentrated into recycling about 88-90% alcohol, then system is cooled to -5~0 DEG C, and stirring and crystallizing 3~4 hours, filtering, filtrate was returned
It receives solvent to apply with mother liquor material, filter cake is washed with a small amount of 50% ethanol water, and 70 DEG C or less drying obtain dehydrogenation methyl testis
Plain product 92.5g, 165~168 DEG C of fusing point, HPLC content 99.5%, weight yield 92.5%.
Embodiment 2
A, the preparation of Grignard Reagent
In a 1000ml there-necked flask, 35g magnesium powder, 800ml tetrahydrofuran, stirring is added, heat preservation is passed through in 40-45 DEG C
120g bromomethane after having led to, continues to be stirred to react 2~3 hours, until magnesium powder disappears substantially, it is spare to obtain Grignard Reagent；
B, the preparation of danabol
In a 1000ml there-necked flask, 100gIDD, 500ml toluene is added, stirring is warming up to 50~55 DEG C, slowly drips
In addition stating the about 800ml grignard reagent solution got ready, drip off within about 1-1.5 hours, be further continued for insulated and stirred and react 2~3 hours,
TLC detects reaction end, and after having reacted, 2N hydrochloric acid is slowly added dropwise to PH2-3, in 50~55 DEG C of continuation hydrolysis 2- after dripping off
3 hours, completely, after having reacted, the mixture of about 90-95%THF and toluene, the THF of recycling was concentrated under reduced pressure out in TLC detection hydrolysis
Mixture processing with toluene is applied.600ml tap water is added in above-mentioned raffinate again, and system is cooled to 5~10 DEG C, stirs
It mixes crystallization 2~3 hours, filters, filter cake originally water washing to neutrality, 70 DEG C or less drying obtain danabol crude product
93.8g HPLC content 98.5%, weight yield 93.8%.
C, the purification of danabol
In a 1000ml there-necked flask, the danabol crude product of the above-mentioned B step preparation of 100g is added, 500ml is different
Propyl alcohol is stirred at 30-35 DEG C and is made it completely dissolved, and 5g active carbon is then added, and is heated reflux 1.5-2 hours, then
It is cooled to 55-60 degree, is filtered while hot, filter cake about 100ml isopropanol foam washing, filter cake send producer to recycle, and filtrate merges with washing lotion
Normal pressure is concentrated into recycling about 88-90% isopropanol afterwards, then system is cooled to -5~0 DEG C, stirring and crystallizing 3~4 hours, filters,
Filtrate recycling design is applied with mother liquor material, and filter cake is washed with a small amount of 50% isopropanol water solution, and 70 DEG C or less drying obtain dehydrogenation
Methyl testosterone product 93.8g, 165.5~167.5 DEG C of fusing point, HPLC content 99.3%, weight yield 94.6%.
Embodiment 3
A, the preparation of Grignard Reagent
In a 1000ml there-necked flask, 35g magnesium powder, 800ml ether is added, stirring is kept the temperature in 30-35 DEG C of dropwise addition 150g
Iodomethane after having led to, continues to be stirred to react 4~6 hours, until magnesium powder disappears substantially, it is spare to obtain Grignard Reagent；
B, the preparation of danabol
In a 1000ml there-necked flask, 100gIDD, 500ml benzene is added, stirring is warming up to 50~55 DEG C, is slowly added dropwise
The above-mentioned about 800ml grignard reagent solution got ready, drips off for about 1-1.5 hours, is further continued for insulated and stirred and reacts 2~3 hours, TLC
Reaction end is detected, after having reacted, slowly dropwise addition 2N hydrochloric acid is small in 50~55 DEG C of continuation hydrolysis 2-3 after dripping off to PH2-3
When, completely, after react, the mixture of about 90-95% ether and benzene is concentrated under reduced pressure out in TLC detection hydrolysis, the ether of recycling with
The mixture processing of benzene is applied.600ml tap water is added in above-mentioned raffinate again, and system is cooled to 5~10 DEG C, stirring analysis
2~3 hours brilliant, filtering, filter cake originally water washing to neutrality, 70 DEG C or less dry, and obtain danabol crude product
91.2g HPLC content 98.7%, weight yield 91.2%.
C, the purification of danabol
In a 1000ml there-necked flask, the danabol crude product of the above-mentioned B step preparation of 100g, 500ml third is added
Ketone is stirred at 30-35 DEG C and is made it completely dissolved, and 5g active carbon is then added, and is heated reflux 1.5-2 hours, is then dropped
Temperature filters, filter cake about 100ml acetone foam washing, filter cake send producer to recycle, and filtrate is normal after merging with washing lotion while hot to 55-60 degree
Pressure is concentrated into recycling about 88-90% acetone, then system is cooled to -5~0 DEG C, and stirring and crystallizing 3~4 hours, filtering, filtrate was returned
It receives solvent to apply with mother liquor material, filter cake is washed with a small amount of 50% aqueous acetone solution, and 70 DEG C or less drying obtain dehydrogenation methyl testis
Plain product 90.8g, 165~168 DEG C of fusing point, HPLC content 99.7%, weight yield 90.8%.
Method synthetic route provided by the invention is short, and technological operation is easy, production economy environmental protection.It is raw to overcome above-mentioned tradition
Many deficiencies such as synthesis material is expensive in production. art, synthetic route is long, complex operation, environmental protection treatment hardly possible, production cost height.
The above content is combine specific preferred embodiment to the further description of the invention made, and it cannot be said that originally
The specific implementation of invention is only limited to these instructions.For those of ordinary skill in the art to which the present invention belongs, not
Under the premise of being detached from present inventive concept, several simple deductions and replacement can also be made, all shall be regarded as belonging to guarantor of the invention
Protect range.
Claims (7)
1. a kind of preparation method of danabol product, which is characterized in that the method includes using Isosorbide-5-Nitrae-hero diene
Diketone, that is, IDD is raw material, in the presence of methyl-magnesium-halide, organic solvent and acid, in 17 introducing α-CH3With β-OH, it is prepared into
Added to the danabol, then by obtained danabol in acetone or C4 or less low-carbon alcohols with active carbon
Heat reflux is decolourized and is recrystallized, and danabol product is obtained.
2. the method according to claim 1, wherein the methyl-magnesium-halide is methyl-magnesium-chloride, methyl bromide
Magnesium or methylpyridinium iodide magnesium.
3. the method according to claim 1, wherein the organic solvent is toluene, benzene, chloroform, tetrahydrofuran
One or more of with dioxane, preferred tetrahydrofuran.
4. the method according to claim 1, wherein it is described acid be organic acid or inorganic acid, and preferably acetic acid,
One of p-methyl benzenesulfonic acid, hydrochloric acid and sulfuric acid, more preferable hydrochloric acid.
5. the method according to claim 1, wherein reaction temperature is 30~100 DEG C, and including in reaction process
Methyl-magnesium-halide is first added into organic solvent and IDD, grignard addition reaction occurs, then add acid and obtain grignard addition reaction
Grignard object hydrolysis, be then recovered under reduced pressure organic solvent and plus water carry out elutriation after obtain the danabol.
6. the method according to claim 1, wherein the method also includes first using phytosterol through microorganism
The IDD is prepared after fermentation.
7. according to the method described in claim 6, it is characterized in that, the method also includes first using in soybean oil production process
The isolated phytosterol of deodorization distillate.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1507489A (en) * | 2001-05-11 | 2004-06-23 | �ſ���ѧ��˾ | Microorganism having ability to convert sterol into androst-4-ene-3,17-di-one/androsta-1,4-diene-3,17-dione and preparation method and use thereof |
| CN105294797A (en) * | 2015-11-17 | 2016-02-03 | 华中药业股份有限公司 | Preparation method for methyltestosterone |
| CN107501373A (en) * | 2017-08-29 | 2017-12-22 | 湖南科瑞生物制药股份有限公司 | A kind of preparation method of danabol |
-
2018
- 2018-12-18 CN CN201811555281.1A patent/CN109456379B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1507489A (en) * | 2001-05-11 | 2004-06-23 | �ſ���ѧ��˾ | Microorganism having ability to convert sterol into androst-4-ene-3,17-di-one/androsta-1,4-diene-3,17-dione and preparation method and use thereof |
| CN105294797A (en) * | 2015-11-17 | 2016-02-03 | 华中药业股份有限公司 | Preparation method for methyltestosterone |
| CN107501373A (en) * | 2017-08-29 | 2017-12-22 | 湖南科瑞生物制药股份有限公司 | A kind of preparation method of danabol |
Non-Patent Citations (2)
| Title |
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| BIE SONGTA,ET AL.: "Bioconversion methyl-testosterone in a biphasic system", 《PROCESS BIOCHEMISTRY》 * |
| 胡小泓 等: "大豆油脱臭馏出物中提取植物甾醇的研究", 《中国油脂》 * |
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