CN1563070A - Androstane 4 ene-3 beta, 6 beta, 17 beta-trihydric alcohol and preparation method - Google Patents
Androstane 4 ene-3 beta, 6 beta, 17 beta-trihydric alcohol and preparation method Download PDFInfo
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- CN1563070A CN1563070A CN 200410017078 CN200410017078A CN1563070A CN 1563070 A CN1563070 A CN 1563070A CN 200410017078 CN200410017078 CN 200410017078 CN 200410017078 A CN200410017078 A CN 200410017078A CN 1563070 A CN1563070 A CN 1563070A
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Abstract
The invention belongs to the field of organic chemical synthesis technology, and relates to a compound androst-4-ene-3 bota, 6 beta, 17 beta-triol and its preparation method. Said invention uses dehydroepiandrosterone as raw material, and utilizes epoxidation-hydrolization reaction to obtain 3 beta, 5 alpha, 6 beta-trihydroxyandrostane-17-ketone, and utilizes oxidation-dehydration reaction to obtain androst-4-ene-3,6-17-trione, then adopts reduction reaction to obtain the invented adrost-4-ene-3 beta, 6 beta, 17 beta-triol. Said invention uses dehydroepiandrosterone as raw material, and utilizes several simple unit reactions to synthesize said new compound androst-4-ene-3-beta, 6 beta, 17 beta-trial. As compared with androst-4-ene-3,6,17-trione it has the characteristics of that it can be easily absorbed in the body.
Description
Technical field
The invention belongs to the synthetic field of organic chemistry, relate to compound androstane-4-alkene-3 β, 6 β, 17 beta-triols and preparation method thereof.
Background technology
Androstane-4-alkene-3,6, the 17-triketone is a kind of aromatase inhibitor, energy passivation aromatase enzyme, thus have the estrogenic effect of inhibition.Analyze supposition according to the relevant expert, its derivative also has similar effect, and its compatibility is used, and can produce better effect.At present, appropriate authority is just developed as healthcare products and anti-breast cancer medicines both at home and abroad.According to the literature, androstane-4-alkene-3,6, the synthetic method of 17-triketone, the raw and auxiliary material cost is higher, and the source is difficult.Above-claimed cpd and derivative and preparation method's research has caused that the relevant personnel pay close attention to.Androstane-4-alkene-3,6, the synthetic method of 17-triketone, the domestic and international report that does not still have document or patent.
Summary of the invention
It is simple, convenient to the purpose of this invention is to provide a kind of preparation, the new compound androstane-4-alkene-3 β that total recovery and purity are high, 6 β, 17 beta-triols.
Another object of the present invention provides new compound androstane-4-alkene-3 β, 6 β, the preparation method of 17 beta-triols.
The present invention is raw material with the dehydroepiandros-sterone, use simple unit process, comprise: epoxidation-hydrolysis, oxidation-dehydration and reduction reaction have been synthesized the new compound androstane-4-alkene-3 β of formula (I), 6 β, 17 beta-triols, whole processing method is simple, and is easy to operate, and product total recovery and purity are all very high.
New compound androstane-4-alkene-3 β of the present invention, 6 β, 17 beta-triols have in vivo than androstane-4-alkene-3, and 6, the characteristics of the easier absorption of 17-triketone.
The present invention is achieved through the following technical solutions,
The synthesis route of employing formula (II) is a raw material with the dehydroepiandros-sterone, makes 3 β through epoxidation-hydrolysis reaction, 5 α, and 6 β-trihydroxy-etioallocholane-17-ketone generate androstane-4-alkene-3,6,17-triketone through oxidation-dehydration reaction.
The present invention adopts the synthesis route of formula (III), with androstane-4-alkene-3, and 6, the 17-triketone is a raw material, generates androstane-4-alkene-3 β, 6 β, 17 beta-triols through reduction reaction.
The present invention is a raw material with the dehydroepiandros-sterone, makes androstane-4-alkene-3 β, 6 β, and the method for 17 beta-triols comprises the steps,
1) epoxidation-hydrolysis reaction: a. is dissolved in chloroform with dehydroepiandros-sterone, adds peroxyacetic acid, 30 ℃ of stirring reactions; B. reaction finishes, and adds vitriolization again; C. washing is filtered, and makes 3 β, 5 α, 6 β-trihydroxy-etioallocholane-17-ketone.
2) oxidation-dehydration reaction: β a.3,5 α, 6 β-trihydroxy-etioallocholane-17-ketone is dissolved in Glacial acetic acid, adds chromic acid, stirring reaction; B. be warming up to 50 ℃; C. elutriation filters, washing, dry androstane-4-alkene-3,6, the 17-triketone of getting.
3) reduction reaction: a. androstane-4-alkene-3,6, the 17-triketone is dissolved in methyl alcohol; B. stir under the room temperature and add potassium boron hydrogen down; C. room temperature reaction; D. elutriation,, filter, washing, drying makes androstane-4-alkene-3 β, 6 β, 17 beta-triols.
The present invention has following advantage: is raw material with the dehydroepiandros-sterone,, synthesized new compound androstane-4-alkene-3 β with some simple unit processes, and 6 β, 17 beta-triols, whole processing method is simple, and is easy to operate, and product total recovery and purity are all very high.
Embodiment:
Embodiment 1
With the dehydroepiandros-sterone is feedstock production androstane-4-alkene-3 β, 6 β, 17 beta-triols
1, preparation 3 β, 5 α, 6 β-trihydroxy-etioallocholane-17-ketone
Dehydroepiandros-sterone 1kg is dissolved in chloroform 5L, adds peroxyacetic acid 250ml, 30 ℃ of stirring reactions 1 hour, reaction finishes, and adds 10% sulfuric acid 2L, stirs 4 hours in 35 ℃.Then, wash with water, filter, drying makes 3 β, 5 α, 6 β-trihydroxy-etioallocholane-17-ketone 1.02kg.
2, preparation androstane-4-alkene-3,6, the 17-triketone
With 3 β, 5 α, 6 β-trihydroxy-etioallocholane-17-ketone 1.02kg is dissolved in Glacial acetic acid 5.1L, adds 0.4 times of chromic acid, stirring at room reaction 2 hours.Being warming up to 50 ℃ stirred 1 hour.Elutriation filters, washing, dry androstane-4-alkene-3,6, the 17-triketone 0.9kg of getting.Get androstane-4-alkene-3 with ethyl alcohol recrystallization again, 6,17-triketone elaboration 0.75kg.MS (m/z) 300 (M
+); M.p.228～230 ℃; [α]
D 20+ 37.5 °; Content: 99.5% (HPLC).
3, preparation androstane-4-alkene-3 β, 6 β, 17 beta-triols
With androstane-4-alkene-3,6,17-triketone 1kg is dissolved in methyl alcohol 15L, stirs under the room temperature to add potassium boron hydrogen 0.1kg, room temperature reaction 2 hours down.Reaction is finished, and elutriation filters, washing, and drying makes androstane-4-alkene-3 β, 6 β, 17 beta-triol 0.95kg.With methyl alcohol-chloroform recrystallization, get androstane-4-alkene-3 β, 6 β, 17 beta-triol elaboration 0.9kg.MS(m/z)306(M
+)。
Claims (3)
1, compound androstane-4-alkene-3 β, 6 β, 17 beta-triols have the structure of following formula.
2, the compound androstane-4-alkene-3 β of claim 1,6 β, the preparation method of 17 beta-triols is characterized in that with the dehydroepiandros-sterone being raw material, make 3 β through epoxidation-hydrolysis reaction, 5 α, 6 β-trihydroxy-etioallocholane-17-ketone generate androstane-4-alkene-3 through oxidation-dehydration reaction, 6, the 17-triketone, synthesis route is
With androstane-4-alkene-3,6, the 17-triketone is a raw material, generates androstane-4-alkene-3 β through reduction reaction, 6 β, 17 beta-triols, synthesis route are,
3, according to the compound androstane-4-alkene-3 β of claim 2,6 β, the preparation method of 17 beta-triols is characterized in that comprising the steps,
1) epoxidation-hydrolysis reaction: a. is dissolved in chloroform with dehydroepiandros-sterone, adds peroxyacetic acid, 30 ℃ of stirring reactions; B. reaction finishes, and adds vitriolization again; C. washing is filtered, and makes 3 β, 5 α, 6 β-trihydroxy-etioallocholane-17-ketone.
2) oxidation-dehydration reaction: β a.3,5 α, 6 β-trihydroxy-etioallocholane-1 7-ketone is dissolved in Glacial acetic acid, adds chromic acid, stirring reaction; B. be warming up to 50 ℃; C. elutriation filters, washing, dry androstane-4-alkene-3,6, the 17-triketone of getting.
3) reduction reaction: a. androstane-4-alkene-3,6, the 17-triketone is dissolved in methyl alcohol; B. stir under the room temperature and add potassium boron hydrogen down; C. room temperature reaction; D. elutriation,, filter, washing, drying makes androstane-4-alkene-3 β, 6 β, 17 beta-triols.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410017078 CN1563070A (en) | 2004-03-19 | 2004-03-19 | Androstane 4 ene-3 beta, 6 beta, 17 beta-trihydric alcohol and preparation method |
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| CN 200410017078 CN1563070A (en) | 2004-03-19 | 2004-03-19 | Androstane 4 ene-3 beta, 6 beta, 17 beta-trihydric alcohol and preparation method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103073608A (en) * | 2013-02-26 | 2013-05-01 | 昆明理工大学 | Androstane-4, 6, 8 (9), 13 (14)-tetraene-3, 11, 16-triketone and application thereof |
| CN103073607A (en) * | 2013-02-26 | 2013-05-01 | 昆明理工大学 | 12[beta]-hydroxyandrostane-4,6,8(9),13(14)-tetraene-3,11,16-triketone and application thereof |
-
2004
- 2004-03-19 CN CN 200410017078 patent/CN1563070A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103073608A (en) * | 2013-02-26 | 2013-05-01 | 昆明理工大学 | Androstane-4, 6, 8 (9), 13 (14)-tetraene-3, 11, 16-triketone and application thereof |
| CN103073607A (en) * | 2013-02-26 | 2013-05-01 | 昆明理工大学 | 12[beta]-hydroxyandrostane-4,6,8(9),13(14)-tetraene-3,11,16-triketone and application thereof |
| CN103073607B (en) * | 2013-02-26 | 2014-09-03 | 昆明理工大学 | 12[beta]-hydroxyandrostane-4,6,8(9),13(14)-tetraene-3,11,16-triketone and application thereof |
| CN103073608B (en) * | 2013-02-26 | 2014-09-03 | 昆明理工大学 | Androstane-4, 6, 8 (9), 13 (14)-tetraene-3, 11, 16-triketone and application thereof |
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