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Method for preparing androstane-1,4,6-triene-3,17-diketone

A technology of triene and androster, which is applied in the field 1, can solve the problems of many impurities, danger, and high cost, and achieve the effects of reducing pollution, having technical and economic advantages, and improving the total conversion rate

Inactive Publication Date: 2010-03-03
TIANJIN JINYAO GRP
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] The disadvantages of this route are poor reaction selectivity and more impurities, and according to the MSDS file of DDQ (http: / / www.sciencelab.com / xMSDS-2_3_Dichloro_5_6_dicyano_1_4_benzoquinone-9923726, p.4), DDQ is a skin Contact, inhalation, and swallowing are very dangerous chemical substances. More importantly, the physical properties of the by-products are relatively close to those of the product. It is extremely difficult to refine industrially, and DDQ is converted into chlorinated phenols after dehydrogenation. Difficult to degrade in nature, very serious environmental pollution
And the raw material that prior art adopts is dehydroepiandrosterone, and cost is higher

Method used

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  • Method for preparing androstane-1,4,6-triene-3,17-diketone
  • Method for preparing androstane-1,4,6-triene-3,17-diketone
  • Method for preparing androstane-1,4,6-triene-3,17-diketone

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0029] (1) Get 10g of androst-4-ene 3,17-dione (compound I) into the reaction flask, then add 40ml of absolute ethanol, stir, and pass N 2 , kept at -10°C, added 10ml of triethyl orthoformate, 0.15g of PTS, kept at -10°C for 4 hours until the reaction was complete, added 2ml of pyridine, cooled to -10°C, stood still, filtered, and dried to obtain androster -3-Ethoxy-3,5-dien-17-one 11.0g (Compound II)

[0030] (2) Add the compound (II) obtained in step (1) into the reaction flask, then add 30ml DMF, 1ml water, and pass N 2 Stir, cool down to 0°C, add NBS three times within 30 minutes, 3g each time, add 9g in total, keep at 5-10°C for 2 hours until the reaction is complete, then add Li 2 CO 3 5g, LiBr 2.5g, heat up to 70-80°C, react for 1 hour until the end of the reaction, cool, dilute and filter to obtain 9.8g androst-4,6-diene-3,17-dione (compound III)

[0031] (3) Biological fermentation

[0032]

[0033]

[0034] 300ml seed medium

[0035] Fermentation medium 3...

Embodiment 2

[0042] (1) Get 10g of androst-4-ene 3,17-dione (compound I) into the reaction flask, then add 80ml of methanol, stir, and pass N 2 , kept at 0°C, added 9ml of isopropenyl acetate, 0.08g of PTS, kept at 0°C for 4 hours to complete the reaction, added 1ml of pyridine, added 1000ml of water to dilute, filtered, and dried to obtain androst-3-ethoxy- 3,5-dien-17-one 10.8g (compound II)

[0043] (2) Add the compound (II) obtained in step (1) into the reaction flask, then add 30ml of dioxane, 1ml of water, and pass N 2 Stir, cool down to 10°C, add NBS three times within 30 minutes, 2.4g each time, add 7.2g in total, keep at 0-5°C for 2 hours until the reaction is complete, then add Li 2 CO 3 4g, LiBr 2g, heat up to 50-60°C, react for 1 hour until the end of the reaction, cool, dilute and filter to obtain 9.5g androst-4,6-diene-3,17-dione (Compound III)

[0044] (3) Biological fermentation

[0045]

[0046] 300ml seed medium

[0047] Fermentation medium 300ml

[0048] The above...

Embodiment 3

[0054] (1) Get 10g of androst-4-ene 3,17-dione (compound I) into the reaction flask, then add 50ml of acetone, stir, and pass N 2 , keep at 0°C, add 15ml of triethyl orthoformate, PTS 0.3, keep at 10°C for 4 hours until the reaction is complete, add 4ml of pyridine, add 500ml of water to dilute, let it stand, filter, and dry to obtain androst-3-b Oxy-3,5-dien-17-one 11.1g (compound II)

[0055] (2) Add the compound (II) obtained in step (1) into the reaction flask, then add 60ml DMF, 1ml water, and pass N 2 Stir, cool down to 0°C, add NBS three times within 30 minutes, 3g each time, add 9g in total, keep at 10-15°C for 2 hours until the reaction is complete, then add Li 2 CO 3 5g, LiBr 2.5g, heat up to 60-70°C, react for 1 hour until the end of the reaction, cool, dilute and filter to obtain 9.9g androst-4,6-diene-3,17-dione (compound III)

[0056] (3) Biological fermentation

[0057]

[0058] 300ml seed medium

[0059] Fermentation medium 300ml

[0060] The above pro...

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Abstract

The invention provides a method for preparing androstane-1,4,6-triene-3,17-diketone. The method comprises the following steps: adding a compound (I) into a polar organic solvent, and adding an ester reagent and an acid catalyst into the mixture to preparing a compound (II); adding the compound (II) into the organic solvent, adding a halogen reagent and water into the mixture for halogenating reaction; after the reaction is completed, adding lithium salt for reaction to prepare a compound (III); and carrying out 1,2 position dehydrogenation of the compound (III) by a method for biofermentationby adopting an arthrobacter nicotinovorans to prepare the target product.

Description

Technical field: [0001] The present invention relates to a preparation method of a steroid structure, in particular to the preparation of a 1,4,6-triene structure steroid intermediate Background technique: [0002] Androst-1,4,6-triene-3,17-dione is an important steroid intermediate, which can be used to prepare 1α-hydroxydhydroepiandrosterone (CAS: 20998-18-9), etc. Material, literature HELVETICA CHIMICA ACTA-Vol.64, Fasc.6(1981)-Nr-180,1870~1873 discloses androsta-1,4,6-triene-3,17-dione is used for the synthesis of 1α- Uses of hydroxydehydroepiandrosterone. Document J chem.Soc.1968,2568-2570 and document J org.chem.1974.Vol 392931-2933 disclose the main synthetic route of 1,4,6-triene structure steroid intermediate as dehydroepiandrosterone (CAS: 53-43-0) as raw material, using 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) as a dehydrogenation reagent to prepare in one step, the route is as follows: [0003] [0004] The disadvantages of this route are poor reacti...

Claims

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Application Information

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IPC IPC(8): C12P33/02C07J1/00C12R1/06
Inventor 金玉鑫赵春霞
Owner TIANJIN JINYAO GRP
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