Preparation method of 3beta-acetoxyandrostane-5-ene-17-one

A technology of acetoxyandrostene and androstane, which is applied in the field of organic compound preparation, can solve the problems of many by-products and low total yield, and achieve the effects of convenient operation, cost reduction, and enhancement of market competitiveness

Active Publication Date: 2021-02-23
EAST CHINA NORMAL UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0007] The combination of chemical-biological catalysis is the latest method to produce 3β-acetoxyandrost-5-en-17-one, but this method still has the defects of many by-products and low overall yield

Method used

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  • Preparation method of 3beta-acetoxyandrostane-5-ene-17-one
  • Preparation method of 3beta-acetoxyandrostane-5-ene-17-one
  • Preparation method of 3beta-acetoxyandrostane-5-ene-17-one

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0050] Example 1 Preparation of 3β-acetoxyandrost-17-one-6α-boronic acid

[0051] Add 10g of the compound androstane-3β-hydroxy-17-one-6α-boronic acid, 30ml of acetic anhydride and 10ml of pyridine into a 100ml three-necked flask, heat up to 80°C for 1 hour under stirring, and the reaction of the raw materials is complete. Cool down to room temperature, add 70ml of water, solid precipitates, stir for 15 minutes, filter with suction, wash with water until neutral, and dry to obtain 11g of white solid compound 3β-acetoxyandrost-17-one-6α-boronic acid. 1 H NMR (400MHz, DMSO-d6 ):δ7.39(s,2H),4.58-4.52(m,1H),2.35(dd,J=19.2,8.7Hz,1H),2.04-1.99(m,1H),1.96(s,3H), 1.86-1.79(m,1H),1.71-1.67(m,2H),1.64-1.53(m,4H),1.46-1.40(m,3H),1.27-1.10(m,5H),0.99-0.90(m ,2H),0.87-0.81(m,1H),0.80(s,3H),0.77(s,3H),0.72-0.66(m,1H). 13 C NMR (100MHz, DMSO-d 6 ): δ 219.8, 169.7, 72.9, 53.650.6, 47.0, 44.8, 36.1, 35.3, 34.9, 34.7, 33.2, 32.4, 31.3, 27.1, 26.4, 21.3, 21.0, 20.0, 13.4, 12.3.

Embodiment 2

[0052] Example 2 Preparation of 3β-acetoxyandrost-6α-hydroxyl-17-one

[0053] Add 11g of compound 3β-acetoxyandrost-17-one-6α-boronic acid and 25ml of methanol into a 100ml three-necked flask, stir to dissolve, cool down to 10°C, add 4g of 30% hydrogen peroxide, stir for 30 minutes, heat up to 20°C for reaction After 2 hours, the raw material reacted completely and was extracted with 10% sodium bisulfite. Recover methanol under reduced pressure, evaporate to dryness, add 40ml of water and 50ml of dichloromethane, stir and wash for 5 minutes to separate layers, wash with water (10ml×3) to pH = 7, add 10g of anhydrous sodium sulfate to dry, suction filter, and recover dichloromethane under reduced pressure methane to obtain 9.7 g of oily 3β-acetoxyandrost-6α-hydroxyl-17-one. 1 H NMR (400MHz, CDCl 3 ):δ4.71-4.65(m,1H),3.51-3.38(m,1H),2.46(dd,J=19.2,8.7Hz,1H),2.26-2.21(m,1H),2.14-2.10(m ,2H),2.03(s,3H),1.99-1.92(m,1H),1.87-1.80(m,2H),1.76-1.72(m,1H),1.69-1.61(m,3H),1.56-1.46 (...

Embodiment 3

[0054] Example 3 Preparation of 3β-acetoxyandrost-17-one-6α-ol p-toluenesulfonate

[0055] Add 9.7 g of the above-mentioned oily 3β-acetoxyandrost-6α-hydroxy-17-one and 30 ml of pyridine into a 100 ml three-necked flask, and stir to dissolve. Cool down to 0°C and add 8g of p-toluenesulfonyl chloride, stir and react at room temperature for 12 hours, and the reaction is complete. Add 100ml of water, stir, solid precipitates out, filter with suction, wash with water, and dry to obtain 13.0g of 3β-acetoxyandrost-17-one-6α-ol p-toluenesulfonate as a white solid. 1 H NMR (400MHz, CDCl 3 ): δ7.77(d, J=7.8Hz, 2H), 7.33(d, J=7.8Hz, 2H), 4.58-4.51(m, 1H), 4.45-4.39(m, 1H), 2.47-2.40( m,4H),2.19-2.16(m,1H),2.10-2.03(m,1H),1.99(s,3H),1.85-1.78(m,4H),1.73-1.60(m,2H),1.52- 1.15(m,8H),1.08-0.95(m,2H),0.84(s,6H),0.74-0.69(m,1H). 13 C NMR (100MHz, CDCl 3 ):δ220.2,170.3,144.6,134.4,129.7(2C),127.7(2C),81.2,72.4,53.3,50.9,48.7,47.7,37.7,37.2,36.7,35.7,34.0,31.2,28.2,26.8,21.7, 21.6, 21.3, ...

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Abstract

The invention discloses a method for preparationof 3beta-acetoxyandrostane-5-ene-17-one by utilizing androstane-3-beta hydroxyl-17-one-6alpha-boric acid separated from androstane-5-ene-17-one chemicalreduction reaction solid waste through the four steps of reactions of esterification, oxidation, sulfonic acid esterification and elimination. According to the method, the steroid solid waste can beeffectively recycled, the synthesis method is efficient, the reaction conditions are mild, and the cost of related products is correspondingly reduced while the environmental pollution is reduced.

Description

technical field [0001] The invention belongs to the technical field of organic compound preparation, and relates to the reuse of androstane-3β-hydroxyl-17-one-6α-boronic acid separated from solid waste in androst-5-en-17-one chemical reduction reaction. Specifically, it relates to a method for preparing 3β-acetoxy androst-5-en-17-one by reutilizing the by-product androstane-3β-hydroxyl-17-one-6α-boronic acid. Background technique [0002] Compound 3β-acetoxyandrost-5-en-17-one is the starting material for a series of heavy steroid drugs, such as abiraterone acetate, drospirenone, etc.; important steroid drugs, including mifepristone, Telapristone, Norgesmet, etc., and the starting materials or intermediates of estrogen drugs such as norethindrone, estrone, estradiol, estriol; in the field of new steroid drug discovery, including tumor, joint plays an extremely important role in areas such as inflammation, depression, and birth control (WO9925192) [0003] The traditional s...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07J1/00
CPCC07J1/0011Y02P20/55
Inventor 杨帆刘宇飞戴龙华汤杰于丽芳刘婷
Owner EAST CHINA NORMAL UNIV
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