A kind of preparation method of 3β-acetoxy androst-5-ene-17-one

A technology for acetoxyandrostane and androstane, which is applied in the field of organic compound preparation, can solve the problems of low total yield and many by-products, and achieves the effects of cost reduction, convenient operation and novel method

Active Publication Date: 2022-07-08
EAST CHINA NORMAL UNIV
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  • 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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  • A kind of preparation method of 3β-acetoxy androst-5-ene-17-one
  • A kind of preparation method of 3β-acetoxy androst-5-ene-17-one
  • A kind of preparation method of 3β-acetoxy androst-5-ene-17-one

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

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

[0051] 10g of compound androstane-3β-hydroxy-17-keto-6α-boronic acid, 30ml of acetic anhydride and 10ml of pyridine were added to a 100ml three-necked flask, and the temperature was raised to 80°C under stirring for 1 hour, and the reaction of the raw materials was complete. It was cooled to room temperature, 70 ml of water was added, the solid was precipitated, stirred for 15 minutes, suction filtered, washed with water until neutral, and dried to obtain 11 g of a 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,...

Embodiment 2

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

[0053] Add 11g of compound 3β-acetoxyandrost-17-keto-6α-boronic acid and 25ml of methanol to a 100ml three-necked flask, stir and dissolve, cool to 10°C, add 4g of hydrogen peroxide with a content of 30%, stir for 30 minutes, and heat up to 20°C for reaction After 2 hours, the reaction of the raw materials was completed, and it was quenched with 10% sodium bisulfite. Recover methanol under reduced pressure, add 40 ml of water and 50 ml of dichloromethane, stir and wash for 5 minutes after evaporating to dryness, and then stir and wash for 5 minutes. Methane to obtain 9.7 g of oily substance 3β-acetoxyandrost-6α-hydroxy-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 (m, 2H), 1.38-1.21 (m, 4H), 1.13-1.05 (m, 2H), 1.02-0.93 (m, 1H), 0.8...

Embodiment 3

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

[0055] 9.7 g of the above-mentioned oily substance 3β-acetoxyandrost-6α-hydroxy-17-one and 30 ml of pyridine were added to a 100 ml three-necked flask, and the mixture was stirred and dissolved. The temperature was lowered to 0° C., 8 g of p-toluenesulfonyl chloride was added, and the reaction was stirred at room temperature for 12 hours, and the reaction was complete. 100 ml of water was added, stirred, the solid was precipitated, suction filtered, washed with water, and dried to obtain 13.0 g of 3β-acetoxyandrost-17-one-6α-alcohol 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....

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Abstract

The invention discloses an androstane-3β-hydroxy-17-ketone-6α-boronic acid obtained by separating androstane-3β-hydroxy-17-ketone-6α-boronic acid from a chemical reduction reaction solid waste of androst-5-ene-17-ketone through esterification, oxidation and sulfonic acid. A method for preparing 3β-acetoxyandrost-5-ene-17-ketone by esterification and elimination four-step reaction. The method of the invention can effectively recycle and reuse the steroid solid waste, the synthesis method is efficient, the reaction conditions are mild, the environmental pollution is reduced, and the cost of related products is correspondingly reduced.

Description

technical field [0001] The invention belongs to the technical field of organic compound preparation, and relates to the reuse of androstane-3β-hydroxy-17-one-6α-boronic acid separated from androstane-5-en-17-one chemical reduction reaction solid waste. In particular, it relates to a method for preparing 3β-acetoxyandrost-5-en-17-one by reusing the by-product androstane-3β-hydroxy-17-keto-6α-boronic acid. Background technique [0002] The compound 3β-acetoxyandrost-5-en-17-one is the starting synthetic material of a series of heavy steroid drugs, such as abiraterone acetate, drospirenone, etc.; important steroid drugs, including mifepristone, Trapristone, norgestimate, etc., as well as the starting materials or intermediates of estrogen drugs such as norethisterone, estrone, estradiol, estriol, etc.; in the field of new steroid drug discovery, including tumors, joints Inflammation, depression, birth control and other fields all play an extremely important role (WO9925192) ...

Claims

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Application Information

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Patent Type & Authority Patents(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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