Method for preparing epiandrosterone with androstenedione as raw material

A technology of androstenedione and epiandrosterone, which is applied in the field of preparation of epiandrosterone, can solve the problems of complex reaction process and low product yield, and achieve the effects of high yield and purity, simple recovery method, and pollution reduction

Active Publication Date: 2020-05-22
WUHAN INSTITUTE OF TECHNOLOGY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, there are two reduction reactions in the reaction process of this method, which are respectively lithium ammonia reduction reaction and borohydrogen reduction hydrolysis reaction. The reaction process is complicated and the product yield is relatively low.

Method used

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  • Method for preparing epiandrosterone with androstenedione as raw material
  • Method for preparing epiandrosterone with androstenedione as raw material
  • Method for preparing epiandrosterone with androstenedione as raw material

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0043] In the first step, add 100g (0.349mol) of androstenedione), 200mL (2.12mol) of acetic anhydride, and 200mL of dichloromethane into a 1000mL three-necked flask protected by nitrogen in turn, and the temperature is controlled at about 20°C. Stir until all the materials are dissolved. Then add 4g (0.023mol) p-toluenesulfonic acid, and condense to reflux. The reaction was monitored by TLC, and the reaction was stopped after 20 hours. The reaction solution was poured into ice water for water analysis, and the solid was filtered out and dried in a vacuum oven to obtain 108 g of crude product (2), with a weight yield of 108%.

[0044] In the second step, take 40mL (0.366mol) of trimethyl orthoformate, 80mL (1.44mol) of ethylene glycol, and 8g (0.046mol) of p-toluenesulfonic acid in a three-necked flask, react at 40°C for 2 hours, and then add 100g (0.305mol) ) product (2) crude product, TLC monitoring (V 石油醚 :V 乙酸乙酯 =2:1) ​​Response. After 6 hours, the reaction was basicall...

Embodiment 2

[0048] The first step is the same as in Example 1.

[0049] In the second step, take 30mL (0.275mol) of trimethyl orthoformate, 100mL (1.80mol) of ethylene glycol, and 20g of p-toluenesulfonic acid in a 1L three-necked flask, react at 20°C for 2 hours, and then add 80g (0.244mol) of The crude ene esterification product obtained in one step was monitored by TLC. After 9 hours, the reaction was basically complete. Triethylamine was added to quench the reaction, and the solvent was removed under reduced pressure. The mixture was poured into ice water for water analysis, and the solid was filtered out and dried in vacuo to obtain 89 g of crude product of ketal product (3). Rate 102.5%.

[0050] Subsequent steps are the same as in Example 1.

Embodiment 3

[0052] The first step and the second step are the same as in Example 1.

[0053] The third step is to take 100g (0.269mol) of the crude ketal product obtained in the previous step, add 40mL of methanol solution to dissolve, then add 10g of sodium tert-butoxide, stir at 80°C for 1h until the product (2) completely disappears, and then add 10g of palladium Carbon, reacted in 80℃, 2MPa autoclave for 24 hours. After the reaction was completed, vacuum filtration was performed, palladium carbon was recovered, methanol and water were removed, and 103 g of product (4) after esterification and reduction was obtained, with a weight yield of 103%. The purity of the product determined by HPLC was 96%.

[0054] The fourth step is the same as in Example 1.

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Abstract

The invention relates to a method for preparing epiandrosterone by taking androstenedione as a raw material, and a target product epiandrosterone is obtained through the four-step reactions of a 3-carbonyl alkene esterification reaction, a 17-carbonyl ketal protective reaction, a hydrolysis and palladium carbon catalytic reduction reaction and an acid hydrolysis reaction of androstenedione. Compared with the existing synthesis method, the source of the raw material of the method is rich, the price is low, the synthesis condition is mild, the reduction effect of a catalyst is good, the yield ishigh, the production cost is relatively low, and the method is suitable for industrial production.

Description

technical field [0001] The invention relates to the technical field of synthesis of pharmaceutical intermediates, in particular to a new method for preparing epiandrosterone using androstenedione as a raw material. Background technique [0002] As a steroid hormone intermediate, epiandrosterone can not only be used to synthesize high-end androgen drugs such as rocuronium bromide and vecuronium bromide, but also can be used as an additive for beauty products, and has anti-cancer, anti-aging, It has a broad prospect in industry, and its structural formula is as follows: [0003] [0004] The traditional synthetic method of epiandrosterone is to use diosgenin as raw material, after esterification, cracking, oxidation and hydrolysis, acetic acid pregnant dienolone (diene for short, denoted as II) is obtained, and the diene is then subjected to oximation, backman Rearrangement and hydrolysis to obtain dehydroepiandrosterone (DHEA), and DHEA undergoes hydrogenation reduction t...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07J1/00
CPCC07J1/0011
Inventor 肖春桥池汝安陶琪
Owner WUHAN INSTITUTE OF TECHNOLOGY
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