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Synthetic method of 25‑hydroxy‑7‑ketocholesterol

A technology of hydroxycholesterol and synthesis method, applied in the directions of steroids, organic chemistry, etc., can solve the problems of difficult industrialization, great hidden dangers of environmental protection, troublesome post-processing, etc., and achieves the effects of less three wastes, environmental friendliness and low cost.

Active Publication Date: 2018-02-27
ZHEJIANG UNIV OF TECH +2
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] The above method uses PCC, an oxidizing reagent containing heavy metal Cr, which requires a large amount and troublesome post-treatment, and produces a large amount of Cr-containing wastewater, which is difficult to handle, has great environmental protection risks, and is difficult to realize industrialization.

Method used

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  • Synthetic method of 25‑hydroxy‑7‑ketocholesterol

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0025] At room temperature (20-25°C), dissolve 4.86 g (10 mmol) of 25-hydroxycholesterol diacetate in 50 mL of butanone, add 1.63 g (10 mmol) of N-hydroxyphthalimide, 48 mg of benzoyl peroxide, stirred evenly, continued to feed air, reacted for 8 hours, TLC traced to the complete reaction of 25-hydroxycholesterol diacetate, cooled down to 0°C, and precipitated catalyst N-hydroxyphthaloyl Amine, filter and recover N-hydroxyphthalimide, add 0.49g dehydrating agent Pt / C to the filtrate, stir and react at 0°C for 10 hours, after the reaction is complete, filter and recover Pt / C, add sodium hydroxide Aqueous solution, pH ≥ 13, hydrolyzed at 50°C for 1 hour, separated to remove the water phase, and concentrated the organic phase to obtain a light yellow solid. The crude product was recrystallized with 20 mL of methanol to obtain 3.62 g of 25-hydroxy-7-ketocholesterol. 87% yield, white solid, melting point 178~180℃, 1 HNMR (CDCl 3 , 400MHz): δ 5.67 (d, 1H, 6-CH), 3.66 (m, 1H, 3-CH)...

Embodiment 2

[0028] At room temperature (20-25°C), dissolve 4.86 g (10 mmol) of 25-hydroxycholesterol diacetate in 50 mL of butanone, add 1.63 g (10 mmol) of N-hydroxyphthalimide, 48 mg of benzoyl peroxide, stirred evenly and continued to pass in the air, reacted for 8 hours, TLC traced to the complete reaction of 25-hydroxycholesterol diacetate, cooled down to 0°C, and the catalyst N-hydroxyphthaloyl was precipitated Imine, filtered, recovered N-hydroxyphthalimide, added 2.02g (20 mmol) triethylamine and 3.81g (20 mmol) p-toluenesulfonyl chloride to the filtrate, stirred and reacted at 0°C for 8 hours, After the reaction is complete, filter to remove salt, add 20% aqueous sodium hydroxide solution, control pH ≥ 13, hydrolyze at 50°C for 1 hour, remove the aqueous phase by layering, and concentrate the organic phase to obtain a light yellow solid. The crude product is recrystallized with 20 mL of methanol 3.41 g of 25-hydroxy-7-ketocholesterol was obtained as a white solid with a yield of ...

Embodiment 3

[0030] At room temperature (20-25°C), dissolve 4.86 g (10 mmol) of 25-hydroxycholesterol diacetate in 50 mL of acetone, add 1.15 g (10 mmol) of N-hydroxysuccinimide, and 48 mg Oxidize benzoyl, stir evenly and continue to feed air, react for 12 hours, after TLC tracking the reaction is complete, cool down to 0°C, precipitate the catalyst, filter, recover N-hydroxysuccinimide, add Pt / C to the filtrate 0.49g, stirred and reacted at 0°C for 10 hours. After the reaction is complete, filter and recover Pt / C, add aqueous sodium hydroxide solution, control pH ≥ 13, hydrolyze at 50°C for 1 hour, remove the aqueous phase by layering, and concentrate the organic phase to obtain a light yellow solid. The crude product is recrystallized with 20 mL of methanol 3.37 g of 25-hydroxy-7-ketocholesterol was obtained, with a yield of 81%, as a white solid with a melting point of 177-179°C.

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Abstract

The present invention relates to a synthesis method for 25-hydroxy-7-ketocholesterol. The method comprises: using a 25-hydroxycholesterol derivative as a raw material in an organic solvent, initiating by an initiator in the presence of an N-hydroxy catalyst; reacting 1-40 hours at a temperature of 0 DEG C-150 DEG C with air or oxygen; performing dehydration reaction for 1-20 hours by adding a dehydrant at a temperature of -20 DEG C-100 DEG C after completion of the reaction; then performing hydrolysis reaction for 1-2 hours at a temperature of 50 DEG C-80 DEG C; and obtaining 25-hydroxy-7-ketocholesterol after separation treatment of the reaction solution. The raw materials and reagents used in the present invention are readily available and environmentally-friendly. The synthesis method for 25-hydroxy-7-ketocholesterol provided by the present invention avoids the use of the metal Cr, the oxidant PCC and the like that pollute the environment seriously, and is good in reaction sclectivity, high in yield, low in cost, simple in treatment thereafter, less in three wastes, easy in product separation and high in purity.

Description

technical field [0001] The invention relates to a method for synthesizing 25-hydroxyl-7-ketocholesterol. Background technique [0002] 25-hydroxy-7-ketocholesterol can be used as a synthetic 25-hydroxyvitamin D 3 The key intermediate of 25-hydroxyvitamin D 3 Also known as calcifediol, vitamin D 3 The active metabolite has stronger physiological activity and does not need to be metabolized by the liver. [0003] 25-Hydroxyvitamin D 3 The market prospect is very good, so the market potential of the key intermediate 25-hydroxy-7-ketocholesterol is very large. Before the present invention, 25-hydroxyl-7-ketocholesterol was generally obtained from 25-hydroxycholesterol ester by oxidation and hydrolysis with PCC (Steroids, 2000, 65 (9), 529-535; PCT Int. Appl., 2010066689). Methods as below: [0004] [0005] The above method uses PCC, an oxidizing agent containing heavy metal Cr, which is used in a large amount and is cumbersome to post-treatment, produces a large amoun...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07J9/00
CPCC07J9/00
Inventor 金灿苏为科王子强刘建刚
Owner ZHEJIANG UNIV OF TECH
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