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Method for synthetizing dehydropregnenolone acetate and isotype substance thereof

A kind of technology of gestational dienolone acetate and similar substances, applied in the field of steroid drug raw material manufacturing, can solve the problems of large consumption of organic solvent, complicated operation and the like, and achieve the effects of saving organic solvent and reducing production and labor costs

Inactive Publication Date: 2012-03-28
TIANJIN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the product needs to be purified by column chromatography, which consumes a large amount of organic solvent
[0004] In the applicant's patent application (CN101974057A), applicants and others use water as a solvent and vanadium compounds as catalysts, and hydrogen peroxide oxidizes pseudosapogenin to synthesize diene. The advantage is that the reaction does not require an organic solvent, but the product needs to be processed by a volatile solvent Extraction, the operation is more complicated

Method used

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  • Method for synthetizing dehydropregnenolone acetate and isotype substance thereof
  • Method for synthetizing dehydropregnenolone acetate and isotype substance thereof
  • Method for synthetizing dehydropregnenolone acetate and isotype substance thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0018] Oxidation of pseudodiosgenin acetate to gestational dienolone acetate:

[0019] Put 50 g of diosgenin in a pressurized kettle, add acetic anhydride and acetic acid to dissolve, heat for 1 hour, recover acetic acid and acetic anhydride under reduced pressure, and recrystallize the obtained crude pseudodiosgenin acetate with methanol to obtain pseudodiosgenin B Pure esters.

[0020] In the reaction flask, add 10g (20mmol) pseudodiosgenin acetate and 25mL acetic acid, then add 0.07g (0.2mmol) Na(NH 4 ) 2 VO 4 .Na 2 NH 4 VO 4 , 4.56g (40mmol) hydrogen peroxide (30%H 2 o 2 ), the reaction was stirred at 5°C for 10 hours. Add 1.9g sodium acetate, react for 2 hours at 80°C, add water, precipitate out, crystallize with ethanol, and obtain 5.5g acetate dienolone by filtration, the product yield is 77%, m.p.165-167°C, proton nuclear magnetic resonance spectrum ( 400MHz, CDCl 3 )δ: 6.72(dd, J=2Hz, 1H, 16-H), 5.40(d, J=5.2Hz, 1H, 6-H), 4.62(m, 1H, 3-H), 2.02(s, 3H , 3-CH...

Embodiment 2

[0022] Oxidation of sisal-genin acetate to 3β-acetoxy-5α-pregna-16(17)-en-20-one:

[0023] Put 50g of sisal sapogenin in a pressurized kettle, add acetic anhydride and acetic acid to dissolve, heat for 1 hour, recover acetic acid and acetic anhydride under reduced pressure, and recrystallize the obtained crude pseudo sisal sapogenin acetate with methanol to obtain pseudo sisal Pure saponin acetate.

[0024] In the reaction flask, add 10g (20mmol) pseudosisalin acetate and 15mL acetic acid, then add 0.15g (0.8mmol) V 2 o 5 , 22.8g (200mmol) hydrogen peroxide (30%H 2 o 2 ), stirred and reacted at 40° C. for 2 hours. Add 1.9g of sodium acetate, react at 110°C for 5 hours, add water, precipitate out, crystallize with ethanol, and obtain 5.6g of 3β-acetoxy-5α-pregna-16(17)-en-20-one by filtration. The rate is 78%. m.p.162-165℃, hydrogen nuclear magnetic resonance spectrum (400MHz, CDCl 3 )δ: 6.70(dd, J=2Hz, 1H, 16-H), 4.70(m, 1H, 3-H), 2.04(s, 3H, 3-CH 3 COO), 2.27 (s, 3H, ...

Embodiment 3

[0026] Oxidation of pseudo-9(11)-deshydrosisalin acetate to 3β-acetoxy-5α-pregna-9(11),16(17)-dien-20-one:

[0027] In the reaction flask, add 10g (20mmol) pseudo-9(11)-dehydrosisalin acetate and 35mL acetic acid, then add 69.6g (200mmol) vanadium acetylacetonate, 5.7g (50mmol) hydrogen peroxide (30%H 2 o 2 ), stirred and reacted at 40° C. for 2 hours. Add 1.9g of sodium acetate, react at 110°C for 0.5 hours, add water, precipitate out, crystallize with ethanol, and filter to obtain 6.5g of 3β-acetoxy-5α-pregna-9(11), 16(17)-diene- 20-keto. Yield 91%. m.p.165-189℃, hydrogen nuclear magnetic resonance spectrum (400MHz, CDCl 3 )δ: 6.72(dd, J=2Hz, 1H, 16-H), 5.37(d, J=5.6Hz, 1H, 11-H), 4.69(m, 1H, 3-H), 2.04(s, 3H , 3-CH 3 COO-), 2.29 (s, 3H, 21-H), 0.82 (s, 3H, 18-H), 0.87 (s, 3H, 19-H) ppm.

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Abstract

The invention discloses a method for preparing dehydropregnenolone acetate and an isotype substance thereof. The method comprises the following steps of: adding pseudo steroid sapogenin acetic ester, a vanadium-containing compound catalyst and hydrogen peroxide into acetic acid according to a molar ratio; performing a stirring reaction for 2 to 10 hours at a temperature of 5 to 110 DEG C; adding sodium acetate into the obtained product and preserving heat for 0.5 to 4 hours at a temperature of 80 to 110 DEG C; adding water to precipitate; and crystallizing precipitates by methanol or ethanol to obtain the dehydropregnenolone acetate and the isotype substance thereof. The method has the advantages that various defects of the existing method are overcome; the product does not need to be subjected column chromatography purification; the production and labor cost is reduced; a great amount of organic solvents are saved; and a used oxidizing agent is hydrogen peroxide and is low and safe, no byproduct is generated, and the method has low production cost and is beneficial to the environment.

Description

technical field [0001] The invention relates to a preparation method of acetic acid gestational dienolone and its congeners, belonging to the raw material manufacturing technology of steroid medicines. Background technique [0002] Pregnancy dienolone acetate, also known as diene, is an important intermediate of steroid drugs, and its output in my country exceeds 1,000 tons. Since the forties of last century, this product has been produced by Marker degradation reaction (Marker: J.Am.Chem.Soc., 1940,62,2537; J.Am.Chem.Soc., 1941,63,774; Marker : J.Am.Chem.Soc., 1947,69,1267), the productive rate of gained acetic acid pregnancy dienolone is about 65%, and a big defect of this method is to use stoichiometric chromium trioxide as oxidant , Chromium trioxide is toxic and a strong carcinogen, for which there have been many improvements in recent years. Foreign researchers used ruthenium trichloride to catalyze the oxidation (Konwar: IN 2004DE01757) and KMnO 4 Oxidation (Konwar...

Claims

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Application Information

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IPC IPC(8): C07J13/00
Inventor 李春葆李博
Owner TIANJIN UNIV
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