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Preparation method of 16-dehydropregnenolone acetate and 16-dehydropregnenolone acetate congeners

A technology of gestational dienolone acetate and its congeners is applied in the field of green preparation of gestational dienolone acetate and its congeners, can solve the problems of complex production process, pollute the environment, increase costs and the like, achieve high yield, The effect of reducing production and labor costs

Inactive Publication Date: 2011-02-16
TIANJIN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] 1) Oxidation and elimination reactions are carried out in organic solvents, and the solvents are not easy to recover, which increases the cost and pollutes the environment
[0005] 2) The catalyst cannot be recycled, which increases the cost and pollutes the environment
[0006] 3) Oxidation and elimination reactions cannot be carried out simultaneously in one pot, and an equivalent amount of alkali is required to eliminate them, which makes the production process complicated

Method used

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  • Preparation method of 16-dehydropregnenolone acetate and 16-dehydropregnenolone acetate congeners
  • Preparation method of 16-dehydropregnenolone acetate and 16-dehydropregnenolone acetate congeners
  • Preparation method of 16-dehydropregnenolone acetate and 16-dehydropregnenolone acetate congeners

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0031] Oxidation of pseudodiosgenin acetate to gestational dienolone acetate:

[0032] 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.

[0033] In the reaction bottle, suspend 10g (20mmol) pseudodiosgenin acetate in 15mL water, add 10g tetrafluoroethylene particles (particle size 0.5-5cm), 1.2g (3mmol) methyl trioctyl ammonium chloride, 0.15 g(0.8mmol)V 2 o 5 , 5.7g (50mmol) hydrogen peroxide (30%H 2 o 2 ), mechanically stirred in an oil bath at 85°C for 5.5 hours. Pour out the water layer and keep it for the next recycling. The residue is continuously extracted with petroleum ether until there is no product in the chromatographic detection. The remaining residue is reserved for the next recycling. Concentrate the extract to reco...

Embodiment 2

[0035] Recycle catalyst oxidation pseudodiosgenin acetate to become the reaction system of gestational dienolone acetate (connected to Example 1):

[0036] Add the reclaimed water layer and crystallization mother liquor recovery to the residual system after petroleum ether extraction, then add 10g (20mmol) pseudodiosgenin acetate, 5.7g (50mmol) hydrogen peroxide (30%H 2 o 2 ), mechanically stirred in an oil bath at 85°C for 5.5 hours. Pour out the water layer (reserved for next recycling), and the residue is continuously extracted several times with petroleum ether until no product is detected by chromatography (residue is reserved for next recycling), concentrated and recovered petroleum ether (reserved for next recycling), and then purified with methanol Recrystallization (methanol and its residues recovered from the mother liquor are reserved for the next cycle) to obtain acetic acid pregnant dienolone, and the product characterization data are the same as in Example 1. T...

Embodiment 3

[0038] Oxidation of sisal-genin acetate to 3β-acetoxy-5α-pregna-16(17)-en-20-one:

[0039] 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.

[0040] In a reaction flask, suspend 10g (20mmol) of pseudosisalin acetate in 50mL of water, add 10g of tetrafluoroethylene particles, 1.2g (3mmol) of methyl trioctyl ammonium chloride, 0.15g (0.8mmol) of V 2 o 5 , 5.7g (50mmol) hydrogen peroxide (30%H 2 o 2 ), mechanically stirred in an oil bath at 85°C for 5.5 hours. Pour out the water layer (reserve for next cycle use), the residue is continuously extracted several times with normal hexane until no product is detected by chromatography (residue is reserved for next cycle use), concentrated crystallization (n-hexane and its r...

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Abstract

The invention discloses a preparation method of 16-dehydropregnenolone acetate and 16-dehydropregnenolone acetate congeners. The method comprises the following steps of: performing one-pot reaction on pseudo-steroid sapogenin acetate, a vanadium-containing compound catalyst, a quaternary ammonium compound catalyst and hydrogen peroxide in a molar ratio at the temperature of between 55 and 100 DEG C with mechanical stirring in a reactor for 3 to 24 hours so as to obtain a reaction solid-liquid mixture; and performing post-treatment on the reaction solid-liquid mixture so as to obtain the 16-dehydropregnenolone acetate and the 16-dehydropregnenolone acetate congeners, namely, 3 beta-acetoxyl group-5 alpha-pregnene-16(17)-alkene-20-ketone, 3 beta-acetoxyl group-5 beta-pregnene-16(17)-alkene-20-ketone or 3 beta-acetoxyl group-5 alpha-pregnene-9(11),16(17)-diene-20-ketone. The preparation method has the advantages that: oxidation and elimination are realized in one pot; an organic solvent is not used in the reaction; and the catalysts are used circularly, so that high yield, low cost and environmental protection are realized.

Description

technical field [0001] The invention relates to a green preparation method of acetic acid gestational dienolone and its congeners, which belongs to the raw material manufacturing technology of steroid medicines. Background technique [0002] Steroid drugs are the second largest class of drugs after antibiotics, and the annual output value of steroid drugs in the world reached 20 billion US dollars in 2000. Pregnancy dienolone acetate (referred to as "diene" in the industry) is an important steroid drug raw material, with a production capacity of about 1,000 tons in my country and about 4,000 tons in the world. [0003] Pregnancy dienolone acetate is produced by the Marker method (Marker: J.Am.Chem.Soc., 1940, 62, 2537; J.Am.Chem.Soc., 1941, 63, 774; Marker: J.Am.Chem .Soc., 1947,69,1267), that is, cracking diosgenin is pseudodiosgenin, and pseudodiosgenin is oxidized in acetic acid through chromium trioxide, and then eliminated under alkaline conditions, the yield of gained...

Claims

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Application Information

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IPC IPC(8): C07J13/00
CPCY02P20/584
Inventor 李春葆崔晓雪刘天真李博褚国彪
Owner TIANJIN UNIV
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