阅读说明：本技术 一种双烯醇酮醋酸酯提取工艺 (Process for extracting dehydropregnenolone acetate ) 是由 陈孝华 邓海锋 张兴军 于 2020-12-18 设计创作，主要内容包括：本发明涉及双烯醇酮醋酸酯提取技术领域,且公开了一种双烯醇酮醋酸酯提取工艺,包括以下步骤：取5-15份乙酸酐和10-30份乙酸混合,并将10-30份皂角苷投入乙酸酐和乙酸混合液内。该双烯醇酮醋酸酯提取工艺,通过使用乙酸酐和乙酸与皂角苷进行开环反应,使得到的溶液能够被氧化,然后通过使用双氧水来取代传统的三氧化铬作为氧化剂,不仅生产成本低,且几乎无污染,多余的双氧水处理起来也比较简单,只需要倒入亚硫酸钠使之与双氧水反应,得到硫酸钠和水,而硫酸钠在最后一步过滤中可以得到分层回收,相比采用三氧化铬作为氧化剂,生产成本低且污染性低,得到的产物也能回收利用,反应过程也比较温和,容易控制,达到了环保性好的目的。(The invention relates to the technical field of dehydropregnenolone acetate extraction, and discloses a dehydropregnenolone acetate extraction process, which comprises the following steps: mixing 5-15 parts of acetic anhydride and 10-30 parts of acetic acid, and adding 10-30 parts of saponin into the mixed solution of acetic anhydride and acetic acid. According to the dehydropregnenolone acetate extraction process, acetic anhydride, acetic acid and saponin are subjected to a ring-opening reaction, so that the obtained solution can be oxidized, hydrogen peroxide is used for replacing the traditional chromium trioxide as an oxidant, the production cost is low, almost no pollution is caused, the treatment of redundant hydrogen peroxide is simpler, sodium sulfite is only required to be poured to react with the hydrogen peroxide, sodium sulfate and water are obtained, the sodium sulfate can be recovered in a layered manner in the last filtering step, compared with the process of adopting chromium trioxide as the oxidant, the production cost is low, the pollution is low, the obtained product can be recycled, the reaction process is mild and easy to control, and the purpose of good environmental friendliness is achieved.)

1. The process for extracting the dehydropregnenolone acetate is characterized by comprising the following steps of:

1) mixing 5-15 parts of acetic anhydride and 10-30 parts of acetic acid, adding preferably 10-30 parts of saponin into the mixed solution of acetic anhydride and acetic acid, and heating and refluxing for 1-3 hours to obtain a ring-opening mixed solution;

2) cooling the ring-opening mixed solution obtained in the step 1) to 45 ℃, adding 2-6 parts of oxidant for oxidation reaction, and reacting for 1-3 hours under the stirring action to obtain an oxide mixed solution;

3) adding 2-6 parts of an impurity removing agent into the oxide mixed solution obtained in the step 2), stirring for 0.5-1.5 hours, adding a proper amount of water, and heating for hydrolysis for 1-3 hours to obtain a hydrolysis solution;

4) adding 15-25 parts of hexahydrobenzene into the hydrolysis solution obtained in the step 3) for extraction and liquid separation to obtain a residue, adding 5-15 parts of ethanol into the residue, and heating and dissolving to obtain a dissolved solution;

5) and (3) cooling and standing the solution obtained in the step 4), precipitating white crystals, and then filtering the solution to obtain the dehydropregnenolone acetate solid.

2. The extraction process of dehydropregnenolone acetate as claimed in claim 1, wherein the extraction process comprises the following steps: the heating reflux temperature in the step 1) is 200 ℃, and the heating reflux pressure in the step 1) is 0.05 MPa.

3. The extraction process of dehydropregnenolone acetate as claimed in claim 1, wherein the extraction process comprises the following steps: the oxidant in the step 2) is hydrogen peroxide, and the oxidation reaction in the step 2) is completed in a stirring reaction kettle.

4. The extraction process of dehydropregnenolone acetate as claimed in claim 1, wherein the extraction process comprises the following steps: the impurity removing agent in the step 3) is sodium sulfite, and the hydrolysis temperature in the step 3) is 80 ℃.

5. The extraction process of dehydropregnenolone acetate as claimed in claim 1, wherein the extraction process comprises the following steps: the heating and dissolving temperature in the step 4) is 60 ℃, and the liquid obtained after the extraction and liquid separation in the step 4) is a cyclohexane layer.

6. The extraction process of dehydropregnenolone acetate as claimed in claim 1, wherein the extraction process comprises the following steps: the liquid obtained after filtering in the step 5) except the solid of the dehydropregnenolone acetate contains sodium sulfate and acetic acid, and both the sodium sulfate and the acetic acid can be recycled in a layered manner.

Technical Field

The invention relates to the technical field of dehydropregnenolone acetate extraction, in particular to a dehydropregnenolone acetate extraction process.

Background

The dehydropregnenolone acetate is an important intermediate for synthesizing steroid hormone raw material medicines, and can be used as a raw material for producing adrenal hormone medicines, glucocorticoid medicines, steroid anti-inflammatory medicines, sex hormone medicines, female oral contraceptives and the like.

Various processes for extracting dehydropregnenolone acetate in the market at present generally have the defect of poor environmental protection effect, and the conventional dehydropregnenolone acetate process generally adopts chromium trioxide and other substances as an oxidant to complete an oxidation reaction, but the oxidation mode reaction is severe, and the generated intermediate is difficult to treat and has strong pollution, so that the dehydropregnenolone acetate extraction process is provided to solve the problems.

Disclosure of Invention

Technical problem to be solved

Aiming at the defects of the prior art, the invention provides a dehydropregnenolone acetate extraction process, which has the advantages of good environmental protection effect and the like, and solves the problems that substances such as chromium trioxide and the like are generally adopted as oxidants to complete oxidation reaction in the conventional dehydropregnenolone acetate process, but the oxidation mode has violent reaction, and the generated intermediate is difficult to treat and has strong pollution.

(II) technical scheme

In order to achieve the purpose of good environment protection effect, the invention provides the following technical scheme: a technology for extracting dehydropregnenolone acetate comprises the following steps:

1) mixing 5-15 parts of acetic anhydride and 10-30 parts of acetic acid, adding preferably 10-30 parts of saponin into the mixed solution of acetic anhydride and acetic acid, and heating and refluxing for 1-3 hours to obtain a ring-opening mixed solution;

2) cooling the ring-opening mixed solution obtained in the step 1) to 45 ℃, adding 2-6 parts of oxidant for oxidation reaction, and reacting for 1-3 hours under the stirring action to obtain an oxide mixed solution;

3) adding 2-6 parts of an impurity removing agent into the oxide mixed solution obtained in the step 2), stirring for 0.5-1.5 hours, adding a proper amount of water, and heating for hydrolysis for 1-3 hours to obtain a hydrolysis solution;

4) adding 15-25 parts of hexahydrobenzene into the hydrolysis solution obtained in the step 3) for extraction and liquid separation to obtain a residue, adding 5-15 parts of ethanol into the residue, and heating and dissolving to obtain a dissolved solution;

5) and (3) cooling and standing the solution obtained in the step 4), precipitating white crystals, and then filtering the solution to obtain the dehydropregnenolone acetate solid.

Preferably, the heating reflux temperature in the step 1) is 200 ℃, and the heating reflux pressure in the step 1) is 0.05 Mpa.

Preferably, the oxidant in the step 2) is hydrogen peroxide, and the oxidation reaction in the step 2) is completed in a stirring reaction kettle.

Preferably, the impurity removing agent in the step 3) is sodium sulfite, and the hydrolysis temperature in the step 3) is 80 ℃.

Preferably, the heating and dissolving temperature in the step 4) is 60 ℃, and the liquid obtained after the extraction and liquid separation in the step 4) is a cyclohexane layer.

Preferably, the liquid obtained after the filtration in the step 5) contains sodium sulfate and acetic acid except the solid of the dehydropregnenolone acetate, and both the sodium sulfate and the acetic acid can be recycled in layers.

(III) advantageous effects

Compared with the prior art, the invention provides a dehydropregnenolone acetate extraction process, which has the following beneficial effects:

1. according to the dehydropregnenolone acetate extraction process, acetic anhydride, acetic acid and saponin are subjected to a ring-opening reaction, so that the obtained solution can be oxidized, hydrogen peroxide is used for replacing the traditional chromium trioxide as an oxidant, the production cost is low, almost no pollution is caused, the treatment of redundant hydrogen peroxide is simpler, sodium sulfite is only required to be poured to react with the hydrogen peroxide, sodium sulfate and water are obtained, the sodium sulfate can be recovered in a layered manner in the last filtering step, compared with the process of adopting chromium trioxide as the oxidant, the production cost is low, the pollution is low, the obtained product can be recycled, the reaction process is mild and easy to control, and the purpose of good environmental friendliness is achieved.

2. According to the dehydropregnenolone acetate extraction process, the residues are washed and dissolved by ethanol, impurities in dehydropregnenolone acetate can be removed, the purity of dehydropregnenolone acetate crystals obtained finally after filtration is higher, the cost of hydrogen peroxide, sodium sulfite, hexahydrobenzene, ethanol and other substances used in the extraction process is lower, the extraction cost is effectively reduced, the layered hexahydrobenzene can be recovered from residual liquid for reuse after the hexahydrobenzene is used for extraction, acetic acid can be recovered from liquid obtained after final filtration for ring-opening reaction, the extraction cost is saved, and the purpose of low cost is achieved.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The first embodiment is as follows: a technology for extracting dehydropregnenolone acetate comprises the following steps:

1) mixing 5 parts of acetic anhydride and 10 parts of acetic acid, adding preferably 10 parts of saponin into the mixed solution of the acetic anhydride and the acetic acid, and heating and refluxing for 1 hour to obtain an open-loop mixed solution;

2) cooling the ring-opening mixed solution obtained in the step 1) to 45 ℃, adding 2 parts of oxidant for oxidation reaction, and reacting for 1 hour under the stirring action to obtain an oxide mixed solution;

3) adding 2 parts of impurity removing agent into the oxide mixed solution obtained in the step 2), stirring for 0.5 hour, adding a proper amount of water, and heating for hydrolysis for 1 hour to obtain a hydrolysis solution;

4) adding 15 parts of hexahydrobenzene into the hydrolysis solution obtained in the step 3) for extraction and liquid separation to obtain a residue, adding parts of ethanol into the residue, and heating and dissolving to obtain a dissolved solution;

5) and (3) cooling and standing the solution obtained in the step 4), precipitating white crystals, and then filtering the solution to obtain the dehydropregnenolone acetate solid.

Example two: a technology for extracting dehydropregnenolone acetate comprises the following steps:

1) mixing 10 parts of acetic anhydride and 20 parts of acetic acid, adding preferably 20 parts of saponin into the mixed solution of the acetic anhydride and the acetic acid, and heating and refluxing for 2 hours to obtain an open-loop mixed solution;

2) cooling the ring-opening mixed solution obtained in the step 1) to 45 ℃, adding 4 parts of oxidant to carry out oxidation reaction, and reacting for 2 hours under the stirring action to obtain an oxide mixed solution;

3) adding 4 parts of impurity removing agent into the oxide mixed solution obtained in the step 2), stirring for 1 hour, adding a proper amount of water, and heating for hydrolysis for 2 hours to obtain a hydrolysis solution;

4) adding 20 parts of hexahydrobenzene into the hydrolysis solution obtained in the step 3) for extraction and liquid separation to obtain a residue, adding 10 parts of ethanol into the residue, and heating and dissolving to obtain a dissolved solution;

5) and (3) cooling and standing the solution obtained in the step 4), precipitating white crystals, and then filtering the solution to obtain the dehydropregnenolone acetate solid.

Example three: a technology for extracting dehydropregnenolone acetate comprises the following steps:

1) mixing 15 parts of acetic anhydride and 30 parts of acetic acid, adding preferably 30 parts of saponin into the mixed solution of the acetic anhydride and the acetic acid, and heating and refluxing for 3 hours to obtain an open-loop mixed solution;

2) cooling the ring-opening mixed solution obtained in the step 1) to 45 ℃, adding 6 parts of oxidant for oxidation reaction, and reacting for 3 hours under the stirring action to obtain an oxide mixed solution;

3) adding 6 parts of impurity removing agent into the oxide mixed solution obtained in the step 2), stirring for 1.5 hours, adding a proper amount of water, and heating for hydrolysis for 3 hours to obtain a hydrolysis solution;

4) adding 25 parts of hexahydrobenzene into the hydrolysis solution obtained in the step 3) for extraction and liquid separation to obtain a residue, adding 15 parts of ethanol into the residue, and heating and dissolving to obtain a dissolved solution;

5) and (3) cooling and standing the solution obtained in the step 4), precipitating white crystals, and then filtering the solution to obtain the dehydropregnenolone acetate solid.

The invention has the beneficial effects that: the method has the advantages that the acetic anhydride, acetic acid and saponin are subjected to ring-opening reaction to enable the obtained solution to be oxidized, then the hydrogen peroxide is used for replacing the traditional chromium trioxide as an oxidant, the production cost is low, almost no pollution is caused, the excessive hydrogen peroxide is simpler to treat, sodium sulfite is only required to be poured to react with the hydrogen peroxide to obtain sodium sulfate and water, the sodium sulfate can be recycled in a layered mode in the last step of filtration, compared with the method that the chromium trioxide is used as the oxidant, the production cost is low, the pollution is low, the obtained product can be recycled, the reaction process is mild and easy to control, the purpose of good environmental friendliness is achieved, impurities in the dehydropregnenolone acetate can be removed by washing and dissolving residues through ethanol, the dehydropregnenolone acetate crystal finally obtained through filtration is higher in purity, and the hydrogen peroxide used in the extraction process, The cost of sodium sulfite, hexahydrobenzene, ethanol and other substances is low, the extraction cost is effectively reduced, layered hexahydrobenzene can be recovered from the residual liquid for reuse after the hexahydrobenzene is used for extraction, acetic acid can be recovered from the liquid obtained after final filtration for ring-opening reaction, the extraction cost is saved, and the purpose of low cost is achieved.

Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.