CN114736144A - Industrial preparation method of docusate calcium - Google Patents
Industrial preparation method of docusate calcium Download PDFInfo
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- CN114736144A CN114736144A CN202210455718.4A CN202210455718A CN114736144A CN 114736144 A CN114736144 A CN 114736144A CN 202210455718 A CN202210455718 A CN 202210455718A CN 114736144 A CN114736144 A CN 114736144A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/42—Separation; Purification; Stabilisation; Use of additives
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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Abstract
The invention belongs to the technical field of pharmaceutical chemicals, and particularly relates to an industrial preparation method of docusate calcium. According to the preparation method, maleic anhydride and 2-ethylhexanol are used as initial raw materials, p-toluenesulfonic acid is used for catalyzing the raw materials to form ester, the ester is sulfonated with sodium bisulfite in an alcohol water solution, then calcium salt is prepared through 'one-pot boiling', a docusate calcium crude product is obtained, and finally pure water is used for refining, and a docusate calcium finished product is obtained. The method solves the problem of 2-ethylhexanol and sodium bisulfite residue, the yield of docusate calcium refining reaches 95%, the whole process route is short, the yield is high, the quality is reliable, the cost is low, and the method is suitable for industrial production and has extremely high application value.
Description
Technical Field
The invention belongs to the technical field of pharmaceutical chemicals, and particularly relates to an industrial preparation method of docusate calcium.
Background
Calcium Docusate (Docusate calcium) with the chemical name 1,4-Bis (2-ethylhexyl) succinate sulfonate calcium salt, i.e., 1,4-Bis (2-ethylhexyl) sulfonate, calcium salt, CAS:128-49-4, molecular formula: C40H74CaO14S2, molecular weight: 883.22. it is used for treating constipation, and can be used as cathartic or stool softener. The efficacy of docusate calcium is consistent with that of docusate sodium, but the docusate sodium is a viscous product, is extremely inconvenient to dry, store and transport, and is difficult to realize industrial production. The docusate calcium is powdery solid, the product quality is easy to control, the transportation and the storage are convenient, and the docusate calcium can also be prepared into various other dosage forms, so that the docusate calcium has a wider prospect.
The prior art is mostly a preparation method of docusate sodium, and a preparation process of docusate calcium is not reported yet. Usually, maleic anhydride and 2-ethylhexanol are esterified under the action of inorganic acid or organic acid, and the obtained maleic acid di (2-ethyl) hexyl ester is sulfonated with sodium bisulfite to obtain docusate sodium. The esterification reaction usually uses excessive 2-ethyl hexanol, and the 2-ethyl hexanol has high boiling point and poor water solubility and is extremely difficult to remove cleanly. Even if the yield of maleic acid di (2-ethyl) hexyl ester is sacrificed and the amount of 2-ethylhexanol is reduced, the residue is inevitably generated due to the influence of esterification equilibrium reaction. In addition, the docusate sodium has excellent water solubility and fat solubility, and is difficult to refine and purify, and especially when excessive sodium bisulfite is used, the removal of inorganic salts is a difficult process.
In order to overcome the problems of docusate sodium, the invention reports an industrial preparation method of high-purity docusate calcium, and the docusate calcium is powdery solid, is convenient for post-treatment refining, drying, storage and transportation, is beneficial to product quality control, has strong market value and practical significance, can replace docusate sodium, and realizes industrialization.
Disclosure of Invention
The invention aims to overcome the defects in the preparation process of docusate sodium in the prior art and make up the blank of the domestic docusate calcium production process.
Therefore, the invention provides an industrial preparation method of docusate calcium, which comprises the following steps:
(1) esterification reaction: maleic anhydride and excessive 2-ethylhexanol are condensed into maleic acid di (2-ethyl) hexyl ester under the catalysis of p-toluenesulfonic acid, the maleic anhydride is supplemented after the reaction is finished, the maleic anhydride reacts with residual 2-ethylhexanol to obtain maleic acid mono (2-ethyl) hexyl ester, and the maleic acid mono (2-ethyl) hexyl ester impurity is removed through washing;
(2) and (3) sulfonation reaction: performing sulfonation reaction on the maleic acid di (2-ethyl) hexyl ester obtained in the step (1) and sodium bisulfite to obtain docusate sodium;
(3) preparation of calcium salt: directly reacting docusate sodium with calcium chloride to generate docusate calcium, concentrating after the reaction is finished, adding an organic solvent, filtering to remove salt, then adding pure water, evaporating to remove the organic solvent, crystallizing, and filtering to obtain a crude product of the docusate calcium;
(4) refining and purifying: and (3) adding the crude docusate calcium product into pure water for refining, and filtering to obtain a pure docusate calcium product.
Specifically, the esterification reaction in the step (1) is specifically as follows: the molar ratio of 1: and (1.9-2.2) condensing maleic anhydride and 2-ethylhexanol into maleic acid di (2-ethyl) hexyl ester under the catalysis of p-toluenesulfonic acid, wherein the solvent is toluene, 0.01-0.25 equivalent of maleic anhydride is added after the reaction is finished, the maleic anhydride reacts with residual 2-ethylhexanol to obtain maleic acid mono (2-ethyl) hexyl ester, and a washing solvent is used for removing impurities of the maleic acid mono (2-ethyl) hexyl ester.
Specifically, the molar mass of the p-toluenesulfonic acid in the step (1) is 0.5-5% of that of the maleic anhydride; the volume mass ratio of the toluene to the maleic anhydride is (0.5-2): 1.
specifically, the washing solvent in the step (1) includes at least one of water and an alkaline solution.
Specifically, the sulfonation reaction in the step (2) is specifically as follows: mixing a mixture of 1: and (1.05-1.3) refluxing and reacting the maleic acid di (2-ethyl) hexyl ester and sodium bisulfite in an alcohol-water mixed solvent, and ensuring complete sulfonation of the maleic acid di (2-ethyl) hexyl ester through intermediate control to obtain docusate sodium.
Specifically, the volume ratio of alcohol to water in the alcohol-water mixed solvent in the step (2) is 1: (1-3); the alcohol in the alcohol-water mixed solvent comprises at least one of methanol, ethanol and isopropanol.
Specifically, the calcium salt prepared in the step (3) is specifically: reacting docusate sodium with calcium chloride at room temperature to generate docusate calcium, wherein the molar ratio of the calcium chloride to the sodium bisulfite in the step (2) is (0.5-1): 1, concentrating after the reaction is finished until the water content is 0-50%, adding an organic solvent for crystallization, filtering to remove salt, then adding pure water into the filtrate, distilling to remove the organic solvent, crystallizing, and filtering to obtain a crude product of the docusate calcium.
Specifically, the organic solvent in step (3) includes at least one of methanol, ethanol, isopropanol, acetone, acetonitrile, and tetrahydrofuran.
Specifically, the volume-mass ratio of the organic solvent to the theoretical yield of the docusate calcium in the step (3) is (1-10): 1; the volume ratio of the pure water to the organic solvent is (2-20): 1.
specifically, the refining and purification in the step (4) are specifically as follows: adding the crude docusate calcium into pure water for refining, wherein the mass volume ratio of the crude docusate calcium to the pure water is 1: (3-20), refluxing and pulping at 10-100 ℃ to obtain a dispersed product, cooling and filtering to obtain a pure docusate calcium.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the industrial preparation method of the docusate calcium provided by the invention takes maleic anhydride and excessive 2-ethylhexanol as starting materials, under the catalytic action of p-toluenesulfonic acid, the maleic anhydride can be firstly reacted with the 2-ethylhexanol to generate mono (2-ethyl) hexyl maleate at room temperature, the reaction is easy to carry out, and the monoester and the 2-ethylhexanol are dehydrated at high temperature to generate di (2-ethyl) hexyl maleate. At this point the reaction reached an equilibrium where maleic anhydride was not present, but residual 2-ethylhexanol was present. In order to control the 2-ethylhexanol residue problem, the invention adds maleic anhydride at the end of the reaction to change the residual 2-ethylhexanol into monoester in a mode of breaking the reaction balance, the reaction process is rapid and sufficient, the generated maleic acid mono (2-ethyl) hexanol is acidic, has good water solubility and is easy to dissolve in alkaline aqueous solution, and the problem of 2-ethylhexanol residue can be smoothly solved by washing with water.
(2) The industrial preparation method of the docusate calcium provided by the invention reduces the feeding amount of sodium bisulfite as much as possible in the sulfonation reaction stage, adjusts the proportion of alcohol and water, and reduces the cost of raw and auxiliary materials. The preparation process of the calcium salt and the preparation process of the docusate sodium are carried out in a one-pot mode, and the docusate sodium directly reacts with calcium chloride without post-treatment after completely reacting to obtain the calcium salt. The calcium salt is easily soluble in organic solvent and insoluble in water, most of water can be removed by concentration, and inorganic salt impurities can be separated out by adding alcohol solution. And refining and purifying in water, removing residual inorganic salt, and obtaining high-purity docusate calcium, wherein the product is powdery solid and is easy to dry and post-treat.
(3) The industrial preparation method of the docusate calcium provided by the invention takes maleic anhydride and 2-ethylhexanol as initial raw materials, and high-purity docusate calcium is obtained through esterification, sulfonation, calcium salt preparation, refining and purification.
Detailed Description
The technical solutions in the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. Although representative embodiments of the present invention have been described in detail, it will be understood by those skilled in the art that various modifications and changes may be made thereto without departing from the scope of the invention. Therefore, the scope of the present invention should not be limited to the embodiments, but should be defined by the appended claims and equivalents thereof.
The invention provides an industrial preparation method of docusate calcium, which comprises the following steps:
(1) esterification reaction: the molar ratio of 1: (1.9-2.2), preferably 1: 2.0, maleic anhydride and 2-ethyl hexanol are condensed into di (2-ethyl) hexyl maleate under the catalysis of p-toluenesulfonic acid, the solvent is toluene, and the molar mass of the p-toluenesulfonic acid is 0.5-5%, preferably 1%, of the maleic anhydride; the volume mass ratio of the toluene to the maleic anhydride is (0.5-2): 1, preferably 1: 1. stirring for dissolving, heating, refluxing, separating water, and stopping heating when the temperature in the container is 145 deg.C and no water is separated. After the reaction is finished, 0.01 to 0.25 equivalent of maleic anhydride is added, preferably 0.05 equivalent of maleic anhydride is added, the mixture is continuously stirred and reacts for 0.5 to 1 hour, the mixture reacts with residual 2-ethylhexanol to obtain maleic acid mono (2-ethyl) hexyl ester, the mixture is cooled to room temperature, the mixture is sequentially washed by pure water, saturated sodium bicarbonate and pure water, and the mixture is decompressed and concentrated to remove impurities of the maleic acid mono (2-ethyl) hexyl ester, so that the maleic acid di (2-ethyl) hexyl ester is obtained. Based on the initial amount of maleic anhydride, the yield can reach 97%.
(2) And (3) sulfonation reaction: mixing the maleic acid di (2-ethyl) hexyl ester obtained in the step (1) and sodium bisulfite according to the proportion of 1: (1.05-1.3) in an alcohol-water mixed solvent, and the molar ratio is preferably 1: 1.1. the volume ratio of alcohol to water in the alcohol-water mixed solvent is 1: (1-3), preferably 1: 1.5, the alcohol in the alcohol-water mixed solvent comprises at least one of methanol, ethanol and isopropanol, and preferably ethanol. And (3) carrying out reflux reaction until no layering phenomenon exists, analyzing and controlling the residue of the maleic acid di (2-ethyl) hexyl ester to meet the standard, and ensuring that the maleic acid di (2-ethyl) hexyl ester is sulfonated to obtain docusate sodium.
(3) Preparation of calcium salt: reacting docusate sodium with calcium chloride at room temperature to generate docusate calcium, preferably performing reflux reaction, wherein the molar ratio of the calcium chloride to the sodium bisulfite in the step (2) is (0.5-1): 1, preferably 0.6: 1, the reaction time is more than 1 hour, preferably 2 to 3 hours. Concentrating until the water content is 0-50% after the reaction is finished, adding an organic solvent, stirring at room temperature for crystallization, filtering to remove salt, then adding pure water into the filtrate, distilling to remove the organic solvent, crystallizing, filtering and drying to obtain a crude product of the docusate calcium, wherein the total yield is about 92%. The organic solvent comprises at least one of methanol, ethanol, isopropanol, acetone, acetonitrile and tetrahydrofuran, preferably absolute ethanol and isopropanol, and especially absolute ethanol. The volume-mass ratio of the organic solvent to the theoretical yield of the docusate calcium is 1: (1-10), preferably 1: (1.5-3); the volume ratio of the pure water to the organic solvent is (2-20): 1, preferably (3-6): 1.
(4) refining and purifying: adding the docusate calcium crude product into a mixture with the mass volume ratio of 1: refining in pure water of (3-20), and pulping at 10-100 deg.C under reflux for more than 0.5 hr to obtain dispersed product, preferably pulping at 40-50 deg.C for 2-3 hr. Cooling and filtering, and drying the filter cake under reduced pressure to obtain the pure docusate calcium with the refining yield of about 95 percent.
The specific synthetic route is as follows:
the effect of the method for the industrial production of docusate calcium of the present invention is examined below with specific examples.
Example 1:
the embodiment provides an industrial preparation method of docusate calcium, which comprises the following steps:
(1) esterification reaction: in a 1000L reactor equipped with a water separator, mechanical stirring, a reflux condenser and a thermometer, 271kg (2.085kmol) of 2-ethylhexanol, 102kg (1.041kmol) of maleic anhydride, 100L of toluene and 2kg (0.012kmol) of p-toluenesulfonic acid were sequentially added with stirring and heated to reflux. The internal temperature is gradually increased from 120 ℃ to 145 ℃, the water obtained by separation is collected to reach the theoretical value, no water is evaporated, the water is continuously separated by refluxing for 0.5h, and the water separation is stopped. 5kg (0.051kmol) of maleic anhydride is added and stirred for 0.5 h. And cooling to room temperature to obtain a colorless or light yellow reaction solution. The mixture was washed with 400kg of pure water, 200kg of saturated sodium bicarbonate solution (2 washes), and 400kg of pure water in this order, and the organic phase was put in a 70-80 ℃ water bath and concentrated under reduced pressure to obtain 343.8kg (1.011kmol) of a pale yellow oily esterified maleic acid bis (2-ethyl) hexyl ester, having a GC purity of 98.6% and a 2-ethylhexanol content of 0.08%, and a yield of 97.1% based on the initial maleic anhydride charge.
(2) Sulfonation reaction: 343.8kg (1.011kmol) of maleic acid di (2-ethyl) hexyl ester prepared in the step (1), 180kg of ethanol, 115.6kg (1.112kmol) of sodium bisulfite and 340kg of pure water are sequentially added into a 2000L reaction kettle provided with a reflux condenser tube and a thermometer, heated to reflux and reacted for 18 h. The reaction liquid turns yellow and clear from white suspension, sampling and analyzing are carried out, the residue of the maleic acid di (2-ethyl) hexyl ester is controlled to meet the standard, and the sulfonation of the maleic acid di (2-ethyl) hexyl ester is ensured to obtain docusate sodium.
(3) Preparation of calcium salt: and (3) adding 73.9kg (0.666kmol) of calcium chloride into the docusate sodium prepared in the step (2) at room temperature, and carrying out reflux reaction for 3 hours to separate out a large amount of white solid. Concentrating under reduced pressure, and controlling water content to less than 50% to obtain viscous substance. Adding 700L of absolute ethyl alcohol at room temperature, stirring for 0.5h for dissolution, precipitating inorganic salt, and filtering for desalting. The filtrate was transferred to a kettle and 700L of pure water was added to precipitate a white thick solid. Concentrating under reduced pressure, removing ethanol, supplementing 1000L pure water, stirring at room temperature, crystallizing for 3 hr, and filtering to obtain wet crude product. Vacuum drying at 50-60 deg.C until water content is qualified to obtain 421.8kg (0.478kmol) of docusate calcium crude product with effective content of 98.6% and yield of 94.6%.
(4) Refining and purifying: 421.8kg (0.478kmol) of crude docusate calcium is added into 1500L of pure water, heated to 40-50 ℃ and stirred for 2 h. Cooling to room temperature, filtering, vacuum drying filter cake at 50-60 deg.C until water content is qualified to obtain 401.5kg (0.455kmol) pure docusate calcium with effective content of 99.3%, clarity detection and residue on ignition meeting standard, and refining yield of 95.2%.
The above examples are merely illustrative of the present invention and should not be construed as limiting the scope of the invention, which is intended to be covered by the claims.
Claims (10)
1. An industrial preparation method of docusate calcium is characterized by comprising the following steps:
(1) esterification reaction: maleic anhydride and excessive 2-ethylhexanol are condensed into maleic acid di (2-ethyl) hexyl ester under the catalysis of p-toluenesulfonic acid, the maleic anhydride is supplemented after the reaction is finished, the maleic anhydride reacts with residual 2-ethylhexanol to obtain maleic acid mono (2-ethyl) hexyl ester, and the maleic acid mono (2-ethyl) hexyl ester impurity is removed through washing;
(2) sulfonation reaction: performing sulfonation reaction on the maleic acid di (2-ethyl) hexyl ester obtained in the step (1) and sodium bisulfite to obtain docusate sodium;
(3) preparation of calcium salt: directly reacting docusate sodium with calcium chloride to generate docusate calcium, concentrating after the reaction is finished, adding an organic solvent, filtering to remove salt, then adding pure water, evaporating to remove the organic solvent, crystallizing, and filtering to obtain a crude product of the docusate calcium;
(4) refining and purifying: and (3) adding the crude docusate calcium product into pure water for refining, and filtering to obtain a pure docusate calcium product.
2. The industrial preparation method of docusate calcium as claimed in claim 1, wherein the esterification reaction in step (1) is specifically: the molar ratio of 1: and (1.9-2.2) condensing maleic anhydride and 2-ethylhexanol into maleic acid di (2-ethyl) hexyl ester under the catalysis of p-toluenesulfonic acid, wherein the solvent is toluene, 0.01-0.25 equivalent of maleic anhydride is added after the reaction is finished, the maleic anhydride reacts with residual 2-ethylhexanol to obtain maleic acid mono (2-ethyl) hexyl ester, and a washing solvent is used for removing impurities of the maleic acid mono (2-ethyl) hexyl ester.
3. The industrial process for the preparation of docusate calcium according to claim 2, wherein: the molar mass of the p-toluenesulfonic acid in the step (1) is 0.5-5% of that of maleic anhydride; the volume mass ratio of the toluene to the maleic anhydride is (0.5-2): 1.
4. the industrial process for the preparation of docusate calcium according to claim 2, wherein: the washing solvent in the step (1) comprises at least one of water and alkaline solution.
5. The industrial preparation method of docusate calcium as claimed in claim 1, wherein the sulfonation reaction in step (2) is specifically: mixing a mixture of 1: and (1.05-1.3) refluxing and reacting the bis (2-ethyl) hexyl maleate and sodium bisulfite in an alcohol-water mixed solvent, and ensuring complete sulfonation of the bis (2-ethyl) hexyl maleate by intermediate control to obtain docusate sodium.
6. The industrial process for the preparation of docusate calcium according to claim 5, wherein: in the step (2), the volume ratio of alcohol to water in the alcohol-water mixed solvent is 1: (1-3); the alcohol in the alcohol-water mixed solvent comprises at least one of methanol, ethanol and isopropanol.
7. The industrial preparation method of docusate calcium according to claim 1, wherein the calcium salt prepared in step (3) is specifically: reacting docusate sodium with calcium chloride at room temperature to generate docusate calcium, wherein the molar ratio of the calcium chloride to the sodium bisulfite in the step (2) is (0.5-1): 1, concentrating after the reaction is finished until the water content is 0-50%, adding an organic solvent for crystallization, filtering to remove salt, then adding pure water into the filtrate, distilling to remove the organic solvent, crystallizing, and filtering to obtain a crude product of the docusate calcium.
8. The industrial process for the preparation of docusate calcium according to claim 7, wherein: the organic solvent in the step (3) comprises at least one of methanol, ethanol, isopropanol, acetone, acetonitrile and tetrahydrofuran.
9. The industrial process for the preparation of docusate calcium according to claim 7, wherein: the volume mass ratio of the organic solvent to the docusate calcium in the step (3) is (1-10): 1; the volume ratio of the pure water to the organic solvent is (2-20): 1.
10. the industrial preparation method of docusate calcium as claimed in claim 1, wherein the refining and purification in step (4) is specifically: adding the crude docusate calcium into pure water for refining, wherein the mass volume ratio of the crude docusate calcium to the pure water is 1: (3-20), refluxing and pulping at 10-100 ℃ to obtain a dispersed product, cooling and filtering to obtain a pure docusate calcium.
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