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CN111777625A - Preparation method of ceftizoxime sodium for injection - Google Patents

Preparation method of ceftizoxime sodium for injection Download PDF

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Publication number
CN111777625A
CN111777625A CN202010506830.7A CN202010506830A CN111777625A CN 111777625 A CN111777625 A CN 111777625A CN 202010506830 A CN202010506830 A CN 202010506830A CN 111777625 A CN111777625 A CN 111777625A
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ceftizoxime
sodium
preparation
solution
acid
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CN111777625B (en
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贾全
张锁庆
田洪年
任峰
张建丽
刘树斌
魏宝军
杨梦德
贺娇
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Ncpc Hebei Huamin Pharmaceutical Co ltd
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D501/00Heterocyclic compounds containing 5-thia-1-azabicyclo [4.2.0] octane ring systems, i.e. compounds containing a ring system of the formula:, e.g. cephalosporins; Such ring systems being further condensed, e.g. 2,3-condensed with an oxygen-, nitrogen- or sulfur-containing hetero ring
    • C07D501/14Compounds having a nitrogen atom directly attached in position 7
    • C07D501/16Compounds having a nitrogen atom directly attached in position 7 with a double bond between positions 2 and 3
    • C07D501/207-Acylaminocephalosporanic or substituted 7-acylaminocephalosporanic acids in which the acyl radicals are derived from carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D501/00Heterocyclic compounds containing 5-thia-1-azabicyclo [4.2.0] octane ring systems, i.e. compounds containing a ring system of the formula:, e.g. cephalosporins; Such ring systems being further condensed, e.g. 2,3-condensed with an oxygen-, nitrogen- or sulfur-containing hetero ring
    • C07D501/02Preparation
    • C07D501/12Separation; Purification

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  • Organic Chemistry (AREA)
  • Cephalosporin Compounds (AREA)

Abstract

The invention relates to a preparation method of ceftizoxime sodium for injection, belonging to the technical field of medicines. The method comprises the following steps: (a) reducing the temperature of the purified water to 0-5 ℃; adding ceftizoxime acid into purified water, and adding a buffer solution; (b) adding a salt forming agent into the solution obtained in the step (a), controlling the temperature to be 0-5 ℃, and stirring until the solution is clear; (c) adding sodium chloride into the solution obtained in the step (b), and stirring until the solution is clear; (d) adding activated carbon into the filtrate obtained in the step (c) for decoloring, and filtering after decoloring; (e) controlling the temperature of the solution obtained in the step (d) to be 13-15 ℃, adding ethanol for the first time, then adding ceftizoxime sodium seed crystal, growing crystals, adding ethanol again after a large amount of crystals are produced, cooling, continuing to grow crystals, filtering, washing and drying to obtain ceftizoxime sodium powder; (f) and (e) aseptically packaging the ceftizoxime powder obtained in the step (e) to obtain the ceftizoxime sodium powder injection for injection. The product is easy for packaging powder injection.

Description

Preparation method of ceftizoxime sodium for injection
Technical Field
The invention relates to the technical field of medicines, in particular to a preparation method of ceftizoxime sodium for injection.
Background
Ceftizoxime sodium was first marketed in japan in 1982 under the trade name Ceftizox, the third generation of cephalosporin antibiotics developed by japan tenuzolk chemical industries, ltd. It is commonly used as third generation cephalosporin antibiotics. The traditional Chinese medicine composition is clinically used for treating lower respiratory tract infection, urinary tract infection, abdominal cavity infection, pelvic cavity infection, septicemia, skin soft tissue infection, bone and joint infection, meningitis caused by streptococcus pneumoniae or haemophilus influenzae and simple gonorrhea caused by sensitive bacteria. The chemical name is as follows: (6R,7R) -7- [ [2, 3-dihydro-2-imino-4-thiazolyl) (methoxyimino) acetyl ] amino ] -8-oxo-5-thia-1-azabicyclo [4.2.0] oct-2-ene-2-carboxylic acid sodium salt. The structural formula is as follows:
Figure BDA0002526830280000011
the synthesis preparation of ceftizoxime sodium and the purification process of the product are more, but the sterile crystallization preparation process of ceftizoxime sodium for injection is not introduced much, and the methods introduced in the patent and literature mainly comprise the following steps:
the patent "a method for refining ceftizoxime sodium" (CN109553626A) provides ceftizoxime sodium prepared by adding concentrated hydrochloric acid and sodium bicarbonate into ceftizoxime acid, the product has poor color grade, and various solvents are used in the crystallization process, so that the solvents are not beneficial to recycling; the patent of new ceftizoxime sodium crystal form for reducing anaphylactic reaction and a preparation thereof (CN105622635A) also has the problem that the crystallization of various solvents is difficult to recover.
The ceftizoxime sodium product prepared by the patents of a ceftizoxime sodium preparation and refining method (CN102911186A) and a ceftizoxime sodium preparation method (CN102807573A) also has the problem of poor color grade; meanwhile, the product purity is low, and the medication safety is influenced.
The patent (CN102079750A) provides a method for converting ceftizoxime sodium into ceftizoxime acid and then converting the ceftizoxime acid into ceftizoxime sodium, and the method has the advantages of complex process and high production cost. The same patent of high-purity ceftizoxime sodium and a preparation method thereof (CN101348492A) also has the problem of complex process.
A process for preparing ceftizoxime sodium (CN102603771A) features that sodium hydroxide is used as salt-forming agent, and the dissolving procedure is performed at high pH value to destroy the structure of product and influence its quality, resulting in high content of impurities.
Disclosure of Invention
The invention aims to provide a preparation method of ceftizoxime sodium for injection, which is a method for preparing ceftizoxime sodium for injection by using single solvent crystallization.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of ceftizoxime sodium for injection comprises the following steps:
(a) reducing the temperature of the purified water to 0-5 ℃; adding ceftizoxime acid into purified water, and adding a buffer solution;
(b) adding a salt forming agent into the solution obtained in the step (a), controlling the temperature to be 0-5 ℃, and stirring until the solution is clear;
(c) adding sodium chloride into the solution obtained in the step (b), and stirring until the solution is clear;
(d) adding activated carbon into the solution obtained in the step (c) for decoloring, and filtering after decoloring;
(e) controlling the temperature of the filtrate obtained in the step (d) to be 13-15 ℃, adding ethanol for the first time, then adding ceftizoxime sodium seed crystal, growing crystals, adding ethanol again after a large amount of crystals are produced, cooling, continuing to grow crystals, filtering, washing and drying to obtain ceftizoxime sodium powder;
(f) and (e) aseptically packaging the ceftizoxime sodium powder obtained in the step (e) to obtain the ceftizoxime sodium powder injection for injection.
The technical scheme of the invention is further improved as follows: in the step (a), the amount of the purified water is 2.0-2.5 times of the weight of the ceftizoxime acid.
The technical scheme of the invention is further improved as follows: in the step (a), the buffer solution is acetic acid-sodium acetate buffer solution; the adding amount is 0.1-0.2 time of the weight of ceftizoxime acid; preparing an acetic acid-sodium acetate buffer solution: 54.6g of sodium acetate is dissolved in 20mL of 1mol/L acetic acid solution, and then the solution is diluted to 500mL by adding water.
The technical scheme of the invention is further improved as follows: in the step (b), the salt forming agent is sodium acetate solution, and the molar ratio of the sodium acetate to the ceftizoxime acid is 1.05-1.15: 1; the water consumption for dissolving the sodium acetate is 4 to 5 times of the weight of the ceftizoxime acid; the addition time is 60-120 min.
The technical scheme of the invention is further improved as follows: in the step (c), the amount of the added sodium chloride is 0.1-0.2 time of the mass of the ceftizoxime acid.
The technical scheme of the invention is further improved as follows: the dosage of the active carbon used in the step (d) is 10 to 15 percent of the weight of the ceftizoxime acid, and the decoloring time is 30 to 60 min.
The technical scheme of the invention is further improved as follows: in the step (e), ethanol is added for the first time, the volume usage amount of the ethanol is 7-8 times of the weight of the ceftizoxime acid, and the amount of the added crystal seeds is 5% -7% of the weight of the ceftizoxime acid.
The technical scheme of the invention is further improved as follows: in the step (e), ethanol is added again, and the volume dosage of the ethanol is 55-60 times of the weight of the ceftizoxime acid.
The technical scheme of the invention is further improved as follows: in the step (e), the temperature is reduced, the crystal growing temperature is 0-2 ℃ in the crystal growing process, and the crystal growing time is 60-90 min.
Due to the adoption of the technical scheme, the invention has the following technical effects:
1. according to the ceftizoxime sodium for injection, the organic solvent used for crystallization is a single solvent and can be recycled, so that the product quality and the stability can be effectively improved; the addition of the buffer solution and the sodium chloride in the crystallization system can effectively improve the fluidity of the product and is easier for subpackaging the powder injection.
2. The preparation method is simple in technological process operation, and the prepared ceftizoxime sodium product for injection has the advantages of good stability, low color grade index, low impurity content and high product content.
3. The invention provides a novel method for preparing ceftizoxime sodium for injection; and industrialization is easy to realize.
4. The ceftizoxime sodium powder injection preparation for injection prepared by the invention has smaller angle of repose and better powder flowability, and can meet the requirement of flowability in the production process.
5. The invention is more suitable for preparing powder injection.
Detailed Description
The present invention will be described in further detail with reference to specific examples below:
a method for preparing ceftizoxime sodium for injection, which is easy to subpackage powder injection preparations.
The preparation method comprises the following steps:
(a) reducing the temperature of the purified water to 0-5 ℃; adding ceftizoxime acid into purified water, and adding a buffer solution; wherein the amount of the purified water is 2.0-2.5 times of the weight of the ceftizoxime acid. Preferably, the buffer used is an acetic acid-sodium acetate buffer; the adding amount is 0.1-0.2 times of the weight of ceftizoxime acid. The preparation method of the acetic acid-sodium acetate buffer solution comprises the following steps: 54.6g of sodium acetate is dissolved in 20mL of 1mol/L acetic acid solution, and then the solution is diluted to 500mL by adding water.
(b) Adding a salt forming agent into the solution obtained in the step (a), controlling the temperature to be 0-5 ℃, and stirring until the solution is clear. Preferably, the salt forming agent is sodium acetate solution, and the molar ratio of the sodium acetate to the ceftizoxime acid is 1.05-1.15: 1; the water consumption for dissolving the sodium acetate is 4 to 5 times of the weight of the ceftizoxime acid; the addition time is 60-120 min.
(c) Adding sodium chloride into the solution obtained in the step (b), and stirring until the solution is clear; preferably, the amount of the added sodium chloride is 0.1 to 0.2 times of the mass of the ceftizoxime acid.
(d) Adding activated carbon into the solution obtained in the step (c) for decoloring, and filtering after decoloring; preferably, the dosage of the active carbon is 10-15% of the weight of ceftizoxime acid, and the decoloring time is 30-60 min.
(e) And (d) controlling the temperature of the filtrate obtained in the step (d) to be 13-15 ℃, adding ethanol for the first time, then adding ceftizoxime sodium seed crystal, growing crystals, adding ethanol again after a large amount of crystals are obtained, cooling, continuing to grow crystals, filtering, washing and drying to obtain ceftizoxime sodium powder. Preferably, the volume usage of the ethanol added for the first time is 7-8 times of the weight of the ceftizoxime acid, and the amount of the added crystal seeds is 5% -7% of the weight of the ceftizoxime acid; and adding ethanol again, wherein the volume dosage of the ethanol is 55-60 times of the weight of the ceftizoxime acid. Cooling, and growing crystal at 0-2 deg.C for 60-90 min.
(f) And (e) aseptically packaging the ceftizoxime sodium powder obtained in the step (e) to obtain the ceftizoxime sodium powder injection for injection.
The following are specific examples:
example 1
Ceftizoxime sodium for injection is prepared by the method. The specific operation content is as follows:
adding 60mL of purified water into a reaction tank, cooling to 0-5 ℃, adding 30.0g of ceftizoxime acid under stirring, adding 3g of acetic acid-sodium acetate buffer solution under stirring, controlling the temperature of the system to be 0-2 ℃, slowly adding sodium acetate solution (6.75g of sodium acetate is dissolved in 120mL of purified water) for 60min, and uniformly stirring until the solution is clear. After the solution is clear, 3.0g of sodium chloride is added into the feed liquid, and the mixture is stirred again until the solution is clear.
Adding 3.0g of activated carbon into the solution, stirring for 60min, filtering, performing sterile filtration, feeding into a crystallization tank, washing with 10mL of purified water, and combining into the crystallization tank.
Controlling the crystallization temperature to be 15 ℃, adding 210mL of ethanol, adding 1.5g of sterile ceftizoxime sodium seed crystal, growing the crystals for 30min, after a large amount of crystals are produced, adding 1650mL of ethanol, and controlling the adding time to be 120 min. After the addition, the temperature is reduced to 0-2 ℃, the crystals are grown for 60min, and then the filter cake is filtered and washed by 200mL of ethanol. Vacuum drying at 40 deg.C until water content is less than or equal to 8.5%. Discharging to obtain 29.5g of ceftizoxime sodium sterile powder; the yield after seed crystal removal is 93.3%; and (3) carrying out sterile subpackaging on the ceftizoxime sodium powder to obtain the ceftizoxime sodium powder injection for injection.
Example 2
Adding 70mL of purified water into a reaction tank, cooling to 0-5 ℃, adding 30.0g of ceftizoxime acid under stirring, adding 6g of acetic acid-sodium acetate buffer solution under stirring, controlling the temperature of the system to be 0-5 ℃, slowly adding a sodium acetate solution (7.38g of sodium acetate is dissolved in 150mL of purified water) within 120min, and uniformly stirring until the solution is clear. After the solution is clear, 6.0g of sodium chloride is added into the feed liquid, and the mixture is stirred again until the solution is clear.
Adding 4.5g of activated carbon into the solution, stirring for 30min, filtering, performing sterile filtration, feeding into a crystallization tank, washing with 10mL of purified water, and combining into the crystallization tank.
Controlling the crystallization temperature at 13 ℃, adding 240mL of ethanol, adding 2.1g of sterile ceftizoxime sodium seed crystal, growing the crystals for 60min, after a large amount of crystals are produced, adding 1800mL of ethanol, and controlling the adding time for 120 min. After the addition, the temperature is reduced to 0-2 ℃, the crystals are grown for 120min, and then the filter cake is filtered and washed by 200mL of ethanol. Vacuum drying at 40 deg.C until water content is less than or equal to 8.5%. Discharging to obtain 30.2g of ceftizoxime sodium sterile powder. The yield after seed crystal removal is 93.7%; and (3) carrying out sterile subpackaging on the ceftizoxime sodium powder to obtain the ceftizoxime sodium powder injection for injection.
Example 3
Adding 50L of purified water into a reaction tank, cooling to 0-5 ℃, adding 20.0kg of ceftizoxime acid under stirring, adding 2kg of acetic acid-sodium acetate buffer solution under stirring, controlling the temperature of the system to be 0-5 ℃, slowly adding sodium acetate solution (4.68kg of sodium acetate is dissolved in 80L of purified water) within 120min, and uniformly stirring until the solution is clear. After the solution is clear, 3kg of sodium chloride is added into the feed liquid, and the mixture is stirred again until the solution is clear.
Adding 2kg of activated carbon into the solution, stirring for 30min, filtering, performing sterile filtration, feeding into a crystallization tank, washing with 6L of purified water, and combining to the crystallization tank.
Controlling the crystallization temperature at 13 ℃, adding 160L of ethanol, adding 1kg of sterile ceftizoxime sodium seed crystal, growing the crystals for 60min, after a large amount of crystals are produced, adding 1200L of ethanol, and controlling the adding time for 120 min. After the addition, the temperature is reduced to 0-2 ℃, the crystals are grown for 120min, and then the filter cake is filtered and washed by 120L of ethanol. Vacuum drying at 40 deg.C until water content is less than or equal to 8.5%. Discharging to obtain 19.8kg of ceftizoxime sodium sterile powder. The yield after seed crystal removal is 94.0%; and (3) carrying out sterile subpackaging on the ceftizoxime sodium powder to obtain the ceftizoxime sodium powder injection for injection.
The following are comparative examples of examples, for a total of 5 comparative examples.
Comparative examples 1 to 4
Comparative examples 1-4 were prepared similarly to example 1, except that: no buffer was added to the procedure of comparative example 1; comparative example 2 crystalline system no sodium chloride was added; in comparative example 3, the added buffer solution is 0.3 times of the weight of ceftizoxime acid; in comparative example 4, 0.3 times the weight of ceftizoxime acid was added.
Comparative example 5 was conducted in accordance with the method for producing ceftizoxime sodium in example 1 described in patent document CN 109553626A.
The quality tests were carried out on the examples and comparative examples, and the data are given in the following table:
TABLE 1
Figure BDA0002526830280000071
According to the data in the table 1, the process is determined to be within the scope of the claims, the product quality is stable, the LOD, the content, the color grade and the impurity level are equivalent, and the process reproducibility is good; especially, the product has high content and good purity. And (3) analyzing that the content of the product and the color grade quality index are influenced by introducing too much buffer solution and inorganic salt into the crystallization system through a comparative example 3 and a comparative example 4.
The example 3 samples were subjected to a 6 month accelerated stability study and the data are given in the following table:
Figure BDA0002526830280000072
according to the experimental data in table 2, it can be seen that the product has stable moisture, content, color grade and impurity quality after accelerated experiment, and all indexes meet the quality requirements of 2015 edition of Chinese pharmacopoeia.
In order to better verify that the ceftizoxime sodium product prepared by the invention has certain advantages in fluidity, 3 samples of ceftizoxime sodium for injection obtained in examples 1-3, ceftizoxime sodium for injection sold in markets and ceftizoxime sodium for injection obtained in comparative examples 1-5 are taken for sample repose angle detection and comparison, and the results are shown in table 3.
TABLE 3
Figure BDA0002526830280000081
According to the detection results in the table 3, compared with the market available 1-2 and the comparative examples 1-5, the ceftizoxime sodium powder injection preparation for injection prepared by the invention has smaller angle of repose, and according to the powder property, the better the powder flowability is, the smaller the angle of repose is; the powder particles have rough surfaces, and the larger the adhesiveness, the larger the angle of repose. The product prepared by the method has good fluidity, and can meet the requirement of fluidity in the production process; the comparative sample was relatively poor in flowability.
The upper and lower limit values and interval values of the process parameters (such as temperature, time, molar ratio and the like) of the invention can realize the invention, and the examples are not listed.
In conclusion, the invention designs reasonable process routes and process parameters, and the product prepared by the method is more suitable for subpackaging powder injection preparations, so that the ceftizoxime sodium for injection is prepared.

Claims (9)

1. A preparation method of ceftizoxime sodium for injection is characterized by comprising the following steps: the method comprises the following steps:
(a) reducing the temperature of the purified water to 0-5 ℃; adding ceftizoxime acid into purified water, and adding a buffer solution;
(b) adding a salt forming agent into the solution obtained in the step (a), controlling the temperature to be 0-5 ℃, and stirring until the solution is clear;
(c) adding sodium chloride into the solution obtained in the step (b), and stirring until the solution is clear;
(d) adding activated carbon into the solution obtained in the step (c) for decoloring, and filtering after decoloring;
(e) controlling the temperature of the filtrate obtained in the step (d) to be 13-15 ℃, adding ethanol for the first time, then adding ceftizoxime sodium seed crystal, and growing the crystals; after a large amount of crystals are discharged, adding ethanol again, cooling, continuing to grow crystals, filtering, washing and drying to obtain ceftizoxime sodium powder;
(f) and (e) aseptically packaging the ceftizoxime sodium powder obtained in the step (e) to obtain the ceftizoxime sodium powder injection for injection.
2. The preparation method of ceftizoxime sodium for injection according to claim 1, wherein the preparation method comprises the following steps: in the step (a), the amount of the purified water is 2.0-2.5 times of the weight of the ceftizoxime acid.
3. The preparation method of ceftizoxime sodium for injection according to claim 1, wherein the ceftizoxime sodium is prepared by mixing a solution of ceftizoxime sodium and a solution of ceftizoxime sodium; in the step (a), the buffer solution is acetic acid-sodium acetate buffer solution; the adding amount is 0.1-0.2 time of the weight of ceftizoxime acid; preparing an acetic acid-sodium acetate buffer solution: 54.6g of sodium acetate is dissolved in 20mL of 1mol/L acetic acid solution, and then the solution is diluted to 500mL by adding water.
4. The preparation method of ceftizoxime sodium for injection according to claim 1, wherein the preparation method comprises the following steps: in the step (b), the salt forming agent is sodium acetate solution, and the molar ratio of the sodium acetate to the ceftizoxime acid is 1.05-1.15: 1; the water consumption for dissolving the sodium acetate is 4 to 5 times of the weight of the ceftizoxime acid; the addition time is 60-120 min.
5. The preparation method of ceftizoxime sodium for injection according to claim 1, wherein the preparation method comprises the following steps: in the step (c), the amount of the added sodium chloride is 0.1-0.2 time of the mass of the ceftizoxime acid.
6. The preparation method of ceftizoxime sodium for injection according to claim 1, wherein the preparation method comprises the following steps: the dosage of the active carbon used in the step (d) is 10 to 15 percent of the weight of the ceftizoxime acid, and the decoloring time is 30 to 60 min.
7. The preparation method of ceftizoxime sodium for injection according to claim 1, wherein the preparation method comprises the following steps: in the step (e), ethanol is added for the first time, the volume usage amount of the ethanol is 7-8 times of the weight of the ceftizoxime acid, and the amount of the added crystal seeds is 5% -7% of the weight of the ceftizoxime acid.
8. The preparation method of ceftizoxime sodium for injection according to claim 1, wherein the preparation method comprises the following steps: in the step (e), ethanol is added again, and the volume dosage of the ethanol is 55-60 times of the weight of the ceftizoxime acid.
9. The preparation method of ceftizoxime sodium for injection according to claim 1, wherein the preparation method comprises the following steps: in the step (e), the temperature is reduced, the crystal growing temperature is 0-2 ℃ in the crystal growing process, and the crystal growing time is 60-90 min.
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