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CN119385942A - A kind of nalbuphine hydrochloride injection and preparation method thereof - Google Patents

A kind of nalbuphine hydrochloride injection and preparation method thereof Download PDF

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Publication number
CN119385942A
CN119385942A CN202510012484.XA CN202510012484A CN119385942A CN 119385942 A CN119385942 A CN 119385942A CN 202510012484 A CN202510012484 A CN 202510012484A CN 119385942 A CN119385942 A CN 119385942A
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injection
citric acid
sodium citrate
nalbuphine hydrochloride
mass ratio
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CN119385942B (en
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郭娜
刘秀芝
陈艳
马育彪
代纯
王颖
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Chengdu Easton Biopharmaceuticals Co Ltd
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00Medicinal preparations containing organic active ingredients
    • A61K31/33Heterocyclic compounds
    • A61K31/395Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins
    • A61K31/435Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins having six-membered rings with one nitrogen as the only ring hetero atom
    • A61K31/47Quinolines; Isoquinolines
    • A61K31/485Morphinan derivatives, e.g. morphine, codeine
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61JCONTAINERS SPECIALLY ADAPTED FOR MEDICAL OR PHARMACEUTICAL PURPOSES; DEVICES OR METHODS SPECIALLY ADAPTED FOR BRINGING PHARMACEUTICAL PRODUCTS INTO PARTICULAR PHYSICAL OR ADMINISTERING FORMS; DEVICES FOR ADMINISTERING FOOD OR MEDICINES ORALLY; BABY COMFORTERS; DEVICES FOR RECEIVING SPITTLE
    • A61J3/00Devices or methods specially adapted for bringing pharmaceutical products into particular physical or administering forms
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/02Inorganic compounds
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/06Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite
    • A61K47/08Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite containing oxygen, e.g. ethers, acetals, ketones, quinones, aldehydes, peroxides
    • A61K47/12Carboxylic acids; Salts or anhydrides thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00Medicinal preparations characterised by special physical form
    • A61K9/0012Galenical forms characterised by the site of application
    • A61K9/0019Injectable compositions; Intramuscular, intravenous, arterial, subcutaneous administration; Compositions to be administered through the skin in an invasive manner
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00Medicinal preparations characterised by special physical form
    • A61K9/08Solutions
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61PSPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P25/00Drugs for disorders of the nervous system
    • A61P25/04Centrally acting analgesics, e.g. opioids

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
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  • Engineering & Computer Science (AREA)
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  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
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  • Pain & Pain Management (AREA)
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  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

The invention belongs to the field of pharmaceutical preparations, and in particular relates to a nalbuphine hydrochloride injection and a preparation method thereof. The invention solves the problem that the impurities of the dual nalbuphine are easy to generate in the prior art by changing the components and the content of the prescription, obviously improves the stability of the preparation and reduces the risks possibly brought by various potential side effects. Meanwhile, the preparation process is optimized, the process time consumption is greatly shortened, and the exposure time of the product is reduced.

Description

Nalbuphine hydrochloride injection and preparation method thereof
Technical Field
The invention belongs to the field of pharmaceutical preparations, and in particular relates to nalbuphine hydrochloride injection and a preparation method thereof.
Background
Nalbuphine is a semisynthetic opioid agonist-antagonist analgesic that is chemically similar to the opioid oxymorphone and the opioid antagonist naloxone. Nalbuphine exhibits both agonism of the opioid kappa receptor and antagonism of the mu receptor. Nalbuphine is administered by intravenous injection, intramuscular injection, subcutaneous injection, and intrathecal administration, and can be used for effectively controlling severe and deep pain caused by heart, lung, abdomen, bone diseases, obstetrical surgery, severe burn, and advanced cancer. The nalbuphine can be used within 2-3 minutes after intravenous administration, and can be used within 15 minutes after intramuscular or subcutaneous injection.
Nalbuphine hydrochloride is white or white-like crystalline powder and is easy to dissolve in water. The prior art describes that nalbuphine hydrochloride injection (trade name: nubain) is stable in a slightly acidic environment, but forms a dual nalbuphine impurity when the pH is raised above 6, and the formation of the impurity is also influenced by light and heavy metal ions, so that the nalbuphine hydrochloride injection loses stability within the shelf life of the medicament.
Patent RU 2254852 (2005.06.27 publication) discloses a nalbuphine injection containing 0.8-2.2. 2.2 wt% nalbuphine hydrochloride, 0.5-3.5 wt% buffer mixture, 0.001-0.2 wt% complexing agent, 0.15-0.25 wt% stabilizer and water for injection. The patent reduces the production of the impurity bisnalbuphine by the addition of complexing agent EDTA, but side effects associated with intravenous EDTA over 5 days may occur, such as hypokalemia, renal and hepatic exacerbation. In addition, such drugs may cause adverse reactions in diabetics, low-potassium patients, heart rate disorder patients and cardiovascular disease patients. RU 2254852 patent specification does not have information about the safety of the proposed drug.
Patent RU 2483731 (2013.06.10 publication) discloses a nalbuphine hydrochloride injection with remarkable analgesic effect, which contains nalbuphine hydrochloride 1.0-2.0 wt%, citric acid 1.26-wt%, sodium citrate 0.94-wt%, sodium chloride 0.1-wt%, sodium metabisulfite 0.1-wt% and water for injection. The injection is added with the antioxidant sodium metabisulfite to improve the stability of the medicine, but is not suitable for asthma patients sensitive to sulfur-containing components.
Based on the problems existing in the prior art, there is still a need for nalbuphine hydrochloride injection with good stability and few side effects, so as to reduce the generation of impurities of the dual nalbuphine, improve the stability of the preparation, and be applicable to various patient groups.
Disclosure of Invention
The invention provides a nalbuphine hydrochloride injection and a preparation method thereof, which solve the technical problem that impurities of the nalbuphine in the prior art are easy to generate, remarkably improve the stability of the preparation and reduce the risks possibly brought by various potential side effects.
The first aspect of the invention provides a nalbuphine hydrochloride injection, which comprises the following components of 5-20 mg nalbuphine hydrochloride, 1.5-7.5 mg sodium chloride, a buffer mixture and water for injection.
The pH value of the injection is about 3.0-4.0.
In some embodiments, each unit of nalbuphine hydrochloride injection comprises 10-20 mg nalbuphine hydrochloride, 2-7 mg sodium chloride, buffer mixture and water for injection.
In some embodiments, each unit of nalbuphine hydrochloride injection comprises 10mg nalbuphine hydrochloride, 4-7.5 mg sodium chloride, buffer mixture and water for injection.
The buffer mixture comprises citric acid and sodium citrate. In some embodiments, the mass ratio of citric acid to sodium citrate is 1:0.55-0.9, preferably the mass ratio of citric acid to sodium citrate is 1:0.65-0.75. In some embodiments, the mass ratio of citric acid to sodium citrate is 1:0.50, 1:0.60, 1:0.65, 1:0.70, 1:0.80, 1:0.85.
In some embodiments, each unit of nalbuphine hydrochloride injection comprises 10-20 mg nalbuphine hydrochloride, 1.5-7.5 mg sodium chloride, citric acid, sodium citrate and water for injection. Further, in some embodiments, each unit of nalbuphine hydrochloride injection comprises 10-20 mg nalbuphine hydrochloride, 2-7 mg sodium chloride, citric acid, sodium citrate and water for injection, wherein the mass ratio of the citric acid to the sodium citrate is 1:0.55-0.9, and the preferred mass ratio is 1:0.65-0.75.
In some embodiments, the mass ratio of nalbuphine hydrochloride to citric acid+sodium citrate is about 1:0.35-0.75, preferably about 1:0.45-0.55.
In some embodiments, each unit of nalbuphine hydrochloride injection comprises 10 mg nalbuphine hydrochloride, 4-7.5 mg sodium chloride, citric acid, sodium citrate and water for injection, wherein the mass ratio of the citric acid to the sodium citrate is 1:0.55-0.9, preferably 1:0.65-0.7, and the mass ratio of the nalbuphine hydrochloride to the citric acid+sodium citrate in the buffer mixture is about 1:0.35-0.75, preferably about 1:0.45-0.55.
In some embodiments, the nalbuphine hydrochloride injection further comprises a complexing agent, wherein the mass ratio of citric acid to sodium citrate in the complexing agent to the buffer stabilizer is 1:0.005-0.015, and preferably the mass ratio is 1:0.01-0.012.
Preferably, the complexing agent is calcium sodium edetate.
In some embodiments, each unit of the nalbuphine hydrochloride injection comprises 10-20 mg nalbuphine hydrochloride, 1.5-7.5 mg sodium chloride, citric acid, sodium citrate, sodium calcium edetate and water for injection.
Further, in some embodiments, each unit of the nalbuphine hydrochloride injection comprises 10-20 mg parts of nalbuphine hydrochloride, 2-7 mg parts of sodium chloride, citric acid, sodium citrate and calcium sodium edetate, wherein the mass ratio of the citric acid to the sodium citrate is 1:0.55-0.9, preferably 1:0.65-0.75, and the mass ratio of the citric acid and the sodium citrate to the calcium sodium edetate is 1:0.005-0.015, preferably 1:0.01-0.012.
In some embodiments, each unit of nalbuphine hydrochloride injection comprises 10mg parts of nalbuphine hydrochloride, 4-7.5 parts of mg parts of sodium chloride, citric acid, sodium citrate, sodium calcium edetate and water for injection, wherein the mass ratio of the citric acid to the sodium citrate is 1:0.55-0.9, preferably 1:0.65-0.75, the mass ratio of the nalbuphine hydrochloride to the citric acid+sodium citrate in the buffer mixture is about 1:0.35-0.75, preferably about 1:0.45-0.555, and the mass ratio of the citric acid+sodium citrate to the sodium calcium edetate is about 1:0.005-0.015, preferably 1:0.01-0.012.
The second aspect of the invention provides a preparation method of the nalbuphine hydrochloride injection, which comprises the following steps:
step a, adding water for injection into a liquid preparation tank, adjusting the water temperature, and filling nitrogen;
B, adding auxiliary materials with the prescription amount into a liquid preparation tank, stirring until the auxiliary materials are completely dissolved, and then continuously adding nalbuphine hydrochloride with the prescription amount, stirring until the raw materials are completely dissolved;
c, cleaning, sterilizing and drying the ampoule, filling and sealing, and filling nitrogen before and after filling and sealing;
And d, sterilizing and packaging.
In some embodiments, in the preparation method of the nalbuphine hydrochloride injection, the temperature of the water temperature in the step a is 40-60 ℃.
In some embodiments, in the preparation method of the nalbuphine hydrochloride injection of the present invention, the auxiliary materials in the step b include sodium citrate, anhydrous citric acid and sodium chloride.
In some embodiments, in the preparation method of the nalbuphine hydrochloride injection of the present invention, the auxiliary materials in the step b include sodium citrate, anhydrous citric acid, calcium sodium edetate and sodium chloride.
The invention has the beneficial effects that:
1. the nalbuphine hydrochloride injection has good stability, obviously reduces the content of the dual nalbuphine and obviously inhibits the generation of dual nalbuphine impurities in storage. Meanwhile, the use of sulfur-containing antioxidants and EDTA is avoided, so that various possible side effects can be obviously reduced, and the method is applicable to wider patient population;
2. In the aspect of the preparation process, the preparation process can obviously shorten the process time consumption, reduce the production cost, reduce the exposure time of the product based on the reduction of the process time limit, and reduce the pollution risk of the product on the side surface.
Detailed Description
The present invention is described in further detail below with reference to examples, but is not limited to the following examples, and any equivalents in the art, which are in accordance with the present disclosure, are intended to fall within the scope of the present invention.
In the present application, the terms "comprises," "comprising," and "includes" and their equivalents are to be construed as open, non-exclusive meaning, that "including but not limited to," means that other unspecified elements, components, and steps may be contemplated in addition to those listed. In this document, singular terms encompass plural referents and vice versa, unless the context clearly dictates otherwise.
In the present application, the term "about" means ± 5% based on the original data.
In the present application, pharmaceutical excipients or agents are commercially available.
Examples 1 to 7 contain the following ingredients per unit preparation
The preparation method comprises the following steps:
and a, adding water for injection into a liquid preparation tank, and filling nitrogen.
Adding the sodium citrate, the anhydrous citric acid and the sodium chloride with the prescription amount into a liquid preparation tank, stirring until the auxiliary materials are completely dissolved, continuously adding the nalbuphine hydrochloride with the prescription amount, stirring until the raw materials are completely dissolved, filtering and sterilizing;
c, cleaning, sterilizing and drying the ampoule, filling and sealing, and filling nitrogen before and after filling and sealing;
And d, sterilizing and packaging at the temperature of 121 ℃ for 15min.
The samples of examples 1-7 were tested for pH, with the pH of the sample of example 1 being slightly acidic and the pH of the samples of examples 2 and 7 being approximately 2.8 and 4.2, respectively, and the pH of the products of examples 3-6 being in the range of 3.0-4.0, without the addition of other pH adjusters.
The samples of examples 1 to 7 were left for 6 months at 60.+ -. 2 ℃ to examine the properties and pH changes as follows.
TABLE 1a results of Property changes in samples of examples 1-7
TABLE 1b results of pH changes for examples 1-7 samples
Test results show that the mass ratio of citric acid to sodium citrate is 1:0.55-0.9, and the pH value of the injection can be regulated stably as in examples 3-6, so that the generation of impurities is reduced.
Examples 8-13 contain the following ingredients per unit formulation
Comparative example 1 nalbuphine hydrochloride injection was prepared as described in example 4-1 with reference to RU2254852C 1.
Comparative example 2 nalbuphine hydrochloride injection was prepared as described in example 1 with reference to RU2483731C 1.
The injection samples of examples 8-13 and comparative examples 1-2 were left under light of 4500.+ -.500 lx for 5 days, and were sampled for measurement of pH, content, bisbuprenorphine (P0Z 5) and other related substances, and the mass change of the samples under the above conditions was examined, and the results are shown in Table 2.
Table 2 test results
The inventor finds that the stability of the injection can be obviously improved by adjusting the dosage of citric acid/sodium citrate and adjusting the proportion of nalbuphine hydrochloride to citric acid and sodium citrate, the experiment ensures that the osmotic pressure of each embodiment is consistent by adjusting the dosage of sodium chloride under the condition of keeping the proportion of citric acid and sodium citrate unchanged, the proportion of nalbuphine hydrochloride to citric acid and sodium citrate is changed, and the experiment result shows that the generation of impurities in the nalbuphine hydrochloride injection sample, especially the generation of dual nalbuphine impurities, is easily influenced by illumination, and the stability of the embodiments 8-13 under the illumination condition is obviously improved compared with the comparative examples 1-2.
Examples 14 to 19 contain the following ingredients per unit of preparation
The injectable products of examples 14-19 and comparative examples 1-2 were allowed to stand for 6 months at 60.+ -. 2 ℃ to examine the percentage of the bisbuprenorphine impurity and other impurities, and the results are shown in Table 3a.
Table 3a test results
The injection products of examples 14-19 were left under light 4500.+ -.500 lx for 5 days, and the percentage of the impurities of the bisbuprenorphine (P0Z 5) and other impurities were examined, the results are shown in Table 3b.
Table 3b test results
The test result shows that the stability of the nalbuphine hydrochloride injection under the high-temperature and light conditions can be further improved obviously by further adding the sodium calcium edetate into the prescription and controlling the ratio of the sodium calcium edetate to the citric acid/sodium citrate. The samples of examples 14-19 showed a significant improvement in stability at high temperature and under light conditions, consistent with the pharmaceutical quality requirements, over comparative examples 1-2.
The preparation process according to the prescription composition of examples 16 and 17 is as follows
The preparation process comprises the following steps:
Step a, adding water for injection into 6 liquid preparation tanks respectively, and placing each 2 liquid preparation tanks into 25 ℃ water baths (1-1 batch and 2-1 batch), 40 ℃ water baths (1-2 batch and 2-2 batch) and 60 ℃ water baths (1-3 batch and 2-3 batch) respectively;
Step b, adding sodium citrate, anhydrous citric acid and sodium chloride with the prescription of the example 16 into 1-1 batch, 1-2 batch and 1-3 batch liquid preparation tanks, adding sodium citrate, anhydrous citric acid and sodium chloride with the prescription of the example 17 into 2-1 batch, 2-2 batch and 2-3 batch liquid preparation tanks, stirring until the auxiliary materials are completely dissolved, continuing to add nalbuphine hydrochloride with the corresponding prescription amount, stirring until the raw materials are completely dissolved, recording the dissolution time of the raw materials, reducing the temperature of liquid medicine, and filtering for sterilization;
Step c, cleaning, sterilizing and drying the ampoule, filling and sealing, and filling nitrogen before and after filling and sealing;
and d, sterilizing at 121 ℃ for 15min, and packaging.
The properties, pH, content, and other related substances of each batch of samples were examined, and the results are shown in Table 4a.
Table 4a test results
The test result shows that the dissolution time of the raw materials at 25 ℃ is longer, the liquid preparation temperature is determined to be 40-60 ℃ in consideration of the feasibility of large-scale production, and the production time consumption can be obviously reduced, so that the exposure time of the product is reduced, and the quality of the product meets the requirements.
Secondly, the influence of oxygen on the degradation of the product is examined, namely, the nitrogen filling can reduce the oxygen content in the product and slow down the degradation speed of the product, so that the influence of different nitrogen filling modes of liquid preparation and filling and sealing on the stability of the product is examined. Samples were prepared according to the recipe of examples 16-17, and the preparation method was the same as in example 1 except for the nitrogen dosing mode, which was examined and designed as follows:
Before preparing the liquid, the injection water is filled with nitrogen to below 1.0mg/L, and the liquid medicine is filled with nitrogen to a dissolved oxygen value lower than 1.0mg/L and then encapsulated. And (2) filling nitrogen in the encapsulation, wherein the nitrogen is filled before and after the encapsulation.
The samples are placed at the high temperature of 60 ℃ plus or minus 2 ℃ and are sampled respectively for 0 day and 30 days, the properties, the pH value, the related substances and the content are detected, the headspace residual oxygen is increased for 0 day, and the test results are shown in Table 4b.
Table 4b test results
Test results show that the nitrogen-filled and filled samples of the liquid preparation filling and sealing process are not filled with nitrogen, namely, the nitrogen-filled and filled samples of the liquid preparation filling and sealing process are not filled with nitrogen after being heated for 30 days, the impurity P0Z5 is obviously increased and exceeds the quality standard limit (0.5%), the characters are changed, other detection indexes are not obviously changed, and the nitrogen-filled and filled samples of the liquid preparation filling and sealing process are filled with nitrogen after being mixed liquid preparation filling and sealing process, namely, the impurity P0Z5 is slightly increased and has consistent growing trend after being heated for 30 days.
Those skilled in the art will recognize that the scope of the application is not limited to the various embodiments and examples described above, but is capable of various modifications, substitutions, or rearrangements without departing from the spirit of the application, which are intended to be within the scope of the application.

Claims (9)

1. The nalbuphine hydrochloride injection is characterized by comprising 5-20 mg nalbuphine hydrochloride, 1.5-7.5 mg sodium chloride, a buffer mixture and water for injection, wherein the pH value of the injection is 3.0-4.0, the buffer mixture comprises citric acid and sodium citrate, and the mass ratio of the citric acid to the sodium citrate is 1:0.55-0.9.
2. The injection according to claim 1, wherein the mass ratio of nalbuphine hydrochloride to citric acid and sodium citrate is 1:0.35-0.75.
3. The injection according to claim 2, wherein the mass ratio of nalbuphine hydrochloride to citric acid and sodium citrate is 1:0.45-0.55.
4. The injection according to claim 1, wherein each unit of injection comprises 10-20 mg nalbuphine hydrochloride, 2-7 mg sodium chloride, citric acid, sodium citrate and water for injection, wherein the mass ratio of the citric acid to the sodium citrate is 1:0.55-0.9.
5. The injection according to claim 1, further comprising a complexing agent, wherein the complexing agent is edetate sodium calcium.
6. The injection according to claim 5, wherein the mass ratio of citric acid + sodium citrate to complexing agent in the buffer mixture is 1:0.005-0.015.
7. The injection according to claim 6, wherein each unit of injection contains 10-20 mg parts of nalbuphine hydrochloride, 2-7 parts of mg parts of sodium chloride, citric acid, sodium citrate and calcium sodium edetate, wherein the mass ratio of citric acid to sodium citrate is 1:0.55-0.9, the mass ratio of nalbuphine hydrochloride to citric acid and sodium citrate is 1:0.35-0.75, and the mass ratio of citric acid and sodium citrate to complexing agent is 1:0.005-0.015.
8. A process for the preparation of nalbuphine hydrochloride injection as claimed in any one of claims 1 to 7 comprising the steps of:
step a, adding water for injection into a liquid preparation tank, adjusting the water temperature, and filling nitrogen;
B, adding auxiliary materials with the prescription amount into a liquid preparation tank, stirring until the auxiliary materials are completely dissolved, and then continuously adding nalbuphine hydrochloride with the prescription amount, stirring until the raw materials are completely dissolved;
step c, cleaning, sterilizing and drying the ampoule, filling and sealing, and filling nitrogen before and after filling and sealing;
And d, sterilizing and packaging.
9. The method according to claim 8, wherein the water temperature is adjusted to 40-60 ℃ in step a.
CN202510012484.XA 2025-01-06 2025-01-06 A kind of nalbuphine hydrochloride injection and preparation method thereof Active CN119385942B (en)

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CN115919858A (en) * 2022-01-24 2023-04-07 中国人民解放军总医院第一医学中心 Analgesic pharmaceutical composition, preparation method and application thereof
WO2023150579A2 (en) * 2022-02-01 2023-08-10 HUMANWELL PHARMACEUTICAL US, Inc. Pharmaceutical formulations containing nalbuphine
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030113372A1 (en) * 2001-11-26 2003-06-19 Hu Oliver Yoa-Pu Controlled-release pharmaceutical preparation containing nalbuphine and a process for preparing the same
RU2254852C1 (en) * 2004-01-23 2005-06-27 Ефим Давыдович Нежинский Injection solution with expressed analgesic effect and method for its preparing
RU2483731C1 (en) * 2012-04-24 2013-06-10 Федеральное государственное унитарное предприятие "Московский эндокринный завод" Solution for injections containing nalbuphine
CN105440045A (en) * 2014-08-20 2016-03-30 宜昌人福药业有限责任公司 Nalbuphine acidic salt refining technology
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