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CN114047262B - A method for separating and determining easily hydrolyzed large polar compounds - Google Patents

A method for separating and determining easily hydrolyzed large polar compounds Download PDF

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CN114047262B
CN114047262B CN202111197761.7A CN202111197761A CN114047262B CN 114047262 B CN114047262 B CN 114047262B CN 202111197761 A CN202111197761 A CN 202111197761A CN 114047262 B CN114047262 B CN 114047262B
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solution
impurity
separating
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acyclovir
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CN114047262A (en
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王宝盛
李晓晖
张志海
夏艳开
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Hubei Hongyuan Pharmaceutical Technology Co ltd
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • G01N30/60Construction of the column
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • G01N2030/022Column chromatography characterised by the kind of separation mechanism
    • G01N2030/027Liquid chromatography

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Abstract

The invention discloses a method for separating and measuring easily-hydrolyzed large polar compounds, which comprises the following steps of dissolving acyclovir in a diluent to form a sample solution, detecting a standard substance solution and the sample solution by adopting high performance liquid chromatography, wherein the liquid chromatography comprises a chromatographic column, a hybrid silica gel column, a mobile phase A, a buffer solution, a mobile phase B, acetonitrile, isocratic elution, a mobile phase flow rate of 0.4-0.6 ml/min, a column temperature of 25-35 ℃, a detection wavelength of UV254nm, a sample injection amount of 20 μl and a running time of 50min. The method can inhibit hydrolysis in the process of sampling the easily-hydrolyzed large polar compound impurity, truly reflects the detection amount of the impurity, has high precision, operates at room temperature, has good reproducibility, and can effectively separate and determine the content of the easily-hydrolyzed large polar compound.

Description

Method for separating and measuring easily-hydrolyzed large polar compound
Technical Field
The invention relates to the technical field of pharmaceutical analysis, in particular to a method for separating and measuring easily-hydrolyzed large polar compounds, and specifically relates to a method for separating and measuring the impurity content of easily-hydrolyzed large polar compounds in acyclovir.
Background
Acyclovir (Acyclovir) is an antiviral drug.
The chemical structural formula:
Acyclovir is a synthetic purine nucleoside analogue. Is mainly used for various infections caused by herpes simplex virus, and can be used for treating HSV infections caused by primary or recurrent skin, mucous membrane, external genital infections and immunodeficiency. Is the first choice for treating HSV encephalitis, and has better effect on reducing morbidity and mortality than the arabinoside. It can also be used for treating herpes zoster, EB virus, and immunodeficiency complicated with varicella. Topical application to skin only, acyclovir has less skin absorption.
In the quality control of acyclovir, partial impurities are extremely unstable, and can be rapidly hydrolyzed in a system such as water, weak acid or weak base, for example, diacetylguanine (impurity A) in the acyclovir can be rapidly hydrolyzed and deacylated in the water to be changed into monoacetylguanine (impurity B) and guanine, so that the contents of diacetylguanine, monoacetylguanine and guanine in acyclovir cannot be truly reflected in the detection process.
Chinese patent CN202010731803.X reports that the comparison of qualified finished products by ultraviolet dual-wavelength absorbance ratio detection method can rapidly and accurately control the reaction end point and the quality of the finished products, and the ultraviolet spectrophotometry has poor specificity and cannot accurately quantify the content of monoacetylguanine in the reaction liquid and diacetylguanine.
The ultra high pressure liquid chromatography (UPLC) method for measuring the purity of diacetylguanine (the research of the detection method of the beta-furfront, liu Chunyan, mo Wenjuan, N-2, 9-diacetylguanine, international medical and health guide, volume 19 in 2013, 1675-1677) is reported by the Yuanfeng et al, and the better separation can be realized due to the high column efficiency of the UPLC, the short chromatographic column and the short analysis time, wherein the retention time of the monoacetylguanine and the diacetylguanine is only 1.1 minutes and 2.0 minutes. The ultrahigh pressure liquid chromatography analysis speed is high, so that the hydrolysis can be inhibited. At the same time we repeated the paper using HPLC detection, but the diacetylguanine retention time was 2 minutes, the monoacetylguanine and diacetylguanine co-flowed, the diacetylguanine and diacetylguanine chromatographic peaks were fully coincident, only one chromatographic peak was shown in the liquid chromatogram, indicating that under the reference conditions, diacetylguanine was completely free from monoacetylguanine separation.
Therefore, there is a need for a high performance liquid chromatography method for separating and determining impurities in acyclovir, which can solve the problems, inhibit degradation of the easily hydrolyzed large polar compound impurities in acyclovir, completely separate related impurities, and has the advantages of simple operation and good reproducibility.
Disclosure of Invention
Because the ultra-high pressure liquid chromatograph is high in price and the equipment is not equipped in a general medicine enterprise, the method for analyzing the easily hydrolyzed large polar compound by using the common HPLC has certain practicability, meanwhile, the HILIC chromatographic column is skillfully utilized to be different from the common C-18 chromatographic column, the hydrolysis of the diacetyl guanine in the chromatographic analysis process is reduced when the HILIC chromatographic column is used for a large proportion of organic phases, meanwhile, the large polar compound is kept strongly, the problem that the diacetyl guanine is unstable and cannot be quantified in the analysis process is solved, and the method has innovativeness.
The method is also suitable for detecting the EP impurity Q in the acyclovir Wei Chengpin, and the European pharmacopoeia 10.0 (EP 10.0) analysis method is adopted to detect the impurity Q in the acyclovir Wei Chengpin, so that the impurity Q is hydrolyzed under the chromatographic condition to generate acyclovir, the accuracy in the verification of the analysis method cannot meet the requirement of the regulation, and the fact that the content of the impurity Q in the acyclovir Wei Chengpin cannot be accurately quantified by the EP10.0 analysis method is explained. By adopting the analysis method for detecting the large polar compounds which are easy to hydrolyze, the hydrolysis problem of the impurity Q in liquid chromatography analysis can be well inhibited.
In order to solve the technical problems, the invention provides a method for separating and measuring easily hydrolyzed large polar compounds, which comprises the following steps:
Dissolving a sample containing a large polar compound which is easy to hydrolyze in a diluent to form a sample solution, and detecting the standard substance solution and the sample solution by adopting high performance liquid chromatography;
Wherein the diluent is 10% dimethyl sulfoxide acetonitrile solution;
liquid chromatography conditions:
The chromatographic column is a hybrid silica gel column, the mobile phase A is trifluoroacetic acid solution, the mobile phase B is acetonitrile, isocratic elution is adopted, the flow rate of the mobile phase is 0.4-0.6 ml/min, the column temperature is 25-35 ℃, the detection wavelength is UV254nm, the sample injection amount is 20 mu l, and the running time is 50min.
As a preferred aspect of the above technical solution, the method for separating and determining a readily hydrolyzable large polar compound provided by the present invention further includes some or all of the following technical features:
As an improvement of the above technical scheme, the sample containing the easily hydrolyzable large polar compound is acyclovir or diacetylguanine.
As an improvement of the technical scheme, the sample containing the easily-hydrolyzed large polar compound is acyclovir, wherein the sample contains an impurity A, an impurity B and an impurity Q, and the specific names and chemical structures of the compounds are as follows:
Impurity A is diacetylguanine with structural formula
Impurity B is monoacetylguanine with structural formula
The impurity Q is acyclovir EP impurity Q, and the structural formula is
Acyclovir has the structural formula:
As an improvement of the technical scheme, in the process of the method for separating and measuring the easily hydrolyzed large polar compound, the following solution needs to be prepared:
Dissolving 10mg of impurity B in a 100ml volumetric flask, diluting to scale with 10% dimethyl sulfoxide acetonitrile solution, and shaking;
Mixing standard solution, namely placing 10mg of diacetylguanine sample into a 100ml measuring flask, dissolving 0.5ml of impurity B stock solution with 10% dimethyl sulfoxide acetonitrile solution, diluting to scale, and shaking uniformly;
Taking 10mg of diacetylguanine sample, dissolving the diacetylguanine sample in a 100ml volumetric flask by using a 10% dimethyl sulfoxide acetonitrile solution, diluting the solution to a scale, and shaking the solution uniformly;
blank solution 10% dimethyl sulfoxide acetonitrile solution.
As an improvement of the technical scheme, the isocratic elution is specifically performed according to the following volume ratio of 96-94% of A+4-6% of B.
As an improvement of the technical scheme, the isocratic elution is specifically performed according to the following volume ratio of 95% A+5% B.
As an improvement of the technical scheme, the hybrid silica gel column is a bonded dihydroxypropyl hybrid silica gel column.
As an improvement of the technical scheme, the pH value of the buffer solution is 3.0-4.0.
As an improvement of the technical scheme, the pH value of the buffer solution is regulated by trifluoroacetic acid.
Compared with the prior art, the method has the advantages that the problems can be solved, the degradation of the easily-hydrolyzed large polar compound impurities can be restrained, the content of the easily-hydrolyzed large polar compound is truly embodied, the method is simple, acyclovir and the impurities can be completely separated, the precision is high, the room-temperature operation is performed, the solution reproducibility is good, and the reagent is cheap.
The foregoing description is only an overview of the present invention, and is intended to be implemented in accordance with the teachings of the present invention in order that the same may be more clearly understood and appreciated, as well as the other objects, features and advantages of the present invention, as described in detail below in connection with the preferred embodiments.
Drawings
In order to more clearly illustrate the technical solution of the embodiments of the present invention, the drawings of the embodiments will be briefly described below.
FIG. 1 is a liquid chromatogram of a blank solution prepared in example 1;
FIG. 2 is a liquid chromatographic analysis chart of the mixed standard solution of example 1;
FIG. 3 is a linear plot of impurity A in the linear solution prepared in example 1;
FIG. 4 is a linear plot of impurity B in the linear solution prepared in example 1;
FIG. 5 is a graph of the mixed solution prepared in example 2;
FIG. 6 is a graph of a sample solution prepared in example 2.
Detailed Description
The following detailed description of the invention, which is a part of this specification, illustrates the principles of the invention by way of example, and other aspects, features, and advantages of the invention will become apparent from the detailed description.
Example 1
1) Preparing a solution:
Blank solution 10 dimethyl sulfoxide acetonitrile solution;
and (3) weighing 20mg of impurity A reference substance in a 100ml measuring flask, precisely weighing, dissolving in DMSO, diluting to a scale, and uniformly mixing.
Dissolving 10mg of impurity B in a 100ml volumetric flask, diluting to scale with 10% dimethyl sulfoxide acetonitrile solution, and shaking;
Mixing standard solution, namely placing 10mg of diacetylguanine sample into a 100ml measuring flask, dissolving 0.5ml of impurity B stock solution with 10% dimethyl sulfoxide acetonitrile solution, diluting to scale, and shaking uniformly;
Taking 10mg of diacetylguanine sample, dissolving the diacetylguanine sample in a 100ml volumetric flask by using a 10% dimethyl sulfoxide acetonitrile solution, diluting the solution to a scale, and shaking the solution uniformly;
and (3) precisely removing 14.0ml to 100ml of the impurity B stock solution from the linear stock solution A, adding acetonitrile to dilute to a scale, and shaking uniformly to obtain the product.
And (3) accurately transferring the impurity linear 10% solution to a 10ml measuring flask by taking 0.5ml of the linear stock solution A, diluting to a scale by adding acetonitrile, and uniformly mixing.
And (3) accurately transferring the impurity linear 20% solution to a 10ml measuring flask by taking 1.0ml of the linear stock solution A, diluting to a scale by adding acetonitrile, and uniformly mixing.
And (3) accurately transferring the impurity linear 40% solution to a 10ml measuring flask by taking 2.0ml of the linear stock solution A, diluting to a scale by adding acetonitrile, and uniformly mixing.
And (3) accurately transferring the linear stock solution A4.0 ml into a 10ml measuring flask, diluting with acetonitrile to a scale, and mixing uniformly.
And (3) accurately transferring the impurity linear 100% solution into a 10ml measuring flask by taking 5.0ml of the linear stock solution A, adding acetonitrile to dilute to a scale, and uniformly mixing.
Impurity linear 200% solution, co-linear stock solution A
And (3) precisely transferring 1.0ml to 100ml of the impurity A stock solution to the linear stock solution B, adding acetonitrile to dilute to a scale, and shaking uniformly to obtain the product.
Diacetylguanine linear LOQ solution, taking quantitative limiting solution.
The diacetyl guanine linear solution-1 is prepared by precisely transferring 1.0ml of the linear stock solution B into a 10ml measuring flask, adding acetonitrile to dilute to a scale, and uniformly mixing.
Diacetylguanine linear solution-2, precisely transferring linear stock solution B4.0 ml into a 10ml measuring flask, diluting with acetonitrile to scale, and mixing.
Diacetylguanine linear solution-3, precisely transferring linear stock solution B5.0 ml into a 10ml measuring flask, diluting with acetonitrile to scale, and mixing.
Diacetylguanine linear solution-4. Co-linear stock solution B
2) And detecting the standard substance solution and the sample solution by adopting high performance liquid chromatography, wherein the conditions of the high performance liquid chromatography are as follows:
High performance liquid chromatograph, agilent 1260VWD;
Chromatographic column YMC HILIC hybrid silica gel column (250 mm. Times.4.6 mm. Times.5 μm);
mobile phase a trifluoroacetic acid solution (ph=3.0);
Mobile phase B, acetonitrile;
isocratic elution: a: b=5:95
The flow rate of the mobile phase is 0.5ml/min;
Column temperature is 30 ℃;
the detection wavelength is UV254nm;
the sample injection amount is 20 μl.
FIG. 1 is a liquid chromatogram of a blank solution prepared in example 1, and FIG. 2 is a liquid chromatogram of a mixed standard solution of example 1.
A linear test:
and (5) sequentially sampling according to the sequence of the blank sample and the linear solution.
Drawing a standard curve:
Analysis was performed under the set chromatographic conditions. Calibration curves were drawn from standard series mass concentrations and peak areas. And (3) carrying out linear regression by taking the proportion of the linear solution as an abscissa (%) and the peak area as an ordinate (Y) to obtain a regression equation and a correlation coefficient. In the measurement range, each impurity and valacyclovir have good linear relation, and the linear correlation coefficient R is not less than 0.9990. The data are shown in tables 1-2. FIG. 3 is a linear plot of the impurity A in the linear solution prepared in example 1, and FIG. 4 is a linear plot of the impurity B in the linear solution prepared in example 1;
TABLE 1 liquid chromatography impurity A chromatographic peak analysis results for example 1 Linear solution
TABLE 2 liquid chromatography impurity B chromatography peak analysis results for example 1 Linear solution
Example 2
1) Preparing a solution:
Blank solution, 10% dimethyl sulfoxide acetonitrile solution;
Taking 10mg of impurity Q, dissolving the impurity Q in a 10ml volumetric flask by using a 10% dimethyl sulfoxide acetonitrile solution, diluting to a scale, and shaking uniformly;
Acyclovir Wei Zhubei liquid, namely weighing a 10mg acyclovir sample in a 10ml measuring flask, precisely weighing, dissolving with a 10% dimethyl sulfoxide acetonitrile solution, diluting to a scale, and uniformly mixing.
Mixing standard solution, namely taking 1ml of impurity Q stock solution, 0.1ml of acyclovir stock solution into a 10ml measuring flask, dissolving with 10% dimethyl sulfoxide acetonitrile solution, diluting to scale, and shaking uniformly;
taking a sample solution, namely taking 10mg of acyclovir sample, dissolving the acyclovir sample in a 10ml volumetric flask by using a 10% dimethyl sulfoxide acetonitrile solution, diluting the acyclovir sample to a scale, and shaking the acyclovir sample uniformly;
2) And detecting the standard substance solution and the sample solution by adopting high performance liquid chromatography, wherein the conditions of the high performance liquid chromatography are as follows:
High performance liquid chromatograph, agilent 1260VWD;
Chromatographic column YMQ HILIC hybrid silica gel column (250 mm. Times.4.6 mm. Times.5 μm);
mobile phase a trifluoroacetic acid solution (ph=3.0);
Mobile phase B, acetonitrile;
isocratic elution: a: b=5:95
The flow rate of the mobile phase is 0.5ml/min;
Column temperature is 30 ℃;
the detection wavelength is UV254nm;
the sample injection amount is 20 μl.
FIG. 5 is a liquid chromatogram of the mixed solution prepared in example 2, and FIG. 6 is a liquid chromatogram of the sample solution of example 2.
The mixed solution is continuously injected for 6 needles, the areas of the impurity Q and the acyclovir Wei Feng are not obviously changed, which indicates that the impurity Q is not degraded into acyclovir under the chromatographic condition, and the result is as follows:
TABLE 3 stability investigation results of example 2 mixed solution
Component (A) 1 2 3 4 5 6 Average value of RSD%
Acyclovir 37.962 38.256 38.115 38.194 37.998 38.537 38.177 0.55
Impurity Q 35.404 35.144 34.716 34.397 34.249 34.585 34.749 1.27
The present invention can be realized by the respective raw materials listed in the present invention, and the upper and lower limits and interval values of the respective raw materials, and the upper and lower limits and interval values of the process parameters (such as temperature, time, etc.), and examples are not listed here.
While the invention has been described with respect to the preferred embodiments, it will be understood that the invention is not limited thereto, but is capable of modification and variation without departing from the spirit of the invention, as will be apparent to those skilled in the art.

Claims (6)

1.一种分离测定易水解大极性化合物的方法,其特征在于,包含如下步骤:1. A method for separating and determining easily hydrolyzed large polar compounds, characterized in that it comprises the following steps: 将含有易水解大极性化合物的样品溶于稀释剂中,形成样品溶液,采用高效液相色谱对标准品溶液和样品溶液进行检测,即可;The sample containing the easily hydrolyzed polar compound is dissolved in a diluent to form a sample solution, and the standard solution and the sample solution are tested by high performance liquid chromatography; 其中,稀释剂是10%二甲亚砜乙腈溶液;Wherein, the diluent is 10% dimethyl sulfoxide acetonitrile solution; 液相色谱条件:Liquid chromatography conditions: 色谱柱:杂化硅胶柱;流动相A:三氟乙酸溶液;流动相B:乙腈;采用等度洗脱;流动相流速:0.4~0.6ml/min;柱温:25~35℃;检测波长:UV254nm;进样量:20μl;运行时间:50min;Chromatographic column: hybrid silica gel column; mobile phase A: trifluoroacetic acid solution; mobile phase B: acetonitrile; isocratic elution; mobile phase flow rate: 0.4-0.6 ml/min; column temperature: 25-35 °C; detection wavelength: UV254 nm; injection volume: 20 μl; running time: 50 min; 所述含有易水解大极性化合物的样品为阿昔洛韦或双乙酰鸟嘌呤;The sample containing the easily hydrolyzed polar compound is acyclovir or diacetylguanine; 所述方法用于分离测定样品阿昔洛韦中杂质Q、或者样品双乙酰鸟嘌呤中单乙酰鸟嘌呤杂质;The method is used to separate and determine the impurity Q in the sample acyclovir, or the monoacetylguanine impurity in the sample diacetylguanine; 杂质Q为阿昔洛韦EP杂质Q,结构式为Impurity Q is acyclovir EP impurity Q, with the structural formula 双乙酰鸟嘌呤的结构式为 The structural formula of diacetylguanine is 单乙酰鸟嘌呤的结构式为阿昔洛韦的结构式为: The structural formula of monoacetylguanine is The structural formula of acyclovir is: 2.如权利要求1所述的分离测定易水解大极性化合物的方法,其特征在于:所述采用等度洗脱具体为按照下述体积比进行等度洗脱:96~94%A+4~6%B。2. The method for separating and determining easily hydrolyzed polar compounds as claimed in claim 1, characterized in that: the isocratic elution is specifically carried out according to the following volume ratio: 96-94% A + 4-6% B. 3.如权利要求1所述的分离测定易水解大极性化合物的方法,其特征在于:所述采用等度洗脱具体为按照下述体积比进行等度洗脱:95%A+5%B。3. The method for separating and determining easily hydrolyzed polar compounds as claimed in claim 1, characterized in that: the isocratic elution is specifically carried out according to the following volume ratio: 95% A + 5% B. 4.如权利要求1所述的分离测定易水解大极性化合物的方法,其特征在于:所述杂化硅胶柱为键合二羟丙基杂化硅胶柱。4. The method for separating and determining easily hydrolyzed large polar compounds as claimed in claim 1, characterized in that the hybrid silica gel column is a bonded dihydroxypropyl hybrid silica gel column. 5.如权利要求1所述的分离测定易水解大极性化合物的方法,其特征在于:所述三氟乙酸溶液的pH值为3.0~4.0。5. The method for separating and determining easily hydrolyzed large polar compounds according to claim 1, wherein the pH value of the trifluoroacetic acid solution is 3.0 to 4.0. 6.如权利要求5所述的分离测定易水解大极性化合物的方法,其特征在于:所述三氟乙酸溶液的pH值采用三氟乙酸调节。6. The method for separating and determining easily hydrolyzed large polar compounds as claimed in claim 5, characterized in that the pH value of the trifluoroacetic acid solution is adjusted by trifluoroacetic acid.
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JP3160439B2 (en) * 1993-09-03 2001-04-25 住化ファインケム株式会社 Method for producing acetylguanine
US5565565A (en) * 1994-08-04 1996-10-15 Syntex (U.S.A.) Inc. Preparation of N-9 substituted guanine compounds
CN111879713B (en) * 2020-07-27 2022-05-31 湖北省宏源药业科技股份有限公司 Method for judging reaction end point of diacetylguanine and controlling quality of finished product

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104359992A (en) * 2014-12-02 2015-02-18 湖北华世通潜龙药业有限公司 Method for analyzing acyclovir for injection by adopting high performance liquid chromatography (HPLC)
CN110940754A (en) * 2019-12-18 2020-03-31 湖北省宏源药业科技股份有限公司 High performance liquid chromatography method for separating and measuring impurities in valacyclovir hydrochloride

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