CN112255347B - Method for measuring ethirimol isomer - Google Patents
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Abstract
The invention discloses a method for measuring an ethirimol isomer, which comprises the following steps of firstly preparing an ethirimol isomer standard sample solution and an ethirimol sample solution; then, continuously measuring the standard sample solution for a plurality of times by using a liquid chromatography, calculating the response value of the ethirimol isomer during each measurement, and respectively measuring the standard sample solution and the sample solution for a plurality of times according to the following chromatographic conditions until the relative change of the response values of the two adjacent times is less than 1.5%, so as to obtain the chromatograms of the standard sample solution and the sample solution; and finally, calculating the mass fraction of the ethirimol isomer in the sample solution according to the formula (1). The standard deviation of the determination method is 0.24, the variation coefficient is 0.25%, the average recovery rate is 99.3%, and the linear correlation coefficient is 0.991, so that the ethirimol isomer and the ethirimol can be completely separated, the chromatographic peak shape is good, the integral calculation result is accurate, the repeatability is good, and the reliability of the obtained result is high.
Description
Technical Field
The invention belongs to the technical field of analysis, and particularly relates to a method for determining an ethirimol isomer.
Background
Bupirimate is a systemic hydroxypyrimidine fungicide developed by the chemical industry group of empire kingdom (now Daidan), can effectively control each development stage of powdery mildew germs, and is mainly used for preventing and controlling fruits and vegetables with high economic value, such as apples, strawberries, cucumbers and the like. The currently published and reported synthetic routes are all prepared by reacting ethirimol and N, N-dimethylaminosulfonyl chloride, the synthesis of ethirimol is divided according to characteristic raw materials and mainly comprises a nitroguanidine method and an ethylguanidine method, the nitroguanidine method has the advantage of high selectivity (no isomer), but the nitroguanidine is an insensitive explosive and has potential safety risk; the ethylguanidine method has high safety, but the existence of a certain proportion of ethirimol isomer can greatly influence the quality control of bupirimate. With the severe situation of the current chemical safety production, the industrial value of ethirimol prepared by an ethylguanidine method and further the synthesis of bupirimate is gradually highlighted.
It is therefore of great importance to monitor the amount of ethirimol isomers contained in ethirimol prepared by the ethylguanidine process efficiently. However, no quantitative determination method for ethirimol isomer exists in the reported analytical methods. Therefore, a quantitative analysis method of the bupirimate isomer, which is simple to operate and high in accuracy and does not influence the stability of the bupirimate, is urgently needed to effectively monitor the content of the bupirimate isomer and achieve the purpose of controlling the quality of the bupirimate product.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for measuring an ethirimol isomer, which solves the problem of quantitative analysis of the ethirimol isomer.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
a method for determining an ethirimol isomer, the method comprising the steps of:
step 1, dissolving an ethirimol isomer standard sample in a solvent to prepare an ethirimol isomer standard sample solution;
step 2, dissolving an ethirimol sample to be measured in a solvent to prepare an ethirimol sample solution;
and 3, continuously measuring the standard sample solution for a plurality of times by using liquid chromatography, wherein the chromatographic conditions during measurement are as follows: the column temperature is 20-40 ℃; the mobile phase comprises an organic solvent and water, wherein the organic solvent is acetonitrile or methanol; wherein the volume fraction of the water is 70-90%, the volume fraction of the organic solvent is 10-30%, and the sum of the total volume fractions is 100%; the flow rate of the mobile phase is 0.5 to 1.5ml/min, and the detection wavelength of the liquid chromatogram is 180 to 260nm;
calculating the response value of the ethirimol isomer at each time of determination until the relative change of the response values of two adjacent times is less than 1.5%, respectively performing N times of determination on the standard sample solution and the sample solution according to the chromatographic conditions, wherein N is more than or equal to 2, and obtaining chromatograms of the standard sample solution and the sample solution;
relative change in response value = (previous response value-next response value)/previous response value;
step 4, calculating the mass fraction X of the ethirimol isomer in the sample solution by adopting a formula (1),
in the formula (1), A 1 The average value of the peak areas of ethirimol isomers in the chromatograms of all standard sample solutions is represented; a. The 2 The average value of the peak areas of the ethirimol isomers in all the sample solutions is shown; m is 1 Representing the mass of the ethirimol isomer standard sample in g; m is 2 The mass of the ethirimol sample to be determined is expressed in g.
Preferably, when the standard sample solution and the sample solution are measured, the standard sample solution, the sample solution, and the standard sample solution are measured in this order to obtain four chromatogram graphs.
Preferably, the solvent in step 1 and step 2 is methanol or acetonitrile.
Specifically, the chromatographic column in the liquid chromatography detection is a C18 chromatographic column modified by polar groups.
Compared with the prior art, the invention has the beneficial effects that:
the standard deviation of the method for measuring the ethirimol isomer is 0.24, the coefficient of variation is 0.25%, the average recovery rate is 99.3%, and the linear correlation coefficient is 0.991, so that the ethirimol isomer and the ethirimol can be completely separated, the chromatographic peak shape is good, the integral calculation result is accurate, the repeatability is good, and the reliability of the obtained result is high.
Drawings
FIG. 1 is a chromatogram of ethirimol and its isomers under liquid chromatography conditions in example 2.
FIG. 2 is a graph of a linear correlation test of the method of the present invention.
Detailed Description
The invention aims to determine the content of ethirimol isomers in ethirimol for synthesizing bupirimate, and further select the ethirimol with the ethirimol isomers meeting requirements. The ethirimol isomer of the present invention has the structural formula (1):
the method for measuring the ethirimol isomer provided by the invention comprises the following steps of:
step 1, dissolving an ethirimol isomer standard sample in a solvent to prepare an ethirimol isomer standard sample solution;
step 2, dissolving an ethirimol sample to be measured in a solvent to prepare an ethirimol sample solution;
the solvent in step 1 and step 2 of the present invention is preferably methanol or acetonitrile.
Step 3, measuring by using liquid chromatography, wherein the chromatographic conditions are as follows: the column temperature is 20-40 ℃; the mobile phase comprises an organic solvent and water, wherein the volume fraction of the water is 70-90%, the volume fraction of the organic solvent is 10-30%, the sum of the volume fractions is 100%, and the organic solvent is acetonitrile or methanol; the flow rate of the mobile phase is 0.5 to 1.5ml/min, and the detection wavelength of the liquid chromatogram is 180 to 260nm; preferably, the column is a C18 column modified with polar groups.
After the baseline of the instrument is stable, continuously measuring the standard sample solution for a plurality of times according to a liquid chromatography, calculating the response value of the ethirimol isomer during each measurement, and respectively measuring the standard sample solution and the sample solution for N times according to chromatographic conditions when the relative change of the response values of two adjacent times is less than 1.5%, wherein N is more than or equal to 2, so as to obtain the chromatograms of the standard sample solution and the sample solution.
Wherein, the relative change of the response value = (previous response value-next response value)/previous response value. In the art, the magnitude of the response value refers to the magnitude of the peak area.
Preferably, the four chromatographic profiles are obtained by performing the measurement in the order of the standard solution, the sample solution and the standard solution.
Step 4, respectively averaging the peak areas of the ethirimol isomers in the sample solution and the standard solution to obtain A 1 And A 2 Calculating the mass fraction X of the ethirimol isomer in the sample solution by adopting a formula (1),
in the formula (1), A 1 The average value of the peak areas of ethirimol isomers in the chromatograms of all standard sample solutions is represented; a. The 2 Represents the average value of peak areas of ethirimol isomers in all the sample solutions; m is a unit of 1 The mass of the ethirimol isomer standard sample is expressed in g; m is 2 The mass of the ethirimol sample to be determined is expressed in g.
The following embodiments of the present invention are provided, and it should be noted that the present invention is not limited to the following embodiments, and all equivalent changes based on the technical solutions of the present invention are within the protection scope of the present invention.
The high performance liquid chromatograph used in the implementation process is a SHIMADZU LC-15C liquid chromatograph produced by Shimadzu of Japan, and is provided with an LC-15C infusion pump, an SPD-15C ultraviolet detector, a CTO-15C column incubator and an LC solution chromatography workstation.
Example 1
The amount of ethirimol sample to be measured in this example was 210 kg.
Operating conditions of the high performance liquid chromatography: and (3) chromatographic column: shim-pack GIST C18-AQ (5 μm,4.6 mm. Times.250 mm); mobile phase: acetonitrile: water =10 (V/V); flow rate: 1.0mL/min; column temperature: 35 ℃; detection wavelength: 235nm; the injection volume was 5. Mu.L.
Preparing a standard sample solution: accurately weighing 0.02g (accurate to 0.0002 g) of ethirimol isomer standard sample, placing the ethirimol isomer standard sample in a 50mL volumetric flask, dissolving the ethirimol standard sample with methanol, metering to a scale, and shaking up for later use.
Preparation of sample solution: accurately weighing 0.02g (accurate to 0.0002 g) of ethirimol-containing sample, placing the ethirimol-containing sample in a 50mL volumetric flask, dissolving the ethirimol-containing sample with methanol, fixing the volume to a scale, and shaking up for later use.
And (3) sample determination: under the operating conditions, after the baseline of the instrument is stabilized, continuously measuring the standard solution for a plurality of times, calculating the relative response value of the ethirimol isomer until the relative change of the response values of the adjacent 2 times is less than 1.5%, and measuring according to the sequence of the standard sample solution, the sample solution and the standard sample solution. The results were calculated using the average of the areas obtained in 2 replicates.
And (4) calculating a result: and (3) respectively averaging the peak areas of the ethirimol isomers in the 2-needle sample solution and the 2-needle standard solutions before and after the sample solution, and calculating the mass fraction X of the ethirimol isomer in the sample according to the formula (1). The calculated mass fraction of ethirimol isomer in the sample was 3.8%.
Example 2
The amount of ethirimol sample to be measured in this example was 220 kg.
Operating conditions of the high performance liquid chromatography: and (3) chromatographic column: shim-pack GIST C18-AQ (5 μm,4.6 mm. Times.250 mm); mobile phase: acetonitrile: water =20 (V/V); flow rate: 1.0mL/min; column temperature: 35 ℃; detection wavelength: 235nm; the injection volume was 5. Mu.L.
Preparing a standard sample solution: accurately weighing 0.02g of ethirimol isomer standard sample (accurate to 0.0002 g), placing the ethirimol isomer standard sample in a 50mL volumetric flask, dissolving the ethirimol standard sample in methanol, metering to a scale, and shaking up for later use.
Preparation of sample solution: accurately weighing 0.02g (accurate to 0.0002 g) of ethirimol-containing sample, placing the ethirimol-containing sample in a 50mL volumetric flask, dissolving the ethirimol-containing sample with methanol, fixing the volume to a scale, and shaking up for later use.
And (3) sample determination: under the operating conditions, after the baseline of the instrument is stable, the standard solution is continuously measured for a plurality of times, the relative response value of the ethirimol isomer is calculated until the relative change of the response values of the adjacent 2 times is less than 1.5%, and the measurement is carried out according to the sequence of the standard sample solution, the sample solution and the standard sample solution. The results were calculated using the average of the areas obtained in 2 replicates.
And (4) calculating a result: and respectively averaging the peak areas of the ethirimol isomers in the 2-pin sample solution and the 2-pin standard solution before and after the sample solution, wherein the mass fraction X of the ethirimol isomer in the sample is calculated according to the formula (1). The mass fraction of the ethirimol isomer in the sample is calculated to be 2.8%.
Example 3
The number of ethirimol samples to be determined in this example was 215 kg.
Operating conditions of the high performance liquid chromatography: a chromatographic column: shim-pack GIST C18-AQ (5 μm,4.6 mm. Times.250 mm); mobile phase: acetonitrile: water =30 (V/V); flow rate: 1.0mL/min; column temperature: 35 ℃; detection wavelength: 235nm; the injection volume was 5. Mu.L.
Preparing a standard sample solution: accurately weighing 0.02g (accurate to 0.0002 g) of ethirimol isomer standard sample, placing the ethirimol isomer standard sample in a 50mL volumetric flask, dissolving the ethirimol standard sample with methanol, metering to a scale, and shaking up for later use.
Preparation of sample solution: accurately weighing 0.02g (accurate to 0.0002 g) of ethirimol-containing sample, placing the ethirimol-containing sample in a 50mL volumetric flask, dissolving the ethirimol-containing sample with methanol, fixing the volume to a scale, and shaking up for later use.
And (3) sample determination: under the operating conditions, after the baseline of the instrument is stable, the standard solution is continuously measured for a plurality of times, the relative response value of the ethirimol isomer is calculated until the relative change of the response values of the adjacent 2 times is less than 1.5%, and the measurement is carried out according to the sequence of the standard sample solution, the sample solution and the standard sample solution. The results were calculated using the average of the areas obtained in 2 replicates. .
And (4) calculating a result: and (3) respectively averaging the peak areas of the ethirimol in the 2-needle sample solution and the standard solutions of the front and rear 2 needles of the sample solution, and calculating the mass fraction X of the ethirimol isomer in the sample according to the formula (1).
The mass fraction of the ethirimol isomer in the sample was calculated to be 3.6%.
Example 4
In the existing batch of ethirimol samples, the quantity is 220 kg, and the content of ethirimol isomers in the batch of goods needs to be detected.
Operating conditions of the high performance liquid chromatography: a chromatographic column: shim-pack GIST C18-AQ (5 μm,4.6 mm. Times.250 mm); mobile phase: methanol: water =20 (V/V); flow rate: 1.0mL/min; column temperature: 35 ℃; detection wavelength: 235nm; the injection volume was 5. Mu.L.
Preparing a standard sample solution: accurately weighing 0.02g of ethirimol isomer standard sample (accurate to 0.0002 g), placing the ethirimol isomer standard sample in a 50mL volumetric flask, dissolving the ethirimol standard sample in methanol, metering to a scale, and shaking up for later use.
Preparation of sample solution: accurately weighing 0.02g (accurate to 0.0002 g) of ethirimol-containing sample, placing the ethirimol-containing sample in a 50mL volumetric flask, dissolving the ethirimol-containing sample with methanol, fixing the volume to a scale, and shaking up for later use.
And (3) sample determination: under the operating conditions, after the baseline of the instrument is stable, the standard solution is continuously measured for a plurality of times, the relative response value of the ethirimol isomer is calculated until the relative change of the response values of the adjacent 2 times is less than 1.5%, and the measurement is carried out according to the sequence of the standard sample solution, the sample solution and the standard sample solution. The results were calculated using the average of the areas obtained in 2 replicates.
And (4) calculating a result: and respectively averaging the peak areas of the ethirimol isomers in the 2-pin sample solution and the 2-pin standard solution before and after the sample solution, wherein the mass fraction X of the ethirimol isomer in the sample is calculated according to the formula (1). The mass fraction of the ethirimol isomer in the sample was calculated to be 2.7%.
At present, a method for determining the content of ethirimol by adopting a liquid chromatography is disclosed in part of existing methods, but trifluoroacetic acid is used in the method, so that the method has certain corrosivity on equipment after long-term use, and when the liquid chromatography system is used for determining the synthesis of bupirimate, the residual trifluoroacetic acid can influence the detection accuracy because the bupirimate is easy to decompose when encountering acid.
The method of the invention was tested for validation as follows:
the method has the following precision:
six ethirimol samples are weighed respectively, and six times of parallel determination are carried out according to the method. The results are shown in table 1, and the standard deviation of the ethirimol isomer is 0.24, and the coefficient of variation is 0.25%, which indicates that the method has high precision.
TABLE 1 method precision test determination results
Accuracy test of the method
Adding different amounts of ethirimol isomer standard solutions into samples with known contents by adopting a standard addition method, measuring the contents of the ethirimol isomer standard solutions according to the chromatographic conditions, and calculating the recovery rate, wherein the recovery rate is between 98.4% and 100.3%, and the average recovery rate is 99.3%.
TABLE 2 determination of precision test of method
Method of linear correlation test
Accurately weighing 0.1g (accurate to 0.0002 g) of an ethirimol isomer standard sample in a 50mL volumetric flask, dissolving the ethirimol isomer standard sample with methanol, fixing the volume to a scale, preparing 2000mg/L standard mother liquor, preparing standard solutions with mass concentrations of 1200, 1000, 750, 500, 300 and 150mg/L by using the standard mother liquor, and analyzing the standard solutions respectively to obtain response values. And drawing a standard curve by taking the mass concentration of the standard solution as an abscissa and the response value as an ordinate. The obtained ethirimol isomer standard curve y =22638x, and the correlation coefficient is 0.991, which shows that the linear relation between the response value and the mass concentration of the ethirimol isomer is good in the range of the mass concentration of 150-1200 mg/L.
TABLE 3 results of the Linear correlation test
Claims (3)
1. The method for measuring the ethirimol isomer is characterized by comprising the following steps of:
step 1, dissolving an ethirimol isomer standard product in a solvent to prepare an ethirimol isomer standard sample solution;
step 2, dissolving an ethirimol sample to be measured in a solvent to prepare an ethirimol sample solution;
and 3, continuously measuring the standard sample solution for a plurality of times by using liquid chromatography, wherein the chromatographic conditions during measurement are as follows: the column temperature is 20 to 40 ℃; the mobile phase comprises an organic solvent and water, wherein the organic solvent is acetonitrile or methanol; wherein the volume fraction of the water is 70-90%, the volume fraction of the organic solvent is 10-30%, and the sum of the total volume fractions is 100%; the flow rate of the mobile phase is 0.5 to 1.5ml/min, and the detection wavelength of the liquid chromatogram is 235nm;
calculating the response value of the ethirimol isomer at each time of determination until the relative change of the response values of two adjacent times is less than 1.5%, respectively performing N times of determination on the standard sample solution and the sample solution according to the chromatographic conditions, wherein N is more than or equal to 2, and obtaining chromatograms of the standard sample solution and the sample solution;
relative change in response value = (previous response value-next response value)/previous response value;
step 4, calculating the mass fraction of ethirimol isomer in the sample solution by adopting a formula (1)X，
In the formula (1), A 1 The average value of the peak areas of ethirimol isomers in the chromatograms of all standard sample solutions is represented; a. The 2 The average value of the peak areas of the ethirimol isomers in all the sample solutions is shown; m is 1 Representing the mass of the ethirimol isomer standard sample in g; m is 2 Representing the mass of the ethirimol sample to be determined in g;
the ethirimol isomer has a structural formula as follows:
the chromatographic column in the liquid chromatography detection is a C18 chromatographic column modified by polar groups.
2. The method for measuring an ethirimol isomer as claimed in claim 1, wherein the measurement is carried out on the standard sample solution and the sample solution in the order of the standard sample solution, the sample solution and the standard sample solution, and four chromatographic profiles are obtained.
3. The method for measuring an ethirimol isomer as claimed in claim 1, wherein the solvents used in the steps 1 and 2 are both methanol or acetonitrile.
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| DK2686303T3 (en) * | 2011-03-18 | 2016-03-29 | Bayer Ip Gmbh | N- (3-carbamoylphenyl) -1 H -pyrazole-5-carboxamide derivatives and their use for controlling animal pests |
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| GB1444548A (en) * | 1972-11-17 | 1976-08-04 | Ici Ltd | Manufacture of pyrimidines |
| CN101307024A (en) * | 2008-07-16 | 2008-11-19 | 西安近代化学研究所 | Method for synthesizing 5-nbutyl-2-ethylamido-6-methylpyrimidine-4-dimethyl amine sulfonic acid ester |
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