CN111366643B - Detection method of OLED material intermediate - Google Patents
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- 239000000463 material Substances 0.000 title claims abstract description 14
- 238000004458 analytical method Methods 0.000 claims abstract description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 20
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- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 9
- 239000012086 standard solution Substances 0.000 claims description 9
- 238000007865 diluting Methods 0.000 claims description 7
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- 239000012043 crude product Substances 0.000 abstract description 4
- 238000003908 quality control method Methods 0.000 abstract description 3
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- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
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Abstract
The invention discloses a detection method of an intermediate of an OLED material, the intermediate is a compound with a structure shown in a formula (I), a liquid phase mass spectrum (LC-MS) and NMR are utilized to carry out specificity confirmation on a sample which is crystallized for many times and purified by an SPE column, the sample is determined as a standard sample after the confirmation is successful, DAD is used for determining the optimal detection wavelength, the retention time is used for subsequent detection of a crude product of the compound, and the detection conditions are as follows: the chromatographic column is Venusil XBP 4.6 multiplied by 150mm, the grain diameter of the filler is 5 mu m, and the column temperature is 40 ℃; the mobile phase is methanol to water, the proportion is set as the following table, the flow rate is 1.0ml/min, the detection and analysis time is not less than 15 minutes, and the sample detection time is 7.02 minutes. And drawing a standard curve by using the standard sample, and carrying out quantitative detection on the sample. The method has the advantages of convenient post-pretreatment, simple operation and high result accuracy, meets the requirement of enterprises on the quality control of the intermediate, uses the short chromatographic analysis column in the detection, reduces the consumption of the mobile phase, and reduces the resource consumption and the pollution to the environment.
Description
Technical Field
The invention belongs to the field of analytical chemistry, and particularly relates to a qualitative and quantitative detection method of a novel OLED material intermediate based on HPLC.
Background
Organic Light-Emitting diodes (OLEDs), also known as Organic electroluminescent displays and Organic Light-Emitting semiconductors, have the advantages of self-luminescence, wide viewing angle, high contrast, low power consumption, high response rate, full color, and simple process, and have been rapidly developed in recent years.
The organic luminescent material is a novel material obtained by chemical synthesis, and the (E) -3- (3, 5-di-tert-butylphenyl) -1- (2-methoxybenzo [ b, d ] furan-3-yl) prop-2-ene-1-ketone is an important intermediate of the organic luminescent material of a Pt complex, and the structural formula is shown as the following (I). The structural accuracy directly influences whether the product can be successfully synthesized in the next step, and the quantitative accuracy influences the calculation of the material feeding amount and the final yield.
The OLED industry has high requirements on materials, and a simple and rapid analysis method with high sensitivity and good specificity is required in the whole production process. The specificity of a standard substance which is crystallized for many times and purified by an SPE column is confirmed by LC-MS and NMR, the optimal detection wavelength is determined by DAD, and the quality of a crude compound is qualitatively, quantitatively and analytically contained by a High Performance Liquid Chromatography (HPLC), so that the quality of the intermediate is effectively guaranteed.
Disclosure of Invention
The invention provides a method for detecting a novel OLED material intermediate with a structure shown in a formula (I), which is simple and convenient in pretreatment and can accurately detect the content of a sample.
The detection method of the novel OLED material intermediate with the structure shown in the formula (I) adopts HPLC qualitative and quantitative detection, and the detection conditions are as follows: the chromatographic column is Venusil XBP 4.6 multiplied by 150mm, the grain diameter of the filler is 5 mu m, and the column temperature is 40 ℃; the mobile phase is methanol to water, the proportion is set as shown in the table, the flow rate is 1.0ml/min, and the detection and analysis time is not less than 15 minutes.
The mobile phase ratio was set as follows:
the novel OLED material intermediate with the structure of the formula (I) has a retention time of 7.02 minutes.
Analytical detection prior to qualitative and quantitative detection by HPLC, the detection method further comprising: liquid phase mass spectrometry (LC-MS) qualitative, and the conditions are as follows: an ion source: ESI + APCI dual ion source for Shimadzus DUIS-2020, ion mode: positive/negative, interface voltage: 4.5KV (positive), -4.5KV (negative), Q-array radio frequency voltage: 60V, interface temperature: 350 ℃, DL temperature: 250 ℃, heating block temperature: 400 ℃, flow rate of drying gas: 15L/min, atomizing gas flow rate: 1.5L/min.
Qualitative by 1HNMR, Varian 400MHz superconducting nuclear magnetic resonance spectrometer, conditions: the solvent was CDCl3, and the concentration of the solution was 20 mg/mL.
Spectral scanning of the standard sample by the DAD detector: dissolving the standard substance in DCM to prepare a solution with a concentration of 100mg/L, performing spectrum scanning on the solution of the standard substance, and determining that the absorption degree is maximum and the concentration and the absorption degree present a positive relationship, namely the optimal detection wavelength, wherein the detection wavelength is 325 nm.
The detection method also comprises quantitative detection of an HPLC method, and (1) standard curve drawing: weighing 100mg of a standard substance, accurately measuring the standard substance to 0.1mg, adding a proper amount of DCM (DCM) into a 100mL volumetric flask, dissolving, fixing the volume to a scale, shaking up to obtain 1mg/mL of a mother solution of the standard substance, gradually diluting the mother solution into 100mg/L, 80mg/L, 60mg/L, 40mg/L, 20mg/L, 10mg/L and 5mg/L of series standard substance solutions, bottling the solutions through a 0.45um organic filter membrane, detecting on a machine, and drawing a curve by taking a peak area as a vertical coordinate and a concentration as a horizontal coordinate; (2) quantifying the sample: weighing about 50mg of a sample, accurately measuring the sample to 0.1mg, dissolving a proper amount of DCM in a 25mL volumetric flask, fixing the volume, shaking up, transferring 1mL of the sample in the 25mL volumetric flask by using a pipette, fixing the volume of the DCM, shaking up, filtering a proper amount of 0.45um organic filter membrane, bottling, detecting on a machine, reading the content by using a standard curve, and calculating the actual content according to the following formula;
in the formula:
x-sample content,% c-sample concentration read from the curve, mg/L
V-total dilution volume, mL m-sample weight, mg.
The method is realized by the following specific technical scheme: the specificity of the standard product after repeated crystallization and SPE column purification is confirmed by liquid phase mass spectrum (LC-MS) and NMR methods, the optimal detection wavelength is determined by DAD, a proper chromatographic column is selected, a proper column temperature is determined, a mobile phase is adjusted, a standard curve is drawn, and the common crude product is quantified by an external standard method.
1.1 liquid phase mass spectrometry (LC-MS) characterization, with the conditions:
an ion source: shimadzus DUIS-2020 double ion source (ESI + APCI)
Ion mode: positive/negative
Interface voltage: 4.5KV (positive), -4.5KV (negative)
Q array radio frequency voltage: 60V
Interface temperature: 350 deg.C
DL temperature: 250 deg.C
Temperature of the heating block: 400 deg.C
Flow rate of drying gas: 15L/min
Flow rate of atomizing gas: 1.5L/min
1.2 characterization by NMR, Varian 400MHz superconducting nuclear magnetic resonance spectrometer, conditions: the solvent was CDCl3 solution with a concentration of 20mg/mL (1H spectrum).
1.3 spectral scanning by a DAD detector: dissolving a standard substance in DCM, preparing the concentration of 100mg/L, scanning the solution of the standard substance within the range of 200 nm-700 nm, determining that the absorption wavelength with the maximum absorbance and the positive relation between the concentration and the absorbance is the detection wavelength, and finally selecting the detection wavelength to be 325 nm.
1.4 selecting a suitable chromatography column: the research compares that firstly Inertsutasin C184.6 multiplied by 250mm 5 μm, secondly Inertsil ODS-SP 4.6 multiplied by 250mm 5 μm, thirdly Venusil XBP 4.6 multiplied by 250mm 5 μm, fourthly Waters Xbridge C184.6 multiplied by 150mm3.5 μm, thirdly Inertsutasin C184.6 multiplied by 150mm 5 μm, and fourthly Inertsil ODS-SP 4.6 multiplied by 150mm 5 μm, and finally the chromatographic column selected is Venusil XBP 4.6 multiplied by 150mm 5 μm, and comprehensively considering the total analysis time and the separation degree of impurities.
1.5 determination of the appropriate column temperature: the results of the separation of impurities, the peak pattern, the total analysis time and the like at 4 column temperatures of 30 ℃, 35 ℃, 40 ℃, 45 ℃ and the like are respectively considered, and the finally selected column temperature is 40 ℃.
1.6 adjusting the mobile phase:
1.6.1 the mobile phase MEOH is compared with ACN, respectively, and the MEOH is finally selected as the organic phase.
1.6.2 the mobile phase is MEOH, flow rate 1.5 ml/min: determining impurities with minimum polarity by using a lower-polarity mobile phase and a higher flow rate, and analyzing the condition of the impurities after a main peak;
1.6.3 the mobile phase is MEOH-H 2 O-7-3 (v-v), flow rate 1.0 ml/min: increasing the retention time of the main substance by using a higher-polarity mobile phase, determining the existence condition of impurities in front of the main peak, and inspecting whether the main peak is wrapped by unseparated impurities;
1.6.4 flow rate: 1.0ml/min, better impurity separation has been achieved by adjusting the mobile phase gradient, shorter analysis time, the final selected mobile phase ratio is set as follows:
1.7 standard curve is drawn: weighing 100mg (accurate to 0.1mg) of a standard substance into a 100mL volumetric flask, adding an appropriate amount of DCM (DCM) to dissolve the standard substance, fixing the volume to the scale, shaking up to obtain 1mg/mL of a standard substance mother solution, gradually diluting the standard substance mother solution into 100mg/L, 80mg/L, 60mg/L, 40mg/L, 20mg/L, 10mg/L and 5mg/L series of standard solutions, bottling the standard substance mother solution through a 0.45um organic filter membrane, detecting the standard substance mother solution on a machine by taking a peak area as a vertical coordinate and a concentration as a horizontal coordinate, and drawing a curve.
1.8 sample quantification: weighing about 50mg (accurate to 0.1mg) of a sample in a 25mL volumetric flask, dissolving a proper amount of DCM, fixing the volume, shaking up, transferring 1mL in the 25mL volumetric flask by using a pipette, fixing the volume of DCM, shaking up, passing a proper amount of 0.45um organic filter membrane, bottling, detecting on a machine, reading out the content by using a standard curve, and calculating the actual content according to a formula.
And (4) conclusion: the invention establishes a novel OLED intermediate content detection method based on HPLC, only uses a common C18 column and a simple MEOH-H2O mobile phase system to achieve the purpose of separating main substances from impurities, has simple pretreatment, high result precision and accuracy and shorter analysis time, and provides effective guarantee for the quality control of the intermediate.
Description of the drawings:
FIG. 1 is a LC-MS diagram of a compound of the present invention.
FIG. 2 is a DAD spectrum of a compound of the present invention.
FIG. 3 is a HPLC chart of the compounds of the present invention under different chromatographic columns (long columns).
FIG. 4 is a HPLC chart of the compounds of the present invention under different chromatographic columns (short columns).
FIG. 5 is a HPLC plot of compounds of the invention at different column temperatures.
FIG. 6 is a HPLC plot of compounds of the invention in different mobile phases.
FIG. 7 is a graph of a standard curve of a compound of the present invention.
FIG. 8 is an HPLC plot of a standard and sample of a compound of the invention.
The specific implementation mode is as follows:
a novel OLED intermediate content detection method based on HPLC is characterized in that specificity of a standard product which is crystallized for many times and purified by an SPE column is confirmed by liquid phase mass spectrum (LC-MS) and NMR, the optimal detection wavelength is determined by DAD, retention time is used for qualitative detection in follow-up detection, a proper chromatographic column is selected, a proper column temperature is determined, a mobile phase is adjusted, a standard curve is drawn, and qualitative and quantitative analysis and impurity analysis are carried out on a crude product of a compound.
The method comprises the following specific steps:
laboratory instruments and reagents:
shimadzu LC-20AD dual pump HPLC equipped with DAD detector; a Varian 400MHz superconducting NMR spectrometer; shimadzu LC-MS2020(DUIS-ESI + APCI Dual ion Source); analytical balance (mettlerlotol); millipore ultra-pure water machine; 0.45 mu organic filter membrane; HPLC grade methanol, acetonitrile; glassware is commonly used in other laboratories.
1. Liquid phase mass spectrometry (LC-MS) is qualitative, and the setting conditions are as follows:
an ion source: shimadzus-2020 Dual ion Source (ESI + APCI)
Ion mode: positive/negative
Interface voltage: 4.5KV (positive), -4.5KV (negative)
Q array radio frequency voltage: 60V
Interface temperature: 350 deg.C
DL temperature: 250 deg.C
Temperature of the heating block: 400 deg.C
Flow rate of drying gas: 15L/min
Flow rate of atomizing gas: 1.5L/min
And 5 mu L of standard solution with the concentration of 100mg/L is injected, the base peak is +411(+ H), and the analysis result is consistent with the theoretical value. (see attached FIG. 1)
2. Qualitative by NMR, Varian 400MHz superconducting nuclear magnetic resonance spectrometer, conditions: solvent CDCl3 sample concentration was 20mg/mL (1H spectrum).
And (4) result analysis: 1H NMR (400MHz, CDCl3) δ 7.98(d, J ═ 7.7Hz,2H),7.81(s,1H),7.62(s,1H),7.58(s,1H),7.51(s,2H),7.44(s,2H),7.38(d, J ═ 4.3Hz,2H),4.01(s,3H),1.35(s,18H), the analytical results were consistent with the theoretical values.
3. Spectral scanning by DAD detector: the standard substance is dissolved in DCM, the concentration of the prepared sample is 100mg/L, the standard substance solution is scanned within the range of 200 nm-700 nm, two absorption peaks are provided, namely 210nm and 325nm respectively, and the detection wavelength finally selected is 325nm because 210nm is close to the ultraviolet cut-off wavelength of the mobile phase. (see attached FIG. 2)
4. Selecting a suitable chromatographic column: research and comparison are carried out on INertsutasin C184.6 multiplied by 250mm 5 mu m, Inertsil ODS-SP 4.6 multiplied by 250mm 5 mu m, Venusil XBP 4.6 multiplied by 250mm 5 mu m, Waters Xbridge C184.6 multiplied by 150mm3.5 mu m, Inertsutasin C184.6 multiplied by 150mm 5 mu m, Inertsil ODS-SP 4.6 multiplied by 150mm 5 mu m and Venusil XBP 4.6 multiplied by 150mm 5 mu m, and the analysis time of the long column is generally longer from the result, and short columns are optimized for improving the efficiency and reducing the consumption of mobile phases and reducing the resource consumption and the pollution to the environment; from the results of 4 short columns, the small-particle-size high-efficiency column of Waters Xbridge C184.6X 150mm3.5 μm has obvious advantages in analysis time, but the column pressure is too high, and the service life of the instrument is influenced for the non-ultrahigh liquid phase; the final column selected was Venusil XBP 4.6X 150mm 5 μm from a total analysis time taken in combination with the degree of separation of impurities. (see FIGS. 3 and 4)
5. Determination of the appropriate column temperature: the results of the separation degree, the peak pattern, the total analysis time and the like of the impurities at 4 column temperatures of 30 ℃, 35 ℃, 40 ℃, 45 ℃ and the like are respectively considered, the results show that the separation degree of the impurities and the main substances at the 4 column temperatures all meet the requirements, the total analysis time is 45 ℃ shortest, but the difference is not great from the time phase at the column temperature of 40 ℃, and the finally selected column temperature is 40 ℃ because the high column temperature damages a chromatographic column and an instrument. (see the attached FIG. 5)
6. Adjusting the mobile phase:
6.1 comparing MEOH with ACN, the experimental results show that although ACN has a certain advantage for separating impurities, the difference in total analysis time is not large, and methanol can achieve impurity separation by adjusting the proportion of the water phase in the mobile phase at a later stage. (see the attached figure 6)
6.2 the mobile phase is MEOH, flow rate 1.5 ml/min: and (4) determining impurities with minimum polarity by using a lower-polarity mobile phase and a higher flow rate, and analyzing the condition of the impurities after the main peak.
6.3 mobile phase MEOH-H2O ═ 7-3(v-v), flow rate 1.0 ml/min: and (3) increasing the retention time of the main substance by using a higher-polarity mobile phase, determining the existence condition of the impurities in front of the main peak, and inspecting whether the main peak is wrapped by the unseparated impurities.
6.4 flow rate: 1.0ml/min, the mobile phase ratio was set as follows:
as a result: impurities were well separated from the main peak, with the maximum retained impurity being 29.3min and the total analysis time being 35 min.
6.5 flow rate: 1.0ml/min, the mobile phase ratio was set as follows
As a result: impurities were well separated from the main peak with a total analysis time of 25 min.
6.6 flow rate: 1.0ml/min, the mobile phase ratio was set as follows
As a result: the separation degrees of the main peak and the first impurity before and after the main peak are respectively 2.56 and 2.98, both are more than 1.5, and the total analysis time is 15 min.
6.7 flow rate: 1.0ml/min, the mobile phase ratio was set as follows
As a result: the separation degrees of the main peak and the first impurity before and after are respectively 1.37 and 1.48, and the separation degree requirement of more than 1.5 is not met.
7. Final chromatographic conditions: the chromatographic column is Venusil XBP 4.6 multiplied by 150mm 5 μm, the flow rate is 1.0ml/min, the column temperature is 40 ℃, the detection wavelength is 325nm, and the proportion of the mobile phase is set as follows:
8. drawing a standard curve: weighing 100mg (accurate to 0.1mg) of a standard substance into a 100mL volumetric flask, adding an appropriate amount of DCM (DCM) to dissolve the standard substance, fixing the volume to the scale, shaking up to obtain 1mg/mL of a standard substance mother solution, gradually diluting the standard substance mother solution into 100mg/L, 80mg/L, 60mg/L, 40mg/L, 20mg/L, 10mg/L and 5mg/L series of standard solutions, bottling the standard substance mother solution through a 0.45um organic filter membrane, detecting the standard substance mother solution on a machine by taking a peak area as a vertical coordinate and a concentration as a horizontal coordinate, and drawing a curve. (see FIG. 7)
9. Quantifying the sample: weighing about 50mg (accurate to 0.1mg) of a sample in a 25mL volumetric flask, dissolving a proper amount of DCM, fixing the volume and shaking up, transferring 1.0mL in the 25mL volumetric flask by using a pipette, fixing the volume of DCM, shaking up, passing a proper amount of a 0.45um organic filter membrane, bottling, detecting on a machine, determining the nature by using retention time (see attached figure 8), reading the content by using a standard curve, and calculating the actual content according to the following formula.
In the formula:
x-sample content,% c-sample concentration read from the curve, mg/L
V-total dilution volume, mL m-sample weight, mg
10. Methodology validation
And verifying the finally determined detection method by precision, accuracy, linear range and the like.
10.1 precision-6 parallel
Weighing about 50mg (accurate to 0.1mg) of a sample in a 25mL volumetric flask, dissolving a proper amount of DCM, fixing the volume and shaking up, transferring 1.0mL in the 25mL volumetric flask by using a pipette, fixing the volume of DCM, shaking up, passing a proper amount of 0.45um organic filter membrane, bottling, detecting on a machine, reading out the content by using a standard curve, calculating the actual content according to a content formula, and performing parallel experiments for 6 parts, wherein the result is shown in the following table:
| number of | 1# | 2# | 3# | 4# | 5# | 6# | Mean value of | RSD,％ |
| Results of detection,% | 46.91 | 47.36 | 46.83 | 46.99 | 47.11 | 46.16 | 46.89 | 0.86 |
As a result: the parallel RSD of sample 6 was 0.86%, and the precision was good.
10.2 accuracy test-recovery by adding Standard
Weighing about 50mg (accurate to 0.1mg) of a sample into a 25mL volumetric flask, then respectively adding three horizontal standard samples of 5mL (equivalent added standard 5mg), 10mL (equivalent added standard 10mg) and 20mL (equivalent added standard 20mg) of standard mother liquor of 1mg/mL into the volumetric flask, carrying out 3 parallel experiments at each point of adding standard, dissolving a proper amount of DCM, fixing the volume and shaking up, transferring 1.0mL into the 25mL volumetric flask by a pipette, fixing the volume and shaking up after DCM, taking a proper amount of organic filter membrane passing 0.45um, bottling and testing, reading out the content by a standard curve, calculating the actual content according to a content formula, calculating the recovery rate according to the following recovery rate formula, and obtaining a result table:
as a result, the recovery rate of the three concentration points is between 98.57% and 99.86%, and the recovery rate is good.
The recovery rate calculation formula is as follows:
in the formula:
p-recovery,% c 1 -adding the standard measurement value%
c 2 Sample background measurement,% c 3 -adding a scalar quantity,%
3. Linearity and range
Weighing 100mg (accurate to 0.1mg) of a standard sample in a 100mL volumetric flask, adding an appropriate amount of DCM (DCM) for dissolution, fixing the volume to the scale, shaking up to obtain 1mg/mL of a standard mother solution, gradually diluting the standard mother solution into 100mg/L, 80mg/L, 60mg/L, 40mg/L, 20mg/L, 10mg/L and 5mg/L of standard solutions, bottling the standard solutions through a 0.45um organic filter membrane, detecting, taking the peak area as the ordinate and the concentration as the abscissa, drawing a curve, and obtaining a correlation coefficient R which is 0.99995, which shows that the concentration and the peak area in the concentration range present a good linear relationship. (see FIG. 7)
In summary, the patent develops and verifies a novel method for detecting the content of an OLED intermediate based on HPLC, and utilizes liquid phase mass spectrometry (LC-MS) and NMR methods to specially confirm a standard product which is crystallized for many times and purified by an SPE column, determines the optimal detection wavelength by DAD, qualitatively detects a subsequent crude product of the compound by retention time, selects a proper chromatographic column, determines a proper column temperature, adjusts a mobile phase, draws a standard curve, and quantifies a sample. The method has the advantages of simple post-pretreatment, convenient operation, high precision and accuracy, and capability of being verified by methodology, is suitable for monitoring the synthesis reaction process, and meets the requirement of enterprises on the quality control of the intermediate body.
Claims (8)
1. The detection method of the novel OLED material intermediate with the structure shown in the formula (I) adopts HPLC qualitative and quantitative detection, and the detection conditions are as follows: the chromatographic column is Venusil XBP C184.6 multiplied by 150mm, the grain diameter of the filler is 5 mu m, and the column temperature is 40 ℃; the mobile phase is methanol to water, the proportion is set in the following table, the flow rate is 1.0ml/min, and the detection and analysis time is not less than 15 minutes;
the mobile phase ratio was set as follows:
2. the detection method according to claim 1, wherein the novel OLED material intermediate of formula (I) has a retention time of 7.02 min.
3. The assay of claim 1, further comprising an analytical test prior to the qualitative and quantitative HPLC assay, the standard being spectrally scanned by a DAD detector: dissolving the standard substance in DCM, preparing a solution with the concentration of 100mg/L, scanning the standard solution, determining that the absorbance of the standard solution is maximum and the concentration and the absorbance have a positive relationship, and finally selecting the detection wavelength to be 325 nm.
4. The detection method of claim 3, further comprising qualifying the liquid mass spectrum of the standard prior to the qualitative and quantitative HPLC detection, provided that the ion source: ESI + APCI Dual ion Source for Shimadzu DUIS-2020, ion mode: positive/negative, interface voltage: 4.5KV, -4.5KV, Q array radio frequency voltage: 60V, interface temperature: 350 ℃, DL temperature: 250 ℃, heating block temperature: 400 ℃, flow rate of drying gas: 15L/min, atomizing gas flow rate: 1.5L/min.
5. The assay of claim 4, further comprising 1HNMR qualitative, Varian 400MHz superconducting NMR spectrometer of the standard prior to the HPLC qualitative and quantitative assay, conditions: the solvent was CDCl3, and the sample concentration was 20 mg/mL.
6. The detection method according to claim 5, further comprising quantitative detection calculation by HPLC method, wherein (1) the standard substance shown in formula (I) is subjected to qualitative detection by 1HNMR and qualitative detection by liquid mass spectrometry, and then qualitative and quantitative detection by HPLC is adopted, and a standard curve is drawn at the same time: weighing a standard sample of formula (I), adding a solvent to fix the volume, gradually diluting the standard sample into a series of standard solutions, filtering, detecting, and drawing a curve by taking a peak area as a vertical coordinate and a concentration as a horizontal coordinate; (2) weighing a sample to be detected, dissolving, quantifying, filtering, detecting, reading the content by using a standard curve, and calculating the actual content according to the following formula;
in the formula:
x-sample content,% c-sample concentration read from the curve, mg/L
V is total dilution volume, mL m is sample weighing and mg.
7. The detection method of claim 6, wherein the HPLC qualitative and quantitative detection method is characterized in that a standard curve is drawn at the same time: weighing 100mg of a standard sample shown in the formula (I), accurately measuring the standard sample to 0.1mg, adding an appropriate amount of DCM (DCM) into a 100mL volumetric flask, dissolving, diluting to a constant volume to a scale, shaking uniformly to obtain a 1mg/mL standard product mother solution, gradually diluting to 100mg/L, 80mg/L, 60mg/L, 40mg/L, 20mg/L, 10mg/L and 5mg/L series standard solutions, bottling through a 0.45um organic filter membrane, detecting, and drawing a curve by taking a peak area as a vertical coordinate and a concentration as a horizontal coordinate.
8. The detection method according to claim 7, wherein the step (2) is operated by: weighing about 50mg of sample, accurately measuring to 0.1mg, dissolving an appropriate amount of DCM in a 25mL volumetric flask, fixing the volume, shaking up, transferring 1mL of sample into the 25mL volumetric flask by a pipette, fixing the volume of DCM, shaking up, filtering an appropriate amount of sample through a 0.45um organic filter membrane, bottling, detecting on a machine, and reading out the content by using a standard curve.
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