Method for chiral resolution of clodinafop-propargyl enantiomer
By employing high-performance liquid chromatography-mass spectrometry (HPLC-MS/MS) with a combination of polysaccharide derivative chiral columns and specific mobile phases, the problem of enantiomer separation of clodinafop-propargyl was solved, achieving efficient separation of clodinafop-propargyl enantiomers and supporting research on pesticide environmental behavior and bioactivity.
Patent Information
- Application Number
- CN202610285926.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-03-10
- Publication Date
- 2026-05-05
AI Technical Summary
Existing technologies have failed to effectively chirally separate the R and S configurations of clodinafop-propargyl, and enantiomeric studies are insufficient, affecting the evaluation of the pesticide's environmental behavior and biological activity.
High-performance liquid chromatography-mass spectrometry (HPLC-MS/MS) was used to separate enantiomers of chlorpyrifos using a chiral column based on polysaccharide derivatives and a specific combination of mobile phases, including methanol or acetonitrile as mobile phase A and pure water as mobile phase B. The column temperature was 30-35 °C and the flow rate was 0.5-0.8 mL/min.
It achieves efficient, simple and sensitive separation of enantiomers of chlorpyrifos, with a separation degree of over 1.5 and effective baseline separation, which is suitable for subsequent pesticide research.
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Figure CN121974828A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of chemical synthesis technology, specifically relating to a method for chiral resolution of enantiomers of acetamiprid. Background Technology
[0002] The Food and Agriculture Organization of the United Nations (FAO) defines pesticides as chemical substances used to control pests, including single or mixed formulations of herbicides, insecticides, fungicides, and disinfectants. In recent years, of the pesticides widely used to ensure high crop yields, only a small portion are effective against target organisms; the majority of pesticide residues enter the environment, polluting soil and water bodies, leading to long-term exposure of humans and other organisms to low doses of pesticides. With increasing environmental and health awareness, research on the environmental behavior of pesticides is receiving growing attention. Chiral pesticides, as a special class of pesticides, have attracted significant attention. Currently, approximately 40% of commercially available pesticides have chiral structures, but most are still used in racemic form. Because chiral enantiomers can exhibit significant differences in environmental behavior, biological activity, and toxicity, racemic pesticides not only have low utilization rates but may also increase environmental risks and pose a potential threat to non-target organisms. Therefore, studying chiral pesticides at the enantiomer level is of great significance for developing environmentally friendly, highly efficient, and low-toxicity optically pure monomeric pesticides.
[0003] Buturon was developed and introduced to the market by Bayer AG of Germany in 1965 for pre- and post-emergence weed control in cereal and corn fields. Currently, there are no literature reports on the bioactivity, toxicity, and environmental risks of the R and S enantiomers of buturon. Therefore, establishing a chiral resolution method for buturon enantiomers is particularly important for further research.
[0004]
[0005] Acetylene Summary of the Invention
[0006] This invention provides a method for chiral separation of enantiomers of propargyl, using high performance liquid chromatography-mass spectrometry to achieve the separation of the R and S configurations of propargyl.
[0007] The technical solution adopted in this invention is:
[0008] A method for chiral resolution of enantiomers of acetamiprid includes the following steps:
[0009] 1) Preparation of test solution: Weigh propargyl, dissolve and dilute with an organic solvent to prepare propargyl test solution;
[0010] 2) The enantiomers of chlorpyrifos in the test solution were separated by high performance liquid chromatography-mass spectrometry. The stationary phase was a chiral column of polysaccharide derivative, the mobile phase A was an organic solvent, and the mobile phase B was pure water. Isocratic elution was performed.
[0011] 3) Measured using an ultraviolet detector or a mass spectrometer.
[0012] Furthermore, in the above-mentioned method for chiral resolution of enantiomers of acetamiprid, in step 1), the organic solvent is one of methanol and acetonitrile.
[0013] Furthermore, in the above-mentioned method for chiral resolution of enantiomers of chlorpyrifos, in step 1), the concentration of the chlorpyrifos test solution is 10-500 ng / mL.
[0014] Preferably, the concentration of the chlorpyrifos test solution is 10 ng / mL.
[0015] Furthermore, in the above-mentioned method for chiral separation of enantiomers of acetamiprid, in step 2), the polysaccharide derivative chiral chromatographic column is a polysaccharide derivative chiral chromatographic column with covalently bonded amylose-tris(3-chloro-5-methylphenylcarbamate) on a silica gel surface.
[0016] Furthermore, in the above-mentioned method for chiral resolution of enantiomers of acetylene, in step 2), the mobile phase A is acetonitrile or methanol, and the mobile phase ratio A:B is 40:60-100:0 by volume. Isocratic elution is performed, the column temperature is 30-35 ℃, and the flow rate is 0.5-0.8 mL / min.
[0017] Preferably, the mobile phase A is acetonitrile, and the mobile phase ratio A:B is 80:20 by volume. Isocratic elution is performed, the column temperature is 35℃, and the flow rate is 0.6 mL / min.
[0018] Furthermore, in step 3) of the above-mentioned method for chiral resolution of enantiomers of acetamiprid, a mass spectrometer is used for determination.
[0019] The beneficial effects of this invention are: This invention uses high performance liquid chromatography-mass spectrometry to directly chirally separate clodinafop-propargyl, and its mobile phase consists of acetonitrile and pure water. This method has the advantages of simple operation, high sensitivity, mild conditions, and short separation time. Attached Figure Description
[0020] Figure 1 This is the chromatographic separation chromatogram of Example 1.
[0021] Figure 2 This is the chromatographic separation chromatogram of Example 2.
[0022] Figure 3This is the chromatographic separation chromatogram of Example 3.
[0023] Figure 4 This is the chromatographic separation chromatogram of Example 4. Detailed Implementation
[0024] The advantages of the present invention will be further illustrated below with reference to the accompanying drawings and specific embodiments.
[0025] Exemplary embodiments will now be described in detail, examples of which are illustrated in the accompanying drawings. When the following description relates to the drawings, unless otherwise indicated, the same numerals in different drawings denote the same or similar elements. The embodiments described in the following exemplary embodiments do not represent all embodiments consistent with the disclosure of this invention. Rather, they are merely examples of apparatuses and methods consistent with some aspects of the invention disclosed as detailed in the appended claims.
[0026] The terminology used in this disclosure is for the purpose of describing particular embodiments only and is not intended to be limiting of this disclosure. The singular forms “a,” “the,” and “the” as used in this disclosure and the appended claims are also intended to include the plural forms unless the context clearly indicates otherwise. It should also be understood that the term “and / or” as used herein refers to and includes any and all possible combinations of one or more of the associated listed items.
[0027] Example 1
[0028] A method for chiral resolution of enantiomers of acetamiprid includes the following steps:
[0029] 1) Weigh a certain amount of clodinafop-propargyl, dissolve it in methanol and dilute to volume to prepare a clodinafop-propargyl test solution with a concentration of 10 ng / mL.
[0030] 2) Chiral separation was performed using high performance liquid chromatography-mass spectrometry.
[0031] The high-performance liquid chromatography-mass spectrometry (HPLC-MS / MS) system used was an Agilent system, with a chiral column of polysaccharide derivatives as the stationary phase, and a CHIRALPAK column was used. ® The IG chiral column is a chiral column of polysaccharide derivatives of amylose-tris(3-chloro-5-methylphenylcarbamate) covalently bonded to the surface of silica gel. It has a size of 250 mm × 4.6 mm and a particle size of 5 μm.
[0032] Mobile phase A was methanol, and mobile phase B was pure water. The mobile phase ratio was calculated by volume, and the ratio of A:B was 40:60-100:0 for 0-10 min, with gradient elution. The column temperature of the chiral column for polysaccharide derivatives was 35 ℃; the flow rate was 0.6 mL / min; and the injection volume was 10 μL.
[0033] 3) Determination was performed using a mass spectrometer detector.
[0034] The results are as follows Figure 1 .Depend on Figure 1 It can be seen that although the enantiomers of acetamiprid are effectively separated, the ratio of the two peaks is not uniform.
[0035] Example 2
[0036] A method for chiral resolution of enantiomers of acetamiprid includes the following steps:
[0037] 1) Weigh a certain amount of clodinafop-propargyl, dissolve it in methanol and dilute to volume to prepare a clodinafop-propargyl test solution with a concentration of 10 ng / mL.
[0038] 2) Chiral separation was performed using high performance liquid chromatography-mass spectrometry.
[0039] The high-performance liquid chromatography-mass spectrometry (HPLC-MS / MS) system used was an Agilent system, with a chiral column of polysaccharide derivatives as the stationary phase, and a CHIRALPAK column was used. ® The IG chiral column is a chiral column of polysaccharide derivatives of amylose-tris(3-chloro-5-methylphenylcarbamate) covalently bonded to the surface of silica gel. It has a size of 250 mm × 4.6 mm and a particle size of 5 μm.
[0040] Mobile phase A was methanol, and mobile phase B was pure water. The mobile phase ratio was calculated by volume, and the ratio of A:B was 70:30-100:0 for 0-10 min, with gradient elution. The column temperature of the chiral column for polysaccharide derivatives was 35 ℃; the flow rate was 0.6 mL / min; and the injection volume was 10 μL.
[0041] 3) Determination was performed using a mass spectrometer detector.
[0042] The results are as follows Figure 2 .Depend on Figure 2 It can be seen that although the enantiomers of acetamiprid are effectively separated, the ratio of the two peaks is not uniform.
[0043] Example 3
[0044] A method for chiral resolution of enantiomers of acetamiprid includes the following steps:
[0045] 1) Weigh a certain amount of clodinafop-propargyl, dissolve it in methanol and dilute to volume to prepare a clodinafop-propargyl test solution with a concentration of 10 ng / mL.
[0046] 2) Chiral separation was performed using high performance liquid chromatography-mass spectrometry.
[0047] The high-performance liquid chromatography-mass spectrometry (HPLC-MS / MS) system used was an Agilent system, with a chiral column of polysaccharide derivatives as the stationary phase, and a CHIRALPAK column was used. ® The IG chiral column is a chiral column of polysaccharide derivatives of amylose-tris(3-chloro-5-methylphenylcarbamate) covalently bonded to the surface of silica gel. It has a size of 250 mm × 4.6 mm and a particle size of 5 μm.
[0048] Mobile phase A was methanol, and mobile phase B was pure water. The mobile phase ratio was calculated by volume, and the A:B ratio was 70:30-100:0 for 0-5 min, with gradient elution. The column temperature of the chiral column for polysaccharide derivatives was 35 ℃; the flow rate was 0.6 mL / min; and the injection volume was 10 μL.
[0049] 3) Determination was performed using a mass spectrometer detector.
[0050] The results are as follows Figure 3 .Depend on Figure 3 It can be seen that although the enantiomers of acetamiprid are effectively separated, the ratio of the two peaks is not uniform.
[0051] Example 4
[0052] A method for chiral resolution of enantiomers of acetamiprid includes the following steps:
[0053] 1) Weigh a certain amount of clodinafop-propargyl, dissolve it in methanol and dilute to volume to prepare a clodinafop-propargyl test solution with a concentration of 10 ng / mL.
[0054] 2) Chiral separation was performed using high performance liquid chromatography-mass spectrometry.
[0055] The high-performance liquid chromatography-mass spectrometry (HPLC-MS / MS) system used was an Agilent system, with a chiral column of polysaccharide derivatives as the stationary phase, and a CHIRALPAK column was used. ® The IG chiral column is a chiral column of polysaccharide derivatives of amylose-tris(3-chloro-5-methylphenylcarbamate) covalently bonded to the surface of silica gel. It has a size of 250 mm × 4.6 mm and a particle size of 5 μm.
[0056] Mobile phase A was acetonitrile, and mobile phase B was pure water. The volume ratio of mobile phase A:B was 80:20, and isocratic elution was performed. The column temperature of the chiral column for polysaccharide derivatives was 35 ℃; the flow rate was 0.6 mL / min; and the injection volume was 10 μL.
[0057] 3) Determination was performed using a mass spectrometer detector.
[0058] The results are as follows Figure 4 .Depend on Figure 4It can be seen that the enantiomers of acetamiprid are effectively separated, and the two peaks are in uniform proportion. The calculated resolution is R=7.63, achieving effective baseline separation.
[0059] In summary, this invention employs high-performance liquid chromatography-mass spectrometry (HPLC-MS) under specific chromatographic conditions: mobile phase A is acetonitrile, mobile phase B is pure water, the mobile phase ratio (A:B) is 80:20 (by volume), isocratic elution is performed, the column temperature is 35 °C, and the flow rate is 0.6 mL / min. This allows for effective chiral separation of chlorpyrifos and effective separation of its enantiomers. The calculated resolution reaches 1.5 or higher, achieving effective baseline separation.
[0060] The separated acetamiprid can be used for subsequent industrial applications. It should be noted that the embodiments of the present invention are highly feasible and do not constitute any limitation on the present invention. Any person skilled in the art may modify or alter the above-disclosed technical content to create equivalent effective embodiments. However, any modifications or equivalent changes made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention's technical solution shall still fall within the scope of the present invention's technical solution.
Claims
1. A method for chiral resolution of enantiomers of acetamiprid, characterized in that, Includes the following steps: 1) Preparation of test solution: Weigh propargyl, dissolve and dilute with an organic solvent to prepare propargyl test solution; 2) The enantiomers of chlorpyrifos in the test solution were separated by high performance liquid chromatography-mass spectrometry. The stationary phase was a chiral column of polysaccharide derivative, the mobile phase A was an organic solvent, and the mobile phase B was pure water. Isocratic elution was performed. 3) Measured using an ultraviolet detector or a mass spectrometer.
2. The method for chiral resolution of enantiomers of acetamiprid as described in claim 1, characterized in that, In step 1), the organic solvent is one of methanol and acetonitrile.
3. The method for chiral resolution of enantiomers of acetamiprid as described in claim 1, characterized in that, In step 1), the concentration of the acetamiprid test solution is 10-500 ng / mL.
4. The method for chiral resolution of enantiomers of acetamiprid as described in claim 3, characterized in that, In step 1), the concentration of the acetamiprid test solution is 10 ng / mL.
5. The method for chiral resolution of enantiomers of acetamiprid as described in claim 1, characterized in that, In step 2), the polysaccharide derivative chiral chromatographic column is a polysaccharide derivative chiral chromatographic column with linear starch-tris(3-chloro-5-methylphenylcarbamate) covalently bonded to the surface of silica gel.
6. The method for chiral resolution of enantiomers of acetamiprid as described in claim 1, characterized in that, In step 2), the mobile phase A is acetonitrile or methanol, and the mobile phase ratio A:B is 40:60-100:0 by volume. Isocratic elution is performed, the column temperature is 30-35 ℃, and the flow rate is 0.5-0.8 mL / min.
7. The method for chiral resolution of enantiomers of acetamiprid as described in claim 6, characterized in that, In step 2), mobile phase A is acetonitrile, and the volume ratio of mobile phase A:B is 80:
20. Isocratic elution is performed, the column temperature is 35 °C, and the flow rate is 0.6 mL / min.
8. The method for chiral resolution of enantiomers of acetamiprid as described in claim 1, characterized in that, In step 3), a mass spectrometer detector is used for determination.