CN113866292A - Method for measuring content of o-chlorobenzyl magnesium chloride - Google Patents
Method for measuring content of o-chlorobenzyl magnesium chloride Download PDFInfo
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- CN113866292A CN113866292A CN202111066974.6A CN202111066974A CN113866292A CN 113866292 A CN113866292 A CN 113866292A CN 202111066974 A CN202111066974 A CN 202111066974A CN 113866292 A CN113866292 A CN 113866292A
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- Prior art keywords
- magnesium chloride
- content
- chlorobenzyl magnesium
- derivative
- temperature
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- PHSLYQFWLCWIBU-UHFFFAOYSA-M magnesium;1-chloro-2-methanidylbenzene;chloride Chemical compound [Mg+2].[Cl-].[CH2-]C1=CC=CC=C1Cl PHSLYQFWLCWIBU-UHFFFAOYSA-M 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 20
- -1 Grignard reagent o-chlorobenzyl magnesium chloride Chemical class 0.000 claims abstract description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Substances OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 57
- 238000004817 gas chromatography Methods 0.000 claims description 18
- 238000004811 liquid chromatography Methods 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000000523 sample Substances 0.000 claims description 14
- 239000012488 sample solution Substances 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 13
- 239000011550 stock solution Substances 0.000 claims description 11
- 239000012295 chemical reaction liquid Substances 0.000 claims description 10
- 238000001514 detection method Methods 0.000 claims description 10
- 239000012086 standard solution Substances 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000001212 derivatisation Methods 0.000 claims description 5
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 5
- 238000010812 external standard method Methods 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 238000010813 internal standard method Methods 0.000 claims description 5
- 238000009834 vaporization Methods 0.000 claims description 5
- 230000008016 vaporization Effects 0.000 claims description 5
- WDNZKGYAWFIMJL-UHFFFAOYSA-M [Cl-].[Mg+]CC1=CC=CC=C1Cl Chemical class [Cl-].[Mg+]CC1=CC=CC=C1Cl WDNZKGYAWFIMJL-UHFFFAOYSA-M 0.000 claims description 4
- 238000003556 assay Methods 0.000 claims description 4
- 230000005526 G1 to G0 transition Effects 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- YTJSFYQNRXLOIC-UHFFFAOYSA-N octadecylsilane Chemical group CCCCCCCCCCCCCCCCCC[SiH3] YTJSFYQNRXLOIC-UHFFFAOYSA-N 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 238000004448 titration Methods 0.000 abstract description 7
- 239000007818 Grignard reagent Substances 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 6
- 238000004445 quantitative analysis Methods 0.000 abstract description 3
- 238000004458 analytical method Methods 0.000 abstract description 2
- 238000005303 weighing Methods 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 12
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 4
- 229940117389 dichlorobenzene Drugs 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- MNHVNIJQQRJYDH-UHFFFAOYSA-N 2-[2-(1-chlorocyclopropyl)-3-(2-chlorophenyl)-2-hydroxypropyl]-1,2-dihydro-1,2,4-triazole-3-thione Chemical compound N1=CNC(=S)N1CC(C1(Cl)CC1)(O)CC1=CC=CC=C1Cl MNHVNIJQQRJYDH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000005825 Prothioconazole Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000004795 grignard reagents Chemical class 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000003747 Grignard reaction Methods 0.000 description 2
- 241000209140 Triticum Species 0.000 description 2
- 235000021307 Triticum Nutrition 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 239000003899 bactericide agent Substances 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 2
- 229940106681 chloroacetic acid Drugs 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- BQPPJGMMIYJVBR-UHFFFAOYSA-N (10S)-3c-Acetoxy-4.4.10r.13c.14t-pentamethyl-17c-((R)-1.5-dimethyl-hexen-(4)-yl)-(5tH)-Delta8-tetradecahydro-1H-cyclopenta[a]phenanthren Natural products CC12CCC(OC(C)=O)C(C)(C)C1CCC1=C2CCC2(C)C(C(CCC=C(C)C)C)CCC21C BQPPJGMMIYJVBR-UHFFFAOYSA-N 0.000 description 1
- CHGIKSSZNBCNDW-UHFFFAOYSA-N (3beta,5alpha)-4,4-Dimethylcholesta-8,24-dien-3-ol Natural products CC12CCC(O)C(C)(C)C1CCC1=C2CCC2(C)C(C(CCC=C(C)C)C)CCC21 CHGIKSSZNBCNDW-UHFFFAOYSA-N 0.000 description 1
- XYTLYKGXLMKYMV-UHFFFAOYSA-N 14alpha-methylzymosterol Natural products CC12CCC(O)CC1CCC1=C2CCC2(C)C(C(CCC=C(C)C)C)CCC21C XYTLYKGXLMKYMV-UHFFFAOYSA-N 0.000 description 1
- FPTJELQXIUUCEY-UHFFFAOYSA-N 3beta-Hydroxy-lanostan Natural products C1CC2C(C)(C)C(O)CCC2(C)C2C1C1(C)CCC(C(C)CCCC(C)C)C1(C)CC2 FPTJELQXIUUCEY-UHFFFAOYSA-N 0.000 description 1
- 241000221785 Erysiphales Species 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- BKLIAINBCQPSOV-UHFFFAOYSA-N Gluanol Natural products CC(C)CC=CC(C)C1CCC2(C)C3=C(CCC12C)C4(C)CCC(O)C(C)(C)C4CC3 BKLIAINBCQPSOV-UHFFFAOYSA-N 0.000 description 1
- LOPKHWOTGJIQLC-UHFFFAOYSA-N Lanosterol Natural products CC(CCC=C(C)C)C1CCC2(C)C3=C(CCC12C)C4(C)CCC(C)(O)C(C)(C)C4CC3 LOPKHWOTGJIQLC-UHFFFAOYSA-N 0.000 description 1
- CAHGCLMLTWQZNJ-UHFFFAOYSA-N Nerifoliol Natural products CC12CCC(O)C(C)(C)C1CCC1=C2CCC2(C)C(C(CCC=C(C)C)C)CCC21C CAHGCLMLTWQZNJ-UHFFFAOYSA-N 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 229930182558 Sterol Natural products 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000017858 demethylation Effects 0.000 description 1
- 238000010520 demethylation reaction Methods 0.000 description 1
- QBSJHOGDIUQWTH-UHFFFAOYSA-N dihydrolanosterol Natural products CC(C)CCCC(C)C1CCC2(C)C3=C(CCC12C)C4(C)CCC(C)(O)C(C)(C)C4CC3 QBSJHOGDIUQWTH-UHFFFAOYSA-N 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 210000002257 embryonic structure Anatomy 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- CAHGCLMLTWQZNJ-RGEKOYMOSA-N lanosterol Chemical compound C([C@]12C)C[C@@H](O)C(C)(C)[C@H]1CCC1=C2CC[C@]2(C)[C@H]([C@H](CCC=C(C)C)C)CC[C@@]21C CAHGCLMLTWQZNJ-RGEKOYMOSA-N 0.000 description 1
- 229940058690 lanosterol Drugs 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 150000003432 sterols Chemical class 0.000 description 1
- 235000003702 sterols Nutrition 0.000 description 1
- QPDUQKTYZRXRBC-UHFFFAOYSA-N triazole-4-thione Chemical compound S=C1C=NN=N1 QPDUQKTYZRXRBC-UHFFFAOYSA-N 0.000 description 1
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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
- 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
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
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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
- G01N30/02—Column chromatography
- G01N30/26—Conditioning of the fluid carrier; Flow patterns
- G01N30/28—Control of physical parameters of the fluid carrier
- G01N30/34—Control of physical parameters of the fluid carrier of fluid composition, e.g. gradient
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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
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/64—Electrical detectors
- G01N30/68—Flame ionisation detectors
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- 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
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/74—Optical detectors
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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
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
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- G01N2030/067—Preparation by reaction, e.g. derivatising the sample
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Abstract
The invention relates to a method for measuring the content of o-chlorobenzyl magnesium chloride, which belongs to the technical field of chemical analysis. According to the method, the active Grignard reagent o-chlorobenzyl magnesium chloride is derived to generate the stable o-chlorobenzyl magnesium chloride acetone derivative, and then the quantitative analysis is carried out to improve the quantitative accuracy, so that the problems that the o-chlorobenzyl magnesium chloride which is possibly partially damaged in the conventional titration process is also titrated, the titration end point is easy to have a reverse color phenomenon, and the operation is difficult to control, so that the result accuracy is lower are solved.
Description
Technical Field
The invention relates to a method for measuring the content of o-chlorobenzyl magnesium chloride, belonging to the technical field of chemical analysis.
Background
The o-chlorobenzyl magnesium chloride is a key intermediate for preparing the bactericide prothioconazole. Prothioconazole is a novel spectrum triazolethione bactericide developed by Bayer companies, is mainly used for preventing and treating diseases of cereal crops such as cereals, wheat, beans and the like, and particularly has excellent prevention and treatment effects on wheat stripe rust and powdery mildew. The mechanism of action is to inhibit the demethylation of lanosterol, the precursor of sterol, or the 14-position of 2, 4-methylenedihydrolanostane in fungi. Because of low toxicity and no toxicity to embryos, the compound is safe to people and environment and is generally concerned by people.
The synthesis of the high-content o-chlorobenzyl magnesium chloride Grignard reagent is the key of the prothioconazole synthesis process, and whether the content of the o-chlorobenzyl magnesium chloride is accurate or not determines the scientificity of reaction feeding, so that the accuracy of the o-chlorobenzyl magnesium chloride content determination has important significance. The conventional method for measuring the content of the o-chlorobenzyl magnesium chloride is a titration method, and because the Grignard reagent has high activity and cannot contact water, air and the like, the o-chlorobenzyl magnesium chloride needs to be carefully removed by an injector with good tightness in the measuring process and then titrated, the o-chlorobenzyl magnesium chloride which is possibly partially damaged in the titration process is also titrated, so that the result deviation is caused, the titration end point is easy to have a reverse color phenomenon, and the operation is difficult to control, so that the result accuracy is low.
Disclosure of Invention
The invention aims to provide a method for measuring the content of o-chlorobenzyl magnesium chloride, which is accurate and reliable.
In order to achieve the purpose, the invention adopts the technical scheme that:
a method for measuring the content of o-chlorobenzyl magnesium chloride comprises the steps of reacting o-chlorobenzyl magnesium chloride in reaction liquid with a derivative reagent to obtain an o-chlorobenzyl magnesium chloride derivative, measuring the content of the derivative by adopting a gas chromatography or a liquid chromatography, and calculating the content of the o-chlorobenzyl magnesium chloride according to the content of the derivative.
The technical scheme of the invention is further improved as follows: the derivatization reagent is acetone, and the o-chlorobenzyl magnesium chloride derivative is an o-chlorobenzyl magnesium chloride acetone derivative.
The technical scheme of the invention is further improved as follows: in the reaction process, under the protection of nitrogen, firstly transferring a certain amount of acetone into a vacuum reaction bottle, then transferring a certain amount of reaction liquid into the vacuum reaction bottle, uniformly shaking, finally transferring a certain amount of acid, and uniformly shaking to obtain the o-chlorobenzyl magnesium chloride acetone derivative reaction liquid.
The technical scheme of the invention is further improved as follows: the gas chromatography assay comprises the steps of:
(1) preparing an internal standard stock solution;
(2) preparing a standard solution;
(3) preparing a sample solution;
(4) performing gas chromatography detection, and calculating the content of the derivative by an internal standard method.
The technical scheme of the invention is further improved as follows: the gas chromatography conditions of the step (4) are as follows:
a chromatographic column: DM-624, 30m × 0.53mm, 3.0 um;
nitrogen gas: 10mL/min, air: 300mL/min, hydrogen: 30 mL/min;
sample introduction amount: 1 mu L of the solution;
vaporization temperature: 250 ℃;
detecting the temperature: 250 ℃;
column temperature: the initial temperature is 65-75 ℃, the temperature is kept for 0-3min, the temperature is increased to 160 ℃ at the temperature increasing rate of 10 ℃/min, then the temperature is increased to 238 ℃ at the temperature increasing rate of 40 ℃/min, and the temperature is kept for 13 min;
a detector: FID.
The technical scheme of the invention is further improved as follows: the liquid chromatography assay comprises the steps of:
(1) preparing a standard solution;
(2) preparing a sample solution;
(3) performing liquid chromatography detection, and calculating the content of the derivative by an external standard method.
The technical scheme of the invention is further improved as follows: the liquid chromatography conditions of the step (3) are as follows:
a chromatographic column: the stationary phase is octadecylsilane chemically bonded silica;
mobile phase: 0.03-0.1% trifluoroacetic acid aqueous solution-methanol, wherein the proportion of 0.03-0.1% trifluoroacetic acid aqueous solution is 10-30%, and the proportion of methanol is 90-70%;
wavelength: 210 nm;
flow rate: 1.0 mL/min;
column temperature: 35 ℃;
sample introduction amount: 5 μ L.
Due to the adoption of the technical scheme, the invention has the following technical effects:
according to the method, the active Grignard reagent o-chlorobenzyl magnesium chloride is derived to generate the stable o-chlorobenzyl magnesium chloride acetone derivative, and then the quantitative analysis is carried out by adopting gas chromatography or liquid chromatography, so that the quantitative accuracy can be improved, and the problems that the o-chlorobenzyl magnesium chloride which is possibly partially damaged in the conventional titration process is also titrated, the titration end point is easy to have a reverse color phenomenon, and the operation is difficult to control, so that the result accuracy is lower are solved.
The invention carries out quantitative analysis after the derivatization of the Grignard reagent by introducing the derivatization reagent, provides reliable data for synthesis, can effectively utilize the Grignard reagent, reduces side reactions and improves the conversion rate of the synthesis reaction.
Drawings
FIG. 1 is a gas chromatogram of an o-chlorobenzyl magnesium chloride acetone derivative according to the present invention;
FIG. 2 is a liquid chromatogram of an o-chlorobenzyl magnesium chloride acetone derivative of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the drawings and specific embodiments, and the present invention is not limited to the following embodiments, and all simple modifications and changes made in the content of the present specification, or the direct and indirect application to other related fields, are within the scope of the present invention.
The instrument comprises the following steps: an Agilent 7820 gas chromatograph, an FID detector and an Agilent workstation; agilent 1260 series high performance liquid chromatograph equipped with ultraviolet detector, autosampler, column oven, and Agilent workstation.
Reagent: dichlorobenzene (analytically pure), trifluoroacetic acid (chromatographically pure), methanol (chromatographically pure), water (newly distilled water twice), and a reaction solution sample (Hebei Wignefar Biochemical Co., Ltd.).
Preparing an o-chlorobenzyl magnesium chloride acetone derivative working standard: 20g of acetone and 10g of Grignard reaction solution are introduced into a 100ml vacuum reaction tube, the mixture is shaken up, 10g of chloroacetic acid is introduced again, the mixture is shaken up, and the obtained reaction solution is rotary evaporated at 30-40 ℃ to obtain 5.6g of crude product. And (3) carrying out column chromatography on the crude product, selecting 200-mesh 300-mesh silica gel to fill the column, eluting and receiving by adopting petroleum ether and ethyl acetate in a ratio of 50:1-5:1 after sample loading, simultaneously carrying out chromatographic monitoring, combining and desolventizing high-purity eluent to obtain 2.1g of the o-chlorobenzyl magnesium chloride acetone derivative with the content of 98.7%, and obtaining the o-chlorobenzyl magnesium chloride acetone derivative working standard product.
Preparing an o-chlorobenzyl magnesium chloride acetone derivative reaction solution: 10g of acetone and 0.5g of Grignard reaction solution are introduced into a 100ml vacuum reaction tube, and the mixture is shaken up, 1g of chloroacetic acid is introduced again, and the mixture is shaken up to obtain the o-chlorobenzyl magnesium chloride acetone derivative reaction solution.
The content of the o-chlorobenzyl magnesium chloride is measured by adopting gas chromatography or liquid chromatography:
the content of o-chlorobenzyl magnesium chloride is determined by gas chromatography:
(1) preparing an internal standard stock solution: weighing 1.3g of dichlorobenzene in a 200mL volumetric flask, dissolving with methanol, fixing the volume, and shaking up for later use;
(2) preparation of a standard solution: weighing 0.03g (accurate to 0.0002g) of o-chlorobenzyl magnesium chloride acetone derivative working standard in a 50mL volumetric flask, transferring 5mL of internal standard stock solution in the volumetric flask, dissolving with methanol, fixing the volume and shaking up;
(3) preparation of sample solution: weighing about 0.5g (accurate to 0.0002g) of o-chlorobenzyl magnesium chloride acetone derivative reaction liquid into a 50mL volumetric flask, transferring 5mL of internal standard stock solution into the volumetric flask, dissolving with methanol, fixing the volume, and shaking up;
(4) performing gas chromatography detection under the following conditions:
a chromatographic column: DM-624, 30m × 0.53mm, 3.0 um;
nitrogen gas: 10mL/min, air: 300mL/min, hydrogen: 30 mL/min;
sample introduction amount: 1 mu L of the solution;
vaporization temperature: 250 ℃;
detecting the temperature: 250 ℃;
column temperature: the initial temperature is 65-75 deg.C, the temperature is maintained for 0-3min, the temperature is increased to 160 deg.C at a rate of 10 deg.C/min, then to 238 deg.C at a rate of 40 deg.C, and the temperature is maintained for 13min
A detector: FID;
calculating the content x of the derivative by an internal standard method1The formula is as follows:
content of derivative
In the formula:
r2-average value of peak area ratio of o-chlorobenzyl magnesium chloride acetone derivative to internal standard in sample solution;
r1-average value of peak area ratio of o-chlorobenzyl magnesium chloride acetone derivative to internal standard in standard sample solution;
m1-mass in g of o-chlorobenzyl magnesium chloride acetone derivative working standard;
m2-mass in g of sample of o-chlorobenzyl magnesium chloride acetone derivative;
the content of the P-o-chlorobenzyl magnesium chloride acetone derivative as a working standard substance in unit percent;
(5) calculating the content x of the o-chlorobenzyl magnesium chloride according to the content of the derivative, wherein the calculation formula is as follows:
in the formula:
185.33-molecular weight of o-chlorobenzyl magnesium chloride;
184.66-molecular weight of O-chlorobenzyl magnesium chloride acetone derivative.
(II) determining the content of the o-chlorobenzyl magnesium chloride by liquid chromatography:
(1) preparation of a standard solution: accurately weighing 0.025g (accurate to 0.0002g) of o-chlorobenzyl magnesium chloride acetone derivative working standard in a 50ml volumetric flask, dissolving with methanol, fixing the volume, and shaking up;
(2) preparation of sample solution: accurately weighing about 1.0g (accurate to 0.0002g) of o-chlorobenzyl magnesium chloride acetone derivative-containing reaction liquid in a 50ml volumetric flask, dissolving with methanol, fixing the volume and shaking up;
(3) performing liquid chromatography detection under the following conditions:
a chromatographic column: c18(250 mm. times.4.6 mm, 5 um);
mobile phase: 0.03-0.1% trifluoroacetic acid aqueous solution-methanol (10-30: 90-70);
wavelength: 210 nm;
flow rate: 1.0 ml/min;
column temperature: 35 ℃;
sample introduction: 5 ul;
calculating the content x of the derivative by external standard method1The formula is as follows:
content of derivative:
in the formula:
A2-average value of the peak area of the o-chlorobenzyl magnesium chloride acetone derivative in the sample solution;
A1-average value of peak area of o-chlorobenzyl magnesium chloride acetone derivative in standard sample solution;
m1-mass in g of o-chlorobenzyl magnesium chloride acetone derivative working standard;
m2-mass in g of sample of o-chlorobenzyl magnesium chloride acetone derivative;
the content of the P-o-chlorobenzyl magnesium chloride acetone derivative as a working standard substance in unit percent;
(4) calculating the content x of the o-chlorobenzyl magnesium chloride according to the content of the derivative, wherein the calculation formula is as follows:
content of o-chlorobenzyl magnesium chloride:
in the formula:
185.33-molecular weight of o-chlorobenzyl magnesium chloride
184.66 molecular weight of O-chlorobenzyl magnesium chloride acetone derivative
Example 1
Determining the content of o-chlorobenzyl magnesium chloride by gas chromatography:
(1) preparing an internal standard stock solution: weighing 1.3g of dichlorobenzene in a 200mL volumetric flask, dissolving with methanol, fixing the volume, and shaking up for later use;
(2) preparation of a standard solution: weighing 0.0310g of o-chlorobenzyl magnesium chloride acetone derivative working standard in a 50mL volumetric flask, transferring 5mL of internal standard stock solution in the volumetric flask, dissolving with methanol, fixing the volume, and shaking up;
(3) preparation of sample solution: weighing 0.5003g of o-chlorobenzyl magnesium chloride acetone derivative reaction liquid (batch number: 20210311) in a 50mL volumetric flask, transferring 5mL of internal standard stock solution in the volumetric flask, dissolving with methanol, fixing the volume, and shaking up;
(4) performing gas chromatography detection, calculating the content of the derivative by an internal standard method,
the gas chromatography conditions were as follows:
a chromatographic column: DM-624, 30m × 0.53mm, 3.0 um;
nitrogen gas: 10mL/min, air: 300mL/min, hydrogen: 30 mL/min;
sample introduction amount: 1 mu L of the solution;
vaporization temperature: 250 ℃;
detecting the temperature: 250 ℃;
column temperature: the initial temperature is 70 deg.C, the temperature is maintained for 1min, the temperature is increased to 160 deg.C at a rate of 10 deg.C/min, the temperature is increased to 238 deg.C at a rate of 40 deg.C, and the temperature is maintained for 13min
A detector: FID;
content of derivative:
(5) calculating the content of the o-chlorobenzyl magnesium chloride according to the content of the derivative:
example 2
Determining the content of o-chlorobenzyl magnesium chloride by liquid chromatography:
(1) preparation of a standard solution: accurately weighing 0.0274g of o-chlorobenzyl magnesium chloride acetone derivative working standard substance in a 50ml volumetric flask, dissolving with methanol, fixing the volume, and shaking up;
(2) preparation of sample solution: 0.9071g of o-chlorobenzyl magnesium chloride acetone derivative reaction liquid (batch number: 20210311) is accurately weighed in a 50ml volumetric flask, dissolved by methanol and subjected to constant volume, and shaken up;
(3) performing liquid chromatography detection, calculating the content of the derivative according to an external standard method,
the liquid chromatography conditions were as follows:
a chromatographic column: c18(250 mm. times.4.6 mm, 5 um);
mobile phase: methanol-0.03% aqueous trifluoroacetic acid (80: 20);
wavelength: 210 nm;
flow rate: 1.0 ml/min;
column temperature: 35 ℃;
sample introduction: 5 ul;
content of derivative:
(4) calculating the content of the o-chlorobenzyl magnesium chloride according to the content of the derivative:
example 3
Determining the content of o-chlorobenzyl magnesium chloride by gas chromatography:
(1) preparing an internal standard stock solution: weighing 1.3g of dichlorobenzene in a 200mL volumetric flask, dissolving with methanol, fixing the volume, and shaking up for later use;
(2) preparation of a standard solution: weighing 0.0348g (accurate to 0.0002g) of o-chlorobenzyl magnesium chloride acetone derivative working standard in a 50mL volumetric flask, transferring 5mL of internal standard stock solution in the volumetric flask, dissolving with methanol, fixing the volume and shaking up;
(3) preparation of sample solution: weighing about 0.5205g (accurate to 0.0002g) of o-chlorobenzyl magnesium chloride acetone derivative reaction solution (batch number: 20210412) in a 50mL volumetric flask, transferring 5mL of internal standard stock solution in the volumetric flask, dissolving with methanol, fixing the volume and shaking up;
(4) performing gas chromatography detection, calculating the content of the derivative by an internal standard method,
the gas chromatography conditions were as follows:
a chromatographic column: DM-624, 30m × 0.53mm, 3.0 um;
nitrogen gas: 10mL/min, air: 300mL/min, hydrogen: 30 mL/min;
sample introduction amount: 1 mu L of the solution;
vaporization temperature: 250 ℃;
detecting the temperature: 250 ℃;
column temperature: the initial temperature is 75 ℃, the temperature is kept for 3min, the temperature is increased to 160 ℃ at the temperature increasing rate of 10 ℃/min, the temperature is increased to 238 ℃ at the temperature increasing rate of 40 ℃, and the temperature is kept for 13min
A detector: FID;
content of derivative:
(5) calculating the content of the o-chlorobenzyl magnesium chloride according to the content of the derivative:
example 4
Determining the content of o-chlorobenzyl magnesium chloride by liquid chromatography:
(1) preparation of a standard solution: accurately weighing 0.0254g of o-chlorobenzyl magnesium chloride acetone derivative working standard substance in a 50ml volumetric flask, dissolving with methanol, fixing the volume, and shaking up;
(2) preparation of sample solution: 1.0212g of o-chlorobenzyl magnesium chloride acetone derivative reaction liquid (batch number: 20210412) is accurately weighed in a 50ml volumetric flask, dissolved by methanol and subjected to constant volume, and shaken up;
(3) performing liquid chromatography detection, calculating the content of the derivative according to an external standard method,
the liquid chromatography conditions were as follows:
a chromatographic column: c18(250 mm. times.4.6 mm, 5 um);
mobile phase: methanol-0.1% trifluoroacetic acid in water (70:30)
Wavelength: 210 nm;
flow rate: 1.0 ml/min;
column temperature: 35 ℃;
sample introduction: 5 ul;
content of derivative:
(4) calculating the content of the o-chlorobenzyl magnesium chloride according to the content of the derivative:
Claims (7)
1. a method for measuring the content of o-chlorobenzyl magnesium chloride is characterized by comprising the following steps: reacting o-chlorobenzyl magnesium chloride in the reaction solution with a derivatization reagent to obtain an o-chlorobenzyl magnesium chloride derivative, then measuring the content of the derivative by adopting gas chromatography or liquid chromatography, and calculating the content of the o-chlorobenzyl magnesium chloride according to the content of the derivative.
2. The method for determining the content of o-chlorobenzyl magnesium chloride according to claim 1, which comprises the following steps: the derivatization reagent is acetone, and the o-chlorobenzyl magnesium chloride derivative is an o-chlorobenzyl magnesium chloride acetone derivative.
3. The method for determining the content of o-chlorobenzyl magnesium chloride according to claim 2, which comprises the following steps: in the reaction process, under the protection of nitrogen, firstly transferring a certain amount of acetone into a vacuum reaction bottle, then transferring a certain amount of reaction liquid into the vacuum reaction bottle, uniformly shaking, finally transferring a certain amount of acid, and uniformly shaking to obtain the o-chlorobenzyl magnesium chloride acetone derivative reaction liquid.
4. The method for determining the content of o-chlorobenzyl magnesium chloride according to claim 2, which comprises the following steps: the gas chromatography assay comprises the steps of:
(1) preparing an internal standard stock solution;
(2) preparing a standard solution;
(3) preparing a sample solution;
(4) performing gas chromatography detection, and calculating the content of the derivative by an internal standard method.
5. The method for determining the content of o-chlorobenzyl magnesium chloride according to claim 4, which comprises the following steps: the gas chromatography conditions of the step (4) are as follows:
a chromatographic column: DM-624, 30m × 0.53mm, 3.0 um;
nitrogen gas: 10mL/min, air: 300mL/min, hydrogen: 30 mL/min;
sample introduction amount: 1 mu L of the solution;
vaporization temperature: 250 ℃;
detecting the temperature: 250 ℃;
column temperature: the initial temperature is 65-75 ℃, the temperature is kept for 0-3min, the temperature is increased to 160 ℃ at the temperature increasing rate of 10 ℃/min, then the temperature is increased to 238 ℃ at the temperature increasing rate of 40 ℃/min, and the temperature is kept for 13 min;
a detector: FID.
6. The method for determining the content of o-chlorobenzyl magnesium chloride according to claim 2, which comprises the following steps: the liquid chromatography assay comprises the steps of:
(1) preparing a standard solution;
(2) preparing a sample solution;
(3) performing liquid chromatography detection, and calculating the content of the derivative by an external standard method.
7. The method for determining the content of o-chlorobenzyl magnesium chloride according to claim 6, which comprises the following steps: the liquid chromatography conditions of the step (3) are as follows:
a chromatographic column: the stationary phase is octadecylsilane chemically bonded silica;
mobile phase: 0.03-0.1% trifluoroacetic acid aqueous solution-methanol, wherein the proportion of 0.03-0.1% trifluoroacetic acid aqueous solution is 10-30%, and the proportion of methanol is 90-70%;
wavelength: 210 nm;
flow rate: 1.0 mL/min;
column temperature: 35 ℃;
sample introduction amount: 5 μ L.
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