CN102768250B - Method for chiral separation and measurement of methyl lactate optical isomers by capillary gas chromatography - Google Patents
Method for chiral separation and measurement of methyl lactate optical isomers by capillary gas chromatography Download PDFInfo
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- CN102768250B CN102768250B CN201210256626.XA CN201210256626A CN102768250B CN 102768250 B CN102768250 B CN 102768250B CN 201210256626 A CN201210256626 A CN 201210256626A CN 102768250 B CN102768250 B CN 102768250B
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Abstract
The invention discloses a method for chiral separation and measurement of methyl lactate optical isomers by chiral capillary column gas chromatography. The preferred chromatographic conditions are as follows: chiral capillary column having inner wall coated with 2,3,6-tri-O-capryl-beta-cyclodextrin as chiral stationary phase; chromatographic column with length of 20-30 m, inner diameter of 250-320 micrometer, and stationary phase film thickness of 0.31 micrometer; inert gas as mobile phase with flow rate of 25-35 cm/s; hydrogen flame ionization detector; injection port temperature of 200-280 DEG C; detector temperature of 250-280 DEG C; and chromatographic column temperature of 50-80 DEG C. The inventive method can completely achieve baseline separation of D-methyl lactate and L-methyl lactate enantiomer chromatographic peaks, with separation degree of 5.49. The method can be utilized for simultaneous quantitative determination of D-methyl lactate and L-methyl lactate isomers.
Description
Technical field
The present invention relates to the method for capillary gas chromatography chiral separation determination methyl lactate optical isomer.
Background technology
Methyl lactate: chemistry 2 hydroxy propanoic acid methyl esters by name, molecular weight 104.1, molecular formula C
4h
8o
3.Methyl lactate is important Organic Chemicals and important fine chemicals, is widely used in the industries such as food, beverage, medicine.
The optical isomer of methyl lactate is laevoisomer (-)-methyl lactate and dextroisomer (+)-methyl lactate.According to the method for expressing of Fisher projection: levo form (-)-methyl lactate is D-form, and dextroisomer (+)-methyl lactate is L-configuration; According to the configuration expression mode of perspective formula: levo form (-)-methyl lactate is R-configuration, and dextroisomer (+)-methyl lactate is S-configuration.
Methyl lactate structural formula:
Optically pure methyl lactate isomeride is the important intermediate of the optically pure aryloxy group phenoxy propionic acid herbicide of preparation and some chiral drugs.As to adopt S-methyl lactate isomeride be raw material, the efficient isomeride S-brufen of synthetic anti-inflammation and analgesic drugs brufen, has reduced production cost, has improved production efficiency.Metalaxyl is one of disinfectant use in agriculture of at present domestic and international consumption maximum, the golden metalaxyl that the R-metalaxyl isomeride of take is principal ingredient has higher bactericidal activity than metalaxyl, and the Pfansteihl methyl esters of take has better optical selective when primary raw material synthesizes golden metalaxyl.Methyl lactate is also the important intermediate of preparation optical activity Herbicide Jing quizalofop-ethyl etc., as take S-methyl lactate as raw material, can synthetic herbicide cyhalofop-butyl; With the synthetic fragrant phenoxy lactic acid ester herbicide of Pfansteihl methyl esters, the pesticide intermediates such as synthesis of optically active agricultural chemicals haloxyfop-P-methyl.
Methyl lactate optical isomer plays an important role in the synthetic production of chiral medicinal, agricultural chemicals as important industrial chemicals, detect the optical purity of methyl lactate optical isomer, for raw material and the product quality of grasping chiral medicinal, agricultural chemicals, have great importance.
Methyl lactate optical isomer is known by the method for capillary gas chromatography separation, but the factors such as the specification of chiral stationary phase, chiral chromatographic column, the column temperature of chromatographic column, split ratio, flow rate of mobile phase have a significant impact testing result, or are not suitable for target detection thing.As; adopt document (Chromatographia; 2010; 71 (5/6): 539-544) reported 2; the kapillary chiral column that 3-bis--O-allyl-6-O-decoyl group-beta-cyclodextrin is chiral stationary phase carries out the separation of methyl lactate optical isomer, and the degree of separation of methyl lactate D/L isomeride is only 1.74.
Summary of the invention
One of object of the present invention is to provide the new purposes of 2,3,6-, tri--O-decoyl group-beta-cyclodextrin.
Provided by the present invention 2,3, the new purposes of 6-tri--O-decoyl group-beta-cyclodextrin is its application in separating lactic acid methyl esters optical isomer as Chiral GC Stationary Phase.
Described 2,3,6-tri--O-decoyl group-beta-cyclodextrin, its structural formula is suc as formula shown in I:
In formula I, R has the structure shown in formula II:
Wherein, n=6.
Above-mentioned 2; 3; 6-tri--O-decoyl group-beta-cyclodextrin prepares by following method: use the active caprylyl chloride of reactivity worth; under pyridine exists; one step derives 2 of beta-schardinger dextrin-, 3 and 6-position hydroxyl for caprylyl; and make 2,3,6-tri--O-caprylyl-beta-cyclodextrin derivative through column chromatography purifying.
The optical isomer of methyl lactate described in the present invention is Pfansteihl methyl esters and D-ALPHA-Hydroxypropionic acid methyl esters.
Two of object of the present invention is to provide a kind of separated method that detects methyl lactate optical isomer.
The separated method that detects methyl lactate optical isomer provided by the present invention; be to adopt chiral capillary column vapor-phase chromatography, wherein, the chiral capillary column adopting is that inwall scribbles 2; the chiral capillary column that 3,6-, tri--O-decoyl group-beta-cyclodextrin is chiral stationary phase.
Concrete chromatographic condition is as follows:
Adopt inwall to scribble the chiral capillary column that 2,3,6-, tri--O-decoyl group-beta-cyclodextrin is chiral stationary phase; Chromatogram column length is 20m～30m, chromatographic column internal diameter is 250 μ m～320 μ m, in chromatographic column, chiral stationary phase thickness is 0.25～0.35 μ m (preferred column length is 20m, and chromatographic column internal diameter is 250 μ m, and in chromatographic column, fixedly phase thickness is 0.31 μ m).
Mobile phase adopts inert gas as nitrogen or helium (preferred nitrogen); Flow rate of mobile phase is 25～35cm/s (being preferably 29cm/s).
Sample introduction adopts split sampling or Splitless injecting samples (preferably split sampling); Sample introduction split ratio is 20: 1～50: 1 (preferably 50: 1); Detecting device is flame ionization ditector (FID); Injector temperature is 200 ℃～280 ℃ (preferably 250 ℃); The temperature of detecting device is 250 ℃～280 ℃ (preferably 280 ℃); Chromatogram column temperature is 50～80 ℃ (preferably 60 ℃).
The preparation of sample solution: adopting organic solvent is the solution that contains methyl lactate 0.1mg/mL by sample preparation; Wherein, described organic solvent is selected from acetone, chloroform or methyl alcohol, preferably acetone.
The sample solution (0.4～1.0 μ L) of preparation is injected to capillary gas chromatograph, record chromatogram, and analyze.Adopt methyl lactate D isomeride and L isomeride in above-mentioned chromatographic condition separation determination methyl lactate, both can be carried out to baseline separation, degree of separation can reach 5.49, all over being reported at present the degree of separation obtaining on other chiral stationary phase and separation method.
Chromatographic condition of the present invention can be used for the quantitative of methyl lactate optical isomer simultaneously.
The separation method of capillary gas chromatography separating lactic acid methyl esters optical isomer provided by the invention; adopt 2; 3; the kapillary chiral column that 6-tri--O-decoyl group-beta-cyclodextrin is chiral stationary phase detects methyl lactate optical isomer; cavity in cyclodextrine derivatives structure and substituting group and isomeride have optionally formed isomeride inclusion complex, thereby reach separated.The method can be used for the mensuration of methyl lactate optical isomer product purity in actual production.For raw material and the product quality of grasping chiral medicinal, agricultural chemicals, have great importance.
Accompanying drawing explanation
Fig. 1 is according to the condition separating lactic acid methyl esters D isomeride of embodiment 2 and the capillary gas chromatography figure of L isomeride; Wherein (1) number peak is methyl lactate D isomeride; (2) number peak is methyl lactate L isomeride.
Fig. 2 is according to the condition separating lactic acid methyl esters D isomeride of comparative example and the capillary gas chromatography figure of L isomeride; Wherein (1) number peak is methyl lactate D isomeride; (2) number peak is methyl lactate L isomeride.
Embodiment
Below by specific embodiment, the present invention will be described, but the present invention is not limited thereto.
Experimental technique described in following embodiment, if no special instructions, is conventional method; Described reagent and material, if no special instructions, all can obtain from commercial channels.
Embodiment 1:2, the preparation of 3,6-, tri--O-decoyl group-beta-cyclodextrin (CSP2)
0.3g (0.264mmol) beta-schardinger dextrin-is dissolved in the dry chloroform of 15mL, at 0 ℃, adds 2.5mL pyridine, under ice bath, drips 3.2mL caprylyl chloride (21.06mmol), after 0 ℃ of stirring reaction 0.5h, and 60 ℃ of stirring reaction 6h.React complete, after removal of solvent under reduced pressure, be dissolved in 20mL frozen water, use 20mL chloroform extraction 3 times, combined chloroform layer, washes after twice with saturated sodium bicarbonate aqueous solution, then washes twice with water, finally uses anhydrous sodium sulfate drying, and reduced pressure concentration obtains crude product.Through column chromatography (toluene/ethyl acetate=1: 1, v/v) purifying obtains brown thickness product (productive rate 20%).
Structural identification data are as follows:
IR(cm
-1)：2927，2857((CH
2，CH
3))，1746(C＝O)，1462，1377(CH
2，CH
3)，1247(CH
3)，1163，1106，1045(C-O-C)，724(-CH2-)。
1H?NMR(300MHz，CDCl
3)：0.86(9H，CH
3CH
2CH
2)，1.28(30H，CH
3CH
2CH
2CH
2)，1.63(6H，OCH
2CH
2)，2.32(6H，OCOCH
2)，3.0-5.5(6H，CD(H)，OCH
2)。
From above-mentioned data, prepared compound is really target compound 2,3,6-tri--O-decoyl group-beta-cyclodextrin.
1) prepare capillary gas chromatography chiral post
By 2 of embodiment 1 preparation; 3; 6-tri--O-decoyl group-beta-cyclodextrin is as chiral stationary phase; after being dissolved in methylene chloride, adopt traditional static method, fixing phase wall is applied to the quartz capillary column wall with NaCl roughening; prepare capillary gas chromatography chiral post; 2,3,6-, tri--O-decoyl group-beta-cyclodextrin inner wall thickness is 0.31 μ m.
2) chromatographic condition
Instrument: HP6890
+gas chromatograph, flame ionization ditector, shunting/Splitless injecting samples mouth
Chromatographic column: step 1) inwall of preparing scribbles the self-control kapillary chiral column that 2,3,6-, tri--O-decoyl group-beta-cyclodextrin is chiral stationary phase (20m * 0.25mm * 0.31 μ m, length * internal diameter * interior wall thickness);
Mobile phase: high pure nitrogen
Flow rate of mobile phase: 29cm/s;
Injection port: split sampling, split ratio is 50: 1
Injector temperature: 250 ℃
Detector temperature: 280 ℃
Chromatogram column temperature: 60 ℃
The preparation of location solution 1: it is appropriate that precision takes methyl lactate D isomeride, with acetone solution and be diluted to 0.1mg/mL.
The preparation of location solution 2: it is appropriate that precision takes methyl lactate L isomeride, with acetone solution and be diluted to 0.1mg/mL.
The preparation of sample solution: it is appropriate that precision takes methyl lactate, with acetone solution and be diluted to 0.1mg/mL.
Measure: get respectively location solution 1, location solution 2 and each 0.6 μ L of sample solution, inject gas chromatograph, records chromatogram, and wherein, the chromatogram of methyl lactate sample solution is shown in Fig. 1.The degree of separation that calculates methyl lactate D/L isomeride is 5.49.
Comparative example, employing document (Chromatographia, 2010,71 (5/6): the 539-544) separation of method to methyl lactate D, L isomeride
Adopt document (Chromatographia; 2010; 71 (5/6): the inwall of 539-544) having reported scribbles the self-control kapillary chiral column (20m * 0.25mm * 0.31 μ m) that 2,3-, bis--O-allyl-6-O-decoyl group-beta-cyclodextrin is chiral stationary phase and carries out the separation of methyl lactate optical isomer
Chromatographic condition:
Instrument: HP6890
+gas chromatograph, flame ionization ditector, shunting/Splitless injecting samples mouth
Chromatographic column: the capillary gas chromatographic column (20m * 0.25mm * 0.31 μ m) that 2,3-, bis--O-allyl-6-O-decoyl group-beta-cyclodextrin is chiral stationary phase
Mobile phase: high pure nitrogen
Injection port: split sampling, split ratio is 50: 1
Injector temperature: 250 ℃
Detector temperature: 280 ℃
Chromatograph furnace temperature: 60 ℃
The preparation of location solution 1: it is appropriate that precision takes methyl lactate D isomeride, with acetone solution and be diluted to 0.1mg/mL.
The preparation of location solution 2: it is appropriate that precision takes methyl lactate L isomeride, with acetone solution and be diluted to 0.1mg/mL.
The preparation of sample solution: it is appropriate that precision takes methyl lactate, with acetone solution and be diluted to 0.1mg/mL.
Measure: respectively get location solution 1, location solution 2 and each 0.6 μ L of sample solution, inject gas chromatograph, records chromatogram, and wherein, the chromatogram of methyl lactate sample solution is shown in Fig. 2.The degree of separation that calculates methyl lactate D/L isomeride is 1.74.
Claims (8)
1. 2,3 shown in formula I, the application in separating lactic acid methyl esters optical isomer as Chiral GC Stationary Phase of 6-tri--O-decoyl group-beta-cyclodextrin;
In formula I, R has the structure shown in formula II:
Wherein, n=6.
2. application according to claim 1, is characterized in that: described methyl lactate optical isomer is Pfansteihl methyl esters and D-ALPHA-Hydroxypropionic acid methyl esters.
3. a separated method that detects methyl lactate optical isomer, to adopt chiral capillary column vapor-phase chromatography, it is characterized in that: the chiral capillary column adopting is that inwall scribbles the chiral capillary column that 2,3,6-, tri--O-decoyl group-beta-cyclodextrin is chiral stationary phase;
The chromatographic condition of described chiral capillary column vapor-phase chromatography is as follows:
Chromatographic column is: inwall scribbles the chiral capillary column that 2,3,6-, tri--O-decoyl group-beta-cyclodextrin is chiral stationary phase, wherein, chromatogram column length is 20m～30m, and internal diameter is 250 μ m～320 μ m, and the thickness of the film of chiral stationary phase described in chromatographic column is 0.25～0.35 μ m;
Mobile phase is inert gas; Flow rate of mobile phase is 25～35cm/s;
Sample introduction adopts split sampling or Splitless injecting samples; The sample introduction split ratio of described split sampling is 20:1～50:1;
Detecting device is flame ionization ditector; Injector temperature is 200 ℃～280 ℃; The temperature of detecting device is 250 ℃～280 ℃; Chromatogram column temperature is 50～80 ℃.
4. method according to claim 3, is characterized in that: the chromatographic condition of described chiral capillary column vapor-phase chromatography is as follows:
Chromatographic column is: inwall scribbles the chiral capillary column that 2,3,6-, tri--O-decoyl group-beta-cyclodextrin is chiral stationary phase, and wherein, chromatogram column length is 20m, and internal diameter is 250 μ m, and the thickness of the film of chiral stationary phase described in chromatographic column is 0.31 μ m;
Mobile phase is nitrogen; Flow rate of mobile phase is 29cm/s;
Sample introduction adopts split sampling; The sample introduction split ratio of described split sampling is 50:1;
Detecting device is flame ionization ditector; Injector temperature is 250 ℃; The temperature of detecting device is 280 ℃; Chromatogram column temperature is 60 ℃.
5. according to the method described in claim 3 or 4, it is characterized in that: the sample solution adopting in described chiral capillary column vapor-phase chromatography is for adopting the solution of the methyl lactate 0.1mg/mL of organic solvent preparation.
6. method according to claim 5, is characterized in that: described organic solvent is selected from acetone, chloroform or methyl alcohol.
7. method according to claim 6, is characterized in that: described organic solvent is acetone.
8. in claim 3-7, the method described in any one is being carried out the application in assay to methyl lactate optical isomer.
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