CN102755882B - Application of Beta-cyclodextrin derivatives in preparing gas chromatography chiral stationary phases - Google Patents
Application of Beta-cyclodextrin derivatives in preparing gas chromatography chiral stationary phases Download PDFInfo
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Abstract
The invention discloses a novel application of Beta-cyclodextrin derivatives. According to the invention, the structural formula of the Beta-cyclodextrin derivatives is shown as Formula I, wherein R has the following structure shown in the description, and n is 1 to 10. The novel application of Beta-cyclodextrin derivatives reforms to the application in preparing gas chromatography chiral stationary phases. The Beta-cyclodextrin derivatives shown in the Formula I are taken as gas chromatography chiral stationary phases, so that certain isomers can be successfully separated, and the Beta-cyclodextrin derivatives have excellent separation capacity in separating 2-chlorine methyl propionate isomers and pantothenic acid lactone isomers.
Description
Technical field
The present invention relates to the application of beta cyclodextrin derivative in preparative gas chromatography chiral stationary phase.
Background technology
Chirality is one of the mankind's natural essential attribute of depending on for existence, and large biological molecule such as protein, polysaccharide, nucleic acid etc. all have chirality.There is optically active chiral material be extensively formed in the bodies of aminal and plant.Research finds, have medicine and the agricultural chemicals of chiral centre, its different enantiomter has different biologically actives, and some enantiomters even have toxic and side effect.Therefore, obtain the study hotspot that optically pure medicine, agricultural chemicals, spices, essence, food additives, new material etc. have become corresponding field, and identify chipal compounds absolute configuration, measure its optical purity, and study enantiomer analytical method simply and easily and also therefore become important research topic.
At present, existing multiple method can be used to the optical purity measuring chipal compounds, wherein use the capillary gas chromatography of chiral stationary phase be separated enantiomter have efficient, sensitive, quick, Chiral Separation Ability strong, be separated the advantages such as applied widely, reproducible, be widely used.
It is use chiral stationary phase that capillary gas chromatography directly carries out chiral separation, different and cause different retention times by the effect power of two enantiomters and chiral stationary phase, thus is separated.Chiral stationary phase mainly comprises chiral amino acid derivative, chiral metal complex, a few class such as cyclodextrine derivatives.
Wherein, cyclodextrine derivatives class chiral stationary phase is a very important class in capillary gas chromatography chiral Stationary liquid, this kind of chiral stationary phase generally obtains by replacing various different group at different the position of substitution of cyclodextrin molecular, cyclodextrine derivatives class chiral stationary phase mainly contains alpha-cyclodextrin derivative, beta-cyclodextrin derivative, and a few class such as gamma-cyclodextrin derivative.
Current use amount is maximum, and the important capillary gas chromatography chiral Stationary liquid of a most widely used class is beta-cyclodextrin derivative, and its general structure is as follows:
Wherein, R
1, R
2, R
3can be identical substituting group, also can be different substituting groups.
The beta-cyclodextrin derivative reported does Chiral GC Stationary Phase, mainly contains the 2-position at beta-schardinger dextrin-, 3-position, and the equal substituent methyl in 6-position, and 2,3,6-tri-obtained-O-methyl-B-cyclodextrin; Replace amyl group in the 2-position of beta-schardinger dextrin-and 6-position, replace 2, the 6-bis--O-amyl group-3-O-acetyl group-beta-cyclodextrins etc. of acetyl group in 3-position.
Also do capillary gas chromatography chiral Stationary liquid without any a kind of cyclodextrine derivatives at present, the demand of all Chiral Separation in real work can be met.Along with the appearance of increasing synthesising racemation mixture, therefore in the urgent need to developing the new chiral stationary phase with high separability energy, a greater variety of racemic mixture can be split.
Owing to cyclodextrin molecular replacing different groups, its Chiral Separation ability is different.Develop various novel cyclodextrine derivatives, to be satisfied with the actual demand of different Chiral Separation, there is certain practical significance.
Summary of the invention
The object of this invention is to provide the novelty teabag of beta-cyclodextrin derivative.
The novelty teabag of beta-cyclodextrin derivative provided by the present invention is its application in preparative gas chromatography chiral stationary phase.
Beta-cyclodextrin derivative described in the present invention, its structural formula is such as formula shown in I:
(formula I)
In formula I, R has the structure shown in formula II:
(formula II)
Wherein, n is 1-10, preferred n=3.
When n is 3, R is valeryl, and described beta-cyclodextrin derivative is specially 2,3,6-tri--O-valeryl group-beta-cyclodextrin.
Beta-cyclodextrin derivative shown in formula I is prepared by following method: under pyridine exists; the active alkyl acyl chloride of excessive reactivity worth and beta-schardinger dextrin-is adopted to react; by 2 of beta-schardinger dextrin-, the hydroxyl of 3 and 6 all derives and obtains for alkanoyl.
Chiral GC Stationary Phase described in the present invention specifically can be capillary gas chromatography chiral Stationary liquid.
Using the beta-cyclodextrin derivative shown in formula I as chiral stationary phase, be dissolved in after in carrene, adopt traditional static method, Stationary liquid wall is applied to the quartz capillary column wall with NaCl roughening, preparation chiral capillary gas chromatography chiral column.Evaluated by capillary gas chromatography, result shows that prepared chiral stationary phase has good chiral recognition, can to multiple chipal compounds (as 2-methyl chloropropionate isomers, pantolactone isomers, 2 bromopropionic acid methyl esters, trans-chrysanthemate methyl esters, propine alantol acetic acid esters, propylene alantol acetic acid esters, cis-2,3-epoxy-1-amylalcohol acetic acid esters or cis-2,3-epoxy-1-amylalcohol) be separated.Can be applicable to the control of the analysis of daily chemical object light isomers and the quality of production.
Because alkanoyl (especially valeryl) has longer carbochain and the centrifugation of acyl group simultaneously; prepared beta-cyclodextrin derivative is as Chiral GC Stationary Phase; can successfully be separated some enantiomers; especially in the separation to 2-methyl chloropropionate isomers and pantolactone isomers, show excellent separating power; for solution optical voidness medicine, agricultural chemicals; Chiral Separation problem in the production process of the products such as spices, essence, food additives, new material, has important value.
Accompanying drawing explanation
Fig. 1 is the chromatogram that 2 bromopropionic acid methyl esters splits on 2,3,6-tri--O-valeryl group-beta-cyclodextrin chiral stationary phase, column temperature 70 DEG C.
Fig. 2 is the chromatogram of the fractionation of 2-methyl chloropropionate on 2,3,6-tri--O-valeryl group-beta-cyclodextrin chiral stationary phase, column temperature 70 DEG C.
Fig. 3 is the chromatogram that pantolactone splits on 2,3,6-tri--O-valeryl group-beta-cyclodextrin chiral stationary phase, column temperature 130 DEG C.
Fig. 4 is the chromatogram that cis-2,3-epoxy-1-amylalcohol splits on 2,3,6-tri--O-valeryl group-beta-cyclodextrin chiral stationary phase, column temperature 70 DEG C.
Detailed description of the invention
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 1:2,3,6-tri-preparation of-O-valeryl group-beta-cyclodextrin
0.3g (0.264mmol) beta-schardinger dextrin-is dissolved in the dry chloroform of 15mL, at 0 DEG C, adds 2.5mL pyridine, under ice bath, drips 2.5mL valeric chloride (21.06mmol), after 0 DEG C of stirring reaction 0.5h, and 60 DEG C of stirring reaction 6h.React complete, after removal of solvent under reduced pressure, be dissolved in 20mL frozen water, with 20mL chloroform extraction 3 times, combined chloroform layer, after washing twice with saturated sodium bicarbonate aqueous solution, then wash twice with water, finally use anhydrous sodium sulfate drying, reduced pressure concentration obtains crude product.Viscous brown product (productive rate 20%) is obtained through column chromatography (toluene/ethyl acetate=1: 1, v/v) purifying.
Structural identification data are as follows:
IR(cm
-1)：2958，2930，2872(CH
2，CH
3)，1740(C＝O)，1462，1380，1343，(CH
2，CH
3)，1257，1241(CH
3)，1164，1107，1043(C-O-C)，755，734。
1H NMR(300MHz，CDCl
3)：0.89(9H，CH
3CH
2)，1.36(12H，CH
3CH
2CH
2)，1.58(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-valeryl group-beta-cyclodextrin.
Embodiment 2: beta-cyclodextrin derivative does the evaluation of capillary gas chromatography chiral Stationary liquid
Employing capillary gas chromatography is evaluated.By prepared 2; 3; 6-tri--O-valeryl group-beta-cyclodextrin is as chiral stationary phase; be dissolved in after in carrene; adopt traditional static method; Stationary liquid wall is applied to the quartz capillary column wall with NaCl roughening, preparation chiral capillary gas chromatography chiral column, with the Methane determination dead time.Evaluation result is in table 1 and Fig. 1-4.
The result of table 12,3,6-tri--O-valeryl group-beta-cyclodextrin chiral stationary phase partial enantiomeric sample
Carrier gas high-purity N
2(99.99%); Vaporizer temperature: 250 DEG C; Flame ionization ditector temperature: 280 DEG C; Split ratio: 30: 1.
Claims (1)
1. the beta-cyclodextrin derivative shown in formula I is being separated the application in enantiomter as Chiral GC Stationary Phase; Described enantiomter be selected from following any one: 2-methyl chloropropionate isomers, pantolactone isomers, 2 bromopropionic acid methyl esters isomers, trans-chrysanthemate methyl esters isomers, propine alantol acetate isomers, propylene alantol acetate isomers, cis-2,3-epoxy-1-amylalcohol acetate isomers and cis-2,3-epoxy-1-amylalcohol isomers;
In formula I, R has the structure shown in formula II:
Wherein, n is 3.
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Non-Patent Citations (3)
| Title |
|---|
| Chromatographic Properties of 2,3-Di-O-allyl-6-O-acyl-b-cyclodextrins as Chiral Stationary Phases of Capillary GC;Xueyan Shi,etal;《Chromatographia》;20100331;第71卷(第5-6期);摘要 * |
| Enantiomer Separation by Gas Chromatography on Cyclodextrin Chiral Stationary Phases;Wilhelm Keim等;《Journal of High Resolution Chromatography》;19910831;第14卷(第8期);第509页第2.4节和第510页表1 * |
| Wilhelm Keim,etal.Enantiomer Separation by Gas Chromatography on Cyclodextrin Chiral Stationary Phases.《Journal of High Resolution Chromatography》.1991,第14卷(第8期),第509页第2.4节和第510页表1. * |
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