CN102649049A - 2,3-two-O- MOM methoxymethyl-6-O-benzyl-Beta-cyclodextrin gas chromatograph-mass spectrometer chiral stationary phase and preparation method thereof - Google Patents
2,3-two-O- MOM methoxymethyl-6-O-benzyl-Beta-cyclodextrin gas chromatograph-mass spectrometer chiral stationary phase and preparation method thereof Download PDFInfo
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- CN102649049A CN102649049A CN2011100429032A CN201110042903A CN102649049A CN 102649049 A CN102649049 A CN 102649049A CN 2011100429032 A CN2011100429032 A CN 2011100429032A CN 201110042903 A CN201110042903 A CN 201110042903A CN 102649049 A CN102649049 A CN 102649049A
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Abstract
The invention relates to capillary gas chromatograph-mass spectrometer chiral stationary phase 2,3-two-O- MOM methoxymethyl-6-O-benzyl-Beta-cyclodextrin and a preparation method thereof. The chiral stationary phase is characterized in that MOM methoxymethyl is introduced to 2-place and 3-place of Beta-cyclodextrin molecules, and then benzyl is introduced to 6-place of Beta-cyclodextrin molecules, so as to obtain novel Beta-cyclodextrin derivatives. The novel Beta-cyclodextrin derivatives produced by the method are suitable to serve as the chiral stationary phase of capillary gas chromatograph-mass spectrometer and have a certain degree of chiral recognition capability and thus can successfully separate enantiomers of certain chiral compounds.
Description
Technical field
The present invention relates to 2,3-two-O-methoxyl methyl-6-O-benzyl-beta-schardinger dextrin-chiral stationary phase and preparation method thereof belongs to gas-chromatography enantiomer separation field.
Background technology
Chirality is one of essential attribute of mankind's nature of depending on for existence, and large biological molecule such as protein, polysaccharide, nucleic acid etc. all have the chirality characteristic.Discover to have the medicine of chiral centre and the enantiomter chirality of agricultural chemicals and often exist significant difference at aspects such as biologically active, metabolic processes.Therefore, obtain optically pure medicine and become corresponding hot research fields.Study each single optical siomerism body structure of chiral drug and active relation, the ratio of effective body and invalid body in the mensuration racemic modification, and in environment and biotransformation, effective body is monitored, all require the chirality agricultural chemicals is carried out compartment analysis.This alanysis testing generally is especially to realize with the direct separation on the chromatogram chiral stationary phase with the chromatogram means, and wherein the gas chromatography chiral stationary phase process is so that it is quick, sensitive, separating property is good, quantitatively accurately, with an organic solvent do not wait advantage to cause people's attention.
Capillary gas chromatography directly carries out chiral separation and is to use chiral stationary phase, causes different retention times through two enantiomters are strong and weak different with the effect of chiral stationary phase, thereby obtains separating.Chiral stationary phase mainly comprises several types of chiral amino acid derivative, chiral metal complex, cyclodextrine derivatives etc.At present, with fastest developing speed in the gas chromatography chiral separate study, the widest chiral stationary phase of application is various types of cyclodextrine derivatives.This type chiral stationary phase generally replaces various group through the different the position of substitution at cyclodextrin molecular and obtains, and cyclodextrins chiral is fixing to be divided into several types in alpha-cyclodextrin derivative, beta-cyclodextrin derivative, gamma-cyclodextrin derivative etc. according to D-glucopyranose unit number difference contained in the cyclodextrin molecular.Wherein the general structure of the most widely used beta-cyclodextrin derivative is following:
Wherein, R
1, R
2, R
3Can be identical substituting group, also can be different substituting groups.
This type chiral stationary phase is that present use amount is maximum, and the most widely used one type of important capillary gas chromatography chiral is phase fixedly.But; Appearance along with increasing synthesising racemation mixture; These chiral stationary phases also not all are suitable for separating different types of racemic mixture, therefore press for to develop the new chiral stationary phase that high score leaves performance that has, and can split a greater variety of racemic mixtures.
Discover the different group of replacement on the cyclodextrin molecular, its chiral separation ability is different.Of the present invention is to introduce methoxyl methyl in the 2-position and the 3-position of beta-schardinger dextrin-molecule; Introduce benzyl in the 6-position, and the novel beta-cyclodextrin derivative that obtains is used as fixedly phase of capillary gas chromatography chiral; Be used for Chiral Separation, still do not have report at present both at home and abroad.
Summary of the invention
Provided by the invention 2,3-two-O-methoxyl methyl-6-O-benzyl-beta-schardinger dextrin-is suitable as fixedly phase of capillary gas chromatography chiral, can the chipal compounds of multiple structure be separated.
Described in the invention 2,3-two-O-methoxyl methyl-6-O-benzyl-beta-schardinger dextrin-chiral stationary phase is meant in the 2-position of beta-schardinger dextrin-molecule and 3-position introduces methoxyl methyl, and benzyl is introduced in the 6-position, and the novel beta-cyclodextrin derivative that makes.The present invention includes described is 2 of initiation material with the beta-schardinger dextrin-; The preparation of 3-two-O-methoxyl methyl-6-O-benzyl-beta-schardinger dextrin-; And using saidly 2,3-two-O-methoxyl methyl-6-O-benzyl-beta-schardinger dextrin-is done the fixing enantiomer that splits mutually of capillary gas chromatography chiral.
Described in the invention 2,3-two-O-methoxyl methyl-6-O-benzyl-beta-schardinger dextrin-capillary gas chromatography chiral is fixing to have following structure mutually:
R wherein
1Be methoxyl methyl, have following structure:
R
2Be benzyl, have following structure:
The present invention also provides a kind of above-mentioned 2; The preparation method of 3-two-O-methoxyl methyl-6-O-benzyl-beta-schardinger dextrin-chiral stationary phase; It is characterized in that: be solvent with the dimethyl sulfoxide (DMSO) at first, under alkali condition, cylite and β-CD reaction; Hydrogen in the substituted cyclodextrin molecule on the hydroxyl of 6-position has synthesized 6-O-benzyl-β-CD.In the presence of diisopropylethylamine, 6-O-benzyl-β-CD and chloromethyl ether react in anhydrous methylene chloride then, have replaced 2, the hydrogen on the hydroxyl of 3-position, and make 2,3-two-O-methoxyl methyl-6-O-benzyl-beta-schardinger dextrin-.
Of the present invention 2,3-two-O-methoxyl methyl-6-O-benzyl-beta-schardinger dextrin-capillary gas chromatography chiral fixedly among the preparation method of phase, may further comprise the steps:
Beta-schardinger dextrin-molecule and cylite reaction are made 6-O-benzyl-beta-schardinger dextrin-;
6-O-benzyl-beta-schardinger dextrin-and chloromethyl ether reaction are made 2,3-two-O-methoxyl methyl-6-O-benzyl-beta-schardinger dextrin-.
The present invention make 2,3-two-O-methoxyl methyl-6-O-benzyl-beta-schardinger dextrin-is as the fixing phase of capillary gas chromatography chiral.Through the capillary gas chromatography evaluation, the result shows that prepared novel chiral is fixing and has certain chiral Recognition ability mutually, can separate multiple chipal compounds.Simultaneously, prepared novel chiral is fixing to have good stability mutually, has the potentiality that are applied to daily Pharmaceutical Analysis and quality of production control.
Description of drawings:
Fig. 1: cis-dichlor chrysanthemic acid methyl esters is at chiral stationary phase 2, the fractionation on 3-two-O-methoxyl methyl-6-O-benzyl-beta-schardinger dextrin-, 100 ℃ of column temperatures
Fig. 2: trans-dichlor chrysanthemic acid methyl esters is at chiral stationary phase 2, the fractionation on 3-two-O-methoxyl methyl-6-O-benzyl-beta-schardinger dextrin-, 100 ℃ of column temperatures.
Fig. 3: cis-chrysanthemumic acid methyl esters is at chiral stationary phase 2, the fractionation on 3-two-O-methoxyl methyl-6-O-benzyl-beta-schardinger dextrin-, 100 ℃ of column temperatures.
Fig. 4: trans-chrysanthemumic acid methyl esters is at chiral stationary phase 2, the fractionation on 3-two-O-methoxyl methyl-6-O-benzyl-beta-schardinger dextrin-, 100 ℃ of column temperatures.
Fig. 5: cis-chrysanthemumic acid ethyl ester is at chiral stationary phase 2, the fractionation on 3-two-O-methoxyl methyl-6-O-benzyl-beta-schardinger dextrin-, 80 ℃ of column temperatures.
Fig. 6: trans-chrysanthemumic acid ethyl ester is at chiral stationary phase 2, the fractionation on 3-two-O-methoxyl methyl-6-O-benzyl-beta-schardinger dextrin-, 80 ℃ of column temperatures.
Fig. 7: cis-time chrysanthemumic acid methyl esters is at chiral stationary phase 2, the fractionation on 3-two-O-methoxyl methyl-6-O-benzyl-beta-schardinger dextrin-, 80 ℃ of column temperatures.
The specific embodiment: followingly the present invention is specifically set forth, but be not limited thereto through instance.
The preparation of example 1:6-O-benzyl-beta-schardinger dextrin-.
The 3g beta-schardinger dextrin-is dissolved in the 60mL dimethyl sulfoxide (DMSO), adds 1.2g NaOH, be warming up to 70 ℃ of reaction 2h behind the stirring at room 30min, be cooled to room temperature then, drip the 3.3mL cylite, be warming up to 60 ℃ of reaction 8h behind the stirring at room 12h.Reaction is poured mixed liquor in the water into after finishing, and chloroform extraction three times is used the hydrochloric acid solution of 0.5mol/L then successively, and saturated sodium bicarbonate and sodium chloride solution are washed till neutrality.Anhydrous sodium sulfate drying, rotary evaporation remove to desolvate and obtain crude product.
Example 2:2, the preparation of 3-two-O-methoxyl methyl-6-O-benzyl-beta-schardinger dextrin-
0.5g 6-O-benzyl-β-CD is dissolved in the 20mL anhydrous methylene chloride, adds the 3.8mL diisopropylethylamine.5 ℃ drip the 1.5mL chloromethyl ether down, temperature rising reflux reaction 24h.Reaction finishes mixed liquor is poured in the water, and chloroform extraction three times is used the hydrochloric acid solution of 0.5mol/L then successively, and saturated sodium bicarbonate and sodium chloride solution are washed till neutrality.Anhydrous sodium sulfate drying, rotary evaporation remove to desolvate and obtain crude product.Through purified obtain product (the column chromatography eluant, eluent is: benzinum: ethyl acetate=1: 1, v/v).
IR(cm
-1)：2931，1454，1362，1267，1209，1149，1032，737，701
1HNMR(600MHz，CDCl
3)：7.44-7.28(-CH
2-Ph-
H)，5.28(H
1)，5.04(-C
H 2-Ph)，3.96(H
5)，4.71-4.56
(CH
3-O-C
H 2O-)，3.84-3.70(H
3，H
4，H
6)，3.27-3.24(C
H 3-O-CH
2O-)，2.63(H
2)；
13CNMR(600MHz，CDCl
3)：138.34-128.29(-CH
2-
Ph)，99.35(C
1)，99.21-96.71(-O
CH
2OCH
3)，77.37
(C
2)，76.93(-
CH
2-Ph)，73.02(C
3，C
4),71.10(C
5)，71.01(C
6)，56.18-55.26(-OCH
2O
CH
3)
Example 3:2,3-two-O-methoxyl methyl-6-O-benzyl-beta-schardinger dextrin-is as the fixedly evaluation of phase of capillary gas chromatography chiral
The employing capillary gas chromatography is estimated.With prepared 2; 3-two-O-methoxyl methyl-6-O-benzyl-beta-schardinger dextrin-is as chiral stationary phase, be dissolved in the carrene respectively after, adopt traditional static method; Fixing phase wall is applied to the quartz capillary column wall with the sodium chloride roughening, preparation chiral capillary gas chromatography chiral column.Evaluation result is seen table and figure.
Table 1 prepared 2,3-two-O-methoxyl methyl-6-O-benzyl-beta-schardinger dextrin-chiral stationary phase splits the result of part enantiomer sample.
High-purity N is used in carrier gas
2(99.99%); Vaporizer temperature: 250 ℃; Flame ionization ditector temperature: 250 ℃; Split ratio 30: 1.
Claims (6)
1.2; 3-two-O-methoxyl methyl-6-O-benzyl-beta-schardinger dextrin-capillary gas chromatography chiral is phase fixedly; It is characterized in that: methoxyl methyl is introduced in 2-position and 3-position at the beta-schardinger dextrin-molecule; Introduce benzyl in the 6-position, and the novel beta-cyclodextrin derivative that makes is used as fixedly phase of capillary gas chromatography chiral.
2. described 2 according to claim 1,3-two-O-methoxyl methyl-6-O-benzyl-beta-schardinger dextrin-capillary gas chromatography chiral is phase fixedly, and it is characterized in that: described chiral stationary phase has following structural formula:
R wherein
1Be methoxyl methyl, have following structure:
R
2Be benzyl, have following structure:
3. claim 1 described 2; 3-two-O-methoxyl methyl-6-O-benzyl-beta-schardinger dextrin-capillary gas chromatography chiral is the preparation method of phase fixedly; It is characterized in that: be solvent with the dimethyl sulfoxide (DMSO) at first, under alkali condition, cylite and β-CD reaction; Hydrogen in the substituted cyclodextrin molecule on the hydroxyl of 6-position has synthesized 6-O-benzyl-β-CD.In the presence of diisopropylethylamine, 6-O-benzyl-β-CD and chloromethyl ether react in anhydrous methylene chloride then, have replaced 2, the hydrogen on the hydroxyl of 3-position, and make 2,3-two-O-methoxyl methyl-6-O-benzyl-beta-schardinger dextrin-.
4. according to claim 3 described 2; 3-two-O-methoxyl methyl-6-O-benzyl-beta-schardinger dextrin-capillary gas chromatography chiral is fixedly among the preparation method of phase; It is characterized in that: described 2,3-two-O-methoxyl methyl-6-O-benzyl-beta-schardinger dextrin-capillary gas chromatography chiral is fixing to have following structure mutually:
R wherein
1Be methoxyl methyl, have following structure:
R
2Be benzyl, have following structure:
5. described 2 according to claim 3,3-two-O-methoxyl methyl-6-O-benzyl-beta-schardinger dextrin-capillary gas chromatography chiral fixedly among the preparation method of phase, may further comprise the steps:
Beta-schardinger dextrin-molecule and cylite reaction are made 6-O-benzyl-beta-schardinger dextrin-;
6-O-benzyl-beta-schardinger dextrin-and chloromethyl ether reaction are made 2,3-two-O-methoxyl methyl-6-O-benzyl-beta-schardinger dextrin-.
6. claim 1 is described 2,3-two-O-methoxyl methyl-6-O-benzyl-beta-schardinger dextrin-capillary gas chromatography chiral enantiomer that fixedly is separated.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105241983A (en) * | 2015-09-30 | 2016-01-13 | 赵林萍 | Chromatographic column for detecting pesticide residue in food |
| CN105353061A (en) * | 2015-09-30 | 2016-02-24 | 赵林萍 | Production method of gas chromatography column for chiral pesticide residue detection in food |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5403898A (en) * | 1992-05-04 | 1995-04-04 | Brigham Young University | Single arm attached cyclodextrin polysiloxanes and use thereof as chiral stationary phases in chromatographic separation of enantiomers |
| CN101015789A (en) * | 2007-01-05 | 2007-08-15 | 中国农业大学 | Beta-cyclodextrin derivative capillary gas chromatography chiral fixed phase and preparing method thereof |
| CN101306354A (en) * | 2007-05-17 | 2008-11-19 | 华东理工大学 | Cyclodextrin chiral chromatogram fixed phase and preparation method thereof |
| CN101372516A (en) * | 2008-08-14 | 2009-02-25 | 广州研创生物技术发展有限公司 | Beta-cyclodextrin derivative, preparation thereof and use as chiral selector |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5403898A (en) * | 1992-05-04 | 1995-04-04 | Brigham Young University | Single arm attached cyclodextrin polysiloxanes and use thereof as chiral stationary phases in chromatographic separation of enantiomers |
| CN101015789A (en) * | 2007-01-05 | 2007-08-15 | 中国农业大学 | Beta-cyclodextrin derivative capillary gas chromatography chiral fixed phase and preparing method thereof |
| CN101306354A (en) * | 2007-05-17 | 2008-11-19 | 华东理工大学 | Cyclodextrin chiral chromatogram fixed phase and preparation method thereof |
| CN101372516A (en) * | 2008-08-14 | 2009-02-25 | 广州研创生物技术发展有限公司 | Beta-cyclodextrin derivative, preparation thereof and use as chiral selector |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105241983A (en) * | 2015-09-30 | 2016-01-13 | 赵林萍 | Chromatographic column for detecting pesticide residue in food |
| CN105353061A (en) * | 2015-09-30 | 2016-02-24 | 赵林萍 | Production method of gas chromatography column for chiral pesticide residue detection in food |
| CN105353061B (en) * | 2015-09-30 | 2017-07-14 | 河南中标检测服务有限公司 | Preparation method for the gas chromatographic column of Chiral pesticide residue detection in food |
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