CN101015789A - Beta-cyclodextrin derivative capillary gas chromatography chiral fixed phase and preparing method thereof - Google Patents
Beta-cyclodextrin derivative capillary gas chromatography chiral fixed phase and preparing method thereof Download PDFInfo
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Abstract
The invention relates to a novel beta-cyclodextrin derivant capillary gas spectrum chiral fixed phase and relative preparation. The invention is characterized in that the invention leads allyl group with two keys into 2 and 3 positions of beta-cyclodextrin molecule, and leads valeryl group, enanthoyl group or caprylyl group into 6 position of beta-cyclodextrin molecule, to obtain novel beta-cyclodextrin detrivant. The inventive detrivant can be used as chiral fixed phase of capillary gas spectrum, with some chiral recognize ability to separate antimer of chiral compound.
Description
Technical field:
The field that the present invention relates to is the chiral chromatogram enantiomer separation, and novel beta-cyclodextrin derivative capillary gas chromatography chiral described in the invention is fixed and is used for this chiral chromatogram Chiral Separation mutually.
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 chirality.Having optically active chiral material extensively is formed in the bodies of aminal and plant.Discover to have the medicine and the agricultural chemicals of chiral centre, its different enantiomter has different biologically actives, the enantiomter that has even have toxic and side effect.Therefore, oneself becomes the research focus in corresponding field to obtain optically pure medicine, agricultural chemicals, spices, essence, food additives, new material etc., and identify chipal compounds absolute configuration, measure its optical purity, and study simply and easily that therefore the enantiomer analytical method also becomes important research project.
At present, existing several different methods can be used to measure the optical purity of chipal compounds, wherein use the capillary gas chromatography of chiral stationary phase separate enantiomter have efficiently, sensitive, fast, advantages such as the chiral separation ability is strong, separation is applied widely, good reproducibility, be widely used.
Capillary gas chromatography directly carries out chiral separation and is to use chiral stationary phase, causes different retention times by two enantiomters are strong and weak different with the effect of chiral stationary phase, thereby obtains separating.Chiral stationary phase mainly comprises chiral amino acid derivative, chiral metal complex, several classes such as cyclodextrine derivatives.
Wherein, cyclodextrine derivatives class chiral stationary phase is a very important class during capillary gas chromatography chiral is fixed mutually, this class chiral stationary phase generally replaces various group by the different the position of substitution at cyclodextrin molecular and makes, cyclodextrine derivatives class chiral stationary phase mainly contains the alpha-cyclodextrin derivative, beta-cyclodextrin derivative, and several classes such as gamma-cyclodextrin derivative, wherein the general structure of the most widely used beta-cyclodextrin derivative is as follows:
Wherein, R
1, R
2, R
3Can be identical substituting group, also can be different substituting groups.
This class chiral stationary phase is present use amount maximum, and the important capillary gas chromatography chiral of a most widely used class is phase fixedly.But, appearance along with increasing synthesising racemation mixture, these chiral stationary phases can not all be suitable for separating different types of racemic mixture, therefore press for exploitation new have the chiral stationary phase of high score from performance, can split a greater variety of racemic mixtures.
Discover the different group of replacement on the cyclodextrin molecular, its chiral separation ability difference.Of the present invention is to introduce pi-allyl in the 2-position and the 3-position of beta-schardinger dextrin-molecule, introduce acyl group in the 6-position, and the novel beta-cyclodextrin derivative that obtains is used as fixedly phase of capillary gas chromatography chiral, is used for Chiral Separation, does not still have report at present both at home and abroad.
Summary of the invention:
Novel beta-cyclodextrin derivative provided by the invention is suitable as fixedly phase of capillary gas chromatography chiral, can the chipal compounds of multiple structure be separated.
Novel beta-cyclodextrin derivative chiral stationary phase described in the invention is meant in the 2-position of beta-schardinger dextrin-molecule and 3-position introduces the pi-allyl with two keys, introduces valeryl or heptanoyl group or caprylyl in the 6-position, and the novel beta-cyclodextrin derivative that makes.The present invention includes described is the preparation of the novel beta-cyclodextrin derivative of initiation material with the beta-schardinger dextrin-, and uses described novel beta-cyclodextrin derivative to do the fixing enantiomer that splits mutually of capillary gas chromatography chiral.
Novel beta-cyclodextrin derivative capillary gas chromatography chiral described in the invention is fixed has following structure mutually:
Wherein, R
1Be double bond containing pi-allyl, have following structure:
-CH
2-CH＝CH
2
R
2Be valeryl, or be heptanoyl group, or be caprylyl to have following structure:
Wherein, n is 3, or is 5, or is 6
The present invention also provides a kind of preparation method of above-mentioned novel beta-cyclodextrin derivative chiral stationary phase; it is characterized in that: at first use tert-butyl chloro-silicane to do protecting group; the 6-position primary hydroxyl of beta-schardinger dextrin-is protected; again beta-schardinger dextrin-2-position and 3-position hydroxyl are derived and be pi-allyl; after at last protecting group tert-butyl group dimethylsilyl being sloughed; 6-position hydroxyl derived is valeryl or heptanoyl group or caprylyl, and makes novel beta-cyclodextrin derivative.
Among the preparation method of chiral stationary phase of the present invention, chiral stationary phase has following structure:
Wherein, R
1Be double bond containing pi-allyl, have following structure:
-CH
2-CH＝CH
2
R
2Be valeryl, or be heptanoyl group, or be caprylyl to have following structure:
Wherein, n is 3, or is 5, or is 6
Novel beta-cyclodextrin derivative capillary gas chromatography chiral of the present invention fixedly among the preparation method of phase, may further comprise the steps:
Beta-schardinger dextrin-molecule and tert-butyl chloro-silicane reaction are made 6-O-tert-butyl group dimethylsilyl-beta-schardinger dextrin-;
6-O-tert-butyl group dimethylsilyl-beta-schardinger dextrin-and bromopropene reaction are made 2,3-two-O-pi-allyl-6-O-tert-butyl group dimethylsilane-beta-schardinger dextrin-;
With 2,3-two-O-pi-allyl-6-O-tert-butyl group dimethylsilane-beta-schardinger dextrin-is sloughed protecting group, obtains 2,3-two-O-allyl group-beta-cyclodextrin
With 2,3-two-O-allyl group-beta-cyclodextrin and valeric chloride or oenanthyl chloro or caprylyl chloride reaction obtain 3 kinds of products:
Product 1:2,3-two-O-pi-allyl-6-O-valeryl group-beta-cyclodextrin
Product 2:2,3-two-O-pi-allyl-6-O-oenanthyl group-beta-cyclodextrin
Product 3:2,3-two-O-pi-allyl-6-O-decoyl group-beta-cyclodextrin.
Among the preparation method of novel beta-cyclodextrin derivative chiral stationary phase of the present invention, prepared chiral stationary phase is listed as follows, and correspondence is the code name title of chiral stationary phase in the bracket:
2,3-two-O-pi-allyl-6-O-valeryl group-beta-cyclodextrin (CSP1)
2,3-two-O-pi-allyl-6-O-oenanthyl group-beta-cyclodextrin (CSP2)
2,3-two-O-pi-allyl-6-O-decoyl group-beta-cyclodextrin (CSP3)
The present invention adopts and at first uses tert-butyl chloro-silicane to do protecting group; the 6-position primary hydroxyl of beta-schardinger dextrin-is protected; again beta-schardinger dextrin-2-position and 3-position hydroxyl are derived and be pi-allyl; after at last protecting group tert-butyl group dimethylsilyl being sloughed; 6-position hydroxyl derived be valeryl or heptanoyl group or caprylyl; and make novel beta-cyclodextrin derivative, be used as fixedly phase of capillary gas chromatography chiral.By 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: the fractionation of propine alcohol ketone acetic acid esters on chiral stationary phase CSP1,120 ℃ of column temperatures
Fig. 2: the fractionation of propylene alcohol ketone acetic acid esters on chiral stationary phase CSP1,120 ℃ of column temperatures
Fig. 3: the fractionation of 2 bromopropionic acid methyl esters on chiral stationary phase CSP1,60 ℃ of column temperatures
Fig. 4: the fractionation of 2-methyl chloropropionate on chiral stationary phase CSP1,60 ℃ of column temperatures
Fig. 5: cis-2, the 3-epoxy-fractionation of 1-amylalcohol acetic acid esters on chiral stationary phase CSP1,70 ℃ of column temperatures
Fig. 6: 1-(2, the 4-the dichlorophenyl)-fractionation of ethanol on chiral stationary phase CSP1,120 ℃ of column temperatures
Fig. 7: the fractionation of 2 hydroxy propanoic acid methyl esters on chiral stationary phase CSP1,60 ℃ of column temperatures
Fig. 8: the fractionation of propine alcohol ketone acetic acid esters on chiral stationary phase CSP2,120 ℃ of column temperatures
Fig. 9: the fractionation of propylene alcohol ketone acetic acid esters on chiral stationary phase CSP2,120 ℃ of column temperatures
Figure 10: the fractionation of 2 bromopropionic acid methyl esters on chiral stationary phase CSP2,60 ℃ of column temperatures
Figure 11: the fractionation of propine alcohol ketone acetic acid esters on chiral stationary phase CSP3,120 ℃ of column temperatures
Figure 12: the fractionation of propylene alcohol ketone acetic acid esters on chiral stationary phase CSP3,120 ℃ of column temperatures
Figure 13: the fractionation of 2 bromopropionic acid methyl esters on chiral stationary phase CSP3,60 ℃ of column temperatures
Figure 14: the fractionation of 2-methyl chloropropionate on chiral stationary phase CSP3,60 ℃ of column temperatures
Figure 15: 1-(2, the 4-the dichlorophenyl)-fractionation of ethanol on chiral stationary phase CSP3,120 ℃ of column temperatures
The specific embodiment: below by example the present invention is specifically addressed, but is not limited thereto.
The preparation of example 1:6-O-tert-butyl group dimethylsilyl-beta-schardinger dextrin-(6-O-TBS-beta-schardinger dextrin-)
3.36g (2.96mmol) beta-schardinger dextrin-is dissolved in the 45 mL dry pyridines, under 0 ℃, drip the 30mL dry pyridine solution of 3.44g (22.78mmol) tert-butyl chloro-silicane, 0 ℃ of stirring reaction 3 h, after stirring reaction spends the night under the room temperature, in the impouring equivalent frozen water, stir, white precipitate occurs after leaving standstill, collect white precipitate, after twice of 200 mL washing, filtration drying gets product.
1H NMR (300MHz, CDCl
3): 0.66ppm (6H, Si-C
H 3), 0.87 (9H, C (C
H 3)
3), 3.3～4.0 (H on the CD ring, 6H), 4.89～4.95 (1H, different H of CD), 5.2～5.31 (1H, O
H), 6.6～6.8 (1H, OH)
Example 2:2, the preparation of 3-two-O-pi-allyl-6-O-tert-butyl group dimethylsilane-beta-schardinger dextrin-
The 2g50% sodium hydride adds three-neck flask, add the dry dimethyl formamide (DMF) of 90mL, after being cooled to 0 ℃, drip the 60mLDMF liquid of 3g6-O-tert-butyl group dimethylsilyl-beta-schardinger dextrin-(6-O-TBS-beta-schardinger dextrin-), dropwise, room temperature reaction is after 2 hours, ice bath is chilled to 0 ℃, drip the 8mL bromopropene, ice bath reacted 1 hour down, and reaction is 24 hours under the room temperature.Reaction finishes, and removes excessive sodium hydride with methyl alcohol, remove DMF under reduced pressure after, with chloroform 50mL * 3 extractions, the combined chloroform layer is washed chloroform layer 2 times with saturated sodium-chloride water 50mL, 50mL washing 3 times, the decompression of dry back concentrates, and gets product.
IR(cm
-1)：3080(C＝CH
2)，2940，2900，2860(CH
2，CH
3)，1643(C＝C)，1460，1375，1360(CH
2，CH
3)，1250，1210((CH
3)
3)，1160，1090，1045(C-O-C)，920(CH＝CH
2)，838，775(si-C)
1H NMR(300MHz，CDCl
3)：0.029(Si(C
H 3)
2)，0.88(C(C
H 3)
3，C
H 3)，1.25(CH
3C
H 2-)，3.3-4.2(CD(
H)，OC
H 2)，5.1-5.28(CD(
H)，CH＝C
H 2)，5.9(C
H＝CH
2)
Example 3:2, the preparation of 3-two-O-allyl group-beta-cyclodextrin
With 5mL tetrabutyl amine fluoride (1molL
-1THF liquid) add 3.1g 2, in oxolane (THF) the 10mL liquid of 3-two-O-pi-allyl-6-O-tert-butyl group dimethylsilane-beta-schardinger dextrin-, back flow reaction 70min, after decompression concentrates, add 20mL chloroform lysate, chloroform layer is washed 3 times with the 20mL saturated sodium-chloride, after 20mL washes twice, anhydrous sodium sulfate drying, concentrate product.
IR(cm
-1)：3445(O-H)，3079(C＝CH
2)，2940，2924，2850(CH
3，CH
2)，1644(C＝C)，1458，1415，1350(CH
3，CH
2)，1160，1090，1040(C-O-C)，923(CH＝CH
2)
1H NMR(300MHz，CDCl
3)：0.88(C
H 3CH
2)，1.25(CH
3C
H 2)，3.3-4.4(CD(
H)，OC
H 2)，5.0-5.28(CD(
H)，CH＝C
H 2)，5.9(C
H＝CH
2)
Example 4:2, the preparation of 3-two-O-pi-allyl-6-O-valeryl group-beta-cyclodextrin (CSP1):
0.8mL valeric chloride is added into 0.52,70 ℃ add thermal response 7h in the 10mL dry pyridine solution of 3-two-O-pi-allyl-β-CD.Reaction finishes in the impouring 30mL frozen water, with behind 30mL * 3 chloroform extractions, chloroform layer washed twice with saturated sodium bicarbonate aqueous solution after, wash twice again with water, use anhydrous sodium sulfate drying at last.Decompression concentrate crude product.Column chromatography (1: 1 toluene/ethyl acetate) purifying gets brown thickness product (20%yields).
IR(cm
-1)：3079(C＝CH
2)，2950，2928，2868(CH
3，CH
2)，1740(C＝O)，1648(C＝C)，1460，1417，1380(CH
2，CH
3)，1165，1095，1050(C-O-C)，924(CH＝CH
2)
1H NMR(300MHz，CDCl
3)：0.89(C
H 3CH
2)，1.30(CH
3C
H 2C
H 2)，1.58(OCH
2C
H 2)，2.32(COC
H 2)，3.2-5.5(CD(
H))，OC
H 2，CH＝C
H 2)，5.9(C
H＝CH
2)
Example 5:2, the preparation of 3-two-O-pi-allyl-6-O-oenanthyl group-beta-cyclodextrin (CSP2):
Each operating procedure just replaces valeric chloride with oenanthyl chloro with example 4, gets pale brown look thickness product.
IR(cm
-1)：3079(C＝CH
2)，2950，2928，2864(CH
3，CH
2)，1740(C＝O)，1649(C＝C)，1460，1417，1380(CH
2，CH
3)，1149，1095，1040(C-O-C)，924(CH＝CH
2)
1H NMR(300MHz，CDCl
3)：0.88(C
H 3CH
2)，1.28(CH
3C
H 2C
H 2)，1.59(OCH
2C
H 2)，2.33(COC
H 2)，3.2-4.5(CD(
H)，OC
H 2)，5.0-5.28(CD(
H)，CH＝C
H 2)，5.9(C
H＝CH
2)
Example 6:2, the preparation of 3-two-O-pi-allyl-6-O-decoyl group-beta-cyclodextrin (CSP3):
Each operating procedure just replaces valeric chloride with caprylyl chloride with example 4, gets pale brown look thickness product.
IR(cm
-1)：3080(C＝CH
2)，2950，2927，2859(CH
3，CH
2)，1739(C＝O)，1649(C＝C)，1460，1418，1350(CH
2，CH
3)，1151，1095，1040(C-O-C)，923(CH＝CH
2)
1H NMR(300MHz，CDCl
3)：0.86(C
H 3CH
2)，1.28(CH
3C
H 2C
H 2)，1.63(OCH
2C
H 2)，2.32(COC
H 2)，3.2-4.5(CD(
H)，OC
H 2)，5.1-5.28(CD(
H)，CH＝C
H 2)，5.9(C
H＝CH
2)
Example 7: novel beta-cyclodextrin derivative is done the fixedly evaluation of phase of capillary gas chromatography chiral
The employing capillary gas chromatography is estimated.With prepared novel beta-cyclodextrin derivative as chiral stationary phase, after being dissolved in the carrene respectively, adopt traditional static method, fixing phase wall is applied to quartz capillary column wall with the NaCl roughening, preparation chiral capillary gas chromatography chiral column is measured the dead time with methane.Evaluation result sees Table and schemes.
Show the result that prepared novel beta-cyclodextrin derivative chiral stationary phase splits part enantiomer sample
| Fixing phase | The sample title | Column temperature | Capacity factor measure | Separation factor | |
| CSP1 | The 2 bromopropionic |
60℃ | 6.65 | 7.61 | 1.14 |
| The 2- |
60℃ | 3.24 | 3.45 | 1.07 | |
| The 2 hydroxy propanoic |
60℃ | 4.46 | 4.93 | 1.10 | |
| Propine alantol acetic acid esters | 120℃ | 61.57 | 63.42 | 1.03 | |
| Propylene alantol acetic acid esters | 120℃ | 34.38 | 35.45 | 1.03 | |
| 1-(2, the 4-dichlorophenyl)-ethanol | 120℃ | 54.65 | 59.61 | 1.09 | |
| Cis-2,3-epoxy-1-amylalcohol |
70℃ | 23.19 | 23.96 | 1.03 | |
| Cis-2,3-epoxy-1- |
70℃ | 22.99 | 23.40 | 1.02 | |
| CSP2 | The 2 bromopropionic |
60℃ | 6.56 | 7.28 | 1.11 |
| The 2 hydroxy propanoic |
60℃ | 5.21 | 5.54 | 1.06 | |
| Propine alantol acetic acid esters | 120℃ | 56.89 | 58.46 | 1.03 | |
| Propylene alantol acetic acid esters | 120℃ | 31.77 | 32.67 | 1.03 | |
| CSP3 | The 2 bromopropionic |
60℃ | 5.66 | 6.28 | 1.11 |
| The 2- |
60℃ | 2.79 | 2.92 | 1.05 | |
| The 2 hydroxy propanoic |
60℃ | 3.95 | 4.26 | 1.08 | |
| Propine alantol acetic acid esters | 120℃ | 50.20 | 51.54 | 1.03 | |
| Propylene alantol acetic acid esters | 120℃ | 29.08 | 28.83 | 1.03 | |
| 1-(2, the 4-dichlorophenyl)-ethanol | 120℃ | 50.04 | 54.07 | 1.08 | |
| Cis-2,3-epoxy-1-amylalcohol |
70℃ | 19.47 | 19.98 | 1.03 |
The carrier gas high-purity N
2(99.99%); Vaporizer temperature: 250 ℃; Flame ionization ditector temperature: 280 ℃; Split ratio: 30: 1.
Claims (6)
1, the fixing phase of novel beta-cyclodextrin derivative capillary gas chromatography chiral; it is characterized in that: the pi-allyl with two keys is all introduced in 2-position and 3-position at the beta-schardinger dextrin-molecule; introduce valeryl or heptanoyl group or caprylyl in the 6-position, be used as fixedly phase of capillary gas chromatography chiral and make novel beta-cyclodextrin derivative.
2, according to the fixing phase of the described novel beta-cyclodextrin derivative capillary gas chromatography chiral of claim 1, it is characterized in that: described chiral stationary phase has following structural formula:
Wherein, R
1Be double bond containing pi-allyl, have following structure:
-CH
2-CH＝CH
2
R
2Be valeryl, or be heptanoyl group, or be caprylyl to have following structure:
Wherein, n is 3, or is 5, or is 6
3, the fixing preparation method of phase of the described novel beta-cyclodextrin derivative capillary gas chromatography chiral of a kind of claim 1; it is characterized in that: at first use tert-butyl chloro-silicane to do protecting group; the 6-position primary hydroxyl of beta-schardinger dextrin-is protected; again beta-schardinger dextrin-2-position and 3-position hydroxyl are derived and be pi-allyl; after at last protecting group tert-butyl group dimethylsilyl being sloughed; 6-position hydroxyl derived be valeryl or heptanoyl group or caprylyl; and make novel beta-cyclodextrin derivative, be used as fixedly phase of capillary gas chromatography chiral.
4,, it is characterized in that fixedly among the preparation method of phase according to the described novel beta-cyclodextrin derivative capillary gas chromatography chiral of claim 3: described novel beta-cyclodextrin derivative capillary gas chromatography chiral is fixing to have following structure mutually:
Wherein, R
1Be double bond containing pi-allyl, have following structure:
-CH
2-CH＝CH
2
R
2Be valeryl, or be heptanoyl group, or be caprylyl to have following structure:
Wherein, n is 3, or is 5, or is 6
5,, may further comprise the steps fixedly among the preparation method of phase according to the described novel beta-cyclodextrin derivative capillary gas chromatography chiral of claim 3:
Beta-schardinger dextrin-molecule and tert-butyl chloro-silicane reaction are made intermediate: 6-O-tert-butyl group dimethylsilyl-beta-schardinger dextrin-;
6-O-tert-butyl group dimethylsilyl-beta-schardinger dextrin-and bromopropene reaction are made 2,3-two-O-pi-allyl-6-O-tert-butyl group dimethylsilane-beta-schardinger dextrin-;
With 2,3-two-O-pi-allyl-6-O-tert-butyl group dimethylsilane-beta-schardinger dextrin-is sloughed protecting group, obtains 2,3-two-O-allyl group-beta-cyclodextrin;
With 2,3-two-O-allyl group-beta-cyclodextrin and valeric chloride or oenanthyl chloro or caprylyl chloride reaction obtain 3 kinds of novel beta-cyclodextrin derivatives:
Product 1:2,3-two-O-pi-allyl-6-O-valeryl group-beta-cyclodextrin
Product 2:2,3-two-O-pi-allyl-6-O-oenanthyl group-beta-cyclodextrin
Product 3:2,3-two-O-pi-allyl-6-O-decoyl group-beta-cyclodextrin.
6, the described novel beta-cyclodextrin derivative of claim 1 is as the capillary gas chromatography chiral enantiomer that fixedly is separated.
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