CN100386142C - Method of fust preparing linkage type polysaccharide chiral fixed phase - Google Patents
Method of fust preparing linkage type polysaccharide chiral fixed phase Download PDFInfo
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- CN100386142C CN100386142C CNB2003101052700A CN200310105270A CN100386142C CN 100386142 C CN100386142 C CN 100386142C CN B2003101052700 A CNB2003101052700 A CN B2003101052700A CN 200310105270 A CN200310105270 A CN 200310105270A CN 100386142 C CN100386142 C CN 100386142C
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- polysaccharide
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- chloride
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Abstract
The present invention relates to a method for synthesizing a bonding type polysaccharide chiral fixed phase. The method comprises the following steps: (1) making polysaccharide and a derivative reagent of the polysaccharide react with trimethoxysilane or triethoxysilane containing functional radicals which can react with hydroxy on the polysaccharide in a reactor containing an organic solvent, and carrying out centrifugal separation to collect a solid for use; (2) coating the prepared polysaccharide derivative containing trimethoxy or triethoxy on the surface of a naked silica gel substrate which is generally used as a chromatographic filling material, then placing the silica gel substrate in the reactor, adding toluene and pyridine in a certain proportion, cooling the mixture after reaction, washing the product respectively by using tetrahydrofuran and methanol, and carrying out vacuum drying to obtain a bonding type polysaccharide chiral fixed phase. The present invention has the advantages of wide application range, simple and convenient preparation, high speed, good repeatability and extensive solvent selectivity. The present invention can realize commercial production and compensate the disadvantage that the similar stationary already commercialized is limited by a moving phase.
Description
Technical field
The present invention relates to the preparation of chromatogram, is a kind of quick method for preparing the bonded polysaccharide chiral stationary phase specifically.
Background technology
Polysaccharides chiral is fixing being used for showing huge advantage aspect chirality Chiral Separation and the preparation, has boundless application prospect.At present, commercial polysaccharide derivates is fixing to be to adopt the method for physics coating that polysaccharide derivatives is fixed on the chromatography matrix mutually, therefore has the problem of chiral selector loss, and the component of the phase that flows in actual applications has been subjected to bigger restriction.Because this shortcoming has low-down solubility under the mobile phase condition that some enantiomer suits on this type of fixes mutually, even insoluble, thereby has limitation in chiral separation is used.Adopt the method for chemical bonding to prepare that polysaccharides chiral is fixing to appear in the newspapers mutually, but existing preparation chemical bond mould assembly polysaccharides chiral fixedly the method for phase still have the deficiency of all many-sides; (document 1.Chemically bonded chiral stationary phaseprepared by the polymerization of cellulose p-vinylbenzoate such as K.Kimata; K.Kimata, R.Tsuboi, K.Hosoya, N.Tanaka, Anal.Methods Instrum.1,23-9 (1993) .) three substitution reactions are taken place in 4-vinyl benzene formyl chloride and cellulose hydroxyl, can make cellulose iii (4-vinyl benzoic acid ester), utilize wherein vinyl and the silica gel polymerisation handled of acryloyl chloride, can make bonding type cellulose derivative chiral stationary phase; This method limitation is to introduce other derivatization functional group, and universality is poor.(document 2.Polysaccharide derivatives and theiruse for preparing stationary chiral phases suitable for separating isomers such as L.Oliveros; L.Oliveros, C.Minguillon, P.Lopez, PCT Int.Appl.WO 9518833 (1995) .) with the 10-hendecene acyl chlorides and 3 of different proportion, 5-dimethylphenyl isocyanate mixed liquor and fibrin reaction, with the mixed derivative that obtains under the inducing of AIBN with pi-allyl silica gel generation copolyreaction; What introduce in cellulose is vinyl, and it is not very high that post is imitated.The functional group that has polymerization under the illumination effect is incorporated into (document 3.Photochemically cross-linked polysaccharidederivatives as supports for the chromatographic separation of enantiomers in the polysaccharide molecule; E.Francotte, PCT WO 96/27615 (1996) .), make fixedly phase by light polymerization, process complexity, complex operation.Reach (document 4. separating agent for optical isomer, its method for making and purposes such as history in the village; Reach history in the village, the clear people in field, city, 94190414 (1994)) by the hydroxyl on the polysaccharide derivatives 6-position, utilize the vulcabond bifunctional reagent, polysaccharide derivatives is linked to the silica gel surface, be the immobilized method of a kind of selectivity, reactions steps is various, and the time is long.
Therefore, chemical bond mould assembly polysaccharides chiral is fixed and is not also realized commercialization production mutually at present, is badly in need of quick, the easy chemical bonding method of development.
Summary of the invention
The object of the present invention is to provide a kind of quick method for preparing the bonded polysaccharide chiral stationary phase, the method by chemical bonding is fixed on polysaccharide derivatives on the chromatography matrix, thereby avoids the loss of chiral selector.
For achieving the above object, the technical solution used in the present invention is: the triethoxysilane functional group is incorporated in the polysaccharide, by with chromosorb on chemical reaction between the silicon hydroxyl polysaccharide derivates direct chemical is fixed on the chromatography matrix surface to be used as chiral chromatogram fixing mutually; Concrete reactions steps is as follows:
1) contains the preparation of trimethoxy or triethoxy polysaccharide derivatives
Polysaccharide is placed the reactor that fills organic solvent, under stirring condition, slowly add the excessive modified polysaccharide derivatization reagent that is usually used in, add simultaneously contain can with the trimethoxy silane or the triethoxysilane of hydroxyl reaction functional group on the polysaccharide, reaction system is warming up to 90-95 ℃, reacts after 10-20 hour, reaction system is cooled to room temperature, centrifugation, it is standby to collect solids;
2) chemical bonding
With above-mentioned preparation contain trimethoxy or the triethoxy polysaccharide derivatives is coated on the exposed silica matrix surface that is usually used in chromatograph packing material, polysaccharide derivates accounts for the 40-50% of silica matrix weight, be placed in the reactor then, add toluene and pyridine, under 80～90 ℃ of conditions, reacted 5～8 hours; Be cooled to room temperature, use oxolane, methanol wash product more respectively, vacuum drying can make the bonded polysaccharide chiral stationary phase.
Described can be isocyanates or acyl chloride group with the functional group of hydroxyl reaction on the polysaccharide; Can with the triethoxysilane of hydroxyl reaction functional group on the polysaccharide (OC
2H
5)
3Si (CH
2)
3NCO, (OC
2H
5)
3Si (CH
2)
3NH-COHN-(CH
2)
6-NCO, (OC
2H
5)
3Si (CH
2)
3NH-COHN-C
6H
6-CH
2-C
6H
6-NCO etc.; The derivatization reagent of polysaccharide be the benzene isocyanates (as; Phenyl isocyanate, 3,5-dimethylphenyl isocyanate, 3,5-dichloride base phenyl isocyanate, to methyl-phenyl isocyanate etc.) and the chlorobenzoyl chloride compounds (as; Chlorobenzoyl chloride, right-methyl benzoyl chloride, 3,5-dinitrobenzoyl chloride, anisoyl chloride etc.); Polysaccharide (polysaccharide derivates is by polysaccharide and contains the function groups reagent of triethoxysilane functional group and the product of the non-selective competitive reaction of derivatization reagent) is cellulose, starch, shitosan, this glycan, glucan etc., the best when wherein polysaccharide is cellulose and starch; Wherein the centrifugation agents useful for same is methyl alcohol, ethanol etc.; The volume ratio of toluene and pyridine is 4-5: 1.
The present invention has the following advantages:
1. have wide range of applications.The prepared polysaccharides chiral of the present invention is phase fixedly, be that method by chemical bonding is fixed on the chromatography matrix polysaccharide derivatization thing (by the triethoxy in γ-isocyanates propyl-triethoxysilicane, polysaccharide derivates and silica matrix are fixed on the silica gel surface by the form that forms chemical covalent bond are used as chiral stationary phase), can use different derivatization reagents, the column efficiency height, so can be used for liquid chromatogram, gas-chromatography, thin-layer chromatography etc., column performance is good, is particularly useful for high performance liquid chromatography; Can be used for the chirality Separation of Enantiomers, also can be used for the preparation of optically pure compound; Can use and be usually used in also can using oxolane, carrene, chloroform etc. as mobile phase additive in the fixing mobile phase condition that goes up mutually of polysaccharides chiral.
2. simple for production, quick.This method only needs through two step chemical reactions, can in 24h, synthesize chiral stationary phase, by γ-isocyanates propyl-triethoxysilicane bifunctional reagent triethoxy is introduced in the polysaccharide unit molecule, by itself and the effect of silicon hydroxyl polysaccharide derivates is fixed on the silica gel surface (by the triethoxy in γ-isocyanates propyl-triethoxysilicane again, with polysaccharide derivates and silica matrix under the condition of heating, by the form that forms chemical covalent bond chiral selector is fixed on the silica gel surface and is used as chiral stationary phase, manufacturing process is simple, and is easy to operate); Can be incorporated into the silica gel surface by any position keys on the glucose unit, be a kind of non-selective immobilized method, and reactions steps is few, and the time is short, for preparing fastest a kind of method in the bibliographical information at present.Simultaneously, the method can also be avoided crosslinked between the cellulose, is better than traditional vulcabond method.Utilize this method can prepare multiple polysaccharide derivates chiral stationary phase easily and fast.
3. the use good reproducibility can be realized commercialization production.The present invention first can be directly and the functional group of silica matrix reaction, be incorporated in the polysaccharide derivatives as triethoxy, by the chemical reaction between itself and the silicon hydroxyl directly with chiral selector immobilized to the silica gel preparation bonded polysaccharide chiral stationary phase, the chiral stationary phase of preparation is applicable to that liquid chromatography separates and prepare the chirality enantiomer; Method by chemical bonding is fixed on polysaccharide derivatives on the chromatography matrix, the problem that just can avoid chiral selector to run off, thereby can have better mobile more compatible mutually than corresponding coating-type chiral stationary phase.Among the present invention, adopt bifunctional reagent's method that the triethoxysilane functional group is incorporated in the polysaccharide derivates, utilize triethoxy and the effect of silicon hydroxyl can prepare the bonded polysaccharide chiral stationary phase fast, this type of chiral stationary phase can remedy the now commercial similar fixing deficiency of restriction mutually that is subjected to mutually to flow, and has solvent selectivity widely.
The specific embodiment
Below by specific embodiment in detail the present invention is described in detail
Embodiment 1
Get the 1g cellulose, put it in the reactor that fills the 30mL pyridine, under the condition of electromagnetic agitation, slowly add 5mL phenyl isocyanate and 0.3mL γ-isocyanates propyl-triethoxysilicane, reaction system is warming up to about 90 ℃, reacts 10 hours, after reaction system is cooled to room temperature, reactant liquor is poured in the beaker that fills a large amount of methyl alcohol, separate out precipitation,, collect solids precipitation and centrifugal separation, drying can make the cellulose carbanilate derivative that contains triethoxy;
With the preparation derivative in 40% (w/w) ratio be coated on silica gel (5 μ,
) on the surface, be placed in the 50mL round-bottomed flask, adding 10mL toluene and 2mL pyridine, reaction is 5 hours under 80 ℃ of conditions.Oxolane, the thorough washed product of methyl alcohol are used in cooling more respectively, and vacuum drying can make bonding type cellulose carbanilate chiral stationary phase.
Embodiment 2
Difference from Example 1 is, the 3g cellulose placed fill the 100mL pyridine, add 3 of capacity 10mL, the triethoxy amine propyl group isocynate silane of 5-dimethylphenyl isocyanate and 0.9mL, at 90-95 ℃, react about 10h, can make triethoxy cellulose carbanilate analog derivative.
Reflection ratio between control triethoxy amine propyl group isocynate silane and the polysaccharide derivatization reagent, be generally 1: 15 (v/v) preferable.
What the present invention adopted is a kind of non-selective chemical bonding, and promptly polysaccharide derivates is by the 2-on its glucose unit, or 3-, or the arbitrary hydroxyl on the 6-position is fixed on the chromosorb.The present invention also can adopt the selective chemical bonding method, promptly only by the hydroxyl on the 6-position on its glucose unit polysaccharide derivates is fixed to the chromatography matrix surface.Chiral Recognition ability by the derivative chiral stationary phase of the same race of this two kinds of methods preparation does not have tangible difference, but for some polysaccharide derivates, as 3,5-dimethylphenyl isocyanate derivative, by the selective chemical bonding method fixing have higher splitter on mutually and imitate.
Claims (5)
1. the fixing method of phase of a compound key mould assembly polysaccharides chiral is characterized in that, is undertaken by following reactions steps:
1) contains the preparation of trimethoxy or triethoxy polysaccharide derivatives
Polysaccharide is placed the reactor that fills organic solvent, under stirring condition, slowly add the excessive derivatization reagent that is usually used in the modified polysaccharide class, add simultaneously contain can with the trimethoxy silane or the triethoxysilane of the functional group of hydroxyl reaction on the polysaccharide, reaction system is warming up to 90-95 ℃, reacts after 10-20 hour, reaction system is cooled to room temperature, centrifugation, it is standby to collect solids;
Wherein polysaccharide is cellulose, starch, shitosan, this glycan or glucan; The derivatization reagent that is usually used in the modified polysaccharide class is benzene isocyanates or chlorobenzoyl chloride compounds; Can with the functional group of hydroxyl reaction on the polysaccharide isocyanates or acyl chloride group;
2) chemical bonding
With above-mentioned preparation contain trimethoxy or the triethoxy polysaccharide derivatives is coated on the exposed silica matrix surface that is usually used in chromatograph packing material, polysaccharide derivates accounts for the 40-50% of silica matrix weight, be placed in the reactor then, add a certain proportion of toluene and pyridine mixtures, under 80-90 ℃ of condition, reacted 5-8 hour; Be cooled to room temperature, use oxolane, methanol wash product more respectively, vacuum drying can make the bonded polysaccharide chiral stationary phase;
Wherein the volume ratio of toluene and pyridine is 4-5: 1.
2. according to the fixing method of phase of the described compound key mould assembly of claim 1 polysaccharides chiral, it is characterized in that: described containing can be (OC with the triethoxysilane of the functional group of hydroxyl reaction on the polysaccharide
2H
5)
3Si (CH
2)
3NCO, (OC
2H
5)
3Si (CH
2)
3NH-COHN-(CH
2)
6-NCO or (OC
2H
5)
3Si (CH
2)
3NH-COHN-C
6H
6-CH
2-C
6H
6-NCO.
3. according to the fixing method of phase of the described a kind of compound key mould assembly polysaccharides chiral of claim 1, it is characterized in that: described benzene isocyanates is a phenyl isocyanate, 3,5-dimethylphenyl isocyanate, 3,5-dichloride base phenyl isocyanate or to methyl-phenyl isocyanate; The chlorobenzoyl chloride class be chlorobenzoyl chloride, right-methyl benzoyl chloride, 3,5-dinitrobenzoyl chloride or anisoyl chloride.
4. according to the fixing method of phase of the described compound key mould assembly of claim 1 polysaccharides chiral, it is characterized in that: wherein the centrifugation agents useful for same is methyl alcohol or ethanol.
5. according to the fixing method of phase of the described compound key mould assembly of claim 1 polysaccharides chiral, it is characterized in that: described silica matrix is a Bio-sil.
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|---|---|---|---|
| CNB2003101052700A CN100386142C (en) | 2003-12-05 | 2003-12-05 | Method of fust preparing linkage type polysaccharide chiral fixed phase |
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| CNB2003101052700A CN100386142C (en) | 2003-12-05 | 2003-12-05 | Method of fust preparing linkage type polysaccharide chiral fixed phase |
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| CN100386142C true CN100386142C (en) | 2008-05-07 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20090010236A (en) * | 2006-05-09 | 2009-01-29 | 고쿠리츠 다이가쿠 호우징 나고야 다이가쿠 | Filler for optical isomer separation |
| CN101152624B (en) * | 2006-10-01 | 2010-09-29 | 中国科学院大连化学物理研究所 | Alcoholic hydroxyl group hydrophily color spectrum stationary phase and method for preparing the same |
| CN102423699B (en) * | 2011-09-02 | 2013-08-07 | 武汉工程大学 | Preparation method of coating-type polysaccharide chiral stationary phase |
| CN105080516A (en) * | 2014-05-13 | 2015-11-25 | 中科院大连化学物理研究所淮安化工新材料研究中心 | Bonding type hybrid mesoporous silica gel chiral chromatographic stationary phase and preparation method therefor |
| CN104689809B (en) * | 2015-03-21 | 2017-04-26 | 台州学院 | Preparation and application of positive charge type polysaccharide derivative chiral stationary phase |
| CN110003350A (en) * | 2018-01-05 | 2019-07-12 | 中国科学院化学研究所 | Polysaccharide derivates and preparation method thereof and purposes as chiral stationary phase |
| CN111229186A (en) * | 2018-11-29 | 2020-06-05 | 中国科学院大连化学物理研究所 | Chromatographic stationary phase material and preparation method and application thereof |
| CN112375226B (en) * | 2020-10-12 | 2023-03-17 | 苏州纳微科技股份有限公司 | Bonded amylose derivative and preparation method and application thereof |
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| JPH0570599A (en) * | 1991-03-04 | 1993-03-23 | Daicel Chem Ind Ltd | Polysaccharide derivative, its preparation and separating agent |
| WO1995018833A1 (en) * | 1994-01-05 | 1995-07-13 | Conservatoire National Des Arts Et Metiers | Polysaccharide derivatives and their use for preparing stationary chiral phases suitable for separating isomers |
| WO1996027615A1 (en) * | 1995-03-07 | 1996-09-12 | Novartis Ag | Photochemically cross-linked polysaccharide derivatives as supports for the chromatographic separation of enantiomers |
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| WO2001098370A1 (en) * | 2000-06-23 | 2001-12-27 | National University Of Singapore | Materials comprising oligo- or polysaccharide cross linked and chemically bonded to a support via urea linkages useful for chromatography and electrophoresis applications |
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2003
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Patent Citations (5)
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|---|---|---|---|---|
| JPH0570599A (en) * | 1991-03-04 | 1993-03-23 | Daicel Chem Ind Ltd | Polysaccharide derivative, its preparation and separating agent |
| CN1042418C (en) * | 1993-06-22 | 1999-03-10 | 大世吕化学工业株式会社 | Optical isomer separating agent and process for producing the same |
| WO1995018833A1 (en) * | 1994-01-05 | 1995-07-13 | Conservatoire National Des Arts Et Metiers | Polysaccharide derivatives and their use for preparing stationary chiral phases suitable for separating isomers |
| WO1996027615A1 (en) * | 1995-03-07 | 1996-09-12 | Novartis Ag | Photochemically cross-linked polysaccharide derivatives as supports for the chromatographic separation of enantiomers |
| WO2001098370A1 (en) * | 2000-06-23 | 2001-12-27 | National University Of Singapore | Materials comprising oligo- or polysaccharide cross linked and chemically bonded to a support via urea linkages useful for chromatography and electrophoresis applications |
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|---|
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