CN103601823A - Preparation method for beta-cyclodextrin chiral stationary phase - Google Patents
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Abstract
A disclosed preparation method for a beta-cyclodextrin chiral stationary phase comprises: taking SiO2 microballoons as a raw material, and bonding beta-cyclodextrin (beta-CD) to the surface of SiO2 microballoons by employing 3-aminopropyltriethoxysilane (KH550), trimethylchlorosilane and 4,4'-methylenediphenyl diisocyanate (MDI) to obtain the beta-cyclodextrin chiral stationary phase. The method has continuity, simple operation and short synthetic period, and the synthetic product is convenient to be subjected to derivatization; no metal ion-containing catalysts such as NaOH, NaN3, CuI(PPh3) and the like are introduced according to the method, so that the chiral stationary phase is prevented from pollution, and the method relatively accords with the separation requirement of high-purity liquid chromatogram. The method is applicable to separation of benzene ring-containing chiral medicament intermediates and pyrethroid pesticide compounds.
Description
Technical field
The present invention relates to the technology of preparing of high performance liquid chromatography (HPLC) column packing chiral stationary phase, be specifically related to the preparation method of beta-cyclodextrin chiral stationary phase.
Background technology
" Thalidomide " of 1953-1961---" reaction stops " teratogenesis event has caused about 12000 sea dog a visit from the storks, and the disaster consequence of " reaction stops " has just entered just because of the enantiomer in medicine not being carried out to chiral separation purification that market causes." reaction stops event " caused the great attention of international community, also caused the research boom of scientific circles for chiral separation.On January 5th, 1992, U.S. food and Drug Administration (FDA) regulation: while declaring chiral drug, must know quantity and the relative content that is set out in each isomer in the sample using in pharmacology, toxicity and clinical study.The high performance liquid chromatography (HPLC) that adopts chiral stationary phase not only can be rapidly and efficiently separated enantiomer, and have to the great potential of lot splitting development, be the study hotspot of chiral chromatography separation field in recent years.Wherein, beta-cyclodextrin chiral stationary phase is because selectivity is high, good stability, and applied range, receives much concern as multi-mode chiral stationary phase.
In general, in the building-up process of beta-cyclodextrin chiral stationary phase, current research mainly concentrates on the derivatize of cyclodextrin and the mechanism aspect of chiral separation, and technology, with theoretical increasingly mature, is discussed more.And for the composite part of bonded stationary phase, the report of concrete technology of preparing is few, be summarized as follows now:
List-(6-O-p-methylphenyl alkylsulfonyl)-beta-cyclodextrin (β-CDOTs) is good 6 single substitution reaction products, can carry out the full derivatize of series.Ning Zhong etc. has reported " under 10% sodium hydroxide solution condition; synthesized list-(6-O-p-methylphenyl alkylsulfonyl)-beta-cyclodextrin; productive rate reaches 61% " in " Tetrahedron Letters; 1998:2919-2920 "; weak point is to have introduced metal ion, can cause the minimizing in the life-span of the hangover of high performance liquid chromatography (HPLC) chromatographic peak and chromatographic column.After this study on the synthesis mostly based on this.Such as; Zhou Ailing etc. have reported at " SCI; 2003; 24 (9): 1610-1614 " and " with quadrol, have replaced list-(6-O-p-methylphenyl alkylsulfonyl)-beta-cyclodextrin; generate 6-quadrol-beta-cyclodextrin; with the addition of 3-isocyanate group propyl-triethoxysilicane; then with the full derivatize of phenyl isocyanate; by transesterification reaction, be covalently bound on 5 μ m silica gel again, successfully synthesized the full derivatized beta of phenylcarbamate-cyclodextrin bonded silica gel chiral fixed phase ".Permitted will just waited in " analytical chemistry; 2006; 34(1): 77-79 " " employing epoxy chloropropane is coupling agent; with 6-quadrol-beta-cyclodextrin synthesized 6-monosubstituted-phenylcarbamate derived β-CD ", the method process is simple, be easy to derivatize, but has existed the chemical bond of ligation firm not, and derivatize process isocyanate group is understood and silica gel on the problem such as residual hydroxyl reaction.
In recent years, along with deepening continuously of research, in the synthetic field of chiral stationary phase, constantly there is new synthetic method to be seen in report.Such as Zhang etc. " is applied to click-reaction first in cyclodextrin bonded chiral stationary phase synthetic; directly the mono-substituted nitrine cyclodextrin in 6-position is fixed on to the beta-cyclodextrin chiral stationary phase that alkynyl-modified Silica Surface has been prepared novel underivatized by single step reaction " in " Journal of Chromatography A; 2008; 1191 (1/2): 188-192 ", the method condition is simple, reaction process is insensitive to water and air, and product is stable.But same, the method has been introduced metal ion, in reaction, may generate copper particle and make reaction be difficult for purifying.
What all in all, obtain at present extensive concern is the application of isocyanate ester compound in histological cytology.Such as Kazuo Nakamura etc. links up silica gel and beta-cyclodextrin with 3-isocyanate group propyl-triethoxysilicane in " Journal of Chromatography A; 1995; 694:111-118 ", synthetic chiral stationary phase has good separating power for medicine isomer ".The method is not introduced metal ion, easy and simple to handle, and synthesis cycle is short, is convenient to derivatize, is worthy to be popularized.
Summary of the invention
The present invention seeks to develop a kind of underivatized beta-cyclodextrin histological cytology method, the method synthesis cycle is short, non-metal catalyst is introduced and be convenient to carry out later stage derivatize.
The concrete preparation process of underivatized beta-cyclodextrin chiral stationary phase is as follows:
A.3-aminopropyl triethoxysilane (KH550) is modified
In reactor, add SiO
2microballoon and dry toluene solvent, with the water trap 0.5～1h that dewaters, according to 3-aminopropyl triethoxysilane and SiO
2the ratio of microsphere volume mass ratio 0.5～1mL/g drips 3-aminopropyl triethoxysilane, and stirring reaction 4～6h under 90-100 ℃ of condition, is cooled to room temperature, with dry toluene washing 4～6 times, obtains product 1.Used silica gel microballoon is single SiO of dispersion
2microballoon, size distribution is at 5～8 μ m.
Its chemical formula is as follows:
B. trimethylchlorosilane is modified
In product 1, add dry toluene solvent, according to trimethylchlorosilane and SiO
2the ratio of microsphere volume mass ratio 0.4～0.6mL/g drips trimethylchlorosilane, and stirring reaction 4～6h under 50～60 ℃ of conditions, is cooled to room temperature, with dry toluene washing 4～6 times, obtains product 2;
Its chemical formula is as follows:
C. bonding 4,4 '-diphenylmethanediisocyanate (MDI)
According to product 2 and 4,4 '-diphenylmethanediisocyanate reaction mol ratio 1:1, calculates and adds 4, the Theoretical Mass of 4 '-diphenylmethanediisocyanate;
In product 2, add dry toluene, then add 4 of 2～3 times of above-mentioned theory quality, 4 '-diphenylmethanediisocyanate, in product 2, passes into N
2, stirring reaction 4～6h under 80～90 ℃ of conditions, is cooled to room temperature, with dry toluene washing 4-6 time, obtains product 3;
Its chemical formula is as follows:
D. bonding beta-cyclodextrin (β-CD)
According to product 3, react mol ratio 1:1 with beta-cyclodextrin, calculate the Theoretical Mass that adds beta-cyclodextrin.In product 3, add dry toluene solvent, take beta-cyclodextrin and join in product 3 according to 1～2 times of the Theoretical Mass of above-mentioned calculating, pass into N
2, stirring reaction 6～8h under 80～90 ℃ of conditions, is cooled to room temperature, and dry toluene washing is 1～2 time successively, washing with acetone 1～2 time, washing with alcohol 2～3 times, obtains final product 4;
Its chemical formula is as follows:
E. product purification
Product 4 is put into the cable type extractor according that is lined with nylon membrane, with pyridine heating and refluxing extraction 4～6h, until beta-cyclodextrin white solid no longer increases in flask; Product after purifying is to 50-60 ℃ of dry 1-2 hour, obtains underivatized beta-cyclodextrin chiral stationary phase.
In above-mentioned steps A-D, the add-on of dry toluene solvent accounts for the 1/3-1/2 of reactor.
Get the sample that step e obtains and carry out infrared spectra (IR), nucleus magnetic resonance (
13c-NMR) characterize, result is as Fig. 1, shown in Fig. 2.
Fig. 1,2 result are analyzed as follows: in ir data, 1654.9 is relevant with the characteristic absorbance of amido linkage with 1552.9,1600.0 and 1514.2 is that the broad peak of the skeletal vibration charateristic avsorption band 1109.2 of phenyl ring is SiO
2, the ehter bond in cyclodextrin and-the coefficient result of OH.In nuclear magnetic data, the 1.701st, in trimethylchlorosilane-Si-CH3, in the 9.977th, KH550, on aminopropyl, be directly connected with Si-CH
2-peak, in the 40.277th, KH550 on aminopropyl with-be directly connected-CH of NH-
2-peak, remaining on aminopropyl-CH in the 21.469th, KH550
2-peak, 59.847,72.957,81.466,102.85 is relevant with the absorption of C on cyclodextrin, the peak of the upper phenyl ring of 119.22,124.52,129.26,136.81st, MDI, the 157.36th, the peak of carbonyl on urea groups and acid amides ester bond.The two confirms mutually, can reach a conclusion: each step reaction of building-up process is all normally carried out, and beta-cyclodextrin (β-CD) passes through 3-aminopropyl triethoxysilane (KH550), and 4,4 '-diphenylmethanediisocyanate (MDI), will successfully be bonded to SiO
2microsphere surface.
Beneficial effect of the present invention:
(1) use can with the silane coupling agent 3-aminopropyl triethoxysilane of silicon hydroxyl good combination, after coupling, produce firmly-Si-O-Si-key, be difficult for wash-out, can increase bonding effect and extend the high performance liquid chromatography chromatographic column life-span;
(2) at bonding after 3-aminopropyl triethoxysilane (KH550), the creationary small molecules silane coupling agent trimethylchlorosilane (CH that increased
3)
3the reaction link of Si-Cl, is compared to former bonding techniques, has avoided to a great extent Silica Surface excess silicon hydroxyl to chromatographic separation and 4, the impact of 4 '-diphenylmethanediisocyanate (MDI) bonding reaction;
(3) the creationary main body as connecting arm that contains two-NCO group selected, connection portion generates firmly amido linkage, is difficult for wash-out;
(4) method adopting has continuity, easy and simple to handle, and synthesis cycle is short, and synthetic product is convenient to carry out derivatize, does not introduce NaOH, NaN
3, CuI (PPh
3) etc. contain metal ion catalyzer, can avoid polluting chiral stationary phase, more meet the separation requirement of high-purity liquid chromatography.
(5) in the synthetic field of chiral stationary phase and the compartment analysis field of high performance liquid chromatography (HPLC) have very large using value, the chirality pharmaceutical intermediate compound that applicable separation contains phenyl ring and pyrethrin compound.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of embodiment 1 gained beta-cyclodextrin chiral stationary phase
Fig. 2 is the nucleus magnetic resonance of embodiment 2 gained beta-cyclodextrin chiral stationary phases
13c-NMR figure
Embodiment
Embodiment 1
In 100mL there-necked flask, add the dry toluene of 7.5g activated silica gel and 70mL, by water trap reflux, stir and dewater after 0.5h, drip 4.2mL3-aminopropyl triethoxysilane, stirring reaction 4h under 100 ℃ of conditions.Be cooled to room temperature, with after dry toluene washing 5 times, drip 2.3mL trimethylchlorosilane, stirring reaction 4h under 50 ℃ of conditions.Be cooled to room temperature, with dry toluene washing 5 times, sample and do ultimate analysis.Calculate and take 3.0g4,4 '-diphenylmethanediisocyanate joins in reaction system, passes into N
2, stirring reaction 6h under 80 ℃ of conditions, is cooled to after room temperature, with dry toluene washing 5 times.Calculate and take 5.5g β-CD and join reaction system, pass into N
2, stirring reaction 8h under 80 ℃ of conditions.Be cooled to after room temperature, dry toluene washing is 2 times successively, washing with acetone 2 times, and washing with alcohol 3 times, and purify by cable type extractor according, obtain β-CD chiral stationary phase.
Embodiment 2
In 100mL there-necked flask, add the dry toluene of 5g activated silica gel and 70mL, by water trap reflux, stir and dewater after 0.5h, drip 3.4mL3-aminopropyl triethoxysilane, stirring reaction 4h under 100 ℃ of conditions.Be cooled to room temperature, with after dry toluene washing 5 times, drip 1.8mL trimethylchlorosilane, stirring reaction 4h under 50 ℃ of conditions.Be cooled to room temperature, with dry toluene washing 5 times, sample and do ultimate analysis.Calculate and take 1.1g4,4 '-diphenylmethanediisocyanate joins in reaction system, passes into N
2, stirring reaction 6h under 80 ℃ of conditions, is cooled to after room temperature, with dry toluene washing 5 times.Calculate and take 3.9g β-CD and join reaction system, pass into N
2, stirring reaction 8h under 80 ℃ of conditions.Be cooled to after room temperature, dry toluene washing is 2 times successively, washing with acetone 2 times, and washing with alcohol 3 times, and purify by cable type extractor according, obtain β-CD chiral stationary phase.
Claims (2)
1. a preparation method for beta-cyclodextrin chiral stationary phase, concrete preparation process is as follows:
A.3-aminopropyl triethoxysilane is modified
In reactor, add SiO
2microballoon and dry toluene solvent, with the water trap 0.5～1h that dewaters, according to 3-aminopropyl triethoxysilane and SiO
2the ratio of microsphere volume mass ratio 0.5～1mL/g drips 3-aminopropyl triethoxysilane, and stirring reaction 4～6h under 90-100 ℃ of condition, is cooled to room temperature, with dry toluene washing 4～6 times, obtains product 1;
Its chemical formula is as follows:
B. trimethylchlorosilane is modified
In product 1, add dry toluene solvent, according to trimethylchlorosilane and SiO
2the ratio of microsphere volume mass ratio 0.4～0.6mL/g drips trimethylchlorosilane, and stirring reaction 4～6h under 50～60 ℃ of conditions, is cooled to room temperature, with dry toluene washing 4～6 times, obtains product 2;
Its chemical formula is as follows:
C. bonding 4,4 '-diphenylmethanediisocyanate (MDI)
According to product 2 and 4,4 '-diphenylmethanediisocyanate reaction mol ratio 1:1, calculates and adds 4, the Theoretical Mass of 4 '-diphenylmethanediisocyanate;
In product 2, add dry toluene, then add 4 of 2～3 times of above-mentioned theory quality, 4 '-diphenylmethanediisocyanate, in product 2, passes into N
2, stirring reaction 4～6h under 80～90 ℃ of conditions, is cooled to room temperature, with dry toluene washing 4-6 time, obtains product 3;
Its chemical formula is as follows:
D. bonding beta-cyclodextrin (β-CD)
According to product 3, react mol ratio 1:1 with beta-cyclodextrin, calculate the Theoretical Mass that adds beta-cyclodextrin;
In product 3, add dry toluene solvent, then add the beta-cyclodextrin of 1～2 times of above-mentioned theory quality in product 3, pass into N
2, stirring reaction 6～8h under 80～90 ℃ of conditions, is cooled to room temperature, and dry toluene washing is 1～2 time successively, washing with acetone 1～2 time, washing with alcohol 2～3 times, obtains final product 4;
Its chemical formula is as follows:
E. product purification
Product 4 is put into the cable type extractor according that is lined with nylon membrane, with pyridine heating and refluxing extraction 4～6h, until beta-cyclodextrin white solid no longer increases in flask; Product after purifying is to 50-60 ℃ of dry 1-2 hour, obtains underivatized beta-cyclodextrin chiral stationary phase;
In above-mentioned steps A-D, the add-on of dry toluene solvent accounts for the 1/3-1/2 of reactor.
2. the preparation method of beta-cyclodextrin chiral stationary phase according to claim 1, is characterized in that used silica gel microballoon is for single SiO of dispersion
2microballoon, size distribution is 5～8 μ m.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103965484A (en) * | 2014-04-09 | 2014-08-06 | 南昌大学 | Preparation method and application of omega-diamine derivatization beta-cyclodextrin bonded SBA-15 chiral stationary phase |
| CN104119459A (en) * | 2014-03-03 | 2014-10-29 | 南昌大学 | Preparation method of cyclodextrin hybrid alkyl skeleton chiral stationary phase |
| CN104151450A (en) * | 2014-08-08 | 2014-11-19 | 北京师范大学 | Chiral pseudo-stationary phase for capillary electrochromatography, and preparation method for chiral pseudo-stationary phase |
| CN105749889A (en) * | 2014-12-15 | 2016-07-13 | 中国科学院兰州化学物理研究所 | Preparation method of cyclodextrin-silicon-based multifunctional chiral stationary phase |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103111271A (en) * | 2013-03-04 | 2013-05-22 | 福州大学 | Preparation method of chitosan-grafted beta-cyclodextrin bonded silica gel absorbent |
| CN103406113A (en) * | 2013-07-11 | 2013-11-27 | 哈尔滨工程大学 | Preparation method of immobilized beta-cyclodextrin derivative type chiral stationary phase |
-
2013
- 2013-11-29 CN CN201310628374.3A patent/CN103601823B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103111271A (en) * | 2013-03-04 | 2013-05-22 | 福州大学 | Preparation method of chitosan-grafted beta-cyclodextrin bonded silica gel absorbent |
| CN103406113A (en) * | 2013-07-11 | 2013-11-27 | 哈尔滨工程大学 | Preparation method of immobilized beta-cyclodextrin derivative type chiral stationary phase |
Non-Patent Citations (2)
| Title |
|---|
| CHUAN-QI YIN ET AL.: "Immobilization of (1S,2R)-(1)-2-Amino-1,2-Diphenylethanol Derivates on Aminated Silica Gel with Different Linkages as Chiral Stationary Phases and Their Enantioseparation Evaluation by HPLC", 《CHIRALITY》 * |
| KAZUO NAKAMURA ET AL.: "Preparation and chromatographic characteristics of a chiral-recognizing perphenylated cyclodextrin column", 《JOURNAL OF CHROMATOGRAPHY A》 * |
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| CN103965484A (en) * | 2014-04-09 | 2014-08-06 | 南昌大学 | Preparation method and application of omega-diamine derivatization beta-cyclodextrin bonded SBA-15 chiral stationary phase |
| CN103965484B (en) * | 2014-04-09 | 2017-02-22 | 南昌大学 | Preparation method and application of omega-diamine derivatization beta-cyclodextrin bonded SBA-15 chiral stationary phase |
| CN104151450A (en) * | 2014-08-08 | 2014-11-19 | 北京师范大学 | Chiral pseudo-stationary phase for capillary electrochromatography, and preparation method for chiral pseudo-stationary phase |
| CN105749889A (en) * | 2014-12-15 | 2016-07-13 | 中国科学院兰州化学物理研究所 | Preparation method of cyclodextrin-silicon-based multifunctional chiral stationary phase |
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| CN113307978A (en) * | 2021-05-07 | 2021-08-27 | 昆明理工大学 | Inorganic microsphere modified by cyclodextrin grafted chiral proline metal complex and preparation method and application thereof |
| CN113307978B (en) * | 2021-05-07 | 2022-09-27 | 昆明理工大学 | Inorganic microsphere modified by cyclodextrin grafted chiral proline metal complex and preparation method and application thereof |
| CN115282928A (en) * | 2022-08-04 | 2022-11-04 | 杭州佳嘉乐生物技术有限公司 | Novel separation medium and application thereof |
| CN115282928B (en) * | 2022-08-04 | 2023-08-15 | 杭州佳嘉乐生物技术有限公司 | Novel separation medium and application thereof |
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