CN103752293B - Allophanamide base/urea groups-Carbamic acid ester type liquid phase chromatogram stationary phase and preparation method thereof - Google Patents
Allophanamide base/urea groups-Carbamic acid ester type liquid phase chromatogram stationary phase and preparation method thereof Download PDFInfo
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Abstract
A kind of Stationary Phase of HPLC, is characterized in that structure is:
wherein: Gel is the particulate containing hydroxyl; R
1for methyl or ethyl; X is-O or-NH; N=3-17.A kind of method preparing above-mentioned Stationary Phase of HPLC, it is characterized in that comprising the steps: by alkanol or alkanamine successively with vulcabond reagent, silane coupler reacts 2 ~ 24 hours under organic solvent existence condition, then under nitrogen or argon atmosphere protection, by above-mentioned reactant liquor and a kind of particulate containing hydroxyl in organic solvent in 80 ~ 130 DEG C of stirring reactions 2 ~ 24 hours, filter, use organic solvent and methanol wash successively, gained solid in vacuum drying chamber under 40 ~ 100 DEG C of conditions dry 6 ~ 24 hours, obtain the chromatographic stationary phases containing two urea groups or a urea groups and carbamate based structures, particulate with hydroxyl is silica gel, hydroxyapatite or polymer.
Description
Technical field
The present invention relates to a kind of Stationary Phase for HPLC and preparation method thereof, specifically, is a kind of novel reversed phase liquid chromatographic stationary phase being embedded in two urea groups or a urea groups and a carbamate groups in the hydrocarbon chain of Bonded Phase.
Background technology
Reversed-phase liquid chromatography is the important clastotype of one in liquid chromatogram, has now been widely used in the isolation and purification of material in the fields such as food, medicine, biology, environment.In this chromatogram mode, Stationary liquid is the spherical silica gel or the high molecular polymer that are bonded with long chain alkane, and mobile phase is the mixed solution that methyl alcohol or acetonitrile and water form.According to statistics, since the seventies in last century, reversed-phase liquid chromatography occurred first, it is carry out (ZhangM, WangH, Chen, H, etal.ActaChim.Slov.2011,58,60-68 under the pattern of reverse-phase chromatography that the liquid chromatogram of existing about 80% is separated; QiuH, MallikAK, TakafujiM, etal.AnalChim.Acta2012,738:95-101; SilvaCR, AiroldiC, CollinsKE, CollinsCH.J.Chromatogr.A2005,1087,29-37; Zhang Weiqing, Hu Changqin. Acta Pharmaceutica Sinica 2010,45,555-559).
At present, the silylating reagent containing long chain alkane and silica gel normally react by the Stationary liquid in reversed-phase liquid chromatography to be prepared and obtains (HeL, ZhangJ, SunY, etal.J.Chromatogr.A2010,1217,5971-5977; Jiang Zitao, Zuo Yumin. chromatogram 2001,19,297-300; Analogy sunrise, Zhao Rui, Liu Guoquan. SCI 2000,21,1043-1044).But still there is a large amount of silicone hydroxyl through the Silica Surface of modification, this just makes some polar compound, particularly alkali compounds there will be the phenomenons such as chromatographic peak profile broadening and hangover in the process be separated.The reagent such as trim,ethylchlorosilane or HMDS is adopted to carry out deactivation process to silica gel; i.e. " end group sealing "; the peak shape of chromatographic peak can be improved; but because sealing is difficult to accomplish completely; therefore limited efficiency (BairMD is improved; DorseyJG.J.Chromatogr.A2012,1220,35-43; Guo Zhiqiang, Chen Lei, Wan Qianhong. analytical chemistry 2009,37,1572-1576).In order to improve the separating property of reversed-phase liquid chromatography further, some scholars eliminate the impact of silicone hydroxyl by the principle of space protection.Such as, (KirklandJJ, AdamsJrJB, VanStratenMA, etal.Anal.Chem.1998,70, the 4344-4352 such as Kirkland; KirklandJJ, HendersonJW.J.Chromatogr.Sci.1994,32,473-480) introduce the comparatively macoradical such as isopropyl or isobutyl group at alkyl side chain, the interaction of silicone hydroxyl and sample molecule is weakened by the principle of " three-dimensional protection ".Other scholars, as (WirthMJ, FatunmbiHO.Anal.Chem.1992,64,2783-2786 such as Wirth; WirthMJ, FatunmbiHO.Anal.Chem.1993,65,822-826; FairbankRWP, XiangY, WirthMJ.Anal.Chem.1995,67,3879-3885) then eliminate silicone hydroxyl mutually to the impact be separated by the polymerization of introducing level.But this kind of silane reagent preparation process is complicated, and expensive.
In recent years, some scholars, by embedded polar group in long chain alkane, eliminate the impact of silicone hydroxyl by the principle of electron screening, improve the selective of chromatographic stationary phases separation further simultaneously.Such as, (BuszewskiB, the Gadzala-KopciuchRM such as Buszewski, MarkuszewskiM, etal.Anal.Chem.1997,69,3277-3284) adopt chain alkyl acid or its carboxylic acid halides and alkylamino silica gel to react, thus introduce amide group in chain alkyl.But this method solvent-oil ratio is large, and the Silica Surface of end product exists the amino of non-acidylate, thus affect the uniformity of Stationary liquid surface ligand distribution and the reappearance of batch preparation.O ' Gara etc. (O ' GaraJE, AldenBA, WalterTH, etal.Anal.Chem.1995,67,3809-3813) method that adopts chloroplatinic acid to reduce prepares N-octyl substituted carbamate Stationary liquid, although the alkyl linked chain of the N-obtained by this method to be evenly distributed and batch is prepared reproducible at Silica Surface, but Stationary phase preparation process is loaded down with trivial details, and agents useful for same is expensive.
Summary of the invention
The object of this invention is to provide a kind of novel HPLC stationary phases and preparation method thereof.This Stationary liquid is the reversed phase liquid chromatographic stationary phase being embedded in two urea groups or a urea groups and a carbamate groups in hydrocarbon chain.This Stationary phase preparation method is simple, and raw material is easy to get, and can be used for the separation of most of polarity and non-polar compound.
Technical scheme of the present invention is:
A kind of Stationary Phase of HPLC, is characterized in that structure is:
Wherein: Gel is the particulate containing hydroxyl; R
1for methyl or ethyl; X is-O or-NH; N=3-17.
Prepare a method for above-mentioned Stationary Phase of HPLC, it is characterized in that comprising the steps:
By alkanol or alkanamine successively with vulcabond reagent, silane coupler reacts 2 ~ 24 hours under organic solvent existence condition, then under nitrogen or argon atmosphere protection, by above-mentioned reactant liquor and a kind of particulate containing hydroxyl in organic solvent in 80 ~ 130 DEG C of stirring reactions 2 ~ 24 hours, filter, use organic solvent and methanol wash successively, gained solid in vacuum drying chamber under 40 ~ 100 DEG C of conditions dry 6 ~ 24 hours, obtain the chromatographic stationary phases containing two urea groups or a urea groups and carbamate based structures, particulate with hydroxyl is silica gel, hydroxyapatite or polymer, silane coupler used has following structure:
X
3Si(CH
2)
3NH
2
Wherein X is methoxy or ethoxy.
Vulcabond reagent used has following structure:
The method of above-mentioned preparative high-performance liquid chromatographic Stationary liquid, is characterized in that: described organic solvent is benzene, toluene, chlorobenzene, dimethylbenzene, ethylbenzene, acetonitrile or oxolane.
Tool of the present invention has the following advantages:
1. novel structure.The present invention is embedded in two polar groups in hydrophobic hydrocarbon chain, i.e. two urea groups or a urea groups and a carbamate groups, this eliminates filling surface silicone hydroxyl to the impact be separated by contributing to by the principle of electron screening, and in Stationary liquid aglucon, introduce polar group can further improve the selective of separation simultaneously.
2. Stationary phase preparation process is simple and reliable, and raw material is easy to get, and is conducive to realizing batch production.
3. applied range.Stationary liquid provided by the invention is a kind of general type reverse-phase chromatography Stationary liquid, has good separating property, have good market application foreground for polarity and non-polar compound.
Accompanying drawing explanation
Fig. 1 is the chromatogram that the Stationary liquid adopting embodiment 1 to prepare is separated 1. uracils, 2. toluene, 3. naphthalene and 4. biphenyl.
Fig. 2 is the chromatogram that the Stationary liquid adopting embodiment 1 to prepare is separated 1. aniline and 2. phenol, and compares with Shimadzu general commodity chromatographic column.
Detailed description of the invention
Below in conjunction with example, the present invention will be further described.Example is only limitted to the present invention is described, but not limitation of the invention.
Embodiment 1
5mL1 is added in 100mL flask, 6-hexylidene diisocyanate (HDI) and 40mL toluene, separately getting 3.7mL n-hexyl alcohol is dissolved in 8mL toluene, slowly drop under agitation in flask, 5h is reacted at 90 DEG C, then add 7mL aminopropyltriethoxywerene werene, at 90 DEG C, react 5h, cool drying is for subsequent use.Separately get the silica gel of 2.5g through HCl treatment in 200mL flask; in 150 DEG C of vacuum drying after 5 hours; add above-mentioned reactant liquor; stirring and refluxing 14 hours under nitrogen protection; filter; use toluene and methanol wash successively, gained solid in vacuum drying chamber under 80 DEG C of conditions dry 12 hours, obtains the chromatographic stationary phases containing a urea groups and a carbamate groups.Elementary analysis: C:13.1%, N:1.9%.Infrared spectrum: 2974,2935 and 2866cm
-1alkyl characteristic absorption peak, 1641cm
-1carbonyl characteristic absorption peak, 1576cm
-1amido link characteristic absorption peak.Elementary analysis and the results of FT-IR confirm that Stationary liquid structure is:
Embodiment 2
30mL1 is added in 500mL flask, 6-hexylidene diisocyanate (HDI) and 250mL toluene, separately getting 22mL n-hexyl alcohol is dissolved in 40mL toluene, slowly drop under agitation in flask, 7h is reacted at 90 DEG C, then add 35mL aminopropyltriethoxywerene werene, at 90 DEG C, react 7h, cool drying is for subsequent use.Separately get the silica gel of 30g through HCl treatment in 1000mL flask; in 150 DEG C of vacuum drying after 5 hours; add above-mentioned reaction solution; stirring and refluxing 20 hours under nitrogen protection; filter; use toluene and methanol wash successively, gained solid in vacuum drying chamber under 80 DEG C of conditions dry 12 hours, obtains the chromatographic stationary phases containing a urea groups and a carbamate groups.Elementary analysis: C:12.8%, N:1.8%.Infrared spectrum: 2974,2936 and 2867cm
-1alkyl characteristic absorption peak, 1641cm
-1carbonyl characteristic absorption peak, 1574cm
-1amido link characteristic absorption peak.Elementary analysis and the results of FT-IR confirm that Stationary liquid structure is:
Embodiment 3
5mL1 is added in 100mL flask, 6-hexylidene diisocyanate (HDI) and 40mL toluene, separately getting 3.7mL n-hexylamine is dissolved in 8mL toluene, slowly drop under agitation in flask, 2h is reacted at 50 DEG C, then add 7mL aminopropyltriethoxywerene werene, at 90 DEG C, react 5h, cool drying is for subsequent use.Separately get the silica gel of 2.5g through HCl treatment in 200mL flask; in 150 DEG C of vacuum drying after 5 hours; add above-mentioned reactant liquor; stirring and refluxing 14 hours under nitrogen protection; filter; use toluene and methanol wash successively, gained solid in vacuum drying chamber under 80 DEG C of conditions dry 12 hours, obtains the chromatographic stationary phases containing two urea groups.Elementary analysis: C:13.2%, N:2.7%.Infrared spectrum: 2975,2935 and 2866cm
-1alkyl characteristic absorption peak, 1641cm
-1carbonyl characteristic absorption peak, 1577cm
-1amido link characteristic absorption peak.Elementary analysis and the results of FT-IR confirm that Stationary liquid structure is:
Embodiment 4
5mL1 is added in 100mL flask, 6-hexylidene diisocyanate (HDI) and 40mL toluene, separately getting 2.5mL n-butanol is dissolved in 8mL toluene, slowly drop under agitation in flask, 4h is reacted at 90 DEG C, then add 7mL aminopropyltriethoxywerene werene, at 90 DEG C, react 5h, cool drying is for subsequent use.Separately get the silica gel of 2.5g through HCl treatment in 200mL flask; in 150 DEG C of vacuum drying after 5 hours; add above-mentioned reactant liquor; stirring and refluxing 14 hours under nitrogen protection; filter; use toluene and methanol wash successively, gained solid in vacuum drying chamber under 80 DEG C of conditions dry 12 hours, obtains the chromatographic stationary phases containing a urea groups and a carbamate groups.Elementary analysis: C:5.1%, N:0.8%.Infrared spectrum: 2974,2935 and 2866cm
-1alkyl characteristic absorption peak, 1641cm
-1carbonyl characteristic absorption peak, 1576cm
-1amido link characteristic absorption peak.Elementary analysis and the results of FT-IR confirm that Stationary liquid structure is:
Embodiment 5
5mL1 is added in 100mL flask, 6-hexylidene diisocyanate (HDI) and 40mL toluene, separately getting 5.0g octadecanol is dissolved in 8mL toluene, slowly drop under agitation in flask, 24h is reacted at 90 DEG C, then add 7mL aminopropyltriethoxywerene werene, at 90 DEG C, react 5h, cool drying is for subsequent use.Separately get the silica gel of 2.5g through HCl treatment in 200mL flask; in 150 DEG C of vacuum drying after 5 hours; add above-mentioned reactant liquor; stirring and refluxing 14 hours under nitrogen protection; filter; use toluene and methanol wash successively, gained solid in vacuum drying chamber under 80 DEG C of conditions dry 12 hours, obtains the chromatographic stationary phases containing a urea groups and a carbamate groups.Elementary analysis: C:16.0%, N:1.6%.Infrared spectrum: 2974,2935 and 2866cm
-1alkyl characteristic absorption peak, 1641cm
-1carbonyl characteristic absorption peak, 1576cm
-1amido link characteristic absorption peak.Elementary analysis and the results of FT-IR confirm that Stationary liquid structure is:
Embodiment 6
5mL1 is added in 100mL flask, 6-hexylidene diisocyanate (HDI) and 40mL chlorobenzene, separately getting 3.7mL n-hexyl alcohol is dissolved in 8mL chlorobenzene, slowly drop under agitation in flask, 5h is reacted at 90 DEG C, then add 7mL aminopropyltriethoxywerene werene, at 90 DEG C, react 5h, cool drying is for subsequent use.Separately get the hydroxyapatite of 3.0g through HCl treatment in 200mL flask; in 150 DEG C of vacuum drying after 8 hours; add above-mentioned reactant liquor; stirring and refluxing 2 hours under nitrogen protection; filter; use chlorobenzene and methanol wash successively, gained solid in vacuum drying chamber under 80 DEG C of conditions dry 24 hours, obtains the hydroxylapatite chromatography Stationary liquid containing a urea groups and a carbamate groups.Elementary analysis: C:7.3%, N:1.0%.Infrared spectrum: 2974,2935 and 2866cm
-1alkyl characteristic absorption peak, 1641cm
-1carbonyl characteristic absorption peak, 1576cm
-1amido link characteristic absorption peak.Elementary analysis and the results of FT-IR confirm that Stationary liquid structure is with embodiment 1, and wherein Gel is hydroxyapatite.
Embodiment 7
5mL1 is added in 100mL flask, 6-hexylidene diisocyanate (HDI) and 40mL oxolane, separately getting 3.7mL n-hexyl alcohol is dissolved in 8mL oxolane, slowly drop under agitation in flask, 5h is reacted at 90 DEG C, then add 7mL aminopropyltriethoxywerene werene, at 90 DEG C, react 5h, cool drying is for subsequent use.Separately get the polystyrene/divinylbenzene microballoon of 2.5g bonding glucolactone in 200mL flask; in 150 DEG C of vacuum drying after 8 hours; add above-mentioned reactant liquor; stirring and refluxing 2 hours under nitrogen protection; filter; use oxolane and methanol wash successively, gained solid in vacuum drying chamber under 80 DEG C of conditions dry 24 hours, obtains the polymer chromatography Stationary liquid containing a urea groups and a carbamate groups.Elementary analysis: N:1.3%.Infrared spectrum: 2930 and 2864cm
-1alkyl characteristic absorption peak, 1645cm
-1carbonyl characteristic absorption peak, 1570cm
-1amido link characteristic absorption peak.Elementary analysis and the results of FT-IR confirm that Stationary liquid structure is with embodiment 1, and wherein Gel is polystyrene/divinylbenzene microballoon.
Embodiment 8
5mL1 is added in 100mL flask, 6-hexylidene hexamethylene diisocyanate (HDI) and 40mL toluene, separately getting 3.7mL n-hexyl alcohol is dissolved in 8mL toluene, slowly drop under agitation in flask, 5h is reacted at 90 DEG C, then add 6.5mL aminopropyl trimethoxysilane, at 90 DEG C, react 5h, cool drying is for subsequent use.Separately get the silica gel of 2.5g through HCl treatment in 200mL flask; in 150 DEG C of vacuum drying after 5 hours; add above-mentioned reactant liquor; under nitrogen protection in 80 DEG C of stirring reactions 14 hours; filter; use toluene and methanol wash successively, gained solid in vacuum drying chamber under 80 DEG C of conditions dry 12 hours, obtains the chromatographic stationary phases containing a urea groups and a carbamate groups.Difference from Example 1 is to use aminopropyl trimethoxysilane to replace aminopropyl triethoxysilane.Elementary analysis: C:12.6%, N:1.7%.Infrared spectrum: 2974,2935 and 2866cm
-1alkyl characteristic absorption peak, 1641cm
-1carbonyl characteristic absorption peak, 1576cm
-1amido link characteristic absorption peak.Elementary analysis and the results of FT-IR confirm that Stationary liquid structure is:
Embodiment 9
With Stationary liquid prepared by embodiment 1, homogenate method is filled in 150mm, and in the stainless steel column of internal diameter 4.6mm, gained chromatographic column is for separating of sample mixture.Fig. 1 evaluates the conventional aromatic hydrocarbons mixture of reverse-phase chromatography Stationary liquid, i.e. the chromatogram of 1 uracil, 2 toluene, 3 naphthalenes, 4 biphenyl.Chromatographic condition is as follows: mobile phase methanol is 80 to 20 with the volume ratio of water, flow velocity 1mL/min, column temperature 25 DEG C degrees Celsius, determined wavelength 254nm.
Embodiment 10
The Stationary liquid prepared by embodiment 1, be same as the obtained chromatographic column of embodiment 9 method, be separated two kinds of polar compounds, i.e. 1 aniline and 2 phenol, chromatographic results is as Fig. 2 a, chromatographic condition is: mobile phase methanol is 65 to 35 with the volume ratio of water, and all the other conditions are with embodiment 9.Fig. 2 b is that application Shimadzu commodity chromatographic column is separated with 2 phenol the chromatogram obtained to 1 aniline, and chromatographic condition is with Fig. 2 a.
Can be seen by the result of above-described embodiment, bonded stationary phase preparation process of the present invention is simple, and raw material is easy to get, and saves organic solvent.The reversed phase liquid chromatographic stationary phase obtained can be effective to the separation of polarity and non-polar compound.Meanwhile, compared with existing general commodity chromatographic column, can effectively improve Stationary liquid to polar compound be separated selective.
Claims (3)
1. a Stationary Phase of HPLC, is characterized in that structure is:
Wherein: Gel is the particulate containing hydroxyl; R
1for methyl or ethyl; X is-O or-NH; N=3-17.
2. prepare the method for Stationary Phase of HPLC described in claim 1 for one kind, it is characterized in that comprising the steps: by alkanol or alkanamine successively with vulcabond reagent, silane coupler reacts 2 ~ 24 hours under organic solvent existence condition, then under nitrogen or argon atmosphere protection, by above-mentioned reactant liquor and a kind of particulate containing hydroxyl in organic solvent in 80 ~ 130 DEG C of stirring reactions 2 ~ 24 hours, filter, successively by the organic solvent and the methanol wash that do not comprise methyl alcohol, gained solid in vacuum drying chamber under 40 ~ 100 DEG C of conditions dry 6 ~ 24 hours, obtain the chromatographic stationary phases containing two urea groups or a urea groups and carbamate groups, particulate with hydroxyl is silica gel, hydroxyapatite or polymer, silane coupler used has following structure:
X
3Si(CH
2)
3NH
2
Wherein X is methoxy or ethoxy, and vulcabond reagent used has following structure:
3. the method for preparative high-performance liquid chromatographic Stationary liquid according to claim 2, is characterized in that: described organic solvent is benzene, toluene, chlorobenzene, dimethylbenzene, ethylbenzene, acetonitrile or oxolane.
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| CN114699799B (en) * | 2022-03-03 | 2023-06-23 | 江苏汉德科技有限公司 | Preparation method of carbamate chromatographic packing with ion exchange characteristic |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0903578A2 (en) * | 1997-08-11 | 1999-03-24 | Phenomenex, Inc. | A composition and column used in HPLC, a method for preparing the composition, and a method for separating different chemicals in a sample |
| CN102172519A (en) * | 2011-03-01 | 2011-09-07 | 北京化工大学 | Silica gel bonded cellulose derivative chromatographic filler and preparation method and use thereof |
| CN103041792A (en) * | 2013-01-23 | 2013-04-17 | 常州南京大学高新技术研究院 | Carbamic acid ester type liquid phase chromatogram stationary phase and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0903578A2 (en) * | 1997-08-11 | 1999-03-24 | Phenomenex, Inc. | A composition and column used in HPLC, a method for preparing the composition, and a method for separating different chemicals in a sample |
| CN102172519A (en) * | 2011-03-01 | 2011-09-07 | 北京化工大学 | Silica gel bonded cellulose derivative chromatographic filler and preparation method and use thereof |
| CN103041792A (en) * | 2013-01-23 | 2013-04-17 | 常州南京大学高新技术研究院 | Carbamic acid ester type liquid phase chromatogram stationary phase and preparation method thereof |
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