CN1580760A - Method for preparing pyrenly bonded silicagel fixed phase - Google Patents
Method for preparing pyrenly bonded silicagel fixed phase Download PDFInfo
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- CN1580760A CN1580760A CN 200410013164 CN200410013164A CN1580760A CN 1580760 A CN1580760 A CN 1580760A CN 200410013164 CN200410013164 CN 200410013164 CN 200410013164 A CN200410013164 A CN 200410013164A CN 1580760 A CN1580760 A CN 1580760A
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Abstract
The present invention relates to a preparation mthod of pyrenyl bonded silica gel fixed phase. Said method includes the following steps; heating pyrenyl butyric acid and sulfur oxychloride according to the mole ratio of 1:1.2-1.5, making reflux reaction for 8-24 hr., reduced pressure distilling out sulfur oxychloride to obtain pyrenyl butyryl chloride, then using coupling agent 3-aminopropyl trimethoxysilane as intermediate adaptor for connecting pyrenyl butyryl chloride and silica gel, making bonding reaction so as to obtain the invented pyrenyl bonded silica gel fixed phase, in which the weight ratio of pyrenyl butyryl chloride, silica gel and coupling agent is 1:0.15-0.55:0.25-0.85. Said invented product can be used for separating fullerence, perchlorinated aromatic hydrocarbon, nitro-aromatic hydrocarbon and aromatic hydrocarbon with condensed rings.
Description
Technical field
The present invention relates to the preparation method of pyrenyl bonded silica gel stationary phase.
Background technology
High performance liquid chromatography is one of contemporary most widely used analytical approach and separation means, the preparation that it not only can be used for multiple potpourri separates, and can be used for qualitative and quantitative analysis simultaneously, be widely used in each department of scientific research and the every field of social production.In liquid chromatographic system, the core component of decision analysis result and separation degree quality is chromatographic column.Therefore, the development of novel column packing is the important topic that the chromatogram worker pays close attention to always.In modern age liquid chromatography stationary phase, be that the chemically bonded phase packing of matrix accounts for about 80% in the application of whole high performance liquid chromatography with the silica particles.This be since silica gel except pore structure with excellent mechanical intensity, easily control and specific surface area, better chemical stability and thermal stability and single-minded advantages such as surface chemical reaction, also having an outstanding advantage is exactly that abundant silicon hydroxyl is contained on its surface, with organosilicon reaction, can form chemically stable Si-O-Si-C key, this is the basis that silica gel can carry out surface chemistry bonding or modification.Silica gel surface bond organic molecule is mainly finished by Silanization reaction, and can be on bonding organic molecule basis enterprising single step reaction introduce polarity, ion-exchange, encircle group such as chirality greatly.According to different separate object, often selecting the bonding organic molecule of different structure and functional group is modifier, to reach best chromatographic performance.Modifier at present commonly used comprises C18, C4, C8, amino, hydroxyl etc., and wherein C18, C4, C8 etc. are usually used in the different material of separating hydrophobicity, is that the stationary phase of representative is most widely used with octadecyl bonded silica alkanisation silica particles especially.
In recent years, in environment and Pharmaceutical Analysis, caused people's attention for using the high performance liquid chromatography separation to be rich in the medicine of electronics, agricultural chemicals, environmental contaminants etc.And contain the bonded stationary phase of aromatic hydrocarbons owing to can be specially adapted to solve this class separation problem with this class solute generation π-π or n-π effect.In general, the separating mechanism of aromatic hydrocarbons bonded stationary phase mainly is based on following four types of intermolecular interactions: (1) π-π effect; (2) dipole-dipole effect or the transferance of title electric charge; (3) hydrophobic effect; (4) other, as electrostatic interaction, inclusion complexing etc.
Phenyl bonded silica gel stationary phase is to occur the earliest, develop one of the most perfect stationary phase in the aromatic hydrocarbons stationary phase.Remove this, the big Polycyclic aromatic hydrocarbons bonded silica gel stationary phase that contains a plurality of phenyl ring has also caused people's attention, fix equal as naphthyl, anthryl, pyrenyl, coronene bonded silica gel, compare with phenyl bonded stationary phase, because the aromatic ring group molecular volume of silica gel surface institute bonding increases, the phenyl ring number increases, the pi-electron density of aromatic ring also increases, and the π between the solute-π effect, the electric charge transferance strengthens, to the separation selectivity increase of solute.In all big Polycyclic aromatic hydrocarbons stationary phase, it is the most extensive that pyrenyl bonded silica gel stationary phase is used, this stationary phase is an electron donor stationary phase that contains big pi-electron system, this stationary phase not only has very strong plane recognition capability, and have high charge transport capability, can separate well that fullerene, cyclohexane derivant, polychlorinated biphenyl and polychlorinated biphenyl two are disliked because of compounds etc.C.H.Lochm ü ller etc. and Nobuo Tanaka etc. have all prepared pyrenyl bonded silica gel stationary phase.C.H.Lochm ü ller etc. pass through the n-BuLi lithiumation with 3-bromine pyrene, generate 3-lithium pyrene, react with allyl bromide, bromoallylene then, obtain 3-pyrene allyl, itself and dimethyl silicane hydroxide are carried out the addition reaction of hydrogen silicon, thereby obtain [3-(3-pyrenyl) propyl group] dimethylchlorosilane, carry out coupling reaction and obtain pyrenyl bonded silica gel stationary phase with silica gel again, preparation 2-(1-pyrenyl) ethyl dimethylsilane such as same Nobuo Tanaka are carried out coupling reaction with silica gel again.The synthetic route of preparation such as C.H.Lochm ü ller pyrenyl bonded silica gel stationary phase is as follows:
In sum,, prepare the preparation complexity of pyrenyl silane coupling agent in the pyrenyl bonded silica gel stationary phase in the past although pyrenyl bonded silica gel stationary phase has extensive use because of its special nature, loaded down with trivial details.Thereby the cost height that causes the pyrenyl bonded silica gel, preparation is complicated, is difficult to promote the use of.Therefore, the present invention proposes a kind of new method of pyrenyl butyric acid bonded silica gel stationary phase.To analyze the reaction of pure pyrenyl butyric acid and dry thionyl chloride, generate the pyrenyl butyl chloride.Select the 3-TSL 8330 to make coupling agent, pyrenyl is bonded on the silica gel by generating acyl ammonia.
Summary of the invention
The invention provides a kind of preparation method of the pyrenyl bonded silica gel stationary phase for preparing simply, is easy to use.
Technical scheme provided by the invention is: the preparation method of pyrenyl bonded silica gel stationary phase, and by 1: 1.2～1.5 molar ratio heating reflux reaction 8～24 hours, decompression steamed thionyl chloride, makes the pyrenyl butyl chloride with pyrenyl butyric acid and thionyl chloride; By the middle aptamers of coupling agent 3-TSL 8330, carry out bonding reaction and make pyrenyl bonded silica gel stationary phase then as connection pyrenyl acyl chlorides and silica gel; Wherein the weight ratio of the consumption of pyrenyl acyl chlorides and silica gel, coupling agent is 1: 0.15～0.55: 0.25～0.85 (weight ratio is calculated silicon hydroxyl molar weight according to the silica gel specific surface and calculated).
According to the present invention, with the 3-TSL 8330 is the middle aptamers that connects pyrenyl acyl chlorides and silica gel, can adopt progressively the bonded silica gel method with middle aptamers elder generation coupling silica gel again with the pyrenyl acyl chloride reaction, or with the bonded silica gel method or first middle aptamers and pyrenyl acyl chloride reaction are obtained preparing pyrenyl bonded silica gel stationary phase with the last bonded silica gel of the silylating reagent of pyrenyl.
According to the present invention, can be earlier with silica gel in dry toluene with coupling agent 3-TSL 8330 in N
2Be catalyzer, 100-120 ℃ reaction 8～24 hours in the atmosphere, with the triethylamine, cooling, suction filtration, washing, vacuum drying makes the amino coupling agent bonded silica gel, then with amino bonded silica gel and pyrenyl acyl chlorides in dry toluene, in N
2In the atmosphere, with the triethylamine catalyzer, 100-120 ℃ reaction 8～24 hours, cooling, suction filtration, washing obtains pyrenyl bonded silica gel stationary phase.
Perhaps, under condition of ice bath, in the anhydrous toluene solution of the pyrenyl acyl chlorides of 0.1-1 grams per milliliter, add the triethylamine of catalytic amount, dropwise add amino coupling agent with the rate of addition of 0.2～2ml/min, then in N
2In the atmosphere, 0～100 ℃ the reaction 8～24 hours, add silica gel again, in N
2In the atmosphere, 100-120 ℃ reaction 8～24 hours, cooling, suction filtration, washing obtains pyrenyl bonded silica gel stationary phase.
The preparation method of above-mentioned pyrenyl bonded silica gel provided by the invention makes connector between pyrenyl and silica gel with coupling agent.Its synthetic route is:
With coupling agent 3-TSL 8330 and silica gel reaction,, thereby pyrenyl is bonded on the silica gel earlier again by amino of the reactive group on the coupling agent and part pyrenyl acyl chloride reaction; Its synthetic route is
Perhaps, earlier with coupling agent 3-TSL 8330 and part pyrenyl acyl chloride reaction, last and silica gel reaction; Its synthetic route is
Method of the present invention and the described method of aforementioned background art are compared, be not difficult to find out that latter reaction's step is many, intermediate product needs purification processes, and the process complexity is loaded down with trivial details, and the cost height is unfavorable for popularizing and uses.And in the building-up process of the present invention, no subsidiary reaction, the productive rate height, it is solid-liquid reactions that two steps were arranged, product is easy to handle, the pyrenyl acyl chlorides that generates is more stable in air, facile hydrolysis not, and process is simple, favorable reproducibility, cost is low, and as being raw material with the pyrenyl butyric acid, the every gram of stationary phase cost is not higher than 150.00 yuan of Renminbi.Thereby help the widespread use of pyrenyl bonded silica gel stationary phase.
The present invention prepares pyrenyl bonded silica gel stationary phase and can be used for separating fullerene, perchloro-aromatic hydrocarbons, nitro-aromatic, condensed-nuclei aromatics etc.
Embodiment
Embodiment 1:
(1) the pyrenyl butyl chloride is synthetic: the pyrenyl butyric acid solid 0.5g of the vacuum drying of learning from else's experience is in the 50ml round-bottomed flask, add dry thionyl chloride 20ml, oil bath reflux stirring reaction 24h, decompression distillation all steams thionyl chloride, and remaining solid is the pyrenyl butyl chloride, be black, because of it is big Polycyclic aromatic hydrocarbons acyl chlorides, as the easy hydrolysis of micromolecule acyl chlorides is more unstable in air.Stand-by.
(2) amino coupling agent bonded silica gel reaction: get 2.5g through the silica gel of vacuum drying in the 100ml there-necked flask, add the dry toluene and the 1.5g 3-TSL 8330 of the treated mistake of 55ml, magnetic agitation splashes into 3 (about 0.5ml) triethylamines.In N
2In the atmosphere in 100-120 ℃ of oil bath reflux, the reaction 24h after, the cooling, suction filtration is used toluene successively, washing with acetone is stand-by behind 120 ℃ of following vacuum drying 5h.
(3) preparation of pyrenyl butyric acid bonded silica gel: get amino bonded silica gel in (2) in the 100ml there-necked flask, join the toluene solution (the most handy toluene solution) that dissolves the pyrenyl butyl chloride fully through heated drying, magnetic agitation splashes into 3 (about 0.5ml) triethylamines.In N
2In the atmosphere in 100-120 ℃ of oil bath reflux, the reaction 24h after, the cooling, suction filtration is used toluene, washing with acetone successively.
Embodiment 2:
(1) the pyrenyl butyl chloride is synthetic: the pyrenyl butyric acid solid 0.5g of the vacuum drying of learning from else's experience is in the 50ml round-bottomed flask, add dry thionyl chloride 20ml, oil bath reflux stirring reaction 12h, decompression distillation, thionyl chloride is all steamed, and remaining solid is the pyrenyl butyl chloride.Stand-by.
(2) pyrenyl butyl chloride and amino coupling agent generate acid amides: add the 20ml dry toluene in the pyrenyl butyl chloride that generates in (1), heating makes its dissolving fully, pours in the 100ml there-necked flask, feeds dry N
2, cooling, the condition of ice bath dropwise (0.5ml/min) add 1.5g 3-TSL 8330 and 0.5g triethylamine, normal-temperature reaction 12h behind the 10min.
(3) preparation of pyrenyl butyric acid bonded silica gel: get 2.5g and directly add through the silica gel of vacuum drying in the reaction of (2), in N
2In the atmosphere in 100-120 ℃ of oil bath reflux, the reaction 24h after, the cooling, suction filtration is used toluene, washing with acetone successively.
Embodiment 3:
(1) the pyrenyl acetyl chloride is synthetic: the pyrenyl acetate solid 0.5g of the vacuum drying of learning from else's experience adds dry thionyl chloride 20ml, oil bath reflux stirring reaction 12h in the 50ml round-bottomed flask, decompression distillation, thionyl chloride is all steamed, and remaining solid is the pyrenyl acetyl chloride, and is stand-by.
(2) amino coupling agent bonded silica gel reaction: get 2.5g through the silica gel of vacuum drying in the 100ml there-necked flask, add the dry toluene and the 1.5g 3-TSL 8330 of the treated mistake of 55ml, magnetic agitation adds the 1ml triethylamine.In N
2In the atmosphere in 100-120 ℃ of oil bath reflux, the reaction 24h after, the cooling, suction filtration is used toluene successively, washing with acetone is stand-by behind 120 ℃ of following vacuum drying 5h.
(3) preparation of pyrenyl acetate bonded silica gel: get amino bonded silica gel in (2) in the 100ml there-necked flask, add and dissolve fully in the heated drying toluene solution of pyrenyl acetyl chloride, magnetic agitation adds the 1ml triethylamine.In N
2In the atmosphere in 100-120 ℃ of oil bath reflux, the reaction 24h after, the cooling, suction filtration is used toluene, washing with acetone successively.
Embodiment 4:
(1) the pyrenyl acetyl chloride is synthetic: the pyrenyl acetate solid 0.5g of the vacuum drying of learning from else's experience is in the 50ml round-bottomed flask, add dry thionyl chloride 20ml, oil bath reflux stirring reaction 12h, decompression distillation, thionyl chloride is all steamed, and remaining solid is the pyrenyl acetyl chloride.Stand-by.
(2) pyrenyl acetyl chloride and amino coupling agent generate acid amides: add the 20ml dry toluene in the pyrenyl acetyl chloride that generates in (1), heating makes its dissolving fully, pours in the 100ml there-necked flask, feeds dry N
2, cooling, the condition of ice bath dropwise (0.5ml/min) add 1.5g 3-TSL 8330 and 0.5g triethylamine, normal-temperature reaction 24h behind the 10min.
(3) preparation of pyrenyl acetate bonded silica gel: get 2.5g and directly add through the silica gel of vacuum drying in the reaction of (2), in N
2In the atmosphere in 100-120 ℃ of oil bath reflux, the reaction 24h after, the cooling, suction filtration is used toluene, washing with acetone successively.
Embodiment 5: change the pyrenyl butyric acid among embodiment 1 and the embodiment 2 into pyrenyl propionic acid or other pyrenyl carboxylic acids, can make corresponding pyrenyl carboxylic acid bonded silica gel under identical condition.
Embodiment 6: pyrenyl butyric acid bonded silica gel stationary phase separates fullerene: under the normal temperature, be stationary phase with pyrenyl butyric acid bonded silica gel, toluene is moving phase, and flow velocity is 1ml/min, and the detection wavelength is 380nm, sample introduction C
60And C
70, sampling volume reaches 0.8mL (C
60And C
70Saturated solution), both all can obtain baseline separation, separation factor reaches 2.0.Illustrate that this stationary phase can be used for C
60And C
70Preparation separate.After the solution concentration of residual carbon slag after 150ml Benzene Chloride Soxhlet is extracted to the preparation fullerene, as sample feeding, be moving phase with toluene, flow velocity is 1ml/min, and the detection wavelength is 410nm, and the high fullerene of part can obtain separating.
Embodiment 7: pyrenyl butyric acid bonded silica gel stationary phase separates perchloro-aromatic hydrocarbons: under the normal temperature, with toluene is moving phase, and flow velocity is 1ml/min, and the detection wavelength is 300nm, perchloro-aromatic hydrocarbons such as sample introduction perchloro-benzene, perchloro-acenaphthylene, perchloro-benzo acenaphthylene mix sample, have obtained good separating effect.
Embodiment 8: pyrenyl butyric acid bonded silica gel stationary phase separates condensed-nuclei aromatics: under the normal temperature, be moving phase with pure methyl alcohol, flow velocity is 1ml/min, and the detection wavelength is 254nm, 16 kinds of complicated condensed-nuclei aromaticss of sample introduction, and major part has obtained separation.
Embodiment 9: to embodiment 6,7, each separate object is estimated under corresponding conditions in 8, obtains identical result with other pyrenyl carboxylic acid bonded silica gel stationary phase except that pyrenyl butyric acid bonded silica gel stationary phase.
Claims (4)
1. the preparation method of pyrenyl bonded silica gel stationary phase is characterized in that: by 1: 1.2～1.5 molar ratio heating reflux reaction 8～24 hours, decompression steamed thionyl chloride, makes the pyrenyl butyl chloride with pyrenyl butyric acid and thionyl chloride; By the middle aptamers of coupling agent 3-TSL 8330, carry out bonding reaction and make pyrenyl bonded silica gel stationary phase then as connection pyrenyl acyl chlorides and silica gel; Wherein the weight ratio of the consumption of pyrenyl acyl chlorides and silica gel, coupling agent is 1: 0.15～0.55: 0.25～0.85.
2. preparation method according to claim 1, it is characterized in that: serve as the middle aptamers that connects pyrenyl acyl chlorides and silica gel with the 3-TSL 8330, employing with middle aptamers elder generation coupling silica gel again with the method for pyrenyl acyl chloride reaction, or middle aptamers and pyrenyl acyl chloride reaction are obtained preparing pyrenyl bonded silica gel stationary phase earlier with the method for the last bonded silica gel of silylating reagent of pyrenyl.
3. preparation method according to claim 2 is characterized in that: earlier with silica gel in dry toluene with coupling agent 3-TSL 8330 in N
2Be catalyzer, 100-120 ℃ reaction 8～24 hours in the atmosphere, with the triethylamine, cooling, suction filtration, washing, vacuum drying makes the amino coupling agent bonded silica gel, then with amino bonded silica gel and pyrenyl acyl chlorides in dry toluene, in N
2In the atmosphere, with the triethylamine catalyzer, 100-120 ℃ reaction 8～24 hours, cooling, suction filtration, washing obtains pyrenyl bonded silica gel stationary phase.
4. preparation method according to claim 2, it is characterized in that: under the condition of ice bath, the triethylamine that adds catalytic amount in the anhydrous toluene solution of the pyrenyl acyl chlorides of 0.1-1 grams per milliliter dropwise adds amino coupling agent with the rate of addition of 0.2～2ml/min, then in N
2In the atmosphere, 0～100 ℃ the reaction 8～24 hours, add silica gel again, in N
2In the atmosphere, 100-120 ℃ reaction 8～24 hours, cooling, suction filtration, washing obtains pyrenyl bonded silica gel stationary phase.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100446850C (en) * | 2006-12-26 | 2008-12-31 | 武汉大学 | Preparation method of humic acid bonded silica gel |
| CN102335598A (en) * | 2011-07-20 | 2012-02-01 | 武汉大学 | Preparation method of phenothiazine bonded silica gel |
| CN104549184A (en) * | 2015-01-31 | 2015-04-29 | 苏州汇通色谱分离纯化有限公司 | Preparation method of special chromatography separation medium for separating fullerene and derivatives of fullerene |
-
2004
- 2004-05-17 CN CN 200410013164 patent/CN1284621C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100446850C (en) * | 2006-12-26 | 2008-12-31 | 武汉大学 | Preparation method of humic acid bonded silica gel |
| CN102335598A (en) * | 2011-07-20 | 2012-02-01 | 武汉大学 | Preparation method of phenothiazine bonded silica gel |
| CN104549184A (en) * | 2015-01-31 | 2015-04-29 | 苏州汇通色谱分离纯化有限公司 | Preparation method of special chromatography separation medium for separating fullerene and derivatives of fullerene |
| CN104549184B (en) * | 2015-01-31 | 2017-02-15 | 苏州汇通色谱分离纯化有限公司 | Preparation method of special chromatography separation medium for separating fullerene and derivatives of fullerene |
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| CN1284621C (en) | 2006-11-15 |
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