CN1152257C - Ester-type reverse bonded fixed phase and its preparing process - Google Patents
Ester-type reverse bonded fixed phase and its preparing process Download PDFInfo
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- CN1152257C CN1152257C CNB011107448A CN01110744A CN1152257C CN 1152257 C CN1152257 C CN 1152257C CN B011107448 A CNB011107448 A CN B011107448A CN 01110744 A CN01110744 A CN 01110744A CN 1152257 C CN1152257 C CN 1152257C
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Abstract
In the present invention, a silicon coupling agent containing beta-(3, 4-epoxy cyclohexyl) radicals is used to prepare a high performance liquid chromatogram, and alkyl acid firstly reacts with the silicon coupling agent and then is bonded on a particulate carrier containing hydroxy. Since the stereoscopic space protection action of cyclohexyl in an obtained stationary phase can suppress the mutual action between alkaline substances and silicon hydroxy, the stationary phase can be effectively and especially used for the separation of alkaline organic compounds. Usually, the requirements of the separation analysis of samples can be satified only by regulating the proportion of methanol to water in a flowing phase. Simultaneously, surface radicals of end products obtained by the synthetic route of the present invention are distributed more uniformly.
Description
Technical field
The invention belongs to a kind of liquid-phase chromatographic analysis with ester-type reverse bonded stationary phase and preparation method.
Background technology
Reversed-phase high-performance liquid chromatography (RP-HPLC) is because it is widely used, and about 600 kinds of commercial now reversed-phase high-performance liquid chromatography post, wherein most alkyl chain are from C2-C18, and this can realize the analysis separation requirement to most material.In numerous inverse bonded fillers, it is to be bonded to earlier on the silica gel matrix by middle coupling reagent (as amino, epoxy radicals, thiazolinyl etc.) that part is arranged, and obtains with the acyl chlorides that contains alkyl chain, alcohol or acid reaction again.
The still residual a considerable amount of silanol bases in silica gel surface after modification, this make some polar compound particularly the interaction of alkaline organic compound and residual silicon alcohol radical usually cause the chromatographic peak profile hangover, the peak broadens, even produces irreversible adsorption.In order to address this problem, often to adopt damping fluid be moving phase or separate under higher pH value.But the bonding phase that adopts some to contain three-dimensional blocking group sometimes, the separation that can under better simply moving phase condition, be satisfied with to polar compound.
Goal of the invention
The object of the present invention is to provide a kind of ester-type reverse bonded stationary phase, this ester-type reverse bonded stationary phase can be used for the liquid chromatography of organic compound effectively and separate under simple moving phase condition, particularly to the separation of alkaline organic compound.
Another object of the present invention also is to provide a kind of preparation method of ester-type reverse bonded stationary phase, and this procedure is simple, and material is easy to get, and end product is good reproducibility in batches, the stability height.
The invention provides a kind of ester-type reverse bonded stationary phase, the silicone couplet that this stationary phase utilization contains β-(3, the 4-epoxycyclohexyl) group is a spacerarm, receives on the carrier of hydroxyl after reacting with alkyl acid again, get ester-type reverse bonded stationary phase, the structural formula of this stationary phase is:
Wherein R is that carbon number is from the individual alkyl of 1-20.
Said fixing mutually in, better composition is that R is a carbon number from 4-18 alkyl.
Above-mentioned its synthetic route of ester type bonded stationary phase provided by the invention is:
Wherein R is that carbon number is from the individual alkyl of 1-20.
The invention provides a kind of preparation method of ester-type reverse bonded stationary phase, this method comprises following synthesis step:
1) pre-service of particulate carrier: add hydrochloric acid or salpeter solution in the ratio that adds 20%5ml in the 1g particulate carrier, after the ultrasonic dispersing, backflow 4-6 hour, be dipped to neutrality with double distilled water, in 100～120 ℃ of dryings, preserve stand-by.
2) contain β-(3, the 4-epoxycyclohexyl) silicone couplet of group and alkyl acid reaction: contain β-(3 by 1ml, the 4-epoxycyclohexyl) ratio of the silicone couplet of group adding 20ml organic solvent will contain β-(3, the 4-epoxycyclohexyl) silicone couplet of group and organic solvent place flask, add organic base while stirring, stir after 0.5-2 hour, add the organic solution that contains alkyl acid, following 60 ℃-90 ℃ reactions of nitrogen protection 4-8 hour, the cooling of reaction back is standby;
3) preparation of ester type bonded stationary phase: the acid-treated hydroxyl particulate of learning from else's experience; 120 ℃-160 ℃ vacuum drying 4-6 hour; under driving, vacuum adds product (I) and the organic solvent that second step makes; nitrogen protection; 90-120 ℃ stirring reaction 8-24 hour, filter, use toluene and methanol wash for several times respectively; vacuum drying 6-12 hour, obtain ester type bonded stationary phase.
Particulate is the porous that has hydroxyl, withstand voltage, particle that epigranular distributes, can be silica gel, hydroxyapatite, titania or zirconia unformed, ball-type;
Used coupling agent is to contain β-(3, the 4-epoxycyclohexyl) single, double or trifunctional compound, can be β-(3, the 4-epoxycyclohexyl) ethyl-methyl dimethoxy silane, β-(3, the 4-epoxycyclohexyl) ethyl chlorodimethyl silane or β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane;
Carbon number in the used alkyl acid is from 1-20, and preferably carbon number is from 4-18;
Organic solvent is benzene, toluene or dimethylbenzene;
Organic base is triethylamine, trimethylamine or pyridine.
The silicone couplet that the present invention will contain β-(3, the 4-epoxycyclohexyl) group first is used for the preparation of high performance liquid chromatography, and changes synthetic route, and promptly alkyl acid is bonded on the particulate carrier of hydroxyl earlier with after the silicone couplet effect again.Because the space multistory protective effect of cyclohexyl suppresses the interaction of alkaline matter and silicon hydroxyl in the resulting stationary phase of the present invention; the liquid chromatography that therefore can be used for organic compound is effectively separated; particularly to the separation of alkaline organic compound, the ratio of methyl alcohol and water just can satisfy the compartment analysis requirement of sample in the common only need adjusting moving phase.The more even distribution of end product surface group of adopting synthetic route of the present invention to obtain simultaneously.
Embodiment
Can further be well understood to the present invention by embodiment given below, but the present invention is not limited only to following example.
Embodiment 1: get the sad and 25ml toluene of 3.7ml and stir in three-neck flask, add the 2.5ml triethylamine then, stirred 1 hour, slowly drip 2.7ml β-(3 then, the 4-epoxycyclohexyl) mixed solution of ethyl trimethoxy silane and 15ml toluene, 70 ℃ of backflows are after 6 hours, and cool drying is preserved stand-by; Get 4g through acid-treated 5 microns Kromasil silicon balls in reactor, 160 ℃ of vacuum drying 5 hours add above-mentioned intermediate product under vacuum drives; under the nitrogen protection, 100 ℃ were refluxed 12 hours, filtered; after solids was used toluene and methanol wash, vacuum drying 4 hours got end product.
Embodiment 2: get the 2.3ml butyric acid and 40ml benzene stirs in three-neck flask, add the 2ml pyridine, react after 0.5 hour, drip 3.0ml β-(3, the 4-epoxycyclohexyl) ethyl chlorodimethyl silane and 20ml benzene mixed liquor, 90 ℃ were refluxed 4 hours, when getting 120 ℃ of vacuum drying 4 of 5g apatite, 90 ℃ anti-℃ at 16 hours, and all the other conditions are with embodiment 1.
Embodiment 3: get the 6.2ml stearic acid and 60ml dimethylbenzene stirs in three-neck flask, add the 3ml trimethylamine, react after 2 hours, add 4.2ml β-(3, the 4-epoxycyclohexyl) ethyl-methyl dimethoxy silane and 20ml dimethylbenzene, 60 ℃ were refluxed 8 hours, and got 110 ℃ of vacuum drying of 5g titanium dioxide microballoon sphere 6 hours, 120 ℃ were reacted 24 hours, and all the other conditions are with embodiment 1.
Embodiment 4: with the stationary phase of embodiment 1 preparation, the filling of homogenate method is in 150mm, and in the stainless steel column of internal diameter 4.6mm, the gained chromatographic column is used for the sample separation potpourri.Fig. 1 is for estimating C
8The normal aromatic hydrocarbons mixture that adopts of stationary phase, the i.e. chromatogram of 1 uracil, 2 nitrobenzene, 3 naphthalenes, 4 acenaphthenes.Chromatographic condition is as follows: mobile phase methanol is 75 to 25 with the volume ratio of water, flow velocity 0.8ml/min, and 25 ℃ of column temperatures detect wavelength 254nm.
Embodiment 5: with the chromatographic column of embodiment 4 preparations, separated 1 benzene, 2 naphthalenes, 3 biphenyl, 4 luxuriant and rich with fragrance potpourris, Fig. 2 is its chromatogram, and its chromatographic condition is with embodiment 4.
Embodiment 6: with the chromatographic column of embodiment 4 preparation, separated several alkaline mixts, i.e. and 1 aminophylline, 2 pyridines, 3 procaines, 4 caffeines, chromatogram result such as Fig. 3, its chromatographic condition is with embodiment 4.
Embodiment 7: with the chromatographic column of embodiment 4 preparations, neutral, acid and alkaline organic mixture have been separated, i.e. 1 uracil, 2 pyridines, 3 aniline, 4 phenol, 5 neighbours, right-toluidine, 6 toluene, 7 ethylbenzene, Fig. 4 is its chromatogram, mobile phase methanol is 55 to 45 with the volume ratio of water, and all the other conditions are with embodiment 4.
With traditional inverse bonded stationary phase relatively, the resulting stationary phase of the present invention only need regulate that methyl alcohol just can well separate alkali compounds with the ratio of water in the moving phase.As moving phase is methyl alcohol: under the condition of water (V/V)=75: 25, the theoretical cam curve that pyridine, para-totuidine, aminophylline, papaverine separate on Kromasil-C8 is respectively 10450,8680,22010,6120 pieces/meter, and dissymmetry factor is respectively 2.06,0.78,1.45,1.41.And the theoretical cam curve that these four kinds of alkaline matters separate on the resulting stationary phase of the present invention is respectively 36780,41110,31700,204440 pieces/meter, and dissymmetry factor is respectively 1.28,1.23,1.23,1.38.The resulting stationary phase of the present invention has bigger superiority at the separation alkaline matter as can be seen from contrast.Adopt preparation process of the present invention simple simultaneously, good reproducibility.
Claims (9)
1, a kind of ester-type reverse bonded stationary phase obtains with the particulate carrier covalent bonding of hydroxyl after it is characterized in that adopting the silicone couplet contain β-(3, the 4-epoxycyclohexyl) group to react with alkyl acid again, and structure is:
Wherein R is that carbon number is from the individual alkyl of 4-18.
2, a kind of preparation method of ester-type reverse bonded stationary phase is characterized in that, this method comprises following synthesis step:
1) pre-service of particulate carrier: add hydrochloric acid in the ratio that adds 20% 5ml in the 1g particulate carrier, after the ultrasonic dispersing, backflow 4-6 hour, be dipped to neutrality with double distilled water, in 100～120 ℃ of dryings, preserve stand-by;
2) contain β-(3, the 4-epoxycyclohexyl) silicone couplet of group and alkyl acid reaction: contain β-(3 by 1ml, the 4-epoxycyclohexyl) ratio of the silicone couplet of group adding 20ml organic solvent will contain β-(3, the 4-epoxycyclohexyl) silicone couplet of group and organic solvent place flask, add organic base while stirring, stir after 0.5-2 hour, add the organic solution that contains alkyl acid, 60-90 ℃ was reacted 4-8 hour under the nitrogen protection, and the cooling of reaction back is standby;
3) preparation of ester type bonded stationary phase: the acid-treated hydroxyl particulate of learning from else's experience; 120-160 ℃ vacuum drying 4-6 hour; under driving, vacuum adds product (I) and the organic solvent that second step makes; nitrogen protection; 90-120 ℃ stirring reaction 12-24 hour, filter, use toluene and methanol wash for several times respectively; vacuum drying 6-12 hour, obtain ester type bonded stationary phase.
3, the preparation method of ester-type reverse bonded stationary phase according to claim 2 is characterized in that used particle is silica gel, the hydroxyapatite of unformed, ball-type or the polymkeric substance that contains hydroxyl.
4, the preparation method of ester-type reverse bonded stationary phase according to claim 3 is characterized in that used particle is the silica gel of ball-type.
5, the preparation method of ester-type reverse bonded stationary phase according to claim 2 is characterized in that used coupling agent is for containing the single, double or trifunctional compound of β-(3, the 4-epoxycyclohexyl).
6, the preparation method of a kind of ester type bonded stationary phase according to claim 5, it is characterized in that used coupling agent is β-(3, the 4-epoxycyclohexyl) ethyl-methyl dimethoxy silane, β-(3, the 4-epoxycyclohexyl) ethyl chlorodimethyl silane or β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane.
7, the preparation method of ester-type reverse bonded stationary phase according to claim 2 is characterized in that the carbon number in the used alkyl acid is 4-18.
8, the preparation method of ester-type reverse bonded stationary phase according to claim 2 is characterized in that used organic solvent is benzene, toluene or dimethylbenzene.
9, the preparation method of ester-type reverse bonded stationary phase according to claim 2 is characterized in that used organic base is triethylamine, trimethylamine or pyridine.
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