CN103951665A - Method for preparing novel tropenol amino acid anionic chiral ionic liquid, immobilization method thereof and method for resolving DL-phenylalanine and DL-tryptophan by using same - Google Patents
Method for preparing novel tropenol amino acid anionic chiral ionic liquid, immobilization method thereof and method for resolving DL-phenylalanine and DL-tryptophan by using same Download PDFInfo
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Abstract
The invention discloses a method for preparing a novel tropenol amino acid anionic chiral ionic liquid, an immobilization method thereof and methods for resolving racemic phenylalanine and tryptophan by using the same. The ionic liquid structure disclosed by the invention is represented by a general formula (I) as shown in the specification and is mainly characterized in that the ionic liquid and an inorganic salt solution are formed into aqueous two phases and enriched in the upper layer. The method for resolving the DL-phenylalanine comprises the steps of adding quantitative copper acetate and DL-phenylalanine to the ionic liquid, then adding the quantitative salt solution to form aqueous two phases, layering by centrifuging, enabling D-type phenylalanine to be enriched in the ionic liquid phase and L-type phenylalanine to be enriched in the solid phase. The formula (II) represents a silica-gel-immobilized ionic liquid structure disclosed by the invention. The method for resolving the DL-tryptophan and phenylalanine comprises the steps of enabling the ionic liquid to adsorb metal Cu2<+> to be saturated and to be used as filler of a column chromatography and firstly eluting D-configuration amino acids prior to L-configuration amino acids. Compared with the existing research, the novel tropenol amino acid anionic chiral ionic liquid disclosed by the invention is prominently characterized in that the ionic liquid structure having the formula (I) has strong capability in phase forming and can be used for resolution of water-soluble type DL-phenylalanine, an organic solvent is not needed and the effect is better.
Description
Technical field
The present invention relates to preparation and immobilization based on tropanol and amino acid whose chiral ionic liquid, its application comprises that double water-phase splits DL-phenylalanine and column chromatography for separation DL-Trp and DL-phenylalanine, belongs to the field of extracting and separating and chromatographic separation.
Background technology
The bio-active substance confrontation human bodies such as chiral amino acid and animal life activity play a part very important.Prepare enantiomer-pure chipal compounds significant in fields such as life science, pharmaceutical chemistry, fine chemistry, materials chemistries.At present, the method for conventional chiral amino acid Chiral Separation comprises enzyme Split Method, membrane separation process and chemical resolution method.Wherein Enzymatic Resolution is expensive, poor stability; Membrane separation process is because the preparation of film difficulty has limited its large-scale production and application greatly; Chemical resolution method exists operational path complicated conventionally, and yield is low, and resolving agent reclaims the problems such as difficulty.Therefore, research and develop the method for splitting of new amino acid isoreactivity material significant.
Ionic liquid is the low-temperature molten salt (fusing point is usually less than 150 ℃) that a class is comprised of organic cation and organic or inorganic negatively charged ion, there is non-volatile, high thermal stability, selective dissolution ability and structure and the feature such as can design, compare organic solvent environmental protection.Design, complex functionality chiral ionic liquid are also applied to some amino acid whose fractionation and rarely have at present report, but existing result of study tentatively demonstrates the good separation performance of ionic liquid.
2005, (Fukumoto, the K. such as Fukumoto; Yoshizawa, M.; Ohno, h. Room temperature ionic liquid from 20 natural amino acids. J. Am. Chem. Soc. 2005,127,2398 – 239) with natural amino acid, synthesized serial imidazoles amino acid anion chiral ionic liquid.After this, about amino acid anion chiral ionic liquid, as catalyzer or the solvent of asymmetric synthesis, a large amount of concerns have been obtained.
Yet, about such ionic liquid, for extracting the research of fractionation, do not draw attention always, until 2010, (the Fei Tang such as Tang, Qianli Zhang, Dandan Ren, Zhou Nie, Qian Liu, Shouzhuo Yao. Functional amino acid ionic liquids as solvent and selector in chiral extraction. Journal of Chromatography A, 1217 (2010) 4669 – 4674) use the extraction of imidazoles proline(Pro) anionic ion liquid-ethyl acetate system to split DL-amino acid, enantiomeric excess value maximum can reach 50%, but need to use water-fast organic solvent, be unfavorable for environmental protection.(the Tang Fei such as Tang afterwards, Yang Fei, Li Yingxi, Deng, salt-salt double-aqueous phase system based on ionic liquid: a kind of DL-Amino Acid chiral separation system [A] of green. the 28th Annual Conference of Chinese Chemical Society the 1st sub-venue summary collection [C]) adopt the double-aqueous phase system extraction that imidazoles L-PROLINE anionic ion liquid and Cu2+ inner complex form in dipotassium hydrogen phosphate solution to split water-fast DL-tyrosine, enantiomeric excess value reaches 92%.But using the concentration of salt is 45%, saltiness is too high causes aftertreatment difficulty, and applicable separate object only limits to water-fast tyrosine.
Hydrophilic ionic-liquid, because its viscosity is large, general reclaims more difficultly, and the recovery of amino acid anionic type ionic liquid is also so, and ionic liquid immobilization can be addressed this problem.2007, (the Wen Chen such as Chen, Yuanyuan Zhang, Liangbo Zhu, et al. A Concept of Supported Amino Acid Ionic Liquids and Their Application in Metal Scavenging andheterogeneous Catalysis. J. AM. CHEM. SOC. 2007, 129, 13879-13886.) imidazoles proline(Pro) anionic ion liquid is bonded on polystyrene support, and be applied to metal adsorption, its metal complex also can be used for the heterogeneous Ullmann reaction of catalysis and hydrogen reducing reaction.If this type of immobilization ionic liquid can be applied to the fractionation of enantiomorph, solve ionic liquid and reclaimed difficult problem, make its application meet Sustainable development.
Present inventor's design, synthesized a class tropanol amino acid anionic chiral ionic liquid, with amino acid anionic ionic liquid (the Changzeng Wu having reported at present, Jianji Wang, huiyong Wang, et al. Effect of anionic structure on the phase ormation andhydrophobicity of amino acid ionic liquids aqueous two-phase systems. Journal of Chromatography A, 1218 (2011) 8587 – 8593) compare, there is better one-tenth phase ability, only need inorganic salt still less just can form two-phase.The extraction that such ionic liquid is applied to water miscible DL-phenylalanine splits research, in extraction process, ionic liquid is rich in D-phenylalanine mutually, along with increasing of the DL-phenylalanine amount being split, there is insoluble solids phase in ionic liquid mutually below, this solid is rich in L-Phe.In addition, the present invention also uses silica gel to synthesize immobilized ionic liquid as the carrier of amino acid anionic ion liquid, and splits DL-Trp and DL-phenylalanine using it as column chromatography filler, and has obtained desirable fractionation effect.
Summary of the invention
The object of this invention is to provide a class and become amino acid anion chiral ionic liquid that phase ability is stronger and preparation method thereof, study under its condition without any organic solvent, complete its extraction to water-soluble DL-phenylalanine and split.
Another object of the present invention is to provide the method for the supported on silica-gel of this amino acid anion chiral ionic liquid, and complete this immobilization ionic liquid to DL-Trp and-fractionation of DL phenylalanine research.
The present invention solves this technical problem by following scheme: a kind of tropanol amino acid anion chiral ionic liquid (formula I) of novel structure and its silica gel immobilization structure (formula II), containing tropanol mother nucleus structure, be partly its positively charged ion, L-PROLINE radical ion is its negatively charged ion.
The preparation method of tropanol amino acid anion chiral ionic liquid is: by tropanol and 1 ~ 1.3 times of molar weight CH3(CH2) nBr(n=1 ~ 7) be dissolved in appropriate solvent (in ethyl acetate, acetone, acetonitrile and toluene a kind of), heating (40 ~ 110 ℃) to solid is no longer separated out, and filters and obtains white solid product.By the aqueous solution of this solid product, by a certain amount of strong basicity polystyrene ion-exchange chromatography, gained solution, after concentrated, adds 1.0 ~ 1.2 times to the L-PROLINE of tropanol molar weight, stirring at normal temperature 12 ~ 24h.Underpressure distillation, except after anhydrating, adds appropriate acetonitrile vigorous stirring, and adularescent insolubles is separated out, and removes by filter after insolubles, and underpressure distillation is removed acetonitrile solvent and obtained light yellow viscous liquid.Synthetic route:
The process for fixation of tropanol amino acid anionic ion liquid, γ-chloropropyl-3-methoxy silane of tropanol, 1 ~ 1.2 times of molar weight and salt compounded of iodine (potassiumiodide or sodium iodide) are dissolved in ethanol, back flow reaction 12 ~ 24h, underpressure distillation removes desolventizing and obtains white solid, a small amount of ethyl acetate washing.Gained white product is dissolved with toluene, add again the activated silica gel of 1 ~ 3 times of quality to be placed in the lump the single port flask with water trap, temperature rising reflux reaction, the by-product carbinol producing in reaction is transferred in water trap, when in water trap, methyl alcohol volume no longer changes, filter, wash products therefrom with water, and at normal temperatures with 1.0 ~ 1.2 times of L-PROLINE sodium water solutions to tropanol molar weight stir 40 ~ 48h(or first and aqueous sodium hydroxide solution mix and blend 40 ~ 48h obtain alkaline immobilization ionic liquid, after washing with water, add again 1.0 ~ 1.2 times to the L-PROLINE of tropanol molar weight), filter, wash with water, after dry, obtain target immobilization ionic liquid.Synthetic route:
A kind of tropanol amino acid anion chiral ionic liquid aqueous two-phase extraction splits the method for DL-phenylalanine, it is characterized in that: in ionic liquid, add successively the neutralized verdigris of 0.22 ~ 0.81 times of molar weight, the water of the DL-phenylalanine of certain molar weight, 49.13 ~ 180.14 times of molar weights and the salt of 2.54 ~ 7.62 times of molar weights, form double water-phase, centrifugal.When adding the DL-phenylalanine of 0.09 ~ 0.35 times of molar weight, ionic liquid is rich in D-phenylalanine mutually; When adding the DL-phenylalanine of 0.35 ~ 0.62 times of molar weight, there is insoluble solids phase in ionic liquid below, and ionic liquid liquid phase is rich in D-phenylalanine, and solid phase is rich in L-Phe.Salt in aforesaid method is a kind of in dipotassium hydrogen phosphate, potassiumphosphate, salt of wormwood.
A kind of supported on silica-gel tropanol amino acid anionic chiral ionic liquid splits the method for DL-Trp and DL phenylalanine, it is characterized in that: this immobilization ionic liquid is fully mixed after vibration with copper sulfate solution, filter, wash with water, be placed in vacuum drying oven and dry, then get 1.2g, wet method dress post is in 10 * 200mm glass column, wet method loading amino acid solution (5mg/mL), moving phase speed is 0.1mL/min.
In aforesaid method, for guaranteeing that immobilization ionic liquid absorbing copper ionic weight reaches capacity, the mass ratio of copper sulfate and immobilization ionic liquid is greater than 0.05, and mixing duration of oscillation is greater than 1h.Splitting DL-Trp moving phase used is water, and splitting DL-phenylalanine moving phase used is ethanol.
The present invention compares with background technology, has the following advantages:
1. tropanol amino acid anionic ionic liquid involved in the present invention, the tropanol in positively charged ion is one of natural tropine hydrolysate, the imidazoles extensively being used in synthetic than ionic liquid, more environmental protection, meets Sustainable development.
2. tropanol amino acid anionic ionic liquid involved in the present invention, it becomes phase ability stronger compared with imidazoles plasma liquid with salts solution.The concentration 37.5% of required salts solution in split process, glyoxaline ion liquid than same amino acid negatively charged ion, become mutually required salt amount to reduce Liao Jin 8%(Tang Fei, Yang Fei, Li Yingxi, Deng, the salt-salt double-aqueous phase system based on ionic liquid: a kind of DL-Amino Acid chiral separation system [A] of green. the 28th Annual Conference of Chinese Chemical Society the 1st sub-venue summary collection [C]).The salt using is also not only confined to single dipotassium hydrogen phosphate, can be any in potassiumphosphate, dipotassium hydrogen phosphate and salt of wormwood.
3. tropanol amino acid anionic ionic liquid involved in the present invention, can be used for extraction and splits water miscible DL-phenylalanine, and without using any organic solvent.Solve the problem that amino acid anionic ionic liquid before this can not split water-soluble racemize chirality thing, expanded the use range of amino acid anionic ionic liquid, avoided the use of organic solvent, there is better environmental protection characteristic.
4. tropanol amino acid anionic ionic liquid involved in the present invention, compare the enantiomeric excess value 50.6% that the extraction of glyoxaline ion liquid-ethyl acetate system splits DL-phenylalanine, tropanol amino acid anionic ionic liquid double-aqueous phase system has improved nearly 20%.
5. supported on silica-gel tropanol amino acid anionic chiral ionic liquid involved in the present invention, than organic polymer carrier, is used silica gel cheap and easy to get as the carrier of amino acid anionic chiral ionic liquid first.
6. supported on silica-gel tropanol amino acid anionic chiral ionic liquid involved in the present invention, has successfully split DL-Trp and DL-phenylalanine, the water that the moving phase of use is green safety and the cheap organic solvent ethanol easily reclaiming.
Embodiment
Provide example below so that the invention will be further described.Be necessary to be pointed out that at this following instance can not be interpreted as limiting the scope of the invention, if the person skilled in the art in this field makes some nonessential improvement and adjustment according to foregoing invention content to the present invention, still belong to protection scope of the present invention.
Synthesizing of embodiment 1(ionic liquid)
In the single necked round bottom flask of 100mL, add 0.05mol tropanol, and use 50mL acetic acid ethyl dissolution, then add 0.06mol monobromethane, be warming up to 40 ℃, return stirring reaction 12h, filters to obtain white bromine salt, productive rate 92.60%.Take 0.01mol bromine salt, use 50mL deionized water dissolving, move in the chromatography column that installs 50g strong basicity polystyrene anion_exchange resin.After stopping 15min, slowly emit liquid in post, collect pH and be more than or equal to 8 part.Then slowly splash in the single port flask that fills 0.011mol L-PROLINE stirring at normal temperature 12h.At 60 ℃, decompression except anhydrating, adds 100mL acetonitrile, and violent stirring 2h, removes by filter after insolubles, and acetonitrile is removed in decompression at 40 ℃, obtains faint yellow thick transparent liquid, dry, productive rate 92.03%.
Synthesizing of embodiment 2(ionic liquid)
In the single necked round bottom flask of 100mL, add 0.05mol tropanol, and dissolve with 50mL acetonitrile, then add 0.055mol bromination of n-butane, be warming up to 80 ℃, return stirring reaction 16h, filters to obtain white bromine salt, productive rate 88.32%.Take 0.01mol bromine salt, use 50mL deionized water dissolving, move in the chromatography column that installs 50g strong basicity polystyrene anion_exchange resin.After stopping 15min, slowly emit liquid in post, collect pH and be more than or equal to 8 part.Then slowly splash in the single port flask that fills 0.012mol L-PROLINE stirring at normal temperature 16h.At 60 ℃, decompression except anhydrating, adds 100mL acetonitrile, and violent stirring 2h, removes by filter after insolubles, and acetonitrile is removed in decompression at 40 ℃, obtains faint yellow thick transparent liquid, dry, productive rate 93.48%.
Synthesizing of embodiment 3(ionic liquid)
In the single necked round bottom flask of 100mL, add 0.05mol tropanol, and use 50mL acetone solution, then add 0.05mol bromo normal hexane, be warming up to 60 ℃, return stirring reaction 20h, filters to obtain white bromine salt, productive rate 79.38%.Take 0.01mol bromine salt, use 50mL deionized water dissolving, move in the chromatography column that installs 50g strong basicity polystyrene anion_exchange resin.After stopping 15min, slowly emit liquid in post, collect pH and be more than or equal to 8 part.Then slowly splash in the single port flask that fills 0.012mol L-PROLINE stirring at normal temperature 20h.At 60 ℃, decompression except anhydrating, adds 100mL acetonitrile, and violent stirring 2h, removes by filter after insolubles, and acetonitrile is removed in decompression at 40 ℃, obtains faint yellow thick transparent liquid, dry, productive rate 88.57%.
Synthesizing of embodiment 4(ionic liquid)
In the single necked round bottom flask of 100mL, add 0.05mol tropanol, and dissolve with 50mL toluene, then add 0.06mol n-octane bromide, be warming up to 110 ℃, return stirring reaction 24h, filters to obtain white bromine salt, productive rate 72.75%.Take 0.01mol bromine salt, use 50mL deionized water dissolving, move in the chromatography column that installs 50g strong basicity polystyrene anion_exchange resin.After stopping 15min, slowly emit liquid in post, collect pH and be more than or equal to 8 part.Then slowly splash in the single port flask that fills 0.01mol L-PROLINE stirring at normal temperature 24h.At 60 ℃, decompression except anhydrating, adds 100mL acetonitrile, and violent stirring 2h, removes by filter after insolubles, and acetonitrile is removed in decompression at 40 ℃, obtains faint yellow thick transparent liquid, dry, productive rate 80.16%.
The preparation of embodiment 5(immobilization ionic liquid)
0.02mol tropanol is dissolved in ethanol, adds successively 0.024mol γ-chloropropyl-3-methoxy silane and 0.024mol potassiumiodide, be warming up to 80 ℃ of back flow reaction 24h, underpressure distillation obtains white solid, a little ethyl acetate washing, the 6.29g that weighs, productive rate 62.31%.Get 5.0g silica gel, add the hydrochloric acid of 30mL massfraction 10%, after ultrasonic 1h, filter, be washed with water to neutrality, dry at 120 ℃.Take the white solid product of 5.0g previous step and activated silica gel as in the 100mL single port flask with water trap, add 40mL toluene, temperature rising reflux reacts to liquid volume in water trap and no longer changes.Filter, wash to obtain silica gel bonded product with water.Take 0.8gNaOH, be dissolved in 50mL water, add above-mentioned silica gel bonded product, under normal temperature, stir 48h, filter, washing is to neutral.In 100mL single port flask, then add 0.02mol L-PROLINE and 40mL water, under normal temperature, stir 48h, filter, water and methanol wash for several times, vacuum-drying at 60 ℃.
The preparation of embodiment 6(immobilization ionic liquid)
0.02mol tropanol is dissolved in ethanol, adds successively 0.022mol γ-chloropropyl-3-methoxy silane and 0.022mol sodium iodide, be warming up to 80 ℃ of back flow reaction 18h, underpressure distillation obtains white solid, ethyl acetate washing, the 5.83g that weighs, productive rate 57.72%.Get 15.0g silica gel, add the hydrochloric acid of 100mL massfraction 10%, after ultrasonic 1h, filter, be washed with water to neutrality, dry at 120 ℃.The above-mentioned white solid product of 5.0g and activated silica gel, as in the 100mL single port flask with water trap, are added to 40mL toluene, and temperature rising reflux reacts to liquid volume in water trap and no longer changes.Filter, wash to obtain silica gel bonded product with water.Take 0.8g KOH, be dissolved in 50mL water, add above-mentioned silica gel bonded product, under normal temperature, stir 1h, filter, washing is to neutral.In 100mL single port flask, then add 0.022mol L-PROLINE and 40mL water, under normal temperature, stir 44h, filter, water and methanol wash for several times, vacuum-drying at 60 ℃.
The preparation of embodiment 7(immobilization ionic liquid)
0.02mol tropanol is dissolved in ethanol, adds successively 0.02mol γ-chloropropyl-3-methoxy silane and 0.02mol potassiumiodide, be warming up to 80 ℃ of back flow reaction 12h, underpressure distillation obtains white solid, a little ethyl acetate washing, the 5.2g that weighs, productive rate 51.48%.Get 1g silica gel, add the hydrochloric acid of 20mL massfraction 10%, after ultrasonic 1h, filter, be washed with water to neutrality, dry at 120 ℃.The above-mentioned white solid product of 5g and activated silica gel, as in the 100mL single port flask with water trap, are added to 40mL toluene, and temperature rising reflux reacts to liquid volume in water trap and no longer changes.Filter, wash to obtain silica gel bonded product with water.Take 0.8g KOH, be dissolved in 50mL water, add above-mentioned silica gel bonded product, under normal temperature, stir 1h, filter, washing is to neutral.In 100mL single port flask, then add 0.024mol L-PROLINE and 40mL water, under normal temperature, stir 40h, filter, water and methanol wash for several times, vacuum-drying at 60 ℃.
Embodiment 8(aqueous two-phase extraction splits DL-phenylalanine)
Get 6.8 * 10
-4mol ionic liquid (R=Et), as in 5mL centrifuge tube, adds 70mg neutralized verdigris, and vibration 5min, then adds 30mg DL-phenylalanine, vibration 5min, then add 1g water to shake up, finally add 0.6g dipotassium hydrogen phosphate, vibration 5min.Supercentrifuge 10000r/min is centrifugal, and ionic liquid layer is a phase, D-phenylalanine >L phenylalanine wherein, and e. e. value is 3.72%.
Embodiment 9(aqueous two-phase extraction splits DL-phenylalanine)
Get 6.8 * 10
-4mol ionic liquid (R=n-Bu), as in 5mL centrifuge tube, adds 70mg neutralized verdigris, and vibration 5min, then adds 30mg DL-phenylalanine, vibration 5min, then add 1g water to shake up, finally add 0.6g dipotassium hydrogen phosphate, vibration 5min.Supercentrifuge 10000r/min is centrifugal, and ionic liquid layer is a phase, D-phenylalanine >L phenylalanine wherein, and e. e. value is 10.25%.
Embodiment 10(aqueous two-phase extraction splits DL-phenylalanine)
Get 6.8 * 10
-4mol ionic liquid (R=n-Hexyl), as in 5mL centrifuge tube, adds 70mg neutralized verdigris, and vibration 5min, then adds 30mg DL-phenylalanine, vibration 5min, then add 1g water to shake up, finally add 0.6g dipotassium hydrogen phosphate, vibration 5min.Supercentrifuge 10000r/min is centrifugal, and ionic liquid layer is a phase, D-phenylalanine >L phenylalanine wherein, and e. e. value is 15.34%.
Embodiment 11(aqueous two-phase extraction splits DL-phenylalanine)
Get 6.8 * 10
-4mol ionic liquid (R=n-Octyl), as in 5mL centrifuge tube, adds 70mg neutralized verdigris, and vibration 5min, then adds 30mg DL-phenylalanine, vibration 5min, then add 1g water to shake up, finally add 0.6g dipotassium hydrogen phosphate, vibration 5min.Supercentrifuge 10000r/min is centrifugal, and ionic liquid layer is a phase, D-phenylalanine >L phenylalanine wherein, and e. e. value is 24.87%.
Embodiment 12(aqueous two-phase extraction splits DL-phenylalanine)
Get 6.8 * 10
-4mol ionic liquid (R=n-Octyl), as in 5mL centrifuge tube, adds 70mg neutralized verdigris, and vibration 5min, then adds 20mg DL-phenylalanine, vibration 5min, then add 1g water to shake up, finally add 0.6g dipotassium hydrogen phosphate, vibration 5min.Supercentrifuge 10000r/min is centrifugal, and ionic liquid layer is a phase, D-phenylalanine >L phenylalanine wherein, and e. e. value is 12.64%.
Embodiment 13(aqueous two-phase extraction splits DL-phenylalanine)
Get 6.8 * 10
-4mol ionic liquid (R=n-Octyl), as in 5mL centrifuge tube, adds 70mg neutralized verdigris, and vibration 5min, then adds 40mg DL-phenylalanine, vibration 5min, then add 1g water to shake up, finally add 0.6g dipotassium hydrogen phosphate, vibration 5min.Supercentrifuge 10000r/min is centrifugal, and ionic liquid layer is divided into liquid-solid two-phase, wherein liquid phase: D-phenylalanine >L phenylalanine, and e. e. value is 38.30%; Solid phase: L-Phe >D phenylalanine, e. e. value is 64.84%.
Embodiment 14(aqueous two-phase extraction splits DL-phenylalanine)
Get 6.8 * 10
-4mol ionic liquid (R=n-Octyl), as in 5mL centrifuge tube, adds 70mg neutralized verdigris, and vibration 5min, then adds 50mg DL-phenylalanine, vibration 5min, then add 1g water to shake up, finally add 0.6g dipotassium hydrogen phosphate, vibration 5min.Supercentrifuge 10000r/min is centrifugal, and ionic liquid layer is divided into liquid-solid two-phase, wherein liquid phase: D-phenylalanine >L phenylalanine, and e. e. value is 34.43%; Solid phase: L-Phe >D phenylalanine, e. e. value is 61.80%.
Embodiment 15(aqueous two-phase extraction splits DL-phenylalanine)
Get 6.8 * 10
-4mol ionic liquid (R=n-Octyl), as in 5mL centrifuge tube, adds 70mg neutralized verdigris, and vibration 5min, then adds 70mg DL-phenylalanine, vibration 5min, then add 1g water to shake up, finally add 0.6g dipotassium hydrogen phosphate, vibration 5min.Supercentrifuge 10000r/min is centrifugal, and ionic liquid layer is divided into liquid-solid two-phase, wherein liquid phase: D-phenylalanine >L phenylalanine, and e. e. value is 21.50%; Solid phase: L-Phe >D phenylalanine, e. e. value is 59.69%.
Embodiment 16(aqueous two-phase extraction splits DL-phenylalanine)
Get 6.8 * 10
-4mol ionic liquid (R=n-Octyl), as in 5mL centrifuge tube, adds 30mg neutralized verdigris, and vibration 5min, then adds 40mg DL-phenylalanine, vibration 5min, then add 1g water to shake up, finally add 0.6g dipotassium hydrogen phosphate, vibration 5min.Supercentrifuge 10000r/min is centrifugal, and ionic liquid layer is divided into liquid-solid two-phase, wherein liquid phase: D-phenylalanine >L phenylalanine, and e. e. value is 5.10%; Solid phase: L-Phe >D phenylalanine, e. e. value is 30.0%.
Embodiment 17(aqueous two-phase extraction splits DL-phenylalanine)
Get 6.8 * 10
-4mol ionic liquid (R=n-Octyl), as in 5mL centrifuge tube, adds 90mg neutralized verdigris, and vibration 5min, then adds 40mg DL-phenylalanine, vibration 5min, then add 1g water to shake up, finally add 0.6g dipotassium hydrogen phosphate, vibration 5min.Supercentrifuge 10000r/min is centrifugal, and ionic liquid layer is divided into liquid-solid two-phase, wherein liquid phase: D-phenylalanine >L phenylalanine, and e. e. value is 25.50%; Solid phase: L-Phe >D phenylalanine, e. e. value is 71.80%.
Embodiment 18(aqueous two-phase extraction splits DL-phenylalanine)
Get 6.8 * 10
-4mol ionic liquid (R=n-Octyl), as in 5mL centrifuge tube, adds 110mg neutralized verdigris, and vibration 5min, then adds 40mg DL-phenylalanine, vibration 5min, then add 1g water to shake up, finally add 0.6g dipotassium hydrogen phosphate, vibration 5min.Supercentrifuge 10000r/min is centrifugal, and ionic liquid layer is divided into liquid-solid two-phase, wherein liquid phase: D-phenylalanine >L phenylalanine, and e. e. value is 16.61%; Solid phase: L-Phe >D phenylalanine, e. e. value is 60.53%.
Embodiment 19(aqueous two-phase extraction splits DL-phenylalanine)
Get 6.8 * 10
-4mol ionic liquid (R=n-Octyl), as in 5mL centrifuge tube, adds 70mg neutralized verdigris, and vibration 5min, then adds 40mg DL-phenylalanine, vibration 5min, then add 0.6g water to shake up, finally add 0.6g dipotassium hydrogen phosphate, vibration 5min.Supercentrifuge 10000r/min is centrifugal, and ionic liquid layer is divided into liquid-solid two-phase, wherein liquid phase: D-phenylalanine >L phenylalanine, and e. e. value is 8.1%; Solid phase: L-Phe >D phenylalanine, e. e. value is 68.41%.
Embodiment 20(aqueous two-phase extraction splits DL-phenylalanine)
Get 6.8 * 10
-4mol ionic liquid (R=n-Octyl), as in 5mL centrifuge tube, adds 70mg neutralized verdigris, and vibration 5min, then adds 40mg DL-phenylalanine, vibration 5min, then add 1.4g water to shake up, finally add 0.6g dipotassium hydrogen phosphate, vibration 5min.Supercentrifuge 10000r/min is centrifugal, and ionic liquid layer is divided into liquid-solid two-phase, wherein liquid phase: D-phenylalanine >L phenylalanine, and e. e. value is 23.28%; Solid phase: L-Phe >D phenylalanine, e. e. value is 62.64%.
Embodiment 21(aqueous two-phase extraction splits DL-phenylalanine)
Get 6.8 * 10
-4mol ionic liquid (R=n-Octyl), as in 5mL centrifuge tube, adds 70mg neutralized verdigris, and vibration 5min, then adds 40mg DL-phenylalanine, vibration 5min, then add 1.8g water to shake up, finally add 0.6g dipotassium hydrogen phosphate, vibration 5min.Supercentrifuge 10000r/min is centrifugal, and ionic liquid layer only has solid phase, L-Phe >D phenylalanine, and e. e. value is 60.82%.
Embodiment 22(aqueous two-phase extraction splits DL-phenylalanine)
Get 6.8 * 10
-4mol ionic liquid (R=n-Octyl), as in 5mL centrifuge tube, adds 70mg neutralized verdigris, and vibration 5min, then adds 40mg DL-phenylalanine, vibration 5min, then add 2.2g water to shake up, finally add 0.6g dipotassium hydrogen phosphate, vibration 5min.Supercentrifuge 10000r/min is centrifugal, and ionic liquid layer only has solid phase, L-Phe >D phenylalanine, and e. e. value is 62.24%.
Embodiment 23(aqueous two-phase extraction splits DL-phenylalanine)
Get 6.8 * 10
-4mol ionic liquid (R=n-Octyl), as in 5mL centrifuge tube, adds 70mg neutralized verdigris, and vibration 5min, then adds 40mg DL-phenylalanine, vibration 5min, then add 1g water to shake up, finally add 0.3g dipotassium hydrogen phosphate, vibration 5min.Supercentrifuge 10000r/min is centrifugal, and ionic liquid layer is divided into liquid-solid two-phase, wherein liquid phase: D-phenylalanine >L phenylalanine, and e. e. value is 23.08%; Solid phase: L-Phe >D phenylalanine, e. e. value is 61.31%.
Embodiment 24(aqueous two-phase extraction splits DL-phenylalanine)
Get 6.8 * 10
-4mol ionic liquid (R=n-Octyl), as in 5mL centrifuge tube, adds 70mg neutralized verdigris, and vibration 5min, then adds 40mg DL-phenylalanine, vibration 5min, then add 1g water to shake up, finally add 0.9g dipotassium hydrogen phosphate, vibration 5min.Supercentrifuge 10000r/min is centrifugal, and ionic liquid layer is divided into liquid-solid two-phase, wherein liquid phase: D-phenylalanine >L phenylalanine, and e. e. value is 22.22%; Solid phase: L-Phe >D phenylalanine, e. e. value is 60.95%.
Embodiment 25(aqueous two-phase extraction splits DL-phenylalanine)
Get 6.8 * 10
-4mol ionic liquid (R=n-Octyl), as in 5mL centrifuge tube, adds 70mg neutralized verdigris, and vibration 5min, then adds 40mg DL-phenylalanine, vibration 5min, then add 1g water to shake up, finally add 0.73g potassiumphosphate, vibration 5min.Supercentrifuge 10000r/min is centrifugal, and ionic liquid layer is divided into liquid-solid two-phase, wherein liquid phase: D-phenylalanine >L phenylalanine, and e. e. value is 15.30%; Solid phase: L-Phe >D phenylalanine, e. e. value is 74.41%.
Embodiment 26(aqueous two-phase extraction splits DL-phenylalanine)
Get 6.8 * 10
-4mol ionic liquid (R=n-Octyl), as in 5mL centrifuge tube, adds 70mg neutralized verdigris, and vibration 5min, then adds 40mg DL-phenylalanine, vibration 5min, then add 1g water to shake up, finally add 0.48g salt of wormwood, vibration 5min.Supercentrifuge 10000r/min is centrifugal, and ionic liquid layer is divided into liquid-solid two-phase, wherein liquid phase: D-phenylalanine >L phenylalanine, and e. e. value is 15.11%; Solid phase: L-Phe >D phenylalanine, e. e. value is 75.82%.
Embodiment 27(immobilization ionic liquid splits DL-Trp)
This immobilization ionic liquid of 2g and 20mL massfraction 5% are obtained to copper sulfate solution to be mixed after vibration 2h, filter, wash with water, be placed in vacuum drying oven and dry, then get 1.2g, add 5mL water, wet method fills post in 10*200mm glass column, the wet method loading 1mL DL-Trp aqueous solution (5mg/mL suspension liquid), and water is moving phase, pneumatic pump pressurization, moving phase speed is 0.1mL/min.Every 5min sampling, HPLC analyzes.D-trp is better than L-Trp and first goes out peak, and after 5min, L-Trp starts to be eluted, and 20min sampling enantiomeric excess value is reduced to 60%, 45min sampling enantiomeric excess value and reduced to 0.
Embodiment 28(immobilization ionic liquid splits DL-phenylalanine)
This immobilization ionic liquid of 2g and 20mL massfraction 5% are obtained to copper sulfate solution to be mixed after vibration 2h, filter, wash with water, be placed in vacuum drying oven and dry, then get 1.2g, add 5mL water, wet method fills post in 10*200mm glass column, the wet method loading 1mL DL-phenylalanine aqueous solution (5mg/mL), and ethanol is moving phase, pneumatic pump pressurization, moving phase speed is about 0.08mL/min.Every 5min sampling, HPLC analyzes.D-phenylalanine is better than L-Phe and first goes out peak, before 45min by wash-out out are all D-phenylalanines, L-Phe just starts by wash-out out afterwards, 55min sampling enantiomeric excess value is reduced to 40%, 70min sampling enantiomeric excess value and is reduced to 0.
Claims (5)
1. general formula (I) represents tropanol amino acid anion chiral ionic liquid, it is characterized in that requirement R group is for-(CH2) nCH3(n=1 ~ 7) in a kind of; Formula (II) represents that it is immobilized rear structure.
2. the preparation method of tropanol amino acid anion chiral ionic liquid claimed in claim 1: by the CH3(CH2 of tropanol and 1.0 ~ 1.2 times of molar weights) nBr(n=1 ~ 7) be dissolved in appropriate solvent (ethyl acetate, acetone, a kind of in acetonitrile and toluene) in, temperature rising reflux 12 ~ 24h, filtration obtains white solid product, with this product of water dissolution, through strong basicity polystyrene ion-exchange chromatography exchange negatively charged ion, concentrated gained solution, add 1.0 ~ 1.2 times to the L-PROLINE of tropanol molar weight, stirring at normal temperature 12 ~ 24h, underpressure distillation is except after anhydrating, with acetonitrile washing, remove the L-PROLINE that has neither part nor lot in reaction, filtration underpressure distillation is removed acetonitrile solvent and is obtained light yellow viscous liquid.
3. the process for fixation of tropanol amino acid anionic ionic liquid claimed in claim 1, by tropanol, γ-chloropropyl-3-methoxy silane and salt compounded of iodine (tropanol: γ-chloropropyl-3-methoxy silane: the mol ratio of salt compounded of iodine is 1:1:1 ~ 1:1.2:1.2, salt compounded of iodine is sodium iodide or potassiumiodide) be dissolved in ethanol, back flow reaction 12 ~ 24h, underpressure distillation removes desolventizing and obtains white solid, and wash by ethyl acetate, gained white product is dissolved with toluene, add again the activated silica gel of 1 ~ 3 times of quality to be placed in the lump the single port flask with water trap, temperature rising reflux reacts to liquid volume in water trap and no longer changes, filter, wash to obtain silica derivative product with water, and at normal temperatures with 1.0 ~ 1.2 times of L-PROLINE sodium water solutions to tropanol molar weight stir 40 ~ 48h(or first and aqueous sodium hydroxide solution mix and blend 40 ~ 48h obtain alkaline immobilization ionic liquid, after washing with water, add again 1.0 ~ 1.2 times to the L-PROLINE of tropanol molar weight), filter, wash with water, after dry, obtain target product immobilization ionic liquid.
4. tropanol amino acid anion chiral ionic liquid claimed in claim 1 splits the method for DL-phenylalanine: in ionic liquid, add a certain amount of neutralized verdigris and DL-phenylalanine, add again a certain amount of salts solution to form double water-phase, after centrifugal, ionic liquid is rich in D type mutually, insoluble solids is rich in L-type mutually, it is characterized in that: each composition order of addition is chiral ionic liquid-neutralized verdigris-DL phenylalanine-salts solution, the mol ratio of neutralized verdigris and ionic liquid is 0.22 ~ 0.81, the mol ratio of DL-phenylalanine and ionic liquid is 0.09 ~ 0.62, the mol ratio of water and ionic liquid is 49.13 ~ 180.14, the mol ratio of salt and ionic liquid is 2.54 ~ 7.62, the salts solution adding is a kind of in potassium phosphate solution, dipotassium hydrogen phosphate solution and solution of potassium carbonate, in extraction split process, along with increasing of the DL-phenylalanine amount adding, there is insoluble solid phase in ionic liquid mutually below.
5. immobilized tropanol amino acid anion chiral ionic liquid claimed in claim 1 splits the method for DL-Trp and DL phenylalanine: this immobilization ionic liquid is fully mixed after vibration with copper sulfate solution, filter, wash with water, being placed in vacuum drying oven dries, then get 1.2g, wet method dress post is in 10 * 200mm glass column, wet method loading amino acid solution (5mg/mL), moving phase speed is 0.1mL/min, it is characterized in that: the mass ratio of copper sulfate and immobilization ionic liquid is greater than 0.05, and the mixing and absorption time is greater than 1h, to guarantee that the amount of immobilization ionic liquid absorbing copper ion reaches capacity, splitting DL-Trp moving phase used is water, and splitting DL-phenylalanine moving phase used is ethanol.
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| CN109999769A (en) * | 2019-03-11 | 2019-07-12 | 常州大学 | A kind of preparation method of the functional solid phase carrier for efficient separating Tryptophan enantiomer |
| CN113277954A (en) * | 2021-06-17 | 2021-08-20 | 英德市匠心新材料股份有限公司 | Amino acid metal chelate micro-nano powder and preparation method thereof |
| CN113292574A (en) * | 2020-02-21 | 2021-08-24 | 四川大学 | Chiral polycyclic tropane compounds, preparation method and application thereof |
| CN115611811A (en) * | 2022-10-13 | 2023-01-17 | 上海工程技术大学 | Chiral ionic liquid and application thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109999769A (en) * | 2019-03-11 | 2019-07-12 | 常州大学 | A kind of preparation method of the functional solid phase carrier for efficient separating Tryptophan enantiomer |
| CN113292574A (en) * | 2020-02-21 | 2021-08-24 | 四川大学 | Chiral polycyclic tropane compounds, preparation method and application thereof |
| CN113277954A (en) * | 2021-06-17 | 2021-08-20 | 英德市匠心新材料股份有限公司 | Amino acid metal chelate micro-nano powder and preparation method thereof |
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| CN115611811A (en) * | 2022-10-13 | 2023-01-17 | 上海工程技术大学 | Chiral ionic liquid and application thereof |
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