CN109999769A - A kind of preparation method of the functional solid phase carrier for efficient separating Tryptophan enantiomer - Google Patents
A kind of preparation method of the functional solid phase carrier for efficient separating Tryptophan enantiomer Download PDFInfo
- Publication number
- CN109999769A CN109999769A CN201910181937.6A CN201910181937A CN109999769A CN 109999769 A CN109999769 A CN 109999769A CN 201910181937 A CN201910181937 A CN 201910181937A CN 109999769 A CN109999769 A CN 109999769A
- Authority
- CN
- China
- Prior art keywords
- preparation
- solid phase
- phase carrier
- silicon dioxide
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B57/00—Separation of optically-active compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
- C07D209/18—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D209/20—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals substituted additionally by nitrogen atoms, e.g. tryptophane
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
Abstract
The present invention relates to a kind of preparation method of functional solid phase carrier for efficient separating Tryptophan enantiomer, specific steps include: a) to prepare chiral precursor through single step reaction using left-handed phenylalaninol as reaction raw materials;B) silicon dioxide microsphere containing imidazole group is prepared;C) it is bonded one step of reaction raw materials prepared by above-mentioned two step to obtain target functionality silicon dioxide microsphere;D) Tryptophan enantiomer is selectively split as solid extracting agent using functionalized silica microballoon prepared by step c, through the available higher single configuration tryptophan of optical purity of detection, ee value is up to 93.0% or more.The beneficial effects of the present invention are: functionalized silica method for preparing microsphere is simple, chiral separation has many advantages, such as that easy to operate, at low cost, resolution yield is high.
Description
Technical field
The present invention relates to a kind of preparation methods of functional solid phase carrier for efficient separating Tryptophan enantiomer, belong to
Isolation technics and field of material preparation.
Background technique
Silicon dioxide microsphere has many advantages, such as morphology controllable, property stabilization, homogeneous grain diameter, is widely used to materialized
The multiple fields such as, chromatography, medicine.In addition, the organic molecule containing particular functional group is covalently bound to silicon dioxide microsphere
Surface can satisfy certain specific demands.For example, hydrophobic carbon octadecyl is rolled into a ball key in view of the great amount of hydroxy group of silicon ball surface
Silicon ball surface is closed, very widely used today reverse-phase chromatography filler can be prepared into.Therefore, the functionalization of silicon ball surface has been
Caused extensive concern.Its common synthetic method be using the silylation reagent containing organic group, toluene or its
He is heated to reflux obtained in organic solvent.However, it is necessary to it is noted that existing method have the defects that it is certain, comprising:
(1) small organic molecule of silane-group containing is not common, needs to carry out complicated organic reaction and carries out multistep synthesis, it is caused to be difficult
Applied in industrial production;(2) increase of reaction step will affect the monodispersity of silicon dioxide microsphere, to influence its separation
Efficiency.Therefore, novel functional method is designed and developed to have great importance.
A kind of compound that ionic liquid, which refers to, to be in a liquid state at room temperature, and be made of completely anions and canons.Ionic liquid
Have many advantages, such as lower vapour pressure, good electric conductivity and non-combustible.On this basis, numerous seminars trial will be organic
Functional group is introduced into ionic liquid to meet specific demand.By the development of recent two decades, it is widely used to each
A field.But chiral ionic liquid as chiral zinc porphyrin molecular linkage to silicon dioxide microsphere surface relevant report not
It is common.In summary, it is intended that design a kind of new functional silicon ball of synthetic method preparation, and used as chiral resolution material
In the chiral resolution research of tryptophan.
Summary of the invention
The purpose of the invention is to provide a kind of functional solid phase carriers for efficient separating Tryptophan enantiomer
Preparation method.The functionalized silica microballoon of preparation is carried out efficient separating as solid extracting agent tryptophan enantiomer to grind
Study carefully.
A kind of preparation method of the functional solid phase carrier for efficient separating Tryptophan enantiomer, comprising the following steps:
A, it prepares chiral precursor: at room temperature, weighing the left-handed phenylalaninol of 0.755g and be dissolved in 25-35mL methylene chloride, magnetic force stirs
It mixes, then weighs 0.525g 2- chloroethyl isocyanide ester and be added dropwise in above-mentioned solution, after reaction 3-4 hours, vacuum distillation is removed
Solvent, chloroform remove by-product, are dried in vacuo to get chiral precursor;
B, it prepares the silicon dioxide microsphere containing imidazole group: it is molten to prepare the ethanol/water mixing that 80-100mL volume ratio is 9:1
Liquid is added in Xiang Shangshu solution and sequentially adds 0.5g silicon dioxide microsphere, 1.15gN- 3- chloropropyl imidazoles, 5mL ammonium hydroxide, room temperature
Lower magnetic agitation 12-15 hours, after fully reacting, high speed centrifugation obtains yellow solid, is successively cleaned with ethyl alcohol, water, vacuum drying,
Up to the silicon dioxide microsphere containing imidazole group;
C, functionalized silica microballoon: sequentially added into 100mL round-bottomed flask 0.768g step a preparation chiral precursor,
It is small to be heated to reflux 36-48 for the silicon dioxide microsphere containing imidazole group, the 50mL acetonitrile of 0.7g step b preparation, magnetic agitation
When, after fully reacting, high speed centrifugation obtains brown solid, is successively cleaned with ethyl alcohol, water, is dried in vacuo to get functional titanium dioxide
Silicon microballoon;
D, Solid Phase Extraction: weighing 30mg dl-tryptophan enantiomer and 10mg copper chloride is dissolved in 20-30mL water, thereto plus
Enter the functionalized silica microballoon of 400mg step c preparation, vibrate 2 minutes, high speed centrifugation, take supernatant, vacuum rotary steam removes
Water, vacuum drying, obtains optically pure dextrorotation tryptophan.
Further, it is 300-400r/min that magnetic stirring speed is reacted in step a, cleans chloroform volume used and is
20mL。
Further, magnetic stirring speed is 300-400r/min in step b, and cleaning ethyl alcohol volume used is 20-30mL,
Water volume is 20-30mL.
Further, magnetic stirring speed is 300-400r/min in step c, and cleaning ethyl alcohol volume used is 20-30mL,
Cleaning water volume used is 20-30mL.
Further, centrifugal rotational speed is 8000-10000r/min in step d.
The beneficial effects of the present invention are: functionalized silica method for preparing microsphere is simple, chiral separation has operation
Simply, the advantages that at low cost, chiral resolution high income.
Detailed description of the invention
This experiment is further illustrated with reference to the accompanying drawing.
Fig. 1 is the field emission scanning electron microscope figure of the functionalized silica microballoon prepared in embodiment one.
Specific embodiment
Presently in connection with specific embodiment, the present invention will be further described, following embodiment be intended to illustrate invention rather than
Limitation of the invention further.
The optical purity of the present invention for splitting obtained tryptophan is identified as follows:
ee=(CL-CD)/(CL-CD)
In formula, ee indicates the excessive value of L-type enantiomer, CLAnd CDRespectively indicate the concentration of L-Trp and D-trp.
Embodiment one:
The preparation of functionalized silica microballoon comprising the following three steps:
(1) at room temperature, it weighs the left-handed phenylalaninol of 3.02g to be dissolved in 120mL methylene chloride, revolving speed is that 300r/min magnetic force stirs
It mixes, then weighs 2.1g 2- chloroethyl isocyanide ester and be added dropwise in above-mentioned solution, white precipitate occur and subtract after reaction 4 hours
Solvent is distilled off in pressure, and 60mL chloroform removes by-product, is dried in vacuo to get chiral precursor 4.88g, yield 95%.
(2) at room temperature, the ethanol/water mixed solution that 150mL volume ratio is 9:1 is prepared, is added successively in Xiang Shangshu solution
1.0g silicon dioxide microsphere, 2.30g is addedN- 3- chloropropyl imidazoles, 10mL ammonium hydroxide, revolving speed are that 300r/min magnetic agitation 15 is small
When, after fully reacting, revolving speed is that 10000r/min high speed centrifugation obtains yellow solid, is successively cleaned with 40mL ethyl alcohol, 40mL water, very
Sky is dry to get the silicon dioxide microsphere 1.78g containing imidazole group.
(3) chiral precursor of 1.536g step a preparation is sequentially added into 100mL round-bottomed flask, prepared by 1.4g step b
Silicon dioxide microsphere containing imidazole group, 60mL acetonitrile, revolving speed are 300r/min magnetic agitation, are heated to reflux 48 hours, instead
After answering completely, revolving speed is that 10000r/min high speed centrifugation obtains brown solid, is successively cleaned with 40mL ethyl alcohol, 40mL water, vacuum is dry
It is dry to get functionalized silica microballoon 2.52g;
Embodiment two:
It weighs 300mg dl-tryptophan enantiomer and 100mg copper chloride is dissolved in 150mL water, 4g step c system is added thereto
Standby functionalized silica microballoon vibrates 5 minutes, 10000r/min high speed centrifugation, takes supernatant, and vacuum rotary steam removes water,
Vacuum drying, obtains optically pure dextrorotation tryptophan 126mg, yield 84%, and ee value is 93%.
Claims (5)
1. a kind of preparation method of the functional solid phase carrier for efficient separating Tryptophan enantiomer, steps are as follows:
A, it prepares chiral precursor: at room temperature, weighing the left-handed phenylalaninol of 0.755g and be dissolved in 25-35mL methylene chloride, magnetic force stirs
It mixes, then weighs 0.525g 2- chloroethyl isocyanide ester and be added dropwise in above-mentioned solution, after reaction 3-4 hours, vacuum distillation is removed
Solvent, chloroform remove by-product, are dried in vacuo to get chiral precursor;
B, it prepares the silicon dioxide microsphere containing imidazole group: it is molten to prepare the ethanol/water mixing that 80-100mL volume ratio is 9:1
Liquid is added in Xiang Shangshu solution and sequentially adds 0.5g silicon dioxide microsphere, 1.15gN- 3- chloropropyl imidazoles, 5mL ammonium hydroxide, room temperature
Lower magnetic agitation 12-15 hours, after fully reacting, high speed centrifugation obtains yellow solid, is successively cleaned with ethyl alcohol, water, vacuum drying,
Up to the silicon dioxide microsphere containing imidazole group;
C, functionalized silica microballoon: sequentially added into 100mL round-bottomed flask 0.768g step a preparation chiral precursor,
It is small to be heated to reflux 36-48 for the silicon dioxide microsphere containing imidazole group, the 50mL acetonitrile of 0.7g step b preparation, magnetic agitation
When, after fully reacting, high speed centrifugation obtains brown solid, is successively cleaned with ethyl alcohol, water, is dried in vacuo to get functional titanium dioxide
Silicon microballoon;
D, Solid Phase Extraction: weighing 30mg dl-tryptophan enantiomer and 10mg copper chloride is dissolved in 20-30mL water, thereto plus
Enter the functionalized silica microballoon of 400mg step c preparation, vibrate 2 minutes, high speed centrifugation, take supernatant, vacuum rotary steam removes
Water, vacuum drying, obtains optically pure dextrorotation tryptophan.
2. a kind of preparation side of the functional solid phase carrier for efficient separating Tryptophan enantiomer according to claim 1
Method, it is characterized in that: reacting magnetic stirring speed in the step a is 300-400r/min, cleaning chloroform volume used is 20mL.
3. a kind of preparation side of the functional solid phase carrier for efficient separating Tryptophan enantiomer according to claim 1
Method, it is characterized in that: magnetic stirring speed is 300-400r/min in the step b, high speed centrifugation revolving speed is 8000-10000r/
Min, cleaning ethyl alcohol volume used is 20-30mL, water volume 20-30mL.
4. a kind of preparation side of the functional solid phase carrier for efficient separating Tryptophan enantiomer according to claim 1
Method, it is characterized in that: magnetic stirring speed is 300-400r/min in the step c, high speed centrifugation revolving speed is 8000-10000r/
Min, cleaning ethyl alcohol volume used is 20-30mL, and cleaning water volume used is 20-30mL.
5. a kind of preparation side of the functional solid phase carrier for efficient separating Tryptophan enantiomer according to claim 1
Method, it is characterized in that: centrifugal rotational speed is 8000-10000r/min in the step d.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910181937.6A CN109999769A (en) | 2019-03-11 | 2019-03-11 | A kind of preparation method of the functional solid phase carrier for efficient separating Tryptophan enantiomer |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910181937.6A CN109999769A (en) | 2019-03-11 | 2019-03-11 | A kind of preparation method of the functional solid phase carrier for efficient separating Tryptophan enantiomer |
Publications (1)
Publication Number | Publication Date |
---|---|
CN109999769A true CN109999769A (en) | 2019-07-12 |
Family
ID=67166815
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201910181937.6A Pending CN109999769A (en) | 2019-03-11 | 2019-03-11 | A kind of preparation method of the functional solid phase carrier for efficient separating Tryptophan enantiomer |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN109999769A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110591105A (en) * | 2019-09-05 | 2019-12-20 | 常州大学 | Preparation and application of rotaxane molecule with electrochemical activity |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1994557A (en) * | 2006-12-04 | 2007-07-11 | 浙江大学 | Teicoplanin p-chlorophenyl isocyanate chiral stationary phase filling and method for preparing same |
US20120083603A1 (en) * | 2007-01-31 | 2012-04-05 | Sigma-Aldrich Co. Llc | High stability polyionic liquid salts |
CN103951665A (en) * | 2014-04-16 | 2014-07-30 | 四川大学 | 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 |
CN105903457A (en) * | 2016-06-12 | 2016-08-31 | 中国科学院青岛生物能源与过程研究所 | Imidazole ionic liquid chiral stationary phase and preparation method and application |
-
2019
- 2019-03-11 CN CN201910181937.6A patent/CN109999769A/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1994557A (en) * | 2006-12-04 | 2007-07-11 | 浙江大学 | Teicoplanin p-chlorophenyl isocyanate chiral stationary phase filling and method for preparing same |
US20120083603A1 (en) * | 2007-01-31 | 2012-04-05 | Sigma-Aldrich Co. Llc | High stability polyionic liquid salts |
CN103951665A (en) * | 2014-04-16 | 2014-07-30 | 四川大学 | 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 |
CN105903457A (en) * | 2016-06-12 | 2016-08-31 | 中国科学院青岛生物能源与过程研究所 | Imidazole ionic liquid chiral stationary phase and preparation method and application |
Non-Patent Citations (3)
Title |
---|
DATONG WU等: "Enhancement of visual chiral sensing via an anion-binding approach:Novel ionic liquids as the chiral selectors", 《ANALYTICA CHIMICA ACTA》 * |
PENGFEI CAI等: "Fluorescence recognition of chiral amino alcohols by using a novel ionic liquid sensor", 《ANALYST》 * |
崔兴等: "手性离子液体拆分对映体技术研究进展", 《高校化工工程学报》 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110591105A (en) * | 2019-09-05 | 2019-12-20 | 常州大学 | Preparation and application of rotaxane molecule with electrochemical activity |
CN110591105B (en) * | 2019-09-05 | 2021-11-30 | 常州大学 | Preparation method of electrochemical-active rotaxane molecule for chiral recognition |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN109261128B (en) | Boric acid type magnetic COFs material, preparation method and application thereof | |
Shephard et al. | Site‐Directed Surface Derivatization of MCM‐41: Use of High‐Resolution Transmission Electron Microscopy and Molecular Recognition for Determining the Position of Functionality within Mesoporous Materials | |
Baig et al. | A highly active magnetically recoverable nano ferrite-glutathione-copper (nano-FGT-Cu) catalyst for Huisgen 1, 3-dipolar cycloadditions | |
US6417339B1 (en) | Dendrimers based on saccharides | |
CN107267494A (en) | The@Fe of enzyme@ZIF 83O4Magnetic Nano enzyme reactor and preparation method thereof | |
Yuan et al. | Organocatalytic asymmetric synthesis of arylindolyl indolin-3-ones with both axial and central chirality | |
CN110694688B (en) | Bimetallic functionalized ZnCo-MOF catalytic material prepared by dry glue one-pot method and preparation method and application thereof | |
CN109999769A (en) | A kind of preparation method of the functional solid phase carrier for efficient separating Tryptophan enantiomer | |
Xiong et al. | Enantioselective synthesis of chiral multicyclic γ-lactones via dynamic kinetic resolution of racemic γ-keto carboxylic acids | |
Xing et al. | Cooperative chiral salen Ti IV catalyst supported on ionic liquid-functionalized graphene oxide accelerates asymmetric sulfoxidation in water | |
CN102432608B (en) | Method for synthesizing optically active tetrahydro-beta-carboline derivative through catalysis of chiral spirocyclic phosphoric acid | |
CN105964306B (en) | It is a kind of based on poly ion liquid magnetic nano-particle, preparation method and its application in three component reactions | |
CN103880790A (en) | Synthetic method for furan coupling compound | |
CN111560365B (en) | Preparation method and application of carbon nanotube-based imprinting immobilized enzyme | |
CN104119459A (en) | Preparation method of cyclodextrin hybrid alkyl skeleton chiral stationary phase | |
CN111253425B (en) | Synthesis method of 1, 3-bis [2- (3, 4-epoxycyclohexyl) ethyl ] tetramethyldisiloxane | |
CN108250381B (en) | Preparation method and application of selenium-containing phenolic resin microspheres | |
CN107793347B (en) | Method for synthesizing asymmetric [60] fullerene pyrrolidine derivative | |
CN109096212B (en) | Method for synthesizing 5-I-1,2, 3-triazole compound by water phase one-pot method | |
CN109704985B (en) | Method for synthesizing condensed ring aromatic alkyl amide embedded liquid chromatography stationary phase | |
CN110129308B (en) | Surface charge-controlled functionalized dendritic mesoporous SiO 2 Immobilized chloroperoxidase reactor and application thereof | |
CN111229189B (en) | Self-assembly type amino acid derivative functionalized magnetic-carbon nanotube composite material and preparation method and application thereof | |
CN109097025B (en) | Preparation method of adjustable fluorescent nitrogen dots | |
Bezlepkina et al. | Optimized synthesis of functional organosilicon monomers and polymers exploiting new types of CuAAC recoverable heterogeneous catalysts | |
JP6982262B2 (en) | Purification method |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
WD01 | Invention patent application deemed withdrawn after publication | ||
WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20190712 |