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Preparation of p-tolyl/4-chlorophenyl isocyanate-modified cationic cyclodextrin chiral resolution material through click chemistry and application of chiral resolution material

A technology of chlorophenylisocyanate and toluenesulfonyl cyclodextrin, which is applied in separation methods, solid adsorbent liquid separation, and other chemical processes, can solve the difficulties in the development of bonded arms and the unstable groups of functional bonded arms , Cyclodextrin falling off and other problems, to achieve the effect of improving chiral recognition ability, increasing separation throughput, and reducing the difficulty of immobilization

Inactive Publication Date: 2016-04-20
TIANJIN UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

But there are still some problems: (1) there are unstable groups in the functional bonding arm, cyclodextrin is prone to fall off, and the reproducibility of chromatographic separation materials is poor; (2) the controllable bonding arm with multiple recognition sites It is difficult to develop, and only several specific chiral drugs can be resolved; (3) for the modification of cyclodextrin, although dipole-dipole, π-π bonds, hydrophobic interactions, etc. can be introduced, it is difficult to guarantee Stability to different chromatographic separation conditions; for different modified cyclodextrin chiral stationary phases, only specific enantiomers can be resolved, which is highly targeted

Method used

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  • Preparation of p-tolyl/4-chlorophenyl isocyanate-modified cationic cyclodextrin chiral resolution material through click chemistry and application of chiral resolution material
  • Preparation of p-tolyl/4-chlorophenyl isocyanate-modified cationic cyclodextrin chiral resolution material through click chemistry and application of chiral resolution material
  • Preparation of p-tolyl/4-chlorophenyl isocyanate-modified cationic cyclodextrin chiral resolution material through click chemistry and application of chiral resolution material

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Experimental program
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Effect test

preparation example Construction

[0036] Such as figure 1 Shown in the present invention, the preparation method of the cationic cyclodextrin chiral resolution material modified by toluene / chlorophenylisocyanate, the steps are as follows:

[0037] Step 1, the preparation of mono-6-(1-allylimidazole) cyclodextrin:

[0038] Add mono-6-p-methylbenzenesulfonyl cyclodextrin and 1-allyl imidazole in an organic solvent, the organic solution used is toluene, ethanol, acetonitrile, pyridine, N,N-dimethylformamide, di One of the methyl sulfoxides. The mono-6-p-toluenesulfonyl cyclodextrins used were mono-6-p-toluenesulfonyl-α-cyclodextrin, mono-6-p-toluenesulfonyl-β-cyclodextrin and One of the mono-6-p-toluenesulfonyl-γ-cyclodextrins. The molar ratio of the mono-6-p-methylbenzenesulfonyl cyclodextrin to 1-allylimidazole is 1:2 to 1:5, react at 50 to 150°C for 20 to 40 hours, and then the reaction system Pour into acetonitrile to precipitate a solid, wash twice with acetonitrile, and dry to obtain mono-6-(1-allylimid...

Embodiment 1

[0059] 5 g of mono-6-p-toluenesulfonyl-β-cyclodextrin, 20 mL of DMF and 2 mL of 1-allyl imidazole were sequentially added into a 100 mL three-necked flask, and the reaction was stirred at 90° C. for 36 hours. Acetonitrile was added, and a large amount of white solid was precipitated, which was filtered by suction and dried in vacuum at 60° C. for 3 hours. Mono-6-(1-allyl imidazole)-β-cyclodextrin was obtained.

[0060] Dissolve mono-6-(1-allylimidazolium)-β-cyclodextrin in a 300mL beaker, install the chloride-type anion resin in an ion-exchange column, and wash it with water continuously until the resin is neutral. The mono-6-(1-allylimidazole)-β-cyclodextrin solution was poured into an ion exchange column, rinsed continuously with a large amount of water, and the obtained filtrate was spin-dried with a rotary evaporator to obtain the product.

[0061] Add 2.14 g of mono-6-(1-allylimidazole)-β-cyclodextrin, 50 mL of pyridine, and 12 mL of p-toluene / chlorophenyl isocyanate int...

Embodiment 2

[0069] Add 10.5g of mono-6-p-toluenesulfonyl-β-cyclodextrin, 15mL of DMF and 3.5mL of 1-allyl imidazole to a 250mL three-necked flask in sequence, and stir at 70°C for 24 hours. Acetonitrile was added, and a large amount of white solid was precipitated, which was filtered by suction and dried in vacuum at 60° C. for 3 hours. Mono-6-(1-allyl imidazole)-β-cyclodextrin was obtained.

[0070] Dissolve mono-6-(1-allylimidazole)-β-cyclodextrin in a 100mL beaker, install the nitrate anion resin in an ion exchange column, and wash it with water continuously until the resin is neutral. The mono-6-(1-allylimidazole)-β-cyclodextrin solution was poured into an ion exchange column, rinsed continuously with a large amount of water, and the obtained filtrate was spin-dried with a rotary evaporator to obtain the product.

[0071] Add 1.5 g of mono-6-(1-allylimidazole)-β-cyclodextrin, 30 mL of pyridine, and 5.5 mL of p-toluene / chlorophenyl isocyanate into a 100 mL three-necked flask. N 2 pr...

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Abstract

The invention discloses a method for preparing a p-tolyl / 4-chlorophenyl isocyanate-modified cationic cyclodextrin chiral resolution material through click chemistry. According to the method, 4-chlorophenyl isocyanate and p-tolyl isocyanate groups are introduced for function derivation of allylimidazole cyclodextrin, then mercapto-alkene click reaction is carried out to realize controllable bridging of allylimidazole cyclodextrin and mercapto-modified silica gel, and a hydrophobic modified cyclodextrin monomolecular layer is constructed on the surface of porous silica gel through thioether bonds, so the novel cyclodextrin chiral resolution material with definite structure and a plurality of action sites is prepared. The p-tolyl / 4-chlorophenyl isocyanate-modified cationic cyclodextrin chiral resolution material can be applied to chiral separation of compounds in a reversed-phase chromatographic mode and shows excellent resolution capability to medicines of different classes, e.g., isoxazolines, flavanones, bendrofluazide and 4-chromanol. The mercapto-alkene click reaction provided by the invention provides a highly-universal effective approach for preparation of a controllable chiral resolution material with stable structure.

Description

technical field [0001] The invention belongs to the field of chiral resolution of drug racemates, and relates to chromatographic chiral resolution materials: functional derivation of allyl imidazolium salt cyclodextrin by introducing p-chlorophenyl isocyanate and p-methylphenyl isocyanate groups , and then through the "mercapto-ene" click reaction to controlly bridge the allyl imidazolium salt cyclodextrin and the mercapto-modified silica gel, construct a hydrophobic modified cyclodextrin monolayer on the surface of the porous silica gel through the thioether bond, and prepare the Two novel cyclodextrin chiral resolution materials with well-defined structures and multiple action sites. The separation material can be used for chiral resolution and preparation of medicines in various chromatographic techniques. Background technique [0002] For compounds with chiral activity, such as most drugs, their pharmacological and toxicological activities are closely related to the chi...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J20/29B01J20/30B01D15/38
CPCB01J20/29B01D15/3833B01J2220/4812B01J2220/80
Inventor 王勇李晓旋张阳
Owner TIANJIN UNIV
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