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Synthesis and application of catechol derivatives and their biomimetic polymers

A technology of catechol and derivatives, which is applied in the synthesis field of catechol derivatives and biomimetic polymers, can solve the need for cumbersome protection and deprotection of phenolic hydroxyl groups, and catechol compounds cannot be synthesized with biomimetic polymers , long synthetic route, etc.

Active Publication Date: 2021-06-15
HUAZHONG NORMAL UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In these synthetic methods, adopt dopamine and dopamine to carry out derivation or grafting, the source of raw material is limited, the price is expensive, and reaction method is single; Adopt the synthetic method of (3,4-dimethoxy)benzene derivative, synthetic route is long , requiring cumbersome protection and deprotection of phenolic hydroxyl groups, etc.
In addition, the synthesis of pyrocatechol derivatives is also very difficult, and the method for the synthesis of pyrocatechol derivatives reported in the literature at present mainly takes phenol as starting material, and obtains through steps such as formylation and redox (CN103265391 , CN102653506, CN 106278825), these methods have poor selectivity, complex products, and difficult purification; transition metal catalysis can also be used to synthesize catechol derivatives (Angew.Chem.Int.Ed.2013,52,5398-5401.) , this method requires additional directed groups, the source of raw materials is limited and the synthesis cost is expensive; it is also reported that catechol derivatives are obtained through oxidation from cyclohexanone (CN105801381), although this method has good selectivity, but Limited by the substrate cyclohexanone derivatives, the obtained catechol compounds cannot be used in the synthesis of biomimetic polymers

Method used

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  • Synthesis and application of catechol derivatives and their biomimetic polymers
  • Synthesis and application of catechol derivatives and their biomimetic polymers
  • Synthesis and application of catechol derivatives and their biomimetic polymers

Examples

Experimental program
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Embodiment 1

[0026] The synthesis of embodiment 1 pyrocatechol derivatives

[0027] The general method for the synthesis of catechol derivatives: add secondary amine (0.03mol), formaldehyde solution (37% solution, 0.03mol), 50mL water in a 150mL flask, stir and react for 30min at 25°C, N 2 Under atmosphere, an aqueous solution (10 mL) of catechol (0.03 mol) was slowly added, and the reaction was continued for 3 h, and the end point of the reaction was monitored by TLC. Dilute hydrochloric acid (1 mol / L) was added to the reaction solution to adjust the pH value of the reaction solution to about 2, and the raw material of catechol was recovered by extraction with ether, and the water phase was retained. Add NaOH solution to adjust the pH value of the aqueous phase to about 8, extract 3 to 5 times with 100 mL ethyl acetate, and remove the organic phase with anhydrous Na 2 SO 4 Drying, precipitation, recrystallization from an appropriate amount of acetonitrile to obtain the 4-substituted cat...

Embodiment 2

[0039] The synthesis of embodiment 2 polyurethane biomimetic polymer (CPU)

[0040] In a 100mL three-necked flask, add polyethylene glycol (molecular weight 1000, 4.0g, 4mmol) and 20mL N,N-dimethylformamide (DMF, anhydrous) that were dewatered under vacuum at 100°C, and heat up to 70°C. N 2 With mechanical stirring, slowly add isophorone diisocyanate (1.78g, 8mmol) dropwise, react for 2h, control -NCO content at 5.8% of theoretical value (use di-n-butylamine method for titration, bromophenol blue as indicator) , cooled to room temperature, slowly added dropwise 5 mL of a DMF solution containing 4-(N,N-bis(2-hydroxyethyl)aminomethyl)catechol (II-c) (0.91g, 4mmol), 60°C Reaction 2h. Cool to room temperature, add anhydrous diethyl ether to precipitate, centrifuge to obtain a yellow thick or jelly, and vacuum dry at 40°C for 48 hours to obtain catechol-containing biomimetic polyurethane CPU with a yield of 85%.

[0041] 1 H NMR (600MHz, DMSO-d6) δ6.6-7.1 (broad peak, benzene r...

Embodiment 3

[0042] The synthesis of embodiment 3 polyacrylate biomimetic polymer (CPA)

[0043] First, the methacrylated intermediate II-d (catechol-containing acrylate) was synthesized. 4-(N-(2-hydroxyethyl)--N-methylaminomethyl)catechol (II-d, 1.97g, 10mmol) was dissolved in 50mL of anhydrous tetrahydrofuran, and triethylamine ( 2.02g, 10mmol), slowly dropwise added 10mL of anhydrous tetrahydrofuran solution containing 2-methacrylic anhydride (2.31g, 15mmol) under ice-cooling, and reacted at room temperature for 12h. After column chromatography (eluent: ethyl acetate / petroleum ether, volume ratio 1 / 2), 2-(N-(3,4-dihydroxybenzyl)-N-methylamino)ethylmethyl Acrylate (yellow oil, 1.91 g, yield 72%). 1 H NMR (600MHz, CDCl 3 )δ6.76(s,1H),6.71(d,J=7.9Hz,1H),6.63(d,J=7.5Hz,1H),6.18(s,2H),6.10(s,1H),5.56( s, 1H), 4.31 (t, J = 5.6Hz, 2H), 3.48 (s, 2H), 2.76 (t, J = 5.6Hz, 2H), 2.31 (s, 3H), 1.92 (s, 3H).

[0044] In a three-necked flask, add methacrylation intermediate II-d (1.33g, 5mmol), p...

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Abstract

The invention discloses a synthesis method and application of a class of catechol derivatives and a biomimetic polymer, belonging to the field of macromolecular biomaterials and functional materials. The present invention uses cheap and easy-to-get catechol, formaldehyde, and secondary amines as raw materials to obtain catechol derivatives substituted with 4-position aminomethyl groups and catechol derivatives substituted with 3-position amine methyl groups through Mannich reaction. Phenol derivatives. The biomimetic polymer is a catechol-containing polyurethane biomimetic polymer or a catechol-containing polyacrylate biomimetic polymer, and the biomimetic polymer containing a catechol structure is obtained through addition polymerization or free radical polymerization of polymer monomers. The catechol derivatives obtained in the present invention can be used for the synthesis of biomimetic polymers containing catechol structural units; the biomimetic polymers synthesized by catechol derivatives have excellent coating forming ability, resistance The protein adsorption ability and the ability to form hydrogels have application value in medical adhesives, medical hydrogels, coating materials, etc.

Description

technical field [0001] The invention relates to the field of macromolecular biomaterials and functional materials, in particular to a synthesis method and application of a class of catechol derivatives and bionic polymers. Background technique [0002] Catechol units widely exist in biomolecules in nature, and have important diverse biological activities and functions. Among them, mussel silk podoprotein (mfps) containing catechol units has the ability of adhesion and wet adhesion on any surface. Function has received extensive attention in recent years [Science.2007,318,426-430.Nat Mater.2008,7,8-9.]. Inspired by the function of mussel fibropodia, specifically designed catechol-containing polymers have important potential applications [Chem.Rev.2014,114,5057-5115.Chem.Soc.Rev.2011,40,4244- 4258.]. For example, the amphiphilic polymer (mPEG-DOPA) containing catechol structure can form a coating with anti-protein adsorption ability on various surfaces (Langmuir, 2005, 21, 6...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C213/02C07C215/50C07C227/18C07C229/16C08G18/32C08F220/36C08F220/28C09D175/04C09D133/14
CPCC07C213/02C07C227/18C08F220/28C08F220/36C08G18/10C09D133/14C09D175/04C08F220/286C07C229/16C07C215/50C08G18/3215
Inventor 张爱东段江涂海洋吴文海
Owner HUAZHONG NORMAL UNIV
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