Phenolic hydroxyl-containing amino acid-N-thiocarboxylic anhydride monomer and synthesis and polymerization method thereof

A technology of phenolic hydroxyl amino acid and thiocarboxylic anhydride, which is applied in the field of polymer synthesis, can solve problems such as direct synthesis of polyamino acids that have not yet been seen, and achieve good biocompatibility and biodegradability, cheap and easily available raw materials, and high initiation activity. Effect

Active Publication Date: 2018-05-04
ZHEJIANG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] There is no report on the direct synthesis of polyam

Method used

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  • Phenolic hydroxyl-containing amino acid-N-thiocarboxylic anhydride monomer and synthesis and polymerization method thereof
  • Phenolic hydroxyl-containing amino acid-N-thiocarboxylic anhydride monomer and synthesis and polymerization method thereof
  • Phenolic hydroxyl-containing amino acid-N-thiocarboxylic anhydride monomer and synthesis and polymerization method thereof

Examples

Experimental program
Comparison scheme
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Example Embodiment

[0031] Example 1

[0032] Add 36.2g (0.20mol) tyrosine, 32.0g (0.80mol) sodium hydroxide, 36.0g (0.20mol) S-ethoxythiocarbonylthioglycolic acid (XAA) into the reaction flask, and use 150mL to deionize Dissolved in water, stirred and reacted at room temperature for 72 hours to synthesize 31.3 g of N-ethoxythiocarbonyl substituted tyrosine (0.12 mol, yield 58.2%). The latter is combined with PBr in ethyl acetate 3 The reaction to form a ring yields 9.63 g Tyr-NTA monomer (0.043 mol, yield 35.7%).

[0033] Add 0.223g (1.00mmol) of Tyr-NTA to the reaction flask, dissolve it with 2.0mL of tetrahydrofuran (THF), and add 0.12mL of n-butylamine in THF (0.170mol / L, 0.020mmol), Tyr-NTA and normal The molar ratio of butylamine is 50:1. After sealing, it is placed in an oil bath at 40℃ to react for 4 days. After the reaction, the mixture is poured into ether for precipitation and filtration. The resulting polymer is vacuum dried for 1 day to obtain polytyrosine The yield was 94.2%. The obta...

Example Embodiment

[0034] Example 2

[0035] Other polymerization conditions are the same as in Example 1, except that benzylamine is used as the initiator to initiate the ring-opening polymerization of Tyr-NTA, the solvent is N-methylpyrrolidone (NMP), and the molar ratio of Tyr-NTA to benzylamine is 20: 1. React in a thermostat at 80°C for 12 hours to obtain polytyrosine with a yield of 85.8%. The number average absolute molecular weight of the obtained polymer was 3.0 kDa.

Example Embodiment

[0036] Example 3

[0037] Other polymerization conditions are the same as in Example 1, except that the amino-terminated polyethylene glycol (PEG-NH 2 ) Initiate ring-opening polymerization of Tyr-NTA, the solvent is N,N-dimethylacetamide (DMAc), Tyr-NTA and PEG-NH 2 The molar ratio is 10:1, and the reaction is conducted in a constant temperature bath at 0°C for 2 days, and the yield of the obtained polyamino acid is 99.0%. The number average absolute molecular weight of the obtained copolymer was 3.7 kDa.

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Abstract

The invention discloses a synthesis and polymerization method of a phenolic hydroxyl-containing amino acid-N-thiocarboxylic anhydride (NTA) monomer. An amino acid (comprising N-substituted glycine)-NTA monomer with unprotected phenolic hydroxyl is synthesized for the first time; in the synthesis method, raw materials are cheap and easy to obtain, a synthesis route is simple and the structure of atarget product is clear. In controllable ring-opening polymerization on the monomer, polymerization reaction conditions are moderate; organic amine can trigger one or more of amino acid-NTA to be subjected to the ring-opening polymerization in a solvent and react at the temperature of 0 DEGC to 150 DEG C for 0.5 hour to 4 days, so that a corresponding polyamino acid homopolymer or copolymer is prepared. A chain length of the polymer can be controlled through a feeding ratio of the monomer/an initiator and structural characteristics are clear. The invention provides a novel method for synthesizing an amino acid polymer with a side chain containing phenolic hydroxyl, and the novel method has a great application prospect in the field of biological materials.

Description

technical field [0001] The invention belongs to the field of polymer synthesis, and in particular relates to a synthesis and polymerization method of a phenolic hydroxyl-containing amino acid-N-thiocarboxylic anhydride (NTA) monomer. Background technique [0002] Polyamino acids have excellent biocompatibility and degradability, and are widely used in biomedical fields, such as drug carriers and tissue engineering (J.Am.Chem.Soc.2007, 129, 5362-5363). Amino acid-N-carboxylic anhydride (N-carboxyanhydride, NCA for short) and amino acid-N-thiocarboxylic anhydride (N-thiocarboxyanhydride, NTA for short) are two common cyclic monomers for synthesizing polyamino acids. Early studies found that the hydroxyl group has nucleophilicity and can initiate the polymerization of NCA monomers (Angew. Chem., Int. Ed., 2006, 45, 5752-5784). Therefore, NCA monomers with hydroxyl groups need to protect the hydroxyl groups during synthesis and polymerization, and need to be deprotected after p...

Claims

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Application Information

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IPC IPC(8): C07D277/34C08G69/42
CPCC07D277/34C08G69/42
Inventor 凌君苗岳栋岑佳宇
Owner ZHEJIANG UNIV
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