Method for preparing photoactived amino acid through resolution

An amino acid and photoactivation technology, applied in organic chemistry methods, cyanide reaction preparation, chemical instruments and methods, etc., can solve the undiscovered AES combined chiral reagent resolution, the first separation of diastereomer product yield And problems such as low optical purity, resolution product yield and optical purity, etc., to achieve the effect of high resolution efficiency, high purity and high recovery rate

Active Publication Date: 2011-11-16
河北凯力昂生物科技有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the yield and optical purity of the first diastereoisomeric product obtained by using this method to resolve the racemic amino acid is relatively low
[0005] In 1994, Ryuzo Yoshioka (Bull.Chem.Soc.Jpn., 67, 3012-3020) and others used (-)-1-phenylethanesulfonic acid to resolve racemic p-hydroxyphenylglycine, and preferentially precipitated the less soluble Diastereomeric salt, yield is 87.6% (calculated as 100% with half the theoretical amount of diastereomeric salt), the optical purity of L-p-hydroxyphenylglycine is 95% o.p, the yield of resolution product and Relatively low optical purity
There is no report on the resolution of racemic amino acids and other compounds with AES combined chiral reagents

Method used

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  • Method for preparing photoactived amino acid through resolution
  • Method for preparing photoactived amino acid through resolution
  • Method for preparing photoactived amino acid through resolution

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0022] (1) In 3500mL aqueous solution, add 167.2g of racemic p-hydroxyphenylglycine, 186.8g of combined AES resolving agent is heated to reflux until the solution is clear, after stirring for 5 hours, it is naturally cooled to 68°C, crystals are precipitated, filtered, and 6mL The filter cake was washed with ice water, rinsed with 2 mL of methanol, and dried to obtain 174.5 g of the filter cake.

[0023] The main resolving agent in the combined AES resolving agent is (+)-1-phenylethanesulfonic acid, and the auxiliary resolving agent is 1-(4'-bromophenyl)-ethanesulfonic acid, the molar ratio of the two is It is 99:1.

[0024] (2) Dissolve the above filter cake into 500mL methanol / water solution (volume ratio is 1:1), stir, add 10% NaOH dropwise to the pH of the solution = 5.4, stir for 1h, let stand for 1h, filter, and use for filter cake Rinse with a small amount of ice water and dry to obtain 81.4 g of D-(-)-p-hydroxyphenylglycine with a yield of 97.4%. [α] 20 D -158.0° (...

Embodiment 2

[0031] (1) In 3000mL aqueous solution, add 167.2g of racemic p-hydroxyphenylglycine, 195g of combined AES resolving agent is heated to reflux until the solution is clear, after stirring for 5h, it is naturally cooled to 65°C, crystals are precipitated, filtered, and washed with 6mL of ice The filter cake was washed with water, rinsed with 2 mL of methanol, and dried to obtain 173.7 g of the filter cake.

[0032] The main resolving agent in the described combined AES resolving agent is (-)-1-phenylethanesulfonic acid, and the auxiliary resolving agent is 1-(4'-nitrophenyl)-ethanesulfonic acid, both moles The ratio is 80:20.

[0033](2) Dissolve the above filter cake into 510mL methanol / water solution (volume ratio is 1:1), stir, add 10% KOH dropwise to the pH of the solution=5.4, stir for 1h, let stand for 1h, filter, and use for filter cake Rinse with a small amount of ice water and dry to obtain 81.7 g of L-(+)-p-hydroxyphenylglycine with a yield of 97.8%. [α] 20 D +157.7...

Embodiment 3

[0040] (1) In 3500mL aqueous solution, add 167.2g of racemic p-hydroxyphenylglycine, 189.1g of combined AES resolving agent is heated to reflux until the solution is clear, after stirring for 5h, it is naturally cooled to 70°C, crystals are precipitated, filtered, and 5mL The filter cake was washed with ice water, rinsed with 1 mL of methanol, and dried to obtain 174.2 g of the filter cake.

[0041] The main resolving agent in the combined AES resolving agent is (-)-1-phenylethanesulfonic acid, and the auxiliary resolving agent is 1-(4'-chlorophenyl)-ethanesulfonic acid, the molar ratio of the two is It is 91:9.

[0042] (2) Dissolve the above filter cake into 480mL methanol / water solution (1:9 by volume), stir, and add Na 2 CO 3 Solution to pH=5.4, stirred for 1 h, allowed to stand for 1 h, filtered, rinsed the filter cake with a small amount of ice water, and dried to obtain 80.5 g of L-(+)-p-hydroxyphenylglycine with a yield of 96.3%. [α] 20 D +157.3° (c=1, 1N HCl), op...

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Abstract

In the invention, the method comprises the steps of: employing a combined AES (1-Arylethanesulfonic acids) resolving agent composed of photoactivated 1-phenyl ethanesulfonic acid as a main resolving agent and racemized substituted phenyl ethanesulfonic acid as an assistant resolving agent to resolve racemized amino acid in an aqueous solution or organic solvent or organic solvent / aqueous solution, heating the mixture to reflux until the solution is clarified, stirring and cooling the solution, separating out crystals, filtering the crystals, washing the filter cake, and stoving the filter cake, thus obtaining a configured photoactived amino acid. And treating the filtrate in the same way can generate another configured photoactived amino acid. The resolving agent, after ion exchange, concentration and recovery, can be used circularly. The combined AES resolving agent of the invention has good selectivity and high resolution efficiency for racemized amino acid, and the two types of configured photoactived amino acid obtained have high purity, and the optical purity can be over 97%o.p. Besides, the yield of product is high, about more than 95%. As the resolving agent has high utilization rate and recovery rate, the production cost can be reduced.

Description

technical field [0001] The invention relates to a method for splitting racemic amino acids to prepare photoactive amino acids, in particular to a method for splitting and preparing L-type and D-type amino acid isomers by using a combined AES splitting agent, and belongs to the technical field of compound preparation. Background technique [0002] L-type amino acids are widely used in food, feed, medicine and other fields; D-type amino acids have an irreplaceable role in life activities and drug preparation, especially as intermediates of β-lactam antibiotics. L-type amino acids can be obtained from natural compounds, while D-type amino acids rarely exist in natural products and are not easy to obtain. The preparation of photoactive amino acids includes the preparation of L-type amino acids and D-type amino acids, and the preparation methods mainly include asymmetric synthesis, biological enzyme method and racemic resolution method. [0003] The asymmetric synthesis method r...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07B57/00C07C227/34C07C229/36C07C229/08C07C279/14C07C277/08C07C229/26
Inventor 孙凤霞王玮张旭王德彬张炳烛
Owner 河北凯力昂生物科技有限公司
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