Method for producing p-vinylphenols

A technology of vinyl phenol and phenol, applied in the field of biocatalysis for preparing p-vinyl phenol, can solve problems such as unreported tyrosine

Inactive Publication Date: 2018-01-02
UNIVERSITY OF GRAZ
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, this reaction has not been reported so far for derivatives of tyrosine

Method used

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  • Method for producing p-vinylphenols
  • Method for producing p-vinylphenols
  • Method for producing p-vinylphenols

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1 to 4

[0076] One-pot reaction of steps a) to c) at different pH values

[0077]

[0078] Using the three enzymes in the artificial synthesis examples 1 to 3, the three-step one-pot reaction using 2-fluorophenol 1a (R=F) was carried out under the following conditions: 1a (23mM); BTS (pyruvate) (46mM) ; TPL (4mg); TAL (20mg); FAD (5mg); Aqueous buffer (50mM): KPi is used for pH 7-8, CHES is used for pH 9-10; Time: 6 hours; 20 ° C; with 850 rpm / min shaking. The pH was varied between 7 and 10, samples were taken at time intervals and analyzed by means of HPLC for the content of 2-fluoro-4-vinylphenol 4a (R=F).

[0079] Figure 4 The results of these reactions are shown. The results show that the conversion at pH 7 (Example 1; about 30%) or at pH 10 (Example 4; about 45%) is significantly lower than at pH 8 (Example 2; about 85%) and pH 9 (Example 3; about 80%), almost the same conversion was obtained for them, this aspect can be attributed to the two enzymes TPL and TAL at pH 7 ...

Embodiment 5 to 8

[0084] One-pot reaction with co-solvent at pH 8

[0085] Therefore, Example 2 above was repeated at pH 8 with varying amounts of co-solvent mixed in and the amount of final product, p-vinylphenol 4a determined. In Example 5 Example 2 was repeated without a co-solvent for comparative purposes, while in Example 6 DMSO was used as a representative of the water-miscible solvent (5 Vol.-%), in Example 7 Diethyl ether was used as a representative of the water-immiscible solvent (5 Vol.-%), and in Example 8, a double amount of diethyl ether (10 Vol.-%) was added based on the volume of the aqueous buffer solution, respectively.

[0086] Figure 7 The results of these experiments are shown. It can be seen that the presence of water-miscible DMSO made practically no difference in the conversion of product 4a, whereas the non-water-miscible diethyl ether increased the conversion by more than 10 at 10 Vol.-% after 6 h reaction time percentage points, but even 20 percentage points at 5 ...

Embodiment 9

[0089] Optimal conditions for a one-pot reaction

[0090] After successful optimization of pH and co-solvent, the experiment in Example 7 was repeated under the following conditions: 1a (23 mM); pyruvate (46 mM); TPL (4 mg); TAL (20 mg); FAD (5 mg); KPi buffer Agent (50mM), pH 8; 5Vol.-%Et 2 O, time: 6 h; 30° C.; shaking at 850 rpm; and here the amounts of reactant 1 a and products 2 a to 4 a were determined at time intervals by means of HPLC.

[0091] Figure 8 The results of this experiment are shown, in which the amount of reactant 1a drops very rapidly at the beginning, and after 6 hours a conversion of more than 95% to the final product 4a is obtained.

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Abstract

The invention relates to a biocatalytic method for producing p-vinylphenols, comprising a three-stage one-pot reaction according to the following reaction scheme: (A) wherein a) an optionally substituted phenol (1) is bound to pyruvic acid (BTS) to form the optionally substituted tyrosine (2) by means of catalytic action of a tyrosine phenol-lyase (TPL) and in the presence of ammonium ions, b) ammonia is eliminated from the tyrosine (2) by means of catalytic action of a tyrosine-ammonia-lyase (TAL) or phenyl-ammonia-lyase (PAL), in order to produce an optionally substituted p-coumaric acid (3), and c) the p-coumaric acid (3) undergoes a decarboxylation by means of catalytic action of a phenolic acid decarboxylase (PAD), in order to produce the desired, optionally substituted p-vinyl phenol(4); d) wherein the resultant CO2 is removed from the reaction system, in order to move the chemical equilibrium of all three reaction steps in the direction of the products.

Description

[0001] The invention relates to a biocatalytic method for preparing p-vinylphenol. Background technique [0002] Vinylphenol derivatives are used as useful components in polymer chemistry and can be used, for example, to assemble dielectric layers in the manufacture of chemical and biological sensors. Halogenated derivatives are used, for example, in the manufacture of flame retardants and chalcones, a class of organic compounds known to have a wide range of biological activities. [0003] The selective para-vinylation of non-activated phenols to p- or 4-vinylphenol is not known. Thus, direct vinylation of non-activated arenes with tin catalysts leads to selective ortho derivatives (Yamaguchi et al., J. Am. Chem. Soc. 117, 1151-1152 (1995)), whereas Lewis acid (such as GaCl 3 ) catalysis affords a mixture of ortho and para regioisomers (Yamaguchi et al., Angew. Chem. Int. Ed. 36, 1313-1315 (1997)). However, neither of these methods was performed on phenol derivatives. More...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C12P7/22
CPCC12N9/88C12P7/22C07C39/20C12P7/42C12P13/22
Inventor 沃尔夫冈·克劳蒂尔爱德华多·布斯托罗伯特·西蒙
Owner UNIVERSITY OF GRAZ
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