CN106083625B - A kind of chemical modification method of tyrosine - Google Patents
A kind of chemical modification method of tyrosine Download PDFInfo
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- CN106083625B CN106083625B CN201610373440.0A CN201610373440A CN106083625B CN 106083625 B CN106083625 B CN 106083625B CN 201610373440 A CN201610373440 A CN 201610373440A CN 106083625 B CN106083625 B CN 106083625B
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
- C07C227/16—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions not involving the amino or carboxyl groups
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Abstract
The present invention provides a kind of chemical modification methods of tyrosine, and compared with prior art, the present invention reaches 8g/L, significantly larger than solubility of the tyrosine in DMF and methanol using LiBr dissolving dissolving tyrosine, solubility.High tyrosine concentration not only promotes the progress of reaction, improves reaction efficiency, moreover, the stable system, reaction condition is mild, and 40 DEG C of water-bath can react, and not need to high temperature, the performance of modification tyrosine or protein is not destroyed, possibility is provided for efficiently modification tyrosine.
Description
Technical field
The invention belongs to protein modification arts, and in particular to a kind of chemical modification method of tyrosine.
Background technology
Tyrosine, abbreviation Tyr or Y are a kind of aromatic amino acids, are also 20 kinds of histone aminos for being used for synthetic protein
One of acid, it belongs to nonessential amino acid.It is widely used in bulk pharmaceutical chemicals, food additives and biochemical reagents etc..
At present, more multi-functional attracted more and more people's to by chemical modification modified feedstock property, making it have
Research.For example by ultraviolet-absorbing group modification to tyrosine molecule, the light stability of its own can be promoted；If by quinoline promise
On the structural modifications to tyrosine molecule such as ketone, ether ketone, the functions such as its antibacterial, automatically cleaning can be assigned.If by the function junket ammonia of synthesis
Acid is used to prepare albuminous membranae or azelon etc., will obtain functional protein material.
But because tyrosine has higher dissolving selectivity, so, in the prior art to the chemical modification of tyrosine into
Fruit is not notable.
Invention content
The present invention provides a kind of chemical modification methods of tyrosine, according to the design feature of tyrosine, utilize Mannich
The chemical modification to tyrosine is realized in reaction, and tyrosine solubility is high, and reaction efficiency is high, and reaction condition is mild, does not destroy modification
The performance of tyrosine or protein.
A kind of chemical modification method of tyrosine provided by the invention, includes the following steps：
(1) primary amino compound and aldehyde are dissolved in water, reaction is stirred at room temperature, is prepared containing the molten of cationic imide
Liquid；
(2) tyrosine is dissolved in LiBr solution, carries out acidification, heating stirring is reacted to solution clear, obtained
To the LiBr solution of tyrosine；
(3) under agitation, the solution of the solution containing cationic imide prepared by step (1) is added to step (2)
In the LiBr solution of the tyrosine of preparation, heating stirring reaction is filtered to get product.
Tyrosine in the present invention, aldehyde, primary amino compound the ratio of amount of substance be 1:3-4:1-1.3；
Aldehyde is selected from, but not limited to, formaldehyde, acetaldehyde described in step (1)；The primary amino compound is selected from, but not limited to, aniline
Or ortho-nitraniline.
Further, acetic acid or formic acid can also be added in system in step (1), it is 4 to adjust pH value, makes primary amine groups
Object generation ammonium salt is closed, to increase its solubility.
Step is stirred to react 20-35min in (1).
A concentration of 0.01-0.05mol/L of primary amino compound or aldehyde in water in step (1).
A concentration of 9.0-10mol/L of LiBr solution in step (2)；The heating stirring is specially：At 30-60 DEG C of water-bath
Stirring.
Acidification is specially described in step (2)：Acetic acid is added in step (2) reaction system, the acetic acid of addition
The ratio of volume and LiBr liquor capacities is 1:10-15.
A concentration of 4-8g/L of the LiBr solution of tyrosine in step (2).
Heating stirring described in step (3) is reacted：2-6h is stirred to react under 40 DEG C of water-baths.
Compared with prior art, the present invention reaches 8g/L, significantly larger than junket ammonia using LiBr dissolving dissolving tyrosine, solubility
Solubility of the acid in DMF and methanol.(tyrosine is less than 0.36g/L in DMF solubility, and tyrosine is small in the solubility of methanol
In 0.38g/L.) high tyrosine concentration not only promotes the progress of reaction, improves reaction efficiency, moreover, the stable system,
Reaction condition is mild, and 40 DEG C of water-bath can react, and not need to high temperature, does not destroy the performance of modification tyrosine or protein,
Possibility is provided efficiently to modify tyrosine.
Description of the drawings
Fig. 1 is the UV spectrograms of 1 reaction system of embodiment；
Fig. 2 is the comparison diagram of tyrosine solution and product in embodiment 1；
I is tyrosine solution；II is product；
Fig. 3 is the UV spectrograms of 2 reaction system of embodiment；
Fig. 4 is the comparison diagram of tyrosine solution and product in embodiment 2；
I is tyrosine solution；II is product；
Fig. 5 a are cationic imide component reaction process；
Fig. 5 b are the process of the present invention.
Specific embodiment
Embodiment 1
A kind of chemical modification method of tyrosine, includes the following steps：
(1) it is 1 according to tyrosine (Tyr), formaldehyde, aniline amount of substance ratio:3:1 weighs reagent, by aniline (8.9*10- 4Mol) with formaldehyde (2.67*10-3Mol) be dissolved in water (20ml), 20-30min stirred under room temperature, be prepared containing imines just from
The solution of son；
(2) by tyrosine 0.16g (8.9*10-4Mol it) is dissolved in the LiBr solution of a concentration of 9.8mol/L of 20mL, is added dropwise
2mL acetic acid, 40 DEG C of stirring in water bath are dissolved to clear liquid, obtain the LiBr solution of tyrosine；
(3) under agitation, the solution of the solution containing cationic imide prepared by step (1) is added to step (2)
In the LiBr solution of the tyrosine of preparation, 5h, rufous liquid are reacted in 40 DEG C of stirring in water bath.
Obtained target product, structural formula is as shown below, target product structure by liquid-mass spectrogram, infrared spectrum,
Uv atlas is proved.This example confirms that Mannich modification synthetic reactions have occurred in tyrosine under the reaction system, simultaneously
The yield for calculating target product is 92.5%, and the solubility of tyrosine and modification tyrosine reaction production can be promoted under the reaction system
The production rate of object.
It can be obtained by Fig. 1, after reaction, because of the increase of conjugated system, there is characteristic absorption in visible region, show
New product is generated, reaction system compares as shown in Figure 2.
Embodiment 2
A kind of chemical modification method of tyrosine, includes the following steps：
(1) it is 1 according to tyrosine (Tyr), formaldehyde, ortho-nitraniline amount of substance ratio:3:1 weighs reagent, by ortho-nitrophenyl
Amine (5*10-4Mol) with formaldehyde (1.5*10-3Mol water (25ml)) is dissolved in, 30-40min is stirred at 40 DEG C, is prepared containing Asia
The solution of amine cation；
(2) tyrosine 0.09g is dissolved in the LiBr solution of a concentration of 9.8mol/L of 20mL, 2mL acetic acid, 40 DEG C of water is added dropwise
Stirring and dissolving is bathed to clear liquid, obtains the LiBr solution of tyrosine；
(3) under agitation, the solution of the solution containing cationic imide prepared by step (1) is added to step (2)
In the LiBr solution of the tyrosine of preparation, 5h, rufous liquid are reacted in 40 DEG C of stirring in water bath.
Target product is obtained, structural formula is as shown below.This example further demonstrates tyrosine under the reaction system
Mannich modification synthetic reactions have occurred, while the yield for having calculated the target product is 89.9%, can be carried under the reaction system
Rise the solubility of tyrosine and the production rate of modification tyrosine reaction product.
It can be obtained by Fig. 3, after reaction, because of the increase of conjugated system, there is characteristic absorption in visible region, show
New product is generated, reaction system compares as shown in Figure 4.
Claims (4)
1. a kind of chemical modification method of tyrosine, which is characterized in that the chemical modification method of the tyrosine includes following step
Suddenly：
（1）Primary amino compound and aldehyde are dissolved in water, reaction is stirred at room temperature, the solution containing cationic imide is prepared；
（2）Tyrosine is dissolved in LiBr solution, carries out acidification, heating stirring reacts to solution clear, obtains junket
The LiBr solution of propylhomoserin；
（3）Under agitation, by step（1）The solution containing cationic imide prepared is added to step（2）The junket ammonia of preparation
In the LiBr solution of acid, heating stirring reaction is filtered to get product；
Step（1）Described in aldehyde be selected from formaldehyde or acetaldehyde；The primary amino compound is selected from aniline or ortho-nitraniline；Primary amino group
A concentration of 0.01-0.05mol/L of compound in water；
Step（2）A concentration of 4-8g/L of the LiBr solution of middle tyrosine；
Step（2）Described in acidification be specially：In step（2）Acetic acid is added in reaction system；The volume of the acetic acid of addition
Ratio with LiBr liquor capacities is 1:10-15.
2. the chemical modification method of tyrosine according to claim 1, which is characterized in that the tyrosine, aldehyde, primary amino group
The ratio of the amount of the substance of compound is 1: 3-4 : 1-1.3.
3. the chemical modification method of tyrosine according to claim 1, which is characterized in that step（2）Described in heat and stir
It mixes specially：It is stirred at 30-60 DEG C of water-bath.
4. the chemical modification method of tyrosine according to claim 1, which is characterized in that step（3）Described in heat and stir
Mixing reaction is specially：2-6h is stirred to react under 40 DEG C of water-baths.
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| CN201610373440.0A CN106083625B (en) | 2016-05-31 | 2016-05-31 | A kind of chemical modification method of tyrosine |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103741507A (en) * | 2013-12-27 | 2014-04-23 | 浙江理工大学 | Covalent bond tinting method applicable to silks |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103741507A (en) * | 2013-12-27 | 2014-04-23 | 浙江理工大学 | Covalent bond tinting method applicable to silks |
Non-Patent Citations (2)
| Title |
|---|
| 基于Ｍannich反应的水溶性芳伯胺染料对蚕丝染色及性能研究;范素菊 等;《浙江理工大学学报(自然科学版)》;20160131;第35卷(第1期);1-8 * |
| 芳伯胺染料的合成及其对蚕丝的Ｍannich法染色研究;李鑫 等;《浙江理工大学学报(自然科学版)》;20150331;第33卷(第2期);164-168 * |
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Effective date of registration: 20201214 Address after: Room 801, 85 Kefeng Road, Huangpu District, Guangzhou City, Guangdong Province Patentee after: Yami Technology (Guangzhou) Co., Ltd Address before: 241000 Beijing Middle Road, Jiujiang District, Wuhu City, Anhui Province Patentee before: ANHUI POLYTECHNIC University |
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Effective date of registration: 20210118 Address after: Room 201, No.5, Lane 3399, Kangxin Road, Pudong New Area, Shanghai Patentee after: SHANGHAI LINKCHEM TECHNOLOGY Co.,Ltd. Address before: Room 801, 85 Kefeng Road, Huangpu District, Guangzhou City, Guangdong Province Patentee before: Yami Technology (Guangzhou) Co., Ltd |