CN106083625A - A kind of chemical modification method of tyrosine - Google Patents
A kind of chemical modification method of tyrosine Download PDFInfo
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- CN106083625A CN106083625A CN201610373440.0A CN201610373440A CN106083625A CN 106083625 A CN106083625 A CN 106083625A CN 201610373440 A CN201610373440 A CN 201610373440A CN 106083625 A CN106083625 A CN 106083625A
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- tyrosine
- chemical modification
- modification method
- solution
- reaction
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- NOVXQRMCFXAYNS-UHFFFAOYSA-N NC(Cc(cc1CNc2ccccc2)ccc1O)C(O)=O Chemical compound NC(Cc(cc1CNc2ccccc2)ccc1O)C(O)=O NOVXQRMCFXAYNS-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- 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
Abstract
The invention provides the chemical modification method of a kind of tyrosine, compared with prior art, the present invention utilizes LiBr to dissolve tyrosine, and dissolubility reaches 8g/L, significantly larger than tyrosine dissolubility in DMF and methanol.High tyrosine concentration not only promotes the carrying out of reaction, improves reaction efficiency, and, this stable system, reaction condition is gentle, and water-bath 40 DEG C can react, it is not necessary to high temperature, do not destroy modification tyrosine or the performance of protein, provide possible for efficiently modifying tyrosine.
Description
Technical field
The invention belongs to protein modification art, be specifically related to the chemical modification method of a kind of tyrosine.
Background technology
Tyrosine, is called for short Tyr or Y, is a kind of aromatic amino acid, is also 20 kinds of histone amino for synthetic protein
One of acid, it belongs to non essential amino acid.It is widely used in crude drug, food additive and biochemical reagents etc..
At present, to by chemical modification modified feedstock character so that it is have and more multi-functional attracted more and more people's
Research.Such as ultraviolet-absorbing group is modified on tyrosine molecule, the light stability of himself can be promoted；If by quinoline promise
The structural modifications such as ketone, ether ketone, on tyrosine molecule, can give the functions such as its antibacterial, automatically cleaning.If the function cheese ammonia by synthesis
Acid is used for preparing albuminous membranae or azelon etc., will obtain functional protein material.
But, because tyrosine has higher dissolving selectivity, so, in prior art, the chemical modification to tyrosine becomes
Fruit is the most notable.
Summary of the invention
The invention provides the chemical modification method of a kind of tyrosine, according to the construction features of tyrosine, utilize Mannich
Reaction, it is achieved the chemical modification to tyrosine, tyrosine dissolubility is high, and reaction efficiency is high, and reaction condition is gentle, does not destroy modification
Tyrosine or the performance of protein.
The chemical modification method of a kind of tyrosine that the present invention provides, comprises the following steps:
(1) primary amino compound and aldehyde being dissolved in water, reaction is stirred at room temperature, prepare containing cationic imide is molten
Liquid；
(2) being dissolved in by tyrosine in LiBr solution, carry out acidification, heated and stirred, reaction, to solution clear, obtains
LiBr solution to tyrosine；
(3) solution of the solution containing cationic imide under agitation, step (1) prepared joins step (2)
In the LiBr solution of the tyrosine of preparation, heated and stirred is reacted, and filters, obtains product.
In the present invention, the ratio of the amount of the material of tyrosine, aldehyde, primary amino compound is 1:3-4:1-1.3；
Described in step (1), aldehyde is selected from, but not limited to, formaldehyde, acetaldehyde；Described primary amino compound is selected from, but not limited to, aniline
Or ortho-nitraniline.
Further, can also add acetic acid or formic acid in step (1) in system, regulation pH value is 4, makes primary amine groups
Compound generates ammonium salt, to increase its dissolubility.
Stirring reaction 20-35min in step (1).
In step (1), primary amino compound or aldehyde concentration in water are 0.01-0.05mol/L.
In step (2), the concentration of LiBr solution is 9.0-10mol/L；Described heated and stirred is particularly as follows: at water-bath 30-60 DEG C
Stirring.
Acidification described in step (2) particularly as follows: in step (2) reaction system add acetic acid, the acetic acid of addition
The ratio of volume and LiBr liquor capacity is 1:10-15.
In step (2), the concentration of the LiBr solution of tyrosine is 4-8g/L.
The reaction of heated and stirred described in step (3) is particularly as follows: stir reaction 2-6h under 40 DEG C of water-baths.
Preparing cationic imide component reaction process is:
Inventor gives in course of reaction, be not primary amino compound, be secondary amino group, agent is modified, please
Check whether rationally.
The process of the present invention is:
Compared with prior art, the present invention utilizes LiBr to dissolve tyrosine, and dissolubility reaches 8g/L, significantly larger than cheese ammonia
Acid dissolubility in DMF and methanol.(, at DMF dissolubility less than 0.36g/L, tyrosine is little at the dissolubility of methanol for tyrosine
In 0.38g/L.) high tyrosine concentration not only promotes the carrying out of reaction, improves reaction efficiency, and, this stable system,
Reaction condition is gentle, and water-bath 40 DEG C can react, it is not necessary to high temperature, does not destroy modification tyrosine or the performance of protein,
There is provided possible for efficiently modifying tyrosine.
Accompanying drawing explanation
Fig. 1 is the UV spectrogram of embodiment 1 reaction system；
Fig. 2 is tyrosine solution and the comparison diagram of product in embodiment 1；
I is tyrosine solution；II is product；
Fig. 3 is the UV spectrogram of embodiment 2 reaction system；
Fig. 4 is tyrosine solution and the comparison diagram of product in embodiment 2；
I is tyrosine solution；II is product.
Detailed description of the invention
Embodiment 1
The chemical modification method of a kind of tyrosine, comprises the following steps:
(1) it is that 1:3:1 weighs reagent, by aniline (8.9*10 according to tyrosine (Tyr), formaldehyde, aniline thing mass ratio- 4Mol) with formaldehyde (2.67*10-3Mol) be dissolved in water (20ml), under room temperature stir 20-30min, prepare containing imines just from
The solution of son；
(2) by tyrosine 0.16g (8.9*10-4Mol) it is dissolved in the LiBr solution that 20mL concentration is 9.8mol/L, dropping
2mL acetic acid, 40 DEG C of stirring in water bath are dissolved to clear liquid, obtain the LiBr solution of tyrosine；
(3) solution of the solution containing cationic imide under agitation, step (1) prepared joins step (2)
In the LiBr solution of the tyrosine of preparation, react 5h, rufous liquid 40 DEG C of stirring in water bath.
Having obtained target product, structural formula is as follows, and target product structure is by liquid-mass spectrum, infrared spectrum, purple
Outer spectrogram is proved.This example confirms that under this reaction system, tyrosine there occurs that Mannich modifies synthetic reaction, surveys simultaneously
The productivity calculating target product is 92.5%, can promote the dissolubility of tyrosine and modify tyrosine product under this reaction system
Production rate.
Can be obtained by Fig. 1, after reaction terminates, because of the increase of conjugated system, in visible region, there is characteristic absorption, show
Generating new product, reaction system contrasts as shown in Figure 2.
Embodiment 2
The chemical modification method of a kind of tyrosine, comprises the following steps:
(1) it is that 1:3:1 weighs reagent, by ortho-nitrophenyl according to tyrosine (Tyr), formaldehyde, ortho-nitraniline thing mass ratio
Amine (5*10-4Mol) with formaldehyde (1.5*10-3Mol) it is dissolved in water (25ml), stirs 30-40min at 40 DEG C, prepare containing Asia
The solution of amine cation；
(2) tyrosine 0.09g is dissolved in the LiBr solution that 20mL concentration is 9.8mol/L, drips 2mL acetic acid, 40 DEG C of water
Bath stirring and dissolving, to clear liquid, obtains the LiBr solution of tyrosine；
(3) solution of the solution containing cationic imide under agitation, step (1) prepared joins step (2)
In the LiBr solution of the tyrosine of preparation, react 5h, rufous liquid 40 DEG C of stirring in water bath.
Having obtained target product, structural formula is as follows.This example demonstrates tyrosine under this reaction system further and sends out
Having given birth to Mannich and modified synthetic reaction, the productivity simultaneously having calculated this target product is 89.9%, can promote under this reaction system
The dissolubility of tyrosine and the production rate of modification tyrosine product.
Can be obtained by Fig. 3, after reaction terminates, because of the increase of conjugated system, in visible region, there is characteristic absorption, show
Generating new product, reaction system contrasts as shown in Figure 4.
Claims (10)
1. the chemical modification method of a tyrosine, it is characterised in that the chemical modification method of described tyrosine includes following step
Rapid:
(1) primary amino compound and aldehyde are dissolved in water, reaction are stirred at room temperature, prepare the solution containing cationic imide；
(2) being dissolved in by tyrosine in LiBr solution, carry out acidification, heated and stirred, reaction, to solution clear, obtains cheese
The LiBr solution of propylhomoserin；
(3) solution of the solution containing cationic imide under agitation, step (1) prepared joins step (2) to be prepared
Tyrosine LiBr solution in, heated and stirred react, filter, obtain product.
The chemical modification method of tyrosine the most according to claim 1, it is characterised in that described tyrosine, aldehyde, primary amino radical
The ratio of the amount of the material of compound is 1:3-4:1-1.3.
The chemical modification method of tyrosine the most according to claim 1 and 2, it is characterised in that aldehyde described in step (1) selects
From but be not limited to formaldehyde, acetaldehyde.
The chemical modification method of tyrosine the most according to claim 1 and 2, it is characterised in that described primary amino compound
It is selected from, but not limited to, aniline or ortho-nitraniline；Primary amino compound or the aldehyde concentration in water is 0.01-0.05mol/L.
The chemical modification method of tyrosine the most according to claim 1, it is characterised in that in step (1) in system also
Can add acetic acid or formic acid, regulation pH value is 4.
The chemical modification method of tyrosine the most according to claim 1, it is characterised in that heat described in step (2) and stir
Mix particularly as follows: stir at water-bath 30-60 DEG C.
The chemical modification method of tyrosine the most according to claim 1, it is characterised in that described in step (2) at acidifying
Reason is particularly as follows: add acetic acid in step (2) reaction system.
The chemical modification method of tyrosine the most according to claim 7, it is characterised in that the acetic acid added in step (2)
Volume and the ratio of LiBr liquor capacity be 1:10-15.
The chemical modification method of tyrosine the most according to claim 1 or 5, it is characterised in that tyrosine in step (2)
The concentration of LiBr solution is 4-8g/L.
The chemical modification method of tyrosine the most according to claim 1, it is characterised in that heat described in step (3) and stir
Mix reaction particularly as follows: 2-6h is reacted in stirring under 40 DEG C of water-baths.
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| Application Number | Priority Date | Filing Date | Title |
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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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| CN201610373440.0A CN106083625B (en) | 2016-05-31 | 2016-05-31 | A kind of chemical modification method of tyrosine |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020011629A1 (en) | 2018-07-07 | 2020-01-16 | Ivica Cepanec | Composition of powderous instant drink, its preparation and use |
Citations (2)
| 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 |
| CN105218842A (en) * | 2015-09-25 | 2016-01-06 | 江南大学 | A kind of enzyme process prepares the method for fibroin/elastin composite film material |
-
2016
- 2016-05-31 CN CN201610373440.0A patent/CN106083625B/en active Active
Patent Citations (2)
| 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 |
| CN105218842A (en) * | 2015-09-25 | 2016-01-06 | 江南大学 | A kind of enzyme process prepares the method for fibroin/elastin composite film material |
Non-Patent Citations (2)
| Title |
|---|
| 李鑫 等: "芳伯胺染料的合成及其对蚕丝的Ｍannich法染色研究", 《浙江理工大学学报(自然科学版)》 * |
| 范素菊 等: "基于Ｍannich反应的水溶性芳伯胺染料对蚕丝染色及性能研究", 《浙江理工大学学报(自然科学版)》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020011629A1 (en) | 2018-07-07 | 2020-01-16 | Ivica Cepanec | Composition of powderous instant drink, its preparation and use |
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| CN106083625B (en) | 2018-07-03 |
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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 |