CN109384685A - A kind of preparation method of amino-acid ester - Google Patents
A kind of preparation method of amino-acid ester Download PDFInfo
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- CN109384685A CN109384685A CN201811454777.XA CN201811454777A CN109384685A CN 109384685 A CN109384685 A CN 109384685A CN 201811454777 A CN201811454777 A CN 201811454777A CN 109384685 A CN109384685 A CN 109384685A
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- acid ester
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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
- C07C227/18—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 involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of preparation methods of amino-acid ester, belong to organic compound synthesis field；It is using sulfur trioxide as catalyst and to tie up aqua, and catalytic amino acid reacts the sulfate for preparing amino-acid ester with alcohol, then reaction system is concentrated after removing reaction dissolvent and is dissolved in water, then prepares amino-acid ester with ammonium hydroxide neutralization.A kind of preparation method for amino-acid ester that technical solution of the present invention provides has the advantages that reaction process is mild, high income, purity are good, easy to operate, at low cost.A kind of preparation method of amino-acid ester of the invention centrifuge mother liquor concentration condensed water can straight row biochemical treatment, solid by-product be high-purity sulfuric acid ammonium, can be used as chemical fertilizer use, reaction process green non-pollution, this is advantageous to environmental protection.
Description
Technical field
The present invention relates to organic compounds to synthesize field, and in particular to a kind of preparation method of amino-acid ester.
Background technique
Amino acid esters compound is important Organic Chemicals and organic synthesis intermediate, due to the spy of amino-acid ester
Different physicochemical property, make it medicine, chemical industry, pesticide, fragrance, food, in terms of be all widely used.Amino acid is not
It is same as common organic aliphatic acid, it is connected with amino and carboxyl simultaneously, belong to amphoteric compound, so, the choosing to enzymatic synthesis condition
Select tightened up requirement；This is also restricted the application of typical catalyst, from initial Protic Acid Catalyzed to phase transfer
Catalysis etc. is constantly searching for always making the method and condition that amino acid is quick, facilitates esterification in the industry.The ammonia generallyd use at present
It is that raw material is esterified that the preparation method of base acid esters, which is with amino acid, alcohol, thionyl chloride etc., and thionyl chloride can divide in reaction process
The water generated in solution reaction process, carries out reaction thoroughly, but the sulfur dioxide of strong corrosive is generated in the art production process
And hydrogen chloride gas, the waste water containing sodium chloride and sodium sulfite salt-mixture is generated after lye absorbs, wastewater treatment is very tired
Difficulty does not adapt to environmental development demand.The preparation method of amino-acid ester also has with gas chlorination hydrogen, sulfuric acid, p-methyl benzenesulfonic acid etc.
For the amino-acid ester for preparing of catalyst, the greatest problem of such technique is that the reaction time is longer, needs to consume a large amount of water entrainer,
And product purity is not high, purification difficult.In the test for carrying out amino-acid ester synthesis using resin as catalyst, it is lower that there are yields,
Resin is easy swelling and is crushed, and needs the problems such as regenerating.The synthesis of amino-acid ester has received more and more attention, it is in preparation side
Improvement on improvement in method, especially catalyst choice, it will the production of amino-acid ester is made to become closer to Green Chemistry work
Industry requirement, cost can be lower and lower.
Summary of the invention
Summary of the invention technical solution of the present invention provides one kind in line with the purpose for solving problems of the prior art
The preparation method of amino-acid ester；A kind of preparation method of amino-acid ester described in technical solution of the present invention has reaction process temperature
With high income, the feature that purity is good, easy to operate, at low cost, environmentally friendly.A kind of ammonia described in technical solution of the present invention
The preparation method of base acid esters, which is characterized in that it is the following steps are included: (1) is urged using sulfur trioxide as catalyst and aqua is tied up
Change amino acid to react with alcohol, generate the sulfate liquor of amino-acid ester, the sulfate solid after solvent up to amino-acid ester is evaporated off；
(2) amino acid is prepared with ammonium hydroxide neutralization after the sulfate solid of amino-acid ester obtained in step (1) being dissolved with water
Ester is drying to obtain high-purity amino-acid ester again after being separated by solid-liquid separation.A kind of preparation method of the amino-acid ester it is main
Chemical equation is as follows: described selects sulfur trioxide for catalyst, and esterification can be made flat to target product direction
It is steady to carry out, while water caused by esterification can be absorbed and be decomposed again, and then promote esterification complete.
Preferably, the step (1) are as follows: after amino acid, alcohol are added in reaction flask, open stirring, after cooling slowly
Be added dropwise sulfur trioxide, subsequent insulation reaction to reaction carry out thoroughly, subsequent evaporating solvent under reduced pressure up to amino-acid ester sulfate.
The molar ratio of amino acid and alcohol is 1:1.05-3.0 (when other solvents are added) or 1:3-20 (with alcohol in the step (1)
When as reaction dissolvent), when amino acid is reacted with high boiling liquid alcohol, then the ratio 1:1.05-1.25 of amino acid and alcohol.
The molar ratio of amino acid and sulfur trioxide is 1:1.05-1.50 in the step (1).Sulfur trioxide in the step (1)
Dropping temperature be 0-5 DEG C, insulation reaction temperature be 5-45 DEG C.Amino acid in the step (1) and (2) has general formula I,
Alcohol has general formula II: R1 can be alkyl, aryl in formula, and R can be alkyl or the aryl in addition to phenyl and benzyl.It is preferred that
Ground, a kind of preparation method of amino-acid ester, which is characterized in that the reaction dissolvent is selected from methanol, ethyl alcohol, dichloromethane
One of alkane, chloroform, acetone, ether, hexamethylene, petroleum ether.A kind of system of amino-acid ester described in technical solution of the present invention
Preparation Method, beneficial effect brought by it is: esterification reaction process is mild, high income, good product purity, easy to operate, cost
Low, advantages of environment protection is suitble to industrialized production.
Specific embodiment
Specific embodiment is to express that the purpose of the present invention, technical solution clearly, below with reference to embodiment pair
The present invention carry out in detail, be fully described by that is obvious, described embodiment is that a part of technical solution of the present invention is implemented
Example, and it is not all.
To being equipped in the 1000ml four-hole bottle of blender, condenser pipe, thermometer methanol 500ml is added, to hydroxyl in embodiment 1
Base phenylglycine 150g opens stirring, starts that sulfur trioxide 86.2g is added dropwise, after completion of dropwise addition, is warming up to 35-40 DEG C and is protected
Temperature is reacted, and is controlled in HPLC, is concentrated under reduced pressure after reaction, and 800g5 DEG C of obtained solid after methanol of water dissolution is steamed, and system is molten
Start that ammonium hydroxide is added dropwise after clear, dropping temperature≤20 DEG C are neutralized to pH value=8-9, and neutralization is centrifuged after terminating through cooling, pure water leaching
It washes, it is dry, obtain solid p-hydroxyphenylglycine methyl ester 156.6g, molar yield 96.3%.
Methanol 500ml is added to being equipped in the 1000ml four-hole bottle of blender, condenser pipe, thermometer in embodiment 2, and benzene is sweet
Propylhomoserin 151.2g opens stirring, starts that sulfur trioxide 96.1g is added dropwise, after completion of dropwise addition, warms naturally to room temperature and reacted,
It controls in HPLC, is concentrated under reduced pressure after reaction, steam 800g5 DEG C of water dissolution of obtained solid after methanol, start after system dissolved clarification
Ammonium hydroxide is added dropwise, dropping temperature≤20 DEG C are neutralized to pH value=8-9, and cool down centrifugation after neutralization, and pure water elution is dry, must consolidate
Body Phenylglycine methyl ester 158.5g, molar yield 95.9%.
Ethyl alcohol 65ml, dichloromethane is added to being equipped in the 1000ml four-hole bottle of blender, condenser pipe, thermometer in embodiment 3
Alkane 400ml, D-pHPG 150.0g open stirring, start that sulfur trioxide 86.0g is added dropwise, after completion of dropwise addition, are warming up to
40-45 DEG C of progress insulation reaction, it controls in HPLC, is concentrated under reduced pressure after reaction, steam after methanol 800g5 DEG C of obtained solid
Water dissolution starts after system dissolved clarification that ammonium hydroxide is added dropwise, and dropping temperature≤20 DEG C are neutralized to pH value=8-9, cool down after neutralization from
The heart, pure water elution is dry, obtains solid D-pHPG ethyl ester 170.2g, molar yield 97.2%.
Propyl alcohol 350ml, silk ammonia is added to being equipped in the 1000ml four-hole bottle of blender, condenser pipe, thermometer in embodiment 4
Sour 100.0g opens stirring, starts that sulfur trioxide 87.6g is added dropwise, after completion of dropwise addition, warms naturally to room temperature and reacted,
It controls in HPLC, is concentrated under reduced pressure after reaction, steam 800g5 DEG C of water dissolution of obtained solid after methanol, start after system dissolved clarification
Ammonium hydroxide is added dropwise, dropping temperature≤20 DEG C are neutralized to pH value=8-9, and cool down centrifugation after neutralization, and pure water elution is dry, must consolidate
Body serine propyl ester 143.6g, molar yield 97.9%.
Methanol 200ml is added to being equipped in the 1000ml four-hole bottle of blender, condenser pipe, thermometer in embodiment 5, relies ammonia
Sour 50.0g opens stirring, starts that sulfur trioxide 30.9g is added dropwise, after completion of dropwise addition, warms naturally to room temperature and reacted, HPLC
Middle control, is concentrated under reduced pressure after reaction, steams 300g5 DEG C of water dissolution of obtained solid after methanol, starts to be added dropwise after system dissolved clarification
Ammonium hydroxide, dropping temperature≤20 DEG C are neutralized to pH value=8-9, and cool down centrifugation after neutralization, and pure water elution is dry, obtain solid and rely
Propylhomoserin methyl esters 52.5g, molar yield 95.8%.
Methanol 200ml, color ammonia is added to being equipped in the 1000ml four-hole bottle of blender, condenser pipe, thermometer in embodiment 6
Sour 50.0g opens stirring, starts that sulfur trioxide 22.5g is added dropwise, after completion of dropwise addition, warms naturally to room temperature and reacted, HPLC
Middle control, is concentrated under reduced pressure after reaction, steams 300g5 DEG C of water dissolution of obtained solid after methanol, starts to be added dropwise after system dissolved clarification
Ammonium hydroxide, dropping temperature≤20 DEG C are neutralized to pH value=8-9, and cool down centrifugation after neutralization, and pure water elution is dry, obtain solid color
Propylhomoserin methyl esters 51.9g, molar yield 97.1%.
The present invention will not be limited to the embodiments shown herein, all within spirit of that invention and principle, institute
Any modification, equivalent substitution, improvement and etc. of work, should all be included in the protection scope of the present invention.Institute's protection scope of the present invention
It is to fit to the widest scope consistent with principle provided in this article and features of novelty.
Claims (7)
1. a kind of preparation method of amino-acid ester, which is characterized in that it the following steps are included: (1) using sulfur trioxide as catalyst
With tie up aqua, catalytic amino acid is reacted with alcohol, generates the sulfate liquor of amino-acid ester, is evaporated off after solvent up to amino-acid ester
Sulfate solid, after (2) dissolve the sulfate solid of amino-acid ester obtained in step (1) with water, then in ammonium hydroxide and making
Standby amino-acid ester out, is separated by solid-liquid separation, is drying to obtain high-purity amino-acid ester.
2. a kind of preparation method of amino-acid ester according to claim 1, which is characterized in that the step (1) are as follows: will
After amino acid and alcohol are added in solvent, stirring is opened, sulfan is added dropwise, then insulation reaction, HPLC monitoring reaction knot
Beam.
3. a kind of preparation method of amino-acid ester according to claim 1, which is characterized in that ammonia in the step (1)
The molar ratio of base acid and sulfur trioxide is 1:1.05-1.50.
4. a kind of preparation method of amino-acid ester according to claim 1, which is characterized in that three in the step (1)
The dropping temperature of sulfur oxide is 0-5 DEG C, and insulation reaction temperature is 5-45 DEG C.
5. a kind of preparation method of amino-acid ester described in -4 according to claim 1, which is characterized in that the amino acid has
General formula, the alcohol have general formula II: R1 can be alkyl, aryl in formula, and R can be alkyl or in addition to phenyl and benzyl
Aryl.
6. a kind of preparation method of amino-acid ester according to claim 1, which is characterized in that in the step (1): a
When amino acid is reacted with low-boiling liquid alcohol, the low-boiling point liquid alcohol can be used as reaction dissolvent, be added without other solvents；
When other solvents are added, then the ratio of amino acid and alcohol is 1:1.05-3.0；B is reacted when amino acid with high boiling liquid alcohol
When, then the ratio 1:1.05-1.25 of amino acid and alcohol.
7. a kind of preparation method of amino-acid ester according to claim, which is characterized in that the reaction dissolvent is selected from
One of methanol, ethyl alcohol, methylene chloride, chloroform, acetone, ether, hexamethylene, petroleum ether.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811454777.XA CN109384685A (en) | 2018-11-30 | 2018-11-30 | A kind of preparation method of amino-acid ester |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811454777.XA CN109384685A (en) | 2018-11-30 | 2018-11-30 | A kind of preparation method of amino-acid ester |
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| CN109384685A true CN109384685A (en) | 2019-02-26 |
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| CN201811454777.XA Withdrawn CN109384685A (en) | 2018-11-30 | 2018-11-30 | A kind of preparation method of amino-acid ester |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113004160A (en) * | 2021-03-15 | 2021-06-22 | 淮北市博康生物科技有限公司 | Synthetic method of L-serine methyl ester sulfate |
-
2018
- 2018-11-30 CN CN201811454777.XA patent/CN109384685A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113004160A (en) * | 2021-03-15 | 2021-06-22 | 淮北市博康生物科技有限公司 | Synthetic method of L-serine methyl ester sulfate |
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Application publication date: 20190226 |