CN108558688A - A method of preparing Beta-alanine using β-aminopropionitrile - Google Patents
A method of preparing Beta-alanine using β-aminopropionitrile Download PDFInfo
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- CN108558688A CN108558688A CN201810438024.3A CN201810438024A CN108558688A CN 108558688 A CN108558688 A CN 108558688A CN 201810438024 A CN201810438024 A CN 201810438024A CN 108558688 A CN108558688 A CN 108558688A
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- alanine
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- aminopropionitrile
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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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- 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
- C07C227/38—Separation; Purification; Stabilisation; Use of additives
- C07C227/40—Separation; Purification
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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
- C07C227/38—Separation; Purification; Stabilisation; Use of additives
- C07C227/40—Separation; Purification
- C07C227/42—Crystallisation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of methods preparing β alanines using β aminopropionitriles, it is related to drug technical field of organic synthesis, using β aminopropionitriles as raw material, first intermediate β alanine sodium is generated through hydrolysis in the presence of rough vacuum, alkaline matter, hydrolyze the recovered recycling of ammonia generated, neutralized react generates β alanine crude products to intermediate β alanines sodium again with acidic materials, and β alanine crystal is made through recrystallizing in β alanines crude product.Whole process of the present invention is simple for process, the used time is short, easily controllable, energy-saving, so as to get crude product purity i.e. up to 98% or more, and after primary purification i.e. can reach 99.5% or more.
Description
Technical field：
The present invention relates to drug technical field of organic synthesis, and in particular to preparing β-ammonia using β-aminopropionitrile using a kind of
The method of base propionic acid.
Background technology：
Beta-alanine, clear crystal is soluble easily in water, is slightly soluble in ethyl alcohol, does not dissolve in ether and acetone.Beta-alanine master
It is used for synthetic pantothenic acid and calcium pantothenate, carnosine, Sodium Pamidronate, Balsalazide etc., it can also be used to produce plating corrosion inhibiter, be used as life
Object reagent and organic synthesis intermediate are additionally operable to plating corrosion inhibiter and biochemical reagents.Therefore, Beta-alanine medicine, feed,
The application in the fields such as food is very extensive.
At present there are mainly two types of the synthetic methods of Beta-alanine：First method is generated as raw material using acrylic acid, ammonia
Beta-alanine；Second method is to degrade to generate Beta-alanine under alkaline condition using amber Asia amide as raw material.But the
A kind of method needs to use acrylic acid in production process, which is easy polymerization, and reaction process needs to break chemical balance；Second
Kind of method severe reaction conditions and side reaction it is more, need to repeatedly purify.
In order to synthesize the Beta-alanine of high yield, high-purity while reducing cost, reducing three wastes yield, this
Beta-alanine is made using β-aminopropionitrile as raw material, through hydrolyzing, neutralizing technique in company.
Invention content：
Technical problem to be solved by the present invention lies in providing, one kind is simple for process, the used time is short, easily controllable, energy-saving
The method for preparing Beta-alanine using β-aminopropionitrile.
The technical problems to be solved by the invention are realized using technical solution below：
A method of Beta-alanine being prepared using β-aminopropionitrile, using β-aminopropionitrile as raw material, first low true
Intermediate Beta-alanine sodium is generated through hydrolysis in the presence of reciprocal of duty cycle, alkaline matter, hydrolyzes the recovered recycling of ammonia of generation,
Neutralized react generates Beta-alanine crude product to intermediate Beta-alanine sodium again with acidic materials, and Beta-alanine crude product is through weight
Beta-alanine crystal is made in crystallization.
The rough vacuum is -50 ± 10kpa.
The alkaline matter is inorganic base, the one kind of inorganic base in sodium hydroxide, potassium hydroxide.
The acidic materials are inorganic acid, the one kind of inorganic acid in hydrochloric acid, sulfuric acid.
The Beta-alanine crude product carries out decolorization before recrystallization using decolorising agent.I.e. using β-aminopropionitrile as
Raw material first generates intermediate Beta-alanine sodium through hydrolysis in the presence of rough vacuum, alkaline matter, hydrolyzes the ammonia of generation
Recovered recycling, neutralized react generates Beta-alanine crude product, β-ammonia to intermediate Beta-alanine sodium again with acidic materials
Beta-alanine crystal is made through bleaching agent bleaching, recrystallization in base propionic acid crude product.
The decolorising agent selects activated carbon.
The decolorising agent is obtained by the modified processing of 4A molecular screen primary powders, and preparation method is：First by 4A molecular screen primary powders
It is placed in 100-110 DEG C of baking oven and dries to constant weight, roasting 3h at 450-500 DEG C, adding when through naturally cooling to 40 DEG C or less
Enter in absolute ethyl alcohol, and N- hydroxyethyl acrylamides, allyl glycidyl ether and azodiisobutyronitrile is added, is then heated to
Reflux state insulated and stirred is reacted, and gained mixture is recycled ethyl alcohol through being concentrated under reduced pressure after reaction, condensate residue is through super
Micro mist is made in atomizer, is most obtained afterwards through granulationSpherical decolorising agent.
The matter of the 4A molecular screen primary powders, N- hydroxyethyl acrylamides, allyl glycidyl ether and azodiisobutyronitrile
Amount is than being 15-25: 1-5: 1-5: 0.05-0.5.
The decolorizing effect of 4A molecular sieves itself is limited, far away from activated carbon, but through above-mentioned modification (N- hydroxylethyls
Aggregated react under azodiisobutyronitrile initiation generates acrylic resin, third generated to amide with allyl glycidyl ether
Decolorising agent is made after three dimensions interacts with 4A molecular screen primary powders in olefin(e) acid resin) after significantly increase the decolorizing effects of 4A molecular sieves
(decolorizing effect for reaching the activated carbon that can match in excellence or beauty).
The reaction route of the present invention is as follows：
Side reaction：
The reaction principle of the present invention：
β-aminopropionitrile is hydrolyzed into Beta-alanine sodium under alkaline condition, is increased using highly basic as catalyst
Add reaction speed；On the other hand it is that the ammonia separate out that reaction generates is made by highly basic, the ammonia for generating reaction through vacuum system
It is discharged from reaction system；Avoid simultaneously in follow-up and when ammonia and Beta-alanine generation amides etc. are miscellaneous in acid condition
Matter reduces crude product purity.Beta-alanine sodium neutralizes to obtain Beta-alanine crude product through acid, and high-purity can be obtained through a water recrystallization
Beta-alanine.
The beneficial effects of the invention are as follows：The present invention is hydrolyzed under alkaline condition using β-aminopropionitrile, while through vacuum system
The ammonia that reaction system generates is discharged system in time, improves reaction efficiency, shortens the reaction time, and subsequently neutralization is avoided to generate amides
Impurity.Whole process is simple for process, the used time is short, easily controllable, energy-saving, so as to get crude product purity i.e. up to 98% or more,
And it can reach 99.5% or more after primary purification.
Specific implementation mode：
In order to make the technical means, the creative features, the aims and the efficiencies achieved by the present invention be easy to understand, tie below
Specific embodiment is closed, the present invention is further explained.
Embodiment 1
By β-aminopropionitrile 100g, 30% sodium hydroxide solution 200g be warming up to 100-120 DEG C, vacuum degree be -50 ±
10kpa reacts 2-4h, and the ammonia for reacting generation absorbs recycling through water.Reaction terminates to be cooled to 10-30 DEG C, with hydrochloric acid tune under stirring
PH to 6-8 is saved, white solid wet product 120g is filtered to obtain after repetition measurement is constant.Water 200g is added to dissolve Beta-alanine crude product 120g,
And adding activated carbon decolorizing, filtrate is cooled to -10-10 DEG C of crystallizations and centrifuges to obtain Beta-alanine 108g, HPLC detection purity after filtering
It is 99.7%, whiteness 99.6%.
Embodiment 2
By β-aminopropionitrile 100g, 30% potassium hydroxide solution 200g be warming up to 100-120 DEG C, vacuum degree be -50 ±
10kpa reacts 2-4h, and the ammonia for reacting generation absorbs recycling through water.Reaction terminates to be cooled to 10-30 DEG C, with hydrochloric acid tune under stirring
PH to 6-8 is saved, white solid wet product 118g is filtered to obtain after repetition measurement is constant.Water 200g is added to dissolve Beta-alanine crude product 118g,
And adding activated carbon decolorizing, filtrate is cooled to -10-10 DEG C of crystallizations and centrifuges to obtain Beta-alanine 107g, HPLC detection purity after filtering
It is 99.6%, whiteness 99.6%.
Embodiment 3
By β-aminopropionitrile 100g, 30% sodium hydroxide solution 200g be warming up to 100-120 DEG C, vacuum degree be -50 ±
10kpa reacts 2-4h, and the ammonia for reacting generation absorbs recycling through water.Reaction terminates to be cooled to 10-30 DEG C, with hydrochloric acid tune under stirring
PH to 6-8 is saved, white solid wet product 119g is filtered to obtain after repetition measurement is constant.Water 200g is added to dissolve Beta-alanine crude product 120g,
And adding bleaching agent bleaching, filtrate is cooled to -10-10 DEG C of crystallizations and centrifuges to obtain Beta-alanine 109g, HPLC detection purity after filtering
It is 99.7%, whiteness 99.6%.
The preparation of decolorising agent：First 24g 4A molecular screen primary powders are placed in 100-110 DEG C of baking oven and are dried to constant weight, then at
3h being roasted at 450-500 DEG C, being added in absolute ethyl alcohol when through naturally cooling to 40 DEG C or less, and 3g N- hydroxylethyls are added
Amide, 3g allyl glycidyl ethers and 0.24g azodiisobutyronitriles are then heated to the reaction of reflux state insulated and stirred, instead
Gained mixture is recycled into ethyl alcohol through being concentrated under reduced pressure after answering, condensate residue is made micro mist through micronizer, most passes through afterwards
Granulation obtainsSpherical decolorising agent.
Embodiment 4
By β-aminopropionitrile 100g, 30% sodium hydroxide solution 200g be warming up to 100-120 DEG C, vacuum degree be -50 ±
10kpa reacts 2-4h, and the ammonia for reacting generation absorbs recycling through water.Reaction terminates to be cooled to 10-30 DEG C, with hydrochloric acid tune under stirring
PH to 6-8 is saved, white solid wet product 120g is filtered to obtain after repetition measurement is constant.Water 200g is added to dissolve Beta-alanine crude product 120g,
And adding bleaching agent bleaching, filtrate is cooled to -10-10 DEG C of crystallizations and centrifuges to obtain Beta-alanine 108g, HPLC detection purity after filtering
It is 99.7%, whiteness 99.6%.
The preparation of decolorising agent：First 24g 4A molecular screen primary powders are placed in 100-110 DEG C of baking oven and are dried to constant weight, then at
3h being roasted at 450-500 DEG C, being added in absolute ethyl alcohol when through naturally cooling to 40 DEG C or less, and 3g N- hydroxylethyls are added
Amide, 3g allyl glycidyl ethers and 0.24g azodiisobutyronitriles are then heated to the reaction of reflux state insulated and stirred, instead
Gained mixture is recycled into ethyl alcohol through being concentrated under reduced pressure after answering, condensate residue is made micro mist through micronizer, most passes through afterwards
Granulation obtainsSpherical decolorising agent.
Reference examples
By β-aminopropionitrile 100g, 30% sodium hydroxide solution 200g be warming up to 100-120 DEG C, vacuum degree be -50 ±
10kpa reacts 2-4h, and the ammonia for reacting generation absorbs recycling through water.Reaction terminates to be cooled to 10-30 DEG C, with hydrochloric acid tune under stirring
PH to 6-8 is saved, white solid wet product 120g is filtered to obtain after repetition measurement is constant.Water 200g is added to dissolve Beta-alanine crude product 120g,
And adding bleaching agent bleaching, filtrate is cooled to -10-10 DEG C of crystallizations and centrifuges to obtain Beta-alanine 106g, HPLC detection purity after filtering
It is 99.7%, whiteness 98.9%.
Decolorising agent uses4A molecular sieves (the global molecular sieve Co., Ltd in Henan).Embodiment 1-4 with compare
Activated carbon is identical as the additive amount of decolorising agent in example.
By embodiment 1-4 it is found that the present invention has the de- of the activated carbon that matches in excellence or beauty using the molecular sieve modified decolorising agents obtained of 4A
Color effect, products made thereby whiteness can reach 99.6% under identical crystallization condition；And the 4A molecular sieves of non-modified processing are de-
Color effect is poor, and products made thereby whiteness is only 98.9% under identical crystallization condition, and not up to 99%.
The above shows and describes the basic principles and main features of the present invention and the advantages of the present invention.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent thereof.
Claims (8)
1. a kind of method preparing Beta-alanine using β-aminopropionitrile, it is characterised in that：Using β-aminopropionitrile as raw material,
Intermediate Beta-alanine sodium first is generated through hydrolysis in the presence of rough vacuum, alkaline matter, the ammonia for hydrolyzing generation passes through back
It receives and recycles, neutralized react generates Beta-alanine crude product, beta-amino third to intermediate Beta-alanine sodium again with acidic materials
Beta-alanine crystal is made through recrystallizing in acid crude.
2. the method according to claim 1 for preparing Beta-alanine using β-aminopropionitrile, it is characterised in that：It is described low
Vacuum degree is -50 ± 10kpa.
3. the method according to claim 1 for preparing Beta-alanine using β-aminopropionitrile, it is characterised in that：The alkali
Property substance be inorganic base, the one kind of inorganic base in sodium hydroxide, potassium hydroxide.
4. the method according to claim 1 for preparing Beta-alanine using β-aminopropionitrile, it is characterised in that：The acid
Property substance be inorganic acid, the one kind of inorganic acid in hydrochloric acid, sulfuric acid.
5. the method according to claim 1 for preparing Beta-alanine using β-aminopropionitrile, it is characterised in that：The β-
Alanine crude product carries out decolorization before recrystallization using decolorising agent.
6. the method according to claim 5 for preparing Beta-alanine using β-aminopropionitrile, it is characterised in that：It is described de-
Toner selects activated carbon.
7. the method according to claim 5 for preparing Beta-alanine using β-aminopropionitrile, it is characterised in that：It is described de-
Toner is obtained by the modified processing of 4A molecular screen primary powders, and preparation method is：4A molecular screen primary powders are first placed in 100-110 DEG C of baking
It being dried to constant weight in case, 3h is roasted at 450-500 DEG C, be added in absolute ethyl alcohol when through naturally cooling to 40 DEG C or less, and
N- hydroxyethyl acrylamides, allyl glycidyl ether and azodiisobutyronitrile is added, is then heated to reflux state heat preservation and stirs
Reaction is mixed, gained mixture is recycled into ethyl alcohol through being concentrated under reduced pressure after reaction, condensate residue is made micro- through micronizer
Powder is most obtained through granulation afterwardsSpherical decolorising agent.
8. the method according to claim 7 for preparing Beta-alanine using β-aminopropionitrile, it is characterised in that：The 4A
Molecular screen primary powder, N- hydroxyethyl acrylamides, allyl glycidyl ether and azodiisobutyronitrile mass ratio be 15-25:1-
5:1-5:0.05-0.5。
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110343052A (en) * | 2019-08-13 | 2019-10-18 | 广州怡和生物科技有限公司 | A kind of preparation method of Beta-alanine |
| CN110903207A (en) * | 2019-12-16 | 2020-03-24 | 江苏兄弟维生素有限公司 | Method for producing aminopropionic acid and sodium sulfate by using β -formylaminopropionitrile and application of aminopropionic acid and sodium sulfate |
| CN111333525A (en) * | 2020-04-15 | 2020-06-26 | 大连韦德生化科技有限公司 | Continuous production process of β -alanine |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102827010A (en) * | 2012-08-31 | 2012-12-19 | 江苏兄弟维生素有限公司 | Novel beta-aminopropanoic acid synthesis technology |
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- 2018-05-09 CN CN201810438024.3A patent/CN108558688A/en not_active Withdrawn
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102827010A (en) * | 2012-08-31 | 2012-12-19 | 江苏兄弟维生素有限公司 | Novel beta-aminopropanoic acid synthesis technology |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110343052A (en) * | 2019-08-13 | 2019-10-18 | 广州怡和生物科技有限公司 | A kind of preparation method of Beta-alanine |
| CN110903207A (en) * | 2019-12-16 | 2020-03-24 | 江苏兄弟维生素有限公司 | Method for producing aminopropionic acid and sodium sulfate by using β -formylaminopropionitrile and application of aminopropionic acid and sodium sulfate |
| CN111333525A (en) * | 2020-04-15 | 2020-06-26 | 大连韦德生化科技有限公司 | Continuous production process of β -alanine |
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