CN104557579B - Method for preparing betaine - Google Patents
Method for preparing betaine Download PDFInfo
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- CN104557579B CN104557579B CN201410746886.4A CN201410746886A CN104557579B CN 104557579 B CN104557579 B CN 104557579B CN 201410746886 A CN201410746886 A CN 201410746886A CN 104557579 B CN104557579 B CN 104557579B
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Abstract
The invention relates to betaine, particularly a method for preparing betaine. The method mainly solves the following technical problems in the prior art: diazomethane used as the raw material has the defects of high tendency to explosion, high flammability and strong stimulation, and thus, is inconvenient for transportation, storage and use; when chloroacetic acid is used as the raw material, the salt content in the product is too high; and when choline is used as the raw material, the market price of the noble metal is higher, and thus, the manufacturing cost is higher. The method comprises the following steps: adding choline chloride, acetone or acetonitrile and a catalyst into a reactor, sufficiently stirring uniformly, dropwisely adding a sodium hypochlorite solution and a sodium chlorite solution into the mixture while stirring, after finishing addition, sufficiently stirring to react, adding a proper amount of sodium thiosulfate solution to remove the unreacted oxidizer, distilling to remove most of the solvent, removing inorganic salt ions from the residues through an ionic macroporous adsorbent resin to obtain a betaine water solution, dewatering, filtering, and carrying out vacuum drying to obtain the betaine fine product.
Description
Technical field
The present invention relates to a kind of glycine betaine, especially relate to a kind of method preparing glycine betaine.
Background technology
In recent years, glycine betaine, as a kind of important feed addictive, participates in living organism metabolism in feeding process, carries
For active methyl, constitute transmethylase with cysteine, participate in methyl reaction.Thus in feeding process glycine betaine use
Growing up healthy and sound of herding and poultry can effectively be ensured, and obtain more preferable meat after slaughter.It is in modern animal husbandry
Application be increasingly taken seriously.
At present, the main preparation methods of glycine betaine have following several：One kind is using glycine and diazomethane reaction system
Standby form (Chemische Berichte, 83,420-431,1950), but because diazomethane is gas at normal temperatures, and
And belong to explosive, flammable, high poison and tool strong and stimulating, therefore transport, store and using being also required to special condition, easily exist
Potential safety hazard；
Second method is to be prepared from (US 5696287) with trimethylamine and chloroacetate reaction, and the method is domestic at present
Commonly used production method, but salt is contained it is impossible to meet some containing a small amount of sodium chloride in the glycine betaine of this method preparation
Amount has the field of particular/special requirement；
The third method is to be raw material (WO 2001040818) with choline, uses oxygen oxygen under noble metal (as Pt) catalysis
Change and obtain glycine betaine, but the method uses noble metal, and the use of oxygen is also required to special condition, therefore cost relatively
Height, is unfavorable for mass producing.
Content of the invention
The present invention is to provide a kind of method preparing glycine betaine, its mainly solve existing for prior art with diazonium first
Alkane is raw material, and diazomethane is gas at normal temperatures, belongs to explosive, flammable, high poison and tool strong and stimulating, therefore transport, storage
With using being also required to special bar, easily there is potential safety hazard；This invention also solves with monoxone as raw material, and produce
The higher problem of salt content in product；And this invention also solves with choline as raw material, and precious metal marketplace price is higher, thus
The technical problem of the higher grade of manufacturing cost.
The above-mentioned technical problem of the present invention is mainly addressed by following technical proposals：
A kind of method preparing glycine betaine of the present invention is it is characterised in that described method includes：
A. add Choline Chloride, acetone or acetonitrile in the reactor, catalyst stirs, wherein Choline Chloride with
The mass ratio of acetone or acetonitrile, catalyst is 1：4～8：1:0.02；
B. dropping while stirring adds liquor natrii hypochloritis and sodium chlorite solution, Choline Chloride and time chlorine in the mixture
The mass ratio of acid sodium solution is 1：2.40～2.95, Choline Chloride is 1 with the mass ratio of sodium chlorite solution：12.9～14.3,
Add and be sufficiently stirred for after finishing reacting；
C. after the completion of reaction, stir the appropriate hypo solution of lower addition and remove unreacted oxidant, then lead to
Cross and most of solvent is distilled off, it is water-soluble that residue obtains glycine betaine through ionic macroporous absorbent resin removing inorganic ion
Liquid, air-distillation removes most of water, the solid of precipitation is collected by filtration, obtains glycine betaine fine work after vacuum drying.
The reaction equation of the present invention is：
Reactor is the three-necked bottle equipped with reflux condensing tube, thermometer, constant pressure funnel and magnetic stirring apparatus, this
Bright each step raw material is commercially available, wide material sources, in liberal supply, and low price, can effectively control production cost.This
Bright reaction condition is relatively mild and process is simple, and each step reaction is more conventional operation, it is to avoid using diazomethane so that raw
The security produced and environmental protection aspect have obtained effective guarantee.
The present invention is mainly in R＆D process and encounters some on the selection of oxidation system and oxidant proportioning consumption and be stranded
Difficulty, the product quality that different oxidation systems obtains is uneven, the product jaundice that oxidizer excessively obtains, and yield
Relatively low；Oxidizer is very few to obtain incomplete product, isolates and purifies difficulty.But we are ground by this field of having accumulated
The experience of sending out, has redesigned the orthogonal experiment of set of system, thus having found out preferably reaction condition, and achieves preferably
Effect.
Preferably, catalyst is 2,6- lupetidine nitrogen oxides or 2 in described step a, 2,6,6- tetramethyls
Piperidine nitroxide.
Preferably, described liquor natrii hypochloritis is 10% with the concentration of sodium chlorite solution.
Preferably, the temperature of stirring reaction is 20～30 DEG C in described step b.
Preferably, in described step b stirring reaction time be 6～10 hours.
Preferably, hypo solution adds until starch potassium iodide paper no longer becomes blue in described step c.
Preferably, described vacuum drying condition is 60 DEG C/10mmHg, the time being dried is 6 hours.
Therefore, the present invention has using the various raw materials being readily obtained, and each step reaction condition is gentle, process is simple, each step
Reaction is routine operation, and the security of production is guaranteed, and effectively avoids using expensive raw material, reduces
The cost of product, is allowed to large-scale application and is possibly realized, and the final product outward appearance that obtains and proterties and content all reach
To higher level.
Specific embodiment
Below by embodiment, technical scheme is described in further detail.
Embodiment 1：A kind of method preparing glycine betaine of this example, its step is：
A. add chlorine in the three-necked bottle equipped with reflux condensing tube, thermometer, constant pressure funnel and magnetic stirring apparatus
Change choline (139.5g, 1.0mol), acetonitrile 1100g and catalyst 2,2,6,6- tetramethyl piperidine nitrogen oxides (2.79g)；
B. in the mixture while stirring dropping add mass concentration ratio be 10% liquor natrii hypochloritis (409.7g) and
Mass concentration ratio is 10% sodium chlorite solution (1990g), continues stirring reaction 10 hours after completion of dropping.
C., after reaction terminates, stirring is lower to add appropriate hypo solution to the constant indigo plant of starch potassium iodide paper, then
It is removed by distillation most of solvent, volume concentration to 10%, residual solution removes inorganic salts through ionic macroporous absorbent resin
Ion obtains aqueous solutions of betaine, and air-distillation removes most of water, volume concentration to 10%, has solid to separate out, is collected by filtration
Solid, is dried 6 hours under 60 DEG C/10mmHg, obtains glycine betaine 105.4g, yield about 90.1%.
The fusing point of the glycine betaine fine work obtaining is 227.1-227.9 DEG C (decomposition), 1H-NMR (d-DMSO):δ3.37(9H,
S), 4.52 (2H, s) .MS (EI), m/z 118 (M+H).
Embodiment 2：A kind of method preparing glycine betaine of this example, its step is：
A. add chlorine in the three-necked bottle equipped with reflux condensing tube, thermometer, constant pressure funnel and magnetic stirring apparatus
Change choline (139.5g, 1.0mol), acetonitrile 560g and catalyst 2,6- lupetidine nitrogen oxides (2.79g)；
B. in the mixture while stirring dropping add mass concentration ratio be 10% liquor natrii hypochloritis (335.3g) and
Mass concentration ratio is 10% sodium chlorite solution (1810g), continues stirring reaction 6 hours after completion of dropping.
C., after reaction terminates, stirring is lower to add appropriate hypo solution to the constant indigo plant of starch potassium iodide paper, then
It is removed by distillation most of solvent, volume concentration to 10%, residual solution removes inorganic salts through ionic macroporous absorbent resin
Ion obtains aqueous solutions of betaine, and air-distillation removes most of water, volume concentration to 10%, has solid to separate out, is collected by filtration
Solid, is dried 6 hours under 60 DEG C/10mmHg, obtains glycine betaine 89.3g, yield about 76.3%.
The fusing point of the glycine betaine fine work obtaining is 227.1-227.9 DEG C (decomposition), 1H-NMR (d-DMSO):δ3.37(9H,
S), 4.52 (2H, s) .MS (EI), m/z 118 (M+H).
Embodiment 3：A kind of method preparing glycine betaine of this example, its step is：
A. add chlorine in the three-necked bottle equipped with reflux condensing tube, thermometer, constant pressure funnel and magnetic stirring apparatus
Change choline (139.5g, 1.0mol), acetonitrile 850g and catalyst 2,2,6,6- tetramethyl piperidine nitrogen oxides (2.79g)；
B. in the mixture while stirring dropping add mass concentration ratio be 10% liquor natrii hypochloritis (365.5g) and
Mass concentration ratio is 10% sodium chlorite solution (1900g), continues stirring reaction 8 hours after completion of dropping.
C., after reaction terminates, stirring is lower to add appropriate hypo solution to the constant indigo plant of starch potassium iodide paper, then
It is removed by distillation most of solvent, volume concentration to 10%, residual solution removes inorganic salts through ionic macroporous absorbent resin
Ion obtains aqueous solutions of betaine, and air-distillation removes most of water, volume concentration to 10%, has solid to separate out, is collected by filtration
Solid, is dried 6 hours under 60 DEG C/10mmHg, obtains glycine betaine 98.7g, yield about 84.4%.
The fusing point of the glycine betaine fine work obtaining is 227.1-227.9 DEG C (decomposition), 1H-NMR (d-DMSO):δ3.37(9H,
S), 4.52 (2H, s) .MS (EI), m/z 118 (M+H).
Embodiment 4：A kind of method preparing glycine betaine of this example, its step is：
A. add chlorine in the three-necked bottle equipped with reflux condensing tube, thermometer, constant pressure funnel and magnetic stirring apparatus
Change choline (139.5g, 1.0mol), acetone 1000g and catalyst 2,2,6,6- tetramethyl piperidine nitrogen oxides (2.79g)；
B. dropping adds liquor natrii hypochloritis (405g) and the matter that mass concentration ratio is 10% while stirring in the mixture
Amount specific concentration is 10% sodium chlorite solution (1950g), continues stirring reaction 10 hours after completion of dropping.
C., after reaction terminates, stirring is lower to add appropriate hypo solution to the constant indigo plant of starch potassium iodide paper, then
It is removed by distillation most of solvent, volume concentration to 10%, residual solution removes inorganic salts through ionic macroporous absorbent resin
Ion obtains aqueous solutions of betaine, and air-distillation removes most of water, volume concentration to 10%, has solid to separate out, is collected by filtration
Solid, is dried 6 hours under 60 DEG C/10mmHg, obtains glycine betaine 103.6g, yield about 88.5%.
The fusing point of the glycine betaine fine work obtaining is 227.1-227.9 DEG C (decomposition), 1H-NMR (d-DMSO):δ3.37(9H,
S), 4.52 (2H, s) .MS (EI), m/z 118 (M+H).
Embodiment 5：A kind of method preparing glycine betaine of this example, its step is：
A. add chlorine in the three-necked bottle equipped with reflux condensing tube, thermometer, constant pressure funnel and magnetic stirring apparatus
Change choline (139.5g, 1.0mol), acetone 600g and catalyst 2,6- lupetidine nitrogen oxides (2.79g)；
B. dropping adds liquor natrii hypochloritis (350g) and the matter that mass concentration ratio is 10% while stirring in the mixture
Amount specific concentration is 10% sodium chlorite solution (1830g), continues stirring reaction 7 hours after completion of dropping.
C., after reaction terminates, stirring is lower to add appropriate hypo solution to the constant indigo plant of starch potassium iodide paper, then
It is removed by distillation most of solvent, volume concentration to 10%, residual solution removes inorganic salts through ionic macroporous absorbent resin
Ion obtains aqueous solutions of betaine, and air-distillation removes most of water, volume concentration to 10%, has solid to separate out, is collected by filtration
Solid, is dried 6 hours under 60 DEG C/10mmHg, obtains glycine betaine 92.8g, yield about 79.3%.
The fusing point of the glycine betaine fine work obtaining is 227.1-227.9 DEG C (decomposition), 1H-NMR (d-DMSO):δ3.37(9H,
S), 4.52 (2H, s) .MS (EI), m/z 118 (M+H).
Embodiment 6：A kind of method preparing glycine betaine of this example, its step is：
A. add chlorine in the three-necked bottle equipped with reflux condensing tube, thermometer, constant pressure funnel and magnetic stirring apparatus
Change choline (139.5g, 1.0mol), acetone 900g and catalyst 2,2,6,6- tetramethyl piperidine nitrogen oxides (2.79g)；
B. dropping adds liquor natrii hypochloritis (380g) and the matter that mass concentration ratio is 10% while stirring in the mixture
Amount specific concentration is 10% sodium chlorite solution (1920g), continues stirring reaction 9 hours after completion of dropping.
C., after reaction terminates, stirring is lower to add appropriate hypo solution to the constant indigo plant of starch potassium iodide paper, then
It is removed by distillation most of solvent, volume concentration to 10%, residual solution removes inorganic salts through ionic macroporous absorbent resin
Ion obtains aqueous solutions of betaine, and air-distillation removes most of water, volume concentration to 10%, has solid to separate out, is collected by filtration
Solid, is dried 6 hours under 60 DEG C/10mmHg, obtains glycine betaine 96.4g, yield about 82.4%.
The fusing point of the glycine betaine fine work obtaining is 227.1-227.9 DEG C (decomposition), 1H-NMR (d-DMSO):δ3.37(9H,
S), 4.52 (2H, s) .MS (EI), m/z 118 (M+H).
The foregoing is only the specific embodiment of the present invention, but the architectural feature of the present invention is not limited thereto, Ren Heben
The technical staff in field in the field of the invention, all cover among the scope of the claims of the present invention by the change made or modification.
Claims (3)
1. a kind of method preparing glycine betaine is it is characterised in that described method includes：
A. Choline Chloride, acetone or acetonitrile are added in the reactor, catalyst stirs, wherein Choline Chloride and acetone
Or the mass ratio of acetonitrile, catalyst is 1：4～8：0.02, catalyst is 2,6- lupetidine nitrogen oxides or 2,2,6,6-
Tetramethyl piperidine nitrogen oxides；
B. dropping adds liquor natrii hypochloritis and sodium chlorite solution, Choline Chloride and sodium hypochlorite while stirring in the mixture
The mass ratio of solution is 1：2.40～2.95, Choline Chloride is 1 with the mass ratio of sodium chlorite solution：12.9～14.3, secondary chlorine
Acid sodium solution is all 10% with the concentration of sodium chlorite solution, adds and is sufficiently stirred for after finishing reacting；The temperature of stirring reaction is 20
～30 DEG C, the time of stirring reaction is 6～10 hours；
C. after the completion of reaction, stir the appropriate hypo solution of lower addition and remove unreacted oxidant, then by steaming
Evaporate the most of solvent of removing, residue removes inorganic ion through ionic macroporous absorbent resin and obtains aqueous solutions of betaine,
Air-distillation removes most of water, the solid of precipitation is collected by filtration, obtains glycine betaine fine work after vacuum drying.
2. a kind of method preparing glycine betaine according to claim 1 is it is characterised in that thiosulfuric acid in described step c
Sodium solution adds until starch potassium iodide paper no longer becomes blue.
3. a kind of method preparing glycine betaine according to claim 1 is it is characterised in that described vacuum drying condition is
60 DEG C/10mmHg, the time being dried is 6 hours.
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| CN201410746886.4A CN104557579B (en) | 2014-12-09 | 2014-12-09 | Method for preparing betaine |
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| CN201410746886.4A CN104557579B (en) | 2014-12-09 | 2014-12-09 | Method for preparing betaine |
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| CN104557579B true CN104557579B (en) | 2017-02-22 |
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| DE19524338A1 (en) * | 1995-07-04 | 1997-01-09 | Degussa | N-Substd. aminoacid prepn., used in sweeteners and pharmaceuticals - by oxidn. of corresp. amino-alcohol with hypochlorite in presence of TEMPO |
| JP2002511440A (en) * | 1998-04-09 | 2002-04-16 | メルク エンド カムパニー インコーポレーテッド | Oxidation method using TEMPO |
| ES2228569T3 (en) * | 1999-08-06 | 2005-04-16 | Akzo Nobel N.V. | PROCESS TO PREPARE BETAINAS. |
| JP2009114143A (en) * | 2007-11-08 | 2009-05-28 | Nissan Chem Ind Ltd | Process for producing carboxylic acid from primary alcohol |
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Denomination of invention: A method for preparing betaine Effective date of registration: 20221014 Granted publication date: 20170222 Pledgee: Xiaoshan Branch of Agricultural Bank of China Ltd. Pledgor: HEALTHY (HANGZHOU) HUSBANDRY SCI-TECH CO.,LTD. Registration number: Y2022980018382 |
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