CN108774146A - A kind of preparation method of glycine betaine methyl ester hydrochloride - Google Patents
A kind of preparation method of glycine betaine methyl ester hydrochloride Download PDFInfo
- Publication number
- CN108774146A CN108774146A CN201810932980.7A CN201810932980A CN108774146A CN 108774146 A CN108774146 A CN 108774146A CN 201810932980 A CN201810932980 A CN 201810932980A CN 108774146 A CN108774146 A CN 108774146A
- Authority
- CN
- China
- Prior art keywords
- glycine betaine
- ester hydrochloride
- methyl ester
- preparation
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
- 229960003237 betaine Drugs 0.000 title claims abstract description 34
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 title claims abstract description 31
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 150000004702 methyl esters Chemical class 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- QABLOFMHHSOFRJ-UHFFFAOYSA-N methyl 2-chloroacetate Chemical compound COC(=O)CCl QABLOFMHHSOFRJ-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims abstract description 26
- 150000001412 amines Chemical class 0.000 claims abstract description 10
- 238000004821 distillation Methods 0.000 claims abstract description 10
- 230000035484 reaction time Effects 0.000 claims description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 16
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 abstract description 8
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 230000007062 hydrolysis Effects 0.000 abstract description 4
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 11
- 239000003513 alkali Substances 0.000 description 6
- 235000016068 Berberis vulgaris Nutrition 0.000 description 5
- 241000335053 Beta vulgaris Species 0.000 description 5
- -1 hydrogen Calcium oxide Chemical class 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005956 quaternization reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 238000005852 acetolysis reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229930013930 alkaloid Natural products 0.000 description 1
- 150000003797 alkaloid derivatives Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- OLBJZJZARFENTH-UHFFFAOYSA-L calcium;2-chloroacetate Chemical compound [Ca+2].[O-]C(=O)CCl.[O-]C(=O)CCl OLBJZJZARFENTH-UHFFFAOYSA-L 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000010931 ester hydrolysis Methods 0.000 description 1
- 229960004275 glycolic acid Drugs 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 150000003385 sodium Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
Classifications
-
- 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
- C07C227/04—Formation of amino groups in compounds containing carboxyl groups
- C07C227/06—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid
- C07C227/08—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid by reaction of ammonia or amines with acids containing functional groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of preparation methods of glycine betaine methyl ester hydrochloride, comprise the concrete steps that：Methyl chloroacetate is added into reaction bulb, then passes to front three amine gas and is reacted, after reaction, air-distillation deviates from unreacted methyl chloroacetate to get glycine betaine methyl ester hydrochloride；Wherein, the mol ratio of methyl chloroacetate and trimethylamine is 1.2~2：1.The preparation method of the present invention, realize the Quantitative yield of trimethylamine, avoid the hydrolysis of methyl chloroacetate, product yield reaches 99% or more, stable quality, simple for process, low energy consumption, it is low fundamentally to overcome monoxone facile hydrolysis, conversion ratio in traditional soda technique, trimethylamine is excessive, and discharge amount of exhaust gas is big, easily causes the key technology difficulty of environmental pollution.
Description
Technical field
The present invention relates to a kind of preparation methods, and in particular to a kind of preparation method of glycine betaine methyl ester hydrochloride.Belonging to
Learn synthesis technical field.
Background technology
Beet alkali hydrochlorate is a kind of quaternary alkaloid, possesses excellent bioactivity, in medicine, pesticide, feed
The industries such as additive and cosmetics have a wide range of applications, and glycine betaine methyl ester hydrochloride be prepare beet alkali hydrochlorate must not
The key intermediate species that can lack, its preparation directly affect the preparation of beet alkali hydrochlorate.
The chemical synthesis of beet alkali hydrochlorate, can according to the type of alkali mostly using monoxone and trimethylamine as base stock
To be subdivided into the calcium method technique different with two class of sodium method.The calcium method technique of existing literature report is substantially all using monoxone, hydrogen
Calcium oxide and trimethylamine reaction prepare glycine betaine methyl ester hydrochloride, are then acidified the synthesis strategy for preparing beet alkali hydrochlorate again,
But during monoxone and calcium hydroxide reaction prepare calcium chloroacetate, monoxone hydrolytic side reactions inevitably occur
Hydroxyacetic acid is generated, trimethylamine is excessive, and discharge amount of exhaust gas is big, easily causes environmental pollution, and energy consumption is high.Sodium method technique is main
Monoxone, sodium hydroxide and trimethylamine are raw material, although raw material is easy to get, technique chlorine in the preparation process of sodium chloroacetate
Acetolysis side reaction is more, causes the yield of the technique only 86% or so, and the production cycle of technique is long, the utilization rate of equipment and
Turnover rate is relatively low, and sodium chloride residual is more in the product prepared, influences product quality.Therefore, there is an urgent need to develop a kind of high
Imitate energy saving, environmental-friendly glycine betaine methyl ester hydrochloride preparation method.
Invention content
The purpose of the present invention is to overcome above-mentioned the deficiencies in the prior art, provide a kind of preparation of glycine betaine methyl ester hydrochloride
Method is to prepare glycine betaine methyl ester hydrochloride by excessive methyl chloroacetate and trimethylamine quaternization reaction, avoids chloroethene
Sour first ester hydrolysis, realizes the Quantitative yield of trimethylamine, reduces the generation of exhaust gas, and with short production cycle, simple for process,
Low energy consumption.
To achieve the above object, the present invention uses following technical proposals：
A kind of preparation method of glycine betaine methyl ester hydrochloride, comprises the concrete steps that：Methyl chloroacetate is added into reaction bulb, so
After be passed through front three amine gas and reacted, after reaction, air-distillation deviates from unreacted methyl chloroacetate to get glycine betaine
Methyl ester hydrochloride；Wherein, the mol ratio of methyl chloroacetate and trimethylamine is 1.2~2：1, reaction equation is as follows：
Preferably, reaction temperature is 25~40 DEG C.
Preferably, the reaction time is 1~4 hour.
Preferably, the unreacted methyl chloroacetate cycle is anti-for preparing for glycine betaine methyl ester hydrochloride next time
It answers.
Beneficial effects of the present invention：
The present invention carries out quaternization reaction to prepare glycine betaine methyl esters by excessive methyl chloroacetate and front three amine gas
Hydrochloride, after reaction air-distillation go out unreacted methyl chloroacetate, obtain product glycine betaine methyl ester hydrochloride, the chlorine of abjection
Methyl acetate recycle utilizes.
The preparation method of the present invention, realizes the Quantitative yield of trimethylamine, avoids the hydrolysis of methyl chloroacetate, and product is received
Rate reaches 99% or more, stable quality, simple for process, low energy consumption, and it is easy fundamentally to overcome monoxone in traditional soda technique
Hydrolysis, conversion ratio are low, and trimethylamine is excessive, and discharge amount of exhaust gas is big, easily causes the key technology difficulty of environmental pollution.
Specific implementation mode
With reference to embodiment, the present invention will be further elaborated, it should explanation, following the description merely to
It explains the present invention, its content is not defined.
Embodiment 1：
After methyl chloroacetate 129.6g (1.2mol) is added into reaction bulb, it is passed through front three amine gas 59g (2mol), is kept
Temperature is to react 1h at 25 DEG C, and then air-distillation deviates from unreacted methyl chloroacetate to get product glycine betaine methyl esters hydrochloric acid
Salt, the methyl chloroacetate of abjection is directly used in prepares reaction next time.The yield of glycine betaine methyl ester hydrochloride is 99.2%, purity
It is 99.18%.
Embodiment 2：
After methyl chloroacetate 129.6g (1.2mol) is added into reaction bulb, it is passed through front three amine gas 59g (2mol), is kept
Temperature is to react 4h at 25 DEG C, and then air-distillation deviates from unreacted methyl chloroacetate to get product glycine betaine methyl esters hydrochloric acid
Salt, the methyl chloroacetate of abjection is directly used in prepares reaction next time.The yield of glycine betaine methyl ester hydrochloride is 99.4%, purity
It is 99.06%.
Embodiment 3：
After methyl chloroacetate 162g (1.5mol) is added into reaction bulb, it is passed through front three amine gas 59g (2mol), keeps temperature
For degree to react 1h at 40 DEG C, then air-distillation deviates from unreacted methyl chloroacetate to get product glycine betaine methyl ester hydrochloride,
The methyl chloroacetate of abjection is directly used in prepares reaction next time.The yield of glycine betaine methyl ester hydrochloride is 99.4%, and purity is
99.02%.
Embodiment 4：
After methyl chloroacetate 162g (1.5mol) is added into reaction bulb, it is passed through front three amine gas 59g (2mol), keeps temperature
For degree to react 4h at 30 DEG C, then air-distillation deviates from unreacted methyl chloroacetate to get product glycine betaine methyl ester hydrochloride,
The methyl chloroacetate of abjection is directly used in prepares reaction next time.The yield of glycine betaine methyl ester hydrochloride is 99.6%, and purity is
99.09%.
Embodiment 5：
After methyl chloroacetate 216g (2mol) is added into reaction bulb, it is passed through front three amine gas 59g (2mol), keeps temperature
It is to react 3h at 40 DEG C, then air-distillation deviates from unreacted methyl chloroacetate to get product glycine betaine methyl ester hydrochloride, takes off
The methyl chloroacetate gone out is directly used in prepares reaction next time.The yield of glycine betaine methyl ester hydrochloride is 99.6%, and purity is
99.10%.
Embodiment 6：
After methyl chloroacetate 216g (2mol) is added into reaction bulb, it is passed through front three amine gas 59g (2mol), keeps temperature
It is to react 2h at 35 DEG C, then air-distillation deviates from unreacted methyl chloroacetate to get product glycine betaine methyl ester hydrochloride, takes off
The methyl chloroacetate gone out is directly used in prepares reaction next time.The yield of glycine betaine methyl ester hydrochloride is 99.5%, and purity is
99.07%.
Although the above-mentioned specific implementation mode to the present invention is described, not to the limit of the scope of the present invention
System, based on the technical solutions of the present invention, those skilled in the art need not make the creative labor can make it is each
Kind modification or deformation are still within protection scope of the present invention.
Claims (5)
1. a kind of preparation method of glycine betaine methyl ester hydrochloride, which is characterized in that comprise the concrete steps that：Chloroethene is added into reaction bulb
Sour methyl esters then passes to front three amine gas and is reacted, and after reaction, unreacted methyl chloroacetate is deviate from air-distillation,
Up to glycine betaine methyl ester hydrochloride；Wherein, the mol ratio of methyl chloroacetate and trimethylamine is 1.2~2：1, reaction equation is such as
Under：
2. a kind of preparation method of glycine betaine methyl ester hydrochloride according to claim 1, which is characterized in that reaction temperature is
25~40 DEG C.
3. a kind of preparation method of glycine betaine methyl ester hydrochloride according to claim 1, which is characterized in that the reaction time is
1~4 hour.
4. a kind of preparation method of glycine betaine methyl ester hydrochloride according to claim 1, which is characterized in that the reaction time is
2~4 hours.
5. a kind of preparation method of glycine betaine methyl ester hydrochloride according to claim 1, which is characterized in that the unreacted
Preparation reaction of the methyl chloroacetate cycle for glycine betaine methyl ester hydrochloride next time.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810932980.7A CN108774146A (en) | 2018-08-16 | 2018-08-16 | A kind of preparation method of glycine betaine methyl ester hydrochloride |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810932980.7A CN108774146A (en) | 2018-08-16 | 2018-08-16 | A kind of preparation method of glycine betaine methyl ester hydrochloride |
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| Publication Number | Publication Date |
|---|---|
| CN108774146A true CN108774146A (en) | 2018-11-09 |
Family
ID=64029337
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| Application Number | Title | Priority Date | Filing Date |
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| CN201810932980.7A Pending CN108774146A (en) | 2018-08-16 | 2018-08-16 | A kind of preparation method of glycine betaine methyl ester hydrochloride |
Country Status (1)
| Country | Link |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110568119A (en) * | 2019-10-09 | 2019-12-13 | 山东省化工研究院 | method for simultaneously detecting betaine hydrochloride and methyl chloroacetate quaternary ammonium salt |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD294708A5 (en) * | 1990-05-30 | 1991-10-10 | Berlin-Chemie,De | NEW BIOLOGICAL ACTIVE OMEGA (ALKYLAMINO) CARBON ACID PHENYLESTER |
| CN1263085A (en) * | 1998-12-28 | 2000-08-16 | 花王株式会社 | Preparation method of betaine alkyl ester mixture |
| CN101691335A (en) * | 2009-10-26 | 2010-04-07 | 大庆市富杰化工有限公司 | Carboxylic acid higher alcohol ester-trimethyl ammonium chloride and application thereof in clay stabilizer |
| CN102126964A (en) * | 2010-12-10 | 2011-07-20 | 江南大学 | Method for preparing high-content alpha-lauryl betaine by solvent-free quaternization |
| CN102267918A (en) * | 2011-06-23 | 2011-12-07 | 杭州海尔希畜牧科技有限公司 | Method for preparing betaine hydrochloride |
| CN102391139A (en) * | 2011-08-24 | 2012-03-28 | 山东大学 | Energy-saving and environmentally-friendly process for synthesizing alkyl betaine |
| CN107986988A (en) * | 2017-11-28 | 2018-05-04 | 云南大学 | Protonated betaine type ionic liquid of hydroxamic acid functionalization and preparation method thereof |
| CN109942445A (en) * | 2019-02-26 | 2019-06-28 | 山东瑞弘生物科技有限公司 | Beet alkali hydrochlorate synthetic method |
-
2018
- 2018-08-16 CN CN201810932980.7A patent/CN108774146A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD294708A5 (en) * | 1990-05-30 | 1991-10-10 | Berlin-Chemie,De | NEW BIOLOGICAL ACTIVE OMEGA (ALKYLAMINO) CARBON ACID PHENYLESTER |
| CN1263085A (en) * | 1998-12-28 | 2000-08-16 | 花王株式会社 | Preparation method of betaine alkyl ester mixture |
| CN101691335A (en) * | 2009-10-26 | 2010-04-07 | 大庆市富杰化工有限公司 | Carboxylic acid higher alcohol ester-trimethyl ammonium chloride and application thereof in clay stabilizer |
| CN102126964A (en) * | 2010-12-10 | 2011-07-20 | 江南大学 | Method for preparing high-content alpha-lauryl betaine by solvent-free quaternization |
| CN102267918A (en) * | 2011-06-23 | 2011-12-07 | 杭州海尔希畜牧科技有限公司 | Method for preparing betaine hydrochloride |
| CN102391139A (en) * | 2011-08-24 | 2012-03-28 | 山东大学 | Energy-saving and environmentally-friendly process for synthesizing alkyl betaine |
| CN107986988A (en) * | 2017-11-28 | 2018-05-04 | 云南大学 | Protonated betaine type ionic liquid of hydroxamic acid functionalization and preparation method thereof |
| CN109942445A (en) * | 2019-02-26 | 2019-06-28 | 山东瑞弘生物科技有限公司 | Beet alkali hydrochlorate synthetic method |
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| Title |
|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110568119A (en) * | 2019-10-09 | 2019-12-13 | 山东省化工研究院 | method for simultaneously detecting betaine hydrochloride and methyl chloroacetate quaternary ammonium salt |
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Application publication date: 20181109 |