CN105130833A - Preparation method of high-purity betain hydrochloride - Google Patents
Preparation method of high-purity betain hydrochloride Download PDFInfo
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- CN105130833A CN105130833A CN201510626649.9A CN201510626649A CN105130833A CN 105130833 A CN105130833 A CN 105130833A CN 201510626649 A CN201510626649 A CN 201510626649A CN 105130833 A CN105130833 A CN 105130833A
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Abstract
The invention provides an environment-friendly preparation method of high-purity betain hydrochloride, and the preparation method specifically comprises the steps of adding chloroacetic acid, a trimethylamine aqueous solution and Lewis base serving as a catalyst into a reaction vessel, reacting for 1 to 4 hours under the conditions that the temperature is 50 to 55 DEG C, and the pressure is 0.01 to 0.02 MPa, and removing water from reaction liquid through reduced pressure distillation after reacting; cooling the reaction liquid to the room temperature, adding ethyl alcohol into the reaction liquid, heating to 40 to 50 DEG C for dissolving, then cooling to 0 to 10 DEG C for separating crystals out, and obtaining the needed betain hydrochloride through filtering and drying a filter cake, wherein the Lewis base is water or N, N-dimethyl formamide. The preparation method is simple in process, short in production cycle, moderate in reaction conditions, simple in purifying of products, and high in product purity and yield, has no need of removing salt, and no generation of three wastes, has relatively high economical efficiency and environmental protection property, and is suitable for industrial production; the raw materials are easy to obtain.
Description
Technical field
The invention belongs to technical field of organic synthesis, particularly relate to a kind of preparation method of high-purity betaine hydrochloride.
Background technology
The chemical name of beet alkali hydrochlorate is hydrochloric acid Trimethyl glycine, is a kind of Amine quarter alkaloid, and molecular formula is C
5h
11nO
2hCl, its structural formula is as follows:
Beet alkali hydrochlorate can be dissolved in water and alcohol, is insoluble in trichloromethane, ether, and its aqueous solution is in acid, and ability less than 200 DEG C high temperature have very strong antioxidant property.Trimethyl-glycine is found in Europe at the beginning of last century, is mainly present in the molasses of beet, but its usefulness is until be just found the seventies in last century.It is a kind of water-soluble alkaloid be extensively present in animal vegetable tissue, its chemical structure and amino acid, choline are similar, there is efficient methyl donor, mitigation, stress regulate osmotic pressure, improve a poor appetite, stablize micro-element, replace some methionine, improve the effects such as efficiency of feed utilization, be widely used in word material, foodstuff additive and household chemicals field at present, there are boundless market outlook.
The preparation method of beet alkali hydrochlorate has natural beet sirup extraction method and chemical synthesis.The former due to raw material sources limited and make its application have certain limitation; Traditional chemical synthesis adopts Mono Chloro Acetic Acid and highly basic to react and first generates chloracetate, and then reacts with Trimethylamine 99, an alkali metal salt of generation and trimethyl-glycine, and obtain beet alkali hydrochlorate crude product by salting-out effect, then recrystallization obtains finished product.There is following several respects defect in the method: 1, this reaction is by SN1 nucleophilic substitution, and Cl atom is left away comparatively slow, and therefore the reaction times is longer; 2, because of Mono Chloro Acetic Acid can be hydrolyzed under basic conditions, eliminate, the side reaction such as polymerization, generate a large amount of by product, make product yield and quality cause great impact; 3, the salt generated is difficult to be separated removing with trimethyl-glycine.Many defects above, make the reaction times longer, plant factor is low, and power consumption energy consumption, without increase, causes cost higher.Concrete reaction is:
ClCH
2cOOH+NaOH=ClCH
2cOON
a+ H
2o (main reaction)
ClCH
2COON
a+N(CH
3)
3＝N(CH
3)
3CH
2COO
-+N
aCl
ClCH
2cOOH+2NaOH=HOCH
2cOON
a+ N
acl (side reaction 1)
HOCH
2cOON
a+ ClCH
2cOOH=HOCH
2cOOH+ClCH
2cOON
a(side reaction 2)
In recent years to this research as adopted the methods such as strong cation-exchanging resin method, solvent method, all there are the problems such as cost is high, aftertreatment is difficult, supersalinity waste water cannot process, which greatly limits the industrialized development of trimethyl-glycine.
Chinese patent ZL201010123877.1 with Mono Chloro Acetic Acid, Trimethylamine 99 and water-removal agent for raw material, it is reacted in organic solvent and within 5-8 hour, generates beet alkali hydrochlorate, technique is simple, with short production cycle, product is without other byproducts, but the organic solvent used in reaction process needs recycling, does not meet the requirement of green production.
Summary of the invention
In order to solve Problems existing in existing beet alkali hydrochlorate technology of preparing, the invention provides a kind of preparation method of beet alkali hydrochlorate of environmental protection, product purity, yield are high, and production technique is simple, produce without the three wastes and by product in production process, there is the meaning of economic environmental protection.
The technical scheme that technical solution problem of the present invention is taked is:
A preparation method for high-purity betaine hydrochloride, specifically comprises the following steps:
(1) add in reaction vessel by Mono Chloro Acetic Acid, trimethylamine aqueous solution and catalyzer Lewis base, in 50-55 DEG C, under pressure 0.01-0.02MPa, reaction 1-4 hour, after reaction terminates, reaction solution dewaters through underpressure distillation.Mono Chloro Acetic Acid, through transition state, becomes carbonium ion, then generates beet alkali hydrochlorate with the effect of nucleophilic reagent Trimethylamine 99, belongs to typical Huffman alkyl substitution.Temperature of reaction is the important factor affecting nucleophilic substitution reaction, and the nucleophilic substitution reaction speed of Mono Chloro Acetic Acid and Trimethylamine 99 is 50-55 DEG C of the best, and the speed of reaction that all can cause too high or too low for temperature reduces.
(2) step (1) gained reaction solution is cooled to room temperature, then adds ethanol wherein, be heated to 40-45 DEG C of dissolving, then be cooled to 0-10 DEG C of crystallization, after filtration, filtration cakes torrefaction obtains required beet alkali hydrochlorate.
As preferably, described in step (1), the mass concentration of trimethylamine aqueous solution is 30-33%.
As preferably, described in step (1), Lewis base is water or DMF.
As preferably, in Mono Chloro Acetic Acid and trimethylamine aqueous solution, the molar ratio of Trimethylamine 99 is 1:1.3-1.7, and described catalyzer and chloroacetic molar ratio are 1:0.005-0.01.Trimethylamine 99 is larger than reaction theory mol ratio with chloroacetic best molar ratio, reason is: Trimethylamine 99 and Mono Chloro Acetic Acid connect acid amide because acid-base neutralisation reacts to generate, some Trimethylamine 99 is as acid binding agent simultaneously, and control the pH value of reaction, therefore Trimethylamine 99 amount ratio theoretical amount is many.
As preferably, described in step (1), the quality of Mono Chloro Acetic Acid and ethanol is 1:4.
More preferably, described Lewis base is DMF.
Concrete reaction formula is:
ClCH
2COOH+N(CH
3)
3→(CH
3)
3N
+CH
2COO
-·HCl
Reaction mechanism is:
The first step:
Second step:
Beneficial effect of the present invention is:
1, adopt Louis's alkali as a catalyst, make reaction fast abundant, simultaneously owing to not having the generation of side reaction, product purity and yield improve (high purity more than 97%, yield reaches more than 99% in Mono Chloro Acetic Acid) all greatly.
2, technique is simple, with short production cycle, and reaction conditions is gentle, does not need desalination, and product is purified simple, produces, have higher economy and the feature of environmental protection without the three wastes.
3, do not need to use expensive alkali and hydrochloric acid, cheaper starting materials is easy to get, and is applicable to suitability for industrialized production.
Embodiment
Explain the present invention further below in conjunction with embodiment, but embodiment does not limit in any form to the present invention.
Embodiment 1
Be the trimethylamine aqueous solution of 33% by 37.8g (0.4mol) Mono Chloro Acetic Acid, 93.14g (0.52mol) mass concentration, 0.15gN, dinethylformamide adds in pressure reaction still, in 50 DEG C, reaction after 2 hours under 0.01MPa, reaction solution dewaters through underpressure distillation, reaction solution is cooled to room temperature, add 151.2g ethanol again, adularescent crystallization, is heated to 40 DEG C and dissolves completely to it, then is cooled to 10 DEG C of adularescent crystal precipitations, filter, dry beet alkali hydrochlorate 62.47g, its HPLC purity is 97.60%, and yield is 99.30%.
Embodiment 2
Be the trimethylamine aqueous solution of 30% by 37.8g (0.4mol) Mono Chloro Acetic Acid, 118.00g (0.60mol) mass concentration, 0.072g water adds in pressure reaction still, in 52 DEG C, reaction after 1 hour under 0.015MPa, reaction solution underpressure distillation dewaters, reaction solution is cooled to room temperature, add 37.8g ethanol again, adularescent crystallization, be heated to 42 DEG C dissolve completely to it, be cooled to 5 DEG C of adularescent crystal again to separate out, filter, dry beet alkali hydrochlorate 61.87g, its HPLC purity is 98.32%, and yield is 99.07%.
Embodiment 3
Be the trimethylamine aqueous solution of 32% by 37.8g (0.4mol) Mono Chloro Acetic Acid, 125.38g (0.68mol) mass concentration, 0.23gN, dinethylformamide adds in pressure reaction still, in 55 DEG C, reaction after 4 hours under 0.02MPa, reaction solution underpressure distillation dewaters, reaction solution is cooled to room temperature, add 113.4g ethanol again, adularescent crystallization, is heated to 45 DEG C and dissolves completely to it, then is cooled to 0 DEG C of adularescent crystal precipitation, filter, dry beet alkali hydrochlorate 61.17g, its HPLC purity is 98.57%, and yield is 99.81%.
Below only list the preferred embodiments of the invention, protection scope of the present invention is not restricted to this, and any change that those skilled in the art do within the scope of the claims in the present invention all falls in scope.
Claims (6)
1. a preparation method for high-purity betaine hydrochloride, is characterized in that, described preparation comprises the following steps:
(1) Mono Chloro Acetic Acid, trimethylamine aqueous solution and catalyzer Lewis base are added in reaction vessel, in 50-55 DEG C, under pressure 0.01-0.02MPa, reaction 1-4 hour, after reaction terminates, reaction solution dewaters through underpressure distillation;
(2) step (1) gained reaction solution is cooled to room temperature, then adds ethanol wherein, be heated to 40-45 DEG C of dissolving, then be cooled to 0-10 DEG C of crystallization, after filtration, filtration cakes torrefaction obtains required beet alkali hydrochlorate.
2. the preparation method of high-purity betaine hydrochloride as claimed in claim 1, it is characterized in that, described in step (1), the mass concentration of trimethylamine aqueous solution is 30-33%.
3. the preparation method of high-purity betaine hydrochloride as claimed in claim 1, it is characterized in that, described in step (1), Lewis base is water or DMF.
4. the preparation method of high-purity betaine hydrochloride as claimed in claim 1, it is characterized in that, in Mono Chloro Acetic Acid described in step (1) and trimethylamine aqueous solution, the molar ratio of Trimethylamine 99 is 1:1.3-1.7, and described catalyzer and chloroacetic molar ratio are 1:0.005-0.01.
5. the preparation method of high-purity betaine hydrochloride as claimed in claim 1, it is characterized in that, described in step (1), the quality of Mono Chloro Acetic Acid and ethanol is 1:4.
6. the preparation method of high-purity betaine hydrochloride as claimed in claim 3, it is characterized in that, described Lewis base is DMF.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109593518A (en) * | 2018-12-06 | 2019-04-09 | 古莱特科技股份有限公司 | A kind of solid acid de-plugging system for acidification of oil field de-plugging |
| 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 |
| CN110818580A (en) * | 2019-11-27 | 2020-02-21 | 山东省化工研究院 | Synthesis process of betaine hydrochloride |
| CN112174843A (en) * | 2020-10-10 | 2021-01-05 | 衢州学院 | Preparation method for low-ignition residue betaine hydrochloride and co-production sodium fluosilicate |
| CN113563214A (en) * | 2021-07-06 | 2021-10-29 | 山东鲁泰控股集团有限公司石墨烯高分子复合材料研发中心 | Synthetic method of aminoacetic acid |
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| CN1224710A (en) * | 1998-12-16 | 1999-08-04 | 山东大学 | Synthesis of hydrochloride of betaine |
| CN1374293A (en) * | 2002-03-18 | 2002-10-16 | 浙江大学 | Green synthesis process of betaine hydrochloride |
| US20060009656A1 (en) * | 2004-07-09 | 2006-01-12 | Jiashu Zhang | Method of producing betaine compound |
| CN102617374A (en) * | 2011-01-31 | 2012-08-01 | 中牧实业股份有限公司 | Method for preparing betaine hydrochloride |
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2015
- 2015-09-28 CN CN201510626649.9A patent/CN105130833A/en active Pending
Patent Citations (5)
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| CN1196351A (en) * | 1997-12-30 | 1998-10-21 | 河北省固安县宏峰化工有限公司 | Synthesis and separation of trimethyl glycine (betaine) |
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| CN1374293A (en) * | 2002-03-18 | 2002-10-16 | 浙江大学 | Green synthesis process of betaine hydrochloride |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109593518A (en) * | 2018-12-06 | 2019-04-09 | 古莱特科技股份有限公司 | A kind of solid acid de-plugging system for acidification of oil field de-plugging |
| 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 |
| CN110818580A (en) * | 2019-11-27 | 2020-02-21 | 山东省化工研究院 | Synthesis process of betaine hydrochloride |
| CN112174843A (en) * | 2020-10-10 | 2021-01-05 | 衢州学院 | Preparation method for low-ignition residue betaine hydrochloride and co-production sodium fluosilicate |
| CN112174843B (en) * | 2020-10-10 | 2022-07-01 | 衢州学院 | Preparation method for low-ignition residue betaine hydrochloride and co-production sodium fluosilicate |
| CN113563214A (en) * | 2021-07-06 | 2021-10-29 | 山东鲁泰控股集团有限公司石墨烯高分子复合材料研发中心 | Synthetic method of aminoacetic acid |
| CN113563214B (en) * | 2021-07-06 | 2024-02-02 | 山东鲁泰控股集团有限公司石墨烯高分子复合材料研发中心 | Synthesis method of glycine |
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