CN102503862A - Method for synthesizing sulfuric acid amino ethyl ester - Google Patents
Method for synthesizing sulfuric acid amino ethyl ester Download PDFInfo
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- CN102503862A CN102503862A CN2011102814975A CN201110281497A CN102503862A CN 102503862 A CN102503862 A CN 102503862A CN 2011102814975 A CN2011102814975 A CN 2011102814975A CN 201110281497 A CN201110281497 A CN 201110281497A CN 102503862 A CN102503862 A CN 102503862A
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- sulfuric acid
- ethyl ester
- amino ethyl
- acid amino
- thanomin
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Abstract
The invention discloses method for synthesizing sulfuric acid amino ethyl ester, which belongs to the technical field of organic chemical synthesis. The method comprises the following steps of: undergoing a neutralizing and salifying reaction on ethanolamine and sulfuric acid; controlling the temperature of the neutralizing and salifying reaction to generate sulfuric acid hydroxyethyl ammonium salt; transferring the sulfuric acid hydroxyethyl ammonium salt into a reactor under the heating and decompressing conditions, dehydrating and undergoing an esterification reaction; controlling the heating temperature and decompressing vacuum degree of the esterification reaction till a material is pasty; adding cold water into the pasty material; stopping reacting instantly; precipitating sulfuric acid amino ethyl ester out in the form of crystal; and filtering and dehydrating to obtain pure sulfuric acid amino ethyl ester, wherein a generated mother liquor generated by filtering is recycled as cold water. The method has the advantages that: pure sulfuric acid amino ethyl ester can be obtained; and environmentally-friendly production is represented, raw materials can be saved and synthesizing cost can be lowered.
Description
Technical field
The present invention relates to a kind of method of synthetic sulfuric acid amino ethyl ester, belong to organic chemical industry's synthesis technical field.
Background technology
The sulfuric acid amino ethyl ester, formal name used at school hydrogen sulfate-2-amino ethyl ester is also claimed thanomin sulfuric ester, thanomin sulfuric acid hydrogen ester, cholamine sulfuric acid hydrogen ester, 2-aminoethylsulfuric acid, is that the midbody of thanomin esterification process production taurine product is an intermediate product.
The sulfuric acid amino ethyl ester also can be used as merchandise sales, is the raw material of producing ethyleneimine etc., and ethyleneimine can be the midbody of synthesizing polyethylene imines, also can be used as the midbody of producing Mercaptamine etc.
The sulfuric acid amino ethyl ester is made through esterification by thanomin and sulfuric acid usually; Because thanomin is a kind of organic bases simultaneously; Alkalescence is stronger; Acid-base neutralisation reaction at first can take place with sulfuric acid in it, so this reaction is different from the esterification of general carboxylic acid and alcohol, reaction reality is carried out in two steps: in salify and dehydration esterification.
1) in and salify:
NH
2CH
2CH
2OH+H
2SO
4→[NH
3CH
2CH
2OH]
+·OSO
3H
-
2) dehydration esterification:
The principle of thanomin and sulfuric acid generation esterification is clear and definite, and the method for water is removed in esterification can be different, have the esterification concrete grammar of report to have two kinds: the one, and heating decompression dehydration esterification process; Under the vacuum decompression condition; With the salify material thermal dehydration esterification of sulfuric acid and thanomin, the vitriol oil is excessive in the reaction, the vitriol oil dehydration of in reaction, having held concurrently; Vacuum tightness that reaction needed is higher and temperature, the pressurized, heated dehydration becomes solid until material; Practical fine chemicals handbook is then introduced thanomin is diluted to mass percent concentration is 85%, under agitation slowly drips the vitriol oil, and temperature is controlled at 10～30 ℃ when dripping sulfuric acid; Dropwised insulated and stirred 1 hour; Continue the intensification decompression dehydration again to there being crystallization to separate out, crystallisation by cooling filters, and washes after drying on a small quantity and gets product; Yield can reach 90% (chapter is thought rule. practical fine chemicals handbook. Beijing: the .1996 of Chemical Industry Press, 6:146-147).
The 2nd, the organic solvent azeotropic dewatering; Sulfuric acid and Monoethanolamine MEA BASF at first also be in and salify, do under the condition of band aqua normal pressure/or vacuum decompression simultaneously then at organic solvent; The esterification of heating salify material dewatering, the band aqua is organic solvent toluene, butanols etc.; Because the existence of band aqua, temperature of reaction and vacuum requirements are not high relatively, and reaction back ester also is difficult for forming bulk.The south pillar (improvement of southern pillar .2-aminoethyl sulfuric acid preparation. Chinese Journal of Pharmaceuticals; 1989; 2:71) adopting ammonium sulfate and strong sulfuric acid response to generate monoammonium sulfate reacts with thanomin again; With the water that methylbenzene azeotropic is taken and generated, the ammonium sulfate used water recrystallization in the bullion sulfuric ester is removed, and the mother liquor of sulfur acid ammonium and unreacted thanomin can be used as the raw material of batch reaction down.
The former shortcoming in above-mentioned two kinds of methods is: actual in taurine production what adopt is the esterification process of direct heating decompression dehydration; Be a kind ofly can be called the working method of frying dry method; Promptly heat decompression dehydration not being with under the aqua condition; Add the thermal material thickness that becomes gradually, material will be through being listed as following variation:
Limpid fluxion → thickness → pasty state → dried pasty state → powdery/dry-powdered
Material is exactly the operation of a kind of similar " stir-fry " to pasty state, utilizes to be stirred in the reaction kettle bottom with pasty material grinding " stir-fry is done and fried pine ".If the salify material proportion is accurate, esterification is that vacuum condition and agitation condition are all controlled the ideal words, can reach the desired result that material dewatering becomes the powdery sulfuric ester at last so.For esterification is accomplished as far as possible, often select excess sulfuric acid more than 10%, generally often be difficult to complete reaction so reality is carried out esterification with the stir-fry dry method, and need with excessive free acids of neutralization such as yellow soda ash after the reaction.The esterification process of this use heating decompression dehydration exists equipment requirements high, and energy consumption is big; Very high with the normal requirement of equipment operation to equipment itself on the industrial production, the overstriking anchor formula that needs heavy-duty motor to drive customization stirs.It is nearer apart from Polycondensation Reactor and Esterification Reactor to stir anchor in the reaction kettle, and still running stirring by force when material is converted into pasty state and even solid is easy to produce vibrations this moment and damages mechanical seal, the friction damage reaction kettle of ester and the enamel of stirring.Cut off the power supply with regard to motor overload occurring when often occurring being stirred to pasty state in the actual production, stir stall; If untimely being dissolved in water when reaction can proceed to powdery once in a while, negative pressure of vacuum can be taken away pulverulent material.
The latter's existing problems are: organic solvent azeotropic dehydration esterification process is achieved success at laboratory stage, but on producing, implements to also have very big distance.Subject matter is: (1) organic solvent itself belongs to hazardous chemical, in buying, transport, storing in a warehouse certain Hazard Factor is arranged; (2) reaction process has the vitriol oil to participate in, and solvent need distill reclaimer operation, and production process increases Hazard Factor; (3) a large amount of organic solvents using and reclaiming, increase purchase cost and running cost.
In view of above-mentioned prior art, be necessary to improve, for this reason, the applicant has done actively and good try has found the way of dealing with problems, and the technical scheme that will introduce below produces under this background.
Summary of the invention
Task of the present invention is to provide a kind of and helps to improve crystalline purity, helps avoiding causing environmental pollution and uses and embody green production and be of value to the method that improves product yield, saves the synthetic sulfuric acid amino ethyl ester of equipment running cost.
Task of the present invention is accomplished like this, a kind of method of synthetic sulfuric acid amino ethyl ester, and it is that thanomin and sulfuric acid are neutralized into reactant salt; And control is neutralized into the reactant salt temperature, generates sulfuric acid hydroxyethyl ammonium salt, sulfuric acid hydroxyethyl ammonium salt is changed in the reaction vessel under the heating reduced pressure, dewater and esterification; And control esterification Heating temperature and reduced vacuum degree to material in the pasty state the time, join cold water in the material in the pasty state; Moment stopped reaction, separate out the sulfuric acid amino ethyl ester with crystalline form, through filtering and dehydration; Obtain purified sulfuric acid amino ethyl ester, filter the mother liquor that produces and recycle as cold water.
In a concrete embodiment of the present invention, described thanomin and sulfuric acid reaction are that sulfuric acid is dropped in the thanomin with the dropping mode, and the control dropping time.
In another concrete embodiment of the present invention, it is to be controlled to be 20-60 ℃ with being neutralized into the reactant salt temperature that described control is neutralized into the reactant salt temperature.
In another concrete embodiment of the present invention, described control esterification Heating temperature is to be 90-130 ℃ with heating and temperature control, and described control reduced vacuum degree is to be 5-20kPa with pressure-controlling.
In another concrete embodiment of the present invention, described cold water join add-on in the material in the pasty state be said thanomin quality 2-6 doubly.
Also have among the concrete embodiment of the present invention, said thanomin and said vitriolic mol ratio are 1: 1.02-1.20.
more of the present invention and among concrete embodiment, described sulfuric acid is the vitriol oil.
In of the present invention and then concrete embodiment, the mother liquor that produces when described filtration occurs then this mother liquor being concentrated the esterification of post-heating decompression dehydration separately when superfluous.
Of the present invention again more and among concrete embodiment, the described control dropping time is that the dropping time is controlled to be 2-4hr, sulfuric acid dropwises back insulation 10-30min.
Technical scheme provided by the invention owing to will being changed over to the esterification of reaction vessel decompression thermal dehydration by the sulfuric acid hydroxyethyl ammonium salt that thanomin and sulfuric acid reaction generate, and is used the cold water cancellation, thereby can be obtained purified sulfuric acid amino ethyl ester; The mother liquor of gained in the link will be as cold water and cyclically utilizing cancellation water owing to will filter and dewater, thereby can not undermine environment and embody green production, and can economize in raw materials and reduce synthetic cost.Lab scale sulfuric acid amino ethyl ester yield reaches more than 99.0%, and contents on dry basis is more than 99.0%, not have discharge of wastewater, and product stability is good, and 12 months content of normal temperature storage is in the no considerable change of butt.
Embodiment
Embodiment 1:
With 61mL and mass percent concentration is that 98.5% thanomin (1mol) is inserted in the there-necked flask of 500mL; And place ice bath; The state bottom of stirring on the limit all drops to the vitriol oil (1.02mol) of 55.4mL in 2hr with the dropping mode lentamente and is neutralized into reactant salt (abbreviating salt-forming reaction as) in the thanomin, and insulation 10min promptly is incubated 10min after dripping sulfuric acid; In this reaction process; Temperature is controlled to be 60 ℃, obtains the salify material, promptly obtaining chemical name is the salify material of sulfuric acid hydroxyethyl ammonium salt; The salify material of sulfuric acid hydroxyethyl ammonium salt is transferred to reaction vessel promptly is transferred in the four-hole tetrafluoro flask or four-hole quartz flask that places digital display (numeral shows) control-temperature electric heating cover, insert vacuum pump apparatus and open and stir and heating, dehydration (vacuum hydro-extraction) esterification under the heating reduced pressure; Wherein: the esterification Heating temperature is 130 ℃, and decompression pressure is 20kPa until material in the pasty state the time, promptly in the pasty state during material; Moment stopped reaction, specifically: also promptly stir at need, with 2 times of cold water to thanomin; That is, the cold water with 122mL is added in the pasty material instantaneous stopped reaction; Be cancellation, close vacuum and stirring is cooled to room temperature, this moment, the sulfuric acid amino ethyl ester was just separated out with crystalline form; Through filtering and dehydration, obtain purified sulfuric acid amino ethyl ester, used cold water is collected and recycle when filtering the mother liquor that produces as cancellation; And when filtering the mother liquor appearance surplus that is produced, then this mother liquor is concentrated the esterification of heating decompression dehydration separately.
Embodiment 2:
With 61mL and mass percent concentration is that 98.5% thanomin (1mol) is inserted in the there-necked flask of 500mL; And place ice bath; The state bottom of stirring on the limit all drops to the vitriol oil (1.2mol) of 65.2mL in 4hr with the mode that drips lentamente and is neutralized into reactant salt in the thanomin; After dripping the vitriol oil, being incubated 30min, in this reaction process, is that the salt-forming reaction temperature is controlled to be 20 ℃ with temperature; Obtain the salify material, promptly obtaining chemical name is the salify material of sulfuric acid hydroxyethyl ammonium salt; The salify material of sulfuric acid hydroxyethyl ammonium salt is transferred to reaction vessel promptly is transferred in the four-hole tetrafluoro flask or four-hole quartz flask that places digital display (numeral shows) control-temperature electric heating cover, insert vacuum pump apparatus and open and stir and heating, dehydration (vacuum hydro-extraction) esterification under the heating reduced pressure; Wherein: the esterification Heating temperature is 90 ℃, and decompression pressure is 5kPa until material in the pasty state the time, also promptly in the pasty state during material; Also promptly stir at need, with 6 times of cold water, promptly to thanomin; The cold water of 366mL is added water in the pasty material instantaneous stopped reaction, i.e. cancellation; Close vacuum and stirring is cooled to room temperature, this moment, the sulfuric acid amino ethyl ester was just separated out with crystalline form, through filtering and dehydration; Obtain purified sulfuric acid amino ethyl ester; The mother liquor that filter to produce during as cancellation used cold water collect and recycle, and occur then this mother liquor being concentrated separately and heating the decompression dehydration esterification when superfluous when filtering the mother liquor that is produced.
Embodiment 3:
With 61mL and mass percent concentration is that 98.5% thanomin (1mol) is inserted in the there-necked flask of 500mL; And place ice bath; The state bottom of stirring on the limit all drops to the vitriol oil (1.1mol) of 59.7mL with the dropping mode lentamente that to be neutralized into reactant salt in the thanomin be salt-forming reaction in 3hr; After dripping the vitriol oil, be incubated 20min, in this reaction process, the salt-forming reaction temperature be controlled to be 30 ℃; Obtain the salify material, promptly obtaining chemical name is the salify material of sulfuric acid hydroxyethyl ammonium salt; The salify material of sulfuric acid hydroxyethyl ammonium salt is transferred to reaction vessel promptly is transferred in the four-hole tetrafluoro flask or four-hole quartz flask that places digital display (numeral shows) control-temperature electric heating cover, insert vacuum pump apparatus and open and stir and heating, dehydration (vacuum hydro-extraction) esterification under the heating reduced pressure; Wherein: the esterification Heating temperature is 110 ℃, and decompression pressure is 10kPa until material in the pasty state the time, also promptly in the pasty state during material; Also promptly stir at need, with 4 times of cold water, promptly to thanomin; The cold water of 244mL is added water in the pasty material instantaneous stopped reaction, i.e. cancellation; Close vacuum and stirring is cooled to room temperature, this moment, the sulfuric acid amino ethyl ester was just separated out with crystalline form, through filtering and dehydration; Obtain purified sulfuric acid amino ethyl ester; The mother liquor that filter to produce during as cancellation used cold water collect and recycle, and occur then this mother liquor being concentrated separately and heating the decompression dehydration esterification when superfluous when filtering the mother liquor that is produced.
Claims (9)
1. the method for
a kind of synthetic sulfuric acid amino ethyl ester is characterized in that it is that thanomin and sulfuric acid are neutralized into reactant salt, and control is neutralized into the reactant salt temperature; Generate sulfuric acid hydroxyethyl ammonium salt, sulfuric acid hydroxyethyl ammonium salt is changed in the reaction vessel under the heating reduced pressure, dewater and esterification, and control esterification Heating temperature and reduced vacuum degree; To material in the pasty state the time, cold water is joined in the material in the pasty state, moment stopped reaction; Separate out the sulfuric acid amino ethyl ester with crystalline form; Through filtering and dehydration, obtain purified sulfuric acid amino ethyl ester, filter the mother liquor that produces and recycle as cold water.
2. the method for
synthetic sulfuric acid amino ethyl ester according to claim 1 is characterized in that described thanomin and sulfuric acid reaction are that sulfuric acid is dropped in the thanomin with the dropping mode, and the control dropping time.
3. the method for
synthetic sulfuric acid amino ethyl ester according to claim 1 is characterized in that it is to be controlled to be 20-60 ℃ with being neutralized into the reactant salt temperature that described control is neutralized into the reactant salt temperature.
4. the method for
synthetic sulfuric acid amino ethyl ester according to claim 1; It is characterized in that described control esterification Heating temperature is is 90-130 ℃ with heating and temperature control, described control reduced vacuum degree is to be 5-20kPa with pressure-controlling.
5. the method for
synthetic sulfuric acid amino ethyl ester according to claim 1, it is characterized in that described cold water join add-on in the material in the pasty state be said thanomin quality 2-6 doubly.
6. the method for
synthetic sulfuric acid amino ethyl ester according to claim 1 is characterized in that said thanomin and said vitriolic mol ratio are 1: 1.02-1.20.
7.
is characterized in that according to the method for claim 1 or 2 or 6 described synthetic sulfuric acid amino ethyl esters described sulfuric acid is the vitriol oil.
8. the method for
synthetic sulfuric acid amino ethyl ester according to claim 1 when it is characterized in that surplus appears in the mother liquor that produces when described filtration, then concentrates the esterification of post-heating decompression dehydration separately to this mother liquor.
9.
The method of synthetic sulfuric acid amino ethyl ester according to claim 2 is characterized in that the described control dropping time is that the dropping time is controlled to be 2-4hr, and sulfuric acid dropwises back insulation 10-30min
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103664707A (en) * | 2013-12-14 | 2014-03-26 | 内蒙古河西航天科技发展有限公司 | Acid sulfuric acid-beta-amino ester as well as synthesis method and application thereof |
| CN108892627A (en) * | 2018-08-03 | 2018-11-27 | 苏州华道生物药业股份有限公司 | The technique of one pot process taurine |
| CN110003072A (en) * | 2019-03-15 | 2019-07-12 | 宁夏倬昱新材料科技有限公司 | A kind of preparation method of 2- methylaziridine |
| CN110511165A (en) * | 2019-08-01 | 2019-11-29 | 苏州汉德创宏生化科技有限公司 | A kind of synthetic method of taurine precursor 2- ethylaminoethanol sulfuric ester |
| CN111777875A (en) * | 2020-07-03 | 2020-10-16 | 确成硅化学股份有限公司 | White carbon black for reducing rolling resistance of tire |
| CN115368279A (en) * | 2022-09-15 | 2022-11-22 | 浙江金科日化原料有限公司 | Preparation method of granular ethanolamine sulfate crystal |
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| US4597911A (en) * | 1983-12-14 | 1986-07-01 | Air Products And Chemicals, Inc. | Production of amino aliphatic and cycloaliphatic hydrogen sulfates |
| DE10124300A1 (en) * | 2001-05-17 | 2002-11-21 | Basf Ag | Production of sulfur semi-esters comprises reacting sulfuric acid with amino alcohols in the presence of a suspension agent using a vortex and distilling |
| CN1385420A (en) * | 2002-05-17 | 2002-12-18 | 江阴南极星生物制品有限公司 | Water-saving type high-efficient novel process for preparing tauvine by sulfuric acid method |
| CN101225063A (en) * | 2008-02-04 | 2008-07-23 | 重庆大学 | Method for preparing cysteamine hydrochloride by basic hydrolysis |
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| US4568747A (en) * | 1981-10-30 | 1986-02-04 | The Dow Chemical Company | Process for making 2-aminoethyl ether |
| US4597911A (en) * | 1983-12-14 | 1986-07-01 | Air Products And Chemicals, Inc. | Production of amino aliphatic and cycloaliphatic hydrogen sulfates |
| DE10124300A1 (en) * | 2001-05-17 | 2002-11-21 | Basf Ag | Production of sulfur semi-esters comprises reacting sulfuric acid with amino alcohols in the presence of a suspension agent using a vortex and distilling |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103664707A (en) * | 2013-12-14 | 2014-03-26 | 内蒙古河西航天科技发展有限公司 | Acid sulfuric acid-beta-amino ester as well as synthesis method and application thereof |
| CN108892627A (en) * | 2018-08-03 | 2018-11-27 | 苏州华道生物药业股份有限公司 | The technique of one pot process taurine |
| CN108892627B (en) * | 2018-08-03 | 2021-02-26 | 苏州华道生物药业股份有限公司 | Process for synthesizing taurine by one-pot method |
| CN110003072A (en) * | 2019-03-15 | 2019-07-12 | 宁夏倬昱新材料科技有限公司 | A kind of preparation method of 2- methylaziridine |
| CN110511165A (en) * | 2019-08-01 | 2019-11-29 | 苏州汉德创宏生化科技有限公司 | A kind of synthetic method of taurine precursor 2- ethylaminoethanol sulfuric ester |
| CN111777875A (en) * | 2020-07-03 | 2020-10-16 | 确成硅化学股份有限公司 | White carbon black for reducing rolling resistance of tire |
| CN115368279A (en) * | 2022-09-15 | 2022-11-22 | 浙江金科日化原料有限公司 | Preparation method of granular ethanolamine sulfate crystal |
| CN115368279B (en) * | 2022-09-15 | 2024-03-01 | 浙江金科日化新材料股份有限公司 | Preparation method of granular ethanolamine sulfate crystals |
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