CN107573223A - A kind of method of highly efficient distilling production tetraethyl orthocarbonate - Google Patents
A kind of method of highly efficient distilling production tetraethyl orthocarbonate Download PDFInfo
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- CN107573223A CN107573223A CN201710950038.9A CN201710950038A CN107573223A CN 107573223 A CN107573223 A CN 107573223A CN 201710950038 A CN201710950038 A CN 201710950038A CN 107573223 A CN107573223 A CN 107573223A
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- tetraethyl orthocarbonate
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- efficient distilling
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Abstract
The present invention relates to field of fine chemical, relate in particular to a kind of method of highly efficient distilling production tetraethyl orthocarbonate, low polar aprotic solvent is the method use to handle tetraethyl orthocarbonate, extraction is not only played, and in distillation process, a small amount of moisture content azeotropic can be taken out of, avoid product from being degraded in distillation process；By adding solid base, rectification system pH value is improved, prevents that pH value decline causes product constantly to decompose in distillation process.A kind of highly efficient distilling, and the tetraethyl orthocarbonate of steady production high sterling are obtained by abovementioned technology.With existing technics comparing, the technique have the characteristics that efficiently, it is stable, can continuous rectification separating high-purity product, product purity reaches more than 99.5%.
Description
Technical field
The present invention relates to field of fine chemical, relates in particular to a kind of side of highly efficient distilling production tetraethyl orthocarbonate
Method.
Background technology
Tetraethyl orthocarbonate is the intermediate of drug for hypertension Candesartan, CAS：6280-87-1, its outward appearance are colourless
Transparency liquid, molecular weight 192.25, its structural formula are：(C2H5O)4C。
Tritox is used reported in United States Patent (USP) 2002/0061984, it is former that caustic alcohol reacts in absolute ethyl alcohol preparation
The method of carbonic acid tetra-ethyl ester.In that patent, Cymag caused by reaction uses strong oxidizer hydrogen peroxide, hypochlorous acid in aqueous phase
Sodium etc. carries out oxidation processes.The method has following shortcomings in commercial scale：(1) strong oxidizer such as hydrogen peroxide is being used,
Cyanogen root is very exothermic reaction in sodium hypochlorite processing water, and is released with a large amount of gases, is handled in commercial scale plant uneasy
Entirely；(2) cyanogen root is also available resources, all destroyed with oxidative treatment, can not be used, the wasting of resources.Separately having makes
Tetraethyl orthocarbonate is prepared in absolute ethyl alcohol with trichloronitromethane, caustic alcohol, it is domestic generally to be given birth to using trichloronitromethane
Production method.Due to the characteristic of tetraethyl orthocarbonate, the facile hydrolysis under neutral or solutions of weak acidity, hydrolysate has certain acidity
It is further exacerbated by product hydrolysis；Production process is due to using ethanol so that treating that moisture content is very high in the crude product of rectifying, distillation process
Middle product is constantly degraded in the presence of water, hardly results in the product of high-purity, universal tetraethyl orthocarbonate purity domestic at present
Between 98%-99%, as modern medicine development in recent years is to tetraethyl orthocarbonate quality requirements more and more higher, purity 98%-
99% tetraethyl orthocarbonate can not fully meet the demand in market.
The content of the invention
It is an object of the invention to provide a kind of method of highly efficient distilling production tetraethyl orthocarbonate.
To solve the above problems, the technical solution adopted by the present invention is as follows：
(1) caustic alcohol and absolute ethyl alcohol are added in reaction vessel, the absolute ethyl alcohol weight is 3~8 times of caustic alcohol；
(2) trichloronitromethane is added to reaction vessel, it is 60~70 DEG C to control reacting liquid temperature, adds follow-up continuation of insurance temperature
Reaction 1~10 hour, obtains the ethanol solution of tetraethyl orthocarbonate；The mol ratio of the trichloronitromethane and caustic alcohol is
1.0: 3.1~4.5；
(3) ethanol solution for the tetraethyl orthocarbonate that air-distillation step (2) obtains, the ethanol weight distilled out are anhydrous
The 70~75% of amount of alcohol added；Solid in reaction solution is added water to after the completion of distillation all to dissolve；Then add low polar aprotic
Solvent extraction reaction solution so that tetraethyl orthocarbonate is extracted to low polar aprotic solvent phase；The addition of low polar aprotic solvent
For 3~6 times of caustic alcohol weight；
(4) organic phase that step (3) is obtained by extraction enters rectifying column, adds stabilizer alkali；Normal pressure by controlling reflux ratio,
First normal pressure steams 60~90% low polar aprotic solvent；
(5) again by controlling reflux ratio, rectification under vacuum goes out tetraethyl orthocarbonate.
Preferably, the absolute ethyl alcohol dosage in the step (1) is 4~5 times of caustic alcohol weight.
Preferably, the mol ratio of the trichloronitromethane and caustic alcohol is 1.0: 3.3~3.5.
Preferably, the low polar aprotic solvent is petroleum ether, n-hexane, hexamethylene, normal heptane or normal octane.
Preferably, the addition of the low polar aprotic solvent is 4~5 times of caustic alcohol weight.
Preferably, the stabilizer alkali in the step (4) is：Sodium carbonate, sodium hydroxide, potassium hydroxide, sodium methoxide, ethanol
One kind or any two kinds of mixture in sodium, potassium ethoxide, sodium isopropylate, sodium tert-butoxide or potassium tert-butoxide；
Preferably, the addition of the stabilizer alkali in the step (4) for trichloronitromethane weight 0.01~
0.5%；Further, the addition of the stabilizer alkali is the 0.05~0.1% of trichloronitromethane weight.
Preferably, reflux ratio scope is 1~10 in the step (4)；More preferably 1~2.
Preferably, stabilizer alkali is directly put into from tower bottom of rectifying tower solid dog-house in the step (4).
Preferably, reflux ratio scope is 1~10 in the step (5)；More preferably 3~5.
Preferably, the pressure limit of rectification under vacuum is -0.095~-0.098MPa in the step (5).
It is using the beneficial effect of technical scheme：By the present invention in that with low polar aprotic solvent, not only rise
Extraction, and low polar solvent and etoh solvent, water electrode sex differernce are big so that and water content is very low in extract, in rectifying
During and can a small amount of moisture content azeotropic is taken out of, avoid effect of the product due to water in distillation process from constantly degrading；It is another
Aspect improves rectification system pH value, prevents that pH value decline causes product constantly to decompose in distillation process by adding solid base.It is logical
Cross a kind of method that abovementioned technology obtains highly efficient distilling and the tetraethyl orthocarbonate of steady production high sterling.With existing work
Skill compares, the technique can continuous rectification separating high-purity tetraethyl orthocarbonate, and purity ＞ 99.5%, single impurity content ＜
0.1% (in mass).
Embodiment
The present invention is further described specifically with reference to embodiments, but is not limited to this.
Embodiment 1
(1) caustic alcohol 320kg, absolute ethyl alcohol 1280kg are put into 2000L that is clean, drying reactor；
(2) control temperature that trichloronitromethane 97kg is added dropwise, adds follow-up continuous insulation reaction 3 between 65 DEG C~70 DEG C
Hour, air-distillation recovery absolute ethyl alcohol 900kg；
(3) add water 1600kg, residue is all dissolved, adds normal heptane 1280kg extractions；
(4) organic phase enters rectifying column, adds caustic alcohol 0.05kg, it is 1~2 that normal pressure, which controls reflux ratio, and first normal pressure steams
Normal heptane 1024kg；
(5) control again reflux ratio be 3~5, under -0.098MPa pressure rectifying go out product tetraethyl orthocarbonate, add up to
Obtain product：104kg, purity 99.7%, individual event impurity ＜ 0.1%, yield 91%.
Embodiment 2
(1) caustic alcohol 320kg, absolute ethyl alcohol 1600kg are put into 2000L that is clean, drying reactor；
(2) control temperature that trichloronitromethane 91.4kg is added dropwise, adds follow-up continuous insulation reaction between 65 DEG C~68 DEG C
3 hours, air-distillation recovery absolute ethyl alcohol 1120kg；
(3) add water 1920kg, residue is all dissolved, adds normal heptane 1280kg extractions；
(4) organic phase enters rectifying column, adds caustic alcohol 0.5kg, it is 1~2 that normal pressure, which controls reflux ratio, and first normal pressure steams just
Heptane 896kg；
(5) control again reflux ratio be 4~6, under -0.095MPa pressure rectifying go out product tetraethyl orthocarbonate, add up to
Obtain product：102kg, purity 99.7%, individual event impurity ＜ 0.1%, yield 90%.
Embodiment 3
(1) caustic alcohol 320kg, absolute ethyl alcohol 1280kg are put into 2000L that is clean, drying reactor；
(2) control temperature that trichloronitromethane 97kg is added dropwise, adds follow-up continuous insulation reaction 3 between 60 DEG C~65 DEG C
Hour, air-distillation recovery absolute ethyl alcohol 900kg；
(3) add water 1600kg, residue is all dissolved, adds n-hexane 1280kg extractions；
(4) organic phase enters rectifying column, adds caustic alcohol, sodium tert-butoxide 0.05kg, it is 1~2 that normal pressure, which controls reflux ratio, first
Normal pressure steams normal heptane 1024kg；
(5) control again reflux ratio be 3~5, under -0.098MPa pressure rectifying go out product tetraethyl orthocarbonate, add up to
Obtain product：103kg, purity 99.7%, individual event impurity ＜ 0.1%, yield 91%.
Embodiment 4
(1) caustic alcohol 320kg, absolute ethyl alcohol 1600kg are put into 2000L that is clean, drying reactor；
(2) control temperature that trichloronitromethane 91.4kg is added dropwise, adds follow-up continuous insulation reaction between 65 DEG C~68 DEG C
3 hours, air-distillation recovery absolute ethyl alcohol 1120kg；
(3) add water 1920kg, residue is all dissolved, adds n-hexane 1280kg extractions；
(4) organic phase enters rectifying column, adds caustic alcohol, sodium tert-butoxide 0.5kg, it is 2~3 that normal pressure, which controls reflux ratio, first
Normal pressure steams normal heptane 1152kg；
(5) control again reflux ratio be 3~5, under -0.095MPa pressure rectifying go out product tetraethyl orthocarbonate, add up to
Obtain product：102kg, purity 99.7%, individual event impurity ＜ 0.1%, yield 90%.
All documents that the present invention refers to all are incorporated as referring in this application, are individually drawn just as each document
It is used as with reference to such.
Claims (10)
- A kind of 1. method of highly efficient distilling production tetraethyl orthocarbonate：It is characterized in that comprise the following steps：（1）Caustic alcohol and absolute ethyl alcohol are added in reaction vessel, the absolute ethyl alcohol weight is 3 ~ 8 times of caustic alcohol；（2）Trichloronitromethane is added to reaction vessel, it is 60 ~ 70 DEG C to control reacting liquid temperature, adds follow-up continuous insulation reaction 1 ~ 10 hours, obtain the ethanol solution of tetraethyl orthocarbonate；The mol ratio of the trichloronitromethane and caustic alcohol is 1.0:3.1~ 4.5；（3）Air-distillation step（2）The ethanol solution of obtained tetraethyl orthocarbonate, the ethanol weight distilled out are absolute ethyl alcohol The 70 ~ 75% of addition；Solid in reaction solution is added water to after the completion of distillation all to dissolve；Then add low polar aprotic solvent extraction Extract reaction solution so that tetraethyl orthocarbonate is extracted to low polar aprotic solvent phase；The addition of low polar aprotic solvent is ethanol 3 ~ 6 times of sodium weight；（4）Step（3）The organic phase being obtained by extraction enters rectifying column, adds stabilizer alkali；Normal pressure is by controlling reflux ratio, often first Pressure steams 60 ~ 90% low polar aprotic solvent；（5）Again by controlling reflux ratio, rectification under vacuum goes out tetraethyl orthocarbonate.
- 2. the method for highly efficient distilling production high sterling tetraethyl orthocarbonate according to claim 1, it is characterised in that described The step（1）In absolute ethyl alcohol dosage be 4 ~ 5 times of caustic alcohol weight.
- 3. the method for highly efficient distilling production high sterling tetraethyl orthocarbonate according to claim 1, it is characterised in that described The mol ratio of trichloronitromethane and caustic alcohol is 1.0：3.3~3.5.
- 4. the method for highly efficient distilling production high sterling tetraethyl orthocarbonate according to claim 1, it is characterised in that described Step（3）In low polar aprotic solvent be petroleum ether, n-hexane, hexamethylene, normal heptane or normal octane.
- 5. the method for highly efficient distilling production high sterling tetraethyl orthocarbonate according to claim 4, it is characterised in that described Step（3）In the addition of low polar aprotic solvent be 4 ~ 5 times of caustic alcohol weight.
- 6. the method for highly efficient distilling production high sterling tetraethyl orthocarbonate according to claim 1, it is characterised in that described The step（4）In stabilizer alkali be：Sodium carbonate, sodium hydroxide, potassium hydroxide, sodium methoxide, caustic alcohol, potassium ethoxide, isopropyl One kind or any two kinds of mixture in sodium alkoxide, sodium tert-butoxide or potassium tert-butoxide.
- 7. the method for highly efficient distilling production high sterling tetraethyl orthocarbonate according to claim 6, it is characterised in that described Step（4）In stabilizer alkali addition be trichloronitromethane weight 0.01 ~ 0.5%.
- 8. the method for highly efficient distilling production high sterling tetraethyl orthocarbonate according to claim 7, it is characterised in that described Step（4）In stabilizer alkali addition be trichloronitromethane weight 0.05 ~ 0.1%.
- 9. the method for the highly efficient distilling production high sterling tetraethyl orthocarbonate according to any one of claim 1 ~ 8, its feature It is, the step（4）Middle reflux ratio scope is 1 ~ 10.
- 10. the method for the highly efficient distilling production high sterling tetraethyl orthocarbonate according to any one of claim 1 ~ 8, its feature It is, the step（5）Middle reflux ratio scope is 1 ~ 10.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1203223A (en) * | 1997-05-26 | 1998-12-30 | 武田药品工业株式会社 | Production method of aminobenzene compound |
| CN103804157A (en) * | 2014-01-14 | 2014-05-21 | 常州吉恩化工有限公司 | Method for producing tetraethyl orthocarbonate with coproduction of 5-chlorovaleronitrile |
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2017
- 2017-10-13 CN CN201710950038.9A patent/CN107573223B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1203223A (en) * | 1997-05-26 | 1998-12-30 | 武田药品工业株式会社 | Production method of aminobenzene compound |
| CN103804157A (en) * | 2014-01-14 | 2014-05-21 | 常州吉恩化工有限公司 | Method for producing tetraethyl orthocarbonate with coproduction of 5-chlorovaleronitrile |
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