CN107573248A - The recovery method of resolving agent R phenyl ethylamines in prepared by R-DHLA - Google Patents
The recovery method of resolving agent R phenyl ethylamines in prepared by R-DHLA Download PDFInfo
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- CN107573248A CN107573248A CN201710874343.4A CN201710874343A CN107573248A CN 107573248 A CN107573248 A CN 107573248A CN 201710874343 A CN201710874343 A CN 201710874343A CN 107573248 A CN107573248 A CN 107573248A
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Abstract
The recovery method of resolving agent R phenyl ethylamines, this method comprise the following steps in being prepared present invention is disclosed a kind of R-DHLA：Agitating device needed for preparation, material or solution containing R phenyl ethylamine salt are put into the reaction vessel equipped with agitating device, pH value is adjusted at 20 DEG C~25 DEG C to 10~14, stratification, obtains organic layer, and solvent is distilled off in organic layer, the cut in 187~189 DEG C is collected, obtains R phenyl ethylamines；The material or solution of the R phenyl ethylamines salt are R-DHLA into salt mother liquor；The R-DHLA into salt mother liquor be the waste liquid containing R lipoic acids R phenyl ethylamines salt and S lipoic acid R phenyl ethylamine salt mixtures.The invention provides a kind of process for cleanly preparing, improves the utilization ratio of R phenyl ethylamines, R phenyl ethylamines is recycled, and reduces R phenyl ethylamines consumption and cost, mitigates environmental protection pressure, realizes green productive target.
Description
Technical field
The present invention relates to belong to resolving agent R- phenyl ethylamines in clean manufacturing field, more particularly to a kind of preparation of R-DHLA
Recovery method.
Background technology
R- phenyl ethylamines are a kind of conventional resolving agents, are widely used in the fractionation of racemization organic acid, and it is organic to prepare high-purity dextrorotation
Acid.English name：D(+)-alpha-Methylbenzylamine；Chemical name：R (+)-ɑ-methylbenzylamine；CAS NO：3886-69-
9；Molecular formula：C8H11N；Molecular weight：121.18；Structural formula：
。
The outward appearance of R- phenyl ethylamines is colourless to weak yellow liquid；Boiling point：187-189ºC；Specific rotatory power：[a] D20=+ 37~
+40°；Content（GC）≥99%.
R- phenyl ethylamines, with ɑ-lipoic acid into salt, form LA R- phenyl ethylamines salt and S-- sulphur are pungent as a kind of resolving agent
Sour R- phenyl ethylamines salt mixture, using the difference of two kinds of salt solubility in organic solvent, alternative separates out LA R-
Phenyl ethylamine salt, more S-- lipoic acid R- phenyl ethylamines salt dissolve the purpose for, reaching make two kinds of salt separation in organic solvent.
Either high purity salt, or the mixture of two kinds of salt, after sodium hydrate aqueous solution processing, it is pungent to be respectively formed R- sulphur
Sour sodium or S-- sodium thioctate, dissociate R- phenyl ethylamines., can be R- using difference of the R- phenyl ethylamines in water and organic solvent
Phenyl ethylamine is enriched with into organic solvent, makes LA sodium water solution or the S-- sodium thioctates aqueous solution and R- phenyl ethylamines organic molten
Agent solution is separated, and obtains the R- phenyl ethylamines of higher degree, and redistillation removes organic solvent, collects 187-189 DEG C of fraction, obtains
To qualified R- phenyl ethylamines.
R- phenyl ethylamines form ionic bond with ɑ-lipoic acid into salt, and R- benzene second is returned to after sodium hydrate aqueous solution processing
Amine.If without the recycling of R- phenyl ethylamines, the cost of raw material of product is not only increased, and the waste water of phenyl ethylamine containing R-
Processing also increases treatment cost and environmental protection pressure, is unfavorable for the production of product.On the utilization process of R- phenyl ethylamines, mesh
Before have not been reported.
The content of the invention
The purpose of the present invention is exactly to solve the above-mentioned problems in the prior art, there is provided a kind of R-DHLA system
The recovery method of standby middle resolving agent R- phenyl ethylamines.
The purpose of the present invention will be achieved by the following technical programs：Resolving agent R- phenyl ethylamines in prepared by R-DHLA
Recovery method, this method comprises the following steps：
Agitating device needed for preparation, the material or molten containing R- phenyl ethylamine salt is put into the reaction vessel equipped with agitating device
Liquid, pH value is adjusted at 20 DEG C~25 DEG C to 10~14, stratification, obtains organic layer, solvent is distilled off in organic layer, collects
Cut at 187~189 DEG C, obtain R- phenyl ethylamines.
Preferably, the material of the R- phenyl ethylamines salt or solution are R-DHLA into salt mother liquor.
Preferably, the R-DHLA into salt mother liquor be containing LA R- phenyl ethylamines salt and S-- lipoic acid R- benzene
The waste liquid of ethamine salt mixture.
Preferably, the material of the R- phenyl ethylamines salt or solution are R-DHLA refinement mother liquor.
Preferably, the R-DHLA refinement mother liquor is to contain LA R- phenyl ethylamines salt and S-- lipoic acid R- benzene
The waste liquid of ethamine salt mixture.
Preferably, the material of the R- phenyl ethylamines salt or solution are LA R- phenyl ethylamine salt fine work and toluene.
Preferably, the LA R- phenyl ethylamine salt fine work is the product containing LA R- phenyl ethylamine salt.
Preferably, the weight ratio of the LA R- phenyl ethylamine salt fine work and toluene is 1：5.
Preferably, 10% strong alkali aqueous solution is added dropwise at 20 DEG C~25 DEG C.
Preferably, the strong alkali aqueous solution is one kind in sodium hydroxide, potassium hydroxide.
The advantages of technical solution of the present invention, is mainly reflected in：The technical program can improve the utilization ratio of R- phenyl ethylamines, make
R- phenyl ethylamines can recycle, and reduce R- phenyl ethylamines consumption and cost, mitigate environmental protection pressure, realize green production mesh
Mark.
Embodiment
The purpose of the present invention, advantage and feature, it will be explained by the non-limitative illustration of preferred embodiment below.This
A little embodiments are only the prominent examples using technical solution of the present invention, all to take equivalent substitution or equivalent transformation and formed
Technical scheme, all fall within the scope of protection of present invention.
Resolving agent R- phenyl ethylamines R-DHLA preparation in ɑ-lipoic acid into salt, utilize LA R- phenyl ethylamine salt
With the dissolubility difference of S-- lipoic acid R- phenyl ethylamines salt in a solvent, play a part of separating LA and S- lipoic acids.And
Either LA R- phenyl ethylamines salt, or S-- lipoic acid R- phenyl ethylamine salt, after sodium hydrate aqueous solution is handled, by shape
It is dissolved in water into LA sodium or S- sodium thioctates, the R- phenyl ethylamines after dissociating are extracted with organic solvent, are transferred to organic molten
In agent, redistillation removes organic solvent, and rectifying obtains R- phenyl ethylamines, can continue on for R-DHLA system after analysis is qualified
It is standby.
R- phenyl ethylamines are formed with three kinds and existed in prepared by R-DHLA：Contain LA R- phenyl ethylamines into salt mother liquor
Salt and S-- lipoic acid R- phenyl ethylamine salt mixtures；Contain LA R- phenyl ethylamines salt and S-- lipoic acid R- benzene in refinement mother liquor
Ethamine salt mixture；LA R- phenyl ethylamine salt fine work.
Present invention is disclosed a kind of R-DHLA prepare in resolving agent R- phenyl ethylamines recovery method, this method include with
Lower step：
Agitating device needed for preparation, the material or molten containing R- phenyl ethylamine salt is put into the reaction vessel equipped with agitating device
Liquid, is added dropwise 10% strong alkali aqueous solution at 20 DEG C~25 DEG C, and the strong alkali aqueous solution is one in sodium hydroxide, potassium hydroxide
Kind, regulation pH value to 10~14, stratification, organic layer is obtained, solvent is distilled off in organic layer, collects evaporating at 187~189 DEG C
Part, obtain R- phenyl ethylamines.
Embodiment 1：
Agitating device needed for preparation, the material or molten containing R- phenyl ethylamine salt is put into the reaction vessel equipped with agitating device
Liquid, pH value is adjusted at 20 DEG C~25 DEG C to 10~14, stratification, obtains organic layer, solvent is distilled off in organic layer, collects
Fraction at 187~189 DEG C, obtain R- phenyl ethylamines.
In the present embodiment, the material of the R- phenyl ethylamines salt or solution are R-DHLA into salt mother liquor, specifically, institute
It is useless containing LA R- phenyl ethylamines salt and S-- lipoic acid R- phenyl ethylamine salt mixtures that R-DHLA, which is stated, into salt mother liquor
Liquid.
Further, into the reaction vessel equipped with agitating device put into R-DHLA into salt thiacyclohexane mother liquor about
1290g（The 3.3g of phenyl ethylamine containing R-）, the sodium hydrate aqueous solution of dropwise addition 10% at 20 DEG C -25 DEG C, adjust pH value to be stood to 10-14
Layering, organic layer are washed with water 130g, stratification, organic layer heating, solvent are distilled off, then are heated up, and collect 187-189 DEG C
Under fraction, obtain R- phenyl ethylamine 3.1g, yield 93.9%.
R-DHLA is put into the reaction vessel equipped with agitating device into salt toluenic mother liquor about 460g（Phenyl ethylamine containing R-
4.5g）, the sodium hydrate aqueous solution of dropwise addition 10% at 20 DEG C -25 DEG C, pH value is adjusted to 10-14, stratification, organic layer water
50g is washed, stratification, organic layer heating, solvent is distilled off, then is heated up, and is collected the fraction at 187-189 DEG C, is obtained R-
Phenyl ethylamine 4.1g, yield 91.1%.
Embodiment 2：
Agitating device needed for preparation, the material or molten containing R- phenyl ethylamine salt is put into the reaction vessel equipped with agitating device
Liquid, pH value is adjusted at 20 DEG C~25 DEG C to 10~14, stratification, obtains organic layer, solvent is distilled off in organic layer, collects
Fraction at 187~189 DEG C, obtain R- phenyl ethylamines.
In the present embodiment, the material of the R- phenyl ethylamines salt or solution are R-DHLA refinement mother liquor, specifically, institute
It is useless containing LA R- phenyl ethylamines salt and S-- lipoic acid R- phenyl ethylamine salt mixtures to state R-DHLA refinement mother liquor
Liquid.
Further, R-DHLA refined toluene mother liquor about 375g is put into the reaction vessel equipped with agitating device
（The 4.6g of phenyl ethylamine containing R-）, the sodium hydrate aqueous solution of dropwise addition 10% at 20 DEG C -25 DEG C, tune pH value to 10-14, stratification,
Organic layer is washed with water 40g, stratification, organic layer heating, solvent is distilled off, then is heated up, and collects evaporating at 187-189 DEG C
Part, obtain R- phenyl ethylamine 4.2g, yield 91.3%.
R-DHLA purified acetic acid ethyl ester mother liquor about 125g is put into the reaction vessel equipped with agitating device（Benzene containing R-
Ethamine 2.1g）, the sodium hydrate aqueous solution of dropwise addition 10% at 20 DEG C -25 DEG C, pH value is adjusted to 10-14, stratification, organic layer
Washed with water 20g, stratification, organic layer heating, solvent is distilled off, then heated up, collected the fraction at 187-189 DEG C, obtain
To R- phenyl ethylamine 1.9g, yield 90.5%.
Embodiment 3：
Agitating device needed for preparation, the material or molten containing R- phenyl ethylamine salt is put into the reaction vessel equipped with agitating device
Liquid, pH value is adjusted at 20 DEG C~25 DEG C to 10~14, stratification, obtains organic layer, solvent is distilled off in organic layer, collects
Fraction at 187~189 DEG C, obtain R- phenyl ethylamines.
In the present embodiment, the material of the R- phenyl ethylamines salt or solution are LA R- phenyl ethylamine salt fine work and first
Benzene, specifically, the material or solution of the R- phenyl ethylamines salt are the product containing LA R- phenyl ethylamine salt.
Further, LA R- phenyl ethylamine salt fine work 32.8g is put into the reaction vessel equipped with agitating device
With toluene 164g, the sodium hydrate aqueous solution of dropwise addition 10% at 20 DEG C -25 DEG C, pH value is adjusted to 10-14, stratification, organic layer
Washed with water 20g, stratification, organic layer heating, solvent is distilled off, then heated up, collected the fraction at 187-189 DEG C, obtain
To R- phenyl ethylamine 11.5g, yield 94.8%.
The technical program can improve the utilization ratio of R- phenyl ethylamines, R- phenyl ethylamines is recycled, and reduce R- phenyl ethylamines
Consumption and cost, mitigate environmental protection pressure, realize green productive target.
The present invention still has numerous embodiments, all technical sides formed using equivalents or equivalent transformation
Case, it is within the scope of the present invention.
Claims (10)
1. the recovery method of resolving agent R- phenyl ethylamines in prepared by R-DHLA, it is characterised in that：This method comprises the following steps：
Agitating device needed for preparation, the material or molten containing R- phenyl ethylamine salt is put into the reaction vessel equipped with agitating device
Liquid, pH value is adjusted at 20 DEG C~25 DEG C to 10~14, stratification, obtains organic layer, solvent is distilled off in organic layer, collects
Cut at 187~189 DEG C, obtain R- phenyl ethylamines.
2. the recovery method of resolving agent R- phenyl ethylamines in prepared by R-DHLA according to claim 1, it is characterised in that：
The material or solution of the R- phenyl ethylamines salt are R-DHLA into salt mother liquor.
3. the recovery method of resolving agent R- phenyl ethylamines in prepared by R-DHLA according to claim 2, it is characterised in that：
The R-DHLA is useless containing LA R- phenyl ethylamines salt and S-- lipoic acid R- phenyl ethylamine salt mixtures into salt mother liquor
Liquid.
4. the recovery method of resolving agent R- phenyl ethylamines in prepared by R-DHLA according to claim 1, it is characterised in that：
The material or solution of the R- phenyl ethylamines salt are R-DHLA refinement mother liquor.
5. the recovery method of resolving agent R- phenyl ethylamines in prepared by R-DHLA according to claim 4, it is characterised in that：
The R-DHLA refinement mother liquor is useless containing LA R- phenyl ethylamines salt and S-- lipoic acid R- phenyl ethylamine salt mixtures
Liquid.
6. the recovery method of resolving agent R- phenyl ethylamines in prepared by R-DHLA according to claim 1, it is characterised in that：
The material or solution of the R- phenyl ethylamines salt are LA R- phenyl ethylamine salt fine work and toluene.
7. the recovery method of resolving agent R- phenyl ethylamines in prepared by R-DHLA according to claim 6, it is characterised in that：
The material or solution of the R- phenyl ethylamines salt are the product containing LA R- phenyl ethylamine salt.
8. the recovery method of resolving agent R- phenyl ethylamines in prepared by R-DHLA according to claim 7, it is characterised in that：
The weight ratio of the LA R- phenyl ethylamine salt fine work and toluene is 1：5.
9. the recovery method of resolving agent R- phenyl ethylamines in prepared by R-DHLA according to claim 1, it is characterised in that：
10% strong alkali aqueous solution is added dropwise at 20 DEG C~25 DEG C.
10. the recovery method of resolving agent R- phenyl ethylamines, its feature exist in prepared by R-DHLA according to claim 9
In：The strong alkali aqueous solution is one kind in sodium hydroxide, potassium hydroxide.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109400556A (en) * | 2018-12-29 | 2019-03-01 | 上海应用技术大学 | A kind of synthetic method of D- (-)-pantoic acid lactone |
| CN112390779A (en) * | 2019-08-16 | 2021-02-23 | 南京海润医药有限公司 | Preparation method of dextro lipoic acid |
| CN113087630A (en) * | 2021-04-06 | 2021-07-09 | 宣城美诺华药业有限公司 | Method for recycling and applying perindopril intermediate resolving agent (R) - (+) -alpha-phenylethylamine |
| CN114181192A (en) * | 2021-11-21 | 2022-03-15 | 福建科宏生物工程股份有限公司 | Resin deamination method in R-lipoic acid synthesis process |
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| CN104860830A (en) * | 2015-04-08 | 2015-08-26 | 东北制药集团股份有限公司 | Preparation method for R-(+)-alpha-phenylethylamine salt and R-(+)-alpha-phenylethylamine |
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Patent Citations (3)
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| CN102442994A (en) * | 2011-10-31 | 2012-05-09 | 江苏同禾药业有限公司 | Racemization method of S-lipoic acid and preparation method of R-lipoic acid |
| CN104086439A (en) * | 2014-06-30 | 2014-10-08 | 浙江华海药业股份有限公司 | Method for recovering pregabalin intermediate resolving agent (R)-(+)-alpha-phenylethylamine |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109400556A (en) * | 2018-12-29 | 2019-03-01 | 上海应用技术大学 | A kind of synthetic method of D- (-)-pantoic acid lactone |
| CN112390779A (en) * | 2019-08-16 | 2021-02-23 | 南京海润医药有限公司 | Preparation method of dextro lipoic acid |
| CN112390779B (en) * | 2019-08-16 | 2022-09-06 | 南京海润医药有限公司 | Preparation method of dextro lipoic acid |
| CN113087630A (en) * | 2021-04-06 | 2021-07-09 | 宣城美诺华药业有限公司 | Method for recycling and applying perindopril intermediate resolving agent (R) - (+) -alpha-phenylethylamine |
| CN114181192A (en) * | 2021-11-21 | 2022-03-15 | 福建科宏生物工程股份有限公司 | Resin deamination method in R-lipoic acid synthesis process |
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Application publication date: 20180112 |