CN105859546B - The method of S-MA is recycled from tomoxetine hydrochloride production waste liquid - Google Patents
The method of S-MA is recycled from tomoxetine hydrochloride production waste liquid Download PDFInfo
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- CN105859546B CN105859546B CN201610242781.4A CN201610242781A CN105859546B CN 105859546 B CN105859546 B CN 105859546B CN 201610242781 A CN201610242781 A CN 201610242781A CN 105859546 B CN105859546 B CN 105859546B
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- C07C51/02—Preparation of carboxylic acids or their salts, halides or anhydrides from salts of carboxylic acids
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- C07C51/42—Separation; Purification; Stabilisation; Use of additives
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Abstract
The present invention relates to a kind of methods that S-MA is recycled from tomoxetine hydrochloride production waste liquid, belong to S-MA recovery technology field.The present invention is that inorganic acid, the pH value of regulation system is added into tomoxetine hydrochloride production waste liquid；Then organic solvent is added, stirs, stands, liquid separation；Organic phase vacuum distillation, is precipitated S-MA crude product after being evaporated；Organic solvent is added into S-MA crude product, is warming up to dissolution, slow cooling crystallization, growing the grain filters, and washs, and it is dry, obtain S-MA fine work.Present invention process is stable, reaction condition is easily controllable, no pollution to the environment, at low cost, the rate of recovery is high, is easy to industrialize.
Description
Technical field
The present invention relates to a kind of methods that S-MA is recycled from tomoxetine hydrochloride production waste liquid, belong to S-MA
Recovery technology field.
Background technique
Tomoxetine hydrochloride is a kind of chemicals treated for children and teen-age hyperactivity.Tomoxetine hydrochloride
For the hydrochloride form of R- atomoxetine.The source of R- atomoxetine is the chiral resolution of racemization atomoxetine.Racemization support Moses
The chiral resolution in spit of fland includes following steps: racemization atomoxetine is held in the palm first with S-MA (chiral resolving agent) at salt with R-
Moses spit of fland-S-MA salt form Crystallization Separation.R- atomoxetine-S-MA salt dissociates under alkaline condition, obtains R-
Atomoxetine, while also obtaining the waste liquid of S-MA sodium-salt aqueous solution.R- atomoxetine is reacted with HCl, generates atomoxetine hydrochloride
Xi Ting.
The waste liquid of the S-MA sodium-salt aqueous solution generated in tomoxetine hydrochloride production process becomes mixed with other substances
Waste liquid is closed, is not isolated and purified and is recycled comprehensive utilization, pollution not only is caused to environment, but also cause certain money
Source waste.
Summary of the invention
The purpose of the present invention is to provide it is a kind of from tomoxetine hydrochloride production waste liquid in recycle S-MA method,
Process stabilizing, reaction condition are easily controllable, no pollution to the environment, at low cost, the rate of recovery is high, are easy to industrialize.
To achieve the goals above, the technological means that the application takes is as follows:
A method of S-MA is recycled from tomoxetine hydrochloride production waste liquid, comprising the following steps:
(1) when the temperature of control tomoxetine hydrochloride production waste liquid is 10~30 DEG C, and inorganic acid is added thereto, adjusts
The pH of system is 1.0~5.0；The time for adjusting pH process controls in 30~40min；After having adjusted pH value, then into system plus
Enter organic solvent, stir, stand, liquid separation, divide and remove lower layer's water phase, retains upper organic phase；
(2) organic phase obtained by step (1) is evaporated under reduced pressure, solid is precipitated after being evaporated in recycling design, obtains S- almond
Acid crude；
(3) organic solvent will be added in S-MA crude product obtained by step (2), is warming up to dissolution, is cooled in 2~6h
0~30 DEG C, 1~5h of growing the grain, is filtered at this temperature, washing, at 50~55 DEG C, is dried in vacuo 5~6h, is obtained S-MA
Fine work.
In step (1), the tomoxetine hydrochloride production waste liquid is R- atomoxetine-S-MA salt in alkaline condition
The S-MA sodium-salt aqueous solution waste liquid of free process down, the quality percentage that tomoxetine hydrochloride produces S-MA in waste liquid contain
Amount is 8~12%.
In step (1), the inorganic acid includes hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid.The inorganic acid of above selection is all
It is strong acid, is almost ionized into hydrogen ion and acid radical anion in water.Mandelic acid is weak acid, can only partial ionization, and can
It is inverse.After inorganic acid strong acid is added in the sodium-salt aqueous solution of mandelic acid, the hydrogen ion in system just will increase, so that mandelic acid
Ionization process inversely carries out, and almond acid radical anion is promoted to become almond acid molecule.
Inorganic acid completion of dropwise addition in 30~40min is best, it is possible to reduce exothermic effect when inorganic acid is added is reduced
The security risk of production.
In step (1), the pH value of the regulation system is 2.0~3.0.PH value could make almond acid group negative less than 5.0
Ion conversion is at mandelic acid.PH value is lower, and yield is higher；When pH value is 2.0~3.0, yield has reached highest, then reduces pH
It is worth nonsensical.
In step (1), the addition organic solvent is lipid or ether organic solvent；The body of organic solvent and waste liquid is added
Product ratio 0.2~2.0.
In step (3), the organic solvent is the mixed solution of ethyl acetate and normal heptane, ethyl acetate and normal heptane
Mass ratio is 1:2~1:8；The mass volume ratio of S-MA crude product and mixed solvent is 1:4~1:10.Ethyl acetate is almond
The benign solvent of acid, normal heptane are bad solvent.
The mass ratio of ethyl acetate and normal heptane is that could dissolve mandelic acid, the matter of ethyl acetate and normal heptane less than 1:2
When amount is than being 1:3~1:4, yield highest.
In step (3), the organic solvent is the mixed solution of ethyl acetate and normal heptane, ethyl acetate and normal heptane
Mass ratio is 1:3~1:4；The mass volume ratio of S-MA crude product and mixed solvent is 1:8~1:9.
In step (3), the cleaning solvent is normal heptane, and the mass volume ratio of S-MA crude product and cleaning solvent is 1:
1~1:5.
Compared with prior art, the invention has the following advantages that
The maximum innovative point of the application is to be recycled mandelic acid；In the prior art, containing the waste liquid of mandelic acid
Usually regard chemical engineering sewage, entrust to special chemical engineering sewage factory, the modes such as physical chemistry and biodegrade of progress are handled.
Mandelic acid is weak acid, can only partial ionization, and it is reversible.
Inorganic acid is all strong acid, is almost ionized into hydrogen ion and acid radical anion in water.
After inorganic acid strong acid is added in the sodium-salt aqueous solution of mandelic acid, the hydrogen ion in system just will increase, so that flat
The ionization process of peach acid inversely carries out, and almond acid radical anion is promoted to become almond acid molecule.
Almond acid molecule is separated from the water out, is the method for extraction.
Extraction: using the difference of solute solubility in immiscible solvent, with a kind of solvent solute from another molten
The operating method extracted in solution composed by agent.
Mandelic acid is organic acid, and the dissolubility of mandelic acid in organic solvent is greater than dissolubility in water.
Organic solvent is added in water, mandelic acid can be extracted into organic phase from water phase, divides and removes water phase, decompression is steamed
After dry organic phase, mandelic acid can be obtained.
Operation of the present invention is simple, and process conditions are mild, easily controllable, and (HPLC content is 99.0% to products obtained therefrom purity is high
More than), 80.0% or more yield thoroughly solves S-MA in tomoxetine hydrochloride production waste liquid and asks the pollution of environment
Topic, while the tomoxetine hydrochloride in waste liquid is recycled and is purified, and the three wastes are reduced, and realizes circular economy, drop
Low production cost, process stabilizing are suitble to industrialized production.
Specific embodiment
Below with reference to embodiment, the present invention is further illustrated, but is not intended to limit implementation of the invention.
Embodiment 1
(1) tomoxetine hydrochloride that 200mL mandelic acid containing 10wt%S- is added into 1000mL three-necked flask produces waste liquid；
Stirring is opened, concentrated hydrochloric acid is added dropwise at 25 DEG C, the pH value of regulation system is 3.0；Then 160mL ethyl acetate is added, is stirred at 25 DEG C
Mix 30min；Stop stirring, stands 20min at 25 DEG C；Liquid separation divides and removes lower layer's water phase, retains upper organic phase.
(2) organic phase obtained by upper step is transferred in 500mL single-necked flask, is evaporated under reduced pressure at 35 DEG C, recycling design,
Solid is precipitated after being evaporated, obtains S-MA crude product 18.3g；
(3) 18.3g S-MA crude product and 146mL mixed solvent (ethyl acetate: just are added into 500mL three-necked flask
Heptane=1:3)；Stirring is opened, is warming up to 65 DEG C, stirring 20min dissolution；Slow cooling crystallization, about 5h are cooled to 5 DEG C；0~5
DEG C growing the grain 2h is filtered after growing the grain, and 55mL normal heptane washs filter cake, dry under vacuum degree >=-0.08MPa, temperature 50 C
5 hours, S-MA fine work 16.5g, total recovery 82.5% are obtained, HPLC content is 99.45%.
Embodiment 2
(1) tomoxetine hydrochloride that 300mL mandelic acid containing 10wt%S- is added into 1000mL three-necked flask produces waste liquid；
Stirring is opened, the concentrated sulfuric acid is added dropwise at 25 DEG C, the pH value of regulation system is 2.5；Then 300mL ethyl acetate is added, is stirred at 25 DEG C
Mix 30min；Stop stirring, stands 20min at 25 DEG C；Liquid separation divides and removes lower layer's water phase, retains upper organic phase.
(2) organic phase obtained by upper step is transferred in 1000mL single-necked flask, is evaporated under reduced pressure at 35 DEG C, recycled molten
Solid is precipitated after being evaporated in agent, obtains S-MA crude product 26.8g；
(3) 26.8g S-MA crude product and 214mL mixed solvent (ethyl acetate: just are added into 500mL three-necked flask
Heptane=1:4)；Stirring is opened, is warming up to 70 DEG C, stirring 20min dissolution；Slow cooling crystallization, about 5h are cooled to 5 DEG C；0~5
DEG C growing the grain 2h is filtered after growing the grain, and 80mL normal heptane washs filter cake, dry under vacuum degree >=-0.08MPa, temperature 50 C
5 hours, S-MA fine work 25.1g, total recovery 83.7% are obtained, HPLC content is 99.35%.
Embodiment 3
(1) tomoxetine hydrochloride that 300mL mandelic acid containing 10wt%S- is added into 1000mL three-necked flask produces waste liquid；
Stirring is opened, phosphoric acid is added dropwise at 25 DEG C, the pH value of regulation system is 2.0；Then 300mL ethyl acetate is added, is stirred at 25 DEG C
30min；Stop stirring, stands 20min at 25 DEG C；Liquid separation divides and removes lower layer's water phase, retains upper organic phase.
(2) organic phase obtained by upper step is transferred in 1000mL single-necked flask, is evaporated under reduced pressure at 35 DEG C, recycled molten
Solid is precipitated after being evaporated in agent, obtains S-MA crude product 26.4g；
(3) 26.4g S-MA crude product and 238mL mixed solvent (ethyl acetate: just are added into 500mL three-necked flask
Heptane=1:4)；Stirring is opened, is warming up to 70 DEG C, stirring 20min dissolution；Slow cooling crystallization, about 5h are cooled to 5 DEG C；0~5
DEG C growing the grain 2h is filtered after growing the grain, and 80mL normal heptane washs filter cake, dry under vacuum degree >=-0.08MPa, temperature 50 C
5 hours, S-MA fine work 24.4g, total recovery 81.3% are obtained, HPLC content is 99.27%.
Embodiment 4
(1) tomoxetine hydrochloride that 200mL mandelic acid containing 10wt%S- is added into 1000mL three-necked flask produces waste liquid；
Stirring is opened, concentrated hydrochloric acid is added dropwise at 25 DEG C, the pH value of regulation system is 3.0；Then 160mL ether is added, is stirred at 25 DEG C
30min；Stop stirring, stands 20min at 25 DEG C；Liquid separation divides and removes lower layer's water phase, retains upper organic phase.
(2) organic phase obtained by upper step is transferred in 500mL single-necked flask, is evaporated under reduced pressure at 35 DEG C, recycling design,
Solid is precipitated after being evaporated, obtains S-MA crude product 17.5g；
(3) 17.5g S-MA crude product and 140mL mixed solvent (ethyl acetate: just are added into 500mL three-necked flask
Heptane=1:3)；Stirring is opened, is warming up to 65 DEG C, stirring 20min dissolution；Slow cooling crystallization, about 5h are cooled to 5 DEG C；0~5
DEG C growing the grain 2h is filtered after growing the grain, and 53mL normal heptane washs filter cake, dry under vacuum degree >=-0.08MPa, temperature 50 C
6 hours, S-MA fine work 16.2g, total recovery 81.0% are obtained, HPLC content is 99.53%.
Embodiment 5
(1) tomoxetine hydrochloride that 300mL mandelic acid containing 10wt%S- is added into 1000mL three-necked flask produces waste liquid；
Stirring is opened, the concentrated sulfuric acid is added dropwise at 25 DEG C, the pH value of regulation system is 2.5；Then 300mL ether is added, is stirred at 25 DEG C
30min；Stop stirring, stands 20min at 25 DEG C；Liquid separation divides and removes lower layer's water phase, retains upper organic phase.
(2) organic phase obtained by upper step is transferred in 1000mL single-necked flask, is evaporated under reduced pressure at 35 DEG C, recycled molten
Solid is precipitated after being evaporated in agent, obtains S-MA crude product 27.0g；
(3) 27.0g S-MA crude product and 243mL mixed solvent (ethyl acetate: just are added into 500mL three-necked flask
Heptane=1:4)；Stirring is opened, is warming up to 70 DEG C, stirring 20min dissolution；Slow cooling crystallization, about 5h are cooled to 5 DEG C；0~5
DEG C growing the grain 2h is filtered after growing the grain, and 81mL normal heptane washs filter cake, dry under vacuum degree >=-0.08MPa, temperature 50 C
6 hours, S-MA fine work 25.4g, total recovery 84.7% are obtained, HPLC content is 99.31%.
Embodiment 6
(1) tomoxetine hydrochloride that 300mL mandelic acid containing 10wt%S- is added into 1000mL three-necked flask produces waste liquid；
Stirring is opened, the concentrated sulfuric acid is added dropwise at 25 DEG C, the pH value of regulation system is 2.5；Then addition 300mL methyl tertiary butyl ether(MTBE), 25 DEG C
Lower stirring 30min；Stop stirring, stands 20min at 25 DEG C；Liquid separation divides and removes lower layer's water phase, retains upper organic phase.
(2) organic phase obtained by upper step is transferred in 1000mL single-necked flask, is evaporated under reduced pressure at 35 DEG C, recycled molten
Solid is precipitated after being evaporated in agent, obtains S-MA crude product 25.9g；
(3) 25.9g S-MA crude product and 233mL mixed solvent (ethyl acetate: just are added into 500mL three-necked flask
Heptane=1:3)；Stirring is opened, is warming up to 70 DEG C, stirring 20min dissolution；Slow cooling crystallization, about 5h are cooled to 5 DEG C；0~5
DEG C growing the grain 2h is filtered after growing the grain, and 78mL normal heptane washs filter cake, dry under vacuum degree >=-0.08MPa, temperature 50 C
6 hours, S-MA fine work 23.8g, total recovery 79.3% are obtained, HPLC content is 99.40%.
Embodiment 7
(1) tomoxetine hydrochloride that 300mL mandelic acid containing 10wt%S- is added into 1000mL three-necked flask produces waste liquid；
Stirring is opened, phosphoric acid is added dropwise at 25 DEG C, the pH value of regulation system is 2.0；Then 300mL methyl tertiary butyl ether(MTBE) is added, at 25 DEG C
Stir 30min；Stop stirring, stands 20min at 25 DEG C；Liquid separation divides and removes lower layer's water phase, retains upper organic phase.
(2) organic phase obtained by upper step is transferred in 1000mL single-necked flask, is evaporated under reduced pressure at 35 DEG C, recycled molten
Solid is precipitated after being evaporated in agent, obtains S-MA crude product 25.4g；
(3) 25.4g S-MA crude product and 229mL mixed solvent (ethyl acetate: just are added into 500mL three-necked flask
Heptane=1:4)；Stirring is opened, is warming up to 70 DEG C, stirring 20min dissolution；Slow cooling crystallization, about 5h are cooled to 5 DEG C；0~5
DEG C growing the grain 2h is filtered after growing the grain, and 76mL normal heptane washs filter cake, dry under vacuum degree >=-0.08MPa, temperature 50 C
6 hours, S-MA fine work 23.1g, total recovery 77.0% are obtained, HPLC content is 99.46%.
Claims (2)
1. a kind of method for recycling S-MA from tomoxetine hydrochloride production waste liquid, which comprises the following steps:
(1) when the temperature of control tomoxetine hydrochloride production waste liquid is 10~30 DEG C, and inorganic acid is added thereto, adjusts body
The pH of system is 2.0~3.0；The time for adjusting pH process controls in 30~40min；After having adjusted pH value, then it is added into system
Organic solvent stirs, and stands, liquid separation, divides and removes lower layer's water phase, retains upper organic phase；
(2) organic phase obtained by step (1) is evaporated under reduced pressure, recycling design is precipitated solid after being evaporated, obtains S-MA
Crude product；
(3) organic solvent will be added in S-MA crude product obtained by step (2), is warming up to dissolution, 0 ~ 30 is cooled in 2 ~ 6h
DEG C, 1 ~ 5h of growing the grain, is filtered at this temperature, washing, at 50~55 DEG C, is dried in vacuo 5~6h, is obtained S-MA fine work；
In step (1), the tomoxetine hydrochloride production waste liquid is that R- atomoxetine-S-MA salt is swum under alkaline condition
S-MA sodium-salt aqueous solution waste liquid from process, the mass percentage that tomoxetine hydrochloride produces S-MA in waste liquid are
8~12%；
In step (1), the addition organic solvent is esters or ether organic solvent；The volume ratio of organic solvent and waste liquid is added
0.2~2.0.
In step (3), the organic solvent is the mixed solution of ethyl acetate and normal heptane, the quality of ethyl acetate and normal heptane
Than for 1:3~1:4；The mass volume ratio of S-MA crude product and mixed solvent is 1:8~1:9；
In step (3), the cleaning solvent is normal heptane, the mass volume ratio of S-MA crude product and cleaning solvent be 1:1~
1:5。
2. the method for S-MA is recycled from tomoxetine hydrochloride production waste liquid as described in claim 1, which is characterized in that
In step (1), the inorganic acid is hydrochloric acid or sulfuric acid or phosphoric acid or hydrobromic acid.
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| US4983771A (en) * | 1989-09-18 | 1991-01-08 | Hexcel Corporation | Method for resolution of D,L-alpha-phenethylamine with D(-)mandelic acid |
| CA2537804A1 (en) * | 2003-09-05 | 2005-03-17 | Teva Pharmaceutical Industries Ltd | A recycling process for preparing sertraline |
| US7439399B2 (en) * | 2004-06-28 | 2008-10-21 | Teva Pharmaceutical Fine Chemicals | Processes for the preparation of atomoxetine hydrochloride |
| CN103450008B (en) * | 2013-09-02 | 2015-02-25 | 江苏宝众宝达药业有限公司 | Method for recovering mandelic acid from waste water |
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