CN107522636B - A method of recycling camphorsulfonic acid - Google Patents
A method of recycling camphorsulfonic acid Download PDFInfo
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- CN107522636B CN107522636B CN201710824834.8A CN201710824834A CN107522636B CN 107522636 B CN107522636 B CN 107522636B CN 201710824834 A CN201710824834 A CN 201710824834A CN 107522636 B CN107522636 B CN 107522636B
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- camphorsulfonic acid
- acid
- camphorsulfonic
- camsilate
- aqueous solution
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/42—Separation; Purification; Stabilisation; Use of additives
- C07C303/44—Separation; Purification
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
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- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of methods for recycling camphorsulfonic acid, for the aqueous solution containing camsilate generated in ephedrine production process.By acid precipitation, camphorsulfonic acid aqueous solution is obtained after being filtered to remove inorganic salts, then is concentrated, adds sulfuric acid crystallization, is filtered, washed to obtain camphorsulfonic acid.Present invention process simple and stable, optical purity of products is high, and the rate of recovery is 90% or more, and low energy consumption, and the three wastes are few and are easy to administer, and production is at low cost, is suitable for large-scale industrial production.
Description
Technical field
The invention belongs to technical field of fine, and in particular to what is generated in ephedrine production process contains camsilate
Aqueous solution recycling camphorsulfonic acid method.
Background technique
D- (+)-camphorsulfonic acid (No. CAS: 3144-16-9), L- (-)-camphorsulfonic acid (No. CAS: 35963-20-3) are camphor tree
The optical isomer of brain sulfonic acid, D- (+)-camphorsulfonic acid are made by natural camphor is sulfonated, it is also possible to which artificial camphor sulfonation is split
It is made, L- (-)-camphorsulfonic acid is split by artificial camphor sulfonation and is made.The two can be used as medicine intermediate, amino acids, Chinese ephedra
The resolving agent of the chiral materials such as plain class.
DL- methylamino propiophenone is the key intermediate for synthesizing ephedrine, can use D- (+)-camphorsulfonic acid or L- (-)-
Camphorsulfonic acid is split, and methylamino propiophenone camsilate adds calcium hydroxide or barium hydroxide to alkalize, and after extracting and demixing, is obtained
To the aqueous solution of camsilate, to reduce cost, camphorsulfonic acid need to be recycled.
At home and abroad in document report, the preparation of camphorsulfonic acid and the common method of recycling are ion-exchange-resin process, fiber crops
The impurity that the aqueous solution of camsilate contains in flavine production process is more, and spent ion exchange resin recycling easily loses resin
It is living, it is not easy to regenerate, and the installation area of ion exchange resin is big, processing capacity is low, and water consumption is big, and energy consumption is high, generates three
Useless more, higher cost.Another method is that the aqueous solution of camsilate adds sulfuric acid, oxalic acid etc., filters out inorganic salts, obtains
Camphorsulfonic acid aqueous solution evaporated under reduced pressure, is added aceticanhydride, and the organic solvents such as ethyl acetate through cooling, separate, are dried to obtain camphor sulphur
Acid, because solubility is larger in a solvent for camphorsulfonic acid, primary recovery is lower, and the unit consumption of organic solvent is larger, higher cost.
Summary of the invention
The object of the present invention is to provide a kind of methods for recycling camphorsulfonic acid, of the existing technology above-mentioned scarce to overcome
It falls into, meets the needs of industrialized production.
The technical scheme is that a kind of method for recycling camphorsulfonic acid, includes the following steps:
(1) aqueous solution containing camsilate generated in ephedrine production process, referred to as camsilate are collected
Aqueous solution；
(2) sulfuric acid is added in camphorsulfonic acid saline solution and carries out metathesis reaction, filter out the camphor tree obtained after inorganic salts
Brain sulfonic acid aqueous solution；
(3) camphorsulfonic acid aqueous solution is concentrated, camphorsulfonic acid concentrate is made；
(4) it by camphorsulfonic acid concentrate successively by primary cooling, enriching sulfuric acid, reducing temperature twice, crystallization, separation, then uses
Glacial acetic acid washing is dried to obtain camphorsulfonic acid.
Further, in step (1), the camsilate is D- (+)-camphorsulfonic acid calcium salt, D- (+)-camphorsulfonic acid
One of barium salt, L- (-)-camphorsulfonic acid calcium salt or L- (-)-camphorsulfonic acid barium salt；Camsilate is D- (+)-camphor sulphur
Acid calcium salt or D- (+)-camphorsulfonic acid barium salt, the camphorsulfonic acid that step (4) obtains are D- (+)-camphorsulfonic acid；Camsilate
For L- (-)-camphorsulfonic acid calcium salt or L- (-)-camphorsulfonic acid barium salt, the camphorsulfonic acid that step (4) obtains is L- (-)-camphor sulphur
Acid.
Further, in step (3), the concentration of camphorsulfonic acid concentrate is 18~25 Baume degrees (25 DEG C).
Further, in step (4), the weight ratio of camphorsulfonic acid concentrate and the concentrated sulfuric acid is 1: 0.2~1.5.
Further, in step (4), the temperature once to cool down is -10~60 DEG C.
Further, in step (4), the temperature of reducing temperature twice is -10~10 DEG C.
Further, in step (4), the time of crystallization is 5~15 hours.
It is an advantage of the invention that simple process, stablizes, the rate of recovery of camphorsulfonic acid is further split up to 90% or more
Verifying, gained this product optical purity are high；And it is easy to operate, low energy consumption, and the three wastes are few and are easy to administer, and production cost is low, is suitble to
Large-scale industrial production.
Specific embodiment
Below with by test, present invention is further described in detail with embodiment:
Embodiment 1:
D- (+)-adiphorin aqueous solution 1000ml (content 25.7%) is taken, 5g303 charcoal is added to be heated to 80~85
DEG C decoloration 30~40 minutes, filtering, destainer was cooled to 30 DEG C or less dropwise addition sulfuric acid to metathesis reaction terminal (sample detection sulphur
The micro- excess of acid), it is filtered after continuing stirring 1 hour, obtains D- (+)-camphorsulfonic acid aqueous solution and be concentrated under reduced pressure, until Baume degrees
For 18 (25 DEG C), concentrate weight 428g.Concentrate is cooled to 50 DEG C hereinafter, the dropwise addition 128g concentrated sulfuric acid, is cooled to -10
~-5 DEG C keep the temperature 5.5 hours, filter, are washed with a small amount of glacial acetic acid, dry that D- (+)-camphorsulfonic acid 237.7g, yield are
92.5%, 197.8 DEG C of fusing point, optically-active+21.6.
Embodiment 2:
D- (+)-camphorsulfonic acid barium aqueous solution 1000ml (content 28.2%) is taken, 5g303 charcoal is added to be heated to 80~85
DEG C decoloration 30~40 minutes, filtering, destainer is cooled to 30 DEG C of dropwise addition sulfuric acid, and to metathesis reaction terminal, (sample detection sulfuric acid is micro-
It is excessive), it is filtered after continuing stirring 1 hour, obtains D- (+)-camphorsulfonic acid aqueous solution and be concentrated under reduced pressure, until Baume degrees is 20
(25 DEG C), concentrate weight 455g.Concentrate is cooled to 20 DEG C hereinafter, the dropwise addition 227g concentrated sulfuric acid, is cooled to -5~0 DEG C of heat preservation
It 10 hours, filters, is washed with a small amount of glacial acetic acid, dry D- (+)-camphorsulfonic acid 263g, yield 93.3%, fusing point 198.0
DEG C, optically-active+21.3.
Embodiment 3:
By L- (-)-adiphorin aqueous solution 1000ml (content 26.4%), 5g303 charcoal is added to be heated to 80~85
DEG C decoloration 30~40 minutes, filtering, destainer is cooled to 30 DEG C of dropwise addition sulfuric acid, and to metathesis reaction terminal, (sample detection sulfuric acid is micro-
It is excessive), it is filtered after continuing stirring 1 hour, obtains L- (-)-camphorsulfonic acid aqueous solution and be concentrated under reduced pressure, until Baume degrees is 22
(25 DEG C), concentrate weight 406g.Concentrate is cooled to 10 DEG C hereinafter, the 406g concentrated sulfuric acid is added dropwise, and it is small to keep the temperature 12 at 0~5 DEG C
When, it filters, is washed with a small amount of glacial acetic acid, dry L- (-)-camphorsulfonic acid 244.7g, yield 92.7%, 198.2 DEG C of fusing point,
Optically-active+21.80.
Embodiment 4:
L- (-)-camphorsulfonic acid barium aqueous solution 1000ml (content 27.1%) is taken, 5g303 charcoal is added to be heated to 80~85
DEG C decoloration 30~40 minutes, filtering, filtrate was cooled to 30 DEG C of dropwise addition sulfuric acid to metathesis reaction terminal (the micro- mistake of sample detection sulfuric acid
Amount), it is filtered after continuing stirring 1 hour, obtains L- (-)-camphorsulfonic acid aqueous solution and be concentrated under reduced pressure, until Baume degrees is 24
(25 DEG C), concentrate weight 387g.Concentrate is cooled to 0 DEG C hereinafter, the 464g concentrated sulfuric acid is added dropwise, and it is small to keep the temperature 15 at 5~10 DEG C
When, it filters, is washed with a small amount of glacial acetic acid, dry L- (-)-camphorsulfonic acid 247.9g, yield 91.5%, 198.6 DEG C of fusing point,
Optically-active+21.5.
Claims (2)
1. a kind of method for recycling camphorsulfonic acid, includes the following steps:
(1) aqueous solution containing camsilate generated in ephedrine production process is collected, referred to as camsilate is water-soluble
Liquid；
(2) sulfuric acid is added in camphorsulfonic acid saline solution and carries out metathesis reaction, obtain camphorsulfonic acid after filtering out inorganic salts
Aqueous solution；
(3) camphorsulfonic acid aqueous solution is concentrated, camphorsulfonic acid concentrate is made；
(4) camphorsulfonic acid concentrate is used into glacial acetic acid successively by primary cooling, enriching sulfuric acid, reducing temperature twice, crystallization, separation
It washs, be dried to obtain camphorsulfonic acid；
In step (1), the camsilate is D- (+)-camphorsulfonic acid calcium salt, D- (+)-camphorsulfonic acid barium salt, L- (-)-
One of camphorsulfonic acid calcium salt or L- (-)-camphorsulfonic acid barium salt；Camsilate is D- (+)-camphorsulfonic acid calcium salt or D-
(+)-camphorsulfonic acid barium salt, the camphorsulfonic acid that step (4) obtains are D- (+)-camphorsulfonic acid；Camsilate is L- (-)-camphor
Sulfonic acid calcium salt or L- (-)-camphorsulfonic acid barium salt, the camphorsulfonic acid that step (4) obtains are L- (-)-camphorsulfonic acid；
In step (3), camphorsulfonic acid concentrate concentration under the conditions of 25 DEG C of temperature is 18~25 Baume degrees；
In step (4), the weight ratio of camphorsulfonic acid concentrate and the concentrated sulfuric acid is 1: 0.2~1.5, and the temperature once to cool down is -10
~60 DEG C, the temperature of reducing temperature twice is -10~10 DEG C.
2. the method for recycling camphorsulfonic acid according to claim 1, it is characterised in that: in step (4), the time of crystallization is
5~15 hours.
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| CN201710824834.8A CN107522636B (en) | 2017-08-30 | 2017-08-30 | A method of recycling camphorsulfonic acid |
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| CN201710824834.8A CN107522636B (en) | 2017-08-30 | 2017-08-30 | A method of recycling camphorsulfonic acid |
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| CN107522636A CN107522636A (en) | 2017-12-29 |
| CN107522636B true CN107522636B (en) | 2019-08-13 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101786970A (en) * | 2010-03-16 | 2010-07-28 | 天津市中央药业有限公司 | Recovering and applying method of clopidogrel resolving agent |
| CN102093263A (en) * | 2011-01-13 | 2011-06-15 | 浙江新华制药有限公司 | Recycling method of levorotation camphorsulfonic acid serving as clopidogrel resolving agent |
| CN106496077A (en) * | 2016-09-30 | 2017-03-15 | 厦门欣赛科技有限公司 | A kind of method for reclaiming camphorsulfonic acid from camphorsulfonic acid synthesis mother liquid |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1265391A (en) * | 2000-01-31 | 2000-09-06 | 李健府 | Preparation of levorotary Alpha-methylamino-phenylacetone and repeated usage of separating agent |
-
2017
- 2017-08-30 CN CN201710824834.8A patent/CN107522636B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101786970A (en) * | 2010-03-16 | 2010-07-28 | 天津市中央药业有限公司 | Recovering and applying method of clopidogrel resolving agent |
| CN102093263A (en) * | 2011-01-13 | 2011-06-15 | 浙江新华制药有限公司 | Recycling method of levorotation camphorsulfonic acid serving as clopidogrel resolving agent |
| CN106496077A (en) * | 2016-09-30 | 2017-03-15 | 厦门欣赛科技有限公司 | A kind of method for reclaiming camphorsulfonic acid from camphorsulfonic acid synthesis mother liquid |
Non-Patent Citations (1)
| Title |
|---|
| "驱虫药四咪唑析分剂-d-樟脑磺酸的回收";合肥制药厂三车间;《安徽化工》;19760930;第33-34页 |
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Effective date of registration: 20190517 Address after: 024000 No. 8 Mengxin Street, Hongshan Economic Development Zone, Hongshan District, Chifeng City, Inner Mongolia Autonomous Region Applicant after: Chifeng Arker Pharmaceutical Technology Co.,Ltd. Applicant after: Chifeng Mengxin Pharmaceutical Co.,Ltd. Address before: 024000 No. 8 Mengxin Street, Hongshan Economic Development Zone, Hongshan District, Chifeng City, Inner Mongolia Autonomous Region Applicant before: Chifeng Arker Pharmaceutical Technology Co.,Ltd. |
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