CN103435469B - Method for preparing high-optical purity R-(+)-2-chloropropionic acid - Google Patents
Method for preparing high-optical purity R-(+)-2-chloropropionic acid Download PDFInfo
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- CN103435469B CN103435469B CN201310383205.8A CN201310383205A CN103435469B CN 103435469 B CN103435469 B CN 103435469B CN 201310383205 A CN201310383205 A CN 201310383205A CN 103435469 B CN103435469 B CN 103435469B
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- chloropropionic acid
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- GAWAYYRQGQZKCR-UHFFFAOYSA-N 2-chloropropionic acid Chemical compound CC(Cl)C(O)=O GAWAYYRQGQZKCR-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title abstract description 7
- 239000012044 organic layer Substances 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims abstract description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 15
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 9
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 7
- 230000007062 hydrolysis Effects 0.000 claims abstract description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000003197 catalytic effect Effects 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 150000004702 methyl esters Chemical class 0.000 claims description 13
- 238000010792 warming Methods 0.000 claims description 10
- 238000004821 distillation Methods 0.000 claims description 7
- 238000009413 insulation Methods 0.000 claims description 6
- 239000010410 layer Substances 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000013517 stratification Methods 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 238000013022 venting Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000003287 optical effect Effects 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract 3
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 abstract 2
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 229940101629 l- methyl lactate Drugs 0.000 abstract 1
- LPEKGGXMPWTOCB-VKHMYHEASA-N methyl (S)-lactate Chemical compound COC(=O)[C@H](C)O LPEKGGXMPWTOCB-VKHMYHEASA-N 0.000 abstract 1
- 239000008213 purified water Substances 0.000 abstract 1
- 238000009991 scouring Methods 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000003756 stirring Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 4
- 239000003814 drug Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 235000008935 nutritious Nutrition 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000857 drug effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing high-optical purity R-(+)-2-chloropropionic acid. The method comprises the following steps: (1) adding L-methyl lactate and pyridine to a three-opening bottle, heating the three-opening bottle to 63-68 DEG C, slowly dropwise adding thionyl chloride to the three-opening bottle, heating the three-opening bottle to 72-78 DEG C after dropwise adding is finished, and carrying out thermal reaction; (2) cooling the three-opening bottle to 25-30 DEG C, slowly dropwise adding purified water to the three-opening bottle, scouring off the un-reacted thionyl chloride, hydrogen chloride and sulfur dioxide, and then stewing and separating out an organic layer; and (3) adding the separated organic layer to a four-opening bottle with a rectifying tower device, adding 10% of sulfuric acid aqueous solution to the organic layer to carry out catalytic hydrolysis, heating to 105-110 DEG C to carry out normal-pressure reaction, then carrying out gradient vacuum reaction rectification, and collecting the fraction of 100-105 DEG C, so as to obtain the high-optical purity R-(+)-2-chloropropionic acid. The preparation method is high in optical purity, high in yield, simple in process and short in production period.
Description
Technical field
The present invention relates to the Intermediate Preparation methods such as a kind of medicine, nutritious supplementary, be specifically related to a kind of preparation method of high-optical-purity R-(+)-2-chloropropionic acid.
Background technology
R-(+)-2-chloropropionic acid is synthesis medicine, and one of important intermediate such as nutritious supplementary, because optical antipode is all different in biological activity, toxicity and metabolic mechanism etc., therefore the preparation of single enantiomer is very important.Chiral medicinal market development grows in recent years; high-efficiency low-toxicity that is more and more stricter along with environmental protection standard and drug effect requires more and more higher; the investigation and application of single enantiomer medicine has seemed more and more important, and therefore the preparation of high-optical-purity R-(+)-2-chloropropionic acid has great importance.
Summary of the invention
The object of the invention is: provide that a kind of technique is simple, chemical purity is high, cost is low, pollute less, be suitable for the preparation method of high-optical-purity R-(+)-2-chloropropionic acid of suitability for industrialized production.
For achieving the above object, present invention employs following technical scheme.
The preparation method of described high-optical-purity R-(+)-2-chloropropionic acid, be characterized in: comprise the following steps: (one), in anti-application container, add Pfansteihl methyl esters and pyridine, anti-application container is warming up to 63 DEG C ~ 68 DEG C, slowly sulfur oxychloride is dripped in anti-application container, after dropwising, anti-application container is warming up to 72 ~ 78 DEG C, insulation reaction, generates the mixture containing R-(+)-2-methyl chloropropionate, hydrogenchloride and sulfurous gas, (2), anti-application container is cooled to 25 ~ 30 DEG C, slowly desalt is dripped in anti-application container, wash away hydrogenchloride and the sulfurous gas of unreacted sulfur oxychloride and generation, then stratification, separate the organic layer containing R-(+)-2-methyl chloropropionate, (3), being added by the organic layer that step (two) separates is furnished with in the four-hole bottle of device of spiral-screen column, aqueous sulfuric acid catalytic hydrolysis is added in organic layer, be warming up to 105 DEG C ~ 110 DEG C, synthesis under normal pressure, collect tower top temperature lower than the azeotropic cut of 90 DEG C, when GC follows the tracks of R-(+)-2-methyl chloropropionate≤0.5% (wt) in four-hole bottle, lower organic layer in the azeotropic cut of collection is added in four-hole bottle again, and by the water layer on upper strata and methanol layer venting, then the water of equal volume is dripped in four-hole bottle, guarantee that acid concentration is constant, continue rectifying, repeat above distillation operation 2 times or 3 times, until flow out without azeotrope, when GC follows the tracks of R-(+)-2-methyl chloropropionate≤0.5% (wt) in four-hole bottle, control vacuum 0.090MPa ~ 0.095MPa and continue distillation, collect less than 80 DEG C cuts, when in cut when R-(+)-2-chloropropionic acid >=99.5% (wt), moisture content≤0.5% (wt), control the cut that vacuum 0.098MPa ~ 0.1MPa collects 100 DEG C ~ 105 DEG C, obtain R-(+)-2-chloropropionic acid of high-optical-purity.
Further, the preparation method of aforesaid high-optical-purity R-(+)-2-chloropropionic acid, wherein, in step (), the mol ratio of Pfansteihl methyl esters and pyridine is 240:1; The mol ratio of Pfansteihl methyl esters and sulfur oxychloride is 1:1.05, and sulfur oxychloride was added dropwise to complete at 1 ± 0.2 hour, dropwises rear insulation reaction 3 ± 0.5 hours.
Further, the preparation method of aforesaid high-optical-purity R-(+)-2-chloropropionic acid, wherein, the mass concentration of the aqueous sulfuric acid in step (three) is 8% ~ 12%.
Further, the preparation method of aforesaid high-optical-purity R-(+)-2-chloropropionic acid, wherein, purity >=99% of described Pfansteihl methyl esters.
Beneficial effect of the present invention: one, adopt the aqueous sulfuric acid catalytic hydrolysis of 10%, avoid sodium hydroxide hydrolysis chiral impurity many, can reduce chiral impurity well and produce, improve optical purity, ensure yield; Two, while reaction, the methyl alcohol of generation is distilled out, guarantee to react completely, promote the speed of reaction; Three, energy consumption is reduced greatly, and technique is simple, with short production cycle, product purity is high, cost is low, pollution is few, is suitable for industrially scalable application.
Embodiment
Below in conjunction with preferred embodiment, the preparation method to high-optical-purity R-(+)-2-chloropropionic acid of the present invention is further described.
Embodiment 1.
(1) in the 3000ml four-hole bottle that stirring, thermometer, constant pressure dropping funnel, prolong and tail gas adsorption device are housed, 1000g (9.6mol) Pfansteihl methyl esters and 3g (0.04mol) pyridine is added, four-hole bottle be warming up to 65 DEG C and keep constant temperature, in four-hole bottle, slowly drip 1200g (10.1mol) sulfur oxychloride, about 1h is added dropwise to complete.After dropwising, four-hole bottle is warming up to 75 DEG C, about insulation reaction 3h, until GC tracing detection Pfansteihl methyl esters≤0.5% (wt).Purity >=99% of Pfansteihl methyl esters selected in the present embodiment.
(2) four-hole bottle is cooled to room temperature 25 DEG C, slowly 800ml water is dripped in four-hole bottle, wash away hydrogenchloride and the sulfurous gas of unreacted sulfur oxychloride and generation, then stratification, the lower organic layer separated containing R-(+)-2-methyl chloropropionate is about 1200g.
(3) organic layer is placed in is furnished with thermometer, in the 3000ml four-hole bottle of device of spiral-screen column, in four-hole bottle, add some can avoid the kapillary fragment of bumping and the aqueous sulfuric acid 1200g of mass concentration 10%, stir and be heated to temperature 105 DEG C, synthesis under normal pressure, collect the azeotropic cut (methyl alcohol of tower top temperature less than 90 DEG C, water and R-(+)-2-methyl chloropropionate), about about 3h, to flowing out without cut, when GC follows the tracks of R-(+)-2-methyl chloropropionate≤0.5% (wt) in four-hole bottle, lower organic layer in the azeotropic cut of collection is added in four-hole bottle again, and by the water layer on upper strata and methanol layer venting, then the water of equal volume is dripped in four-hole bottle, guarantee that acid concentration does not change, continue rectifying, repeat above distillation operation 2 ~ 3 times, until flow out without azeotrope, when GC follows the tracks of R-(+)-2-methyl chloropropionate≤0.5% (wt) in four-hole bottle.Control vacuum 0.090MPa ~ 0.095MPa and continue distillation, collect less than 80 DEG C cuts (being mainly water), when in cut when R-(+)-2-chloropropionic acid >=99.5% (wt), moisture content≤0.5% (wt), control the cut that vacuum 0.098MPa ~ 0.1MPa collects 100 DEG C ~ 105 DEG C, obtain R-(+)-2-chloropropionic acid of high-optical-purity, obtain sterling R-(+)-2-chloropropionic acid 896g, total recovery 86%.
Comparative example 1.
(1) in the 3000ml four-hole bottle that stirring, thermometer, constant pressure dropping funnel, prolong and tail gas adsorption device are housed, 1000g (9.6mol) Pfansteihl methyl esters and 3g (0.04mol) pyridine is added, four-hole bottle be warming up to 65 DEG C and keep constant temperature, in four-hole bottle, slowly drip 1200g (10.1mol) sulfur oxychloride, about 1h is added dropwise to complete.After dropwising, four-hole bottle is warming up to 75 DEG C, insulation reaction 3h, now GC tracing detection Pfansteihl methyl esters≤0.5% (wt).
(2) four-hole bottle is cooled to room temperature 25 DEG C, slowly 800ml water is dripped in four-hole bottle, wash away unreacted sulfur oxychloride and hydrogenchloride and sulfurous gas, then stratification, the lower organic layer separated containing R-(+)-2-methyl chloropropionate is about 1200g.
(3) organic layer is placed in the 3000ml four-hole bottle being furnished with thermometer, device of spiral-screen column, about reducing temperature to 0 DEG C, the aqueous sodium hydroxide solution of slow dropping 20% is about 2000ml, makes solution pH value control between 10 ~ 11 after 1h dropwises, and stirs 1h; When GC follows the tracks of R-(+)-2-methyl chloropropionate≤0.5% (wt).In the product after hydrolysis, slowly drip concentrated hydrochloric acid 1100ml, 1h dropwises rear control solution pH value and is less than 1, adds some kapillary fragments and avoids bumping.Stir and be heated to temperature 105 DEG C, control vacuum 0.090MPa ~ 0.095MPa and continue distillation, collect less than 80 DEG C cuts (being mainly water), when in cut when R-(+)-2-chloropropionic acid >=99.5% (wt), moisture content≤0.5% (wt), control the cut that vacuum 0.098MPa ~ 0.1MPa collects 100 DEG C ~ 105 DEG C, obtain R-(+)-2-chloropropionic acid of high-optical-purity, obtain sterling R-(+)-2-chloropropionic acid 645g, total recovery 61.93%.
Learn from above comparative example 1, more chiral impurity can be produced with in sodium hydroxide hydrolysis process; But just few a lot of with sulphuric acid hydrolysis chiral impurity, total recovery is also greatly improved.
Claims (4)
1. the preparation method of high-optical-purity R-(+)-2-chloropropionic acid, it is characterized in that: comprise the following steps: (one), in anti-application container, add Pfansteihl methyl esters and pyridine, anti-application container is warming up to 63 DEG C ~ 68 DEG C, slowly sulfur oxychloride is dripped in anti-application container, after dropwising, anti-application container is warming up to 72 ~ 78 DEG C, insulation reaction, generates the mixture containing R-(+)-2-methyl chloropropionate, hydrogenchloride and sulfurous gas; (2), anti-application container is cooled to 25 ~ 30 DEG C, slowly desalt is dripped in anti-application container, wash away hydrogenchloride and the sulfurous gas of unreacted sulfur oxychloride and generation, then stratification, separate the organic layer containing R-(+)-2-methyl chloropropionate; (3), the organic layer that step (two) separates is added be furnished with in the four-hole bottle of device of spiral-screen column, aqueous sulfuric acid catalytic hydrolysis is added in organic layer, be warming up to 105 DEG C ~ 110 DEG C, synthesis under normal pressure, collect tower top temperature lower than the azeotropic cut of 90 DEG C, when GC follows the tracks of R-(+)-2-methyl chloropropionate≤0.5% (wt) in four-hole bottle, lower organic layer in the azeotropic cut of collection is added in four-hole bottle again, and by the water layer on upper strata and methanol layer venting, then drip the water of equal volume in four-hole bottle, continue rectifying; Repeat above distillation operation 2 times or 3 times, until flow out without azeotrope, when GC follows the tracks of R-(+)-2-methyl chloropropionate≤0.5% (wt) in four-hole bottle, control vacuum 0.090MPa ~ 0.095MPa and continue distillation, collect less than 80 DEG C cuts, when in cut when R-(+)-2-chloropropionic acid >=99.5% (wt), moisture content≤0.5% (wt), control the cut that vacuum 0.098MPa ~ 0.1MPa collects 100 DEG C ~ 105 DEG C, obtain R-(+)-2-chloropropionic acid of high-optical-purity.
2. the preparation method of high-optical-purity R-(+)-2-chloropropionic acid according to claim 1, is characterized in that: in step (), the mol ratio of Pfansteihl methyl esters and pyridine is 240:1; The mol ratio of Pfansteihl methyl esters and sulfur oxychloride is 1:1.05, and sulfur oxychloride was added dropwise to complete at 1 ± 0.2 hour, dropwises rear insulation reaction 3 ± 0.5 hours.
3. the preparation method of high-optical-purity R-(+)-2-chloropropionic acid according to claim 1 and 2, is characterized in that: the mass concentration of the aqueous sulfuric acid in step (three) is 8% ~ 12%.
4. the preparation method of high-optical-purity R-(+)-2-chloropropionic acid according to claim 1 and 2, is characterized in that: purity >=99% of described Pfansteihl methyl esters.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5049676A (en) * | 1989-05-30 | 1991-09-17 | Rhone-Poulenc Chimie | Process for the preparation of optical isomers of 2-chloropropionic acid esters |
| CN1786019A (en) * | 2005-10-14 | 2006-06-14 | 邢将军 | Manufacturing method of proglu-dipeptide |
| CN101284772A (en) * | 2008-06-11 | 2008-10-15 | 河北华晨药业有限公司 | Synthetic method of D-(+)-2-chloro-propanoyl chloride |
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2013
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5049676A (en) * | 1989-05-30 | 1991-09-17 | Rhone-Poulenc Chimie | Process for the preparation of optical isomers of 2-chloropropionic acid esters |
| CN1786019A (en) * | 2005-10-14 | 2006-06-14 | 邢将军 | Manufacturing method of proglu-dipeptide |
| CN101284772A (en) * | 2008-06-11 | 2008-10-15 | 河北华晨药业有限公司 | Synthetic method of D-(+)-2-chloro-propanoyl chloride |
Non-Patent Citations (2)
| Title |
|---|
| 光学活性物质S-2-氯丙酸乙酯的合成;方正东等;《广州化工》;20111231;第39卷(第24期);64-65 * |
| 李丰等.R-(+)-2-氯丙酸的合成.《安徽医药》.2006,第10卷(第4期),第252页. * |
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Effective date of registration: 20231119 Address after: 400025 room 15-2, building 4, No. 11, Tianlan Avenue, Cuntan street, Jiangbei District, Chongqing Patentee after: Hutianhua Chemical (Group) Co.,Ltd. Address before: 215619 Zhangjiagang Sanlian Chemical Technology Co., Ltd., Dongsha Chemical Zone, Nanfeng Town, Zhangjiagang City, Suzhou City, Jiangsu Province Patentee before: ZHANGJIAGANG SANLIAN CHEMICAL TECHNOLOGY Co.,Ltd. |