WO2004063141A1 - 光学活性ジアシル酒石酸の回収方法 - Google Patents
光学活性ジアシル酒石酸の回収方法 Download PDFInfo
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- WO2004063141A1 WO2004063141A1 PCT/JP2003/016474 JP0316474W WO2004063141A1 WO 2004063141 A1 WO2004063141 A1 WO 2004063141A1 JP 0316474 W JP0316474 W JP 0316474W WO 2004063141 A1 WO2004063141 A1 WO 2004063141A1
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- Prior art keywords
- optically active
- tartaric acid
- acid
- salt
- amine
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Definitions
- the present invention relates to a method for decomposing a salt of amine and optically active ditartaric acid to recover optically active ditartaric acid.
- Optically active diacyl tartaric acid is an important compound as an optical resolving agent for producing an optically active amine, which is important as a raw material for pharmaceuticals.
- Optically active diacyl tartaric acid is obtained from the diastereomeric salt obtained in the optical resolution step. Collecting and recycling tartaric acid is essential for building resource-saving industrial processes.
- Diastereomeric salt consisting of optically active amine and optically active diacetyltartaric acid
- a diastereomeric salt of (S) -1,2, -propanediamine and dibenzoylurine D-tartaric acid is added to a 9% aqueous hydrochloric acid solution.
- a method of recovering the precipitated dibenzoyl-1-D-tartaric acid by filtration Japanese Patent No.
- a salt dissolving method in which disodium L-tartrate is left in the aqueous layer and (4aR, 8aR) -l-n-propyl- 16-oxodecahydroquinoline is extracted with methylene chloride (Nippon Tokuhei 6 — Japanese Patent Application Publication No. 7-006 (Preparation Example 1)) is also known, but does not describe a method for recovering g-p-toluoyl L-tartaric acid from g-p-toluoyl mono-L-disodium tartrate.
- An object of the present invention is to provide a method for industrially recovering an optically active diacetyl tartaric acid which is easy to recycle by decomposing a salt of an amine and an optically active ditartaric acid. Furthermore, a diastereomeric salt of optically active amine and optically active diacetyl tartaric acid obtained by optical resolution is decomposed to recover optically active optically active diacetyl tartaric acid, and the obtained optically active diacetyl tartaric acid is subjected to the optical resolution step.
- the aim is to provide a way to recycle.
- a method for recovering an optically active diacetyl tartaric acid from an aqueous solution of an amine and an optically active diacetyl tartaric acid a method for recovering an optically active diacetyl tartaric acid by adding an optically active diacetyl tartaric acid to an acidic aqueous solution in advance.
- This is a method for recovering an optically active diacetyl tartaric acid, which is a diastereomeric monosalt obtained by optically resolving a racemic amine with an optically active diacetyl tartaric acid.
- a recycling process in which the optically active diacyl tartaric acid obtained in the salting process is recovered, and the recovered optically active diacyl tartaric acid is recycled to the optical resolution process as a raw material for the optical resolution process A method for recovering optically active ditartaric acid, comprising the steps of: In this method, an optically active ditartaric acid is added to an aqueous solution in advance.
- the amine used as a raw material and the salt of an optically active diacetyl tartaric acid include: an optically inactive amide and a salt of an optically active diacetyl tartaric acid; a racemic amide; Both diastereomeric salts of active diacyl tartaric acid, optically active amines and salts of optically active diacyl tartaric acid can be used.
- any of the crystalline diastereomeric monosalts obtained by optically resolving a racemic amine with optically active diacyltartaric acid and separation by filtration, and any diastereomer salt of an optically enantiomer contained in the filtered mother liquor can be used.
- the optical purity of the amine contained in the salt can be any value.
- the kind of the amine is not particularly limited, but examples of the optically inactive amine include benzylamine and cyclohexylamine.
- the racemic amine is not particularly limited, but aliphatic amines such as 1,2-diaminopropane, 3-aminobutane, 3-aminopentanenitrile, 21-cyclopropylaminocyclohexanol, mononaphthylethylamine, Aromatic amines such as ⁇ -phenylethylamine, 1-methyl-3-phenylpropylamine, mono (p-chlorophenyl) ethylamine, mono (tolyleethyl) amine, 3-aminopyrrolidine, 3-amino-1 And heterocyclic amines such as —benzylpyrrolidine and 3-phenyl-1-propylpyridine.
- Aromatic amines such as ⁇ -phenylethylamine, 1-methyl-3-phenylpropylamine, mono (p-chlorophenyl) ethylamine, mono (tolyleethyl) amine, 3-aminopyrrolidine,
- Optically active dibenzoyltartaric acid includes optically active dibenzoyltartaric acid, optically active di-P-toluoyltartaric acid, optically active di-m-toluoyltartaric acid, optically active diotartoic acid, optically active dianisoyltartaric acid, optically active di-m-methoxybenzoyltartaric acid
- Benzoic acid esters such as optically active di-o-methoxybenzoyl tartaric acid
- phenyl acetic acid esters such as optically active diphenyl acetyl tartaric acid
- aliphatic carboxylic acids such as optically active diacetyl tartaric acid and optically active dipropionyl tartaric acid.
- Examples thereof include stels, and are preferably optically active dibenzoyl tartaric acid, optically active di-p-toluoyl tartaric acid, optically active di-m-toluoyl tartaric acid, optically active di-toluoyl tartaric acid, optically active dianisoyl tartaric acid, and optically active di-m-methoxy tartaric acid.
- Benzoyl Tartaric acid is an optically active di-o-methoxybenzoyl tartaric acid.
- the diastereomer salt of amide and ditartaric acid any combination can be used. For example,
- Salts such as 1-methyl-3-phenylpropylamine, 2-cyclopropylaminocyclohexanol, and 3-phenyl-1-propylpiperidine are preferred.
- the optically active diacyl tartaric acid includes both the D-form and the L-form, and means that the optical purity is 98% e e or more.
- the acidic aqueous solution is not particularly limited, but is preferably an aqueous solution of an inorganic acid such as hydrochloric acid, sulfuric acid, phosphoric acid, or nitric acid, preferably an aqueous solution of hydrochloric acid, sulfuric acid, or phosphoric acid, and particularly preferably an aqueous solution of hydrochloric acid or sulfuric acid.
- the acid concentration is 2 to 40% by weight, preferably 5 to 30% by weight, and more preferably 7 to 20% by weight.
- the amount of the acid used may be at least the equivalent of the amine contained in the diastereomer salt, but is preferably 1.5 to 3.0 equivalents, more preferably 1.8 to 2.5 equivalents.
- optically active ditartaric acid is generally a bulky compound
- the acid concentration and amount used are adjusted so that the slurry of optically active ditartaric acid precipitated by salt exchange has a concentration of 5 to 15%, which can be efficiently stirred. It is preferable to decide.
- optically active tartaric acid salt When an optically active tartaric acid salt is added directly to a stirred acidic aqueous solution, the optically active ditartaric acid precipitates at once, forming a block, and the optically active tartaric acid salt is also involved in the block, so that salt exchange proceeds smoothly. Absent. In particular, when an optically active amine is industrially produced by dividing it with an optically active tartaric acid derivative, the recovery of the optically active amine also decreases, which is not preferable.
- optically active diacyl tartaric acid dissolves in the aqueous solution as a dinatrium salt, so that salt exchange proceeds smoothly, but when diluted to a concentration at which dinatridium diacyltartrate does not precipitate, the free state is obtained.
- a large amount of organic solvent must be used, or a halogen-based solvent such as chloroform with high extraction ability must be used. Not preferred.
- optically active ditartaric acid is hydrolyzed by an alkali, not only the recovery rate of the optically active ditartaric acid is reduced, but also the optically active optically active dibasic tartaric acid salt obtained by crystallization and filtration after dissolving the optically active dibasic tartaric acid salt in the aqueous solution. It is not preferable for recycling because the chemical purity of activated ditartaric acid also decreases.
- the same kind of optically active diacetyl tartaric acid as that contained in the salt with the amine or the diastereomer salt with the optically active amine is added to the aqueous acid solution in advance. deep.
- the amount of addition depends on the kind of the optically active ditartaric acid and the salt exchange conditions, but is preferably 0.05 to 3% by weight, particularly preferably 0.1 to 2% by weight of the aqueous acid solution.
- the addition rate of the amine salt or diastereomer salt is high, a large amount of the optically active tartaric acid to be added in advance is used, and when the addition rate is low, the salt exchange can be performed well even with a small addition amount. Although there is no problem with salt exchange even if the addition amount is large, it is not preferable because the recycled amount of the recovered optically active diacyl tartaric acid increases and the production method does not become efficient.
- the temperature for salt exchange is preferably 0 to 50 ° C, more preferably 20 to 40 ° C. In this range, the salt exchange proceeds well, but when the temperature is higher than 50 ° C, the salt exchange rate is increased.However, depending on the type of optically active diacyl tartaric acid that precipitates, the salt is in a melt state, so that blocks are easily formed. Is not preferred.
- the time required for salt exchange varies depending on the temperature of salt exchange, the type of salt, and the like, but is usually 1 to 10 hours.
- the salt exchange situation is difficult to grasp because the amine salt and diastereomeric salt are added to the slurry of optically active diacyl tartaric acid added in advance, but the crystal form of the salt of amine and diastereomeric salt and the optically active tartaric acid.
- the salt exchange status can be grasped if detailed observations are made.
- a method of quantifying the amount of dissolved amine in an acid aqueous solution can be adopted. You.
- the organic solvent in which the optically active ditartaric acid is dissolved is not removed because the recovery rate of the optically active ditartaric acid decreases.
- the filtration mother liquor is a mixed solution of water and a water-soluble organic solvent, an aqueous solution from which the organic solvent has been previously removed under reduced pressure can be used. If the mother liquor is an aqueous solution, it can be used as it is. However, if the concentration is too low in the desalting step, the concentration is adjusted and the concentration is adjusted.
- a salt exchange method for mer salt may be employed.
- optically active ditartaric acid and an organic carboxylic acid such as an inorganic acid or acetic acid are used in combination in the optical resolution step, these acids are contained in the filtered mother liquor. Similarly, it can be used as it is in the desalting step. If the acid is not a water-soluble acid, it is mixed into the precipitated optically active ditartaric acid, but the salt may be adjusted when recycled to the optical resolution step.
- the optically active diacyl tartaric acid recovered by salt exchange with an aqueous acid solution containing the optically active diacyl tartaric acid has a good slurry property. Filtration under reduced pressure, filtration under pressure, or centrifugal elimination can be used to recover the precipitated optically active ditartaric acid.
- the optically active ditartaric acid recovered by this method has good filtration properties.
- the optically active diacetyl tartaric acid recovered by this method has no decrease in optical purity and high chemical purity.
- the method of optical resolution is not particularly limited.
- the optical resolution can be achieved by mixing racemic amine and optically active ditartaric acid in a solvent to synthesize a diastereomer salt, and then precipitating the diastereomer salt. Examples Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto.
- the optical purity of the optically active disiltartaric acid was analyzed by HPLC equipped with a column for optical purity analysis (CHI RALCEL 0 J manufactured by Daicel Chemical Industries, Ltd.). Chemical purity was analyzed on a HPLC equipped with an ODS column.
- the optical purity of 1,2-diaminopropane contained in the precipitated diastereomeric salt was 76% ee.
- the obtained diastereomer monosalt was recrystallized from water, filtered and dried to obtain 20.8 g of diastereomer monosalt.
- the optical purity of 1,2 diaminopropane contained in the precipitated diastereomer monosalt was 98.5% ee.
- Example 3 Into a 30 Oml 4-liter flask equipped with a stirrer, Dim funnel, dropping funnel and thermometer, 5.3 g (0.06 mol) of 95% sulfuric acid and 50 g of water were charged at 25 to 30 ° C. While stirring with 0.1 g of P-toluoyl-D-tartaric acid was added, and the mixture was stirred until a smooth slurry was obtained. A solution obtained by concentrating 203.5 g of the filtered mother liquor obtained in Example 1 to 80 g under reduced pressure was slowly added dropwise thereto over 2 hours. After continuing stirring for further 2 hours, the precipitated crystals were filtered and dried to obtain 13.lg of g-p-toluoyl-D-tartaric acid. The optical purity was 99.5% ee, and racemization did not occur at the same time in the optical resolution step and the salt solution step. No impurity peak was detected by HP LC.
- Example 3 Example 3
- the amount of di-P-toluoyl-D-tartaric acid obtained was 150.2 g from purity analysis.
- 900 ml of water and 48.lg of 95% sulfuric acid were charged into a 2 L three-necked flask equipped with a stirrer, a Dimroth and a thermometer, and stirred at 25 to 30 ° C.
- 10.0 g of g-p-toluoyl-D-tartaric acid was added and stirred for 20 minutes until a smooth slurry was obtained.
- Example 5 A 2 L three-necked flask equipped with a stirrer, Dimroth and thermometer was charged with 900 ml of water and 81.9 g of 95% sulfuric acid, and stirred at 25 to 30 ° C. To this, 1 g of the diastereomer salt obtained in the same manner as in Example 4 was added every 5 minutes, and the mixture was stirred for 1 hour. However, the lump adhered to the flask wall and did not form crystals. Further, the remaining diastereomeric salt was added in about 2 hours, and the mixture was stirred at room temperature for 1 ⁇ . However, di-p-toluoyl-D-tartaric acid in a crystalline form was not obtained.
- Example 5 A 2 L three-necked flask equipped with a stirrer, Dimroth and thermometer was charged with 900 ml of water and 81.9 g of 95% sulfuric acid, and stirred at 25 to 30 ° C. To this, 1 g of the diastereomer salt
- the mother liquor of the centrifugal dehydration of di-P-toluoyl-D-tartaric acid of Example 4 was charged into a 2 L three-necked flask equipped with a stirrer, a gym port, and a thermometer. It concentrated under reduced pressure until it became. The concentrate was cooled to 20 to 30 ° C, and 85 g of a 48% aqueous sodium hydroxide solution was added dropwise with stirring to release (R) -2-cyclopropylaminocyclohexanol.
- the extract was extracted twice with 300 g of toluene, and the toluene layer was washed with 60 g of water and concentrated under reduced pressure to obtain a concentrated solution containing 59.8 g of (R) -2-cyclopropylaminocyclohexanol 1 10 g was obtained.
- the concentrate was vacuum distilled to 91-94. 9 ⁇ 1.1 as a fraction of 1 kPa (R) — 2— 55.3 g of cyclopropylaminocyclohexanol was obtained.
- the optical purity was 99.0% ee, and there was no decrease in optical purity in the salt-removal process and distillation process. Comparative Example 2
- the optical purity of 1,2-diaminopropane contained in the precipitated diastereomer salt was 92.5% ee, and dibenzoyl L-tartaric acid was 10.6 g.
- 91 g of 4% hydrochloric acid aqueous solution was charged into a 30-Om 1 three-necked flask equipped with a stirrer, Dimroth, and thermometer, and dibenzoyl-L-tartaric acid lg was added while stirring at 25 to 30 ° C. Stir until a slurry is obtained.
- 0.5 g of the above diastereomer salt was added, and the mixture was stirred for 10 minutes to confirm that dibenzilol L-tartaric acid precipitated by salting out was crystallized.
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/542,498 US7358384B2 (en) | 2003-01-16 | 2003-12-22 | Processes for the recovery of optically active diacyltartaric acids |
JP2004566292A JP4392661B2 (ja) | 2003-01-16 | 2003-12-22 | 光学活性ジアシル酒石酸の回収方法 |
AU2003289487A AU2003289487A1 (en) | 2003-01-16 | 2003-12-22 | Processes for the recovery of optically active diacyltartatic acids |
EP03780993A EP1586551A4 (en) | 2003-01-16 | 2003-12-22 | METHOD FOR OBTAINING OPTICALLY ACTIVE DIACYLTARTIC ACIDS |
Applications Claiming Priority (2)
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JP2003008023 | 2003-01-16 | ||
JP2003-8023 | 2003-01-16 |
Publications (1)
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WO2004063141A1 true WO2004063141A1 (ja) | 2004-07-29 |
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PCT/JP2003/016474 WO2004063141A1 (ja) | 2003-01-16 | 2003-12-22 | 光学活性ジアシル酒石酸の回収方法 |
Country Status (6)
Country | Link |
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US (1) | US7358384B2 (ja) |
EP (1) | EP1586551A4 (ja) |
JP (1) | JP4392661B2 (ja) |
CN (1) | CN1315777C (ja) |
AU (1) | AU2003289487A1 (ja) |
WO (1) | WO2004063141A1 (ja) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2010519262A (ja) * | 2007-02-22 | 2010-06-03 | インデナ・ソチエタ・ペル・アチオニ | (2r,3s)−3−フェニルイソセリンメチルエステル酢酸塩の製造方法 |
JP2011503122A (ja) * | 2007-11-16 | 2011-01-27 | 江▲蘇▼恒瑞医▲薬▼股▲分▼有限公司 | 4,5−ジメトキシ−1−(メチルアミノメチル)−ベンゾシクロブタンの分離 |
JP2018521085A (ja) * | 2015-07-24 | 2018-08-02 | セルジーン コーポレイション | (1r,2r,5r)−5−アミノ−2−メチルシクロヘキサノール塩酸塩の合成方法及びそれに有用な中間体 |
Families Citing this family (1)
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CN112358398A (zh) * | 2020-11-19 | 2021-02-12 | 山东新华制药股份有限公司 | D-(+)-二对甲苯甲酰酒石酸的回收制备方法 |
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- 2003-12-22 AU AU2003289487A patent/AU2003289487A1/en not_active Abandoned
- 2003-12-22 CN CNB200380108907XA patent/CN1315777C/zh not_active Expired - Fee Related
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Publication number | Priority date | Publication date | Assignee | Title |
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JP2010519262A (ja) * | 2007-02-22 | 2010-06-03 | インデナ・ソチエタ・ペル・アチオニ | (2r,3s)−3−フェニルイソセリンメチルエステル酢酸塩の製造方法 |
JP2011503122A (ja) * | 2007-11-16 | 2011-01-27 | 江▲蘇▼恒瑞医▲薬▼股▲分▼有限公司 | 4,5−ジメトキシ−1−(メチルアミノメチル)−ベンゾシクロブタンの分離 |
JP2018521085A (ja) * | 2015-07-24 | 2018-08-02 | セルジーン コーポレイション | (1r,2r,5r)−5−アミノ−2−メチルシクロヘキサノール塩酸塩の合成方法及びそれに有用な中間体 |
JP2021046426A (ja) * | 2015-07-24 | 2021-03-25 | セルジーン コーポレイション | (1r,2r,5r)−5−アミノ−2−メチルシクロヘキサノール塩酸塩の合成方法及びそれに有用な中間体 |
JP7165178B2 (ja) | 2015-07-24 | 2022-11-02 | セルジーン コーポレイション | (1r,2r,5r)-5-アミノ-2-メチルシクロヘキサノール塩酸塩の合成方法及びそれに有用な中間体 |
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JPWO2004063141A1 (ja) | 2006-05-18 |
US7358384B2 (en) | 2008-04-15 |
JP4392661B2 (ja) | 2010-01-06 |
CN1315777C (zh) | 2007-05-16 |
CN1738791A (zh) | 2006-02-22 |
AU2003289487A1 (en) | 2004-08-10 |
EP1586551A1 (en) | 2005-10-19 |
US20060058546A1 (en) | 2006-03-16 |
EP1586551A4 (en) | 2006-07-26 |
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