EP1127153A1 - Procede pour la production de derives d'acide aspartique - Google Patents

Procede pour la production de derives d'acide aspartique

Info

Publication number
EP1127153A1
EP1127153A1 EP99950763A EP99950763A EP1127153A1 EP 1127153 A1 EP1127153 A1 EP 1127153A1 EP 99950763 A EP99950763 A EP 99950763A EP 99950763 A EP99950763 A EP 99950763A EP 1127153 A1 EP1127153 A1 EP 1127153A1
Authority
EP
European Patent Office
Prior art keywords
acid
aspartic acid
solution
crude
salts
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP99950763A
Other languages
German (de)
English (en)
Inventor
Torsten Groth
Winfried Joentgen
Michael Schwamborn
Hartwig Wendt
Nikolaus Müller
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Publication of EP1127153A1 publication Critical patent/EP1127153A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P13/00—Preparation of nitrogen-containing organic compounds
    • C12P13/04—Alpha- or beta- amino acids
    • C12P13/20—Aspartic acid; Asparagine

Definitions

  • the present invention relates to a process for the preparation of aspartic acid derivatives of the general formula (I)
  • R represents a radical of the series H, Na, K, NH 4 , Ca, Mg, Li or Fe,
  • R 3 for a residue of the series H, -CH 2 -COOR "-CH 2 -CH 2 -COOR" -CH 2 -CH 2 -OH ;
  • -CH, -CHOH-CH, or -CH, -CHOH-CH, OH characterized in that carbohydrates are fermented in the presence of fumaric acid-producing microorganisms, the resulting fumaric acid-containing fermentation solution is purified, the resulting fumaric acid ammonium salt solution is converted by enzyme catalysis to a crude aspartic acid solution and the crude aspartic acid solution thus obtained after addition of
  • Aspartic acid derivatives of the formula (I) according to the present invention are, for example, iminodisuccinic acid and hydroxyiminodisuccinic acid and their salts.
  • JP 5 320 109 produces iminodisuccinic acid from maleic acid and aspartic acid in the presence of alkali and alkaline earth compounds.
  • Aspartic acid can be used both in the S or R form or as a racemate.
  • JP 8 012 631 maleic acid monomethyl ester is reacted with aspartic acid under alkaline conditions.
  • S-aspartic acid is used to avoid R, R-iminodisuccinic acid.
  • hydroxyiminodisuccinic acid is prepared from epoxysuccinic acid and aspartic acid in the presence of calcium hydroxide.
  • Crude solution after addition of alkali metal hydroxide and concentration with distillation of ammonia water to the aspartic acid derivatives of formula (I) can be converted in high yield and quality, because it was surprisingly found that when concentrating the crude aspartic acid mixed with alkali metal hydroxide almost all of the ammonia can be removed and consequently no undesired side reactions can occur in the subsequent reaction.
  • the concentration is carried out in order to bring the aspartic acid alkali salts formed after the addition of alkali metal hydroxide to the crude aspartic acid solution to a concentration suitable for the subsequent reaction, because the subsequent Reactants used in the reaction can also react with water to form undesirable secondary components.
  • carbohydrates from cereal starch, wheat starch or molasses, in particular dextrose in the presence of organic and inorganic nitrogen sources and minerals, such as urea, ammonium sulfate, zinc sulfate, iron chloride, magnesium sulfate and ammonium hydrogen phosphate, fumaric acid-producing microorganisms, such as, for example, Rhizopus arrhizus , Rhizopus oryzac and Rhizopus nigricans, and vitamins fermented at temperatures of 25 - 35 ° C.
  • organic and inorganic nitrogen sources and minerals such as urea, ammonium sulfate, zinc sulfate, iron chloride, magnesium sulfate and ammonium hydrogen phosphate, fumaric acid-producing microorganisms, such as, for example, Rhizopus arrhizus , Rhizopus oryzac and Rhizopus nigricans, and vitamins fermented at temperatures of 25 - 35 ° C.
  • the fumaric acid formed is neutralized either by adding ammonium, alkali or alkaline earth hydroxides, ammonium, alkali or alkaline earth carbonates or ammonium, alkali or alkaline earth hydrogen carbonates, preferably by adding calcium carbonate, or by suitable extraction processes from the Fermentation mixture removed.
  • the fumaric acid is released again by adding the bases mentioned above, preferably by adding ammonia or aqueous ammonia solution from the extractant, for example as the fumaric acid ammonium salt.
  • the sparingly soluble fumaric acid calcium salt is filtered off and converted into fumaric acid ammonium salt by means of ammonia, ammonium carbonate or ammonium hydrogen carbonate.
  • the fumaric acid ammonium salt solution thus obtained which can consist of fumaric acid monoammonium salt or fumaric acid diammonium salt or a mixture of both, is purified before the enzymatic conversion to crude aspartic acid solution.
  • the cleaning can be carried out by recrystallization, membrane filtration, solvent extraction, absorbents such as activated carbon or processes supported by ion exchangers.
  • the fumaric acid ammonium salt solution obtained from the fermentation process is converted with an ion exchanger into the fumaric acid monoammonium salt, which is further purified by crystallization. This salt is used in the next process step before
  • the 0.5 - 2 molar fumaric acid diammonium salt solution produced in the cleaning step is now in the presence of a suitable enzyme and trace elements such as calcium, magnesium, manganese, strontium or iron at temperatures of 20 to 60 ° C and a pH of 7-9 converted into a raw aspartic acid solution delt, which mainly consists of aspartic acid monoammonium salt, but can also be present in a mixture with aspartic acid diammonium salt.
  • the aspartic acid contained is predominantly in the S form, preferably in> 90% of theory. Th. In the S-form, particularly preferably in> 99% of theory. Th. In the S-shape.
  • the conversion which is carried out with a yield of 90-100% of theory.
  • Th. Based on the fumaric acid salt used, is carried out using aspartase, which can be used in the form of bacterial cultures, permeabilized cells, cell extracts or in purified form. In a preferred embodiment, aspartase is used in immobilized form.
  • the aspartic acid alkali metal salt solution will be adjusted to a suitable concentration for use in the subsequent reaction.
  • concentrations can be between 20 and 75% by weight, preferably between 30 and 70% by weight, particularly preferably between 40 and 65% by weight, based on the aspartic acid alkali metal salt contained in the solution.
  • ammonia water is distilled off, which can be used again, for example, in the work-up process of the fermentation solution containing fumaric acid.
  • the aspartic acid-alkali metal salt solution comes from a crude aspartic acid solution in which trace elements and, if appropriate, impurities can be contained.
  • the trace elements such as calcium, magnesium, manganese, iron and strontium, depending on the aspartic acid alkali metal salt concentration and the pH of the solution, can cause cloudiness.
  • These turbidities are filtered off at temperatures of 5-60 ° C., preferably 10-50 ° C., particularly preferably 15-40 ° C.
  • the aspartic acid alkali metal salt solution thus prepared becomes
  • Aspartic acid derivatives of the formula (I) are u. a. Iminodisuccinic acid, hydroxyiminodisuccinic acid, ethylenediaminedisuccinic acid, aspartic acid-N, N-diacetic acid, aspartic acid-N, N-dipropionic acid, N, N-dihydroxyethylaspartic acid, N, N-di- (2-hydroxypropyl) aspartic acid and N, N-
  • Di- (2,3-dihydroxypropyl) aspartic acid and its Na, K, NH 4 , Ca, Mg, Li and Fe salts Di- (2,3-dihydroxypropyl) aspartic acid and its Na, K, NH 4 , Ca, Mg, Li and Fe salts.
  • Iminodisuccinic acid, hydroxyiminodisuccinic acid, ethylenediaminedisuccinic acid, and aspartic acid-N, N-diacetic acid and their Na, K, NH 4 , Ca, Mg, Li and Fe salts are preferably prepared according to the process of the invention.
  • the aspartic acid / alkali metal salt solution prepared by the process according to the invention is reacted with unsaturated mono- or dicarboxylic acids, such as, for example, acrylic acid, methacrylic acid, maleic acid or fumaric acid and their alkali metal salts, preferably sodium salts.
  • unsaturated mono- or dicarboxylic acids such as, for example, acrylic acid, methacrylic acid, maleic acid or fumaric acid and their alkali metal salts, preferably sodium salts.
  • Ethylene oxide and propylene oxide are used as epoxides
  • 2,3-epoxypropanol is used as epoxy alcohol
  • epoxy succinic acid and its alkali metal salts are used as epoxy acid.
  • 1,2-dibromoethane is used as the alkyl halide and chloroacetic acid, for example, as the haloalkanoic acid.
  • chloroacetic acid for example, as the haloalkanoic acid.
  • formaldehyde and alkali metal cyanides or alkali metal hydroxides and HCN used for the cyanomethylation.
  • Maleic acid, epoxysuccinic acid, chloroacetic acid and bromoacetic acid and their salts, and 1,2-dichloroethane, 1,2-dibromoethane, formaldehyde and NaCN are preferably used.
  • the reactants mentioned can be in the form of gas or in liquid, solid or dissolved
  • the concentration of the resulting reaction mixtures is 20 to 75% by weight, preferably 30 to 70% by weight, particularly preferably 40-65% by weight, based on the solid contained.
  • the pH values are 3-13, preferably 5-12, particularly preferably 6-11.5.
  • the reaction temperatures are 20-200 ° C., preferably 30-175 ° C., particularly preferably 40-150 ° C.
  • the molar ratios between the aspartic acid alkali metal salt and the reactant can be 1: 0.5-5, preferably 1: 0.9-4, particularly preferably 1: 1.4-3.
  • the reaction times can be between 0.1 and 100 h, preferably between 0.5 and 50 h, particularly preferably between 1 and 25 h.
  • the reactants can be used individually, in succession or as mixtures.
  • the compounds of the formula (I) obtained by the process according to the invention can be used as complexing agents for alkaline earth metal ions and heavy metal ions in detergents and cleaning agents, in the pharmaceutical, cosmetic, textile and paper sectors, in the building materials and electroplating industry and in agriculture.
  • the use as a water softener, bleach stabilizer, micro-nutrient fertilizer and retarder is particularly noteworthy.
  • EDTA ethylenediaminetetraacetic acid
  • DTPA diethylenetriaminepentaacetic acid
  • NTA nitrilotriacetic acid
  • Phosphates are complexing agents that are used for eutrophication of water contribute. In summary, these are ecotoxicological properties that are perceived as disadvantageous today.
  • the aspartic acid derivatives of the formula (I) and their mixtures are now biodegradable complexing agents. They are quickly and largely degraded in sewage treatment plants and surface waters and therefore have almost no accumulation potential in the environment. As a result, heavy metals in the vicinity can no longer be remobilized. You can also no longer get into the drinking water treatment.
  • the aspartic acid derivatives of the formula (I) and their mixtures are prepared by the process according to the invention from crude aspartic acid solutions which were previously obtained from carbohydrates by fermentation, isolation and purification of the intermediate fumaric acid and the enzyme catalysis to form aspartic acid.
  • the route from dextrose to aspartic acid ammonium salt solution described in WO 98/16652 is followed in a corresponding manner.
  • the aspartic acid ammonium salt solution of WO 98/16652 corresponds to the crude aspartic acid solution of the process according to the invention.
  • the following examples therefore begin with the use of the raw aspartic acid solution or with the use of an aspartic ammonium salt solution.
  • a 2 molar S-aspartic acid monoammonium salt solution is used as an example.
  • the reaction mixture is concentrated in vacuo at 102 ° C. and the residue is completely dried at 100 mbar and 100 ° C. 353 g of solid with 5.2% by weight tartaric acid Na 2 salt and 3.6% by weight aspartic acid Na 2 salt are obtained.
  • the yield of hydroxyiminodisuccinic acid Na 4 salt is approx. 90% of theory

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  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Zoology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Microbiology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Biotechnology (AREA)
  • Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • General Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Genetics & Genomics (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé pour la production de dérivés d'acide aspartique de la formule générale (I), et de leurs mélanges. Dans ladite formule, R1, R2, R3 ont les significations indiquées dans la description. Ces dérivés sont produits à partir de glucides par fermentation en présence de micro-organismes.
EP99950763A 1998-11-02 1999-10-20 Procede pour la production de derives d'acide aspartique Withdrawn EP1127153A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19850359 1998-11-02
DE1998150359 DE19850359A1 (de) 1998-11-02 1998-11-02 Verfahren zur Herstellung von Asparaginsäurederivaten
PCT/EP1999/007948 WO2000026398A1 (fr) 1998-11-02 1999-10-20 Procede pour la production de derives d'acide aspartique

Publications (1)

Publication Number Publication Date
EP1127153A1 true EP1127153A1 (fr) 2001-08-29

Family

ID=7886349

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99950763A Withdrawn EP1127153A1 (fr) 1998-11-02 1999-10-20 Procede pour la production de derives d'acide aspartique

Country Status (5)

Country Link
EP (1) EP1127153A1 (fr)
JP (1) JP2002528131A (fr)
AU (1) AU6341599A (fr)
DE (1) DE19850359A1 (fr)
WO (1) WO2000026398A1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1086944B1 (fr) 1999-09-03 2005-05-25 Nippon Shokubai Co., Ltd. Composition de dérivés d'amino-acide et procédé pour la préparation d'un dérivé d'amino-acide
DE10248022B4 (de) * 2002-10-15 2008-11-13 Lanxess Deutschland Gmbh Verwendung chelatisierter Pflanzenspurennährstoffe
ES2395736T3 (es) 2007-05-03 2013-02-14 Atotech Deutschland Gmbh Procedimiento para aplicar un revestimiento metálico a un substrato no conductor
US8362077B2 (en) * 2008-08-15 2013-01-29 Pibed Limited Chemical compositions for skin care emulsions and heavy duty hand cleansers
EP2305856A1 (fr) 2009-09-28 2011-04-06 ATOTECH Deutschland GmbH Processus d'application d'un revêtement métallique sur un substrat non conducteur
CN104447370B (zh) * 2014-04-03 2015-09-23 石家庄开发区德赛化工有限公司 一种亚氨基二琥珀酸盐螯合剂的制备方法
CN107814734A (zh) * 2017-10-17 2018-03-20 山东泰和水处理科技股份有限公司 绿色螯合剂天冬氨酸二乙酸四钠的制备方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2992428B2 (ja) * 1993-09-17 1999-12-20 三菱レイヨン株式会社 アミノポリカルボン酸類およびその製造方法
GB2316073B (en) * 1993-11-03 1998-05-13 Ass Octel Alkylation of amino acids
JPH0812631A (ja) * 1994-06-24 1996-01-16 Nitto Chem Ind Co Ltd イミノジコハク酸とそのアルカリ金属塩の製造法およびそれらを含む生分解性キレート剤
EP0771793B1 (fr) * 1995-10-31 2001-04-04 Nippon Shokubai Co., Ltd. Procédé de préparation de composés époxydés
ATE217650T1 (de) * 1996-09-20 2002-06-15 Dsm Fine Chem Austria Gmbh Verfahren zur herstellung von z-l-asparaginsäure- dinatriumsalz aus fumarsäure
IL119414A (en) * 1996-10-13 2000-08-31 Amylum Nv Process for the production of aspartic acid condensate

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0026398A1 *

Also Published As

Publication number Publication date
JP2002528131A (ja) 2002-09-03
DE19850359A1 (de) 2000-05-04
WO2000026398A1 (fr) 2000-05-11
AU6341599A (en) 2000-05-22

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