WO1997028271A1 - Procede de preparation d'amines optiquement actives - Google Patents

Procede de preparation d'amines optiquement actives Download PDF

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Publication number
WO1997028271A1
WO1997028271A1 PCT/EP1997/000239 EP9700239W WO9728271A1 WO 1997028271 A1 WO1997028271 A1 WO 1997028271A1 EP 9700239 W EP9700239 W EP 9700239W WO 9728271 A1 WO9728271 A1 WO 9728271A1
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WO
WIPO (PCT)
Prior art keywords
formula
amine
alkyl
radical
process according
Prior art date
Application number
PCT/EP1997/000239
Other languages
German (de)
English (en)
Inventor
Claus Dreisbach
Uwe Stelzer
Original Assignee
Bayer Aktiengesellschaft
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 Aktiengesellschaft filed Critical Bayer Aktiengesellschaft
Priority to JP9527273A priority Critical patent/JP2000504224A/ja
Priority to CA002244917A priority patent/CA2244917A1/fr
Priority to KR1019980705922A priority patent/KR19990082197A/ko
Priority to EP97902188A priority patent/EP0877815A1/fr
Publication of WO1997028271A1 publication Critical patent/WO1997028271A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/82—Purification; Separation; Stabilisation; Use of additives
    • C07C209/86—Separation
    • C07C209/88—Separation of optical isomers
    • 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
    • C12P13/02—Amides, e.g. chloramphenicol or polyamides; Imides or polyimides; Urethanes, i.e. compounds comprising N-C=O structural element or polyurethanes
    • 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
    • C12P41/00—Processes using enzymes or microorganisms to separate optical isomers from a racemic mixture
    • 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
    • C12P41/00—Processes using enzymes or microorganisms to separate optical isomers from a racemic mixture
    • C12P41/006—Processes using enzymes or microorganisms to separate optical isomers from a racemic mixture by reactions involving C-N bonds, e.g. nitriles, amides, hydantoins, carbamates, lactames, transamination reactions, or keto group formation from racemic mixtures
    • C12P41/007—Processes using enzymes or microorganisms to separate optical isomers from a racemic mixture by reactions involving C-N bonds, e.g. nitriles, amides, hydantoins, carbamates, lactames, transamination reactions, or keto group formation from racemic mixtures by reactions involving acyl derivatives of racemic amines

Definitions

  • the present invention relates to a new process for the preparation of known, optically active amines which are used as intermediates for the preparation of
  • Lipases from Pseudomonas for example Amano P, or from Pseudomonas spec DSM 8246 can be used as hydrolases.
  • the optically active, primary and secondary amines can be prepared by first enantio racemic amine in the presence of a hydrolase with an ester which has an electron-rich heteroatom in the acid part in the vicinity of the carbonyl carbon atom - selectively acylated
  • R 1 and R 2 are different
  • R 1 represents methyl, ethyl or a radical of the formula (II)
  • R 3 is a C ⁇ C- Q alkylene radical or a C 2 -C, 0 - AI may learn keny,
  • R 4 is a C j -C Q alkyl radical, a C 6 -C 10 aryl radical or a C 7 -C 14 aralkyl radical and
  • R 2 represents C - C 10 alkyl or optionally substituted C 6 -C ] 4 aryl
  • R 5 and R 6 are the same or different and each represents optionally substituted C - 20 alkyl or optionally substituted C 6 -C] 0 aryl are C and R 5 additionally also be hydrogen,
  • R .1 J , R- and R have the meanings given above,
  • (R) amines are to be understood as those optically active compounds of the formulas (I) and (IV-R) which have the (R) configuration on the asymmetrically substituted carbon atom.
  • (S) amines are those optically active compounds of the To understand formulas (I) and (IS) which have the (S) configuration at the chirate center In the formulas for (R) - and (S) amines, the asymmetrically substituted carbon atom is identified by *.
  • Suitable substituents for alkyl and aryl radicals are, for example, up to 3 identical or different substituents from the group comprising C 1 -C 6 -alkyl, C - C 6 -alkoxy, halogen, nitro and cyano radicals substituted with alkyl radicals
  • Alkyl residues are branched alkyl residues
  • R 1 and R 2 are different from each other, wherein
  • R 1 preferably represents methyl, ethyl or a radical of the formula (III) in which R 3 represents a methylene or ethylene radical, R 4 represents a methyl, ethyl,
  • Phenyl or benzyl and X are O and
  • R 2 preferably represents C r C 4 alkyl
  • R 1 very particularly preferably represents -CH 2 -O-CH 3 and R 2 represents methyl
  • R 5 preferably represents C 1 -C 6 -alkyl which is optionally substituted once or twice by C 4 -C 4 -alkyl or optionally em 2 to 2 times by C-C 4- alkyl, C ] -C 4 -alkoxy, chlorine, bromine, nitro and / or cyano-substituted phenyl.
  • R 5 particularly preferably represents unsubstituted C r C 4 -alkyl.
  • R 6 is preferably and independently of R 5 particularly preferably represents one of the radicals set forth in Trains t R 5 as preferred and particularly granted ⁇ most preferably, R 5 is methyl and R 6 is ethyl
  • optically active amines of the formula (I-S) can be prepared in high yield and very good optical purity by the process according to the invention on the basis of the known state of the art
  • the method according to the invention has a number of advantages. It enables the production of a large number of optically active amines with high yield and excellent optical purity. It is also favorable that it is possible to work with a relatively high substrate concentration, the reaction times are short and continuous operation is possible. It is also advantageous that the required biocatalyst is available in large quantities and is stable even at elevated temperatures. The biocatalyst can be used in a relatively small amount in relation to the substrate. Finally, the implementation of the reaction and the isolation of the desired substances also pose no difficulties.
  • racemic amines of the formula (I) required as starting materials for the process according to the invention are known or can be prepared by methods known per se.
  • the esters of the formula (III) required are likewise known or can be prepared by methods known per se.
  • the required lipase can be used both natively and in immobilized form.
  • Immobilizations are, for example, the use of lipase in microencapsulated form or bound to an organic or inorganic carrier material.
  • Support materials include, for example, diatomaceous earth, ion exchangers, zeolites, polysaccharides, polyamides and polystyrene resins, in particular Celite ® and Lewatit ® types.
  • lipase from Candida antarctica in is suitable
  • an ester of the formula (III) Based on one mol of racemic amine of the formula (I), for example 0.5 to 20 mol of an ester of the formula (III) can be used. When working without an additional diluent, this amount of ester is preferably 1 to 10 mol, in particular 1 to 5 mol. When working with the addition of a diluent, this amount of ester is preferably 1 to 7 mol, in particular 1 to 4 mol.
  • the process according to the invention can be carried out, for example, at temperatures in the range from 0 to 90 ° C., in particular from 10 to 60 ° C. Usually one works at atmospheric pressure, optionally under an inert gas, for example nitrogen.
  • the procedure can be such that the respective racemic amine of the formula (I), the respective ester of the formula (III), if appropriate a diluent and lipase from Candida antarctica are combined in any order and the resulting mixture at the respective reaction temperature until the desired conversion is reached.
  • the amount of lipase based on the racemic amine of the formula (I) can be varied within wide limits. For example, 0.1 to 40% by weight of immobilized lipase, eg B use Novozym ® 435, based on the racemic amine of the formula (I), or a corresponding amount of native lipase. This amount is preferably 0.5 to 30% by weight of immobilized lipase or the corresponding amount of native lipase
  • (R) -amine of the formula (IV-R) For example, one can at least 0.000001 grams of immobilized lipase, for example Novozym ® 435, per g of racemic amine of the formula (I) or a corresponding amount of native lipase used preferably amounts to this quantity 0 , 00001 to 0.1 g of immobilized lipase or a corresponding amount of native lipase
  • the desired (S) -amine of the formula (I-S) can be separated off, for example, by distillation or extraction. Distillation is preferred
  • the residue remaining after this separation can be discarded or used in any way.
  • the acylated (R) -amine of formula (IV) contained therein can be isolated, for example by distillation, and obtained as such or after its isolation from the acylated (R) -amine of formula (IV) in a manner known per se split off the acyl group and thus obtain the (R) -amine corresponding to the (S) -amine of formula (IS) prepared or racemize the acylated (R) -amine obtained and reuse it in the process according to the invention after removal of the acyl group
  • Active ingredients with insecticidal, fungicidal or herbicidal properties are particularly suitable for the preparation of herbicidally active N-thienylchloroacetamides (see, for example, EP-A 296 463 and EP-A 210 320)
  • Candida antarctica lipase (Novozym ® 435) filled in suspension in MTBE. The bed volume was 17 ml.
  • the immobilized Candida antarctica lipase was separated by filtration from the reaction mixture obtained according to Example 1 and the filtrate was worked up by distillation. At normal pressure, first ethyl acetate, ethanol and MTBE passed over, then at 99 ° C. (S) -2-amino-1-methoxypropane and finally at 13 mbar and 105 to 1 10 ° C (R) -N-acetyl-2-amino-l-methoxypropane
  • Example 5 The procedure was as in Example 1, but not fresh immobilized antarctica lipase was used, but rather that which had been recovered according to Example 3. The yield and the ee value for (S) -2-amino-1-methoxypropane were as in Example 1 Example 5

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

Abstract

On obtient des (S)-amines optiquement actives déterminées, par réaction dans un premier temps d'amines racémiques appropriées en présence de lipase de candida antarctica et éventuellement en présence d'un diluant, avec un ester, le mélange obtenu étant séparé dans un second temps.
PCT/EP1997/000239 1996-01-19 1997-01-20 Procede de preparation d'amines optiquement actives WO1997028271A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP9527273A JP2000504224A (ja) 1996-02-01 1997-01-20 光学的に活性なアミン類の製造方法
CA002244917A CA2244917A1 (fr) 1996-02-01 1997-01-20 Procede de preparation d'amines optiquement actives
KR1019980705922A KR19990082197A (ko) 1996-01-19 1997-01-20 광학 활성 아민의 제조 방법
EP97902188A EP0877815A1 (fr) 1996-02-01 1997-01-20 Procede de preparation d'amines optiquement actives

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19603575.9 1996-02-01
DE19603575A DE19603575A1 (de) 1996-02-01 1996-02-01 Verfahren zur Herstellung von optisch aktiven Aminen

Publications (1)

Publication Number Publication Date
WO1997028271A1 true WO1997028271A1 (fr) 1997-08-07

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PCT/EP1997/000239 WO1997028271A1 (fr) 1996-01-19 1997-01-20 Procede de preparation d'amines optiquement actives

Country Status (6)

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EP (1) EP0877815A1 (fr)
JP (1) JP2000504224A (fr)
KR (1) KR19990082197A (fr)
CA (1) CA2244917A1 (fr)
DE (1) DE19603575A1 (fr)
WO (1) WO1997028271A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000011203A1 (fr) * 1998-08-20 2000-03-02 Basf Aktiengesellschaft Dissociation des racemates d'amides primaires catalysee par enzyme
WO2001038292A2 (fr) * 1999-11-25 2001-05-31 Basf Aktiengesellschaft Procede de preparation d'amines optiquement actives
EP1451171A1 (fr) * 2001-12-06 2004-09-01 Posco Procede de production d'amines chirales
WO2024041972A1 (fr) 2022-08-23 2024-02-29 Bayer Aktiengesellschaft Acides nucléiques codant pour des protéines lipases améliorées

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19749555A1 (de) * 1997-11-10 1999-05-12 Henkel Kgaa Enzymatisch-katalysierte N-Acylierung von Aminosäuren, Proteinhydrolysaten und/oder deren Derivaten
DE102005028492A1 (de) 2005-06-20 2006-12-28 Basf Ag Verfahren zur Herstellung von optisch aktiven Aminoalkylphenolen

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4332738A1 (de) * 1993-09-25 1995-03-30 Basf Ag Racematspaltung primärer und sekundärer Amine durch Enzym-katalysierte Acylierung

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4332738A1 (de) * 1993-09-25 1995-03-30 Basf Ag Racematspaltung primärer und sekundärer Amine durch Enzym-katalysierte Acylierung

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 125, no. 19, 4 November 1996, Columbus, Ohio, US; abstract no. 247285, N. OEHRNER ET AL.: "Kinetic resolution of amine and thiol analogs of secondary alcohols catalyzed by the candida antarctica lipase B" page 1097; XP002030210 *
ENZYME MICROB. TECHNOL., vol. 19, no. 5, 1996, pages 328 - 331 *
M. T. REETZ ET AL.: "Highly efficient lipase-catalyzed kinetic resolution of chiral amines", CHIMIA, vol. 48, 1970, pages 570, XP000671431 *
V. GOTOR ET AL.: "Synthesis of optically active amides from .beta-furyl and .beta.-phenyl esters by way of enzymatic aminolysis", JOURNAL OF THE CHEMICAL SOCIETY, PERKIN TRANSACTIONS 1, 1993, LETCHWORTH GB, pages 2453 - 56, XP002030209 *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000011203A1 (fr) * 1998-08-20 2000-03-02 Basf Aktiengesellschaft Dissociation des racemates d'amides primaires catalysee par enzyme
US6465223B1 (en) 1998-08-20 2002-10-15 Basf Aktiengesellschaft Enzyme-catalyzed racemic cleavage of primary amines
WO2001038292A2 (fr) * 1999-11-25 2001-05-31 Basf Aktiengesellschaft Procede de preparation d'amines optiquement actives
WO2001038292A3 (fr) * 1999-11-25 2002-02-28 Basf Ag Procede de preparation d'amines optiquement actives
JP2003514888A (ja) * 1999-11-25 2003-04-22 ビーエーエスエフ アクチェンゲゼルシャフト 光学活性アミンの製造方法
US7078226B1 (en) 1999-11-25 2006-07-18 Basf Aktiengesellschaft Method for producing optically active amines
US7358396B2 (en) 1999-11-25 2008-04-15 Basf Aktiengesellschaft Preparation of optically active amines
JP4776846B2 (ja) * 1999-11-25 2011-09-21 ビーエーエスエフ ソシエタス・ヨーロピア 光学活性アミンの製造方法
EP1451171A1 (fr) * 2001-12-06 2004-09-01 Posco Procede de production d'amines chirales
EP1451171A4 (fr) * 2001-12-06 2004-11-10 Posco Procede de production d'amines chirales
WO2024041972A1 (fr) 2022-08-23 2024-02-29 Bayer Aktiengesellschaft Acides nucléiques codant pour des protéines lipases améliorées

Also Published As

Publication number Publication date
KR19990082197A (ko) 1999-11-25
EP0877815A1 (fr) 1998-11-18
CA2244917A1 (fr) 1997-08-07
JP2000504224A (ja) 2000-04-11
DE19603575A1 (de) 1997-08-07

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