EP1725674A1 - Procede pour produire des alcools secondaires chiraux - Google Patents

Procede pour produire des alcools secondaires chiraux

Info

Publication number
EP1725674A1
EP1725674A1 EP05707624A EP05707624A EP1725674A1 EP 1725674 A1 EP1725674 A1 EP 1725674A1 EP 05707624 A EP05707624 A EP 05707624A EP 05707624 A EP05707624 A EP 05707624A EP 1725674 A1 EP1725674 A1 EP 1725674A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
alcohol
formula
amino
defined above
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Withdrawn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
EP05707624A
Other languages
German (de)
English (en)
Inventor
Thomas Dax
Michael Stanek
Peter Pöchlauer
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.)
Patheon Austria GmbH and Co KG
Original Assignee
DSM Fine Chemicals Austria Nfg GmbH and Co KG
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 DSM Fine Chemicals Austria Nfg GmbH and Co KG filed Critical DSM Fine Chemicals Austria Nfg GmbH and Co KG
Publication of EP1725674A1 publication Critical patent/EP1725674A1/fr
Withdrawn legal-status Critical Current

Links

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
    • C12P41/00—Processes using enzymes or microorganisms to separate optical isomers from a racemic mixture
    • C12P41/003—Processes using enzymes or microorganisms to separate optical isomers from a racemic mixture by ester formation, lactone formation or the inverse reactions
    • C12P41/004—Processes using enzymes or microorganisms to separate optical isomers from a racemic mixture by ester formation, lactone formation or the inverse reactions by esterification of alcohol- or thiol groups in the enantiomers or the inverse reaction
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
    • 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
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
    • 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
    • Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups

Definitions

  • the present invention relates to a process for the production of chiral, secondary alcohols in an optical purity of up to 100% ee and in up to 100% yield.
  • S means a “spectator” ligand, a neutral ligand that is difficult to exchange, and from the group of olefins, dienes or aromatics, such as benzene, toluene, xylene, cumene, cymene, naphthalene, anisole, chlorobenzene, indole, cyclopentadiene - nyl derivatives, tetraphenyl, cyclopentadienone, dihydroindole, tetrahydronaphthalene, gallic acid, benzoic acid and phenylglycine, and L is a neutral ligand which is relatively easy to replace by another ligand and from the group of acetonitrile, DMSO, methanol, water, THF,
  • the transition metal compound can also be converted into a transition metal complex in which the neutral ligand is exchanged with another ligand or by complexing the transition metal compound with a ligand.
  • a base is added to activate the catalyst.
  • the base can be selected from the group of alkali or alkaline earth carbonates or bicarbonates. Examples include sodium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, etc.
  • the catalyst is used in an amount of 0.005 to 0.1 mol% based on ketone or racemic alcohol, preferably 0.01 to 0.03 mol%.
  • C 2 -C 6 alkenyl esters of aliphatic Ci to C ⁇ carboxylic acids can be used as acyl donors, 1-propenyl, vinyl or isopropenyl propionate or butyrate are preferred.
  • the entire amount of the acyl donor, which is used in an amount of 0.5 to 1.0 equivalents based on the ketone, can be charged or added slowly.
  • a small amount of activated carbon and a filter aid are preferably added to the reaction mixture and stirred for some time.
  • the mixture is filtered off, the filter cake is washed with solvent and the filtrate is diluted with solvent. It is cooled, inoculated and the product crystallizes at temperatures from -20 to 0 ° C.
  • the (S) -alcohol of the general formula (I) thus obtained is washed with solvent and dried at room temperature under vacuum.

Landscapes

  • 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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)

Abstract

L'invention concerne un procédé servant à produire des alcools secondaires chiraux de formule (I). Dans la formule (I), A représente un cycle aromatique, hétérocyclique ou alicyclique ou une combinaison cyclique ayant 4 à 20 atomes de C, n vaut 0, 1, 2, 3, 4 ou 5, R représente halogène, OH, un groupe de protection O, NO2, N,N-R2,R3-amine, R2 et R3 représentant alkyle C1-C6, phényle ou benzyle, N,N-R2,R3-amino-alkyle C1-C6, alkyle C1-C6, haloalkyle C1-C6, alcoxy C1-C6, alcoxycarbonyle C1-C4 ou CN, et R1 représente N,N-R2,R3-amine, N,N-R2,R3-amino-alkyle C1-C6, alkyle C1-C12, haloalkyle C1-C6, alcoxycarbonyle C1-C4 ou alcoxy C1-C6-alkyle C1-C6 ou R1 représente un reste alkylène C2-C5 qui forme une combinaison cyclique avec le reste A. Selon ce procédé, a) éventuellement une cétone de formule (II) est réduite à l'alcool racémique correspondant de formule (III) au moyen d'un alcool C1-C6 aliphatique, en présence d'un catalyseur à base de métal de transition et d'une base, et b) l'alcool de formule (III) est transformé, en présence d'un catalyseur d'estérification et d'un donneur acyle, en un mélange constitué de (R)-ester de formule (IV), dans laquelle R4 représente H ou alkyle C1-C5, et de (S)-alcool de formule (I). Le (S)-alcool est ensuite isolé du mélange réactionnel par cristallisation ou distillation en fonction de son état d'agrégation.
EP05707624A 2004-03-18 2005-02-25 Procede pour produire des alcools secondaires chiraux Withdrawn EP1725674A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AT0047104A AT500556A1 (de) 2004-03-18 2004-03-18 Verfahren zur herstellung von chiralen, sekundären alkoholen
PCT/EP2005/001977 WO2005095628A1 (fr) 2004-03-18 2005-02-25 Procede pour produire des alcools secondaires chiraux

Publications (1)

Publication Number Publication Date
EP1725674A1 true EP1725674A1 (fr) 2006-11-29

Family

ID=34960671

Family Applications (1)

Application Number Title Priority Date Filing Date
EP05707624A Withdrawn EP1725674A1 (fr) 2004-03-18 2005-02-25 Procede pour produire des alcools secondaires chiraux

Country Status (7)

Country Link
US (1) US20070196904A1 (fr)
EP (1) EP1725674A1 (fr)
JP (1) JP2007529207A (fr)
CN (1) CN1934267A (fr)
AT (1) AT500556A1 (fr)
NO (1) NO20064686L (fr)
WO (1) WO2005095628A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102851349A (zh) * 2012-09-27 2013-01-02 南京工业大学 同时获得两种单一手性仲醇的方法
CN105132394B (zh) * 2015-09-24 2018-03-16 中国科学院南海海洋研究所 一种脂肪酶lipase6及其编码基因和应用
CN109735582B (zh) * 2018-12-24 2022-06-21 浙江工业大学 一种脂肪酶催化在线合成环己醇类β-氨基醇衍生物的方法
CN110240538B (zh) * 2019-06-27 2022-04-22 万华化学集团股份有限公司 一种制备高碳支链仲醇的方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3743824C2 (de) * 1987-12-23 1997-03-06 Hoechst Ag Verfahren zur enzymatischen Racematspaltung von racemischen Alkoholen mit/in Vinylestern durch Umesterung
JP3638643B2 (ja) * 1994-10-14 2005-04-13 高砂香料工業株式会社 光学活性１−オクテン−３−オールの製造法
AU2002365968A1 (en) * 2001-11-19 2003-06-10 Merck And Co., Inc. Process for the synthesis of (r)-1-(3,5-bis(trifluoromethyl)-phenyl)ethan-1-ol and esters thereof by dynamic kinetic resolution

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2005095628A1 *

Also Published As

Publication number Publication date
CN1934267A (zh) 2007-03-21
US20070196904A1 (en) 2007-08-23
JP2007529207A (ja) 2007-10-25
AT500556A1 (de) 2006-01-15
NO20064686L (no) 2006-12-18
WO2005095628A1 (fr) 2005-10-13

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