WO2009006662A2 - Procédé de clivage oxydatif de composés aromatiques de vinyle - Google Patents

Procédé de clivage oxydatif de composés aromatiques de vinyle Download PDF

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Publication number
WO2009006662A2
WO2009006662A2 PCT/AT2008/000250 AT2008000250W WO2009006662A2 WO 2009006662 A2 WO2009006662 A2 WO 2009006662A2 AT 2008000250 W AT2008000250 W AT 2008000250W WO 2009006662 A2 WO2009006662 A2 WO 2009006662A2
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WO
WIPO (PCT)
Prior art keywords
peroxidases
laccases
oxidation
enzyme
peroxidase
Prior art date
Application number
PCT/AT2008/000250
Other languages
German (de)
English (en)
Other versions
WO2009006662A3 (fr
WO2009006662A4 (fr
Inventor
Wolfgang Kroutil
Miguel Lara
Original Assignee
Universität Graz
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
Priority claimed from AT0106207A external-priority patent/AT505436B1/de
Application filed by Universität Graz filed Critical Universität Graz
Priority to US12/668,640 priority Critical patent/US20100184174A1/en
Priority to JP2010515315A priority patent/JP2010532664A/ja
Priority to DE112008001786T priority patent/DE112008001786A5/de
Publication of WO2009006662A2 publication Critical patent/WO2009006662A2/fr
Publication of WO2009006662A3 publication Critical patent/WO2009006662A3/fr
Publication of WO2009006662A4 publication Critical patent/WO2009006662A4/fr

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    • 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
    • C12P7/24—Preparation of oxygen-containing organic compounds containing a carbonyl group
    • 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
    • C12P7/24—Preparation of oxygen-containing organic compounds containing a carbonyl group
    • C12P7/26—Ketones

Definitions

  • the invention relates to processes for the oxidative cleavage of ethylenic double bonds conjugated with aromatic rings using enzyme catalysts.
  • an oxidation process for alkenes would be desirable, which avoids the above disadvantages and in particular a non-toxic, easily available bares oxidizing agent, such as oxygen, can be used.
  • peroxidases and laccases are capable, under specific conditions, of catalyzing the oxidative cleavage of special ethylenic double bonds by oxygen to aldehydes and ketones.
  • oxygen is normally not (or, in the case of laccases, at least not a preferred) substrate for such enzymes and, on the other hand, the resulting oxidation products are those commonly produced in ozonolysis reactions.
  • peroxidases can actually - like the
  • 0 name indicates - only process peroxide bonds, and furthermore haloperoxidases give only halogenated, e.g. chlorinated or brominated oxidation products.
  • the present invention is to provide a process for the oxidative cleavage of aromatic ring-conjugated ethylenic double bonds, i. optionally substituted vinylaromatics of the following formula (1), which is characterized in that one or more compounds of For ⁇
  • substituents R 1 may be identical or different and are selected from: a) saturated or unsaturated hydrocarbon groups having 1 to 10 carbon atoms, in which one or more carbon atoms are optionally replaced by a heteroatom selected from oxygen, nitrogen and sulfur, and the groups optionally -6 alkyl with one or more substituents selected from Ci, Ci -6 alkylene, Ci_6-alkoxy, amino, Ci -6 alkylamino, and Ci- 6 - dialkylamino groups, halogens, hydroxy, oxo, and cyano b) amino, d -6- alkylamino and Ci -6- dialkylamino groups, and c) halogens, hydroxy and cyano, wherein any two of the substituents R 1 may be connected to an alicyclic or aromatic ring, and wherein the substituents R 2
  • aryl alkenes can be prepared by using oxygen, an omnipresent, innocuous oxidizing agent, and by specific natural enzymes that are readily and inexpensively available by biological or biotechnological means, to the desired aldehydes and ketones, e.g. Vanillin, to be oxidized.
  • oxygen oxygen
  • an omnipresent, innocuous oxidizing agent oxygen
  • specific natural enzymes that are readily and inexpensively available by biological or biotechnological means
  • the at least one enzyme is selected from fungal peroxidases and laccases, haloperoxidases, lignin peroxidases, horseradish peroxidase and bovine milk peroxidase, more preferably fungal peroxidases from Coprinus cinereus (scrubby Tintling), from laccases from Coriolus.
  • the process is preferably carried out in a buffer in order to be able to keep the reaction conditions, in particular the pH, stable during the oxidation.
  • the reaction is carried out in bis-tris buffer, acetate buffer, formate buffer or phosphate buffer.
  • the pH of the reaction mixture is preferably adjusted to 2 to 7, more preferably to 2 to 4, since in these areas the respective enzymes have their maximum activity.
  • the process according to the invention is carried out under O 2 overpressure so as to increase the yields.
  • O 2 overpressure so as to increase the yields.
  • the oxidation is preferably carried out under an O 2 overpressure of 1 to 6 bar, preferably 2 to 3 bar. Even higher values result in little or no additional improvement, often even lower turnovers, and would significantly increase the expenditure on equipment. In the above pressure ranges, for example, a conventional Parr apparatus can be used easily.
  • the process is carried out under the action of light, ie under irradiation, since in this way the yields, in particular when laccases are used as enzymes, can be increased many times over.
  • the process is carried out in the presence of an organic solvent or solvent mixture, which is preferably selected from C 1-4 -alkanols, dimethylsulfoxide, toluene, acetone, dioxane, tetrahydrofuran, dimethylformamide and mixtures thereof, and preferably 5 in a proportion of 1 to 20, more preferably 5 to 15, Vol .-% of the reaction mixture is contained.
  • the invention thus relates to the use of fungal peroxidases and laccases, fungal halogen peroxidases, bacterial halogenated
  • Figs. 1 to 3 show the change in conversion in the process according to the invention with the addition of various organic solvents. ! 0
  • the reactor was purged with pure molecular oxygen and the pressure was adjusted to 2 bar oxygen. After 24 h at 170 U / min and 25 0 C, the reaction mixtures were transferred to 2 ml test tubes, and the wells were washed with EtOAc (600 ul). These 600 .mu.f were added to the respective Eprouvetten so that also a first extraction of the aqueous reaction mixtures through-
  • the pH adjusting buffers were as follows: pH 0 - trimethylammonium formate / formic acid, 20 mM pH 3 - trimethylammonium formate / formic acid, 20 mM pH 4 - sodium acetate / acetic acid, 50 mM pH 5 - sodium acetate / acetic acid, 50 mM pH 6 - Bis Tris buffer, 50mM »5 pH 7 - Bis Tris buffer, 50mM
  • trans-anethole can be oxidized to p-anisaldehyde in sometimes very good yield by enzyme catalysis, and that peroxidases are clearly superior to laccases, although the latter can also be used for preparative purposes. Examples 37 to 40
  • Example 33 Analogously to Example 33, instead of trans-anethole, ⁇ , ⁇ -dimethylstyrene was oxidized with radish peroxidase, batch 1, in this case to benzaldehyde. The results of both experiments and those of Example 43 are shown in Table 7 for comparison.
  • trans-anethol was oxidized by means of Coprinus cinereus peroxidase, batch 1 or horseradish peroxidase, batch 1 as catalyst.
  • DMSO dimethyl sulfoxide
  • DMF dimethylformamide
  • Tween 80 polyoxyethylene (20) sorbitan monooleate
  • THF tetrahydrofuran
  • trans-anethole was oxidized with horseradish peroxidase as the catalyst, replacing the 900 ⁇ l of aqueous buffer with increasing percentages of DMSO.
  • Table 13 shows the conversion achieved for each DMSO content. The data are also shown graphically in FIG.
  • horseradish peroxidase at a level of 40% DMSO in the Medium is about as active as without organic solvent. At higher concentrations the activity decreases rapidly, and from 60% DMSO substantially no enzymatic effect is detectable. With 20 to 30% DMSO in the medium, the conversion was increased by about 20%. The best results, ie an approximately 40% increase in sales, were achieved with 5 to 15% solvent.
  • Horseradish peroxidase lot 1: Sigma-Aldrich, P2088 horseradish peroxidase, lot 2: Sigma-Aldrich, P8250, 031 K74711 horseradish peroxidase, lot 3: Sigma-Aldrich, P6140, 051 K7490 horseradish peroxidase, lot 4: Roche , POD10108090001, Lot .: 93350720
  • Laccase of Rhus vernicifera Sigma-Aldrich, L-2157, Lot .: 67H0281
  • Laccase of Agaricus bisporus Fluka, 40452, Lot. & Filling code 443928/1 42703431 Laccase DeniLite Il Base: Novozymes, OM30402613, Chemical Abtracts Service (CAS) Registry No .: 80498-15-3 references

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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)
  • Enzymes And Modification Thereof (AREA)

Abstract

L'invention concerne un procédé de clivage oxydatif de composés aromatiques de vinyle de formule (1), caractérisé en ce que des composés de formule (1) sont oxydés en présence d'oxygène moléculaire avec au moins une enzyme choisie parmi les peroxydases et les laccases en tant que catalyseur selon le schéma réactionnel suivant pour former des aldéhydes ou des cétones de formules (2) et (3) : dans lesquelles n représente un nombre entier de 0 à 5; les R1 sont choisis parmi les groupements hydrocarbonés saturés ou insaturés ayant 1 à 10 atomes de carbone, dans lesquels des atomes de carbone sont éventuellement remplacés par des hétéroatomes et sont éventuellement substitués, les groupements amino, C1-6-alkylamino et C1-6-dialkylamino, les halogènes, hydroxy et cyano, deux des substituants R1 pouvant être reliés en un cycle; R2 et R3 représentent à chaque fois indépendamment l'un de l'autre l'hydrogène ou une des options de R1 ; R2 et/ou R3 pouvant être reliés avec un R1 en un cycle; R2 ou R3 pouvant à chaque fois représenter une liaison chimique.
PCT/AT2008/000250 2007-07-10 2008-07-09 Procédé de clivage oxydatif de composés aromatiques de vinyle WO2009006662A2 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US12/668,640 US20100184174A1 (en) 2007-07-10 2008-07-09 Process for the oxidative cleavage of vinylaromatics using peroxidases or laccases
JP2010515315A JP2010532664A (ja) 2007-07-10 2008-07-09 ビニル芳香族化合物の酸化的開裂法
DE112008001786T DE112008001786A5 (de) 2007-07-10 2008-07-09 Verfahren zur oxidativen Spaltung von Vinylaromaten

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
ATA1062/2007 2007-07-10
AT0106207A AT505436B1 (de) 2007-07-10 2007-07-10 Enzymkatalysiertes verfahren zur oxidativen spaltung von ethylenischen doppelbindungen
AT0190207A AT505437B1 (de) 2007-07-10 2007-11-23 Verfahren zur oxidativen spaltung von mit aromatischen ringen konjugierten ethylenischen doppelbindungen
ATA1902/2007 2007-11-23

Publications (3)

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WO2009006662A2 true WO2009006662A2 (fr) 2009-01-15
WO2009006662A3 WO2009006662A3 (fr) 2009-04-09
WO2009006662A4 WO2009006662A4 (fr) 2009-06-04

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013029076A1 (fr) 2011-08-26 2013-03-07 Universität Graz Dissociation enzymatique d'alcène
US11642469B2 (en) 2008-05-02 2023-05-09 Sanofi-Aventis Deutschland Gmbh Medication delivery device

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996022381A1 (fr) * 1995-01-19 1996-07-25 V. Mane Fils Procede de preparation de substances aromatiques par voie biochimique
US6297403B1 (en) * 1997-06-06 2001-10-02 Consortium für elektrochemische Industrie GmbH Process for the preparation of aldehydes and ketones

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996022381A1 (fr) * 1995-01-19 1996-07-25 V. Mane Fils Procede de preparation de substances aromatiques par voie biochimique
US6297403B1 (en) * 1997-06-06 2001-10-02 Consortium für elektrochemische Industrie GmbH Process for the preparation of aldehydes and ketones

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
MANG, H. ET AL.: "Biokatalytische einstufige Alkenspaltung von Arylalkenen: ein enzymatisches Äquivalent zur reduktiven Ozonisierung" ANGEWANDTE CHEMIE, Bd. 118, Nr. 31, 2006, Seiten 5325-5328, XP002513947 in der Anmeldung erwähnt *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11642469B2 (en) 2008-05-02 2023-05-09 Sanofi-Aventis Deutschland Gmbh Medication delivery device
WO2013029076A1 (fr) 2011-08-26 2013-03-07 Universität Graz Dissociation enzymatique d'alcène
US9273291B2 (en) 2011-08-26 2016-03-01 Universitat Graz Enzymatic alkene cleavage

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WO2009006662A3 (fr) 2009-04-09
WO2009006662A4 (fr) 2009-06-04

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