EP0981638A1 - Procede d'oxydation selective de composes organiques - Google Patents

Procede d'oxydation selective de composes organiques

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Publication number
EP0981638A1
EP0981638A1 EP98920932A EP98920932A EP0981638A1 EP 0981638 A1 EP0981638 A1 EP 0981638A1 EP 98920932 A EP98920932 A EP 98920932A EP 98920932 A EP98920932 A EP 98920932A EP 0981638 A1 EP0981638 A1 EP 0981638A1
Authority
EP
European Patent Office
Prior art keywords
group
oxidase
carbon atoms
hydrogen peroxide
formula
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Withdrawn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
EP98920932A
Other languages
German (de)
English (en)
Inventor
Michael Brian D'amore
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.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
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 EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP0981638A1 publication Critical patent/EP0981638A1/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Withdrawn legal-status Critical Current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
    • 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
    • C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
    • C12N11/14—Enzymes or microbial cells immobilised on or in an inorganic carrier
    • 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
    • C12P1/00—Preparation of compounds or compositions, not provided for in groups C12P3/00 - C12P39/00, by using microorganisms or enzymes
    • 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
    • C12P17/00—Preparation of heterocyclic carbon compounds with only O, N, S, Se or Te as ring hetero atoms
    • C12P17/02—Oxygen as only ring hetero atoms
    • C12P17/04—Oxygen as only ring hetero atoms containing a five-membered hetero ring, e.g. griseofulvin, vitamin C
    • 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
    • C12P3/00—Preparation of elements or inorganic compounds except carbon dioxide

Definitions

  • the invention relates to a process for oxidizing organic compounds; more particularly to a process using an oxidase to generate hydrogen peroxide and employing the generated peroxide to oxidize an oxidizable organic substrate in the presence of a metal-containing catalyst.
  • Hydrogen peroxide is often employed as an oxidizing agent for the production of organic chemicals. It has been used as a reactant in both concentrated and dilute solutions. However, the use of added hydrogen peroxide can pose problems either because of the expense of purification and handling or because of certain safety hazards associated with its use in chemical processes.
  • a wide variety of organic compounds may be oxidized utilizing hydrogen peroxide, for example, olefins can be oxidized to epoxides (oxiranes) using this reagent. Large scale use of hydrogen peroxide has been inhibited because of the explosion hazard involved in handling this compound, especially when it is concentrated. A process is disclosed in U.S. Patent No.
  • the invention also provides for an enzyme system comprising: (a) an insoluble carrier of silicon oxide and an oxide of at least one metal selected form the group consisting of, Ag, Co, Ce, Mn, Fe, Cu, Cr, Ti, V, Mo and W; and (b) an oxidase enzyme capable of producing hydrogen peroxide when reacted with a hydrogen or electron donor in the presence of oxygen.
  • the organic compound is selected from the group consisting of:
  • Enzymes which produce hydrogen peroxide from oxygen, which can come from air, and a substrate are known in the art. These enzymes are collectively known as oxidases. The following are some examples of oxidases which catalyze the oxidation of the listed substrate in the presence of oxygen and produce hydrogen peroxide as one of the products.
  • Glucose oxidase catalyzes the conversion of ⁇ -D-glucose to D-glucono-l,5-lactone and H2O 2 .
  • Secondary-alcohol oxidase catalyzes the conversion of a secondary alcohol to a ketone and H2O 2 .
  • Methanol oxidase catalyzes the conversion of methanol to formaldehyde and H2O 2 .
  • Oxalate oxidase (E.C.
  • substrates e.g., secondary alcohols
  • hydrogen or electron donors are all examples of hydrogen or electron donors.
  • Enzyme immobilization procedures are also known in the art and include covalent coupling to insoluble organic or inorganic supports, entrapment in gels and adsorption to ion exchange resins or other adsorbent materials.
  • Hydrogen peroxide-activating metals include, for example, silver, cobalt, cerium, manganese, iron, copper, molybdenum, tungsten, vanadium, titanium, chromium and mixtures thereof.
  • Metallosilicates containing the above metals can be prepared in a similar manner to that described in R. Neumann et al. "Metal Oxide (Ti0 2 , M0O 3 , W0 3 ) Substituted Silicate Xerogels as Catalysts for the Oxidation of Hydrocarbons with Hydrogen Peroxide", Journal of Catalysis, 166, pp. 206-127 (1997).
  • a presently preferred metal is tetrahedrally coordinated titanium.
  • Metallosilicates which can contain tetrahedrally coordinated titanium include the following molecular sieve structures: silicalite-1 (TS-1), silicalite-2 (TS-2), zeolite-beta, silicon analogs of ZSM-48 and MCM-41. (See R. Murugavel and H. W. Roesky, "Titanosilicates: Recent Developments in Synthesis and Use as Oxidation Catalysts", Angew. Chem. Int. Ed. Engl., 36, No. 5, pp.
  • crystalline titanium silicalite is used as the inorganic support.
  • porous crystalline titanium silicalite which corresponds to the formula, xTiO 2 (l-x)Si0 2 , where x is between about 0.0005 and about 0.04 has been disclosed in U.S. Patent No. 4,410,501.
  • TS-1 has been shown to catalyze numerous reactions including the following selective oxidations; aromatic hydroxylations, alkane oxidations and alkene epoxidations.
  • the oxidation reactions are performed using dilute (40% or less) aqueous hydrogen peroxide. The reactions are typically run at 100°C or less and at atmospheric pressure.
  • amorphous titania/silica coprecipitate where the weight ratio of ⁇ O 2 to SiU 2 is between 0.0005:1 and 0.5:1 can also catalyze the above named oxidation reactions.
  • This material is commercially available or it can be prepared by the procedure disclosed in D.C.M. Dutoit et al., "Titania-Silica Mixed Oxides", Journal of Catalysis, 164, pp. 433-439 (1996).
  • Olefins useful in the process of this invention may be any organic compound having at least one ethylenically unsaturated functional group (i.e., a carbon-carbon double bond) and may be a cyclic, branched or straight chain olefin.
  • the olefin is reacted with the in-situ generated hydrogen peroxide to produce an epoxide (oxirane).
  • the olefin may contain aryl groups such as phenyl.
  • the olefin is an aliphatic compound containing from 2 to 20 carbon atoms. Multiple double bonds may be present in the olefin, e.g., dienes, trienes and other polyunsaturated substrates.
  • the double bond may be in a terminal or internal position of the olefin or may form part of a cyclic structure as in cyclohexene.
  • suitable organic compounds include unsaturated fatty acids or esters and oligomeric or polymeric unsaturated compounds such as polybutadiene.
  • the olefin may optionally contain functional groups such as halide, carboxylic acid, ether, hydroxy, thiol, nitro, cyano, ketone, acyl, ester, amino and anhydride.
  • Preferred olefins include ethylene, propylene, butenes, butadiene, pentenes. isoprene and hexenes. Mixtures of olefins may be epoxidized and the resulting mixtures of epoxides used in mixed form or separated into the component epoxides.
  • Cyclic ketones useful in the process of this invention include cyclopentanone, cyclohexanone.
  • the cyclic ketone is reacted with the in-situ generated hydrogen peroxide to produce lactones.
  • cyclopentanone is converted to valerolactone and cyclohexanone is converted to caprolactone.
  • ammonia cyclohexanone is converted to cyclohexanone oxine.
  • Alicyclic hydrocarbons of the formula R 8 R 9 CH 2 wherein R 8 and R 9 together form a link selected from the group consisting of, (-CH 2 -) p , wherein p is an integer from 4 to 11 useful in the process of this invention include cyclohexane and cyclododecane.
  • Alicyclic hydrocarbons of the formula R 8 R 9 CH 2 are reacted with the in-situ generated hydrogen peroxide to produce ketones and alcohols. For example, cyclohexane is converted to a mixture of cyclohexanol and cyclohexanone and cyclododecane is converted to a mixture of cyclododecanol and cyclododecanone.
  • Aliphatic hydrocarbons of the formula C q H 2 q- ⁇ - 2. wherein q is an integer from 1 to 20 useful in the process of this invention include hexane and heptane. Aliphatic hydrocarbons of the formula C q H 2q+2 are reacted with the in-situ generated hydrogen peroxide to produce alcohols and ketones.
  • Alcohols according to the formula R ⁇ R 1 ⁇ HOH, wherein R 10 and R 1 ] are as defined above include 2-butanol, cyclohexanol and cyclododecanol. These alcohols are oxidized to 2-butanone, cyclohexanone and cyclododecanone, respectively.
  • the enzyme substrate e.g., glucose
  • olefin molar ratio is typically in the range of from about 1 : 100 to about 1 :0.5, most preferably in the range of 1 : 1 or less.
  • the reaction is conducted within the pH range of from about 2 to about 8.
  • the pH of the reaction may be maintained within the desired range by use of a buffering agent if desired.
  • Suitable buffers include sodium or potassium phosphate, gluconate, citrate, formate and acetate based systems.
  • the reaction may be conducted in the organic compound which is being reacted with hydrogen peroxide, if the compound is a liquid under reaction conditions.
  • the reaction may also be conducted in solvents, such as water, aqueous buffer solutions or organic solvents.
  • Some preferred organic solvents are hydrocarbons such as hexane, benzene, methylene chloride, acetonitrile, lower aliphatic alcohols, ketones and dioxane, dimethylformamide and dimethylsulfoxide and mixtures thereof.
  • the solvents which are used are ones in which the substrate and products of the reaction are highly soluble and in which the enzyme maintains adequate stability and activity.
  • the reaction is typically conducted under aerobic conditions and in the temperature range of from about 15°C to about 50°C, preferably about 20°C to about 30°C.
  • the olefin, the immobilized enzyme, enzyme substrate, and buffer agent if used are mixed together in water or mixed aqueous and organic media in a stirred tank reactor.
  • the reaction can be conducted in a batch, semi-batch or continuous mode.
  • the immobilized enzyme catalyst can be packed into a fixed bed reactor and the olefin, glucose and buffer agent passed through the catalyst.
  • titanosilicalite (0.99 g; prepared in a manner similar to that described in U.S. Patent No. 4,410,501 and having a Ti:Si0 2 weight ratio of
  • a glucose oxidase solution (5 mL, 1000 units/ml; a commercial sample, E.C. 1.1.3.4 was used) adjusted to pH 7 with phosphate. After stirring for 4 hrs the solids were isolated by suction filtration and washed with water 3 times. The solids were stored wet in the refrigerator.
  • EXAMPLE 2 Catalyst A (75 mg wet) was added to a mixture of 1-hexene (1.94 g) and glucose (0.22 g) in pH 6 phosphate buffer (1.48 g). The resultant slurry was shaken at room temp for 60 hrs under 500 psig (3548 kPa) air. Analysis of the organic layer showed the presence of 2-n-butyloxirane and n-hexanal in 98 and 2% selectivities, respectively.
  • Titanosilicalite (4. 75 mg) was added to a mixture of 1-hexene (1.94 g), glucose (0.21 g) in pH 6 phosphate buffer (1.50 g), and glucose oxidase solution (0.65 g). The resultant slurry was shaken at room temp for 60 hrs under 500 psig (3548 kPa) air. Analysis of the organic layer showed the presence of 2-n-butyloxirane and n-hexanal in 92 and 8% selectivities respectively.
  • a reaction mixture consisting of titanosilicalite (55 mg), 1-hexene (2 mL), glucose solution (0.15 g) in pH 6 buffer (1 mL), and pH 4 buffer (0.5 mL) were stirred in the presence of air for 4 hrs. No oxirane was detected.
  • reaction mixture consisting of 1-hexene (4 mL), glucose oxidase solution (0.5 mL) and glucose (0.15 g) in pH 6 buffer (1 mL) was stirred in air for 4 hrs. No oxirane was detected.

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

Abstract

L'invention concerne un procédé d'élaboration de composés organiques oxygénés par oxydase visant à fournir du H2O2 pour l'oxydation d'un substrat organique oxydable en présence d'un catalyseur à base de métal. L'invention concerne aussi un système d'enzymes constitué d'un vecteur insoluble d'oxyde de silicium et d'un oxyde de Ag, Co, Ce, Mn, Fe, Cu, Cr, Ti, V, Mo ou W en combinaison avec une oxydase pouvant fournir du H2O2 dans la réaction avec un donneur d'hydrogène ou d'électrons en présence d'oxygène.
EP98920932A 1997-05-16 1998-05-12 Procede d'oxydation selective de composes organiques Withdrawn EP0981638A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US4670997P 1997-05-16 1997-05-16
US46709P 1997-05-16
PCT/US1998/008882 WO1998051811A1 (fr) 1997-05-16 1998-05-12 Procede d'oxydation selective de composes organiques

Publications (1)

Publication Number Publication Date
EP0981638A1 true EP0981638A1 (fr) 2000-03-01

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EP98920932A Withdrawn EP0981638A1 (fr) 1997-05-16 1998-05-12 Procede d'oxydation selective de composes organiques

Country Status (3)

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EP (1) EP0981638A1 (fr)
JP (1) JP2001525670A (fr)
WO (1) WO1998051811A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19928158C2 (de) 1999-06-19 2003-09-04 Haarmann & Reimer Gmbh Verfahren zur Herstellung von aromatischen Carbonylverbindungen aus Styrolen
DE10054082A1 (de) * 2000-10-31 2002-05-16 Forschungszentrum Juelich Gmbh Verfahren zur enzymatischen Oxidation von Substraten mit H2O2
CN115845915B (zh) * 2021-09-24 2024-09-10 北京旭阳科技有限公司 改性钛硅催化剂、其制备方法以及使用其制备硝基烷烃的方法

Family Cites Families (7)

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Publication number Priority date Publication date Assignee Title
GB1385319A (en) * 1971-09-22 1975-02-26 Nat Res Dev Enzyme preparations
US4247641A (en) * 1979-05-29 1981-01-27 Cetus Corporation Method for producing epoxides and glycols from alkenes
ES481444A1 (es) * 1978-06-12 1980-02-01 Cetus Corp Un metodo para la fabricacion de epoxidos o glicoles a par- tir de olefinas.
CA1128540A (fr) * 1978-09-25 1982-07-27 Union Carbide Corporation Epoxydation d'olefines a l'aide d'eau oxygenee produite sur place
US4351902A (en) * 1980-06-16 1982-09-28 Cetus Corporation Production of 2-keto-D-gluconic acid and hydrogen peroxide
GB9201872D0 (en) * 1992-01-29 1992-03-18 Exxon Chemical Patents Inc Improved oxidation of saturated hydrocarbon chains
US5453511A (en) * 1993-12-23 1995-09-26 Arco Chemical Technology, L.P. Bis-piperidinium compounds

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9851811A1 *

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Publication number Publication date
JP2001525670A (ja) 2001-12-11
WO1998051811A1 (fr) 1998-11-19

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