+

WO1998051811A1 - Process for the selective oxidation of organic compounds - Google Patents

Process for the selective oxidation of organic compounds Download PDF

Info

Publication number
WO1998051811A1
WO1998051811A1 PCT/US1998/008882 US9808882W WO9851811A1 WO 1998051811 A1 WO1998051811 A1 WO 1998051811A1 US 9808882 W US9808882 W US 9808882W WO 9851811 A1 WO9851811 A1 WO 9851811A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
oxidase
carbon atoms
hydrogen peroxide
formula
Prior art date
Application number
PCT/US1998/008882
Other languages
French (fr)
Inventor
Michael Brian D'amore
Original Assignee
E.I. Du Pont De Nemours And Company
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 E.I. Du Pont De Nemours And Company filed Critical E.I. Du Pont De Nemours And Company
Priority to EP98920932A priority Critical patent/EP0981638A1/en
Priority to JP54926498A priority patent/JP2001525670A/en
Publication of WO1998051811A1 publication Critical patent/WO1998051811A1/en

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
    • 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.

Landscapes

  • 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)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
  • Immobilizing And Processing Of Enzymes And Microorganisms (AREA)

Abstract

A process for the manufacture of oxygenated organic compounds by employing an oxidase to generate H2O2 is disclosed. The generated H2O2 is used to oxidize an oxidizable organic substrate in the presence of a metal-containing catalyst. An enzyme system of an insoluble carrier of silicon oxide and an oxide of Ag, Co, Ce, Mn, Fe, Cu, Cr, Ti, V, Mo or W, coupled with an oxidase enzyme capable of producing H2O2 when reacted with a hydrogen or an electron donor in the presence of oxygen, is also disclosed.

Description

TITLE PROCESS FOR THE SELECTIVE OXIDATION OF ORGANIC COMPOUNDS FIELD OF THE INVENTION 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.
BACKGROUND OF THE INVENTION 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. 4,247,641 (Neidleman et al.) for the generation of hydrogen peroxide in situ by using glucose oxidase to oxidize glucose to gluconic acid and hydrogen peroxide. This patent further discloses that the hydrogen peroxide-generating system may be present in the immobilized state using techniques for enzyme immobilization familiar to those skilled in the art. In addition, the catalytic oxidation of alkanes and alkenes by titanium silicates is disclosed in C. B. Khouw et al., "Studies on the Catalytic Oxidation of Alkanes and Alkenes by Titanium Silicates", Journal of Catalysis 149, 195-205 (1994). Such catalysts are used for the selective oxidation of n-octane using aqueous H2O2 and organic hydroperoxides as the oxidants at temperatures below 100°C. The absence of water is deemed critical for catalytic activity.
In this regard, there is a need for processes that generate hydrogen peroxide in situ and utilize it at about the same rate that it is generated in order to provide both a safe and an efficient process for oxidizing organic compounds. The present invention satisfies that need and otherwise overcomes certain deficiencies inherent in the prior art. Other objects and advantages of the invention will become apparent to those skilled in the art upon reference to the detailed description which follows hereinafter. SUMMARY OF THE INVENTION The invention provides a process for oxidizing organic compounds comprising the steps of:
(A) contacting, in a zone of reaction, a hydrogen or an electron donor (e.g., glucose or carbon monoxide) and oxygen in the presence of an oxidase (e.g., glucose oxidase) to form hydrogen peroxide, said oxidase being immobilized on an metallosilicate containing a hydrogen peroxide-activating metal; and
(B) contacting, within the zone of reaction, said formed hydrogen peroxide with an oxidizable organic compound.
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. •
Preferably, in the process of the invention, the organic compound is selected from the group consisting of:
(a) an olefin according to the formula R1R2C=CR3R4, wherein R1, R2, R3 and R4 are each independently -H; alkyl, wherein the alkyl group has from 1 to 16 carbon atoms; alkylaryl, wherein the alkylaryl group has from 7 to 16 carbon atoms; cycloalkyl, wherein the cycloalkyl group has from 6 to 10 carbon atoms; or alkylcycloalkyl, wherein the alkylcycloalkyl group has from 7 to 16 carbon atoms; and wherein said olefin can optionally contain halogen atoms (i.e., Cl, Br, F and I);
/CH2
(CH2)n CO \ / (b) cyclic ketones according to the formula c"2 wherein n is an integer from 2 to 9;
(c) compounds of the formula Cg^R5, wherein R5 is -H,-OH; Cj to C3 straight chain, saturated or unsaturated hydrocarbon radicals; -CO2H; -CN; -COCm, wherein m is an integer from 1 to 6; -OCm, wherein m is an integer from 1 to 6; or NR6R7, where R6 and R7 are each independently -H or Cj to C3 alkyl groups;
(d) alicyclic hydrocarbons according to the formula R8R9CH2, wherein R8 and R9 together form a link of (-CH2-)p, wherein p is an integer from 4 to 11; (e) aliphatic hydrocarbons of the formula CqH2q+2, wherein q is an integer from 1 to 20; and
(f) alcohols according to the formula R'OR1 'CHOH, wherein R10 and Rl ' are each independently -H; alkyl, wherein the alkyl group has from 1 to 16 carbon atoms; alkylaryl, wherein the alkylaryl group has from 7 to 16 carbon atoms; cycloalkyl, wherein the cycloalkyl group has from 6 to 10 carbon atoms; cycloalkyl wherein R10 and R1 ' taken together form a link containing 4 to 11 -CH2- groups; or alkylcycloalkyl, wherein the alkylcycloalkyl group has from 7 to 16 carbon atoms. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
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 (E.C. 1.1.3.4) catalyzes the conversion of β-D-glucose to D-glucono-l,5-lactone and H2O2. Secondary-alcohol oxidase (E.C. 1.1.3.18) catalyzes the conversion of a secondary alcohol to a ketone and H2O2. Methanol oxidase (E.C. 1.1.3.31) catalyzes the conversion of methanol to formaldehyde and H2O2. Oxalate oxidase (E.C. 1.2.3.4) catalyzes the conversion of oxalate to carbon dioxide and H2O2- Aryl-aldehyde oxidase (E.C. 1.2.3.9) catalyzes the conversion of an aromatic aldehyde to an aromatic acid and H2O2. Carbon monoxide oxidase (E.C. 1.2.3.10) catalyzes the conversion of CO + H2O to carbon dioxide and H2O2. Amine oxidase (E.C. 1.4.3.4) catalyzes the conversion of RCH2NH2 + H2O to RCHO + NH3 and H2O2. Ethanolamine oxidase
(E.C. 1.4.3.8) catalyzes the conversion of ethanolamine + H2O to glycolaldehyde and H2O2- Nitroethane oxidase (E.C. 1.7.3.1) catalyzes the conversion of nitroethane + H2O to acetaldehyde and H2O2. Sulfite oxidase (E.C. 1.8.3.1) catalyzes the conversion of sulfite + H2O to sulfate and H O2. Some of the oxidases (e.g., glucose oxidase) are commercially available. Others can be extracted from microorganisms using procedures known in the art.
The above-described substrates (e.g., secondary alcohols) 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. (See for example, G. F. Bickerstaff ed., "Immobilization of Enzymes and Cells," Humana Press, Totowa, New Jersey, 1997. This monograph discloses many examples of immobilization techniques.) 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 (Ti02, M0O3, W03) 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. 477-479 (1997) for a discussion of titanosilicates, their synthesis and use as oxidation catalysts.) In a preferred embodiment, crystalline titanium silicalite is used as the inorganic support. The preparation of porous crystalline titanium silicalite (TS-1) which corresponds to the formula, xTiO2(l-x)Si02, 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.
An amorphous titania/silica coprecipitate where the weight ratio of ΗO2 to SiU2 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).
A wide variety of organic compounds can be oxidized by the process of this invention. Presently preferred organic compounds are listed above in the Summary of the Invention.
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. Preferably, 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. Other, non-limiting examples of 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.
Olefins especially preferred for the process of this invention include those of the formula R1R2C=CR3R4, wherein R1, R2, R3 and R4 are each independently selected from the group consisting of H and Cj to C12 straight chain, saturated or unsaturated hydrocarbon radicals.
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. For example, cyclopentanone is converted to valerolactone and cyclohexanone is converted to caprolactone. Also, in the presence of ammonia cyclohexanone is converted to cyclohexanone oxine.
Compounds of the formula CgH5R5, wherein R5 is selected from a group as defined in the Summary of the Invention, are reacted with the in-situ generated hydrogen peroxide to produce phenols. For example, phenol, itself, is converted to hydroquinone and toluene is converted to catechol.
Alicyclic hydrocarbons of the formula R8R9CH2, wherein R8 and R9 together form a link selected from the group consisting of, (-CH2-)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 R8R9CH2 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 CqH2q-ι-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 CqH2q+2 are reacted with the in-situ generated hydrogen peroxide to produce alcohols and ketones.
Alcohols according to the formula R^R1 ^HOH, wherein R10 and R1 ] 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) to 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. Preferably, 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. Alternatively, the immobilized enzyme catalyst can be packed into a fixed bed reactor and the olefin, glucose and buffer agent passed through the catalyst. Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilize the present invention to its fullest extent. The following specific embodiments are, therefore, to be construed as merely illustrative, and are not to limit the remainder of the invention in any way whatsoever. All percentages are by weight unless otherwise indicated.
EXAMPLES Catalyst Preparation
A. To titanosilicalite (0.99 g; prepared in a manner similar to that described in U.S. Patent No. 4,410,501 and having a Ti:Si02 weight ratio of
1.0%) was added a 10 vol% solution of 3-aminopropyltriethoxysilane in toluene (30 mL). The mixture was refluxed for 16 hours and the resultant slurry filtered, the solids washed with toluene, acetone and air dried. The dry solid was further dried at 115°C for 16 hours. The dried solids were mixed with 50 wt% aqueous glutaraldehyde (1.25 g) in pH 7 phosphate buffer (23 mL) for one hr. After decanting the aqueous layer the solids were washed 10 times with deionized water. To the wet solids was added 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.
B. To titanosilicalite (1.01 g) was added a 1 vol% solution 3-aminopropyltriethoxysilane in acetone (25 mL). The acetone was removed by evaporation at reduced pressure in a rotary evaporator. The resultant powder was dried at 115°C for 16 hrs. Subsequent treatment with glutaraldehyde and glucose oxidase was the same as that of A.
EXAMPLE 1 A reaction mixture consisting of catalyst A (50 mg), 1-hexene (2 mL), glucose (0.16 g) in pH 6 buffer (1 mL) were stirred at room temp in air for 4 hrs. Analysis showed the presence of the 2-n-butyloxirane.*
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.
EXAMPLE 3 A reaction was conducted in the same manner as Example 1 using Catalyst B (75 mg wet) and gave 2-n-butyloxirane and n-hexanal in 97 and 3% selectivities, respectively.
EXAMPLE 4 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.
EXAMPLE 5 A reaction mixture consisting of catalyst A (50mg), 2-butanol (2.3g), glucose (0.1 Og) in water (0.94g) was stirred at room temperatures in air for 24 hours. Analysis of the reaction mixture showed the presence of 2-butanone in about 30% yield based on the initial amount of glucose. COMPARATIVE EXAMPLE A
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.
COMPARATIVE EXAMPLE B
A 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.
Although particular embodiments of the present invention have been described in the foregoing description, it will be understood by those skilled in the art that the invention is capable of numerous modifications, substitutions and rearrangements without departing from the spirit or essential attributes of the invention. Reference should be made to the appended claims, rather than to the foregoing specification, as indicating the scope of the invention.

Claims

CLAIMS:
1. A process for oxidizing organic compounds comprising the steps of:
(A) contacting, in a zone of reaction, a hydrogen or an electron donor and oxygen in the presence of an oxidase to form hydrogen peroxide, said oxidase being immobilized on an metallosilicate containing a hydrogen peroxide- activating metal; and
(B) contacting, within the zone of reaction, said formed hydrogen peroxide with an oxidizable organic compound.
2. The process of Claim 1 wherein the organic compound is selected from the group consisting of:
(a) an olefin according to the formula R1R2C=CR3R4, wherein R1, R2, R3 and R4 are each independently -H; alkyl, wherein the alkyl group has from 1 to 16 carbon atoms; alkylaryl, wherein the alkylaryl group has from 7 to 16 carbon atoms; cycloalkyl, wherein the cycloalkyl group has from 6 to 10 carbon atoms; or alkylcycloalkyl, wherein the alkylcycloalkyl group has from 7 to 16 carbon atoms; and wherein said olefin can optionally contain halogen atoms;
(b) cyclic ketones according to the formula
Figure imgf000011_0001
, wherein n is an integer from 2 to 9; (c) compounds of the formula C6H5R5, wherein R5 is -H,-OH; Cj to C3 straight chain, saturated or unsaturated hydrocarbon radicals; -CO2H; -CN; -COCm, wherein m is an integer from 1 to 6; -OCm, wherein m is an integer from 1 to 6; or NR6R7, where R6 and R7 are each independently -H or C to C3 alkyl groups; (d) alicyclic hydrocarbons according to the formula
R8R9CH2, wherein R8 and R9 together form a link of (-CH2-)p, wherein p is an integer from 4 to 11;
(e) aliphatic hydrocarbons of the formula CqH q+2, wherein q is an integer from 1 to 20; and
(f) alcohols according to the formula R10R! !CHOH, wherein R10 and R1 ' are each independently -H; alkyl, wherein the alkyl group has from 1 to 16 carbon atoms; alkylaryl, wherein the alkylaryl group has from 7 to 16 carbon atoms; cycloalkyl, wherein the cycloalkyl group has from 6 to 10 carbon atoms; cycloalkyl wherein R10 and R1 { taken together form a link containing 4 to 11 -CH2- groups; or alkylcycloalkyl, wherein the alkylcycloalkyl group has from 7 to 16 carbon atoms.
3. The process of Claim 1 wherein the hydrogen or electron donor is glucose or carbon monoxide.
4. The process of Claim 1 wherein the oxidase is glucose oxidase.
5. The process of Claim 1 wherein the hydrogen peroxide-activating metal is selected from the group consisting of silver, cobalt, cerium, manganese, iron, copper, molybdenum, tungsten, vanadium, titanium, chromium and mixtures thereof.
6. The process of Claim 5 wherein the hydrogen peroxide-activating metal is tetrahedrally coordinated titanium.
7. The process of Claim 1 wherein the oxidase is immobilized on crystalline titanium silicalite.
8. An enzyme system comprising: (a) an insoluble carrier of silicon oxide and an oxide of at least one metal selected from 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.
9. The enzyme system of Claim 8 wherein the hydrogen or electron donor is glucose or carbon monoxide.
10. The enzyme system of Claim 8 wherein the oxidase enzyme is glucose oxidase.
PCT/US1998/008882 1997-05-16 1998-05-12 Process for the selective oxidation of organic compounds WO1998051811A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP98920932A EP0981638A1 (en) 1997-05-16 1998-05-12 Process for the selective oxidation of organic compounds
JP54926498A JP2001525670A (en) 1997-05-16 1998-05-12 Method for selective oxidation of organic compounds

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US4670997P 1997-05-16 1997-05-16
US60/046,709 1997-05-16

Publications (1)

Publication Number Publication Date
WO1998051811A1 true WO1998051811A1 (en) 1998-11-19

Family

ID=21944957

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1998/008882 WO1998051811A1 (en) 1997-05-16 1998-05-12 Process for the selective oxidation of organic compounds

Country Status (3)

Country Link
EP (1) EP0981638A1 (en)
JP (1) JP2001525670A (en)
WO (1) WO1998051811A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1061132A1 (en) * 1999-06-19 2000-12-20 Haarmann & Reimer Gmbh Method for synthesis of aromatic carbonyl compounds from styroles using lipases
DE10054082A1 (en) * 2000-10-31 2002-05-16 Forschungszentrum Juelich Gmbh Process for the enzymatic oxidation of substrates with H2O2
CN115845915A (en) * 2021-09-24 2023-03-28 北京旭阳科技有限公司 Modified titanium-silicon catalyst, preparation method thereof and method for preparing nitroalkane by using same

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2246695A1 (en) * 1971-09-22 1973-03-29 Nat Res Dev ENZYME PREPARATION, METHOD OF ITS MANUFACTURING AND ITS USE FOR THE INVESTIGATION OF CHOLESTEROL
EP0007176A2 (en) * 1978-06-12 1980-01-23 Cetus Corporation Method for producing epoxides and glycols from alkenes
EP0009262A1 (en) * 1978-09-25 1980-04-02 Union Carbide Corporation Epoxidation of olefins using in situ generated hydrogen peroxide
US4247641A (en) * 1979-05-29 1981-01-27 Cetus Corporation Method for producing epoxides and glycols from alkenes
EP0042221A2 (en) * 1980-06-16 1981-12-23 Cetus Corporation Production of 2-keto-d-gluconic acid and hydrogen peroxide
WO1993015035A1 (en) * 1992-01-29 1993-08-05 Exxon Chemical Patents Inc. Improved oxidation of saturated hydrocarbon chains
EP0659685A1 (en) * 1993-12-23 1995-06-28 ARCO Chemical Technology, L.P. Epoxidation process and catalyst therefor

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2246695A1 (en) * 1971-09-22 1973-03-29 Nat Res Dev ENZYME PREPARATION, METHOD OF ITS MANUFACTURING AND ITS USE FOR THE INVESTIGATION OF CHOLESTEROL
EP0007176A2 (en) * 1978-06-12 1980-01-23 Cetus Corporation Method for producing epoxides and glycols from alkenes
EP0009262A1 (en) * 1978-09-25 1980-04-02 Union Carbide Corporation Epoxidation of olefins using in situ generated hydrogen peroxide
US4247641A (en) * 1979-05-29 1981-01-27 Cetus Corporation Method for producing epoxides and glycols from alkenes
EP0042221A2 (en) * 1980-06-16 1981-12-23 Cetus Corporation Production of 2-keto-d-gluconic acid and hydrogen peroxide
WO1993015035A1 (en) * 1992-01-29 1993-08-05 Exxon Chemical Patents Inc. Improved oxidation of saturated hydrocarbon chains
EP0659685A1 (en) * 1993-12-23 1995-06-28 ARCO Chemical Technology, L.P. Epoxidation process and catalyst therefor

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 73, no. 7, 17 August 1970, Columbus, Ohio, US; abstract no. 32199, NORDSCHOW, CARLETON D.: "Galactose measurement in human fluids using a generalized substrate- oxidase -ternary conjugate system" XP002075477 *
CLIN. CHIM. ACTA (1970), 28(1), 89-95 CODEN: CCATAR *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1061132A1 (en) * 1999-06-19 2000-12-20 Haarmann & Reimer Gmbh Method for synthesis of aromatic carbonyl compounds from styroles using lipases
US6331655B1 (en) 1999-06-19 2001-12-18 Haarmann & Reimer Gmbh Process for the preparation of aromatic carbonyl compounds from styrenes
DE10054082A1 (en) * 2000-10-31 2002-05-16 Forschungszentrum Juelich Gmbh Process for the enzymatic oxidation of substrates with H2O2
CN115845915A (en) * 2021-09-24 2023-03-28 北京旭阳科技有限公司 Modified titanium-silicon catalyst, preparation method thereof and method for preparing nitroalkane by using same

Also Published As

Publication number Publication date
EP0981638A1 (en) 2000-03-01
JP2001525670A (en) 2001-12-11

Similar Documents

Publication Publication Date Title
Dusi et al. Epoxidation of functionalized olefins over solid catalysts
JP5558578B2 (en) Propylene oxide production method
Kumar et al. Oxidative organic transformations catalyzed by titanium-and vanadium-silicate molecular sieves
EP1056683A2 (en) Process for the selective oxidation of organic compounds
US5081267A (en) Epoxidation process
US6160137A (en) Method for producing propylene oxide
AU729005B2 (en) A process for the epoxidation of alkenes
Sels et al. Application of heterogenized oxidation catalysts to reactions of terpenic and other olefins with H 2 O 2
US6307072B2 (en) Method for production of oxygen-containing organic compound
EP0981638A1 (en) Process for the selective oxidation of organic compounds
US6504039B2 (en) Supported catalyst and the process for preparing the same
Clerici Catalytic oxidations with hydrogen peroxide: new and selective catalysts
EP1044196A2 (en) Process for the selective oxidation of organic compounds
CN110950822A (en) Method for catalyzing olefin epoxidation
US6251851B1 (en) Process for the selective oxidation of organic compounds
WO1999039826A1 (en) Method for improving the operational life of supported catalysts covered with gold particles and used for oxidising unsaturated hydrocarbons
KR100907545B1 (en) Method for preparing direct epoxy compound using palladium on niobium-containing support
EP0970951A1 (en) A manganese oxidation catalyst, a method for its preparation and use thereof for catalytic epoxidation, catalytic cis-dihydroxylation and combined expoxidation-cis-dihydroxylation of olefins
KR20010040709A (en) Method for Regenerating Supported Catalysts covered with Gold Particles and used for Oxidising Unsaturated Hydrocarbons
Pan et al. EPOXIDATION OF PROPYLENE ON TITANIUM-SILICA CATALYSTS MODIFICATION WITH POLYMERIC SURFACTANTS
MXPA99010971A (en) A process for the epoxidation of alkenes
IL133057A (en) Process for the catalytic epoxidation of alkenes
CZ20001646A3 (en) Process of selective oxidation of organic compounds
MXPA00004647A (en) Process for the selective oxidation of organic compounds
MXPA00007650A (en) Method for the direct catalytic oxidation of unsaturated hydrocarbons in gaseous phase

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): JP US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 1998920932

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 09403615

Country of ref document: US

ENP Entry into the national phase

Ref country code: JP

Ref document number: 1998 549264

Kind code of ref document: A

Format of ref document f/p: F

WWP Wipo information: published in national office

Ref document number: 1998920932

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 1998920932

Country of ref document: EP

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载