FR2862302A1 - Method of catalyzed oxidation of olefin to produce enol, ketenes and epoxy compound - Google Patents

Abstract

Method of catalyzed oxidation of olefin to produce enol, ketenes and epoxy compound using air or oxygen, or other oxidant, the reaction pressure being controlled to be 1-10 atm, the temperature being 20-150 deg. C, mu-oxygen single metalloporphyrin or double metalloporphyrin, or their carrier is selected as catalyst, or they form composite catalyst along with filtering metallic salts or oxidants. According to the present invention, the oxidation agent uses air or oxygen, or mixture gas of oxygen and inert gas, or other chemical oxidation agent, the reaction pressure is controlled to be 1-10 atm, the temperature being 20-150 deg. C, mu-oxygen single metalloporphyrin or double metalloporphyrin, or their carrier is separately selected as catalyst, or they form composite catalyst along with filtering metallic salts or oxidants, the catalyst concentration being 1-50PPM, reaction time being 0.5-5 hours, thus alpha, beta-enol, alpha, beta-ketene and epoxy compounds are obtained through catalytic oxidation of olefin or cyclomonoolefin.

Description

PROCESS FOR THE CATALYTIC OXIDATION OF OLEFINS IN ENAMEL, OLEFIN-KETONES

AND EPDXYDES

  Technical Field The present invention relates to a process for the preparation of α, β-enols, u, β-olefin-ketones and epoxides by the selective oxidation of olefins or cycloolefins with air or a chemical oxidant, catalyzed by a metal porphyrin.

  STATE OF THE ART The oxidation of olefins by air generally requires high temperatures and catalysis by noble metals such as gold or silver. The low selectivity of the reaction with respect to the carbon-carbon double bond and allyl hydrogen leads to numerous side reactions, difficulties in product separation, and low reaction efficiency. . The chemical oxidation of olefins can not be controlled and used because of the formation of considerable deep oxidation products. The means for decreasing secondary reactions in the oxidation of olefins by air and using the chemical oxidation of olefins is the application of a suitable catalyst to increase the selectivity of the reaction. At present, there are reports regarding the use of monometallic porphyrins as homogeneous catalysts for catalyzing the oxidation of olefins with NaClO, etc. This process can increase the selectivity of the olefin oxidation reaction, but the NaClO will oxidize the monometallic porphyrins simultaneously and thus cause them to lose their catalytic performance.

  Therefore, this process has not been industrialized. Content of the Invention The object of the present invention is to provide a process for the oxidation of olefins or cycloolefins to produce α,--enols, α,--olefin-ketones and epoxides with good selectivity and high conversion and recovery rates, able to avoid the formation of deep oxidation products and produce very pure and easy to separate products.

  The technical solution of the present invention resides in the catalytic oxidation of olefins or cycloolefins to produce α, β-enols, α, β-olefin-ketones and epoxides in the presence of an oxidant such as air or oxygen or a mixture of oxygen and an inert gas or other chemical oxidants under a reaction pressure of 1 to 10 atm, at a reaction temperature of 20 to 150 C, and during a reaction time from 0.5 to 5 hours, which uses p-oxymonometallic porphyrins or bimetallic porphyrins of general formula (I) or (II) or p-oxymonometallic porphyrins or supported bimetallic porphyrins of general formula (I) or (II) only as a catalyst, or a composite consisting of uoxymonometric porphyrins or bimetallic porphyrins of general formula (I) or (II) and a transition metal salt or oxide as a composite catalyst with a catalyst concentration of 1 to 50 p pm.

  Said chemical oxidant may be NaClO, H2O2r peroxyacetic acid, etc. When sn uses a chemical oxidant, the reaction is carried out in a solvent such as water, acetic acid, ethyl acetate, benzene or toluene, etc., at a reaction temperature of 20 to 80 ° C. and under atmospheric pressure.

  The olefins may be C3 to C18 alkenes, C5 to C8 monocyclic olefins, polycyclic olefins, aromatic olefins, and derivatives thereof.

  The composite catalyst comprises a metal porphyrin of the general formula (I) or (II) as a main catalyst with an average concentration of 1 to 50 ppm and a salt or oxide or inorganic salt of a transition metal as an additive with a molar ratio of main catalyst to the additive of 1: 1-20. R I (I)

RI (IIl

  The metal atom M in the general formula (I) may be a transition metal atom or metals of the lanthanide series such as Fe, Mn, Co, Cr, Cu, Ni, Pt, Pd, Tb, etc. . The substituents R 1, R 2 and R 3 on the benzene rings may be hydrogen, hydrocarbyls, alkoxy, hydroxy, nitro, halogen, amido, amino, glycityl, substituted glycityl, and cyclodextrin. The ligand X can be acetic acid, acetylacetone, halogen, and other anions of acidic groups.

  The metal atoms M1 and M2 in the general formula (II) may be transition metal atoms such as Fe, Mn, Cr, etc. The substituents R 1, R 2 and R 3 on the benzene rings may be hydrogen, hydrocarbyl, alkoxy, hydroxy, nitro, halogen, amido, amino, glycityl, and cyclodextrin.

  In the present invention, the pressure is preferably in the range of 4 atm to 8 atm, the temperature is preferably in the range of 500C to 1100C, and the catalyst concentration is preferably in the range of from 2 ppm to 8 ppm.

  The additive to the composite catalyst can be a salt or an oxide of a metal such as Cu, Zm, Fe, Co, Mn, Cr, Ni, etc., or a phosphate, a phosphonate, an amine or an ammonium salt or a reducing gas such as hydrogen or CO. These additives can obviously improve the catalytic performance of metal porphyrins for the oxidation of olefins and cycloolefins by air.

  The support for supporting said metal porphyrins comprises a silica gel, a molecular sieve, an alumina, a zeolite, diatomaceous earth, activated carbon, sepiolite, porous ceramics, polyvinyl chloride, poly (vinyl chloride), polystyrene, cellulose, chitosan, chitin, and their derivatives.

  Embodiments of the invention

Example 1

  5 mg of porphyrin metal of structural formula (1), in which R1 = R2 = R3 = CH3 and M = Mn, and 20 mg of CuCl2 are added to 300 ml of cyclohexene, in which 4 atm of air are introduced. After stirring for 3 hours at 55 ° C., the cyclohexene conversion is 4.2% and the yield of α, 3-cyclohexenol, α-cyclohexene-ketone and cyclohexane epoxide in the reaction product is 90 30

Example 2

  3 mg of porphyrin metal of structural formula (II), in which R 1 = R 2 = OH, R 3 = Cl and M 1 = M 2 = Fe, and 20 mg of sodium phosphate, are added to 400 ml of styrene, into which are introduced 5 atm of air.

  After stirring for 4 hours at 80 ° C., the conversion of styrene is 10.8% and the yield of phenylethane epoxide in the reaction product is 60 ° C.

Example 3

  7 mg of porphyrin metal of structural formula (I), in which R 1 = OCH 3, R 2 = R 3 = H, and M 1 = Co, and 24 mg of triethylamine, are added to 400 ml of 2-butene, in which 8 atm of air. After stirring for 2 hours at 80 ° C., the conversion of butene is 30.8% and the yield of butane epoxide and butyraldehyde in the reaction product is 80.degree.

Example 4

  6 mg of porphyrin metal of structural formula (II), in which R1 = NC) 2, R2 = R3 = H, and M1 = M2 = Mn, supported on a molecular sieve, are added to a mixture of 100 ml of -pinene and 300 ml of acetic acid, to which 50 g of NaClO are added slowly while stirring at 70 ° C. After 1 hour of reaction under atmospheric pressure, the conversion of α-pinene is 50.3% and the yield of epoxide, enol and olefinecetone in the reaction product is 90

Example 5

  4 mg of porphyrin metal of structural formula (1), in which R1 = R2 = N (CH3) 2, R3 = C2H5, and M1 = Cr, supported on poly (vinyl chloride), are added to 400 mg of propylene in which 10 atm of oxygen are introduced. After stirring for 4 hours at 50 ° C., the conversion of propylene is 26% and the yield of propylene oxide, acrolein and acroleic acid in the reaction product is 88%.

Example 6

  5 mg of porphyrin metal of structural formula (1), in which R 1 = C 4 H 9, R 2 = R 3 = H, and M = Fe, and 30 mg of cobalt acetate are added to a mixture of 300 ml of cyclopentene and 100 ml of benzene, into which 6 atm of a mixture of air containing 6% oxygen and 2% hydrogen. After stirring for 1 hour at 100 ° C., the conversion of cyclopentene is 18.5% and the yield of epoxide, enol and olefin-ketone in the reaction product is 92%.

Example 7

  8 mg of porphyrin metal of structural formula (I), in which R 1 = R 2 = R 3 = Cl, and M = Fe, supported on 3 g of cellulose, are added to 500 ml of cyclohexene, in which 6 atm of a mixture of air containing 2% CO. After stirring for 0.5 hour at 110 ° C., the conversion of cyclohexene is 20.5% and the yield of epoxide, enol and olefin-ketone in the reaction product is 83%.

Example 8

  3 mg of porphyrin metal of structural formula (II), in which R 1 = R 2 = H, R 3 = 2,3,4, -tetraacetylglucosyl, and M 1 = M 2 = Fe, are added to 100 ml of benzocyclopentene, into which 6 atm of air. After 1 hour of reaction at 120 ° C., the conversion of benzocyclopentene is 35% and the yield of epoxide, enol and olefin-ketone in the reaction product is 94%.

Example 9

  8 mg of porphyrin metal of structural formula (II), in which R1 = OC2H5i R2 = R3 = H, and M1 = M2 = Cr, and 50 mg of NiO, are added to 500 ml of allylbenzene, in which 8 atm of air. After stirring for 0.5 hour at 130 ° C., the conversion of allylbenzene is 12.4% and the yield of epoxide, enol and olefin-ketone in the reaction product is 86%.

Example 10

  6 mg of porphyrin metal of structural formula (1), in which R 1 = R 2 = R 3 = CH 3 and M = Cu, and 10 mg of triphenylphosphine, are added to 500 ml of cycloheptene, into which 5 atm of air are introduced. . After stirring for 3 hours at 75 ° C., the conversion of cycloheptene is 10.5% and the yield of epoxide, enol and olefin-ketone in the reaction product is 90%.

Claims (8)

  A process for the catalytic oxidation of olefins and cycloolefins to produce enols, olefin-ketones and epoxides, characterized by the presence of an oxidant such as air or oxygen or a mixture of oxygen and an inert gas under a reaction pressure of 1 to 10 atm, at a reaction temperature of 20 to 150 C, and for a reaction time of 0.5 to 5 hours, using poxymonometric porphyrins or bimetallic porphyrins of formula general (I) or (II) or porphyrins} ioxymonometallic or supported bimetallic porphyrins of general formula (I) or (1I) alone as catalyst, or a composite consisting of P-oxymonometallic porphyrins or bimetallic porphyrins of general formula (I ) or (II) and a transition metal salt or oxide as a composite catalyst with a catalyst concentration of 1 to 50 ppm; R. Rt (I) (II) the metal atom M in the general formula (I) may be a transition metal atom or metals of the lanthanide series such as Fe, Mn, Co, Cr, Cu, Ni , Pt, Pd, Tb; substituents R 1, R 2 and R 3 on benzene rings which may be hydrogen, hydrocarbyls, alkoxy, hydroxy, nitro, halogen, amido, amino, glycityl, substituted glycityl, and cyclodextrin; and the ligand X may be acetic acid, acetylacetone, halogen, and other anions of acidic radicals; the metal atoms M1 and M2 in the general formula (II) may be transition metal atoms such as Fe, Mn, Cr; the substituents R 1, R 2 and R 3 on the benzene rings may be hydrogen, hydrocarbyl, alkoxy, hydroxy, nitro, halogen, amido, amino, glycityl, and cyclodextrin.   2. Method according to claim 1, characterized in that said composite catalyst comprises metal porphyrins of general formula (I) or (II) or supported metal porphyrins of general formula (I) or (II) as main catalyst with a concentration primary catalyst of 1 to 50 ppm, and a salt or oxide or inorganic salt as an additive with a molar ratio of the main catalyst to the additive of 1: 1-20.   3. The process according to claim 1, characterized in that said chemical oxidant may be NaClO, H202, or peroxyacetic acid.   4. Method according to claim 1 or 2, characterized in that, when a chemical oxidant is used, the reaction is carried out in a solvent such as water, acetic acid, ethyl acetate, benzene, or toluene, at a reaction temperature of 20 to 80 C and at atmospheric pressure.   5. Process according to claim 1 or 2, characterized in that said olefins are C3 to C10 alkenes, C5 to C8 monocyclic olefins, polycyclic olefins, aromatic olefins and their derivatives.   6. Method according to claim 1 or 2, characterized in that the pressure range is from 4 to 8 atm, the temperature range is from 50 to -110 C, and the catalyst concentration is from 2 to 8 ppm.   7. Method according to claim 1 or 2, characterized in that the additive to the composite catalyst is a salt or an oxide of a metal such as Cu, Zn, Fe, Co, Mn, Cr, Ni, or a phosphate, a phosphonate, an amine or an ammonium salt, or a reducing gas such as hydrogen or CO.   8. Process according to claim 1 or 2, characterized in that the support for supporting the metallic porphyrin comprises a silica gel, a molecular sieve, an alumina, a zeolite, diatomaceous earth, activated charcoal, a sepiolite, porous ceramics, polyvinyl chloride, polyvinyl chloride, polystyrene, cellulose, chitosan, chitin, and derivatives thereof.