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CN-121974791-A - Method for hydroformylation of olefins

CN121974791ACN 121974791 ACN121974791 ACN 121974791ACN-121974791-A

Abstract

The application belongs to the field of organic chemistry, and in particular relates to a method for hydroformylation of olefins, which comprises the following steps: under the action of a metal catalyst and a ligand and under the illumination condition, carrying out hydroformylation on olefin, carbon monoxide and hydrogen shown in a formula (I) to obtain aldehyde. The method provided by the application can be realized at normal temperature and normal pressure, does not need special equipment, has low potential safety hazard and low energy consumption, greatly reduces the cost of large-scale production of aldehyde, and provides a green and efficient new synthesis process for industrial production. Formula (I).

Inventors

  • HUANG HANMIN
  • LIU HONGCHI

Assignees

  • 中国科学技术大学

Dates

Publication Date
20260505
Application Date
20260127

Claims (10)

  1. 1. A process for the hydroformylation of olefins comprising the steps of: under the action of a metal catalyst and a ligand and under the illumination condition, carrying out hydroformylation on olefin, carbon monoxide and hydrogen shown in a formula (I) to obtain aldehyde; Formula (I); In the formula (I), R 1 、R 2 、R 3 and R 4 are independently selected from hydrogen, a substituted or unsubstituted C1-C60 aliphatic group, a substituted or unsubstituted C4-C60 aromatic group, a substituted or unsubstituted C4-C60 heterocyclic group, a substituted or unsubstituted C1-C40 amide group, or adjacent groups in R 1 、R 2 、R 3 and R 4 are connected to form a substituted or unsubstituted C3-C40 alicyclic group, a substituted or unsubstituted C3-C40 heterocyclic group, and at least one of R 1 、R 2 、R 3 and R 4 is selected from hydrogen; The substituent groups are selected from one or more of C1-C20 alkyl groups, C3-C20 cycloalkyl groups, C6-C20 aryl groups, C4-C20 heterocyclic groups, C2-C20 ester groups, C2-C20 ketocarbonyl groups, C1-C20 amide groups, C1-C20 alkoxy groups, C4-C20 aromatic oxygen groups, C2-C20 acyloxy groups, halogen, cyano groups, nitro groups, sulfonic acid groups, phosphate groups and amino groups.
  2. 2. The method according to claim 1, wherein the total pressure of the carbon monoxide and the hydrogen is 1atm to 50atm, the temperature of the hydroformylation reaction is 10 ℃ to 150 ℃, and the wavelength of the illumination is 380nm to 525nm.
  3. 3. The method according to claim 1, wherein the metal catalyst is selected from the group consisting of compounds of one or more elements of cobalt, nickel, copper, ruthenium, rhodium, iridium and palladium; The ligand is selected from an organophosphine ligand and/or a nitrogen-containing organic ligand.
  4. 4. A process according to claim 3, wherein the metal catalyst is selected from nickel chloride, nickel bromide, nickel iodide, nickel acetate, nickel sulfate, nickel acetylacetonate, nickel nitrate, cobalt octacarbonyl, cobalt chloride, cobalt bromide, cobalt acetylacetonate, cobalt nitrate, copper chloride, copper bromide, copper iodide, copper acetate, copper acetylacetonate, ruthenium trichloride, tris ruthenium dodecacarbonyl, (1, 5-cyclooctadiene) dichloride, rhodium acetate, rhodium dimerized acetate, rhodium acetylacetonate, bis rhodium tetracarbonyl dichloride, (1, 5-cyclooctadiene) chlororhodium dimer, bis-carbonyl acetylacetonate rhodium, iridium acetate, iridium chloride, 1,5- (cyclooctadiene) iridium chloride dimer, palladium chloride, palladium bromide, palladium iodide, palladium carbon, tetrakis triphenylphosphine palladium, tris (dibenzylideneacetone) dipalladium, palladium acetate, palladium acetylacetonate, (1, 5-cyclooctadiene) palladium dichloride, (1, 5-cyclooctadiene) palladium dibromide, palladium chloride, bis-acetonitrile, bis-palladium and bis-benzonitrile acetate; The ligand is selected from one or more of triphenylphosphine, 1, 2-bis (diphenylphosphine) ethane, 1, 3-bis (diphenylphosphine) propane, 1, 4-bis (diphenylphosphine) butane, 1' -binaphthyl-2, 2' -bisdiphenylphosphine, 5-bisdiphenylphosphine-9, 9-dimethylxanthene, 4, 5-bis-tertiary butyl phosphine-9, 9-dimethylxanthene, 4, 5-dicyclohexylphosphine-9, 9-dimethylxanthene, 4, 6-bis (diphenylphosphine) phenazine, bis (2-diphenylphosphine) ether, bis (2-dicyclohexylphosphine) ether, 2' -bipyridine, 6' -dimethyl-2, 2' -bipyridine, terpyridine and 1, 10-phenanthroline.
  5. 5. The method of claim 1, wherein the molar ratio of the metal catalyst to olefin is (0.001:1) - (0.1:1).
  6. 6. The method of claim 1, wherein the molar ratio of metal catalyst to coordinating atoms in the ligand is (1:1) - (1:5).
  7. 7. The method of claim 1, wherein the molar ratio of carbon monoxide to hydrogen is (1:5) - (5:1).
  8. 8. The process according to claim 1, wherein the reaction medium of the hydroformylation reaction is selected from one or more of benzene, chlorobenzene, fluorobenzene, toluene, benzotrifluoride, xylene, mesitylene, anisole, 1, 4-dioxane, tetrahydrofuran, acetonitrile, benzonitrile, acetone, dichloromethane, 1, 2-dichloroethane, chloroform, carbon tetrachloride, ethylene glycol dimethyl ether, methyl tert-butyl ether, methylcyclopentyl ether, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and dimethylsulfoxide.
  9. 9. The method of claim 8, wherein the concentration of the olefin in the reaction medium is 0.1mol/mL to 0.5mol/mL.
  10. 10. The method of claim 1, further comprising the step of: After the hydroformylation reaction is finished, performing column chromatography on the obtained reaction product; the mobile phase of the column chromatography is n-hexane and ethyl acetate with the volume ratio of (1-100): 1.

Description

Method for hydroformylation of olefins Technical Field The invention belongs to the field of organic chemistry, and particularly relates to a method for hydroformylation of olefins. Background The hydroformylation reaction is a reaction in which a mixture of CO and H 2 (synthesis gas) is added to an olefin under the action of a catalyst to form an aldehyde. The reaction is one of the most useful homogeneous catalytic reactions in industrial production, the annual yield is more than ten millions of tons, and the reaction is used for producing various large-scale chemical raw materials. Butyraldehyde synthesized from propylene, for example, can be further converted to 2-ethylhexanol by condensation reduction and is widely used as a plasticizer, and long-chain alcohols can be obtained by hydroformylation and reduction of long-chain olefins and are widely used in the production of detergents. Thus, the hydroformylation reaction has been continuously and intensively studied and improved for over eighty years. The first report of Roelen in 1938 was the hydroformylation reaction, called oxo reaction, in which cobalt was used as a catalyst to synthesize aldehydes by hydroformylation using olefins at a temperature of 150 to 180 ℃ and a pressure of 30 MPa. Because of its high industrial value, the first plant was established in germany at extremely rapid rates, and then rapidly popularized worldwide. Companies such as basf, exxon, saxol, shell developed a second generation hydroformylation catalyst in the middle of the 20 th century, improved recovery means for cobalt-based catalysts and use phosphine ligands to modulate regioselectivity. The method is mainly used for producing aldehydes such as butyraldehyde from small molecular olefins such as propylene and the like, and has been used until now. However, the reaction still needs the synthesis gas with the pressure of 4-30 MPa at the temperature of 120-190 ℃, and the requirement on special equipment is high and the potential safety hazard is large. In the 70 s of the 20 th century, the Dow, basff and Mitsubishi companies developed the third generation of hydroformylation catalysts. By using a rhodium-based catalyst coordinated with phosphine ligands, the reaction efficiency is greatly improved. The reaction temperature is reduced to 85-130 ℃, and the pressure of the synthesis gas is reduced to 1.8-6 MPa. The Zhang Xumu problem group reported asymmetric hydroformylation in 2006. By using rhodium coordinated with an aryl phosphine-phosphoramidite bidentate chiral ligand as a catalyst, asymmetric hydroformylation of aromatic olefins and vinyl acetate can be achieved with an equivalent conversion of 98% ee at 60 ℃ and a synthesis gas pressure of 10 atm. The Dydio group reports binuclear palladium catalyzed hydroformylation in 2020. The hydroformylation of olefins was achieved using Xantphos and palladium iodide as catalysts at a synthesis gas pressure of 10MPa at 100 ℃. The coordination promoting function of iodide ions is proved by mechanism research. Although the above reaction realizes the hydroformylation reaction of olefin, higher temperature and pressure are generally required, the requirement on special equipment is high, the potential safety hazard is large, and the energy consumption is large. Disclosure of Invention In view of the above, the present invention aims to provide a method for hydroformylation of olefins, which can be carried out at normal temperature and pressure and has universality for various kinds of olefins. The invention provides a method for hydroformylation of olefins, which comprises the following steps: under the action of a metal catalyst and a ligand and under the illumination condition, carrying out hydroformylation on olefin, carbon monoxide and hydrogen shown in a formula (I) to obtain aldehyde; Formula (I); In the formula (I), R 1、R2、R3 and R 4 are independently selected from hydrogen, a substituted or unsubstituted C1-C60 aliphatic group, a substituted or unsubstituted C4-C60 aromatic group, a substituted or unsubstituted C4-C60 heterocyclic group, a substituted or unsubstituted C1-C40 amide group, or adjacent groups in R 1、R2、R3 and R 4 are connected to form a substituted or unsubstituted C3-C40 alicyclic group, a substituted or unsubstituted C3-C40 heterocyclic group, and at least one of R 1、R2、R3 and R 4 is selected from hydrogen; The invention takes alkene, carbon monoxide and hydrogen as raw materials, and carries out hydroformylation reaction under the action of metal catalyst and ligand and under the condition of illumination, thus obtaining the product aldehyde. The method provided by the invention can be realized at normal temperature and normal pressure, does not need special equipment, has low potential safety hazard and low energy consumption, greatly reduces the cost of large-scale production of aldehyde, and provides a green and efficient new synthesis process for industrial production. The invention takes olefin show