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US-12617743-B2 - Process for preparing the dialdehyde of vinylcyclohexene

US12617743B2US 12617743 B2US12617743 B2US 12617743B2US-12617743-B2

Abstract

Process for preparing the dialdehyde of vinylcyclohexene.

Inventors

  • Robert Franke
  • Carolin Schneider
  • Ralf Jackstell
  • Matthias Beller

Assignees

  • EVONIK OPERATIONS GMBH

Dates

Publication Date
20260505
Application Date
20230630
Priority Date
20220706

Claims (12)

  1. 1 . Process comprising the process steps of: a) initially charging vinylcyclohexene; b) adding a compound of formula (I): where R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 are selected from: —H, —(C 1 -C 12 )-alkyl, -Ph; c) adding a Pt compound capable of forming a complex; d) adding an iodine compound; e) feeding in CO and H 2 ; f) heating the reaction mixture from steps a) to e), to convert the vinylcyclohexene to the dialdehyde and g) converting the dialdehyde to the diol.
  2. 2 . Process according to claim 1 , where R 1 and R 4 are —H.
  3. 3 . Process according to claim 1 , where R 5 , R 6 , R 7 , R 8 are -Ph.
  4. 4 . Process according to claim 1 , where R 2 and R 3 are —(C 1 -C 12 )-alkyl.
  5. 5 . Process according to claim 1 , where R 2 and R 3 are —CH 3 .
  6. 6 . Process according to claim 1 , wherein the compound (I) has the structure (1):
  7. 7 . Process according to claim 1 , wherein the Pt compound is selected from: Pt(II)I 2 , Pt(IV)I 4 , diphenyl(1,5-COD)Pt(II), Pt(II)(acac) 2 , Pt(0)(PPh 3 ) 4 , Pt(0)(DVTS) solution (CAS: 68478-92-2), Pt(0)(ethylene)(PPh 3 ) 2 , tris(benzylideneacetone)Pt(0), Pt(II)(OAC) 2 solution, Pt(0)(t-Bu) 2 , Pt(II)(COD)Me 2 , Pt(II)(COD)I 2 , Pt(IV)IMe 3 , Pt(II)(hexafluoroacetylacetonate) 2 .
  8. 8 . Process according to claim 1 , wherein PtI 2 is added in an amount, measured in mol % based on vinylcyclohexene, so that the value is in the range of 0.1 mol % to 5 mol %.
  9. 9 . Process according to claim 1 , comprising the additional process step e′): e′) adding a solvent.
  10. 10 . Process according to claim 1 , wherein the conversion of the dialdehyde to the diol is carried out using “Shvo's catalyst” (CAS 104439-77-2).
  11. 11 . Aldehyde mixture comprising the compounds (2a) and (2b):
  12. 12 . Alcohol mixture comprising the compounds (3a) and (3b):

Description

The present invention relates to a process for preparing the dialdehyde of vinylcyclohexene. US 2009/0171125 A1 describes a process for hydroformylation of cyclic olefins. Here, a Rh catalyst is used. The present invention has the object of providing a novel hydroformylation process. The process here is to afford an increased yield compared to the method known from the prior art. This object is achieved by a process according to claim 1. Process comprising the process steps of: a) initially charging vinylcyclohexene;b) adding a compound of formula (I): where R1, R2, R3, R4, R5, R6, R7, R8 are selected from: —H, —(C1-C12)-alkyl, -Ph;c) adding a Pt compound capable of forming a complex;d) adding an iodine compound;e) feeding in CO and H2;f) heating the reaction mixture from a) to e), to convert the vinylcyclohexene to the dialdehyde. In this process, process steps a) to e) can be effected in any desired sequence. Typically, however, CO and H2 are added after the co-reactants have been initially charged in steps a) to d). It is also possible here for process steps c) and d) to be effected in one step, for example by adding PtI2. In one variant of the process, the Pt compound and the iodine compound are added in one step, by adding PtI2. The expression (C1-C12)-alkyl encompasses straight-chain and branched alkyl groups having 1 to 12 carbon atoms. These are preferably (C1-C8)-alkyl groups, more preferably (C1-C6)-alkyl, most preferably (C1-C4)-alkyl. Suitable (C1-C12)-alkyl groups are especially methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 2-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 2,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethylbutyl, 1-ethyl-2-methylpropyl, n-heptyl, 2-heptyl, 3-heptyl, 2-ethylpentyl, 1-propylbutyl, n-octyl, 2-ethylhexyl, 2-propylheptyl, nonyl, decyl. In one variant of the process, R1 and R4 are —H. In one variant of the process, R5, R6, R7, R8 are -Ph. In one variant of the process, R2 and R3 are —(C1-C12)-alkyl. In one variant of the process, R2 and R3 are —CH3. In one variant of the process, the compound (I) has the structure (1): In one variant of the process, the Pt compound is selected from: Pt(II)I2, Pt(IV)I4, diphenyl(1,5-COD)Pt(11), Pt(II)(acac)2, Pt(0)(PPh3)4, Pt(0)(DVTS) solution (CAS: 68478-92-2), Pt(0)(ethylene)(PPh3)2, tris(benzylideneacetone)Pt(0), Pt(II)(OAC)2 solution, Pt(0)(t-Bu)2, Pt(II)(COD)Me2, Pt(II)(COD)I2, Pt(IV)IMe3, Pt(II)(hexafluoroacetylacetonate)2. In one variant of the process, the Pt compound is selected from: Pt(II)I2, Pt(II)(acac)2. In one variant of the process, the Pt compound is Pt(II)I2. In one variant of the process, the iodine compound is selected from: alkali metal halide, alkaline earth metal halide. NH4X, alkylammonium halide, dialkyl halide, trialkyl halide, tetraalkyl halide, cycloalkylammonium halide. In one variant of the process, the iodine compound is selected from: Pt(II)I2, Lil. In one variant of the process, PtI2 is added in an amount, measured in mol % based on vinylcyclohexene, so that the value is in the range of 0.1 mol % to 5 mol %. In one variant of the process, PtI2 is added in an amount, measured in mol % based on vinylcyclohexene, so that the value is in the range of 0.1 mol % to 3 mol %. In one variant of the process, PtI2 is added in an amount, measured in mol % based on vinylcyclohexene, so that the value is in the range of 0.1 mol % to 1 mol %. In one variant of the process, this process comprises the additional process step e′): e′) adding a solvent. In one variant of the process, the solvent is selected from: THF, DCM, ACN, heptane, DMF, toluene, texanol, pentane, hexane, octane, isooctane, decane, dodecane, cyclohexane, benzene, xylene, Marlotherm, propylene carbonate, MTBE, diglyme, triglyme, diethyl ether, dioxane, isopropanol, tert-butanol, isononanol, isobutanol, isopentanol, ethyl acetate. In one variant of the process, the solvent is selected from: THF, DCM, ACN, heptane, DMF, toluene, texanol. In one variant of the process, CO and H2 are fed in at a pressure in a range from 1 MPa (10 bar) to 6 MPa (60 bar). In one variant of the process, CO and H2 are fed in at a pressure in a range from 1 MPa (20 bar) to 6 MPa (50 bar). In one variant of the process, the reaction mixture is heated to a temperature in the range from 30° C. to 150° C. In one variant of the process, the reaction mixture is heated to a temperature in the range from 80° C. to 140° C. In one variant of the process, the process comprises the additional process step g): g) converting the dialdehyde to the diol. In one variant of the process, the conversion of the dialdehyde to the diol is carried out using “Shvo's catalyst” (CAS 104439-77-2). In addition to the proces