Process for the hydroformylation of olefins using platinum and bis(2-diphenylphosphinophenyl) ether

By using platinum and bis(2-diphenylphosphine phenyl)ether (DPEphos) as catalysts, the hydroformylation reaction is carried out using specific step sequences and conditions, the problem of insufficient yield in the prior art is solved, and the problem of achieving the The effect of efficient conversion of olefins into aldehydes.

CN116265426BActive Publication Date: 2025-02-14EVONIK OXENO GMBH & CO KG
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Patent Information

Application Number
CN202211612422.5
Authority / Receiving Office
CN · China
Patent Type
Patents(China)
Current Assignee / Owner
Priority Date
2021-12-17
Filing Date
2022-12-15
Publication Date
2025-02-14
Estimated Expiration
2042-12-15

AI Technical Summary

Technical Problem

The existing hydroformylation methods have insufficient yields, making it difficult to achieve efficient conversion of olefins into aldehydes.

Method used

Using platinum and bis(2-diphenylphosphine phenyl)ether (DPEphos) as catalysts, through specific step sequences and conditions (such as pre-adding of olefins, addition of Pt compounds, bromine compounds or iodine compounds, introduction of CO and H2, and Heat) to carry out hydroformylation reaction.

Benefits of technology

The yield of the hydroformylation reaction is significantly improved, and the effect of efficient conversion of olefins into aldehydes is achieved.

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Patent Text Reader

Abstract

The present invention relates to a process for the hydroformylation of olefins using platinum and bis(2-diphenylphosphinophenyl) ether.
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Description

Technical Field

[0001] The present invention relates to a process for the hydroformylation of olefins using platinum and bis(2-diphenylphosphinophenyl) ether (DPEphos). Background Art

[0002] P. Meessen et al., Journal of Organometallic Chemistry, 551, (1998), 165-170 describe the use of bis(2-diphenylphosphinophenyl)ether (DPEphos)PtCl2 for the hydroformylation of methyl 3-pentenoate (bis(2-diphenylphosphinophenyl)ether (DPEphos)). Summary of the invention

[0003] The object of the present invention is to provide a novel hydroformylation process which should provide increased yields compared with the processes known from the prior art.

[0004] This object is achieved by the method according to the invention.

[0005] The method comprises the following steps:

[0006] a) adding olefin in advance;

[0007] b) adding a compound of formula (I):

[0008]

[0009] Where R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 Selected from: -H, -(C1-C 12 )-alkyl, -(C6-C 20 )-aryl, and R 5 , R 6 , R 7 , R 8 At least two of the groups are -(C6-C 20 )-aryl;

[0010] c) adding a Pt compound capable of forming a complex;

[0011] d) adding a bromine compound or an iodine compound;

[0012] e) introducing CO and H2;

[0013] f) heating the reaction mixture obtained from a) to e), wherein the olefin is converted into an aldehyde.

[0014] Here, process steps a) to e) can be carried out in any desired order. Usually, however, CO and H2 are added after the reaction partners in steps a) to d) have been previously added.

[0015] Here, process steps c) and d) can be carried out in one step by adding PtBr2 or PtI2.

[0016] In a preferred variation of the process, the Pt compound and the bromine compound or the iodine compound are added in one step by adding PtBr2 or PtI2.

[0017] Terminology (C1-C 12 )-Alkyl includes straight-chain and branched alkyl groups having 1 to 12 carbon atoms. These are preferably (C1-C8)-alkyl, more preferably (C1-C6)-alkyl, most preferably (C1-C4)-alkyl.

[0018] Suitable (C1-C 12 )-alkyl, in particular 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.

[0019] Terminology (C6-C 20 )-Aryl includes monocyclic or polycyclic aromatic hydrocarbon groups having 6 to 20 carbon atoms. These are preferably (C6-C 14 )-aryl, more preferably (C6-C 10 )-aryl.

[0020] Suitable (C6-C 20 )-aryl, in particular phenyl, naphthyl, indenyl, fluorenyl, anthracenyl, phenanthrenyl, naphthacene, Preferred (C6-C 20 )-Aryl is phenyl, naphthyl and anthracenyl.

[0021] In a variation of this approach, R5 , R 6 , R 7 , R 8 Yes-(C6-C 20 )-aryl.

[0022] In a variation of this approach, R 5 , R 6 , R 7 , R 8 Yes - Ph.

[0023] In a variation of this approach, R 1 and R 4 Yes -H.

[0024] In a variation of this approach, R 2 and R 3 Yes -H.

[0025] In one variation of this method, the compound of formula (I) has structure (1):

[0026]

[0027] In one variation of the method, the Pt compound is selected from: Pt(II)I2, Pt(II)Br2, Pt(IV)I4, Pt(IV)Br4, diphenyl(1,5-COD)Pt(II), Pt(II)(acac)2, Pt(0)(PPh3)4, Pt(0)(DVTS) solution (CAS:68478-92-2), Pt(0)(ethylene)(PPh3)2, Pt(II)Br2(COD), tri(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.

[0028] In one variation of the method, the Pt compound is selected from: Pt(II)I2, Pt(II)Br2.

[0029] In one variation of the method, the iodine compound or the bromine compound is selected from the group consisting of alkali metal halides, alkaline earth metal halides, NH4X, alkylammonium halides, dialkylhalogenides, trialkylhalogenides, tetraalkylhalogenides and cycloalkylammonium halides.

[0030] In one variant of the process, the bromine compound added in process step d) is Pt(II)Br2.

[0031] In one variation of the process, the bromine compound is added in an amount of 0.1 to 10, measured in equivalents based on Pt.

[0032] In one variant of the process, the iodine compound added in process step d) is Pt(II)I2.

[0033] In one variation of the method, the iodine compound is added in an amount of 0.1 to 10, measured in equivalents based on Pt.

[0034] In one variant of the method, the method comprises the additional method step e'):

[0035] e') Adding solvent.

[0036] In one variation of the process, the solvent is selected from the group consisting of THF, DCM, ACN, heptane, DMF, toluene, Texanol, pentane, hexane, octane, isooctane, decane, dodecane, cyclohexane, benzene, xylene, Marlotherm, propylene carbonate, MTBE, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, ethyl ether, dioxane, isopropanol, tert-butyl alcohol, isononanol, isobutyl alcohol, isoamyl alcohol, and ethyl acetate.

[0037] In one variation of the process, the solvent is selected from: THF, DCM, ACN, heptane, DMF, toluene, Texanol.

[0038] In one variation of the process, CO and H2 are introduced at a pressure of 1 MPa (10 bar) to 6 MPa (60 bar).

[0039] In one variation of the process, CO and H2 are introduced at a pressure of 2 MPa (20 bar) to 5 MPa (50 bar).

[0040] In one variation of the method, the heating is to a temperature of 25°C to 150°C.

[0041] In one variation of the method, the heating is to a temperature of 30°C to 130°C.

[0042] In one variation of the process, the olefin is selected from the group consisting of ethylene, propylene, 1-butene, cis- and / or trans-2-butene, isobutene, 1,3-butadiene, 1-pentene, cis- and / or trans-2-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, hexene, tetramethylethylene, heptene, 1-octene, 2-octene, di-n-butene or mixtures thereof. DETAILED DESCRIPTION

[0043] The present invention will be described in detail below by means of working examples.

[0044] Experimental Description

[0045] PtX2 (X = halogen), ligand and oven-dried stirring rod were loaded into the vial. The vial was then sealed with a diaphragm (PTFE-coated styrene-butadiene rubber) and a phenolic resin cap. The vial was evacuated and refilled with argon three times. Toluene and 1-octene were added to the vial using a syringe. The vial was placed in an alloy plate (Legierungsplatte) and transferred to a 4560 series autoclave from Parr Instruments under an argon atmosphere. After purging the autoclave three times with CO / H2, the synthesis gas pressure was increased to 40 bar at room temperature. The reaction was carried out at 120°C for 20h. After the reaction was completed, the autoclave was cooled to room temperature and carefully decompressed. The yield and selectivity were determined by GC analysis.

[0046] Hydroformylation of 1-octene

[0047]

[0048] Reaction conditions:

[0049] 10.0 mmol of 1-octene, 0.1 mol% PtX2, 2.2 equivalents of ligand, solvent: toluene, p(CO / H2): 40 bar, T: 120°C, t: 20 h.

[0050] Yield:

[0051]

[0052] As shown by experimental results, this object is achieved by the method according to the present invention.

Claims

1. A method for hydroformylating olefins, comprising the following steps: a) adding olefin in advance; b) adding a compound of formula (I): Where R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 Selected from: -H, -(C1-C 12 )-alkyl, -(C6-C 20 )-aryl, and R 5 , R 6 , R 7 , R 8 At least two of the groups are -(C6-C 20 )-aryl; c) adding a Pt compound capable of forming a complex; d) adding a bromine compound or an iodine compound; e) introducing CO and H2; f) heating the reaction mixture obtained from a) to e), wherein the olefin is converted into an aldehyde.

2. The method according to claim 1, Where R 5 , R 6 , R 7 , R 8 Yes-(C6-C 20 )-aryl.

3. The method according to any one of claims 1 or 2, Where R 5 , R 6 , R 7 , R 8 Yes - Ph.

4. The method according to claim 1 or 2, Where R 1 and R 4 Yes -H.

5. The method according to claim 1 or 2, Where R 2 and R 3 Yes -H.

6. The method according to claim 1 or 2, The compound of formula (I) has the structure (1):

7. The method according to claim 1 or 2, The Pt compound is selected from: Pt(II)I2, Pt(II)Br2, Pt(IV)I4, Pt(IV)Br4, diphenyl(1,5-COD)Pt(II), Pt(II)(acac)2, Pt(0)(PPh3)4, Pt(0)(DVTS) solution CAS: 68478-92-2, Pt(0)(ethylene)(PPh3)2, Pt(II)Br2(COD), tri(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.

8. The method according to claim 1 or 2, In process step d), a bromine compound is added which is Pt(II)Br2.

9. The method according to claim 8, The amount of the bromine compound added is 0.1 to 10, measured in equivalents based on Pt.

10. The method according to claim 1 or 2, In process step d), an iodine compound is added which is Pt(II)I2.

11. The method according to claim 10, The iodine compound is added in an amount of 0.1 to 10, measured in equivalents based on Pt.

12. The method according to claim 1 or 2, It comprises the additional method step e'): e') Adding solvent.

13. The method according to claim 12, The solvent is selected from the group consisting of THF, DCM, ACN, heptane, DMF, toluene, Texanol, pentane, hexane, octane, isooctane, decane, dodecane, cyclohexane, benzene, xylene, Marlotherm, propylene carbonate, MTBE, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, ethyl ether, dioxane, isopropanol, tert-butyl alcohol, isononanol, isobutyl alcohol, isopentanol, and ethyl acetate.

14. The method according to claim 1 or 2, CO and H2 are introduced at a pressure of 1 MPa (10 bar) to 6 MPa (60 bar).

15. The method according to claim 1 or 2, The heating is carried out to a temperature of 25°C to 150°C.

Citation Information

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