Process for the hydroformylation of olefins using platinum and Thixantphos

Abstract

The present invention relates to a process for the hydroformylation of olefins using platinum and Thixantphos.

Description

Technical Field

[0001] The present invention relates to a process for the hydroformylation of olefins using platinum and Thixantphos. Background Art

[0002] P. Meessen et al., Journal of Organometallic Chemistry, 551, (1998), 165-170 describe the use of ThixantphosPtCl2 for the hydroformylation of methyl 3-pentenoate

[0003] (Thixantphos). Summary of the invention

[0004] The object of the present invention was to provide a novel hydroformylation process which should provide good yields.

[0005] This object is achieved by a method according to claim 1 .

[0006] The method comprises the following steps:

[0007] a) adding olefin in advance;

[0008] b) adding a compound of formula (I):

[0009]

[0010] 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;

[0011] c) adding a Pt compound capable of forming a complex;

[0012] d) adding bromine or iodine compounds;

[0013] e) introducing CO and H2;

[0014] f) Heating the reaction mixture obtained from a) to e), wherein the olefin is converted into the aldehyde.

[0015] Here, process steps a) to e) can be carried out in any desired order. However, usually, CO and H2 are added after the reaction participants in steps a) to d) have been previously added.

[0016] Here, process steps c) and d) can be carried out in one step by adding PtBr2 or PtI2.

[0017] 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.

[0018] 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.

[0019] 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.

[0020] Terminology (C6-C 20 )-aryl includes monocyclic or polycyclic aromatic hydrocarbon groups having 6 to 20 carbon atoms. These preferably (C6-C 14 )-aryl, more preferably (C6-C 10 )-aryl.

[0021] Suitable (C6-C 20 )-aryl is especially phenyl, naphthyl, indenyl, fluorenyl, anthracenyl, phenanthrenyl, naphthacene, chrysene, pyrenyl, corundum. Preferred (C6-C 20 )-Aryl is phenyl, naphthyl and anthracenyl.

[0022] In a variation of this approach, R 5 , R 6 , R 7 , R 8 Yes-(C6-C20 )-aryl.

[0023] In a variation of this approach, R 5 , R 6 , R 7 , R 8 Yes - Ph.

[0024] In a variation of this approach, R 1 and R 4 Yes - (C1-C 12 )-alkyl.

[0025] In a variation of this approach, R 1 and R 4 It is -CH3.

[0026] In a variation of this approach, R 2 and R 3 Yes -H.

[0027] In one variation of this method, the compound of formula (I) has structure (1):

[0028] .

[0029] 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.

[0030] In one variation of the method, the Pt compound is selected from: Pt(II)I2, Pt(II)Br2.

[0031] 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.

[0032] In one variant of the process, the bromine compound added in process step d) is Pt(II)Br2.

[0033] 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.

[0034] In one variant of the process, the iodine compound added in process step d) is Pt(II)I2.

[0035] 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.

[0036] In one variant of the method, the method comprises the additional method step e'):

[0037] e') Add solvent.

[0038] 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, ethyl acetate.

[0039] In one variation of the process, the solvent is selected from: THF, DCM, ACN, heptane, DMF, toluene, Texanol.

[0040] In one variation of the process, CO and H2 are introduced at a pressure of 1 MPa (10 bar) to 6 MPa (60 bar).

[0041] In one variation of the process, CO and H2 are introduced at a pressure of 2 MPa (20 bar) to 5 MPa (50 bar).

[0042] In one variation of the method, the heating is to a temperature of 25°C to 150°C.

[0043] In one variation of the method, the heating is to a temperature of 30°C to 130°C.

[0044] 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

[0045] The present invention will be described in detail below by means of working examples.

[0046] Experimental Description

[0047] A vial was charged with PtX2 (X = halogen), ligand and an oven-dried stirring bar. The vial was then sealed with a septum (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 80°C for 18 h. After the reaction was completed, the autoclave was cooled to room temperature and carefully depressurized. The yield and selectivity were determined by GC analysis.

[0048] Hydroformylation of 1-octene

[0049]

[0050] Reaction conditions:

[0051] 1.0 mmol of 1-octene, 0.5 mol% PtI2, 2.0 equivalents of ligand, solvent: toluene, p(CO / H2): 40 bar, T: 80°C, t: 18 h.

[0052] Ligand Yield (%) #timg# <![CDATA[PtI2*: 99。]]>

[0053] *The method of the present invention

[0054] Halogen changes

[0055] Reaction conditions:

[0056] 10 mmol of 1-octene, 0.1 mol% of PtX2, 2.2 equivalents of ligand (1), solvent: toluene, p(CO / H2): 40 bar, T: 80°C, t: 20 h.

[0057] Yield:

[0058] PtI2: 95%

[0059] PtBr2: 48%

[0060] PtCl2: <1%.

[0061] 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; 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 - (C1-C 12 )-alkyl.

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 the group consisting of: 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.

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