PLATINUM COMPLEXES HAVING FERROCENE DIPHOSPHINE LIGANDS FOR CATALYSIS OF THE HYDROXYCARBONYLATION OF ETHYLENICALLY UNSATURATED COMPOUNDS

Abstract

Platinum complexes having ferrocene-diphosphine ligands for catalysis of the hydroxycarbonylation of ethylenically unsaturated compounds.

Claims

1. Complex comprising Pt and a compound of formula (I) ##STR00007## where R.sup.1, R.sup.2, R.sup.3, R.sup.4 are each independently selected from —(C.sub.1-C.sub.12)-alkyl, —(C.sub.6-C.sub.20)-heteroaryl.

2. Complex according to claim 1, wherein at least two of the R.sup.1, R.sup.2, R.sup.3, R.sup.4 radicals are a —(C.sub.6-C.sub.20)-heteroaryl radical having at least six ring atoms.

3. Complex according to claim 1, wherein the R.sup.1 and R.sup.3 radicals are each a —(C.sub.6-C.sub.20)-heteroaryl radical having at least six ring atoms.

4. Complex according to claim 1, wherein the R.sup.1 and R.sup.3 radicals are each 2-pyridyl.

5. Complex according to claim 1, wherein R.sup.2 and R.sup.4 are —(C.sub.1-C.sub.12)-alkyl.

6. Complex according to claim 1, wherein R.sup.2 and R.sup.4 are tert-butyl.

7. Complex according to claim 1, wherein the compound (I) has the structure (1): ##STR00008##

8. Process comprising the process steps of: a) initially charging an ethylenically unsaturated compound; b) adding a complex according to claim 1, or a compound of formula (I) ##STR00009## where R.sup.1, R.sup.2, R.sup.3, R.sup.4 are each independently selected from —(C.sub.1-C.sub.12)-alkyl, —(C.sub.6-C.sub.20)-heteroaryl and a substance comprising Pt; c) adding an acid; d) feeding in CO; e) heating the reaction mixture from a) to d), with conversion of the ethylenically unsaturated compound to a carboxylic acid.

9. Process according to claim 8, wherein the ethylenically unsaturated compound is selected from: ethene, propene, 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.

10. Process according to claim 8, wherein the acid in process step c) is selected from: acetic acid, perchloric acid, sulfuric acid, phosphoric acid, methylphosphonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, tert-butanesulfonic acid, p-toluenesulfonic acid, 2-hydroxypropane-2-sulfonic acid, 2,4,6-trimethylbenzenesulfonic acid, dodecylsulfonic acid, camphorsulfonic acid.

11. Process according to claim 8, wherein the acid in process step c) is acetic acid.

12. Process according to claim 8, wherein the substance comprising Pt is selected from: platinum dichloride (PtCl.sub.2), platinum(II) acetylacetonate [Pt(acac).sub.2], platinum(II) acetate [Pt(OAc).sub.2], dichloro(1,5-cyclooctadiene)platinum(II) [Pt(cod).sub.2Cl.sub.2], bis(dibenzylideneacetone)platinum [Pt(dba).sub.2], bis(acetonitrile)dichloroplatinum(II) [Pt(CH.sub.3CN).sub.2Cl.sub.2], (cinnamyl)platinum dichloride [Pt(cinnamyl)Cl.sub.2].

13. Process according to claim 8, wherein the substance comprising Pt is selected from: platinum dichloride (PtCl.sub.2), platinum(II) acetylacetonate [Pt(acac).sub.2], platinum(II) acetate [Pt(OAc).sub.2].

Description

[0019] The invention further relates to the use of a complex according to the invention for catalysis of an hydroxycarbonylation reaction.

[0020] Process comprising the process steps of:

[0021] a) initially charging an ethylenically unsaturated compound;

[0022] b) adding a complex as described above, or [0023] a compound of formula (I)

##STR00004##

[0024] where

[0025] R.sup.1, R.sup.2, R.sup.3, R.sup.4 are each independently selected from —(C.sub.1-C.sub.12)-alkyl, —(C.sub.6-C.sub.20)-heteroaryl and a substance comprising Pt;

[0026] c) adding an acid;

[0027] d) feeding in CO;

[0028] e) heating the reaction mixture from a) to d), with conversion of the ethylenically unsaturated compound to a carboxylic acid.

[0029] In this process, process steps a), b), c) and d) can be effected in any desired sequence. Typically, however, the addition of CO is effected after the co-reactants have been initially charged in steps a) to c). In addition, CO can also be fed in in two or more steps, in such a way that, for example, a portion of the CO is first fed in, then the mixture is heated, and then a further portion of CO is fed in.

[0030] The ethylenically unsaturated compounds used as reactant in the process according to the invention contain one or more carbon-carbon double bonds. These compounds are also referred to hereinafter as olefins for simplification. The double bonds may be terminal or internal.

[0031] In one variant of the process, the ethylenically unsaturated compound does not comprise any further functional groups apart from carbon-carbon double bonds.

[0032] In one variant of the process, the ethylenically unsaturated compound is selected from: ethene, propene, 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.

[0033] In one variant of the process, the acid in process step c) is selected from: acetic acid, perchloric acid, sulfuric acid, phosphoric acid, methylphosphonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, tert-butanesulfonic acid, p-toluenesulfonic acid (PTSA), 2-hydroxypropane-2-sulfonic acid, 2,4,6-trimethylbenzenesulfonic acid, dodecylsulfonic acid, camphorsulfonic acid.

[0034] In one variant of the process, the acid in process step c) is acetic acid (AcOH).

[0035] In one variant of the process, the substance comprising Pt is selected from: platinum dichloride (PtCl.sub.2), platinum(II) acetylacetonate [Pt(acac).sub.2], platinum(II) acetate [Pt(OAc).sub.2], dichloro(1,5-cyclooctadiene)platinum(II) [Pt(cod).sub.2Cl.sub.2], bis(dibenzylideneacetone)platinum [Pt(dba).sub.2], bis(acetonitrile)dichloroplatinum(II) [Pt(CH.sub.3CN).sub.2Cl.sub.2], (cinnamyl)platinum dichloride [Pt(cinnamyl)Cl.sub.2].

[0036] In one variant of the process, the substance comprising Pt is selected from: platinum dichloride (PtCl.sub.2), platinum(II) acetylacetonate [Pt(acac).sub.2], platinum(II) acetate [Pt(OAc).sub.2].

[0037] CO is fed in in step d) preferably at a partial CO pressure between 0.1 and 10 MPa (1 to 100 bar), preferably between 1 and 8 MPa (10 to 80 bar), more preferably between 2 and 6 MPa (20 to 60 bar).

[0038] The reaction mixture is heated in step e) of the process according to the invention preferably to a temperature in the range from 60° C. to 160° C., preferably from 80° C. to 140° C., particularly preferably from 80° C. to 120° C., in order to convert the ethylenically unsaturated compound to an acid.

[0039] The invention is to be illustrated in detail hereinafter by a working example.

Conversion of 1-octene to the Acid

[0040] ##STR00005##

[0041] Reaction conditions: 1-octene (1.0 mmol), PtCl.sub.2 (0.01 mmol, 1.0 mol %), ligand: bidentate phosphine ligand (0.022 mmol, 2.2 mol %), sulfuric acid [0.3 M] 0.5 mL, AcOH (1.5 mL), pressure (CO): 40 bar, temperature: 120° C., reaction time: 18 h.

[0042] The reaction was carried out in a process according to the invention using ligand (1), and also using ligand (2) as a comparative experiment:

##STR00006##

[0043] The process according to the invention using ligand (1) afforded a yield of 41% here. Conversely, in the comparative experiment using ligand (2), a yield of only 13% could be achieved.

[0044] The cost of Pt is below that of Pd. The object is thus achieved by a complex according to the invention.