# US 2018/0022772 A1 · 1, 1' -bis(phosphino)ferrocene ligands for alkoxycarbonylation

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- Number: US 2018/0022772 A1
- Document ID: US20180022772A1
- Status: Published application
- Kind: A1
- Application number: 15/649,759
- Filed: 2017-07-14
- Published: 2018-01-25
- Earliest claimed: 2016-07-19
- Assignees: Evonik Degussa GmbH
- Applicants: Evonik Degussa GmbH
- Inventors: Kaiwu DONG; Helfried NEUMANN; Ralf JACKSTELL; Matthias BELLER; Dirk FRIDAG; Dieter HESS; Katrin Marie DYBALLA; Frank GEILEN; Robert FRANKE
- Web page: https://patentgrep.com/patent/US20180022772A1

## CPC

- C07F 17/02: of metals of Groups 8, 9 or 10 of the Periodic Table
- C07C 67/38: by addition to an unsaturated carbon-to-carbon bond
- C07F 15/0066: {without a metal-carbon linkage}
- C07C 213/02: by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
- C07C 2527/185: with iron group metals or platinum group metals
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS

## Abstract

Diastereomer mixture comprising diastereomers of the formulae (I.1) and (I.2) where R2, R4 are each independently selected from —(C1-C12)-alkyl, —(C3-C12)-cycloalkyl, —(C3-C12)-heterocycloalkyl, —(C6-C20)-aryl; the R1, R3 radicals are each a —(C3-C20)-heteroaryl radical; R1, R3 may each independently be substituted by one or more substituents selected from —(C1-C12)-alkyl, —(C3-C12)-cycloalkyl, —(C3-C12)-heterocycloalkyl, —O—(C1-C12)-alkyl, —O—(C1-C12)-alkyl-(C6-C20)-aryl, —O—(C3-C12)-cycloalkyl, —S—(C1-C12)-alkyl, —S—(C3-C12)-cycloalkyl, —COO—(C1-C12)-alkyl, —COO—(C3-C12)-cycloalkyl, —CONH—(C1-C12)-alkyl, —CONH—(C3-C12)-cycloalkyl, —CO—(C1-C12)-alkyl, —CO—(C3-C12)-cycloalkyl, —N—[(C1-C12)-alkyl]2, —(C6-C20)-aryl, —(C6-C20)-aryl-(C1-C12)-alkyl, —(C6-C20)-aryl-O—(C1-C12)-alkyl, —(C3-C20)-heteroaryl, —(C3-C20)-heteroaryl-(C1-C12)-alkyl, —(C3-C20)-heteroaryl-O—(C1-C12)-alkyl, —COOH, —OH, —SO3H, —NH2, halogen; and R2, R4, if they are —(C1-C12)-alkyl, —(C3-C12)-cycloalkyl, —(C3-C12)-heterocycloalkyl or —(C6-C20)-aryl, may each independently be substituted by one or more substituents selected from —(C1-C12)-alkyl, —(C3-C12)-cycloalkyl, —(C3-C12)-heterocycloalkyl, —O—(C1-C12)-alkyl, —O—(C1-C12)-alkyl-(C6-C20)-aryl, —O—(C3-C12)-cycloalkyl, —S—(C1-C12)-alkyl, —S—(C3-C12)-cycloalkyl, —COO—(C1-C12)-alkyl, —COO—(C3-C12)-cycloalkyl, —CONH—(C1-C12)-alkyl, —CONH—(C3-C12)-cycloalkyl, —CO—(C1-C12)-alkyl, —CO—(C3-C12)-cycloalkyl, —N—[(C1-C12)-alkyl]2, —(C6-C20)-aryl, —(C6-C20)-aryl-(C1-C12)-alkyl, —(C6-C20)-aryl-O—(C1-C12)-alkyl, —(C3-C20)-heteroaryl, —(C3-C20)-heteroaryl-(C1-C12)-alkyl, —(C3-C20)-heteroaryl-O—(C1-C12)-alkyl, —COOH, —OH, —SO3H, —NH2, halogen. The invention further relates to Pd complex mixtures comprising the diastereomers according to the invention, and to the use thereof in an alkoxycarbonylation process.

## Claims

### Claim 1

Diastereomer mixture comprising diastereomers of the formulae (I.1) and (I.2)
where
R2, R4 are each independently selected from —(C1-C12)-alkyl, —(C3-C12)-cycloalkyl, —(C3-C12)-heterocycloalkyl, —(C6-C20)-aryl;
the R1, R3 radicals are each a —(C3-C20)-heteroaryl radical;
R1, R3 may each independently be substituted by one or more substituents selected from —(C1-C12)-alkyl, —(C3-C12)-cycloalkyl, —(C3-C12)-heterocycloalkyl, —O—(C1-C12)-alkyl, —O—(C1-C12)-alkyl-(C6-C20)-aryl, —O—(C3-C12)-cycloalkyl, —S—(C1-C12)-alkyl, —S—(C3-C12)-cycloalkyl, —COO—(C1-C12)-alkyl, —COO—(C3-C12)-cycloalkyl, —CONH—(C1-C12)-alkyl, —CONH—(C3-C12)-cycloalkyl, —CO—(C1-C12)-alkyl, —CO—(C3-C12)-cycloalkyl, —N—[(C1-C12)-alkyl]2, —(C6-C20)-aryl, —(C6-C20)-aryl-(C1-C12)-alkyl, —(C6-C20)-aryl-O—(C1-C12)-alkyl, —(C3-C20)-heteroaryl, —(C3-C20)-heteroaryl-(C1-C12)-alkyl, —(C3-C20)-heteroaryl-O—(C1-C12)-alkyl, —COOH, —OH, —SO3H, —NH2, halogen;
and
R2, R4, if they are —(C1-C12)-alkyl, —(C3-C12)-cycloalkyl, —(C3-C12)-heterocycloalkyl or —(C6-C20)-aryl, may each independently be substituted by one or more substituents selected from —(C1-C12)-alkyl, —(C3-C12)-cycloalkyl, —(C3-C12)-heterocycloalkyl, —O—(C1-C12)-alkyl, —O—(C1-C12)-alkyl-(C6-C20)-aryl, —O—(C3-C12)-cycloalkyl, —S—(C1-C12)-alkyl, —S—(C3-C12)-cycloalkyl, —COO—(C1-C12)-alkyl, —COO—(C3-C12)-cycloalkyl, —CONH—(C1-C12)-alkyl, —CONH—(C3-C12)-cycloalkyl, —CO—(C1-C12)-alkyl, —CO—(C3-C12)-cycloalkyl, —N—[(C1-C12)-alkyl]2, —(C6-C20)-aryl, —(C6-C20)-aryl-(C1-C12)-alkyl, —(C6-C20)-aryl-O—(C1-C12)-alkyl, —(C3-C20)-heteroaryl, —(C3-C20)-heteroaryl-(C1-C12)-alkyl, —(C3-C20)-heteroaryl-O—(C1-C12)-alkyl, —COOH, —OH, —SO3H, —NH2, halogen.

### Claim 2 (depends on 1)

Diastereomer mixture according to claim 1,
where the molar ratio of (I.1) to (I.2) is in the range from 10:90 to 70:30.

### Claim 3 (depends on 1)

Diastereomer mixture according to claim 1,
where R2, R4 are each independently selected from —(C1-C12)-alkyl, cyclohexyl and phenyl.

### Claim 4 (depends on 1)

Diastereomer mixture according to claim 1,
where R1, R3 are each a heteroaryl radical having five to ten ring atoms.

### Claim 5 (depends on 1)

Diastereomer mixture according to claim 1,
where R1, R3 are each pyridyl.

### Claim 6 (depends on 1)

Diastereomer mixture according to claim 1,
where R1, R3 are each identical radicals and R2, R4 are each identical radicals.

### Claim 7 (depends on 1)

Diastereomer mixture according to claim 1,
where the diastereomers I.1 and I.2 are compounds of the formula (8.1) and (8.2)

### Claim 8 (depends on 1)

Complex mixture comprising a first complex comprising Pd and a diastereomer of formula (I.1) and a second complex comprising Pd and a diastereomer of formula (I.2); each formula according to claim 1.

### Claim 9 (depends on 1)

Process comprising the following process steps:
a) initially charging an ethylenically unsaturated compound;
b) adding a diastereomer mixture according to claim 1 and a compound comprising Pd;
c) adding an alcohol;
d) feeding in CO;
e) heating the reaction mixture, with conversion of the ethylenically unsaturated compound to an ester.

### Claim 10 (depends on 9)

Process according to claim 9,
wherein the ethylenically unsaturated compound comprises 2 to 30 carbon atoms and optionally one or more functional groups selected from carboxyl, thiocarboxyl, sulpho, sulphinyl, carboxylic anhydride, imide, carboxylic ester, sulphonic ester, carbamoyl, sulphamoyl, cyano, carbonyl, carbonothioyl, hydroxyl, sulphhydryl, amino, ether, thioether, aryl, heteroaryl or silyl groups and/or halogen substituents.

### Claim 11 (depends on 9)

Process according to claim 9,
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, and mixtures thereof.

### Claim 12 (depends on 9)

Process according to claim 9,
wherein the ethylenically unsaturated compound comprises 6 to 22 carbon atoms.

### Claim 13 (depends on 9)

Process according to claim 9,
wherein the compound comprising Pd in process step b) is selected from palladium dichloride, palladium(II) acetylacetonate, palladium(II) acetate, dichloro(1,5-cyclooctadiene)palladium(II), bis(dibenzylideneacetone)palladium, bis(acetonitrile)dichloropalladium(II), palladium(cinnamyl) dichloride.

### Claim 14 (depends on 9)

Process according to claim 9,
wherein the alcohol in process step c) is selected from methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 2-propanol, tert-butanol, 3-pentanol, cyclohexanol, phenol, and mixtures thereof.

### Claim 15 (depends on 1)

A process for the catalysis of an alkoxycarbonylation reaction, comprising introducing the compound according to claim 1.

### Claim 16 (depends on 8)

Process comprising the following process steps:
a) initially charging an ethylenically unsaturated compound;
b) adding a complex mixture according to claim 8;
c) adding an alcohol;
d) feeding in CO;
e) heating the reaction mixture, with conversion of the ethylenically unsaturated compound to an ester.

### Claim 17 (depends on 16)

Process according to claim 16,
wherein the ethylenically unsaturated compound comprises 2 to 30 carbon atoms and optionally one or more functional groups selected from carboxyl, thiocarboxyl, sulpho, sulphinyl, carboxylic anhydride, imide, carboxylic ester, sulphonic ester, carbamoyl, sulphamoyl, cyano, carbonyl, carbonothioyl, hydroxyl, sulphhydryl, amino, ether, thioether, aryl, heteroaryl or silyl groups and/or halogen substituents.

### Claim 18 (depends on 16)

Process according to claim 16,
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, and mixtures thereof.

### Claim 19 (depends on 16)

Process according to claim 16,
wherein the alcohol in process step c) is selected from methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 2-propanol, tert-butanol, 3-pentanol, cyclohexanol, phenol, and mixtures thereof.

### Claim 20 (depends on 8)

A process for the catalysis of an alkoxycarbonylation reaction comprising;
introducing the complex mixture according to claim 8.