1, 1′-bis(phosphino)ferrocene ligands for alkoxycarbonylation

Patent metadata

Field	Value
Publication number	US-9938310-B2
Application number	US-201715649759-A
Country	US
Kind code	B2
Filing date	Jul 14, 2017
Priority date	Jul 19, 2016
Publication date	Apr 10, 2018
Grant date	Apr 10, 2018

Abstract

Diastereomer mixture comprising diastereomers of the formulae (I.1) and (I.2)

where

R 2 , R 4 are each independently selected from —(C 1 -C 12 )-alkyl, —(C 3 -C 12 )-cycloalkyl, —(C 3 -C 12 )-heterocycloalkyl, —(C 6 -C 20 )-aryl;

the R 1 , R 3 radicals are each a —(C 3 -C 20 )-heteroaryl radical.

The invention further relates to Pd complex mixtures comprising the diastereomers according to the invention, and to the use thereof in an alkoxycarbonylation process.

First claim

The invention claimed is:

1. Diastereomer mixture comprising diastereomers of the formulae (I.1) and (I.2)

where
R 2 , R 4 are each independently selected from —(C 1 -C 12 )-alkyl, —(C 3 -C 12 )-cycloalkyl, —(C 3 -C 12 )-heterocycloalkyl, —(C 3 -C 20 )-aryl;
the R 1 , R 3 radicals are each a —(C 3 -C 20 )-heteroaryl radical;
R 1 , R 3 may each independently be substituted by one or more substituents selected from —(C 1 -C 12 )-alkyl, —(C 3 -C 12 )-cycloalkyl, —(C 3 -C 12 )-heterocycloalkyl, —O—(C 1 -C 12 )-alkyl, —O—(C 1 -C 12 )-alkyl-(C 6 -C 20 )-aryl, —O—(C 3 -C 12 )-cycloalkyl, —S—(C 1 -C 12 )-alkyl, —S—(C 3 -C 12 )-cycloalkyl, —COO—(C 1 -C 12 )-alkyl, —COO—(C 3 -C 12 )-cycloalkyl, —CONH—(C 1 -C 12 )-alkyl, —CONH—(C 3 -C 12 )-cycloalkyl, —CO—(C 1 -C 12 )-alkyl, —CO—(C 3 -C 12 )-cycloalkyl, —N—[(C 1 -C 12 )-alkyl] 2 , —(C 6 -C 20 )-aryl, —(C 6 -C 20 )-aryl-(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl-O—(C 1 -C 12 )-alkyl, —(C 3 -C 20 )-heteroaryl, —(C 3 -C 20 )-heteroaryl-(C 1 -C 12 )-alkyl, —(C 3 -C 20 )-heteroaryl-O—(C 1 -C 12 )-alkyl, —COOH, —OH, —SO 3 H, —NH 2 , halogen;

and
R 2 , R 4 , if they are —(C 1 -C 12 )-alkyl, —(C 3 -C 12 )-cycloalkyl, —(C 3 -C 12 )-heterocycloalkyl or —(C 6 -C 20 )-aryl, may each independently be substituted by one or more substituents selected from —(C 1 -C 12 )-alkyl, —(C 3 -C 12 )-cycloalkyl, —(C 3 -C 12 )-heterocycloalkyl, —O—(C 1 -C 12 )-alkyl, —O—(C 1 -C 12 )-alkyl-(C 6 -C 20 )-aryl, —O—(C 3 -C 12 )-cycloalkyl, —S—(C 1 -C 12 )-alkyl, —S—(C 3 -C 12 )-cycloalkyl, —COO—(C 1 -C 12 )-alkyl, —COO—(C 3 -C 12 )-cycloalkyl, —CONH—(C 1 -C 12 )-alkyl, —CONH—(C 3 -C 12 )-cycloalkyl, —CO—(C 1 -C 12 )-alkyl, —CO—(C 3 -C 12 )-cycloalkyl, —N—[(C 1 -C 12 )-alkyl] 2 , —(C 6 -C 20 )-aryl, —(C 6 -C 20 )-aryl-(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl-O—(C 1 -C 12 )-alkyl, (C 3 -C 20 )-heteroaryl, —(C 3 -C 20 )-heteroaryl-(C 1 -C 12 )-alkyl, —(C 3 -C 20 )-heteroaryl-O—(C 1 -C 12 )-alkyl, —COOH, —OH, —SO 3 H, —NH 2 , halogen.

2. 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.

3. Diastereomer mixture according to claim 1 , where R 2 , R 4 are each independently selected from —(C 1 -C 12 )-alkyl, cyclohexyl and phenyl.

4. Diastereomer mixture according to claim 1 , where R 1 , R 3 are each a heteroaryl radical having five to ten ring atoms.

5. Diastereomer mixture according to claim 1 , where R 1 , R 3 are each pyridyl.

6. Diastereomer mixture according to claim 1 , where R 1 , R 3 are each identical radicals and R 2 , R 4 are each identical radicals.

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

8. 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 .

9. 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.

10. 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.

11. 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.

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

13. 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.

14. 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.

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

16. 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.

17. 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.

18. 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.

19. 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.

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

Assignees

• Evonik Degussa Gmbh

Inventors

• Dong Kaiwu
• Neumann Helfried
• Jackstell Ralf
• Beller Matthias
• Fridag Dirk
• Hess Dieter
• Dyballa Katrin Marie
• Geilen Frank
• Franke Robert

Classifications

• C07C67/62

  Use of additives, e.g. for stabilisation · CPC title

• C07F17/02 Primary

  of metals of Groups 8, 9 or 10 of the Periodic Table · CPC title

• C07C67/38

  by addition to an unsaturated carbon-to-carbon bond · CPC title

• C07F9/5045

  Complexes or chelates of phosphines with metallic compounds or metals · CPC title

• C07F15/0066

  without a metal-carbon linkage · CPC title