Method for preparing di- or tricarboxylic esters by alkoxycarbonylation of dienes having conjugated double bonds

Patent metadata

Field	Value
Publication number	US-9981903-B2
Application number	US-201715651105-A
Country	US
Kind code	B2
Filing date	Jul 17, 2017
Priority date	Jul 19, 2016
Publication date	May 29, 2018
Grant date	May 29, 2018

Abstract

The invention relates to a method for preparing di- or tricarboxylic esters by alkoxycarbonylation of dienes having conjugated double bonds. The method includes the steps of initially charging a diene having two conjugated double bonds, adding a phosphine ligand according to formula (I) and a catalyst precursor, adding an alcohol, feeding in CO, and heating the reaction mixture with conversion of the diene to a di- or tricarboxylic ester.

First claim

The invention claimed is:

1. A method for preparing di- or tricarboxylic esters in a reaction mixture, comprising the method steps of:
a) initially charging a diene having two conjugated double bonds, wherein the diene is selected from compounds of the formula (II)

where R 7 , R 8 , R 9 , R 10 may each independently be selected from —H, —(C 1 -C 12 )-alkyl, or —(C 6 -C 20 )-aryl;
b) adding a phosphine ligand and a catalyst precursor selected from palladium dichloride, palladium dibromide, palladium diiodide, palladium(II) acetylacetonate, palladium(II) acetate, bis(dibenzylideneacetone)palladium, bis(acetonitrile)dichloropalladium(II), or palladium (cinnamyl) dichloride;
c) adding an alcohol;
d) feeding in CO;
e) heating the reaction mixture, with conversion of the diene to a di- or tricarboxylic ester;
wherein the phosphine ligand is a compound according to formula (I)

where
R 1 , R 2 , R 3 , R 4 are selected from —(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl, —(C 3 -C 12 )-cycloalkyl, —(C 3 -C 12 )-heterocycloalkyl, or —(C 3 -C 20 )-heteroaryl;
R 5 , R 6 are selected from —H, —(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl, —(C 3 -C 12 )-cycloalkyl, —(C 3 -C 12 )-heterocycloalkyl, or —(C 3 -C 20 )-heteroaryl;
and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , in the case that these are —(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl, —(C 3 -C 12 )-cycloalkyl, —(C 3 -C 12 )-heterocycloalkyl or —(C 3 -C 20 )-heteroaryl, may be each substituted independently of one another 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 , or halogen, and
wherein steps a), b), c), and d) may be effected in any sequence.

2. The method according to claim 1 ,
where R 1 , R 2 , R 3 , R 4 are selected from —(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl, or (C 3 -C 20 )-heteroaryl.

3. The method according to claim 1 ,
where R 5 , R 6 are selected from —H or —(C 1 -C 12 )-alkyl.

4. The method according to claim 1 ,
where R 1 , R 2 , R 3 , R 4 are each —(C 6 -C 20 )-aryl and R 5 , R 6 are each selected from —H or —(C 1 -C 12 )-alkyl.

5. The method according to claim 1 ,
wherein the diene has 4 to 30 carbon atoms.

6. The method according to claim 1 ,
wherein the catalyst precursor is selected from palladium dichloride, palladium dibromide, palladium diiodide, palladium(II) acetylacetonate, palladium(II) acetate, or bis(dibenzylideneacetone)palladium.

7. The method according to claim 1 ,
wherein the catalyst precursor is selected from palladium dichloride, palladium dibromide, or palladium diiodide.

8. The method according to claim 1 ,
wherein the alcohol in method step c) has 1 to 12 carbon atoms.

9. The method according to claim 1 ,
wherein the alcohol in method step c) is selected from methanol, ethanol, 1-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol, cyclohexanol, 2-ethylhexanol, isononanol, 2-propylheptanol, benzyl alcohol, 1-phenylethanol or 2-phenylethanol.

10. The method according to claim 1 ,
wherein the alcohol in method step c) is selected from methanol, ethanol, isopropanol, n-butanol or 2-phenylethanol.

11. The method of claim 1 , wherein R 7 , R 8 , R 9 , R 10 may each independently be selected from —H, —(C 1 -C 6 )-alkyl, or phenyl.

Assignees

• Evonik Degussa Gmbh

Inventors

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

Classifications

• C07C67/38 Primary

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

• B01J2531/824

  Palladium · CPC title

• B01J31/2495

  Ligands comprising a phosphine-P atom and one or more further complexing phosphorus atoms covered by groups B01J31/1845 - B01J31/1885, e.g. phosphine/phosphinate or phospholyl/phosphonate ligands · CPC title

• C07C69/44

  Adipic acid esters · CPC title

• B01J27/13

  Platinum group metals · CPC title