Monophosphine compounds and palladium catalysts based thereon for the alkoxycarbonylation of ethylenically unsaturated compounds

Patent metadata

Field	Value
Publication number	US-10294191-B2
Application number	US-201615213449-A
Country	US
Kind code	B2
Filing date	Jul 19, 2016
Priority date	Jul 23, 2015
Publication date	May 21, 2019
Grant date	May 21, 2019

Abstract

The invention further relates to Pd complexes comprising the compound according to the invention and to the use thereof in alkoxycarbonylation.

First claim

The invention claimed is:

1. Compound of formula (I)

where
R 1 is selected from the group consisting of —(C 1 -C 12 )-alkyl, —(C 3 -C 12 )-cycloalkyl and —(C 3 -C 12 )-heterocycloalkyl;
R 2 is selected from the group consisting of phenyl, pyrimidyl and 2-imidazolyl;
R 3 is 2-imidazolyl;
and R 1 , R 2 and R 3 may each independently be substituted by one or more substituents selected from the group consisting of —(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-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 and halogen.

2. Compound according to claim 1 ,
where R 1 is —(C 1 -C 12 )-alkyl.

3. A compound having formulae (1)

4. Complex comprising Pd and a compound of formula (I)

where
R 1 is selected from the group consisting of —(C 1 -C 12 )-alkyl, —(C 3 -C 12 )-cycloalkyl and —(C 3 -C 12 )-heterocycloalkyl;
R 2 is selected from the group consisting of phenyl, pyrimidyl and 2-imidazolyl;
R 3 is imidazolyl;

and R 1 , R 2 and R 3 may each independently be substituted by one or more substituents selected from the group consisting of —(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-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 and halogen.

5. Process comprising the following process steps:
a) initially charging an ethylenically unsaturated compound;
b) adding a compound of formula (I)

where
R 1 is selected from the group consisting of —(C 1 -C 12 )-alkyl, —(C 3 -C 12 )-cycloalkyl and —(C 3 -C 12 )-heterocycloalkyl;
R 2 is selected from the group consisting of phenyl, pyrimidyl and 2-imidazolyl;
R 3 is imidazolyl;
and R 1 , R 2 and R 3 may each independently be substituted by one or more substituents selected from the group consisting of —(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-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 and halogen, and a compound comprising Pd,
or adding a complex according to claim 4 ;

c) adding an alcohol;
d) feeding in CO;
e) heating the reaction mixture, with conversion of the ethylenically unsaturated compound to an ester.

6. Process according to claim 5 ,
wherein the ethylenically unsaturated compound is selected from the group consisting of 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.

7. Process according to claim 5 ,
wherein the compound comprising Pd in process step b) is selected from the group consisting of palladium dichloride, palladium(II) acetylacetonate, palladium(II) acetate, dichloro(1,5-cycloocta-diene)palladium(II), bis(dibenzylideneacetone)palladium, bis(acetonitrile)dichloro-palladium(II) and palladium(cinnamyl) dichloride.

8. Process according to claim 5 ,
wherein the alcohol in process step c) is selected from the group consisting of methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 2-propanol, tert-butanol, 3-pentanol, cyclohexanol, phenol and mixtures thereof.

9. Process according to claim 5 , wherein the alcohol in process step c) is an aliphatic alcohol.

10. A process for catalysis of an alkoxycarbonylation reaction, comprising: introducing a compound of formula (I)

where
R 1 is selected from the group consisting of —(C 1 -C 12 )-alkyl, —(C 3 -C 12 )-cycloalkyl and —(C 3 -C 12 )-heterocycloalkyl;
R 2 is selected from the group consisting of phenyl, pyrimidyl and 2-imidazolyl;
R 3 is imidazolyl;
and R 1 , R 2 and R 3 may each independently be substituted by one or more substituents selected from the group consisting of
—(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-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 and halogen or a complex according to claim 4 .

Assignees

• Evonik Degussa Gmbh

Inventors

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

Classifications

• C07F9/5045

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

• B01J31/2409

  with more than one complexing phosphine-P atom · CPC title

• B01J31/12

  containing organo-metallic compounds or metal hydrides · CPC title

• C07F9/572

  Five-membered rings · CPC title

• B01J2231/49

  Esterification or transesterification · CPC title