Bisphosphites having an unsymmetric central biaryl unit

Patent metadata

Field	Value
Publication number	US-9982001-B2
Application number	US-201514958143-A
Country	US
Kind code	B2
Filing date	Dec 3, 2015
Priority date	Dec 4, 2014
Publication date	May 29, 2018
Grant date	May 29, 2018

Abstract

Bisphosphites having an unsymmetric central biaryl unit.

First claim

The invention claimed is:

1. A compound having one of the four general structures I to IV:

where
R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 are selected from the group consisting of —H, —(C 1 -C 12 )-alkyl, —O—(C 1 -C 12 )-alkyl, —O—(C 6 -C 20 )-aryl, —(C 6 -C 20 )-aryl, —S-alkyl, —S-aryl, halogen, COO—(C 1 -C 12 )-alkyl, CONH—(C 1 -C 12 )-alkyl, —CO—(C 1 -C 12 )-alkyl, —CO—(C 6 -C 20 )-aryl, —COOH, —OH, —SO 3 H, —CN, —NH 2 , and —N[(C 1 -C 12 )-alkyl] 2 ;
R 1 ′, R 2 ′, R 3 ′, R 4 ′, R 5 ′, R 6 ′, R 7 ′, R 8 ′, R 1 ″, R 2 ″, R 3 ″, R 4 ″, R 5 ″, R 6 ″, R 7 ″, R 8 ″ are selected from the group consisting of —H, —(C 1 -C 12 )-alkyl, —O—(C 1 -C 12 )-alkyl, —O—(C 6 -C 20 )-aryl, —(C 6 -C 20 )-aryl, —S-alkyl, —S-aryl, halogen, COO—(C 1 -C 12 )-alkyl, CONH—(C 1 -C 12 )-alkyl, —CO—(C 1 -C 12 )-alkyl, —CO—(C 6 -C 20 )-aryl, —COOH, —OH, —SO 3 H, —NH 2 , and —N[(C 1 -C 12 )-alkyl] 2 ;
R 9 ′, R 10 ′, R 11 ′, R 12 ′, R 9 ″, R 10 ″, R 11 ″, R 12 ″ are selected from:
—H or —(C 6 -C 20 )-aryl;
and the two radicals in at least two of the four following radical pairs are not the same radical: R 1 and R 8 , R 2 and R 7 , R 3 and R 6 , R 4 and R 5 ;
where the alkyl and aryl groups mentioned may be substituted.

2. The compound according to claim 1 , where the compound has the general structure (I).

3. The compound according to claim 1 , where the compound has the general structure (II).

4. The compound according to claim 1 , where the compound has the general structure (III).

5. The compound according to claim 1 , where the compound has the general structure (IV).

6. The compound according to claim 1 , where R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 are selected from the group consisting of —H, —(C 1 -C 12 )-alkyl, —O—(C 1 -C 12 )-alkyl, —O—(C 6 -C 20 )-aryl, —S-alkyl, and —S-aryl.

7. The compound according to claim 1 , where R 1 ′, R 2 ′, R 3 ′, R 4 ′, R 5 ′, R 6 ′, R 7 ′, R 8 ′, R 1 ″, R 2 ″, R 3 ″, R 4 ″, R 5 ″, R 6 ″, R 7 ″, R 8 ″ are selected from the group consisting of —H, —(C 1 -C 12 )-alkyl, —O—(C 1 -C 12 )-alkyl, —O—(C 6 -C 20 )-aryl, —S-alkyl, and —S-aryl.

8. The compound according to claim 1 , where R 9 ′, R 10 ′, R 11 ′, R 12 ′, R 9 ″, R 10 ″, R 11 ″, R 12 ″ are each —(C 6 -C 20 )-aryl.

9. The compound according to claim 1 , where at least R 1 and R 8 are not the same radical.

10. The compound according to claim 1 , where R 9 ′, R 10 ′, R 11 ′, R 12 ′, R 9 ″, R 10 ″, R 11 ″, R 12 ″ are each the same radical.

11. The compound according to claim 1 ,
where the two radicals in at least one of the four following radical pairs are not the same radical: R 1 ′ and R 8 ′, R 2 ′ and R 7 ′, R 3 ′ and R 6 ′, R 4 ′ and R 5 ′,
and the two radicals in at least one of the four following radical pairs are not the same radical: R 1 ″ and R 8 ″, R 2 ″ and R 7 ″, R 3 ″ and R 6 ″, R 4 ″ and R 5 ″.

12. The compound according to claim 1 ,
where the two radicals in at least one of the four following radical pairs are not the same radical: R 1 ′ and R 8 ′, R 2 ′ and R 7 ′, R 3 ′ and R 6 ′, R 4 ″ and R 5 ′,
and the two radicals in the four following radical pairs are the same radical: R 1 ″ and R 8 ″, R 2 ″ and R 7 ″, R 3 ″ and R 6 ″, R 4 ″ and R 5 ″.

13. A complex comprising:
a compound according to claim 1 ,
a metal atom selected from the group consisting of Rh, Ru, Co, and Ir.

14. A method for catalysis of a hydroformylation reaction, comprising:
introducing the compound according to claim 1 .

15. A process comprising the following process steps:
a) initially charging an olefin,
b) adding a complex according to claim 13 ,
or a compound having one of the four general structures I to IV:

where
R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 are selected from the group consisting of
—H, —(C 1 -C 12 )-alkyl, —O—(C 1 -C 12 )-alkyl, —O—(C 6 -C 20 )-aryl, —(C 6 -C 20 )-aryl, —S-alkyl, —S-aryl, halogen, COO—(C 1 -C 12 )-alkyl, CONH—(C 1 -C 12 )-alkyl, —CO—(C 1 -C 12 )-alkyl, —CO—(C 6 -C 20 )-aryl, —COOH, —OH, —SO 3 H, —CN, —NH 2 , and —N[(C 1 -C 12 )-alkyl] 2 ;
R 1 ′, R 2 ′, R 3 ′, R 4 ′, R 5 ′, R 6 ′, R 7 ′, R 8 ′, R 1 ″, R 2 ″, R 3 ″, R 4 ″, R 5 ″, R 6 ″, R 7 ″, R 8 ″ are selected from the group consisting of
—H, —(C 1 -C 12 )-alkyl, —O—(C 1 -C 12 )-alkyl, —O—(C 6 -C 20 )-aryl, —(C 6 -C 20 )-aryl, —S-alkyl, —S-aryl, halogen, COO—(C 1 -C 12 )-alkyl, CONH—(C 1 -C 12 )-alkyl, —CO—(C 1 -C 12 )-alkyl, —CO—(C 6 -C 20 )-aryl, —COOH, —OH, —SO 3 H, —NH 2 , and —N[(C 1 -C 12 )-alkyl] 2 ;
R 9 ′, R 10 ′, R 11 ′, R 12 ′, R 9 ″, R 10 ″, R 11 ″, R 12 ″ are selected from:
—H or —(C 6 -C 20 )-aryl;
and the two radicals in at least two of the four following radical pairs are not the same radical: R 1 and R 8 , R 2 and R 7 , R 3 and R 6 , R 4 and R 5 ;
where the alkyl and aryl groups mentioned may be substituted,
and a substance including a metal atom selected from the group consisting of Rh, Ru, Co, and Ir,
c) feeding in H 2 and CO,
d) heating the reaction mixture, with conversion of the olefin to an aldehyde.

Assignees

• Dyballa Katrin Marie
• Franke Robert
• Fridag Dirk
• Boerner Armin
• Selent Detlef
• Evonik Degussa Gmbh

Inventors

• Dyballa Katrin Marie
• Franke Robert
• Fridag Dirk
• Börner Armin
• Selent Detlef

Classifications

• C07F15/0073

  Rhodium compounds · CPC title

• C07F15/0046

  Ruthenium compounds · CPC title

• C07C45/50

  by oxo-reactions · CPC title

• B01J31/185

  Phosphites ((RO)3P) , their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof · CPC title

• B01J2531/0241

  Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution · CPC title