Heterocyclic selenamonophosphites protected on a hydroxyl group and processes for preparation thereof

Patent metadata

Field	Value
Publication number	US-10100071-B2
Application number	US-201615370437-A
Country	US
Kind code	B2
Filing date	Dec 6, 2016
Priority date	Dec 7, 2015
Publication date	Oct 16, 2018
Grant date	Oct 16, 2018

Abstract

Novel heterocyclic selenamonophosphites protected on the hydroxyl group, processes for preparation thereof and the use thereof as ligand.

First claim

The invention claimed is:

1. A heterocyclic selenaphosphite compound having a general structure (I)

where R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are each independently selected from: —H, —(C 1 -C 12 )-alkyl, —O—(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl, —O—(C 6 -C 20 )-aryl, -halogen, —OC═O—(C 1 -C 12 )-alkyl, —S-alkyl, —S-aryl, —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, —SO 3 H, —CN, or —N[(C 1 -C 12 )-alkyl] 2 , where the alkyl groups are linear, branched or cyclic, where the alkyl and aryl groups are each independently unsubstituted or substituted, where each substituted —(C 1 -C 12 )-alkyl group and substituted —(C 6 -C 20 )-aryl group have at least one substituent and the at least one substituent is each independently selected from —(C 3 -C 12 )-cycloalkyl, —(C 3 -C 12 )-heterocycloalkyl, —(C 6 -C 20 )-aryl, fluorine, chlorine, cyano, formyl, acyl, or alkoxycarbonyl, and
where the —R 1 group is selected from: —(C 1 -C 12 )-alkyl, —(C 1 -C 12 )-alkyl-O—(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl, —(C 1 -C 12 )-alkyl-O—(C 6 -C 20 )-aryl, —(C 6 -C 20 )-aryl-O—(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl-O—(C 6 -C 20 )-aryl, —(C═O)—O—(C 1 -C 12 )-alkyl, -acetyl,
where the alkyl groups are linear, branched or cyclic, where the alkyl and aryl groups mentioned are each independently unsubstituted or substituted, where substituted —(C 1 -C 12 )-alkyl groups and substituted —(C 6 -C 20 )-aryl groups have at least one substituent and the at least one substituent in each case is independently selected from —(C 3 -C 12 )-cycloalkyl, —(C 3 -C 12 )-heterocycloalkyl, —(C 6 -C 20 )-aryl, fluorine, chlorine, cyano, formyl, acyl, or alkoxycarbonyl,
and the —R 1 * group is an organofunctional phosphite group.

2. The compound according to claim 1 , wherein in the heterocyclic selenaphosphite of the general structure (I) —R 1 * is an organofunctional phosphite group selected from the structures (II), (III), (IV, (V), (VI) and (VII)

where the radicals
R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 in structure (II),
R 10 , R 11 , R 12 , R 13 , R 14 , R 10 *, R 11 *, R 12 *, R 13 *, R 14 * in the structure (III),
R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , R 31 , and R 32 in structure (IV),
R 43 , R 44 , R 45 , R 46 , R 47 , R 48 , R 49 , R 50 , R 51 , R 52 , R 53 and R 54 in structure (V), and
R 55 , R 56 , R 57 , R 58 , R 59 and R 60 in structure (VII).
in each case in the respective structure are independently selected from: —H, —(C 1 -C 12 )-alkyl, —O—(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl, —O—(C 6 -C 20 )-aryl, or -halogen, where the alkyl groups are linear, branched or cyclic, where the alkyl and aryl groups are each independently unsubstituted or substituted, where each substituted —(C 1 -C 12 )-alkyl group and each substituted —(C 6 -C 20 )-aryl group has at least one substituent and the at least one substituent in each case is independently selected from —(C 3 C 12 )-cycloalkyl, —(C 3 -C 12 )-heterocycloalkyl, —(C 6 -C 20 )-aryl, fluorine, chlorine, cyano, formyl, acyl or alkoxycarbonyl.

3. The compound according to claim 1 , wherein the —R 1 group in the structure (I) is selected from: —(C 1 -C 12 )-alkyl, —(C 1 -C 12 )-alkyl-O—(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl, —(C 6 -C 20 )-aryl-O—(C 1 -C 12 )alkyl, —(C 1 -C 12 )-alkyl-O—(C 6 -C 20 )-aryl, —(C 6 -C 20 )-aryl-O—(C 6 -C 20 )-aryl, —(C═O)—O—(C 1 -C 12 )-alkyl, where the alkyl groups are linear, branched or cyclic, where the alkyl and aryl groups mentioned are each independently unsubstituted or substituted, where substituted —(C 1 -C 12 )-alkyl groups and substituted —(C 6 -C 20 )-aryl groups have at least one substituent and the at least one substituent in each case is independently selected from —(C 3 -C 12 )-cycloalkyl and/or —(C 6 -C 20 )-aryl.

4. The compound according to claim 1 , wherein the heterocyclic selenaphosphite of the general structure (I) is compound of structure (Ia)

where R 2 , R 4 , R 7 and R 9 are each independently selected from:
—(C 1 -C 12 )-alkyl, —O—(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl, —O—(C 6 -C 20 )-aryl, or -halogen, where the alkyl groups are linear, branched or cyclic,
where the —R 1 group is selected from: —(C 1 -C 12 )-alkyl, —(C 1 -C 12 )-alkyl-O—(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl, —(C 1 -C 12 )-alkyl-O—(C 6 -C 20 )-aryl, —(C 6 -C 20 )-aryl-O—(C 1 -C 12 )-alkyl, or —(C 6 -C 20 )-aryl-O—(C 6 -C 20 )-aryl, where the alkyl groups are linear, branched or cyclic,
and the —R 1 * group in structure (Ia) is an organofunctional phosphite group.

5. The compound according to claim 4 , wherein the —R 1 * in the heterocyclic selenaphosphite of the structure (Ia) is selected from the structures (II), (III), (IV), (V), (VI) and (VII)

where the radicals
R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 in structure (II),
R 10 , R 11 , R 12 , R 13 , R 14 , R 10 *, R 11 *, R 12 *, R 13 *, R 14 * in the structure (III),
R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , R 31 , and R 32 in structure (IV),
R 43 , R 44 , R 45 , R 46 , R 47 , R 48 , R 49 , R 50 , R 51 , R 52 , R 53 and R 54 in structure (V), and
R 55 , R 56 , R 57 , R 58 , R 59 and R 60 in structure (VII),
in each case for each structure are independently selected from: —H, —(C 1 -C 12 )-alkyl, —O—(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl, —O—(C 6 -C 20 )-aryl, or -halogen, where the alkyl groups are linear, branched or cyclic.

6. The compound according to claim 4 , wherein the —R 1 * in the heterocyclic selenaphosphite of the structure (Ia) is selected from structure (III)
and the —R 1 group is selected from —(C 1 -C 12 )-alkyl, —(C 1 -C 12 )-alkyl-O—(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl, —(C 1 -C 12 )-alkyl-O—(C 6 -C 20 )-aryl, —(C 6 -C 20 )-aryl-O—(C 1 -C 12 )-alkyl, or —(C 6 -C 20 )-aryl-O—(C 6 -C 20 )-aryl, where the alkyl groups are linear, branched or cyclic,

where R 2 , R 4 , R 7 and R 9 in structure (Ia) are each independently selected from —(C 1 -C 12 )-alkyl, or —O—(C 1 -C 12 )-alkyl, where the alkyl groups are linear, branched or cyclic, and

with R 10 , R 11 , R 12 , R 13 , R 14 , R 10 *, R 11 *, R 12 *, R 13 *, R 14 * in the structure (III) each independently selected from: —H, —(C 1 -C 12 )-alkyl, —O—(C 1 -C 12 )-alkyl, where the alkyl groups are linear, branched or cyclic.

7. A rhodium hydroformylation catalyst, comprising: the compound according to claim 1 as a ligand.

8. A process for preparing at least one heterocyclic selenephosphite of the general structure (I)

where R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are each independently selected from: —H, —(C 1 -C 12 )-alkyl, —O—(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl, —O—(C 6 -C 20 )-aryl, -halogen, —OC═O—(C 1 -C 12 )-alkyl, —S-alkyl, —S-aryl, —

Assignees

• Evonik Degussa Gmbh

Inventors

• Dyballa Katrin Marie
• Franke Robert
• Weilbeer Claudia
• Selent Detlef
• Börner Armin

Classifications

• C07C391/02

  having selenium atoms bound to carbon atoms of six-membered aromatic rings · CPC title

• C07F9/65522

  condensed with carbocyclic rings or carbocyclic ring systems · CPC title

• C07F9/65527 Primary

  condensed with carbocyclic rings or carbocyclic ring systems · CPC title

• C07F9/65744

  condensed with carbocyclic or heterocyclic rings or ring systems · CPC title

• C07F9/65517

  condensed with carbocyclic rings or carbocyclic ring systems · CPC title