Metal carbene olefin metathesis catalysts

Patent metadata

Field	Value
Publication number	US-10501488-B2
Application number	US-201615762918-A
Country	US
Kind code	B2
Filing date	Sep 23, 2016
Priority date	Sep 24, 2015
Publication date	Dec 10, 2019
Grant date	Dec 10, 2019

Abstract

This invention relates generally to metal carbene olefin metathesis catalyst compounds, to the preparation of such compounds, compositions comprising such compounds, methods of using such compounds, articles of manufacture comprising such compounds, and the use of such compounds in the metathesis of olefins and olefin compounds. The invention has utility in the fields of catalysts, organic synthesis, polymer chemistry, and industrial and fine chemicals industry.

First claim

What is claimed is:

1. A metal carbene olefin metathesis catalyst represented by the structure of Formula (V):

wherein
Q is a two-atom linkage having the structure —CR 11 R 12 —CR 13 R 14 — or —CR 11 ═CR 13 —, wherein R 11 , R 12 , R 13 , and R 14 are independently hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, or functional groups;
R 3 and R 4 is unsubstituted phenyl or phenyl substituted with one or more substituents selected from the group consisting of C 1 -C 20 alkyl, substituted C 1 -C 20 alkyl, C 1 -C 20 heteroalkyl, substituted C 1 -C 20 heteroalkyl, C 5 -C 24 aryl, substituted C 5 -C 24 aryl, C 5 -C 24 heteroaryl, C 6 -C 24 aralkyl, C 6 -C 24 alkaryl, or halide;
X 1 and X 2 are independently halogen; and are bonded to Ru in a trans orientation;

L 2 is represented by Formula (1) or Formula (2):

wherein: R 1p , R 2p , R 3p are each independently substituted or unsubstituted C 6 -C 10 aryl, or substituted or unsubstituted C 1 -C 10 alkyl, or substituted or unsubstituted C 3 -C 8 cycloalkyl,

wherein: R 8p , R 9p , R 10p are each independently substituted or unsubstituted C 6 -C 10 aryl, or substituted or unsubstituted C 1 -C 10 alkyl, or substituted or unsubstituted C 3 -C 8 cycloalkyl,
m is 0, 1, or 2;
R 1 and R 2 are independently hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, or R 1 and R 2 may be linked together to form a ring that may be substituted or unsubstituted; and with the proviso that the catalyst of Formula (V) is not of structure:

2. The metal carbene olefin metathesis catalyst according to claim 1 , wherein:
m is 0;
Q is a two-atom linkage having the structure —CR 11 R 12 —CR 13 R 14 —, wherein R 11 , R 12 , R 13 , and R 14 are each hydrogen;
R 3 and R 4 are each phenyl substituted with up to three substituents selected from methyl or isopropyl;
X 1 and X 2 are Cl;
R 1 is hydrogen, R 2 is phenyl, vinyl, optionally substituted with one or more moieties selected from C 1 -C 6 alkyl, or C 1 -C 6 alkoxy; or R 1 and R 2 may be linked together to form a phenylindenylidene.

3. The metal carbene olefin metathesis catalyst according to claim 2 , wherein:
L 2 is represented by Formula (1):

wherein: R 1p , R 2p , R 3p are each independently substituted or unsubstituted C 6 -C 10 aryl, or substituted or unsubstituted C 1 -C 10 alkyl, or substituted or unsubstituted C 3 -C 8 cycloalkyl.

4. The metal carbene olefin metathesis catalyst according to claim 3 , wherein:
R 1p is selected from the group consisting of methyl, ethyl, isopropyl, n-butyl, sec-butyl, tert-butyl, 4-methoxyphenyl, benzyl and phenyl; and R 2p and R 3p are each phenyl.

5. The metal carbene olefin metathesis catalyst according to claim 4 , wherein the catalyst is selected from the group consisting of:

6. The metal carbene olefin metathesis catalyst according to claim 1 , wherein:
m is 0;
Q is a two-atom linkage having the structure —CR 11 R 12 —CR 13 R 14 —, wherein R 11 , R 12 , R 13 , and R 14 are independently hydrogen;
R 3 and R 4 are each phenyl substituted with up to three substituents selected from methyl or isopropyl;
X 1 and X 2 are Cl;
R 1 is hydrogen, R 2 is phenyl, vinyl, optionally substituted with one or more moieties selected from C 1 -C 6 alkyl, or C 1 -C 6 alkoxy; or R 1 and R 2 may be linked together to form a phenylindenylidene.

7. The metal carbene olefin metathesis catalyst according to claim 6 , wherein:
L 2 is represented by Formula (2):

wherein: R 8p , R 9p , R 10p are each independently substituted or unsubstituted C 6 -C 10 aryl, or substituted or unsubstituted C 1 -C 10 alkyl, or substituted or unsubstituted C 3 -C 8 cycloalkyl.

8. The metal carbene olefin metathesis catalyst according to claim 7 , wherein: R 8p and R 9p are each independently selected from methyl, ethyl, isopropyl, n-butyl, sec-butyl, tert-butyl, 4-methoxyphenyl, benzyl, or phenyl; and R 10p is phenyl.

9. The metal carbene olefin metathesis catalyst according to claim 8 , wherein the catalyst is selected from the group consisting of:

10. A ROMP composition comprising at least one resin composition and at least one metal carbene olefin metathesis catalyst, wherein the resin composition comprises at least one cyclic olefin and wherein the at least one metal carbene olefin metathesis catalyst is selected from the group consisting of:

11. The ROMP composition according to claim 10 , wherein the at least one cyclic olefin is a norbornene derivative.

12. A ROMP composition comprising at least one resin composition and at least one metal carbene olefin metathesis catalyst according to claim 1 , wherein the resin composition comprises at least one cyclic olefin.

13. The ROMP composition according to claim 12 , wherein the at least one cyclic olefin is a norbornene derivative.

14. A ROMP composition comprising at least one resin composition and at least one metal carbene olefin metathesis catalyst according to claim 4 , wherein the resin composition comprises at least one cyclic olefin.

15. The ROMP composition according to claim 14 , wherein the at least one cyclic olefin is a norbornene derivative.

16. A ROMP composition comprising at least one resin composition and at least one metal carbene olefin metathesis catalyst according to claim 8 , wherein the resin composition comprises at least one cyclic olefin.

17. The ROMP composition according to claim 16 , wherein the at least one cyclic olefin is a norbornene derivative.

Assignees

• Umicore Ag & Co Kg

Inventors

• Giardello Michael A
• Trimmer Mark S
• Wang Li-Sheng
• Duffy Noah H
• Johns Adam M
• Rodak Nicholas J
• Fiamengo Bryan A
• Phillips John H

Classifications

• C08G2261/418

  Ring opening metathesis polymerisation [ROMP] · CPC title

• C08G61/08

  of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring · CPC title

• C08G2261/3325

  derived from other polycyclic systems · CPC title

• C07F15/0046 Primary

  Ruthenium compounds · CPC title

• C08G2261/3324

  derived from norbornene · CPC title