Catalysts and methods for forming alkenyl substituted arenes

Patent metadata

Field	Value
Publication number	US-11833494-B2
Application number	US-202318163647-A
Country	US
Kind code	B2
Filing date	Feb 2, 2023
Priority date	Mar 25, 2015
Publication date	Dec 5, 2023
Grant date	Dec 5, 2023

Abstract

Embodiments of the present disclosure provide for Rh(I) catalysts, methods of making alkenyl substituted arenes (e.g., allyl arene, vinyl arene, and the like), methods of making alkyl substituted arenes, and the like.

First claim

The invention claimed is:

1. A method of making a substituted arene, comprising reacting an arene and olefin with a catalyst and an oxidant, with the proviso that the method is performed in the absence of CO, wherein the catalyst is:
L 2 Rh(L′)X;

wherein:
each L is independently a neutral ligand coordinated to Rh(I) through a carbon donor, nitrogen donor, a phosphorus donor, an oxygen donor, or a sulfur donor; wherein each L is independently selected from an amine, a pyridine, a phosphine, a phosphite, an ether, a ketone, or an imine;
L′ is a neutral ligand selected from an amine, a pyridine, a phosphine, a phosphite, an ether, a ketone, or an imine;
X is a monoanionic ligand selected from a halide, an alkyl, an alkenyl, a carbocycle group, a heterocyclo, an aryl, a heteroaryl, or a carboxylate;
wherein the oxidant is a copper(II) salt, iodate, periodate, nitrogen dioxide, silver salt, peroxide, dioxygen, air, or a combination thereof;
wherein the arene is benzene or naphthalene, wherein the arene is optionally substituted with 1-4 substituents selected from the group consisting of halo, methyl, carboxylate, nitro, and alkoxy;
wherein the olefin is:

and
R is hydrogen, a halide, an alkyl, an alkenyl, a carbocycle group, a heterocyclo, an aryl, or a heteroaryl;
to form a product, wherein the product is

2. The method of claim 1 , wherein the reacting is at a reaction temperature of 100° C. to 300° C.

3. The method of claim 1 , further comprising:
reacting the product with a second catalyst in the presence of H 2 .

4. The method of claim 1 , wherein the arene is selected from the group consisting of benzene, naphthalene, toluene, xylene, mesitylene, chlorobenzene, fluorobenzene, bromobenzene, iodobenzene, dichlorobenzene, difluorobenzene, or dibromobenzene.

5. The method of claim 1 , wherein the arene is benzene, naphthalene, or toluene.

6. The method of claim 1 , wherein the olefin is ethylene, propylene, pentene, hexene, or isobutylene.

7. The method of claim 1 , wherein the arene and olefin are present in a molar ratio of arene to olefin of 1:100 to 1000:1.

8. The method of claim 1 , wherein the catalyst is present in an amount of 5 mol % to 0.00001 mol % relative to arene.

9. The method of claim 1 , wherein the olefin is a gaseous olefin at a pressure of 10 psig to 5000 psig.

10. The method of claim 1 , wherein the olefin is a gaseous olefin at a pressure of 10 psig to 90 psig.

Assignees

• The Univ Of Virginia Patent Foundation
• Univ Virginia Patent Foundation

Inventors

• Gunnoe Thomas B
• Vaughan Benjamin Austin
• Webster-Gardiner Michael S

Classifications

• B01J31/1815 Primary

  with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine · CPC title

• B01J31/00

  Catalysts comprising hydrides, coordination complexes or organic compounds (catalyst compositions used only in polymerisation reactions C08 {; catalytic antibodies C12N9/0002}) · CPC title

• B01J31/189

  containing both nitrogen and phosphorus as complexing atoms, including e.g. phosphino moieties, in one at least bidentate or bridging ligand · CPC title

• B01J31/2226

  Anionic ligands, i.e. the overall ligand carries at least one formal negative charge · CPC title

• B01J31/2291

  Olefins · CPC title