Catalysts and methods for forming alkenyl and alkyl substituted arenes

Patent metadata

Field	Value
Publication number	US-10967364-B2
Application number	US-201615561212-A
Country	US
Kind code	B2
Filing date	Mar 24, 2016
Priority date	Mar 25, 2015
Publication date	Apr 6, 2021
Grant date	Apr 6, 2021

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:

wherein A 1 and A 2 are independently selected from the group consisting of a halogen and an acetate group; and R 21 , R 22 , R 23 , and R 24 are each independently selected from an olefin:
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 2 , wherein the reaction temperature is 100° C. to 250° C.

4. The method of claim 1 , further comprising:
reacting the product with a second catalyst in the presence of H 2 , wherein the second catalyst is selected from the group consisting of: Pt/C, Pd/C, Raney Ni, Wilkinson's Catalyst, and PtO 2 .

5. 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.

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

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

8. 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.

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

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

11. 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

• B01J2540/22

  comprising fluorine, e.g. trifluoroacetate · 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

• B01J31/2291

  Olefins · CPC title

• B01J31/2226

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

• B01J2231/46

  C-H or C-C activation · CPC title