Bridged phthalocyanine- and napththalocyanine-metal complex catalysts for oxidation reactions

Patent metadata

Field	Value
Publication number	US-11826740-B2
Application number	US-202217861715-A
Country	US
Kind code	B2
Filing date	Jul 11, 2022
Priority date	Jul 9, 2021
Publication date	Nov 28, 2023
Grant date	Nov 28, 2023

Abstract

Various embodiments disclosed relate to bridged phthalocyanine- and napththalocyanine-metal complex catalysts and methods using the same for oxidation reactions. In various embodiments, the present invention provides a method of oxidation including contacting an oxidizable starting material including an alkene with a catalyst and an oxidant, to provide an oxidized product.

First claim

What is claimed is:

1. A method of oxidation, comprising:
contacting an oxidizable starting material comprising an alkene with a catalyst and an oxidant, to provide an oxidized product;
wherein the catalyst has the structure

wherein
M is a metal,
axial ligand L is a solvent molecule,
at each occurrence, R A and R B are independently chosen from —H, halide, an organic group, and a hydrophilic group, or R A and R B together form a fused aromatic ring with the ring upon which R A and R B are substituted, R A and R B together having the structure:

and
at each occurrence, R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are each independently chosen from —H, halide, an organic group, and a hydrophilic group.

2. The method of claim 1 , wherein the oxidant comprises oxygen.

3. The method of claim 1 , wherein the contacting is conducted in the presence of air to provide oxygen as the oxidant from the air.

4. The method of claim 1 , wherein the contacting is performed in the absence of solvent other than the oxidizable starting material.

5. The method of claim 1 , wherein the contacting oxidizes the alkene in the oxidizable starting material to an oxidized group in the oxidized product, the oxidized group comprising an epoxide, a ketone, an aldehyde, or a combination thereof.

6. The method of claim 5 , wherein the alkene is a terminal alkene, and wherein the oxidized group is an aldehyde.

7. The method of claim 1 , wherein the oxidizable starting material is styrene and the oxidized product is benzaldehyde, styrene oxide, oligomerization and/or polymerization products of styrene and/or of the oxidation products thereof, or a combination thereof.

8. The method of claim 1 , wherein the oxidizable starting material is cyclohexene and the oxidized product is cyclohexene oxide, 2-cyclohexene-1-ol, 2-cyclohexene-1-one, 2,3-epoxy-1-cyclohexanol, 2,3-epoxycyclohexanone, or a combination thereof.

9. The method of claim 1 , wherein the contacting comprises:
contacting styrene with the catalyst and oxygen provided by air in the absence of added solvent, to provide benzaldehyde.

10. The method of claim 1 , wherein the contacting comprises:
contacting cyclohexene with the catalyst and oxygen provided by air in the absence of added solvent, to provide cyclohexene oxide, 2-cyclohexene-1-ol, 2-cyclohexene-1-one, 2,3-epoxy-1-cyclohexanol, 2,3-epoxycyclohexanone, or a combination thereof.

11. The method of claim 1 , wherein the catalyst is a purified catalyst that is about 95 wt % pure to about 100 wt % pure.

12. The method of claim 1 , wherein axial ligand L is chosen from CH 3 CN, MeOH, and H 2 O.

13. The method of claim 1 , wherein the catalyst is supported on a solid substrate.

14. The method of claim 1 , wherein at each occurrence, the hydrophilic group is chosen from —C(O)OH, —O—C(O)OH, —P(O)(OH) 2 , —OP(O)(OH) 2 , —S(O)(O)OH, —OS(O)(O)OH, a salt thereof, a substituted or unsubstituted (C 1 -C 50 )hydrocarbyl ester thereof, and a combination thereof.

15. The method of claim 1 , wherein the hydrophilic group is the hydrophilic group is —S(O)(O)OH.

16. The method of claim 1 , wherein at one more occurrences at least one of R 2 , R 3 , R 4 , and R 5 is —S(O)(O)OH.

17. The method of claim 1 , wherein M is chosen from Co and Fe.

18. The method of claim 1 , wherein the catalyst has the structure:

wherein axial ligand L, is H 2 O.

19. The method of claim 1 , wherein the catalyst has the structure:

wherein
M is a metal,
L is a solvent molecule, and
at each occurrence, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are independently chosen from —H, halide, an organic group, and a hydrophilic group.

20. The method of claim 19 , wherein
R 1 and R 6 are —H, and
at each occurrence, R 2 , R 3 , R 4 , and R 5 are independently chosen from —H and a hydrophilic group.

Assignees

• Wisys Tech Foundation Inc

Inventors

• Mcgaff Robert William

Classifications

• B01J31/183 Primary

  with more than one complexing nitrogen atom, e.g. phenanthroline · CPC title

• C07C29/50

  with molecular oxygen only · CPC title

• C07C45/34

  in unsaturated compounds · CPC title

• C07C45/36

  in compounds containing six-membered aromatic rings · CPC title

• C07D301/06 Primary

  in the liquid phase · CPC title