Dinuclear copper catalyst for the oxidation/oxygenation of hydrocarbons

Patent metadata

Field	Value
Publication number	US-11795129-B2
Application number	US-202318111678-A
Country	US
Kind code	B2
Filing date	Feb 20, 2023
Priority date	Jan 27, 2021
Publication date	Oct 24, 2023
Grant date	Oct 24, 2023

Abstract

The subject invention provides synthetic compounds, and compound complexes having catalytic activities towards oxidation or oxygenation, and/or dehydrogenation of various substrates comprising C−H bonds. The catalysts of the subject invention comprise a dinuclear Cu(I)/Cu(II) center that can convert between a resting state and a reactive species. The subject invention also provides methods of using such catalysts for the oxidation of substrates comprising C−H bonds, e.g., hydrocarbons, to synthesize chemicals for use as pharmaceuticals and industrial feedstock.

First claim

We claim:

1. A dinuclear copper catalyst comprising a dinuclear Cu(II) complex and a stabilizing counter ion, the dinuclear Cu(II) complex having a general structure of formula (B):

where is

and wherein R 1 , R 3 , R 4 , R 5 , R 6 , R 3 ′, R 4 ′, R 5 ′, R 6 ′, R 3 ″, R 4 ″, R 5 ″, R 3 ′″, R 4 ′″, and R 5 ′″, are each independently selected from the group consisting of hydrogen, —NO 2 , —OH, alkyl, substituted alkyl, aryl, heteroalkyl, alkenyl, substituted alkenyl, alkoxy, substituted alkoxy, acyl, carboxyalkyl, halogen, and amino; and R 2 ″, R 6 ″, R 2 ′″, and R 6 ′″ are each independently selected from the group consisting of —NO 2 , —OH, alkyl, substituted alkyl, aryl, heteroalkyl, alkenyl, substituted alkenyl, alkoxy, substituted alkoxy, acyl, carboxyalkyl, halogen, and amino.

2. The dinuclear copper catalyst of claim 1 , the stabilizing counter ion having a general structure of:

wherein R 1 , R s ″, R 4 ″, R 5 ″, R 3 ″″, R 4 ′″, and R 5 ′″, are each independently selected from the group consisting of hydrogen, —NO 2 , alkyl, substituted alkyl, alkoxy, halogen, amino, and hydroxyl; and R 2 ″, R 6 ″, R 2 ′″ and R 6 ′″ are each independently selected from the group consisting of —NO 2 , alkyl, substituted alkyl, alkoxy, halogen, amino, and hydroxyl.

3. The dinuclear copper catalyst of claim 2 , wherein R 1 , R 2 ″, R 4 ″, R 6 ″, R 2 ′″, R 4 ′″, and R 6 ′″ are —NO 2 .

4. The dinuclear copper catalyst of claim 1 , wherein R 1 , R 3 , R 4 , R 5 , R 6 , R 3 ′, R 4 ′, R 5 ′, R 6 ′, R 3 ″, R 4 ″, R 5 ″, R 3 ′″, R 4 ′″, and R 5 ′″, are each independently selected from the group consisting of hydrogen, —NO 2 , —OH, alkyl, substituted alkyl, alkoxy, and halogen; and R 2 ″, R 6 ″, R 2 ′″, and R 6 ′″ are each independently selected from the group consisting of —NO 2 , —OH, alkyl, substituted alkyl, alkoxy, and halogen.

5. The dinuclear copper catalyst of claim 1 , wherein R 3 , R 4 , R 5 , R 6 , R 3 ′, R 4 ′, R 5 ′, and R 6 ′ are each independently selected from the group consisting of hydrogen, F, Cl, Br, I, Me, CF 3 , OMe, and tert-Bu.

6. The dinuclear copper catalyst of claim 1 , wherein at least one of R 1 , R 3 , R 4 , R 5 , R 6 , R 3 ′, R 4 ′, R 5 ′, R 6 ′, R 2 ″, R 3 ″, R 4 ″, R 5 ″, R 6 ″, R 2 ′″, R 3 ′″, R 4 ′″, R 5 ′″, an R 6 ′″ is —NO 2 .

7. The dinuclear copper catalyst of claim 1 , wherein

8. The dinuclear copper catalyst of claim 1 , wherein R 1 , R 2 ″, R 3 ″, R 4 ″, R 6 ″, R 2 ′″ R 3 ′″, R 4 ′″, and R 6 ′″ are —NO 2 .

9. The dinuclear copper catalyst of claim 1 , wherein R 3 , R 4 , R 5 , R 6 , R 3 ′, R 4 ′, R 5 ′, and R 6 ′ are hydrogen, and R 1 , R 4 ″, and R 4 ′″, are each independently selected from the group consisting of hydrogen, —NO 2 , —OH, alkyl, substituted alkyl, aryl, heteroalkyl, alkoxy, substituted alkoxy, acyl, carboxyalkyl, halogen, and amino.

10. The dinuclear copper catalyst of claim 1 , wherein R 1 , R 3 ″, R 4 ″, R 5 ″, R 3 ′″, R 4 ′″, and R 5 ′″ are each independently selected from the group consisting of hydrogen, —NO 2 , alkyl, halogen, amino, and hydroxyl.

11. The dinuclear copper catalyst of claim 1 , wherein R 1 , R 2 ″, R 3 ″, R 4 ″, R 5 ″, R 6 ″, R 2 ′″, R 3 ′″, R 4 ′″, R 5 ′″ and R 6 ′″ are —NO 2 .

12. The dinuclear copper catalyst of claim 1 , wherein R 1 , R 2 ″, R 3 ″, R 4 ″, R 5 ″, R 6 ″, R 2 ′″, R 3 ′″, R 4 ′″, R 5 ′″ and R 6 ′″ are —NO 2 ; and R 3 , R 4 , R 5 , R 6 , R 3 ′, R 4 ′, R 5 ′, and R 6 ′ are H.

13. A composition comprising the dinuclear copper catalyst of claim 1 .

Assignees

• Raptis Raphael G
• Mathivathanan Logesh
• The Florida International Univ Board Of Trustees

Inventors

• Raptis Raphael G
• Mathivathanan Logesh

Classifications

• C07C37/60 Primary

  by oxidation reactions introducing directly hydroxy groups on a =CH-group belonging to a six-membered aromatic ring with the aid of other oxidants than molecular oxygen or their mixtures with molecular oxygen · CPC title

• B01J31/1815 Primary

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

• C07C5/367

  Formation of an aromatic six-membered ring from an existing six-membered ring, e.g. dehydrogenation of ethylcyclohexane to ethylbenzene · CPC title

• C07C29/48

  by oxidation reactions with formation of hydroxy groups · CPC title

• C07C45/28

  of CHx-moieties · CPC title