Metallic porphyrin complexes as catalysts in epoxidation reactions

• US 4,822,899 A
• Filed: 04/12/1985
• Issued: 04/18/1989
• Est. Priority Date: 04/12/1985
• Status: Expired due to Fees

• Current Assignee: University of Michigan
• Original Assignee: University of Michigan
• Inventors: Quinn, Robert, Groves, John T.
• Primary Examiner(s): Raymond, Richard L.
• Application Number:
  US06/722,956
• Time in Patent Office: 1,467 Days
• Field of Search: 549/533
• US Class Current: 549/533
• CPC Class Codes: B01J 2231/72 Epoxidation
• CPC Class Codes: B01J 2531/025 Ligands with a porphyrin ring system or analogues thereof, e.g. phthalocyanines, corroles
• CPC Class Codes: B01J 2531/57 Niobium
• CPC Class Codes: B01J 2531/74 Rhenium
• CPC Class Codes: B01J 2531/821 Ruthenium
• CPC Class Codes: B01J 2531/822 Rhodium
• CPC Class Codes: B01J 2531/825 Osmium
• CPC Class Codes: B01J 2531/827 Iridium
• CPC Class Codes: B01J 31/1815 with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
• CPC Class Codes: C07D 301/02 Synthesis of the oxirane ring
• CPC Class Codes: C07D 301/06 in the liquid phase
• CPC Class Codes: C07F 15/0053 without a metal-carbon linkage

Abstract

Metallic porphyrin complexes are useful as catalysts for the epoxidation of olefins at ambient temperature and pressure using oxygen, which preferably is supplied either as air or pure oxygen, without need for a coreductant.

Claims

1. A process for the epoxidation of olefins, the process comprising contacting an olefin with a catalytic amount of a metallic porphyrin complex wherein the metal is Ru, Os, Rh, Ir, Nb or Re, in the substatial absence of coreductants and peroxidic oxidants under reaction conditions such that an epoxide of the olefin is formed.

2. The process of claim 1 wherein the complex is a ruthenium porphyrin complex.

3. The process of claim 1 wherein the olefin is ethylene, propylene or butylene.

4. The process of claim 1 wherein the complex is represented by the formula:

##STR3## wherein the metal is represented by M, X is O or a weakly coordinating ligand, and wherein each R independently is an aromatic moiety having sufficient size to prevent formation of a dimer complex.

5. The process of claim 4 wherein the contacting is conducted in the presence of oxygen.

6. The process of claim 4 wherein the contacting is conducted at ambient pressure.

7. The process of claim 4 wherein the temperature is ambient.

8. The process of claim 4 wherein the oxygen is supplied as air.

9. The process of claim 4 wherein the contacting occurs in the presence of a solvent.

10. A process for the epoxidation of olefins comprising contacting under reaction conditions an olefin with oxygen and a catalytic amount of a catalyst represented generally by the formula:

##STR4## wherein each R_a and R_b independently is aryl, haloaryl, alkyl, halo, haloalkyl, haloalkaryl, aralkyl, alkaryl or haloaralkyl; and

each n independently is from zero to 3.

11. The process of claim 10 conducted in the substantial absence of a coreductant.

12. The process of claim 10 wherein the contacting is at ambient temperature and pressure.

13. The process of claim 10 wherein the oxygen is supplied as air.

14. The process of claim 10 conducted in the presence of a solvent, the solvent comprising a solvent selected from the group consisting of benzene, toluene, xylene, chlorobenzene or methylene chloride.

15. The process of claim 10 wherein the oxygen atoms are trans, and each R_a independently is lower alkyl of from about 1 to about 4 carbon atoms.

16. The process of claim 15 wherein n is 1 and each R_b is methyl in the para position.

17. The process of claim 15 wherein each R_b is methyl.

18. The process of claim 10 wherein the olefin is ethylene, propylene or butylene.

19. An aerobic process for the selective epoxidation of olefins, the process comprising contacting an olefin with air at about ambient temperature and pressure in the presence of dioxo[5,10,15,20-tetrakis(2,4,6-trimethylphenyl)-21H,23H-porphinato(2-)-N21,N22,N23,N24]-ruthenium and in the substantial absence of a peroxidic oxidant under reaction conditions such that an epoxide of the olefin is formed.