Porphyrins

• US 4,892,941 A
• Filed: 04/15/1988
• Issued: 01/09/1990
• Est. Priority Date: 04/17/1987
• Status: Expired due to Fees

• Current Assignee: Clariant Finance (Bvi) Limited, Repligen Corporation, The United States of America As Represented By The Secretary of Agriculture
• Original Assignee: University of British Columbia
• Inventors: Maione, Theodore E., Nakano, Taku, Wijesekera, Tilak P., Dolphin, David H., Farrell, Roberta L., Kirk, Thomas K.
• Primary Examiner(s): Raymond, Richard L.
• Application Number:
  US07/181,859
• Time in Patent Office: 634 Days
• Field of Search: 540/145
• US Class Current: 540/145
• CPC Class Codes: B01J 2531/025 Ligands with a porphyrin ring system or analogues thereof, e.g. phthalocyanines, corroles
• CPC Class Codes: B01J 2531/842 Iron
• CPC Class Codes: B01J 2531/96 Water
• CPC Class Codes: B01J 31/1815 with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
• CPC Class Codes: C07C 2601/14 The ring being saturated
• CPC Class Codes: C07C 2601/16 the ring being unsaturated
• CPC Class Codes: C07C 29/50 with molecular oxygen only
• CPC Class Codes: C07C 35/08 containing a six-membered rings
• CPC Class Codes: C07C 35/18 with unsaturation at least in the ring
• CPC Class Codes: C07C 45/28 of CHx-moieties
• CPC Class Codes: C07C 45/29 of hydroxy groups
• CPC Class Codes: C07C 45/294 with hydrogen peroxide
• CPC Class Codes: C07C 45/30 with halogen containing compounds, e.g. hypohalogenation
• CPC Class Codes: C07D 301/02 Synthesis of the oxirane ring
• CPC Class Codes: C08H 6/00 Macromolecular compounds derived from lignin, e.g. tannins, humic acids
• CPC Class Codes: D21C 3/003 with organic compounds D21C3/20 and D21C3/222 take precedence

Abstract

Disclosed are tetraphenyl porphyrins which are beta-substituted by fluoro or chloro and/or bear electronegative substituents on the phenyl including one or two water solubilizing substituents. The new porphorins are particularly suitable as catalysts in a variety of oxidative reactions and methods.

Claims

1. A compound of the formula:

##STR5## wherein M is a transition metal capable of sustaining oxidation, said M being optionally axially ligated to a ligand, each Y and Y^o independently H, fluoro or chloro, each R ring is ##STR6## X and X^o are independently H or a non-water solubilizing electronegative group, and X₁, X₂ and X₃ are independently H or an electronegative group, subject to the provisos that;

(1) when none of X₁, X₂ and X₃ is in a water solubilizing group, then at least one of Y and Y^o on each porphyrin ring is other than H,

(2) when Y and Y^o are both H, at least one but not more than two of X₁, X₂ and X₃ is water solubilizing group and at least two of X, X^o, X₁, X₂ and X₃ is a non-water solubilizing electronegative group, or the water soluble salts thereof in which said water solubilizing groups are in corresponding water soluble salt form,

(3) no more than two of X₁, X₂ and X₃ is a water solubilizing group,

or a compound of the formula I in which the water solubilizing groups are in water soluble salt form.

2. A compound of claim 1 of the formula:

##STR7## wherein M is a transition metal capable of sustaining oxidation, said M optionally axially ligated to a ligand, each Y and Y^o independently H, fluoro or chloro, each R ring is ##STR8## X and X^o are independently H, fluoro, chloro, bromo or NO₂, X₁, X₂ and X₃ are independently, H, fluoro, chloro, bromo, SO₃ H, COOH or NO₂, subject to the provisos that

(1) when none of X₁, X₂ and X₃ is SO₃ H or COOH, then at least one Y and Y^o on each porphyrin ring is other than H,

(2) when Y and Y^o are both H, at least one but not more than two of X₁, X₂ and X₃ is SO₃ H or COOH, and at least two of X and X^o and the X₁, X₂ and X₃ which are not SO₃ H or COOH are independently fluoro, chloro, bromo or NO₂, and

(3) no more than two of X₁, X₂ and X₃ are SO₃ H or COOH, or a compound of the formula I in which SO₃ H and COOH groups are in water soluble salt form.

3. A compound of claim 2 in which at least one Y and Y^o on each porphyrin ring is fluoro or chloro.

4. A compound of claim 3 in which both Y and Y^o on each porphyrin ring are independently fluoro or chloro.

5. A compound of claim 3 in which both Y and Y^o on each porphyrin ring are chloro.

6. A compound of claim 3 in which at least two of X, X^o, X₁, X₂ and X₃ is fluoro, chloro or bromo.

7. A compound of claim 5 in which at least two of X, X^o, X₁, X₂ and X₃ are fluoro, chloro or bromo.

8. A compound of claim 6 in which at least two of X, X^o, X₁, X₂ and X₃ are chloro.

9. The compound of claim 7 in which at least two of X, X^o, X₁, X₂ and X₃ are chloro.

10. The compound of claim 5 in which each of X, X^o, X₁, X₂ and X₃ are H and M is Fe.

11. The compound of claim 9 in which X and X^o are each chloro, X₁, X₂ and X₃ are each H and M is Fe.

12. The compound of claim 11 in chloride axially ligated form.

13. The compound of claim 9 in which X, X^o, X₁, X₂ and X₃ are each chloro and M is Fe.

14. A compound of claim 2 in which at least one but not more than two of X₁, X₂ and X₃ is SO₃ H or COOH and at least two of X, X^o, X₁, X₂ and X₃ are independently fluoro, chloro or bromo, or a salt form thereof.

15. A compound of claim 14 in which one of X₁, X₂ and X₃ is SO₃ H or COOH and at least two of X, X^o, X₁, X₂ and X₃ are fluoro or chloro, or a salt form thereof.

16. A compound of claim 15 in which one of X₁, X₂ and X₃ is SO₃ H or a salt form thereof.

17. Compound of claim 16 in which Y and Y^o on each porphyrin ring are independently fluoro or chloro.

18. The compound of claim 16 in which Y and Y^o are each H on each porphyrin ring, X and X^o are each chloro, X₁ is SO₃ H, X₂ and X₃ are each H and M is Fe, or a salt form thereof.

19. The compound of claim 18 in chloride axially ligated form.

20. The compound of claim 17 in which Y and Y^o are chloro on each porphyrin ring, X and X^o are each chloro, X₁ is SO₃ H, X₂ and X₃ are each H and M is Fe, or a salt thereof.

21. The compound of claim 5 in which X, X^o, X₁ and X₃ are H, X₂ is SO₃ H and M is Fe, or a salt form thereof.

22. A compound of claim 14 in which Y and Y^o on each porphyrin ring are chloro.

23. The compound of claim 1 in which no more than one of X₁, X₂ and X₃ is a water solubilizing group.

24. A compound of claim 1 in which Y and Y^o are H, X and X^o are chloro, X₁ and X₂ are H and X₃ is an electronegative group.

25. A compound of claim 24 in which X₃ is a water solubilizing group, or a water soluble, salt form thereof.

26. A compound of claim 23 in which X₃ is a water solubilizing group in free acid form.

27. Compound of the formula ##STR9## wherein each Y or Y^o is independently H, fluoro, chloro, each R ring is ##STR10## X and X^o are independently H or a non-water solubilizing electronegative group, and X₁, X₂ and X₃ are independently H or an electronegative group, subject to the provisos that:

(1) when none of X₁, X₂ and X₃ are in a water solubilizing group, then at least one of Y and Y^o on each porphyrin ring is other than H;

(2) when Y and Y^o are both H, at least one but not more than two of X₁, X₂, and X₃ is a water solubilizing group and at least two of X, X₀, X₁, X₂ and X₃ is a water-solubilizing electronegative group or the water soluble salts thereof in which said water solubilizing groups are in corresponding water soluble salt form;

(3) no more than two of X₁, X₂ and X₃ is a water solubilizing group,

or a compound of the formula I in which the water solubilizing groups are in water soluble salt form.

28. A compound according to claim 27 wherein both Y and Y^o are not both H.