Methods of making porphyrins and related compounds with Lewis acids
The present invention provides methods of making porphyrins and related compounds such as chlorins by condensing suitable starting materials (e.g., a dipyrromethane-dicarbinol plus dipyrromethane) in a polar solvent in the presence of a Lewis acid. The reactions are preferably carried out in a manner that minimizes rearrangement of the reaction product.
1. A method of making a porphyrin macrocycle compound, comprising:
condensing a dipyrromethane-dicarbinol with a dipyrromethane in a weakly polar solvent in the presence of a weak Lewis acid to produce a porphyrin macrocycle condensation product.
2. A method according to claim 1 , wherein said dipyrromethane-dicarbinol has at least one porphyrinic macrocycle covalently coupled thereto.
3. The method according to claim 2 , wherein said porphyrinic macrocycle compound is metalated.
4. The method according to claim 3 , wherein said condensing step is carried out without demetalation of said porphyrinic macrocycle.
5. The method according to claim 1 , wherein said solvent has a dielectric constant of about 20 or less at room temperature.
6. The method according to claim 1 , wherein said solvent is non-aqueous.
7. The method according to claim 1 , wherein said solvent is selected from the group consisting of hydrocarbons, chlorinated hydrocarbons, ethers, esters, glymes, tributyl borate, carbon disulfide, and mixtures thereof.
8. The method according to claim 1 , wherein said solvent comprises a chlorinated aliphatic hydrocarbon.
9. The method according to claim 1 , wherein said Lewis acid is selected from the group consisting of CsCl, SmCl 3 .6H 2 O, InCl 3 , CrF 3 , AlF 3 , Sc(OTf) 3 , TiF 4 , BEt 3 , GeI 4 , EuCl 3 .nH 2 O, LaCl 3 , and Ln(OTf) 3 where Ln=lanthanide.
10. The method according to claim 1 , wherein said porphyrin macrocycle compound is produced with not more than 5 percent rearrangement thereof.
11. A method of making a porphyrin macrocycle compound, comprising:
self-condensing a dipyrromethane-monocarbinol in a weakly polar solvent in the presence of a weak Lewis acid to produce a porphyrin macrocycle compound as a condensation product.
12. A method according to claim 11 , wherein said dipyrromethane-monocarbinol has at least one porphyrinic macrocycle covalently coupled thereto.
13. The method according to claim 12 , wherein said porphyrinic macrocycle is metalated.
14. The method according to claim 13 , wherein said condensing step is carried out without demetalation of said porphyrinic macrocycle.
15. The method according to claim 11 , wherein said solvent has a dielectric constant of about 20 or less at room temperature.
16. The method according to claim 11 , wherein said solvent is non-aqueous.
17. The method according to claim 11 , wherein said solvent is selected from the group consisting of hydrocarbons, chlorinated hydrocarbons, ethers, esters, glymes, tributyl borate, carbon disulfide, and mixtures thereof.
18. The method according to claim 11 , wherein said solvent comprises a chlorinated aliphatic hydrocarbon.
19. The method according to claim 11 , wherein said Lewis acid is selected from the group consisting of CsCl, SmCl 3 .6H 2 O, InCl 3 , CrF 3 , AlF 3 , Sc(OTf) 3 , TiF 4 , BEt 3 , Gel 4 , EuCl 3 .nH 2 O, LaCl 3 , and Ln(OTf) 3 , where Ln=lanthanide.
20. The method according to claim 11 , wherein said porphyrin macrocycle compound is produced with not more than 5 percent rearrangement thereof.
21. A method of making a chlorin macrocycle compound, comprising:
condensing a bromo-dipyrromethane-monocarbinol and a 1,3,3-trimethyl-2,3,4,5-tetrahydrodipyrrin in a weakly polar solvent in the presence of a weak Lewis acid to produce said chlorin macrocycle compound as a condensation product.
22. A method according to claim 21 , wherein said bromo-dipyrromethane has at least one porphyrinic macrocycle covalently coupled thereto.
23. The method according to claim 22 , wherein said porphyrinic macrocycle is metalated.
24. The method according to claim 23 , wherein said condensing step is carried out without demetalation of said porphyrinic macrocycle.
25. The method according to claim 21 , wherein said solvent has a dielectric constant of about 20 or less at room temperature.
26. The method according to claim 21 , wherein said solvent is non-aqueous.
27. The method according to claim 21 , wherein said solvent is selected from the group consisting of hydrocarbons, chlorinated hydrocarbons, ethers, esters, glymes, tributyl borate, carbon disulfide, and mixtures thereof.
28. The method according to claim 21 , wherein said solvent comprises a chlorinated aliphatic hydrocarbon.
29. The method according to claim 21 , wherein said Lewis acid is selected from the group consisting of CsCl, SmCl 3 .6H 2 O, InCl 3 , CrF 3 , AlF 3 , Sc(OTf) 3 , TiF 4 , BEt 3 , Gel 4 , EuCl 3 .nH 2 O, LaCl 3 , and Ln(OTF) 3 where Ln=lanthanide.
30. The method according to claim 21 , wherein said chlorin macrocycle compound is produced with not more than 5 percent rearrangement thereof.
31. A method of making a porphyrin macrocycle compound, comprising:
condensing a tripyrrane and a 2,5-pyrrole-dicarbinol in a weakly polar solvent in the presence of a weak Lewis acid to produce said porphyrin macrocycle compound.
32. A method according to claim 31 , wherein said tripyrrane has at least one porphyrinic macrocycle covalently coupled thereto.
33. The method according to claim 32 , wherein said porphyrinic macrocycle compound is metalated.
34. The method according to claim 33 , wherein said condensing step is carried out without demetalation of said porphyrinic macrocycle.
35. The method according to claim 31 , wherein said solvent has a dielectric constant of about 20 or less at room temperature.
36. The method according to claim 31 , wherein said solvent is non-aqueous.
37. The method according to claim 31 , wherein said solvent is selected from the group consisting of hydrocarbons, chlorinated hydrocarbons, ethers, esters, glymes, tributyl borate, carbon disulfide, and mixtures thereof.
38. The method according to claim 31 , wherein said solvent comprises a chlorinated aliphatic hydrocarbon.
39. The method according to claim 31 , wherein said Lewis acid is selected from the group consisting of CsCl, SmCl 3 .6H 2 O, InCl 3 , CrF 3 , AlF 3 , Sc(OTf) 3 , TiF 4 , BEt 3 , Gel 4 , EuCl 3 .nH 2 O, LaCl 3 ,and Ln(OTf) 3 where Ln=lanthanide.
40. The method according to claim 31 , wherein said porphyrin macrocycle compound is produced with not more than 5 percent rearrangement thereof.
41. A method of making a tetrasubstituted porphyrin macrocycle compound, comprising:
tetramerizing a pyrrole-carbinol in a weakly polar solvent in the presence of a weak Lewis acid to produce said tetrasubstituted porphyrin macrocycle compound.
42. A method according to claim 41 , wherein said pyrrole-carbinol has at least one porphyrinic macrocycle covalently coupled thereto.
43. The method according to claim 42 , wherein said porphyrinic macrocycle compound is metalated.
44. The method according to claim 43 , wherein said condensing step is carried out without demetalation of said porphyrinic macrocycle.
45. The method according to claim 41 , wherein said solvent has a dielectric constant of about 20 or less at room temperature.
46. The method according to claim 41 , wherein said solvent is non-aqueous.
47. The method according to claim 41 , wherein said solvent is selected from the group consisting of hydrocarbons, chlorinated hydrocarbons, ethers, esters, glymes, tributyl borate, carbon disulfide, and mixtures thereof.
48. The method according to claim 41 , wherein said solvent comprises a chlorinated aliphatic hydrocarbon.
49. The method according to claim 41 , wherein said Lewis acid is selected from the group consisting of CsCl, SmCl 3 .6H 2 O, InCl 3 , CrF 3 , AlF 3 , Sc(OTf) 3 , TiF 4 , BEt 3 , Gel 4 , EuCl 3 .nH 2 O, LaCl 3 , and Ln(OTf) 3 where Ln=lanthanide.
50. The method according to claim 41 , wherein said porphyrin macrocycle compound is produced with not more than 5 percent rearrangement thereof.