Methods and intermediates for the synthesis of porphyrins
A method of making a porphyrin (I) is carried out by condensing (i) a bis(imino)dipyrromethane of Formula II: with (ii) a dipyrromethaneto produce a reaction product; then (b) optionally oxidizing said reaction product with an oxidizing agent; and then (c) optionally demetallating said reaction product to produce the porphyrin. Methods of making compounds of Formula II are also described.
1. A compound of Formula II:
wherein:
R is alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, cycloalkylalkenyl, cycloalkylalkynyl, aryl, arylalkyl, arylalkenyl, arylalkynyl, alkoxy, or acyl;
R 1 is H, alkyl or aryl;
R 2 , R 3 , R 4 , and R 5 are each independently selected from the group consisting of H, halo, loweralkoxy, and loweralkylthio; and
A is aryl.
2. The compound of claim 1 , wherein A is an aromatic hydrophilic group, an aromatic surface attachment group, an aromatic cross-coupling group or an aromatic bioconjugatable group.
3. The compound of claim 2 , wherein A is an aromatic alkene, alkyne, alcohol, thiol, selenyl, phosphono, carboxylic acid, formyl, halo or amine containing-group.
4. The compound of claim 1 , wherein R 2 , R 3 , R 4 , and R 5 are each independently selected from the group consisting of H and halo.
5. The compound of claim 1 , wherein R 2 , R 3 , R 4 , and R 5 are each H.
6. The compound of claim 1 , wherein said compound has the formula:
7. A method of making a compound of Formula II:
wherein:
R is alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, cycloalkylalkenyl, cycloalkylalkynyl, aryl, arylalkyl, arylalkenyl, arylalkynyl, alkoxy, or acyl;
R 1 is H, alkyl or aryl;
R 2 , R 3 , R 4 , and R 5 are each independently selected from the group consisting of H, halo, loweralkoxy, and loweralkylthio; and
A is aryl; said method comprising:
reacting a dipyrromethane of Formula IV:
wherein A, R 1 , R 2 , 4 and R 5 are as given above, with a compound of Formula V:
wherein R is as given above in an organic solvent to produce said compound of Formula II.
8. The method of claim 7 , wherein A is an aromatic surface attachment group, an aromatic cross-coupling group or an aromatic bioconjugatable group.
9. The method of claim 8 , wherein A is an aromatic alkene, alkyne, alcohol, thiol, selenyl, phosphono, carboxylic acid, formyl, halo or amine containing-group.
10. The method of claim 7 , wherein R 2 , R 3 , R 4 , and R 5 are each independently selected from the group consisting of H and halo.
11. The method of claim 7 , wherein R 2 , R 3 , R 4 , and R 5 are each H.
12. The method of claim 7 , wherein said solvent is selected from the group consisting of methylene chloride, chloroform, tetrahydrofuran, nitromethane, toluene, acetonitrile, and mixtures thereof.