Preparation of metallotexaphyrins

1 . A process for replacing a metal cation, M 1 , from a compound of Formula I

wherein:

M 1 represents a metal cation selected from Ca +2 and Mg +2 ;

Q represents an integer of from about −5 to about +5;

L represents a charge balancing species;

“n” represents an integer of from 0 to +5;

R 1 , R 1a , R 2 , R 3 , R 4 , R 4a a R 7 , and R 8 are independently selected from acyl, acyloxy, optionally substituted alkenyl, optionally substituted alkoxy, optionally substituted alkyl, optionally substituted alkynyl, optionally substituted amino, optionally substituted aryl, optionally substituted aryloxy, carboxyl, (optionally substituted alkoxy)carbonyl, (optionally substituted amino)carbonyl, (optionally substituted alkoxy)carbonyloxy, (optionally substituted amino)carbonyloxy, cyano, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halogen, optionally substituted heteroaryl, optionally substituted heteroaryloxy, optionally substituted heterocyclyl, optionally substituted heterocyclooxy, hydrogen, hydroxyl, nitro, optionally substituted azo, S—R 31 , SO—R 31 , SO2—R 31 , and the moiety X—Y;

R 6 and R 9 are independently selected from acyl, acyloxy, optionally substituted alkenyl, optionally substituted alkoxy, optionally substituted alkyl, optionally substituted alkynyl, optionally substituted amino, optionally substituted aryl, optionally substituted aryloxy, carboxyl, (optionally substituted alkoxy)carbonyl, (optionally substituted amino)carbonyl, (optionally substituted alkoxy)carbonyloxy, (optionally substituted amino)carbonyloxy, cyano, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, fluoro, chloro, bromo, optionally substituted heteroaryl, optionally substituted heteroaryloxy, optionally substituted heterocyclyl, optionally substituted heterocyclooxy, hydrogen, hydroxyl, nitro, optionally substituted azo, sulfanyl, sulfinyl, sulfonyl, and the moiety X—Y;

X is a covalent bond or a linker;

Y is a catalytic group, a chemotherapeutic agent or a site-directing group; and R 31 represents acyl, optionally substituted alkenyl, optionally substituted alky, optionally substituted alkoxy, optionally substituted alkoxycarbonyl, optionally substituted alkynyl, optionally substituted aminocarbonyl, optionally substituted aryl, carboxy, optionally substituted cycloalkyl, optionally substituted heteroaryl, or optionally substituted heterocyclyl;

to form a compound of Formula II with a metal cation M 2

wherein: M 2 represents a metal cation selected from TI +3 , Ti +3 , In +3 , Cr +2 , Mn +2 , Fe +2 , Gd +3 , Co +3 , Ni +2 , Zn +2 , Yb +2 , Cd +2 , Nd +3 , Sm +3 , Eu +3 , Tb +3 , Dy +3 , Y +3 , Fe +3 , Ga +3 , Bi +3 , Lu +3 , Tc +2 Tc +3 , Tc +4 , U +3 , Np +3 , Pu +3 , Am +3 , Cm +3 and Cf +3 ,

Q, L, “n”, R 1 , R 1a , R 2 , R 3 , R 4 , R 4a , R 7 , and R 8 are as indicated above;

said process comprising treating, in a suitable medium, a compound of Formula I with a compound of formula A

M 2 -Z (2-4)   formula A

wherein M 2 is as defined above and Z represents OAc, PO 4 , NO 3 , OTFA, AcAc, Br, I or Cl, optionally in the presence of a base and at a temperature of from about 25° C. to about 100° C., to form a compound of Formula II.

2 . A process of claim 1 wherein M 2 represents TI +3 , In +3 , Mn +2 , Fe +2 , Gd +3 , Co +3 , Dy +3 , Y +3 , Fe +3 , Bi +3 , Lu +3 , Y +3 , Tc +2 , Tc +3 or Tc +4 ; and

L is selected from OAc, PO 4 , NO 3 , OTFA, AcAc, Br, I and Cl.

3 . A process of claim 2 wherein M 2 represents TI +3 , Mn +2 , Gd +3 , Co +3 , In +3 , Bi +3 , Dy +3 , Y +3 or Lu +3 .

4 . A process of claim 3 wherein the suitable medium is selected from EtOH, MeOH, DMF, CH 2 Cl 2 , CHCl 3 , THF, IPA, pyridine, 2,6-lutidine, CH 3 CN, Et 3 N, DMSO, acetyl acetone and mixtures thereof.

5 . A process of claim 4 wherein the suitable medium is selected from EtOH, MeOH, CH 3 CN, or mixtures thereof.

6 . A process of claim 5 wherein the temperature ranges from about 40° C. to about 80° C.

7 . A process of claim 6 wherein the temperature ranges from about 60° C. to about 70° C.

8 . A process of claim 7 wherein Z in formula A is selected from Cl and OAc.

9 . A process of claim 8 wherein the compound of formula A are selected from InCl 3 , In(OAc) 3 , TI(OAc) 3 , Gd(OAc) 3 , Lu(OAc) 3 , and Mn(OAc) 2 .

10 . A process of claim 9 wherein the metal M 2 is selected from TI +3 , Mn +2 , Gd +3 , In +3 and Lu +3 .

11 . A process of claim 9 wherein the optional base is selected from sodium acetate, sodium citrate, pyridine, 2,6-lutidine, triethyl amine, and sodium phosphate.

12 . A process of claim 11 wherein the compound of Formula I is treated with a compound of formula A in the presence of a base selected from sodium acetate, sodium citrate, triethylamine, and 2,6-lutidine.

13 . A process of claim 12 wherein the base is selected from sodium acetate, triethylamine, and 2,6-lutidine.