3-,8-substituted deuteroporphyrin derivatives, pharmaceutical agents containing the latter and process for their production

A process for the production of a porphyrin complex which is a ligand of general formula I ##STR11## and at least one ion of an element with atomic numbers 21-32, 37-39, 42-51 or 57-83, in which

• R.sup.1 is a hydrogen atom, a straight-chain C.sub.1 -C.sub.6 alkyl radical, a C.sub.7 -C.sub.12 aralkyl radical or a group OR' in which
• R' is a C.sub.1 -C.sub.3 alkyl radical,
• R.sup.2 is a group .dbd.CO--Z or a group --(NH).sub.o --(A).sub.q --NH--D, in which
• Z is a group --OL, with L meaning an inorganic or organic cation or Z is a C.sub.1 -C.sub.4 alkyl radical,
• A is a phenylenoxy or a C.sub.1 -C.sub.12 alkylene or C.sub.7 -C.sub.12 -aralkylene group interrupted by one or more oxygen atoms,
• o an q, independently of one another, are the numbers 0 or 1 and
• D is a hydrogen atom or a group --CO--A--(COOL).sub.o --(H).sub.m, with m equal to 0 or 1 and the sum of m and o equal to 1,
• or R.sup.2 has one of the definitions for R.sup.3,
• R.sup.3 is a group --(C.dbd.M)(NR.sup.4).sub.o --(A).sub.q --(NR.sup.5)--K,
• in which M is an oxygen atom or two hydrogen atoms,
• R.sup.4 is a group --(A).sub.q --H and
• K is a complexing agent of formula (IIa) or (IIb) and in which R.sup.5, if K is a complexing agent of formula (IIa), has the same meaning as R.sup.4, and R.sup.5, if K is a complexing agent of formula (IIb), has the same meaning as D,
• provided that a direct oxygen-nitrogen bond is not allowed,
• and K is a complexing agent of general formula (IIa) or (IIb) ##STR12## wherein L.sup.1 is a C.sub.1 -C.sub.6 alkyl radical or an inorganic or organic cation and L.sup.2, L.sup.3 and L.sup.4, independently of one another, have the meaning of L.sup.1 or a hydrogen atom,
• provided that at least two free carboxylic acid groups are present in the complexing agent, and optionally other anions to compensate for optionally present charges in the metalloporphyrin, comprising:
• a) reducing a porphyrin of general formula (IIIa) ##STR13## b) reacting a porphyrin of general formula (IIIb) ##STR14## with aminophenol, or c) reacting a porphyrin of general formula (IIIc) ##STR15## in which R.sup.1 has the indicated meaning, V and Y each stand for a hydrogen atom or together for a multivalent metal ion of an element with atomic numbers 21-32, 37-39, 42-51 or 57-83, and
• X stands for a halogen atom, a group --OR', or for a group --O-- with a compound of the formula H--NR.sup.4 --(A).sub.q --NR.sup.4 --H,
• in which A, R.sup.4 and q have the indicated meaning, optionally subsequently reducing the carbonyl groups or performing Hofmann degradation of the amide
• to yield a porphyrin of general formula IV ##STR16## in which R.sup.6 stands for a group --(C.dbd.M)--(NR.sup.4).sub.o --(A).sub.q --NR.sup.4 --H,
• in which M, R.sup.4, A, o and q have the indicated meaning and in which R.sup.6 ' has the same meaning as R.sup.6 or stands for a group --OR', then
• reacting IV with a complexing agent of general formula V, ##STR17## in which R' has the indicated meaning, and optionally ester groups present are saponified or
• reacting IV with a compound of formula VI ##STR18## in which A' is a group A shortened by one carbon atom and M.sup.1, M.sup.2 and M.sup.3, independently of one another, stand for R.sup.1 or a metal ion equivalent of the elements with atomic numbers 21-32, 37-39, 42-51 or 57-83, under reductive amination conditions, thereafter the thus obtained product--optionally after complete or partial cleavage of the ester groups--is reacted with at least one metal oxide or metal salt of the elements with the above-mentioned atomic numbers, and acylated with a nucleofuge-D' reagent or first acyclated and then reacted with said metal oxide or metal salt, in which D' has the meaning indicated under D, with the provision that D' does not stand for hydrogen and finally, optionally, acidic hydrogens optionally present are then completely or partially substituted by cations of inorganic or organic bases.