New tetrapyrrole polyaminomonocarboxylic acid therapeutic agents

Claim 2

A therapeutic composition comprising a fluorescent mono, di or polyamide of an amino mono- carboxylic acid and a tetrapyrrole containing at least one carboxy group of the structure: wherein Z is the amino acid residue, "n" is an integer from 1 to 4 inclusive, and X is the tetrapyrrole residue, or a salt thereof, and a pharmaceutically acceptable carrier therefor.

Claim 3

The composition according to Claim 1 wherein the amino acid is an alpha amino acid.

Claim 4

A therapeutic composition comprising a fluorescent mono, di or polyamide of an aminomonocarboxylic acid and a tetrapyrrole compound of the formula: or the corresponding di- or tetrahydrotetrapyrroles wherein R 1 is methyl; R 2 is H, vinyl, ethyl, CH 2 CH 2 CO 2 H, or = CHCHO ; R 3 is methyl R 4 is H, vinyl, ethyl, CH 2 CH 2 CO 2 H, =CHCHO; O] R 5 is methyl; R 6 is H, CH 2 CH 2 CO 2 H, CH 2 CH 2 CO 2 R or CO 2 H; R 7 is CH 2 CH 2 CO 2 H, CH 2 CH 2 CO 2 R, or R 8 is methyl or R 9 is H, COOH, CH 2 COOH or methyl; provided that when R 1 , R 2 , R 3 , R 4 , R 7 and R 8 represent two substituents or are divalent and attached to the same carbon, the respective pyrrole ring to which attached is a dihydropyrrole; R is lower alkyl or benzyl; R 6 and R 9 , taken together are with the proviso that at least one of R 1 -R 9 includes a free carboxyl group, or salts thereof; and a pharmaceutically acceptable carrier therefor.

Claim 5

A therapeutic composition comprising a fluorescent mono, di or polyamide of an aminomonocarboxylic acid and a tetrapyrrole compound of the formula: or the corresponding di- or tetrahydrotetrapyrroles wherein R 1 is methyl; R 2 is H, vinyl, ethyl, CH 2 CH 2 CO 2 H, or = CHCHO ; R 3 is methyl R 4 is H, vinyl, ethyl, CH 2 CH 2 CO 2 H, =CHCHO; O] R 5 is methyl; R 6 is H, CH 2 CH 2 CO 2 H, CH 2 CH 2 CO 2 R or CO 2 H; R 7 is CH 2 CH 2 CO 2 H, CH 2 CH 2 CO 2 R, or R 8 is methyl or R 9 is H, COOH, CH 2 COOH or methyl; provided that when R 1 , R 2 , R 3 , R 4 , R 7 and R 8 represent two substituents or are divalent and attached to the same carbon, the respective pyrrole ring to which attached is a dihydropyrrole; R is lower alkyl or benzyl; R 6 and R 9 , taken together are with the proviso that at least one of R 1 -R 9 includes a free carboxyl group, or salts thereof; and a pharmaceutically acceptable carrier therefor.

Claim 6

A therapeutic composition comprising a fluorescent mono, di or polyamide of an amino-monocarboxylic acid and a tetrapyrrole compound of the formula: or the corresponding di- or tetrahydrotetrapyrroles wherein R 1 is methyl; R 2 is H, vinyl, ethyl, CH 2 CH 2 CO 2 H, or =CHCHO; R 3 is methyl R 4 is H, vinyl, ethyl, CH 2 CH 2 CO 2 H, =CHCHO; or R 5 is methyl; R 6 is H, CH 2 CH 2 CO 2 H, CH 2 CH 2 CO 2 R or CO 2 H; R7 is CH 2 CH 2 CO 2 H, CH 2 CH 2 CO 2 R, or R 8 is methyl or R 9 is H, COOH, CH 2 COOH or methyl; provided that when R 1 , R 2 , R 3 , R 4 , R 7 and R 8 represent two substituents or are divalent and attached to the same carbon, the respective pyrrole ring to which attached is a dihydropyrrole; R is lower alkyl or benzyl; R 6 and R 9 , taken together are with the proviso that at least one of R 1 -R 9 includes a free carboxyl group, or salts thereof; and a pharmaceutically acceptable carrier therefor.

Claim 7

A therapeutic composition comprising a fluorescent mono, di or polyamide of an amino-monocarboxylic acid and a tetrapyrrole compound of the formula: or the corresponding di- or tetrahydrotetrapyrroles wherein R 1 is methyl; R 2 is H, vinyl, ethyl, CH 2 CH 2 CO 2 H, or =CHCHO; R 3 is methyl R 4 is H, vinyl, ethyl, CH 2 CH 2 CO 2 H, =CHCHO; or R 5 is methyl; R 6 is H, CH 2 CH 2 CO 2 H, CH 2 CH 2 CO 2 R or CO 2 H; R7 is CH 2 CH 2 CO 2 H, CH 2 CH 2 CO 2 R, or R 8 is methyl or R 9 is H, COOH, CH 2 COOH or methyl; provided that when R 1 , R 2 , R 3 , R 4 , R 7 and R 8 represent two substituents or are divalent and attached to the same carbon, the respective pyrrole ring to which attached is a dihydropyrrole; R is lower alkyl or benzyl; R 6 and R 9 , taken together are with the proviso that at least one of R 1 -R 9 includes a free carboxyl group, or salts thereof; and a pharmaceutically acceptable carrier therefor.

Claim 8

The composition according to Claim 4 wherein the tetrapyrrole is a porphyrin, chlorin or bacteriochlorin.

Claim 9

Composition according to Claim 1 or 4 wherein the amide-containing substituents are asymmetrically arranged on the tetrapyrrole molecule.

Claim 10

Composition according to Claim 4 wherein the amide is: diserinyl mesoporphyrin IX, diglycyl mesoporphyrin IX, di-α-(DL)-alanyl mesoporphyrin IX, di-β-alanyl mesoporphyrin IX , di-ε -amino-n-caproyl mesoporphyrin IX, diglycyl trans-mesochlorin IX , diglycyl trans-mesochlorin e 6 , diglycyl mesochlorin e 4 , diglycyl hematoporphyrin IX, diglycyl chlorin e 6 , diclycyl protoporphyrin IX, diclycyl deuteroporphyrin, di-α-(DL)-alanyl trans-mesochlorin IX, di-α-(DL)-alanyl mesochlorin e 6 , di- α-(DL)-alanyl mesochlorin e 4 , di-α-(DL)-alanyl hematoporphyrin IX, di-α-(DL)-alanyl chlorin e 6 , ci-α-(DL)-alanyl protoporphyrin IX, ci-α-(DL)-alanyl deutoroporphyrin, di-β-(DL)-alanyl trans-mesochlorin IX, di- β- (DL)-alanyl mesochlorin e 6 , di-β-(DL)-alanyl mesochlorin e 4 , di-β-(DL)-alanyl hematoporphyrin IX, di-β-(DL)-alanyl chlorin e 6 , di-β-(DL)-alanyl protoporphyrin IX , di-β-(DL)-alanyl deuteroporphyrin , di-L-α-serinyl chlorin e 6 , di-L- α -serinyl trans-mesochlorin e 6 , di-L- α-serinyl trans-mesochlorin IX , di-L-α-serinyl trans-mesochlorin e 4 , di-L-α-serinyl hematoporphyrin IX , di-L- α -serinyl protoporphyrin IX , di-L- α-serinyl deuteroporphyrin, di- ε-amino-n-caproyl-hematoporphyrin IX, di- ε -amino-n-caproyl-chlorin e 6, di-ε -amino-n-caprolyl-protoporhyrin IX, di-ε -amino-n-caproyl-deuteroprorphyrin, mono-L-serinyl mesochlorin e 6 , mono-L-serinyl Deuterochlorin e 6 , mono-L-serinyl-2-formyl chlorin e 6 , mono-L-serinyl-2-acetyl chlorin e 6 , mono-L-cysteinyl chlorin e 6 , mono-L-asparaginyl chlorin e 6 , mono serinyl chlorin e 6 , mono-(DL)glycyl chlorin e 6 , alanyl chlorin e 6 , mono-L- valyl chlorin e 6 , mono-L-leucyl chlorin e 6 , mono-L-isoleucyl chlorin e 6 , mono-L-prolyl chlorin e 6 , mono-L-methionyl chlorin e 6 , mono-L-threoninyl chlorin e 6 , tyrosyl chlorin e 6 , glutaminyl chlorin e 6 , lysyl chlorin e 6 , arginyl chlorin e 6 , histidyl chlorin e 6 , β -alanyl chlorin e 6 , mono-ε -amino-n-caproyl chlorin e 6 , mono-L-serinyl 2-formyl chlorin e 6 , mono-L-serinyl deuterochlorin e 6 , mono-L-serinyl mesochlorin e 6 , monoglycyl mesoporphyrin IX, mono alanyl mesoporphyrin IX, mono-β -alanyl mesoporphyrin IX, mono-ε-amino-n-caproyl mesoporphyrin IX, mono-β -alanyl-hematoporphyrin IX, threoninyl-2-formylchlorin e 6 , mono-1-threoninyl deutcrochlorin e 6 , or mono-L-threoninyl mesochlorin e 6 .

Claim 11

A therapeutic composition comprising a compound according to Claim 1 and a pharmaceutical carrier therefor.

Claim 12

Use of a fluorescent mono, di or polyamide of an amino monocarboxylic acid and a tetrapyrrole containing at least one carboxy group of the structure: wherein Z is the amino acid residue, "n" is an integer from 1 to 4 inclusive, and X is the tetrapyrrole residue, or a salt thereof, and a pharmaceutically acceptable carrier therefor, for the preparation of a therapeutic composition for photodiagnosis and/or phototherapy of tumors. Claims for Austria 1. Use of a fluorescent mono, di or polyamide of an amino monocarboxylic acid and a tetrapyrrole containing at least one carboxy group of the structure: wherein Z is the amino acid residue, "n" is an integer from 1 to 4 inclusive, and X is the tetrapyrrole residue, or a salt thereof, and a pharmaceutically acceptable carrier therefor, for the preparation of a therapeutic composition for photodiagnosis and/or phototherapy of tumors.

Claim 13

Use according to claim 1, characterized in that the amino acid is an alpha amino acid.

Claim 14

Use according to claim 1, characterized in that the composition comprises a fluorescent mono, di or polyamide of an aminomonocarboxylic acid and a tetrapyrrole compound of the formula:

Claim 15

or the corresponding di- or tetrahydrotetrapyrroles wherein R 1 is methyl; R 2 is H, vinyl, ethyl, CH 2 CH 2 CO 2 H, or =CHCHO; R 3 is methyl R 4 is H, vinyl, ethyl, CH 2 CH 2 CO 2 H, =CHCHO; or R 5 is methyl; R 6 is H, CH 2 CH 2 CO 2 H, CH 2 CH 2 C0 2 R or CO 2 H; R7 is CH 2 CH 2 CO 2 H, CH 2 CH 2 CO 2 R, or R 8 is methyl o R 9 is H, COOH, CH 2 COOH or methyl; provided that when R 1 , R 2 , R 3 , R 4 , R 7 and R 8 represent two substituents or are divalent and attached to the same carbon, the respective pyrrole ring to which attached is a dihydropyrrole; R is lower alkyl or benzyl; R 6 and R 9 , taken together are with the proviso that at least one of R 1 -R 9 includes a free carboxyl group, or salts thereof; and a pharmaceutically acceptable carrier therefor.

Claim 16

or the corresponding di- or tetrahydrotetrapyrroles wherein R 1 is methyl; R 2 is H, vinyl, ethyl, CH 2 CH 2 CO 2 H, or =CHCHO; R 3 is methyl R 4 is H, vinyl, ethyl, CH 2 CH 2 CO 2 H, =CHCHO; or R 5 is methyl; R 6 is H, CH 2 CH 2 CO 2 H, CH 2 CH 2 C0 2 R or CO 2 H; R7 is CH 2 CH 2 CO 2 H, CH 2 CH 2 CO 2 R, or R 8 is methyl o R 9 is H, COOH, CH 2 COOH or methyl; provided that when R 1 , R 2 , R 3 , R 4 , R 7 and R 8 represent two substituents or are divalent and attached to the same carbon, the respective pyrrole ring to which attached is a dihydropyrrole; R is lower alkyl or benzyl; R 6 and R 9 , taken together are with the proviso that at least one of R 1 -R 9 includes a free carboxyl group, or salts thereof; and a pharmaceutically acceptable carrier therefor.

Claim 17

Use according to claim 1, characterized in that the therapeutic composition comprises a fluorescent mono, di or polyamide of an amino-monocarboxylic acid and a tetrapyrrole compound of the formula: or the corresponding di- or tetrahydrotetrapyrroles wherein R 1 is methyl; R 2 is H, vinyl, ethyl, CH 2 CH 2 CO 2 H, or =CHCHO; R 3 is methyl R 4 is H, vinyl, ethyl,