1,7-DIARYL-1,6-HEPTADIENE-3,5-DIONE DERIVATIVES, METHODS FOR THE PRODUCTION AND USE THEREOF

Abstract

1,7-diaryl-1,6-heptadiene-3,5-dione derivatives, methods for the production and use thereof.

Claims

1. A method for the inactivation of microorganisms, wherein the method comprises the following steps: (A) bringing the microorganisms into contact with at least one photosensitizer, wherein the photosensitizer is at least one 1,7-diaryl-1,6-heptadiene-3,5-dione derivative with formula (100): ##STR00198## and/or at least one 1,7-diaryl-1,6-heptadiene-3,5-dione derivative with formula (101): ##STR00199## or respectively a pharmacologically acceptable salt and/or ester and/or complex thereof, wherein the residues Q.sup.3, Q.sup.3a, Q.sup.4 and Q.sup.4, respectively independently of each other, represent one substituted or unsubstituted, monocyclic or polycyclic aromatic residue or one substituted or unsubstituted, monocyclic or polycyclic heteroaromatic residue, wherein K represents hydrogen or a cation, and wherein M.sup.z+ represents a cation of a metal, wherein z is the formal oxidation number of the metal M and z represents a whole number from 1 to 7, and wherein (a1) at least one of the residues Q.sup.3, Q.sup.3a, Q.sup.4 and Q.sup.4, respectively independently of each other, is an unsubstituted, monocyclic or polycyclic heteroaromatic residue, which has at least 5 ring atoms, wherein the ring atoms contain at least one carbon atom and at least one nitrogen atom which optionally can be protonated, or (a2) at least one of the residues Q.sup.3, Q.sup.3a, Q.sup.4 and Q.sup.4, respectively independently of each other, is substituted with at least one organic residue W1, wherein the at least one organic residue W1 has the general formula (4), (5), (6), (7), (8), or (9):
(C(D)(E)).sub.h-X,(4)
-A-(C(D)(E)).sub.h-X,(5)
(C(D)(E)).sub.k-aryl-(C(D)(E)).sub.l-X,(6)
-A-(C(D)(E)).sub.k-aryl-(C(D)(E)).sub.l-X,(7)
((C(D)(E)).sub.mA).sub.p-(C(D)(E)).sub.n-X,(8)
-A-((C(D)(E)).sub.m-A).sub.p-(C(D)(E)).sub.n-X,(9) wherein h represents a whole number from 1 to 20, wherein k represents a whole number from 0 to 10, wherein 1 represents a whole number from 0 to 10, and wherein m, n and p, respectively independently of each other, represent a whole number from 1 to 6, and wherein A, respectively independently of each other, represents oxygen or sulphur, wherein D and E, respectively independently of each other, represent hydrogen, halogen, G-R.sup.(I), or G-C(=G)-R.sup.(II), wherein G, respectively independently of each other, represents oxygen or sulphur, and wherein the residues R.sup.(I) and R.sup.(II), respectively independently of each other, represent hydrogen, methyl, ethyl, n-propyl, n-butyl, n-pentyl, phenyl or benzyl, wherein phenyl and benzyl may be unsubstituted or substituted, wherein aryl represents a substituted or unsubstituted aromatic group or a substituted or unsubstituted heteroaromatic group which does not contain a nitrogen atom, wherein X, respectively independently of each other, is an organic residue which (i) contains at least one neutral nitrogen atom which can be protonated, or (ii) contains at least one positively charged, preferably quaternary, nitrogen atom, or (iii) contains at least one positively charged, preferably quaternary, phosphorus atom, and wherein the residues R1, R2, R3, R4 and R5, respectively independently of each other, represent hydrogen, halogen, alkyl containing 1 to 12 C atoms, cycloalkyl containing 1 to 12 C atoms, alkylaryl containing 1 to 12 C atoms, aryl containing 5 to 20 C atoms, ether containing 2 to 12 C atoms or glycol containing 2 to 12 C atoms, or wherein (b) the residue R3 is an organic residue W2, wherein the one organic residue W2 has the general formula (4), (5), (6), (7), (8), (9), or (10):
(C(D)(E)).sub.h-X,(4)
-A-(C(D)(E)).sub.h-X,(5)
(C(D)(E)).sub.k-aryl-(C(D)(E)).sub.l-X,(6)
-A-(C(D)(E)).sub.k-aryl-(C(D)(E)).sub.l-X,(7)
[(C(D)(E)).sub.m-A].sub.p(C(D)(E)).sub.n-X,(8)
-A-[(C(D)(E)).sub.m-A].sub.p(C(D)(E)).sub.n-X,(9)
-(-C(D)=C(E)-).sub.r-X,(10) and wherein, optionally, at least one of the residues Q.sup.3, Q.sup.3a, Q.sup.4 and Q.sup.4, respectively independently of each other, is substituted with at least one organic residue W1 which has the general formula (4), (5), (6), (7), (8), or (9), wherein h represents a whole number from 1 to 20, wherein k represents a whole number from 0 to 10, wherein 1 represents a whole number from 0 to 10, and wherein m, n, p, and r, respectively independently of each other, represent a whole number from 1 to 6, and wherein A, respectively independently of each other, represents oxygen or sulphur, wherein D and E, respectively independently of each other, represent hydrogen, halogen, G-R.sup.(I), or G-C(=G)-R.sup.(II), wherein G, respectively independently of each other, represents oxygen or sulphur, and wherein the residues R.sup.(I) and R.sup.(II), respectively independently of each other, represent hydrogen, methyl, ethyl, n-propyl, n-butyl, n-pentyl, phenyl or benzyl, wherein phenyl and benzyl may be unsubstituted or substituted, wherein aryl represents a substituted or unsubstituted aromatic group or a substituted or unsubstituted heteroaromatic group which does not contain a nitrogen atom, wherein X, respectively independently of each other, is an organic residue which (i) contains at least one neutral nitrogen atom which can be protonated, (ii) contains at least one positively charged nitrogen atom, or (iii) contains at least one positively charged phosphorus atom, and wherein the residues R1, R2, R4 and R5, respectively independently of each other, represent hydrogen, halogen, alkyl containing 1 to 12 C atoms, alkylaryl containing 1 to 12 C atoms, aryl containing 5 to 20 C atoms, ether containing 2 to 12 C atoms or glycol containing 2 to 12 C atoms, and (B) irradiating the microorganisms and the at least one photosensitizer with electromagnetic radiation of a suitable wavelength and energy density.

2. The method as claimed in claim 1 wherein, in the compound with formula (100), K is a cation M.sup.z+ of a metal M, wherein z is the formal oxidation number of the metal M and wherein z represents a whole number from 1 to 7, and wherein the compound has the formula (102): ##STR00200## wherein L.sup.1 and L.sup.2, respectively independently of each other, represent water, fluoride, chloride, bromide, iodide, phosphate, hydrogen phosphate, dihydrogen phosphate, sulphate, hydrogen sulphate, tosylate, mesylate or at least one carboxylation of a carboxylic acid containing 1 to 15 carbon atoms and/or mixtures thereof.

3. The method as claimed in claim 1, wherein the irradiation of the microorganisms and of the at least one photosensitizer with electromagnetic radiation of a suitable wavelength and energy density is carried out in the presence of at least one oxygen-donating compound and/or at least one oxygen-containing gas.

4. A compound with formula (1): ##STR00201## wherein the residues Q.sup.1 and Q.sup.2, respectively independently of each other, represent one substituted or unsubstituted, monocyclic or polycyclic aromatic residue, wherein the compound with formula (1) does not contain an OH group which is bonded directly to the organic residue Q.sup.1 or Q.sup.2, and wherein K represents hydrogen or a cation, and wherein (a) at least one of the residues Q.sup.1 and Q.sup.2, respectively independently of each other, is substituted with at least one organic residue W1a, wherein the at least one organic residue W1a has the general formula (5a), (6a), (7a), (8a), or (9a):
-A-(C(D)(E)).sub.h-X.sup.a,(5a)
(C(D)(E)).sub.k-aryl-(C(D)(E)).sub.l-X.sup.a,(6a)
-A-(C(D)(E)).sub.k-aryl-(C(D)(E)).sub.l-X.sup.a,(7a)
((C(D)(E)).sub.m-A).sub.p-(C(D)(E)).sub.n-X.sup.a,(8a)
-A-((C(D)(E)).sub.m-A).sub.p-(C(D)(E)).sub.n-X.sup.a,(9a) wherein h represents a whole number from 1 to 20, wherein k represents a whole number from 0 to 10, wherein 1 represents a whole number from 0 to 10, and wherein m, n and p, respectively independently of each other, represent a whole number from 1 to 6, and wherein A, respectively independently of each other, represents oxygen or sulphur, wherein D and E, respectively independently of each other, represent hydrogen, halogen, G-R.sup.(I), or G-C(=G)-R.sup.(II), wherein G, respectively independently of each other, represents oxygen or sulphur, and wherein the residues R.sup.(I) and R.sup.(II), respectively independently of each other, represent hydrogen, methyl, ethyl, n-propyl, n-butyl, n-pentyl, phenyl or benzyl, wherein phenyl and benzyl may be unsubstituted or substituted, wherein aryl represents a substituted or unsubstituted aromatic group or a substituted or unsubstituted heteroaromatic group which does not contain a nitrogen atom, wherein X.sup.a, respectively independently of each other, represents a residue with formula (20c), (20d), or (21): ##STR00202## wherein each of the residues R.sup.(VII), R.sup.(VIII), and R.sup.(IX), respectively independently of each other, represents hydrogen, an aryl residue containing 5 to 12 C atoms, an alkylaryl residue containing 5 to 12 C atoms, an alkyl residue, which may be linear or branched, containing 1 to 8 C atoms, or an ether residue, which may be linear or branched, containing 1 to 8 C atoms, and wherein the residues R1, R2, R3, R4 and R5, respectively independently of each other, represent hydrogen, halogen, alkyl containing 1 to 12 C atoms, cycloalkyl containing 1 to 12 C atoms, alkylaryl containing 1 to 12 C atoms, aryl containing 5 to 20 C atoms, ether containing 2 to 12 C atoms or glycol containing 2 to 12 C atoms, or wherein (b) the residue R3 is an organic residue W2a which contains at least one neutral nitrogen atom which can be protonated, and/or at least one positively charged nitrogen atom and/or at least one positively charged phosphorus atom, wherein the one organic residue W2a has the general formula (4b), (5b), (6b), (7b), (8b), or (9b):
(C(D)(E)).sub.h-X.sup.b,(4b)
-A-(C(D)(E)).sub.h-X.sup.b,(5b)
(C(D)(E)).sub.k-aryl-(C(D)(E)).sub.l-X.sup.b,(6b)
-A-(C(D)(E)).sub.k-aryl-(C(D)(E)).sub.l-X.sup.b,(7b)
[(C(D)(E)).sub.m-A].sub.p(C(D)(E)).sub.n-X.sup.b,(8b)
-A-[(C(D)(E)).sub.m-A].sub.p(C(D)(E)).sub.n-X.sup.b,(9b) and wherein, optionally, at least one of the residues Q.sup.1 and Q.sup.2, respectively independently of each other, is substituted with at least one organic residue W1b which has the general formula (4b), (5b), (6b), (7b), (8b), or (9b), wherein h represents a whole number from 1 to 20, wherein k represents a whole number from 0 to 10, wherein 1 represents a whole number from 0 to 10, and wherein m, n and p, respectively independently of each other, represent a whole number from 1 to 6, and wherein A, respectively independently of each other, represents oxygen or sulphur, wherein D and E, respectively independently of each other, represent hydrogen, halogen, G-R.sup.(I), or G-C(=G)-R.sup.(II), wherein G, respectively independently of each other, represents oxygen or sulphur, and wherein the residues R.sup.(I) and R.sup.(II), respectively independently of each other, represent hydrogen, methyl, ethyl, n-propyl, n-butyl, n-pentyl, phenyl or benzyl, wherein phenyl and benzyl may be unsubstituted or substituted, wherein aryl represents a substituted or unsubstituted aromatic group or a substituted or unsubstituted heteroaromatic group which does not contain a nitrogen atom, wherein X.sup.b, respectively independently of each other, is an organic residue which (i) contains at least one neutral nitrogen atom which can be protonated, or (ii) contains at least one positively charged nitrogen atom, or (iii) contains at least one positively charged phosphorus atom, and wherein the residues R1, R2, R4 and R5, respectively independently of each other, represent hydrogen, halogen, alkyl containing 1 to 12 C atoms, alkylaryl containing 1 to 12 C atoms, aryl containing 5 to 20 C atoms, ether containing 2 to 12 C atoms or glycol containing 2 to 12 C atoms.

5. The compound as claimed in claim 4, wherein K represents a cation M.sup.z+ of a metal M, wherein z is the formal oxidation number of the metal M and is a whole number from 1 to 7 and wherein the compound has the formula (2): ##STR00203## wherein L.sup.1 and L.sup.2, respectively independently of each other, represent water, halide, cyanide, thiocyanate, phosphate, hydrogen phosphate, or a carboxylation of a carboxylic acid containing 1 to 10 carbon atoms.

6. A compound with formula (3): ##STR00204## wherein M.sup.z+ represents a cation of a metal, wherein z is the formal oxidation number of the metal M and is a whole number from 1 to 7 and wherein Q.sup.1 and Q.sup.2, respectively independently of each other, represent one substituted or unsubstituted, monocyclic or polycyclic aromatic residue, and wherein the residues Q.sup.1a and Q.sup.2a, respectively independently of each other, represent one substituted or unsubstituted, monocyclic or polycyclic aromatic residue or one substituted or unsubstituted, monocyclic or polycyclic heteroaromatic residue, and wherein (a) at least one of the residues Q.sup.1 and Q.sup.2, respectively independently of each other, is substituted with at least one organic residue W1a which has the general formula (5a), (6a), (7a), (8a), or (9a):
-A-(C(D)(E)).sub.h-X.sup.a,(5a)
(C(D)(E)).sub.k-aryl-(C(D)(E)).sub.l-X.sup.a,(6a)
-A-(C(D)(E)).sub.k-aryl-(C(D)(E)).sub.l-X.sup.a,(7a)
((C(D)(E)).sub.m-A).sub.p-(C(D)(E)).sub.n-X.sup.a,(8a)
-A-((C(D)(E)).sub.m-A).sub.p-(C(D)(E)).sub.n-X.sup.a,(9a) wherein at least one of the residues Q.sup.1a and Q.sup.2a, respectively independently of each other, is substituted with at least one organic residue W1c which has the general formula (5c), (6c), (7c), (8c), or (9c):
-A-(C(D)(E)).sub.h-X.sup.c,(5c)
(C(D)(E)).sub.k-aryl-(C(D)(E)).sub.l-X.sup.c,(6c)
-A-(C(D)(E)).sub.k-aryl-(C(D)(E)).sub.l-X.sup.c,(7c)
((C(D)(E)).sub.m-A).sub.p-(C(D)(E)).sub.n-X.sup.c,(8c)
-A-((C(D)(E)).sub.m-A).sub.p-(C(D)(E)).sub.n-X.sup.c,(9c) wherein h represents a whole number from 1 to 20, wherein k represents a whole number from 0 to 10, wherein 1 represents a whole number from 0 to 10, and wherein m, n and p, respectively independently of each other, represent a whole number from 1 to 6, and wherein A, respectively independently of each other, represents oxygen or sulphur, wherein D and E, respectively independently of each other, represent hydrogen, halogen, G-R.sup.(I), or G-C(=G)-R.sup.(II), wherein G, respectively independently of each other, represents oxygen or sulphur, and wherein the residues R.sup.(I) and R.sup.(II), respectively independently of each other, represent hydrogen, methyl, ethyl, n-propyl, n-butyl, n-pentyl, phenyl or benzyl, wherein phenyl and benzyl may be unsubstituted or substituted, wherein aryl represents a substituted or unsubstituted aromatic group or a substituted or unsubstituted heteroaromatic group which does not contain a nitrogen atom, and wherein X.sup.a, respectively independently of each other, represents a residue with formula (20c), (20d), (21), or (24): ##STR00205## wherein each of the residues R.sup.(VII), R.sup.(VIII), and R.sup.(IX), respectively independently of each other, represents hydrogen, an aryl residue containing 5 to 12 C atoms, an alkylaryl residue containing 5 to 12 C atoms, an alkyl residue, which may be linear or branched, containing 1 to 8 C atoms, or an ether residue, which may be linear or branched, containing 1 to 8 C atoms, and wherein each of the residues R.sup.(XV), R.sup.(XVI), and R.sup.(XVII), respectively independently of each other, represents an aryl residue containing 5 to 12 C atoms, an alkylaryl residue containing 5 to 12 C atoms, an alkyl residue, which may be linear or branched, containing 1 to 8 C atoms, or an ether residue, which may be linear or branched, containing 1 to 8 C atoms, and wherein X.sup.c, respectively independently of each other, is an organic residue which (i) contains at least one neutral nitrogen atom which can be protonated, or (ii) contains at least one positively charged nitrogen atom, or (iii) contains at least one positively charged phosphorus atom, and wherein the residues R1, R1.sup.a, R2, R2.sup.a, R3, R3.sup.a, R4, R4.sup.a, R5 and R5.sup.a, respectively independently of each other, represent hydrogen, halogen, alkyl containing 1 to 12 C atoms, cycloalkyl containing 1 to 12 C atoms, alkylaryl containing 1 to 12 C atoms, aryl containing 5 to 20 C atoms, ether containing 2 to 12 C atoms or glycol containing 2 to 12 C atoms, or wherein (b) the residue R3 or R3a, respectively independently of each other, is an organic residue W2a, wherein the one organic residue W2a has the general formula (4b), (5b), (6b), (7b), (8b), or (9b):
(C(D)(E)).sub.h-X.sup.b,(4b)
-A-(C(D)(E)).sub.h-X.sup.b,(5b)
(C(D)(E)).sub.k-aryl-(C(D)(E)).sub.l-X.sup.b,(6b)
-A-(C(D)(E)).sub.k-aryl-(C(D)(E)).sub.l-X.sup.b,(7b)
[(C(D)(E)).sub.m-A].sub.p(C(D)(E)).sub.n-X.sup.b,(8b)
-A-[(C(D)(E)).sub.m-A].sub.p(C(D)(E)).sub.n-X.sup.b,(9b) and wherein, optionally, at least one of the residues Q.sup.1, Q.sup.1a, Q.sup.2 and Q.sup.2a, respectively independently of each other, is substituted with at least one organic residue W1b which has the general formula (4b), (5b), (6b), (7b), (8b), or (9b), wherein h represents a whole number from 1 to 20, wherein k represents a whole number from 0 to 10, wherein l represents a whole number from 0 to 10, and wherein m, n, p, and r, respectively independently of each other, represent a whole number from 1 to 6, and wherein A, respectively independently of each other, represents oxygen or sulphur, wherein D and E, respectively independently of each other, represent hydrogen, halogen, G-R.sup.(I), or G-C(=G)-R.sup.(II), wherein G, respectively independently of each other, represents oxygen or sulphur, and wherein the residues R.sup.(I) and R.sup.(II), respectively independently of each other, represent hydrogen, methyl, ethyl, n-propyl, n-butyl, n-pentyl, phenyl or benzyl, wherein phenyl and benzyl may be unsubstituted or substituted, wherein aryl represents a substituted or unsubstituted aromatic group or a substituted or unsubstituted heteroaromatic group which does not contain a nitrogen atom, wherein X.sup.b, respectively independently of each other, is an organic residue which (i) contains at least one neutral nitrogen atom which can be protonated, (ii) contains at least one positively charged nitrogen atom, or (iii) contains at least one positively charged phosphorus atom, and wherein the residues R1, R1.sup.a, R2, R2.sup.a, R4, R4.sup.a, R5 and R5.sup.a, respectively independently of each other, represent hydrogen, halogen, alkyl containing 1 to 12 C atoms, alkylaryl containing 1 to 12 C atoms, aryl containing 5 to 20 C atoms, ether containing 2 to 12 C atoms or glycol containing 2 to 12 C atoms.

7. The compound as claimed in claim 6, wherein the compound with formula (3) has the formula (3a): ##STR00206## wherein M.sup.z+ represents a cation of a metal, wherein z is the formal oxidation number of the metal M and represents a whole number from 1 to 7, and wherein Q.sup.1 and Q.sup.2, respectively independently of each other, represent one substituted or unsubstituted, monocyclic or polycyclic aromatic residue, and wherein (a) at least one of the residues Q.sup.1 and Q.sup.2, respectively independently of each other, is substituted with at least one organic residue W1a which has the general formula (5a), (6a), (7a), (8a), or (9a):
-A-(C(D)(E)).sub.h-X.sup.a,(5a)
(C(D)(E)).sub.k-aryl-(C(D)(E)).sub.l-X.sup.a,(6a)
-A-(C(D)(E)).sub.k-aryl-(C(D)(E)).sub.l-X.sup.a,(7a)
((C(D)(E)).sub.m-A).sub.p-(C(D)(E)).sub.n-X.sup.a,(8a)
-A-((C(D)(E)).sub.m-A).sub.p-(C(D)(E)).sub.n-X.sup.a,(9a) wherein h represents a whole number from 1 to 20, wherein k represents a whole number from 0 to 10, wherein 1 represents a whole number from 0 to 10, and wherein m, n and p, respectively independently of each other, represent a whole number from 1 to 6, and wherein A, respectively independently of each other, represents oxygen or sulphur, wherein D and E, respectively independently of each other, represent hydrogen, halogen, G-R.sup.(I), or G-C(=G)-R.sup.(II), wherein G, respectively independently of each other, represents oxygen or sulphur, and wherein the residues R.sup.(I) and R.sup.(II), respectively independently of each other, represent hydrogen, methyl, ethyl, n-propyl, n-butyl, n-pentyl, phenyl or benzyl, wherein phenyl and benzyl may be unsubstituted or substituted, wherein aryl represents a substituted or unsubstituted aromatic group or a substituted or unsubstituted heteroaromatic group which does not contain a nitrogen atom, and wherein X.sup.a, respectively independently of each other, represents a residue with formula (20c), (20d), (21), or (24): ##STR00207## wherein each of the residues R.sup.(VII), R.sup.(VII), and R.sup.(IX), respectively independently of each other, represents hydrogen, an aryl residue containing 5 to 12 C atoms, an alkylaryl residue containing 5 to 12 C atoms, an alkyl residue, which may be linear or branched, containing 1 to 8 C atoms, or an ether residue, which may be linear or branched, containing 1 to 8 C atoms, and wherein each of the residues R.sup.(XV), R.sup.(XVI), and R.sup.(XVII), respectively independently of each other, represents an aryl residue containing 5 to 12 C atoms, an alkylaryl residue containing 5 to 12 C atoms, an alkyl residue, which may be linear or branched, containing 1 to 8 C atoms, or an ether residue, which may be linear or branched, containing 1 to 8 C atoms, and wherein the residues R1, R2, R3, R4, and R5, respectively independently of each other, represent hydrogen, halogen, alkyl containing 1 to 12 C atoms, cycloalkyl containing 1 to 12 C atoms, alkylaryl containing 1 to 12 C atoms, aryl containing 5 to 20 C atoms, ether containing 2 to 12 C atoms or glycol containing 2 to 12 C atoms, or wherein (b) the residue R3, respectively independently of each other, is an organic residue W2a, wherein the one organic residue W2a has the general formula (4b), (5b), (6b), (7b), (8b), or (9b):
(C(D)(E)).sub.h-X.sup.b,(4b)
-A-(C(D)(E)).sub.h-X.sup.b,(5b)
(C(D)(E)).sub.k-aryl-(C(D)(E)).sub.l-X.sup.b,(6b)
-A-(C(D)(E)).sub.k-aryl-(C(D)(E)).sub.l-X.sup.b,(7b)
[(C(D)(E)).sub.m-A].sub.p(C(D)(E)).sub.n-X.sup.b,(8b)
-A-[(C(D)(E)).sub.m-A].sub.p(C(D)(E)).sub.n-X.sup.b,(9b) and wherein, optionally, at least one of the residues Q.sup.1, and Q.sup.2, respectively independently of each other, is substituted with at least one organic residue W1b which has the general formula (4b), (5b), (6b), (7b), (8b), or (9b), wherein h represents a whole number from 1 to 20, wherein k represents a whole number from 0 to 10, wherein 1 represents a whole number from 0 to 10, and wherein m, n, p, and r, respectively independently of each other, represent a whole number from 1 to 6, and wherein A, respectively independently of each other, represents oxygen or sulphur, wherein D and E, respectively independently of each other, represent hydrogen, halogen, G-R.sup.(I), or G-C(=G)-R.sup.(II), wherein G, respectively independently of each other, represents oxygen or sulphur, and wherein the residues R.sup.(I) and R.sup.(II), respectively independently of each other, represent hydrogen, methyl, ethyl, n-propyl, n-butyl, n-pentyl, phenyl or benzyl, wherein phenyl and benzyl may be unsubstituted or substituted, wherein aryl represents a substituted or unsubstituted aromatic group or a substituted or unsubstituted heteroaromatic group which does not contain a nitrogen atom, wherein X.sup.b, respectively independently of each other, is an organic residue which (i) contains at least one neutral nitrogen atom which can be protonated, (ii) contains at least one positively charged nitrogen atom, or (iii) contains at least one positively charged phosphorus atom, and wherein the residues R1, R2, R4, and R5, respectively independently of each other, represent hydrogen, halogen, alkyl containing 1 to 12 C atoms, alkylaryl containing 1 to 12 C atoms, aryl containing 5 to 20 C atoms, ether containing 2 to 12 C atoms or glycol containing 2 to 12 C atoms.

8. The compound as claimed in claim 5, wherein M is selected from the group which consists of B, Al, Zn, Cu, Mg, Ca, Fe, Si, Ga, Sn, Rh, Co, Ti, Zr, V, Cr, Mo, Mn, Ru, Pd, Ir, Ni, and combinations thereof.

9. The compound as claimed in claim 4, wherein the residues Q.sup.1, Q.sup.1a, Q.sup.3 and Q.sup.3a, respectively independently of each other, are an aromatic residue with general formula (11a), (12a), (13a), (14a), (15a), (16a), (17a), (18a), or (19a): ##STR00208## ##STR00209## and wherein the residues Q.sup.2, Q.sup.2a, Q.sup.4 and Q.sup.4a, respectively independently of each other, represent an aromatic residue with general formula (11b), (12b), (13b), (14b), (15b), (16b), (17b), (18b), or (19b): ##STR00210## ##STR00211## and wherein respectively, at least 1 residue R.sup.6a to R.sup.10a, R.sup.11a to R.sup.17a, R.sup.18a to R.sup.24a, R.sup.25a to R.sup.33a, R.sup.34a to R.sup.42a, R.sup.43a to R.sup.51a, R.sup.52a to R.sup.60a, R.sup.61a to R.sup.69a, R.sup.70a to R.sup.78a, R.sup.6b to R.sup.10b, R.sup.11b to R.sup.17b, R.sup.18b to R.sup.24b, R.sup.25b to R.sup.33b, R.sup.34b to R.sup.42b, R.sup.43b to R.sup.51b, R.sup.52b to R.sup.60b, R.sup.61b to R.sup.69b, or R.sup.70b to R.sup.78b, respectively independently of each other, is an organic residue W1a or an organic residue W1b or an organic residue W1c, and wherein the residues R.sup.6a to R.sup.10a, R.sup.11a to R.sup.17a, R.sup.18a to R.sup.24a, R.sup.25a to R.sup.33a, R.sup.34a to R.sup.42a, R.sup.43a to R.sup.51a, R.sup.52a to R.sup.60a, R.sup.61a to R.sup.69a, R.sup.70a to R.sup.78a, R.sup.6b to R.sup.10b, R.sup.11b to R.sup.17b, R.sup.18b, to R.sup.24b, R.sup.25b to R.sup.33b, R.sup.34b to R.sup.42b, R.sup.43b to R.sup.51b, R.sup.52b to R.sup.60a, R.sup.61b to R.sup.69b to R.sup.70b to R.sup.78b, which are not an organic residue W1a or an organic residue W1b or an organic residue W1c, respectively independently of each other, are identical or different and represent hydrogen, halogen, hydroxyl, thiol, nitro, carboxylate, aldehyde containing 1 to 8 C atoms, ketone containing 2 to 8 C atoms, O-alkyl containing 1 to 12 C atoms, S-alkyl containing 1 to 12 C atoms, O-alkenyl containing 2 to 12 C atoms, S-alkenyl containing 2 to 12 C atoms, O-aryl containing 5 to 20 C atoms, S-aryl containing 5 to 20 C atoms, ether containing 2 to 12 C atoms, thioether containing 2 to 12 C atoms, carboxylic acid ester containing 1 to 12 C atoms, carboxylic acid amide containing 1 to 12 C atoms, thioester containing 1 to 12 C atoms, alkyl containing 1 to 12 C atoms, alkenyl containing 2 to 12 C atoms, cycloalkyl containing 3 to 12 C atoms, cycloalkenyl containing 3 to 12 C atoms, alkylaryl containing 1 to 12 C atoms, aryl containing 5 to 20 C atoms or heteroaryl, which does not contain a nitrogen atom, containing 4 to 20 C atoms.

10. The compound as claimed in claim 9, wherein the residues Q.sup.1, Q.sup.1a, Q.sup.3 and Q.sup.3a, respectively independently of each other, are an aromatic residue with general formula (11a), (12a) or (13a) and wherein the residues Q.sup.2, Q.sup.2a, Q.sup.4 and Q.sup.4a, respectively independently of each other, are an aromatic residue with general formula (11b), (12b) or (13b), and wherein respectively at least 1 residue R.sup.6a to R.sup.10a, R.sup.11a to R.sup.17a, R.sup.18a to R.sup.24a, R.sup.6b to R.sup.10b, R.sup.11b to R.sup.17b or R.sup.18b to R.sup.24b, respectively independently of each other, is an organic residue W1a or an organic residue W1b or an organic residue W1c, wherein the residues R.sup.10a, R.sup.11a to R.sup.17a, R.sup.18a to R.sup.24a, R.sup.6b to R.sup.10b, R.sup.11b to R.sup.17b and R.sup.18b to R.sup.24b, which are not an organic residue W1a or an organic residue W1b or an organic residue W1c, respectively independently of each other, are identical or different and represent hydrogen, halogen, hydroxyl, thiol, nitro, carboxylate, aldehyde containing 1 to 8 C atoms, ketone containing 2 to 8 C atoms, O-alkyl containing 1 to 12 C atoms, S-alkyl containing 1 to 12 C atoms, O-alkenyl containing 2 to 12 C atoms, S-alkenyl containing 2 to 12 C atoms, O-aryl containing 5 to 20 C atoms, S-aryl containing 5 to 20 C atoms, ether containing 2 to 12 C atoms, thioether containing 2 to 12 C atoms, carboxylic acid ester containing 1 to 12 C atoms, carboxylic acid amide containing 1 to 12 C atoms, thioester containing 1 to 12 C atoms, alkyl containing 1 to 12 C atoms, alkenyl containing 2 to 12 C atoms, cycloalkyl containing 3 to 12 C atoms, cycloalkenyl containing 3 to 12 C atoms, alkylaryl containing 1 to 12 C atoms, aryl containing 5 to 20 C atoms or heteroaryl, which does not contain a nitrogen atom, containing 4 to 20 C atoms.

11. The compound as claimed claim 4, wherein the organic residue X.sup.b and/or X.sup.c, respectively independently of each other, represents a residue with formula (20a), (20b), (21), (22a), (22b), (23a), (24b), or (24): ##STR00212## wherein each of the residues R.sup.(IVa), R.sup.(Va), R.sup.(IVb), R.sup.(Vb), R.sup.(VIb), R.sup.(VII), R.sup.(VIII), R.sup.(X), R.sup.(XI), R.sup.(XII), R.sup.(XIII), R.sup.(XIV), R.sup.(XV), R.sup.(XVI), and R.sup.(XVII), respectively independently of each other, represents hydrogen, an aryl residue containing 5 to 12 C atoms, an alkyl residue, which may be linear or branched, containing 1 to 8 C atoms, or an ether residue, which may be linear or branched, containing 1 to 8 C atoms, and wherein the residue with formula (22a) and the residue with formula (23a): ##STR00213## represent a substituted or unsubstituted heterocyclic residue with 5 to 7 ring atoms, which comprise at least 1 carbon atom and at least 1 nitrogen atom as well as, optionally, 1 or 2 oxygen atoms, wherein 1 nitrogen atom forms a double bond, and wherein the residue with formula (22b) and the residue with formula (23b): ##STR00214## represent a substituted or unsubstituted heterocyclic residue with 5 to 7 ring atoms, which comprise at least 1 carbon atom and at least 1 nitrogen atom as well as, optionally, 1 or 2 oxygen atoms, wherein 1 nitrogen atom forms a single bond.

12. The compound as claimed in claim 4, wherein the organic residue W2a and/or W1 b and/or W1c, respectively independently of each other, represent an organic residue with general formula (31a), (31b), (32), (34), (35), (37a) or (37b): ##STR00215## wherein Y.sup.? is an anion which, respectively independently of each other, represents fluoride, chloride, bromide, iodide, sulphate, hydrogen sulphate, phosphate, hydrogen phosphate, dihydrogen phosphate, tosylate, mesylate, or at least one carboxylation of a carboxylic acid containing 1 to 15 carbon atoms.

13. The compound as claimed in claim 4, wherein the organic residue W1a, respectively independently of each other, represents an organic residue with general formula (31a), (31b), (32) or (34): ##STR00216## and wherein Y.sup.? is an anion which, respectively independently of each other, represents fluoride, chloride, bromide, iodide, sulphate, hydrogen sulphate, phosphate, hydrogen phosphate, dihydrogen phosphate, tosylate, mesylate, or at least one carboxylation of a carboxylic acid containing 1 to 15 carbon atoms.

14. The compound as claimed in claim 4, wherein the compound is at least one compound with formula (40) to (63), (68), (69a), (69b) or (70): ##STR00217## ##STR00218## ##STR00219## ##STR00220## ##STR00221##

15. The method as claimed in claim 1, wherein the at least one photosensitizer is a compound with formula (1): ##STR00222## wherein the residues Q.sup.1 and Q.sup.2, respectively independently of each other, represent one substituted or unsubstituted, monocyclic or polycyclic aromatic residue, wherein the compound with formula (1) does not contain an OH group which is bonded directly to the organic residue Q.sup.1 or Q.sup.2, and wherein K represents hydrogen or a cation, and wherein (a) at least one of the residues Q.sup.1 and Q.sup.2, respectively independently of each other, is substituted with at least one organic residue W1a, wherein the at least one organic residue W1a has the general formula (5a), (6a), (7a), (8a), or (9a):
-A-(C(D)(E)).sub.h-X.sup.a,(5a)
(C(D)(E)).sub.k-aryl-(C(D)(E)).sub.l-X.sup.a,(6a)
-A-(C(D)(E)).sub.k-aryl-(C(D)(E)).sub.l-X.sup.a,(7a)
((C(D)(E)).sub.m-A).sub.p-(C(D)(E)).sub.n-X.sup.a,(8a)
-A-((C(D)(E)).sub.m-A).sub.p-(C(D)(E)).sub.n-X.sup.a,(9a) wherein h represents a whole number from 1 to 20, wherein k represents a whole number from 0 to 10, wherein 1 represents a whole number from 0 to 10, and wherein m, n and p, respectively independently of each other, represent a whole number from 1 to 6, and wherein A, respectively independently of each other, represents oxygen or sulphur, wherein D and E, respectively independently of each other, represent hydrogen, halogen, G-R.sup.(I), or G-C(=G)-R.sup.(II), wherein G, respectively independently of each other, represents oxygen or sulphur, and wherein the residues R.sup.(I) and R.sup.(II), respectively independently of each other, represent hydrogen, methyl, ethyl, n-propyl, n-butyl, n-pentyl, phenyl or benzyl, wherein phenyl and benzyl may be unsubstituted or substituted, wherein aryl represents a substituted or unsubstituted aromatic group or a substituted or unsubstituted heteroaromatic group which does not contain a nitrogen atom, wherein X.sup.a, respectively independently of each other, represents a residue with formula (20c), (20d), or (21): ##STR00223## wherein each of the residues R.sup.(VII), R.sup.(VIII), and R.sup.(IX), respectively independently of each other, represents hydrogen, an aryl residue containing 5 to 12 C atoms, an alkylaryl residue containing 5 to 12 C atoms, an alkyl residue, which may be linear or branched, containing 1 to 8 C atoms, or an ether residue, which may be linear or branched, containing 1 to 8 C atoms, and wherein the residues R1, R2, R3, R4 and R5, respectively independently of each other, represent hydrogen, halogen, alkyl containing 1 to 12 C atoms, cycloalkyl containing 1 to 12 C atoms, alkylaryl containing 1 to 12 C atoms, aryl containing 5 to 20 C atoms, ether containing 2 to 12 C atoms or glycol containing 2 to 12 C atoms, or wherein (b) the residue R3 is an organic residue W2a which contains at least one neutral nitrogen atom which can be protonated, and/or at least one positively charged nitrogen atom and/or at least one positively charged phosphorus atom, wherein the one organic residue W2a has the general formula (4b), (5b), (6b), (7b), (8b), or (9b):
(C(D)(E)).sub.h-X.sup.b,(4b)
-A-(C(D)(E)).sub.h-X.sup.b,(5b)
(C(D)(E)).sub.k-aryl-(C(D)(E)).sub.l-X.sup.b,(6b)
-A-(C(D)(E)).sub.k-aryl-(C(D)(E)).sub.l-X.sup.b,(7b)
[(C(D)(E)).sub.m-A].sub.p(C(D)(E)).sub.n-X.sup.b,(8b)
-A-[(C(D)(E)).sub.m-A].sub.p(C(D)(E)).sub.n-X.sup.b,(9b) and wherein, optionally, at least one of the residues Q.sup.1 and Q.sup.2, respectively independently of each other, is substituted with at least one organic residue W1b which has the general formula (4b), (5b), (6b), (7b), (8b), or (9b), wherein h represents a whole number from 1 to 20, wherein k represents a whole number from 0 to 10, wherein 1 represents a whole number from 0 to 10, and wherein m, n and p, respectively independently of each other, represent a whole number from 1 to 6, and wherein A, respectively independently of each other, represents oxygen or sulphur, wherein D and E, respectively independently of each other, represent hydrogen, halogen, G-R.sup.(I), or G-C(=G)-R.sup.(II), wherein G, respectively independently of each other, represents oxygen or sulphur, and wherein the residues R.sup.(I) and R.sup.(II), respectively independently of each other, represent hydrogen, methyl, ethyl, n-propyl, n-butyl, n-pentyl, phenyl or benzyl, wherein phenyl and benzyl may be unsubstituted or substituted, wherein aryl represents a substituted or unsubstituted aromatic group or a substituted or unsubstituted heteroaromatic group which does not contain a nitrogen atom, wherein X.sup.b, respectively independently of each other, is an organic residue which (i) contains at least one neutral nitrogen atom which can be protonated, or (ii) contains at least one positively charged nitrogen atom, or (iii) contains at least one positively charged phosphorus atom, and wherein the residues R1, R2, R4 and R5, respectively independently of each other, represent hydrogen, halogen, alkyl containing 1 to 12 C atoms, alkylaryl containing 1 to 12 C atoms, aryl containing 5 to 20 C atoms, ether containing 2 to 12 C atoms or glycol containing 2 to 12 C atoms, and/or a pharmacologically acceptable salt and/or ester and/or complex thereof.

16. A non-medical method for the inactivation of microorganisms selected from the group consisting of viruses, archaea, bacteria, bacterial spores, fungi, fungal spores, protozoa, algae and blood-borne parasites, wherein said method comprises contacting the microorganism with a photosensitizer compound as claimed in claim 4 and/or a pharmacologically acceptable salt and/or ester and/or complex thereof.

17. A method for surface cleaning and/or irradiation of an article, said method comprising contacting microorganisms on said article with a photosensitizer compound as claimed in claim 4, and/or a pharmacologically acceptable salt or ester and/or complex thereof.

18. The method as claimed in claim 17, wherein the surface cleaning and/or irradiation is carried out on a material selected from the group consisting of medical products, food packaging, textiles; building materials, electronic devices, furniture and hygiene articles.

19. A method for decontaminating fluids, said method comprising contacting the fluid with a photosensitizer compound as claimed in claim 4 and/or a pharmacologically acceptable salt and/or ester and/or complex thereof.

20. A method for decontaminating foodstuffs, said method comprising contacting the foodstuff with a photosensitizer compound as claimed in claim 4 and/or a pharmacologically acceptable salt and/or ester and/or complex thereof.

21. A coated article, wherein a surface of the article is provided with at least one compound as claimed in claim 4.

22. A compound with formula (100): ##STR00224## and/or with formula (101): ##STR00225## or respectively a pharmacologically acceptable salt and/or ester and/or complex thereof, for use as a photosensitizer in the medical treatment for the inactivation of microorganisms, wherein Q.sup.3, Q.sup.3a, Q.sup.4 and Q.sup.4a, respectively independently of each other, represent one substituted or unsubstituted, monocyclic or polycyclic aromatic residue or one substituted or unsubstituted, monocyclic or polycyclic heteroaromatic residue, wherein K represents hydrogen or a cation, and wherein M.sup.z+ represents a cation of a metal, wherein z is the formal oxidation number of the metal M and z represents a whole number from 1 to 7, and wherein (a1) at least one of the residues Q.sup.3, Q.sup.3a, Q.sup.4 and Q.sup.4a, respectively independently of each other, is an unsubstituted, monocyclic or polycyclic heteroaromatic residue, which has at least 5 ring atoms, wherein the ring atoms contain at least one carbon atom and at least one nitrogen atom which preferably-optionally can be protonated, or (a2) at least one of the residues Q.sup.3, Q.sup.3a, Q.sup.4 and Q.sup.4a, respectively independently of each other, is substituted with at least one organic residue W1, wherein the at least one organic residue W1 has the general formula (4), (5), (6), (7), (8):
(C(D)(E)).sub.h-X,(4)
-A-(C(D)(E)).sub.h-X,(5)
(C(D)(E)).sub.k-aryl-(C(D)(E)).sub.l-X,(6)
-A-(C(D)(E)).sub.k-aryl-(C(D)(E)).sub.l-X,(7)
((C(D)(E)).sub.m-A).sub.p-(C(D)(E)).sub.n-X,(8)
-A-((C(D)(E)).sub.m-A).sub.p-(C(D)(E)).sub.n-X,(9) wherein h represents a whole number from 1 to 20, wherein k and l, respectively independently of each other, represents a whole number from 0 to 10, and wherein m, n and p, respectively independently of each other, represent a whole number from 1 to 6 and wherein A, respectively independently of each other, represents oxygen or sulphur, wherein D and E, respectively independently of each other, represent hydrogen, halogen, G-R.sup.(I), or G-C(=G)-R.sup.(II), wherein G, respectively independently of each other, represents oxygen or sulphur, and wherein the residues R.sup.(I) and R.sup.(II), respectively independently of each other, represent hydrogen, methyl, ethyl, n-propyl, n-butyl, n-pentyl, phenyl or benzyl, wherein phenyl and benzyl may be unsubstituted or substituted, wherein aryl represents a substituted or unsubstituted aromatic group or a substituted or unsubstituted heteroaromatic group which does not contain a nitrogen atom, wherein X, respectively independently of each other, is an organic residue which (i) contains at least one neutral nitrogen atom which can be protonated, or (ii) at least one positively charged nitrogen atom or (iii) at least one positively charged phosphorus atom, and wherein the residues R1, R2, R3, R4 and R5, respectively independently of each other, represent hydrogen, halogen, alkyl containing 1 to 12 C atoms, cycloalkyl containing 1 to 12 C atoms, alkylaryl containing 1 to 12 C atoms, aryl containing 5 to 20 C atoms, ether containing 2 to 12 C atoms or glycol containing 2 to 12 C atoms, or wherein (b) the residue R3 is an organic residue W2, wherein the one organic residue W2 has the general formula (4), (5), (6), (7), (8), (9), or (10):
(C(D)(E)).sub.h-X,(4)
-A-(C(D)(E)).sub.h-X,(5)
(C(D)(E)).sub.k-aryl-(C(D)(E)).sub.l-X,(6)
-A-(C(D)(E)).sub.k-aryl-(C(D)(E)).sub.l-X,(7)
[(C(D)(E)).sub.m-A].sub.p(C(D)(E)).sub.n-X,(8)
-A-[(C(D)(E)).sub.m-A].sub.p(C(D)(E)).sub.n-X,(9)
-(-C(D)=C(E)-).sub.r-X,(10) and wherein, optionally, at least one of the residues Q.sup.3, Q.sup.3a, Q.sup.4 and Q.sup.4a, respectively independently of each other, is substituted with at least one organic residue W1 which has the general formula (4), (5), (6), (7), (8), or (9), wherein h represents a whole number from 1 to 20, wherein k and l, respectively independently of each other, represents a whole number from 0 to 10 and wherein m, n, p, and r, respectively independently of each other, represent a whole number from 1 to 6, and wherein A, respectively independently of each other, represents oxygen or sulphur, wherein D and E, respectively independently of each other, represent hydrogen, halogen, G-R.sup.(I), or G-C(=G)-R.sup.(II), wherein G, respectively independently of each other, represents oxygen or sulphur, and wherein the residues R.sup.(I) and R.sup.(II), respectively independently of each other, represent hydrogen, methyl, ethyl, n-propyl, n-butyl, n-pentyl, phenyl or benzyl, wherein phenyl and benzyl may be unsubstituted or substituted, wherein aryl represents a substituted or unsubstituted aromatic group or a substituted or unsubstituted heteroaromatic group which does not contain a nitrogen atom, wherein X, respectively independently of each other, is an organic residue which (i) contains at least one neutral nitrogen atom which can be protonated, (ii) contains at least one positively charged nitrogen atom or (iii) contains at least one positively charged phosphorus atom, and wherein the residues R1, R2, R4 and R5, respectively independently of each other, represent hydrogen, halogen, alkyl containing 1 to 12 C atoms, alkylaryl containing 1 to 12 C atoms, aryl containing 5 to 20 C atoms, ether containing 2 to 12 C atoms or glycol containing 2 to 12 C atoms.

Description

COMPARATIVE EXAMPLE 3

[1015] In a further test, the stability and phototoxicity of the following compounds were tested.

##STR00197##

[1016] The compound CRANAD-2 is a good fluorophore which has a fluorescence quantum yield which is comparable with rhodamine or Cy5 dyes.

[1017] Incubation with CRANAD-2 and the bacterial strains S. aureus ATCC 25923 and E. coli ATCC 25922 employed, as well as irradiation with electromagnetic radiation and determination of the phototoxicity were carried out as described in sections c.1) and c.2) above. An inactivation of the tested bacterial strains S. aureus ATCC 25923 and E. coli ATCC 25922 upon illumination in the presence of CRANAD-2 could not be ascertained with either of the methods.

[1018] Because of the amine substituents directly on the aromatic ring, which can act as electron pair donors, the photophysics are displaced into a singlet process and substantially less energy is available for triplet processes. A good transfer of energy into the triplet level should be the prerequisite for a photodynamic effect which, however, was not observed for the compound CRANAD-2.

[1019] Incubation with the compound (71) (SACUR-01d) and the bacterial strains S. aureus ATCC 25923 and E. coli ATCC 25922 employed as well as irradiation with electromagnetic radiation and determination of the phototoxicity were carried out as described in sections c.1) and c.2) above. Hardly any inactivation of the tested bacterial strains S. aureus ATCC 25923 and E. coli ATCC 25922 was observed with either of the methods upon illumination in the presence of compound (71) (SACUR-01d), because the decomposition of the compound in the measurement solution meant that no reliable values were obtained. Compound (71) (SACUR-01d) exhibited a low stability in aqueous solution which was comparable with the natural basic substance curcumin. The free OH groups contribute greatly to this photo-instability because due to them, the compound can readily transform into the quinoid mesomer, and thus cleavage of one half of the molecule with the formation of ferulic acids or substituted vanillins is facilitated.

[1020] The molar extinction coefficient for compound (71) (SACUR-01d) at 420 nm in the aqueous solutions A-C given below varied between 8000 and 16000 M.sup.?1 cm.sup.?1 and thus was significantly smaller than the value known for curcumin (?.sub.420, H2O=23800 M.sup.?1 cm.sup.?1) (see Arnaut L G, Formosinho S J. J. Photochem. Photobiol. A: Chem. 75, 1993, pages 1 to 20). These results show that the compound (71) does not have sufficient stability in aqueous solution to establish a photodynamic effect after irradiation.

[1021] Aqueous solution A: distilled water.

[1022] Aqueous solution B: isotonic sodium chloride solution (0.9% by weight NaCl).

[1023] Aqueous solution C: PBS buffer, pH 7.4 (composition: see Sambrook, J.; Maniatis, T.; Russel, D. W.: Molecular cloning: a laboratory manual. Cold Spring Harbor Laboratory Press; 3rd edition (2001)).