Claims
- 1. An N- and O-substituted aminophenol derivative of formula: ##STR104## wherein G is the residue of an organic or inorganic acid or a glycoside residue,
- R.sup.1 and R.sup.2, which are the same or different, are hydrogen or halogen, SO.sub.3 H, PO.sub.3 H.sub.2 or a salt of the acid residues, hydroxyl, nitro, carboxyl, carboxamido or cyano or alkyl, alkenyl, alkoxy, alkylsulphinyl, alkylsulphonyl, alkoxycarbonyl, alkylcarbonyl, aryl or aralkyl unsubstituted or substituted at least once by hydroxyl, carboxyl, halogen, cyano, SO.sub.3 H or PO.sub.3 H.sub.2 or a salt of one of the acid residues or,
- when two substituents of R.sup.1 and R.sup.2 are present on neighbouring carbon atoms, together represent a 1,4-butadiendiyl radical which is unsubstituted or substituted at least once by SO.sub.3 H, PO.sub.3 H.sub.2 or a salt of the acid groups, an alkyl or a carboxyl group,
- R.sup.3 is hydrogen, --CO--COOH, SO.sub.3 H, SO.sub.3 H, PO.sub.3 H.sub.2 or a salt of the acid groups, an alkylcarbonyl radical unsubstituted or substituted at least once by halogen, COOH, SO.sub.3 H or PO.sub.3 H.sub.2 or a salt of the acid groups or an arylcarbonyl radical unsubstituted or substituted at least once by SO.sub.3 H, PO.sub.3 H.sub.2 or a salt of the acid groups, and
- L is a pyrazolo-heterocylic radical of the general formula: ##STR105## wherein X-Y signifies NR.sup.8 --CO or N.dbd.CR.sup.9, wherein R.sup.8 is hydrogen or an alkyl and R.sup.9 is alkyl, alkenyl, alkoxy, alkylthio, aryl, aralkyl, in each case substituted or substituted by hydroxyl, dialkylphosphinyl, carboxyl SO.sub.3 H, PO.sub.3 H.sub.2, a salt of one of the acid groups or alkoxycarbonyl; amino, which is unsubstituted or substituted by one or two alkyl radicals which alkyls are unsubstituted or substituted by at least one hydroxyl, carboxyl or alkoxycarbonyl radical and wherein when amino is substituted by two alkyl radicals, the alkyl radicals can be joined to form a ring which, apart from the first nitrogen atom of the amino group, is uninterrupted or is interrupted by oxygen, sulphur or a second nitrogen atom, or amino is unsubstituted or substituted by one or two acyl radicals, alkoxy- or aralkoxycarbonyl radicals, H.sub.2 N--CO, alkyl, aralkyl- or arylcarbamoyl radicals; or R.sup.9 hydrogen, carboxyl, alkoxycarbonyl, carboxamido or halogen, and
- Z signifies NR.sup.10 --N.dbd.N, wherein R.sup.10 is hydrogen or an alkyl or aralkyl radical, or
- Z is an unsaturated 3-5 member chain of nitrogen atoms or of carbon atoms, or said chain having at least one nitrogen or sulphur atom, whereby carbon atoms in the chain are unsubstituted or substituted by alkyl, alkoxy, hydroxylalkyl, alkylthio, hydroxyl, aralkyl, aryl, carboxyl, carboxamido, alkoxycarbonyl, cyano, amino, which is unsubstituted or substituted by one or two alkyl radicals which alkyl is unsubstituted or substituted by at least one hydroxyl, carboxyl or alkoxycarbonyl radicals or halogen, as well as nitrogen which are not attached via a double bone are unsubstituted or substituted by alkyl or aralkyl or two neighbouring chain substituents form an alkylene which, alkylene is unsubstituted or substituted or anellated with aryl and tautomers thereof,
- with the proviso that when G is an alkanecarboxylic acid radical, R.sup.3 is hydrogen, an arylcarbonyl radical or an alkylcarbonyl radical unsubstituted or substituted at least once by halogen and L is pyrazolo-heterocyclic radical of formula (III), wherein X-Y signifies N.dbd.CR.sup.9, whereby R.sup.9 has the above-given meaning, Z does not form a 1,2,4-triazole ring in which a nitrogen atom not connected via a double bond is substituted with hydrogen.
- 2. The compound of claim 1 wherein G is a galactoside, glycoside, mannoside, N-acetylglucosaminide or an oligosaccharide radical consisting of 2 to 10 monosaccharide units.
- 3. The compounds of claim 1 wherein G is an N-acetyl-.beta.-D-glucosaminidyl radical.
- 4. The compounds of claim 1 wherein G is PO.sub.3 MM', SO.sub.3 M, a carboxyl-bound alkanecarboxylic acid, amino acid or oligopeptide residue and M and M' are hydrogen, alkali metal, alkaline earth metal or ammonium ions.
- 5. The compound of claim 1 wherein alkanecarboxylic acid residues of G are acetic, propionic, butyric, palmitic, stearic, oleic, linoleic or linolenic; and amino acid residue of G is glycine, alanine, valine, leucine, isoleucine, phenylalanine or tyrosine and a glycoside radical of G is .beta.-glucosidically bound N-acetyl-2-D-glucosamine.
- 6. The compound of claim 1 wherein alkyl alone or combined is methyl, ethyl, propyl, isobutyl or tert.-butyl the twice-substituted amino is morpholino, hydroyalkyl is 2-hydroxyethyl, 1-hydroxyethyl or hydroxymethyl, aryl is phenyl, aralkyl is benzyl, aralkoxy is benzyloxy, alkenyl is vinyl or allyl, halogen is fluorine or chlorine, acyl is acetyl, phenylacetyl or benzoyl, alkylene is butadiendiyl, dialkylphosphinyl is dimethylphosphinyl and L is a pyrazoloheterocyclic radical of formula III wherein X-Y is N--CR.sup.9 wherein R.sup.9 is hydrogen or alkoxy.
- 7. The compound of claim 1 wherein L is from the group consisting of formulas (XIII) to XXIII and XXIV as follows: ##STR106## and tautomers thereof.
- 8. The compound of claim 1 wherein L is selected from the group consisting of formulas XIII, XIV, XV, XVII, XVIII, XX and tautomers thereof.
- 9. A compound of formula: ##STR107## in which R.sup.1 -R.sub.3 have the meanings given in claim 1 and L is a pyrazolo-heterocyclic radical of formula: ##STR108## wherein X-Y and Z have the meanings given in claim 1, with the proviso that when R.sup.3 is an arylcarbonyl radical or an alkylcarbonyl radical unsubstituted or substituted at least once by halogen and X-Y is C.dbd.NR.sup.9, then Z does not form a 1,2,3-triazole ring in which a nitrogen atom not connected via a double bond is substituted with a hydrogen atom.
- 10. A compound of formula: ##STR109## wherein R.sup.1 and R.sup.2 have the meanings given in claim 1 and L is a pyrazolo-heterocyclic radical of the general formula ##STR110## in which X-Y and Z have the meanings given in claim 1.
- 11. A method for the preparation of a compound of claim 1 or 2 comprising using a compound of claim 9 or 10.
- 12. A compound of claim 1 prepared by the process of claim 25.
- 13. A compound of claim 3 prepared by the process of claim 26.
- 14. The aminophenol derivative designated .beta.-glucosidically-bound-N-acetyl-2-D-glucosaminide of 4-hydroxyphenyl-2-methylpyrazolo-[1,5-a]pyridine-3-ylamine or of 4-hydroxyphenyl-pyrazolo-[1,5-a]-pyridine-3-ylamine.
- 15. A diagnostic agent for determination of a hydrolase, comprising a chromogenic enzyme substrate and an appropriate buffer substance wherein the chromogenic substrate is a compound of the formula ##STR111## wherein G is the residue of an organic or inorganic acid or a glycoside residue,
- R.sup.1 and R.sup.2, which are the same or different, are hydrogen or halogen, SO.sub.3 H, PO.sub.3 H.sub.2 or a salt of the acid residues, hydroxyl, nitro, carboxyl, carboxamido or cyano or alkyl, alkenyl, alkoxy, alkylsulphinyl, alkylsulphonyl, alkoxycarbonyl, alkylcarbonyl, aryl or aralkyl unsubstituted or substituted at least once by hydroxyl, carboxyl, halogen, cyano, SO.sub.3 H or PO.sub.3 H.sub.2 or a salt of one of the acid residues or,
- when two substituents of R.sup.1 and R.sup.2 are present on neighboring carbon atoms, together represent a 1,4-butadienydiyl radical which is unsubstituted or substituted at least once by SO.sub.3 H, PO.sub.3 H.sub.2 or a salt of the acid groups, an alkyl or a carboxyl group,
- R.sup.3 is hydrogen, --CO--COOH, SO.sub.3 H, PO.sub.3 H.sub.2 or a salt of the acid groups, an alkylcarbonyl radical unsubstituted or substituted at least once by halogen, COOH, SO.sub.3 H or PO.sub.3 H.sub.2 or a salt of the acid groups or an arylcarbonyl radical unsubstituted or substituted at least once by SO.sub.3 H, PO.sub.3 H.sub.2 or a salt of the acid groups, and
- L is a radical of the formula: ##STR112## wherein R.sup.4 and R.sup.5, which are the same or different, are alkyl or together represent a saturated 3-6 member hydrocarbon chain which is uninterrupted or interrupted by oxygen, sulphur or nitrogen and wherein alkyl or the hydrocarbon chain is unsubstituted or substituted at least once by hydroxyl, carboxyl, alkoxycarbonyl, alkoxy, SO.sub.3 H OR PO.sub.3 H.sub.2, a salt of one of the acid groups or halogen, and
- R.sup.6 and R.sup.7, which can be the same or different, are hydrogen or halogen, hydroxyl or carboxamido or an alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, aryl or aralkyl radical unsubstituted or substituted at least once by hydroxyl, carboxyl, halogen, SO.sub.3 H or PO.sub.3 H.sub.2 or a salt of one of the acid groups, or
- L is a pyrazol-heterocylic radical of the general formula: ##STR113## wherein X-Y signifies NR.sup.8 --CO or N.dbd.CR.sup.9, wherein R.sup.8 is hydrogen or an alkyl and R.sup.9 is alkyl, alkenyl, alkoxy, alkylthio, aryl, aralkyl, in each case unsubstituted or substituted by hydroxyl, dialkylphosphinyl, carboxyl SO.sub.3 H, PO.sub.3 H.sub.2, a salt of one of the acid groups or alkoxycarbonyl; amino, which is unsubstituted or substituted by one or two alkyl radicals which alkyls are unsubstituted or substituted by at least one hydroxyl, carboxyl or alkoxycarbonyl radical and wherein when amino is substituted by two alkyl radicals, the alkyl radicals can be joined to form a ring which, apart from the first nitrogen atom of the amino group, is uninterrupted or is interrupted by oxygen, sulphur or a second nitrogen atom, or amino is unsubstituted or substituted by one or two acyl radicals, alkoxy- or aralkoxycarbonyl radicals, H.sub.2 N--CO, alkyl-, aralkyl- or arylcarbamoyl radicals; or R.sup.9 hydrogen, carboxyl, alkoxycarbonyl, carboxamido or halogen, and
- Z signifies NR.sup.10 --N.dbd.N, wherein R.sup.10 is hydrogen or an alkyl or aralkyl radical, or
- Z is an unsaturated 3-5 member chain of nitrogen atoms or of carbon atoms, or said chain having at least one nitrogen or sulphur atom, whereby carbon atoms in the chain are unsubstituted or substituted by alkyl, alkoxy, hydroxyalkyl, alkylthio, hydroxyl, aralkyl, aryl, carboxyl, carboxamido, alkoxycarbonyl, cyano, amino, which is unsubstituted or substituted by one or two alkyl radicals which alkyl is unsubstituted or substituted by at least one hydroxyl, carboxyl or alkoxycarbonyl radicals or halogen, as well as nitrogen which are not attached via a double bond are unsubstituted or substituted by alkyl or aralkyl or two neighboring chain substituents form an alkylene which, alkylene is unsubstituted or substituted or anellated with aryl and tautomers thereof,
- with the proviso that when G is an alkanecarboxylic acid radical, R.sup.3 is hydrogen, an arylcarbonyl radical or an alkylcarbonyl radical unsubstituted or substituted at least once by halogen and L is pyrazolo-heterocyclic radical of formula (III), wherein X-Y signifies N.dbd.CR.sup.9, whereby R.sup.9 has the above-given meaning, Z does not form a 1,2,4-triazole ring in which a nitrogen atom not connected via a double bond is substituted with hydrogen with the proviso that when G is alkanecarboxylic acid radical, R.sup.3 is hydrogen, an alkylcarbonyl radical or an alkylcarbonyl radical unsubstituted or substituted at least once by halogen and L is a pyrazolo-heterocyclic radical of formula III wherein X-Y is N.dbd.CR.sup.9, wherein R.sup.9 has the meaning in claim 1 then Z can form a 1,2,4-triazole ring in which a nitrogen atom not connected by a double bond is substituted by hydrogen.
- 16. The diagnostic agent of claim 15, comprising an oxidizing agent.
- 17. The diagnostic agent of claim 15 further comprising an 1-arylsemicarbazide of the formula:
- Ar--NH--NH--CONH.sub.2 (XII)
- wherein Ar is an aryl radical unsubstituted or substituted by alkyl, alkoxy or halogen.
- 18. The diagnostic agent of claim 17 designated o-methyl, p-methyl, o-methoxy, m-methoxy-, p-methoxy, o-chloro-m-chloro, m-methyl- and unsubstituted phenyl semicarbazides and naphthyl semicarbazide.
- 19. The diagnostic agent of claim 15 wherein the components are in carrier-bound form.
- 20. The diagnostic agent of claim 17 wherein the components are in carrier-bound form.
- 21. An N- and O-substituted aminophenol derivative of formula: ##STR114## wherein G is the residue of an organic or inorganic acid or a glycoside residue,
- R.sup.1 and R.sup.2, which are the same or different, are hydrogen or halogen, SO.sub.3 H, PO.sub.3 H.sub.2 or a salt of the acid residues, hydroxyl, nitro, carboxyl, carboxamido or cyano or alkyl, alkenyl, alkoxy, alkylsulphinyl, alkylsulphonyl, alkoxycarbonyl, alkylcarbonyl, aryl or aralkyl unsubstituted or substituted at least once by hydroxyl, carboxyl, halogen, cyano, SO.sub.3 H or PO.sub.3 H.sub.2 or a salt of one of the acid residues or,
- when two substituents of R.sup.1 and R.sup.2 are present on neighbouring carbon atoms, together represent a 1,4-butadiendiyl radical which is unsubstituted or substituted at least once by SO.sub.3 H, PO.sub.3 H.sub.2 or a salt of the acid groups, an alkyl or a carboxyl group,
- R.sup.3 is an alkylcarbonyl substituted at least once by halogen, and
- L is a radical of the formula: ##STR115## wherein R.sup.4 and R.sup.5, which are the same or different, are alkyl or together represent a saturated 3-6 member hydrocarbon chain which is uninterrupted or interrupted by oxygen, sulphur or nitrogen and wherein alkyl or the hydrocarbon chain is unsubstituted or substituted at least once by hydroxyl, carboxyl, alkoxycarbonyl, alkoxy, SO.sub.3 H OR PO.sub.3 H.sub.2, a salt of one of the acid groups or halogen, and
- R.sup.6 and R.sup.7, which can be the same or different, are hydrogen or halogen, hydroxyl or carboxamido or an alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, aryl or aralkyl radical unsubstituted or substituted at least once by hydroxyl, carboxyl, halogen, SO.sub.3 H or PO.sub.3 H.sub.2 or a salt of one of the acid groups, or
- L is a pyrazolo-heterocylic radical of the general formula: ##STR116## wherein X-Y signifies NR.sup.8 --CO or N.dbd.CR.sup.9, wherein R.sup.8 is hydrogen or an alkyl and R.sup.9 is alkyl, alkenyl, alkoxy, alkylthio, aryl, aralkyl, in each case unsubstituted or substituted by hydroxyl, dialkylphosphinyl, carboxyl SO.sub.3 H, PO.sub.3 H.sub.2, a salt of one of the acid groups or alkoxycarbonyl; amino, which is unsubstituted or substituted by one or two alkyl radicals which alkyls are unsubstituted or substituted by at least one hydroxyl, carboxyl or alkoxycarbonyl radical and wherein when amino is substituted by two alkyl radicals, the alkyl radicals can be joined to form a ring which, apart from the first nitrogen atom of the amino group, is uninterrupted or is interrupted by oxygen, sulphur or a second nitrogen atom, or amino is unsubstituted or substituted by one or two acyl radicals, alkoxy- or aralkoxycarbonyl radicals, H.sub.2 N--CO, alkyl-, aralkyl- or arylcarbamoyl radicals; or R.sup.9 hydrogen, carboxyl, alkoxycarbonyl, carboxamido or halogen, and
- Z signifies NR.sup.10 --N.dbd.N, wherein R.sup.10 is hydrogen or an alkyl or aralkyl radical, or
- Z is an unsaturated 3-5 member chain of nitrogen atoms or of carbon atoms, or said chain having at least one nitrogen or sulphur atom, whereby carbon atoms in the chain are unsubstituted or substituted by alkyl, alkoxy, hydroxyalkyl, alkylthio, hydroxyl, aralkyl, aryl, carboxyl, carboxamido, alkoxycarbonyl, cyano, amino, which is unsubstituted or substituted by one or two alkyl radicals which alkyl is unsubstituted or substituted by at least one hydroxyl, carboxyl or alkoxycarbonyl radicals or halogen, as well as nitrogen which are not attached via a double bone are unsubstituted or substituted by alkyl or aralkyl or two neighbouring chain substituents form an alkylene which, alkylene is unsubstituted or substituted or anellated with aryl and tautomers thereof,
- with the proviso that when G is an alkanecarboxylic acid radical, R.sup.3 is hydrogen, an arylcarbonyl radical or an alkylcarbonyl radical unsubstituted or substituted at least once by halogen and L is pyrazolo-heterocyclic radical of formula (III), wherein X-Y signifies N.dbd.CR.sup.9, wherein R.sup.9 has the above-given meaning, Z does not form a 1,2,4-triazole ring in which a nitrogen atom not connected via a double bond is substituted with hydrogen.
- 22. An N- and O-substituted aminophenol derivative of formula: ##STR117## wherein G is a glycoside residue or an inorganic acid residue,
- R.sup.1 and R.sup.2, which are the same or different, are hydrogen or halogen, SO.sub.3 H, PO.sub.3 H.sub.2 or a salt of the acid residues, hydroxyl, nitro, carboxyl, carboxamido or cyano or alkyl, alkenyl, alkoxy, alkylsulphinyl, alkylsulphonyl, alkoxycarbonyl, alkylcarbonyl, aryl or aralkyl unsubstituted or substituted at least once by hydroxyl, carboxyl, halogen, cyano, SO.sub.3 H or PO.sub.3 H.sub.2 or a salt of one of the acid residues or,
- when two substituents of R.sup.1 and R.sup.2 are present on neighbouring carbon atoms, together represent a 1,4-butadienyl radical which is unsubstituted or substituted at least once by SO.sub.3 H, PO.sub.3 H.sub.2 or a salt of the acid groups, an alkyl or a carboxyl group,
- R.sup.3 is hydrogen, --CO--COOH, SO.sub.3 H, PO.sub.3 H.sub.2 or a salt of the acid groups, an alkylcarbonyl radical unsubstituted or substituted at least once by halogen, COOH, SO.sub.3 H or PO.sub.3 H.sub.2 or a salt of the acid groups or an arylcarbonyl radical unsubstituted or substituted at least once by SO.sub.3 H, PO.sub.3 H.sub.2 or a salt of the acid groups, and
- L is a radical of the formula: ##STR118## wherein R.sup.4 and R.sup.5, which are the same or different, are alkyl or together represent a saturated 3-6 member hydrocarbon chain which is uninterrupted or interrupted by oxygen, sulphur or nitrogen and wherein alkyl or the hydrocarbon chain is unsubstituted or substituted at least once by hydroxyl, carboxyl, alkoxycarbonyl, alkoxy, SO.sub.3 H OR PO.sub.3 H.sub.2, a salt of one of the acid groups or halogen, and
- R.sup.6 and R.sup.7, which can be the same or different, are hydrogen or halogen, hydroxyl or carboxamido or an alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, aryl or aralkyl radical unsubstituted or substituted at least once by hydroxyl, carboxyl, halogen, SO.sub.3 H or PO.sub.3l H.sub.2 or a salt of one of the acid groups, or
- L is a pyrazolo-heterocylic radical of the general formula: ##STR119## wherein X-Y signifies NR.sup.8 --CO or N.dbd.CR.sup.9, wherein R.sup.8 is hydrogen or an alkyl and R.sup.9 is alkyl, alkenyl, alkoxy, alkylthio, aryl, aralkyl, in each case unsubstituted or substituted by hydroxyl, dialkylphosphinyl, carboxyl SO.sub.3 H, PO.sub.3 H.sub.2, a salt of one of the acid group or alkoxycarbonyl; amino, which is unsubstituted or substituted by one or two alkyl radicals which alkyls are unsubstituted or substituted by at least one hydroxyl, carboxyl or alkoxycarbonyl radical and wherein when amino is substituted by two alkyl radicals, the alkyl radicals can be joined to form a ring which, apart from the first nitrogen atom of the amino group, is uninterrupted or is interrupted by oxygen, sulphur or a second nitrogen atom, or amino is unsubstituted or substituted by one or two acyl radicals, alkoxy- or aralkoxycarbonyl radicals, H.sub.2 N--CO, alkyl-, aralkyl- or arylcarbamoyl radicals; or R.sup.9 hydrogen, carboxyl, alkoxycarbonyl, carboxamido or halogen, and
- Z signifies NR.sup.10 --N.dbd.N, wherein R.sup.10 is hydrogen or an alkyl or aralkyl radical, or
- Z is an unsaturated 3-5 member chain of nitrogen atoms or of carbon atoms, or said chain having at least one nitrogen or sulphur atom, whereby carbon atoms in the chain are unsubstituted or substituted by alkyl, alkoxy, hydroxyalkyl, alkylthio, hydroxyl, aralkyl, aryl, carboxyl, carboxamido, alkoxycarbonyl, cyano, amino, which is unsubstituted or substituted by one or two alkyl radicals which alkyl is unsubstituted or substituted by at least one hydroxyl, carboxyl or alkoxycarbonyl radicals or halogen, as well as nitrogen which are not attached via a double bone are unsubstituted or substituted by alkyl or aralkyl or two neighbouring chain substituents form an alkylene which, alkylene is unsubstituted or substituted or annellated with aryl and tautomers thereof,
- with the provisio that when G is an alkanecarboxylic acid radical, R.sup.3 is hydrogen, an arylcarbonyl radical or an alkylcarbonyl radical unsubstituted or substituted at least once by halogen and L is pyrazolo-heterocyclic radical of formula (III), wherein X-Y signifies N.dbd.CR.sup.9, whereby R.sup.9 has the above-given meaning, Z does not form a 1,2,4-triazole ring in
- 23. The compound of claim 22 wherein G is a galactoside, glycoside, mannoside, N-acetylglucosaminide or an oligosaccharide radical consisting of 2 to 10 monosaccharide units.
- 24. The compounds of claim 22 wherein G is an N-acetyl-.beta.-D-glucosamindyl radicals.
- 25. A process for the preparation of a compound of the formula wherein ##STR120## G is the residue of an organic or inorganic acid or a glycoside residue, R.sup.1 and R.sup.2, which are the same or different, are hydrogen or halogen, SO.sub.3 H, PO.sub.3 H.sub.2 or a salt of the acid residues, hydroxyl, nitro, carboxyl, carboxamido or cyano or alkyl, alkenyl, alkoxy, alkylsulphinyl, alkylsulphonyl, alkoxycarbonyl, alkylcarbonyl, aryl or aralkyl unsubstituted or substituted at least once by hydroxyl, carboxyl, halogen, cyano, SO.sub.3 H or PO.sub.3 H.sub.2 or a salt of one of the acid residues or,
- when two substituents of R.sup.1 and R.sup.2 are present on neighboring carbon atoms, together represent a 1,4-butadiendiyl radical which is unsubstituted or substituted at least once by SO.sub.3 H, PO.sub.3 H.sub.2 or a salt of the acid groups, an alkyl or a carboxyl group,
- R.sup.3 is hydrogen, --CO--COOH, SO.sub.3 H, PO.sub.3 H.sub.2 or a salt of the acid groups, an alkylcarbonyl radical unsubstituted or substituted at least once by halogen, COOH, SO.sub.3 H or PO.sub.3 H.sub.2 or a salt of the acid groups or an arylcarbonyl radical unsubstituted or substituted at least once by SO.sub.3 H, PO.sub.3 H.sub.2 or a salt of the acid groups, and
- L is a radical of the formula: ##STR121## wherein R.sup.4 and R.sup.5, which are the same or different, are alkyl or together represent a saturated 3-6 member hydrocarbon chain which is uninterrupted or interrupted by oxygen, sulphur or nitrogen and wherein alkyl or the hydrocarbon chain is unsubstituted or substituted at least once by hydroxyl, carboxyl, alkoxycarbonyl, alkoxy, SO.sub.3 H OR PO.sub.3 H.sub.2, a salt of one of the acid groups or halogen, and
- R.sup.6 and R.sup.7, which can be the same or different, are hydrogen or halogen, hydroxyl or carboxamido or an alkyl, alkoxy, alkylcarbonyl, aryl or aralkyl radical unsubstituted or substituted at least once by hydroxyl, carboxyl, halogen, SO.sub.3 H or PO.sub.3 H.sub.2 or a salt of one of the acid groups, or
- L is a pyrazolo-heterocylic radical of the general formula: ##STR122## wherein X-Y signifies NR.sup.8 --CO or N.dbd.CR.sup.9, wherein R.sup.8 is hydrogen or an alkyl and R.sup.9 is alkyl, alkenyl, alkoxy, alkylthio, aryl, aralkyl, in each case unsubstituted or unsubstituted by hydroxyl, dialkylphosphinyl, carboxyl SO.sub.3 H, PO.sub.3 H.sub.2, a salt of one of the acid groups or alkoxycarbonyl; amino, which is unsubstituted or substituted by one or two alkyl radicals which alkyls are unsubstituted or substituted by at least one hydroxyl, carboxyl or alkoxycarbonyl radical and wherein when amino is substituted by two alkyl radicals, the alkyl radical can be joined to form a ring which, apart from the first nitrogen atom of the amino group, is uninterrupted or is interrupted by oxygen, sulphur or a second nitrogen atom, or amino is unsubstituted or substituted by one or two acyl radicals, alkoxy- or aralkoxycarbonyl radicals, H.sub.2 N--CO, alkyl-, aralkyl- or arylcarbamoyl radicals; or R.sup.9 hydrogen, carboxyl, alkoxycarbonyl, carboxamido or halogen, and
- Z signifies NR.sup.10 --N.dbd.N, wherein R.sup.10 is hydrogen or an alkyl or aralkyl radical, or
- Z is an unsaturated 3-5 member chain of nitrogen atoms or of carbon atoms, or said chain having at least one nitrogen or sulphur atom, whereby carbon atoms in the chain are unsubstituted or substituted by alkyl, alkoxy, hydroxyalkyl, alkylthio, hydroxyl, aralkyl, aryl, carboxyl, carboxamido, alkoxycarbonyl, cyano, amino, which is unsubstituted or substituted by one or two alkyl radicals which alkyl is unsubstituted or substituted by at least one hydroxyl, carboxyl or alkoxycarbonyl radicals or halogen, as well as nitrogen which are not attached via a double bond are unsubstituted or substituted by alkyl or aralkyl or two neighboring chain substituents form an alkylene which, alkylene is unsubstituted or substituted or anellated with aryl and tautomers thereof,
- with the proviso that when G is an alkanecarboxylic acid radical, R.sup.3 is hydrogen, an arylcarbonyl radical or an alkylcarbonyl radical unsubstituted or substituted at least once by halogen and L is pyrazolo-heterocyclic radical of formula (III), wherein X-Y signifies N.dbd.CR.sup.9, whereby R.sup.9 has the above-given meaning, Z does not form a 1,2,4-triazole ring in which a nitrogen atom not connected via a double bond is substituted with hydrogen,
- comprising
- reacting a compound of formula:
- G--D (IV)
- wherein G is the residue of an organic or inorganic acid or a glycoside residue and D is a reactive group and wherein any functional groups of G are unprotected or protected with protective groups of peptide carbohydrate chemistry with a compound of the formula: ##STR123##
- 26. The process of claim 25 further comprising for the preparation of a compound wherein G is an N-acetyl-.beta.-D glucosaminidyl radical
- reacting as a compound of formula (IV), a compound of formula: ##STR124## wherein W is halogen, R is a hydroxyl protective group conventional in carbohydrate chemistry and B is an azide group, a protected amino group or NH--COCH.sub.3 or B and W together form the group: ##STR125## with a compound of formula: ##STR126## in which R.sup.1 -R.sup.3, L and A have the meanings given above, and removing the amino protective group when B is a protected amino group or converting azide to amino when B is an azide by reduction into an amino group and converting the amino group by acetylation into an --NHCOCH.sub.3 radical and removing subsequently the hydroxyl protective groups.
- 27. A process for the preparation of a compound of the formula ##STR127## in which R.sup.1 and R.sup.2, which are the same or different, are hydrogen or halogen, SO.sub.3 H, PO.sub.3 H.sub.2 or a salt of the acid residues, hydroxyl, nitro, carboxyl, carboxamido or cyano or alkyl, alkenyl, alkoxy, alkylsulphinyl, alkylsulphonyl, alkoxycarbonyl, alkylcarbonyl, aryl or aralkyl unsubstituted or substituted at least once by hydroxyl, carboxyl, halogen, cyano, SO.sub.3 H or PO.sub.3 H.sub.2 or a salt of one of the acid residues or,
- when two substituents of R.sup.1 and R.sup.2 are present on neighboring carbon atoms, together represent a 1,4-butadiendiyl radical which is unsubstituted or substituted at least once by SO.sub.3 H, PO.sub.3 H.sub.2 or a salt of the acid groups, an alkyl or a carboxyl group,
- R.sup.3 is hydrogen, --CO--COOH, SO.sub.3 H, PO.sub.3 H.sub.2 or a salt of the acid groups, an alkylcarbonyl radical unsubstituted or substituted at least once by halogen, COOH, SO.sub.3 H or PO.sub.3 H.sub.2 or a salt of the acid groups or an arylcarbonyl radical unsubstituted or substituted at least once by SO.sub.3 H, PO.sub.3 H.sub.2 or a salt of the acid groups, and L is a pyrazolo-heterocyclic radical of formula: ##STR128## wherein X-Y signifies NR.sup.8 --CO or N.dbd.CR.sup.9, wherein R.sup.8 is hydrogen or an alkyl and R.sup.9 is alkyl, alkenyl, alkoxy, alkylthio, aryl, aralkyl, in each case unsubstituted or substituted by hydroxyl, dialkylphosphinyl, carboxyl SO.sub.3 H, PO.sub.3 H.sub.2, a salt of one of the acid groups or alkoxycarbonyl; amino, which is unsubstituted or substituted by one or two alkyl radicals which alkyls are unsubstituted or substituted by at least one hydroxyl, carboxyl or alkoxycarbonyl radical and wherein when amino is substituted by two alkyl radicals, the alkyl radicals can be joined to form a ring which, apart from the first nitrogen atom of the amino group, is uninterrupted or is interrupted by oxygen, sulphur or a second nitrogen atom, or amino is unsubstituted or substituted by one or two acyl radicals, alkoxy- or aralkoxycarbonyl radicals, H.sub.2 N--CO, alkyl-, aralkyl- or arylcarbamoyl radicals; or R.sup.9 hydrogen, carboxyl, alkoxycarbonyl, carboxamido or halogen, and
- Z signifies NR.sup.10 --N.dbd.N, wherein R.sup.10 is hydrogen or an alkyl or aralkyl radical, or
- Z is an unsaturated 3-5 member chain of nitrogen atoms or of carbon atoms, or said chain having at least one nitrogen or sulphur atom, whereby carbon atoms in the chain are unsubstituted or substituted by alkyl, alkoxy, hydroxyalkyl, alkylthio, hydroxyl, aralkyl, aryl, carboxyl, carboxamido, alkoxycarbonyl, cyano, amino, which is unsubstituted or substituted by one or two alkyl radicals which alkyl is unsubstituted or substituted by at least one hydroxyl, carboxyl or alkoxycarbonyl radicals or halogen, as well as nitrogen which are not attached via a double bond are unsubstituted or substituted by alkyl or aralkyl or two neighboring chain substituents form an alkylene which, alkylene is unsubstituted or substituted or anellated with aryl and tautomers thereof, with the proviso that when R.sup.3 is an arylcarbonyl radical or an alkylcarbonyl radical unsubstituted or substituted at least once by halogen and X-Y is C.dbd.NR.sup.9, then Z does not form a 1,2,3-triazole ring in which a nitrogen atom not connected via a double bond is substituted with a hydrogen atom comprising reducing a compound of formula: ##STR129## in which R.sup.1, R.sup.2 and L have the meanings given above, and, when R.sup.3 is not hydrogen, acylating the anilino group and subsequently cleaving any ester bond present, or reacting a compound of claim 1, in which L is a pyrazolo-heterocyclic radical of formula: ##STR130## in which X-Y have the meanings given above and G is the residue of an organic or inorganic or a glycoside residue, with an appropriate hydrolase.
- 28. A process for the preparation of a compound of the formula ##STR131## wherein R.sup.1 and R.sup.2, which are the same or different, are hydrogen or halogen, SO.sub.3 H, PO.sub.3 H.sub.2 or a salt of the acid residues, hydroxyl, nitro, carboxyl, carboxamido or cyano or alkyl, alkenyl, alkoxy, alkylsulphinyl, alkylsulphonyl, alkoxycarbonyl, alkylcarbonyl, aryl or aralkyl unsubstituted or substituted at least once by hydroxyl, carboxyl, halogen, cyano, SO.sub.3 H or PO.sub.3 H.sub.2 or a salt of one of the acid residues or,
- when two substituents of R.sup.1 and R.sup.2 are present on neighboring carbon atoms, together represent a 1,4-butadiendiyl radical which is unsubstituted or substituted at least once by SO.sub.3 H, PO.sub.3 H.sub.2 or a salt of the acid groups, an alkyl or a carboxyl group, comprising reacting a compound of the formula ##STR132## wherein G is the residue of an organic or inorganic acid or a glycoside residue, L is a pyrazolo-heterocyclic radical of formula: ##STR133## in which X-Y signifies NR.sup.8 --CO or N.dbd.CR.sup.9, wherein R.sup.8 is hydrogen or an alkyl and R.sup.9 is alkyl, alkenyl, alkoxy, alkylthio, aryl, aralkyl, in each case unsubstituted or substituted by hydroxyl, dialkylphosphinyl, carboxyl SO.sub.3 H, PO.sub.3 H.sub.2, a salt of one of the acid groups or alkoxycarbonyl; amino, which is unsubstituted or substituted by one or two alkyl radicals which alkyls are unsubstituted or substituted by at least one hydroxyl, carboxyl or alkoxycarbonyl radical and wherein when amino is substituted by two alkyl radicals, the alkyl radicals can be joined to form a ring which, apart from the first nitrogen atom of the amino group, is uninterrupted or is interrupted by oxygen, sulphur or a second nitrogen atom, or amino is unsubstituted or substituted by one or two acyl radicals, alkoxy- or aralkoxycarbonyl radicals, H.sub.2 N--CO, alkyl-, aralkyl- or arylcarbamoyl radicals; or R.sup.9 hydrogen, carboxyl, alkoxycarbonyl, carboxamido or halogen, and
- Z signifies NR.sup.10 --N.dbd.N, wherein R.sup.10 is hydrogen or an alkyl or aralkyl radical, or
- Z is an unsaturated 3-5 member chain of nitrogen atoms or of carbon atoms, or said chain having at least one nitrogen or sulphur atom, whereby carbon atoms in the chain are unsubstituted or substituted by alkyl, alkoxy, hydroxyalkyl, alkylthio, hydroxyl, aralkyl, aryl, carboxyl, carboxamido, alkoxycarbonyl, cyano, amino, which is unsubstituted or substituted by one or two alkyl radicals which alkyl is unsubstituted or substituted by at least one hydroxyl, carboxyl or alkoxycarbonyl radicals or halogen, as well as nitrogen which are not attached via a double bond are unsubstituted or substituted by alkyl or aralkyl or two neighboring chain substituents form an alkylene which, alkylene is unsubstituted or substituted or annellated with aryl and tautomers thereof, with a hydrolase and oxidizing the reaction product to produce the compound of the formula (VII).
- 29. A process for the preparation of a compound of the formula ##STR134## wherein R.sup.1 and R.sup.2, which are the same or different, are hydrogen or halogen, SO.sub.3 H, PO.sub.3 H.sub.2 or a salt of the acid residues, hydroxyl, nitro, carboxyl, carboxamido or cyano or alkyl, alkenyl, alkoxy, alkylsulphinyl, alkylsulphonyl, alkoxycarbonyl, alkylcarbonyl, aryl or aralkyl unsubstituted or substituted at least once by hydroxyl, carboxyl, halogen, cyano, SO.sub.3 H or PO.sub.3 H.sub.2 or a salt of one of the acid residues or,
- when two substituents of R.sup.1 and R.sup.2 are present on neighboring carbon atoms, together represent a 1,4-butadiendiyl radical which is unsubstituted or substituted at least once by SO.sub.3 H, PO.sub.3 H.sub.2 or a salt of the acid groups, an alkyl or a carboxyl group,
- comprising reacting a compound of formula:
- NH.sub.2 --L (VIII)
- wherein L is a pyrazolo-heterocyclic radical of formula: ##STR135## X-Y signifies NR.sup.8 --CO or N.dbd.CR.sup.9, wherein R.sup.8 is hydrogen or an alkyl and R.sup.9 is alkyl, alkenyl, alkoxy, alkylthio, aryl, aralkyl, in each case unsubstituted or substituted by hydroxyl, dialkylphosphinyl, carboxyl SO.sub.3 H, PO.sub.3 H.sub.2, a salt of one of the acid groups or alkoxycarbonyl; amino, which is unsubstituted or substituted by one or two alkyl radicals which alkyls are unsubstituted or substituted by at least one hydroxyl, carboxyl or alkoxycarbonyl radical and wherein when amino is substituted by two alkyl radicals, the alkyl radicals can be joined to form a ring which, apart from the first nitrogen atom of the amino group, is uninterrupted or is interrupted by oxygen, sulphur or a second nitrogen atom, or amino is unsubstituted or substituted by one or two acyl radicals, alkoxy- or aralkoxycarbonyl radicals, H.sub.2 N--CO, alkyl-, aralkyl- or arylcarbamoyl radicals; or R.sup.9 hydrogen, carboxyl, alkoxycarbonyl, carboxamido or halogen, and
- Z signifies NR.sup.10 --N.dbd.N, wherein R.sup.10 is hydrogen or an alkyl or aralkyl radical, or
- Z is an unsaturated 3-5 member chain of nitrogen atoms or of carbon atoms, or said chain having at least one nitrogen or sulphur atom, whereby carbon atoms in the chain are unsubstituted or substituted by alkyl, alkoxy, hydroxyalkyl, alkylthio, hydroxyl, aralkyl, aryl, carboxyl, carboxamido, alkoxycarbonyl, cyano, amino, which is unsubstituted or substituted by one or two alkyl radicals which alkyl is unsubstituted or substituted by at least one hydroxyl, carboxyl or alkoxycarbonyl radicals or halogen, as well as nitrogen which are not attached via a double bond are unsubstituted or substituted by alkyl or aralkyl or two neighboring chain substituents form an alkylene which, alkylene is unsubstituted or substituted or anellated with aryl and tautomers thereof, with a phenol of formula: ##STR136## wherein R.sup.1 and R.sup.2 have the meanings given above and V is a hydrogen or halogen atom or a COOH or SO.sub.3 H group, in the presence of an oxidation agent.
- 30. A process for the preparation of a compound of the formula ##STR137## wherein R.sup.1 and R.sup.2, which are the same or different, are hydrogen or halogen, SO.sub.3 H, PO.sub.3 H.sub.2 or a salt of the acid residues, hydroxyl, nitro, carboxyl, carboxamido or cyano or alkyl, alkenyl, alkoxy, alkylsulphinyl, alkylsulphonyl, alkoxycarbonyl, alkylcarbonyl, aryl or aralkyl unsubstituted or substituted at least once by hydroxyl, carboxyl, halogen, cyano, SO.sub.3 H or PO.sub.3 H.sub.2 or a salt of one acid residues or,
- when two substituents of R.sup.1 and R.sup.2 are present on neighboring carbon atoms, together represent a 1,4-butadienyl radical which is unsubstituted or substituted at least once by SO.sub.3 H, PO.sub.3 H.sub.2 or a salt of the acid groups, an alkyl or a carboxyl group, comprising reacting a compound of formula:
- L--H (X)
- in which L is a pyrazolo-heterocyclic radical of formula: ##STR138## wherein X-Y signifies NR.sup.8 --CO or N.dbd.CR.sup.9, wherein R.sup.8 is hydrogen or an alkyl and R.sup.9 is alkyl, alkenyl, alkoxy, alkylthio, aryl, aralkyl, in each case unsubstituted or substituted by hydroxyl, dialkylphosphinyl, carboxyl SO.sub.3 H, PO.sub.3 H.sub.2, a salt of one of the acid groups or alkoxycarbonyl; amino, which is unsubstituted or substituted by one or two alkyl radicals which alkyls are unsubstituted or substituted by at least one hydroxyl, carboxyl or alkoxycarbonyl radical and wherein when amino is substituted by two alkyl radicals, the alkyl radicals can be joined to form a ring which, apart from the first nitrogen atom of the amino group, is uninterrupted or is interrupted by oxygen, sulphur or a second nitrogen atom, or amino is unsubstituted or substituted by one or two acyl radicals, alkoxy- or aralkoxycarbonyl radicals, H.sub.2 N--CO, alkyl-, aralkyl- or arylcarbamoyl radicals; or R.sup.9 hydrogen, carboxyl, alkoxycarbonyl, carboxamido or halogen, and
- Z signifies NR.sup.10 --N.dbd.N, wherein R.sup.10 is hydrogen or an alkyl or aralkyl radical, or
- Z is an unsaturated 3-5 member chain of nitrogen atoms or of carbon atoms, or said chain having at least one nitrogen or sulphur atom, whereby carbon atoms in the chain are unsubstituted or substituted by alkyl, alkoxy, hydroxyalkyl, alkylthio, hydroxyl, aralkyl, aryl, carboxyl, carboxamido, alkoxycarbonyl, cyano, amino, which is unsubstituted or substituted by one or two alkyl radicals which alkyl is unsubstituted or substituted by at least one hydroxyl, carboxyl or alkoxycarbonyl radicals or halogen, as well as nitrogen which are not attached via a double bond are unsubstituted or substituted by alkyl or aralkyl or two neighboring chain substituents form an alkylene which, alkylene is unsubstituted or substituted or anellated with aryl and tautomers thereof, with a compound of formula: ##STR139## wherein R.sup.1 and R.sup.2 have the meanings given above and Hal is halogen.
- 31. A process for the preparation of a compound of the formula ##STR140## wherein R.sup.1 and R.sup.2, which are the same or different, are hydrogen or halogen, SO.sub.3 H, PO.sub.3 H.sub.2 or a salt of the acid residues, hydroxyl, nitro, carboxyl, carboxamido or cyano or alkyl, alkenyl, alkoxy, alkylsulphinyl, alkylsulphonyl, alkoxycarbonyl, alkylcarbonyl, aryl or aralkyl unsubstituted or substituted at least once by hydroxyl, carboxyl, halogen, cyano, SO.sub.3 H or PO.sub.3 H.sub.2 or a salt of one of the acid residues or,
- when two substituents of R.sup.1 and R.sup.2 are present on neighboring carbon atoms, together represent a 1,4-butadiendiyl radical which is unsubstituted or unsubstituted at least once by SO.sub.3 H, PO.sub.3 H.sub.2 or a salt of the acid groups, an alkyl or a carboxyl group, comprising reacting a compound of formula:
- L--E (XXV)
- wherein E is a nitro or nitroso group and L is a pyrazoloheterocyclic radical of formula: ##STR141## wherein X-Y signifies NR.sup.8 --CO or N.dbd.CR.sup.9, wherein R.sup.8 is hydrogen or an alkyl and R.sup.9 is alkyl, alkenyl, alkoxy, alkylthio, aryl, aralkyl, in each case unsubstituted or substituted by hydroxyl, dialkylphosphinyl, carboxyl SO.sub.3 H, PO.sub.3 H.sub.2, a salt of one of the acid groups or alkoxycarbonyl; amino, which is unsubstituted or substituted by one or two alkyl radicals which alkyls are unsubstituted or substituted by at least one hydroxyl, carboxyl or alkoxycarbonyl radical and wherein when amino is substituted by two alkyl radicals, the alkyl radicals can be joined to form a ring which, apart from the first nitrogen atom of the amino group, is uninterrupted or is interrupted by oxygen, sulphur or a second nitrogen atom, or amino is unsubstituted or substituted by one or two acyl radicals, alkoxy- or aralkoxycarbonyl radicals, H.sub.2 H--CO, alkyl-, aralkyl- or arylcarbamoyl radicals; or R.sup.9 hydrogen, carboxyl, alkoxycarbonyl, carboxamido or halogen, and
- Z signifies NR.sup.10 --N.dbd.N, wherein R.sup.10 is hydrogen or an alkyl or aralkyl radical, or
- Z is an unsaturated 3-5 member chain of nitrogen atoms or of carbon atoms, or said chain having at least one nitrogen or sulphur atom, whereby carbon atoms in the chain are unsubstituted or substituted by alkyl, alkoxy, hydroxyalkyl, alkylthio, hydroxyl, aralkyl, aryl, carboxyl, carboxamido, alkoxycarbonyl, cyano, amino, which is unsubstituted or substituted by one or two alkyl radicals which alkyl is unsubstituted or substituted by at least one hydroxyl, carboxyl or alkoxycarbonyl radicals or halogen, as well as nitrogen which are not attached via a double bond are unsubstituted or substituted by alkyl or aralkyl or two neighboring chain substituents form an alkylene which, alkylene is unsubstituted or substituted or anellated with aryl and tautomers thereof, with an organo-metallic compound of formula: ##STR142## wherein R.sup.1 and R.sup.2 have the meanings given above, Q is a hydroxyl group or a dialkylamino radical and Me is a lithium atom or a magnesium atom substituted by halogen and subsequently working up in an aqueous medium.
Priority Claims (1)
Number |
Date |
Country |
Kind |
39 42 355.7 |
Dec 1989 |
DEX |
|
Parent Case Info
This is a divisional application of application Ser. No. 07/633,231, filed Dec. 21, 1990, now U.S. Pat. No. 5,334,505.
US Referenced Citations (6)
Foreign Referenced Citations (5)
Number |
Date |
Country |
0034323 |
Aug 1981 |
EPX |
0268167 |
May 1988 |
EPX |
0433853 |
Jun 1991 |
EPX |
1448348 |
Jun 1966 |
FRX |
8902473 |
Mar 1989 |
WOX |
Divisions (1)
|
Number |
Date |
Country |
Parent |
633231 |
Dec 1990 |
|