Process for the manufacture of metal complexes of isoindoline azines

Claim 1

A process for the manufacture of a 1:1 metal complex of an azine of the formula ##STR113## wherein the ring A is unsubstituted or is substituted by two to four halogen atoms, by one or two alkyl of 1 to 4 carbon atoms, by one or two alkoxy of 1 to 4 carbon atoms, by phenyl, by phenoxy, by nitro, by benzoylamino, or by an alkanoylamino of 2 to 6 carbon atoms, Y is a radical of the formula ##STR114## wherein R' is an alkoxycarbonyl, alkylcarbamoyl, carbamoyl, thiocarbamoyl or sulfamoyl group, a benzylcarbamoyl group, a phenylsulfamoyl or phenylsulfonyl group which is unsubstituted or substituted by halogen atoms or alkyl groups of 1 to 4 carbon atoms, a group of the formula ##STR115## wherein Z 1 is an oxygen or a sulfur atom, X 1 is a hydrogen, chlorine or bromine atom, a nitro, trifluoromethyl, carbamoyl or sulfamoyl group, an alkyl, alkoxy or alkylsulfamoyl group of 1 to 4 carbon atoms, an alkanoylamino, alkylcarbamoyl or alkoxycarbonyl group of 2 to 6 carbon atoms, a phenoxy, benzoylamino, phenylcarbamoyl or phenylsulfamoyl or phenylazo group which is unsubstituted or substituted by chlorine or bromine atoms or methyl groups, and X 2 is a hydrogen, chlorine or bromine atom, an alkyl or alkoxy group of 1 to 4 carbon atoms, W is O, S, or NH, and R" is a radical of the formula (10), R is hydrogen, alkyl of 1 to 4 carbon atoms, phenyl or naphthyl, Q is a group of formula (2) ##STR116## wherein R 1 is a hydroxyl or mercapto group and B is an isocyclic or heterocyclic radical selected from the group consisting of phenylene, naphthylene, a 5- or 6-membered heterocyclic ring which may be fused with a benzene nuclei and which contains a nitrogen, oxygen or sulfur atom β-oriented to the C* atom and which may contain a further nitrogen atom in the ring and a fused benzene ring or a further heterocyclic ring, which 5- or 6-membered heterocyclic ring is selected from the group consisting of 2,4-dihydroxyquinoline, 2,4-dihydroxy-5,6,7 or 8-chloroquinoline, 2,4-dihydroxy-6,8- or 7,8-dichloroquinoline, 2,4-dihydroxy-6,7 or 8-methylquinoline, 2,4-dihydroxy-6-chloro-8-methylquinoline, 2-methyl-4-hydroxyquinoline, 2-methyl-4-hydroxy-6-chloroquinoline, 2-methyl-4-hydroxy-6-methoxyquinoline, 3-hydroxyisoquinoline, barbituric acid, 2-methyl-4,6-dihydroxypyrimidine, 4-hydroxycoumarin, 4-hydroxy-6-methylcoumarin, 4-hydroxy-6-methoxycoumarin, 4-hydroxy-6-chlorocoumarin, 4-hydroxy-6-chloro-5,7-dimethylcoumarin, 1-phenyl-3-methylpyrazol-5-one, 1-phenyl-3-carboxypyrazol-5-one, 1-phenyl-3-carbamoylpyrazol-5-one, 1-phenyl-3-methoxycarbonylpyrazol-5-one, 1-phenyl-3-ethoxycarbonylpyrazol-5-one, 1-o-chlorophenyl-3-methylpyrazol-5-one, 1-p-chlorophenyl-3-methylpyrazol-5-one, 1-o-methylphenyl-3-methylpyrazol-5-one, and 1-p-methylphenyl-3-methylpyrazol-5-one, or Q is a radical of the formula ##STR117## wherein E is an acyl group, an unsubstituted or a substituted carbamoyl or thiocarbamoyl group, V is an acyl, cyano or nitro group or an unsubstituted or substituted carbamoyl or thiocarbamoyl group, T is the radical of a heteroaryl amine selected from the group consisting of 2-aminothiophene, 2-aminothiazole, 2-amino-5-nitrothiazole, 2-amino-5-methylsulfonylthiazole, 2-amino-5-cyanothiazole, 2-amino-4-methyl-5-nitrothiazole, 2-amino-4-methylthiazole, 2-amino-4-phenylthiazole, 2-amino-4-(4'-chloro)-phenylthiazole, 2-amino-4-(4'-nitro)-phenylthiazole, 2-aminopyrazole, 3-amino-1-phenylpyrazole, 3-aminoindazole, 5-methylsulfonyl-2-aminothiazole, 5-benzoyl-2-aminothiazole, 2-aminoimidazole, 4,5-dicyano-2-aminoimidazole, 4,5-diphenyl-2-aminothiazole, 2-amino-3,4-thiadiazole, 2-amino-3,5-thiadiazole, 3-amino-1,2,4-triazole, 2-amino-3,4-oxadiazole, 3-aminopyridine, 2-aminopyridine-N-oxide, 2-amino-benzthiazole, 2-amino-6-chlorobenzthiazole, 2-amino-6-methyl-benzthiazole, 2-amino-6-methoxy-benzthiazole, 2-amino-6-chloro-4-nitrobenzthiazole, 2-amino-6-bromo-4-cyanobenzthiazole, 2-amino-6-cyano-4-methylbenzthiazole, 2-amino-6-methyl-4-nitrobenzthiazole, 2-amino-6-methoxy-4-nitrobenzthiazole, 2-amino-6-butoxy-4-chlorobenzthiazole, 2-amino-4-chloro-5-methoxy-benzthiazole, 2-amino-4-bromo-6-methoxybenzthiazole, 2-amino-4,6-dichlorobenzthiazole, 2-amino-4,6-dibromobenzthiazole, 2-amino-4-methyl-6-(trifluoromethyl)-benzthiazole, 2-amino-4-methyl-6-propionyl-benzthiazole, 2-amino-4-chloro-6-methylsulfonyl-benzthiazole, 3-amino-benzisothiazole, 3-amino-5-chloro-benzisothiazole, 2-amino-3-cyanotetrahydrobenzthiophene, 2-amino-benzimidazole, 2-amino-6-chlorobenzimidazole, 2-amino-6-bromo-benzimidazole, 2-amino-6-methyl-benzimidazole, 2-amino-6-methoxybenzimidazole, 2-amino-6-ethoxy-benzimidazole, 2-amino-6-methylsulfonyl-benzimidazole, 2-amino-6-acetylaminobenzimidazole, 3-amino-isoindoleninone-1, 1,4-diaminophthalazine and 1-amino-4-chlorophthalazine, as well as their imine forms, or T is a radical of the formula ##STR118## wherein Z 1 is an oxygen or a sulfur atom, n is 1 or 2, X 3 is an alkyl, cycloalkyl, aralkyl or aryl radical, or an amino group which is unsubstituted or substituted by an alkyl, cycloalkyl, aralkyl or aryl radical, and the metal is selected from the group consisting of zinc, cadmium, manganese, conbalt, iron, copper and nickel, which comprises condensing a hydrazone of the formula ##STR119## with an ortho ester of formula R--C(OR.sub.2).sub.3 ( 6) where A, Y and R are defined above and R 2 is alkyl of 1 to 4 carbon atoms, benzyl or phenyl, then reacting the product of the condensation of the hydrazone of formula (5) and the ortho ester of formula (6) with a compound of formula H--Q where Q is defined above, in the presence of a metal salt selected from the group consisting of the formates, acetates and stearates of zinc, cadmium, manganese, cobalt, iron, copper and nickel, at a temperature of 100°-200° C. in a polar organic solvent.