Metal complexes of bis-hydrazones

The present invention relates to new metal complexes of bis-hydrazones of the formula ##STR2## wherein A denotes an isocyclic or heterocyclic radical, R denotes a H atom, an alkyl group or an aryl radical, M denotes a divalent transition metal and zinc or cadmium, X.sub.1 and X.sub.2 independently of one another represent alkyl, cycloalkyl, aralkyl or aryl radicals, or conjointly form a fused carbocyclic or heterocyclic aromatic ring, L denotes a ligand having one or more coordinating N or S atoms, and n denotes the number 1 - 5.
Preferred bis-hydrazone metal complexes are those of the formula ##STR3## wherein A, L, R and M have the meaning indicated, X.sub.3 denotes a H or halogen atom, an alkoxy or arylmercapto group containing 1 - 6 C atoms, an aralkoxy group having an alkyl radical of 1 - 4 C atoms, an aryloxy group, a nitro, carboxyl or carbamoyl group, alkylcarbamoyl or alkanoylamino group containing 2 - 6 C atoms or an arylcarbamoyl group, X.sub.4 denotes a H or halogen atom, X.sub.5 denotes a H or halogen atom, an alkoxy or alkylmercapto group containing 1 - 6 C atoms, an aralkoxy group having an alkyl radical of 1 - 4 C atoms, or an aryloxy group and X.sub.6 denotes a H or halogen atom, a nitro, carboxyl or carbamoyl group, an alkylcarbamoyl or alkanoylamino group containing 2 - 6 C atoms, or an arylcarbamoyl group and m denotes the number 1 - 3.
Compounds of particular interest are those of the formula ##STR4## wherein A, R, X.sub.3 -X.sub.6 and M have the meaning indicated and R' denotes a hydrogen atom, an OH group, an aliphatic or cycloaliphatic radical or an aromatic radical which is preferably free from strongly electron-attracting groups, or an amino, alkylamino, arylamino, acyl or acylamino group or a group of the formula ##STR5## wherein R.sub.2 and R.sub.3 denote H atoms or alkyl or aryl groups and R"' denotes a H atom or an amino, alkyl or phenyl group.
Preferred metal complexes are also those of the formula ##STR6## wherein A, R, M, X.sub.3 - X.sub.6 have the meaning indicated and B, conjointly with the N atom, forms a heterocyclic ring system, preferably a pyridine ring.
Preferred metal complexes are also those of the formula ##STR7## wherein A, R, M, X.sub.3 - X.sub.6 have the meaning indicated and B.sub.1 is an alkylene group containing 2 - 10 C atoms, or an arylene group.
In the metal complexes of the formula indicated, M denotes, for example, a Co.sup.2.sup.+ or Zn.sup.2.sup.+ atom but preferably denotes a Cu.sup.2.sup.+ atom and in particular a Ni.sup.2.sup.+ atom.
In the formulae indicated X.sub.4 and X.sub.6 perferably represent H or chlorine atoms, and X.sub.3 and X.sub.5 preferably represent H or chlorine atoms or alkoxy groups containing 1 - 4 C atoms.
R preferably denotes a H atom, an alkyl group containing 1 - 4 C atoms, or a phenyl group.
In the formulae indicated, A preferably denotes a radical of the formula ##STR8## wherein Y.sub.1 and Y.sub.2 denote H or halogen atoms, alkyl or alkoxy groups having 1 - 4 C atoms, or nitro groups.
Preferred metal complexes are also those of the formula indicated wherein A denotes a radical of the formula ##STR9## wherein R.sub.8 denotes an OH group, an alkyl group containing 1 - 4 C atoms, or a phenyl radical which is optionally substituted by halogen atoms or alkyl or alkoxy groups containing 1 - 4 C atoms.
The new metal complexes are obtained if a bishydrazone of the formula ##STR10## is treated, in the presence of a ligand L which has the abovementioned meaning, with agents which donate the divalent transition metals or zinc and cadmium.
The starting material is preferably a bis-hydrazone of the formula ##STR11## wherein A, R and X.sub.3 - X.sub.6 have the abovementioned meaning.
In formula (VIII) A preferably represents a radical of the formula (VI) or (VII).
The bis-hydrazones of the formula (VIII) are obtained a) by condensing a mono-hydrazone of the formula ##STR12## with a hydroxyaldehyde or hydroxyketone of the formula ##STR13## or b) by condensing a compound of the formula ##STR14## wherein V denotes a group of the formula ##STR15## wherein Z.sub.1 denotes an imino or thio group and the Z.sub.2 denote halogen atoms, alkoxy groups, particularly methoxy groups, of sec. amino groups, with a mono-hydrazone of the formula ##STR16## or c) by condensing a mono-hydrazone of the formula (X) with an azomethine of the formula ##STR17## wherein Ph denotes a phenyl radical which is optionally substituted by halogen atoms, alkyl or alkoxy groups, containing 1 - 4 C atoms, alkoxycarbonyl groups containing 2 - 6 C atoms or nitro or trifluoromethyl groups, and, in the formulae (VIII), (IX) and (XI), A and R have the meaning indicated and, in the formulae (VIII), (X) and (XII), X.sub.1 and X.sub.2 have the meaning indicated.
The hydrazones of the formula (X) are obtained by reacting hydrazine with a compound of the formula (XII). The following should be mentioned as examples of compounds of the formula (XII): 3-imino-4,5-dichloro-pyrrolinone, 3-imino-4,5-dimethyl-pyrrolinone, 3-imino-4,5-dimethyl-pyrrolinone, 3-imino-4,5-dicyclohexyl-pyrrolinone, 3-imino-4,5-diphenyl-pyrrolinone, 3-imino-isoindolinone, 4,5,6,7-tetrachloro-3-imino-isoindolinone, 5,6-dichloro-3-imino-isoindolinone, 4,5,7-trichloro-6-methoxy-3-imino-isoinodlinone, 4,5,7-trichloro-6-ethoxy-3-imino-isoindolinone, 5,7-dichloro-4,6-dimethoxy-3-imino-isoinodolinone, 5,7-dichloro-4,6-diphenoxy-3-imino-isoindolinone, 4,5,7-trichloro-6-methylmercapto-3-imino-isoindolinone, 4,5,7-trichloro-6-phenylmercapto-3-imino-isoindolinone, 3-imino-4,5-benzo-isoindolinone, 4,5,6,7-tetraphenoxy-3-imino-isoindolinone, 5- or 6-methyl-3-imino-isoindolinone, 5- or 6-phenyl-3-imino-isoindolinone, 4- or 7-chloro-3-imino-isoindolinone, 5- or 6-chloro-3-imino-isoindolinone, 4- or 7-nitro-3-imino-isoindolinone, 5- or 6-nitro-3-imino-isoindolinone, 5- or 6-methoxy-3-imino-isoindolinone, 5- or 6-ethoxy-3-imino-isoindolinone, 5- or 6-phenoxy-3-imino-isoindolinone, 5-or 6-methylmercapto-3-imino-isoindolinone, 5- or 6-methylsulphonyl-3-imino-isoindolinone, 5- or 6-acetylamino-3-imino-isoindolinone, 3-imino-4,7-dithia-4,5,6,7-tetrahydro-isoindolinone, 3-imino-4,7-diaza-isoindolinone, 3,3-dimethoxy-4,5,6,7-tetrachloro-isoindolinone, 3,3-dimethoxy-4,5,6,7-tetrabromo-isoindolinone, 3,3,6-trimethoxy- 4,5,7-trichloro-isoindolinone, 3,3-dimethoxy-4,5,7-trichloro-6-butoxy-isoindolinone, 3,3-dimethoxy-4,5,7-trichloro-6-phenoxy-isoindolinone, 3,3-dimethoxy-4,5,7-trichloro-6-(p-chlorophenoxy)-iso-indolinone, 3,3-dimethoxy-4,5,7-trichloro-6-(o-methylphenoxy)-iso-indolinone, 3,3-dimethoxy-4,5,7-trichloro-6-methylmercapto-iso-indolinone, 3,3,-dmethoxy-4,5,7-trichloro-6-ethylmercapto-isoindolinone and 3,3,4,6-tetramethoxy-5,7-dichloro-isoindolinone.
The pyrrolinones and isoindolinones mentioned are known compounds.
In accordance with process a), the hydrazones of the formula (X) are condensed with hydroxyaldehydes or hydroxyketones of the formula (XI).
Aldehydes and ketones of particular interest are those of the formula ##STR18## wherein Y.sub.1 and Y.sub.2 have the meaning indicated, R" denotes a H atom or a methyl group and Z denotes a NH group or an O atom, and, in particular, the hydroxyquinolines of the formula ##STR19## wherein R", Y.sub.1 and Y.sub.2 have the meaning indicated.
Aldehydes and ketones of particular interest are also those of the following formulae ##STR20## wherein R.sub.9 denotes a cyano, carboxyl or carbamoyl group and R"and R.sub.8 have the meaning indicated above, or aldehydes and ketones of the formula ##STR21## wherein R" and R.sub.9 have the meaning indicated above, and also aldehydes or ketones of the formula ##STR22## wherein R.sub.10 denotes a H atom or an alkyl or aryl group, and wherein R", Y.sub.1 and Y.sub.2 have the meaning indicated above, or aldehydes and ketones of the formula ##STR23## wherein Y.sub.3 denotes a H atom or a carboxyl, carbamoyl, phenylcarbamoyl or alkoxycarbonyl group containing 2 - 6 C atoms, and Y.sub.4 denotes a H or halogen atom or a methoxy, nitro or cyano group, or pyrazolone-aldehydes or pyrazolone-ketones of the formula ##STR24## wherein R.sub.11 denotes an alkyl group containing 1 - 4 C atoms, an alkoxycarbonyl group containing 2 - 5 C atoms, a carboxyl group, a carbamoyl group or a group of the formula wherein M.sub.2 denotes a Ca, Sr, Ba or Mn atoms, and Y.sub.5 and Y.sub.6 denote H or halogen atoms, alkyl or alkoxy groups containing 1 - 4 C atoms, nitro, acylamino, carbamoyl or sulphamoyl groups or groups of the formula ##EQU1## wherein M.sub.2 denotes a Ca, Sr, Ba or Mn atoms and R" has the meaning indicated above.
The following aldehydes or ketones should be mentioned as examples:
1.hydroxybenzaldehydes:
Salicylaldehyde, 4-chloro-2-hydroxybenzaldehyde, 5-chloro-2-hydroxybenzaldehyde, 3-nitro-2-hydroybenzaldehyde, 5-nitro-2-hydroxybenzaldehyde, 3,5-dichloro-2-hydroxybenzaldehyde, 3,5-dibromo-2-hydroxybenzaldehyde, 5-phenylazo-2-hydroxybenzaldehyde, 5-(2'-chloro-phenylazo)-hydroxybenzaldehyde, 5-(2',5'-dichloro-phenylazo)-2-hydroxybenzaldehyde, 5-(2'-methyl-phenylazo)-2-hydroxybenzaldehyde, 5-(2'-methoxyphenylazo)-2-hydroybenzaldehyde, 5-(2'-methoxy-4'-nitrophenylazo)-2-hydroxybenzaldehyde and 5-(2'-methoxy-5'-carbamoyl-phenylazo)-2-hydroxybenzaldehyde.
2. Hydroxynaphthaldehydes: 2-Hydroxynaphthaldehyde, 6-bromo-2-hydroxynapthaldehyde, 5-nitro-2-hydroxynaphthaldehyde, 2-hydroxy-3-carboxynaphthaldehyde, 2-hydroxy-3-methoxycarbonyl-naphthaldehyde, 2-hydroxy-3-phenylcarbamoyl-naphthaldehyde, 2-hydroxy-3-(4'-chlorophenylcarbamoyl)-naphthaldehyde, 2-hydroxy-3-(4'-chloro-2'-methylphenylcarbamoyl)-naphthaldehyde, 2-hydroxy-3-(2',5'-dimethoxy-3'-chloro-phenylcarbamoyl-naphthaldehyde, 2-hydroxy-6-bromo-3-carboxynaphthaldehyde and 2-hydroxy-6-bromo-3-phenylcarbamoylnaphthaldehyde.
3. Heterocyclic aldehydes and ketones:
2,6-Dihydroxy-4-methyl-5-cyano-3-pyridinealdehyde, 2,6-dihydroxy-4-methyl-5-carboxy-3-pyridinealdehyde, 2,6-dihydroxy-4-methyl-5-carbamoyl-3-pyridinealdehyde, 2,4-dihydroxy-3-quinolinealdehyde, 5-chloro-2,4-dihydroxy-3-quinolinealdehyde, 6-chloro-2,4-dihydroxy-3-quinolinealdhyde, 7-chloro-2,4-dihydroxy-3-quinolinealdehyde, 8-chloro-2,4-dihydroxy-3-quinolinealdehyde, 6,8-dichloro-2,4-dihydroxy-3-quinolinealdehyde, 7,8-dichloro-2,4-dihydroxy-3-quinolinealdehyde, 6-methyl-2,4-dihydroxy-3-quinolinealdehyde, 7-methyl-2,4-dihydroxy-3-quinolinealdehyde, 8-methyl-2,4-dihydroxy-3-quinolinealdehyde, 6-chloro-8-methyl-2,4-dihydroxy-3-quinolinealdehyde, 2,4-dihydroxy-3-acetyl-quinoline, 2,4-dihydroxy-3-acetyl-6-methyl-quinoline, 2,4-dihydroxy-3-acetyl-6-chloro-quinoline, 2,4-dihydroxy-3-benzoyl-quinoline, 2-methyl-4,6-dihydroxy-5-pyrimidinealdehyde, 2-phenyl-4,6-dihydroxy-5-pyrimidinealdehyde, 2,4,6-trihydroxy-5-pyrimidinealdehyde, 2,4,6-trihydroxy-5-acetylpyrimidine, 4-hydroxy-3-quinaldinealdehyde, 6-chloro-4-hydroxy-3-quinaldinealdehyde, 6-methoxy-4-hydroxy-3-quinaldinealdehyde, 3-hydroxy-isoquinolone-4-aldehydes and other aldehydes. 4-hydroxycoumarin-3-aldehyde, 1-phenyl-3-methyl-4-formyl-5-pyrazolone, 1-phenyl-3-carboxy-4-formyl-5-pyrazolone, 1-phenyl-3-methoxycarbonyl-4-formyl-5-pyrazolone, 1-phenyl-3-ethoxycarbonyl-4-formyl-5-pyrazolone, 1-(2'-chlorophenyl)-3-methyl-4-formyl-5-pyrazolone, 1-(4'-chlorophenyl)-3-methyl-4-formyl-5-pyrazolone, 1-(2'-methylphenyl)-3-methyl-4-formyl-5-pyrazolone, 1-(4'-methylphenyl)-3-methyl-4-formyl-5-pyrazolone and 1-phenyl-3-carbamoyl-4-formyl-5-pyrazolone.
Instead of the aldehydes or ketones, it is also possible to use imines thereof, particularly the phenylimines of the formula XIV (process c), which can be obtained by known methods.
The mono-hydrazones of the formula (XIII) required for process b) are obtained, for example, by reacting the corresponding hydroxyketones or hydroxyaldehydes with hydrazine. The condensation of the hydrazone with the oxo compound or the isoindolinone is appropriately carried out in water or an organic solvent at elevated temperature, preferably between 50.degree. C and the boiling point of the solvent used. The following examples of solvents should be mentioned: water, alcohol, glacial acetic acid, dioxane, dimethylformamide, N-methylpyrrolidone, butyrolactone, glycol monoethyl ether, ethylene glycol, carbitol, glycol monomethyl ether, xylene, chlorobenzene, o-dichlorobenzene, nitrobenzene or mixtures thereof.
Since the resulting azomethines are sparingly soluble in the solvents mentioned, they can be isolated easily by filtration. Impurities which may be present can be removed by washing.
In certain cases it is possible to dispense with the isolation of the bis-azomethine and to carry out the reaction of the components (X) and (XI) or (XII) and (XIII) respectively in the same vessel, in the presence of the metal donor and the ligand L.
The process c) proves particulary advantageous for the manufacture of metal complexes of the formula (III) wherein R' deontes a phenyl radical.
As metal donors, the salts of zinc, manganese, cobalt, iron, preferably copper, and, in particular, nickel, should be mentioned. It is preferable to use the formates or acetates of these metals.
Ligands L which can be used are those having one or more coordinating N or S atoms.
N-containing ligands which can be used are preferably ammonia or primary aliphatic, cycloaliphatic or aromatic amines or amines, as well as secondary and tertiary heterocyclic amines, the N atoms of which are constituents of one or more rings.
Ligands of particular interest are those of the formula R'--NH.sub.2 or ##STR25## wherein R' and B have the abovementioned meaning.
It is possible to use the most diverse monoamines or polyamines, for example alkylamines having 1 - 10 C atoms, dialkylamines having 2 - 12 C atoms, phenyalkylamines, the alkyl radical of which contains 1 - 4 C atoms, mono- or di-cycloalkylamines having 5 - 6 C atoms in the cycloalkyl radical, heterocyclic, aromatic and cycloaliphatic amines or monoaminobenzenes.
Diamines which can be used are preferably those of the formula H.sub.2 N--B.sub.2 --NH.sub.2 wherein B.sub.2 denotes an alkylene group containing 2 - 10 C atoms, a p-phenylene group or a group --Ph--X--Ph wherein X denotes a direct bond, an O or S atom, a methylene or ethylene group or a group of the formula --NH--, --SO.sub.2 -- or --CO-- or --N=N--, or heterocyclic diamines.
Other N-containing ligands which should be mentioned are hydroazine, alkylhydrazines having 1-6 C atoms, arylhydrazines and hydrazones, hydroxylamine, amidines and hydrazides, and preferred S-containing ligands which should be mentioned are the mercaptans.
The following ligands should be mentioned as examples: Ammonia, methylamine, ethylamine, ethanolamine, methoxyethylamine, N-propylamine, isopropylamine, n-butylamine, n-hexylamine, cyclohexylamine, n-octylamine, n-decylamine, n-propylamine, di-(2'-aminoethyl))-amine, tri-(2'-aminoethyl)-amine, ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine, 1,6-hexylenediamine, benzylamine, aniline, 4-amino-4'-dimethylaminoazobenzene, 2-, 3- or 4-methylaniline, dimethylanilines, chloroaniline, 2,4, 3,4 or 2,5-dichloroaniline, 3-trifluoromethylaniline, 2-, 3- or 4-methoxyaniline, 2-, 3- or 4-ethoxyaniline, 4,4'-diamino-diphenyl oxide, 4,4'-diaminodiphenyl sulphide, 4,4'-diamino-diphenylmethane, 4,4'-diamino-diphenyl-sulphone, 4,4'-diamino-diphenyl-ketone, 4,4'-diamino-azobenzene, 4'-amino-4'-dimethylamino-azobenzene, 2,2'-dimethyl-4,4'-diaminoazobenzene, 2,2'-dimethoxy-4,4'-diaminoazobenzene, tri-(4-aminophenyl)-amine, 1,2,3,-tri-(4'-aminophenoxy)-propane, tetra-(4'-aminophenoxymethyl)-methane, 1-(2'-amino-ethylamino)-anthraquinone, 1-(4'-amino-phenylamino-anthraquinone, pyridine, picolines, lutidines, quinoline, isoquinoline, pyrrolidone, piperidine, piperazine, N-methyl-piperazine, morpholine, 2-amino-benzimidazole, 2-amino-benzthiazole, diethylenediamine, triethylenediamine, guanidine, 3-amino-benzoic acid amide, 3-amino-benzoic acid anilide, 3- or 4-acetylamino-aniliner, 3- or 4-benzoylamino-aniline, hydrazine, methylhydrazine, phenylhydrazine, 1,3,5-trihydrazino-s-triazine, 4-methylphenyl-hydrazine, acetaldehydehydrazone, benzaldehydehydrazone, acetonehydrazone, acetophenonehydrazone, cyclohexanonehydrazone, hydroxylamine, formamidine, formamide, dimethylformamide, acetamide, benzamide, acetohydrazide, benzhydrazide, semicarbazide and decanetriol.
The polyfunctional ligands can be reacted according to choice with one or more mols of the bis-hydrazone metal complex. Among the polyfunctional ligands, the diamines are preferred. The molar ratio between metal complex and diamine is appropriately chosen in such a way that each amino group is linked to one metal atom.
The addition of the ligand can take place before or at the same time as the addition of the metal ion.
The reaction of bis-hydrazones with the ligands and the metal donors is appropriately carried out at between 50.degree. and 150.degree. in an organic solvent, appropriately in one of the abovementioned solvents.
The new bis-hydrazone metal complexes are valuable pigments which can be used in a finely divided form for pigmenting high-molecular organic material, for example cellulose ethers and esters, such as ethylcellulose, nitrocellulose, cellulose acetate or cellulose butyrate, natural resins or synthetic resins, such as polymerisation resins or condensation resins, for example aminoplasts, particularly urea-formaldehyde and melamine-formaldehyde, alkyd resins, phenoplasts, polycarbonates, polyolefines, such as polystyrene, polyvinyl chloride, polyethylene, polypropylene, polyacrylonitrile, polyacrylic acid esters, polyamides, polyurethanes or polyesters, rubber, casein, silicone and silicone resins, on their own or as mixtures.
It is immaterial here whether the high molecular compounds mentioned are present as plastic compositions or melts or in the form of spinning solutions, lacquers, paints or printing inks. Depending on the application, it proves advantageous to use the new pigments as toners or in the form of preparations.
The new pigments are distinguished by a surprisingly good heat stability, high tinctorial strength and pure shade and, very often, by a surprisingly increased insolubility.

In the examples which follow, unless otherwise specified, the parts denotes parts by weight and the percentages denote percentages by weight.
EXAMPLE 1
1.32 parts of 2,4-dihydroxyquinoline-3-N-phenylaldimine and 1.50 parts of 4,5,6,7-tetrachloro-isoindolin-1-on- 3-ylidenehydrazine are stirred for 10 minutes at 100.degree. C in 75 parts by volume of methylcellosolve; the mixture is reacted with 1.25 parts of nickel acetate tetrahydrate and is warmed for a further 4 hours at 100.degree. C. The reaction product is filtered off while hot, rinsed with alcohol and acetone and dried at 80.degree. C in vacuo. This gives 2.67 parts (86% of theory) of a yellow pigment of the formula:
______________________________________ ##STR26##Micro-analysis: % C H N Cl Ni______________________________________calculated 46.49 2.11 11.29 22.87 9.46found 45.8 2.2 11.5 22.8 9.2______________________________________
EXAMPLE 2
2.35 parts of the bis-hydrazones (formed, for examples, from 2,4-dihydroxyquinoline-3-aldehyde and 4,5,6,7-tetrachloroisoindolin-1-on-3-ylidenehydrazine), 0.47 part by volume of aniline and 1.25 parts of nickel acetate tetrahydrate are stirred for 3 hours at 100.degree. C in 75 parts by volume of methylcellosolve. The thick mass is filtered at 85.degree.-90.degree. C and the product is washed with alcohol and acetone and dried, 2.75 parts (89% of theory) of the pigment of the formula according to Example 1 being obtained.
______________________________________Micro-analysis: % C H N Cl Ni______________________________________calculated 46.49 2.11 11.29 22.87 9.46found 46.5 2.1 11.4 22.7 9.5______________________________________
The complexes of Examples 3 - 9 were prepared in accordance with Example 1 and those of Examples 10 - 13 were prepared in accordance with Example 2: ##STR27## wherein the symbols have the meaning indicated in Table 1.
TABLE 1__________________________________________________________________________ ShadeEx- inample Y.sub.1 Y.sub.2 Y.sub.3 Y.sub.4 X.sub.6 X.sub.5 X.sub.4 X.sub.3 M Yield PVC__________________________________________________________________________3 H H H H Cl OCH.sub.3 Cl Cl Ni 91% yellow4 H H H H Cl OCH.sub.3 Cl OCH.sub.3 Ni 87% yellow5 H H H H Cl OCH.sub.3 Cl OCH.sub.3 Cu 78% greenish- tinged yellow6 H H Cl H Cl Cl Cl Cl Ni 88% yellow7 H H Cl H Cl OCH.sub.3 Cl Cl Ni 90% yellow8 H H Cl H Cl OCH.sub.3 Cl OCH.sub.3 Ni 87% yellow9 Cl Cl H H Cl OCH.sub.3 Cl OCH.sub.3 Ni 90% yellow10 H H H H Cl OCH.sub.3 Cl Cl Ni 88% yellow11 H H H H Cl OCH.sub.3 Cl OCH.sub.3 Ni 93% yellow12 H H H H Cl OCH.sub.3 Cl OCH.sub.3 Cu 85% greenish- tinged yellow13 H H H H H H H H Ni 85% yellow__________________________________________________________________________
The metal complexes of formula A, which contain the ligand L instead of aniline and which were prepared in accordance with Example 2, are shown in Examples 14-92 in Table 2. ##STR28##
TABLE 2__________________________________________________________________________Ex- Shade inample Y.sub.1 Y.sub.2 Y.sub.3 Y.sub.4 X.sub.3 X.sub.4 X.sub.5 X.sub.6 R M n L Yield PVC__________________________________________________________________________14 H H H H OCH.sub.3 Cl OCH.sub.3 Cl H Ni 1 4-Chloroaniline 90% yellow15 H H H H OCH.sub.3 Cl OCH.sub.3 Cl H Ni 1 4-Methylaniline 89% yellow16 H H H H OCH.sub.3 Cl OCH.sub.3 Cl H Ni 1 4-Methoxyaniline 90% yellow17 H H H H OCH.sub.3 Cl OCH.sub.3 Cl H Ni 1 5-Aminobenzimidazole 94% yellow18 H H H H OCH.sub.3 Cl OCH.sub.3 Cl H Ni 1 Benzylamine 89% yellow19 H H H H OCH.sub.3 Cl OCH.sub.3 Cl H Ni 1 Cyclohexylamine 87% yellow20 H H H H OCH.sub.3 Cl OCH.sub.3 Cl H Ni 1 2,2,6,6-Tetramethyl-4 71% yellow aminopiperidine21 H H H H OCH.sub.3 Cl OCH.sub.3 Cl H Ni 1 Pyridine 86% yellow22 H H H H OCH.sub.3 Cl OCH.sub.3 Cl H Ni 1 n-Octylamine 87% yellow23 H H H H OCH.sub.3 Cl OCH.sub.3 Cl H Ni 1 2-Ethanolamine 86% yellow24 H H H H OCH.sub.3 Cl OCH.sub.3 Cl H Ni 1 NH.sub.3 74% yellow25 H H H H Cl Cl Cl Cl H Ni 1 NH.sub.3 92% yellow26 H H H H Cl Cl Cl Cl H Ni 2 4,4'-Diaminodiphenyl- 92% yellow sulphone27 H H H H OCH.sub.3 Cl OCH.sub.3 Cl H Ni 2 4,4'-Diaminodiphenyl- 86% yellow sulphone28 H H H H OCH.sub.3 Cl OCH.sub.3 Cl H Ni 2 Hexamethylenediamine 96% yellow29 H H H H Cl Cl CH.sub.3 O H H Ni 1 NH.sub.3 34.4% yellow30 H H H H CH.sub.3 O Cl CH.sub.3 O Cl H Zn 1 NH.sub.3 59.3% yellow31 H H H H Cl Cl PhO Cl H Ni 1 NH.sub.3 83.3% yellow32 H H H H H H H H H Ni 1 NH.sub.3 90.0% yellow33 H H CH.sub.3 H Cl Cl CH.sub.3 O Cl H Ni 1 NH.sub.3 92.1% yellow34 H H CH.sub.3 H Cl Cl Cl Cl H Ni 1 NH.sub.3 79.5% yellow-orange35 H H Cl H Cl Cl CH.sub.3 O Cl H Ni 1 NH.sub.3 93.1% yellow36 H H Cl H Cl Cl Cl Cl H Ni 1 NH.sub.3 97.0% yellow37 H H H H Cl Cl CH.sub.3 O Cl CH.sub.3 Ni 1 NH.sub.3 83.3% yellow-brown38 H H H H H H H H CH.sub.3 Ni 1 NH.sub.3 91.2% yellow39 H H H H H CH.sub.3 CH.sub.3 O Cl H Cu 1 NH.sub.3 81.5% greenish- tinged yellow40 H H H H Cl Cl CH.sub.3 O Cl H Ni 1 Hydroxylamine 94.2% yellow41 H H H H Cl Cl Cl Cl H Ni 1 Morpholine 85.6% yellow42 H H H H Cl Cl CH.sub.3 O Cl H Ni 1 Benzylamine 93.6% yellow43 H H H H Cl Cl PhO Cl H Ni 1 Benzylamine 89.6% yellow44 H H H H Cl Cl Cl Cl H Ni 1 Benzylamine 97.5% yellow45 H H H H H H H H H Ni 1 Benzylamine 85.1% yellow46 H H CH.sub.3 H Cl Cl Cl Cl H Ni 1 Benzylamine 88.5% yellow47 H H Cl H Cl Cl Cl Cl H Ni 1 Benzylamine 77.2% yellow48 H H CH.sub.3 H Cl Cl CH.sub.3 O Cl H Ni 1 Benzylamine 87.5% yellow49 H H Cl H Cl Cl CH.sub.3 O Cl H Ni 1 Benzylamine 90.9% yellow50 H H H H Cl Cl CH.sub.3 O Cl CH.sub.3 Ni 1 Benzylamine 90.6% yellow51 H H H H H H H H CH.sub.3 Ni 1 Benzylamine 92.0% yellow52 H H H H CH.sub.3 O Cl CH.sub.3 O Cl H Ni 1 NH.sub.2CHNH 89.3% yellow53 H H CH.sub.3 H CH.sub.3 O Cl CH.sub.3 O Cl H Ni 1 Aniline 90.3% yellow54 H H CH.sub.3 H Cl Cl Cl Cl H Ni 1 Aniline 92.1% yellow55 H H H H CH.sub.3 O Cl CH.sub. 3 O Cl CH.sub.3 Ni 1 Aniline 80.6% yellow56 H H H H H H H H CH.sub.3 Ni 1 Aniline 84.6% yellow57 H H H H Cl Cl Cl Cl H Ni 1 Pyridine 96.0% yellow58 H H H H Cl Cl CH.sub.3 O Cl H Ni Pyridine 96.0% yellow59 H H H H CH.sub.3 O Cl CH.sub.3 O Cl H Cu 1 Pyridine 94.4% greenish- tinged yellow60 H H Cl H Cl Cl Cl Cl H Ni 1 Pyridine 91.5% yellow61 H H CH.sub.3 H Cl Cl Cl Cl H Ni 1 Pyridine 96.8% yellow62 H H H H Cl Cl CH.sub.3 O Cl CH.sub.3 Ni 1 Pyridine 90.3% yellow-brown63 H H H H H H H H CH.sub.3 Ni 1 Pyridine 83.3% yellow64 H H H H CH.sub.3 O Cl CH.sub.3 O Cl H Ni 1 2-Quinoline 87.5% yellow65 H H H H CH.sub.3 O Cl CH.sub.3 O Cl H Ni 1 Phenylhydrazine 93.0% yellow66 H H H H CH.sub.3 O Cl CH.sub.3 O Cl H Ni 1 Benzhydrazide 90.0% yellow67 H H H H CH.sub.3 O Cl CH.sub.3 O Cl H Ni 1 Decanethiol 88.6% yellow-brown68 H H H H CH.sub.3 O Cl CH.sub.3 O Cl H Ni 2 Ethylenediamine 87.5% yellow69 H H CH.sub.3 H Cl Cl CH.sub.3 O Cl H Ni 2 Ethylenediamine 85.7% yellow70 H H CH.sub.3 H Cl Cl Cl Cl H Ni 2 Ethylenediamine 90.1% yellow71 H H Cl H Cl Cl Cl Cl H Ni 2 Ethylenediamine 82.1% yellow72 H H Cl H Cl Cl CH.sub.3 O Cl H Ni 2 Ethylenediamine 89.7% yellow73 H H H H H H H H CH.sub.3 Ni 2 Ethylenediamine 86.4% yellow74 H H H H CH.sub.3 O Cl CH.sub.3 O Cl H Ni 2 Propylenediamine 92.9% yellow75 H H Cl H Cl Cl Cl Cl H Ni 2 Propylenediamine 86.2% yellow76 H H H H Cl Cl Cl Cl H Ni 2 Hexamethylenediamine 93.1% yellow77 H H Cl H Cl Cl Cl Cl H Ni 2 Hexamethylenediamine 93.6% yellow78 H H H H H H H H CH.sub.3 Ni 2 Hexamethylenediamine 94.7% yellow79 H H H H Cl Cl CH.sub.3 O Cl H Ni 2 Piperazine 82.1% yellow80 H H H H CH.sub.3 O Cl CH.sub.3 O Cl H Ni 2 Piperazine 71.4% yellow81 H H H H Cl Cl Cl Cl H Ni 2 Piperazine 35.3% yellow82 H H CH.sub.3 H Cl Cl Cl Cl H Ni 2 Piperazine 94.3% yellow83 H H CH.sub.3 H Cl Cl CH.sub.3 O Cl H Ni 2 Piperazine 65.5% yellow84 H H Cl H Cl Cl Cl Cl H Ni 2 Piperazine 78.2% yellow85 H H H H H H H H CH Ni 2 Piperazine 90.9% yellow86 H H H H CH.sub.3 O Cl CH.sub.3 O Cl H Ni 2 p-Phenylenenediamine 98.3% yellow87 H H H H Cl Cl CH.sub.3 O Cl H Ni 2 4,4'-Diamino- diphenylsulphone88 H H H H CH.sub.3 O Cl CH.sub.3 O Cl H Ni 2 Terephthaldialdehyde 96.7% yellow bis-hydrazone89 H H H H CH.sub.3 O Cl CH.sub.3 O Cl H Ni 2 Terephthalic acid 100% yellow-brown bis-hydrazide90 H H H H CH.sub.3 O Cl CH.sub.3 O Cl H Ni 2 2-Methyl-4,4'- 94.7% yellow Diaminobenzene91 H H H H CH.sub.3 O Cl CH.sub.3 O Cl H Ni 3 87.5% yellow92 H H H H Cl Cl Cl Cl C.sub.6 H.sub.5 Ni Ethylenediamine reddish- tinged yellow__________________________________________________________________________
The metal complexes of the formula (B) wherein the symbols have the meaning indicated in Table 3, are obtained in accordance with the instructions of Example 2. ##STR29##
The metal complexes of the formula (C) wherein the symbols have the meaning indicated in Table 4, are obtained in accordance with the instructions of Example 2 if 4-hydroxycoumarin3-aldhyde is used instead of 2,4-dihydroxyquinolinealdehyde. ##STR30##
TABLE 3__________________________________________________________________________Ex-ample X.sub.3 X.sub.4 X.sub.5 X.sub.6 R M n L Yield Shade__________________________________________________________________________ 93 Cl Cl Cl Cl Phenyl Ni 1 Aniline 89% yellow 94 Cl Cl OCH.sub.3 Cl Phenyl Ni 1 Aniline 89% yellow 95 OCH.sub.3 Cl OCH.sub.3 Cl Phenyl Ni 1 Aniline 84% yellow 96 OCH.sub.3 Cl OCH.sub.3 Cl Phenyl Ni 1 n-Octylamine 81% yellow 97 Cl Cl Cl Cl p-Tolyl Ni 1 Aniline 85% yellow 98 Cl Cl OCH.sub.3 Cl p-Tolyl Ni 1 Aniline 85% yellow 99 OCH.sub.3 Cl OCH.sub.3 Cl p-Tolyl Ni 1 n-Octylamine 87% yellow100 Cl Cl Cl Cl H Ni 1 NH.sub.3 98.1% yellow101 Cl Cl Cl Cl OH Ni 1 NH.sub.3 71.0% yellow102 Cl Cl Cl Cl OH Cu 1 NH.sub.3 92.3% yellow103 CH.sub.3 O Cl CH.sub.3 O Cl OH Ni 1 NH.sub.3 92.0% yellow104 CH.sub.3 O Cl CH.sub.3 O Cl OH Cu 1 NH.sub.3 96.0% greenish-tinged yellow105 Cl Cl PhO Cl OH Ni 1 NH.sub.3 89.3% yellow106 Cl Cl Cl Cl Ph Ni 1 NH.sub.3 95.2% yellow107 Cl Cl CH.sub.3 O Cl Ph Ni 1 NH.sub.3 92.4% yellow108 Cl Cl CH.sub.3 O Cl p-Tolyl Ni 1 NH.sub.3 96.6% yellow109 Cl Cl CH.sub.3 O Cl Ph Ni 1 Benzylamine 93.9% yellow110 Cl Cl CH.sub.3 O Cl p-Tolyl Ni 1 Benzylamine 85.3% yellow111 Cl Cl CH.sub.3 O Cl p-Tolyl Ni 1 NH.sub.2CHNH 92.4% yellow112 Cl Cl CH.sub.3 O Cl Phenyl Ni 1 Pyridine 93.4% yellow113 Cl Cl Cl Cl Phenyl Ni 1 Pyridine 98.5% yellow114 Cl Cl CH.sub.3 O Cl Phenyl Cu 1 Aniline 87.5% greenish-tinged yellow115 Cl Cl Cl Cl Phenyl Ni 1 Benzylamine 97.0% yellow-orange116 Cl Cl Cl Cl Phenyl Ni 1 Morpholine 98.1% yellow117 Cl Cl Cl Cl OH Ni 1 Benzylamine 85.4% yellow118 Cl Cl Cl Cl OH Ni 1 Aniline 78.4% yellow119 Cl Cl Cl Cl Phenyl Ni 1 N-Methylpiperazine 91.7% yellow120 Cl Cl Cl Cl Phenyl Ni 1 N-Phenylpiperazine 97.8% yellow121 Cl Cl Cl Cl Phenyl Ni 1 2-Aminobenzimidazole 94.6% brown122 Cl Cl Cl Cl Phenyl Ni 1 Hydrazine hydrate 99.5% yellow123 Cl Cl Cl Cl Phenyl Ni 1 2-Aminobenzthiazole 87.6% yellow-brown124 CH.sub.3 O Cl CH.sub.3 O Cl Phenyl Ni 1 Benzylamine 83.3% yellow125 Cl Cl Cl Cl OH Ni 2 Ethylenediamine 70.9% yellow126 Cl Cl CH.sub.3 O Cl OH Ni 2 Ethylenediamine 92.3% yellow127 CH.sub.3 O Cl CH.sub.3 O Cl OH Ni 2 Ethylenediamine 84.6% yellow128 Cl Cl Cl Cl H Ni 2 Ethylenediamine 87.9% yellow129 Cl Cl CH.sub.3 O Cl Phenyl Ni 2 Ethylenediamine 93.1% yellow130 Cl Cl CH.sub.3 O Cl p-Tolyl Ni 2 Ethylenediamine 90.1% yellow131 Cl Cl Cl Cl OH Ni 2 Propylenediamine 82.5% yellow132 Cl Cl Cl Cl OH Ni 2 Piperazine 93.5% yellow133 Cl Cl Cl Cl H Ni 2 Piperazine 96.0% yellow134 Cl Cl Cl Cl Phenyl Ni 2 Piperazine 100% yellow135 Cl Cl CH.sub.3 O Cl Phenyl Ni 2 Piperazine 86.6% yellow136 Cl Cl CH.sub.3 O Cl p-Tolyl Ni 2 Piperazine 93.3% yellow137 Cl Cl Cl Cl Phenyl Ni 2 4,4'-Diaminodiphenylsulphone 88.2% yellow138 Cl Cl Cl Cl Phenyl Ni 2 4,4' -Diaminocyclohexane 95.8% yellow139 Cl Cl Cl Cl Phenyl Ni 2 2-Methyl-4,4'-diamino- 89.9% yellow azobenzene140 Cl Cl Cl Cl Phenyl Ni 2 1,3-Diphenyldiaminopropane 90.1% yellow141 CH.sub.3 O Cl CH.sub.3 O Cl Phenyl Ni 2 Piperazine yellow142 CH.sub.3 O Cl CH.sub.3 O Cl p-Tolyl Ni 2 Piperazine yellow143 CH.sub.3 O Cl CH.sub.3 O Cl Phenyl Ni 2 Ethylenediamine yellow144 CH.sub.3 O Cl CH.sub.3 O Cl Phenyl Ni 2 Ethylenediamine yellow__________________________________________________________________________
TABLE 4__________________________________________________________________________Ex- Shade inample Y.sub.1 Y.sub.2 Y.sub.3 Y.sub.4 X.sub.3 X.sub.4 X.sub.5 X.sub.6 M n L Yield PVC__________________________________________________________________________145 H H H H Cl Cl Cl Cl Ni 1 NH.sub.3 98.2% yellow146 H H H H Cl Cl CH.sub.3 O Cl Ni 1 NH.sub.3 100% yellow147 H H CH.sub.3 H Cl Cl Cl Cl Ni 1 NH.sub.3 94.4% yellow148 H H CH.sub.3 H Cl Cl CH.sub.3 O Cl Ni 1 NH.sub.3 85.7% yellow149 H H Cl H Cl Cl Cl Cl Ni 1 NH.sub.3 98.5% yellow150 H H Cl H Cl Cl CH.sub.3 O Cl Ni 1 NH.sub.3 82.4% yellow151 H CH.sub.3 Cl CH.sub.3 Cl Cl Cl Cl Ni 1 NH.sub.3 85.0% yellow152 H H H H Cl Cl Cl Cl Ni 1 NH.sub.3 97.6% yellow153 H H H H Cl Cl CH.sub.3 O Cl Ni 1 NH.sub.3 87.5% yellow154 H H CH.sub.3 H Cl Cl Cl Cl Ni 1 NH.sub.3 97.1% yellow155 H H CH.sub.3 H Cl Cl CH.sub.3 O Cl Ni 1 NH.sub.3 90.6% yellow156 H H Cl H Cl Cl Cl Cl Ni 1 Benzylamine 94.1% yellow157 H H Cl H Cl Cl CH.sub.3 O Cl Ni 1 Benzylamine 90.0% yellow158 H CH.sub.3 Cl CH.sub.3 Cl Cl Cl Cl Ni 1 Benzylamine 87.5% yellow159 H H CH.sub.3 H Cl Cl Cl Cl Ni 1 Benzylamine 89.7% yellow160 H H Cl H Cl Cl Cl Cl Ni 1 Benzylamine 98.3% yellow161 H H H H Cl Cl Cl Cl Ni 1 Pyridine 99.2% yellow162 H H CH.sub.3 H Cl Cl Cl Cl Ni 1 Pyridine 94.5% yellow163 H H Cl H Cl Cl Cl Cl Ni 1 Pyridine 93.6% yellow164 H H H H Cl Cl Cl Cl Ni 1 Morpholine 92.9% yellow165 H H H H Cl Cl Cl Cl Ni 2 Ethylenediamine 94.0% yellow166 H H H H Cl Cl CH.sub.3 O Cl Ni 2 Ethylenediamine 85.7% yellow167 H H CH.sub.3 H Cl Cl Cl Cl Ni 2 Ethylenediamine 96.5% yellow168 H H CH.sub.3 H Cl Cl CH.sub.3 O Cl Ni 2 Ethylenediamine 92.9% yellow169 H H Cl H Cl Cl Cl Cl Ni 2 Ethylenediamine 89.2% yellow170 H CH.sub.3 Cl CH.sub.3 Cl Cl Cl Cl Ni 2 Ethylenediamine 78.4% yellow171 H H H H Cl Cl Cl Cl Ni 2 Ethylenediamine 91.0% yellow172 H H H H Cl Cl Cl Cl Ni 2 Hexamethylenediamine 86.3% yellow173 H H H H Cl Cl Cl Cl Ni 2 Triethylenediamine 93.0% yellow174 H H H H Cl Cl Cl Cl Ni 2 Piperazine 94.7% yellow175 H H H H Cl Cl CH.sub.3 O Cl Ni 2 Piperazine 82.1% yellow176 H H CH.sub.3 H Cl Cl CH.sub.3 O Cl Ni 2 Piperazine 89.7% yellow177 H H Cl H Cl Cl Cl Cl Ni 2 Piperazine 89.6% yellow178 H H H H Cl Cl Cl Cl Ni 2 4,4'-Diamino- 71.5% yellow diphenylsulphone__________________________________________________________________________
The metal complexes of the formula (D) in Table 5 were synthesised as described in Example 2. ##STR31##
TABLE 5__________________________________________________________________________Example X.sub.3 X.sub.4 X.sub.5 X.sub.6 R M n L Yield Shade in PVC__________________________________________________________________________179 Cl Cl Cl Cl H Ni 1 NH.sub.3 91.6% orange180 Cl Cl CH.sub.3 O Cl H Ni 1 NH.sub.3 100% yellow-orange181 Cl Cl Cl Cl H Ni 1 Benzylamine 94.5% orange182 Cl Cl CH.sub.3 O Cl H Ni 1 Benzylamine 100% orange183 Cl Cl Cl Cl H Ni 1 Aniline 92.0% brown184 Cl Cl Cl Cl H Ni 1 Pyridine 97.4% brown185 Cl Cl CH.sub.3 O Cl H Ni 2 Ethylenediamine 96.4% orange__________________________________________________________________________
The metal complexes of the formula (E) wherein the symbols have the meaning indicated in Table 6, are obtained in accordance with the instructions of Example 2. ##STR32##
TABLE 6__________________________________________________________________________Example X.sub.3 X.sub.4 X.sub.5 X.sub.6 M n L Yield Shade in PVC__________________________________________________________________________186 H H H H Ni 1 NH.sub.3 78.6% yellow187 CH.sub.3 O Cl CH.sub. 3 O Cl Ni 1 NH.sub.3 90.0% yellow188 Cl Cl Cl Cl Ni 2 Ethylenediamine 88.0% yellow189 H H H H Ni 2 Ethylenediamine 85.7% yellow190 Cl Cl CH.sub.3 O Cl Ni 2 Ethylenediamine 87.1% yellow191 CH.sub.3 O H CH.sub.3 O Cl Ni 2 Ethylenediamine 87.1% yellow192 H H H H Ni 2 Piperazine 66.7% yellow193 Cl Cl CH.sub.3 O Cl Ni 2 Piperazine 54.8% yellow194 CH.sub.3 O Cl CH.sub.3 O Cl Ni 2 Piperazine 83.9% yellow__________________________________________________________________________
Metal complexes of the formula (F) wherein the symbols have the meaning indicated in Table 7, are obtained in accordance with instructions of Example 2. ##STR33##
TABLE 7__________________________________________________________________________Example X.sub.3 X.sub.4 X.sub.5 X.sub.6 M n L Yield Shade in PVC__________________________________________________________________________195 Cl Cl Cl Cl Ni 1 NH.sub.3 88.5% yellow196 Cl Cl CH.sub.3 Cl Ni 1 NH.sub.3 92.6% yellow197 Cl Cl CH.sub.3 O Cl Ni 1 Benzylamine 84.4% yellow198 Cl Cl Cl Cl Ni 1 Benzylamine 71.9% yellow199 Cl Cl Cl Cl Ni 1 Aniline 90.0% yellow200 CH.sub.3 O Cl CH.sub.3 O Cl Ni 1 Aniline 86.5% yellow201 Cl Cl Cl Cl Ni 1 Pyridine 93.5% yellow202 Cl Cl Cl Cl Ni 2 Ethylenediamine 80.1% yellow203 Cl Cl CH.sub.3 O Cl Ni 2 Ethylenediamine 85.7% yellow204 Cl Cl Cl Cl Ni 2 4,4'-diamino- 74.0% yellow diphenylsulphone__________________________________________________________________________
The metal complexes of the formula (G) wherein the symbols have the meaning indicated in Table 8, are obtained in accordance with the instructions of Example 2. ##STR34##
TABLE 8__________________________________________________________________________Ex- Shade inample X.sub.3 X.sub.4 X.sub.5 X.sub.6 R M n L Yield PVC__________________________________________________________________________205 Cl Cl Cl Cl H Ni 1 NH.sub.3 92.0% red206 Cl Cl Cl Cl COOH Ni 1 NH.sub.3 97.5% orange207 Cl Cl Cl Cl Ni 1 NH.sub.3 100% orange208 Cl Cl Cl Cl H Ni 1 Benzylamine 88.1% orange209 Cl Cl Cl Cl Ni#STR35## Benzylamine 68.9% orange210 Cl Cl Cl Cl H Ni 1 Aniline 95.3% brown211 CH.sub.3 O Cl CH.sub.3 O Cl Ni#STR36## 1 Aniline 78.4% brown212 Cl Cl Cl Cl H Ni 1 Pyridine 94.6% red213 Cl Cl Cl Cl Ni#STR37## 1 Pyridine 94.7% brown214 Cl Cl Cl Cl H Ni 1 Morpholine 86.0% red215 Cl Cl Cl Cl Ni#STR38## 1 Morpholine 93.1% red216 Cl Cl Cl Cl H Ni 1 N-methylpip- 79.4% orange erazine217 Cl Cl Cl Cl H Ni 1 N-phenylpip- 93.6% red erazine218 Cl Cl Cl Cl H Ni 2 Ethylene- 95.2% red diamine219 Cl Cl CH.sub.3 O Cl H Ni 2 Ethylene- 85.2% orange diamine220 Cl Cl Cl Cl Ni#STR39## 2 Ethylene- diamine 91.0% red221 Cl Cl Cl Cl Ni#STR40## 2 Piperazine 99.0% orange222 Cl Cl Cl Cl H Ni 2 Piperazine 95.3% red223 Cl Cl Cl Cl COOH Ni 2 Piperazine 91.4% red-brown224 Cl Cl Cl Cl H Ni 2 4,4'-diamino- 88.8% orange diphenylsulphone225 Cl Cl Cl Cl COOH Ni 2 1,4-diamino- 70.5% red-brown cyclohexane__________________________________________________________________________
Metal complexes of the formula (H) wherein the symbols have the meaning indicated in Table 9, are obtained in accordance with the instructions of Example 2. ##STR41##
TABLE 9__________________________________________________________________________Example X.sub.3 X.sub.4 X.sub.5 X.sub.6 R.sub.1 R.sub.2 M n L Yield Shade in__________________________________________________________________________ PVC226 Cl Cl Cl Cl H H Ni 1 NH.sub.3 98.7% organge227 Cl Cl CH.sub.3 O Cl Cl Cl Ni 1 NH.sub.3 96.3% red-brown228 Cl Cl Cl Cl Cl Cl Ni 1 Benzylamine 92.0% orange229 Cl Cl Cl Cl Cl Cl Ni 1 Aniline 91.7% yellow-orange230 Cl Cl Cl Cl Cl Cl Ni 1 Pyridine 100% yellow-orange231 Cl Cl Cl Cl Cl Cl Ni 1 Morpholine 95.4% orange232 Cl Cl Cl Cl H H Ni 1 Morpholine 91.3% yellow-orange233 Cl Cl Cl Cl Cl Cl Ni 2 Ethylenediamine 86.7% red-brown234 Cl Cl Cl Cl Cl Cl Ni 2 Ethylenediamine 71.4% red-brown235 Cl Cl Cl Cl Cl Cl Ni 2 Piperazine 99.3% red-brown236 Cl Cl Cl Cl H H Ni 2 Piperazine 94.0% yellow-orange237 Cl Cl Cl Cl Cl Cl Ni 2 4,4'-Diamino- 98.3% yellow diphenylsulphone__________________________________________________________________________
The metal complexes of the formula (I) wherein the symbols have the meaning indicated in Table 10, are obtained in accordance with the instructions of Example 2. ##STR42##
TABLE 10__________________________________________________________________________ Shade inExample X.sub.3 X.sub.4 X.sub.5 X.sub.6 R M n L Yield PVC__________________________________________________________________________238 Cl Cl Cl Cl CH.sub.3 Ni 1 NH.sub.3 81.9% yellow239 Cl Cl CH.sub.3 O Cl CONH.sub.2 Ni 1 NH.sub.3 91.3% yellow240 Cl Cl CH.sub.3 O Cl CONH.sub.2 Ni 1 Benzylamine 77.8% yellow241 Cl Cl Cl Cl CH.sub.3 Ni 1 Aniline 82.8% yellow242 Cl Cl Cl Cl CH.sub.3 Ni 2 Ethylenediamine 84.1% yellow243 Cl Cl CH.sub.3 O Cl CONH.sub.2 Ni 2 Ethylenediamine 90.0% yellow__________________________________________________________________________
The metal complexes of the formula (J) wherein the symbols have the meaning indicated in Table 11, are obtained in accordance with the instructions of Example 2. ##STR43##
TABLE 11__________________________________________________________________________Ex- ample X.sub.3 X.sub.4 X.sub.5 X.sub.6 M n L Yield Shade__________________________________________________________________________ in PVC244 Cl Cl Cl Cl Ni 1##STR44## NH.sub.3 91.7% red245 Cl Cl Cl Cl Ni " 1 Benzylamine 84.5% orange246 Cl Cl Cl Cl Ni " 1 Pyridine 92.0% orange247 Cl Cl Cl Cl Ni " 2 Ethylenediamine 90.5% orange248 Cl Cl Cl Cl Ni 1##STR45## NH.sub.3 96.9% yellow249 Cl Cl Cl Cl Ni " 2 Piperazine 96.0% orange250 Cl Cl Cl Cl Ni 1##STR46## NH.sub.3 54.6% yellow251 Cl Cl Cl Cl Ni " 1 Benzylamine 71.4% yellow252 Cl Cl Cl Cl Ni " 1 Aniline 71.8% yellow253 Cl Cl Cl Cl Ni " 1 Pyridine 88.5% yellow254 Cl Cl Cl Cl Ni 2##STR47## Ethylenediamine 94.6% yellow255 Cl Cl Cl Cl Ni " 2 Piperazine 96.0% yellow256 Cl Cl Cl Cl Ni 2##STR48## Piperazine 92.5% yellow257 Cl Cl Cl Cl Ni " 2 Ethylenediamine 89.8% yellow258 Cl Cl Cl Cl Ni " 1 NH.sub.3 93.8% yellow__________________________________________________________________________
EXAMPLE 259
189 parts of 2,4-dihydroxyquinoline-3-aldehyde and 2.99 parts of 4,5,6,7-tetrachloroisoindolin-1-onylidenehydrazine are stirred for 15 minutes at 100.degree. C in 150 parts by volume of methylcellosolve. After adding 0.93 part of aniline, followed by 2.50 parts of nickel acetate tetrahydrate, the yellow suspension is stirred for a further 4 hours at 100.degree. C. The reaction product is then filtered off while hot, washed well with methylcellosolve, alcohol and acetone and dried at 80.degree. C in vacuo. This gives 6.0 parts (97% of theory) of an analytically pure, yellow pigment having the formula indicated in Example 1.
For those examples in which L denotes NH.sub.3, a gentle stream of ammonia is passed in during the metallisation.
Half a mol of diamine was used for the examples in which n denotes 2, and a third of a mol of triamine was used for Example 91.
EXAMPLE 260
2 g of the pigment prepared in accordance with Example 1 are ground on a triple roll mill together with 36 g of hydrated alumina, 60 g of linseed oil varnish of medium viscosity and 2 g of cobalt linoleate. The yellow prints produced using the resulting colorant paste are deep and outstandingly fast to light.
EXAMPLE 261
0.6 g of the pigment prepared in accordance with Example 1 is mixed with 67 g of polyvinyl chloride, 33 g of dioctyl phthalate, 2 g of dibutyl-tin dilaurate and 2 g of titanium dioxide and the mixture is processed on a roll mill for 15 minutes at 160.degree. C to give a thin sheet. The yellow coloration thus produced is deep and fast to migration, heat and light.
EXAMPLE 262
10 g of titanium dioxide and 2 g of the pigment prepared in accordance with Example 2 are ground for 48 hours in a ball mill together with 88 g of a mixture of 26.4 g of coconut alkyd resin, 24.0 g of melamine-formaldehyde resin (50% solids content), 8.8 g of ethylene glycol monomethyl ether and 28.8 g of xylene.
If this lacquer is sprayed onto an aluminium foil, predried for 30 minutes at room temperature and then stoved for 30 minutes at 120.degree. C, a yellow lacquering is obtained, which is distinguished by good depth of colour and by very good fastness to overlacquering, ligth and weathering.

Metal complexes of bis-hydrazones

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