CA1104758A - Water-insoluble disazomethine mixed metal-complex compounds, process for preparing them and their use as colorants - Google Patents
Water-insoluble disazomethine mixed metal-complex compounds, process for preparing them and their use as colorantsInfo
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- CA1104758A CA1104758A CA273,737A CA273737A CA1104758A CA 1104758 A CA1104758 A CA 1104758A CA 273737 A CA273737 A CA 273737A CA 1104758 A CA1104758 A CA 1104758A
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-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B55/00—Azomethine dyes
- C09B55/005—Disazomethine dyes
- C09B55/007—Disazomethine dyes containing only carbocyclic rings
Abstract
Abstract of Disclosure:
New valuable, water-insoluble mixed diaminophenylene-disazomethlne-naphthalene metal-complex compounds had been found consisting of two or more metal-complex dlsazomethine compounds of different constitution or different metal com-plexes which are prepared according to this invention by re-acting one or several o-phenylene diamines with one or several hydroxy-naphthaldehydes at which process metallization is carried out by addition of one or several metal-yielding agents of one or several different metals before, during or after the conden-sation reaction of the amino and aldehyde compounds.
The new mixed metal-complex compounds are suitable as colorants, especially as pigments for the coloring of printing pastes, printing inks, high-molecular plastic masses, lacquers, paints and spinning masses which colored materials possess very good fastness properties to, for example, light, to weather, to solvents or to migration,and the colorants themselves possess an excellent fastness to heat and have a high tinctorial strength, a good transparency, a good dispersability and, in general, pure shades.
New valuable, water-insoluble mixed diaminophenylene-disazomethlne-naphthalene metal-complex compounds had been found consisting of two or more metal-complex dlsazomethine compounds of different constitution or different metal com-plexes which are prepared according to this invention by re-acting one or several o-phenylene diamines with one or several hydroxy-naphthaldehydes at which process metallization is carried out by addition of one or several metal-yielding agents of one or several different metals before, during or after the conden-sation reaction of the amino and aldehyde compounds.
The new mixed metal-complex compounds are suitable as colorants, especially as pigments for the coloring of printing pastes, printing inks, high-molecular plastic masses, lacquers, paints and spinning masses which colored materials possess very good fastness properties to, for example, light, to weather, to solvents or to migration,and the colorants themselves possess an excellent fastness to heat and have a high tinctorial strength, a good transparency, a good dispersability and, in general, pure shades.
Description
~1~4~58 Novel mixed metal-complex compounds have been found which consist of at least two, for example, two, three, four or five, es-pecially two, three or four, preferably two or four o~ the compounds of th~e yeneral formula (I) 1 ~ 3 ~,N
CH = = C~ (I) ~ O - ~é - ~
wherein each Z which may be identical or different from one another, represents hydrogen, halogen, such as fluorine, chlorine, bromine, lower alkoxy, preferably one having 1 to 4 carbon atoms, a nitro or cyano group, Me is a bivalent metal atom, preferably nickel, copper, cobalt, zinc, cadmium or manganese, especially nickel or copper, is hydrogen, halogen, such as chlorine, bromine, fluorine, lower alkoxy or lower alkyl, preferably one having 1 to 4 carbon atoms, a phenoxy group, a phenoxy group substituted by substituents, prefer-ably one or two substituents, selected from the group halogen, such as chlorine or bromine, lower alkyl and lower alkoxy, a hydroxy, cyano, trifluoromethyl, carboxy, lower carboxylic acid alkyl ester group, preferably one having 1 to 4 carbon atoms in the alkyl moiety, a lower alkanoyl group, preferably one having 1 to 4 carbon atoms in the alkyl moiety, a benzoyl group or a benzoyl group substituted by substituents, preferably 1 or 2 substituents, selected from the group halogen, lower alkyl and lower alkoxy, R2 is hydrogen, ~ ~ - 2 , . ..
~: :
:
- . :
:: ..
.-,: ~ :
~ '; ,'~ ,. ~ .
1~4758 halogen, such as chlorine, bromine, fluorine, lower alkoxy, preferably one h~ving 1 to 4 carbon atoms, lower al~yl, prefer-ably one having 1 to 4 carbon atoms, a phenoxy group, a phenoxy group substituted by substituents, preferably 1 or 2 substituents,selected frcm the group halogen, lower alkyl and lower alkoxy, a hydroxy, cyano, trifluoromethyl, carboxy, lower carboxylic acid alkyl ester group, preferably one having 1 to 4 carbon atoms in the alkyl moiety, a lower alkanoyl group, preferably one having 1 to 4 carbon atoms in the alkyl moiety, a benzoyl group or a benzoyl group substituted by substituents, preferably 1 or 2 substituents~selected from the group halogen, lower alkyl and lower alkoxy and R3 is hydrogen, halogen, such as chlorine, bromine, fluorine, a lower alkoxy group, preferably one having 1 to 4 carbon atoms, or a lower alkyl group, preferably one having 1 to 4 carbon atoms.
Mixed metal-comp~ex compounds consisting of one or several such as 1, 2 or 3 or 4 metal-complex compounds of the above formula I having, preferably one or two, components, wherein R1 = R2 = R3 = hydrogen, and having, preferably one or two, components wherein at least one substituent, i.e. one or two, of the series Rl, R2 and R3 is no hydrogen atom, are preferred.
Among these last-mentioned preferred metal-mixed complexes there may especially be mentioned those which contain as com-ponents of the formula (I) besides the one or several such as 1, 2 or 3 compounds wherein R1 = R2 = R3 is hydrogen, one or several, such as 1, 2 or 3, substituted metal complex disazo-methine compounds of the formula (I), wherein R1 stands for hydrogen, R2 for chlorine or bromine or an alkyl group having , - . .
1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon a~oms, a phenoxy group which may be substituted by 1 or 2 substituents selected from the group halogen, such as chlorine or bromine, :lower alkyl and lower alkoxy, a hydroxy group, cyano, ~rifluoro-methyl, carboxy or carboxylic acid alkyl ester group having 1 to 4 carbon atoms and R3 stands for hydrogen or chlorine or bromine or an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, as well as each ~, identical or different, represents hydrogen, chlorine or bromine atom, a methoxy, ethoxy, propoxy, nitro or cyano group.
Those mixed metal-complex compounds thereof are preferred which contain in totai 10 to 50 mol % of one or several such as 1, 2 or 3, compounds of the formula (I) as mixed complex compounds, wherein at least one, i.e.one or two of the substi-tutents R1, R2, R3 is not identical to hydrogen, and Me and Z
are defined above.
Among the mixed complex compounds consisting of one or several, such as 1, 2 or 3 or 4 components of the above formula (I) with R1 = R2 = ~3 represen.ting hydrogen, there are further-more preferred those the portion of which of one or several such as 1 or 2 or 3, nickel complex compounds is not more than 95 mol%, preferably 60 to 95, especially 60 to 92 mol%.
Among the above-mentioned mixed complexes there are es-pecially preferred those which contain beside one or several, preferably one or two components with R1 = R2 = R3 identical to hydrogen especially with different metal atoms, also contain one or several, preferably one or two components having es-pecially dif~erent metal atoms but having identical structure , .
, .. . : : : : .:: .
. : . .
-~: . .
. . , .. , , , . . , , ;
....
.
- ~
-: :~ :: -~47~B
with regard to the substituents in the phenylene and naphthylene xadicals, in which R1 is hydrogen, halogen, preferably chlorine or bromine, alkyl having 1 to 3 carbon atoms, alkoxy having I to 3 carbon atoms, a hydroxy, carboxy or carboxylic acid alkyl ester group having 1 to 4 carbon atoms in the alkyl moiety, R2 is hydrogen, halogen, preferably chl.orine or bromine, alkyl having 1 to 3 carbon atoms, alkoxy having 1 to 3 carbon atoms, a hydroxy, carboxy or carboxylic acid alkyl ester group having 1 to 4 carbon atoms in the alkyl moiety, and R3 is hydrogen, halogen,preferably chlorine or bromine, alkyl having 1 to 3 carbon atoms or alkoxy having 1 to 3 carbon atoms, wherein at least one of the substituents R1, R2 and R3 is not identical to hydrogen.
Very interesting are also mixed complex compounds of the general formula (Ia) '~ ' ' ' CH = N N = CH (Ia) ~ O - Me - ~
wherein X is hydrogen or halogen, such as chlorine or bromine, or an alkoxy group having 1 to 4 carbon atoms, especially a methoxy or ethoxy group, and Me stands for nickel or copper, the portion of mixed complex component with X identical to hydrogen being in total between 60 and 95 mol% and the portion o~ mixed complex component(s) with Me identical to ~ickel being in total between 100 to 85 mol~.
. .
! `, . .
~' ' ' . , .
'' ' 4~5~
Especially interesting are mixed complexes which consist of, in total, 90 to 60 mol% one, two or three, nickel complex components of the formula (I) wherein R1 = R2 = R3 = hydrogen, and of, in total, 10 to 40 mol% of one, two or three nickel complex compounds of the formula (I) wherein R1 is hydrogen, halogen, preferably chlorine or bromine, an alkyl group having 1 to 3 carbon atoms, alkoxy having 1 to 3 carbon atoms, a hydroxy, carboxy or carboxylic acid alkyl ester group having 1 to 4 carbon atoms in the alkyl moiety R2 is hydrogen, halogen, preferably chlorine or brom.ine, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a hydroxy, carboxy or carboxylic acid alkyl ester group having 1 to 4 carbon atoms, in the alkyl moiety, and R3 is hydrogen, halogen, preferably chlorine or bromine, alkyl having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, wherein at least one of the substituents R1, R2 and R3 are not identical to hydrogen.
There are furthermore interesting mixed complexes consisting of one or several, such as 1,2 or 3 or 4 compounds of the formula (I), wherein R1 = R2 = R3 represents hydrogen, with a portion of 95 to 60 mol~ of one or several, such as 1, 2 or 3, nickel com-plex compounds and of 5 to 40 mol~ of one or several luch as 1, 2 or 3 copper complex compounds.
Among all the above mentioned mixed complex compounds those are preferred which contain as components compounds of the formula (I) in which each Z, identical or different, stands for hydrogen, bromine or methoxy; especially, among all the above-mentioned mixed complex compounds are preferred in which each Z
is hydrogen.
The mixed complex compounds of the invention are available : ;~; ' . ' ' :' ' .
-.
.: .: .
- ,, ~ - . . :. ~.
~: :. . .. .. ~ :.
47~8 in most cases as mixed crystals, but they are no mechanical mixtures of i.ndividual compounds of the formula (I).
The novel mixed complex compounds may be obtained in usual Tnanner by condensing in mixture with one another 2 mols of one aldehyde of the formula (II) ~HO
~ OH (II) or, on the whole, ~ mols of two or several aldehydes of the formula (II) wherein Z has the above meaning with 1 mol of an o-phenylene-diamine of the formula (III) R ~2 R (III) - )~
or with, on the whole, 1 mol of two or several diamines of the formula ~III) wherein R1, R2 and R3 have the above meanings, and treating the disazomethine compound obtainea, - if starting from uniform reactants (II) and (III) in each case, - during the condensation reaction or subsequently with metallizing agents of two or several different metals Me having the above meaning, or treating the disazomethine compounds mixture obtained, if starting from reactants (II) and (III) at least one of which con-sting of at least two compounds, during the condensation reaction or subsequently with one or several metallizing agents of one or two or several different metals Me of the above meaning.
The novel mixed complex compounds of the present invention may also be prepared by reducing one or several o-nitroanilines .
, ~ ,.
:
. .
' ~ -:
7S~3 o:E the formula ~IV)
CH = = C~ (I) ~ O - ~é - ~
wherein each Z which may be identical or different from one another, represents hydrogen, halogen, such as fluorine, chlorine, bromine, lower alkoxy, preferably one having 1 to 4 carbon atoms, a nitro or cyano group, Me is a bivalent metal atom, preferably nickel, copper, cobalt, zinc, cadmium or manganese, especially nickel or copper, is hydrogen, halogen, such as chlorine, bromine, fluorine, lower alkoxy or lower alkyl, preferably one having 1 to 4 carbon atoms, a phenoxy group, a phenoxy group substituted by substituents, prefer-ably one or two substituents, selected from the group halogen, such as chlorine or bromine, lower alkyl and lower alkoxy, a hydroxy, cyano, trifluoromethyl, carboxy, lower carboxylic acid alkyl ester group, preferably one having 1 to 4 carbon atoms in the alkyl moiety, a lower alkanoyl group, preferably one having 1 to 4 carbon atoms in the alkyl moiety, a benzoyl group or a benzoyl group substituted by substituents, preferably 1 or 2 substituents, selected from the group halogen, lower alkyl and lower alkoxy, R2 is hydrogen, ~ ~ - 2 , . ..
~: :
:
- . :
:: ..
.-,: ~ :
~ '; ,'~ ,. ~ .
1~4758 halogen, such as chlorine, bromine, fluorine, lower alkoxy, preferably one h~ving 1 to 4 carbon atoms, lower al~yl, prefer-ably one having 1 to 4 carbon atoms, a phenoxy group, a phenoxy group substituted by substituents, preferably 1 or 2 substituents,selected frcm the group halogen, lower alkyl and lower alkoxy, a hydroxy, cyano, trifluoromethyl, carboxy, lower carboxylic acid alkyl ester group, preferably one having 1 to 4 carbon atoms in the alkyl moiety, a lower alkanoyl group, preferably one having 1 to 4 carbon atoms in the alkyl moiety, a benzoyl group or a benzoyl group substituted by substituents, preferably 1 or 2 substituents~selected from the group halogen, lower alkyl and lower alkoxy and R3 is hydrogen, halogen, such as chlorine, bromine, fluorine, a lower alkoxy group, preferably one having 1 to 4 carbon atoms, or a lower alkyl group, preferably one having 1 to 4 carbon atoms.
Mixed metal-comp~ex compounds consisting of one or several such as 1, 2 or 3 or 4 metal-complex compounds of the above formula I having, preferably one or two, components, wherein R1 = R2 = R3 = hydrogen, and having, preferably one or two, components wherein at least one substituent, i.e. one or two, of the series Rl, R2 and R3 is no hydrogen atom, are preferred.
Among these last-mentioned preferred metal-mixed complexes there may especially be mentioned those which contain as com-ponents of the formula (I) besides the one or several such as 1, 2 or 3 compounds wherein R1 = R2 = R3 is hydrogen, one or several, such as 1, 2 or 3, substituted metal complex disazo-methine compounds of the formula (I), wherein R1 stands for hydrogen, R2 for chlorine or bromine or an alkyl group having , - . .
1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon a~oms, a phenoxy group which may be substituted by 1 or 2 substituents selected from the group halogen, such as chlorine or bromine, :lower alkyl and lower alkoxy, a hydroxy group, cyano, ~rifluoro-methyl, carboxy or carboxylic acid alkyl ester group having 1 to 4 carbon atoms and R3 stands for hydrogen or chlorine or bromine or an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, as well as each ~, identical or different, represents hydrogen, chlorine or bromine atom, a methoxy, ethoxy, propoxy, nitro or cyano group.
Those mixed metal-complex compounds thereof are preferred which contain in totai 10 to 50 mol % of one or several such as 1, 2 or 3, compounds of the formula (I) as mixed complex compounds, wherein at least one, i.e.one or two of the substi-tutents R1, R2, R3 is not identical to hydrogen, and Me and Z
are defined above.
Among the mixed complex compounds consisting of one or several, such as 1, 2 or 3 or 4 components of the above formula (I) with R1 = R2 = ~3 represen.ting hydrogen, there are further-more preferred those the portion of which of one or several such as 1 or 2 or 3, nickel complex compounds is not more than 95 mol%, preferably 60 to 95, especially 60 to 92 mol%.
Among the above-mentioned mixed complexes there are es-pecially preferred those which contain beside one or several, preferably one or two components with R1 = R2 = R3 identical to hydrogen especially with different metal atoms, also contain one or several, preferably one or two components having es-pecially dif~erent metal atoms but having identical structure , .
, .. . : : : : .:: .
. : . .
-~: . .
. . , .. , , , . . , , ;
....
.
- ~
-: :~ :: -~47~B
with regard to the substituents in the phenylene and naphthylene xadicals, in which R1 is hydrogen, halogen, preferably chlorine or bromine, alkyl having 1 to 3 carbon atoms, alkoxy having I to 3 carbon atoms, a hydroxy, carboxy or carboxylic acid alkyl ester group having 1 to 4 carbon atoms in the alkyl moiety, R2 is hydrogen, halogen, preferably chl.orine or bromine, alkyl having 1 to 3 carbon atoms, alkoxy having 1 to 3 carbon atoms, a hydroxy, carboxy or carboxylic acid alkyl ester group having 1 to 4 carbon atoms in the alkyl moiety, and R3 is hydrogen, halogen,preferably chlorine or bromine, alkyl having 1 to 3 carbon atoms or alkoxy having 1 to 3 carbon atoms, wherein at least one of the substituents R1, R2 and R3 is not identical to hydrogen.
Very interesting are also mixed complex compounds of the general formula (Ia) '~ ' ' ' CH = N N = CH (Ia) ~ O - Me - ~
wherein X is hydrogen or halogen, such as chlorine or bromine, or an alkoxy group having 1 to 4 carbon atoms, especially a methoxy or ethoxy group, and Me stands for nickel or copper, the portion of mixed complex component with X identical to hydrogen being in total between 60 and 95 mol% and the portion o~ mixed complex component(s) with Me identical to ~ickel being in total between 100 to 85 mol~.
. .
! `, . .
~' ' ' . , .
'' ' 4~5~
Especially interesting are mixed complexes which consist of, in total, 90 to 60 mol% one, two or three, nickel complex components of the formula (I) wherein R1 = R2 = R3 = hydrogen, and of, in total, 10 to 40 mol% of one, two or three nickel complex compounds of the formula (I) wherein R1 is hydrogen, halogen, preferably chlorine or bromine, an alkyl group having 1 to 3 carbon atoms, alkoxy having 1 to 3 carbon atoms, a hydroxy, carboxy or carboxylic acid alkyl ester group having 1 to 4 carbon atoms in the alkyl moiety R2 is hydrogen, halogen, preferably chlorine or brom.ine, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a hydroxy, carboxy or carboxylic acid alkyl ester group having 1 to 4 carbon atoms, in the alkyl moiety, and R3 is hydrogen, halogen, preferably chlorine or bromine, alkyl having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, wherein at least one of the substituents R1, R2 and R3 are not identical to hydrogen.
There are furthermore interesting mixed complexes consisting of one or several, such as 1,2 or 3 or 4 compounds of the formula (I), wherein R1 = R2 = R3 represents hydrogen, with a portion of 95 to 60 mol~ of one or several, such as 1, 2 or 3, nickel com-plex compounds and of 5 to 40 mol~ of one or several luch as 1, 2 or 3 copper complex compounds.
Among all the above mentioned mixed complex compounds those are preferred which contain as components compounds of the formula (I) in which each Z, identical or different, stands for hydrogen, bromine or methoxy; especially, among all the above-mentioned mixed complex compounds are preferred in which each Z
is hydrogen.
The mixed complex compounds of the invention are available : ;~; ' . ' ' :' ' .
-.
.: .: .
- ,, ~ - . . :. ~.
~: :. . .. .. ~ :.
47~8 in most cases as mixed crystals, but they are no mechanical mixtures of i.ndividual compounds of the formula (I).
The novel mixed complex compounds may be obtained in usual Tnanner by condensing in mixture with one another 2 mols of one aldehyde of the formula (II) ~HO
~ OH (II) or, on the whole, ~ mols of two or several aldehydes of the formula (II) wherein Z has the above meaning with 1 mol of an o-phenylene-diamine of the formula (III) R ~2 R (III) - )~
or with, on the whole, 1 mol of two or several diamines of the formula ~III) wherein R1, R2 and R3 have the above meanings, and treating the disazomethine compound obtainea, - if starting from uniform reactants (II) and (III) in each case, - during the condensation reaction or subsequently with metallizing agents of two or several different metals Me having the above meaning, or treating the disazomethine compounds mixture obtained, if starting from reactants (II) and (III) at least one of which con-sting of at least two compounds, during the condensation reaction or subsequently with one or several metallizing agents of one or two or several different metals Me of the above meaning.
The novel mixed complex compounds of the present invention may also be prepared by reducing one or several o-nitroanilines .
, ~ ,.
:
. .
' ~ -:
7S~3 o:E the formula ~IV)
2 (IV) R1 ~ ~ 3 wherein R1, R2 and R3 have the above meaning, according to usual methods and reacting the diamine compound of the formula IIII) or their mixtures obtained without intermediate isolation with one or several hydroxynaphthaldehyde compounds of the formula (II) in a molar ratio of 1:2 and metallizing according tG the above-mentiQned preparation process.
Aldehydes of the formula (II) are especially those in which Z is hydrogen, chlorine or bromine, a methoxy, ethoxy or propoxy group, a nitro or cyano group. They may be obtained in known manner by formylation of the corresponding 2-hydroxy-naphthalenes, especially according to the method of Duf~.
Diamines of the formula (III) are especially those in which the benzene nucleus is substituted by at least one halogen atom, for example one or two chlorine or bromine atoms, one or two lower alkyl groups having 1 to 4 carbon atoms, such as methyl, ethyl, propyl or butyl groups, one or two lower alkoxy groups having 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy or butoxy groups, a phenoxy group, which may be substituted by halogen atoms, lower alkyl and/or alkoxy groups, a hydroxy group, a cyano group, a trifluoromethyl, carboxy or lower carboxylic acid alkyl ester group such as a methyl, ethyl, propyl or butyl ester group.
The condensation of the aldehyde~s) with the diamine : : ~ : , .
.. . ..... 1. . ~:.
, :: - ~ - . .
HOE 76/F 0~9 75~
mixture is expediently carried out in water or in an organic solvent at an elevated temperature, preferably betw~en about 60C and the boiling point of the solvent used. There are especially considered as solvents: water, ethanol, glacial acetic acid, dimethylformamide, N-methylpyrrolidone, glycolmono-or -dimethylether, xylene or the mixtures thereof.
The disazomethine mixtures obtained are difficultly soluble in the solvents mentioned and may be easily isolated by filtra-tion. Possible contaminations may be removed by washing out. In order to convert the disazomethine mixtures obtained into the mixed complex compounds of the invention the metal-free com-pounds are treated with compounds or mixtures of compounds which yield two-valent metal, for example with salts of nickel, copper, cobalt, zinc, cadmium or manganese, preferably the formiates or acetates thereof.
The complexation of a disazomethine of the formula (V) Z Z
Q
~H = N ~ = CH ~ (V) OH - OH
wherein Z has the above meaning is preferably effected with a mixture of metal-yielding agents of imperatively up to 5 mol%
of a metal different from nickel, thus with metal-yielding agents which contain metal-yielding reagents of one or several metals Me of the above meaning different from nickel, i.e. con-tain at most 95 mol~ of a nickel-yielding agent.
Metallization is expediently carried out in one of the above-mentioned solvents or in a mixture thereof.
;~
' ' ' ;~ , :
.~ .
..:
.
~IOE 75/F 049 lP~75~
Metallization may also be carried out before or, as al-ready mentioned, simultaneously with the azomethine condensa-tion/ by treating the aldehyde flrst individually with a ~etal-yielding agent in one of the above solvents or in a mix-ture thereof and then condensing with the diamine, or conden sing the aldehyde together with the diamine in the presence of the metal-yielding agents in the solvents mentioned.
The novel mixed complex compounds have proved to be very good coloring agents and represent especial]y good pigments which are suitable, especially after a conditioning usual for pigments, for example for the dyeing of plastic masses (which are masses of plastics or synthetic resins free from solvents or containing solvents or free from softening agents or containing softening agents). furthermore for the pigmentation of paints on an oily or aqueous base as well as of different lacquers, for the dyeing of viscose and cellulose acetate or for the pigmentation of polyethylene, polystyrene, polyvinyl chloride, rubber and syn~
thetic leather, but which may be preferably used for the pre-paration of metal effect lacquers.
They may also be used in printing inks for graphic industry, for the coloring of the paper mass, for coating textiles or for the pigment print. The colourings obtained have an excellent fastness to migration overwarnishing hleeding to light, to weather and ~o solvents, they have an excellent fastness to heat and are characterized by a high tinctorial strength, a good transparency, a good dispersability and often surprisingly pure shades.
In contradistinction to the next comparable known indi-vidual compounds of the above formula I wherein R1= R2 = R3 =
:. ~ . , ~ ., ., ~ :
:-. i: :. .
hydrogen or one of these substituents is a nitro, carboxylic acid amide or sulfonic acid amide group (cf. German Offenlegungs-schrift No 2,308,594, German Offenlegungsschrift No. 2,007,844 and French Patent Specification No. 1,~16,293), the mixed complex compounds of the instant invention are characterized by a better fastness to migration and to solvents, for example an improved fastness to bleeding and overvarnishing, by an elevated trans-parency and a better dispersability as well as especially a higher tinctorial strength and a pure shade.
Especially with regard to the next comparable pigment corres-ponding to the above formula I with R1 = R2 = R3 = hydrogen, Z
identical to hydrogen and Me identical to nickel (cf. German Offenlegungsschrift No. 2,308,594), a considerably improved fastness to overvarnishing, a considerably elevated tinctorial strength and a purer, more yellow shade of the mixed complex pigments has surprisingly been found, which could not be forseen with regard to the formation of the mixed complex.
For a crystal structure has been found for the mixed complex compounds of the present invention by X-ray difraction accor-ding to Debye - Scherrer which is surprisingly different from the known individual pigments of the formula I.
The following Examples serve to illustrate the invention and especially describe preferred mixed complex compounds and variants of the preparation processes mentioned. Parts and percentages are by weight.
E X ~ M P L E
A mixture of 51,6 parts of 2-hydroxy-1-naphthaldehyde, 48 parts of sodium acetate and 900 parts of water is ground for 15 minutes in a dispersing device ("dispergator") at room .
. :
.~ .
. .
7~;8 temperature. Then a solution of 46 parts of nickel sulfate in 150 parts of water is added, and the whole is dispersed for half an hour, the temperature increasing to 30 - 40C.
The finely divided suspension of the 2-hydroxy-1-napht-haldehyde nickel complex obtained is introduced into a three neck flask (reflux cooler, stirrer, thermometer), and after addition of a mixture of 4,6 parts of 4-methyl-o-phenylene-diamine and 12,2 parts of o-phenylene-diamine, the whole is heated within 2 hours steadily to 95C, in the course of which the pH value decreases from 7.8 to about 4.
The whole is then mixed with a solution of 48 parts of sodium acetate in 150 parts of water and stirring is continued for 150 minutes at boiling temperature; the mix~ure is filtered hot, washed with 4000 parts of water and dried. 70.7 Parts (98.2 ~ of the theory) of a mixed complex compound correspondin~
to the formula --- ((CH3)0,25; Ho.75) -~ CH = ~ N = OH ~ ~
are obtained, which dyes plastics in yellowish red shades and may be used in an excellent manner for the preparation of lacquers fast to light and to weather, especially metal effect lacquers where it shows a high tinctorial strength and an ex-cellent fastness to overvarnishing.
If the humid filter cake of the nickel comples is stirred with 5-times the amount of dimethylformamide for 5 hours at 100C, which i5 then suction-filtered, washed with dimethyl-~ .
. ~ :
- . :-,. : :
..
.~ :
~OE 76/E 049 7~8 formamide and water and subsequent dried , an improved pigment is obtained which has a better covering power, a better dis-persing capacity and a purer shade with otherwise comparable properties.
If the 4-methyl-o-phenylene-diamine is replaced by 3-methyl-o-phenylene-diamine, a pigment having comparable properties and fastness properties and a more bluish shade and a higher tinc-torial strength is obtained with the same yield.
E X A M P L E 2 to 11 If instead of the mixture of o-phenylene-diamine and 4-methyl~o-phenylene-diamine per 2 mols of hydroxynaphthaldehyde n mols of an other substituted o-phenylene-diamine and 1-n rnols of o-phenylene-diamine are added, and the operation is carried out as indicated in Example 1, there are also obtained mixed complex compounds of compounds of the formula Ia with the yields and shades listed in Table 1.
Table,1 CH = N ,~ = CH
O -~ Ni O
.
a= substituted or unsubstituted benzene nucleus n= portion of substituted benzene nucleus a, cal-culated on 1.00 1-n = portion of unsubstituted benzene nucleus a , ' ' - HOE 76/~' 049 4t75~
~cample L ~ ~ n n yield~ shade_ , Cl 0,15 98,2 % sc~rl-~
~ . ' CN 0~40 ga, 5 % i--r~d~
- ~$ ' ' 3CH3 ~~ 94,8 % red~n~
~, , .
. . .
Cl Cl 0,10 99~0 ~ yello~-b,r~wn ,' , ~ ' ' ' '.
6 COOH 0~10 96,8 % bordeau red ' .
7 ~ CH3 0,60 90~3 % blulsh red :
~ 8 OC~3 ' 0,20 95~2 yO bordeau-~ed " . ~ .
9 COOCH~ 0,20 97~2 Yo red-~' ,, , <~ .
: 10 OH 0~05 92~7 % bluish red - ._ 11 Cl ~CH30~15 ~8~0 % orange-red~-' ~$ ' .. ., _. . _ . . _ _ _ __,_ . . ... . . .
~47S8 _ A mixture of 51.6 parts of 2~hydroxy-1-naphthaldehyde, 16,2 parts of o-phenylene-diarnine and 250 parts of dimethyl-formamide are heated for 3 hours at 100C, then cooled. The orange deposit which has precipitated is suction-filtered, washed with dimethylformamide and then suspended in 600 parts of ethanol. The suspension is mixed with a mixture of 24.3 parts of nickel acetate and 2.85 parts of copper acetate, heated for 4 hours to be boil, suction-filtered hot, washed with hot ethanol, then with water and dried. 69.4 Parts (97.0 % of the theory) of a bordo red compound of the formula ~ CH ~ ~ CH ~
are obtained, wherein Me is identical to nickel and copper in the molar ratio of 9:1, which compound permits to prepare ~olor-intense printing inks, and may especially be used in lacquers in an excellent manner, preferably in metal effect lacquers wherein it shows an excellent fastness to solvents, to light and to weather.
If the o-phenylene-diamine is replaced by aliquote amounts o~ 4-chloro-o-phenylene-diamine and the operation is otherwise carried out in the indicated manner, a slightly more yellow pigment is obtained in the same yield, which has comparably good properties.
.
A mixture of 17.2 parts of 2-hydroxy-1-naphthaldehyde, 8.77 . .
:
:
~;!!4751~
parts of nickel acetate and 100 parts of glacial acetic acid is stirred for one hour at room temperature. The whole is mixed ~with a mixture of 4.32 parts of o-phenylenediamine and 1.77 parts of 4.5-dichloro-o-phenylene-diamine and heated for 4 hours ~o the boil. The precipitate formed is suction-filtered, washed with hot ethanol, then with water and dried at 80C. 22.8 Parts (92.8 % of the theor~) of an orange mixed complex of the formula ~Ho 8i Clo.~) (Clo 2; ~0.8) ~ 0~ C~ ~ ~ (Me = ~i:Zn = ~9:1) is obtained, which has good pigment properties and is especially suitable for the preparation of car lacquers having a high fastness to light and to weather.
~ Subsequently heating of the aqueous filter ca~e with 3-times the amount of N-methylpyrrolidone for 4 hours at 80 -90C provides a pigment having a purer shade and an improved dispersability.
If in Example 13 the 2-hydroxy-1-naphthaldehyde is re-placed by corresponding amounts of 6-methoxy-2-hydroxy-1-naphthaldehyde and the operation is carried out in the manner indicated, a somewhat redder pigment having comparable fastness properties but a higher tinctorial strength is obtained.
_ _ _ _ _ .
If instead of the mixture of o-phenylene-diamine and 4,5-dichloro-o-phenylene-diamine of Example 13 n mols of the sub-. stituted o-phenylene-diamines listed in Table 2 and 1-n mol of ,,, ....... . ----:`.
. .: .:
- ~ . : :~
. ~ ,.
4~S8 o-phenylene-diamine are used and reacted in ana].ogous manner with 2 mols of 2-hydroxy-1-naphthaldehyde and with aliquote amounts of the metal acetate mixtures indicated in Table 2, instead of the mixtures of nickel and zinc acetate of Exampl.e 13 r and the operation is carried out according to Example 13, further mixed complex co.mpounds are obtained from compounds of the above general formula Ia with the yields and shades listed in Table 2.
--Tâble-2=
Ex~m~ n [~ln Me Yie1~d ---Shade;
14 0,33 COCH3 Ni:Co 9?, 3 % blui-sh red~.
~ 19:1 - -0~15 COOC2X5 Ni:Cu 94~8 % yel~o.wishL.red ~ 12:1 - .~
16 0~45 ~r Ni Co 99~1 ~red:br~o.wn-.
17 0,075 ~o~ Ni Zn 97,8 %bor.~Q=~e~
18 0,8 ~ Cl 7 2 19 0,30H~C OCH3 Co:Zn 94,0 %~luish~red --~) 10 ~
- 17 - ¦
: .
.
~L~4758 E~-ample-~ n L ] Me Yiel;d ~ Shade~
- n ", , . , " .. . .. . . ~ . ~
0~75 COOCH3 Ni:Cu 98~2 ~ yellowish r~cl - ~ 20:1 ~------C~l 21 0~175 ~H~ 3 Ni:Cu 91~7 ~ r~=o~ran~
~ 3 20:1 A mixture of 6.9 parts of o-nitraniline and 9.1 parts of
Aldehydes of the formula (II) are especially those in which Z is hydrogen, chlorine or bromine, a methoxy, ethoxy or propoxy group, a nitro or cyano group. They may be obtained in known manner by formylation of the corresponding 2-hydroxy-naphthalenes, especially according to the method of Duf~.
Diamines of the formula (III) are especially those in which the benzene nucleus is substituted by at least one halogen atom, for example one or two chlorine or bromine atoms, one or two lower alkyl groups having 1 to 4 carbon atoms, such as methyl, ethyl, propyl or butyl groups, one or two lower alkoxy groups having 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy or butoxy groups, a phenoxy group, which may be substituted by halogen atoms, lower alkyl and/or alkoxy groups, a hydroxy group, a cyano group, a trifluoromethyl, carboxy or lower carboxylic acid alkyl ester group such as a methyl, ethyl, propyl or butyl ester group.
The condensation of the aldehyde~s) with the diamine : : ~ : , .
.. . ..... 1. . ~:.
, :: - ~ - . .
HOE 76/F 0~9 75~
mixture is expediently carried out in water or in an organic solvent at an elevated temperature, preferably betw~en about 60C and the boiling point of the solvent used. There are especially considered as solvents: water, ethanol, glacial acetic acid, dimethylformamide, N-methylpyrrolidone, glycolmono-or -dimethylether, xylene or the mixtures thereof.
The disazomethine mixtures obtained are difficultly soluble in the solvents mentioned and may be easily isolated by filtra-tion. Possible contaminations may be removed by washing out. In order to convert the disazomethine mixtures obtained into the mixed complex compounds of the invention the metal-free com-pounds are treated with compounds or mixtures of compounds which yield two-valent metal, for example with salts of nickel, copper, cobalt, zinc, cadmium or manganese, preferably the formiates or acetates thereof.
The complexation of a disazomethine of the formula (V) Z Z
Q
~H = N ~ = CH ~ (V) OH - OH
wherein Z has the above meaning is preferably effected with a mixture of metal-yielding agents of imperatively up to 5 mol%
of a metal different from nickel, thus with metal-yielding agents which contain metal-yielding reagents of one or several metals Me of the above meaning different from nickel, i.e. con-tain at most 95 mol~ of a nickel-yielding agent.
Metallization is expediently carried out in one of the above-mentioned solvents or in a mixture thereof.
;~
' ' ' ;~ , :
.~ .
..:
.
~IOE 75/F 049 lP~75~
Metallization may also be carried out before or, as al-ready mentioned, simultaneously with the azomethine condensa-tion/ by treating the aldehyde flrst individually with a ~etal-yielding agent in one of the above solvents or in a mix-ture thereof and then condensing with the diamine, or conden sing the aldehyde together with the diamine in the presence of the metal-yielding agents in the solvents mentioned.
The novel mixed complex compounds have proved to be very good coloring agents and represent especial]y good pigments which are suitable, especially after a conditioning usual for pigments, for example for the dyeing of plastic masses (which are masses of plastics or synthetic resins free from solvents or containing solvents or free from softening agents or containing softening agents). furthermore for the pigmentation of paints on an oily or aqueous base as well as of different lacquers, for the dyeing of viscose and cellulose acetate or for the pigmentation of polyethylene, polystyrene, polyvinyl chloride, rubber and syn~
thetic leather, but which may be preferably used for the pre-paration of metal effect lacquers.
They may also be used in printing inks for graphic industry, for the coloring of the paper mass, for coating textiles or for the pigment print. The colourings obtained have an excellent fastness to migration overwarnishing hleeding to light, to weather and ~o solvents, they have an excellent fastness to heat and are characterized by a high tinctorial strength, a good transparency, a good dispersability and often surprisingly pure shades.
In contradistinction to the next comparable known indi-vidual compounds of the above formula I wherein R1= R2 = R3 =
:. ~ . , ~ ., ., ~ :
:-. i: :. .
hydrogen or one of these substituents is a nitro, carboxylic acid amide or sulfonic acid amide group (cf. German Offenlegungs-schrift No 2,308,594, German Offenlegungsschrift No. 2,007,844 and French Patent Specification No. 1,~16,293), the mixed complex compounds of the instant invention are characterized by a better fastness to migration and to solvents, for example an improved fastness to bleeding and overvarnishing, by an elevated trans-parency and a better dispersability as well as especially a higher tinctorial strength and a pure shade.
Especially with regard to the next comparable pigment corres-ponding to the above formula I with R1 = R2 = R3 = hydrogen, Z
identical to hydrogen and Me identical to nickel (cf. German Offenlegungsschrift No. 2,308,594), a considerably improved fastness to overvarnishing, a considerably elevated tinctorial strength and a purer, more yellow shade of the mixed complex pigments has surprisingly been found, which could not be forseen with regard to the formation of the mixed complex.
For a crystal structure has been found for the mixed complex compounds of the present invention by X-ray difraction accor-ding to Debye - Scherrer which is surprisingly different from the known individual pigments of the formula I.
The following Examples serve to illustrate the invention and especially describe preferred mixed complex compounds and variants of the preparation processes mentioned. Parts and percentages are by weight.
E X ~ M P L E
A mixture of 51,6 parts of 2-hydroxy-1-naphthaldehyde, 48 parts of sodium acetate and 900 parts of water is ground for 15 minutes in a dispersing device ("dispergator") at room .
. :
.~ .
. .
7~;8 temperature. Then a solution of 46 parts of nickel sulfate in 150 parts of water is added, and the whole is dispersed for half an hour, the temperature increasing to 30 - 40C.
The finely divided suspension of the 2-hydroxy-1-napht-haldehyde nickel complex obtained is introduced into a three neck flask (reflux cooler, stirrer, thermometer), and after addition of a mixture of 4,6 parts of 4-methyl-o-phenylene-diamine and 12,2 parts of o-phenylene-diamine, the whole is heated within 2 hours steadily to 95C, in the course of which the pH value decreases from 7.8 to about 4.
The whole is then mixed with a solution of 48 parts of sodium acetate in 150 parts of water and stirring is continued for 150 minutes at boiling temperature; the mix~ure is filtered hot, washed with 4000 parts of water and dried. 70.7 Parts (98.2 ~ of the theory) of a mixed complex compound correspondin~
to the formula --- ((CH3)0,25; Ho.75) -~ CH = ~ N = OH ~ ~
are obtained, which dyes plastics in yellowish red shades and may be used in an excellent manner for the preparation of lacquers fast to light and to weather, especially metal effect lacquers where it shows a high tinctorial strength and an ex-cellent fastness to overvarnishing.
If the humid filter cake of the nickel comples is stirred with 5-times the amount of dimethylformamide for 5 hours at 100C, which i5 then suction-filtered, washed with dimethyl-~ .
. ~ :
- . :-,. : :
..
.~ :
~OE 76/E 049 7~8 formamide and water and subsequent dried , an improved pigment is obtained which has a better covering power, a better dis-persing capacity and a purer shade with otherwise comparable properties.
If the 4-methyl-o-phenylene-diamine is replaced by 3-methyl-o-phenylene-diamine, a pigment having comparable properties and fastness properties and a more bluish shade and a higher tinc-torial strength is obtained with the same yield.
E X A M P L E 2 to 11 If instead of the mixture of o-phenylene-diamine and 4-methyl~o-phenylene-diamine per 2 mols of hydroxynaphthaldehyde n mols of an other substituted o-phenylene-diamine and 1-n rnols of o-phenylene-diamine are added, and the operation is carried out as indicated in Example 1, there are also obtained mixed complex compounds of compounds of the formula Ia with the yields and shades listed in Table 1.
Table,1 CH = N ,~ = CH
O -~ Ni O
.
a= substituted or unsubstituted benzene nucleus n= portion of substituted benzene nucleus a, cal-culated on 1.00 1-n = portion of unsubstituted benzene nucleus a , ' ' - HOE 76/~' 049 4t75~
~cample L ~ ~ n n yield~ shade_ , Cl 0,15 98,2 % sc~rl-~
~ . ' CN 0~40 ga, 5 % i--r~d~
- ~$ ' ' 3CH3 ~~ 94,8 % red~n~
~, , .
. . .
Cl Cl 0,10 99~0 ~ yello~-b,r~wn ,' , ~ ' ' ' '.
6 COOH 0~10 96,8 % bordeau red ' .
7 ~ CH3 0,60 90~3 % blulsh red :
~ 8 OC~3 ' 0,20 95~2 yO bordeau-~ed " . ~ .
9 COOCH~ 0,20 97~2 Yo red-~' ,, , <~ .
: 10 OH 0~05 92~7 % bluish red - ._ 11 Cl ~CH30~15 ~8~0 % orange-red~-' ~$ ' .. ., _. . _ . . _ _ _ __,_ . . ... . . .
~47S8 _ A mixture of 51.6 parts of 2~hydroxy-1-naphthaldehyde, 16,2 parts of o-phenylene-diarnine and 250 parts of dimethyl-formamide are heated for 3 hours at 100C, then cooled. The orange deposit which has precipitated is suction-filtered, washed with dimethylformamide and then suspended in 600 parts of ethanol. The suspension is mixed with a mixture of 24.3 parts of nickel acetate and 2.85 parts of copper acetate, heated for 4 hours to be boil, suction-filtered hot, washed with hot ethanol, then with water and dried. 69.4 Parts (97.0 % of the theory) of a bordo red compound of the formula ~ CH ~ ~ CH ~
are obtained, wherein Me is identical to nickel and copper in the molar ratio of 9:1, which compound permits to prepare ~olor-intense printing inks, and may especially be used in lacquers in an excellent manner, preferably in metal effect lacquers wherein it shows an excellent fastness to solvents, to light and to weather.
If the o-phenylene-diamine is replaced by aliquote amounts o~ 4-chloro-o-phenylene-diamine and the operation is otherwise carried out in the indicated manner, a slightly more yellow pigment is obtained in the same yield, which has comparably good properties.
.
A mixture of 17.2 parts of 2-hydroxy-1-naphthaldehyde, 8.77 . .
:
:
~;!!4751~
parts of nickel acetate and 100 parts of glacial acetic acid is stirred for one hour at room temperature. The whole is mixed ~with a mixture of 4.32 parts of o-phenylenediamine and 1.77 parts of 4.5-dichloro-o-phenylene-diamine and heated for 4 hours ~o the boil. The precipitate formed is suction-filtered, washed with hot ethanol, then with water and dried at 80C. 22.8 Parts (92.8 % of the theor~) of an orange mixed complex of the formula ~Ho 8i Clo.~) (Clo 2; ~0.8) ~ 0~ C~ ~ ~ (Me = ~i:Zn = ~9:1) is obtained, which has good pigment properties and is especially suitable for the preparation of car lacquers having a high fastness to light and to weather.
~ Subsequently heating of the aqueous filter ca~e with 3-times the amount of N-methylpyrrolidone for 4 hours at 80 -90C provides a pigment having a purer shade and an improved dispersability.
If in Example 13 the 2-hydroxy-1-naphthaldehyde is re-placed by corresponding amounts of 6-methoxy-2-hydroxy-1-naphthaldehyde and the operation is carried out in the manner indicated, a somewhat redder pigment having comparable fastness properties but a higher tinctorial strength is obtained.
_ _ _ _ _ .
If instead of the mixture of o-phenylene-diamine and 4,5-dichloro-o-phenylene-diamine of Example 13 n mols of the sub-. stituted o-phenylene-diamines listed in Table 2 and 1-n mol of ,,, ....... . ----:`.
. .: .:
- ~ . : :~
. ~ ,.
4~S8 o-phenylene-diamine are used and reacted in ana].ogous manner with 2 mols of 2-hydroxy-1-naphthaldehyde and with aliquote amounts of the metal acetate mixtures indicated in Table 2, instead of the mixtures of nickel and zinc acetate of Exampl.e 13 r and the operation is carried out according to Example 13, further mixed complex co.mpounds are obtained from compounds of the above general formula Ia with the yields and shades listed in Table 2.
--Tâble-2=
Ex~m~ n [~ln Me Yie1~d ---Shade;
14 0,33 COCH3 Ni:Co 9?, 3 % blui-sh red~.
~ 19:1 - -0~15 COOC2X5 Ni:Cu 94~8 % yel~o.wishL.red ~ 12:1 - .~
16 0~45 ~r Ni Co 99~1 ~red:br~o.wn-.
17 0,075 ~o~ Ni Zn 97,8 %bor.~Q=~e~
18 0,8 ~ Cl 7 2 19 0,30H~C OCH3 Co:Zn 94,0 %~luish~red --~) 10 ~
- 17 - ¦
: .
.
~L~4758 E~-ample-~ n L ] Me Yiel;d ~ Shade~
- n ", , . , " .. . .. . . ~ . ~
0~75 COOCH3 Ni:Cu 98~2 ~ yellowish r~cl - ~ 20:1 ~------C~l 21 0~175 ~H~ 3 Ni:Cu 91~7 ~ r~=o~ran~
~ 3 20:1 A mixture of 6.9 parts of o-nitraniline and 9.1 parts of
3-nitro-4- amino-benzoic acid are hydrogenated in 300 parts of isopropanol under the catalysis of Raney-Nickel. After taking up the theoretical amount of hydrogen, pressure is released, the catalyst is filtered off hot and is washed with 100 parts of warm glacial acetic acid. The combined filtered products are added to a solution of 34.4 parts of 2-hydroxy-1-napht-haldehyde in 100 parts of glacial acetic -cid and heated for 3 hours to the boiling point. Then it is suction-filtered and washed with hot isopropanol.
The metallization with nickel acetate according to Example 12 provides 48.9 parts (98.1 % of the theory) of a red brown pigment which corresponds, as to their technical properties, to the pigment described in Example 6.
A mixture of 51.6 parts of 2-hydroxy 1-naphthaldehyde, 46 parts of nickel sulfate and 1000 parts of water are ground in a disk attrition mill on circulating by pumping, and during ~. . ~
::. .
: , . .
;.: - ...... .
: ,. .
t : ' . .
' " ' ~Q~
this process a temperature of from 20 to 30C is adjusted with the aid of a heat exchanger. During the whole reaction the apparatus is co~ered by a layer of nitrogen. A mixture of 11.34 parts of o-phenylene-diamine and 6.21 parts of 4-methoxy-o-phenylene-diamine is added, and the whole is heated in 2 hours to 60C, in further two hours to 90C. The bluish red deposit formed is suction-filtered hot, washed neutral with hot water and dried.
69.1 Parts (94.8 ~ of the theory) of a mixed complex of the formula ((OCH3)o.3; ^7 O _ "Ni - O
are obtained which permits the preparation of especially color-intense lacquers, especially metal effect lacquers having an excellent fastness to light and to weather.
.
If in Example 23 the mixture of the o-phenylene-diamines is replaced by n mols of the substituted phenylene diamines indi-cated in Table 3 and 1-n mol of o-phenylene-diamine and the 2-molar amounts of 2-hydroxynaphthaldehyde, and the operation is carried out in analogous manner ~s indicated in Example 23 or in one of the other preceeding Examples mixed complexes of compounds of the above formula Ia, as indicated in Table 3, with the yields and shades listed in Table 3 are also obtained.
. ~ ~ .. . ~ - , " :' ' .
Table ~ 4758 HOE 76/F 049 ~~ ] n Yield~ shade 24 Cl O, 4099 ,1 % scarl-e~~3~:
~) ' .
C00C4H9 0,05 97~8 % red .--- ~ , - .
26 C2H5 0~20 .- 97~3 % yello~sh red . -27 . ~ Cl 0~2098~3 % bl~is~ ~ed 28 ~ C0 ~ 0,1599~3 % bordo--~ed 29 0 ~ CH3 0,0598~7 % ~ord ~ed 0~10 9~8 ~ ~_s-carle~-:
`'- ~$' ''' 31 ~3C C~3 0, 5594 ~ 9 % red orange ~- - .
32 H3C 0,1595,1 % . red -~ 33 ~ 0,2598,9 % ~ sca-rlet:.
..
~The.mixed comprex:compounds of-Exahlple ~-,-2, 5,--1-2~-and 33 are ~-~' espe~ally preferred.
. - 20 -, ...... .
:
:.,,; . .:
The metallization with nickel acetate according to Example 12 provides 48.9 parts (98.1 % of the theory) of a red brown pigment which corresponds, as to their technical properties, to the pigment described in Example 6.
A mixture of 51.6 parts of 2-hydroxy 1-naphthaldehyde, 46 parts of nickel sulfate and 1000 parts of water are ground in a disk attrition mill on circulating by pumping, and during ~. . ~
::. .
: , . .
;.: - ...... .
: ,. .
t : ' . .
' " ' ~Q~
this process a temperature of from 20 to 30C is adjusted with the aid of a heat exchanger. During the whole reaction the apparatus is co~ered by a layer of nitrogen. A mixture of 11.34 parts of o-phenylene-diamine and 6.21 parts of 4-methoxy-o-phenylene-diamine is added, and the whole is heated in 2 hours to 60C, in further two hours to 90C. The bluish red deposit formed is suction-filtered hot, washed neutral with hot water and dried.
69.1 Parts (94.8 ~ of the theory) of a mixed complex of the formula ((OCH3)o.3; ^7 O _ "Ni - O
are obtained which permits the preparation of especially color-intense lacquers, especially metal effect lacquers having an excellent fastness to light and to weather.
.
If in Example 23 the mixture of the o-phenylene-diamines is replaced by n mols of the substituted phenylene diamines indi-cated in Table 3 and 1-n mol of o-phenylene-diamine and the 2-molar amounts of 2-hydroxynaphthaldehyde, and the operation is carried out in analogous manner ~s indicated in Example 23 or in one of the other preceeding Examples mixed complexes of compounds of the above formula Ia, as indicated in Table 3, with the yields and shades listed in Table 3 are also obtained.
. ~ ~ .. . ~ - , " :' ' .
Table ~ 4758 HOE 76/F 049 ~~ ] n Yield~ shade 24 Cl O, 4099 ,1 % scarl-e~~3~:
~) ' .
C00C4H9 0,05 97~8 % red .--- ~ , - .
26 C2H5 0~20 .- 97~3 % yello~sh red . -27 . ~ Cl 0~2098~3 % bl~is~ ~ed 28 ~ C0 ~ 0,1599~3 % bordo--~ed 29 0 ~ CH3 0,0598~7 % ~ord ~ed 0~10 9~8 ~ ~_s-carle~-:
`'- ~$' ''' 31 ~3C C~3 0, 5594 ~ 9 % red orange ~- - .
32 H3C 0,1595,1 % . red -~ 33 ~ 0,2598,9 % ~ sca-rlet:.
..
~The.mixed comprex:compounds of-Exahlple ~-,-2, 5,--1-2~-and 33 are ~-~' espe~ally preferred.
. - 20 -, ...... .
:
:.,,; . .:
Claims (20)
1. A mixed metal-complex compound consisting of at least two compounds of the general formula (I) (I) wherein each Z, which may be identical or different from one another, is hydrogen, halogen, lower alkoxy, nitro or cyano, Me stands for a bivalent metal atom, R1 is hydrogen, halogen, lower alkoxy, lower alkyl, phenoxy unsubstituted or substituted by substituents selected from the group halogen, lower alkyl and lower alkoxy, or is hydroxy, cyano, trifluoromethyl, carboxy, lower carboxylic acid alkyl ester, lower alkanoyl,benzoyl, benzoyl substituted by substitutents selected from the group halogen, lower alkyl and alkoxy, R2 is hydrogen, halogen, lower alkoxy, lower alkyl, phenoxy, phenoxy substituted by substituents selected from the group halogen, lower alkyl and lower alkoxy, or is hydroxy, cyano, trifluoromethyl, carboxy, lower carboxylic acid alkyl ester, lower alkanoyl, benzoyl:, benzoyl substituted by substituents selected from the group halogen, lower alkyl and lower alkoxy, and R3 is hydrogen, halogen, lower alkoxy or lower alkyl.
2. A mixed complex compound as claimed in claim 1, consisting of one or several metal complex compounds of the formula (I) wherein R1 = R2 = R3 = hydrogen, and of one or several mixed metal complex compounds, wherein at least one substituent of the series of R1, R2 and R3 does not represent hydrogen and Me and Z are defined as in claim 1.
3. A mixed complex compound as claimed in claim 1, consisting or one or several metal complex compounds of the formula (I) in which R1 = R2 = R3 = hydrogen, and of one or several mixed metal-complex compounds, wherein R1 is hydrogen, R2 is chlorine or bromine or alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, phenoxy unsub-stituted or substituted by substituents selected from the group halogen, such as chlorine or bromine, lower alkyl and lower alkoxy, or is hydroxy, cyano, trifluoromethyl, carboxy or carboxylic acid alkyl ester having 1 to 4 carbon atoms in the alkyl moiety and R3 is hydrogen, chlorine, bromine, alkyl having 1 to 4 carbon atoms or alkoxy having 1 to 4 carbon atoms, and Z, identical or different, each is hydrogen, chlorine, bromine, methoxy, ethoxy, propoxy, nitro or cyano, and Me is defined as in claim 1.
4. A mixed complex compound as claimed in claim 1, containing 10 to 50 mol% of one or several compounds of the formula (I) in which at least one of the substituents R1, R2 and R3 is not identical to hydrogen, and Me and Z are defined as in claim 1.
5. A mixed comp]ex compound as claimed in claim 1, consisting of compounds of the formula (I), wherein R1 = R2 = R3 =
hydrogen and Me and Z have the meanings indicated in claim 1, with a portion of 60 to 95 mol% of one or several nickel complex compounds.
hydrogen and Me and Z have the meanings indicated in claim 1, with a portion of 60 to 95 mol% of one or several nickel complex compounds.
6. A mixed complex compound as claimed in claim 5, in which Z is hydrogen.
7. A mixed complex compound as claimed in claim 1, consisting of mixed complex components of the formula wherein X is hydrogen, halogen or alkoxy having 1 to 4 carbon atoms and Me is nickel or copper, with a portion of 60 to 95 mol% of one or two or three, mixed complex components wherein X is hydrogen, and a portion of 100 to 85 mol% of one or two or three mixed complex components wherein Me is nickel.
8. A mixed complex compound as claimed in claim 1, consisting of about 25 mol% of the compound of the formula and about 75 mol% of the compound of the formula
9. A mixed complex compound as claimed in claim 1, consisting of about 15 mol% of the compound of the formula and about 85 mol% of the compound of the formula
10. A mixed complex compound as claimed in claim 1, consisting of about 10 mol% of the compound of the formula and about 90 mol% of the compound of the formula
11. A mixed cornplex compound as claimed in claim 1, consisting of about 90 mol% of the compound of the formula and about 10 mol% of the compound of the formula
12. A mixed complex compound as claimed in claim 1, consisting of about 25 mol% of the compound of the formula and about 75 mol% of the compound of the formula
13. A process for the preparation of a mixed metal complex compound of claim 1, which comprises condensing 2 mols of an aldehyde of the formula (II) (II) wherein Z is defined as in claim 1, or on the whole 2 mols of two or several aldehydes of the formula (II) with 1 mol of an o-phenylene-diamine of the formula (III) (III) wherein Rl, R2, R3 is defined as in claim 1, or with, on the whole, 1 mol of two or several diamines of the formula (III), in mixture with one another, and treating the dis-azomethine compound obtained - if starting from uniform reactants (II) and (III) in each case, - during condensa-tion or subsequently with metallizing agents of two or several metals Me having the meaning given in claim 1, or treating the disazo-methine mixtures ohtained, - if at least one of the reactants (II) and (III) consists of at least two different compounds, - during condensation or subsequently with one or several metallizing agents of one or two or several different metals Me having the meaning given in claim 1.
14. A process for the preparation of the mixed complex compounds defined in claim 1, which comprises reducing one or several o-nitranilines of the formula (IV) (IV) wherein Rl, R2 and R3 is defined as in claim 1, according to usual methods and reacting it (them) obtained without intermediate isolation with one or several hydroxynaphth-aldehyde compounds of the formula (II) as defined in claim 13 in the molar ratio of 1:2 and treating (metallizing) the disazomethine compound obtained - if starting from uniform reactants (II) and (III) as defined in claim 13 in each case - during condensation or subsequently with a metallizing agent of two or several different metals Me having the meaning as in claim 1, or treating (metallizing) the disazomethine mixtures obtained if at least one of the reactants (II) and (III) consists of two different compounds during condensation or subsequently with one or several metallizing agents of one or two several different metals Me having the meaning as in claim 1.
15. A process for the preparation of the mixed complex compounds defined in claim 1, wherein 2 mols of one or several aldehydes of the formula (II) as defined in claim 13 are metallized with one or several agents yielding metals Me having the meaning in claim 1, and subsequently condensing with, on the whole, 1 mol of one or several diamines of the formula (III) as defined in claim 13.
16. A material selected from printing inks, printing pastes, high-molecular plastic masses, lacquers, paints and spinning masses, pigmented with a mixed metal-complex compound according to claim 1.
17. A material as claimed in claim 16 which is a printing ink.
18. A material as claimed in claim 16 which is a metal effect lacquer.
19. In a process for coloring a printing paste, a high-molecular plastic mass, a lacquer, a paint, a spinning mass or a printing ink wherein a colorant is incorporated into said material, the improvement consisting of using coloring agent a mixed metal-complex compound of claim 1.
20. In a process for coloring a metal effect lacquer wherein a colorant is incorporated into said material, the improvement consisting of using coloring agent a mixed metal-complex compound of claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19762610308 DE2610308A1 (en) | 1976-03-12 | 1976-03-12 | WATER-INSOLUBLE DISAZOMETHINE MIXED COMPLEXES, PROCESS FOR THEIR MANUFACTURING AND THEIR USE AS A COLORANT |
| DEP2610308.2 | 1976-03-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1104758A true CA1104758A (en) | 1981-07-14 |
Family
ID=5972218
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA273,737A Expired CA1104758A (en) | 1976-03-12 | 1977-03-11 | Water-insoluble disazomethine mixed metal-complex compounds, process for preparing them and their use as colorants |
Country Status (11)
| Country | Link |
|---|---|
| JP (1) | JPS52111924A (en) |
| AU (1) | AU2310577A (en) |
| BE (1) | BE852430A (en) |
| BR (1) | BR7701508A (en) |
| CA (1) | CA1104758A (en) |
| DE (1) | DE2610308A1 (en) |
| DK (1) | DK106477A (en) |
| FR (1) | FR2343784A1 (en) |
| GB (1) | GB1553441A (en) |
| IT (1) | IT1085518B (en) |
| NL (1) | NL7702423A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3621215A1 (en) * | 1986-06-25 | 1988-01-07 | Bayer Ag | FLUORINE O-PHENYLENE DIAMINE AND O-AMINOPHENOLE |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1416293A (en) * | 1963-12-04 | 1965-10-29 | Basf Ag | Pigment dyes and process for their production |
| DE2305071C2 (en) * | 1973-02-02 | 1975-04-17 | Farbwerke Hoechst Ag, Vormals Meister Lucius & Bruening, 6000 Frankfurt | Water-insoluble disazomethine dyes, process for their preparation and their use |
| DE2515523C3 (en) * | 1975-04-09 | 1980-05-29 | Hoechst Ag, 6000 Frankfurt | Water-insoluble disazomethine compounds, process for their preparation and their use as colorants |
-
1976
- 1976-03-12 DE DE19762610308 patent/DE2610308A1/en not_active Withdrawn
-
1977
- 1977-03-07 NL NL7702423A patent/NL7702423A/en not_active Application Discontinuation
- 1977-03-10 IT IT2115277A patent/IT1085518B/en active
- 1977-03-10 AU AU23105/77A patent/AU2310577A/en not_active Expired
- 1977-03-11 DK DK106477A patent/DK106477A/en unknown
- 1977-03-11 BR BR7701508A patent/BR7701508A/en unknown
- 1977-03-11 CA CA273,737A patent/CA1104758A/en not_active Expired
- 1977-03-11 JP JP2613677A patent/JPS52111924A/en active Pending
- 1977-03-14 BE BE175761A patent/BE852430A/en unknown
- 1977-03-14 FR FR7707476A patent/FR2343784A1/en active Pending
- 1977-03-14 GB GB1070777A patent/GB1553441A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| NL7702423A (en) | 1977-09-14 |
| AU2310577A (en) | 1978-09-14 |
| IT1085518B (en) | 1985-05-28 |
| BE852430A (en) | 1977-09-14 |
| GB1553441A (en) | 1979-09-26 |
| FR2343784A1 (en) | 1977-10-07 |
| DE2610308A1 (en) | 1977-09-15 |
| BR7701508A (en) | 1977-11-08 |
| DK106477A (en) | 1977-09-13 |
| JPS52111924A (en) | 1977-09-20 |
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| Date | Code | Title | Description |
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| MKEX | Expiry |