CA1045119A - Disazo pigments and process for their manufacture - Google Patents

Abstract

Abstract of the Disclosure Disazo pigments of the formula wherein A denotes a phenylene or naphthylene radical, R
denotes an aryl, alkyl or alkenyl group optionally substi-tuted by halogen ato?s, by hydroxyl, alkoxy or alkylmercapto groups containing 1-6 C atoms, by alkoxycarbonyl groups con-taining 2-6 C atoms or cyano, aryl, aryloxy, arylmercapto or heterocyclic radicals, or denotes a heterocyclic radical, and the X and Y denote H atoms or substituents which do not confer solubility in water are useful for coloring plastics lacquers and printing inks in yellow to orange shade of good fastness properties.

Description

It has been found that new, valuable disazo pigments of the formula X X

( I ) II ~ NHCOR ~NHCOR
N N ::
CH3COCHCONH . A - NHOClHCOCH

~ wherein A denotes a phenylene or naphthylene radical, R
denotes an aryl, alkyl or alkenyl group optionally substi- .
tuted by halogen atoms, by hydroxyl, alkoxy or alkylmercapto groups containing 1 - 6 C atoms, by alkoxycarbonyl groups . ;
containing 2 - 6 C atoms or cyano, aryl, aryloxy, arylmer- .:
capto or heterocyclic radicals, or denotes a heterocyclic .~ .
radical and the X and Y denote H atoms or substituents which do not confer solubility in wa-ter9 are obtained when a diazo or diazoamino compound of an am m e of the formula ' X

H2N ~ (II) ; ~;.
NHCOR
. . .
: .
.. .
:~ ~ is:coupled ~ith a bis-acetoacetyl-arylenediamine of the :
formula .
~ CH3COCH2CONH-A-NHOCCH2COCH3 in the molar ratio of 2~
Pigments of particular interest are those of the :,:

2 - ~

1~)45~9L9 formula (I), wherein the NHCOR group is in the para-position to the azo group, and/or wherein R denotes an alkyl group, containing 1-6 C atoms, or a phenyl group optionally substi-tuted by halogen atoms, hydro~l groups or alkyl or alkoxy groups containing 1-4 C atoms and wherein X denotes a H atom, an alkyl or alkoxy group containing 1-4 C atoms, a nitro or cyano group or an alkoxycarbonyl group, containing 2-5 C
atoms, and Y denotes a H or halogen atom or an alkyl or alkoxy group containing 1-4 C atoms.
A in the formula (I) preferably represents a radi-cal o~ the formula . ~ `

. .

wherein Xl and Yl denote H or halogen atoms, alkyl or alkoxy : -groups containing 1-4 C atoms, phenoxy, trifluoromethyl, nitro or~cyano groups, or alkoxycarbonyl or alkanoylamino groups containing 2-5 C atoms, and especially a radical of the formula X.l, -- f ::
~ , Y:2 ' ..

: wherein X2 and Y2 denote H or chlorine atoms or alkyl or ., ; 3 ~
..

1a~45~1 ~9 alkoxy groups containing 1-4 C atoms.
: Diazo components used are preferably those of the formula (II), wherein R denotes an alkyl group containing 1 - 6 C atoms, or a phenyl group optionally substituted by halogen atoms, hydroxyl groups, alkyl or alkoxy groups con-taining 1-4 C atoms or alkoxycarbonyl groups containing 1-4 :
C atoms, and wherein X denote~ a H atom, an alkyl or alkoxy group containing 1-4 C atoms, a nitro or cyano group or an ~
alkoxycarbonyl group containing 2-5 C atoms and Y denotes a H or halogen atom or an alkyl or alkoxy group containing 1 - 4 C atoms.
The following may be mentioned as examples o~ diazo components: l-amino-3-acetylamino-benzene, 1-amino-2- ~
chloro-5-acetylamino-benzene, 1-amino-2-methyl-5-acetylamino- ::.
benzene, 1 amino-2-methoxy-5-acetylamino-benzene, l-amino-4-methyl-5-acetylamino-benzene, 1-amino-4-methoxy-5-acetylamino-benzene, l-amino-2-ethoxy-5-acetylamino-benzene, 1-amino-2- .
methoxy-5-propionylamino-benzene, 1-amino-2-chloro-5-propionylamino-benzene, l-amino-2~methyl-5-butyrylamino- :
benzene, l-amino-4-acetylamino-benzene, 1-amino-2-chloro-~
acetylamino-benzene, l-amino-2-methyl-4-acetylamino-benzene, .. ;
l-amino-2-methoxy-4-acetylamino-benzene, 1-amino-2-nitro-4 acetylamino-benzene, l-amino-3-chloro-4-acetylamino benzene~
l-amino-3-methoxy-4-acetylamino-benzene, 1-amino-3-cyano-4- c acetylamino-benzene, 1-amino-3-methyl-4-ace-tylamino-benzene, ::~
1-amino-2-chloro-4-propionylamino-benzene, 1-amino-2-methyl- ~
4-butyrylamino-benzene, 1-amino-2-methoxy-3-acetylamino- .
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-. , 104~
benzene, l-amino-2-chloro-3-acetylamino-benzene, l-amino-2,5-dichloro-4-acetylamino-benzene, 1-amino-2,5-dimethyl-4-acetylamino-benzene, 1-amino-2,5-dimethoxy-4-acetylamino- -benzene, l-amino-2,5-diethoxy--4-acetylamino-benzene, l-amino-

3,5-dichloro-4-acetylamino-benzene, 1-amino-2-me-thyl-5-chloro-4-acetylamino-benzene, 1-amino-2-chloro-5-methyl-4-acetylamino-benzene, l-amino-2-methoxy-5-chloro-4-acetylamino-benzene, l-amino-2-methoxy-5-methyl-4-acetylamino-benzene, l-amino-2-methoxy-5-nitro-4-acetylamino-benzene, 1-amino-2-methoxy-5-chloro-4-propionylamino-benzene, 1-amino-2-chloro-

4-methyl-5-acetylamino-benzene, 1-amino-2-acetylamino-benzene, l-amino-2-propionylamino-benzene, 1-amino-5-methyl-2-acetylamino-benzene, 1-amino-5-methoxy-2-acetylamino-benzene~
l-amino-5-trifluoromethyl-2-acetylamino-benzene, 1-amino-5-chloro-2-acetylamino-benzene, 1-amino-4-chloro-2-acetylamino-benzene, l-amino-4-methyl-2-acetylamino-benzene, l-amino-~ .
methoxy-2-acetylamino-benzene, 1-amino-3-chloro-2-acetylamino-benzene, l-amino-4,5-dichloro-2-acetylamino-benzene, 1-amino-2-chloro-5-methoxy-4-acetylamino-benzene, 1-amino-4- : .
chloro-5-methoxy-2-acetylamino-benzene, 1-amino~2,5-diacetylamino-benzene, l-amino-2-methoxy-5-benzoylaminobenzene, l-amino-2-methoxy-5-(o-chlorobenzoylamino)-benzene, l-amino-2-methoxy-5-(p-chlorobenzoylamino)-benzene, 1-amino-2-- -methoxy-5-(2',4'-dichlorobenzoylamino)-benzene, 1-amino-2-methoxy-5-(2'-thienylamino)-benzene, 1-amino-2-methoxy-5-(2'-~uroylamino)-benzene, 1-amino-2-methoxy-4~benzoylamino-benzene, l-amino-2-metho ~-4-(o-chlorobenzoylamino)-benzene, :
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l-amino-2-methoxy-4-(p-chlorobenzoylamino)-benzene, l-amino-2-methoxy-4-(2',4'-dichlorobenzoylamino)-benzene, l-amino-2-methoxy-4-(o-methylbenzoylamino)-benzene, 1-amino-2-methoxy-4-(p-methylbenzoylamino)-benzene, 1-amino-2-methoxy-4-(o-methoxybenzoylamino)-benzene, 1-amino-2-methoxy-5-(o-methylbe~zoylamino)-benzene, l-amino-2-methoxy-5-(p-methylbenzoylamino)-benzene, l-amino-2-methoxy-5-(o-methoxybenzoylamino)-benzene, l-amino-2-methoxy-5-(p-methoxybenzoylamino)-benzene, l-amino-2-methoxy-3-benzoylaminobenzene, l-amino-2-me-thoxy-6-benzoylaminobenzene, l-amino-2,5-dimethoxy-4-benzoylaminobenzene, 3-amino-4- -methoxy-carbanilic acid benzyl ester, 3-amino-4-methoxy- -carbanilide, l-amino-2,5-dimethoxy-4-(o-chlorobenzoylamino)-benzene, l-amino-2,5-dimethoxy-4-(p-chlorobenzoylamino)-benzene, l-amino-2,5-dimethoxy-4-(2',4'-dichlorobenzoylamino)-benzene, l-amino-2,5-dimethoxy-4-(o-methylbenzoylamino)- :
benzene~ l-amino-2,5-dimethoxy-4-(p-methylbenzoylamino)-benzene, l-amino-2,5-dimethoxy-3-benzoylaminobenzene, 1-amino-2-methoxy-5-methyl-4-benzoylaminobenzene, 1-amino-2-methoxy-5-methyl-4-(o-chlorobenzoylamino)-benzene, l-amino-2-me-thoxy-5-methyl-4-(p-chlorobenzoylamino)-benzene, l-amino-~ 2-methoxy-5-methyl-4-(2',4/-dichlorobenzoylamino) benzene, l-~mino-2-methoxy-5-methyl-4-(o-methylbenzoylamino)-benzene, ;
l-amino-2-methoxy-5-methyl-4-(p-methylbenzoylamino)-benzene, ;
l-amino-2~methoxy-5-methyl-4-(o-meth~xybenzoylamino)-benzene, l-amino-2-methoxy-5-methyl-4-(2'-thienylamino)-benzene, ~:
l-amino-2-methoxy-5-methyl-4-(2'-furoylamino)-benzene, i ~

~: , ~ ~45~

l-amino-2-methoxy~5-chloro-4-benzoylaminobenzene, l-amino-2-methoxy-5-chloro-4- ( o-chlorobenzoylamino )-benzene, l-amino-2-methoxy-5-chloro-~ (p-chlorobenzoylamino ) -benzene, l-amino-2-methoxy-5-chloro-4- ( 2 ', 4 ' -dichlorobenzoylamino )-benzene, l-amino-2-methoxy-5-chloro-4- ( o-methylbenzoylamino ) -benzene, l-amino-2-methoxy-5-chloro-4- (p-methylbenzoylamino )-benzene, l-amino-2-methoxy-5-chloro-1~ ( o-methoxybenzoylamino )-benzene, l-amino-2-methoxy-5-chloro-~ ( 2 ' -thienylamino ~-benzene, l-amino-2-methoxy-5-chloro 4- ( 2 ' -.~uroylamino ) -benzene, 1-amino-2-methoxy-5-nitro-4-benzoylaminobenzene, 1-amino-2-methoxy-5-nitro-4- ( o-chlorobenzoylamino )-benzene, l~amino-2- : .
methoxy-4-phenacetylaminobenzene, 1-amino-2-methoxy-5-phen- ; .
acetylaminobenzene ~ l-amino-2-methoxy-3-phenacetylamino- -benzene, l-amino-2, 5-dimethoxy-4-phenacetylaminobenzene, 1- ~: :
amino-2-methoxy-5-methyl-4-phenacetylaminobenzene, 1 amino-2-methoxy-5-chloro-4-phenacetylaminobenzene, 1-amino-2-methoxy-5-naphthylacetylaminobenzene, 1-amino-2-methoxy-5-phenoxy~
acetylaminobenzene, l-amino-2-methoxy-5- (p-chlorophenoxy-acetylamino)-benzene, l-amino-2-methoxy-5-phenylthioacetyl-aminobenzene, l-amino-2-methoxy-4-phenylthioacetylaminobenzene, l-amino-2, 5~dimethoxy-4-phenylthloacetylaminobenzene, 1- ; . .
amino-2-methoxy-5-methyl-4-phenylthioacetylaminobenzene, 1-amino-2-methoxy-5-chloro-4-phenylthioacetylaminobenzene, 1- :
amino-2,5-diethoxy-4-(2' ,4'-dichlorophenylthioacetylamino)-benzene, l-amino-2-ethoxy-5-benzoylaiminobenzene, 1-amino-2-ethoxy-5- ( o-chlorobenzoylamino ) -benzene, 1-aimino-2-ethoxy- .

7_ .:
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5-(p-chlorobenzoylamino)-benzene, 1-amino-2-ethoxy-5-(2',4?_ dichlorobenzoylamino)-benzene, l-amino-2-ethoxy-4-(o-chloro-benzoylamino)-benzene9 1-amino-2-ethoxy-4-(p-chlorobenzoyl- -amino)-benzene, l-amino-2-ethoxy-4-(2',4'-dichlorobenzoyl-amino) benzene, l-amino-2-ethoxy-5-(o-methylbenzoylamino)-benzene, l-amino-2-ethoxy-5-(p-methylbenzoylamino)-benzene, l-amino-2-ethoxy-4-(o-methylbenzoylamino)-benzene, l-amino-2-ethoxy-4-~p-methylbenzoylamino)-benzene, 1-amino-2-ethoxy-5-(o-methoxybenzoylamino)-benzene, 1-amino-2-ethoxy-4-(o- ~.;.
methoxybenzoylamino)-benzene, l-amino-2,5-diethoxy-4-benzoyl- . .
aminobenzene, l-amino-2,5-diethoxy-4-(o-chlorobenzoylamino)- ;
benzene, 1-amino-2,5-diethoxy-4-(p-chlorobenzoylamino)- :, benzene, l-amino-2,5-diethoxy-4-(2',4'-dichlorobenzoylamino)- ~ ~
benzene, l-amino-2,5-diethoxy-4-(o-methylbenzoylamino)-benzene, ;: .:
l-amino-2,5-diethoxy-4-(p-methylbenzoylamino)-benzene, 1-amino-2,5-diethoxy-4-(o-methoxybenzoylamino)-benzene, l-amino- ;
2-ethoxy-5-methyl-4-benzoylaminobenzene, 1-amino-2-ethoxy-5- `~:
chloro-4-benzoylaminobenzene, 1-amino-2-ethoxy-4-phenacetyl- ~:-aminobenzene, l-amino-2-ethoxy-5-phenacetylaminobenzene, 1- :
amino-2,5-diethoxy-4-phenacetylaminobenzene, 1-amino-2 ? 5~ `;
diethoxy-4-phenoxyacetylaminobenzene, 1-amino-2,5-diethoxy~
4-~p-chlorophenoxyacetylamino)-benzene, 1-amino~2,5-diethoxy-4-phenylthioacetylaminobenzene, 1-amino-2-methyl-5-benzoyl-aminobenzene, l_amino-2-methyl-4-benzoylaminobenzene, 1-a~ino~2,5-dimethyl-4-benzoylaminobenzene, 1-amino-2-methyl-5-chloro-4-benzoylaminobenzene, 1-amino-2-methyl-5-phen-- : .
~ ';.' ~ ' '~

~ ~ 5 ~ ~9 acetylaminobenzene, l-amino-2-methyl-4-phenacetylamino-benzene, l-amino-2-methyl-5-phenoxyacetylaminobenzene~
amino-2-methyl-4-phenoxyacetylaminobenzene, l-amino-2,5- ~
dimethyl-4-phenacetylaminobenzene, l-amino-2,5-dimethyl-4-phenoxyacetylaminobenzene, l-amino-2,5-dimethyl-4- (p-chloro-phenoxyacetylamino)-benzene, l-amino-2,5-dimethyl-4-phenyl-thioacetylaminobenzene, l-amino-2-chloro-5-benzoylaminoben-zene, l-amino-2-chloro-4-benzoylaminobenzene, l-amino-2,5-dichloro-4-benzoylaminobenzene, 1-amino-2-chloro-5-methyl-4-benzoylaminobenzene, 1-amino-2-chloro-5-phenacetylaminoben-zene, l-amino-2-chloro-4-phenacetylaminobenzene, l-amino-2-chloro-5-phenoxyacetylaminobenzene, 1-amino-2-chloro-4-phenoxy-acetylaminobenzene, 1-amino-2,5-dichloro-4-phenacetylaminoben-zene, l-amino-2,5-dichloro-4-phenoxyacetylaminobenzene, l-amino-2,5-dichloro-4-(p-chlorophenoxyacetylamino)-benzene, :~
l-amino-2,5-dichloro-4-phenylthioacetylaminobenzene, l-amino- - ::
2-nitro-5-benzoylaminobenzene, 1-amino-2-nitro-4-benzoylamino- -~
benzene, l-amino-2-nitro-5-methyl-4-benzoylaminobenzene, l-amino-2-nitro-5-chloro-4-benzoylaminobenzene, l-amino-2-nitro-4-phenacetylaminobenzene, l-amino-2-nitro-4-phenoxy-acetylaminobenzene, l-amino-2-nitro-4-(p-chlorophenoxyacetyl- ..
amino)-benzene, l-amino-2-nitro-4-phenylthioacetylaminoben- ~.... .
zene, l-amino-2-chloro-5-methyl-4-(3',5'-dichloro-4'-hydroxy- ~ .
benzoylamino)-benzene, l-amino-2-chloro-5-methyi-4-(3' 9 5'-dibromo-4'-hydroxy-benzoylamino)-benzene, -amino-4-53',5'-dichloro-6'-hydroxy-benzoylamino)-benzene and l-amino-2,5-"

-- ~ l 1(~4S~9 dichloro-4-(2'-hydroxy-benzoylamino)-benzene.
: The diazo components mentioned are known compounds.
Coupling components used are preferably those of the formula .
~, .
. . I l '' CH3COC~I2CONH ~ :~
~1 ~ 3 : ' ., . , ~

wherein Xl and Yl have the indicated meaning, and especially those of the formula . .;~

CH3COCH2CONH - ~ NHCOCH2COCH

,Y2 ' . .
',"`.

~herein X2 and Y2 have the indicated meaning.
ese are known compounds which are obtained by the action of diketene or acetoacetic acid esters on the corres-ponding phenylenediamines such as, for example: 194-~henylenediamine, 2 chloro-1,4-phenylenediamine, 2-methyl-: 1,4-phenylenediamine, 2-me-thoxy-1,4-phenylenedîamine, '.

2-ethoxy-1,4-phenylenediamine, 2-phenoxy-1,4-phenylenediarnine, 2-aminocarbonyl-1,4-phenylenediamine, 2-methoxycarbonyl-1,4-phenylenediamine, 2,3-dic:hloro-1,4~phenylenediamine, 2,5-dichloro-1,4-phenylenediamine, 2,6-dichloro-1,4-phenylene-diamine, 2-chloro-5-methyl-1,4-phenylenediamine, 2-chloro-5-methoxy-1,4-phenylenediamine, 2-,5-dimethyl-1,4 phenylene-diamine, 2-methyl-5-methoxy-1,4-phenylenediamine, 2,5-di-methoxy-1,4-phenylenediamine, 2,5-diethoxy-1,4-phenylene-diamineg 2,3,5-trichloro-1,4-phenylenediamine, 2,3,5,6-tetra-: chloro-1,4-phenylenediamine, 2,3,5,6-tetramethyl-1,4-phenylene-diamine, 2,5-dimethyl-3,6-dichloro-1,4-phenylenediamine, 1,3-phenylenediamine, 4-chloro-1,3-phenylenediamine, 2-methyl-1,3-phenylenediamine, 4-methyl-1,3-phenylenediamine, 4-methoxy-1,3-phenylenediamine, 2,4-dichloro-1,3-phenylenediamine, 2~5-dichloro-1,3-phenylenediamine, 4,6-dichloro-1,3-phenylene-diamine, 4,6-dimethyl-1,3-phenylenediamine, 2,6-dimethyl-1,3 phenylenediamine, 1,4-naphthylenediamine, 1,5-naphthylene-diamine and 2,6-naphthylenediami~e.
The coupling is preferably carried out in a weakly .
acid mediumJ suitably in the presence of customary agents which assist the coupling. As such there may in particular be mentioned dispersing agents 9 for example aralkylsul-phonate~s, such as dodecylbenzenesulphonate, or 1,1'-dinaphthylmethane-2,21-disulphonic acid or polycondensation :
products of aIkylene oxides. The dispersion of the coupling component can also advantageously contain protective colloids .;
: ', ' '' ': ~ ' .,.

104S~
for example methylcellulose or minor amounts of iner~ `
sparingly water-soluble, or water-insoluble 9 organic sol-vents, for example optionally halogenated or nitrated aro-ma~ic hydrocarbons, such as benzene, toluene, xylene, chlorobenzene, dichlorobenzene or nitrobenzene, as well as aliphatic halogenoh~drocarbons, such as, for example, carbon tetrachloride or trichloroethylene, and also wa~er-miscible organic solvents, such as acetone, methyl ethyl ketone, methanol, ethanol or isopropanol.
The coupling can also be advantageously carried out by continuously combining an acid solution of the diazonium ~;
salt with an alkaline solution of the coupling component in a mixing nozzle, whereupon immediate coupling of the compo-nents takes place. Care mus-t be taken that the diazo componentsand coupling componentsare present in equim~olecular j amounts in the mixing nozzle7 a slight excess o~ the diazo component proving advantageous; This is mostsimply ef~ected by checking the pH value of the liquid in the mixing nozzle.
Vigorous turbulent intermixing of the two solutions in the mixing nozzle must also be ensured. The colorant dispersion ~produced is continuously withdrawn from the mixing nozzle and the colcrant separated off by filtration.
The coupling can also be carried out by heating a diazoaminc compound of the~amine to he used as the diazo compcnent with the diacetoacetylphenylenediamine in an ~organic solvent, i~ approprlate in an aqueous-organic sol-venb, pre~erably in the presence of an acid ~ .~

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The diazoamino compounds to be used according to the process are obtained in accordance with known processes, by coupling a diazonium salt of the amine which serves as the diazo component with a primary or preferably with a secondary amine. The most diverse amines can be used for this purpose, for example aliphatic amines, such as me-thyl- -amine, ethylamine, ethanolamine, propylamine, butylamine, hexylamine and especially dimethylamine, diethyIamine, diethanolamine, methylethanolamine~ dipropylamine or dibutylamine, aminoacetic acid, methylaminoacetic acid, butylaminoacetic acid, aminoethanesulphonic acid, methyl-aminoethanesulphonic acid, guanylethanesulphonic acid and ~-aminoethylsulphuric acid, cycloaliphatic amines such as cyclohexylamine, N-methylcyclohexylamine and dicyclohexyl-amine, aromatic amines, such as 4-aminobenzoic acid~
sulphanilic acid, 4-sulpho-2-aminobenzoic acid, (4~sulpho- ~
phenyl)-guanidine9 4-N-methylaminobenzoic acid, 4- -ethylaminobenzoic acid, l-aminonaphthalenesulphonic acid~
l-aminonaphthalene-2,4-disulphonic acid, heterocyclic amines such as piperidine, morpholine, pyrrolidine an~
dihydroindole and finally also sodium cyanamide or dicyan-diamide.
As a rule, the diazoamino compounds obtained are sparingly soluble in cold water and can, if necessary after ;
salting out, be isolated in a crystalline form from the .. :
reaction medium. In many cases9 the moist press cakes can ~be used for the further reaction. In individual cases it ~
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~0451~9 can prove appropriate to dehydrate the diazoamides by vacuum drying prior to the reaction or to remove the water by azeo-tropic distillation aPter suspending the moist press cake in a solvent.
The coupling of the diazoamino compounds with the coupling oomponent is then carried out in an organic solvent, for example chlorobenzene, o-dichlorobenzene, nitrobenzene, pyridine, ethylene glycol, ethylene glycol monomethyl ether or monoethyl ether, dimethylformamide, N-methylpyrrolidone, formic acid or acetic acid. ~en using solvents which are water~miscible it is not necessary to use the diazoamino com-pound in the anhydrous form. For example, the water-moist filter cakes can be used. The scission of the diazoamino compound which precedes the coupling takes place in an acid medium. If neutral solvents are used, the addition of an acid, for example hydrogen chloride, sulphuric acid, formic acid, acetic acid or chloroacetic acid is necessary.
The coupling is suitably carried out with warming~
preferably at temperatures between 80 to 180C, and in general takes places very rapidly and completely.
By virtue of their insolubility, the pigments obtained can be isolated from the reaction mixtures by fil-tration. It proves advantageous to carry out an after- -~
treatment of the pigments obtained, with an organic solvent which preferably boils above 100C. Benzenes substituted by halogen atoms, alkyl groups or nitro groups, such as xylenes, chlorobenzene, o-dichlorobenzene or nitrobenzene9 prove to . , ~O~L5~l~9 .
be particularly suitable, as do pyridine bases, such as pyridine, picoline or quinoline 3 and also ketones, such as cyclohexanone, ethers, such as ethylene glycol monomethyl ether or monoethyl ether, and amides, such as dimethylforma-mide or N-methylpyrrolidone.
Finally, the coupling can also be carried out by suspending the amine which is to be diazotised together with the coupling component, in the molar ratio o~ 2:1, in an organic solvent and treating the suspension with a diazo tising agent~ especially an ester of nitrous acid, such as methyl nitrite, ethyl nitrite, butyl nitrite, amyl nitrite or octyl nitrite.
The new colorants are valuable pigments which can be used, in a finely divided form, for pigmenting high molecular organic material, for example cellùlose ethers and cellulose esters, high molecular polyamides and high molecular polyurethanes or poiyeste~, acetylcellulose, nitrocellulose, natural resins or synthetic resins, such as polymerisation resins or condensation resins, ~or example aminoplasts,- in particular urea-~ormaldehyde and melamine-formaldehyde resins, alkyd resins, phenoplasts3 polycarb-onates, polyole~ines, such as polystyrene, polyvinyl ohloride, polyethylene, polypropylene, polyacrylonitrile, polyacrylic acid esters, thermoplastic or curable acrylic resins, rubber, caseinS silicone and silicone resins, individually or as mixtures. It is immaterial whe-ther the high molecular compounds mentioned are in the form of plastic ..:
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~0~5~19 . ' ' masses or melts or in the form of spinning solutions, lacquers or paints. The new pigments prove to be particu-- larly suitable ~or printing inks. Depending on the application, it proves advantageous to use the new pigments as toners or in the form of preparations; The preparations can for example contain, alongside the pure pigment, natural resins, for example abietic acid or its esters, ethylcellu-lose, cellulose acetobutyrate, alkaline earth metal salts of higher fatty acids, fatty amines, for example stearylamine or rosinamine, vinyl chloride/vinyl acetate copolymers, polyacrylonitrile or polyterpene resins or water-soluble dyestuffs, for example dyestuff-sulphonic acids or their alkaline earth metal salts. The colourations obtained wi-th the new colorants are distinguished by good fastness to light and to migration, great depth of colour, brilliance and heat stability.
Depending on the particle size and particle size -distribution, highly transparent to very opaque colourations can be obtained with the pigments according to the inven-tion in a great diversity of substrates. If the pigments are obtained in a form which is too ~inely granular, they ~ -can be converted to a coarser form, with improved hiding power, by recrystallisation in an aqueous and/or organic - medium, ~or example in organic solvents, as a rule by a - heat treatmen-t, for example at temperatures between 160 and 300C and, if appropria-te, under elevated pressure. On the other hand, excessively coarse pigments can be con~erted to .. .
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a finely granular, transparent form by sui-table comminution measures, for example by wet grinding processes or dry grinding processes.
` In the examples which follow the parts, unless otherwise stated, denote parts by weight and the percentages denote percentages by weight.
Example 1 47.2 parts of 1-amino-2-chloro-5-methoxy-4-acetylamino-benzene are dissolved in 1,500 parts by volume of glacial acetic acid at room temperature. The light yellow solution is stirred with 60 parts by volume of concentrated hydro-chloric acid, the mixture is cooled to 6C, 60 parts by ;
volume of 4N sodium nitrite solution are added dropwi-se over the course of 10 minutes and the resulting diazo solution is clarified by filtration. The filtrate is brought to~pH 4 by ~;~
addition of 50 parts of 60~o strength sodium acetate;
At the same time, 34 parts of 2-methoxy-5-chloro- !;
1,4-bis-acetoacetylaminobenzene are dissolved in 2,000 parts of water by addition of 30 parts by volume of 40% strength sodium hydroxide solution. After addition o~ 2 parts o~
kieselguhr the resulting suspension is clarified by filtra-tion and the residue is rinsed with 70 parts by volume o~
water. A clear light yellow solution is thus obtained, to ;~
which the diazo solution is added dropwise at 5C over the course of 20 minutes. This produces a yellow precipitate.
The suspension obtained is heated to 75C over the course of ~ .
one hour and filtered hot. The residue is washed until free ..
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from salt and dried in vacuo at 60C. 78 parts, corresponding to 97% of theory, of a yellow pi~ment of the formula C1 f OCH3 0CH3 70CH3 Cl C~ Co~ N=/~-cHco~ HoccEl-N=N~NlloccH3 are obtained;
I~ this pigment is after-treated in dimethyl~ormamide (one hour at 140C) and milled into polyvinyl chloride, fast yellow colourations are obtained. :~
The table which follows describes further colorants which are obtained by coupling the diazotized bases o~ Column :
I with the bis-acetoacetic acid aryiides o~ the diamines of Column II. Column III indicates the colour shade o~ a PVC
~ilm coloured with 0.2~o Of this pigment.

: :

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N ~ ~ C ~ ~ ~ ~ i ~ C ~ ;

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H h S~ Na) Ei h N h i . O ~W o ~ ~ oh ~? ~1 o N

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. ,'"'~,;
_ ~ , rl _ ' '' '~'.. ' ;: ~ ~ . '' ~ ~ - 29_ ~0~5~9 2 g of the pigment prepared according to Example 1 are ground with 36 g of hydrated aluminium oxide, 60 g of a linseed oil varnish of medium viscosity and 2 g of cobalt linoleate on a triple roll mill. The yellow prints produced with the resulting colour paste are deeply coloured and have outstanding fastness to light.
Example 130 0;6 g of the pigment prepared according to Example 1 are 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 converted to a thin film on a roll mill over the course of 15 minutes at 160C. The yellow colouration thus produced is deep and fast to migration, heat and light.
Example 131 10 g of titanium dioxide and 2 g of the pigment prepared according to Example 1 are ground with 88 g of a mixture of 26.4 g of coconut alkyd resin, 24.0 g of melamine-formaldehyde resin (50/0 solids content~, 8.8 g of ethylene glycol monomethyl ether and 28.8 g of xylene for 48 hours in a ball mill.
If this lacquer is ~yed onto an aluminium ~oil, pre-dried for 30 minutes at room temperature and -then s-toved for 30 minutes at 120C, a yellow lacquering is ob-tained, -;
which has good depth of colour and is distinguished by very good fa~tness to overlacquering, light and weathering _ 30 - -.

5 ~9 Example 132 3.2 parts of l-amino-~acetylamino-benzene and 3.1 parts of 2,5-dimethyl-1,4-bis-acetoacetylamino-benzene are dissolved in 200 parts of dic~orobenzene and 50 parts of glacial acetic acid at 50C. After cooling to room tempera-ture, 2.5 parts of tert.-butyl nitrite in 100 ml of dichlorobenzene are added dropwise over the course of 15 minutes, during which the temperature rises to 40C and the pigment formation starts.
The mixture is then stirred for 2 hours at 40-50C --and 18 hours at 103 - 140C. The colorant assumes a uni-formly crystalline form. Orange crystalline aggregates of 10 - 20 ~ length are detectable under the microscope. The'!' ' product is filtered off at 140C and washed with hot dichloro-benzene until the filtrate emerges colourless, the dichlorobenzene is displaced by methanol and the product is finally washed with hot water. After drying, 5.5 parts of an orange-yellow colorant of the formula ~- ~ NHcocH3 ~ ~ NHCOCH3 '-1 ' 1- . ..
CH3COCHCONH- ~ NHOCCHOCH3 - , ' ~?~

~L~4~
are obtained.
The pigment thus prepared is outstandingly suitable for the production of printing inks, having good flow, for the graphic trade, and gives very deep, pure yellow prints of good gloss and transparency.
The treatment in the organic solvent can also be ,.
carried out directly with the moist filter cake without prior drying. Thus, the moist press cake can be stirred in picoline at 100-120C, ~iltered off and washed with methanol and subsequently with dilute hydrochloric acid or the moist press cake is stirred into chlorobenzene, o-dichlorobenzene 3 or nitrobenzene, freed from water by azeotropic distillation and then worked up as described above.

.

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.

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~ 32 -

Claims (12)

CLAIMS:

1. A disazo pigment of the formula wherein A denotes a phenylene or naphthylene radical, R
denotes an aryl, alkyl or alkenyl group optionally substi-tuted by halogen atoms, by hydroxyl, alkoxy or alkylmercapto groups containing 1-6 C atoms, by alkoxycarbonyl groups eon-taining 2-6 C atoms or cyano, aryl, aryloxy, arylmercapto or heteroeyclic radicals, or denotes a heterocyclic radical, and the X and Y denote H atoms or substituents which do not confer solubility in water.

2. A disazo pigment according to Claim 1, wherein R
denotes an alkyl group containing 1-6 C atoms.

3. A disazo pigment according to Claim 1, wherein R
denotes a phenyl group which is optionally substituted by halogen atoms, hydroxyl groups or alkyl or alkoxy groups containing 1-4 C atoms or alkoxycarbonyl groups containing 1-4 C atoms.

4. A disazo pigment according to Claim 1, wherein X
denotes a H atom, an alkyl or alkoxy group containing 1-4 C
atoms, a nitro or cyano group or an alkoxycarbonyl or alkanoylamino group containing 2-5 C atoms, and Y denotes a H or halogen atom or an alkyl or alkoxy group containing 1-4 C atoms.

5. A disazo pigment according to Claim 1, wherein the -NHCOR group is in the para-position to the azo group.

6. A disazo pigment according to Claim 1, wherein A
represents a radical of the formula wherein X1 and Y1 denote H or halogen atoms, alkyl or alkoxy groups containing 1-4 C atoms, phenoxy, trifluoromethyl, nitro or cyano groups, or alkoxycarbonyl groups containing 2-5 C atoms.

7. A disazo pigment according to Claim 1, wherein A
denotes a radical of the formula wherein X2 and Y2 denote H or chlorine atoms or alkyl or alkoxy groups containing 1-4 C atoms.

8. The compound according to Claim 1 of the formula

9. The compound according to Claim 1 of the formula

10. The compound according to Claim 1 of the formula

11. The compound according to Claim 1 of the formula

12. The compound according to Claim 1 of the formula