DE2326298A1 - NEW DISAZOPIGMENTS, PROCEDURES FOR THEIR PRODUCTION AND USE - Google Patents

Description

CIBA-GEIGYAG. CH-4002 Basal

Dr. P. Zumsiein sen. - Dr. E. Ässmann fcSLttoenigsberger - Dip !. Phys. R. Holzbauer Dr. F. Zumsisin jun.

Petantonw8lti @ iifsöncliera 2, ßs-ätil-söajssiraSis

Case 3-8201 / +

New disazo pigments, processes for their production and

Use.

It was found that new valuable disazopxgmenten of the formula.

309849/1145

CIL-CO-CH-CO-Jffl-

Xrt ^ N

Z-R.

IiH-O C-CH-CO-CIL

(D

arrives, wherein R, an alkyl, alkoxyalkyl or cycloalkyl group containing 1 to 6 carbon atoms, an aryl or AraIkylgruppe, R ^ a hydrogen, bromine or especially chlorine atom, R ^ is an H atom, if R2 is a chlorine or bromine atom and R- is a carboxylic acid ester group when R ^ is a Η atom, Z is a sulfur or oxygen atom, X is a hydrogen or halogen atom, an alkyl or alkoxy group containing 1 to 4 carbon atoms, a Nitro, cyano, trifluoromethyl group or an alkoxycarbonyl group containing 1 to 6 carbon atoms, Y a hydrogen or halogen atom, an alkyl or alkoxy group containing 1 to 4 carbon atoms, a nitro, trifluoromethyl or cyano group or an alkoxycarbonyl group containing 1 up to 6 carbon atoms, or X and Y together represent a fused-on benzene ring if a diazo or diazoamino compound of an amine of the formula

Z-R

(II)

ZR _n

with a bis-acetoacetylphenylenediamine of the formula

"309849/1 US

CH ₅ -CO-CH ₂ -CO-NH-

(III)

NH-CO-CH ₂ -CO-CH ₅

couples in a molar ratio of 2: 1.

Since the dyes according to the invention are Pigments are water-solubilizing groups, especially acidic water-solubilizing groups, such as sulfonic acid or carboxylic acid groups excluded.

Of particular interest are disazo pigments.

formula

CH ₅ -CO-CH-CO-NH-

-NH-CO-CH-CO-CH ₃

where R _{2 is} a hydrogen, bromine or, in particular, chlorine atom, R, is an H atom, if R _{£ is} a chlorine or bromine atom and R4 is an alkoxycarbonyl, haloalkoxycarbonyl, phenalkoxycarbonyl, one optionally with halogen atoms, alkyl - Or alkoxy groups containing 1-4 carbon atoms substituted phenoxycarbonyl group or a heterocyclic carboxylic acid ester group when R _{9 is} a Η atom, X _{1 is} a hydrogen or halogen atom, an alkyl or alkoxy group containing 1-6 carbon atoms, Y is a Hydrogen or

309849 / 1U5

Halogen atom or a phenyl group, m is the number 1 to 4, X ^ and Yr, hydrogen or halogen atoms, alkyl or alkoxy groups, containing 1 to 4 carbon atoms, mean ^ and especially disazo pigments of the formula

(Cl)

(Cl)

(Cl)

CH-CO-CH-CO-NH-

^ -KH — σο — c:

(V)

(Cl),

where X ^ and Y ^ have the meaning given and η is the number 1 to 5 means.

Amines of the formula are preferably used as diazo components

(Va)

309849/1 US

wherein R ^ ^e ^ - ⁿ ΒΤ ^ΟΠ1 ~ or in particular chlorine atom, X-, a hydrogen or halogen atom, an alkyl or alkoxy group containing 1 to 6 carbon atoms, Y ^ a hydrogen or halogen atom or a phenyl group and m is the number 1 to mean and in particular those of the formula

(VI)

where η is the number 1 to 5.

The following aminobenzenes are examples:

3-chloro-2,4-diphenoxy-aniline 3-bromo-2,4-diphenoxy-aniline 3-chloro- 2,4-dl- (2'-chlorophenoxy) -aniline 3-chloro-2,4-di- (4'-chlorophenoxy) -aniline 3-chloro- 2,4-di- (2 ', 4'-dichlorophenoxy) -aniline 3-chloro-2,4-di- (2', 4 ', 5'-trichlorophenoxy ) -aniline 3-chloro- 2,4-di- (2 ¹ , 3 *, 4 ', 6 ^! -tetrachlorophenoxy) -aniline 3-chloro-2,4-di- (2 ¹ , 3', 4 ^!, 5 ', 6'-pentachlorophenoxy) -aniline 3-chloro- 2,4-di- (4'-pheny! Phenoxy) -aniline 3-bromo-2,4-di- (4'-chlorophenoxy) -aniline 3- Chloro-2,4-di- (pheny! Mercapto) -aniline

3 0 9 8 U 9 I 1 US

3-chloro-2,4-di- (4'-methylphenylmercapto) aniline 2326 298

3-chloro-2,4-dibenzyloxy-aniline 3-chloro-2,4-di (ß-methoxyethoxy) aniline 3-chloro-2,4-di (β-ethoxyethoxy) aniline 3-chloro-2,4-di (cyclohexyloxy) aniline.

3-Amino-4,6-diphenoxy-benzoic acid methyl ester 3-Amino-4,6-diphenoxy-benzoic acid ethyl ester 3-Amino-4,6-diphenoxy-benzoic acid iso-propyl ester, 3-Amino-4,6-diphenoxy-benzoic acid phenyl ester 3-Amino-4,6-diphenoxy-benzoic acid 2'-methylphenyl ester 3-Amino-4,6-diphenoxy-benzoic acid-4'-chlorophenyl st er

3-Amino-4,6-diphenoxy-benzoic acid-2'-methyl-4'-chlorophenyl ester

3-Amino-4,6-diphenoxy-benzoic acid benzyl ester 3-Amino-4,6-diphenoxy-benzoic acid 4'-methoxy-benzyl ester 3-Amino-4,6-diphenoxy-benzoic acid 3'-oxypyridyl ester

The coupling components preferably correspond to the formula

(VII)

wherein X ₂ and Y ^ are hydrogen or halogen atoms, alkyl or alkoxy groups containing 1 to 4 carbon atoms, ',

The coupling components are obtained in a simple manner
Way by the action of diketene or acetoacetic ester on the corresponding known phenylenediamines such as:

1,4-phenylenediamine

2-chloro-1,4-phenylenediamine

2-bromo-1,4-phenylenediamine

2-trifluoromethyl-1,4-phenylenediamine 2-cyano-1,4-phenylenediamine

2-methyl-1,4-phenylenediamine

30984 9/1145

2-methoxy-1,4-phenylenediamine ^ '* f- 232.6298

2-ethoxy-1,4-phenylenediamine 2-propoxy-1,4-phenylenediamine 2-iso-propoxy-1,4-phenylenediamine 2-butoxy-1,4-phenylenediamine 2-phenoxy-1,4-phenylenediamine 2-nitro -1,4-phenylenediamine 2-methoxycarbonyl-1,4-phenylenediamine 2-carboxylic acid ethyl ester-1,4-phenylenediamine 2,5-diethoxycarbony1-1,4-phenylenediamine 2,3-dichloro-1,4-phenylenediamine 2,5- Dichloro-1,4-phenylenediamine 2,6-dichloro-1,4-phenylenediamine 2,6-bis-trifluoromethy1-1,4-phenylenediamine 2,6-dibromo-1,4-phenylenediamine 2-chloro-5-methyl- 1,4-phenylenediamine 2-chloro- * 5-methoxy-1,4-phenylenediamine 2-chloro-5-ethoxy-1 _s 4-phenylenediamine 2,5-dimethyl-1,4-phenylenediamine 2-methyl-5-methoxy -1 j, 4-phenylenediamine 2-methyl-5-ethoxy-1, 4-phenylenediamine 2-methyl-5-propoxy-1,4-phenylenediamine 2-methyl-5- i-propoxy-1 ₃ 4- phenylenediamine 2-methyl-5-buthoxy-1,4-phenylenediamine I3-phenylenediamine 4-chloro-1,3-phenylenediamine 4-bromo-1j 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-phenylenediamine 4,6-dimethyl-1,3-phenylenediamine 2,6-dimethyl-1,3-phenylenediamine

2,5-Di.ittettiaxy-1,4-phenylenedlamine 2,5-diethoxy-1,4-phenylenediamine 1,5-naphthylenediamine

309849/1 US

The coupling takes place preferably in a weakly acidic medium, expediently in the presence of conventional ones Coupling promoting means. As such, dispersants may be mentioned in particular, for example aralkyl sulfonates, such as dodecylbenzenesulfonate or 1,1'-dinaphthylmethane-2,2'-di sulfonic acid or polycondensation products of alkylene oxides. The dispersion of the coupling component can also be advantageous Protective colloids, for example methyl cellulose or smaller amounts of inert ones, which are sparingly soluble or insoluble in water organic solvents, for example optionally halogenated or nitrated aromatic hydrocarbons, such as benzene, toluene, xylene, chlorobenzene, dichlorobenzene or nitrobenzene and aliphatic halogenated hydrocarbons, such as carbon tetrachloride or trichlorethylene, furthermore water-miscible organic solvents such as acetone, methyl ethyl ketone, methanol, ethanol or isopropanol. The coupling can also be carried out advantageously in such a way that an acidic solution of the diaz'onium salt with a alkaline solution of the coupling component in a mixing nozzle continuously combined, with an immediate coupling of the Components takes place. Care must be taken that the diazo component and coupling component are in equimolecular amounts in the Mixing nozzles are present, it proving to be advantageous to use a small excess of the diazo component. The easiest way to do this is to check the p ^ value

309849/1145

the liquid in the mixing nozzle. Also is in the Mixing nozzle to ensure a strong swirling of the two solutions. The resulting dye dispersion is the The mixing nozzle is continuously withdrawn and the dye is separated off by filtration.

Thanks to their insolubility, the pigments obtained can be isolated from the reaction mixtures by filtering them off. It proves to be advantageous to post-treat the pigments obtained with a preferably liber 100 ⁰ C boiling organic solvent. Particularly suitable are benzenes substituted by halogen atoms, alkyl or nitro groups, such as xylenes, chlorobenzene, o-dichlorobenzene or nitrobenzene, and pyridine bases such as pyridine, picoline or quinoline, and ketones such as cyclohexanone, ethers such as ethylene glycol monomethyl or monoethyl ether, Amides, such as dimethylformamide or N-methyl-pyrrolidone, and sulfoxone.

The aftertreatment is preferably carried out by heating the pigment in the solvent to 100 to 150 ^° C., which in many cases results in a coarsening of the grain, which has a favorable effect on the lightfastness and migration fastness of the pigments obtained.

309849/1146

Finally, the coupling can also be carried out in such a way that the amine to be diazotized with the coupling component suspended in an organic solvent in a molar ratio of 2: 1 and with a diazotizing agent, in particular an ester of nitrous acid, such as methyl ,. Treated ethyl, butyl, amyl or octyl nitrite.

The new dyes are valuable pigments which can be used in finely divided form for pigmenting high molecular weight organic material, for example cellulose ethers and esters, such as ethyl cellulose, cellulose acetate, cellulose butyrate ₉ natural resins or synthetic resins such as polymerization resins or condensation resins, e.g. aminoplasts, especially urea - and melamine-formaldehyde resins ", alkyd resins, phenoplasts, polycarbonates, polyesters, polyamides or polyurethanes, polyolefins such as polyethylene or polypropylene, polyvinyl chloride, polystyrene, polyacrylonitrile, polyacrylic acid esters, rubber, casein, silicone and silicone resins, individually or in mixtures.

It does not matter whether the mentioned high molecular compounds as plastic masses, melts or in the form of spinning solutions, lacquers, paints or printing inks. Depending on the intended use, it turns out to be It is advantageous to use the new pigments as toners or in the form of preparations.

309849/1145

The preparations can, for example, in addition to the core pigment still natural resins, for example abietic acid or esters thereof, Aethy cellulose!, Cellulose acetate butyrate ₉ alkaline earth metal salts of higher fatty acids fatty amines, such as stearylamine or rosin amine _s vinyl chloride-vinyl acetate as copolymers, polyacrylonitrile or polyterpene or water ·-soluble dyes, for example Farbstoffsulfonsäuren or contain their alkaline earth salts.

It is surprising that the inventive Pigments, despite their simpler structure, the same distinctive Have migration fastness like the pigments of GB-PS 1.076 "942, which contain two additional carbonamide groups.

In the following examples, the parts mean unless otherwise indicated, parts by weight, percentages percentages by weight, and temperatures are in degrees Celsius specified.

309849/1 1 45

example 1

46.5 parts of 3-chloro-2,4-di- (4'-pheny! Phenoxy) aniline are dissolved in 600 parts by volume of glacial acetic acid and then 26 parts by volume of concentrated hydrochloric acid are added with stirring, the sparingly soluble chlorohydrate of the base being formed. It is then cooled to 0 ° to 5 ° by external cooling and 100 parts of ice, and diazotized by adding dropwise 25 parts by volume of 4-n-sodium nitrite. The yellow diazo solution is stirred for 30 minutes at 0 to 5 ° and then clarified by filtration with the addition of some decolorizing charcoal. The filtrate is adjusted by adding 58 parts of crystallized sodium acetate to a p "of 3 _5. 5

At the same time, 15 parts of 2,5-bis-aeetoaeetylaiaino-4-chloro-1-methoxybenzene are dissolved with 11 parts by volume of 40% sodium hydroxide solution, 100 parts by volume of ethanol and 300 parts of water, and 5 parts of n-butyl sulforicinoleate are added. This solution tvärd with decolorizing skohle then clarified by filtration _s can they "anter vigorous stirring igäh'CBnd 1 to lh hours to Diasolosung sutropfen" then stirred superiority at room temperature, "heated to 80 ° ρ filtered hot trad washed with hot water until salt-free," , Mach'dem drying one obtains 56 _S 5 parts of a yellow dye of the formula

14th

(VIII)

Cl

CEL-CO-CH-CO-NH-

-NH-CO-CH-CO-CH.

OCR,

56 parts of the pigment thus obtained are in 800 parts by volume of o-dichlorobenzene for 4 hours at 140 bis Stirred at 145 °. The pigment now forms uniformly crystalline Needles with a length of 20 to 25 μ, one filtered at 100 °, washes with hot o-dichlorobenzene until the filtrate is colorless expires, displaces the o-dichlorobenzo by methanol and Finally, wash with hot water. After drying, 39.5 parts of a bright yellow pigment are obtained. It colors plastics such as PVC in neutral yellow tones with excellent fastness to migration, light and varnish. the Treatment in the organic solvent can also be carried out directly with the moist filter cake without prior drying. The moist press cake can be mixed with Cellosolveo-dichlorobenzene in a ratio of 1: 2 at 100 to 110 ° until it is converted into a uniform crystalline form will; or the moist press cake is stirred in chlorobenzene, o-dichlorobenzene or nitrobenzene and azeotroped Distillation freed from the water and then as described above

3098 49/1 US

worked up.

In the table below, further dyes are described that are obtained by coupling the diazotized bases of the Column I can be obtained with the bis-acetacetic arylides of the diamines of column II. Column III gives the color tone with 0.27ο pigment and "5% titanium dioxide colored PVC film.

309849/1 145

Table I.

example

Diasoba s®

ΡΙιΊ

aniline

3-chloro-2 "4-'di- (2 ' ₉ 4' -dichlor-

3-chloro-2 _B 4-di- (2 ^S , 4 '- dichloro «

3 ° chlorine = - 2 "4- di- (2 '" 4 ⁵ - dichlor = pheno2sy) = aniline

3 ~ chlorine = 2,4-di- (2 * ρ 4 ^g

■ aniline

■ 2.4

tn t α ί

3-chloro-2 ₀ 4-dl- (2 ' j ft ^f "5 ' - tri-

clalorpheaossy) - aniline

S ^ Chl © ^ ¹ »21.4 ° ol ° (4 °" |

3 "Uh'Lu'is ^ t _? ^ Ul" (4 ° «•» jiAiaayl'pbo

Bis-acetoacety! Compound of diamine

2 ° methyl "= 5-chloro-1,4-phenylenediamine

~ Methyl »5» chlorine = 1.4 ° phenylenediamixi

2 = MetHoxy 1,4-phenylenediamine

j 5-dimethyl-1,4-phenylenediamine

2 = methyl = 5 = chlorine = 1 _s 4 = phenylenediamine

2-Metho2sy ° 1 ₉ 4 = phenylenediamine

2 «M® tliyl» 5- ehlof «1,4-phenylenediamine

0.2% coloring + 5% TiOo in PVC

neutral yellow

pale yellow

'' reddish yellow

reddish yellow

neutral yellow

reddish yellow

reddish yellow

greenish yellow

reddish yellow ".

reddish yellow

TableJE (continued)

at
game
No. Diasobase Bi's-acetoacetyl compound of diamine 0.2% dye
exercise + 51
TiO ₂ in PVC 12th 3 - => chlorine = * 2.4 «= di- (4 ^s » ehlorphenyl-
mercapto) aniline 2-methoxy-5-chloro-1,4-phenylenediamine bright
yellow 13th 3- chlorine = 2.4 ° di «(4 - chlorine-
pheny! mercapto) aniline 2,5-dichloro-1,4-phenylenediamine bright
yellow 14th 3 ° chlorine = 2.4 «= di- (2 ^t = chlorophenoxy) -
aniliii 2.5 = dimethoxy-1,4-phenylenediamine reddish
yellow 15th 3 »chlorine» 2 _s 4 »di» (2 ^f ₀ 4 ^B »diehlor-
phenoxy) »aniline 2 ₉ 5-Dimethoxy-1 _s 4-phenylenediamine reddish
yellow 16 ■ 3 »chlorine = 2 _> 4-di» (2 ^l . ₉ 4 ⁱ , 5 ^t »trichlor» -
phenoxy) aniline 2,5-dimethoxy = · 1,4-phenylenediamine orange 17th 7th
3 »chloro-2,4 = di- (2'-chlorophenoxy) -.
aniline 1.4 ° r phenylenediamine yellow 18th 3 »chlorine- 2 , 4- di (2 ', 4 ' - dichlorophene ■
OSEy) aniline 1,4-phenylenediamine yellow

Table I (continued)

19th 3-chloro-2,4-di- (4'-phenylphenoxy) -
aniline 1,4-phenylenediamine yellow 20th 3-chloro-2,4-di- (4'-phenylphenoxy) -
aniline 2-methy1-5-chloro-
1,4-phenylenediamine yellow 21 3-chloro-2,4-di- (4'-chloropheny1-
mercapto) aniline 1,3-phenylenediamine ' yellow O
co
QO 22nd 3-chloro-2,4-di- (2 ' _? 4 ⁱ -dichlor-
phenoxy) aniline 1,3-phenylenediamine yellow 23 3-chloro-2,4-di- (2 ', 4', 5 ^! - tri-
chlorphenoxy) aniline 1,3-phenylenediamine yellow «Η 24 3-chloro-2 _P 4-di- (2 ' _? 4' ₉ 5 ⁱ -tri-
chlorophenoxy) aniline 2,5-dietoxy-1,4-phenylenediamine orange 25th 3-chloro-2 ₅ 4-di- (2 ', 4 ^!, 5'-tri-
chlorophenoxy) aniline 1,4-phenylenediamine yellow 26th 3-bromo-2,4-di- (4'-chlorophenoxy) -
aniline 2,5-dimethoxy-1,4-phenylenediamine orange

K) CD K>

Table I (continued)

27 3-chloro-2,4-di- (4'-chlorophenoxy) -
aniline 1,5-naphthylenediamine reddish
yellow 28 3-amino-4,6-diphenoxy-benzoic acid
re-methyl ester 1,4-phenylenediamine light yellow 29 3-amino-4,6-diphenoxy-benzoic acid
re-methyl ester 2-Methy1-5-chloro-1,4-pheny-
lenediamine yellow 30th 3-amino-4,6-diphenoxy-benzoic acid
methyl ester 2-methoxy-5-chloro-1,4-pheny-
lenediamine yellow co
O 31 3-atnino-4, 6-diphenoxy-benzoic acid
methyl ester 2 _S 5-dimethyl-1,4-phenylene-
diamine reddish
yellow co
OO 32 3-amino-4,6-diphenoxy-benzoic acid
phenyl ester 2-methoxy-5-chloro-1,4-pheny-
lenediamine yellow i & 33 3-amino-4,6-diphenoxy-benzoic acid
benzyl ester 2-methoxy-5-chloro-1,4-pheny-
lenediamine greenish
yellow .P- 34 ■ 3-amino-4,6-diphenoxy-benzoic acid
3'-oxypyridyl ester 2-methoxy-5-chloro-1,4-pheny-
lenediamine orange
yellow 35 3-amino-4,6-diphenoxy-benzoic acid
iso-propyl ester 2-Methy1-5-chloro-1,4-phenylene
diamine yellow 36 3-amino-4,6-diphenoxy-2-methyl-4'-
bea ^ oesäure-chlor-plieiiylester 2-Methy1-5-chloro-1,4-phenylene
diamine yellow 37 3-amino-4, 6-diphenoxy-4'-methoxy-
bsnaoeeaur & feenaylester 2-Methy1-5-chloro-1,4-phenylene
diamine greenish
yellow

CD K) CO OO

Example 38

65 parts of stabilized polyvinyl chloride, 35 parts of dioctyl phthalate and 0.2 parts of according to Example 1, paragraph 2 _S dye obtained are stirred together and then back on a two-roll calender for 7 minutes at 140 ° and hergewalzt. A yellow-colored film of very good fastness to light and migration is obtained.

■ 09849/1141

Example 39

1.00 g of the pigment prepared according to Example 1 is mixed with 4.00 g of printing varnish with the composition 29.4 % linseed oil stand oil (300 poise), 67.2% linseed oil stand oil (20 poise), 2.1% cobalt octoate (8 % Co) and 1.3% lead octoate (24% Pb) finely ground on an EngeIsmann grinder and

then with the help of a cliché in the letterpress process

printed at 1 g / m on art paper. A strong, pure orange-tinged yellow shade with good transparency is obtained and good shine. In three- or four-color printing, very brilliant ones can be produced by overprinting on blue Create shades of green.

The pigment is also suitable for other printing processes, such as gravure printing, offset printing, flexographic printing and also gives very good results here.

309849/1 145

Claims (1)

Claims MH-OC-CH-CO-CH ₅ wherein R, an alkyl, alkoxyalkyl or cycloalkyl group, containing 1 to 6 carbon atoms, an aryl or aralkyl group, R is a hydrogen, bromine or, in particular, chlorine atom, and Ro is an H atom when R £ is a chlorine or bromine atom and Ro represents a carboxylic acid ester group when R £ is an H atom, Z is a sulfur or oxygen atom, X is a hydrogen or halogen atom, an alkyl or alkoxy group containing 1 to 4 carbon atoms, a nitro, cyano, Trifluoromethyl group or an alkoxycarbonyl group containing 1 to 6 carbon atoms, Y a hydrogen or halogen atom, an alkyl or alkoxy group containing 1 to 4 carbon atoms, a nitro, trifluoromethyl or cyano group or a Alkoxycarhonyl group containing 1 to 6 carbon atoms, or X and Y represent a fused-on benzene ring. 309849/1 US Disazo pigments according to claim 1 of the formula CE ₃ -CO-CH-CO-NH- -EH-CO-CH-CO-CH, where R ^ is a hydrogen, bromine or, in particular, chlorine atom, R / is an H atom, if R _? denotes a chlorine or bromine atom and R- denotes an alkoxycarbonyl, haloalkoxycarbonyl, phenalkoxycarbonyl, a phenoxycarbonyl group optionally substituted by halogen atoms, alkyl or alkoxy groups containing 1-4 C atoms or a heterocyclic carboxylic acid ester group when R2 is an H atom means X, an H or halogen atom, an alkyl or alkoxy group containing 1-6 carbon atoms, Y-. an H or halogen atom or a phenyl group, m the number 1 to 4, Xo and Y ^ H or halogen atoms, alkyl or alkoxy groups containing 1 to 4 carbon atoms. 3. Disazo pigments according to claim 2 of the formula (egg), CSL-CO-CH-CO-M- 3098A9 / 1UB where X2 and Y2 have the meaning given and η the Number 1 to 5 means. 4. Process for the preparation of disazo pigments of the formula '- "" NH-OC-CH-CO-CH, wherein R, an alkyl, alkoxyalkyl or cycloalkyl group, containing 1 to 6 carbon atoms, an aryl or aralkyl group, R ~ a hydrogen, bronw or especially chlorine atom, Ro stands for a Η atom when R2 is a chlorine or bromine atom and R, stands for a carboxylic acid ester group, when R ^ is an H atom, Z is a sulfur or oxygen atom, X is a hydrogen or halogen atom, an alkyl or alkoxy group containing 1 to 4 carbon atoms, a nitro, Cyano, tri-fluoromethy! Group or an alkoxycarbony! Group, containing 1 to 6 carbon atoms, Y is hydrogen or Halogen atom, an alkyl or alkoxy group containing 1 to 4 carbon atoms, a nitro, trifluoromethyl or cyano group or an alkoxy carbon group containing 1 to 6 carbon atoms or X and Y denote a fused-on benzene ring, characterized in that a diazo or diazoamino compound is used of an amine of the formula 3Q9S49 / 1US _ 24.- ZR ₁ R ₂ H ₂ N - <'^) ZR ₁ with a bis-acetoacetylphenylenediamine of the formula CH ₃ -CO-CH ₂ -CO-NH -NH-CO-CH ₂ -CO-CH couples in a molar ratio of 2: 1. 5. The method according to claim 4, characterized in that that the diazo component is an amine of the formula H. used, wherein R ^ is an H ₃ bromine or especially chlorine atom. R / - stands for an H atom, if R ~ is a chlorine or bromine atom and Rf, for an alkoxycarbonyl, haloalkoxycarbonyl, phenalkoxycarbonyl, a 1-4 C- optionally containing halogen atoms, alkyl or alkoxy groups Atoms substituted • phenoxycarbonyl group or a heterocyclic carboxylic acid ester group, if R _{2 is} an H atom, X-, an H- or 309849/1 1 45 AH f O / 7 Halogen atom, an alkyl or alkoxy group containing 1 to ₉ carbon atoms Y, an H or halogen atom or a phenyl group and m denotes the number 1 to 4. "'6." Process according to claim 3, characterized in that the diazo component is an amine of the formula wherein η is the number 1 to 5 is used. 7. The method according to claim 3, characterized in that that you have a coupling component of the formula CH ₃ -CO-CH ₂ -CO-NH Art / * ^J used, wherein X ₉ and Y ₉ H or halogen atoms, alkyl or alkoxy groups containing 1 to 4 carbon atoms. 8. A method for pigmenting high molecular weight organic material, characterized by the use of Dyes according to claims 1 to 3. 9. High molecular weight organic material containing a dye according to claims 1 to 3. FO 3.33 (Me) Me / bro April 4, 1973 30 98 49/1