DE2228773A1 - - Google Patents

Description

CIBA-GEIGYAG, CH-4002 Basel i ^ fiL * / '

Case 3-7558 / +

Dr. F. Zumstoin Sr. - Dr. E. As3mann Dr.R.Koenig3h, ergcr - Dip !. Phys.R. Hoizbauer

Dr. F. Zumsicin jun.

P ο t ο η I α η w ö I t «

8 Munich 2, Bräuhausstraße 4 / III

New monoazo dye pigments and processes for their

Manufacturing

The present invention relates to valuable, new mono azo dye pigments of the formula

R ₂

^ CONH-R-NHCONH-R. 3 4

where .R is an aryl radical, especially a benzene radical, R a naphthalene radical _} in which the azo, hydro>: y and carboxylic acid arid groups are in the 1, 2, 3-position, R an at least bicyclic aromatic radical, especially a naphthalene or Anthraquinone residue or the remainder of the formula

wherein X is a direct bond or a bridge member, for example a Q atom, an alkylene group, a -CH = CH- or -N = N- group, Y, and Y ^ H or halogen atoms, alkyl or alkoxy groups, R / is an alkyl, aryl or aralkyl radical or cycloalkyl radical mean. Dyes of the formula are of particular interest

2 0 9 8 5 2/1121

(in)

N H C O N H

wherein Z is a hydrogen or halogen atom, an alkoxy or a nitro group, X, a hydrogen or halogen atom, X ₂ and Xo are hydrogen or halogen atoms, alkyl, alkoxy, phenoxy, nitro, carbophenoxy, alkali metal , Carbamido, carboxylic acid alkylamido, sulfonic acid, alkyl or aryl esters, sulfonamides, sulfonic acid mono- and dialkylamino, sulfonic acid mono- and diarylamido or trifluoromethyl groups, Y, hydrogen or halogen atoms, alkyl - Or alkoxy groups, Z ₁ denotes a hydrogen or halogen atom, Z2 and Z ^ denote hydrogen or halogen atoms, alkyl, alkoxy, carbalkoxy or trifluoromethyl groups, or dyes of the formula

(IV)

NHCONH

wherein V is a hydrogen or halogen atom, an alkyl, alkoxy or carbalkoxy group, W and Z, hydrogen or halogen atoms

2 09852/1121

Z ₁ - and Z, - hydrogen or halogen atoms, alkyl, alkoxy,

Mean carbalkoxy or trifluoromethyl groups

and Z, Y, Z,: Z and Z have the meaning given.

Since the dyes according to the invention are ura Pigments are water-soluble groups, in particular acidic, water-solubilizing groups, such as Sulfonic acid or carboxylic acid groups, of course locked out. ·

The new dyes are obtained if a) a carboxylic acid halide of the formula

(V)

wherein R and R ^ the. have given meaning, with a lion ο ami η the formula.

H ₀ NR ₀ 2 3

condensed, where R "and R have the meaning given,

or '· "" · - ■

b) a diazo or diazoanino compound of an aromatic Amine with a naphthol of the formula

^on

C0NH-R _o -KHC0NH-R, 3

clutch.

20986? / 1 1? 1

The carboxylic acids on which the halogenines are based are retained by coupling the diazo compound of an aminobenzene, especially one of the formula

or one of the formula

(VIII)

(ix)

with a 2,3-hydroxynaphthoic acid, especially one of the formula · '·

COOH

wherein Z is a hydrogen or halogen atom, an alkoxy or

• *

means a nitro group. \

The following are examples of aminobenzenes of the formula (7):

Aniline and especially halogenated anilines such as 2-, 3- or 4-chloroaniline, 3,4-dichloroaniline, 2,3-dichloroaniline, 2,4-dichloroaniline, 2,5-dichloroaniline, 2,6-dichloroaniline, 2,3 , 4-trichloroaniline, 2QgSg ^ yI "JjI

2, 4, 6-Trichloran.ilin, 3,4,5-trichloroaniline,

2,4,6-triraethylaniline, '·

2-, 3- or 4-broiaaniline,

2,4-dibromaniline,. . ■ ·. ·

2,5-bibromaniline, 2-! Ie thy 1-5-chi or anil in,

2-Methy1-4-chloroaniline, '■

• 2-methyl-3-chloroaniline, · '

2-chloro-5-trif luorniethy! Aniline, * ·;

also nitroanilines, such as

2-, 3-or. 4-H it ro anil in, 4-chloro-2-nitroaniline, "

2-chloro-4-nitroaniline,

4-methyl-3-nitroaniline, ~ *. ■ '

2,4-dimethyl-3-nitroaniline,

2-methyl-5-nitroaniline,. · ·

2-methy1-4-nitroaniline, also alkoxy and phenoxy anilines, such as

2- and 4-Hethoxyanilin,. .

2- and 4-ethoxyaniline, '. ·

3-Ch1οr-4-methoxyanil in, 2-kethoxy-4-nitroaniline,

2-methoxy-5-nitroaniline,. ■

2-methoxy-5-chloraniline, 2-methoxy-4-chloroaniline, 2-methoxy-5 ~ tri fluorine thy! Aniline, 2-nitro-4-tri fluorine thyl aniline, 3,5-ditrifluoromethyl aniline 4- Nitro-2-trif luo rtaethylaniline 2-Amino-4-trifluoroethyl-4 '' - chloro-diphenyl ether, 2-Nitro-4-etho: <yaniline , 2-Ketho: vy-4-chloro-5-Eiet.hylani ' lin, 2-amino-4-chloro-diphenyl ether, -2J4 ¹ dichloro-diphenyl _{ether t} .

209852/1121

2-Anino-4, 4 '-dichlorodiphenyl ether, so / ie 1-Amino-2-carboxylic acid thys ter, l-Amino-2-chloro-5-carboxylic acid _{methyl ester>} 2-amino-5-nitrobenzoic acid methyl ester, l ~ Amino-2-methyl-5-carboxylic acid methyl ester, l-amino-2-riethy 1-5-carboxylic acid phenyl ester, l-amino-2-chloro-5-carboxylic acid methyl amide, 2-amino-4-trifluoromethyl-diphenyl ether , l-Amino-2-raethoxy-5-carboxylic acid ethyl ester, l-Amino-2-methoxy-5-carboxylic acid amide, 2-Amino-terephthalic acid dimethyl ester, Amino-isophthalic acid dimethyl ester, 3-Ainino- Phthalic acid dimethyl ester, 4-amino-phthalic acid diethyl ester. ·. ·

Examples of aminobenzenes of formula (8) are:

4-Kethyl-3-aninobenzoic acid-2'-chloro-5 '~ trifluorinethyl anilide, 4 ~ chloro-3-aminobenzoic acid-2', S'-dichloroanilide, 4-chloro-3-aminobenzoic acid-2 ^I -chlo £ - 5 ^l -carboDiethoxyanilid _J 4-chloro-3-aminobenzoic acid ^3-t -chloranilid, 4-chloro-3-aminobenzoic acid 2-chloro-5 -''- '-trif luormethylani'lid, A-chloro-S-S-aiainobenzoesäure '-triflu'ormethylanilide, A-chloro-S-aminobenzoic acid-S', 5'-bis-trifluoromethylanilide, 4 ^ -Chlor-3-aminobenzoic acid-2 ^l , 4 ', S'-trichloroanilide, 2,4-dichloro 3-aniinobenzoic acid-2 ', 5 ^L dichloro anilide, 2,4-dichloro-3-aniinobenzoic acid "3 ^l -trif luoriaethylanilide, 2,4-dichloro-3-aiainobenzoic acid e-3' -chloro anilide , 5- * Amino-4-raethoxy-2-chlorobenzoic acid ~ 3'-trifluoromethylanilide, 4-methyl-3-aminobenzoic acid-2 ', 5 ^f -dichloroanilide, 4-methyl-3-aainobenzoic acid ™ 3'-trifluomethyl anilide, 4 -Methoxy-3-aninobenzoic acid ~ 3'-chloroanilide, 4-i'iethoxy-3-aniinobenzoic acid-2 ^f , 5'-dichloroanilide, 4-methoxy-3-aminobenzoic acid-2 ', 4', 5'-urlchloroanilide, 4 -Carbomethoxy-3-aiui nob en zoe säure anil id,

209862/1121

4-methoxy-3-arainobenzoic acid-3 '- trifluorne thy 1 anilide, A-carbethoxy-3-aainobenzoic acid-2', 5'-dichloroic acid, 4-methoxy-3-aminobenzoic acid-3 '»5 '-bis-trifluorniethylanilid, A-methoxy-3-aminobenzoic acid-2'-chloro-5'-trifluoromethylanilide, 4-methoxy-3-aminobenzoic acid-2 ^l _J 5'-dimethoxy-4 ^t -chloranilid, 4-methoxy-3 -aminobenzoic acid-2 ', 5'-dimethyl-4'-chloroanilide.

The azo dye carboxylic acids obtained are with agents that are capable of converting carboxylic acids into their halides, e.g. chlorides or bromides, so in particular with phosphorus halides, such as phosphorus pentabromide or phosphorus trichloride or pentachloride, phosphorus oxyhalides and preferably with thionyl chloride.

Treatment with such acid-halogenating agents is expedient in indifferent organic solvents, such as dimethylformamide, chlorobenzenes. e.g. mono- or di- ' chlorobenzene, toluene, xylene or nitrobenzene carried out, in the case of the last 5, optionally with the addition of Dimethylformamide. -. ■ ·.

When preparing the carboxylic acid halides, it is usually ■ expedient to use those prepared in an aqueous medium To dry azo compounds first or to free them azeotropically from water by boiling in an organic solvent. This azeotropic drying can, if desired, be carried out immediately before the treatment with the acid-halogenating agents be made. "

The azo dye carboxylic acid chlorides obtained are condensed one with amines of the formula (5), preferably with an amine of the formula

20985? / 11.? 1

-δ

where X is a direct bond or a --CH group and Z ₁ , Z ", Z, have the meaning given.

The following are examples of amines of the formula (5) or (9):

N,

^N i

N.

NJ.

N.

N.

^: N.

- (A (4 - (4 - (A "(4

(4 · - (4 "(A

¹ -Ainino-3, 3 '-di chi orb iphenyl) -Ii -Phenyl-urns tof f ^l -amino-3,3 ^t -dichlorobiphenyl) -N ₂ - (4 ^l ' -Chlorpheny1) -urea ¹ -amino- 3,3'-dichlorobiphenyl) -N ~ (4 ^'f -Metboxyphenyl) -harns toff -Ami η o-3, 3 -di * chi orb iphenyl) -N - (4''-Me thy Iphenyl) -harns toff '-Ami no-3, 3 ^l -dichlorobiphenyl) -N - (4 ^t ' -Ae t boxy phenyl) -urs toft ¹ -amino-3,3'-dichlorobiphenyl) -N- (2 "- me thyIphenyl) urea '-amino-3,3'-dichlorobiphenyl) -N _o - (2 ^II -chlorophenyl) urea

Z <.

.N ₀ - (S ¹ '-chlorphenyl) -barns tof f

'-Amino-3,3 ^f -dichlorobiphenyl) -N- <3 ", 4" - dichlorophenyl) -urine-

material

-Araino - 3,3'-dichlorobiphenyl) -N £ '(3 ^l ' -Trif luorme thylphenyl) -

urea

^l- Amino-3,3'-dichlorobiphenyl) -N ^ (4 "- TrifluoromethylphenyI) -" ^: · .- ■ · * .. ■ '· urea

'-Amino-3, 3 ^l -dichlorobiphenyl) -Nr- (4 ^l ' -carbociethoxyphenyl) -

urea

Ν
N
N

- (4'-Araino-S.S'-dichlorobiphenyl) -N - (a-naphthyl) -urea

- (4

- (4

'-Amino-3,3'-dichlorobiphenyl) -N- (cyclohexyl) -urea

^l -Aniino-3,3'-dichlorobiphenyl) -N- (methyl) -urea N - (4'-AmInO-S, ^ ¹ -dichlorbiphenyI) -N ₂ - (η-butyl) -urea ff '-amino- 2,2'-dichlorobiphenyl) -N-phenyl-urea

- (4 - (4 - (4 - (4 - (4

'-Aminobiphenyl) -N -phenylurea

'-Aminobiphenyl) -N- (4 ^f ' -chlorpheny1) -urea '-aminobiphenyl) -N - (2''- methylphsny1) -urea' -aninobiphenyl) -N - (3 ¹ ', 5 ¹ ' -di trif luoriaethyl phenyl) -

2Γ0 9 8 57 / -1 1? 1 urea

N ₁ - (4'-aminobiphenyl) -N ₂ - (3 ¹ '-chloro-4 "-methylphenyL) -urea

N '- (4'-aminobiphenyl) -N ₂ -a-naphthyl urea N ₁ - (4' -aminobiphenyl) - ^ - methyl urea

N, - (4'-Amino-diphenylether) -N ₂ - (4 "-chlorophenyl) -urea

N-, - (4'-amino-diphenylmethane) -N ₂ - (4 "-chlorophenyl) -urea

Ν -.- (4'-amino-stilbene) -N ₂ -phenyl-urea N ₁ - (4'-amino-azobenzoI) -N - ^(1: 4 '-chlorophenyl) -urea

N - (4'-Amino-3,3'-dime thyIbiphenyI) -N - (4 '' - chlorophenyl) -urea N ₁ - (4'-Amino-3 > 3'-dimethoxybiphenyI) -N- (4 ''-methyIphenyI) -

. urea

Nr- (5-Aminοτ 1-naphthyl) -N -Eheny1-urea

N ₁ -C 4 - Amino-1-naphthyl) -N - (4'-chlorophenyl) urea

N _- "(4-Araino-l-anth" rachinony 1) -N- - (4'-chlorophenyl) -urea

N - (5-Amino-1-anthraquinony1) -N -Pheny1-urea

N - {6-Amino-2-anthraquinony1) -N - (4'-chlorophenyl) -urea N - (4'-Amino-3,3 ', 5,5'-tetrachlorobiphenyl) -N -pheny1-urea N - (4'-Amino-3,3 ', 6,6'-tetrachlorobiphenyl) -N _? ~ (4'l-methyl-

phenyl) urea

N - (4'-Amino-3,3'-dimethy1-6,6'-dichiorbiphenyI) -N -pheny1-

urea

N ₁ - (4 ^l -amino-3,3 ^l -dimethoxy-6,6 ^! -DichiorbiphenyI) -N -pheny1-

urea

H- - (4 '-amino-3, 3 * -dicarboaiethoxybipheny I) -N - (4' '-chlorphanyl) -

urea

N .- (4'-Amino-3,3'-dicarboaethoxybiphenyl) -N -pheny1-urea

N ₁ - (Z'-amino- (7 ^f ) diphenylene oxide) -N -pheny1-urea

N - (2'-Ainino- (7 ') - fluorene) -N - (4 ¹ ' -chlorophenyl) -urea

N, (2'-Amino- (7 ') - carbazo1) -N -pheny1-urea 1 - 2

N ₁ - (S '- amino- (6') - ca rbazole) -N -phenyl-urea N- (2'-aiaino- (7 ^I ) -fluorenone) -N-phenyl-urea

209852/112 1

N - (2'-AnInO- (7 ^f ) -diphenylsulfon) -N -4 "-chiorpheny1-urea 4.-Amino-4" - -phenylureido-2., 5-dipheny 1-Ί, 3, 4 -oxdiazole

3'-Αΐηίηο-4 ', 4' '- dichloro-3' 'phenylureido-2,5-diphenyl-

1,3,4-oxdiazole. . . · - "· -" ~

The condensation between the Carbonsäüehalogeniden type mentioned and the amines is expedient carried out in an anhydrous medium. On this condition it is generally surprisingly easy even at temperatures that are in the boiling range of normal organic solvents, such as toluene, monochlorobenzene, dichlorobenzene, trichlorobenzene, nitrobenzene and the like. To speed up It is generally recommended to use an acid-binding agent, such as anhydrous sodium acetate, for the implementation or use pyridine. The dyes obtained are partly crystalline and partly amorphous and are mostly very good yield and pure condition. It is useful to deposit the acid chlorides obtained from the carboxylic acids for the time being. In some cases, however, you can do without Damage to a separation of the acid chlorides are dispensed with and the condensation immediately afterwards to the production of the carboxylic acid chlorides.

2 0 9 8 5 2/11 :? 1

- ir -

According to the embodiment Cb) of the method according to the invention The new dyes can be obtained by using a diazotized aminobenzene, in particular one of formula (7) or (8) couples with a naphthol of formula (6).

The coupling takes place through the gradual addition of the aqueous alkaline Solution of the coupling component to the acidic solution of the Diazoniuinsalzes instead. The solution to the coupling component Alkali hydroxydraenge to be used is expedient dimensioned so that they -for the neutralization of the mineral acid liberated from the diazonium salt during the coupling sufficient. The coupling becomes useful at a ρ value

performed from 4 to 6. The ρ value is advantageous by

Addition of a buffer discontinued. The salts, especially alkali salts of formic acid, are used as buffers, Phosphoric acid or especially acetic acid into consideration. Contains the alkaline solution of the coupling component appropriate e.g. in wetting, dispersing or emulsifying agents, for example an aralkyl sulfonate, such as dodecyl benzene sulfonate or the sodium salt of 1,1'-naphthylmethanesulfonic acid, Polycondensation products of alkylene oxides, such as the product of the action of ethylene oxide on p-tert.-octylphenol, also alkyl esters of suIforicinoleates, for example n-butyl sulforicin oleate. The dispersion of the coupling component can also be advantageous protective colloids, for example Methyl cellulose or small amounts of inert organic solvents that are sparingly soluble or insoluble in water contain, for example optionally halogenated or nitrated aromatic hydrocarbons such as benzene, toluene, Xylene, chlorobenzene, dichlorobenzenes or nitrobenzene, as well as aliphatic halogenated hydrocarbons such as e.g. carbon tetrachloride or trichlorethylene, also water-miscible organic solvents such as acetone, ethyl ethyl ketone, Methanol, ethanol or isopropanol.

209952/1171. V

r 12-

Han can also carry out the coupling advantageously in such a way that that one nit an acidic solution of the diazonium salt an alkaline solution of the coupling component in a mixing nozzle continuously combined, with an immediate Coupling of the components takes place.

The resulting dye dispersion is continuously fed to the mixing nozzle removed and the dye separated off by filtration.

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

The aryldiazoamino compounds to be used according to embodiment b) of the process according to the invention are obtained by known processes by reacting an aryldiazonium salt with a primary or, preferably, with a secondary amino compound. A wide variety of amines are suitable for this purpose, for example aliphatic amines, such as methylamine, ethylamine, ethanolamine, propylamine, butylamine, hexylamine and, in particular, dimethylamine, diethylamine, diethanolamine, methylethanolamine, dipropylamine or dibutylamine, aminoacetic acid, methylaminoacetic acid, methylaminoacetic acid, methylaminoacetic acid, aminoacetic acid, methylaminoacetic acid, ethylaminoacetic acid, butylaminoacetic acid, butylamine. Guanylethanesulfonic acid, ß'-Aminoäthy1sulfur acid, alicyclic amines, such as cyclohexylamine, N-Hethylcyclohexy1-atnine, dicyclohexylamine, aromatic amines, such as 4-aninobenzoic acid, sulfani1 acid, 4-sulfo-2-amylinobenzoic acid, 4-sulfo-2-amylinobenzoic acid, 4-sulfo-2-amylinobenzoic acid -N-Methylaininobenzoic acid, A-Ethylaminobenzoic acid, 1-Arcinonap'n thai in-4-sulfonic acid, l-Ani no ~ naphthalene-2,4-disulfonic acid, heterocyclic amines, vie

'2 098 5? / 11 ?!

Piperidine, morpholine, pyrrolidine, dihydroitidol and finally also sodium cyanamide or dicyandiamide.

As a rule, the diazoamino compounds obtained are sparingly soluble in cold water and, if necessary, can be added Salting out in crystallized fora from the reaction nediura be separated. In many cases the moist press cakes can be used for the clutch. In individual In some cases, it may be expedient to dehydrate the diazoamides by vacuum drying prior to the reaction.

The coupling of the diazoamino compound with the coupling component takes place in an organic solvent, for example Chlorobenzene, o-dichlorobenzene, nitrobenzene, Pyridine, ethylene glycol, ethylene glycol monoethyl ether or monomethyl ether, dimethylformamide, formic acid or acetic acid. When using solvents that are miscible with water, it is not necessary to use the diazoamino compounds to be used in anhydrous form. For example, the watery, moist suction cup can be used will.

The coupling is expediently carried out in the warm, preferably at temperatures between 80 and 180 ° C., in an acidic medium

carried out and is generally very quick and

Completely. If you use neutral solvents, so is

the addition of an acid, for example hydrogen chloride,

Sulfuric acid, formic acid or acetic acid, beneficial,

Thanks to their insolubility, the pigments obtained can

isolated from the reaction mixture by filtration.

A post treatment with organic solvents like this in the case of pigments is required, which on your watery coupling path is therefore unnecessary in most cases. -

209852 / 11.71 '. ·' .-

The new dyes are valuable pig-nients, which in finely divided form for pigmenting high molecular weight organic material can be used, e.g. cellulose ethers and esters, super polyalides or Super-polyurethanes or polyesters, acetyl cellulose, Nitrocellulose, 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, polyolefins, such as polystyrene, polyvinyl chloride, polyethylene, Polypropylene, polyacrylonitrile, polyacrylic acid ester, Gunmi, Casein, silicone and silicone resins, individually or in mixtures.

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

Compared to analogous dyes in the British patent specification l'O77 077, which in the arylide group instead of the benzidine group Have the benzene group, have the dyes according to the invention a better migration.

The dye of Example 38 of the present invention is distinguished from example 52 of British patent specification 1,777,077 by a stronger and more beautiful shade as well as better migration authenticity.

In the following examples, the parts mean, if nothing else is indicated, parts by weight, percentages Weight percentages and temperatures are in degrees Celsius specified;

209852/1121

Example 1 . - · ~

20.5 parts of the diazotized by coupling! 2-nitro-4-trifluoromethyl aniline dyestuff obtained with 2,3-hydroxynaphthoic acid v / earth with 550 parts of o-dichlorobenzene, 8.3 parts of thionyl chloride and 1 part of Dimethylforiaaeid heated with stirring to 135 to 1.45 for 2 hours, everything going into solution. After the reaction device has cooled down the uniformly crystalline azo dye monocarboxylic acid chloride is isolated by filtration.

washed with 400 parts of eenzene, then with 200 parts of petroleum ether. After drying at 50 im 17.5 parts of a red crystal powder.

washed. After drying at 50 in vacuo, one obtains

6.35 parts of the azo dye carboxylic acid chloride thus obtained are stirred in 500 parts of o-dichlorobenzene and 1.2 parts of pyridine and heated to 80-90. Then a warm solution of 6.6 parts of Nj- (4'-amino-3,3 ^! -Dichlorodiphenyl) -H - (4 "-chlorophenyl) urea in 20 parts of dimethylformamide and 20 parts of o-dichlorobenzene is added and heated for 12 hours to 140 to 145; the sparingly soluble pigment which precipitates out in fine crystalline form is filtered off while hot and washed with hot o-dichlorobenzene until the filtrate runs off clear, then washed with cold methanol and finally ¹⁵¹ % hot water. After drying at 80 in vacuo, 9.9 parts of a soft-grain powder are obtained which is practically insoluble in the usual solvents and which colors the polyvinyl chloride film and lacquers in orange shades of excellent lightfastness, migration and varnish fastness. The pigment corresponds to the formula "-

KO ^ ₂ 209852/1 121

oh \ = / ^j (XU)

COiIH- '' ^ ft \ ^ _ iinrr.?in_^ v \

Cl

Example 2 ^

27.5 parts of the dye obtained by coupling 4-chloro-3-ainobenzoic acid- (2'-chloro-5'-trifluoromethyl) phenyl amide with 2,3-hydroxynaphthoic acid by coupling diazotised in glacial acetic acid, hydrochloric acid and sodium nitrite are mixed with 600 parts of chlorobenzene, 11.5 parts of thionyl chloride and 3.5 parts of dimethyl formamide and heated to 55 to 60 hours with stirring. After the reaction mixture has cooled, the uniformly crystalline monocarboxylic acid chloride of the dye is isolated by filtration, washed with cold benzene and dried at 50 ° in vacuo.

1.4 parts of this chloride are stirred in 100 parts of o-dichlorobenzene and heated to 60. A warm solution of 0.85 part of N - (4'-aminobiphenyl) -N (Pheny1) -urea in 4 parts of di-ethyl-formamide is then added and the mixture is heated to 140 to 145 for 12 hours. The crystalline, sparingly soluble Pigrcent is then filtered off while hot and washed with hot o-dichlorobenzene, cold methanol and hot water and dried at 70 to 80 in vacuo. The obtained dye of the formula

(XIII)

is a red pigment that is found in common solvents is difficult to insoluble and what the polyvinyl chloride film as well as paints in excellent light, migration and varnish right red tones,

209852/112 1

Example 3

47.5 parts of the dye, which is diazotized by coupling in glacial acetic acid, hydrochloric acid and sodium nitrite! 2,4,5-Trichloroaniline with 2,3-hydroxynaphthoic acid is obtained in a mixture with 650 parts of o-dichlorobenzene, 20 parts of thionyl chloride and 2 parts of dimethyl formamide with stirring for two hours at 135 to 145 ° C., everything dissolving. After the reaction mixture has cooled, the uniformly crystalline monocarboxylic acid chloride of the dye is isolated by filtration, washed with 400 parts of benzene and then with 200 parts of petroleum ether. After drying at 50 to 60 ^Q ci vacuum, 39 parts of the dye acid chloride as a red crystal powder.

6.3 parts of this chloride / earth in 500 parts of o-dichlorobenzene and 1.2 parts of pyridine are stirred and heated to 80 to 85.degree. Then you give a warm solution of 5.5 parts N- - (4'-Amiηo-diphenylmethai) -N- (4 '' - chlorophenyl) urea in 20 parts of dimethylformamide and heated for 12 hours to 140 to 145 C. The finely crystalline sparingly soluble pigments are filtered off with hot water and washed with hot o-dichlorobenzene until the filtrate runs off clear, then with cold methanol and finally with hot water washed. After drying at 80 to 85 in vacuo, 9.0 parts of a soft powder are obtained, which in the usual Solvents is practically insoluble and which is the polyvinyl chloride foil and paints in excellent light, orange tones that are resistant to migration and varnish.

2 0 9 8 5 2/1 12 1

- 13 -

222677-3

The Pignent corresponds to.!: The formula

(XIV)

CII- / V-NHCONII

There are other monoazo pigments in the table below which are obtained by following the in Paragraph 1 described method 1 mole of the diazo compound of the amines mentioned in column 1 to 1 haul of the coupling component the 2,3-hydroxynaphthoic acid mentioned in column II couples the obtained ilonoazo carboxylic acid transferred into the acid chloride und.mit 1 Hol of the in column III called amine condensed. Column IV denotes the hue of a polyvinyl colored with the pigment obtained chlorine idf oil ie.

2 0 9352/112 1

No. I. II III IV 4th 2,5 dichloro
aniline 2,3-hydroxy
naphthic acid Ν .- (4'-Amino-3,3'-dichlorobiphenyl) -N ₂ - (4 ^M -
chlorophenyl) urea orange 5 Il Il Ni- (4'-amino-3,3'-dichlorobiphenyl) -N ₂ -
a-naphthyl urea Red 6th Il M. N, - (4'-Amino-diphenylmethane) -N ₂ - (4 "-chlor-
pnenyl) urea Red 7th Il Il N ₁ - (4'-Amino-biphenyl) -N ₂ - (4 "-ethoxyphenyl) -
urea Red 8th M. 6-methoxy-2,3-
Hydroxynaphtho e -
acid N- (4'-aminobiphenyl) -N ₂ -phenyl-urea bordo 9 M. 6-nitro-2,3-
Hydroxynaphtho e -
acid Il Red - 10 Il ' 2,3-hydroxy
naphthic acid N ₁ - (4 .'-Amino-3,3'-dichlorobiphenyl) -N ₂ - (4 ^M -
methyl! phenyl) urea Scarlet fever 11 Il M. N ₁ - (4'-aminobiphenyl) -N ₂ - (4 "-chlorophenyl) -
urea Red 12th Il Il N ₁ - (4'-aminobiphenyl) -Ng-methylurea Red 13th Il Il N ^ - (4 '-aminobiphenyl) -N-j-cyclohexyl urea Red .14 It 6-bromo-2,3-
Hydroxyriaphtho e-
acid N -, - (4'-aminobiphenyl) -N ₉ - (4 "-methylphenyl) -
urea ^c Red

No. I. II III IV 15th 2-chloro-5-tri-
fluoromethyl
aniline 2,3-hydroxy
naphthic acid N ₁ - (4'-aminobiphenyl) -N ₂ - (4 "-ethoxyphenyl) -
urea orange 16 Il Il N ₁ - (4 '-aminobiphenyl) -N ₂ -phenylurea Scarlet fever 17th Il ti N ₁ - (4 ^r -amino-3,3'-dichlorobiphenyl) -N ₂ - (4 "-
chlorophenyl) urea orange 18th Il It N ^ - (4'-aminobiphenyl) -No- (4 "-chlorphenyl) -
urea Red 19th 2,4,5-trichloro
aniline Il ti Red 20th Il Il N ₁ - (4'-Amino-3,3'-dichlorobiphenyl) -N ₂ - (4 "-
methylphenyl) urea Red 21st M. Il, N ₁ - (4'-aminobiphenyl) -N ₂ -methyl urea orange 22nd Il Il N, - (4'-Amino-3,3'-dichlorobiphenyl) -N ₂ - (4 "-
chlorophenyl) urea orange 23 Il Il N ₁ - (4'-aminobiphenyl) -N ₂ - (4 "-methylphenyl) -
urea Brown 24 2-methoxy-5-
trifluorine
methylaniline Il N, - (4 ¹ -amino-3,3'-dichlorobiphenyl) -N ₂ - (4 "-
chlorophenyl) urea Red

O CO CO

No. I. II Il III IV 25th 2-nitro-5-tri-
fluoromethyl
aniline Il N ₁ - (4'-aminobiphenyl) -N ₂ - (4 "-chlorophenyl) -
urea Brown 26th 2- (4'-chlorine) -
phenoxy-5-tri-
fluoromethyl
aniline Il N ₁ - (4'-amino-3,3'-dichlorobiphenyl) -N ₂ -phenyl-
urea ■ Brown 27 2-methoxy-5-
chloraniline Il N ₁ - (4'-Amino-3,3'-dichlorobiphenyl) -N ₂ -
(a-naphthyl) urea bluish tint
Red 28 M. Il Ν -, - (4'-Amino-biphenyl) -N ₂ - (4 "-chlorophenyl) -
.urea bluish tint
Red 29 2-methoxy
4-chloroaniline Il It Red 30th 2-methoxy
4-nitroaniline Il Il bordo 31 Anthranilic acid
methyl ester Il N ₁ - (4'-Amino-3,3'-dichlorobiphenyl) -N ₂ - (4 ^M -
methylphenyl) urea orange 32 Il Il N ₁ - (4 '-Aminobiphenyl) -N ^ phenyl-urea f bluish tint
Red 33 Il Il Ν ·, - (4'-aminobiphenyl) -N ₂ - (4 ^M -methylphenyl) -
urea bluish tint
Red 34 2-ethylsulfony!
5-trifluoro
methylaniline N ₁ - (4'-Amino-3,3'-dichlorobiphenyl) -N ₂ - (4 ⁿ -
chlorophenyl) urea orange

Q)

O Vi

4J O Vi

(U

ß °

CD

O year

4-> O Vl

4Y O

(U

ß °

CD

CU

cd Vi O

r-J

Xi

CN

C. (U X! ft •H

O <t CQ

CN

53

ß Q)

ft • Η

, η

Vl

Xi MI

CJ M-I

• Η O

Ό 4Y

I CQ

^ Cd

CO Xi

I I

• Η >>

ε β

<CJJ

I Xi

crack

3 O

β Q) Xi ft

4-1 CU

CNJ

(U

τ-Ι

O β

M-J M-J O 4J CQ β

M-I M-J

O JJ

CQ

Xi ι

β (U

ft

CN

Q) Xi

ft • Η Xi

• Η

γ-Ι

SS

β Q)

ft Vi O r-l

CM

Q) Xi ft

• Η

E ¹ W

<2 M-J

O

- 4Y

-ί CQ

Vl

i-jcd

β ft

yy cu β ι

CN

! 3

β Q) Xi ft

<2 4-y

I O

- 4Y

<f CQ

ι Vj

t-Jcd

CN

β (U C

CJ M-J n-l O

• σ 4J

I CQ

co u

• cd

CO, β

ßrH

J =

Q)

Xi ft

Φ I Vl

O CQ

UQ) TJ O

^ i

K 4J

ι Xi

Ks ft CN β

β ο

M-J ΐ-Ι

O β

d r-J I-J

CQ M-J T-J

r-J T-I >

β =

>> U d N 4Jr-J β I >>.

o m χ;

PQ I 4J I ΐ-Ι CU

cn t * n

CO »ι - Ι

I-J T-J

>> β

yes cd JJ Vi CU O

I rß

CN CJ

I.

in xi

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Οββ HOH

ι cd β

CN CJ Cd

Vt I. I. ι Vj O Q) ω JC U 4Y υ 3 O CQ ι xd CU CQ 4Y I. CU CU > ", O O R. β
CU β β ι JC " • Η CU νΐ Jl Xt ι CO

m co

CO

co

οο co

approx

co

209852/1121

No. I. II III IV '. 44 3-amino-4-chloro
benzoic acid (4 -
methoxyphenyl
ester 2,3-hydroxy
naphthoic acid N ₁ - (4'-aminobiphenyl) -N ₉ -phenyl-urea
Ju ί * Red 45 3-amino-4-
schlorbenzoe-
acid-2'-chlorine-
5'-trifluoro
methylanilide Il N ₁ - (4 '-Aminobiphenyl) -N ₂ - (4 "-Aethoxyphenyl) -
urea Red 46 ι: Il N ₁ - (4'-Amino-3,3'-dimethoxybiphenyl) -N ₂ -
(4 ^M -chlorophenyl) -urea Red 47 Il Il N ₁ - (4'-aminobiphenyl) - (3 "-chlorophenyl) -
urea Red 48 Il Il N ₁ - (4'-Amino-3,3'-dichlorobipheny1) -N ₂ -
(4 ~ "-chlorophenyl) -urea. Red 49 4-chloro-3-amino
benzoic acid-3'-
trifluoromethyl
anilide Il It Red 50 Il Il N ₁ - (4'-aminobiphenyl) -N ₂ - (4 "-chlorophenyl) -
urea Red 51 M. Il N ₁ - (4'-aminobiphenyl) -N ₂ - (4 "-ethoxyphenyl) -
urea Red

No. I. II III IV 52 3-amino-4-chloro
benzoic acid
anilide 2,3-hydroxy
naphthoic acid N ₁ - (4 '-Aminobiphenyl) -N ₂ - (2''-methylphenyl) -
urea Red 53 Il Il N, - (4'-Amino-3,3'-dimethylbiphenyl) -N ₂ -
(4 '' - chlorophenyl) urea orange 54 Il It N ₁ - (4'-Amino-3,3'-dichlorobiphenyl) -N, -
pnenyl urea Red 55 M. It N -, - (4 '-Aminobiphenyl) -N ₉ - (4''-chlorophenyl) -
urea Red 56 3-amino-4-chloro
benzoic acid-2'-
methyl-3 ¹ -chlor
anilide Il Red 57 Il Il N ₁ - (4'-aminobiphenyl) -N ₂ -cyclohexyl-urine
material Red 58 3-amino-4-chloro
benzoic acid
3'-carbomethoxy
anilide Il It Red 59 ti Il N ₁ - (4 ¹ -Aminobiphenyl) -N ₉ - (4 ¹ '-chlorophenyl) -
urea ^Δ Red 60 3-amino-4-
methoxybenzoic
acid anilide Il N ₁ - (4'-aminobiphenyl) -N ₉ - (4 '' - chlorophenyl) -
urea bluest,
Red

3-amino-4-methyl-benzoic acid, 2 ', 4'-dimethyl-anilide

3-amino-4-methy benzoic acid isopropylamide

Il

3-Amino-4-methoxy-benzenesulfonic acid phenyl ester

3-Amino-4-chlorobenzoic acid-2'-methoxyanilide . ,

3 - Amino - 4-methylbenzoic acid 4 ¹ -chlorophenyl ester

3-Amino-benzoic acid-3 ¹ -trifluoromethylanilide

II

2,3-hydroxynaphthoic acid

Il

Il

Il

Il

Il III

N, - (4 ¹ -Aminobiphenyl) -Na- (4 ¹ '-methylphenyl)
urea

N - (4'-aminobiphenyl) -N «-phenyl urea

N ₁ - (4 ¹ -aminobiphenyl) -N ₉ - (4 "- ethoxyphenyl) ■
urea

Il

N ₁ - (4 ¹ -Aminobiphenyl) -N ₉ - (4 ¹ '-chlorophenyl) -

Il

N ₁ - (4 ¹ -Aminobiphenyl) -N ₉ - (4 * '-chlorphenyl)
urea

IV

bluish, red

bluish, red

bluish, red

Red

Red

Red

Red

ISJ GC "

No. I. II III IV Red 68 2,5 dichloro
aniline 2,3-hydroxy
naphthoic acid N ₁ - (4 ¹ -Aminobiphenyl) -N ₂ - (3 '' - chlorophenyl) -
urea Red 69 2,4,5-trichloro
aniline Il N ₁ - (4'-aminobiphenyl) -N ₂ - (4 '' - ethoxyphenyl) -
urea Red 70 11 Il N ₁ - (5'-amino) -l-naphthyl-N ₂ - (4 '' - chlorophenyl) -
urea Red 71 2,5 dichloro
aniline 11 It Brown 209ί 72 Il Il N ₁ - (4 ¹ -amino) -1-naphthyl-N ₂ - (4 * '- chloro) phenyl-
urea Red 152/1 12 73 3-amino-4-chloro
benzoes acre
s'-tr if luor-
methylanilide Il Il Red 74 3-amino-4-chloro
benzoic acid
anilide 11 Ν, - (4'-amino-diphenylaether) -N ₂ - (4 '' - chlorine-
pnenyl) urea Red 75 3-amino-4-chloro
benzoic acid-5 ¹ -
trifluoromethyl
2'-chloroanilide Il Il orange 76 2-amino-tereph-
thalic acid-di-
methyl ester Il N ₁ - (4 ¹ -amino-3,3 ¹ -dichlorobiphenyl) -N ^ phenyl-
urea

ro ro ro

ro ο to QO cn

No. I. II III ' IV 77
!
t 2-amino- t ereph-
thalic acid-di-
methyl ester 2,3-hydroxy
naphthoic acid Ν, - (4 ¹ -amino-3,3idichlorobiphenyl) rN ₂ - (4 "-
chlorophenyl) urea orange 78 3-amino-4-
chlorobenzoe
acid amide ! » Il Red 79- 3 -Amino - 4 -me -
ethyl benzene
sulfonic acid
ethyl ester. It Il red . 80 3-amino-4-
methyl benzene
sulfonic acid
diaethylamide Il Il Red 81 3-amino-4-
methyl benzene
sulfonic acid
ethylamide Il N ₁ - (4 '-Aminobiphenyl) -N ₉ (-4 ^1' -chlorophenyl) -
urea . Red 82 3-amino-4-
methyl benzene
sulfonic acid
phenylamide Il Il Red 83 2,5 dichloro
aniline M. N ₁ - (4 ¹ "amino-3,3 '-dichlorobiphenyl) -N" - (4 "-
trifluoromethylphenyl) urea Red

N / A

ro

ro oo

CO

ro ο to oo 'SI

• si

No. I. II. III IV 84 2.5, -dichlor-
aniline 2,3-hydroxy
naphthoic acid N ₁ - (4 ¹ -amino-3,3'-dichlorobiphenyl) -N ₂ - (4 "-
carbomethoxyphenyl) urea Red 85 3-amino-4-
c arbomethoxy
benzoic acid
4'-chloroanilide Il N ₁ - (4 * -amino-3,3'-dichlorobiphenyl) -N ₂ - (4 ^f V-
chlorophenyl) urea Red 86 3-amino-4,6-
dichlorobenzoe
acid anilide Il Il . Red 87 2,5 dichloro
aniline It N, - (5-Amino-l-anthraquinonyl) -Nn-phenyl-
urea Red 88 M. It N ₁ - (4 ¹ -aminostilbene) -N ₂ - (4 '' - chlorophenyl) -
urea Red 89 2,4,5-trichloro
aniline Il Il Brown 90 3-amino-4-
chlorobenzoe
acid-2'-chlorine-
5'-trifluorme-
thylanilide M. Il Red 91 ti Il N ₁ - ^ ¹ -amino-azobenzene) -N ₂ - (4 '' -chlorophenyl) -
urea Red

NO

00

ro ro co

CO

• I } ^ j
O O
U U 2228773 ■ "■ * • rphenyl) - O
-ml υ ι
CM
53 III O Lno-azobens
* ^ t ti ι rnstoi α)
I Lj ydrox
hoesä M. • yes
cn α. CM β ι
* mm
ilor- O O r ^ ti
yes u M. Q · Η in «H m · η sf -rl
** C * *> f * j
CM CU CM Approx cm cn No.

209852/1121

Example 94

8.1 parts of 2,5-dichloro-l-aminobenzene are used in the usual V In each case with aqueous hydrochloric acid, ice and sodium uranium nitrite diazotized. .

On the other hand, 24 parts of N, - £ 4 '- (2 "- hydroxy-3" - naphthoy l-araino) -b iphenyl JN ₁ . -phenylurea dissolved in a mixture of 250 parts of ethylene glycol ethyl ether and 10 parts of 30% sodium hydroxide solution in the cold. 4 parts of the condensation product of 8 moles of ethylene oxide and 1 mole of p-tert-octylphenol are added to the solution and the naphthol is then precipitated with 30% acetic acid with thorough stirring. Coupling is carried out by adding the diazo solution described in paragraph 1 while maintaining a ρ value of 6 to 7 and a temperature of 20 to 25 °. To complete the coupling, stirring is continued for 2 hours at the same temperature, and the resulting pigment suspension is acidified to the Congo by adding hydrochloric acid and filtered off. It is washed with hot water until no more chlorine ions can be detected in the filtrate. After drying at 80 to 90 under reduced pressure gives a good yield de _n red pigment of the formula '· .- "■ ■.

(XV) '

CONH-f / \ V-NHCONH- fy

The properties of the pigment can be improved by post-treatment in an organic solvent such as nitrobenzene.

209852 / 11.21.

It is difficult to insoluble in the usual solvents

and colors the polyvinyl chloride film and varnish in red

Shades of good migration, varnish and lightfastness.

209857/1 1.2 1

Example 95

2.1 parts of the diazoamino compound of the formula

^S0 2 ^C 2 ^H 5

0 II N-N = N-Ti

(XVI)

produced by coupling diazotized 3-amino-4-ethy1 - sulfonyl-benzotrifluoride on morpholine in an alkaline medium, and 2.35 parts of N - [4 '- (2 "-hydroxy-3" -naphthoy 1) aminobiphenylj -N - (phenyl) urea are suspended in 130 parts of o-dichlorobenzene, heated to 121 to 125 and treated with 3 parts of trichloroacetic acid. The mixture is then stirred for one hour at 145 to 150, the cleavage of the diazoamino compound and the coupling to the pigment being ended. The red pigment is filtered off while hot and washed with hot o-dichlorobenzene _s cold methanol and hot water. After drying in vacuo, 2.1 parts of a red mono azo dye of the formula '

(XVII)

It is poorly or insoluble in the usual solvents and colors the polyvinyl chloride film and lacquers in red shades of good migration, overcoating and lightfastness

7 0 9 8 5? η 1 2 1

· -2220773

Example 96

65 parts of stabilized polyvinyl chloride, 35 parts of dioctyl phthalate and 0.2 parts of the dye obtained in Example 1 are stirred together and added rolled back and forth on a two-roll calender for 7 minutes at 140. A pure orange color is obtained Film with very good light and migration fastness.

209852/1121

Claims (14)

Claims
1. Monoazopignent of the formula "" --CONH-R- -NHCONIIR, 3 4. wherein R is an aryl radical, R a haphthalene radical, in which the azo, the hydroxyl and the CO group in the 1,2,3-position stand, R an at least bicyclic aromatic radical and R an alkyl, cycloalkyl, aryl or Mean aralkyl radical. 2. Monoazopigraente genäss claim 1. wherein in the specified Formula R is a benzene radical and R is a radical of the formula Ti —O ~ ^{: Y} 2 ^Y 2 means where X ₁ · a direct bond or an -O atom, an alkylene group or a -CH = CH- or -N = N- group, Y- and Y «H- or halogen atoms, alkyl or alkoxy groups mean. 3. Monoazo pigments according to Claims 1 and 2 of the formula 209852/1121 = Κ on γ CONH -J / V rx .NHCONH- wherein Z is a hydrogen or halogen atom, an alkoxy or a nitro group, X a hydrogen or halogen atom, X "and X- hydrogen or halogen atoms, alkyl, Alkoxy, phenoxy, nitro, carbophenoxy, carbalkoxy, Carbamido, carboxylic acid alkylamido, sulfonic acid alkyl or aryl ester, sulfonamido, sulfonic acid mono- and dialkylamido, Sulfonic acid mono- and diarylamido or trifluoromethyl groups , Y ₁ hydrogen or halogen atoms, alkyl or alkoxy groups, Z, a hydrogen or halogen atom, Z «and Z- hydrogen or Halogen atom, alkyl, alkoxy, carbalkoxy or trifluoromethyl groups mean. 4. Monoazo pigments according to claim 3 of the Forrael NHCONH ^Λ 2 ^Ζ 3 V7orin V denotes a hydrogen or halogen atom, an alkyl, alkoxy or carbalkoxy group, Vi and Z, hydrogen or halogen atoms, Z _r and 7, hydrogen or halogen atoms, alley, alkoxy, carbalkoxy or trifluoromethyl groups and Z, Y, Z, 7. and Z have the specified Badcut. '. »3. 209852/1121 5. Process for the production of monoazo pigments of formula NN- R ₁ I ₂ / ^0H "" -CONIl-R -NHCONH-R. · 3 4 wherein R _{1 is} an aryl radical, R "is a naphthalene radical in which the azo, the hydroxyl and the CO group are in the 1,2,3-position, R an at least bicyclic aromatic radical and R an alkyl, cycloalkyl, Mean aryl or aralkyl radical, characterized in that a) a carboxylic acid halide the formula N = N - R ₁ --COHaI wherein R, and R have the meaning given and Hai Halogen atom means with a monoamine in the formula H ₉ NR-NHCONHR condensed, wherein R and R, have the meaning given ^ or b) a diazo or diazoamino compound of an aromatic one Amine with a naphthol of the formula (VII) CONh-R ₃ -NHCONH-R, clutch. 6. The method according to claim 5, characterized in that one starts from a carboxylic acid halide of the formula given in which R _{1 is} a benzene radical. 7. The method according to claim 6, characterized in that one of a carboxylic acid chloride of the formula 209857/11? 1 COCl emanates from what Z is a hydrogen or halogen atom, · an alkoxy or a nitro group, X a hydrogen or halogen atom, X "and X- hydrogen or halogen atoms, alkyl, alkoxy, phenoxy, nitro, carbophenoxy, carbalkoxy, carbamido, Carboxylic acid alkylamido, sulfonic acid alkyl and aryl ester, Sulfonic acid amido, sulfonic acid mono and dialkylamido, Sulphonic acid mono and diarylamido or trifluoromethyl groups. 8. The method according to claim 7, characterized in that that one of a carboxylic acid chloride of the formula ^ COHH ΛεΓΪ N = / ^Z starts out, in which Z has the meaning given, V is a hydrogen or halogen atom, an alkyl, alkoxy, or carbalkoxy group, W and Z, hydrogen or halogen atoms, Z and Z hydrogen or halogen atoms, "alkyl, 5 6 Mean alkoxy, carbalkoxy or trifluoromethyl groups. 209852/1121 9. The method according to claims 6-8, characterized in that that one of a monoarain of the formula starts out, wherein R has the meaning given in claim 5 X is a direct bond or a -Q atom, an alkylene group or a -CH-CH- or -N = N group, Y and Y ₉ denote H or halogen atoms, alkyl or alkoxy groups. 10. The method according to claim 9, characterized in that that you can get from a monoamine of the formula NHCONH - (/ 'cvf ² starts, in which Y is an H or halogen atom, an alkyl or alkoxy group, 7 denotes a hydrogen or calogen atom, Z and Z_ denote hydrogen or halogen atoms, alkyl, alkoxy, carbalkoxy or trifluoromethyl groups. 11. The method according to claim 5b, characterized in that one of the diaao or diazomino compound Amine of the formula 209852/1121 7228773 starts out, wherein X ^, X ₂ and X ^ have the meaning given in claim 7. 12. The method according to claim 5b, characterized in that that you can get from a naphtol of the formula starts, wherein Y ^, Y ₂ , Z, Z ^, Z ₂ and Z ^ have the meaning given in claims 7 and 10. 13. A method for pigmenting high molecular weight organic material characterized by the use of dyes according to claims. 1-4. 14. The pigmented material obtained according to claim 13.