DE1903649A1 - New water-insoluble azo compounds and processes for their production - Google Patents

Description

DR. BERQ D = PI -.- 'NQ. STAPF

PATEN rANW.-aTE θ MÜNCHEN 2, HILBLESTRASSE 20

CIBA AKTIENGESELLSCHAFT, BASEL (SWITZERLAND)

/ E - 5. 1969

Germany

P 19 03 6 * August 19

New water-insoluble azo compounds and processes for their preparation.

It has been found that one can produce valuable new azo compounds the formula

OH

wherein R, the remainder of a diazotizable amine and R ^ is an H atom or an organic, in particular an aromatic residue, bodeutot, if one

903341/14 * 3

a) a carboxylic acid halide of the formula

N
OH

condensed with ammonia or an amine, or b) a diazotized ψ amine or its diazoamino compound with a naphthol of the formula

clutch. '.-

Particularly valuable dyes are obtained by using a carboxylic acid chloride of the formula. -. ■; . - _; -.

I OH

₀ Μ

COCl

where X ,, Xp and X are hydrogen or halogen atoms, alkyl, Alkoxy, aryloxy, nitro, cyano, trifluoromethyl, carboxylic acid ester, Carboxamide, sulfonic acid ester or sulfonic acid,

Amine / amide groups mean with a / of the formula. ■■ -. .

condensed, in which Y, and Y hydrogen or halogen atoms, Alkyl or alkoxy groups and Y., a hydrogen or halogen atom or represents an acylamino group.

The carboxylic acids on which the halides are based are obtained, in particular, by coupling a diazotized amine of a diazotized aminobenzene with a nitro-2-hydroxy-3-napthoic acid the formula

for example 5- * 7- or 8- but especially 6-nitro-2-hydroxy - ^ - naphthoic acid ..

Diazo components that may be mentioned are: aniline and, in particular, halogenated anilines, such as 2-, 3- or - + - chloroaniline, 3,4-dicloroaniline, 2,3-dichloroaniline, 2,4-dichloroaniline, 2,5-dichloroaniline, 2,6-dichloroaniline, 2,4,5-trichloroaniline,

^ 09841/1493

2, 4, 6-trichloroaniline, 2, J3, or 4-bromoaniline, 2,4-dibromoaniline, 2, 5-dibromoaniline, 2-Me thy1-5-chloroaniline, 2-methyl-4-chloroaniline, 2-methy1 -3-chloroaniline, 2-chloro-5-trifluoromethylaniline, also nitroanilines, such as 2-, 3- and 4-nitroaniline, 4-chloro-2-nitroaniline, 2-chloro-4-nitroaniline3 4-methyl-3-nitroaniline, 2 _} 4-Dimethyl - ^ - nitroaniline, 2-Methy1-5-nitroaniline, 2-methyl-4-nitroaniline, also alkoxy- and phenoxyanilines, such as 2- and 4-methoxyaniline, 2- and 4-ethoxyaniline, ^ -chlorine -4-methoxyaniline, 2-methoxy-5-nitroaniline,

2-methoxy-5-chloroaniline, 2-methoxy-4-chloroaniline, 2-methoxy-5-trifluoromethylaniline, 2-Arnino-4-trif luormethy 1-4'-chloro-dipheny lather, 2-nitro-4-ethoxyaniline, 2-methoxy-4-chloro-5-nie thy la niline,

309841/1493

2-Amino-4-chloro-diphenyl ether, 2-amino-2 ^l , 4 ^l -dichloro-diphenyl ether, 2-amino-4,4'-dichloro-diphenyl ether, and l-amino-2-carboxylic acid methyl ester, l-amino - ^ - chloro ^ -carboxylic acid methyl ester, 2-amino-5-nitrobenzoic acid methyl ester, 4-amino-3-nitro-benzotrifluoride, 2-amino-5-nitro-benzotrifluoride, l-amino ^ -chlorobenzene ^ -carboxylic acid methylamide, 2 _J 5-Öiπlethoxy-4-benzoylamino-aniliri, 2,5-dimethyl-4-benzoylamino-aniline, 2-chloro-5-ethoxy-4-benzoylamino-aniline, 2-methoxy-5-methyl-4-benzoylamino-aniline, 4-methyl-3-aminobenzoic acid amide, ^ -Methyl-J-aminobenzoic acid anilide, 4-methyl-3-3ffiinobenzoic acid-2'-chloro-5'-fcrifluoro-ethylanilide, 4-chloro-3-aminobenzoic acid-3 ' s 5'- bis-trifluoromethylanilide, 4-chloro-3-aminobenzoic acid-2 *, 4 ', 5'-trichloranilid, 2,4-dichloro-5-aminobenzoic acid-2', 5'-dichloroanilide, 2, 4-dichloro-5-aminobenzoic acid ¹ -2, 4'-dlchloranilid, 2,4-dichloro-5-amlnobenzoesäure-3 -trifluormethylanilid ^i, 2 _J 4-dichloro-5-aminobenzoic acid-3'-chloroanilide, 2,4-dichloro-5-aminobenzoic acid-amide , 5-Amino-4-methoxy-2-chlorobenzoic acid-3 ^> -trifluoromethylanilide, 4-Methy1-3-aminobenzoic acid-2 ^f , 5'-i

^ -Methoxy - ^ - aminobenzoic acid amide,

^ i-Methoxy - ^ - aminobenzoic acid anilide,

4-methoxy - ^ - aminobenzoic acid - ^ '- chloranilide,

4-methoxy-3-aminobenzoic acid-2 ^T , 5'-dichloroanilide,

4-methoxy-3-aminabenzoic acid-2 ', 4', 5'-trichloroanilide,

4-carbomethoxy-3-aniinobenzoic acid anilide _i

^ -Methoxy-J-arainobenzoic acid - ^ '- trifluoroniethylanilide, _ ...

4-carbethoxy-3-aminobenzoic acid-2 ', 5'-dichloroanilide,

4-methoxy-3-sminobenzoic acid-5 ', 5'-bis-trifluorobenzoic acid,

4-Methoxy-3-aniinobenzoic acid-2 '-ehlor-5' -trif luorroetljy lanilid, 4-methoxy-3-aminobenzoic acid-2 ', 5'-dimethoxy-4'-4-methoxy-3-a-min.obenzoic acid-2 ¹ , 5'-dimethyl ~ 4'-chloroanllide,
4-methoxy-3-asiinobenzenesulfonic acid-2 ', 5' -dlchlorasilld,
4-Chlpr-3-aminobenzenesulfonic acid-2 ^l -c3ilor-5 ¹ -fcrif luormetlaylanilid,

Me obtained azo dyestuff carboxylic acids are with
Treated agents that are capable of converting carboxylic acids into their halides, for example chlorides or bromides, in particular with phosphorus halides, such as phosphorus pentabrOinide or phosphorus trichloride or pentachloride, phosphorus oxyhalides and
preferably with thionyl chloride,

The treatment with such acid-halogenating agents is two-fold in inert organic solvents, such as dimethylforraaride, chlorobenzenes, for example mono- or dichlorobenzene. Toluene, xylene or nitrobenzene carried out; -'in the case of the latter, if necessary with the addition of Tue

In the production of the carboxylic acid halides it is usually expedient to dry the azo compounds prepared in an aqueous medium first or by boiling in to free an organic solvent azeotropically from water. If desired, this azeotropic drying can be carried out immediately made before treatment with the acid-halogenating agents will.

The obtained azo dye carboxylic acid chlorides are now condensed with an aromatic amine as aromatic Amines are both mono- and diamines, in the latter case the condensation with the acid halide must take place in a molar ratio of 1: 2. The monoamines used are preferably aminobenzenes, in particular those of the formula

Examples are:
Aniline,

2-chloroaniline,
3-chloroaniline,
4-chloroaniline,
2,4-dichloroaniline,
2, _{5-dichloroaniline;} ■. - • 2-methyl-aniline ,,. ..-, .-. ■ -.-. · ■
3-methyl-aniline, qoO)

SAÖ

4-methyl-aniline, 2,4-dimethylaniline, 2,5-dimethylaniline, 2-methoxyaniline, 3-methoxyaniline, 4-methoxyaniline, 2,5-dimethoxyeniline, 2-ethoxyaniline, 4-ethoxyaniline, 2-methyl-4- chloroaniline, 2-methyl-3-chloroaniline, 2,5-dimethy1-4-chloroaniline, 2,5-dimethoxy-4-chloroaniline, 2,4-dimethoxy-5-chloroaniline, 2-methoxy-4-chloro- 5-methylaniline, 3-nitrobenzene, 1-aminonaphthalene, 2-arr, inonaphthalene, 4-formir.ylamino-aniline, 4-acetylamino-aniline, 4-propionylamino-aniline, 4-benzoylamino-aniline, P-chloro ^ -faenzoylamino -aniline, 2, S-dichloro ^ -benzoylamino-aniline, 2,5-dichloro-4- (4'-chlorobenzoylamino) -aniline, 2,5-diehlor-4- (2 ', 4 ^f -dichlorobenzoylamino) -aniline ,

909841 / U93 ■

2, 5-dichloro-4- (2 ', 5'-dichlorobenzoylamino) aniline, 2,5-dichloro-4- (4'-methyl-benzoylamino) aniline, 2,5-dichloro-4- (4'-phenylbenzoylamino ) -aniline, 2-methyl-4-benzoylamino-aniline, 2,5-dimethyl-4-benzoylamino-aniline, 2,5-dimethyl 1-4- (4'-chlorobenzoylamino) -aniline, 2,5-dimethyl 1-4 - (2 ', 4'-dichlorobenzoylamino) -aniline, 2,5-Dimethy1-4- (2', 5'-dichlorobenzoylamino) -aniline, 2, 5-Dimethy1-4- (4'-methylbenzoylamino) -aniline, 2 _} 5-Dimethyl-4- (4'-phenylbenzoylamino) -aniline, 2,5-Dimethy1-4- (4'-methoxybenzoylamino) -aniline, 2-chloro-5-methyl-4-benzoylamineΌ-aniline, 2- Chloro-5-methyl-4- (4'-chlorobenzoylamino) -aniline, 2-chloro-5-methyl-4- '(2', 5 ^f -dichlorobenzoylamino) -aniline, 2-chloro-5 ~ methy1-4- (4'-methylbenzoylamino) aniline, 2-chloro-5-methyl-4- (4'-phenylbenzoylamino) aniline, 2-methoxy-4-benzoylamino-sniline, 2-methoxy-5-chloro - ^ - (benzoylamino ) -aniline _i 2-methoxy-5-chloro-4- (4'-chlorobenzoylamino) -aniline, 2-methoxy-5 "-chloro-4- (2 ', 5' -dichlorobenzoylamino) -aniline, 2-methoxy- 5-chloro-4- (4'-methylbenzoylamino) aniline, 2-met hoxy-5-chloro-4- (4'-phenylbenzoylamino) -aniline, 4- (4'-carbomethoxy) -benzoylamino-aniline, 2 _J 5-dichloro-4- (4'-oarbethoxy) -benzoylamino-aniline, 2 , 5-Dimethy 1-4- (4'-carbomethoxy) -benzoylamirio-aniline,

309841 / U93

_ ₁₀ _

4- (4'-chloro) -benzoylamino-aniline, 4- (4 ^r -methyl) -benzoylamino-aniline, 4- (4'-methoxy) -benzoyla.mino-aniline, 4- (3'-acetylamino) - benzpylamino-aniline, 4- (4'-phenyl-benzoylamino-aniline, 4-aminophenylurea, 4-amino-2,5-dimethylphenylurea,

4-amino-2,5-dichlorophenylurea, -

4-amino-2-methylphenylurea, 4-Amino-2-chlorophenylurea, 4-Amino-2-methoxyphenylurea, 4-amino-2-chloro-5-methoxyphenylurea, 4-amino-2-methyl-5-chlorophenylurea, 4-amino-2-chloro-5-methy! Pheny! Urea, 4-amino-2,5-oleethoxyphenylurea, 4-aπlino-2-bromophanylurea,

4-Amino-2 _> 5-dimethy1-diphenylurea , 4-amino-2-m3thoxy-5-chlorophenylurea ^

4-amino-4-diphenylharnstoffι Ghlor-5-aminobenzoeaaure- ^(2: 5 ^f -diehlor) -aniiid,

4-Methoxy-3- ⁱ aminobenzoic acid- (2 ', 5' 4-chloro-3-aminσb8nzoic acid- (3 ^f -trifluoromethyl) -4-chloro-3-aminobenzoic acid * - (2 ', 5'-dimethy 1-4 '-chlor) -anilide, 5-amino- 2, 4-dichlorobenzoic acid-e- (3'-1rifluoromethy 1) -anilide, 4-chloro-3-ßΠ! inobenzoic acid- (5'-trifluoromethyl-2'-chloro ) -anilide, 4-methoxy - ^ - amirxObenzoic acid- (5 ^! -trif luormethy 1-2'-chloro) -anilide,

909841 / U93

4-chloro-3-aroinobenzoic acid (5'-carbomethoxy-2'-chloro) anilide, ^ methoxy-jsaminobenzoic acid (5 ^!, 8 ^! -Dichloro-a-naphthyl) -amide, 4-methoxy-5-aπlinobenzoic acid - (5 ^t -carbomethoxy-2'-chloro) -anilide, 4-chloro-3-aminobenzoic acid- (2 ', 5'-dimethyl-4'-chloro) -anilide, 4-chloro-j5-aniinobenzoic acid-e- (^ _'J 5'-ditrifluoromethyl) anilide, 4-chloro-3- (4-chloro-5 ^{T t} amino) -benzoylaminobenzoesäurephenylester, 4-chloro - ^ - (4'-chloro-3 ^r -amino) - benzoylaininobenzoesäure-4 '-chlorphenylester ^t,

5- (4 ⁱ -chloro-3'-amino) -benzoylamino-2,4-dichlorobenzoic acid phenyl ester,

5- (4 '-Chlor-3 ^! -C-mino) -benzoylamino-2,4-dichlorobenzoic acid benzy 1-ester,

5- (4 ^! -3hlor-3 ^! -Amino) -benzoylanino-2,4-dichlorobenzoic acid-4 "-chlorophenyl ester,

5- (4 '-Chlor-jj'-a ^ -i ⁿ o) -benzoylamino-2,4-dichlorobenzoic acid-4 "-chlorotenzylesber,

4-chloro-3- (4'-chloro-3'-amino) -benzoylair.inobenzoic acid-4 "-chlorobenzyl ester,

^ J-chloro-3 ~ (4 '-ohlor-3' -srr.ino) -benzoylaninobenzoic acid-4 "-methoxybenzyl ester.

Heterocyclic monoamines such as aminophenmorpholones can also be used as monoamines for the condensation., Aminobenzimidazolone, aminobenzoxazolone, aminoacridone or amino-naphthalimide or aminonaphthostyrile.

./. 11a 9 0 984-1 / 1433

ÖO OH. '/ ItW ^

From the series of aromatic diamines, diaminobenzenes or diaminodiphenyls may be mentioned in particular. 1,4-Diaminobenzenes of the formula are preferably used

^Z l

^Z 2

909841/1493

where Z, and Z _? Mean hydrogen or halogen atoms, alkyl or alkoxy groups, or diamino-diphenyls of the formula

wherein V denotes a hydrogen or halogen atom, an alkyl or alkoxy group.

The following diamines may be mentioned as examples: 1,4-diaminobenzene,
1,3-diaminobenzene,
1,3-diamino-4-methylbenzene, lj ^ -diamino- ^, 6-dichlorobenzene, 1,3-di & ßiino-4-chlorobenzene, 1,3-diamino-2,5-dichlorobenzene, I ₃ 4-diamino-2 -chlorobenzene, 1,4-Diarr.ino-2-bromobenzene _i 1,4-diamino-2 ₅ 5-dichlorobenzene, l ^ -Diamino-S-methylbenzene, 1,4-diamino-2,5-dimethylbenzene, 1, 4-diamino-2-methoxybenzene, 1,4-diamino-2,5-dimethoxybenzene, 1,4-diamino-2,5-diethoxybenzene, 1J _> 3-diamino-4,6-dimethylbenzene, 1,3-diamino -2,6-dimethylbenzene,

9098A1 / U93

2-cyano-1,4-phenylenediamine, 2-trifluoromethyl-1,4-phenylenediamine, 2-chloro-5-methyl-1,4-phenylenediamine, 2-chloro-5-methoxy-1,4-phenylenediamine, 2 -Methy1-5-methoxy-1,4-phenylenediamine, 4,4'-diaminodiphenyl,
3,3'-dichloro-4,4'-diaminodiphenyl, 3,3'-dimethy1-4,4'-d! Aminodiphenyl, 3,3'-dimethoxy-4,4'-diaminodiphenyl,

3 ^ 3 ', 5, 5 ^f -Tetrachloro-4,4'-diaminodiphenyl, 2,2 \ 5j5 ^! -Tetraohlor-4,4'-diaminodiphenyl, 3,3'-DiChIOr-S ₅ 5'-dimethyl-4,4'-diaminodiphenyl, 4 _i 4'-diarr.inodiphenyl ketone, 4,4'-diaminodiphenylir.ethane, 4 , 4 ^! -Diaminodiphenylsulfon, 4,4'-Diaminodiphenylather, 2,8-Diaminoehrysen,

4,11-Diaminofluoranthene ₅ 2,6- or 1,5-D.iaminonaphthalin, Diaminobenzthiazolej such as 2- (4 ^T -aminophenyl) -6-aminobenzthiazole.

The condensation between the carboxylic acid chlorides of the type mentioned at the beginning and the amines is expedient carried out in anhydrous medium. Under this condition it generally occurs surprisingly easily at Temperatures that are in the boiling range of normal organic solution

90984Ϊ / 1493-

medium, such as toluene, monochlorobenzene, dichlorobenzene, trichlorobenzene, Nitrobenzene and the like. To accelerate the reaction, it is generally advisable to use an acid-binding agent Use agents such as anhydrous sodium acetate or pyridine. Some of the dyes obtained are crystalline and partly amorphous and are mostly obtained in a very good yield and in a pure state. It is useful to use the Carboxylic acids obtained acid chlorides first of all to be deposited. In some cases, however, a deposit can occur without damage the acid chlorides can be dispensed with, and the condensation can be carried out immediately after the production of the carboxylic acid chlorides take place.

According to embodiment b) of the invention Procedure nan comes to the new dyes, if you use a diazotized amine, in particular an aminobenzene or its Diazoamino compound with a nitro-2,3-hydroxynaphthoic acid arylide the formula

OH
ONH-R ₂

preferably with one of the formula

OH

909841 / UI3

wherein Y, and Y _{p are} hydrogen or halogen atoms, alkyl or alkoxy groups and Y_ is a hydrogen or halogen atom or an acylamino group ^ coupling.

The 2,3-hydroxynaphtholic acid arylides required for this purpose are by methods known per se by condensation of the corresponding nitro-2,3-hydroxynaphthoic acid halides available with the corresponding amines in an organic solvent »

The coupling takes place by gradually adding the aqueous alkaline solution of the coupling component to the acidic solution of the diazonium salt. The amount of alkali metal hydroxide to be used to dissolve the coupling component is expediently calculated so that it is sufficient to neutralize the mineral acid released from the diazonium salt during the coupling. The coupling is expediently carried out at a p "value of 4 to 6 o The p _T , value is advantageously set by adding a buffer. Suitable buffers are, for example, the salts, in particular alkali salts of formic acid, phosphoric acid or, in particular, acetic acid. The alkaline solution of the coupling component expediently contains a wetting agent, dispersing agent or emulsifying agent, for example an aralkyl sulfonate, dodecylbenzene sulfonate or the sodium salt of Ι, Ι -'-naphthylmethanesulfonic acid, polycondensation products of alkylene oxides, such as the product of the action of p- - phenol, also alkyl esters of sulforicinoleates, for example n-butylsulforig ^ wieflty DJ ^ -Mspersion of the coupling

ßAO

⁴ If

component can also advantageously contain protective colloids, for example methyl cellulose or smaller amounts of inert ones, in water contain sparingly soluble or insoluble organic solvents, 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 hydrocarbon tetrachloride or trichlorethylene, also with water miscible organic solvents such as acetone, ethylene, Glycol monomethyl ether, methyl ethyl telephone, methanol, ethanol or isopropanolo

The coupling can also be carried out advantageously in such a way that an acidic solution of the diazonium salts is used an alkaline solution of the coupling component in a mixing nozzle continuously combined, with an immediate The components are coupled »Ea must be observed> that diazo component and coupling component are present in equimolecular amounts in the mixing nozzle, with a lower Excess coupling component proves to be advantageous.

The easiest way to do this is to check the p _TT value of the

Liquid in the mixing nozzle causes “There is also in the mixing nozzle to ensure a strong swirl of the two solutions. The resulting dye dispersion becomes the mixing nozzle continuously withdrawn and the dye separated by filtration O

909841/1493

SAD

The coupling can also be carried out in such a way that a diazoamino compound containing the radical R- is used with the nitro-2,3-hydroxynaphthoic acid arylide in an organic Solvent, if appropriate in an aqueous-organic solvent, preferably in the presence of an acid, heated.

The aryldiazoamides to be used according to the process are obtained by known processes by coupling an aryldiazonium salt with a primary or, preferably, with a secondary amine. For this purpose, a variety of amines, for example aliphatic amines such as methylamine, ethylamine, ethanolamine, propylamine, butylamine, hexylamine and particular Dinsthylamin, diethylamine, Diäthanolarcin, methylethanolamine, dipropylamine or dibutylamine, aminoacetic acid, methylaminoacetic acid, Butylaminoessigsäure, amino Methylaminoathansulfonsäure suitable ethanesulfonic acid, , Guanylathane sulfonic acid, ß-aminoethy! Sulfuric acid, alicyelic amines such as cyclohexylamine N-methylcyclohexylamine, dicyclohexylamine, aromatic amines such as 4-aninobenzoic acid, sulfanilic acid, 4-sulfo-2-aminobenzoic acid, (4-sulfophenyl) -guanoic acid , 4-ethylaminobenzoic acid, l-aminonaphthalene-4-sulfonic acid, l-aminonaphthalene-2,4-disulfonic acid, heterocyclic amines such as piperidine, morphine, pyrrolidine, dihydroindole and finally sodium cyanamide or dicyandiamide.

As a rule, the diazoamino compounds obtained are sparingly soluble in cold water and can optionally

9098A1 / U93

SAD ORiGlN ^ L.

separated from the reaction medium in crystallized form after salting out. In many cases, the damp Press cake can be used for further implementation. In individual cases it can prove to be useful that the Diazoamides prior to implementation by vacuum drying dewater or after slurrying the moist press cake in a solvent, the water by azeotropic distillation to remove.

The coupling of the diazoamino compound with the naphthol takes place in an organic solvent, for example chlorobenzene, o-dichlorobenzene, nitrobenzene, pyridine, ethylene glycol, Ethylene glycol monomethyl or monoethyl ether, dimethylformamide, Formic acid or acetic acid = when using solvents that are miscible with water, it is not necessary to use the diazoamino compounds in anhydrous form. For example, the watery-moist Nutsoh cake can be used. The one preceding the clutch Cleavage of the diazo & ^. Ino compound takes place in an acidic medium. If neutral solvents are used, it is necessary to add an acid, for example hydrogen chloride, sulfuric acid, formic acid or acetic acid.

The coupling is expediently in the heat, preferably carried out at temperatures between 80 to 180 C and is generally very rapid and complete.

Thanks to their insolubility, the pigments obtained can be isolated from the reaction mixtures by filtration.

909841 / U9 3

O & 'GfNAL

As the by-products remain in reading, those obtained drop Pigments in excellent purity on «An aftertreatment with organic solvents for pigments that are based on the aqueous coupling path are obtained, is indicated «Another advantage of the method according to the invention is the high yield, the favorable pigment form and the constancy of the properties of the pigments obtained.

The pigments obtainable according to the process can

w can be used for a wide variety of pigment applications thanks to their favorable properties, e.g. in finely divided form for dyeing rayon and viscose or cellulose ethers and esters or superpolyamides or super-polyurethanes or polyesters in the spinning mass, as well as for the production of colored lacquers or lacquer formers, solutions or products made from acetyl cellulose, nitrocellulose, natural resins or synthetic resins, such as polymerization resins or condensation resins, e.g. aminoplasts, alkyd resins, phenoplasts,

"Polyolefins, such as polystyrene, polyvinyl chloride, polyethylene, Polypropylene, polyacrylonitrile, rubber, casein, silicone and silicone resins., They are also beneficial in the manufacture of colored pencils, cosmetic preparations or laminating plates.

Compared to analogous dyes in the 2,3-Hydroxynaphtο-ylrest have no nitro group, the dyes according to the invention show the surprising technical effect of a significant better migration authenticity.

909841 / U93

1903 & 49f

In the following examples, unless otherwise stated, parts are parts by weight, percentages ⁽ percentages by weight, and temperatures are given in degrees Celsius).

909841/1493

Example 1.

54.4 parts of the dye carboxylic acid obtained by coupling diazotized 2-chloro-5-trifluoromethyl-aniline with 6-nitro-2-hydroxy-3-napthoic acid are in dry and powdery form in 400 parts by volume o- 13.5 parts by volume of thionyl chloride and 0.4 parts by volume of dimethylformamide are added to dichlorobenzene. The mixture is heated to 100 ° to 105 ° for three hours with stirring and then allowed to cool. The * coarse-needle crystals are filtered off and placed in a vacuum.

60 to 70 ° dried. 4-9 parts of the dye carboxylic acid chloride are obtained.

2.29 parts of this chloride together with 1.32 parts of 2,5-dimethyl-4-benzoylaminoanilin in 100 parts by volume of o-dichlorobenzene and heated for 0.5 parts by volume of pyridine for 17 hours at l40 to 150 ^0th The pigment formed is then filtered off while hot and washed out successively with hot o-dichlorobenzene, cold ammonia-alkaline methanol, dimethylformamide and hot water. After drying in vacuo at 60 to 70, a red-orange, soft-grained powder is obtained. The pigment corresponds to the formula

90 984 XtH * h \ ^ u

and colors polyvinyl chloride in reddish orange tones of very good light and migration fastness. .

In the following table weitere- Pigrnentfarbstoffe are reported, which are obtained, if the aniline derivatives listed in column I of 6-nitro-2-hydroxy-3-naphthoic acid according to the procedure of Example 1 coupling, converting the Azofarbstoffcarbonsäure obtained with thionyl chloride into the acid chloride and. the latter with the amine listed in column II condensed column III indicates the color of the colored polyvinyl chloride film.

9 0 9841/1493 ^{$ AD}

2,5-dichloro-l-amino benzene

Il

4-benzoylamino-1-aminobenzene

4- (2 ', 4'-dichloro-benzoylamino) -l-aminobenzene

4- (4'-methoxy-benzoylamino) -l-aminobenzene

4- (4'-methyl-b.enzoylamino) -1-aminobenzene

2,5-dimethoxy-4-benzorylamino-1-aminobenzene

j 2-methyl-5-methoxy-4-

j benzoylamino-aniline

III

bordeaux

light brown

pink

2,4,5-trichloro-l aminobenzene! 4-BenzoylaminO'-l-amino-: light-bofbenzene i deaux

13]

"" ■ I 4- (4V-methoxy-benzoyl-

amino) -l-aminobenzene

¹¹ j 2,5-I> imethyl-4-benzo-

] ylamino-1-aminoben zol '1

2-chloro-5-trifluoro- {4-benzoylamino-l-ami- -

methyl-1-aminobnezol \ nobenzol_

¹¹ ! 4- (2 ', 5'-dichloro-ben-

zoylamino) -l-amino-

! benzene

j 4- (4'-methoxy-benzoyl ] amino) -l-aminobenzene

j 4- (4 * -phenyl-benzoyl- \ amino) -l-aminobenzene

Il 2,5-dimethyl-4-benzoylamino-1-aminobenzene

gray-brown

Brown '

yellow Red

yellow Red

yellow Red

light brown

red length

0 $ 0 * 1/14 »3

15 16 17 18 19 20

21

2-meth.oxy-5-n.itrO- j 1-aminobenzene

2-methoxy-5-nitro-1-aminobenzene

2-methoxy-5-chloro 1-aminobenzene

25i

.

26 * 2-nitro-4-chloro-rli aminobenzene '

27! ^; "- ■■ · ■.

20 ■ '- ■■ » f

4-benzoylamino-1-aminobenzene

bright red

4- (2 ", 5'-dichloro-benzo-; bordeaux ylamino) -1-aminobenzene:

4_ (4 "-Methoxy-benzoylamino) -1-aminobenzene

light burgundy

4-acetylamino-1-amino-carmine

"benzene, \

2,5-dimet.hoxy-4-benzoyl- {brown amino-1-aminobenzene i

2-methyl-5-methoxy-4-benzoylamino-1-aminobenzene

4 -Be n'zoyl amino-1-aminobenzene

4- (2 ', 5'-dichloro-benzoylamino) -1-aminobenzene

4 .- (4 '-Metuoxy-benzoylamino) -1-aminobenzene

4-acetylamino-1-aminobenzene

2, 5-TPiy4

ylamino-1-aminobenzene

4, -Benzoylamino-l'-aminobenzene

4- (4-chlorobenzbylamino) -1-aminobenzene

• 4- (2 ', 5'-Diciloro-benzoylamino) -1-aminobenzene

blue red

bordeaux

carmm

blue red

gray-violet

blue red

bright red

bright red

bordeaux

- -99 -

II

III

! 29 ι 2-nitro-4-chloro ^: l-aminobenzene

2-methoxy-4-nitro

5-chloro-l-amino-

benzene

32 I 33

34

38 39 40

2-methoxy-4-nitro-

5-chloro-l-amlnoben-

zol

2-methoxy-4-nitro- | l-aminobenzene

4-nitro-2-trifluoromethyl aniline

41 \ 2-Nitro-4-trifluoro · \ methy! Aniline 4 -. (4 ^r -Methyl-be-nzoylamino) -1-aminobenzene

2,5-dimethyl-4-benzoylamino-1-aminobenzene

4-benzoylamino-1-aminobenzene.

4- (4 -chloro-benzoylamino) -l-aminobenzene

4- (2, 5 '-Dichlar-benzoylamino) -l-aminobenzene

4- (4'-methyl-benzoylamino) -l-aminobenzene

2, S-Diy
amino-1-aminobenzene

4-benzoylamino-1-aminobenzene

4- (4 · chloro-benzoylamino) -l-aminobenzene

4_ (2 ·, 5'-dichlorobenzoyiamino) -1-aminobenzene

Red

brown-red bordeaux

light purple brown red

violet · .: brown red ' Red

Red ; ";·.-"" Red '

4- (4 '-Methyl-benzoylami-i' red no) -l-aminobenzene

4-Benzoylamino-1-amino- \ .scharlaöh benzene j 'ν

ti - .. -. ' ■ - "" ■ · .. j. Orange '

■ - 86 -

III

42 y. j \ 43

44 45

46

47 48

49

50

51 52

53 54

2-! Tiiro-4-trifluoro-i 4-chloro-3-arninobenzoe- ■ methyl aniline! acid-2'-chloro-5'-tri-

! fluoromethylanilide

4-Iue thoxy-3-amino- benzoic anilide

4-methoxy-3-amino benzoic anilide

benzoic acid-2 ·, 4 'dichloroanilide

4-methoxy-3-aminobenzene-sulfo-N-dimethy1amide

2, 5 ~ dietethoxy-4-benzoylaminoaniline

Aniline m-nitroaniline

p-chloroaniline

orange

s bluish red

bordeaux

aniline

3-I <ethylaniline

4-carbomethoxy-3- | Aniline aminobenzoic acid- j amide |

4-aminobenzoic acid -ami d

4-methyl-3-aminobenzoic acid amide 4-methoxyaniline
o-ethoxy-aniline

■ bluish red • j

- j blue-red

i blue

; Red

i red

.j ■

\ red

2-methyl-4-methoxyanilini red

4-chloro-3-amino- \ 4-methoxyaniline benzoic acid-2 ', 5'-;dichloranilide;

4-chloro-3-amino- ^; - 2-Aciino-naphthalene benzoic acid-2 ', 4'-I dichloroanilide j

3-Iuethyl-4-aminobenzoic acid amide .2-methoxyaniline

Red

Red

blue red

9 0 9841. bath

I. II III ' 55
i 4-aminobenzoic acid
4 • -chloranilide 2-methylaniline Scarlet fever 56 4-methyl-3-amino
benzene sulfonic acid
H-butylamide 2-aminonaphthalene
* bordeaux 57 4-methoxy-3-amino
benzoic acid (3'-tri
fluorine thyl) -anili d 4-benzoylamino-l-
■ aminobenzene bordeaux 58 It 5-chloro-2 _r 4-dimen-
thoxy-1-aminobenzene bordeaux 59 4-chloro-3-amino-
benzoic acid- (2 ·, 5 ^c -
dichloro anilide Il Red
• 60 4-chloro-3-amino-
benzoic anilide 4-benzoylamino-l-
aminobenzene Red 61 2,5-dichloroanilixi 4-amino-naphthostyril Brown 62 Il e-methoxy-T-araixio-phen-
morpholone- (3) yellow-brown 63 Il ö-chloro-T-amino-phen-
morpholone- (3) brown orange 64 Il 6 -Me thy l-7-aiaino-phen-
morpholone- (3) brown orange 65 Il 7-amino-phenmorpholone-
(3) bordeaux 66 Il 2-amino acridone Red 67 Z-chloro-S-trifluor-
Ethyl aniline 6 -lie thy l-7- »mino-phen-
morpholone- (3) yellow-brown 68 N 3-aaino-nmphthalieid orange

tetto / uti

- aer -

I. II III : 2-chloro -5-trifluoro-
• methyl aniline 7-amino-2-oxy-4-methyl
quinoline. Scarlet fever 70 - S-amino-ö-methyl-benzi-
midazolone yellow-brown 71 l- (3 ^r -amino-4 * -
chlQr-benzoylamineQ) -
3-trifluoromethyl
benzene 2-amino acridone bordeaux 72 ir 7-amino-6-chloro-phen-
morpiiolon- (3) brown orange 73. . l- ( I'-Amlna-A -
Chlorobenzoylamino)
-3-triflaomethyl-
benzene 7-amino-6-me thy1-phen-
morpiiolon- (3) yellow-brown 74 It 4-amino-aaphthpstyril yellow-brown 75 2,5-dichloroaniline S-aminotenzoxazole αη-2 Brown 76 2 »4 1 5-irichloroaniline
I. η Brown

909H1 / UI3

Example 2 »

Is used instead of 6-2iitro ~ 2-hydroxy-3-naphthoic acid the 8-nitro-2-hydroxy-3-'iiaphthioic acid and If the procedure is otherwise as indicated in Example 1, pigment dyes with similar properties are obtained;

I. II III 1 2 1 5-dichloro-1-amino
benzene 4-benzoylamino-1-
aminobenzene helibordeaux 2 dd 4 .- (4 «-Methyl-benzo-
y 1 ami no) -1-aiaino-
benzene light brown 5 2-chloro-5 ~ trifluoro-
methyl-1-aminoben-
Sol 4-Benzoyle »tno-l-
«Cinema Sol brownXb 4th ir 4- (4 ^f -Methyl-b »nzo-
yl amino} -1-mö.eq--
benzene brownish yellow

90M41 / UII

Example 3.

The nitration of 2-acetoxy-3-naphthoic acid in 86 Ji ige r nitric acid at -10 ° results in 3 isomers; Probably 5-, 6- and 8-nitro-2-hydroxy-3-naphthoic acid.

If this mixture is used instead of 6-nitro-2-hydroxy-3-naphthoic acid and the procedure is otherwise as indicated in Example 1, figment dyes with similar properties are obtained.

I. • II III 1 2,5-dichloro-l-amino-
benzene 4-uenzoylamino-l-
aminobenzene yellowish red 2 Il 4- (4 «-Methyl-benzo-
ylamino) -l-aminoben-
zol bordeaux 3 It 4- (4'-methoxy-benzo-
ylamino) -l-aminoben-
zol light burgundy 4th a-chloro-S-trifluor "
as thy 1-1-smlnobsnsol 4-benzoylamino-l-
aminobsnzol orange 9 M. 4- (4t. Thylbsnio- _Me
ylaeino) -l-sjiino-
beniol orange t N 4- (4 -utthoxybsnio-
y1 smino) -1-bec-
bsmol trsiift

Example 4. - / '

69 parts of the dye carboxylic acid, which one through Coupling of diazotized 2,4,5-trichloroaniline with 6-nitro-2,3., · Hydroxynaphthoic acid is obtained in 300 parts by volume of chlorobenzene with 22.8 parts of thionyl chloride and 1 part by volume of dimethylformamide heated to 100 to 110 for 3 hours and then left to cool are filtered off and dried in vacuo at 60 to 70 » 74.7 parts of the dyestuff carbonic acid chloride are obtained.

-2.3 parts of this chloride are combined with 0 ^ 27 parts of 1,4-Dia.minobenzene in 100 parts by volume of o-dichlorobenzene warmed to 130 to 140 ° for 15 hours. Then it will be the resulting pigment is filtered off while hot and one after the other, with hot o-dichlorobenzene, cold dimethylformamide, ammonia-alkaline Methanol and hot water. After drying, a bright brown-violet powder is obtained. That Pigment corresponds to the formula

Cl

98 417149 3

8ADORfGfNAL

Incorporated in polyvinyl chloride, this pigment gives a brown-red color with very good light- and immigration awareness.

Additional pigment dyes are shown in the table below listed, which are obtained if the aniline derivatives listed in column I according to the details of Example 2 diasotie'rt and coupled with 6-nitro-2,3-oxynaphthoic acid, which obtained aso-dye carboxylic acid with thionyl chloride into the acid ~ chloride and the latter in a ratio of 2: 1 with the condensed diamine listed in column II. Column III indicates the color of the pigmented polyvinyl chloride film.

- I. II hi '- ^: ■ I 1-j 2,5-dichloro-l-amino-
benzene 1,4-diaminobenzOl Brown . 2 Il 1,3-Diaminobenzene. bordeaux, 3 Il .j
f 1,4-hiamino-2,5-di-
methyl benzene Brown . 4th -, · "■■ i
.- ■ "'" _: 1,4-diamino-2,5-di-
chlorobenzene bordeaux -, ■ 5 Il
. ; 3.3 ^f -I>chloro-4,4'-
diamino-1,! - diphenyl marron 6th Il
.. .- - '- -.
2,2'-dichloro-4,4'-
diamino-1,1'-di
phenyl bordeaux 7th 3,3 * -Dime thoxy-4,4 '■.
,. -diamino-1,1'-di
phenyl blue red ' 8th 2,4,5-trichloro-l-ami-
"nobenzol · _
1,4-biaminobenzene red-brown ~~ \ 9 / »- .-. : 1,3-diaminobenzene Brown . 10 Il : "1,4-diamino-2-me-;
ethyl-5-methpxyben- '
zo! gray-brown 11th Il 1 , 4-diamino-2-me-
ethyl 5-chlorobenzene Brown 12th H 1,4-diamino-2,5-di-
• dimethylbenzene Brown 13th Il 1,4-diamino-2,5-di-
chlorobenzene light brown - _; '14
15th It
!; · ..-:.:,,:.: ■.-.... 1,4-di amino. 2 - chi or
be * izol * ". .- ·; '
4,4 · -Diamino-1,1'-.
diphenyl; light brown f
; .- 'J.
light burgundy

ORIGINAL INSPECTgO

T "

II

III

Ιό '-2,4, ^ - ITiChIOr-I- j 3 »3' -Dichlor-4,4 '-di · I aminobenzene I amino-1,1'-diphenyl

17 2,4,5-2richlor-1-aiuinobenzene

18 "■

19 2-chloro-5-triflu- "ormethyl-1-aminobenzene

20 "

21 "·

2 * 2 ^l -dichloro-4,4 ^l -diamino-1,1'-diphenyl

light brown

red-purple

3,3'-dimethyl 1-4) 4'-di-; Brown amino-1,1-diphenyl;

2-methoxy-5-nitro-1-aminobenzene 1,4-diaminobenzene

1,3-diaminobenzene

1,4-diamino-2,5-di
chlorobenzene

j 1,4-1 i ami no-2-ch lor
ί benzene

\ 3,3'-dichloro-4,4'-dij amino-1,1-diphenyl

2.2 r - ZlGhIQT-G , 4'-diamino-r-1,1'-diphenyl

3,3'-dimethoxy-4,4'-diamino-1,1'-diphenyl

1,4-diaininobenzene

1,3-diaininobenzene

1,4-diarriino-2-niethoxy-5 -me xhy I b e riz ο 1

1,4-diamino-2-methyl-5-chlorobenzoi

1,4-diamino-2,5-dir-diethylbenzene

:Brown

! ■ -! Brown

yellow

^: yellow-red. ,yellow Red

"blue red

ι "; ■ gray-blue

'bordeaux.; bordeaux

^; bordeaux

ί blue

9 1 s

1,4-Liamino-2,5-dichloro | gray-blue benzene>,

■ ■■ ^'~;! !

4,4'-Ρχο.ΐαίηο ^ 1,1 '^ di- · dark burgundy

8 41 / Ü9 3

33 36
'- 3-5 I. 1 II- 9036Λ9 .1 bordeaux ί ^; - 34
1 2-methoxy-5-nitro- '
1-aminobenzene 3, 3'-DiChIOrMf 4 '-
dia'mino-1,1'-diphenyl III blue red 35 2-methoxy-5-nitro-l-
aminobenzene] 2,2'-dichloro-4,4'-
diphenyl helibordeaux blue red 36 3,3'-dimei; hyl-4,4 ^< -
dianiino-1,1'-diphenyl blue red
- - ί bordeaux 37 Il 2.2 ¹ -Dimethy1-4,4'-di-
amino-1,1'-diphenyl I.
blue red [ 38 Il 3,3'-dimethoxy-4,4'-
diamino-1,1-diphenyl blue red 39 2-methoxy-5-chloro
1-aminobenzene 1, 4-diaminobenzene blue red 40 Il 1,3-diaminobenzene blue red 41 Il 1,4-diamino-2-methyl-
5-chlorobenzene gray-blue. j
j 42 Il l ^ -Diamino ^ -me- _:
thoxy-5-methylbenzene gray-blue 43 Il 1,4-diamino-2,5-di-
methylbenzene blue red Il 4,4'-diamino-1,1'_ vi olett 44 diphenyl Red Blue 45 Il 3,3i-dichloro-4,4'-di
amino-1,1'-diphenyl 46 Il 3,3'-dimethyl-4,4 ^l -
diamino-1,1-diphenyl 47 Il 3,3'-dimethoxy-4,4 * -
diamino-1,1'-diphenyl 2-nitro ^ 5-chlorine-l-
amincbenzoT 1,4-diaminobenzene

BAO ORIGINAL

3 * 5 -

j 48 j 2-nitro-5-chloro-1-S I aminobenzene

49 y

53 54 55

56 y

58

{59! 60 I.

II-

2-methoxy-4-nitro-5-chloro-l-aemino- benzene

II

1,4-diamino-2,5-dime thy! benzene

III brown

1,4-diamino-2,5-di- j light red chlorobenzene ΐ

4,4'-diamino-1, l ^f - I light red diphenyl

3,3'-Bichlor H-, 4'-diamino-1,1 '-diphenyl

2,2'-dichloro-4,4'-diamino-1,1 · -Diphenyl

3,3'-dimethyl-4,4'-diamino-1,1-diphenyl

violet

Red

brownish red

3.3 ^L -dimethoxy-4,4'-; brown-red diamino-1,1'-diphenyl {

I purple

1,4-diaminobenzene

1,4-diamino-2,5-dime-! brown-red thy! benzene 1

1,4-diamino-2,5-dichlorobenzene

4,4'-diamino-1,1-diphenyl

3,3'-dichloro-4,4'-diamino-1,1 '.-diphenyl

3,3'-dimethyl-4,4'-diamino-1,1'-diphenyl ^f

3,3'-dimethoxy-4,4'-diamino-1,1'-diphenyl ¹

brownish red

violet

blai

brownish red

brownish red

909841/1493

SS

- .57 -

III

j 70. »

^ -Methoxy ^ -nitro-laminobenzene

2-nitro-4-trifluorometh-yl aniline

71 j 4-nitro-2-trifluoro-

methylaniline

2-Amino-4-trifluoro-1 methyldiphenyl ether

2,5-dichloro-1-aminobenzene 4,4'-diamino-1,1'-diphenyl

1,4-diaminobenzene

2,2'-dichloro-4,4'-di- " amino-1,1'-diphenyl

31 3'-dichloro-4,4'-di- ■ amino-1,1'-diphenyl

violet

1 purple

brownish red

gray-brown

3,3'-dimethy 1-4,4'-di-j blue amino-1,1'-diphenyl i

1,4-diamino-2,5-dimethylbenzene

3,3'-dimethoxy-4,4'-diamino-1,1'-diphenyl

1,4-phenylenediamine

2,5-dichloro-1,4-phenylenediamine

1,4-phenylenediamine

1,4-phenylenediamine

2-chloro-1,4-pheny-. lenediamine

4> 4'-diamino-diphe-

3-chloro-1,4-diamino-. benzene

violet

violet

brown orange

orange

blue red

Scarlet fever

Scarlet fever

Red

brownish red

ι
ι: - 4-methyl-3-amino
benzoic acid -methy1-
ester ,. . — J. III -; 76 i
2,5-dichloro-1-amino- ^;
benzene -
Il 2,5-dimethoxy-1,4 ^; -
diamino benzene '; bordeaux 77 2-amiriobenzoic acid
methyl ester '
I. 4-Meithyl-3-amino- Il bordeaux 78 t
Il ester 1,4-diaminobenzOl red-brown 79 S-methyl-g-chlorine-l-
«Uainobenzol 2,5-dimethyl-1,4-dl-j
aminobenzene red-brown 80 4 * 4 * -diaminodiphenyl red brown j
■ 81 2,5-dimethyl-1,4-di-
aminobenzene bordeaux 82 2,5-dimethoxy-1 * 4-
diaminobenzene bordeaux 85 Il Brown 84 4,4 • -Gdiaminodiphenyl brownish red

90914

Example 5. "■

Used instead of 6-nitro-2-hydroxy-3-naphthoic acid the 8-nitro-2-hydroxy-3-naphthoic acid and otherwise changes as indicated in Example 4, is obtained Pigment dyes with similar properties:

II

III

2., 5-dichloro-1-aminobenzene

1,4-diaminobenzene

1,4-egg-amino-2,5-dime thy benzene

4,4'-diamino-1,1'-diphenyl

2-chloro ~ 5-trifluoromethyl-1-aminobenzene

diamino-1,1'-diphenyl 1,4-diaminobenzene

1,4-diamino-2,5-dimethylbenzene

4,4'-diamino-1,1'-diphenyl

3,3'-dichloro-4,4'-d amino-1,1'-diphenyl

bordeaux brown-red brown-red bordeaux orange-brown Brown

yellowish brown light burgundy

909841/1493

PAD ORIGINAL

Example 6,

The nitration of 2-acetoxy-3-naphthoic acid in 86% nitric acid at -10 ° results in three. Isomers: • probably 5- ,. 6- and 8-Mtro-2-hydroxy-3-naphthoic acid.

If you use 6-nitro-2-hydroxy-3-naphthoic acid this mixture and otherwise proceed as in Example 4 given, pigment dyes with similar properties are obtained.

II

III

1 \ 2,5-dichloro-1-amino- j 1,4-diaminobenzene \ benzene |

4 2-chloro-5-trifluoromethylaminobenzene

It

bordeaux

j 4,4'-diamino-1, l'-di-j.:. bordeaux \ phenyl I

3,3'-dichloro-4,4'-diamino-1 , 1'-diphenyl

1,4-diaminobenzene

ί "4,4'-Diamino - !, l'-di-I phenyl -

3,3'-Diehlor-4,4'-di- ■ amino-1,! '- diphenyl

Brown

brownish orange

brownish red

Brown

98U / H93

Example γ.

9.8 parts of 5-trifluoromethyl-2-chloro-1-aminobenzene become added to a mixture of 15 parts of ice, 25 parts of 30% hydrochloric acid, 10 parts of glacial acetic acid and stirred for one hour. Ice is added until the temperature reaches -3. gives 13 * .4 parts of 4N sodium nitrite solution within 5 minutes too, so that potassium iodine starch paper turns a distinct blue color shows; then another 2.6 parts of 4N sodium nitrite solution are added added dropwise and stirred at 0 to 5 for a further hour. The aqueous solution of sulfamic acid is then added until the blue color on the potassium iodine starch paper has disappeared. ■

On the other hand, 22.8 parts of δ-nitro - ^ - hydroxy - ^ - naphthoic acid-e- (4'-benzoy'lamino-2 ^t , 5 ^f -dimethy]) - phenylamide dissolved in 50 parts of ethanol, 10 parts of 30% Sodium hydroxide solution, 200 parts of water and 100 parts of ethylene glycol monoethyl ether. 1 part of the condensation product of 8 moles of ethylene oxide and 1 mole of p-tert-octylphenol is added to the solution and then the naphthol is precipitated with 70 parts of ice water with thorough stirring. A value of 3 to 4 and a temperature of 35 to 40 °. To end the coupling, the mixture is stirred for 2 hours at the same temperature, the pigment suspension formed is acidified to Congo by adding hydrochloric acid and filtered off. Wash with hot water until no more chlorine ions can be detected in the filtrate.

9Q9841 / 1493

After drying, the dyestuff thus obtained corresponds in shade and structural formula to that according to Example 1 obtained product. For special applications, the pigment can be cleaned as follows: The water-based Nutschkuchen is entered in a mixture of 100 parts of o-diehlobenzene and 110 parts of ethylene glycol monoalkyl ether, Stirred for 30 minutes at 90 to 100 and filtered the whole thing. The filter residue is first rinsed with ethylene glycol monoethyl ether and then washed with methanol and in vacuo at 70 dried up to 80 °.

The table below lists further pigment dyes that are obtained if one follows the instructions of Example 7, the aniline derivatives listed in column I with the 2,3-hydroxynaphthoic acid arylides listed in column II clutch. Column III indicates the color of the colored polyvinyl chloride film.

9 0 98A1 / U93

Ψί

I. I. I III, 1 J2,5-dichloro-aniline 6 -STitr o-2-liydroxy-3-
naphthoic acid (4 * -benzo-
ylamino-2 * _f 5 -'- dimethyl)
-phenylamide ; Red_
■ 2.
- Il 6-nitro-2-hydroxy-3-
naphthoic acid- (4 ^{r -ben-}
zoylamino) phenylamide - ¹ scarlet
Ϊ 3 5-Chlcr-2,4-dimetho-
xy-aniline Il bordeaux 4th 4-nitro-2-methoxy-ani-
lin Il " Red 5 4-methoxy-3-amino
benzoic anilide Il blue red 6th 4-chloro-3-amino-ben-
aoic acid- (3'-trifluoro-
me thy1) -aniIid Il Red 7th 4-methyl-3-amino-ben-
^ acid- (2j5'-di-
chlorine) anilide Il
■ Red 8th 4-methyl-3-aminobenzoe-
acid (5'-trifluorme-:
th.yl-2'-chloro) anilide 6-uritro-2-hydroxy
3-naphthoic acid- (4 -
[4 "-phenylJ -benzoyl-
amino) phenylamide Scarlet fever

909841/1493

' Example 8.

17.5 parts of 2,5-dichloroaniline are mixed with 100 parts. water melted at 60 ° and with thorough stirring 50 parts by volume 30% hydrochloric acid added, with ice and 27 * 5 parts by volume 4N sodium nitrite solution diazotized at 0 in the usual way and filtered cold.

On the other hand, 55.7 g parts of bis (6 "-nitro-2"-hydroxy-;y'-naphthoyl) -3.3 ^! -Dimethoxy-4, V-diamino-diphenyl dissolved at 20 ° in 550 parts of ethylene glycol monoethyl ether and 20 parts by volume of 30% sodium hydroxide solution and 1000 parts of water and filtered. The two solutions are continuously fed to a mixing nozzle, if necessary after dilution with water where an immediate coupling of the components takes place. By regulating the supply of the solutions and by buffering with NaJ3juO- solution (borax), it is ensured that the p “value in the mixing nozzle is between 8 and 9. The temperature should fluctuate between 15 and 20. This can be regulated by adding water to the component solutions. The pigment suspension formed is filtered off and the filter residue is washed out thoroughly. The pigment press cake is then heated to 115 ° with 100 parts of ethylene glycol monoethyl ether while stirring, water and small amounts of the ethylene glycol monoethyl ether being distilled off. The suspension is then held at 110 to 115 ° for a further 2 hours and then filtered off while hot. The filter residue is first

9 09841 / H93

with hot ethylene glycol monoethyl ether, then with methanol and then washed with water. After drying in a vacuum at 60 to 70 ° a red, soft-grained one is obtained Powder. The pigment corresponds to the formula

Cl

I OH

_C0NH

and colors plastics, such as polyvinyl chloride, and paints in brilliant blue-tinged red shades of excellent Migration, varnish and lightfastness.

Further pigment dyes are shown in the table below listed, which is obtained if the aniline derivatives listed in column I according to the information in Example 8 with the 2, ^ - hydroxynaphthoic acid arylides listed in column II kuppelt / Kolonne III indicates the color of the colored polyvinyl chloride film.

9841VT49 3 ./. 4 ₅ a

I. ; II -III
I. 1 2,5 dichloro aniline . Bis-Xe'-Uitro ^ '-hy-
[ droxy - ^ '- naphthoyll-
• l ^ -di-aminobenzene reddish
Brown CVJ 4-nitro-2-methoxy
aniline Il bordeaux
i 3 5-chloro-4-nitro-2-
. methoxyaniline Il
^; bordeaux 4th 2,5-dichloroaniline
- Bis- (6'-Kitr0-2 «-hy-
droxy-3'-naphthoyl) -
2,5-dichloro-1,4-diami-
note zol Red 5 Il
-
- -
Bi s- (6 "-M tr 0-2" -hy
droxy — 3 "-naphthoyl) -
3,3'-di chloro-4,4'-di--
amino-diphenyl Brown
!
? 6th 4-methoxy-3-amino
"benzoic acid- (3 '-tri-
fluoromethyl) anilide
i Il blue ^ ]
stinging \
Red
1

09841/14 93

Example _Q_. '

46.6 parts of 6-nitro-2-hydroxy-j5-naphthoic acid are stirred in 500 parts of toluene with 2 parts of dimethylformamide and added dropwise at 70 25 parts of thionyl chloride. ' Man stirs for 2 hours at 70-80 °. After this "f" time, the strong development of hydrochloric acid ceased. It is left to room temperature catch a cold, filtered, washes with petroleum ether. and dries at 40-45 in vacuo. One gets in this way * 47 parts of ö-nitro ^ -hydroxy - ^ - naphthoic acid chloride accordingly $ 93.5 of theory.

Analysis; ^v Calculated C 52.51 H 2.42 Cl 14.10 N 5.56 Found C 52.49 H 2.45 Cl 13 * 95 N 5.51

25.2 parts of 6-nitro-2-hydroxy-3-naphthoic acid chloride are stirred in 200 parts of toluene and 10 parts of aniline are added. After a short time, a thick, light yellow crystal paste forms. The mixture is heated to 110 for 2 hours, during which time a strong elimination of hydrochloric acid can be observed '. It is then left to cool, filtered, washed with toluene, then with methanol and finally with hot water. - _;

After drying at 90-95 ° in vacuo, 29 parts of 6-nitro-2-hydroxy-3-naphthoic acid anilide as a light yellow powder with a melting point F 267.5 to 269 ^0th This naphthanilide dissolves clearly in dilute sodium hydroxide solution with a yellow-orange color.

9098417U93

Example 10.

30.8 parts of 6-nitro-2-hydroxy-3-naphthoic anilide are used in 50 parts of ethanol and 200 parts of water with 15 parts Sodium hydroxide solution $ 30 dissolved. At the same time there will be 1β, 2 parts 2,5-dichloroaniline with 25 parts of hydrochloric acid and 25 parts 4N sodium nitrite diazotized at 0 and the diazo solution filtered clear. The diazo solution becomes crystalline with 25 parts at 0 ° Sodium acetate set to p "4 and while stirring the

π.

Coupling solution added dropwise. When the addition is complete, shows the reaction mixture only traces of excess diazo compound. The mixture is stirred at room temperature until no more diazo compound can be detected, then heated to 8O-85 and the azo dye formed is filtered off. It is washed salt-free with hot water and dried at 90-95 in a vacuum. You get 46 parts of a bright red pigment of the formula

Cl HO COHN-

-N = N-

Cl

Compared to the analogous pigment, this pigment shows red 2 CI. I2.3IO significantly improved properties. Above all this pigment shows better sublimation fastness properties and significantly improved solvent fastness properties. At the same time will also the lightfastness improves. This pigment can be specially used for the production of printing inks, for emulsion dyes,

90 9841/1493

so

for mass coloring of paper and in pigment printing Find. His significantly improved migration and transfer.,. ".., _ However, its fastness to lacquer also allows it to be used in plastics such as polyvinyl chloride or in rubber as well as in paints.

The table below lists pigment dyes which are obtained by coupling the diazo compound of the in. Column I indicated amine on a 6-nitro-2-hydroxy-3-naphthoic acid arylamide that by condensation of 6-nitro-2-

the column II / ν hydroxy-3-naphthoic acid chloride with the arylamines / were obtained. Column III indicates the color of a polyvinyl chloride film colored with this pigment.

909841/1493

I '

III

2,5-dichloroaniline J 4-methyl aniline

■ j

j scarlet

2,4,5-trichloroaniline

2-methbxy-aniline 2-methylaniline red

2-methyl-4-chloro-ani-j 2-methyl-4-chl. Qrani "-. J blue-red j

lin

1 t_ *! * ■

llin

aniline 2-methyl-5-chlorani-! ruby

lin

2,5-dichloroaniline! 2,5-dimethoxyaniline 5-Ni'tro-2-methylani- \ aniline · lin I.

2-methylaniline

4-ghloraniline

4-nitro-2-methylaniline

12! 2-nitr0-4-methy 1-aniline

2-Kitr0-4-chlorine aniline

5-! Iitro-2-methoxyaniline

4-nitro-2-methoxyaniline

j 2-IvIethylaniline '

i 3-nitro-aniline j

; "2-methylaniline

i t

{2-methylaniline t 2-methoxyaniline
3-nitroaniline

2-methylaniline dark brown s

] J

! Red . i

Red

bluish-red ;

bordeaux

marron

marron

ruDin

marron

blue red

bordeaux

09841/1493 ßAO

Sl

ί 17th I. II . ·; Ill 18th 4-uritro-2-methoxy-
aniline 1-aminonaphthalene bordeaux 19th .2-Kitro-4-methoxy-
aniline Il
i red-violet 20th 2-chloro-5-trifluoro-
methylaniline aniline orange 21 4-chloro-2-trifluoro-
methylaniline 2-methoxyaniline Scarlet fever 22nd 2,5-di-trifluorom-
thylaniline 4-methylaniline • "• ο orange
■ j-run -: ■ - ■ 23 2-nitro-4-trifluoro
methylaniline .
2,5-dimethoxyaniline
:
J Brown
■ ': ■■■■ ■ 24 4-Mtro-2-trifluor-
methylaniline I 2,4-dichloroaniline
:
I. ■
blue red '
■ 25th 4-amino-3-chloro
phenyl-methylsul-
■ sound
; " i - -
2-chloroaniline
i -
^: scarlet 26th : 4-chloro-2-amino-di-
! phenyl ether
; . ·. " I 2-methoxyaniline ^; ■ scarlet fever--
! red I. Γ
I 4-trifluoromethyl-2-
amino-4'-chloro-di-
I phenyl ether ti
j
1 ■ J scarlet

27I 2-chloro-5-trifluoro- | methylaniline j

4-acetylamino aniline

Red

9 09841 / U 93

1903643

Example 11.

24.2 parts of 4-methoxy-j5-aminobenzoic acid anilide are stirred in 100 parts of glacial acetic acid and 25 parts by volume of hydrochloric acid J> 0% and cooled to -5 by adding ice, then at 0-2 with 25 parts by volume. Share 4N sodium nitrite solution diazotized. When the diazotization is complete, it is filtered clear with a little blood charcoal and the diazo solution is adjusted to 0 and p = 4 by adding ice and crystalline sodium acetate. To this solution is allowed to drip under stirring ₀ sodium hydroxide solution, a solution of 30.8 parts of 6-nitro-2- hydroxy-· jj-naphthoic acid anilide in 50 parts of ethanol, 200 parts water and 15 parts JoF.

When the dropwise addition is complete, the mixture is stirred at room temperature until no more diazo compound can be detected. Then warmed up it is filtered briefly to 90-95 ° *, and washed with hot Salt-free water.

The moist press cake obtained is divided into 500 parts Stirred o-dichlorobenzene and azeotropically distilled off the water. After an internal temperature of 145 has been reached, the mixture is released 100 cool, filtered and washed with hot o-dichlorobenzene, then with methanol and finally with hot Water. After drying at 90-95 ° in vacuo, one obtains 51 parts of a soft-grained bluish-red pigment that makes plastics and paints in pure bluish-red tones with very good migration and Fastness to overcoating colors.

9 0 9.841 / US3 '

The pigment of the formula

shows significantly improved migration and overcoating *. fastness, as well as a better light fastness than CI, Pigment-Red 32 (ei. 12.320).

According to the example. 7 or by one of the known coupling methods, the azo pigments listed in the table below can be prepared if an amine from column I is used as the diazo component and an amine from column ΙΓ is used for the preparation of the 6-nitro-2-hydroxynaphthoesaurylide '.
Column III describes the hue of a polyvinyl chloride film colored with the pigment obtained. ·

0 9841 / U93

I. II III 1 4-methoxy-jS-aminobenzoic acid
anilide 3-nitroaniline bordeaux 2 4-methoxy-3-aminobenzoic acid-.
2 ', 4'-dimethylanillide 4-chloroaniline blue red 4-chloro-3-aminobenzoic acid
2 ', 5'-dichloroanilide 4-methoxyaniline Red 4th 4-chloro-3-aminofeenzoic acid
2 ', 4'-dichloroanilide 2-aminonaphtha 1 ■
in yellow,
Red ■ 5 2, 4-dichloro-5-aminobenzoe-
acid amide 4-methoxy anilir Scarlet fever 6th 2, 4-DiGhlor-5-aminobenzoic
acid-2 ' , 5'-dichloroanilide aniline Scarlet fever 7th 4-methyl-3-aminobenzoe-
acid amide. 4-methoxyanilir Red 8th 3-methyl-4-aminobenzoic acid
amide 2-methoxyanilir blue red 9 4-amino-benzoic acid-4'-chloro-
anilide 2-methylaniline Scarlet fever 10 4-methyl-3-aminobenzoic acid
amide 2-aminonaphthal in bordeaux 11th 4-methoxy-3-aminobenzoic acid
3'-trifluoromethyl aniline 5-chloro-2,4-di-
methoxy aniline ruby 12th 4-methoxy-3-aminobenzene sulfo-
N-diaethylamide carmin 1> 4-carbomethoxy-3-aminobenzoe-
acid amide aniline yellow,
Red 14th 4-methyl - ^ - aminobenzenesulfo-
N-propylamide. 2-aminonapti-
thalin Red 15th 4-methoxy-3-aminobenzene-1-
ethyl sulfone 5-chloro-2,4-di-
methoxyaniline Red

909841 / U93

St.

I. II .. ■■ - ■■ III. 16 4-methoxy-3-amino
benzene-1-benzylsul-
hairdryer 4-methoxy-2-methyl-
aniline Scarlet fever 17th 2-4-dimethyl-5-ben-
zoyl-amino-aniline 2-aminonaphthalene bluish tint
Red 18th 2-chloro-5-niethoxy-
4-benzoylamino-ani-
lin aniline corinth 19th 2-methoxy-5-methyl-
4-benzoylamino-ani-
lin 4-methoxyaniline blue violet

90 98417U93

Claims (1)

Claims. 1. Water-insoluble azo compounds of the formula NR ₁ N
OH where R is the radical of a diazotizable amine and R_ is Mean hydrogen atom or an organic radical. 2. Water-insoluble azo compounds according to Claim I in which R ₁ and R ^ are benzene radicals. 3 · Water-insoluble azo compounds according to claims 1 and 2, of the formula where X-., X_ and X, hydrogen or halogen atoms, alkyl, Alkoxy, aryloxy, nitro, cyano, trifluoromethyl, carbonic acid amide, sulfonic acid ester ^ acid ester or sulfonic acid amide groups, Y and Y "hydrogen or halogen atoms, alkyl or alkoxy groups and Y-, a hydrogen or halogen atom or an acylamino group mean. 909841/1493 4 «Water-insoluble azo compounds according to An Proverbs 1 and 2 of the formula ONH wherein X ,, X ₀ and X-, have the meaning given, Y, a hydrogen or halogen atom, Y _c ^ hydrogen or halogen atoms, alkyl, alkoxy, trifluoromethyl or nitro groups, Z is a hydrogen or halogen atom, Z represents a hydrogen or halogen atom, an alkyl or alkoxy group. Water-insoluble azo compounds according to claims 1 and 2 of the formula O ₂ N ^ ^VVN GONH- HO -R NHC NO, where R is an AisrJsirest, Χ _χ , X _g and X ^ have the meaning given. 9 0 9 8 41/14 9 3 6. Water-insoluble azo compounds according to claim 5, wherein R is a phenylene or diphenylene radical. Y _# Water-insoluble azo compounds according to claim 5, in which R is a radical of the formula Z ' ^Z 2
denotes, wherein Z, and Z "denote hydrogen or halogen atoms, alkyl or alkoxy groups. ' 8. Water-insoluble azo compounds according to claim.5 > in which R is a radical of the formula VV denotes in which V denotes a hydrogen or halogen atom, an alkyl or alkoxy group. 90 98 A 1 / U 93 .60 , 9 · "* ■■ Process for the production of water-insoluble azo compounds the formula ■ I OH ..-..- ^τ v-ou . ^V ' ^VN COWH-R ₂ wherein R is the radical of a diazotizable amine and R is a hydrogen atom or denotes an organic radical, characterized in that a) a carboxylic acid halide of the formula N-y OH condensed with ammonia or an anine, or b) a diazotized one Amine or its diazoamino compound with a naphthol of the formula. '' ONH-R. clutch. 90 984 1 / U93 10. The method according to claim 9, characterized in that one of a carboxylic acid halide of the formula given starts out, wherein R, denotes a benzene radical. 11 .. The method according to claim 9, characterized in that * one of a carboxylic acid chloride of the formula OCl starts out, where X ,, Xp and X hydrogen or halogen atoms, Alkyl, alkoxy, aryloxy, nitro, cyano, trifluoromethyl, carboxylic acid ester, carboxamide, sulfonic acid ester or Sulfonic acid amide groups. 12. The method according to claims 9 to H _4, characterized in that an aminobenzene is used as the aromatic amine » 15 · Method according to claim 12 *, characterized in that that you can get an aminobenzene of the formula ^Y l used, in which Y and Y _{2 are} hydrogen or halogen atoms, alkyl or alkoxy groups and Y is a hydrogen or Hätogenatom or an acylamino group. 9 OB 841/14 93 l4. Process according to claim 12, characterized in that an aminobenzene of ⁵ . formula -. used, wherein Y ^ a hydrogen or halogen atom, Y and Ys- "hydrogen or halogen atoms, alkyl, alkoxy, trifluoromethyl or nitro groups, Z a hydrogen or halogen atom, Z _p a'Wwasserstoff- or halogen atom, a Denotes alkyl or alkoxy group. 15 · Process according to claims 9 "to 11, characterized in that that the carboxylic acid halide with a diaminobenzene or diaminodiphenyl condensed in a molar ratio of 2: 1. 16. The method according to claim 15 »characterized in that that you can get a diaminobenzene of the formula. h "m < > m " used, in which Z, and Z _{p are} hydrogen or halogen atoms, alkyl or alkoxy groups. 17. The method according to claim 15, characterized in that that a diaminodiphenyl of the formula V V used, wherein V is a hydrogen or shark atom, a Denotes alkyl or alkoxy group. 9841/1493 .Ιδ.- Method according to claim 9, characterized in that that one starts from a diazotized aminobenzene. 19. The method according to claim l8, characterized in that that one of an aminobenzene of the formula starts out, wherein X ₁ , X ₂ and X have the meaning given. 20. The method according to claim 9 j, characterized in that that the coupling component is a dinaphthol of the formula ογγγ used, wherein R is an arylene radical. 21. The method according to claim 20, characterized in that a dinaphthol is used in which R is a Denotes phenylene or diphenylene radical. 22. The method according to claim 20, characterized in that that a dinaphthol is used in which R is a radical of the formula Z, Z ₂ 9O9841 / U93 means, in which Z, and Zp hydrogen or halogen atoms, Mean alkyl or alkoxy groups. -2Y. Method according to claim 20, characterized in that that a dinaphthol is used in which R is a radical of the formula VV means in which V is a hydrogen or halogen atom, a Denotes alkyl or alkoxy group. 24. Process for pigmenting high molecular weight organic compounds, characterized by the Use of the compounds according to Claims 1 to 8. 25. / The pigmented obtained according to claim 24 Material, ' 909841/14