DE1956710A1 - Water-insoluble disazo dyes - Google Patents

Description

FARBENFABRIKEN BAYER AG

LEVERKU S EN-Btyerwerk J J, NOV. 1969 Ρ «tent department Κ / bU

Water-insoluble disazo dyes

The present invention relates to valuable, new, sulfonic acid and carboxylic acid group-free disazo dyes general formula

K, -N = N- / 'I ^X V NH-CO-CO-NH -Jf ' VN = NK ₀ (I)

in which K ₁ and Kp are identical or different and represent the remainder of a coupling component and R ₁ and Rp independently of one another represent hydrogen or a substituent (with the exception of sulfonic acid and carboxylic acid groups).

Suitable substituents R _{1 and R 2} are halogen atoms, such as fluorine, chlorine and bromine, alkyl radicals having 1 to k carbon atoms and alkoxy radicals having 1 to 4 carbon atoms.

Suitable radicals K and K ₂ are optionally mono- to trisubstituted 2-hydroxynaphthalene-3-carboxylic acid arylamide and acetoacetic acid arylamide radicals in the respective aryl radical, as well as l-aryl pyrazolone-5 radicals, which are optionally in the phenyl radical and in the pyrazolone radical also in 3-position can carry further substituents.

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10982 1 / 200Λ

Particularly preferred substituents in the aryl radical - preferably Phsnylrest - are halogen atoms such as fluorine, chlorine and bromine, Alkyl, alkoxy, alkylsulfonyl and alkylsulfamoyl groups each having 1 to 4 carbon atoms, acyl, acyloxy, acylamino and Alkoxycarbonyl groups each with 2 to 5 carbon atoms, phenoxy groups, phenylsulfonyl groups, phenylsulfamyl, cyano, Nitro, carbamoyl, trifluoromethyl and hydroxyl groups.

Particularly preferred substituents in the j5-3 position des 5-pyrazolone radicals are alkyl radicals with 1 to 4 carbon atoms, Carbamoyl, carboxyl and alkoxycarbonyl radicals with 2 to 5 carbon atoms.

Preferred substituents in the 1-aryl radical - preferably 1-phenyl radical - of 5-pyrazolone are chlorine, fluorine, alkyl and alkoxy radicals with 1 to 4 carbon atoms, as well as a nitro, Cyano, carbamoyl, sulfaraoyl or acetylamino group.

The new dyes can be produced by various processes.

This is obtained in a particularly favorable manner if one uses diamines of the general formula

H ₂ N - //; \> - NH-CO-CO-NH-V! V- ^NH o (H)

in which R- and FU have the abovementioned meaning, tetrazotized and coupled to coupling components K, H or KpH, which are free of sulfonic acid and carboxylic acid groups, or successively to K, H and KpH, where K ^ and K _{2 have} the abovementioned meaning.

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Some of the tetrazo components (II) are known. They are obtained in a manner known per se by reacting 1 mole of oxalic acid dichloride with 2 moles of a suitable 4-nitroaniline derivative and subsequent catalytic reduction of the nitro group.

/ Ms tetrazo components (H) are possible, for example:

4,4'-diamino-oxariilide, 4,4'-diamino-2,2'-dichloro-oxanilide, 4,4'-diamino- Z>, 3'-dichloro-oxanilide, 4,4'-diamino-2 , 2 ', 5.5' -

tetrachloro-oxanilide, 4,4 -'-diamino - ^ * 3 '-difluoro-oxanilide,

4,4'-diamirio-;5,3'-dibromo-oxanilide,4,4'-diamino-2,2',-5,5'-tetrafluoro-oxanilide,4,4'-diamino-2,2', 5. » 5 '-tetrabrom-oxanilide, 4,4 ^l diamino-2,2'-dichloro-5,5'-dimethoxy-oxanilide, 4,4'-diamino-5,5'-dichloro-2,2'-dimethyl -oxanilide, 4,4'-diamino-5,5'- f dichloro-2,2'-dimethoxy-oxanilide, 4,4'-diamino-5,5'-dichloro-2,2'-diethoxy-oxanilide, 4,4'-diamino-2,2'-dimethyl-oxanilide, 4,4'-diamino-2,2'-dimethoxy-oxanilide, 4,4'-diamino-2,2 ', 5 * 5'-tetramethyl -oxanilide, 4,4'-diamino- ^ 2,2 ', 5, 5 ¹ -tetramethoxyoxanilide, 4,4'-diamino-2,2'-dimethoxy-5,5'-dimethyl-oxanilide,

4,4'-diamino - ^, 3 ^! >3>5'-tetrachloro-oxanilide.

Particularly suitable coupling components are:

a) from the pe ine of Hydroxynaphthalincarbonsäureary! amide:

2-hydroxy-naphthoic acid- (3) -anilide, 2-hydroxy-naphthoic acid- (5) _ (2'-methyl) -anilide, 2-hydroxy-naphthoic acid- (3) - (4'-methyl) -anilide, 2-hydroxy-naphthoic acid- (3) - (2'-methoxy) -anilide, 2-hydroxy-naphthoic acid- (3) - (2 ', 5 ^l -dimethoxy) -anilide, 2-hydroxy-naphthoic acid- (3) - (4 -'-methoxy) -anilide, 2-hydroxynaphthoic acid- (3) - (3'-nitro) -anilide, 2-hydroxy-naphthoic acid- (3) _ (2-chloro) -anilide, 2-hydroxy -naphthoic acid- (3) - (3'-tri-

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1 0 9 R? I /? π ru

BATH ORIGINAL

fluoromethyl) anilide, 2-hydroxynaphthoic acid (3) - (4'-fluoro) anilide, 2-hydroxynaphthoic acid (5) - (4'-chloro) anilide, 2-hydroxynaphthoic acid ( 3) - (2 ', 4 ^l -dimethyl) -anilide, 2-hydroxy-aaphthoic acid- (3) - (2'-raethyl-5 ¹ -chlor) -anilide, 2-hydroxy-naphthoic acid- (3) - ( 2'-raethyl-4 ^l -ohlor) -anilide _J 2-hydroxy-naphthoic acid- (3) - (2 ', 5'-dimethoxy-4'-chloro) -anilide, 2-hydroxy-naphthoic acid- (5) - (2 ', 4'-dimethoxy-5 ^f -chlor) -anilide, 2-hydroxy-naphthoic acid- (j5) - (2'-methyl-4'-methoxy) -anilide, 2-hydroxy-naphthoic acid- (3) - (2'-methoxy-5'-chloro) -anilide, 2-hydroxy-naphthoic acid- (3) - (4'-methoxy-2 * -chlor) ~ ianilide, 2-hydroxy-naphthoic acid- (3) - ( 2 ^l -methyl-3'-chloro) -anilide, 2-hydroxy-naphthoic acid- (3) - (naphthyl- (l ')) - amide, 2-hydroxynaphthoic acid- (3) - (naphthyl- (2')) -amid, 2-hydroxy-naphthoic acid- (3) - (2'-ethoxy) -anilide, 2-hydroxy-naphthoic acid- (3) - (4'-ethoxy) -anilide, 2-hydroxy-naphthoic acid- (3) - (2 ^f -methoxy-5'-methyl) -anilide, 2-hydroxy-naphthoic acid- (3) - (4 ^! -Acetylamino) -anilide, 2-hydroxy-naphthoic acid- (3) - (2 ', 5'-dichloro) -anilide, 2-hydroxy-naphthoic acid- (4'-acetylamino-2,5-dichloro) -anilide, 2-hydroxy-naphthoic acid- (3) - (2 ^f -methoxy- 4'-methyl) -anilide, 2-hydroxy-naphthoic acid- (3) - (2 ^! , 4'-diethoxy) -anilide, 2-hydroxy-naphthoic acid- (3) - (4 · -nitro) -anilide.

b) from the series of acetoacetic aryl & mj-cle Acetoacetic anilide, acetoacetic acid-2-chloro-anilide, acetoacetic acid-2,4-dimethyl-anilide, Acetoacetic acid-2-methylanilide, acetoacetic acid ^ iS-dimethoxy ^ -chloro-anilide, acetoacetic acid-2-methoxy-anilide, Acetoacetic acid naphthyl- (l) -araid, acetoacetic acid ^ -methyl ^ -chloro-anilide, acetoacetic acid-2-methyl-4-chloro-anilide, Acetoacetic acid-2,4-dichloro-anilide, acetoacetic acid ^ -nitro ^ -chloro-anilide, acetoacetic acid-2-nitro-4-methyl-anilide, Acetoacetic acid ^ -nitro ^ -methoxy-anilide, acetoacetic acid-4-ethoxy-anilide, acetoacetic acid-4-acetylaminoanilide, Acetoacetic acid-4-benzoylamino-anilide, acetoacetic acid-2-methoxy-4-methyl-anilide, Acetoacetic acid-4-methyl-anilide,

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Acetoacetic acid - ^ - chloro ^ -nitro-anilide, acetoacetic acid-2,4-dinitro-anilide, acetoacetic acid - ^^ - dichloro-anilide, acetoacetic acid-2methyl-5-nitroanilide _i acetoacetic acid-2,4-dimethoxy-5-chloroanilide.

c) from the series of the l-phenyl-pyrazolone-5

1- (3'-sulfamoyl-phenyl) -3-methyl-pyrazolone-5, 1- (4'-sulfamoyl-phenyl) -3-methyl-pyrazolone-5, 1- (3'-benzoylamino-phenyl) -3-methyl -pyrazolone-5, l- (4'-Benzoylamino-phenyl) -3-methylpyrazolone-5, 1- ^ 3 '- (4 "-chloro-benzoyl-araino) -phenyl7-3-methylpyrazolone-5, l-phenyl -pyrazolone-S-carboxylic acid - ^ - amide, l-phenyl-pyrazolone-5-carboxylic acid-3-N-ethyl-aπlid, 1-phenylpyrazolone-5-carboxylic acid-3-anilide, l-phenyl-pyrazolone-5-carboxylic acid -3- (4-methyl) -anilide _# 1- (3'-carbamoyl-phenyl) - ^ - j

methyl-pyrazolon-5 * 1- (4'-carbamoyl-phenylJ - ^ - methyl-pyrazolon ^, 1- (3'-carbanilino-phenyl) -3-methyl-pyrazolon-5j l- (4'-carbanilino-phenyl ) -3-methyl-pyrazolone-5, l- (4'-chlorophenyl) -pyrazolone-S-carboxylic acid - ^ - amide, l- (4'-fluorophenyl) -pyrazolone-5-carboxylic acid-5-anilide, l- (2'-Methylphenyl) -pyrazolon-5-carboxylic acid-3-araid, 1- (3'-Nitropüenyl) -pyrazolone-5-carboxylic acid-3-anilide, 1- (2 ', 5' -Dichlorphenyl) -pyrazolon- 5-carboxylic acid-j5-anilide, l- (4'-Ciilorphenyl) -3-methyl-pyrazolon-5, l- (2'-methoxyphenyl) -3-methyl-pyrazolon-5 * l- (4'-methylphenyl) -3-methyl-pyrazolone-5, l- (3'-cyanophenylJ - ^ - methyl-pyrazolone ^, l- (3'-nitrophenyl) - ^ - methyl-pyrazolone-S, l-phenyl-3-methylpyrazolone-5 , l- (2'-chlorophenyl) -3-methyl-pyrazolone-5, l- (3'-chlorophenyl) -5-methyl-pyrazolone-5 * l- (2 ^t , 5 ^f -diohlophenyl) -3- \ methyl-pyrazolone-5, l- (4'-nitrophenyl) -5-methyl-pyrazolone-5, l-phenyl-pyrazolone-S-carboxylic acid - ^ - ethyl ester, l- (3'-nitrophenyl) -pyrazolone-S- carboxylic acid I-ethyl ester, 3-methyl-pyrazolone-5

The preparation of the new dyes takes place in detail so that the corresponding diamine in glacial acetic acid / propionic acid with Nitrosylsulfuric acid or in hydrochloric acid (19 * 5 ° Be) tetrazotized with aqueous sodium nitrite solution and in the presence of a

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Ionic, cationic or non-ionic surface cells By means of, for example, an alkyl sulfonate and / or polycondensation product from octyl alcohol and ethylene oxide and / or in the presence of an organic solvent such as Pyridine, dimethylformamide or 1,2-dichlorobenzene with the corresponding azo components is implemented.

According to a further process, the new dyes are obtained if 2 moles of aminoaryl monoazo dyes of the general formula are used

K-N = N

in which K denotes the remainder of a coupling component and R, and Rp have the abovementioned meaning, Reacts with approximately 1 mole of oxalyl chloride.

This reaction is conveniently carried out in a suitable organic solvent such as toluene, chlorobenzene or 1,2-DichlOFbenzol carried out.

Occasionally it proves to be beneficial to dissolve the pigments thus obtained in an organic solvent such as n-butanol, To heat pyridine, dimethylformamide, toluene, chlorobenzene or 1,2-dichlorobenzene in order to achieve the Increase color strength, solvent fastness and light fastness.

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Thanks to their good lightfastness and very good solventfastness, the new dyes can be used for the most diverse Pigment applications are used. They are suitable for the production of very real pigmented compositions, such as Mixtures with other substances, paints, printing inks, colored paper and colored macromolecular substances.

Mixtures with other substances can be understood as meaning, for example, those with inorganic white pigments such as titanium dioxide. The term paint stands, for example, for physically or oxidatively drying paints, stoving paints, reactive paints, two-component paints, emulsion paints for weatherproof coatings and glue paints. Printing inks are to be understood as meaning those for paper, textile and metal printing. The macromolecular substances can be of natural origin such as rubber, obtained by chemical modification such as acetyl cellulose, cellulose butyrate or viscose, or produced synthetically such as polymers, polyaddition products and polycondensates. Plastic compounds such as polyvinyl chloride, polyvinyl acetate, polyvinyl propionate, polyesters, for example polyethylene terephthalate, polyamides, super polyamides, polymers and copolymers of acrylic esters, methacrylic esters, acrylonitrile, acrylamide, butadiene, styrene, and polyurethanes and polycarbonates may be mentioned.

example 1

A mixture of 8.9 g of 4,4'-diamino-2,2 ', 5,5'-tetrachloroxanilide in 100 ml of glacial acetic acid and 20 ml of propionic acid is stirred overnight, then cooled to 0 ° and treated with 13.8 g of nitrosylsulfuric acid (41 #ig) slowly offset. The tetrazonium

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binding is stirred for 4 hours at 0-5 ° C. 8.6 g of 1-p-tolyl-3-methyl-pyrazolone-5 are dissolved in 100 ml of glacial acetic acid, diluted with 100 ml of ice water and with 2 g of urea and 0.2 g a polycondensation product from octyl alcohol and ethylene oxide. The tetrazonium suspension is at approx. 5 ° C poured to the pyrazolone. The mixture is blunted with 250 ml of 20% sodium acetate solution and stirred overnight. The reaction mixture is heated to 70 - 80 ° C, stirred for 15 minutes, Vacuumed hot and washed with hot water. After drying at 50 ° C, the orange-yellow pigment becomes extracted with 100 ml of toluene.

. Cl

Cl

\ Ή —- CO — CO

~ -NH— (TVV-N-N-

-CH,

A mixture of 65 g of polyvinyl chloride, 35 g of diisooctyl phthalate, 2 g of dibutyltin mercaptide, 0.5 g of titanium dioxide and 0.5 g of the above pigment, which was finely divided by grinding with sodium chloride in the presence of N-methylpyrrolidone, is placed on a roller mixer dyed at I65 C ^0. An orange-yellow colored mass is obtained which can be used for the production of foils or shaped bodies. The brilliant coloring is characterized by good lightfastness and very good migration fastness.

Le A 12 433

109B? 1 /? 0 (H.

The 4.4 ^l -Diamino-2.2 ^! , 5i5'-tetrachloro-oxanilide is prepared as follows: A suspension of 82.8 g of 2,5-dichloro-4-nitroaniline in 1.5 l of toluene is dried azo-tropically, and 26 g of oxalyl chloride are added at room temperature. After 1 hour, the mixture is heated to 60 ° C. and stirred at 60 ° C. for 5 hours. The pale yellow product is filtered off with suction at room temperature, washed with methanol and dried at 80.degree. The 4,4'-dinitro-2.2 ^t , 5,5'-tetrachloroxanilide melts at 301-302 ° C and contains 11.95 % nitrogen ^(N ber. ^N > 96). 40 g of 4,4-dinitro-2,2 ', 5,5'-tetrachloroxanilide are catalytically reduced (Raney nickel) with hydrogen in 1.2 l of dimethylformamide at 75 ° C., filtered off while hot and diluted with 2 l of water at room temperature . The yellow crystals are filtered off with suction at room temperature, i

washed with water and dried at 50-80 ° C. The 4,4'-diamino-2.2 ^l , 5.5 ^t -tetrachloro-oxanilide melts at - 350 ° C and contains 13.65 % nitrogen (Ν _ηβ _ 13 * 72).

Example 2

A suspension of 8.9 g of 4.4 ^! -Diamino 2.2 ', 5.5 ^! -tetrachloroxanilide in 80 ml of hydrochloric acid (19.5 ° Be) is stirred at 20 ° C for 1/2 hour, cooled to 0 ° C and tetrazotized with 150 ml of a 2 # sodium nitrite solution. After about 1/2 hour, the tetrazonium salt solution is filtered off with suction and the excess nitrite is removed with a little amidosulfonic acid. In 500 ml of water, 20 ml of 10 η sodium hydroxide solution and 0.5 g of a polycondensation product made from octyl alcohol and ethylene oxide, 14 g of l- (2 ', 3 ^! . After cooling to room temperature, the naphthol is precipitated by pouring in 50% acetic acid and the tetrazonium salt solution is poured in. The mixture is blunted with about 250 ml of 20% sodium acetate solution and stirred

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5i room temperature overnight, heated to 80 ° C and sucked hot off the dye. After drying at 50 ° C., the disazo dye is extracted at 80 ° C. with 100 ml of n-butanol.

8 g of the dye, which were finely divided by grinding in a vibrating mill with 2 ml of xylene and ΙβΟ g of sodium chloride and washing out the common salt, are coated with a stoving varnish made from 25 g of coconut alkyd resin (40 % coconut oil), 10 g of melamine resin, 5 ml of toluene and 7 ml of glycol monomethyl ether dispersed in a ball mill. The mixture is applied to the substrate to be painted, the paint is cured for half an hour by stoving it at 110.degree. C. and carmin-red, brilliant paintwork is obtained with very good overpainting properties and good lightfastness.

The tetrazo and coupling components listed in the table below also give valuable pigments with the specified hues, if one as in the previous examples is working.

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Totraz ok omponont c:

Coupling component:

Hue:

4 =

4.4'-diamino-3.3'-dichloro-oxanilide

4.4 * -Diamino-oxanilide

4.4'-diamino-2.25.5 ^f ~ totraethoxyoxanide

4.4 * -Diamino-2.2 ^r .5.5 * -tetramethoxyoxanilide

4,4'-diamino-3,3 ', 5,5 * -tetrachloroxanilide

2-hydroxy-naphthoo3 acid-3- (2'-methoxy) -anilide Bordo

2-IIydroxy-naphthoic acid-3- (2'-ethoxy) -anilide Bordo

1- (3'-Chlorophenyl) -3-methyl-pyrazolone-5 yellow orango

2-hydroxy-naphthoic acid-3- (2'-methyl-4'-methoxy) -

anilid blauos red

l-p-tolyl-3-methyl-pyraz; olon-5

Acctoacctylamino-2.4-dimcLhyl bonzol-2-hydroxy-naphthocsäuro-3- (2 ^t -üthoxy) -anilide

golden orango

GcIb

blue

2-IIydroxy-naphthoosiiuro-3- (2 '. 4' -dimothoxy-5-

chlorine anilide blue

l-p-tolyl-S-mothyl-parazolon-o

Red

2-hydroxy-naphthoic acid-3- (2 · .4 * -dimothoxy-5'-

chlorine anilide blue

2-hydroxy-napthoic acid-3- (2'-ra ^

2-Hydroxy-napthoic acid- (2'-methyl-4'-methoxy) anilide

2-hydroxy-napthoic acid (2'-ethoxy) anilide 2-hydroxy-napthoic acid (4'-ethoxy) anilide

Bordo

Marron

Bordo

Bordo orange

Tetrazo component:

Coupling component:

Hue:

_H 4.4 ^? -Diamino-5.5 ^t -dichlor-2.2 ¹ · W dimethyl-oxanilide

TO

»I» I

tt ft

4.4 ^t -diamino-5.5 ^t -dichloro-2.2 ^l dimethoxy-oxanilide

4.4'-diamino-2.2'-dichioroxanilide "

»T» f 2-Hydroxy-naphthoic acid-3- (2 ^f -methyl) -anilide

2 ~ hydroxy-naphthoic acid-3- (2 ^t -ethoxy) -anilide
2-Hydroxy-naphthoic acid-3- (4 * -methoxy) -anilide

2-Hydroxy-naphthoic acid-3- (2'-methyl-4 ^f -methoxy) -anilide

2-Hydroxy-naphthoic acid-3- (3'-nitro) -anilide
lp-Tolyl-S-methyl-pyrazolone-S
l-acetoacetylamino ^ .S-dimethoxy ^ -chlorobenzene
1-acetoacetylamino ^ -acetylamino-benzene

2-Hydroxy-naphthoic acid-3- (2'-methyl ^ * - mothoxy) -anilide

2-Hydroxy-naphthoic acid-3- (2 * -ethoxy) -anilide
2-hydroxy-naphthoic acid-3- (4'-ethoxy) -anilide
lp-Tolyl-S-Methyl-pyrazolone-S

2-Hydroxy-naphthoic acid-3- (2'-methyl-4- ^t -methoxy) -anilide

2-hydroxy-naphthoic acid-3- (2 ^T .4'-dimethoxy-5 * -
chlorine) anilide

2-hydroxy-naphthoic acid-3- (2 * .5 * -dimethoxy-4 * -
chior) anilide

2-hydroxy-naphthoic acid-3- (2 * -methyl-4 ^f -chlor)
anilide

l-phenyl-S-methyl-pyrazolone-S
1- (3'-Carbaniyl-phenyl) -3-ynethyl-pyrazolon-5

violet

Marron Marron

Marron Bordo Orange Yellow Green Yellow

Violet violet violet orange

Bordo Bordo Bordo

Bordo

yellow orange

yellow orange

tr *

Tetrazokoraponente:

Coupling component:

Hue·

IO

4s-

oxanilide

O I. tf dd co OO I. NJ dd dd - » " η dd dd O dd It dd dd dd dd dd dd

2-Hydroxy-naphthoic acid-3- (2'-methyl) -anilide

2-hydroxy-naphthoic acid-3- (2'-methoxy) -anilide
2-hydroxy-naphthoic acid-3- (4'-methoxy) -anilide

2-hydroxy-naphthoic acid-3- (2'.4'-dimethoxy-5-chloro) anilide

2-Hydroxy-naphthoic acid-3- (3'-nitro) -anilide
2-hydroxy-naphthoic acid-3- (4 ^t-nitro) -anilide

2-Hydroxy-naphthoic acid-3- (2'-methyl-3 * -chlor) -anilide

2-Hydroxy-naphthoic acid ^{3r (2 f} -methyl-4'-methoxy)
anilide

l-phenyl-S-methyl-pyrazolone-o

l-CS'-nitrophenyD-S-methyl-pyrazolone-S

1- (3 ^f -chlorophenyl) -3-methyl-pyrazolone-5

1- (4 * -chlorophenyl) -3-methyl-pyrazolone-5

1- (3'-carbamylphenyl) -3-methyl-pyrazolone-5

1-phenyl-S-carbethoxy-pyrazolone-S

l-acetoacetylamino ^ .S-diinethoxyHL-chlorobenzene

l-acetoacetylamino-2,4-dimethyl-benzene

1-acetoaoetylamino ^ -chlorobenzene

1-acetoacetylamino-2-methoxy-4-methylbenzene

Bordo

Bordo Bordo

Marron

Bordo

Bordo

Bordo

Bordo

yellow orange

orange

yellow orange

yellow orange

yellow orange

orange

Yellow

red yellow

Yellow yellow

Example 3

A mixture of 8.9 g of 4,4'-diamino-2,2 ^f , 5,5'-tetrachloroxanilide in 50 ml of glacial acetic acid and 40 ml of hydrochloric acid (19.5 ° Be) is stirred at 20 ° C. for 1 hour Cooled to 0 ° C and mixed with 150 ml of a 2% sodium nitrite solution. After 3 hours, the excess nitrite is removed with sulfamic acid. In 500 ml of water, 20 ml of 10 η sodium hydroxide solution and 0.5 g of a polycondensation product of octyl alcohol and ethylene oxide, 7 g of 2-hydroxy-naphthoic acid-3- (2'-ethoxy) -anilide and 6 g of 2-hydroxy-naphthoic acid-3 - (2'-methyl) -anilide briefly dissolved at 80 - 90 C and suctioned off. After cooling to 20 ° C., the naphthol is precipitated by pouring in 50% acetic acid and the tetrazonium compound is added. With about 300 ml of 20% sodium acetate solution, the mixture is blunted, stirred at 20 ° C. overnight, heated to 80 ° C. and the dye is filtered off with suction while hot. After drying, the disazo dye mixture is extracted with 100 ml of 1,2-dichlorobenzene.

With a printing ink made by rubbing 35 g of the finely divided above dye and 65 g linseed oil and addition of 1 g siccativ (co-naphthenate 50 #ig in white spirit) Bordo-red offset prints of high brilliance and color strength and good lightfastness and very good lacquer fastness are obtained. use this printing ink in letterpress, collotype, stone or steel engraving leads to border-red prints of similar fastness properties.

Example 4

To a suspension of 23 * 3 S of the aminophenylazo dye the formula

OH CO-NH

N = N

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obtained by combining the conventionally diazotized 2,5-dichloro-p-phenylenediamine with an equimolar amount of 2-hydroxy-naphthoic acid-2- (2'-methyl) anilide in the aqueous Medium at pH 5-6 in 250 ml of 1,2-dichlorobenzene is added 20-30 ° C 3.2 g of oxalyl chloride and stir for 1 hour. Afterward the mixture is heated slowly (for 3 hours) to 160 ° to 170 ° C. and refluxed for 8 hours. You leave on overnight Cool to 20 ° C, suction filtered, washed with toluene, methanol and warm water and obtained after drying at 50 ° C bluish-red crystals.

Example 5

To a suspension of 17 »3 g of the aminophenylazo dye J of the formula

obtained by combining the conventionally diazotized 2,5-dichloro-p-phenylenediamine with an equimolar amount of 1-phenyl-3-methyl-pyrazolone-5 in an aqueous medium at pH k-5 in 250 ml of 1,2-dichlorobenzene 3.2 g of oxalyl chloride at 20-30 ° C. and stir for 1 hour. The mixture is then heated to 160-170 ° C. for 3 hours and refluxed for 8 hours. The mixture is allowed to cool to 20 ° C. overnight, filtered off with suction, washed with toluene, methanol and warm water and, after drying at 50 ° C., orange-yellow crystals are obtained.

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Claims (15)

xb e η tans test_e JLy) Disazo dyes free of sulfonic acid and carboxylic acid groups the general formula NH-CO-CO-NH in which K, and K "represent the same or different radicals of coupling components and R ₁ and R _9, independently of one another, represent hydrogen or substituents * with the exception of sulfonic acid and carboxylic acid groups. 2.) Disazo dyes free of sulfonic acid and carboxylic acid groups the general formula in which K ₁ 'and K ₃ ^{1 are} identical or different radicals of the 2-hydroxy-naphthoic acid-3-arylamide or pyrazolone series, and R' and Rp ^{1 are} independent of one another Le A 12 - 16 - for halogen atoms, preferably chlorine, Alkyl radicals with 1 to 4 carbon atoms, or alkoxy groups with 1 to 4 carbon atoms
stand. 3.) Disazo dyes free of sulfonic acid and carboxylic acid groups the general formula NH-CO-CO-NH Cl in which X, and X _{2 are} independently chlorine, alkyl radicals and alkoxy radicals each having 1 to 4 carbon atoms or hydrogen and X is hydrogen, chlorine, alkyl radicals and alkoxy radicals each having 1-4 carbon atoms. Le A 12 433 - 17 - T098M /? 004 4.) Disazo dyes free of sulfonic acid and carboxylic acid groups the general formula Cl ■ Cl NH-CO-CO-NH - ^ [^ - N = N Cl Cl in which Y is hydrogen, alkyl radicals with 1 to 4 carbon atoms, carbamoyl, carboxyl and alcoxycarbomyl radicals with 2 to 5 carbon atoms means, Z for hydrogen, chlorine, fluorine, nitro, cyano or alkyl radicals with 1 to 4 carbon atoms and η represents the numbers 1 to 3. 5.) Disazo dye of the formula Le A 12 453 - 18 - 109871/2004 19567 ΊΟ 6.) Disazo dye of the formula Cl Cl N = N C = O " ^0H Cl NH OCH, NH-CO-CO-NH Cl HO C = O NH OCH- 7.) Disazo dye of the formula Cl Cl N = N C = O * ^0H Cl NH OC ₂ H NH-CO-CO-NH Cl HO C = O
NH OC ₂ H ₅ 8.) Disazo dye of the formula Cl ^r = N - ^ _ V-NH-CO-CO-NH OH Cl Cl CH- Le A 12 - 19 - 109821/7004 9.) Disazo dye of the formula CONH ₂ V-T-N = N Cl NH-CO-CO-NH Cl CONH. 10.) Process for the preparation of sulfonic acid and carboxylic acid egruppe-free disazo dyes, characterized in that that one diamines of the general formula NH-CO-CO-NH R, in which R ₁ and R ₂ independently represent hydrogen or substituents, tetrazotized and coupled to coupling components, choosing the external components free of sulfonic acid and carboxylic acid groups . 11.) Process for the preparation of sulfonic acid and carboxylic acid groups-free Disazo dyes, characterized in that one diamines of the general formula Le A 12 433 - 20 - 109821/7004 NH-CO-CO-NH in which R ₁ 'and R ₂ ' independently represent hydrogen, halogen atoms, preferably chlorine, alkyl radicals with 1 to 4 carbon atoms, or alkoxy groups with 1 to 4 carbon atoms, tetrazotized and on 2-hydroxy-naphthoic acid-3-arylamide- or Coupling pyrazolone residues and choosing the starting components free of sulfonic acid and carboxylic acid groups. 12.) Process for the preparation of sulfonic acid and carboxylic acid groups-free Disazo dyes, characterized in that 2 moles of identical or different aminoaryl monoazo dyes are used the general formula R. K-N = N in which K denotes the remainder of a coupling component and R, and Rp independently of one another for Are hydrogen or substituents, Reacts with approximately 1 mole of oxalyl chloride while leaving the starting products free of sulfonic acid and carboxylic acid groups chooses. Le A 12 433 - 21 - 109821/2004 13.) Process for the preparation of sulfonic acid and carboxylic acid groups re ien disazo dyes, characterized in that 2 moles of identical or different aminoaryl monoazo dyes are used the general formula in which K ^{1 is} the remainder of a coupling component from the 2-hydroxy-naphthoic acid-3-arylaniicl, acetoacetic acid arylamide or pyrazolone series and R ¹ and Rp independently of one another represent halogen atoms, preferably chlorine, alkyl radicals having 1 to 4 carbon atoms, or alkoxy groups with 1 to 4 carbon atoms, Reacts with approximately 1 mole of oxalyl chloride and thereby the starting products free of sulfonic acid and carboxylic acid groups chooses. 14.) Use of the sulfonic acid and carboxylic acid groups-free Disazo dyes of claim 1 for pigmenting lacquers and paints, for mass coloring polymers, polycondensates, Polyaddition products and vulcanizates, as well as for coloring printing inks and printing inks. 15.) Varnishes, paints, polymers, polycondensates, polyaddition products, vulcanizates, printing inks and printing inks, pigmented or mass-colored with disazo dyes of claim 1. Le A 12 433 - 22 - 109821/2004