DE1544527C - Process for the production of azo dyes - Google Patents

Description

The present invention relates to the preparation of valuable new azo dyes of the formula

NHR

N = NR ₁ (I)
OH

where Y Tür is a sulfonic acid group, R is hydrogen or an optionally substituted alkyl radical and R _{1 is} the radical of a diazo component containing sulfonic acid groups.

A particularly valuable group of dyes in the context of the formula (I) corresponds to the formula

HO ₁ S

(H)

where R | the remainder of a sulfonic acid group-containing diazo component of the benzene or naphthalene series means.

The new dyes are obtained by using the diazo compound of an amine of the formula

R ₁ - NH ₂

wherein R _{1 has} the above meaning with 1 mol of a coupling component of the formula

NHR

OH

35

(IH)

NH-CO

in which R and Y have the meanings already given, combined. The coupling takes place in acidic, preferably an aqueous medium and is peri-position to the hydroxyl group or in that of the NHR group neighboring α-position of the naphthalene component (III).

One can also proceed in such a way that, instead of the diazo compound of an amine of the formula R ₁ - NH _2, the diazo compound of an amine of the formula R ₂ - NH _{2 is} used, in which R _{2 is} an aromatic radical containing sulfonic acid groups, which is customary in azo chemistry Reactions such as reduction, saponification, acylation and / or condensation, can be converted _{into the radical R 1} , and then converts _{the radical R 2} into the radical R _{1 following the coupling.}

The dyes (II) preferred in the context of the dyes of the formula (I) are obtained by coupling the Diazo compounds of the amines listed with 2 - amino - 8 - hydroxynaphthalene - 5 - sulfonic acid in available analogously.

Coupling components of the formula (III) are, for example, in British Patent 5148 (1894) described (cf. N.Donaldson, "The Chemistry and Technology of Naphthalene Compounds", P. 323).

Suitable diazo components R ₁ - NH ₂ for the preparation of monoazo dyes are, for example, 4-amino-4'-acylaminodiphenyl-3-sulfonic acids (where acyl ζ. B. acetyl, propionyl, fumaroyl, benzoyl, m- or p-chlorobenzoyl, m- or p-toluyl, m- or p-nitrobenzoyl, m-trifluoromethylbenzoyl, terephthaloyl, isophthaloyl, benzenesulfonyl or a benzenesulfonyl radical substituted in the benzene nucleus), unsymmetrical ureas, such as N - phenyl-N ', 4' - (4 - aminodiphenyl - 3 - sulfonic acid) - urea, which can be substituted in the phenyl nucleus, for example by chlorine in the p- or m-position, aminophenylureas of the formula

NH —CO —NH

SO ₃ H
in which T, hydrogen or substituents, such as e.g. B. chlorine, means amino compounds of the formula

H ₂ N-

NH-

-CO

SO., H

in the T ₂ z. B. a triazinyl radical, a pyrimidyl radical, such as the dichloropyrimidyl, trichloropyrimidyl or 2-methylsulfonyl-5-chloro-6-methylpyrimidyl radical, also the 2-methylsulfonylnicotinoy! Radical, the 2,6-dichloro or 2,6-dimethylsulfonyl - isonicotinoyl radical, which can mean 2,3-dichloroquinoxalinoyl- (6) - or 2,3-dichloroquinoxaline-6-sulfonyl radical and m is a number from 0 to 2.

Examples of amines of the formula R ₂ - NH ₂ are: l-amino-4-nitrobenzene-2-sulfonic acid, l-amino-4-acylaminobenzene-2-sulfonic acids, such as /.B. I-amino-4-acetylaminobenzene-2-sulfonic acid, I-amino-4- (4'-nitr () benzoylamino) -ben / ol-2-silf () iic acid, I-amine () - 4 - (. T. -nitrobcn /. «ylamint)) - bcn / ol-

2-sulfonic acid, I-amino-4- (4'-nitro-3 '- methylbenzoylamino) -benzene-2-sulfonic acid and I-amino-4- (4'-nitrobenzenesulfonamido) -benzene-2-sulfonic acid, also 4-amino-4 '- (4 "-nitrobenzoylamino) -diphenyl-3-sulfonic acid, 4-Amino-4 '- (3 "-nitrobenzoylamino) -diphenyl - 3 -sulfonic acid, 4-Amino-4' - (3 - nitro-4" - methylbenzoylamino) - diphenyl - 3 - sulfonic acid, 4 - amino - 4 '- acetylaminodiphenyl - 3 - sulfonic acid, 2 - amino - 6 - nitronaphthalene - 4,8 - disulfonic acid, 4 - amino - 4 '- nitrostilbene - 2,2' - disulfonic acid and 4 - Amino -4'-acetylaminostilbene-2,2'-disulfonic acid. The new dyes are valuable products that are very good at dyeing and printing hydroxyl groups and amide group-containing monomers

suitable, such as for dyeing native and regenerated cellulose, wool, silk, super polyamide fibers and the like. The dyeings obtained, especially those on cellulose fiber materials, are characterized by good results Fastness properties, in particular due to very good lightfastness.

In J. Gen. Chem., 21, 1951, p. 1259, the dye is Aniline - * 2 - amino - 8 - hydroxynaphthalene - 5 - sulfonic acid described, while from German patents 866 702 and 912131 dyes of the type substituted sulfoaniline -> 2 - amino - 8 - hydroxynaphthalene-6-sulfonic acid are known. None of these literature references indicate that by exchanging the diazo or coupling components dyes with excellent properties can also be obtained. So it was completely surprising and not foreseen that by introducing a sulfo group into the diazo component of the dye of the first-mentioned literature reference, dyes with higher lightfastness can be obtained by replacement the coupling components of the * dyes of German patents 866 702 and 912131 the coupling component of the dye described in the first reference, however, dyes with much better solubility in water.

NH

HO ₁ S

SO ₃ H

is finished. The dye is salted out, isolated and dried. It sets when dry dark powder that dissolves in water with a red color. The dye dyes cotton in red Shades with very good lightfastness.

If the acylating agent used is cyanuric chloride instead of dichloroquinoxaline carboxylic acid chloride In the following examples, parts stand for parts by weight, unless otherwise stated.

example 1

23.9 parts (0.1 mole) of 2-amino-8-hydroxynaphthalene-5-sulfonic acid (produced according to the details of British patent specification 5148 [1894]) are in 400 parts of water dissolved neutrally and acidified to Congo with hydrochloric acid. This becomes the suspension

ίο ι files prepared as usual diazotization mixture of 21.8 " (0.1 mol) l-amino- ^ nitrobenzene-I-sulfonic acid 0 ° C. and 140 parts by volume of 20% sodium acetate solution were added dropwise over the course of 90 minutes. To When the coupling is complete, it is salted out with sodium chloride and isolated.

The paste obtained is dissolved neutrally in 1000 parts of water, and a solution of 42 parts of crystallized sodium sulfide in 100 parts of water is added ^{at 60 ° C.} After the reduction of the nitro

20: group to the amino group becomes Congo acidic with sodium chloride isolated and the paste freed from sulfur in the usual way.

2,3-Dichloroquinoxaline-6-carboxylic acid chloride is then added to the solution of the aminoazo dye, while neutralizing with soda solution at about 40 ^{° C., until the dye has formed}

NH- CO

or tetrachloropyrimidine, dyes are obtained that color cotton in red tones.

Other dyes of this type are listed in the following table. In the first column the Amino compound of the diazo radical, in the second the acylating agent, in the third the hue specified:

Amino compound

NH-CO

NO,

NH-CO-

tl:

NO,

Acylating agents

Phenyl isocyanate

p-chlorophenyl isocyanate
m-chlorophenyl isocyanate

Cyanuric chloride

+ 2. p-sulfanilic acid
+ 3. aniline

Cyanuric chloride

+ 2. p-sulfanilic acid
+ 3. N-methylaniline

hue

purple

purple
purple

Red-violet
Red-violet

Example 2

23.9 parts (0.1 mole) of 2-amino-X-hydroxynuphlhulin-5-sulfonic acid are dissolved neutrally in 400 parts of water, made Congo acidic with a little hydrochloric acid and with a diazotization mixture of 0.1 mol acetyl benzidine monosulfonic acid the formula

NH-COCH ₃

SO ₁ H

offset at OC. 280 parts by volume of 20% sodium acetate solution are added dropwise and stirred for so long.

until the coupling is finished. The precipitated coupling product is used in place of the acetylbenzidine monolation product is suctioned off and dried. If sulfonic acid other diazo components are obtained receives a dye that turns purple in water with red monoazo dyes, which are shown in the following table Color dissolves. are listed:

H ₂ N

NH - CO - NH

- NH- ^

SO ₁ H

ΓΤι MU / r N

SO ₃ H

SO ₃ H

7th ν- XTTT rT \

SO ₃ H Cl

H ₂ N

SO, H

H ₂ N ^ f V-NH- r

NH-CO- / ^ NH-CO

Cl CH ₃

SO ₁ H

N = /

SO ₂ CH ₃

S0, CH,

Red-violet

purple

rr \ / r \ s MU Cf \. -

purple

Red-violet

Red-violet

Red-violet

Red-violet

Be i s ρ i e 1

The solution of 0.1 mol of Z-methylamino-S-hydroxynaphthalener5-sulfonic acid is in an acidic medium with the usual prepared diazonium salt solution of 0.1 mol of l-amino- ^ acetylaminobenzene-Z-sulfonic acid combined and coupled by adding sodium acetate solution at 0 to 10 ° C and pH 3 to 3.5. To When the coupling is complete, the resulting dye of the formula

CH ₃ in usually e.g. B. salted out with sodium chloride, isolated and dried. The dried dye is a dark powder that dissolves in water with a red color and dyes wool in shades of blue-tinged red.

If 1-amino-3-acetyIaminobenzene-6-sulfonic acid is used as the diazo component, this gives a dye of the formula

SO, H

NH SO ₃ H

CH,

NH

CH ₃ -CO-NH

HO

\

/ -SO ₃ H COCH ₃ -NH

which dissolves in water with a red color and dyes wool in shades of blue-tinged red.

Claims (2)

Patent claims: 1. A process for the preparation of azo dyes, characterized in that the diazo compound of an amine of the formula R ₁ - NH ₂ , wherein R _{1 is} the radical of a sulfonic acid group-containing diazo component, with 1 mole of a coupling component of the formula wherein Y is a sulfonic acid group and R is hydrogen or an optionally substituted alkyl radical, in the peri-position to Hydroxyl group to form a compound of the formula NHR wherein Y, R and R _{1 have} the meanings given, couples. 2. The method according to claim 1, characterized in that a sulfonic acid group-containing diazo compound of the benzene or naphthalene series is combined with 2-amino-8-hydroxynaphthalene-5-sulfonic acid in the 1 position. 109 * 17/98 *