DE1794217A1 - Monoazo dyes containing sulfonic acid groups - Google Patents

Description

Badische Anilin- & Soda-Fabrik AG

Our sign.-0.Z. 25 803 Bg / Stä ■ 67OO Ludwigshafen, September 24, 1968

Monoazo dyes containing sulfonic acid groups

The invention relates to monoazo dyes of the general formula I containing sulfonic acid groups

N = NK- (SO ₃ H) _n

in the A an optionally further substituted arylene or aralkylene radical, η denotes the numbers 0, 1 or 2 and K denotes the radical of a coupling component.

A radicals are derived, for example, from anilines, naphthylamines, benzylamines or phenylethyamines. As a substituent for the benzene rings of these compounds are, for example, halogens or alkyl or alkoxy groups, e.g. chlorine, bromine, methyl, Ethyl, n- or i propyl, n-, i- or t-butyl, methoxy or To call ethoxy.

In particular, the radicals -A- may be mentioned, for example:

-2-

109831/1804

CH-

CH-

179421?

O.Z. 25 803

CH-

, 0CH-

Cl

CH.

Br

CH,

OCH-

CH ₂ -CH ₂

The coupling components K-H are in particular anilines, Aminonaphthalenes, indoles or pyrazolones are possible, however, naphthols, phenols or quinolones, acylacetarylamides, Pyrazoles or compounds ^ such as peri-Napthindandione- (1,3) ^ also useful.

In addition to sulfonic acid groups that may be present, the coupling components can also contain further substituents, such as Chlorine or bromine, alkyl or alkoxy groups each with expediently 1 to 4 carbon atoms, hydroxy, cyano, methyl sulfone, ethyl sulfone, Wear sulfonamide, acylamino, carboxy, carbalkoxy, amino or sulfonic acid groups.

In addition to the substituents already mentioned, there are individual

l, butyl, methoxy, ethoxy, N-methyI-

- 3 - ... O.Z,

sulfonaroid, Ν, Ν-dimethylsulfonamide, N-ethylsulfonamide, N, N-diethylsulfonamide, N-phenylsulfonamide, acetylamino, propionylamino, Benzoylamino, benzenesulfonylamino, p-toluenesulfonylamino, Carbomethoxy, carboethoxy, N-methylamino, N-ethylamino, N-phenylamino, Ν, Ν-dimethylamino, Ν, Ν-diethylamino, N-methyl-N-ß-hydroxyäthylamino, N-Ethyl-N-ß-cyanoethylamino or N-ethyl-N-ß-hydroxyäthylamino into consideration.

The following coupling components are mentioned in detail:

2-naphthylamine-1-sulfonic acid 2-naphthylamine-5-sulfonic acid 2-naphthylamine-6-sulfonic acid 2-naphthylamine-7-sulfonic acid 1-hydroxy-Y-aminoO-sulfonic acid 2-naphthylamine-5,7-disulfonic acid 1-hydroxy-S-acetylamino- ^, 6-disulfonic acid, re 1-Hydrox-y-8-benzylamino-4,6-disulfonic acid l-Hydroxy-S-tosylamino- ^ iö-disulfonic acid 2- <Meithylaminonaphthalin-.5-sulfonic acid 2-phenylindole

1-methyl-a ^ phenylindQl ^ -iPhenylindol ^ -sulfonic acid 1-ß - Carboxyäthy1-2-phenylindole-5-sulfonic acid l -Phenyl -> - methylpyrazolon- (5) 1 ^, (4 '-Sulfophenyl) - 3-methyl-pyrazolone- (5) 1- (2 ^f , 5'-dichloro-4 ¹ -sulfophenyl) -3-methylpyrazolone- (5) diethylaniline or

Diphenylamine. u

109831/180

Technically particularly valuable dyes correspond to the general formula II

A "-SQ, H

II -NK ₁ - (SO ₃ H) _n "

in the -A -, - a phenylene-, chi or phenylene-, methyl phenylene-, Dimethylphenylene, A "thylphenylene, methoxyphenylene or Naphthylene radical or a radical of the formula

or
CHp CHp-CHp

and K, the remainder of a coupling component of the aminobenzene, aminonaphthalene, indole or pyrazolone series and η denotes has given meaning. Of the dyes of the formula II those in which A. is an optionally substituted phenylene radical are preferred.

Diazo compounds, for example, can be used to produce the new dyes of amines of the general formula

A-SO, H
1 y

with coupling components of the general formula '■ - * · "■■ · ■ - 109831 / 180A

IMWW15D

179421?

5 -. O.Z. 25 803

convert, where A, K and η have the meanings given for formula I. Diazotization and coupling are carried out according to known methods Methods and offer no special features.

Some of the new dyes can also be prepared by using dyes of the general formula

N = N-K-H

sulfated according to methods known from the literature.

The new dyes are ideal for dyeing Fibers and textile material made of wool and in particular made of synthetic polyamides such as nylon-6 or nylon-6,6 and also for mixtures of these fibers with one another or with other fiber material. Greenish-tinged yellow is obtained on these fibers to violet dyeings with excellent fastness properties, of which the light and wetness properties in particular are to be emphasized are.

Information on parts and percentages in the following examples relate to weight.

-6- ~ - - * - i trj 109831/1804

- 6 - ο.Ζ. 25,805

example 1

. 803

The solution of 31 * 8 parts of the compound of the formula

in 500 parts of water, concentrated hydrochloric acid and 125 parts of ice with 30 parts by volume, after addition of 25 parts by volume are added 23 # aqueous NatriumnitrjELösung, while kept at a temperature of 0 to 5 ⁰ C, and after stirring for two hours at the same temperature as usual by a if necessary existing excess nitrite freed. To the suspension of the diazonium salt were then added at 0 to 5 ⁰ C gradually a solution of sodium salt of-23.4 parts of 2-aminonaphthalene-lsulfonsäure in 200 parts by volume of water. A pH of 4 to 5 is then set in the coupling mixture by adding a concentrated aqueous sodium acetate solution. After the coupling has ended, the dye is filtered off with suction, washed with 10% sodium chloride solution and dried at 70.degree. The dye of the formula is obtained

as a dark red powder that produces pure red tones on polyamide fabric, which are characterized by excellent lightfastness and highest Distinguish wet fastness properties.

10 9 8 3 1/18 0 4 -7-

ο.Ζ. 25th

Other dyes with similar properties can be used Prepare in an analogous manner from the diazo and coupling components listed in the following table:

Example diazo component coupling component

Hue of the dye on polyamide

SO ₃ H

2-amino-naphthalene 5-sulfonic acid

Scarlet fever

2-amino-naphthalene-6-sulfonic acid

Scarlet fever

2-amino-naphthalene 7-sulfonic acid

Scarlet fever

2-amino-naphthalene-8-sulfonic acid

Scarlet fever

2-amino-naphthalene-1-sulfonic acid

Red

2-amino-naphthalene-5-sulfonic acid

Scarlet fever

2-amino-naphthalene-1-sulforic acid

Red

109831/1804

-8th-

O.Z. 25th

Example diazo component, coupling component, shade of the

Coloring on polyamide

.CO

2-amino-naphthalene red 1-sulfonic acid

10

NH,

, CO

-N "

CH,

(technical mixture of isomers) 2-amino-naphthalene-1-sulfonic acid

Red

2-amino-naphthalene-5-sulfonic acid

Scarlet fever

12 Cl-

NH,

, CO

2-amino-naphthalene-1-sulfonic acid

Red

13th

'CO

2-amino-naphthalene-scarlet 5-sulfonic acid

2-amino-naphthalene- 'scarlet fever 5,7-disulfonic acid

15th

SO ^ H

ν:

, co

'CO

2-amino-naphthalene red 1-sulfonic acid

16 2-amino-naphthalene-scarlet 5-sulfonic acid

109831 / 180A -9-

.ζ. 25W21?

Example diazo component

17th

Coupling component hue of the

Coloring on polyamide

2-amino-naphthalene red 1-sulfonic acid

18th

2-amino-naphthalene 5-sulfonic acid

Scarlet fever

19th

2-amino-naphthalene-5,7-sulfonic acid

Scarlet fever

20th

SO ₃ H

.co

'CO

NH

\ l \ 2-Amino ~ naphthalene-1-sulfonic acid

Red

example

36.8 parts of the compound of formula

SO, H

NH,

are diazotized as described in Example 1. Then you add
to the suspension of the diazonium salt slowly a solution of
Sodium salt of 24.5 parts of 7-amino-1-hydroxynaphthalene-O-sulfonic acid in 300 parts by volume of water and then, by slowly adding a concentrated aqueous sodium acetate solution, first a pH value of 2 and, after the coupling is complete, a pH value in the coupling mixture -Value of 4 a. After that there are 100 parts

109831/1804 -10-

ORjQINAL Ι1 #! * £ ίΤΈ0

O.Z.

Sodium chloride is added and the precipitated dye is filtered off with suction, washed with the above sodium chloride solution and dried. The dye of the formula is obtained

as a violet powder, which dissolves in water with a ruby red color, and polyamide fabric in bluish, red tones of
excellent light fastness and highest wet fastness properties.

Using, analogously to the procedure given, gives of the diazo components in the table below and of 7-amino-1-hydroxy-naphthalene-3-sulfonic acid as a coupling component, dyes with similarly good coloring propertiesί

example

22nd

Diazo component

NH,

NH,

S0, H

Hue of the coloring on Polymaid,

bluish red

bluish red

, CO

-W /> N

109831/1804

bluish red

-11-

O. Z. 25 803

example

25th

Diazo component

Hue of the dye on polyamide

bordo

Example 26

31.8 parts of the compound of formula

SO H

are diazotized as described in Example 1. The suspension of the diazonium salt is then in proportions in a solution of 20.3 Parts of 2-phenylindole given in 500 parts of dimethylformamide, the temperature being kept at 0 to 5 ° C. by external cooling and the gradual addition of 300 parts of ice. Afterward the coupling mixture is adjusted to pH by adding a concentrated aqueous sodium acetate solution 4 to 5 a. When the coupling is complete, the dye formed is isolated and dried as usual. He corresponds to the formula

O N = N

and falls as a brick-red powder that dissolves in water golden yellow color dissolves and synthetic polyamide fibers in red

109831/1804

-12-

r # Jy * ξ

O. Z. 25 803

dyes permanent yellow shades of excellent lightfastness and the highest wet fastness properties.

Other dyes with similarly good properties can be prepared in an analogous manner from the diazo and coupling components of create the following table:

Example diazo component coupling component

SO ₃ H

■ ν:

, co

SO, H

NH,

NH,

SO, H

NH,

, co

"CO

CH ₂ CH ₂ COOH

Hue of the dye on polyamide.

golden yellow

yellow

yellow

golden yellow

golden yellow

golden yellow

109831/1804

-13-

.Z. 25 8-3

Example diazo component

34

Coupling component

Hue of the dye on polyamide

golden yellow

golden yellow

35

36

SOYEi

Nt

XO

'CO

NH,

orange

golden yellow

example

35.2 parts of the compound of formula

SO ₃ H

Cl-

are diazotized analogously to Example 1. The suspension of the diazonium salt is then dissolved in proportions in a solution of 34 parts of the sodium salt of 1- (2 ^l , 5 ^t -dichloro-4 ^t -sulfophenyl) 3-methyl-pyrazolone (5) and 25 parts of sodium carbonate in 200 parts by volume of water registered. It is cooled by adding 125 parts of ice. After the coupling has ended, 150 parts of sodium chloride are used

109831/1804 ~ ¹⁴ "

O.Z. 25 805

and sucks the excreted after stirring overnight Dye off, washes it with 10 ^ iger sodium chloride solution and dries it. A yellow powder is obtained corresponding to the formula

SO ₃ H ₀

Cl - // KN-N

N =

Cl

SO ₃ H

which dissolves in water with a yellow color and on tissue Polycaprolactam produces greenish yellow colorations with very good fastness properties.

Other dyes with similarly good properties can be prepared in an analogous manner from the diazo and coupling components of the following table.

Example diazo component

SO ₃ H

, CO

co

NH,

Coupling component hue of the

Coloring on polyamide

1-phenyl-3-methyl yellow pyrazolone (5)

39

1- (2 * -chlorophenyl) -3-methyl-pyrazolone (5)

greenish yellow

2-hydroxy-naphthalene yellow-brown

8-acetylamino-1-hydroxynaphthalene-3,6-disulfonic acid

10 9 8 31/18 0

Red

-15-

.Z. 25 803

Example diazo component coupling component

SO, H

N ¹

NH

.CO 'CO

Hue of the dye on polyamide

8-benzoylamino-1-hydroxynaphthalene-4,6-disulfonic acid

Red

4-hydroxyehinolone (2)

yellow

NH,

, CO

^S0 3 ^H

NH,

.co

* CO

l-phenyl-3-methyl-
pyrazolone (5) yellow 1- (2'-chlorophenyl) -3-
methyl-pyrazolone (5) greenish
yellow 1-phenyl-3-methyl-
pyrazolone (5) yellow 1- (2 ¹ -Chlor-5 ¹ -sulfo-
pheny1) -3-methyl-
pyrazolone (5) greenish
yellow

Perinaphthinandione- (1,3) greenish

yellow

-16-

109831 / 180A

Claims (5)

Claims 1. Monoazo dyes containing sulfonic acid groups: general formula N = NK- (SO ₃ H) _n in the-A-one possibly still Arylene or aralkylene radical, η the numbers O, 1; take care of the rest of a coupling component " 2 iipd, K. 2. Monoazo color containing sulfonic acid groups #%. 0: ffe _i Formula A--, 1 in the -A.- a phenylene-, Chlorfhgn # le | a _} - ", _? Whore thylphenylenr ·, Äthylphenylen ^,
Naphthylene radical or a radical "of F or CH, and K, the remainder of a coupling component 4er Änjinobenzol-, 109831/1804 - 17 - O.Z. 25 805 Aminonaphthalene, indole or PyrazDlon series and n has the meaning given. 3. A process for the preparation of dyes according to the formula in claim 1, characterized in that one diazo compounds of amines of the general formula A-SO, H with coupling components of the general formula HK- (SO ₅ H) _n converts, where A, K and η are those specified for claim 1 Have meanings. 4. A process for the preparation of dyes according to the formula in claim 1, characterized in that compounds of the general formula N = N-K-H sulfated, where A and K are those given for claim 1 Have meanings. -18- _Λ , ^ -.... .. 10983 1/1804 -.18 - O.ζ. 25 803 5. The use of the dyes according to the formula in claim 1 for dyeing fibers and textile material made of wool or synthetic polyamides. Badische Anilin- & Soda-Fabrik AG 10 9 8 31/18 0