DE2110771B2 - Trisazo dyes and their use for dyeing hydroxyl-containing and nitrogen-containing fiber materials - Google Patents

Description

A = phenyl, optionally substituted by halogen, methyl, ethyl, methoxy, ethoxy, Nitro or sulfo,

B = hydroxyphenyl, diaminophenyl optionally substituted by methyl or ethyl

A '- N =

H ₂ N OH

^ 'Y VN = N (SO ₃ H) _n

CONH

or aminohydroxyphenyl and π = 1 or 2,

where the rings C and D _{can be substituted by Ci -C 4} -alkyl, Cl or Br.

2. Trisazo dyes of the formula

CONH

wherein

A '= nitrophenyl, chlorophenyl, methylphenyl

and B and η have the meaning given in formula (I) to have.

3. Use of the trisazo dyes of claims 1 to 2 for dyeing containing hydroxyl groups and nitrogenous fiber materials.

The present invention relates to trisazo dyes of the general formula

H, N OH

A-N = N -

Vn = N-ZcV- conh - / dV-n = n

(SO ₃ H) _n

wherein A =

Phenyl, optionally by halogen, methyl, ethyl, methoxy, ethoxy, nitro or sulfo substituted,

- Hydroxyphenyl, diaminophenyl or aminohydroxyphenyl optionally substituted by methyl or ethyl and

= I or 2,

where the rings C and D by Ci -Q-alkyl, Cl or Br can be substituted.

Suitable radicals A are, for example, phenyl,

4 *> Halophenyl such as chlorophenyl, bromophenyl, alkylphenyl such as methylphenyl, ethylphenyl, alkoxyphenyl such as methoxyphenyl, athoxyphenyl, nitrophenyl, sulfophenyl.

Suitable radicals B are, for example, hydroxyphenyl, hydroxymethylphenyl, hydroxy-ÜJhylphenyl, ami nohydroxyphenyl, diaminophenyl, diaminomethylphenyl.

Examples of substituents for rings C and D are methyl, ethyl, propyl, butyl ν, and also chlorine and bromine.

Preferred dyes are those of the formula

H ₂ N OH

'-N = N / Vy-N = N / ~ V- CONH ~ / ~~ V N-N "B

(SO ₁ H) _n

A '- nitrophenyl, chlorophenyl, methylphenyl and B and π have the meaning given in formula (I) to have.

The new dyes of the formula (I) are obtained from the formula known manner by acidic coupling of amines of the formula

A-NH ₂ (III)

on aminohydroxynaphthalenesulfonic acids of the formula

H ₁ N OH

(SO ₃ H) _n (V)

HO NH,

(SO ₃ H) _n

(IV)

subsequent half-sided coupling with an octrazotized amine of the formula

NH ₂ (VI)

H ₂ N - ^ fC> - CONH

where π = 1 or 2, to monoazo dyes 15 to disazo dyes of the formula

H ₂ N OH

CONH

-Ni

(VII)

(SO ₃ H) _n

where X is an anion, preferably the anion of an inorganic acid such as sulfuric acid or hydrochloric acid and subsequent coupling with coupling components

B-H (VIII)

in which B denotes hydroxyphenyl, diaminophenyl or aminohydroxyphenyl which is optionally substituted by alkyl.

Suitable amines (III) are, for example Aniline, 2-chloro-aniline, 3-chloro-aniline, 4-chloro-aniIin, 1 - aminobenzoi-2-su ^ onic acid, 1 - aminobenzene-3-sulfonic acid, 1 - aminobenzene-4-sulfonic acid, 1 - amino-2-methylbenzene,

1 - amino-4-methyl-benzene, 1 - amino-2-nitro-benzene, 1-amino-4-nitro-benzene, 1-amino-4-methoxy-benzene. Suitable amino-hydroxy-naphthalenesulfonic acids (IV) are for example

l-amino-e-hydroxy-naphthalinO.e-disulfon-

acid, l-amino-S-hydroxy-naphthalirM.e-disulfon-

acid, l-Amino-e-hydroxy-naphthalene ^ -sulfonic acid.

H, N

QiN-C ^ N = N - // Y VN = N-

SO ₁ H

shows next comparable to that known from British Patent 3 38111, Example 5 Dye has the surprising advantage of better drawability on cotton,

example 1

13.8 parts of 1-amino-4-nitro-benzene are used in the usual Way diazotized. A neutral solution of 31.9 parts of 1-amino-8-hydroxynaDnthalin-3,6-disulfonic acid in 150 ml of water is allowed to run into this diazotization.

Suitable diamines (I V) are, for example: 4-Amino-benzoyl-4'-amino-anilide

4-Amino-2-chloro-benzoyl-4'-amino-anilide 4-Amino-3-methyl-benzoyl-4'-amino-aiiilide 4-Amino-benzoyl-4'-amino-2'-chloro-aniIide 4-Amino-benzoyl-4'-amino-3'-methyl-anilide. Suitable coupling components (VIII) are, for example

Phenol, methylphenol, ethylphenol, 1,3-diaminobenzene, 1 - amino-3-hydroxybenzene, 13-diamino-4-methylbenzene.

The coupling of (V) with (VI) and of (VII) with (VIII) takes place in a manner known per se in an aqueous alkaline medium.

The new dyes are ideal for dyeing natural and synthetic fiber materials containing hydroxyl groups and nitrogen lien, for example cellulose fibers in all processing states, especially of cotton and Regenerated cellulose, as well as wool, semi-wool, silk, nylon, leather and paper. You get green to black Dyeings with good fastness properties, especially good water and perspiration fastness properties Post-treatment with cation-active aids. The dye of the formula

CONH

-N = N-

OH

After stirring overnight, the coupling is complete. The coupling is brought into solution at pH 7 by sprinkling in 15 parts of sodium carbonate. 22.7 parts now be 4-Aminobenzoy) -4'-aminoanilide tetrazotized in a mixture of 23 parts water and 56 parts of 30% strength aqueous hydrochloric acid at O to 1O ⁰ C with 13.8 parts of sodium nitrite. After the first coupling has been mixed with 20 parts of sodium carbonate, it runs to the tetrazotization of 4-aminobenzoyl-4'-aminoanilide previously congoneutraj with sodium carbonate solution. After about 15 minutes the half-page is

Coupling is complete. A solution of 9.4 parts of phenol in 100 parts of water and 17 parts is then added Sodium carbonate too. The coupling stirs overnight. Then the dye is salted out with rock salt, filtered off and dried. The dye dyes cotton in a green tone.

Further dyes that can be prepared according to the invention are listed in the table below Components summarized with details of the color shades.

Example A-NH ₂

(SO ₃ H).

H ₂ N - "/ c \ - ~ C0NH

NH ₁

H-B

Color ion

on

cotton

4-nitro- l-amino-8-hydroxyaniline naphthalene-3,6-di-

sulfonic acid

2-chloro-1-aniino-8-hydroxyaniline naphthalene-3,6-di-

sulfonic acid 4-aminobenzoy] -4'-aminoanilide

4-aminobenzoy! -4'-aminoaniIide

1,3-diamino benzene

1,3-diaminobenzene

green-

pithy

black

black

Staining example

In a staining beaker with a capacity of 500 ml, which is located in a heatable water bath, 260 ml would be added Water at 50 to 60 ° C and 10 ml of 10% sodium sulfate solution and 1 m! 10% sodium carbonate solution added 0.25 g of dye is made into a paste with 2 ml of cold water and 30 ml of warm water are added Water (50 to 60 ° C) too; the dye dissolves in the process.

The dye solution is de; added liquor presented and 10 g of cotton fabric üi this dye liquor kept constantly in motion. The temperature of the dye liquor is increased to 85 to 90 ^° C. in the course of 30 minutes and dyeing is continued for 60 minutes at this temperature. The dyed material is removed from the dye liquor, the adhering liquor is removed by wringing out, the material is rinsed for 5 to 10 minutes with cold water and dried at 60 to 70 ° C.

Claims (1)

Patent claims: 1. Trisazo dyes of the formula H ₂ N OH A-N = N (SO ₃ H) _n wherein