DE2110771A1 - Trisazo dyes - Google Patents

Description

FARBENFABRIKEN BAYER AG

My / Pk LEVERKUSEN Etyerwerk '_; ■ . IV ¹ SrZ 1971

P »tent department

Trisazo dyes

The present invention relates to trisazo dyes of the general formula

NH ₂ OH (I)

AN = Nj ^ si ^^ s.-N = N- / CA-CONH- // pA-N = NB

wherein

A = radical of an aromatic-carbocyclic or -heterocyclic Diazo component,

B = hydroxyphenyl, diaminophenyl or aminohydroxyphenyl optionally substituted by alkyl and

η = 1 or 2,

where the rings C and D can have further substituents.

Le A13620

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Suitable radicals A are, for example, phenyl and halophenyl such as chlorophenyl, bromophenyl, alkylphenyl such as Ytethy! phenyl, Ethylphenyl, alkoxyphenyl such as methoxyphenyl, ethoxyphenyl, Nitrophenyl, sulfophenyl, the remainder of the dehydrothiotoluidinsulfonic acid as well as benzothiazolyl- (2),

Suitable radicals B are, for example, hydroxyphenyl, hydroxymethyl! Phenyl, Hydroxy-ethy-phenyl, amino-hydroxyphenyl, diaminophenyl, Diaminomethylphenyl.

Examples of substituents for the rings C and D are mentions C ^ -C ^ -alkyl such as methyl, ethyl, propyl, butyl as well Halogen such as chlorine and bromine.

Preferred dyes are those of the formula

-N = SN- ß \ -CONH- ß \ -N = NB

A'-N = N-

LHUJ

(SO ₃ H) _n

A '= nitrophenyl, halophenyl, especially chlorophenyl,

Alkylphenyl, in particular methylphenyl, and B and η have the meaning given in formula (I).

The new dyes of the formula (I) are obtained in a manner known per se by acidic coupling of amines of the formula

A-NH ₂ (III)

on aminohydroxynaphthalenesulfonic acids of the formula

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OH NH ₂

(IV)

where η = 1 or 2, to monoazo dyes !! the formula

NH ₂ OH

A-N = N-

(SO ₃ H) _n

(V)

subsequent half-sided coupling w.vt; a tetrazotized amine the formula

- / ~ C ~ A -CONH-

to disazo dyes of the formula

(VI)

NH ₂ OH

A-N = N-

-N = N- rf C \ -CONH - // D

X ^y (VII)

where XÖ is an anion, preferably the anion of an inorganic one 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 (ill) are, for example, aniline, 2-chloroaniline, 3-chloro-aniline, 4-chloro-aniline, l-aminobenzene-2-sulfonic acid, l-amino-benzene-3-sulfonic acid, l-aminobenzene-4-sulfonic acid, .lr-amino-2-methylbenzene, l-amino-4-methyl-benzene, l-amino-2-nitro-benzene, 1-amino-4-nitro-benzene, l-amino-4-methoxy-benzene, Dehydrothiotoluidinesulfonic acid, 2-aminobenzothiazole.

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Suitable amino-hydroxy-naphthalenesulfonic acids (IV) are for example l-amino-8-hydroxynaphthalene-3,6-disulfonic acid, l-amino-8-hydroxy-naphthalene-4,6-disulphonic acid, l-amino-8-hydroxy-naphthalene-4-sulphonic acid.

Suitable diamines (IV) are, for example:

4-amino-bezoyl-4 ^! -amino-anilide 4-amino-2-chloro-benzoyl-4 ^! -amino-anilide 4 ~ amino-3-methyl-benzoyl-4 ^t -amino-anilide 4-amino-benzoyl-4'-amino-2'-chloro-anilide 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, 1,3-diamino-4-methylbenzene.

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

The new dyes are outstandingly suitable for dyeing hydroxyl-containing and nitrogen-containing ones natural or synthetic fiber materials, for example cellulose fibers in all processing states, in particular 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, in particular good water and perspiration fastness properties after aftertreatment with cationic active substances Tools.

Example 1 ;

13.8 parts of l-amino-4-nitro-benzene are used in the usual way diazotized. A neutral solution of 31.9 parts of 1-amino-8-hydroxynaphthalene-3,6-disulf is allowed into this diazotization run acid in 150 ml of water. After stirring overnight

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the clutch is finished. The coupling is brought into solution at pH 7 by sprinkling in 15 parts of sodium carbonate. 22.7 parts now be 4-Aminqbenzoyl-4'-aminoanilide tetrazotized in a mixture of 23 parts water and 56 parts of 30% aqueous hydrochloric acid at 0-1O ⁰ G 13.8 parts of sodium nitrite. After the first coupling has been admixed with 20 parts of sodium carbonate, it proceeds to the tetrazotization of 4-aminobenzoyl-4'-aminoanilide, which was previously rendered positively with sodium carbonate solution. The half-sided coupling is completed after approx. 15 minutes. A solution of 9.4 parts of phenol in 100 parts of water and 17 parts of sodium carbonate is then added. 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 which can be prepared according to the invention are listed in the table below by component summarized with details of the color shades.

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Example A-NH ₉ No.

OH NH

(SO ₃ H) _n

Vv-CONH- / 'D ^ -

H-B shade on cotton

4-nitro-1-amino-8-hydroxyaniline naphthalene-3,6-disulfonic acid

4-aminobenzoyl-4 aminoanilide

1,3-diamino
benzene

greenish black

2-chloroaniline black

Le A 13

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Coloring example :

In a dyeing beaker of 500 ml capacity, which is located in a heated water bath, 260 ml of water at 50 to - 60 ⁰ C and 10 ml submitted lO & Lger sodium sulfate solution and 1 ml of 10% sodium carbonate solution added. Mix 0.25 g of dye with 2 ml of cold water and add 30 ml of warm water (50 - 60 ° C); the dye dissolves in the process. The dye solution is added to the liquor and 10 g of cotton fabric is kept in constant motion in this dye liquor. Within 30 minutes, increasing the temperature of the dye bath at 85 to 90 ⁰ C and dyed for 60 minutes at this temperature further. It removes the colored material of the dyeing liquor, removed the adhering liquor by wringing, the material flushed 5-10 minutes with cold water and dried at 60-70 ⁰ C.

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Claims (1)

Patent claims : 1. Trisazo dyes of the formula NH ₂ OH A-N = N- N = N - // c \\ - CONH - // D ^x > -N = NB A = residue of an aromatic-earbocyclic or -heterocyclic Diazo component, B = hydroxyphenyl, diaminophenyl optionally substituted by alkyl or aminohydroxyphenyl and η = 1 or 2, where the rings C and D have further substituents can have. 2. Trisazo dyes of the formula NH ₂ OH A'-N = N- -N = N - // Vy-CONH-A \ -N = NB (SO ₃ H) _n wherein A ¹ = nitrophenyl, halophenyl, especially chlorophenyl, Alkylphenyl, in particular Methy! Phenyl and B and η have the meaning given in formula (I). J Process for the preparation of trisazo dyes, characterized in that disazo dyes of the formula NH ₂ OH A-N = N- -CONH- / "D ^ VN ₂ ® Le A13620 - 8 -209838/1153 wherein A = radical of an aromatic-carbocyclic or -heterocyclic Diazo component,. X ^ = for an anion, preferably the anion of an inorganic one Acid such as sulfuric acid or hydrochloric acid and η = 1 or 2 mean and rings C and D may have substituents combined with coupling components B-H, wherein B denotes hydroxyphenyl, diaminophenyl or aminohydroxyphenyl which is optionally substituted by alkyl. 4. Trisazo dyes produced by the process of claim 3. 5. Use of the trisazo dyes of claims 1-2 for Dyeing fiber materials containing hydroxyl groups and nitrogen. 6. With the dyes of claims 1-3 colored hydroxyl groups and nitrogenous fiber materials. Le A 15 620 - 9 - 20983 8/1153