DE2128328A1 - Polyazo dyes - Google Patents

Description

FARBENFABRIKEN BAYER AG

L EV ERKUSEN -Bayerwerk

Central area '-''ri J .'.'-. V ι 1

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My / Ku

Polyazo dyes

The invention relates to new polyazo dyes in Form of the free acid of the formula

correspond to where

R = H, alkyl, alkoxy (ο- or m-position to the azo group) R ₁ = H or an electron-donating substituent

(m- or p-position to the azo group) R ₂ = C ^ -Cg-alkyl, preferably methyl or ethyl K = radical of an optionally further substituted

Hydroxy-benzoic acid or hydroxy-naphthoic acid »

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in particular the remainder of the o-hydroxybenzoic acid

Preferred alkyl radicals R are those with 1-6 carbon atoms, in particular methyl and ethyl, preferred alkoxy radicals R OCH ₅ and

OC ₂ H ₅ . '

As electron-donating substituents (cf. J.W. Baker "Electron Theory of Organic Chemistry" - Georg Thieme Verlag, Stuttgart 1960, e.g. Table S 42) come into consideration, for example: alkyl, preferably methyl, ethyl and cyclohexyl ; -Hydroxy, alkoxy, preferably methoxy and ethoxy; Aryloxy is preferably phenoxy and phenoxy substituted in the phenyl nucleus by chlorine or methyl; Amino »acyl-amino preferably C.-C.-alkyl-carbonylamino, benzoylamino, 4-nitro-benzoylamino; 4-chlorobenzoylamino; Acyl-N-alkylamino preferably Acyl-N-methylamino or Acy1-U-äthylamino, where acyl has the meaning given above, halogen, preferably chlorine,

Preferred dyes are those of the formulas:

(H)

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-OH

COOH

(III)

worm

E,

have the above meaning.

Dyes of the formula III in which are particularly preferred R. stands for hydrogen.

The dyes of the formula (I) are prepared according to the scheme

NH ₂ OH

D - N = N

HO ₃ S

(H-acid)

SO ₃ H

R-,

D =

Coupling component KH

where R, R- ^ and R _{2 have} the meaning given above

by bis coupling of the bis-diazotized diaminodiphenyl component (V) on the one hand with the coupling component KH, where K has the meaning given above, and on the other hand with the H-acid monoazo dye (IV) in any order.

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The coupling is carried out in the usual way, preferably in aqueous medium, optionally with the addition of coupling accelerators such as urea, formamide, dimethylformamide, (Poly) glycol ethers or alkyl ethers or pyridine, preferably carried out at alkaline pH values

The monoazo dyes (IV), which in the usual way - for example by acidic coupling of the diazotized diazo component D-NHp with Η-acid in the presence of coupling accelerators such as sodium acetate or benzoate, urea, (poly) glycol or * alkyl ethers, formamide or dimethylformamide - can be built up, for example, from the following aromatic amines D-NHp: aniline, 2-, 3- or 4-methy! aniline, 2- or 4-ethylaniline, 4-tert. Butylaniline, 4-cyelohexylaniline, 2,4-, 2j5-, 3,4- or 3,5-dimethylaniline, 2-, 3- or 4-methoxy- (or ethoxy) -aniline, 2- or 4-amino-diphenyl ethers , 2-Amino-2 · or 4 or 4 ^f -methyl (or chlorine). Or 2 «, 4'- or 4,4 ^t -dimethyl (or chlorine) diphenyl ether, 3- or 4-acetyl or Propionyl- or oxylyl-amino-aniline, 3-aminophenylurea, 3- or 4-benzoyl (or 3'-, 4'-chlorine or -CH, or nitrobenzoyl) -aminoaniline, 4-acetyl, -proionyl or -enzoyl-methyl or ethylaminoaniline, 2-methyl-4- or -5-acetyl (or benzoyl, formyl, oxalyl) -amino-aniline, 4-methylamino-aniline, -acetyl- or -oxylylamino-aniline , 3 "- or 4-chloro-aniline, 2-methyl-3-, -4- or -5-chloro-aniline, 3-methyl-4- or -5-chloro-aniline, 4-methy1-3- chloro-aniline, 4-methyl-3-methoxy-aniline, 2-methyl-4- or -5-methoxy-aniline, 3-methyl-2-methoxy-aniline, 2-methoxy-4 or -5-chloro-aniline , 2,4- or 2,5-dimethoxyaniline, 3-methoxy-4-chloro-aniline, 4-methoxy-3-chloro-aniline, 2-methoxy-5-acetylamino-aniline, 3-methoxy-4-acet yl- or -oxalyl-amino-aniline.

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As coupling components KH of the hydroxybenzoic acid series for example:

Salicylic acid, 3 or 4-hydroxybenzoic acid, 5-chloro-2-hydroxybenzoic acid, 4-chloro-3-hydroxybenzoic acid, 3- »4- or 5-methy 1-2-hydroxy "benzoic acid, 5-tert * butyl-2-hydroxybenzoic acid, ^ -Methoxy ^ -hydroxybenzoic acid, 2,4 or 3,5-dihydroxybenzoic acid, 4-hydroxybenzenedicarboxylic acid (1,2) or - (1,3), 2-hydroxybenzoic acid sulfonic acid (5), 3, 4 or 5 amino (IDZW. Acetylamino or benzoylamino) -2-hydroxyl-benzoic acid, as Coupling component of the hydroxy-naphthoic acid series come for example in question 1-hydroxynaphthoic acid (2), 2-hydroxy-naphthoe acid (3) and 2-hydroxy-5,6,7,8-tetralhydroxynaphthalene-carboxylic acid (3) .

Suitable diaminodiphenyl compounds (V) are for example 3,3-dimethoxy-4,4 ^{f t} -diaminodiphenyl and 3,3'-diethoxy-4,4'-diaminodiphenyl.

The new dyes are valuable products for dyeing and printing hydroxyl-containing or N-containing materials, especially fiber materials, preferably those of vegetable origin Nature, such as cotton, jute and regenerated materials such as rayon or viscose. Also paper pulp and Paper products can be dyed easily, as can leather and hides. The dyeings have good coloristic properties. Also the dyeings finished with cation-active auxiliaries or those produced by high-quality finishing (crease-resistant) are characterized by good properties.

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example 1

24.4 parts (θ, 1 mol) of 3.3 ^l -dimethoxy-4,4'-diaminodiphenyl (dianisidine) are added in the usual manner to 150 parts of water and 28 parts by volume of hydrochloric acid (d 1.14) at 10-15 and 46 parts 30 current sodium nitrite solution bis-diazotized. This bisdiazotization solution is combined with a solution of 13.8 parts (θ, 1 mol) of salicylic acid, 300 parts of water and 50 parts of 20 J & iger soda solution, 140 parts of urea are added and pH 9.5 to 10 is maintained by adding soda solution half-sided coupling is finished. The soda-alkaline solution of 42.2 parts (0.1 mol) of the dye 1-amino-8hydroxy-2- (benzolazo) -naphthalene-3-6-disulfonic acid (aniline -— »Η-acid) in 500 is then added Share water and keep the pH value at 9 with soda solution. After coupling is complete, the dye of the formula -

COOH

in the usual way at about 80 susgealted with sodium chloride, sucked off, dried and ground.

A dark dye powder is obtained, which turns green in water Color dissolves. Cotton is dyed in the usual way; one receives one green color with good coloristic properties.

If one uses aniline - ^ - * Η-acid instead of the monoazo dye H-acid dyes with the following aniline-diazokoraponentem4-methyl-, 3-methyl, 2-methyl, 4-methoxy, 3-methoxy, 4-acetylamino, 3-acetylamino, 4-amino, 4-acetyl-methylamino, 4-chloro, 3-chloro, 2 -methyl-5-chloro-, 4-benzoylamino-, 4- (4'nitrobenzoyl) -amino- ^ t-methyl-3-chloro-, this gives dyes that dissolve in water with a green color and dye cotton in green tones. If the first coupling component used (instead of salicylic acid) is 5-methyl-2-hydroxybenzoic acid or 4-methyl-2-hydroxybenzoic acid and the above-mentioned H-acid-

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Monoazo dyes as a coupling component so dyes are obtained which dissolve in water with a green color and give green colorations.

Example 2

The alkaline coupling of 0.1 mol of bis-diazotized 4,4'-diamino-3,3'-dimethoxydiphenyl (Dianisidine) on the one hand with 0.1 mol of 1-hydroxy-naphthoic acid- (2) and on the other hand with 0.1 mole of the dye aniline - ^ Η-acid gives the dye of the formula

COOH

The dye dissolves in water with a green color and dyes cotton in green tones. If those prepared from substituted anilines in Example 1 are used H-acid dyes as a coupling component are also used get green dyes.

Example 5

If 0.1 mol of bis-diazotized dianisidine is coupled with soda-alkaline on the one hand with the monoazo dye aniline - ^ - * Η-acid on the other hand with 3-hydroxynaphtholic acid- (2), a blue dye is obtained. Blue polyazo dyes are also obtained with the monoazo dyes in addition to the substituted anilines given in Example 1.

Example 4

If 0.1 mol of bis-diazitized dianisidine is coupled under alkaline conditions in the presence of urea with 0.1 mol of 3-hydroxy-benzoic acid and 0.1 mol of the dye aniline-H-acid, a green dye is obtained. Even with the Monoazo-

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dyes 4-chloroaniline - ^ H-acid, 4-acetylaminoaniline - ^ H-acid, 4-methoxyaniline - ^ -> Η-acid as a two ^ coupling component are green dyes obtain.

example 3

0.1 mol of bisdiazotized dianisidine are soda-alkaline in the presence of Urea combined with 0.1 mol of 4-hydroxybenzoic acid and then with

0.1 mol of the monoazo dye aniline> ■ Η-acid or 4-chloroaniline or

4 — methoxyaniline or 4-aminoaniline, 4 — acetyl — aminoaniline or 4 — methyl— aniline-mi-acid coupled. Green dyes are obtained.

Example 6

0.1 mol of bis-diazotized dianisidine become soda-alkaline in the presence of Urea with 0.1 mol of 5,6,7,8-tetrahydronaphthalene-2-hydroxy-3-carboxylic acid coupled and then with the solution of 0.1 mol of the dye aniline —-> Η-acid combined at pH 9-10. The coupling product represents one green dye.

Similar green dyes are obtained with the H-acid monoazo dyes des 4-chloro-, 4-methoxy-, 4-methyl, 4-acetylamine, 4-amino-aniline.

Example 7 "

The bis-diazotization used in Examples 1 to 6 is substituted dee 4,4'-diamono-3,3'-dimethoxydiphenyl the equivalent amount of the 4,4'-diamino-3,3'-diethoxydiphenyl will turn green and blue, respectively Obtain dyes.

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Claims (6)

Patent claims: 1. Polyazo dyes in the form of the free acid of the formula OR ₉ ORp correspond to where H = H, alkyl, alkoxy (o- or m-position to the azo group) R ₁ = H or an electron-donating substituent (m- or p-position to the azo group.) Rg = Cj-Cg-alkyl »preferably methyl or ethyl K - radical of an optionally further substituted hydroxy-benzoic acid or hydroxy-naphthoic acid $ 2. Polyazo dyes in the form of the free acid of the formula R H QOOH correspond wherein R, R ₁ - and Rg have the meaning given in claim 1 · A 15 812 - 9 a. 209853 / 3. Polyazo dyes in perm of the free acid of the formula = IT OE ₂ OR ₂ COOH correspond . wherein E and R have the meaning given in claim 1 « 4. Process for the preparation of polyazo dyes ^ dg
that one is a tetrazotized amine of the formula ORr wherein R _{2 is} CL-Cg alkyl, in any order with an azo dye of the formula D-N = N HO ₃ S NH ₂ OH SO-H where 13 for the remainder Le A 13 812 is where 203 8 5 3/112 R = H or o- or m-8-position alkyl to the azo bridge or alkoxy. R ₁ = H or to the azo bridge o- or m-position electron-donating substituent and a coupling component K-H, where K = radical of an optionally further substituted hydroxybenzoic acid or hydroxynaphthoic acid. 5. Use of the dyes of claims 1-3 for dyeing and printing of hydroxyl-containing and N-containing materials. 6. With the dyes of claims 1-3 dyed or printed hydroxyl-containing or N-containing materials. Le A 13 812 - 11 - 209 853/1124