DE2034543C3 - Disazo dyes containing sulfonic acid groups and a method for dyeing and printing natural and synthetic polyamide fiber materials using these dyes - Google Patents

Description

2 (1 Phenylcarbonylamino group or a carbamoylamino group optionally substituted by alkyl radicals having 1 to 7 carbon atoms or phenyl radicals, R3 and R _{4 are} hydrogen, optionally by halogen, cyano, hydroxy, Ci-C ₄ -alkyl, C ₂ -C ₅ -alkylcarbonyloxy or C ₂ -C5 alkoxycarbonyloxy groups substituted alkyl radicals with 1 to 4 carbon atoms, or optionally benzyl or phenylethyl radicals substituted _{by chlorine, Ci -C 4} alkyl or Ci-C ₄ alkyl radicals, m is an integer from 0-3 and η is an integer Number from 0 to 2 are.

2. A method for dyeing and printing natural and synthetic polyamide fiber materials, characterized in that one dyes according to claim 1 used

The present invention relates to sulfonic acid group-containing disazo dyes of the general r> formula

SO ₁ H

(R.L

N ">

(I)

in which Ri halogen atoms, optionally halogen-substituted alkyl radicals with 1 to 4 carbon atoms, alkoxy radicals with 1 to 4 carbon atoms, carbonamide and sulfonamide groups optionally substituted by alkyl radicals with 1 to 4 carbon atoms or phenyl radicals or carboxylic acid ester and sulfonic acid ester groups with 2 to 7 carbon atoms, R2 denotes methyl and methoxy radicals, halogen, the formylamino group or alkylcarbonylamino groups with 1 to 4 carbon atoms in the alkyl radical, X denotes a hydroxyl or alkoxy group with 1 to 4 carbon atoms and preferably for a formylamino group , an optionally substituted by halogen alkylcarbonylamino group having 1 to 4 carbon atoms in the alkyl, optionally substituted by halogen, CF ₃ or alkyl phenylcarbonylamino group or optionally substituted by alkyl of 1 to 7 carbon atoms or phenyl carbamoylamino group, R3 and _R4 is hydrogen , optionally by halogen, cyano, hydroxy, Ci - Ct- alkoxy, C ₂ -Cs-alkylca rbonyloxy or C ₂ -C ₅ alkoxycarbonyloxy groups substituted alkyl radicals with 1 to 4 carbon atoms, or optionally by chlorine, Ci-C ₄ -alkyl or Ci-C ₄ -alkoxy substituted benzyl or

4 '. Phenylethyl radicals, m represent an integer from 0-3 and η represent an integer from 0-2, as well as their production and use for dyeing and printing natural and synthetic polyamide fiber materials.

Preferred dyes are those of the formula I in which X stands for an acylamino group.

Suitable substituents Ri are, for example:

Fluorine, chlorine, bromine, -CH ₃ , -C ₂ H ₅ , n- and 1-C ₃ H ₇ , n-, i- and tC ₄ H ₉ , -CH ₂ Cl and CF ₃ ; -OCH ₃ , -OC ₂ H ₅ , n- and 1-OC ₃ H ₇ and n-OC ₄ H ₉ .

Examples of possible substituents R ₂ are:

Fluorine, chlorine, bromine, acetylamino and Propionylamino.

Examples of radicals X include: Acetylamino, Chloroacetylamino,

Propionylamino groups;

Benzoyl, 4-chlorobenzoyl, 3- or

4-methylbenzoyl, 3-CF ₃ benzoylamino groups;

-NHCONHCH ₃ , -NHCONHC ₄ H ₉ ,

—NHCONH

h ^r >

Suitable radicals R ₃ and R ₄ are, for example:

-CH ₃ , -C ₂ H ₅ , nC ₃ H ₇ , nC ₄ H ₉ , 2-chloroethyl, 2-cyanoethyl, 2-hydroxyethyl, 2-methoxyethyl, 2-acetoxyethyl.

The new dyes of the formula (I) are obtained by adding aminoazo compounds of the formula

(H)

Ri, R ₂ , m and π have the meaning given above, diazotized, with compounds of the formula

SO ₃ H

(HI)

wherein

X, R3 and R _{4 have} the meaning given above, couples and - in the event that R 3 and / or R _{4 are} hydrogen - optionally then alkylates or aralkylates _{the -NR 3} R _{4 -GmPPe}

The coupling takes place in the usual way, preferably in an aqueous, weakly acidic medium; possibly acid acceptors, for example pyridine, are added The isolation is normally carried out at pH 7, optionally by salting out with sodium chloride or potassium chloride.

Any alkylation or aralkylation to be carried out takes place by reaction with suitable compounds such as esters of strong mineral acids or organic sulfonic acids and preferably low molecular weight alcohols, such as

Alkyl halides, aralkyl halides, Dialkyl sulfates and aryl sulfonic acid esters.

Examples are:

Dimethyl sulfate, diethyl sulfate, methyl iodide, Ethyl chloride, propyl broinide, benzyl bromide, Benzosulfonic acid methyl ester, ethyl p-toluene sulfonate and p-chlorobenzenesulfonic acid butyester.

The reaction with the alkylating or aralkylating agents takes place predominantly in alcoholic form and / or alcoholic-aqueous solution in the presence of acid acceptors, such as, for example, alkali metal carbonates and bicarbonates. One achieves that way primarily a monoalkylation or monoaralkylation.

Some of the aminoazo compounds of the formula (II) are known. These compounds are obtained by acidic coupling of a diazotized amine of the formula

-NH,

(IV)

Ri and m have the meaning given above, with an amine of the formula

(V) bo

R2 and π have the meaning given above.

If appropriate, its N-methanesulfonic acid can be used instead of the amine (V). From the so The coupling product obtained can be obtained, after alkaline saponification, the aminoazo compound (II).

Suitable aminoazo compounds of the formula II are:

4-amino-azobenzoi, 4'-chloro-4-amino-azobenzene, 3'-chloro-4-amino-azobenzoL 2'-chloro-4-amino-azobenzoL 2 ', 5'-dichloro-4-amino-azobenzene, 2 ', 4'-dichloro-4-amino-azobenzoI, 3 ', 4'-dichloro-4-amino-azobenzene, 4'-methyl-4-amino-azobenzoI, 3'-methyl-4-amino-azobenzene, 2'-methyl-4-amino-azobenzene, 4'-chloro-2-methyl-4-amino-azobenzene, 4'-chloro-2-acetylamino-4-amino-azobenzene, 23'-dimethyl-4-amino-azobenzoI, 2,4'-dimethyl-4-amino-azobenzene, 2-methoxy-4-amino-azobenzene, 4'-chloro-2-methoxy-4-amino-azobenzene, 2 _r 5-dimethoxy-4-arnino-azobenzene, ^ S-dimethoxy ^ -amino-azobenzene, 2-methyl-5-methoxy-4-amino-azobenzene, 2-methyl-5-ethoxy-4-amino-azobenzene, 2,3'-dimethyl-5-methoxy-4-amino-azobenzene, 4'-trifluoromethyl-4-amino-azobenzene, 2'-trifluoromethyl-4'-chloro-4-amino-azobenzene, 2'-TΓifluoπnethyl-4'-chloro-2-methyl-4-amino-

azobenzene, 4'-trifluoromethyl-2-acetylamino-4-amino azobenzene,

3'-chloro-4'-trifluoromethyl-4-amino-azobenzene, S'-chloro ^ '- trifluoromethyl ^ -methyM-amino azobenzene,

4-Amino-azobenzene-4'-sulfonic acid amide, 4-Amino-azobenzene-3'-sulfonic acid anilide, 4-Amino-azobenzene-4'-carboxylic acid methyl ester, 4-Amino-azobenzene-4'-carboxamide.

Suitable coupling components of the formula III are, for example:

2-amino-4-acetylamino ■ benzenesulfonic acid, 2-N, N-dimethylamino-4-acetylamino-benzene-

sulfonic acid, 2-N, N-diethylamino-4-acetylamino-benzene sulfonic acid,

2-N-ethylamino-4-acetylamino-benzenesulfonic acid, 2-N-propylamino-4-acetylamino-benzene-

sulfonic acid, 2-N, N-bis (2-hydroxyethyl) -amino-4-acetyl-

amino-benzenesulfonic acid, 2-N, N-diethylamino-4-benzoylamino-benzene-

sulfonic acid, 2-amino-4-phenylcarbamoylamino-benzene sulfonic acid,

2-amino-4-propionylamino-benzenesulfonic acid, 2-N, N-dimethylamino-4-propionylamino-benzene-

sulfonic acid, 2-N, N-diethylamino-4-chloroacetylamino-benzene-

sulfonic acid, 2-N, N-dimethylamino-4-formylamino-benzene-

sulfonic acid, 2-N, N-diethylamino-4-methylcarbamoylamino-

benzenesulfonic acid, 2-amino-4-methylcarbamoylamino-benzene sulfonic acid,

2-amino-4-hydroxy-benzenesulfonic acid, 2-Amino-4-methoxy-benzenesulfonic acid, 2-N, N-diethylamino-4-ethoxybenzenesulfonic acid.

The new dyes are particularly suitable for dyeing and printing natural and synthetic, fiber materials containing amide groups, for example those made from wool, silk and synthetic materials Super polyamide fibers. The dyeings obtained, especially those on synthetic polyamide materials, are characterized by good fastness properties; especially due to good wet fastness properties and very good ones Lightfastness. Also the neutral drawability and the combination behavior with other suitable ones Coloring for such materials is remarkably good.

Surprisingly, the dye show the formula

SO ₃ H dye of the formula

h, n

n = n

CH, SO ₃ H
and the dye of the formula

OCH,

N = N

SO ₃ H

NH,

SQ, H

CH,

NHCOCH.,

compared to that from
Dye of the formula

SO ₃ H

the GB-PS 9 52 061 known

OCH.,

nh,

2 (1

NHCOCH.,

CHj

compared to the 23 known from FR-PS 7 84 909 improved light fastness.

example

19.7 parts by weight (0.1 mole) of 4-aminoazobenzo! are with 200 parts of water and 28 parts of 28% Hydrochloric acid is stirred intensively and diazotized in the customary manner at 10 ° with 70 parts of 10% strength nitrite solution. To When the addition of nitrite is complete, the mixture is stirred for a further hour, clarified with activated charcoal, if necessary, and removed excess nitrous acid with sulfamic acid.

The diazonium salt solution is added at 0-5 ° to a r, Solution of 28.6 parts by weight (0.1 mol) of 2-N.N-diethylamino-4-acetylamino-benzenesulfonic acid in 2000 parts of water and at the same time pyridine is added dropwise so that the pH remains constant at 3. After 5 hours it will mixed with 120 ml of pyridine (pH 5-6). It is left to react overnight. To isolate the Reaction mixture with sodium hydroxide solution to pH 9-10, separates the precipitated dye and dries the Paste at 100 °. The dye obtained corresponds to the formula in the form of the free acid

SO ₃ H

N (C ₂ H ₅ ), NHCOCH ₃

and represents a red powder that dissolves in hot water. Polyamide material becomes light- and wet-fast stained. The shade obtained is a scarlet red.

Dyeing process

30 milligrams of the dye are dissolved in 100 parts of hot water, 4 milliliters of 10% acetic acid added and with a 10 gram strand of polyamide fibers placed in the dyebath. The dyebath is brought to boiling temperature within 20 minutes and then 1

Table I.

Hour held. It is then rinsed and dried at 70 to.

Other dyes of this type are listed in the following table:

Diazo component Coupling component

hue

1) 4-aminoazobenzene

2) 4-aminoazobenzene

3) 4'-trifluoromethyl-4-amino-azobenzene

4) 4'-methoxy-2-methyl-4-amino-azobenzene

5) 2'-chloro-4-amino-azobenzene

6) 2'-chloro-4-amino-azobenzene

7) 4'-chloro-4-amino-azobenzoI

8) 4'-chloro-4-amino-azobenzene

2-Amino-4-acetamino-benzenesulfonic acid scarlet fever

2-N, N-dimethylamino-4-acetamino-benzene-scarlet

sulfonic acid 2-N, N-dimethylamino-4-acetamino-benzene-red

sulfonic acid 2-N, N-dimethylamino-4-acetamino-benzene-scarlet

sulfonic acid

2-Amino-4-acetaminobenzenesulfonic acid red

2-N, N-diethylamino-4-acetamino-benzene red

sulfonic acid

2-Amino-4-acetamino-benzenesulfonic acid scarlet fever

2 ^^ - 01311 ^ 13111 ^ 0-4-30613111 ^ 0 ^ 6 ^ 01- Red

sulfonic acid

continuation

Diazo component Coupling components SO ₃ H ! • "arbton 9) 2 \ 5'-dichloro-4-α! Viino-azobenzene 2-N, N-diethylamino4-acetamino-benzene-
sulfonic acid -4 ^ $ ^ N = N- <r V-NH ₂ Red ΊΟ) 2,3'-Dimethyl-4-amino-azobenzene 2-Amino4-acetaminobenzenesulfonic acid NHCOCH ₃ Scarlet fever 1 Ij 4-aminoazobenzene-4'-carboxamide 2-N, N-diethylamino4-acetamino-benzene-
sulfonic acid Red 12) 4-aminoazobenzene 4'-carboxylic acid methyl
cster 2-N, N-DiiuhyIarnino4-acetamino-benzene-
sulfonic acid Red 13) 2-methyl-4-amino-azobenzene 2-Amino4-acetaminobenzenesulfonic acid Scarlet fever 14) 2-MethyI4-amino-azobenzene 2-N, N-diethylamino4-acetamitlO-benZOl-
sulfonic acid c Scarlet fever 15) 2-methoxy-4-amino-azobenzene 2-N, N-bis (2-hydroxyethyl) -amino4-acet-
aminobenzenesulfonic acid Scarlet fever 16) 2-acetamino-4-amino-azobenzene 2-N, N-bis (2-hydroxyethyl) -amino4-3cet-
aminobenzenesulfonic acid Scarlet fever 17) 4-aminoazobenzene 2-Amino4-phenylcaΓbamoyl-amino-benzene-
sulfonic acid orange 18) 2-methyl-4-amino-azobenzene sulfonic acid orange 19) 4-aminoazobenzene 2-N, N-diethylamino4-benzoylamino-benzene-
sulfonic acid orange 20) 4-aminoazobenzene 2-amino-4-hydroxy-benzenesulfonic acid orange 21) 4-aminoazobenzene 2-amino-4-methoxy-benzenesulfonic acid orange 22) 4-aminoazobenzene 2-N, N-dimethylamino4-methoxy-benzene-
sulfonic acid orange 23) 2-methyl-4-amino-azobenzene 2-N, N-dimethylamino4-methoxy-benzene-
sulfonic acid orange Example 2 21.9 parts by weight (0.05 mole) of the dye <f 'V-N = N-

prepared according to Example 1 dissolve in one liter of 4% and react for a further hour. Pour for insulation

boiling ethanol and 10.6 parts by weight (0.1 mol) are added to 1 liter of ice-water and the precipitate is filtered off

Add soda. 12.6 are drained off over the course of one hour. After drying, a dye is obtained

Parts by weight (0.1 mol) of benzyl chloride are added and the formula is:

SO ₃ H

-N = N

It is a red powder that mimics polyamide fibers
the described dyeing method stains in bright scarlet tones

The following Table II lists additional dyes
listed that were subjected to the alkylation.

Table II

NHCHn

NHCOCH ₃

Dye according to Table 1 No.

Alkylating agents

hue

60

Dye after Table 1 No.

Alkylating agents

hue

65

Dimethyl sulfate
Diethyl sulfate

Scarlet fever
Scarlet fever

1 7 10 13 13 21 21 22

Benzyl chloride diethyl sulfate diethyl sulfate benzyl chloride diethyl sulfate Dimethyl sulfate

Ethyl chloride benzyl chloride

Scarlet fever

Red

Scarlet fever

Scarlet fever

Scarlet fever

orange

orange

orange

Claims (1)

Claims: 1. Disazo dyes containing sulfonic acid groups of the formula (R. L SO, H in which Ri halogen atoms, optionally halogen-substituted alkyl radicals with 1 to 4 carbon atoms, alkoxy radicals with 1 to 4 carbon atoms, carbonamide and sulfonamide groups optionally substituted by alkyl radicals with 1 to 4 carbon atoms or phenyl radicals or carboxylic acid esters and sulfonic acid ester groups with 2 up to 7 carbon atoms, R ₂ denotes methyl and methoxy radicals, halogen, the formylamino group or alkylcarbonylamino groups with 1 to 4 carbon atoms in the alkyl radical, X denotes a hydroxyl or alkoxy group with 1 to 4 carbon atoms and preferably for a formylamino group , an alkylcarbonylamino group optionally substituted by halogen and having 1 to 4 carbon atoms in the alkyl radical, an optionally _{substituted by halogen, CF 3} or alkyl 1")