DEG0012615MA - - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

Registration date: September 9, 1953. Advertised January 12, 1956

GERMAN PATENT OFFICE

PATENT APPLICATION

CLASS 22a GROUP 1
G 12615 IVb / 22a

Dr. Guido Schetty and Dr. Hans Ackermann, Basel (Switzerland)

have been named as inventors

J. R. Geigy A. G., Basel (Switzerland)

Representative: Dr.-Ing. Dr. jur. H. Mediger, patent attorney, Munich 9

Process for the preparation of chromium-containing monoazo dyes

The priority of registration in Switzerland from 10 ¹ . September 1ÖÖ2 is used

Complex chromium compounds of certain metallizable monoazo dyes that are not acidic, water-solubilizing Containing groups are very suitable for real dyeing of wool and wool-like ones Fibers. While yellow, orange, red, brown, purple and gray chromium-containing dyes Technically relatively easily accessible is the production of blue dyes, which in relative Coloring pure shades, more difficult. The present

Lo ündung now concerns the production of such blue ones chromium-containing dyes without acidic, water-solubilizing groups, wool and wool-like artificial ones Polypeptide fibers from neutral to weakly acidic dye bath in relatively pure blue Color shades of good evening color very real. .

It has been found that new blue chromium-containing monoazo dyes are obtained if monoazo dyes, which contain no acidic, water-solubilizing groups and the general formula (I) treated with chromium-releasing agents in such amounts that at least 2 dye molecules ι Chromatom is bound in a complex.

OH

(I)

509 628/154

G 12615 IVb / 22a

In this formula, R and R 'denote low molecular weight, unsubstituted or substituted, preferably hydroxyl-substituted alkyl groups, in which the hydroxyl group can also be modified, X is hydrogen 5 or a nonionic substituent such as halogen, Y _{1 is} hydrogen, an alkyl, oxalkyl, cycloalkyl or a phenyl group and Y _{2 is} hydrogen or an alkyl group, two Y ₁ and Y ₂ corresponding alkyl groups also among themselves or optionally

ίο ring-shaped with the inclusion of an oxygen atom can be connected.

Diazo components for the preparation of dyes which can be used according to the invention are 2,5-dialkoxy and the 2,5-bisoxalkoxy-i-aminobenzene compounds particularly suitable, which may still be nonionic in the 4-position, for example by Halogen, can be substituted. Diazo compounds with substituted alkyl radicals R and R 'are for example from 1,4-Dioxybenzenes by oxalkylation of

ao hydroxyl groups, mononitration, optionally modification of the hydroxyl groups by alkylation 'or esterification, and can be prepared by reducing the nitro to the amino group.

Usable azo components are obtained from i-oxynaphthalene-3-sulfonic acid by acylation of the Hydroxyl group, conversion of the sulfonic acid group into the sulfonic acid halide group according to customary methods, Exposure to excess ammonia or primary aliphatic, alicyclic, aromatic or hydrogenated heterocyclic amines or secondary aliphatic or araliphatic Amines and saponification of the 1 position acyloxy to the hydroxyl group. Usable in this procedure organic amino compounds are, for example, methyl, ethyl, propyl, butylamine, aminoethanol, the cyclohexylamine, the aniline, the toluidines, the xylidines, the anisidines, the phenetidines, the piperidines, the Morpholine, dimethyl or diethylamine and monomethyl or monoethylamine. The coupling is expediently carried out in an alkaline medium. The salts of the trivalent are used as chromating agents Chromium suitable, possibly also its complex compounds, for example chromium sulfate, Chromium formate, chromium acetate and possibly also. Alkali salts of chromium salicylic acid. The split of the alkyl radical R during the chromation is due to the action of the chromium donating Means favored at higher temperature. One works preferably at temperatures above 100 ° in aqueous solution or suspension under pressure, expediently in the presence of wetting and dispersing agents, like Turkish red oil, at 120 to 160 °. One can also in alcohol under pressure or in higher-boiling organic solvents and diluents in the open

Chromate the vessel, for example in ethylene glycol, in ethylene glycol monomethyl or monoethyl ether, in formamide, in acetamide or in the urea melt at 135 to 155 ⁰ '' The new, complex chromium compounds are obtained as dark, blue to gray-black powders, which Dissolve in hot water with blue, in concentrated sulfuric acid with purple color. If necessary, their solubility in water can be made by mixing

628/154

with small amounts of. alkaline salts, such as sodium carbonate or trisodium phosphate. or with anionic wetting and dispersing agents such as soap or synthetic detergents to be further improved. They dye wool and wool-like synthetic polypeptide fibers such as super polyamide fibers, from neutral to weakly acidic bath in very real, clear, blue tones. The wool dye are good lightfast and show favorable behavior in artificial light. In particular is the chromium-containing azo dye according to the invention of the composition i-amino-2,5-dimethoxybenzene -> i-oxynaphthalene-3-sulfonic acid amide the chromium-containing known from Example 1 of Patent 467 861 Dye of the composition 4-chloro-2-aminoi-oxybenzene -> - i-Oxynaphthalene-3,8-disulfonic acid amide in the drawability from neutral bath in the sea water fastness, milled fastness, rub fastness and Clearly superior to lightfastness.

The following examples illustrate the invention. Unless otherwise noted, they are Parts understood as parts by weight. Parts by weight are in the same proportion as parts by volume Kilograms to liters.

example 1
OCH, OH

OCH

; 15.3 parts of i-amino-2,5-dimethoxybenzene are dissolved in 250 parts of hot water with 35 parts of concentrated hydrochloric acid, cooled to ⁰ 3 and diazotized (as 33 percent strength solution) by the addition of ice with 6.9 parts of sodium nitrite. The diazonium solution is poured at 0 to 3 ⁰ to a solution of 26.4 parts of i-oxynaphthalene-3-sulfonsäuredimethylarnid, 10.5 parts by volume of ion-sodium hydroxide solution and 33 parts of anhydrous sodium carbonate in 500 parts of water. After the formation of the dye has ended, it is isolated by adding saline solution. The dry dyestuff is heated in 450 parts of acetamide with 16 parts of chromium acetate (corresponding to 4.6 parts of Cr ₂ O ₃ ) at 140 to 145 ° until the starting ^{dye has completely disappeared, which after about I 1} Z ₂ hours of ' Case is. Thereafter, it is diluted with 700 parts of hot water, hydrochloric acid is added until a strong Congo blue reaction is obtained, the dyestuff which has precipitated out is filtered off after cooling and washed out with cold water. Thereafter dissolving it with 15 parts by volume of ion-sodium hydroxide solution and 1000 parts of hot water and it falls at 40 ⁰ by addition of 25 parts of sodium salt. After cooling, the chromium-containing dye is filtered off and dried. It is a dark blue powder that is easily soluble in hot water and dyes the wool from a neutral or weakly acidic bath in flowery, reddish-blue tones. The colors are very light-

G 12615 IVb / 22a

! real, they are also characterized by good flexing and IMeawaterfastness off.

A similar dye is obtained if I is used instead of i-amino-2,5-dimethoxybenzene 18.75 parts I used i-amino-4-chloro-2,5-dimethoxybenzene.

In a dyebath which contains, in 400 parts of water, 0.2 part I of the dye according to paragraph 1 of this example and 10.3 parts of ammonium acetate, 10 parts of wool are added at 40 ^° and the mixture is heated to the boil until the liquor is practically exhausted which is the case after about 1 hour. The wool, dyed a full blue, is rinsed and dried.

OCH

Example 2 OH

OCH

CH ₂ - CH ₂

CH ₂ - · CH ₂

15.3 parts of i-amino-2, -5-dimethoxybenzene are diazotized as in Example 1 and at ο to 3 ⁰ in a solution of 30.6 parts of i-oxynaphthalene-3-sulfonic acid piperidide, 10.5 parts by volume of ion- Sodium hydroxide solution and 33 parts of anhydrous soda poured into 500 parts of water. When the formation of the dye has ended, the dye is isolated by adding sodium chloride. The dried dye mixture is heated for about 4 hours in 750 parts of glycol with 27 parts of chromium acetate (corresponding to 7.6 parts of Cr ₂ O ₃₎ and 13 parts by volume of ion-sodium hydroxide solution to 145 to 155 ^0th The still hot solution is then poured into 2400 parts of 12 percent sodium chloride solution, and the dye which has separated out is filtered off, washed and dried. The dye is obtained as a gray-black powder. He dyes wool from neutral or weakly acidic baths in blue tones.

According to the information in Examples 1 and 2, the following chromium-containing dyes, for example, can also be used represent:

table

OR

OH

OR

, Y ₁ -NY ₂

No.

Coloring on wool

9
10

II
12th

-CH ₃
-CH ₃

-CH ₃

-CH ₃
C ₂ H ₆
-CH ₂ CH ₂ OH

-CH ₃

CrI ₃
-CH ₃
-CH ₃
-CH ₃

-CHXH ₉ OH

-CH ₃ H -CH ₃ H -CH ₃ H -CH ₃ H -C ₂ H ₆ H CH ₂ CH ₂ OH H -CH ₃ H -CH ₃ H -CH ₃ H -CH ₃ H CH ₃ Cl CH ₂ CH ₂ OH Cl

—Co Hc
-CH ₃

-CH

C ₂ H ₅
-CH ₂ CH ₃

-H
-CH,

C ₆ H ₅

-CH ₃

-CH ₃

, CH ₂ - CH ₂ ,

-CH CH ₂

C XI2 C ΐ ± 2

-C ₆ H ₅
—Η

CH2CH2

-H

—Η

-CH ₃

, CH ₂ - CH ₂ .

-CH

CH ₂

blue

greenish blue

grayish blue

'. blue blue blue

greenish blue

blue

gray-blue

blue

blue

greenish blue

'509 628/154

Claims (2)

G 12615 IVb / 22a Patent claims: ι. Process for the production of chromium-containing monoazo dyes ^ which are not acidic, water-solubilizing Contain groups, characterized in that there are dyes of the general formula 0 —R OH R '- O Yi-NY ₂ wherein R and R 'are low molecular weight unsubstituted or substituted alkyl groups, X is hydrogen or nonionic substituents such as halogen, and Y _{1 is} hydrogen, an alkyl, oxalkyl, cyclo-I alkyl or phenyl group, Y _{2 is} hydrogen or a! Denote alkyl group, where Y ₁ and Y ₂ also] among themselves or with the inclusion of an oxygen! atoms can be ring-shaped alkyl groups I, treated with chromium-releasing agents in such quantities that there are at least 1 atom of chromium for 2 dye molecules I, and under conditions which cause the chromating of the dye] with elimination of the radical R. 2. The method according to claim i, characterized in that that such dyes of the formula given in claim ι are chromated, wherein R and R 'represent the same alkyl or oxalkyl groups. Referred publications:
German patent specification No. 467 861. 1 509 628/154 1.56