DE1135591B - Process for the production of copper-containing monoazo dyes - Google Patents

Description

GERMAN

PATENT OFFICE

115033 IVc / 22a

REGISTRATION DATE: JUNE 26, 1958

NOTICE THE REGISTRATION ANDOUTPUTE EDITORIAL: AUGUST 30, 1962

The invention relates to a method of manufacture of copper-containing monoazo dyes which, in the metal-free state, correspond to the following formula:

N = N-B-N-C

R N

(I)

wherein the phenyl nucleus A is free from sulfonic acid groups, but by alkyl, halogen, alkoxy, alkylsulfonyl, Alkylcarbonyl, acylamino, nitro, carboxylic acid or substituted or unsubstituted sulfonic acid amide can be substituted,

X denotes a substituent which is capable of forming a metal complex compound,

B denotes a naphthalene nucleus which has a sulfonic acid group and a hydroxyl group in the o-position to the azo group, R is a hydrogen atom or an alkyl group and Y represents a halogen atom.

X in the above formula can e.g. B. a hydroxy, methoxy, carboxy or carboxymethoxy group mean.

The alkyl group denoted by R preferably contains 4 or fewer carbon atoms.

The copper-containing monoazo dyes contain one atom of copper for each molecule of the copper-free ones Compounds according to formula (I).

The copper-containing monoazo dyes can be obtained by adding at least a molar part of one Cyanuric halide is reacted with a molar part of one of the copper-containing compounds, which in the metal-free State of the formula

Method of manufacture
of copper-containing monoazo dyes

Applicant:

Imperial Chemical Industries Limited,
London

Representative:

Dr.-Ing. H. Fincke, Berlin-Lichterfelde, Drakestr. 51, Dipl.-Ing. H. Bohr and Dipl.-Ing. S. Staeger,

Munich 5, patent attorneys

Claimed priority:

Great Britain July 5, 1957 and May 2, 1958
(No. 21 323)

William Elliot Stephen, Colin George Tilley
and Cyril Eric Vellins, Manchester, Lancashire

(Great Britain),
have been named as inventors

A> -N = N-B-NH

(II)

correspond, in which X, B and R have the meaning given above and the phenyl nucleus A is free from Is sulfonic acid groups, but otherwise - as described above - can be substituted.

The compounds of formula II can be obtained by adding one molar part of the diazo compound Benzene series amine which is free from sulfonic acid groups and which is in the o-position to the Amino group carries a substituent which can form a metal complex compound with a Molar part of an aminonaphthol monosulfonic acid or an alkylaminonaphthol monosulfonic acid coupled will. The connections are then treated with a copper-releasing substance to remove the copper-containing Get connections.

The coupling of the diazotized amine with the amino or alkylaminonaphtholsulfonic acid is preferably carried out in an alkaline medium.

Suitable azo components are, for. E.g .: 2-amino-5-naphthol-7-sulfonic acid, 2-Amino-8-naphthol-6-sulfonic acid, 2 - ethylamino - 5 - naphthol - 7 - sulfonic acid, 1-amino-S-naphthol-6-sulfonic acid, 1-amino-8-naphthol-4-sulfonic acid and 1-amino-5-naphthol-7-sulfonic acid.

The preferred amines for use as diazo components are 2-aminophenols, which have a sulfonic acid amide group contain.

Examples of diazo components are: 2-aminophenol, 4-nitro-2-aminophenol, 4-chloro

203 638/347

3 .... 4

2-aminophenol, 5-nitro-2-aminophenol, anthranil- In such an application, the

acid, 4-ethanesulfonyl-2-aminophenol, 2-amino-copper-containing dyes orange, red and phenol-4-sulfonic acid amide, 3-amino-4-hydroxyaceto- reddish blue shades that have good lightfastness, phenone, 5-nitro-2-aminophenoxyacetic acid, 2-amino very good fastness to treatments with phenol-4-sulfonic acid methylamide, o-anisidine, 2-amine 5 moisture, especially with thorough washing anisole-4-sulf acid diethylamide, 4-chloro-2-amino treatments and good storage life in moist, anisole, 2,5 - dimethoxyaniline, aminoterephthalic acid slightly acidic air, like this one often in department stores and 2-aminoisophthalic acid. is encountered, own.

To the copper-free "· compounds of the formula (II) in comparison with those in the German patent

Converted into their copper complex compounds, the dyes described in io 528 166 are the process used the copper-free compounds with a dye obtained according to washfast, copper donors / such as copper sulfate and The invention is illustrated by the following examples,

Copper ammonium sulfate, according to known in which the parts and percentages refer to the Treated procedures, e.g. B. by heating the copper weight, explained free compound with an aqueous solution of the 15

copper donor. In those cases where example 1

metallizable group of the copper-free compound Diazotized 2-aminophenol-4-sulfonic acid amide

is an alkoxy group, the dealkylating is coupled with 2-amino-5-naphthol-7-sulphonic acid and copper is advantageously carried out by using a copper the aminoazo compound thus obtained by boiling the ammonium salt and by usually 20 with an aqueous solution of copper sulphate, which contains several hours at about 100 ⁰ C in an aqueous, a little acetic acid, is heated in the copper complex ammonium alkaline agent. connection transferred.

The process is preferably carried out at temperatures. This copper complex compound becomes so much

carried out below 5 ° C. The preferred reaction- dissolved in water, that the solution 51.75 parts of the medium is water, which also contains water-soluble or- 25 aminoazo compound; this solution becomes ganic solvents such as acetone or dioxane, a suspension of 18.4 parts of cyanuric chloride can contain. It is desirable to add an acid-binding ice-cold water. The mixture is agent, preferably sodium carbonate or sodium ^{bicarbonate 2 hours at a temperature between 0 and 5 0} C to add the agent as far as stirred, sodium carbonate being added in portions if possible at a pH value of 6 to 7 during the 30th to keep the mix versus litmus reaction time. to neutralize.

The dyes can then be added according to the usual method of sodium chloride in the proportion of 100 parts

for the isolation of water-soluble dyes added to every 1000 parts of the reaction mixture are isolated, usually by precipitation of the dye and the compound which separates out and filtered off Dried substance in the form of its sodium salt by adding 35. The copper-containing monoazo-sodium chloride thus obtained to the reagent and dye contains 1.98 organically bound chlorine filters and drying the resulting precipitate, atoms on each azo group present and insists To the disappearance caused by hydrolysis essentially from the dichlorotriazmyl derivative of the copper-containing used as starting material bound to the triazine nuclei of the dyes To reduce halogen atoms, it is preferred to use the 40 aminoazo compound.

The pH of the reaction medium to about 6.5 at the end of the dye will be one-tenth of its

the reaction time and weight of a mixture of disodium hydrophose prior to the isolation of the dyes. It has also proven advantageous to use phate and potassium dihydrophosphate in the ratio to add certain agents acting as buffering agents, mixed 1: 1.8. The mixture thus obtained is colored which when dissolved in water an aqueous solution with 45 cellulosic fibers ruby red, if after the a pn value between 5 and 8 is used at this point in the method described above. It Manufacturing process result. there are now three suitable staining processes that

Suitable buffer substances are mixtures of water that can be used:

soluble salts of phosphoric acid or dialkyl (1) 100 parts of cotton fabric are in a

aminoarylsulfonic acids in which the alkyl groups 5 ° 2% aqueous solution of the dye padded contain at least 2 carbon atoms, as well as their and expressed until the weight of the fabric is 200 parts alkali metal salts, the "aqueous solutions with one. The fabric is dried, my aqueous pH value of about 6.5 These buffer substances solution, which contains 1% anhydrous soda and 30% sodium, can also advantageously be added to the dried coloring chloride, padded and again expressed, powdered material, since the stability of the 55 to be is 200 parts by weight. dye in the powder thus decided comparable the tissue is overall then 1 minute at 100 ⁰ C

is enlarged. · Steams, then rinsed in water, 5 minutes in one

The dyes are in the form of their alkali metal salts, diluted soap solution, boiled again in water easily soluble in water. They are particularly useful rinsed and dried. It is evenly ruby red for dyeing cellulosic textiles dyed in 60 and has a very good light and washing connection with a treatment with an acid-fastness.

binding means, e.g. B. according to the method which (2) A printing paste is prepared by

is described in the Belgian Patent Specification 543,218, 2 parts of the dye, 5 parts of urea, 40 parts of the dyed textile material with an acid 5 ° / ^s oig aqueous solution of sodium alginate, 52 parts of binding agent. is treated, or after mixing water and 1 part sodium bicarbonate with one another processes in which an acid-binding agent is mixed.

Agent on the textile material before or during the The printing paste is treated on a cotton fabric with the "^ dye is applied, applied by means of a roller and the treated

Tissue dried and then steamed for 5 minutes. The fabric is then rinsed in water, in a diluted soap solution boiled for 5 minutes, rinsed again in water and dried. The fabric is Ruby red in places, depending on how the printing paste was applied. The hue is very real to light and washing treatment, with very slight stains on the neighboring white parts of the fabric occur when the printed fabric is subjected to thorough laundering tests.

(3) 2 parts of the dye are dissolved in 3000 parts of water at 20 ⁰ C. 100 parts of viscose yarn are added to the solution and then 90 parts of sodium chloride are added. The yarn is swirled in the solution for 30 minutes, then 6 parts of calcined soda are added. After a further hour, the yarn is taken out, rinsed in water, washed for 15 minutes in a boiling 0.3% strength aqueous solution of a detergent, then rinsed again in water and dried.

In the following table, additional examples are given, which are described in Example 1 Manner were obtained, however, from the diazo and azo components, which in the first and second column of the table are assumed. The last column gives the color tones of the copper-containing monoazo dyes that are obtained when these are used for dyeing cellulose-containing Fabrics according to the procedures described in Example 1 can be used.

Diazo component Anthranilic acid Azo component colour (2) 2-aminophenol-4-sulfonic acid amide 2-aminoterephthalic acid 2-amino-8-naphthol-6-sulfonic acid Bluish red (3) 4-chloro-2-aminophenol 4-nitro-2-aminophenol the same matt red-violet (4) Anthranilic acid 2-aminophenol-4-sulfonic acid amide the same Orange brown (5) 4-ethanesulfonyl-2-aminophenol Anthranilic acid the same Bluish red (6) the same 4-ethanesulfonyl-2-aminophenol 2-amino-5-naphthol-7-sulfonic acid the same (7) the same the same dull orange (8th) 2-aminophenol-4-sulfonic acid amide the same Orange brown (9) 4-ethanesulfonyl-2-aminophenol the same Bluish red (10) 2-methylamino-5-naphthol-
7-sulfonic acid the same (H) the same Orange brown (12) the same Bluish red (13) 2-methylamino-8-naphthol-
6-sulfonic acid the same (14) l-amino-8-naphthol-4-sulfonic acid dull purple (15) 2-butylamino-8-naphthol-6-sulfone-
acid Bluish red

Claims (3)

PATENT CLAIMS: 1. Process for the production of copper-containing monoazo dyes ^ which in their metal-free State of the formula: ^X X ₁ , -K s \ <- A --_N = N - B - N - C C-Y ^v - ^/ III RN N C Y correspond, in which the PhenylkemA is free of sulfonic acid groups, but by alkyl, halogen, Alkoxy, alkylsulfonyl, alkylcarbonyl, acylamino, nitro, carboxylic acid or substituted or unsubstituted sulfonic acid amide can be substituted, X one for metal complex formation denotes suitable substituents, B denotes a naphthalene nucleus which is a sulfonic acid group
and contains a hydroxyl group in o-position to the azo group, R a hydrogen atom or a
Alkyl group and Y denotes a halogen atom,
or of copper-containing monoazo dyes, which in their metal-free state of the formula: OH HO correspond, the dichlorotriazinylamino group being bonded to the naphthalene nucleus in one of the two positions designated as 2 and 3, characterized in that at least 1 molar part of a cyanuric acid halide is reacted with 1 molar part of a copper-containing compound which, in its metal-free state, has the formula: corresponds to, wherein X and B have the meaning given above and R is a hydrogen atom or denotes an alkyl group and the phenyl nucleus A is free of sulfonic acid groups, but by N N -Cl Cl Alkyl, halogen, alkoxy, alkylsulfonyl, alkylcarbonyl, Acylamino, nitro, carboxylic acid or substituted or unsubstituted sulfonic acid amide can be substituted. 2. The method according to claim 1, characterized in that the copper-containing monoazo dye is isolated at a pH of about 6.5. 3. The method according to claim 2, characterized in that the copper-containing dye in Presence of a mixture of water-soluble salts of phosphoric acid or a mixture of dialkylaminoarylsulfonic acid in which the alkyl group contains at least 2 carbon atoms, is isolated with its alkali metal salt, which corresponds to an aqueous solution of about pH = 6.5. Considered publications:
German patent specification No. 528 166. When the application was announced, a coloring table with an explanation was displayed. © 209 638/347 8.62