DE1130098B - Process for the production of azo dyes - Google Patents

Description

GERMAN

PATENT OFFICE

F28808IVc / 22a

REGISTRATION DATE: JUNE 27, 1959

NOTICE
THE REGISTRATION
AND ISSUE OF
EDITORIAL: MAY 24, 1962

It has been found that valuable azo dyes can be used obtained when 2,5-diaminonaphthalene-4,8-di- or -8-monosulfonic acid with a diazoazo compound in O-position to the 5-position amino group couples, triazolated the dye obtained, further diazotized, in o-position to a phenolic or enolic hydroxyl group and the resulting o-oxyazo dye converted into a metal complex compound.

Diazoazo compounds suitable for the process for the first coupling can be obtained by diazotization of aminomonoazo or aminopolyazo compounds, of which the following may be mentioned: 4-Aminoazobenzene-4'-sulfonic acid, 4 - Aminoazobenzene-3,4'-disulfonic acid, the aminodisazo compounds from 4-Aminoazobenzene-3,4'-disulfonic acid and 3-toluidine, from 2-naphthylamine-4,8-disulfonic acid + 3-toluidine + 3-toluidine, from 2-naphthylamine-6,8-disulfonic acid + 2-anisidine + 2-toluidine, 4 "-aminobenzoyl-4'-aminoazobenzene-3 ', 4-disulfonic acid, and the aminoazo compound

Process for the production of azo dyes

Applicant:

Paint factories Bayer Aktiengesellschaft, Leverkusen-Bayerwerk

Dr. Karl-Heinz Schündehütte, Dr. Fritz Suckfüll,

Dr. Horst Nickel, Leverkusen,

and Dr. Karl-Heinz Schmidt, Cologne-Flittard, have been named as inventors

C ₂ H ₅ O

= CH- /

^x -NH ₂

SO ₃ H

The triazolation is carried out by processes known per se, for example by oxidation with ammoniacal CuII salt solution.

Oxy compounds which are suitable for the second coupling and which couple in the o-position to the oxy group are for example 4-cresol, 4-methylphenol-3-sulfonic acid, 2-naphthol, 2-naphthol-6-sulfonic acid, 2-naphthol-3,6-disulfonic acid, l-naphthol-4-sulfonic acid, 1-naphthol-3,6-disulfonic acid, l-ethoxy-8-naphthol-3,6-disulfonic acid, 2-benzoylamido-5-naphthol-7-sulfonic acid, 1-chloro-2-amido-5-naphthol-7-sulfonic acid and phenylmethylpyrazolone-4-sulfonic acid.

The conversion of the o-oxyazo dyes obtained into their metal complex compounds can, for example carried out according to the process of oxidizing copper plating described in the German patent documents 807289, 889196, 893699 or 1006098. From the copper complex dyes can be changed in a known manner by removing copper and reacting with other metal salts Metal complex compounds, for example nickel complex compounds, are produced.

The azo dyes which can be produced by these processes can be illustrated by the following general formula will:

HO, S O

-Me-

-N = NR ₂

Nf

R ₁ -N- ^ N ^x

wherein R _{1 is} the remainder of the diazoazo compound R ₁ - N = N ₃ R _{2 is} the remainder of an azo component in which the azo group is bonded in the o-position to the phenolic or enolic hydroxyl group, X is hydrogen or a sulfonic acid group and Me is a metal suitable for complex formation , preferably copper.

Further embodiments of the process for the preparation of the dyes consist in that one the order of certain procedural steps changes. So you can, for example, the triazolation after Further diazotization and coupling to hydroxyl

209 601/402

perform group. If the radicals R ₁ and R _{2 have} groups that are capable of further reactions, for example nitro groups that can be reductively linked with nitro groups of a second component to form azo or azoxy groups, such conversion reactions can be inserted as intermediate stages or after Complete the above procedure.

OCH ₃

The azo dyes are suitable for dyeing vegetable fibers, especially cotton and Viscose. The dyeings on these fibers are distinguished by good fastness properties.

Compared to that from example 1 (p. 4 to 5, line 14) the German patent 959398 known copper complex dye possesses the copper complex compound obtainable according to the process by oxidative copper plating of the azo dye

NH

N = N- / \ - N- N

N-

SO ₃ H

SOoH

_N = N—

HO ₃ S OH

OH

better etchability of the cotton dye.
example 1

27.7 parts by weight (0.1 mole) of 4-aminoazobenzene-4'-sulfonic acid are diazotized as usual and the suspension of the diazonium salt with a solution of 31.8 parts by weight (0.1 mole) of 2,5-diaminonaphthalene-4,8-disulfonic acid and 25 parts by weight of sodium acetate in 1000 parts by volume of water at 0 ° C combined. After the coupling has ended, the reaction solution is brought to pH I by adding hydrochloric acid, the Dye deposited with 150 parts by weight of sodium chloride and isolated.

The paste obtained is dissolved in 1000 parts by volume of hot water and mixed with a solution of 56 parts by weight of crystallized copper sulfate in 140 parts by volume of water and 130 parts by volume of 25% strength ammonia solution. The mixture is then stirred at 90 to 95 ° C. for about 3 hours until the triazolation has ended. After cooling to room temperature, it is acidified with hydrochloric acid, 200 parts by weight of sodium chloride are added and the aminotriazole is isolated. 0.1 mol of the aminotriazole compound is slightly soda-alkaline dissolved in 900 parts by volume of water, 69 parts by volume of 10% sodium nitrite solution are added and added at 15 ° C with stirring to a mixture of 42 parts by volume of hydrochloric acid (rf = 1.14) and 50 parts by volume of water. After the end of the diazotization, the usual alkaline soda solution is coupled with 30.4 parts by weight (0.1 mol) of 2-oxynaphthalene-3,6-disulfonic acid and the dye is isolated. The paste obtained is dissolved in 1700 parts by volume of hot water, made slightly acetic acid and mixed with 140 parts by volume of 20% strength sodium acetate solution and a solution of 25 parts by weight of crystallized copper sulfate in 120 parts by volume of water. At about 40 ⁰ C for about 250 parts by volume to 3% hydrogen peroxide then added over 90 minutes, until the oxidative coppering is complete. The coppered dye of the formula

HO, S O

O SO, H

H0 ₃ S- <

> —N = N

is precipitated and isolated with sodium chloride. Example 2

It is dried a dark powder that will settle 47.5 parts by weight (0.1 mole) of the water through it

dissolves with brown-violet color and cotton in 55 coupling of 4-diazoazobenzene-2,4 -'-disulfonic acid Dyes corinth shades with good fastness properties. aminoazo dye obtainable with 3-methylaniline

the formula

CH,

HO ₅ S- <

> _N = N

-N = N-X

) - NH,

converted as usual into the diazonium compound and this with a solution of 31.8 parts by weight of 2,5-diaminonaphthalene-4,8-disulfonic acid and 25 GeSO ₃ H

parts by weight of sodium acetate combined in 1000 parts by volume of water, the result is a diaminotrisazo dye, which by treatment with copper sulphate in ammonia

Lischer solution is converted into the aminotriazole. After further diazotization, it becomes alkaline with soda in the usual way with 30.4 parts by weight of 2-oxynaphthalene-3,6-disulfonic acid coupled and the isolated dye, as indicated in Example 1, in the copper complex compound the formula

HO ₃ SO Cu O SO ₃ H

CH

HO ₃ S-

-N = N

N N SO, H

SO, H

SO, H

convicted. The dye is a dark powder that is dried in brown tones with good cotton Dyes fastness properties.

In the final coupling, instead of the 2-oxynaphthalene-3,6-disulfonic acid equivalent amounts 1-oxynaphthalene-4-sulfonic acid, 2-benzoylamino-5-oxynaphthalene-7-sulf acid or l- (4'-sulfophenyl) -3-methylpyrazolon- (5) used, after over-

HO ₃ S

Guide to the copper complex compounds obtained dyes, the cotton also in brown Color tones.

53.9 parts by weight
formula

N = N

Example 3 of the aminoazo dye of

NH ₂

CH _S CH ₃

SO, H

are dissolved neutral in 500 parts by volume of water, 69 parts by volume of sodium nitrite solution (10 / ig ° ₀₎ were added and mixed at 2O ⁰ C with 28 parts by volume of hydrochloric acid (d = 1.14). When the diazotization is complete, as indicated in Example 1, the coupling is carried out with 31.8 parts by weight (0.1 mol) of 2,5-diaminonaphthalene-4,8-disulfonic acid

35 and the diaminotrisazo dye obtained converted into the aminotriazole.

After further diazotization, alkaline soda is coupled with 22.4 parts by weight of 1-oxynaphthalene-4-sulfonic acid and the dye thus obtained is oxidatively converted into the copper complex compound. The dye the formula

HO, S O

HO, S

-N = N-

SO, H

CH _a

CH ₃

SO ₃ H

dried is a dark powder that will be obtained in cotton when one is used in the cotton dyes brown shades of good fastness properties. 55 aminodisazo dye the 3-methylaniline second

Place replaced by 2-methylaniline.

When using equivalent amounts of 2-oxynaphthalene-3,6-disulfonic acid or 2-benzoylamino-5-oxynaphthalene-7-sulfonic acid as the naphthol component the final clutch are after oxidative

Coppering obtained dyes, the cotton also 60 substance of the formula if dye in brown tones. Similar dyes

HO ₃ S example 4
53.9 parts by weight (0.1 mol) of the aminoazo color

^ -NH,

HO ₃ S

CH ₃ CH ₃

are, as indicated in the example, diazotized and coupled with 31.8 parts by weight of 2,5-diaminonaphthalene-4,8-disulfonic acids. The obtained diaminotrisazo dye is converted into the aminotriazole compound, further diazotized and soda-alkaline with 2-benzoylamino-5-oxynaphthalene-7-sulfonic acid coupled. Conversion into the copper complex compound leads to Dye of the formula

HG ₃ S Cu

HOoS

HO ₃ S-

N = N-

-NH-CO- <

CH ₃

When dried, it is a dark powder and dyes cotton in brown shades with good fastness properties.

The use of l-oxynaphthalene-4-sulfonic acid or 2-oxynaphthalene-3,6-disulfonic acid as the final component leads to dyes, the cotton dye in similar brown tones.

Example 5

47.7 parts by weight (0.1 mole) of the aminoazo dye of the formula

CH ₃ -O

= N-

-CH = CH-

NH ₂

SO ₃ H SO ₃ H

are diazotized in the usual way, with a 31.8 diazotization is soda-alkaline with 2-oxynaphthalene-

parts by weight 2,5-diaminonaphthalene-4,8-disulfonic acid 30 3,6-disulfonic acid coupled and the resulting color

coupled and, as indicated in Example 1, in the substance oxidatively in the copper complex compound of

Aminotriazole compound transferred. According to the next formula

HO ₃ SO Cu O SO ₃ H

N = N

CH ₃ -O-,

-N = N

-CH = CH- _:

SO, H

SO ₃ H SO ₃ H

converted. It is dried a dark powder, the cotton in brown tones of good fastness properties colors.

When using l-oxynaphthalene-4-sulfonic acid, 2-benzoylamino-5-oxynaphthalene-7-sulfonic acid or 1- (4'-sulfophenyl) -3-methylpyrazolone- (5) as the final component dyes are also obtained after conversion into the copper complex compound which Dye cotton in brown tones.

Claims (3)

PATENT CLAIMS: 1. A process for the preparation of azo dyes, characterized in that 2,5-diaminonaphthalene-4,8-di- or -8-monosulfonic acid is coupled with a diazoazo compound in o-position to the 5-position amino group, the dye obtained is triazolized, further diazotized , couples in the o-position to a phenolic or enolic hydroxyl group and converts the o-oxyazo dye obtained into a metal complex compound, preferably a copper complex compound. 2. The method according to claim 1, characterized in that one of 2-acylamino-5-aminonaphthalene-4,8-di- or -8-monosulfonic acid goes out and the 2-position acylamino group before the Further diazotization to the amino group saponified. 3. The method according to claim 1 and 2, characterized in that 2-amino or 2-acylamino-5-aminonaphthalene-4,8-di- or -8-monosulfonic acid with a diazoazo compound in the o-position to the 5-position amino group, then initially, optionally after saponification, the 2-position amino group is further diazotized and in the o-position to a phenolic or enolic hydroxyl group, triazolated and in the Metal complex compound transferred. Documents considered: German Patent No. 959 398. A coloring table was displayed when the application was announced. © 20Ϊ 601/402 5.