DE161462C - - Google Patents

Description

IMPERIAL

PATENT OFFICE.

It has been found that the condensation of 1: 3: 4-DinitiOchlorbenzol and Potassium rhodium and subsequent reduction obtainable diamidodinitrodiphenyl disulfide of the formula

S.
I.
S.

tetrazotized with nitrous acid provides a body with the most diverse Azo dye components become new sulfine

C ₆ H ₅ -N-.

C ₁₀ H ₇ -N-

^s C ₆ H ₃ -N = NCl + C ₁₀ H ₇ -Ν -C ₂ H ₅

When this dye is treated with alkaline sulfur, it breaks down into a soluble one Alkali salt of probably the following formula:

able to combine azo dyes. All of these azo dyes are characterized in that the sulfur atoms into the salt-forming sulfhydrate group by alkaline reducing agents can be converted so that those members of this dye group which have neither a sulfo group nor a carboxyl group and therefore in alkalis are completely insoluble, upon addition of a reducing agent, such as. B. sulfuric alkali, in solution and on unheated cotton from a salty bath in the manner of sulfur dyes wind up. The process of dye formation, ζ. B. the dye from monoethyl - β - naphthylamine and tetrazotized Diamidodinitrodiphenyldisulfid, can be expressed by the following reaction equation:

C ₆ H, -N = N-

C ₁₀ H ₆

NC ₂ H ₅

55

+ 2 HCl.

\ / ^N0 * C ₆ H ₈ -N = N-

C ₁₀ H ₆ -N-

C ₀ H

60

C ₆ H ₃ -N:

.NC ₁₀ H ₆ -N-

C ₂ H ₅

S-Na.

These dyes therefore differ in characteristic ways from those from the patents 54921, 58641 and 57557 known azo dyes, which differ from derive so-called amidomercaptans (A. W. Hofmann, Ber. d. former Ges. XIII, p. 1223); the the latter are phenylthiazole derivatives, which only in the presence of salt-forming

Sulpho or carboxylic acid groups are able to deliver soluble dyes.

By the oxidizing effect of the air, by air-containing water vapor or by treatment With oxidizing agents or metal salts, these dyes then revert to the insoluble disulfide form or to metal mercaptides over, so that some very washfast colorations are obtained as a result

ίο be.

These dyes can also be produced on the fiber itself in the manner of paranitraniline red or deposited on the most varied of pigments and used as varnishes will.

The water- and alkali-soluble dyes in this group dye wool and silk acid bath.

Since the tetrazo compound of diamidodinitrodiphenyl disulfide with the azo dye components - aromatic amines, phenols, a wide variety of chrysoidins, bismarck brown, monoazo dyes and primary disazo dyes of m-amidophenol and resorcinol, pyrazolone derivatives, methyl ketone derivatives of the doderate derivatives used, such as the doderate derivatives used so far, are used, such as the doderate derivatives used to date, oxalol derivatives, oxaline derivatives benzene and Naphtalinreihe, it is evident that the new group of Sulfmazofarbstoffe able to deliver precisely those dye nuances that after the previously known way of producing Schwefelfai ^- could be manufactured imperfectly bstoffen either not at all or the nuances ie from yellow orange and red to purple.

The following examples serve to illustrate the present invention:

Example I. 17 parts of the diamidodinitrodiphenyl disulfide obtained by partial reduction of dinitrorhodanophenyl (prepared by condensation of 1 x 3 x 4-dinitrochlorobenzene with potassium rhodan in an alcoholic solution) are finely ground with water and 30 parts of concentrated hydrochloric acid and then gradually with a solution with thorough stirring added 7 parts of sodium nitrite. The tetrazotized base gradually goes into solution. After the nitrous acid has disappeared, the clear, if necessary, filtered, yellowish colored solution of the tetrazotized base is introduced into a cooled solution of 14Y ₂ parts β-naphthylamine and 13 parts hydrochloric acid. To complete the combination, if necessary, a sodium acetate solution is added, warmed up and the insoluble dye which has separated out is filtered off. It forms a dark red powder that is insoluble in water and alkalis, but dissolves in dilute alkaline sulfur with an orange-red color and precipitates again as a red precipitate on the addition of acids. It dissolves in concentrated sulfuric acid with a green-blue color and separates out again in the form of red flakes when it is put into water. It stains unheated cotton from a sulfur-alkali salt bath red.

Example II. If, in the above example, the β-naphthylamine is replaced by a monoalkyl-β-naphthylamine, e.g. monoethyl-ß-naphthylamine, replaced, a bluish red sulfinazo dye is obtained. The same places when dried and ground is a bluish-red powder that cannot be dissolved in water, still dissolves in alkalis, little in hot alcohol, but fairly easily in is soluble in hot benzene with a red color. The solution of the dye in concentrated Sulfuric acid is blue-green; when they are introduced into water, the dye falls in crimson flakes. In hot, dilute solutions of alkaline sulfur it dissolves with a blue-red color and dyes the unheated cotton from the salty liquor with a bluish red tint. The colorations in the air or in air-containing water vapor or with various agents, such as chromium potassium, copper or zinc vitriol, Formaldehyde, hydrogen peroxide, nitric acid, etc. post-treated show a excellent wash fastness.

Example III. The solution of the tetrazotized base obtained according to Example I is with thorough stirring with a solution of 13 parts of phenyl methyl ketol in concentrated Hydrochloric acid added.

The resulting insoluble dye precipitate dissolves in alkaline sulfur and turns unheated cotton yellow.

Nitro-ß-naphthylamine 2 x 5 or 2 x 8

(NH ₂ : NO ₂ = 2: 5 or 2: 8)

in combination with the above solution of the tetrazotized base gives a red, and Nitro - m - phenylenediamine an orange dye. Similar dyes, which color orange to brown, arise when one the tetrazotized base on m-amidophenol, resorcinol, m-phenylenediamine or m-tolylenediamine can act. Brown dyes are also produced by combining the tetrazotized base with a chrysoidin the diazoderivatives of aniline and naphthylamine and phenylenediamine, tolylenediamine or m-amidophenol.

A larger number of the new dyes is shown in the table below compiled:

ι Mol. Tetrazotized Dinitrodiamidodiphenyldisulfid

I. 2.

3-

4 ·

5-6.

7 · 8th.

9- ίο.

II.

12th

ΐ3
ΐ4

19th
2O. 21. 22.

23 ·

24.

25 ·
20th
27
28.
29
3O-

32 ·

33
34 ·
35 ·
36.
37 ·
38.

39 ·
40

combined with

ß-naphthylamine (2 mol.)

Monoethyl-ß-naphthylamine (2 mol.)

ß-naphtol (2 mol.)

m-toluenediamine (2 mol.) . . .

α-naphthylamine (2 mol.)

m-Amidodirnethylaniline (2 moles). .

m-phenylenediamine (2 mol.)

Phenyl-ß-naphthylamine (2 mol.)

Tolyl-ß-naphthylamine (2 mol.)

Phenyl-tt-naphthylamine (2 mol.)

Diphenylamine (2 mol.) ..

Benzyl-ß-naphthylamine (2 mol.)

m-oxyphenylparatolylamine (2 mol.)

Ethoxydiphenylamine (2 mol.)

m-Oxydinitrodiphenylamine (2 mol.)

Resorcinol (2 moles); . . .

Resorcinol (r mol.)

Chrysoin (2 moles)

Chrysoin (1 mole)

Diazobenzene-m-amidophenol (2 mol.)

Bismarck brown J (2 mol.)

m-phenylenediamine (1 mol.)

Phen} 'lpyrazolone (2 mol.)

Methyl ketol (2 mol.)

Nitro-m-phenylenediamine (2 mol.)

Chrysoidin (2 moles). . .

Dinitrophenyl-m-phenylenediamine (2 moles).

2 7-dioxynaphthalene (2 moles)

Diethyl-m-amidophenol (2 mol.)

1 x 5 hydrochloric acid amidonaphtol (2 moles). . 2 · 5-amidonaphthol sulfate (2 mol.)

2: 7-naphthylamine sulfonic acid (2 mol.)

Naphtionate (2 mol.)

m-Toluenediaminesulfonic acid (2 mol.) .... 2 x 5 x 7-amidonaphthol sulfonic acid (2 mol.).

y-acid (2 mol.)

N.W. acid (2 mol.)

H-acid (2 mol.)

Chromotropic acid (2 mol.)

Phenyl-1 x 8-acid (2 mol.)

dyes unheated cotton

Orange red

blue red

bluish red

brown orange

brownish red

orange brown

orange

blue red

purple red

brownish red

orange

salmon red

brown orange

orange

Brown

Brown

red-brown

Brown

Brown

yellow-brown

red-brown

orange brown

yellow

sulfur yellow

orange yellow

brown orange

orange brown

bordeaux

salmon red

purple brown

red-brown;

dyes wool red-orange

Red

yellow-brown brown-red violet-red

Red

violet-red violet-red violet-red.

Claims (1)

Patent claim:
Process for the preparation of sulfinazo dyes, consisting in that tetrazotized diamidodinitrodiphenyl disulfide coupled with azo dye components will. BERLIN. PRINTED IN THE REICHSDRUCKEREI.