DE282890C - - Google Patents

Description

IMPERIAL

PATENT OFFICE.

In patent specification 229267 there is a method for the preparation of vat dyes described, which consists in the fact that one Oxythionaphten generally condensed with azo dyes.

Those used in the cited patent for condensation with the oxythionaphthene Azo dyes contain α-naphthol in Example I and i-oxynaphthalene-4-sulfonic acid in Example II and in Example III i-aminonaphthalene-7-sulfonic acid as azo dye components. To in Examples II and III, the reaction does not proceed in the same way as when using Orange I (Example 1); rather, it becomes the oxythionaphtha, as has now been established is, for the most part, oxidized. According to Example I, the reaction proceeds in the sense of the BiI-

SO _a H

CH ₂ + -> ■

Oxythionaphtha

OH

Sulphanilic acid azo-a-naphthol dung of the indigoid dye, but that The product obtained only provides gray-blue nuances on the fiber, compared to indigo and similar dyes of this class offer no particular advantage. For this reason the process has not acquired any technical importance.

It has now been shown that in the reaction between an oxyazo dye and the oxythionaphthene cleavage of the coupled azo body occurs with regeneration . the original diazotized component and formation of the indigoid dye. From the vat dye from Orange I, for example, an indigoid dye is obtained with elimination of sulfanilic acid according to the following scheme:

NH,

SO ₃ H

55

60

indigoid dye

70

In the course of further investigation it has been found that when using such 'oxyazo dyes which have a heteronuclear, by suitable atoms or Contain atomic groups substituted naphthol nucleus that deepens the hues down to black with the formation of very real dyes.

As a particularly valuable group for the

ίο heteronuclear substitution have here

. Halogen, the alkyloxy group and in particular proved the amino group, whose hydrogen atoms in turn are replaced by other radicals can be, e.g. B. by an acidyl group.

In particular, α-oxyazo dyes are used, the heteronuclear arylamino-, benzoylaminonaphthols, Aryltriazole-, Aryltriazin-, Arylthiazole-, Arylimidazole- and Arylazimidooxynaphtaline, Contain oxycarbazole. On the other hand, it is not recommended that the hydroxyl-free naphthalene core should be used Substituents are present such as the hydroxyl, carboxyl or sulfo group would cause excessive solubility.

For example, one arrives at a dye that has valuable vivid black tones generated on the fiber when the azo dye is made from sulfanilic acid and i-benzoylamino-5-oxynaphthalene or an oxycarbazole condensed with oxythionaphthene.

Example 1.

44.8 parts of the oxyazo dye from sulfanilic acid, diazotized and with i-benzoylamino-5-oxynaphthalene coupled alkaline, are in 500 parts of water with the addition of 10 parts Borax was dissolved hot and about 15 parts of oxythionaphthene were added in portions. Here the azo dye solution is gradually decolorized with the precipitation of a black dye. The mass is heated for some time until the reaction is complete, then is filtered off and washed with hot water.

Is used in place of the oxyazo dye from diazotized sulfanilic acid and I-Benzoylamino-5-oxynaphthalene those from 2-benzoylamino-5-oxynaphthalene are obtained an analogously composed dye.

Example 2.

41.6 parts of the oxyazo dye from sulfanilic acid, diazotized and coupled with 1 x 2-pheno-5-oxynaphtocarbazole, are dissolved in 500 parts of hot water with the addition of 10 parts of borax and gradually add 15 parts of 3-oxy to the boiling liquid (1) thionaphten added. To complete the reaction for about ^x / ₂ hour boiled, then filtered off and washed precipitated vat dye with hot water.

Example 3.

38.5 parts of that obtained from diazotized sulfanilic acid and i-acetylamino-5-oxynaphthalene Oxyazo dye is boiled in 500 parts of water with the addition of 10 parts of borax solved. 15 parts of 3-oxy (i) thionaphtene are added in portions to the solution obtained and the mixture is boiled until condensation is accomplished. The precipitated dye is, as described above, filtered off and washed.

In the present process, the oxythionaphthene can be replaced by its substitution products, homologues or analogs will.

Finally it has been established that the The value of such dyes is in many cases increased if one or both Hydrogen atoms of amino groups formed or substituted by the entire amino group Replaced hydrogen, chlorine or other elements or groups of elements.

The properties of some typical representatives of the process as claimed falling dyes are listed in the table below.

50
Dye off Appearance
of
dye
powder solubility in
conc.
H ₂ SO ₄ Vat coloring
on
Wool 55 sulfanilic acid diazotized
+ i-benzoylamino-5-oxynaphthalene
+ 3-Oxy (1) thionaphtene blue
black in
hot
Nitrobenzene Brown brownish yellow greenish black Sulfanilic acid diazotized
■ + 1 · a-pheno-s-oxynaphtocarbazole
60 _j_ ₃ _0xy (ι) thionaphten Brown
black easy
soluble,
dirty
green greenish black brownish yellow Brown
black easy
soluble,
Brown

Dye off
5 Appearance
of
dye
powder solubility in
conc.
H ₂ SO ₄ Vat coloring
on
Wool Sulfanilic acid diazotized
+ i-acetylamino-5-oxynaphthalene
+ 3-Oxy (1) thionaphtene green
black in
hot
Nitrobenzene greenish black brownish yellow greenish black ¹ sulfanilic acid diazotized
'+ i-acetylamino-5-oxynaphthalene
+ 5-chloro-7-methyl-3-oxy (i) thio
naphtha violet-
black easy
soluble,
blue greenish black brownish yellow greenish black Sulfanilic acid diazotized
+ ι · 5-acetylaminooxynaphthalene
+ ö-chloro-3-oxy (1) thionaphtene gray-green easy
soluble,
dirty
green greenish black brownish yellow greenish black easy
soluble,
blue black

Claims (2)

Patent Claims:
i. Process for the preparation of indigoid vat dyes, characterized in that oxy thionaphthene, its substitution products, homologues or analogs are condensed with those oxyazo dyes which contain at least one heteronuclear substituted naphthol radical, in particular oxycarbazoles or aminonaphthols, or their substitution products as a component. hold, and the products obtained are post-halogenated if necessary. 2. The method according to claim i, characterized in that one in the after Process of claim 1 obtainable amidated vat dyes present Amino groups replaced by hydrogen or other atoms or atom groups, or one or both hydrogen atoms the amino group substituted.