DE88595C - - Google Patents

Description

IMPERIAL

PATENT OFFICE.

by oxidation.

In the main patent and the first additional patent No. 87976, the oxidation of a series of dyes of the aniline series to corresponding azo dyes of the benzidine series has been described. The azo dyes used here were monoazo compounds of the type X - N = N - Y (where X is an oxidable radical of amines of the benzene series with a free para position, such as aniline, o-toluidine, o-anisidine, anthranilic acid etc. and Y is an amine or Phenol or amidophenol or a sulfonic acid thereof as the second component).

It has now been shown that one. corresponding oxidation can also be carried out in the case of dis- and polyazo dyes, provided that these are derived from the first components (radical X) mentioned above. As well as

1. secondary disazo dyes of the type

I. X-N-N-Z-N-N-Y

(where Z denotes the radical of a middle component which further supplies diazotizable amidoazo compounds, e.g. a-naphthylariin, aniline) such as

2. primary disazo dyes of the formula

XN = N \ _n χι — N = N / ^u

(U = end component which allows a diazo group to enter twice, eg m-phenylenediamine, resorcinol, X ¹ = first component different from X , ζ. B. sulfanilic acid, naphthoic acid), furthermore

Polyazo dyes which correspond to one of the two types or both at the same time, for example

XN = N \ _n

III.

and X ¹ - N = N-

N = N / '

4. Disazo dyes derived from m-phenylenediamine as the first component

provide dyes of the benzidine series through oxidative chaining of two molecules by means of the oxidizable radical X , which usually differ from the starting materials by a darker shade and by their (possibly increased) affinity for unheated cotton fibers.

That the connection of the two molecules of the starting materials (including those of the Type II or III) actually leads to normal azo dyes of the benzidine group partly by comparison with the corresponding congo dyes directly represented, partly by reductive cleavage and detection of the benzidine formed in this way (tolidine,

Dianisidins) have been specifically detected. So was z. B. Benzidine through its reactions (Sulphate) and dye formation proven with reductive cleavage of the oxidizing dyes from:

Aniline,
Naphthoic acid

o-toluidine,
Sulfanilic acid

m-phenylenediamine,

Resorcinol,

Aniline,
Naphthoic acid

Aniline - azo -Ct ₁ - naphthyl-

amine - ß ₃ - sulfonic acid azo

Sulfanilic acid azo

K ₁ ß ₄ -Dioxynaphthaleneß ₂ ß ₃ -disulfonic acid,

m - phenylenediamine.

A concatenation of the radicals denoted by X and X ¹ is excluded because only ¹ radicals suitable as X of not ox3 ^r dablen first Components used. Particularly suitable as such are sulfanilic acid and naphthoic acid, the azo derivatives of which do not convert into congo dyes by oxidation.

The procedure is always closely based on that of the main patent and the first amendment at. The same is explained in more detail in the following examples, which vary in many ways permit.

Example i.

Oxidation of a dye of type I.

io parts amidoazobenzene-azo-ß-γ naphtoldisulfosäure in 150 parts of concentrated sulfuric acid at - stirred by 5 ^0th When the solution is complete, 3.0 parts of 80 pCt. Of brownstone, finely ground, are added with continued stirring and cooling. As soon as the initially yellowish red color of the solution has turned violet, it is poured onto ice, to which sodium bisulfite is added to bind any excess manganese peroxide in the manner discussed earlier. The deposited dye acid is filtered off, washed, pressed, converted into the sodium salt and this, if necessary, purified by dissolving. It is soluble in water, stains unheated cotton red, and dissolves violet in concentrated sulfuric acid.

In a similar way one obtains z. B. further substantive from the following disazo compounds Dyes of the following properties:

(a = solubility, b = dyeing on unstained cotton, c = color of the solution in concentrated sulfuric acid):

Source material a No outer dye
b off
C. Amidoazobenzene-azo-ß ₁ -amido-a ₃ -naphthol-ß ₄ -sulfonic acid soluble blue-violet blue Amidoazo-o-toluene-azo-ß-naphthol disulfonic acid R soluble violet blue Amidoazo-o-toluene-azo-ßj-amido-as-naphtol-ß ^ sulfonic acid soluble blue blue o-Toluidine-azo-a-naphthylamine-azo-ai-naphtol-ao-sulfonic acid .... soluble blue-violet blue Anüin-azo-a ₁ -naphthylamine-ß ₃ -sulfonic acid-azo-a ₁ -naphtol-a ₂ -sulfo-
acid ... soluble blue blue Aniline-azo - ^ - Amido-ßj-naphtolether-ß ^ sulfonic acid-azo-c ^ -naphtol-
^ -sulfonic acid soluble blue-gray
red-brown blue-gray
violet Aniline-azo-m-amidophenol-azo-ai-naphthol-a ^ -sulfonic acid soluble violet blue Anthranilic acid-azo-ßj as-amidonaphtol-azo-aj-naphtol - ^ - sulfo-
acid ... soluble violet blue Aniline-azo-ß ^ amido-cig-naphtol-ß ^ sulfonic acid-azo-ß-naphtol .... soluble violet-
black blue-violet Aniline - azo - ß _L - amido - α ₄ - naphtol-ß ₃ - sulfonic acid-azo-cq- naphtol-
«2-sulfonic acid soluble black blue. Aniline-azo-aj a ₄ -amidoiiaphtol-ß ₂ ß ₃ -disulfonic acid-azo-ß-naphtol .. soluble

Example 2.

Oxidation of a dye of type II.

This is a representative of this type

Aniline-azo-,), -., ....
Primulin azo ^ phenylenediamine.

The process for the oxidation of this dye is closely related to that of the example ι on. A water-soluble dye is obtained, which is cotton noun turns reddish brown, and dissolves violet in concentrated sulfuric acid.

In a similar way one obtains z. B. further from:

A u s g a η g s ra a t e r i a 1 a No outer dye
b off
C. DehydSotoluidinsulfonic acid- \ m-phenylenediamine soluble red-brown violet Aniline-azo- j _m .p _heny iendiamm soluble red-brown blue Sulphanilic acid azo- S "^» J ¹ soluble brownish red violet Aniline or o-toluidine azo- jm - phenylenediamine or m-
Naphthoic acid azo j toluenediamine soluble brownish red o-anisidine-azo- j _m phenvlenediamine soluble Brown Brown Aniline- (or o-toluidine) -azo-),} ".-_, .. ·"
Sulphanilic acid azo- j resorcinol soluble Brown blue-violet o-anisidine-azo- \ _R : soluble
soluble
soluble Brown
Brown
reddish
Brown blue-violet
brownish red
respectively
blue-violet
brownish yellow Sulfanilic acid azo ) soluble Brown violet Aniline azo! Resorcinol .. soluble Brown violet Naphthoic acid azo- j
o-Toluidine- (or o-Anisidine) _-azo- ) Ώαί. _η . _
Sulphanilic acid azo- j resorcinol
Aniline azo) _resorcinol __ soluble greenish black reddish
black Amidosalicylic acid azo- j ^lvcsul ^ ¹¹¹ soluble greenish black violet
black o-toluidine-azo- j _m- amidophenol soluble blue black blue. Maphtionsaure-azo-) ^r Aniline-azo-) _{ß amido} . _{a naph} tol
Naphthoic acid azo-S ^{] 3 F} Sulfanilic acid, J ^ ^. Amidonaphtol-as-sulfonic acid Sulfanilic acid, j ^ "^ amidonaphtol-ao-sulfonic acid Naphtio ^a ns ^O äure-azo- ] ^ -4-Dioxynaphtalin-ß, ß ₃ -disulfonic acid ....

Example 3.

Again in an analogous manner, the polyazo dyes described above can be Type III oxidizing:

Starting material a No uer dye
BIC black green Aniline azo)
Dehydrothiotoluidinsulfonic acid-> m-plienylenediamine
azo - a - naphthylamine - azo-) soluble Brown blue-violet Aniline-azo- j
α-naphthylamine disulfonic acid-> m-phenylenediamine
azo-a-naphthylamine-azo-) soluble Brown violet. Aniline-azo-cii-naphtylamine- \
ß ₃ -sulfonic acid azo-> m-phenylenediamine
Sulfanilic acid azo ) soluble purple brown

Example 4.

The method is also applicable to those disazo dyes which differ from the Tetrazo compound of m-phenylenediamine and

2 Derive molecules of a second component. So the dye delivers

azo-resorcinol

m-phenylenediamine

azo-resorcinol

by oxidation a substantive brown, soluble in alkali, which is more concentrated Sulfuric acid dissolves brownish-red.

Claims (4)

Patent Claims: 1. Process for the preparation of polyazo dyes of the benzidine series, consisting of that one used in place of those in the main patent and the first additional patent Monoazo dyes of the aniline series from amines of the benzene series with a free para position here uses dis- and polyazo dyes which use the same amine as the primary component contain. 2. The special embodiment of the process protected by claim 1, consisting in the fact that secondary disazo dyes are used which are derived from amidoazobenzene, amidoazo-o-toluene, aniline-azo-α-naphthylamine, aniline-azo- U ₁ -naphthylamine -ßg- or ß ₄ -sulfonic acid, anilinazo-aj-amido-ßj-naphthol ether and its sulfonic acids, aniline-azo-ßj-amido-a ₃ -naphtholß ₄ -sulfonic acid, aniline - azo - ßj - amido - α ₄ -naphthol -ß ₃ -sulfonic acid and aniline-azo-a, Ci ₁ - amidonaphtol-ß ₂ ß ₃ -disulfonic acid, as well as the corresponding ο - Toluidine combinations by further diazotizing and combining with the end components mentioned in the main patent and first additional patent. 3. The special embodiment of the process protected by claim 1, according to which the primary disazo dyes are used as disazo dyes, which are composed of aniline - azo - m - phenylenediamine or m - toluylenediamine, aniline - azo - resorcinol, aniline-azo-cij a ₄ - Amidonaphtol-c ( ₂ - and -a ₃ - ..sulfonic acid and -ß ₂ ß ₃ -disulfonic acid, anilinazo-cij a ₄ -dioxynaphthalene-ß ₂ ß ₃ -disulfonic acid, and the corresponding ο-toluidine combinations by combining with the diazo compound of a other primary amines, such as sulfanilic acid, naphthoic acid, dehydrothiotoluidinsulfonic acid, and primulin are formed. 4. The special embodiment of the process protected by claim 1, according to which the polyazo dyes used are those primary azo dyes which are derived from the primary disazo dyes mentioned in claim 3, that instead of the aniline etc. contained therein, one of the in claim secondary Disazokörper referred to as aniline 2-azo-aj-naphthylamine-ß ₃ -sulfosäure occurs, or DAF in place of the amine further introduced a Amidoazoverbindung as a - naphthylamine disulfonic acid - azo - α - naphthylamine occurs.