DE84504C - - Google Patents

Description

IMPERIAL

PATENT OFFICE,

In the main patent it was shown that in the condensation of alphyl-p-amido-otoluidines *) with . Very nitroso compounds of secondary or tertiary aromatic amines Valuable red to violet azine dyes are produced.

Further investigations have now shown that red to violet azine dyes are also used which are identical or at least analogous to the products of the main patent, if one considers the ρ-nitroso compounds of the aromatic amines by their ρ - azo derivatives or by the p-quinonimides replaced. It can be both the amidoazo derivatives and quinonimides of the benzene, such as the of the naphthalene series. The connections between the two series behave perfectly equivalent. Among the amidoazo compounds, the action products of any diazo or tetrazo compounds to primary, secondary or tertiary aromatic amines should be understood.

It has also been shown that the same dyes are formed if 1 molecule of Alphyl-p-amido -ο -toluidine with ι Molecül of a ρ-diamine, as it is characterized by reduction

*) With Alphyl, according to Bamberger's suggestion (Ber. XXVII, p. 2583 note), aromatic Radicals such as phenyl, etc., designated.

the nitroso or azo derivatives of the aromatic amines can be obtained in one subject to suitable solvent of the joint oxidation.

Example I.

2.3.4 kg of phenyl-ρ-amido- ο- toluidine chlorohydrate are dissolved in phenol, 34 kg of dimethylamidoazobenzene are added with constant stirring and gently heated for so long, until the amidoazo compound is gone. Now it is diluted with water, with sodium hydroxide solution made alkaline, completely salted out the dye with table salt, pressed off and washed with saline. The Prefskuchen is boiled with water for so long the dye still dissolves, the solution filtered, acidified with hydrochloric acid and with sodium chloride pleases. The dye stains tannic cotton in lively purple-red tones and is identical to the dye which is produced by the condensation of phenyl -ρ-amido- ο -toluidine with nitrosodimethylaniline according to the process of the main patent.

In an analogous manner, one obtains from the by combining diazo or tetrazo compounds with monoethylaniline, monomethyl - ο - toluidine, diphenylamine, diethylaniline, Methyldiphenylamine, methylbenzylaniline sulfonic acid, methyldiphenylamine sulfonic acid

union azo compounds and phenyl (or p-tolyl) p-amido-o-toluidine the corresponding dyes described in the main patents.

Example II.

2.5 kg of p-tolyl-p-amido-o-toluidine chlorohydrate are dissolved in phenol, 4.1 kg of amidoazobenzene sulfate are added and the mixture is stirred warmed up in a water bath until the amidoazo compound has disappeared. so is diluted with water and oversaturated with caustic soda, squeezed out, the Prefskuchen Boiled with water as long as the dye still dissolves, the solution is filtered, acidified with hydrochloric acid and salted out the dye. He dyes on tannin cotton a clear bluish red. The dyeings are washable and lightfast the end.

A red with less bluish tint is obtained in an analogous manner from phenyl- ρ-amido-otoluidine and amidoazo-o-toluene.

Example III.

2 kg of phenyl-p-amido-o-toluidine are with 4.3 kg of benzene azo-α-naphthylamine chlorohydrate mixed, added to 20 kg of glacial acetic acid; it is now heated to water bath temperature until the azo body has disappeared, Then the melt is diluted with approx. 2 1 hydrochloric acid of 20 ° B. and water and the dye salted out. Dissolving in hot water, filtering and salting out gives him in. It dyes tannic cotton in bluish red tones. The colorations are alkali, acid and lightfast. A similar, not quite as bluish coloring product is created when replacing the phenyl-p-amido-o-toluidine with the corresponding p-tolyl derivative. If the benzolazo-anaphtylamine is used instead of the equivalent in the above examples Quantities of the azo compounds of substituted a-naphthylamines are obtained, for example

from benzolazomonoethyl-a-naphthylamine a bluish red,

- Benzolazomonobenzyl-a-naphthylamine - - -,

- Benzolazodimethyl-a-naphtylamine - Violettroth,

- Benzolazophenyl-a-naphthylamine - red violet,

- Benzolazo-p-tolyl-a-naphthylamine - violet.

Example IV.

2.5 kg of p-tolyl-p-amido-o-toluidine chlorohydrate are dissolved in alcohol, 1.8 kg of quinone dichlorodiimide are gradually added to the slightly warmed solution with stirring and Warmed up gently until the quinone dichlorodiimide has disappeared. Now the Alcohol is distilled off, the residue taken up in hot water, the solution with sodium hydroxide solution made alkaline, squeezed, the prefecture cake boiled with water for a long time, as the dye still goes into solution, the solution filtered, acidified with hydrochloric acid, and the dye salted out.

It is identical to the dye which is obtained according to Example II.

Example V.

2 kg of phenyl-p-amido-o-toluidine are dissolved in fuel, 2.3 kg of dichloro-α-naphthoquinonediimide (obtained by oxidation of " _x a. ₂ -naphthylenediamine with chlorinated lime") are gradually added to the cold solution and on the water bath heated gently until the reaction has ended.

The alcohol is then distilled off, the residue taken up in hot water The solution is filtered and the dye is salted out. It is identical to that obtained in Example III.

Example VI.

2 kg of phenyl-p-amido-o-toluidine and 1.4 kg p-Amidodimethylaniline are available in approx. 20 kg 5oproc. Acetic acid dissolved; A solution of 3 kg of sodium dichromate is added to the cold solution slowly run in 5 l of water with constant stirring and heat until the color of the solution is purely fuchsin red has become and is no longer increasing in intensity.

The dye is salted out, taken up in water for cleaning, the solution made alkaline with sodium hydroxide solution, filtered, the filtrate acidified with hydrochloric acid, and the dye salted out. He. is identical to the dye of Example I.

Example VII.

2.4 kg of phenyl - ρ - amido - ο - toluidine chlorohydrate and 2.3 kg of Ci ₁ α ₂ - naphthylenediamine chlorohydrate are in approx. 10 kg 3oproc. Acetic acid dissolved; A solution of 3 kg of sodium dichromate in 5 l of water is slowly added to the warm solution with constant stirring and heated until the color of the solution has become pure red and no longer increases in intensity. The dye is salted out, taken up in hot water for cleaning, the solution filtered and salted out again.

The dye is identical to that obtained in Example III. Instead of sodium dichromate other oxidizing agents can be used.

In the above examples, the p-amidoazo compounds mentioned there can through any other, the ρ-amidodimethylaniline

Claims (1)

or Ci ₁ ct ₂ - naphthylenediamine by any other ρ-diamines, the benzo- or naphthoquinone dichlorodiimide by other p-quinonimides or chlorimides, the phenyl or. p-Tolyl-p-amido-o-toluidine can be replaced by other alphyl-p-amido-o-toluidines. All the products thus created are closely related in their properties to those described above at. Instead of the solvents mentioned in the examples BEZW. Thinner (phenol, Alcohol, dilute or concentrated acetic acid) can use other solvents, e.g. B. Glycerin, water, etc., can be applied. Patent claims: i. Process for the preparation of red to violet azine dyes, consisting therein that instead of using the method of the main patent, alphyl-p-amido-o-toluidines are used to condense with nitroso compounds, here alphyl-p-amido-o-toluidine a) with p-amidoazo compounds of the benzene or naphthalene series or their substitution products brings into reaction, b) with quinonimides of the benzene or naphthalene series or their substitution products treated, c) with ρ-diamines of the benzene or naphthalene series or their substitution products together oxidized. The execution of the process protected by claim ι using Phenyl-ρ-amido-o-toluidine or p-tolylp - amido - ο - toluidine. The execution of the process protected by claim ι using a) the ρ-azo compounds of the aniline, o-toluidine, Monoäthylanilins, monomethyl - ο - toluidine, diphenylamine, Dimethylanüins, Diäthylanilins, Methyldiphenylamins, ct-Naphtylamins, Monoä'thyl - et- naphty amine, monobenzyl - a naphtylamins, dimethyl a-naphthylamine, phenyl-a-naphthylamine, ρ-tolyl- a- naphthylamine, methylbenzylaniline sulfonic acid and methyldiphenylamine sulfonic acid; b) of benzo- or naphthoquinone dichlorodiimide; c) by reducing the nitroso compounds used in the main patent or the azo compounds mentioned in this claim under a) obtainable ρ - diamines.