DE1183187B - Process for the preparation of dyes of the anthraquinone series - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

Boarding school Class: C 09 b

GERMAN

PATENT OFFICE

EDITORIAL

German KL: 22 b -3/03

Number: 1183 187

File number: C 25496IV c / 22 b

Filing date: November 13, 1961

Opening day: December 10, 1964

The present invention relates to the preparation of new water-soluble anthraquinone dyes the formula

NH ₂

SO ₃ H

(1)

/ ^c \

N N

Il

• N —C

C -N -R

Process for the preparation of dyes of the anthraquinone series

Applicant:

CIBA Aktiengesellschaft, Basel (Switzerland)

Representative:

Dr.-Ing. F. Wuesthoff, Dipl.-Ing. G. Pulse and
Dipl.-Chem. Dr. rer. nat. E. Frhr. v. Bad luck man,
Patent Attorneys, Munich 9, Schweigerstr. 2

Named as inventor:

Dr. Arthur Bühler, Rheinfelden (Switzerland)

Claimed priority:

Switzerland of November 14, 1960 (12 720)

NH ₂

SO ₃ H

NH (2)

where m, η and ρ are each an integer, small number, R the radical of an aminobenzenesulfonic acid or carboxylic acid bonded to the triazine ring via its nitrogen atom, X the radical of a saturated secondary amine bonded via its nitrogen atom or a primary amine which is a hydroaromatic Has a chain, a branched chain or an aliphatic chain containing oxy or alkoxy groups, Y is a chlorine or hydrogen atom or a low molecular weight alkyl group and Z is a sulfonic acid group or a hydrogen atom.

For the preparation of these dyes, according to the invention, trihalotriazines, in particular the 2,4,6-trichloro-1,3,5-triazine in any order on the one hand with a dye of the formula

wherein Y, Z, m and ρ have the meaning given in the explanation of the formula (1), and on the other hand with an aminobenzenesulfonic acid or an aminobenzenecarboxylic acid and with a saturated, secondary amine or a primary amine, which has a hydroaromatic chain, a branched or condensed has an aliphatic chain containing oxy or alkoxy groups.

As examples of anthraquinone dyes that can be used as starting materials in the present process, the following may be mentioned: - Amino - 4 - (3 '- aminophenylamino) - anthraquinone-2-sulfonic acid, l-amino-4- (3'-amino- 6'-methylphenylamino) - anthraquinone - 2 '- sulfonic acid, 1 - amino-4- [N-methyl-N- (3'-N ^/ -methylaminophenyl) -arnino] -anthraquinone-2-sulfonic acid.

«9 757/283

As aminobenzenesulfonic acid or carboxylic acid, there may be mentioned: l-aminobenzoI-2-, -3- or -4-sulfonic acid, l-aminobenzene-2-, -3- or -4-carboxylic acid, 1 - aminobenzene - 2,5 - disulfonic acid, 4 - chlorine-

1 - aminobenzene - 2 - sulfonic acid, 1 - aminobenzene

2 - carboxylic acid - 5 - sulfonic acid and 1 - methylaminobenzene-3- or -4-sulfonic acid, while saturated amines such. B. Cyclohexylamine, N-methyl-cyclohexylamine, Mono- and diethanolamine, y-methoxypropylamine, Dimethyl, diethyl, di-n-butylamine, 2-ethylhexylamine, isopropylamine can be mentioned.

According to the method according to the invention, one can e.g. B. implement 1 mole of cyanuric chloride with 1 mole of one of the specified amines or with 1 mole of an aminobenzenesulfonic or carboxylic acid to primary condensation products which still have two reactive halogen atoms. You can also first convert the anthraquinone dyes with cyanuric chloride or bromide to form primary condensation products. According to the invention, these primary condensation products are further condensed to binary and finally to ternary condensation products, advantageously at a somewhat elevated temperature, e.g. B. between 30 and 9O ⁰ C, preferably between 55 and 80 ⁰ C. It can be reached ² S characterized in that the condensation proceeds more rapidly and completely than at low temperatures.

The condensations according to the invention are expediently carried out in the presence of acid-binding agents such as Sodium acetate, sodium hydroxide or carbonate.

The products of the formula (1) obtained by the specified process are new. You are valuable Dyes that are used for dyeing and printing a wide variety of materials, especially those containing nitrogen Textile materials such as silk, leather and especially wool, as well as synthetic synthetic fibers Super polyamides and super polyurethanes are suitable. They are suitable for normal acid dyeing, z. B. from baths containing sulfuric acid, especially for dyeing from weakly alkaline, neutral or weakly acidic bath, preferably from a bath with a pH between 5 and 7 lies. The good cotton reserve is striking. Draw the dyeings and prints thus obtained by a special evenness and purity of their color tones, by a good lightfastness and through excellent wash and milled fastness.

Compared to the dye known from Swiss Patent 181 718, the Dyes wool in purple tones, and compared to those from Swiss patents 181 719 and 181 720 known dyes that dye wool in cloudy green tones have the invention obtained dyes have the advantage of delivering purer, brilliant blue dyeings that are more wet-fast, in particular, they are more washable and waterfast than those made with the previously known products Swiss patents 181719 and 181 720 can be obtained.

In the following examples, unless otherwise stated, the parts mean parts by weight, the percentages by weight and the temperatures are given in degrees Celsius. The relationship between parts by weight and parts by volume is the same as that between the liter and the Kilogram.

example

19 parts of l-aminobenzene-3-sulfonic acid are used in Suspended 200 parts of water and dissolved by adding sodium hydroxide solution at pH 7 and reduced to 0 ° chilled. A suspension of 20 parts of cyanuric chloride in 80 parts is added to the cooled solution Acetone, 100 parts of water and 100 parts of ice, stirred for about 30 minutes at 0 to 5 °, whereby is kept at pH 7 by adding dilute sodium hydroxide solution.

40.9 parts of 1-amino-4- (3'-aminophenylamino) anthraquinone-2-sulfonic acid are dissolved in 1000 parts of 40 ° warm water and neutralized, mixed with the solution of the monocondensation product and stirred for about 1 hour at 35 to 40 °, by adding dilute sodium hydroxide solution the pH is kept between 5 and 7. When the condensation is complete, there are 45 parts N-methylcyclohexylamine was added and the reaction mixture was refluxed for a few hours cooked. After cold stirring, the mixture becomes weakly Congo acidic with dilute hydrochloric acid placed and the precipitated dye separated off by filtration.

When dried it is a blue powder that dissolves in water with blue and in concentrated sulfuric acid dissolves with violet-red color and wool from a weakly acidic bath in full, even, reddish-blue tones with good fastness properties colors.

According to this method, from cyanuric chloride, the acids indicated in column I, the Anthraquinone dyes indicated in column II and the amines in column III of the following table Similar dyes that color wool in the shades mentioned in column IV.

I. II III IV NH ₂ Av-NH ₂ Cyclohexylamine blue SO ₃ H nhV the same X
the same Di-n-butylamine blue iH N-NH ₂ /

continuation

πι

NH ₂

NH ₂

SO ₃ H

SO ₃ H

the same
the same

NH ₂

SO ₃ H

the same
the same

the same
the same
the same

SO ₃ H

the same

1-aminobenzene-4-sulfonic acid

the same

the same.

the same

like. like. like.

the same

the same

the same. the same. 2-ethylhexylamine

blue

Benzylamine

N-phenyl-jS-hydroxyethylamine

2-ethylhexylamine

Blue blue

blue

Cyclohexylamm blue N-methylcyclohexyl-
amine blue Cyclohexylamine blue Dibutylamine blue 2-ethylhexylamine blue N-methylcyclohexyl-
amine blue N-methylaniline blue

Morpholine

2-ethylhexylamine
2-ethylhexylamine

blue

Blue blue

Dyeing prescription

2 parts of the dye obtainable in accordance with paragraphs 1 to 3 of this example are dissolved in 4000 parts of water, 10 parts of crystallized sodium sulfate are added and 100 parts of well-wetted wool are added to the dyebath thus obtained at up to 50 °. Then 2 parts of 40% acetic acid are added, the mixture is brought ^{to the boil within 1} 1/2 hours and the color is boiled for% hours. Finally, the wool is rinsed with cold water and dried. The wool is dyed in even, washable blue tones with good lightfastness.

If you dye in the presence of 4 parts of ammonium acetate instead of 2 parts of 40% acetic acid, this also gives real colorations.

Claims (6)

Patent claims: 1. Process for the preparation of dyes of the anthraquinone series, characterized in that that trihalotriazines, especially in particular the 2,4,6-trichloro-1,3,5-triazine j _n any order on the one hand with a dye of the formula NH ₂ SO ₃ H NH where m and ρ are each an integer, small number, Y is a chlorine or hydrogen atom or a low molecular weight alkyl group and Z is a sulfonic acid group or a hydrogen atom, and on the other hand condensed with an aminobenzenesulfonic acid or an aminobenzenecarboxylic acid and with a saturated secondary amine or a primary amine, which has a hydroaromatic chain, a branched chain or an aliphatic chain containing oxy or alkoxy groups. 2. The method according to claim 1, characterized in that cyanuric chloride and the three other reactants in a molar ratio of about 1: 1: 1: 1. 3. The method according to any one of claims 1 and 2, characterized in that from Anthraquinone dye of the formula
O NH ₂ SO ₃ H NH ₂ goes out. 4. The method according to any one of claims 1 to 3, characterized in that cyanuric chloride first with the aminobenzenesulfonic acid or carboxylic acid to dihalotriazine compounds condensed and this reacts with the anthraquinone dye. 5. The method according to claim 4, characterized in that the third chlorine atom replaced in the triazine ring by the remainder of a cyclic, secondary, hydroaromatic amine. 6. The method according to any one of claims 1 to 5, characterized in that the condensation to the secondary condensation product between 30 and 90 ⁰ C, preferably between 55 and 80 ⁰ C, is carried out. Considered publications:
Swiss patents No. 181 718,
719, 181 720. When the application was announced, a coloring table provided with explanations was displayed. 409 757/283 12.64 © Bundesdrucketei Berlin