DE1218638B - Process for the production of dyes - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

Number:
File number:
Registration date:
Display day:

C09b

German class: 22 b -3/15

M55092IVc / 22b
December 12, 1962
June 8, 1966

The invention relates to the preparation of new dyes of the general formula

NH-X

O Y

wherein X represents a 2-benzothiazolyl group, which is optionally substituted in the 6-position by a nitro or amino group, one of the radicals Y. represents an NH2 group and the other represents a hydrogen atom. It also concerns the production of Mixtures of these compounds.

These dyes are prepared by adding 2-chlorobenzothiazole or its in the δ-position by a nitro or amino group substituted derivatives with diamino-anthraquinones, for example 1,8-diamino-anthraquinone, 2,6-diamino-anthraquinone, 1,4-diamino-anthraquinone, 1,6-diamino-anthraquinone or with mixtures of 1,6-, 1,7-, 1,8-, 2,6-, 2,7-diamino-anthraquinones. The reaction products consist for the most part of a single 2-benzothiazolyl-amino group substituted anthraquinone derivatives, but in the course of the reaction can form a small amount of disubstituted derivatives take place.

The reaction can be carried out in the presence of organic solvents; it runs particularly well in phenol in the range between 120 and 22O ⁰ C from.

The dyes which can be prepared according to the invention have a good affinity for synthetic ones Fibers, especially as opposed to polyester-based fibers which they dye in shades that have good fastness properties to light and sublimation.

It is already from the French patent specification 1 193 733 and the German Auslegeschrift 1 085 993 known to acylate all free NH2 groups of an anthraquinone with 2-chlorobenzothiazole. It was in no way predictable that it would, even from perfectly symmetrical diamino-anthraquinones starting out, in which the amino groups ζ. B. in the 1.5, 1.8, 1.4, 2.6 or 2.7 position are arranged, it would be possible to obtain dyes in which only one of the two amino groups is acylated by 2-chlorobenzothiazole.

Process for the production of dyes

Applicant:

Etablissements Kuhlmann, Paris

Representative:

Dr. M. Eule, Dipl.-Chem. Dr. rer. nat. WJ Berg
and Dipl.-Ing. O. Stapf, patent attorneys,
Munich 2, Hilblestr. 20th

Named as inventor:

Andre Simonnet, Creil, Oise;

Louis Cabut, Nogent-sur-Oise (France)

Claimed priority:

France of December 14, 1961 (881955)

Color the monoamino - monobenzothiazolylamino - anthraquinone dyes according to the invention Ethylene glycol polyterephthalate in yellow to reddish blue shades, the significantly greater lightfastness and sublimation fastness than the starting products and clearly stronger colorations result as the corresponding dyes bearing two benzothiazole amino groups. Opposite to the α-benzoylamino-α-benzothiazolyl-aminoanthraquinone Example 1 of French patent specification 1,193,733 gives the corresponding α-aminoa-benzothiazolylamino-anthraquinone a redder and stronger coloring, which also has a greater lightfastness having.

Dye swatches were made with ethylene glycol poly terephthalate satin using diaminoanthraquinone, bis (benzothiazolylamino) anthraquinones, and benzothiazolylamino aminoanthraquinones. These samples were subjected to a sublimation resistance test in a thermal test device (30 seconds at a pressure of 30 g / cm ^{2) and a lightfastness test in a fadeometer.} The staining swatches each previously dispersed with 4% one in the ratio 30:70

609 578/490

Dye produced showed the behavior evident from Tables A, A ', B, B' and C. The dyes used in each case can be seen from the list below.

Panels A, A '

1,8-diamino-anthraquinone,

1,8-bis (benzothiazolylamino) anthraquinone,

8-Benzothiazolylamino-1-amino-anthraquinone.

Panels B, B '

1,5-diamino-anthraquinone,

l, 5-bis (benzothiazolylamino) anthraquinone,

5-benzothiazolylamino-1-amino-anthraquinone.

Panel C '

5-benzothiazolylamino-1-benzoylaminoanthraquinone.

The superiority presented at the beginning is from the tables of the dyes produced according to the invention are actually evident.

In the following examples the parts mentioned are parts by weight.

example 1

1,8-diamino-anthraquinone 9.6 parts are slowly introduced in 40 parts of phenol, which was brought to a temperature of 90 to 100 ⁰ C. The mixture is heated to 150 to 160 ^° C. and 7.14 parts of 2-chlorobenzothiazole are added over the course of 7 hours. The temperature is then held at 150 to 160 ^° C. for 15 hours. After cooling to 12O ⁰ C the mixture 3.7% sodium soda is introduced into 500 parts of a, stirred for 1 hour, filtered, the precipitate is washed with water until neutral, dried in air and dried. The dye obtained in this way, which was previously dispersed, dyes polyester fibers in a red shade which has very good fastness properties to light and sublimation.

Example 2

45

4.8 parts of 2,6-diamino-anthraquinone are introduced into 40 parts of molten phenol. The mixture is heated to 130 ^° C., 3.8 parts of 2-chlorobenzothiazole are slowly added, and ^{the mixture is then heated to 150 to 160 °} C. for a further 24 hours. After cooling to 90 ^° C., it is diluted with 500 parts of ethyl alcohol, filtered and washed Residue with boiling ethanol. The alcoholic filtrates are then introduced into 3600 parts of water. Make alkaline with soda lye, filter and wash the precipitate with water until it is neutral. The product obtained in this way dyes polyester fibers in a golden yellow shade with remarkable fastness properties to sublimation.

one and washes the residue with a little 100% sulfuric acid. The filtrates are introduced into 2000 parts of ice water, filtered and washed Precipitate with water until neutral, air dry and dry. One receives on this Way, after reduction with sodium sulfide, 35 parts of a mixture of diamino-anthraquinone, which in particular consists of 1,6-diamino-anthraquinone.

9.6 parts of this mixture are slowly added to 80 parts of molten phenol. The mixture is heated to 120 ⁰ C below. If this temperature is achieved, one introduces 7.6 parts of 2-chlorobenzothiazole and sets the reaction continued characterized in that the mixture is heated 24 hours on 150 to 16O ⁰ C. After cooling to 120 ^° C., the mixture is introduced into 1000 parts of 5% strength soda solution; stir for 1 hour, filter, wash the precipitate until neutral, air dry and dry. In this way, 17.2 parts of a brownish powder are obtained. This dye mixture, which has been dispersed beforehand, dyes polyester fibers in brown. Color shade which has good fastness properties to light and sublimation.

Example 4

9.6 parts of 1,4-diamino-anthraquinone are slowly introduced into 60 parts of molten phenol. The mixture is heated to 150 to 160 ^° C., 7.14 parts of 2-chlorobenzothiazole are added over the course of 8 hours and the reaction is ended, this temperature being maintained for a further 14 hours. The dye is then separated off, as indicated in Example 3, and in this way 16.3 parts of a blue, very dark powder which dyes polyester fibers in a reddish-blue shade with very good fastness properties to light and sublimation.

Example 5

10 parts of dihydro-1,4-diamino-anthraquinone are introduced into 60 parts of molten phenol. The mixture is heated to 150 ° C. and air is passed through until the oxidation in 1,4-diamino-anthraquinone has ended. The 2-chlorobenzothiazole is then allowed to react as described in Example 4. Of the obtained dye dyes polyester fibers in a bluish-red shade similar to that of them from Example 4 is very similar and which has very good fastness properties compared to Owns light and sublimation.

Claims (1)

Claim: -Process for the production of dyes of the general formula Example 3 " 60 130 parts of anthraquinone are slowly introduced into 700 parts of 20% strength oleum with stirring. After heating to 70 ^° C. in order to dissolve the anthraquinone, the mixture is cooled to 40 ^° C. and 210 parts of nitrating acid are added. The nitration is ^{effected at 90 °} C. in 10 hours. Filtered after allowing to cool NH-X wherein X represents a 2-benzothiazolyl group, which if necessary in 6-position by a Nitro or amino group is substituted. one of the radicals Y is an NH2 group, the other one Denotes hydrogen atom, or mixtures of these dyes, characterized in that that one has 2-chlorobenzothiazoI or its in the 6-position by a nitro or amino group substituted derivatives with diaminoanthraquinones or mixtures thereof. Documents considered: German Auslegeschrift No. 1 085 993; French patent specification No. 1 193 733. When the application was announced, five coloring tables (A, A ', B, B' and C) were displayed.