DE2500237B1 - ANTHRACHINOID DISPERSION COLORS, THEIR PRODUCTION AND THEIR USE - Google Patents

Description

The invention relates to new anthraquinoid disperse dyes based on -tetrasubstituted Anthraquinone.

The new dyes have the formula

O ₉ NO NH

(D

HO O NH,

40

45

in which X stands for a bromine or chlorine atom.

The dyes dye synthetic fibers, especially those made from linear polyesters, in clear blue Shades. The dyeings have a high degree of heat-setting, wash-fastness and light-fastness on.

The dyes of the formula I are expediently by halogenating 1,4-diamino-, 1,4-bis- (N-alkylamino) - or 1-amino ^ -N-alkylamino-S-hydroxy-8-nitroanthraquinones in solvents which are inert under the reaction conditions, optionally in Presence of halogenation catalysts obtained. As starting compounds come z. B. Consider: M-diamino-S-hydroxy-e-nitroanthraquinone, 1 -Amino ^ -N-alkylamino-S-hydroxy-S-nitroanthraquinone with 1 to 4 carbon atoms in alkyl, such as 4-N-methylamino, 4-N-ethylamino, 4-N-propylamino, 4-N- (n-butylamino) -, 4-N- (2'-butylamino);

4-N-isopropylamino-1-amino-5-hydroxy-8-nitroanthraquinone and

1,4-bis (N-alkylamino) -5-hydroxy-1-nitroanthraquinone with 1 to 4 carbon atoms per alkyl, such as

1,4-bis (N-ethylamino) -1,4-bis (N-isopropylamino) -, 1,4-bis (N-propylamino) -,
1,4-bis- (N-butylamino) -, 1,4-bis- (N-2'-butylamino) - and also

1,4-bis (N-methylamino) -5-hydroxy-8-nitroanthraquinone

or mixtures of these compounds. The starting compounds are from economic and technical Reasons 1 ^ -Diamino-S-hydroxy-e-nitroanthraquinone, 1-Amino-4-N- (2-butylamino) -5-hydroxy-8-nitroanthraquinone is preferred

As inert solvents are, for. B. chlorinated aliphatic and aromatic hydrocarbons, such as dichloroethane, Tetrachloroethane, o-dichlorobenzene, trichlorobenzene, Ν, Ν-dimethylformamide, N-methylpyrrolidone and preferably nitrobenzene suitable The halogenation is advantageously carried out in the presence of halogenation catalysts, such as sulfur, iron (III) chloride, antimony V-chloride, iron powder or preferably in Presence of iodine.

In addition to chlorine and bromine, sulfuryl chloride can also be used as halogenating agents.

The halogenation is expediently carried out by suspending the starting compound in the solvent, optionally adding the halogenation catalyst and then adding dropwise or introducing the halogenating agent with stirring at room temperature. The reaction mixture is then stirred at the desired temperature until the reaction is complete Temperatures between 20 and 90 ⁰ C, preferably between 40 and 70 ⁰ C to the end.

In the case of the implementation of l-amino-4-N-alkylamino- or 1,4-bis (N-alkylamino) -5-hydroxy-8-nitroanthraquinones, the halogenation is advantageously carried out in the presence of water.

The reaction is usually complete after 1 to 10 hours, depending on the temperature chosen. The dye is isolated from the reaction mixture after cooling to 20 to 40 ° C. in a manner known per se.

The bromination can also be carried out in such a way that initially only about half of the suspension is added the required amount of bromine is added and then the hydrogen bromide formed during the bromination with an oxidizing agent, e.g. B. with alkali bromate, oxidized to bromine

The oxidizing agent is expediently used in the form of an aqueous solution.

The new disperse dyes have a higher than 1,4-diamino-5-hydroxy-8-nitroanthraquinone Color strength and better heat-setting fastness

The parts and percentages given below relate to weight.

example 1

50 parts of 1-amino-8-nitro-4-N- (2'-butylamino) -5-hydroxyanthraquinone are suspended in 500 parts of nitrobenzene and 2 parts of iodine are added. Then you drip with stirring, 45 parts of bromine in the course of 15 minutes. The temperature of the reaction mixture rises in the process to 30 to 35 ° C. A solution of 5 parts is then left within 15 minutes Sodium bromate in 50 parts of water are added dropwise, the temperature in the reaction mixture increasing to 40 to 45.degree increases. The reaction mixture is stirred for a further 4 hours at 60 to 65 ° C. and allowed to come to room temperature cool and suck the precipitated reaction product away. The filter residue is with nitrobenzene and then

washed with methanol. After drying, 24.5 parts of a dye of the formula are obtained

HO O NH ₂

in the form of a blue powder.

Analysis: Ci ₄ H ₈ BrN ₃ Os.

Calculated: C44.8, H 2.3, Br 21.1, N 11.1%;
found: C 44.5, H 2.1, Br 21.1, N 11.1%.

Example 2

5 parts of 1,4-diamino-5-hydroxy-8-nitroanthraquinone are suspended in 50 parts of nitrobenzene and 0.2 Parts of iodine are added to the mixture, while stirring at room temperature within 10 minutes 4.5 parts of bromine drop. The reaction mixture is stirred for a further 2 hours at 60 to 65 ° C and then cooled to room temperature. The precipitated reaction product is filtered off with suction and washed first with nitrobenzene and then with methanol.

After drying, 3.2 parts of a bromo-1 ^ -diamino-S-hydroxy-e-nitroanthraquinone are obtained as blue powder. The dye has the same properties as those of Example 1.

The yield can be increased significantly if the reaction mixture before Sucking off the dye adds methanol or petroleum ether.

Example 3

5 parts of 1,4-diamino-5-hydroxy-8-nitroanthraquinone are added to 50 parts of nitrobenzene and 0.2 parts of iodine suspended and with stirring at room temperature with 5

ίο parts sulfuryl chloride added. The retraction mixture is stirred for 15 minutes at room temperature and 30 minutes at 60 to 65 ° C. After cooling down 200 parts of methanol are added. The reaction product is filtered off with suction, with methanol and hot water washed and dried.

3.2 parts of a dye with a chlorine content of 10.8% corresponding to the monochlorine compound are obtained.

Analysis: Ci ₄ H ₈ ClN ₃ O ₅ .
Calculated: Cl 10.6%;
found. Cl 10.8%.

Example 4

One works as indicated in Example 3. Instead of 5 parts of sulfuryl chloride, however, at 60 to 65 ° C Introduced chlorine until no starting product can be detected in the reaction mixture

A dye with a chlorine content of 15% is obtained. The dye is a mixture of the mono- and dichloro compound of 1,4-diamino-5-hydroxy-8-nitroanthraquinone. For the monochloro compound _{Ci 4} H _{8 ClN 3} O ₅ , a content of 10.6% Cl is calculated, for the dichloro compound Ci ₄ H ₇ Cl ₂ N ₃ O ₅ of 19.3% Cl.

Claims (3)

Patent claims: 1. disperse dyes of the formula O ₇ NO NH, IO HO O NH, in which X stands for a bromine or chlorine atom 2. Process for the preparation of the dyes according to Claim 1 by halogenation of Aminoanthraquinone derivatives in solvents, optionally in the presence of halogenation catalysts, characterized in that M-diamino-S-hydroxy-e-nitroanthraquinone, l-Amino ^ -N-alkylamino-S-hydroxy-e-nitroanthraquinone or 1,4-bis (N-alkylamino] h5-hydroxy-8-nitroanthraquinone or mixtures thereof halogenated 3. Use of the dyestuffs according to Claim 1 for dyeing synthetic fiber material Fibers.