DE1085989B - Process for the production of azo dyes - Google Patents

Description

GERMAN

It has been found that valuable azo dyes are obtained if diazo compounds are used in o-Position to the diazo group is a metal complex-forming group or one under the conditions the metallization have substituents which can be converted into a metal complex-forming group, with 5,5'-Dioxy-2,2'-azonaphthalene-7,7'-disulfonic acid couples and the resulting dyes into their metal complex compounds convicted.

As metal complex-forming groups in the diazo components the hydroxyl group, the carboxyl group or a heterocyclically bonded one may be mentioned NH group. As residues, which under the conditions of metallization in a metal complex-forming Group can be converted, for example: alkoxy groups, halogen atoms, the Sulfonic acid group and a hydrogen atom.

5,5'-dioxy-2,2'-azonaphthalene-7,7'-disulfonic acid can by a process known per se by reacting 2-diazo-5-l> enzenesulfonyloxynaphthalene-7-sulfonic acid with salts of sulphurous acid to form the symmetrical azo body and subsequent cleavage of the benzenesulfonic acid residue can be obtained with sodium hydroxide solution at about 90 ° C.

The diazo compounds to be used according to the invention can have substituents customary in azo chemistry, such as sulfonic acid, carboxylic acid, nitro, alkyl, halogen, sulfonic, sulfonic acid amide and azo groups contain. Suitable diazo components are, for example, aminobenzene, l-amino-2-chloro-enzene-4-sulfonic acid, 1 - Amino - 2 - methoxybenzene - 5 - sulfonic acid, 1-aminobenzene-2-carboxylic acid, 1-amino-2-chloronaphthalene-7-sulfonic acid. 2-aminonaphthalene-4,8-disulfonic acid. l-amino-2-oxy-4-nitrobenzene, l-amino-2-oxybenzene-5-sulfonic acid, 5-methyl-4-aminobenzotriazole, 2-ethyl-4-amino-5-methoxy-1,1'-azobenzene-4'-sulfonic acid.

Two identical or different diazo compounds can be used for the coupling Kind of use.

A modification of the process consists in coupling a diazo compound of the type described in an alkaline medium with 2-amino-5-oxynaphthalene-7-sulfonic acid, converting the aminoazo compounds obtained into their metal complex compounds, preparing the diazo compounds from these in acetic acid solution and 2 Molecules of the same or different diazoazo compounds of this type are converted into a symmetrical or asymmetrical disazo or polyazo dye with 5,5'-dioxy-2,2'-azonaphthalene-7,7'-disulfonic acid as the middle component by the action of salts of sulfurous acid. In this case, too, as in the case of the first-mentioned method, the metallization can be a method of production
of azo dyes

Applicant:

Paint factories Bayer Aktiengesellschaft, Leverkusen-Bayerwerk

Dr. Fritz Suckfüll, Leverkusen,

Dr. Horst Nickel, Cologne-Stammheim,

Dr. Karl-Heinz Schmidt, Cologne-Flittard,

and Dr. Karl-Heinz Schündehütte, Leverkusen,

have been named as inventors

in any phase, if desired, also in the final phase as an aftertreatment process on the Fiber.

The transfer of the metal-free dyes or those occurring in the manufacturing process Intermediate products in their metal complex compounds, preferably in the copper and nickel complex compounds, takes place by known processes, for example by reaction with copper salts in aqueous, weakly acidic solution, by dealkylating metallization of o-oxy-o'-alkoxyazo compounds or by coppering with replacement of the chlorine substituent of o-oxy-o'-chloroazo dyes. In the event that the diazo component is located o-to the azo bridge, into a metal complex-forming Group transferable substituent denotes a hydrogen atom or a sulfonic acid group, can the production of copper complex compounds of the ο, ο'-dioxyazo dyes by oxidative Copper plating according to the process of German patents 807 289, 889 196, 893 699 or 1 006 098 be performed.

The metal-containing or on the fiber with metal salts obtainable by the present process Post-treated dyes are particularly suitable

009 568/282

others for dyeing fibers made from natural and regenerated cellulose. The colorations stand out characterized by good fastness properties.

OCH,

The coloring with the copper complex compound of the azo dyes obtainable according to the process formula

OH

OH

OCH,

HO

-N = N -

■ - N = N
HO ₃ S

COOH

CH ₁

shows in comparison to the nachgekup obtained according to the example of the US Pat. No. 2,369,516 _x - N = N -

_ N _{= N} _
-SO ₃ H

CH,

ferten coloring on better lightfastness.

example 1

30.3 parts by weight (0.1 mol) of 2-aminonaphthalene-4,8-disulfonic acid are diazotized as usual and at 0 ^: C with the solution of 23.7 parts by weight (0.05 mol) of the azo compound of the formula

HO

OH

(I)

H0, S -

-N = N

-SO ₃ H

combined in 1800 parts by volume of water and 140 parts by volume of 20% soda solution. After the coupling is complete, the resulting dye is treated with sodium chloride deposited and isolated.

The dye paste obtained is dissolved in 1400 parts by volume of hot water and in acetic acid, with Sodium acetate buffered medium with 25 parts by weight of crystallized copper sulfate and about 280 vol. Around 3% of hydrogen peroxide is oxidatively coppered at 60 ° C. The obtained copper complex compound of the dye of the formula

HO ₃ S

OH

HO

OH

HO SHO,

-N = N-HO ₃ S-

Y- N = N -. '
J-SO ₃ H

S0, H

S0, H

is salted out with sodium chloride and isolated. The dried dye is a dark powder that turns out to be Dissolves in water with a blue color and dyes cotton in blue tones.

100 parts by weight of cotton are placed in a dyebath at room temperature which contains 2 parts by weight of this dye, 1 part by weight of soda and 20 parts by weight of sodium sulfate dissolved in 4000 parts by volume of water. Within 30 Alinuten the dyebath at 90 ^c C and is heated for 30 minutes at 90 to ^95: kept C. The cotton is then rinsed and dried. A greenish blue dyeing of very good fastness properties is obtained on cotton.

Example 2

20.3 parts by weight (0.1 mole) of 1-amino-2-methoxybenzene-5-sulfonic acid are diazotized as usual and soda-alkaline with 23.7 parts by weight (0.05 mol) of the azo compound of the formula (I) at 0 ° C Example 1 coupled. The dye deposited with sodium chloride is isolated and used according to known methods Methods of demethylating coppered. The obtained copper complex compound of the dye of the formula

OH

HO

OH

HO

N = N-

HO ₃ S-

-N = NN = N-SO ₃ H

SO ₃ H

SO ₃ H

is a dark powder after drying that dissolves in water with a purple color and cotton in colors blue-violet tones.

Example 3

The solution of 23.7 parts by weight (0.05 mol) of the azo compound of the formula (I) from Example I in 1800 parts by volume of water is at 20 ° C with a like Customarily prepared diazonium salt solution from 13.7 parts by weight (0.1 mol) of 1-aminobenzene-2-carboxylic acid combined, treated with 70 parts by volume of 20% sodium acetate solution and then 140 parts by volume 20% soda solution was added dropwise. After the coupling has ended, the dye is isolated with sodium chloride. The dried dye is a dark powder that dissolves in water with a bordeaux red color and Cotton - the fibers are treated with Ktipfersalts - dyes in purple tones.

Example 4

13.7 parts by weight (0.1 mole) of aminobenzene-2-carboxylic acid are diazotized and soda-alkaline as usual

with 23.9 parts by weight (0.1 mol) of 2-amino-5-oxynaphthalene-7-sulfonic acid coupled and the compound obtained isolated. The dye paste is dissolved in 1400 parts by volume of water with a weak soda-alkaline solution and with 69 parts by volume of 10% sodium nitrite solution offset. The mixture is allowed to add 42 parts by volume of 30% strength hydrochloric acid and 50 parts by volume at 0 ° C Running water. After the reaction has ended, the diazonium salt is isolated. The paste will be in 200 parts by volume of water are mixed, 35 parts by volume of 20% sodium acetate solution are added and 14 parts by weight are added crystallized sodium sulfite in 70 parts by volume of water. After the reaction has ended is heated to 40 ° C, the precipitated dye is separated off and redissolved. The dye obtained is identical to the dye prepared according to Example 3.

Example 5

23.7 parts by weight (0.05 mol) of the compound (I) from Example 1 are mixed with the diazonium salt solution of 14.8 parts by weight (0.1 mole) of 5-methyl-4-aminobenzotriazole. The isolated dye paste is taken up in 2800 parts by volume of hot water and precipitated and isolated with sodium chloride. The dried dye is a dark puI-

ver, which dyes cotton after the fiber has been treated with copper salts in gray tones.

Example 6

The diazonium salt is added to the solution of 23.7 parts by weight (0.05 mol) of the compound (I) from Example 1 from 32.2 parts by weight (0.1 mol) of 4-arnino-3-methoxy-6-methyl- (1.1 ') "azobenzene-4'-sulfonic acid given and coupled with alkaline soda. After the coupling is complete, the dye is isolated and used in the usual way Coppered demethylating way. The dried dye is a dark powder and dyes cotton in gray-green tones.

¹ S example 7

23.7 parts by weight (0.05 mol) of the azo compound of the formula (I) from Example 1 are in soda-alkaline Solution first with the diazo compound from 9.5 parts by weight (0.05 mol) of 2-amino-1-oxybenzene 4-sulfonic acid coupled and then with the diazo compound from 16.1 parts by weight (0.05 mol) 2 - methyl - 4-amino-5-methoxy- (1,1 ') -azobenzene-4'-sulfonic acid combined. The deposited dye will under demethylating conditions into the copper complex compound of the probable formula

HO ₃ S

Cu

/ - N = N

ϊ— N == N

I- SO ₃ H

\ _ N = N

V-SO ₃ H

CH ₃

HO ₃ S

converted. The dried dye is a dark powder that dissolves in water with a bluish gray color dissolves and dyes cotton in gray tones.

OH

HO

The same dye can be obtained by adding the dye after the first coupling has taken place

OH

HOoS

N = N-HO ₃ S

-N =

SO, H

converted into the copper complex compound, then coupled with the second diazo component and finally demethylating copper.

Claims (2)

Patent claims: 1. A process for the preparation of azo dyes «, characterized in that diazo compounds which have a metal complex-forming group in the o-position to the diazonium group or a substituent which can be converted into a metal complex-forming group under the conditions of metallization, with 5,5'-dioxy-2 , 2'-azonaphthalene-7,7'-disulfonic acid is coupled and the dyes obtained are converted into their metal complex compounds. 2. Modification of the method according to claim 1, characterized in that a diazo compound, in the o-position to the diazonium group a metal complex-forming group or one below convertible into a metal complex-forming substituent under the conditions of metallization Have group, couples with 2-amino-5-oxynaphthalene-7-sulfonic acid in an alkaline medium, the aminoazo compounds obtained, if appropriate, into their metal complex compounds transferred, from these in acetic acid solution produces the diazonium compounds, 2 moles of the same or various diazonium compounds of this kind by the action of salts of the sulphurous Acid into a symmetrical or asymmetrical polyazo dye with 5,5'-dioxy-2,2'-azonaphthalene-7,7'-disulfonic acid transferred as a central component and optionally aftertreated the dye with metal donating agents. Considered publications:
U.S. Patent No. 2,369,516. A coloring table was displayed when the application was announced. © 009 568/282