DE1178961B - Process for the production of copper-containing monoazo dyes - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Boarding school Class: C 09 b

German class: 22a-l

Number: 1178 961

File number: J17923IV c / 22 a

Filing date: April 5, 1960

Opening day: October 1, 1964

The invention relates to the production of new metallized monoazo dyes which are used for coloring of cellulose textiles are valuable.

In contrast to the copper complexes known from Austrian patent specification 201 744 of azopyrazolone dyes color those obtained by the process of the present invention Dyes on adjacent fabrics during wash treatments which did not react to remove Dye are not required.

According to the invention a process for the production of new metallized azo dyes, namely proposed the copper complexes of such azo compounds, which in the form of the free acids of the formula

/ TV-M =

N = N-

R N-C

-N-C N

Process for the production of copper-containing
Monoazo dyes

Applicant:

Imperial Chemical Industries Limited, London

Representative:

Dr.-Ing. H. Fincke, Dipl.-Ing. H. Bohr
and Dipl.-Ing. S. Staeger, patent attorneys,
Munich 5, Müllerstr. 31

Named as inventor:

Cyril Eric Vellins,

Alistair Howard Berrie, Manchester,

Lancashire (UK)

Claimed priority:
Great Britain 10 April 1959 (12161),
dated February 5, 1960

N = C

(SO ₃ H) _n

correspond, in which the benzene ring A can carry further substituents, E the remainder of an acetoacetarylide, l-phenyl-5-pyrazolons or l-phenyl-5-aminopyrazoles, R is a hydrogen atom or an alkyl radical with not more than 4 carbon atoms, X is a Hydroxy, carboxy, methoxy or ethoxy group, Y a chlorine or bromine atom and π 1, 2 or 3 means.

Examples of other substituents that may be present in benzene ring A include: Nitro, chlorine, bromine, alkoxy, for example methoxy, alkyl, for example methyl, carboxy, sulfo, Alkylsulfonyl, for example methylsulfonyl, acylamino, for example acetylamino, sulfamoyl and substituted sulfamoyl, for example dimethylsulfamoyl and ethylsulfamoyl.

The process according to the invention for the preparation of the new metallized azo dyes as above described, is that a monoazo compound, which in the form of its free acid of formula

NH (SO ₃ H) _n

wherein A, E, R, X and η have the meanings given above, is treated with cyanuric chloride or cyanuric bromide and a copper-donating agent.

The monoazo compound can with the cyanuric chloride or treated with cyanuric bromide and the product thus obtained then with the copper delivering means are treated. However, it is preferred to use the monoazo compound with the copper supplying agent and then the copper complex thus obtained with the cyanuric chloride or cyanuric bromide to treat.

Treatment of the monoazo compound with the copper donating agent can be any of the processes known for the preparation of copper complexes of azo compounds be, for example, by adding a copper-donating agent to an aqueous solution of the Monoazo compound is, the mixture thus obtained is heated, sodium chloride is added, and the precipitate the copper complex of the monoazo compound is filtered off.

The treatment of the copper complex of the monoazo compound with the cyanuric chloride or cyanuric bromide is expediently carried out by mixing an aqueous solution of said copper complex with a suspension of cyanuric chloride or cyanuric bromide in water or a mixture

40 »689/308

of water and a water-miscible organic liquid, for example acetone, preferably stirred at a temperature between 0 and 5 ° C, the pH of the mixture through Addition of sodium carbonate is kept between 6 and 7, salt is added and the resulting new metallized azo dye filtered off. As examples of the copper-supplying agents used in The following may be used in the process according to the invention: copper sulfate, copper acetate and copper ammonium sulfate.

The monoazo compounds used in the process according to the invention can be diazotized of an amine of the formula

NH ₂

wherein A and X have the meanings given above, and coupling of the diazo compound thus obtained with a coupling component of the formula H - E - NHR, in which E and R are as indicated above Have meanings, are prepared, the amine and the coupling component be chosen so that the monoazo compound obtained has one, two or three sulfonic acid groups contains.

Examples of suitable amines which can be used to obtain the monoazo compounds used in the process according to the invention may be mentioned: anthranilic acid, A- or 5-sulfonanthranilic acid, A- or 5-nitroanthranilic acid, 4-, 5- or 6-chloranthranilic acid, 2-aminoterephthalic acid, 4-methanesulfonylanthranilic acid, 2-aminophenol, A- or 5-nitro-2-aminophenol, 4-, 5- or o-chloro ^ -aminophenol, 2-aminophenol-4,6-disulfonic acid, 4-chloro 2-aminophenol-6-sulfonic acid, 6 - chloro - 2 - aminophenol -A- sulfonic acid, Picraminsäure, 4-nitro-2-aminophenol-6-sulfonic acid, 6-nitro-2-aminophenol-4-sulfonic acid, o-anisidine, A- or 5-nitro-2-anisidine, A- or 5-chloro-2-anisidine, cresidine, 2-aminophenol-4-sulfonic acid, 4,5-dichloro-2-aminophenol - 6 - sulfonic acid, 4-methyl - 5 - nitro-2-aminophenol-6-sulfonic acid, 2-aminophenol-4-methylsulfone, 2-aminophenol-4-sulfonamide, 2-aminophenol - 4 - N -methylsulfonamide, 4 - bromo - 2 - aminophenol, 4-methoxy- 2-aminophenol, 4-acetylamino-2-aminoph enol-6-sulfonic acid and 2-aminophenol-4-N, N-dimethylsulfonamide.

As examples of coupling components of the formula H - E - NHR which are used can, in order to obtain the monoazo compounds used in the process according to the invention, may be mentioned: l-PhenyI-5-pyrazolone., such as 1- (3'- or 4'-aminophenyl) -3-methyl-5-pyrazolone, 1- (3'- or 4'-aminophenyl) -3-carboxy-5-pyrazolone, l- (3'-amino-4'-sulfophenyl) -3-methyl-5-pyrazolone, l- (4'-amino-3'-sulfophenyl) -3-methyl-5-pyrazolone, l- (2'-methyl-5'-aminophenyl) -3-methyl-5-pyrazolone, l-phenyl-S-amino-S-pyrazolone, l- (3'- or 4'-aminophenyl) - 3 - carbethoxy - 5 - pyrazolone, 1 - (2 '- chloro-5'-aminophenyl) -3-methyl or -carboxy-5-pyrazolone, 1- (4'-methylaminophenyl) -3-carboxy-5-pyrazolone, 1- (3'-amino-4'-sulfophenyl) -3-carboxy-5-pyrazolone and l- (4'-amino-3'-suIfophenyl) -3-carboxy-5-pyrazolone, Acetoacetaryiide, such as acetoacet-3-ammoanilide, Acetoacet-4-aminoanilide and acetoacet-4-aminoanilide-3-sulfonic acid and l-phenyl-5-aminopyrazoles such as l- (3'-aminophenyi) -3-methyl-5-aminopyrazole and 1- (3'-amino-4'-sulfophenyl) -3-methyl-5-aminopyrazole.

The new metallized azo dyes described above are preferably obtained from the media in which they were made isolated at pH 6 to 7 and it was found that the loss of chlorine or bromine atoms from the triazine ring present in the dyes Addition of buffering agents which give a pH value between 6 and 7, especially which give a pH of about 6.5 can be lowered significantly. As examples of such Pulping agents should be mentioned: Mixtures of disodium hydrogen phosphate and sodium dihydrogen phosphate or potassium dihydrogen phosphate and mixtures of sodium diethyl metanilate and sodium hydrogen sulfate. The buffering agents can be added at any time during the preparation of the dyes, but it is preferred to add the buffering agents to the reaction mixture before the isolation of the dye and after filtering off the dye, the dye paste thus obtained before drying, which is preferably is carried out at a temperature below 65 ° C, with additional buffering agent Mix. The dried dye mixtures are generally more stable than the unbuffered dried ones Dyes.

The new metallized azo dyes described above are valuable for dyeing cellulose textiles made from natural or regenerated cellulose. For dyeing such textiles you can use the new metallized azo dyes either after a dyeing or printing process on the above Textiles are applied in connection with a treatment with an acid-binding agent, for example sodium hydroxide, sodium carbonate or sodium bicarbonate, which before, during or can be carried out after the dye application.

The new metallized azo dyes described above result when applied to cellulose textiles are used, yellow to brown shades with excellent fastness to light, Wet treatments such as washing and bleaching agents. A preferred class of the invention The new metallized azo dyes produced are the copper complexes of the azo compounds, which in the form of the free acids of the formula

C-Z

HO-C N

\ _N /

where A, R, X and Y correspond to the above

have given meanings, Z denotes a methyl or carboxyl group, and the benzene rings A and A 'together contain two or three sulfonic acid groups. In this preferred class means Y is preferably a chlorine atom and R is preferably a hydrogen atom.

Examples of metallized azo dyes that fall into this preferred class are mentioned the copper complexes of the azo compounds, which are in the form of the free acids of the formula

correspond, wherein A, X and Z have the meanings given above, and the benzene ring A or contains two sulfonic acid groups.

C-Z

; N \

NH-C

C-Cl

Il

I.

Cl

correspond, in which A, X and Z have the meanings given, and the benzene ring A is or contains two sulfonic acid groups. Particularly valuable metallized ones falling into the preferred class Azo dyes are the copper complexes of the azo compounds, which are in the form of free acids the formula

C-Z

Cl

C-Cl

example 1

Diazotized 4-chloro-2-aminophenol-6-sulfonic acid is treated with 1 - (3'-amino - 4'-sulfophenyl) - 3 - methyl-5-pyrazolone coupled, the monoazo compound thus obtained with an acetic acid-containing aqueous Copper sulfate solution stirred for 1 hour at a temperature of 80 ° C and the copper complex of the monoazo compound by addition of sodium chloride and. ~ filtering the precipitating solid product isolated.

A solution of 50.35 parts of the above copper complex in 500 parts of water is added to a suspension of 18.4 parts of cyanuric chloride in a mixture of 200 parts of ice and 300 parts of water, and the resulting mixture is added for 2 hours at a temperature between 0 and 5 ° C., the pH of the mixture being kept between 6 and 7 by the gradual addition of sodium carbonate. 100 parts of sodium chloride are then added and the dye which separates out is filtered off. The dye paste thus obtained is mixed with 3 parts of disodium hydrogen phosphate and 5.4 parts of potassium dihydrogen phosphate and then dried ^{at 20 ° C.}

Analysis of the dye mixture thus obtained showed 1.75 atoms of organically bound chlorine for every dye molecule.

When used on cellulose textiles in connection with a treatment with an acid-binding agent, the dye gives yellowish-brown shades with excellent fastness to washing, bleaching agents and light.
The following table gives further examples of the color shades obtained on cellulose textiles when the monoazo compound used in Example 1 is replaced by the monoazo compound, which is obtained by diazotizing the amine listed in the second column of the table and coupling the diazo compound thus obtained with that in the third column of the Coupling component listed in the table was obtained.

example Amine Coupling component Hue on
Cellulose textiles 2 2-aminophenol-4,6-disulfonic acid l- (3'-aminophenyl) -3-methyl-
5-pyrazolone Reddish yellow 3 the same 1-phenyl-S-amino-S-pyrazolone Yellowish brown 4th the same l- (3'-Ammo-4'-sulfophenyl) -3-methyl-
5-pyrazolone Reddish yellow 5 4-nitro-2-aminophenol-6-sulfonic acid the same Reddish yellow 6th 6-chloro-2-aminophenol-4-sulfonic acid the same Yellowish brown 7th 5-sulfoanthranilic acid the same Greenish yellow 8th the same 1 - (3'-Ammo-4'-sulfophenyl) -
5-pyrazolone-3-carboxylic acid Greenish yellow

continuation

example Amine Anthranilic acid Coupling component Hue on
Cellulose textiles 9 2-aminophenol-4-sulfonic acid l- (3'-amino-4'-sulfophenyl) -3-methyl-
5-pyrazolone Greenish yellow 10 4-sulfoanthranilic acid the same Reddish yellow 11 2-aminophenol-4-sulfonamide the same Greenish yellow 12th 6-nitro-2-aminophenol-4-sulfonic acid the same Reddish yellow 13th 4-chloro-5-nitro-2-aminophenol-
6-sulfonic acid the same Yellowish brown 14th 4,5-dichloro-2-aminophenol-6-sulfone
acid the same Yellowish brown 15th 4-methyl-5-nitro-2-aminophenol-
6-sulfonic acid the same Yellowish brown 16 2-aminophenol-4,6-disulfonic acid the same Yellowish brown 17th the same Acetoacet-3-aminoanilide Greenish yellow 18th 4-chloranthranilic acid Acetoacet-4-aminoanilide Greenish yellow 19th 2-aminophenol-4-N, N-dimethyl-
sulfonamide l- (3'-amino-4'-sulfophenyl) -3-methyl-
5-pyrazolone Greenish yellow 20th 2-aminophenol-4,6-disulfonic acid l- (2'-methyl-3'-amino-5'-sulfophenyl) -
3-methyl-5-pyrazolone Reddish yellow 21 5-sulfoanthranilic acid 1 - (3'-aminophenyl) -3-methyl-
5-aminopyrazole Yellowish brown 22nd l- (3'-amino-4'-sulfophenyl) -3-methyl-
5-aminopyrazole Dull yellow

Claims (4)

Patent claims: 1. Process for the preparation of copper-containing monoazo dyes, which in the form of the free Acids of the formula / a \ -n = n - correspond, in which the benzene ring A can carry further substituents, E the remainder of one Acetoacetarylids, l-phenyl-5-pyrazolones or l-phenyl-5-aminopyrazole, R is a hydrogen atom or an alkyl radical with not more than 4 carbon atoms, X a hydroxy, carboxy, R N-C -N-C N N = C - (SO ₃ H) _n Y Methoxy or ethoxy group, Y is a chlorine or bromine atom and η is 1, 2 or 3, thereby characterized in that a monoazo compound which is in the form of the free acid the formula NH
(SO ₃ H) _n corresponds, in which A, E, R, X and η have the meanings given above, is treated with cyanuric chloride or cyanuric bromide and a copper-donating agent. 2. The method according to claim 1, characterized in that the treatment with the Copper-supplying agents before treatment with cyanuric chloride or cyanuric bromide is carried out. 3. The method according to claim 1 or 2, characterized in that a monoazo compound is used, which is in the form of the free acid of the formula IO 20th corresponds to, wherein A, R, X and Y have the meanings given in claim 1 and Z is a methyl or carboxy group and the benzene rings A and A 'together are two or contain three sulfonic acid groups. 10 4. The method according to claim 3, characterized in that a monoazo compound is used which is in the form of the free acid of the formula NH ₂ SO ₃ H corresponds, in which A and X have the meanings given in claim 1, the benzene ring A contains one or two sulfonic acid groups and Z has the meaning given in claim 3 Has. Considered publications:
Austrian patent specification No. 201 744. When the application was announced, a coloring table with explanations was laid out. Wi StIBOt 9.U Q Buaadcketti Berlin