DE1217522B - Process for the production of azo dyes - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

Number:
File number:
Registration date:
Display day:

C09b

German KL: 22a-l

1,217,522
C25420lVc / 22a
November 2nd, 1961
May 26, 1966

The present invention relates to a process for the preparation of new azo dyes that are derived from sulfonic acid and carboxyl groups are free and those of the general formula

OH

SO ₂ -XRN = NQ

(1)

correspond to where

OH

the remainder of one bonded to the azo bridge adjacent to the hydroxyl group and in para position phenol alkylated to the hydroxyl group, R an arylene radical of the benzene series without salt-forming Substituents, X an oxygen atom, a

-NH- or - N-

Alkyl

in particular a - N (CH3) group, Y a halogen atom, a lower, possibly non-salt-forming group Substituent alkyl or alkoxy group or preferably a hydrogen atom and Z a Hydrogen atom, an alkoxy group or, preferably, a halogen atom or a lower alkyl group means. ■

The new dyes are produced by adding couplings in the vicinity of the hydroxyl group and phenols alkylated in the position parallel to the hydroxyl group with diazo compounds from amines the general formula

^. J _{- SO 2} - X - R - NH ₂

(2)

in which R, X, Y and Z have the meaning given in the explanation of the formula (1), combined. Particularly suitable coupling components are sulfonic acids and carboxyl-free phenols general formula

OH

Ri

Process for the production of azo dyes

Applicant:

CIBA Aktiengesellschaft, Basel (Switzerland)

Representative:

Dr.-Ing. Dr. jur. F. Redies,

Dipl.-Chem. Dr. rer. nat. B. Redies,

Dr. rer. nat. D. Türk and Dipl.-Ing. Ch. Gille,

Patent Attorneys, Opladen, Rennbaumstr. 27

Named as inventor:

Dr. Christian Zickendraht, Binningen;

Dr. Arthur Bühler, Rheinfelden (Switzerland)

Claimed priority:

Switzerland of November 3, 1960 (12 331)

wherein Ri is a hydrogen atom or an acylamino group, R _{2 is} a hydrogen atom or an alkyl group and R3 is an alkyl group.

Usable phenols are, for example, p-cresol, 3,4-dimethylphenol, 4-isobutylphenol, 4-isoamylphenol, 4 - methyl - 2 - acylaminophenols, such as the - methyl - 2 - acetylamino-, - 2 - methanesulfonylamino- or -2-n-butyrylaminopnenol, also the phenols, which is a tertiary amyl, isooctyl, secondary butyl or cyclohexyl group in parallel to the hydroxyl group exhibit.

Diazo compounds to be coupled with these phenols are obtained by diazotizing aminobenzenes, the. one by a sulfonyl radical of the general formula

(3)

[wherein Y and Z have the meanings given in the explanation of the formula (1)] acylated amino or Oxy group, no free oxy group and no other NH2 group.

Examples of such aminobenzenes are the following:

609 570/492

l-amino-3- or -4-benzenesulfonylaminobenzene, l-amino-3- or -4-benzenesulfonyloxybenzene,
l-amino-3- or -4- (4'-methylbenzene-

sulfonylamino) benzene,
l-amino-3- or -4- (4'-methylbenzene-

sulfonyloxy) benzene,
l-amino-2-chloro-3- (4'-methylbenzene-

sulfonylamino) benzene,
l-amino-2-methyl-3- (4'-methylbenzene-

sulfonylamino) benzene,
. l-amino-3- or -4- (3'-chlorobenzene-

sulfonylamino) benzene,
l-amino-3- or -4- (N-methyl-N, p-methyl-

benzenesulfonylamino) benzene,
l-amino-3- or -4- (N-methyl-N-benzene-

sulfonylamino) benzene.

The use of aminobenzenes of the general formula is particularly advantageous

SO ₂ -X

IO

wherein one of symbols A and B is an NEfe group and the other is a chlorine atom, a hydrogen atom or a methyl group, X a - O-, - N (CHs) - or —NH bridge, Y a hydrogen atom and Z a chlorine atom or a lower alkyl group means.

The diazotization of the amines mentioned and the coupling take place according to methods which are customary per se instead of. The coupling is expediently carried out in an alkaline, e.g. B. alkali carbonate and / or alkali hydroxide Medium made.

The dyes which can be prepared according to the invention can also be used after a modification of the process mentioned getting produced. This consists in that one first consists of one of the phenols mentioned above and a diazotized aminobenzene in the remainder of the diazo component still a single oxy or Amino group-containing basic dye and then in this through the remainder of the formula (3) Condensation, e.g. B. introduces with the corresponding sulfonic acid chloride.

The dyes obtained in this way are new; in the dry state they are largely insoluble in water Powder.

They are soluble in organic solvents such as esters, and especially in alcohol and acetone. she are for coloring natural or artificial resins, waxes, lacquers and plastic materials, e.g. B. off Cellulose ethers or esters, for example for dyeing acetate silk as well as for dyeing natural or synthetic polymers or condensation products suitable /

With the dyes according to the invention z. B. Acetate rayon using the spin dye method color in clear, real yellow tones.

Compared to the dye obtained according to Example 2 of German Auslegeschrift 1,061,924 The dyeings produced on acetate rayon show those obtained with the new dyes Acetate rayon dyeings have a better resistance to over dyeing.

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 volume and parts by weight is the same as that between liters and kilograms.

example 1

13.2 parts of 4-methylbenzene-1-sulfonic acid (4'-aminophenyD-ester, obtained by condensation of 4-methylbenzene-1-sulfochloride with 4-nitro-1-oxybenzene and catalytic ^ reduction of the nitro ester obtained, are in 100 parts of water and Dissolved 14.6 parts of hydrochloric acid and diazotized at 0 ° to 5 ° with 3.45 parts of sodium nitrite. One unites with a solution of 7.5 parts of 4-tert-amyl-1-oxybenzene in 100 parts of water, 6.7 parts of 30% Sodium hydroxide solution and 2.5 parts of sodium carbonate, stir for some time and filter. The dried one Dye is a yellow, water-insoluble powder that easily dissolves in alcohol or acetone is soluble and dyes acetate silk in the mass in yellow lightfast and washfast tones.

Example 2

14.6 parts of 4-methylbenzene-1-sulfonic acid (4'-aminophenyl) amide, obtained by condensation of 4-methylbenzene-l-sulfochloride with 4-nitro-l-aminobenzene and reduction of the nitrosulfamide obtained, are 30% in 100 parts of water and 13.3 parts Dissolved sodium hydroxide solution and, after adding 3.45 parts of sodium nitrite to 24 parts of hydrochloric acid and ice discharged. The diazo suspension is neutralized with sodium carbonate and then with a Solution of 7.5 parts of 4-tert-amyl-1-oxybenzene in 100 parts of water and 6.7 parts of a 3O% Sodium hydroxide solution combined. The mixture is stirred for some time and filtered. The dried dye represents is a water-soluble yellow powder which is readily soluble in alcohol or acetone. With a solution in nitro lacquer, lightfast yellow tones are obtained on suitable substrates.

By using the diazo compounds of the amines mentioned in column I of the following table are, and the phenols listed in column II are obtained by the above method dyes which Acetate silk dyes using the spinning dye method in the shades specified in column III.

I. II
Coupling component ΠΙ
nuance OH 1 / - \ _ / - "\ _
\ / \ / " ψ yellow C ₄ H ₉

continuation

II coupling component

nuance

SO ₂ -O

NH ₂

SO ₂ -O-

NH ₂

SO ₂ NH

NH ₂

SO ₂ - HN

Cl

NH ₂

SO ₂ - Ν- <V-NH ₂ CH ₃

SO ₂ -O

NH ₂

SO ₂ - O

NH ₂

SO ₂ -HN

NH ₂

OH

CH ₃ OH

CH ₃

CH ₃ OH

CH ₃ OH

CH ₃

CH ₃ OH

CH ₃ OH

C5H11 OH

CH ₃

CH ₃ OH

CH ₃

yellow

yellow

yellow

Yellow orange

yellow

yellow

yellow

yellow

Claims (3)

Patent claims: 1: Process for the production of azo dyes, characterized in that that one can be coupled in the adjacent position to the hydroxyl group and in the para position to the hydroxyl group alkylated phenols, free of sulfonic acid and carboxyl groups, with diazo compounds from amines of the formula -ο- SO ₂ -XR-NH ₂ wherein R is a benzene ring free of free oxy and amino groups, X is an oxygen atom or a nitrogen bridge of the formula (where η is a small integer), Y is a hydrogen or chlorine atom, a low molecular weight, optionally non-salt-forming alkyl or alkoxy group containing substituents and Z is a hydrogen or chlorine atom, an alkyl or alkoxy group, with formation of sulfonic acid and carboxylic acid group-free azo dyes of the general formula OH SO ₂ -XRN = NQ OH 35 40 the remainder of a bonded to the azo bridge adjacent to the hydroxyl group and in Para position to the hydroxyl group of alkylated phenol, R an arylene radical of the benzene series without salt-forming substituents, X an oxygen atom, a -NH- or - N- Alkyl in particular a —N (CH3) group, Y a halogen atom, a lower one, possibly not salt-forming alkyl or alkoxy group bearing substituents or, preferably, a hydrogen atom and Z represents a hydrogen atom, an alkoxy group or, preferably, a halogen atom or means a lower alkyl group, combined. 2. The method according to claim 1, characterized in that there is used as diazo components the amine diazo compounds of the formula SO ₂ - X is used, in which one of the symbols A and B is an NH ₂ group and the other is a chlorine or hydrogen atom or a methyl group, X is an --O-, -N (CH ₃ ) - or - NH bridge, Y is a hydrogen atom and Z represents a chlorine atom or a lower alkyl group. 3. The method according to any one of claims 1 and 2, characterized in that the coupling components sulfonic acid and carboxyl group-free phenols of the formula OH is used in which Ri is a hydrogen atom or an acylamino group, R _{2 is} a hydrogen atom or an alkyl group and R3 is an alkyl group. Considered publications:
German interpretative document No. 1 061 924. When the application was announced, a coloring table with explanations was laid out. 609 570/492 5.66 © Bundesdruckerei Berlin