DE1134780B - Process for the preparation of monoazo dyes - Google Patents

Description

GERMAN

PATENT OFFICE

C15031IVc / 22a

REGISTRATION DATE: JUNE 21, 1957

NOTICE THE REGISTRATION ANDOUTPUTE

Disclosure ·. AUGUST 16, 1962

The invention relates to a method of manufacture of valuable monoazo dyes that have a halogenated Have triazine residue. These monoazo dyes contain at least two sulfonic acid groups and correspond to the general formula

X-D-N = N-A (1)

wherein A is one bonded to the azo group in the 4-position 5-pyrazolone radical and X one via a nitrogen bridge to radical D of a diazo component bonded dihalotriazine radical of the formula

C —halogen

Process for the preparation of monoazo dyes

Applicant: CIBA Aktiengesellschaft, Basel (Switzerland)

Representative: Dipl.-Ing. E. Splanemann, patent attorney, Hamburg 36, Neuer Wall 10

Claimed priority:

Switzerland from June 29 and August 3, 1956

(No. 34 867 and No. 36 152)

halogen

mean, where D and A together contain at least one bicyclic aryl radical.

The sulfonic acid groups can be distributed as desired in the dye molecule.

In addition to at least one bicyclic aryl radical and at least two sulfonic acid groups, the contain Dyes of the formula (1) a dihalotriazine radical of the formula given, preferably a dichlorotriazine radical the formula

C-

Cl

Cl

to the remainder of the diazo component via a nitrogen bridge, especially via one of the formula

- N -

is bound, where η is a positive integer with a value of at most 5. the

- N

group

can be bonded to the diazo component via a - SO _{2 group or preferably directly.} A Dr. Alfred Fasciati, Bottmingen (Switzerland), has been named as the inventor

such halotriazine-containing diazo components can be prepared by processes known per se from 1 mole of cyanuric chloride and 1 mole of an aromatic compound which, in addition to a reactive hydrogen atom bonded to a nitrogen atom, also has a substituent which can be converted into an amino group, e.g. B. have a nitro group, which is converted _{into an NH 2 group after the reaction with cyanuric chloride.} However, because of their easier accessibility, the diazo components of this type obtainable from 1 mole of cyanuric chloride and 1 mole of an aromatic diamine are particularly valuable. Both bicyclic aromatic compounds and, preferably, monocyclic diamines are suitable as aromatic diamines; the starting materials are to be selected so that the azo dye obtainable according to the process contains at least one bicyclic aryl radical. The condensation of the aromatic compounds mentioned with cyanuric chloride is expediently carried out in the presence of acid-binding agents, such as sodium acetate or sodium carbonate. During the condensation process, two of the three exchangeable chlorine atoms remain in the condensation product formed, e.g. B. by working in a weakly acidic to neutral medium and / or at temperatures that are kept as low as possible.

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3 4

As examples of so - obtainable amines, the given pyrazolones by coupling with diazo

Diazo compounds in the present process as bonds of the primary cyanuric

Starting materials come into consideration, the fol- chloride condensation products are also indicated

mentioned: monoacylated amines are produced.

The primary condensation products of 1 mole 5 The condensation of the finished dyes with

Cyanuric chloride with 1 mol: cyanuric trihalides are also carried out in such a way that

4,4'-diaminodiphenyl-3-sulfonic acid, ^only _Ä ^one ? ^{of the three} halogen atoms is exchanged.

4,4'-diaminostilbene-2,2'-disulfonic acid, j? ^s the production medium, the color

4- (4'-Aminoben _z oylamino) -l-äminobenzol-2-sul-, ^stofl f ^ζ · | · ^{isolated by} salting out and filtering

fonic acid. You can optionally after adding

4- (4'-aminobenzoylamino) -2-aminobenzene-1-sul-puffene, e.g. B. after adding a mixture

Fonsäure equal parts of mono- and dialkali phosphates dried

1,3- oder'l, 4-diaminobenzene or processed to dry dye preparations;

because of the presence of labile halogen atoms

and in particular the primary condensation products 15 i _m molecule, it is advisable to be carefully vorzu-

go ^out for. B. not too high drying temperatures

1 mole of cyanuric chloride and _to choose and optionally under reduced

1 mole of 1,3-diaminobenzene-4-sulfonic acid, pressure to work. By spray drying the

1 mol of 1,4-diaminobenzene-3-sulfonic acid or a whole preparation mixture of the dyes can

1 mole of 2-methoxy-l, 4-diaminobenzene-5-sulfonic 20 _to dry preparations usually directly, ie, without

acid. Intermediate isolation of the dyes, win.

For the preparation of the dyes of the formula (1) According to the process and its modification

these primary condensate valuable monoazo dyes are obtained according to the invention, which at least

diazotized sation products and with a bicyclic aryl radical and at least two in the 4-position

coupling 5-pyrazolones combined. 25 sulf onic acid groups and the general

As 5-pyrazolones which can couple in the 4-position, formula (I) - correspond.

are mentioned z. B. 3-methyl-5-pyrazolone, 1-Phe- These dyes are suitable for dyeing and

nyl-3-methyl-5-pyrazolon, l-phenyl-S-methyl-S-pyra printing on a wide variety of materials, especially

zolon-2'-, -3'- or -4'-sulfonic acid, l-phenyl-5-pyrazzo- special cellulosic materials of fibrous structure-

ion-3-carboxylic acid, l- (2'-chlorophenyl) -3-methyl-5- 30 door, such as pulp, linen, regenerated cellulose and

pyrazolon-5'sulfonic acid, l- (3'-nitrophenyl) -5-pyra- especially cotton.

zolon-3-carboxylic acid, l- (2 ', 5'-dichlorophenyl) -3-methyl- They are particularly suitable for dyeing

5-pyrazolone-4'-sulfonic acid, l- (2 ', 5'-dichlorophenyl) - the so-called cold dyeing process, after which the

5-pyrazolone-3-carboxylic acid-4'-sulfonic acid and the coloration at room temperature to moderately increased

corresponding pyrazolone-3-carboxamides. 35 temperature in aqueous and possibly also salt

When choosing the diazoverbin-containing, alkaline-reacting baths to be used,

fertilize and 5-pyrazolones but care must be taken, they deliver strong, level and brilliant

that only those colors are combined with one another, in contrast to that in the French

Dyes are formed which, in addition to the halotriazine radical, patent specification 1106359, table example 32,

at least one bicyclic aryl radical and at least 40 known nearest comparable dye, which after the

have two sulfonic acid groups. The process of exhaustion from a cold bath is practically non-existent

The diazotization of those used as starting materials draws up.

Amines can be prepared by methods known per se, e.g. B. The direct dyeing process made from strongly salty

with the help of mineral acid, especially hydrochloric acid, containing baths or after printing or after

and sodium nitrite. The coupling of the so 45 the padding process to the to be dyed

obtained diazo compounds with the materials mentioned applied, inventive color

Pyrazolones takes place under such conditions that substances can there by alkali treatment and ge

the replaceable, if necessary, heat treatment present in the starting materials can be fixed.

Halogen does not react, d. H. useful in weakly those with the dyes on cellulosic fibers

Dyeings obtainable from an acidic to as weakly alkaline medium as possible 5 ° are generally noticeable

and at the lowest possible temperatures. by the purity of their hues, by a good one

A modification of the process is that lightfastness and above all by excellent

the specified triazine residue is not converted into the washfastness as a washout.

raw materials serving diazo components, but in the following example the parts mean

imports the corresponding finished azo dyes, 55 parts by weight unless otherwise specified,

which in the remainder of the diazo component is a percentage by weight, and the temperatures

Nitrogen atom bound, reactive water - are given in degrees Celsius, substance atom and the formula

D-N = N-A (2) example

where D is the remainder of one preferably 33.6 parts of the primary condensation product

at most bicyclic diazo component and A denotes 1 mole of cyanuric chloride and 1 mole of 1,3-diamino

The remainder of a benzene-4-sulfonic acid bonded to the azo group in the 4-position is dissolved in 300 parts of water,

5-pyrazolones mean, with D and A together 300 parts of ice and 20 parts of 30% hydrochloric acid at least a bicyclic aryl radical and at least 65 stirs and at 0 to 2 ° with 25 parts by volume of 4n sodium

contain two sulfonic acid groups. diazotized nitrite solution. The obtained Congo acid di-

The dyes of the formula (2) can be azo suspension with 15 parts of sodium bicarbonate

known methods, e.g. B. from the above and then to one cooled to 0 to 2 °

Solution of 36.8 parts of 1- (2'-naphthyl) -3-methyl-5-pyrazolone-4 ', 8'-disulfonic acid in 104 parts by volume of 1 N sodium hydroxide solution. After finished Coupling, the dye is deposited by adding potassium chloride, filtered, with sodium chloride solution washed and dried at 30 ° in vacuo. It dissolves easily in cold water and stains at 25 to 35 ° cellulose fibers from an alkaline bath containing sodium chloride in pure yellow tones that are remarkable are wet and lightfast.

According to this procedure, the primary condensation products in column I are obtained the following table given formulas and the azo component dyes mentioned in column II, dye the cotton in the shades listed in column III.

I.
Diazo component II
Azo component

III staining

on cotton

Cl-C

Cl-C

Cl

C-NH-

SO ₃ H

NH ₉

C-NH- '

-SOoH

N, - N
C.

Cl

NH ₉

N C-NH-; '
Il SO ₃ H C. Il
N \, ■ · \
/ \ -NH N. C. Cl

CH ₂ - C CH ₃ Green- II pungent yellow O = C N

SO ₃ H

CH ₂ - C - CH ₃

I 11

O = C N

N '

SO ₃ H

CH I CO

CH = CH-; V-NH

SO ₃ H

CH ₂ - C - CH ₃

O = C N

Cl-

-Cl

SO, H

Reddish yellow

Reddish yellow

Cl-C

C-NH- <

> -CO-NH- /

N _n N

V /

Cl

Cl-C

C-NH

Ν _χ Ν
C.

Cl

sO ₃ H

NH ₂ CH ₂
O = C

-C-

SO ₃ H

CH.2

O = C _x , N

CH3

VSO ₃ H

SO ₃ H

Yellow

yellow

Dyeing prescription

2 parts of the dye obtained in accordance with paragraph 1 of the example are mixed with 8 parts of urea, dissolved in 100 parts of water. A cotton fabric is impregnated with this solution at 40 ° on a padder and squeezes off the excess liquid so that the fabric 75% of its weight in dye solution holding back. The so impregnated goods are dried, then at room temperature in a Impregnated solution containing 30 g sodium carbonate and 300 g sodium chloride per liter to 75% Liquid absorption squeezed off and steamed for 60 seconds at 100 to 101 °. Then it is rinsed, one Soaped for 15 minutes in a 0.3% solution of an ion-free detergent at boiling temperature, rinsed and dried again. The result is a bright yellow, fixed coloration that is fast to the boil.

Claims (5)

Claims 1. A process for the preparation of monoazo dyes, characterized in that diazo components which have a 2,4-dihalo-1,3,5-triazine radical bonded via a nitrogen bridge are combined with 5-pyrazolones which couple in the 4-position , isolated and dried, choosing the starting materials so that at least one bicyclic aryl radical and at least two sulfonic acid groups are present in the azo dye formed. 55 60 65 2. The method according to claim 1, characterized in that one contains sulfonic acid groups l-naphthyl-5-pyrazolones with diazotized amines the formula N
Cl-C C-NH-R-NH ₂ I Il I NN SO ₃ H I. Cl combined, wherein R is a monocyclic radical of the benzene series. 3. The method according to claim 1, characterized in that diazo compounds from amines of the formula containing sulfonic acid groups Cl-C NH ₂ SO ₃ H used. 4. Modification of the method according to one of claims 1 to 3, characterized in that 1 mole of a monoazo dye of the formula HN-D-N = Ν --Α where η is a whole positive number, preferably 1, D is the radical of a diazo component and A is a 5-pyrazolone radical bonded to the azo group in the 4-position, where D and A together contain at least one bicyclic aryl radical and at least two sulfonic acid groups, with one mole of one Trihalotriazine, preferably with one mole of the 2,4,6-trichloro-1,3,5-triazine, condensed. 10 5. The method according to claim 4, characterized in that at least 1 mole of cyanuric chloride with one mole of a dye of the formula H ₂ NRN = N-Pz condensed, where R is a sulfonic acid group-containing radical of the benzene series and Pz the in 4-position bonded to the azo group of a 1-naphthyl-5-pyrazolone containing sulfonic acid groups means. Considered publications:
French Patent No. 1 106 359. Legacy Patents Considered:
German Patent No. 1,066,302. When the application was announced, a staining table and two priority documents were displayed. © 209- 630/245 8.