DEC0010403MA - - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

Registration date: December 10, 1954 Announced on October 4, 1956

GERMAN PATENT OFFICE

PATENT APPLICATION

CLASS 22a GROUP 1 INTERNAT. CLASS C 09b

C 10403 IVb / 22a

Dr. Hans Bolliger, Basel (Switzerland)

has been named as the inventor

CIBA Aktiengesellschaft Basel (Switzerland)

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

Process for the preparation of new monoazo dyes

The priority of registrations in Switzerland from December 15, 1953 and November 15, 1954

is used

DißErfindiungibetrifftneue valuable, sulfonsäureamiidgruppenihalitigie ¹ monoazo dyes of the Py razoloinreiihei, in serving the nitrogen atom of Sulfonsäureamidgnippe carries a © a -CO- group bonded alkyl group containing a halogen atom.

This halogen atom is expediently in the ^ -position, but preferably in the α-position of the aliphatic A radical which is bonded to the nitrogen atom of the sulfonic acid amide group via a —CO group is. This nitrogen atom can further see through an aliphatic, cycloaliphatic, araliphatic or aromatic radical. The dyes of the are particularly valuable present invention, the at least one sulfonic acid amide group the formula

- SO ₂ -N -CO -CH ₂ -halogen

contain, where η is an integer.

In addition to one group of this type, the dyes according to the invention can contain other monoazo dyes contain common substituents, such as

609 656/439

C 10403 IVb / 22 a

other solubilizing groups, e.g. B. a "SO ₂ NH ₂ -GrUpPe,. A sulfonic group, such as a methyl sulfone group, carboxy groups or sulfonyl säufegiruppeni, further non-water-solubilizing substituents such as halogen atoms, nitro, acylamino, alkyl or alkoxy groups.

The dyes according to the invention are expediently prepared in accordance with known methods Methods in the SuIi ons acid amide group

ίο siilfoinsäuireaimidigrUippenhalitigßr dyes on the pyrazoilone side introduces an acyl group which already contains a halogen atom, possibly a chioir atom. For this purpose, a sulfonic acid amide group-containing dye of the pyrazolone series, whose sulfonic acid amide group still has at least one hydrogen atom, can be treated with an acylating agent capable of introducing the remainder of an aliphatic halocarboxylic acid, e.g. B. with a halide or anhydride of an aliphatic, preferably a ß- or α-chlorine atom containing carboxylic acid,

. z. B. with an aliphatic α- or / J-chlorocarboxylic acid halide convert, so that the sulfamide group, for example, in a group of the formula (1) is converted.

As to be considered; Korairnendiei aliphatic carboxylic acid halides or anhydrides are the following: α- or / J-chloropropionic acid chloride, Bromoacetyl bromide and chloroacetyl chloride and the corresponding haloalkylcarboxylic anhydrides.

The starting dyes containing sulfamide groups can be prepared by conventional methods, e.g. B. by coupling the following diazo compounds and pyrazolones can be obtained:

A. Components containing sulfonic acid amide groups, such as: diazo compounds from i-aminobenzene-2-, -3- or -4-sulfonic acid amide, i-aminobenzene-2-, -3- or -4-sulfonic acid methyl-, ethyl-, -butyl-, -hexyl- or -phenylamide, ^ -Methyl-T-aminobenzene ^ - or -3 - sulfonic acid a.mid, 2-methoxy-I-anlinobenzene-3-, -4- or -5-sulfonic acid amide, 2 - aminonaphthaMn-6 - sulfonic acid amide, and pyrazolones, in particular 3-Metlhiyl - 5 - pyrazolone, such as 1 - (a-naphthyl) -3-methyl-S-pyrazolone ^ '- sulfonic acid amide, i-phenyl-3-methyl-5-pyrazolone'-, -3'- or -4'- sulfonic acid amide, i-Phenyl ^ -methyl-S-pyrazolone'-, -3'- or -4'-sulfomSiäuiremethyliamdd, 1 - phenyl - 3 - methyl-5 -p y r az olon- 2'- chloro- 5'- sulphonic acid earn id.

B. sulfonic acid amide group-free components that are to be combined with one of the components mentioned under A, such as diazo compounds of aniline, β-, m- or p-chloraniliin, 2,5-dichlori -aminobemzo !, nitiraniline, toluidine, also ι-aminobenzenes or -4-methylsulfon, i-aminöbenizoi-3-od, er-4-sUilfoinsäureamid, i-aminobenzene-3- or -4-sulfonic acid, ι -AminO'-2-oxynaphthaliin-4 - sülfonsäutre, uind pyrazoloins, such as 1 - Phenyl-3-methyl.-S-pyrazol (on, i- (2'-, 3'- or 4'-ChIoT-phenyl) -3-methyl-5-pyrazalone :, i- (4'-nitrophenyl) -3 -methyl- 5-pyrazolone, i-phenyli-3-meithyl-5-pyrazolon-3 '-' or ^ '- suilfonsäuire, 1-phenyl-5-pyrazolon-3-carboxylic acid ¹ .

The monoazo dyes obtainable from the above components, which by coupling one of the Diazo compounds mentioned under B with one of the pyrazolones mentioned under A or above all by coupling one of the diazo compounds listed under A with one of the under A or B Said pyrazolones can be produced in alkaline, neutral or acidic agents partly known.

The inventive reaction of the dyes containing sulfamide groups obtained in this way with the specified aliphatic halocarboxylic acid halides or anhydrides can be used in anhydrous, inert solvents such as dioxane, tetrahydrofuran, toluene, xylene, benzene, methyl ethyl ketone, Ethyl acetate etc., or also, in, aqueous agent, expediently in the presence of acid-binding agents, e.g. B. in the presence of tertiary organic Bases, such as pyridine or from alkalis.

It is advantageous to use an excess of acid halide or anhydride, i. H. one uses a larger amount of acid halide than that for reaction with dien in the Reaktiomsgemiech present acylable sulphonic acid amide group in this Color tofftnolieküls necessary amount.

After implementation, the resulting new dyes z. B. separated by salting out and filtration from the reaction medium will.

The dyes obtained in this way are new. They are monoazo dyes of the pyrazolone series, the one Sulfonic acid amide group of the formula

-SO ₂ -N-CO-B

(2)

contain, in which X is a hydrogen atom or a hydrocarbon radical and B is an aliphatic radical which contains a halogen atom, preferably a chlorine atom in β or α-position, where in the event that X is a hydrocarbon radical, the dye molecule is a solubilizing group, preferably a sulfonic acid group,! must contain.

These new dyes can be used for dyeing and printing a wide variety of materials, in particular nitrogen-containing natural or synthetic fibers such as leather, silk, wool and structures made of superpolyamides or super-polyurethanes can be used. They are suitable for dyeing from weakly acidic, neutral to slightly alkaline bath. The colors obtainable in this way are uniform and are characterized by good lightfastness and excellent washing, fulling and alkali fastness out.

Compared to the closest comparable dyes known from German patent specification 892 809 the dyes according to the invention have the advantage of much better fastness to washing.

In the following example, the parts are parts by weight, unless otherwise specified and the percentages are percentages by weight.

6O9S56 / 439

C10403IVb / 22a

example

39.2 parts of the dye obtained in the customary manner from i- (2'-Chlorpheriiyl) -ß-methyl-S-pyrazolone and di-, azotiertetm i-Amitnobenzol'- 3 - siilfonsäureamid; in 200 parts of dioxane with the addition van Voilumitiei 50: le: n, dissolved 30 ⁰ /o.igem Natriumhydlroxyd. After cooling to + 5 °, a solution of 22.6 parts of chloroacetyl chloride in 50 parts of dioxane is added dropwise over half an hour. After completion of the addition of a small amount of acetic acid to p _H = 5 is set to 6 by addition. After addition of 500 parts of water is heated to 50 ⁰ and added to the clear solution while stirring with 100 parts of sodium chloride. After one. the precipitated product is filtered, washed with 10% sodium chloride solution and dried at about 60 ° in vacuo, the dye of the formula is obtained

CH,

: n— /

\ -N = N-C = C

OH

SO ₂ NH-COCH ₂ -Cl

as a red-yellow powder; it dissolves in water with

■ yellow color and dyes wool from neutral to weakly acidic bath in pure yellow tones of excellent wash, milled and lightfastness.

Similar dyes are obtained by using the

Dye of the formula

CH ₃

or the dye of the formula

N- /

N - or the dye of the formula
GH ₃

C = N

WN = N-C = C

H ₈ CI

OH

SO ₂ NH ₂

or the dye of the formula
CH ₃

OCH,

N = N-C = C

OH
SO ₂ NH ₂

or the dye of the formula
CH ₃

C = N,

Cl

Cl

SO ₉ NH,

is used and proceeds in the same way.

Claims (1)

Patent claims: 1. Process for the preparation of new monoazo dyes by acylation of acylatable ones Dyes of the pyrazolone series containing sulfonic acid amide groups, characterized in that that the acylating agent used is those monocarboxylic acid derivatives which are the remainder of an aliphatic halocarboxylic acid are capable of introducing, and the dyes used as sulfonic acid amide groups are those dtiie contain a solubilizing group, preferably a sulfonic acid group, if the sulfonic acid amide group carries a hydrocarbon radical. 2. The method according to claim 1, characterized in that dyes containing sulfonic acid groups, the sulfonic acid amide group of which has at least one hydrogen atom, are reacted with aliphatic carboxylic acid halides or anhydrides which preferably contain a ß- or α-halogen atom. 609 © 6/439 C 10403 IVb / 22a 3. The method according to claim 2, characterized in that one starts from sulfonic acid group-free monoazo dyes which _{contain a - SO 2} NH ₂ group. 4. The method according to claim 2, whereby ge ^ - indicates that one starts from sulfonic acid group-containing monoazo dyes, the one Sulfonic acid amide group of the formula -SO ₂ -NH-X contain, wherein X is a hydrocarbon radical means. 5. The method according to claim 2 to 4, characterized in that one uses aliphatic ^ ß- or α-halogen, preferably chlorocarboxylic acid chlorides. 6. The method according to any one of claims 1 to 5, characterized in that one. Pyrazolone dyes are used which _{contain a - SO 2} NH ₂ group and correspond to the formula R — N = N — Pz, where R is a benzene radical and Pz is an s-methyl-S-pyrazolone radical bonded to the azo group in the 4-position. , 7. Method: according to claim 6, characterized in, that the starting material is a pyrazolone dye of the formula HO R-N = N-Cf XNR ₁ -X CH, used, in which R and R _{1 are} each a benzene radical, one of the two X is hydrogen and the other is a - SO ₂ NH ₂ group. 8. The method according to claim 1 to 7, characterized characterized in that the reaction is carried out in a water-containing medium. 9. The method according to claim ι to 8, characterized in that there is an excess used on acid halide. 10. The method according to claim 1 to 9, characterized characterized in that chloroacetyl chloride is used as the acylating agent. Publications considered: German Patent No. 892 809.