CS197333B2 - Process for preparing monoazodyes - Google Patents

Description

The invention relates to a process for the preparation of novel valuable monoazo dyes of the general formula I,

where it means

X is a heterocyclic fiber-reactive substituent, such as a 2,4-dichlorotriazinyl group, or an aliphatic halogenated acylamino group, such as. is α, β-dichloropropionylamino or _; a, (S-dibromopropionylamino group or α-chloroacrylamino group or α-bromoacrylamino group,

R1 is a benzene radical containing sulfonic acid groups, optionally substituted by a halogen atom, a C2 -C4 acylamino group or a methyl group,

R2 is amino, (C1 -C4) alkylamino or phenylamino, n a positive integer of not more than 2.

In particular, the invention relates to dyes which correspond to the general formula II,

X is a heterocyclic, fiber-reactive substituent, preferably an aliphatic halogenated acylamino group wherein α, β-idichloropropionylamino or α, β-dibromopropionylamino- or α-chloroacrylamino- or α-bromoacrylamino, n is as defined in point 1,

Y is a halogen atom, an acylamino group having 2 to 4 carbon atoms, or in particular a methyl group or a hydrogen atom, and

R 3 is phenyl or C 1 -C 4 alkyl, especially methyl, or hydrogen.

The novel monoazo dyes can be produced by treating the dye of formula 3,

where it means

X3 is acylamino having up to 13 carbon atoms;

R1, R2 and n are as defined above, acylated with a chloride having a reactive acyl radical of formula

XC1.

for example α, + dibromopropionyl chloride, α-bromoacryloyl chloride or cyanurohloride in the presence of an acid binding agent.

The aminoazo dye starting materials can be prepared by known methods such that some of the coupling components of the general formula IV

coupling in an acidic environment with the diazo compounds in the amine of formula V,

wherein n, Z, R 2 and R 1 have the meanings given in formula I, and X is a free amino group or substituent which can be converted to such a group, for example a nitrosubstituted or acetylamino substituent which is appropriately modified after coupling, for example by reaction or saponification.

Chloride-releasing reactive acyl residues include compounds with unsaturated bonds, such as those derived from chloromaleic acid, propiolic acid, acrylic, bromoacrylic, chloroacrylic or chlorocrotonic acid, as well as compounds with movable halogen atoms, such as those derived from chloroacetic acid, sulfochloroacetic acid, or chloropropionic acid; (3-bromopropionic, α, + dlchloropropionic or α, β-dibromopropionic, 3,5-dinitro-4-chlorobenzoyl chloride, 3,5-dinitro-4-chlorobenzenesulfonic acid chloride as the acid chlorides of some acid-containing heterocyclic compounds containing a labile halogen atom bonded to a heterocyclic ring, that is, heterocyclic compounds containing at least two halogen atoms, such as tetrahalopyridazines, for example 2,4,5,6-tetrachloropyridazine, halopyrimidines, for example

2,4,6-tri- or

2,4,5,6-tetrachloropyrimidine,

5-bromo-2,4,6-trichloropyrimidine,

5-acetyl-2,4,6-trichloropyrimidine, 2,4-dichloropyrimidine-5-sulfonic acid,

5-hitro- or

5-cyano-2,4,6-trichloropyrimidine,

5-nitro-6-methyl-2,4-dichloropyrimidine, 2-chlorobenzthiazole-6-carboxylic acid chloride, 2-chlorobenzthiazole-6-sulfonic acid chloride, chloride-2,6-dichloropyrimidine-4-carboxylic acid chloride, chloride 2, 3-dichloroquinoxaline-6-carboxylic acids, 2,4-dichloropyrimidine-5-sulfonic acid chloride, and the corresponding bromopyrimidines, in particular di- and tri-halo-triazines, such as cyanuric chloride, 2-methyl-, 2-ethyl or 2-phenyl- 4,6-dichlorotriazine and in particular the dichlorotriazines of formula VI,

C1-C-Cl

I I!

N N

AND

A wherein A denotes an oxygen-linked or sulfur-linked hydrolysis residue containing compounds or mercapto compounds, or in particular an NH 2 group or a nitrogen-linked amine residue which, when aromatic, preferably contains a strongly acidic group forming solubility in the water.

The condensation with acid halides or anhydrides or heterocyclic halogenated compounds is conveniently carried out in the presence of an acid scavenger such as sodium carbonate. It is of course necessary to proceed in such reactions so that the unsaturated bond or interchangeable halogen atom is still present in the finished product.

Useful coupling components of Formula IV include:

2-amino-naphthalene-5-, -6- or

-7-sulfonic acid, 2-N-methylaminonaphthalene-6-sulfonic acid, 2-N-phenylaminonaphthalene-6-sulfonic acid, 2-amino-8-oxynaphthalene-6-sulfonic acid, 2-N-methylamino-8-oxynaphthalene 6-sulfonic acid and 2-N-phenylamino-8-oxynaphthalene-6-sulfonic acid.

The dyes obtained according to the invention are novel. They are suitable for dyeing and printing a wide variety of materials, in particular of animal origin, such as leather, silk and, in particular, wool, as well as synthetic fibers, for example synthetic silk adapted to natural silk, polyamides or polyurethanes, etc. The sulfonic acid coupling component is particularly suitable for use from an acid bath or a sulfuric acid bath, while dyes containing sulfonamide groups can be dyed from weak acid or neutral baths. The dyes and prints obtained using the new dyes from neutral or acid baths are distinguished by valuable color shades, high light fastness, uniformity of dyeing and good resistance to washing and fulling, also on chlorinated wool, especially in acid environments. In contrast to the known dyes according to French Patent No. 1 139 039, which do not have a sulfone group in the R 1 residue, the dyes obtained according to the invention and the highest comparable solubility show a generally better wet stability and especially better behavior in the presence of leveling agents, especially polyglycol ether derivatives having on average at least 10 —CH2 —CH2 —O— groups and derived from primary monoamines containing an aliphatic hydrocarbon radical of at least 20 carbon atoms.

In the examples below, unless otherwise indicated, parts and percentages are by weight.

Example 1 β

is neutralized in 1000 parts of water with 2N sodium hydroxide solution and mixed with 16.4 parts of anhydrous sodium acetate. While vigorously stirring, a solution of 25 parts of α, β-dibroimpropionyl chloride is added dropwise at 0 to 5 ° C over 30 minutes. After a short time, the amine group is completely acylated. The dye thus obtained is separated in a known manner by the addition of sodium chloride, filtered and dried. The dye thus obtained stains the wool from the bath neutral or acidified with acetic acid and gives a bluish red shade, stable in wet and light.

If 17 parts of α-bromoacrylic chloride are used in place of the 25 parts of α, β-dibromipropionyl chloride, a similar blue-red dye is obtained.

In a similar manner, the following dyes of the following general formula can be prepared which dye wool from a neutral bath to an acetic acid bath to the shade indicated in the last column of the formula.

parts of dye formula x ‘

R1 R2 ¹ n

Zi

Z2 Z3 Color shade

(S-dibromophenyl H-propionyl)

SOsH

α, β-dlbrom- propionyl phenyl CH3 2 α, β-dibromo- propionyl p-chloro- phenyl H 1 α, β-dibromo- propionyl phenyl H 1 2- (3-methoxy- ethylaminoj- -4-chlortri- azinyl-6 Example 2 p-methyl- phenyl H 1

54.4 parts of dye formula

H red with a hint of blue

H red-violet

SOiH

II SOsH H red SO3H H H red H SOsH H red wool from neutral to acetic acid acidified bath red shades, stable in wet and light.

is neutralized in 1000 parts of water with 2N sodium hydroxide solution and 26.5 parts of finely powdered 2,3-dichloroquinoxaline-6-carboxylic acid chloride are added with vigorous stirring and at 30 to 40 ° C while neutralizing the liberated hydrochloric acid is added with the addition of 2N of sodium carbonate solution at pH 6 to 7 is stirred until the amine group, which is in the para position to the diazocapsule, is fully acylated. The dye thus obtained is separated in a conventional manner by the addition of sodium chloride, separated by filtration and dried. The dye thus obtained stains

Prescription for coloring

Dissolve 2 parts of dye in 4000 parts of water, add 10 parts of crystalline sodium sulphate and 0.5 parts of oleylamine ethylene oxide adduct and place 100 parts of well-wetted wool at 40-50 ° C in the bath. Then 2 parts of 40 ^1% acetic acid bath is brought to the boiling point within half an hour and three quarters of an hour at the boil dyes. The wool is then rinsed with cold water and dried. The wool is colored in wash-resistant red shades with good light fastness.

Production of ethylene oxide addition product

100 parts of technical oleylamine are mixed with 1 part of finely divided sodium and heated to 140 ° C, then ethylene oxide is added at 135-140 ° C. Once the ethylene oxide is rapidly bound, the reaction temperature is lowered to 120 to 125 ° C and the ethylene oxide feed is continued until 113 parts of ethylene oxide are bound. The reaction product thus obtained is practically completely soluble in water.

Claims (2)

A process for the preparation of monoazo dyes of the general formula 1, wherein is X a heterocyclic fiber-reactive substituent, such as a 2,4-dichlorotriaziinyl group or an aliphatic halogenated acylamino group, such as a .alpha.-dichloropropionylamino or .alpha.,. Beta.-dibromopropionylamino or .alpha.-chloroacrylamino group or .alpha.-bromoacrylamino group; R 1 is a benzene radical containing sulfonic acid groups optionally substituted by a halogen atom, a C 2 -C 4 acylamino group or a methyl group, R 2 is amino, C 1 -C 4 alkylamino or phenylamino, n a positive integer of not more than 2, characterized in that the dye of formula (3) is: INVENTION where it means Xs acylamino of up to 13 carbon atoms, R 1, R 2 and n are as defined above, acylating with a chloride having a reactive acyl radical of formula XCl, for example α, β-dibromopropionyl chloride, n-bromoacryloyl chloride or cyanuric chloride in the presence of an acid binding agent. 2. A process as claimed in claim 1, wherein the dyes of the general formula (I) are represented by the formula (I) X3 is acylamino having up to 13 carbon atoms, Y is methyl or a hydrogen atom and n is an integer of not more than 2, reacted with α, β-dichloropropionic acid chloride or α, β-dibromopropio chloride (new acid or α-chloroacrylic acid chloride or α-bromoacrylic acid chloride).