CH653047A5 - Azobenzene DISPERSE DYES. - Google Patents

Description

653047

2nd

PATENT CLAIMS 1. The azo compounds of general formula I

R

according to claim 6, resulting dye recrystallized in an organic solvent.

° 2N- ^ C ^ N = N— (O Ro NH-R.

(I)

CH2-CH = CHC1

It has been found that the azo compounds of the general formula I

wherein

Ri hydrogen, chlorine, bromine or iodine,

R2 is hydrogen, chlorine or bromine,

Rj Ci-4-alkyl-carbonyl, Ci-4-alkoxy-carbonyl, Ci-4-alkoxy- is ethoxycarbonyl, Ci-2-alkoxy-ethoxy-ethoxycarbonyl or Ci-2-alkylsulfonyl and

R4 is cyan-C2-3-alkyl or y-chloroallyl.

2. The azo compounds according to claim 1, wherein R 1 is chlorine and R 2 is hydrogen.

3. The azo compounds according to claim 1, wherein R3 is Ci-2-alkyl-carbonyl, Ci-2-alkoxy-carbonyl, Ci-2-alkoxy-ethoxycarbonyl or methylsulfonyl and R4 is cyanoethyl.

4. The azo compounds according to claim 1, wherein R 1 is chlorine, R 2 is hydrogen, R 3 is Ci-2-alkylcarbonyl and R 4 is cyanoethyl.

5. Azo compounds according to claim 1, in the form of the β-crystal modification of the dye 2-chloro-4-nitro-2'-ace-30 tyIamino-4 '- (N-ß-cyanoethyl-Ny-chloroallyl) -amino-1, 1 '-azo-benzene, characterized by relatively strong lines in the X-ray diffraction diagram (CuKai line) at grating distances (interplanar distances) D = 8.4.6.7.5.65.3.86.3.65, 3.58 and 3.51 Â.

6. A process for the preparation of azo compounds of the general formula I, characterized in that a diazotized amine of the formula II

= N-N

R2

(I)

CH2-CH = CHC1

20th

25th

wherein

Ri is hydrogen, chlorine, bromine or iodine, preferably chlorine or bromine,

R2 is hydrogen, chlorine or bromine, preferably hydrogen, R3 Ci-4-alkylcarbonyl, Ci-4-alkoxycarbonyl, Ci-4-alkoxy-ethoxycarbonyl, Ci-2-alkoxy-ethoxy-ethoxycarbonyl or Ci-2-alkylsulfonyl and

R4 is cyan-C2-3-alkyl or y-chloroallyl, excellent as disperse dyes, in particular for dyeing, pad dyeing or printing on fibers or threads or articles made therefrom from fully or semi-synthetic, hydrophobic, high molecular weight organic substances.

The new dyes of the formula I are prepared by coupling a diazotized amine of the formula II

35

° 2N ~~ (2) ~ m2

(II)

f1

° 2n- (0) ~ Nh2

R2

with a compound of formula III

<9> -f <R4

/ - ^ CH2 ~ CH = CHC1 NH-R3

40

(II)

(III)

couples.

7. A process for the preparation of the color-stable β-modification of the disperse dye according to claim 5, characterized in that after the preparation according to claim 6, by diazotization of 2-chloro-4-nitro-aniline and domes with 3- (N -ß-cyanäthyl-Ny-chlorallyl-amino) -acetanilide dye, at a pH above 3, in an aqueous suspension subjected to heat treatment by heating to temperatures above 65 ° C.

8. A process for the preparation of the color-stable β-modification of the disperse dye according to claim 5, characterized in that after the coupling,

with a compound of formula III 'R,

45

<Ö> - <4

^ CH? -CH = CHC1

NH-R

(III)

50 diazotization and coupling take place in analogy to known methods.

The amines of formula II are known. Unless they are also known, the compounds of the formula III can easily be prepared analogously to known processes. Preferably, independently of one another, R 1 is chlorine, R 2 is hydrogen, R 3 is Ci-2-alkylcarbonyl, Ci-2-alkoxycarbonyl, Ci-2-alkoxyethoxycarbonyl or methylsulfonyl, in particular Ci-2-alkoxycarbonyl and R * cyanoethyl .

The disperse dye 2-chloro-60 4-nitro-2 '-acetylamino-4' - (N-ß-cyanoethyl-Ny-chlorallyl) -l, l'-azobenzene, from which in particular the ß-crystal mo diffication is characterized by excellent stability in all staining conditions. After coupling, this dye is obtained in aqueous medium in the a-crystal modification, 65 which is not stable under all staining conditions and easily converts to the ß-crystal form.

The a-crystal form is converted into the more valuable ß-crystal modification either (directly after the

653047

Coupling) by heating the aqueous suspension of the dye, at a pH above 3, preferably around 4, to temperatures above 65 ° C, preferably between 75 and 85 ° C, or by recrystallizing the dye in an organic solvent, e.g. Acetone or a lower alcohol, preferably ethanol.

When converting to aqueous suspension, it is advantageous to use in the presence of an anionic, cationic or nonionic surfactant, especially a dispersant, e.g. Polyvinyl sulfonates, dinaphthylmethane disulfonates, alkali salts of lignosulfonic acids or sulfite cellulose waste.

The a-crystal modification obtained in the production by diazotization and coupling is characterized by lines in the X-ray diffraction diagram (Cu Kai line) at grating distances (interplanar distances) D: 19.0 (w, d), 15.5 (w), 10.0 (vw , d), 8.5 (m), 7.9 (m), 3.4 (s, d) and 3.28 (w, d) A from, the ß-crystal modification according to the invention by lines at lattice spacing 16.0 (vw), 8.4 (s), 8.0 (w), 6.7 (m), 5.65 (m), 5.10 (w), 5.05 (w), 4.25 (w), 4.15 (w), 4.02 (w), 3.92 (w), 3.86 (m), 3.78 (w), 3.65 (m), 3.58 (m), 3.51 (vs), 3.39 (vw), 3.34 (w), 3.28 (w), 3.22 (w), 3.01 (vw) and 2.74 (vw) Â. The brackets mean: vw = very weak, w = weak, m = medium strong, s = strong, vs = very strong, d = diffuse.

The a-crystal modification is only of limited use as a disperse dye for dyeing at temperatures above 70 ° C., in particular for dyeing so-called cross-wound bobbins (which are flushed with the dye liquor) because the dye, which was first ground to a fine dispersion, slightly recrystallized (rearranged for ß-modification) and again forms large crystals that are deposited on the surface of the substrate instead of penetrating into it (in dissolved form). The new ß modification is particularly suitable for dyeing all types of polyester materials.

The processing of the new compounds of formula I into coloring preparations takes place in a generally known manner, e.g. by grinding in the presence of dispersants and / or fillers. With the preparations which may have been dried in vacuo or by atomization, after adding more or less water, dyeing, padding or printing can be carried out in a so-called long or short liquor.

The dyes are excellently absorbed from aqueous suspensions on textile material made from fully synthetic or semi-synthetic, hydrophobic, high-molecular organic substances. They are particularly suitable for dyeing or printing textile material from linear, aromatic polyesters, as well as from cellulose-2'A-acetate, cellulose triacetate and synthetic polyamides.

You dye or print according to known, e.g. the methods described in French Patent No. 1,445,371.

The dyeings obtained have good general fastness properties; The lightfastness, the thermal fixing, sublimation and pleating fastness are to be emphasized. They are exceptionally wet-fast, e.g. water, sea water, wash and sweat law, solvent law, especially dry cleaning law, lubricant, rubbing, over-dyeing, ozone, smoke gas and chlorine law; they are extremely resistant to the effects of the various permanent pressing processes and the so-called “soil release” equipment. The etchability, the reduction resistance (when dyeing with wool) and the reserve of wool and cotton are good.

In the following examples, parts are parts by weight and percentages are percentages by weight; the temperatures are given in degrees Celsius.

example 1

a) 250 parts of water, 88 parts of conc. Hydrochloric acid and 34.5 parts of 2-chloro-4-nitroaniline are stirred for 12 hours, then with 40 parts of ice and over the course of 40 minutes,

s at 0 to 2 °, with 13.8 parts of sodium nitrite, dissolved in 50 parts of water. While cooling to 0 to 5 °, stirring is continued for 2 hours, then small residues are filtered off. A solution of 55.5 parts of 1- (N-β-cyanoethyl-Ny-chloroallyl) -amino-3-acetylaminobenzene in is added to this diazonium salt solution in the course of 45 minutes with stirring and cooling (by adding ice) to 0 ° to 5 ° 100 parts of glacial acetic acid and 200 parts of hydrochloric acid (30%) were added dropwise.

b) After the coupling has been completed, the dye suspension is brought to pH 4 with about 400 parts of 30% sodium hydroxide solution

is set, the temperature rising to 40 to 45 °. The dye suspension is then heated to 80 to 85 ° by means of directly introduced steam and this temperature is kept under stirring for about 45 minutes. The dye is then filtered off, washed neutral with water and dried.

c) Instead of, as described under b), in aqueous suspension, the dye can also be filtered off after coupling, washed neutral with water, dried and recrystallized from ethanol or acetone. This is also how you get it

2s color-stable ß modification. Xmax. of this dye (in dimethylformamide) = 515 nm.

d) The coupling component, l- (N-β-cyanoethyl-N-y-chloroallyl) amino-3-acetylamino benzene, is prepared as follows: 40.6 parts of 1-N-β-cyanoethylamino-3-acetylamino

30 benzene are stirred in 50 parts of water, 10 parts of magnesium oxide, 27 parts of 92 percent 1,3-dichloropropene (ice, trans) are added and the mixture is stirred at 80 ° for 24 hours. The mixture is then cooled to ambient temperature, 200 parts of water are added and the reaction product is extracted with Chlo-35 roform.

Application example

The dye obtained in Example 1, b) or c), which is present in the dye-stable crystal form, is ground by means of sand grinding in the presence of dispersants, e.g. Lignin sulfonates, and subsequent atomization into an ultradisperse dye preparation with an average particle size ^ 1 n and a coupage ratio of 3:10.

45 6 parts of the ultradisperse dye preparation are dispersed with 1000 parts of water and added to the circulating liquor (13,000 parts, still containing 30 parts of ammonium sulfate and 0.3 part of formic acid as a buffer mixture) at 60 °. The pre-cleaned and pressed cross-wound bobbin (1000 parts of PE yarn so on a plastic sleeve) is then inserted, the dyeing autoclave is closed and heated from 60 ° to 130 ° in 35 minutes. After 15 minutes at 130 °, the mixture is cooled to 80 °, the liquor drained off and the colored bobbin washed thoroughly with cold water. It is then swung and dried in a drying cabinet.

You get a deep, perfectly level, pure, red color, free of filtering, with excellent wet and rub fastness. The liquor is practically colorless, the dyeing equipment shows no deposits and can be used immediately for the next dyeing.

The following table shows further dyes of the formula I and the shade of their colorations on polyester fiber material. These dyes are produced in analogy to Example 1 above, section a) and subsequent addition of the coupling suspension with about 500 parts of water, filtering, acid-free washing and drying.

E.g.

No.

2nd

3rd

4th

5

6

7

8th

9

10th

11

12

4th

table

Ri Rî Ri R4 Nuance ^ max

Cl

H

-COC2H5

-CH2CH2CN

red

516

Br

H

-COCHs

-CH2CH2CN

red

517

H

H

-COCH3

-CH2CH2CN

Scarlet fever

495

Cl

Cl

-CO-OCH2CH2OC2H5

-CH2CH2CN

red

517

Cl

H

-COCH3

-CH2CH = CHC1

red

521

Cl

H

-CO (CH2> CH3

-CH2CH2CN

red

516

Cl

H

-COOCH3

-CH2CH2CN

red

511

Cl

H

-COO (CH2) 3CH3

-CH2CH2CN

red

513

Cl

H

-C00CH2CH20C2H5

-CH2CH2CN

red

511

Cl

H

-S02CH3

-CH2CH2CN

red

508

Cl

H

-S02CH3

-CH2-CH = CH-C1

red

514