DE2004488A1 - Water-soluble azo dyes for wool and poly-amide fibres - Google Patents

Abstract

Water-soluble azo dyes for wool and polyamide fibres. Dyes are of formula (in which D is the group of an aromatic or heterocyclic diazo or tetrazo component, m is 1 or 2, n is 1 to 4, is alkyl, phenyl opt. substd., A2 is CN, carbonamide or carbalkoxy, A3 is CH3 or CH3O and A4 is H or CH3.) Pref. A1 is CH3, A2 is -CONH2, A3 is -H or -CH3, A4 is -H and n is 1 to 3. They give yellow to blue shades of good to very good fastness on wool and synthetic polyamides.

Description

New water-soluble azo dyes The invention relates to azo dyes of the general formula I. in which D is the residue of an aromatic or heterocyclic diazo or tetrazo component, m is the number 1 or 2, n is the number 1 to 4, A1 is methyl, methyl, propyl, butyl, phenyl, methoxyphenyl, tolyl, chlorophenyl, bromophenyl or nitrophenyl, A2 Cyano, carbonamide or carbalkoxy, A3 denotes hydrogen, methyl, methoxy and A4 denotes hydrogen or methyl.

Carbalkoxy groups for A2 have, for example, 2 to 9 carbon atoms. In detail are, for example, carboethoxy, carbbutoxy or carbohexoxy.

Diazo or tetrazo components are diazotizable, aromatic or heterocyclic amines with 1 or two diazotizable NH2 groups. Examples of substituents are fluorine, chlorine, bromine, nitro, cyano, methyl, methyl, methoxy, xthoxy, phenoxy, trifluoromethyl, acetylamino, acetyl, benzoyl, methylsulfonyl, ethylsulfonyl, arylazo, carboxy, carbalkoxy, carbophenoxy, carbamoyl, N-mono- or disubstituted carbamoyl, and the radicals of the formulas are considered, where R1 is an alkyl group with 1 to 4 carbon atoms or a phenyl or tolyl group and R2 and R3 are hydrogen atoms or alkyl groups with 1 to 4 carbon atoms or a radical R2 or R3 is an aryl group, the radicals R2 and R3 can together with the nitrogen, optionally under the influence of a further hetero atom, form a ring, for example a pyrrolidine, piperidine or morpholine ring.

Carbalkoxy radicals as substituents for components D contain for example the following alcohol components: methanol, methanol, propanol, butanol, isobutanol, hexanol, ethyl hexanol, cyclohexanol, benzyl alcohol, phenol, ß-hydroxyethanol, ß-methoxyethanol, ß-ethoxyethanol or ß-butoxyethanol or the compounds of Formulas: HO- (CH2CH2o) 2CH5, Ho (CH2CH2o) 2C2H5, HO (CH2CH20) 3CH3 'HO (CH2CH2O) 3C2H5, HOCH2CH2OCOCH5, as well as the compounds ß-hydroxypropanol, -hydroxypropanol, g-hydroxybutanol or hydroxyhexanol.

Examples of N-mono- or disubstituted carbamoyl radicals are: N-methyl carbonamide, N-ethyl carbonamide, N-butyl carbonamide, N-cyclohexyl carbonamide, N (ß-ethylhexyl) -carbonamide, N-ß-Hydroxygthylcarbonamid, N-ß-Methoxyäthylcarbonamid, N-ß- or N - # - hydroxypropyl carbonamide, N, N-dimethyl carbonamide, N, N-diethyl carbonamide, N, N-Dipropylcarbonamid, N-Methyl-N-ß-hydroxyäthylcarbonamid, N-g-Methoxy- or Äthoxypropylcarbonamid, Pyrrolidide or morpholide.

Specifically, for example, the following benzene derivatives may be used as the diazo component called: Aniline, o-, m- or p-toluidine, o-, m- or p-nitroaniline, o-, m- or p-cyananiline, o-, m- or p-chloroaniline, 3,4-dichloroaniline, 2,5-dichloroaniline, 2,4,5-trichloroaniline, 2-chloro-4-nitroaniline, 2-cyano-4-nitroaniline, 5-nitro-4-aminotoluidine, 2-,) - or 4-methoxyaniline, N-acetyl-p-pbenylenediamine, N-benzenesulfonyl-m-phenylenediamine, 4-aminodiphenylurea, 4-aminoacetophenone, 4-aminobenzophenone, 2-aminobezophenone, 4-methylsulfonylaniline, 2-aminodiphenylsulfone, 4-aminoazobenzene, 3-methoxy-4-amino-6-methylazobenzene, 3,6-dimethoxy-4-aminoazobenzene, 2-, 5- or 4-aminobenzoic acid, 2->) - or 4-aminobenzoic acid methyl ester, ethyl ester, -propylester, -butylester, -isobutylester, -ß-ethylhexylester, -cyclohexylester, -benzyl ester, -phenyl-ester, -ß-methoxyethyl ester, -ß-ethoxyethyl ester, -ß-butoxyethyl ester, methyl diglycol ester, ethyl diglycol ester, methyl triglycol ester, ethyl triglycol ester, -ß-hydroxyethyl ester, -ß-acetoxyethyl ester, -ß- (ß'-hydroxyethoxy) -ethyl ester, -ß-hydroxypropyl ester, -γ-hydroxypropyl ester, - # - hydroxybutyl ester, # -hydroxyhexyl ester, 4-nitroanthranilic acid, 4-nitroanthranilic acid methyl ester, iso-butyl ester, methyl diglycol ester, 3- or 4-aminophthalic acid, 5-aminoisophthalic acid or aminoterephthalic acid dimethyl ester, -di-ethyl ester, -di-propyl ester, -di-butyl ester, -di-methyl diglycol ester, -di-ethyl diglycol ester or di-benzyl ester.

Also to be mentioned are: 3- or 4-aminobenzoic acid - amide, -methylamide, -n-butylamide, -propylamide, -iso-butylamideJ -cyclohexylamide, -methoxypropylamide, -ethoxypropylamide, -ß-hydroxyethylamide, -anilide, 2-, 3- or 4-aminobenzoic acid dimethylamide, -diethylamide, -di-n-propylamide, -pyrrolidide, -morpholide, -N-methyl-N-ß-hydroxyethylamide, 5-Aminoisophthalic acid diamide, -dimethylamide, -dimethoxypropylamide, -di-nbutylamide, 5-aminosophthalic acid or aminoterephthalic acid bisdi-methylamide, bis-diethylamide, 3- or 4-aminophthalic acid imide, -ß-hydroxyethylimide, -ß-hydroxypropylimide, -γ-hydroxypropylimide, -methylimide, -ethylimide, -propylimide, -n-butylimide, -X-methoxypropylimide, -ß-phenylethylimide, - (2'-ethyl) -hexylimide, -phenylimide, -4'-chlorophenylimide, 3- or 4-aminobenzene sulfonic acid amide, -methylamid, -äthylamid, propylamid, n-butylamid, -isobutylamid, -cyclohexylamid, -γ-methoxypropylamide, -ß-hydroxyethylamide, -anilide, 2-, 3- or 4-aminobenzene-sulfonic acid-dimethylamide, -diethylamide, -di-propylamide, -pyrrolidide, -morpholide, -N-methylanilide, Methylsulfonic acid 2 ', - 3'- or 4'-aminophenyl ester, butylsulfonic acid 2',) '- - or 4'-aminophenyl ester, benzenesulfonic acid 2 '-, -)' - or 4 '-aminophenyl ester, 4-methylbenzenesulfonic acid-2 ', - 3'- or-4'-aminophenyl ester, 4-chlorobenzenesulfonic acid-2' -, - 3'- or-4'-aminophenyl ester, dimethylaminosulfonic acid-2 ', -3'- or-4'-aminophenyl ester, Di-n-butylaminosulfonic acid 2 ', - 3'- or 4'-aminophenyl ester, morpholine-N-sulfonic acid 3'-aminophenyl ester, N-methylaniline-N-sulfonic acid 3'-aminophenyl ester.

Also to be mentioned are: o-, m- or p-aminobenzenesulfonic acid, 2-chloro-1-aminobenzene-5-sulfonic acid, 4-chloro-1-aminobenzene-3-sulphonic acid, 4-chloro-1-aminobenzene-2-sulphonic acid, 3-chloro-1-aminobenzene-6-sulphonic acid, 1-amino-2,5-dichlorobenzene-4-sulfonic acid, 1-amino-3,4-dichlorobenzene-6-sulfonic acid, 2-nitro-l-aminobenzene-4-sulfonic acid, 4-nitro-l-aminobenzene-2-sulfonic acid, 3-chloro-4-methyl-1-aminobenzene-6-sulfonic acid, 2-methyl-l-aminobenzene-4-sulfonic acid, 4-nitro-l-aminobenzene-2-methylsulfone, 2-methoxy-4-nitro-1-aminobenzene-5-sulfonic acid, 4-methyl-l-aminobenzene-2-sulfonic acid, 2-methoxy-l-aminobenzene-5-sulfonic acid, 2-methoxy-4-nitro-1-aminobenzene-5-sulfonic acid, 3- or 4-acetamino-l-aminobenzene-2-sulfonic acid, 2,4-dimethyl-l-aminobenzene-5-sulfonic acid, 4-ethoxy-1-aminobenzene-3-sulfonic acid; Aniline-2,5-disulfonic acid, aniline-2,4-disulfonic acid, l-aminonaphthalene-5,6-disulfonic acid, 2-aminonaphthalene-3,6-disulfonic acid, 2-aminonaphthalene-6,8-disulfonic acid, 1-amino-2-ethoxy-naphthalene-6-sulfonic acid, 2-aminonaphthalene-4,7-disulfonic acid, 2-aminonaphthalene-4,8-disulfonic acid, l-aminonaphthalene-2 -, - 5 -, - 4 -, - 5 -, - 6 -, - 7- or -8-sulfonic acid, 2-aminonaphthalene-1 -, - 5 -, - 6 -, - 7- or -8-sulfonic acid, 1-amino-4-p-toluenesulfonaminoanthraquinone-2-sulfonic acid, 1-amino-2-methoxy-4-p-toluenesulfonic acid aminoanthraquinone, l-amino-4- (p-toluene) -sulfonamide, 5-aminotriazole, 2-amino-5-nitrothiazole, 2-aminothiazole, 2-amino-5-phenyl-thiadiazole, p-aminophenylpyrrolidone, 5-amino-5-chiorindazole, 3-aminoindazole, 2-aminobenzothiazole, 2-amino-6-methoxybenzthiazole, 2-amino-6-ethoxybenzthiazole, 2-amino-6-carbkthoxybenzthiazole, 6-methyl-2- (4'-aminophenyl) -benzthiazole, 2- (4'-aminophenyl) -6-methyl-5-sulfonic acid benzothiazole, 2- (4'-Aminophenyl) -6-methyl-7-sulfonic acid benzothiazole, 2- (4'-Amino-3'-sulfonic acid phenyl) - 6-methyl-5-sulfonic acid benzothiazole, 2- (4'-Amino-3'-methylphenyl) -4,6-dimethylbenzthiazole, 3- or 4-aminophthalic acid hydrazide, 3- or 4-aminophthalic acid arylhydrazides, 3- or 4-aminophthalic acid p-toluylimide, 3- or 4-aminophthalic acid-p-tolylimide-2'-sulfonic acid, 3- or 4-aminophthalic acid-4'-chloro-2'-sulfonic acid tolylimide, 2- (3 "-aminophenyl) -5'-oxynaphthimidfazole [1 ', 2', 4,5] -7'-sulfonic acid, m- or p-aminophenylene oxide, N-ethyl-3-aminocarbazole, 4-aminodiphenyl, 4,4'-diaminodiphenl-3-sulfonic acid, 4,4'-diaminodiphenyl-2,2'-disulfonic acid, 4,4'-diamino-3,3'-dimethoxydiphenyl, 4,4'-diaminodiphenylmethane, 4,4'-diamino-2,2 ' dichlorodiphenylmethane, 4.4? -Diamino-3,3'-dichlorodiphenylmethane, 4-nitro-4-aminostilbene-2,2'-disulfonic acid, 4,4'-diaminostilbene, 4,4'-diamino-2,2'-dimethyldiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diaminodiphenylamine-2-sulfonic acid, 4-nitro-4'-aminophenylamine-2-sulfonic acid, p-aminodiphenylamine, p-aminodiphenylamine-2-sulfonic acid, 4,4'-diaminophenylamine, 4,4'-diaminodiphenylamine-2-sulfonic acid, 4-methoxy-4'-aminodiphenylamine, 3-methoxy-4-aminodiphenylamine, 4,4'-diaminoazobenzene, 4-amino-4'-nitroazobenzene, 4-aminoazobenzene-4'-sulfonic acid, 4-aminoazobenzene-3,4'-disulfonic acid, 4-amino-3-methoxy-2'-chloro-4'-nitroazobenzene, 4-amino-3,2'-dimethylazobenzene, 4-amino-2,3'-dimethylazobenzene, 4-amino-3,2'-dimethylazobenzene-4'-sulfonic acid, l-aminonaphthalene-4-azobenzene, l-amino-2-ethoxynaphthalene-6-sulfonic acid-4- (azobenzene-2 '-, - 3'- or-4'-sulfonic acid), 4-amino-4'-chlorodiphenyl ether, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide-2,2'-disulfonic acid, p-aminophenylbenzyl ether, 3- or 4-aminophthalic acid-1 "-naphthylimide, -2'-nephthylimide, 3- or 4-aminophthalic acid- (1'- or -2'-naphthylsulfonic acid) -imide, 3- or 4-aminophthalic acid- (4 ' -chlorophenyl sulfonic acid) imide,) or 4-aminophthalic acid benzyl amide or benzyl sulfonic acid imide, 3- or 4-aminophthalic acid cyclohexylimide, 2- (5'- or 4'-aminophthalylimido) acetic acid and their alkyl esters, preferably methyl esters.

A group of particularly valuable dyes corresponds to the general formula I a, one in the A5 is hydrogen or / or methyl and p is the number 1, 2 or 3 and m and D have the meaning given.

Preferred diazo and tetrazo components are derived from benzene, naphthalene, Diphenyl, stilbene and azobenzene.

The coupling components have the general formula II in A1 to A4 have the meaning given.

Some examples of coupling components are summarized in Table 1: Table 1: Coupling components of the general formula II A1 A2 A5 A4 1 CH — CN H. H 0 2 -CH -C + H 5 -C 3 - NH2 3 -CH -C 'HH oC, H, 25th 4 -C3H7 (n) -CN HH 5 -CH? -C 5 CH5 -CO -CH3 H NNH --2 0 6 -CH5 -C / J -CH5 -SO5H NH2 -H 5 7 -CH3 C 8 ° -H -S03H 2 8 -eN -HH -ON -CH3 H Furthermore, Al can denote the substituents methyl, butyl, p-tolyl, p-methoxyphenyl, p-nitrophenyl, p-chlorophenyl or p-bromophenyl and A4 denotes methyl or methoxy.

The new dyes are yellow to blue and surrender to us on wool synthetic polyamides, e.g. polycaprolactam, yellow to blue colors, the have good to very good fastness properties.

To prepare the new dyes, diazo or tetrazo compounds of the amines of the general formula D- (NH2) m (m = 1 or 2) with the coupling components of the general formula implement, wherein at least one of the components carries a sulfonic acid group.

The coupling is carried out as usual in an aqueous medium, optionally under Addition of solvents, carried out in the event of a weakly acidic to weakly alkaline reaction.

Parts and percentages in the following examples relate to unless otherwise noted, on the weight.

Synthesis of a coupling component 158 parts of 2-cyanomethylbenzimidazole and 86 parts of piperidine are mixed with 500 parts by volume of methanol and 100 parts by volume of dimethylformamide at room temperature. 150 parts of ethyl acetoacetate are then added, the mixture is heated to boiling for 14 hours, then poured into 2000 parts of ice water and acidified with 150 parts of 50 percent hydrochloric acid. The resulting precipitate is filtered off, washed with 500 parts of water and dried at 1200C.

Yield: 215 g; Melting point 3500C (2erz.) The transformation the cyano group into a carboxamide group or into a carboxylic acid ester group happens according to methods known per se.

Example 1 12 parts of benzidine-2,2'-disulfonic acid are mixed with 100 parts Water 7 parts of soda and then with 18 parts by volume of 25 percent sodium nitrite solution offset. The resulting solution is added in small portions to a cooled to OOC Solution of 15 parts by volume of 50 percent hydrochloric acid in 100 parts of water. After one hour Stirring 0 ° C, the diazonium salt mixture is added in small portions to a 0 ° C cooled solution of 17.7 parts of coupling component 8 (Table I) in 220 parts Dimethylformamide, 400 parts of water, 6 parts of 50 percent sodium hydroxide solution and 7 parts Soda. After the coupling has ended, the resulting dye is obtained by adding 50 parts of sodium chloride precipitated, filtered off and washed with 10 percent sodium chloride solution washed neutral.

After drying at 70 ° C., red crystals are obtained which dissolve in water with a red color. The dye has the formula Color shade on polycaprolactam: red anal. The procedure given gives the following dyes using the coupling components from Table I and further diazo components: Example Color shade on polycaprolactm red red scarlet scarlet red example shade of coloring on. Polycaprolactam 0 0 HH S05Na soda 2 5 5 2 C-NH 7 g NN <red \ bH .d - 1 'y% -;' - -. - -; J '' - 'k- AN - "2.- A 8, ore. 9 'NF bordo H H S05Na H CN CH3 CH CN N AN = NiN-NC,> N = NAN - "$ NfN-Bla <H% II0 S OdO 5 OO .. .. H2N-C CH3 CH5 C-NH2 3 t 10 X 4 v N> purple i) HS% Na H0 S05Na 0-Na 5 EXAMPLE 11 8.6 parts of 2-nitro-4-chloro-1-aminobenzene are admixed with 20 parts of 30 percent hydrochloric acid and 50 parts of water, then the mixture is cooled to 0 ° C. and in proportions of 15 parts by volume 25 percent Sodium nitrite solution added. The mixture is stirred for a further 2 hours and any excess of nitrous acid which may be present is eliminated as usual. The diazonium salt mixture is then mixed with 12 parts by volume of 50 percent sodium acetate solution and 200 parts of ice water and in small portions in a solution, cooled to OOC, of 16.7 parts of coupling component 7 (Table 1) in 300 parts of water, 5 parts of 50 percent sodium hydroxide solution and Given 10 parts of soda. After the coupling has ended, 50 parts of sodium chloride are added to the mixture and the mixture is acidified to pH 5.5 to 6 with 10 percent strength acetic acid. The precipitated dye is filtered off with suction and washed with 10 percent sodium chloride solution. After drying at 70 ° C., red-brown crystals are obtained which dissolve in water with a red color. The dye has the formula: and colors polycaprolactam red-brown.

Using coupling components from Table I and further diazo components, the following dyes are obtained analogously to the procedure given, the following abbreviations being applicable: with SO3H group = Y-S03H with CH3 group = Y-CH5 Example shade of the color on polycaprolactam red red yellow-orange orange orange-red orange Example of the color shade on polycaprolactam orange yellow-orange orange orange orange red red Example of the color shade on polycaprolactam Example 26 8.7 parts of 1-aminobenzene-4-sulfonic acid are mixed with 125 parts of water and 6 parts of sodium carbonate. Then 16 parts by volume of 23 percent sodium nitrite solution are added and the mixture is added in small portions at OOC to a mixture of 75 parts of ice and 15 parts by volume of 0 percent hydrochloric acid. The mixture is stirred at the same temperature for a further 2 hours and any excess of nitrous acid which may be present is eliminated as usual. The diazonium salt mixture is then added in small portions to a solution, cooled to 0 ° C., of 12.5 parts of coupling component 2 (Table I) in 450 parts of water, 5 parts of 50 percent sodium hydroxide solution and 6 parts of sodium carbonate. After the coupling has ended, the dye formed is precipitated by adding 50 parts of sodium chloride, filtered off and washed neutral with 10 percent sodium chloride solution.

After drying at 700C, red crystals are obtained that dissolve in water with an orange-red color and have the formula correspond.

Color shade of the dyeing on polycaprolactam: orange The dyes represented by formulas in the following table are obtained in a similar manner: Example shade of the dyeing on polycaprolactam orange scarlet orange orange reddish brown red scarlet scarlet -17 Example shade of the coloring on polycaprolactam yellow-orange orange orange orange Example 59 15.7 parts of 4-amino-azobenzene-4'-sulfonic acid are dissolved in 500 parts of hot water, and 16 parts by volume of 25 percent strength sodium nitrite solution are added. The solution is added to a mixture of 20 parts by volume of 30 percent strength hydrochloric acid and 200 parts of ice within 10 minutes at OOC. The mixture is stirred at the same temperature for a further 2 hours and any excess of nitrous acid is removed as usual. The diazonium salt mixture is then added to a solution, cooled to 00, of 12.5 parts of coupling component 2 (Table I) in 100 parts of dimethylformamide, 400 parts of water, 5 parts of 50 percent strength sodium hydroxide solution and 7 parts of sodium carbonate. After coupling has ended, the dye formed is precipitated by adding 50 parts of sodium chloride to the coupling mixture, filtered off, washed neutral with 10 percent sodium chloride solution and dried at 70.degree.

The dye of the formula is obtained in green shimmering crystals that dissolve in water with a red color.

Color shade of the dyeing on polycaprolactam: scarlet red Analogously to the procedure given, the following dyes are obtained using coupling components from Table I and further diazo components: Example shade of the dyeing on polycaprolactam red scarlet-red red red BAD ORIGNA red 1 1 Example shade of the coloring on polycaprolactam O CH rl C-0-C4H9 (n) 45 NaODS) N = N e N = NX 4H9 (n) - Red SO, well 46 NaO3S 5 N = N-) N = NX scarlet red 2nd floor 2H5 25th 47 NaO3S) N = N 4 N = NX-S05Na reddish-blue S05Na Cl 48 SO, Ne orange-red 0 0 <O, 9 N = NX-S03Na oN 49 Ct -N = NX-SODNa yellow H CII S% Na 'SO5Na CH3 5X N = NX red OCH, 51 v N = NX-CH3 cm, red 50 Well 3 1 OS 1 1 LQ 20- Example shade of color on polycaprolactam red orange red red orange red Example of the color shade on polycaprolactam Example 59 7.5 parts of 2-aminobenzothiazole are introduced at 0 to 500 parts into 50 parts of 60 percent sulfuric acid. After stirring for one hour at the same temperature, 18.6 parts of 41 percent nitrosylsulfuric acid are added and the mixture is stirred for a further 3 hours at 0 to a given excess of nitrosylsulfuric acid, which is then destroyed as usual and the diazonium salt mixture is then added in small portions to one A solution, cooled to 0 ° C., of 11.6 parts of coupling component 7 (Table I) in 80 parts of dimethylformamide, 5 parts of 50 percent strength sodium hydroxide solution and 300 parts of water. During the coupling at 0 ° to 50 ° C., 72 parts of 50 percent sodium hydroxide solution are added so that the pH of the reaction mixture is 6 to 9, preferably 7. After coupling has ended, the resulting dye is precipitated by adding 30 parts of sodium chloride, filtered off, washed neutral with 10 percent sodium chloride solution and dried at 70 ° C. Red crystals are obtained which dissolve in water with a red color and of the formula correspond. Color shade on polycaprolactam: red. -22- The dyes shown in the table below are obtained analogously.

Example shade of color on polycaprolactam red red Example 62 19 parts of 2,5-dichloro-aniline-4-sulfonic acid (benzenesulfonyl) amide are dissolved in 45 parts of dimethylformamide and 50 parts of hot water Parts of water, 100 parts of ice and 15 parts of 30 percent hydrochloric acid are added.

15 parts by volume of 23 percent sodium nitrite solution are then added dropwise at 0 ° to 50 ° C., the mixture is stirred for 1 hour at the same temperature and any excess nitrous acid is then destroyed as usual. The diazonium salt mixture is added in small portions to a d? Lf OOC cooled solution of 16.7 parts of coupling component 7 (Table I) in 350 parts of sodium carbonate. When the coupling has ended, it is acidified with hydrochloric acid to pH = 3.5 to 4 and the dye is precipitated by adding 150 parts of sodium chloride all. M <'in filters the dye of the formula and dry it at 70 C.

Orange crystals are obtained which also dissolve in water. Color of the coloring on polycaprolactam: orange.

Example shade of color on .polycaprolactam orange Analogously to the procedures given in the examples, one obtains using the coupling component of the formula dye the polyamide in the specified shade using the diazo component dyes specified in the table below: Example shade of the dyeing on polycaprolactam orange orange orange orange Example hue of the coloring on polycaprolactam orange orange orange red scarlet red golden yellow golden yellow Example of the color shade on polycaprolactam golden yellow red red red Analogous to the procedures given in the examples, one obtains using the coupling component of the formula color the polycaprolactam in the specified shade with the diazo component dyes indicated in the following table.

Example shade of color on polycaprolactam red-orange orange orange-red rusty blue red orange Example of the color shade on polycaprolactam orange orange orange orange orange orange orange Example of the color shade on polycaprolactam orange orange orange red orange-red orange orange Example of the color shade on polycaprolactam orange-red bluish-tinged red bluish-tinged red bordo bluish-tinged red golden-yellow Woven or knitted fabric made of synthetic polyamide.

The temperature of the dyebath is' 400 within 50 minutes brought to 1000C and held there for 60 minutes. The dyed material is rinsed and dried. The coloration obtained is scarlet and brilliant, of good lightfastness and good fastness properties.

Example 109 In 420 parts of water there is 0.04 part of the dye of Example 14, 0.3 part of 30 percent acetic acid, 0.5 part of ammonium acetate (anhydrous), 1 part of sodium sulfate and 0.1 part of a commercially available leveling agent dissolved, then 7 parts of a woven or knitted fabric made of wool are introduced. The temperature of the dye bath is increased from 400C to 1000C within 45 minutes and held there for 60 minutes. The material then colored is rinsed and dried.

The coloration obtained is orange, of good lightfastness and good Usability.

Claims (3)

Claims 1. New water-soluble azo dyes of the general formula in which D the residue of an aromatic or heterocyclic diazo or tetrazo component, m the numbers 1 or 2, n the numbers 1 to 4, A1 methyl, ethyl, propyl, butyl, phenyl, methoxyphenyl, tolyl, chlorophenyl, bromophenyl or nitrophenyl, A2 Cyan, carbonamide or carbalkoxy A3 denotes hydrogen, methyl, methoxy and A4 denotes hydrogen or methyl. 2. Dyestuffs according to Claim 1 of the general formula in which A5 is hydrogen or a methyl group and p is the number 1, 2 or 5 and m and D have the meaning given. 3.The use of the dyes according to claim 1 and 2 for dyeing of textile material made from natural or synthetic polyamides. -4. A process for the preparation of dyes according to claim 1, characterized in that diazo or tetrazo compounds of amines of the general formula D- (NH2) m (m = 1 or 2) with coupling components of the general formula implements.