DE2023295A1 - Water insoluble azo dyes for dyeing polyesters polyamides cellulose - esters and polypropylene - Google Patents

Abstract

Dyes have formula: (where n=1 or 2, D is the residue of an (hetero)aromatic diazo-or tetrazo component A1 is lower alkyl a phenyl, tolyl, methoxyphenyl, chlorophenyl, bromophenyl or nitrophenyl gp or a (substd)carbalkoxy gp with 2-9C A2 is a nitrile, carboxylic acid amide or (substd) carbalkoxy gp with 2-9C; A3 is H, lower alkyl or lower alkoxy, and A4 is H, alkyl, or (substd) sulphonamide gp. Used for dyeing textiles of cellulose esters, polyamides, nickel-contg polypropylene or polyesters or as pigments. The dyes are yellow to blue.

Description

Water-insoluble azo dyes The invention relates to sulfonic acid group-free azo dyes of the general formula 1 in which n is the number 1 or 2, D is the radical of an aromatic or heteroaromatic diazo or tetrazo component, A1 is an alkyl group with 1 to 5 carbon atoms, a phenyl, tolyl, methoxyphenyl, chlorophenyl, bromophenyl or nitrophenyl group or an optionally substituted carbalkoxy group with a total of 2 to 9 carbon atoms, A2 a cyano, carbonamide or optionally substituted carbalkoxy group with a total of 2 to 9 carbon atoms, A3 a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, an alkoxy group with 1 to 5 carbon atoms and A4 denotes a hydrogen atom, an alkyl group or an optionally substituted sulfonamide group.

Carbalkoxy groups for A1 and A2, which are the same or different can have 1 to -8 carbon atoms in the alkoxy radical. Examples are: Carbomethoxy, Carbopropoxy, Carbohexoxy, Carbo- (t-ethoxy) -propoxy, Carbo- (ß-phenoxy) -ethoxy and preferably carboethoxy, carbobutoxy, carbo (ß-methoxy) ethoxy, carbo (a-ethoxy) ethoxy or carbo (methoxy) propoxy.

As N-mono- or -disubstituted sulfonamide residues for A4 e.g. into consideration: N-methylsulfonamide, N-ethylsulfonamide, N-butylsulfonamide, N-cyclohexylsulfonamide, N- (ß-ethylhexyl) -sulfonamide, N- (ß-methoxyethyl) -sulfonamide, N, N-dimethylsulfonamide, N.N-diethylsulphonamide, N.N-dipropylsulphonamide, pyrrolidide or morpholide.

Alkyl groups for A1, A3 and A4 are, for example, methyl, methyl, n- or i-propyl, n- or i-butyl or amyl.

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, ethoxy, 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 one of the radicals R2 or R3 is an aryl group.

The radicals R2 and R3 can optionally be used together with the nitrogen form a ring under the influence of another hetero atom, e.g. a pyrrolididine, Piperidine or morpholine ring.

Carbalkoxy radicals as substituents for components D contain for example the following alcohol components: methanol, ethanol, propanol, butanol, iso-butanol9 hexanol, ethylhexanol, Cyclohexanol, benzyl alcohol, Phenol, ß-hydroxyethanol, B-methoxyethanol, ß-thoxySthanol or B-butoxyethanol or the compounds of the formulas: H0- (CN CH20) 2CH, Ho (cHCH2o) 2C2H5, HO (CH2CH2O) 3CH3, HO (CH2CH20) 3C2H5, HOCH2CH2OCOCH3, as well as the compounds ß-hydroxypropanol, hydroxypropanol, # -Hydroxybutanol or # -hydroxyhexanol.

Examples of N-mono- or disubstituted carbamoyl radicals are: N-methylcarbonamide, N-ethylcarbonamide, N-butylcarbonamide, N-cyclohexylcarbonamide, N (ß-Ethylhexyl) -carbonamide, N-ß-Hydroxyäthylcarbonamid, N-ß-Methoxyäthyloarbonamid, N-B- or N-t-hydroxypropyl carbonamide, N, N-dimethyl carbonamide, N-diethyl carbonamide, N, N-Dipropylcarbonamid, N-Methyl-N-ß-HydroxySthylcarbonamid, N-Methoxy- or Xthoxypropylcarbonamid, Pyrrolidide or morpholide.

Specifically, the following benzene derivatives may be used as diazo components, for example called: aniline, o-, m- or p-toluidine, o-, m- or p-nitroaniline, o-, m- or p-cyananiline, 4-methylsulfonylaniline, o-, m- or p-chloroaniline, 3,4-dichloroaniline, 2,5-dichloroaniline, 2w4,5-trichloroaniline, 2-chloro-4-nitroaniline, 4-chloro-2-nitroaniline, 2-cyano-4-nitroaniline, 3-nitro-4-aminotoluidine, l-amino-2-nitrobenzene-4-methylsulfone, l-amino-4-nitrobenzene-2-methylsulfone, l-amino-4-nitrobenzene-2-ethylsulfone, 2-, 3- or 4-methoxyaniline, N-acetyl-p-phenylenediamine, N-benzenesulfonyl-m-phenylenediamine, 4-aminodiphenylurea, 4-aminoacetophenone, 4-aminobenzophenone, 2-aminobenzophenone, 4-methylsulfonylaniline, 2-aminodiphenylsulfone, 4-aminoazobenzene, 3-methoxy-4-amino-6-methyazobenzene, 3,6-dimethaxy-4-aminoazobenzene, 2-, 3- or 4-aminobenzoic acid, methyl 2-, 3- or 4-aminobenzoate, ethyl ester, -propylester, -butylester, -isobutylester, ß-ethylhexylester, -cyclohexylester, -benzylester, -phenylester, -B-methoxyäthyiester, -ß-ethoxyäthylester, -ß-butoxyäthylester, methyl diglycol ester, ethyl diglycol ester, methyl triglycol ester, ethyl triglycol ester, -ß-hydroxyethyl ester, -ß-acetoxyethyl ester, -ß- (B'-hydroxyethoxy) ethyl ester, -ß-hydroxypropyl ester, -r-hydroxypropyl ester, -6-hydroxybutyl ester, D-hydroxyhexyl ester, 4-nitroanthranilic acid, 4-nitroanthranilic acid methyl ester, -iso-butyl ester, methyldiglycol ester, 3- or 4-aminophthalic acid, 5-aminoisophthalic acid or aminoterephthalic acid dimethyl ester, di-ethyl ester, di-propyl ester; -di-butyl ester, -di-methyldiglycol ester, -di-ethyldiglycol ester or -di-benzyl ester.

Also to be mentioned are: 3- or 4-aminobenzoic acid amide, -methylamide, -n-butylamide, -propylamide, -iso-butylamide, -cyclohexyamide, -methoxypropylamide, -ethoxypropylamide, -ß-hydroxyethylamide, -anilide, 2-, 3- or 4-aminobenzoic acid-dimethylamide, -diSthylamide, -di-n-propylamide, -pyrrolidide, -morpholide, -N-methyl-N-ß-hydroxyethylamide, 5-ami noisophthalic acid diamide, -dimethylamide, -dimethoxypropylamide, -di-nbutylamide, 5-aminoisophthalic acid- or aminoterephthalic acid bisdi-methylamide, bis-diethylamide, 3- or 4-aminophthalic acid imide, -ß-hydroxy-ethylimide, ß-hydroxypropylimide, t-hydroxypropylimide, -methylimide, -thylimide, -propylimide, -n-butylimide, -T-methoxypropylimide, -ß-phenylethylimide, - (2'-ethyl) -hexylimide, -phenylimide, -4'-chlorophenylimide, 3- or 4-aminobenzene-sulfonic acid amide, -methylamide, -äthylamid, propylamid, n-butylamid, -isobutylamid, -oyc lohexylamid, -t-methoxypropylamid, -ß-hydroxyethylamide, -anilide, -tolylamide, 2-, 3- or 4-aminobenzene sulfonic acid dimethylamide, -diethylamide, -di-propyl amide, -pyrrolidide, -morpholide, -N-methylanilide, methylsulfonic acid-2 ' -s -3'- or -4'-aminophenyl ester, butylsulfonic acid 2 ', -3'- or -4'-aminophenyl ester, Benzenesulfonic acid 2 ', -3'- 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 as diazo and tetrazo components are: 2-amino-5-nitrothiazole, 2-aminothiazole, 2-amino-5-phenyl-thiadiazole, 3-amino-5-chloro-indazole, 3-aminoindazole, 2-aminobenzothiazole, 2-amino-6-methoxy-benzothiazole, 2-amino-6-ethoxy-benzothiazole, 2-amino-6-carbethoxy-benzothiazole, 6-methyl-2- (4'-aminophenyl) -benzthiazole, 2- (4'-amino-3'-methyl-phenyl) -4.6-dimethyl-benzothiazole, 3- or 4-aminophthalic acid-p-tolylimide, 4-aminodiphenyl, 4.4'-diamino-3.3'-dimethoxydiphenyl, 4.4'-diamino-diphenylmethane, 4.4'-diamino-2.2'-dichlorodiphenyl, 4.4'-diamino-3.3 ' -dichlorodiphenyl, 4.4'-diamino-3.3'-dimethyl-diphenyl, 4.4'-di-aminostilbene, 4.4'-diamino-2.2'-dimethyl-diphenyl, 4.4'-diaminazobenzene, 4.4'-diamino-3.3'-dinitro-diphenyl, 4-amino-4'-nitro-azobenzene, 4-amino-3-methoxy-2'-chloro-4'-nitro-azobenzene, 4-amino-3.2'-dimethylazobenzene, 4-amino-2,3'-dimethyl-azobenzene, l-amino-4-phenylazo-naphthalene, 4-amino-4'-chloro-diphenyl ether, 4.4'-di-aminodiphenyl ether, 4.4'-diamino-diphenyl sulfone, 4.4'-diamino-diphenylthioether, 1. 1-bis (-p-aminophenyl) 7-cyclohexane, p-aminophenylbenzyl ether, 3- or 4-aminophthalic acid benzylimide, 3- or 4-aminophthalic acid cycloheylimide, 2- (3'- or 4'-aminophthalylimido) -acetic acid methyl ester, ethyl ester or propyl ester, l-aminoanthraquinone, l-amino-3-chloro-anthraquinone, l-amino-4-chloroanthraquinone, l-amino-67-dichloro-anthraquinone, l- (bis-p-aminophenyl) -cyclohexane, 4-Amino-2 .5-dimethyl-2 '.4' -dimethoxy-5 '-chlorazobenzene, 4-Amino-3.2'-dimethoxy-5-methyl-5'-chloroazobenzene, 4-amino-2.5-dimethyl-2'-methoxy-5'-chloro-azobenzene, 4-amino-2-methyl-5-methoxy-2'-carboxy-azobenzene, 4-amino-2,5-dimethoxyazobenzene, 4-amino-2-methyl-5-methoxy-azobenzene, 3- or 4-aminobenzoic acid-p-anisidide, 3- or 4-aminobenzoic acid-p-toluidide, 3- or 4-aminobenzoic acid-p-chloro-anilide, 3- or 4-aminobenzoic acid-m-chloroanilide.

A group of particularly valuable dyes corresponds to the general formula I a in which A5 denotes an alkyl group with 1 to 5 carbon atoms, A6 denotes a carbonamide or carbalkoxy group and A7 denotes a hydrogen atom, a methoxy group or an alkyl group with 1 to 5 carbon atoms and D and n have the meaning given.

Preferred groups for R5 are again methyl and propyl.

The carbalkoxy groups for A6 are those with 4 to 7 0 atoms, ie e.g. carbopropoxy, carbobutoxy, carbohexoxy, carbo-ß-methoxyethoxy or carbo-t-methoxypropoxy, preferred.

A particular alkyl group for A7 is methyl.

Preferred diazo and tetrazo components are derived from benzene and azobenzene and diphenyl, i.e. aniline, aminoazobenzene and benzidine derivatives are preferred.

Preferred substituents for all 3 derivative groups are methyl, ethyl, Methoxy, ethoxy or chlorine. For the aniline derivatives, there are also carbalkoxy, N-mono- and N, N-disubstituted carbon or sulfonamide groups and also methyl and ethyl sulfone into consideration.

Preferred carbalkoxy radicals are those with 2 to 50 atoms, e.g.

Carbomethoxy, ethoxy, propoxy, butoxy, -B-methoxyethoxy, -ßethoxy-ethoxy or t-methoxypropoxy.

Preferred substituents on the N atoms of the carbon and sulfonamides are alkyl radicals with 1 to 5 carbon atoms which are substituted by hydroxyl or alkoxy could be. In particular, e.g.

Methyl to butyl and hydroxyethyl, hydroxypropyl, methoxyethyl, methoxypropyl or xthoxyethyl. N-monosubstituted carbons and sulphonamides are found in US Pat Usually preferred.

The new dyes are yellow to blue. They are suitable for coloring of cellulose esters and polyamide fiber material and especially of polyesters. With Some of the new dyes can also be colored with polypropylene containing nickel. the The dyeings obtained with the dyes show good to very good fastness properties.

Part of the new dyes is' in the common organic Solvents very sparingly soluble to insoluble. These dyes also have good fastness properties and are suitable as pigments.

To prepare the dyestuffs of the formula I, diazo or tetrazo compounds of amines of the general formula II D- (NH23n, (n = 1.2) II with coupling components of the general formula III can be used realize.

The diazotization or tetrazotization takes place according to the customary methods. The coupling is also as usual in an aqueous medium, optionally under Addition of solvents, carried out in the event of a weakly acidic to weakly alkaline reaction.

Some examples of coupling components are summarized in Table I, Table I: Coupling components of the general formula III No. A i A> A 1 -CH3 -ON HH 2 CR3 -CN -CH H 3 3 3 -COSH2 HH 4 -CR3 -CONE2 -CE3 H 5 -OH3 -COOC, B, (n) H -S02 t 0 6 zCH) ~ CN HH 7 -CR3 -CooCH2eN OCE3 HH 8 -CR3 -aOOCH2CH2CH20CH3 HHH 9 -C, 3z7 (n) -CN HH 10 -C3H7 (n) -CN I -OH 37 3 II 11 -03R7 (n) -CONH2 HH 12 -c3R7 (n) -CONH2 -OH H 3 13 F3 7 () -COOCH2CH20CH3 II H 14 -CE7 (n) -COOCHgn) H. 15 -c R (n) -CooC3H7 (n) HH 37 16 O -CN HH 17 4 -CONH2 18 -00004H9 (n) H. 19 o Cl -CODE H II H No. A: A A3 20 4 -COQCR2CH20CH3 acc. To H. 21 o CH3 -COSH2 H acc 22 -CR3 -CN lt -S02NHCH2CH3QCH) 23 -CR3 -CQNH2 H -S02NHCH2CH20CH3 24 -OR3 -CONH2 H -SQ2lfICH2CH2CH2CH3 25 -COOC2H) -Cli lt 26 -COOC2H, -C0yEI2 acc 27 -O00C4lt9 (n) -COOC4lt9 (n) according to 28 -COOCClt2OCH3 -CN H acc 29COOCII2C92e-CN according to 30 -COOCN CH2 <-COEH2 according to H 31 -C °° CóH13 (n) -CN according to H 32 -C °° c6 3 (n) -CO according to 33 -Olt3 -CONH2 -CR3 -S02NHCHg 34 CR3 CONH2 -CE3 -CR3 35 -OH3 -CONH2 C4lt9 (n) H 36 -OH3 -C0NH2 NOR3 H Data on parts and percentages in the following examples are based on weight, unless otherwise stated. The parts of space relate to parts by weight as the liter to the kilogram.

Example 1 10.4 parts of p-aminobenzoic acid-t-methoxypropylamide become 50 parts of water and 12 parts by volume of 30 percent hydrochloric acid are added. Then adds 150 parts of ice and then 15 parts by volume of 23 percent by volume are added with stirring Add sodium nitrite solution.

After stirring for two hours at 0 to 5 ° C., any excess of nitrous acid is destroyed as usual and the diazonium salt mixture is then added in portions to a solution, cooled to OOC, of 12.5 parts of coupling component 3 in 400 parts of water, 5 parts of 50 percent sodium hydroxide solution and 6 parts of sodium carbonate. After the coupling has ended, the resulting dye is of the formula filtered off, washed with water and dried at 700C. A red powder is obtained which dissolves in dimethylformamide with an orange-red color and dyes polyethylene terephthalate fabric in orange shades with very good fastness properties.

Example 2 9.0 parts of p-aminobenzoic acid n-propyl ester are dissolved in 80 parts of water and 12 parts by volume of 50 percent strength hydrochloric acid. 80 parts of ice and 15 parts by volume of 23 percent sodium nitrite solution are added. The mixture is stirred for 2 hours and then destroys any excess of nitrous acid such as Ublieh, the diazonium salt mixture is then added in portions to a solution of 12.5 parts of coupling component 3 in 300 parts of water, 5 parts of 50 percent sodium hydroxide solution and 5 parts of sodium carbonate. After stirring overnight, the precipitated paraffin of the formula filtered off, washed with water and dried at 70 ° C. A red powder is obtained which dissolves in dimethylformamide with an orange-red color and dyes polyethylene terephthalate fabric in orange shades with very good fastness properties.

Color of the dyeing on polycaprolactam: orange Analogously to the procedure given, the following dyes are obtained using coupling components from Table 1 and further diazo components: Table 2 No. n A1 A2 A n shade of color . 5 on i? Olart he 3 02115000 OIS2 -CII -CONH2 H 1 3 4 C2H5 °° 4ES -C3H7 (n) -CONX2 Ey 1 orange 110 5 C $ Ig (n) tC <2 -OH -COOC4H9 (n) H 1 orange 3 O> -CH3 -CON I2 i - 3 2 11 1 orange OZOCóH1 (n) 7 yH2 -CH3 -CONH2 0117> 1 orange CONHC] l2 HSCH2 CH3 8 O2NNH2 -C3H7 (n) -C3H7 (n) H 1 orange rust coocqHg (n) OH 9 CH3C-N oNH2 0113 -O113 H 1 red OCH 10>% -CR3 0113 -02115 1 red OCH3 O0 11 g H2 vCH3 000C4H9 (n) H 1 red OCH3 12 H2N02S 42 2 oCH3 ecooC + H9 (n) H 1 orange 13 CE30CHSCH2CEF0 O E2 -O3H7 (n) ON TI 1 orange-sharp- laughing red 14 C1 wF CR3 GONH2 OCH3 1 orange 0190OH2OC2115 , No., D A1 A2 'A3' n shade of color . ~. . . ~ on polyester 15 ß 2 -CH3 -COOC2% E 1 orange 2FCH2CH20C2H5 16 -CH, OH3 H lt l orange NH 2 17 e NH2 -OH -COXH2 C4Hg (n 1 orange-red 3 18 CH3 -CE3 -CN2 lt 1 orange-red OH3 19 CH30-NLI2 -CE3 -CONH lt 1 red Nlt2 20 <-CH3 -OH3 .CONlt2 lt 1 orange : oocCR2L ~ OksI 21 CH3COOCN C v O> H2 .0113 -O0NH2 lt 1 orange 22 C1 t -03H7 (n) -CO 0113 1 orange NO2 23 0} - t02 2 CH3 -COOCH9 (n) CH3 1 orange-ro, NO2 24 <CR3 I 3 -COOCH9 H 1 scarlet red 25 CH (OC CH2) 2 °° W 4 s / -COIfflH2 H 1 orange 26 CX3 (° CH2CH2) °° 4 - i ^ 5 CONlt2 H 1 orange Xr. D A1 A2 3 n Tint of the wing 27 H3 + 2 41I3 <2 E 1 w 28 4 NE2 -0113 -C0004H9 (n) H 1 snge 29 OJ- -O0004H9 H 1 orange-red S020113 0113 30 5 H28 FOH2 H | 2 be-red 0113 Cflt, 31 HN3 <INH -OOHI 0113 2 orange-red 0113 0113 32 eUtifi H 2 -C 0113 33 -0113 -C0% H 2 orange-red 34 1tiQna. -33P (n) -C0 BI 2 orange-red 35 NN to 0 -CB3 ~ ffi C0 HE 2 orange-red 36 NN t S> 2 -G dC 3 2 -0, red 37 N4 S -c3H7 (n) ~ C0 K 2 red 38 NN b S b wO OCm 3 39; OE> B) -0113 .O0NH lt 2 bluish-red 41 R2NCsIIMR2 C3H7 (n) COMH2 H 2 brloatueti0hi Xr. D 1 2 3 n shade of the Str- exercise ex 9 eH ° E3 1 ~: E3 l - 9 irot BOH red 42 CR3 (0OH2CH2) O0IH2 001112 H 1 orange 0 43 G4s9 (n) -0 4 NH2 tt -CQNH2 R 1 orange 0 44 C4I9 (n> -2 -CN 1 -CN H 1 orange-red 45 | H21> - "-e ~ 38. -CB, 1} -OOJH2 | 2 | | orange-red 013 46 5 {-C- {for H2 013 -CONE2 H 1 red 0 47 n-04H, 01I-CI2UC0 <> HC2 -013 -CQNE2 H 1 orange 0215 48 n -GE3 -COOC, H, (n) E 1 orange 49 0II211102SH2 -013 -CONE2 OG2E5 1 orange-red ? 12 0-01 3 50 1 2 S-1PB, 2 013 -CONE2 CH3 1 orange 0i12 0120120013 51 CH3802 t NE2 -01 -CX H 1 claw- 3 red 52 n -CE3 -CORH2 H 1 orange-red arbton d. Shade d. Coloring on Coloring on Mr. 2 11 3 n terephMli $ 3 terphthalate 53 1I0; H11 $ NHH2 NH2 3H7 <n) -CONE2 H 1 scarlet- cl 54 CH3S02 4 NH2 -OH3 -CONH2 -OH3 1 orange-red 55 CHOCE2CH200C 1112 -CHn -CONH2 H 1 orange 56 n -cE3 -cOE2 -ch 1 orange N02. 57 C1 + ff2 -OH3 COOCH2CH2CH2 H 1 orange-red 3 58 OH3 (0H2) 3? HOH2ME2 to NH2 CH3 COOCH2CE20 ¢ H3 H 1 orange C2H5 25th 59> X. -OH3 -COOCH2CH20CH3 H 1 orange 60> -CE) -COOCH2CH20CH3 H 1 orange-red 61 CH30CH2CH200C toNH2 -OH3 -CONE2 H 1 orange Example 62 7.8 p-Aminoazobenzene is stirred for several hours with 100 parts of water and 0.15 part of the reaction product of oleylamine with approximately 12 mol of ethylene oxide at room temperature. After adding 16 parts by volume of 30 percent hydrochloric acid and 150 parts of ice, 12 parts by volume of 23 percent sodium nitrite solution are added to the mixture at 0 ° C. The mixture is stirred for 2 hours at 0 ° C. to 50 ° C., any excess of nitrous acid which may be present is destroyed as usual and the diazonium salt mixture is added in portions to a solution, cooled to oQc, of 10.2 parts of coupling component 4 in 270 parts of water, 4 parts of 50% percent caustic soda and 8 parts soda. After the coupling has ended, the dyestuff which has precipitated is of the formula filtered off, washed with water and dried. 15 parts of a dark red powder are obtained which dissolve in dimethylformamide with a red color. Color of the dye on polyethylene terephthalate fabric: red-brown.

Example 63 7.8 parts of p-aminoazobenzene are diazotized as indicated in Example 62. The diazonium salt mixture is added in portions to a solution, cooled to 0 ° C., of 16 parts of coupling component 27 in 200 parts of dimethylformamide, 400 parts of ice water, 4 parts of 50 percent strength sodium hydroxide solution and 10 parts of sodium carbonate. After the coupling has ended, 10 parts of 20 percent strength acetic acid are added to the mixture, and the dyestuff of the formula which has precipitated out is added is filtered off and washed with water. After drying at 70 ° C., a red-brown powder is obtained which dissolves in dimethylformamide with a red fold and dyes polyethylene terephthalate fabric in red-brown shades.

Analogously to the procedure given, the dyes listed in Table 3 are obtained by using coupling components from Table 1 and further diazo components: Table 3 No. D A1 A2 A color I c cr 64 ON = NON -OH3 -CN H red 65 ft -OH3 -GQOC4H (n) H red 66 -CE3 CONH2 H red-brown 67 "-C3H7 (n) -CONHa H red brown 68 XN = N 9% -OH3 -CN H red OH CH3 69? CH3 -0OOCH2CH2OCH3 H red N. D A1 - A2 ~ A3 shade 70 5 NN 4% NH, -OH3 -CONH2 H red-brown 3 3 71 QN = NQ WH2 -COOC2H5 -CONN H red CH) CH3 72 n -OH3 0000H2OH? 0H29 5 red CH3 73 -C3H7 (n) -eN H red 74 n -OH3 -CONHp OH red 75 n -CHi -COOC4Hg (n) H red J H3 76 ß NsN n% -COOCH2CH20 o -CONN H bluusti- chig> chig red dH3 77 n C3H7 (n) -CN H bluish- chig red 78 n -CH, -CQNN CH3 red 79 tl -OH3 -CONH2 H red OCH 8o ON = N 4F -OH3 -GooCH2CH2OCH H bluusti- 3 too c chig red OH3 No. D A1 A2 A3 color . . STILL, 81 N = NiNH2 -CH3 COOC -00O06H1 (n) 11 'bluish- 3 3 chig red CH3 3 OCH3 82 N = N / \ NH3 -OH3 -CN H bluish- OCH3 3 83, -OH3 -CONH2 H 84-Ooo (0H2) 300H3 -CONH2 3 85 n -CH3 -COOC4Hg (n) H 86, CH, -OH3 -Coo (CH2) 3oCH3 H 87 ON = NONH2 -Ooo (0H2) 3 STILL, -CN H red-brown 88 "-CONHC4Hg (n) -CN H red brown OCH3 CH3 89 ßN = N> NH2 000 (0112) 300113 -CN -GN H red Cl CH3 O H3 J 3 90 βN = NSNH2 -COOC4Hg (n) -OOOO4H (n) H blausjbi C1 C 3 91., COOC6E3 (n) -CN CH3 bluusti- 3 chig red No. D A1 A2 A3 color 92 (CH2N = NqNH2 -O3117 (n) -OONH2 11 red N02 93 ON = N e NH2 -COOC2H5 -CN H red 94 '°' O NH2 -COOC2H5 CNH H brown- orange 0 95 CH3 (CH2) 3CHCH2NHC O NH2 -C °° c2H5 -CN H brown 2 5 96 HNHO0 ,, / \ NH O (CH2) 30CH3 Q "orange- 2 brown Example 97 10.1 parts of 4,4'-diaminodiphenyl sulfone are introduced into 50 parts of 96 percent strength sulfuric acid at 20 to 2500 parts. The mixture is then cooled to 0 ° to 5 ° C. and 20 parts of 41 percent strength nitrosylsulfuric acid are added dropwise. After stirring for 30 minutes at 50 ° C., the diazonium salt mixture is poured onto 250 parts of ice and any excess of nitrous acid which may be present is destroyed as usual. The diazonium salt mixture is then added in portions to a solution, cooled to OOC, of 15 parts of coupling component 3 in 300 parts of dimethylformamide, 300 parts of water and 6 parts of 50 percent sodium hydroxide solution. At the same time, 600 parts of ice and about 100 parts of 50 percent sodium hydroxide solution are added so that the pH is 6.5 to 8 and the temperature is 0 to 5 ° C. during coupling.

After the coupling has ended, the resulting dye is of the formula filtered off, washed with water and dried at 700C. A red-brown powder is obtained which dissolves in N-methylpyrroidone with a red color. Color of the pigment spread: orange-brown.

Example 98 10.9 parts of 3.3'-dichloro-4.4'-diamino-diphenyl become 300 parts of water and 12 parts by volume of 30 percent hydrochloric acid are added. One warms up the mixture to 700C, allowed to cool and then treated with 100 parts of ice and in Shares with 18 parts by volume of 23 percent sodium nitrite solution. After 2 hours Stirring at 0 ° to 50 ° C. eliminates any excess of nitrous acid as usual. The diazonium salt mixture is then added in portions in a solution, cooled to OOC, of 18.8 parts of the coupling component 17 in 600 parts of water, 300 parts of dimethylformamide, 6 parts of 50 percent sodium hydroxide solution and 6 parts of sodium carbonate.

After the coupling has ended, the dyestuff which has precipitated is of the formula suctioned off and washed with water. The red dye obtained is very sparingly soluble or insoluble in the usual solvents. 20 parts of the pigment are rubbed with 80 parts of book or offset varnish in the usual way on a three-roller mill. The printing ink produced in this way gives prints of excellent color strength, brilliance and good lightfastness when processed in letterpress and offset printing.

When using the pigments given in the other examples printing inks with corresponding properties are obtained.

Analogously to the procedures given in Examples 88 and 89 are obtained using other diazo components and coupling components in the dyes listed below in Table 4.

Table 4 No. D A1 A2 A3 color cl 99 HN m H2 Ol -CN H bluish tinge- a -CN H bluish- Cl 100 "ru -CONH2 H red rn 101 ft "CH3 -CONH2 -SO2N 0 red C1 102 H, N4h PH2 CH) -CONH2 H orange C1 103 lt -CONH2 11 orange 104 n C1 -OONH2 H orange OH3 105 H2NXNHz 1, OONH2 H purple OH3 No. D A1 A2 A color 3 0011 3 106 112N / ~ \ / \ NH2 C1 t -CONH2 .11 purple OCH3 CH, 107 H2N) \ NH2 O -CONH2 H red CH3 108 "C1 O -OONH2 H red 109 CH X NH2 -CONH2 H orange-red 3 110 <2 -CONH2 H red '"a- N02 111 C1 4 NN "-OONH2 H red N02 112 C1 b NH2 CH3 -CONH2 S ° 2N ° red SO2NO 113 H2N ON = NO NH2 C1 O -CONH2 H violet 114 H2N O S02 O NH2 O -OONH2 H orange- -- - Brown No. D A1 A2 A3 color 115 H2NS02 / \ NH2 C1 e -OONH2 H orange- - - Brown NO 2 116 H2N X kNH2 112 -CH) -CH, CONH2 H red-brown 02N 117 e -CONH2 H red-brown 118 "e -CN H red 119 "OH3 -CN H red 120 "ß C1 -CONH2 11 red-brown \ = / O 121 C1 ON zu2> -CON H yellow-orange 0 Example 122 15.6 parts of 1-aminoanthraquinone are introduced into 150 parts by volume of 96 percent strength sulfuric acid at room temperature. After the mixture has been cooled to 1000, 22.5 parts of 40 percent strength nitrosylsulfuric acid are added in proportions, the mixture is stirred for 4 hours at 20 to 30 ° C. and the diazonium salt mixture is then poured onto 700 parts of ice. Any excess of nitrous acid present is destroyed by adding urea, then the precipitated diazonium salt is filtered off and washed with 200 parts of water.

The diazonium salt is stirred with 200 parts of water and 0.3 part of the reaction product of oleylamine with approximately 12 mol of ethylene oxide at room temperature. This mixture is then added in proportions to a solution of 23.7 parts of coupling component 19 in 100 parts of dimethylformamide, 5 parts of 50 percent sodium hydroxide solution, 150 parts of water and 6 parts of sodium carbonate. After the coupling has ended, the red dye which has precipitated is of the formula filtered off and washed with water. After drying at 70 ° C., a red powder is obtained which dissolves in hot N-methylpyrrolidone with a red color.

Color of the pigment spread: orange Analogously to the procedure given, the following dyes are obtained with further coupling components and diazo components: Table 5 No. D A1 A2 A color O NH 123 W CH3 ON H brown CH, CN H 124 "O CONH H orange- 2 1 00NH2 H brown O NH2 125 b CH3 CN H red-brown O a ~ 97 ~ No. D A1 A2 A3 color c o H2 126 <C1 e ON H red O C1 O NH2 127 l CH3 CN H red-brown Example 128 7.5 parts of 2-aminobenzothiazole are introduced at 0 to 500 parts into 50 parts of 60 percent strength 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 500. Any excess nitrosylsulfuric acid that may be present is then destroyed as usual and the diazonium salt mixture is then added in small portions to one OOC cooled solution of 11.2 parts of coupling component 1 in 100 parts of dimethylformamide, 5 parts of 50 percent sodium hydroxide solution and 350 parts of water. During the coupling, about 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 the coupling has ended, the dyestuff which has precipitated is of the formula filtered off, washed with water and dried at 700C. It is obtained as a red powder which dissolves in dimethylformamide with a red color and dyes polypropylene fabric containing nickel in bluish red shades.

Example 129 If the procedure is as in Example 128, but instead of 11.2 parts of coupling component 11, 12.5 parts of coupling component 3 are used, a red dye of the formula is obtained the nickel-containing polypropylene fabric colors.

Analogously to the procedure described in Example 128, one obtains with further coupling components and diazo components in the table below described dyes with similar good properties.

Table 6 No. D A1 A2 A3 color 130 aszNH2 -OH3 -COOC4Hg HH bordo 131 "-O3H7 (n) -CONH2 H red No. D A1 AA color L. OH IN CH, CH, 0 132 3 Äic5 / xNH2 OH3 OONH2 lt red 133 "0113 -COQC4 N (n) 11 red 0 .t 134 NH, -CH, CONH, H red 134 OH3 O0NH2 11 red 135 2 5 X> NH2 -0113 -OONH2 11 red 0 n 136 (n) C4H9oC -CHr CONH H, red ~ 'YH2 137 CH3CH2, C, Sf -0113 -CONH2 H red 0 138 Ct NH2 -0113 -CONH2 H orange c tsPNH 139 NS zuNH2 C3H7 (n) -CONH2 H red 140 iÄw71H2 -0113 -OONH2 H orange C <NH2 141 u N -CH3 -CONH2 H red H -30- Example 142 6.9 parts of 1-amino-2-nitrobenzene are dissolved in 13 parts of 96 percent sulfuric acid, optionally with warming, then 15 parts of ice are added in arm parts, the mixture is stirred in 35 parts of water and 75 parts of ice and added rapidly Add 16 parts by volume of 23 percent sodium nitrite solution. After stirring for one hour at 0 ° to 50 ° C., any excess nitrous acid present is eliminated as usual and the diazonium salt mixture is then added to a solution, cooled to 0 ° C., of 15 parts of coupling component 26 in 200 parts of dimethylformamide, 400 parts of ice water, 4 parts of 50 percent sodium hydroxide solution and 15 parts of sodium carbonate.

When the coupling is complete, 20 parts of 10 percent hydrochloric acid are added to the mixture, and the dyestuff of the formula which has precipitated out is added filtered off and washed with water. After drying at 70 ° C., a red-brown powder is obtained which dissolves in dimethylformamide with a red color and dyes polyethylene terephthalate fabric in brown shades.

Table 7 No. D A2 A3 color NO2 145 CH3Q2S 4 NS2 r% orange- 143 OH32 NH2 -O3H7 (n) OOOC2H5 H red 144 -03H7 (n) -CONH2 orange No. DA A2 A3 color 145 OeNj / 02N Q NH2 -CH) -O0NH2 O4H9 (n) orange S02C2H5 146. -OH (n) -CONN -cH3 orange- Red

Claims (4)

Claims 1. Water-insoluble azo dyes of the general formula in which n is the number 1 or 2, D is the radical of an aromatic or heteroaromatic diazo or tetrazo component, A1 is an alkyl group with 1 to 5 carbon atoms, a phenyl, tolyl, methoxyphenyl, chlorophenyl, bromophenyl or Iquitrophenyl group or a optionally substituted carbalkoxy group with a total of 2 to 9 carbon atoms A2 a cyano, carbonamide or optionally substituted carbalkoxy group with a total of 2 to 9 carbon atoms, A3 a hydrogen atom, an alkyl group with 1 to 50 atoms, an alkoxy group with 1 to 5 C atoms and A4 denotes a hydrogen atom, an alkyl group or an optionally substituted sulfonamide group. 2. Dyes according to claim 1 of the general formula in which A5 denotes an alkyl group with 1 to 50 atoms, A6 denotes a carbonamide or carbalkoxy group and A7 denotes a hydrogen atom, a methoxy group or an alkyl group with 1 to 5 carbon atoms and D and n have the meaning given. 3.The use of the dyes according to claim 1 or 2 for coloring of textile material made of cellulose esters, polyamides, nickel-containing polypropylene, Polyesters or as pigments. 4. A process for the preparation of dyes according to claim 1, characterized in that diazo compounds of amines of the general formula D (NH2) n with coupling components of the general formula implements.