GB2031452A

GB2031452A - Azo dyes which contain sulfonic acid groups and oxdiazolyl radicals

Info

Publication number: GB2031452A
Application number: GB7930419A
Authority: GB
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 1978-09-04
Filing date: 1979-09-03
Publication date: 1980-04-23
Also published as: DE2838534A1; FR2434845A1; IT7925212A0; IT1122500B; GB2031452B; JPS5536294A

Abstract

The present invention relates to azo dyes which contain one to three sulfonic acid groups and an oxdiazolyl radical and which in the form of the free acid corresponds to the formula I <IMAGE> where K is the radical of a coupling component, n is 1, 2 or 3, R<1> is hydrogen, chlorine, bromine, a sulfonic acid ester group, unsubstituted or substituted sulfamyl or hydroxysulfonyl, R<2> is hydrogen, chlorine, bromine, nitro, methyl or trifluoromethyl, R<3> is hydroxyl, C1-C8-alkyl, aralkyl or unsubstituted or substituted aryl and Z is C1-C8-alkylene or aralkylene. The compounds according to the invention are exceptionally suitable for dyeing natural polyamides e.g. wool, nylons and leather.

Description

SPECIFICATION Azo dyes which contain sulfonic acid groups and oxdiazolyl radicals The present invention relates to azo dyes which contain one or more sulfonic acid groups and an oxdiazolyl radical.

According to the invention there are provided azo dyes which contain 1 to 3 sulfonic acid groups and an oxdiazolyl moiety and which in the form of the free acid correspond to the formula I

where K is the radical of a coupling component, n is 1, 2 or 3, R' is hydrogen, chlorine, bromine, a sulfonic acid ester group, unsubstituted or substituted sulfamyl or hydroxysulfonyl, R2 is hydrogen, chlorine, bromine, nitro, methyl or trifluoromethyl, R3 is hydroxyl, C,-C8-alkyl, aralkyl or unsubstituted or substituted aryl and Z is C1-C8-alkylene or aralkylene.

The radicals K of the coupling components are predominantly derived from the phenol, aniline, naphthol, naphthylamine, aminonaphthol, acetoacetarylide, pyrazolone, aminopyrazole, pyridone, diaminopyridine, triaminopyridine, diaminopyrimidine, triaminopyrimidine, barbituric acid, quinoline, isoquinoline or indole series.

For example, the coupling components may correspond to one of the formulae

where B1 and B2 independently of one another are hydrogen, C,-C4-alkyl, C2-C4-alkyl which is substituted by hydroxyl, chlorine, cyano, C1-C4-alkoxy, C,-C4-alkanoyloxy or C,-C4-alkoxycarbonyl, C4-C9-alkyl which is interrupted by oxygen and substituted by hydroxyl, C1-C4-alkoxy, phenoxy or benzyloxy, cyclohexyl, benzyl, phenylethyl or phenyl, B3 is hydrogen, hydroxysulfonyl, chlorine, methyl or C,-C4-alkanoylamino, B4 is phenyl which is unsubstituted or substituted by hydroxysulfonyl, chlorine, bromine, methyl, ethyl methoxy or ethoxy, B5 is hydrogen, C,-C4-alkyl, cyclohexyl or benzyl, or is phenyl which is unsubstituted or substituted by chlorine, bromine, methyl, ethyl or hydroxysulfonyl, Be is hydroxyl or amino, B7 is hydrogen, methyl, carbamyl, C,-C4-alkoxycarbonyl or carboxyl, B8 is cyano or carbamyl, B9 is hydrogen, hydroxyl or methyl, B'O is a radical B' or

B" is a radical B1 or

B12 is methyl or phenyl, B13 is hydrogen, methyl, ss-cyanoethyl, ss-hydroxyethyl, ss-carboxyethyl or ss-carbamylethyl and p is 0, 1 ro 2.

Specific examples of radicals B' and B2, in addition to those already mentioned, are: CH3, C2H5, C3H7, C4Hg, C2H4OH, CH2CHOHCH3, CH2CHOHCH2CL, CH2CH2CN, CH2CH2OCH3, CH2CH2OC2H5, CH2CH2OC4H9,

CH2CH2OCOCH3, CH2CH2OCOC2H5, CH2CH2COOCH3, CH2CH2COOC2H5, CH2CH2COOC4H9, CH2CH2OCH2CH2OH, (CH2)3OCH2CH2OH, (CH2)30(CH2)40H, (CH2)3OC2H4OCH3, (CH2)3OC2H4OC2H5, (CH2)3OC2H4OC4H9, (CH2)3OC2H4OCH2C6H5, (CH2)3OC2H4OC6H5, (CH2)3O(C2H4O)2CH3 and (CH2)30(C2H40)2C2H5.

Examples of preferred diazo components are:

Examples of preferred coupling components are those of the formulae

Specific examples of radicals R3, in addition to hydroxyl, are:

CH2C8H5, C2H4C6H5, C6H5, C6H4CI or C6H4CH3.

Examples of Z are

where n may be from 1 to 6.

Examples of sulfonic acid ester radicals and unsubstituted or substituted sulfamyl radicals R' are SO2R, where R preferably is phenoxy which is unsubstituted or substituted by chlorine, bromine, methyl, ethyl, methoxy or ethoxy or is a radical of the formula N(CH3)2. N(c'2H5)2, N(C3R7)2, N(C4H9)2' N(C6H13)2,

On natural polyamides and on nylons, the dyes of the formula I give yellow to red dyeings having very good lightfastness and wetfastness. The deep colors and clear hues achievable with many of the dyes deserve particular mention. The dyes may be used in the form of their alkali metal salts (with Li, Na or K) or of their unsubstituted or substituted ammonium salts. The dyes are also suitable for dyeing leather.

Dyes of particular industrial importance are those of the formula la

where R4 is hydrogen, chlorine, unsubstituted or substituted sulfamyl or hydroxysulfonyl, R5 is hydrogen, chlorine or trifluoromethyl, Z is C,-C3-alkylene or aralkylene, m is 1 or 2 and K1 is the radical of a coupling component of the aniline, naphthol, naphthylamine, aminonaphthol, acetoacetarylide, pyrazolone, aminopyrazole, pyridone, diaminopyridine, diaminopyrimidine or indole series.

A dye of the formula I may be prepared by reacting a diazonium compound of an amine of the formula

with a coupling component of the formula HK then sulfonic acid groups being present in the diazo component and/or the coupling component.

In the Examples which follow, parts and percentages are by weight, unless stated otherwise.

EXAMPLE 1 A solution of 29 parts of the sodium salt of the formula (3) in 200 parts of water is added to a mixture of 300 parts of ice and 35 parts by volume of 10 N hydrochloric acid. 30 parts by volume of a 23 per cent strength aqueous sodium nitrite solution is run in under the surface of this mixture at 0-5"C, the batch is stirred for a further 3 hours at this temperature, and excess nitrous acid is decomposed in the conventional manner by adding amidosulfonic acid.

A solution of 25 parts of acetoacetic acid 2,4-dimethoxyanilide in 250 parts by volume of glacial acetic acid, followed by 750 parts by volume of a 55 percent strength aqueous sodium acetate solution are run into the above diazotized mixture at 0-5 C. The dye is filtered off and washed with dilute sodium chloride solution; it is a yellow powder which gives a greenish yellow solution in hot water. On nylon or wool fabrics, it gives greenish yellow dyeings of exceptional lightfastness and wetfastness.

EXAMPLE 2 A solution of 1 9 parts of 1 phenyl-3-methyl-5-aminopyrazole in 20 parts of 10 N hydrochloric acid and 500 parts of water, followed by 400 parts by volume of a 55 per cent strength sodium acetate solution, is run slowly, at 0-5,C, into the diazotized mixture obtained as described in Example 1, paragraph 1. The dye thus obtained is filtered off, washed with dilute sodium chloride solution and then with a small amount of water, and is dried at 1 00'C. It is a yellow powder which dyes nylon fibers in yellow hues having very good lightfastness and wetfastness.

EXAMPLE 3 A solution of 25 parts of 2,6-bis(2-hydroxyethylamino)-3-cyano-4-methylpyridine in 1 5 parts by volume of concentrated hydrochloric acid and 500 parts of water is added gradually, at 0-5,C, to the diazotized mixture prepared as described in Example 1, paragraph 1, and thereafter sufficient saturated sodium acetate solution to give a pH of from 4 to 5 is added.

After completion of coupling, the dye is filtered off, washed with a small amount of water and dried at 100"C. An orange powder is obtained, which gives a golden yellow solution in hot water and dyes nylon textiles in yellowish orange hues having very good lightfastness and wetfastness.

EXAMPLE 4 The diazotized mixture obtained as described in Example 1 paragraph 1 is added, at 0-5 C, to a solution of 32 parts of N-ethyl-N-benzyl-aniline-3'-sulfonic acid in 10 parts of 50 per cent strength sodium hydroxide solution and 500 parts of water, whilst also adding 500 parts of ice and 20 parts of sodium carbonate. The dye is precipitated from the resulting dye solution by adding 1,000 parts by volume of saturated sodium chloride solution, and is filtered off, washed with dilute sodium chloride solution and dried. The yellowish brown powder readily dissolves in water and gives orange dyeings, having very good lightfastness and wetfastness, on nylon filaments.

EXAMPLE 5 37.5 parts of the compound of the formula (12) are dissolved in 250 parts of glacial acetic acid and 50 parts of propionic acid. 32 g of 40 per cent strength nitrosylsulfuric acid are added dropwise at 0-5,C and the mixture is stirred for a further 2 hours at the same temperature. The excess nitrous acid is then destroyed by adding urea in the conventional way.

The resulting diazotized mixture is added, at 0-5"C, to a mixture obtained as follows: 26 parts of 2-amino-8-hydroxynaphthalene-6-sulfonic acid are dissolved in 300 parts of water with the aid of 7.5 parts by volume of 50 per cent strength sodium hydroxide solution. 60 parts by volume of 10 per cent strength hydrochloric acid and 300 parts of ice are then added to the solution.

Saturated sodium acetate solution is then slowly added dropwise to the coupling mixture until the pH reaches 2-3.

After completion of coupling, the mixture is neutralized (to pH 6-8) with 50 per cent strength sodium hydroxide solution and the dye is then filtered off, washed with water and dried. A black powder is obtained, which gives a bluish violet solution in hot water and dyes nylon fabrics in blue hues having good lightfastness and wetfastness.

EXAMPLE 6 146 parts of the diazo component of the formula

are dissolved, at 30-50"C, in 2,500 parts by volume of water giving a pH of 7-9. 1 60 parts by volume of a 23 per cent strength aqueous sodium nitrite solution are added, followed by 2,000 parts by weight of ice. 1 80 parts by volume of an aqueous 36 per cent strength hydrochloric acid solution are then added rapidly.After stirring for 2 hours at 0-5"C, the suspension obtained is combined with a solution obtained by mixing 1 46 parts of the coupling components of the formula

2,000 parts by volume of water and 100 parts by volume of 36 per cent strength concentrated hydrochloric acid and subsequently adding 2,000 parts of ice. 600 parts of sodium chloride are added to the batch and the latter is then brought to a pH of 3.5-3.7 by adding sodium acetate.

After stirring the batch for a further 30 minutes, the pH is raised to 5-5.5. Coupling is complete after stirring overnight. The mixture is then heated to 50-70"C, 100 g of sodium chloride are added and the dye which has precipitated is filtered off and washed with a small amount of cold water. After drying, 296 parts of the dye of the formula

are obtained. This dye gives a yellow solution in water and dyes polycaprolactam fabrics in strong, exceptionally lightfast, reddish yellow hues having very good wetfastness. The dyeings on wool are also very lightfast.

EXAMPLE 7 1 8.2 parts of the diazo component of the formula

are dissolved in 280 parts by volume of water, the solution having a pH of 7 to 9. 14 parts by volume of a 23 per cent strength sodium nitrite solution are added and the mixture is cooled to 0-5"C with ice. After having added 1 5 parts by volume of concentrated hydrochloric acid, the mixture is stirred for 2 hours at 0-5'C. Excess nitrous acid is then destroyed with amidosulfonic acid and the mixture is buffered to pH 4.7 with sodium acetate. After adding a solution of 10.4 parts of the coupling component of the formula

in 50 parts by volume of dimethylformamide, the mixture is stirred for 3 hours and the pH is then raised to 5-5.5.After having been stirred overnight, the suspension is brought to pH 6.5 with sodium hydroxide solution and is heated with steam to 80 C. The dye which precipitates, of the formula

is filtered off, washed with a small amount of cold water and dried. 29 parts of a reddish brown powder are obtained; this gives a golden yellow solution in water and dyes polycaprolactam and wool in exceptionally fast yellow hues. The dye also dyes leather in orange hues having good lightfastness and wetfastness.

The following dyes can be produced in an analogous manner and have the stated hue when used for dyeing polycaprolactam.

TABLE 1

Example No. X R1 R2 Hue 8 ci H (CH2)3O(CH2)4OH yellow 9 H H n l 10 H (CH2)2OCH3 (CH2)2OCH3 " 11 H " (CH2)3OCH3 " 12 H " (CH2)3OC@H@ 13 Cl n n reddish yellow 14 NO2 " (CH2)2OCH3 red 15 N02 (CH2)2OH red 16 NO2 (CH2)3OCH3 (CH2)2OCH3 red 17 NO2 " (CH2)3CH3 red 18 H (CH2)3OCH3 (CH2)3OC2H5 reddish yellow 19 H (CH2)3OC2H5 (CH2)3OCH3 " 20 H " (CH2)2O(CH2)2OH yellow 21 H (CH2)3OCH3 (CH2)2OH " 22 H (CH2)3OCH3 (CH2)3OH yellow TABLE 1 (cont.) Example. X R1 R2 Hue No.

23 H (CH2)3OCH3 CH2-CH-CH3 yellow OH 24 Cl " " reddish yellow 25 Cl " (CH2)3OH " 26 Cl " (CH2)2OH " 27 Br (CH2)3OH (CH2)3OH " 28 H H (CH2)3O(CH2)2O(CH2)2OCH3 yellow TABLE 2

Example R1 R2 R3 R4 R5 Hue No.

C 5 3 ri 0 0 0 ari ri aci rl 29 H CH3 reddish Sl T V U o V1 I V fs N ~ O O H TABLE 2 (cont.) Example R1 R2 R3 R4 R5 Hue No.

32 CH2SO3Na SO3H (cH2)30cH3 (cH2)30H CH3 yellow o rl = = = = = = = = = = t 35 H CH2CH2OH CH2CH2OH I, c n :: u U Cl (CH2)30H (CH2)30H 'I II crf Z o I V H H = Cr)me cu n cu h hy h -4 T cq U : cw: N N : : : 2Tr Cl H II II VI U U I: U U u U Cur, O O O n N e (M U FJ :r: N x V 5: U ~ U w o :: U V :]: X I ~l < T U1 U ra z Z O O fe | U T U ct O o H O4 TABLE 2 (cont.) Example R1 R2 R3 R4 R5 Hue No.

5 o . * s w O Cr) CH2-SO3Na rd Z m u) A 48 IV H fromr I 0 21 52 SUUZS UU 49 CH2SO3H n (VC'I(VmCVC N 71 I' I= T 121 := 2 X I X X X T T 2 U u U U u v u VI st v U 52 II H (CH2)20CH3 (CH2)20CH3 II II vl o m c?n rZ 54 VI H (CH2)2sO3H (Vcr)VI VI 1N : : : CU N N: N N X I T I X X ssJ U U U U U U X = T = U T = U T 1 r tO Z O m n I U] > V U t In tD N o O H N f TABLE 2 (cont.) Example R1 R2 R3 R4 R5 Hue No.

s CO rl Url 55 h t a t cd a) z I, 56 CH2 -SO2OH3 II rc\ 6 CU X = t U = U U m m u o O h 57 OH2OH2SO3H S02N(02H5)2 (O)2OH (CH2)20H N U v u o\ cu CU xO\ V t S II If C2H5 V X 0n 0 I' 60 1, t 61 = It tt pglJ OJ V V V N x n V O s~ U) t U] - t t t mn v O cu Q X o cu o n m N N VCiJ vx vm Om = ~ = t U) s 08 0 H o U) TABLE 2 (cont.) Example R1 R2 R3 R4 R5 Hue No.

a) hO C cd k n X V CH2CH2SO3H t CH2OH2SO3H 04H9(fl) t = = U F M X X X X U U U O 0 0 64 y(CH3)2 H (0H2)30I{ (OH2)30H t? II x ^cu ^cu tn mn o v v v O U U U CR V V = V 65 OH2CHSO3H H Ov CU O rC\ L: yr\ 66 OH2CH2O2OH3 S02NH -SO3H H2)3OOH3 (0H2)30CH3 II cu v v 0S uz n l a/ i n cu to t t v n n N O O O GQ N < % G] CM o 0d V n CU Cd 2 O t: = V = VGQ V V CU TABLE 3

Example R1 R2 K Hue No.

a k 0 C M bO E: rl d k k P t O U CU V \ / v CH 68 It Cl '1 U 69 It H 0\\OH2Ofl2ON orange 02H5 o 0O N V V S S es o TABLE 3 (cont.) Example No.R1 R2 K Hue

a O k (11 e rc H a > < t b) 2 t cu cu i i 71 II Cl II U z b-v CU X It i N0NH2 V OONH2 HO 110H0 cu cu e OH2 a-n < -VN uo 3: OH5 H500 OONH2 I?Ln n CM I I rl rl v H H ~E 0N 0n uz UN cD o H N se s > > > ci es TABLE 3 (cont.) Example No.R1 R2 K Hue

6 m d Co do o Q)rl a-r t = rl ari o k rc Vt R SO H 3 77 0 SO O a V = = X u- cB x :U n O H H = GO = V V x < 1 rN 0 o l$Vr cu - z I Vcu v s ao o C s F S TABLE 3 (cont.) Example No.R1 R2 K Hue

9 as h U trt vt H OH yellow X X e H30 OOOH 82 It H It HO A' N 1CH3 OOOH 83 It H HO j)'N 'I O Q CM rCM V H OJ r os oO TABLE 3 (cont.) Example No.R1 R2 K Hue

84 OH2OH2SO3H H OOOH yellow HO &commat; = t = t-n P v COOH 85 tt H I' HO m 0 re 86 Ii H HO- o (OH3)3 tt = v p: v X X 5: X X on vcM v] o cu u] v Scu cu v vt t LA OD CO D TABLE 3 (cont.) Example No. R1 R2 K Hue

o H = = h O V O V V9 Cl O rl 2 V ,0.

X u 90 CH2CH2SO3H H COOH It HO OH o o :32 b1 SC O NC V U) V CU CU (M V V V a O oo CO TABLE 4

Example R1 R2 R3 R4 R5 Hue No.

s o 37=r= CU Ln 3: U 91 CH2CH2SO5H H NH(0H2)20H (CH2)20M o rr3 CU yc\ CU CU r;U Z CU CU N V V 5v X =e u ON N V o CM V N TABLE 4 (cont.) Example No.R1 R2 R3 R4 R5 Hue

3 0 rl H 95 CH2CH2SO3H H =tor= =t= = t = t 3 (U " CU CU II H ) - C) Z = t t t t Z 0 o cu rc\ 3= n t 100 II H II (CH2)50CH5 II 0 h h hh R CU CUCUCU CUCU G1 N N N N CU N 101 C = t It (CM2 t : It 3: U UUU UUr e ~ w w > N V 104 II H It (CH2)20(0H2)20H II It yr\ o zr\ v U O n N m O ~ N n V :C CM OJ V O H Cd n * n Ln xo Cs CO Gss O O O O O s TABLE 4 (cont.) Example No.R1 R2 R3 R4 R5 Hue

o H o o 5 106 ) H Ooh3 OH2SO3H N t== yellow CU CU n ~s =n Xn n V It 505H On U U e Z ~ = Z - V = 108 tt It 3: 109 CH2CH2SO5H 505C6H5 OH5 CH2S05H n OH5)2 yellow CU U ooi CJ CU N (U N u E: rC\ CU c\v 110 zt S02N(0H5)2 It = It " V V V = w V ~ Ct V 2: t V W n = V Z n 1t N O O O t] ~ GO A XD F O rI N n O O O O I H I < H , < H , < H H H H TABLE 4 (cont.) Example R1 R2 R3 R4 R5 Hue No.

0 P; OH2CH2SO3H H NH2 (CH2)20(cH2)20H : yellow X Ic\ U U X O 0 115 1I H OH5 OH N 0 x x x u u cu x v kZ It H NH(0H2)50CH5 NH(0H5)500H5 NH(CH5)500H5 = = Vti O 117 II H NH(0H2)200H5 NH(0H2)20CH5 NH(OH2)200H5 tt N = = CU X X o n V t cu yc\ Cy 0 3:: e x J Fc\ cu OH SO < u Na V O = t V ~ z Z O Z t Z X II FI 5 120 OH OH V CU U (U Ln 3: 5: X X rc\ cu Z U O U CU e u 121 It Cl V Z; Z; Z SZ = Z O H V O n Ch U O N Z U] t n o V wV V = > Lf > co o H r1 ,~ < r1 r1 1 OJ N TABLE 4 (cont.) TABLE 4 (cont.) Example No.R1 R2 R3 R4 R5 Hue

o a a) aa h = NH02H5 NH = t k5t CH2SO3H V OH2OH2SO3H v \o u ;z o u v Soch pc\ =e: rCI C\ Q S O 0 NH NH It OH3 SO 3H 2 OH2OH2SO3H i NH-O3H6OH NH-03H60H > R t Z > n 128 t u i t N CU N n t P: r Z Z t0 po0= mN N N VN V V = V V = = CU n st 1 vD ts 00 CM N N C'l N N Ctl H H H H H H H TABLE 4 (cont.)

Example Diazo component | Coupling component | Hue CH2CH2S03H NH2 129 NH2 H red OCH3 SO3H CH2CH2S03H 130 i NH2 II VI 0,N-F-CH2CM2SO2CH3 dull 131 C1qNH2 IV bluish red SO3H CH 132 formula (7) CH3 yellow HO ss SO3H CH3 133 IV 77(JN3 II HO ISo 3M ISO,H 1 34 .. HO , CH3 .. 134 II HO 'CH VI SO3H

TABLE 4 (cont.)

Example Diazo component Coupling component Hue CO0H MN 135 formula (7) HO f yellow SO 3H OH 37(3 II HO ?r 136 .. C1,44 SO 3H 137 It U orangforange H03S NH 2 138 It - SO 3H IV MO 3 H3 CH, 139 II | H2N45 yellow SO 3H TABLE 4 (cont.)

Example Diazo component Coupling component Hue CM3 140 formula (7) H2 ) > yellow bt S03H H3C CN 141 " (12) ssNHCH2CH2oso3H red NH-CM2 -CM2SO 3H SO3H 142 " (3) 503H yellow H3C CM3 SO H 3 143 " (9) CH3-CO-CM2-CO-NH vOCH3 .. OCH3 0 144 II (9) red bright 3

TABLE 4 (cont.)

Example Diazo component Coupling component Hue 5 CM3 10 HO 145 formula (7) t yello15 SO 3H 20 146 formula (10) .. n 25 147 formula (6) .. n CM3 30 148 .. HO g S03H 40 149 n H N N/2 > n 503H 50 CM3 CON 55 150 formula (3) NM-C4M yellowish 150 formula (3) 9 > NH-C4H,(n) orange ) NH-CH2-CH2 t S03H 60 TABLE 4 (cont.)

Example g Diazo component | Coupling component ss Hue C,H 151 formula (9) /C2M5 orange sjM\N\C2Hs OH 152 formula (11) bright' N,' red SO3H CM3 CO 0CM 153 formula (3) H2C-CO-NH T OCH3 yell Cl CM3 CO 0CM3 154 t( H2C-CO-NH :H3 CM3 CH3 0CM OCH, H2 CCONHt 156 IV H2NAN'N tt 2' TABLE 4 (cont.)

Example Diazo component Coupling component Hue 157 formula (3) M2AW""N yellow ' 158 II N/N H2 CM2 159 formula (5) CH3 HO MO ( 160 formula (1) HO / N' (, CM3 3 CM3 11NI CH, C2H5 SO3M 162 O N CH2 4 i ora ge TABLE 4 (cont.)

example Diazo component Coupling component t Hue 5 NM2 163 formula (6) ss red 10 HO , SO3H 15 CH3 CN OH 20 164 .. > NH CH2 CH2 CH2CH2 H yellowish NM-CH2-CM2 -O-CH2-CM2-OH orange 25 CM3 CN yellow 165 II NM-CH2-CM2-OH 30 2 CM3 CN 35 166 .. ss NH CH2 CH2 0 C 2C 2 40 40 NH2 COOC2H5 45 167 It y " 45 50 CO-NH 168 IV HO1 C " 55 H 60 60 CH3 1 3 OCH 169 formula (3) CO X 65 H2C-CO--NH)\ OCH3 TABLE 4 (cont.)

Example Diazo component Coupling component Hue CM3 170 formula (3) HO N N yellow MO 171 rye It 3 IV HO (CM3 CM3 ' II 172 formula (1) HO Cl Cl CM3 173 formula (2) H2N b ti MN 174 j H2 N TwflN It CM2 TABLE 4 (cont.)

xample Diazo component I Coupling component Hue 5 < ula (5) | 2 C H (5) | orange 10 C,H, 15 MN it bright SO3H red 20 CM3 CN 25 177 .. $ NH-CH2-CH2- H yellowish NH-CH2-CH2-OH 30 CM3 CN 35 178 .. $%lH-CH2CH2OCM2CH2OH 40 NH-CH2-CH2-O-CH2-CH2OH 40 OH 45 179 ,. C yellow 50 CH3 CM CN 55 180 $ II CH2CH20CH2CH20H 60 NH2 TABLE 4 (cont.)

Example Diazo component Coupling component Hue CH3 . 181 formula (5) CH3 3 yellow H2 C-CO-NHOCM3 CM3 182 . HO N'N .. J1 183 (, HO CH3 183 II MO IV CM3 CM3 184 VI HOsNN . Cl 1 Cl CM3 185 II H2N 7&num;N 'I 186 II It M2N C1M 2D

TABLE 4 (cont.)

Example Diazo component Coupling component Hue 5 187 formula (13) N CH2 9 S i orange 10 SO3M 15 MN 188 .. red bright 0 SO H CH3 CN 25 W 189 .. a NH CH2 CH2 OH yellowish orange 30 NH-CH2-CH2-OH CM3CN 35 190 .. ss NHCH2CH2-0-CH2CH20H 40 N 40 NH-CM2-CH2-O-CH2-CH2-OH 45 SO3M 191 II yN1IA yellow 50 CM3 55 OH3 CN 192 II -NMMM-0-H H 20H NH2222 1 60 TABLE 4 (cont.)

Example Diazo component Coupling coin p' ,aloe 'yellow 193 formula (4) HO OM 194 VI HO 3 ft Cl Cl OH3 195 IV MC2)NI Cl ff CM I 3 0CM3 CO 196 H2C-CO-NH t I n H2O-C0-NH\ 0CM3 197 H . 198 IV t CH3 II CM3

TABLE 4 (cont.)

Example Diazo component Coupling component | Hue SO3M 199 formula (I) HSC6 y̆) yellow CM 3 CM3 200 .. ss HC2H4 NHCH2CH2OH OH 201 II ẏ)N H2 red HO3S CH3 202 VI yellow w-NMCH2CH2oCH3 NMCM2CM2OH CM 3 N 203 " ss HCH2CH2 CH2CH2 NHCH2CH2OCM2 CM2 OH C1M3 0CM3 CO 204 t CH2-CONHgXOCH3 A01, TABLE 4 (cont.)

Example | Diazo component Coupling component Hue O-N 205 g > 2CM2SO3M s MN CH3 yellow C6M5 206 n HO -N/VN n C6H5 CH MO 207 n t n Cm SO3M 208 II NMC2M5 deep red TABLE 4 (cont.)

Example Diazo component Coupling component Hue 1 209 }aN 2 2 3 W golden MO3S o NH2 > H-C4Hg(n) yellow NH-C4Hg(n) CH3 CN 210 IV X));;sm)\)3;o(;;2)40H "I - NH( -CH3),0(CH,)40H C H3 211 1' N1C\M3 yellow H tJ S03H OH 212 II N(C4H9)2 II NH-(CH2)30H TABLE 4 (cont.)

Example Diazo component Coupling component L Hue 5 N (CH)SO H CM3 CN 10 213 223 H-CH(n) orange HO N49 H03S NH2 NM-CH2-CM2SO3M 15 20 O N%CM2CM2SO3M 20 CM3 l g yellow \=/ HO C4M9 30 0-N 35 215 +CH2CH2S03H n n U NH2 40 CM 3 45 216 5 tl 5J MO CM2CH2OH2 | TABLE 4 (cont.)

Example Diazo component Coupling component Hue 5 kN CH, CONH, 10 217 kN CH2CH2S03H OH3 CONM2 greenish Br ffi\NM2 \{O yellow MO C4M9 15 TABLE 4 (cont.)

Example R1 R2 R3 Hue 218 CH3 C2H4OH C4H9(n) orange 219 C2H5 " " " 220 " " C2H4C6H5 " 221 " C2H5 " " 222 " " C2H4C6H4SO3H " 223 -(CH2)5- " " 224 -CH2CH2OCH2CH2- " "

Claims

1. An azo dye which contains 1 to 3 sulfonic acid groups and an oxdiazolyl moiety, and which in the form of the free acid corresponds to the formula I

where K is the radical of a coupling component, n is 1, 2 or 3, R1 is hydrogen, chlorine, bromine, a sulfonic acid ester group, unsubstituted or substituted sulfamyl or hydroxysulfonyl, R2 is hydrogen, chlorine, bromine, nitro, methyl or trifluoromethyl, R3 is hydroxyl, C,-C8-alkyl, aralkyl or unsubstituted or substituted aryl and Z is C1-C8-alkylene or aralkylene.

2. A dye as claimed in claim 1 having 1 or 2 sulfonic acid groups and which in the form of the free acid corresponds to the formula

where R4 is hydrogen, chlorine, unsubstituted or substituted sulfamyl or hydroxysulfonyl, R5 is hydrogen, chlorine or trifluoromethyl, Z is C1-C3-alkylene or aralkylene, m is 1 or 2 and K1 is the radical of a coupling component of the aniline, naphthol, naphthylamine, aminonaphthol, acetoacetarylide, pyrazolone, aminopyrazole, pyridone, diaminopyridine, diaminopyrimidine or indole series.

3. A dye as claimed in claim 1 and identified in any of the foregoing Examples.

4. A process for the preparation of a dye as claimed in claim 1, wherein a diazonium compound of an amine of the formula

is reacted with a coupling component of the formula HK R1, R2, R3, Z and K having the meanings given in claim 1 and the n sulfonic acid groups being present in the diazo component and/or the coupling component.

5. A process as claimed in claim 4, wherein a diazonium compound corresponding to an amine identified as any of formulae 1 to 14 is used.

6. A process as claimed in claim 4 or 5, wherein a coupling component according to any of formulae (a) to (j) hereinbefore is used.

7. A dye formulation for dyeing natural polyamides and dyeing nylons, which comprises a dye as claimed in any of claims 1 to 3 or prepared by a process as claimed in any of claims 4 to 6 together with one or more conventional constituents of dyeing formulations.

8. A process for dyeing natural or synthetic polyamides or leather wherein a dye as claimed in any of claims 1 to 3 or prepared by a process as claimed in any of claims 4 to 6 is used in the form of an alkali metal salt or unsubstituted or substituted ammonium salt.