Azo dyes containing sulfonic acid groups and oxdiazolyl radicals

Abstract

Compounds which in the form of the free acids have the formula I ##STR1## where K is the radical of a coupling component, n is 1, 2 or 3, R.sup.1 is hydrogen, chlorine, bromine or hydroxysulfonyl, R.sup.2 is hydrogen, chlorine, bromine, nitro, methyl or trifluoromethyl and R.sup.3 is hydrogen, alkyl of 1 to 8 carbon atoms (which may or may not be interrupted by oxygen and may be unsubstituted or substituted by hydroxyl, alkoxy of 1 to 8 carbon atoms, phenyl or phenoxy), benzyl, phenylethyl, cyclohexyl, phenyl (which may be unsubstituted or substituted by chlorine, bromine, nitro, methyl, ethyl, methoxy, ethoxy, phenoxy, dialkylamino, where alkyl is of 1 to 4 carbon atoms, or hydroxysulfonyl), naphthyl, pyridyl, thienyl or furyl. The compounds of the formula I may be used for dyeing nitrogen-containing fibers; the dyeings obtained are very fast and have brilliant hues.

Description

The present invention relates to compounds which in the form of the free acids correspond to the formula I ##STR2## where K is the radical of a coupling component, n is 1, 2 or 3, R.sup.1 is hydrogen, chlorine, bromine or hydroxysulfonyl, R.sup.2 is hydrogen, chlorine, bromine, nitro, methyl or trifluoromethyl and R.sup.3 is hydrogen, alkyl of 1 to 8 carbon atoms (which may or may not be interrupted by oxygen and may be unsubstituted or substituted by hydroxyl, alkoxy of 1 to 8 carbon atoms, phenyl or phenoxy), benzyl, phenylethyl, cyclohexyl, phenyl (which may be unsubstituted or substituted by chlorine, bromine, nitro, methyl, ethyl, methoxy, ethoxy, phenoxy, dialkylamino, where alkyl is of 1 to 4 carbon atoms, or hydroxysulfonyl, naphthyl, pyridyl, thienyl or furyl.

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

Specific examples of coupling components are those of the formula ##STR3## where B.sup.1 and B.sup.2 independently of one another are hydrogen, alkyl of 1 to 4 carbon atoms, alkyl of 2 to 4 carbon atoms which is substituted by hydroxyl, cyano, alkoxy of 1 to 4 carbon atoms, alkanoyloxy of 1 to 4 carbon atoms or alkoxycarbonyl (where alkoxy is of 1 to 4 carbon atoms), alkyl of 4 to 9 carbon atoms which is interrupted by oxygen and substituted by hydroxyl, alkoxy of 1 to 4 carbon atoms, phenoxy or benzyloxy, cyclohexyl, benzyl, phenylethyl or phenyl, B.sup.3 is hydrogen, hydroxysulfonyl, chlorine, methyl or alkanoylamino of 1 to 4 carbon atoms, B.sup.4 is phenyl which may be unsubstituted or substituted by hydroxysulfonyl, chlorine, bromine, methyl, ethyl, methoxy or ethoxy, B.sup.5 is hydrogen, alkyl of 1 to 4 carbon atoms, cyclohexyl, benzyl or phenyl which may be unsubstituted or substituted by chlorine, bromine, methyl, ethyl or hydroxysulfonyl, B.sup.6 is hydroxyl or amino, B.sup.7 is hydrogen, methyl, carbamoyl or alkoxycarbonyl where alkoxy is of 1 to 4 carbon atoms), B.sup.8 is cyano or carbamoyl, B.sup.9 is hydrogen, hydroxyl or methyl, B.sup.10 is a radical B.sup.1 or ##STR4## B.sup.11 is a radical B.sup.1 or ##STR5## B.sup.12 is methyl or phenyl, B.sup.13 is hydrogen, methyl, .beta.-cyanoethyl, .beta.-hydroxyethyl, .beta.-carboxyethyl or .beta.-carbamoylethyl and p is 0, 1 or 2.

Specific examples of radicals B.sup.1 and B.sup.2, in addition to those already mentioned, are: CH.sub.3, C.sub.2 H.sub.5, C.sub.3 H.sub.7, C.sub.4 H.sub.9, C.sub.2 H.sub.4 OH, CH.sub.2 CHOHCH.sub.3, CH.sub.2 CHOHCH.sub.2 Cl, CH.sub.2 CH.sub.2 CN, CH.sub.2 CH.sub.2 OCH.sub.3, CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5, CH.sub.2 CH.sub.2 OC.sub.4 H.sub.9, ##STR6## CH.sub.2 CH.sub.2 OCOCH.sub.3, CH.sub.2 CH.sub.2 OCOC.sub.2 H.sub.5, CH.sub.2 CH.sub.2 COOCH.sub.3, CH.sub.2 CH.sub.2 COOC.sub.2 H.sub.5, CH.sub.2 CH.sub.2 COOC.sub.4 H.sub.9, CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH, (CH.sub.2).sub.3 OCH.sub.2 CH.sub.2 OH, (CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH, (CH.sub.2).sub.3 OC.sub.2 H.sub.4 OCH.sub.3, (CH.sub.2).sub.3 OC.sub.2 H.sub.4 OC.sub.2 H.sub.5, (CH.sub.2).sub.3 OC.sub.2 H.sub.4 OC.sub.4 H.sub.9, (CH.sub.2).sub.3 OC.sub.2 H.sub.4 OCH.sub.2 C.sub.6 H.sub.5, (CH.sub.2).sub.3 OC.sub.2 H.sub.4 OC.sub.6 H.sub.5, (CH.sub.2).sub.3 O(C.sub.2 H.sub.4 O).sub.2 CH.sub.3 and (CH.sub.2).sub.3 O(C.sub.2 H.sub.4 O).sub.2 C.sub.2 H.sub.5.

Examples of preferred diazo components are: ##STR7##

Preferred coupling components have the formulae ##STR8##

On natural polyamides and synthetic nylons, the dyes of the formula I give yellow to red dyeings with very good lightfastness and wetfastness. The depth of color and the clear hue achievable with many dyes deserve particular mention. The dyes may be used in the form of their alkali metal salts (the alkali metal being Li, Na or K) or of their ammonium salts (where ammonium may be unsubstituted or substituted).

Dyes of particular industrial importance are those of the formula Ia ##STR9## where R.sup.4 is hydrogen, chlorine or hydroxysulfonyl, R.sup.5 is hydrogen, chlorine or trifluoromethyl, R.sup.6 is methyl, alkoxyethyl (where alkoxy is of 1 to 4 carbon atoms), phenoxyethyl, phenyl which may be unsubstituted or substituted by hydroxysulfonyl, or pyridyl, m is 1 or 2 and K.sup.1 is a coupling component of the aniline, naphthol, naphthylamine, aminonaphthol, acetoacetarylide, pyrazolone, aminopyrazole, pyridone, diaminopyridine or indole series.

The dyes of the formula I may be manufactured by reacting a diazonium compound of an amine of the formula ##STR10## with a coupling component of the formula

HK; the n sulfonic acid groups may be present in the diazo component and/or in the coupling component.

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

EXAMPLE 1

A solution of 34 parts of the sodium salt of the formula (2) in 200 parts of water is added to a mixture of 300 parts of ice and 35 parts by volume of 10-molar hydrochloric acid. 30 parts by volume of a 23% strength aqueous sodium nitrite solution is run in under the surface of this mixture at 0.degree.-5.degree. C., stirring is continued for 3 hours at this temperature, and the excess nitrous acid is then destroyed 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 is run into the resulting diazotized mixture at 0.degree.-5.degree. C., after which 750 parts by volume of a 55% strength aqueous sodium acetate solution are run in. 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 with excellent lightfastness and wetfastness.

EXAMPLE 2

A solution of 19 parts of 1-phenyl-3-methyl-5-aminopyrazole in 20 parts of 10-molar hydrochloric acid and 500 parts of water is run slowly, at 0.degree.-5.degree. C., into the diazotized mixture obtained as described in Example 1, paragraph 1, after which 400 parts by volume of a 55% strength aqueous sodium acetate solution are run in. The dye obtained is filtered off and washed with dilute sodium chloride solution and then with a little water. After drying at 100.degree. C., a yellow powder is obtained, 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 15 parts by volume of concentrated hydrochloric acid and 500 parts of water is added gradually, at 0.degree.-5.degree. C., to the diazotized mixture prepared as described in Example 1, paragraph 1, and sufficient saturated sodium acetate solution is then added to give a pH of from 4 to 5. The dye is filtered off after completion of coupling, washed with a little water and dried at 100.degree. C. An orange powder is obtained, which gives a golden yellow solution in hot water and dyes nylon textiles in yellowish orange hues which have very good lightfastness and wetfastness.

EXAMPLE 4

The diazotized mixture obtained as described in Example 1, paragraph 1, is added at 0.degree.-5.degree. C. to a solution of 32 parts of N-ethyl-N-benzyl-aniline-3'-sulfonic acid in 10 parts of 50% strength sodium hydroxide solution and 500 parts of water, 500 parts of ice and 20 parts of sodium carbonate also being added. The dye is precipitated from the resulting 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 obtained readily dissolves in water and gives orange dyeings, having very good lightfastness and wetfastness, on nylon filaments.

EXAMPLE 5

24 parts of the compound of the formula (1) are dissolved in 250 parts of glacial acetic acid and 50 parts of propionic acid. 32 g of 40% strength nitrosylsulfuric acid are added dropwise at from 0.degree. to 5.degree. C. and the mixture is then stirred for 2 hours at the same temperature. The excess nitrous acid is then destroyed in the conventional manner by adding urea.

The diazotized mixture obtained is added at 0.degree.-5.degree. C. to a mixture which has been obtained by dissolving 26 parts of 2-amino-8-hydroxynaphthalene-6-sulfonic acid in 300 parts of water containing 7.5 parts by volume of 50% strength sodium hydroxide solution, and then adding 60 parts by volume of 10% strength hydrochloric acid and 300 parts of ice to the solution.

Sufficient saturated sodium acetate solution is then slowly added dropwise to the coupling mixture until the pH has reached 2-3.

After completion of coupling, the mixture is neutralized with 50% strength sodium hydroxide solution to a pH of 6-8, and the dye is then filtered off, washed with water and dried. A dark red powder is obtained, which gives a red solution in hot water and dyes nylon fabrics in red hues having very good lightfastness and wetfastness.

EXAMPLE 6

24 parts of the compound of the formula (6) are stirred into 120 parts of water and 40 parts of concentrated hydrochloric acid at room temperature. The mixture is then made up to 500 parts by volume with water and ice. After adding 30 parts by volume of a 23% strength sodium nitrite solution of from 5.degree. to 10.degree. C., the mixture is stirred for 2 hours and excess nitrous acid is destroyed in the conventional manner.

The diazonium salt solution thus obtained is coupled with 26 parts of 2-amino-8-hydroxynaphthalene-6-sulfonic acid by the method described in Example 5, paragraph 2. The dye thus obtained gives red dyeings, having very good lightfastness and wetfastness, on nylon fabrics.

If the methods described in the preceding Examples are followed, starting from the components indicated in the Table, the corresponding dyes are obtained.

__________________________________________________________________________Diazo component ##STR11## Hue of aEx- dyeingample R Coupling component on nylon__________________________________________________________________________ 7 CH.sub.3 ##STR12## red 8 CH.sub.2CH.sub.2OCH.sub.3 " " 9 CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH.sub.3 " "10 ##STR13## " "11 ##STR14## " "12 ##STR15## " "13 ##STR16## " "14 ##STR17## " "15 CH.sub.2CH.sub.3 " "16 ##STR18## " "17 ##STR19## " "18 ##STR20## " "__________________________________________________________________________ __________________________________________________________________________Ex-ample Diazo component Coupling component Hue__________________________________________________________________________19 ##STR21## ##STR22## red20 ##STR23## " red21 ##STR24## " red22 Formula (1) ##STR25## yellow23 " " yellow24 " ##STR26## yellow25 " " yellow26 " ##STR27## yellow27 " ##STR28## orange28 " ##STR29## orange29 " ##STR30## yellow30 " ##STR31## yellow31 " ##STR32## yellowish orange32 " ##STR33## yellow33 " ##STR34## yellow34 " ##STR35## yellowish red35 Formula (7) ##STR36## yellow36 Formula (8) " yellow37 Formula (6) " yellow38 " ##STR37## yellow39 " ##STR38## "40 " ##STR39## yellowish orange41 " ##STR40## orange42 " ##STR41## yellowish red43 Formula (2) ##STR42## yellow44 " ##STR43## yellow45 " ##STR44## yellow46 " ##STR45## yellow47 " ##STR46## yellow48 " ##STR47## yellow49 " ##STR48## yellow50 " ##STR49## "51 " ##STR50## "52 " ##STR51## orange53 " ##STR52## red54 " ##STR53## yellowish orange55 " ##STR54## yellow56 " ##STR55## yellow57 " ##STR56## yellow58 " ##STR57## yellow59 Formula (3) ##STR58## yellow60 " ##STR59## yellow61 " ##STR60## yellow62 " ##STR61## yellow63 " ##STR62## yellow64 " ##STR63## yellow65 " ##STR64## orange66 " ##STR65## yellowish red67 " ##STR66## yellowish orange68 " ##STR67## yellowish orange69 " ##STR68## yellow70 " ##STR69## yellow71 " ##STR70## yellow72 " ##STR71## yellow73 " ##STR72## yellow74 " ##STR73## yellow75 " ##STR74## yellow76 " ##STR75## yellow77 " ##STR76## orange78 " ##STR77## yellowish red79 " ##STR78## yellowish orange80 " ##STR79## yellowish orange81 " ##STR80## yellow82 " ##STR81## yellow83 Formula (4) ##STR82## yellow84 " ##STR83## yellow85 " ##STR84## yellow86 " ##STR85## yellow87 "88 " ##STR86## " - ##STR87## yellow89 " ##STR88## yellowish orange90 " ##STR89## yellowish orange91 ##STR90## ##STR91## orange92 " ##STR92## red93 " ##STR93## yellow94 ##STR94## ##STR95## yellow95 " ##STR96## orange96 ##STR97## ##STR98## red97 " ##STR99## yellow98 " ##STR100## "99 ##STR101## ##STR102## orange100 ##STR103## " "101 " ##STR104## yellow102 " ##STR105## yellowish orange103 " ##STR106## yellow104 Formula (5) ##STR107## red105 " ##STR108## orange106 " ##STR109## "107 " ##STR110## yellowish red108 " ##STR111## yellowish orange109 " ##STR112## yellowish orange110 " ##STR113## yellowish orange111 ##STR114## ##STR115## yellow112 " ##STR116## "113 " ##STR117## orange114 Formula 14 ##STR118## red115 " ##STR119## yellow116 " ##STR120## yellow117 " ##STR121## yellowish orange118 " ##STR122## orange119 " ##STR123## yellowish red120 ##STR124## ##STR125## red121 " ##STR126## yellow122 ##STR127## ##STR128## orange123 " ##STR129## red124 " ##STR130## yellow125 " ##STR131## "126 " ##STR132## "127 ##STR133## ##STR134## yellow128 ##STR135## ##STR136## yellow129 " ##STR137## yellowish red130 Formula (2) ##STR138## yellow131 " ##STR139## yellowish orange132 " ##STR140## orange133 " ##STR141## yellowish red134 " ##STR142## yellow135 " ##STR143## orange136 ##STR144## ##STR145## red137 " ##STR146## yellow138 " ##STR147## yellowish red139 " ##STR148## yellow140 ##STR149## ##STR150## yellow141 " ##STR151## red142 " ##STR152## yellow143 " ##STR153## yellow144 " ##STR154## yellow145 " ##STR155## yellow146 " ##STR156## yellow147 " ##STR157## yellow148 " ##STR158## bluish__________________________________________________________________________ red __________________________________________________________________________Example Dye Hue__________________________________________________________________________149 ##STR159## golden yellow150 ##STR160## reddish yellow151 ##STR161## "152 ##STR162## orange153 ##STR163## bluish red154 ##STR164## dull bluish red__________________________________________________________________________

Claims

1. An acid azo dye which in the form of the free acid has the formula ##STR165## where R.sup.1 is hydrogen, chlorine or bromine,

R.sup.2 is hydrogen, chlorine, bromine, nitro, methyl or trifluoromethyl,

R.sup.3 is hydrogen; C.sub.1 to C.sub.8 alkyl; C.sub.1 to C.sub.8 alkyl substituted by hydroxy, C.sub.1 to C.sub.8 alkoxy or phenoxy; C.sub.2 to C.sub.8 alkyl interrupted by oxygen and substituted by hydroxy or phenyl; benzyl; phenylethyl; cyclohexyl; phenyl; phenyl substituted by chlorine, bromine, nitro, methyl, ethyl, methoxy, ethoxy, phenoxy or di-C.sub.1 to C.sub.4 -alkylamino; naphthyl; pyridyl; thienyl; or furyl;

n is 1, 2 or 3 and

K is ##STR166## where B.sup.1 and B.sup.2 independently of one another are hydrogen; C.sub.1 to C.sub.4 alkyl; C.sub.2 to C.sub.4 alkyl substituted by hydroxy, cyano, C.sub.1 to C.sub.4 alkoxy, C.sub.1 to C.sub.4 alkanoyloxy or C.sub.1 to C.sub.4 alkoxycarbonyl; C.sub.3 to C.sub.9 alkyl interrupted by oxygen and substituted by hydroxy or phenyl; cyclohexyl; benzyl; phenylethyl or phenyl;

B.sup.3 is hydrogen, chlorine, methyl, C.sub.1 to C.sub.4 alkanoylamino or hydroxysulfonyl,

B.sup.4 is phenyl or phenyl substituted by chlorine, bromine, methyl, ethyl, methoxy or ethoxy,

B.sup.5 is hydrogen, C.sub.1 to C.sub.4 alkyl, cyclohexyl, benzyl, phenyl or phenyl substituted by chlorine, bromine, methyl or ethyl,

B.sup.6 is hydroxy or amino,

B.sup.7 is hydrogen, methyl, carbamoyl or C.sub.1 to C.sub.4 alkoxycarbonyl,

B.sup.8 is cyano or carbamoyl,

B.sup.9 is hydrogen, hydroxy or methyl,

B.sup.10 is B.sup.1 or ##STR167## B.sup.11 is B.sup.1 or ##STR168## B.sup.12 is methyl or phenyl, B.sup.13 is hydrogen, methyl, .beta.-cyanoethyl, .beta.-hydroxyethyl, .beta.-carboxyethyl or .beta.-carbamoylethyl and

p is 0, 1 or 2 and the n hydroxysulfonyl groups are present in the radicals R.sup.3 or K or in the ring bearing the substituents R.sup.1 and R.sup.2.

2. A dye according to the formula in claim 1, in which R.sup.1 is hydrogen.

3. A dye according to the formula in claim 1, in which R.sup.1 is hydrogen and R.sup.2 is hydrogen, chlorine, nitro or trifluoromethyl.

4. A dye according to the formula in claim 1, in which R.sup.3 is C.sub.1 to C.sub.4 alkyl, C.sub.1 - to C.sub.4 alkyl substituted by C.sub.1 to C.sub.8 alkoxy, phenoxy, benzyloxy or phenylethoxy, phenyl or phenyl substituted by chlorine, methyl, methoxy or ethoxy.

5. A dye according to the formula in claim 1, in which

K is ##STR169## B.sup.1 to B.sup.11 having the meanings given in claim 1.

6. The dye according to claim 1 of the formula ##STR170##

7. The dye according to claim 1 of the formula ##STR171##

8. The dye according to claim 1 of the formula ##STR172##

9. The dye according to claim 1 of the formula ##STR173##

10. The dye according to claim 1 of the formula ##STR174##