Acid azo dyes from a 3-amino-benzisothiazole-[2,1]-5-sulfonic acid diazo component

Abstract

Acid monoazo dyes of the formula ##STR1## in which X is hydrogen, chloro, bromo, nitro, C.sub.1 to C.sub.4 alkyl, methoxy, ethoxy or C.sub.2 to C.sub.4 alkanoylamino and K is a radical of a coupling compound as defined below. The dyes are suitable for dyeing natural or synthetic polyamides giving colorations with very good fastness properties.

Description

The invention relates to compounds which in the form of the free acids have the formula (I): ##STR2## in which X is hydrogen, chloro, bromo, nitro, C.sub.1 to C.sub.4 alkyl, methoxy, ethoxy or NHCO-alkyl, the alkyl being C.sub.1 to C.sub.4 ;

K is a radical of the formula: ##STR3## R.sup.1 is hydrogen, chloro, methyl, methoxy or ethoxy; R.sup.2 is hydrogen, chloro, methyl, ethyl, benzyl, sulfobenzyl, methoxy, ethoxy, carboxy, NHCO-(C.sub.1 to C.sub.4 alkyl), NHCOCH.sub.2 Cl, NHCOCHCl.sub.2, NHCONH.sub.2 or SO.sub.3 H; R.sup.3 is hydrogen, C.sub.1 to C.sub.4 alkyl, C.sub.2 or C.sub.3 hydroxyalkyl or dihydroxyalkyl, .beta.-sulfoethyl, .gamma.-sulfopropyl, .beta.-cyanoethyl, .beta.-hydroxy-.gamma.-chloropropyl, C.sub.1 to C.sub.4 alkoxyethyl, acetoxyethyl, .beta.-chloroethyl, .gamma.-aminopropyl, .gamma.-acetylaminopropyl, .beta.-carboxyethyl, .beta.-carbamoylethyl, benzyl, sulfobenzyl, phenylethyl, sulfophenylethyl or cyclohexyl; R.sup.4 is C.sub.1 to C.sub.4 alkyl, C.sub.2 or C.sub.3 hydroxyalkyl, .beta.-cyanoethyl, .beta.-chloroethyl, C.sub.1 to C.sub.4 alkoxyethyl, benzyl or sulfobenzyl; R.sup.5 is amino, acetylamino, chloroacetylamino, phenoxyacetylamino, benzoylamino, chlorobenzoylamino or dichlorobenzoylamino; R.sup.6 is methyl, chloromethyl, phenyl, chlorophenyl or acetylamino; R.sup.7 is C.sub.1 to C.sub.8 alkyl, C.sub.2 or C.sub.3 hydroxyalkyl, phenyl-(C.sub.1 to C.sub.4 alkyl), cyclohexyl or phenyl; R.sup.8 is hydrogen, chloro, methyl, methoxy or hydroxysulfonyl; m is zero, 1 or 2; and n is 1 or 2.

Examples of individual radicals X in addition to those already specified are: CH.sub.3, C.sub.2 H.sub.5, C.sub.3 H.sub.7, C.sub.4 H.sub.9, NHCOCH.sub.3, NHCOC.sub.2 H.sub.5, NHCOC.sub.3 H.sub.7 and NHCOC.sub.4 H.sub.9.

Examples of individual alkyl and alkoxyalkyl radicals for R.sup.3 and R.sup.4 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 OCH.sub.3, C.sub.2 H.sub.4 OC.sub.2 H.sub.5, C.sub.2 H.sub.4 OC.sub.3 H.sub.7 and C.sub.2 H.sub.4 OC.sub.4 H.sub.9.

Examples of R.sup.7 in addition to those already specified are: CH.sub.3, C.sub.2 H.sub.5, C.sub.3 H.sub.7, C.sub.4 H.sub.9, C.sub.5 H.sub.11, C.sub.6 H.sub.13, C.sub.8 H.sub.17, ##STR4## C.sub.6 H.sub.5 CH.sub.2, C.sub.6 H.sub.5 C.sub.2 H.sub.4, ##STR5## C.sub.6 H.sub.5 C.sub.3 H.sub.6 and C.sub.6 H.sub.5 C.sub.4 H.sub.8.

Compounds of the formula (I) may be prepared by reacting a diazo compound of an amine of the formula (II): ##STR6## with a coupling component of the formula (III):

HK (III) in which X and K have the meanings given above.

Particular industrial importance attaches to compounds of the formula (Ia): ##STR7## in which X.sup.1 is hydrogen, chloro or bromo; and

K.sup.1 is a radical of the formula ##STR8##

Preferred radicals are therefore:

for R.sup.2 hydrogen, methyl, chloro, acetylamino or SO.sub.3 H; for R.sup.3 and R.sup.4 C.sub.1 to C.sub.4 alkyl, C.sub.2 H.sub.4 OH, CH.sub.2 CHOHCH.sub.3, CH.sub.2 CHOHCH.sub.2 OH, CH.sub.2 --CH.sub.2 --OCOCH.sub.3, CH.sub.2 CH.sub.2 Cl, CH.sub.2 CH.sub.2 CN, CH.sub.2 CHOHCH.sub.2 Cl, CH.sub.2 CH.sub.2 OCH.sub.3, C.sub.2 H.sub.4 OC.sub.2 H.sub.5, C.sub.3 H.sub.6 NHCOCH.sub.3 or CH.sub.2 C.sub.6 H.sub.4 SO.sub.3 H; and for R.sup.1 hydrogen, methoxy or methyl.

Dyes of the formula (I) are red to greenish blue and are particularly suitable for the coloration of natural and synthetic polyamides such as wool, nylon-6, nylon-6,6 and furs.

Dyeings are obtained having very good fastness properties of which fastness to light and wet treatments such as fastness to washing, water, perspiration, fulling and sea water are to be emphasized. The dyes moreover have a very high color strength. In the case of fur dyeing the dyes have good fastness to hot pressing and can be combined to produce brown and black shades.

The following Examples illustrate the invention. The parts and percentages are by weight unless otherwise stated.

EXAMPLE 1

23 parts of 3-aminobenzoisothiazole-5-sulfonic acid is dissolved in 200 parts of water with 4.8 parts of caustic soda, a solution of 6.9 parts of sodium nitrite in water is added and the whole is dripped into a mixture of 200 parts of ice and 46.4 parts of 32% hydrochloric acid while stirring. The suspension of the diazonium salt is stirred for about one hour at 0.degree. to 5.degree. C. and then the excess of nitrite is destroyed with a small amount of sulfamic acid. A solution of 21.63 parts of 3-(N,N-diethylamino)-acetylaminobenzene in 100 parts of water and 11.6 parts of 32% hydrochloric acid is added. After the whole has been stirred for about fifteen minutes the pH is adjusted to 4 to 5 with a solution of 57.5 parts of sodium acetate. The reaction mixture is further stirred until coupling is completed and the dye is then suction filtered and dried at 70.degree. C. at subatmospheric pressure. A dark powder is obtained having the formula: ##STR9## It is soluble in water to give a reddish blue color and gives reddish blue dyeings of good fastness properties on nylon 6, furs, wool and leather.

Dyes having similar tinctorial properties and set out in the following Table are prepared analogously to Example 1.

__________________________________________________________________________No. Diazo component Coupling component Hue on nylon 6__________________________________________________________________________ ##STR10## ##STR11## blue3 " ##STR12## blue4 " ##STR13## reddish blue5 " ##STR14## reddish blue6 " ##STR15## reddish blue7 " ##STR16## reddish blue8 " ##STR17## reddish blue9 " ##STR18## reddish blue10 " ##STR19## blue11 " ##STR20## reddish blue12 " ##STR21## reddish blue13 " ##STR22## blue14 " ##STR23## reddish blue15 " ##STR24## reddish blue16 " ##STR25## blue17 " ##STR26## reddish blue18 " ##STR27## violet19 " ##STR28## violet20 " ##STR29## reddish blue21 " ##STR30## violet22 " ##STR31## violet23 " ##STR32## reddish blue24 " ##STR33## reddish blue25 " ##STR34## reddish blue26 " ##STR35## violet27 " ##STR36## greenish blue28 " ##STR37## dark blue29 " ##STR38## red__________________________________________________________________________

EXAMPLE 30

23 parts of 3-aminobenzoisothiazole-5-sulfonic acid is diazotized analogously to Example 1. A neutral solution of 24 parts of 3-(N,N-diethylamino)-benzenesulfonic acid in 100 parts of water is then added to the suspension of the diazonium salt. The mixture is then adjusted to a pH of 4 to 5 with sodium acetate and further stirred until the coupling is ended. The dye of the composition: ##STR39## is salted out with 160 parts of sodium chloride, suction filtered and dried at 70.degree. C. It dyes nylon 6, wool and fur fast reddish blue shades.

The dyes collected in the following Table may be prepared as described in Example 30; the coupling components of Examples 31 to 40 are dissolved in dilute hydrochloric acid.

__________________________________________________________________________No. Diazo component Coupling component Hue on nylon 6__________________________________________________________________________31 ##STR40## ##STR41## reddish blue32 " ##STR42## reddish blue33 " ##STR43## reddish blue34 " ##STR44## violet35 " ##STR45## reddish blue36 " ##STR46## reddish blue37 " ##STR47## violet38 " ##STR48## reddish blue39 " ##STR49## reddish blue40 " ##STR50## reddish blue41 " ##STR51## reddish blue42 " ##STR52## reddish blue43 " ##STR53## greenish blue44 " ##STR54## greenish blue45 " ##STR55## reddish blue46 " ##STR56## reddish blue47 " ##STR57## blue48 " ##STR58## reddish blue49 " ##STR59## reddish blue50 " ##STR60## blue51 " ##STR61## blue52 " ##STR62## reddish blue53 " ##STR63## blue54 " ##STR64## reddish dark blue55 " ##STR65## violet56 " ##STR66## reddish blue57 " ##STR67## reddish blue58 " ##STR68## reddish blue__________________________________________________________________________

EXAMPLE 59

23 parts of 3-aminobenzoisothiazole-5-sulfonic acid is diazotized as described in Example 1 and an aqueous solution of 25 parts of 3-(N,N-dihydroxyethylamino)-acetylaminobenzene is added to the suspension of the diazonium salt. After coupling has taken place the dye solution is evaporated to dryness. The powder obtained which has the formula: ##STR69## dyes nylon 6, wool and fur clear and fast dark blue hues.

The dyes comprised within the following Table may be prepared according to Example 59.

__________________________________________________________________________No. Diazo component Coupling component Hue on nylon 6__________________________________________________________________________60 ##STR70## ##STR71## reddish blue61 " ##STR72## reddish blue62 " ##STR73## violet63 " ##STR74## reddish blue64 " ##STR75## blue65 " ##STR76## dark blue66 " ##STR77## reddish blue67 " ##STR78## reddish blue68 " ##STR79## reddish blue69 " ##STR80## violet__________________________________________________________________________The following dyes are also obtained analogously to Example 1:No. Diazo component Coupling component Hue on nylon 6__________________________________________________________________________70* ##STR81## ##STR82## blue71* " ##STR83## reddish blue72* " ##STR84## reddish blue73* " ##STR85## reddish blue__________________________________________________________________________ *The coupling components are dissolved in the necessary amount of acetone

The following dyes may be prepared analogously to Example 30:

__________________________________________________________________________No. Diazo component Coupling component Hue on nylon 6__________________________________________________________________________74 ##STR86## CH.sub.3 COCH.sub.2 CONHC.sub.6 H.sub.5 red75 " ##STR87## red76 " ##STR88## red77 " ##STR89## red78 " ##STR90## red79 " ##STR91## red80 " ##STR92## red81 " ##STR93## bluish red82 " ##STR94## bluish red83 " ##STR95## bluish red84 " ##STR96## bluish red__________________________________________________________________________

Claims

1. An acid dye which in the form of the free acid has the formula ##STR97## wherein: X is hydrogen, chloro, bromo, nitro, C.sub.1 - to C.sub.4 -alkyl, methoxy, ethoxy or NHCO-(C.sub.1 to C.sub.4 -alkyl)

R.sup.1 is hydrogen, chloro, methyl, methoxy or ethoxy.

2. A dye as set forth in claim 1 of the formula: ##STR98##

3. A dye as set forth in claim 1 wherein R.sup.1 is hydrogen, methoxy or methyl.

4. A dye as set forth in claim 1 which in the form of free acid has the formula: ##STR99## wherein: X.sup.1 is hydrogen, chloro or bromo.

5. A dye as set forth in claim 1 wherein R.sup.1 is methoxy.

6. A dye as set forth in claim 1 wherein R.sup.1 is methyl.

7. A dye as set forth in claim 1 wherein R.sup.1 is hydrogen.