DE2244537A1 - AZO DYES - Google Patents

Description

The invention relates to new azo dyes that as green reactive dyes for dyeing cellulose textile materials can be used.

It has been found that green reactive dyes with a very good fastness to light and washing or bleaching treatments, which also produce very strong hues during dyeing resulting in salt-containing alkaline baths, can be obtained by using certain copper monoazoamino compounds and certain yellow amino compounds with the help of a chloro-striazine bridging group connects.

309811/1071

ORIGINAL INSPECTED

According to the invention, the dyes of the formula

O ~~ .Cu_ 0 P «

I ^ ^N \ _R

-Il ⁽¹⁾

I Cl

suggest in what

X stands for NO ₀ or SO _x H-2 3

Y stands for H, CH _x or OCH _x or can also be SO _x H, provided X stands for NO ₂ ,

η represents O or 1, R represents H or CH, and R _{1 represents} a group of the formula

CH-CH - (/ V— NO ₀ (2)

or - NR ₂ -R ₅ -NNR ₄ (3)

is where

R _{0 represents} H or CH.

R, ^ Ur is a 1,4-naphthylene _{radical, which can be substituted by SC x} H and / or OCH, or a 1,4-phenylene radical, which can be substituted by CH ,, OCH ,, Cl, SO _x H, CO ₂ H, NHCONH ₂ or iJHCORc substituted

can be, where R, hydrogen or an alkyl group with up to 3 carbon atoms means, stands,

309811/1071

R ^ stands for a sulfophenyl or sulfonaphthyl group, which in the case of fhenyl reiter by Cl, NO ₂ , GH, O, CH ,, acetylamino, 4 ^l -nitro-2'-8ulfophenylvinyl, 4'-nitro-2'-sulfoaniiino or CO ₂ H can be substituted.

According to the invention, a method is proposed for the preparation of the novel dyes \ which is carried out by reacting cyanuric chloride with 1 mol of an amino compound of the formula

NHR

and with 1 mol of 4-nitro-4 -'-- amino3tilbene-2,2SdISuIfOnSaUrB or an amino compound of the formula

R ₄ - N - N ■ - R ₃ - NHR ₂ (5)

converts, where the symbols X, Y, n, R, R ₂ , R * and R _{4 have} the meanings given above.

The process according to the invention can be carried out in an expedient manner by adding a suspension of the oyanuric chloride in an aqueous medium first with the first of the amino compounds a temperature of 0 to 5 ° C until a chlorine atom of the cyanuric chloride is reacted, then the second amino compound is added and the reaction occurs at a slightly higher one Tempei-atur, usually in a range of

3 0 9 811/10 7 1

40 to 45 ° C until a second chlorine atom of the cyanuric chloride responded. The condensations are preferably carried out at a pH of 6 to 7, with an acid-binding Agent is added to neutralize the hydrochloric acid formed during the reaction. When the reaction is over then the new dyes can be isolated by the usual techniques used for the isolation of water-soluble ones Reactive dyes are known), for example by salting out and filtration or by spray drying the reaction mixture, in which the dye was made. If necessary, stabilizers can be added, such as e.g. mixtures of alkali metal hydrogen phosphates.

The compounds of formula (4) used in the above process can be prepared by using an amine the formula

(6)

wherein Rg «H or C ^w ₇ , diazotized, and with an aminonaphtholsulfonic acid of the formula

(7)

HO _x S

couples, where the symbols X. Y, R and η are those given above Aside meanings, and the azo compound obtained in aqueous solution rides a copper salt, for example copper

30981 1/107 1

22A4537

sulfate or copper acetate, converts the reaction under Demethylating conditions is carried out provided H ^ for CH, stands.

Examples of amines of the formula (6) are:

5-nitro-2 ~ aminophenol, 2,5-Dimethox3ranilin-4-3ulfonic acid, 2,5-dimethoxy-4-nitroanillin, 5-nitro-o-anieidin,

2-M3tho3cy-5-methyl-4-nitra aniline and ^{2-Pfethoxy-4-nitro-5-r} inilin Bulfonsäure.

Examples of aminonaphthols of the formula (7) are: 2-Am ± no-5-naphthol-7-3 sulfonic acid, 2-amino-8-naphthol-6-sulfonic acid, 2-methyl aino-5-naplithol-7-8 sulfonic acid, 1- amino ~ 8-naphthol-4,6-3i6- and disulf oic acid, 1 ~ chloro-2-amino-5-naphthol-7-3ulf oic acid, 2-amino-5-naphthol-1 _t 5-disulfonic acid and 2 ~ Anino -8-naphthol-3,6-diaulfonic acid.

The compounds of the formula (5) used in the above process can be obtained by using aminoazobensol sulfonated or that an aniline or kaphthylamine sulfonic acid, which may be further substituted, diazotized and benzene or benzene with an amine coupling in the p-position Naphthalene series couples. Example © for Diaz © components are: A.uilin-0-, m- and p-sulfonic acid,

- and -5-sulfonic acid,
- and -5-sulfonic acid,
Aniline 2,4-, 2,5- and 5,5-disulfonic acid, i-aminonaphthalene-5 "and 6-aulfonic acid. 2-aminonaphthalene-1,5-, 4,8- and 6,8-disulfous acid and 2- aminonaphthalene-3,6 ₁ 8- ur \ d 4,6,8-trisulfonsäur ©.

309811/1071

Examples of coupling components 3incl the aniline,

o- and m-anisidine, anthranilic acid, ο- \ ind m-toluidine, 2 » 3- dimethoxyaniline, cresidine,

m-aminoacetanilide, m-aminophenylurea, 1 ~ aminonaplvfchalin-6, 7- and 8-sulfonic acid, 1 ~ aminonap! Ithalin-6,8-disulfonic acid, N-ethylaniline, N-methyl-o-anisidine and N-fl-hydroxyethyl-m-toluldine.

The new reactive dyes are suitable for dyeing cellulosic parts, which consist of or contain natural or regenerated cellulose. For dyeing such materials Preferably, the new dyes are produced by either a printing or dyeing process on cellulosic fabrics applied, together with an acid-binding agent, such as caustic soda or sodium carbonate or phosphate, silicate or carbonate. The acid binding agent can on the cellulose textile material before, during or after application de3 dye can be applied. The new dyes are particularly suitable for applying from salty alkaline Dye baths which, when used, cause an unusually high proportion of the dye present to react with the fiber. As a result, strong green tones appear on the textile material obtained that have excellent fastness to light and wet treatments, in particular washing and bleaching treatments, demonstrate.

The invention is illustrated in more detail by the following examples, in which all parts and processes * are expressed in weight.

309811/1071

example 1

To a suspension of 1.65 parts of cyanuric chloride in 40 parts of water icLrd at 0 to 5 ° C a solution of 5 * 9 parts of the disodium salt of the copper complex, of 2- (4'-Nitro-2 ^! -Hydro3cyphenylaBo) ™ 8- amino-1-naphthol-3} 6-disulfonic acid in 300 parts of water. The mixture is stirred for 1 hour at 0 to 5 ° C., the pH being kept at 6 to 7 by adding 5 parts of 2u sodium carbonate solution.

Then a solution of 6.0 parts of the trisodium salt of 2- (4'-amino-2'-ureidophenylazo) -naphthalene-3,6,8-trisulfonic acid, water is added in 200 parts, and the mixture is heated to 40 ^e C and stirred for 18 st at 40 ^° C., the pH being kept at 6 to 7 by adding 5 parts of 2N sodium carbonate solution.

Then werderfreak _A 60 parts of salt added and dae mixture is cooled to 2O ⁰ C, stirred for 2 st and filtered. The residue on the filter is washed with 2 χ 20 parts of a 10% saline solution UUD dried at 40 ⁰ C.

The product obtained in this way stains cellular textile materials from salty, alkaline dye baths in green shades, which have an excellent fastness against washing and bleaching treatment a and against Own light.

18 11/10 7 1

BATH ORIGINAL

The following table shows further dyes according to the invention, which are produced in a manner similar to that in Example 1

. _,. . _M consecutive ■ ■. ■ are obtained, namely by ι condensation of cyanuric chloride old 1 mol of the copper complex of the aminoazo compound described in the second column and the amine described in the third column.

309811/1071

E.g. 8-aaino-2- (4'-nitro-5'-methoxy-2 '-
hydroxyphenylazo) -1 -naphthol-3 · ,, 6-
disulfonic acid 2- (4 '-aaiino-2' -methylphenylazo) naphthalene-
4 _v 8-disulfonic acid c \ i - do - 4-Amino-4'-nitrostilbene-2,2'-disulfonic acid 5 - do - 2- (4 ♦ -.Amino-2'-ureidophenylazo) naphthalene-
3,6,8-trisulfonic acid 4th - do - 4- (4 "-Me thy laminophenyl az ο) -4 '-nitro st i Ib en-
2,2 ■ '-di sulfonic acid 8 ~ Amino-2- (4-nitro-2-hydroxyphenylazo) -
1-naphthol-3,6-disulfonic acid - do - 6th - do - 4-amino-4'-nitrostilbene-2,2'-disulfonic acid 7th - do - 2- (4'-amino-2'-ethylphenylaso) naphthalene-
4,8-disulfonic acid 8th 8-amino-2- (5'-methoxy-2'-hydroxy-
phenylazo) -1-naphtho1-3,6-di sulfOn-
acid - do - 9 - do - 4-Amino-4 · -nitrostilbene-2,2'-disulfonic acid 10 - do - 4 -. (4 "-Methylaminophenylazo) -4 '-nitrostilbene-
2,2 * -disulfonic acid 11 - do - 2- (4-amino-2'-ureidophenylazo) naphthalene-
3,6,8-trisulfonic acid 12th

E.g. 8-Amino-2- (4'-nitro-2'-hydrcxyphenylazo) -
1 -naphthol- ?, 5 ', 6-trieulfonaic acid
- do -
- do -
j '- do -
! 2- (4'-amino-2'-ureidophenylazo) naphthalene
3,6,8-trisulfonic acid
2- (4'-amino-2'-ureidophenylazo) naphthalene
4,8-disulfonic acid
4-Amino-4 · -nitrostilbene-2,2'-disulfonic acid
ti
4- (4 "-Hethyiaminoph6nyIazo) -4 -nitrostil-
ben-2,2'-disulfonic acid 13th
14th
a
15th
16

Claims (2)

22U537 Claims Dyes of the formula wherein X stands for HO ₂ or SO _x H, Ϊ stands for H, CH _x or OCH _x or can also be SO _x H, provided 3 3 ■ ο J stands for HO ₂ , η stands for 0 or 1, H stands for H or CH _x and R _{1 stands} for a group of the formula NH -ξ > - CH-CH — VV ^ - NO ₀ (2) SO ₃ H
or - UH ₂ - fi, - N »H - E ^ (3) stands, in front R _{2 represents} H or CH _x , Rz for a 1,4-liaphthylene radical, which is _{substituted by SO x} H imd / or OCH, or a 1,4-phenylene radical, which is substituted by CH ,, OCH _x , Cl, SO _x H ₁ CO ₂ H, HHCOIiH ₂ or HHCOHc 22U537 may be substituted, where R ₁ - is hydrogen or an alkyl group with up to 3 carbon atoms, R _{4 is} a sulfophenyl or sulfoaaphthyl group, which in the case of phenyl is further by Cl, NO ₂ , ΟΗχΟ, CHj, acetylamino, V -Nitro - ^ '- sulfophenylvinyl, 4'-nitro-2 ^f -Bulfoanilino or CO ₂ H can be substituted. 2. Process for the preparation of the dyes according to Claim 1, characterized in that one cyanuric chloride with 1 NoI of an amino compound of the formula NHR and with 1 Hol ^ -nitro-V-aminoetilbene - ^^ - disulfonic acid or an amino compound of the formula R ₄ -HHH ₅ - NHR ₂ (5) converts, where the symbols X, Y, n, R, R ₂ , H and R _{4 have} the meanings given in claim 1. Use of the dyestuffs according to Claim 1 together with an acidic blending agent for dyeing or printing cellulose textile materials. 30981 1/1071