CA1117937A

CA1117937A - Reactive dyes, their preparation and use

Info

Publication number: CA1117937A
Application number: CA000329858A
Authority: CA
Inventors: Gert Hegar
Original assignee: Individual
Current assignee: BASF Schweiz AG
Priority date: 1978-06-16
Filing date: 1979-06-15
Publication date: 1982-02-09
Also published as: FR2428664A1; JPS55796A; JPS6250509B2; FR2428664B1; GB2024236B; CH635860A5; BR7903811A; BE877007A; DE2924000C2; ES481610A1; GB2024236A; DE2924000A1; CS205148B2

Abstract

Abstract The present invention relates to reactive dyes of the formula (1) , in which A is a benzene or naphthalene radical which can contain as further substituents one or more alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, acylamino groups having 1 to 6 carbon atoms, benzoylamino, amino, ureido, hydroxy, carboxy, halogen or sulfo groups, the benzene radical B can contain as further substituents those named under A, R1 and R2 independently of one another are each a hydrogen atom or an alkyl radical having 1 to 4 carbon atoms which can be substituted by chloro, hydroxy, cyano, carboxy or sulfo, and R3 is a hydrogen atom, an alkyl radical having 1 to 4 carbon atoms which can be substituted by the substituents named under R1 and R2, alkoxy-alkyl having 1 to 4 carbon atoms in the alkoxy radical and 1 to 4 carbon atoms in the alkyl radical, benzyl which can be substituted by sulfo or methyl, cyclohexyl, naphthyl which can be substituted by sulfo, an unsubstituted phenyl radical or a substituted phenyl radical of the formula in which R4 is C1-4-alkyl, C1-4alkoxy- C1-4-alkoxyalkoxy, acetylamino, ureido, carboxyl, halogen, sulfo, sulfomethyl, trifluormethyl, sulfamoyl, carbamoyl, nitro or hydroxyl and R5 is a hydrogen atom or one of the substituents named under R4, and if several substituents R4 are present these can be identical or different, or in which R2 and R3 together with the N atom form a six-membered heterocyclic radical, and the radical or radicals of the formula

Description

r~t7 ; CIBA-GEIG~ AG ~ 1 -Basel (Switzerland) _11758/-Reactive dyes~ their preparation and use The invention relates to reactive dyes of the formula [A ~ ~ N =N - ~ 3 1 ~ 1 ~C~ 2 (1) , F
in which A is a benzene or naphthalene radical which can contain as further substituents one or more alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carhon atoms, acylamino groups having 1 to 6 carbon~atoms, ben~oylamino, amino, ureido, hydroxy, carboxy, halogen or sulfo groups, the benzene radical B can contain as further substituents those named under A9 Rl and R2independently of one another are each a hydrogen atom or an alkyl radical having 1 to 4 carbon atoms which can be substituted by chloro, hydroxy, cyano, carboxy or sulfo, and R3 is a hydrogen atom, an alkyl radical having 1 to 4 carbon atoms which can be substituted by the substituents named under Rl and R2, alkoxy-alkyl having 1 to 4 carbon atoms in the alkoxy radical and 1 to 4 carbon atoms in the alkyl radical, benzyl which can be substituted by sulfo or methyl, cyclohexyl, naphthyl which can be substituted by sulfo, an unsubstituted phenyl radical ~`
or a substituted phenyl radical of the formula H

R5 (R~ 3 in which R4 is Cl ~-alkyl, Cl 4-alkoxy, Cl ~-alkoxyalkoxy, acetylamino, ureido, carboxyl, halogen, sulfo,sulfomethyl, trifluormethyl, sulfamoyl, carbamoyl, nitro or hydroxyl and R5 is a hydrogen atom or one of the substituents named .

~ . , : . ` `: :

- 2 -under R4, and if several substituents R4 are present these can be identical or di~ferent, or in which R2 and R3 together with the N atom form a six-membered heterocyclic radical, and the radical or radicals of the formula - N - C C - N - R
. ., , 3 1 ~C~N R2 (2) F
is or are bonded to A and/or to the naphthalene nucleus, which carries one of the two complex forming oxygen atoms.
The radicals A and B can contain the substituents customary in azo dyes. The following are examples o~
further substituents: alkyl groups having 1 to 4 carbon atoms, such as methyl 7 ethyl 9 propyl, isopropyl and butyl, alkoxy groups having 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy and butoxy, acylamino groups having 1 to 6 carbon atoms, such as acetylamino, propionyl amino and benzoylamino, amino groups, such as -NH2, methyl-amino and ethylamino, the ureido, hydroxyl and carboxyl group, halogen, such as ~luorine, chlorine and bromine, and the sulfonic acid group.
me radical A contains in particular one or more sulfonic acid groups as further substituents. The radical B contains a further substituent in particular in the para-position relative to the complex-~orming oxygen atom. Alkyl radicals Rl and R2 can be substituted, for example by chlorine, hydroxyl, cyano, carboxyl and sul~o~
Examples of Rl and R2 are: methyl, ethyl, propyl, iso-propyl, butyl, isobutyl, sec.-butyl, tert.-butyl hydroxyethyl, ~-chloroethyl, ~-cyanoethyl, ~-cyanomethyl, r-cyanopropyl, ~-carboxyethyl, sul~omethyl and ~-sulfo-ethyl. Examples of R3 are: hydrogen, the same sub-stituted and unsubstituted alkyl radicals as mentioned above for Rl and R2, alkoxyalkyl having 1 to 4 carbon atoms in the alkoxy radical and 1 to 4 carbon atoms in the aIkyl radical, such as methoxyethyl, methoxypropyl, ethoxyethyl, i . , ; -:. . , :, ethoxypropyl and methoxybutyl, cyclohexyl, benzyl, 4-sulfo-benzyl, 4-methylben~yl and especially phenyl, which can be substituted by Cl 4-alkyl, Cl 4-alkoxy, Cl 4-alkoxyalkoxy, acetylamino, ureido, carboxyl, halogen, sulfo, sulfomethyl, trifluoromethyl, sulfamoyl, carbamoyl, nitro or hydroxyl, in which case the conditions given in the explanation of the formula (1) apply, or naphthyl, which can be substituted by sulfo; furthermore, R2 and R3 can be cyclised to a six-membered N-heterocyclic ring, which can contain a further hetero atom, such as nitrogen, oxygen and sulfur. Examples of the amino radical -NR2R3 in the formula (1) are: -NH2, methyl-amino, ethylamino, propylaminog isopropylamino, butylamino, ~-methoxyethylamino, ~-methoxypropylamino, ~,N-dimethyl-amino, N,N-diethylamino, N-methyl-N-phenylamino, N-ethyl-N-phenylamino, ~-chloroethylamino, ~-hydroxyethylamino, Y-hydroxypropylamino, benzylamino, cyclohexylamino, morpho-lino, piperidino, piperazino and in particular aro~atic amino groups, such as phenylamino, toluidino, xylidino, chloroanilino, anisidino, phenetidino, 3- and 4-sulfo-anilino, 2,5-disulfoanilino, sulfomethylanilino, N-sulfo-methylanilino, 3- and 4-carboxyphenylamino, 2-carboxy-5-sulfophenylamino, 2-carboxy-4~sulfophenylamino, 4-sulfo-naphth-l-yl-amino, 3,6-disulfonaphth-l~yl-amino, 3,6,8-trisulfo-naphth-l-yl-amino and 4,6,8-trisulfonaphth-1-yl-amino.
The ractive dyes of the formula (1) can contain one radical or two radicals of the formula (2). If a reactive dye of the formula (1) contains only one radical of the formula (2) this is bonded either to A or to the naphthalene nucleus which carries one of the two complex-forming oxygen atoms; however, if the dye contains two radicals of the formula (2) one of these radicals is bonded to A and the other is bonded to the above-mentioned naphthalene nucleus.
Preferred reactive dyes are those of the formula '~
,. ,~

.

, ", ::

7~'7 LA N ~N = N~ (53~ 1 N C 11 RZ

(3) in which X is hydrogenl alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms or halogen and A9 Rl, R2 and R3 are as defined under formula (1), and especially reactive dyes of the formula (3) in which A is a benæene radical, which can be substituted by sul~o, methyl 9 meth-oxy, carboxyl and chlorine, or a naphthalene radical, which can be substituted by sulfo, Rl is hydrogen, methyl or ~-hydroxyethyl, R2 is hydrogen, methyl or ethyl, R3 is hydrogen, methyl, ethyl, butyl, methoxypropyl, ~-hydroxy-ethyl, ~-sul~oethyl, phenyl, which can be substituted by sulfo, methyl, methoxy, ethoxy, acetylamino, ureido, carboxyl, chlorine, bromine, sulfomethyl, tri~luoromethyl, sulfamoyl and carbamoyl, in which case the conditions given in the explanationoft~efor~a (1) apply, or naphthyl, which can be substituted by sulfo, and X is hydrogen, methyl, ethyl, methoxy, ethoxy or chloriné.
Preferred reactive dyes are in particular those of the formula O
N = N ~ N = N ~ } - N - C C - N - R3 (~3~ X ~03S . R1 N~N ~2

(4) F
in which Rl is hydrogen or methyl, R2 is hydrogen, methyl :.
or ethyl, R3 is hydrogen, phenyl, which can be substitu-ted by sulfo, methyl, ethyl, methoxy, ethoxy, acetylamino, carboxyl, chlorine, sulfamoyl and carbamoyl, in which case the conditions given in the explanation of the formula (1) apply, or naphthyl, which can be substituted by sulfo, and X is hydrogen, methyl, ethyl, methoxy, ethoxy or .~` ~.

. ! , . : . .. .

chlorine.
A valuable reactive dye of the category defined by the formula (4) is the reactive dye o~ the ~ormula S03H ~ ~ Cu - ~
~ N ~ N ~ - N = N ~ N ~ C C - NH
S03H CH3 N03 , 2

(5). F
me preparation o~ the reactive dyes o~ the for-mula (1) comprises subjecting a dye of the formula O--Cu - O -A - N = N ~ N = N ~ (S03H)1_3 t Rl )1 2

(6) in which the amino group or groups of the formula - NH (7) Rl is or are bonded to A and/or to the naphthalene nucleus which carries one of the tWQ complex-forming oxygen ato7ns, 1 or 2 mols of 2~4~6-trifluoro-s-triazine o~ the ~ormula C~,N~c F
N N (8) ~C' F
and 1 or 2 mols of an amino compound o~ the formula ~ 3 (9) to condensation reactions with one another, the said .. ... - ,.... . ........ .
i , ' ' ' ~ ;:

,.,. :
: , , ., C~

reactions being carried out in any order.
In a preferred embodiment the starting materials used are dyes of the formula ~ O - Cu Q ~
A - N = N ~ N - N ~ I f ~=~ ~ (S03~) 1 3 ~ Rl Jl 2 (10) in which X is hydrogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms or halogen and A and R
are as defined under formula (1).
The starting materials used are in particular dyes of the formula (10) in which A is a benzene radical, which can be substituted by sulfo, methyl, methoxy, carboxyl and chlorine, or a naphthalene radical, which can be substitu-ted by sulfo, Rl is hydrogen, methyl or ~-hydroxyethyl and X is hydrogen, methyl, ethyl, methoxy, ethoxy or chlorine, and amino compounds of the formula (9) in which R2 is hydrogen, methyl or ethyl and R3 is hydrogen, methyl, ethyl, butyl, methoxypropyl, ~-hydroxyethyl, ~-sul~oethyl, phenyl, which can be substituted by~sulfo, methyl, methoxy, ethoxy, acetylamino, ureido, carboxyl, chlorine, bromine, sulfomethyl, trifluoromethyl, sulfamoyl and carbamoyl, in which case the conditions given in the explanation ofthefor-mula (1) apply, or naphthyl, which can be substituted by sul~o.
The preferred reactive dyes of the formula (4) are obtained by sub~ecting a dye of the ~ormula Cu--O
(503H~1_2 X U35 ~ ~ (11), 2,4,6-tri~luoro-s-triazine o~ the formula (8) and an amino ,. . , . ;, ~ .

7~ 7 compound of the formula (9) to condensation reactions with one another, the said reactions being carried out in any order and Rl, R2, R3 and X in the formulae (11) and (9) being as defined under formula (4).
Since the individual process steps indicated above, i.e. multiple condensation reactions in different orders, can, if desired, in some cases also be carried out simul-taneously, different process variants are possible.
The starting materials to be used for each partial reac-tion can be seen from formula (1). In general, the reaction is carried out in successive steps, and the order of the simple reactions between the individual reactants of the formulae (6), (8) and (9) can be freely chosen.
The two most important process variants comprise 1. subjec~ing a dye of the formula (6) to a condensation reaction with 1 or 2 mols of 2,4,6-trifluoro-s-triazine of the ~ormula (8) and subjecting the resulting mono- or di-primary condensation product to a condensation reaction with 1 or 2 mols of an amino compound of the formula (9);
and 2. subjecting 2,4,6-trifluoro-s-triazine of the ~ormula

(8) to a condensation reaction with an amino compound o~
the formula (9) and subjecting 1 or 2 mols of the result-ing primary condensation product to a condensation reac-tion with a dye of the formula (6).
~ he preferred procedure for the preparation of the reactive dye of the formula (5) comprises subjecting the dye of the formula S03H 0 Cu ---G
N - N ~ N = N ~ NH

03H 3 03 ~ CH3 (12) to a condensation reaction with 2,4,6-trifluoro-s-triazine and subjecting the resulting primary condensation product -~

~- .. , . . i,... : :, ;, ~ ~ , , ,1; . . . .

' !, ' ', ., ; , ~ :

to a condensation reaction with ammonia, The dyes of the ~ormula (6) which are to be used as starting materials are obtained by coupling a diazotised aminobenzene or aminonaphthalene, which can be further substituted as indicated above, with an ortho-alkoxy- or -hydroxy-aminobenzene, which likewise can be ~urther sub-stituted as indicated above, such as o-anisidine, cresi-dine, 2,5-dimethoxyaniline or 2-acetylaminophenol, diazo-tising the resulting monoazo compound, if necessary after saponifying the amino group to be diazotised, and coupling the resulting product with a naphtholsulfonic acid or aminonaphtholsulfonic acid and preparing the copper complex of the resulting disaæo dye, especially with dealkylation, by reaction with copper donors.
The dia~otisation of the diazo componentsis as a rule effected by the action of nitrous acid in aqueous/
mineral acid solution at low temperature and the coupling reaction with the coupling componentsis carriedoutat weakly acid or neutral to weakly alkaline pH values.
Salts which contain copper as the cation) for example copper sulfate, copper chloride or copper acetate, can be used as the copper donor. In some cases it is advantageous to use complex copper compounds, for example in the form of copper/ammine complexes, such as copper tetraammine sulfates obtained from copper sulfate and ammonia, pyridine or monoethanolamine, or in the form of compounds which contain the copper bonded as a complex, for example complex copper compounds o~ the alkali metal salts of aliphatic aminocarboxylic acids or hydroxy-carboxylic acids, such as of glycocoll, of lactic acid and, in particular, of tartaric acid, such as sodium copper tartrate.
The treatment with the copper donor is carried out in an aqueous or organic-aqueous medium, ~or example at room temperature if the starting compounds are easily metallisable or, if dealkylation has to take place at the same time as metallisation, by warming to temperatures ,. . ~ j, , . - -t7 _ g _ between 50 and 120C in an open vessel, for example under refl~x, or, if necessary, in a closed vessel under pressure, the pH conditions being determined by the nature of the metallisation process chosen; for example,the copper complex is prepared at an acid pH using copper sul-fate and at an alkaline pH using copper tetraammine sul-fate.
If desired, solven-ts, such as, for example, alco-hol, dimethylformamide and the like, can also be added during the metallisation.
Examples of starting compounds for the preparation of the dyes of the formula (6) are:
a) aminobenzenes and aminonaphthalenes (radical A):
aniline, o-, m- and p-toluidines, o- 9 m~ and p-anisidines, o-, m- and p-chloroanilines, 2,5-dichloroaniline, a- and ~-naphthylamine, 2,5-dimethylaniline, 5-nitro-2-amino-anisole, 4-aminodiphenyl, aniline-2-, -3- and -4-carboxylic acids, 2-aminodiphenyl ether, 2-, 3- or 4-aminobenzene-sulfonamide or -sulfomono-methyl- or -ethyl-amides or -sulfonyldimethyl- or -sulfonyldiethyl-amides, aniline-2~, -3- and -4-sulfonic acid, aniline-2,5-disulfonic acid, 2,4-dimethylaniline-6-sul~onic acid, 4-chloro-5-methyl-aniline-2-sulfonic acid, aniline-2,4-disulfonic acid, aniline-3,5-disulfonic acid, 2-amino-4- or -5-sulfobenzoic acid, 2-methylaniline-3,5-disulfonic acid, 2-methylaniline-5-sulfonic acid, 2-methoxyaniline-3,5-disulfonic acid, 2-chloroaniline-4-sulfonic acid, 2,3-dimethylaniline-4,6-disulfonic acid, 2,5-dimethylaniline-4,6-disulfonic acid9 5-chloro-4-methylaniline-2-sul~onic acid, 3-acetylamino-aniline-6-sulfonic acid, 4-acetylaminoaniline-2-sulfonic acid, 4-chloroaniline-2-sulfonic acid, 3,4-dichloro-aniline-6-sulfonic acid, 4 methylaniline-2-sulfonic acid, 3-methylaniline-6-sulfonic acid, 2,4-dimethoxyaniline-6-sulfonic acid, 4-methoxyaniline-2-sulfonic acid, 5-methoxy-aniline-2-sulfonic acid, 2,5-dichloroaniline-4-sulfonic acid, 2,4-dimethylaniline-S-sul~onic acid, 2-methoxy-aniline-5-sulfonic acid, 2-methylaniline-4-sulfonic acid, r ~, : , . ' ' ~ :

, ", . ;

4-nitroaniline-2-sulfonic acid3 4-ethoxyaniline-2-sulfonic acid, 4-ethylaniline-2-sulfonic acid, 4-acetylaminoaniline, 4-ethoxyaniline-3-sul~onic acid, 3,4-dichloroaniline, o-, m- and p-nitroaniline, m- and p-aminoacetanilide, 4-amino-2-acetyl-aminotoluene-5-sulfonic acid, 4-methoxyaniline-3-sulfonic acid, l-aminonaphthalene-2-, -4-, 5-, -6-, -7-or -8-sulfonic acid, 2-aminonaphthalene-1-, -5- or -6-sulfonic acid, l-aminonaphthalene-3,6- or -5,7-disulfonic acid, 2-aminonaphthalene-1,5- 9 -1 ~ 7-, -3,6-, -5,7-, -4,8-or -6,8-disulfonic acid, 1-aminonaphthalene-2~5,7-tri-sulfonic acid, 2-aminonaphthalene-1,5,7-, -3,6,8- or -4,6,8-trisulfonic acid, 1-amino-2-hydrox~-6~nitro-naphthalene-4-sulfonic acid, 2-amino-1-hydroxynaphthalene-4,8-dis~lfonic acid, 1-amino-3-acetylaminobenzene (saponi-fied), l-amino-3-acetylaminobenzene-5- or -6-sulfonic acid (saponified), l-amino-4-acetylaminobenzene-2-sul~onic acid (saponified), l-amino-3-(N acetyl-N-methylamino)-ben~ene (saponified), 3- or 4-nitroaniline (reduced), 2-methoxy-4- or -5-nitroaniline (reduced)~ 2-methoxy-3-nitro-5-methylaniline (reduced) and 2-methoxy-3-nitro-5-chloroaniline.
b) o-Alkoxy- or o-hydroxy-aminobenzenes (radical B):
l-amino-2-methox~-5-methylbenzene, 1-amino-2,5-dimethoxy-benzene, l-amino-2-methoxybenzene~ l-amino-2-methoxy-5-chlorobenzene, l~amino-2-methoxy-5-ethylbenzene, l-amino-2,5-diethoxybenzene, 1-amino-2-ethoxybenzene and 2-acetyl-aminophenol (saponified).
c) Naphtholsulfonic acids and aminonaphtholsulfonic acids:
2-amino-8-hydroxynaphthalene-6-sulfonic acid, 2-amino-6-hydroxynaphthalene-8-sulfonic acld, 2-amino-5-hydroxy-naphthalene-7-sulfonic acid~ 2-amino-5-hydroxynaphthalene-1,7-disulfonic acid, 2-aminobenzoylamino-5-hydroxy-naphthalene-7-sulfonic acid, 2-(4l-aminophenylamino)-5-hydroxynaphthalene-~',7-disulfonic acid, 2 amino-8-hydroxynaphthalene-3,6-disulfonic acid 9 l-aminobenzoyl-amino-8-hydroxynaphthalene-3,6-disul~onic acid, 2 amino-5-hydroxynaphthalene-4,8-disulfonic acid, 1-amino-8-hydroxy-.
., ., . . -~ ..

. .; .

naphthalene-3,6- or -4,6-disul~onic acid, 2-N--phenylamino-5-hydroxynaphthalene-7-sulfonic acid, 2~N-methylamino-5-hydroxynaphthalene-7-sulfoni.c acid, 2 N-acetyl-N-methyl-amino 5-hydroxynaphthalene-7-sulfonic acid, 2-N-(2'-hydroxyethylamino)-5-hydroxynaphthalene-7-sulfonic acid, 2-N-methylamino-8 hydroxynaphthalene-6-sulfonic acid, 3-amino-2-hydroxynaphthalene-7~sul~onic acid, l-hydroxy-naphthalene-3,6-disulfonic acid, 1-hydroxynaphthalene-4,8-disulfonic acid, l-hydroxynaphthalene-3,8-disulfonic acid, l-hydroxynaphthalene-3,6,8-trisul~onic acid and l-hydroxy-naphthalene-4-, -5- or -8-sulfonic acid.
The preparation of the dyes o~ the formula (6) is not described in every case in the illustrative examples given below, but is obvious from what has been stated above.
Further starting materials which can be used ~or the preparation o~ the reactive dyes of the formula (1) are 2,4,6-trifluoro-s-triazine o~ the ~ormula (8) (cyanuric fluoride) and also, for example, the ~ollowing amino com-pounds o~ the ~ormula (9): ~mmonia~ methylamine, dimethyl-amine, ethylamine, diethylamine, propylamine, isopropyl-amine, butylamine, dibutylamine, isobutylamine, sec.-butyl-amine, tert.-butylamine, methoxyethylamine, ethoxyethyl-amine, methoxypropylamine, chloroethylamine, hydroxyethyl-amine, dihydroxyethylamine, hydroxypropylamine, amino-ethanesul~onic acid, ~-sulfatoethylamine, benzylamine, cyclohexylamine, aniline, m- and p-toluidine, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- and 3,5-dimethylaniline, m- and p-chloro-aniline, N-methylaniline, N-ethylaniline, 3- or 4-acetyl-aminoaniline, m- and p-nitroaniline, m- and p-aminophenol, 2-methyl-4-nitroaniline, 2~methyl-5-nitroaniline, 2,5-dimethoxyaniline, 3-methyl-4-nitroaniline, 2-nitro-4-methylaniline, 3-nitro-4-methylaniline, 3-amino-4-methyl-aniline, 4-amino-3-methylaniline, 2-amino-4-methylanilîne, m- and p-anisidine, m- and p-phenetidine, 2-methoxy-5-methylaniline, 2-e-thoxy-5 methoxyaniline, 4-bromoaniline, 3-aminobenzamide, 4-aminophenylsul~amide, 3--tri~luoro-1~' - ~. - , . , -; - ,: , . . . ...
: ~, ., -. - , .. .

- - ; . . , : .:

~Y7~

methylaniline, 3- and 4-aminophenylurea 9 1-naphthylamine, 2-naphthylamine, 2-amino-1-hydroxynaphthalene, 1-amino-4-hydroxynaphthalene, 1-amino-8-hydroxynaphthalene, 1-amino-2-hydroxynaphthalene, 1-amino-7-hydroxynaphthalene, methanilic acid, sulfanilic acid, anilina-2,4-disulfonic acid, aniline-2,5-disulfonic acid, aniline-3,5-disulfonic acid, m- and p-aminobenzoic acid, 4-aminophenylmethane-sulfonic acid, aniline-N-methanesulfonic acid, ~-amino-toluene-4-sulfonic acid, 2-aminotoluene-5-sulfonic acid, p-aminosalicylic acid, 1-amino-4-carboxy-benzene-3-sulfonic acid, l-amino-2-carboxy-benzene-5 sulfonic acid, 1-amino-5-carboxy-benzene-2-sulfonic acid, 1-naphthylamine-2-, -3-, -4-, -5-, -6-, -7- and -8-sulfonic acid,~l-naphthylamine-2,4-, -2,5-, -2,7-, -2,8-, -3,5-9 -3,6-, -3,7-, ~3,8- 9 -4,6-, -4,7-, -4,8- and -5,8-disulfonic acid, 2-naphthylamine-1,5-, -1,6-, -1,7-, -3,6-, -3,7-, -4,7-, -4,8-, -5,7- and -6,8-disulfonic acid, l-naphthylamine-2,4,6-, -2,4,7-, -2,5,7-, -3,5,7-, -3,6,8- and -4,6,8-trisul~onic acid, 2-naphthylamine-1,3,7-, -1,5,7-, -3,5,7-, -3,6,7-, -3,6,8- and -4,6,8-trisulfonic acid, morpholine, piperidine and piperazine.
The condensation reactions o~ the 2,4,6-trifluoro-s-triazine of the formula (8) with the dyes of the formula (6) and the amino compounds of the formula (9) are prefer-ably carried out in aqueous solution or suspension, at low temperature and at a weakly acid or neutral to weakly alkaline pH value and in such a way that at least one -fluorine atom still remains as a detachable radical in the finished reactive dye of the formula (1). Advantageously,the hydrogen fluoride liberated during the condensation reac-tion is neutralised continuously by adding aqueous alkali metal hydroxides, carbonates or bicarbonates.
The copper complex dyes of the formula (1) are fibre-reac-tive since they contain a detachable ~luorine atom in the s-triazine radical or in each of the two s-triazine radicals.
Fibre-reactive compounds are to be understood as 2-naphthylamine~ 3- J-4- ,-5-,-6-,-7-, and -8-sulfonic acid ,Ç~

, . . -- . ~
.

' . ' , ;' '~ ~
.., ,~ , -~ 7 meaning those which are able to react with the hydroxyl groups o~ cellulose or with the amino groups o~ natural or synthetic polyamides with the formation of covalent chemi-cal bonds.
The reactive dyes of the formula (l) can be iso-lated and processed to usable, dry dye preparations.
Isolation is preferably e~fected at temperatures which are as low as possible, by salting out and ~iltering. The dyes filtered o~ can be dried, i~ desired after adding extenders and/or buffers, for example after adding a mix-ture of equal parts of monosodium phosphate and disodium phosphate; preferably, drying is carried out at tempera-tures which are not too high and under reduced pressure.
In certain cases the dry preparations according to the invention can be prepared direct, i e. without intermediate isolation of the dyes, by spray~drying the entire prepara-tion mixture.
me reactive dyes o~ the ~ormula (l) are novel.
mey are distinguished by high reactivity and yield dye-ings which have good wet ~astness properties and good fastness to light. It should be pointed out in par-ticular that the dyes have good solubility and electrolyte solubility coupled with good exhaustion characteristics and high dye ~ixation and that the non-~ixed portions can be removed easily.
The reactive dyes of the ~ormula (l) are suitable for dyeing and printing very diverse materials, such as silk, leather, wool, high molecular weight polyamide fibres and high molecular weight polyamide/urethanes, but especially cellulose-containing materials having a fibrous structure, such as linen, cellulose, regenerated cellulose and in particular cotton. They are suitable both for the exhaustion process and ~or dyeing by the pad dyeing method, according to which the goods are impregnated with aqueous dye solutions, which if desired can also contain salts, and the dyes are ~ixed a~ter an alkali treatment or in the presence of alkali, if necessary under the action R~ :
f~`

:, ' .

: ' "' " ' ., "' ' . '~' : ' .

~ ¢~ ~7 of heat.
They are also suitable for printing, especially on cotton, but likewise also ~or printing nitrogen-containing fibres, for example wool, silk or mixed fabrics containing wool.
It is advisable to suoject the dyeings and prints to thorough rinsing with cold and hot water, if necessary with the addition of an agent which acts as a dispersant and promotes the diffusion o~ the non-fixed portions.
In the following examples, parts are by weight and temperatures are in degrees centigrade.
Example 1 lO parts of the dye of the formula 503H ~ ~ Cu~ f ~ N = N ~ N - N - ~ CH3 are dissolved in 70 parts of water at pH 7 and the solu-tion is cooled to 0 by adding 40 parts of ice.
2 parts of 2,4,6-trifluorotriazine are added dropwise, with good stirring, a pH value of 6.5 being maintained by adding sodium carbonate solution at the same time.
~ parts by volume of concentrated aqueous ammonia solution are then added and the mixture is stirred for 2 hours at 5 to 10. me resulting reactive dye is precipitated by sprinkling in sodium chloride and filtered off, the dye paste is mixed with an aqueous solu-tion of disodium phosphate and the mixture is dried.
The resulting dye dyes cotton from a long liquor in intense navy blue shades.
Navy blue dyes with similar characteris~ics are obtained when the amines listed in the table below are used in place of ammonia.

~ `t ..

. ~ : : , :
~, .

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.lExample Amines 2 N-methylamine 3 N-methylaniline 4 3,5 dimethylaniline 4-methoxyaniline 6 3-am~nobenzenesulfonic acid 7 4-aminobenzoic acid 8 4-methylaniline

9 3-methylaniline 4-aminobenzenesulfonic acid 11 2-amino-4-methylmethoxybenzene 12 3-trifluoromethylaniline 13 4-aminobenzylsul~onic acid 14 butylamine 2-aminoethanesulfonic acid 16 2-aminoethanol 17 aniline 18 ~-aminoacetanilide 19 4-aminophenylurea 2-aminonaphthalene-6-sulfonic acid 21 2-aminonaphthalene-4,8-disulfonic acid , . .. ~
Example 22 25.3 parts of aniline-2,4-disulfonic acid are diazotised in a conventional manner and the resulting product is coupled in weakly acid solution with 13.7 parts of 3-amino-4-methoxytoluene. The resulting aminoazo dye is precipitated by adding sodium chloride, filtered o~f and dissolved in water again. It is diazotised by adding hydrochloric acid and sodium nitrite and the result-ing product is coupled at a pH value of 8 to 8.5 with 29.5 parts of N-acetyl-N-methyl-2-amino-5-hydroxynaphtha-lene-7-sulfonic acid. 100 parts by volume of concen~-trated aqueous ammonia solution and 140 parts by volume of 1 N copper sulfate solution are now added to the resulting deep violet solution and the mixture is stirred under A`
.. .. . .
.. . ~ . ~ ......................... ...

: ,: : ' ':

7~3'7 _ 16 --reflux at 95 for 12 hoursr The copper complex is precipitated from the deep blue solution by adding sodium chloride and is filtered o~f with suction. In order to saponify the acetyl group, the dye is warmed in 1 N
sodium hydroxide solution for 2 hours at 85; after cool-ing to 25, the mixture is acidified to pH 3 with hydro-chloric acid and the product is filtered off with suction.
35.5 parts of the copper complex dye are dissolved in 250 parts of water to give a neutral solution and the solution is cooled to 0. 150 parts of ice are added and 7.1 parts of 2,4,6-trifluoro-1,3,5-triazine are added dropwise to the solution at a pH of 6 to 7. After the condensation reaction has gone to completion, a solution of 5.4 pàrts of 4-aminotoluene in acetone is added and the condensation reaction is carried out at 5 to 10 and pH
7.5. ~he dye is isolated as a blue-black powder by evaporating the reaction mixture to dryness. It dyes cotton in fast navy blue shades Copper complexes of aminodisazo dyes are ~obtained analogously from the components A = starting componentr B = middle component and N = final component, by two coupling reactions and preparation of the copper complex with demethylation, and, on a condensation reaction with cyanuric fluoride and a second triazine substituent T, these copper complexes yield further fast dyesO

~`

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::
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. ... .... . ..

~7~37 ~ D ~a j aSc .. ~ ~ I
~ _ C ~ o 'O
~ ~ 3 3 ~
a) O ~I El ~ ' o~
C O ~D ~ ~ ~ ~ ~ ~ O S
.,1 ~OO~1 oo~ooo~OOOO~O
~ ~ O ~ 1 ~ S
~ a ~ a~ 3 ~ a ~
_ . ... . ..
, ~
c O~ s S~a X ~ S~ S s ~ 3 ~ I s s sx o ~ o s ~ s s ~
El ~ 4 S o R t~ C ~o o ~ ~ S q~ C ~ o o I 'l 'l X~C X~a , 7 , ~ o~ o~o X o X~
~:~ ~ ~ 3 ,1 ~ u~ ~ o ~ o R I E3 ~ ~ o ~ o c~C ~ ~" S ,~S q~ S ~ ~ R ~ R S s ~I S 0~ s z~c ~ a~ S ~S ~ aG ~e ,'d '' 2~ ~

0~ - 4 ~ 4 = ~ C
~ '1 " ~ ., c R ~ ~a o N N C ~
o 7 ~I c ~ D D ~, ,1 ~ ~ R I
C ;~ = ~ = = = = vl 3 1 o~ u~ 6 Co S ~J s7 ~o ~ C C R ~ O ~ R
Ul 'r~ 6~ a~ 6 ~: .~ c~ ~
. . . _ . . __ .. .___ ___ . __ .

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. C C 'C ~ S ~ C C
~ C .~ CJ r~ I N C C ~1 e~ S~ ~ ~c ~ s :~ ~ ~ C +~ ~a v ~ S El ~ C ~ ~ ~ ~ 3 0 s ' ~ ~ aS aN ~ a .... ..

s ~ s s ~ s s ~ ~ s ~a s ~c ~ 'c ~'c ~ c 0q-~ 0 0 0~1 0q'~ 0~1 Z: S0 S~ S0 S0 ~S'O = = = =
1 0 N ~ al ac ~ Q ~ C ~
N,l ~,1 0~1 0,1 NS 0 --~ +S~

~ S 8 S ~ ~I S
I
C C ~ Y C ~ C C ~ C
I N ~a ~ D
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~? "s~ q~ ~ C ~ c ~ a o ~ ~ D~ C(5 D
I 0 1 ~ I 0 1 0 D 0 .Q 0 = .0 C: : -~, a I c c c~ c c 1~ a ... ... . . _. __ Z ~ N ~ ~ u~~ ;t ~0 ` . `. `' ~ ' `:' ' `

~ 19 --Exam~le 50 14 parts of the copper complex disazo dye of the formula S03H 0~ CU ~o - N - N ~ N - N ~ ~S03H

(in the form of the trisodium salt) are dissolved in 100 parts of water and the solution is cooled to 0 by adding ice. 1.4 parts of disodium hydrogen phosphate are added and 2.75 parts of 2,4,6-tri-fluoro-1,3,5-triazine are now added dropwise, with good stirring, the pH value o~ the reaction solution being kept at 6.5 by adding sodium hydroxide solution at the same time, After the reaction, which is followed by thin layer chromatography, has gone to completion, 2.2 parts of 3-aminotoluene are added and the mixture is allowed to warm to 20, the hydrogen fluoride liberated during the condensation reaction again being neutralised continuously. A dark dye powder is obtained by concen-trating the resulting dye solution in vacuo. The dye dyes materials made of cellulose fibres in fast blue shades.
ample 51

10 parts of the copper complex disazo dye of the ~ormula fO3H P ---~Cu - O
- N = N ~ H03 ~ ~ N,CH3 O~H 3 are dissolved in 100 parts of water at pH 7 A solu-tion of 3.3 parts of 2-(4t-methylphen~lamino)-4,6-di-fluoro-1,3,5-triazine in 15 parts o~ acetone is added and the mixture is stirred for 8 hours at 15, the pH value being kept at 6.5 to 7 by the dropwise addition of 1 N

.. ~ .

.. . . ... . . .. .. ... ...

7 ~ 3 sodium hydroxide. After the indicated reaction time, no further starting material is detectable by chromato-graphy. The dye is precipitated by sprinkling sodium chloride into the solution and is filtered off and dried.
It is identical to the product obtained according to Example 8.
Example 52 14 parts of 2,4,6-trifluoro-1,3,5-triazine are added dropwise, at 0, to a solution of 34.6 parts of the disodium salt of the dye of the formula S03H ~ ~~~ Cu -__ f ~ - N = N ~ N = N ~ ~
H2N ~H3 H035 N-H

in 600 parts of water, with good stirring, the pH value being kept at 6 by adding sodium bicarbonate solution.
After the reaction has gone to completion, 19 parts of 3-aminobenzenesulfonic acid are added and the mixture is stirred for 3 hours at pH 7.5 and a temperature of 25.
The resulting dye of the formula NH ~ NH ~ N=N ~ N - N ~ ~ ~ ~H
S03H CH3 ~3H

dyes cotton in ~ast dark blue shades.
r~ein~ Instructions I
2 parts of the dye obtained according to Example 1 ?re dissolved in 100 parts of water with the addition of 0.5 part of sodium m-nitrobenzenesulfonate. A cotton fabric is impregnated with the resulting solution so that its liquor pick-up is 75% and then dried.
The fabric is then impregnated with a solution which is at 20 and contains, per litre, 5 grams of sodium .. . . . .

~ - ~ ., : i , ~ 7 hydroxide and 300 grams of sodium chloride and squeezed off to a liquor pick-up of 75% and the d~Jeing is steamed for 30 seconds at 100 to 101, rinsed, soaped for a quarter of an hour in a 0.3% boiling solution of a non-ionic det,er-gent, rinsed and dried~

2 parts of the dye obtainable according to Example 1 are dissolved in 100 parts of water.
The solution is added to 1,900 parts of cold water, 60 parts of sodium chloride are added and 100 parts of a cotton fabric are put into this dyebath.
The temperature is raised to 40 and after 30 minutes 4 parts by volume of 30% sodium hydroxide solution, 10 parts of calcined sodium carbonate and a further 60 parts of sodium chloride are added. The temperature is kept at 40 for 30 minutes and the dyeing is then rinsed and soaped for 15 minutes in a 0.3% boiling solution of a non-ionic detergent, rinsed and dried.

.3 , , . . ~. :; . . : .

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A reactive dye of the formula (1) in which A is a benzene or naphthalene radical which can contain as further substituents one or more alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, acylamino groups having 1 to 6 carbon atoms, benzoylamino, amino, ureido, hydroxy, carboxy, halogen or sulfo groups, the benzene radical B can contains as further substituents those named under A, R1 and R2 independently of one another are each a hydrogen atom or an alkyl radical having 1 to 4 carbon atoms which can be substituted by chloro, hydroxy, cyano, carboxy or sulfo, and R3 is a hydrogen atom, an alkyl radical having 1 to 4 carbon atoms which can be substituted by the substituents named under R1 and R2, alkoxyalkyl having 1 to 4 carbon atoms in the alkoxy radical and 1 to 4 carbon atoms in the alkyl radical, benzyl which can be substituted by sulfo or methyl, cyclohexyl, naphthyl which can be substituted by sulfo, an unsubstituted phenyl radical or a substituted phenyl radical of the formula in which R4 is C1-4-alkyl, C1-4-alkoxy, C1-4-alkoxyalkoxy acetylamino, ureido, carboxyl, halogen, sulfo, sulfomethyl, trifluoromethyl, sulfamoyl, carbamoyl, nitro or hydroxyl and R5 is a hydrogen atom or one of the substituents named under R4, and if several substituents R4 are present these can be identical or different, or in which R2 and R3 together with the N atom form a six-membered heterocyclic radical, and the radical or radicals of the formula (2) is or are bonded to A and/or to the naphthalene nucleus, which carries one of the two complex-forming oxygen atoms.

2. A reactive dye according to claim 1, of the formula (3) in which X is hydrogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms or halogen and A, R1, R2 and R3 are as defined in claim 1.

3. A reactive dye according to claim 2, in which A is a benzene radical, which can be substituted by sulfo, methyl, methoxy, carboxyl and chlorine, or a naphthalene radical, which can be substituted by sulfo, R1 is hydrogen, methyl or .beta.-hydroxyethyl, R2 is hydrogen, methyl or ethyl, R3 is hydrogen, methyl, ethyl, butyl, methoxypropyl, .beta.-hydroxyethyl, .beta.-sulfoethyl, phenyl, which can be substitu-ted by sulfo, methyl, methoxy, ethoxy, acetylamino, ureido, carboxyl, chlorine, bromine, sulfomethyl, trifluoromethyl, sulfamoyl and carbamoyl, in which case the conditions given in claim 1 apply, or naphthyl, which can be sub-stituted by sulfo, and X is hydrogen, methyl, ethyl, methoxy, ethoxy or chlorine.

4. A reactive dye according to claim 2, of the formula (4) in which R1 is hydrogen or methyl, R2 is hydrogen, methyl or ethyl, R3 is hydrogen, phenyl, which can be substitu-ted by sulfo, methyl, ethyl, methoxy, ethoxy, acetylamino, carboxyl, chlorine, sulfamoyl and carbamoyl, in which case the conditions given is claim 1 apply, or naphthyl, which can be substituted by sulfo, and X is hydrogen, methyl, ethyl, methoxy, ethoxy or chlorine.

5. The reactive dye according to claim 4, of the formula (5)

6. A process for the preparation of a reactive dye of the formula (1) in which A is a benzene or naphthalene radical which can contain as further substituents one or more alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, acylamino groups having 1 to 6 carbon atoms, benzoylamino, amino, ureido, hydroxy, carboxy, halogen or sulfo groups, the benzene radical B can contains as further substituents those named under A, R1 and R2 independently of one another are each a hydrogen atom or an alkyl radical having 1 to 4 carbon atoms which can be substituted by chloro, hydroxy, cyano, carboxy or sulfo, and R3 is a hydrogen atom, an alkyl radical having 1 to 4 carbon atoms which can be substituted by the substituents named under R1 and R2, alkoxy-alkyl having 1 to 4 carbon atoms in the alkoxy radical and 1 to 4 carbon atoms in the alkyl radical, benzyl which can be substit-uted by sulfo or methyl, cyclohexyl, naphthyl which can be sub-stituted by sulfo, an unsubstituted phenyl radical or a substituted phenyl radical of the formula in which R4 is C1-4-alkyl, C1-4-alkoxy, C1-4-alkoxyalkoxy, acetylamino, ureido, carboxyl, halogen, sulfo, sulfomethyl, trifluoromethyl, sulfamoyl, carbamoyl, nitro or hydroxyl and R5 is a hydrogen atom or one of the substituents named under R4, and if several substituents R4 are present these can be identical or different, or in which R2 and R3 together with the N atom form a six-membered heterocyclic radical, and the radical or radicals of the formula (2) is or are bonded to A and/or to the naphthalene radical, which carries one of the two complex-forming oxygen atoms, which comprises subjecting a dye of the formula (6) in which the amino group or groups of the formula (7) is or are bonded to A and/or to the naphthalene nucleus which carries one of the two complex-forming oxygen atoms, 1 or 2 mols of 2,4,6-trifluoro-s-triazine of the formula (8) and 1 or 2 mols of an amino compound of the formula (9) to condensation reactions with one another, the said reactions being carried out in any order

7. A process according to claim 6, wherein the start-ing material used is a dye of the formula (10) in which X is hydrogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms or halogen and A and R
are as defined in claim 6.

8. A process according to claim 7, wherein the start-ing materials used are a dye of the formula (10) in which A is a benzene radical, which can be substituted by sulfo, methyl, methoxy, carboxyl and chlorine, or a naphthalene radical, which can be substituted by sulfo, R1 is hydrogen, methyl or .beta.-hydroxyethyl and X is hydrogen, methyl, ethyl, methoxy, ethoxy or chlorine, and an amino compound of the formula (9) in which R2 is hydrogen, methyl or ethyl and R3 is hydrogen, methyl, ethyl, butyl, methoxypropyl, .beta.-hydroxyethyl, .beta.-sulfoethyl phenyl, which can be substitu-ted by sulfo, methyl, methoxy, ethoxy, acetylamino, ureido, carboxyl, chlorine, bromine, sulfomethyl, trifluoromethyl, sulfamoyl and carbamoyl, in which case the conditions given in claim 6 apply, or naphthyl, which can be substituted by sulfo.

9. A process according to claim 7, for the prepara-tion of a reactive dye of the formula (4) in which R1 is hydrogen or methyl, R2 is hydrogen, methyl or ethyl, R3 is hydrogen, phenyl, which can be substitu-ted by sulfo, methyl, ethyl, methoxy, ethoxy, acetylamino, carboxyl, chlorine, sulfamoyl and carbamoyl, in which case the conditions given in claim 6 apply, or naphthyl, which can be substituted by sulfo, and X is hydrogen, methyl, ethyl, methoxy, ethoxy or chlorine, which comprises sub-jecting a dye of the formula (11), 2,4,6-trifluoro-s-triazine of the formula (8) and an amino compound of the formula (9), in which R2 and R3 are as defined above, to condensation reactions with one another, the said reactions being carried out in any order.

10. A process according to claim 9, for the prepara-tion of the reactive dye of the formula (5) which comprises subjecting the dye of the formula (12) to a condensation reaction with 2,4,6-trifluoro-s-triazine and subjecting the resulting primary condensation product to a condensation reaction with ammonia

11. A process for dyeing or printing a material, which comprises contacting the material with a reactive dye as defined in claim 1.

12. A process according to claim 11, for dyeing cellulose fibres.

13. A textile material, dyed or printed by the process of claim 11 or 12.