GB2029850A

GB2029850A - Reactive dyes their preparation and use

Info

Publication number: GB2029850A
Application number: GB7920997A
Authority: GB
Original assignee: Ciba Geigy AG
Current assignee: Novartis AG
Priority date: 1978-06-19
Filing date: 1979-06-15
Publication date: 1980-03-26
Also published as: CA1117938A; JPS6261622B2; BR7903817A; ES481659A1; CS209926B2; BE877051A; CH638555A5; DE2924228A1; JPS55799A; FR2429244B1; FR2429244A1; GB2029850B; DE2924228C2

Abstract

Reactive dyes of the formula <IMAGE> in which D1 is a benzene or naphthalene radical, which can be substituted, D2 is a benzene radical, which can be substituted, R1 is hydrogen or C1-4-alkyl, the bridge member -N(R1)- is bonded to a ring carbon atom of D2, R2 is hydrogen or C1-4-alkyl, which can be substituted, and R3 is hydrogen or substituted or unsubstituted alkyl, cycloalkyl, aralkyl or aryl.

Description

SPECIFICATION Reactive dyes their preparation and use The present invention relates to reactive dyes, their preparation and their use.

The invention provides reactive dyes of the formula

in which D, is a benzene or naphthalene radical, which can be substituted, D2 is a benzene radical, which can be substituted, R, is hydrogen or C, 4-alkyl, the bridge member -N(R,)- is bonded to a ring carbon atom of D2, R2 is hydrogen or C, 4-alkyl, which can be substituted, and R3 is hydrogen or substituted or unsubstituted alkyl, cycloalkyl, aralkyl or aryl.

The radicals D, and D2 can contain the substituents customary in azo dyes. Examples of suitable further substituents are the following: alkyl groups having 1 to 4 carbon atoms, such as methyl, ethyl, 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, propionylamino and benzoylamino, carbamoyl, sulfamoyl, amino groups, such as -N H2, methylamino and ethylamino, the ureido, hydroxyl and carboxyl group, halogen, such as fluorine, chlorine and bromine, and the sulfonic acid group.

The radicals D, and D2 contain in particular one or more sulfonic acid groups as further substituents. C, 4-alkyl R, can be: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec.-butyl and tert.-butyl. An alkyl radical R2 can be substituted, for example by chlorine, hydroxyl, cyano, methoxy, carboxyl and sulfo.Examples of R2 are: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec.-butyl, tert.-butyl, sshydroxyethyl, ss-chloroethyl, ss-cyanoethyl, cyanomethyl, ycyanopropyl, ssmethoxyethyl, ffcarboxyethyl, sulfomethyl and fi-sulfoethyl. Examples of R3 are: hydrogen, the same substituted and unsubstituted alkyl radicals which have been mentioned above for R2, methoxypropyl, ethoxyethyl, ethyoxypropyl and methoxybutyl, cyclohexyl, benzyl, 4-sulfobenzyl, 4-methylbenzyl, phenethyl and in particular phenyl, which can be substituted by C, 4-alkyl, C, 4-alkoxy, acetylamino, ureido, carboxyl, halogen, sulfo, sulfomethyl, trifluoromethyl, sulfamoyl and carbamoyl, or naphthyl, which can be substituted by sulfo; R2 and R3 can also be closed to form a six-membered N-heterocyclic ring, which can contain a further heteroatom, such as nitrogen, oxygen and sulfur.Examples of the amino radical -NR2R3 in formula (1) are: -NH2, methylamino, ethylamino, propylamino, isopropylamino, butylamino, ss-methoxyethy- lamino, y-methoxypropylamino, N,N-dimethylamino, N,N-diethylamino, N-methyl-N-phenylamino, N-ethyl-N-phenylamino, P-chloroethylamino, P-hydroxyethylamino, y-hydroxypropylamino, benzylamino, cyclohexylamino, morpholino, piperidino, piperazino and, in particular, aromatic amino groups, such as phenylamino, toluidino, chloroanilino, anisidino, phenetidino, 2-, 3- and 4-sulfoanilino, 2,5-disulfoanilino, sulfomethylanilino, N-sulfomethylanilino, 3- and 4-carboxyphenylamino, 2-carboxy-5-sulfophenylamino, 2-carboxy-4-sulfophenylamino, 4-sulfonaphth- 1 -yl-am- ino, 3,6-disulfonaphth-l -yl-amino, 3,6,8-trisulfonaphth-1 -yl-amino and 4,6,8-trisulfonaphth-1 -yl- amino.

The disazo dyes of the formula (1) are fibre-reactive since they contain a detachable fluorine atom in the s-triazine radical.

Fibre-reactive compounds are to be understood as meaning those which are able to react with the hydroxyl groups of cellulose or with the amino groups of natural or synthetic polyamides with the formation of covalent chemical bonds.

The radical D, does not contain a reactive radical.

Preferred reactive dyes are those of the formula

in which one Y is hydrogen and the other Y is sulfo and D1, R2 and R3 are as defined under formula (1).

Preferred reactive dyes are especially those of the formula (2) in which D, is a benzene radical, which can be substituted by sulfo, methoxy and chlorine, or a naphthalene radical, which can be substituted by sulfo and nitro, R2 is hydrogen, methyl or ethyl and R3 is hydrogen, ethyl, sshydroxyethyl, butyl, phenyl, which can be substituted by methyl, methoxy, ethoxy, chlorine, acetylamino, ureido, carboxyl and sulfo, or naphthyl, which can be substituted by sulfo, or in which the amino group -NR2R3 is the morpholino radical.

Particularly preferred reactive dyes are those of the formula

in which R2 is hydrogen, methyl or ethyl and R2 is hydrogen or phenyl, which can be substituted by methyl, methoxy, chlorine and sulfo.

A valuable reactive dye of the category defined by formula (3) is the reactive dye of the formula

The preparation of the reactive dyes of the formula (1) comprises diazotisation, coupling and condensation reactions using a coupling component of the formula

a a diazo component of the formula D,N H2 (6), a further diazo component of the formula

2,4,6-trifluoro-s-triazine of the formula

and an amino compound of the formula

the said reactions being carried out in any order.

In a preferred embodiment the coupling component of the formula (5) which is used is a compound of the formula

in which one Y is hydrogen and the other Y is sulfo, and the diazo component of the formula (7) which is used is a compound of the formula

The starting materials used are in particular compounds of the formulae (6) and (9) in which D, is a benzene radical, which can be substituted by sulfo, methoxy and chlorine, or a naphthalene radical, which can be substituted by sulfo and nitro, R2 is hydrogen, methyl or ethyl and R3 is hydrogen, ethyl, ss-hydroxyethyl, butyl, phenyl, which can be substituted by methyl, methoxy, ethoxy, chlorine, acetylamino, ureido, carboxyl and sulfo, or naphthyl, which can be substituted by sulfo, or in which the amino group -NR2R3 is the morpholino radical.

The preferred reactive dyes of the formula (3) are obtained by diazotisation, coupling and condensation reactions using a diazo component of the formula

1 amino-8-hydroxynaphthalene-3, 6-disulfonic acid, 1, 3-diaminobenzene-4-sulfonic acid, cyanuric fluoride and an amino compound of the formula (9), in which R2 and R3 are as defined under formula (3), the said reactions being carried out in any order.

Since the individual process steps indicated above, i.e. diazotisation, coupling and condensation, can be carried out in different orders, and, if desired, some process steps can also be carried out at the same time, various process variants are possible. The starting materials to be used for each partial reaction can be seen from formula (1). In general, the reaction is carried out in successive steps and the order in which the simple reactions between the individual reactants of the formulae (5) to (9) are carried out can be freely chosen.

Important process variants comprise 1. reacting a coupling component of the formula (5) with diazotised diazo components of the formulae (6) and (7) to give a disazo compound, subjecting the latter to a condensation reaction with 2,4,6-trifluoro-s-triazine of the formula (8) and subjecting the primary condensation product to a condensation reaction with an amino compound of the formula (9).

The last two reaction steps can also be carried out in a different order, by first subjecting the 2,4,6-trifluoro-s-triazine to a condensation reaction with an amino compound of the formula (9) and subjecting the resulting primary condensation product to a condensation reaction with the abovementioned disazo compound.

The procedure employed for the preparation of the abovementioned disazo compound is advantageously first to couple a diazotised diazo component of the formula (6) with a coupling component of the formula (5) and then to couple the resulting monoazo compound with a diazotised diazo component of the formula (7).

2. diazotising a diazo component of the formula (6) and coupling the resulting compound with a coupling component of the formula (5) and also subjecting 2,4,6-trifluoro-s-triazine of the formula (8) to a condensation reaction with an amino compound of the formula (9), subjecting the primary condensation product to a condensation reaction with a diazo component of the formula (7) and diazotising the resulting secondary condensation product and coupling the resulting product with the monoazo compound prepared initially.

The preferred procedure for the preparation of the reactive dye of the formula (4) comprises diazotising sulfanilic acid and 1 ,3-phenylenediamine-4-sulfonic acid and coupling the reaction product with 1 -amino-8-hydroxy-naphthalene-3, 6-disulfonic acid, subjecting the resulting intermediate of the formula

to a condensation reaction with cyanuric fluoride and subjecting the primary condensation product to a condensation reaction with m-chloroaniline.

The diazotisation of the diazo components is as a rule effected by the action of nitrous acid in aqueous-mineral acid solution at low temperature.

The coupling of the diazo component of the formula (6) with the coupling component of the formula (5) in the ortho-position relative to the H2N group is effected in strongly acid solution, at pH values of 1 to 2; the coupling of the diazo component of the formula (7) with the coupling component of formula (5) in the ortho-position relative to the HO group is effected in the weakly acid or neutral to weakly alkaline range, at pH values between 6.5 and 8.

In general, it is necessary first to carry out the coupling reaction in acid solution. In some cases, for the coupling reactions in which a diaminobenzenesulfonic acid is used as the diazo component of the formula (7), it is advantageous not to use this as itself, but, instead of this, to use an amino-acylamino-benzenesulfonic acid, for example 5-acetylaminoaniline-2-sulfonic acid, from which the acetyl group is detached by saponification after the coupling reaction has gone to completion, before carrying out the further condensation reaction. Furthermore, it is also possible to use a nitro-amino compound, for example 5-nitroaniline-2-sulfonic acid, as the diazo component of the formula (7) and, after the coupling reaction has taken place, to reduce the nitro group to the amino group with sodium sulfide or sodium hydrosulfide.

The condensation reactions of 2,4,6-trifluoro-s-triazine of the formula (8) with the diazo components of the formula (7) and the amino compounds of the formula (9) are preferably effected in aqueous solution or suspension, at low temperature and at a weakly acid or neutral to weakly alkaline pH value, so 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 reaction is neutralised continuously by adding aqueous alkali metal hydroxides, alkali metal carbonates or alkali metal bicarbonates.

The preparation of the diazo intermediates is not described in all cases in the illustrative examples which follow, but is obvious from what has been stated above.

Examples of starting compounds for the preparation of the reactive dyes of the formula (1) are: (a) Coupling components of the formula (5) 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid (H-acid), 1-amino-8-hydroxynaphthalene-4,6- disulfonic acid (K-acid) and 1-amino-8-hydroxynaphthalene-4-sulfonic acid.

(b) Diazo components of the formula (6) aniline, o-, m- and p-toluidines, o-, m- and p-anisidines, o-, m- and p-chloroanilines, 2,5dichloroaniline, a- and ss-naphthylamine, 2,5-dimethylaniline, 5-nitro-2-aminoanisole, 4-aminodiphenyl, aniline-2-, -3- and -4-carboxylic acids, 2-aminodiphenyl ether, 2-, 3- or 4-aminobenzenesulfonamide or 2-, 3- or 4-aminobenzenesulfonic acid mono-methyl- or -ethyl-amides or 2-, 3- or 4-aminobenzenesulfonic acid dimethyl- or diethyl-amides, aniline-2-, -3- and -4-sulfonic acid, aniline-2,5-disulfonic acid, 2,4-dimethyl-aniline-6-sulfonic acid, 4-chloro-5-methylaniline-2sulfonic 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-methoxyaniline3, 5-disulfonic acid, 2-chloroaniline-4-sulfonic acid, 2, 3-dimethylaniline-4, 6-disulfonic acid, 2,5dimethylaniline-4,6-disulfonic acid, 5-chloro-4-methylaniline-2-sulfonic acid, 3-acetylamino-aniline-6-sulfonic acid, 4-acetylaminoaniline-2-sulfonic acid, 4-chloroaniline-2-sulfonic acid, 3,4dichloroaniline-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-methoxyaniline-2-sulfonic acid, 2, 5-dichloroaniline-4-sulfonic acid, 2,4-dimethylaniline-5-sulfonic acid, 2-methoxyaniline-5-sulfonic acid, 2-methylaniline-4-sulfonic acid, 4-nitroaniline-2-sulfuric acid, 4-ethoxyaniline-2-sulfonic acid, 4-ethylaniline-2-sulfonic acid, 4-acetylaminoaniline, 4-ethoxyaniline-3-sulfonic acid, 3,4-dichloroaniline, o-, m- and p-nitroaniline, m- and p-aminoacetanilide, 4-amino-2acetylaminotoluene-5-sulfonic acid, 4-methoxyaniline-3-sulfonic acid, 1-aminonaphthalene-2-, -4-, -5-, -6-, -7-or -8-sulfonic acid, 2-aminonaphthalene-1-, -5- or -6-sulfonic acid, 1-aminonaphthalene-3,6- or -5,7-disulfonic acid, 2-aminonaphthalene-1 ,5-, -1,7-, -3,6-, -5,7-, -4,8- or -6,8-disulfonic acid, 1 -aminonaphthalene-2,5, 7-trisulfonic acid, 2-aminonaphthalene-l ,5, 7-, -3,6,8- or -4,6, 8-trisulfonic acid, 1 -amino-2-hydroxy-6-nitronaphthalene-4-sulfonic acid, 2-amino 1 -hydroxynaphthalene-4, 8-disulfonic acid, 1 -amino-3-acetylaminobenzene (saponified), 1-amino 3-acetylaminobenzene-5- or -6-sulfonic acid (saponified), 1 -amino-4-acetylaminobenzene-2-sul fonic acid (saponified), 1-amino-3-(N-acetyl-N-methylamino)-benzene (saponified), 3- or 4-nitroan iline (reduced), 2-methoxy-4- or -5-nitroaniline (reduced), 2-methoxy-3-nitro-5-methylaniline (reduced) and 2-methoxy-3-nitro-5-chloroaniline.

(c) Diazo components of the formula (7) 1,3- and 1,4-diaminobenzene, 1,3- and 1,4-diaminoanisole, 1,3and 1,4-diaminotoluene, 1,3 diamino-4-chlorobenzene, 1, 3-diamino-4-ethylbenzene, 1, 3-diamino-4-ethoxybenzene, 1,3-diam inobenzene-4-sulfonic acid, 1 ,4-diaminobenzene-2-sulfonic acid, 1 ,4-diaminobenzene-2, 5-disul- fonic acid, 1 ,4-diaminobenzene-2, 6-disulfonic acid and 1, 3-diaminobenzene-4, 6-disulfonic acid.

(d) 2,4,6-Trifluoro-s-triazine of the formula (8) (cyanuric fluoride) (e) Amino compounds of the formula (9) ammonia, methylamine, dimethylamine, ethylamine, diethylamine, propylamine, isopropylamine, butylamine, dibutylamine, isobutylamine, sec.-butylamine, tert.-butylamine, hexylamine, methox yethylamine, ethoxyethylamine, methoxypropylamine, chloroethylamine, hydroxyethylamine, dihydroxyethylamine, hydroxypropylamine, aminoethanesulfonic acid, ,8-sulfatoethylamine, ben zylamine, cyclohexylamine, aniline, o-, m- and p4oluidine, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- and 3,5 dimethylaniline, o-, m- and p-chloroaniline, N-methylaniline, N-ethylaniline, 3- or 4-acetylami noaniline, o-, m- and p-nitroaniline, o-, 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, o-, m- and p-anisidine, o-, m- and p-phenetidine, 2-methoxy-5-methylaniline, 2 ethoxy-5-methoxyaniline, 4-bromoaniline, 3-aminobenzamid, 4-aminophenylsulfamide, 3-trifluo romethylaniline, 3- and 4-aminophenylurea, 1-naphthylamine, 2-naphthylamine, 2-amino-1 - hydroxy-naphthalene, 1-amino-4-hydroxy-naphthalene, 1 -amino-8-hydroxy-naphthalene, 1-am ino-2-hydroxy-naphthalene, 1-amino-7-hydroxy-naphthalene, orthanilic acid, metanilic acid, sul fanilic acid, aniline-2,4-disulfonic acid, aniline-2, 5-disulfonic acid, aniline-3,5-disulfonic acid, anthranilic acid, m- and p-aminobenzoic acid, 4-aminophenylmethanesulfonic acid, aniline-N methanesulfonic acid, 2-aminotoluene-4-sulfonic acid, 2-aminotoluene-5-sulfonic acid, p-amino salicylic acid, 1 -am ino-4-carboxy-benzene-3-sulfonic acid, 1 -amino-2-carboxybenzene-5-sulfonic acid, 1-amino-5-carboxy-benzene-2-sulfonic acid, 1-naphthylamine-2-, -3-, -4-, -5-, -6-, -7- and -8-sulfonic acid, 2-naphthylamine-1-, -3-, -4-, -5-, -6-, -7- and -8-sulfonic acid, 1-naphthylamine 2,4-, -2,5-, -2,7-, -2,8-, -3,5-, -3,6-, -3,7-, -3,8-, -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, 1 naphthylamine-2,4,6-, -2,4,7-, -2,5,7-, -3,5,7-, -3,6,8- and -4,6,8-trisulfonic acid, 2-naphthy lamine-1,3,7-, -1,5,7-, -3,5,7-, -3,6,7-, -3,6,8- and -4,6,8-trisulfonic acid, 2-, 3- and 4 aminopyridine, 2-aminobenzthiazole, 5-, 6- and 8-aminoquinoline, 2-aminopyrimidine, morpho line, piperidine and piperazine.

The reactive dyes of the formula (1) can be isolated and processed to usable, dry dye preparations. Isolation is preferably effected at temperatures which are as low as possible, by salting out and filtering. If desired, the dyes filtered off can be dried after adding diluents and/or buffers, for example after adding a mixture of equal parts of monosodium phosphate and disodium phosphate; preferably, drying is carried out at temperatures 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 mixture in which they were prepared.

The reactive dyes of the formula (1) are novel. They are distinguished by high reactivity and give dyeings which have good wet fastness properties and good fastness to light. Particular mention should be made of the fact that the dyes have good solubility and electrolyte solubility coupled with good uptake characteristics and good fixing of the dye, and that the portions not fixed can be removed easily. The dyeings are dischargeable.

The reactive dyes of the formula (1) are suitable for dyeing and printing very diverse materials, such as silk, leather, wool, high molecular weight polyamide fibres and high molecular weight polyurethanes, but especially cellulose-containing materials of fibrous struc ture, such as linen, cellulose, regenerated cellulose and in particular cotton. They are suitable both for the exhaustion process and for dyeing by the pad dyeing method, according to which the goods are impregnated with aqueous dye solutions, which can also contain salts, and the dyes are fixed after an alkali treatment or in the presence of alkali, if necessary with the action of heat.

They are also suitable for printing, especially of cotton, but are likewise also suitable for printing nitrogen-containing fibres, for example wool, silk or mixed fabrics containing wool.

It is advisable to subject the dyeings and prints to thorough rinsing with cold and hot water, if necessary with the addition of an agent which acts as a dispersing agent and promotes the diffusion of the non-fixed portions.

In the following Examples parts are by weight and the temperatures are given in degrees Centigrade.

Example 1 A neutral solution of 70.2 parts of the disazo dye of the formula

in 500 parts of water is cooled to O to 5"C by adding 300 parts of ice. 10 parts of cyanuric fluoride are allowed to run in in the course of 5 to 10 minutes, with vigorous stirring, and at the same time the pH of the reaction mixture is kept between 6 and 7 by the dropwise addition of 2 N sodium hydroxide solution. After the acylation has gone to completion, 10.7 parts of otoluidine are added to the solution of the difluorotriazine dye and the reaction mixture is warmed to 30 to 35"C and the pH is kept between 7 and 8 by dropwise addition of 2 N sodium hydroxide solution.After the reaction has gone to completion, 5 parts of disodium hydrogen phosphate are added to the solution of the monofluorotriazine dye and the solution is evaporated to dryness in a rotary evaporator at 40 to 45"C.

The dye thus obtained dyes cotton in navy blue shades.

Similar dyes, which also dye cotton in navy blue shades, are obtained when the above example is repeated using equivalent amounts of the amines listed below in place of o-toluidine.

Example Amines 2 m-Toluidine 3 p-Toluidine 4 2,4-Dimethylaniline 5 2,5-Dimethylaniline 6 2,6-Dimethylaniline 7 Ethanolamine 8 Aniline 9 N-Methylaniline 10 N-Ethylaniline 11 m-Chloroaniline 1 2 p-Chloroaniline 13 Acetyl-m-phenylenediamine 14 Acetyl-p-phenylenediamine 15 o-Anisidine 1 6 p-Anisidine 1 7 4-Aminophenyl-urea 1 8 3-Aminophenyl-urea 1 9 p-Aminobenzoic acid 20 Metanilic acid 21 2-Aminonaphthalene-6-sulfonic acid 22 Ammonia 23 m-Anisidine 24 4-Ethoxyaniline 25 Morpholine 26 Taurine Further dyes, which dye cotton in the shades listed in column Ill, are obtained when the amino group-containing disazo dyes listed in column I are reacted with cyanuric fluoride and the amines listed in column II.

Example I ll Ill CI CI 'CI blue C o o o o NH2 - 2 1 =I = CDS CDD Z > D mS S 28 N=N o N=N 3-Aminotoluene blue = ' E c~ E SO3H H2N OH SO3H 29 CH3O N=N NN=N/\ n-Butylamine greenish-tinged - Q blue HO3S SO3H NH2 H2N OH SO3H 30 HO3S N N--N Aniline-3- greenish-tinged N SO3H sulfonic acid blue HO3S NH2 SO3H H2N OH SO3H 31 )%N1N N N/\ 4-Aminoanisole blue HO3S SO3 HNH2 HO3S ;t 2t ~ t) t f E x N cO a) o 11 N N N n n

Table cont.

t I ll Ill SO3H H2N OH SO3H m: o O: 32 1NN-NMNN-N/\ 3-Chloroaniline strongly greenish ra, i ra, ra, N O NH2 tinged blue SO3H O H2N O o c = ~ > > E 33 N H035 N SO3H Ethylamine blue-green SO3H SO3H H2N OH SO3H 34 1)N=NN-N/\ N-Methylaniline strongly greenish HO3S NH2 tinged blue SO3H SOCH H2 SO3H 35 N N-N A%N=N/\ 3-Aminotoluene strongly greenish S 9 tinged blue g mc 2 o 2A 9 ~ m ot Xot x N n t U) UJ 0) Table cont.

~ 2 c Q SO3H H2 NOH SO3H 36 N N=N N N=N\ Metanilic strongly greenish r0 02N HO3 S SO3H NH2 503H 37 HO3SN=N H$ OH SO3H Ammonia blue NH2 503H em f ~ 0N f O CL UJ Q CD Example 38 A neutral solution of 17.3 parts of orthanilic acid in 200 parts of water is cooled to 0 C by adding 250 parts of ice. 9 parts. of cyanuric fluoride are allowed to run in in the course of 10 minutes, with vigorous stirring, and the pH is kept between 6 and 7 by the dropwise addition of 2 N sodium hydroxide solution.When no further unchanged orthanilic acid is detectable, a neutral solution of 1 8.8 parts of m-phenylenediamine-sulfonic acid in 50 parts of water is added to the solution of the primary condensation product, the temperature is allowed to rise to 20 to 25"C and the pH of the reaction mixture is kept between 6.5 and 7.0. After the reaction has gone to completion, the secondary condensation product is salted out by adding 15% by volume of potassium chloride and filtered off.

25 parts of 4 N sodium nitrite solution are added to a neutral suspension of 45.6 parts of the secondary condensation product described above in 1 50 parts of water and the mixture is cooled to O to 5"C with ice. 30 parts of 10 N hydrochloric acid are added and after several hours the excess nitrite is destroyed with sulfamic acid.

The yellow suspension of the diazo compound which is thus obtained is then poured into an ice-cold neutral solution of 50.3 parts of the dye

acid "sulfanilic acid----,H-acid" in 1 50 parts of water, to which 30 parts of sodium bicarbonate have also been added prior to the coupling reaction.

A clear solution forms (volume about 750 parts) and the dye formed is salted out from this by adding 10% by volume of a mixture of sodium chloride and potassium chloride in a ratio of 1:1. After filtering, the dye paste is mixed with a concentrated aqueous solution of 5 parts of disodium hydrogen phosphate and dried in vacuo at 50"C.

The dye thus obtained dyes cotton in navy blue shades.

Example 39 10 parts of cyanuric fluoride are added dropwise in the course of about 10 minutes to an icecold, neutral solution of 1 7.3 parts of orthanilic acid in 400 parts of water, the pH value of the reaction mixture being kept between 6 and 7 by adding 1 N sodium hydroxide solution at the same time.

The primary condensation product thus obtained is then poured into a neutral solution of 70.2 parts of the disazo dye of the formula

in 500 parts of water and the reaction mixture is warmed to 30 to 35"C and the pH value is kept between 7 and 8 by the dropwise addition of 1 N sodium hydroxide solution.

After the acylation has gone to completion, 5 parts of disodium hydrogen phosphate are added to the solution of the monofluorotriazine dye and the solution is evaporated to dryness in a rotary evaporator at 40 to 45"C. The dye thus obtained dyes cotton in navy blue shades.

When the procedure of the above example is repeated except that 18.72 parts of 4aminotoluene-3-sulfonic acid are used in place of orthanilic acid, a dye is obtained which also dyes cotton in navy blue shades.

Example 40 2 parts of the dye obtained according to Example 1 are 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 the liquor pick-up is 75% and is then dried.

The fabric is then impregnated with a solution, at 20 , which contains, per litre, 5 grams of sodium hydroxide and 300 grams of sodium chloride, and squeezed off to a liquor pick-up of 75% and the dyeing 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 detergent, rinsed and dried.

Example 41 2 parts of the dye obtained 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 maintained at 40 for 30 minutes and the dyeing is then rinsed and soaped for 1 5 minutes in a 0.3% boiling solution of a non-ionic detergent, rinsed and dried.

Claims

1. A reactive dye of the formula

in which D1 is a benzene or naphthalene radical, which can be substituted, D2 is a benzene radical, which can be substituted, R, is hydrogen or Ct 4-alkyl, the bridge member -N(R1)- is bonded to a ring carbon atom of D2, R2 is hydrogen or C1 4-alkyl, which can be substituted, and R3 is hydrogen or substituted or unsubstituted alkyl, cycloalkyl, aralkyl or aryl.

2. A reactive dye according to claim 1, of the formula

in which one Y is hydrogen and the other Y is sulfo and D1, R2 and R3 are as defined in claim 1.

3. A reactive dye according to claim 2, in which D1 is a benzene radical, which can be substituted by sulfo, methoxy and chlorine, or a naphthalene radical, which can be substituted by sulfo and nitro, R2 is hydrogen, methyl or ethyl and R3 is hydrogen, ethyl, sshydroxyethyl, butyl, phenyl, which can be substituted by methyl, methoxy, ethoxy, chlorine, acetylamino, ureido, carboxyl and sulfo, or naphthyl, which can be substituted by sulfo, or in which the amino group -NR2R3 is the morpholino radical.

4. A reactive dye according to claim 3, of the formula

in which R2 is hydrogen, methyl or ethyl and R3 is hydrogen or phenyl, which can be substituted by methyl, methoxy, chlorine and sulfo.

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

6. A reactive dye of formula I as defined in claim 1 substantially as described with reference to any of Examples 1 to 39.

7. A process for the preparation of a reaction dye of formula I according to claim 1 which comprises diazotisation, coupling and condensation reactions using a coupling component of the formula

a diazo component of the formula D1-NH2 (6) wherein D1 is as defined in claim 1, a further diazo component of the formula

wherein R1 and D2 are as defined in claim 1, 2,4,6-trifluoro-s-triazine of the formula

and an amino compound of the formula

wherein R2 and R3 are as defined in claim 1, the said reactions being carried out in any order.

8. A process according to claim 7, wherein the coupling component of the formula (5) which is used is a compound of the formula

9.A process according to claim 8, wherein the starting materials used are compounds of the formulae (6) and (9) in which D1 is a benzene radical, which can be substituted by sulfo, methoxy and chlorine, or a naphthalene radical, which can be substituted by sulfo and nitro, R2 is hydrogen, methyl or ethyl and R3 is hydrogen, ethyl, ss-hydroxyethyl, butyl, phenyl, which can be substituted by methyl, methoxy, ethoxy, chlorine, acetylamino, ureido, carboxyl and sulfo, or naphthyl, which can be substituted by sulfo, or in which the amino group -NR2R3 is the morpholino radical.

10. A process according to claim 9, for the preparation of a reactive dye of the formula

in which R2 is hydrogen, methyl or ethyl and R3 is hydrogen or phenyl, which can be substituted by methyl, methoxy, chlorine and sulfo, which comprises diazotisation, coupling and condensation reactions using a diazo component of the formula

1 -amino-8-hydroxynaphthalene-3, 6-disulfonic acid, 1, 3-diaminobenzene-4-sulfonic acid, cyanuric fluoride and an amino compound of the formula (9), in which R2 and R3 are as defined under formula (3), the said reactions being carried out in any order.

11. A process according to claim 10, for the preparation of the reactive dye of the formula

which comprises diazotising sulfanilic acid and 1 ,3-phenylenediamine-4sulfonic acid and coupling the reaction product with 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid, subjecting the resulting intermediate of the formula

12. A process for the preparation of a reactive dye of formula I, substantially as described with reference to any of Examples 1 to 39.

1 3. A reactive dye of formula I when produced by a process claimed in any of claims 7 to 12.

14. A method of dyeing or printing organic material wherein there is used a reactive dye as claimed in any of claims 1 to 6.

1 5. A method as claimed in claim 14 substantially as described with reference to Example 40 or 41.

16. Dyed or printed organic material when produced by a method claimed in claim 14 or 15.

1 7. A dyeing or printing preparation comprising a reactive dye as claimed in any of claims 1 to 6.

18. A dyeing or printing preparation as claimed in claim 1 7 substantially as described in Examples 40 or 41.