GB1564778A

GB1564778A - Fibrereactive mono-azo dyes containing at least two halotriazine radicals

Info

Publication number: GB1564778A
Application number: GB2840877A
Authority: GB
Original assignee: Ciba Geigy AG
Current assignee: Novartis AG
Priority date: 1976-07-08
Filing date: 1977-07-06
Publication date: 1980-04-16
Also published as: JPS61391B2; FR2357614A1; FR2357614B1; LU75328A1; BE856579A; CH633822A5; JPS537730A; DE2730581A1

Abstract

New fibre-reactive azo dyes of the formula <IMAGE> where the grouping <IMAGE> is a radical of the formula <IMAGE> or the formula <IMAGE> one of the two radicals X1 and X2 is a 2,4-di-fluoro-s-triazine radical or a 2-fluoro-4-amino, hydroxy, alkoxy, aryloxy, alkylthio or arylthio-s-triazine radical and the other is a 2,4-difluoro, chloro or bromo-s-triazine radical or a 2-fluoro, chloro or bromo-4-amino, hydroxy, alkoxy, aryloxy, alkylthio or arylthio-s-triazine radical, R is a bridge member and n is 0 or 1, obtained when an azo compound of the formula <IMAGE> where D, R and n are each as defined under the formula (1), a copper-donating agent, one equivalent of a 2,4,6-trifluoro-s-triazine or of a 2,4-difluoro-6-amino, hydroxy, alkoxy, aryloxy, alkylthio or arylthio-s-triazine and an equivalent of a 2,4,6-trifluoro, chloro or bromo-s-triazine or of a 2,4-difluoro, chloro or bromo-6-amino, hydroxy, alkoxy, aryloxy, alkylthio or arylthio-s-triazine are reacted by coppering and acylation in any desired order to form a fibre-reactive azo dye of the formula (1). The fibre-reactive azo dyes of the formula (1) are notable for high reactivity and a high degree of fixation, and they dye cellulose-containing materials in fast blue shades.

Description

(54) FIBRE-REACTIVE MONO-AZO DYES CONTAINING AT LEAST TWO HALO-TRIAZINE RADICALS (71) We, CIBA-GEIGY AG, a Swiss body corporate, of Basle, Switzerland, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- The present invention provides fibre-reactive azo dyes of the formula

wherein the group

is a radical of the formula

or of the formula

one of the two symbols X, and X2 is a fluoro-s-triazine radical and the other is a iluoro(chloro or bromo)-s-triazine radical, R is a bridge member and n is 0 or 1.

Possible radicals X1 and X2 are in particular a 2,4-difluoro-s-triazin-6-yl radical or a 2-fluoro-4-substituted s-triazin-6-yl radical or a 2,4-difluoro(chloro or bromo)s-triazin-6-yl radical or a 2-fluoro(chloro or bromo)-4-substituted s-triazin-6-yl radical, wherein the substituent in 4-position is -NH2, C1 "-alkylamino optionally substituted by C1-4-alkoxy, halogen hydroxy, sulpho, sulphato and phenyl N,N-di C1-6-alkylamino, N,N-di-hydroxy-C1-6-alkylamino, cyclohexylamino, N-C1-6-alkyl N-phenylamino, phenylamino optionally substituted by C1-4-alkyl, C1-4-alkoxy, halogen, nitro, acetylamino, hydroxy, carboxy and suipho, naphthylamino optionally substituted by hydroxy and suipho, pyridinylamino, benzthiazolylamino, quinolinylamino, pyrimidinylamino, morpholinyl, piperidinyl, piperazinyl, -OH, Cw-alkoxy optionally substituted by C, 4-alkoxy, C4-alkoxy-C1-alkoxy or carboxy, cyclohexyloxy, phenoxy optionally substituted by halogen, nitro, carboxy or sulpho, naphthoxy optionally substituted by sulpho, C1-6-alkylthio optionally substituted by carboxy, thioureido, phenylthio or naphthylthio.

The bridge member R can be of any kind. For example it can be a chain-like aliphatic radical, an aromatic radical or also a heterocyclic radical, and it can also be composed of several different radicals, for example aromatic and heterocyclic radicals. Preferably R is an aromatic radical which is bonded through an intermediary member to the amino group of the l-amino-8-hydroxynaphthalene 3.6- or -4,6-disulphonic acid component in formula (1), for example

The bridge member R is thus preferably derived from an acyl compound, for example a halogenoacyl compound, which contains an additional free amino group to which the external halogeno-s-triazine radical X2 can be fused. In particular, R is an m- or p-benzoyl radical.

If only one of the two symbols X, and X2 is a fluoro-s-triazine radical and the other is a chloro- or bromo-s-triazine radical, either X1 or X2 can be the fluoro-striazine radical; but preferably in this case X1 is the fluoro-s-triazine radical.

Preferred fibre-reactive radicals are those of the formula (1) wherein n is 0 and X1 and X2 are identical radicals.

Important subgroups of the fibre-reactive azo dyes of the formula (1) are: a) fibre-reactive azo dyes of the formula

wherein each of Y1 and Y2 independently is a fluorine atom, a substituted or unsubstituted amino group, a hydroxyl group, or an unsubstituted or substituted alkoxy, aryloxy, alkylthio or arylthio group: and b) fibre-reactive azo dyes of the formula

wherein each of Y1 and Y2 independently is a fluorine atom, an unsubstituted or substituted amino group, a hydroxyl group, or an unsubstituted or substituted alkoxy, aryloxy, alkylthio or arylthio group.

The dyes of the formula (1) are fibre-reactive, since they contain removable fluorine, chlorine or bromine atoms in the fluoro-s-triazine and fluoro(chloro or bromo)-s-triazine radicals X1 and X2.

By fibre-reactive compounds are meant those compounds which are able to react with the hydroxyl groups of cellulose or with the amino groups of natural or synthetic polyamides to form covalent chemical bonds.

In Patent Specification 1,188,606 there is disclosed a class of similar dyestuffs, whose general formula is

in which D represents the radical of an organic non-anthraquinoid dyestuff, R is hydrogen or a C1 to C4 alkyl or hydroxyalkyl group, Q is an alkylene, aralkylene, arylene, -CO- or -SO2-group, n is the number 0 or 1, R1 is an amino group which may contain substituents linked to the amino group by a single bond, an optionally etherified hydroxy group, an optionally etherified thio group, or an optionally substituted hydrocarbon radical, and the group

is linked directly to a carbon atom of an aromatic carbocyclic ring of the dyestuff D, which may be in the form of a copper complex.

The dyestuffs of the present invention, which contain as coupling components the l-amino-8-hydroxynaphthalene disulphonic acid and two or more triazine rings, have a higher degree of fixation, and the preferred dyes of this invention, wherein the non-chromophoric group bound to the triazine ring is a substituted or unsubstituted amino group, exhibit better stability of the dye fibre linkage to acid hydrolysis.

The manufacture of the fibre-reactive azo dyes of the formula (1) comprises reacting an azo compound of the formula

wherein D, R and n are as defined in formula (1), a copper donor, and compounds which are suitable for introducing the radicals X, and X2, to give a fibre-reactive azo dye of the formula (1).

In particular, the fibre-reactive azo dyes of the formula (1) are obtained by reacting an azo compound of the formula (7), wherein D, R and n are as defined in formula (1), a copper donor, one equivalent of 2,4,6-trifluoro-s-triazine or of a 2,4difluoro-6-amino(hydroxy, alkoxy, aryloxy, alkylthio or arylthio)-s-triazine, and a further equivalent of 2,4,6-trifluoro(chloro or bromo)-s-triazine or of a 2,4-difluoro (chloro or bromo)-6-amino(hydroxy, alkoxy, aryloxy, alkylthio or arylthio)-striazine, by coppering and acylating to give a fibre-reactive azo dye of the formula (1), and, if 2,4,6-trifluoro-s-triazine or 2,4,6-trifluoro(chloro or bromo)-s-triazine is used as acylating agent, optionally replacing a halogen atom in the s-triazine ring by an amino, hydroxyl, alkoxy, aryloxy, alkylthio or arylthio group, by condensation with ammonia, an amine, water, an alcohol, an aromatic hydroxy compound or an aliphatic or aromatic thiol compound. Coppering and acylation can be carried out in optional sequence.

The preferred embodiment of the process for the manufacture of the fibrereactive azo dyes of the formula (1) comprises reacting an azo compound of the formula (7), wherein D has the indicated meaning and n is 0, a copper donor, and 2 equivalents of 2,4,6-trifluoro-s-triazine or of a 2,4-difluoro-6-amino(hydroxy, alkoxy, aryloxy, alkylthio or arylthio)-s-triazine, by coppering and acylation to give a fibre-reactive azo dye of the formula (1), and, if 2,4,6-trifluoro-s-triazine is used as acylating agent, optionally replacing a halogen atom in the s-triazine ring by an amino, hydroxyl, alkoxy, aryloxy, alkylthio or arylthio group, by condensation with ammonia, an amine, water, an alcohol, an aromatic hydroxy compound or an aliphatic or aromatic thiol compound.

The important fibre-reactive azo dyes of the formulae (5) and (6) are obtained by a) reacting an azo compound of the formula

in optional sequence, with a copper donor and with 2 equivalents of 2,4,6-trifluoros-triazine, and, before or after the acylation, replacing a fluorine atom in the striazine ring by an amino, hydroxy, alkoxy, aryloxy, alkylthio or arylthio group by condensation with ammonia, an amine, water, an alcohol, an aromatic hydroxy compound or an aliphatic or aromatic thiol compound; or b) reacting an azo compound of the formula

in optional sequence with a copper donor and with 2 equivalents of 2,4,6-trifluoros-triazine and, before or after the acylation, replacing a fluorine atom in the striazine ring by an amino, hydroxyl, alkoxy, aryloxy, alkylthio or arylthio group by condensation with ammonia, an amine, water, an alcohol, an aromatic hydroxy compound or an aliphatic or aromatic thiol compound.

The fibre-reactive azo dyes of the formula (5) are also obtained by acylating azo compounds of the formula

with one equivalent of 2,4,6-trifluoro-s-triazine or of a 2,4-difluoro-6-amino (hydroxy, alkoxy, aryloxy, alkylthio or arylthio)-s-triazine and a further equivalent of 2,4,6-trifluoro(chloro or bromo)-s-triazine or of a 2,4-difluoro(chloro or bromo)6-amino(hydroxy, alkoxy, aryloxy, alkylthio or arylthio)-s-triazine, and if 2,4,6trifluoro-s-triazine or 2,4,6-trifluoro(chloro or bromo)-s-triazine is used as acylating agent, optionally replacing a halogen atom in the s-triazine ring by an amino, hydroxyl, alkoxy, aryloxy, alkylthio or arylthio group, by condensation with ammonia, an amine, water, an alcohol, an aromatic hydroxy compound or an aliphatic or aromatic thiol compound, and subsequently converting the dye by oxidative coppering into the copper complex.

The o,o'-dihydroxyazo compound of the formulae (7), (8) or (9) and the omonohydroxyazo compounds of the formula (10), used for the manufacture of the fibre-reactive azo dyes of the formula (1), can be prepared in the following manner: 1) by diazotisation of 2-amino-6-nitro-naphthalene-4,8-disulphonic acid, coupling to the N-acetyl compound of l-amino-8-hydroxynaphthalene-3,6- or -4,6disulphonic acid (H- or K-acid), oxidative coppering of the resultant o-monohydroxyazo compound and subsequent reduction of the nitro group to the amino group and simultaneous decoppering and saponification of the acetylamino group; 2) by diazotisation of the nitrodiazoxy acid, coupling to the H- or K-acid and subsequent reduction of the nitro group to the amino group; 3) by diazotisation of 2-amino-6-nitro(or acetylamino)-naphthalene-4,8-disulphonic acid, coupling to the H- or K- acid or to the respective N-acetyl derivative thereof, and subsequent conversion of the nitro group or acetylamino group into the amino group by reduction or saponification.

The diazotisation is normally effected by treatment with nitrous acid in aqueous-mineral acid solution at low temperature, and the coupling is carried out at weakly acid or neutral to weakly alkaline pH values.

If the starting material is an azo compound of the formula (7), wherein n is 1, then the radical -R-NH2 must be introduced into the H- or K-acid. This is accomplished preferably by acylation of the amino group in the l-position of the Hor K-acid with corresponding acyl compounds which contain an additional free amino group or a group which can be converted into an amino group. Examples of such acyl compounds are: p-nitrobenzoylchloride (subsequently reduced), 2,4 dichloro-6-(3 '-amino-4'-sulphophenylamino)-s-triazine and 2,4-difluoro-6-(4'amino-2',5'-disulphophenylamino)-s-triazine. The introduction of the radical -R-NH2 can be effected before or, if appropriate, after the coupling.

As starting materials for the manufacture of the fibre-reactive azo dyes of the formula (1) there may also be mentioned: 2,4,6-trifluoro-s-triazine, 2,4,6-trichloros-triazine, 2,4,6-tribromo-s-triazine, 2,4-difluoro(chloro or bromo)-6-amino (hydroxy, alkoxy, aryloxy, alkylthio or arylthio)-s-triazines, wherein the amino, hydroxy, alkoxy, aryloxy, alkylthio or arylthio substituent can be for example the radical of one of the amines, alcohols, aromatic hydroxy compounds, aliphatic or aromatic thiol compounds listed hereinafter or the hydroxyl radical of water. These compounds can also however, as described above, be subsequently condensed with a dihalogeno-s-triazine radical which is already linked to the azo dye, in order to replace a halogen atom in the dihalogeno-s-triazine radical by an amino, hydroxy, alkoxy, aryloxy, alkylthio or arylthio substituent.

Examples of the above mentioned amino, hydroxy and thiol compounds are: ammonia, methylamine, dimethylamine, ethylamine, diethylamine, propylamine, isopropylamine, butylamine, dibutylamine, isobutylamine, sec.-butylamine, tert.butylamine, hexylamine, methoxyethylamine, ethoxyethylamine, methoxypropylamine, chloroethylamine, hydroxyethylamine, dihydroxyethylamine, hydroxypropylamine, aminoethanesulphonic acid, p-sulphatoethylamine, benzylamine, cyclohexylamine, aniline, o-, m- and p-toluidine, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- and 3,5dimethylaniline, o-, m- and p-chloroaniline, N-methylaniline, N-ethylaniline, 3- or 4-acetylaminoaniline, o-, m- and p-nitroaniline, o-, m- and p-aminophenol, 2methyl4-nitro-aniline, 2-methyl-5-nitroaniline, 2,5-dimethoxyaniline, 3-methyl-4nitro-aniline, 2-nitro-4-methyl-aniline, 3-nitro-4-methyl-aniline, o-, mand p-phenylenediamine, 3-amino-4-methyl-aniline, 4-amino-3-methylaniline, 2-amino-4-methyl-aniline, o-, m- and p-anisidine, o-, m- and -phenetidine, napthylamine-( I), naphthylamine-(2), 1 ,4-diaminonaphthalene, 1,5-diamino-naphthalene, 2-amino-I -hydroxy-naphthalene, 1 -amino-4-hydroxy- naphthalene, l-amino-8-hydroxy-naphthalene, 1-amino-2-hydroxy-naphthalene, 1amino-7-hydroxy-naphthalene, orthanilic acid, metanilic acid, sulphanilic acid, aniline-2,4-disulphonic acid, aniline-2,5-disulphonic acid, anthranilic acid, m- and p-aminobenzoic acid, 2-aminotoluene-4-sulphonic acid, 2-amino-toluene-5-sulphonic acid, p-aminosalicylic acid, 1 -amino-4-carboxy-benzene-3-sulphonic acid, I-amino-2-carboxy-benzene-5-sulphonic acid, 1 -amino-5-carboxy-benzene-2-sul- phonic acid, l-naphthylamine-2-, -3-, -4-, -5-, -6-, -7- and -8-sulphonic acid, 2naphthylamine-l-, -4-, -5-, -6-, -7- and -8-sulphonic acid, l-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-disulphonic acid, 2naphthylamine-1,5-, -1,6-, -1,7-, -3,6-, -3,7-, -4,7-, -4,8-, -5,7-, and -6,8-disulphonic acid, I-naphthylamine-2,4,6-, -2,4,7-, -2,5,7-, -3,5,7-, -3,6,8- and -4,6,8-trisulphonic acid, 2-naphthylamine-1,3,7-, -1,5,7-, -3,5,7-, -3,6,7-, -3,6,8- and -4,6,8-trisulphonic acid, 2-, 3- and 4-aminopyridine, 2-aminobenzthiazole, 5-, 6- and 8-aminoquinoline, 2-aminopyrimidine, morpholine, piperidine, piperazine, water, methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, sec.-butanol, tert.-butanol, hexanol, cyclohexanol, p-methoxyethanol, ii-ethoxyethanol, 3, methoxypropanol, y-ethoxypropanol, p-ethoxy-p-ethoxyethanol, glycolic acid, phenol, o-, m- and p-chlorophenol, o-, m- and p-nitrophenol, o-, m- and p-hydroxybenzoic acid, o-, m- and p-phenolsulphonic acid, phenol-2,4-disulphonic acid, anaphthol, -naphthol, I-hydroxynaphthalene-8-sulphonic acid, 2-hydroxy naphthalene-l-sulphonic acid, l-hydroxynaphthalene-5-sulphonic acid, IThy- droxynaphthalene-4-sulphonic acid, 1-hydroxy-naphthalene-6- or -7-sulphonic acid, 2-hydroxynaphthalene-6-, -7- or -8-sulphonic acid, 2-hydroxynaphthalene-4-sulphonic acid, 2-hydroxynaphthalene-4,8- or -6,8disulphonic acid, 1-hydroxynaphthalene-3,6 or -3,8-disulphonic acid, 1hydroxy naphthalene-4,8-disulphonic acid, 2-hydroxynaphthalene-3,6-disulphonic acid, methanethiol, ethanethiol, propanethiol, isopropanethiol, n-butanethiol, thioglycolic acid, thiourea, thiophenol, cx-thionaphthol, p-thionaphthol.

The condensation reactions of the 2,4-difluoro-6-amino(hydroxy, alkoxy, aryloxy, alkylthio or arylthio)-s-triazines or of the 2,4-difluoro(chloro or bromo)-6amino (hydroxy, alkoxy, aryloxy, alkylthio or arylthio)-s-triazines with the azo compounds of the formulae (7), (8), (9) or (10) as well as of the 2,4,6-trifluoro-striazine or of the 2,4,6-trifluoro(chloro or bromo)-s-triazine with the azo compounds of the formulae (7), (8), (9) or (10) and optionally amines, water, alcohols, aromatic hydroxy compounds or aliphatic or aromatic thiol compounds, are carried out preferably in aqueous solution or suspension, at low temperature and a weakly acid or neutral to weakly alkaline pH value.Advantageously, the hydrogen fluoride, chloride or bromide set free during the condensation reactions are neutralised continuously by the addition of aqueous alkali hydroxides, carbonates or bicarbonates.

As copper donors it is possible to use for example salts which contain copper as cation, for example copper sulphate and copper acetate. In many cases it is advantageous to use complex copper compounds, for example in the form of copper-amine complexes, such as copper tetramminesulphates from copper sulphate and ammonia, pyridine or monoethanolamine, or in the form of compounds which contain copper bound as a complex, for example complex copper compounds of the alkali salts of aliphatic aminocarboxylic acids or hydroxycarboxylic acids, such as of glycocol, of lactic acid and, in particular, of tartaric acid, such as sodium copper tartrate.

The treatment with the copper donors can be carried out by methods which are known per se, for example at room temperature, if easily metallisable starting compounds are used, or by heating to temperatures between 50 and 120"C in an open vessel, for example with reflux cooling or optionally in a closed vessel under pressure, while the pH conditions are provided by the nature of the chosen metallising procedure, for example an acid coppering with copper sulphate and an alkaline coppering with copper tetramminesulphate. If desired, a solvent, for example alcohol or dimethyl formamide, can also be added during the metallising.

In the oxidative coppering, an oxidant, in particular hydrogen peroxide, is added to the reaction mixture, and the reaction is in other respects carried- out in the described manner.

The fibre-reactive azo dyes of the formula (1) are characterised by a pronounced reactivity and a high degree of fixation. They are suitable for dyeing and printing a very wide variety of materials, such as silk, leather, wool, polyamide and polyurethane fibres, and especially cellulosic materials of fibrous structure, 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 process, in which the goods are impregnated with aqueous and, if appropriate, also with saltcontaining dye solutions, and the dyes are fixed after treatment with alkali or in the presence of alkali, optionally with the application of heat.

They are also suitable for printing, in particular on cotton, and also for printirig nitrogen-containing fibres, for example wool, silk or blends containing wool.

It is advisable to rinse the dyeings and prints thoroughly with cold and hot water, if appropriate with the addition of an agent which acts as a dispersant and promotes the diffusion of non-fixed dye.

In the following Examples, the parts and percentages are by weight, and all the ring systems shown are to be understood as aromatically unsaturated.

Example I With good stirring, a solution of 2.97 parts of cyanuric fluoride in 5 parts of toluene is added dropwise in the course of 5 to 10 minutes to an ice-cold neutral solution of 7.25 parts of the copper complex of the formula

in 150 parts of water and the pH of the reaction mixture is kept between 6 and 7 with IN sodium hydroxide solution. When the acylation is complete, a neutral solution of 3.46 parts of metanilic acid in 20 parts of water is added to the suspension of the diprimary condensation product and the mixture is warmed to 30"--35"C. During the second condensation, the pH is kept between 7 and 8 with 1N sodium hydroxide solution. The dye is salted out of the resultant clear solution by addition of 10 -O by volume of potassium chloride and collected by filtration.The isolated dye is mixed with a concentrated aqueous solution of 1 part of disodium hydrogen phosphate and dried in vacuo at 500 C. It dyes cotton in clear blue shades.

Similar dyes are obtained by reacting the copper complexes listed in column I of Table I in accordance with the particulars of Example 1 firstly with cyanuric fluoride and then with the amines listed in column II, using sufficient amine to replace one fluorine atom in each triazine ring.

TABLE 1.

I II HO 0 O-C'i-O irn 3 2 su iphanilic H2 C 3 S03H ll2 HO3$O3H SO3H ammonia H 03S Cu 0 hli2 o- toluidine UN HO 2 3 80311 80311 H Q3S 0 - Clt---- 0 NHCONH 1TH2 3N=N 80311 tani lic H2≈ 3 S03H acid 80311 H03S 0 < = 0 NO C < NENH{pHl;2 3 1 Il 2 Sii I" N < clss S03H etani1ic 112 HO3SO3H C1 acid 80311 1 H032; 0Cu 0 t I9so3S 1X44 Nc,N 3 3 21 < ho3 < \303H OCi1( CH3 ) HO S SO OCH(o)2 803H 2 TABLE 1 (Cont'd.)

\ I II O----Cu ~- O NIl2 '; ;^ N=N N="-jeji acid 11035 S03H NH2 I{03S 0- -Cu -s- O NH2 I N=NM aniLine H2N 80311 11038 50311 ir o-toluidine N-methylaniline 2-aminonaphthalene 6-sulphonic acid It 4-aminosalicylic acid (I 2-aminonaphtralene 4 ,8-disulphonic acid II me thy lamine 'I p-aminobenzoic acid 11035 0-Cu -0 NH2 N=N < S03H metanilic acid 112N \H035 50311 SO3H TABLE 1 (Cont'd).

-II HO3S O----Cu NH2 J NH, 2 S03H S03H S02H II 2-aminonaphthalene 6-sulphonic acid O---- ~ O -s- O NH2 I 3 NH=NO3S. S03H o-toluidine NH, tl sulphanilic acid ri - ammonia O Cu 0 NH2 HO ti S I metanil4c acid S SO311 2 n ethylamine 2-aminonaphthalene - 5-sulphonic acid II 4- aninosalicylic acid TABLE 1 (Cont'd).

I II C1 S03H H03S 0-Cu -O NH NIt-$)NH2 ammonia CY N=N- n SO3H S03K HO3 S SO3H Example 2 With good stirring, a solution of 2.97 parts of cyanuric fluoride in 5 parts of toluene is added dropwise in the course of 5 to 10 minutes to an ice-cold neutral solution of 3.46 parts of orthanilic acid in 75 parts of water and the pH of the reaction mixture is kept between 6 and 7 with 1N sodium hydroxide solution.When the acylation is complete, the suspension of the primary condensation product is poured into a neutral solution of 7.25 parts of the copper complex of the formula

and the reaction mixture is warmed to 300--350C, while keeping the pH between 7 and 8 by the dropwise addition of IN sodium hydroxide solution. The reactive dye is then salted out with potassium chloride, collected by filtration and mixed with a concentrated aqueous solution of 1 part of disodium hydrogen phosphate and dried in vacuo at 500 C. It dyes cotton in clear blue shades.

Further dyes which dye cotton in the shades indicated in column III of Table 2 are obtained by acylation of the copper complexes listed in column I with the difluorotriazine derivatives of the amines listed in column II.

TABLE 2.

H a) ~ = = H cu p Q X 2 2-amino-toluene-5-suiphonic blue < u c) H so c X X o u o c c c u anthranilic P4 acid I0 I a 1 1H C U W i t cu roP o acid 7 1 ar I ; re Ur o rl 0 L1 rl hl r( CV I rl re I O C P) d Q) C Ip E C C *-r td ctl re tia C c N=N orthanilic W D i i < 10 C C Le C cum O ns ~ .

HO SO- Cu--O NHCONH2 N=N aniline-2,5-disulphonic acid I' M so M SO 11 H O O Ag 1 W A TABLE 2 (Cont'd).

H q} H .n a u c 1 o 03 c n a s cr p r( NH rl (II O a, H ts Co 7 HO O I co u r or o a C m C foC ca c I r( cl rl C Br Ero L) O U) rg ri o e^4 r C4 X disuiphonic acd --- HO SN=N NH 3 2 2-aminotoluene-4-sulpnonic 110350311 acid NH2 n n H S g T V m T t m | Oi eN 04 mN . ;t 20 TABLE 2 (Cont'd).

H H 01 r-1 r3 I-r C) Q :: H03S N=y 2-aminonaphthalene- blue i SO3111103550311 1-suiphonic acid 1 a I a c c arEJ 1 3 o, cl re ra ct m oo ri -c( m X Q &num; 74 94 e: II aniline-2,4-disulphonic t c u I (p 1 u acid a LI ae (PC hl rl N IO co a, < o, o H ca c c C eo dri m rl C -ro 66 E D X g C 11035){-:-; SO3H orthanilic acid m Q I co co O X . ~ , In Iacid II 2-aminonaphthalene- 1-sul- II t acid H VZ : s H o 3 H O j Dyeing Procedure I 2 Parts of the dye obtained according to Example 1 are dissolved in 100 parts of water while adding 0.5 part of sodium m-nitrobenzenesulphonate. A cotton fabric is impregnated with the resultant solution to a liquor pick-up of 75% and then dried.

The fabric is then impregnated with a warm solution of 20 C which contains, per litre, 5 g of sodium hydroxide and 300 g of sodium chloride, and squeezed out to a pick-up of 75%. The dyeing is steamed for 30 seconds at 100 to 101 C, rinsed, soaped for a quarter of an hour in a 0.3% boiling solution of a non-ionic detergent, rinsed and dried.

Dyeing Procedure II 2 Parts of the dye obtained according to Example 1 are dissolved in 100 parts of water. The solution is added to 1900 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 400C and 40 parts of calcined sodium carbonate and another 60 parts of sodium chloride are added after 30 minutes. The temperature is kept for 30 minutes at 40 C. The dyeing is rinsed and then soaped for 15 minutes in a 0.3% boiling solution of a non-ionic detergent, rinsed and dried.

WHAT WE CLAIM IS: 1. Fibre-reactive azo dyes of the formula

wherein the group

is a radical of the formula

or of the formula

one of the two symbols X, and X2 is a fluoro-s-triazine radical and the other is a fluoro(chloro or bromo)-s-triazine radical, R is a bridge member and n is 0 or 1.

2. Fibre-reactive azo dyes according to claim 1 of the formula (1), wherein D, R and n are as defined in claim 1 and one of the two symbols X, and X2 is a 2,4 difluoro-s-triazin-6-yl radical or a 2-fluoro-4-substituted-s-triazin-6-yl radical and the other is a 2,4-difluoro(chloro or bromo)-s-triazin-6-yl radical or a 2-fluoro (chloro or bromo)-4-substituted-s-triazin-6-yl radical, the 4 substituent in each case being NH2, C1-6-alkylamino optionally substituted by C1-4-alkoxy, halogen, hydroxy, sulpho, sulphato and phenyl, N,N-di-C1-6-alkyl, amino, N,N-di-hydroxy C1-6-alkylamino, cylclohexylamino, N-C1-6-alkyl-N-phenylamino, phenyl amino optionally substituted by C1-4-alkyl, C1-4-alkoxy, halogen, nitro, acetylamino, hydroxy, carboxy and sulpho, naphthylamino optionally substituted by hydroxy and sulpho, pyridinylamino, benzthiazolylamino, quinolinylamino, pyrimidinyl amino, morpholinyl, piperidinyl, piperazinyl, -OH, C,- ,-alkoxy optionally sub stituted by C,-alkoxy, CF4-alkoxy-CF4-alkoxy or carboxy, cyclohexyloxy, phenoxy optionally substituted by halogen, nitro, carboxy or sulpho, naphthoxy optionally substituted by sulpho, C, -alkylthio optionally substituted by carboxy, thioureido, phenylthio or naphthylthio.

**WARNING** end of DESC field may overlap start of CLMS **.

Claims

**WARNING** start of CLMS field may overlap end of DESC **.

Dyeing Procedure I

2 Parts of the dye obtained according to Example 1 are dissolved in 100 parts of water while adding 0.5 part of sodium m-nitrobenzenesulphonate. A cotton fabric is impregnated with the resultant solution to a liquor pick-up of 75% and then dried.

The fabric is then impregnated with a warm solution of 20 C which contains, per litre, 5 g of sodium hydroxide and 300 g of sodium chloride, and squeezed out to a pick-up of 75%. The dyeing is steamed for 30 seconds at 100 to 101 C, rinsed, soaped for a quarter of an hour in a 0.3% boiling solution of a non-ionic detergent, rinsed and dried.

Dyeing Procedure II 2 Parts of the dye obtained according to Example 1 are dissolved in 100 parts of water. The solution is added to 1900 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 400C and 40 parts of calcined sodium carbonate and another 60 parts of sodium chloride are added after 30 minutes. The temperature is kept for 30 minutes at 40 C. The dyeing is rinsed and then soaped for 15 minutes in a 0.3% boiling solution of a non-ionic detergent, rinsed and dried.

WHAT WE CLAIM IS: 1. Fibre-reactive azo dyes of the formula

wherein the group

is a radical of the formula

or of the formula

one of the two symbols X, and X2 is a fluoro-s-triazine radical and the other is a fluoro(chloro or bromo)-s-triazine radical, R is a bridge member and n is 0 or 1.
2. Fibre-reactive azo dyes according to claim 1 of the formula (1), wherein D, R and n are as defined in claim 1 and one of the two symbols X, and X2 is a 2,4 difluoro-s-triazin-6-yl radical or a 2-fluoro-4-substituted-s-triazin-6-yl radical and the other is a 2,4-difluoro(chloro or bromo)-s-triazin-6-yl radical or a 2-fluoro (chloro or bromo)-4-substituted-s-triazin-6-yl radical, the 4 substituent in each case being NH2, C1-6-alkylamino optionally substituted by C1-4-alkoxy, halogen, hydroxy, sulpho, sulphato and phenyl, N,N-di-C1-6-alkyl, amino, N,N-di-hydroxy C1-6-alkylamino, cylclohexylamino, N-C1-6-alkyl-N-phenylamino, phenyl amino optionally substituted by C1-4-alkyl, C1-4-alkoxy, halogen, nitro, acetylamino, hydroxy, carboxy and sulpho, naphthylamino optionally substituted by hydroxy and sulpho, pyridinylamino, benzthiazolylamino, quinolinylamino, pyrimidinyl amino, morpholinyl, piperidinyl, piperazinyl, -OH, C,- ,-alkoxy optionally sub stituted by C,-alkoxy, CF4-alkoxy-CF4-alkoxy or carboxy, cyclohexyloxy, phenoxy optionally substituted by halogen, nitro, carboxy or sulpho, naphthoxy optionally substituted by sulpho, C, -alkylthio optionally substituted by carboxy, thioureido, phenylthio or naphthylthio.
3. Fibre-reactive azo dyes according to claim 1 wherein n is 0 and X, and X2

are identical radicals.
4. Fibre-reactive azo dyes according to claim 1 of the formula

wherein each of Y, and Y2 independently is a fluorine atom, an unsubstituted or substituted amino group, a hydroxyl group, or an unsubstituted or substituted alkoxy, aryloxy, alkylthio or arylthio group.
5. Fibre-reactive azo dyes according to claim I of the formula

wherein each of Y, and Y2 is independently a fluorine atom, an unsubstituted or substituted amino group, a hydroxyl group, or an unsubstituted or substituted alkoxy, aryloxy, alkylthio or arylthio group.
6. The fibre-reactive azo dye according to claim 1 of the formula
7. The fibre-reactive azo dye according to claim 1 of the formula
8. A process for the manufacture of fibre-reactive azo dyes of the formula

wherein the group

is a radical of the formula

or ot the formula

one of the two symbols X, and X2 is a fluoro-s-triazine radical and the other is a fluoro(chloro or bromo)-s-triazine radical, R is a bridge member and n is 0 or 1, which process comprises reacting an azo compound of the formula (7)

in which D, R and n are as defined in formula (1), a copper donor, and compounds which are suitable for introducing the radicals X, and X2, to give a fibre-reactive azo dye of the formula (1).
9. A process for the manufacture of fibre-reactive azo dyes according to claim 8, wherein an azo compound of the formula (7), wherein D, R and n are as defined in claim 8, a copper donor, one equivalent of 2,4,6-trifluoro-s-triazine or of a 2,4difluoro-6-amino(hydroxy, alkoxy, aryloxy, alkylthio or arylthio)-s-triazine, and a further equivalent of 2,4,6-trifluoro(chloro or bromo)-s-triazine or of a 2,4-difluoro (chloro or bromo)-6-amino(hydroxy, alkoxy, aryloxy, alkylthio or arylthio)-striazine, are reacted by coppering and acylation to give a fibre-reactive azo dye of the formula (1), and, if 2,4,6-trifluoro-s-triazine or 2,4,6-trifluoro(chloro or bromo)s-triazine is used as acylating agent, a halogen atom in the s-triazine ring is optionally replaced by an amino, hydroxyl, alkoxy, aryloxy, alkylthio or arylthio group, by condensation with ammonia, an amine, water, an alcohol, an aromatic hydroxy compound or an aliphatic or aromatic thiol compound.
10. A process according to claim 8, wherein an azo compound of the formula (7), wherein D is as defined in claim 8 and n is 0, a copper donor, and 2 equivalents of 2,4,6-trifluoro-s-triazine or of a 2,4-difluoro-6-amino(hydroxy, alkoxy, aryloxy, alkylthio or arylthio)-s-triazine, are reacted by copperin and acylation to give a fibre-reactive azo dye of the formula (1), and, if 2,4,6-trinuoro-s-triazine is used as acylating agent, a halogen atom in the s-triazine ring is optionally replaced by an amino, hydroxyl, alkoxy, aryloxy, alkylthio or arylthio group, by condensation with ammonia, an amine, water, an alcohol, an aromatic hydroxy compound or an aliphatic or aromatic thiol compound.
Il. A process according to claim 8, wherein an azo compound of the formula

in optional sequence, is reacted with a copper donor and acylated with 2 equivalents of 2,4,6-trifluoro-s-triazine, and, before or after the acylation, a fluorine atom in the s4riazine ring is replaced by an amino, hydroxyl, alkoxy, aryloxy, alkylthio or arylthio group by condensation with ammonia, an amine, water, an alcohol, an aromatic hydroxy compound or an aliphatic or aromatic thiol compound.
12. A process according to claim 8, wherein an azo compound of the formula

in optional sequence, is reacted with a copper donor and acylated with 2 equivalents of 2,4,6-trifluoro-s-triazine and, before or after the acylation, a fluorine atom in the s-triazine ring is replaced by an amino, hydroxyl, alkoxy, aryloxy, alkylthio or arylthio group by condensation with ammonia, an amine, water, an alcohol, an aromatic hydroxy compound or an aliphatic or aromatic thiol compound.
13. A process for the manufacture of fibre-reactive azo dyes of the formula (5), wherein azo compounds of the formula

are acylated with one equivalent of 2,4,6-trifluoro-s-triazine or of a 2,4-difluoro-6amino(hydroxy, alkoxy, aryloxy, alkylthio or arylthio)-s-triazine and a further equivalent of 2,4-6-trifluoro(chloro or bromo)-s-triazine or of a 2,4-difluoro(chloro or bromo)-6-amino(hydroxy, alkoxy, aryloxy, alkylthio or arylthio)-s-triazine, and, if 2,4,6-trifluoro-s-triazine or 2,4,6-trifluoro(chloro or bromo)-s-triazine is used as acylating agent, a halogen atom in the s-triazine ring is optionally replaced by an amino, hydroxyl, alkoxy, aryloxy, alkylthio or arylthio group, by condensation with ammonia, an amine, water, an alcohol, an aromatic hydroxy compound or an aliphatic or aromatic thiol compound, and subsequently oxidatively coppered.
14. A process according to either of claims 8 and 13 for the manufacture of the fibre-reactive azo dye of the formula

wherein the copper complex of the formula

obtained by coppering of the corresponding azo compound, is condensed with 2 equivalents of cyanuric fluoride and the resultant diprimary condensation product is condensed with 2 equivalents of metanilic acid to give the fibre-reactive azo dye of the above formula.
15. A process according to claim 8 for the manufacture of the fibre-reactive azo dye of the formula

wherein the copper complex of the formula

obtained by coppering of the corresponding azo compound, is condensed with 2 equivalents of cyanuric fluoride and the resultant diprimary condensation product is condensed with 2 equivalents of metanilic acid to give the fibre-reactive azo dye of the above formula.
16. Any fibre-reactive dye according to claim 1 identified herein.
17. A process according to claim 8, substantially as herein described.
18. A process of preparing a dyestuff according to claim 1 substantially as described in any one of the Examples herein.
19. A fibre-reactive azo dye according to claim 1 when obtained according to any one of claims 8 to 15, 17 or 18.
20. A process of dyeing with a dyestuff according to claim I substantially as described in either of the dyeing procedures herein.
21. A process for dyeing or printing which comprises the use of the azo dyes according to any of claims 1 to 7, 16 and 19.
22. A process according to claim 21 for dyeing cellulose fibres.
23. Dyeing and printing preparations which contain the fibre-reactive dyes according to any of claims 1 to 7, 16 and 19.
24. The dyed or printed textile material obtained according to claim 21 or 22.