DE2109900A1 - Reactive dyes - Google Patents

Description

PATENT LAWYERS DR. -ING. H. FINCKE DIPL.-INQ. H; DRILL DIPL.-ING. S. STAEGER

Fern calls '24 * 0 OK

■ MUNOHEN S, 31

March 2, 1971

Folder 22503 - Dr. K.
Gases D 22565

Imperial Chemical Industries Ltd. London, UK

Reactive dyes

Priority: 2.3.1970 - Great Britain

The invention relates to new reactive dyes that especially when dyeing cellulosic textile materials are of value.

According to the invention, dyes of the general formula

109840/1532

DNO C - ₁ ^ f

I) II R ^ 3-NH - X (1)

RN N ^

I. Cl

suggested, wherein R stands for H or an alkyl group, D for the residue of a 1 d-metal complex aminoazio compound of the formula D-NHR, and X for the remainder of a colorless organic acid which has a cellulose-reactive substituent has, stands.

In the formula (1), the symbol D can represent, for example, the radical of a mono- or bisazo compound which has the form a 1: 1 copper or nickel complex may have. The expression 1: 1- as used here means that a metal atom has formed a complex with an azo group, so that a bisazo compound contains 2 atoms of metal per molecule can. *

As examples of groups represented by X, the following should be mentioned: aliphatic sulfonyl groups which contain a halogen atom or a sulfate-ter group in the B position to the sulfur atom, for example ß-sulfatoethyl sulfone, α, β-unsaturated acyl radicals of aliphatic carboxylic acids, for example acrylic acid, α-chloroacrylic acid, propiolic acid, maleic acid and mono- and dichloromaleic acid; as well as the acyl radicals of acids that contain a substituent that reacts with the cellulose in the presence of an alkali, for example the radical of a halogenated aliphatic acid, such as ß-chloroacetic acid, ß-chloro- and 3-RtOBiOP ¹⁰ P ¹⁰¹¹ * acid and &, ß-dichloro * and α, ß-dibromopropionic acid. Further examples are tetrafluoro-cyclobutane-carbonyl *, trifluorocyclobutene-carbonyl-, tetrafluoro-cyclobutyl-ethenyl-carbonyl-,

109840/1632

Trifluoro-cyclobutene-ethenyl-carbonyl and heterocyclic Radicals containing 2 to 3 nitrogen atoms in the heterocyclic Ring and at least one cellulose reactive substituent on a carbon atom of the ring.

Examples of such heterocyclic radicals should be mentioned are: 2,3 - dichloro-quinoxaline-5 · - or -6-sulfonyl-, 2,3-dichloro-quinoxaline-5- or -6-carbonyl-, 2,4-dichloroquinazoline-6- or -7-sulfonyl-, 2,4,6-trichloro-quinazoline-7- or -8-sulfonyl-, 2,4,7- or 2,4,8-trichloro-quinazoline-6-sulfonyl-, 2,4-dichloro "quinazoline-6-caΓbonyl-, 1,4-dichlorophthalazine-6-carbonyl-, 4,5-dichloro-pyridazon-i-yl-, 2,4-dichloro-pyrimidine-5-carbonyl-, 1- (phenyl-4-carbonyl) -4,5-dichloro-pyridazon, 1- (Phenyl-4-sulfony1) -4,5-dichloropyridazone and especially s-triazin-2-yl- and I ^ rrimidin-2-yl- or -4-yl radicals that participate in at least one of the remaining 2-, 4- and 6-positions a bromine atom or preferably a Chlorine atom, a sulfonic acid group, a thiocyano group, an aryloxy or arylthio group with an electronegative one Substituents, for example sulfophenoxy, sulfophenylthio, Nitrosulfophenoxy, disulf © phenoxy and sulfonaphthozy, or a group of the J-formula

- S - C * * Y ¹ (2)

wherein Y stands for a group of alomes which are necessary for the formation of a 5- or 6-membered heterocyclic ring which can carry substituents or can form part of a condensed ring system, or a quaternary Am & onium or I ^ yridinium group or a group of

109840/1532

formula

S.
-SOH '(3)

R ^

1 2
where R and R are identical or different alkyl,

Represent cycloalkyl, aryl or aralkyl groups or

1 2
wherein R and R together with the nitrogen atom one

5- or 6-membered heterocyclic ring, or a group of the formula

-S-G

s *

wherein R and R can be the same or different and each a hydrogen atom or an alkyl, aryl or aralkyl group represent, included.

In the case in which the pyrimidine ring or the triazine ring carries only one such reactive substituent that hung on the remaining carbon atoms may contain a non-reactive substituent.

By the term "non-reactive substituent" is a Meant group that is linked by a covalent bond to a carbon atom of the triazine or pyrimidine nucleus is which covalent bond is not broken under the conditions used for the application of the reactive dye will. Examples of such substituents should be mentioned: primary amino and hydroxyl groups,

109340/1532

as well as mono- or disubstituted amino groups, etherified hydroxyl and etherified mercapto groups. In the case of substituted amino groups, this class includes, for example, mono- and dialkylamino groups in which the alkyl group contains at most 4 carbon atoms and which can also contain substituents, such as. B. hydroxyl or alkoxy groups, as well as phenylamino and naphthy! Amino groups, which preferably contain sulfonic acid substituents. In the case of etherified hydroxyl and mercapto groups, this class includes, for example, alkoxy and alkylthio groups, preferably those having a low molecular weight, ie those having up to 4 carbon atoms, and phenoxy, phenylthio, naphthoxy and naphthylthio groups. Specific examples of all these classes should be mentioned: methylamino, ethylamino, dimethylamino, ß-hydroxyethylamino, di (ß-hydroxyethyl) amino, ß-chloroethylamino, cyclohexylamine, anilino, sulfophenylamino, disulfophenylamino -, IT-MethyIsulfophenylamino-, if-ß-Hydroxyäthylsulfophenylamino-, SuIfo-o-tolylamino-, Oarboxyphenylamino- and Sulfocarboxyphenylamino-, Methoxy-, Ithoxjr-, Butoxy-, Phenoxy-, Methylphenoxy-, Ohlorophehoxy- and. Chlorine atoms or cyano, nitro, carboxy and carbalkoxy groups in the 5-8 position of a pyrimidyl radical fall into the category of non-reactive substituents.

A preferred class of the new dyes is represented by the Formula 1 shown, wherein D is the radical of a 1: 1 copper complex an ο, ο · -dihydroxyasonaphthalene-polysulfonic acid and in particular for a radical of the formula

109840/1532

(5)

wherein η is 1 or 2, stands.

Another preferred class of the new dyes is represented by Formula 1, wherein D is a radical one 1: 1 copper complex of an ο, ο '-Diuoydroxyphenylazonaphthalinpolysulfonsäure and especially for a radical of the formula "

(6)

wherein η has a value of 1 or 2 and the benzene ring ₃ H may be further substituted by Cl ₁ P ₂ or SO, represents.

Another particularly preferred class of the new dyes is formed by those in which D is a radical one 1: 1 copper complex of a phenylazo-o'-hydroxyphenylazo-onaphthol the general formula,

0 chi 0

(HO ₃ S,

N-H

(7)

109840/1532

where Σ, H, OEU or ΟΗ, Ο "means and m and η each independently of one another are 1 or 2, stands.

Another particularly valuable class of the new dyes is formed by those in which D is a radical a 1: 1 copper complex of a 2- (ο-hydroxyphenyl or o-hydroxynaphtny1-azo) -8-amino-1-naphthol-5 »7-disulfonic acid, such as for a radical of the formula

NH.

(δ)

stands.

Another particularly valuable class of dyes will be formed by those in which D is a radical of a bis 1: 1 copper complex of a dihydroxydiphenyl-disazo-dinaphthol stands in which one or both naphthalene nuclei are replaced by a » dical of the formula

-N- CT G-NH

SO ₃ H

NH-X

(9)

Cl

is substituted. For example, D means a radical of the formula «'

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21Q9900

Gu O

(10)

where m and η are independently 1 or 2 and T , H ₁ KH2 or a group of the formula 9 can

According to the invention, a process for the preparation of the new dyes is also proposed, which is carried out thereby is that one is an amine of the formula

D-N-

N .H

(1-1)

Cl

with an acid chloride or an acid anhydride of a colorless acid containing a cellulose-reactive substituent, implements.

The above method can be conveniently carried out by stirring the participants in an aqueous medium at a Temperature of ö-80 ° C are carried out, the pH of the Medium is preferably kept at 5 to 7.

109840/1532

Examples of halides or anhydrides of colorless acids that can be used are: carbyl sulfate and the anhydrides or acid halides of δ, B-unsaturated aliphatic acids, such as chloromaleic anhydride, propiolyl chloride and acrylyl chloride, the acid chlorides of halogenated aliphatic acids, such as, for example, chloroacetyl chloride, sulfochloroecetyl chloride, ß-bromo- and ß-chloropropionyl chloride and α, Β-dichloro and ei, ß-dibromopropionyl chloride, 2,2,3,3-tetrafluorocyclobutane carbonyl chloride, ß- (2.2 , 3,3-tetrafluoro-cyclobutyl) acrylyl chloride, 2,3,3-trifluoro-cyclobut-i-en-carbonyl chloride, ß- (2,3,3-trifluorocyclobut-1-enyl) acrylylchloria, and heterocyclic compounds, the at least 2 nitrogen atoms in the heterocyclic ring and also 2 or more halogen atoms, especially chlorine atoms in the ortho positions to the nitrogen atoms, such as 2,3-dichloroquinoxaline ~ 5- or -6-carbonyl chloride, 2,3-dichloro-quinoxaline-5- and -6-sulfonyl chloride , 2,4-Dlchloro-quinazoline-6- and -7-sulfonyl chloride, 2,4,6-trichloro-quinaaolin-7- and -8-sulfonylchlori4, 2,4-7- and 2,4, e-trichloro- quinazoline-e-sulfonyl chloride, 2,4-dichloro-quinazoline-6-carbonyl chloride, 1 ^ -dichloro-phthala- * in-6-carbonyl chloride, 2 ^ -dichloro-pyrimidine ^ -carbonyl chloride, β- (4,5-dichloropyridazonyl -i-) propionyl chloride, 1- (4 ^t -chloro-formyl-phenyl) -4,5-dichloro-6-pyridazon, 1,4'-chlorosulfonylphenyl - ^^ - dichloro-e-pyridazon, 2, 4,6-tribromo and 2,4,6-trichloropyrimidine, 2,4,5,6-tetrachloropyrimidine, 5-methyl-2,4,6-trichloropyrimidine, 5-liter-nitro-2,4,6-trichloropyrimidine , 2,4-dichloro-5-nitro-6-methylpyryaidin, 2,4-dichloro-5-nitropyrimidine, 2,4,6-trichloro-5-cyanopyrimidine, 5-lthoxycarbonyl-2,4-dichloropyrimidine, 2,4 -Dichloropyrimidine-5-carbonyl chloride, cyanuric bromide, cyanuric chloride; the primary condensation products of cyanuric bromide or cyanuric chloride with ammonia, an alkali metal sulfite or thiocyanate or a colorless organic mercaptan, a colorless *

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organic hydroxy compound or a primary or secondary amine, such as methanol, ethanol, isopropanol, phenol, o-, m- and p-chlorophenol, o-, m- and p-Gresol, o-, m- and p-sulfophenol, thiophenol, thioglycolic acid, dimethyldithiocarbamic acid, Mercaptobenzothiazole, thioacetamide, methyl, Dimethyl, ethyl, diethyl, n-propyl, iaopropyl, butyl, Hexyl- and cyclohexylamine, toluidine, piperidine, morpholine, Ethoxyethylamine, ethanolamine, aminoacetic acid, aniline-2,4-, -2,5- and -3,5-disulfonic acid, orthanilic acid, metanilic acid and sulfanilic acid, 2-, 3- and 4-aminobenzoic acid, 4- and 5-sulfo-2-aminobenzoic acid, 4- and 5-sulfo-o-tdluidin, 5-amino-2-hydroxybenzoic acid, 2-amino-ethane sulfonic acid, Aminonaphthalene mono- and disulfonic acid and N-methylaminoethane sulf acid, as well as the secondary condensation · » products of cyanuric chloride with alkali metal sulfites, alkali metal thiocyenates, Phenols and thiophenols with an electronegative substituent and compounds of the formulas,

S IT-SC Τ ^Ί (12) HSC-

B 'and H - S - C

wherein Y, R, E, H ^ and R ^{4 have} the meanings given above. The amines of the formula (11) can for their part be obtained by condensing equimolecular proportions of cyanuric chloride, a phenylenediamine disulfonic acid and a compound of the formula B-JHF with one another.

109140/1632

As examples of phenylenediamine disulfonic acids which can be used, there should be mentioned; 1,4-diaminobensol-2,5 * disulfonic acid and 1,3-diaminobenzene-4-, 6-disulfonic acid.

As examples of classes of compounds of the formula D - NHS, which can be used should be mentioned: (a) 1: 1 metal complexes and in particular 1: 1 copper complexes of monoazo compounds of the formula

OH

r%. (15)

₁ where D is a mono- or dicyclic aryl radical, which is free of azo groups and has an OH or COgH group in o-position to the azo group and in which the NHR *? group precautionary note on the 6-, 7- or 8-position of naphthalene * is bound to the nucleus, which has a sulfonic acid group la of the 5 * or 6-position of the naphthalene nucleus.

In this class, the related dyes should also be considered in which the HHR group is not attached to the Naphthalene nucleus but to a benzoylamino or aniline— group is bound in the 6-, 7- or 8-position of the naphthalene nucleus is present.

Particularly valuable dyes are obtained from those in which D _{1 is} a sulfonated o-hydroxyphenyl or o-hydroxynaphthyl radical, the ethenyl radical continuing

103840/1632

can be substituted, for example by halogen atoms such as chlorine, alkyl radicals such as methyl, acylamino groups such as Acetylamino and alkoxy radicals such as methoxy.

(b) 1: 1 metal complexes and in particular 1: 1 copper complexes of disazo compounds of the formula (15) where D _{1 is} a radical of the azobenzene, azonaphthalene or rienylazonaphthalene series, which is a metallizable group in the ortho position to the azo group shown and in which the naphthalene nucleus is substituted by the group HHE and optionally by sulfonic acid as in class (a).

(c) 1 ^ metal complexes and in particular 1: 1 copper complexes of mono- or qisazo compounds of the formula,

HHD ₂ -H = RE (16) R

wherein Dg is an arylene radical with a metallizable group in the ortho position to the azo group, for example a radical of the azobenzene, azonaphthalene or hjenylazonaphthalene series, or preferably a maximum of a dicyclic arylene radical of the benzene or haphthalene series, and E is the radical of a haphtholeulphonic acid or daa an enolized or enolizable ketoffiethylene compound, (such as, for example, an Aeetoaeetarylid or a 5 ~ pyrazolone), wherein the OH group is in the ortho-position ζην azo group. D2 preferably denotes an ecddfcal of the o-hydroxyphenyl series which contains a sulfonic acid group. (d) lii-Metallkoffiplexe and in particular 1: 1-Eupferkomples: e of mono- or digazo-compounds de-i * formula,

D ₁ - N »H - K ₂ - IiIiR (17)

109840/1632

- Ip-

where D / j for a radical as above for D ^ in the classes (a) - and (b) defined type and where Kp denotes Radical of an enolizable etomethylene compound (such as an acetoaoetylid or a 5 ~ yra bolone) means, the OH group being in the a ^ position to the azo group.

As examples of specific compounds of the formula D-HHR the following should be mentioned:

the Eupfer complex of 6 ^J , 8-diainino-1,1'-dihydroxy-2,2'-azonaphthalene-4 · ', 5>7> 8 * -tetrasulfonic acid, the copper complex of 8-amino ~ 1-hydroxy-2 ~ (2 '- hydroxy-3 ^l chloro-5'-sulfophenylazo) naphthalene-3 »5-disulfonic acid, the copper complex of 8-amino-1-hydroxy-5» 7-disulfo-2- (2 · -hydroxy-5 '-amino-3 * -sulfophenylazo) naphthalene, the copper complex of 1,2'-dihydroxy-6', 8-diamino-1 ', 2-azonaphthalene-4 ·', 5 »7-trisulfonic acid, the copper complex of 6 -Amino-8'-benzoylamino-1,1'- dinydroxy-2.2 ^t ~ a »onaphthalene-3 ' Λ * & , 8-tetrasulfonic acid, the copper complex of 8-amino-1-hydroxy-2- (2'-hydroxy-5'-sulfophenylazo) naphthalene-3 »6-disulfonic acid, the copper complex of e-amino-1-hydroxy-2- (2 ^l -hydrary-5 ^l aulfophenylaeo) naphthalene-3-sulfonic acid, the copper complex ron 6- Amino-1-hydroxy-2- (2 * -hydroxy-5 ¹ sulfophenylazo) naphthalene-3 _t 5- ^ iaulfonic acid, the copper complex of 8-amino-1,1'-dihydroxy-2,2'-azonaphthaline Λ ', 6,8'-tetrasulfonic acid. the copper complex of S-amino-i-hydroxy- ^ C ^ · ¹ - (2 "-SuIfO-phenylazo) -2 '-methoxy-5' -methylphenylazq3naphthalin-3l6-disulfonic acid,

the copper complex of 6-amino-1-hydroxy ~ 2 - [/ l- ^I - (2 ⁿ , 5 ^ll -dieulfophenylazo) -2'-methoxy-5'-methylphenylazojnaphthalene-3,5-disulfonic acid,

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the copper complex of 1- (3 ^l ~ amino-4 ^l -sulfophenyl) -3-niethyl-4-

O "- (2" », 5" »- disulfophenylazo) -2" -methoxy-5 "-methylphenyl-

azqj -5-pyrazolone,

the copper complex of 7 - (^ ^l ~ amino ~ 3 ^l -sulfoanilino) -1-hy-

droxy-2- [4 "- (2" ·, 5 "'- disulfophenylazo) -2 ^fl -methoxy-5" methyl-

phenylazoJnaphthalene-3-sulfonic acid, and the copper complex of 6- ( ⁱ t -'-Amino-3'-sulfoanilino) -1-hy droxy-2- (2 ⁿ ~ carboxyphenylazo) naphthalene-3-oic acid sulf.

According to the invention there is also a method of manufacture of the new dyes proposed, which is carried out by adding cyanuric chloride with 1 MbI of a compound of the Formula D-HHH and 1 mole of a colorless amine of the formula

BHX (18)

SO ₅ H

wherein the symbols D, B. and Z have the meanings given above own, urneßtat.

The process can conveniently be carried out by stirring the reactants in an aqueous medium at a pH of 5 to 7, adding an acid-binding agent to neutralize the hydrochloric acid released during the reaction the replacement of the first chlorine atom, it is preferred to carry out the reaction at a temperature of. 0-20 ⁰ C, and for a replacement of the swelte $ '

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Chlorine atoms, it is preferred to use a temperature of 50-5O ^e C. In general, it is possible to carry out a reaction with the two amines in any order, but in those cases in which X represents a dichloro-s-triaaine group , it is preferred to first react the cyanuric chloride with an amine of the formula (18) and then the product with the compound D-HHR.

The amines of formula 18 can in turn be obtained by that one has a phenylenediaminedisulfonic acid with 1 molecular Part of the acid chloride or anhydride, a colorless organic one Acid which contains a cellulose-reactive substituent, converts.

A modification of this process can be used to prepare those new dyes in which the by X represented a cellulose-reactive group a dichloro-strlazine group is. In this modified process, 1 mole of the hienylenediaicine disulfonic acid is mixed with 2 kol of cyanuric chloride implemented, and the product obtained is then reacted with 1 ha of the compound of the formula D-NHH, surprisingly the most plumb condensation runs almost completely in eleventh asymmetrical way, although we value that tin considerable proportion of a symmetrically substituted 2 * roduct is formed by reaction of the compound D-NHH with both diehloro-s-triazine groups.

According to the invention there is also a method of manufacture of the dyes of the formula according to the invention

109MD / U32

KA- 3Γ-Ν-Β 'Ii I T L. HH.I (19)

suggested, where A is a 1,2-phenylene or a 1,2-naphthylene redical represents and B represents a 1,2-naphthylene radical, where the group NR is bonded to Δ or to B and where E and X have the meanings given above - The process is carried out by connecting the Fornel

■ OIL '

Subjects a copper salt in the presence of an oxidizing agent to the action.

This process can be conveniently carried out in an aqueous medium at pH 1 to 3, 2.B. in the presence of an acetic acid / acetate buffer, at a temperature in the range of 10-7O ⁰ O. Suitable oxidizing agents are, for example, alkali metal peroxides, percarbonates, perborates, organic peracids, acyl peroxides or air in the presence of an oxygen transfer catalyst, such as anthraquinone-2-sulfone

109840 / U32

acidic or decahydronaphthalene. The preferred oxidizing agent is hydrogen peroxide.

Djs process is particularly suitable for the production of Dyes of the formula (1) in which D represents a radical of the formula (5) or of the formula (8).

The invention also relates to a process for the preparation of the dyes in which X represents a 2-s-triazinyl nucleus which a chlorine or bromine atom is bonded to the carbon 4 atom contains and the at the 6-carbon atom an amino group or contains bound substituted amino group. The procedure will carried out by using a dye according to the invention, where X is a 4,6-dichloro- or ^, e-dibromo-s-triazine ^ group, treated with ammonia or an amine.

The method can thereby be carried out in an expedient manner be that the reactants 5L in an aqueous medium at a pH of 5 to 7 and preferably at a Temperature of 30-5O ° C is stirred, with one for neutralization adding an acid-binding agent to the hydrochloric acid formed during the reaction, or alternatively using a superchulic alcohol or amine for this purpose.

The dichloro- or Mbromo-s-triaainfarbetoff used can can be prepared by any of the methods described above. If necessary, he can before the further implementation isolated and purified, but in general ·· is not necessary. The ammonia or the AoIn can dtm reaction * * * be added to the mixture in which the dichloro- or dibremo-i-trlazine dye has been prepared.

109140/1832

The new dyes can be obtained from the reaction mixtures in which they have been prepared by conventional techniques that are available for the isolation of water-soluble reactive dyes, such as salting out and filtration or spray drying the reaction mixture in which the dye has been prepared. If necessary, stabilizers, such as, for example, alkali metal hydrogen phosphates, can be added will.

The new reactive dyes are useful for coloring cellulose textile materials, e.g. for coloring textile materials, natural or regenerated cellulose such as cotton, linen and viscose rayon. To color such materials, the new dyes are either by a printing process or preferably by a dyeing process on the cellulose textile material in common with a treatment by an acid-binding agent, such as caustic soda, sodium carbonate, sodium alicate or sodium carbonate, which acid-binding agent on the material before, during or after the application of the Dye can be applied. When the new dyes are applied to this, they react with it the Iellulaa * and result in the most varied of color tones • iaer vorsfleliöh · »Waeehechtfaeit. SI «are because of your ·· high The proportion that looks up at the material is remarkable, especially when it is applied from salt baths are applied or separated by printing. They also show themselves through a low top coloration Adjacent undyed materials either during washing out • Tone of the dyestuff not absorbed after printing or during vaschverxichen.

The invention is illustrated in more detail by the following examples Purifies, Ui where all ropes are expressed in weight.

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example 1

A solution of 8.0 parts of the tetrasodium salt of the copper complex s of 8-amino-1,1 · -dihydroxy-2,2 * -azonaphthalene-314 ', e ^' - tetrasulfonic acid (prepared according to the procedure of Example 1 of the British patent 950 871) in 125 parts of water is added to a suspension of 1.85 parts of cyanuric chloride and 14 parts of acetone in 112 parts of ice water at 0-5 ° C., the pH of the mixture being adjusted to between 5 and 7 by adding a 10% aqueous sodium carbonate solution is held. When the condensation ends, a solution of 4.0 parts of the disodium salt of 1,4-diaminobenzene-2,5-disulfonic acid and 30 parts of water is added, and the temperature is raised to 35 to 40 ^° C., the pH is kept between 4.5 and 5.0 by the gradual addition of 10 aqueous sodium carbonate solution. When the condensation is over, a solution of 2.0 parts of cyanuric chloride in 15 parts of acetone is added to the solution of the aminoazo dye at 0-5 ° C., the pH being maintained by adding 10% aqueous Hatrinacarbnatlösung «Irish 5 and. When the condensation is over, a solution of 3.0 parts of aniline in 10 parts of acetone is added, and the temperature is raised to 35-4O ⁰ C, the pH by adding 10% aqueous sodium carbonate], oil between 5 and 7 is held. When the condensation is over, the dye is precipitated by adding sodium chloride, filtered off and dried. It is found that the dye contains 2 atoms of chlorine per azo group. When applied to cellulosic materials in the presence of an acid binder, bright blue shades with good fastness to light and washing are obtained *

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Table I shows further examples according to the invention, which are shown in in a manner similar to that of Example 1. The second column contains the compound of the formula S-HHB used; the third column contains the phenylenediaminedisulfonic acid used; and the fourth column contains that amine used in the most fluid condensation. The last column describes the dye of cellulose textiles, which have been colored with the obtained dye.

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OT ft »

1 1: {-Copper complex τοη 6-Aiali> o-2- (2 ^l -hydroxy-3 ^l ,
5 * -dieulf oph # nylaso) -1-n * pathol-3,5-disulfonic acid 1,4-Dlaminoben-
xol-2,5-diflulfone-
acid ammonia Red 2 1 χ 1-Eupf erkomplex τοη 8-Am ± no-1,1 '-dihydroxy-
2,2 * -azonaphthalenes »4 *, 6,8 '-tetraeulfonaäure * 1,3-diaminobenzene
4,6-disulfonic acid -do- blue 3 - do -
- do - - do -
-do - 1 — Aminonaph
thaline, 6.8-
tri sulfoneäuü
m-sulfoaniline -do-
-do- 5 * - do - - do - p-sulfoaniline -do- 6th Λ : 1 -Eupfer complex of o-methylamlno-2- &'- (2 ¹ *, 5 "-
dlftulf ophenylajio) -2 · -hydroxy-5 '-methylphenylaB ^ J
1-naphthol-2-sulfonic acid 1 j / i — f ^ fliBi nob * MifrOl-
2,5-disulfonic acid aniline > lukewarm 7th 1 1 1 -Eupper complex of β-ΑζηΙηο ^ - [4 '- (2 ⁿ , 5 "-di-
sulf ophenylaBo) -2 * -hydroxy-5 * -methylphenylasqH
1- & apnthol-3,5-dieulf oaefture 1,3-diaminobenzene
4,6-disulfonic acid ammonia blue 8th - do - - do - m-sulfoaniline -do- 9 -do- - do - 3,5-disulfo-
aniline -do- 10 • do - - do - 2,5-disulfo-
aniline -do-,. ₍ .

-11 1s1-Kupferkoapl «ac of 6-AeiA0-2- (2'-hydroxy
5 ¹ -sulfophtnylaso) -1-naphtnol-3,5-dieulfon- 1,3-diaminobenaol
4,6-disulf ongäl «5? E 2,5-disulf ο ··
aniline bluish
ot j j 12th - do - - do - m-Sulfoanilln - do - I purple J 13th - do - 1,4-Dlamlnobenzene-
2,5-diaulfonic acid ammonia - do - j - do - 14th - do - - do - toluene - do - - do - J
- do - 15th - do - ammonia reddish
blue j 16 * ι T-copper complex. from 7 - "\ 2 ·« - «yaroxy — 5 -cnlo—
ro-5'-Bulfophenylaio) -1-amino-e-DAphthol - ?, 6
diaulfonic acid " - do - p-sulfoanaline - do - O
«Ο 17th
1β - do - 1 _t 3-diaminobenzene
4,6-di-sulfonic acid
- do - 1 -Aminonaphthalln-
3,6,8-trlsulfone
acid
ammonia O 19th - do -
- do - - do - 4-sulfo-2-amino-
toluene , 20 1: i-Kupferlcoiaple3c of 8-amino-2- (2'-hydroxy-
3'-BulfO-5'-aminophenylaso) -1-naphthol-5,7-
dieulfoneätEr « 1,4-diaminobenzene m-sulfoaniline - do - *

O CD (O O O

• 3§

S 5

• d

ι ι

I.

O

VIr-I Vl

• AS "i

m '

ir ».

CU

H Φ O U U 3

2S

O O

a m

5 I.

• ti

ti

•egg*

a ^

OJ

et

US Φ CU CM

105840/1832

H Φ O U

H I.

οί

• ö

s a

- 24 - Example 2

A solution of -1.85 parts of cyanuric chloride in 10 parts of acetone is converted to a neutral solution of 8.0 parts of the tetrasodium salt of the 1: 1 copper complex of 8-amino-1,1'-dihydroxy-2,2'-azonaphthalene 3i4 ', 6,8'-tetrasulfonic acid in 160 parts of water at 0-5 ° C was added. The mixture is stirred st at 0-5 ⁰ O 2, wherein the pH is maintained by addition of 10% sodium carbonate 5 to 7 The mixture is then filtered. A neutral solution of 3 »1 part of the disodium salt of 1,4-diamino-benzol2,5 ■ diBulfon8äure in 30 parts water is then added, and the mixture is heated to 35-4-O ⁰ C, wherein the pH by the addition is kept between 4.5 and 5 * 0 by 10% sodium carbonate solution. After the condensation has ended, the product is precipitated by adding a 25% strength potassium chloride solution and filtered off.

The product is redissolved in 250 parts of Eiswaseer, and a solution of 2 * 0 parts of cyanuric chloride in 12 parts of acetone is added. The mixture is stirred st at 0-5 ⁰ G 3, wherein the pH by addition of 10% sodium carbonate solution is between 6 and 7 held. The end of the reaction is determined by TLC. The solution is filtered and the product is isolated by the addition of sodium hydride and filtered off. The product is stabilized before drying by adding 3.0 parts of a mixture of 2 parts potassium hydrogen orthophosphate and 1 part disodium hydrogen orthophosphate to the paste. The product, which contains 3 atoms of hydrolyzable chlorine per azo group, dyes cellulose fibers in bright blue dyes with good fastness to vaping and light when it is in the presence of an acid-binding agent

109840/1532

is applied. Example 3

A neutral solution of 96 parts of I ₅ Hatriuiasalzee of metanilic acid in 20 parts of water is added to a stirred suspension of 1.85 parts of cyanuric chloride in a Ilischunv; of 10 parts acetone and 60 parts water was added at 0-5 ⁰ C. The pH is constantly maintained at 4.0-4.5 by the addition of 1N sodium hydroxide solution and stirring is continued under these conditions for 1 hour. After filtering, the resulting solution is added to a neutral solution of 3.12 parts of the disodium salt of 1,4-diaminobenzene- · 2,5-disulfone acid , and the mixture is then added

Stirred for 4 hours at 30-35 ° C., during which the pH is kept at 4 to 4.5 by adding 1N sodium hydroxide. Bach cooling to 0-5 ⁰ C., the solution added to a suspension of 2.0 parts cyanuric chloride in a mixture of 10 parts acetone and 30 parts of water at 0- £ ° C is added. The pH is maintained at 6.0 Ma 7.0 by adding 1N sodium hydroxide and stirring is continued under these conditions for 3 et. After the reaction is over, the QeBitch is filtered and the filter is filtered into a solution of 8.0 parts of the tear, triuosalree de 1: i-copper complexes of 8-amino-1,1'-dihydroxy-2,2 · -Assonaphthalene-3,4 ', 6.8 · * * te tra sill fonsäure added in 60 parts of water. The mixture is heated to 30-35 ° C., the pH being adjusted between

5 and 7 is held. After the reaction ends, winidas product salted out, filtered off and dried. Because «product which contains 2 atoms of hydrolyzable chlorine each Contains azo group, when it is in the presence of an acid binding agent is applied to cellulosic materials.

109840/1532

blue shades with an excellent fastness to light and vashening.

Table II shows further examples of the invention Dyes prepared in a manner similar to Example 2 or 3. In column 2 is the one used Compound of the formula D-UHR indicated; in column 3 the phenyleadiaminedisulfonic acid used is indicated; and in column 4 is the acid chloride or acid anhydride of a color acid which has a cellulose-reactive substituent contains, indicated that instead of the cyanuric chloride in the second 'paragraph of Example 2 ode, r instead of the condensation product of cyanuric chloride and metanilic acid of Example 3 was used. The last column describes the shade of cellulose textiles obtained with the Dye have been dyed.

1 111 -Copper complex of 6-amino ~ 2- (2 '-hydroxy-3',
5'-disulfophenylazo) -1-naphthol- ^ t5-dieulfonic acid 1
2 , 4-diaminobenzene
, 5-dieulfonic acid 2,4,6-trichloro-
pyrimidine do - do - • 2 - do - - do - Carbyl sulfate do - do - 3 - do - - do - 2,4-dichloropy-
rimidine-5-carbo-
nyl chloride do - do - 4th - do - - do - 2,3-dichlorochi-
noxaline-e-carbo-
nylchlorld do - do - 5 - do -
* - do - 2,4-DlChIOrO - ^ -
amino-s-triazine blue do - O
«D
09
O 6th 111-copper complex of 8-amino-1,1 · dihydroxy-2,2 '■
azonaphthalene-3,4 »-6,6'-tetraulfonic acid - do - 2,4-dichloropyri-
Eiidin-5-carbonyl-
claloria - 7th - * do - - do - Carbyl sulfate - 532 δ - do - - do -
• 2,4,6-trichloro-
pyrimidine 9 - do -
* - do - 2,3-Biciaorochi-
noxaline-6-carbo-
nylon chloride 10 - do - 1
4th , 3-diaminobenzene
, 6-disulfonic acid 6- (3 ', 6', 8'-TrI-
sulfonaphth-1-yl-
amino) -2,4-dichlo-
ro-s-triazine 11 - do - - do - 6- (m-sulfoanilino>
2,4-dichloro-e-
triazine
• bluish
pot - -

j. - do - 1,3-diaminobenzene ~
A-, 6 ~ disulf onsäujc " 6-amino-2,4-dichloro-
s-triazine blue - do -
L """ - do - 6- (p-sulfoanilino) -
2, ^ - dichloro-s-triaziÄ - do - | '^ "j * - do -
a 'j!
? Γ 2 \ 5- & i8uliOic Acid 6 — Aiiillno — 2 ^ b- dich.lorO "
s-triazine marine
blue 1.3 ~ Maminobenzene
4 ₁ 6-diaulfonic acid Cyanuric chloride blue - dd - 2, ^ - dichloro-6-amino-
s-triazine - do - - ** ikscu i-saphtbol ^ fe-disulfoiisittrt - do - 2,4-DiChIOrO-S- (m-sul-
jToaniliao) -s-triazine - do - * £ ** within the meaning of § ■ - do - - do -
• 2, ^ - Dichlo'ro-eC 3,5-
disulfoanilino) -e-
triazine - do - Ξ!] V j - do -
- ** ■; ί - do -
• 2,4-dichloro-6- (2.5-
dieulfoanilino) -a-
triazine - do - 18th 19th
j
ί

1: 1 copper complex of 6-amino-2- (2'-hydroxy "5'-sulfophenyiaso)-1-naphthol"?"5-dlenlfonic acid

- do -

- do -

- do -

- do. -

1: 1 copper complex of 7- (2'-hydroxy-3'-ch.lo · ro-5'-sulfophenylazo) -1-amino-8-naphthol-316-disulfonic acid

- do -

- do -

- do -

, 4-diaminobenzene-2,5-di-sulfonic acid

- do -

- do -

1,3-diaminobenzene 4,6-di-sulfonic acid

- do -

1,4-diaminoben, jsol 2,5-di-sulfonic acid

- do -

- do -

- do -

2,4 ~ dichloro-6-amino-s-triazine

bluish red

meth.oxy-a-triaziJ3

(2 ^l -methyl-5 '~
sulfoanilino) -s-triazine

(m-sulfoanilino) -s-triazine

2,4-dichloro-6- (2,5-disulfoanilino ) -s-triazine

xalin ~ 6-carb onyl chloride

Carbyl sulfate

2,4-dichloropyrimidine-5-carbonyl chloride

2,4,6-trichloropyrimidine

- do -

- do -

- do -

- do purple

- do -

- do -

- do -

29 1: 1 copper complex of 7- (2'-hydroxy ^ ¹ -chloro-
5 * -gulf ophenylazo) -1 -amino-e-naphthol-J » 6-di-
ffulfon # Äup9 1,4-diaminobenzene (p-sulfoanilino) -
8-triazine purple 50 - do - - do - 2,4-dichloro-6-
amino-8-triazine - do - 31
32 - do -
- do -
♦ - do -
1,3-diaminobenzene
4,6-di-sulfonic acid methoxy-e-triazine
2, A-dichloro-6- (3 'ι
6 ¹ , av-trisulfonaphtb.
1-ylamino) 8-triazine - do -
- do - 33 - do - - do - methoxy-s-triazine - do - _. - do - - do - amino-a-triazine - do - 35 1: 1 copper complex of 8-amino-2- (2 ^l -hydroxy-3 ¹ ·
«Ulf 0-5 '-aminophenylazo) -1 -naphthol-5 * 7-Ai-
sulfonic acid 1,4-diaminobenzene
2,5-diaulfonic acid
9 2,4-dichloro-6-
(m-eulfoanilino) -
s-triazine reddish
blue 56 • - do -
• 1 »3-diaminobenzene 2,4 ~ dichloro-6- (2 · -
metfayl-5 ¹ -eulfoani
lino) -β-triazine - do -

5? ! 1s1- £ TOferk © srolex from 6 *, 8-Diaaino-1,1 '-
dibs ^ ros7-2,2 "'-asonaphthalene-4 ·, 5» 7-tri-
sulionate ι - do - 1, ^ - diaminolsenzene-
2.5 ~ iisulxonic acid 2,4 - DiChIoXO-G-C2 '-
iaetli7l-5 '-sulf o ~
anilino) ~ s-triazia marine
blue 33 - do - - do - 2,4-dichloro ~ € -
ä-fchoxy-s-triazine, - do. - 39 - do - - do - 2,4-DiChIOrO-G-
amino-s-triazine - do - 40 - do - 1, J-diamiaobenzene-
4,6-d.isulx casä-ure - do - "do - I do - - do - 2, A-dichloro-6- (2'-
iaetlijl-5 '~ stilf o-
anilino) -s-triazine - do - - do - 2 _t 4-dicliloro-6-
asethoxy-s -triasin
• - do - - do - 2,4-dichloro-6- (ia-
aulfoaniliao) -s-
triazine - do -

44 Bi8-1j1-Kupferkofflpler of 4,4'-UIe-Ce "-
imino — 3 ", 6 -disulfο — 1" —hydroaeynAplrth-2 "-
rlazo) -3,3'-dihydroxy-diphenyl 1,4-diaminobenzene
2,5-diaulfonic acid 2,4-dichloropyrimidine
5-0 carbonyl chloride blue .45 - do - - do - Cyanuric chloride - do - 46 - do - * do - 2,4-DiChIOrO-O-C 2 ·, 5'-
disulfoanilino) -s-triasine - do - 47 - do - - do.-.- Carbyl sulfate - do - 48 * do - - do - 2,4,6-trichloropyrimidine - do - 109! 49 - do - - do - 2,3-dichloroquinoxaline
6-carbonyl chloride - do - / 078 50 - do - 4,6-dieulfone acid Cyanuric chloride - do - 1S32 51 - do - - do - 8-triazine - do - 52 - do - - do - 2 ^ -Dichloro-e-amino-
8-triazine - do - 53 - do - • - do - 2 ^ -Dichloro-e-Cm-sulfo-
anilino) -e-triazine - do - 54 - do - - do - 2,4-dichloro-6-C2 ', 5'-rdi
sulfoanilino) -a-triazine - do -

- 53 -

Example 4

A solution of 1.85 parts of cyanuric chloride in 15 parts of acetone is added to a solution of 3.63 parts of the disodium salt of 1-amino-8-naphthol-36-disulfonic acid in 100 parts of ice water. The mixture is stirred at 0-5 ° C until the reaction is complete, and the pH is then raised to 6. The solution is filtered and a solution vnn 4.1 g of the disodium "umsalzes of 1,4-diaminobenzene-2,5-disulfonic acid .in 20 parts sugegeben water, and the mixture is heated to 35-40 ⁰ C, the pH being kept between 4 and 4.5 by adding 10% sodium carbonate solution. After the condensation has ended, the product is isolated by adding 10% sodium chloride solution and filtered off. The fast is dissolved in 100 parts of ice cream and a solution of 2.0 parts of cyanuric chloride in 10 parts of acetone is added. The mixture is stirred at 0-5 ° C. until the acylation has ended, the pH being kept between 6 and 7 by adding 10% sodium carbonate solution. ₉

Ammonia liquid (Speslflsches weight 0.88, 3.0 ml) then added, and the temperature is raised to 25-3O * C, until the amination is over. The pH is adjusted with acetic acid lowered to 7, and 41 «solution is obtained by adding« from SI « cooled to 0-5 * C. A suspension in the usual way prepared from 3.0 parts of 2-haphthylamine-4,8-disulfonic acid Diazonium salts are then slowly added, keeping the pH at 5 by adding sodium acetate. After the coupling is over, the product is added by adding isolated from potassium chloride, filtered off and dried.

109840/1532

- 254 -

11.2 parts of the product obtained are dissolved in 100 parts of water at 25 ° C. The pH is lowered _v by the addition of 2N hydrochloric acid to 3 »5 and a LÖ3ung of 3 parts of copper (II) sulfate pentahydrate in 15 parts of water is added" The pH of the mixtures is prepared by adding sodium acetate to 4.5 to 5 »O raised, and 17th parts of a 20% strength hydrogen peroxide solution are dispensed for 1 hour. The mixture is stirred for a further hour and the product is isolated by adding potassium chloride, filtered off and dried. The product contains 2 atoms of hydrolyzable chlorine per λζο group. When it is applied to cellulose textile materials in the presence of an acid-binding agent, it gives bright blue shades with good fastness to light and vaechen.

The same dye can be obtained when 2,4-dichloro-6-amino-s-triazine is used instead of the second condensation with cyanuric chloride and subsequent amination, wherein the reaction is carried out at a pH between 6 and 7 and * at 35 ° C.

Other dyes with similar properties can be used in similar You can get earth instead of 2,4-dichloro-6-amino-s-triazine the following compounds are used: 2,4-dichloro-6- (a-sulfoanilino) -s-triazine 2,4-dichloropyriiaidin-5-carbonyl chloride Carbyl sulfate

2,4,6-trichloropyrimidine
2,3 ~ dichloroquinoxaline-6-carbonyl chloride or if the 1,4-diaminobenzene-2,5-disulfonic acid is replaced by 1,3-diaminobenzene-4,6-disulfonic acid, and if the

The following compounds can be used for the subsequent condensation before coupling:. _φ

109840/1532

2,4-dichloro-6-amino-s-triazine 2,4-dichloro-6- (m-sulfoanilino) -s-triazine 2,4-dichloro-6- (p-sulfoanilino) -a-triazine

2,4-dichloro-6- ( ^{3x, 6 ', 8 f} -trisulfonaphth-1 ^l -ylamino) -e-triazine

2,4-dichloro-S-anilino-s-triazine

Example 5

A solution of 4-6 parts of cyanuric chloride in 30 parts of acetone is added to a neutral solution of 1.34 parts of 1,3-diaminobenzene-4-, 6-di8ulfonic acid in 200 parts of water at 0-5 ° C. The mixture is stirred at 0-5 ⁰ C st 24, wherein the pH is maintained by addition of 10biger Nstriumcarbonatlösung 6 to 7 Non-etched cyanuric chloride is removed by filtration, and the liquid becomes a neutral solution of 8.0 parts of the tetrasodium salt of the copper complex of 8-amino-1,1'-dihydroxy-2,2'-azonaphthalene-3,4 ', 6,8'-tetrasulfonic acid in 60 parts of water was added. The solution is heated to 25 ⁰ C, the pH is maintained by addition of 10 $ strength Hatriumcarbonatloeung 6 to 7 When the condensation has ended, the product is isolated by the same procedure as in Example 2. It is found that it contains 5 liters of hydrolyzable chlorine 4 * a group. It dyes cellulose fibers in the presence of an acid-binding agent in bright blue shades with good fastness to light and vashing.

In Table III some other fax items according to the invention are indicated, which can be prepared in a similar Veise by adding the specified metal complex of the formula D-HHR and the specified diaminobenzene disulfonic acid for the condensation. with 2 molecular fractions of cyanuric chloride is used.

109840/1532

«Ο do

cn id

1 111 -Eupf erkompleac of 8-Aaino-1,1 '-dlbydros7 ~ 2.2-
& zomaphthalene-3 * V "6,8'-t" traeulfona acid 1,4-diaminobenzene-2,5-
dissilfonic acid bright blue 2 lii-Kupferkoinplex voa a-AÄlno ^ -ßl -'- Ca ¹¹ ^ "· ^ !! -
eulf ophenylas5O) -2 '-hydroxy-5 * -mettiylplienylaaqj -
1 -naph.thol-3 »6-dialulfoic acid •
1,3-ϋ1βπι1ηοΙ) θΐιζο1-4 »6 ^
dialfonic acid blue 3 Bie-iti-copper complex clay 4,4- ^l -ble- (8 ⁿ -aniino-
3 ", 6" -dieulf 0-1 "-hydroatynaphth-a ^ -ylaao) ^, V -
dihydroxydiphenyl - do - - do - - do - 1,4-diaminobenaol ~ 2.5-
dieulfone & ur - do -

J *

K)

co * to

Claims (1)

Claims NH-X wherein H stands for H or an alkyl group, D for the best one 1: 1 metal complex aminoazb compound of the formula D-BEH, and Σ for the remainder of a colorless organic acid which contains a cellulose-reactive substituent. 2. Process for the preparation of the dyestuffs according to Claim 1, characterized in that an amine of the formula At v SO, H * I ^E. \ J ßl with the acid chloride or acid anhydride of a colorless acid, which contains a cellulose-reactive substituent, was set fit « 109840/1532 3. Process for the preparation of the dyes according to Claim 1 characterized in that one cyanuric chloride Bit 1 KoI one Compound of the formula D-BHR and 1 mole of a colorless one. Amines the formula « HHX wherein the symbols D, R and X have the meaning given in claim 1, uasetst. 4. The method according to claim 3 «for the production of those Dyes in which the alt cellulose reactive group represented by X is a dichloro-s-triasin group, thereby characterized in that 1 hol of ifcenylenediamine disulfonic acid is reacted with 2 hol of cyanuric chloride and the * obtained Product then alt 1 Hol of a compound of the formula D-SHR umaetst. 5v procedure * u? Production of the dyes according to AASpruob I, (O _mmm QVL Ov ¹ 0 'α -ι * ar- b-JL -ι - c 0 ^ Cu ^. have, wherein A is a 1,2-phenylene or 1,2-uaphthylenre.dical 109840/1532 represents and B represents a 1,2-haphthylene radical, where the Group HB let bound to A or B and B and Z have the meanings given in claim, characterized in that dafi one compound of the formula I. ΟΒΛ H . ΟΗ \ H „ _{η w} ^ J · Γ J- »HI ι, 'SO3H Cl subjected to the action of a copper salt in the presence of an oxidizing agent 6. Process but preparation of the dyes of claim 1, in which Σ «inen 2-e-Triazinylkem, the one to the carbon atom in the 4-position bonded chlorine or a bromine atom and an amino or substituted amino group bonded to the carbon atom in the 6-position, characterized in that a dye is added Claim 1, la the Z · && · ^, 6-Diohloro- or 4,6-Dlbro'o-etrlasln - ^ - 71-grapp · means, with ammonia or an amine treated. * I I 1098 * 0/1532