DE2845846A1 - AZO DYES AND THE PROCESS FOR THEIR MANUFACTURING AND THEIR USE FOR COLORING CELLULOSE TEXTILE MATERIALS - Google Patents

Description

October 2, 1978

PATENT ADVOCATE

DR.RICHARD KMEISSL 2845846

Widsnmayerslr. 45

D-8000 MUNICH 22 y

Tel. 089/295125

Folder 24512

ICI Case Dd 29872 / DT

IMPERIAL CHEMICAL INDUSTRIES LTD. London, UK

Azo dyes and processes for their preparation and their use for dyeing cellulose textile

materials

Priority: November 3, 1977 - Great Britain

909819/0646

DESCRIPTION:

The invention relates to new azo dyes and their Copper complexes, especially those dyes that carry a group that is reactive with cellulose.

According to the invention, dyes are proposed which have the formula in the free acid form:

(1)

(SO, H) in

R ^{1 represents} H or CH ₃ ,

R is H or C _1-4 alkYl,

Y stands for an acyl group,

Q stands for a group reactive with cellulose, η stands for 1 to 4,
χ stands for 0 or 1,
m stands for 1 to 3,

wherein the ring A can be further _{substituted by SO 3} H, the group R (Q) N. (CH2) - is in the m- or p-position to the azo group and, if Q contains an s-triazine ring, a carbon atom of the same is directly connected to the group NR.

It is preferred that R is methyl and especially H.

It is preferred that η be 1. It is preferred that R is H.

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The acyl group Y is a non-chromophoric group free of substituents reactive with cellulose.

A preferred class of acyl groups Y includes the optionally substituted alkanoyl groups having 1 to 3 carbon atoms. Substituents for this group are, for example, SO ₃ H, OH, Cl.

Another preferred class of acyl groups Y comprises the aroyl groups, in particular the optionally substituted benzoyl groups. Suitable substituents for this form of Y are, for example, SO ₃ H and Cl.

Another preferred class of acyl groups Y comprises the arylsulfonyl groups, in particular those which may be substituted Benzenesulfonyl groups.

Examples of groups Y in formula (1) are acetyl, suIfoacetyl, Benzoyl, sulfobenzoyl, benzenesulfonyl and toluenesulfonyl, e.g., p-toluenesulfonyl.

¹ It is usually preferred that m is 2 or 3, especially when other water-solubilizing substituents are absent throughout the dye.

Preferred dyes have no further substituent on the ring A or one or two further substituents selected from COOH, C _1. -Alkyl, C _1-4 -alkoxy, halogen, in particular Cl, CN, NO _3, and OH.

Examples of groups reactive with cellulose are aliphatic sulfonyl groups which have a sulfate ester group in the β-position to the sulfur atom, such as ß-sulfatoethylsulfonyl groups; a, ß-unsaturated acyl radicals from aliphatic carboxylic acids, such as acrylic acid,-chloroacrylic acid, oc-bromoacrylic acid, propiolic acid, maleic acid

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and mono- and dichloromaleic acid; Acyl radicals from acids, containing a substituent that reacts with cellulose in the presence of an alkali, such as radicals of halogenated aliphatic acids, for example chloroacetic acid, ß-chloro- and ß-bromopropionic acid and (Χ, β-dichloro- and -dibromopropionic acid; and radicals of vinylsulfonyl or ß-chloroethylsulfonyl or ß-sulfatoethylsulfonyl-endo-methylenecyclohexanecarboxylic acid. Further examples of groups reactive with cellulose are TetrafluorocyclobutylcarbonyI, Trifluorocyclobutenylcarbcnyl, Tetrafluorocyclobutyläthenylcarbonyl and Trifluorocyclobutenyläthenylcarbonyl; activated halogenated 1,3-dicyanobenzene radicals, such as 2,4-dicyano-3,5-difluoro-6-chlorophenyl, 2,4-dicyano-3,5-difluoro-6-nitrophenyl, 2,4-dicyano-3,5,6-trifluorophenyl, 2,4-dicyano- ~ 3,5,6-trichlorophenyl, 2,4,6-tricyano-3,5-difluorophenyl and 2,4,6-tricyano-3,5-dichlorophenyl; and heterocyclic radicals containing 1, 2 or 3 nitrogen atoms in the heterocyclic Ring and at least one cellulose-reactive substituent on a carbon atom of the ring .

It should be noted that many reactive groups can be defined as both heterocyclic groups and acyl groups because they are composed of an acyl group bearing a heterocyclic substituent. If in such cases the heterocyclic ring bears the substituent reactive with cellulose, then for the sake of simplicity these rings are usually referred to as heterocyclic reactive groups in this description .

Examples of such heterocyclic groups are: 2,3 ^w dichloroquinoxaline-5- or -β-ΞμΙίοηγΙ, 2,3-DiChIOrOChInOXaUn-S- or -6-carbonyl, 2,4-dichloroquinazoline-6- or -7-sulfonyl, 2 , 4,6-trichloroquinazoline-7- or -8-sulfonyl,

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2,4 _f 7- or 2,4,8-trichloroquinazoline-6-sulfonyl, 2,4-dichloroquinazoline-6-carbonyl, 1 ^ -Dichlorophthalazin-ö-carbonyl, 4,5-dichloropyridazon-i-yl-ethylcarbonyl, 2,4-dichloropyrimidine-5-carbonyl, 4- (4 ', 5'-dichloropyridaz-6'-on-1-yl) benzoyl, 2-chlorobenzothiazole-6-carbonyl, 3,6-dichloropyrazine-4-carbonyl and 4- (4 ', 5'-dichloropyridaz-6'-on-1'-yl) phenylsulfonyl ;.

activated 4,6-dihalopyridin-2-yl and 2,6-dihalopyridin-4-yl groups, such as.

3,4,5,6-tetrafluoropyridin-2-yl, 2,3,5,6-tetrafluoropyridin-4-yl, 2,5,6-trifluoro-3-cyanopyridin-4-yl, 2,5 ', 6-trichloro-3-cyanopyridin-4-yl, 2,6-Difluoro-3-cyano-5-chloropyridin-4-yl and 2,6-difluoro-3,5-dichloropyridin-4-yl; and most particularly triazinyl and pyrimidinyl groups.

Examples of special pyrimidinyl groups are pyrimidin-2-yl- and -4-yl groups which contain an atom reactive with cellulose or a group reactive with cellulose, in particular Cl, Br or F, contained in at least one of the free 2-, 4- and 6-positions. The 5-position can have various substituents such as Cl or CN, which are normally not reactive with cellulose, but which reduce the reactivity of substituents in other positions of the pyrimidine ring can improve. Specific examples of such pyrimidinyl groups are:

2,6-dichloropyrimidin-4-yl, 4,6-dichloropyrimidin-2-yl, 2,5,6-trichloropyrimidin-4-yl, 4,5,6-trichloropyrimidin-2-yl, S-chloro ^ -methylsulfonyl-e-methylpyrimidiri- 4-yl / 2,6-dichloro-5-cyanopyrimidin-4-yl, 4,6-dichloro-5-cyanopyrimidin-2-yl, 2,6-difluoro-5-chloropyrimidin-4-yl,

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4,6-di fluoro-5-chloropyrimidin-2-yl, 2,6-Difluoro-5-cyanopyriniidin-4-yl and 4,6-difluoro-5-cyanopyrimidin-2-yl.

Examples of particular triazinyl groups are triazin-2-yl groups which have atoms or groups reactive with cellulose at one or both of the 4- and 6-positions. In this case, a wider range of cellulose reactive atoms or groups are available, such as activated aryloxy and various other groups bonded through a sulfur atom, but the preferred reactive atoms or groups are F, Br and especially Cl; quaternary ammonium groups, such as, for example, tri-lower alkylammoium groups, such as, for example, (CHo) ₃ N and pyridinium groups, in particular those which are derived from pyridinecarboxylic acids, especially from nicotinic acid.

The triazinyl groups that contain only one reactive atom or one reactive group on the nucleus in the 4- or 6-position, may have a non-cellulose-reactive substituent in the remaining 4- or 6-position.

Examples of such non-reactive substituents are alkyl or arylthio groups, alkoxy or aryloxy groups and very particularly substituted amino groups.

Preferred forms of these groups are, for example, lower alkoxy groups, i.e. C 1, -alkoxy groups such as methoxy, ethoxy, -n-propoxy, Isopropoxy and butoxy, and lower alkoxy-lower alkoxy groups, such as ß-methoxyethoxy, ß-ethoxyethoxy, phenoxy and sulfophenoxy, amino groups, lower alkylamino groups, such as methylamino, ethyl amino and butylamino, di (lower alkyl) amino groups such as dimethylamino, diethylamino, Methylathy1amino and dibutylamino, and groups of the latter two types in which the alkyl groups are substituted, in particular by OH, CN or SO-H, e.g.

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β-Hydroxyäthy1amino, Di (ß-hydroxyäthyl) amino, ß-Cyanoäthylamino, Di (ß-cyanoäthyl) amino _f ß-Sulfoäthylamino, ß-Hydroxypropylamino, (ß-Hydroxybutyl) äthylamino and (ß-Hydroxyäthyl) methylamino, like eg Cycloalkylamino Cyclohexylamino, cyclic amino groups, such as, for example, morpholino and piperazino, naphthylamino groups which _{are substituted by 1, 2 or 3 groups of the formula SO 3} H, and optionally substituted phenylamino groups.

Particularly preferred optionally substituted phenylamino groups are groups of the formula:

(2)

where G is H, methyl, ethyl, α-sulfomethyl, β-carboxy, β-hydroxy or β-cyanoethyl and Z and X are each independently selected from H, COOH, SO ₃ H, CH ₃ , C ₂ H ₅ , OCH ₃ , OC ₂ H _n , Cl, Br, CN, NO ₂ , NHCOOCH ₃ and ß-sulfatoethylsulfonyl.

Specific examples of such groups are anilino, o-, m- and p-sulfoanilino, o-, m- and p-carboxyanilino, 4- and 5-sulfo-2-carboxyanilino, 4- and 5-sulfo-o-tolylamino, 2,4-, 2,5- and 3,5-disulfoanilino, 2,4-dicarboxyanilino, 4- and 5-sulfo-2-methoxyanilino, N-methyl-o-, -m- and -p-sulfoanilino, N-nJ-sulfomethylanilino and N- (ß-hydroxyethyl) -3-sulfoanilino.

If necessary, the cellulose-reactive group Q can have the form

- Ht - Dm - Q ¹ .

assume, wherein Ht stands for an s-triazine nucleus, which is a cellulose-reactive atom or one with cellulose

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carries reactive group, Dm stands for a diamine radical which connects Ht and Q ¹ through the two amino groups, and Q " ^{1 stands} for a group reactive with cellulose, which has the meaning given above for Q.

In particular, it is usually preferred that the cellulose-reactive atom or the cellulose-reactive group on Ht stands for F, Br or, in particular, Cl and that Q ^{1 stands} for an s-triazine group as defined for Q above.

When the symbol Q stands for an s-triazine ring that bears a halogen atom and a non-reactive substituent, then the latter can be the residue of a colored amine, for example the azo, anthraquinone or phthalocyanine series, but is in particular a radical of the formula (1) minus the group Q, so that the dye has a total of 2 radicals of the formula (1) contains fewer of the group Q which are linked by a halogen-s-triazine radical, or two such radicals which are linked by two halo-s-triazine groups and a diamine radical Dm, as indicated above. In these dyes, the halogen can be F or Br, but it is usually preferred that it be Cl.

Examples of diamines DmH ₂ , which can provide the remainder Dm, are:

heterocyclic diamines such as piperazine, aliphatic diamines such as alkylene, hydroxyalkylene or sulfatoalkylenediamines, especially those with 2 to 6 carbon atoms, e.g. ethylenediamine, 1,2- and 1,3-propylenediamine, 1,6-diaminohexane, ß-hydroxyethylaminoethylamine, 2-hydroxy-1,3-diaminopropane and 2-sulfato-1,3-diaminopropane,

other aliphatic oil _r ω -D! amino compounds, - such as triethylenetetramine and di (ß-aminoethyl) ether,

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Naphthylenediaminesulfonic acids, such as 2,6-diaminonaphthalene-1,5- and -4,8-disulfonic acid and 1,5-diaminonaphthalene-3,7-disulfonic acid,

Diamine derivatives of mono- and dicyclic compounds the benzene series, such as phenylenediamines and their mono-and disulfonic acids, for example m- and p-phenylenediamine, 1, 3-phenylenediamine-5-sulfonic and -4,6-disulfonic acid and 1,4-phenylenediamine-2-sulfonic and 2,5-disulfonic acid, Diamines of the formula:

where ρ and q each represent 0 or 1 and E represents a direct bond or a group of the formula SO ₉ , OCH ₉ , C ₂ H ₂ , C ₂ H ₄ , NH or NHCONH, such as 4,4'- Diaminostilbene-2,2'-disulfonic acid, benzidine-2-sulfonic and -2,2'-disulfonic acid, 3,3'- and 4,4'-diaminodiphenylurea, 4,4'-diaminodiphenylurea-2,2 ¹ - and -3,3'-disulfonic acid, 4,4'-diaminodiphenylamine-2,2'-disulfonic acid, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane-2,2'-disulfonic acid, 4,4'-diaminodiphenyl ether , 4,4'-diaminodiphenyl sulfone and 4,4'-diaminodiphenylethane-2,2'-disulfonic acid and the N-lower alkyl and N, N'-di (lower alkyl) derivatives of the above diamines, such as 4-methylamino and 4-ethylamino aniline-2-sulfonic acid and N, N'-dimethyl-4,4'-diaminodiphenylam .no-2,2'-disulfonic acid.

It is often preferred that the group Q be a dichlorotriazinyl group is, in which case the dyes are often opposed by a higher degree of resistance acid hydrolysis are excellent when applied to cellulosic fabrics applied than is usually the case with dyes that contain these reactive groups wear.

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The dyes combine this property with good coloring power and easy application. The colored ones Textile materials often show good resistance to washing treatments, chemical discoloration and exposure.

In suitable cases, the dyes of the formula (1) can be converted into metal complexes, in particular 1: 1 copper complexes and used as such.

The invention also relates to dyes which, in the form of the free acid, have the formula:

where R, R, Y, Q, n, m and χ have the meanings given above with reference to formula (1), B for H or OH, as well as the 1: 1 copper complexes of dyes of formula (4), in which B is OH.

In this case it is particularly preferred that Q stands for dichlorotriazinyl, difluorochloropyrimidinyl, trichloropyrimidinyl or dxchlorocyanopyrimidinyl, η stands for 1, R stands for CH ₃ or in particular H, χ stands for 0 or 1, Y stands for acetyl or benzoyl and m for 2 if χ is 1, or 2 or 3 if χ is 0.

The copper complexes of the dyes are particularly preferred of formula (4) in which B is OH, d.s. So dyes that have the formula in the form of the free acid:

(5)

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have, wherein R, R, Q, Y, m, η and χ are based on the above of the formula (4) have given meanings.

These copper complex dyes can not only easily be applied, whereby they give uniform strong dyeings with good light and wash fastness, but they also show good resistance to bleaching.

The invention further relates to a process for the preparation of the dyes of the formula (1) with the exception of those wherein Q is ß-sulfatoethylsulfonyl, which is carried out by a compound of Formula (1), in which Q stands for H, with a compound Q. Hai, in which Q stands for a group reactive with cellulose according to above definition with the exception of ß-Sulfatqäthylsulfonyl and Hai stands for halogen. .

The above process can suitably be carried out in an aqueous medium and preferably in the presence of an acid-binding medium Means such as sodium carbonate, bicarbonate or hydroxide and one for the reactivity of the compound Q.Hai suitable temperature, usually in the range of 0-100 ° C.

In the case in which Q stands for ß-sulfatoethylsulfonyl, For example, the dyes can be prepared using the above procedure with carbyl sulfate in place the connection Q.Hai is used.

Specific examples of Q.Hai compounds result from the examples given for Q above. It is normally preferred that Hai be chlorine. For example Q.Hai stands for ß-chloropropionyl chloride, cyanuric chloride, Methoxydichloro-s-triazine or 2,4,5,6-tetrachloropyrimidine. In some cases, however, it is more convenient for Hai to represent a different halogen such as fluorine when this as a cellulose-reactive substituent in Q

909819/0646

lies. So Q. Hal can be 2,4,6-trifluoro-5-chloropyrimidine, to introduce the difluoro-5-chloropyrimidinyl group.

Compounds of the formula (1) in which Q is H and the can be used for the above process / can be obtained by using naphthols of the formula:

NS ¹ Y).

with diazonium salts !! of amines of the formula:

coupling, where R, R-, Y, m, η and χ are the ones given above; Have meanings and the ring A can be substituted as described above.

This coupling can take place among the usual ones for such reactions Conditions are executed.

Examples of naphthols of the formula (6) are:

1-N-acetylamino-e-naphthol-S, 6-disulfonic acid, 1-N-SuIfoacetylamino-S-naphthol-S, 6-disulfonic acid, 1-N-Benzoylamino-S-naphthol-S, 6-disulfonic acid, 1-N-acetylamino-8-naphthol-4,6-disulfonic acid, 1-N-SuIfoacetylamino-8-naphthol-4,6-disulfonic acid, 1-N-Benzoylamino-8-naphthol-4,6-disulfonic acid, 2-N-acetylamino-5-naphthol-7-sulfonic acid, 2-N-sulfoacetylamino-5-naphthol-7-sulfonic acid,

2-N-methyl-N-acetylamino-5-naphthol-7-sulfonic acid,

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away

1-naphthol-4,8-disulfonic acid,

1-naphthol-3,6-disulfonic acid,

1-N-benzenesulfonylamino-8-naphthol-3,6-disulfonic acid and 1-N-p-Toluenesulfonylamino-8-naphthol-4,6-disulfonic acid.

When the reactive group Q has the formula

- Ht - Dm - Q *

as defined above, then the reactant has Q. Hai as used in the above process will, the formula:

Shark - Ht - Dm - Q ¹

This compound can be obtained by adding a diamine DmH ₂ with 1 mole of carbyl sulfate or Q. Hai, as defined above, and 1 mole of an s-triazine compound of the formula:

shark

shark

where Y is a cellulose reactive substituent stands, implements. In a preferred case in which Ht stands for a chloro-s-triazinyl group, Y stands for Cl, ■ that is, the above s-triazine compound is derived from cyanuric chloride consists.

The reactive dyes of the formula (1), wherein those with cellulose reactive group Q is an s-triazine nucleus which is substituted by a Cl, Br. Or F atom and an amino or Amino group is substituted can also be obtained by using a dye of the formula (1), wherein

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Q for a dichloro, dibromo or difluoro-s-triazine group is, reacts with ammonia or an amine.

The process can expediently be carried out by placing the reactants in an aqueous medium, optionally in the presence of a water-soluble organic solvent at a temperature of 30-60 ° C stirs, preferably keeping the pH at 5-8 by adding an acid-binding agent to the during the To neutralize reaction formed hydrogen halide. Suitable acid-binding agents are alkali metal hydroxides, carbonates and bicarbonates, or an excess of ammonia or aliphatic amine, provided that this or this forms one of the reactants.

If a diamine is used in the ratio of 1 mole to 2 moles of the dichloro, dibromo or difluoro-s-triazinyl dye, then the product obtained is of the type mentioned above, the dye having a total of 2 groups of formula (1) minus Q. linked by two chloro, bromo or fluoro-s-triazine groups and a diamine radical. In the above process, any of the above-mentioned diamines DmH ₂ can be used.

If, alternatively, the dichloro, dibromo or difluorotriazine dye is reacted with a diamine D111H2 in equimolar amounts, then the resulting product contains a free amino group and can then be reacted with carbyl sulfate or a compound of the formula Q.Hai as defined above, whereby the dye obtained contains a cellulose-reactive group of the formula -Ht - Dm - Q ¹ as defined above, in which Ht is chloro-, bromo- or fluorotriazinyl.

Alternatively, dyes of this type can be obtained by first converting the diamine with 1 mole of Q.

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sets and the resulting monoamine is reacted with 1 mol of dichloro, dibromo or difluoro-s-triazine dye.

If in the above reaction 1 mole of diamine with 1 mole of Q. Hai
or with a dye with a dichloro, dibromo
or difluoro-s-triazinyl group is reacted, then it is usually preferred that the diamine have amino groups
contains different reactivity in order to avoid the simultaneous formation of undesired by-products from 1 mol
of the diamine with 2 moles of the other reactant
to be kept low.

In those cases in which Q stands for a triazinyl group which has a quaternary ammonium or pyridinium substituent as a substituent reactive with cellulose,
these dyes can often be conveniently obtained by adding the corresponding chloro, bromo
or fluorotriazinyl dye is reacted with the corresponding tertiary amine or pyridine. Such a reaction
is normally in an aqueous medium at 30 to
100 ° C executed.

Metal complex dyes can be obtained by conventional plating methods which are conventional
before or after the reaction by which the cellulose reactive group Q is introduced.

For example, the dyes of the formula (5) according to the invention can be prepared by using a dye of the
Formula (4), in which Q is H, is reacted with a suitable copper plating reagent, namely before or after the reaction with a compound Q. Hai or carbyl sulfate as defined above.

The copper plating reagent for use in the above reaction is chosen according to the nature of the B substituent on the color

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selected substance of formula (4).

So if B stands for OH, then the copper plating reagent is a copper salt, especially a simple copper salt such as copper sulfate. The Verkupferungsreaktion is normally carried out in an aqueous medium -in the presence of an acid-binding agent at a temperature of 10 to 100 ⁰ C, in particular 2O-5O ° C.

When B is H, the copper plating reagent consists of a copper salt and an oxidizing agent such as e.g. from a simple copper salt, such as sulfate or acetate, plus hydrogen peroxide. This oxidative Copper plating is usually carried out in an aqueous medium at a temperature of 10-100 ° C, especially 20-5O ° C, executed. The pH of the medium is usually kept between 2 and 7, in particular between 4 and 5. In some In some cases the presence of acetate ions has been found useful.

The dyes prepared by the above methods can be isolated by any conventional means, for example by spray drying or by precipitation and filtration.

The dyes are shown above in the free acid form and can be isolated in this form. However, it has often proven to be useful to do this To isolate dyes in the form of their salts, in particular in the form of their alkali metal salts, very particularly sodium salts.

The dyes of the invention can be used for dyeing a a wide range of textile materials containing hydroxyl or amino groups are used, such as wool, silk, synthetic polyamides and natural or regenerated cellulose, for example cotton or viscose rayon,

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the usual methods of dyeing such materials with water-soluble reactive dyes are used. For example, in the case of cellulose, they are preferably used together with a treatment with an acid-binding agent Agents such as caustic soda, sodium carbonate, phosphate, silicate or bicarbonate, are used, with these acid-binding agents are applied to the cellulosic textile material before, during or after the application of the dye can be. The method, technique and conditions for applying the dye to the textile material are selected according to various factors, such as the nature of the fiber and the physical <η shape of the textile material. For example, set up The methods vary according to whether the fiber is loose or spun into yarns, which in turn are strands or yarns can be wound on spools or made into a cloth or garment by knitting or weaving could be. All the usual methods of dyeing or printing can be used to make the dyes to apply to the textile materials. It can also be tere dyes and / or pigments applied simultaneously or successively with the dyes according to the invention using such combinations and conditions as determined by the properties of the Dyes and / or pigments are dictated. Such mixed dyeings are particularly valuable if the textiles, which Containing groups of the formula OH or NH2, with others Textile fibers are mixed that are free from such groups, such as with polyesters. The dyeing can be done in batches are performed, for example exhaustion techniques with pool, winch, jet, stirring or jigging devices can be used, in particular for strands, woven or knitted goods or garments. However, the dyes can also be produced by a "pack dyeing technique" are applied to fibers that are wound up in cylindrical or conical bobbins "or warp beams.

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are wrapped, especially if their carriers are perforated. The dyes can also be found in loose fibers permeable containers such as cages, where pressure and / or vacuum is applied to facilitate penetration and circulation through the packs. Alternatively, continuous or semi-continuous dyeing processes, such as those using padding techniques, e.g. pad mangling, come to use, wherein the textile material is impregnated with a dye liquid and then through Rollers is passed to control the amount of fluid retained, with one or more Post-treatments follow, e.g. drying, jigger or reel development, baking, steaming, further padding in others Solutions, such as those with acid-binding agents as mentioned above, should be stored in moist conditions Room temperature or elevated temperatures, passing over heated rollers or passing through intermittent or continuous Washing procedures. These aftertreatments can also include finishing stages, for example antistatic or anti-crease agents are applied. Textiles in web form can also be produced using textile printing processes be colored, such as printing with engraved or patterned rolls or screen printing or transfer printing, such as wet transfer printing. Details of these and other suitable printing methods are in "The Principles and Practice of Textile Printing "by E. Knecht, I.B. Fothergill and G. Hurst, 4th edition 1952, ed. by Griffin, or in "An Introduction to Textile Printing" by W. Clarke, 4th edition 1974, ed. by Newnes Butterworth, described.

The new dyes according to the invention form a valuable one Class of cellulose reactive dyes that have good, result in deep and equalized colors of the textile substrates. These textiles often have a good resistance

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ability to withstand the various washing treatments and chemical fading and fading by light, as mentioned above.

The invention is further illustrated by the following examples in which all parts are expressed by weight and where the weight / volume ratios are expressed in kg / l.

Example 1

Production of

NHCOCiL

15.9 parts of 4-aminobenzylamine hydrochloride are in one Mixture of 50 parts of ice and water and 39 parts of concentrated hydrochloric acid and dissolved by adding 6.9 parts of sodium nitrite dissolved in 50 parts of water are diazotized. The solution of the diazonium salt thus obtained is during 1/2 st to 286 parts of a 15.6% solution of 1-naphthol-8-acetylamino-3,6-disulfonic acid a pH of 7 and below 10 C added. The product is precipitated by adding 10% (w / v) sodium chloride, filtered off, washed with two portions of 200 parts of a 10% (w / v) saline solution, again in

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1500 parts of water with pH δ-9 dissolved below 5 ° C and reacted with 20 parts of cyanuric chloride, this pH and temperature conditions are maintained. To When the reaction has ended, the product is precipitated by adding 10% (w / v) sodium chloride and filtered off, with 87.3 parts of a red powder with a molecular weight of 1027 are obtained, the cellulose fibers in medium red Dyes shades with excellent fastness properties when applied together with an acid-binding agent will.

Example 2

Production of

Cl -

Cl

* N

0-

-Cu-

N = N

HO ₅ S-

KHCOCH

87.3 parts of the product from Example 1 are dissolved in 4000 parts of water and copper-plated oxidatively at pH 4-5 by adding 25 parts of copper sulfate pentahydrate and then, dropwise, 20 volumes of hydrogen peroxide until the reaction has ended. The solution is adjusted to pH 6.5 and the product is precipitated by adding 20% (w / v) sodium chloride, filtered off, washed with a little 10% (w / v) sodium chloride solution and dried. This gives 65.3 parts of a red powder with a MW of 1129, which dyes cellulose fibers in reddish-violet shades with excellent fastness properties.

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-SrS-

Examples 3-15

According to the method of Example 1, the amine indicated in column II of the following table is diazotized and coupled with the naphthol indicated in column III, whereupon the product obtained is reacted with the halogen compound indicated in column IV. The product is, if specified, with the specified column -in V amino compound in an aqueous solution at a pH of 6-7 and at a temperature be- see ^# 20 and 35 ° C implemented. The color obtained on application to cellulose fibers can be found in column VI.

1 II III IV V VI 3 ß- (4-aminophenyl) -
ethylamine 1-acetylamino
8-hydroxy
naphthalene-
3,6-disulfone
acid Cyanur
chloride Red 4th 4-aminobenzyl
amine 11 Cyanuric
fluoride ammonia M. 5 Il 1-hydroxy
naphthalene-
3,6,8-tri-
sulfonic acid It Il yellowish
Red 6th Il 1-benzoyl
amino-8
hydroxynaph
thalin-3,6-
disulfonic acid Il Metanil
acid red . 7th Il 1-acetylamino
8-hydroxy
naphthalene-
3,6-disulfone
acid 2,4,6-
Trifluo-
ro-5-
chloro-
pyrimi-
din • Il

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Continuation of the table

I. II III IV V VI 8th 4-aminobenzyl
amine 1-kydroxynaph-
thalin-4,8-di ~
sulfonic acid Cyanur
chloride aniline yellowish
Red 9 Il 1-acetylamino
8-hydroxynaph-
thalin-3,6-
disulfonic acid 2,4,6-tri-
chloro-5-
cyanopyri-
midin red ' 10 Il 1-hydroxynaph-
thalin-3,6-
disulfonic acid 2,4,5,6-
Tetrachlo
ropyriini-
din yellowish
Red 11 Il 1-benzylamino
8-hydroxy-naph-
thalin-4,6-
disulfonic acid Cyanuric
fluoride SuIf-
anil-
acid Red 12th Il Il Cyanur
chloride Il 13th 4-amino-N-
methylbenzyl
amine 1-acetylamino
8-hydroxynaph-
thalin-3,6-
disulfonic acid Il Il 14th 3-aminobenzyl
amine 1-benzoylamino
8-hydroxynaph-
thalin-3,6-di-
sulfonic acid Il Il 15th Il 1-hydroxynaph-
thalin-3,6-
disulfonic acid Il yellowish
Red

909819/0646

Examples 16-28

The dyes produced in Examples 3-15 are each subjected to oxidative copper plating using the method described in Example 2. In any case, the copper-plated dye stains cellulose in a purple hue when combined with
an alkali is applied.

Examples 29-34

Dyes are according to the procedure of Examples 3-15
with the components of columns II to V of the table below. These dyes are then copper-plated according to Example 2. The copper-plated dyes
dye cellulose in the shades given in column VI.

I. II III IV V VI 29 4-aminoben-
zylamine 1-hydroxynaph-
thalin-4,8-
disulfonic acid Cyanur
chloride violet 30th Il 1-hydroxynaph-
thalin-3,6,8-
trisulfonic acid Il 31 4-amino-N-
methylbene
zylamine 1-hydroxynaph-
thalin-3,6-
disulfonic acid Il ammonia It 32 4-aminoben-
zylamine 1-hydroxynaph-
thalin-4,8-
disulfonic acid Il Il Il 33 4-aminoben-
zylamine 1-hydroxynaph-
thalin-3,6,8-
trisulfonic acid 2,4,6-
Trifluo-
ro-5-chlo-
ropyrimi-
din ■ ·
I.

909819/0646

2Jr -

Continuation of the table

I. II III IV V VI 34 4-amin above ζ y 1 -
amine 1-benzoyl
amino-8
hydroxynaph
thalin-3,6-
disulfonic acid Cyanur
chloride violet

Claims (16)

PATENT CLAIMS: 1. Dyes that, in the free acid form, have the formula: have, in which R ^{1 represents} H or CH ₃ , R stands for K or C,. -Alkyl, Y stands for an acyl group, Q stands for a group reactive with cellulose, η stands for 1 to 4, χ stands for O or 1, ra stands for 1 to 3, where the ring A can be further _{substituted by SO 3} H, the group R (Q) N. (CH2) - is in the m- or p-position to the azo group and, if Q contains an s-triazine ring, a carbon atom of the same is directly connected to the group NR. 2. Dyestuffs according to Claim 1, characterized in that R represents H or methyl. 3. Dyestuffs according to Claim 2, characterized in that R represents H. 4. Dyes according to one of claims 1 to 3, characterized in that η is 1. 5. Dyestuffs according to one of claims 1 to 4, characterized in that R stands for H. 6. Dyes according to one of claims 1 to 5, characterized in that Y is acetyl, sulfoacetyl, benzoyl, ORIGINAL INSPECTED Sulfobenzoyl, benzenesulfonyl or toluenesulfonyl stands. 7. Dyestuffs according to one of claims 1 to 6, characterized in that the ring A has no further substituents having. 8. Dyes according to any one of claims 1 to 7, characterized in that Q is a triazinyl or pyrimidinyl group stands. 9. Dyestuffs according to Claim 8, characterized in that Q stands for a dichlorotriazxnyl group. 10. Dyes, which are metal complexes of suitable dyes according to claim 1. 11. Dyes that, in the free acid form, have the formula have, in which R, R, Y, Q, n, m and χ the in an • Claim 1 have the meanings given, B stands for H or OH, and the 1: 1 copper complexes of the dyes of formula (4), in which B is OH. 12. Dyestuffs according to claim 11, characterized in that Q is dichlorotriazinyl, difluorochloropyrimidinyl, trichloropyrimxdinyl or dichlorocyanopyrimidinyl, η is 1, R is CH ₃ or H, χ is 0 or 1, Y is acetyl or benzoyl and m is 2 if χ is 1, or 2 or 3 if χ is 0. 909819/0646 13. Dyes according to claim 11 or 12, characterized in that that they have the formula: NE ¹ Y) exhibit. 14. Process for the preparation of the dyes according to claim 1, characterized in that a compound of the formula (1) of claim 1, wherein Q is H, with carbyl sulfate or a compound Q.Hai, wherein Q is a group reactive with cellulose with the exception of ß-sulfatoethylsulfonyl and Hal stands for halogen, converts. 15. Process for the preparation of the dyes according to claim 13, characterized in that a compound is used of formula (4) of claim 11, wherein Q is H, with carbyl sulfate or a compound of Formula Q.Hai, in which Q stands for a group reactive with cellulose with the exception of ß-sulfatoethylsulfonyl and Hal stands for halogen, reacting before or after a reaction with a copper plating agent performs. 16. Use of the dyes according to one of the claims 1 to 15 together with a treatment with an acid binding agent for dyeing cellulosic textile materials. 909819/0846