DE2331518A1 - NEW COLORS, THEIR PRODUCTION AND USE - Google Patents

Description

Case 1-8245 / 1-1-2. '

GERMANY 2331518

Attorney file 24 049 June 20, 1973

New dyes, their manufacture and use

The present application relates to new reactive dyes which contain at least one group of the formula

-N-C _n ^

contain, in which R is a hydrogen atom or an alkyl radical, X is chlorine, bromine or fluorine and Z is a radical of the formula

OH

0 ~ Me ⁺

I I

-N-P = O (2a) or - N P = O (2b)

¹ J IL ₊

R ^! OH R '0 Me

where Me is a cation and R ^{f is} a hydrogen atom or an alkyl radical. Particularly suitable cations are those of the alkali metals, such as Li, K and, in particular, Na ⁺ , and also NIk. Instead of two monovalent cations, the product can also contain a divalent metal ion, e.g.

OX Ox. O X.

Mg, Ca ^ ⁺ or Zn ⁺ .

Examples of the substituted or unsubstituted alkyl radicals defined by R and R ^{1 may be mentioned:}

309 ^ 82/1319

C v> O 1 v> I «J

'Low molecular weight alkyl radicals such as methyl, ethyl, propyl and butyl, which substituents such as methoxy, ethoxy ^ and hydroxyl groups may contain.

Each of the groups of the formula (I) is attached to an im

Dye present carbon atom bound. This carbon atom can be a member of an aryl nucleus present in the dye or be a member of an alkyl chain which is bonded directly to an aryl radical present in the dye or to an aryl radical is bonded through a bridging atom or a bridging group. As examples of such bridging atoms or Groups should be mentioned:

-0 -, - -S-, -CO-, -SC ^ -, -NH-, -N-alkyl, -CONH-, -SOpNH- and j -SO ₀ -N-alkyl. - ¹

* i · - - '""' The dyes according to the invention can from are of any known class of dyes

preferably of the mono- or polyazo series or the nitro, anthraquinone, formazan ore Phthaloeyanine series. They preferably contain at least one water-solubilizing group, e.g.

a carboxylic acid or, in particular, a sulfonic acid group.

Metal complex dyes are also possible, especially

Copper, chromium or cobalt complexes.

The production of the new reactive dyes

expediently takes place in such a way that a dye,

the at least one group of the formula -NH-R (3)

contains, wherein R has the meaning given above, with

a compound of the formula

309882/1319

XN X

TY

Ti N ⁽⁴⁾

Y f

KH - P = O ¹ OH

wherein X is chlorine, bromine or fluorine, or with salts of these Acid converts.

The condensation is carried out in a manner known per se. It is advantageous to work in the present of acid-binding agents such as sodium carbonate, bicarbonate or acetate in a pH range of: 2 to 7.5 and below conditions such that only one halogen atom is exchanged at a time, so that there is still one in the finished dye molecule

Halogen atom is present, which can react with the substrate to be colored •. The pH range can also be increased by gradual Addition of sodium hydroxide solution must be observed. Expediently, one lays the amino group-containing dye compound as a solution or suspension in water or a water-miscible solution

medium, such as dioxane, and add a neutral, aqueous solution of (4,6-dihalo-s-triazin-2-yl) phosphoramic acid to this mixture. Both reactants can be used in mixtures of water and water-miscible organic solvents, such as acetone, dioxane, tetrahydrofuran or glycol ethers can be dissolved or suspended.

When the condensation has ended, the precipitated dye is filtered off. If necessary, sodium chloride can be used or potassium chloride added in order to obtain the full

H - to ensure permanent precipitation of the dye. Instead of To precipitate the dye with sodium chloride, the solution can also be evaporated in vacuo after the condensation has ended or atomize.

If desired, the new dyes can be in the presence of the medium in which they were formed a buffer and / or dried afterwards will. Examples of buffers that can be used for this purpose are: phosphate-derived buffers, etc. Sodium dihydrate phosphate and disodium hydrogen phosphate, citrates such as sodium citrate, borates, and alkali salts of Dialkylmetanilic acid, such as sodium diethyl metanilate, which

preferably used in conjunction with sodium hydrogen phosphate will. - - '

According to the invention, a modified one is also used

Process for the production of the new dyes claimed, which is applicable for the production of azo dyes. This consists in coupling a diazotizable primary aromatic amine with a coupling component, where the primary aromatic amine and the coupling component together contain at least one group of the formula (I) have to.

This modified process according to the invention can conveniently be carried out by adding sodium nitrite to a solution or suspension of the primary amine, which can be an aminoazo compound, in a dilute aqueous hydrochloric acid solution, - the thus obtained

309882/1319

■ ε ·

Diazo solution or suspension is added to an aqueous solution of the coupling component and the dye which has separated out filtered off. If necessary, sodium chloride can be added to completely precipitate all of the azo dye to ensure.

Those primary amines and coupling components which contain at least one group of the formula (I) can be prepared by condensing the corresponding primary amine or the corresponding coupling component which contain at least one group of the formula (3) with (4,6- "'.- ■ Dihalogen-s-triazin-2-yl) phosphoramic acid or salts thereof are obtained.

For the compounds of the formula (4) required as an intermediate, in particular (4,6-diehlor-striazin-2-yl) -phosphoramic acid, a production process by GlDerka, ch et al. in Khim.Org. Soedin. Fosfora,. .Akad. Nauk SSSR, Otd. Obshch. Tekh. Khim 1967, 89-93. Thereafter, (4,6-dichloro-s-triazin-2-yl) -phosphoramic acid is obtained from (4,6-dichloro-s-triazin-2-yl) -phosphorimide trichloride by treatment with 100% formic acid in dry Ethylene chloride produced. This formolysis requires the reaction mixture to be heated for up to 15 hours.

It has now surprisingly been found that the phosphoramic acid of the formula (I) also by hydrolysis in aqueous medium in the presence of an acid binding agent can be obtained. This new method has the advantage that

the reaction takes place so quickly at room temperature,

30988? / 1319

that it will be finished in less than an hour. In addition, one can use the ^r in the Hydrol3 se resulting aqueous solution containing a salt of Phosphoramidsäure directly for the reaction with amino group containing dyes or dye intermediates. When working according to the known process, however, isolation would generally be necessary.

The new process for the preparation of compounds of the formula (4) is thus characterized that you can get a compound of the formula

(5)

wherein X has the meaning given, hydrolyzed in an aqueous medium in the presence of an acid-binding agent.

The hydrolysis is expediently carried out at a pH of from 4 to 10, preferably from 7 to 8. This The area can be most beneficial with a phosphate buffer can be set. In order to keep the pH constant there are a base, preferably aqueous sodium hydroxide solution, is added during the reaction. The medium in which the hydrolysis is carried out can be purely aqueous or a mixture of water

3098R2 / 1319

jrait an organic solvent that is miscible with water and compared to PCl ₇ . - Group is inert, such as dioxane, tetrahydrofuran, acetone or a glycol ether.

The reaction temperature can be in the range of

about 0 ° C - 50 ° C. However, it is preferable to work at Room temperature, or below.

The (4,6-dihalo-s-triazin-2-yl) phosphorimide trichloride can be obtained from 4,6-dihalo-2-amino-s-triazine by reacting with phosphorus pentachloride. This reaction is expediently carried out in an inert solvent like dioxane through. The resulting phosphorimide trichloride does not need to be isolated, but the solution obtained can be used directly for hydrolysis. (4,6-Dichloro-s-triazin-2-yl) - ^ ± Dsphorimidtrichlorid is most easily accessible. , ''

The dye compounds of the azo series which are used as starting materials and which contain at least one -NHR group can be obtained by various processes. One method is to diazotize an aromatic primary amine and to couple the resulting diazonium compound with a coupling component containing an -NHR group. As examples of aromatic primary amines which can be used in this way to obtain aminoazo compounds, there may be mentioned: aniline, o-, m- and p-toluidines, o-, m- and p-anisidines, o-, m- and p-chloroaniline, 2,5-dichloroaniline, α- and ß-naphthylamine, 2,5-dimethylaniline, 5-nitro-2-aminoanisole, ² I-aminodiphenyl, aniline

309852/1319

ι 2,3- and -4-carboxylic acids, 2-aminodiphenyl ethers, 2-, J> - or 4-aminobenzenesulfonamide, or -sulfomonomethyl- or -äthylamide or -sulfondimethyl- or -sulfondiäthylamide, dehydrothio ~ p-toluidine monosulfonic acid or dehydrothio-p -toluidine disulfonic acid, aniline-2, -3- and -4-sulfonic acids, aniline-2,5-da sulfonic acid, 2,4-dimethylaniline-6-sulfonic acid, 3-aminobenzotrifluoride-4-sulfonic acid, 4-chloro-5-methylaniline -2 ~ sulfonic acid. 5-chloro-4-niethylaniline-2-sulfonic acid, ^ -acetylaminoaniline-sulfonic acid, 4-acetylaminoaniline-2-sulfonic acid, 4-chloroaniline-2-sulfonic acid, 3 * ^ - dichloroaniline-6-sulfonic acid, 4-methylaniline ~ 2-sulfonic acid, 3-methylaniline-6-sulfonic acid, 2,4-dimethoxyaniline-6-sulfonic acid, 4-methoxyaniline-2-sulfonic acid and 5-methoxyaniline-2-sulfonic acid, 2,5-dichloroaniline-4-sulfonic acid, 2- Naphthylamine-4,8-and-6,8-disulfonic acid, 1-naphthylamine-2-, -4-, -5-, -6- or -7-monosulfonic acid, 1-naphthylamine-3,6-disulfonic acid, 2- Naphthylamines * 6- and -5,7-disulfonic acid, 2-naphthylamine-3i6,8-trisulfonic acid, m- and p-nitroaniline, 4-nitroaniline-2-sulfonic acid, 3-nitroaniline-6-sulfonic acid, m- or p- Aminoaeetanilid and 4-Amino ~ 2-acetylawinotoluene-5-

sulfonic acid. ■ '

As examples of coupling components which

can be used may be mentioned: 2-amino- and 2-methylamino-5-naphthol-7-sulfonic acid, 2-amino and ^su o 2-methylamino-8-naphthol-7-l ^ns äure, 1-amino-? and l-ethylamino-8-naphthol-6-sulphonic acid and corresponding I >, 6- and 4,6-disulphonic acids, l- (3'- or 4 ^! -aminobenzoylamino) ~ 8-naphthol-3,6- and -4 , 6-disulfonic acid, aniline, o- and m-anisidine, o-

309882/1319

CJBA-GEIGY AG

and m-toluidine, 2,5-dimethylaniline, 3-A.nino-melhox> toluene, 2,5-dimethoxyaniline, N- ^ methylaniline, N-ethyl-o-toluidine, N-methyl-m-anisidine, J- Methylamino - ^ - methoxytoluene, l- (3'-aminophenyl) - ^ - methyl-, -carboxy- and -carboethoxy- ^ - pyrazolone, l- (4 ^t -aminophenyl) -3-methyl-, - -carboxy- and -carboethoxy-5-pyrazolone and 1- (V -amino-3! carboxyphenyl) -3-methyl-5-pyrazolone,
1-Ethyl-3-sulfomethyl-4-methyl-5-carbgmyl-6-hydroxypyridon-2.

The aminoazo compounds to be used in the process according to the invention are not restricted to compounds containing only one azo group. Disazo compounds can, for example, by tetrazotizing an aromatic diamine containing two primary amino groups and coupling the tetrazo compound obtained in this way with 2 mol of one of the coupling components defined above or with 1 mol of one of two of the coupling components defined above or with 1 mol of one of the coupling components defined above and with 1 molar proportion of a coupling component containing no amino group. Examples of such aromatic diamines are: benzidine, 3,3'-bimethoxybenzidine, benzidine-2,2'-disulfonic acid, benzidine-3,3'-eicarboxylic acid, benzidine-3,3'-diglycolic acid and 4.4 ^! -Diaminostilbene-2,2'-disulfonic acid. Furthermore, disazo or polyazo compounds can be obtained by using primary aromatic amines or diamines containing azo groups. Examples of such primary aromatic amines or diarnines containing azo groups are: 4-aminoazobenzene-V-sulfonic acid,

309882/1319

CIBA-GEIGY AG

/O

4 '-Amirio-2'mnethylphenylazo ^ -naphthalin ^ i, 8-disulphonic acid, 4-amino-5-methoxy-2-methyl-4 ^f -nitro-2 ^f -sulphoazobenzene.

Instead of starting from -NHR group-free * amines, a coupling component containing an -NHR group, if desired, can also be coupled with a diazonxum compound containing an -NHR group. Such diazonium compounds can be obtained by known processes by diazotizing primary aromatic amines which contain a second amino group or a monosubstituted amino group. Examples of such primary aromatic amines are: p-phenylenediamine, 1,4-phenylenediamine-2-sulfonic acid, 1,4-phenyl end! ami η -2-carboxylic acid, 1,4-diamino «naphthalene-2-sulfonic acid. Examples of coupling components which can be used in this way are the coupling components listed above and also β-naphthol, 2-naphthol-6- or -7-sulfonic acid, 2-naphthol-3,6- or -6.8 -disulfonic acid, 1-naphthol-4-sulfonic acid, 1-phenyl ^ -methyl ^ -pyrazolone, 1- (V -sulfophenyl) -3-methyl-5-pyrazolone, 1- (2 ', 5'-Diehlor-4 ¹ -sulfophenyl) -3-methyl-5-pyrazolone, 2-benzoylamino-5-naphthol-7-sulfonic acid, l-3enzoylamino-8-naphthol-3j6- or -4,6-disulfonic acid, phenol, p-cresol, acetoacetanilide and Acetoacet-2-methoxyaniline-5-sulfonic acid.

Other methods of making the one

-NHR group-containing dye compounds of the azo series, which are used in the method according to the invention

3 09882/1319

can consist of reducing a nitro group-containing dye or treating an azo or polyazo compound which contains at least one acylamino group with aqueous acid or aqueous alkali in order to hydrolyze the acylamino group or groups. Such azo or polyazo compounds can be obtained from primary aromatic amines and / or coupling components which contain acylamino groups. Examples of such primary aromatic amines are: monoacetylbenzidine, 4-amino-1-acetylaminonaphthalene-6-sulfonic acid, 4-amino-V-acetylaminodiphenyl-3-sulfonic acid, 4-atnino-3-sulfoacetanilide, 3-amino-4-sulfoacetanilide and ^ -amino-V-acetylaminostilbene-2,2'-disulfonic acid, and examples of such coupling components are: S-acetylamino ^ -sulfonaphthpl-Y-sulfonic acid, SN-acetyl-N-methylaniino ^ -naphthol-T-sulfonic acid, 2-Acetylamino- and 2-N-Acety1-N-methy! Amino-8-naphthol-δ-sulfonic acids and 1-acetylamino-8-naphthol-3> 6 ~ and -h, 6- disulfonic acids.

As examples of dye compounds of the

Anthrachinoneihe which may be in the process of this invention as Ausgangsprodukte.verwendet be mentioned: anthraquinone, which is an above-defined group of -NHR -.Formel to an alkylamino or arylamino group, plural marriage itself to the α-position of the anthraquinone nucleus attached, contain. Examples of such anthraquinone compounds include: l ~ amino-4- (V-aminoaniline) -anthraquinone-2,3'-disulphonic acid and the corresponding 2,3 ', 5- and 2,3', 6-trisulphonic acids, l ~ amino -4- (4 "-amino-

309882/1319

4'-benzoylaminoaniline) -anthraquinone-2,3 ~ disulfonic acid and the corresponding -2, 3 ', 5-trisulfonic acid, l-amino-4- (4' - (4 "-aminophenylazo) -anilino) -anthraquinone ~ 2, 2 ", 5-trisulfonic acid, l-amino-4- (4'-amino-3'-carboxyanilino) -anthraquinone -2,5-disulfonic acid, l-amino- ^ - (3'-aminoanilino) -anthraquinone 2 ₃ h ^x , 5-trisulfonic acid and the corresponding 2,4-disulfonic acid l-amino-4- (4 ^r - (4 "-aminophenyl) -anilino) -anthraquinone-2,3", 5-trisulfonic acid, 1-amino-4- (4'-methylamino) -anilinoanthraquinone-2,3'-disulfonic acid and the corresponding 2, 3 *, 5-trisulfonic acid, l-amino-4- (4'-n-butylamino) -anilinoanthraquinone-2,3'-disulfonic acid , 1-Amino-4- (4'-methylamino-3'-carboxyanilino) -anthraquinone-2-sulfonic acid, l-amino-4 ~ (3 * -ß-hydroxyethylamino) -anilinoanthraquinone-2,5-disulfonic acid, l- (4 ^! -Aminoanilino) -anthraquinone-2,3'-disulfonic acid and 1-amino-4- (4 '-amino-2 ^1- methpxyanilino) -anthraquinones, 3'-disulfonic acid.

Such dye compounds of the anthraquinone series can even consist of anthraquinone compounds which are a Halogen atom or a nitro group to the corresponding ä-Stei- ' Development of the anthraquinone nucleus contained bound, or from the leuco derivative of a 1,4-di-hydroxy-, -diamino- or -aminohydroxyanthraquinone by reacting the corresponding anthraquinone compound with at least one molar proportion of an aliphatic or aromatic diamine.

Dye compounds of the phthalocyanine series which are used in the process according to the invention

309882/1319

are preferably metal-containing phthalocyanines, such as copper phthalocyanines, which have at least one water-solubilizing agent Group, such as a sulfonic acid group, and at least one group of the formula -NHR, as defined above, contain.

The -NHR group or groups can be bonded to the benzene rings of the phthalocyanine nucleus directly or via a divalent bridge, for example via a -phenylene-, -CO-phenylene-, -SOp-phenylene-, -NH-phenylene- \ -S -Phenylene, -C) -phenylene-, -CEUS-phenylene-, -CHgO-phenylene-, -CTlg-phenylene-, -SCHg-phenylene-, -SOgCHg-phenylene-, phenylene-, -CHg-, -SO ₃ NR -arylene-, -Ni ^ CO-phenyleii-, phenylene-, -SO ₂ O-phenylene-, -CHg-, -CH ₂ NR ₁ -phenylene-, -CHgNH-CO-phenylene, -SO ₉ NR ₁ - Alkylene-, -CHgNR ₁ -alkyiene-, -CONR ₁ -phenylene-, -CH ₂ -, -CONR -arylene-, -SO ₂ - or a -CO bridge. In the above-mentioned divalent bridges, R- means. Hydrogen, alkyl or cycloalkyl, arylene is a divalent aromatic radical, optionally substituted, for example, by halogen, alkyl or alkoxy, in which the terminal bonds can be bonded to the same or different nuclei, and Alkyien is a divalent aliphatic radical containing heteroatoms, such as nitrogen, in the May include atomic chain, for example the radical -CHpCH ^ -NH-CIIpCHp-.

As examples of such divalent aromatic rides denoted by arylene are mentioned: aromatic nuclei, for example a benzene, naphthalene, acridine and carbazole nucleus, which have further substituents can carry, and remnants of the formula

309882/1319

where the benzene rings carry further substituents and -D- denotes a bridging group, for example -CH = CH-, -NH-, -S-, -0-, -SO ₂ -, -NO-N-, -N = N -, --NH-CO-NH-CO-NH-,

-0-CHpCHpO- or

IT N

Il I! —C C—

As particular examples of dye compounds of the phthaloeyanine series which can be used in the process according to the invention, there may be mentioned: copper phthalocyanine-4-N- (4-araino-3-sulfophenyl) -sulfonamld-4'4 ", 4" ^! trisulfonic acid, salt phthalocyanine-4,4'-di-N- (4'-amino-4 ¹ sulfophenyl) -carbonamide-4 ", 4"'- dicarboxylic acid and copper-4- (4'-amino-3'-sulfobenzoyl) phthalocyanine.

Mixtures of aminophthalocyanines can also be used. For example, a mixture (4-amino-3-sulfophenyl) -sulfonamiddisulfonsäure be used from about equal parts Kupferphthalocyamn-N- (4-amino-3-sul 'f ophenyl) -sulfonamidtrisulfonsäure Kupferphthalocyaniddi and-N-.

The aminophthalocyanines containing a sulfonic acid can be obtained either by sulfonation of known phthalocyanines containing primary or secondary amino groups or by synthesis from mixtures of phthalic acid derivatives

309882/13 19

and sulfonated phthalic acid derivatives. The sulfonating agent used is, for example, oleum, e.g. a 20% solution of sulfur trioxide in sulfuric acid.

Furthermore, they can by heating together suitable derivatives of sulfonated phthalic acid and substituted Phthalic acids are obtained by the generally known processes, for example by heating them together a mixture of 4-sulfophthalic anhydride and 4-p-nitrobenzoylphthalic anhydride, Urea, copper (II) chloride and ammonium molybdate in ο-dichlorobenzene at around 150 C. Also, by sulfonation of the corresponding primary and secondary amines or by converting a primary (or secondary N-alkyl or cycloalkyl) nitroaniline with a phthalocyanine, which contains chloromethyl and sulfonic acid or carboxylic acid groups, made phthalocyanines that are used as the starting product. Furthermore, such aminophthalocyanines can also by reacting a Phthalocyanine, which contains chlorosulfonyl groups, with a monoacetylalkylenediamine or an amino-N-benzylacetamide in the presence of water and treating the product thus obtained (which contains both sulfonamide and sulfonic acid groups contains) are prepared with aqueous alkyl to hydrolyze the acetylamino group, or by reaction of a phthalocyanine, which contains chloromethyl and sulfonic acid or carboxylic acid groups, with a monoethylalkylenediamine and treating the product thus obtained with aqueous alkali to hydrolyze the acetylamino groups.

3 09 8 8 2/1319

In addition, by direct sulfonation or by common Heating a mixture of suitable carboxy or sulfophthalic acid derivatives with substituted phthalic acid derivatives, for example by heating the anhydrides with urea and a catalyst in an organic solvent and reduction of the nitrophthalocyanine sulfone obtained in this way or carboxylic acid or hydrolysis of the acylamine phthalocyanine sulfonic or carboxylic acid thus obtained, or by Reaction of a phthalocyanine compound which contains carboxylic acid chloride groups contains, with a diaminobenzene sulfone ore -carboxylic acid, an aminobenzenesulfonic acid or an aminobenzoic acid, which also contains a nitro group, and reduction of the nitro compound thus obtained, or finally by reacting a phthalocyanine compound containing carboxylic acid chloride groups with an N-aminobenzylaeetamide and subsequent hydrolysis of the product thus obtained with aqueous alkali.

Dye compounds of the nitro series which can be used in the process according to the invention are preferably those of the formula

¹ (8)

NO ₂ -D'-NQ

309882/1319

where D 'denotes a naphthalene or benzene nucleus, which can be further substituted, the nitrogen atom M is in the ortho position to the nitro group, Z' denotes hydrogen or an optionally substituted hydrocarbon radical and Q denotes hydrogen or an organic radical bonded to the nitrogen through a carbon atom and wherein Q and Z 'are not both hydrogen, and Q ^{can be bonded to Z' when Z * is a hydrocarbon radical or to D 1} in the ortho position to the nitrogen atom N to form a heterocyclic ring, and which at least one group of the formula -NHR as defined above.

Dye compounds of the Formaza series which can be used according to the invention are the metal complexes of formazans of the formula
, NN - A - Y ₁

Q-CH

\ n - N - B - Y ₂

which contain at least one radical of the formula -NHR. Q, here denotes a monovalent radical, for example an aromatic or heterocyclic radical, an alkyl, nitro, cyano, low molecular weight alk anoyl, benzoyl or a low molecular weight, ie _{containing r} 1-4 carbon atoms, carbalkoxy group. A and B are residues of diazo components and Y and Y _? mean substituents which are capable of complex formation with a heavy metal atom. A, B and Q can be substituted with sulfo groups.

The dye molecule should contain a total of 1 to 5 sulfo groups.

309882/1319 -17a-

Particular examples of dye compounds containing at least one -NHR group which can be used as starting materials in the process according to the invention are the compounds of the following classes:
1. Azo compounds of the formula

OH

(9) H0 _v S "

where D see a bicyclic at most, free from NIIR groups Is aryl radical and the -NHR group is preferably 5-, 7- or 8-position of the naphthalene nucleus is bonded, and which optionally has a further sulfonic acid group in 5- or 6-position of the naphthalene nucleus.

3 09882/1319

D can be a residue of the naphthalene or

Benzene series mean, for example a stilbene, diphenyl-benzothiazolylphenyl- or diphenylamine residue. In this class, attention should also be paid to the related dyes, in which the -NHR group, instead of being attached to the naphthalene nucleus, to one attached to the 6-, 7- or 8-position of the naphthalene nucleus Benzoylamino or anilino group is bound.

Particularly valuable starting dyes are those in which D is a sulfonated phenyl or naphthyl radical, in particular those in which a -SO, H group contained in the ortho position to the azo bond; the phenyl radical can be further substituted, for example by halogen atoms, such as chlorine, low molecular weight alkyl radicals such as methyl., Alkylcarbonylamino or alkoxycarbonylamino groups such as acetylamino, methoxy or ethoxycarbonyiamino, ureido and alkoxy radicals such as methoxy.

Furthermore, D can mean a radical from the azobenzene, azonaphthalene or phenylazonaphthalene series. 2, azo compounds of the formula

DNN— <> —NHR. (10)

30988 2- / 13 19

where D denotes an at most bicyclic aryl radical, as described in class 1 and preferably a disulfonaphthyl or stilbene radical, and the benzene nucleus of the coupling component denotes further substituents such as halogen atoms or low molecular weight, ie ibis. 4 C-atoms containing alkyl, alkoxy, alkylcarbonylamino, alkoxycarbonylamino, or uridyl groups.
3 · Azo compounds of the formula

where D "is an arylene radical, such as a radical of the azobenzenes, azonaphthalene or phenylazonaphthalene series, or preferably an at most bicyclic arylene radical of the benzene or naphthalene series, and Ap is the radical of a naphtholsulfonic acid or the radical of an enolized or enolizable ketomethylene compound (such as an acetoacetarylide or a 5-pyrazide) with the OH group in the ortho position to the azo group. Dp preferably denotes a radical from the benzene series which contains a sulfonic acid group. H. Azo compounds of the formula

j DN = NA-NHR <12) \

wherein D is a radical of the DEFINE for D. Class 1 above and ten types A, the radical of a ketomethylene compound enolizable (viie an acetoacetarylide or a 5-Py ^r azolon) with the OH group in the ortho-position to the azo group mean. 5. The metal complex compounds, for example the copper, chromium and cobalt complexes, of the dyes of the formulas (9), (11)

309882/1319

and (12), in which D, D ₂ , A, A ₂ and A ^ have the meanings given in each case and furthermore a metallizable group (for example a hydroxyl, lower alkoxy or carboxylic acid group) in the ortho position to the azo group in D or Dp is available.
6. Anthraquinone compounds of the formula

(13)

NlI-Z "-NHR

in which the antbrachinone nucleus can contain an additional sulfonic acid group in the * j-, 6-, 7- or 8-position and Z "denotes a bridge member which is preferably a divalent radical of the benzene series, for example a phenylene, mesrtylene, diphenylene or -4,4 '-Stilbenöder azobenzene radical. Preferably, Z "should contain one sulforic acid group for each benzene ring present. .7 · Phthalocyanine compounds of the formula

'n (14) Pc J

- (SO ₂ NH-Z "'-

where Pc is a phthalocyanine nucleus, preferably copper phthalocyanine, ω -OH and / or -NH ₂ , Z " ^{1 is} a bridge member,

3 09882/1319

preferably an aliphatic cyclosliphatic or aromatic bridge, and η and m are each 1, 2 or 3 and can be the same or different, provided that n + m is not greater than 4.
8. Nitro dyes of the formula

V - NH-B-NHR

where V and B denote monocyclic aryl nuclei and the nitro group in "V is in the ortho position to the NH group. 9 · Metal complexes of formazan dyes of the formula N = NA-Y ₁

Q - CH

\ N - N - A - Υ _Λ

Jl L] Cn- l Oders)

where Q is an organic radical, a nitro or cyano group, A and B radicals of diazo component !! of the benzene, naphthalene or heterocyclic series and Y ₁ and Y _r each denote a substituent which is bonded in the o-position to the azo group and capable of complexing with a heavy metal, and R has the meaning given. The radical Q is above all a radical of the benzene series, such as phenyl or sulfophenyl, or a low molecular weight alkyl radical, such as methyl, and A and B are preferably phenyl radicals substituted with sulfonamides or alkylsulfonyl groups. Particularly suitable substituents Y and Y are the hydroxyl and carboxyl groups. Suitable heavy metals are copper, chromium, cobalt and nickel.

The following in Fr a ire are used as starting dyes in the mentioned dye classes at KDi el swej Re: * '

In class 1:

6-Amino-1-hydroxy-2- (2'-sulfophenylazo) -naphtha! In-3-sulfone-

acid,

6-methylamino-1-hydroxy-2- (V-acetylamino-2 ¹ -sulfophenylazo)

naphthalene-3-sulfonic acid,

8-Amino-1-hydroxy-2- (2 ^f -sulfophenylazo) -naphthalene- ^, 6-di--

sulfonic acid.

8-Amlno-1-hydroxy-2- (V-chloro-2'-sulfphenylazo) -naphthalene-

3,5-disulfonic acid,

7-amino-2- (2 ', 5' -disulfophenylazo) -1-hydroxynaphthalene-

3-sulfonic acid,

7-methylamino-2- (2 ¹ -sulfophenylazo) -l-hydroxynaphthalene-

3-sulfonic acid,

7-methylamino-2- (V-methoxy-2'-sulfophenylazo) -1-hydroxy-

naphthalene-3-sulfonic acid,

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8- (3 "-Aminobenzoylamino) -1-hydroxy-2- (2'-sulfophenylazo) -naphthalene-3,6-disulfonic acid, ·.

8-Amino ~ 1-hydroxy-2,2 ^T -azonaphthalene-1 ¹ , 3 ', 5', 6-tetrasulfonic acid,

8-amino-l-hydroxy-2,2 ^t -azonaphthalin-1 ', 3,5'-trisulfonic acid, 6-amino-1-hydroxy-2,2'-azonaphthalene-1', * -trisulfonsaure 3.5, 6-M.ethylamino-1-hydroxy-2,2'-azonaphthalene-1 ', 3 ^ 5 * -trisulfonic acid,

7-Amino-1-hydroxy-2j 2'-azonaphthalene-1 ', 3-disulfonic acid, 8-amino-1-hydroxy-2- (4 ^! -Hydroxy-3'-carboxyphenylazo) -naphthalene-3,6-disulfonic acid ,

6-amino-1-hydroxy-2- (4 ^f -hydroxy-3'-carboxyphenylazo) -naphthalene-3,5-disulfonic acid,

8-Amino-1-hydroxy-2- (4 '- (2 "-sulfophenylazo) -2 ¹ -methoxy-5'-methylphenylazo) -naphthalene-3,6-disulfonic acid, 8-amino-1-hydroxy-2- (4 '- (4 "-methoxyphenylazo) -2 ^! -Carboxyphenylazo) -naphthalene ^, 6-disulfonic acid , 8-amino-1-hydroxy-2- (4' - (2" -hydroxy-3 ", 6" -disulfo-1 "-naphthylazo) -2'-carboxyphenylazo) -naphthalene-3,6-disulfonic acid, 4,4'-bis (8" -amino-1 "-hydroxy-3", 6 "-disulfo- 2 "-naphthylazo) -

'3,3'-dimethoxydiphenyl,

"6-Amino-1-hydroxy-2- (V - (2" -sulfophenylazo) -2'-methoxy-5'-methylphenylazo) -nephthalene-3,5-disulfonic acid, In class 2:

2_ (4 ^! -Amino-2 ^T -methylphenylazo) -naphthalene-4,8-disulfonic acid, 2- (4'-amino-2'-acetylaminophenylazo) -naphthalene-5 »7-disulfonic acid,

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4-nitro ~ 4 '- (4 "-methylaminophenylazo) -stilbene-2.2 ^l -disulfone-

s & ure, "

4-nitro-4 '- (4 "-amino-2" -methyl-5 "-methoxy-phenylazo) -stilbene-

2,2'-disulfonic acid,

4-Amino-4 '- (4 "-methoxyphenylazo) -stilbene-2,2'-disulfonic acid,

4-Amino-2-methylazobenzene-2 ^f , 5'-disulfonic acid.

Tn class 3 ^;

1_ (2 ', 5'-dichloro-4'-sulfophenyl) -3-methyl- ⁱ ^ - (3 "-amino-4" -

sulfophenylazo) -5-pyrazolone,

1- (4'-SuIfophenyl) -3 ~ earboxy-4- (4 "-amino-3" -sulfophenyll- (2'-methyl-5 ^f -sulfophenyl) -3-methyl -4- (4 "-amino- 3 "-sulfo-

phenylazo) -5-pyrazolone,

1- (2'-sulfophenyl) -3-methyl-4- (3 "-amino-4" -sulfophenylazo) -

5-pyrazolone,

4-Amino-4 '- (3 "-methyl-1" -phenyl-4 "-pyrazole-5" -onyla zo) -

stilbene-2,2 ¹ -disulfonic acid,

4-Amino-4 '- (2 "-hydroxy-3 ⁿ , 6" -disulfο-1 "-naphthylazo) -stilbene-

2,2'-disulfonic acid,

8-acetylamino-l-hydroxy-2- (3 ^f -amino-4'-sulfophenylazo) -

naphthalene-3,6-disulfonic acid _i

7- (3'-sulfophenylamino) -l-hydroxy-2- (4'-amino-2 ¹ -carboxy-

phenylazo) naphthalene-3-sulfonic acid,

8-phenylamine-1-hydroxy-2- (4 ^! -Amino-2 ¹ -sulfophenylazo) -

naphthalene-3,6-disulfonic acid,

6-acetylamino-l-hydroxy-2- (5 ^r -amino-2 ¹ -sulfophenylazo) -

naphthalene-3-sulfonic acid,

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In class 4:

l- (3 'aminophenyl) -3-methyl-4- (2 _"i 5" _J -disulfophenylazo) -5-pyrazolone,

1- (3'-aminophenyl) -3-carboxy-4- (2'-carboxy-V -sulfophenyl-, azo) -5 ~ pyrazolone ,

4-Amino-4 '- (3 "-methyl-4" - (2 " ^f , 5"' T-disulfophenylazo) -l ⁿ pyrazole-5 "-onyl) -stilbene-2 _i 2'-disulfonic acid,
1- (3 '-Arainophenyl) -3-carboxy-4 - (4 "- (2 ^nt , 5"' -disulfophenylazo) -2 "-methoxy-5" -methylphenylazo) -5-pyrazolone,
In class> 5:

The copper complex of 8-amino-1-hydroxy-2- (2 ^! -Hydroxy-5 "-sulfophenylazo) -naphthalene-3,6-disulfonic acid,
the copper complex of 6-amino-1-hydroxy-2- (2'-hydroxy-5'-sulfophenylazo) -naphthalene-3-sulfonic acid,

the copper complex of 6-amino-1-hydroxy-2- (2'-hydroxy-5 ¹ ■ sulfophenylazo) -naphthalene-3,5-disulfonic acid,
the copper complex of 8 ~ amino-1-hydroxy-2- (2'-hydroxy-V-chloro-5 ^f -sulfophenylazo) -naphthalene-3,6-disulfonic acid,
the copper complex of 6- (4 ^f -amino-3 ¹ -sulfoanilino) -1-hydroxy 2- (2 "-carboxy'phenylazo) -naphthalene-3-sulfonic acid,
the 1: 2 chromium complex of 7-amino-6'-nitro-1,2'-dihydroxy-2, l'-azonaphthalene-3,4'-disulfonic acid,

the 1 ^: 2 chromium complex of 6-amine-1-hydroxy-2- (2'-carboxyphenylazo) -naphthalene-3-sulfonic acid,

the 1 ^: 2 chromium complex of 8-amino-l-hydroxy ~ 2- (4 ^f -nitro-2'-hydroxyphenylazo) -naphthalene-3,6-disulfonic acid,

309882/1319

fr

'the D ί; 2-cobalt complex of 6- (4' -amino-3 * -sulfoanilino) -1-hydroxy-2-r5 "-chlor-2" -hydroxyphenylazo) -naphthalene-3-sulfonic acid,

the 1: 2 chromium complex of 1 ~ (3'-amino-4'-sulfophenyl) -3-methyl-4- (2 "-hydroxy-4" -sulfo-1% naphthylazo) -5-pyrazolone, the i; 2-chromium complex of 7- (4'-sulfoanilino) -1-hydroxy-2 ~ (4 "-amino-2" -carboxyphenylazo 1. ^{) - naphthalene-I} -. ^ UIfonic acid ,. the 1: 2 chromium complex of 1- (3'-aminophenyl ") -3-methyl-4- (4" -nitro-2 "-carboxyphenylazo) -5-pyrazolone. Iri class 6:

; - ^: l-Amino-4- (3 ^l -amino-4 '-sulfoanilino) -anthraquinone-2-sulfonic acid,
1-Amino -4- (4'-amino-3'-sulfoanilino) ~ anthraquinone-2,5-di-

sulfonic acid,

1-Amino-4- (4 '- (4 "-amino-3 ♦ ^I -sulfophenyl) -anilino) -anthra-

quinone-2,5-disulfonic acid ,

1-Amino-4- (4 '- (4 "-amino-2" -sulfophenylazo) -anilino) -anthra-

, quinone-2,5-disulfonic acid,

l-Amino-4- (4'-methylamino-3-sulfoanilino) -anthraquinone-2-

sulfonic acid. .

In class 7:

3_ (3 ^! _Amino-4'-sulfophenyl) -sulfamyl copper phthalocyanine-

tri-3-sulfonic acid,

Di-4- (3 '-amino-4'-sulfophenyl) -sulfamyl copper phthalocyanine-

di-4-sulfonic acid,

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23'JIbIb

3- (3'-aminophenylsulfamyl) sulfamyl copper phthalocyanine di-3-sulfonic acid.
In class 8:

In grade 9 =

Copper complex of the 2 ^f -Carboxy-2 "-hydroxy-2" -

amino-1, 3j 5- triphenylformazan-4 ¹ , 5 ">3"'-trisulfonic acid. Copper complex of 2 ', 2 "'dihydroxy-3'-amino-5 ¹ -methylsulfonyl 1,3,5-triphenyl-3", 5 ", 4"'- trisulfonic acid

, JKupferkonipiex the 2 '-carboxy-4'-amino-2 "~ hydroxy ~ 1,3j5-triphenylformazan-3", 5 " , 2"' - trisulfonic acid copper complex of the 2 ', 2 "-dicarboxy-4"' - amino -1,3 * 5-triphenylformazan-4 ' , 4 "-disulfonic acid

Copper complex of the 2 ', 2 "-dihydroxy-5" -amino-1,, 5-diphenyl-3-ynethylf ormazan-5j 3 "-disulfonic acid

Copper complex of 2 ', 2 "-dihydroxy-5'-amino-1,3 * 5-triphenylformazan-3 * , 3"> 5 "-trisulfonic acid

^ KüpferkompTex ^ der 2 '-Carboxy-3' -amino-2 "-hydroxy-3" ^f (l " ¹¹ -phenyl-3""-methyl-pyrazole-5""-onyl-4""- azo) - 1,3 »5-triphenylformazan-3", 5 ", 2"",5""- tetrasulfonic acid ..

Nickel complex of 2 ^f , 2 "-dicarboxy-l, 5-diphenyl-3- (m-aminobenzoyl) -formazan-4J 4" -dj sulfonic acid,

The new, according to the invention obtained dyes are valuable for dyeing natural and artificial textile materials, for example textile materials made of cotton, regenerated cellulose, v / olle, silk, cellulose acetate, polyamides, polyacrylonitrile, modified Polyacrylonitrile and for this purpose can use the dyes

309882/1319

onto the textile material by dyeing, padding or printing using printing pastes containing the usual thickeners or oil-in-water emulsions or water-in OeI emulsions contain, are applied, whereby the textile materials in lively tones with excellent fastness properties, especially against wet treatments such as washing, and against light, to be colored.

They are particularly valuable for coloring

Cellulosic textile materials. For this purpose, the dyes are preferably applied to the cellulosic textile material with a treatment with an acid-binding agent * for example sodium carbonate, sodium tetasilicate, tri-, sodium phosphate or sodium hydroxide, which is applied to the cellulosic textile material before, during or after treatment with the Dye can be applied, applied. Instead, if the dyed textile material is subsequently heated or to be steamed, a compound such as sodium bicarbonate or sodium trichloroacetate is used which releases an acid-binding agent when heated or steamed.

The new dyes can be applied to nitrogen-containing textile materials, such as solid and polyamide textile materials, from a weakly alkaline, neutral or acidic dyebath. The dyeing process can be carried out with a constant or essentially constant p, _r -

Il

Value can be performed, or, if desired, the p, value can be performed of the dyebath at any stage of the dyeing process by adding acids or acidic salts or alkalis

309882/1319

) of the alkaline salts can be changed.

The new dyes can also be used in conjunction with a resin-forming mixture and a saiaren catalyst on textile materials, preferably cellulose text.i ! materials, are applied, drying the textile material if desired after the treatment and it is then heated to a temperature above 100 G, preferably between 130 and 170 ° C.

After dyeing or printing, it is advisable to remove the unfixed as completely as possible Dye. For this purpose, the dyeings and prints are thoroughly rinsed with warm and cold water and a soaping process subjected in the presence of nonionic dispersants and / or wetting agents.

In the following examples, unless otherwise stated, the parts mean parts by weight, the percentages are percentages by weight, and the temperatures are in Degrees Celsius.

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ZA -β

Example 1

a) (4,6-Dichloro-s-triazin-2-yl) phosphorimide trichloride: 16.5 parts of sharply dried h, 6-dichloro-2-amino-s-triazine are mixed with 20.8 parts of phosphorus pentachloride in 100% Parts by volume of dioxane slowly heated with vigorous stirring. The reactants go into solution with strong evolution of HCl. The reaction mixture is boiled under reflux overnight. Then let it cool down.

The solution of (4,6-dichloro-s-triazin-2-yl) phosphorimide trichloride thus obtained is used directly for hydrolysis. However, the product can also be distributed through distribution of the dioxane in a vacuum and possibly subsequent sublimation can be kept pure.

Instead of 4,6-dichloro-2-amino-s-triazine kar-n also an equivalent amount of 4,6 ~ dibrorno- or 4,6-difluoro-2-amino-s-triazine can be used.

b) (4 _i 6-dichloro-s-triazin ~ 2-yl) -phosphoramic acid: The solution of (2,6-dichloro-s> -triazin-2-yl-) obtained according to (a)

Phosphorimide trichloride in dioxane is dissolved in a solution of 20 parts of disodium hydrogen phosphate with vigorous stirring at room temperature dripped in 500 parts by volume of water. By adding about 500 parts by volume of NaOH solution at the same time the pH is kept between 7 and 8.

The resulting solution of the disodium salt of (4,6-dichloro-s-triazin-2-yl) phosphoramic acid is directly als Acylierungsmittel.für dyes containing amino groups used. . "

309882/1319

In the same way, the corresponding
4,6-dibromo and 4,6-difluoro compounds by hydrolysis of (4., 6-Dlbromo-s-triazin-2-yl) phosphorimide trichloride or (4j6-difluoro-s-triazin-2-yl) - phospborirnid-trichlorid can be produced.

If, instead of the 4,6-dichloro-2-amino-str.iazine, an equivalent amount of k, 6 -Dl chi or -2-methylamino-s-triazine is used and the procedure is otherwise exactly as described, a solution of the N is obtained - (4,6-Dichloro-s-triazln-2-yl) -N-methyl-phosphorarnidic acid, which can be used directly as an acylating agent.

309882/1319

Example 2

220 parts by volume of a neutral aqueous solution containing 4.9 parts of (4,6-dichloro-s-triazin-2-yl) phosphoramic acid are mixed with 4 parts of anhydrous sodium acetate. A solution of 7.9 parts of 2-amino-8-hydroxy-1- (4'-amino-2 ^f -sulfophenylazo) -naphthalene-6-sulfonic acid in 100 parts by volume of water is added with thorough stirring, and that

Whole heated to 40-42 ° C.

After acylation of the amino group has taken place

the dye is salted out with sodium chloride, filtered off and dried in vacuo at 50-60 °. The dye thus obtained dyes cotton in bluish red tones.

By reacting 1 equivalent of those containing amino groups listed in column I of the table below Dyes with 1 equivalent of (4,6-dichloro-s-triazin-2-yl) phosphoramic acid one obtains dyes which dye cotton in the nuances indicated in column II.

I. 1 I. II 2- (4'-Amino-2'-methylphenylazo) - golden yellow 2 naphthalene-3, 6,8-trisulfonic acid l- (2 ^f , 5 ^f -diehlor-4'-sulfophenyl) - greenish 3-methyl-4- (5 "-amino-2" -sulfo- yellow 3 " phenylazo) -5-pyrazolone l-amino-4- (3 ^f -amino-2 ¹ , 4 ', 6' -tri- reddish methylanilino) anthraquinone-2,5 ^! - blue disulfonic acid

309882/1319

2Ff II • Λ 6-amino-1-hydroxy-2- (2 '- orange sulfophenylazo) -naphthalene- 3 ~ sulfonic acid 5 8-amino-l-hydroxy-2- (2'- bluish-resistant sulfophenylazo) -naphtha! in- Red 3,6-disulfonic acid 6th 8-acetylamino-1-hydroxy ~ 2 ~ Red (5 ¹ -amino-2 ¹ -sulfophenylazo) -naphthalene ^ * 6-disulfonic acid 7th Copper complex compound blue 8-amino-l-hydroxy-2- (l'-hy- droxy-4 ^1, 8'-disulfonaphth- yl- [2 '-azo] -naphthalene - 3i6-di- sulfonic acid 8th Copper complex compound violet 8-amino-l-hydroxy-2- (2 ^f -hy- hydroxy-3'-chloro-5-sulfophenyl azo) -naphthalene-3,6-disulfone- ι acid c 9 Copper complex of 2'-carboxy-ή ¹ - blue amirio-2 "-hydroxy-1,3 _; .5-triphenylf- formazan-3 ", 5" , 2 "'- trisulfonic acid

309882 / .1319

I. II 10 1: 2 chromium complex compound Brown _from 6- amino-1-hydroxy-2- (2 ^! -Carboxyphenylazo) -naph thalin -3-sulfonic acid 11 Mono-p-aminophenylamide der turquoise Copper phthalocyanine-3,3 '> 3 "> 3 "'- tetrasulfonic acid

309882/1319

Example 3

7.25 parts of ni-phenylenediamine sulforic acid are dissolved in 250 parts by volume of water at room temperature with a neutral solution of sodium hydroxide solution, and 5 parts of anhydrous sodium acetate are added. A solution of 6.1 parts of (H, 6-dichloro-s-triazin-2-yl) phosphoramic acid in 100 parts by volume of water is added to the solution obtained, with vigorous stirring, and the mixture is left to react for about 24 hours. After a clear filtration, the reaction product is separated off by adding 20 % by volume of potassium chloride and dried at 50% in vacuo.

7.9 parts of the amine of the formula thus obtained

-MH- (K NJ - NH-P-OH

NN

οί

are dissolved in 200 parts of water with 10 parts of 2N sodium nitrite solution and 5 parts of 10N hydrochloric acid are added, whereupon the diazo compound partially precipitates in crystalline form.

The resulting suspension of the diazo compound is then poured into a neutral solution of 8.5 parts of 1-hydroxy-S-benzoylamino-naphthalene ^, β-disulfonic acid in 50 parts V / water, which also contains 10 parts of sodium bicarbonate. After the coupling is complete, the dye is salted out with common salt, filtered off and dried in vacuo at 6o °. .

The dye obtained in this way dyes cotton in blue

pungent red tones,

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If the above-described diazo compound is combined with the coupling components of column I of the following Table gives dyes which dye cotton in the nuances given in column II.

I. IX 1 1-ethyl-4-methyl-6- strong green hydroxy-3-sulfomethyl pungent yellow pyridon- (2) 2 Barbituric acid greenish yellow 3 8-acetylamino-l-hydroxy- Red naphthalene-3,5-disulfone- acid Acetoacetanilide-4-sul- greenish fonic acid yellow

309882/1319

2331 Γ) 18

Example 4

12.76 parts of 1-hydroxy-8-amino-naphthalene-3j6-disulfonic acid are in 250 parts of water at room temperature with sodium hydroxide solution Clearly dissolved and with 13 »1 parts of anhydrous sodium acetate offset. A solution of 9.8 parts (4,6-dicblor-s-triazin-2-yl) phosphoramic acid is added with vigorous stirring in 200 parts of water and let react for about 24 hours.

The reaction coupling component obtained in this way is then added to the solution of 5 * 92 parts Orthanilic acid in the usual way produced diazo component.

After the coupling has ended, the resulting dye is precipitated with a mixture of sodium chloride and potassium chloride, filtered off and dried in vacuo at 5Ο-6Ο.

The dye thus obtained dyes cotton in bluish red shades.

The following table shows the other colors

Dyes listed, which are made from the diazo components also listed and coupling components whose amino group with the Reactive component is linked analogously to the information in Example 4 - or by reacting the corresponding aminoazo dyes with the reactive component - are built up and dyed or dyed on cellulose materials by one of the processes described can be printed.

3 0 9 8 8 2/1319

Diazo component [
^ Coupling component hue 1-aminobenzene-2-
sulfonic acid 1-amino-8-hydroxynaph-
thaiin-4,6-disulfonic acid Red η 1- (3'-aminobenzoylamino) -
8-hydroxynaphthalene ~ 3,6-
disulfonic acid dd 1-aminο-2-carboxy-
benzene-4-sulfonic acid 1-amino-8-hydroxynaph-
thaiin ~ 3i6-disulfonic acid dd 1-amino-4-methyl-
benzene-2-sulfone
acid It dd l-amino-3-aeetyl-
aminobenzene-6-sul-
fonic acid Il dd l-amino-3- (2 '- [4 "-
sulfophenylamino] -
4 ^! -chlor-l ', 3 ^f , 5'-
triazine-6 ^! -yl) -
aminobenzene-6-sul-
fonic acid • It dd l-amino-3- (2 '- [4 "-
sulfophenylamino] -
4'-methylamino-tri- 2-amino-5-hydroxynaph-
thaiine-7-sulfonic acid orange 6 ') - aminobenzene-6-
sulfonic acid 1-aminobenzene-2-
sulfonic acid 2-methylamino-5-hydroxy
naphthalene-7-sulfonic acid dd 1-amino-4-acetyl-
amino-6-sulfonic acid Il Scarlet fever

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Example 5

To a solution of 3 ^ »7 parts of sodium 2-aminonaphthalene-4,8-disulphonic acid and 7 parts of sodium nitrite in 300 parts of water, 28 parts by volume of concentrated hydrochloric acid are added while cooling with ice, and the mixture is stirred at 0 ° to 10 ° for 1/2 hour . After excess nitrous acid has been removed, 10.7 parts of 3 "AmI dissolved in 10 parts by volume of concentrated hydrochloric acid and 150 parts of water are added, and the coupling is completed by blunting the mixture to p". 3 to 5. The aminoazo dye formed is salted out, filtered off with suction, washed and then redissolved in 700 parts of water with the addition of sodium hydroxide solution at p. 7. The aqueous solution is then mixed with 25.5 parts (4,6-dichloro-s-triazin-2-yl ) phosphoramic acid, dissolved neutrally in 200 parts by volume of HO . The mixture is heated to 40 ° and the hydrochloric acid released is blunted with soda solution until no free amino group can be detected any longer. The 4-chloro-6- (3'- Methyl-4 '- [' 4 ", 8" -disulfonaphthyl-2 "-azo] -phenylamino) -s-triazine-2-phosphoramic acid is salted out with 80 parts of sodium chloride, pressed off, washed and dried at 40 ° to 50 ° in vacuo . It is a yellow powder that is soluble in water with a yellow color.

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Example 6

The solution of 21 parts of the sodium salt of
1,4-Diaminobenzene-6-sulfonic acid in 100 parts of water is mixed with the neutral solution of 24.5 parts of (4,6-dichloro-striazin-2-yl) phosphoramic acid in 200 parts by volume of HO
Stirred at 20 ° to 40 ° with constant blunting of the hydrochloric acid released to 6 to 7 until a sample gives a clear, yellowish red coloration during diazotization and coupling to 1-hydroxynaphthalene-4-sulfonic acid. The resulting intermediate dye product is mixed directly with 7 parts of sodium nitrite and 28 parts after adding ice
concentrated hydrochloric acid and then combined with a solution of 47 parts of the sodium salt of 1-benzoylamino-8-hydroxynaphthalene-3,6-disulfonic acid and 12 parts of soda in 200 parts of water, the coupling to the 4-chloro-6- (3 '-sulfo-4' ~ [l "-benzoylamino-2" -hydroxy-3 " , 6" -disulfo-naphthyl-7 "-azo] -phenylamino) -striazine-2-phosphoramic acid, which is salted out, *
suctioned off, washed and dried at 40 to 50 in a vacuum. The dye dissolves easily in water with a red color and, according to one of the processes described, gives clear blue-tinged red dyeings and prints on cellulose materials.

309882/1319

70.01.335

The following table shows the colors and the

p-value of the coupling medium of dyes given, η

the analogous to the information in Example 6 from a diazo component, which contains a further, preferably acylatable amino group, from a coupling component and can be produced from a reactive component which can be linked to the diazo component. For dyeing and printing of cellulosic materials with the dyes in the table the procedures mentioned can be used.

309882/13 19

Diazo component

Coupling component

1,3-diaminobenzene-4-sulfonic acid

1,3-diaminobenzene-4-sulfonic acid

ο ι

2-aminonaphthalene-5 _i 7-disulfonic acid ■

2-aminonaphthalene-3 , β-disulfonic acid

1- (2 ', 4'-dichloro-1', 3 ', 5'-triazin-6'-yl-amino) -8-hydroxynaphthalene-3,6-disulfonic acid

l- (2 ', 4'-dihydroxy-

p _T , of the coupling

mediums

^ y
arino) -8-hydroxynaphthalene-3, β-disulfonic acid.

1- (2 ', 4'-DiChIOr-I ¹ , 3', 5'-triazin-6'-yl-amino) -8-hydroxynaphthalene-4,6-disulfonic acid

until 5
until 5
till 8

till 8

till 8

J.

hue

orange

Red

NJ CO CO λ

16 6 Λ b Ί 8

Example 7

If you proceed according to the instructions in Example 2, but instead of the K, 6-dichloro-s ~ triazin-2-yl) phosphoramic acid, the corresponding amount of N- (4,6-dichloro-striazin-2-yl) -N- methyl phosphoramic acid is used, a dye is obtained which, when applied by the usual methods, dyes cellulose materials in real bluish red tones.

Example 8

To a neutral solution of 27.2 parts 2- (2'-ureido-4'-aminophenylazo) -naphthalenes ^ 6,8-trisulfonic acid in 250 parts by volume v / ater one leaves slowly and with thorough stirring 15 parts of 4,6-dichloro-s-triazin-2-yl-phosphorimide-trichlorld, which is dissolved in 50 parts by volume of dioxane run. By adding 2N sodium hydroxide solution the p "value of the reaction mixture is kept between 7 and 8. After the addition is complete, it is salted out with about sodium chloride, based on the volume of the solution, Sucks off and dries the precipitated 4-chloro-6- (3'-ureido-4 '- [3 ", 6", 8 "-trisulfonaphthyl-2" -azo] -phenylamino-striazin-2-yl) -phosphoramic acid. With this dye, the dyeing process mentioned below gives golden yellow Dyeings on cellulose material.

309882/13 19

If one proceeds as indicated above, but instead of the aminoazo dye used there equivalent amounts of the aminoazo dyes built up from the components listed in the table below used, valuable new reactive dyes are also obtained.

In the table, the term "saponified" means that an acylamino group contained in the aminoazo dye has been subsequently saponified, while the term "reduced" means that there is one in the diazo component contained nitro group is reduced after coupling to the amino group, whereby the desired aminoazo dye trains.

309882/1319

Diazo component

Azo component

^! pH of the coupling medium

l-amino - ^ - nitrobenzene-! 2-sulfonic acid

1- (4'-sulfophenyl) -3-methylpyrazolone- (5)

(4-hour nitro group then reduced '

-Amino- ¹ ! -nitrobenzene 2-sulfonic acid

l- (4'-sulfophenyl) -3-carboxypyrazolone- (5)

1- (3'-sulfophenyl) -3-methyl-5-aminopyrazole

l-amino-3-acetylaminobenzene-6-sulfonic acid

(3-position acetylamino group then saponified)

1-amino-2-methylbenzene-4,6-disulfonic acid

2-aminonaphthalene-3j 6-disulfonic acid

2-aminonaphthalene-3,7-disulfonic acid

2-acetylamino-5-naphthol-7-sulfonic acid (saponified)

2-acetylamino-8-naphthol-6-sulfonic acid (saponified)

1-acetylamino-8-hydroxynaphthalene-3j6-disulfonic acid (saponified)

l-acetylamino-8-hydroxynaphthalene-4 ^ 6-disulfonic acid (saponified) to β

to 6 β to 7 to 7

to 8 to 8 to 8

till 8

Shade on cellulose

yellow

reddish yellow

yellow

yellow

orange

Red

. bluish red

bluish red

Diazo component

Azo component

CD CO CO OO

1-Amino-2,4-dimethylbenzene ■ β-sulfonic acid

4-aminoazobenzene-3 * 4'-di ■ sulfonic acid

pH of the coupling medium

2-acetylamino-8-hydroxy naphthalene ~ 3i6-disulfone acid (saponified)

1-amino-3-acetylaminobenzene

1-Αη, ιηο-2- (4'-amino-2 'sulfophenyl- [1'] - azo) -8-hydroxynaphthalene-3,6-disulfonic acid

- I

till 8

until 6

.8th

Color on \ Cellulose i

Red

yellow-brown

black

Example Q

66.3 parts of the copper complex of 2-amino-6- (2 ', 8'-dihydroxy-naphthylazo) -naphthol-5-tetrasulfonic acid-4,8,3', 6 '(prepared according to the information in German Patent 1,117 235 by coupling diazotized 1-amino-8- (benzenesulfonyloxy) -naphthalene-disulfonic acid- (3 ^ iri soda-alkaline medium with the equivalent amount of the 2-ethylamino-5-hydroxynaphthalene-disulfonic acid- (4,8), conversion of the monoazo compound in the copper complex by oxidative coppering and hydrolysis of the acetyl and the benzenesulfonyl group) is dissolved in 2500 parts by volume of water from 6o to 65 at p _IT 6 to 6.5 and at 10 to

Jl

27 parts of (4,6-dichloro-s-triazin ~ 2-yl) phosphoramic acid, dissolved neutrally in 250 parts by volume of water, are added. During the condensation, a p _tT of 6 to 7 is maintained by adding sodium carbonate solution. When the reaction has ended, the dye is salted out and isolated. When dried, the dye is a dark powder that dissolves in water with a blue color and dyes cotton fabric in very clear blue tones when wet.

309882/1319

- ή 7- Example 10

96 parts (based on 100 $ ige goods) of the copper phthalocyanine tetrasulfochloride freshly prepared in the usual manner by the action of chlorosulfonic acid and thionyl chloride on copper phthalocyanine or the isomeric, from l-sulfobenzene-3i ^ -dicarboxylic acid via the. Corresponding copper phthalocyanine tetrasulfonic acid built up copper phthalocyanine tetrasulfochloride are suspended in the form of the moist, well washed absorbent cake in 500 parts of water / water and 500 parts of ice, the solution of 50 parts of 1,3 * -dierninobenzene in 500 parts of water is added and the P ₁ , with soda set to 8.5. The suspension is stirred for 24 hours at room temperature and the ρ _{Η is} always kept at 8.5 by continuously adding soda. The resulting condensation product is precipitated at _pH 1 to 2 by the addition of sodium chloride, suction filtered, washed and then re-dissolved neutral in 1000 parts of water. A neutral solution of 85 parts (4,6-dichior-striazin-2-yl) -phosphoramic acid in 400 parts of water is added to the blue solution and the mixture is stirred at 0 to 10, while constantly blunting with soda solution to ρ 6, until no free ones Amino groups are more detectable. The reactive dye of the formula obtained in this way

309882/1319

so

O N

Il OH

N- / ^ ¹¹

Cu phthalocyanine

1 j _zQ ^ "^ ^ =

Cl

is washed out of salt and dried at 30 to HO in vacuo. It is a dark blue powder that is soluble in water with a blue color and dyes cotton and regenerated cellulose in clear blue shades of good wet, frost and lightfastness using one of the dyeing or printing processes mentioned.

Instead of the 96 parts of copper phthalic cyanine tetrasulfochloride can - with otherwise the same working method as in example 10 - also 87 parts (based on 100 ^ ige Goods) of the copper or copper obtained by the action of chlorosulfonic acid on copper or nickel phthalocyanine Nickel phthalocyanine trisulfochloride In the form of the moist, suction cake well washed with ice water can be used; reactive dyes which also have a clear blue color are then obtained.

If one works as indicated in Example 10, but from 87 parts of copper phthalocyanine trisulfochloride

309882/1319

goes out and instead of the 50 parts of the sodium salt of 1,3-diaminobenzene 90 parts of the sodium salt of 4,4'-diaminodiphenyl-2,2'-disulfonic acid or 90 parts of the sodium salt of 4,4'-diaminostilbene-2,2'- disulfonic acid is used, reactive dyes are obtained which dye cellulose materials by one of the processes mentioned above in clear blue tones which are fast to wet, rub and lightfast. If one starts from the 4'4 ", 4 ^m , 4""- tetraphenyl-Cu-phthalocyanine, one obtains after sulfochlorination and conversion with 1,3-phenylenediamine and acylation with (2,4-dichloro-s-triazine-6 -yl) -phosphoramic acid a reactive dye that dyes cellulose materials in the presence of acid-binding agents in clear, wet and lightfast green tones.

309882/1319

Example 11

84.5 parts of the copper complex of 2- (2 '-methyl-4' -aminophenylazo) -6- (2 ", 8" -dihydroxy-naphthylazo) naphthol-5-tetrasulfonic acid-4,8,, 3 ", 6 "are dissolved in 3000 parts by volume of water at p" β and with stirring at a temperature of 20 to 30 with a neutral solution of 26 parts (4 _i 6-dichloro-s-triazin-2-yl) phosphoramic acid in 250 Parts of water are combined and a p _TT of 6 is maintained with 2N potassium carbonate solution. The mixture is stirred until the condensation has ended, and the dye is precipitated and isolated by adding a little sodium chloride. The residue is washed with acetone and dried at room temperature under reduced pressure. A dark powder is obtained which dissolves in water with a green color and dyes cotton in green shades according to the specified procedures.

309882/1 319

Example 12

52.4 parts of the sodium salt of 4 - ([4 "-aminophenyl] amino) -2'-nitrodiphenylamine-3,4 ^! -Disulfonic acid are dissolved in 1000 parts of water and mixed with 26 parts (4,6-dichloro-s- triazin-2-yl) -phosphorarnidsaure, neutral dissolved in 250 parts of water, stirred for one hour at 0 ° to 10 °. the liberated acid is continuously dulled with soda to a p "value of" 6 to 7. The educated

reactive nitro dye of formula 0

Il OH

Νϊΐ

is salted out, filtered off, washed and dried. It dyes cellulose fibers from a long liquor or afterwards one of the usual Klotz method in the presence of soda as an acid-binding agent in wet and rub-fast depths Violet brown tones.

309882/1319

Example 13

79 * 6 parts of l-amino-S-hydroxynaphthalene- ^ o-disulfonic acid dissolved in 500 parts of water and a suspension of the diazo salt of (.2-chloro-4- (3 '-amino-4' sulfophenyl ) -s-triazin-ö-yl) -phosphoramic acid (prepared from 47 parts 1, 3 "" diamino-benzenesulfonic acid according to Example 3). A p "of 3 ^ 0 is set with sodium acetate solution, and when the coupling is complete, salt is removed with sodium chloride and the crystalline reaction product is filtered off with suction and washed with 10% sodium chloride solution. The dye is dried at 60 in a vacuum.

Example l4

38.6 parts of the monoazo dye from Example 13 are dissolved in 46θ parts of water and 6.7 parts of soda and the diazonium solution of 4.7 parts of aniline is added at 0 to 5 while maintaining a ρ of 8 to 8.5. The mixture is left to stir for about 3 hours, a p _TT of 5 * 5 is set with hydrochloric acid, and the mixture is filtered off with suction and washed with 5% sodium chloride solution. The dye of the formula

HO NH ₂ SO, H Cl

-N = N-AA N = N <> M ^ ^C ^ W °

^ ^ y, _NH C _n W ^ C — NH-p /

309882/1319

-53--

is dried at 60 ° in a vacuum and gives a black on cotton and up to 10% coloration

Rayon.

If, in this example, the diazo components given in the table below are used instead of aniline in an equivalent amount, valuable dyes are also obtained, the cotton in the color specified shades.

Diazo component

2-aminobenzene-1-sulfonic acid 2-amino-5-chlorobenzene-1-sulfonic acid 2-amino-5-methylbenzene-1-sulfonic acid 2-amino-5-nitrobenzene-1-sulfonic acid 2-aminonaphthalene-1-sulfonic acid Dihydro-p-toluidine disulfonic acid 2-aminonaphthalene-1,5-disulfonic acid

Color black

309882/1319

Example 13

If you proceed according to the information in Example 4, but instead of the (4,6-dichloro-striaziri-2-yl) used there -phosphoramic acid the equivalent amount of N- (2,4-dichloro ~ s-triazin-6-yl) -N-methylphosphoramic acid one also obtains a dye which dyes cotton in bluish red shades.

Example l6

If, according to the procedure of Example 3, 1,3 ~ Pheriylenediarnin-4-sulfonic acid is not used with the (4,6-dichloro-s-triazin-2-yl) phosphoramic acid, but rather with the equivalent amount of N- (2,4-dichloro-s-triazin-6-yl) -N-methyl-phosphoramic acid um, dlazotiert the intermediate product and couples to l-hydroxy-8-benzoylarninonaphthalene-3j6-disulfonic acid, in this way a dye is obtained which dyes cotton in bluish red tones.

309882/1319

Example 17

8.2 parts of the diazo compound prepared according to Example 3

/ the (2-chloro-4- (3 ^! -amino-4'-sulfο-phenyl) -s-triazin-6-yl) -phosphoramic acid are at ρ 6 to 7 according to the usual methods to 9.3 parts 1- Hydroxy-8- (2'-chloro-4 '-methoxys-triazin-6 ^f -yl) -aminonaphthalene-3,6-disulfonic acid coupled. The bisreactive one isolated by salting out

Dye of the formula

0 HO NH

HO Il _w Ϊ

^^ AN = N

Cl Cl

dyes cotton in red tones.

Instead of the coupling components mentioned in Example 17, those in the table below are used listed, but otherwise proceeds exactly as in this example, one also obtains bis-reactive dyes, the cotton by one of the processes listed below in the specified color shades with very good fastness properties to dye.

3 09882/1319

Coupling component

I shade

2-chloro-4- (8'-hydroxy-3 ^1, 6'-disulfonaphthyl) - j amino-6- (2 "-sulfophenyl) amino-s-triazine f

2-chloro-4- (8'-hydroxy-4 ', 6'-disulfonaphthyl) -amlno-6- (2 "-cyano-prop-2" -oxy) -s-triazine

2,4-dichloro-6- (8'-hydroxy-4 ', 6 * -disulfonaphthyl) - | amino-s-triazine

Red

2-chloro-4-amino-6 ~ (8'-hydroxy-3'j6'-disulfonaphthyl) -amino-s-triazine

2-chloro-4- (8'-hydroxy-4 ', 6'-disulfonaphthyl) -amino-6-ß-ethoxy-ethoxy-s-triazine

2,4-dichloro-5-N- (8'-hydroxy-4 ', 6'-disulfonaphthyl) carbonaniido-pyriniidin

2-chloro-4-ureido-6- (8'-hydroxy-3 ¹ , 6'-disulfonaphthyl) amino-s-triazine

2- (2'-methyl-4 ^t - (2 ", 4" -dichloro-s-triazine-6 "-yl) -! Yellow amino-5'-sulfo-phenyl) -3-methyl-pyrazolone-5!

2- (2'-methyl-4 ^f - (2 "-chloro-4" -methoxy-s-triazine- | "6 ^H -yl) -amino-5'-sulfo-phenyl) -3-methylpyrazolone-5

2- (2'-methyl-4 ^I - (2 "-chloro-4" - (3 ^I "-sulfo-phenyl) -s-triazine-6" -yl) ~ amino-5 '-sulfophenyl) -3 -methylpyrazolone-5

2- (2'-sulfo-4 '- (2 "-chlor-4" -amino-s-triazin-6 "-yl) -amino-phenyl-3-carboxy-pyrazolone-5

309882/1319

Example l8

12.76 parts of 1-hydroxy-S-aminonaphthalene-jjö-disulfonic acid are dissolved in 250 parts of water at room temperature with sodium hydroxide solution, and 10 parts of anhydrous sodium acetate are added. A neutral solution of 8.8 parts of (4,6-dichloro-s-triazin-2-yl) phosphoraniidic acid in 200 parts by volume of water is added with vigorous stirring and the mixture is left to react for about 24 hours. At the same time 7.5 parts of rn-phenylenediaminesulfonic acid are dissolved in 250 parts by volume of water at room temperature with sodium hydroxide solution, and 10 parts of anhydrous sodium acetate are added. A neutral solution of 1/10 parts (4,6-dichloro-s-triazin-2-yl) phosphoramic acid in 200 parts by volume of water is added to the resulting solution with vigorous stirring and the mixture is left to react for about 24 hours. After a clear filtration, the reaction product is mixed with 20 parts of 2N sodium nitrite solution and 10 parts of 10N hydrochloric acid, whereupon the diazo compound precipitates partially in crystalline form. The resulting suspension of the diazo compound is then poured into the solution of the coupling component, the p-value being changed by simultaneous addition of sodium hydroxide solution

6 and 7 holds. After the coupling has ended, the dye is salted out with sodium chloride, filtered off and added in vacuo dried. The bis-reactive dye obtained in this way dyes cotton in bluish red shades.

309882/1319

From the diazo components listed in the table below and coupling components can, analogously to the information in Example 18, build up bis-reactive dyes, which, for example, dyed on cellulose materials by the dyeing process listed below, dyeings in-den in Color shades given in the table.

I clutch component color!

Diazo component

2-amino-4- (2 '-chlor-4' methoxy-s-triazin-6'-yl) aminobenzenesulfonic acid

2-Amino-5- (2 ', 4'-dxchloros-triazin-6 ¹ -yl) -aminobenzenesulfonic acid

2-chloro-4- (3'-sulfophenyl) - [amino-6- (3 "-amino-4" -sulfophenyl) -amino-s-triazine (2-chloro-4- (8'-hydroxy-3 ¹ , 6 ^! -Disulfonaphthyl) -amino-striazin-6-yl) -phosphoramic acid

(2-chloro-if- (8 ^I -hydroxy-4 ', 6'-disulfo-naphthyl) -amino-striazin-6-yl) -phosphoramide acid

2-chloro-4-isopropoxy-6- (3'-amino-4'-sulfophenyl) -s-triazine

2-chloro-4- (ß-ethoxy) -ethoxy-6- (3'-amino-4'-sulfophenyl-s-triazine (2-chloro-4- (2'-sulfo-3 '- (3 "- methyl-pyrazol- 5-on-2-yl) -4'-methyl-phenyl) -amino-s-triazin -6-yl) -phosphoramic acid

(2-Chloro-4- (8'-hydroxy-3 \ 6'-disulfonaphthyl) -amino-striazin-6-yl-phosphoramic acid

Red

Red

Red

yellow

(2-Chloro-4- (4 '- (3 ^l! - methyl -5 -one -2 -yl) -5' -sulfophenyl) -s-triazin-6-yl) -phosphoramic acid

Red

Red

yellow

309882/1319

Example IQ

9.76 parts of 4-amino-4 '- (4 "-N-methylaminophenylazo) -stilbene-2,2'-disulfonic acid are dissolved in 200 parts of water, sets the p "value with 10N sodium hydroxide solution to 6.5 and gives 100 parts of a neutral solution containing 5 parts of (4,6-dichloro-s-triazin-2-yl) phosphoramic acid are. By simultaneous addition of 5N sodium hydroxide solution

the p _TT kept constant at 6.5. Towards the end of the reaction II

is heated to 30 to 35 °. If no free amino groups more are detectable, the bis-reactive dye formed is salted out, filtered off with suction and dried. A yellow powder is obtained which dyes cotton in yellow shades of high fastness.

Example 20

The same dye as in Example 19 is obtained if instead of the solution of (4,6-dichloro-s-triazin-2-yl) phosphoramic acid in water an equivalent amount of (4,6-dichloro-s-triazin-2-yl) phosphoramide trichloride, dissolved in dioxane, adds.

309882/1319

Example 21

Is used instead of (4,6-dichloro-s-triazin-6-yl) -phosphoramidsaure in Example l8, the equivalent amount (N-4, 6-Dlchior-s-triazin-6-yl) -N-methyl-phosphoramidsäure , a red, bis-reactive dye is also obtained.

309882/13 19

. -4fr -

Dyeing instruction I

2 parts of dye are with the addition of 0.5

Parts of sodium m-nitrobenzenesulfonate dissolved in 100 parts of water. A cotton fabric is impregnated with the resulting solution so that it increases by 75 % of its weight and then dried.

Then the fabric is impregnated with a 20 warm solution containing 5 grams of sodium hydroxide and 300 grams of sodium chloride per liter, squeezed to 75 % weight gain, the dyeing is dampened for 60 seconds at 100 to 101 °, rinsed, soaped for a quarter of an hour in one 0.3 # boiling solution of an ion-free detergent • rinses and dries.

Dyeing instructions II

2 parts of dye are dissolved in 100 parts of water.

The solution is added to 3900 parts of cold water, 80 parts of sodium chloride are added and 100 parts of a cotton fabric are added to this dyebath.

The temperature is increased in 45 minutes

to 90 °, 40 parts of trisodium phosphate and another 80 parts of sodium chloride being added after 30 minutes. The temperature is kept at 90 ° for 30 minutes, the dyeing is then rinsed and soaped for 15 minutes in a 0.3 # boiling solution of an ion-free detergent, and then rinsed . dries.

309882/1319

Printing specification: ■

2 parts of dye are sprinkled into 100 parts of a stem thickening containing "Feile 5 $ -ige" sodium alginate thickening, J> 2 parts of water, 20 parts of urea, 1 part of sodium m-nitrobenzenesulfonate and 2 parts of sodium bicarbonate, with rapid stirring.

Printed with the printing paste thus obtained

a cotton fabric is steamed on a roller printing machine and the printed fabric obtained is steamed in saturated steam for H minutes. The printed fabric is then thoroughly rinsed in cold and hot water, whereby the non-chemically fixed parts can be removed from the fiber very easily, and then dried.

309882/1319

Claims (1)

Claims 1 * reactive dyes which contain at least one group of the formula R _N / \ (D - N - C G - Z contain, in which R is a hydrogen atom or an alkyl radical, X is chlorine, bromine or fluorine and Z is a radical the formula OH 0T ¹ Me ⁺ - N ^- P = O (2a) or - N— P ^ O (2b) R 'OH R ¹ - 0 "-Me ⁺ where Me is a cation and R 'is a hydrogen atom or an alkyl radical. .
2. A reactive dye according to claim 1, wherein the dye molecule contains at least one sulfo group and from the series of the azo, meta, complex azo, anthraquinone, Phthalocyanine ^. . Formaζan or nitro dyes originates. 3- reactive dyes according to claim 1 of the formula D-N = N-A where D is the radical of a diazo component at most bicyclic, in particular a sulfonated phenyl or naphthyl rest, and A is bound to the azo bridge in the 2-position Radical of a l-hydroxynaphthalene-3-sulfonic acid means the in the 6-, 7- or 8-position one optionally via one 30 9882/131 ^ ' 6Q> Benzoylamino bridge bonded radical of the formula X J wherein R, X and Z are those given in claim 1. Have meaning, and which optionally has a further sulfonic acid group in the 5- or 6-position.
4. "Reactive dyestuff according to claim 1 of the formula D-N = N-A wherein D is the residue of a diazo component at most bicyclic, preferably a sulfonated phenyl, naphthyl or stilbenyl radical, and A, a benzene radical which in the 4-position to the azo group is a radical of the formula -R ' W ^X N N C C-Z wherein R, X and Z are as indicated in claim 1 ' Have meaning. 5 · reactive dyes according to claim 1 of the formula wherein Ap is the remainder of a naphtholsulfonic acid or the remainder an enolized or enolizable ketomethylene compound with the OH group in the ortho position to the azo group 3 09882/1319 and Dp is an aryl radical, preferably at most Beeyclic Aryl radical of the benzene or naphthalene series means, the one remainder of the formula JS R W ^V N Il « - N C C-Z wherein R, X and Z are those given in claim 1. Have meaning. 6. A reactive dye according to claim 1 of the formula D-N = N-A, wherein D is the residue of a diazo component at most bicyclic, in particular a sulfonated phenyl or naphthyl radical, and A, the radical of an enolized or enolizable one Ketoinethylene compound with the OH group in δ-position to Azo group means which is a radical of the formula I 1 8 N-σ σ-ζ wherein R, X and Z are those given in claim 1 Have meaning. 309882/1319 7r reactive metal complex compounds according to Claim 1 of azo dyes of the claims 3j and 6 given formulas, in which the radicals D, Dp, A, Ap and A have the meaning given and also in D or Dp in ο-position to the azo group a hydroxyl, have low molecular weight alkoxy or carboxylic acid group, 8. anthraquinone dyes geniäss claim 1 of formula wherein Y is hydrogen or a sulfonic acid group, Z " Bridge member, preferably a phenylene, diphenylene, 4,4-stilbene or 4,4'-azobenzene radical and R, X and Z have the meaning given in claim 1. 9 Phthalocyanine dyes according to claim 1 the formula ■ ⁽⁸⁰ 2- ^ω > η R r ^ N Pc ^^ (SO ₀ NH-Z "· -NC, CZ 309882/1319 wherein R, X and Z have the meaning given in claim 1, Pc is a ph'thalocyanine nucleus, preferably copper phthalocyanine, ω-ΟΗ and / or -NH _? , Z "'is a bridge member, -preferably an aliphatic, cycloaliphatic or aromatic bridge, and η and ni are each 1, 2 or 3 and can be the same or different, provided that η · + m is not greater than 4. 10. Nitro dyes according to Claim 1 of the formula V-NH-B-N-C C-Z wherein R, X and Z have the meaning given in claim 1 have, V and B are monocyclic ^ aryl nuclei and the nitro group in V is in the ortho position to the NH group ^ Reactive metal complex compounds according to Claim 1 of formazan dyes of the formula X ' = N-A-Y, Q- CH = N-B-Y 2 - · C-Z 309882/1319 - 66-- wherein Q is an organic radical, a nitro or cyano group, A and B radicals of diazo components of the benzene, naphthalene or heterocyclic series and Y, and Y _p each bonded in the o-position to the azo group, capable of complexing with a heavy metal Mean substituents
and in which R, X and Z have the meaning given in claim 1 and η is 1 or 2. 12. A reactive dye according to claim 1, which is two identical or contain different groups of the formula (I) in which R, X and Z have the meanings given in claim 1. 309882/1319 13. Process for the production of reactive paint substances which have at least one group of the formula NC β - Z (1) Ν / contain, wherein R is a hydrogen atom or an alkyl rest, X is chlorine, bromine or fluorine and Z is a radical of the formula - + -OH 0 ... He - ' -N -P = O (2a) or - N- P = O (2b) R 'OH R 0 ":. Me is, where Me is a cation and R 'is a hydrogen atom or is an alkyl radical, characterized in that that one dyes or intermediate dye products that at least one group of the formula -NK-R (3) have, wherein R has the meaning given, with a compound of the formula N N ^ j (4a) or X - \\ - ^ - oo -BN _0H . NN _ft - _M "+ £ ".. ■ T- I Y Unc · YI N 'Ρ ^ ^f OH · ^Rt Ο · "- Me ⁺ (4b) - 70-- and R '/ ·' converts, in which X, Me / have the meaning given. lh. Process according to claim 13, characterized in that dyestuffs containing amino groups from the series of the azo-metal complex azo., Anthraquinone, phthalocyanine / forma an or nitro dyestuffs which contain at least one sulfo group, with a (4,6- Dihalogen-s-triazin-2-yl) _ phosphoramic acid of the formula (4a) or (4b). Process according to claim 13, characterized in that one dyes of the formula D-N = N-A wherein D is the radical of a diazo component of a highest bicyclisehen, especially a sulphonated phenyl or naphthyl radical, and A in the 2-position to the azo bridge bonded radical l-hydroxynaphthalene-3-sulfonic acid, in the 6-, 7- or 8 ₇ position _{a radical of the formula c,} optionally bonded via a benzoylamine bridge -NH. has, wherein R has the meaning given, and in 5- or 6-position optionally has a further Sulfonic acid group, mit.einer (4,6-dihalogen-s-triazin-2-yl) phosphoramic acid of formula (4a) or (4b). ' 16. The method according to claim 13, characterized in that that you can get dyes of the formula DN = NA ₁
where D is the remainder of an at most bicyclic diazo component 30 9 882/1319 duck, preferably a sulfonated phenyl, naphthyl or stilbenyl radical, and A, is a benzene radical which in the 4-position to the azo group is a radical of the formula - NH has, wherein B has the meaning given, with a (4,6-Dihalogen-s-triazin-2-yl) -phosphoramic acid of the formula (4a) or (4b). 17 · Method according to claim 13. » known thereby draws that one dyes of the formula D ₂ -N = NA ₂ wherein Ap is the remainder of a naphtholsulfonic acid or the remainder an enolized or enolizable ketomethylene compound with the OH group in the ortho position to the azo group and Dp is an aryl radical, preferably at most a bicyclic one Aryl radical of the benzene or naphthalene series denotes a radical of the formula: -NH has, wherein R has the meaning given, with a (4,6-dihalogen-s-triazin-2-yl) phosphoramic acid of the formula (4a) or (4b) implemented. l8. Method according to claim 13, characterized in that that one dyes of the formula D-N-N-A. where D is the residue of a highest bicyclic diazo component 309882/1319 ente, in particular a sulfonated phenyl or naphthyl radical, and A. the radical of an enolized or enolizable Ketomethylene compound with the OH group in the o-position to the azo group, which is a radical of the formula R - NH has, wherein R has the meaning given, with a (4, 6 ~ Dihalogen-s-triazin-2-yl) -phosphoramic acid of the formula (4a) or (4b) implemented. 19. The method according to claim 13, characterized in that that one metal complex dyes, which azo dyes of the formulas given in claims 15, 17 and 18 contain, in which the radicals D, D ", A, Ap and A., the specified Have meaning and also in D or Dp in ο-position to the azo group have a hydroxyl, low molecular weight alkoxy or carboxylic acid group, with a (4,6-dihalo-s-triazin-2-yl) phosphoramic acid of formula (4a) or (4b). 20. The method according to claim 13, characterized in that that one anthraquinone dyes of the formula ΕΙ NH co NH- Z "- NH 309882/1319 wherein Y is hydrogen or a sulfonic acid group, Z " Bridge member, preferably a phenylene, diphenylene, 4,4'-stilbene or 4,4'-azobenzene radical and R denotes the has given meaning, with a (4,6-dihalogeno-s-triazin-2-yl) phosphoramic acid of formula (4a) or (4b). 21. The method according to claim 13, characterized in that that one phthalocyanine compounds of the formula - (SO— ω) , 2 η - (SO ₂ NH - Z "'- wherein Pc is a phthalocyanine nucleus, preferably copper phthalocyanine, ω-ΟΗ and / or -NH ₂ ^'Z "' ^{is a C} kenglied ^Br Ü, preferably an aliphatic, cycD.oaliphatische or aromatic bridge, and η and m are each 1, 2 or 3 and may be the same or different, provided that η - «- m is not greater than 4, and where R has the meaning given, with a (4,6-dihalo-s-triazin-2-yl) phosphoramic acid of the formula (4a) or (4b) implemented 22. The method according to claim 13, characterized in that draws that nitro dyes of the formula V-NH-B-NHR NO ₂ wherein V and B are monocyclic aryl nuclei and the 309882/1319 - ir ¹ ^ " Nitro group in V is in the ortho position to the NH group and in which R has the meaning given, with a (4,6-dihalo-s-triazin-2-yl) phosphoramic acid of formula (4a) or (4b). 23, - method according to claim 13, characterized in, that one metal complex compounds of formazan dyes of the formula N = N - A - Y Q-CH NH ν - -J η NN - A - Y ₂ R i where Q is an organic radical, a nitro or cyano group, A and B radicals of diazo component !! of the benzene, naphthalene or heterocyclic series and Y and Y each one Substituents bound in the o-position to the azo group and capable of complex formation with e: "em heavy metal mean, η has the value 1 or 2 and R has the meaning given, with a (4,6-dihalo-s-triazin-2-yl) phosphoramic acid of the Formula (4a) or (4b) implemented. 309882/1319 24. The method according to claim 13 * thereby characterized in that dyes or intermediate products are used, which have at least one group of formula (3) with compounds of formula (4a) or (4b) converts in such a way that reactive dyes are formed which contain two identical or different groups of the Formula (I), wherein R, X and Z have the in Claim 13 have given meanings. 25. Process for dyeing and printing Textile material, in particular that made of cellulose, characterized by the use of .der according to Claims 1 to 12 defined or according to claims 13 to 24 produced dyes. Material. 27. Formula The colored obtained according to claim 25 Method for producing a compound of 309882/1319 ϊηϊ XNX YY ^N ¥ OH ⁽⁴⁾ OH ι I MH - P = 0 OH wherein X is chlorine, bromine or fluorine, as well as salts of these Connection, characterized in that a connection the formula XNX flW yy yy i * N = P-Cl Nile * 'i where X has the meaning given, in an aqueous Medium hydrolyzed in the presence of an acid-binding agent. 28. The method according to claim 27, characterized in that that the hydrolysis is carried out at a pH of 7 to 8. 29. The method according to claims 27 and 28 ^ thereby
characterized in that one in aqueous phosphate buffer or
a mixture thereof with an organic solvent
is working. 30 9 8.8 2/1 319 30. The method according to claims 27 to 29 * characterized in that one works at room temperature or below. 31. Process according to claims 27 to 30 * characterized in that one of (4,5-dichloro-striazin-2-yl) phosphorimide trichloride goes out. 309882/1319