DE2102217B2 - REACTIVE COLORS, METHOD OF MANUFACTURING AND USING them - Google Patents

Description

χ.

wherein F ₁ and F ₂ each represent a radical of an organic dye, R ₁ and R ₃ independently of one another are hydrogen, methyl or ethyl, X ₁ and X _{2 are} each a halogen atom and R _{2 is} hydrogen, an alkyl radical with 1 to 5 carbon atoms or a

NO,

optionally substituted by cyano, chlorine, bromine, hydroxy or alkoxy with 1 to 3 carbon atoms, alkyl radical with 1 to 3 carbon atoms, a phenyl radical or a benzyl radical.
2. Dyestuffs according to Claim 1 of the formula

F ₁ -NH-C

C.
Cl

y \

C-N-C C-NH-F ₂

Il i I Il

NR ₂ N

C. Cl

where F ₁ and F _{2 are the} same dye _{radicals and R 2 is} a phenyl radical.

3. Dyestuffs according to claim 1, of the formula (3), in which F ₁ and F _{2 are} identical dyestuff _{radicals and R 2 is} hydrogen or an alkyl radical having 1 to 5 carbon atoms.

4. Process for the preparation of dyes of the formula (1) according to Claim 1, characterized in that that one compounds of the formula

X ₄ -C

C-N-C

NNR ₂ NN

C C

(4)

wherein X ₁ , X ₂ , X ₃ and X _{4 are} halogen atoms and R _{2 has} the meaning given under formula (1), with dyes of the formula F ₁ -N (R ₁ ) H and F ₂ -N (R ₃ ) H , where F ₁ , F ₂ , R ₁ and R _{3 have} the meanings given under formula (1), condensed to form dyes of formula (1), it being possible for the order of the partial reactions to differ from f> ₀ .

5. The method according to claim 4, characterized in that compounds of the formula (4) in which X ₁ , X ₂ , X ₃ and X ₄ are chlorine atoms and R _{2 is} a phenyl radical, with amino group-containing dyes of the formulas F _; - NH ₂ and F ₂ -NH ₂ , in which F _{1 and F 2 are} identical dye residues, converts.

6. The method according to claim 4, characterized in that compounds of the formula (4) in which Xi, X ₂ , X ₃ and X ₄ are chlorine atoms and R _{2 is} hydrogen or an alkyl radical having 1 to 5 carbon atoms, with dyes containing amino groups Formulas F ₁ - NH ₂ and

mean implements.

7. Use of dyes according to claims 1 to 3 or of according to claims 4 to 6 available dyes for dyeing and printing cotton and regenerated Cellulose.

Reactive dyes, the two with each other via a diamine Containing linked triazine residues are known. In these, there is always a between the reactive residues more or less large bridge member is present, and there are both reactive radicals on different nitrogen atoms bound.

From Austrian patents 2 98 630, 98 631 and 2 98 632, especially the Austrian one Patent specification 2 98 631, dyes are also known which contain a bis-triazinyl-hydrazinresl.

It has now been found, surprisingly, that reactive dyes can be produced which have two linked to one another via a single amino group Contain reactive radicals, so that both reactive radicals with linked to the same nitrogen atom.

The present invention now relates to dyes which have two via the nitrogen atom of an amino group contain interconnected fiber-reactive triazine residues, namely dyes of the formula

wherein F ₁ and F ₂ each represent a radical of an organic dye, R ₁ and R ₃ independently of one another are hydrogen, methyl or ethyl, X ₁ and X _{2 are} each a halogen atom and R _{2 is} hydrogen, an alkyl radical having 1 to 5 carbon atoms or an optionally through Denotes cyano, chlorine, bromine, hydroxy or alkoxy substituted with 1 to 3 carbon atoms, a phenyl radical or a benzyl radical.

The third substituent R ₂ on the nitrogen atom of the amino group, which connects the two reactive radicals with one another, can preferably be a methyl, ethyl, / f-methoxyethyl or piopyl radical or a phenyl or benzyl radical.

The preferred reactive group is the monochler-1,3,5-triazine radical.

The dyes can be of any known class of dyes, and preferably belong the mono- or polyazo series or the nitro, anthraquinone or phthalocyanine series. Preferably they contain at least one water-solubilizing group, in particular a carboxylic acid or Sulfonic acid group. If desired, the dyes can also be coordinated metal, such as contain coordinated copper, chromium or cobalt. There are also basic dyes into consideration.

Dyes according to Claim 1 of the formula are preferred

N N

F ₁ -NH-C C -NC 'C -NH-F,

I Il I I Il

NNR ₂ NN

C C

Cl Cl

where F ₁ and F _{2 are the} same dye _{radicals and R 2 is} a phenyl radical.

Of particular importance are dyes according to claim 1 of the formula (3) in which F ₁ and F ₂ denote the same dye _{radicals and R 2 is} hydrogen or an alkyl radical having 1 to 5 carbon atoms.

The invention also relates to a method for producing dyes from Füimc! (1) [and also of the formula (3)], in which compounds of the formula

N N

"Ύ Yh 'Y * ^m

NNR ₂ NN

x,

wherein X ₁ , X ₂ , X ₃ and X _{4 are} halogen atoms and R _{2 has} the meaning given under formula (1), with dyes of the formula F ₁ —N (R ₁ ) H and F ₂ —N (R ₃ ) H , where F ₁ , F ₂ , R ₁ and R _{3 have} the meanings given in the formula (1), condensed to form dyes of the formula (1), it being possible for the order of the partial reactions to be different.

The preparation of the starting compounds of the formula (4) is in the Journal of the heterocyclic, ("hem .. Vol. 7, No. 3, pages 519 to 325 (1970).

According to a preferred embodiment of the process according to the invention, the procedure is that compounds of the formula (4) in which X ₁ , X ₂ , X ₃ and Xa are chlorine atoms and R _{2 is} a phenyl radical, with amino group-halligon dyes of the formulas F ₁ -NH ₂ and F ₂ —NH ₂ , in which F ₁ and F _{2 represent the} same dye radicals.

According to a further advantageous embodiment of the process according to the invention, one works in such a way that compounds of the formula (4) in which X ₁ , X ₂ , X ₃ and X ₄ are chlorine atoms and R _{2 is} hydrogen or

4u an ÄlkyirSSi with 1 uiS j rvGiiiCnSiöiiSiGrnCri uCuCU- tet, with amino group-containing dyes of the formulas F ₁ - NH ₂ and F ₂ --NH ₂ , in which F ₁ and F _{2 represent the} same dye radicals.

The reaction to produce the tetrahalogen compound of formula (4) with the halotriazines, such as. B. 2,4,6-Trichloro- (-tribromo- or -trifluoro) -1,3,5-triazines is carried out expediently in the presence of acid-binding agents, such as. B. sodium carbonate, and in an organic solvent or at a relatively low temperature in an aqueous medium.

One proceeds advantageously so that one first 1 mole of ammonia or primary amine, such as z. B. aniline, reacted with 1 mole of trihalotriazine and the product obtained then with 1 mole of the the same or a different trihalotriazine condensed. The reactions can be known per se Way in the presence of an acid-releasing agent, such as. B. sodium hydroxide made will. This is how the connections are obtained

to the general formula (4).

Primary amines are preferably used as amines, i.e. / .. B. alkylamines, such as methylamine, Ethylamine, propylamine. Isopropylamine, butylamine, Amylamine, / ί-chloro- or / ί-bromoethylamine.

f'5 // - Cyanätliylamin, // - Hydroxyäthylamin,; -Hydroxypropylamin, Methoxymethylamine, // - Mcthoxyäthylamin, --Methoxypropylamin, Älhoxymethylamin, / C-ethoxyethylamine. ; ■ -Athoxypropylamine. y-lso-

propoxypropylamine, benzylamine or axylamine such as Aniline or the ammonia itself

The bisreactive grouping of the formula (4) obtained in this way is then reacted with a dye which contains at least one acylatable —NHR ₁ or _{—NHR 3} group, in which R ₄ and R _3, independently of one another, represent a hydrogen atom, a methyl or ethyl radical .

One arrives so z. B. to compounds of formulas (1) and (3j. Ίο

The reaction takes place in a manner known per se, preferably also in the presence of one acid binding agent.

The dye compounds of the azo series which are used as output products and which _{contain at least one -NHR 1} or _{-NHR a} group can be obtained by various processes. One method consists in diazoiating an aromatic primary amine and coupling the diazonium compound thus obtained with a coupling component containing _{an —NHR 1} or —NHR _{3 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-chlorailines,

2,5-dichloroaniline, \ - and / i-naphthylamine,

2,5-dimethylaniline,

5-nitro-2-am inoanisole,

4-aminodiphenyl,

Aniline-2,3- and -4-carboxylic acids, 2-aminodiphenyl ethers,

2-, 3- or 4-aminobenzenesulfonamide or -sulfomonomethyl- or

-äthylamide or

-sulfondimethyl- or -sulfondiä thylamide,

Dehydrothio-p-toluidine monosulfonic acid or Dehydrothio-p-toluidinedisulfonic acid, aniline-2, -3- and -4-sulfonic acids, Aniline-2,5-disulfonic acid, 2,4-dimethylaniline-6-sulfonic acid, 3-aminobenzo-trifluoride-4-sulfonic acid, 4-chloro-5-methylaniline-3-sulfonic acid, 5-chloro-4-methylaniline-2-sulfonic acid,

S-acetylaminoaniline-δ-sulfonic acid, see above

4-acetylamimoaniline-2-sulfonic acid, 4-chloroaniline-2-sulfonic acid,

3,4-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.

l-naphthylamine-2-, -4-. -5-, -6- or -7-monosulfonic acid,

l-naphthylamine-3,6-disulfonic acid.

2-naphthylamine-3,6- and -5.7-disulfonic acid.

2-naphlhylamine-3,6,8-trisulfonic acid, 6s

m- and p-nitroaniline,

4-nitroaniline-2-sulfonic acid,

VNilroaniline-6-sulfonic acid.

m- or p-Amüflacetanilid and ^ Amino-l-acetyfaminotoiuol-S-sulfonic acid.

Examples of coupling components that can be used are:

2-amino and
2-methylamino-5-naphthol-7-sulfonic acid, 2-amino and
2-methylamino-8-naphthol-7-sulfonic acid, 1-amino and

1 -ethylamino-S-naphthol-o-sulfonic acid and

corresponding 3,6- and 4,6-disulfonic acids,

H3'- or 4'-aminobenzoylamino) -8-naphthol-3,6- and -4,6-disulfonic acid,

Aniline,

o- and m-anisidine,

o- and m-toluidine,

2,5-dimethylaniline,

3-amino-methoxytoluene,

2,5-dimethoxyaniline,

N-methylaniline,

N-ethyl-o-toluidine,

N-methyl-m-anisidine,

3-methylamino-4-methoxytoluene.

l- (3'-aminophenyl) -3-methyl-, -carboxy- and -carboethoxy-5-pyrazolone,

1- (4'-aminophenyl) -3-methyl-, -carboxy- and carboethoxy-5-pyrazolone and 1- (4'-Amino-3'-carboxyphenyl) -3-methyl-5-pyrazolone.

The aminoazo compounds to be used in the process according to the invention are not all limited to compounds containing only one azo group. Disazo compounds can, for example by tetrazotization of an aromatic diamine containing two primary amino groups and Coupling of the tetrazo compound thus obtained with 2 molar proportions of one of the coupling components defined above or with 1 molar fraction of each of two of the coupling components defined above or with 1 mole of one of the coupling components defined above and with 1 mole fraction of one no amino group containing coupling component are obtained. As examples of such aromatic diamines may be mentioned: benzidine-3,3'-dimelhoxybenzidine, benzidine-2,2'-disulfonic acid, benzidine-3,3'-dicarboxylic acid. Benzidine-3,3'-diglycolic acid and 4,4'-diaminostilbene-2,2'-disulfonic acid. Furthermore, disazo or polyazo compounds by using azo group-containing primary aromatic amines odei Diamines are obtained. As examples of such azo group-containing primary aromatic Amines or diamines may be mentioned: 4-Aminoazo benzene - 4 '- sulfonic acid, 4' - Amino - 2 '- methylphenyl azo - 2 - naphthalene - 4,8 - disulfonic acid, 4 - amino S-methoxy ^ -methyW-nitro ^ '- sulfazobenzene.

Instead of -NHR ₁ - ₃ -Gruppet assumed free amines or NHR can also gewünschtenfallseinc-N HR ₁ -bzw.-NHR, -Gruppi containing coupling component having a '-NHR ₁ -, or - NHR ₃ group-containing Coupling the azonium compound. Such diazonium compounds can be obtained by known processes by diazotizing primary or aromatic amines which contain a second amino group or a monocubstituted amino group

Examples of such primary aromatic amines are: p-phenylenediamine, 1,4-phenylenediamine-2-sulfonic acid, 1,4-phenylenediamine-2-carboxylic acid, 1,4-diaminonaphthalene-2-sulfonic acid. Examples of coupling components which can be used in this way are the mentioned above coupling components and also ß-naphthol, 2-naphthol-o- or -7-sulfonic acid, 2 - naphthol - 3,6 - or - 6,8 - disulfonic acid, 1 - naphthol - 4 - sulfonic acid, 1 - phenyl - 3 - methyl-5-pyrazolone, 1 - (4'-sulfophenyl) -3-methyl-5-pyrazolone, 1 - (2 ', 5' - dichloro - 4 '- sulfophenyl) -3 - methyl-5 - py razolon, 2 - benzoylamino - 5 - naphthol - 7 - sulfonic acid, 1 - benzoylamino - 8 - naphthol - 3,6 - or ■ 4,6-disulfonic acid, phenol, p-cresol, acetoacetanilide and acetoacet-2-methoxyaniline-5-sulfonic acid.

Further processes for preparing the _{dye compounds of the azo series containing a —N1IR 1} or —NHR ₃ group, which can be used in the process according to the invention, consist in reducing a nitro group-containing dye or an azo or polyazo compound which contains at least one acylamino group contains to treat 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 - 4 '- acetylaminodiphenyl - 3 - sulfonic acid, 4-amino-3-sulfoacetanilide, 3-amino-4- sulfoacetanilide and 4 - amino - 4 '- acetylaminostilbene-2,2'-disulfonic acid; and as examples of such coupling components are mentioned: 2-acetylamino-5-naphthol-7-sulfonic acid, 2-N-acetyl-N-methylamino-5-naphthol-7-sulfonic acid, 2-acetylamino- and 2-N-acetyl-N - methylamino - 8 - naphthol-6-sulfonic acids and 1-acetylamino-S-naphthol ^ ö- and -4,6-disulfonic acids.

As examples of dye compounds of the anthraquinone series which can be used in the present process as starting materials, may be mentioned anthraquinone compounds having a group defined above of the formula - NHR ₁ or NHR ₃ at an alkylamino or arylamino group, which itself to the " »Position of the anthraquinone nucleus is bound. Examples of such anthraquinone compounds are:

l-amino-4- (4'-aminoanilm) -anthraquinone-

2,3'-disulfonic acid and the corresponding

2,3 ', 5-, 2,3', 6- and 2,3 ', 7-trisulfonic acids,

1-Amino-4- (4 '' -amino ^ '- benzoylaminoaniline) -

anthraquinone-2,3-disulfonic acid

and the corresponding

-2,3 ', 5-trisulfonic acid,

l-Amino-4- [4 '- (4 "-aminophenylazo) -anilino] -

anthrachiinon-2 | 2 ", 5-trisulfonic acid,

1-amino-4- (4'-amino-3 '-carboxyanilino) -

anthraquinone-2,5-disulfonic acid,

l-Aminoi-4- (3'-aminoanilino) -anthraquinone-

2,4 ', 5-trisulfonic acid and

the corresponding 2,4-disulfonic acid,

1 -Arnino-4- [4 '- (4 "-aminophenyl) -anilino] -

anthraquinone-2,3``, 5-trisulfonic acid,

l-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,

l-Amino-4- (4'-methylamino-3'-carboxyanilino) -anthraquinone-2-sulfonic acid,
1-amino-4- (3'-ii-hydroxyethylamino) -anilinoanthraquinone-2,5-disulfonic acid,
ι ο 1 - (4'-aminoanilino) anthraquinone-2,3-disulfonic acid and
1-Amino-4- (4'-amino-2'-methoxyanilino) -anthraquinone-2,3'-disulfonic acid.

Such dye compounds of the anthraquinone series can even be made from anthraquinone compounds, which a halogen atom or a nitro group to the corresponding α-position of the anthraquinone nucleus contain bound, or from the leuco derivative of a 1,4-dihydroxy-, -diamino- or -aminohydroxyanthraquinone by reacting the corresponding anthraquinone compound in at least one molar proportion an aliphatic or aromatic diamine can be obtained.

Dye compounds of the phthalocyanine series which can be used in the process according to the invention are preferably metal-containing phthalocyanines, such as copper phthalocyanines, which contain at least one water-solubilizing group, such as a sulfonic acid group, and at least one group of the formula -NHR ₁ or -NHR ₃ , as defined above, contain. The _{—NHR 1} or —NHR ₃ 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—, —SO ₂ -phenylene— . —NH-phenylene “, —S-phenylene“, - O-phenylene “. - CH ₂ S-phenylene -, - CH ₂ O-phenylene -. —CH ₂ -phenylene -, - SCHz-phenylene—, SO ₂ CH ₂ -phenylene—, -SO ₂ NR ₁ -phenylene—, -CH ₂ -,

- SO ₂ NR ₁ - Arylene -, - NR ₁ CO - Phenylene -, NR ₁ SO ₂ - Phenylene -, - SO ₂ O - Phenylene _{---, -CH 2} -, - CHzNRj-Phenylene -, -CH ₂ NH- CO-phenylene, - SO ₂ NR _r alkylene, -CH ₂ -NR r alkylene. —CONR ₁ phenylene—, —CH ₂ -, —CONR ₁ -arylene—, —SO ₂ - or a —CO— bridge. In the abovementioned divalent bridge members, R ₁ denotes hydrogen, alkyl or cycloalkyl, and arylene denotes a bivalent aromatic, optionally e.g. B. by halogen, alkyl or alkoxy substituted radical, in which the terminal bonds can be bonded to the same or different nuclei, and alkylene is a divalent aliphatic radical which can include heteroatoms, such as nitrogen, in the atomic chain, for example the radical

- CH ₂ CH ^ --NH - CH ₂ CH ₂ -.

As examples of such divalent aromatic radicals denoted by arylene are mentioned: aromatic nuclei, for example a benzene, Naphthalene, acridine and Carbazolkera, which can carry further substituents, and residues of formula

in which the benzene rings can carry further substituents and —D— a bridging group

means, for example

-CH = CH- -NH- - S— -Ο -

-SO ₂ - -NO = N- -N = N-

- NH-CO — NH-CO —NH-

- Ο — CH ₂ CH ₂ O- or

N N

Z " ¹

C-

As specific examples of the phthalocyanine series dye compounds used in the invention Methods that can be used are: copper phthalocyanine-4-N- (4-amino-3-sulfophenyl) -sulfonamide-4 ', 4 ", 4'" - trisulfonic acid, Cobalt phthalocyanine 4,4'-di-N- (4'-amino-4'-sulfophenyl) carbonamide - 4 ", 4 '" - dicarboxylic acid and copper 4- (4'-amino-3'-sulfobenzoyl) -phthalocyanine.

Mixtures of aminophthalocyanines can also be used be used. For example, a mixture of approximately equal parts of copper phthalocyanine can be used N - (4 - amino - 3 - sulfophenyl) sulfonamide trisulfonic acid and copper phthalocyanide di-N- (4-amino-3-sulfophenyl) sulfonamide disulfonic acid be used.

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 and sulfonated phthalic acid derivatives. The sulfonating agent used is, for example, oleum, ζ. B. a 20% solution of sulfur trioxide in sulfuric acid. Furthermore, they can be obtained by jointly heating suitable derivatives of sulfonated phthalic acid and substituted phthalic acids by the generally known processes, for example by jointly heating a mixture of 4-sulfophthalic anhydride and 4-p-nitrobenzoylphthalic anhydride, urea, cupric chloride and ammonium molybdate o-dichlorobenzene at about 150 ⁰ C. also, by sulfonation of the corresponding primary and sekundäten amines or by reacting a primary (or secondary alkyl or N-cycloalkyl) -Nitroanilins with a phthalocyanine containing chloromethyl and sulfonic acid or carboxylic acid groups, Phthalocyanines are produced, which are used as starting materials. Furthermore, such aminophthalocyanines can also be obtained by reacting a phthalocyanine containing 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) with aqueous alkali to hydrolyze the Acetylamino group are produced or by reacting a phthalocyanine which contains chloromethyl and sulfonic acid or carboxylic acid groups with a monoacetylalkylenediamine and treating the product thus obtained with aqueous alkali to hydrolyze the acetylamino groups. In addition, by direct sulfonation or by joint heating of 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 reducing the nitrophthalocyanine sulfonic or carboxylic acid or hydrolysis of the resulting Acylaminophthalocyaninesulfonic or carboxylic acid or by reacting a phthalocyanine compound which contains carboxylic acid chloride groups with a diaminobenzenesulfonic or carboxylic acid, an aminobenzenesulfonic acid or an aminobenzoic acid, which also contains a nitro group, and reducing the nitro compound obtained in this way or finally by reacting a phthalocyanine compound which contains carboxylic acid chloride groups contains, with an N-aminobenzylacetamide and subsequent hydrolysis of the product thus obtained with aqueous alkali.

Nitro-series dye compounds which are used in the process of the invention are preferably those of the formula

NO ₂ -DNQ

where D is a naphthalene or benzene nucleus, which may be further substituted, the nitrogen atom N is in the ortho position to the nitro group. Z is hydrogen or an optionally substituted one

Hydrocarbon radical and Q is hydrogen or an organic radical bonded to nitrogen through a carbon atom and in which Q and Z are not both hydrogen and Q is on Z when Z is a hydrocarbon radical. or can be bonded to D in the ortho position to the nitrogen atom N to form a heterocyclic ring, and which _{contain at least one group of the formula —NHR 1} or —NHR ₃ , as defined above.

As particular examples of at least one

- NHR ₁ - or - NHR ₃ group-containing coloring substance compounds which can be used as starting products in the process according to the invention, the compounds of the following classes may be mentioned:

1. Monoazo compounds of the formula

OH

-NHR

wherein D _{1 is} an at most bicyclic, from azo

and -NHR, - or - NHR _r groups free aryl

rest means and the -NHR ₁ - or -NHR ₃

Group preferably to the 6-, 7- or 8-position

of the naphthalene nucleus is bound, and which one

Sulphonic acid group in the 5- or 6-position of the naphtha

linkerns.

D, can be a residue of naphthalene odc Benzene series mean which contains no azo substituents, for example a stilbene, diphenyl, Ben /

thiazoylphenyl or diphenylamine radical. In this class, attention should also be paid to the related dyes in which the —NHR ₁ or —NHR ₃ group, instead of being bonded to the naphthalene nucleus, is bonded to a 6-, 7- or 8-position of the naphthalene nucleus Benzoylamino or anilino group is bound.

Particularly valuable starting dyes are those in which D, denotes a sulfonated phenyl or naphthyl radical, especially those which _{contain an - SO 3} H group in the ortho position to the azo bond; the phenyl radical can be further substituted, for example by halogen atoms such as chlorine, alkyl radicals such as methyl, acylamino groups such as acetylamino, and alkoxy radicals such as methoxy.

2. Disazo compounds of the formula IV, in which D _{1 is} a radical of the azobenzene, azonaphthalene or phenylazonaphthalene series and the naphthalene nucleus is substituted by the —NHR ₁ or —NHR ₃ group and, if desired, by sulfonic acid, as in class 1.

3. Monoazo compounds of the formula

D ₁ -N = NK ₂ -NHR

(VII)

where D _{1 is} a radical of the types defined _{for D 1} in classes 1 and 2 above _{and K 2 is} the radical of an enolizable ketomethylene compound (such as an acetoacetarylide or a 5-pyrazolone) with the OH group in the ortho position to the azo group.

6. The metal complexes, for example the copper, chromium and cobalt complexes, of the dyes of the formulas IV, VI and VII, in which D ₁ , K and K _{2 have} the meanings given in each case and also a metallizable group (for example dnc hydroxyl, lower Alkoxy or carboxylic acid group) in ortho control to the azo group in D, is present.

IO

D ₁ -N = N- / ~~ V-NHR (V)

where D ₁ denotes an at most bicyclic aryl radical, as described in class 1, and preferably a disulfonaphthyl or stilbene radical, and the benzene nucleus denotes further substituents. such as halogen atoms or alkyl, alkoxy, carboxylic acid and acylamino groups.
4. Mono- or disazo compounds of the formula

HND ₁ -N = NK (VI)

wherein D _{1 is} an arylene radical. like a remainder of the azobenzene. Azonaphthalene or Phenylazonaphthalinrcihc. or preferably an at most bicyclic arylene radical of the benzene or naphthalene series and K is the radical of a naphtholsulfonic acid or the radical of an enolized or collapsible ketomethylene compound (such as an acetoacetarylide or a 5-pyrazolone) with the OH group in the ortho position to the azo group. D ₁ preferably denotes a radical of the benzene series which contains a sulfonic acid component
5. Mono- or disazo compounds of the formula

7. Anthraquinone compounds of the formula
O

NHR

SO ₃ H

O NH - Ζ '- NHR

wherein the anthraquinone nucleus contains an additional sulfonic acid group in the 5-, 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, diphenylene or 4,4 '-Stilbene or azobenzene residue. Preferably, Z 'should contain one sulfonic acid group for each benzene ring present.
8. Phthalocyanine compounds of the formula

Pc

(SO ₂ NH-Z '-NHRL

where Pc is a phthalocyanine nucleus, preferably copper phthalocyanine, - OH and / or - NH ₂ , Z 'eir bridge member, preferably an aliphatic, cyclo aliphatic or aromatic bridge, and η and n are each 1, 2 or 3 and are the same or different can, provided that η + m is not magnitude; than is 4.
9. Nitro dyes of the formula

V-NH-B -NHR

NO ₂

where V and B are monocyclic aryl rings unc the nitro group in V in the ortho position to the NH Group stands.

The following are, for example, possible starting dyes in the dye classes mentioned

In class 1

6-amino-1-hydroxy-2- (2'-sulfophenylazo) -

naphthalene-3-sulfonic acid,

6-methylamino-1-hydroxy-2- {4'-acety! Amino-

2'-sulfophenylazo) -naphthalene-3-sulfonic acid.

8-amino-1- hydroxy-2- {2'-sulfophenylazo) -

naphthalene-3,6-disulfonic acid,

8-amino-1-hydroxy-2- (4'-chloro-2'-sulfophenyl-

azo} -naphthane-3,5-disulfonic acid,

7-Amino-2- (2 ', 5' - disuhOphenylazo) -l -bydroxynaphthaIm-3-sulfonic acid,

7-methylamino-2- {2'-suifophenylazo) -1-hydroxy naphthalene-3-sulfonic acid,

7-MethyJamino-2- <4'-nietboxy-2'-sulfophenyl-

azo) -l -hydroxynaphthalene-3-sulfonic acids, g-il'-AminobenzoylanimoVHiydroxy ^^ '- sulfo pbenylazo) -naphtbalni-3,6-disulfonic acid,

8-amino-l -bydroxy - ^ '- azonaphthalene-

1 '3'4', 6-tetrastifonic acid,

8-Amino-l -hydroxy - ^ '- azonaphthalene-1', 3,5 ^r -trisulfonic acid,

6-Amino-1-hydroxy-Z ^ i'-azonapbthalin-

1 '^' - trisulfonic acid,

6-methylamino-1-hydroxy-2 _T 2'-azonaphthalene

7-amino-1-hydroxy-2,2'-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'-hydroxy-3'-carboxyphenylazo) -naphthalene-3,5-disulfonic acid.

In class 2

8-Amino-1-hydroxy-2- [4 '- (2 "-sulfophenylazo) -2'-methoxy-5'-methylphenylazo] -naphthalen- 3,6-disulfonic acid,

8-Amino-1-hydroxy-2- [4 '- (4 "-methoxyphenylazo) -2'-carboxyphenylazo] -naphthalene- 3,6-disulfonic acid,

8-Amino-1-hydroxy-2- [4 '- (2 "-hydroxy-3", 6 "-disulfo-1" -naphthylazo) -2'-carboxy- phenyIazo] -naphthalene-3,6-disulfonic acid, 4,4'-bis- (8 "-amino-1" -hydroxy-3 ", 6" -disulfo-2 "-naphthyIazo) -3,3'-dimethoxydiphenyl.

6-Amino-1-hydroxy-2- [4 '- (2 "-sulfophenylazo) -2'-methoxy-5'-methylphenylazo] -naphthalene- 3,5-disulfonic acid.

In class 3

2- (4'-Amino-2'-methylphenylazo) -naphthalene-4,8-disulfonic acid,

2- (4'-Amino-2'-acetylaminophenylazo) -naphthalene-5,7-disulfonic acid,

4-nitro-4 '- (4 "-methylaminophenylazo) -stilbene-2,2'-disulfonic acid,

4-nitro-4 '- (4 "-amino-2" -methyl-5 "-methoxyphenylazo) -stilbene-2,2'-disulfonic acid, 4-Amino-4 '- (4 "-methoxyphenylazo) -stilbene-2,2'-disulfonic acid,

4-Amino-2-ynethylazobenzene-2 ', 5'-disulfonic acid c.

In grade 4

1- (2 ', 5'-dichloro-4'-sulfophenyl) -3-methyl-4- (3 "-amino-4" -sulfophenylazo) -5-pyrazolone, 1- (4'-sulfophenyl) -3-carboxy-4- (4'-amino-3 ' '-sulfophenylazo) -5-pyrazolone, 1- (2'-methyl-5'-sulfophenyl) -3-methyl-4- (4 "-amino-3" -sulfophenylazo) -5-pyrazolone, 1- (2'-sulfophenyl) -3-methyl-4- {3 "-amino-4 "-sulfophenylazo) -5-pyrazolone, 4-amino-4 '- (3" -metltiyl-1 "-phenyl-4" -pyrazole-5 "-onylazo) -stilbene-2,2'-disulfonic acid, 4-amine o-4 '- (2 "-hydroxy-3", 6 "-disulfo-1' '-naphthylazo) -stilbene-2 ^' - disulfonic acid, SAlilhdliS'i ^ 'f phenylazo) naphthalene-3,6-disulfonic acid, 7- (3'-sulfophenylaminoH-hydroxy-2- (4'-amiiao-2'-carboxyphenylazo) i- naphthalmic-3-sulfonic acid,

8-phenylamino-1-hydroxy-2- (4 "-amino-2'-sulfophenylazo) -naphthalene-3,6-disulfonic acid, 6-AcetyIamino-1-hydroxy-2- (5'-araino-2'-sulfophenylazo) -naphthalene-3-sulfonic acid.

In class S

H3'-aminophenyl) -3-methyl-4- (2 ', 5'-disulfophenylazo) -5-pyrazolone,
1- (3'-aminophenyl) -3-carboxy-4- (2'-carboxy-4'-sulfophenylazo) -5-pyrazolone, 4-amino-4 '- [3 "-methyl-4" - (2'"_>5"'- disulfophenylazo) -l "-pyrazole-5" -onyl] -s.tilbene-2,2'-disulfonic acid,

1- (3'-aminophenyl) -3-carboxy-4- [4 "- (2 ', 5' -disulfophenylazo) -2" -methoxy-5 "-methylphenyl- azo] -5-pyrazolone.

In grade 6

The copper complex of 8-amino-l-hydroxy-2- (2'-hydroxy-5 "-sulfophenylazo) -naphthalene- 3,6-disulfonic acid,

the copper complex of 6-amino-l-hydroxy-2- (2'-hydroxy-5'-sulfophenylazo) -naphthalene- 3-sulfonic acid,

the copper complex of 6-amino-l-hydroxy-2- (2'-hydroxy-5'-sulfophenylazo) -naphthalene- 3,5-disulfonic acid,

the copper complex of 8-amino-l-hydroxy-2- (2'-hydroxy-3'-chloro-5'-sulfophenylazo) - naphthalene-3,6-disulfonic acid, the copper complex of 6-methylaminol-hydroxy-2- (2'-carboxy-5'-sulfophenylazo) - naphthalene-3-sulfonic acid,

the copper complex of 8-amino-1-hydroxy-2- [4 '- (2 "-sulfopnenylazo) -2'-methoxy-5'-methyl- phenylazo] -naphthalene-3,6-disulfonic acid, the copper complex of 6-amino-1-hydroxy-2- [4 '- {2 ", 5" -disulfophenylazo) -2'-methoxy- 5'-methylphenylazo] naphthalene-3,5-disulfonic acid,

the copper complex of 1 - (3'-amino-4'-sulfophenyl) -3-methyl-4- [4 "- (2 '", 5' "- disulfophenyl- azo) -2 "-methoxy-5'-methylphenylazo] -5-pyrazolone,

the copper complex of 7- (4'-amino-3'-sulfoanilino) -l-hydroxy-2- [4 "- (2 '", 5' "- disulfophenyl- azo) -2 "-methoxy-5" -methylphcnylazo] -naphthalene-3-sulfonic acid,

the copper complex of 6- (4'-amino-3'-sulfoanilino) -l-hydroxy-2- {2 "-carboxyphenylazo) - naphthalene-3-sulfonic acid,

the 1,2-chromium complex of 7-amino-6'-nitrol ^ '- dihydroxy ^ l'-azonaphthalene-S ^' - disulfone- acid,

the 1,2-chromium complex of 6-amino-1-hydroxy-2- (2'-carboxyphenylazo) -naphthalene-3-sulfone- acid,

iier 1,2-chromium complex of 8-amino-1-hydroxy-

2- (4'-nitro-2'-hydroxyphenylazo) -naphthalene-

3,6-disulfonic acid,

the 1,2-cobalt complex of 6- (4'-amino-3'-sulfo

anilino) -l-hydroxy-2- <5 "-chlor-2" -hydroxy-

phenylazo) -naphthalene-3-sulfonic acid,

the 1 ^ bromo complex of l- {3'-amino-4'-sulfo

phenyl) -3-methyl-4- (2 "-hydroxy-4" -sulfo-

1 "-naphthylazo) -5-pyrazolone,

the O-chromium complex of 7- (4'-sulfoanilino) -

l-hydroxy-2- (4 "-amino-2" -carboxyphenylazo) -

naphthalene-3-sulfonic acid,

the 1,2-chromium complex of l- (3'-aminophenyl)

3-methyl-4 ^ 4'-nitro-2 "-carboxyphenylazo) -

5-pyrazolone.

In grade 7

1-Amino-4- (3'-ainino-4'-sulfoanilino) -

anthraquinone-2-sulfonic acid, l-amino-4- (4'-ainino-3'-sulfoanilino) -anthraquinone-2,5-disulfonic acid, 1-Amino-4- [4 '- {4 "-amino-3'-sulfophenyl) -

anilino3-anthraquinone-2,5-disulfonic acid,

l-Alnino-4-Γ4'-ί4 "-aminΓ» -7 "-sll1fnnhmv1a7oV

anilino] anthraquinone-2,5-disulfonic acid,

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

anthraquinone-2-sulfonic acid.

In grade 8

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,

3- (3'-aminophenylsulfamyl) -3-sulfamyl copper

phthalocyanine-di-3-sulfonic acid.

In grade 9

4-Amino-2'-nitro-diphenylamine-3,4'-disulfonic acid.

It should be noted that there are fiber-reactive dyes which have two over the remainder of an aromatic or aliphatic diamines containing halotriazine radicals linked to one another by condensation of 2 moles of dihalotriazinyl dye with 1 mole of diamine. This procedure is also in the case of the dyes of the above-mentioned Austrian patents 298 630, 298 631 and 298 632 applicable because the hydrazine is like a diamine

ίο responds. In the production of the invention However, dyes must have 2 halotriazines on one and the same nitrogen atom for condensation primary amine used react. However, this is no longer possible when entering the triazine ring Dye residue is bound. The reaction

N F ₁ -NH-C -Cl H + - Ν —Η
ι + Cl-C N
Λ \ C-NH-F ₂
η N
\ /
C. Λ N ^ Y Il
N
/ \ /
C. \
C-
H Il
N
/

Cl

namely does not lead to the desired product of the formula

Cl

As with aniline above, this reaction is unlikely to work with other primary amines, e.g. B. methylamine, Ethylamine or ammonia feasible. The dyes according to the invention were thus able to conventional route can not be obtained, but only from the bis (dihalotriazinyl) amines. Your manufacture became possible only after one had learned bis (dihalogentriazinyl) amines of the formula (4) (cf. Journal of the Heterocyclic Chem., Vol.7, No. 3, pp. 519-525 [1970]). Since you The dyes according to the application were only obtained via these intermediate compounds and were produced not readily available to the person skilled in the art.

The new dyes according to the invention are suitable for dyeing and printing a wide variety of materials, such as B. silk, leather, wool, blended fabrics containing wool, synthetic fibers made from super polyamides, Super-polyurethanes, piolyhydroxylated materials, such as. B. cellulosic materials fibrous Structure such as linen, pulp, regenerated cellulose, cotton and the like. The dyes are preferably used for dyeing and printing cellulose materials, especially cotton, z. B. after the exhaust process from long liquor, from alkaline, possibly highly salty aqueous baths and especially after the foulard larhe process. after which the goods with aqueous and possibly also salt-containing dye solutions is impregnated, and the dyes after an alkali treatment or in the presence of alkali, may be fixed under the action of heat, used.

However, the new dyes of the present invention are particularly excellent for use suitable for dyeing and printing cotton and regenerated cellulose.

The dyes are characterized by a high reactivity, so that dyeings at lower temperatures or with a shorter fixing time than are usually used for comparable dyes can be. The new dyes achieve high degrees of fixation and good binding stabilities between dye and fiber. The dyeings obtained show good wet fastness properties, such as. B. washing, Full or water fastness and also, depending on the structure of the chromogen, easy washability.

Recommended to improve the wet fastness

the dyeings and prints obtained are thoroughly rinsed with cold and hot water, optionally with the addition of a dispersing agent and the diffusion of the non-fixed components subject to promotional agent.

In the following examples, unless otherwise stated, the parts are parts by weight, the percentages are percentages by weight, and the temperature Temperatures are given in degrees Celsius. The relationship between parts by weight and parts by volume is the same like between grams and cubic centimeters.

example 1
21.8 parts of the dye of the formula

SO ₃ H

HO ₃ S

-N-N

-NH,

SO ₃ H NHCONH ₂

are dissolved neutral in 250 parts of water at room temperature with sodium hydroxide solution and 13.1 parts added anhydrous sodium acetate. Then add a to the dye solution while stirring vigorously Solution of 7.78 parts of N, N-bis (4,6-dichloro-s-triazinyl- (2)) aniline in 40 files acetone.

After acylation of the amino group has taken place, the dye is salted out with potassium chloride and filtered off and dried in vacuo at 50 to 60 °. The dye thus obtained dyes cotton a golden yellow Tones.

Similar dyes are obtained if in place of the acylation of the above aminoazo dye of 7.78 parts of N, N-bis (4,6-dichloro-s-triazinyl- (2)) - aniline corresponding amounts

b) N, N-bis (4,6-dichloro-s-triazinyl- (2)) -2'-chloroaniline,

c) N, N-bis (4,6-dichloro-s-triazinyl- (2)) -2'-methylaniline,

d) N, N-bis (4,6-dichloro-s-triazinyl- (2)) - 2,4'-dimethylane: lin,

e) N, N-bis (4,6-dichloro-s-triazinyl- (2)) - 2 ', 6'-dimethylaniline,

f) N, N-bis (4,6-dichloro-s-triazinyl- (2)) ethylamine,

g) N, N-bis (4,6-dichloro-s-triazinyl- (2)) -methylamine or

h) N, N-bis [4,6-dichloro-s-triazinyl- (2)] amine

be used.

Example 2

'5

17.52 parts of the dye of the formula

NH

35

10

11th

12th

NH,

40

13th

are dissolved neutrally in 600 parts of water at room temperature and as described in Example 1 reacted with 7.78 parts of N, N-bis- (4,6-dichloro-s-triazinyl- (2)) - aniline.

After acylation, the precipitated dye is filtered off and in vacuo at 50 to 60 ' dried. The dye thus obtained dyes cotton in blue-tinged red shades.

Example 3

By reacting 2 equivalents of the amino groups listed in column I of the table below Dyes with 1 equivalent of N, N-bis- [4,6-dichloro-s-triaizinyl- (2)] - aniline obtained dyes, the cotton in the specified in column II Nuances of colors.

14th

15th

16

17th

18th

60

19th

4-amino-2-methyl-5-methoxy yellow azobenzenes ',?' - disulfonic acid

2- (4'-Amino-2'-methylphenyl-yellow azo) -riaphthalene-4,8-disulfonic acid

20 2- (4'-amino-2'-acetylamino-

phenylazo) naphthalene-5,7-disulfonic acid

2- (4'-aminophenylazo) -naphthalene-4,6,8-trisulfonic acid

2- (4'-amino-2'-methylphenyl-

azo) naphthalene-3,6,8-trisulfonic acid

4-Amino-4 '- (2 "-hydroxy-3", 6 "-disulfonaphthylazo- [1"]) - stilbene-2,2'-disulfonic acid

4-Amino-4 '- (4 "-methoxyphenyIazo) -stiben-2,2'-disulfonic acid

4-Amino-4 '- (1 ", 2" -naphthylene) -triazole-stilbene- 2,2'-5 ", 7" -tetrasulfonic acid

1- [Naphthyl- (2 ') - azo] -4- (4 "-aminophenylazo) -naphthalene-4'.6', 7,8'-tetrasulfonic acid

4-nitro-4 '- (4 "-methylaminophenylazo) -stilbene-2,2'-disulfonic acid

4-Amino-2'-nitrodiphenylamine-3,4'-disulfonic acid

phenyl) -3- methyl-4- (4 "-amino-2" -sulfophenylazo) -5-pyr- azolone

1- (2 ', 5'-dichloro-4'-sulfophenyl) -3-methyl-4- (5 "-amino-2" -sulfophenylazo) -5-pyrazolone

1 - [4 ', 8' -Disulfonaphthyl- (2 ')] - 3-methyl-4- (5 "-amino-2" -sulfophenylazo) -5-pyrazolone

l- (4'-sulfophenyl) -3-carboxy-4- (5 "-amino-2" -sulfophenyl- azo) -5-pyrazolone

1 - (3'-aminophenyl) -3-methyl-4- (2 ", 5" -disulfophenylazo) -5-pyrazolone

1-Amino-4- (4'-aminoani! Ino) -anthraquinone-2,3-disulfonic acid

l-amino-4- (3'-aminoanilino) -anthraquinone-2,4'-disulfone-

1 -Amino-4- (3'-amino-2 ', 4', 6'-trimethylanilino) - anthraquinone-2,5'-disulfone-

acid

I -amino-4- (4'-amino-2 ', 3', 5'.6'-tetramethylanilino) - anthraquinone-2,6-disulfonic acid

golden yellow

yellow golden yellow

orange

reddish yellow

yellow

brown orange

yellow

yellow golden yellow

greenish yellow

yellow

yellow

yellow

greenish blue

reddish blue

reddish blue

blue

continuation
I.

21 6-amino-1-hydroxy-. orange 5 Al 30th 43 40 2- (2'-sulfophenylazo) -naph- thalin-3-sulfonic acid 22nd 6-methylamino-l-hydroxy Scarlet fever 2- (4'-methoxy-2'-sulfophenyl- ίο 39 azo) -naphthalene-3-sulfonic acid 23 7-amino-2- {2 ', 5'-disulfo- Red 44 phenylazo) -l -hydroxy- naphthalene-3-sulfonic acid 24 8-amino-1-hydroxy- bluish tint ¹⁵ 40 2- (2'-sulfophenylazo) - Red naphthalene-3,6-disulfonic acid 25th 8-amino-l-hydroxy bluish red 2- (4'-methyl-2'-sulfophenyl- azo) -naphthalene-3,6-disulfon-
acid 20th
41 26th 8-amino-1-hydroxy- bluish red 2,2'-azonaphthalene 1 ', 3,5', 6-tetrasulfonic acid ₂ 27 1-hydroxy-2- (2 ', 5'-disulfo- Scarlet fever phenylazo) -8- {3 "-amino- benzoylamino) naphthalene 3,5-disulfonic acid 28 8-acetylamino-1-hydroxy- Red 2- (5'-amino-2'-sulfophenyl- azo) -naphthalene-3,6-disulfone- acid 29 2-amino-8-hydroxy bluish red 1 - (4'-amino-2'-sulfophenyl- azo) -naphthalene-3,6-disi: lfon- acid 30th 2-hydroxy-1- (4'-amino- Red i2 '~ su! fo ¹ ^ IiCn νΐϊΐτ / ^ ν. naphthalene-6,8-disulfonic acid 31 1 -Hvdroxv-2- (4'-amino- Red

yy (
2'-sulfophenylazo) -naphthalene-3,6-disulfonic acid l-hydroxy-2- (5'-amino-4'-methyl-2'-sulfophenylazo) -naphthalene-3,6-disulfonic acid 1,8-dihydroxy-2 - (5'-amino-2'-sulfophenylazo) -naphthalene-3,6-disulfonic acid, 8-chloro-1-hydroxy-2- (5'-amino-2'-sulfophenylazo) -naphthalene-3,6-disulfonic acid

8-phenylamino-1-hydroxy-2- (4'-amino-2'-suIfophenyl- azo) -naphthalene-3,6-disulfonic acid

7- (3'-sulfophenylamino) -1-hydroxy-2- (4 "-amino-2", 5 "-disulfophenylazo) -naphthalene-3-sulfonic acid Copper complex compound from 8-amino-1-hydroxy-2- (2'-hydroxy-5'-sulfophenyl-azo) -naphthalene-3,6-disulfonic acid

45

Red

bluish red

Scarlet fever

violet

Brown

.50

fto

violet

fts

Copper complex compound from 8-amino-l-hydroxy-2- (l '-hydroxy-4 \ 8'-disulfo- ^ hhi

blue

3,6-disulfonic acid

Copper complex compound blue from 8-amino-1-hydroxy-2- (2'-hydroxy-5'-amino- 3'-sulfophenylazo) -naphthalene-5,7-disulfonic acid

Copper complex compound blue from 8-amino-1-hydroxy-2- [2'-hydroxy-6'-aminonaphthyl- (1> azo] -naphthalene-5,7,4'-trisulfonic acid

Ruby copper complex compound from 6-methylamino-1-hydroxy-2- (2'-hydroxy-5'-sulfophenylazo) -naphthalene-3-sulfonic acid

Violet copper complex compound from 8-amino-1-hydroxy-2- (2'-hydroxy-3'-chloro-5'-sulfophenylazo) -naphthalene-3,5-disulfonic acid

Purple copper complex compound from 6- (4'-Amino-3'-sulfophenylamino) -l -hydroxy-2- (2 "-hydroxy-3", 5 "-disulfophenylazo) -naphthalene-3-sulfonic acid

Blue copper complex compound from 8-amino-1-hydroxy-2 (2'-hydroxy-3'-aniino-5-sulfophenylazo) -naphihalin-5,7-disulfonic acid

Copper complex of blue

2- (2 ', 8-dihydroxy-3', 6'-disulfonaphthyl-1-azo) -1 -hydroxy-6-aminonaphthalene-4,8-disulfonic acid

2- (2 ', 5'-disulfo-phenylazo) - bluish-7- (2 "-sulfo-5" -aminophenyl green azo) -1 -amino-8-hydroxynaphthalene-3,6-disulfonic acid

Copper-N- (2-hydroxyphenyl blue 3,5-disulfonic acid) N '- (2'-carboxy-4'-aminophenyl) -ms-2 "-sulfophenyl-formazan

1: 2 chromium complex compound from 6-amino-1-hydroxy-2- (2'-carboxyphenyla / .o) -naphthalene-3-sulfonic acid

1: Z-Chromkoniplexverbin- dark blue Formation from 8-amino-1-hydroxy-2 (2'-hydroxy-5'-nilrophenyl-azo) -naphthalene-3,6-disulfonic acid

continuation

50 1: 2 cobalt coraplex connection corinth
dung from 8-Ammo-l-hydroxy-

2- (2'-hydroxy-5 '-nitrophenylazo) -naphthalene-3,6-isulfopic acid

51 Mono-p-aminophenylamide turquoise
the copper phthalocyanine

3,3 \ 3 ", 3" '-Tctrasulfonic acid

52 copper phthalocyanine tri-turquoise
sulfonic acid-sulfonic acid-

(3'-amino) phenylamide

53 copper phthalocyanine tri-turquoise
sulfonic acid-sulfonic acid- (4'-amino-3'-suIfo) -phenyIamide

54 copper phthalocyanine disulfone turquoise
acid disulfonic acid (4'-amino-3'-sulfo) -phenylamide

55 copper phthalocyanine trisulfonic acid-sulfonic acid- (2'-amino> ethylamide

turquoise

Example 4

7.52 parts of m-phenylenediamine sulfonic acid are used in 250 parts of water at room temperature dissolved neutrally with sodium hydroxide solution and 13.1 parts of anhydrous Sodium acetate added. A solution of 7.78 parts is added to the resulting solution with vigorous stirring N, N-bis (4,6-dichloro-s-triazinyl) - (2)) - aniline in 40 parts of acetone and allowed 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 in vacuo at 50 °.

13.8 parts of the diamine thus obtained of the presumed formula

are dissolved in 400 parts of water, with 20 parts of 2N sodium nitrite solution and 10 parts of 10N hydrochloric acid added, whereupon the tetrazo compound partially precipitates crystalline.

The resulting suspension of the tetrazo compound is then poured into a neutral solution of 16.92 parts of 1-hydroxy-8-benzoylaminonaphthalene-3,6-disulfonic acid in 300 parts of water, which also contains 20 parts of sodium bicarbonate. After finished Coupling, the dye is salted out with 15 vol .-% sodium chloride, filtered off and in a vacuum 60 ° dried.

The dye obtained in this way dyes cotton in shades of blue-tinged red.

If the tetrazo compound described above is combined with the coupling components of column I. of the following table, dyes are obtained which contain cotton in the nuances indicated in column II to dye.

1 I.
l- (2 ', 5'-dichloro-4'-sulfo- Π
greenish phenyl) -3-methyl-5-pyrazolone yellow 2 1 -EthyM-methyl-o-hydroxy- strong green 3-sulfomethyl-pyridone- (2) pungent yellow 3 6-ureido-l -hydroxv-naphtha- orange lin-3-sulfonic acid 4th 1 - (4'-sulfophenyl) -3-carboxy- greenish 5-pyrazolone yellow 5 Barbituric acid c greenish yellow

6o

6th 8-acetylamino-l-hydroxy- Example 5 Red naphthalene-3,5-disulfonic acid 7th 2- hydroxynaphthalene- orange 3,6-disulfonic acid c 8th 2-hydroxynaphthalene orange 6,8-disulfonic acid 9 1 -EthyM-methyl-o-hydroxy- greenish pyridon- (2) -3-carbonamide yellow 10 1 -hydroxynaphthalene- orange 3,6-disulfonic acid 11th 1 -hydroxynaphthalene- Red 4,8-disulfonic acid 12th l- (4 ', 6', 8'-trisulfo- yellow naphthyl- [2 ']) -3-methyl- 5-PyrazoIon 13th Acetoacetanilide ^ sulfonic acid greenish yellow 14th 1 -EthyM-methyl-o-hydroxy- grunstichiu pyridon- (2) yellow

12.76 parts of 1-hydroxy-S-amino-naphthalene-1-disulfonic acid are dissolved in 250 parts of water at room temperature with sodium hydroxide solution and clear with 13.1 parts of anhydrous sodium acetate are added. A solution of is added while stirring vigorously 7.78 parts of N, N-bis (4,6-dichloro-s-triazinyi) - (2)) - aniline in 40 parts of acetone and allowed to react for about 24 hours.

For a clear solution of the reactive The coupling component is then added to the one prepared in the customary manner from 6.92 parts of Orthaniisäurc Diazo component.

After the coupling is complete, the resulting dye is treated with a mixture of sodium chloride and Potassium chloride isolated, filtered off and dried in vacuo at 50 to 60 °.

The dye thus obtained dyes cotton in blue-tinged red shades.

Example 6

A neutral solution of 10.62 parts of 1-amino-4- (3'-amino-2 ', 4', 6'-trimethylanilino) -anthraquinone-2,5'-disulfonic acid 13 parts of anhydrous sodium acetate are added and an acetone is added Solution of 7.78 parts of N, N-bis- [4,6-dichloro-s-triazinyl- (2)] - aniline. After condensation has taken place there a neutral solution of 10.9 parts of 2- (4'-amino-2'-ureidophenylazo) naphthalene-3,6,8-trisulfonic acid is added to the reaction mixture and lets react for another 24 hours.

In this way, a dye is obtained which dyes cotton in green shades.

Dyeing instruction 1

2 parts of the dye obtained in Example 1 are added with 0.5 parts of m-nitrobenzenesulfonic acid Sodium dissolved in 100 parts of water. A cotton fabric is made with the solution obtained impregnated so that it increases by 75% of its weight, and then dried.

The fabric is then impregnated with a 20 ^{° C.} solution which contains 5 g of sodium hydroxide and 300 g of sodium chloride per liter, squeezes to a 75% weight gain, and the dyeing is dampened for 20 to 30 seconds at 100 to 101 °.

soaps for a quarter of an hour in a 0.3% boiling solution of an ion-free detergent, rinses and dries.

,. Printing specification

2 parts of the dye prepared according to Example 2 are converted into 100 parts with rapid stirring a stem thickening containing 45 parts of 5% sodium alginate thickening, 32 parts of water, 20 parts ίο urea, 1 part sodium m-nitrobenzenesulfonate and 2 parts of sodium bicarbonate, sprinkled.

The printing paste thus obtained is used to print a cotton fabric on a roller printing machine and steams the resulting printed matter for 1 to 2 minutes at 100 ° in saturated steam. The printed fabric is then rinsed thoroughly in cold and hot water, whereby the Non-chemically fixed parts can be easily removed from the fiber and then dried.

Dyeing instructions II

2 parts of the dye obtainable according to Example 1 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 are added a cotton fabric in this dye bath.

The temperature is increased to 90 ° in 45 minutes, 40 parts of trisodium phosphate after 30 minutes and another 80 parts of sodium chloride are added. The temperature is held for 30 minutes to 90 °, then rinses and soaps the dye for 15 minutes in a 0.3% boiling solution an ion-free detergent, rinses and dries.

The result is a color that is washable and lightfast.
There were also a number of dyes from Austrian patent 2 98 631 of the general formula type (A)

N N

F-NH-C C -C -N N-C C -C -NH-F

I I! I! ! ! I

NN CH, CH ₃ NN

C C

I!

Cl Cl

and the corresponding dyes according to the invention of the general formula type (B)

F-NH-C

I Il

N N

CI

C-NH-F

(B)

CH ₃ NN

N /

Cl

produced which each had the same chromophoric residues F. The chromophoric residues F had the following "

Claims (1)

1. Dyes of the formula Patent claims: N N y \ y \ F ₁ -NC C-N-C CNF ₂ R ₁ N N R, N