DE1644206B2 - HYDRO-SOLUBLE REACTIVE DYES, THEIR PRODUCTION AND USE FOR THE COLORING OF CELLULOSE MATERIALS, WOOL, SILK, POLYAMIDE AND POLYURETHANE FIBERS - Google Patents

Description

The present invention relates to water-soluble reactive dyes of the formula

D-N-

(D

- NH- A

-NH-A

IS

D residue of a dye of the azo, anthraquinone or "^ Azaporphin series, which contains at least one sulfonic acid group and

R is hydrogen or methyl.

In the dyes of the general formula (I) is

- N (R) group linked directly to a carbon atom of the pyridazine ring, presumably in the 4-position. On the other hand, the - N (R) group is either directly or via a further bridge member, such as -SO ₂ - or -CO-, as in the case of amide groups, or via an alkylene group, an alkylene-CO-, an arylene -, Arylen-SCh-, Arylen-CO- group or a triazine or diazine ring or an arylenamidosulfonyl group attached to an aromatic ring of the dye D. If such further bridge members contain heterocyclic ring systems, as in the case of triazinyl or pyrimidinyl radicals, then these too can still have reactive atoms or groups, such as halogen atoms or other substituents known in large numbers. 4S

Among the multitude of binding possibilities of the fluoropyridazine ring to D is the direct binding of the

- N (R) groups on a carbon atom of a carbocyclic ring of D are preferred. Suitable Brükkenglieder including the - N (R) group, for example, (A represents a trifluoro- yridazinrest ^D):

- NH-A -N (CH ₃ ) -A

- CONH-A -SO ₂ NH-A

- CON (CH ₃ ) - A -SO ₂ N (CH ₃ YES

- HN-CO -NH-A
-HN-CH ₂ -CO-NH-A

- N (CH ₃ ) -CH ₂ -CONH-A ⁽ ~ " -HN-CH ₂ -CH ₂ -NH-A

6 s NH

NII

(SQ ₁ H) ₁

HNOC <

-NU-A

(SO ₁ II) _1. ,

SO, NH- <f V-NH-

_odcr:

NH-A

^ (SO ₃ H) _{1 or:}

NH-A OCH ₂ (CH ₂ NH-A

-HN

CH ₂ (CH ₂ NH-A

CONH-A

) O _{or cr} , NH-A

and the corresponding N-methylamides or N-methylamines of the compounds mentioned.

The new dyes can belong to a wide variety of classes, e.g. B. the series of metal-free or metal-containing mono- or polyazo dyes, metal-free or metal-containing azaporphine dyes, such as Copper or nickel phthalocyanine dyes, the anthraquinone, oxazine, dioxazine, triphenylmethane, Nitro, azomethine, benzanthrone and dibenzanthrone dyes and the polycyclic condensation compounds of anthraquinone, benzanthrone and dibenzanthrone compounds. In the context of these dye classes Among other things, dyes of the following general compositions are particularly valuable:

! .Azo dyes

(H)

wherein B and E represent aromatic, carbocyclic or heterocyclic radicals, in particular B den Remainder of a carbocyclic diazo component of the benzene or naphthalene series, and E is the remainder of one enolic or phenolic coupling component,

2 s

z. B. a 5-pyrazolone, an acetoacetic acid arylamide, an oxynaphthalene or an aminonaphthalene; Incidentally, B and E can be any in azo dyes Have customary substituents, including other azo groups; R stands for a —CHβ group or preferably for a hydrogen atom.

The azo dyes can be both metal-free and metal-containing, with the metal complexes being the Copper, chromium and cobalt complexes are of preferred interest.

Important azo dyes are, for example, those of the benzene-azo-naphthalene series, the benzene-azo-1-phenyl-5-pyrazolone series, the benzene-azo-aminonaphthalene series, the naphthalene-azo-naphthalene series, the naphthalene-azo-1 -phenylpyrazolone-5 series and the stilbene-azobenzene series.

In the case of metal complex azo dyes are located the metal complex-bonded groups are preferably in the o-positions to the azo group, e.g. B. in shape from

o.o'-dihydroxy-.o-hydroxy-o'-carboxy-,
o-carboxy-o'-amino and o-hydroxy-o'-carboxy, o-carboxy-o'-amino and
o-hydroxy-o'-amino-azo groups.

Particularly outstanding types of monoazo dyes of the type obtainable according to the invention are made by illustrates the following formulas:

(SO, H) o_ ₃

_ _{N =} ^ NC C-CH ₃ (or COOH)

'/.· (OdCrH ₂ N-) HO-C N

N (R ') A

(Hl)

H; Cl; CH ₃ -J- Ι- (SO ₃ H) ₁ _ ₂

H; Cl; CH,

I; l; OCH,; NH-acyl OH

(HO, S), _t = tH — 4 "

O Me

(o) I ^ N (R ') - Λ

(I-10., SVrr-i --- «· ί-N N / V'X

S \\ X I

N (R ') - Λ
- (SO ₃ H), ...,

Me = Cu; Cr; Co

(IV)

H; OH; NO,

S /

Cu O

N N

NIl Λ

NlI ₂ (oiler N ll-iicyl)
(SO ₃ Il) _{1 3}

(Vl)

709 M1 / 2

ίο

NH,

Α — ΗΝ

(SO ₃ H) ₀ -,

(VI)

(SO ₃ H) ₁ _3

NH ₂ (or NH-alkyl)

/ Λ

A-HN

(VIII)

(SO ₃ H) ₀ _,
ί (ο) means o-position of the respectively indicated residues in the aryl nucleus, and A stands for the rest of the form

Acyl stands for an acyl radical; the cores drawn in dashed lines indicate that they are present or absent.
2. Anthraquinone dyes

O NH ₂

O NH

(1 )
ι

; ν

■ ·· ■ ι

where I. Substiluent. R hydrogen odor melhyl, and /> O 2, where at least one 1. or 1. ' for a sulfoi acid group chair.

3. Phthalocyanine dyes Kupfcrphlhalocyuniiis, I. and I / HIr substituents

especially sulfonic acid groups, r for a whole zu

([) from I) to 2, η for the number O or I ₁ R for ei

I '| · methyl group or preferably hydrogen. The Phtli

Pc SO NII <f O> I («'locyanine residue l'c is preferred as a further substance

'ten 1-2 sulfonyl and / or I -2 sulfonyl

groups, such as -SO ₁₁ NH ,, - SO ^ NI 1-ulkyl. -SO, N (, kyl) r and - SOjN I l (aryl) - (Lnippen, where "alkyl" I stands for alkyl groups with 1-3 carbon atoms, where t I 'I ds l' dyes Xl at least one sulfonic acid group

I · 'have.

The previous compilation of an Ai In this Rirmcl, Pc stands for the remainder of a nickel or a choice of suitable azo, anthi aehinon and azaporph

IXI)

Dyes does not represent a restriction of the general formulas, neither with regard to the preparative possibilities for the preparation of such dyes in the context of the new products nor with regard to the valuable application properties of these products. The new dyes can also have any substituents customary in dyes, such as sulfonic acids, carboxylic acid, sulfonamide and carbonamide groups, which can be further substituted on the amide nitrogen atom, sulfonic acid ester and carboxylic acid ester groups, alkyl, aralkyl and aryl radicals, alkylamino, aralkylamino, Arylamino, acylamino, nitro, cyano, halogen, such as Cl ₁ Br and F, hydroxy, alkoxy, thioether, azo groups and the like. The dyes can also contain other fixable groups, such as mono- or dihalotriazinylamino-, mono-, di- or trihalopyrimidinylamino-, 2,3-dihaloquinoxaline-6-carbonyl- or -6-sulfonylamino-, 1,4-dihalophthalazine-6-carbonyl - or -6-sulfonylamino, 2-halogen or 2-alkylsulfonyl or 2-arylsulfonylbenzthiazole-5-carbonyl or -5-sulfonylamino, alkylsulfonylpyrimidinyl, arylsulfonylpyrimidinyl, esterified sulfonic acid, oxy-fluoro-amide, and oxalkylsulfonid groups Have haloalkylamino, acryloylamino, haloacylamino groups or other reactive groups.

The new dyes are obtained when you look into dyes or dye precursors per se known method introduces at least one trifluoro-pyridazine radical and in the case of the use of Dye precursors are converted into the dyes in a manner known per se. One prefers to lead in Dyes or dye precursors via an amino group -N (R) - attached to a fluorine-substituted one Pyridazine ring

(XU)

a. In the case of the use of dye precursors these are then in a known manner, in particular by diazotic and / or coupling and / or condensation reaction converted into the desired final dyes.

The introduction of the radical XII via an amino group -N (R) - in dyes or dye precursors Various preparative methods can be used realize. So one can contain amino or amide groups Dyes or dye precursors which have a reactive Wusscrstoffatom on the amide or Have atnidnitrogen, with compounds

(XlII)

wherein

X stands for an anionically separable radical,

implement and in the case of the use of dye precursors these in a suitable manner in the convert desired end dyes. Among the reactive substances that can be split off as anionic radicals tuenten X, the fluorine substituent has a preferred interest. Further anionic suitable on a case-by-case basis Removable residues are, for example, quaternary ammonium groups, such as

.o -N (CH ₃ J ₃ and -N (C ₂ H ₅ ).,

A suitable compound XIII is 3,4,5,6-tetrafluoropyridazine.
In the condensation reaction with the dyes or dye precursors containing amino or amide groups, these pyridazine derivatives react with elimination of the radical X, probably in the 4-position.

Said and other fluoropyridazine compounds which can be used according to the invention can generally be obtained easily by reacting the corresponding chlorine or bromine compounds with alkali metal fluorides, e.g. B. with potassium fluoride, NaF, KSO ₂ F, SbFj, AgF ₂ , or by reacting appropriate OH compounds with SF ₄ , COF ₂ , COCIF or cyanuric fluoride, or by heating appropriate diazonium tetrafluoborates.

The implementation of the amino or amide group-containing dyes or dye precursors with a minor

o} least bifunctional Fluorpyridazinverbindungen, such as compounds of the formulas (XLII) is depending on the nature of the starting compounds used in an organic, organic-aqueous or aqueous medium at temperatures of from -1O ⁰ C to 100 ⁰ C, preferably 0

.15 to 50 ⁰ C, carried out in the presence of alkaline condensing agents, such as aqueous alkali metal carbonate or alkali metal hydroxide solutions.

When using dye intermediates the condensation products obtained are converted into the desired final dyestuffs in a conventional manner converted. This method has preferred interest for the preparation of azo dyes by for example a diazo and / or coupling component that has a reactive amino or amide group has, initially milder active component (XIH) condensed and the intermediate product obtained then by diazolization and / or coupling and / or condensing into an azo dye. This can be followed by further conversion reactions be carried out, as they are customary in A / .ofiirbstoffen, / .. B. Induction and metallization effects.

Also in the representation of other dyes, especially those of the phthalocyanine and anthraquinone groups, the condensation of a reactive component (XIII) can initially be carried out with an intermediate product take place, / .. B. with m-Phcnylenediamine or einet m-PhenylcndiaminsulfonsUufc, and the reaction product obtained then with an anthraquinone sulfate

(«Ι fonsHiirehalogenid or with a copper odet Nickylphthalocyaninsulfonsuiirehalogcnid to one reactive Phthnlocynninfurbsloff are further condensed.

The procedure according to the variously described

(κ, Oral dyes can, as already for some « Abundance crwllhnt, further for dyes (! Usual reactions are subjected, for example incl mun mctnllisicrbnrc dyes with mcttillabgcbenclei

Means here treated in particular with chromium, cobalt, copper or nickel salts, dyes that have reducible groups, in particular nitro groups, reduced. Dyes containing acylatable groups, in particular have acylatable amino groups, acylated, or by adding dyes subsequently treated with sulfonating agents such as chlorosulfonic acid, oleum or SO3 in chlorinated hydrocarbons, to introduce (further) sulfonic acid groups into the products. The last-mentioned procedure has sometimes of particular importance in the series of anthraquinone and phthalocyanine dyes.

If the dyes prepared according to the process contain groups which form metal complexes, so can this by the action of metal-releasing agents, e.g. B. of copper, nickel, chromium or cobalt salts in their Metal complex compounds are transferred. They can also perform other common conversion reactions such as diazotization, coupling, acylation and condensation reactions.

The reaction of dyes containing amino groups with reactive components of the formula (XIlI) gives Groups of particularly preferred dyes if the dyes of the formulas (II) to (XI) are used as a basis lying amino group-containing starting dyes is used.

When displaying phthalocyanine dyes !! can first be one with the reactive component (XIIl) or (XIV) produce monocondensed diaminoaryl compound and then preferably with Condense copper or nickel phthalocyanine sulfonic acid halides, simultaneously or subsequently other amino compounds such as ammonia, aliphatic amino compounds and / or aromatic Amino compounds can also be used. Phthalocyanine, preferably obtained in this way Copper or nickel phthalocyanine sulfonamide dyes that contain a certain amount of sulfonarylamide groups, which carry the reactive groups, and also contain a certain proportion of non-reactive sulfonamide groups ■ and / or free sulfonic acid groups. You can also use copper or

Nickel phthalocyanine sulfonic acid ^ aminoarylVamide,
which may additionally have N-substituted sulfonamide groups of a different type and free sulfonic acid groups, condense on the amino group of the aminoaryl radical with reactive components (XIII) to form the new dyes.

The dyes according to the invention with a fluoropyridazinyl reactive group show the surprising advantage of providing deeper colorations when dyeing cotton from inager liquor compared to the next-comparable dyes known from BE-PS 6 04 068 with chloropyridazinyl reactive group.

In the following examples, unless otherwise stated, parts are used for w / w parts.

example 1

For the solution of 34.7 parts of 2-aminonaphthalene-4,8-disulfonic acids! Sodium and 7 parts of sodium nitrite in 300 parts of water are added with ice-cooling 28 parts by volume of concentrated hydrochloric acid and the mixture is stirred for half an hour at 0-10 ° C. After excess nitrous acid has been removed, 10.7 parts of 3-aminololuene are added in 10 parts by volume of concentrated hydrochloric acid and 150 parts of water, and the coupling completes by blunting the mixture to pH 3 to 5. The aminoazo dye formed is salted out, filtered off with suction, washed and then again in 1400 parts of water and 200 parts of acetone with the addition of Dissolved sodium hydroxide solution at pH 7. 20 parts of 3,4,5,6-tetrafluoropyridazine are added dropwise to this solution at 30 to 40 ^° C. and a pH of 6 to 7 is maintained with 2 η sodium hydroxide solution resulting dye of the likely formula

HO ₃ S

SO ₃ H

Salted out with sodium chloride and the product thus obtained is filtered off with suction and washed with 5% NaCl solution and dried in vacuo at 50 ° C.

When you put cellulosic fabric with a printing paste

printed, the kilogram contains 15 grams of the dye, 100 g urea, 300 ml water, 500 g alginate thickening (60 g sodium alginate per kg thickening) and 20 g soda and which was made up to 1 kg with water, dries, 8 minutes at 102 ⁰ C steams, rinsed with hot water and soaped at the boil, so you get a strong reddish yellow print of good quality

• (o Wash and lightfastness.

Example 2 0.1 mol of the copper complex compound of the formula

SO ₃ Na

NaO ₃ S

OH

N = N

NaO ₃ S 0 Cu 0 SO ₃ Na

(produced according to the information in German patent specification 1117 235 by coupling diazotized

1-Amino-8- (benzene-sulfonyloxy) -naphthalene-disulfonic acid- (3,6) in a soda-alkaline medium with the equiva-

so small amount of 2-acetylamino-5-hydroxynaphthalenedisulfonic acid (4.8), Conversion of the monoazo compound into the copper complex by oxidative copper plating and hydrolysis of the acetyl and the benzenesulfonyl group) is carried out in 2500 parts by volume of water at 60 to 65 ° C

S5 pH 6 to 6.5, and dissolved 3,4,5,6-Tctrafluor-pyridazin added at 30 to 40 ⁰ C with 0.15 mo. During the condensation, a pH of 6 to 7 is maintained by adding sodium carbonate solution. When the reaction has ended, the dye is salted out and isolated

do The dye turns into a dark powder when dried that dissolves in water with a blue color.

100 weight of a cotton weight at room temperature with an aqueous solution that is 2 ° / of the dye, 15 g / l sodium hydrogen carbonate and

ds 150 includes g / l urea, padded, zwischcngctrock net, heated for 5 minutes at 140 ⁰ C, then rinsed un soaped at the boil. The fabric is dyed wetfast in very clear blue tones.

Example )

46 parts of the monoazo dye obtained analogously to the information in Example 1 by coupling diazotized 2-aminonaphthalene-4,8-disulfonic acid to 1-amino-2-melhoxy-5-methylbene-ol are dissolved in 400 parts of water and 100 parts of acetone at 25 Dissolved up to 30 ^° C., added 20 parts of 3,4,5,6-tetrafluoropyridazine while maintaining a pH of 6 to 7 by means of 2N soda solution; the condensation is continued until a sample no longer shows a color ion change on acidification. The resulting dye has the likely formula

11 OjS

OCII.,

χ 7— N-

SO., H

CH,

Diazo component Clutch Reactive Color component compo volume nent 1-aminonaphtha- 1-amino A. yellow lin-3,6-disulfone- 3-methylbenzene acid 2-aminonaphtha- the same A. yellow lin-5,7-disulfone- acid 2-aminonaphtha- the same A. yellow lin-6,8-disulfone- acid 4-aminoazobe the same A. Brown zol-3,4'-disulfone- yellow acid

.10

and is salted out, filtered off with suction, washed and ^{dried at 3O 0} C in a vacuum.

Cotton fabric is impregnated with a solution at 20 to 25 ° C containing 20 g of the above dye and 0.5 g of a non-ionic wetting agent (e.g. a polyethylated oleyl alcohol) and 150 g of urea and 15 g of sodium bicarbonate per liter of liquor. The fabric is then squeezed between two rubber rollers to a moisture content of approx. 100%. After intermediate drying at 50 to 6O ⁰ C for 5 minutes at 140 ° C is heated and purged the coloration thus obtained thoroughly with hot water and for 20 minutes boiling with a solution containing per liter 5 g of Marseilles soap and 2 g sodium carbonate. After rinsing and drying, a strong reddish yellow coloration with good wet, rub and lightfastness is obtained.

The table below shows the diazo components Coupling components and the reactive components that can be linked to the amino group are listed, from which analogous to the information in Examples 4s 1 and 2 dyes can be built up, their Color shades - obtained using one of the application methods described - also in the table are recorded.

so

Diazo component coupling component

Reactive l'arbkompoton
iienk-

l-amine () -3-acetyl-A
aminobcnzol

yellow

yellow

2- <3'-Suir <) - 4'- like A

aminophynyl) -6-

methyl-benzlhia-

/ ol-7-sulfonic acid

2-aminonaphtha-

lin-4,8-disulfone-

acid

Abbreviations for the reactive component:

A = 3,4,5, h -trjfluoropyridazine.

Example 4

8.3 parts of l-amino-4- [4'-aminocyclohexylamino] anthraquinone-2-sulfonic acid are dissolved in 160 parts of water and 80 parts of dioxane with the addition of 1.3 parts of 45% strength sodium hydroxide solution and at 0 to 10 ° C. 3.8 parts of 3,4,5,6-Tetrafk'or-pyndazine were added dropwise. A pH of 11 to 12 is maintained by adding 2N sodium hydroxide solution. When the acylation is complete, the pH is adjusted to 4.5 by adding hydrochloric acid. The crystalline product is filtered off with suction and washed with 3% sodium chloride solution until it is colorless. The dye obtained is dried in vacuo at 30 to 40 ^° C., it dyes wool in clear, washable blue shades.

NH

SO ₃ H

O NH- <H> -NH

Example 5

In the solution of 21 parts of the sodium salt of 1,3-diaminobenzene-6-sulfonic acid in 200 parts of water, 16 parts of 3,4,5,6-tetrafluoropyridazine and at 20 to 30 ⁰ C with constant blunting of the hydrofluoric acid liberated are added with thorough stirring pH 6 to 7 stirred until a sample gives a clear, yellowish-red color when diazotized and coupled to 1-hydroxynaphthalene-4-sulfonic acid. After adding ice, the resulting intermediate dye is diazotized directly with 7 parts of sodium nitrite and 28 parts of concentrated hydrochloric acid and then 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 are combined, coupling to the dye of the formula

OH
SO ₃ Na I NH-OC-C ₆ H ₅

N = N

NaO ₃ S

SO ₃ Na

takes place, which is salted out, vacuumed, washed and at

709 541/23

30 to 40 ^a C is dried in vacuo. The dye dissolves easily in water with a red color and, by one of the processes described above, gives clear bluish-tinged red dyeings and prints on cellulose materials.

The following table shows the color tones and the pH of the coupling medium of dyes listed, the analogous to the information in Example 5 from a diazo component, which is another, bevoi train! acylatable amino group, from a coupling component and from one with the Dia / x component connectable reactive component are provided. For dyeing and printing vo Cellulose paints with the dyes in the table can use the above-mentioned methods will.

Diazo component

Coupling component reactive- pll des kompo- Kuppnenle lung

m eil iu ms

hue

2-aminonaphthalenes, 7-disullbns; iurc A

2-Aminonaphlhiilin-3,6-disulfonic acid c Λ

2-N-methylamino-H-hydroxynaphthalene-A
6-suJibic acid

l- (3 ', 5'-dichloro-r, 2'-thiazoi-4'-carbonamido) - A
8-hydroxynaphthalene-3,6-disulfonic acid

2-hydroxynaphthalene-3,6-disulfonic acid
1- (3'-SuHbphenyl) -3-methyl-pyrazolone-5
1- (2 ', 5'-dichloro-4'-sulpho-phenyl) -3-methylpyrazolone-5

1- (5 \ 7'-DisulfonaphthyI-2 ') -3-rnelhylpyrazolone-5

2-Acetylamino-5-hydraxynaphtl ^ aIin-7-s u I ΙΌ η acid abbreviations for the reactive components as in the table for example 3.

1,3-I) iaminobenzene-4-suHbic acid

the same

the same

the same

the same
the same
the same

the same
the same

4-5 4-5

4-5 7-8

orange orange orange

Red

A. 8th shariach A. 6th yellow A. 6th yellow A. 6th yellow A. 6-7 shariach

Example 6

51.6 parts of that obtained by diazotizing 1-hydroxy-2-aminobenzene-4-sulfonic acid and coupling on 2-amino-5-hydroxynaphthalene-7-sulfonic acid in water / pyridine in the presence of soda and subsequent treatment with a copper donating agent obtained dye of the formula

45 30 to 40 ⁰ C dried. Fabrics made of cellulose materials can be dyed or printed with this dye by one of the above-mentioned processes in ruby tones which are fast to wet, rub and lightfast.

In the table below are the heavy metal complexes further aminoazo dyes and the reactive components linked to the amino group as well as the color tones of these dyes on cellulose materials are listed. The manufacture of aminoazo dyes, Their metal complexes and their conversion with the reactive components can be analogous to the information in Example 6 take place.

NaO ₃ S

NH ₇ aminoazo dye

SO ₃ Na

are dissolved in 1500 parts of water at pH 7. 18 parts are added at 20.degree. To 30.degree. C. with thorough stirring 3,4,5,6-tetrafluoropyridazine and constantly dulls the hydrofluoric acid released with soda solution on one pH from 6 to 7. If no free amino group can be detected any more, the reactive dye formed becomes the formula

O Cu O

Grain reactive plexus composite-bonded heavy metal

hue

l-Hydroxy-2-aminobenzene-4,6-disulfonic acid - *
2-amino-5-hydroxynaphthalene-7-sulfonic acid

N = N

Cu

Cu

NH

NaO ₃ S

SO ₃ Na
salted out, pressed, washed and in a vacuum

fts l-Hydroxy-2-aminobenzene-4-sulfonic acid - *
2-Ethylamino-5-hydroxynaphthalene-7-suHbic acid

l-amino-2-hydroxy-o-Cu
nitronaphthalene-4-sulfonic acid - *

2-amino-5-hydroxynaphthalene-7-sulfonic acid

ruby

ruby

ruby

Aniinoa / tilarbsloll Ki) hi Reactn, I'arhlon IhIIUIl'IIi
Heavy
metal - ν no, l-amino-2-hydroxy-5-
mclhylsuH'onyl-benzene -
l-amino-8-hydroxynaph-
thalin-3,6-disuHbic acid Cu Λ violet the same Co Λ Gray the same Cr A. green-
steadily
black / l-amino-2-methylbenzene
4-sullOnsiiure -
l-amino-2-hydroxy-5-
methylbenzene - »
l-amino-8-hydroxynaph-
thalin-4,6-disullic acid Cr A. green-
pithy
black /

(l-Amino ^ -chlorobenzene- Cu A marinc-

4-sulfonic acid - blue

1-1 hydroxy-2-acetylamino

benzene), saponified,

l-amino-8-hydroxynaph-

thalin-3,6-disulfonic acid

(l-Amino-2-chlorobenzene-Co A gray

4-sulfonic acid -

l-hydroxy-2-acetylamino-

benzene), saponified, - *

l-amino-8-hydroxynaph-

thalin-3,6-disulfonic acid

l-amino-8-hydroxynaph- Co A. black

thalin-4-sulfonic acid -

l-hydroxy-2,6-diamino-

benzene-4-sulfonic acid - *

1,3-dihydroxybenzene

AminiKi / nlarhslon

Koni- Reaklivplcxgekum | io-Imndenes nenle Sciiwcr-Hi flail

! ■ arbton

l-amino-8-hyclroxynaph- Co A black

ihalin-.i.d-disull'onsa'ure -

l-llydroxy-2,6-dianiino-

benzene-4-sulfonic acidc -

2-1 hydroxynaphthalene

l-amino-8-hydroxynaph-Co A black

thalin-4-suH'onsaure «-
,. l-llydroxy-2,6-diaminoben / .ol-4-sulfonic acid
.V-methyl-pyrazolone- (5)

Abbreviations for the reactive components as in Table / Example 3.
, ₀ Be is ρ ie I 7

9ö parts (based on 100% goods) of the copper phthalocyanine tetrasulfochloride freshly produced in the customary manner by the action of chlorosulfonic acid and thionyl chloride on copper phthalocyanine or the isomeric copper phthalocyanine built up from 1-sulfobenzene-3,4-diearboxylic acid via the corresponding copper phthalocyanine tetrasulfonic acid Tetrasulfochlorids are suspended in the form of the moist, well washed suction cake in 500 parts of water and 500 parts of ice, the solution of 50 parts of 1,3-diaminobenzene in 500 parts of water is added and the pH is adjusted to 8.5 with soda. The suspension is stirred for 24 hours at room temperature and the pH is always kept at 8.5 by continuously adding soda. The resulting condensation product is precipitated at pH 1 to 2 by adding sodium chloride, filtered off with suction, washed and then redissolved in 1000 parts of water until neutral. In the blue solution 50TeUe be entered 14.5,6-tetrafluoro-pyridazine, and stirred under constant blunting with sodium carbonate solution to pH 7, as long as at 20 to 3O ⁰ C with vigorous stirring until no free amino groups are no longer detectable. The reactive dye of the formula obtained in this way

Cu phthalocyanine

(SO ₃ Na) _n

SO, - HN HN

4-n
Π'2-J

is salted out, washed and dried at 30 to 4O ⁰ C in vacuo. Egg is a dark blue powder which is soluble in water and has a blue color and dyes cotton and regenerated cellulose by one of the above-mentioned dyeing or printing processes in clear blue shades of good wet, rub and lightfastness.

Instead of the 96 parts of copper phthalocyanine tetrasulfochloride, you can use the same procedure as in Example 7 - also 87 parts (based on 100% strength goods) of the by the action of chlorosulfonic acid Copper or nickel phthalocyanine trisulfochloride available in the form of copper or nickel phthalocyanine moist absorbent cake well grown with ice water can be used; one then also gets clear blue coloring reactive dyes.

If one works as indicated in Example 7, however, from 87 parts of copper phthalocyanine trisulfochlo rid goes out and instead of the 50 parts of the sodium salts: the 1,3-diaminobenzene 90 parts of the sodium salt de 4,4'-diaminodiphenyl-2,2'-disulfonic acid or 90 parts of the sodium salt of 4,4'-diaminostilbene-2,2'-disulfone acid is used, reactive dyes are obtained, welclr

ds cellulose materials according to one of the above) Procedure in wet, rubbing and lightfast clear blue: coloring shades.

If one goes from the 4 ', 4 ", 4'", 4 "" - Tetraphenyl-Cu-phthalc

cyanine is obtained after sulfochlorination and conversion with 1,3-phenylenediamine and acylation with 3,4,5,6-Tetrafluoropyridazine a reactive dye, the cellulose materials in the presence of acid-binding Dyes agent in clear, wet and lightfast green tones. s

Example 8

63 parts of 1-amino-4- (4'-aminophenvl) -; imino-anthraquinone-2,5,8-irisulfonic acid are dissolved in 630TeUL ¹ U of water and adjusted to pH 6 with sodium hydroxide solution; 20 parts of 3,4,5,6-tetrafluoropyridazine are then added dropwise at 20 to 30 ^° C. and a pH of 6 to 7 is maintained with soda solution. After the reaction has ended, the mixture is salted out with 10 parts of sodium chloride, filtered off with suction and washed with 5% strength potassium chloride solution. The resulting dye is dried in vacuo at 30 to 40 ° C. It probably has the following formula

HO ₃ SO NH ₂

H, N

SO., H

SO., H

-N = N

HO ₃ SO Cu O SO ₃ H

by coupling the diazonium compound from e-acetamino ^ -aminonaphthalene ^ S-disulfonic acid with 2-oxynaphthalene-3,6-disulfonic acid and saponification and conversion of the monoazo compound into the copper complex is obtained in 2000 parts by volume Dissolved water at pH 6.5 and combined with 20 parts of 3,4,5,6-tetrafluoropyridazine. The reaction mixture is stirred at 20 to 30 ° C until the condensation has ended, the pH of the reaction solution through Adding soda solution at 6 to 7 kept wild. After the reaction has ended, the dye is salted out, isolated and dried in vacuo.

The dried dye is a dark powder that dissolves in water with a purple color and Cotton in the presence of alkali in biaustichrgvio guide tones colors.

Example 11

The aqueous solution of 0.1 mol of the copper complex of the formula

IIO, S O Cu O

Ί 1 I , ■

II, N

A / V

SO ₃ H

SO ₃ H

manufactured according to the information of the German Patentee writing 10 61 460 or 10 85 988, is in the usual way brought to reaction with 20 parts of 3,4,5,6-tetrafluoropyridazine. The pH is kept at 6 by adding soda to 7 and isolates the dye by salting out after the reaction has ended. It sets when dry ^ represents a dark powder which dissolves in water with a purple color. Cotton fabric is available in light and light dyed wet-fast purple tones.

and dyes cotton in greenish blue tones.
B is ρ ie I 9

If one proceeds as indicated in Example 6, but instead of the copper-containing one used there Amino monoazo dye from the equivalent amount of the chromium complex of the diazotized by coupling 1 amino-2-nydiOxy-3-chlorobenzene-5-sulfonic acid with 1- [3 '- (3 "-aminophenyl)] - sulfonylimido-sulfonyl-phenyl-3-methylpyrazolone- (5) obtained aminoazo dye off, a reactive dye is obtained, which cellulose materials according to one of the above Process in good wet, rub and lightfast yellow-brown tones.

Example 10

0.1 mole of the paste of the aminoazo compound of the formula

Example 12

27.5 parts of Z-methylamino-S-hydroxynaphthaün-y-sulfonic acid Sodium is dissolved in 150 parts of water, mixed with 20 parts of 3,4,5,6-tetrafluoropyridazine and at 30 ° C with constant blunting of the resulting hydrogen fluoride with a total of 34 parts by volume 16% soda solution to pH 6 to 7 stirred. After a short time, the acylation is complete, the pH is 7 and changes no longer.

30 parts of sodium bicarbonate are then added and the diazo suspension is left at 20 ° C. over the course of 15 minutes from 34 parts of the disodium salt of 2-aminonaphthalene-l, 7-disulfonic acid in 200 parts of water to drip. The orange reactive dye of the formula which was formed immediately

NaO ₃ S

NaO ₃ S

is completely separated after stirring for one hour by adding 80 parts of sodium chloride, filtered off, with Washed dilute sodium chloride solution and dried at 35 ° C in a vacuum. He dyes cellulose materials the above processes in reddish orange tones with very good and good wet fastness properties Chlorine resistance.

In an analogous manner, those listed in column 2 of the table below are obtained by acylation Aminonaphtholsulfonic acids with 3,4,5,6-tetrafluoropyridazine and coupling the acylaminonaphtholsulfonic acids formed with the diazo components mentioned in column 1 orange to red reactive dyes.

23

24

Diazo Componcnlc

AniinonaphtliolsuHonsiiurc

harbton aiii 'cotton

2-aminonaphthalene-1,7-disulfonic acid

the same

the same
the same

2-Aminonaphlhahn-1,5-disulfonic acid

^des ß '

^{of the} S '
the same

the same

2-aminonaphthalene-'Oj-trisulfonic acid c

the same

2-amino-5-hydroxy-orange

naphlhalin-7-suiron-

acid

2-amino-5-hydroxy-orange naphthalene-1,7-di-

suironsüurc '

2-amino-8-hydroxy scarlet fever

naphthalene-6-sullbn-

acid

2-amino-8-hydroxy scarlet fever

naphthaleneO / i-di-

sulfonic acid

2-methylamino orange

S-hydrov.ynaphthalene-

2-Am.no-S-hydroxy- orange naphtha! .n-7-suiron-

2-Am.noo-hydroxy-orange naphthalene - !, 7-disulfonic acid c

2-ammo-8-hydroxy-scarlet naphthalene-6-sulfone-Uia / ocomponcnlc

2-aminonaphthalene, .S-disiilfonsiiuri:

2-AminonaphlliaMn-1,7-disulfonic acid

cJos «1.

ΛιηίιιοιιιιρΙιΙΙιοΙ suIfoiisjimf

ΙίιιΙ> ιομ mil lliiiiin wool

2-amino-8-hydroxy scarlet fever

naphthalene-3,6-di-

sulfonic acid c

2-AminoS-hydroxy-orange

r * .sph.lh = £! in- ~ -Mjifon-

acid c

2-meth>! Ammontang ':

5-hvdroKynaphtr.isiin-

; -Airvfro-ii -? Ii4 ¹ f. '»^.

l-amino-K-hydroxy blue

naphlhaliiiY.-siilloii.

acid

I-Amino-H-Iiydtoxy blue

naplilhalin-.V> - <li-

sullOnsilure

l-amino-K-hydroxy blue naphthalene-4,6 <lisulfon acid

I Amino-K-hydroxy blue naphthalene-sulfone

2-aminoriaphlhalin _li5i7 . _lr jsuirr, n.saurc

! -Amino ^ -chlorheri- / . «(-2-sulfbnsäurc

l-Amino-2-methylxybcn / .ol-S-sulfonic acid c

! -Aminobenzenes carb () n% aure-4-sulfone-

l-amino-H-hydroxy bliiu

l-amino-K-hydroxy naphthalene -;} /, di-

(JcskI,

dc _W l.

blue hl;, ..

i-amino-4-acctylaminobe

fonvaurc

> »Ί i * ρ ι c I IJ, ä Tttit dti by KuftfAiinn '«> a fla /. «;! i ⁱ rf!' ·.?

r ( b "x pH 7 in 4% Tsvl <™

, JuV.fo ♦ «**« * «« tj.yimwtv, - ^ tti ax

I ¹ - ^! Tvi'fliW;!.]; HIi ¹ ^ i.! Π '· ί ^; · Λ TiTi'r:;'·,' ,. · ¹ · ,; '.

ϋ ·. · ^| ίιΤ, '. ιΐ!'ίι'ΐ'··' .- ι'ι '; ¹

, Λ \

Ι '· V. "iT ,,: rii! I \ ^< ! IljJ'V !! i'iil!>''■ | ι · • t.iWüi'rj-H ·· ¹ ··,

w. <> M \\ r. ; · Αι «« ι »f-wiw,» (^ f

i. ί.Ί * lUl '| f, \ -'.! ►Hu

25th
Example 14

20 parts of 3,4,5,6-tetrafluoro are added to a neutral solution of 60 parts of the trisodium salt of the aminoazo dye obtained by coupling diazotized 2-aminonaphthalene-3,6,8-trisulfonic acid with 1-amino-3-meihyibenzene in an acetic acid medium in 500 parts of water -pyridazine and the mixture is stirred for one hour at 30 ⁰ C being maintained by the continuous addition of sodium hydroxide solution, a pH = 7. The partially precipitated acylation product is completely separated out and filtered off at pH 7 by adding 100 parts of sodium chloride.

For purification, the reactive dye obtained in this way can be dissolved again in 2500 parts of water at 30 ° C. clarified and deposited again by salting out the filtrate with 350 parts of common salt. The dye has the formula

SO ₃ Na

NaO ₃ S

SO ₃ Well!

CH,

and sets after filtering. Drying at 35 ^° C. and grinding is a yellow powder which dissolves easily in water with a yellow color and dyes Ceüuloseliasern in very real reddish-yellow shades by one of the above-mentioned dyeing processes in the presence of acid-binding agents. Real yellow dyeings are also obtained as wool and polyamide fibers.

Similar dyes can be found. if you proceed as above, but instead of the 60 parts of 4-amino-2-methylphenyl- (l ') -azonaphthalene- (2) -3.6,8-sulfonic acid rem sodium corresponding amounts of the amino compounds given in column 1 and the in Coupling components indicated in column 2 in the usual manner by diazotization and coupling in Acetic acid medium obtained aminoazo dyes used and acylated with 3.43.6-tetrafluoropyridazine.

Diazo component

Color ion mi

lomponenic

2-Aniinonjphirulin- l-Aminoo-melhyi st.uk red-

U5-i1isulfonsaure t * -mcthox> beiuo I stichi ^ cib

iics $ .l l-amini> 3-meth> l- yellow

benzene

lic si I l-Aminonaphihalin- rotsiichic

tvsulfonsJure yellow

desgl I - Smino-3-acc {\ I- reddish-

aminobcn.'ol yellow

can! · * ■ -V minor · he in I- reddish-

rwmsloft pc Ib

dcvcl l-Amimv .'- hvdrwy. rotsltchiE

2- \ mmonjrhthalin-5. * - d »sulfonic acid

oc be

strong ml

1- \ minoniphilhaiin- reddish-

- · 'cc! B

26th

Diazo component

Coupling component

Hue on cotton

2-aminonaphthalene-5,7-disulfonic acid

des & l.

ίο the same.

1-aminonaphthalene-3.7-disulfonic acid
, ς desgl.

the same

, ₀ 2-aminonaphthalene-3, t> -disulfonic acid

the same
the same
the same

the same

the same

2-aminonaphthalene
- _<5 6, S-disulfonsa'ua ^s

the same
descl.

l-amino-3-acetylaminobenzene

3-aminophenyl urine dead

reddish yellow

reddish yellow

l-amino-3-hydroxy- reddish-

aceiylaminobenzene yellow

l-amino-3-3methyl- strong red-

6-methoxybenzene light yellow

l-amino-3-niethyl- reddish-

benzene yellow

1-aminonaphthalene- reddish-

6-sulfonic acid same

1-aniino-3-methylbenzene

l-amino-3-diethyl

6-methoxybenzene

l-aniino-3-acetyl-

aminobenzene

3-aniinophenyl-

urinary stolT

1-Amino-3-hydroxyacetylaminobeniol
1-Aiuinonaphthalinh-sulfonic acid

reddish yellow

strong reddish yellow

pungent yellow

yellow

reddish yellow

reddish yellow

l-aniino-3-acetyl-red-tinged aminones / ol yellow

naphthalene-fi-sullOn- stichiggeU acid

1-anvinonaphthalene-

(vsuUbnsaure celb

2-aminonaphihaliw- like

the same

the same

yellow

de cf.

2 · Vminonaptuh.iltiv
.>. bS-tnsull "ons.uito
de sgl

dosgl
de sgl
doscl

\ i C Sg I

iicscl

thalnv golb "-suH'onsäiiiv

l-Amino-2-inotl \ o \\ - strongly rotnaphthaliw-o-siiUOiv slichiggol acid

\ nilin

.colb

\ nilin

λιυιηο

lAMstiohii ·.

golb

1-Ammo. «Iuotlnl ivisttchig · bon; ol gdb

go give

ο wwMl \ ox \ ov, iiiy.c

l Viuiwo *, woM loMuhit:

bow; oil

1 Vwwno <inoih.in uMviuiin:

27

-ortsotzunu

Diazo component

Coupling component

Shade au! "Cotton

2-aminonaphthalene-3,6,8-trisulfonic acid

the same
the same
the same
the same
the same
the same
the same
the same

2-aminonaphihalin-4,6,8-trisulfonic acid

the same

the same
the same

l-aminonaphthalene-2,4,7-trisulfonic acid c

the same

4-nitro-4'amino-

stilbcn-2,2'-di-

sulfonic acid c

the same

4-nilro-4'-umino-

stilbcn-2,2'-di-

suHbnsiiiirc

Aniline-2, S-'JisullOnsiiurc

the same
the same
the same
the same
the same

Aniline-2,4-disuHOnsiiurc

2,5-dimethoxyaniline

3-methyl-6-methoxyaniline

N-methylaniline
2-aminotoluene

1-amino-2,5-dimethylbenzene

1-amino-2-methoxybenzene

1-amino-3-methoxybenzene

1-aminonaphthalene-6-sul fonic acid

1-aminonaphthalene-7-sulphonic acid

1-amino-3-methylbenzene

Aminobenzene

aniline

l-amino-3-acctylaminobenzene

1-amino-3-methylbenzene

yellowish orange

yellowish orange

reddish yellow

reddish yellow

strong reddish yellow

strong reddish yellow

reddish yellow

reddish yellow

reddish yellow

reddish yellow

reddish yellow

yellow

reddish yellow

yellow

1-Aniinonaphtlialin-yellow 6-sulfonic acid

l-Amino-3-acctytaminobcn / .ol

3-AminophynylhurnstolT

reddish yellow

rotslichiggclb

l-amino-3-hyclroxy- reddish-

acclylaminobcinzol yellow

I-aminonaphthalene- reddish-

6-suH'onsiiurc yellow

1-aminonaphlhalin-

7-sulfomiiurc yellow

Ι-Ληιίηο-3-mulhyl yellow benzene

l-amino-.vicctyl-yellow aminobenzene

l-Amitu> -2-melhoxy- soldering-

5-methylbenzene yellow

l-amino-2,5- (li-

melhoxybenzene yellow

Example 15 65 parts of the dye of the formula

NaO., S

NH ₂

SO ₃ Na

(made by coupling diazotized 1-hydroxy-2-aminobenzene-4,6-disulfonic acid on 2-amino-8-hydroxynaphthalene-6-sulfonic acid and coppering of the obtained Azo dye) are dissolved neutrally in 700 parts of water. 25 parts of 3,4,5,6-tetrafluoropyridazine are added added and stirred at 20 to 30 ° C with constant blunting of the liberated acid with soda solution to pH 6 to 7, until no more free amino groups can be detected. The resulting reactive dye der formula

F F

NaO ₃ S

SO ₃ Na

is salted out, filtered, washed and dried at 30 to 40 ⁰ C. It dyes cellulose materials in very real ruby tones using one of the methods given above.

Dyes with similar properties are obtained from the procedure analogously to the above Copper complexes prepared from the diazo and azo components listed in the table below Azo dyes.

Diazo component

Coupling component

Hue on cotton

l-llydroxy-

2-aminobenzene-

4-suironsiiurc

l-Amino-2-molhoxy-reddish-5-methylbenzene yellow l-llyilmxy-2-aminobcn / .olss 4,6-disiiHOnsäiirc
the same

the same
the same
the same

2-methylamino ruby

5-hydroxynaphlha-

lin-7-sulfonic acid

2-amino-8-hy- ruby

droxynaphthalene

3,6-disiiironsiiiirc

2-amino-5-hy- ruby

dmxyniiphlhalin-

1,7-ilisiiHOnsiiiirc

2-AniiiHi-8-hy- ruby

dmxynaphlhalin-

3 .ft-tl i s u I Γο η sä n re

2-methyluminum ruby

5-hydiOxynaphtha-

lin-7-suHOnsiiure

l-amino-S-hy-violet

dmxynaphlhalin-

3, d-distiUbnsiiurc

l-amino-K-hy-violet

droxynaphlhiilin-

4,6-iliMiHOnsiiiire

29

Fort sctziiiiE

Diazo component

Coupling component

Hue on cotton

1-Hydroxy-2-amino-1-amino-8-hy-violet benzene-5-sulfone-hydroxynaphthoic acid 3,6-disulfonic acid

likewise. l-amino-8-hy-violet

hydroxynaphthalene-4,6-disulfonic acid

1-Hydroxy-2-amino-1-amino-8-hy-bluish-4-acetylaminodroxynaphthalene violet benzene-6-sulfonic-3,6-disulfonic acid

the same

l-ethoxy-8-hy- bluishdroxynaphthalene-violet 3,6-disulfonic acid (4-position acetylamino group then saponified)

1-Hydroxy-2-amino-1-amino-8-hy-blue 4-acetylamino-hydroxynaphthalenebenzene-6-sulfone-2,4-disulfonic acid

likewise. l-amino-8-hy-blue

droxynaphthalene

2,4,6-trisulfonic acid

1-Hydroxy-2-amino-1-amino-8-hy-blue 6-acetylamino-hydroxynaphthalenebenzene-4-sulfone-2,4-disulfonic acid

(6-position acetylamino group saponified) l-amino-2-hydroxy-l-amino-8-hy-blue 6-nitronaphthalene-droxynaphthalene-4-sulfonic acid 2,4-disulfonic acid

(6-position nitro group subsequently reduced to -NH ₂ )

l-amino-2-hydroxy-l-amino-8-hy-blue 6-nitronaphthalene-oxynaphthalene-4-sulfonic acid c 2,4,6-trisulfonic acid

(Sixth nitro group reduced to -NII ₂ ) 1-Hydroxy-2-amino-1-amino-8-hy-blue 6-acctylamino-hydroxynaphthalenebenzene-4-sulfone-2,4,6-trisulfonic acid

(6-position acetylamino group saponified)

Example 16

The procedure is as indicated in Example 5, but the dia / .oticrtc active group-containing intermediate is coupled in a soda-alkaline medium instead of with parts of the sodium salt of i-benzoylamino-8-hydroxynaphthalene-3,6-disulfonsihirc with 40 parts of the sodium salt of 1 - acetylamino-B-hydroxynaphthalene-S.edisulfonsiUirc and isolates the resulting dye of the formula OII

SO ₁ Ma

HN

Vt

NaO ₁ S

NlI- C'O-Cll,

S (), Na

soluble dyestuff dyes cellulose materials by the pad-steaming or pad-heat setting process (at 140 ⁰ C) in weißätzbaren, wet, frictional and lightfast blaustichigroten tones.

Example 17

The solution of 19.5 parts of the sodium salt of l-aminobenzene-2,5-disulfonic acid and 6.9 parts of sodium nitrite in 200 parts of water is made into a mixture

ίο allowed to run in 100 parts of ice and 28 parts by volume of concentrated hydrochloric acid; then the mixture is stirred for half an hour at 0 to 10 ^° C. and then excess nitrous acid is removed. To the resulting diazo suspension is added at 0 to 10 ⁰ C, the cooled and thereby again partially crystallized solution of 26.2 parts of the potassium salt of l-aminonaphthalene-8-sulfonic acid in 250 parts of hot water and blunts the strongly acidic coupling mixture at 10 to 20 ⁰ C by carefully adding sodium hydroxide solution to pH 4. The coupling is completed quickly; the aminoazo dyestuff formed is completely salted out with 100 parts sodium chloride, filtered off with suction, washed and redissolved in 500 parts of water at 20 ⁰ C and pH 6 to 7th The aqueous solution is partially mixed with 20 parts of 3,4,5,6-Tctrafluor-pyridazine and stirred with soda solution to pH 6 to 7 for one hour at 20 to 30 ° C while continuously blunting the liberated acid. If no more aminoazo dye can be detected, the partially precipitated reactive dye becomes of the formula

NH

> -SO, Na

SOjNa

jo salted out with table salt, filtered off and dissolved again in 800 parts of warm water for cleaning. After the solution has cleared, the pure dye is separated out from the filtrate by adding 60 to 90 parts of common salt. After filtering, drying at 35 ° C. and grinding, a yellow powder is obtained which easily dissolves in water with a yellow color and which dyes the pulp fibers in a very good yellow shade, very good in wet, light and chlorine-fast by one of the above-mentioned dyeing processes in the presence of acid-binding agents . Even

.so on wool and polyamide fibers there will be real yellow colorations obtain.

If one proceeds as indicated above, but instead of 19.5 parts of the sodium salt of 1-aminobenzene-2,5-disulphonic acid equivalent amounts of the diazo component listed in the table below !! on the 1-ainonaphthalene-8-sulfonic acid coupling, received after acylation with 3,4,5,6-Tctrafluor-pyridazin also valuable yellow to brown reactive dyes.

Diazo component

! • color on cellulose fiber

in the manner indicated in Example 5. The one in water 2-aminonaphthalene-4, K-tlisulfonsäurc strongly red

stichiggclb

2-aminonaphthalene-5,7-ilisulfonic acid strong red

sticlhißgclb

31

oilscl / unii
) i; i / okompi> ni: nU '

2-aminonaphthalene-6,8-disulfonic acid 2-aminonaphthalene-3,6,8-trisulfonic acid 2-aminonaphthalene-4,6,8-trisulfonic acid 4-Aminoazoben7.ol-3.4'-disulfonic acid

4-Amino-2-acetylaminoa7.oben7.ol-2 ', 5'-disulfonic acid

NH,

SChNa

SO ₃ Na

(l-aminobenzene-2,5-disulfonic acid acidic on l-aminonaphthalene-6-sulfonic acid coupled)

NH,

SO ₃ Na

SO ₁ Na

(in 6- or 7-position)
(l-aminobenzene-2,5-disulfonic acid acidic to the technical mixture of l-aminonaphthalene-6- and -7-sulfonic acid coupled)

NaO ₃ S

SO ₃ Na

N = N

NH,

l'iirhton on

('cllull) Sl'filSLT

. strong reddish yellow

strong reddish yellow

strong reddish yellow

yellowish brown

orange brown

reddish brown

reddish brown

40

45

purple-tinged brown

SO ₃ Na SO ₃ Na

(1-Aminonaphthalene ^ .SJ-trisulfonic acid acidic to l-aminonaphthalene-6-sulfonic acid coupled)

NaO ₃ S

SO ₁ Na

N = N

SO, well

OCH ₃

NH,

reddish brown

(l-Aminonaphthalene-2,5,7-sulfonic acid acidic on l-amino-2-methoxy-5-methylbenzene coupled)

Example 18

When you put cellulosic fabric with a printing paste printed, the kilogram of 30 g of the dye described in Example 5, 10Og urea, 300 g water, 500 g alginate thickener (60 g sodium alginate per kilogram of thickening), 10 g soda and 10 g des Contains the sodium salt of 3-nitrobenzenesulfonic acid and which has been made up to 1 kilogram with water, then intermediate drying and then in a suitable steamer for 200 seconds at 103 to 115 ° C steams, after rinsing and boiling .. soaps you get a strong blue-tinged red print of good quality Wet, rub and light fastness.

Example 19

A mixture of the solutions of 65.5 parts each of the chromium 2:! Complex and the cobalt 2: 1 complex of the dye of the formula

HO NH ₁

O, N

SO ₃ Na

SO ₃ Na

in 400 parts of water with 50 parts of 3,4,5,6-tetrafluoropyridazine for about 3 hours at 10 to 20 ° C while maintaining pH 6 to 7 stirred. No aminoazo dye if chromatographed (Co complex: blue; Cr complex: blue-green) is more detectable, the resulting mixture of the two Salted out reactive dyes with potassium chloride, filtered off and dried.

The dye replenishes on cellulosic materials the pad dyeing process or in print in the presence of acid-binding agents strong, very good wet and lightfast black tones.

If one proceeds accordingly, however, the mixture of the chromium 2: 1 and cobalt 2: 1 complex If the following aminoazo dyes are used, valuable black dyes are also obtained:

Diazo component

Coupling component

Coupling pll

1-hydroxy-2-amino-4-nitrobenzene

l-hydroxy-2-amino-

4-nitronaphthalene

7-sulfonic acid

l-hydroxy-8-amino-9

naphthalene-3,6-di-

sulfonic acid

also 9

20th

example

To the neutral solution of 53.1 parts of the disodium salt of the 1-amino-4-nitrobenzene-2-sulfonic acid obtained by coupling diazotizing agents with 1- (2'-chloro-5'-sulfophenyl) -3-methyl-pyrazolone- ( 5) and subsequent reduction of the nitro group with sodium sulfide obtained aminoazo dye in 300 parts of water and 20 parts of 3,4,5,6-tetrafluoropyridazine. The mixture is stirred for 2 hours at 30 ^° C., the acid being released

33

continuously with soda solution to a pH value of blunt. The deposited dye of the formula

SC) ₅ Na

-ecu,

HO

Cl

NaO ₃ S

is filtered off, dissolved in 3000 parts of water at pH 6 to warm and from the filtered solution through Addition of common salt precipitated again. After filtering off, drying and powders one obtains einl L-same well water-soluble powder, the Cellulosemaicm-Men from long fleet at 30 "C or after dum | Klolz cold dwell process with soda as an acid-binding agent Means in clear washing, rubbing and lichiechieti Shades of yellow. .

If you proceed as indicated above, but instead of the amino acid 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 means as well Unless otherwise stated, the term "saponified" denotes an acylamino group contained in the aminoazo color pe has been subsequently saponified, while dei | Expression "reduced" means that one is in the diazo component contained nitro group is reduced to the amino group after coupling, whereby the dei forms the desired aminoazo dye.

Diazo component

Azokompononlc

pH of the shade

Coupling on mediums cellulose

5-6

1-Amine-nitrobenzene ^ -sulfonic acid 1- (4'-sulfophenyl) -3-methyl-pyrazolone- (5)

(4-position nitro group then reduced)

l-Amino-4-nitrobenzene-2-sulphonic acid l- (4'-SuHbphnyl) -3-earboxy-pyrazolone- (5) 5-6

yellow

the same
l-Amino-O-acetylaminobenzene-o-sulfonic acid

(3-position acetylamirio group followed by l-amino-O-acetylaminobenzene-O-sulphonic acid 2 mol l-amino-3-ace (ylaminobenzene-6-suironic acid (stranded)

1 mol of l-amino-3-acetylaminobenzene-6-sulfonic acid (saponified) l-amino-5-acetylaminonaphthalene-3,7-disulfonic acid (saponified)
1-amino-2-methylbenzene-4,6-disulfonic acid

the same

1-Amino-2-methylbenzene-4,6-disulionic acid 1-aminobenzene-2-S-sulfonic acid 2-aminonaphthalene-3,6-disulfonic acid 2-aminonaphthalene-3,7-disulfonic acid 2-aminonaphthalene-4,8-disulfonic acid 2-aminonapithalin-3,6-disulfonic acid c 2-aminonaphthalene-4,8-disulphonic acid l-amino ^ -methoxybenzene ^ -sulphonic acid the same

1- (3'-sulfophenyl) -3-methyl-5-aminopyra / .ol 1- (3'-sulfophenyl) -3-methyl-5-aminopyrazole

saponified) t-0e-hydroxyethyl) -3-methyl-pyiazolon- (5) 1 mol of bis-pyrazolone from 4,4'-bis-hydrazinodibenzyl-2,2'-disulfonic acid and ethyl acetoacetate
1- (4'Sulfophenyl) -3-carboxy-pyrazolone- (5)

the same

2-acetylamino-5-naphthol-7-sulfonic acid

(saponified)

2-acetylamino-8-naphthol-6-sulfonic acid

(saponified)

l-chloro ^ -acetylamino-S-naphthol ^ -sulfonic acid (saponified)

l-acetylamino-S-hydroxynaphthalene ^ .o-disulfonic acid (saponified)

the same

the same.

l-acetylamino-S-hydroxynaphthalene ^ o-disulfonic acid (saponified)

the same

2- (N-acetyl-N-methylamino) -5-hydroxynaphthalene-7-sulfonic acid (saponified)

2- (N-Acetyl-N-methylamino) -8-hydroxynanhthalene-6-sulfonic acid (saponified)

5-6 Red
pithy
yellow 6-7 yellow 6-7 yellow 5-6 yellow 5-6 yellow 5-6 yellow 5-6 reddish
yellow 7-8 orange 7-8 Red 7-8 orange 7-8 Red 7-8 blue-
stichigroi 7-8 blue-
stichigroi 7-8 blue-
stichigro 7-8 blue-
stichigro 7-8 blue-
stichigro 7-8 yellow- süc'iiigru 7-8 Red

nrlsi'lzimu

) ia / oki> niponente

i-Aminohenzene-2-sylbic acid

l-aminobenzene-3-sulphonic acid
1-ainobenzene-4-sulfonic acid
1-Amino-4-methylethylbenzene-2-sulfonic acid, 1-Amino-2,4-methylethylbenzene - () - suHbnsiiurc

the same
the same

4-Aminoaz.obcnzul-3,4'-disuHbic acid

the same

the same

the same

the same

36

A / okoinponcnic

pll ilcs l-'iirbtnn

Coupling * - aiii 'mediums cellulose

2- (N-AL-eiyl-N-nKlhylaminii) -N-hydroxy-7-χ naphihalin-h-sullbnsiiure (vurseil't)

also 7-8

also 7-8

also 7-8

2- (N-Acelyl-N-melhykimmo) -8-hydroxy-7-8 naphthulm-6-sulfonic acid (saponified)

2-Acclylamino-8-hydroxynaphthalene- 7-8 (i-sulfonic acid (saponified)

2-acelylamino-X-hsdroxynaphinalin-7-8 3,6-disulfonic acid (saponified)

l - / \ mii "io-3-; Reivl;) minobenzene 5-6

l-amino-3-hydroxyacetylaminobenzene 5-6

l-aminonaphthalene-6-sulfonic acid 5-6

l-aminonaphlhalin-7-sulfonic acid 5-6

l-Amino-2- (4'-amino-2'-sulfophenyl- (l '(- azo) - 8 8-hydroxynuphthalene-3,6-disulfonic acid

Red

red red red red

Red Red

yellow-brown yellow-brown yellow-brown yellow-brown black

example

52 parts of 1-amino-4- (4'-N-methylamino-methylanilino) -anthraquinone-2,2'-disulfonic acid are dissolved in 550 parts of water and adjusted to pH 6 with sodium hydroxide solution. Then 20 parts are added dropwise at room temperature 3,4,5,6-Tetrafluoropyridazine and maintains a pH of 7 with 2N sodium hydroxide solution. The implementation will followed chromatographically. The reaction product crystallized in blue needles is suctioned off and washes the filter residue with 3% saline solution. Clear blue dyeings are obtained on cotton good wet fastness properties and good light fastness.

The resulting dye corresponds to the likely formula

O NH,

SOjH

The amino-anthraquinone derivatives listed in the following table can in principle be used in the same way convert to valuable reactive dyes, the color shades of which are indicated on cotton.

Water-soluble amino-linthraquinone derivative

l-Amino ^^ '- N-methylaminomethylanilinoVanlhraquinone ^ .o ^' - trisulfonic acid 1-Amino-4- (4'-N-methylaminomethylanilino) -anthraquinone-2,5,8-trisulfonic acid l-Amino ^^ '- N-methylaminomethylanilinoVünthraquinone-l ^ -disulfonic acid

l-Amino-4- (4'-aminoanilino) anthraquinone-2,6-disulfonic acid

l-Amino-4- (4'-aminoanilino) anthraquinone-2,5-disulfonic acid

l-Amino-4- (3'-aminoanilino) anthraquinone-2,6-disulfonic acid

l-Amino ^ -P'-aminoanilinoVanthraquinone-Z.S-disulfonsa'urc l-Amino-4- (3'-aminoanilino) -anthraquinone-2,4'-disulfonic acid dye ion on cotton

greenish blue

greenish blue

blue

blue green

greenish blue

blue

blue

somewhat reddish blue

'nrlscl / unu

38

Water-soluble amino-untreated derivative

l-Amino-4- (3'-aminoaniiino) -anthnichi non-2,4 ', (i'-trisuiroiisaurc
! -Aminii-4- (4'-aminocyulohL'xylamino) -anlhraquinone-2,5, S-tiisulfonsaiire
l-Amino-4- (4'-N-melhylaniinomelliyianilino) -anthracliinon-2, .V-disullonic acid
.! ■ Amino-4- (4 '- [' 4 "- aminobünzoylaniinoJ-aiiilino) -anlhraquinone - :, 5, K-irisulfonic acid

t-ai'htiiii nut liati-nwnlk-

rotstichiyblau clear blue
blue
blue-green

-A _m iH> 4- (4M.4 ^ aminuben / oisulfamido] -an, lino) -an.hrachinon-2.5, _H-S trisulfon iiure grünstichiublau
-Amino-4- (4 "-aminoslilbenamino) -anthraL'hinon-2,2 ', 2" -insulfic acid

O NH,

clear rolslicliiu blue

SO ₁ NH SO,

V-NH,

Example 22

8.2 parts of 1-amino-4- [3'-aminoanilino] anthruchinone-terminated acylation, the dye is at 20 "C mi

2-sulfonic acid are salted out in a mixture of 160 parts of table salt and the reaction product

Sucked off water and 80 parts of dioxane with the addition of 1.05, washed with 2% sodium chloride solution and unc

Part dissolved sodium carbonate. At 20 ⁰ C are added dropwise 3.8 ₃ o in vacuo at 30 ° C dried.

Parts 3,4,5,6-tetrafluoropyridazine and lasts through. The dye dyes wool in a very wet-fast blue

Addition of 2N soda solution a pH of 6 to 7. According to tones.

O NH ₂

SO., H

Example 23

If you follow the instructions in Example 5 7 to 8 with the solution of 40.5 parts of the

proceeds, but from!, S-Diaminobenzene-ö-sulfonic acid disodium salt of 2-sulfoacetylamine-5-hydroxy-

re and 3,4,5,6-tetrafluoropyridazine obtained dye-50 naphthalene-7-sulfonic acid is obtained one

Intermediate product after diazotization at 0 ° C and pH reactive dye of the formula

SO ₃ H

OH

NH-CO-CH ₂ -SO ₃ H

the cellulose materials according to the usual application methods with soda as the acid-binding agent ir real shades of orange.

Example 24

If one proceeds as indicated in Example 21, but instead of the Aminoazofarb substance used there 53.1 parts of the disodium salt of the by coupling

of diazotized 1-amino-4-n! trobenzene-2-sulfonic acid with l- (2'-chloro-5'-sulfophenyl) -3-methyl-pyrazolone- (5 and subsequent reduction of the nitro group mi

Sodium sulfide obtained aminoazo dye with the 3,4,5,6-tetrafluoropyridazine acylated, so is obtained also a valuable reactive dye, with which cellulose materials after the usual dyeing and printing processes can be printed in true yellow tones.

Similar reactive dyes are obtained if, instead of the above-mentioned aminoazo dye, one of the aminoazo dyes built up from the components listed in the table below with 3,4,5,6-tetrafluoropyridazine acylated:

Example 25
58 parts of the dye of the formula

NaO ₃ S

NH-CH ₃

Diazo component Azo component

hue

l-amino-4-nitrobenzene-2-sulfonic acid (reduced)

the same

the same

the same

l-Amino-3-acctylaminobenzene-6-sul
fonsäure (saponified)

the same

so,

the same

l- (2'-methyl-4'-sulfophenyl) -3-methyl-pyrazolone- (5)

1- (2 ', 5'-DiSViIfO-

phenyl) -3-methyl-

pyrazolone- (5)

l- (2'-methyl-

4'-sulfo-6'-chloro-

phenyl) -3-methyl-

pyrazolone- (S)

l- (2 ', 5'-dichloro-

4'-sulfophenyl) -

3-methyl-pyrazo-

lon- (5)

l- (2'-methyl-

4'-sulfophynyl) -

3-methyl-pyrazo-

lon- (5)

l- (4'-suilbphenyl) -

3-methyl-pyrazo-

lon- (5)

l- (2'methyl-

4'-sulfophenyl) -

3-carboxy-pyrazo-

lon- (5)

l- (2'-chloro-4'-sul (o-

phcnyD-3-carboxy-

pyrazolone- (5)

yellow

yellow yellow

yellow

greenish yellow

greenish yellow

greenish gclb

grünstichiggclb (prepared by coupling diazotized 1-hydroxyis i-amino ^ -chlorobenzene-S-sulfonic acid to 2-methylamino-8-hydroxynaphthalene-6-sulfonic acid and coppering of the azo dye obtained) are dissolved in 700 parts of water in a neutral manner. Are added dropwise 20 parts of 3,4,5,6-tetrafluoro-pyridazin added and stirred at 20 to 30 ⁰ C with continuous dulling of the liberated hydrofluoric acid with sodium carbonate solution to pH 6 to 7 to any free amino group is no longer detectable. The reactive dye formed of the formula

40

NaO ₃ SI NaO ₃ S
Cl

is salted out, filtered, washed and dried at 30 to 40 ⁰ C. It dyes cellulose materials in very real violet tones using one of the methods given above.

Dyes with similar properties are obtained from the procedure analogously to the above Copper complexes obtained by simple demethylating or oxidizing copper plating are obtained from the ir The table below lists diazo and azo components produced mono- and diazo dye fe:

Din / .okompoticnte

A / .okomponcntc pH of the shade

Clutch

m u di u ms

l-Hydroxy ^ -amino ^ -chloibcnzol-S-suiron- 2-Amino-8-hydmxynaphthulin-3, (i-ilisuiron- 10 acid acid

likewise l-amino-8-hydmxynaphlhiilin-3, (vdisuiron- H)

acid

2-aminonaphthiilin-4, ii, 8-trisultonsiiurc 2-lly (lroxy-6-acclylaniiniinaphthalin-4-suirim-H ⁽ >

(oxidizing gckuplerl) acid (vcrscifl)

l-amino ^ -hydroxy-d-nitronaphlhalin-. l-l-lytlroxy-8-iilhoxynaphthalin-3, (> - itisiiiron- IO 4-siillOnsiiurc (reduced) acid

l-lydiOxy-2-aminobcnzi) l-4, (i-disuironic acid 2-lyiliOxy-3-iiniinoniiphlliiilin-5.7-disuHon-10

acid

2-aminonaphthalene-4,8-disulfonic acid 2-hydroxy-3-aninonophthalene-. ^l >, 7-disuiron- 8 ^Λ )

(oxidizing cladded) ^siilirc

rulstichi violetl

blaii-

stichi (> -

violet

reddish
blue

blue

mt

blue

709 M.

continuation

¹ XX

Diazo component

Λ / .okomponcntc

pH of the shade

Tipping

mcdiums

2-aminonaphthalene-4,6,8-trisulfonic acid
(oxidizing copper)

B-methoxy ^ -amino-o-methyl-azobenzene-2 ', 4'-disulfonic acid (demethylating
coppered)

the same
the same

B-methoxy- ^ amino-o-methyl-azobenzene-2 ', 5'-disulfonic acid (demethylating
coppered)

the same
the same

2-Hydroxy-3-aminonaphthalene-7-sulfonic acid 8-9

2-methylamino-5-hydroxy naphthalene-10

7-sulfonic acid

2-amino-8-hydroxynaphthalene-3,6-disulΓone-10
acid

2-Amino-5-hydroxy naphthalene-1,7-disulfone-10
acid

2-methylamino-5-hydroxynaphthalene-7-sulfonic acid

10

2-amino-8-hydroxynaphthalene-3,6-disulfone-10
acid

2-Amino-5-llydroxynaphthalene-1,7-disulfone-10
acid

blue

navy blue

man blue

navy blue
navy blue

navy blue

navy blue

Example 26

0.1 mole of the 3 aminoazo dye of the formula
SO ₃ H

HO ₃ S

SO ₃ H

SO, H
SO ₃ H

- manufactured according to the information of the German 40

Patent 11 15 865 by coupling the diazonium compound from 2-aminonaphthalene-4,8-disulfonic acid with l-aniinonaphthalene-6-sulfonic acid, further diazotization of the aminoazo dye obtained, coupling with the equivalent amount

2,5-diaminonaphthalene-4,8-disulphonic acid and conversion to the aminotriazole - is released, and in 1000 parts by volume of water at pH 6 under stirring at a temperature of 20-30 ⁰ C with 20 parts of 3,4,5,6-Tctrafluor -pyridazine added. The slowly released hydrofluoric acid is blunted with soda solution until the reaction has ended. The dye is then deposited, isolated and dried at about 5O ⁰ C in vacuum by the addition of sodium chloride. It is a yellow powder that is soluble in water with a yellow color.

Example 27

30.4 parts of 2-amino-8-oxynaphthalene-3,6-disulfonic acid are dissolved neutrally in 300 parts of water, heated to 30 to 40 ° C and 20 parts of 3,4,5,6-Tetrafltior-pyridaz'in added. 40 parts become grounded in the course of one hour 15% soda solution added so that the pH value is 6 to 7. The acylation product partially fills out.

F. a freshly prepared diazonitim salt solution from I3, h Share p-Aminobenzylsulfonsaurc at 0 to 5 "C in the suspension of the mixed with 12.5 parts of soda

so Acylierungspioduktes dripped. After five hours Stirring at ice bath temperature is then salted out with sodium chloride, filtered off with suction, with dilute sodium chloride solution washed and dried at 30 ° C. in a vacuum drying cabinet. The dye obtained corresponds to

ss the formula

NaO ₃ S Cl I

N N

NiiO., P

If one seduces as indicated above, but instead of 30.4 parts of 2-amino-8-oxynaphthalene-3,6 · clisulfonsüurc 30.4 parts of 2-amino-5-oxynaphthalene-l, 7-

> N

disulfousUure with 3,4,5,6-Tclrnfluor-pyridazin ncyin. " and coupling the reactive coupling component with diazotized p-amino benzylsulfonic acid.

a readily soluble reactive dye is obtained, the fabric containing cellulose fibers in brilliant colors reddish shades of orange.

Cotton or cellulose tissue is impregnated on a padder at 20 to 25 ° C with a solution containing 30 g of the in this example, paragraph 1, per liter of liquor described dye, containing 100 g urea and 20 g soda, squeezes to a moisture content from approx. 100% and rolls up the damp tissue again. After standing at room temperature for 24 hours the fabric rinsed, soaped at the boil in the usual way and dried. A brilliant scarlet color is obtained Coloring of good wet and light fastness.

Cotton or cellulose fabric is impregnated on a padder at 20 to 25 ° C with a solution containing 30 g of the dye described in this example, paragraph 1, 100 g of urea and 20 g of soda per liter of liquor, squeezed to a moisture content of about 100% and attenuates 3 minutes at 103 ⁰ C. After rinsing, soaping at the boil and drying is likewise obtained a brilliant scarlet dyeing of good wet and light fastness.

Cotton fabric is impregnated with a solution at 20 to 25 ° C containing 20 g of the dye obtainable according to this example, paragraph 1, and 0.5 g of a nonionic wetting agent (e.g. a polyoxyethylated oleyl alcohol) and 150 g of urea per liter of liquor and contains 15 grams of sodium bicarbonate. The fabric is then squeezed between two rubber rollers to a moisture content of approx. 100%. After intermediate drying at 50 to 6O ⁰ C. for 8 minutes at 140 ° C is heated and purged the coloration thus obtained thoroughly with hot water and for 10 minutes boiling with a solution containing per liter 5 g of Marseilles soap and 2 g sodium carbonate. After rinsing and drying, a strong, scarlet coloration with good wet and light fastness is obtained.

If you print cellulose fabric with a printing paste containing 30 g of the kilogram in this example, Paragraph 1, described dye, 100 g urea, 300 g water, 500 g alginate thickening (60 g sodium alginate per kilogram of thickening), 10 g of soda and 10 g of the sodium salt of 3-nitrobenzenesulfonic acid and which was made up to 1 kilogram with water, then dried in between and then in one Suitable steamer steams 3 minutes at 103 to 115 ° C, so you get after rinsing and boiling Soaps have a strong scarlet color with good fastness properties.

100 parts of wool are placed in a bath at 40 ° C. in which 1.5 parts of the in this example, paragraph 1, described dye and 6 parts of 30% acetic acid and 0.5 parts of a contains polyoxyethylated hydroxyl-containing stearylamine derivatives. The dye bath is in 30 Bring to a boil for minutes, then boil dyeing for an hour. Preserves after rinsing and drying you get a brilliant, washable, millfast and lightfast scarlet coloration.

example

28.9 parts of 2-aminol-methylbenzene-3,5-disulfonic acid (monosodium salt) are diazotized and the diazo compound is coupled with 13.7 g of l-amino-S-methoxy-S-methylbenzene in a weakly acidic medium. The monoazo dye obtained is isolated and then or immediately diazotized in solution without isolation and coupled under alkaline conditions with 25.3 parts of 2-methylamino-5-hydroxynaphthalene-7-sulfonic acid. The disazo dye obtained is ausgcsalzcn by addition of sodium chloride, suction filtered and the isolated product with about 50 parts of crystalline copper sulfate, 40 parts of diethanolamine, 50 parts Ammoniiak (D: 0.88) metallized in 5 hours at 95 to 100 ⁰ C. The dye is isolated from the coppering solution by adding salt and carefully acidifying it.

The copper-plated aminodisazo dye is then acylated in an aqueous solution at pH 6 to 7 at a temperature of 20 to 30 ° C. with 20 parts of 3,4,5,6-tetrafluoropyridazine, the pH value in the range indicated by the addition of soda is held. After bcendctei acylation of the dyestuff is isolated with Natriumchloric and dried at 35 ⁰ C. In the form of the free sulfonic acid, the dye corresponds to the formula

O-Cu-O

he dives cellulose fabric according to the reactive dye known processes in nut and lightfast mnrincblnucn tones.

In a similar way, further inventive Make mtlQc dyes if you do the above Monoazo dye from 2-amino-1-inicthylbenzene-3,5-disulfonic acid and i-amino ^ -methoxy-S-methylbenzene with the aminonaphlholsulfonic acids listed in the following table and 3,4,5,6-tetrafluoropyridzine do koitib in accordance with the regulation given above ned:

Coupling component

h.s 2-Ainino-5-hydroxynnphthttlin-l, 7-disulfonsylurc,

2-Amino-8-hydroxynaphthulin-3, b-disulfonsliurc.

The dyestuffs obtained have b-line color.

Example 29

0.1 mol of 4-ureido-2-amino-1-hydroxybenzene-5-sulfonic acid is diazotized and soda alkalically with 0.1 mol 1-Amino-e-hydroxynaphthalene ^^ - disulfonic acid coupled. The coupling solution is adjusted to a content of 2 mol / liter with caustic soda and then 3 hours boiled under reflux to saponify the ureido group. After cooling, it is mixed with hydrochloric acid neutralized. By adding 25 parts of copper sulfate and 100 parts of 2η sodium hydroxide solution, the dye becomes 45 ° C and a pH value of 4 to 6 metallized and after 30 minutes at pH 6 to 7 and temperatures of

Acylated from 20 to 30 ^° C. with 0.1 mol of 3,4,5,6-tetrafluoropyridazine. The obtained dye of the formula

O-Cu

NH,

S Ο., H

SO ₃ H

is salted out. A blue coloration is obtained on cotton.

Claims (7)

Claims:. Reactive dyes of the formula D - N <: N D the remainder of a dye of the azo, anthraquinone or azaporphin series, the at least one Contains sulfonic acid group, and R is hydrogen or methyl. 2. Reactive azo dyes of the formula [B-NN-EJ-N - { N R Λ Ν wherein B is the remainder of a carbocyclic diazo component of the benzene or naphthalene series and E is the remainder of an enolic or phenolic coupling component, in particular one 5-pyrazolones, an oxynaphthalene or an aminonaphthalene, where B or E have at least one sulfonic acid group, and R is hydrogen or —CHj. 3. Reactive azo dyes of the formulas (SC) ₁ H) ₀ .. ,, N (R) A - N = -N-C HO (or H ₂ N-) C —CH, (or COOH) Il N
^V OH ^ J- (SO ₃ H) ₁ _ ₂ H; Cl; CH, _{H; CI; CH3} H; OCH,; NH-acyl OH - N - = N N (R) -A H; Cl; NO ₂ H; OH; NO ₂ N (R) -A
(SO ₃ H) ₁ _ ₃ (SO ₃ H λ, _ ₂ , Ο — Cu-O NH ₂ (or NH-acyl) NH-A V j> ■ N N ·: · A-NH 5c / SO, H (SO., H) o_, forward to A for the rest NH, (or NH-alkyl) HO - <ν SO ₃ H - (SO ₃ H) ₁ _ ₃ N N stands. R denotes a —CH ₃ group or a hydrogen atom and in which (o) indicates the ortho position of the respective substituents in the aryl nucleus and Me denotes Cu, Cr or Co. 4. Reactive anthraquinone dyes of the formula O NH where L and L 'are sulfonic acid groups, ρ is a number from 0 to 2 and R is hydrogen or —CH ₃ , the dyes having at least one sulfonic acid group. 5. Reactive phthalocyanine dyes of the formula Pc-SO ₂ NH (CH ₂₇ , Pc for the remainder of a nickel or copper phthalocyanines, L and L 'for sulfonic acid groups, r for 0,1 or 2, q for the number O or 1, R stands for hydrogen or a methyl group and the phthalocyanine residue Pc as further substituents 1 to 2 sulfonic acid and / or 1 to 2 sulfonic acid amide groups, such as -SO ₂ NH ₂ , -SO ₂ -NH-alkyl, -SO ₂ N (AlICyI) ₂ - and -SO ₂ NH -ary! -Grunpen, where “alkyl” stands for alkyl radicals with 1 to 3 carbon atoms and where the dyes have at least one sulfonic acid group. 6. Use of the dyestuffs according to Claims 1 to 5 for dyeing and printing hydroxyl-containing groups Materials, in particular textile materials made from native or regenerated cellulose. 7. Use of the dyes according to claims I to 5 for dyeing Γ-ί hooked materials, preferably of wool, silk, synthetic super polyamide and polyurethane fibers.