DE2647312A1 - REACTIVE COLORS - Google Patents

Description

Bayer Aktiengesellschaft ^ 2647312

Central area of patents, trademarks and licenses

5090 Leverkusen, Bayerwerk My / Jo / bc

19.Oct. 1976

Reactive dyes

The invention relates to reactive dyes of the formula _χ

f- W-N-V-T N) (I)

^Z Y wherein
X is a cleavable under reactive dyeing conditions

Group,
Y -N-CH-SO-.H or

II ^J

R ₁ Q

N-CH-SO ₁ H

II ^J

R ₁ Q

R ₁ optionally substituted alkyl, R ₂ hydrogen, optionally substituted alkyl or aralkyl,

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F the remainder of an organic dye,

W and V a direct bond or a bridge link,

Q is hydrogen or optionally substituted alkyl, D is hydrogen, optionally substituted alkyl

or aryl,
E optionally substituted alkylene or arylene

and
η 1,2,3 or 4 mean.

Suitable bridge members W are, for example:

-SO ₀ -, -CO-, -alkylene-CO-, -arylene-, -arylene-SO, -, -arylene-CO-, -alkylene- or -amino-CO-.

Suitable bridge members V are, for example:

-CO-arylene-N (R ₃ ) -, -CO-alkylene-N (R ₃ ) -, -CO-aralkylene-N (R ₃ ) -, -CO-alkarylene-N (R ₃ ) -,

-SO ₂ -arylene-N (R ₃ ) -, -SO ₂ -alkylene-N (R ₃ ) -, -SO ^ aralkylene-N (R ₃ ) -, -SO ₂ -alkarylene-N (R ₃ ) - ,

-Alkylene-N (R ₃ ) -, -aralkylene-N (R ₃ ) -, -alkarylene-N (R ₃ ) -, -arylene-N (R ₃ ), -CO-aralkylene-0-, -CO- Alkarylene-0-, -S0 ₂ -arylene-0-, -S0 ₂ -aralkylene-0-, -S0 ₂ -alkarylene-0-, alkylene-O-, -aralkylene-O-, -alarylene -0-, -Arylene-0-,

where R ₃ denotes hydrogen, optionally substituted alkyl or aralkyl and the phenylene and arylene groups can carry further substituents.

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Arylene and aryl D, E and in the bridging units W and V are, for example, phenylene, naphthylene or phenyl and naphthyl, for example, by SuIfο, carboxy, mono- optionally substituted by C ^ -C _"f alkyl benzyl or phenyl, or di-substituted sulfonamide or carboxamide, optionally in the phenyl nucleus by C.-C »alkyl, C ₁ -C ₄ -alkoxy, chlorine, nitro, carboxy or substituted SuIfο Phenylsulfonylaminosulfonyl or Phenylöulfonylaminocarbonyl, C ₁ -C ₄ -Alkylsulfonylaminosulfonyl, C. -C ₄ ~ alkylsulphonylaminocarbonyl, Cj-C ^ -Alkylsulfonyl, optionally by Cj-C ^ -alkyl, C ₁ -C ₄ -AIkOXy, chlorine, bromine, nitro, ■ sulfonyl or carboxy substituted phenylsulfonyl, C ₁ -C ₄ -alkylamino, optionally by C, - C ₄ alkyl, C ₁ -C ₄ alkoxy, chlorine, bromine, nitro, sulfo or carboxy substituted phenylamino or benzylamino, nitro, cyano, halogen such as chlorine and bromine, hydroxy, C ₁ -C ₄ alkylcarbonyloxy, benzoyloxy, C. ₁ -C ₄ -AIkOXy, C.-C ₄ -alkyl mercapto, C.-C ₄ -alkyl, optionally by C _{1 -C 4 -alkyl, C 1} -C ₄ -AIkOXy, chlorine, bromine, nitro, sulfo or carboxy substituted phenyl or benzyl, trifluoromethyl, C ₁ -C ₄ -alkylcarbonylamino, Cj - ^ - alkylsuflonylamino or optionally by -C - C »-alkyl, C ₁ - C ₄ -AlkOXy, chlorine, bromine, nitro, sulfo or carboxy-substituted benzoylamino or benzenesulfonylamino can be substituted.

Aralkyl R and aralkylene or alkarylene in the bridge member are understood to mean, in particular, benzyl and benzylene, which may be substituted in the phenyl nucleus by C 1-4 alkyl, C ₁ -C ₄ alkoxy, chlorine, bromine, nitro, sulfo or carboxy can.

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Suitable alkyl Rj, R ₂ , Q or D and alkylene E and in the bridge member are in particular Cj-C-alkyl and C ₃ -C ₄ -alkylene, which can be substituted by halogen such as fluorine, chlorine or bromine, hydroxy or cyano.

As groups X which can be split off under reactive dyeing conditions, particular mention should be made of: halogen such as fluorine, chlorine, bromine and iodine, C ₁ -C ₄ alkylsulfonyl, optionally by chlorine, bromine, C 1 -C 4 alkyl, C 1 -C 4 alkoxy , carboxy or SuIfο substituted phenylsulfonyl or benzylsulfonyl, thiocyanato, isothiuronium, tri-Cj-Cg-alkyl ammonium, optionally substituted by C.-C ₄ alkyl, C ₁ -C ₄ -alkoxy, chlorine, bromine, nitro, or carboxy substituted phenyl SuIfο - or benzyl-dialkylammonium, pyridinium, NC ₁ -C ₄ -alky1 ~ morpholinium, NC ₁ -C -alkylpiperidinium, N, N ^L di-C, -C ₄ -alkylpiperazinium or N, N-di-C ₁ -C ₄ -alkylhydrazinium.

Organic or inorganic colorless anions are possible as anions for the ammonium residues mentioned, which have practically no influence on the properties of the dyes. For example, chloride, bromide, Iodide, methosulfate, p-toluenesulfonate, benzenesulfonate, p-chlorobenzenesulfonate, phosphate, acetate, formate and To name oxalate.

The new reactive dyes can be of the most varied Belong to classes, for example the series of metal-free or metal-containing mono- or polyazo dyes, the metal-containing formazans, the metal-free or metal-containing azaporphin dyes such as copper or Nilphthalocyanine dyes, the anthraquinone,

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Oxazine, dioxazine, triphenylmethane, nitro, azomethine, benzanthrone or dibenzanthrone dyes and the polycyclic condensation compounds of anthraquinone, benzanthrone and dibenzanthrones

Preferred dyes correspond to the formula

(ID

X ₁ halogen, in particular fluorine, chlorine or bromine,

¹ -N-CH-SO ₃ H or

D ₁ D ₁

'' N-CH- £

Vi

R ₄ C ₁ -C ₄ -AlCyI, Q ₁ hydrogen or ι D ₁ hydrogen or ι

E ₁ C ₂ -C ₄ alkylene or m- or p-phenylene which is optionally substituted by sulfonic acid groups,

W _{1 is} a direct bond, C ₂ ~ C ₄ alkylene or m- or optionally substituted by sulfonic acid groups

p-phenylene, R ₅ hydrogen or C ₁ -C ₄ -AlkVl and

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U _{1 is} 1 or 2 and F is as defined above.

Very particularly preferred dyes correspond to the formula ^X 2

> ", (HD

F and n .. have the meaning given above,

W_ -CH ₂ ^- CH ₂ - or optionally through 1 or 2 sulfo groups

substituted m- or p-phenylene, R ₆ hydrogen or methyl

or

N-CH ₂ -SO ₃ H CH ₃

X- fluorine or chlorine, D ₂ hydrogen or methyl, E ₂ ethylene or optionally by 1 or

Sulpho groups are substituted m- or p-phenylene.

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Within the formulas (I), (II) and (III), F corresponds to, in the following as a dye

F-H

described without a reactive component, preferably the following formulas.

1. Azo dyes of the formula

A-N = N-B (IV)

wherein

A is the radical of a heterocyclic or carbocyclic diazo component, preferably from the Benzene, naphthalene or triazole series and

B the remainder of a heterocyclic, carbocyclic or CH-acidic coupling component, in particular the remainder of an optionally further substituted phenol, naphthol, aniline, naphthylamine, 5-aminopyrazole, 5-pyrazolones, pyridons, aminopyridines, acetoacetic acid arylides, indoles or pyrimidines represents.

The substituents W, W ₁ and W ₂ are linked to the azo dye via a carbon atom of the diazo component and / or the coupling component.

Particularly valuable dyes of this series are those which have water-soluble groups, such as sulfonic acid or carboxy groups. The azo dyes can be metal-free or in the form of metal complexes, copper, chromium and cobalt complexes being preferred.

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The metal complex-forming groups, preferably hydroxyl, carboxy and amino groups, are in Ortho position to the azo group.

The diazo components A and the coupling components B can, for example, have the following substituents be substituted:

SuIfo, nitro, halogen such as fluorine, chlorine and bromine, optionally C ₁ -C _{alkyl substituted by chlorine, C 1 -C 4} alkoxy, hydroxy or cyano, optionally C 1 -C 4 alkoxy, hydroxy or cyano substituted ₁ -C ₄ -alkoxy, CiC ^ alkylmercapto, Cj-C ^ alkylsulfonyl, optionally phenyl or naphthyl, trifluoromethyl, amino, substituted _{by SuIfο, amino, Cj-C.-alkyl, C 1} -C _{4 alkoxy, nitro or halogen,} Hydroxy, C.-C.-alkylcarbonylamino, C.-C.-alkylsulfonylamino, optionally benzoylamino or benzenesulfonylamino substituted by suIfo, C -C _{-alkyl, C 1 -C 4} -alkyl, nitro or halogen, or benzenesulfonylamino, optionally in the phenyl nucleus SuIfo, C ₁ -C ₄ -AlkYl, C ₁ -C ₄ -AlkOXy, nitro or halogen-substituted phenyl-C. -C ₄ ~ alkyl, optionally in the phenyl nucleus or naphthalene nucleus by hydroxy, amino, sulfo, Cj-C ^ alkyl, C ₁ -C ₄ -AIkOXy, nitro or halogen substituted phenylazo or naphthylazo, Cj-C ^ -alkylcarbonyloxy, optionally by C.-C ₄ -alkyl, C ₁ -C ₄ -alkoxy, nitro or halogen-substituted benzoyloxy, aminocarbonyl, mono- or di-C ₁ -C ^ j-alkylamino, ureido, carboxy, cyano, optionally on nitrogen

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carbonamide or sulfonamide substituted by C ₁ -C ₄ -AlCyI, phenyl or benzyl, where alkyl is substituted by sulfo- or sulfato and phenyl and benzyl by sulfo, C.-C.-alkyl, C ₁ -C ₄ -alkoxy, halogen or nitro may be further substituted, or Cj-C ^ -alkylsulphonylaminosulphonyl or phenylsulphonylaminosulphonyl optionally substituted in the phenyl nucleus by methyl, methoxy, chlorine or nitro.

Preferred azo dyes F-H correspond to the formula

R-

wherein

A ₁ means a phenyl or naphthyl radical which by SuIfo, nitro, chlorine, C ₁ -C ₄ -A ^ yI, C ₁ -C ₄ alkoxy, optionally substituted by SuIfο, amino or C | -C ₄ alkyl-substituted phenyl or naphthyl, amino, acetylamino, optionally substituted by amino, SuIfο or C.-C ₄ alkyl-substituted benzyl, optionally substituted by amino, Cj-C alkyl, SuIfο, C ₁ -C ₄ -alkoxy or hydroxy-substituted phenylazo or naphthylazo or Trifluoromethyl can be substituted,

Z Hydroxy, alkoxy optionally substituted by hydroxy or C ₁ -C ₄ -AIkOXy or optionally substituted by C ₁ -C ₄ -A ^ yI, phenyl or benzyl, where alkyl is substituted by cyano, hydroxy

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or C ₁ -C ₄ -AlkOXy and phenyl and benzyl can be further substituted by methyl, methoxy, chlorine, nitro or sulfo,

R_, R ₀ and R _n independently of one another are hydrogen, C ₁ - / ο y ι

C ₄ alkyl, C ₁ -C ₄ -alkoxy, amino, C -C alkylcarbonylamino, optionally substituted by C, -C ₄ alkyl-substituted phenyl, amino, hydroxy or SuIfο.

Further preferred azo dyes correspond to the formula

R-

A ₁ -N = N

(VI)

wherein

, R-, R _R , Rg and Z have the meaning given above.

More preferred azo dyes correspond to the formula ^R 10s

A ₁ -N = N.

(VII)

wherein

A _{1 has} the meaning given above, Z ₁ amino or hydroxy, R ₁₀ C.-C ₄ alkyl, preferably methyl or carboxy and R ₁₁ optionally by chlorine, Cj-C.-alkyl, sulfo, C ₁ -C ₄ -AlkOXy or amino substituted phenyl or Mean naphthyl.

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Another preferred group of azo compounds corresponds to the formula

HO

(VIII)

wherein A _{1 has} the meaning given above.

Dyes are also particularly valuable

Formula r

^K 7

CO-CH ₃ I / R ₈ A ₁ -N = N-CH-CO-NH- / ^ S (IX)

wherein A .., R ^, Rg and Rg have the abovementioned meaning

to have.

Azo dyes of the formula are also preferred

(X)

HO ^0H

wherein

R ₁₂ C ₁ -C ₄ alkyl or hydroxy,

R ₁ 2 denotes cyano, SuIf0-C ₁ -C.-alkyl or aminocarbonyl and A-) has the meaning given above,

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and the formula

(XI)

R ₁ , - ΗΝ where '->

NH-R

15th

R ₁ -j and A _{1 have} the meaning given above,

R ₁₄ C ₁ -C ₄ alkyl or amino and

R _{15 is} hydrogen or C ₁ -C ₄ -alkyl.

Preferred dyes within the formulas (V) to (XI) are those in which A _{1 is} the radical of an amine of the formula r

(XII)

Ί8

wherein

R _{16 is} hydrogen, sulfo, hydroxy, carboxy or amino,

R _{17 is} hydrogen, chlorine, nitro, aminosulfonyl, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkyl, amino, sulfo, hydroxy or optionally phenyl or naphthylazo substituted in the phenyl or naphthyl nucleus by hydroxy, sulfo or amino, and

R ₁₈ denotes hydrogen, chlorine, nitro, C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkoxy,

and the formulas

16 or R

(XIII)

(XIV)

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represents where

R ₁ g, R ₁ 7 and R ₁ Q have the abovementioned meanings and

R ₁ O denotes hydrogen, chlorine, nitro, aminosulfonyl, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, amino, sulfo, hydroxy or phenylazo or naphthylazo optionally substituted in the phenyl or naphthyl nucleus by hydroxy, sulfo or amino .

2. Anthraquinone dyes of the formula

0 NH ₀

(XV)

where ^Λ 20

L is hydrogen or a substituent, R_ is hydrogen, alkyl or aralkyl and ρ is an integer 1 to 6,

the reactive radical being bonded to the 4-position amino group via the bridge member W.

L preferably represents hydrogen, halogen, in particular chlorine, amino, hydroxy or very particularly preferably sulfo,

R represents hydrogen, C.-C ₄ alkyl or benzyl and ρ represents 1 or 2.

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3. Azaporphine dyes of the formula

■ Ρ WV)! .- «i * * ^V O Ί V AVX j

wherein

Pc is the radical of a _{copper or nickel phthalocyanine optionally substituted by C.-C 4} -alkyl, C ₁ -C ₄ -AlkOXy, SuIfο or optionally by C ₁ -C ₄ -AlkYl, benzyl or phenyl mono- or disubstituted sulfonamide and

R _{? 1 is} hydrogen, alkyl or aralkyl, preferably hydrogen, C ₁ -C ₄ -AlkYl or benzyl and

m 1 to 4 mean.

The reactive group is connected to the bridge link W

Nitrogen atom attached to the sulfonamide group.

Azaporphin dyes are preferred in which Pc is optionally substituted by 1 - 3.5 sulfonic acid or sulfonamide groups substituted copper or nickel phthalocanine.

4. Formazan dyes of the formula

■ I I

N N

^R 22

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wherein

M is a heavy metal atom, preferably a copper atom,

G- and G ~ aromatic carbocyclic or aromatic heterocyclic rings which have the substituents in o-position to the formazan nitrogen atoms wear a and b,

a and b hydrogen, hydroxy, carboxy or aminosulfonyl,

W, a direct bond or a pontic, R is alkyl or aryl and

the aromatic carbocyclic or aromatic heterocyclic rings G ₁ and G- may have further substituents such as Cj-C ₄ -alkyl, C.-C ^ -alkoxy, chlorine, bromine, amino or preferably sulfo.

Suitable aromatic carbocyclic and aromatic heterocyclic rings G ₁ and G- are preferably benzene and naphthalene rings.

Suitable bridge members W ₃ are, for example, -CONH-, -CO- or -SO ₂ .

Suitable alkyl R ₂₂ is optionally substituted by C ₁ -C ₄ -alkoxy-substituted C- | -C ₄ -alkyl.

Suitable aryl R ₂₂ is phenyl or naphthyl optionally substituted by C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkyl, chlorine, bromine, sulfo, amino or phenylazo, the phenylazo groups being substituted by C ₁ -C ₄ -alkyl, C ₁ -C ₄ -AIkOXy, nitro, chlorine, sulfo or amino can be substituted by pus.

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The dyes of the formula (I) are obtained by adding dyes or dye precursors which at least contain an amino, amide or hydroxyl group with at least one reactive hydrogen atom, with compounds the formula

(XVIII)

U is a cleavable residue and

X and Y have the meaning given,

implements.

In the case of dye precursors, these are after Conversion with (XVIII) converted into the desired dyes in a suitable manner, for example by diazotization and Couple.

_{Preferred residues U which can be split off are fluorine, chlorine, bromine, sulfonate, C 1} -C 4 -alkylsulfonyl, tri-C.-C.-alkylammonium, benzyl-di-C.-C.-alkylammonium, C 1 -C. -alkoxy or phenoxy optionally substituted by methyl, methoxy, chlorine, bromine or nitro.

Dyes containing amino or amide groups are preferred or dye precursors reacted with the compounds (XVIII). You work depending on the type of used Starting compounds in organic, organically aqueous or aqueous medium at temperatures of -10 up to 80 C, preferably in the presence of alkaline condensate

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sationsmittel such as pyridine, aqueous alkali or Alkali hydroxide solutions.

U preferably represents halogen such as fluorine, chlorine or bromine.

Another variant of the preparation of the new dyes (I) consists in that one contains amino or amide groups Dyes or dye precursors which have at least one exchangeable hydrogen on the amino or amide group atom have with a compound of the formula

N
X

implements what

U ₁ denotes an anionically exchangeable radical, preferably halogen such as fluorine, chlorine or bromine, and

X and U have the meaning already mentioned.

The product obtained is in any order with the compound of formula

Y-H (XX)

Y has the meaning already mentioned,

implemented and, in the case of dye precursors, the desired dye prepared, for example by diazotization and coupling.

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The compound of the formula (XX), provided it has the formula

R ₁ -NH-CH-SO ₃ HQ

corresponds, is in a manner known per se by condensation in any order from the primary Amine

wherein

R _{1 has} the meaning already given, the aldehyde

Q-CHO wherein
Q has the meaning already given and

Sodium hydrogen sulfite or sulfur dioxide produced.

The compound of the formula (XX) that of the formula

.X

HN-E-N-C N

I I

R ₁ Q

corresponds, by condensation of a compound of the formula (XIX), a diamine of the formula

HN-E-NH,

D D where

D and E have the meaning already mentioned, and one Amine of the formula

HN-CH-SO ₃ HR ₁ Q

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worxn

R. and Q have the meaning already mentioned,

produced in the usual way by condensation in any order.

The dyes obtainable by the processes described above can be further customary for dyes Are subjected to reactions, for example by using metallizable dyes with metal donating agents, especially treated with chromium, cobalt, copper or nickel salts. Dyes that have reducible groups, in particular Nitro groups, can have reduced. Dyes that contain acylatable groups, especially acylatable amino groups have acylated and dyes that can be sulphurized can be mixed with chlorosulphonic acid, thionyl chloride, Oleum or sulfur trioxide are sulfated.

It is preferred to use dyes of the formula containing amide or amino groups

A-N = N-B

-W ₁ -NH R

5 _

(XXI)

wherein

A, B, W-, R ₅ and n- have the meaning mentioned,

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O NH,

(XXII)

L, R _{? N} / W-, R ₁ - and ρ have the meaning mentioned,

-SO ₀ -NW ₁ -NH ^R 21 ^R 5

(XXIII)

_l in

wherein Pc, R

W ₁ , Rr and m have the meaning mentioned and

fr

^W 3

(XXIV)

"5 m

G ₁ , G ₂ , a, b, W ₃ , R ₂₂ # W ₁ and R _{5 have} the meaning mentioned

have and m is 1 or 2,

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with compounds of the formulas (XVIII) or (XIX), the latter reaction being the reaction with compound (XX) follows.

The products of the formulas (XXI) to (XXIV) with compounds of the formula are preferred

^(xxv)

^Y 1

X. and Y .. have the meaning mentioned and U means fluorine, chlorine or bromine

or with compounds of the formula

U (XXVI)

U , Χ-, and Y _{0 have} the meaning already mentioned, 2 ^{z z}

implemented.

The new dyes are valuable products that are suitable for a wide variety of applications. As water soluble Compounds they find preferred interest for the dyeing and printing of hydroxyl-containing and nitrogen-containing Textile materials, in particular textile materials made from native and regenerated cellulose, also made of wool, silk, synthetic polyamide and polyurethane fibers.

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The products are particularly suitable as reactive dyes for dyeing cellulose materials according to the techniques known for this purpose.

For dyeing cellulose, the dyes are preferred used in an aqueous solution that reacts with alkaline substances, such as alkali hydroxide or alkali carbonate, or with compounds that change into alkaline substances, such as alkali bicarbonate can. Further auxiliaries can be added to the solution, but these are not undesirable with the dyes Should react wisely. Such additives are, for example, surface-active substances such as alkyl sulfates or Substances that prevent the migration of the dye or auxiliary products in the dyeing process, such as urea (for improvement solubility and fixation of the dyes), or Indifferent thickeners such as oil-water emulsions, tragacanth, starch, alginate or methyl cellulose.

The solutions or pastes produced in this way are applied to the material to be colored, for example by padding in a padder (short liquor) or by printing, and then ^{heated to an elevated temperature, preferably from 40 to 150 °} C., for some time. The heating can be carried out in the hot flue, in the steamer, on heated rollers or by placing in heated concentrated salt baths, either on its own or in any order one after the other.

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36 2S47312

When using a padding or dye liquor without alkali, passage of the dry goods through one becomes alkaline reacting solution to which common salt or Glauber's salt is added. The addition of salt reduces this the migration of the dye from the fiber.

The material to be colored can also be pretreated with one of the aforementioned acid-binding agents treat with the solution or paste of the dye and finally, as indicated, at an elevated temperature fix.

For dyeing from a long liquor, an aqueous solution of the dye (liquor ratio 1: 5 to 1:40) is added Room temperature and colors 40 to 90 minutes, if necessary by increasing the temperature up to 85 C, under partial addition of salt, e.g. sodium sulfate, and then Alkali, for example sodium phosphates, sodium carbonate or alkalis. This is where the chemical reaction between the dye and the fiber occurs. After chemical Fixing, the dyed material is rinsed with hot water and then soaped, leaving non-fixed residues of the dye removed. The dyeings obtained are extremely fast, in particular wetfast and lightfast.

In the so-called cold padding process, subsequent heating of the padded fabric can be saved by storing the fabric for some time, for example 20 to 40 hours, at room temperature. In this process , a stronger alkali is used than in the dyeing process described above from a long liquor .

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For printing on materials containing hydroxyl groups, a printing paste is made from the dye solution, a thickener, such as sodium alginate and a compound that reacts alkaline or releases alkali when heated, such as sodium carbonate, sodium phosphate, potassium carbonate, potassium acetate or sodium and potassium bicarbonate are used and the printed material is rinsed and soaped.

If the dyes contain groups forming metal complexes, the dyeings and prints can often be treated with metal-releasing agents such as copper salts, e.g. copper sulfate, chromium, cobalt and nickel salts, such as chromium acetate, cobalt sulfate or nickel sulfate, in their fastness properties be improved.

Textile materials containing amide groups, such as wool, silk, synthetic polyamide and polyurethane fibers, are used in the generally dyed by the dyeing methods customary for this purpose in the acidic to neutral range, sometimes with a final Increasing the pH of the dyebath, e.g. to pH 6.5 to pH 8.5, is an advantage.

The dyes are for example on synthetic polyamide fabric applied as solutions or preferably in dispersed form and then, optionally together after-treated with (preferably smaller amounts) acid-binding agents such as sodium carbonate. Particularly favorable results are obtained with dyes that are insoluble or only sparingly soluble in water. These will be after

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conventional techniques and with the addition of the known auxiliaries processed into a dye dispersion and used as such in the dye and / or padding bath or in a printing paste - the auxiliaries suitable for this application include compounds that prevent the migration of the dye on the fiber, such as cellulose ethers, alkali metal chlorides and sulfates, such as condensation products of ethylene oxide and fatty alcohols or phenols, sulphonated fatty alcohols, solvents such as thiodiglycol, also thickeners, such as starch, tragacanth, alginate, gum arabic, etc wetting agent ..

The post-treatment of the dyeings, impregnations and prints obtained on polyamide fiber fabrics is preferably carried out at a temperature of 50-110 C and with a duration from 5 to 60 minutes. Here, too, the colorations can be used in the event that the dyes used form metal complexes Contain groups with metal-releasing agents, such as copper salts, e.g. copper sulfate or chromium, Cobalt and nickel salts, such as chromium acetate, cobalt sulfate or nickel sulfate, are sometimes improved in their fastness properties will.

Draw the colors available with the new dyes generally have good to very good fastness properties, in particular excellent wet fastness properties the end.

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The invention also relates to compounds in the form of the free acid of the formula

Cl

N / "Ν- CH- SO ₃ H (XXVII)

Cl> ^ R ₄ Qi

correspond to where

Q ₁ and R. have the meanings given above,

and the use of these compounds as intermediates for the preparation of reactive dyes.

The compounds (XXVII) are used in particular as alkali and ammonium salts. It is obtained by Cyanuric chloride with amines of the formula

R ₄ -NH-CH-SO ₃ H (XXVIII)

Q- and R _{4 have} the meaning given above,

condensed.

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example 1

13.7 g of methylaminomethanesulfonic acid (MAMS) are added to a suspension, cooled to ^{0 ° C., of 19.4 g of cyanuric chloride in 100 ml of water.} The condensation is brought to an end at 0-5 ° C. within 2 hours with the addition of soda solution (20%). The solution is cleared of small residues of cyanuric chloride and then mixed with 18.8 g of 2,4-diaminobenzenesulfonic acid. The condensation is carried out at 45-50 ° C. and pH 7 is kept constant by adding 20% strength soda solution. This condensation takes about 2 1/2 hours. The end product is a dark brown solution. This solution is adjusted to pH 1 with concentrated hydrochloric acid and diazotized with an aqueous sodium nitrite solution (consumption of 7 g of sodium nitrite dissolved in 25 ml of water). The diazotization is allowed to stir for about 1 hour and then the excess nitrite (potassium iodide starch paper) is removed with sulfamic acid.

30.8 g of 1- (2,5-dichloro-4-sulfophenyl) -3-methyl-5-pyrazolone are dissolved in 100 ml of water, neutralized with sodium hydroxide solution, and cooled to 0.degree. The diazonium salt solution described above is added at this temperature and the coupling is brought to an end by adding sodium acetate solution. The resulting dye is salted out, suction filtered and vacuum drying cabinet at a temperature of about 30 ⁰ C dried with sodium chloride. Cotton or rayon are dyed by this dye in accordance with the printing or dyeing instructions customary for reactive printing or reactive dyeing in lightfast and wetfast, clear greenish yellow shades.

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As a free acid, the dye corresponds to the following formula

H ₃ CN-CH ₂ SO ₃ H

SO ₃ H

If 2,4-diaminobenzenesulfonic acid is replaced in Example 1, 1- (2,5-dichloro-4-sulfophenyl) -3-methyl-5-pyrazolone and Methylaminomethanesulfonic acid (MAMS) by the compounds specified in the table under A, B and C, is obtained one more valuable dyes with the specified shades. EAMS stands for ethylaminomethanesulfonic acid.

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L 17 232 No. A. B. C. Hue on
cotton 2 2,4-diaminobenzenesulfonic acid 5-amino-3-methyl-1 - (2-ethyl-4-
sulfo-phenyl) pyrazole EAMS yellow 3 ■ ι 5-Amino-3-phenyl-1 - (2-methoxy-5-
sulfophenyl) pyrazole MAMS yellow 4th Il Il EAMS yellow 5 2,5-diaminobenzenesulfonic acid Il MAMS yellow OO 6th 2,4-diaminobenzenesulfonic acid 1- (ß-carboxyethyl) -S-pyrazolone-S-
carboxylic acid MAMS greenery,
yellow O
(O
OO ι
VO 7th Il 1- (ß-cyanoethyl) -S-pyrazolone-S-
carboxylic acid MAMS greenery,
yellow 17 / 8th Il 6-hydroxy-1,4-dimethyl-3-sulfo-
methyl-2-pyridone MAMS greenery,
yellow O:
«· * 9 1,4-dianilnobenzene-2,5-disul-
f onic acid Il neutral
yellow 10 2,4-diaminobenzenesulfonic acid 4,6-dihydroxy-1-methyl-3- (N-me-
ethylaminocarbonyl) -2-pyridone EAMS yellow yyyy 11 Il 1-naphthol-4,7-disulfonic acid MAMS Orange red 12th 2,5-diaminobenzenesulfonic acid 2,4-diamino-5-cyano-6- (3-sulfo-
phenyl) pyridine MAMS yellow 13th 2,4-diamino-5-chlorobenzene sulphate
f onic acid (4-Amijno-3,5-disulfophenyl) -
acetoacetanilide MAMS greenery,
yellow 14th 2, 4-Dianiinobenzolsulfonsäure 6-ureido-1-naphthol-3-sulfonic acid MAMS orange ^

No.

Color on cotton

U)

to

15 2,4-diaminobenzenesulfanoic acid

17 1,4-diamine benzene

18 2,5-Diatninobenzenesulfanic acid

19 20

21 2,4-DiantLno-5-methcocybenzenesulfonic acid

22 2,5-diaminobenzenesulfanic acid

23

24

25 4,6-diamino-1,3-benzenedisulfanoic acid 7- (4-sulfophenylamino) -1 -naphthol-EAMS 3-sulfonic acid

8-acetylambio-i-naphthol-3,6-di-MAMS sulfonic acid

p-cresol MAMS

1- (4-sulfophenyl) -S-carboxy-S-MAMS pyrazolone

Barbituric acid MAMS

7-phenyleniino-1-naphthol-3,6-di-MAMS sulfonic acid

"EAMS

7-Amino-1-naphthol-3-sulfonic acid MAMS (sourly coupled)

7-methylamino-1-naphthol-3-sul-EAMS fonsäure (acid coupled)

7-Atdno-1-naphthol-4-sulfonic acid EAMS (sourly coupled)

1- (4-sulfophenyl) -3-sulfanethyl-MAMS 5-pyrazolone

brown red

yellow rotst. yellow

greenish yellow brown

brownish red

Red

Red

red-purple

yellow

£ ■ No. A B

¹ 26 2,5-DiandxK ± ienzenesulfonic acid 5- (2-sulfophenylazo) -6-phenyl-

; amino-1-naphthol-3-sulfonic acid to

27 2,5-diaminonaphthalene-i-sulfonic-8-benzoylamino-1-naphthol-3,6-acid disulfonic acid

28 2,8-diaminonaphthalene-i-sulfonic-8-benzoylamino-1-naphthol-3,5-acid disulfonic acid

29:

co 1 sulfonic acid

P. 30

aa disulfonic acid

C. Hue on cotton MAMS Red MAMS bluest. Red MAMS bluest. Red MAMS Red MAMS Red

Example 31

29.2 g of cyanuric chloride are condensed with 22.5 g of MAMS as in Example 1 at pH 7 and 3 ° C. After the condensation one gives 54.5 g of the disodium salt of 8-amino-1-naphthol-3,6-disulfonic acid are added and the mixture is condensed at 50 ° C. and pH 2.5 (20% strength Soda solution). After the condensation, the pH is adjusted to 6 and the suspension of the diazonium salt of 25.1 g of 2-aminobenzenesulfonic acid added. At this pH value, the coupling is performed (sodium carbonate solution), salted out (sodium chloride) , sucked off and dried in a vacuum. This dye produces strong red prints on cotton and rayon and dyeings. In the form of the free acid, this dye corresponds to the formula

Comparable dyes are obtained by using 2-aminobenzenesulfonic acid, 8-amino-1-naphthol-3,6-disulfonic acid and MAMS
replaced by the compounds listed under A, B and C in the following table.

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U)

U)
U)

No.

6-aminobenzene-1,3-disulfonic acid

33

34 35

36 37 38 39 40 41

42 43

2-aminonaphthalene-4,8-disulfonic acid

2-aminobenzenesulfonic acid

2-amino-5- (4-sulfophenylazo) benzenesulf onic acid

2-Amino-1-sulfcmethyljiaphthalene-5-sulfonic acid

2-amino-5- (4-sulfophenylazo) benzenesulfonic acid

1-Amino-4- (2,5-disulfophenylazo) -naphthalene-6-sulfonic acid

1-Amino-4- (2,5-disulfophenylazo) -3-ureidoaniline naphthalene-6-sulfonic acid

2,5-dimethoxy-4- (2,5-disulfophenylazo) -aniline

3-methyl-1 - / S-amineM, 8-disulfonaphthyl- (2i7-5-pyrazolone

m-Toluidine 6-amino-1-naphthol-3-sulfonic acid

1-aminonaphthalene-6-sulfonic acid

1-aminonaphthalene-7-sulfonic acid

N-ethyl-3-ureidoaniline

4- / 4,8-disulfonaphthylazo (2) J- naphthalene-7-sulfonic acid

1-aminonaphthalene-7-sulfonic acid

1-amino-4- / 4,8-disulfonaphthylazo (2) 7 ~ naphthalene-6-sulfonic acid 1-aminonaphthalene-6,8-disulfonic acid

1-aminonaphthalene-8-sulfonic acid

C. Hue on
cotton MAMS yellow MAMS yellow MAMS orange MAMS bluest,
Red MAMS Red EAMS yellow-brown EAMS red-brown MAMS rotst.
Brown MAMS Brown EAMS Brown

MAMS

brown-red

No.

U)

44 3-.Ainopyrene-5,8,1Otrisulfonic-2,4-diaminobenzenesulfonic acid

8-Amino-1-naphthol-3,6-disulfonic acid

NJ
U) 45 acid NJ aniline

46 2-Att1ino-5-ItethyIbenzolsιllfonsäure

47 2-Ainonaphthalin-i -sulfonsäxire

48 2-aminonaphthalene-1,5-disulfonic acid (1.5)

49

8-amino-1-naphthol-3,5-disulfonic acid

50 2-AmiJio-i-sulfanethylnaphthalene-8-andno-1-naphthol-3,5-disulfone-5-sulfonic acid acid

51 2-MethO3cy-4- (2-sulfophenylazo) -5- 8-amino-1-naphthol-3,6-disulfoninethylaniline acid

C. Hue on
cotton MAMS Scarlet fever
Red MAMS bluest,
Red MAMS Red Bordo red MAMS Red EAMS Red MAMS ruby MAMS blue

Example 52

The diazonium salt of the condensation product prepared as in Example 1 from 57 g of 2,4-diaminobenzenesulfonic acid and 58 g of cyanuric chloride and 45 g of MAMS are added to 0.3 mol of the disodium salt of 8-amino-1-naphthol-3,6-disulfonic acid at pH 2.5 coupled.

The solution of the aminoazo dye is made with the diazonium salt coupled from 52 g of 2-aminobenzenesulfonic acid at pH 7 to 8 (sodium hydroxide solution). The dye will salted out, vacuumed, dried and corresponds to the

formula

OH NH ₂

HP ₅ S

N = N-SO ₃ H

CH ₂ SO ₃ H

Cotton and rayon are dyed in lightfast and washfast blue-gray tones.

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Example 53

The same components as in Example 52 are used, but 2-aminobenzenesulfonic acid is first coupled at pH 2.5 on 8-amino-1-naphtho1-3,6-disulfonic acid and then that Diazonium salt from the condensation product of 2,4-diaminobenzenesulfonic acid. Cyanuric chloride and MAMS at pH 7 to 8 on the monoazo dye, a dye is obtained which dyes cotton or rayon in blue-gray tones. In the form of the free acid, it corresponds to the formula

'SO ₅ HHO ₅

Example 54

A solution of 13.8 g of sodium nitrite and 41.6 g of the disodium salt of 4,4'-diamino-5,5'-dimethyldiphenyl-2.2 ^l -disulfonic acid in 450 ml of water is cooled to 0-5 ° C. and then slowly added with stirring to 70 ml, cooled to 0-5 ⁰ C of concentrated hydrochloric acid. The mixture is left to stir for 2 hours

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and then destroys the excess of sodium nitrite by adding sulfamic acid.

The solution of the condensation product of 38.7 g of cyanuric chloride and 27.5 g Methylaminomethansulfonsäure is treated with 38.4 g acetoacetate (4-aminoanilide) and condensed 7 and about 50 ⁰ C with the addition of 20% sodium carbonate solution at pH. After the condensation, the solution is cooled to 0-5 ⁰ C and added the diazonium salt solution. With the addition of soda solution, the coupling is carried out, the dye is salted out, filtered off with suction and dried. In the form of the free acid, it corresponds to the formula

H ₃ CN-CH ₂ -SG ₃ H _-

and dyes cotton and rayon yellow. Example 55

According to Example 1, the diazonium salt of the condensation product is prepared from 75.2 g of 2,5-diamino-benzenesulfonic acid, 77.5 g of cyanuric chloride and 60 g of methylaminomethanesulfonic acid.

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72.6 g of the disodium salt of 8-amino-1-naphthol-3,6-disulfonic acid are first at pH 2.5 with one half and then at pH 8 with the second half of the above Diazonium salt coupled. It is then salted out, filtered off with suction and dried in vacuo. Be with the dye Cotton and rayon dyed or printed in blue-tinged gray tones. In the form of the free acid it corresponds to formula

' ^S ° 3 ^H OH NH ₂

, Cl

CH ₂ SO ₈ H

Example 56

The solution of the diazonium salt obtained according to Example 1, paragraph 1 from the amine obtained by the condensation of cyanuric chloride, MAMS and 2,4-diaminobenzenesulfonic acid is coupled to the solution of the coupling component at 0 C and pH 7, which is produced by condensation of 1- (4-aminophenyl) -S-sulfomethyl-S-pyrazolone, cyanuric chloride and MAMS in

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Lehung on Example 31 is obtained. The dye obtained after uncoupling, salting out, suction and drying formula

H-N

SO..H CH _O -SO, H N = N - <^ I

C ^ ₁

CH-I J N-CH ₂ -SO-H

Cl

dyes cotton in wet-fast yellow tones.

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No. diazo component

Coupling component

O
CD
OO

U)

Remainder on the cyanuric chloride

57 2,4-Diatninobenzenesulfonic acid

58 2,5-diaminobenzenesulfonic acid

59 2- (3-sulfo-4-aminophenyl) -5,9-disulfo-7-aminonaphthotriazole

60 2,6-diaminonaphthalene-4,8-disulfonic acid

61 2,5-diaminobenzenesulfonic acid

62 "63

64 2,4-diaorninobenzenesulfonic acid 65

1- (3-aminophenyl) -5-pyrazolonecarboxylic acid

1- (4-aminophenyl) -5-pyrazolone-3-carboxylic acid

m-Touidin

6-amino-1-naphthol-3-sulfonic acid 7-amino-1-naphthol-3-sulfonic acid

8-amino-1-naphthol-3,6-disulfonic acid

8-amino-1-naphthol-3,5-disulfonic acid

EAMS

MAMS MAMS

MAMS

Shade on cotton

rotst. yellow

rotst. yellow yellow

golden yellow

MAMS yellow. Red MAMS red-brown MAMS Red MAMS Red EAMS Red

Example 66

137.7 g of the copper complex azo dye, from the diazonium salt of 2-amino-5-sulfobenzenecarboxylic acid by coupling with 3-methyl-1 - / 6-amino-4,8-disulfonaphthyl- (2) _ / - 5-pyrazolone and Copper plating in acetate-buffered solution with copper (II) sulfate solution obtained, are dissolved in 3.5 l of water at pH 5 and cooled to 2 ° C. 38.8 g of cyanuric chloride are added and keeps pH and temperature constant. After the condensation, 30 g of MAMS are added, heated to 50 ° C. and made with 20% soda solution to pH 7. It is salted out at room temperature, filtered off with suction and dried. The dye that is in the form the free acid of the formula

SO ₅ H

Cu complex

N-CH ₈ CH ₂ SO ₃ H

corresponds, dyes cotton and rayon in a very lightfast and washable yellow.

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ssr

Example 67

18.9 g of 2-aminophenol-4-sulfonic acid are diazotized and with pH 8 coupled to 31.9 g of 8-amino-1-naphthol-3,5-disulfonic acid. After coupling, the mixture is heated to 90 ° C. for 1 hour at pH 5 with 16 g of copper sulfate. The copper complex azo dye is salted out and sucked off. The moist paste is dissolved in 600 ml of water and condensed at pH 4.5 and 2 ° C first with 19.4 g of cyanuric chloride and then at pH 7 and 50 ° C with 13.7 g of MAMS, each with the aid of 20% soda solution · It is salted out, filtered off with suction and dried in vacuo. Cellulose fibers are made from this dye colored blue-violet. In the form of the free acid, it corresponds to the formula:

SO ₃ H

SO ₃ H

Cu complex

Further copper complex reactive dyes are obtained if instead of 2-aminophenol-4-sulfonic acid, 8-amino-1-naphthol-3,5-disulfonic acid and MAMS uses components A, B and C listed in the table below.

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No.

ex" ι O CD OO I. - » -J -s, O

68 69

70 71 72

2-amino-5-sulfobenzoic acid 6-Amino-1-naphthol-3-sulfonic acid

MAMS

2-aminonaphthalene-4,8-disulfonic acid

7 3 2-Anüjio-6-nitronaphthalene-4,8-disulfonic acid

- (β-Aminoäthylaitiino) -1 -naphthol- MAMS

3-sulfonic acid

6- (3-Amino-4-sulfophenyl) -1-naph-MAMS thol-3-sulfonic acid

8-Amino-1-naphthol-3,5-disulfonic acid MAMS

8-Aminc) -1-naphthol-3,6-disulfonic acid MAMS 6-amino-1-naphthol-3-sulfonic acid MAMS

74 2,4-diaminophenol-6-sulfanic acid 8- (3-sulfophenylaminocarbonvlamino) -

1-naphthol-3,5-disulfonic acid

75 2,4-diaminophenol ■ 8-amino-1-naphthol-5,7-disulfonic acid MAMS

76 6-Amino-2-naphthol-4-sulfonic acid 8-Amino-1-naphthol-5,7-disulfonic acid MAMS

77 2,4-Diaminophenol-5-sulfonic acid 1- (4-sulfophenyl) -5-pyrazolone-3-EAMS

•: carboxylic acid

78 4- (2-sulfophenyl) -2-metoxy-5-methylaniline

79 2,5-diaminobenzenesulfonic acid

6-amino-1-naphthol-3,5-sulfonic acid

EAMS

4- (2-Hydroxy-4-sulfophenylazo) -resor- MAMS a

Shade on cotton

brownish red

bluish purple

bluish purple

rotst. blue

bluish, red blue

bluish, purple

bluish, purple

blue brown

blue brown

Example 80

109 g of the from the diazonium salt of 8-amino-1-phenylsulfony are dissolved loxynaphthalene-3,6-disulfonic acid by coupling at pH to 6-acetylamino-1-naphthol-4,8-disulfonic acid, oxidative Copper plating with copper sulphate and hydrogen peroxide and hydrolysis of the N-acetyl and O-phenylsulphonyl groups Copper complex azo dye neutral in 4 l of water, and condensed successively with 29.5 g of cyanuric chloride at pH 6 and 0 to 5 ° C and with 20.5 g MAMS at pH 7 and 55 ° C. In the form of the free acid, it corresponds to the formula

HO ₃ S,

SO ₃ H

HO ₃ S OH

HO SO ₈ H

CH ₂ SO ₃ H

Cu complex

and dyes cotton and rayon blue. Example 81

In Example 80, 8-amino-1-phenylsulfonyloxynaphthalene-3 is replaced , 6-disulfonic acid by the equivalent amount of 8-amino-1-phenylsulfonyl-naphthalene-3,5-disulfonic acid, so you get a dye that dyes cotton and rayon in very real shades of blue.

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Example 82

18/9 g of diazotized 2-aminophenol-4-sulfonic acid are added 64.7 g of the from the diazonium salt of 6-amino-1-naphthol-4,8-disulfonic acid by coupling to 6-amino-1-naphthol-3-sulfonic acid and subsequent oxidative coppering coupled copper complex azo dye. After salting out and vacuuming the moist dye paste is dissolved in 13 l of water, coppered a second time with 25 g of copper sulfate at pH 5 and 50 ° C. in one hour and isolated again. In 1.9 l of water, the dye paste is stirred and first condensed with 19.4 g of cyanuric chloride at pH 5 and 3 C and then with 13.7 MAMS at pH 7 and 55 ° C. The dye, that in the form of the free acid of the formula

HO ₃ S.

Bis-copper complex , cotton and rayon dyes blue.

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Example 83

47.4 g of the by coupling the diazonium salt of 2-amino-4,6-dinitrophenol to 2-aminonaphthalene-6-sulfonic acid and subsequent cobalting with cobalt sulfate heptahydrate
pH 5 and room temperature obtained 1: 1 complex
in 1250 ml of water at pH 11 and 45 ° C. with 55.4 g of the azo dye obtained by coupling the diazonium salt of 2-amino-4-nitrophenol-6-sulfonic acid to 6-amino-1-naphthol-3-sulfonic acid, for 1 : 2-cobalt complex implemented. This reaction takes about 2.5 hours. Then it is salted out with table salt and suctioned off.

The paste is suspended in 1.5 l of water and added with 27.3 g of the condensation product of cyanuric chloride and MAMS pH 7 and 50 ° C condensed.

It is then salted out, filtered off with suction and dried in vacuo. The asymmetrical 1: 2 cobalt complex produced in this way dyes cotton and rayon in dark brown shades.
In the form of the free acid, it corresponds to the formula

SO ₃ H

O ₂ N

N-CEjSO ₈ H
CH ₈

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■ Symmetrical 1: 2 cobalt complex azo dyes are obtained, if the diazo component is the compounds A and the coupling component is the compounds B of the following Table used.

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No.

Shade on cotton

84 2-aminophenol-4-sulfonic acid Acetoacetic acid (4-aminoanilide)

yellow

co I. O co co OO - »

sulfanic acid

85 2-imix> -4-metrol-6-sulfone-4-aminophenol acid

86

87 2-Amino-4-nitro-phenol

88 1-Aninc> ^ - nitro-2-rhenol-4-sulfonic acid -5.7-di-

8-aman-1-naphthol-3,6-disulfonic acid

2-amino-5-naphthol-7-sulfonic acid

Brown

rotst. Brown

Gray

Gray

Example 89

If, in Example 83, the metal-free azo dye is replaced by the equivalent amount of that obtained by coupling at pH 8 from the diazonium salt of 2-amino-4,6-dichlorophenol 8-amino-1-naphthol-3,6-disulfonic acid produced azo dye, in this way a dye is obtained which dyes cotton and rayon navy blue. Corresponds in the form of the free acid he's the formula

Example 90

77.8 g of the dye prepared from 2-amino-6-nitrophenol-4-sulfonic acid and 2-naphthol by diazotization and coupling are stirred in 500 ml of water at 80.degree.

The 1: 1 chromium complex is carried into this suspension at pH 8 for 1 hour a, which one by diazotizing 44.7 g of 2-amino-4-chlorophenol-6-sulfonic acid, coupling at pH 8 on 72.6 g of 8-amino-1-naphthol-3,5-disulfonic acid, chromating with 32 g chromium trichloride is obtained in acidic solution, salting out and suction.

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The asymmetrical 1: 2 chromium complex azo dye is isolated between condensed with 38.8 g of cyanuric chloride at pH 5 and 3 ° C and with 27.4 g of MAMS at pH 6.5 and 45 ° C. Man salt out, vacuum and dry. The dye in the form of the free acid of the formula

N-CH ₈ CH ₈ SO ₈ H

SO ₈ H

corresponds, dyes cotton and rayon blue-gray. Example 91

In Example 90, 2-amino-4-chlorophenol-6-sulfonic acid is replaced by the corresponding amount of 2-amino-4-nitrophenol-6-sulfonic acid, in this way an asymmetrical 1: 2 chromium complex dye is obtained with which cellulose materials can be dyed or printed in blue-gray tones. Symmetrical 1: 2 chromium complex azo dyes of the following Table are obtained if the diazo component is used in column A and the coupling component in column B specified compounds according to the procedure of Example 90, with cyanuric chloride and finally with the in column C compounds mentioned condensed.

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Le A 17 No. A. B. C. Hue on
cotton 232 92 2-aminobenzoic acid 6-Amino-1-naphthol-3-sulfonic acid MAMS Brown 93 Il 6-amino-1-naphthol-3,5-disulfone
acid MAMS Brown 94 2-amine> -4-chlorophenol 8-Amino-1-naphthol-3,6-disulfone
acid MAMS blue-gray 608 95
96 Il
2-amino-4-nitrophenol 8-amino-1-naphthol-3,5-disulfone
acid
Il EAMS
EAMS blue-gray
blue-gray co 97 2-atnina-5-nitropheriol Il MAMS blue-gray 7/011 I.
ui
I. 98
99 Il
2-amino-4-nitxo0ienol 8-amino-1-naphthol-3,6-disulfone
acid
Il MAMS
MAMS blue-gray
blue-gray 100 1-amino-6-nitro- 2-Amino-5-naphthol-7-sulfQn- MAMS Gray

2-naphthol-4-sulfonic acid

acid

Example 101

In Example 90, 8-amino-1-naphthol-SjS-disulfonic acid is replaced by the equivalent amount of 8-amino-1-naphthol-3,6-disulfonic acid, a dye is obtained with which one Can dye or print cotton and rayon blue-gray.

Other excellent gray to black dyes are obtained by mixing cobalt and chromium complex dyes obtained, for example by mixing Example 100 with Example 88 and Example 99 with Example 87, the mixing ratio can vary between 30:70 and 70:30.

Example 102

19.4 g of cyanuric chloride are added to 100 ml of water with 18.8 g 2,4-Diaminobenzenesulfonic acid condensed at pH 5 and 3 ° C. It is then acidified with concentrated hydrochloric acid and diazotized with an aqueous sodium nitrite solution. Man lets stir for an hour and removes the excess of sodium nitrite with sulfamic acid.

30.8 g of 1- (2,5-dichloro-4-sulfopheny}) -3-diethyl-5-pyrazolone are in 150 ml of water with the aid of sodium hydroxide solution dissolved neutrally and cooled to 0 ° C. The diazonium salt solution is added and the coupling is carried out at pH 4 bis

After the coupling is first condensed with 6.1 g of ethylenediamine at 40 ° C and pH 6, and then with 19.4 g of cyanuric chloride at pH 6 and 3 ° C, and finally with 13.7 g MAMS at 50 ⁰ C and pH. 7 The dye is salted out, filtered off with suction and dried in vacuo. In the form of the free acid, it corresponds to the formula

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C ^ ₅ SO ₃ H

Cellulose materials are stained with a greenish yellow, extremely washable, by this dye.

Other valuable bis-reactive dyes are obtained if one instead of 2,4-diaminobenzenesulfonic acid, 1- (2,5-dichloro-4-sulfophenyl) -3-methyl-5-pyrazolone, Ethylenediamine and MAMS use the compounds given in the following table under A, B, C, D.

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No.

LO to shade on cotton

103 2,4-diandnobenzenesulfanic acid

104

105 2 , 5-diaminobenzenesulfonic acid

106 2-itamo-5-iiethoxybenzenesulfonic acid (2,5-dichloro-4-sulfophenyl) ■
3-methyl-5-pyrazolone

(2-methyl-4-sulfophenyl) -3-methyl-5-aminopyrazole

6-amino-1-naphthol-3-sulfonic acid

N-methyl-EAMS yellow ethylenediamine

p-phenylene MAMS yellow diamine

N, N-Dimethyl-MAMS yellow ethylenediamine

4,6-diamino- MAMS scarlet benzene-1,3-disulfonic acid

Example 107

159.9 g of the disodium salt of the condensation product from equivalent amounts of 1-amino-4-bromoanthraquinone-2-sulfonic acid and 2,4-diaminobenzenesulfonic acid are dissolved in 4 l of water, cooled to 0 C and treated with a solution of 58.1 g of cyanuric chloride in 240 ml of acetone at pH 5-5.5 and 0-5 ° C are added. After the condensation, 45 g of MAMS are added and the second condensation is carried out at 50 ^° C. and pH 7. The dye is salted out, filtered off with suction and dried in vacuo. The dye stains cotton and cellulose in washable and lightfast reddish blue tones. In the form of the free acid, it corresponds to the formula _Λ

CH ₂ SO ₃ H

Other valuable anthraquinone dyes are obtained, if 2,4-diaminobenzenesulfonic acid is replaced by the amino compounds given in the table below.

Mr. Diamino Compound Shade on Cotton

108 1,4-diamino-2,3,5,6-tetramethyl blue benzene

109 4,4-diaminobiphenyl-3-sulfonic acid blue

110 4,4'-diaminostilbene-2,2'-disulfonic acid blue

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Example 111

106.5 g of the copper complex dye of the formula

wherein Cu-Pc denotes copper phthalocyanine and the sulfonic acid and sulfonamide groups are in the 3-position, are condensed with 58 g of cyanuric chloride at 0-5 ⁰ C and pH 6.5 and then with 41 g MAMS at 45 ° C and pH 7 implemented. After salting out, suctioning off and drying, a dye is obtained with which cotton and rayon can be dyed or printed in bright blue tones. In the form of the free acid, it corresponds to the formula

Cu-Pc

SO ₃ H

, SO ₃ H .Cl

Example 112

In Example 111, 2,5-diaminobenzenesulfonic acid is replaced by the equivalent amount of ethylenediamine, you get a corresponding dye, with which cotton or cellulose in can color brilliant shades of blue.

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Example 113

63.1 g of 3,10-di- (β-aminoethylamino) -6,13-dichlorotriphenyldioxazine-4,11-disulfonic acid are suspended in 1.5 l of water with the condensation product of 18.4 g of cyanuric chloride and 12.5 g MAMS implemented at pH 6-7 and a temperature of 30-35 C. It is salted out, filtered off with suction and dried in vacuo. The dye dyes cellulose fibers blue.

H ₀ NCH ₀ -CH-NH 2 2 2

I _x NH -CH ₀ -CH ₀ -NH

Cl

CH ₂ SO ₃ H

Example 114

The diazonium salt from 22.1 g of 2-aminophenol-4-sulfonic acid is coupled to 19.2 g of U- formylphenyl acetic acid ethyl ester at pH 8. The mixture is boiled for 30 minutes at pH 10 and the solution of the saponification product is coupled at pH 5 with the diazonium salt of 23.0 g of 2-amino-5-acetylaminobenzenesulfonic acid.

The acetylamino group is then saponified by heating at 9.5 for one hour, and the formazan dye is salted out, isolated and reacted at pH 3 with 25.0 g of copper (II) sulfate pentahydrate. Salt and isolate. The moist phase is successively with 19.4 g of cyanuric chloride at pH 5 and 2 ° C and 13.7 g MAMS condensed at pH 7 and 50 ° C. Cotton and rayon are made with the dye of the formula

Le A 17 232

- 57 -

8 0 9 8 1 7 / ö Π 3

HO ₃ S '

CK ₂ -SO ₅ H

Cu complex

Colored lightfast and washfast blue.

Example 115

The diazonium salt from 73.8 g of 2-amino-6-acetylaminophenol-4-sulfonic acid is coupled at pH 9 to the hydrazone, prepared from 31.8 g of benzaldehyde and 45.6 g of 2-hydrazinobenzoic acid. The acetylamino group is then saponified at pH 10 by heating to 95 ° C. for one hour. With more concentrated Hydrochloric acid is adjusted to pH 3 and the formazan is reacted with 75.0 g of copper (II) sulfate pentahydrate.

After salting out and filtering, the moist phase is stirred in 1.5 g of water and added successively with 58.2 g of cyanuric chloride pH 6.5 and 3 ° C and with 41.1 g MAMS at pH 7 and 50 ° C condensed. With the dye, which is in the form of the free acid formula

Le A 17 232 - 58 -

009817/0113

SO ₈ H CB ₂ SO ₃ H

Cu complex

cotton and cellulose can be dyed or printed in lightfast and washfast blue shades.

Example 116

0.1 mole of the hydrazone, prepared from 2-hydrazino-4-sulfobenzoic acid and 4-amino-2-formylbenzenesulfonic acid are dissolved neutral in 500 ml water, acidified and diazotized at 0-5 ⁰ C and aqueous sodium nitrite solution. The mixture is stirred for one hour, excess nitrite is destroyed with sulfamic acid and 12.6 g of barbituric acid are sprinkled in. The coupling is carried out at pH 6-7.

The dye is isolated between and dissolved in 600 ml of water. At pH 8-9, the diazonium salt from 36.0 g of 2-amino-6- ^ 4-chloro-6- (N-methyl-N-sulfomethylamino) -triazinyl- (2) _7-phenol is added and the coupling is carried out at pH 8-9 finished. It is then reacted with 75.0 g of copper sulfate pentahydrate at pH 11, salted out, isolated and dried in vacuo. With the dye, which is in the form of the free acid of the formula

Le A 17 232 - 59 -

809817/0113

HO ₃ S

/ CH ₂ SO ₃ H

Cu complex

cotton and rayon can be dyed or printed dark green.

Example 117

Replace barbituric acid in Example 116 with the equivalent Amount of 5-amino-3-methyl-1- (4-methyl-2-sulfophenyl) pyrazole, so a dye is obtained which dyes cotton and rayon olive. In the form of the free acid, it corresponds to the formula

Cl

N-CH ₂ SQ ₅ H CH ₃

/ W w

HO ₈ S

NH ₂ SO ₃ H

Le A 17 232

Cu complex - 60

809817/0113

Example 118

137 g MAMS are at pH 7 and 0-5 ° C for 2 hours with a Suspension of 2.5 l of water and 184.5 g of cyanuric chloride reacted.

Small residues are then filtered off, the filtrate potassium chloride is added, the precipitate is filtered off with suction and dried in vacuo at room temperature. You get one colorless, crystalline precipitate, that of the formula

Cl

he

is equivalent to.

The elemental analysis gives the following values:

Calc .: 19.3% C 1.6% H 22.8% Cl 18.0% N 10.3% S Found: 19.5% C 1.7% H 22.4% Cl 18.1% N 10.5% S.

Le A 17 232 - 61 -

809817 / Ot13

Claims (21)

Claims 9 fi Λ 7 "VI 2 1) reactive dyes of the formula ^R 2 / Y wherein X is a cleavable under reactive dyeing conditions Group,
Y -N-CH-SO ₃ H or R ₁ Q N-CH-SO "Η R ₁ Q R ₁ optionally substituted alkyl, R _{2 is} hydrogen, optionally substituted alkyl or aralkyl, F is the radical of an organic dye, W and V are a direct bond or a bridge member, Q is hydrogen or optionally substituted alkyl, D is hydrogen, optionally substituted alkyl or aryl, E optionally substituted alkylene or arylene and η 1,2,3 or 4 mean. Le A 17 232 - 62 - 809817/6113 2) reactive dyes according to claim 1 of the formula wherein X ₁ halogen, in particular fluorine, chlorine or bromine, or ^R 4 ^Q 1 D ₁ υ. -s ¹ 'N-CH-SO ₃ H ^R 4 C ₁ -C ₄ Q ₁ hydrogen or D ₁ hydrogen or E ₁ C ₂ -C ₄ alkylene or m- or p-phenylene which is optionally substituted by sulfonic acid groups, W _{1 is} a direct bond, C ₂ -C ₄ alkylene or m- or optionally substituted by sulfonic acid groups p-phenylene,
R _{5 is} hydrogen or C ₁ -C ₄ -alkyl and n _{1 is} 1 or 2 and F is as defined in claim 1. Le A 17 232 - 63 - 809817 / 0H3 3) reactive dyes according to claim 1 of the formula ^Y 2 wherein F and n _{1 have} the meaning given in claim 2, W ₂ -CH ₂ -CH ₂ - or optionally by 1 or 2 sulfo- group-substituted m- or p-phenylene, Rf- hydrogen or methyl -N ' or -NE ₂ -N- ^ _N D ₂ D ₂ ^ < N-CH ₂ -SO ₃ H CH ₃ Fluorine or chlorine, Hydrogen or methyl, Ethylene or optionally by 1 or 2 Sulfo-substituted m- or p-phenylene mean . Le A 17 232 - 64 - 809817/0113 4) reactive dyes according to claim 1 of the formula AN = NB "'' wherein V, W, X, Y, R ₂ and η have the meaning given in claim 1, A is the remainder of a heterocyclic or carbocyc union diazo component, preferably from the benzene, naphthalene or triazole series and B the remainder of a heterocyclic, carbocyclic or CH-acidic coupling component, in particular the remainder of an optionally further substituted phenol, naphthol, aniline, naphthylamine, 5-aminopyrazole, 5-pyrazolones, pyridones, aminopyridines, acetoacetic acid arylides, indoles or pyrimidines represents and the substituent W via a carbon atom of the diazo component or the coupling component with the an azo dye is linked. 5) reactive dyes according to claim 1 of the formula Le A 17 232 - 65 - 809817 / 0T13 wherein V, W, X, Y, R- and η have the meaning given in claim 1 own and A ₁ denotes a phenyl or naphthyl radical, phenyl or naphthyl which is optionally substituted by sulfo, nitro, chlorine, C ₁ -C ₄ -alkYl, C ₁ -C ₄ -alkoxy, optionally substituted by sulfo, amino or C ₁ -C _{4 -alkyl} , Amino, acetylamino, benzyl optionally substituted by amino, sulfo or C ₁ -C ₄ alkYl, optionally substituted by amino, C ₁ -C ₄ alkYl, sulfo, C ₁ -C ₄ alkoxy or hydroxy substituted phenylazo or naphthylazo or trifluoromethyl can be substituted, Z Hydroxy, alkoxy optionally substituted by hydroxy or C ₁ -C ₄ -AlkOXy or optionally substituted by C ₁ -C ₄ -AlkYl, phenyl or benzyl, where alkyl is substituted by cyano, hydroxy or C ₁ -C ₄ -AlkOXy and phenyl and Benzyl can be further substituted by methyl, methoxy, chlorine, nitro or sulfo, R ^, Rg and Rg independently of one another are hydrogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkyl, amino, Cp ^ -alkylcarbonylamino, phenyl, amino, hydroxy or sulfo which is optionally substituted _{by C 1} -C _{4 -alkyl} mean and Le A 17 232 - 66 - 809817/0113 the substituent W is linked to the azo dye via a carbon atom of the diazo component or the coupling component. 6) reactive dyes according to claim 1 of the formula -N = N W-N-V wherein V, W, X, Y, R2 and η have the meaning given in claim 1 own and A., R7, Rg, Rg and ζ the meaning given in claim 5 to have. 7) reactive dyes according to claim 1 of the formula Le A 17 232 - 67 - 809817/0113 wherein V, W, X, Y, R "and η have the meaning given in claim 1 own, A ₁ the Be specified in claim 5 meaning and Z ₁ amino or hydroxy, R. C ₁ -C ₄ -AlkYl, preferably methyl or Carboxy and R ₁₁ possibly by chlorine, C ₁ -C ₄ - Alkyl, SuIfo, C ₁ -C ₄ -AIkOXy or amino-substituted phenyl or naphthyl mean,
and W via a carbon atom of the diazo component or the coupling component is linked to the azo dye. 8) reactive dyes according to claim 1 of the formula wherein V, W, X, Y, R ₂ and η have the meaning given in claim 1 and A ₁ the Be specified in claim 5 have meaning and W via a carbon atom with the diazo component te is linked. Le A 17 232 - 68 - 809817/0113 9) reactive dyes according to claim 1 of the formula CO-CH ₃ A ₁ -N = N-CH-CO-NH R ₉ wherein V, W, X, Y, R ₂ and η are those in claim 1 and A ₁ , R ₇ , Ro and R_ have the meaning given in claim 5 and W via a carbon atom of the diazo component or the coupling component is linked to the azo dye. 10) reactive dyes according to claim 1 of the formula R ₁₀ , ^Λ1 X , -N = N HO OH wherein V, W, X, Y, R ₂ and η are given in claim 1 and A ₁ given in claim 5 have meaning R ₁₂ C ₁ -C ₄ alkyl or hydroxy and R ₁₃ cyano, SuIfO-C ₁ -C ₄ ~ alkyl or amino mean carbonyl and Le A 17 232 - 69 - 809817 ^ 0113 W via a carbon atom of the diazo component or the coupling component is linked to the azo dye. 11) reactive dye according to claim 1 of the formula A ₁ -N = N NH-R ₁ . 1 5 wherein V, W, X, Y, R ₂ and η have the meaning given in claim 1, A ₁ and R ₁ 2 have the meaning given in claim 10, R ₁₄ C ₁ -C ₄ alkyl or amino and R ₁ C denotes hydrogen or C ₁ -C _{4 -alkyl} ten and W via a carbon atom of the diazo component or coupling component is linked to the azo dye. 12) reactive dyes according to claim 1 of the formula W-N-V- ^ N R 20 ^ - L Ν ^ Λ Le A 17 232 - 70 - 809817/0113 wherein V, W, X, Y, R ₂ and η have the meaning given in claim 1 and Hydrogen or a substituent, R hydrogen, alkyl or aralkyl and ρ is an integer 1 to 6. 13) reactive dyes according to claim 12, wherein L stands for hydrogen, halogen, amino, hydroxy or sulfo, R 2o stands ^for hydrogen, Cj-C ₄ -alkyl or benzyl and ρ stand for 1 or 2. 14) reactive dyes according to claim 1 of the formula Pc SO ₀ - N R. 21 y wherein V, W, X, Y, R ₂ and η have the meaning given in claim 1, Pc is the radical of a copper or nickel phthalocyanine optionally substituted by _{C 1} -C ₄ -alkyl, C _{1 -C 4 -AlkOXy, SuIfο or optionally mono- or disubstituted by Cj-C 4} -alkyl, benzyl or phenyl and R _{21 is} hydrogen, alkyl or aralkyl, preferably hydrogen, C ₁ -C ₄ -A ^ yI or benzyl and m 1 to 4 mean. Le A 17 232 - 71 - 809817/0113 15) reactive dyes according to claim 1 of the formula a. ■ I wherein V, W, X, Y, R ₂ and η have the formula given in claim 1 own, M is a heavy metal atom, preferably a copper atom, G ₁ and G _{0 are} aromatic, carbocyclic or aromatic herterocyclic rings that carry the substituents a and b in the o-position to the formazan nitrogen atoms, a and b are hydrogen, hydroxy, carboxy or aminosul- fonyl, Wj is a direct bond or a bridge member, R ₂ 2 is alkyl or aryl and the aromatic carbocyclic or aromatic heterocyclic rings G ₁ and G _{2 can have} further substituents such as C ₁ -C ₄ -AlkYl, C ₁ -C ₄ -AIkOXy, chlorine, bromine, amino or preferably sulfo. Le A 17 232 - 72 - 809817/0113 16. Process for the preparation of dyes according to claim 1, characterized in that dyes or dye precursors which contain at least one amino, amide or hydroxyl group with at least one reactive hydrogen atom are mixed with compounds of the formula ^ü A 'J U is a removable radical and X and Y have the meaning given in claim 1, converts and in the case of dye precursors, the conversion products converted into the dyes in a suitable manner. 17. A method for the preparation of dyes according to claim 1, characterized in that dyes containing amino and amide groups or dye precursors which are attached to the amino or the amide group have at least one exchangeable hydrogen atom, with a compound of the formula implements what U ^ an anionically exchangeable radical, preferably Halogen such as fluorine, chlorine or bromine means U is a removable radical and X has the meaning given in claim 1 , Le A 17 232 - 73 - * ₍ 809817/0113 and the product obtained in any order with the compound of the formula Y-H wherein Y has the meaning given in claim 1, converts and, in the case of dye precursors, the Finishes dye in the usual way. 18. Process for dyeing and printing hydroxyl groups and nitrogenous textile materials, thereby characterized in that the dyes according to claim 1 are used. 19. With the dyes according to claim 1 dyed and printed hydroxyl-containing and nitrogen-containing Textile materials. 20. Compounds of the formula Cl N / Vn-CH-SO-H ^ Ni! ³ Cl ^R 4 ^Q 1 wherein R- and Q _{1 have} the meaning given in claim 2. 21. Use of compounds according to claim 20 as intermediates for the preparation of reactive dyes. L «A 17 232 - 74 - 809817/0113