DE2360708C3 - Polyazostilbene dyes and their use - Google Patents

Description

The invention relates to polyazo dyes in the form of the free acid of the formula

A -N = N-

- CH ■ - ·

SO, H

H, N OH

-N = N- ^{; V} "■ '■"' TN = N- D

correspond, in which R is an o- or p-position by a C, -C ₄ -alkyl radical etherified hydroxyl group. D door a possibly by C ₁ -C ₄ -AIk) I. C ₁ -C ₄ alkoxy. Halogen, nitro, hydroxy. Carboxy. Cyan. Alkylcarbonylamino with 2 to 5 carbon atoms. Arylcarbonylamino, aryloxy, arylazo. Sulfo. Arylamino. C ₁ -C ₄ mono or dialkylamino substituents phenyl. Naphthyl, triazolyl or benzothiazolyl radical, which, in the event that the sulfo group in the naphthalene ring is in the 4-position, of the o-position. metallizable groups is free. where under aryl in each case optionally by methyl. Methoxy.

SO ₁ H HO ₁ S

SO ₁ H

Chlorine. Nitro and sulfo substituted phenyl is to be understood. and A further substituents from the series C ₁ -C ₄ -AlCyI, C, -C ₄ -alkoxy, halogen, nitro, hydroxy. Carboxy. Cyan, alkylcarbonylamino with 2 to 5 carbon atoms. Arylcarbonylamino, aryloxy, arylazo, sulfo. Arylamino. May contain C ₁ -C ₄ -MonO- or -dialkylamino, where aryl may optionally be replaced by methyl. Methoxy, chlorine. Nitro and sulfo substituted phenyl is to be understood.

Preferred dyes correspond to the formula in the form of the free acid

H, N OH

R ₁ O-; A -N- N-

-CH =

Si) ₁ H

SO ₁ H HO ₁ S

-N = NO ₁
SO ₁ H

(II)

wherein R is a C _{1 -C 4 alkyl radical and D 1 is} an optionally substituted by C 1 -C 4 alkyl. C ₁ -C ₄ alkoxy. Halogen. Nitro. Hydroxy. Carboxy. Cyan. Alkylcarbonylamino with 2 to 5 carbon atoms, arylcarbonylamino. Aryloxy. Arylazo. Sulfo, arylamino. C, -C ₄ -Mono- or -Di-

alkylamino substituted phenyl or naphthyl. 50 form of the free acid of the formula Triazolvl- or Benzthiazolvlrest mean, where

under aryl, optionally by methyl, methoxy. Chlorine. To understand nitro and sulfo substituted phenyl is. and A has the meaning given in claim 1.

Very particular preference is given to dyes which are in

, N OH

R ₁ O-

-CH -CIl r-N = -N- D,

Sf) Jl

correspond, where R _{1 has} the abovementioned meaning and D _{1 is} optionally by halogen. C ₁ -C ₄ -alkyl, Cr-C ₄ -alkcixy, nitro. Sulfo. C ₂ -C ₅ AlCyI-carbonylamino. Benzoylamino and by methyl. Methoxy. Chlorine, nitro. Sulfo. substituted benzoylamino substituted phenyl.

In the context of the dyes of the formula III, these are of particular importance. where D, for SO ₁ H HC) ₁ S
a remainder of the formula

SO ₁ H

, -NHR,

in which R _{1 is} C 2 -C ₅ -alkylcarbonyl or benzoyl which is optionally substituted by methyl, methoxy, chlorine, nitro or sulfo.

The dyes of the formula are obtained by coupling diazotized amines of the formula

f A.-N = N-

CH-CH- -NH,

SO ₁ H

wherein A and R have the meaning given above, with l-amino-N-hydroxynaphthalene-3.6- or -4.6-disulfonic acid in an acidic, aqueous medium and subsequent coupling of the disazo dyes formed formula

* A "; —N = N-

H, N OH

- CH == CH - ■ "-N = N-; ■ ',
SO, H ■ SO ₅ H HO ₃ S 'SO ₁ H

with diazotized amines of the formula

/ VJ)

in an aqueous alkaline medium.

The amines of the formula: IV are obtained in a manner known per se by diazotizing 4-nitro-4 ' - aminostilbene - 2,2'-disulfonic acid. Coupling with an optionally substituted as indicated Phenol. Etherification of the phenolic hydroxyl group and reduction of the nitro group.

Suitable amines (VI) are, for example, aniline. 2-chloroaniline, 3-chloroanil: in, 4-chloroaniline, J-aminobenzene-2-sulfonic acid, 1-aminobenzene-3-sulfonic acid. 1-aminobenzoI-4-sulfonic acid. 1-amino-2-methylbenzene. l-annino-4-methylbenzene. 1-amino-2-nitrobenzene. 1-amino-4-nitrobenzene. 1-amino-4-methoxybenzene. I-amino-4-acetylaminobenzene. 1-amino-4-benzoylaminobenzene, 1-Amino-4- (4-nitrobenzoylamino) benzene. 1-Amino-2-sulfo-4- (benzoylamino) benzene. 1-Amino-2-sulfo-4- (4'-nitrobenzoylamino) benzene. 1 - aminonaphthiiline. 1 - aminonaphthalene-4-sulfonic acid, l-aminonaphthalene-6- or -7-sulfonic acid. 2-aminonaphthalene-6-sulfonic acid. 2-aminobenzothiazole. 3 - amino - 1,2,4 - triazole. 5 - amino-1.2.4 - triazole - carboxylic acid - (3). 4 - [6 - methylbenzthiazolyl- (2)] - aniline, 4- [6-methylbenzthiazolyl- (2)] - anilinesulfonic acid, 4-aminoazobenzene-4'-sulfonic acid. 4-AminoazobenzoI-4'-hydroxy-3'-carboxylic acid.

The new dyes are outstandingly suitable for dyeing and printing hydroxyl-containing products and nitrogen-containing natural or synthetic fiber materials, for example Cellulose fibers in all processing states. especially of cotton and regeperatccllulose. as well as leather and paper. Green dyeings with good fastness properties are obtained.

Example I.

71 g of 4-amino-4 '- (p-methoxyphenylazo) -stilbene-2,2-disulfonic acid are stirred in 350ml water at 45C. After adding 15 ml of 1N sodium hydroxide solution is heated to 60 C. 33.3 ml of a 30% aqueous sodium nitrite solution are added and the mixture is left the solution in a template of 135 g of ice. 270 ml of water and run in 45 ml of 1η hydrochloric acid with rapid stirring. The reaction mixture is 1 hour at about 25 C. Immediately before coupling I, excess sodium nitrite is mixed with a little sulfamic acid removed and with about 60 ml of a 2 ()% igen. aqueous sodium acciar jösuni! to a pH dulled by about 2. Then 41.6 g of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid., Which in

^ 5 400 ml of water dissolved neutrally at about 35 C, mixed with 150 g of urea and adjusted to pH 3 with about 15 ml of 1 η hydrochloric acid immediately before the 1st coupling, run quickly into the suspension of the diazotized amine. The pH is adjusted to 2.5 with 20 ⁿ oiger. aqueous sodium acetate solution adjusted.

After several hours of stirring at 25 to 30 ° C., the coupling is complete. 13 g of aniline are diazotized in known way and there are to the solution of the disazo dyes, the previously with about 45 g of 1 N sodium hydroxide solution

.15 was made neutral and treated with 70 g of sodium carbonate. After stirring for several hours, the Clutch finished. The mixture is heated to 70 ° C. and 250 g of sodium chloride are added to precipitate the dye. After stirring for about 1 hour, it is filtered off. After drying at 90 ° C., about 350 g of dye are obtained, that dyes cotton green.

In a staining beaker of 500 ml, which is located in a heated water bath, are 26OmI of water at 50 to 60 ° C. and 10 ml of 10% sodium sulfate solution and 1 ml of 10% Sodium carbonate solution added. 0.25 g of the dye are mixed with 2 ml of cold water to form a paste processed, to which 30 ml of water at 50 to 60 "C are added, whereupon the dye goes into solution.

so The dye solution is added to the first solution, and 10g of a cotton fabric is introduced into the dye bath and continuously agitated therein. The temperature of the dyebath is brought to 85 to 90 ° C. within 30 minutes and held at this temperature for 1 hour. Then, the dyed material is taken up, released from an attached ink solution by wringing out, rinsed with cold water for 5 to 10 minutes and dried at 60 to 70 ⁰ C.

Further dyes are obtained by using the dis-

azo dye precursors with those in the table

listed Diazokompor.enten D - NH ₂ converts.

Replaced in example I and in examples 2

to 19 the l-amino-S-hydroxynaphthalene-S.o-disulfonic acid through an equal amount of 1-amino-8-hyclroxy-4,6-disulfonic acid. in this way one obtains other valuable dyes which produce green dyeings on cotton to practice.

example

Diazotized Ληιίη D- Nile,

4-chloroaniline 1-aminobenzene-4-sulfonic acid 1-amino-4-methylbenzene 1-amino-4-nitrobenzene 1-amino-4-methoxybenzene

1-amino-4-acctylaminobenzene 1-amino-4-benzoylaminobenzene

1-Amino-4- (4-nitrobenzoylamino) benzene

1-amino-2-sulfo-4-benzoylaminobenzene

23 60 708 I arbton at on spat! cotton No. green 11th urün 12th green 13th green i ° green 14th green 15th green 16 green 17th 18th u r i i η 19th

Diazotiettes amine D - NH ₂

1-Amino-2-sulfo-4- (4-nitrobenzoyl-green aminol-benzene

4-Aminoazobenzene-4'-sulfonic acid green 4-Amino-4'-hydroxy-azobenzene green 3'-carboxylic acid

1-aminonaphthalene-4-sulfonic acid green 2-aminonaphthalene-6-sulfonic acid green 3-amino-1,2,4-triazole green

5-Amino-1,2,4-triazolecarboxylic acid (3) green 4- [6-Methylbenzthiazolyl- (2)] - aniline green 4- [6-Methylbenzthiazolyl- (2)] - green

aniline monosulfonic acid

609 63

718

Claims (3)

Claims: 1. Polvuzostilbcnfuibstoffc. those in the form of the free acid of the formula H, N OH A: —N = N- -CH = CH —f -N = N- -N = N-D SO, H correspond, in which R is an o- or p-hydroxyl group etherified _{by a C 1 -C 4 -alkyl radical.} D is an optionally by C ₁ -C ^ - alkyl, C ₁ -C ₄ -alkoxy, halogen, nitro, hydroxy, carboxy, cyano, alkylcarbonylamino group having 2 to 5 carbon atoms. Arylcarbonylamino, aryloxy, arylazo, sulfo, arylamino. C, -C ₄ -MonO- or -dialkylamino-substituted phenyl, naphthyl, triazolyl or benzothiazolyl radicals which, in the event that the sulfo group in the naphthalene ring is in the 4-styrene ring, of the o-position. metallizable groups is free. where under aryl in each case optionally by methyl. Methoxy. Chlorine. SO, H HO ₁ S SO, H Nitro and sulfo substituted phenyl is to be understood. and A further substituents from the series C, -C ₄ -alkyl, C, -C ₄ -alkoxy, halogen, nitro, hydroxy. Carboxy, cyano, alkylcarbonylamino with 2 to 5 carbon atoms. Arylcarbonylamino, aryloxy, arylazo, sulfo, arylamino. C _{1 -C 4} mono- or dialkylamino, where aryl is to be understood as meaning phenyl which is optionally substituted by methyl, methoxy, chlorine, nitro and sulfo. 2. Polyazo dyes according to claim 1. in the form of the free acid of the formula H, N OH R ₁ -O-; Λ -N = N- -CH = CH -, - N = N- N = ND ₁ S Ο., Η in which R _{1 is} a C _{1 -C 4} -alkyl radical, D _{1 is} an optionally _{substituted by C 1} -C ₄ -Alk) I. C ₁ -C ₄ alkoxy, halogen. Nitro. Hydroxy. Carboxy. Cyan. Alkylcarbonylaminp with 2 to 5 carbon atoms. Arylcarbonylamino. Aryloxy, arylazo, sulfo. Arylamino. C ₁ -C ₄ -MonO- or -dialkylamino substituted phenyl- or naphthyl-, triazolyl- or SO, HHO, S SO ₁ H Benzthiazolyl radical, where aryl optionally by methyl. Methoxy, chlorine. Nitro and sulfo substituted phenyl is to be understood, and A has the meaning given in claim 1. 3. Polyazostilbene dyes according to Claim 1. those in the form of the free acid of the formula H, N OH R ₁ -O- -N = N -CH = CH -Γ '-N = N- - N --- = N - SO., H correspond, in which D ^ door szee also by halogen. C, -C ₄ alkyL C, -C ₄ alkoxy. Nitro, sulfo. C ₂ -C ₅ alkylcarbonylamino. Benzoylamino. that by methyl. Methoxy. Chlorine. Nitro. Sulfo sub- wherein R _{2 is} Q-Cj-alkylcarbonyl or optionally by methyl. Methoxy. Chlorine. Nitro or sulfo substituted benzoyl. 5. Process for dyeing and printing SO, H HO ₃ S SO, H may be substituted, is substituted phenyl and R _{1 is a C 1 -C 4} -alkyl radical. 4. Dyestuffs according to Claim 3, in which D _{2 is} a radical of the formula -NHR ₂ hydroxyl-containing or nitrogen-containing natural or synthetic fiber materials, characterized in that polyazostilbene dyes in the form of the free acid of the formula H, N OH Λ --N = N- CH- = CH- __ V zzzr V -N = N-D SO, H correspond, in which R is an o- or p-hydroxyl group etherified _{by a C 1 -C 4 -alkyl radical.} D door an optionally by C ₁ -C ₄ -alkyl. C ₁ -C ₄ alkoxy. Halogen, nitro. Hydroxy, carboxy, cyan. Alkylcarbonylamino mil, 2 to SO ₁ H HOjS SOjH 5 carbon atoms, arylcarbonylamino, aryloxy, arylazo. Sulfo, arylamino. C ₁ -C ₄ -MonO or -dialkylamino substituted phenyl, naphthyl, triazolyl or benzthiazolyl radical, which, in the event that the sulfo group in Naphthalinrin.u in 4 position, from o-stiindigen. metalisable groups is free, with aryl in each case optionally by methyl, methoxy, chlorine. Nitro and sulfo substituted phenyl is to be understood. and A further substituents from the series C ₁ -Q-alkyl. C ₁ -C ₄ alkoxy. Halogen. Nitro. Hydroxy, carboxy, cyan. Alkylcarbonylamino with 2 to 5 carbon atoms, arylcarbonylamino, aryloxy. Arylazo, sulfo, arylamino, C _{1 -C 4} mono- or dialkylamino, where aryl may optionally be substituted by methyl, methoxy, chlorine. Nitro and sulfo substituted phenyl is to be understood.