CH617220A5 - Process for preparing new polyazo dyes - Google Patents

Description

617 220

2nd

The present invention relates to a process for the preparation of new polyazo dyes of the general formula

K - N - N — 1-1 1 \

N - K,

(l)

wherein

-X— = —N = or-NO =,

I = a benzene, naphthalene, pyridine or pyrimidine ring, the nitrogen atoms of which are in the 4- or 6-position, based on the triazole nucleus,

J = the atoms which are necessary to form a 5- or 6-membered aromatic or heterocyclic ring which may have a fused-on aromatic or alicyclic ring,

K] and K2 = residues of coupling components of the aromatic or heterocyclic series, or of azo dyes, where they can be identical or different, and where

I and J unsubstituted or with water-solubilizing groups and alkyl, hydroxyl, alkoxy, aryloxy, alkanoyl, aroyl, alkyl or arylsulfonyl, alkanoylamino unsubstituted or N-substituted carbamoyl or sulfamoyl, alkoxycarbonyl , Alkoxysulfonyl, nitro, cyano or trifluoromethyl groups are substituted and all the above-mentioned alkyl, alkoxy or alkanoyl groups have 1 to 4 carbon atoms, characterized in that coupling components of the formulas KjH or K2H with tetrazo compounds from diamines of the formula

R2 = a cyclohexyl, phenyl, benzyl, benzoyl or phenylsulfonyl group or one of the meanings given for Rj and the phenyl ring of the above-mentioned benzyl, phenyl, benzoyl or phenylsulfonyl groups with chlorine or bromine atoms or one of 1 to 4-carbon alkyl group may be substituted,

At and A2 = a) a phenyl, alkylphenyl or naphthyl radical which has at least one halogen atom or one, -COOH, -SO3H, hydroxy-, alkoxy-, -N02, -NH2, N-alkyl-, N- Aryl or N, N-dialkylamino, alkanoylamino, -NH-CO -COOH, arylsulfonyloxy, or substituted with an alkylamino group containing a -COOH, -SO3H or hydroxy group or with a fiber-reactive group,

; b) a naphthyl radical with a phenylamino, naphthylamino, benzoylamino, phenylsulfonylamino, (p- or m-benzoylamino) benzoylamino, -NH-CO-NH2 or NH-CO-NH-aryl group, the can carry a fiber-reactive radical, substituted or to a divalent radical of the formula

NH,

or

(2)

is condensed, where —U— = -S- or —NH— and the phenylamino, benzoylamino or phenylsulfonylamino groups mentioned on the phenyl nucleus can carry -OH, -NH2, -COOH, alkyl or alkoxy groups,

4o c) a residue of the formula couples.

Within the present definition, disazo compounds corresponding to the formula below are of particular practical interest, as are their oxidation products, a nitrogen atom in the 1- or 3-position of the triazole ring being replaced by the = NO bridge or its metal complexes:

COOH

50

Al-N = N

V N 1

N

N = N-A

2nd

(3)

wherein Z is a hydrogen atom or an -NH2, -N02, S03H or aminophenylcarbonamide group or a fiber-reactive group, or of the formula

55

HO

wherein I 'and J' with chlorine or bromine atoms, -OH, -S03H, -COOH, methyl, ethyl, methoxy, ethoxy, phenoxy, ß-hydroxyethyl, hydroxymethoxy, carboxymethoxy, acetyl, Benzoyl, methyl or ethylsulfonyl, acethylamino, methoxy or ethoxycarbonyl, nitro, cyano, trifluoromethyl

/ Rl thyl groups or groups of the formula -Y-NC can be substituted, where -Y- = -CO- or -S02- R2

Rj = a hydrogen atom, an alkyl or a hydroxyalkyl group,

-N- <X

V7. «

Y

CH_

N-

wherein Z 'is a hydrogen or chlorine atom or an —NH2, —SO3H, alkyl, hydroxyl or COOH group or a fiber-reactive group, or of the formula

3rd

617 220

rG9- (S03H) n where n is 1 or 2, or of the formula

OH

or

J ^ \

where Y 'can be substituted by an S03H group, or the formula in which, in the formulas given above, the alkyl, alkoxy or alkanoyl groups have 1 to 4 carbon atoms, and A and and A2 can represent identical or different radicals.

Within the present definition, triazole compounds corresponding to the formulas below are of particular practical interest, as are their oxidation products, a nitrogen atom in the 1- or 3-position of the triazole ring being replaced by the = NO bridge or its metal complexes

N = N-

Ar

> N <

I '

-N = N-

/

(4)

B-N = N-A,

or in which I ', J', Aj and A2 have the meanings given in the explanation of the formula (3) 4 s = (-hydroxynaphthylene-CO-NH) 2-L or (-hydroxynaphth), ethylene-NH-CO-NH ) 2-L, where

B = a phenylene radical which is unsubstituted or with alkyl, ^ = e'n diphenylene or a phenylene radical which by

Alkoxy-, -NH2, SO3H, -NH-CO-COOH or carboxyalkyl-alkoxy, alkyl or H03S groups can be substituted, amino groups or substituted with fiber-reactive groups, E = e'n unsubstituted or with chlorine atoms, 02N- ,

so H2N, N, N-dialkylamino, sulfoalkylamino, phenylamino, benzoylamino, acetyliamino, hydroxy, H02C, H03S, sulfamoyl, alkoxy, alkyl, phenylaminocarbonyl, phenoxy groups or fiber-reactive groups substituted phenyl or

55 = an unsubstituted or with H2N, 02N, hydroxy,

or H03S groups or fiber-reactive groups of substituted naphthyl radical, where the phenylamino and phenylaminocarbonyl groups mentioned can carry H02C, hydroxyl or alkyl groups on the phenyl nucleus, all have alkyl and alkoxy groups (, 'of 1 to 4 carbon atoms, and the azo dye groups residues -BN = N-A2 and -CN = NE can be metallized with Cr, Co, Ni or in particular Cu.

Within the present definition, tetrazo compounds 65 corresponding to the formulas below are of practical interest, as are their oxidation products, phenylene, naphthylene, diphenylene methane, diphenylene urine, a substance, dinaphthylene methane or in the 1- or 3-position of the triazole ring Di- (p-phenylene-l-pyra- nitrogen atom is replaced by the = NO bridge or its zolon-4-yI) urea residue metal complexes: (Form S8)

= a naphthylene radical which is unsubstituted or substituted by hydroxyl, alkoxy or S03H groups, or = aryl-NHCO-phenyl, naphthyl-NH-CO-phenyl-CO-NH-phenyl or

HO

T

COOH

C = a substituted with alkyl, hydroxylalkyl, H2N, HO, H03S, HOzC groups or fiber-reactive groups

617 290

4th

- - N = N>

■ jr (lN

A.

or

(6)

A-N = N

• 4 •

\ N]

m> - <2 /

N = N — Ai where A3 =

_B1-N = N-B2-N = N-A2, -B-N = N-C-N = N-E, -C-N = N-B-N = N-E or -C-N = N-D-N = N-A,

(7)

-CH (cyclohexyl) -, -CH (phenyl) -, -CH (chlorophenyl) -, -CH2-CH2-, -CH2, -CO-NH-, -NH-CO-NH-, NH-CS-NH- or -NO = N-.

Particularly valuable disazo dyes are those of the formula

A '~

A1

-N = N

"KJrzy

N = N-A '

2nd

(8th)

andA4 andA5 = -B-N = N = A2 or -C-N = N-E,

in which

I ', J', Aj and A2 have the meanings given in the explanation of the formula (3), B, B and B2 have the meanings given in the explanation of the formula (4) and C and E have the meanings given in the explanation of the formula (5) , A4 and 5 as well as B! and B2 can be the same or different and

D = an unsubstituted or substituted with a chlorine atom, an alkyl, alkoxy, hydroxy or S03H group

= an unsubstituted or substituted with an S03H group naphthylene radical or

= an unsubstituted or substituted with a chlorine atom, a nitro, hydroxy, -COOH, -S03H, alkyl, alkoxy or carboxyalkoxy group, diphenylene or -phenylene-V-phenylene radical, with —V— = -NH -, -O-, -S—,

where Aj 'and A2' =

a) a naphthyl radical bearing at least one HO or H2N group, which may be substituted by further HO, H2N, HO3S or carboxy groups or by chlorine atoms, or b) a phenyl radical bearing at least one HO or H2N group which with other HO, H2N, H03S, carboxy, nitro, -NHCOCOOH, methyl, methoxy, ethoxy, phenyl or tolylsulfonyloxy, acetylamino, phenyl or tolylamino, carboxyalkylamino , N-mono- or N, N-dialkylamino groups may be substituted, or c) a naphthyl radical substituted with a carboxyalkylamino, alkylamino or arylamino group, or d) a hydroxynaphthyl radical carrying at least one sulfo group, which is substituted with alkylamino, Carboxyalkylamino, acetylamino, benzoylamino, phenyl or tolylsulfonylamino or phenylamino groups, which may have methyl, methoxy, carboxy or HO group on the phenyl nucleus, or e) a 3-methyl, 3- Carboxy or 3-carboxyethoxy-l-phenyl or -1-sulfonaphthyl -5-pyrazolone or a 5-amine o-3-methyl-l-phepyI-2-pyrazoline, which may carry -S03H, HO, nitro, carboxy or methyl group or chlorine atoms on the phenyl nucleus, wherein

I 'and J' may have the substituents given in the explanation of the formula (3) and where Aj 'and A2' may be the same or different.

Particularly valuable trisazo dyes are those of the formulas or n = n-

-b'-n = n-a "

• cL

(9)

N = N ~

-c'-m-e1

(10)

wherein

I 'and J' can carry the substituents given in the explanation of the formula (3),

A ", A2" have one of the meanings given for A1 'and A2' in the explanation of the formula (8) under paragraphs a) and b) or

= a hydroxyl or aminonaphthyl radical carrying a phenylamino group, where they can be identical or different,

Ml B '= a phenylene radical substituted with methyl, methoxy or NH-CO-COOH groups or

= a naphthylene radical which can be substituted by HO or H03S groups,

f, s C '= a phenylene or naphthylene radical carrying at least one HO or H2N group, which may be substituted by further HO, H2N, H03S or methyl groups

E '= a phenyl radical, the H03S, HO, H2N, carboxy,

5

617 220

Can carry nitro, methyl, acetylamino or sulfamoyl groups or chlorine atoms, or.

= a naphthyl radical which can carry H03S, HO or carboxy groups, it being possible for the azo dye radicals-B'-N = N-A2 "and -C-N = N-E 'to be metallized with Cr, Co, Ni and Cu.

Particularly valuable tetrakisazo dyes are those of the formula

Oil)

wherein A4 'and A5' can be the same or different, A2 ", E ', B' and C 'those used in the explanation of the formulas (8) and (9), I' and J 'those used in the explanation of the formula (3 ) have the meanings given.

In addition to the metal complex dyes mentioned in the explanations of the formulas (4), (5), (9) and (10), those which are obtained by the metallization of azo dyes of the following formulas can also be described as particularly valuable:

■ ß

K ^ -N = N- | 2 ^^ N- <J «> - H = N-K ^ (12)

or

Ki -n = n_ki

(13)

5

where Kj '= A!'

-C'-N = N-E 'or

»(HO3S) n- ^ 0—,

K2 '= A /

= -B'-N = N-A2 "or-C'-N = N-E 'where n = 1 or 2, 15 B' and A2" which in the explanation of the formula (9)

C 'and E' used in the explanation of formula (10)

I 'and J' have the meanings given in the explanation of the formula (3),

I "and J" carry a metallizable HO, carboxy, methoxy, 211 ethoxy, hydroxymethoxy or carboxymethoxy group and K, 'carry a metallizable HO, H2N, methoxy or -NHCOCOOH in the o-position to the azo bridge, where I "and J" may be further substituted with substituents specified for I 'and J' in the explanation of the formula (3). 25 The coupling components K (H and K2H used in the present production process can be coupling-capable monoazo and even disazo dyes as well as metal complex dyes; they can be fiber-reactive residues, ie residues which react with the hydroxyl groups of cellulose or with the Ami-10 nogroups of polyamides to form react one or more covalent bonds.

The triazole diamines of the formula (2) which are used as starting materials here are prepared by methods known per se, e.g. Correspondingly substituted o-amino noazo bodies of the formulas

h2n-

: -

-NO,

- NH,

■ -, x or H ^ N-

NHCOCH,

subject to oxidation.

Examples of diamines of the formula (2) which are suitable for the diazotization and coupling are: 2 ', 5-diamino-2-phenylbenztriazole, 3', 5-diamino-2-phenylbenztriazole, 2 ', 5-diamino-4'-chlorine -2-phenylbenztriazole, 3 ', 5-diamino-6-chloro-2-phenylbenztriazole, 2', 5-diamino-4'-methyl-2-phenylbenztriazole, 3 ', 5-diamino-2'-methyl-2- phenylbenztriazole, 3 ', 5-diamino-4-methyl-2-phenylbenztriazole, 3', 5-diamino-6-methyl-2-phenylbenztriazole, 3 ', 5-diamino-7-methyl-2-phenylbenztriazole, 3', 5-diamino-4 ', 6-dimethyl-2-phenylbenztriazole, 3', 5-diamino-2 ', 6-dimethyl-2-phenylbenztriazole, 3', 5-diamino-4,4'-dimethyl-2-phenylbenztriazole , 3 ', 5-diamino-2', 7-dimethyl-2-phenylbenztriazole, 2 ', 5-diamino-4'-methoxy-2-phenyIbenztriazol, 3', 5-diamino-6-methoxy-2-phenylbenztriazole, 3 ', 5-diamino-6,6' -dimethoxy-2-phenylbenztriazole, 3 ', 5-diamino-6'-methoxy-2-phenylbenztriazole, 3', 5-diamino-4'-methyl-6-chloro 2-phenylbenztriazole, 3 ', 5-diamino-6'-methyl-6-chloro-2-phenylbenztriazole, 3', 5-diamino-6'-methoxy-6-chloro-2-phenylbenz triazole, 3 ', 5-diamino-6'-methyl-6-methoxy-2-phenylbenztriazole, 3', 5-diamino-6-methyl-6'-methoxy-2-phenylbenztriazole,

3 ', 5-diamino-2'-methyl-5'-methoxy-2-phenylbenztriazole, j, 3', 5-diamino-4-chloro-4'-methoxy-2-phenylbenztriazole, 3 ', 5-diamino- 2'-methyl-4'-methoxy-4-nitro-2-phenylbenzotriazole,

2- (4'-aminophenyl) -5-amino-benzotriazole, which is not further substituted or in the 3'- and 6-position by two carboxy, so sulfo, carboxymethoxy, hydroxy, methyl or methoxy groups or is substituted by two chlorine atoms, in the 3 'or 6 position by a sulfo, carboxy or ethoxy group, in the 2' and 7 position by two sulfo or nitro groups or by two chlorine atoms, 55 4 ', 5- Diamino-3'-chloro-2-phenylbenztriazole, 4 ', 5-diamino-5-chloro-2-phenylbenztriazole, 4', 5-diamino-2'-methyl-2-phenylbenztriazole, 4 ', 5-diamino-3 '-methyl-2-phenylbenztriazole,

4 ', 5-diamino-2', 5 '-dimethyl I-2-phenylbenztriazole, "o 4', 5-diamino-2 ', 5', 6-trimethyl-2-phenylbenztriazole, 4 ', 5-diamino- 3'-methoxy-2-phenylbenztriazole, 4 ', 5-diamino-6-methoxy-2-phenylbenztriazole, 4', 5-diamino-2 ', 5'-dimethoxy-2-phenylbenztriazole, 4', 5-diamino 2 ', 6,5'-trimethoxy-2-phenylbenztriazole, "5 4', 5-diamino-6'-methyl-6-chloro-2-phenylbenztriazole, 4 ', 5-diamino-3'-methyl-6- chloro-2-phenylbenztriazole, 4 ', 5-diamino-6-methyl-3'-chloro-2-phenylbenztriazole, 4', 5-diamino-7-methyl-5 '-chloro-2-phenylbenztriazole,

617 220

6

4 ', 5-diamino-3'-methoxy-6-chloro-2-phenylbenztriazole,

4 ', 5-diamino-6-methoxy-3'-chloro-2-phenylbenztriazole,

4 ', 5-diamino-2'-methyl-5'-methoxy-2-phenylbenztriazoI,

4 ', 5-diamino-6-methyl-3'-methoxy-2-phenylbenztriazole,

4 ', 5-diamino-3'methyl-6-methoxy-2-phenyIbenztriazoI,

4 ', 5-diamino-2'-methyl-6-methoxy-2-phenylbenztriazole,

4 ', 5-diamino-7-methyl-3'-methoxy-2-phenyIbenztriazol,

4 ', 5-diamino-2', 5'-dimethyl-6-methoxy-2-phenylbenztriazole,

4 ', 5-diamino-6-methyl-2', 5'-dimethoxy-2-phenylbenztriazole,

4 ', 5-diamino-7-methyl-2', 5'-dimethoxy-2-phenylbenztriazole,

4 ', 5-diamino-2'-methyl-6,5'-dimethoxy-2-phenylbenztriazole,

2- (3'-methyl-4'-amino-6'-suIfophenyl) -5-amino-6-methyl-,

2- (3'-methoxy-4'-amino-6'-sulfophenyl) -5-amino-6-methoxy-

benzotriazole as well as their nitrogen at the 1 or 3 permanent nitrogen

oxidized derivatives.

Examples of usable coupling components which are referred to in the above description as KjH and K2H are:

2-amino-, 2,7-diamino-, 1, N-carboxymethylamino- or 2, N-phenylamino-naphthalene,

1-amino-naphthalene-4- or -5-sulfonic acid, 2-amino-naphthalene-6- or -7-sulfonic acid or -5,7- or -3,6-disulfonic acid,

2, N-methyl- or 2, N-ethylamino-naphthalene-7-sulfonic acid,

3,6-diamino-naphthalene-2,7-disulfonic acid, l-naphthol-5-sulfonic acid, -4.7 -, - 3.8-, -4.8- or -3,6-disulfonic acid or -2, 6,8-trisulfonic acid,

1-naphthol-4-sulfonic acid (Nevile-Winter acid),

2-naphthol,

2-naphthol-6-sulfonic acid (Schaeffer's acid), 2-naphthol-8-sulfonic acid, -3-carboxylic acid or -3,7-disulfonic acid,

2-naphthol-3,6-disulfonic acid (R acid),

2-naphthòl-6,8-disulfonic acid (G acid),

2,7-dihydroxy-naphthalene, 4,7-dihydroxy-naphthalene-2-sulfonic acid, 4,6-dihydroxy-naphthalene-1-sulfonic acid, -1-sulfo-3 '-carboxylic acid or -2-sulfo-7-carboxylic acid,

l-naphthol-8-chloro-5-sulfonic acid or -3,6-disulfonic acid, l-naphthol-8-ethoxy-3,6-disulfonic acid,

7-amino-2-naphthol,

5-amino or 6-amino-5-chloro-l-naphthol-3-sulfonic acid,

8-amino-1-naphthol-5,7-disulfonic acid,

3-amino-2-naphthol-7-sulfonic acid,

6, N-ethyl, 6-carboxymethyl, 6-phenyl, 6, p-tolyl,

6, p-methoxyphenyl, 6-benzoyl-, 6, m-carboxyphenyl-, 6- (2,4-dimethoxyphenyl) -, 6- (3-carboxy-4-hydroxyphenyl) -l-naphthol-3-sulfonic acid , 6- (l -hydroxy-3-sulfo-naphth-6-yI) -amino-

1-naphthol-3-sulfonic acid (Di J acid),

7, N-methyl, ethyl, phenyl, acetyl, benzoyl or 7, N, N-dimethylamino-l-naphthol-3-sulfonic acid,

8, N-benzoylamino-l-naphthol-5-sulfonic acid, 8-N-acetylamino-l-naphthol-3,5-disulfonic acid, 3-methyl-l-phenyl-, (p-tolyl) -, (p or m -sulfophenyl) -, (4-sulfo-o-tolyl) -, (3-carboxy-2-hydroxy-5-sulfophenyl) -, (6-sulfonaphth-2-yl) -, (2-chloro-5- or 6-sulfophenyl) -, (4,8- or 5,7-disulfonaphth-2-yl) -5-pyrazolone, 3-carboxy-l- (m-nitro- or p-suIfophenyl) -6-pyrazo! One, 5-amino-3-methyl-l-phenylpyrazoline,

2-methyl indole,

2,4-quinoline diol,

Ethoxy-, phenylsulfoxy- or (p-methylphenyl) sulfoxybenzene,

2-methyl-, 2- (o-methylphenylamino) -, 3-phenylamino- or 3-amino-6-chlorophenol,

Salicylic acid,

l-phenol-2- or 3-sulfonic acid,

5- or 6-methylphenol-2-carboxylic acid,

3-aminophenol-4- or 6-sulfonic acid,

0- or m-toluidine,

m-ethylaminoacetanilide,

m-carboxymethylamino-aniline or -o-methylaniline,

4-nitro-, chloro- or methoxy-m-phenylenediamine, s 2-methyl- or 2-methoxy-5-acetylamino-aniline,

2-methoxy-aniline,

3,5-diamino-4-chloro- or 2,4-diamino-5-methyl-benzene-l-sulfonic acid,

as well as the following diazotizable coupling components: m 1-amino-naphthalene,

1-amino-naphthalene-6- or -7-sulfonic acid,

7- or 8-amino-l-naphthol-3,6-disulfonic acid (H acid),

8-amino-1-naphthol-5-sulfonic acid, 6-amino-1-naphthol-3-sulfonic acid (J acid),

15 3-amino or 3-amino-4-methyl-oxanilic acid,

3-methyl-6-methyl- or -6-methoxy-aniline,

and the following coupling components having a second coupling-capable position: 1,8-dihydroxy-naphthalene-4-sulfonic acid, zw 1,8-dihydroxy-naphthalene-3,6-disulfonic acid, (chromotropic acid),

8-amino-1-naphthol-5-sulfonic acid or 3,6-, or 4,6-disulfonic acid

8-amino-l-naphthol-3,5-disulfonic acid (K acid), 25 6-amino-l-naphthol-3-sulfonic acid (y acid),

Resorcinol,

Phenol,

1,3-phenylenediamine,

4-sulfo, 4-methyl or 5-sulfo-2-methyl-l, 3-phenylenedi-.w amine, as well as the following monoazo compounds:

4- (4'-sulfo-, 4'-acetylamino-, 2 ', 4'-disulfo-phenylazo) -l, 3-phenylenediamine,

4- (4'- or 2'-hydroxy-3'-carboxy-phenylazo) -l, 3-phenylene-diamine,

, 5 6-SuIfo-4-phenylazo- or 6-methyl-4 (4'-sulfophenylazo) -1,3-phenylenediamine,

4- [4'-SulfonaphthyI- (l) '- azo] -, 4- [8'-hydroxy-6'-sulfo- or 3,6'-disulfonaphthyl- (2)' - azo] -l, 3- phenylenediamine, 6-methyl-4- [4'-sulfonaphthyl- (l) '- azo] - or 4- [6', 8'- or

40 3,6'-disulfonaphthyl- (2) '- azo] -l, 3phenylenediamine,

5-sulfo-2-methyl-4- [8'-hydroxy-6 'sulfonaphthyl- (2)' -azo] -1,3-phenylenediamine,

4- (3'-Sulfophenylazo) or 4- [5'-SulfonaphthyI- (l) '] - resorci-nol, the copper complex of the 4- (2'-hydroxy- or 1' -

45 hydroxy-2'-carboxy-5'-sulfophenylazo) - or 4- (2'-hydroxy-5'-sulfamoylphenylazo) resorcinol,

5-hydroxy-3- [4'-aminonaphthyl- (l ') - azo] -naphthalene-2,7-disulphonic acid,

4,5-dihydroxy-3- [4 '-sulfonaphthyl- (1)' -azo] -naphthalene-1 -sul-50 fonic acid or 2,7-disulfonic acid, 5-hydroxy-4-amino-3 [2'- chloro-, 2'- or 4'-nitro-, 2 ', 5'-di-chloro- or 4'-sulfo-phenylazo], - 3- [2'-chloro-4'- or 5'-nitro- phenylazo] - or -3 [2'-methyl-5'-nitrophenylazo] -naphthalin-2,7-disulfonic acid, 55 5-hydroxy-4-amino-3 [4'-sulfophenylazo] - or 4-hydroxy- 5-amino-6 [4'-nitrophenylazo] naphthalene-2,8-disulfonic acid, 5-hydroxy-4-amino-3 (phenylazo) -, -3 (4'-sulfo-, 2 ', 5'-disulfo -or4'-chloro-3'-sulfo-phenylazo) -naphthalene-l-sulfonic acid, 4-hydroxy-6 (2 ', 4'-diamino-3'-methyl-6'-sulfophenyIazo) -f, u or - 7-amino-8 (3'- or 4'-nitrophenylazo- or 2'-chloro-4'-sulfophenylazo) -naphthalene-2-sulfonic acid, where all nitro groups present can be subsequently reduced by treatment with sodium sulfide, for example, or as well as disazo connections such as 1,3-di (2 ', 4'-diaminophenylazo) benzene.

05

The above-mentioned coupling components and monoazo compounds can also be coupled with intermediate products capable of forming the dye, at

7

617 220

for example, those that are formed by coupling a diamine of the formula (2) with diazotizable coupling components.

As a double coupling component which react with two equivalents of a diazo component, e.g. such compounds as 4,4'-methylenediphenol and 3,3'-diaminocarbanilide mentioned.

Examples of usable diazotizable components which are referred to in the above description as E-NH2 are:

Sulfanil, metanil, 3-chlorosulfanil or 6-chlorosulfanilic acid,

6-amino-benzene-l, 3- or 1,4-disulfonic acid,

Aniline, o-chloro- or o, m or p-nitroaniline, 2-chloro-4-

nitro-, 2,5-dichloro- or 2-methyl-5-nitro-aniline,

p-aminooxanilic acid,

p-aminoacetanilide,

2-amino-5-nitro-benzenecarbon or sulfonic acid,

3- or 5-amino- or 3-amino-5-sulfo-salicylic acid, 2-amino-l-phenol-4-sulfonic acid or -4-sulfonamide, 1-amino-naphthalene,

1-amino-naphthalene-4-, 5-, 6- or 7-sulfonic acid,

2-amino-naphthalene-6,8-disulfonic acid, 2-amino-8-hydroxy-naphthalene-6-sulfonic or 3,6-disulfonic acid,

5-amino-4H-l, 2,4-triazole-3-carboxylic acid or, as a double diazotizable site component that reacts with two equivalents of a coupling component, 4,8-diamino-naphthalene-2,6-disulfonic acid.

A large number of fiber-reactive groups are known from the literature. The following groupings are therefore only a selection of the possible fiber-reactive groups.

A) Such suitable groups include those which contain at least one fiber-reactive substituent bonded to a 5- or 6-membered heterocyclic ring which optionally has one or more fused rings of an aromatic nature. Examples of fiber-reactive substituents attached to the heterocycle include:

Halogen (such as chlorine, bromine, fluorine) ammonium (including hydrazinium), sulfonium, sulfonyl, azido (N3), rhodamido, thio (such as thiocyanine or residues of the formula

S-G-NsC ^ or-S-C -), thio and oxyethers, the one

N-

groups include, for example, mono- and di-alkylamino groups, in which the alkyl groups preferably contain at most 4 carbon atoms and which may also contain substituents, for example hydroxyl or alkoxy groups, 5 and phenylamino and naphthylamino groups, which preferably contain sulfonic acid substituents; the class of etherified hydroxyl and mercapto groups includes, for example, alkoxy and alkylthio groups, preferably those of low molecular weight, i.e. with up to 4 m carbon atoms, as well as phenoxy, phenylthio, naphthoxy or naphthylthio groups. Chlorine atoms or cyan, nitro, carboxyl or carbalkoxy groups in the 5-position of a pyrimidinyl radical also fall into the category of the non-reactive substituents. They can also be alkyl or acyl groups bonded directly to the heterocycle.

Particularly preferred dyes in the field of new dyes are those on which the fiber-reactive group is a 6-membered diazine or triazine ring in which a carbon atom is replaced by an -O-, -NH-, -NCH3-N-CO- or -N -SOz-2 (1 II

bridge is bound to the dye residue and has at least one fiber-reactive substituent such as a halogen atom or a sulfonyl group.

Among them are of very great interest: 25 l triazine group, symbolized as N-Rel, how

45

Contain electronegative substituents (such as a sulfo or nitro group), sulfiric acid, sulfonic acid and ethylene imino.

The 5- or 6-membered heterocyclic rings mentioned can also contain further, non-fiber-reactive substituents. Examples of such substituents are: primary amino and hydroxyl groups, including mono- or disubstituted amino groups, etherified hydroxyl groups and etherified mercapto groups; the class of substituted amino

a) where G = F, Cl, Br,

-Su = a primary, secondary or tertiary amino group;

how

-NH2, -NHCH3, -NHC2H5, -NHC3H7, -NHC4H9,

NH-hexyl-, NH-cyclohexyl, - (CH3) 2,

-N (C2H5) 2, -NHCH2CH2OH, -N (CH2CH2OH) 2, -NHCH2CH20S03H, -NHCH2CH2OCH3, -NHCH2CH2C1, -NHCH2-CH (OH) 2, -NHCH2CH0H0S03H, morpholino, -prazide , -NH-phenyl, -NH (2-, 3- or 4-sulfophenyl), NH (2-, 3 or 2,4- or 2,5- or 4,5- or 3,5-disulfophenyl), - NH (0-, m- or p-methylphenyl), -NH-carboxyphenyl, -NH-benzyl, -NH (O.Ò'-dimethyl-phenyl), -NH (O-carboxy-sulfophenyl), -NH (m-carboxy-p-hydroxyphenyl), - NH-sulfonaphthyl,

-N (CH3) CH2CH2CN, -N (CH2CH2CN) 2, ~ N (CH3) -CH2CH2S03H, -N (CH3) phenyl, -N (CH3) suIfophe-nyl, -N (CH2CH2OH) sulfophenyl, -N (CH2S03H) phenyl, 1 NHCN, N (CH3) CN, -aminoacetic acid, thioacetamido,

-NH- ^ V ^ rS02-NH-CH2SQ3H, or like amino groups of the formulas

-NH-

or = N

S

617 220

8th

(where Ra = alkoxy, aryloxy, thioalkoxy or thioaryloxy),

= an etherified hydroxyl or mercapto group, such as -OH, -OCH3j -OC2H5, OC3H7, OC4H9, phenyloxy-, -SH, -SCH3, -SC2H5, -SCH2CH2OH -0CH2S02-phenyl, OCH2-CH2OCH3, -S-phenyl, -SCH2COOH , -SCSN (CH3) 2, where the above-mentioned phenyl rings can be substituted by chlorine, methyl or methoxy groups,

= an alkyl or aryl group, such as the phenyl group, which can be replaced by chlorine, bromine, methyl, hydroxyl, methoxy, cyano,

Sulfo, carboxy or nitro groups can be substituted, a methyl or trichloromethyl group, or

= a fiber-reactive substituent, such as CI, Br, F, -S02-carboxyphenyl, -S02-sulfophenyl, -OSO3H, -SCN, nitro- or sulfophenyloxy-, -S-nitro- or sulfophenyl, or b) where -G = - Su = S02-phenyl, -S02-carboxyphenyl, -S02-trichloromethylphenyl or-S02- (ß-sulfoethyl), or c) wherein -G = S02CH3 and

—Su = trichloroethyloxy-, phenoxy-, —NH-sulfophenyl, -N (CH3) phenyl, or d) wherein -G = -Su = nitro- or sulfophenoxy, nitro- or sulfothiophenoxy, -SCN, -0S03H, -N < I, -SCSN (Rb) Rc or

-SC (Rd) = N (Re) where Rb and Rc = alkyl, cycloalkyl, aryl or aralkyl group, and Rd and Re = H, alkyl, aryl-

or aralkyl group, or

© ©

e) wherein-G = -N (CH3) 3, -N (CH3) 2-NH2,

(± y

- N / A nh2

®- / 7 ~ -N

\ =

<& r

—N NH2

_> •

0

-N-N

U

N or -N-N, and

-Su = -NH-phenyl, -NH-sulfophenyl or -N (CH2CH2OH) 2;

2.4-pyrimidine group, symbolized as> N-Re2 or 15 -0-Re2, as in which G! and G2 = F, Cl or Br and

-Su = -H, -F, -Cl, -Br, -N02, -CH3, -CH2COOH, -COOH, -CN, -S03H, -CH2C1, -CHC12, -CCI3, -CBr3, -CF3, -COOCH3 , -COOC2H5 -CH = CH2-halogenovinyl- or -allyl, such as

NO,

> N

CEL

Cl

Sul

> N

ïï-

4th

ci

Su5 Su2 * ^

wherein -Sul = -N02, -COOH, -COOCH3 or -COOC2H5, -S02NH2 optionally N-substituted, -S02phenyl,

-Su2 = -Su, except -N02 and S03H, allyl-, 4 "-S02-methyl, -S02-ethyl or -S02-chlorophenyl,

_CONH2 -Su3 = Su2, N02 or S03H, like and

Su5 Su4 Su6 SA

J— »> N— <JT,

• h ~ ^ so2CH3

H, C0oS SOpCH-

^ N / ^ where

W ^ S0oCH,

2?

g3 = -so2ch3, -so2c2h5, -so2ch2cooh, Su7 J

-so2ch2ch2so3h, -so2ci3 ">

—S02-phenyl _ Q- ^

—Su4 = -H, -CH3, -C2H5, -CH2C1 or OCH3 and V

—Su5 = —H, -Cl, -Br, —N02, -CH3 or CN, «5 XF

g4 = g3 or = Cl, Br, COOH or CH2COOH,

■ Su6 = -H, -Cl,

W = <

4th

wherein

G5 = S03H or COOH, such as ~ Su7 = ~ H> ~ cl> ~ Br '-CH3 or-C2Hs;

9

3. 2-pyrimidine group symbolized as> N-Re'2, like

617 220

or where Su2 and Su3 have the meaning given above;

4. 4-carbonyl or sulfonyl-pyrimidine group, symbolized as> N-Y-Re3, such as

Su3

> N-Y-

G,

N

H = <

GJ

Su8 Gr

> N-Y- ^ ^

n = <,

GJ

or

Su8 Su9

N:

G

8th

wherein

Y = -CO- or S02—,

G6 and G6 '= - CI, -Br, -S02CH3 or -S02C2H5, G7 and G / = -S03H, -Cl or -Br,

-Su8 = -H-, -Br or -Cl,

-Su9 = -alkoxy, -aryloxy, -NH2, -NHalkyl, -N (alkyl) 2, -NHphenyl, -NH (sulfophenyl) or -NH (disulfophenyl); G8 = ammonium;

> N-Y-

or

Gln,> -ï

> -ï- <

SCH,

F

> == N '

where GI0 and G10 '= G6 or G7, and Su 10 = H or CH3.

6. Other diazines, such as

Y-N <

/ \ A

Y-N ^ symbolizes as> N-Y-Re "3,

5. -5-carbonyI or sulfonylpyrimidine group symbolized as> N-Y-Re'3 as

^ N \

vvorin

ß9-

G9 or G9 '= Cl or S02CH3 and the other = CH3 as

SulO

e6,> m-t-

Su9

^ 2-chloro or bromoquinoxaline- (3) - or (6) -Y-N <

3-chloro or bromoquinoxaline (6) -Y-N <

2,3-dichloro- or dibromoquinoxaline- (5) - or (6) -Y-N <

2.4-dichloro- or dibromoquinazoline- (6) - or (7) -Y-N <1,4-dichloro- or dibromopthalazine- (6) -Y-N <

s "2,4,6-Trichloroquinazoline- (7) - or (8) -Y-N <

2,4,7- or 2,4,8-trichloroquinazoline- (6) -Y-N <, or groups of the formulas:

N-CH2CH2-Y-N <or

V

617 220

10th

in which

Y = -CO- or-S02-, or how

2-Methylsulfonyl-quinazolinyl- (4) -N <

3-trichloromethylsulfonyl-pyridazinyl- (6) -N <3-phenylmethysulfonyI-pyridazinyI- (6) -N <3-methylsulfonyl-4-methyl-pyridazinyl- (6) -N <3-methylisulfonyl-pyridazinyl- (6) - N <

3,4,5-Trichloropyridazinyl- (6) -N <3,6-difluoropyridazinyl- (5) -N <

and the group of the formula

CH5S02

S0oCH "

-sulfonyl, 2-chloro or bromobenzoxazole or -benzimidazole-5- or 6-carbonyl or -sulfonyl, 2-chloro-1-methyl-benz-imidazole-5- or 6-carbonyl or -sulfonyl, 2- Chloro- or bromothiazole- or -4-methyl-thiazole-4- or 5-carbonyl or s -sulfonyl, N-oxide of 4-chloro- or -nitroquinoline-5-carbonyl, 2-methylsulfonyl-4-carboxy-pyridine, 2-trichloro- or 2-carboxymethylsulfonylquinoline.

B) Other suitable groups are unsaturated and / or halogenated aliphatic or aromatic residues of a sulfone (II) or carboxylic acid chloride;

a) They can be bound to the dye by an amino group, such as a group of the formula Re4-Y-N <,

h2c h2c

15 pN-CH2-CO-N <or pM-CO-N <

H, C

H, C

, symbolized as> N-Re "2

7. Other 5- or 6-membered heterocycles which are only one in which Y is CO- or SO2-

Nitrogen atom contain: Re4 = C1CH2-, C1CH2CH2-, BrCH2CH2-, BrCH2CHBr-,

2-chloro, 2-bromo, 2-sulfo, 2-methylsulfonyl, 2-ethylsulfo CH3S02C2H4-, C2H5S02C2H4-,

nyl- or 2-phenylsulfonyl-benzothiazole-5- or 6-carbonyl or HS030C2H4-, HS030C2H4S02C2H4-

Ol— ^ 3 ", ClCHg ^ O-, O ~ S0202H4-,

HO.

CH2 = CH-, CH2 = CBr-, CH2 = CC1-, COOH-CH = CCl-, CH2 = CH-CH2-S- ^ ° * ^> -

F

P-

Sn m

Sn-

-P

Sn m i

-CH = CH

Gr '11

or

Sn ^

F-

Gr "

Gr "

where Su "= H or alkyl Su '" = Su "or aryl G" = Cl or F.

b) They can be bonded directly to the dye, such as a group of the formula Re5-S02-, where Re5 = C1C2H4-, HS03C2H4-, HP03C2H4-, CH2 = CH-, ClCH2CH (OH) CH2-, BrCH2CH (OH) CH2-, HIGH2CH (OH) CH2NHC2H4-, (C2H5) 2NC2H4-, HSOjOQH ^ H-, C1CH2CHC1CH2NH-, HSOjSCz ^ NH- or HS030C2H4N (CH3) C3H6NH-,

H2C, v or PN — S02-H2C

or CH2 "CH-CH2-S02".

O

C) Other suitable groups are, for example: a) the CH2-CH-CH2-M group,

c /

i wherein -M- = -N-, -O- or -S-

b) groups that are directly bound to the dyes, such as

-so2f,

x

4th

~ ^ V-F and —N •

'T ^

in the U

55

A large number of other suitable fiber reactive components are known from the literature and therefore do not need to be listed separately.

(, () The tetrazotation of the diamine of the formula (2) is carried out according to methods known per se, for example with the aid of sodium nitrite and hydrochloric acid. The coupling with the coupling components KtH and K2H and any further couplings required can likewise be carried out in a manner known per se be carried out in (5 acidic to alkaline medium.

Like benzidine, the diamines of the formula (2) are particularly suitable for preparing asymmetrical diazo dyes, since the two couplings use very different energies.

11

617 220

to run. The first coupling proceeds very quickly even in acidic medium, while the disazo dye only forms slowly.

According to one embodiment of the above method, the diazotization and / or coupling of a compound which contains a fiber-reactive substituent should, if possible, take place in an acidic or at most weakly alkaline aqueous medium.

According to a further embodiment, a monoazo compound which contains a metal bonded in the form of a complex is used as the coupling component. Such compounds can be obtained, for example, by treatment with metal-donating agents from a monoazo compound which contains a metallizable group, for example an o, o "-dihydroxyazo grouping, o-carboxy-o'hydroxyazo grouping or o-amino-o'-hydroxyazo grouping will.

According to a further embodiment of the above method, metalizable compounds containing fiber-reactive residues are subjected to a treatment with a metal-donating agent for the production of metal complex polyazo dyes. However, this process is preferably limited to the preparation of dyes in which the fiber-reactive substituent is resistant to hydrolysis during the metallization, which is the case, for example,

if he has a 2-chloro-4-amino, 2-chloro-4- (m-sulfophenyl) amino, 2,4-dichloro or 2-chloro-4-phenoxy-s-triazin-6-yl residue represents.

Such fiber-reactive groups can be introduced during the above process in a manner known per se. For example, it can be condensed onto a free amino group -NH2 or -NHCH3 with an acid chloride of the formula Re3-Y-Cl, Re'3-Y-Cl or Re "3-Y-Cl (see paragraphs A4, A5 and A6) or the formula Re4-Y-Cl (see paragraph B) or with the corresponding acid anhydride.

It can also be achieved by azinylating an -NH2 or -NHCH3 group with cyanuric chloride or with a chlorine derivative of the formula Rel-Cl, Re2-Cl, Re'2-Cl or R "2-Cl (see paragraphs AI, A2, A3 and A6 ) or, if the radicals symbolized as Rei, Re2, Re'2 or Re "2 contain a sulfonyl group —S02 — Q, with a sulfonyl derivative of the formula Rel-SOz-Q, Re2-S02Q, Re'2-S02Q or Re" 2-S02Q.

If the radical symbolized as Re2 has two fluorine atoms in the 2- and 6-position, it can also be carried out by reacting a dye or an intermediate product capable of dye formation which contains an HO group with a 2,4,6-trifluoropyrimidine compound.

The introduction of the ethyleneimine residue can take place, for example, by reacting the ethylenein with a dye which has a benzoylamino group or one of the two fiber-reactive -NH-CO-CH2Cl or -SO2F groups, so that the fiber-reactive groups of the formula

According to further embodiments of the present method, further changes can take place according to methods known per se in existing fiber-reactive groups, for example:

- Treatment of an a, ß-dihalo- or ß-halopropionyl group with a hydrogen halide-releasing agent to form an a-haloacrylic or an aryl group;

the treatment of a y-halogen ß-hydroxypropyl-sulfonyl, amino, oxy or mercapto residues to form a -CH2-CH -CH2 group which is attached to the dye by an -S02—,

O

-NH-, -S- or-O-bridge is bound;

the treatment of a dibromo or dichlorotriazine nucleus with ammonia, with a primary or secondary amine or with an alcohol or thioalcohol to replace a halogen atom with another substituent;

- The treatment of a bromine or chlorotriazine nucleus with a tertiary amine to form an ammonium group.

The dyes obtained are used in the dyeing or printing of natural fibers such as leather, wool, silk, of synthetic polyamide or polyurethane materials and mainly of natural or regenerated cellulose fibers.

They result in a large selection of dyeings which generally have better wet fastness properties than the corresponding, previously known benzidine dyes of the German patent 664 188.

As with the above-mentioned benzidine dyes, it can be dyed from neutral to slightly soda-alkaline solution by increasing the amount of salt added to the fiber. The temperature is slowly increased from 30-50 ° C to boiling.

In some cases, an aftertreatment on the colored material can be carried out, such as development by further diazotization and coupling, treatment with formaldehyde (dyes with resorcinol m-aminophenol or m-phenylenediamine as end component) to improve wet fastness or with copper or chromium salts (with complex-forming dyes) to improve light fastness.

In addition to better general wet fastness properties, the present dyes have another advantage over the corresponding benzidine dyes in that they do not show the toxicity of the latter.

Unless otherwise stated, the parts in the examples below mean parts by weight, the percentages by weight and the temperatures are given in degrees Celsius.

Example 1.

8.9 parts conc. Hydrochloric acid with

31.6 parts of finely crushed ice mixed and cooled to -10 ° in a cold bath. Then be

5.37 parts of a 4N sodium nitrite solution were added with stirring. A solution, prepared from, with vigorous stirring at -10 ° C. to the resulting bluish solution of the nitrous acid

1 part of 2- (4'-aminophenyl) -5-amino-benzotriazole in

0.9 parts conc. Hydrochloric acid and

10.5 parts of water flowed in for 15 minutes.

After the addition of the diamine solution has ended, the mixture is stirred for a further 15 minutes at −10 ° and the excess sodium nitrite is then added by adding a solution of approx.

1.6 parts of sulfamic acid in

20 parts of water destroyed. The highly acidic diazo solution is cleared of the little insoluble by a Hyflo bed.

For coupling one with conc. Solution of sodium hydroxide solution

1.35 parts H acid (100%) in

82 parts of water at a pH of 10.5 submitted.

The diazo component is run into this solution at 0-5 ° for 15 minutes,

10th

[5th

20th

25th

V)

.15

40

45

50

fiO

f> 5

617 220

12

Early addition of a 10% aqueous sodium hydroxide solution ensures that the pH remains between 10.2 and 10.5. The solution immediately turns violet and a fine dark blue precipitate soon precipitates. After the addition of the diazo solution has ended, the mixture is stirred for a further 5 minutes at 0-5 ° and then a solution of 0.943 parts of y-acid (100%),

0.55 parts of sodium hydroxide solution conc. and

0.25 parts of soda in

8.4 parts of water fell to the reaction mixture. The blue-violet suspension is left to react at 20-25 ° overnight. Then be

34 parts of table salt are added, stirred at 35-40 ° for 5 hours, then at 20-25 ° overnight, finally filtered off with suction and dried, giving 5.3 parts of the dye of the formula I.

= n-o - \! xt

\ N / S /

-N = N-

k i

horn

S0XH

S05H

The dye dyes cotton substantially in deep blue tones.

If the coupling of the H acid at pH 2.4-3 and the

Coupling of the y-acid tones as performed at pH 10.2-10.5 above.

This gives 5.05 parts of the isomeric dye of the formula II, the substantive cotton and wool from an acidic solution in violet v-m = h-O_ / C0-m-

N

NH2 OH

S0, H o so5H

II

When dyed, both dyes can be diazotized on cotton and coupled further with coupling components. If, for example, a blue cotton cloth dyed with the dye of the formula I is treated with a dilute sulfuric acid sodium nitrite solution and then rinsed with an aqueous solution of m-phenylenediamine, the cloth is dyed black.

According to the information in Example 11, part 2- (4'-aminophenyl) -5-amino-benzotriazole is obtained by equivalent amounts of a diamine of the formula

H2N

XX

N \ N N '

NH,

X

replaced, in which the two X have the meaning given in column 2 of the table below and 1.35 parts of H-40 acid or 0.943 part of y-acid by equivalent amounts of those given in column 3 or column 4 of Table I below Coupling components replaced, so you get dyes that have equally good properties and the cotton in the shades in column 5 45 dyes.

Some of these dyes, like dyes I and II, can be diazotized on cotton in the colored state and coupled further with coupling components. Correspondingly, the dyes indicated in column 2 of table II, numbered according to table I, were diazotized and coupled with the coupling component indicated in column 3, the dyeings indicated in column 4 being obtained on a cotton cloth.

13

617 220

(1) (2) (3)

No. Diamine

1 H naphthionic acid

2 H naphthionic acid

3 H 3,6-diamino-2,7-naphthalene

disulfonic acid

4 H l-NaphthoI-3,6,8-trisulfonic acid

5 H (alk) J acid

6 H (alk) y acid

7 H (alk) H acid

8 Methyl Nevile-Winter acidity

9 methoxy 8-chloro-l-naphthol-5 sulfonic acid

10 methoxy R acid

11 Methoxy Chromotropic Acid

12 methoxy 2- (m-aminophenyl) -6-hydroxy-

1H-Naphth- (1,2) imidazole-8-sulfonic acid

13 methoxy N-carboxymethyl-J-acid

14 methoxy N-acetyl-K-acid

15 Cl 8-ethoxy-1-naphthol-3,6-

disulfonic acid

16 methyl (alk) y acid

17 S03H cresidine

18 methoxy l-naphthol-3,6,8-trisulfonic acid

19 methoxy l-amino-8-hydroxynaphthalene

3,6-disulfonic acid (acidic)

20 methyl l-hydroxy-6-aminonaphthalene

3-sulfonic acid (alkaline)

(4) (5)

Nevile - Winter Acid Red

N-1-naphthylglycine red

(alk) y acid brown

2-naphthol purple

(alk) J acid purple

(alk) y acid black

(alk) H acid blue l-naphthol-3,6-disulfone-blue acid sulfonic acid blue l, 7-dihydroxy-4-sulfonaph-blue thalin-2-carboxylic acid

Di-J-acid blue

(alk) J acid blue

Schaeffer's acid blue

3-Amino-p-acetotoluidide see Table II

8-ethoxy-l-naphthoI-3,6-red disulfonic acid

3-Hydroxy-2-naphthoic acid see Table II

Cresidine see Tab. II

(alk.) l-Hydroxy-6-aminonaph-red-

thalin-3-sulfonic acid brown

(alk.) l-Hydroxy-6-aminonaph-cloudy thalin-3-sulfonic acid violet

Naphthionic acid purple

Table II (1) (2) (3)

1 5 3,5-diamino-p-toluoIesulfon-

acid

2 6 idem

3 7 2-naphthol

4 6 m-phenylenediamine

5 14 2-naphthol

(4)

blue

Blue-black

black

black

blue

6 17 (alk) N-p-carboxyphenyl-y-

acid

7 16 2,4-toluenediamine

black

black

"O Preparation of the starting product 2- (4'-aminophenyl) -5-ami-nobenztriazol-6-sulfonic acid

10 parts of acetyl-p-phenylenediamine (titer: 87%) are diazotized by a known method. The conga-acid diazo solution is allowed to run into a neutral solution of (.? 11.82 parts of 1,3-phenylenediamine-4-sulfonic acid (titer: 92.1%) in 100 parts of water at 10 ° for one hour a 15% sodium carbonate solution keeps the pH between 6.1 throughout the coupling reaction

617 220

14

and 6.3 constant. The mixture is then stirred for a further 2 hours at 10 °. The pH is then adjusted to 8.0 to 8.3 by adding sodium carbonate and the mixture is heated to 75 ° for 5 hours, a clear dark brown solution being formed.

The solution of the azo dye prepared in this way is concentrated at 75 ° with 0.3 part of Irgafomal TP and then with 6 parts. aqueous ammonia added. A solution of 2.9 parts of copper sulfate pentahydrate in 15 parts of water and 6 parts of conc. run in aqueous ammonia and conducts air through the solution with vigorous stirring. After about 4 Vi hours of gas introduction near the boiling point, the oxidation is complete and the thin layer chromatogram no longer shows any unoxidized dye.

This solution is now mixed with 1.4 parts of sodium sulfide (65%), dissolved in 5 parts of water. After stirring for 15 minutes, 11.6 parts of solid sodium hydroxide are added in portions and then refluxed for 4 hours. Then 0.3 parts of sodium hydrosulfite are added for decolorization, and the mixture is again refluxed for 20 minutes. Finally, the precipitated copper sulfide is separated off by clarification filtration, 20 parts of sodium chloride are added to the mother liquor and the solution is stirred overnight. The precipitate is filtered off and washed with brine. After drying, 20 parts of 2- (4'-aminophenyl) -5-amino-benzotriazole-6-sulfonic acid of the formula III below are obtained in the form of a yellow crystal powder with a nitrite value of 63.4%.

H0N N

to

H0, S / AvNk '3

III

10 Example 2

Preparation of a dye from the 2- (4 '-aminophenyl) -5-aminobenztriazole-6-sulfonic acid Tetrazotierung:

10 parts of the 2- (4'-aminophenyl) -5-ami-15 nobenztriazol-6-sulfonic acid obtained above are suspended in 150 parts of water and mixed with 17 parts of 39% hydrochloric acid. Then 11.75 parts of a 4N sodium nitrite solution are suddenly poured in at 0 ° with vigorous stirring. The orange-colored suspension is stirred at 0 ° / z hour. ,,, clutch:

7.02 parts of l-hydroxy-6-aminonaphthalene-3 -sulfonic acid (66%) are concentrated in 180 parts of water with the addition of 2.52 parts. Sodium hydroxide solution dissolved. The diazo solution prepared above is run into this solution at 0 ° for xh hour, 5, the pH being kept between 9.0 and 10.0 by simultaneous addition of a 10% sodium hydroxide solution. Immediately after the addition of the diazo solution has ended, a solution of 9.54 parts of 1-naphthol-3,8-disulfonic acid in 150 parts of water is added to the reaction mixture and the mixture is then stirred at pH 9-10 overnight. After acidification of the reaction mixture to pH 3.5, the cellulose materials can be isolated by lively bluish-tinged red colorants of the formula IV below by filtration.

HO, S OH

3rd

-N = N

Example 3

10 parts of 2- (4'-aminophenyl) -5-aminobenztriazole-6-sulfonic acid (56.6%) are tetrazotized according to the method described in Example 2. A solution of 7.3 parts of l-amino-8-hydroxynaphthalene-3,6-disulfonic acid (80.9% strength) in 130 parts of water and 2.4 parts of conc. Sodium hydroxide solution was allowed to run in for 1 hour, the pH being kept constant at 2.0 to 2.5 by the simultaneous addition of a 10% sodium hydrogen carbonate solution.

HO NH

H0, S 'v v NS0, H 3 3

The partially precipitated solution, stirred overnight at 0 to 5 °, is adjusted to pH 8.0 to 8.2 with sodium carbonate and then at 0 to 5 ° for 1/2 hour with a solution of 4.89 parts of l-hydroxy- 7-aminonaphthalene-3-sulfonic acid! in 130 parts of water, 2.4 parts of conc. Sodium hydroxide solution and 1.1 parts of solid soda, the pH being kept constant at 8.0 to 8.2 during the entire coupling reaction by the simultaneous addition of a 10% sodium carbonate solution. The dye suspension is then stirred overnight at room temperature, then 5 hours at 40 ° and finally mixed with 50 parts of sodium chloride, whereupon the dye of formula V below can be isolated.

-N = N-

15

617 220

It stains cellulose-based substrates substantively in bordeaux tones.

Preparation of a reactive dye from 2- (4 '-aminophenyl) -5-aminobenzotriazole-6-sulfonic acid

20 parts of the dye prepared in Example 2 (nitrite value: 47.4%) are dissolved in 800 parts of water and cooled to 0 °. After the solution is adjusted to pH 7.0 with sodium hydroxide solution, a previously prepared solution of 1.9 parts of cyanuric chloride in 20 parts of acetone is added. By continuously adding sodium hydroxide solution, the pH is now at 6 to 7

held. After no more sodium hydroxide solution is used, the pH is adjusted to 7 and a neutralized solution of 4.1 parts of aniline-2,5-disulfonic acid in 30 parts of water is added. Now the mixture is heated to 40 to 50 ° and again neutralized continuously to pH 7.0 with ln-5 sodium hydroxide solution. After standing at 40 to 50 ° for 3 hours, the mixture is stirred at room temperature overnight and finally salted out with 70 parts of sodium chloride. The isolated dye of formula VI below dyes cellulose-containing materials with high fixation and exhaustion values in bluish red tones according to the usual dyeing methods for reactive dyes.

In Examples 2 and 3, the 2- (4'-aminophenyl) -5-aminobenztriazole-6-sulfonic acid is replaced by an equivalent amount of 2- (4'-aminophenyl) -5-aminobenzotriazoI-2 ', 6-disulfonic acid replaced (produced, for example, by coupling diazotized 4-nitroaniline-2-sulfonic acid to 1,3-phenylene-min-4-sulfonic acid, oxidation of the o-aminoazo dye obtained with copper sulfate in water / ammonia to give 2- (4'-nitro -phenyl) -5-aminobenztriazol-2 ', 6-disulfonic acid and subsequent reduction of the nitro group with sodium sulfide in water), valuable dyes with similar properties and nuances but with improved solubility are also obtained.

According to the example given, 2.10 parts of 2- (4'-aminophenyl) -5-aminobenzotriazole-6-sulfonic acid are obtained by equivalent amounts of a diamine of the formula

: s H0N N

YY \ -onh replaced, where Y has the meaning given in column 2 of the table below, and 7.02 parts of l-hydroxy-6-aminonaphthalene-3-sulfonic acid or 9.54 parts of l-naphthol-3.8 -disulfonic acid replaced by equivalent amounts of the coupling components specified in column 3 or .15 column 4 of the following Table III, cellulose materials are also obtained with substantively coloring dyes with good general fastness properties. The nuances of the colors on cotton can be seen in column 5 of the table.

Table III

(1) (2)

No diamine

00

1 cl

2 methoxy

3 methoxy

4 methoxy

(3)

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

1-Hydroxy-6-aminonaphtha-lin-3-sulfonic acid (alk.)

l-naphthol-3,6,8-trisulfonic acid

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

(4) (5)

1-Hydroxy-6-aminonaphtha- reddish lin-3-sulfonic acid (alk.) Blue

Naphthionic acid (alk.) Violet

1 -hydroxy-6-aminonaphtha- violet lin-3-sulfonic acid (alk.)

1-Hydroxy-6-aminonaphtha- navy blue lin-3-sulfonic acid (alk.)

To prepare the copper complex of the dye designated in Table III with No. 3, 10 parts of dye (nitrite value: 44.6%) with 120 parts of water, 15 parts of conc. Ammonia and 1.8 parts of copper sulfate pentahydrate heated at 105 to 110 ° in the pressure vessel for 15 hours. The still warm solution is separated from the insoluble by a clarifying filtration and then evaporated to dryness. The copper complex obtained (8.5 parts) dyes cotton substantively and leather from a weakly acidic solution in brown-violet shades with good general fastness properties.

Example 4 (, (] A solution of

1 part of 2- (4'-aminophenyl) -5-amino-benzotriazole in 0.9 parts of conc. Hydrochloric acid and

10.5 parts of water, using a mixture of

(, 5 5.37 parts of 4 N aqueous sodium nitrite in

31.6 parts of crushed ice and

8.9 parts conc. Hydrochloric acid by the method described in Example 1

617 220

16

After destroying the excess nitrite using a solution of approx.

1.6 parts of sulfamic acid in

20 parts of water are allowed to leave the diazo solution clarified over a Hyflo bed for 10 minutes to a chilled to 0-5 ° and with the help of

19 parts of a 7.5% aqueous sodium hydroxide solution

0.638 parts of salicylic acid (100%) in

Run in 42 parts of water at pH 12.6 with good stirring.

The simultaneous controlled addition of a 7.5% aqueous sodium hydroxide solution ensures that the pH of the solution remains between 12 and 12.8 during the coupling. After the addition of the diazo component has ended, the brown-red solution is still stirred for 5 minutes, still at 0-5 °. Then a solution of 1.01 parts of y-acid (100%) in 10.1 parts of water and ^ 1.27 parts of sodium hydroxide solution conc. tumbled. The second coupling starts slowly, the solution becomes increasingly dark and cloudy and after about 3 hours a dark brown precipitate is formed. The reaction mixture is left to react at 20-25 ° overnight, then stirred for a further 5 hours at 45 °. Eventually

34 parts of table salt are added, the mixture is stirred at 20-25 ° overnight, then filtered off with suction and dried, giving 2.75 parts of the dye of chemical formula VII, which substantially stains the cotton in warm brown tones.

HO

H00

c - ^>:

-N = N-

SN '

VII

HO

- SO ^ H

NH,

After the first coupling, the approach just described is acidified to pH 4 with 50% aqueous acetic acid after salicylic acid and then with a solution acidified with the aid of hydrochloric acid until the reaction is weak

1.01 parts of y-acid (100%) in

: 20 parts water and

1.3 parts of sodium hydroxide solution conc. added and finally worked up like the dye VII, the isomeric dye of the formula VIII which stains cellulosic materials, such as cotton, paper, viscose, etc., is substantively colored in red tones.

HO

H00C - ^> - ^

\

-N = N-

VIII

The dye VIII dyes wool with chrome stains due to the presence of salicylic acid group.

If instead of the 2- (4'-aminophenyl) -5-aminobenzotriazole, or the salicylic acid or gamma acid, corresponding amounts of a diamine of the formula are used in place of the examples

X

have the meaning given in column 2 of Table IV below and corresponding amounts of one of the coupling components indicated in column 3 or 4, and the procedure is otherwise as described in Example 2, so that dyes with similar properties are obtained, which contain cellulose-containing materials in the Color the shades specified in column 5.

sn As can be seen in Table IV, dyes that have been produced with diamines or coupling components specified in columns 3 or 4 or 5 dye wool with chrome or copper stain in the shades that are resistant to walking in the shades specified in column 6.

4 p

17th

617 220

Table IV

(1) (2) (3)

No. Diamine First coupling component 1 CH3 2,4-DiaminobenzoIsuIfonic acid

(4) (5)

Second clutch component Nuance

2-methyl-phenol-6-carbon-orange acid

2 H 3-amino-2,7-naphthalene-disul-

fonic

3 H 3-amino-2,7-naphthalene-disul

fonic

Phenol * orange

Phenol ** orange

4 CH3 (alk) H acid

5 OCH3 0.77 mol R acid

0.33 mol G acid

6 OCH3 N-acetyl-K acid

7 h

8 h

9 cl

Salicylic acid

Salicylic acid

3-carboxy-1-m-nitrophenyl-5-pyrazolone

(alk) m-anilinophenol black m-toluidine blue

3-amino-p-acetaniside blue

3-carboxy-1 - (p-sulfophenyl) orange -5-pyrazoIon

3-methyl-1- (4,8-disulfo-orange

2-naphthyl) -5-pyrazolone

3-carboxy-l-m-nitrophenyl red 5-pyrazolone ***

10 CI l- (2-chloro-6-sulfophenyl) -3-

methyl-5-pyrazolone

11 OCH3 3-methyl-l-p-tolyI-5-pyrazoIon

1 - (2-ChIoro-6-suIfophenyl) -3-methyl-5-pyrazolone

3-methyl-1-p-tolyI-5-pyrazolone

yellow

red

12 OCH3 3-carboethoxy-l-phenyl-5-pyrazolone

1-phenyl-5-pyrazolone

red

* and post-treatment with C2H5-C1 in a soda-alkaline solution to form a 0-C2H5 group

** And post-treatment with CI-S02 -

-CFL for

Esterification of the hydroxy group

*** and subsequently reducing the nitro group to an -NH2 group

Table V

(1) (2) (3) No. Pickle diamine

1 Cu

2 cr

OH OCH3

(4)

First coupling component l-naphthol-3,8-disulphonic acid

N- (3-carboxy-4-hydroxyphenyl) -J acid

(5) (6)

Second clutch component Nuance

N-phenyl J acid blue

N- (3-Carboxy-4-hydroxyphenyI) blue J acid

3 Cu OCH2COOH 6-amino-5-chloro-l-naphthol-

3-sulphonic acid

4 Cu OCH2COOH N-benzoyl J acid

6-amino-5-chloro-1-naphthol blue 3-suiphonic acid

N- (2,4-DimethoxyphenyI) blue

J acid

Cu

Cr

OCH2COOH 5-imino-3-methyl-l-phenyl-2-pyrazoline

CH,

1- (3-carboxy-2-hydroxy-5-sulfophenyl) -3-methyl-5-pyrazolone

5-imino-3-methyl-l-phenyl red

2-pyrazoline

1 - (3-Carboxy-2-hydroxy-5-sul-yellow fophenyl) -3-methyl-5-pyrazolone

617 220

18th

Example 5

A solution of

1 part of 2- (4'-aminophenyl) -5-amino-benzotriazole in

0.9 parts conc. Hydrochloric acid and

10.5 parts of water, using a mixture of

5.37 parts of 4 N aqueous sodium nitrite in

31.6 parts of crushed ice and

8.9 parts conc. Hydrochloric acid by the method described in Example 1.

After destroying the excess nitrite using a solution of approx.

1.6 parts of sulfamic acid in

The batch is made up of 20 parts of water by adding approx.

7.7 parts of sodium bicarbonate are adjusted to pH 2-3 and then clarified by a Hyflo bed to remove the insoluble matter. The clear diazo solution now becomes a solution of at 0-5 °

2.2 parts of sodium naphthionate (100%) and

2.2 parts sodium acetate in

17.6 parts of water ran in for 10 minutes, the pH of the coupling mixture adjusting to about 5 and the burgundy dye immediately precipitating.

Now the mixture is stirred for 1 hour at 5 °, 5 hours at 20 °, 24 hours at 35 °, 12 hours at 55 °.

Then the mixture is boiled and filtered off at about 50 °, pressed and dried, giving 2.5 parts of the dye of formula IX, which dyes cotton substantially in brilliant tones.

IH If 2- (4'-aminophenyl) -5-amino-benzotriazole uses 2- (4'-aminophenyl) -5-aminobenzotriazole-6,3'-disulfonic acid as the tetrazotizing component in Example 5, a cellulose material is obtained also with high substantivity coloring red dye.

15 Example 6

10 parts of 2- (4'-aminonaphth-1'-yl) -5-aminobenztriazole (84.8%) (prepared by coupling diazotized 4-nitro-1-naphthylamine to m-phenylenediamine, oxidation of the o-aminoazo dye obtained with copper sulfate in pyridine / 2ii water to benzotriazole and subsequent catalytic

Hydrogenation of the nitro group) are tetrazotized in the manner described in Example 2 for the 2- (4'-aminophenyl) -5-aminobenzotriazole-6-sulfonic acid.

This tetrazo solution is kept at 0 to 5 ° and with constant pH at 2 to 2.5 with a solution of 12.1 parts of l-amino-8-hydroxynaphthalene-3,6-disulfonic acid (80.9%) and 4 parts conc. Sodium hydroxide solution in 200 parts of water added over an hour and stirred overnight at 0 to 5 °. Then the resulting blue suspension of the intermediate compound in a solution of l-hydroxy-6-aminonaphthalene-3-sulfonic acid (90.5%) in 200 parts of water and 4 parts of conc. Sodium hydroxide solution allowed to run in at 0 to 5 °, the pH being maintained at 9 to 9.5 by metering in a 10% sodium carbonate solution. The mixture is then stirred overnight at room temperature, then heated to 40 ° for one hour and the dye is finally precipitated by neutralizing the reaction mixture and adding 100 parts of sodium chloride. The dye of formula XIII below dyes cotton substantively and protein-based substrates (e.g. 4i) leather, wool) from a weakly acidic solution in navy blue shades.

XIII

Example 7

10 parts of 4-aza-2- (4'-aminophenyl) -5-aminobenztriazole, 50.4%, (prepared by coupling diazotized 4-aminoacetanilide to 2,6-diaminopyridine, oxidation of the intermediate obtained with copper sulfate in Water / ammonia and subsequent acid saponification of the acetylamino group) are tetrazotized in the manner given in Example 2 for the tetrazotation of 2- (4'-aminophenyl) -5-aminobenzotriazole-6-sulfonic acid.

6 «

The tetrazo compound obtained is in the manner given in Example 6 (acidic first coupling, alkaline second coupling) with 8.78 parts of l-amino-8-hydroxynaphthalene-3,6-disulfonic acid (80.9%) and then with 5, 88 parts of 1-hydroxy-65 6-aminonaphthalene-3-sulfonic acid (90.5% strength) are coupled and the resulting dye is precipitated and isolated. The dye of formula XIV obtained dyes cotton substantively in warm brown shades with good lightfastness.

19th

617 220

HO NH,

XIV

Example 8

10 parts of 2- (3'-aminophenyl) -5-aminobenztriazole are tetrazotinated in the manner given in Example 2 for the tetrazotation of 2- (4'-aminophenyl) -5-aminobenzotriazole-6-sulfonic acid.

The tetrazo compound obtained is acidic in the manner given in Example 6 (first coupling, second coupling

• N = N

alkaline) with 15.75 parts l-amino-8-hydroxynaphthalene-3,6-disulfonic acid (80.9%) and then with 10.54 parts 1-hydroxy-6-aminonaphthalene-3-sulfonic acid (90.5% ig) coupled and the resulting dye isolated by salting out. The i5 dye of Formula XV below dyes cotton substantively in brown-violet tones.

HO NH

HO-S '^ VNS0, H 3 3

N = N

"N

\

N

N '

XV

/

M

Example 9

10 parts of 2- (3'-carboxy-4'-aminophenyl) -5-aminobenztriazole (82%) (prepared by coupling diazotized 2-nitro-5-aminobenzoic acid to m-phenylenediamine, followed by oxidation of the intermediate to benzotriazole with copper sulfate in water / ammonia and reduction of the nitro group with sodium sulfide in water) are tetrazotized in the manner given in Example 2 for the tetrazotation of 2- (4'-aminophenyl) -5-amino-benzotriazole-6-sulfonic acid.

The tetrazo compound obtained is in the manner given in Example 6 (acidic first coupling, alkaline second coupling) with 12 parts of l-amino-8-hydroxy-naphthalene-3,6-disulfonic acid (80.9%) and then with 8. 1 part of 1, 5 hydroxy-6-aminonaphthalene-3-sulfonic acid (90.5% strength) coupled and the dye of the formula XVI below, which dyes cotton substantively in brown-violet tones, isolated by a customary method.

HO NH

H0, £ T VVNS0, .H j J

vW

XVI

If the aqueous solution of dye XVI is treated with 1 mol of copper sulfate in a weakly ammonia-alkaline environment and the solution is then evaporated to dryness, the copper complex of compound XVI is obtained, which dyes cotton substantially in brown tones.

PATENT CLAIMS 1. Process for the preparation of polyazo dyes in substance of the formula

K - N-N - ^ - I Y

1 \ Av '

N = N - K,

X '

wherein

-X- = -N = or-NO =,

05

I = a benzene, naphthalene, pyridine or pyrimidine ring, the nitrogen atoms of which are in the 4- or 6-position relative to the triazole nucleus,

J = the atoms which are necessary to form a 5- or 6-membered aromatic or heterocyclic ring which may have a fused-on aromatic or alicyclic ring,

K! and K2 = residues of coupling components of the aromatic or heterocyclic series, where they can be identical or different, and wherein

I and J unsubstituted or with water-solubilizing groups and alkyl, hydroxy, alkoxy, aryloxy, alkanoyl, aroyl, alkyl or arylsulfonyl, alkanoylamino, unsubstituted or N-substituted carbamoyl or sulfamoyl, alkoxycarbonyl -, Alkoxysulfonyl-, nitro, cyan or trifluoromethyl groups are substituted and all of the above-mentioned alkyl, alkoxy or alkanoyl groups have 1 to 4 carbon atoms, characterized in that coupling compo

617 220

20th

nents of the formulas K ^ H and K2H with tetrazo compounds from diamines of the formula

- NHo y% - ^? R

2 v- '

couples.

2. The method according to claim 1, for producing disazo dyes, characterized in that coupling components of the formulas KrH and K2H explained in claim 1 with tetrazo compounds of diamines of the formula h2n

_ "Nh,

H0C "- © ''

couples, in which I 'and J' with chlorine or bromine atoms, —OH, -SO3H, -COOH, methyl, ethyl, methoxy, ethoxy, phenoxy, β-hydroxyethyl, hydroxymethoxy, carboxymethoxy , Acetyl, benzoyl, methyl or ethylsulfonyl, acetylamino, methoxy or ethoxycarbonyl, nitro, cyano, trifluoromethyl groups or groups of the formula

-Y

/ Ri

-N

can be substituted, where —Y— = -CO- or —S02-, R! = a hydrogen atom, an alkyl or a hydroxyalkyl group, R2 = a cyclohexyl, phenyl, benzyl, benzoyl or phenylsulfonyl group or one of the meanings given for R (and the phenyl ring of the above-mentioned benzyl, phenyl, benzoyl - Or phenylsulfonyl groups with i chlorine or bromine atoms or an alkyl group having 1 to 4 carbon atoms can be substituted.

3. The method according to claim 1 or 2, characterized in that coupling components of the formulas A [H and A2H are used as components K, H or K2H, wherein Ai and A2

a) = a phenyl, alkylphenyl or naphthyl radical which has at least one halogen atom or one -COOH, -S03H, hydroxy, alkoxy, -N02, -NH2, N-alkyl, N-aryl or N, N -Dialkylamino-, alkanoylamino-, -NH-CO-COOH, arylsulfonyl-nyloxy-, or with an -COOH, -S03H or hydroxyl group-containing alkylamino group or with a fiber-reactive group, b) = a naphthyl radical which with a phenylamino, naphthylamino, benzoylamino, phenylsulfonylamino, (p- or m-benzoylamino) benzoylamino, -NH-CO-NH2 or -NH-CO-NH-aryl group, which can carry a fiber-reactive radical , substituted or to a divalent radical of the formula

; Xï> -0 »;

or t> -o nh,

is condensed, where —U— = -S- or —NH- and the phenylamino, benzoylamino or phenylsulfonylamino groups mentioned on the phenyl nucleus can carry —OH, —NH2, —COOH, alkyl or alkoxy groups,

c) a radical of the formula ho,

ho where Z is a hydrogen atom or an -NH2, -N02, -S03H or aminophenylcarbonamide group or a fiber-reactive group, or the formula ho

"Y

! -GL.

ch3

where n is 1 or 2, or the formula oh

-VjO

H3C '

r £)

30 where Y 'can be substituted by an S03H group, or of the formula ch,

wherein Z 'is a hydrogen or chlorine atom or an -NH2, -S03H, alkyl, hydroxyl or COOH group or a fiber-reactive group, or of formula d) is a couplable monoazo or disazo dye, "" wherein in the above formulas which have alkyl, alkoxy or alkanoyl groups of 1 to 4 carbon atoms and A! and A2 can represent the same or different radicals.

C.