DE2208972C3 - Reactive azotriazolyl dyes and their use for dyeing and printing OH- and NH- containing fiber materials - Google Patents

Description

- N-B-Q

have the meaning given in claim 1.

4. Use of the dyes of claims 1-3 for dyeing and printing OH- and NH-containing Fiber materials.

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

(SO ₃ H) _n

correspond to where

A = Cl, CH ₃ , OCH ₃ and K = a) a radical of the formula

Yl

HO

if substituted by C, -C ₄ -alkyl, Cl, C, -C ₄ -alkoxy or SO ₃ H; Naphthyl, optionally substituted by SO ₃ H.

b) a radical of the formula CH ₃

6o

(SO ₃ HL

Y ₁ = CH ₃ , carboxy, carbo-CVQ-alkoxy and Y ₃ = H, C, -C ₄ -alkyl, optionally substituted by Cl. OH or CN, phenyl, given

wonn

R, = H, Cl, CH _{; i} and P = O or I,

c) the 2-hydroxypyridine-6 radical of the formula

HO

e) a radical of a 6-hydroxypyrimidine of the formula HO R ₅

wherein

R ₂ = H, phenyl or CH ₃ , R ₃ = H or CH ₃ , R ₄ = H or CN,

d) a radical of the formula COCH ₃

CH

ίο can be in what

R ₅ = OH, CH ,. Phenyl and R "= OH. NH ₂ , where

R = H or C _{1 -C 4} alkyl. B = direct bond or —CO— or

- SO ₂ - as a bridge to a carbon atom

from Q. O = more detailed in the description

Reactive residue. m = O. 1 or 2, η = O, 1 or 2, c] = O. 1 or 2,

CONH-Y ₂ (SO ₃ H) ₅

wherein

The present invention further relates to processes for the production of the dyes according to the invention and their use for dyeing and printing OH- and NH-containing fiber materials Y ₂ = phenyl, optionally substituted! through like cellulose. Wool and synthetic polyamides. C ₁ -C ₄ -AlCyI, Cl or C ₁ -C ₄ -AIkOXy and Preferred reactive azotriazolyl dyes are

s = 0.1 or 2 or 30 for those in the form of the free acid of the formula

(HO ₃ S) ", where m, ρ and

-Ν — Β — Ο

have the meaning given in claim 1 and

Y ₁ = for a C, -C ₄ -alkyl, carboxyl or a carbalkoxy group with 1-4 C atoms in the alkoxy group and

Y ₂ = a phenyl radical optionally substituted by Cl, €, -Q-alkyl, C, -C ₄ -alkoxy or further substituted and
s = 0, 1 or 2, and those reactive azotriazolyl dyes which are in the form of the free acid of the formula

(HO ₁ S) ₁₁₁

SO ₃ H OH

y y. .

N = N- / "

OH

OH

correspond to where m and
R.

—N — B — Q

have the meaning given above.

The dyes of the general formula (I) are obtained by adding compounds of the formula

H ₂ N-

(IV)

(SO ₃ H) _n

in which n, q and A have the abovementioned meaning and Y ₅ denotes a nitro or acyiamino group, diazotized and with a compound of the formula

(V)

(HO ₃ S) _n ,

O, N

NH ₂

(VI)

(HO ₃ SL

in which m and R have the abovementioned meaning and Y ₆ denotes hydrogen or an acyl group, couples in the o-position to the amino group and then triazolates. After the reduction of the nitro group or saponification of the acyiamino group, which may be required, a reactive component of the formula is used

V —Β —Ο

(VII)

around. where B and Q have the above meanings and V is a removable radical, preferably halogen.
The amino compound of the formula thus obtained

Q — Β — Ν

V-NH,

(HO ₃ SL

(SO ₃ H) _n

(VIII)

is diazoticri and reacted with a coupling component H - K (IX), where K is the above Has meaning.

The reactive dyes can of course also be obtained by adding dyes of the formula

H-N

= N - K

(HOjS) ₁ .

(HO ₃ S) _n

in which mn q, A and R have the abovementioned meaning, reacts with 1 mol of a reactive component of the formula (VII).

Products of the formula (X) are obtained, for example, when a compound of the formula (IV) in which Y _{5 is} a nitro group is diazotized, coupled and triazotized with a compound of the formula (V) in which Y 1 is an acyl group. After the reduction of the nitro group, diazotization is carried out again, coupled with a component (XV) and then

to ßend the acyl group Y ,, split off hydrolytically.

Dyes of the general formula (I) are also obtained by adding compounds of the formula (IV) diazotized and coupled with coupling components H - K and then reduced the nitro group or the acyiamino group saponified. After diazotization of the aminoazc compound of the formula thus obtained

H ₂ N

= N- K

₂ J ^

/ \
(HO ₃ S) _n A,

in which n, q, A and K have the meaning given above, coupling is carried out with compounds of the formula (V) or (VI) and triazolation is carried out. After the reduction of the nitro group or saponification of the acyiamino group, which may be required, the dyes obtained are treated with a reactive component of the formula (VII).

The following compounds, for example, may be used as starting materials for the production of the new dyes called:

a) Amino compounds of the formula (IV):

4-nitro-aniline, 2-chlpr-,

3-chloro-4-nitro-aniline,

2,5-dichloro-, 2,6-dichloro-4-nitro-aniline,

^ Nitro ^ -methyl-aniline,

S-chloro- ^ nitro-l-methyl-aniline,

4-amino-acetanilide, 4-amino-oxanilic acid,

^ S-dichloro- ^ amino-acetanilide,

l-amino-S-acetylamino-toluene,

4-nitro-anflin-sulfonic acid- (2) and - (3),

2-Amino-5-oxalamino-benzenesulfonic acid- (1)

and - (2),

2-amino-5-formylarnino-benzenesulfonic acid,

2-amino-5-acetylamino-benzenesulfonic acid,

809 607/224

S-Nilro-I-amino-benzenecarboxylic acid c-d) and - (2), 2-Amino-5-acetylamino-benzene-carbons; acid- (I) and - (2),

4-nitro-naphthylamine- (I) -sulfonic acid- (5),

4-nitro-naphthylamine- (I) -sulfonic acid- (6), 5

l-Ammo ^ -acetyiamino-naphthalene-silfonic acid- (6) and - (7),

b) Amino compounds of the form! (V) and (Vl):

1,3-diamino-benzene, 1,4-diamino-nuphthulin. 10 2,7-diamino-naphthalene,

2,4-diamino-benzenesulphonic acid, l, 5-diamino-naphthalene-disulphonic acid- (3.7), 1,6-diamino-naphtha! in-disulfonic acid- (4.8).

1,4-diamino-naphthalene-sulfonic acid (6), 15

l-Amino-4-aceiamino-naphthaIine-sulfonic acid- (6),

l-amino-4-acetamino-naphthalene-sulfonic acid- (7),

1-Amino-6- (4-nitrobcnzoyIamino) -naphlhalin- 10 disulfonic acid- (4.8),

l-Amino-4- (3-nitrobenzoylamino) -naphthalenesulfonic acid- (7),

l-amino-4- (4-nitrobenzoylamino) -naphthalene-

sulfonic acid- (6). 25th

c) Coupling components K - H:

3-methylpyrazolone- (5),

l-phenyl-3-methyl-pyrazolone- (5),

1- (2-chlorophenyl) -3-methyl-pyrazolone- (5), 10

l- (2,5-dichlorophenyl) -3-methyl-pyrazolone- (5), 1 - phenyl-3-methyl-pyrazolone- (5) -carboxylic acid- (3) and ethyl ester.

1-PhenyI-3-methyl-pyrazolone- (5) -imide, 1- (2-chlorophenyl) -3-methylpyrazolone- (5) -imide. .is l, o-Tolyl-3-methyl-pyrazolone- | 5) -imide.

1- (2-, 3-, 4-sulfo-phenyl) -3-methyl-pyrazolone- (5).

l- (6-chloro-3-sulfophenyl) -3-methylpyrazolone- (5),

1- (2,5-dichloro-4-sulfo-phenyl) -3-methyl-40

pyrazolone 5),

1- (4-sulfo-2-methyl-phenyl) -3-methylpyrazolone- (5),

! - (6-chloro-4-sulfo-2-methyl-phenyl) -3-methyl-

pyrazolone- (S), 45

1- (4-sulfophenyl) -3-methyl-pyrazolon- (5) -imide, 1- (8-sulfonaphthyl- (2)) -3-methyl-pyrazolon- ( 5) -imide,

1- [6-Su! fo-naphthyl- (2)] -3-methyl-pyrazolone- (5), 1- (4-sulfophenyl) -pyrazolone- (5) -carboxylic acid- (3). 50

! - (o-Chlor- ^ sulfo-i-methyl-phenyl-pyrazolone- (5) -carboxylic acid- (3) -ethyl ester, 1-carboxymethyl-3-methyl-pyrazolone- (5).

1- (2-cyano-ethyl) -3-methyl-pyrazolon- {5),

1 - (2-chloroethyl) -3-methyl-pyrazolone- (5), 55

1-methyl-, ethyl-, propyl-3-pyrazolone- (5), l-methyl ^ -hydroxy- ^ methyl-S-cyanpyridon- (6),

I - phenyl ^ -hydroxy ^ -methyl-S-cyano-

pyridon- (6), 60

2,4,6-trihydroxypyrimidine,

2-methyl-4,6-dihydroxypyrimidine, 2-phenyl-4-amino-6-hydroxypyrimidine, 2-phenyl-4,6-dihydroxypyrimidine,

Acetoacetic anilide, -o-, -m-, -p-anisidide, f> 5

-o-, -m-, -p-toluidid,

Acetoacetic acid-p-chloro-anilide,

Acetoacetic acid (4-chloro-2-methyl-anilide), Acetoacetic acid (2,4- or 2,5- or 2,6-dimethyl-aniüd),

Acetoacetic acid (4-sul fo-anil id), acetoacetic acid (2-methoxy-4-sulfo-5-methylanilide,

Acetoacetic acid (2,4-, 2,5- or 3,5-disulfoanilide),

Eel acetic acid (2,5-disulfo-4-acetylaminoanilide).

Acetoacetic acid - ^ - or 3-sulfo-4-ethoxyanilide),

Acetoacetic acid) 3-sulfo-4-methyl-anilide).

Possible reactive components (VII) are:

Trihalogen-sym.-triazines, such as cyanuric chloride and cyaiiuibroinid,

2,6-dichloro-4-aminotriazine,

2,6-dichloro-4-methylaminotriazine, 2,6-dichloro-4-ethylaminotriazine, 2,6-dichloro-4-oxäthyIaminotriazine, 2,6-dichloro-4-phenylaminotriazine, 2,6-dichloro-4- (o-, m- or p-su! Fophenyl) aminotriazine,

2,6-dichloro-4- (2 ', 5'-, -2', 4'-, or -3 ', 5'-disulfophenyl) aminotriazine,

2,6-dichloro-4-methoxytriazine, 2,6-dichloro-4-ethoxytriazine,

2,6-dichloro-4-phenoxytriazine, 2,6-dichloro-4- (o-, m- or p-sulfophenyl) -oxytriazine,

2,6-dichloro-4-ethylmercaptotriazine, 2,6-dichloro-4-phenylmercaptotriazine, 2,6-dichloro-4- (p-methylphenyl) mercaptotriazine; Tetrahalopyrimidines, such as telrachlor, telrabromine or tetrafluoropyrimidine.

2,4,6-trihalogenopyrimidines, such as 2,4,6-trichloro-, -tribromo- or -trifluoropyrimidine, Dihalopyrimidines, such as 2,4-dichloro-, -dibromo- or -difluoropyrimidine; 2,4,6-trichloro-5-nitro- or -5-methyI- or -5-carbomethoxy- or -S-carboethoxy- or -5-carboxymethyl- or -5-mono-, -di- or -trichloromethyl- or -5-carboxy- or 5-siilfo- or -5-cyano- or -5-vinyl-pyrimidine, 2,4-Difluoro-6-methyipyrimidine, 2,6-Difluoro-4-methyl-5-chloropyrimidine, 2,4-difluoro-pyrimidine-5-ethylsulfone, 2,6-difluoro-4-chloropyrimidine,

2,4,6-Trifluoro-5-chloropyrimidine, 2,6-Difluoro-4-methyl-5-bromopyrimidine, 2,4-DIfIuOr-S ₁ O ^ iChIOr- or -dibromopyrimidine, 4,6-Difluor- 4,5-dichloro- or -dibromopyrimidine, 2,6-difluoro-4-bromopyrimidine,

2,4,6-trifluoro-5-bromopyrimidine, 2,4,6-trifluoro-5-chloromethylpyrimidine, 2,4,6-trifluoro-5-nitropyrimidine, 2,4, b-trifluoro-5-cyanopyrimidine, 2,4,6-trifluoro-pyrimidine-5-carboxylic acid alkyl ester or -5-carboxamides,

^ o-Difluoro-S-methyl- ^ chloropyrimidine, 2,6-difluoro-5-chloropyrimidine,

2,4,6-trifluoro-5-methylpyrimidine, 2,4,6-trifluoro-6-methylpyrimidine, 2,4-difluoro-5-nitro-6-chloropyrimidine, 2,4-difluoro-5-cyanopyrimidine,

2,4-difluoro-5-methylpyrimidine, 6-trifluoromethyl-5-chloro-2,4-difluoropyrimidine, 6-phenyl-2,4-difluoropyrimidine,

o-trifluoromethyl ^^ - difluoropyrimidine, 6-trifluoromethyl-2,4-difluoropyrimidine, 5-fluoromethyl-2,4,6-trifluoropyrimidine, 2,4-difluoro-5-nitro-pyrimidine,

2,4-difluoro-5-trin'uomethyl-pyrimidine, 5

2,4-Difluoro-5-methysulfonyl-pyrimidine, 2,4-Diiluor-5-phcnyI-pyrimidine, 2,4-Difiiior-5-carbonamido-pyrimidine, 2,4-difluoro-5-larbomethoxypyrimidine,

2,4-dilluoro-6-trinuomethyl-pyrimidine. ι ο

2,4-dilluoro-5-bromo-6-irifluoromethyl-pyrimidine, 2,4-difluoro-6-carbonamido-pyrimidine, 2,4-difluoro-6-carbonamido-pyrimidine, 2,4-difluor-6-carbomethoxypyrimidine,

2,4-difluoro-6-phenyl-pyrimidine, ι _s

2,4-di-fluoro-o-cyano-pyrimidine,

2,4,6-trifluoro-5-methylsulfonyl-pyrimidine.

2,4-Dinuor-5-sulfonamido-pyrimidine.

2,4-Difluoro-5-chloro-6-carbomethoxypyrimidine.

5-trifluoromethyl-2,4-difluoropyrimidine, 20

2,4-dichloropyrimidine-5-carboxylic acid chloride, 2,4,6-trichloropyrimidine-5-carboxylic acid chloride, 2-methyl-4-chloropyrimidine-5-carboxylic acid chloride,

2-chloro-4-methylpyrimidine-5-carboxylic acid-25

chloride,

2,6-dichloropyrimidine-4-carboxylic acid chloride; also 2-carboxymethylsulfonyl-4-chloropyrimidine,

2-methylsulfonyl-4-ch] or-6-methylpyrimidine, \ o 2,4-bis-methylsulfonyl-6-methylpyrimidine, 2,4-bis-phenylsulfonyl-5-chloro-6-methylpyrimidine,

2,4,6-Tris-methyl-sulfonyl-pyrimidine, 2,6-bis-methyl-sulfonyl-4,5-d-chloride pyrimidine. 35 2,4-bis-methylsulfonylpyrimidine-5-sulfonic acid chloride,

2-methyl-sulfonyl-4-chloropyriInidine, 2-phenylsulfonyl-4-chloropyrimidine,

2,4-bis-trichloromethyl-sulfonyl-6-methy! - 40

pyrimidine,

2,4-bis-methylsulfonyl-5-chloro-6-methylpyrimidine,

2,4-bis-methylsulfonyl-5-bromo-6-methyl-

pyrimidine, 45

2-methylsulfony! -4,5-dichloro-6-methylpyrimidine, 2-methylsulfonyl-4,5-dichloro-6-chloromethylpyrimidine,

2-MethylsuIfoτ ^ yl-4-chloro-6-methylρyrimidin-

5-sulfonic acid chloride, 50

2-methylsulfonyl-4-chloro-5-nitro-6-methylpyrimidine,

2,4,5,6-tetramethylsulfonyl-pyrimidine,

I-methylsulfonyl ^ chloro-S ^ -dimethylpyrimidine, 2-EthylsulfonyI-4,5-dichloro-6-methylpyrimidine, 55 2-methylsulfonyl-4,6-dichloropyimidine, 2,4,6-Trismethylsulfonyl-5-chlorpyrirπidin, 2-MethyIsulfonyl-4-chloro-6-caΓboxypyrimidin, 2-methylsulfonyl-4-chloφyΓimidine-5-sulfone

acid, 60

2-methylsulfonyl-4-chloro-6-carbonlethoxypyrimidine,

I-methylsulfonyl ^ chloropyrimidine-S-carboxylic acid,

2-methylsulfonyl-4-chloro-5-cyano- '^r; -Tnethoxy- 65

pyrimidine,

l-methylsulfonyM ^ -dichloropyrimidine, 4-methylsulfonyl-6-cnloΓpyrimidine,

2-sulfoethylsulfonyl-4-chloro-6-methyl-pyrimidine, 2-methylsulfonyl-4-chloro-5-bromopyrimidine,
2-methylsulfonyl-4-chloro-5-bromo-6-methylpyrimidine,

2,4-bis-methylsulfonyl-5-t; chloropyrimidine,
2-phenylsulfonyl-4,5-dichloropyrimidine,
2-phenyl-sulfonyl-4,5-dichloro-6-methylpyrimidine, 2-carboxymethylsulfonyl-4,5-dichloro-6-methylpyrimidine,

2- (2'- or 3'- or 4'-carboxy-phenylsulfonyl) -4,5-dichloro-6-methylpyrimidine,
2,4-bis- (2'- or 3'- or 4'-carboxyphenylsulfonyl) -5-chloro-6-methylpyrimidine;
2-methylsulfonyl-6-chloropyrimidine-4- or
-5-carboxylic acid chloride,
2-Ethysulfonyl-6-chloropyrimidin-4- or
-5-carboxylic acid chloride,
2,6-bis (methylsulfonyl) -pyrimidine-4-carboxylic acid chloride,

2-methylsulfonyl-6-methyl-4-chloro- or ₍
^ -bromopyrimidine-S-carboxylic acid chloride or /
-bromide,

2,6-bis (methylsulfonyl) -4-chloropyrimidine-5-carboxylic acid chloride; then also the reactive components of the heterocyclic series with reactive sulfonyl substituents,
3,6-bis-phenylsulfonyIpyridazine,
3-methylsulfonyl-6-chloropyridazine,
3,6-bis-trichloromethylsulfonylpyridazine.
3,6-bis-methylsulfonyl-4-methyl-pyridazine,
2,5,6-tris-methylsulfonylpyrazine,
2,4-bis-methylsulfonyl-1,3,5-triazine,
2,4-bis-methylsulfonyI-6- (3'-sulfophenylamino) -1.3,5-triazine.

2,4-bis-methylsulibnyl-6-N-methylanilino-1,3,5-triazine,

2,4-bis-methylsulfonyl-6-trichloroethoxy-1,3,5-triazine,

2,4,6-Tris-phenylsulfonyI-1,3,5-triazine,
2,4-bis-methylsulibnylquinazoline,
2,4-bis-trichloromethyl-sulfonylquinoline,
2,4-bis-carboxy-methyl-sulfonylquinoline,
2,6-bis- (methylsulfonyl) -pyridine-4-carboxylic acid chloride and 1- (4'-chlorocarbonylphenyl or
2'-chlorocarbonylethyl) -4,5-bis-methyl-sulfonylpyridazon- (6);

2,4-bis-methylsulfonyl-6-phenoxy-1,3,3-t-iazine
and the herocyclic reactive components with mobile halogen 2- or 3-monochloroquinoxaline-6-carboxylic acid chloride or -6-sulfonic acid chloride, 2- or 3-monobromoquinoxaline-6-carboxylic acid bromide or -6-sulfonic acid bromide, 2,3-dichloroquinoxaline-6-carboxylic acid chloride or - 6-sulfonic acid chloride,

2,3-dibromoquinoxaline-6-carboxylic acid bromide
or -6-sulfonic acid bromide,
1 ^ -Dichlorphthalazin-o-carboxylic acid chloride or -6-sulfonic acid chloride and the corresponding bromine compounds, 2,4-dichloroquinazein-6- or -7-carboxylic acid chloride and the corresponding bromine compounds, 2- or 3- or 4- (4 ', 5' -Dichlorpyridazon - 6 '- yl - V) - phenylsulfonic acid chloride or -carboxylic acid chloride and the corresponding bromine compounds, / H4', 5'-dichloropyridazon - 6 '- yl - 1') - ethyl carboxylic acid chloride, 2-chloroquinoxaline-3-carboxylic acid chloride and the corresponding Bromine compounds, N-methyl-N - (2,4 - dichlorotriazinyl - 6) - carbamic acid

chloride, N-methyl-N- (2-chloro-4-methylaminotriazinyl-6) -carbamic acid chloride, N-methyl-N - (2 - chloro - 4 - dimethylamine - triazinyl - 6) -carbamic acid chloride, N-methyl- or N-ethyl-N - (2,4 - dichlorotriazinyl - 6) - amino - acetyl chloride, N-methyl-, N-ethyl- or N-hydroxyethyl-N- (2,3-dichloroquinoxaline-6-sulfonyl- or -6-carbonyl) aminoacetyl chlorides and the corresponding Bromine derivatives, also 2-chlorobenzlhiazole-5- or -6-carboxylic acid chloride or -5- or -6-sulfonic acid chloride and the corresponding bromine compounds, 2-arylsulfonyl- or 2-alkylsulfonyl-benzothiazole-5- or -6-carboxylic acid chloride or -5- or -6-sulfonic acid chloride, such as 2-methyl-sulfonyl- or 2-ethylsulfonyl- or 2-phenylsuifonyl-benzthiazol-5- or -6-sulphonic acid chloride or -5- or -o-carboxylic acid chloride and the corresponding 2-sulfonylbenzothiazole derivatives containing sulfonic acid groups in the fused benzene ring, 3,5-bis-methylsulfonyl-isothiazole-4-carboxylic acid chloride, 2-chlorobenzoxazole-5- or -6-carboxylic acid chloride or sulfonic acid chloride and the corresponding bromine derivatives, 2-chlorobenzimidazole-5- or -6-carboxylic acid chloride or sulfonic acid chloride and the corresponding bromine derivatives, 2-chloro-1-methylbenzimidazoI-5- or -6-carboxylic acid chloride or -sulfonic acid chloride and the corresponding bromine derivatives.

2 - chloro - 4 - methylthiazole - (1,3) - 5 - carboxylic acid chloride or -4- or -5-sulfonic acid chloride, 2-chlorothiazole-4- or -5-sulfonic acid chloride and the corresponding bromine derivatives.

From the series of aliphatic active components come into question:

Acrylic acid chloride.

Mono-, di- or trichloroacroic acid chloride.

3-chloropropionic acid chloride,

3-Phenylsulfonyl-prop: onic acid chloride.

3-methyl sulfonyl propionic acid chloride.

3-ethylsulfonyl-propionic acid chloride.

2-chloroethane sulfochlorine class.
Chloromethanesulfonyl chloride.

I-chloroacetyl chloride.

2,2,3, S-tetrafluorocyclobulin-1 -carboxylic acid

chloride,

/ M2,2,3,3-tetrafluorocyclobulyl-1) acrylic acid chloride.

/ i- (2,3,3-trifliior-2-chloro-cydobutane-l-carbon-

acid chloride,

/ i-methyl-sulfonyl-acrylic acid chloride.

α-methylsulfonyl-acrylic acid chloride and
a-bromoacrylic acid chloride and

/ i-bromoacrylic acid chloride.

The new dyes are particularly suitable for dyeing and printing natural and natural

2s ured cellulosic fiber materials such as cotton and Spun rayon as well as natural and synthetic polyamide fiber material: ii. for example such Wool, silk, poly-caprolactam or the polycondensate of hexamethylenediamine and adipine

τ, ο acid. The dyeings obtained, especially those on cotton and rayon, are distinguished by good fastness healing properties, especially fastness to light and fastness to light.

The dyes of the formulas
a)

HO ₃ S

Ci
Cl

COHN

COOH

Y = N

SO ₃ H

HO ₃ S

Cl

OH

SO ₃ H

according to German patent application P 22 08 972.1-43 show compared to the examples known from British patent 11 82 761 1.1 / 6 and 1/5 surprising advantages in the depth of color in the reactive dyeing of cotton; a) is also surprisingly more lightfast than the dye known from British Patent 11 82 761, Example 1.

15th
The dye of the formula

HO.S

SO ₃ H

SO ₃ H

shows the surprising advantage over the dye known from DT-AS 11 53 842, Example 3, No. 11 the better solubility in water, the dye of the formula

Cl

HO ₃ S

SO ₃ H

CH ₃

I _n SO ₃ H

/ ^ I

^{N = N} y * <>

O I

SO ₃ H

shows compared to that from GB-PS 11 82 761, example I-6 known dye have the surprising advantage in dyeing cotton from long To deliver liquor deeper colorations.

example 1

26.0 g (0.1 mole) of 1-amino-4-oxalylamino-benzenesulfonic acid 6.9 g of sodium nilrite are added in aqueous solution at pH = 7 and in the usual way indirectly diazotized by pouring the solution into 28 ml of hydrochloric acid (28%). The finished diazotization are added to an aqueous suspension of 33.3 g (0.105 mol) of 1,6-diamino-naphthalene-disulfonic acid-4,8 and blunt with 20% sodium acetate solution to pH = 4. Neutralized after the reaction has ended sodium hydroxide solution is added, 90 ml of concentrated ammonia are added and the mixture is heated to 80-90 C. 56 g (0.22 mol) of copper sulphate are then sprinkled in for triazolation and the temperature is maintained until the color is discolored the solution To split off the oxalyl radical and to precipitate copper oxide, it is mixed with Sodium hydroxide (4% of the total volume) and boil for two more hours. Then it is filtered off and represents the filtrate kongost.uer, the triazole being the Formula (I) fails. (Yield approx. 0.08 mol; 80%).

HO ₃ S

SO ₃ H

H, N

SO ₃ H

The product is dissolved in 700 ml of water at pH = 5 and 11 ml of 2,4,6-trifluoro-5-chloro-pyrimidine are left at room temperature a drop. The pH is kept constant by adding soda. When the reaction has ended, 6 g of sodium nitrite are added and the mixture is left pour into 30 ml of hydrochloric acid (28%). After reacting for an hour, any excess nitrous oxide is destroyed Acid with sulfamic acid, sprinkles 17.6 g (0.086 mol) of 1-phenyl-3-carboxy-pyrazolone- (5) and buffers with sodium acetate at pH = 5. After the end of the reaction, it is filtered off and dried at 40 "C. Vacuum. The dyestuff obtained has the formula as the free acid

HO ₃ S

SO ₃ H

COOH

U.N

SO ₃ H

It is an orange-colored powder that binds to Formula 1 after treatment with the Water with yellow color dissolves and cotton in gold- fts reactive component diazoticrl and with a cup

stains yellow tones.

The dyes listed in Table I below are obtained analogously to Example 1 if the distribution component is used implements.

The dyes show the specified shades and dye cotton in these shades.

809 607/224

17th Table 1 Sj
\
N- < 22 08 972
18th SO ₃ H hue Diazo component ^ - '3-methylpyrazolone- (5) HO ₃ SI Coupling components l-Phcnyl-3-methyl-pyrazolone- (5) yellow J = N rr ^ / \ SO ₃ H
F Cl l-phenyl-pyrazolone- (5) -earboxylic acid- (3) -
ethyl ester yellow I. the same l- (2-chloro-phenyl) -3-methyl-pyrazolon- (5) yellow ί the same 1 - (2,5-dichlorophenyl) -3-methyl-
pyrazolone- (S) yellow f the same I - (2-methyl-phenyl) -3-methyl- ■
pyruzolone (5) yellow I.
I. the same 1,3-dimethylpyrazolone- (5) yellow I. the same l-carboxy-methyl-3-methyl-pyrazolone- (5) yellow the same l- (2-carboxy-ethyl) -3-methyl-pyrazolone- (5) yellow : the same l- (2-carboxy-ethyl) -3-carboxy-
pyrazolone- (5) yellow S the same 1- (4-sulfo-phenyl) -3-mcihyl-pyrazolon- (5) yellow (jcsgl. l- (2-methyl-4-sulfo-phenyI-3-methyl-
pyrazolone- (5) yellow the same l- (4-sulfo-phenyl) -pyrazoIon- (5) -carbon-
acidic (3) yellow j the same l- (2,5-dichloro-4-sulfophynyl) -3-methyl-
pyrazolone- (5) yellow ί the same l- (2-sulfo-phcnyI) -3-methyl-pyrazolone- (5) yellow j
ι the same l- (3-sulfamoyl-phenyl) -3-methyl-
pyrazolone- (5) yellow I. the same l- (6-chloro-3-sulfo-phenyl) -3-methyl-ethyl-
pyrazolone- (5) yellow : the same l- (2-chloro-4-sulfo-phenyl) -3-methyl-
pyraznlon- (5) yellow the same 1- (6-C "chloro-4-sulfo-2-methyl-phenyI) -
3-methyl-pyrazolone- (5) yellow the same 1- [6-sulfonaphthyl- (2)] -3-methyl-
pyrazolone- (5) yellow ' the same 1-phenyl-3-methyl-5-aminopyrazole yellow ; the same 1- (3-sulfophynyl) -3-methyl-5-amino-
pyrazole yellow the same Barbituric acid yellow ι the same Acetic acid-o-anisidide yellow the same Acetoacetic acid-o-loluidide yellow ί the same 1- (3-carboxy-phenyl) -3-methyl-
pyrazolone- (5) yellow ; yellow

the same.

desjil.

3,4-dimethyl-2-hydroxy-5-cyano-pyridon- (6)

pyridon- (6)

2-hydroxy-pyridone- (6)

2-hydroxy-4-carboxy-ryridone- (6)

yellow yellow

yellow same

If you put the cold solution of the triazole compound of formula 1 with 15.5 g of cyanuric chloride, which is in 80 ml Dissolved acetone and then poured into ice water

by keeping pH = 6 constant by adding soda, the diazo component the formula

HO ₃ S

to win.

It is diazolized analogously to Example 1. With the coupling components specified in Table I are the corresponding reactive dyes obtained.

If the solution of the compound of the formula (3) is treated with 50 ml of 10% strength ammonia solution at 30-40 ° C (2 hours) the diazo component of the formula is obtained

HO ₃ S

SO ₃ H

It is obtained after acidification with hydrochloric acid, isolated speaking reactive dyes,

and then dissolved neutrally in 700 ml of water and lets 1-amino-benzene-

analogous to Example 1 diazotized. With the in Table I an- 35 3,5-disulphonic acid at pH = 5 (40 ^J C) is obtained

given coupling components become the one the diazo component of the formula

SO ₃ H

SO ₃ H

HO ₃ S

(4a)

SO ₃ H

After diazotization and reaction with the coupling components indicated in Table I, it is used the corresponding reactive dyes obtained.

If you put the compound of formula (I) with 26 g of 2,3-dichloro-quinoxaline-6-carboxylic acid chloride at 35 to 40 ° C. and pH 6 μm, with the acid chloride being kept in suspension, the diazo component is obtained the formula

Cl

HO ₃ S

SO ₃ H

It is diazotized analogously to Example 1 and, with the coupling components given in Table I, gives the corresponding dyes.

If the solution of the triazole compound of the formula (1) is added to 19.3 g of 2-methylsulfonyl-4,5-dichloro-6-methylpyrimidine at 60-65 ° C by neutralizing the hydrochloric acid liberated by adding soda, so the diazo component of the formula is obtained

HO, S SO ₃ H

CH ₁ -O ₇ S

NH,

CH ₃

It is diazoiated analogously to Example 1 and results in the coupling components indicated in Table I the corresponding dyes.

If the compound of formula 1 is used with 2,6-dichloro-4-methoxy-triazine, 2,6-dichloro-4-ethoxy-triazine, 2,6-dichloro-4-i-propoxy-triazine, 2,6-dichloro-4- (2-hydroxyethy) triazine, Tetrachloropyrimidine, 2,4,6-trichloro-5-carboxymethyl-pyrimidine, 2,6-difluoro-5 - chloro - pyrimidine, 2,4,6 - trifluoro - 5 - carboxyethylpyrimidine or 2,4-difluoro-5-chloro-6- (4-nitrophenoxy) pyrimidine in the presence of acid-binding agents Means, as is known from the literature, to. this gives diazo components with further reactive radicals. After diazotization and their coupling with the components indicated in Table I is obtained one the corresponding dyes.

4-Nilraniline is diazotized in a known manner

HO ₃ S is the place of l-amino-4-oxalylamino-benzenesulphonic acid and the procedure is as in Example I. The triazole compound is obtained

HO ₃ S

V-NO, (7)

H ₂ N

The reduction of the nitro group by the usual methods with iron or hydrogen / Raney-Nickcl and subsequent reaction of the compound with 2,4,6-trifluoro-5-chloropyrimidine gives the diazo component

SO ₃ H

Their diazotization and coupling as in Example 1 gives the dyes shown in Table II. they show the specified shades and dye cotton in these shades.

Table II Diazo component

HO ₃ S

Coupling component

hue

NH ₂ 1- (4-sulfo-phenyl) -3-methyl-pyrazolone- (5) yellow

Claims (3)

Patent claims: 1. Azotriazole dyes in the form of the free acid of the formula (D (SO ₃ H) _n (SO ₃ H) _1n correspond to where A = CJ, CH ₃ , OCH ₃ and
K = a) a radical of the formula .1 ° Y ₁ = CH ₃ , carboxy, carbo-C, -C ₄ -alkoxy and Y ₃ = H, qQ-alkyl, optionally substituted by Cl, OH or CN, phenyl, optionally substituted by C ₁ -C ^ - alkyl, Cl , C, -C ₄ -alkoxy or SO ₃ H; Naphthy !. possibly substituted by SO ₃ H. b) a radical of the formula CH ₃ NH ₁ (SO ₃ H) _p 40 45 R ₁ = H, Cl, CH ₃ and
P = O or 1. SO ₃ H c) the 2-hydroxypyridine-6 radical of the formula HO wherein R ₂ = H, phenyl or CH ₃ ,
R ₃ = H or CH ₃ ,
R ₄ = H or CN, d) a radical of the formula
COCH ₃ -CH CONH-Y ₂ (SO ₃ H) ₅ wherein Y ₂ = phenyl, optionally substituted by C, -C ₄ -alkyl, CI or C, -C ₄ -alkoxy and s = 0,1 or 2 or e) a radical of a 6-hydroxypyrimidine of the formula HO can be in what R ₅ = OH, CH ₃ , phenyl and R ₆ = ■■ OH, NH ₂ ,
whereby R = H or C, -C ₄ -alkyl, B = direct bond or —CO— or - SO ₂ - as a brick link to one C atom of Q,
Q = more detailed in the description Reactive residue,
m - O, 1 or 2,
/ 1 = O, I or 2,
q = O, I or 2, 2. Reactive azotriazolyl dyes in the form of the free acid of the formula N = -N- N-Y, (SO ₃ H) ₁ (HO ₁ S) ,,,
correspond to where m, ρ and - N— B- have the meaning given in claim I and Y ₁ = for a Cj-Q-alkyl, carboxyl or a carbalkoxy group with 1-4 C atoms in the alkoxy group, and
Y ₂ = one optionally by Cl, C ₁ -C ₄ -AlkVl. C.-Q-alkoxy or further substituted phenyl radical and s = 0, 1 or 2. 3. Reactive azotriazolyl dyes in the form of the free acid of the formula SO ₃ H N = N- (HO ₃ S) _n , where m and OH Ln