DE1644186C3 - Reactive dyes and their use for dyeing and printing cellulosic materials - Google Patents

Description

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

(HO ₃ S) _1n -

/ f

-N = N- > SO ₃ H V. N- -NH ₂ / -A

.1 °

where X = H, halogen, nitro, A = pyrimidine-1,3 radical or sym.-triazine radical with at least one removable sulfonyl or halogen substituent, m - 2 otier 3, and their use for dyeing and printing cellulosic Materials. Suitable radicals A are, for example, mono- or dihalo-sym.-triazinyl radicals, e.g. B.

2,4-dichlorotriazinyl-6-, 2-amino-4-chlorotriazinyl-6-,

2-alkylamino-4-chlorotriazinyl-6-, such as 2-methylamino-4-chlorotriazinyl-6-, 2-ethylamino- or 2-propylamino-4-chlorotriazinyl-ί »-, 2 - / ^ - Oxäthylamino-4-chlorotriazinyl-6-, 2-Di - / <- oxäthylamino-4-chlorotriazinyl-6- and the corresponding sulfuric acid half-ester, 2-diethylamino-4-chlorotriazinyl-6-, 2-Moφholino- or 2-piperidino-4-chlorotriazinyl-6-,

2-Cyclohι ^ xylamino-4-chlorotriazinyl-6-, 2-arylamino and subst. Arylamino-4-chlorotriazinyl-6-, how

2- Phenylamino ^ chlorotriazinyl-o-, ^

2- (o-, m- or p-sulfophenyl) -amino-4-chlorotriazinyl-6-,

2-alkoxy-4-chlorotriazinyl-6-, such as 2-methoxy- or ethoxy ^ -chlorotriazinyl-o-, 2- (phenylsulfonylmethoxy) -4-chlorotriazinyl-6-. hs 2-aryloxy and subst. Aryloxy ^ -chlorotriazinyl-o-, how

2-1 ^:> henoxy-4-chlorotriazinyl-6-.

2- (p-sulfophenyl) -oxy-4-chlorotriazinyl-6-,

2- {o-, m- or p-methyl or

Methoxyphenyl) -oxy-4-chlorotriazinyl-6-, 2-alkyl mercapto or 2-aryl mercapto or 2- (substituted aryl) -mercapto-4-chlorotriazinyl-6-, such as 2 - (/ <- hydroxyethyl) mercapto-4-chlorotriazinyl-6-,

2- Phenylmercapto ^ -chlorotriazinyl-e-, 2- (4'-methylphenyl) mercapto-4-chlorotriazinyl-6-, 2 - (2 ', 4' - Dinitro) - phenylmercapto - 4 - chlorotriazinyl-6-,

Mono-, di- or trihalopynmidyl radicals, such as 2,4-dichloropyrimidyl-6-,

2,4,5-Trichloφyrimidyl-6-, 2,4-dichloro-5-nitro- or -5-methyl- or -5-carboxymethyl- or -5-carboxy- or -5-cyano- or -5-vinyl- or -5-sulfo- or -5-mono-, -di- or -trichloromethyl- or -S-carboalkoxy-pyrimidyl-o-,

as well as the corresponding bromine and fluorine derivatives of the above-mentioned chlorine-substituted heterocyclic ones Leftovers;

triazine radicals containing sulfonyl groups, such as 2,4-bis- (phenylsulfonyl) -triazinyl-6-, 2- (3'-Carboxyphenyl) sulfonyl-4-chlorotriazinyl-6-.

2- (3'-sulfophenyl) -sulfonyl-4-chlorotriazinyl-6-.

2,4-bis (3 '-carboxyphenylsulfonyl-1'-) -triazinyl-6-;

pyrimidine rings containing sulfonyl groups, such as 2-carboxymethylsulfonyl-pyrimidinyl-4, 2-methylsulfonyl-6-methyl-pyrimidinyl-4.

2-methylsulfonyl-6-ethyl-pyrimidinyl-4, 2-phenylsulfonyl-5-chloro-6-methylpyrimidinyl-4.

2,6-bis-methylsulfonyl-pyrimidinyl-4.

2,5-bis-methylsulfonyl-5-chloro-pyrimidinyl-4.

2,4-bis-methylsulfonyl-pyrimidine-5-sulfonyl.

2-methylsulfonyl-pyrimidinyl-4, 2-phenylsulfonyl-pyrimidinyl-4, 2-trichloromethylsulfonyl-6-methylpyrimiclinyl-4,

i-methylsulfonyl-S-bromo-ö-methylpyrimiclinyl-4,

2-methylsulfonyl-5-chloro-6-methylpyrimidinyl-4,

2-methylsulfonyl-5-chloro-6-ethyl-pyritnidinyl-4, 2-methylsulfonyl-5-chloro-6-chloromethylpyrimidinyl-4,

2-methylsulfonyl-4-chloro-6-methylpyriπlidin-5-sulfonyl,

2-methylsulfonyl-5-nitro-6-methyl-pyrimidinyl-4, 2,5,6-tris-methylsulfonyl-pyrimidinyl-4, 2-methylsulfonyl-5,6-dimethyl-pyrimidinyl-4, 2-ethylsulfonyl-5-chloro-6-methyl-pyrimidinyl-4, 2-methylsulfonyl-6-chloro-pyrimidinyl-4, 2,6-bis-methylsulfonyl-5-chloro-pyrimidinyl-4.

2-methylsulfonyl-6-carboxypyrimidinyl-4, 2-methylsulfonyl-5-sulfo-pyrimidinyl-4, 2-methylsulfonyl-6-carbomethoxy-pyrimidinyl-4.

2-methylsulfonyl-5-carboxy-pyrimidinyl-4.

2-methylsulfonyl-5-cyano-6-methoxypyritnidinyl-4,

2-methylsulfonyl-5-chloro-pyrimidinyl-4.

2-sulfoethylsulfonyl-6-methylpyrimidinyl-4, 2-methylsulfonyl-5-bromo-pyrimidinyl-4.

2-phenylsulfonyl-5-chloro-pyrimidinyl-4.

2-CaΓboxymethylsulfonyl-5-chloro-6-methylpyrimidinyl-4.

The new dyes are obtained by coupling a diazotized one, optionally in the specified Way substituted 2-aminonaphthalene-di- or trisulfonic acid with a compound of the formula

SO ₃ H

where A has the meaning already given.

The coupling takes place in an acidic, aqueous or aqueous-organic medium and attacks in the p-position to the NH ₂ group of the coupling component. Aminonaphthalene di- or trisulfonic acids suitable for the reaction are, for example

2-aminonaphthalene-4,8-disulfonic acid,

2-aminonaphthalene-5,7-disulfonic acid,

2-aminonaphthalene-6,8-disulfonic acid,

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

2-aminonaphthalene-4,6,8-trisulfonic acid. ^2>

2-amino-6-nitronaphthalene-4,8-disulfonic acid.

2-aminonaphthalene-4,7-disulfonic acid,

2-aminonaphthalene-3,6-disulfonic acid,

2-aminonaphthalene-3,7-disulfonic acid.

Coupling components of the formula (11) are obtained by condensation of 1,3-diaminobenzene-4-sulfonic acid, with compounds of the formula

A-W

where A has the meaning given and W is a removable substituent.

In the reaction, generally an acylation reaction is, only the amino group in the p-position to the sulfonic acid group becomes part of the grouping -N (H) -A transferred.

Suitable reactive components A - W are, for example those on which the aforementioned reactive groups A are based, d. H. generally the Halides of the sulfonyl compounds of the acyl components mentioned A. From the large number of for The available connections are mentioned here in excerpts:

Trihalogen-sym.-triazines, such as

Cyanuric chloride and cyanuric bromide,

Dihalo-monoamino- and -mono-subst-

amino-sym.-triazine, such as

2.6-DichlcT-4-aminotriazine,

2,6-dichloro-4-methylaminotriazine,

2.6-dichloro-4-ethylaminotriazine.

2.6-Pich! Or-4-oxethylaminotriazine.

2.6-dichloro-4-phenylaminotriazine.

2.6-dichloro-4- (o-, m- or p-sulfophen \ l) -aminoiriazine.

2.6-dichloro-4- (2 ', 3'-, -2', 4'-. -.V.4- or

-V.S'-disulfophcnyiy-aminotriazine.

Dihaloalkoxy- and -aryloxy-sym.-triazines, such as 2.6-dichloi -4-methoxytriazine.

2,6-dichloro-4-athoxytriazine.

2,6-dichloro-4-phenoxytriazine.

2.6-dichloro-4- (o-, m- or p-sulfophenyl) -

oxytria / in.

for example dihalo-alkylmercapto- and -arylmercaptosym.-triazines, such as 2,6-DicWor-4 ^ - aylmercaptotriazine,!, o-dichloro- ^ phenylmercaptotriazine, 2,6-dichloro-4- (D-methylphenyl) -mercaptotriazine; Tetrahalopyrimidines, such as tetrachloro-, tetrabromo- or tetrafluoropyrimidines, 2,4,6-trihalopyrimidines, such as 2,4,6-trichloro-, -tribromo- or -trifluoropyrimidine, dihalopyrimidines, such as 2,4-dichloro-, dibromo- or difluorine -pyrimidines, 2,4,6-trichloro-5-nitro- or -5-methyl- or -S-carbomethoxj'- or -5-carboälhoxy- or -S-carboxymethyl- or -5-mono-, -di or -trichloromethyl- or -5-carboxy- or -5-sulfo- or -5-cyano- or -5-vinyl-pyrimidine. 2.4.6-trifluoro-5-chlorophyrimidine; Pyrimidine reactive components with removable sulfonyl groups, such as 2-carboxymethylsulfonyl-4-chloropyrimidine, 2-methylsulfonyl-4-chloro-6-methylpyrimidine. 2,4-bis-methylsulfonyl-6-methylpyrimidine. 2,4-bis-phenylsulfonyl-5-chloro-6-methylpyrimidine, 2,4,6-tris-methylsulfonylpyrimidine. 2,6-bis-methylsulfonyl 4,5-di-chloφyΓimidin. 2,4-bis-methylsulfonylpyrimidine-5-sulfonic acid chloride, 2-methylsulfonyl-4-chloropyrimidine. 2-phenylsulfonyl-4-chloropyrimnJin. 2.4-bis-trichloromethylsulfonyl-6-methylpyrimidine, 2,4-bis-methylsulfonyl-5-chloro-6-methylpyrimidine, 2.4-bis-methylsulfonyl-5-bromo-6-methylpyrimidine, 2-methylsulfonyl-4,5- dichloro-6-methytpyπmidin. 2-methylsulfonyl-4,5-dichloro-6-chloromethylpyrimidine, 2-methylsulfonyl-4-chloro-6-methylpyrimine-5-sulfonic acid caloride, 2-methylsulfonyl-4-chloro-5-n; tro-6-meth \ lpyrimidine, 2,4,5,6-tetra-methylsulfonylpyrimidine, I-methylsulfonyl-1-chloro-So-dimethylpyrimidine. 2-ethylsulfonyl-4,5-dichloΓ-6-methylpyrimidine. 2-methylsulfonyl-4,6-dichloropyrimidine. 2.4.6-Tris-methylsulfonyl-5-chloropyrimidine, 2-methylsulfonyl-4-chloro-6-carboxypyrimidine. 2-methylsulfonyl-4-chloφyΓimidine-5-sulfonic acid. 2-methylsulfonyl-4-chloro-6-carbomethoxypyrimidine, 2-methylsulfonyl-4-chloropyrimidine-5-carboxylic acid,

2-methylsulfonyl-4-chloro-5-cyano-6-methoxypyrimidine.

2-methylsulfonyl-4,5-dichloropyrimidine. 4,6-bis-methylsulfonylpyrimidine. 4-Mothylsulfonyl-6-chloιpyΓimidin. 2-sulfoethylsulfonyl-4-chloro-6-methylpyimide m. 2-methylsulfonyl-4-chloro-5-bronip \ rimidin. 2-methylsulfonyl-4-chloro-5-bromo-6-meth \ ipyrimidine.

2.4-bis-rrtethylsulfonyl-5-chloropyπmldιn. 2-l'henylsulfonyl-4,5-dichloropyrimidine. 2-phenylsulfonyl-4,5-diehlor-6-meth> lp \ rimidin.

2-carboxymethylsulfonyl-4,5-dichloro-6-methylpyrimidine,

2-methylsulfonyI-6-chloropyrimidine-4- or
-S-carboxylic acid chloride,
2,4-bis-methylsulfonyl-1,3,5-triazine,
2,4-bis-methylsulfonyl-6- (3'-sulfophenylamino) -1,3,5-triazine,

2,4-bis-methylsulfonyl - <) - N-methylanilino-1,3,5-triazine,

!, ^ Bis-methylsulfonyi-o-phenoxy-1,3,5-triazine,
2,4-bis-methylsulfonyl-6-trichloroethoxy-1,3,5-triazine,
2,4,6-trisphenylsulfonyl-1,3,5-triazine.

A group of particularly valuable dyes obtainable according to the process corresponds to the formula

HO ₃ S

SO ₃ H

(SO ₃ H) ₁ , SO ₃ H

NH ₂
(ΠΙ)

Alkali fastness of the dyeings on cotton. The dye of the formula according to the specification

NH-A '

Here, Y stands for H or NO ₂ , η door the number O or 1 and A 'for a pyrimidine-1,3 radical bonded in the 2- or 4-position, the I or 2 cleavable alkylsulfonyl. Arylsulfonyl-. Has aralkylsulfonyl or heterosulfonyl radicals and which may contain further substituents.

The new dyes are valuable reactive dyes that are excellent for dyeing and Printing of cellulose-containing materials, in particular of native and regenerated cellulose, are suitable, the dyes in the presence of acid-binding Means and optionally applied using elevated temperature. Man achieves dyeings and prints with excellent fastness properties, in particular very good slackness and light fastness.

The dyes are also suitable for dyeing and printing of materials containing NH groups, in particular wool, silk and synthetic materials Super polyamide fibers. The dye is dyed in a weakly acidic medium and the pH of the dye bath is increased for example pH 6.5 to 8.5.

The dye according to the invention of the formula

SO ₃ H

HO, S

SO ₃ H

SO ₃ H

HO ₃ S

N = N

SO ₃ H

\ Cl NH N Cl Cl ί l ^:
1; /

shows compared to that known from US Pat. No. 3,151,105, Example 65, next comparable ble Dye the surprising advantage of the better: o Alkali fastness of the dyeings on cotton, the better over-dye fastness (sulfuric acid) of the dyeings on cotton, it also provides deep Dyeings on cotton.

example

19 parts by weight of 1,3-diaminobenzene-4-sulfonic acid are mixed with water at 60 ° C. in 200 parts by volume Sodium carbonate solution dissolved at pH 6. At 60 C, 25 parts by weight of 2-methyl-

w sulfonyM.S-dichloro-ö-methylpyrimidine entered and the pH of the reaction mixture by dropwise addition of 20% sodium carbonate solution 5 to 6 held. After the condensation has ended, the reaction product is added by adding 60 wt.

vs divide sodium chloride deposited and as light yellow Paste isolated.

This condensation product is dissolved in 400 parts by volume of water at 40 C, is nitrated by addition of a little active charcoal and diatomaceous earth, and the filtrate was cooled by adding ice to 10 to 15 ^U C. The solution of the diazonium compound obtained by customary methods from 38.3 parts by weight of 2-aminonaphthalene-4,6,8-trisulfonic acid in 450 parts by volume of water is added to this solution, and 140 parts by volume of a 20% sodium acetate solution are added to the mixture. The coupling is rapid and complete at pH 4. After 15 minutes the dye separates out in crystalline form. It is isolated and dried at 60 ° C. in a vacuum. The monoazo dye obtained corresponds to the formula

SO ₃ H

HO ₃ S

SO ₃ H

N = N

SO ₃ H

CH ₃ O ₂ S

zcigi compared to that from the US patent and, when dried, represents an orange powder. 31 51 105. Hebeispiel I known next comparable that dissolves in water with a yellow color and tree dye the surprising advantage of the better wool according to the usual techniques of reactive

printing or reactive dyeing in reddish-yellow tones.

In this example, equivalents are used instead of 2-aminonaphthalene-4,6,8-trisulfonic acid Amounts of 2-aminonaphthalene-4,8-disulfonic acid, 2-aminonaphthalene-6,8-disulfonic acid or the 6 - nitro - 2 - aminonaphthalene - 4,8 - disulfonic acid, reactive dyes are obtained with an analogous procedure, which dissolve in water with a yellow color and on cotton in the presence of acid-binding Medium yellowish yellow prints or dyeings.

If, in the process of this example, 1 -4,5-dichloro-6-methylpyrimidine is used instead of 2-methylsulfony in each case equivalent amounts of the reactive components indicated in the table below. so Valuable reactive dyes are also obtained, cotton by the known techniques of reactive dyeing Really in yellow tones colors:

2,4,6-trichlorotriazine-1,3,5,
l ^ -Dichlor-o-aminotriazine-l ^ .S.

2,4-dichloro-6-methylaminotriazine-1,3,5, 2,4-dichloro-6-oxät hy laminotriazine-1,3,5, 2,4-dichloro-6-phenylaminotriazine-1,3,4, 2,4-dichloro-6-o- or -m- or -p-sulfophenyl aminotriazine-1,3,5.

2.4-dichloro-6-N-methyl-N-phenylaminotriazine-1.3.5.

2,4,5,6-tetrachloropyrimidine-1,3, 2,4,6-trichloropyrimidine-1.3, 2,4-bis-methylsulfonyl-6-chloropyrimidine, 2-methylsulfonyl-4-chloro-5-eyan-6-mclhoxvpyrimidine,

2-methylsulfonyl-4-chloro-6-carbomethoxypvrimidine,

2-methylsulfonyl-4-chloropyrimidine-6-carboxylic acid.

2.4.6-trifluoropyrimidine,

2-methylsulfonyl-4,6-dichloropyrimidine, 2-carboxymethylsulfonyl-4-chloro-6-methylpyrimidine.

2-trichloromethylsulfonyl-4-chloro-6-methylpyrimidine.

Claims (2)

Patent claims: 1. Reactive dyes in the form of the free acid of the formula SO ₃ H (HO ₃ S) ₁ where X = H, halogen, nitro, A = pyrimidine-1,3 radical or sym.-triazine radical with at least one removable sulfonyl or halogen substituent, m = 2 or 3. 2. Use of the reactive dyes of claim 1 for dyeing and printing cellulosic Materials.