CS196446B2 - Method of preparing azo compounds usable as dyes - Google Patents

Abstract

1346367 Amino naphthalene sulphonic acids CIBA-GEIGY AG 27 Oct 1971 [27 Oct 1970 4 Oct 1971] 49917/71 Heading C2C [Also in Division C4] Compounds of formula where R 1 is H or C 1 -C 4 alkyl are prepared by sulphonation of the corresponding 2-amino-1- naphthylalkanesulphonic acids in oleum at normal or elevated temperatures. In Example 1, 2 - amino - 1 - sulphomethylnaphthalene is reacted with sulphuric acid monohydrate in oleum at 20-25‹ C. 2-amino-1-α-sulphoethylnaphthalene - 5 - sulphonic acid is prepared analogously. The compounds are used as intermediates in the preparation of azo dyestuffs.

Description

The present invention relates to a process for the preparation of novel azo compounds useful as dyes.

Z čs. U.S. Patent Nos. 125,770 and 135,245 disclose azo dyes which contain a residue of 1-sulfomethyl-2-naphthylazo-6-sulfonic acid or 1-sulfomethyl-2-naphthylazo-7-sulfonic acid. For the preparation of these azo dyes, the 1-sulfomethyl-2-naphthylamine-6-sulfonic acid or 1-sulfo-methyl-2-naphthylamine-7-sulfonic acid used are prepared according to these patents by direct sulfomethylation of the corresponding 2-naphtholsulfonic acids and subsequent Bucherer reaction with ammonia. . However, isomeric 1-sulfomethyl-2-naphthylamino-5-sulfonic acids cannot be prepared in this way, since the 2-naphthol-5-sulfonic acid required as starting material is not available under technical conditions.

It has now been found a new method for preparing technically 1-sulfomethyl-2-naphthylamine-5-sulfonic acid in good yield. Also available by the process of the invention are azo compounds which are prepared by diazotizing 1-sulfomethyl-2-naphthylamino-5-sulfonic acid and reacting with a coupling component. These azo compounds are novel and are valuable dyes.

Accordingly, the present invention relates to a process for the preparation of novel novel compounds useful as dyes of formula (1):

HCttySCyi where

Y is a residue of a series of aminonaphtholsulphoric acid, Z is a reactive residue, and R and R 1 are each a hydrogen atom or a low molecular weight alkyl residue.

The rest of R 1 may have a longer or shorter chain. However, compounds in which R1 is a low molecular weight residue, especially hydrogen, are preferred.

Suitable Y residues are the residues of the coupling components of various kinds, for example the residues of the benzene, naphthalene or pyrazolone series. However, it is preferably used as the coupling components of the 1844848 beta-4 < 4 > nin series of aminonaphtholsulfonic acid, especially 6-amino-1-naphthol-3-sulfonic acids. in

Low molecular weight alkyl radicals R are suitable. for example, butyl, propyl, isopropyl, ethyl and especially methyl. Azo compounds are further preferred. of formula (1) in which R represents a hydrogen atom.

Reactive residues are suitable for reacting with the hydroxyl groups of cellulose or the amino groups of polyamides groups capable of forming a covalent chemical bond. Such a grouping '. is especially a low molecular weight alkanoyl or alkysulfonyl radical substituted with a leaving atom. or a leaving group, a low molecular weight alkenoyl or alkenesulfonyl radical substituted by a leaving group or leaving group, via a carbonyl group. or a sulfonyl group. bonded carbocyclic or heterocyclic 4,5 or 6 rings containing a residue substituted by a leaving group. atom or a leaving group or directly through a carbon atom. trlázinový bonded or pyrimidine radical substitution tuovaný ^7. with a 'cleavable atom' or a cleavable atom. group or contains. . such a rest. As a reactive residue. is preferred over the group "NH". a bonded, halogen-containing atom. a 5- or 6-membered heterocyclic radical, in particular a monochloro-1, 3-triazine radical. '.

Therefore, the azo compounds of formula 2 are preferred,

where,

Z 1 represents an -NH 2 group. an amine, an alcohol, a mercaptan or a phenol residue; a hydrogen atom or a methyl group such as a compound of formula 3.

(3)

The azo compounds of formula (1) are:. prepared by coupling and / or condensation to introduce a reactive residue. This is accomplished by coupling the diazo compound to the amines of general interest. formula 4,

where '...

j · Ц '. ·. · »’. * »- · τ» · ζτ · η ^. · v .-' • zy- —ϊ «» - ·

R1 is as defined above with the coupling component of the general formula. formula 5,

... Y — N — z ‘.

AND

R '. : · (5) where .....

Y and R are as defined above and are hydrogen or reactive. rest ... and when Z 'represents an atom of hydrogen, that is. the prepared azo compound does not contain any reactive residue yet, it is condensed with the acylating agents contained therein. reactive residue.

They are especially coming. considered '2 ^-A-L-mlno sulfůmethýlnaftalen-5-sulfonic' acid. or a diazo compound thereof. 19844 «

WITH

Examples of coupling components include:

aniline,

1,3-toluidine,

1,2- or 1,3-anisidinium 3-aminoacetanilide;

3-amiriophenylurea,,

2.5-dimethylaniline,

2.5-dimethoxyaniline,

2,5-diethoxyl, 2-amino-4-methylanisole, 2-amino-4-acetylaminoamino, 1-naphthylamine, 1-naphthylamine-6-, -7-? or -8-sulfonic acid, ^'\

6-amino-1-naphthob-3-sulfonic acid, 6-methylamino-1-naphthol-3-sulfonic acid,

6-ethylamino-1-naphthol-3-sulfonic acid, 8-amino-1-naphthol-3,6-disulfonic acid and 8-amino-1-naphthol-4,6-disulfonic acid,

7- amino-l-naphthol-3-sulfonic acid, 6-amino-2-naphthol 4-sulfonic acid ₇ 5-amino-l-naphthol-3-sulfonic acid

5-amino-1-naphthi-3,8-diisulfonic acid,

6-amino-1-naphthol-3,7-disulfonic acid, 5-amino-1-naphthol-3,7-disulfonic acid, 1-amlnonaphthalene-6-sulfonic acid,

7-amino-1-naphthol-3,6'-disulfonic acid, 1- (3'- or 4'-aminophenyl) -3-methylpyrazolone- (5) '' of 1- (3'- or 4'-aminophenyl) ) pyrazolone- (5J-carboxylic acid, 1- (4'-aminophenyl) -3-methylpyrazolone- (5J, -2'-sulfonic acid).

The diazotization is carried out in a manner known per se, for example using hydrochloric acid and sodium nitrite. The coupling with the coupling component is also carried out in a manner known per se in an acidic to slightly alkaline medium.

The introduction of the reactive moiety is carried out by acylating the corresponding aminoazo compounds or coupling components which contain an acylated amino group or a group which is, for example, by reduction or saponification, to a convertible acylated amino group such as a nitro group or an acetylamino group.

Suitable acylating agents which contain, in addition to the acylation site, a reactive radical are, in particular, halides or anhydrides of organic acids which contain readily exchangeable atoms or atomic groups.

As the reactive residue containing acylating agents, there may be mentioned, for example: chloro- or bromoacetyl chloride, Ι-chloro- or + (3-bromopropionylchoride), β-3-dichloro- or α, β-dibromopropionyl chloride, chloroformic anhydride, carbylsulfate, acrylic chloride, -chloro- or n-bromoacryl chloride, α-chloro- or α-bromoacryl chloride, α, β-dichloro- or dibromacryl chloride,. trichloroacryl chloride, chlorocrotonyl chloride, propionic chloride, 3,5-dinitro-4-chlorobenzenesulfonic acid or carboxylic acid chloride, 3-nitro-4-chlorobenzenesulfonic acid chloride or -carboxylic acid, 2,2,3,3-tetrafluorocyclobutane-1- ... -carboxylic acids, 2,2,3,3-tetrafluorocyclobutylacrylic acid chloride, [3-chloroethylsulfonylendomethylene-cyclohexanecarboxylic acid chloride, acrylic sulfonylendomethylene-cyclohexanecarboxylic acid chloride, and in particular heterocyclic acid halides and derivatives thereof, such as 2-chlorobenzoxazolecarboxylic acid chlorides, chlorobenzthiazolecarboxylic acid. or sulfonic acids, and in particular the following compounds containing at least 2. nitrogen atoms as 6-membered heterocycle heteroatoms, 4,5-dichloro-1-phenylpyridazone- chloride. carboxylic or -sulfonic acids, 4,5-dichloropyridazonepropionic acid chloride, 1,4-dichlorophthalazincarboxylic acid or -sulfonic acid chloride, 2,3-dichloroquinoxaline-carboxylic acid chloride or -sulfonic acid chloride. 2,4-dichloroquinazoline carboxylic acid. or -sulfonic acids, 2-methanesulfonyl-4-chloro-6-methylpyrimidine, tetrachloropyridazine,

2,4-bis-methanesulfonyl-6-methylpyrimidine,

2,4,6-tri- or 2,4,5,6-tetrachloropyrimidine,

2,4.6-tri- or 2,4,5,6-tetrabrompyrimidine, 2-methanesulfonyl-4,5-dichloro-6-methylpyrimidine,

2,4-chloropyrimidine-5-sulfonic acid, 5-nitro- or 5-cyano-2,4,6-trichloropyrrolidine, 2,6-bis-methanesulfonylpyridine-4-carboxylic acid chloride,

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

2,4-dibromo-5-bromomethyl-6-methylpyrimidine,

2.4-dichloro-5 ^: chloromethylpyrimidine,

2,4-dibromo-5-bromomethylpyrimidine,

2.5.6-trichloro-4-methylpyrimidine,. 2,6-dichloro-4-trichloromethylpyrimidine or particularly

2,4-bis-methylsulfonyl-5-chloro-6-methyl-pyrimidine;

2, 4,6-trimethylsulfonyl-1,3,5-triazinium

2.4- dichloropyrimidine,

3,6-dichloropyridazine, 3,6-dichloropyridazine-5-carboxylic acid chloride,

198448

2,6-dichloro- or 2,8-dibrotin-4-carboethoxypyrimidine,

2,4.5-trichloropyrimidine, 2,4-dichloropyrimidine-6-carboxylic acid chloride, 2,4-dichloropyrimidine-5-carboxylic acid chloride, 2,8-dichloropyrimidine-4-carboxylic acid amide, 2,6 amide -dichloropyrimidine-5-carboxylic acid, 2,6-dichloropyrimidine-4-sulfonic acid amide, 2,6-dichloropyrimidine-5-sulfonic acid amide, 2,6-dibromopyrimidine-4-carboxylic acid amide, 2,6-dibromopyrimidine amide, 5-carboxylic acid, 2,6-dibromopyrimidine-4-sulfonic acid amide, 2,6-dibromopyrimidine-5-sulfonic acid amide. 2,6-dichloropyrimidine-5-carboxylic acid chloride, 2,6-dichloropyrimidine-5-carboxylic acid chloride, 2,8-dlchloropyrimidine-4-sulfonic acid chloride, 2,2-dichloropyrimidine-5-sulfonic acid chloride acids, 2,8-dibromopyrimidine-4-carboxylic acid chloride, 2,6-dibroinpyrimidine-5-carboxylic acid chloride, 2,6-dibromopyrimidine-4-sulfonic acid chloride, 2,8-dibromopyrimidine-5-sulfonic acid chloride,

2.4.5.6-tetrachloropyridazine, 5-bromo-2,4, e-trichloropyrimidine,

5-acetyl-2,4,8-trichloropyrimidine, 5-nitro-8-methyl-2,4-dichloropyrimidine, 2-chlorobenzthiazole-6-carboxylic acid chloride, 2-chlorobenzothiazole-6-sulfonic acid chloride, 5-nitro- 6-methyl-2,4-dichloropyrimidine,

2.4.6- trichloro-5-bromopyrimidine,

2.4.5.6- tetrafluorpyrlmidine,

4,6-difluoro-5-chloropyrimidine,

2.4.6-trifluoro-5-chloropyrimidine,

2.4.5-Trifluoropyrimidine,

2.4.6- trichloro- (-tribromo- or -trifluoro) -1,3,5-trlazine as well as

4,6-dichloro (dibromo- or -difluoro) -1,3,5-triazine, substituted in the 2-position by an aryl or alkyl group, for example phenyl, methyl or ethyl, or an aliphatic or aromatic group, via a sulfur-bonded mercapto compound, optionally via an atom Aliphatic, heterocyclic or aromatic amino compounds bound by a nitrogen atom or, in particular, an NH2 group or a residue via a nitrogen atom As such compounds whose residues may be bound by reaction with trihalogentriazines at the 2-position on the triazine nucleus, for example, the following compounds are mentioned: aliphatic or aromatic mercaptos or hydroxyl compounds such as thioalcohols, thioglycolic acid, thiophenols, alkoxyalkanols, methanol, ethyl alcohol, isopropyl alcohol, glycolic acid, phenol, chlorophenols or nitrophenols, phenolecarboxylic acids and phenolsulfonic acids, naphthols, naphtholsulfonic acids, etc., especially however, ammonia and compounds containing acylated amino groups, such as hydroxylamine, hydrazine, phenylhydrazine, phenylhydrazine sulfonic acid, glycol monoalkyl ether, methylamine, ethylamine, isopropylamine, methoxyethylamine, methoxypropylamine, dimethylamine, diethylamine, methylphenylamine, ethylene, ethylene, ethylene, ethylene.

propanolamines, benzylamine, cyclohexylamine, morpholine, piperidine, plperazine, amino carbonate ester, aminoacetate ethyl ester, aminoethanesulfonic acid, N-methylaminoethanesulfonic acid, in particular aromatic amines such as aniline, N-methylaniline, toluidines, xylanines, chloranines, xylanines, chloranines. .

p-optionally m-aminoacetanilide, aminophenols, anisidine, phenetidine, and especially acidic groups containing anilines, sulfanilic acid, methanilic acid, orthanilic acid, anilindisulfonic acid, aminobenzylsulfonic acid, aniline-n-methanesulfonic acid,

aminobenzenedicarboxylic acids, naphthylaminomonosulfonic acids, naphthylaminodisulfonic acids, naphthylaminotrisulfonic acids, aminobenzoic acids such as 2-hydroxy-5-aminobenzoic acid, further colored compounds or dye compounds, for example 4-nitro-4'-aminostilbendisulfonic acid>nitro-4'-aminodiphenylamine-4,3'-stilbenedisulfonic acid, ^{2-nitro-4-4,3'--aminodifenylamin} idísulfonová acid or especially aminoazobarvlva aminoanthraquinones or phthalocyanines containing at least one further reactive group.

The introduction of the substituent at the 2-position of the triazine residue is also possible after condensation with the coupling component or after reaction with the azo compound of formula (1).

The condensation with acid halides or anhydrides or heterocyclic halogen compounds is conveniently carried out in the presence of acid binding agents such as sodium carbonate. All of these reactions should be carried out so that at least one unsaturated bond or at least one replaceable halogen atom remains in the finished product.

The invention also relates to all amines of general formula (4) useful as diazo compounds, in particular to the compound of general formula 6.

The compounds of formula (4) and (6) are valuable intermediates which are particularly suitable for the preparation of azo dyes. They can be prepared by sulfonating the corresponding 2-amino-1-naphthylalkansulfonic acids with oleo at normal or slightly elevated temperature.

The compounds prepared by the process of the invention are novel. They are valuable dyes suitable for dyeing and printing various materials, in particular polyhydroxylated fibrous structure materials such as cellulose-containing materials, both chemical fibers, such as regenerated cellulose and cellulosic staple, and natural cellulosic materials such as flax, in particular. for dyeing and printing cotton. They are suitable for dyeing by the so-called direct dyeing method of a long alkaline water bath containing possibly a considerable amount of salts, in particular for dyeing by printing and impregnation, in which the dye is applied to the material to be dyed by printing or foulard and fixed with an acid binding medium , optionally under the effect of heat.

In order to improve the stability of the wet, it is recommended that the dyeings or prints obtained be thoroughly rinsed with cold and hot water, optionally with additives, dispersants and diffuser-enhancing agents.

The dyes prepared according to the process according to the invention are characterized, in particular, by a high degree of fixation, increased reactivity and easy washability of the non-fixed dye pedestal, and the dyes obtained have a very good washing stability.

In the following examples, parts and percentages are by weight unless otherwise indicated, and temperatures are given in ° C.

Example 1

237 parts of 2-amino-1-sulfomethylnaphthalene are introduced into 600 parts by volume of sulfuric acid monohydrate with stirring at 20-25 ° C. Then 400 parts by volume of 25% sulfuric oleate are added dropwise over one hour and stirred at normal temperature until no trace of the starting material can be detected in the chromatogram. The reaction mixture is then poured onto 3000 parts of ice and 500 parts of water, the disulfonic acid obtained is precipitated by the addition of 350 parts of sodium sulphate and filtered.

In a similar manner, 2-amino-l, N-sulfoethylnaphthalene (prepared by reaction of 2-naphthol with acetaldehyde bisulfite and subsequent substitution of the hydroxyl group with an amino group according to Bucherer) was obtained by sulfation of the resulting 2-amino-1,1-sulfoethylnaphthalene-5-sulfonic acid.

Example 2

To a neutral aqueous solution of 25.3 parts of 6-methylamino-1-naphthol-3-sulfonic acid was added 24 parts of 2- (2'-ethoxy) ethoxy-4,6-dichloro-1 with stirring at 20-25 ° C. 3,5-triazine is then condensed by the gradual dropwise addition of 2N sodium hydroxide solution at a pH of 6-7. The diazo solution prepared from 31.7 parts of 2-amino-1 is now flowed to the condensation product at 0-5 ° C in the usual manner. sulfomethylnaphthalene-5-sulfonic acid, maintaining the pH at 7 to 8 by adding solid soda. After completion of the coupling, it is warmed to 25 ° C and sodium or potassium chloride is added. dye precipitates.

The precipitated dye is filtered off and dried. Dyes cotton to pure scarlet shades.

Similar dyes are obtained when, instead of 2- (2'-ethoxy) ethoxy-4,6-dichloro-1,3,5-triazine, an equivalent amount of α, β-dibromopropionyl chloride, 2,3-dichloroquinoxaline chloride is used as acylating agent. 6-carboxylic acids, 2,4,5,619 944 'β

-tetrachloropyrimidine, 2,4,6-trlchloro-1,3,5-triazine or. 2-Phenylamino-4,6-dichlorotriazine-3'-sulfonic acid. .

When, instead of 6-methylamino-1-naphthol-3-sulfonic acid, an equivalent amount of the coupling component listed in column II of the following table is used, which is condensed with the acylating agent. as described in column III and then coupled as described above. in the example diazotized with 2-amino-1-sulfonomethylnaphthalene-5-sulfonic acid, additional dyes are obtained which dye the cellulose fibers to the shade shown in column IV.

Number Copier

Acylating agent Hue

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

7-Methylamino-1-naphthol-3-sulfonic acid

5-Amino-1-naphthol-3-sulfonic acid 1-amino-5-hydroxynaphthalene-3,7-

1-Amino-8-naphthol-4-sulfonic acid disulfonic acid

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

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

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

6-amino-1-naphthol-3,7-disulfonic acid 1-amino-8-naphthol-3,6-disulfonic acid 1-amino-8-naphthol-4,6-disulfonic acid 2,4-dlchloropyrimidine chloride . red

-6-carboxylic acids

2,4,5,6-tetrafluoropyrimidine red

2-methyl-4,6-dichloro-1,3,5-. red

-triazine with a hint of blue

2-Amino-4,6-dichloro-1,3,5-triazine red. with a hint of blue

2-Phenylthio-4,6-dlchloro-1,3,5-ruby

-triazine '

2-methoxy-4,6-dichloro-1,3,5-red

-triazine with a hint of blue

2- (2‘-hydroxyethylamino) -4,6- red

-dichloro-1,3,5-triazine

2-Phenylamino-4,6-dichloro-1,3,5-red

-triazine-2‘-sulfonic acid.

2,4,5,6-tetrachlorpyrimidine red

2-Isopropoxy-4,6-dlchloro-1,3,5-ruby

-triazine

2- (3‘-ureido-4‘, 2 “-naphthylazophene-brown nylamine) -4,6-dichloro-1,3,5-triazine-3“, 6 “, 8“-trisulfonic acid · '

Example 3>

31.7 parts of 2-amino-1-sulfomethylnaphthaline-5-sulfonic acid. The acid was diazotized, coupled with 36.2 parts of 8-adtylamino-1-naphthol-3,6-disulfonic acid, and finally saponified the acetyl group for 2 hours with 6% sodium hydroxide solution.

The 32.4 dl of the aminoazo dye obtained is dissolved in water and condensed at 0-5 ° C with 9.22 parts of 2,4,6-trichloro-1,3,5-triazine, maintaining the dropwise addition of 2N sodium hydroxide solution. . pH to .6. After completion of the condensation, 2.7 parts of 1,4-phenylenediamine are added, heated. The reaction mixture was heated to 40 ° C and condensed again by dropwise addition of 2 N sodium hydroxide solution at a pH of 6 to 20 ° C. 7. After the condensation has been completed, the dye is isolated by pouring in sodium chloride. filtered and dried. Dyes cotton to permanent. red shades with a hint of blue.

Prescription-coloring:

Two parts of the dye prepared as described in Example 3 were dissolved in 100 parts of water with the addition of 0.5 m sodium nitrobenzenesulfonate. The cotton fabric thus impregnated with the solution thus obtained is added to 75%. their weight, and then they are dried.

Then. impregnate the fabric with a 20 ° C solution containing 5 per liter. g of sodium hydroxide and .300. g of sodium chloride, squeezed to 75% by weight, increment, steaming for 20 to 20%. 30 seconds at temperature. 100 to. 101 ° C, soap after. .dobu čtvrt

14 hours with 0.3% v boiling detergent solution, rinse and dry.

Printing regulations:

Two parts of the dye prepared as described in Example 2 are poured into 100 parts of the master drip, containing 45 parts of 5% sodium alginate, 32 parts of water, 20 parts of urea, 1 part of sodium nitrobenzenesulfonate and 2 parts of acidic acid. sodium carbonate.

The printing paste thus obtained is printed on a cotton fabric on a roller printing machine and the printed substance obtained is steamed for 1 to 2 minutes at room temperature. 100 ° C saturated steam. The printed substance is then rinsed thoroughly with cold and hot water, whereby chemically unfixed dye portions are removed very easily from the fiber and finally dried.

Example 4

15.9 parts of 2-amino-1-sulfonomethylnaphthalene-5-sulfonic acid is dissolved in 50 parts of water with the addition of 5 parts of 30% aqueous sodium hydroxide solution at pH 7. 3.5 parts of sodium nitrite are added and the resulting solution pour on a mixture of 100 · parts ice and · 15 parts. 30% hydrochloric acid. To the diazonium salt solution thus obtained is added a solution of 7.5 parts of 3-aiminoacetanilide in 50 parts of water and the coupling mixture is slowly neutralized by the addition of 4n sodium acetate solution. After coupling, the dye is precipitated by the addition of potassium chloride. It dissolves in 400 parts water at pH 7 and at a temperature of 20 to 25 ° with good mixing with 10 parts of 2-isopropoxy-4,6-dichloro-1,3,5-triazine. The pH of the condensation is maintained at 6-7 by dropwise addition of sodium hydroxide solution. After completion of the condensation, the dye is precipitated by the addition of potassium chloride. It dyes cotton to yellow tones with a reddish tint, light and wash-resistant.

If it is used instead of 3-aminoacetates, a people equivalent amount. the coupling components listed in column II of the following tables, and in place of the 2-isopropoxy-4,6-dlchloro-1,3,5-triazine equivalent amount of the acylating agent listed in column TII, additional dyes are obtained which dye cellulosic fibers to the shades referred to in column IV.

AND II III IV Number The coupling component Acylating agent Shade on cotton

1 2 3-Aminophenyl urea 3-Aminotoluene 2-amino-4,6-dichloro-1,3,5-riazine α, α-dibromopropionyl chloride. yellow with a reddish tinge  yellow 3 2-Amino-4-methylanisole 2,2,3,3-tetrafluorocyclobutylacrylic acid chloride Yellow with a reddish tinge 4 2-Amino-4-acetylaminoanisole 2-chlorobenzthiazoleullonic acid chloride yellow. with a hint of red 5 aniline 4,5-dichloropyridazone propionic acid chloride yellow 6 1- (4‘-Amino-phenyl-3-methyl-pyrazolone-5) 2,3-dichloroquinoxaline carboxylic acid chloride yellow 7 1- (4‘-Amino) phenyl-3-methylpyrazolone- (5'-3‘-sulfonic acid) 2,4,5,6 - Etrachlorpyrimidine yellow 8 1- (2‘-Aminoethyl) -3-cyano-4- -methyl-6-hydroxypyridone-2 5-Cyano-2,4,6-trichloropyrimidine yellow 9 1-naphthylamine-6-sulfonic acid 2,4-dichloropyrimidine-5'-carboxylic acid chloride yellow 10 1-naphthylamine-8-sulfonic acid 2.4 _; 6-Trifluoro-5-chloropyrimidine yellow 11 1- (4‘-amino) phenyl-3-methyl- py pyrazolone- (S) -2‘-sulfonic acid 2-anlinophenyl-4,6-di-chlorot13,5- -triazine-3‘-sulfonic acid yellow

196448

Example 1 a d. - 5. · -V

55.4 parts of the dipotassium-amino-dye salt prepared as described in Example 4, paragraph 1, are dissolved in 300 parts of water at. temperature - 0 ° C. Adds. 18.5 parts of cyanuric chloride and pH. of the solution is maintained dropwise during condensation. . 2n. of caustic soda to 6-7. After complete condensation, a neutral solution of 53.3 parts of 1-amino-4- (3'-aminophenylamino) anthraquinone-2,4'-disulfonic acid disodium salt in 500 parts of water is added - and heat to 55 ° C. By slowly adding dilute sodium hydroxide solution at said temperature, the pH is maintained at 5 to 6. After the condensation has been completed, the pH is adjusted to 7 with sodium hydroxide solution and the dye is isolated by salting out. Color cotton - for permanent olive green shades. . If a corresponding amount of the phthalocyanine dye of formula 7 is used in place of 1-amino-4- (3'-aminophenylamino) anthraquinone-2,4'-disulfonic acid,

CyPc, 0 ° NH . NH ^L ... (?)

dyeing cotton to green shades is also obtained.

Example 6

To a neutral aqueous solution of 25.3 parts

Claims (5)

SUBJECT EXCLUDED A process for the preparation of azo compounds useful as dyes for dyeing and printing cellulosic fibers of formula (1): -Zaji (1) 6-Methylamino-1-naphthol-s-sulfonic acid - 18.5 parts of cyanuric chloride are added with good stirring at 0 DEG C. and then condensed at that temperature by dropwise addition of 2N sodium hydroxide solution at pH 6 to 7. The diastore solution from 31.7 parts of 2-amino-1-sulfomethytananthene-5-sulfonic acid is prepared in the usual manner at 0 - to - 5 ° C into the condensation product, maintaining the pH at 5- to 6- - by slow addition of sodium bicarbonate. After the coupling, the pH is adjusted to 7 with sodium hydroxide solution and finally poured. - neutral solution of 21 parts of 1,3-phelyl-diamine-4-sulfonic acid sodium salt. Heat to 35 ° C and condense at this temperature, maintaining a pH of 6-7 through the dropwise addition of 2 N sodium hydroxide solution. As soon as 1,3-phenylenediamine-4-sulfonic acid is no longer present in the reaction mixture, it is cooled. The solution was stirred at 0 ° C. 18.5 parts of cyanuric chloride are added and condensed as described above. After completion of the condensation, 25 volumes of 24% aqueous ammonia solution and are added. the dye solution was added. Stir for three hours at 30 to -35 ° C. The dye is isolated from the solution by pouring in a mixture of equal amounts of sodium chloride and potassium chloride. - Dyes cellulosic fiber fabric to constant scarlet shades. , A dye of very similar dyeing properties is obtained when a neutral solution of the sodium salt of 2- (3'-aminophenylamino) -4 is added to said coupling solution - instead of - 1,3-amino-4-sulfonic acid. -phenylamilo-6-chloro-1,3,5-triazine-3'-sulfonic acid, condensed at 30-35 ° C and the resulting dye was isolated by salting out. ezu '·?' characterized in that the diazo compound of the amine of the formula (4), where denotes, is coupled Y the residue of a series of amino-naphthosulfonic acids, Z - reactive group, R and R 1 are hydrogen or C 1 -C 4 alkyl, Y — N — Z ‘I Ø (5) where R1 is as defined above, with the coupling component of formula 5, 196448 / where \ Y and R are as defined above and Z ‘represents a hydrogen atom or a reactive radical, and when Z * represents a hydrogen atom, the compound obtained is condensed with acylating agents containing a reactive radical. 2. A process according to claim 1, wherein the amine diazo compound of formula 4 wherein R1 is hydrogen and the coupling component of formula 5 wherein Y is the radical of a series of aminonaphtholsulfonic acid, Z ' is hydrogen or a 5-membered heterocyclic; a six-membered fiber-reactive residue containing halogen atoms and R represents a hydrogen atom or a methyl group. 3. A process according to claim 1, wherein the amine of the formula 6 and the coupling component of the formula 8 are used. OH (8) where R represents a hydrogen atom or a methyl group which is condensed before or after coupling with 4,6-dichloro-1,3,5-triazine containing in the 2-position an N-group, an amine, alcohol, mercaptan or phenol residue, or 2,4,6-trichloro-1,3,5-trlazineine which following condensation or coupling, it may react with ammonia, amine, alcohol, mercaptan or phenol. 5. A process according to claim 3, wherein 2-N-methylamino-5-hydroxy-naphthalene-7-sulfonic acid is used as the coupling component and 2- (4-ethoxyethoxy-4,6-dichloro-1,3,5). -triazine or 2,4,6-trichloro-1,3,5-triazine, which, following condensation or coupling, is reacted with p-ethoxyethyl alcohol as condensing agent.