DE1219147B - Process for the preparation of metal complex compounds of azo dyes - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

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File number:
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C 09 b

German KL: 22 a -1

1219 147
F32658IVc / 22a November 30, 1960 June 16, 1966

It has been found that valuable new metal complex compounds are obtained from azo dyes, if you have a diazo compound which in the o-position to the diazo group forms a metal complex Contains a group or a substituent which can be converted into such a group, with a coupling component in o-position to a hydroxyl group or a primary or secondary amino group couples, here the starting components are chosen so that the resulting azo dye at least a grouping of the formula

-SO ₂ -N- O ₂ S - Ri
R.

(I) Process for the preparation of metal complex compounds of azo dyes

Applicant:

Paint factories Bayer Aktiengesellschaft, Leverkusen

Named as inventor:

Dr. Rolf Pütter, Düsseldorf;

Dr. Hans Gerhard Hanke, Leverkusen; Dr. Gerhard Wolf ram, Opladen

wherein R and Ri are optionally substituted hydrocarbon radicals represent, contains, and by the azo dye obtained - optionally together with other metal complex-forming azo or azomethm dyes - with metal donating, preferably treated chromium or cobalt releasing agents. The coupling of the starting components takes place in an acidic, neutral or alkaline range, depending on the type of compounds used, in aqueous, aqueous-organic or organic medium by methods known per se.

Suitable diazo components for the preparation of the new dyes are preferably those of Benzene series, the usual substituents in azo dyes, such as halogen, alkyl, alkoxy, nitro, Arylazo, acylamino, sulfonic acid, carboxylic acid, optionally substituted sulfonamide or carbonamide groups and / or groupings of the formula

-SO ₂ -N- O ₂ S - Ri
R.

contain.

Suitable metal complex-forming substituents in the o-position to the amino or diazo group are Hydroxyl and carboxyl groups, as well as methoxy and chlorine substituents, which are produced by known metallization processes be converted into complex-bound OH groups. By oxidative copper plating, it is also possible to get into unoccupied o-positions To introduce diazo group-bound hydroxyl groups. Also the exchange of sulfonic acid groups at this point against OH is known.

In addition to numerous other compounds, the following diazo components, among others, are included to name:

2 - amino - phenol - 4 - sulfo - (methanesulfo) - methylimide, 2 - Amino - phenol - 4 - sulfo - (methanesulfo) - isobutylimide, 2 - Amino - phenol - 4 - sulfo - (methanesulfo) phenylimide, 2 - Amino - phenol - 4 - sulfo- (butanesulfo) isopropylimide, 2 - Amino - phenol - 4 - sulfo - (benzenesulfo) - isopropylimide, 2 - amino - phenol - 5 - sulfo- (methanesulfo) - isopropylimide, 2 - amino - 4 - chlorophenol, 3 - amino - ρ - cresol, 2 - amino - phenol-4 - sulfonic acid, 2 - amino - 4 - chloro - phenol - 5 - sulfonic acid, Anthranilic acid, 4 - nitro - anthranilic acid, 1 - amino - 2 - carboxybenzene - 5 - sulfo - {methanesulfo) isopropylimide.

The coupling components can, inter alia, belong to the oxybenzene, oxy or aminonaphthalene, acylacetic acid amide or heterocyclic series, here in particular the pyrazolone series. In principle, the compounds can have the same substituents that have been mentioned in connection with the substitution of the diazo components. In the process, for example, the following coupling components are used: ^ -naphthol, 2-naphthol-6-sulfonic acid, 2-naphthol-6-sulfo- (methanesulfo) - isopropylimide, 2 - naphthol - 6 - sulfo- (methanesulfo) - phenylimide, 2 - Naphthol - 6 - sulfo- (benzenesulfo) methylimide, / S-naphthylamine, 1-phenyl - 3 - methylpyrazolone - (5), 1 - (3 '- sulfophenyl) -3 - methyl - pyrazolone - (5), 1 - (2 '- chloro - phenyl) -3 - methyl - pyrazolone - (5), 1 - phenyl - 3 - methyl - pyrazolone - (5) - Υ - sulfo - (methanesulfo) - isopropylimide, acetoacetylamino-benzene, acetoacetylamino- benzene-3-suIfo- (methanesulfo) isopropylimide. Substituents of the formula

-SO ₂ -N · O ₂ S - Ri

can be introduced into the starting components by known methods. For example, can

609 579/360

one o-nitrophenolsulfo-alkylamide in organic Medium such as acetone, under alkaline reaction with methanesulfonyl chloride to form the corresponding o-nitrophenol - convert sulfo - (methanesulfo) - alkylimide and then the nitro group in organic Reduce the medium catalytically. The same process can be used for the manufacture of clutch components with the grouping I, if one, for example for the production of a Pyrazolone coupling component, nitrobenzene sulfoalkylamides in acetone under alkaline reaction conditions with methanesulfonyl chloride to the corresponding Imide converts, reduces, diazotizes the amino group, the diazonium salt with sodium sulfite and with saponification of the resulting hydrazine-N-sulfonic acid into the corresponding hydrazinobenzene sulfo - (methanesulfo) - alkylimide - compound, which then in acidic solution with Acetoacetic amide can be condensed to pyrazolone.

A preferred class of dyes obtainable by the present process are those which do not contain any free sulfonic acid groups or carboxylic acid groups which are not involved in complex formation. Such dyes are largely insoluble in water, but remarkably well soluble in alcohols or esters and are therefore particularly suitable for coloring paints.

For the metallization of the process

CH ₃
H ₃ C-SO ₂ -NO ₂ S

To convert it into the chromium complex, the dye is dissolved in 800 parts by volume of hot water and converted into the chromium complex by adding dropwise an aqueous solution of 8 parts by weight of potassium dichromate and 14 parts by weight of grape sugar. After the reaction has ended, the mixture is acidified with hydrochloric acid and the one containing chromium Dye filtered off. After drying and grinding, it presents an orange-brown powder that dissolves in ethyl acetate or alcohol with a red-yellow color.

To convert it into the cobalt complex, the metal-free dye is ^{mixed in an alkaline solution at 90 °} C. with the ammoniacal solution of 15 parts by weight of cobalt sulfate. When the reaction has ended, it is acidified with hydrochloric acid and the cobalt-containing dye is filtered off. After drying and grinding, he presents a yellow-brown powder that dissolves in ethyl acetate or alcohol with a yellow color.

The starting product 2-aminophenol-4-sulfo- (methanesulfo) -methylimide used in this example is obtained by converting 2-nitro-phenol-4-sulfomethylamide in acetone with an alkaline reaction with methanesulfonyl chloride to give 2-nitro-phenol-4 -sulfonated (methansulfo) -methylimid, F. = 182 ° C, and reacting this hydrogenated of a catalyst at 30 to 40 ⁰ C in methanol in the presence.

Example 2

The usual way of 32.2 parts by weight of 2-aminophenol-4-sulfo- (methanesulfo) -isobutylimide, available dyes in substance, the usual methods are used, for. B. the chroming with chromates in the presence of glucose or with salts of trivalent chromium, cobalt formation with cobalt sulfate, the conversion into copper complex compounds with copper sulfate, etc. The Metal complex compounds obtainable according to the process are valuable dyes which, depending on the degree of their solubility for different areas of application, e.g. B. the paint sector used can be.

In comparison to the from the French patent 1 208 272, page 3, table, 1st and 2nd combination, known dyes are characterized by the corresponding N-methylated ones on the disulfimide group Dyes due to their significantly better solubility in the paint solvents butyl acetate and Glycol monomethyl ether acetate.

example 1

The diazo compound prepared in the usual way from 28 parts by weight of 2 - aminophenol - 4 - sulfo - (methanesulfo) - methylimide is added to the solution of 17.4 parts by weight of 1-phenyl-3-methyl-pyrazolone- (5), 10 parts by volume of sodium hydroxide solution (D. . = 1.45) and 25 parts by weight of soda in 400 parts by volume of water. When the coupling is complete, sodium chloride is added and the monoazo dye of the formula below is filtered off:

OH

CH ₃

F. = 164 to 165 ° C, the diazo compound produced becomes the solution of 14.4 parts by weight / S-naphthol given in 20 parts by volume of sodium hydroxide solution (D. = 1.45) and 300 parts by volume of water. After finished Coupling is mixed with common salt and the monoazo dye of the formula below is filtered off:

OH OH

C ₄ H ₉
H ₃ C-SO ₂ -NO ₂ S

To convert it into the cobalt complex, the methanolic solution of the dye is slowly added to the 65 ^° C. ammoniacal solution of 15 parts by weight of cobalt sulfate. The mixture is then stirred for a further 10 minutes at the same temperature and hydrochloric acid is then added until the Congo acidic reaction occurs. After drying and grinding, the dye presents a brown-red powder that dissolves in ethyl acetate and alcohol with a Bordeaux-red color.

Example 3

The diazo compound prepared in the usual way from 30.8 parts by weight of 2-amino-phenol-4-sulfo (methanesulfo) -isopropylimide, mp 122 ° C., is added to the solution of 14.4 parts by weight of ^ -naphthol in 20 parts by volume of sodium hydroxide solution ( D. = 1.45) given. After the coupling is complete, table salt is added

and the monoazo dyes of the formula below filtered off:

C ₃ H ₇
H ₃ C-SO ₂ -NO ₂ S

OH

N = N

According to the chromating instructions given in Example 1, the dye forms a chromium complex, the dried and ground a black powder

10

OH

OH

CH ₃

According to the chromating instructions given in Example 1, a dye is obtained from this dye Chromium complex, which, after drying and grinding, presents a red powder that turns into ethyl acetate and Alcohol with red color dissolves.

The pyrazolone used as starting material in this example, mp = 162 ° C, is obtained, by 3-nitrobenzenesulfo-isopropylamide in Acetone reacts with methanesulfonyl chloride in an alkaline reaction, this in methanol to 3-aminobenzene - sulfo - (methanesulfo) - isopropylimide, m.p. = 118 ° C, hydrogenated. The latter connection will in a known manner by diazotizing, reacting the diazonium salt with sodium sulfite and saponifying the resulting hydrazine-N-sulfonic acid into 3-hydrazinobenzene sulfo- (methanesulfo) isopropylimide convicted. This is condensed in acidic solution with acetoacetic amide to form the pyrazolone.

and dissolves in alcohol and ethyl acetate with a purple-gray color.

Example 4

The diazo compound prepared in the usual way from 2-amino-4-chlorophenol is added to the solution of 14.4 parts by weight of l-phenyl-3-methyl-pyrazolone- (5) -3'-sulfo- (methanesulfo) -isopropylimide, F. = 162 ° C, 10 parts by volume of sodium hydroxide solution (D. = 1.45) and 25 parts by weight of soda in 350 parts by volume of water. When the coupling is complete, sodium chloride is added and the monoazo dye of the formula below is filtered off:

C ₃ H ₇
SO ₂ -NO ₂ S-CH ₃

Example 5

The alkaline solution of 33.6 parts by weight of 1-amino-2-carboxybenzene-5-sulfo (methanesulfo) isopropylimide and 7 parts by weight of sodium nitrite is left at ⁰ ° C. in 30 parts by volume of hydrochloric acid (D. = 1.18), which is mixed with Ice and water has been diluted, pour in. The diazo compound prepared in this way is allowed to flow into the solution of 17.4 parts by weight of 1-phenyl-3-methyl-pyrazolone- (5), 8 parts by volume of sodium hydroxide solution (D. = 1.45) and 30 parts by weight of soda in 300 parts by volume of water. After the coupling has ended, the pH is adjusted to 7.5 by adding acetic acid, the mixture is heated to 65 ^° C. for 4 hours, and sodium chloride is slowly added. The monoazo dye of the formula below is then filtered off, dried and ground:

OH

H ₃ C - SO ₂ - N - O ₂ S * =

The dye powder is introduced into 1000 parts by volume of 1% hydrochloric acid and the mixture is left for a short time stir, vacuum and dry again. The salt-free dye is cooked with for several hours Chromium formate in isopropanol converted into the chromium complex, which after drying and grinding represents a yellow powder and dissolves in ethyl acetate and alcohol with a yellow color.

The starting product used in this reaction l-amino-2-carboxybenzene-5-sulfo (methansulfo) -isopropylamid, F. = 202 ⁰ C is obtained by N-acetylanthranilic acid-5-sulfoisopropylimid in acetone at an alkaline reaction with methanesulphonyl chloride reacting the mixture then treated with hydrochloric acid in excess, and heated for 2 hours at 7O ⁰ C.

Claims (3)

Claims: 6S 1. Process for the preparation of metal complex compounds of azo dyes, since CH ₃ characterized in that one has a diazo compound which is in the o-position to the diazo group a metal complex-forming substituent or one under the conditions of the metallization contains substituents which can be converted into such a group, with a coupling component couples in the o-position to a hydroxyl or primary or secondary amino group, here the starting components as above selects that the resulting azo dye has at least one group of the formula -SO ₂ -N- O ₂ S - Ri wherein R and Ri are optionally substituted Represent hydrocarbon radicals, contains, and the dye thus obtained - if desired together with other metallizable azo or azomethine dyes - with metal donating Means treated. 2. The method according to claim 1, characterized in that the starting components so chooses that the resulting azo dye of sulfonic acid groups and not of the Complex formation involved carboxylic acid groups is free. 3. The method according to claim 1, characterized in that the dye with chromium or cobalt-releasing agents. Documents considered: German Patent No. 1 039 676; Swiss Patent No. 247 715; French patent specification No. 1 208 272. When the application was announced, a coloring table with explanations was laid out. 609 579/360 6.66 © Bundesdruckerei Berlin