DE1077810B - Process for the preparation of monoazo dyes of the pyrazolone series and their chromium complex compounds - Google Patents

Description

GERMAN

The subject of the present process is the preparation of monoazo dyes of the pyrazolone series and their chromium complex compounds. The procedure consists in adding 1 mole of the diazo compound from a l-carboxy-2-aminobenzenesulfonic acid amide of the general formula

COOH

in which R _{1 is} alkyl, alkoxyalkyl, cycloalkyl or aralkyl or aryl free of sulfonic acid and carboxyl groups, R _{2 is} hydrogen or alkyl or, together with —N— and —R ₁ , is a heterocyclic radical and in which the group

—So "—n:

Method of manufacture
of monoazo dyes

the pyrazolone series
and their chromium complex compounds

Applicant:
Sandoz AG, Basel (Switzerland)

Representative: Dr. W. Schalk, Dipl.-Ing. P. Wirth,

Dipl.-Ing. G. E. M. Dannenberg

and Dr. V. Schmied-Kowarzik, patent attorneys,

Frankfurt / M., Große Eschenheimer Str. 39

Claimed priority:
Switzerland of April 2, November 6, 1953 and February 19, 1954

Dr. Piero Maderni, Dr. Hans Ruckstuhl

and Dr. Willi Steinemann, Basel (Switzerland),

have been named as inventors

is in the para position to the carboxyl or amino group, with 1 mol of one in the aryl radical, if appropriate one or more lyophobic substituents from Series of l-aryl-ß-methyl-S-pyrazolons bearing halogen atoms, cyano, alkyl or alkoxy groups and the obtained monoazo dye in substance or on the fiber with a chromium donating agent treated.

The coupling of the diazo compounds with the pyrazolones is advantageously carried out in an alkaline medium ; the monoazo dyes obtained are worked up and isolated in the customary manner Filtering, washing and drying.

According to the invention, l-carboxy ^ -aminobenzene-i- or -5-sulfonic acid amides are used as diazo components into consideration, in which one hydrogen atom of the sulfonic acid amide group is replaced by alkyl, alkoxyalkyl, Cycloalkyl or sulfonic acid and carboxyl groups-free aralkyl or aryl is substituted and that other hydrogen atom can be substituted by alkyl. Both hydrogen atoms of the sulfonic acid amide group can also be replaced by groups which have heterocyclic radicals with the nitrogen atom form.

The l-aryl-3-methyl-5-pyrazolones mentioned as azo components are selected from the series of 1-phenyl-3-methyl-5-pyrazolones and l-naphthyl-3-methyl-5-pyrazolones. 1-Phenyl-3-methyl-5-pyrazolones of the composition HC C-CH _{3 are particularly suitable}

Il

HO-C

The last-mentioned pyrazolones are advantageously monosubstituted in the 3'- or 4'-position or in the 2 ', 3'- or 2', 4'- or 2 ', 5'- or 3', 4'- or 3 ', Disubstituted 5'-positions, halogen atoms, cyano, alkyl, alkoxy groups being possible as substituents come.

Of the l-naphthyl-3-methyl-5-pyrazodonen are the ¹ 1 - naphthyl - (I 'and 2') - 3 - methyl "- S -pyrazolone particularly worth mentioning, furthermore, the partly in naphthyl or completely hydrogenated derivatives.

The monoazo compounds are preferred for conversion into the chromium-containing azo dyes treated in aqueous solution and at elevated temperature with salts of chromium, e.g. B. with sodium or Potassium chromate or bichromate or with complexes

909 760/360

Salts such as sodium or potassium chromium tartrate. They have particularly good dyeing properties metal-containing azo dyes that have 2 molecules of monoazo less than 2 atoms, for example contain about 1 atom of chromium. Such chromium complex compounds are mostly used as 1: 2 complex compounds designated.

Many of the new monoazo dyes are dyes in the unmetallized state, which are used for Dyeing of wool according to the post-chrome plating process and, in particular, according to the single-bath contouring process suitable. This results in level, full yellow tones of very good light, wash and milled fastness achieved. The azo dyes, chromed in substance, dye wool and silk from neutral or weakly acidic dye bath in level full yellow tones with very good fastness properties; they suit also excellent for dyeing artificial nitrogen-containing fibers, such as synthetic polyamide fibers, and of leather.

Compared to the known metal-containing described in German Patent 899 537 The dyeings on wool obtainable from dyes are distinguished by those obtained by the present process Metal-containing dyes produced obtained dyeings due to their better wash fastness off at higher temperatures.

Compared with that from Example 6 of the above Chromkotnplex dye known from the patent specification shows that obtainable by the present process Methoxy derivative of this chromium complex dye has a much better solubility in the usual Solvents for lacquers and textile pulp.

Compared to the closest comparable chromium complex compounds of the monoazo dyes of the German US Pat. No. 842,089 and US Pat. No. 1,796,058, which contains an oxy group in the diazo component instead of a carboxy group in ortho-S division to the amino group, they are distinguished according to the invention available chromium complex dyes due to a better flexing fastness at 50 ° C.

The following examples illustrate the invention. The parts mean parts by weight, the percentages percentages by weight.

45 Example 1

23 parts of 1-carboxy ^ -aminobenzene-S-sulfonic acid methylamide are dissolved in 200 parts of water with 20 parts of 30% sodium hydroxide solution. One sets the solution to 6.9 parts of sodium nitrite and leaves them in drop in a template of 45 parts of concentrated hydrochloric acid and a little ice. The temperature of the reaction mixture is kept at 5 to 10 ° C. The diazo solution obtained is allowed to form a solution at 0 to 5 ° C cold solution of 19.1 parts of l-phenyl-3-methyl-5-pyrazolone, 13 parts of 30% sodium hydroxide solution, 20 parts of sodium carbonate and 300 parts Running water. The mixture is stirred until the coupling reaction, which starts immediately, is complete and the filter is filtered precipitated monoazo dye. It is dried a reddish yellow powder that is concentrated in Sulfuric acid and dissolves in dilute sodium carbonate solution with yellow color and wool in the single bath chromating process colors in lightfast, washfast and whalefast yellow tones.

To prepare the chromium complex compound in substance, a proportion of the filter cake corresponding to 8.3 parts of the dried dye is suspended in 230 parts of water. Is added to the slurry with a complex of 10 parts Natriumchromtartratlösung Kaliumchromisulfat, 23 parts of 13% tartaric acid solution and 9.3 parts of 30 ^fl / cent sodium hydroxide solution and boil the mass 20 hours under reflux. The deposited chromium-containing azo dye is filtered, the filter cake is dissolved in hot, dilute sodium hydroxide solution, precipitated therefrom by adding sodium chloride, filtered again and finally dried in vacuo at 95.degree. It is a brown-yellow powder and dyes wool, silk and synthetic polyamide fibers from a weakly acidic bath in light-, wash- and whackfast yellow tones.

Example 2

In the above example, 19.1 parts of 1-phenyl-3-methyl-S-pyrazolone are replaced by the equivalent Amount of l- (3'-chloro) -phenyl-3-methyl-5-pyrazolone, a monoazo dye is obtained, the wool in the single bath chromating process also dyes in lightfast, washfast and waterfast tones.

To convert into the chromium complex compound, 4.5 parts of the dye are dissolved in at 95 to 97 ° C 250 parts of water with the addition of sodium hydroxide. Add sodium hydroxide to the solution neutralized solution of 3 parts of crystallized sodium dichromate and 20 parts of water and heated with stirring up to the boiling point. Now set to a pjj value by adding acetic acid from 11.2 to 11.3 and cooks until the metallization is finished. The chromium-containing azo dye is precipitated with sodium chloride, filtered and dried in vacuo at 95 ° C. It represents a brownish yellow powder, which is wool, silk and synthetic Dyes polyamide fibers from a weakly acidic bath in lightfast, washfast and whackfast yellow tones.

Example 3

5.7 parts of the according to the details of Example 1 by coupling diazotized 1-carboxy-2-aminobenzene-5-sulfonic acid morpholylamide monoazo compound obtainable with 1- (2 ', 4'-dichloro) -phenyl-3-methyl-5-pyrazolone are dissolved in 200 parts of water at 95 ° C and after adding one with sodium hydroxide neutralized solution of 3 parts of crystallized sodium dichromate and 20 parts of water for 9 hours refluxed. The resulting chromium-containing azo dye is released from the metallizing solution Addition of sodium chloride precipitated, filtered and dried at 70 ° C. It is a yellow powder, the wool Silk and synthetic polyamide fibers from a weakly acidic bath in lightfast, washfast and whackfast yellow Tones colors.

Example 4

If in Example 1 23 parts of l-carboxy-2-aminobenzene-5-sulfonic acid methylamide by the equivalent amount of 1 - carboxy - 2 - aminobenzene - 5 - sulfonic acid (3'-methoxy) propylamide replaced, a monoazo dye is obtained, the metal complex compound of which gives light-, wash- and squeeze-fast yellow colorations.

Example 5

29.2 parts of 1-carboxy ^ -aminohenzene-S-sulfonic acid phenylamide are diazotized at 8 to 12 ° C. The diazo suspension is combined with a solution 19.1 parts of 1-phenyl-3-methyl-5-pyrazolone, 40 parts of sodium carbonate and 200 parts of water. The resulting Monoazo dye is deposited from a strongly alkaline medium, filtered and dried. He is ground a reddish yellow powder, the wool after

the post-chrome plating or the single-bath chrome plating process in yellow light-, wash- and mill-fast Tones colors.

Example 6

The cold solution of 23 parts diazotized! 1-carboxy - 2 - aminobenzene - 5 - sulfonic acid methylamide a cold solution of 23.5 parts of 1-naphthyl (1 ') -3-methyl-5-pyrazolone (M.p. 170 to 72 ° C) in 400 parts of water and 40 parts of 30% sodium hydroxide solution added. The mixture is stirred at 0 to 5 ° C. until the coupling has ended. After adding sodium bicarbonate the precipitated monoazo dye is filtered and dried in vacuo at 95 ° C. A yellow powder is obtained which turns greenish-yellow in water and in dilute sodium hydroxide solution and dissolves in concentrated sulfuric acid with yellow color and wool by the single bath chrome plating process colors in light, milled and carbonized, pure yellow tones.

Example 7

To convert the monoazo dye obtainable according to the above example into the chromium complex compound, 4.7 parts of it in 40 parts of ethyl polyglycol with 1.9 parts of chromium formate are heated at 95 to 105 ° C. for 2 ^{1 hours.} The solution is then poured into 100 parts of 5% sodium chloride solution. The chromium complex compound is nitrated and suspended in approximately 100 parts of water at 70 ° C. By adding sodium hydroxide, the suspension is made phenolphthalein-alkaline, then nitrated from the chromium-containing azo dye and dried at 80 ° C. It is a dark yellow powder, which dissolves in dilute sodium hydroxide solution with yellow and in concentrated sulfuric acid with greenish-yellow color and wool, silk and dyes synthetic polyamide fibers in light-, wash- and squeeze-fast, pure yellow tones.

In the table below there are diazo components (column A) and azo components (B), the for the production of further monoazo dyes for the single bath chroming dyeing process or for chromium-containing monoazo dyes are suitable. Their suitability is indicated in column (C), and in the columns (D) and (E) are the color shades of the dyeings on wool and, if appropriate, synthetic polyamide fibers described.

example Diazo component
(A) Azo component
(B) Suitability as
(C) Colors
Full
(D) on on
nylon
(E) 8th l-carboxy-2-amino-
benzene-5-sulfonic acid
(2'-methoxy) ethylamide l-phenyl-3-methyl-
5-pyrazolone Metachrome dye and
Chromium complex compound
dung for wool and
Polyamides yellow yellow 9 1 -Carboxy-2-amino-
benzene-4-sulfonic acid
methylamide the same Chromium complex compound
dung for wool the same . 10 l-carboxy-2-amino-
benzene-4-sulfonic acid
(3'-methoxy) propyl
amide the same the same the same 11 1 -Carboxy-2-amino-
benzene-5-sulfonic acid
methylamide l- (3'-cyano) -phenyl-
3-methyl-5-pyrazolone Metachrome and
Chromium complex compound
dung for wool and
Polyamides the same yellow 12th the same l- (4'-cyano) -phenyl-
3-methyl-5-pyrazolone the same the same the same 13th the same l- (3'-chloro-4'-cyano) -
phenyl-3-methyl-
5-pyrazolone the same the same the same 14th l-carboxy-2-amino-
benzene-5-sulfonic acid
naphthyl (l ') amide l-phenyl-3-methyl-
5-pyrazolone Metachrome dye the same - 15th l-carboxy-2-amino-
benzene-5-sulfonic acid
benzylamide the same the same the same 16 l-carboxy-2-amino-
benzene-5-sulfonic acid
cyclohexylamide the same the same the same 17th l-carboxy-2-amino-
benzene-5-sulfonic acid
(S'.o'J '^' - tetrahydro) -
naphthyl (l ') amide the same the same Tan
light yellow

7th Azo component 8th Suitability as Hue on
Wool nylon (E) example Diazo component (B) (C) (D) yellow (A) 1 - (3'-B rom) -phenyl- Metachrome dye and yellow 18th l-carboxy-2-amino- 3-methyl-S-pyrazolone Chromium complex compound benzene-5-sulfonic acid dung for wool and (3'-methoxy) propyl Polyamides the same amide l- (2 ', 3'-dichloro) -phenyl- Chromium complex compound the same 19th 1 -Carboxy-2-amino- 3-methyl-5-pyrazolone dung for wool and benzene-5-sulfonic acid Polyamides (3'-methoxy) propyl - amide l-phenyl-3-methyl- Metachrome dye the same 20th l-carboxy-2-amino- 5-pyrazolone benzene-5-sulfonic acid - (4'-chloro) phenylamide l- (3'-chloro) -phenyl- the same the same 21 l-carboxy-2-amino- 3-methyl-5-pyrazolone benzene-5-sulfonic acid - phenylamide l- (4'-ethyl) -phenyl- the same the same 22nd l-carboxy-2-amino- 3-methy 1-5 -py r azolone benzene-5-sulfonic acid yellow phenylamide ! - (S '^' J'.S'-Tetrahydro) - Chromium complex compound the same 23 l-carboxy-2-amino- naphthyl- (2 ') -3-methyl- dung for wool and benzene-5-sulfonic acid 5-pyrazolone Polyamides the same methylamide 1- (1 ', 2', 3 ', 4'-Tefrahydro) - the same the same 24 the same naphthyl- (2 ') -3-methy 1- 5-pyrazolone the same 1-decahydronaph the same the same 25th l-carboxy-2-amino- ethyl- (l ') -3-methyl- benzene-5-sulfonic acid 5-pyrazolone the same ethylamide l-naphthyl- (2 ') -3-me- the same the same 26th l-carboxy-2-amino- thyl-5-pyrazolone benzene-5-sulfonic acid the same methylamide 1- (4'-methoxy) -phenyl- the same the same 27 l-carboxy-2-amino- 3-methyl-5-pyrazolone benzene-5-sulfonic acid desgL methylaraid l- (2 ', 5'-diethoxy) - the same the same 28 the same phenyl-3-methyl- 5-pyr azolone the same ! - (S '^' - dimethyl) - the same the same 29 the same phenyl-3-methyl- 5-pyrazolone the same l-phenyl-3-methyl- the same the same 30th 1 -Carboxy-2-amino- 5-pyrazolone henzene-5-sulfonic acid pyrrilidylamide

Claims (2)

Patent claims: 1. Process for the production of monoazo dyes of the pyrazolone series and their chromium complex compounds, characterized in that 1 mol of the diazo compound is obtained from a 1-carboxy-2-aminobenzenesulfonic acid amide the composition COOH , -NH, SO ₉ -N ' wherein R _{1 is} alkyl, alkoxyalkyl, cycloalkyl or aralkyl or aryl free of sulfonic acid and carboxyl groups, R _{2 is} hydrogen or alkyl or, together with —N— and —R ₁ , a heterocyclic. Radical means and in which the group -SO ₂ -N; is in the para position to the carboxyl or amino group, with 1 mol of one in the aryl radical, if appropriate one or more lyophobic substituents from the 1 077 oil Series of 1-aryl-3-methyl-S-pyrazolons bearing halogen atoms, cyano, alkyl or alkoxy groups couples and the resulting monoazo dye in substance or on the fiber with a treated chromium-releasing agents. 2. The method according to claim 1, characterized in that the plating in substance 10 less than 2 atoms of chromium are used for 2 molecules of monoazo dye. Considered publications: German Patent Specifications No. 821 976, 842 089, 899537; U.S. Patent No. 1,796,058. With the announcement of the application there are two staining boards with explanations and a solubility table with explanation and three priority documents have been laid out.