DE1078714B - Process for the preparation of monoazo dyes and their metal complex compounds - Google Patents

Description

GERMAN

The present invention relates to a process for the preparation of monoazo dyes and their metal complex compounds, which before the metallization of the general formula

OH

N '

(I)

correspond, in which χ is an ethylene or propylene radical, ζ a phenolic or enolic hydroxyl group or a primary or secondary amino group in ortho to the —N = N group, and B the remainder an azo component, and in which B and the nucleus A can be further substituted.

The process for the preparation of the monoazo dyes and their metal complex compounds exists in that one mole of the diazo compound from an aminobenzene of the formula

OH

, -NH,

(Π)

wherein χ and A have the meanings given above, with 1 mole of one in ortho-S division to one phenolic or enolic hydroxyl group or coupling to a primary or secondary amino group Azo component couples and the resulting monoazo dye in substance or on the fiber treated with a metal donor.

Examples of the substituents which nucleus A can carry by definition include: halogen atoms (Chlorine, bromine), nitro, acetylamino, carbomethoxyamino, carbethoxyamino, methyl, ethyl, Sulphonic acid, sulphonic acid (2'-hydroxy) ethylamide and sulphonic acid hydroxypropylamide groups.

As azo components, for example: hydroxybenzenes, hydroxynaphthalenes, aminonaphthalenes, Alkylamino-, cycloalkylamino-, aralkylamino- and arylaminonaphthalenes, l-aryl-3-methyl-S-pyrazolones, Acylacetylaminoalkanes, Acylacetylaminobenzenes Process for the preparation

of monoazo dyes
and their metal 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 from May 17, 1957

Dr. Willy Steinemann, Basel (Switzerland),
has been named as the inventor

and acylacetylaminonaphthalenes. These azo components can carry substituents such as halogen atoms (chlorine, bromine), nitro, acetylamino, carbethoxyamino, Methyl, ethyl, methoxy, ethoxy, sulfonic acid, sulfonic acid amide, sulfonic acid mono- or dimethyl amide, Sulfonic acid (2'-hydr, oxy) ethylamide, sulfonic acid di (2'-hydroxyethyl) amide, sulfonic acid hydroxypropylamide, Sulfonic acid methoxypropylamide, sulfonic acid ethoxyethylamide, sulfonic acid phenylamide, Sulphonic acid N-2'-hydroxyethyl-N-phenylamide, sulphonic acid (2'-carboxy) phenylamide, methylsulphonyl groups or one

N ■

- C

x group

wherein χ has the meaning given above.

The diazotization of the aminobenzenes of the formula (II) is usually carried out at from 0 to 10 ^° C .; the heterocyclic ring

- C

is resistant to acids and alkalis in the cold.

909 768/354

The coupling of the diazo compounds obtained with the one phenolic or enolic hydroxyl group containing azo components takes place at 0 to 10 ° C advantageously in weakly acidic to weakly alkaline or strongly alkaline medium, optionally in the presence of pyridine, while the Coupling with the azo components containing a primary or secondary amino group at 10 to 20 ° C is carried out in a weakly acidic, preferably acetic acid medium. The resulting monoazo compounds are, if necessary, deposited with salt and then filtered off.

The conversion of the monoazo dyes into their metal complex compounds is preferably carried out with Compounds of chromium and cobalt. The metallization is advantageous in aqueous solution or in an organic medium, for example in formamide, or in the concentrated aqueous solution an alkali metal salt of a low molecular weight aliphatic monocarboxylic acid. One lets with advantage for 2 molecules of monoazo dye one less than 2, but at least 1 mol atom of metal act containing amount of a metal donor.

Suitable compounds of chromium are, for. B. Chromifluorid, Chromisulfat, Chromiformiat, Chromiacetat, Potassium chromisulfate or ammonium chromisulfate. Also the chromates, ζ. B. sodium or potassium chromate and bichromate, are particularly suitable for the metallization of monoazo dyes. It is advantageous to work here in a neutral to alkaline medium, with reducing agents if necessary Substances can be added.

As cobalt compounds z. B. cobalt formate, cobaltoacetate and cobaltosulfate. Will the metallization in the concentrated aqueous solution of an alkali metal salt of a low molecular weight aliphatic Monocarboxylic acid made, water-insoluble metal compounds can also be used find, for example, cobalt hydroxide and cobalt carbonate.

The metallization is particularly advantageously carried out in an aqueous or alkaline medium, wherein the metal compounds are added in the presence of those compounds which the metals in Keep a caustic alkaline medium dissolved in complex bonds, such as tartaric acid, citric acid and lactic acid.

The metal complex compounds obtained are, if appropriate after pouring in the organic metallization solutions in water, separated from an aqueous medium by adding salt, then filtered off, optionally washed and then dried.

The resulting metal-containing azo dyes are uniform metal complex compounds in which an 2 molecules of the monoazo compound are essentially bound to 1 atom of metal. The metal complex compounds are so-called 1: 2 complex compounds, in which 1 molecule of monoazo compound with about 0.3 to 0.7 atoms of metal is linked.

The monoazo dyes dye wool, silk, leather and synthetic polyamide fibers after the chromium plating or single bath chrome plating process in yellow, red, purple, blue, green, brown or gray shades of good fastness to washing, fulling, perspiration, light, potting and acids.

The metal-containing azo dyes dye wool, silk, leather and synthetic polyamide fibers neutral or weakly acidic dye bath in yellow, red, purple, blue, green, brown or gray real tones. If their solubility in organic solvents is sufficiently large, they are also suitable for dyeing masses dissolved in organic solvents and intended for spinning Paints and plastics of all kinds. The colorations obtained have good light, washing, perspiration, Flue gas and acid fastness.

The diazo components used in the examples are designated according to the following formulas:

OH

H ₂ C?

2- (3'-amino- ^ - hydroxyphenyl) -oxazoline
OH

NH ₉

N3 1O

H.C «

CH ₂
2- (3'-Amino-4'-hydroxyphenyl) dihydro-1,3-oxazine

In the following examples, the parts are parts by weight, the percentages are percentages by weight, and the Temperatures are given in degrees Celsius.

example 1

19.2 parts of 2- (3'-amino-4'-hydroxyphenyl) oxazoline are poured over with 20 parts of 30% strength hydrochloric acid and 180 parts of water. This mixture is cooled to 0 °, the solution of 6.9 parts of sodium nitrate in 30 parts of water is gradually added and it is stirred for a further 20 to 30 minutes at 0 to 5 ° in order to end the diazotization. Then, the diazo solution is neutralized to a _pH value from 5.0 to 6.0 by dropwise addition of 25 to 30 parts of 20% aqueous sodium carbonate solution and combined them at 0 to 5 ° with a solution of 22 parts of 1-acetylamino-7 hydroxynaphthalm, 4.4 parts of sodium hydroxide, 10 parts of anhydrous sodium carbonate and 250 parts of water. The mixture is stirred for several hours at 0 ° to 5 ° until the coupling has ended. After this time, the dark suspension is heated to 40 °, the monoazo dye is completely precipitated using sodium chloride, filtered off, dried and ground.

It is a black-blue powder that dissolves in water with blue and in concentrated sulfuric acid loosens with bordeaux paint. Its after the re-chrome plating or single bath chrome plating process The blue-gray dyeings produced on wool have excellent wash, milled and light fastness properties.

For dyeing, proceed as follows: In 6000 parts 2 parts of the monoazo dye described above and 10 parts of anhydrous dye are dissolved in water at 40.degree Sodium sulfate. 100 parts of wool are added to the dye liquor prepared in this way and the bath is heated in the process from about 30 minutes to 100 °. After adding 20 parts of 10% acetic acid, dyeing is carried out for 30 minutes at the boiling point, add 20 parts of 10% formic acid to the bath and hold it for 30 minutes 100 °, replacing the evaporated water from time to time. 1 part of sodium dichromate is then added as a 10% aqueous solution to the dye liquor and keeps the temperature at 100 ° for 30 minutes. The re-chromed wool dye is removed from the dye bath, rinsed with water and dried. It is dyed in a level blue-gray shade of very good wash, milled and lightfastness.

The diazo component used to make the monoazo dye of this example is made by Mononitration of 2- (4'-hydroxyphenyl) oxazoline [Prepared by treating 4-hydroxybenzene-carboxylic acid (2'-hydroxy) ethylamide with thionyl chloride or phosphorus oxytrichloride] and reducing the nitro group to the amino group.

Example 2

40 parts of the monoazo dye of Example 1 are dissolved in 400 parts of formamide. Then this solution is heated to 100 to 110 °, it is added within of 30 minutes with 30 parts of potassium chromium sulfate and holds it until the end of the chromium complex formation to 100 to 120 °. Then it is poured into 1200 parts of water, whereupon the chromium-containing azo dye salted out, filtered off and dried. After grinding it is a blue-black powder, which Wool, silk, synthetic polyamide fibers and leather in blue-gray tones from excellent washing, Milling and light fastness dyes.

2 parts of the chromium-containing azo dyes obtained in this way are dissolved in 4000 parts of water at 40 to 50 ° solved. 100 parts of pre-wetted wool are carried into this solution and 2 parts of 100% acetic acid are added dropwise one, whereupon the dyebath is heated to the boil within 30 minutes and it is heated for another 45 minutes holds at this temperature. The dyed wool is then taken out of the liquor and rinsed with water and dried. A dyeing is obtained which has very good fastness to light, washing and milling.

Example 3

40 parts of the monoazo dye of Example 1 are dissolved in a solution of 8 parts of sodium hydroxide in 1500 parts of water at 60 °. In this solution a solution made alkaline by means of aqueous ammonia solution is left within 30 minutes of 15 parts of cobalt sulphate in 600 parts of water flow in, holds at 60 ° for another 10 minutes, and the cobalt complex compound salts and filters it off. The dried and ground cobalt-containing dye is a blue-black powder which dyes wool and synthetic polyamide fibers in very real gray tones.

The following table contains further monoazo dyes and metal-containing azo dyes, which according to the information in Examples 1 to 3 are obtainable. In the table they are by the diazo and azo components [Columns (I) and (H)], by their type of use [Column (III)] and by the color of the metallized dyeings on wool [column (IV)].

Diazo component Azo component use hue example (I) (H) (III) the metallized
Coloring on wool 2- (3'-amino-4'-hydroxy- l-hydroxy-2-acetylamino Cr-K (IV) 4th phenyl) oxazoline 4-methylbenzene Brown the same 2-hydroxynaphthalene Cr-K 5 the same 2-hydroxynaphthalene-6-sulfone Post chrome. Reddish gray 6th acid Reddish gray the same 1-hydroxy-S.S-dichloronaphthalene Cr-K 7th the same 2-aminonaphthalene Co-K Reddish blue 8th the same 2-phenylaminonaphthalene Cr-K Gray 9 the same l-phenyl-3-methyl-S-pyrazolone- Cr-K Blue-gray 10 3'-sulfonic acid amide Orange red the same 1 - acetoacetylamino-2-ethylhexane Cr-K 11 the same l-acetoacetylaminonaphthalene Cr-K yellow 12th 4-sulfonic acid amide yellow the same l-hydroxynaphthalene-4-sulfone Post chrome. 13th acid Reddish blue the same l- (3'-chloro) -phenyl-3-methyl- Cr-K 14th 5-pyrazolone Orange red 2- (3'-amino-4'-hydroxy-5'-acetyl- 2-hydroxynaphthalene-6-sulfone Post chrome. 15th aminophenyl) oxazoline acid Reddish gray 2- (3'-Amino-4'-hydrO'Xy-5'-nitro-
phenyl) oxazoline 2-methylaminonaphthalene Co-K 16 the same l-aminonaphthalene-4-sulfonic acid Co-K Gray 17th (2'-hydroxy) ethylamide Gray

7th (Π) 8th (III) (IV) yellow example (D l-acetoacetylamino-2-methoxy- Cr-K 18th 2- (3'-amino-4'-hydroxy-5'-me- benzene Gray ethylphenyl) oxazoline 2-phenylaminonaphthalene Co-K 19th 2- (3'-amino-4'-hydroxyphenyl) - blue dihydro-1,3-oxazine 1-hydroxy-4-methoxynaphthalene Cr-K 20th 2- (3'-amino-4'-hydroxy-5'-carbo- Reddish gray methoxyaminophenyl) oxazoline 2- [3'-hydroxynaphthyl (2 ')] - Co-K 21 2- (3'-amino-4'-hydroxyphenyl) - oxazoline oxazoline-5'-sulfonic acid Reddish blue (2 "-hydroxy) ethylamide [7'-hydroxynaphthyl- (2 ')] - Cr-K 22nd 2- (3'-amino-4'-hydroxy- 2-ketopiperidine Reddish gray phenyl) oxazoline the same Co-K Brown 23 the same 1- (2'-Hydroxy-5'-methylphenyl) - Cr-K 24 the same 2-ketopiperidine Orange red l-phenyl-S-methyl-S-pyrazolone- Cr-K 25th 2- (3'-amino-4'-hydroxy-5'-carb- 4'-sulfonic acid amide Orange red ethoxyaminophenyl) oxazoline 1- (3'-cyano) -phenyl-3-methyl- Cr-K 26th 2 ~ (3'-amino-2'-hydroxy-5'-chloro- 5-pyrazolone yellow phenyl) -4-methyloxazoline l-acetoacetylamino octane Cr-K 27 2- (3'-amino-2'-hydroxy-5'-ethyl- Brown phenyl) oxazoline l-hydroxy-4-tert. butylbenzene Cr-K 28 2- (3'-amino-4'-hydroxy-5-pro- Reddish gray pionylaminophenyl) oxazoline 2-hydroxy-6-bromonaphthalene Cr-K 29 2- (3 ^/ -amino-4'-hydroxyphenyl) - Gray 4-methyloxazoline 1 -acety lamino-7-hy droxy- Cr-K 30th 2- (3 ^/ -amino-4'-hydroxyphenyl) - naphthalene B or do dihydro-1,3-oxazine l- (3'-chloro) -phenyl-3-methyl- Co-K 31 2- (3'-amino-2'-hydroxy 5-pyrazolone 5'-methylphenyl) dihydro blue 1,3-oxazine l-aminonaphthalene-4-sulfonic acid Co-K 32 2- (3'-amino-4'-hydroxy-5'-nitro- di- (2'-hydroxyethyl) amide phenyl) -4-methyldihydro- yellow 1,3-oxazine l-aeetoacetylamino-l.l ^ .S-tetra- Cr-K 33 the same methylbutane Brown 'N- (4'-hydroxyphenyl) -l-aza- Cr-K 34 2- (3'-amino-4'-hydroxyphenyl) - 2-keto-3-oxacyclohexane Reddish gray dihydro-1,3-oxazine N- [7'-hydroxynaphthyl (1 ')] - Co-K 35 the same l-aza-2-keto-3-oxacyclohexane yellow 1- (4'-acetoacetylaminophenyl) - Cr-K 36 2- (3'-amino-4'-hydroxy- 2-ketopyrrolidine Gray-blue phenyl) oxazoline 1-carbo-isopropoxyamino Post chrome. 37 the same 7-hydroxynaphthalene and meta chrome blue 1-hydroxy-4-methoxynaphthalene Co-K Gray 38 the same 1-Carbo- (2'-methoxy) -ethoxy- Cr-K 39 the same amino-7-hydroxynaphthalene Orange red 1- [naphthyl- (l ')] -3-methyl- Cr-K 40 the same 5-pyrazolone-6'-sulfonic acid Orange red 1- (2 ', 3'-tetramethylene) -phenyl- Cr-K 41 2- (3'-amino-4'-hydroxyphenyl) - 3-methyl-5-pyrazolone-4'-sulfone 4-methyloxazoline acid amide yellow 1-acetoacetylaminobenzene Cr-K 42 the same 4-sulfonic acid phenylamide Gray 2-benzylaminonaphthalene Co-K 43 2- (3'-amino-4'-hydroxyphenyl) - dihydro-1,3-oxazine-5'-sulfone acid (3 "-hydroxy) propylamide

9 Cn) 10 (IV) example (I) 2-cyclohexylaminonaphthalene (III) Blue-gray 44 2- (3'-amino-4'-hydroxyphenyl) -
-i-methyloxazoline-S'-sulfonic acid l-phenyl-S-methyl-S-pyrazolone-
3'-sulfonic acid- (3 "-methoxy) -
propylamide Post chrome. Orange red 45 2- (3'-amino-4'-hydroxyphenyl) -
dihydro-1,3-oxazine-5'-sulfone
acid 1-acetoacetylaminobenzene
4-sulfonic acid methylamide Post chrome. yellow 46 2- (3'-Amino-4'-hydroxyphenyl) -
oxazoline-5'-sulfonic acid 1-naphthyl (2 ') -3-methyl-
5-pyrazolone-6'-sulfonic acid Post chrome. Orange red 47 2- (3'-amino-4 ^/ -hydroxy-5'-chloro-
phenyl) dihydro-1,3-oxazine 2-acetoacetylaminonaphthalene
6-sulfonic acid Post chrome. yellow 48 2- (3'-Amino-4'-hydroxyphenyl) -
4-methyloxazoline 2-phenylaminonaphthalene
3'-sulfonic acid amide Post chrome. Gray 49 the same 2- (4'-acetoacetylaminophenyl) -
oxazoline Co-K yellow 50 2- (3'-amino-4'-hydroxy-
phenyl) oxazoline 2- (4'-acetoacetylaminophenyl) -
4-methyloxazoline Cr-K yellow 51 the same 2- [3'-hydroxynaphthyl (2 ')] -
dihydro-1,3-oxazine Cr-K Reddish gray 52 the same 1-acetoacetylaminobenzene
4-sulfonic acid methylamide Co-K yellow 53 the same l-phenyl-S-methyl-S-pyrazolone-
3'-sulfonic acid-N-2 "-hydroxy-
ethyl-N-phenylamide Cr-K Orange red 54 the same ^ -Hydroxynaphthalene-o-sulfone-
acid phenylamide Cr-K Reddish gray 55 the same 1-acetoacetylaminobenzene
4-sulfonic acid Cr-K yellow 56 2- (3'-amino-4'-hydroxy-5'-bromo
phenyl) oxazoline l-acetylamino-7-hydroxy-
naphthalene Post chrome. Gray 57 2- (3'-amino-4'-hydroxy-5'-chloro-
phenyl) oxazoline l-phenyl-S-methyl-S-pyrazolone-
4'-sulfonic acid-2 "-ethoxy-
ethylamide Cr-K Orange red 58 the same Cr-K

Claims (5)

Patent claims: 1. Process for the production of monoazo dyes and their metal complex compounds, characterized in that 1 mol of the diazo compound is obtained from an aminobenzene of the formula OH NH, in which χ denotes an ethylene or propylene radical and in which the nucleus A is further substituted can be, with 1 mole of an ortho-S division to a phenolic or enolic hydroxyl group or azo component coupling to a primary or secondary amino group and the resulting monoazo dye in bulk or on the fiber with a metal donor treated. 2. The method according to claim 1, characterized in that the monoazo dyes with treated a metal donor so that a metal-containing azo dye is formed, the contains essentially 1 metal atom bound to 2 molecules of monoazo compound in a complex. 3. The method according to claim 1 and 2, characterized in that there are 2 molecules of monoazo dye an amount of a metal donor containing less than 2 but at least 1 metal atom Means to act. 4. The method according to claim 1 to 3, characterized in that one is used as the metal donor Agent used a chromium-releasing agent. 5. The method according to claim 1 to 3, characterized in that one is used as the metal donor Agent used a cobalt-releasing agent. A coloring table was displayed when the application was announced. © 909 768/354 3.60