DE963898C - Process for the production of metal-containing azo dyes - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

ISSUED MAY 16, 1957

GERMAN PATENT OFFICE

PATENT LETTERING

Jfc 963 898 CLASS 22a GROUP 5 INTERNAT. CLASS C 09b

S 44481 IVbJ 22 a

Dr. Reinhard Neier, Basel (Switzerland) has been named as the inventor

Sandoz A. G., Basel (Switzerland)

Process for the production of metal-containing azo dyes

Patented in the territory of the Federal Republic of Germany from June 25, 1955 Patent application approved on November 29, 1956

Grant of patent announced on May 2, 1957 The priority of the application in Switzerland of June 25, 1954 has been claimed

The subject of patent 888 904 is a process for the production of chromable disazo dyes the composition

R-N = N

wherein R is the optionally substituted radical of a diazo component of the benzene or naphthalene series and R _{1 is} in the ortho position to the azo

group containing a hydroxyl group and optionally bearing further substituents Is a residue of any azo component with the exception of i, 3-dioxybenzene, the components are to be chosen so that the disazo dyes formed have at least one water-solubilizing agent Group included.

It has now been found that valuable metal-containing azo dyes are obtained if you have two or several different from each other, according to the

709 514/251

driving patent 888 904 available, water soluble Disazo compounds of the composition

X) H OH

R '_ N = N - ■ -

-azo - R "-

(A)

wherein the benzene nucleus I can carry any other substituents customary in azo dyes, and both OH groups are ortho to —azo—, R ' the remainder of a diazo component of the benzene or naphthalene series, R "—OH the remainder of an azo component the oxybenzene, oxynaphthalene, pyrazolone or acetoacetic acid alkylamide or arylamide series and χ at least one water-solubilizing group from the series of sulfonic acid, carboxyl, alkylsulfonyl and sulfonic acid amide groups, or if one or more water-soluble disazo compounds of the composition (A) and one or more monoazo compounds of the composition

R ₂ -N = NR ₃ -OH

(B)

wherein R _{2 is} the remainder of a sulfonic acid group-free diazo component of the benzene series which contains a substituent capable of forming metal complexes in the ortho position to the N = N group, and R ₃ —OH is the remainder of a sulfonic acid group-free A'zo component of the oxybenzene, oxynaphthalene -, pyrazolone or acetoacetic acid alkylamide or -arylamid series, in which the OH group is adjacent to the —N = N group, or when one or more water-soluble disazo compounds of the composition (A) and one or more monoazo compounds of the composition

R ₂ -N = NR ₄ -NH ₂ (C)

in which R _{2 has} the meaning mentioned above and R ₄ —NH ₂ denotes the residue of a 2-aminonaphthalene free from sulfonic acid groups, treated with metal donating agents, preferably with chromium or cobalt donating agents.

The metal-containing azo dyes obtained according to the present process are mixed metal complex compounds, the integral part of which is the asymmetric 1: 2 complex compounds of the composition

R '-N = N

0 -

azo
R "- O

(D)

Me - z

form, in which R 'and I have the abovementioned meaning, the divalent radical R "- O - the abovementioned corresponds to a monovalent radical R "- OH, the two - O - atoms in the ortho position to - azo - are, in which ζ is the radical of a disazo compound different from the radical y of the same general Composition (A), the remainder of a monoazo compound (B) or the remainder of a monoazo compound (C) denotes and Me denotes a metal atom, preferably a chromium or cobalt atom.

For the preparation of the monoazo compounds of the composition (B), for example, the following can be used aminobenzenes according to the definition into consideration: 2-amino-i-oxybenzene, 2-amino-i-oxy-4-halobenzenes, 2-Amino-i-oxy-4-nitrobenzene, 2-Aminoi-oxy-4-alkylsulfonylbenzenes, 2-Amino-i-oxybenzene-4- or -5-sulfonic acid amide, 2-Amino-i-oxy-6-halogen- or -ö-alkylbenzene-4- or-5-sulfonic acid amides, 2-Amino-i-oxy-4-halobenzene-5- or -6-sulfonic acid amides, the corresponding 2-amino-i-methoxybenzenes, also 2-aminobenzene-i-carboxylic acid, 2-amino-5 - alkylsulfonylbenzene - 1 - carboxylic acids, 2 - aminoi-carboxybenzene-4- or -5-sulfonic acid amide, 2-Aminoi-carboxymethoxybenzene-4- or -5-sulfonic acid amide. The aminobenzenesulfonic acid amides mentioned can pass through on the nitrogen atom of the sulfonic acid amide group Alkyl, oxalkyl, methoxyalkyl, cycloalkyl, aralkyl and / or aryl radicals, which in turn have further substituents may contain, be substituted. As azo components, for example:

a) Oxybenzenes, such as i-oxy-4-alkylbenzenes, i-oxy-

2, 4-dialkylbenzenes, i-oxy-2-acylaminebenzenes,

b) Oxynaphthalenes, such as 2-oxynaphthalene, 1, 5-, 2, 6- or 2, 7-dioxynaphthalene, in the 6- or 7-position substituted by low molecular weight alkyl, alkoxy, methylsulfonyl groups or halogen atoms 2-oxynaphthalenes, 2-oxynaphthalene-4-, -5-, -6- or -7-sulfonic acid amide and those substituted on the nitrogen atom Derivatives, i-acylamino-6- or -7-oxynaphthalenes,

c) Pyrazolones, such as i-aryl-3-alkyl-5-pyrazolones and those carrying further substituents in the aryl nucleus Derivatives, i-aryl-S-pyrazolone-ß-carboxylic acids or -carboxamides,

d) Acetoacetylaminoalkanes, benzenes or naphthalenes.

Suitable monoazo compounds of the composition (C) are those obtained by coupling the above Section mentioned diazo components with 2-aminonaphthaUn, 2-amino-alkylsulfonylnaphthalenes or 2-Ainonaphthalinsulfonsäureamiden available products.

The mixtures of the disazo compounds are used for conversion into the metal complex compounds of the composition (A) and the monoazo compounds of the composition (B) or (C) in this way choose that in 2 moles of azo compound mixture at least 1 mole of a water-soluble disazo compound the composition (A) is included.

The azo compound mixtures are preferably metallized with salts of chromium, e.g. Chromium fluoride, chromium sulfate, chromium acetate, chromiformate, potassium chromium sulfate or ammonium chromium sulfate, and with salts of cobalt, e.g. cobalt acetate, cobalt formate or cobalt sulphate, in aqueous Slurry or solution, or in an organic medium such as formamide, or in the Melt of an alkali salt of a low molecular weight

aliphatic monocarboxylic acid. The implementation of the metallization in aqueous media is particularly advantageous or alkaline medium, the chromium salts being used in the presence of such compounds, which are able to form soluble complex compounds with the former in an alkaline medium, e.g. B. Tartaric acid, citric acid, or lactic acid. The chromates, e.g. sodium or potassium chromate or -bichromate, can be used in an excellent way

ίο use metallization of the azo compounds, in this case in a strongly alkaline medium, possibly with the addition of reducing substances, is being worked on. If the azo compounds contain the methoxy group as a complex-forming group, the metallization is preferably carried out in organic solvents, e.g. glycols (such as Ethylene glycol, ethyl polyglycol, butyl polyglycol), and in the presence of acid-binding agents, for example Sodium acetate.

The metal-containing products obtained are used for working up Azo dyes - if necessary after pouring the organic metallization solutions into Water - precipitated from aqueous medium by adding salt, filtered off, optionally washed and then dried.

The metal-containing azo dyes obtainable according to the invention are readily soluble in water and color Wool, silk, leather and artificial nitrogen-containing fibers in clear shades of very good washing, wool and lightfastness. Compared to the symmetrical metal complex compounds from disazo dyes Composition (A), the mischmetal complexes described here are characterized by technical meaningful color tones, e.g. clear green or brown tones.

Compared to the metal-containing disazo dyes known from German patent specification 889 338 the metal complex compounds according to the invention are distinguished of mixtures of azo dyes due to a significantly improved absorption capacity on wool the end.

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

example 1

28.9 parts of the disazo compound obtainable by coupling diazotized 3-amino-4-oxy-i, i'-azobenzene-3'-sulfonic acid amide with i-carbo- (2'-ethoxy) -ethoxyamino-7-oxynaphthalene and 17, 8 parts of the monoazo compound obtainable by coupling diazotized 2-aminobenzene-i-carboxylic acid with i- (3'-chloro) -phenyl-3-methyl-5-pyrazolone are mixed with 6 parts of sodium hydroxide in 1200 parts of water. To this are added 250 parts of a I5 ° / _o aqueous solution of i-oxybenzene-2-carboxylic acid sodium containing 2.6 parts of chromium in complex bond, and the mixture is boiled so long under reflux, no longer be detected until the starting compounds permit. The chromium complex compound formed is then precipitated from the solution by adding sodium chloride, nitrated, dried and ground.

It is a dark powder that mixes wool, silk, leather and synthetic polyamide and urethane fibers in grass green Tones colors.

The aqueous solution of the chromium complex compound from i-oxybenzene-2-carboxylic acid sodium is obtained in the following manner: 28.9 parts of ammonium chromium sulfate, corresponding to 7.6 parts of chromium (III) oxide, are dissolved in 150 parts of water at 40 °. After adding 2 parts of sodium hydroxide, the mass is stirred until the precipitate which initially separated out has redissolved. Then 27.6 parts of i-oxybenzene-2-carboxylic acid are added and the temperature is increased to 90 °. By adding approximately 15 parts of sodium hydroxide the _pH value is provided to the mixture to 8, after which the mass with dark green color in solution geht._ It provides to a volume of 250 parts, and the solution is allowed to cool.

50 parts of well moistened wool in strand form are placed in a porcelain beaker of 21 content in a solution of 0.5 parts of the obtained according to this example, chromium-containing dye in 1500 parts of water of 40 ^0th The bath is heated to the boil within 30 minutes while the material to be dyed is changed frequently. After a further 30 minutes of boiling time, 0.5 part of 10% acetic acid is added to the dyebath and the wool is dyed at boiling temperature for about 30 minutes until the dye is completely absorbed onto the fiber. The dyed wool is then taken out of the bath, rinsed well in cold water and dried. It is colored in a green tone.

If, instead of wool, 50 parts of polyamide fibers in strand form are used, the result is the same Method of operation when the dyebath is completely exhausted, a fiber material dyed in green tones.

Example 2

22.3 parts of the disazo compound obtainable by coupling diazotized 3-amino-2-oxy-5-methyl-i, i'-azobenzene-3'-sulfonic acid amide with 2-oxynaphthalene and 17.8 parts of the diazotized 2-amino The monoazo compound produced by i-oxy-4-chlorobenzene and i-acetylamino-7-oxynaphthalene are mixed in 300 parts of formamide. After adding 25 parts of ammonium chromisulfate, the suspension is heated to 90 to 100 ° until a solution has formed and the starting compounds can no longer be detected in it. The resulting chromium complex compound is precipitated by diluting the mixture with 600 parts of 20 ° / _o sodium chloride solution. After filtering, drying and grinding it is a dark powder that dyes wool, silk, leather and synthetic polyamide and urethane fibers in blue tones.

Example 3

22.3 parts of the disazo compound from diazotized 3-amino-2-oxy-5-methyl-i, i'-azobenzene-3'-sulfonic acid amide and 2-oxynaphthalene and 18.3 parts of the by coupling of diazotized 2-amino-i-oxy-

5-nitrobenzene with i-acetylamino-7-oxynaphthalene available monoazo compound are stirred with 8 parts of sodium hydroxide in 1000 parts of water at 70 ° to form a fine slurry. Is added dropwise a mixture of 14.2 parts of crystalline Kobaltosulfat, 130 parts of 3 ° / _o aqueous solution of tartaric acid and 18.4 parts 3o ° / ₀ sodium hydroxide solution. After stirring for half an hour, the cobalt complex compound formed is precipitated by adding sodium chloride, then filtered off, dried and ground. It is a dark powder that dyes wool, silk, leather and synthetic polyamide and urethane fibers in shades of blue.

Example 4

22.3 parts of the diazotized by domes! 3-Amino-4-oxy-i, i'-azobenzene-3'-sulfonic acid amide with 2-oxynaphthalene obtainable disazo compound and 20.6 parts of the diazotized! 2-Amino-i-oxybenzene-4-sulfonic acid amide and i-acetoacetylamino-2-ethylhexane available monoazo compound are used together with 4 parts of sodium hydroxide dissolved in 2000 parts of water at 80 °. After adding 10 parts Sodium acetate and 15 parts of crystallized cobalt sulfate are stirred the mass until there are no starting compounds more can be proven. The cobalt complex compound formed is through Addition of sodium chloride precipitated from the solution, then filtered off, dried and ground. she is a brown powder, which contains wool, silk, leather and synthetic polyamide fibers in yellow-brown Tones colors.

Example 5

24.9 parts of the disazo compound obtainable by coupling diazotized i- (3'-amino-4'-oxy) -benzene-i, i'-azonaphthalene-4-sulfonic acid with 2-oxynaphthalene and 17.6 parts of the diazotized 2 -Amino-i-oxy-4-chlorobenzene and i-acetylamino-7-oxynaphthalene-available monoazo compound are mixed in 300 parts of formamide. After adding 25 parts of ammonium chromisulfate, the suspension is heated to 90 to 100 ° until the starting compounds can no longer be detected in it. Quenched by diluting the mixture with 500 parts of 20 ° / _o aqueous sodium chloride solution is precipitated, the resulting chromium complex compound. After filtering off, it is purified by dissolving it in 1500 parts of water in which 10 parts of sodium hydroxide are dissolved, precipitating it with 160 parts of sodium chloride and then filtering it off. After drying and grinding, it is a dark powder, which dyes wool, silk, leather and synthetic polyamide fibers in black tones.

The following table contains a number of other metal-containing azo dyes which are based on one of the above described method can be produced. The columns (I) and (III) contain the parts by weight of those used for mixed metallization, listed in columns (II) and (IV) Azo compounds. The column (V) shows the complex-bound metal, and the column (VI) identifies the metal-containing azo dyes by the shades of their dyeing on wool.

Tabel

at
game (I) 40 6th 28.9 45 7th 28.9 8th 28.9 50 9 28.9 55 IO 28.9 So II 22.3 12th 22.3

(Π)

(III) (IV)

(V)

(VI)

3-Amino-4-oxy-i, i'-azobenzene-3'-sulfonic acid amide -> - i-Carbo- (2'-ethoxy) -ethoxyamino-7-oxynaphthalene

the same

the same

the same

the same

3-Amino-4-oxy-i, i'-azobenzene-3'-sulfonic acid amide -> - 2-0xynaphthalene

the same

16.6

17.8

20.2

21.6

24.9

18.3

7.5 2-aminobenzene-i-carboxylic acid
- »- i-Phenyl-s-methyl-s-pyrazolone

2-aminobenzene-i-carboxylic acid
- * - i-Acetoacetylamino-2-methoxybenzene

2-Amino-i-oxybenzene-4-sulfonic acid phenylamide - »- 2-aminonaphthalene

3-Amino-4-oxy-i, i'-azobenzene-3'-sulfonic acid amide - »- 2-0xynaphthalene

i- (3'-Amino-4'-oxy) -benzolazonaphthalic-6-sulfonic acid
- »· 2-oxynaphthalene

2-amino-i-oxy-4-nitrobenzene
-> i-acetylamino-7-oxynaphthalene

2-amino-i-oxy-4-chlorobenzene
- »- 2-aminonaphthalene

Cr

Cr

Cr

Co

Co

Cr

Co

green

green

Gray-green

Olive brown

Olive brown

Gray

Brown

at
game 5 28 (I) (Π) (III) (IV) (V) (VI) H
10 60 29 22.3 3-amino-4-oxy-i, i'-azobenzene-
3'-sulfonic acid amide -> - 2-oxy
naphthalene 11.9 3-amino-4-oxy-i, i'-azobenzene-
3'-sulfonic acid amide - »- i-Phe-
nyl-3-methyl-5-pyrazolone Cr Brown 15th 22.3 the same 11.1 3-amino-2-oxy-5-methyl-
i, i'-azobenzene-s'-sulfonic acid
amide - »- 2-oxynaphthalene Co Brown ¹⁵ 16 23.1 3-amino-2-oxy-5-methyl-
i, i'-a £ topzol-3 '~ sulfonic acid
amide - * - 2-oxynaphthalene 20th 2-Amino-I-oxy-4-chloro-5-nitro-
benzene h> - i-acetylamino-
7-oxynaphthalene Co blue 17th 23.1 the same 16.5 2-Amino-I-oxy-4-chloro-5-nitro-
benzene -> 2-oxynaphthalene Cr blue ²⁰ 18 23.1 the same 15th 2-amino-i-oxy-4-chlorobenzene
-> - 2-oxynaphthalene Cr blue
violet 19th 23.1 the same 15th the same Co violet ³⁵ 20 23.1 the same 22nd 2-amino-i-oxy-5-nitrobenzene
- + - i-Carbo- (2'-propoxy) -
ethoxyamino-7-oxynaphthalene Cr blue 21 23.1 the same 22nd the same Co blue 30 22 22.3 the same i8.3 2-amino-i-oxy-4-nitrobenzene
-> - i-acetylamino-7-oxy-
naphthaUn Cr Green Blue 23
35 11.2 the same 24.9 i- (3'-Amino-4'-oxy) -benzene-azo-
naphthalene-4-sulfonic acid -y
2-0xynaphtha green Co Brown 24 24.9 i- (3'-Amino-4'-oxy) -benzene-
azo-naphthalene-4-sulfonic acid
-> - 2-oxynaphthalene 17.8 2-aminobenzene-i-carboxylic acid
-v i- (3'-chloro) -phenyl-
3-methyl-5-pyrazolone Cr Brown ⁴⁰ 25 24.9 the same 20th 2-Amino-I-oxy-4-chloro-5-nitro-
benzene - * ■ I-acetylamino-
7-oxynaphthalene Cr Brown 26th
45 21.1 3-Amino-4-oxy-i, i'-azobenzene
-> ■ 2-oxynaphthalene-4-sulfone
acid 16.9 2-amino-i-oxy-4-nitrobenzene
-> ■ i- (3'-chloro) -phenyl-
3-methyl-5-pyrazolone Cr Brown 55 28.9 3-amino-4-oxy-i, i'-azobenzene-
3'-sulfonic acid amide -> -
i-Carbo- (2'-ethoxy) -ethoxy-
amino-7-oxynaphthalene 13.3
6th 2-aminobenzene-i-carboxylic acid
-> - i- (3'-chloro) -phenyl-
3-methyl-5-pyrazolone
2-amino-i-carboxybenzene
5-sulfonic acid phenylamide -> -
i- (3 '-chloro) -phenyl-3-methyl-
5-pyrazolone Cr green 28.9 3-amino-4-oxy-i, i'-azobenzene-
3'-sulfonic acid amide - »-
i-carbo- (2'-methoxy) -eth-
oxyamino-7-oxynaphthalene 34, 2-amino-i-oxy-4-nitrobenzene
-> - i-Acetoacetylaminohexane Co Brown 22.3 3-amino-4-oxy-x, i'-azobenzene-
3'-sulphonic acid amide -y
2-0xynaphthalene 17.8 2-amino-i-oxy-4-chlorobenzene
- * - i-Acetylammo-7-oxynaph-
thalin Cr black 22.3 the same 21.8 2-amino-i-oxybenzene-4-sulfone
acid dimethylamide -> -
i-acetylamino-7-oxynaph-
thalin Cr black

at
game (I) (II) (III) (IV) (V) (VI) 30th 22.3 3-amino-4-oxy-i, i'-azobenzene-
3'-sulfonic acid amide -> -
2-oxynaphthalene 17.8 2-aminobenzene-i-carboxylic acid
- »- i- (3'-chloro) -phenyl-
3-methyl-5-pyrazolone Cr khaki 31 22.3 the same 18.7 2-amino-i-carboxybenzene
5-sulfonic acid methylamide ->
i-phenyl-s-methyl-S-pyrazo-
lon Cr khaki 32 24.6 2-amino-4-oxy-i, i'-azobenzene-
3 '-sulfonic acid- (2''-oxy) -ethyl-
amide - »- 2-oxynaphthalene 18.7 the same Cr khaki 33 23.1 3-amino-4-oxy-i, i'-azobenzene-
3'-sulfonic acid methylamide
- * ■ 2-0xynaphthalene 18.7 the same Cr khaki

Claims (3)

Patent claims: ι. Process for the preparation of metal-containing azo dyes, characterized in that one two or more different water-soluble disazo compounds of the composition ,OH R '- N = N - I OH azo — R "- - χ wherein the benzene nucleus I can carry any other substituents customary in azo dyes and both OH groups in the ortho position to - azo - are, R 'is the remainder of a diazo component of Benzene or naphthalene series, R "- OH the remainder of an azo component of the oxybenzene, oxynaphthalene, Pyrazolone or acetoacetic acid alkylamide or arylamide series and χ at least one water-soluble making group from the series of sulfonic acid, carboxyl, alkylsulfonyl and sulfonic acid amide groups means, or that one or more water-soluble disazo compounds of the composition (A) and one or more Monoazo compounds of the composition R ₂ -N = NR ₃ -OH (B) wherein R _{2 is} the remainder of one of sulfonic acid groups R ₂ -N = NR ₄ -NH ₂ (Q free diazo component of the benzene series, which in the ortho position to the --N = N group contains a substituent capable of forming metal complexes, and R ₃ - OH the remainder of an azo component of the oxybenzene, oxynaphthalene, pyrazolone or acetoacetic acid alkylamide or - arylamide series in which the OH group is adjacent to the —N = N group means, or that one or more water-soluble disazo compounds of the composition (A) and one or more monoazo compounds of the composition wherein R _{2 has} the meaning mentioned above and R ₄ - NH _{2 is} the residue of a 2-aminonaphthalene free from sulfonic acid groups, treated with metal donating agents. 2. The method according to claim 1, characterized in that that one applies about ι atom of metal to 2 moles of azo compound. 3. Process according to Claims 1 and 2, characterized in that one is used as the metal donor Medium chromium or cobalt releasing agent used. Considered publications: German Patent Specifications No. 888 904, 889 338. © 609 709/364 11.56 (709 5147251 5.57)