DE1922900A1 - Chromium-containing azo dyes and process for their preparation - Google Patents

Description

CIBA AKTIENGESELL SCHAF T, BASEL (SWITZERLAND)

Case 646VE
Germany

Chromium-containing azo dyes and process for their preparation.

It has been found that valuable, new chromium-containing azo dyes are obtained which contain an atom of chromium bound to two molecules of different monoazo dyes in a complex manner if one has a metallizable monoazo dye of the formula which is free of carboxylic acid groups and sulfonic acid groups

(1) OH

DN = NA ₉

909848/1139

wherein D is the radical of a neighboring position to the OH group "'- ^{-, and} the azo bridge -an bound diazo component of the benzene series, and A is the radical of a in the position adjacent to enolized-keto group to the azo bridge bound acetoacetamides ^ mean, and a complex chromium compound which is a Atom 'chromium complex on a molecule of the monoazo dye of the formula

(2)

I '■ ■

contains bound, wherein one X is a nitro group and the other X represents a sulfo group in a molecular ratio about 1: 1 with each other »

The monoazo dyes of the formula (I) required in the present process can be known per se Way by coupling in a weakly acidic to alkaline agent of o-oxydiazo compounds of the benzene series with in the o-position to produce acetoacetic acid amides coupling to the enolized keto group. As can be seen from the above information, may the components contain no sulfonic acid groups and no carboxylic acid groups. They also preferably do not have any functionally modified sulfonic acid groups, e.g. none Sulfonic acid amide or sulfonic acid ester groups. It is recommended also choose those components which dyes' result which, in addition to those capable of complex formation, or »

3 0 9 8 4 8/1139 BAD ORIGINAL

involved in this, located in o-position to the azo group Oxy groups do not contain any other oxy groups. Taking these conditions into account, come for the construction of the monoazo dyes of the formula (I), for example, components according to the following considerations:

As diazo compounds those which, in addition to the hydroxyl and the amino group has further substituents such as nitro groups, halogen atoms (e.g. chlorine), alky groups (e.g. methyl), alkoxy groups (e.g. methoxy) or acy! amino groups, especially those with only a few, i.e. at most e.g. 4 carbon atoms (e.g. acetylamino). Those l-oxy-2-aminobenzene derivatives which are in the 4-position are particularly advantageous have a substituent, preferably a nitro group.

Examples are: 4- or 5-chloro-2-amino-1-oxybenzene, 4,6-dichloro-2-amino-1-oxybenzene,
5,4,6-trichloro-2-amino-1-oxybenzene,
4-chloro-5- or -e-nitro-1-amino-1-oxybenzene, 6-nitro-4-methyl-2-amino-1-dxybenzene, 6-nitro-4-acetylamino-2-amino-1-oxybenzene , k _$ 6-dinitro-2-amino-1-oxybenzene and especially 4- or 5-nitro-2-amino-1-oxybenzene, 4-nitro-6-chloro-2-emino-1-oxybenzene and 4-nitr () -6 "teety lamino-S-amino-l-oxybenzene"

900848/1139

Particularly suitable coupling components are those acetoacetic acid amides which are free from sulfur-containing Substituents are.-Examples are: Acetoacetic acid amide, acetoacetic acid-N-isopropyl-, N-butyl-, -N-dimethyl-, -N-diethyl-, -N-dibutyl-, - N-methoxypropyl- or -N-benzylamide, acetoacetic acid-N-methyl- or -ethylanilide, Acetoacetylaminocyclohexane, Acetöaeetylaminobenzol, l-Acetoacetylamino-2,4-dimethoxybenzene, 1-Acetoacetylamino-2,5-dimethyl- or -dimethoxybenzene, l-acetoacetylamino-2- or -4-ethylbenzene, l-acetoacetylamino-2- or -4-chlorobenzene, l-acetoacetylamino-2,5-dichlorobenzene, l-acetoacetylamino-4-meth'y.l- or -4-methoxybenzene, 1-. Acetoacetylarnino-2-ethyl-5-chlorobenzene.

The monoazo dye of the formula (2) can be also produce in a known manner by coupling. Its conversion into the 1: 1 chromium complex takes place according to the usual, methods known per se, e.g. by adding it to an acidic medium with an excess of a trivalent salt Chromium, such as chromium formate, chromium sulfate or chromium fluoride Boiling temperature or, if appropriate, temperatures exceeding 100 C. In general, it is advisable to to carry out the metallization in a known manner, e.g. in the presence of organic solvents such as alcohol or formamide .

In general, it is advantageous not to dry the required starting materials in the present process after their production and excretion, but to process than wet paste further. ¹

9 0 9 8 4 8 - /. 1 13 9 - BADORlGiNAL

The conversion of the 1: 1 chromium complex with the metal-free dyes takes place in an aqueous, neutral solution to slightly alkaline medium, in an open or closed vessel, at normal or elevated temperature, e.g. at Temperatures between 50 and 120 °. Additions of solvents, such as alcohol, formamide, etc. can possibly promote the implementation. It is generally advisable to do so if possible equivalent amounts of the chromium-containing 1:! complex and the metal-free dye to be reacted with one another, with the molecular ratio between the metal-free dye and the l: l complex is expediently at least 0.85: 1 and at most 1: 0.85; an excess of metal-containing dye usually has less of a disadvantageous effect than such of metal-free dye. The closer this ratio is to 1: 1, the more advantageous the result in general.

The new chromium-containing mixed complexes obtainable by the above processes are suitable for dyeing and printing various fabrics, but especially for dyeing animal materials such as silk, wool and Leather, but also for dyeing and printing synthetic fibers made from super polyamides, super polyurethanes or polyacrylonitrile. They are especially suitable for dyeing neutral or weakly acidic, e.g. acetic acid baths. The so obtained

(^ aster ^ jj Colorings are even and have a good light ^ fWaich-, So white, milled, decatured and carbonized fastness. You can

9 09848/1139

in this regard the so-called post-chrome plating or single-bath chrome plating dyes replace and are compared to the latter by the much simpler and shorter dyeing process in Advantage.

A particular advantage of the present dyes is that they are very extensive by already using relatively small amounts of valuable dyestuff covered. Color shades ranging from brown to olive can be achieved.

In the following examples, unless otherwise stated, parts are percentages by weight Percentages by weight and temperatures are given in degrees Celsius.

909848/1 139

Example 1.

4j, 9 parts of the 1: 1 chromium complex of the dye from diazotized 5-nitro-l- * ämino-2-oxybenzene -3-sulfonic acid and 2-oxynaphthalene] and 34.2 parts of the dye from diazotized] 4-nitro-2-aminophenol and acetoacetic anilide are stirred in 2000 parts of hot water and the mixture obtained is neutralized. After adding 4.0 parts Sodium hydroxide and 6.2 parts of sodium acetate is used during Stirred at 95 to 98 for 6 hours. After the reaction has ended is filtered and the dye is separated from the filtrate by adding sodium chloride, filtered off and dried, It is a brown powder that dissolves in water yellow-brown, in conc. Sulfuric acid with a blue-green color dissolves and wool or leather from weakly acidic baths in yellow-brown Dyes shades of good fastness properties.

BATH

909848/1139

Example 2.

43.9 parts of ^{the 1:} 1 chromium complex of the dye from diazotized 3-nitro-1-amino-2-oxybenzene-5-sulfonic acid and 2-oxynaphthalene and 34.2 parts of the dye from diazotized 4-nitro-2-aminophenol and Acetoacetic acid amide are stirred in 2000 parts of hot water and the mixture - · _; 'then neutralized. After adding 4.0 parts of sodium hydroxide, the mixture is stirred at 95 to 98 for 24 hours. ; After the reaction has ended, the dye is separated out from the resulting solution by adding sodium chloride, filtered off and dried. It is a brown powder that looks in water with brown, in conc. Sulfuric acid in blue-green color and dissolves wool or leather from a weakly acid bath \ in brown shades of good fastness properties. '■ -

In the same way, in a molecular ratio ^: 1: 1, the chromium-free dyes mentioned in column I of the table below can either be mixed with the .lrl-chromium complex compound of the monoazo dye from diazotized 3-nitro-1-amino-2-oxybenzene-5- sulfonic acid and 2-oxynaphthalene or with the 1: 1 ~ chromium complex compound of the monoazo dye from diazotized 5-nitro-1-amino-2-oxybenzene-j5-sulfonic acid and 2-oxynaphthalene, resulting in 1: 2 chromium complexes, wool or Dye leather in the shades given in column II.

9098A8 / 1139

HIGH, \ /

oh σ

A-N = N-C-CO-NH

NO,

Cl

HIGH,

OH C II -N = N-C-CO-NH-CH,

NO,

HO CH, \ /

OH C Il

-N = N-C-CO-NH

NO,

OH

HO CH ₃

H ί = Ν — C-CO-NH

NO

(J

-9

II

Brown

brown brown

yellow-brown

909848/1 139

I. 2 909848/1139 II i HIGH,
V 3
OH C
Il 5. Il
AN = NC-CO-NHC CH ₂ ) J-OCH ₃ Brown NO ₂ HIGH-
\ / 3
OH C
H 6th AN = NC-CO-NH
J- ₆ brown purple nu uiu
OH C
Il 7th Il
AN = NC-CC-NH
NO ₂ KJ Brown HO CH ₃
OH C CH-CH
AN = NC-NH-CH y ^H 2 8th. NO ₂ Brown HO CH ₃
OH C CH,
IHP
AN = NC-CO-NH-CH 9i NO Brown

12th

13th

HO CH- \ /

OH C

N = N-C-CO-NH

NO,

HIGH

OH C

ι II,

A-N = N-C-CO-NH

Cl

HIGH- \ /

OH C

_r AJ

OH C

1 "

A-N = N-C-CC-NH

KJ 1 cl

Brown

reddish brown

reddish brown

reddish brown

9 0 9 B 4 8 y 1139

1

OH

HO CH "\ / C

= N-C-CO-NH

Cl

COOH

HN,

CO I CH

HO CH, \ / OH C

-N = N-C-CO-NH

t-ci

OH

Cl

HIGH, \ /

II I = N — C — CO — NH

NO,

H C

H, N = N-C-CO-NH

NO,

OCH,

909848 /

II

yellowish brown

yellowish brown yellowish brown

Brown

1139

BATH ORIGINAL

I. HO \ CH, A-OCH, OH σ II / 3 A-N = N Il
—C — CO — NH
Λ OH C -
i "
Λ) —N = N — C — CO — NH OCH CH-— C -CH- U 18th y HIGH- 3 j 3 Brown NO ₂ CH- 3 19th rotstichj

909848/1139

- 14 dyeing instructions for wool;

100 parts of woolen knitting yarn are introduced at 50 ° into a dyebath containing 2 parts of dye per 4000 parts of water and contains 4 parts of ammonium sulfate. The liquor is brought to the boil in the course of 45 minutes and during leave at this temperature for a further 45 minutes. Thereon the dyed material is removed, rinsed thoroughly with cold water and dried.

Coloring instructions for leather:

100 parts of clothing suede (dry weight) are drummed up at 50 ° C. in a solution of 1000 parts of water / water and 2 parts of 24 # ammonia for 2 hours and then at 60 ° C. in a solution of 1000 parts of water and 2 parts of 24 # ammonia and 6 parts of dye colored for 1 hour. A solution of 40 parts of water and 4 parts of 85 # strength formic acid is then added and dyeing is continued for a further 30 minutes. The leathers are then rinsed thoroughly and, if necessary, treated with 2 parts of a dicyandiamide-formaldehyde condensation product for 30 minutes at 50.degree.

Other suede and glove leather can be dyed in the same way.

9098 4 8/1139

Claims (12)

Claims. 1 / Process for the production of metal-containing azo dyes, which contain an atom of chromium bound to two molecules of different monoazo dyes in complex, characterized in that one of carboxylic acid groups and sulfonic acid groups free, metallizable monoazo dye of the formula OH
DN = NA, where D is the remainder of a position adjacent to the OH group. the Azpbrücke bound diazo component of the benzene series and A is the remainder of a position adjacent to the. enolized keto group Acetoacetic acid amides bound to the azo bridge mean, and a complex chromium compound, which has an atom Chromium complex on a molecule of the monoazo dye der ^Form OH HO. ., .- ■ -.... X — A — N = N- <~~> . wherein one X denotes a nitro group and the other X denotes a sulfonic acid group, contains bound, reacts with one another in a molecular ratio of about 1: 1. 909848/1139 2. The method according to claim 1, characterized in that that a metal-free monoazo dye from a diazotized nitroaminophenol and one of sulfur-containing substituents used free acetoacetic acid amide. 3. The method according to any one of claims 1 and 2, characterized characterized in that the starting material is a metal-free monoazo dye of the formula OH used, wherein X is a hydrogen or chlorine atom, a nitro or an acylamino group and A, a in ß-position denote the azo group bound.acetoacetic acid amide. 4. The method according to any one of claims 1 to 3 * thereby characterized in that the starting material is a metal-free monoazo dye, which is used as a coupling component "residue of a Acetoacetic anilide: contains, its benzene residue, if applicable is substituted, in particular by v Ghlqi? - ■ odej? Bromine atoms, Methyl, ethyl, "methoxy or ethoxy groups" are used. 5. The method according to one of claims 1> Ms 4, characterized in that the reaction is carried out in an aqueous medium, preferably at an elevated temperature, for example between 50 and 120 °. 909848/1139 BAD original 6. Metal compounds that bind an atom of chromium to two molecules of different monoazo dyes in a complex contain, one of which has the formula OH OH - χ wherein one X is a nitro group and the other X is a sulfonic acid group means, and the other of the formula OH D-N = N-A corresponds to where D is the radical of a diazo component of the bonded to the azo bridge adjacent to the OH group Benzene series and A the remainder of an acetoacetic acid amide bonded to the azo bridge adjacent to the enolized keto group mean. 7 · Complex chromium compounds according to claim 6, characterized in that indicated that the benzene azo dye of the formula * DN = NA ₂ corresponds to where D ₁ denotes an o-hydroxyphenyl radical which bears a nitro group and optionally a further substituent, and A _p denotes the radical of a coupling component of the acetoacetic anilide series. 8. Complex chromium compounds according to one of claims 6 and 7 *, characterized in that the acetoacetic acid amide dye of the formula 9 0 9 8 4 8/1139 HIGH,
\ / 3 OH C 1 " X-A-N = N-C-CO-NH- NO ₂ corresponds to where X is a hydrogen or chlorine atom, a nitro or an Acy.laminogruppe. 9. Complex chromium compounds according to one of the claims 6 and 7i characterized in that the benzene azo dye of the formula jjq CH \ / 3
OH C I « (Λ - TSi = N C — CO — NH- corresponds to where Y is a. Hydrogen or chlorine atom or a Means nitro group. 10. dyeing and printing process, characterized in that complex chromium compounds according to any one of claims ¹ 6 to 9 are used. 11. Dyeing process according to claim 10, characterized in that that you have nitrogen-containing fibers, especially wool, silk, leather or super polyamide or super polyurethane fibers with the complex chromium compounds in weakly alkaline, If neutral or weakly acidic bath colors. 12. According to one of the claims 10 and 11, colored or printed material. 909848/1 1 39