DE1010213B - Process for the preparation of monoazo dyes and their metal complex compounds - Google Patents

Description

GERMAN

The invention relates to a method for production of monoazo dyes and their metal complex compounds. The method consists in that 1 mole of the diazo compound from a 2-amino-1 -oxy- or methoxybenzene with 1 mole of a 1-oxyacylamino-7-oxynaphthalene the general composition

NH - C - χ - alkylene - OH

Il ο

HO

wherein χ denotes the single bond or - OCH ₂ -, preferably l-oxyacetylamino-7-oxynaphthalene, couples and treats the monoazo compound obtained in substance or on the fiber with a metal donor.

The new dyes have the general composition in the metal-free state

R-N = N NH-C-x -alkylene-OH

Method of manufacture

of monoazo dyes and their

Metal complex compounds

Applicant:
Sandoz A.-G., Basel (Switzerland)

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

Patent attorneys,
Frankfurt / M., Große Eschenheimer Str. 39-39 a

Claimed priority:
Switzerland from June 29, 1954

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

HO

wherein χ has the abovementioned meaning and R stands for a radical of the benzene series which bears a hydroxyl or methoxy group ortho to the azo group. To produce the diazo compound, for. B. 2-Amino-1 -oxybenzene, 2-Amino -1-oxy-halobenzenes, 2-Amino-l -oxy-nitrobenzenes, 2-Amino-1 -oxy-halogenitrobenzenes, 2-Amino-l-oxy-acylamino- halobenzenes, 2-amino-1-oxy-acylamino-nitrobenzenes, then the large series of 2-amino-1-oxybenzenesulfonic acid amides, their on the nitrogen atom of the sulfonic acid amide group by alkyl, haloalkyl, oxyalkyl, alkoxyalkyl, aralkyl, carbocyclic and heterocyclic radicals further substituted derivatives, 2-amino-1-oxy-alkylsulfonylbenzenes and the corresponding 2-amino-1-methoxy compounds. Special mention should be made of 2-amino-1-oxybenzene-4-sulfonic acid amide, 2-amino-1-oxybenzene-4-sulfonic acid methylamide, 2-amino-1-oxybenzene-4-sulfonic acid (2'-oxy) ethylamide, 2 -Amino-1-oxybenzene-4-sulfonic acid- (3'-methoxy) -propylamide, 2-amino-1-oxybenzene-4-sulfonic acid-benzylamide, 2-amino-1-oxybenzene-4-sulfonic acid-cyclohexylamide-1-amino-1-oxybenzoM -sulfonsäurephenylamid, which can be further substituted on the phenylamide residue by, for example, a ring-bonded carboxyl, acylamino, sulfonic acid amide, sulfonic acid methylamide and sulfonic acid dimethyl amide group, and also 2-amulol-oxy-4-methylsulfonylbenzene.

The most important 1-oxyacylamino-7-oxynaphthalmesindl-oxyacetylamino-7-oxynaphthalene according to the definition and l-carbo- (2'-oxy) ethoxy-amino-7-oxynaphthalene. They are made from the corresponding chloroacylamino compounds obtained by heating in formamide to a higher temperature.

The coupling of the diazotized 2-amino-1-oxy- or -methoxybenzenes with the 1-oxyacylamino-7-oxynaphthalenes according to the definition takes place advantageously in an alkaline medium; the products obtained are worked up and isolated in the customary manner.

With the metal-free monoazo dyes, wool can be treated using a post-metallization or single-bath metallization process dye in wash-, mill- and lightfast shades. Thereby, with chromium-releasing agents, blue-gray, gray to olive, with cobalt-releasing agents Medium obtained blue to gray tones.

The metal-free monoazo dyes are preferably converted into the metal complex compounds chromium and cobalt releasing agents into consideration. Such agents are, for example, the salts of chromium, z. B. Chromifluorid, Chromisulfat, Chromiformiat, Chromiacetat, Potassium or ammonium chromisulphate and sodium or potassium chromate or dichromate, and the Salts of cobalt, e.g. B. cobaltoacetate, cobalt formate and cobaltosulfate. The metallization is advantageous in aqueous slurry or solution or in an organic medium, for example in formamide or in the Melt of an alkali salt of a low molecular weight aliphatic monocarboxylic acid carried out. In the latter

709 548/406

In this case, insoluble heavy metal compounds can also be used, for example cobalt hydroxide and cobalt carbonate. Metallization in an aqueous, caustic alkaline medium is particularly advantageous, the Metal salts are added in the presence of such compounds, which chromium and cobalt in caustic alkaline Keep the medium loosened in a complex bond, e.g. B. tartaric acid, citric acid and lactic acid. Include the Monoazo dyes as a group to be metallized

1 molecule of monoazo compound interferes with less than 1 atom of metal. This creates the so-called 1: 2 complexes based on 2 molecules of monoazo compound contain approximately 1 atom of metal.

The metal-containing azo dyes obtained are, if appropriate after pouring in the organic metallizing solution in water, separated from an aqueous medium by adding sodium chloride, then filtered,

Water diazotized. The diazo suspension is combined at 0 to 5 ° with a solution of 22 parts of 1-oxyacetylamino-7-oxynaphthalene, 6 parts of sodium hydroxide, 20 parts of anhydrous sodium carbonate, 350 parts 5 water and 10 parts of a pyridine base mixture. The mass is stirred vigorously at 0 to 5 ° for a few hours. To At this time the coupling reaction is complete and the monoazo dye, which has almost completely separated out, becomes on known way isolated. It is in the dried state and an ortho-oxy-ortho'-methoxy-azo grouping, so when it is ground it becomes a dark purple powder, which the metallization with splitting of the methoxy group is carried out in water with violet sulfur and in concentrated sulfur. This is done by heating the dye acid which dissolves it with a burgundy red color. Its after that materials at a higher temperature in an organic medium, post-chrome plating processes or single-bath chrome plating, for example dyeings on wool produced in a glycol (e.g. ethyl glycol, butylation process) glycol, ethyl polyglycol). The metallization of the mono 15 gray and have very good washing, fulling and light azo compounds takes place in all cases in such a way that on authenticity.

The new azo component used to prepare the monoazo dye of the example can be prepared by heating l-chloroacetylamino-7-oxynapha thalin in formamide to 160 ° to 180 ° for several hours. A dyebath is prepared from 4000 parts of water, 1 part of the chromable dye obtainable according to Example 1, 1 part of potassium chromate, 7 parts of ammonium sulfate and 10 parts of Glauber's salt and is optionally washed at 40 ° and then dried. 25 100 parts of wool. Heat the bath to boil for 30 minutes and hold it for 90 minutes - wool; they dye this fiber already from neutral and
Silk and tussah silk from a weakly acid dye bath in blue-gray, gray to olive tones of very
good fastness to washing, fulling and light; they suit 30
also suitable for dyeing leather and in particular
exquisite way for dyeing artificial ones
nitrogen-containing fibers such as polyamide fibers. Your good
Solubility in polar solvents, e.g. B. acetone,

Dimethylformamide and tetrahydrofuran, allowed 35 7-oxynaphthalene to be combined. You get the im Furthermore, the new dyes for dyeing art- Example 1 described product very similar monoazo fibers to use the coloring agent from organic solutions.

can be used (e.g. acetate rayon, polyterephthal- l-Carbo- (2'-oxy) -ethoxy-amino-7-oxynaphthalene

acid ester fiber). obtained if you l-Carbo- (2'-chloro) -ethoxy-amino-

In many cases, metal chemical complexes outperform 7-oxynaphthalene after several hours of heating in molded compounds, which submits amide to 160 ° by metallizing mixtures, of two or more monoazo- according to the invention. .

dyes are obtained, the uniform metal example ό

complex compounds in the coloring properties. 43 parts of the monoazo color obtainable according to Example 1

The production of such mixed metal complex compounds are dissolved in 1500 parts of water. One relocates fertilize another subject of the present the solution with 16 parts of sodium dichromate and boils Patent. place them on the reflux condenser until the complex

Compared to the US patent 2 602 080 education, which takes several hours. The known cobalt-containing monoazo dyes are characterized by deposited, filtered and dried chromium-containing cobalt complex compounds of the invention , while the cobalt-containing monoazo dyes
of the patent mentioned only from acetic acid
Bath has good absorption properties on polyamide fibers 55
own. Compared to that from the German patent specification
844 032 known metallizable monoazo dyes
the new monoazo dyes are characterized by
that they have a significantly better absorption capacity on wool
than the known coloring agents show when they are boiled for 60 60 minutes. After a short cooling period, the staining process is carried out using the single-bath chromium plating process. the dyed wool taken out of the bath, with

The following examples illustrate the invention. The parts mean parts by weight that Percentages by weight.

65 Example 1

boiling. The dyed wool is then taken out of the bath, rinsed with water and finally dried.

Example 2

21.6 parts of 2-amino-1-oxybenzene-4-sulfonic acid ethylamide are prepared as described in the previous example with 25 parts of l-carbo- (2'-oxy) -ethoxy-amino-

with red paint dissolves. It dyes wool, silk and synthetic polyamide fibers in blue-gray tones of excellent quality Wash, mill and lightfastness.

In a dye bath consisting of 1 part of the chromium-containing azo dye obtainable according to Example 3, 4000 parts of water and 5 parts of ammonium sulfate, one goes at 40 ° with 100 parts of wool. You heat that Bath to boil within 30 minutes and hold it

Rinsed with water and dried.

Synthetic polyamide fibers are dyed in the same way as silk at a slightly lower temperature, e.g. B. at 95 °.

Example 4

20.2 parts of 2-amino-1-oxybenzene-4-sulfonic acid methyl- 21.5 parts of the according to the information in Example 1 and 23.7

amide in a mixture of 20 parts of 30 ° / ₀ parts of the hydrochloric acid obtainable according to the details of Example 2 and 100 parts of water at 0 to 5 ° with a monoazo dye are in 1000 parts of water at 90 ° solution of 6.9 parts of sodium nitrite and 30 parts of 7 ° dissolved with the aid of 6 parts of sodium hydroxide. Man

1 01Ö 213

then puts the dye solution in a solution of 24 parts of sodium dichromate and 4 parts of sodium hydroxide 100 parts of water and then 80 parts of a 20% strength aqueous glucose solution. Well holds the temperature of the metallization solution to 90 to 95 ° until the complex formation is complete, isolates the chromium-containing azo dye and dries it. It dyes wool, silk and synthetic polyamide fibers in blue-gray tones with excellent wash, wash and lightfastness.

Example 5

44.4 parts of the according to the details of Example 1 by coupling 21.6 parts of 2-amino-1-methoxybenzene-4-sulfonic acid methylamide with 22 parts of 1-oxyacetylamino-7-oxynaphthalene available monoazo dye are dissolved in 400 parts of ethyl glycol. One sets the Solution to 50 parts of potassium chromisulfate and then heated to 140 ° until the complex formation is complete. The metallization mass is poured into 1200 parts of water, the chromium-containing azo dye is salted out and nitrided and dries it. It is identical to the product obtainable according to Example 3.

Example 6

43 parts of the monoazo dye obtainable as described in Example 1 are dissolved in 800 parts of warm water. The solution was treated with a mixture of 28.2 parts Kobaltosulfat, 7.6 parts tartaric acid, 35 parts of 30 ° / ₀ sodium hydroxide solution and 350 parts of water. The complex formation occurs instantaneously. The cobalt-containing azo dye is deposited, filtered off and dried. It dyes wool, silk and synthetic polyamide fibers in reddish gray tones with very good fastness properties.

Example 7

ίο Man 21.5 parts of the monoazo dye obtained according to Example 1 and 23.7 parts of the monoazo dye triggers available according to Example 2 at about 90 ° in 1000 parts of water with hooves of 30 parts of 30 ° / ₀ sodium hydroxide solution. 80 parts of hot aqueous 20% cobalt sulphate solution are added to the solution. When the complex formation is complete, the cobalt-containing azo dye is separated off, filtered off and dried. It dyes wool, silk and synthetic polyamide fibers in blue-gray tones with excellent wash, milled and lightfastness.

The following table 1 contains further metal-containing azo dyes, which according to one of the preceding Examples can be made. To identify them are in column (A) those for the production of 2-Amino-1-oxy- or -methoxybenzenes serving diazo compounds, in column (B) the 1-oxyacylamino-7-oxynaphthalenes and in columns (C) and (D) the shades of the dyeings with the chromium-containing or cobalt-containing azo dyes on wool.

Tabel

at
game
No. (A) (B) (C) (D) Gray the same Gray the same Gray blue the same 8th 2-amino-1-oxy-4-methylsulfonylbenzene l-oxyacetylamino-7-oxynaphthalene Blue-gray Violet gray blue Gray 9 2-Amino-1-oxybenzene-5-sulfonic acid amide the same the same the same Reddish gray 10 2-amino-1-oxybenzene-4-sulfonic acid the same the same the same the same (2'-oxy) ethylamide 11 2-amino-1-oxybenzene-4-sulfonic acid the same the same the same (3'-methoxy) propylamide 12th 2-amino-1-oxy-4-chloro-5-nitrobenzene the same the same Blue-gray 13th 2-amino-1-oxybenzene-4-sulfonic acid the same the same Reddish gray (3'-N-methylsulfaminyl) phenylamide 14th 2-amino-1-oxybenzene-4-sulfonic acid the same the same the same (3'-sulfaminyl) phenylamide 15th 2-amino-1-oxybenzene-4-sulfonic acid the same the same the same (3'-acetylamino) phenylamide 16 2-amino-1-oxy-4-chlorobenzene the same the same 17th 2-amino-1-oxy-5-nitrobenzene the same the same 18th 2-amino-1-oxy-4-chloro-6-nitrobenzene the same the same 19th 2-amino-1-oxy-4-nitrobenzene the same Olive gray 20th 2-amino-1-oxybenzene-4-sulfonic acid 1 -Carbo- (2'-oxy) -ethoxyamino- Blue-gray (2'-methoxy) ethylamide 7-oxynaphthalene 21 2-amino-l-oxy-4-nitro-6-acetylamino- l-Carbo- (2'-oxy) -ethoxyamino- OUv benzene 7-oxynaphthalene 22nd 2-Amino-1-oxybenzene-4-sulfonic acid amide the same Blue-gray 23 2-amino-1-oxybenzene-4-sulfonic acid the same the same (2'-N, N-dimethylsulfaminyl) -phenyl- 24 2-amino-1-oxy-5-nitrobenzene the same the same 25th 2-amino-1-oxybenzene-4-sulfonic acid the same the same (l'-ethyl-2'-oxy) -ethylamide 26th 2-amino-1-oxybenzene-4-sulfonic acid the same the same (4'-N-methylsulfaminyl) phenylamide

7th (B) 8th (C) P) at l-Oxyacetylamino-7-oxynaphthaUn Blue-gray Reddish gray game
No. (A) 27 2-amino-1-oxybenzene-4-sulfonic acid the same the same the same (2'-oxy) propylamide 28 2-amino-1-oxybenzene-4-sulfonic acid the same the same the same di - [(2'-oxy) propyl] amide 29 2-amino-1-oxybenzene-5-sulfonic acid the same the same the same morpholide 30th 2-amino-1-oxybenzene-4-sulfonic acid the same the same the same ethylamide 31 2-amino-1-oxybenzene-4-sulfonic acid the same the same the same diethylamide 32 2-amino-1-oxybenzene-4-sulfonic acid the same the same the same pyrrolidide the same the same the same 33 2-amino-1-oxy-4-methyl-6-acetylbenzene 34 2-amino-1-oxybenzene-4-sulfonic acid the same the same the same cyclohexylamide 35 2-amino-1-oxybenzene-4-sulfonic acid 1- (2'-Oxy) propionylamino-7-oxy ~ the same the same benzylamide naphthalene 36 2-amino-1-oxybenzene-4-sulfonic acid l- (3'-oxy) -buturylamiho-7-oxy- the same the same (2'-oxy) ethylamide naphthalene 37 2-Ajmmo-l-oxybenzene-4-sulfonic acid l-Carbo- (3'-oxy) -propoxy-amino- the same the same (2'-methoxy) ethylamide 7-oxynaphthaUn 38 2-amino-1-oxybenzene-4-sulfonic acid l-carbo- (4'-oxy) -butoxy-amino- the same the same (3'-methoxy) propylamide 7-oxynaphthalene 39 2-amino-1-oxybenzene-4-sulfonic acid (2'-oxy) propylamide

Table 2 contains mixed metal complex compounds of two monoazo dyes, such as, for example, according to the information of Example 4 can be obtained. The metal complex compounds are marked by the content of metal-free monoazo dyes, which are reacted with 1 atom of metal;

they contain about 2 moles of the mixture of the two monoazo compounds per atom of metal. The column (E) gives the metal used to metallize the mixtures and the column (F) the color tones with the new metal-containing azo dyes on wool achieved dyeings again.

Tabel

First metal-free Mole according to the example Second metal-free Mole according to the example (E) (F) example
- \ t_ Monoazo dye 1 1 Monoazo dye 1 8th 1ΝΓ, 1 1 1 . 10 Cr Blue-gray 40 1 1 1 11 Cr the same 41 1.5 1 0.5 11 Cr the same 42 1 2 1 11 Cr the same 43 1 2 1 22nd Cr the same 44 1 10 1 11 Cr the same 45 1.5 11 0.5 15th Cr the same 46 1.5 11 0.5 16 Cr the same 47 1 2 1 22nd Cr the same 48 1 9 1 10 Co Reddish gray 49 1 10 1 20th Co the same 50 1 10 1 22nd Co the same 51 Co the same 52

Claims (3)

Patent claims: 1. Process for the production of monoazo dyes and their metal complex compounds, there- characterized in that 1 mol of the diazo compound is obtained from a 2-amino-1-oxy- or -methoxybenzene with 1 mole of an l-oxyacylamino-7-oxy- naphthalene of general composition
NH - C - χ - alkylene - OH HO wherein χ denotes the single bond or —OCH ₂ -, preferably l-oxyacetylamino-7-oxynaphthalene, couples and treats the monoazo compound obtained in substance or on the fiber with a metal donor. 2. Modification of the method according to claim 1, characterized in that one for the production of azo dyes metallized in substance from a mixture of two or more metal-free Monoazo compounds of the composition specified in claim 1 starts out. 3. The method according to claim 1 and 2, characterized in that there is used as the metal donating agent a chromium or cobalt releasing agent is used. Considered publications:
German Patent No. 844 032;
U.S. Patent No. 2,602,080. © 7109 548/406 6.57