CH312963A - Process for the production of azo dyes - Google Patents

Description

  

  <B> Process </B> for the production <B> of </B> azo dyes It has been found that new valuable azo dyes are obtained if 1 mole of the diazo compound is converted from one in the ortho position to the amino group to a metal component - group that enables complex formation, preferably an oxy or a carboxy group,

      bearing aminobenzene with 1 mole of a sulfone of 1-acetylamino-7-oxynaphthalene of the composition
EMI0001.0019
    where RR is alkyl, cyeloalkyl, aralkyl or aryl, couples and treats the monoazo compound obtained with a metal donor, preferably chromium or cobalt donor.



  The coupling of the diazotized, in the ortho position to the amino group, a group capable of forming a metal complex, preferably an oxy or a carboxy group, carrying aminobenzenes with the 1-sulfonyl aeetylamino-7-oxynaphthalenes is carried out preferably in an alkaline medium.

   As aminobenzenes which carry a group capable of forming metal complexes, preferably an oxy or a carboxy group, in the ortho position to the amino group, z.

   B. 1-oxy-2-amino-4-methylsulfonylbenzene, 1-oxy-2-aminobenzene-4- or -5-sulfonic acid amide, 1-oxy-2-amino-6-chlorobenzene or -methylbenzene or - nitrobenzene-4-sulfonic acid amide, 1-oxy-2-amino-4-chlorobenzene or methylbenzene or nitrobenzene-5- or

       -6-sulfonic acid amide and its on the nitrogen atom of the sulfonic acid amide group by alkyl, cycloalkyl, aralkyl, aryl undl or acyl mono- or disubstituted from, then 1-oxy-2-amino-4-nitrobenzene and its halogenated in the 6-position, alkylated - th and acylaminated representatives.

   Of the latter compounds, 1-oxy-2-amino-4-nitro-6-formylamino or acetylamino or propionylamino or buturylaminobenzene, also 1-oxy-2, may be mentioned in particular - amino - 4-nitro - 6 - carbomethoxyamino or carbopropoxyamino or

       -carbobutoxy-aminobenzene and 1-oxy-2-amino-4-nitro-6-carbäthoxyaminobenzene, whose ethoxy radical is in the 2'-position, for example through the methoxy, ethoxy, butoxy or (2 "ethoxy) ethoxy group can be substituted.

   Other interesting ortho-oxy- or carboxyaminobenzenes are 1- oxy-2-amino-5-nitrobenzene and its derivatives halogenated and alkylated in the 4-position, then 1-oxy-2-amino-6-chlorobenzene or- 6-methylbenzene or -6-nitrobenzene-4-sulphonic acid, 1-oxy-2-amino-4-chlorobenzene or -4-nitrobenzene or

       -4-phenylbenzene-6-sulfonic acid, 2-aminobenzene-1-carboxylic acid, 2-amino-5-methylsulfonylbenzene-1-carboxylic acid and finally 1-carboxy-2-aminobenzene-4- or -5-sulfonic acid amide and its on the nitrogen atom of the sulfonic acid amide group alkylated, cycloalkylated, aralkylated, arylated and (or aylated derivatives.



  Of the 1-sulfonylacetylamino-7-oxynaph- t.halines, which are used as azo components to build up the monoazo compounds, methyl sulfone, ethyl sulfone, cyclohexyl sulfone, benzyl sulfone and phenyl sulfone and its am are mentioned above all Phenyl radical substituted from derivatives.

   They can be obtained, for example, by heating equimolecular amounts of 1-haloacetylamino-7-oxynaphthalene and corresponding sulfinic acids, such as methane, ethane, cyclohexane, phenyl methane or benzenesulfinic acid and their derivatives substituted on the benzene ring, in neutral to slightly alkaline medium.

      The metal-free monoazo dyes dye wool and synthetic polyamide fibers such as nylon and perlon (3-brand product) as well as leather. After treatment with metal-releasing agents, especially with chromium- or cobalt-releasing agents, the colorations become light-, wash- and millfast. Some dyes are also suitable for the built-in metallization process.



  According to the invention, the new products are metallized in substance, the metallization preferably with salts of chromium, such as. B. Chromifluorid, Chromisulfat, Chromiformiat, Chromiacetat, Kaliumchromisulfat and sodium or potassium Ehromat or bichromate, and with salts of cobalt, like z.

   B. cobalt acetate, cobalt formate and cobalt sulphate, in aqueous slurry or solution or in an organic medium, for example in the melt of an alkali salt of a low molecular weight aliphatic monocarboxylic acid.

   In the latter case, insoluble heavy metal compounds can also be used, for example chromium or cobalt hydroxide and cobalt carbonate. The metal-containing dyes obtained are advantageously deposited from an alkaline medium, then filtered and dried.

      Some of the metal-containing dyes have a high neutral drawability on wool; They dye olls from neutral and silk from a weakly acidic dye bath in very level, full shades of excellent lightfastness and very good mill and washfastness; They are also suitable for dyeing synthetic nitrogen-containing fibers, such as polyamide fibers (e.g. nylon, perlon), and leather.



  The following examples illustrate the invention. The parts are parts by weight, the percentages are percentages by weight, and the temperatures are given in degrees Celsius.



       Example <I> 1 </I> 20.2 parts of 1-oxy-2-aminobenzene-4-sulfonic acid methylamide are dissolved in a mixture of 20 parts of 30% strength hydrochloric acid and 80 parts of water and at 0 with.

   a solution of 6.9 parts of sodium nitrite in 40 parts of what water diazotized. The diazo solution is added to an ice-cold solution prepared from 36 parts of 1- (4'-i # ethyl) -phenylsulfonyl-acet y 1 amino-7-oxynaphthalene, 8 parts of sodium hydroxide, 22 parts of sodium carbonate and .100 parts of water Solution and stir the mass until the coupling ends at 0-5,

   it is possible to add 10 percent by volume of pyridine to the coupling mixture to accelerate the latter. The monoazo dye, isolated and dried in a known manner, is dissolved in 100 parts of formamide to convert it into its chromium complex compound. After adding 50 parts of potassium ehromisulfate, the solution is heated to 100-110 for 4 hours, the chromium complex formed is isolated, converted into the sodium salt and dried.

   It is a dark powder that dissolves in water. blue, dissolves in concentrated sulfuric acid with red color and dyes wool, silk and synthetic polyamide fibers from neutral or slightly acidic baths in gray shades of excellent light, wash and milled fastness.



  The new azo component used to prepare the monoazo dye of the example has a melting point of 196-198. They are obtained by boiling equimolar amounts of 1-chloroacetylamino-7-oxynaphth.haline and 4-methylbenzene-1-sulfinic acid in a neutral to weakly alkaline oil. Example <I> 2 </I> 18,

  7 parts of 1-oxy-2-amino-4-methylsulfonyl-benzene are diazotized in a mixture of 20 parts of 30% strength hydrochloric acid and 100 parts of water at 0-5 with a solution of 6.9 parts of sodium nitrite and 30 parts of water. The diazo suspension is combined at 0-5 with a solution of 30 parts of 1-ethylsulphonylaeetylamino-7-oxynaphtha \ lin, 8 parts of sodium hydroxide, 22 parts of sodium carbonate, 25 parts of a pyridine base mixture and 400 parts of water;

   the monoazo dye formed is isolated in a known manner.



  The monoazo dye is converted into its chromium complex compound in a neutral solution with 16 parts of sodium bichromate and heated to about 95 until the complex formation is complete.

   The metal-containing azo dye deposited and dried in a known manner is a dark powder, which dissolves in water with blue color, in concentrated sulfuric acid with red color and wool, silk and synthetic polyamide fibers in blue-gray shades of excellent light, wash and milled fastness colors.



  The new azo component used in this example is obtained by boiling equimolecular amounts of 1-chloroacetylamino-7-oxynaphthalene and ethylsulfinic acid in neutral to weakly alkaline aqueous medium. <I> Example 3 </I> 15.4 parts of 1-oxy- 2-aminobenzene-4-sulfonic acid (2'-carboxy)

          -phenylamide are indirectly diazotized in the usual way and combined at 0-5 in the presence of excess sodium carbonate with a solution of 18 parts of 1-benzylsulfonylacetylamino - 7-oxynaphthalene, 4 parts of sodium hydroxide, 10 parts of pyridine and 200 parts of water. The isolated dye is a dark powder which dissolves in water with a blue color and in concentrated sulfuric acid with a red color.

   It dyes wool according to the single-bath chrome-plating process or according to the post-chrome plating process in beautiful gray tones that have excellent fastness properties.



  The dye is metallized in bulk by one of the chromizing processes described in Examples 1 and 2; the chromium complex compound dyes wool, silk and synthetic polyamide fibers in real gray tones.



  To convert it to the cobalt complex compound, the monoazo dye is dissolved in 300 parts of warm water. The solution is mixed with a mixture of 14.1 parts of cobalt sulfate, 3.8 parts of tartaric acid, 17.5 parts of 30% sodium hydroxide solution and 175 parts of water. The dye complex formation occurs instantaneously.

   The cobalt-containing azo dye dyes wool, silk and synthetic polyamide fibers with reddish gray tones with very good fastness properties.



  The new azo component used in this example is prepared by the method described in Example 1 from 1-chloroacetylamino-7-oxynaphthalene and benzylsulfinic acid.



  <I> Example 4 </I> 11.7 parts of 1-oxy-2-aniino-4-nitrobenzene-6-sulfonic acid are diazotized in a known manner and added in the manner described in Example 1 with 18 parts of 1- (4 '-Methyl) -phenylsulfonyla.cetylamino-7-oxynaphthalene coupled. The new dye dissolves in water with a violet color, in concentrated sulfuric acid with a red color and colors wool in real olive tones using the bath chrome plating process or the post-chrome plating process. Valuable color tones are also obtained if the dyeing on wool is treated with a cobalt-releasing agent.



  To convert the compound into the chromium complex, 30 parts of the monoazo dye described above are dissolved in 200 parts of formamide. This solution is heated to 100-120 for 4 hours after the addition of 20 parts of potassium chromisulfate. Here you salt out the chromium complex compound, filter it off and dry it. It dyes wool, silk and synthetic polyamide fibers from an acid bath in very real olive tones.



  The cobalt complex compound is prepared in the following manner: The solution of 30 parts of the non-metallized monoazo dye described above in 300 parts of 80 hot water is mixed with a mixture of 14.1 parts of cobalt sulphate, 3.8 parts of tartaric acid, 17.5 parts 30% sodium hydroxide solution and 175 parts of water. The cobalt complex dye forms immediately. After a short time, Fr is salted out, filtered off and dried. tr dyes wool, silk and synthetic polyamide fibers in real olive-gray tones.



  Further azo dyes are described in the table below. They are produced according to the instructions in Examples 1-4 and are characterized by diazo and azo components and by the solution color in concentrated sulfuric acid and the hues of the chromed wool dye, the chromium complex compound on wool and the cobalt complex compound on wool.
EMI0005.0001


 

Claims (1)

PATENT CLAIMS I. A process for the preparation of azo dyes, characterized in that 1 mol of the diazo compound from a group ortho to the amino group capable of forming a metal complex carries the aminobenzene with 1 mol of a sulfone of 1-acetylamino-7-hydroxynaphthalene the composition EMI0006.0012 where R is alkyl, cyeloalkyl, Aralkyl or aryl, couples and treats the resulting monoazo compound with a metal donor. II. Use of the metallized monoazo dyes prepared according to patent claim I for dyeing leather. SUBCLAIMS 1. Process according to patent claim I, characterized in that the group which is in the ortho position to the amino group of aminobenzene and which is capable of forming metal complexes is an oxy group. 2. The method according to claim I, characterized in that the ortho-position to the amino group of aminobenzene and capable of forming metal complexes is a carboxy group. 3. Process according to patent claim I, characterized in that the monoazo compound obtained is treated with a chromium-releasing agent. 4. The method according to claim I, characterized in that the monoazo compound obtained is treated with a cobalt-releasing agent.