DE1109289B - Process for the preparation of dyes of the anthraquinone series - Google Patents

Description

It has been found that valuable, non-fume dyes can be used for dyeing textiles made from acetyl cellulose obtained when 1-nitroanthraquinone-2-carboxylic acids with low molecular weight monovalent esterified aliphatic alcohols and hl the resulting esters the nitro groups in per se known Way converted into methylamino groups.

According to a second embodiment of the process, the new dyes are obtained by that one l-methylaminoanthraquinone-2-carboxylic acids with low molecular weight monovalent aliphatic Esterified alcohols.

Low molecular weight monohydric aliphatic alcohols are preferably alcohols with 2 to 5 carbon atoms, for example ethanol, n-propanol, isopropanol, n-butanol, isobutanol and the amyl alcohols, called. It is advantageous to use mixtures of these alcohols for the esterification.

The esterification with low molecular weight monohydric aliphatic alcohols is carried out in itself known manner by, for example, by doing l-nitroanthraquinone-2-carboxylic acid or their derivatives, such as their acid chloride, goes out. l-nitroanthraquinone ^ -carboxylic acid chloride is expediently by reacting with an excess of the alcohol, which is also used as a solvent serves, esterified, or one works in an inert solvent such as benzene or toluene. 1-methylaminoanthraquinone-2-carboxylic acid esterified advantageously by treatment with the alcohols mentioned in the presence of esterification catalysts, for example concentrated sulfuric acid.

The conversion of the nitro group of the 1-nitroanthraquinone-2-carboxylic acid esters into the methylamino group is possible in a simple manner if methylamine is allowed to act on the nitro compounds, expediently in the presence of a solvent such as ethanol or benzene. The methylamine can be used in gaseous form, in liquid form or in the form of a solution. The temperature should be chosen so that no reaction of the esters with methylamine to form acid amides or decarboxylation or transesterification occurs. Therefore, converting the nitro group into the methylamino group at ordinary preferably to slightly elevated temperature and avoids exceeding the temperature of 8O ⁰ C.

The new dyes dye textiles, such as fibers, threads, flakes, woven and knitted fabrics, made of acetyl cellulose, e.g. B. 2 ^1/2 ~ acetate or triacetate, in bright pink tones of very good process for preparing
of dyes of the anthraquinone series

Applicant:

Aniline & Soda Factory in Baden

Corporation,

Ludwigshafen / Rhine

Dr. Karl Maier, Ludwigshafen / Rhine,
has been named as the inventor

_ao wet fastness properties and especially good exhaust gas fastness.

Textiles made from 2V2 acetate fibers are dyed as usual at about 75 to 80 ° C, advantageously with the addition of auxiliaries such as Marseille soap or the reaction product of 1 mole of oleylamine and 10 moles of ethylene oxide or the reaction product of 1 mole of castor oil and 35 to 40 moles of ethylene oxide . Textiles made from triacetate fibers are generally heated at 100 ^° C., if necessary in the presence of one or more of the aforementioned auxiliaries and advantageously with the addition of a so-called "carrier", ζ. B. diallyl phthalate, colored. The dyes are expediently used in finely divided form and advantageously in mixtures with one another.

The dyes can also be spun into the fibers.

Of those known from French patent specification 1,068,386, with glycols or polyglycols esterified dyes, the dyes according to the invention differ in their better wet fastness properties and of the fluoroalkyl ester groups known from U.S. Pat. No. 2,763,668 containing dyes due to the better lightfastness of the dyeings obtained.

The parts given in the examples are parts by weight.

example 1

The acid chloride from 446 parts of 1-nitrohraquinone-2-carboxylic acid is refluxed for 8 hours in 1200 parts of dehydrated toluene with 110 parts of n-propanol.

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110 parts of gaseous methylamine are then passed into the mixture at ordinary temperature and the reaction is completed by heating to 30 to 40 ^° C. for 1 to 2 hours. The excess methylamine is then removed by heating and the reaction mixture is concentrated to a small volume. The dye which separates out from it in the cold is filtered off with suction, washed with methanol and dried. 434 parts of the dye are obtained in the form of red crystals with a melting point of 115 to 116 ° C.

Is dyed with this dye 100 parts of tissue from 2 ^J / 2-acetate in 3000 parts of water containing 1 part of the dye, and 6 parts Marseiller contain soap, for 1 hour at 75 ° C, one obtains exhaust dyeings in pink shades of good Wet fastness properties.

Example 2

15 parts of l-nitroanthraquinone ^ -carboxylic acid chloride are esterified by refluxing in 80 parts of isopropanol for 14 hours. The ester is then converted by reaction with about 15 parts of methylamine (within of 14 hours and at room temperature) into the 1-methylamino derivative. 12 parts of the are obtained Dye in the form of red crystals with a melting point of 123 to 124 ° C.

Is dyed with this dye 100 parts of tissue from triacetate in 2000 parts of water containing 1.5 parts of the dye, 1 part of the reaction product of 1 mole of oleyl amine and 10 moles of ethylene oxide and 4 parts of diethyl phthalate, 2 hours at 100 ⁰ C, so one obtains dyeings in pink shades which are well-fume-proof and have very good wet fastness properties.

Example 3

20 parts of 1-methylaminoanthraquinone-2-carboxylic acid are in the presence of 8 parts of concentrated sulfuric acid for 15 hours with 100 parts Butanol heated to boiling under reflux cooling. The resulting red dye is now poured into it the reaction mixture separated in water and evaporation of the butanol and used for purification recrystallized from alcohol. The yield is 21 parts. The dye delivers on textile goods 2V2 acetate fiber, fume-proof pink dyeings with good wet fastness properties.

Example 4

The acid chloride obtained with the aid of thionyl chloride from 1000 parts of l-nitroanthraquinone-2-carboxylic acid in 3000 parts of toluene as a solvent is refluxed to about 90 for 8 hours after the excess thionyl chloride has been distilled off with a mixture of 120 parts of n-propanol and 180 parts of isobutanol ⁰ C heated. About 450 parts of the solvent mixture are then distilled off and then a solution of 185 parts of methylamine in 185 parts of methanol is stirred into the mixture in small portions. Then stir to complete the implementation. another 1/2 hour at normal temperature and 1/2 hour under boiling and reflux cooling. The reaction mixture is then concentrated to a small volume, the red dye which has separated out in crystallized form is filtered off with suction, washed with methanol and water and dried. The yield of the dye which melts at 86 to 88 ° C and sinters from 83 ° C is 996 parts.

This dye is used to dye 100 parts of 2V2 acetate fiber threads in 1000 parts of water, which 0.5 parts of the dye and 2 parts of the reaction product of 1 mole of castor oil and 40 moles of ethylene oxide contain, for 1 hour at 80 ° C, the result is smoke-resistant dyeings in pink tones very good fastness to light, water, perspiration, sea water and washing.

Example 5

That from 150 parts of l-nitroanthraquinone-2-carboxylic acid Acid chloride obtained in 500 parts of toluene with the aid of thionyl chloride is combined with

Heated 80 parts of n-butanol at approximately 106 ° C for 12 hours. Now cool the mixture Room temperature and carries a solution of 50 parts of methylamine in small portions with stirring in 50 parts of methanol. The reaction mixture is then left for 4½ hours at room temperature and stirred for 1 hour at the boiling point under reflux cooling. You get 151 parts of a red dye with a melting point

81 to 81.5 ° C, the textile material made of 2V2 acetate fibers in dyes exhaust-resistant, strong pink tones with good wet fastness properties.

Example 6

24 parts of 1-nitroanthraquinone-2-carboxylic acid chloride and 15 parts of η-amyl alcohol are refluxed in 110 parts of dry toluene for 14 hours cooked. After cooling, a solution of 20 parts of methylamine is stirred into the mixture in 20 parts of methanol and the reaction mixture is concentrated after stirring for 2 hours at room temperature until the dye crystallizes.

The yield is 22 parts of melting point 87-88 ⁰ C. At tissues from 2V2-acetate of the dye provides real exhaust pink dyeings of good wet fastness properties.

Claims (1)

PATENT CLAIM: Process for the preparation of dyes of the anthraquinone series, characterized in that 1-nitroanthraquinone-2-carboxylic acids are esterified with low molecular weight monohydric aliphatic alcohols and the nitro groups in the esters obtained are converted into methylamino groups in a manner known per se or that l-methylaminoanthraquinone-2- carboxylic acids esterified with low molecular weight monohydric aliphatic alcohols. Considered publications:
French patent specification No. 1068 386. A coloring table was displayed when the application was announced.