DE1117244B - Process for the preparation of acidic anthraquinone dyes - Google Patents

Description

It has been found that valuable acidic anthraquinone dyes are obtained when 1-amino-4-haloanthraquinone-2-sulf onic acids or their salts with isocamphanylmethylamine.

Isocamphanylmethylamine is made from camphene by hydrogenation of the aldehyde, which is known per se Way with the help of the so-called "oxo reaction" by the action of carbon monoxide on camphene in Presence of cobalt or cobalt compounds is obtained in the presence of ammonia. The boiling point of isocamphanylmethylamine is 121 to 123 ° C / 20 mm.

The production of the new dyes by conversion is of particular technical interest of isocamphanylmethylamine with l-amino-4-halogenanthraquinone-2-sulfonic acids, z. B. the 1-amino-4-chloro- or preferably -4-bromoanthraquinone-2-sulfonic acid or their salts. It is advantageous to use water-soluble salts, for example the Alkali metal salts, such as the sodium or potassium salts of these sulfonic acids. Man leads the implementation expediently in the presence of hydrogen halide binding agents, e.g. B. of sodium or Potassium carbonate, sodium bicarbonate, sodium acetate or secondary sodium phosphate and in Presence of copper or copper compounds, ζ. B. of copper salts, such as copper sulfate, copper chloride or copper acetate, in aqueous, aqueous-alcoholic or alcoholic liquid, if appropriate in the presence of dispersants, for example the sodium salt of the condensation product from / 3-naphthalenesulfonic acid and formaldehyde. In particular, low molecular weight alcohols, such as methanol or ethanol, are used as alcohols Consideration.

The reaction takes place at a moderately elevated temperature. The reaction is therefore carried out at from 60 to 100 ^° C., preferably from 70 to 100 ^° C. In most cases, the reaction is complete within 8 to 24 hours. When using the 1-amino-4-bromoanthraquinone-2-sulfonic acids or their water-soluble salts, a reaction time of 6 to 16 hours is generally sufficient.

It is expedient to start from stoichiometric amounts of the reaction participants. However, it is advantageous to 1 mole of the l-amino-4-halogenanthraquinone-2-sulfonic acids or their salts use 1.2 to 2 moles of isocamphanylmethylamine. However, a larger excess of isocamphanylmethylamine is not harmful.

The new dyes come in various forms, for example as alkali metal salts, such as as sodium method of manufacture
of acidic anthraquinone dyes

Applicant:

Aniline & Soda Factory in Baden

Corporation,

Ludwigshafen / Rhine

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

or potassium salts, as amine salts, such as hexamethylene diamine salts, or as free acids, optionally

so in a finely divided state, advantageously from neutral or weakly acidic bath, are colored, deliver on structures, e.g. B. foils, films, and textiles, such as Threads, fibers, flakes, woven and knitted fabrics of all kinds, blue dyeings. Of special The new dyes for dyeing textiles made from linear polyamides, such as Polycaprolactam, polycapryllactam, polyhexamethylene diamine adipate or polycondensed Ω-aminoundecylic acid, whose strong and even reddish-blue colorations are extraordinarily bright color and very good wet fastness properties. Textile goods made from wool color the dyes obtainable according to the invention also in bright blue shades.

The dyes obtainable according to the invention stand out from that of Example 1 of the German Patent 456 114 known, by reacting l-amino-4-bromoanthraquinone-2-sulfonic acid with Hexahydroaniline dye available through the

better color fastness, seawater fastness,

Perspiration fastness, boiling fastness, washing fastness and water fastness of their dyeings on polycaprolactam the end.

The parts given in the examples are parts by weight.

example 1

47 parts of the sodium salt of l-amino-4-bromoanthraquinone-2-sulfonic acid and 19 parts of isocamphanylmethylamine are added to 400 parts of water along with 12 parts of anhydrous potassium carbonate and 1 part copper (I) chloride for 14 hours

109 739/348

75 to 80 ⁰ C heated with stirring. The reaction mixture is then filtered off with suction while it is cold and washed extensively, first with cold and then with hot water. For further purification, the dye is boiled with weakly alkaline sodium carbonate and then with water that has been weakly acidified with a mineral acid. 37 parts of a blue dye are obtained which dyes fabrics made of linear polycaprolactam in bright blue, strong shades with very good fastness properties.

The isocamphanylmethylamine used in paragraph 1 can be prepared as follows: A mixture of equal parts of carbon dioxide and hydrogen is introduced into a mixture of 2750 parts of camphene and 150 parts of Raney cobalt in a pressure vessel at 130 ° C. under a pressure of 150 atmospheres until gas is constantly absorbed . The Umsetzungsgut will now be distilled and separated the mm under a pressure of 1.5 mercury at 75 to 8O ⁰ C for continuous aldehyde.

300 parts of the aldehyde thus obtained are dissolved in 100 parts of methanol together with 10 parts of Raney cobalt and 140 parts of liquid ammonia under a pressure of 200 atmospheres hydrogen in one Pressure vessel heated to 120 ° C. Fractional distillation of the reaction material gives in 72% yield isocamphanylmethylamine with a boiling point of 112 to 115 ° C at 15 mm of mercury or with a boiling point of 121 to 123 ° C at 20 mm of mercury. The isocamphanylmethylamine obtained is characterized by the amine number 333.

Example 2

A mixture of 47 parts of the sodium salt of l-amino-4-bromoanthraquinone-2-sulfonic acid and 19 parts of isocamphanylmethylamine is in a mixture of 300 parts of water and 100 parts of methanol together with 12 parts of anhydrous sodium carbonate and 1 part of copper (I) chloride Stirred for 14 hours at 75 to 80 ° C. The reaction mixture is worked up as indicated in Example 1 and 40 parts of the dye are obtained, which melts ^{at 213 to 215 ° C. after recrystallization from methanol.}

Example 3

A mixture of 47 parts of the sodium salt of 1-amino-4-bromoanthraquinone-2-sulf heated oic acid and 19 parts Isocamphanylmethylamin is in 500 parts of water together with 10 parts of anhydrous sodium carbonate and 1 part of copper sulfate for 14 hours at 75 to 8O ⁰ C and worked up as indicated in Example 1. The yield is 37 parts of dye.

Example 4

50 parts of the potassium salt of l-amino-4-bromoanthraquinone-2-sulfonic acid and 20 parts of isocamphanylmethylamine are in a mixture of 400 parts of water and 150 parts of methanol together with 12 parts of potassium carbonate, 1 part of copper (I) chloride, 0.5 parts of copper powder and 5 parts of diisobutylnaphthalene-oc-sulfonic acid Sodium heated to 80 ° C for 15 hours. The reaction material is worked up as indicated in Example 1. You get 39 parts of the dye.

Claims (1)

PATENT CLAIM: Process for the preparation of acidic anthraquinone dyes, characterized in that 1-amino ^ -halogenanthraquinone ^ -sulfonic acids or their salts are reacted with isocamphanylmethylamine. Considered publications:
German patent specifications No. 456 114, 483 155. A coloring table was displayed when the application was announced. 109 739/348 11.61