DE723822C - Process for the preparation of N-substituted offsets of 1,4-diaminoanthraquinones - Google Patents

Description

A process for preparing N-substituted derivatives of 1, 4-diaminoanthraquinones additional patent 722 59.3 722 593 By the patent protected a process for preparing N-substituted derivatives of i, 4-diaminoanthraquinones, hei which one of leuco i , 4-diaminoanthraquinones with mixtures of different primary amines with. converts aliphatically bonded amino group. This process can be used to prepare 1,4-diaminoanthraquinones with residues of the same or different types in the amino groups.

It has now been found that N-substituted descendants of i, 4-diaminoanthraquinones can also be obtained if one leuco-i-aminoanthraquinone, which have an oxy or methoxy group in the 4-position, or their descendants, z. B. those that still have any atoms or in the other benzene nucleus of the anthraquinone Atomic groups, such as amino or oxy groups, may contain, with mixtures of different types primary amines with an aliphatically bonded amino group.

The implementation conditions generally correspond to those in the main patent described. Here, too, the end products are obtained in excellent and very high yields good purity. They are also for the most diverse ones mentioned in the main patent technical purposes can be used with advantage; in particular, they are characterized by excellent absorption on acetate silk and special clarity and authenticity of the colorations.

Compared to the well-known 1,4-diaminoanthraquinones, which are in a Amino group instead of a hydrogen atom an alkyl or oxalkyl radical and in the other amino group instead of a hydrogen atom contain an aryl radical the dyes obtainable by the present process, in which the Nitrogen of the two amino groups on an aliphatically bonded carbon atom is located, a much better absorption capacity on acetate silk and: a considerably better solubility in hydrocarbons. Example i A mixture is heated of 24.2 parts of leuco-i-amino-4-oxyanthraquinone, 15 parts of a 25 percent aqueous Methylamine solution, 8 parts of n-butylamine and 250 parts of methanol with stirring for 7 hours long to 6o to 7o °. Then one part of copper acetate and 4 parts of piperidine are added and directs air through the boiling mixture for so long until dye formation is finished. After cooling, the resulting i-methylamino-4-n-butylaminoanthraquinone is filtered ab: washes it with methanol and dries it. It forms blue needles, the acetate silk Color in strong blue tones.

Similar dyes are obtained by using mixtures of other aliphatic Amines used, e.g. B. methylamine -j- ethylamine, methylamine - propylamine, ethylamine -f- propylamine, methylamine monooxyethylene diamine or methylamine -; - "-Dimethylaminopropylamine.

Example 2 A mixture of 25.6 parts of leuco-i-amino-4-methoxyanthraquinone is heated, 15 parts of a 25 percent methylamine solution, 7.2 parts of ethanolamine and zoo Divide isobutylal.kohol with stirring to 6o to 7o "until there is no starting material is more detectable. Then 0.6 parts of copper acetate and 6 parts of piperidine are added and passes oxygen through the boiling mixture until the dye is formed. The resulting i-methylamino-4-oxäthylaminoanthraquinone was filtered it is then washed off with methanol and dried. It is a blue powder the acetate silk dyes in strong blue tones.

Instead of methylamine you can also Ä thylamin, Propylamiii, butylamine, i, 2-propanolamine or butanolamine and instead of ethanolamine 1, 3-propanolamine use, taking dyes with similar. Properties. Example 3 A mixture of 24.2 parts of leuco-amino-4-oxyanthraquinone, - 15 parts of a 25 percent aqueous methylamine solution, 11.8 parts of benzylamine and zoo parts of isobutyl alcohol the mixture is heated to 6o to 7o 'while stirring until no more starting material can be detected is. After adding 12.5 parts of nitrobenzene, the mixture is boiled until dye formation has ended. The i-methylamino-4-benzylaminoanthraquinone thus formed is then filtered off wash it off with methanol and dry it. It is a blue powder called acetate silk colors in strong blue tones.

Instead of methylamine, other alkylamines, e.g. B. ethylamine, Propylamine, butylamine or amylamine, and instead of benzylamine, phenylethylamine or use cyclohexylamine. Example 4 A mixture of 24.2 parts is heated Lcuko-i-amino-4-oxyantlirachinone, 6.5 parts of n-propylamine, 8 parts of n-butylamine and zoo parts of methanol to the boil for 8 hours, then add 0.5 parts of copper acetate and 3 parts of piperidine to and. passes air through the boiling mixture for as long as until the dye has formed. The resulting i-n-propylamino-4-n-butylaminoanthraquinone it is filtered off and washed with methanol. It forms blue needles that stand out Dissolve very well in petrol or kerosene with blue paint. Example 5 To a slurry of 50 parts of leuco - 1, 5 - diamino - 4 - oxyanthraquinone in 100 parts of 75 percent Methanol is added 6o parts of a 25 percent strength aqueous methylamine solution and 3o Parts of ethanolamine, the mixture heated for 5 hours with stirring to 6o to 70 ° and then add 1 part of copper acetate and 6 parts of piperidine. By initiating The leuco compound formed is oxidized in air, then allowed to cool and washed Dye out with methanol and dry it. It forms blue needles and dyes acetate silk in strong blue-green tones.

Example 6 To a slurry of 54 parts of leuco i, 5, 8-triamino-4-oxyanthraquinone 60 parts of 25% aqueous methylamine solution are added to 100 parts of 75 percent methanol and 24 parts of n-propylamine, and then heated the mixture with stirring for 8 hours to 6o to 7o °. I part of copper acetate and 6 parts of piperidine are then added and passes air through the boiling mixture until the dye is formed Has. The reaction mixture is then allowed to cool and the blue that has formed is filtered off Powder off, wash it off with methanol and dry it. It dyes acetate silk in blue Tones that are significantly greener than those available with the source material Colorations. Example 7 A mixture of 20 parts of leuco-amino-4-oxyanthraquinone, 8o parts of 1,4-dioxyanthraquinone, 6o parts of a 25 percent aqueous solution of methylamine, 29 parts of ethanolamine and 700 parts of isobutyl alcohol are heated with stirring at about 70 ° for 20 hours. Then let it cool down, sucking up the excreted i-Methylamino-4-oxäthylaminoanthraquinone, washes it with Mefhanol and dries. It is a blue powder and dyes acetate silk in strong blue tones.

Instead of the mixture of methylamine and ethanolamine, one can also use other amine mixtures, e.g. B. those in the second paragraph of Examples 2 and 3 mentioned.

Claims (2)

PATENT CLAIMS: -i. Modification of the process according to patent 722 593 for the production of N-substituted derivatives of i, q.-diaminoanthraquinones, characterized in that leuco-i-aminoanthraquinones, which are in the 4-position, are used here Oxy or methoxy group, or their derivatives with mixtures of various primary amines with an aliphatically bonded amino group. 2. Procedure according to Claim i, characterized in that the Umset .hing in the presence of an oxidizing acting substance performs.