DE234917C - - Google Patents

Description

IMPERIAL

PATENT OFFICE.

PATENT LETTERING

- M 234917 - ■ CLASS Mq. GROUP

or their derivatives.

Patented in the German Empire on May 29, 1910 .

The following is a description of a method that makes it easy to display Aminoanthraquinones and aminonaphtanthraquinones, some of which were previously inaccessible at all or their derivatives.

It has been found that halogenated diaryl ketone-o-carboxylic acids when heated with ammonia under pressure in the presence of copper or copper salts in part convert very smoothly to form amidated diaryl ketone-o-carboxylic acids. You get in this way not only a number of known, but so far only from the corresponding Amino diaryl ketone-o-carboxylic acids represented by reduction in nitro bodies, but also a large number of new derivatives that were previously difficult or impossible were representable.

The aminodiaryl ketone-o-carboxylic acids thus obtained are then converted into aminoanthraquinones by treatment with dehydrating agents, Aminonaphtanthraquinones or their derivatives converted.

The products to be presented, which do not have the character of a coloring agent, should be used as starting materials find use for the representation of dyes.

Example 1.

50 parts by weight of that from 4-chlorophthalic anhydride and toluene 4 (5) -chloro-4'-methyldiphenylketone-2-carboxylic acid obtained in the usual manner (M.p. of the acid dissolved from glacial acetic acid 168 to 170 °) are with 700 parts by weight 20 percent ammonia and ι part by weight of copper powder in a stirred autoclave Heated to 190 to 195 ° for 12 hours. After driving off the ammonia will filtered hot, the filtrate acidified with hydrochloric acid, nitrated again and the acidic filtrate neutralized. The amino acid separates out as a light gray-yellow powder in good yield. The acid is easily soluble in both dilute mineral acids and alkalis. the end When dissolved in dilute hydrochloric acid, it is precipitated by sodium acetate.

For conversion into the corresponding anthraquinone derivative, 10 parts by weight of Amino acid in 100 parts by weight of 90 percent sulfuric acid heated to about 200 ° entered quickly. The temperature of the solution is kept at 200 ° for a few minutes; then the reaction mixture is poured onto ice, the precipitated 2-amino-6 (7) -methylanthraquinone is filtered off, boiled with dilute sodium hydroxide solution and dried. It can be dissolved from xylene for cleaning; you get it in orange-yellow Needles from m.p. 256 to 257 °.

If the toluene used in the above example is replaced by technical grade xylene, so one obtains a chlorodimethyldiphenylketonocarboxylic acid, which is also easily converted into the amino acid or can be converted into the corresponding aminodimethylanthraquinone.

Example 2.

50 parts by weight of the 3 (6) -ChIo r-4'-methyldiphenylketone-2-carboxylic acid obtained in the usual way from 3-chlorophthalic anhydride and toluene (melting point from glacial acetic acid 175 °) are mixed with 700 parts of 20 percent ammonia and ι part of copper powder Stirring autoclave heated to 190 ° to 195 ° for 12 hours. After the ammonia has been driven off, it is strongly acidified and the filtered acidic solution is neutralized. The amino acid falls here as light- ■; ■ gray powder from acids which both mineral 1 and is soluble in alkalis. When heated to about 200 ° with 8% sulfuric acid, the amino acid changes into i-amino-6 (7) -methylanthraquinone, which crystallizes from benzene in brick-red needles with a melting point of 175 °.

Example 3.

50 parts by weight of that obtained from phthalic anhydride and i-chloro-2 · 4-dimethylbenzene 2 '· 4'-Dimethyl-5'-chlorodiphenyl ketone-2-carboxylic acid (m.p. from glacial acetic acid 162 ") with 350 parts by weight of 20 percent ammonia and ι part by weight of copper powder for 24 hours heated to 190 to 195 ° in a stirred autoclave. · The processing is carried out as in the previous examples. The amino acid crystallizes in pale yellow from monochlorobenzene Crystals which decompose at 140 ° melt.

The conversion into the corresponding aminoithraquinone derivative is expedient under the conditions given in Example 1. The crude i-amino-2 obtained in this way · 4-dimethylanthraquinone can be dissolved from benzene in dark red crystal aggregates of m.p. 293 °.

Example 4.

50 parts by weight of that from 4-chlorophthalic anhydride and naphthalene. obtained 4 (5) -chlorophenylnaphthylketone-2-carboxylic acid (Mp. From glacial acetic acid 175 °) are with 350 parts by weight 20 percent ammonia and 1 part by weight of copper powder for 10 hours in a stirred autoclave heated to 190 °. The work-up is carried out as in Example 1. The amino acid provides is a gray alkali and acid-soluble powder, which can be mixed with by briefly heating eight times the amount of 80 percent sulfuric acid to 200 to 2io ° and boiling the Crude product with dilute sodium hydroxide solution easily forms the corresponding aminonaphtanthraquinone can get. This body crystallizes from xylene in bright red, shiny Needles of m.p. 238 °.

Example 5.

50 parts by weight of the chloronaphthylphenyl ketone-o-carboxylic acid obtained from phthalic anhydride and 2-chloronaphthalene (Mp. From glacial acetic acid 217 to 22o °) are with 250 parts by weight 30 percent ammonia and 1 part by weight of copper chloride in a stirred autoclave for 12 hours heated to 170 to 175 °. The reaction mixture is worked up as in previous examples. The amino acid is a dark yellow powder, which is among the conditions given in Example 4 are converted into an aminonaphtanthraquinone made of xylene in shiny, brown-violet needles that melt at 182 ° lized.

Claims (1)

Patent claim: Process for the preparation of aminoanthraquinones and aminonaphtanthraquinones or their derivatives, consisting in that halogenated diarylketonocarboxylic acids heated with ammonia in the presence of copper or copper salts under pressure and the resulting aminodiaryl ketone-o-carboxylic acids treated with dehydrating agents.