DE1128066B - Process for the preparation of dyes of the anthraquinone series - Google Patents

Description

GERMAN

PATENT OFFICE

B 54591 IVc / 22b

REGISTRATION DATE: AUG U S T 28, 1959

NOTICE THE REGISTRATION ANDOUTPUTE EDITORIAL: APRIL 19, 1962

It has been found that new, valuable dyes are obtained if anthraquinone derivatives, which contain at least one reactive amino group, reacts with monohaloaryl ketones.

As anthraquinone derivatives which contain at least one reactive amino group, are Anthraquinone compounds called that bound to the anthraquinone core at least one primary or secondary amino group and optionally further substituents or attached rings wear. Of particular technical interest are anthraquinone compounds that contain one or more have primary amino groups, for example 1- or 2-aminoanthraquinone, 1,5-diaminoanthraquinone, l-amino-4-hydroxyanthraquinone, 1-amino-4-methoxyanthraquinone, l-Amino-4- or -5-benzoylaminoanthraquinone, 1-amino ^^ - dibromoanthraquinone, 2-amino-3,4-phthaloylacridone and 4- or -5-aminoanthrapyrimidine.

Monohaloaryl ketones, such as monochloro or bromoaryl ketones, are, for example, monohaloaryl alkyl ketones and monohalodiaryl ketones, such as 4-bromoacetophenone, 4-chloroacetophenone, 4-chlorophenyldiphenyl ketone, 4-chlorophenylnaphthyl ketone, 4-chlorobenzophenone or 4-bromobenzophenone.

The conversion of the anthraquinone derivatives containing at least one reactive amino group the monohaloaryl ketones are usually carried out in organic solutions and / or Diluents and in the presence of catalysts. It is useful to add the reaction mixture to add acid-binding agents and to separate off any water that may have arisen as a result of the addition of such agents. As organic Solvents and / or diluents are z. B. higher boiling alcohols such as n- or iso-butanol and the amyl alcohols, or aromatic nitrated or halogenated hydrocarbons, such as o-dichlorobenzene, 1,3,5-trichlorobenzene and nitrobenzene, and copper and copper compounds may be mentioned as catalysts. Acid binding agents Means are e.g. B. the alkali salts of carbonic acid, such as sodium or potassium carbonate and sodium bicarbonate, or the salts of strong bases with weak acids such as sodium acetate or sodium dihydrogen phosphate. In some cases it will be preferred to use the organic solvents and / or diluents to be replaced by water or by mixtures of water with water-miscible organic solvents and / or diluents and, if necessary, to work in a closed vessel under pressure. If short implementation

Process for the preparation of dyes of the anthraquinone series

Applicant:

Aniline & Soda Factory in Baden

Corporation,

Ludwigshafen / Rhine

Dr. Willy Braun and Dr. Ernst Hartwig, Heidelberg, have been named as the inventor

times are to be achieved, the implementation of the at least one reactive amino group is carried out containing anthraquinone derivatives with the monohalogenaryl ketones, advantageously in molten form Salts, e.g. B. in alkali metal acetates, such as sodium or potassium acetate, or mixtures thereof and in the presence of the aforementioned catalysts.

Regardless of whether you are in organic liquid, in aqueous liquid, in mixtures of organic solvents and / or diluents with water or in molten alkali metal acetates works, the most favorable reaction temperature is different from case to case and can can easily be determined by experiments. It is usually within the temperature range of 50 to 300 ° C, mostly within the range of 160 to 240 ° C.

In the preparation of the new dyestuffs, it is expedient, if appropriate, for each amino group in the further substituents or attached rings carrying anthraquinone derivatives at least equimolecular Use amounts of monohaloaryl ketones. For example, you go to implementation one mole of a monoaminoanthraquinone compound advantageously from about 1.1 moles of a monohaloaryl ketone the end. However, a larger excess of monohaloaryl ketone is not detrimental to the course of the reaction. The implementation time is usually between 5 and 50 hours.

In molten salts of the type mentioned above, the reaction is already after 30 to 300 minutes completed.

209 560/434

The new dyes are generally obtained in this way in great purity and in very good yields. If necessary, the dyes can also be taken by additional measures, for. B. by sublimation, by recrystallization from suitable solvents such as nitrobenzene, N, N-dimethylformamide or Ν, Ν-dimethylacetamide, or by treatment with aqueous alkali metal hypochlorite solutions further cleaned.

The dyes obtainable according to the invention are not only available as pigments, but also in dissolved form Form suitable for dyeing structures made of natural and synthetic materials. So They can be used as pigments, for example for the spin dyeing of threads made of cellulose acetate, viscose or polyacrylonitrile and / or copolymers of acrylonitrile. Your great heat resistance however, makes the new dyes particularly useful for dyeing polystyrene or linear polyamides suitable in bulk. The colors of the structures colored in the mass usually have excellent lightfastness, which is also ensured by the usual additives such. B. by titanium dioxide, is not affected.

Compared to the known method of French patent 828 581 with monohaloalkylaryl ketones Dyes which can be prepared are characterized by the dyes obtainable by the present process with monohalogenoarylalkyl ketones due to their considerably better lightfastness than those dyed in the mass with these dyes Made of polystyrene.

The parts and percentages given in the examples are weight units.

example 1

35

A mixture of 22.3 parts of 1-aminoanthraquinone, 26 parts of 4-chlorobenzophenone, 8 parts of anhydrous sodium carbonate, 4 parts of anhydrous sodium acetate and 0.5 part of finely divided copper oxide in 100 parts of nitrobenzene is slurried and the mixture is heated to gentle while stirring Simmer until no more water escapes. This takes about 20 to 30 hours. After cooling, the reaction material is filtered off with suction, washed with nitrobenzene and the filter material is treated with steam in the presence of aqueous hydrochloric acid until no more nitrobenzene escapes. Now the goods are washed acid-free and dried. 35 parts of a red crystal powder with a melting point of 209 to 211 ^° C. and a nitrogen content of 3.9% are obtained. The dye is particularly suitable for bulk dyeing of polystyrene and provides red dyeings with excellent light and temperature resistance.

The same dyestuff is obtained in an equally good yield if one takes the place of 4-chlorobenzophenone the appropriate amount of 4-bromobenzophenone is used.

Example 2

A mixture of 23.8 parts of 1,5-diaminoanthraquinone, 52 parts of 4-chlorobenzophenone, 16 parts of anhydrous sodium carbonate, 8 parts of anhydrous Sodium acetate, 1 part finely divided copper oxide and 150 parts nitrobenzene will last as long stirred with gentle boiling until no more water is separated out. For this you need approximately 24 to 30 hours. Working up is carried out in the same way as described in Example 1 is.

50 parts of a red-violet crystal powder which melts at 247 to 248 ° C. and one Has a nitrogen content of 4.6%. The dye dissolves in polystyrene with a bluish red color.

A similar dye is obtained in good yield and purity by using 1,8-diaminoanthraquinone instead of 1,5-diaminoanthraquinone.

Example 3

A mixture of 34 parts of l-amino-4-benzoylaminoanthraquinone, 30 parts of 4-chlorobenzophenone, 8 parts of anhydrous sodium carbonate, 4 parts anhydrous sodium acetate, 0.5 part of finely divided copper oxide and 100 parts of nitrobenzene Stirred under gentle boiling for 20 hours. The resulting water is allowed to escape. After cooling, the reaction material is sucked off and washed with nitrobenzene. The filter material is, as described in Example 1, freed from adhering nitrobenzene, suction filtered, acid-free with water washed, rewashed with methanol and dried.

37 parts of a violet crystal powder which contains 5.4% nitrogen and ^{melts at 228 to 230 °} C. are obtained. The dye dissolves in polystyrene with a purple color.

A dark red dye is obtained if the l-amino-4-benzoylaminoanthraquinone is used replaced by the l-amino-5-benzoylaminoanthraquinone.

Example 4

25 parts of l-amino-4-methoxyanthraquinone, 26 parts of 4-chlorobenzophenone, 8 parts of anhydrous sodium carbonate, 4 parts of anhydrous sodium acetate, 0.5 part of finely divided copper oxide and 100 parts of nitrobenzene are mixed and the resulting water is distilled off for about 20 hours 210 to 212 ⁰ C stirred. After the work-up, in the same way as in the example! takes place, 31 parts of a violet crystal powder which contains 3.3% nitrogen and melts at 195 to 196 ° C are obtained. The dye dissolves in polystyrene with a red-violet color.

Demethylation of this dye gives a much more bluish violet dye.

Example 5

18 parts of anhydrous sodium carbonate and 2 parts of finely divided copper oxide are introduced into a molten mixture of 192 parts of crystallized sodium acetate and 162 parts of potassium acetate. The temperature of the melt is then slowly increased and the water from the sodium acetate is distilled off. After the temperature of 190 ^° C. has been reached, 23.8 parts of finely powdered 1,4-diaminoanthraquinone are introduced into the molten mixture in such a way that no lumps are formed. As soon as the melt has become uniform, 55 parts of 4-chlorobenzophenone are added and the temperature of the melt is slowly increased to 220 to 227 ° C. Man

stir at this temperature until the reaction is complete, which is generally the case after 2 to 3 hours. The melt is then allowed to cool to 90 ° C. and a little water is carefully added in small portions. The mixture is then stirred into water, the reaction material is filtered off with suction, washed with water, the filter material is rubbed with dilute aqueous hydrochloric acid and this suspension is heated ^{to 90 to 95 ° C. for about 1} _{l for 2} hours. The dye is then filtered off with suction , washed acid-free, washed with hot methanol until the filtrate runs off almost colorless, and dried.

50 parts of a dark blue powder which melts at 205 to 206 ° C. and has a nitrogen content are obtained of 4.2%. The dye dissolves in polystyrene with a deep blue color.

Example 6

18 parts of 1-aminoanthraquinone, 20 parts of 4-bromoacetophenone, 9.6 parts anhydrous sodium carbonate, 2.2 parts anhydrous sodium acetate, 0.5 part finely divided Copper oxide and 120 parts of nitrobenzene are mixed and kept under mild conditions Stir at the boil until no more water is separated out. This takes about 8 to 12 hours. Working up is carried out in the same way as is described in Example 1. 23 parts are obtained of a red crystal powder that melts at 217 to 219 ° C and has a nitrogen content of 4.3%. The dye dissolves in polystyrene with a red color.

Claims (1)

PATENT CLAIM: Process for the preparation of dyes of the anthraquinone series, characterized in that anthraquinone derivatives which contain at least one reactive amino group are reacted with monohaloaryl ketones. Considered publications:
French Patent No. 828 581. A coloring table was displayed when the application was announced. © 209 560/434 4.62