DE171939C - - Google Patents

Description

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IMPERIAL

PATENT OFFICE.

TENTSCHRIFT

- JV * 171939 - CLASS 12j ». GROUP

Process for the preparation of benzanthrone quinolines.

Patented in the German Empire on March 26, 1904.

As is known, the ß-aminoalizarin provides in the condensation with glycerol, for. Am sulfuric acid solution, the alizarin blue, d. H. the quinoline of alizarin. All foresight According to this, the ß-aminoanthraquinone would have that of Graebe (Annalen 201, 349) described anthraquinoline quinone must deliver.

The surprising observation has now been made that the reaction in the Use of ß-aminoanthraquinone works differently by going through the quinoline ring formation and involves a second molecule of glycerin. An analogous behavior show other aminoanthraquinones which contain an amino group in the ß-position. , ■ ·.

An explanation for this deviating behavior, the β-aminoanthraquinones from Behavior of the ß-Aminoalizarins and its derivatives is seen in the fact that in the latter containing hydroxyl groups in the way of a second molecule of glycerol stand.

The condensation of the β-aminoanthraquinones with glycerine can act in the presence or absence of nitrobenzene or similar Agents are made. The resulting condensation products have basic properties. They are divorcing when pouring the reaction mass into ice water in yellow flakes for the most part. The remainder can be separated from the filtrate by adding alkalis.

The products partially dissolve in concentrated hydrochloric acid with the formation of salts which dissociate again with water. The solution in concentrated sulfuric acid is red-brown with strong moss-green fluorescence.

The condensation product of ß-aminoanthraquinone and glycerol is not a single body, but a mixture of two or more very similar compounds of a basic nature. A body crystallizing in beautiful yellow needles with a melting point of 251 ° C. and the empirical formula C ₂₀ H _n O Ν can be isolated as an essential component. It appears as a result of the condensation of 1 molecule of ß-aminoanthraquinone with 2 molecules of glycerol according to the equation:

C ^ H ₉ O ₂ N

C ₂₀ H _n ON

2 C, H _a O ₃ ■ =

7 HO

to have originated.

The condensation product of ß ^ aminoanthraquinone and glycerol with the empirical formula C ₂₀ H _n ON is to be called "benzanthronequinoline" (analogous to the name anthraquinonequinoline) and probably has the following constitution:

65

70

■ \ /

here is the nitrogen-free ring

referred to as "Benzanthrona. (About the relative The position of the benzanthrone ring to the pyridine ring in the "BenzanthiOnchinolin" prevails currently no certainty.)

Example.

18 parts by weight of ß-aminoanthraquinone are in 240 parts by weight of sulfuric acid of 66 ⁰ Be. dissolved and mixed with 38 parts by weight of ice in a stirred kettle; 16 parts by weight of glycerol are added to this mixture and the melt is then ^{heated to about 155 °} C .; a reaction occurs with a yellow coloration, after which the cooled melt is poured into ice water. The condensation product separates out in yellow flakes, it is filtered off, washed and dried. The raw product shows the following properties:

It is a yellow-olive powder that is insoluble in water, partially easily soluble in hot alcohol, benzene, glacial acetic acid with a yellow color; the solution in concentrated sulfuric acid is red-brown with strong moss-green fluorescence; in concentrated hydrochloric acid, the product partially dissolves with a yellow color, forming a salt that can be decomposed by water. Recrystallization from toluene from this crude product are obtained two compounds, namely the "Benzanthronchinolin", which up to 234 ⁰ C. shows a melting point of 251 ° C., and then a considerable amount of a second body the melting point 232nd When fused with caustic alkalis, both produce a violet-blue vat dye which is commercially available under the name »Cyananthrena. The product with a melting point of 232 to 234 ^° C. shows at first glance all the properties of a uniform chemical compound. With frequent changes of solvent, however, it is possible, finally, to cut it into Benzanthronchinolin and a body of melting point 322 ⁰ C; in the analysis, this yields numbers which match _{the formula C 17} H ₉ O ₂ N; there is therefore an isomer of the Graebeschen anthraquinonequinoline cited at the beginning.

Completely analogous products deliver z. B. 2 x 6- and 2 x 7-diaminoanthraquinone as well as the Sulphonic acids of the aminoanthraquinones mentioned. So there is the ß-aminoanthraquinone sulfonic acid (See. Example I of the patent specification 138134 cl. 12 q) with glycerol and Sulfuric acid condenses a product that, when dry, turns into a yellow-olive powder represents, which is very difficult in cold water, slightly easier in hot water with yellow color is soluble. Diluted caustic soda easily dissolves it with a yellow-brown color. The solution in concentrated sulfuric acid is red-brown with a strong moss-green fluorescence. Concentrated hydrochloric acid also dissolves the sulfonic acid with a yellow color; on addition water excretes it in yellow flakes.

The condensation products from 2 · 6- respectively. 2 · 7-diaminoanthraquinones are brown to brown-black powders that are insoluble in water and that can be dissolved in hot alcohol, glacial acetic acid etc. partially loosen slightly with red-yellow paint. The solution in concentrated sulfuric acid is red-yellow with a strong yellow-green fluorescence.

Claims (1)

Patent claim: Process for the preparation of benzanthrone quinolines, consisting in that one ß-aminoanthraquinone or other aminoanthraquinones containing a ß-amino group with the exception of 1 · 2-dioxy-3-aminoanthraquinone and its derivatives heated with glycerine with the addition of condensing agents.