DE539102C - Process for the preparation of nitrogen-containing condensation products - Google Patents

Description

Process for the preparation of nitrogen-containing condensation products It has been found that nitrogen-containing condensation products are obtained when polynuclear carbocyclic cyano compounds are treated with condensing agents.

The reaction products obtainable in this way are all heavier soluble than the starting materials and presumably represent polymerization products, which Polyazine structure is likely to represent the latter.

Suitable condensing agents are: anhydrous sulfuric acid, Oleum, chlorosulfonic acid, hydrochloric acid gas; also calcium carbonate, barium oxide, aluminum chloride, Antimony pentachloride. The action of the condensing agent can optionally be used let go in the presence of organic solvents or suspending agents. Man can also condensation of the Cv compounds by heating in high-boiling organic solvents, preferably solvents with basic properties, in the presence of halogen compounds of metals, including in the present case also include the cyanides and rhodanides, for example in the presence of cuprohalides, carry out.

Both the starting materials for the present reaction Cyan compounds of the naphthalene series as well as higher molecular weight carbocyclic compounds into consideration. The condensation products usually obtainable in approximately theoretical yield If necessary, they can be cleaned using the usual methods. They are in general very sparingly soluble in organic solvents, but they mostly dissolve relatively easy in concentrated sulfuric acid.

The polymerization products of the cyano compounds of the anthraquinone series and other cyano compounds capable of vat formation which in themselves have no affinity need to own fiber, usually make valuable strong coloring vat dyes Instead of starting from the cyano compounds themselves, one can use the representation this and the further condensation can often be carried out in one operation. example 200 parts of ß-itaphthonitrile are cooled to about 0 ° in chlorosulfonic acid entered and kept for a few hours at 10 to 20 ° with stirring. Thereon it is diluted with anhydrous sulfuric acid, poured into ice water and filtered off with suction. That The reaction product obtained is a colorless powder which melts to about 29o ° and are obtained crystallized in colorless needles from organic solvents can. Α-Naphthonitrile reacts in a similar way under these reaction conditions.

Example e 125 parts of 2-amino-3-cyananthraquinone are dissolved in 150 parts of 23 ° fgem oleum with stirring, whereupon the mixture is heated to 50 to 80 °. As soon as a sample taken from an olive-brown vat on cotton gives orange colorations, it is allowed to cool and worked on as described in Example i. The condensation product obtained is an orange powder, dissolves in concentrated sulfuric acid with an orange color and is practically insoluble in almost all organic solvents. If necessary, it can be purified by dissolving it in sulfuric acid and diluting the solution with water or dilute sulfuric acid using the crystalline oxonium sulfate.

The same condensation product is also obtained by treating 2-Amino-3-cyananthraquinone with hydrochloric acid, acid chlorides, e.g. B. oxalyl chloride or Phosgene, which is expediently carried out in the presence of diluents at a higher temperature is working. Example 3 2o parts of pure 2-amino-3-cyanantlirachinon are in 100 Parts of nitrobenzene after adding 100 parts of calcium carbonate while stirring for so long cooked until a sample taken from an olive-brown vat on cotton orange-colored Dye supplies. It is suctioned off hot, the residue is treated with steam and suction off, washes neutral and dries. That in quantitative yield in the form of orange The reaction product obtained from needles dissolves in concentrated sulfuric acid yellow-orange color, is practically insoluble in almost all organic solvents and agrees in its properties with the condensation product obtained according to example e match. Example q. 5 parts of i-cyano-2-aminoanthraquinone shown for example from i-chloro-2-aminoanthraquinone by the method of the British patent 261 422, are in 2o parts of quinoline with 2 parts of copper cyanur with stirring so heated to the boil for a long time until a sample taken does not contain unchanged starting material reveals more. After cooling, it is filtered off with suction and the residue is freed Washing with alcohol or hydrochloric acid or by treating with steam of adhering Quinoline as well as copper salts, and if necessary still iiiit ammonia or diluted nitric acid washes. The reaction product, a brown powder, dissolves in concentrated sulfuric acid with a brownish red color and melts above 36o °. It stains cotton from a brown vat in brown tones. Example s io parts i-Amino-2-broinanthraquinone, available e.g. B. by brominating i aminoanthraquinone in glacial acetic acid according to patent specification 16o 169, K1.129, quinoline is added in 4.o parts 4.8 parts of cyanuric copper heated to boiling for about 8 hours with stirring and, as indicated in Example 4, worked up. A purple powder is obtained in this way melts above 360 °, is almost insoluble in organic solvents, in concentrated form Sulfuric acid dissolves with olive green color and from purple vat cotton in dyes strong violet tones of very good fastness. Example 6 5 parts of 2-oxy-3-cyananthraquinone, obtainable, for example, from 2-amino-3-cyanantlirachinon by diazotizing and Boil, three to five times the amount of quinoline with the addition of 2.5 Parts of copper vanur heated to the boil, held for a few hours and, as usual, worked up. The condensation product thus obtained, a yellow-brown powder, dissolves turns yellowish-brown in concentrated sulfuric acid and delivers on cotton from an olive-brown vat yellow colorations which turn to orange with alkali. example 7,000 parts of 2-amino-3-cyananthraquinone are converted into 10,000 parts of quinoline after the addition of 666 parts of barium oxide boiled for a few hours with stirring. As soon as a The sample taken is an orange instead of the green vat of the starting material The vat delivers, it is sucked in quantitative yield in the form of orange needles obtained polymerization product. It is identical to the one available according to the examples Reaction product and melts above 36o °.

Instead of barium oxide, lithium carbonate or calcium oxide can also be used as Use polymerization agent. Example 8 100 parts of 2-amino-3-cyananthraquinone become quinoline with zoo parts aluminum chloride in 10,000 parts with stirring heated to 200 ° for a long time until no unchanged starting material is found in a sample taken is more detectable, d. H. an orange one Küpe delivers. then it is allowed to cool, the suspension medium is driven off with steam, and finally acidified with dilute hydrochloric acid, the reaction product is filtered off, washed neutral and dried. The properties of the polymerization product obtained in this way match the ones Example? available reaction product.

Iron chloride or antimony pentachloride can also be used in place of aluminum chloride use as a polymerization agent.

Claims (1)

PATLNT CLAIM Process for the preparation of nitrogen-containing condensation products, characterized in that polynuclear carbocyclic cyano compounds with Treated condensing agents.