DE502042C - Process for the preparation of new condensation products of the benzanthrone series - Google Patents

Description

Process for the preparation of new condensation products of the benzanthrone series Addition to patent 499320 The main patent 499 320 describes a process for the preparation of new condensation products of the benzanthrone series, in which mixtures of benzanthrone or its substitution products with free 2-position and ketones of the general formula R. -CO-CH2-R, (R - an alkyl, cycloalkyl, aralkyl or aryl group, which can also be substituted, R1 - H or any organic radical that does not participate in the reaction, e.g. alkyl, aryl, etc. j are treated with alkaline condensation agents. The reaction products very probably correspond to the general formula It has now been found that valuable new condensation products can also be obtained if bodies which contain a benzanthronyl radical with a free 2-position, which is in the Bz-i position through the mediation of sulfur to a rice of the general formula R-CO- CH2 (R - an alkyl, cycloalkyl, aryl or aralkyl group, which can also be substituted) is bonded and can also trot any other substituents, treated with alkaline condensing agents. The new compounds thus obtained are probably in accordance with the general formula composed, by the action of alkalis they go into salt-like compounds, which with water, alcohol, acetone or the like. deliver strikingly intensely colored solutions.

The new condensation products are generally formed extremely easy. In some cases they arise from treatment of the Starting materials with dilute aqueous alkali solutions. Usually the reaction works but in a suitable organic solvent or suspension medium such as alcohol or Pyridis, smoother. The yields achieved are generally very high Well.

The new substances can serve as starting materials for the production of dyes. Example 10 parts of Bz-i-Benzanthronylaceto @ nylsulfid of the formula that one z. B. obtained by the action of monochloroacetone on Bz-i-Benzant'bronylnatriummerkaptid, are heated with 5 parts of powdered potassium hydroxide and 5o parts of pyridine with stirring for 6 hours to 35 to q.0 °. At! The reaction is slower at room temperature. The initially red-brown color of the liquid mass gradually turns violet and then blue, and the reaction mixture becomes mushy, it is dissolved in water and the violet solution is acidified with hydrochloric acid. The resulting product can, for. B. by extracting with aqueous sodium sulfur solution, in which the potassium salt of the new compound is sparingly soluble, freed from approximately simultaneously formed Bz-i-benzanthronyl mercaptan and completely purified by crystallization from nitrobenzene.

The orange-brown needle-forming body thus obtained is difficult to dissolve in common organic solvents. With concentrated sulfuric acid it gives cyan, chemicals with water or alcohol Al, already remarkably strong colored red-violet with alkali metal solutions of intense scarlet red fluorescence. EXAMPLE 2 10 parts of Bz-i-benzanthronylacetonyl sulfide are heated to 55 to 60 ° for 8 hours with stirring in 15 parts of 33 percent alcoholic potassium hydroxide solution. After dilution with water, it is neutralized with hydrochloric acid and the crude product is worked up as in Example i. Example 3 100 parts of Bz-i-benzanthronylacetonyl sulfide and 5 parts of powdered anhydrous sodium sulphide are mixed well and heated with 100 parts of pyridine to 55 ° to 60 ° for 7 hours. The blue reaction mass is poured into ice-cold bisulfite liquor and the crude product is worked up as described above. The body obtained in this way is identical to that described in Examples i and 2.

EXAMPLE A mixture of 10 parts of phenacyl-Bz-i-venzanthronyl sulfide of the formula available e.g. B. from co-bromoacetophenone and Bz - i - beiizanthi-ony sodium mercaptide, with 5 parts of potassium is added to 100 parts of pyridine and heated to 55 to 60 ° for 7 hours in the absence of air. The solution diluted with water is then precipitated with hydrochloric acid and the new compound is purified using its sodium salt, which, in contrast to that of the Bz-i-benzanthronyl mercaptan that has been added, is sparingly soluble in water. The new orange-brown colored ketone is sparingly soluble in most organic solvents. In concentrated sulfuric acid it dissolves with a green color, in warm aqueous alkalis or alkali carbonates rather difficultly, in alcoholic alkalis it dissolves more easily with a strikingly strong cornflower blue color. Example 5 One part of Bz-i-benzanthronylacetonyl sulfide is heated to 125 to 130 ° for a few hours with 10 parts of anhydrous sodium sulfide. The mass is extracted with cold water in order to remove excess sodium sulfide and incidentally formed Bz-i-benzanthronyl mercaptan, whereupon the residue is dissolved in hot water and freed from any starting product that may still be present by filtration. By acidifying the red-violet solution, the pure product is obtained, which is identical to that obtained in Examples i and a.

Example 6 A mixture of 10 parts of Bz-i-Benzanthronylchlorph, enacylsulfid of the formula: (obtainable e.g. from p-chlorophenacyl chloride and Bz - i - benzanthronyl sodium mercaptide), 5 parts of potash and 10o parts of pyrudine is heated to 60 to 70 ° until the initially thin-bodied mass has become mushy; it is then diluted with water and acidified with hydrochloric acid. The separately separated crude product can be freed of incidentally formed Bz-iB, enzanthronylm, and Erkaptan by boiling a finite sodium sulfide solution. Recrystallization from nitrobenzene gives the new body in red-brown needles which dissolve in concentrated sulfuric acid and are not green in color, insoluble in cold alkalis and very sparingly soluble in hot alkalis with blue color.

Claims (1)

PATENT CLAIM: Modification of the procedure of the main patent, thereby characterized that such bodies, which contain a benzanthene: ronyl radical with free, the one in the Bz-i position by mediating sulfur to a remainder of the general Formula R-CO-CH. (R = all; yl, cycloalkyl, aryl or aralkyl groups, which are also substituted can be) is bound and can have any further substitutions, treated with alkaline condensing agents.