DE716975C - Process for the preparation of dyes of the pyrene series - Google Patents

Description

Process for the production of dyes of the pyrene series The subject of patent 710 409 is a process for the production of dyes of the perylene series, in which oxy compounds of the perylene or azaperylene series with higher molecular weight unsaturated hydrocarbons or from these by addition of water, hydrogen sulfide, acids, alcohols , Mercaptans or amines-derived compounds are heated in the presence of condensing agents., Instead of the oxy compounds, ketones of the perylene or azaperylene series can also be used, which are converted into -oxy compounds of these series when converted.

It has now been found that similar, liquid or low-melting, Compounds easily soluble in organic liquids and mostly fluorescent compounds can be obtained if the starting materials used instead of the oxy compounds of the perylene or azaperylene series used those of the pyrene series. Instead of the oxy compounds, which, like the oxy compounds of the perylene series, are based on processes known per se can be produced. one can also use connections. proceed out under the terms of implementation pass into those substances, e.g. S. of ketones of the pyrene series, as they - in vat dyes, z. B. the dibenzpyrenquinone series are present. It can also be used as starting materials Use compounds which only form the pyrene ring under the reaction conditions: So you get z. B. by heating .i. i'-Dinaphthyl-8,8'-dicarboxylic acid with dodecyl bromide in the presence of zinc chloride a deep red colored oil, which in organic liquids with yellow transparent color and vivid olive blue Fluorescence is easily soluble. It is also obtained if, instead of i, i'-dinaphthyl-8, 8'-dicarboxylic acid emanates from the anthanthrone obtainable therefrom by ring closure.

Phenols have already been alkylated in the nucleus by means of olefins and at the same time Obtain easily soluble substances in organic solvents, but have them no coloring properties. Action compounds of olefins on aromatic Hydrocarbons such as naphthalene, anthracene or phenanthrene are also included already known. These are probably easily soluble in organic solvents and also fluoresce in these agents, but the amounts are relatively large necessary to achieve a noticeable fluorescence. In contrast, the new ones color Compounds organic means already strong in very small amounts strong on and give them a strong fluorescence. Example i A mixture of So parts Dodecyl bromide, 10 parts of pyranthrone and 10 parts of zinc chloride is so long on Heated for about 200 'until the strong evolution of hydrogen bromide passed and the Source material has disappeared. Allow to cool, dilute with benzene, suck off undissolved constituents, the benzene evaporates and wins by washing the Residue with methanol a red oil, which is in organic liquids, z. B. benzene or gasoline, also in mineral oils. Paraffin oil, fats and waxes easily dissolves with yellow color and gives these substances a strong olive-green fluorescence.

If dodecyl alcohol or dodecyl ether is used instead of dodecyl bromide and passes through hydrogen chloride. the reaction mixture, the same is obtained Link. Instead of dodecyl alcohol, you can also use other high molecular weight alcohols, z. B. octodecyl alcohol, abietinol. or alcohol mixtures. Likewise suitable for the implementation of the olefins corresponding to the high molecular weight alcohols.

End products with very similar properties are obtained. if instead of dodecyl alcohol or ether, one uses dodecyl mercaptan or dodecyl sulfide goes out.

Example 2 A mixture of so parts dodecyl bromide, 5 parts 5 ', 6 '- Phthaloyl - 2 - oxy-4 # 5 = 9 # i o-dibenzpyrene-3, 8-quinone (see patent 671 288) and 5 parts of zinc chloride is stirred at about zoo 'until the starting material disappeared. The mixture mdrd worked up as in Example i, whereby one brown-red oil is obtained that z. B. iii paraffin oil with a brownish yellow color and olive fluorescence easily dissolves.

Example 3 A mixture of 100 parts of dodecyl bromide, 10 parts 4, 5, 9. i o -dibenzopyrene-3, 8-quinone and i o parts zinc dust is under good Stirring heated to about 2oo ', with vigorous evolution of hydrogen bromide a lively implementation begins. The heating continues until there is no hydrogen bromide developed more, then allowed to cool, diluted with benzene and worked according to example i on. A deep red colored oil is obtained in this way in excellent yield very light in paraffin oil with a yellow translucent color and a bluish tinge of olive fluorescence solves.

Example 4 A mixture of 100 parts of dodecyl bromide, 10 parts Anthanthrone and 10 parts of zinc dust are stirred at about zoo to 220 ', until the starting material disappeared and the initially brisk evolution of hydrogen bromide is finished. It is worked up as in Example i and obtained in excellent yield a deep red oil, easily mobile even in the cold, which is found in benzene, gasoline, Paraffin oil, mineral oils and similar substances very easily dissolve and these substances gives a strong, olive-blue fluorescence.

One arrives at the same end product if one uses instead of anthanthrone from i. i'-Dinaphthyl-8, 8'-dicarboxylic acid goes out.

Example 5 A mixture of 50 parts dodecyl bromide, 5th parts. 3, 5-Dioxypyrene and 5 parts of zinc chloride are stirred at about 2od until no source material can be detected anymore. Then you let them cool down and work according to example i. This gives a brownish-red oil that dissolves in paraffin oil yellow see-through color; e and olive-green fluorescence easily dissolves.

Claims (1)

HATE \ TA \ 3PRÜCHE: i. Change in the process of making dyes according to patent 710409, characterized in that oxy compounds of the pyrene series are used here with higher molecular weight unsaturated hydrocarbons or from this by the addition of water and hydrogen sulfide. Acids, alcohols, mercaptans or amine-derived compounds in the presence of condensing agents. a. Process according to claim z, characterized in that the starting materials Ketones of the pyrene series, which are converted into oxy compounds of this series when converted, used. 3. The method according to claim z, characterized in that starting materials used, which only form the pyrene ring under the reaction conditions.