DE871004C - Process for the preparation of compounds of the diacetylene series by oxidation of cupro compounds of the acetylene series with cupric compounds - Google Patents

Description

Process for the preparation of compounds of the diacetylene series by Oxidation of cuprous compounds of the acetylene series with cupric compounds found that compounds of the diacetylene series are obtained in a simple manner if one compounds of the acetylene series, which is bonded to an acetylene carbon atom Contain hydrogen atom and at least one water-solubilizing group. in Shape of their cupro connections with cupri connections at ordinary or deeper Temperature treated. Suitable starting materials of the acetylene series are, for example Propargyl alcohol and its homologues, how to get them for example by reacting obtained from acetylene with aldehydes or ketones, also carboxylic acids of the acetylene series, z. B. propiolic acid, and amines of the acetylene series, z. B. dimethylpropargylamine. To increase the solubility in water, the carboxylic acids can be in the form of their Use salts with alkali metals and the amines in the form of their salts with mineral acids. The conversion of the acetylene compounds into their cuproacetylenides is effected in in a conventional manner by treatment with cupro compounds, optionally in Presence of acid binding agents.

The cupric compounds used as oxidizing agents are the simplest. Cuprichloride or sulphate, are combined in aqueous solution, if necessary with substances capable of complex formation with cupric compounds, e.g. B ;. Ammonia, Ammonium salts or tartaric salts. They go doing it in cupro connections over, which in turn is used to produce the cupro compounds of the starting materials can be used. For example, if the cuprous compound of propargyl alcohol is oxidized with cupric chloride, one can use the resulting cuprous chloride to get out dilute aqueous propargyl alcohol solutions, such as those used, for example, in the Reaction of acetylene with aqueous formaldehyde solution in the presence of copper acetylenide obtained to deposit the cupro compound of the propargyl alcohol.

It is already known by treating cuproacetylenide with cuprichloride Manufacture diacetylene. In the case of the one subject to the same implementation, especially in itself Reactive phenylacetylene can only be oxidized at elevated temperatures satisfactory. Surprisingly, it has now been found that the cupro compounds Unilaterally substituted acetylenes with water-solubilizing groups already contribute Ordinary or low temperature satisfactory - with the help of cupric compounds can be oxidized, although their reactivity is otherwise behind that Phenylacetylene stand back.

It is also known; To oxidize cuproacetylenide with potassium ferricyanide. Here, however, foreign substances get into the solution to be oxidized, which means that it can be reused difficult. In the case of the new process described above, however, only arise Cupro compounds which directly lead to the formation of the cupro compound of the: Acetylene compound used or in a simple manner by oxidation in the cupric compounds transferred and then used again for the oxidation of the acetylene compounds can.

It has also been suggested in the absence of oxidizing agents or to work using oxygen or oxygen-containing gases. In the first case, however, you get poor yields or no result at all, while in the second case there is not only a great risk of explosion, but the water-soluble making groups can also be changed by undesired side reactions.

The parts given in the examples below are parts by weight. Example i 17.1 parts of crystallized cupric chloride, 58.7 parts of ammonium chloride and 195 parts of water are mixed with 12 parts of the moist cupro compound of propargyl alcohol at 0 to 5 °, stirred. The cupro compound disappears in the course of 1 to 2 hours of the propargyl alcohol completely, which indicates the end of the reaction. The solution is shaken out with ether or another suitable solvent. From the ethereal solution is obtained hexadiyne-2, q-diol-i, 6 after evaporation of the ether in the form of white crystals (F. i13 ''). The yield is 80/9 ..

Example 2, To a solution made in a nitrogen atmosphere 10 parts cuprous chloride and 91 parts 25% ammonia produced and with little Hydroxylamine chlorohydrate has been decolorized, 8.5 parts of dimethylaminopropyne-2 are added and neutralized with hydrochloric acid. The mass in which the yellow cupro salt of dimethylpropargylamine is suspended, is at room temperature with 2o parts of cuprichloride and 2o parts Ammonium chloride was stirred in 100 parts of water for 3 hours, the yellow precipitate disappears. After the addition of concentrated ammonia, the N formed can be N'-tetramethyl-i, 6-diaminohexadiyne-2, q. extract with ether. After drying with calcined sodium sulfate and chasing off the ether, the base goes in 85% yield at 15 mm between i25 to r3o ° 'over.

Example 3 20 parts of cuprous chloride are added in a nitrogen atmosphere dissolved in 136 parts of concentrated aqueous ammonia. The solution will be with little Hydroxylamine chlorohydrate solution discolored. Now one drips. under ice cooling 1q. Parts Propiolic acid is added, the solution is neutralized and stirred with q.o parts for 5 hours Cuprichloride and q.o parts of ammonium chloride. The mixture is poured onto ice and treated with a lot of concentrated hydrochloric acid, whereupon the diacetylenedicarboxylic acid formed is extracted with ether. After drying the essential solution and evaporating of the ether, the acid remains in pale yellow crusts in a yield of 60%.

Claims (1)

PATENT CLAIM: Process for the production of compounds of the diacetylene series by oxidation of cuprous compounds of the acetylene series with cupric compounds, thereby characterized in that there are compounds of the acetylene series, which are linked to an acetylene carbon atom-bonded hydrogen atom and at least one water-solubilizing group contained, in the form of their cupro compounds at ordinary or low temperature subject to this oxidation.