DE866075C - Process for the preparation of dyes of the phthalocyanine series - Google Patents

Description

Process for the preparation of dyes of the phthalocyanine series Es it has been found that valuable dyes of the phthalocyanine series are obtained if one water-insoluble phthalocyanines, which at least twice the group - C H2 - S - X, where X is an acyl, thioacyl, carboxyl or thiocarboxyl group or a Functional descendant corresponding to these groups means containing, with treated with alkaline agents, the mercaptans obtained in a known manner in thioethers and these converted into ternary sulfur compounds.

Phthalocyanines of the type indicated are obtained, for example, if you phthalocyanines containing halomethyl groups with salts of thio or Dithiocarboxylic acids or with compounds of the general formula H S - X, in which X a carboxyl or thiocarboxyl group or one of these groups functional descendant means, converts, so z. B. Di-, tri- or tetra- (acetyl- or thioacetylthiomethyl) phthalocyanines of copper, cobalt, iron or those corresponding metal-free compounds tri- (propionylthiomethyl) copper phthalocyanine, Tri- or tetra- (butyrylthiomethyl) copper phthalocyanine, also di-, tri-, tetra- or Penta- (ethyl- or butylxanthogenatomethyl) -phthalocyanine, tri- or tetra- (dithiocarbamido- or -N-ethyl- or N-butyldithiocarbamidomethyl) -phthalocyanine, tri- or tetra- (rhodanomethyl) -phthalocyanine of copper, cobalt, iron or the corresponding metal-free compounds.

These compounds are obtained by treating with alkaline Means, e.g. B. with solutions of alkali metal hydroxides, alcoholates or sulfides; as Alkaline earth hydroxides, ammonia, amines or hydrazine by moderate heating -the corresponding mercaptans. In some cases, simply heating it is enough of the compounds to cause the cleavage to the mercaptan. The transfer of the- The mercaptans obtained in the thioethers are carried out in a known manner by treatment with alkyl esters, such as alkyl halides or alkyl sulfuric acid or sulfonic acid esters. The same means can be used in one operation or in successive operations Processes the conversion of the thioethers into the learning sulfur compounds be made.

The products obtained are soluble in water or dilute formic acid, and dyeings or prints which are lightfast and washfast are obtained on textiles. _ _ The parts mentioned in the following examples are parts by weight. Example i A fine slurry of 10 parts of tetra (acetylthiomethyl) copper phthalocyanine, prepared by heating tetra (chloromethyl) copper phthalocyanine in glycol with the potassium salt of thioacetic acid, in 70 parts of water, after adding 5 parts of sodium hydroxide and 1 part of sodium sulfide heated to 95 to 100 ° with stirring until a clear solution has formed. The mixture is then allowed to cool somewhat, 70 parts of ethyl alcohol and, at 40 °, 20 parts of methyl iodide are added and the mixture is stirred at this temperature until the reaction has ended. Then the precipitated reaction product is sucked off, washed out with water and dried. The thioether obtained in this way is heated with 30 parts of dimethyl sulfate to zoo to 10 ° until a sample has become soluble in water. It is then allowed to cool and the reaction product is precipitated with acetone, which is separated off in the customary manner. It dyes cotton from an aqueous solution in blue tones. EXAMPLES A mixture of 20 parts of tri- (N, N-dibutyldithiocarbamidomethyl) copper phthalocyanine, prepared by heating tri- (chloromethyl) copper phthalocyanine in glycol with dibutylamine and carbon disulfide, 25 parts of 40 ° Joiger sodium hydroxide solution, 100 parts of methanol is stirred for 3 hours at 9o to g5 ° while passing nitrogen through. After cooling, 50 parts of methanol and 40 parts of dimethyl sulfate are added and the mixture is stirred for a further 2 hours at 30 ° to 40 °. Then the precipitated reaction product is suctioned off, washed out with water and acetone and dried. The thioether obtained is then heated to 100 ° with 50 parts of dimethyl sulfate until it has become soluble in water, and after cooling it is precipitated by adding acetone. A dye is obtained which dyes cotton or wool from aqueous or acetic acid solution in blue shades.

Example 3 10 parts of a mixture of di- and tri- (butylxanthogenatomethyl) cobalt phthalocyanine, made by heating a mixture of di- and tri- (chloromethyl) cobalt phthalocyanine with sodium butoxide and carbon disulfide, with a solution of 10 parts Sodium ethylate in ioo parts of ethyl alcohol. Passing nitrogen through for 4 hours heated to boiling. Then the reaction mixture is left to cool, and left with stirring 25 parts of diethyl sulfate flow in and finally stir for some time at 40 ° Further. The excreted reaction product is sucked off, boiled with water, again suctioned off, washed with acetone and dried. The thioether thus obtained is now heated to 100 ° with 30 parts of diethyl sulphate until it has become water-soluble is. After cooling, the water-soluble dye is precipitated with acetone. He dyes cotton from an aqueous solution in blue tones. Example 4 10 parts finely ground metal-free tri (thioacetylthiomethyl) phthalocyanine, prepared by heating of tri- (chloromethyl) phthalocyanine with the potassium salt of dithioacetic acid in glycol to 100 to 105 °, with 50 parts of xo% aqueous potassium hydroxide solution while passing through heated by nitrogen to g5 ° until a clear solution has formed. then it is allowed to cool, 50 parts of methanol and 20 parts of dimethyl sulfate are added and heated the mixture to 40 ° for about 1 hour. The conversion product separated as usual is then heated to 100 to 10 ° with 25 parts of diethyl sulfate until it has become water-soluble. After the usual work-up, a dye is obtained the wool from aqueous solution dyes in greenish blue tones.

Claims (1)

PATENT CLAIM: Process for the production of dyes of the phthalocyanine series, characterized in that; that one water-insoluble phthalocyanines ,. which contain at least twice the group - CH, - S - X, in which X is an acyl, thioacyl, carboxyl or thiocarboxyl group or a functional derivative corresponding to these groups, are treated with alkaline agents and the mercaptans formed are converted into thioethers in a known manner and then converted into tertiary sulfur compounds.