DE1039163B - Process for the production of sulfur-containing dyes - Google Patents

Description

GERMAN

It has been found that new sulfur-containing dyes are obtained when using alkylarylsulfides converts polynuclear dyes, the Halogenmethvlgruppen and at least one) C = O- or) C = N group included. The reaction is advantageously carried out in the presence of such catalysts as they are used in the Friedel-Crafts synthesis and can furthermore, if desired, the products obtained convert into tertiary sulfonium compounds by known methods.

Suitable alkyl aryl sulfides are, for example, methyl, ethyl, propyl, isopropyl, butyl or isobutylphenyl sulfide or the corresponding, z. B. derived from thiocresols, thiodiphenyls or thionaphthols Compounds or their substitution products, insofar as they are in the aromatic radical at least still contain a hydrogen atom capable of conversion according to Friedel-Crafts, such as, for example the thioethers obtainable from 2-, 3- or 4-chlorothiophenol.

Azaporphines and azaporphines containing halomethanol are particularly suitable as dye components Porphines, such as the dis- to octakis (chloromethyl) phthalocyanines of copper, cobalt, nickel, manganese, Iron, aluminum or zinc or the corresponding metal-free compounds, furthermore Phthalocyanines containing bromomethyl groups and tetraphenyl phthalocyanines containing chloromethyl groups as well as benzoporphines and similar substances. But also those containing halomethyl groups Indigo and thioindigo compounds, anthraquinones, beuzanthrones, dibenzanthrones, isodibenzanthrones, Pyranthrones and the halomethyl derivatives of similar polycyclic ketones and quinones and their arylamino compounds can be used for the present procedure.

The implementation takes place according to the following scheme:

[Dye -] - CH ₂ - halogen + HX - SR

-> - [Dye -] - CH ₂ - X - S - R + hydrogen halide.

Here, X denotes an aromatic radical and R denotes an alkyl group.

It is advantageous to work in the presence of catalysts, as used in Friedel-Crafts synthesis, e.g. B. zinc chloride, ferric chloride. Aluminum chloride or boron fluorine id. The reaction can be carried out in the presence of a solvent and diluent carry out; then it is advantageous to use an excess of that used in each case for this purpose Sulphides. In some cases, the addition of a neutral salt, such as sodium chloride or sulfate, favorable, the reaction product being obtained in finely divided form.

Method of manufacture
of sulfur-containing dyes

Applicant:

Aniline & Soda Factory in Baden

Corporation,

Ludwigshafen / Rhine

Dr. Arnold Tartter, Lambsheim (Palatinate),
has been named as the inventor

In general, the reaction takes place at a low temperature; however, one works appropriately at temperatures around 100 ° C and above and continues heating until the evolution of hydrogen halide is finished. After removing the excess sulfide or solvent through Suction. Precipitation, distillation or steam distillation gives the respective end product, the for cleaning any neutral salt that may have been added and of catalysts with water or diluted Acids is aftertreated.

The products thus obtained can be used directly as dyes or by known methods, z. B. by heating with sulfuric acid or aryl sulfonic acid esters, previously in their sulfonium compounds convict. With a small molecular size of the dye, e.g. B. in thioindigo, the introduction is sufficient only one sulfonium group to obtain a water soluble product. Dyes made from larger molecules exist, such as. B. the copper phthalocyanine, but this requires two or several sulfonium groups.

The new sulfonium dyes can be used, for example, in textile dyeing and especially in Textile printing can be used in many ways.

It is already known to use phthalocyanines containing at least two halomethane groups with alkali salts to implement mercaptans and the sulfides obtained, if appropriate by known methods to be converted into tertiary sulfonium compounds. According to this process using thiophenols sulfonium compounds produced

«09 6SS / 38O

however, do not have a good fiber affinity and only have low water solubility. Against these dyes are the sulfonium compounds produced by the new process using thiophenol ethers Much more soluble in water and have an excellent affinity for fibers. The parts mentioned in the following examples are parts by weight.

example 1

25 parts of a mixture of tetrakis and pentakis - (chloromethyl) - copper phthalocyanine become 100 parts of methylphenylthioether gel, heated to 115 ° C. with stirring and at this temperature 10 parts of zinc chloride added to the reaction mixture in small portions within 2 to 3 hours. After heating for 8 hours, the mixture is allowed to cool and then the dye is precipitated with methanol. Man thus receives 33 parts of a blue dye powder, which is made from tetrakis and pentakis (methyl mercaptophenylmethyl) copper phthalocyanine consists.

30 parts of this dye are mixed with 250 parts of dimethyl sulfate at water bath temperature Stirred for 2 hours and after that. Cool with acetone failed. 43 parts of a blue dye are obtained, for example cotton from weakly antic or acetic acid solution in blue shades of good lightfastness.

If the corresponding derivatives are used instead of the chloromethyl derivative of copper phthalocyanine of nickel or iron phthalocyanine, dyes of greenish-blue tones are obtained, while the chloromethyl derivative of tetraphenyl copper phthalocyanine leads to a green dye.

Example 2

In a kneader, 250 parts of tetrakis (chloromethyl) copper phthalocyanine, 150 parts of sodium chloride, 100 parts of zinc chloride and 500 parts of methylphenyl thioether are mixed with a gradual increase in temperature. Hydrogen chloride begins to escape at around 50 ° C. After further slow heating to 100 to HO ⁰ C, the mixture is kept within this temperature range until the evolution of hydrogen chloride subsides, which takes several hours. The moist dye powder is then washed with methanol and water and dried. The dye obtained in this way (320 parts) is sparingly soluble in lower alcohols, but dissolves with a blue color in higher aromatic hydrocarbons, benzyl alcohol or dimethylformamide.

Anhydrous iron (III) chloride can also be used instead of zinc chloride.

150 parts of the dye obtained are suspended in 500 parts of dichlorobenzene and mixed with 250 parts of dimethyl sulfate with stirring, heated on the steam bath for some time. Then you fall with acetone, decanted off, rubbed again with acetone and filtered off with suction. This gives 190 parts of a blue one Dye.

The corresponding Manufacture sulfonium compounds that dye textiles in blue tones from formic acid solution. The tertiary sulfur compounds are processed into printing pastes and printed with them in the usual way For example, cotton batiste, linen or natural silk are obtained after drying and steaming blue prints of good lightfastness.

In a corresponding manner, the chloromethyl derivatives of metal-free phthalocyanines or of the aluminum phthalocyanine. This gives dyes of a slightly stronger green hue.

Example 3

In 75 parts of methylphenylthioether there are 15 parts of a thioindigo containing chloromethyl groups stirred in with a chlorine content of 11.6%. The mixture is heated to about 115 ° C. and held for that long at this temperature until the evolution of hydrogen chloride has ceased. Then the excess the thioether removed by distillation under reduced pressure. The dye thus obtained has a chlorine content of less than 0.5% and exists essentially of mono- (methyl mercaptophenylmethyl) thioindigo.

If the above reaction is carried out with the addition of 10 parts of zinc chloride, it goes significantly faster (you get the same dye in this case after about 6 to 8 hours Reaction time).

10 parts of the methyl mercaptophenylmethyl thioindigo obtained are heated with 75 parts of dimethyl sulfate with stirring for 75 minutes on the steam bath. The reaction product is precipitated by adding benzene, filtered off with suction and dried at low temperature. The yield consists of 12 parts of a water-soluble red-violet dye that is used for printing of cotton, linen, natural silk, acetate silk or polyamide fibers can be used.

Indigo and thioindigo derivatives containing chloromethyl groups can be reacted in a similar manner, such as B. the chloromethyl derivative of 4,4'-dimethyl-6,6'-dichlorothioindigo.

B e i s ρ i e 1 4

In a stirred vessel, 10 parts Tetrakischlormethyl) -Kobaltphthalocyanin mixed 5 parts of zinc chloride and 50 parts Äthylphenylsulfid and initially for 2 hours at 90 ° C, then for 6 hours at HO ⁰ C heated. Then one falls with ligroin, sucks off and washed with water. The yield is 12 parts of a dye which dissolves in dimethylformamide with a blue color.

The ethyl mercaptophenylmethyl cobalt phthalocyanine thus obtained is heated with dimethyl sulfate on a water bath, a tertiary sulfonium compound is obtained, dyes cotton from formic acid solution in blue tones.

Instead of ethylphenyl sulfide, for example 2- or 4- (methylmercapto) -toluene can be used with a similar result or use 2-chloro-1- (methylmercapto) -benzene.

Example

30 parts of a mixture of bis- and tris- (chloromethyl) pyranthrone and 10 parts of zinc chloride are added to 150 parts of methylphenyl sulfide and under

Stirring heated to 110 to 115 ° C for about 10 hours. It is allowed to cool and mixed with methanol, suction filtered, washed with hot water and dried. Alan receives so 39 parts of a reddish yellow dye with a sulfur content of 9.9% and a chlorine content of 0.8%.

20 parts of the mixture of bis- and tris- (methylmercaptophenylmethyl) pyranthrone thus obtained heated with 150 parts of dimethyl sulfate for some time on the steam bath and the sulfonium compound thus obtained then precipitated with acetone. In anticipation

Licher way can benzanthrones, dibenzanthrones, isodibenzanthrones containing chloromethyl groups or implement anthraquinone derivatives,

B e i s ρ i e 1 6

20 parts of tetrakis (chloromethyl) copper phthalocyanine and 12 parts of zinc chloride are used in 100 parts Methyl (o-methylphenyl) sulfide with thorough stirring heated to 100 to 110 ° C for about 12 hours. It is precipitated with acetone, filtered off with suction, washed with water and dried and thus obtain 25 parts of a blue dye. His sulfonium compound obtainable by heating with dimethyl sulfate dyes cotton from an acidic solution in blue tones.

Claims (1)

Claim: Process for the preparation of sulfur-containing dyes, characterized in that one Alkyl aryl sulfides with dyes containing halomethyl groups that differ from polynuclear Derive compounds with at least one} C =O or) C =N group, advantageously in the presence of such catalysts as are used in the Friedel-Crafts synthesis and, if appropriate, convert the products obtained into tertiary sulfonium compounds by known methods convicted. Considered publications:
German patent specification No. 812 945. When the application was announced, two staining tables were displayed. © 80S 638/380 '9 ·.