DE515328C - Process for the preparation of halogen-containing cow dyes - Google Patents

Description

Process for the preparation of halogen-containing vat dyes. Addition to the patent q.99169. anthrone and isodibenzanthrone series, in which dibenzanthrone or isodibenzanthrone or their derivatives are treated in the presence of chlorosulfonic acid and suitable metalloids or compounds of these with bromine or bromine-releasing agents. In the additional patent 51o 6oo it has also been shown that particularly boiling-fast dyes are obtained if the reaction is carried out at temperatures below about 50 ' .

It has now been found that the method of the aforementioned Inventions particularly lightfast dyes obtained, provided that the starting materials are chlorine-free are practically free of chlorine when exposed to bromine or bromine donating agents in any acidic medium in the presence of Catalysts containing metals or their compounds, e.g. B. those that Containing arsenic, antimony, nickel, mercury, manganese or iron. For example, dibenzanthrone is obtained in chlorosulfonic acid using of mercury as a catalyst when using bromine in an amount equal to 4 atoms Bromine corresponds to 1 mol. Dibenzanthrone, and a reaction temperature of 65 ° practically chlorine-free tribromodibenzanthrone. The corresponding tribromoisodibenzanthrone can be used analogously represent. In general, it can also be said here that one is at a lower temperature very boiling reaction products of lower bromine content are obtained, while with higher temperature higher brominated products can be obtained. The described in the Way available brominated products are dyes that have a particularly high level Have light and weather fastness. They dye cotton from purple to blue green-blue vat in green-tinged navy-blue to violet tones, which are each more green-tinged: than the colors of those shown with metalloid carriers in an analogous manner Bromine dyes.

In general, when representing mono-, di-, tri- and tetrabromo derivatives with the amount of bromine that corresponds to the number of in the starting product to be introduced corresponds to bromine atoms, or a small excess of bromine from, while the preparation of penta and hexabromo derivatives mostly requires a greater excess of bromine and a higher temperature. The yields in the bromination are approximately quantitative; the dyes are in their form Pastes, i.e. immediately in a usable form, received. They come off if they do belong to the dibenzanthrone series, in concentrated sulfuric acid in general with purple color; the dyes of the isodibenzanthrone series dissolve in concentrated form Sulfuric acid with green color. Optionally, the raw dyes can according to the usual methods, e.g. B. by crystallization from sulfuric acid or from high-boiling organic solvents, such as nitrobenzene, or by treatment with oxidizing agents, z. B. by treating their aqueous paste with hypachlorite; getting cleaned.

When using chlorine or iodine derivatives of dibenzanthrone or Isodibenzanthrons are naturally obtained as starting materials with mixed substitutes Halogen derivatives. Chlorosulfonic acid can be used as a solvent in many cases in the process be completely or partially replaced by oleum or sulfuric acid.

The bromine derivatives prepared according to the present process Dibenzanthrons or isodibenzanthrons can be incorporated into leuco preparations according to known methods or leucoesters are transferred.

The reaction products can be due to their considerable reactivity also serve as intermediates for the preparation of new dyes. example i 46 parts of pure isodibenzanthrone are dissolved in 46o parts of chlorosulfonic acid. After adding 1.2 parts of manganese and 9 parts of bromine, the temperature is increased 25 to 30 ', stirring until all the bromine has been absorbed. After cooling down it is diluted with concentrated sulfuric acid, poured into water and filtered off with suction. That obtained, monobromoisodibenzanthrone, a blue-violet paste, dried a violet Powder "dissolves in concentrated sulfuric acid with a green color and dyes cotton from a blue vat in extremely clear and strong tones of very good authenticity: Instead of manganese, other metallic catalysts, e.g. B. mercury, arsenic, Bismuth or iron.

The reaction can also take place at a lower temperature; z. B. at - 5 to o ', to be carried out.

When using pure dibenzanthrone instead of isodibenzanthron one obtains monobromodibenzanthrone, a dark blue coloring agent. example 2 46 parts of pure dibenzanthrone are dissolved in 46o parts of chlorosulfonic acid with stirring solved. 4 parts of arsenic are introduced into the solution obtained and 17 parts of bromine are left flow in and increase the temperature slowly to 5o to 6o 'until all the bromine is absorbed is then allowed to cool and isolate the dye in the usual way. This here obtained dibromodibenzanthrone, a violet-blue paste, dried a dark blue Powder, dissolves in concentrated sulfuric acid with purple color and stains Cotton from a violet-blue vat in strong, clear, navy blue colors from -Excellent light and weather fastness.

The dye can, if appropriate, be purified by customary methods will.

Instead of arsenic, other metallic catalysts, e.g. B. iron or Nickel, can be added: When using more bromine, e.g. B. from 24 to 27 parts, this dibromine dye can also be used at lower temperatures, e.g. at 2o to 30 °, being represented.

A dibromo derivative is obtained from isodibenzanthrone in an analogous manner, which dissolves in concentrated sulfuric acid with a green color and turns blue-violet, strong on cotton from a blue vat; delivers clear dyeings of excellent lightfastness. Example 3. 46 parts of pure isodibenzanthrone are dissolved in 46o parts of chlorosulfonic acid. 3 parts of mercury and 35 parts of bromine are added to this solution with stirring, the temperature is slowly increased to 60 'and then kept at between 0 and 65' until all the bromine has been absorbed. After cooling, you work up in the usual way. The dye obtained in the form of a violet paste, a tribromoisodibenzanthrone, is practically chlorine-free and, when dried, is a violet-blue powder that dissolves in concentrated sulfuric acid with a purely green color. On cotton, the dye gives strong, clear violet dyeings of very good fastness, in particular excellent fastness to light and weather.

Instead of mercury, other metallic carriers can be used.

A tribromo derivative is obtained from dibenzanthrone in an analogous manner, which dissolves in concentrated sulfuric acid with a purple color and on cotton from the violet-blue vat supplies navy blue, exquisitely real colors. example 446 parts of dibenzanthrone are dissolved in 46o parts of chlorosulfonic acid with stirring. After adding 4 parts of iron sulfate and 45 parts Bromine is increased the temperature to 6o to 7o ', until most of the bromine has been absorbed. Of the The dye obtained is isolated as in Example i after cooling. That in excellent Yield and purity obtained tetrabromodibenzanthrone, a purple-blue paste, dried a dark blue powder, dissolves in concentrated sulfuric acid with violet color and dyes cotton from violet-tinged blue vat in navy blue Shades of very good fastness, especially excellent light and weather fastness.

Manganese, arsenic or other metallic materials can also be used instead of iron Use catalysts.

A tetrabromo derivative is obtained in an analogous manner from isodibenzanthrone, which dissolves in sulfuric acid with a green color and dyes cotton from a blue vat excellently true blue-violet. EXAMPLE 5 46 parts of dibenzanthrone are dissolved in q60 parts of chlorosulfonic acid with stirring, 2 parts of antimony and 2 parts of manganese are added to this solution and 60 parts of bromine are allowed to flow in at normal temperature, then the temperature is increased to 65 ' and is kept at 65 to 7o' until most of the bromine has been absorbed. Then allowed to cool and isolate the dye according to Example i. The pentabromodibenzanthrone obtained, a violet-blue paste, a dark blue powder when dry, dissolves in concentrated sulfuric acid with a violet color and, from a blue vat on cotton, gives navy blue dyeings of very good fastness.

If larger amounts of bromine are used, hexabromium or higher is obtained brominated dibenzanthrones.

Instead of antimony and manganese, other metallic catalysts can be used or apply several of these.

Pentabromo-, hexabromo- and higher brominated derivatives. These dissolve in concentrated sulfuric acid green color and color the vegetable fiber from the blue vat in more or less bluish purple tones.

EXAMPLE 6 46'reile dibenzanthrone is dissolved in 4.6o parts of monohydrate with stirring, q is added. Add antimony and 27 parts bromine and heat slowly to 6o to 70 ' until all the bromine has been absorbed, then let it cool down and work up as usual. The bromodibenzanthrone obtained, a violet paste, dried a violet-blue powder, dissolves in concentrated sulfuric acid with a violet color and gives violet-blue dyeings of very good fastness on cotton from a violet vat.

Instead of monohydrate, oleum or phosphoric acid can also be used as Solvents or melting of metal chlorides, their melting temperatures through suitable additives can be reduced.

Other metals can represent antimony. Compounds of this or of antimony can also be added. EXAMPLE 7 The dye obtained from dioxydibenzanthrone by alkylation with p-toluenesulfonic acid chloroethyl ester is dissolved in chlorosulfonic acid and brominated at 60 'in the presence of antimony. The dye obtained dyes cotton from a blue vat in green-blue shades of very good fastness. Example 8 53 parts of a dichloroisodibenzanthrone obtainable from pure isodibenzanthrone by treatment with sulfuryl chloride are dissolved in 500 parts of chlorosulfonic acid with stirring. After adding q. 25 parts of bromine are added to parts of antimony, the temperature is slowly increased to 65 to 70 ° and the mixture is stirred at this temperature until most of the bromine has been absorbed. The dye is isolated according to Example i. The resulting reaction product containing chlorine and bromine, a violet paste, a blue-violet powder when dry, dissolves in concentrated sulfuric acid with a green color and gives blue-violet, strong, clear dyeings of good fastness on cotton from a blue vat.

Dibenzanthrones are obtained in an analogous manner from low-chlorinated dibenzanthrones Chlorobromo derivatives. Treats ioddibenzanthron, available from dibenzanthron by treating with iodine in monohydrate, at ordinary temperature in the presence of metallic catalysts with bromine, one obtains bromo iododibenzanthrones which Cotton from a blue vat in greenish navy blue, clear, strong tones of excellent fastness, especially excellent lightfastness, dye.

The bromoiodisodibenzanthrones shown in the same way provide strong, violet-tinged dark blue colors. EXAMPLE g 35 parts of bromine are dissolved in 500 parts of chlorosulfonic acid at ordinary temperature with stirring, then q. Parts of antimony and 46 parts of pure dibenzanthrone in the solution, warmed slowly to 60 'and held at this temperature until most of the bromine has been absorbed. After cooling, it is diluted with '23o parts' of concentrated sulfuric acid, poured into water, boiled briefly and suctioned off while hot.' If necessary, it is washed with dilute soda solution and then with hot water. The dye obtained, a tribromodibenzanthrone, is Obtained as a paste or dried and has the same properties as the dye described in Example 3, Paragraph 3.

The isodibenzanthrone derivative shown in an analogous manner dyes cotton from a blue vat in clear, extremely genuine, blue-violet tones. Example 1o 4.6o Parts of pure dibenzanthrone are converted into 46oo at ordinary temperature while stirring Parts of chlorosulfonic acid dissolved. Then add q.o parts of antimony and let it go slowly 27o parts of bromine flow in, stir for a few hours at ordinary temperature, then heated to 35 to 40 'and held at this temperature until the main amount of the applied bromine is used up. After cooling, the reaction mixture will diluted with about 2,000 parts of concentrated sulfuric acid, poured into ice water, briefly boiled, vacuumed and, after possibly washing through, with diluted soda solution washed neutral. The dye obtained in excellent yield, according to the analysis a dibromodibenzanthrone,, dissolves in concentrated sulfuric acid with violet Color and dye cotton from a blue vat in strong navy blue tones of excellent quality Authenticity.

In an analogous manner, when using larger amounts of bromine and Increase the reaction temperature to 45 to 5o 'tri-, tetra- and higher brominated Dibenzanthrones with excellent dyeing and fastness properties.

Color the bromisodibenzanthrones shown in the corresponding manner Cotton in blue-violet, clear tones of excellent authenticity.

Claims (1)

PATENT CLAIM: Further development of the process of the main patent 499 169 and the additional patent 51o 6oo, characterized in that dibenzanthrone or isodibenzanthrone or its derivatives in any acidic medium Presence of catalysts containing metals or their compounds with Treated with bromine or bromine-releasing agents.