DE733700C - Process for the production of chromable dyes of the phthalein series - Google Patents

Description

Process for the production of chromable dyes of the phthalein series The subject of patent 692,708 is a process for the production of very clear chroinable Dyestuffs of the phthalein series, which is characterized in that i mole of i-oxybenzene-2, 4,5-tricarboxylic acid or its anhydride with a mol. Of an N-substituted m-aminophenol, which contains a reactive nuclear hydrogen atom in the p-position to the nitrogen atom, condensed, or .that i mol. of an N-substituted i-oxy-4 (q .'-amino-6'-oxybenzoyl) -benzene-a, 5-dicarboxylic acid or one mole of an N-substituted i-oxy-3- (d.'amino-6'-oxybenzoyl) -benzene-q., 6-dicarboxylic acid with 1 mol. Of an N-substituted m-aminophenol or with z mol. i, 3-Dioxybenzene-q.-carboxylic acid condensed.

The subject of patent 732 041 is a method of manufacture of dyes of the phthalein series, which is characterized in that one in place of i-oxybenzene-2, q., 5-tricarboxylic acid, or its anhydride or the benzoylbenzoic acids from i mol. i-oxybenzene-2, 4th, 5-tricarboxylic acid and i mol. of an N-substituted m-Aminophenols the isomeric i-oxybenzene-2, 5, 6-tricarboxylic acid or its anhydride or the benzoylbenzoic acids from i-mole. i-Oxybenz.o1-2, 5, 6-tricarboxylic acid and i mole of an N-substituted m-aminophenol used.

Subject of the patent . 693 9'f2 is a process for the production of very clear, soluble dyes of the phthalein series, which is characterized in that i mol. I-oxybenzene-2,4,5-tricarboxylic acid or the equivalent amount of the corresponding acid anhydride with 2 mol. I , 3-Dioxybenzene-.4-carboxylic acid or 2 mol. Of an m-dioxy compound, which has a reactive nuclear hydrogen atom and can contain halogen atoms, condensed and the non-halogenated dyes optionally halogenated.

It has now been found that very clear, chromable dyes of the phthalein series are obtained if one mole of a benzoylbenzoic acid obtained by condensation of one mole of i-oxybenzene-2, 4, 5-tricarboxylic acid or i-oxybenzene-2, 5, 6-tricarboxylic acid or its anhydrides with one mole of an m-dioxy compound which has a reactive nuclear hydrogen atom and can contain halogen atoms, with one mole of i, 3-dioxybenzene-4-carboxylic acid or one mole of one m-Dioxy compound, which has a reactive nuclear hydrogen atom and may contain halogen atoms, condenses and the non-halogenated dyes optionally halogenated. When using, for example, i, 3-dioxybenzene, the benzoylbenzoic acids which are reacted have the following composition: or are isomer mixtures of these benzoylbenzoic acids.

The condensation of the oxybenzenetricarboxylic acids or their anhydrides with an m-dioxy compound containing a reactive nuclear hydrogen atom can be carried out at a temperature of about 13o to 15o ° C, with the Reaction components react with one another essentially with i mole each. Is the Condensation at higher temperatures advanced to the corresponding phthalein dye, so can the benzoylbenzoic acid by treating the resulting dye for one hour can be obtained with about 8oo% sodium hydroxide solution at about 150 ° C.

The new dyes color the animal fiber from acid bath in very clear tones. The fastness properties of the dyeings are enhanced by re-chrome plating much improved. The dyes are also ideal for chrome printing on vegetable fibers, such as cotton and rayon. The colorations of the new dyes stand out from colorations of known analog phthalein dyes for their production Phthalic acid has been used due to better sea water fastness and greater clarity of the shade.

Examples i. 16 parts by weight of i-oxy-4- (4 ', 6'-dioxybenzoyl) -benzene-2, 5-dicarboxylic acid or i-oxy-3- (4, 6 @ -dioxybenzoyl) -benzene-4, 6-dicarboxylic acid (obtainable by condensation of i-oxybenzene-2, 4, 5-tricarboxylic acid or its anhydride with i, 3-dioxybenzene at about 140 ° C. or by treating the dye obtainable according to example i of patent 693 942 with about 7o to 8oo /% sodium hydroxide solution at about 15o ° C, until a sample dissolved in water only shows pale yellow color) and 71/2 parts by weight of i, 2, 3-trioxybenzene are melted with exclusion of air and with stirring for 4 hours at 16o to 17o ° C. The pulverized melt is dissolved in 5% sodium carbonate solution, filtered and the red solution is acidified at boiling hot with dilute hydrochloric acid until the reaction is weakly Congo acid. After standing for several hours, the precipitated dye is filtered off with suction, washed several times with water and dried. The dye presumably has the composition or represents a mixture of these two isomers. It dissolves in sodium carbonate or sodium carbonate alkaline solution with red, in dilute sodium hydroxide solution with green color. He dyes wool from an acid bath in brownish-red shades. The chromed coloration shows gray to deep black tones, depending on the strength of the coloration, which have significantly increased in authenticity compared to the non-chromed coloration.

2.4o parts by weight of i-oxy-4- (4 ', 6'-dioxybenzoyl) -benzene-2,5-dicarboxylic acid or i-oxy-3- (4', 6'-dioxybenzoyl) -benzene-4, 6-dicarboxylic acid (cf. Example i) and 20 parts by weight of i, 3-dioxynaphthalene are heated to 150 to 160 ° C. for 4 hours. The powdered melt is dissolved in sodium bicarbonate solution and the resulting solution is boiled with about one part by weight of animal charcoal for half an hour. The dye is precipitated from the filtered yellow-red solution at the boiling point using dilute hydrochloric acid. After it has completely cooled down, it is deposited as usual. For further purification it can be recrystallized from a lot of glacial acetic acid or dioxane. The dye is a yellow-red, indistinctly crystalline powder and probably has the following composition: or is a mixture of these two isomers. It dissolves in sodium bicarbonate solution with a yellow-red color and yellow fluorescence. Acid bath dyes wool in clear, golden-yellow tones. The chromed coloration is brown and shows greatly improved fastness properties. , 3. 24 parts by weight of i-oxy-4- (4 ', 6' -, dioxybenzoyl) -benzene-2, 5-dicarboxylic acid or i-oxy-3- (4 ';6'-dioxybenzoyl) -benzene-4, 6- Dicarboxylic acid (see Example i), iol / 2 parts by weight of i, 3, 5-trioxybenzene and 23 parts by weight of i-methylbenzene-4-sulfonic acid are heated to between 120 and 130 ° C. for 3 to 4 hours. The pulverized melt is stirred with about 100 parts of water and the dye is filtered off with suction. ! Ulan dissolves it in sodium carbonate solution, filtered, boiled the red solution with one part by weight of animal charcoal, filtered and precipitated the dye from the cold solution with dilute hydrochloric acid. He dyes wool from acid baths orange-yellow. After chrome plating, brown, much more genuine colorations are obtained.

4. 95 parts by weight of i-Oxy-4- (3 ', 5'-dibromo-4', 6'-dioxybenzoyl) -benzene-2, 5-dicarboxylic acid or i-OxY-3- (3 ', 5' = dibromo -4, 6'-dioxybenzoyl) -benzene-4, 6-dicarboxylic acid (obtainable from the benzoylbenzoic acids mentioned in Example r as starting compounds by bromination in ethyl alcohol with the required amount of bromine), 3o parts by weight i, 2; 3-Trioxybenzene and 150 parts by weight of i-methylbenzene-4-sulfonic acid are fused at 130.degree. C. to 130.degree. C. for hours in the absence of air. The cooled, pulverized melt is mixed with 1,000 parts of water and the dye is filtered off with suction. The brown-black residue is dissolved in sodium carbonate solution, filtered and the dye is precipitated with dilute hydrochloric acid. For further purification it can be recrystallized from 50 ° acetic acid. The dye presumably has the following composition: or is a mixture of these two isomers. It dyes wool from an acid bath brown-red. The color is blackened by re-chrome plating and its fastness properties are significantly improved.

5. 32 parts by weight of i-oxy-q .- (4,6'-dioxybenzoyl) -benzene-2, 5 = dicarboxylic acid or i Oxy-3- (4, 6'-dioxybenzoyl) -benzene-4, 6-dicarboxylic acid (see. Example i) and 16 parts by weight i, 3-Dioxy-4-chlorobenzene are q. Melted for hours at 16o to 17o ° C. the Work-up takes place as in the example described above. The dye stains Acid bath wool orange-yellow. The chromed coloration is brown and essential real.

6. 22 parts by weight of the dye shown in Example 2 are distributed in 2o parts by weight of ethyl alcohol and stirring at 20 to 30 ° C 33 parts by weight of bromine were added dropwise. The originally yellow dye goes here with red color gradually in solution. 5 parts by weight are added to the solution Sodium bisulfite liquor and excess dilute sodium carbonate solution and distilled remove the ethyl alcohol with steam. A clear one emerges. red solution that at Add dilute hydrochloric acid to the dye until the lacquer acidic reaction occurs lets fall out as a red precipitate. It is deposited in the usual way. the Solution in concentrated sulfuric acid is red-orange. Wool is made from an acid bath colored bright red. The chromium-plated color is much more genuine.

7. 32 parts by weight of i-oxy-d .- (4, 6'-dioxybenzovl) -benzene-2, 5-dicarboxylic acid or i Oxy-3- (4. ', 6'-dioxybenzoyl) -benzene-4, 6-dicarboxylic acid (see. Example i) fused with 2o parts by weight of i, 3-dioxybenzene for 4 to 5 hours at i 80 ° C. The yellow melt is pulverized after cooling and in dilute sodium hydroxide solution solved. The solution is heated to boiling and acidified with dilute hydrochloric acid. After cooling, the yellow precipitate is filtered off with suction, washed neutral and dried. If necessary, you can dissolve the dye from aqueous ethyl alcohol. By dissolving The dye is easily obtained in dilute alkalis and evaporation of the solution soluble sodium salt.

The dye turns the animal fibers from acid baths yellow. By After homing, the fastness properties are significantly improved.

Similar dyes are obtained if, instead of i, 3-dioxybenzene other m-dioxy compounds with reactive hydrogen atoms are used, and i, 3-Dioxy-4-chloro- 'or -4-bromobenzene and i, 3-Dioxybenzolmonomethyläther.

B. In the bromination of the dye of the above example in Glacial acetic acid as described in Examples -2 and 3 of Patent 693,942 Process, depending on the amount of bromine used, different dyes are obtained, which are similar to the dyes described in the examples mentioned.

9. 32 parts by weight of i-oxy-d .- (4, 6'-dioxybenzoyl) -benzene-2, 5-dicarboxylic acid or i-oxy-3- (a. ', 6'-dioxybenzoyl) -benzene-4, 6- dicarboxylic acid (see Example i) and 17 parts by weight of i, 3-dioxybenzene-4-carboxylic acid are added to about 20 parts by weight of concentrated sulfuric acid and heated to 70 to 80 ° C. for 6 hours with stirring. The mixture obtained is then added to about 10 part by weight of water, saturated with sodium chloride and the yellow precipitate is filtered off with suction. To remove any remaining unchanged benzoylbenzoic acid, the yellow residue is stirred with about 25 parts by weight of slaked lime and 250 parts by weight of water and boiled. After cooling, the sparingly soluble calcium salt of the dye is filtered off with suction, washed with water and the yellow dye is released from it with dilute acids. In the case of condensation, sulfonation takes place at the same time. The dye dyes wool from an acid bath yellow. The authenticity properties are considerably improved by re-chrome plating.

When afterbrominating in alcohol or glacial acetic acid, dyes are obtained, the hue of which shifts increasingly towards red with the number of bromine atoms taken up.

10. 32 parts by weight of i-oxy-3- (4,6'-dioxybenzoyl) -benzene-2,6-dicarboxylic acid or i Oxy-6- (4. ', 6'-dioxybenzoyl) -benzene-2, 5-dicarboxylic acid (available from alkaline cleavage of the symmetrical phthalein dye from 2 mol. 1,3-dioxybenzene and i mol. i-oxybenzene-2, 5, 6-tricarboxylic acid, colorless crystalline compound, which decomposes at about 265 ° C with foaming and red color) and 32 parts by weight 1,3-Dioxy-4-chlorobenzene are stirred at i8o to 19o ° C for 3 to 4 hours merged. The pulverized melt is extracted while hot with 1000 parts of water and the residue dissolved in dilute sodium carbonate solution. From the possibly filtered red-yellow solution, the dye is precipitated with dilute mineral acids.

The dye is a yellow powder. According to the way it is presented, it has the following composition: or is a mixture of these two isomers. It colors the animal fibers from acid baths in bright yellow shades. The authenticity properties are significantly improved by re-chrome plating.

Claims (1)

PATENT CLAIM: Modification of the process for the production of chromable Dyes of the phthalein series according to patent 692 708 and its additional patents 693 942 and 732 041, characterized in that i mol. Of a benzoylbenzoic acid, that by condensation of i mol. i - oxybenzene-2, 4, 5-tricarboxylic acid or i-oxybenzene = 2, 5, 6-tricarboxylic acid or its anhydrides with one mole of an m-dioxy compound, which has a reactive nuclear hydrogen atom, is available and halogen atoms may contain, with i mole of 1, 3-dioxybenzene-4-carboxylic acid or i mole of an m-dioxy compound, which has a reactive nuclear hydrogen atom and contain halogen atoms can be condensed and the non-halogenated dyes optionally halogenated.