CH440509A - Process for the preparation of pyrimidine dyes - Google Patents

Description

  

  Process for the preparation of pyrimidine dyes The present invention relates to a process for the preparation of water-soluble dyes containing at least one trihalogenated pyrimidine ring, which consists in that organic compounds which carry at least two optionally monosubstituted amino groups are on the one hand with a 2,4, 5,6-tetrahalopyrimidine and on the other hand with a phthalocyanine polysulfonic acid chloride sets.



  Of the organic compounds which carry at least two optionally monosubstituted amino groups, diamino compounds of the aromatic series, such as.

   B. 1,3- or 1,4-diaminobenzene, 1,3- or 1,4-diaminobenzene- 6-carboxylic acid or -6-sulfonic acid, 4,4'-diamino-1,1'-diphenyl-5- sulfonic acid or -2,2'-disulfonic acid, 4,4'-diamino-stilbene-2,2'-disulfonic acid, 2,6-diamino-naphthalene-4,8-disulfonic acid.



  Suitable 2,4,5,6-tetrahalopyrimidines are 2,4,5,6-tetrabromopyrimidine and in particular 2,4,5,6-tetra-chloropyrimidine. Of the phthalocyanine polysulfonic acid chlorides to be used, the di-, tri- and tetrasulfonic acid chloride of metal-free phthalocyanine or metal phthalocyanines, eg. B. of nickel phthalocyanine and preferably copper phthalocyanine.

   The sulfonic acid chloride groups are bound directly to the benzene nuclei in the 3- or 4-position.



  The reaction with the 2,4,5,6-tetrahalopyrimidine is preferably carried out in an aqueous, aqueous-organic or organic medium. The halide can be used as such in concentrated form or dissolved in an organic solvent. Particularly suitable solvents for the tetrahalopyrimidines are acetone, benzene, chlorobenzene and toluene.



  The reaction temperature preferably varies between 20 and 100 C. If temperatures higher than about 40 have to be used, it is advisable, with regard to the steam volatility of the tetrahalopyrimidines, to work in closed vessels optionally equipped with a reflux condenser.



  The reaction can be carried out in a weakly alkaline, neutral to weakly acidic medium, preferably in the pi3 range from 3 to 7. To neutralize the resulting one equivalent of hydrogen halide, either an acid-binding agent such as sodium acetate is added to the reaction solution at the beginning, or sodium or potassium carbonate or bicarbonate in solid, powdered form or as a small portion is added during the reaction concentrated aqueous solution added.

    Aqueous solutions of sodium or potassium hydroxide are also suitable as neutralizing agents. The addition of small amounts of a wetting agent or emulsifier to the reaction mixture can accelerate the conversion reaction.



  The reaction is conducted so that only one halogen atom of the 2,4,5,6-tetrahalogenopyrimidine reacts with an exchangeable hydrogen atom of one of the optionally monosubstituted amino groups.



  After the reaction has ended, the product obtained can be used without being isolated from the reaction mass; However, it is often more advantageous for the quality of the dyes to be produced to precipitate it out of its ner optionally previously neutralized solution or suspension with a suitable agent, e.g. B. with sodium or potassium chloride or with an acid if the reaction is carried out in an aqueous or wasserig-organic medium, then suck off, wash, z. B. with water or brine, and optionally to dry.



  The condensation with a phthalocyanine polysulfonic acid chloride is preferably carried out in an aqueous medium and with the addition of an acid-binding agent, the reaction mixture being stirred after the condensation until the excess sulfonic acid chloride groups in sulfonic acid groups and / or, if in the presence of Ammonia or an amine works, are converted into sulfonic acid amide groups. Advantageous condensation conditions are z. B.

   Temperatures from -5 to 50 C, preferably from 0 to 20 C, and pH values from 5 to B.



  The finished dyes are salted out with sodium or potassium chloride from the optionally neutralized condensation solution or suspension, or precipitated with acid, then filtered off with suction, washed neutral with a salt brine and dried.



  The water-soluble dyes carrying at least one trihalogen pyrimidylamino group are suitable for dyeing, padding and printing fibers of animal origin, eg. B. wool, silk, synthetic polyamide fibers, e.g. B. nylon, leather, cellulose fibers, e.g. B. cotton, Lei NEN and regenerated cellulose fibers, z. B. Viskosereyon, Kupferreyon, rayon and from Ge mix and / or structures made of these fibers.

   The optimal application conditions vary depending on the type of fiber and the dyes used. Animal fibers and syntheti cal polyamide fibers will preferably be dyed in an acidic, neutral or weakly alkaline medium and printed or fixed, eg. B. in the presence of acetic acid, formic acid, sulfuric acid, ammonium sulfate, sodium metaphosphate, etc. You can also in the presence of leveling agents such.

   B. polyoxyethylated fatty amines or mixtures of the same with alkyl polyglycol ethers, color acetic acid to neutral and at the end of the coloration the bath by adding small amounts of an alkaline agent such. B. ammonia, sodium bicarbonate, soda, etc., or Ver compounds which react alkaline in the heat, z. B. hexamethylenetetramine, urea, up to neutral len or weakly alkaline reaction. This is followed by thorough rinsing and, if necessary, acidified with a little acetic acid.



  When dyeing and printing fibers and fabrics of animal origin, fibers and structures made of synthetic polyamide often result in a less pronounced bond between the dye molecule and the fiber, depending on the reactivity of the dye, as the dyes are partly thanks to their acidic character Have an affinity for the fiber.



  The dyeing, padding and printing or fixing of the dyes on cellulose fibers is advantageously carried out in an alkaline medium, e.g. B. in the presence of sodium bicarbonate, sodium carbonate, sodium hydroxide solution, potassium hydroxide solution, sodium metasilicate, sodium borate, trisodium phosphate, ammonia, etc. To avoid reduction phenomena, mild oxidants such as 1-nitrobenzene are often advantageous when dyeing, padding or printing the fibers. 3-sulfonic acid sodium, added.

   In the case of cellulose fibers, too, the dyes are usually fixed in the heat.



  The dyeings and prints on cellulose fibers were particularly notable for their excellent wet fastness properties. These are based on the formation of a stable chemical bond between the dye molecule and the cellulose molecule. Often not all of the dye takes part in the chemical reaction with the fiber.

   The proportion of the unreacted dye is removed from the fiber in these cases by suitable operations, such as rinsing and / or soaps, possibly using higher temperatures, with synthetic detergents, such as. B. alkylarylsulfonates, sodium lauryl sulfate, sodium lauryl polyglycol ether sulfate and alkyl polyglycol ethers and mono- and dialkyl phenyl polyglycol ethers, find use.



  In the following example, the parts mean parts by weight, the percentages are percentages by weight and the temperatures are given in degrees Celsius.



  <I> Example </I> 54 parts of 1,3-diaminobenzene are dissolved in 600 parts of water. 65 parts of sodium bicarbonate and 110 parts of 2,4,5,6-tetrachloropyrimidine are added and the mixture is stirred vigorously for 48 hours at room temperature. The precipitate is then filtered off and washed neutral with water. The moist goods are dried at 60 in a vacuum and then finely ground.



  29 parts of this product are mixed in 500 parts of ice water. A moist paste of copper phthalocyanine - 3,3 ', 3 ", 3"' - tetrasulfonic acid chloride, prepared by sulfochlorinating 57.6 parts of copper phthalocyanine, is introduced, the temperature being kept at 0-5. Ammonia solution is then slowly dripped into the well-stirred mixture until a pH of 7.5 is reached.

   The mass is stirred for a further 3 hours at a temperature increasing from 0 to about 15-20 and the pH is kept at 7.5-8 by the gradual addition of ammonia solution. 30 parts of 25% ammonia solution are then added and stirring is continued overnight at room temperature.

   The next day enough 30% sodium hydroxide solution is added until the dye has completely dissolved. The solution is filtered. The dye is separated from the filtrate by adding salt. It is filtered off with suction, washed with saline solution and dried at 80 in a vacuum.

    The result is a dark blue powder that dissolves in water with a turquoise blue color and produces light and wet-fast tones on wool, synthetic polyamide fibers, natural or regenerated cellulose.



  <I> Dyeing instructions </I> 3 parts of the dye obtained according to the above description are dissolved in 100 parts of water to which 1U part of urea is added. 30 parts of a 10% strength sodium carbonate solution and 0.5 part of sodium 1-nitrobenzene-3-sulfonic acid are also added.

   A cellular wool fabric is impregnated with this solution in such a way that it absorbs 75% of its weight in dye solution. After drying, the fabric is dampened for 5 to 10 minutes at 102, then rinsed and soaped at the boil for 15 minutes. After drying, a turquoise-blue dyeing of very good lightfastness and washfastness is obtained.

 

Claims (1)

A process for the preparation of at least one trihalogenated pyrimidine ring containing water-soluble dyes, characterized in that organic compounds which carry at least two optionally monosubstituted amino groups are mixed with a 2,4,5,6-tetrahalopyrimidine and a phthalocyanine polysulfonic acid chloride implements. SUB-CLAIM Process according to patent claim, characterized in that the 2,4,5,6-tetrachloropyrimidine is used as the 2,4,5,6-tetrahalopyrimidine.