DE564770C - Process for the production of ester derivatives from Kuepen dyes - Google Patents

Description

Process for the production of ester derivatives from vat dyes The invention relates to a process for the preparation of ester derivatives of vat dyes.

You can prepare derivatives of vat dyes that one the vat dyes with a metal and chlorosulfuric acid or the like in the presence treated tertiary amines or equivalent substances.

The present process relates to the preparation of derivatives of Vat dyes from the action of a quaternary ammonium haloid that is produced by Obtained reaction between a tertiary organic base and an alkyl halide can be, on vat dyes in the presence of organic tertiary bases, a Metal and a product consisting of a tertiary organic base and a reagent, which can provide the sulfuric anhydride compound of the tertiary base, for example an alkyl chlorosulfonate, sulfuric acid monochloride (chlorosulfuric acid), oleum or Sulfur trioxide is formed.

You can use the quaternary ammonium halide in the presence of a tertiary bring organic base into reaction with a metal and form the resulting mixture add the vat dye. For this purpose one gives the product from a tertiary organic Base and a compound that is the sulfuric anhydride compound of the tertiary Can provide base, for example an alkyl chlorosulfonate, sulfuric acid monochloride (Chlorosulphuric acid), oleum or sulfur trioxide. The following is the invention described in some exemplary embodiments. All parts are parts by weight.

EXAMPLE i Parts of methylpyridinium iodide (prepared for example by adding 3.25 parts of iodomethyl to 1.8 parts of pyridine) are suspended in pyridine in a kettle and 45 parts of finely divided zinc are added with thorough stirring. 1.5 parts of dry indigo are then added to this mixture and the mixture is stirred vigorously.

If enough pyridine is used, a thick, but still workable pulp.

4.8 parts of the addition product are then added to the suspension, which was created by adding pyridine to methylchlorosulfonate. The crowd will stirred well and heated to 30 to 40 ° C. for a short time. The melt is then in the ordinary way worked up. For example, it can be made alkaline with caustic soda and the excess pyridine can be distilled off by steam. The residue in the vessel is then extracted with boiling water and the filtrate concentrated and chilled.

The resulting product can be used for dyeing and printing. Tissues, for example, can be padded and padded in the aqueous solution of the product the dye can be formed on the fiber by adding an acidic oxidizing agent will. In the case of indigo, the reaction appears to be as follows in front of you: The effective reagents in the reaction seem to be the sulfuric anhydride compounds of the tertiary organic bases used. These are formed when the methyl chlorosulfonate is added to the tertiary organic base.

Apparently the sulfuric anhydride compound has the tertiary Base, for example pyridine sulfuric anhydride (or in other words pyridine sulfur trioxide), the empirical formula C5 H5 N # S 03. The literature apparently relates on a body similar to anhydropyridine sulfuric acid and N-pyridine sulfonic acid Pyridinesulfuroanhydride.

Presumably the zinc reacts with the methylpyridinium iodide. After addition of the indigo, a reaction takes place and the melt turns red, apparently as a result the formation of a red compound of the dye, which when it is humid air is exposed, is converted into a yellow derivative of the dye. The end product after adding the product of pyridine and methylchlorosulfonate to the suspension The properties of the red substance and work-up come from the methylpyridine salt of the disulfuric acid ester of leucoindigo extremely close.

Example 2 4 parts of dimethoxydibenzanthrone and 3 parts of zinc become suspended in 28.5 parts of pyridine containing 4.3 parts of chloromethyl in a nitrogen atmosphere. The temperature of the mixture is slowly increased up to 75 ° C. At this temperature for example, the melt becomes deep blue and thickens considerably. The melt will Stirred for 5 to 10 minutes and then cooled to 20 °. Be at this temperature 8 parts of pyridine sulfur trioxide were added. The melt immediately receives a lively crimson color. The temperature is then increased to 55 ° for about 20 minutes and held at this temperature for% hour. The melt is then cooled, mixed with about 25o parts of a 5 ° 10% sodium carbonate solution and steamed distilled. When apparently all of the pyridine is removed, the liquid becomes filtered hot and the solid soluble derivative as a red precipitate from the Filtrates precipitated by the addition of common salt.

. Example 3 A well-stirred mixture of 50 parts of pyridine, xr parts of thioindigo and 8 parts of zinc dust is heated to 70 ° C. in a nitrogen atmosphere. Then 0.75 parts of ethyl bromide are added. The temperature is held at 70 ° for 20 minutes. The melt initially takes on a blood-red, then a green and finally a green-yellow color. It is cooled to 20 ° and 20 parts of pyridine sulfur trioxide are added. The temperature is then increased to 50 ° for an hour and a half and held at that temperature for 1112 hours. The final color of the melt is a greenish white. The melt is then mixed with 400 parts of water containing 30 parts of sodium carbonate and distilled with steam. After the pyridine has been removed, the mixture is filtered and the thioindigo derivative is allowed to crystallize out. Most of the product remaining in the mother liquor can be separated off, either by concentration in vacuo and subsequent crystallization, or by straining with common salt.

Example 4 6 parts of thioindigo, 2 parts of zinc and 3o parts of pyridine, which contain 1.4 parts of chloromethyl are heated to 60 ° C. for ten minutes. the The green-brown melt is then cooled to 20 °. At this temperature = Parts of dimethylaniline sulfur trioxide added. The temperature is increased to 50 ° and held at this temperature for 1/2 hour. The melt is then mixed with sodium carbonate, as described in Example 3, worked up.

Example- 5 zo parts dimethoxydibenzanthrone, 5 parts zinc and 25 parts Pyridine are stirred together in a nitrogen atmosphere. The melt will heated to 35 ° C. At this temperature, 0.75 parts of ethyl bromide are added. The temperature is then increased to 70 ° and at that temperature for 20 minutes held. During this time, the melt will turn blue and thick. She will then. on Cooled 20 ° and mixed with 12 parts of pyridine sulfur trioxide at this temperature. The melt immediately turns crimson, the temperature then increases over the course of = Increased to 75 ° for 5 minutes and held at 70 to 75 ° for 12 hours. she will then worked up with sodium carbonate as described in Example 2.

Example 6 5 parts of ethyl bromide, 15 parts of pyridine sulfur trioxide, 33 Parts of pyridine and zo parts of dimethoxydibenzanthrone are slowly reduced to 70 ° C good stirring. Then 6 parts of copper powder are slowly added in such a way that that the temperature does not exceed 75 °. When all the copper is added, will the temperature held at 75 ° for 30 minutes. The melt is then converted into sodium carbonate water poured and worked up according to the information in Example 2.

The procedure can of course be subject to various modifications, for example, other vat dyes can be used as starting materials. Other metals can be used in place of zinc, as can other bases than pyridine. Instead of methylchlorosulfonate, other bodies can be used, which sulfuric anhydride compounds of tertiary organic bases by reactions with suitable tertiary bases, for example other alkyl chlorosulfonates, Sulfuric acid monochloride (chlorosulfuric acid), oleum or sulfur trioxide.

Using a quaternary ammonium halide seems a smoother one Cause the course of the reaction, for example, a thinner reaction melt at low temperature or using smaller amounts of reagents can be obtained. However, the same advantages will not be necessary in every case achieved because the different vat dyes behave differently.

As indicated above, the method of the invention, if any appears desirable to be carried out in an inert atmosphere. This is not always necessary, but in those cases where that formed with the dye If the intermediate product is not stable, the inert atmosphere is often an advantage.

Among the dyes that can be used according to the invention, the following may be mentioned in particular: indigoid and thioindigoid dyes including Indigo and dichloro and dibromo indigo, including anthraquinone vat dyes Dibenzanthrone, indanthrone, flavanthrone and anthraquinone acridone dyes. The after Products obtainable by the present process are suitable for dyeing and printing of cotton, wool, natural and artificial silk and other animal or vegetable Fibers.

Some of the substances obtained by the present process are also soluble in solvents other than water, for example pyridine and alcohol.

The product is colored in a suitable solvent dissolved. The objects to be colored are immersed in the solution and then with an oxidizing bath, e.g. acidic ferric chloride solution, alkaline hypochlorite, Perborate or permanganate solution, treated as in the examples of British Patent specifications 245 587, 247 787 and 25 = 4g1 are given. Printing can for example can be carried out by methods set forth in British Patent Specification 245,587 are.

Claims (2)

PATENT CLAIMS: _. Process for the production of ester derivatives Vat dyes, characterized in that a quaternary dye is applied to a vat dye Ammonium halide in a tertiary organic base, a metal and the sulfur trioxide compound a tertiary base, expediently in an inert atmosphere, allowed to act. 2. Method according to claim =, characterized in that a metal is first applied allows a quaternary ammonium halide to act in a tertiary organic base, the resulting solution brings together with a vat dye and on the resulting Body lets the sulfur trioxide compound of a tertiary base act.