DE1250830B - Process for the preparation of bistriazinylaminostilbene series whitening agents - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY Int. Cl .:

C07d

GERMAN

PATENT OFFICE

EDITORIAL

CO 7 D,; / 25 1 6 8

. German class .12 ρ-10/05 M, γ

-Number: 1 250 830 ■. .

File number: F 45615 IV d / 12 ρ

Filing date: March 24, 1965 '

Date of deployment: September 28, 1967

·. The invention relates to a method zur.Herstellung of Aufliellungsmittel der Bistriazinvlan'iinostilben- ' Series by condensation "of cyanuric chloride me water-soluble salts of aromatic amines or aromatic aminosulfonic acids in a molar ratio of 1: 1.5 in aqueous medium that of organic solvents free is. with subsequent reaction of the condensation product formed with 4.4'-diaminosilbene-2-.2 '-' disulfonic acid or their salts in a molar ratio of 2: 1 and, if necessary, under further ίο Implementation of the resulting reaction product with amines or amine salts in a molar ratio of 1: 2: that The method is characterized in that the con ·. Densation of the cyanuric chloride with the water-soluble ones Salts of the aromatic amines or the aromatic aminosulfonic acids in the first stage in the absence acid-binding agent takes place. ■.

Water-soluble salts of aromatic amines or aromatic aminosulfonic acids which are suitable for the condensation with cyanuric chloride in the first stage include, for example, the chlorohydrates of aniline, chloroanilines and toluidines or the alkali salts of sulfanilic acid and m'ctanilic acid. ■

The implementation required for the production of Aufliellungsmittel of the Bistriazinylaminostilben-Rcihe ' z'ung of the condensation product formed in the first stage with 4,4'-diaminostilbene-2,2'-disulfonic acid or their salts can then be done in the usual way: The same also applies to any further implementation of the resulting Reaction product with amines or amine salts; as amines for this purpose come into consideration, for example: methylamine, Dimethylamine, ethylamine, diethylamine, monoethanolamine, Diethanolainine, N-methylethanolamine, Tauriii, N-methyltaurine, morpholine, piperidine, pyrrolidine, Aniline, chloranilines, toluidines, sulfanilic acid, metanilic acid and aminobenzoic acids.

In many cases it has been found to be advantageous to carry out the first stage condensation of the cyanuric chloride with the water-soluble amines or the water-soluble salts of water-insoluble amines in the presence of a wetting agent. Suitable wetting agents are, for example, the reaction products of 1 mole of fatty alcohol with 5 to 8 moles of ethylene oxide and the alkali metal or ammonium salts of the acid sulfuric acid esters of such reaction products. '■ · _:. . '■ ·.

'Before the known processes in which the first stage condensation of the cyanuric chloride with aromatic amines or aromatic aminobenzenesulfonic acids or their salts in one Process for the preparation of brightening agents of the bistriazine laminosilbene series

Applicant :, ■ "■ '

Paint factories Bayer Aktiengesellschaft,
Leverkusen

Named as inventor:

Dr. Ernst-August Kleinheidt, Hoclikirchen;

Dr! Heinrich Gold. Cologne-Stammheim

aqueous medium takes place, which contains an organic solvent for the cyanuric chloride, draws the process according to the invention is characterized in that, thanks to the elimination of organic solvents

2p is cheaper and can be carried out more quickly and easily can be. The method according to the invention also has the same advantage over the known one Working method with the cyanuric chloride in the form of a solution in an organic solvent with aromatic amines, which are also used in the Solvents are dissolved, is condensed.

Compared to the also known procedure in which cyanuric chloride in the first stage in one of organic solvent-free aqueous medium with aromatic amines which are insoluble in water Form present, is condensed, the inventive method has the advantage that it to Lightening agents leads that have a particularly high degree of purity and therefore special

result in strong lightening. ... '.

A method has already been described; in which the condensation of cyanuric chloride with water-soluble borrowed salts of aromatic sulfonic acids in one of organic solvents-free aqueous medium carried out in the presence of acid-binding agents will. However, this did not suggest the method according to the invention; because in the description of this procedure it is stated that the Cyanuric chloride does not react if the aqueous medium

45'dium shows a weakly acidic reaction instead of the neutral reaction.

The parts given in the following examples are parts by weight.

example 1

18.5 parts of cyanuric chloride are at room temperature in 100 parts of water, the 0.5 part of the reaction

'·. ■ ■ ■■ _. ■ - T09 649/429

Product of 1 mole of dodccyl alcohol with 5 moles of ethylene oxide added as a wetting agent, entered. The mixture is then added with stirring to a solution of 18.2 parts of 4-Äminobenzolsulfonsäure and 5.9 parts of potassium hydroxide in 100 parts of water, and then first heated 45 minutes for 40 to .45 ^C C and then for 30 minutes at 6O ⁰ C.. The reaction mixture is now mixed with 18.6 parts of the disodium salt of 4,4'-diaminostilbcn-2,2'-disulfonic acid and 16.5 parts of sodium hydrogen carbonate, and initially for 45 minutes at 70 ° C. and then for a further 15 minutes at SS ^ C Thereafter, 22.5 parts of diethanolamine are added at the boiling point ) -a mi no] -stilbcn-2, l'-disulfonic acid is isolated by spraying the solution.

Be is ρ i e 1 2

18.5 parts of cyanuric chloride are added at room temperature to 100 parts of water to which 0.5 part of the agent listed in Example 1 has been added, and the mixture is then stirred with a solution of 18.2 parts of 3-aminobenzenesulfonic acid and 4.2 parts of sodium hydroxide in 100 parts Water added. The Reaklionstcmperatur rises to about 35 ⁰ C. As soon as the added 3-aminobenzene sulfonic acid is consumed - this is the case after about 30 minutes - a solution of 17.4 parts of the disodium salt of 4,4'-diamino, tilbene-2,2'-disulfonic acid and 16 parts of sodium hydrogen carbonate in 200 parts of water is added . The reaction mixture is then heated to 70 to 75 ^° C. for a further 45 minutes. heated and finally mixed with 24 parts of diethanolamine. The resulting tetrasodium salt of 4,4'-bis [2-diethanolaniino-4- (3 "-sulfoanilino) -1.3, 5-triazinyl- (6) -amino] -stilbene-2.2'-disulfonic acid is made by salting out with common salt isolated.

Be is ρ ie T 3

18.5 parts of cyanuric chloride are at rauiritempera-

ture in 200 parts of water, which is 0.5 part of the in the example! . listed wetting agents are added. A solution of 9.8 parts of aniline and 11.3 parts of concentrated hydrochloric acid in 200 parts of water are then added to the mixture, while stirring, and the mixture is heated ^{first to 40 to 45 ° C. and then to 70 ° C. for 1 hour.} The resulting slurry. which 23 parts. 2-anilino-4,6-dichloro-1,3,5-triazine ent-. holds, is then with 17.2 parts of the Dinalrium-. salt of 4,4'-diaminostilbene-2,2'-disulfonic acid and -. mixed with a solution of 2.5 parts of sodium hydrogen carbonate in 200 parts of water. The reaction mixture is heated to 70 to 50 ° C. for 1 hour and then treated with a solution of 24.5 parts of diethanolamine in 100 parts of water. After the temperature of the mixture has been ^{kept at 100 °} C. for about 45 minutes, the solution is filtered off and adjusted to a pH of 3 to 4 with 13 to 14 parts of concentrated hydrochloric acid. The 4,4'-bis- [2-diethan'olamino-4-anilino-1,3,5-triazinyI- (6) -amino] -silbcn-2,2'-disulfonic acid formed precipitates in the form of crystals. .

Claims (1)

Claim: Process for the manufacture of lightening agents the bistriazinylaminostilbene series by condensation of cyanuric chloride with water-soluble salts of aromatic amines or aromatic amines Aminosulfonic acids in a molar ratio of 1: 1 in an aqueous medium free of organic solvents, with subsequent reaction of the condensation product formed with 4,4'-diaminostilbene-2.2'-disulfonic acid or their salts in a molar ratio of 2: 1 and optionally below further reaction of the resulting reaction product with amines or amine salts in MoI-2. thereby g e k e η η ζ e i c h - Ratio 1 net. that the condensation of the cyanuric chloride with _den- water-soluble salts of aromatic amines or aromatic aminosulfonic acids in the first stage in the absence of acid-binding agents. Considered publications:
USA .- 'Patent; No? 2 720 480 (example VII):
J. Soc. or Dyers and Colourists. 53 (1937). Pp. 424 to 429. 709 649/429 9. 67 Bundesdruckerei Berlin