DE2006517A1 - Salts of 3-(benzimidazolyl-2') -7-dialkyl-co - Google Patents

Abstract

Salts of 3-(benzimidazolyl-2')-7-dialkylaminocoumarin sulphonic acid are of formula in which R and R1 are Me or Et or together with N atom form the residue of a 5- or 6-membered heterocyclic ring, R2 is H, Me or Et, R3 is H, Cl or Br or Me, Et, MeO or EtO, and X is radical with a cationic N. The salts are dyes suitable for dyeing solvents, lacquers coating agents, textiles, paper and plastics.

Description

Salts of 3- (benzimidazolyl-2 ') - 7-dialkylaminocoumarin sulfonic acid The invention relates to dyes of the general formula in which R and R1 are methyl or ethyl groups or, together with nitrogen, the remainder of a 5- or 6-membered heterocyclic ring, R2 is a hydrogen atom or a methyl or ethyl group, R3 is a hydrogen, chlorine or bromine atom or a methyl, Ethyl, methoxy or ethoxy group and X is a radical with a cationic nitrogen.

Under 5- or 6-membered heteroeyelic rings, the R and R1 together form with the nitrogen are, for. B. the residues of pyrrolidone, piperidine, morpholins or to understand piperazins.

The radicals X have a positive charge on a nitrogen atom, preferably are to be understood as ammonium cations.

The ammonium cations are preferably derived from primary, secondary or tertiary amines, and the quaternary ammonium radicals should also be mentioned.

Furthermore, there are cyclammonium cations, e.g. B. PyrldinLum-, quinolinium-, Thiazolium or Imidazoliuireste into consideration.

The cations of basic dyes are also of particular importance, in particular of di- or triarylmethane dyes, xanthene, acridine, polymethine or azapolymethine dyes.

In detail, the radicals X may be mentioned, for example: The dyes of the general formula are of particular industrial importance in which R4 denotes a methyl or ethyl group and an ammonium cation with 8 to 26 carbon atoms or the cation of a basic dye of the triarylmethane, xanthone, polymethine or azapolymethine series.

The new dyes are yellow to green, depending on the cation and have a high brilliance. They are suitable for coloring solvents, varnishes, Coating agents, textiles, paper and plastics.

To prepare the new compounds are preferably used Sulphonic acid in water or organic solvents or in mixtures of the two with an equivalent one ums, which is conveniently in water or an organic Solvent is dissolved to.

Another possibility is the double implementation, see B. of the sodium salt of sulfonic acid with an equivalent amount of the cationic Nitrogen compound in the presence of water or organic solvents or Mixtures of both.

This depends on the solubility in the respective diluent Salt lit the organic cation less or less insoluble the end and is isolated by suction or a solution of the salt is formed which is freed from the solvent by evaporation.

example 1 21 parts of 3- (benzimidazolyl-2 ') -7-diethylaminocoumarin-sulfonic acid are finely powdered in 200 parts of ethanol, heated to 70 ° C and added to a pH of 9 with 20 parts of ethylhexoxypropylamine, the acid being the salt goes into solution. When the salt solution cools, a yellow precipitate separates out, which is suctioned off and dried. The yellow dye dissolves with intense yellow-green fluorescence in organic solvents and produces intensely yellow-green fluorescent products when incorporated into thermosetting and thermoplastic plastics, as well as when used as a solvent dye.

Example 2 21 parts of 3- (benzimidazolyl-2 ') -7-diethylaminocoumarin-sulfonic acid are finely powdered and slurried in 200 parts of water, heated to 60 to 70 ° C. and 5 parts of piperidine are added at this temperature to adjust the pH to 8.

The solution is concentrated under reduced pressure, the precipitating Sucked off precipitate and dried. 21 parts of the yellow dye are obtained the formula above.

Example 3 21 parts of 3- (benzimidazolyl-2 ') - 7-diethylaminocoumarin-sulfonic acid are suspended in 100 parts of ethanol and 12 parts of ri-n-butylamine are added at room temperature so that the mixture has a pH of 8.

The suspension is heated to 60 to 70 oO, for a short time at this Stirred temperature and sucked off after cooling.

24 parts of the yellow dye of the formula given above are obtained.

Example 4 21 parts of 3- (benzimidazolyl-2 ') -7-diethylaminocoumarin-sulfonic acid are finely powdered and suspended in 200 parts of ethanol, heated to 70 ° C. and mixed with 11 parts of dihydrotricyclopentadienylamine. The salt formed goes into solution in ethanol. When the solution cools, it precipitates in the form of yellow crystals, which are filtered off with suction and dried. 29 parts of the yellow dye of the formula given are obtained.

Example 5 20 parts of dimethylstearylbenzylammonium chloride are dissolved in 50 parts of water and poured into a solution of 22 parts of sodium 3- (benzimidazolyl-2 ') -7-diethylaminocoumarin-sulfonic acid in 200 parts of water. The initially greasy salt precipitate crystallizes on prolonged stirring. He ird sucked off and dried at 60 0C. 25 parts of the yellow colored salt of the formula given above are obtained.

Example 6 22 parts of 3- (benzimidazolyl-2 ') -7-diethylaminocoumarin-sulfonic acid sodium are dissolved in 350 parts of water and a solution of 12 parts of 1,4-dimethylpyridinium methosulfate in 50 parts of water is added at room temperature. The resulting solution is concentrated and the yellow colored salt which precipitates is filtered off with suction. 25 parts of the abovementioned compound are obtained.

Example 7 20 parts of 3- (benzimidazolyl-2 ') -7-dimethylaminocoumarinsulphonic acid are finely powdered in 200 parts of ethanol, mixed with 11 parts of diphenylguanidine and heated to reflux temperature. The solution, which is clear in the heat, is cooled and the color salt which has precipitated is filtered off with suction. 28 parts of the yellow dye of the formula given above are obtained.

Example 8 23 parts of the dye (CI 45 160) are dissolved in 375 parts of water and combined at room temperature with a solution of 22 parts of 3- (benzimidazolyl-2 ') - 7-diethylaminocoumarin-sulfonic acid sodium in 375 parts of water. The precipitated salt is suctioned off and dried. It dyes organic solvents with a fluorescent orange-red color and can be used for coloring plastics and as a solvent dye.

Example 9 22 parts of 3- (benzimidasolyl-2 ') - 7-diethylaminocoumarin-sulfonic acid sodium are dissolved in 350 parts of water and combined at room temperature with a solution of 28 parts of Victoria Blue B (c. I. 44 045) in 1200 parts of water. The precipitated dye is filtered off with suction and dried at 60.degree.

35 parts of a dark green colored salt of the above are obtained Formula.

Example 10 15 parts of auramine are dissolved in 380 parts of water at 80 ° C., cooled and combined at room temperature with a solution of 22 parts of sodium 3- (benzimidazolyl-2 ') -7-diethylaminocoumarin-sulfonic acid in 350 parts of water. The precipitate, which initially tends to smear, crystallizes after prolonged stirring. It is filtered off with suction and dried at 60.degree. 23 parts of the yellow colored salt of the formula given are obtained.

Example 11 22 parts of 3- (benzimidazolyl-2 ') -7-diethylaminocoumarin-sulfonic acid sodium are dissolved in 200 parts of water at 80 ° C., cooled again to 50 ° C. and treated with a solution of 13 parts of 3,6-diamino-10-methyl- acridioium chloride combined in 100 parts of water.

The resulting colored salt suspension is concentrated to 150 parts by volume, cooled and sucked off the parbsalt. 29 parts of the yellow dye are obtained the formula above.

Example 12 22 parts of 3- (benzimidazolyl-2 ') -7-diethylaminocumrin-sulfonic acid sodium are dissolved in 200 parts of water at 70 to 80 oO, then cooled again to room temperature and treated with a solution of 23 parts of the quaternary dimethylation product of 3- (benzimidazolyl- 2 ') - 7-diethylaminocoumarin combined in 2000 parts of water. The resulting suspension of the colored salt is concentrated to 500 parts by volume and the salt is filtered off with suction.

16 parts of the yellow colored salt of the composition given above are obtained. The new connection is for dyeing plastics and polyacrylonitrile-wool blends suitable.

Analogously to the procedure described in the examples, one obtains using the sulfonic acid of Example 12 or

their alkali salts with the compounds listed as cations in the following table, other dyes with similar properties: Example: Cation hue 13 (CH3) 4N 14 (CH3) 2N-CH26H5 -I 06115 06H5 15 (C4H9) 3NH 16 H2N 9 17 R (R = mixture of 17 H3 C12H25 to C15Hsl) 18 H3NC2H5 0 19 H2N (CH2CH20H) 2 0 20 H3N> 21 6H3 yellow yellow yellow yellow yellow yellow yellow yellow yellow Example of a cation shade 22 CH3 22 S> 3 yellow CH3 CH3 23 m »0112 ON yellow CH3 / ,, NH2 24 H2N = Cs 2 yellow NH2 25 CI 42 555 green 26 CI 42 000 green yellow 27 CI 45 160 (methyl ester) scarlet 28 CI 45 170 scarlet 29 C. 1. 48 015 scarlet 30 CI 48 013 red 31 H, C4 N = N - N (CH3) 2 green CH3 R OH 13 T- ( 32 t> N = N i §-CH3 yellow 6 5 OH3 OH 33 S -CH-NN to yellow CH3 Orange orange green hue

Claims (3)

Petitioner's claims 1. Salts of 3- (benzimidazolyl-2 ') -7-dialkylaminocoumarin sulfonic acid of the general formula in which R and R1 are methyl or ethyl groups or, together with the nitrogen, the remainder of a 5- or 6-membered heterocyclic ring, R2 is a hydrogen atom or a methyl or ethyl group, R3 is a hydrogen, chlorine or bromine atom or a methyl, Ethyl, methoxy or ethoxy group and X is a radical with a cationic nitrogen. 2. Salts according to claim 1 of the general formula in which R4 denotes a methyl or ethyl group and an ammonium cation with 8 to 26 carbon atoms or the cation of a basic dye of the triarylmethane, xanthene, polymethine or azapolymethine series. 3. A method for the preparation of salts according to claim 1, characterized in characterized in that the oumarinsulfonic acid with amines or the alkali metal salts of Reacts sulfonic acid with the cationic nitrogen compound.