DE1289216B - Acidic asymmetric diarylamine derived diaminotriarylmethane dyes and processes for their preparation - Google Patents

Description

The invention relates to new acidic, asymmetric, diaminotriarylmethane dyes derived from diarylamine and a process for their preparation by condensation of monoamino-substituted, or a reactive group containing triarylmethane compounds with an optionally substituted, aliphatic, aromatic or heterocyclic primary amine that does not have any free - Contains SCfeH groups.

The dyes produced according to the invention can be assigned to a hitherto unknown dye category. In the entire literature on triphenylmethane dyes there are only symmetrically substituted ones Connections mentioned. In contrast, according to the method according to the invention, dyes made with unsymmetrical substituents. You can go a long way after this procedure capture a larger range of color tones and also achieve different physical properties.

The previously known dianiinotriarylmethane dyes derived from diaryl are generally symmetrical and by simultaneous disubstitution of the mobile groups in the 4,4'-position been received.

In contrast, the dyes which can be produced according to the invention are produced by selective substitution, namely, first becomes a reactive group through an aromatic sulfonated amine and then the remaining reactive group by an optionally substituted, aliphatic, aromatic or heterocyclic amine that does not contain any free - SOeH groups.

These acidic dyes have a fixed one due to the process used to prepare them chemical structure and, in contrast to the acidic ones, are obtained by sulfonation Triarylmethane dyes, free from isomers. The reaction according to the invention is carried out by heating equimolecular amounts of the starting materials, expediently in the presence of benzoic acid, carried out.

The dyes thus obtained correspond to the following general formula

NH

l \

A OH

In the formula, A denotes a phenyl radical, Ri or at least bonded via other groups

has a —SOaH group free, optionally a —SOeH group.

substituted alkyl, aryl, arylalkyl, alkylaryl 35

or heterocyclic group, R2 a given milled triarylmethane compound of the general

if substituted aromatic radical, that directly means my formula

NH

in which A is a phenyl radical, Ri is an alkoxy group, R2 is an optionally substituted aromatic radical which is bonded directly or via other groups has at least one - SOaH group, means.

Such a compound, which contains a reactive alkoxy group, is reacted in equimolar amounts with an optionally substituted, aliphatic, aromatic or heterocyclic amine which does not contain a free -SCfeH group, expediently in the presence of benzoic acid by adding a few in an oil bath with constant stirring Heated to temperatures between 135 and 150 ⁰ C for hours. The reaction mixture is poured into warm water and washed in a decanter with warm water in order to remove the benzoic acid if necessary.

The dye thus obtained can by dissolving in dilute sodium hydroxide solution and precipitation with dilute Hydrochloric acid.

Further cleaning can be done by washing with

l \

A OH solvents (e.g. ether or petroleum ether) are carried out.

If the dyes are soluble in water, they are immediately thickened and washed ground mass with solvents (e.g. ether, petroleum ether or others) cleaned.

The yield is generally good and is over 80% of theory.

For ρ iel 1

To 10 g of a violet starting dye, which is obtained by reaction of V10 mol ρ, ρ'-dimethoxytriphenylcarbinol and V10 moles and about 10% sulfanilic acid in the presence of 300 ecm of acetic acid, and 10 g of benzoic acid becomes 2.750 g Given aniline and proceed as described above. A water-insoluble dye is obtained. His alcoholic solution is yellowish green and has an absorption maximum at 657 ήΐμ.

The dye conforms to the formula

This dye, of defined chemical structural j ₅ door, has to the dye that is specified in the Color Index, 2nd edition 1956 under the CI No. 42 and the same formula adopted for the one, very different properties. in fact, the latter is soluble in water, while the one prepared in accordance with paragraph 1 is practically insoluble. It is therefore assumed that the dye given in the Color Index has a different structure, since the reaction carried out according to the invention leads with certainty to the dye of the formula given.

Example 2

10 g of the same starting dye as in Example 1 are mixed with 1.8 g of n-butylamine and 10 g Reacted benzoic acid, the procedure described in Example 1 proceeding.

A water-insoluble in alcoholic solution is obtained with a practically quantitative yield blue and an absorption maximum at 615 ηΐμ having dye of the formula

SO ₃

CH ₃ CH ₂ CH ₂ CH ₂

is equivalent to.

If the reactions are carried out with other amines instead of aniline or ßutylamine, so you get dyes with different shades, z. B .:

Absorption maximum

Monoethanolamine 615 ΐημ

r »-aminobutyric acid 611 ηΐμ

Ethylenediamine 616 ιημ

Phenylethylamine 621 ηΐμ

p-phenylenediamine 641 ηΐμ

p-aminodiphenylamine 659 ηΐμ

p-phenetidine 646 ηΐμ

2-amino-1-hydroxydiphenyl 637 ηΐμ

2-chloro-5-aminobenzoic acid 642 ηιμ

1-naphthylamine 636 ιτίμ

2-naphthylamine 651 ηΐμ

Hexamethylene diamine 616 ηΐμ

m-dimethylaminopropylamine 610 ηΐμ

2-aminobenzothiazole 639 ηΐμ

p-aminophenol 643 πΐμ

4-amino-4'-hydroxydiphenyl 657 πΐμ

p-toluidine 646 ηΐμ

Hydroxyethylpropanediamine 616 ηΐμ

2-methoxy-5-phenylsulfone 637 ΐτίμ ^: \

2,4-pimethoxyaniline. ........ 638 ιημ

"'p-Attilnoibenzoic acid 647 ιημ

^: 2-5-Öimqthoxyanilm .... .... 638 ηΐμ

2,4-dimethoxy-S-chloroaniline 636 ηΐμ

2,4-dimethoxy-4-chloroaniline 638 ηΐμ

By converting a calculated amount of the red-violet starting dye produced by the reaction of ρ, ρ'-dimethoxytriphenylcarbino! and 1-aminonaphthalene-3,6-disulfonic acid has been obtained, with aniline a green dye with an absorption maximum at 616 πΐμ is obtained.

By converting a calculated amount of the red-violet starting dye produced by the reaction of ρ, ρ'-dimethoxytriphenylcarbinol and 2-aminonaphthalene-1-sulfonic acid has been obtained, with p-aminobenzoic acid, a green dye with an absorption maximum at 655 ηΐμ is obtained.

By converting a calculated amount of the red-violet starting dye produced by the reaction of ρ, ρ'-dimethoxytriphenylcarbinol and 2-aminonaphthalene-irsulfonic acid has been obtained, with aniline a green dye with an absorption maximum at 647 ηΐμ is obtained.

By converting a calculated amount of the red-violet starting dye produced by the reaction of ρ, ρ'-dimethoxytriphenylcarbinol and o-anilic acid has been obtained, with aniline, a green dye with an absorption maximum at 643 ιημ obtain.

In the reaction of a calculated amount of red-violet Ausgangsfarbstöffs obtained by reaction of ρ, ρ'-Dimethoxytriphenylcarbinpl and 1-aminobenzene-4-oxyäthansuifonsäure has been obtained, with the following amines show the ex

Sorption maxima of the dyes obtained in this way have the following values:

aniline

Anisidine

p-aminodiphenylamine

Monoethanolamine

Amino-tris (hydroxymethyl) methane

Hydroxyethyl propane diamine

dye

green
green
green
Blue green

Blue green
Blue green

Absorption maximum

643
649
668
608

626
620

By converting the red-violet starting dye, obtained by the reaction of ρ, ρ'-dimethoxytriphenylcarbinol and 4-phenoxy-3-sulfoaniline has been, with monoethanolamine becomes a blue-green dye with absorption maximum at πΐμ obtained.

NH

By converting the red-violet starting dye, obtained by the reaction of ρ, ρ'-dimethoxytriphenylcarbinol and 4-phenoxy-3-sulfoaniline has been, with p-phenetidine a green dye with an absorption maximum at 649 πΐμ is obtained.

By converting the red-violet starting dye, which is produced by the reaction of ρ, ρ'-dimethoxytriphenylcarbinol and 2-sulfo-4-chloro-5-carboxyaniline has been obtained, with aniline becomes a green one ίο dye with absorption maximum at 635 ηΐμ obtain.

By converting the red-violet starting dye, which is produced by the reaction of p, p'-dimethoxytriphenylcarbinol and l-amino-4- (2-morpholinomethyl) -phenoxy-3-sulfonic acid has been obtained, with monoethanolamine, a blue-green dye with an absorption maximum at 608 πΐμ is obtained.

Claims (2)

Patent claims: 1. Acidic, asymmetric, diarylaminotriarylmethane dyes derived from diarylamine the general formula NH l \ A OH in which A is a phenyl radical, Ri one of - SO3H groups free, optionally substituted alkyl, aryl, arylalkyl, alkylaryl or heterocyclic ones Group, R2 is an optionally substituted aromatic radical which is directly or via others Groups bonded has at least one —SO3H group, means. 2. Process for the preparation of acidic, asymmetric diaminotriarylmethane dyes derived from diarylamine, characterized in that there is an acidic »derived from the diarylamine and another capable of implementation Group-containing triarylmethane compound of the general formula NH NH l \ A OH in which A is a phenyl radical, Ri is an alkoxy group, Ra is an optionally substituted aromatic radical which is directly or via other groups has bonded at least one —SQjH group, means with an optionally substituted, primary, aliphatic, aromatic or heterocyclic amine that does not contain a free - SOaH group to form a dye the general formula ./■ NH i \ A OH converts, in which A is a phenyl radical, Ri one of - SO3H groups free, optionally substituted alkyl, Ary! -, - AryialkyK alkylaryl or heterocyclic group, Ra an optionally substituted aromatic radical which is directly or Bound via other groups has at least one - SOeH group, means.