DE1569750B2 - Process for the production of basic dyes - Google Patents

Description

respectively.

30th

35

40

wherein R stands for hydrogen, an alkyl, aralkyl or aryl radical, a nitro, cyano, carboxylic acid ester, optionally N-substituted carbonamides, acyl, alkylsulphonyl or arylsulphonyl group, R ₁ for hydrogen, an alkyl, aralkyl, cycloalkyl - or aryl radical, R ₂ for hydrogen, an alkyl, cycloalkyl or aralkyl radical, R _? represents hydrogen, an alkyl or aryl group, a carboxylic ester group, an optionally N-substituted carbonamide group or an alkoxy group, R ₄ ^{] represents} hydrogen, an alkyl, aralkyl, cycloalkyl or aryl radical and in which D represents a heterocyclic ring system, with Treated dehydrating or oxidizing agents.

60

65

(II)

treated with dehydrating or oxidizing agents. The resulting cationic dyes have the formulas

It has been found that valuable basic dyes are obtained if sulfonic acid groups and

X "

(III)

In the general form Eini, II, III and IV R represents hydrogen, an alkyl, aralkyl or aryl group, a · nitro, cyano, carboxylic acid ester, optionally N-substituted carboxamido, acyl, alkyl \ sulfonyl or Arylsulfonyl group, R ₁ hydrogen, j an alkyl, aralkyl, cycloalkyl or aryl radical, i R ₂ hydrogen, an alkyl, cycloalkyl or aralkyl j radical, R ₃ hydrogen, an alkyl or aryl group, a carboxylic acid ester group, a optionally N-substituted carbonamide group or an alkoxy group, R _{4 is} hydrogen, an alkyl, aralkyl, cycloalkyl ^! or aryl radical. D means a heterocyclic ring | system, in particular a furan or thiophene ring, and X stands for an anionic radical. The indolyl methanes can have further substituents (nonionic substituents) in the aliphatic, cycloaliphatic and aromatic radicals, including the benzene rings represented by the formula Have exceptions of sulfonic acid and carboxylic acid groups j. Examples of nonionic substituents are: lower alkyl and alkoxy radicals having 1 to 4 carbon atoms, aralkyl, such as benzyl, aralkoxy, such as benzyloxy, aryl, such as phenyl and phenyl radicals substituted by nonionic radicals, e.g. B. chlorophenyl, methylphenyl, ethylphenyl, nitrophenyl, cyanophenyl groups, aryloxy groups, such as phenyloxy, halogen substituents, especially Cl and Br, carboxylic acid ester groups, especially carboxylic acid methyl ester and ethyl ester groups, optionally N-substituted carbonamide groups, with lower alkyl groups as N-substituents are preferred which may be further substituted, e.g. B. by Cl, Br and OH; the cyano, nitro, hydroxyl or amino group, alkylsulfonyl, such as methylsulfonyl and ethylsulfonyl, arylsulfonyl, such as benzenesulfonyl and p-toluenesulfonyl, acyloxy groups, such as acetoxy and propionyloxy, acylamino groups, such as , Ethylsulfonylamino, methylsulfonylamino, benzoylami-: io-, benzenesulfonylamino groups and acyl radicals, such as the benzoyl and acetyl radicals.

The oxidation of the indolylmethanes of the formulas I 3ZW. II to the basic dyes III and IV er-Olgt in preferably acidic medium, e.g. B. in acetic acid, dilute sulfuric acid, dilute salt ; acid and in mixtures of these acids. To mend Solubility can be organic solvents which are miscible with water, such as alcohol or dimethylformamide or acetonitrile can be added.

Suitable dehydrating or oxidizing agents are the agents customary in triphenylmethane chemistry, e.g. iron (III) and copper (II) salts, their complex compounds, alkali dichromates, lead (IV) oxide and its salts, such as lead tetraacetate, nitrous acid, Peroxide compounds, such as potassium persulfate, y., Hydrogen peroxide, and also atmospheric oxygen, optionally with the addition of oxygen-transferring catalysts, such as metal ions.

The in-

X ~ IV) 'dolylmethane of the formulas I and II can be passed through

Condensation of indolylaryl- or indolylheterylhydroxymethanes ^ alkoxymethanesj-aminomethanes or -anilinomethanes with suitable components of the aminobenzene series, which have at least one interchangeable Contain hydrogen atom on a ring-bonded carbon atom, preferably in acidic Produce medium.

The products obtainable according to the process are valuable dyes that can be used for dyeing and printing of materials made of leather, tanned cotton, cellulose acetate, synthetic super polyamides and polyurethanes as well as for dyeing lignin-containing fibers such as coconut, jute and sisal. You can are also used for the production of writing fluids, stamp inks, ballpoint pen pastes and can also be used in rubber printing. They are especially good for dyeing and Printing of materials made entirely or partially of polymerized acrylonitrile and / or vinylidenecyanide consist, or of materials made of acid-modified polyesters, such as textile materials made of sulfonic acid groups Polyethylene glycol terephthalates. On these materials, they excel at being very good Light fastness, wet fastness, rub fastness and sublimation fastness. They also have very good drawability for these fibers and good over-dyeing fastness. The dyes form with anionic precipitants, such as clay, tannin, phosphotungsten (molybdenum) acids lightfast pigments, which are beneficial in paper printing can be used.

In the following examples, parts stand for parts by weight.

B e i s ρ i e 1 1

9 parts of 1-methyl-2-phenylindolyl (3) - (2'-chloro-4'-diethylaminophenyl) -phenylmethane the formula

CH,

are dissolved in 70 parts of glacial acetic acid and 5 parts of 20% sulfuric acid. The batch is heated to 70 ° C. and 48 parts of 10% lead dioxide are added with stirring. It is stirred for 30 minutes at 70 ° C, then is cooled to 30 ⁰ C and filtered VÖI Bleisülfat. The dye is taken from the filtrate

Saline solution like. The dye obtained corresponds to the formula

HSO

and dyes polyacrylonitrile fibers in real green tones.

Example 12

8.5 parts of 1-methyl-2-phenylindolyl (3) - (4'-methylaminophenyl) - Phenylmethane are dissolved in 100 parts of glacial acetic acid and 10 parts of 20% sulfuric acid. The batch is heated to 70 ° C. and, with stirring, 5.5 parts of sodium dichromate are added to 9 parts of water admitted. It is stirred for 30 minutes at 70 ° C, filtered off and the filtrate in 500 parts of 10% sodium chloride solution poured. The dye obtained is filtered off with suction, dissolved in water and precipitated with common salt. Of the Dyestuff dyes polyacrylonitrile fibers in a reddish tinge; blue tones.

B e i s ρ i e 1 3

8 parts of 2-methylindolyl (3) - (4 '- diethylaminophenyl) -2 "-nitrophenylmethane are dissolved in 50 parts of glacial acetic acid and 5 parts of 20% sulfuric acid and the solution is heated to 60 to 70 ° C. While stirring, 10 parts 7 parts of iron (III) chloride, cryst., water was added in 16 parts. The mixture is stirred for 60 minutes at 100 ⁰ C and poured into 500 parts of 10% sodium chloride solution. The dye is suction filtered and recrystallized from water. It dyes polyacrylonitrile in blue tones.

If in the previous examples the starting components are used as those in the following table cited indolylmethanes, one obtains in an analogous manner likewise valuable basic dyes, dye the polyacrylonitrile fibers in the specified shades.

Indolyl methane

CH

Hue on
Polyacrylonitrile fibers indolyl methane

blue

C ₂ H ₅

CH

Color on polyacrylonitrile fibers

green-

pithy

blue

violet

blue

blue

green-

pithy

blue

Claims (1)

Claim: Process for the preparation of basic dyes, characterized in that one sulfonic acid groups and carboxylic acid groups-free indolylmethanes of the general formulas carboxylic acid group-free indolylmethanes of the general formulas