DE1569750A1 - Process for the preparation of basic dyes - Google Patents

Description

FARBENFABRIKEN BAYER AG

LEVERKUS EN-Beyeiweik Patent department Ut / SK

2 O ₈ April 1967

Process for the production of basic dyes

It has been found that basic dyes are worth getting, if one uses indolylmethanes which are free of sulfonic acid groups and carboxylic acid groups the general formulas

ν:

^R 2

(D or I (II)

C-R,

^Χ 4 ^R 4

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

.R ₁

(III)

bsv.

■ R,

ΩDQflö /

(IV)

In the general formulas (I) ₁ (II), (III) and (IY), R denotes hydrogen, an alkyl, aralkyl or aryl radical, a nitro, cyano, carboxylic acid ester, optionally Η-substituted carbonamide, acyl -, alkylsulfonyl or arylsulfonyl group, R ₁ hydrogen, an alkyl, aralkyl, cycloalkyl or aryl radical, R ₂ hydrogen, an alkyl, cycloalkyl or aralkyl radical, R hydrogen, an alkyl or aryl group, a carboxylic acid ester group, a optionally N-substituted carbonamide group or an alkoxy group, R. hydrogen, an alkyl, aralkyl, cycloalkyl or aryl radical. D denotes a heterocyclic ring system, in particular a furan or thiophene ring and X denotes an anionic radical. The indolylmethanes can contain further substituents (nonionic substituents) in the aliphatic, cycloaliphatic and aromatic radicals, including the benzene rings represented by the formula, with the exception of sulfonic acid and Have carboxylic acid groups. Suitable nonionic substituents are, for example, lower alkyl and alkoxy radicals having 1-4 carbon atoms, aralkyl, such as benzyl, aralkoxy, such as benzyloxy, aryl, such as phenyl and phenyl radicals substituted by nonionic radicals, for example chlorophenyl, methylphenyl -, ethylphenyl, nitrophenyl, cyanophenyl groups, aryloxy groups such as phenyloxy, halogen substituents, especially Cl and Br, carboxylic ester groups, especially carboxylic acid. methyl ester and ethyl ester groups, optionally N-substituted carbonamide groups, with lower alkyl groups being preferred as N-substituents, which may be further substituted, β.B. by. Cl, Br and OH} the cyano, nitro, hydroxyl or amino group,

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Alkylsulfonyl, such as methylsulfonyl and ethylsulfonyl, Arylsulfonyl, such as benzenesulfonyl and p-toluenesulfonyl, Acyloxy groups, such as acetoxy and propionyloxy, acylamino groups, such as acetylamino, propionylamino, ethylsulfonylamino, Methylsulfonylamino, benzoylamino, benzenesulfonylamino groups and acyl radicals, such as the benzoyl and acetyl radical,

The oxidation of the indolylmethanes of the formulas (I) or (II) to the basic dyes (III) or (IV) is preferably carried out in an acidic medium, for example in acetic acid, dilute sulfuric acid, dilute hydrochloric acid and in mixtures of these acids. For better solubility Water-miscible organic solvents such as alcohol, dimethylformamide or acetonitrile can be added. ^s

Suitable dehydrating or oxidizing agents are the agents customary in triphenylmethane chemistry, for example 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, hydrogen peroxide, and air oxygen , optionally with the addition of catalysts which transfer acidic off, such as metal ions.

The indolylmethanes of the formulas (I) and (II) to be used as starting compounds can be obtained by condensation of indolylaryl- or indolylheteryl-hydroxymethanes, -alkoxymethanes, -aminomethanes or -anilinomethanes with suitable components

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the aminobenzene series, which has at least one exchangeable hydrogen atom contain on a ring-bonded carbon atom, preferably in an acidic medium.

The products obtainable according to the process are valuable dyes, which are suitable for dyeing and printing 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 continue are used for the production of writing fluids, stamp inks, ballpoint pen pastes and can also be used in the. Use rubber pressure. They are particularly suitable for dyeing and printing materials that are completely or partially ou polymerized acrylonitrile and / or vinylidene cyanide, or from materials made from acid-modified polyesters, such as Textile materials made from polyethylene glycol terephthalates containing sulfonic acid groups. On these materials they are characterized by very good lightfastness, wet, rub and sublimation fastness the end. They also have very good drawability for these fibers and have good top dye fastness. You dyes form with anionic precipitants such as clay, tannin, Phosphorus tungsten (molybdenum) acids lightfast pigments that are beneficial can be used in paper printing

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

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example 1

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

- ° 6 ^H 5

CH,

are dissolved in 70 parts of glacial acetic acid and 5 parts of 20 # strength 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 7O ⁰ C, then is cooled to 30 ⁰ C and i.ltriert from lead sulfate abf. The dye is precipitated from the filtrate with saline solution. The dye obtained corresponds to the formula

and dyes polyacrylonitrile fibers in real green tones.

HSO

Example 2

8.5 parts of 1-methyl-2-phenylindolyl (3) - (4'-methylaminophenyl) -phenylmethar are dissolved in 100 parts of glacial acetic acid and 10 parts of 2Obiger sulfuric acid. The mixture is β at 70 ⁰ C et RHIT and stirring 5.5 parts of sodium dichromate is added in 9 parts of watter. It is stirred for 30 minutes at 70 ⁰ C, sucked 'and dat filtrate into 500 parts! Cast Obiger Koohealzlöeung.

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The dye obtained is filtered off with suction, dissolved in water and like with table salt. The dye dyes polyacrylonitrile fibers in reddish blue tones.

Example 3

8 parts of 2-methylindolyl (3) - (4 ^f -diäthylaminophenyl) -2 ^M -nitrophenylmethan are dissolved in 50 parts of glacial acetic acid and 5 parts of 20 # sulfuric acid and the solution to 60 - 7O ⁰ C heated. 10.7 parts of iron (III) chloride are crystallized with stirring. added in 16 parts of water. It is stirred for 60 minutes at 100 ⁰ C and poured into 500 parts of sulfuric lO ^ brine. The paraffin is filtered off with suction and recrystallized from water. It dyes polyacrylonitrile fibers in blistering tones.

If one uses the previous examples as starting components If the indolylmethanes listed in the table below are used, valuable basic ones are likewise obtained in an analogous manner Dyes that dye polyacrylonitrile fibers in the specified shades.

Indolyl methane

Color on polyacrylonitrile fibers

^ CH,

blue

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Indolylmethane shade on polyacrylonitrile fibers

^CH

.C. H

C ₉ H ₄ OH

-C ₂ H ₄ OH

OH,

.C

CH

( Green

greenish blue

IT Π

.C H

0 Vh

'CH, purple

X ^H

C ₂ H ₅

IL

01

/ ° 2 ^H 5

C ₂ H ₅

blue

blue

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IndoIy! Methane

Color on polyacrylonitr Ufas era

O ₂ H ₅ greenish blue

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Claims (3)

Claims; where R stands for hydrogen, an alkyl, aralkyl or aryl radical, a nitro, cyano, carboxylic acid ester, optionally N-substituted carbonamide, acyl, alkylsulphonyl or arylsulphonyl group, R. for hydrogen, an alkyl, aralkyl , Cycloalkyl or Arylreat, R ₂ for hydrogen, an alkyl, cycloalkyl or aralkyl radical, R, for hydrogen, an alkyl or aryl group, a carboxylic acid ester group, an optionally N-substituted carbonamide group or an alkoxy group, R, for hydrogen, a Alkyl, aralkyl, cycloalkyl or aryl radical and in which D stands for a heterocyclic ring system, treated with dehydrating or oxidizing agents. 2) Indolylmethane dyes of the formula - 9 009884/1199 15 £ 9750 wherein R is hydrogen, an alkyl, aralkyl or aryl group, a nitro, cyano, carboxylic acid ester, optionally N-substituted carbonamide, acyl, alkylsulfonyl or arylsulfonyl group, R _{1 is} hydrogen, an alkyl, aralkyl, cycloalkyl - or aryl radical, R _{2 is} hydrogen, an alkyl, cycloalkyl or aralkyl radical, R, hydrogen, an alkyl or aryl group, a carboxylic ester group, an optionally N-substituted carbonamide group or an alkoxy group and R. is hydrogen, an alkyl, aralkyl group , Mean cycloalkyl or aryl radical and X stands for an anionic radical. 3) indolylmethane dyes of the formula wherein R _{1 is} hydrogen, an alkyl, aralkyl, cycloalkyl or aryl radical, R _{2 is} hydrogen, an alkyl, cycloalkyl or aralkyl radical, R, hydrogen, an alkyl or aryl group, a carboxylic acid ester group, an optionally N-substituted carbonamide group or is an alkoxy group and R. is hydrogen, an alkyl, aralkyl, cycloalkyl or aryl radical, D is a heterooyclic ring system and X is an anionic radical. Le A 10 691 - 10 - 009884/1699