DE2837953A1 - CATIONIC DYES - Google Patents

Description

BAYER AKTIENGESELLSCHAFT

Central area of patents, trademarks and licenses

5090 Leverkusen, Bayerwerk

Cationic dyes

The invention relates to new cationic dyes in general formula

Ϊ1

^CH

(D

wherein

R and R "independently of one another represent a lower alkyl, alkenyl or hydroxyalkyl radical,

R_ for a lower alkyl, alkenyl or alkoxy group,

R represents H, halogen, a lower alkyl, alkenyl or alkoxy radical and

X stand for an anion,

their manufacture and use for dyeing and printing more natural and synthetic materials.

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r-y-

Lower alkyl and alkoxy groups include, in particular, straight-chain or branched radicals with 1 to 4 carbon atoms. Lower alkenyl radicals are in particular those with 3 or 4 carbon atoms, especially the allyl, butenyl and i-butenyl radicals. Halogen stands primarily for fluorine and chlorine.

The anion X can be derived from inorganic and organic acids. Inorganic anions are, for example, fluoride, chloride, bromide and Iodide, perchlorate, hydroxyl, residues of S-containing acids such as hydrogen sulfate, sulfate, disulfate and aminosulfate; Residues of nitrogen-oxygen acids, like nitrate; Residues of oxo acids of phosphorus, such as Dihydrogen phosphate, hydrogen phosphate, phosphate and metaphosphate; Leftovers carbonic acid, such as hydrogen carbonate and carbonate; further anions of oxygen acids and complex acids, such as methosulfate, ethosulfate, hexafluorosilicate, Cyanate, thiocyanate, tri- and tetrachlorozincate, tri- and tetrabromozincate, borate, tetrafluoroborate, and anions of esters of boric acid, such as the glycerol ester of boric acid, and of esters of phosphoric acid, such as methyl phosphate.

Organic anions are, for example, anions of saturated or unsaturated aliphatic, cycloaliphatic ^ aromatic and heterocyclic carboxylic acids and sulphonic acids, such as residues of formic acid, acetic acid, chloroacetic acid, cyanoacetic acid, hydroxyacetic acid, aminoacetic acid, methylaminoacetic acid, methylaminoacetic acid, sulfonic acid, butyric acid, methylaminoethylsulfonic acid, methylaminoacetic acid, butyric acid. 2-methylbutyric acid, 2-ethylbutyric acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, 2-chloropropionic acid, 3-chloropropionic acid, 2-chlorobutyric acid, 2-hydroxypropionic acid, 3-hydroxypropionic acid, O-ethylglycolic acid, thioglycolic acid, glyceric acid. Ethylene glycol ether propionic acid, phenoxyacetic acid, nonylphenoxyacetic acid, n-valeric acid, i-valeric acid, 2,2,2-trimethylacetic acid, n-caproic acid, 2-ethyl-Tt-caproic acid, stearic acid, oleic acid, ricinoleic acid, palmitic acid, n-pelargonic acid, lauric acid, a mixture of aliphatic carboxylic acids with 9-11 carbon atoms (Versatic acid 911 from SHELL) ₅ acrylic acid, methacrylic acid, crotonic acid, propargylic acid, oxalic acid, malonic acid, succinic acid, adipic acid, pimelic acid,

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Suberic acid, the mixture of isomers of 2,2,4- and 2,4,4-trimethyladipic acid, Sebacic acid, isosebacic acid (mixture of isomers), tartaric acid, citric acid, glyoxylic acid.

Suitable anions of cycloaliphatic carboxylic acids are, for example, the anions the cyclohexanecarboxylic acid, cyclohexene-3-carboxylic acid and anions of araliphatic Monocarboxylic acids are z. B. anions of phenylacetic acid, 4-methylphenylacetic acid and mandelic acid.

Suitable anions of aromatic carboxylic acids are, for example Anions of substituted and unsubstituted benzoic acid, phthalic acid, tetrachlorophthalic acid, 4-hydroxyphthalic acid, 4-methoxyphthalic acid, Isophthalic acid, 4-chloro-iso-phthalic acid, 5-nitro-iso-phthalic acid, Terephthalic acid, nitroterephthalic acid and diphenylcarboxylic acid (3,4), o-vanillic acid, 3-sulfobenzoic acid, benzene tetracarboxylic acid (1,2,4,5), Naphthalenetetracarboxylic acid (1,4,5,8), biphenylcarboxylic acid (4), abietic acid, phthalic acid mono-n-butyl ester, terephthalic acid monomethyl ester, 3-hydroxy-5,6,7,8-tetrahydronaphthalene-carboxylic acid- (2), 2-hydroxynaphthoic acid (1) and anthraquinone carboxylic acid (2). Suitable anions of aromatic sulfonic acids are, for example, the anions of Benzenesulfonic acid, benzenesulfonic acid (1,3), 4-chlorobenzenesulfonic acid, 3-nitrobenzenesulfonic acid, 6-chloro-3-nitrobenzenesulfonic acid, toluenesulfonic acid - (4) , Toluenesulfonic acid (2), toluene - {>) - sulfonic acid, 2-chlorotoluenesulfonic acid (4), 2-hydroxybenzenesulfonic acid, n-dodecylbenzenesulfonic acid.

Colorless anions are preferred. For dyeing from an aqueous medium those anions are preferred which increase the water solubility of the dye not affect too much. For dyeing from organic solvents In many cases, preference is also given to those anions which promote or at least promote the solubility of the dye in organic solvents do not affect negatively.

The anion is generally by the manufacturing process and the any purification of the crude dye that may have been carried out is given. In general, the dyes are zinc chloride double salts, acetates, Methosulphates, ethosulphates or halides (especially as chlorides or bromides). The anions can be exchanged for other anions in a known manner.

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In preferred dyes of the formula I, R and R represent methyl or ethyl,

R- for methyl, ethyl, methoxy or ethoxy,

R, for H, fluorine, chlorine, methyl, ethyl, methoxy or ethoxy and

X for an anion.

Of these, those examples are particularly interesting in which R and R for methyl,

R is methyl or methoxy and

R. stand for H.

The new dyes of the general formula I are made by known processes available as z. B. in German patents T 098 642, 1 137 815 and 1 137 816 are described.

For example, they are obtained by reacting compounds of the formula

^R 2

■ ^R 5 R,

(II)

with dimethylamine.
Have in Formula II

R, R, R »and R, the meaning given for formula I.

R ₁ - denotes a group which can be split off by dimethylamine,

^LeA19099 030011 / 02.3 *

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ζ. B. an alkoxy group, an alkylthio group or a halogen atom.

R ₁ . can also mean hydrogen. The reaction with dimethylamine then takes place in the presence of an oxidizing agent, such as atmospheric oxygen.

The reactions of II with dimethylamine can take place in aqueous solution or suspension, in the presence of organic solvents or mixtures thereof with water at room temperature or elevated temperature. Many connections already react between 0 ° and 20 ⁰ C.

Compounds of the formula II are diazotized in a known manner and coupling of aminobenzenes of the formula

(III),

R_, R, and R ₁ . have the meaning given for formula II,

on imidazole and subsequent reaction of the compounds obtained

(IV),

R ", R and R have the meaning given for formula II,

with alkylating compounds of the formula

R ₁ -X (V) or R ₂ -X (Va)

^{LeA 19} ° "0300 1 1/0234

28379S3

R and R have the meaning given for formula I and

X is a group providing an anion X,

or with oxiranes of the formula

CH ^ - CH - R _£

R _{r represents} H, methyl or ethyl.

Suitable diazo components (III) are, for example: 2-methoxy-4-chloroaniline; 2-methyl-4-chloroaniline; o-anisidine; o-toluidine; 2,4-dimethoxyaniline; 2-methyl-4-methoxyaniline; 2-methyl-5-chloroaniline; 2-ethylaniline; 2,5-dimethylaniline; o-phenetidine; 2-methoxy-5-chloroaniline; 2-methoxy-4,5-dichloroaniline; 2-methyl-5-methoxyaniline; 2-methoxy-5-methylaniline; 2-ethoxy-5-methylaniline; 2-methoxy-4-chloro-5-methylaniline; 2-propoxy-5-methylaniline; 2,4-dimethoxy-5-chloroaniline; 2,5-dimethoxyaniline; 2,5-dimethoxy-4-chloroaniline; 2,5-diethoxyaniline; 2-isopropylaniline; 4-fluoro-2-methylaniline; 5-fluoro-2-methylaniline.

The new dyes are suitable for dyeing, printing and mass dyeing materials containing acidic groups, especially of products made entirely or predominantly of polymerized unsaturated nitriles such as acrylonitrile and vinylidene dicyanide or modified from acidic Polyamides or polyesters are made .. They are suitable furthermore for the other known uses of cationic dyes, such as the dyeing and printing of cellulose acetate, Coconut, jute, sisal and silk, from tannin cotton and paper, for the production of ballpoint pen pastes and Stamp inks and for use in transfer printing and rubber printing. The dyeings and prints on the first-mentioned materials, in particular on polyacrylonitrile, are characterized by their very high real

^LeA19 ° "030011/0234

especially through very good light, wet, friction, decatur, Sublimation and perspiration fastness.

Furthermore, the new dyes have a very good balancing capacity, which allows even in light tones on acrylonitrile fibers without great demands on the dyeing technique without the addition of retarders To achieve colorations.

In addition, the new dyes have good affinity and good Kombinierbarke ¹ '. · Oowohl with other well-migrating dyes as well as dyes with less good balance' assets.

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example 1

30 g of the diazotized by coupling! 2-methoxy-4-chloroaniline Imidazole, subsequent methylation with dimethyl sulfate, dissolving in water and precipitation with NaCl obtained dye of the formula

OCH,

Cl

are concentrated in a mixture of 31 g. Hydrochloric acid and 25 g of a 46% strength dimethylamine solution were stirred. Then drops at 90 ⁰ C until a few ml of a dimethyl amine, until the reaction is complete, which can be detected well in Dunnschichtchromatogramm. The mixture is then cooled, diluted: with 100 ml of saturated evaporated salt solution and the pH is adjusted to 5 with hydrochloric acid. The obtained dye of the formula

Cl

is filtered off. It dyes polyacrylonitrile yellowish red with good fastness properties and. good balance.

If you work in the preparation of the starting dye instead of Di ^ methyl sulfate with diethyl sulfate and then proceed as above given, the dye of the formula is obtained

OCH,

Cl

It colors polyacrylonitrile with a real red shade.

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-X- 4h

Example 2

20 g of the 2-methyl-4-chloraniiin obtained by coupling of diazotized Imidazole, subsequent methylation with dimethyl sulfate, dissolving in water and precipitation with NaCl obtained dye of the formula

N = N

Cl

CH "

are reacted analogously to Example 1 with dimethylamine. The received Dyestuff dyes polyacrylonitrile in a bluish red with good fastness properties.

He has the formula

Cl

Example 3

20 g of that obtained by coupling diazotized 2-methyl-4-methoxyaniline Imidazole, subsequent methylation with dimethyl sulfate, dissolving in water and precipitation with NaCl obtained dye of the formula

OCH,

Cl

are, as described in Examples I and 2, with dimethylamine implemented. The dye obtained is identical to the product prepared according to Example 2.

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Example 4

20 g of the by coupling of diazotized o-toluidine onto imidazole, then Methylation with dimethyl sulfate, dissolving in water and precipitation with NaCl of the dye of the formula obtained

O-

CH "

N = N-

Cl

are with 35 ml of a 46% dimethylamine solution at room temperature stirred with the addition of atmospheric oxygen until shown in the thin-layer chromatogram no more starting dye can be detected.

The mixture is then diluted with 100 ml of saturated evaporated salt solution

and adjust the pH to 5 with hydrochloric acid.

The dye obtained is filtered off. He is identical to that

product described in Example 2.

Following the procedures listed in Examples 1, 3 and 4 is obtained the dyes of the general formula

CH,

CH.

H.

Cl

The following table contains some other examples made with Specification of the color shade on polyacrylonitrile

Color on polyacrylonitrile

bluest. Red

Blue red

bluest. Red

Bordo

Red

Red

Example no. R ₃ A. ^R 4 5 OCH ₃ CH ₃ 6th ir OCH 7th ti Cl 8th CH ₃ CH ₃ 9 CH (CH ₃ ) ₂ H 10 CH ₃ F. Le A i9 099 * μ A

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example No. ^R 3 R. 11 C ₂ H ₅ H 12th OC ₂ H ₅ H example 13th

Color on polyacrylonitrile

bluest. Red Red

20 g of the by coupling of diazotized 2-methoxy-4-chloroaniline Imidazole produced azo dye of the formula

0-

OCH

N = N

are stirred in 30 ml of glacial acetic acid. Then initiates at 5O ⁰ C ethylene oxide, until the completed well in Dunnschichtchromatogramm to be followed implementation. The mixture is then diluted with 500 ml of saturated evaporated salt solution and the dye of the formula is precipitated

C ₉ H OH | 2 4

ZnCl,

C ₂ H ₄ OH with zinc chloride.

If this is used analogously to the method described in Example 1 Dimethylamine to obtain the dye of the formula

Cl -ZnCl,

C ₂ H ₄ OH

It colors polyacrylonitrile red.

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Claims (10)

Claims 1. Dyes of the formula "CIL R, wherein R and R "independently of one another represent a lower alkyl, alkenyl or hydroxyalkyl radical, R_ for a lower alkyl, alkenyl or alkoxy radical, R, for H, halogen, a lower alkyl, alkenyl or Alkoxy radical and X stand for an anion. 2. Dyes according to claim 1 wherein
R and R for methyl or ethyl, for methyl, ethyl, methoxy or ethoxy and stand for H, fluorine, chlorine, methyl, ethyl, methoxy or ethoxy ,. Le A 19 099 030011/0234 2 ^ 37953 3. Dyes according to Claim 2 Methoxy and wherein R and R for Methyl, ^R 3 for Methyl or ^R 4 for H stand. 4. A process for the preparation of dyes of those listed in claim 1 Constitution, characterized in that there are compounds of the formula Reacts with dimethylamine. Have in it R, R, R ", R, and X have the meaning given in claim 1. R is one that can be split off by dimethylamine Group such as an alkoxy group, an alkylthio group or a halogen atom. 5. The method according to claim 4, characterized in that one works in aqueous solution or suspension, in the presence of organic solvents or mixtures thereof with water at temperatures between 0 ° and 120 ⁰ C, preferably at 20 ° -90 °. 6. Process for the preparation of dyes of the constitution stated in claim 1, characterized in that compounds the formula Le A 19 099 03ÖÖ11 / 0234 j / - R.
-.11 R ₂ reacts with dimethylamine in the presence of an oxidizing agent. Have in it
R, R, R, R and X have the meaning given in claim 1. 7. The method according to claim 6, characterized in that, in aqueous solution or suspension, in the presence of organic solvents or their mixtures at 20 ° -90 ° C, working with water at temperatures between 0 ° and 120 ⁰ C, preferably. 8. The method according to claim 6, characterized in that the oxidizing agent Is atmospheric oxygen. 9. Process for dyeing or printing textile materials made of polyacrylonitrile or acid-modified polyester or acid-modified polyamide, characterized in that dyes according to Claim 1 - 3 used. 10. Textile materials which are obtained according to claim 9. Le A 19 099 030011/0234