DE2135833A1 - CATIONIC COLORS, THEIR PRODUCTION AND USE - Google Patents

Description

FARBENFABRIKEN BAYER AG LIVERKUSEN-Bayerwerk Central area Patents, trademarks and other Lizcpzc Patents, trademarks «uad Lizcpzca - ,,.

Mi / Kra "Ο · Μ 1971

Cationic dyes, their manufacture and use

The present invention relates to new cationic dyes of the general formula

(HOOC) _n - A -

To ^v

A is an alkylene chain of 1 bio 6 carbon atoms, which with the Naphthalene ring can be linked, or in the case

η * O an alkyl reet,
D a remainder of the formula

/ R

-M;

in which R represents alkyl, cycloalkyl, aralkyl or aryl and R _{1 represents} hydrogen, alkyl, cycloalkyl, aralkyl or aryl, or a radical of the formula

■ R,

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(CH = CH) _1n -R ₂ - 1 1 1 5 2

in which R ₂ for aryl or A - thienyl, R, for Wass era toff, alkyl, aralkyl or aryl, R. for hydrogen or alkyl, R ₅ for hydrogen, alkyl, aralkyl, aryl or ^ - thienyl, R _ß for Hydrogen or alkyl and m is 0 or 1,

the numbers 0, 1 and 2 and

"' denote an anion, and in the case of η = 0 at least one carboxyl group is also contained in the dye molecule, and in which the acyclic and cyclic radicals can be substituted by nonionic radicals and / or carboxyl groups.

Dyes of the general formula are preferred

HOOC - CH ₂ -CH ₂ -

IT.

At-

II

a dialkylamino, diarylamino or aralkylamino group and

"' mean an anion and in which the acyclic and cyclic radicals can be substituted by nonionic substituents and / or carboxyl groups.

Dyes of the general formulas are particularly valuable

HOOC - CH ₂ -CH ₂ -

At*

III

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R «and Rq an Alltylrest with 1 to 4 G-atoms, which is nonionic can be substituted, Y hydrogen »chlorine or bromine, Z hydrogen» a methyl, lower alkoxy, ITrethane

or ureido group or chlorine and An ' ¹ ""' mean an anion »and

HOOC - CH ₂ -CH ₂ -

At*

wherein ^R 9

Methyl or ethyl,

Methyl, ethyl, ß-chlorine, ß-cyano, ß-aminocarbonyl or

ß-phenyl-ethyl group,

Hydrogen, chlorine or bromine, hydrogen, a methyl, lower alkoxy, urethane or ureido group or chlorine and

mean an anion.

Further preferred dyes are those of the general formula

it).

To ^v

D has the meaning given in formula I, R _{11 is} an alkyl radical having 1 to 5 carbon atoms or a benzyl

rest and An ^ "'mean an anion and

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the naphthalene ring and / or D and / or the benzene ring connected to D contain at least one carboxyl group and in which the acyclic and cyclic radicals can be substituted by nonionic radicals ₀

Particularly preferred among these dyes are those of general formulas

To ^v

VI

worxn R -, -,

an alkyl radical with 1 to 5 carbon atoms or a benzyl

rest,

an alkyl, cycloalkyl, aralkyl or aryl radical,

Hydrogen, chlorine or bromine and

denote an anion, and wherein R ₁₁ , R ₁₂ and the ring A

may contain nonionic substituents and / or carboxyl groups and

To ^v

VII

Methyl, ethyl, ß-cyanoethyl, benzyl, 4-methylbenzyl, 4-chlorobenzyl- or 3,4-dichlorobenzyl, an alkyl group with 1 to 5 carbon atoms, which can also be nonionically and / or substituted by carboxyl groups can,

Hydrogen, chlorine or bromine,

Hydrogen, a methyl, lower alkoxy, urethane or ureido group or chlorine and an anion.

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The invention also relates to processes for production these dyes, their use for dyeing and printing natural and synthetic materials as well materials dyed and printed with these dyes. The anionic residues for 'cationic dyes are used customary organic and inorganic anion into consideration. 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, such as nitrate; residues of Oxygen acids of phosphorus, such as dihydrogen phosphate, hydrogen phosphate, Phosphate "and Meta.phosphate; residues of carbonic acid, such as hydrogen carbonate and carbonate; other anions of oxygen acids and complex acids, such as methosulphate, ethosulphate, Hexafluorosilicate, cyanate, thiocyanate, hexacyanoferrate (IT), hexacyanoferrate (III), tri- and letrachlorozincate, tri- and Setrabromozincate, stannate, borate, divanadate, tetravanadate, Molybdate, tungstate, chromate, bichroniate and tetrafluoroborate, as well as anions of esters of boric acid, such as glycerol entera boric acid and 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 sulfonic acids, such as residues of acetic acid, chloroacetic acid, cyanoacetic acid, hydroxyacetic acid, aminoacetic acid, methylaminoacetic acid, aminoethylsulfonic acid, butyric acid, methylaminoethyl acid ,! -Butyric acid, 2-methyl-butyric acid, 2-ethyl-butyric acid, dichloroacetic acid, trichloroacetic acid, i-erifluoric acid, 2-chloropropionic acid, 3-chloropropionic acid, 2-chlorobutyric acid, 2-hydroxypropionic acid, 3-hydroxypropionic acid, O-ethylglyceric acid, thioglycolic acid acid, malic acid, Dodecyltetraäthylenglykolätherpropionsäure, 3- (nonyloxy) propionic acid, 3- (Isotridecyloxy) propionic acid, 3- (Ißotridecyloxy) -diäbhylenglykolätherpropionsäure, Ätherpropionsäure of AHcoholgeiuischou bit 6 to 10 carbon atoms, thioacetic acid, 6-Ben ^(/, oylajnino-

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2-chlorocaproic acid , nonylphenol tetraafchylene glycol ether-ptopionic acid, monylphenol diethylene glycol ether propionic acid, oodocyl tetra-ethylene glycol ether propionic acid, phenoxyacetic acid, Noiij ?! phenoxyacetic acid, n-valeric acid, i-yaleric acid, 2,2,2-tri- ethylessylgic acid _3, n-caproic acid, 2-ethyl-n-caproic acid, stearic acid ₉ oleic acid, ricinoleic acid, paleitic acid, n-pelargonic acid, lauric acid, a mixture of aliphatic carboxylic acids with 9 to 11 carbon atoms (Versatic acid 911 from SHELL) _{9 of} a mixture of aliphatic carboxylic acids with 15 to 19 carbon atoms (Tersatic acid 1519 from SHELL), the Kolcosfettsäure-YorlaiifSs of? Undecanecarboxylic acid, n-tridecanecarboxylic acid and a coconut fatty acid mixture; of acrylic acid, Metiiaesrjisäure, Crotoneäure, propiolic acid, oxalic acid, malonic acid, Bernsteiäsäure, glutaric acid, adipic acid, pimelic _f suberic acid, azelaic acid, Isoiaerengemisches of of 2,2,4- and 2,4,4-3! rimethyladipinsäure, sebacic acid, Isosebacinßäure (Isomeirengemisch .), Tartaric acid, citric acid, glyoxylic acid, bi-, <fJ -dicarboxylic acid, methylene-bis-thioglyeolic acid,

"^ D-dicarbonsaurep 2,2 '-Bithio-di-n-propioiisäure, 3? Na! Aric _{acid 9} maleic acid ₉ itaconic acid, ethylene-bis-itnino acetic acid, nitrilosulphonic acid, methanesulphonic acid, 1thane; 3ulphonic acid, chloromethB, nsilionic acid, 2-chloroethanesulphonic acid and 2-hydroxyethanesulphonic acid, mersolate, that is, ⁰ O ^-0 I ¹ S ^{i>ara; i} ' ^f i ^IlöU ^ ^foil ~ acid, obtained by the Ohio rider from paraffin oil.

Suitable anions of cycloaliphatic carboxylic acids are e.g. the anions of cyclohexanecarboxylic acid, cyclohexene - '^ - carboxylic acid and anions of araliphatic monocarboxylic acids are e.g. Anions of pheßylacetic acid, 4-methylphenyleosetic acid and

Suitable anions aromatischai ^ CarbonBäuren are flowing anions of benzoic acid, 2-HethylbensäoeBäure, 3-Mel.by'ibenzoesäurej 4-Methylbeni5oesäure _s 4-t-3rt.-butylbenzoic acid, 2 Broiaben2oesäure _s 2-öhlos ⁱ bensoesäai5j 3 -Chi orb 550 it en acid, 4-

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Chlorobenzoic acid, 2,4-dichlorobenzoic acid, 2,5-dichlorobenzoic acid, 2-nitrobenzoic acid, 3-nitrobenzoic acid, 4-nitrobenzoic acid, 2-chloro-4-nitrobenzoic acid, 6-chloro-3- nitro-benzoic acid, -2,4-dinitrobenzoic acid , 3,4-dinitrobenzoic acid, 3,5-dinitrobenzoic acid, 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 2-mercaptobenzoic acid, 4-nitro-3-methylbenzoic acid, 4-aminobenzoic acid, 5-nitro-2-hydroxy, 3-hydroxybenzoic acid -Nitro-2-hydroxybenzoic acid, 4-methoxybenzoic acid, 3-nitro-4-methoxybenzoic acid, 4-chloro-3-hydroxybenzoic acid, 3-chloro-4-hydroxybenzoic acid, 5-chloro-2-hydroxy-3- methylbenzoic acid, A- ethylmercapto-2-chlorobenzoic acid, 2-hydroxy-3-methylbenzoic acid, 6-hydroxy-3-methylbenzoic acid, 2-hydroxy-4-methylbenzoic acid, 6-hydroxy-2,4-dimethybenzoic acid, 6- Hydroxy-3 ~ tert-butylbenzoic acid, phthalic acid, tetrachlorophthalic acid, 4-hydroxyphthalic acid, 4-methoxyphthalic acid, isophthalic acid, 4-chlorobophthalic acid, 5-nitro-isophthalic acid, terephthalic acid, nitroterephthalic acid and di phenylcarboxylic acid (3,4), o-vanillin 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-tetrahydronaphthalenecarboxylic acid (2), 2-hydroxynaphthoic acid "(1) and anthraquinone carboxylic acid (2).

Bind, for example, suitable as anions of heterocyclic carboxylic acids the anions of pyrocucleic acid, dehydroglucic acid, Indolyl (3) acetic acid.

Suitable anions of aromatic sulfonic acids bind, for example, the anions of benzene sulfonic acid, benzene disulfonic acid (1,3), A- chlorobenzenesulfonic acid, 3- nitrobenzenesulfonic acid, 6-chloro-3-nitrobenzenesulfonic acid, toluenesulfonic acid (4), toluenesulfonic acid (2), toluene-w -sulfonic acid, 2 ~ chlorotoluene sulfonic acid- (4),

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1-hydroxybenzenesulfonic acid, n-dodecylbenzenesulfonic acid, 1,2,3, 4-tetrahydronaphthalene sulfonic acid (6), naphthalene sulfoHE acid (1), tfaphthalenedisulfonic acid- (1,4) or - (1,5), naphthalene- ■ trisulfonic acid - (* l, 3,5), naphthol- (l) -sulfonic acids 2), 5-nitronaphthalenesulfonic acid- (2), 8-aminonaphthalenesulfonic acid (1), stilbene disulfonic acid (2,2 ') and biphenylsulfonic acid (2).

A suitable anion of heterocyclic sulfonic acids is e.g. Quinoline sulfonic acid (5) anion.

Furthermore, the anions of arylsulfine-, -phosphon- and "-phosphonous acids, such as benzenesulfinic and benzenephosphoric acids into consideration.

Colorless anions are preferred. For dyeing from water-based Medium, those anions are preferred that increase the solubility in water not affect the dye too much. Such anions are often used for dyeing from organic solvents preferred, which promote the solubility of the dye in organic solvents or at least not adversely affect it.

The anion is generally due to the manufacturing process and any purification of the crude dye that may have been carried out given. In general, the dyes are as halides (especially as chlorides or bromides) or as methosulfates, Ethosulfates, sulfates, benzene or toluene sulfates or as acetates. The anions can act against others in a known manner Anions are exchanged.

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In the dyes according to the invention, by definition be included nonionic substituents. As such are for example suitable: fluorine ,. Chlorine, bromine; Alkyl groups, in particular straight-chain or branched alkyl radicals with 1-6 Carbon atoms; Aralkyl radicals; Alkenyl radicals; Aryl radicals; Alkoxy radicals, in particular alkoxy radicals with 1-4 carbon atoms; Aralkoxy radicals; Aryloxy, alkylthio, preferably alkylthio with 1-5 o atoms; Aralkylthio radicals; Arylthio radicals; Nitro; Cyan; Alkoxycarbonyl, preferably those having an alkoxy radical 1-4 carbon atoms; the. Forraylreat; Alkyl carbonyl radicals, in particular those with an alkyl group with 1-4 carbon atoms; Arylcarbonyl; Aralkylcarbonyl radicals; Alkoxy earbonyloxy radicals, preferably with an alkyl group with 1-4 C atoms; Alkylcarbonylamino radicals, preferably with an alkyl group with 1-4 carbon atoms, arylcarbonylamino radicals; Alkylsulfonylamino » radicals, preferably with an alkyl group with 1-3 carbon atoms; · Arylsulfonyl amino groups, urido; N-aryl or N-alkyl ureido, Aryloxycarbonylamino, alkyloxycarbonylainino; Carbamoyl; N-alkyl-carbamoyl; Ν, Ν-dialkylcarbamoyl; N-alkyl-N-aryl-carbamoyl; Sulfamoyl; N-alkylsulfamoyl; Ν, Ν-dialkyl-sulfamoyl ;. Alkylsulfonyl; Alkenylsulfonyl; Aralkylsulfonyl, where in the mentioned Alkyl radicals are preferably 1-4 carbon atoms; Arylsulfonyl, Carboxylic acid alkyl ester, carboxylic acid aryl ester, sulfonic acid alkyl ester and aryl sulfonate groups.

An alkyl radical is a branched or unbranched, saturated or unsaturated aliphatic radical with 1-6 C atoms understood, the nonionic substituents and / or May contain carboxyl groups, e.g. the methyl, ethyl, n- and iso-propyl, n-, iso- and tert-butyl and the various isomeric pentyl and hexyl radicals and vinyl, allyl or Propenyl radical.

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The dyes of the formula I in which η is one or two are prepared by heating compounds of the formula

VIII

wherein D has the meaning indicated in formula I and D, and the aromatic rings may be / or substituted by nonionic radicals and carboxylic groups with unsaturated or anionic leaving groups substituted aliphatic mono- or dicarboxylic acids to a temperature between about 60 and 15O ⁰ C supplied and possibly by subsequent reaction with anions An '' ^ means. the quaternization while entering can be Chromatographiech easily follow. Instead of color bases VIII can also their salts with proton acids such as hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, lactic acid and Use toluenesulfonic acid if an unsaturated acid is used as the quaternizing carboxylic acid. A particularly suitable unsaturated acid is acrylic acid. Suitable carboxylic acids substituted by groups which can be removed by anion are, for. B, chloro- and bromoacetic acid, ck-bromopropionic acid and -butyric acid, ß-chloro and 3-bromopropionic acid. .

Suitable compounds of the formula VIII are summarized in Tables and 2.

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Table 1

Color bases of the formula

methyl methyl hydrogen hydrogen ethyl ethyl It ti n-propyl n-propyl Il It n-butyl n-butyl ti ti Il H chlorine Il Il Il bromine Il It H Acetylamino It ethyl ethyl chlorine Il It Il bromine Il It Il Il Methoxy Il Il Il Ethoxy Il Il It methyl Il ß-chloroethyl Il hydrogen TI Il hydrogen methyl Il β-cyanoethyl Il It ti Il bromine hydrogen Il ß-amidocarbonyl
ethyl hydrogen ti Il ß-phenylethyl It It

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ASL

Table 2

Color bases. the formula

Rr

hydrogen

Methoxy

Ethoxy

Dimethylamino acetylamino

chlorine

bromine

hydrogen

Phenyl

4-methoxyphenyl phenyl 4-methoxyphenyl

3,4-dimethoxy-. phenyl

4-chlorophenyl 4-methylphenyl Phenyl hydrogen phenyl

2-methoxyphenyl 1 hydrogen 0 »0

"-0

Phenyl phenyl

hydrogen

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AS

The quaternization is most expediently carried out in an excess the respective reactive carboxylic acid, which also serves as a solvent or diluent. It can, however organic diluents such as toluene, chlorobenzene or nitrobenzene can also be added. For work-up you can either the excess reagent or diluent distill off under reduced pressure and purify the reaction product by recrystallization from water or the mixture Pour in water and salt out the dye in the usual way.

The dyes of the formula 1 in which η is zero, are prepared by treating dye bases of the formula VIII which contain a carboxyl group with quaternizing agents which in turn are free of carboxyl groups, such as dimethyl and diethyl sulfate, ethylene chlorohydrin, toluenesulfonic acid methyl and -ß-chloroethyl ester, ß-chloro- and ß-bromopropionitrile and ß-ethoxyethyl bromide. The working method corresponds to the information of German Patent 1,165,790. So that the carboxyl groups are not esterified, an excess of the quaternizing Means to avoid.

The dyes of the formula I can also be prepared according to the procedure of German patents 1,190,126a, 1,190,126b and 1,287,004 by heating naphtholactarnene of the general formula

(R ¹ OOC) - A - N_

η ι r- _IX

with compounds of the general formula

ζ \ - DX

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wherein A, D and η have the meaning given in formula I and the cyclic and acyclic radicals can be substituted by nonionic substituents and / or carboxyl groups, and R ^{1 is} hydrogen or a lower alkyl radical, to 70 to 150 ° in the presence of dehydrating condensing agents such as Phosphorus oxychloride, phosphorus tri- and pentachloride, sulfuryl chloride, thionyl chloride or phosgene, optionally with the addition of τοπ inert diluents such as chloroform, nitrobenzene or chlorobenzene and possibly subsequent saponification of the ester group. In general, a subsequent hydrolysis not ER- length conducive because it already takes place in the course of condensation and / 'or reclaimed. The usual work-up consists in pouring the cooled condensation mixture into water for the purpose of hydrolysis of the excess condensation agent and separation of the dye by adding sodium hydroxide solution and / or common salt. The crude dye obtained in this way is generally already uniform, but can, if desired, be further purified by recrystallization from water, optionally with the addition of activated charcoal.

Suitable naphtholactams IX are, for example, hydroxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy and n-amyloxycarbonylmethyl naphtholactams ß-Hydroxy- unä ß-Ethoxy-carbonylethyl-naphtholactam, ^ -Methoxycarbonylpropyl-naphtholactam and their 4-chloro and 4-bromo derivatives.

Suitable compounds X are e.g.

N-methyl-, N-ethyl-, N-ß-chloroethyl-, N-ß-cyanoethyl-, Nn-propyl-, N-iso-propyl-, Nn-butyl-, N-iso-butyl-, N-benzyl-, N-ß-phenylethyl-, N-cyclohexyl-, N-phenyl-, N-4'-methy! Phenyl-, N-4'-methoxyphenyl-, N-2 ^s -methyl phenyl and N-2'-methoxyphenyl-N-ß-methoxy- (un £ -ethoxy) -carbonylethyl-a.niline, N, N-bis-ß-methoxy- (and -ethoxy) -carbonylethyl »anilIn, -m- Toluidine, -manisidine, -m-phenetidine and -m-Chloraailin, also m-dimethyl- and m-diethylamino-benzoic acid methyl or ethyl ester, N-Ethyi-N - ^ - methoxycarbonylpropyl-aniline and N-ethyl-N-4 '-Methoxycarbonyl-benzyl-aniline.

20 9 8 8 "A ¹ AiI 5 2

The new dyes are suitable for dyeing, printing and mass dyeing materials made from polyacrylonitrile and copolymers of acrylonitrile with other vinyl compounds such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinyl acetate, Vinyl pyridine, vinyl imidazole, vinyl alcohol, acrylic and methacrylic acid esters and -amides, as. Dicyanäthylen, modified by acid synthetic materials, especially those made from acid-modified aromatic polyesters and acid-modified ones Polyamide fibers. Acid modified aromatic polyesters are, for example, polycondensation products from suIfoterephthalic acid and ethylene glycol, d. H. sulfonic acid groups Polyethylene glycol terephthalates (type DACRON 64 from E. I. DuPont de Nemours and Company), as described in the Belgian U.S. Patent No. 549,179 and U.S. Patent No. 2,893,816.

They stand out on these materials compared to previously known dyes by better lightfastness, improved rubbing fastness, cheaper evening color (i.e. less nuance difference between lighting with daylight and artificial light) and one very desirable bathochromic shift of the hue, as well as through a significantly improved solubility and through a much lower tendency to undesired precipitations with foreign ions such as rhodanide, cyanide, oxalate and chlorozincate give.

The new dyes are also suitable for dyeing and printing of other textile and non-textile materials, e.g. those made of leather, tanned cotton, cellulose (e.g. paper, coconut, jute, sisal), acetate silk, synthetic Super polyamides and super polyurethanes.

The parts mentioned in the examples are parts by weight; the temperatures are degrees Celeius.

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example 1

5 parts of the compound of formula

[Jh N (C ₂ H ₅ )

are heated to 100 with 10 to 20 parts of acrylic acid. To The quaternization is almost complete in about 3 hours. The mixture is stirred for a further 1 hour at 100 ° and diluted with water and isolates the resulting dye as a zinc chloride double salt the formula

HOOC-CH ₂ -CH ₂ - N.

Cl ¹

χ ZnCl,

The dye gives reddish-tinged blue dyeings and prints with good fastness properties on polyacrylonitrile.

If one of the following compounds is used as the starting material in an equivalent amount, this procedure also gives valuable new dyes. The raw materials are available according to known processes, e.g. according to the information in German Auslegeschrift 1 165 790.

N.

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R " Z 2135833 R ¹ methyl hydrogen Hue on
Polyacrylonitrile methyl Il methyl blue-violet Il Il chlorine reddish blue H Il Methoxy It It ß-chloroethyl methyl Il Il β-cyanoethyl It Il Il n-butyl hydrogen Il ethyl n-propyl It Il n-propyl n-butyl It It n-butyl Cyclohexyl It Il methyl Benzyl It Il Il ß-phenylethyl methyl blue-violet It Benzyl hydrogen reddish blue Benzyl iso-amyl t! violet iso-amyl ethyl Dimethylamine
carbonylamino reddish blue ethyl It Ethoxycarbonyl
amino blue Il Il

Instead of these color bases, the corresponding salts with hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, Acetic acid, propionic acid, lactic acid or glycolic acid can be used.

Example 2

A solution of 4.2! Dents of the compound of the formula

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in 50 to 200 parts of dimethyl formamide, after the addition of 1.3 Parts of acid-free dimethyl sulfate are stirred at about 100 ° for 3 to 4 hours. After cooling, it is diluted with water and the formed dye of the formula

CH ₃ SO ₄ '

in the usual way, for example by salting out with common salt in the form of the chloride or as zinc chloride double salt, isolated. Of the Dye gives very real and brilliant, reddish-tinged blue dyeings and prints on polyacrylonitrile.

If the compounds given in the following table are used as starting materials, this procedure gives also valuable new dyes. The starting materials can be prepared by saponifying the corresponding nitriles or alkoxycarbonyl compounds are produced.

12th
CH ₂ -CH ₂ -COOH

hydrogen

Il Il Il Il

Chlorine bromine

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Color on polyacrylonitrile

methyl violet ethyl Il Phenyl blue-violet 4-methoxyphenyl reddish blue 4-ethoxyphenyl Il methyl strong rotstichi

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^R 12 Hue on ^Y l ethyl Polyacrylonitrile Acetylamino Phenyl reddish blue chlorine Phenyl blue bromine 4-methoxyphenyl Il It 4-ethoxyphenyl ti It 4-ethoxyphenyl ti Acetylamino ß-carboxyethyl ti chlorine ti blue-violet bromine η-butyl It ti Allyl reddish blue Il Benzyl blue-violet hydrogen 4-chlorobenzyl violet It ti Example 3

21.4 parts of 4-bromo-N-ethyl-naphtholactam- (1.8), 56 parts of phosphorus oxychloride and 13 parts of phosphorus pentoxide are added with stirring heated to 80 °. 16.5 parts of N-ethyl-N-ß-methoxycarbonylethyl-aniline are allowed to run in about 1/2 hour, with the temperature is kept at 80-90 °. The mixture is stirred for a few hours at this temperature and the mixture is then carried to 600 parts of water at 50 °. After the hydrolysis of the excess condensing agent has ended, the dye obtained is Solution adjusted to pH 1.5 to 2 by adding 50 # sodium hydroxide solution and salting out with 100 parts of sodium chloride, whereby the dye of the formula

C ₂ H ₅ -N ₌

CH ₂ -CH ₂ -GOOH

01 '

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precipitated in crystalline form in practically quantitative yield. The dye eats very pure and produces polyacrylonitrile fabrics brilliant, very real, reddish blue dyeings and prints.

If, with the same procedure, instead of N-ethyl-N-ß-methoxycarbonylethyl-aniline, the equivalent amount of N ₁ N-diß-methoxycarbonylethyl-aniline is used, the dyestuff of the formula is obtained in a practically quantitative yield

Cl '

This dye also gives rise to polyacrylonitrile fabrics very real, reddish blue dyeings and prints.

Example 4

20 parts of N-benzyl-naphtholactam-CljS) are according to the information of Example 3 with 16.5 parts of N-ethyl-N-ß-methoxycarbonylethyl-aniline condensed. The dye of the formula is obtained

2 ⁿ 5
0H ₀ -CH ₀ -COOH

Cl '

the polyacrylonitrile colors real blue.

The following are used instead of N-benzyl-naphtholactam Naphtholactam derivatives in an equivalent amount, so you also get very real, blue dyes:

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11

methyl

β-cyanoethyl

n-propyl

Benzyl

4-methylbenzyl 4-chlorobenzyl 3,4-dichlorobenzyl IT, 2-trimethylene

n-butyl

n-amyl iso-Amy1

chlorine

bromine

hydrogen

Chlorine bromine

Il

chlorine

Il

Bromine hydrogen

Chlorine bromine chlorine bromine

Il
Il

chlorine

Example 5

22.7 parts of HT-hydroxycarbonylmethyl-naphtholactam are with 20 to 25 parts of N, N-diethylaniline, 75 parts of phosphorus oxychloride and 20 parts of phosphorus pentoxide heated to 80-90 ° for 5 to 6 hours. The work-up according to the information in the example 3 gives the dye of the formula

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HOOG-OH ₂ -N.

Gl '

which is very real on polyacrylonitrile, · blue dyeings and prints results.

The starting product was made of naphtholactam sodium and chlorine sodium acetic acid can be obtained by condensation in alcohol or dimethylformamide; it melts after recrystallization from ethanol / dioxane (2: 1) at 260 °.

Correspondingly, N-ethoxy carbonylmethyl naphtholactam is obtained from ethyl chloroacetate available, which melts after recrystallization from cyclohexane at 85 °.

Used instead of the naphtholactam derivative given above 25.5 parts of this ethyl ester, the same dye is obtained with saponification of the ester group.

Instead, 25.5 parts of N-ß-methoxycarbonylethyl naphtholactam are used or the equivalent amount of ethoxycarbonylethyl naphtholactam, this gives the homologous dye of the formula

H00G-GH ₂ -CH ₂ -N__

he

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the polyacrylonitrile colors real blue

If the equivalent amount of 2-methoxy-diphenylamine is used instead of the diethylaiiilin, the dye of the formula given below (A = -CHp-) is obtained when using hydroxy- or ethoxycarbonylmethylnaphtholactam and otherwise unchanged. Methoxy- (or -Athoxy) -carbonyläthy! Naphtholactam the homologous dye (A = -CH ₂ CH ₂ -):

HOOC - A - N

Cl '

Both dyes produce excellent, true, blue dyeings and prints on polyacrylonitrile.

Example 6

An aqueous dyebath containing per liter

0.75 g of 30% acetic acid, 0.40 g of sodium acetate and 0.25 g of the formula color

HOOC-CH ₂ -CH ₂ -N

. χ ZnCl,

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is charged at approx. 45 ^° C. with the amount of polyacrylonitrile fibers corresponding to the liquor ratio 1:40, heated to boiling within 20-30 minutes and held at this temperature for 30-60 minutes. After the fibers have been rinsed and dried, a reddish-tinged blue dyeing of good lightfastness is obtained.

Example 7

Acid modified polyglycol terephthalate fibers of the DACRON type 64 (DuPont), or as described in Belgian patent specification 549 179 and in US patent specification 2,893,816 are, are at 20 ° in a liquor ratio 1:40 in an aqueous Bath introduced, the per liter 3 g of sodium sulfate, 0.5 2 g of an oleyl polyglycol ether (50 mol of ethylene oxide), 2.5 5 g diphenyl and 0.3 g of the dye of the first formula of Example 5, and with acetic acid to a pH of 4.5 - 5.5 was set. It is heated within 30 Minutes to 98 ° and keeps the bath at this temperature for 60 minutes. The fibers are then rinsed and dried. A blue dyeing with good fastness properties is obtained.

Example 8

In a staining beaker of 500 ml, which is in a heated Water bath is, 0.75 g of the dye of the first formula of Example 5 are hot with 20 times the amount

Le A13 871 . - 24 -

209884 / 1.1B2

Water, with the addition of a little acetic acid amyote and with dissolved in hot water. The dye liquor still receives an additive of 0.5 g of the product of action of 50 moles of ethylene oxide to 1 mole of oleyl alcohol and is with cold Vv- ^ water on 500 ml filled up. The pH of the dye liquor is adjusted to 4.5 to 5 with acetic acid or sodium acetate.

In this dye bath, 10 g piece goods made of acid-modified polyamide can be constantly kept in motion, while increased in 15 minutes the temperature to 100 ⁰ C. At the boil dyed 15-20 minutes, the material rinsed with cold water and dried subsequently, for example by ironing or in the drying oven at 60-70 ⁰ C. This gives a blue gefärbtef material.

Example 9 ,

A fabric made of polyacrylonitrile is steered with a pressure pad as follows Composition printed:

30 parts of the dye of the first formula of Example 5

50 parts of thiodiethylene glycol

30 parts of cyclohexanol ^; - ·

30 parts of 30 # acetic acid 500 parts of crystal gum

30 parts of aqueous zinc nitrate solution (d = 1.5) and 330 parts of water.

The pressure obtained is dried, steamed for 30 minutes and then rinsed. You get a blue print with very good fastness properties.

Le A 13 871 - 25 -

209 884/1152

Claims (13)

Claims ; wherein A is an alkylene chain τοη 1 to 6 carbon atoms, which with the Haphthalene ring can be linked, or in the case η = 0 is an alkyl radical,
D is a remainder of the formula in which R represents alkyl, cycloalkyl, aralkyl or aryl and R _{1 represents} hydrogen, alkyl, cycloalkyl, aralkyl or aryl, or a radical of the formula ^R 5h ■ a « R, (CH = CH) _m -R,> in which R ₂ for aryl or A.-thienyl, R, for hydrogen, alkyl, aralkyl or aryl, R. for hydrogen or ^ alkyl, Rc for hydrogen, alkyl, aralkyl, aryl © der 4-thienyX, Rg for hydrogen or alkyl and m stand for 0 or 1, the numbers O, 1 and 2 and
mean an anion, and in which in the case of η = 0 at least Le A13 871 -26- 209884/1152 there is still a carboxyl group in the dye molecule, and wherein the acyclic and cyclic radicals are substituted by nonionic radicals and / or carboxyl groups can. 2. Cationic dyes of the general formula HOCfC - CH ₂ -CH ₂ - To ^v where ^L D _{1 is} a dialkylamino, diarylamino or aralkylamino group and At '""' mean an anion and in which the acyclic and cyclic radicals can be substituted by nonionic substituents and / or carboxyl groups. 3. Cationic dyes of the general formula HOOC - CH ₂ -CH ₂ - wherein R ₇ and R _{8 are} an alkyl radical with 1 to 4 carbon atoms which can be nonionically substituted, T hydrogen, chlorine * "oäer bromine, Z ·· - hydrogen, a methyl, lower alkoxy, urethane ' or Ur-eido group or chlorine and An'"*'mean an anion. Le A15 871 - 27 - 209884/1 1 52 4. Cationic ^ dyes of the general formula HOOG - CH ₂ -CH ₂ - To ^v wherein Methyl or ethyl, Methyl, ethyl, ß-chlorine, ß-cyano, ß-aminocarbonyl or ß-phenyl-ethyl group, Hydrogen, chlorine or bromine, hydrogen, a methyl, lower alkoxy, urethane or ureido group or chlorine and mean an anion. 5. Cationic dyes of the general formula At ^ wherein D has the meaning given in formula I, R _{11 is} an alkyl radical having 1 to 5 carbon atoms or a Benayl radical and An ^ "'mean an anion and wherein the kaphthalene ring and / or D and / or that connected to D Benzene ring. Contain at least one carboxyl group and in which the acyclic and cyclic radicals by nonionic c Radicals can be substituted. Le A 13 - 28 - 209884 / 11S2 135833 6. Lationic dyes of the general formula R ₁₁ - y - f \ ll wherein an alkyl radical with 1 to 5 carbon atoms or a benzyl radical, an alkyl, cycloalkyl, aralkyl or aryl radical, hydrogen, chlorine or bromine and
mean an anion, and in which Rm, R-, "and the ring contain nonionic sub-substituents and / or carboxyl groups can. 7. Cationic dyes of the general formula To ^v wherein R ₁₅ methyl, ethyl, ß-cyanoethyl, Benayl, 4-methylbenzyl, 4-chlorobenzyl or 3,4-dichlorobensyl, an alkyl group with 1 to 5 carbon atoms, which are also nonionically and / or substituted by carboxyl groups can, Hydrogen, chlorine or bromine, Hydrogen, a methyl, lower alkoxy, urethane or ureido group or chlorine and
mean an anion. Ie A 13 871 - 29 - 209884 / 11S2 135833 8. Process for the preparation of cationic dyes general formula wherein
A. (HOOC) _n - A - Il At* an alkylene chain of 1 to 6 carbon atoms, which can be connected to the naphthalene ring, or in the case η = 0 an alkyl radical,
a remainder of the formula -NC in which R represents alkyl, cycloalkyl, aralkyl or aryl and R _{1 represents} hydrogen, alkyl, cycloalkyl, aralkyl or aryl, or a radical of the formula (CH = CH) _1n -R ,, in which R «for aryl or ^ -Thienyl, R, for hydrogen, alkyl, aralkyl or aryl, R, for hydrogen or alkyl, R ₅ - for hydrogen, alkyl, aralkyl, aryl or ^ - thienyl, Rg for hydrogen or alkyl and m stand for 0 or 1, " η the numbers 0, 1 and 2 and An ^ "" 'mean an anion, and in which in the case of η = 0 at least there is still a carboxyl group in the dye molecule, and wherein the acyclic and cyclic radicals are substituted by nonionic radicals and / or carboxyl groups can, Le A15 871 - 30 - 209884/1152 characterized in that compounds of the general formula wherein D has the meaning given above, or its salts with unsaturated or substituted by groups that can be split off by anion aliphatic carboxylic acids at 60 to 150 ° and optionally treated with anions an * "'supplying agents; 9. The method according to claim 8, characterized in that there is used as the unsaturated carboxylic acid acrylic acid. 10. Process for the preparation of cationic dyes of the general formula (HOOO) _n - A - IT; I) At ^ wherein
A. an alkylene chain of 1 to 6 carbon atoms, which can be connected to the naphthalene ring, or in the case of η = 0 an alkyl radical,
a remainder of the formula / R Le A13 871 209884/1152 135833 in which R represents alkyl, cycloalkyl, aralkyl or aryl and R _{1 represents} hydrogen, alkyl, cycloalkyl, aralkyl or aryl, or a radical of the formula in which R ₂ for aryl or * - l'hienyl, R * for hydrogen, «alkyl, aralkyl or ₍ aryl, R, for hydrogen or alkyl, R ₅ for hydrogen, alkyl, aralkyl» aryl öäer * v ~ thienyl, R _{6 stands} for hydrogen or alkyl and must often be 1, η the numbers 0, 1 and 2 and An ^ "^ means an anion» and where η * = 0 contains at least one carboxyl group in the dye molecule 5et _t and where the acyclic and cyclic radicals can be substituted by nonionic radicals and / or carboxyl groups, characterized in that compounds of the general formula (R ¹ OOC) _n - A - -H. with compounds of the general formula IeA13 871 209Ö84 / 1152 ORiQfNAL INSPECTED 135833 wherein A, D and η have the meaning given above and the acyclic and cyclic radicals can be substituted by nonionic substituents and / or carboxyl groups, and R ^{1 is} hydrogen or a lower alkyl radical, at 70 to 150 ° in the presence of an anion An ^ ""'converting the condensing agent, optionally with the addition of an inert diluent, and possibly saponifying the ester group. 11. Process for the preparation of cationic dyes of the general formula At ^ has the meaning given in formula I, an alkyl radical with 1 to 5 carbon atoms or a Benayl « rest and mean an anion, and wherein
the haphthalene ring and / or D and / or the benzene ring linked to D contain at least one carboxyl group and in which the. acyclic and cyclic radicals can be substituted by nonionic "radicals, characterized in that compounds of the general formula wherein D has the meaning given above, with compounds of the general formula A 13 871 - 33 - 2 0 9 8 8 4/1152 135833 R ₁₁ - to ₁ wherein R -, -, has the meaning given above and An, one as Anion which can be split off represents, converts and, if necessary, an, exchanged by An. 12. Process for dyeing, printing and bulk dyeing of Materials that are completely or predominantly made of polymer ψ sated unsaturated nitriles such as acyl nitrile or vinylidenecyanide, made of acid-modified polyamides or of acid-modified polyesters, characterized in that dyes of claims 1 to 7 are used. 13. Materials that consist entirely or predominantly of polymerized unsaturated nitriles such as acrylonitrile and tinylidenecyanide, from acid-modified polyamides or from acid-modified ones Polyesters are made, and those colored with dyes of claims 1 to 7, printed or colored in the mass have been. Le A 13 871 - 34- - 209 88 4/1152