DE2232542A1 - CATIONIC AZO DYES - Google Patents

Description

Azo cationic dyes

DU) present invention "relates to cationic azo dyes that are free of sulfonic acid groups and .the general formula

Λ _η \

own what

R is hydrogen, a substituted methyl radical, at least one Alkyl radical containing 2 carbon atoms, an alkoxy, ■ cycloalkyl, aryl, aralkyl or heterocyclic radical,

R ^ Y / as3stoff, an alkyl or aralkyl radical, or

K ind K ^ are connected to a heterocycle, R _{2 is} hydrogen, an alkyl or alkoxy radical or halogen, κ., An alkyl, alkenyl, alkynyl or aralkyl radical, E is the radical of a coupling component and

An ^ "^ mean an anion, ^f

and wherein the cyclic and acyclic radicals are nonionic May contain Suhstituenten and / or carboxyl groups.

Le AH 485 - 1 -

309884/1263

The invention also relates to the preparation of the dyes I and their use for dyeing and printing natural and synthetic materials.

Nonionic substituents within the meaning of the present invention, Findings are the non-dissociating ones customary in dye chemistry Substituents such as cyano, hydroxy, halogen, nitro, alkyl, optionally substituted amino, phenyl, alkoxy, Acyloxy, alkoxycarbonyl, alkoxycarbonyloxy, where alkyl and alkoxy preferably contain 1-4 carbon atoms and acyl in particular represents C 1-4 alkylcarbonyl.

Preferred dyes correspond to the general formula

N = N-K

To ^v

II

R, R ₁ , R ₂ , R ₅ and An have the meaning given in formula I.

have and

K _{1 is} a remainder of the formulas

NO,

represents in which

R. hydrogen, alkyl, alkoxy or halogen, R ₅ hydrogen, alkyl, alkoxy, acylamino or halogen,

Rg hydrogen, alkyl or aralkyl,

Le A U 485

309884/1263

R ^ alkyl, aralkyl or aryl, R ₈ alkyl or aryl, Rn hydrogen, alkyl or aralkyl,

R ₁₀ denotes alkyl, cyano, halogen or nitro, and in which the substituents R to R ₁₀ , insofar as they represent alkyl or aryl radicals, represent further nonionic substituents

can.

Suitable radicals R are ": for example hydrogen, ethyl, iso-propyl, propyl, butyl, sec. Butyl, tert-butyl, iso-butyl, Pentyl, hexyl, octyl, phenoxymethyl, benzyl, 2-phenyl-ethy1, Cyclopentyl, cyclohexyl, phenyl, 4-chlorophenyl, 3-chlorophenyl, 4-nitro-phenyl, 3-nitro-phenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2,4-dimethoxyphenyl, 1-naphthyl, 2-naphthyl, 2,4-dichlorophenyl, 4-dimethylaminophenyl, 2-tolyl, 3-tolyl, 4-tolyl, 2-phenylethylene, 2-rthienyl, 2-furyl, 2-tetrahydrofuryl, as well as methoxy, ethoxy and propoxy.

Furthermore, in the event that R together with R-. completes a cyclic substituent, this together with the carbonamido radical form a cyclic amide or imide, for example a phthalimidox, naphthalimide, maleimido, Succinimido or butyrolactam residue.

Preferred radicals R ₁ are, for example, hydrogen, methyl, methoxy, ethoxy, chlorine and bromine.

Preferred radicals R ₂ are, for example, hydrogen, methyl, methoxy, ethoxy, chlorine and bromine.

Preferred radicals R are, for example, methyl, ethyl, propyl, butyl, 2-cyanoethyl, 2-carbamoylethyl, 2-methoxycarbonyl! ethyl, 2-carboxyethyl, 2-hydroxyethyl, allyl, methallyl, propargyl and benzyl.

Preferred alkyl groups R. and R.sup.- are those with 1-4 carbon atoms, such as CH ₃ -, C ₂ H ₅ -, C ₅ H ₇ -, IsO-C ₅ H ₇ -, C ₄ H ₉ -, iso -C.Hn-, tert. C.Hq-.

Le A 14 485 - 3 - 3 0 9 8 8 4/126 1

Preferred groups Rg and R ₇ are those with 1-4 carbon atoms,

like CH ₃ -, C ₂ H ₅ -, C ₃ H ₇ -, 1SO-C ₃ H ₇ -, C ₄ H ₉ -, IsO-C ₄ H ₉ -,

sec. C ₄ H ₉ -, -C ₂ H ₄ CN, -C ₂ H ₄ OH, -C ₂ H ₄ Cl, -CH ₂ -C ₆ H ₅ , -C ₂ H ₄ -C ₆ H ₅ ,

-C ₂ H ₄ O-ACyI, -C2H ₄ O-CO-O-AIlQrI, -C ₂ H ₄ -O-AIlCyI, -O ₂ H ₄ -CO-O-AIlCyI ₁ -C ₂ H ₄ -O- CO-NH-AIlCyI, where alkyl is preferably C .. -C, alkyl and acyl is preferably C.-C.-alkylcarbonyl or optionally substituted phenylcarbonyl.

Suitable alkyl groups Rg and R ^ ₀ are preferably unsubstituted C.-C ₄ -alkyl radicals such as, for example, CH ₃ -, C ₂ H ₅ -, C ₃ H ₇ -, IsO-C ₃ H ₇ -, C ₄ H ₉ -, IsO -C ₄ H ₉ -.

Suitable alkyl radicals R ₉ are preferably those with 1-4 C atoms which can be further substituted, for _{example by -CN, -CO-NH 2 , -COOH, for example CH 3} -, C ₂ H ₅ -, C ₃ H ₇ - , C ₄ H ₉ , -C ₂ H ₄ CN, -C ₂ H ₄ CONH ₂ , -C ₂ H ₄ -COOH.

Preferred alkoxy groups R ₄ and R ₅ are those with 1-4 carbon atoms, such as -0-CH ₃ , -QC ₂ H ₅ , -0-C ₃ H ₇ , -0-C ₄ Hq, -0-CH ₂ -CH ₂ -OH, -0-CH ₂ -CH ₂ -O-CH ₃ .

Suitable aryl radicals R ₇ and R _g are preferably unsubstituted phenyl.

Suitable acylamino groups R ₅ are, for example, -NH-CHO, -NH-CO-CH ₃ , -NH-CO-C ₂ H ₅ , -NH-CO-C ₄ H ₉ , -NH-CO-C ₂ H ₄ OH, -NH-SO ₂ -CH ₃ , -NH-SO ₂ -C ₆ H ₅ , -NH-CO-CH ₂ -OC ₆ H ₅ , -NH-CO-OH ₂ -C ₆ H ₄ Cl- (P) , -NH-CO-C ₆ H ₅ , -NH-CO-C ₆ H ₃ Cl ₂ ^ (2.5), -NH-CO-CH ₂ -C ₆ H ₅ .

Suitable halogen atoms R ₄ , R ₅ , R ^ ₀ are preferably chlorine or bromine.

Le A 14 485 - 4 -

3 0 9 8 3 \ l ι? ß

The anionic residues are used for cationic dyes customary organic and inorganic anions. Inorganic anions are, for example, fluoride, chloride, bromide nnä iodia., Perchlorate hydroxyl, residues of S-containing acids such as hydrogen sulfate, sulfate, disulfate and aminobuIfate; Residues of nitrogen-oxygen acids, such as nitrate; Residues of sour acids. of phosphorus, such as hydrogen phosphate, hydrogen phosphate, phosphate and metaphosphate; Carbonic acid residues such as hydrogen carbonate and carbonate; more anions · Sauer-Btoffsäuren and Kömplexsäuren, wiq methosulfate, ¹ Äthofiulfat, cyanate, Thiocjrrfnat, tri- and Tetrachloroziilkat, tri- and ietrabromozinkat, stannate, borate and tetrafluoroborate and anions of esters of boric acid as the Glycerinesters of boric acid and esters phosphoric acid, like methyl = phosphate. .

Organic anions are, for example, amounts of saturated or unsaturated aliphatic oycloaliphatic, aromatic and heterocyolic carboxylic acids and sulphonic acids, such as residues of acetic acid, chloroacetic acid, cyanoacetic acid, hydroxyacetic acid, aminoacetic acid, methylaminoacetic acid, methylaminoacetic acid, 3-methylpropionic acid, propionic acid, propionic acid, propiono-2-chloroethyl, methylpropanoic acid hydroxypropionic acid, 3-Hy "droxypropionsäure, O-Aethylglykolsäure, glyceric acid, 3- (No = hyloxy) propionic acid, Aetherpropionsäure of Alkoholgemisohes having 6-10 carbon atoms, ether-Nonylphenoltetraöthylenglykol = propiönsäure, Nonylphenoldiäthylenglykolätherpropionsäü" j re, Dodeoyl-tetraäthylenglykoläther-propiohsäu ^ e, phenoxy = «• acetic acid, 2, fe, 2-trimethyleesetic acid, n-caproic acid, 2-ethyl · · fl-capric acid, stearic acid, oleic acid, ricinoleic acid, palmitic acid, n-pelargonic acid, lauric acid ^ of a mixture alipha =

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tisoher carboxylic acids with 9-11 carbon atoms (Versatic acid 911 from SHELL), a mixture of aliphatic carboxylic acids with 15-19 carbon atoms (Versatio acid 1519 from SHELL) / * s, lokosfettsäure-yorlaufs, der ^ undecancarboxylic acid, n-tridecanecarboxylic acid and a coconut fatty acid mixture; acrylic acid, methacrylic acid, crotonic acid, propargylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, xorkic acid, azelaic acid, the isomeric mixture of 2,2,4- and 2,4,4-trimethylaipic acid. Sebacic acid, iaosebacine acid (mixture of ies), tartaric acid, citric acid, glyoxylic acid, B1-.Bethylether-Ä, rf. n-propionic acid, fumaric acid, maleic acid, ethyl-bis-imihoacetic acid, methanesulphonic acid, ethanesulphonic acid , 2-hydroxyethanesulphonic acid, mersolate, ie C ₈ -C ₁₈ paraffin-sulphonic acid, obtained by chlorosulphonation of paraffin oil.

Suitable anions of cycloaliphatic carboxylic acids are e.g. the anions deif cyclohexanecarboxylic acid, cyclohexene-3-carbonic acid and anions of araliphatic monocarboxylic acids are e.g. Anions de.r phenylacetic acid, 4-methylphenylacetic acid and i Mandelic acid. . ,

Suitable anions of aromatic carboxylic acids are, for example, anions of benzoic acid, 2-methylbenzoic acid, 3-methylbenzoic acid, 4-methylbenzoic acid, 4 ^4- tert.-butylbenzoic acid, 2-bromobenzoic acid, 2-chlorobenzoic acid, 3-chlorobenzoic acid, 4-

Chlorobenzoic acid, 2,4-dichlorobenzoic acid, 2,5-bichlorobenzoic acid, 2-nitrobenzoic acid, 3-nitrobenzoic acid, 4-nitrobenzoic acid Acid, 2-chloro * -4-nitrabenzoic acid, o-chloro-iJ-nitro-benzoic acid, i, 4-Dinitrobeneoic acid, 3,4-Dinitrobenzoic acid, 3,5-Dinitrobenzoic acid, 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, 4-

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3 0 3 SS; / 12 6 Ά

Hydroxybenzoic acid ,. 2-mercaptobenzoic acid, .4; -nitro-3-ynethylbenzoic acid, 4-aminobenzoic acid, 5-nitro-2-hydroxybenzoic acid, 3-nitro-2-hydroxybenzoic acid ,. 4-methoxybenzoic acid, 3-nitro-4- _; methoxybenzoic acid, 47phlorr3- _J hydroxybenzoic acid, 3-chloro-4-hydroxybenzoeeäure, S-chloro ^ -hydroxy ^ -methylbenzoesäure, 4-Äthylmercapto-2-ch.lorbenzoQsäure, 2-hydroxy-3-methyl'benzoeöäure, 6-HydrdXy-3 -methy! benzoic acid, 2-hydoxy-4-methylbenzoic acid, 6-hydroxy-2,4-dimethylbenzoic acid, 6-hydroxy-3-tert.-t) uty! benzoic acid, phthalic acid, tetrachlorophthalic acid, 4-hydroxyphthalic acid, 4-methoxyphthalic acid, isophthalic acid, 4- -Chlorisophthalsäure, 5-nitro-isophthalic acid, terephthalic acid, and iiitroterephthalsäure Diphenylcarbonsäure- (3,4) _l o-Vanillinfeäure, 3-sulfobenzoic acid, BenzoltetracarbQnsäure-Cl ^^^) fraphthalintetracarbonsäure- (l, 4 '5, 8), biphenylcarboxylic acid (4), abietic acid, phthalic acid mono-n-butyl ester, terephthalic acid monononiethyl ester, 3-hydroxy-5,6, TjS-tetrahydronaphthalenecarboxylic acid (2), 2-hydroxynaphthoic acid (1) and anthraquinone 2). . ,,. · .- ·, '·' ■

Examples of suitable anions are heterocyclic carboxylic acids the anions of pyrocucic acid, dehyäroschlimic acid, Indolyl (3) acetic acid.

Suitable anions of aromatic sulfonic acids are e.g. Anions of benzenesulfonic acid, benzenesulfonic acid (l, 3) »4-chlorobenzenesulfonic acid, .3-nitrobenzenesulfonic acid, 6-chloro-3-nitrobenzenesulphonic acid, toluenesulphonic acid- (4) »JColuenesulphone-j acid- (2), toluene-i ^ -sulfonic acid, 2-chlorotoluenesulfonic acid- (4) »

Le A 14 485 - 7 -

3 0 9 ES kl 1? B Ί

l-hydroxybenzenesulfonic acid ,! n-DodecylbeazolStflfonBaure, 1,2,3, 4-Tetrahydronaphthalenesulfonic acid- (6),:. Na phthalinsulfοηε Mure-CD, Naphthalenedisulphonic acid-Cl ^) or - (1,5), naphthalenedisulphonic acid- (1,3,5), Kaphthol- (l) -sulphonic acid- (2), 5-nitronaphthalenoulfonic acid- (2), 8-aminonaphthalene-sulfonic acid- (1),, · stilbene disulfonic acid- (2,2 ') and biphenylsulfonic acid- (2). :

'Preference is given to colorless anions. For dyeing from an aqueous medium, preference is given to those anions which are soluble in water Do not affect the dye too etark, 'For the dyeing Such anions are often also from organic solvents preferred that the solubility of the dye in organic ! Promote solvents or at least not negatively influence them.

The anion is generally produced by the manufacturing process uhd the cleaning of the raw dye that may have been carried out given. In general, the dyes are in the form of halides (especially ale chlorides or bromides) or as methosulfates, Xthosulfate, sulfate, benzene or toluene sulfonate or as Acetates before. The anions can act against others in a known manner Anions are exchanged. j

Particularly preferred dyes have the general formulas

R ₁₁ -CO-NH

To ^v

III

Le A14485

3 0 9 8 S U / 1? G Ά

wherein R ₁₁

To ⁽ 'and

■ -..- -C ₂ H ₅ , -C ₃ H ₇ , ISO-C ₃ H ₇ , -C ₄ H ₉ , IsO-C ₄ H ₉ , BeIcO ₄ H _9,. tert-C ₄ H ₉ , -CH ₂ -OC ₆ H ₅ , -CH ₂ -C ₆ H ₅ , C ₆ H ₅ , -C ₆ H () C ₆ H ₃ Cl ₂ - (2.5), -C ₆ H ₄ -CH ₃ - (O, m and p), -C ₆ H ₄ -O -0-CH ₃ , -0-C ₂ H ₅ ,

Alkyl with 1-4 C atoms, 2-cyanoethyl, 2-carbamoylethyl or benzyl,

Hydrogen, chlorine, bromine, methyl, ethyl, methoxy or ethoxy,

Hydrogen, methyl, ethyl, methoxy, ethoxy, chlorine, bromine, acetyl, methylsulfonyl or benzoylamino, hydrogen, alkyl with 1-4 carbon atoms or benzyl, hydrogen, alkyl with 1-4 carbon atoms, benzyl or phenyl, and
an anion ^ mean

wherein

To ^v

₁₂ and An ^ "'have the meaning given above and methyl, ethyl or phenyl and

Hydrogen, methyl, ß-cyanoethyl, ß-carbamoylethyl and mean ß-carboxyethyl.

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The dyes der'Formel I are prepared by 2-Amino-benzothiazole of the formula

R-GO-N

diazotized, with a coupling component of the formula KH-VI

couples and with a quaternizing agent of the general formula

it ^ -A Vl ±

reacted, where in the formulas V to VII K and the radicals R to Rz have the meaning given in formula I and X denotes a group which can be split off ^{as an anion An * 1 "".}

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Suitable 2-aminot) enzthiazoles of the formula V are, for example way:.

ö-Formylamino '- ^ - aminobenzthiazoli, 6-propionylamino-2-aminobenzothiazole,

ö-Butyrylamino ^ -aminobenzthiazole ,

6- | _ (2-methylpropionyl) -aminoJ-2-aminobenzothiazole, 6- ß3-Methyipropionyi) -amino]] - 2-aminobenzthiazole, 6- (trimethyl-acetyl-amino) -2-aminobenzothiazole, o-pentyicarbonylamino ^ -aminobenzothiazole, 6-heptylcarbonylamino-2-aminobenzothiazole, o-Phenoxyacetylamino ^ -aminobenzothiazole, e-Phenyiacetylamino ^ -aminobenzthiazoi, 6- (ß-phenyl-propionylamino) -2-aminobenzothiazole, 6-benzoylamino-2-aminobenzothiazole, 6- (p-chlorobenzoy! Amino) -2-aminobenzothiazole, 6- (m-chlorobenzoylamino) -2-aminobenzothiazole, 6- (o-chlorobenzoylamino) -2-aminobenzetbjiazole, 6- (2,5-dichlorobenzoylamino) -2-aminobenzothiazole, b- (2,4-Diohlorb.enzoylamino) -2-aminobenzothiazole, 6- (p-nitrobenzoylamino) -2-aminobenzothiazole, 6- (m-nitrobenzoylamino) -2-aminobenzothiazole,

6- (p-Dimethylamino-benzoylamino) -2-aminobenzothiazole,

6- (p-Tolylcarbonylamino) -2-aminobenzothiazole, 6- (m-Telylcarbonylamino) -2-aminobenzothiazole, 6- (o-Tolylcarbonylamino) -2-aminobenzthiazole, 6- (p-Methoxy-benzoylamino) -2-aminobenzthiazole, 6- (2-thenioylamino) -2-aminobenzothiazole, 6- (2-furoylamino) 2-aminobenzothiazole, 6- jj (2-tetrahydrofuroyl) -amino] -2-aminobenzothiazole, 6-cyclohexylcarbonylamino-2-aminobenzothiazole, 6-cyclopentylcarbonylamino -2-aminobenzothiazole, 6-cinnamoylamino-2-aminobenzthiazole, ⁱ t-chloro-6-benzoylamino-2-aminobenzthiazole, 4-methyl-6-benzoylamino-2-aminobenzothiazole, 4-methoxy-6-benzoylamino-2-aminobenzthiazole,

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6 ~ benzoylamineb-7-chloro-2-aminobenzothiazole, 6- (benzoyl-N-methyl-amino) -2-aminobenzothiazole, 6- (propylcarbonyl-N-methyl-amino) -2-aminobenzothiazole, 6- (benzoyl-N -butylanfino-amino) -2-aminobenzothiazole, 6- (cinnamoyl-N-methyl-amino) -2-aminobenzothiazole, 6- (4-chlorobenzoyl-N-methyl-amino) -2-aminobenzothiazole, 6- (4-methylbenzoyl -N-methyl-amino) -2-aminobenzothiazole 6- (4-nitrobenzoyl-N-propyl-amino,) -2-aminobenzothiazole ö _{t-phthalimido} - ^ - aminobenzothiazole, 6 ~ naphthalimido-2-aminobenzothiazole. ι

So far not the 2-aminobenzothiazoles described are familiar from the literature, they can be prepared by processes known per se, for example by selective ones Acylation of the 6-amino group or 6-alkylainino group of 2,6-diaminobenzothiazoles with carboxylic anhydrides or Carboxylic acid chlorides.

Suitable coupling components of the formula VI are, for example way:

N, N-dimethylaniline, Ν, Ν-diethylaniline, N-methyl-Nn-butyl- ■ aniline, Ν, Ν-diethyl-m-toluidine, NN-diethylamino-I-chlorobenzene, N ^ -diethyl-N'-formyl -m-phenylenediamine, N, N-dieth ^ 'l ~ N' -acetyl-m-phenylenediamine, N, N-DiUthy 1-N '-propionyl-mphenylenediamine, N, N-diethylamino-3 ~ methoxybenzene, 1-N , N-diethylamino-2,5-diniethoxybenzene, 1-N, 11-diethylamino-2,5 ”. diethoxybenzene, 1-N, N-diethylamino-2-πlethoxy-3-acetylaminobenzene, N-ethyl-N-ß-chloroethyl aniline, N, N-bis (ß-chloroethyl) aniline, »- (ß-chloroethyl ) -N-butyl-aniline, N- (ß-chloroethyl) -N-ethyl-in-toluldin, N _# N-Bia- (ß-chlorotithyl) -m-toluidine, N-methyl-N-ß-hydroxyäthy1- aniline, N-ethyl-N-ß-hydroxyethylaniline, U, N ~ bis- (ß-hydroxyethyl) -aniline, N-butyl-N- (ß-hydroxyethyl) -aniline, N, N-BIs- (Q, ^ -dihydroxypropyD-aniline, N-ethyl-N-benzyl-aniline, N-ethyl-N-beneyl-m-toluidine, N-ethyl-N-ß-hydroxyethyl-m-toluidine, N, N-Bia- (ß- hydroxyathyl).

¹² 309884/1263

m-toluidine _# 1-N-ethyl-N-ß-hydroxyethylamino-2-methoxy-5-methylbenzene, N-ethyl-N-ß-hydroxyethyl-N ¹ -acetyl-m-phenylenediamine, N ^ -Bla-Cß- hydroxyäthylJ-N'-acetyl-m-phenylenediair.in, 1-N, K-Bia- (ß-hydroxyethyl) -amino-2-nethoxy-.5-acetyla, 7.ir.o-

benzene, 1-N, N-Ble- (ß-hydroxyethyl) -. amino-2-ethoxy-5-acetylamino-benzene, 1 ~ N, N-Bia- (ß-hydroxyethyl) -amino-2-methoxy- 5-propionylamino-benzene, N-ethyl-N-ß-acetoxyethylaniline, N, N-iie - '(ß-acetoxyethyl) aniline, N-butyl-N-Ö-acetoxyethylaniline, l'I-ethyl-N -ß-aoetoxyäthyl-m-.toluidine, N _t N <-Bie- (ß-acetoxyäthy1) -m-toluidine, 1-N-ethyl-N-ß-acetoxyethylamino-2-methoxy-5-methylbenzene, N-Xthy 1-N-ß-acetoxyethyl * -N '' - acetyl-m-phenylenediamine, NN-BiB-Cß-acetoxyäthylJ-N'-acetyl-m-phenylenediamine, 1-N, N-Bi3- (ß-acetoxyethyl) - amino-2-methoxy-5-acetylamino-benzene, 1-N, N-bis- (ß-acetoxyethyl) -amino-2-ethoxy-5-acetylamino-benzene, 1-N, N- (ß-acetoxyethyl) - amino-2-methoxy-5-propionylamino-benzene, N, N-bis- (ß-ethoxycarbonyloxyethyl) aniline, N, N-bis (ß-methoxycarbonyloxyethyl) aniline, N, N-bia- (ß-ethoxycarbonyloxyethyl ) -iss-toluidine, N, lI-bis- (ß-methoxycarbonyloxyethyl) -m-toluidine, N, N-bis (ß-ethoxycarbonyloxyethyl) -N'-aoety1-ra-phenylenediamine, N, N-bis-Cß -methoxycarbonyloxyäthyl) -N'-acetyl-ra-phenylenediamine, 1 -Ii , N-Bia- (ß-ethoxycarbonyloxyethyl) -amino-2-methoxy-5-acetylaminobenzene, 1-N, N-bis (ß-methoxycarbonyloxyethyl) -amino-2-niethoxy-5-acetylamino-benzene, 1- N, N-Bia- (ß-ethoxycarbonyloxyethyl) * - amino-2-ethoxy-5-ac e tylaminobenzene, 1 -N, N-Bie- (ß-methoxycarbonyloxyethyl) -amino-2-ethoxy-5 * «acetylaminobenzene, NN-Bia-iß-carboraethoxy-äthylJ-N'-acetyl-m-phenylenediamine, N-methyl-N-ß-cyanoethyl-anilineN ^ -Bia-iß-cyahäthylJ-aniline, K'-ethyl-N-ß-cyanoethyl -m-toluidine, N-ethyl-N-ß-cyanoethyl-N ¹ -acetylamino-m-phenylenediamine, N-ß-liydroxyethyl-N-ß-cyanoethylaniline, N-ß-acetoxy-ethyl-N-ß-cyanoethyl- m-toluidine, N-ß-methoxycarbonyloxyethyl-N-ß-cyanoethyl-N'-acetylaraino-m-phenylenediamine, !!, N-bis-iß-cyanoethylJ-N'-benzoyl-m-phenylenediamine, N-ß-hydroxyethyl -K-ß-cyanoethyl-N'-phenacetyl-m-phenylenediamine, N, N-diethyl-N'-phenoxyacetyl-m-phenylenediamine, N-ethyl-N-ß-cyanoethyl-N ¹ -phenoxyacetyl-m-phenylenediamine, N, N-Bia- (ß-cyanoethyl) -N'-pchlorbenzoyl-m-phenylenediamine,

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N-methyl-aniline, N-ethyl-aniline, '; Nh-butyl-aniline, N-ß- 'Cy anäthy l-aniline, "NQ-chloroethyl aniline, n-ß-hydroxyethyl aniline, N-ß-acetoxyethyl aniline, N-ß-methoxy and N-ß-Ä 'thoxycarbonyloxyät hy l-aniline, N-ß-carbomethoxyethylaniline, N-ß-cyanoethyl-2-raethyl-aniline, N-methyl-m-toluidine, N-ethyl-m-toluidine, N-ß-cyanoethyl-m-toluidine , N-ß-chloroethyl-m-.toluidine, N-ß-hydroxyethyl-m-toluidine, N-ß-acetoxyethyl-m-toluidine, N ~ ß-methoxycarbonyloxyethyl-m-to] ,, Utjy ^ n _{> ll} , ^ _{= L} Ä ^> _thyl-3-ethylaniline, jN-n-propyl-3-ethyl-aniline, N-ß-cyanoethyl-3-ethyl-aniline, N-ß ^ cyanoethyl-3-methoxy-aniline, N-ß -Chloräthyl-3-raethoxyanilin, -N-ß-Cyanoethyl-3-ethoxy-aniline, N-ß-chloroethyl-3-ethoxy-aniline ^ N-Xthyl-3-chloro-aniline, N-ß-Gyanäthyl-3- chloraniline, JN-ß-chloroethyl-3-chloro-aniline, N-ß-hydroxyethy. l-3-chloro-, aniline, N-ß-acetoxyethyl-3-chloro-aniline, N-ß-cyanoethyl-3- bromo-aniliniN-ethyl-N'-formyl-m-phenylondiatnintN-ethyl-N'-acetylm-phenylenediamine, N-ß-cyanoethyl-N * -formyl-in-phenyleridiamine, N-ß-cyanoethyl-N'-acetyl- m-phenylenediamine, N-ß-cyanoeth yl-N ¹ -hydroxyacetyl-in-phenylenediamine, N-ß-cyanoethyl-N'-propionyl-m-phenylenediamine, N-ß-cyanoethyl-N-benzoyl-m-phenylenediamine, N-ß-cyanoethyl-N'- methoxycarbonyl-m _T phenylenediamine, N-ß-cyanoethyl-N ¹ -ethoxycarbonyl-m-phenylenediamine, N-ß-cyanoethyl-N ¹ -bemsolsulfonyl-m-phenylenediamine, N-ß-cyanoethyl-N ¹ -toluenesulionylm-phenylenediamine, N -ß-Cyanoethyl- ^{N'-methylsulfonyl-m- v} <.. phenylenediamine, N-ß-cyanoethyl-N'-ethylsulfonyl-m ~ phenylenedianine, N-ß-chloroethyl-N'-acetyl-m-phenylenedlumine,, KO -Hydroxyäthyl-N'-acetyl-m-phenylenediamine NQ-Acetoxy- \ äthyl-N'-acetyl-m-phenylenedianiine, N-ß-Methoxycarbonyläthyl- -N '-ac etyl-m-phenylendiamine, N-ß- Carboniethoxyäthyl-N'-acotylm-phenylenediamine, N-Ethyi ^ -methoxy-S-ir.ethyl-aniline, NQ-Cyanäthyl-2-niethoxy-5-nie thy l-aniline, N-ß-Cyanoethyl-Z-ethoxy- SA me thy l-aniline, N-ß-Cyanäthy 1-2, S-dithethy l-aniline, KA thy I-

le A 14 485 · -H- 30988 A / 1263

2-methoxy-5-acetylamino-aniline, N-ß-ChlOrathyl-.2 ~ methoxy-5-acetylamino-aniline, N-ß-cyanoethyl-2-methoxy-5-acetylamino, _T aniline, N-ß-cyanoethyl-S -ethoxy-S-acetylamino-aniline, ■ N-ß-cyanoethyl-2-methoxy-5-formylamino-anllinj NB-cyanoethyl-2-methoxy-5-hydroxyacetylamino-aniline »N-β-cyanoethyl-2-ethoxy-5 -propiorjj'lamino-anilini N-ß-cyanoethyl-2-ethoxy-5-propionylamino-aniline, N-ß-cyanoethyl-2-ethoxy-5-hydroxyacetyiamino-aniliri, ii-ß-cyanoethyl-2-me-thGxy -5-benzoylamino-aniline, N-ß-cyanoethyl-2-methoxy-5-methoxycarbonylamino-aniline, N-ß-cyanoethyl-2-methoxy-5-ethoxycarbonylamino-aniline, N-ß-cyanoethyl-2-methoxy -5-methylsulfonylamino ^ ahiline, N-ß-cyanoethyl-2-methoxy-5-ethylsulfonylamino-ahiline, N-ß-hydroxyethyl-2-meihoxy-5-acetylamino-aniline, N-ß-acetoxyäthy.l-2-me thoxy-5-acetylamino-aniline, N-ß-methoxycarbonyloxyethyl-2-ynethoxy-5-acetylamino-aiiilin, N-ß-cyanoethyl-2-methyl ~ 5-acetylamino-aniline, diphenylamine, N-methyl-diphenylamine _f N-ethyl-diphenylamine, N-propyl-diphenylami & j Ν, Ν-dimethyl-a- naphthylamine, Ν, Ν-diethyl-a-naphthylamine, N-ethyl-N-ß-oyanäthyl-a-naphthylamine, N-ethyl-N-ß-bydroxy = ethyl-a-naphthylamine, Ν, Ν-dipropyl-a- naphthylamine ,, N-butyl-N-ß-hydroxyäthy1-a-naphthylamine, N-ethyl-N-benzyl-a-naph = thylamine, N-ethyl-N- (2-phepyl-ethyl) -a-naphthylamine _t N -Aethyl-a-naphthylamine, N-phenyl-a-naphthylamine, N-propyl-a * · naphthylarain ^

β-methylindole, 2-phenylindole, l-methyl-2-phenylindole, 1,2-di = methylindole, l-fJ-cyanoethyl - ^ - methylindole, l-ß-cyanoithyl-2-phenylindole, y- (2-phenylindolyl -l) -propionic acid, y- (2-, methylindolyl-l) -propionsaureGmid, y- (2-methylindolyl-l) -proa pionic acid, 2-ß-naphthyl-indole, 2-p-biphenylylindole, 2,5- Dimethylindöl, 2, ^ - diraethyl-7-methoxyindole, 2-phenyl-5-ethoxyin = dol, 2-methyl-5-ethoxyindole, 2-methyl-5-chloroindole, 2-methyl-6-chloroindole, 2-methyl -5-nitroindole, 2-methyl-5-cyanoindole, 2 »methyl-7-chloroindole, 2-methyl-5-fluoroindole, 2-methyl-5-broraindole , 2-methyl-5« 7-dichloroindole, 1- ^ Cyanoethyl-2,6-dirae = thylindole

Le AH 485 - 15 -

^ TT- · ■:. :: ■■ ^v 30 ^ 884/1261

The quaternizing agents are alkyl halides, halogen acetamides, ß-halopropionitriles, halohydrins, alkylene oxides, Alkyl esters of sulfuric acid or alkyl esters of organic sulfonic acid into consideration, for example methyl chloride, bromide or iodide, ethyl chloride, bromide or iodide, propyl bromide or iodide, benzyl chloride or bromide, chloroacetamide, ß-chloropropionitrile, Ethylene chlorohydrin, dimethyl sulfate, diethyl sulfate, Methyl benzenesulfonate, methyl p-toluenesulfonate, ethyl, propyl or butyl ester, allyl chloride or brotnide, Methallyl chloride or bromide, trimethyloxonium boron fluoride, propargyl chloride, 1,4-dichloropropene- (2), 1-chloro-butene- (2), 1-chloro-butyne- (3), 1,2-D-chloro-propen- (2), i-chloro-2-vinyl-propen- (2), 1-chloro-pentadiene- (2,4) as well as acrylonitrile, acrylic acid, acrylic acid amide, acrylic acid methyl ester.

The 2-amino-benzothiazoles of the formula V are diazotized in a manner known per se, for example in 85 $ iger Phosphoric acid or in mixtures of 85% phosphoric acid and acetic acid with nitrosylsulfuric acid. The coupling of the diazotized 2-aminobenzothiazoles with the coupling components VI are also carried out in a manner known per se, for example in acidic aqueous or aqueous-organic medium.

The quaternization is expediently carried out in an indifferent one organic solvent, for example in a carbon = hydrogen, chlorinated hydrocarbon or nitro hydrocarbon = material such as benzene, toluene, xylene, tetrachloroethane, chloroform, carbon tetrachloride, mono- or dichlorobenzene or nitro = benzene, in an acid amide or acid anhydride, such as dimethyl = formamide, N-methylacetamide or acetic anhydride, in Di = methyl sulfoxide or in a ketone such as acetone or methyl = ethyl ketone. Instead of an organic solvent, it is also possible to use an excess of the alkylating agent the. The quaternization is carried out at an elevated temperature, if necessary with the addition of acid-binding agents, such as Magnesium oxide, magnesium carbonate, soda, calcium carbonate or sodium bicarbonate and if necessary under pressure, made = men. The most favorable conditions in each case can easily be determined through a preliminary test.

le AU 485 - 16 -

3 0 3 83 \! 1 2 6 Ί

The resulting quaternized dyes bind in the solvents used sclwer "soluble and can be prepared by, ^r filtered off to be isolated. Stay the quaternized dyes with the use of dimethylformamide, bimethylsulfoxyd or acetonitrile partially or completely in solution, they can be prepared by dilution with water and train" of water-soluble salts, for example sodium or potassium chloride, are deposited.

dyes obtained by the process are outstandingly suitable for dyeing and printing cationically dyeable fibers, from polymers and copolymers of acrylonitrile and dicyanethylehs, and from acid-modified fibers made from polyamide and polyester, with real shades being obtained. The dyes can also be used for Dyeing and printing of tanned cellulose materials, silk and leather. They are also suitable for the production of writing fluids, stamps, ballpoint pen pastes and can also be used ■ in rubber printing. ■ " ¹ ^ ■■". · '· ■> .. ... r .: ._ a ·.;. ·:. .. · ■ -.- ■ »

For dyeing with the basic dyes of the general formulas (I) to flCF), flakes, fibers, threads, tapes, woven or knitted fabrics made from polyacrylonitrile or from copolymers of acrylonitrile containing at least 85% of acrylonitrile with other vinyl compounds, such as vinyl chloride, are particularly suitable Vinylidene chloride, vinyl fluoride, vinyl acetate, vinyl pyridine, vinyl imidazo !; Vinyl alcohol, adryl and methacrylic acid esters and amides, as. Dicyanethylene. Likewise, flakes, fibers, threads, tapes, woven or knitted fabric may be made of acid-modified synthetic materials / ¹ in particular from acid-modified aromatic polyesters and acid-modified polyamide fibers are outstandingly colored. Acid-modified aromatic polyesters are terephthalic acid, for example, polycondensates of suif © and ethylene glycol, ie sulfonic Polyäthylenglykolterephthalaten (type DACRON 64 of EI DuPont de Nemours and Company), as they and the US Patent 2,893 8L6 described ^one in Belgian Patent 549,179. ..- v-ir ·, ■ * ■ '' ·. '.x-.z?'.

- ■ ¹⁷ 309884/1263

Dyeing can be carried out from weakly acidic liquor, in which case the dyebath is typically entered at ¹ K) from ⁰ to 60 ° C. and then dyed at boiling temperature. You can also dye under pressure at temperatures above 100 ° C. Furthermore, the dyes can be added to spinning solutions for the production of polyacrylonitrile-containing fibers or they can also be applied to the undrawn fiber.

The colorations of the dyestuffs according to the invention of the formulas (i) to $ 3Z) on materials made of polyacrylonitrile or acidic modified polyester fibers or polyamide fibers is characterized by very good light, wet, rub and sublimation fastness and a high affinity to the fiber.

The dyes can be used individually or in mixtures. They are good for dyeing moldings made from polymers or copolymers of acrylonitrile, as. Dicyanäthylena, acid-modified aromatic polyesters or acid-modified synthetic superpolyamides in chlorinated hydrocarbons are suitable as dyebaths if they have substituents such as the tert-butyl group, or if the anion An in the formulas (i) to (Q?) the anion of a monobasic organic acid is with 4-30 carbon atoms. Such organic acids are, for example: 2 * -Aethyleaprohaäure, Laurinsäure; Oleic acid, linoleic acid, a mixture of aliphatic carboxylic acids with 15-19 carbon atoms (Versatic Acid 1519). a mixture of aliphatic carboxylic acids with 9 - "11 carbon atoms (Versatie-SJture 911), coconut fatty acid forerun, tetradecanoic acid, undeeyreric acid, dimethylpropanoic acid, dimethyl acetic acid, carboxylic acids, their carbon chain is interrupted by heteroatoms, such as nonylphenol tetraethylene glycol ether propionic acid, dodecyl tetraethylene glycol ether propionic acid, 3- (nonyloxy) propionic acid, 3- (isotridecyloxy) propionic acid, ether propionic acid, alcoholic acid, alcoholic acid, alcoholic acid, such as cyclobenzoic carboxylic acids, such as tertiary carbonic carboxylic acids, butyl aromatic carboxylic acids with 6-10 carbonic acids, nonylphenoxyacetic acids. such as hexahydrobenzoic acid, cyclohexenoarboxylic acid, abietic acid, and sulfonic acids; such as tetrapropylene benzene sulfonic acid.

- ¹⁸ - 309884/126 3

In the following examples, "parts" mean parts by weight.

Example 1 *

26.9 parts of 2-amino-6-benzoylamino-benzothiazole are introduced into a mixture of 420 parts of 85% phosphoric acid and 92 parts of glacial acetic acid, stirred for a few hours at room temperature and stirred at 0 ° with 34.5 parts of nitroeylsulfuric acid for 3 hours diazotized. The diazonium solution thus obtained is allowed to flow into a solution of 16 _t 0 parts of Ν, Ν-diethylaniline and part of amidosulfonic acid in 150 parts of 10% hydrochloric acid at 0 ° and buffered to pH 3 with sodium acetate solution. The dye disengages immediately. After filtering off with suction and drying, 43.5 parts of the dye of the formula are obtained

22.9 parts dies.es dye are in proportions to 300 parts Chlorbeh = zol at 100-110 ⁰ C 'fat mixed with 6.5 parts Dimethylsul =. Then it is heated to you temperature for 30 minutes. After cooling, the dye is filtered off, washed old benzene and dried. 2 "8 parts of a powder of the formula which is easily soluble in water and having a dark blue color are obtained

-CO-HN c _r "

CH ₃ OSO ₃

the textile materials made of polyacrylonitrile and other textile materials that can be dyed with cationic dyes dyes blue with excellent light and wet fastness properties with excellent drawability and high color strength.

Le AU 485 - 19 -

309884/126 3

The 2-A.mino-6-benzoylaminobenzothiazole used as the diazo component was manufactured in the following way:

2,6-diamino-benzthiazole is reacted with stöchiometriseher amount of benzoyl chloride in benzene in the presence of one equivalent of triethylamine at 20 ⁰ C, then at 80 ⁰ C. After cooling to 20 ⁰ C is filtered off, dried at 60 ⁰ C, to remove the slurried in water at Triäthylaminhydrochlorids, filtered off again and dried at 60 ⁰ C., to yield the 2-A.mino-6-benzoylaminobenzthiazol of melting point 228-229 ° in 92% yield in the form of almost colorless crystals.

If the procedure described in Example 1 is followed, using the diazo compounds listed in the table below and coupling components and the quaternizing agent mentioned there Similar dyes that dye polyacrylonitrile with similar fastness properties and in the specified shades.

Color based on e.g. diazo component, coupling component, polyacrylonitrile

² a ^c ° -w \ ". q ^ - ^c ° ^h "

= / C ₉ H- blue

/ VN,

₂ H ₆

H ₄ OH

^ C ₂ H ₄ OH

.CoH "0H

Le A 14 485 - 20 -

3 0 9 8 3 · ', / 1?

E.g. diazo component

Coupling component Parbton on

Polyacrylonitrile

-co-:

NH ₂ / C ₂ Hg

fX-ti

^H 5

CH ₂ -f \

blue

/ C ₂ H ₄ OH

C ₄ H ₉

C ₂ H ₅

/ C ₂ H ₈

H ₂

12 CH,

, Go H-

CH ₃

• C ₂ H ₅

/ C ₂ H ₅

C ₂ H ₅

C ₂ H ₄ CN

/ C ₂ H ₄ OH

C ₂ H ₅ ,

H ₄ OH

CH,

C ₂ H ₅

Vn:

^ C ₂ H ₄ OH

C ₂ H ₄ OH

Le A 14 - 21 -

309884/1263

E.g. diazo component

Coupling component color on

Polyacrylonitrile

/ C ₂ H ₅

'N /

CH ₃ CH ₂ OH -9H-

blue

.C ₂ H ₅

C ₄ H ₉

20th

C ₄ H ₉

2i

CH ₂

egg

NHo

C ₃ H ₇

C ₂ H ₅

26th

CH,

27 Le A H - 22 -

3 0 9 8 8 4/1263

Βπρ. Diazo component

Coupling component color on

Polvacrvlnitrile

28

\ -CO-NH

30th

CH ₃

u> - ^N \

CH,

3 ₂ H ₄ CN

J ₂ H ₄ OH C ₄ H ₉

^ C ₄ H,
^ CH ₂ J ~ \

blue

31 Cl-f_VC0-NH 32

NH _a

Vn '

/ C ₂ H ₄ OH, ^N C ₂ H ₄ OH

33

CH,

C ₂ H ₄ OH

36

Cl

C ₂ H ₅

CH ₂ ^ n

CH ₃

C ₂ H ₄ OH

37

Lei 14 309884/126

E.g. diazo component

Coupling component color on polyacrylonitrile

Cl

Cl VCO-NH

¹ p.

H ₄ OH

H ₄ OH

CH ₃

^ CH ₂ -fA

blue

CH,

C ₄ H,

CH ₃ 0- / VCO-NH

/ C ₂ H ₅

/ C ₂ H ₄ OH

CH-

43 / Ca Hk

^ C ₂ H ₄

44

) -NH

CH, , .C ₂ H ₅

C ₂ H ₅

45

/ C ₂ H ₄ OH

46 CH,

C ₄ H ₉

47 CH,

/ C ₃ H ₇

'C ₃ H ₇

le A 14 - 24 -

309834/126

Bap. Diazo component, coupling component hue on

Polyacrylonitrile

-NH ₂

CH ₃

Vn ' ² *

CH,

blue

50

CH ₃

H ₄ OH

H ₄ CN

CH ₃

CH _a

Vn:

, C ₂ H ₄ O-CH ₃

CH ₃

57 C ₃ H ₇ -CO-NH

CH ₃

Vn

/ C ₃ H,

C ₂ H ₅

C ₂ H ₄ CN

H ₄ CN

C ₂ H ₅

Le A 14 - 25 -

309884/1263

Bop. Diazo component

Coupling component color on

Pblyacrvlnitrile

C ₃ H ₇ -CO-NH

/ C ₂ H ₅

blue

60

NC ₂ H,

violet

63

CO-

Vn

H ₄ CN

CH ₃

CH ₃

Λ-Ν- / Λ

blue

₂ H ₄ Cl

65 66 CH,

^ C ₂ H ₄ CN C ₂ H ₄ O-COCH ₃

Vn-

Ie A 14 - 26 -

309884/1263

Bop. Diazo component

Coupling component! Color on ' polyacrylonitrile

71 72

CH ₂ -CH ₂

CH]

CO-N s

Yr **

^ N

-CO-N

CH,

, C ₂ H ₄ OH

"CH ₂ - ^

^ C ₂ H ₅ ^V C, H «

2 ^H 5

NHi-CO-CH,

CH,

C ₂ H ₅ ^CH r π

Λη ΧΙ »

^X C ₂ H ₅

violet

blue

73

75

Il C

JC ₂ H ₄ Cl C ₂ H ₅

C ₂ H ₄ CN

4 β

CH ₃

Le A H - 27 -

309884/126

E.g. diazo component

■ Coupling component color on

Polvacrvlnitrile

> NH ₂

O-CH,

CH,

blue

violet

CH,

78 (CH _{3) 3} C-CO-NH

^ C ₂ H ₅

blue

CH ₃

C ₂ H ₄ OH

/ C ₂ H ₅

• Ν,

CH ₃

^X C _a H ₄ CN

.NH

CH,

violet

C ₂ H ₄ O-CO-NHCH,

blue

/ C ₂ H ₅

Le AH - 28 -

3Ό98 3Λ / > 2 6 Π

E.g. diazo component.

Coupling component color on

. Polyacrylonitrile

90

92

93

O-NH

CO-NH

Le A 14 4-85

OH

AH.

CH _S

₂ H ₄ OH

: C.

CH,

/ C ₂ H ₄ CN CH ₂ - ^ Λ

, C ₂ H ₁ ^ C ₂ H ₄ OH

O ⁰ ^

, NC ₂ H ₄ CN Cl

Jnh

CH,

- 29 -

blue

violet

309884/1263

E.g. diazo component

Earbton on coupling component polyaorylnitrile

95 / ~ VcO-NH

100

/ Vn:

CH ₂

CH ₃

VN "

H ₄ OH

/ C ₄ H, 'C ₂ H ₄ OH

/ C ₂ H ₄ OH

Vn _n

C ₂ H ₅

CH ₃

blue

violet

101

102

O-NH

CV-C ₂ H ₄ COOH CH ₃

.C ₈ H,

NH ₂ blue

103 104

Vn.

H ₉

CH ₃

Le AH - 30 -

309884/1263

E.g. diazo component

"Color shade on coupling component polyacrylonitrile

105

106 ₁₀₇

108 109

110

^ CO-NH

H -CO-N

^ClHl

γ-

CH ₃

/ C ₂ H ₄ OH

\ H ₉ .
JC, H ^ OH

ClI

—- Γ 14

blue

violet

blue

111

If the procedure described in Example 1 is followed, using the diazo and coupling components listed in the table below and the quaternizing agents, corresponding dyes are obtained which dye polyacrylonitrile with similar fastness properties in the specified color shades.

Le A H

309684/1

E.g. diazo component

Coupling component

Quaternizing agent

Hue on
Polyacrylonitrile

112

-CO-NH

CH,

CH, -C1

blue

113 Il

114

Vw ^

CH ₂ CH ₂ CF

-116

OCH,

N '

CH ₅

co ro cn

let A 14

Ex. Diazo component, coupling component, quaternization shade

medium polyacrylonitrile

11 7

CH ₂ = GH-GN

blue

118 .O ₂ H ₅

N ₁

CN

GH ₂ = CH-COOH

119 OCH

_T / ° 2 ^H 5

\ / - ί DD

CH ₀ = GH-COOGH,

120

121

Le A 14 4-85

C ₀ H. -OH
/ ^ 4

ⁱ 2 A-

C ₂ H ₅ Br

OH ₂ = CH-CONH ₂

E.g. diazo component

Coupling component

Quaternizing agent

Hue on
Polyacrylonitrile

CH

122

6 ^H 5

CH ₂ = CH-CONH ₂

violet

123

Cl

0-NH

(C ₂ H ₅ O) ₂ SO ₂

124

CH

CH ₉ - </>

• CH ₃ -Br s blue

CO

W \

CH

CH,

2 X = /

CH ₂ -Br

^w

OH

(C ₂ H ₅ O) ₂ SO,

Le A U

- 34 -

Ex. ■■ 'diazo component coupling component quaternization

middle

Hue on
Polyacrylonitrile

127 f ~ yO-OE ₀ -CO-NH.

OH ₉ CH ₀ ON

S Z 2

OH ₂ = CH-CONH ₂

blue

128 (C ₂ H ₅ O) ₂ SO ₂

129

-OH,

CH ₂ = CH-COOH

Yiolet

¹ N.

ο

C ₂ H ₅ Cl

blue

131

-SO ₂ -OO ₂ H ₅

Ie A 14 - 35 -

E.g. diazo component

Coupling component quaternization

middle

Color on polyacrylonitrile

132

0 It η

C ^

Il 0

CH,

CH ₂ CH ₂ -CF

CH ₂ = CH-COFH ₂

blue

133 C ₃ H ₇ -OO-NH,

κτβζζ

C ₂ hp

C ₀ H _n -Br

134

Cl

135

Cl

O-NH

OCH

CH ₂ -CH ₂ -CF

(C ₂ H ₅ O) ₂ SO ₂

136

Le k

C ₂ H ₅

CH,

^CH 3 ~ W ~ ^SO 2 ~ ^OCH

2 ~ ^OCH 3

E.g. diazo component

Coupling component

Quaternizing agent

Hue on
Polyacrylonitrile

137 Cl-f y-σθ-ΝΗ.

-H

CH ₂ = CH-CO-NH ₂

violet

138 CH ₃ -O-OC-NH

/ VHH,

CH

(C ₂ H ₅ O) ₂ SO ₂

blue

139

HO

-CH ₂ -CN

° 6 ^H 5

C ₂ H ₅ Br

CH ₂ = CH-COOH.

violet

Oi Ca?. ·

141 blue

N) NJ OJ N)

Le A H

- 37 -

E.g. diazo component coupling component quaternization

middle

Color on polyacrylonitrile

142 ^C 3 ^H 7 ^OOC \ -

CH ₂ CH ₂ OH

(C ₂ H ₅ O) ₂ SO ₂

blue

143

CH ₃ ^G 2 ^H 5

144 OCH ₃

C ₂ H ₅

145

146

Le A 14

/ ^G 4 ^H 9

¹ NH

-SO ₂ -OC ₂ H ₅ "

CH ₂ = CH-CO-NH ₂ violet CO
NJ
cn
■ Ο ·

Example - diazo component coupling component quaternization

middle

Hue on
Polyacrylonitrile

147

0, H ₇ OOC.

-CH,

violet

\: 1 48

30-NH

Cl

blue

149

150

O, H ₇ -OO-NH.

151

Ie A 14

° 6 ^H 5

- 39 -

C ₂ H ₅ Br

CH ₂ = CH-CO-NH ₂

violet

blue

INJ OJ

Ex. Diazo component, coupling component, quaternization shade

medium polyacrylonitrile

₅ 2

CH,

_CH CH ₂ -CH ₂ -CN

(C ₂ H ₅ O) ₂ SO ₂

blue

153 154 GH

(C ₂ H ₅ O) ₂ SO ₂

155

) -NH

G ₂ H ₅ -Br

156 .N-CH,

-CH ₂ -Cl

violet

Le A H - 40 -

Ex. Diazo component, coupling component, quaternization
middle ,

! Hue on
Polyacrylonitrile

157

JO-NH

CH ₂ = CH-ON

blue

158

CH ₂ = CH-CO-NH ₂ "

• 159 € VCO-NH

C ₀ H ₁
²

° 2 ^H 5

Cl-CH ₂ -CH = CH ₂

160

'3 ^ ₇

Cl-CH ₂ -CH = CH

161 ₃ H.

Cl-CH ₂ -CH = CH ₂

N) CO N)

Le A 14 - 41 -

E.g. diazo component coupling component quaternization

middle

Hue on
Polyacrylonitrile

162

JO-NH.

/ ^C 2 ^H 4
° 4 ^H 9

H ₄ -OH

Br-CH ₂ -CH = CH ₂

blue

CD OO CO

ISJ CD

Le A H

Example 1S3 '

Yerfälirt one as described in Example 1 'and solves the isolated .farbstoff after the quaternization in 500 parts of water, and Q is obtained by adding sodium chloride and zinc chloride filtering off and drying the dye of the formula

^ZnC1

of textile materials made of polyacrylonitrile dark blue with colors with very good light and wet fastness properties.

The in the examples 2 "to 162 described dyes in the zinc chloride double salts *

Example 164

. Dyeing process for polyacrylonitrile and acid modified polyamide fibers (type Dye I):

0.1 part of the dye shown in Example 1 is made into a paste with about 2 parts of water, possibly with the addition of a little acetic acid, and dissolved with 50 parts of hot water. The dye liquor also contains 0.5-2 g of Avolan IS (condensation product of naphthalenesulfonic acid and formaldehyde) and is made up to 500 parts with cold water. The pH of the dye liquor is adjusted to 4.5-5 with acetic acid or sodium acetate. In this dye bath, 10 g piece goods of Polyacrylnitrilfasem or acid-modified polyamide fibers are kept constantly in motion while increasing in 30 min., The temperature to 100 ⁰ C. At the boil dyeing for 60 minutes the material rinsed with cold water and dried, then 60 - 70 ⁰ G. For the dyeing acid-modified Polyglykolterephthalatfasern

'■ Le A 14 485 - 43 -

. . ,, -. ■ ,,,, · 309884V 1263

(Type Dacron 64) a carrier is added to the dye liquor, for example 1-3 parts of an aromatic oxycarboxylic acid ester or diphenyl.
Printing process;

A fabric made of polyacrylonitrile is coated with a printing paste printed, which was prepared in the following manner: 30 parts by weight of the dye of the formula of Example 1, 50 parts by weight of thiodiethylene glycol, 30 parts by weight of cyclohexanol and 30 parts by weight of 30% acetic acid poured over 330 parts by weight of hot water and the obtained Solution to 500 parts by weight of crystal gum (öummiarabicum as a thickener). Finally, 30 parts by weight of zinc nitrate solution are added. The received Print is dried, steamed for 30 minutes and then flushed. A red print with very good fastness properties is obtained.

Le A 14 485 - 44 -

Claims (7)

Patent claims: R is hydrogen, a substituted methyl radical, an alkyl radical containing at least 2 carbon atoms, an alkoxy, cycloalkyl, aryl, aralkyl or heterocyclic radical, R _{1 is} hydrogen, an alkyl or aralkyl radical, or K and K _{1 denote} are connected to a heterocycle,
R _{2 is} hydrogen, an alkyl or alkoxy radical or halogen, R ^ is an alkyl, alkenyl, alkynyl or aralkyl radical,
K the remainder of a coupling component and
An ^ 'means an anion, · ■. and wherein the cyclic and acyclic radicals are nonionic May contain substituents and / or carboxyl groups. 2. Cationic azo dyes of the general formula ¹ K R-CG-Ii -N = N-K At Le A14 485 - 45 - 309884/1263 worm R is hydrogen, a substituted methyl radical, an alkyl radical containing at least 2 carbon atoms, ^{v is} an alkoxy, cycloalkyl, aryl, aralkyl or heterocyclic radical, R _{1 is} hydrogen, an alkyl or aralkyl radical, or R and R _{1 are} ZiU are connected to a heterocycle, R ^ hydrogen, an alkyl or alkoxy radical or halogen, R, an alkyl, alkenyl, alkynyl or aralkyl radical and knr ~ ' mean an anion and a remainder of the formulas IU .A N. represents in which or Hydrogen, alkyl, alkoxy or halogen, hydrogen, alkyl, alkoxy, acylamino or halogen, hydrogen, alkyl or aralkyl, Alkyl, aralkyl or aryl, Alkyl or aryl, Mean hydrogen, alkyl or aralkyl, alkyl, cyano, halogen or nitro, and in which the substituents R bis as far as they are alkyl or aryl radicals represent, can represent further nonionic substituents . ' 3. Cationic azo dyes of the general formula R ₁₁ -CO-ITH To ^v Le A H 485 309884/1263 -C ₂ H ₅ , -C ₅ H ₇ , ISO-G ₅ H ₇ , -O ₄ H ₉ , ISO-C ₄ H ₉ , SeIcC ₄ H ₉ , ^ Tt-C ₄ K ₉ , -CH ₂ -OC ₆ H ₅ , -CH ₂ -C ₆ H ₅ , C ₆ H ₅ ,, -C ₆ H () C. ₆ H ₃ Cl ₂ - (2.5), -O ₆ H ₄ -CH ₃ - (O ₁ Hi and ρ), -C ₆ H ₄ -O Alkyl with 1-4 C atoms, 2-cyanoethyl, 2-carbamoylethyl or. Benzyl, Wansstoff, - chlorine, bromine, methyl, ethyl, methoxy or Ethoxy., ; Hydrogen, methyl, ethyl, methoxy, ethoxy, chlorine, bromine, acetyl-, methylsulfonyl- or benzoyl-amino, Hydrogen, alkyl with 1-4 carbon atoms or benzyl, hydrogen, alkyl with 1-4 carbon atoms, benzyl "or phenyl and ; a.-Lai on mean. 4. Cationic azo dyes of the general formula At in which - -C ₂ H ₅ , -C ₃ II ₇ , ISO-C ₃ H ₇ , -C ₄ H ₉ , IsO-C ₄ H ₉ , SeV-O ₄ H ₉ tert.O ₄ H ₉ , -CH ₂ -OC ₆ H ₅ , -CH ₂ -C ₆ H ₅ , C ₅ H ₅ , -C ₆ H ₄ Cl - '?:, C ₆ H ₃ Cl ₂ -U ^), -O ₆ H ₄ -CH ₃ - ( O ₁ Tn and p), -C ₆ H ₄ -O-CH ₅ -Ip ,, _Γ) _ΠΤ-Τ —Π — Π DD Alkyl with 1-4 C atoms, 2-cyanoethyl, 2-carbamovlathyl or benzyl, Le A H 485 - 47 - 98 84 / 1283- BATH ORIGINAL Methyl, ethyl or phenyl and Hydrogen, methyl, ß-cyanoethyl, ß-carbamoylethyl
uriä i-carboxyethyl and
'mean an anion. 5. Process for the preparation of cationic azo dyes the general formula R ₁ <+> ! R-CO-N ",. R ₉ ^At wherein R v / asporr.toff, a substituted methyl radical, a roundest :; Alkyl radical containing 2 carbon atoms, an alkoxy, cycloalkyl, aryl, aralkyl or heterocyclic rent, R ₁ Wi ε.-; s rs to ff, mean an alkyl or aralkyl radical, odo:? "and Hj are connected to form a heterocycle,
R _{2 is} hydrogen, an alkyl or alkoxy radical or Ha Io:;. ·. ■: ■ ;, R- a. Al> y, l-, alkenyl, alkynyl or aralkyl radical,
K den Κ '.:.: * A coupling component and
An ^ ~ ^J mean an anion, and in which the cyclic and acyclic radicals can contain non-ionogenic dubstituents and / or carboxyl groups. characterized in that aminobenzothiazoles of the general formula Le A 14 485 - 48 - 309884/1263 BATH ORIGINAL R-GO-N diazotized, with a coupling component of the formula KH j ■ Couples and with a quaternizing agent of general formula converts, where X represents a group which can be split off as an anion An ^ "**. 6. processes for dyeing, printing and mass dyeing materials, which consist entirely or predominantly of polymerized unsaturated nitriles such as acrylonitrile or vinylidenecyanide, from acid modified polyesters or from acid modified Polyamides exist, characterized in that dyes of claims 1-4 are used. 7. Materials that consist entirely or predominantly of polymerized unsaturated nitriles such as acrylonitrile or vinylidenecyanide, from acid-modified polyesters or from Acid modified polyamides are made and colored with dyes of claims 1-4, printed or colored in the mass are. Le A 14 485 - 49 - 309884/1263