DE2141987A1 - CATIONIC COLORS - Google Patents

Description

FARBENFABRIKEN BAYER AG

2H1987

IEVERK U SEN-Bayerwerk Central area Patents, Maiken and Licenses

Wed / Kra 2 and Aug. 1971

Cationic dyes

The invention relates to valuable, new dyes which are free from sulfonic acid and carboxylic acid groups, the general formula

-B-X-F-

R is an alkyl or aralkyl radical,
B is a direct bond or a bridge member, X is a divalent group,
F the remainder of a dye and
^ "'mean an anion.

The invention also relates to the production of the new dyes and their use for dyeing and printing natural and synthetic materials as well as those with materials dyed and printed with these dyes.

The invention preferably relates to azo dyes in general formula

Ie A 13 905 - 1 -

309808/1113

^X l -

To ^v

II

R _{1 is} an alkyl group with 1 to 4 carbon atoms or a phenyl

alkyl group with 1 or 2 carbon atoms in the alkyl chain, X ₁ a -SO ₂ -, -NH-SO ₂ -, -N (alkyl with 1 to 4 carbon atoms) -

SO ₂ -, -CO-, -NH-CO-, -N (alkyl with 1 to 4 carbon atoms) -CO-,

_0-, -s-, -NH-, -N (alkyl with 1 to 4 carbon atoms), -0-C0- or a direct bond if m> 1,

F ₁ the remainder of an azo dye,
ra the numbers 0 to 6 and

An ^ "'mean an anion, xind wherein the cyclic and acyclic Radicals can be substituted by nonionic radicals.

Among these dyes are to be emphasized those of the general ones formula

wherein
^R l

N = N-K

To ^v

III

an alkyl group with 1 to 4 carbon atoms or a phenylalkyl group with 1 or 2 carbon atoms in the alkyl chain, a -SO ₂ -, -NH-SO ₂ -, -N (alkyl with 1 to 4 carbon atoms) -SO ₂ -, -CO-, -NH-CO-, -N (alkyl with 1 to 4 carbon atoms) -CO-, -0-, -S-, -NH-, -N- (alkyl with 1 to 4 Carbon atoms), -0-00- or a direct bond, if. m> 1, the remainder of a coupling component of the aniline, phenol, naphthalene, indole, pyrazole, pyridine or pyrimidine series,

Le A13 903

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m the numbers O to 6 and

An ^ "" 'mean an anion, and in which the cyclic and acyclic radicals substituted by nonionic radicals

could be.

Particularly preferred dyes are those of the general formula

wherein
Ri

T,

To ^v

IV

an alkyl group with 1 to 4 carbon atoms or a phenylalkyl group with 1 or 2 carbon atoms in the alkyl chain, hydrogen, a C-, to C.-alkyl radical, halogen, nitro, methylsulfonyl, C-, to C.-alkoxy- , C-, to C.-alkoxycarbonyl or cyano,
Hydrogen or halogen,

Hydroxy, an amino, C ₁ to C. dialkylamino, C to C. alkylphenylamino, C to C. alkyl benzylamino, pyrrolidino, morpholino or piperidino radical, hydrogen, halogen, a C. ₁ to C.-alkyl, C ₁ to 0, -alkylcarbonylamino or benzoylamino radical, hydrogen or a C ₁ to C.-alkoxy radical or T-, and T ₂ together with the phenyl ring is a naphthyl radical, a -SO ₂ -, - NH-SO ₂ -, -N (alkyl with 1 to 4 carbon atoms) -SO ₂ -, -CO-, -NH-CO-, -N (alkyl with 1 to 4 carbon atoms) -CO- , -0-, -S-, -NH-, -N (alkyl with 1 to 4 carbon atoms), -0-C0- or a direct bond, if m is> 1, the numbers 0 to 3 and

mean an anion and wherein the cyclic and acyclic radicals can be substituted by nonionic radicals.

Le A 13903

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2H1987 H.

Particularly noteworthy among these dyes are those the general formula

wherein ^R 2

To ^v

Methyl, ethyl or benzyl,

a -SO ₂ -, -NH-SO ₂ -, -N (GH -) - SO ₂ - _> -CO-, -NH-CO-, -0-,

-NH- or -O-CO group,

Hydrogen, chlorine, cyano, methyl, trifluoromethyl or

Methoxy ,, hydrogen or chlorine, hydrogen or methoxy,

Hydrogen, methyl, chlorine or acetylamino, methyl, ethyl or by hydroxyl, methoxycarbonyl, Chlorine or cyano substituted ethyl, hydrogen, methyl, ethyl, benzyl or hydroxyl, Methoxycarbonyl, chlorine or cyano substituted ethyl,

the numbers 1, 2 or 3 and denote an anion.

Further preferred dyes have the general formula

^R 2 ~ \ =

) -X ₂ 2

To ^v

VI

wherein R _{2 is} methyl, ethyl or benzyl,

X _{2 is} -S0 ₂ -, -NH-SO ₂ -, -N (CH -) - SO ₂ -, -CO-, -NH-CO-, -0-, -NH- or -O-CO- group ,

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a remainder of the formulas

the numbers 1, 2 or 3, and an anion "mean.

CH,

or HO

Furthermore, "dyes of the general formula are preferred

A-F = F

To ^v

YII

the remainder of a diazo component, methyl, ethyl or benzyl,

Hydrogen, chlorine or a C ₁ to C, alkyl or alkoxy radical, hydrogen, chlorine, methyl, ethyl, acetylamino or, together with the phenyl ring, a naphthyl radical, -NH- or -N (C ₁ to C.-alkyl) - , the numbers 1, 2 or 3 and an anion.

Among these dyes are to be emphasized those of the general ones formula

Door ₇

1 N =.

m,

II,

"8th

To ^v

VIII

R ₂ methyl, ethyl or benzyl,

T ₇ hydrogen, chlorine or a C ₁ to C, alkyl or alkoxy radical,

Tq hydrogen, chlorine, methyl, ethyl, acetylamino or, together with the phenyl ring, a naphthyl radical ₉

Le A 13

309808/1113

2,987

Hydrogen, chlorine, bromine, trifluoromethyl, cyano, methyl, Methoxy, ithoxy, methoxycarbonyl, ethoxycarbonyl, methylsulfonyl or nitro,

Hydrogen, chlorine, bromine, cyano, nitro, formyl, methy1-sulfonyl, C ₁ to C, -alkyl, C ₁ to C, -alkoxy, C ₁ to C.-alkoxycarbonyl, phenoxy, C ₁ to C.-mono- or dialkylaminocarbonyl, C ₁ to C. mono- or dialkylamino-sulfonyl or phenylazo,

Hydrogen, chlorine, bromine, trifluoromethyl, cyano, nitro, methyl, hydroxyl, methoxy, ithoxy, methoxycarbonyl, Ethoxycarbonyl,

-NH- or -N (C ₁ to C ^ alkyl) -,
the numbers 1, 2 or 3 and
mean an anion.

Further preferred dyes are those of the general formula

BH-CO- (OH ₂ ) -Fj

To ^y

IX

Methyl, ethyl or benzyl,

Methyl, ethyl or ethyl substituted by hydroxyl, methoxycarbonyl, chlorine or cyano, hydrogen, methyl, ethyl, benzyl or ethyl substituted by hydroxyl, methoxycarbonyl, chlorine or cyano _t hydrogen, chlorine or a C ₁ to C. alkyl or alkoxy radical ,

Hydrogen, chlorine, bromine, trifluoromethyl, cyano, methyl, methoxy, ethoxy, methoxycarbonyl, ethoxycarbonyl, methyl sulf onyl or nitro,

Hydrogen, chlorine, bromine, cyano, nitro, forrayl, methylsulfonyl, C ₁ to C ^ -alkyl, C ₁ to C ^ -alkoxy, C ₁ to alkoxycarbonyl, phenoxy,

to C ^ mono- or dialkyl

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6 -

3 0 9 8 0 8/1113

7 2ΗΊ987

amino carbonyl, C ₁ to G. mono- or dialkylamino-sulfonyl or phenylazo,

Hydrogen, chlorine, bromine, trifluoromethyl, cyano, nitro, methyl, hydroxyl, methoxy, ithoxy, methoxycarbonyl, Ethoxycarbonyl,

the numbers 1, 2 or 3. and

mean an anion.

Dyes of the general formulas are also particularly preferred

To ^v

Xa

L JT- (OH, L, -X

At

C-)

Xb

worm

R ₂ methyl, ethyl or benzyl,

U hydrogen, chlorine, bromine, trifluoromethyl, cyano, methyl, methoxy, ethoxy, methoxycarbonyl, ethoxycarbonyl, methyl sulf onyl or nitro,

U-, hydrogen, chlorine, bromine, cyano, nitro, formyl, methylsulfonyl, C ₁ to C.-alkyl, C ₁ to C.-alkoxy, C ₁ to C, -alkoxycarbonyl, phenoxy, C ₁ to C.-mono - or dialkylaminocarbonyl, C ₁ to C. mono- or dialkylamino-sulfonyl or phenylazo,

U ₂ hydrogen, chlorine, bromine, trifluoromethyl, cyano, nitro, methyl, hydroxyl, methoxy, ethoxy, methoxycarbonyl, ethoxycarbonyl,

T ₉ -OH, -NH ₂ , -NH (C ₁ to C ^ alkyl), -NH-C ₅ H ₅ , -Ϊ or -N (C ₁ to C ₄

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X ₄ -CO-, -CO-O-, -SO ₂ -NH- or -SO ₂ -N (C ₁ to C m ₂ the numbers 1, 2 or 3 and
^ "'mean an anion.

Nonionic substituents for the purposes of the present invention are the non-dissociating substituents customary in dye chemistry, such as fluorine, chlorine, bromine; Alkyl ^ groups, in particular straight-chain or branched alkyl groups with 1-6 carbon atoms; Aralkyl radicals; Alkenyl radicals; Aryl radicals; Alkoxy radicals, in particular alkoxy radicals having 1-4 carbon atoms; Aralkoxy radicals; Aryloxy radicals, alkylthio radicals, preferably alkylthio radicals having 1-3 carbon atoms; Aralkylthio radicals; Arylthio radicals; Nitro; Cyano; alkoxycarbonyl, preferably those with an alkoxy radical with 1-4 carbon atoms; the pormyl radical; Alkylcarbonyl radicals, in particular those with an alkyl group with 1-4 carbon atoms; Arylcarbonyl; Aralkylcarbonyl radicals; Alkoxycarbonyloxy radicals, preferably with an alkyl group with 1-4 carbon atoms; .Alkylcarbonylaminoreste, preferably ^r with a Alkj lgruppe having 1-4 C Atomenj arylcarbonylamino groups; Alkylsulfonylamino radicals, preferably with an alkyl group with 1-3 carbon atoms;

Arylsulfonyl amino groups; Ureido; N-aryl or N-alkyl ureido, Aryloxycarbonylamino, alkyloxycarbonylaaino; Carbamoyl; N-alkyl-carbamoyl; Ν, Ν-dialkylcarbainoyl; N-alkyl-N-aryl-carbamoyl; Sulfamoyl; N-alkylsulfamoyl? ίί, Ν-Malkyl-sulfamoyl; Alkylsulfonyl; Alkenylsulfonyl; Aralkylsulfonyl, where in the mentioned Alkyl radicals are preferably 1-4 carbon atoms; Arylsulfonyl, Carboxylic acid alkyl esters, carboxylic acid aryl esters, sulfonic acid alkyl esters and aryl sulfonate groups,

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

Le_A 13 903 _ 8 -.

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2U1987

The anionic residues An "* are those for cationic dyes customary organic and inorganic anions.

Inorganic anions are, for example, fluoride, chloride, bromide and iodide, perchlorate, hydroxyl, residues of S-containing acids such as hydrogen sulfate, sulfate, disulfate and amino sulfate; Residues of nitrogen acid, such as nitrate; Residues of oxygen acids of phosphorus such as dihydrogen phosphate, hydrogen phosphate, phosphate and metaphosphate; Carbonic acid residues such as hydrogen carbonate and carbonate; other anions of acidic acids and complex acids, such as methosulfate, ethosulfate, hexafluorosilicate, cyanate, thiqcyanate, hexacyanoferrate (II), hexacyanoferrate (III), iri- and tetrachlorozincate, tri- and tetrabromo zincate, tetrabromo zincate, stannate _s Holybdate, tungstate, chromate, bichromate and tetrafluoroborate, as well as anions of esters of boric acid, such as the glycerol ester of boric acid, and of esters of phosphoric acid, such as methyl phosphate.

Organisehe anions are for example anions of saturated or unsaturated aliphatic cycloaliphatic _t aromatic and heterocyclic !: carboxylic acids and sulfonic acids, such as residues of acetic acid, chloroacetic acid, cyanoacetic acid, hydroxyacetic acid, aminoacetic acid, Methylaminoessigeäure, aminoethyl-sulfoneäure, methylaminoethyl-sulfonic acid, propionic acid, n-butyric acid,? , 2-methyl-butyric acid butyric acid, 2-ethyl-butyric acid, BichloressigBäure, Trichloressigsäurö, eah? rifluoressigsäure _g 2-Ohlorpropioneäure »3-chloropropionic, 2-chloro butter @ äure, 2-hydroxypropanoic, 3-Hydroxyproplon3äurs _f O Xthylglykoleäure, thioglycolic , glycerol, malic, Bodecyitetraäthylenglykolätherproplonsäure, 3 ~ (nonyloxy) -propionsäur © _s ^ - (iBotridecyloxyJ-propionic acid, 3- (Isoti idecyloxy) -diäthylen- glykolätherpropionsäure, Ätherpropionsäure the alcohol mixture bit 6 to IO carbon atoms, Shioeesig @ äure _$ 6?. -Ben3oylaraino-

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2-chlorocaproic, Nonylphenoltetraatb _v "anglykoläther-propion-Bäure, HonylphenoldiäthylenglyM ätfcerpropionsäure, Dodeeyltetraäthylenglykoläther-proTüc-IBAE-are, phenoxy acetic acid, nonyl phenoxy acetic acid, n-Vale ^ aneäure, i-Valerianaäure, 2,2,2-tri-acetic acid methyl _s n -Ospronsäure, 2-ethyl-ri-caproic acid, stearic acid, oleic acid, ricinoleic acid, palmitic acid, n-pelargonic _f lauric acid, a mixture of aliphatic carboxylic acids having 9 to 11 carbon atoms (Yersatic acid 911 of SHELL ·), a mixture of aliphatic carboxylic acids having 15 up to 19 carbon atoms (Versatic acid 1513 from SHELL), the xokosfettsäare-TorlaufB, äer indecanecarboxylic acid, n-2ridecanecarboxylic acid waä a coconut fatty acid mixture j of acrylic acid, methacrylic acid, crotonic acid, propargylic acid »oxalic acid, malonic acid, succinic acid, glutic acid Azelaic acid, dos isomeric from 2,2,4- and 2,4 _i 4 '"! 2'i: ime-fehylaoipic acid, sebacic acid, laosebacic acid (isomeric mixture iscli), tartaric acid, citric acid, glyoxylic acid, di- ■ ethyl ether-ci, ^ - ^t -dicarboxylic acid _f ethylene-bis-thioglycolic acid, dimethyl sulfide- «^ ct-dioarbonic acid, 2,2 '-bithio-di-n propionic acid, fumaric acid, Maleinscure, itaconic acid, ethylene-bis-imiro "acid, Nitrilosul £ oic acid _f Ketliaiisulfonsäure, Äthansulfeiieäure, chloromethanesulfonic, 2-Chloräthansulfonsäure and 2-BÖrdroxyäthansulfonsäure, Mersolat®, ie ^ 8"^{"σ ΐ5} ^^ ^^ ⁹ · ^^^ ⁰¹ acid obtained by chlorosulfonation of paraffin oil.

Suitable anions of cycloaliphatic carboxylic acids are e.g. W the anions of cyclohexanecarboxylic acid, cyclohexene-3-carboxylic acid and anions of araliphatic monocarboxylic acids are, for example, anions of phenylacetic acid, 4-methylphenyl acetic acid and commercial acid.

Suitable anions of aromatic carboxylic acids are, for example, the anions of the Benssoesäure, 2-methylbenzoic acid, 3-methylbenzoic, 4-methylbenzoic acid, 4-tert-Butylbenzoesäiire, 2 ~ _t bromobenzoic acid 2-chlorobenzoic acid, 3-0hlorbenzoesäure, 4-

Le A 15 903 - 10 -

309808/1 1 13

2H1987

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-dinitroberizoic 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 -hydroxybenzoic acid, 3-nitro-2-hydroxybenzoic acid, 4-methox: ybenzoic acid, 3-nitro-4-methoxybenzoic acid, 4-chloro-3-hydroxybenzoic acid, 3-chloro-4-hydroxybenzoic acid, 5-chloro-2-h.yäΓoxy -3-methylbenzoic acid, 4-eth.ylinercapto-2-cb.lorobenzoic acid, 2-hydroxy-3-methylbenzoic acid, 6-hydroxy-3-methylbenzoic acid, 2-hydroxy-4-meth.ylbenzoic acid, 6 -Hydroxy-2,4-dimethy! Benzoic acid, 6-hydroxy ~ 3-tert-buty! Benzoic acid, phthalic acid, tetrachlorophthalic acid, 4-hydroxyphthalic acid, 4-methoxyphthalic acid, isophthalic acid, 4-chloroisophthalic acid, 5-nitro-isophthalic acid, terephthalic acid Nitroterephthalic acid and the like nd Diphenylearbonsäure- (3,4) »o-vanillic acid, 3-sulfobenzoic acid, Benzoltetracarbon8äure- (l, 2 _i 4.5), naphthalenetetracarboxylic acid (1,4,5,8) _s Biphenylcarbonsäure- (4), abietic acid, phthalic acid -mono-n-butyl ester, terephthalic acid monomethyl ester, 3-hydroxy-5, 6,7,8-tetrahydronaphthoic acid (2), 2-hydroxynaphthoic acid (1) and anthraquinone carboxylic acid- ^).

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

Suitable anions of aromatic sulfonic acids are, for example, the anions of benzenesulfonic acid, benzenesulfonic 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-chlorotoluenesulfonic acid- (4),

Le A 13 903 - 11 -

309803/1113

2H1987

kl

i-hydroxybenzenesulfonic acid, n-dodecylbenzene sulfonic acid, 1,2,3, 4-tetrahydronaphthalenesulfonic acid (6), naphthalenesulfοηε-ätire- (1), Naphthalene di-sulfonic acid- (1,4) or - (1,5), naphthalene- ' trisulfonic acid (1,3.5), naphthol (1) sulfonic acid (2), 5-nitronaphthalene sulf onic acid (2), 8-aminonaphthalenesulfonic acid (l), 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 benzenephosphonic acids into consideration.

Colorless anions are preferred. For dyeing from an aqueous medium, preferred anions are those which are water-soluble 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, they are dyes as halides (especially as chlorides or bromides) or as methosulfates, Ethosulfates, sulfates, benzene or toluene sulfonates or as Acetates before. The anions can be exchanged for other anions in a known manner.

Le A 13 903 - 12 -

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2H1987

The new dyes of the formula I are obtained, if one either a grouping of the general formula according to methods known per se

Ck

- B - X - XI

wherein B and X have the meaning given in formula I, in suitable dyes or in dye precursors, which then in turn are converted into the desired dyes ^ and these then with compounds of the general Formula.

R - An ₁ XII

in which R has the meaning given in formula I and An stands for a radical which can be split off as an anion and which can be identical to An or be exchanged for An teann ₉ quat © rniert or a grouping of the general formula

XIII

introduces suitable dyes or dye precursors, Azo dyes of the formula III can be prepared by adding amines of the general formula

diazotized, with compounds of the general formula

H-K

couples and then with compounds of the general formula

R ₁ - An ₁ XVI

Le A 1.3 OUi - L5 -

3 0 90 0 8 / "! 1 1 3

2,987

quaternized. In the Po my XIV to XVI have R ,, K, X-, and m the meaning and definition given in formula III stands for one split off as an anion residue which can be identical to An or can be exchanged for An.

Suitable amines XIV are, for example; Ί-Amino-benzenesulfonic acid- [Jl, 2,4-triazolyl) - (1) J -methylamide, 3-amino-benzenesulfonic acid- ßl, 2, 'i-triazolyl) - (l] i} -methylamide, 4- Amino-benzene sulfonic acid-ß- Ql ₉ 2 ', 4-triazolyl) - (l) I -ethylamide, 3-aminobenzenesulfonic acid-ß- [T 1,2,4-triazolyl- (l) _} - ethylamide, 4-amino-benzenesulfonic acid-γ «Γ (ΐ, 2,4-triazolyl) - (l) J -propylamide, 3-amino-benzenesulfonic acid-γ- Ul _S 2 ₁ 4-triazolyl) - (l) j -propylamide, 4-amino-benzene is fonsäur e-6 # - f] [1 _f 2 _f 4-triazolyl) - (1) I -butylamide, 3-chloro- ^/ i-ate! iino = 'benzenesulfonic acid "- | _ (1,2,4-triazolyl) - (l) I-amide, 3-chloro-4-amino-I) enzol-.sulf oleic acid- JJl, 2,4-triazolyl) - (l) -J

niethylamide, 3-ABiino - ^ - chl or -benz oil su 1 fonsäure- | ll, 2, ^ ~ triazolyl) - (l) _ [-

methylamide, 3 -? "Ciilor- ⁱ i-aiBino-ben2; olsiiIf onic acid-ß- | ( _{1,2 f} 4-triazolyl) - (l) J-

ethylamide, 3-amino - ^ - ehlor ^ benzolEuIf oasäure- = ß- Rl, 2,4-triazolyl) - (l) J -

ethylamide 3 »chloro-4-amino ~ beriZol snlf onic acid-γ- Rl, 2,4-triazolyl) - (l) 7 -

propylamide, 3-amino-4-chlorobenzol sulfonic acid-γ- [II, 2,4-triazolyl) - (l) J-

propylamide, 2-A "» ino-3 - = - chlorobenzenesulfonic acid-γ- Rl, 2, ^ - triazolyl) - (l) j -

propylamide, 3-chloro-4-aminobenzenesulfonic acid-cj- Ql, 2,4-triazolyl) - (l Γ [-

butylamide, 3-chloro-4-aminobenzenesulfonic acid - ^ - (Tl _f 2,4-triazole> I) - (I)] -

butyl-methyl-amide, 3-Amino-'i-chloro-benzo-sulphonic acid-40-U 1, 2, ^ -1 r i. / Ol yl) - (1) | -

but y I-mn Uiy I-ain id,

Or-'ι— mino-honzolHuL foiUiUiu μ j (1, ίϊ, Ί -fcria <i> 1 y 1) U)

-fii-i i Λ,

3) 'IiHJO / 1! 1 :.:

2,987

2, 5-dichloro-ij-aminobenzene sulphonic acid - = - Kl, 2, ^ -triazolyl) - (l Π

-methylamide,

2,5-dichloro-4-aminobenzenesulfonic acid- 1 (1,2,4-triazqlyl) - (l) 1

-methyls-methyl amide,

2 _f 5-dichloro-i-aminobenzenesulfonic acid-ß- Rl, 2,4-triazolyl) - (l) j

-ethylamide,

2, 5-dichloro-4-arainobenzene sulfonic acid (β - \ _ {1,2 "4-triazolyl) -

(l) I -ethyl) -methyl amide,

2, 5-dichloro-4-amino-benz oil sulphonic acid- (β- j_ (l ₉ 2 ₉ ^ = triazolyl) -

(l) I -ethyl) -äthylamid _s 2, 5-dichloro-4-aminobenzene sulfonic acid »j'- j_ (1, 2" 4 = triazolyl) -

(1) I -propylamide, 2,5-dichloro-4-aminobenzenesulfonic acid (y = j (l ₉ 2 " % -triazolyl) -

(I) J-propyl) -methylamide, 2, 5-dichloro-4-aminobenzenesulfonic acid = (γ- [[l, 2 ". ^ - triazolyl) -

(l) J-propyl) ethyl amide j, 2, 5-dichloro-4-aminobenzene sulfonic acid-fO- [(1,2 ₉ 4-triazolyl) -

(l) I -butylamide 2, 5-dichloro- k- amino-benzenesulfonic acid- {tj- Rl, 2, ^ -triazolyl) -

(l) I -butyl) -methylamide 2, 5-dichloro- ^ i-amino-benzene sulphonic acid ^ A ^ = R1,2,4-trazolyl) -

(I) I -butyl) -äthylamid 2,5-dichloro-4-amino-benzenesulfonic acid-iJ- Kl , 2, ^ -triazolyl) -

(l) -pentylamide

2, 5-dichloro-'i-amino-benzene sulphonic acid-ij- (l, 2, ^ -triazolyl) -

(l) I -hexylamide

2-Aπlino-5-methyl-benzenesulfonic acid [(], 2, 4-triazolyl) - (l

methylamide 2-amino-5-methyl-benzene sulfonic acid-ß- j (l, 2, 4-triazolyl) -

äthylamid 2-Amino-5-methyl-benzenesilfonsäure- (ß- [(l, 2, Ί-triazolyl) - (l) J

ethyl) methyl amide

Le A 13 903 - 15 -

O 9 8 O «M Π 3

2H1987

^ -Amino - ^ - methyl-S-chlorobenzenesulfonic acid- f (l, 2,4-triazolyl) -

(l) J-methylamide

2-Amino-4-methyl-5-chlorobenzenesulfonic acid-ß - [(1,2,4-triazo =

IyI) - (1)] ethylamide

2-Amino-4-methyl-5-chlorobenzenesulfonic acid (β - [(1,2,4-triazo =

lyl) - (l) I-ethyl) methylamide

2-Ainino-4-methyl-5-chlorobenzenesulfonic acid-y - [(1,2,4-triazo ^

- (1) J-propylamide

3-methyl-4-aminobenzenesulfonic acid - [_ (l, 2,4-triazolyl) - (l) 1 -

methylamide

3-methyl-4-aminobenzenesulfonic acid-ß- Rl, 2, 4-triazolyl) - (l) ~ j- ^ ethylamide

^W 3-Methy 1-4-amino-benz oil sulphonic acid- (ß- [i, 2,4-triazolyA- (l) ^ -

ethyl) methylamide

3-methyl-4-amino-benzenesulfonic acid-γ- [(l, 2,4-triazolyl) - (l) T-

propylamide

Q1,2,4-Triazoly ^ - (1) J-methyl- (4-aminophenyl) -sulfon Q1,2,4-Triazoly]) - (1 ) \ -methyl- (3-aminophenyl) -sulfon [] 1,2,4-TriazolyJ- (l)] -methyl- (2-aminophenyl) -sulfone ß- Q1,2,4-Triazoly ^ - (1) [-ethyl- (4-aminophenyl) -sulfone ß- ßl, 2,4-Triazoly- (l) I -ethyl- (3-aminophenyl) -bu1 fön vr (1,2,4-Triazolyi- (l) | -propyl- (4-aminophenyl) -sulfon y -fTl, 2,4-Triazoly ^ - (l | -propyl- (3-aminophenyl) -sulphone l ^ - [jl, 2,4-triazoly ^ - (l)] -butyl- (4-aminophenyl) -sulphone [(1,2,4-Triazolyi- (l) j -methyl- (3-chloro-4-aminophenyl) -8ulfone

β - [(1,2,4-Triazoly ^ - (l) I-ethyl- (3-chloro-4-aiainophenyl) sulfone

Y - [(l, 2,4-Triazoly ^ - (l)] - propyl- (3-chloro-4-aminophenyl) sulfonic [(1,2,4-triazolyl) - (I)] - methyl- ( 3-amino-4-chlorophenyl) sulfone ₍

ß - [(l, 2,4-TriazolyÄ- (l)] - ethyl- (3-amino-4-chlorophenyl) -eulfone; y- £ (l, 2,4-triazolyp- (l)] - propyl- (3-amino-4-chlorophenyl) sulfone pl, 2 _{) (} 4-triazoly ^ - (l | -inethyl- (2,5-dichloro-4-aminoplienyl) sulfone

ß-0l »2,4-triazolyl) - (l)

ß0 »,
γ- Q1,2,4-triazolyl) - (l] to- [(1,2,4-triazolyl) - (1]

Ethyi- (2,5-diochloro-4-amino-phenyl) -ulfone, -propyl- (2,5-dichloro-4-fteinophenyl) -eulfone -butyl- ( 2,5-diochloro-4-aminophenyl) -sulfone

Le A 13 903 _ ₁₆ ^

309808/1 113

3-Amino-benzoic acid- JjU, 2,4-triazolyj) - (i) ^ [- methylamide 3-Amino-benzoic acid- jj (l, 2,4-triazoly] ^ - (l) J -methyl) -methylamide 3 Amino-benzoic acid-ß- F (1,2,4-triazolyl) - (l ^ »ethylamide 3-amino-benzoic acid- ( ^r ß- [(1,2 _f 4-triazolyl) - (l) I-ethyl ) -raethyl =

amide

3-Amino-benzoic acid-γ- [(1,2,4-triazolyl) - (I / I-propylamide

3-Amino-benzoic acid- (γ- Γ (ΐ, 2,4-triazolyl) - (1) J-propyl) -me =

thylamide

4-Amino-benzoic acid- [~ (l _r 2,4-triazolyl) - (lJ-methylamide

4-Amino-benzoic acid {f (1,2,4-triazolyl) - (1) 1 -methyl) -methyl =

amide

4-amino-benzoic acid-β- [(1,2,4-triazolyl) - (in-ethylainide 4-Amino-benzoic acid- (ß-R 1,2,4-triazolyl) - (1) I -ethyl) -methyl =

* "amide

4-Amino-benzoic acid ~ y- j_ (1,2,4-triazolyl) - (1)] j-propylamide ^ -Amino-benzoic acid-Cy - [(1,2,4-triazolyl) - (1) J-propyl) -methyl =

amide

^ -Amino-benzoic acid-W- | (1,2,4-triazolyl) - (l) J-butylamide 3-Chloro-4-aminobenzoic acid (p1, 2,4-triazolyl) - (1) J-methyl =

amide

3-chloro-4-aminobenzoic acid --— (M 1,2,4-triazolyl) - (1) 1 -methyl) -

metTiylamide

3-chloro-4-aminobenzoic acid-β- β 1,2,4-triazolyI) - (1) 1 -ethyl =

amide

3-chloro-4-aiaino-benzoic acid-0- £ (1,2,4-triazolyl) - (l)} - ethyl) -

methylamide

-4-amino-benzoic acid- (ß- f (1,2,4-triazolyl) - (1) J -ethyl) -

ethylamide

3-chloro-4-amino-benzoetic acid-y - [(1,2, d-triazolyl) - (1) Ί -propyl: 3-chloro-4-ainino-benzoic acid- (γ- Γ (1,2,4-triazolyl) - (1)

-meth; 3-methyl-4-aminobenzoic acid-ß- [(1,2 ₁ 4-triazolyl) - (l)

amide

propyl) lamide

-ethyls amide

3-methyl-4-aminobenzoic acid-y- {_ (1,2,4-triazolyl) - (1) J-pros

pylamid

2,5-dimethyl-4-aminobenzoic acid-ß- R1,2,4-triazolyl) - (l) l -

ethylamide

2,5-Dinjethyl- '* - aniino-benzoic acid- (y- R 1,2,4-triazolyl) - (1) 1 -

propyl) methylamide

3-methoxy-4-aminobenzoic acid-ß- (1,2,4-trlazolyl) - (l) l -ethyl =

^LJ amid

Le k 13 903 - 17 - ■

309808/1113

3-methoxy-4-aniino-benzoic acid-y «- ί (λ ^, 4-triazolyl) - (l) J-pro =

pylamid

3-methoxy-4-araino-beri: ioet 'J-, e »(W- JJ1,2,4-triazolyl) - (1) 1 -

butyl) methylamide

3-Trifluorraethyl-4-amino-ben2O ": ε ..re- Ri, 2,4-triazolyl) - (1) | -

methylaraill

3-Trifluoromethyl- 4-amino-beiizoic acid "-β- J (1,2,4-triazolyl) - (1)! ■

^L äthylainid - ¹

3-nitro-4-aiairAO-benzoic acid ~ ß- (1,2,4-triazolyl) - (l) j-ethyl =

^LJ amid

3-Nitro-4-aiiiino-benzoic acid - "(ß- | (l, 2,4-triazolyl) - (l) I-ethyl)

^L -metnylamide

3-cyano-4-amino-benzoic acid- (1,2,4-triazolyl- (l) [- methylamide

»3-cyano-4-aminobenzoic acid-ß- Rl, 2,4-triazolyl) - (l) j-ethyl = amide

, ^ - " ⁷¹ Iiazolyl) - (l) 3-acetic acid - ('s-er! Liioanilid) L (1,2,4-triazolyl) ~ (lJ -acetic acid- (3-aminoanilide) [] (l , 2,4-Tria2olyl) - (l ^ -acetic acid- (3-chloro-4-aminoanilide), 2,4-triaolyl) - (lJ -8-acetic acid-N «methyl- (4-aniinoanilide)

-acetic acid ~ N-methyl- (3-aininoanilide)

™ QS3igEäii'e-li-ynethyl- (3-chloro-4-

aminoanilide)

Rl, 2,4-TriazolYl) - (l) T ° acetic acid-N-methyl- (4-amino-3-

chloranilide)

ß- [(1,2,4-triasolyl) - (l) | - propionic acid (V-aminoanilide)

ß- Ql, 2,4-triazolyl) - (l) J-propiansäitre »(3-aiainoanilid)

Q- £ (1,2,4-triazolyl) - (l) I-propionic acid- (3-chlpr-4-aminoanilifi>

Q- Ql, 2,4-triazolyl) - (l)]> - propionic acid- (3-afflino-4-chloroaniline}

S-Ql, 2,4-triazolyl) - (l-propioic acid-N-ethyl- (4-aininoanil '-. Fl- [l (l _s 2,4 = triozolyl) - (lI-propionic acid-N-ffiothyl - (3-aminoenilide) Q- [II, 2,4-triazolyl) ~ (l | «propionic acid-N-iHethyl- (3-chloro-4-

aminoanilide)

ß- 21,2,4-TriazoIyI) - (I | «propionic acid-N-raethyl- (3-amino-4-chloro

anil id)

Cj- jll, 2, 4-triazolyl) - (l-butyric acid- (3-amino-4-chloranilide)

Le \ 13 903 .. to -

onueott / 1 μ.ϊ

• 2U1987

N ~ (Q, 2, ^ - Triazoly ^ - (l)] - methyl) -ii-ömtno-aniline N- (C (I »2,4-triazoly ^ - (l) 3-methyl) -3-amino-aniIine N- (Γ (ΐ, 2,4-triazoly]) - (l) J-methyl) -3-clilor-4-amino-anil in N- (β 1 »2, 4-triazolyl) - (1)] - methyl) -3-nitro - ^ - amino-ani 1 in N- (L (1,2, ^ - triazoly ^ - (l)] - methyl) -3-amino-ii-chloro-aniline N- (β - [(I, 2,4-triazolyi) - (l) 1 -ethyl) - ^ - amino-aniline N- (ß-C (1,2, VrriazolyJ) - (l)] - ethyl) -3-amino-aniline N- (ß-C (l, 2,4-triazoly5- (l3 -ethyl) -3-chloro-4-amino-aniline N- (P - [* (], 2,4-triazolyl) - (] J] -ethyl) -3-methyl - ^ - amino-anil in N- (P- L (I, 2, ^ i-triazolyl) - (l)] -ethyl) -3-nitro-^ -amino-anil in N- (β-LU., 2,4-triazolyl) - (1)] ethyl) -3-amino-4-trifluoromethyl = N- (γ- Ql, 2, ^ - TrIaZoIyTy- (I) j -pro'pyl) - ^ - amino-aniline

Ν- (γ- Qi, 2, ^ - Triazoly ^ ~ (l)] -propyl) -3-amino-4-methylsulfonyl-

aniline

, 2,4-triazolyl) - (l ) '_

1ST- (γ-Ql, 2,4-triazolyl) - (1) j -propyl) -3-amino-4-chloro-aniline

\ l 1, 2, 4-triazolyl) - (l ) ~ \ -methyl- ('i-aminopheny ^ -ketone Ql, 2,4-triazolyl) - (l) I-irethyl- (3-amino- ^ chlorophenyl) ketone

ethyl (^ -amiiioprienyl) ketone
-athyl- (3-ch Lor - ^ - aminophenyl) ketone -äthyl- (3-amJno- ⁱ i-nitro-phenyl) ketone

, L _- ^, - ,. ^ _) - (l) J-propyl (- ^ - aminophenyl) -ketone

Y-Q (1,2,4-triazolyl ') - (1)] propyl (3-chloro - ^ - aminophenyl) ketone y-U (1,2,4-triazo] yl) - (l)] - propyl (3-nitro-4-aminophenyl) ketone

^ -Amino-benzoic acid-ß- ßl, 2,4-triazolyl) - (l) I-ethyl ester ^ Amino-benzoic acid-y-Ql, 2,4-triazolyl) - (l) I -propyl ester 3-chloro-4-aminobenzoic acid-ß-Ql, 2,4-triazolyl) - (l) I -ethyl =

ester

3-Chloro-4-aminobenzoic acid-Y-Q (r, 2,4-triazolyl) - (l)] -propyl =

ester

^ i-Chlor-3-amino-benzoic acid-β-Q (1,2,4-triazolyl) - (I) I -ethyl =

ester

^ -Chloro-3-amino-benzoic acid Yr (l, 2, ⁱ i-triazolyl) - (l)] propyl =

ester

3-Methyl- ^J i-amino-benzoic acid-ß- | jl, 2, ^z i-triazolyl) - (l)] - ethyr =

ester

3-methyl - ^ - amino-benzoic acid-Y-r (l, 2, ii-triazolyl) - (l) J-propyl =

ester

le A 15 905 - 19 - "

309808/1113

2H1987- 2 »

β- βΐ, 2,4-triazolyl) - (l j] ethyl (4-aminophenyl) ether β- | 11,2,4-triazolyl) - (1 J] -ethyl- (3-aminophenyl) -ether β- Q1,2,4-TriazolylJ- (I) I-ethyl- (3-chloro-4-aminophenyl) -ether β- L (1,2,4-triazolyl) - (1)] ethyl (3-nitro-4-aminophenyl) ether ß- [(1,2,4-Triazolyl) - (l) I-ethyl- (3-methylsulfonyl-4-aminophenyl) -

ether ß-ßl, 2,4-triazolyl) - (l) I -ethyl- (3-amino-4-bromophenyl) -ether Y- n ⁱ » ² » ^il - ^Triazol y ¹ ) - ( ¹ U -propyl) - (4-aminophenyl) -ether γ- ßl, 2,4-triazolyl) - (l) J-propyl - (3-cyano-4-aminophenyl) -ether γ- JX 1,2,4-triazolyl) - ( 1) I -propyl- (3-amino-4-chlorophenyl) -ether [(1,2,4-triazolyl) - (Tj] -methyl- (4-aminophenyl) -thioether

β-1,2,4-Triazo3yl) - (1) I -ethyl- (4-aminopheny1) -thioether β- Jj 1,2,4-triazolyl) - (l JJ -ethyl- (3-amino-4-chlorophenyl) -thio =

ether

γ- [~ (1,2,4-triazolyl) - (l)] - propyl (4-aminophenyl) thioether γ- [(I, 2,4-triazo] yl) - (l)] propyl (3-aminophenyl) thioether

Suitable coupling components XV Bind "for example:

Phenol, E-cresol, p-cresol, 3-chlorophenol, N _f N-dimethylaniline,! Ί, Ν-dimethyl-m-toluidine, Ν, Ν-diethylaniline, N, N-diethyl-ia-toluidine, N-ethyl -N-ß-cyanoethylaniline, N-ethyl-N-ß-cyanoethyl-m-toluidine, K, N-bis- (ß-cyanoethyl) -aniline _f N, N-Bi s- (e-cyanoethyl) -m- toluidine, N-ethyl-N- (ß-hydr oxy äthyl) -aniline, N-ethyl-N- (ß-hydroxyethyl) -m «toluidine, N, N-bis- (ß-hydroxyethyl) -aniline, N, N-bis- (ß-hydroxy-ethyl) -m-toluidine, N-ethyl-N-benzylaniline, N-ethyl-N-benzyl-m-toluidine, N-methyl-diphenyl-amln, N-ethyl-N- (ß-methoxycarbonyl-ethyl) -aniline, N, N-bis- (a-methoxycarbonyl-ethyl) -aniline, N-ethyl-N- (ßmethoxycarbonyl-ethyl) -in-toluidine, N, N-bis- (ß-methoxy-carbonylethyl) -m-toluidine, Ν, Ν-diinethyl-m-acetylamino-aniline, N, N-diethyl-m-acetylamino-aniline, N-ethyl-N-ß-hydroxyethyl-macetylamino-aniline, N-ethyl-N- (ß-acetoxyethyl) -m-benzoylamino-anilln, N-ethyl-N- (ß-benzoyloxyethyl) -m-chloroacetylamino-anilln, N-ethyl-N- (ß-phenoxyethyl) -m- hydroxyacetylamino-aniline, N-ethyl-N- (ß-methoxyethyl-m-chloroacetyl aminoaniline, H ^ -diethyl-Z-methoxy-S-acetylamino-aniline, N, N-di-

^Lö - 3.3 903

309808/1113

2H1987 IA

ethyl-S-Klioxy-S-acetylamino-aniline, N-ethyl-N- (ß-chloroethyl) -aniline, I-Xthyl-N-iß-chloroethylJ-m-tol'aidin, N-phenyl- ■ orpholine, 2 -Methyl-indole, 1,2-dimethyl-indole, 1-phenyl-2-methylindole, i-methyl-2-phenyl-indole, 2-ethyl indole, 2-phenyl indole, 1-e-cyanoethyl-2-me thylindole, 1-β-cyanothyl-2-phenylindole, j- (2-phenylindolyl-1) propionic acid amide, 2-ß-naphthylindole, 2-p-biphenylindole, 2,5-dimethylindole, 2-phenyl-5 ~ ethoxyindole, 2-methyl-5-chloroindole, 2-methyl-6-chloroindole, 2-methyl-5-nitro-indole, el naphthol, ß-naphthol, o ^ -naphthylamine _f 1-ethyl-1,2, 3,4-tetrahydroquinoline, 2,6-dihydroxy-3-cyaiio-4-methyl-pyridinj, 2,4,6-tris-ethylaminopyrimidine, 2,4,6-tris-diethylarainopyrimidine, 2,4,6 -Tris-diinethy.lamino-pyrimidine, l-phenyl-3-methyl-5-aminopyrazole, l-phenyl-3-methyl-pyrazolone-5, L- (2-chlorophenyl) -3-methyi ~ pyrazolone-5, l - (3-chlorophenyl) -3-methyl-pyrazolone-5, l- (2,5-dichlorophenyi) -3-methyl-pyrazolone-5, l- (2-nitrophenyl) - * 3-methyl-pyrazolone-5, 1- (3-nitrophenyl) -3-methy1-pyrazolone-5, 1 - (p-Tolyl) -3-methyl-pyra zolon-5, 1-Benzyl-3-methyl-pyrazolon-5, 1- (3-Sulfolanyl) -3-HIe ^ yI-PyCaZOlOn-S, 1-Phenyl- pyrazolone-5-carboxylic acid (3) -aTnid, 1-phenyl-pyrazolone- 5- carbon8-acid-3-ethyl ester, 1-phenyl-3-methoxycarbonylmethylpyrazolone-5, la-cyanoethyl-3-raethyl-pyrazolone-5 _f 1- ß-chloroethyl-3-ethyl-pyrazolone-5, l-ß-aoetyloxyethyl-3-ethyl-pyrazolone-5.

The coupling takes place in a manner known per se, for example in neutral, acidic or weakly alkaline, aqueous medium.

The quaternization is expediently carried out by heating in an inert organic solvent, e.g. B. Kohlemraii # rato | genkohlemrasaerstoffen fen such as benzene, toluene or xylene, Halo = vie Tetraohlorkohlensteff _f "tetrachloroethane, chlorobenzene, o-Dichlorbenzolo Nitrokohlenwasssr ·· substances, such as nitroethane, Nitrobsnrzol ODSR Witrcr ^ phtiiilin or in dimethylformamide, acetonitrile or Dimethyl sulfoxide using preferably equivalent amounts of alkylating agents, for example with methyl chloride, methyl bromide, methyl iodide, ethyl bromide, Bdnzylohlorid _s trimethyloxonium borofluoride, dimethyl sulfate, biethyl sulfate _3- p-Toluenesuironsäuremethyl-, -äthyl «ode ^ -.

Le A.13 903 - 21 -

309808/1113

The resulting quaternized Far ** - T; offe are in the solvents used se: - ^ r soluble and can be isolated by filtering -trde i. Stay the quaternized dyes in? 3> ^ nda-ig of Djraethylforipamid, dimethyl sulfoxide or acetonitrile partially or completely in solution, they may dur "ä diluting isit water and adding water-soluble salts, such as sodium or potassium chloride, can be deposited"

Another way of preparing the azo dyes of the formula III ordered in the coupling of the amines of the general formula

To ^ "^;

XVII

with the coupling component XV »in which the symbols have the meaning given in formula III.

The azo dyes of the formula YII are prepared by either amines of the general formula

A - NH ₂ XVIIl

diazotized, with compounds of the general formula

couples and 'then with compounds of the general formula

R ₂ - An ₁

Le A13 903

- 22 -

quaternized, or amines XVIII after diazotization with Ver bonds, the ..general formula

To ^v

clutch. In formulas XVIII - XXI have A,

T ₇ ,

XXI

Tg, X,

and m _{2 has} the meaning given in formula VII and An stands for a radical which can be split off as an anion and which can be identical to An or can be exchanged for An.

Suitable. Coupling components XIX are for example: N-MeIhy1-N- [θ, 2,4-triazoly]) - (l)] - methyl aniline N-Aethyl-N-iß-Ijil ^^ - trJazoly]) - (lj] - ethyl) -aniline N.-Aethyl-N ~ (y - [(l, 2, ^ ~ triazolyl) - (l) J-propyl) -aniline N-methyl-N-ßl, 2, V-triazoly]) - (l)] - methyl -m-toluidine N -.Aethyl-N- (β-L (l _f 2, ^ i-triazmyl ;-(])] - eth> l) -m-toluidine N-ethyl-N - (y - [(1,2,4-triazolyl) - (!)] propyl) -m-toluidine

N-Methy1-N- Rl, 2,4-triazolyl) - (1) 1-methyl) -2-methoxy-5-- thyl-anil

my

N-Ethy 1-N- (ß- Rl, ² »4-triazolyl) - (1) Ί -ethyl) -2-methxoy-5- ^LJ methyl-aniline

N-Ethy 1-N- (V-Rl, 2,4-triazolyl) - (1) "| -propyl) -2-methoxy-5 ^L - ¹ methyl-aniline

N- (l ^, 2 ^ - triazolyl) - (l) J-methyl) -a-naphthylamine, N- (ß | l, 2, ^ -triazolyl) - (1) J ethyl) -a-naphthylamine

The azo dyes of the formula IX «are prepared by either adding amines of the general formula

XXII

Le A13 903

diazotized, with compounds of the general formula

XXIII

1.CO- (CH ₂ ) -1

couples and then with compounds of the general formula

H ₂ -An ₁ XX

quaternized, or amines XXII after diazotization with compounds of the general formula

7th
JT- (- * ¹ * • At* NH-CO- (CH ₂ )

XXIV

clutch. In the formulas XX, XXII, XXIII and XXIV , U, U ₁ , U ₂ , R ₂ , T ₅ , Τ _β , T ₇ and B _{8 have} the meaning given in the formula IX, and An ₁ represents one which can be split off as an anion Remainder that can be identical with An or can be substituted for An. '

Suitable coupling components XXIII are, for example:

Η 1,2, ^ t-triaz; olyl) - (l)] - es s "ißsäurc - (3-flime thy laraino-onillcl)

[(], 2, 4-TritiKOlyl) - (l) I -acetic acid- (3-dimethylnmino-.i »-methsi

oxy-anilide)

fl-ßl _t 2 _f % -TriazolyI) - (I JJ-propionsKuru- (3-diBiethyloinino-onilid)

ß-l (1,2, '4-Triazolyl) - (in -propionic acid- (3-tlir.iGthylamino- ² i ~

^J methoxy-enilide)

Q1,2, ^ - Triezolyl) - (l JJ -acetic acid- (3-diHtliylnmino-önilitr)

Ql, 2, ^ -triazolyl) - (l) T -seig-smire- (3-tUUthy3oiniiio-4-iiictlioxy ~

«Nillil)

, Sf 4 ~ triazolyl) - (] J [-propionic acid (S-dlMtliylamino-oullifl)

13 903 - 24 -

309808/1113

2,987

The azo dyes of the formulas Xa and Xb are prepared by using either amines of the general formula

U -NH ₂

ü,

XXII

diazotized, with compounds of the general formula

X ₄ - (CH ₂

XXV

couples and then with compounds of the general formula

H ₃ -An ₁ XX

quaternized or amines XXII after diazotization with Ver = bonds of the general formula

At"

XXVI

clutch. In the formulas XX, XXII, XXV and XXVI, U, U ₁ , Ua »T ₉ , .X ₄ , In ₂ and R _{2 have} the meaning given in the formulas Xa and Xb, and An ₁ stands for one as an anion cleavable remainder, which can be identical to An or can be exchanged for An.

Suitable coupling components XXV are, for example:

LeA 13 903

-25 -

309808/1113

2H1987

ß-Aniinonaplitlialin- 5-sulfonic acid- (β- Γ (1,2, '1- fcriazolyl) - (1)] - ethyl) -

ß-aminonaphthalene ~ 5-sulfonic acid- (y- [(1,2,4-triazolyl) - (l) J-pro

pyl) - amide

ß ~ AKiinonaphthalin-5-sulfonic acid- ( _ω - _{Ql 1} 2, U, -fcriazolyl) - (l)] - bufcy "J> -

■ "amide

ß-Auiinonaphthalin- 6- sulfonic acid- [(1,2, ^ - triazolyl) - (1 )} - methyl-

fl-aminonaplithalin-. 6- _B IAF onaSure- (y - [(1,2,4-fcriazolyl) - (1)] - PRCT

'- · PyI) -WiIi (I.

.ß-Araincmaphthalin-6-sulfonsfiure- (u-Q 1,2, * - triazolyl) - (!)] -butyl) - * amide

j a-Ajninonaphthalin-6-eulphonic acid- (β-. [(1,2, H-triazolyl) - (1)] -ethyl) -

- · '·' · amide

α-Amiiiöiiaphthalin-δ-sulfonic acid- (y - [(1,2,4-triazolyl) - (l) J-pro- '· ...'. '■ " pyl) -amide

a-Hyäroxynaphthalin-6-sulfonic acid- (β- Γ (1,2,4-triazolyl) - (!)] -

ethyl) amide

a-IIyäroxynaphthalin-6-sulfonic acid- (/ - Γ (1,2,4-triazolyl) - (!)! - pro

* ■ .pyl) -amid

B-Hyäroxynaphthalin ~ 6-sulfonic acid- (β- [(1,2, ¹ I-triazolyl) - (1 )}

■ ■ · äthylj-

2-Hydroxy ~ naphthalenecarboxylic acid Xβ- [(1,2,4-triazolyl) - (1) 1 -

ethyl) amide

^ a-Hydroxy-naphlihallnoarboxylic acid - ^ - (y- [(1,2,4-triazolyl) - (1)] P- . Propyl) azide

UA 13 §03 - ^a6 "

309808/1113

2U1987 Vr

Suitable diazo components XVIII and XXII are, for example:

4-nitraniline, 2,4-dinitraniline, 2-chloro-4-nitraniline, 4-chloro-2-nitraniline, 2, S ^ dichloro - ^ - nitraniline, 2,6-dichloro-4-nitraniline, 2-methoxy- 4-nitroaniline, 2 ~ cyano-4-nitroaniline, 2-trifluoromethyl-4-chloroaniline, 2-cyano-6-chloro-4-nitroaniline, 2,4-dinitro-6-bromaniline, 4-cyananiline, 3,4- Dicyananiline, 2-cyano-5-chloroaniline, 4-cyano-3-chloroaniline, 2,4-DlCyBn-O-ChIOraniline, J-nitro - ^ - amino-benzoic acid butyl ester, 4-nitro-2,6-dicyananiline, 2- Chloroaniline, 5-chloroaniline, 4-chloroaniline, 2-nitroaniline, 3-nitroaniline, 2-chloro-5-nitroaniline, 2-chloro-4,6-dlnitrioaniline, 2-nitro-3-chloroaniline, 2,4-dicyananiline, 2,3-dichloroaniline, 3,4-dichloroaniline, 2,4,5-trichloroaniline, pentachloroaniline, 2-chloro-4-methylaniline, 2-methyl-4-chloroaniline, ethyl 3-chloro-4-aminobenzoate, ethyl 4-aminobenzoate , 4-aminobenzoic acid methyl ester, 3-nitro-4-aminobenzoic acid ethyl ester, 4-phenyl-sulfonylaniline, 4-aminobenzoic acid dimethylamide, 4-methylsulfonylaniline, 2-trifluourmethyl-4-i-methylsulfonylaniline, 4-methoxyaniline, 3-methoxyaniline, 2-nitro-4-methoxyaniline, 2-methoxy-4-nitroaniline, 2-bromo-4-nitroaniline, 3-bromo-4-nitroaniline, 2-bromo-4-cyananiline _s 3- "BrOi! 3 -4 »eyanftniline, 2-nitro-4-bromaniline, 3-nitro-4-bromaniline, 3-cyano *% - brofflaniline _< 3-chloro-4-nitroaniline _i 3-nitro-4-chloroaniline, 2-trifluoromethyl-4 -nitroaniline, 2-trifluoromethyl-4-cyananiline, 4-trifluoromethyla-diline ^^ - chlorine - ^ - trifluoromethylaniline, 2-nitro-4-trifluoro-methyl aniline, 3-chloro-4-trlfluoromethylaniline, 3-nitro-4 -trifluoromethylaniline, 2,6-dibromotoluidine, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-aminoazobenzene, 2-amino-4-phenyl-thiadia-ZoI- (1,3,5).

The dyes obtained according to the process are outstandingly suitable for dyeing and printing cationically dyeable fibers made from polymers and copolymers of acrylonitrile and

of dicyanoethylene and acidic modified fibers

Le A 1? 903 - Z7 -

309808/1113

Polyamide and polyester, with real shades being obtained. The dyes can also be used for dyeing and printing tannin cellulosic materials, silk and leather. They are also suitable for the production of writing fluids, stamp goods, ballpoint pen pastes and can also be calibrated use in rubber printing.

For dyeing with the basic dyes of the general formulas (I) and (X), flakes, fibers, Threads, tapes, woven or knitted fabrics made from polyacrylonitrile or from mixed poly- merisates 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. Dicyanethylene. Flakes, fibers, threads, tapes, woven or knitted fabrics made from acid-modified synthetic materials, in particular from acid modified aromatic polyesters and acid-modified polyamide fibers can be dyed excellently. Sauer modified Aromatic polyesters are, for example, polycondensation products from sulfonic acid and ethylene glycol, i.e. polyethylene glycol terephthalate containing sulfonic acid groups (type DACRON 64 of E. I. DuPont de Nemours and Company), as described in Belgian patent specification 5 ^ 9,179 and US patent specification 2,893 8l6 are described. '

Dyeing can be carried out from weakly acidic liquor, in which case it is expedient to enter the dyebath at ko ° to 60 ° C. and then dye at boiling temperature. You can also dye under pressure at temperatures above 100 ° C. The dyes can therefore 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 inventive dyes of the formulas (I) to (X> on MKt ^ h «lien made of polyacrylonitrile or acidic» odifl «Urten Pol.yfst-tr fas-τη or polyamide fibers are characterized by very

La A 13 903 - 2S -

309808M113

2H1987

good light, wet, rub and sublimation roughness and by one high affinity to the paser.

ι The paring agents can be used individually or in mixtures. They are good for dyeing moldings made from polymers or copolymers of acrylonitrile, as. Dlcyanäthylens, acid-modified aromatic polyesters or acid-modified synthetic superpolyamides in chlorinated hydrocarbons are suitable as a dyebath if they promote the solubility in chlorinated hydrocarbons carry substituents such as the tert-butyl group, or if the anion An "in the Formulas I to I daa anion of a monobasic organic acid with 4-30 carbon atoms.

Such organic acids are for example: 2-ethylcaproic acid, lauric acid, 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 (Versatic acid 911), coconut fatty acid forerunner, tetradecanoic acid, undecyl eric acid, dimethyl propane 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 carboxylic acids, such as tertiary carbonic carboxylic acids, such as tertiary carboxylic acids, aromatic carboxylic acids, nonylphenoxy-butyl, 6-10 such as hexahydrobenzoic acid, cyolohexenecarboxylic acid, abietic acid. and sulfonic acids such as tetrapropylene benzene sulfonic acid.

In the following examples, parts mean parts by weight.

Ie A 13 903 - 29 -

1 1 11

2 1 1, 1 9 8

example 1

The solution of 33.6 parts of 2,5-dichloro-4-aminobenzene-sulfonic acid (β-Rl, 2,4-triazolyl) - (1 [] -ethyl) -amide

in a mixture of 150 parts of water and 30 parts of conc. Hydrochloric acid is diazotized at 0-3 ⁰ C with a solution of 6.9 parts Natriuwaitrit in 50 parts of water. The clear diazonium salt solution is freed from a small excess of nitrous acid with sulfamic acid and then concentrated to a solution of 17.4 parts of N-ethyl-N- (ßcyanäthyl) aniline in a mixture of 50 parts of water and 25 parts. Given hydrochloric acid. The coupling to the monoazo dye starts immediately; it is brought to an end by the gradual addition of sodium acetate solution and the resulting dye is filtered off after the coupling has ended after neutralization with ammonia solution. One holds 51 parts of a red dye powder.

26 parts of this dye are heated to 90 ° in 200 parts of 1,2-dichlorobenzene, and 6.3 parts of dimethyl sulfate are added in some cases. The mixture is subsequently stirred at 100 ° for 2 hours. After cooling, the dye is filtered off, washed with benzene and dried. 29, M part j of a powder of the formula which is readily soluble in water and has a red color is obtained

Le A 1> 90 5 - H)

Ht)) iii / I il I

2K1987

CH ₃ SO ₄

CH ₃ -

S) ^ - CH ₂ -CH ₂ -N-SO ₂ - ( _v

> N
= / Xc ₂ H ₄ CN

the textile materials made of polyacrylonitrile as well as acid modified polyamide and polyester red with excellent Dyes light and wet fastness.

The sulfonamide used as the diazo component was produced by reacting 2,5 »dichloro-4-acetylamino-benzenesulfochloride with l- (ß-aminoethyl) -triazole- (1,2,4) and subsequent saponification of the acetylamino group.

If one proceeds as described in Example 1, one obtains when using the appropriate diazo and coupling coapo = nenten dyes that color polyacrylonitrile in the specified shades:

Cl

CH ₃ SO ₄

«Τ

Red

₄ • [CH ₃ J ¹

CH ₃ SO ₄ 'CH ₃

CH ₃ SO ₄ · [CH ₃ -

CH ₃ ::,. ) ₄

f:. '. i

CH ₃ J

Cl

CH _a

Cl

Red

Red

CH ₃ ^C " ^H " ^OH

ⁿⁱ NHCOCH ₃

" ⁷ I -

309808/11 13

Cl CH,

CH, SO.

H.

CH,

CH ₃ SO ₄ * CH ₃ -N -CH ₂ -N-SO ₂ -f3- ^{N = N}

Cl ο

Cl
-CH ₈ -N-SO ₈ -Q-N'NQN- ^ J

Cl Cl OH

-CH ₈ -N-SO ₈ - ^ Λ-Ν = Ν-

Yellow

Cl

Red

Golden yellow

Cl

-N-SO ₈ <JN =:

Cl

Cl

CH ₃ SO ₄ - [CH ₃ -N (J.

-CH ₂ -S-SO ₂ ^) - N =

CH ₃

Golden yellow

CH ₃

/ C ₈ H ₄ OCOOCH ₃

, N = / 'C ₈ H ₄ OCOOCH ₃

Scarlet red

Cl * [0, H ₅ -CH ₂ -N _n Jj

) ₃ -N-SO ₈ -f \ -N CH ₃ ^

^ C ₈ H,

Red

ICO-CH ₃ COOC ₈ H ₅

he

yellow

Cl * [C ₆ Ii ₅ -CH ₈ -

Le A 13 -N-SO ₈ CH,

"C ₃ H,

orange

CH ₈

- 32 -

309808/11 13

-N-SO ₂ -ON = N

21A1987

yellow

Cl ^ C ₆ H ₅ -CH ₂ -SfI ^) a "N-SO ₂ -QN = N F3 _CN

^L ^ ^CH 3 k ₃ ΛΛ

HO OH

CH,

r> - N- (CH ₂ ) ₃ -N-SO ₂

C ₂ H ₅ -N 1
LN »* J» COOCH

^ C ₂ H ₅

yellow

Red

CH,

C ₂ H ₅

OOCH,

Red

CH ₃

CH

OOCH ₃ O

Yellow

Cl ¹

[c ₂ H ₅ -tf

C II Cl

) ₃ -N-S0 ₂ -ON = NON \ ² * ^red

^ Z = ⁷ C ₂ H ₅

COOCH ₃

Le A13 903

309808/1 1 13

Example 2

39.3 parts (2-aminobenzenesulfonic acid-R4-methyl-Q1,2,4-triazolium) - (l) ^ methyl] methyl amide) methosulphate

CH ₃ SO ₄

are concentrated in a mixture of 150 parts of water and 20 parts. Hydrochloric acid at 0-3 ° with a solution of 6.9 parts Sodium nitrite diazotized in 50 parts of water. the clear diazonium salt solution is made with sulfamic acid from freed from a small excess of nitrous acid and added to a solution of 14.9 parts of diethylaniline in a mixture of 50 parts of water and 15 parts of conc. Given hydrochloric acid.

The coupling to the monoazo dye starts immediately. she is made by gradually adding sodium acetate solution brought to the end. The resulting dye is deposited by adding 30 parts of sodium chloride and filtered off, The dye has the composition

τ. » A. 13 903 - 34- -

3 0 9 8 0 8 / Π 1 3

2V41987

Ch ₃ -n ^ t- ^ N

CH ₃

-N

= '"-C ₂ H ₅

and dyes textile fabrics made of acid-modified polyacrylonitrile Orange-red polyester and polyamide with very good wet fastness properties and very good light fastness.

The diazo component of this example was prepared by reacting 2-nitro-benzenesulfochloride and 1-methylamino-raethyl-triazole- (1,2,4), subsequent quaternization with dimethyl sulfate and final catalytic reduction the nitro group to the amino staircase.

With further coupling components this results in a slide component the following dyes in an analogous manner:

CH ₃ SQ ₄ ^ [CH ₃ -N

-N-CH ₃ SO ₂

'/ VVJi = N-

-N

'C ₃ H ₄ CN

O ₂ ^CH e

r * t yellow

Le Λ .1 "90 5

309RO8 / 1113

3fr

2Η1987

CH ₃ SO ₄

Ν = Ν ·

H ₉

₄ ^ [CH ₃ -N _n ^

-N-CH ₃ ^NHC0CH 3

CH ₃ SO ₄

CH ₃

C ₂ H ₆ 'C ₂ Hf CN

CH ₃ -N-CH ₃

-N-CH ₃

orange yellow Red

Red golden yellow

Le A13 903

309808/1 1 13

2U1987 IT

Example 3

The solution of 28.7 parts of (β-Ql, 2,4-triazolyl) - (l) ""} - ethyl) - (3-chloro-4-aminophenyl) sulfone

in a mixture of 150 parts of water and 30 parts of conc. Hydrochloric acid is diazotized at 0-3 ° with a solution of 6.9 parts of sodium nitrite in 50 parts of water. The clear diazonium salt solution is freed from a small excess of nitrous acid with sulfamic acid and then concentrated to a solution of 17.4 parts of N-ethyl-N- (β-cyanoethyl) aniline in a mixture of 50 parts of water and 25 parts. Given hydrochloric acid. The coupling to the monoazo dye starts immediately; it is brought to an end by the gradual addition of sodium acetate solution and the resulting dye is filtered off after coupling has ended and after neutralization with ammonia solution. 5 parts of a red pigment powder are obtained.

23.5 parts of this dye are heated to 90 ° in 200 parts of chlorobenzene and partially with 6.3 parts Dimethyl sulfate added. The mixture is subsequently stirred at 100 ° for 2 hours. After cooling, the dye is filtered off, washed with benzene and dried. 29 parts of a powder which is readily water-soluble with a red color are obtained formula

Le A 13 903 - 37 -

309808/1113

21AΊ987

CN

the texile materials made of polyacrylonitrile as well as acid-modified polyamide and polyester dyes red with excellent light and wet fastness properties.

The sulfon used as a diazo component in this example was obtained by reacting 3-chloro-4-nitro-benzene-sulfinic acid and l-bromo-2r * (1.2.4-triazole) - (l) J " ethane and subsequent * catalytic reduction of the nitro group.

The following dyes are obtained in an analogous manner:

Cl CEj

CE, SO ₄ ^ (cEj -N (^ CB ₂ -CE, -SO ₂ "<i ^" ^{N = N} \ 3 J ^ ^yellow

OH,

-S0

yellow

CE, SO ₄ ^ JcE ₁ -K ^ J? ' ⁰¹ ** ~ ^CE *

/ C ₂ B ₅

-so - / "^ n = N- / ⁷ Vn red

Le A13 903

309808/1113

2U1987.

C.

Red

CH ₃ SO ₄

C H.

Ö ^ -ch, -CH, -SO ₂ - ^ J> - ^N = ^N - (^ 3 " ^N ^ ^a orange

NHCOCH ₃

C ₃ H ₄ OH

golden yellow

CB ₃ SO ₄

"SO

! N

yellow

Le A 13

39 -

309808/1113

2H1987

Example 4

The solution of 35.7 parts of 1- (ß- (3-chloro-4-amino-benzoylamino)) -ethyl-4-benzyl- (1,2,4) -triazolium) chloride

in a mixture of 150 parts of water and 20 parts of conc. Hydrochloric acid is diazotized at 0-3 ⁰ C with a solution of 6.9 parts of sodium nitrite in 50 parts of water. The clear diazonium salt solution is freed from a small excess of nitrous acid with sulfamic acid and then concentrated to a solution of 18.8 parts of N-ethyl-N (β-cyanoethyl) -m-toluidine in a mixture of 50 parts of water and 20 parts. Given hydrochloric acid. The coupling to the monoazo dye starts immediately. It is brought to an end by adding sodium acetate solution. The dye is deposited by adding 30 parts of sodium chloride and filtered off. The resulting dye has the composition

and dyes textile fabrics made of polyacrylonitrile, acid-modified polyamide and polyester orange-red with very good results Wet fastness and very good light fastness.

Le A. 13 903

- 40 -

309808/1113

The diazo component of Example 5 gives using further coupling components in an analogous manner the following dyes:

_> ^CH a

// N-CH ₃ -CH ₃ -N- (X _ ^ Ν = Ν- (

yellow

// ν

3-oB, -

Cl CE ₃

yellow

\ 4

H -CH ₃ -Nc / 'Vn-N

orange

NHCOCH ₃

Jl QCE ₄

-CH ₈ -NC ^> ^N = ^N -O- ^N "

NHCOCH ₃

C ₃ H ₅

Red

bordo

Le A 13

- 41 -

309808/11

21 A 1987

Cl

HO

OH

yellow

Red

Cl HO

orange

C _a H ₄ CN C ₂ H ₄ OH

orange

CH,

Le A 13

309808/1113

Example 5

The solution τοη 25.3 parts of l- (3-Aeino - * - ehlor-benzoyl ■ ethyl) -triazole ~ (1.2.4)

in a «Geeisch of 150 parts of water and 50 parts of conc. Hydrochloric acid is at 0-3 ° C with a solution of 6.9 parts Sodium nitrite diazotized in 50 parts of water. The clear Diazoniiunsalzlösung is sit Aaidosulfonsäure from one freed small excess of nitrous acid and then to a solution of 14.9 parts of diethyl aniline in one Mixture of 50 parts of water and 15 parts of water, added hydrochloric acid. The coupling to a monoazofarfeatofi continues immediately one; it is brought to an end by the gradual addition of sodium acetate solution and the resulting dye After the coupling has ended, after neutralization, it is filtered off auonia solution. 39 parts of a red dye powder are obtained.

20.6 parts of this dye are heated to 100 ° in 200 parts of chlorobenzene and some 6.3 parts of dimethyl sulfate are added. Ee is then stirred at 100 ° C. for 2 hours. After cooling down, the dye is filtered off, ■ Washed with benzene and dried. 25.2 parts are obtained an "it orange" red color borrows powder from water the foreel

Le A 13 90? - 43 -

30'980II / Π 1?

Hh

The textile materials made of polyacrylonitrile as well as acid-modified polyamide and polyester have a yellowish red tinge «It dyes with excellent light and wet fastness properties.

The one used as a diazo component in this example Aain was obtained by reacting 3-nitro-4-chlorophenyl-chloromethyl ketone with triazole- (1.2-4), then Quaternization with dimethyl sulfate and final catalytic reduction.

The following dyes are obtained in an analogous manner:

yellow ichig orange

⁴ ' ^Λ "' * ~ * '""*' ^% yellowish

orange

Le A 13 905 - 44 -

309SG8 / 1113

HS ¹

CH ₃ SO ₄ ^v

0 -CB ₈ -C

CH ₃

141987

orange

CH, SO ₄

^s B% i

-CH ₃ -C

N = N

H ₂ -CH ₃ -CN

yellow

CHjSO ₄

N = N

yellow

CH ₃ SO,

-c ¹

COOC ₂ H ₈

N = N

Cl

yellow

CH ₃ SO ₄

orange

CH ₃ SO ₄

Il orange

s C ₂ H ₄ OCOCH ₃ Γ ^ C ₂ H ₄ OCOCH ₃

Le A 13

- 45 -309808 / 11

Example 6

The solution of 26.7 parts of 1 (y- (3-trifluoromethyl-4-aminopheny 1-amino) propyi ^ -4-methyl-triazolium- (1,2,4) methosulfate

in a mixture of 150 parts of water and 30 parts of conc. Hydrochloric acid is added at 0-3 ° with a solution of 6.9 parts Sodium nitrite diazotized in 50 parts of water. The clear diazonium salt solution is with sulfamic acid from a freed small excess of nitrous acid and then to a solution of 17 »4 parts of 1-phenyl-3-methyl-pyrazolone- (5) in a mixture of 100 parts of water, 10 parts of a 40 ^ strength sodium hydroxide solution and 8.4 parts of sodium hydrogen carbonate given. The coupling to the monoazo dye sets in immediately and ends after a short time. The yellow dye is due Addition of 30 parts of sodium chloride deposited and filtered off. The resulting dye has the composition

, CF, CE ₃

CH ₉ SO ₄

and dyes textile fabrics made of polyacrylonitrile, acid modified polyamide and polyester yellow with very good wet fastness properties and very good light fastness.

Le A 13 903 '- 46 -

30980Ö / 1113

2U1987

The diazo component of Example 7 results using further coupling components in an analogous manner the following dyes:

CH ₃ S0 ₄ ^v

CiL as ₄ ^c ~ ^ I. -n ^ F

~ ^CB * ~ ^CE * -N - <^ 3-N = N-

* A .C ₂ H ₈ C ₂ B ₅

Orange red

C ₂ H ₆

orange C ₂ B ₄ -CO-OCH ₃

PR S ^ Ii

-CHj -CH ₁ -XV AN = N- ^ N

Red

CB ₁ SO ₄ CB ₃ SO ₄ NH-CO-CB,

C ₃ H ₈

CF ₃

CH ₃ IO

gold-yellow

eciiarlach

orange

A YJ

- 47 -

CH. SO CH ₃ SO ₄

CH ₃ SO ₄

~ ^CB a -

NH

grtin-

prickly

yellow

CH ₃ SO ₄

(M,

CH ₃ SO ₄

-CH ₂ -CH ₂ "N ^ -

yellow

pungent red

Le A

309808/1113

Example 7

A solution of 23.9 parts of l- (ß- (3-ethyl) -triaz © l- (1.2.4)

51

<x

-CB ^ -CK ₁ -OT

in a mixture of 150 parts of water and. 30 skins hydrochloric acid at 0-3 ° C a Lüsumg from 6 ₉ 9 parts ait Natriuanitrit in 50 parts of water öissstiert "DL® clear Oiazoniumsalzlösung is ait Asaidosulfonsäior © v n a low üeberschuß of nitrous acid liberated UNAE DATRA to a solution of 19.9 Parts of 4-ethyl-N- (ß-chloroethyl) -mtuluidii in a mixture of 50 parts of water «rad 25 parts of conc. Given hydrochloric acid. The coupling of azo dye sets in immediately | it is brought to the end by adding sodium acetate solution and the resulting dye is filtered off after the coupling has ended and after neutralization with ammonia solution. 40.5 parts of a red dye powder are obtained.

22.4 parts of this dye are in 200 parts of 1,2-dichlorobenzene heated to 90 and partially treated with 6.4 parts of benzyl chloride. The mixture is then stirred at 120 ° C. for 2 hours. After cooling, the dye is filtered off, washed with benzene and dried. You get 27 »8 parts an orange-red color, easily water-soluble powder of the formula

Jl

Le A 15 903 - 49 -

2U1987

The textile materials made of polyacrylonitrile as well as acid-modified polyaaid and polyester have a yellowish red tinge colors with excellent light and wet fastness properties.

In an analogous manner, eaan is obtained using further Coupling components containing dyes:

Cl

/ ξ * »τ

ei® fifV * Jf r ™ « - ⁰ ^ - ^ö -0- ^N = ^N -0 ^N C ²

orange

Cl

yellow

yellow

CH.

orange

orange

Le A15 903

- 50 -

309808/1113

2U1987

Cl OCH ₃

Λ-ΓΗ f ^ -Ca, -CHj-0 ^ 3-Ν-

, C ₃ H ₄ O-COGH ₃

Red

NHCOCE ₃

Cl

Le A 1 3

309808/1113

2H1987

Sl

Example 8

A solution of 23.2 parts of 4-aminobenzoic acid-ß / ~ (l, 2,4-triazolyl) - (l) 7-ethyl ester

in a mixture of 150 parts of water and 30 parts of conc. Hydrochloric acid is diazotized at 0-3 ° with a solution of 6.9 parts of sodium nitrite in 50 parts of water. the Clear diazonium salt solution is freed from a slight excess of nitrous acid with sulfamic acid and then to a solution of 14.9 parts of diethyl aniliia in a mixture of 50 parts of water and 20 parts of conc. Given hydrochloric acid. The coupling to the monoazo dye sets in immediately, it is brought to an end by the gradual addition of sodium acetate solution and the resulting Dye is filtered off after neutralization with ammonia solution. 37.1 parts of a red dye powder are obtained. 19.6 parts of this dye are in 200 parts of chlorobenzene heated to 90 ° and partially treated with 6.4 parts of dimethyl sulfate «It is stirred for 2 hours at 90 °. After cooling, the dye is filtered off, washed with benzene and dried. 24.1 parts are obtained an orange-red color, easily water-soluble powder of the formula

0 ^ ₂ H ₅

β Γ ^ VtJ-CH ₂ -CH ₂ -0-C- ^ ^r AN = N- ^ ~ ^ -N CH ₃ SO ₄ - CfL ₁ -Nl * * N- / \ = / VH

the textile materials made of polyacrylonitrile as well as sour modified polyamide and polyester orange with excellent Dyes wet and light fastness.

Le A 15 903 - 52 -

309808/1 1 13

2H1987

The following dyestuff is obtained in an analogous manner using further coupling components

CH ₃ SO ^ I CH ₃ -N ^ J _{1 -CH2}

CH,

_ ₀ y

yellow

CH ₃ SO ₄

-CH ₂ -Cn ₂ -0-C

OH OH

CH ₃ S0 "

¹ ^ -O -CH ₂ -CH ₂ -0-

CH ₃ SO ₄ CH ₃ -N ^ J ^ CH ₃ .CH ₂ _ ₀ -C ^ J

Z »5

orange

I.
CH ₃

CH ₃ S0 "

C ₂ H ₅

^ C ₂ H ₅ NHCOCH ₃

Red

CH ₃ SO ₄

-CH ₂ -CH ₂ -OC- ^ XVN = N - // ^ -N 0 orange

T.P A 15

309808/1113

2U1987

cn ₃ So ₄

O -CH ₂ -0-CC ₂ H ₅

orange

CH,

Vn = n - // Vn > '

η = / 'C ₂ II ₄ -O-CO-CII ₃

CH,

Le A15903

- 54 -

309808/1113

Example 9i

A solution of 13.8 parts of 4-nitroaniline is in a mixture of 30 parts kona. Hydrochloric acid and 250 parts of H ₂ O were stirred at 30 ° for 1 hour. After cooling to 10 °, 350 parts of ice are added and 7 parts of sodium nitrate in 70 parts of water are then iazotized. The filtered diazonium salt solution is freed from a small excess of nitrous acid with sulfamic acid. This diazo solution is allowed to run into a solution with cooling of 31.7 parts of β-aminonaphthalene-6-sulfonic acid / "" (1,2,4-triazolyl) - (l) JT-ethyl-amide

SO ₂ -N-CH ₂ -CH ₂ -N- ^

j η 400 parts of water and 20 parts of conc _o hydrochloric acid. The coupling to the monoazo dye sets in immediately it is carried out by the gradual addition of sodium aceiate solution sn at the end. After suctioning off and drying hJ ₉ 2 parts of a red dye powder

23.3 parts of this dye are heated to 200 parts of chlorobenzene to 90 ° and partially mixed with 6 _S 3 parts of dimethyl sulfate. It is nacbgerührt 2 Stunden.bei 100 ° After cooling, the dye is filtered _eb-s with benzene and dried "to give ES ₉ 5 © part of a slightly red color-soluble powder of the formula

^ Lf H ¹ J "" V-CHa CH ₃ SO ₄ ^N SO ₂ -N-CH ₂ -CH ₂ " ' ^{S 4}

Le A 13 903 - 55 -

309808/1 1! 13th

2H1987

the textile materials made of polyacrylonitrile as well as acid- modified polyamide and polyester dyes red with excellent light and wet fastness properties.

The following dyes are obtained in an analogous manner using further diazo components:

SO ₂ -NII-CH ₂ -CH ₂ -ί

^CH 3 ^S0 4

OCH.,

NH ₂

SO ₂ -NH-CH ₂ -CH ₂

(\ -CH, CII ₃ SO ₄ -CH ₂ -N ^ y ³ J ^{3 4}

orange

Cl NH ₂

N = N

SO ₂ -NH-CH ₂ -CH ₂

, JJi-CH ₃ JCH ₃ SO ₄

golden yellow

NH ₂

SO ₂ -NH-CH ₂ -CH ₂ -i

CH ₃ SO ₄

golden yellow

CH, 0-0 · / Λ-Ν = ν / y

Le A13 905

SO ₂ -NH-CH ₂ -CH ₂

- 56 -

ι ^N N-CH, CH ₃ SO ₄ -N ^ ³ J ³ *

golden yellow

309808/1113

Br NH ₂

O ₂ -NH-CH ₂ -CH ₂ _jj ^ l-CH ₃ J CH ₃ SO ₄

2Η1987

Red

SO ₂ -NH-CH. -CH ₂ -N J ^ ~

CH ₃ S0 ₄ ⁽

orange

Cl

N = N

CH ₃

SO ₂ -NH-CH ₂ -CH ₂ JPV-CH ₃ CH ₃ SO ₄

Scarlet fever

in the _2nd

SO ₂ -NIl-CH ₂ -CH ₂ -: 1 liter

CH ₃ SO ₄

golden yellow

NO ₂ NH ₂

SO ₂ -NH-CH ₂ -CH ₂ -

Red

Br ΝΠ ₂

ο.

SO ₂ -NH-CH ₂ -CH ₂ -: blue

Ie A 13 903

- 57 -

309808/1 1

2H1987 Si

N-sCV © 1 ©

I N-CII ₃ CII ₃ SO ,! red -CH ₂ -N- ^ ³ J ³ *

SO ₂ -NH-CH ₂ -CH ₂

Example 10

A solution of 10.7 parts of ρ-toluidine in a mixture of 150 parts of water and 30 parts of conc. Hydrochloric acid is diazotized at 0-3 ° with a solution of 6.9 parts of sodium nitrite in 50 parts of water. The clear diazonium salt solution fc is freed from a small excess of nitrous acid with amidosulfonic acid and then after cooling to a solution of 41.5 parts of i-methyl- (1,2,4) -triazolium- (l_} _- 7-acetic acid- (3-diethyl-amino-anilide)) methosulfate

HN-CO-CH ₂

® Ί

-CH ₃ CH ₃ SO ₄ 3 J 3 4

given in a mixture of 150 parts of water and 20 parts of concentrated hydrochloric acid. The coupling to the monoazo dye immediately sets EIA and is guided by gradual addition of sodium acetate solution ψ to an end. The resulting dye is deposited by adding 50 parts of sodium chloride and filtered off. The dye has the composition

HN-CO-CH ₂ N-

'CH ₃ SO ₄ ^-

Le A 13 903 " ⁵⁸ "

309808/1113

2H198.7

and dyes textile fabrics made of acid-modified polyacrylonitrile Polyester and polyamide orange with very good wet and light fastness properties.

The coupling component of this example was prepared by reacting chloroacetic acid (3-diethylamino) anilide with triazole (l, 2,4) and subsequent quaternization with Dimethyl sulfate.

With further diazo components, this coupling component produces the following dyes in an analogous manner:

0 ₂ N - </ \\ - N = N

NH-CO-CH ₂

- N

CH ₃ SO ₄

bluish red

OCH ₃

/ C ₂ H ₅

■ Ν
'C ₂ H ₅

NH-CO-CH ₂ N J /

C ₂ H ₅ OC- / MN = N-

C ₂ H ₅

NH-CO-CH ₂

CH ₃ SO ₄

bordo

orange

NH-CO-CH ₂ N- ^

CF,

CH ₃ SO ₂ / Λ-Μ

/ C ₂ Hg 'C ₂ H ₅

NH-CO-CH ₂ -

Le A 13 905 - 59 -

orange

SO ₄ ^ red

309808/1 1 13

4fr

2U1987

CN

Br - //

NH-CO-CH ₂

s ι

-CH ₃ CH ₃ SO ₄

NO.

/ C ₂ H ₅

CF ₃ - (/ Vn-N- / Vn

NH-CO-CII ₂

L ? -CH _a

CH ₃ SO ₄

bluish red

Red

CH _n

-CH,

CH ₃ SO ₄

orange

OTI-CO-CH ₂

CH ₃ SO ₄

reddish blue

CII ₃ SO ₄

Red

Cl

Cl

-N

NH-CO-CH ₂

-CH,

CII ₃ SO ₄

Red

Le A 13

- 60 -

309808/1113

2U1987

- ¹ V ^ -CH ₃ 7 CH ₃ SO ₄ "rub in -CO-CII ₂ N ^ ³ J ^{3 4}

NH-CO-CII ₂

Example 11

Dyeing process for polyacrylonitrile and acid-modified polyamide fibers (type Dye I) s

0.1 part of the dye shown in Example 1 is made into a paste with about 2 parts of l / water, possibly with the addition of a little acetic acid, and dissolved with 50 parts of hot water. The dye liquor is also given an addition of Ο ₉ 5 ~ 2 g ■ Avolan IS (condensation product from naphthalenesulfonic acid isaö FormÄshyd) 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 liquor, 10 g of piece goods made of polyacrylonitrile fibers or acid-modified polyamide fibers are kept in constant motion while the temperature is increased to 100 ° in 30 minutes. At the boiling temperature you dye for 60 minutes, rinse the material with cold water and then dry it at 60-70 °,

For dyeing acid modified polyglycol terephthalate fibers (Type Dacron 64) a carrier is added to the dye liquor, e.g. 1-3 parts of an aromatic oxycarboxylic acid ester or diphenyl.

Le A 13 903 - 61 -

309808/11 13

21A1987

Example 12

Printing method

A fabric made of polyacrylonitrile is printed with a printing paste, which was prepared in the following mannerί 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 figured acetic acid are poured over 330 parts by weight of hot water and the resulting solution added to 500 parts by weight of crystal rubber (gum arabic as thickening agent). Finally, 30 parts by weight of zinc nitrate solution are added. The print obtained is dried, steamed for 30 minutes and then rinsed. A red print with very good fastness properties is obtained.

Le A. 13 903 - 62 -

309808/1113

Claims (16)

Patent claims: 1. Catalytic dyes of the general formula -B-X-F At* an alkyl · = · or aralkyl radical, a direct bond or a bridge member, a divalent group _s denotes the radical of a dye and oin denotes aniene. 2. Cationic dyes of the general formula ¹¹ I - Ϊ-, = Ά an alkyl group with 1 "to 4 carbon atoms or a phenylalkyl group with 1 or 2 O atoms in a or alkyl chain ₉ a -SOp-, -MH-SO ₂ -, -H {allsyl with 1" to 4 carbon atoms) - SO ₂ -, -CO-, -ITH-CO-s -K (alkyl with 1 to 4 carbon atoms) -00-, -0-5 -S- _s -NIi-s, -IiC-alkyl with 1 Me 4 C Atoms), ~ 0 ~ C0 ~ or a direct binary, if m> 1 _{s is} the residue of an azo fiber ₉ the numbers 0 to 6 mean sin anion _s and where the cyclic and acyclic residues can be substituted by "nonionic residues » Le A13 903 - 63 309808/1113 t> H 3. Cationic azo dyes of the general formula 2H1987 an alkyl group with 1 to 4 carbon atoms or a phenylalkyl group with 1 or 2 carbon atoms in the alkyl chain, a -SOg-, -NH-SO ₂ -, -Ii (alkyl with 1 to 4 carbon atoms) -SO ₂ -, -CO-, -NII-CO-, -N (alkyl with 1 to 4 O-atoms) -CO-, -0-, -S-, -NH-, -N (alkyl with 1 to 4 C- Atoms), -0-00- or a direct bond, if m> 1, the remainder of a coupling component of the aniline, phenol, naphthalene, indole, pyrazole, pyridine or pyrimic line, the. Numbers 0 to C> and an Aiiio :: mean, and v / ori.n the cycliRnhen were ficj ^ cliech & n radicals can be substituted by nonionic radicals. 4. Cationic azo dyes of the general formula S ₁ T ₂ To ^v v / o r.in R _{1 is} an alkyl group with 1 to 4 carbon atoms or a phenyl alkyl group with 1 or 2 carbon atoms in the alkyl chain, SV / water, a C ₁ to C-alkyl radical, halogen, nitro, methylsulfonyl, G ₁ to C _{-alkoxy-, C 1} to G ^ -alkoxy- carbonyl or cyano,
-S-, V ( ^r aBserfitoff or halogen, Le A13 905 - 64 - 309808/1113 ORIGINAL iNSPECTED Hydroxy, an amino, C, to C. -Dialky! Amino-, C-. to C.-Alkylphenylamino-, G-, bit C. ~ / lkyl-benzy, amino, pyrrolidino, morpholino or piperidino radical, hydrogen, halogen, a C-, to C «-alkyl, C-, to C ₇ -alkylcarbonylamino or benzoylamino radical, hydrogen or a C. -, to C ^ -alkoxy radical or T-, and Tp together with the phenyl ring a uaphthyl radical, a -SOp-, -HH-SO ₂ -, -N (AlKyI with 1 to 4 carbon atoms) -SO ₂ -, - CO-, -NH-CO-, -Ii (alkyl with 1 to 4 carbon atoms) -CO--, -0-, -S-, -NH-, -N (alkyl with 1 to 4 carbon atoms) , -0-00- or a direct bond, if m> 1, the numbers 0 to 3 and an anion means jUnd v / o r in the cyclic and acyclic radicals can be substituted by nonionic radicals. 5. Kationischa 4zo dyes of the general formula 2 \ = wherein At* Methyl, ethyl or "benzyl. _T a -3O ₂ -, -NII-SO ₇ -, -MT (OH ₃ ) -SO ₂ -, -CO-, -NH-CO-, »0-, -NH- or -O-CO group, Hydrogen, chlorine, cyano, methyl, trifluoromethyl or Methöxy, Hydrogen or chlorine, V / a s s first off or methoxy, Hydrogen, methyl, chloro or acetylaraino, Methyl, ethyl or by Hj ^ droxyl, methoxycarbonyl, Chlorine or cyano substituted ethyl, hydrogen, methyl, ethyl, benzyl or hydroxyl, Methoxycarbonyl, chlorine or cyano substituted aryl, Le A13 903 - 65 - 3 0 9 8 0 8/1113 IHSPECTED 2H1987 m _o the numbers 1, 2 odor ρ and
An * 'means an anion. 6. Cationic azo dyes of the general formula ^K 2 " ¹ R methyl, ethyl or "bensyl, a -SO ₉ -, -NH-SOp-, -Ii (CH-J-SOj, -, -CO-, -NII-CO-, -0-, -NH- or -0-CO group, an ilGSt of Por.j.rlii the numbers 1, 2 or 3, and - denote an anion. CIL- HO 7. Cationic azo dyes of the general formula A-K = IT X ₇ - (CiL.)
3 ^ ni. At wherein A is the remainder of a diazo component, R _{2 is} methyl, ethyl or benzyl, T _? Hydrogen, chlorine or a C ₁ to C alkyl or alkoxy decomposition, Tg hydrogen, chlorine, methyl, ethyl, acetylamino or together with the phenyl ring an Ifaphfchylresü, X ₅ -NH- or -H (C ₁ to C, -alkyl) -, Ie A 13 903 - 66 - 309808/1113 21419 rii _o the numbers 1,?. or 3 and An ^v 'mean an anion. 8. Cationic azo dyes of the general formula -U ^T , 7 - (CH ₂ ) 2. "8th To ^y Methyl, ethyl or benzyl, Hydrogen, chlorine or a C- to G -alkyl or -alkoxy radical, hydrogen, chlorine, methyl, ethyl, acetylamino or, together with the phenyl ring, a naphthyl radical, Vaccjcrctcff, chlorine, bron, Tuifluui-mt; L} i_yl. Cyc-ii. Methyl. Iethoxy, ethoxy, 1-1 ethoxycarbonyl, ethoxycarbonyl, Llethylsulfonyl or ITitro, Vi ^ ssorntoff, chlorine, broin, cyano, nitro, Pormyl, 1-eth.yl-Bulfonyl, C ₁ to C, -Alkyl, C ₁ to _{C 1} to C alkoxy, C 1 to C 1 to C alkoxycarbonyl, phenoxy, C to C 1 to C mono or dialkylaminocarbonyl, C to C to C mono or dialkylamino sulfonyl or phenylazo, hydrogen, chlorine, bromine, trifluoromethyl , Cyano, nitro, methyl, hydroxyl, methoxy, ethoxy, methoxycarbonyl, ethoxycarbonyl, -ITH- or -N (C ₁ to C ^ -alkyl) -, the numbers 1, 2 or 3 and an anion. 9. Cationic azo dyes of the general formula Le A 13 - 67 - ' 309808/11 13 2HT987 NH-CO- (CH ₂ ) _m -1 To ^v wherein R ₂ Methyl, ethyl or benayl, methyl, ethyl or by hydroxyl, methoxycarbonyl, Chlorine or cyano substituted ethyl, hydrogen, .- methyl, ethyl, bensyl or hydroxyl., Methoxycarbonyl, chlorine or cyano-substituted ethyl, hydrogen, chlorine or a C-, to C, -alkyl- or --Alkoxy rest, Hydrogen, chlorine, bromine, trifluoromethyl, cyano, methyl, methoxy, ethoxy, methoxycarbonyl, ethoxycarbonyl, methj ^ l- sulfonyl or nitro, Hydrogen, chlorine, bromine, cyano, nitro, iOrmyl, methyl sulfonyl, C ₁ bit C ^ alkyl, C ₁ bit C ^ alkoxy, C ₁ to C ^ - Alkoxycarbonyl, phenoxy, C ₁ to C ^ mono- or dialkylamino carbonyl, C-, bit C -mono-. Or dialkylatainosulfonyl odor I'heny lasso, Hydrogen, chlorine, bromine, drifluoromethyl, cyano, nitro, Methyl, hydroxyl, methoxy, ethoxy, methoxycarbonyl, Ethoxycarbonyl, " the numbers 1, 2 or 3 and mean an anion. 10. Cationic azo dyes of the general formula UT, N = N- ^ V At* Le A 13 - 68 -309808/1113 2,987 worm At' Methyl, ethyl or benzyl, Hydrogen, chlorine, bromine, trifluoromethyl, cyano, methyl, Methoxy, ethoxy, methoxycarbonyl, ethoxycarbonyl, methyl sulfonyl or nitro, Hydrogen, chlorine, bromine, cyano, nitro, Fortnyl, methylsulfonyl, C ₁ to C.-alkyl, C ₁ to C.-alkoxy, C ₁ to C, -alkoxycarbonyl, phenoxy, C ₁ to C ..- mono- or Dialkylaminocarbonyl, C ₁ to C ^, - mono »or dialkylamino-suXl'onyl or phenylazo, Hydrogen, chlorine, bromine, tri fluorine thy 1, cyano, nitro, methyl, hydroxyl, methoxy, ethoxy, methoxycarbonyl, Athoxycarbonyl, -OH, -HH ₂ , -NH (C ₁ to O ₄ -AlCyI), -NH-C ₆ II ₅ , -K (CH ₅ ) -O ₆ H ₅ or -N (C ₁ to C ₄ -AIk ₁ Yl) ₂ , -CO-, -00-0-, -SOp-NH- or -SOy-N (C-, up to 0 _Λ -Al ¹ ZyI) -, the numbers 1, 2 or 3 and mean an anion. 11. Process for the preparation of colorants of the general formula R - -B-X-P Αη ^Λ wherein R is an alkyl or aralkyl radical, B a direct bond or a bridge member, Ie A 13 905 - 69 -309808/1113 2U1987 X is a divalent group, F the remainder of a dye and An ^ "'em anion means characterized in that there is a grouping of the general formula in which B and X have the meanings given above, into suitable ones Dyes or dye precursors, which in turn are then converted into the desired dyes and then with compounds of the general formula R - wherein R has the meaning given above and An, for one stands as an anion which can be split off and which can be identical to An or can be exchanged for An, quaternized. 12. Process for the preparation of dyes of the general formula wherein R is an alkyl or aralkyl radical, B is a direct bond or a bridge member, X is a divalent group, F. the rest of a dye and At ^v ' mean an anion characterized in that one grouping the general formula Le A 1? 903 - 70 - 309808/1 1 13 2U1987 To ^v 5Γ - B - X - in which R, B and X have the meanings given above, into suitable ones Dyes or dye precursors, which in turn converted into the desired dyes . 13 .. The process of producing azo dyes in general formula CJ * N = N-K To ^v R _{1 is} an alkyl group with 1 to 4 carbon atoms or a phenyl alkyl group with 1 or?. C atoms in the alkyl chain, X ₁ a -SO ₂ -, -MH-SO ₂ -, -N (alkyl with 1 to 4 C atoms) -SO ₂ -S -00-, -NH-CO-, - H "(alkyl with 1 to 4 carbon atoms) -CO-, -0-, -S-, -NH-, -N (alkyl with 1 to 4 carbon atoms), -0-C0- or a direct bond, if m is> 1, K is the remainder of a coupling component of the aniline, phenol, naphthalene, indole, pyrazole, pyridine or pyrite nidine line, m -the numbers 0 to 6 and
An ^ 'denotes an anion, and v / orin the cyclic and acyclic radicals can be substituted by nonionic radicals. characterized in that amines of the general formula Le A13 903 - 71 - 309808/1113 2H1987 ■ in which X ₁ and m have the meaning given above, diazotized with compounds of the general formula H-K where K has the meaning given above, couples and then with compounds of the general formula where R has the meaning given above and An _{1 is} a radical which can be split off as an anion and which can be identical to An or can be exchanged for An, quaternized, or amines of the general formula R ₁ -I -NH, wherein R ₁ , X ₁ , m and An are as defined above, diazotized and reacted with the coupling components mentioned above. 14. Process for the preparation of azo dyes of the general formula _m ³ 'To' A is the remainder of a diazo component, R _{2 is} methyl, ethyl or benzyl, T ₇ hydrogen, chlorine or a C ₁ to C. alkyl or -AikoTry rest, .1. Le A15 905 - 72 309808/1113 2,987 Hydrogen, chlorine, methyl, ethyl, acetylamino or, together with the phenyl ring, a naphthyl radical,
-BH- or -N (C ₁ to C, -alkyl) -,
the numbers 1, 2 or 3 and
mean an anion characterized in that amines of the general formula wherein A has the meaning given above, diasotized with
Compounds of the general formula wherein T ₇ , T _g , X, and m _{2 have} the meanings given above, couples and with compounds of the general formula wherein R _{2 has} the meaning given above and An _{1 is} a radical which can be split off as an anion and which can be identical to An or can be exchanged for An, quaternized,
or that the diazotized amines with compounds of the general formula R, To ^v Le A13 903 73 - 309808/1113 2Η1987 wherein R ₂ , T ₇ , Tg, X-, m ₂ and An ^ ""'have the meaning given above, couples. 15. Process for the preparation of azo dyes of the general formula
U ^ü l / 7
U NH -00- (CH ₂ ) -1tJ | R ₂ methyl, ethyl or bensyl, T ₅ methyl, ethyl or ethyl substituted by hydroxyl, methoxycarbonyl, chlorine or cyano, T ₆ hydrogen, methyl, ethyl, benzyl or ethyl substituted by hydroxyl, methoxycarbonyl, chlorine or cyano, Trj hydrogen, chlorine or a C ₁ to C _/ alkyl or alkoxy rect, U hydrogen, chlorine, bromine, trifluomethyl, cyano, methyl, Methoxy, ethoxy, methoxycarbonyl, ethoxycarbonyl, methylsulfonyl or nitro, U ₁ hydrogen, chlorine, bromine, cyano, nitro, formyl, methylsulfonyl, C-, bia C.-alkyl, C-, to C * -alkoxy, C ₁ to C.-alkoxycarbonyl, phenoxy, C-, to C.-Mono- or Dialkylamino carbonyl, C-, to C "-Mono- or Lialk.ylamino --sulfonyl or Phenylasio, U ₂ hydrogen, chlorine, bromine, trifluoromethyl, cyano, nitro, methyl, hydroxyl, methoxy, ethoxy, methoxycarbonyl, ethoxycarbonyl 1, m the numbers 1, 2 or 3 and An ^ ~ ^J mean an anion, characterized in that amines of the general formula Le A 13 903 - 74- - 309808/1113 wherein U, U-, and U, have the meanings given above, diazotized, with compounds of the general formula T 1-CO- (CH ₂ ) _m -1 wherein T ₁ -, Tg, T ₇ and m _{2 have} the meaning given above, couples and with compounds of the general formula in which R _{2 has} the meaning given above and An _{1 is} a radical which can be split off as an anion, but can be identical to An or can be exchanged for An, quaternized,
or that the diazotized amines with compounds of the general formula NH-CO- (CH where R _g , T ₅ , Tg, I ^ tung have coupled and The above conditions = Le A13 903 - 75 - 309808/1113 2H1987 16. Process for dyeing, printing and bulk dyeing of materials which are entirely or predominantly polymerized unsaturated nitriles such as acrylonitrile or vinylidene cyanide, from acid-modified polyesters or from acid modified polyamides, characterized in that dyes of claims 1 to 10 are used. 17 · Materials composed entirely or predominantly of polymerized unsaturated nitriles such as acrylonitrile or vinylidenecyanide, from acid-modified polyesters or from Acid modified polyamides and dyed with dyes of claims 1 to 10, printed or in bulk have been colored. Le A13 903 - 76 - 309808/1 1