DE2205537A1 - AZO DYES - Google Patents

Description

FARBENFABRIKEN BAYER AG LEVERK US EN-Bayerwerk Cemral area £ 4. Fet), 1972 Pttents, trademarks and licenses

K / Wk

Azo dyes

The present invention relates to azo dyes of the formula

NC -

ν! CN
/ \ - N = N - K /
CH, \
X

in which K stands for the remainder of a coupling component and X stands for chlorine, bromine, cyano, C ₁ -C ₄ -AIkYlSuIfOnYl or the nitro group,

and their manufacture and use for dyeing fiber materials.

Suitable radicals K are, for example, radicals of coupling components of the benzene, naphthalene, pyrazolone, pyridone, acylacetic acid amide, aminopyrazole, indole, imidazole, oxy and aminoquinoline series.

These radicals can optionally carry further nonionic and / or anionic or cationic substituents.

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Nonionic substituents are to be understood as meaning those radicals as are customary in dye chemistry, e.g. For example: C ₁ -C ^ -alkyl, Cj-C ^ -alkoxy-, C ₂ -C ^ -alkylcarbonylamino, arylazo radicals and halogen atoms such as fluorine, chlorine and bromine.

Suitable cationic substituents are in particular ammonium groups.

Carboxylic acid and sulfonic acid groups come as anionic substituents in question.

A preferred group of dyes in the context of the formula I corresponds to the formula

II

in which R ₁ and R _{2 are} hydrogen, an alkyl radical or an aralkyl radical,

R, hydrogen, halogen, an alkyl, alkoxy or represents aryloxy radical,

R ^ for hydrogen, an alkyl, alkoxy, cyano, Alkylsulfonyl, sulfamoyl, amino, acylamino or carbamoylamino group, X represents chlorine, bromine, cyano, methyl sulfonyl or the nitro group. Le A l'l 2jb - 2 -

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Suitable alkyl radicals R ₁ and R ₂ are alkyl radicals with preferably 1 to 4 carbon atoms, optionally substituted by chlorine, bromine, cyano, hydroxyl, acyl, acyloxy, alkoxy, amino, acylamino or ammonium groups.

Suitable aralkyl groups R 'j and R ₂ are in particular benzyl and phenylethyl.

Suitable radicals R- are, in addition to hydrogen, especially chlorine atoms, Methyl and ethyl radicals, methoxy and ethoxy radicals optionally substituted by hydroxyl or acyloxy groups as well as fhenoxy residues.

Suitable alkyl and alkoxy radicals R ^ are in particular methyl, Methoxy, ethyl and ethoxy radicals.

Preferably R ^ represents acylamino and carbamoylamino groups.

The aforementioned acyloxy and acylamino radicals include, in particular, formyl, alkylcarbonyl, arylsulfonyl and To understand alkoxycarbonyl-oxy or -amino radicals, whereby among the alkyl and alkoxy radicals are preferably those with 1 to 4 carbon atoms and, among the aryl radicals, are preferably phenyl radicals.

Particularly preferred dyes of the formula I are those of the formula

Ill

CH ₃ CN f— Vn . ^R 1 ^f N -ξ ~ "NC - ^ > - N = ^ R ₂ ' r Λ V . CH ₃ χ

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in which R- ^{1 represents} hydrogen, -CH 1, -CgHc, -C ₃ Hy, -C ₄ H ₉ , -CH ₂ C ₆ H ₅ , -CH ₂ CH ₂ OH, -CH ₂ CH ₂ Cl, -CH ₂ CH ₂ OCOCH ₃ , -CHgCH ₂ OCOCgH ₅ , -CHgCHgOCOC ₆ H ₅ , -CHgCHgOCOCHgC ₆ H ₅ , -CH ₂ CH ₂ OCOCH ₂ Oc ₆ H ₅ , -CH ₂ CH ₂ OCOOCH ₃ , -CH ₂ CH ₂ OCOOC ₂ H ₅ , -CHgCHgCOOCH ₃ , -CHgCHgCOOC ₂ H ₅ , -CHgCHgCN,

/ N _v , n ± / N.

-CH ₀ CH ₀ -NN, -CH ₀ CH ₀ -N 7, -CH ₀ CH ₀ -N 7 ²² W ²² UN ²² W

-CHgCH ₂ OCH ₂ CH ₂ OH, -CH ₂ CH ₂ OCh ₂ CH ₂ OCOOCH ₃ , -CH ₂ CH ₂ OCH ₂ -CH ₂ CN, -CH ₂ CH ₂ -N (CH ₃ ) g, -CHgCHg-C ₆ H ₅ , -CHgCHg-Ν ^ Λ

NH ₂

β / ^CH 2 " ^C 6 ^H 5 θ

-CH ₂ CH ₂ -N or -CH ₂ CH ₂ -N (CHj) _3. ,

R ₂ ¹ for R ₁ * or -CH ₂ CHg-N N, -CHgCHg-N 7, -CH ₂ CH ₂ -N N-CH ₃ , -CH ₂ CH ₂ -NJ

or -CH ₉ CH ₀ -N / *,

^ά * ■ Vn-CH ₃

R ₃ ^{1 is} hydrogen, -CH ₃ , -C ₂ H ₅ , -OCH ₃ , -OC ₂ H ₅ , -OCH ₂ CH ₂ CN, -Cl- and

R ₄ hydrogen, -CH ₃ , -C ₂ H ₅ , -OCH ₃ , K) C ₂ H ₅ Cl, -

where η 0-4 is -NHCOCHgCl, -NHCOCH ₂ OH ^ NHCOCHgOCOCH ₃ , -NHCOC ₂ H ₅ or -NHCOC ₆ H ₅ and X is chlorine, bromine, cyano, methylsulfonyl or the nitro group.

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The new monoazo dyes of the formula I can be prepared by making diazotized anilines

H ₃ C CN

. (IV)

in which X has the abovementioned meaning, with coupling components of the formula

H-K (V)

in which K has the meaning given above, combined.

The anilines (IV) can advantageously be diazotized in concentrated sulfuric acid or a mixture of concentrated sulfuric acid and concentrated o-phosphoric acid at temperatures around 0 ° C. with nitrosylsulfuric acid.

Suitable coupling components are: phenols, naphthols, Aminonaphthalenes, acetoacetic ester anilides, pyrazolones, indoles capable of coupling, quinolines, pyridones and enolizable ones Ketones and especially aminobenzenes.

Possible aminobenzenes are:

N ₁ N-diethy] aniline, N-ethyl-N-benzylaniline, N-ethyl-N- (ß ~ hydroxyethyl) ~ aniline, N, N-bis- (ß-hydroxyethylaniline), N-ethyl-N- (ß -noetoxyethyl) -aniline _f N-benzyl-N- (ß-acetoxy =: ethyl) -aniline, N, ^ - Bie- (ß-acetoxyethylaniline), N-ethyl-N-

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(ß-benssoyloxyäthyl) -aniline, N-ethyl-N- {ß-pbenylacetyl-oxy = ethyl) ~ aniline, N-ethyl-N- (ß-phenoxyacetyloxyethyl) -aniline _t N-methyl-N ~ (ß-phenoxyacetyl -oxyethyl) aniline, N- (η-butyl) -N- (ß-phenoxyacetyloxyethyl) aniline, N-ethyl-N- (ß-methoxy = carbonyloxyethyl) aniline, N-ethyl-N- (ß-ethoxycarbonyloxy = ethyl) -aniline, N-ethyl-N- (ß-methoxycarbonylethyl) -aniline, N-ethyl-N- (ß-a ^; thoxyoarbonyl ethyl) -aniline, N- (ß-cyanoethyl) - "aniline, N- Ethyl-N- (ß-cyanoethyl) -aniline, N- (ß-hydroxyethyl) -N- (ß-cyanoethyl) -aniline, N- (ß-acetoxyethyl) -N ~ (ß-cyanoithyl) ~ aniline, N- (ß-Benzoyloxyethyl) -N- (ß ~ oyanäthyl) -aniline, N-ethyl-N ~ ß- [j, 2,3-triazolyl- (l) -Hthyll-aniline, N-ethyl-N-ß- | 1,2,4-triazolyl- (1) -äthylj [-aniline, N-ethyl ~ N- [ß-pyrazolyl- (l) -äthyfj-aniline, N-aothyl-N- [ß- (β »-oyanethoxy ) -äthylJ-ani = lin, 3- (N-ethyl-N-benzyl) -amido-toluene _f 3- [Vf-ethyl-N-iß-hydroxyethyl) -amino-toluene, 3-benzyl-N- (ß ~ acetoxyethyl) J-tolu = oil, 3 ~ JN ₁ N-BiS- (ß-hydroxy-ethyl) j-araino-toluene, 3- (ji-aothyl-N- (ß-acetoxyethyl)] -anii no-toluene, 3- | N, N-bis (β-acetoxy = ethyl) I [-aniino-t.oluo], 3- [N, N-bis (β-acetoxyethyl) I-aininotoluene, 3 ~ [N-ethyl ~ N- (ß-bonzoyloxyethyl) I-aminotoluene _f 3- [N ~ ethyl ~ N- (ß-phenyl-acetyloxyethylM-aminotoluene, 3- [K-ethyl-N «(ß- Phynoxyncetyl-oxyethyl) j ~ auiino-toluene, 3- | N-methyl-N- (β-benzoyloxyethyl) l-omino-toluene, 3- | N-butyl-N- (β-phenyl'-ncetyloxyethyl jl -r, raino-toluene, 3- jN-ethyl ~ N- (ß-Rjethoxycarbonyl-oxyUthyl) J-aiüino-toluene, 3-pi-ethyl-N- (ß-Uthoxycarbdnyloxyöthyl) I -amino-toluene, 3- [ ir-ethyl-N- (ß-methA oxyoarbonylethyl) I -amino-toluene, 3- | N- (ß-cyanoethyl)] - οιπ1ιιο-toluene, 3 ~ ^ i-ethyl-N- (ß-oyanäthyl)] - amino-toluene, 3- | κ- (β-hydroxyüthyl) -N- (ß-cyanoethyl)] - araino-toluene, 3- [N- (ß-acetoxy «ethyl) -N ~ (ß-oya« ethyl) j-aminotoluene, 3- [N- (β-benzoyl-oxyfithy ^; i) -N- (ß-cyanoethyl) I-araino-toluoi, 3-N-ethyl-N- [1,2,3-triazo = IyI- (IJ-ethylJ-eminotoluene, 3-N-ethyl-N- [acetoxyethoxy) -ethyl] -amino-toluene, 3- (N-ethyl ~ N-benzoyl-amino-anisole, 3- [jff-ethyl-Le A 14 235-6 -

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N- (ß-hydroxy-ethyl ) \ -amino-anisole, 3 · [Ν, N-Bi s- (ß-hydroxyethyl)] -amino-anisole, 3- {N-ethyl-N- (ß-aeetaxyethyl )] - ainino-anisole, 3- {N, N-bis- (β-acetoxyethyl) I-amino-anisole, 3- [N-ethyl-N- (β-benzoyloxyethyl) I -amino-anisole, 3-JN ~ Ethyl-N- (ß-phenylacet = oxyethyl)] [- amino-anisole, 3- jji-ethyl-N- (ß-phenoxyacetyloxy = ethyl) J-aiaino-anisole, 3- IN-methyl-N- (ß -benzoyloxyäthylM-aminoanisole, 3-j_N-n-butyl-N- (ß-phenyl-aoetyl-oxyethyl) J-araino-anis sol, 3- | N-ethyl-N- (ß-iaethoxy-carbonyl-oxy-ethyl ) T-atBino-anie sol, 3- JN-ethyl-N- {ß-ätboxycarhonyl-oxyäthyl) J-ainino-cniscl, 3 ~ JK-ethyl-N- (ß-ethoxycarbonyl-ethyl) J-amino-anisole, 3- | n ~ (ß-cyanoethyl) J-amino-anisole, 3-Ri-ethyl-N- (ß-cyanoethylfjamiho-anisole, 3- | N-ß-hydroxy-ethyl) -N- (ß-cyano-ethyl) J- aininoanisole, 3- JN- (ß-Ac et oxyäthyl) -N- (ß-cyanoethyl) i | - aniino-anisole, N- (ß-Denz oy 1 oxyäthyl) -N- (ß-cyanoethyl) J -amino- anis oil _t 3- (N-ethyl-N- (ß-acetoxyethyl) -aminoj-chlorobenzene, 3- | N-ethyl-N (ß-cyanoethyl) -amino ^ I-chlorobenzene, 2- [N- (ß -cyanethy 1) -amino ^ jtoluene, 2- [N- (β-acetoxyethyl) -aminol-toluene, 2- | N- (β-benzoyloxyethyl) -amino 1-toluene, 2- [n- (β-cyana "ethyl) -aminol-anisole, 2- | N- (β-acetoxyethyl) -amino [~ anisole, 2-JN- (β-beii2oyloxyethyl) -amino-] anisole, 3- (N, N-diethylamino) -acetanilide , 3- (N, N-Di = äthylaiaino) -formanilid, 3- (N, N-diethyl-amino) -propionäure = anilid, 3- | N-Ethyl-N- (ß-acetoxyethyl) -an] inoj ~ ocetanilid _t 3- | N, N-bis (ß-aeetoxy-ethyl) -aminol-acetanilid, N, H-diethyl-N'-chloro-acetyl-phenylenediaiirin- (1,3), N, N-diethyl- N »-hydroxy * acetyl-phenylondiainine- (1,3)» 2- (N, N-diethylamino) -d-acetyl = asino-anisole, 2- (N, N-diethylaiaino) - ^ - acetylamino-phenetol, 2 - (N-ethyl-N-benzylamino) - '4-acetylamino-ani8ol, 2- ^(N-ethyl-N-r benz3 laroino) - ^ - acetylamino-anisole, 2-fN-Acthyl-N- (ß-Acet = i oxyäthyl) -ämino -'i-acetylainiho-anisole, 2- [N, N-bis- (ß-acetoxysi äthyl) -amino] - ⁱ t-acetylaiaino-anisole, N-ethylaniline, N-ß-hydro « xyethylaniline, N-ethyl, N-13-hydroxyethylaniline, anilino-N-ethyl-N-ethyl -. (ß-benzyldimethyl-aimnoniiir a) chloride, anilino

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N-butyl-N-ethyl- (β-trimethyl-ainaioniuni) "chloride, anilino-N-ethyl-N-ethyl- (β-N-pyridinium) chloride, anilino-N-ethyl-N-ethyl ( ß-l _f 2,3-triazolium- (l) -3-N-roethyl) -chloride, anilino-N-fit.hyl-N-ethyl- (ß ~ 1,2, 't ~ triaiblium- (l) ~ 4-N-ynethyl) chloride _t anilino-N-ethyl-N-ethyl- (ß-i, 3, ^ - triazoliura ~ (l) -3-N- »ethyl) chloride, toluidino (3) -ii-methyl-N-ethyl- (ß-trimethylamraoniuinchlorid).

■ Aue of the series of enolizable xeto compounds selenium beiepielewelee called: Acetylacetone, Bensoylaoeton, Aceteseigeäuremethyl- bsw. -ethyl ester, Aceteeeigeäureanilide and its in the Anllidrest by methyl- » Methoxy and chlorine substituted derivatives as well as indanedione and dimedon. Possible phenols are: phenol, ο-, πι -, - ρ-ΙχββοΙ, methyl salicylate, resorcinol, 2-Hitro-resorcinol, hydroquinone-monomethy1- bew. -Äthyläther, l-hydroxy-4- (ß-cyanoethyl) benzene. As examples of Naphthols are listed: fl-naphthol, 2,6-dihydroxynaphthalene, 2-hydroxy-6-methoxy-naphthalene, 2-hydroxynaphthalene-5 (or 6) -sulfonic acid diethylamine, 2-hydroxynaphthalene-3-carboxylic acid methyl ester, 2-hydroxynaphthalene- 3-carbonsttureanilld and its in the anilldrest by methyl, Methoxy, ethoxy or chlorine substituted derivatives.

Further suitable coupling components in consideration t indole, 2-methyl-indole, 2.5-dimethyl-indole, 2.4-dimethyl-7-methoxyindole, 2-phenyl-indole, 2-phenyl-5- * thoxy-indole, 2-methyl- 5- or 6-chloro-indole, 1,2-dimethyl-indole, 1-methyl-2-phenylindole, 2-methyl-5-nitro-indole, 2-methyl-5-oarbomethoxy-indole, 2-methyl-indoline, 1,2,5,4-Tetrahydroquinoline and its derivatives, such as N-Xthyl-l ^^^ - tetrahydro-quinoline, N- (ß-hydroxyethyl) -l * 2,3t ^ -tetrahydroquinoline, N-benzyl-l, 2,3 # ^ - tetrahydroquinoline, Le A IH 235

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"N- (0-Cyano * thyl) -7-acetylaiiiino-l ₄ 2", 3 _f 4-tetrahydroohinolin _# Pyrazolones such as 3-methyl-pyrazolone- (5), l-phenyl-3-methyl-pyrazolone- ( 5) * X- (fl- cyanoethyl) -3-methyl-pyrazolone- (5) »1,3-dimethylpyrazolone- (5)» l- (fl-acetoxyethyl) -3-methyl-pyrazolone- (5) , l - (o-Chlorophenyl) -3-raethyl-pyrazolone- (5), 1-phenyl-3-carbomethoxy-pyrazolone- (5) * 1-phenyl-5-aminopyrazole, 1- (3-aminophenyl) -pyrazolone - (5) # 1- (4-aminophenyl) pyrazolone- (5) ,. > Methyl-pyrazolon- (5) -carboxylic acid- (1) -araidin, 1-pheny1-pyrazolon- (5) -oarboonic acid- (3) -amide, 2-methyl-4H-ρyrazolo ^ 2.3-a7-benzimidazole, ^ I- (3-Thia-oyclopentyl) 3-methyl-pyrazolone- (5) -S-dioxide7j pyridines such as 2,6-dihydroxy-3-oyan-4-methyl-pyridine, N- (methyl-, xthyl- or phenyl) -6-hydroxy-3-cyano-pyridone- (2) j quinolines such as 8-hydroxy-quinoline, 2,4-dihydroxy-quinoline, N- (methyl- or n-butyl) -4-hydroxyquinolone- (2); Pyrimidines such as barbituric acid or 2,6-bis-methylamino-4-pheny1-aminopyrimidine, 2-ethylamino-4-phenylaraino-6-phenoxy-pyrimidine, 2. ^ - bis-ethylamino-e-phenylamino-pyriroidin imidazole, 4,5-dimethyl -imidazole, 4,5-diphenyl-imidazole, 4-methylimidazole, 4-phenyl-imidazole, thiazoles such as 2-hydroxy-4- (methyl- or phenyl) -thiazole, 2-methylamino- (F-methyl- or -phenyl) -thiazole, 2- (fl-Cyanoethylaraino- ^ ^J fn »ethyl- or phenyl) -thiazole.

The diazo component !! anilines (IV) used so far has not been described and is therefore also part of the present invention.

The new / inilines (IV) are obtained if 2,4-dicyan-3,5-dimethylaniline is used - optionally after prior acylation of the free amino group - halogenated or nitrated in the 6-position, if desired, then the halogen atom introduced in the 6-position in a manner known per se against a cyano, Exchanges nitro or alkylsulfonyl group and removes the N-acylamino protective group which may have been introduced.

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The 2,4-dicyano-3 »5-alffiethylaniline used as the starting material obtained according to the instructions given in German patent application P 21 25 907.4 by thermal decomposition of the dimerization product obtained according to German patent specification 958 922 of 3-methylene-glutaric acid dinitrile or 3-methylglutaconic acid dinitrile.

The halogenation, preferably chlorination and bromination, of 2,4-dicyano-3,5-dimethylaniline is carried out according to known methods Methods by the action of elemental chlorine or bromine - advantageously in the presence of a Lewis acid and a solvent which is inert under the reaction conditions at temperatures from 15 to 120 ° C. Particularly recommended is the implementation of the chlorination in glacial acetic acid / aluminum chloride at 60 - 90 ° C. For the bromination is the presence a catalyst is not absolutely necessary.

The nitration of 2,4-dicyan-3,5-dimethylaniline, which is usually protected by prior acylation, can also be carried out by methods known per se (see, for example, "Organikum ⁿ _f organic-chemical basic internship, Verlag der Wissenschaften, pages 286-290 , 5th edition (1965)) The cleavage of the acyl, preferably acetyl protective group takes place in a known manner by acid or alkaline hydrolysis known methods by reacting the corresponding halides with alkali cyanides or copper (I) cyanide or alkyl sulfinates in preferably polar, basic solvents such as dimethylformamide, pyridine, picoline, dimethylaniline at elevated temperatures, preferably between 50 and 150 ° C (cf. French patents 1 511 ^ 932, 1 584 932 and 2 018 473, US patent 2 195 and German Offenlegungsachrift (DOS) 1 96 6 124). The procedures according to DOS 1 807 642 are recommended for halogen / nitro exchange.

Those dyes of the formula (I) in which X is cyan or alkylsulfonyl, can in some cases also be very advantageously represented in such a way that compounds Le A 14 235 - 10 -

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4USbJ. / TUÜU ORIGINAL INSPECTED

of the formula (I), in which X denotes chlorine or bromine * £ Miv ** 'converts suitable cyanides or alkyl sulfinates according to French patent specification 1,511,932 or 2,013,173.

The new water-insoluble dyes, their mixtures with one another and their mixtures with other dyes are particularly suitable for dyeing in finely divided form synthetic fibers and fabrics made from cellulose tri- and 2 1/2 acetate, polyurethanes and especially from polyamides such as B. polycaprolactam, polyhexymethylene diamine adipate or poly-amino-undecanoic acid and from aromatic polyesters such as polyethylene terephthalate and Poly-1,4-cyclohexanedimethylene terephthalate. The invention Dyes with an ammonium group in the molecule are particularly suitable for dyeing fibers and fabrics made of polyacrylonitrile or from copolymers of acyl nitrile and other vinyl compounds such as acrylic esters, acrylic aides, vinyl chloride « Vinylidene chloride and vinyl pyridine or from copolymers of dicyanethylene and vinyl acetate and for dyeing acidic modified polypropylene, polyester or polyamide fibers.

The water-insoluble liquors are used for dyeing from aqueous liquors It is advisable to use dyes in dispersed form or condensation products from Kreaol, 2-naphthol-6-sulfonic acid and formaldehyde. Further dispersants and / or wetting agents could be added to the dyebath.

When dyeing aromatic polyester fibers or triacetate fibers at temperatures up to 105 ° C. it is generally advantageous to achieve good dye yields. Usual carrier substances to be used.

The dyeing of polyester materials with the invention Dyes can also be produced using the known thermosetting process be performed.

Suitable for dyeing metal-modified polyolefin fibers in particular those dyes of the formula I which are in the

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Coupling component in the o-position to the azo group carry a group capable of chelating, for example an OH, NH ₂ or NH group.

You can use the new water-insoluble dyes for spin dyeing of polyamides, polyesters, and polyurethanes Use polyolefins.

The printing is also carried out in a known whiteness by * guided. One uses, for example, a printing ink which, in addition to the dye, contains the auxiliaries customary in printing, the is applied to the materials to be printed and fixed by subsequent heat treatment.

The dyeings and prints obtained are distinguished by a particularly clear hue and good drawability as well as good general fastnesses. They can be subjected to an after-treatment by putting active detergents on them Lets substances or reducing agents act, thereby in some cases an improvement in some Fastness properties such as rub, sublimation, wet and light fastness can be achieved.

The dyes with an ammonium group obtained according to the process The anion in the coupling component preferably contains the remainder of a strong acid, for example sulfuric acid or their half esters or an aryl sulfonic acid, phosphoric acid or a halogen ion. The mentioned anions introduced into the dye molecule according to the method can also be replaced by anions other acids, e.g. organic acids such as formic acid, acetic acid, lactic acid or tartaric acid. The dye salts can also be used in the form of double salts, especially with zinc chloride.

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Production of azo dyes: %% Q S 5%

Example 1 . ,

2.98 parts of 2,4-dicyano-3,5-diraethyl-6 ~ chloroaniline be finely powdered and acid under stirring at 10 ⁰ C in 15 ml konz.Schwefel entered. Then, 5 parts Nitrosylschwefel acid over 1 hour at ⁰ ° C (4.5 part "nitrosylsulfuric ent = speak 1 g nitrite) was added dropwise and stirred for 2 hours at O ⁰ C to =. The reaction mixture is poured into 50 parts of ice and aqueous sulfamic acid solution is added until excess salt is completely decomposed. The diazoniura salt solution thus obtained is added with stirring to an ice-cold solution of k _t k parts of bis-ß-methoxyearbonyloxyethylaniline in 60 parts of 5% hydrochloric acid, the reaction mixture is neutralized with 10% sodium hydroxide solution at ⁰ ° C. and then the resulting dye the formula

H ₃ C CN

VN = N ^ f VNv

i ^{X /} CH CH OCOOCH,

f VNv

^{X == /} CH ₂ CH ₂ -O-COOCH

filtered off, washed with water and dried. This gives 6.1 g parts of a red powder which is based on terephthalic acid poly: Glycol ester fibers, dyed according to the usual conditions, produce a susceptible and lightfast red-tinged orange.

Other valuable dyes are obtained when diazotized 2,4-dicyano-3.5- »dimethyl-6-chloro (bromine, nitro, cyano, methylsulfonyl) aniline combined with the coupling components of the following table. The dyes color polyester materials in the specified tones; In the table below, X stands for the substituent in the 6-position according to the general formula I.

Le A14 235

- 13 -

3098 Ί -> / 1 QSQ

example

Cl / Br

NO,

Cl

NO,

Cl

CN

(TO;

Le A14 235

Coupling component

I!

^ CH ₂ -CH ₂ -OC-OCH ₃

^ CH ₅ -CH ₅ -OC-OCH, OO

/ CH ₂ -CH ₂ -OC-OCH ₃ ^ CH ₂ -CH ₂ -Og-OCH ₃

N.

$ 6 ^H 5 ¹ HN-CO- ^ "Vci

I /

j HN-CO-f ^ -Cl

HN-CO

i /

CH

/ ° 2 ^H 5 a / ^N CH _o CH _o -0-C0-CH,

₂ CH ₂

j- ^N CHgCH ₂ -O-CO-CH ₃

^: CH,

CH

- 14 309832/1060

Shade of scarlet fever

bluest. Red

blue <red

bluish, red

blue

Dlaust. lot

) runs, lot

lolett

At- (
game
No,

Coupling component Nuance

Cl

CH

12 JSO ₂ -CH ₅

UO,

/ 17 ON

Le A 14 23'i

CH,

H ₂ CH ₂ -CO-OCH ₃ OH ₅ CH ₉ -CO-OCH,

OHgCH ₂ -CO-OCH ₃ ^ CH ₂ CH ₂ -CO-OCH ₃

■ λ * / CH ₅ CH ₅ -CO-QCH,! CH

N,

^ C ₂ H ₅

■ ΓΙ γ **

>

ί i7

C ₂ H ₅

, "CH ₂ -CH ₂ -O-CO-O CH ₃

CH ₃

^ CH ₂ -CH ₂ -O-CO-OCH ₃

.H ₃

- 15 -

309832 / 10ß0 Bot

Eot

violet

"bluest.

Bot

bluest. Eot

violet

Bot

Red

example

Coupling component

nuance

NO,

19! Cn

Br

21 JNO ₂

Cl

23: CN 24 NO,

^ ssf ^ H ₂ -CH ₂ -O-CO-OCH-CH,

CH ₂ CH ₂ -Cl

.CnH

/ ^C 2 ^H 5

fl Vn ^ ⁵

violet

Red

Red

violet

Red

Red

violet

25 jCl

Le Λ

CH blue. Red

3 0 9 8? 1 η 0 6

example
Kr.

Coupling component

nuance

Br

N0 "

Cl

29; cn

NO ₂

Cl

Br

NO ₂

I.α 'S. in 2 previous year

/ 7Λ / C ₂ H ₅

CH ₃

CPl ₃ CI ^ -

CH ₃

DCH ₃

PU

/

HN-CO-CH ₃

PCH ₃

C ₂ H ₅ H

j HN-CO-CH ₃ OCH ₃

H.

I hn-co-ch!

H ₂ C-COOCH ₃

_VnH-CH-COOC H ₃

"I.

H ₂ C-COOCH ₈

NH-CH-COOCH ₃

-U-

/ ι η 6 (j -laust, red, red, blue, violet, red, blue

rotst. orange

orange Red

example
No.

Cl

35 Br

NO ₂

31 cl

i Br

39 j NO ₂

40 i ür

Le A

Clutch component

N (C ₂ Hj

₂ HY ₂

(C ₂ Hj

₂ HY ₂

ι CiJ ₃

Hj

j ₂

-N _t - / \ CH ₂ -CH ₃ -O-CO-OCHj

/ Cn H «

CH ₂ -CH ₂ -0-CO-OCH ₃

CH ₂ -CH ₂ -0-CO-OCH ₈

, C ₂ H ₈

CtT - id 0 9 8 "'M 0 6

nuance

Red

Red

violet

Red

Red

violet

Red

violet

example
No.

43 'Cl

Cl

Br

NO ₂

Coupling component

^ C ₂ H ₅

i / Tvs

-NH-CH ₂ CH ₂ -OH

44! CN i ^ y -NH-CH ₂ CH ₂ -OH

^N0 2 ^: V 7 "NH-CH ₂ CH ₂ -OH

\ n 8

= * ^ CH ₂ -CH ₂ -OCA

■ Ν

-CH ₂ -OC-vJ

ε O

-CH ₂ -OC ^ / J

49 SO ₂ -Cl ₅ . ^ "VnH-C ₂ H ₈

Le A i'f L ^} 3 ^l J

- 19 -

3 0 9 8? ;: / 1 OC Cl Nuance Violet Scarlet Red Blue, Red Red Red Violet Hol,

3game
Kr.

Coupling component

nuance

Br; NO ₈ CN Br NO «Cl Br NO ₂

Le A 14

(/ VNH-C ₂ H ₆

NH-C ₂ H ₆

/ n iic 55

= / ^ CH ₂ CH ₂ -N-

^ H ₂ CH ₂

NN \ = ss /

x .CH ₂ CH ₈ -0-CO-OCH ₅

-N

^ ~ ^y ^ CH ₂ CH ₂ -O-CO-OCH ₃ HN-CO-CH ₈

, 0CH ₈

^ CH ₂ CH ₂ -O-CO-OCH ₃ HN-CO-CH ₈

C ^ zCH ₂ CH ₂ -0-CO-OCH ₃ ζ ^r ^ CH ₂ CH ₂ -0-CO-OCII ₃ HN-CO-CH ₈

20 red

violet

Red

Red

violet

violet

violet

!Blue

30983 2 / 10S0

example
iir.

Coupling component '

'ι Nuance

Cl

Il

CH ₂ -CH ₂ -0-C-CIL ₄ -CH ₃

59! CN 60 j NO ₃

H ₅

It

-CHg —0 — C-CHg -

Il

CH ₂ "" CH ₂ -0-C-CHg ** CHg

61 SO ₂ -CH ₃ (H.

o2 I Br 65 'NO ₂

Cl

H ₅

^ CH ₂ CH ₂ -OH

H"

'CH ₂ CH ₂ -OH

CH ₂ CH ₂ -OH

HN-CO-CH ₈ -CO-CH ₃ RED

Red

violet

Sharlaqh

Red

violet

bluish red

65 'CN

Le Λ l'l c '.

: ^ C ₂ H

: HN-CO-CH ₂ -CO-CH ₃

- 2 L -

30983 {violet

Beiapi el |
No.

Coupling component 1 shade

NO

HN-CO-CH ₂ -CO-CIl ₅ OCH ₈

-0-CO-CH ₈

! HN-CO-CH ₃

CH ₂ CH ₂ -0-CO-CH ₅

SO ₂ -CH ₃

HN-CO-CHg

OCH ₃ '^ CH ₂ CH ₂ -0-CO-CH ₈

CH ₈ -0-CO-CH ₈

NO ₂

Cl

71 I SO ₈ -CH ₃

PCH ₈

JCH ₂ CH ₂ -0-CO-CH ₈ ■ Ν NCH ₂ CH ₈ -0-CO-CH ₈

-0-CO-CH ₈

"CH ₂ CH ₂ -0-CH-CH ₈ HN-CO-CH ₃

/ CH ₂ CH ₂ -0-CO-CH ₈

y = / "^ CiJ _{2 CHs} -0-CO-CH ₈ HN-CO-CH ₃

NO ₈

CH ₂ CH ₈ -0-CO-CH ₈ M.

V = ³ 'OH ₈ CH ₈ -0-CO-CH. HN-CO-CH ₈

rotst blue violet violet

Violet violet blue

CN

Le A IH 235

N.

CH ₃

Il

CH ₈ CH ₂ -OC-CH ₈

- 22 -

Red

1 Π 80

example

Coupling compo ne nt e

nuance

Br

NO,

76 ί Cl 77 'CN 78 j NO ₂ 79! Cl

W.

= * CHj -CH ₈ -0-C-CH ₈

I ₈

^ CH ₂ CH ₂ -OC-CH ₈

,, CH ₂ -C ₆ H ₆ ^ CH ₂ CH ₂ -CN

/ CH ₂ -C ₆ H ₈ ^ CH ₂ CH ₂ -CN

I ₈

) = ^ NiH ₂ CH ₁ -CN JCH ₅

SO ₂ -CH ₅

¹ / CH ₂ -C ₆ H ₅

HN-CO-CH,

OCH,

-C ₆ H ₆

HN-CO-CH ₈ OCH ₈

NO ₈

CH ₂ -C ₆ H ₈ ! HN-CO-CH ₈

Le A IM red

Purple red

Red

Violet violet violet

JBlue

309832/1060

Beiapi el | _

No.

CN

Coupling component

^ CgHg

OC ₂ H ₅

Br

■ ^N0 2

Cl

IHN-CO-CH ₃

! f \ _N

'HN-CO-CIi ₂ -Cl

SO ₂ -CH ₃ '^ V ^N v

CH ₃ -Cl

NO ₀

HN-CO-CH ₂ -Cl

70 i ci

HN-CO-CH ₃

! SO ₈ -OH ₈

Le A IM

N,

C ₂ H ₆ HN-CO-CH ₃ shade

violet

violet

red, blue, blue, red, blue, red violet

bluest.red biausted.hot

309832/1 Q 60

example

No.

clutch component.

nuance

NO ₂

Cl

Br

75 NO ₂

Cl

= / ^N C

C ₂ H

HN-CO-CH ₃ OCH ₃

-CN

OCH ₃

-CHj, CH ₂ -CN

-Cf ^ -CN

/ OCH ₃

CH ₂ CH ₂ -0-CO-Ci ^

77 y Br. ^ y-NH-CH ₈ CH ₂ -0-CO-CH ₃

78 i NO ₂ ^ y -NH _{-CH 2 ClI 2} -O-CO-CH ₃

violet

Red

Red

violet

Red

Red

violet

79 ■ Cl

Le A 1 '»2j ^l i

-H

ysJ ^ CH ₂ CII ₂ -U-CO-CH ₃
HN-CO-CH ₃

Red

0 9 fr Ί 2 / I 0 ti!)

At-

3game | X

No.

Coupling component

nuance

fir

NO ₂

Cl

! Br

NO ₂

Cl

Br

NO ₂

OCfI ₃ E, CfL, -0-CO-CfL. -0-C _e H ₅

Red

OCII ₃

N 'purple

^s CHj5 CH ₂ -0-CO-CfI ₂ -0-C ₈ H ₆ ί

I blue, red

CU ₂ Ci ^ -0-CO-CH ₃ HN-CO-CI%

Z "CfI ₂ CH ₂ -0-CO-CH ₃ HN-CO-CfI,

> = ^/ CfI ₂ CH ₂ -O-CO-CH ₃ HN-CO-CH ₈

CH ₂ Cf] ₂ -CN

OCfI ₃

OCf] ₈ ^ CH ₂ CtI ₂ -CN

OCH ₅ - 26 -

bluish red

violet

Red

Red

violet

1080

At- ι
3game '
No ^.:

Clutch component

nuance

88

Cl

Br

, CH ₂ -CjJ eds

CrLj CH ₂ —Ο — CO — OH ₃

^ CH ₂ -C ₂ H ₅
^ H ₂ CH ₂ -O-CO-CH ₃

NO ₂

CH ₃ -0-CO-CH ₃

CN

^V CH ₂ CH ₂ -CN

SO ₂ -CH ₈

CH ₃ , CH ₂ Ci ^ -OH
CH ₂ CH ₂ -CN

NO ₂

^ CH ₂ CH ₂ -OH
^v CHjj CH ₂ -CN

Cl

/ i purple

CH ₅ ^ CH ₂ CH ₂ -0-CO-CH ₂ -C ₆ H ₆

95, Br

, ^V CH2 CIt, -0-CO-CH ₂ -C ₆ H ₅

CH ₃ - 27 -

ι;

Le Λ

violet

violet

bluish red

bluish red

violet

violet

ι purple

309832/1060

Example no.

Coupling component

. , .uar.ce

NO ₀

Cl

Br

NO ₂

100

Cl

H ₅

V ₁ .

, CII ₃ CH ₂ -O-C0-CH ₂ -C ₆ H ₅

^£ '3

OCH ₃ CH ₂ CH ₂ -O-CO-CH ₃

N '

/ ^C Z

OCH ₃ -0-CO-CH ₃

OCli ₅ , C ₂ H ₆
"" CH ₂ CH ₂ -O-CO-CH ₃

OCH ₃

101

SO ₂ -CH ₃

Le A 14 23 ¹ y

^ CH ₂ CH ₂ -OH

rotst blue

Red

Red

violet

Red

.Red

309832/106

Example no.

«I.

Coupling component

nuance

102

MO,

103

Cl

104

Br

105

NO,

106

107

108

log

Cl

CN

Cl

1 10 Lf? A \ l \

OCH, ^ CHgCH ₂ -OH

\ Vn _v

OCH-'CH ₂ CH ₂ -O-CO-C ₆ H ₅ -

OCH-,

OCIL VCH ₀ CH ₀ -O-CO-C ^ Hk
ά 6 5

OCH,

OCH-O-CO-C ₆ H ₅

^V CH ₂ CH ₂ -Cir

Cl violet

Red

! Red

violet

! Red

Red

violet

orange

Red

0 Ü B 'T ^Ί / 1 0 6 0

Example no. Coupling component

nuance

111 112

Cl

113

CN

114

NO,

115

Cl

116

Br

117

NO,

118

Cl

CH ₀ CH ₀ -CN

^{d 2}

Cl

OIL

Le Λ

NH-CH ₂ CH ₂ -CN

CH

\ n

Cl CH ₀ CH ₀ -O-CO-CH
²

Cl CH ₂ CH ₂ -O-CO-CH,

■> = y CH ₀ CH ₀ -O-CO-CH,

Cl ^{d ά} *

^{2 2}

Red

Red

Red

Tiolet

^! orange

orange

Red

Red

30981 '/ 1060

Example Mr.

119 120 121 122 1 23:

124

NO,

Eq

Br

¥ 0,

Cl

125 126

Le A coupling component

CH,

CBL

Cl ^L 2 2

/ oil c

^ TT

5

Cl

Cl

SO ₂ -GH ₅

NO,

^L 5.

CH,

- 31 ~

nuance

Red

violet

Red

Red

violet

Red

Red

violet

30982 ~ / 10 60

For example

Hi

Coupling component

• Nuance

128

Cl

Br

NO,

Cl

CN

NO,

Cl

Br

Le Λ 14

-CH ₂ CH ₂ -O-CO-C ₆ H ₅

F Λ

a Vn ^ CH ₂ CH ₂ -O-CO-C ₆ H ₅

CH, CH ₉ CH ₂ -CO- OCH

^{ά ά}

CH

CH,

OCH, CH,
^V CH ₂ CH ₂ -CO-OCH ₃

, CH ₉ CH ₉ -O-CO-CH,
^ CH ₂ CH ₂ -O-CO-CH ₃

OH ₉ CH ₉ -O-CO-CH,
^v CH "CHo-0-C0-CH,

Red

Red

violet

Red

! Red

violet

Red

Red

309832/1060

Example no.

Coupling component

ι nuance

NO Cl Br NO Cl CN NO Cl

Le Λ 11 2

OCH ^ CHgCHo-O-OO-CH ₃ = ^ ^N CHgCHg-O-C0-CH ₃

CH. α _w ^CH 2 ^CH ₂ - ° - ^c ° - ^0H 3

^ CH ₂ CHg-O-CO-CH ₃

Λ / ^CH 2 CHo-O-CO-CH

Ks = / ^ CHoCHo-O-CO-CH, CH, * ^{ä 3}

. "OHoCHo-O-CO-CH," CHgCH ₂ -O-CO-CH ₃

_(7Vn , ch ₂ ch ₂ -cn ^ CHgCHg-O-CO-CH-

CH ₃ , "CHoCHo-CN

('\\ r ^{2 s} CHgCHg-O-CO-CH ₃

, _% CHoCHo-CN

/ y wr ² ^ CHgCHg-O-CO-CH

CH, ^ CHgCHg-CN

- 33 purple

Red

Red

violet

Bluest Red

Red

violet

. blues. Red

3098 ^ ° '1 08Q

Example ι game no. Coupling component

nuance

H3

Br

GH.

^v CH ₂ CH ₂ -CN

U4

NO,

CH ^ = ^{7 N} CH ₂ CH ₂ -CN

145

Cl

146

SO ₂ -CH ₃

147

NO,

148

Cl

149

Br

'CH,

CH ₂ CH ₂ -O-CO-C ₆ H ₅

CH ₂ CH ₂ -O-CO-C ₆ H ₅

CH ₂ CH ₂ -CO-OC ₂ H ₅

^V CH ₂ CH ₂ -CO-OC ₂ H ₅

Red

red, blue

Red

Red

violet

Red

Red

150

NO,

violet

Le A

4 23b 309832/1080

At- ; apiel no.

«5"

Coupling component ι Nuance

Cl

SO ₂ -CH ₅

NO,

Cl

SO ₂ -CH ₅

NO,

Cl

Br

Le A 14 23b

CH ₉ CH ₉ -CN

' ²

^v CH ₂ CH ₂ -O-CO _r CH ₅

CH ₉ CH ₉ -CN

' ² CH ₂ CH ₂ -O-CO-CH ₅

CH ₂ CH ₂ -O-CO-CH-

CH ₉ CH ₉ -O-CO-CH

^l 3

^N CH ₂ CH ₂ -O-CO-CH ₅

CH ₂ CH ₂ -CN

CH ₂ CH ₂ -CN orange

orange

Red

orange

'· Orange

Red

Red

Red

309832/1060

Example no.

159

160

161

162 163 164 165 166 167 168

NO

Cl

CN

NO

Cl

CN

NO

Cl

CN

NO

Le A 14

Coupling component ι Nuance

CrjHr

^ CHgCHg-O-CO-CgH ₅

2

CH ₂ CH ₂ -O-CO-CH ₅

CHgCHg-O-CO-CH

z-Hc

- 36 - 309832/1060 purple

Red

Red

violet

Red

ι red

rotst. blue

Scarlet fever

! Red

violet

X ill 3piul SO ₂ -CH ₃ No. Ν · ι ₂ 169 SO ₂ -CH, 170 Br 171 NO ₂ 172 Cl 173 Br 174 NO ₂ 175 176 177

Coupling component

! I ·: u a nc e

Cl

Br

/ ^G 2 ^H 5

/ ^C 2 ^H 5

nch

° 2 ^H 5

^G 2 ^H 5

/ ° 2 ^H 5

/ ^C 2 ^H 5 nCH

^ Vn-CH ₂ -CH ₂ -O-OQ-O-CH ₃

Red

Red

ί purple

Red

Red

violet

Red

Red

violet

Red

Red

violet

Le A IH 23b

- 37 309832/1060

The following dyes produce Muf Folyacrylni fcri if ser-n the specified shades:

example

Coupling component

nuance

GO ₂ -CH ₃

182! Br

NO,

Eq

Br NO, CH SO ₂ -CH ₃

NO,

Le A 14 23t)

^ CH ₉ CH ₉ -N ² Cl

Red

= / ^v CH ₅ CH ₉ -N ² red

²

CH ₉ CH ₉ -N ² ♦ CH ₂ -C ₆ H- ₀₁ (-) violet

^S (CH

^s ch ₂ ch ₂ -n (ch ₃ ),

_C1 (-) red

ρΛ-ν;

βΛ-ν

^ n ' ⁰ * " ⁵ Ns *

for \ r

VLr red

violet

Brf ^ red

Red

violet

309832/1

At-

3game:

No. Coupling component

nuance

190

Cl

violet

191

192 193 194

195 196 197

198

SO ₂ -CH,

NO,

Cl

CN '

NO,

Cl

Br

NO,

Le A 14

fKcf

Cl ¹

violet

CH,

Cl ¹

rotst blue

J 0 ι

\ J only-

OSO ₃ CH ₃ ¹¹ "' ¹ Red

OSO ₃ CH ₃ ¹

CH

CH 'CH ₂ CH ₂ -N (CH ₃ J ₃

N) H ₂ CH ₂ -N (CH _3).

Cl '

violet

bluest. Red

_C1 (-Jj purple

Cl ¹

CH, fcotst. blue

- 39 -

30983 2/1060

Example no. Coupling component

Nua nc e

Cl

CN

NO,

Cl

SO ₂ -CH ₅

Cl

(-) Red

-CH,

for \ r

Cl '

Red

N ^ N-CH

Cl '

violet

f ^ A-iT ^c ^ ^ (-) red

^S CH ₂ CH ₂ -N (CH ₃ ) ₂ ^υχ j

NH

V _W / ^C 2 ^H 5

Cl ¹

Red

NH

NO,

Cl

CrtH

*

Cl ¹

violet

yellow

-MO-

Le A m

309832/1060

example

No.

Clutch component

nuance

CH ₈

206

Br

yellow

Cl

207

NO ₈

OeIb

Cl

The following dyes give the specified color nuances on polyester materials

CH ₈ .

208 209

210

Cl

Br

SO ₈ CH ₈

I.
CH ₈

yellow

I.
CH ₁ CH ₁ CN.

CH,

HO ^ N ^ O
I.
COCH ₁

. - 'ii j -

yellow

Le A 14 2/1060

Coloring examples: M ^

a) polyester:

0.1 g of the well-dispersed dye according to the example is carried 1 at 40 ° C in 1 1 of water, which also contains 0.2 g of Dinaphthylraethansulfonsaures Sodium and 0.3 g of cresotinic acid methylc> 3ter. One goes into this bath with 10 g Fabrics made of polyethylene terephthalate, increases the temperature of the dyebath within about 20 minutes to 100 ° C and stains at this temperature for 60 - 90 minutes. A strong reddish orange coloration with good sublimation and coloration is obtained Lightfastness.

If, in this example, the substrate is replaced by 10 g of a fabric made from cellulose triacetate, one also obtains one clear orange color with good general fastness properties.

b) polyamide:

0.1 g of the dye according to Example 18 are well dispersed Form added at 40 - 50 ° C in 1 liter of water, which also contains 0.5 g of a sulfite cellulose degradation product. 20 g of poly-t-caprolactam yarn are taken into this bath and the temperature is increased in about 20 minutes 95 - 100 ° C and stains 1 hour. After rinsing and drying, a clear, strong red color with good lightfastness results.

c) Po.l yacrylni tril

One KiMt 0.5 g det, dye according to Example 57 with addition of 3 ml of 30% acetic acid in 3 liters of water »into this

Le A 14 235 - H2 -

3098 3 2/1060

Bath is entered at 4o - 50 ° C with 100g polyacrylonitrile yarn, increases the temperature of the dyebath within about ^ O Minutes to 100 ° C and stains at this temperature for about 1 hour. A clear red coloration with excellent results results Fastnesses.

Fiber materials made from acid-modified polyester can be dyed using the same process.

Le A 14 235 - 43 -

309832/1060

The presentation of the new intermediates can be explained using the following examples:

Representation of 2,4-dicyan-3,5-dimethyl-6-chloroaniline s

g of 2,4-dicyan-3,5-dimethylaniline were stirred on the water bath in
Liter conc. Acetic acid dissolved, 0.5 g of Al ₃ Clg are added>

adds and at ÖO - 85 ⁰ C

g chlorine gas introduced: after the largest part has been introduced, evolution of HCl begins; yellow precipitate; then the mixture is stirred for 30 minutes at 80-85 ° until the evolution of HCl has ended. The reaction mixture is poured onto ice / water and the 2,4-dicyano-3,5-dimethyl-6-chloroaniline as sand-colored substance sucked off and recrystallized from toluene. A yield of about 80 pounds is obtained colorless crystals with a melting point of 232-233 ° C. calcd. C 58.4 H 3.9 N 20.4 Cl 17.2 found C 58.8 H 4.4 N 20.5 Cl 17.3

Preparation of 2,4 ~ dicyan-3,5-dimethyl-6-bromaniline

g 2,4-dicyan-3,5-dimethylaniline are concentrated in ml with stirring. Acetic acid dissolved and then dissolved in g of bromine
ml conc. Acetic acid was added dropwise. It will take approx. 30 min.

(until there is no more evolution of hydrogen bromide is observed). The reaction mixture

is increased to approx.
600 g of ice discharged and the 2,4-dicyan-3,5-dimethyl-6-bromaniline removed.

Yield: approx. 80 % of theory, f, m.p .: 230 - 232 ° C.

calcd. C 48 H 3.2 N 16.8 Br 32.0 found. C 48 H 3.4 N 16.7 Br 30.4

Le A 14 235 _ 414 _

30983 2/1060

Preparation of N-acetyl-2,4-dicyan-3,5-dimethylaniline

63 g of 2,4-dicyan-3,5-dimethylaniline were in 500 ml Acetic anhydride heated under reflux for 4 hours and then poured onto ice / water. Colorless crystals with a melting point of 189 ° C. are obtained in about 90% yield.

Representation of the 2.4 -_j_ icyan-3,5-dimethyl-6-nitroaniline

t>, 3 parts of N-acetyl-2,4-iicyan-3,5-dimethylaniline are used in -5 ° C to -10 ° C in a mixture of 30 parts each 98 #iger Nitric acid and conc. Sulfuric acid entered. The reaction mixture is stirred at -5 to 10 ° C. for 4 hours and then carried out on ice. 4 g of colorless crystals of W-acetyl-2,4-dicyan-3,5-dimethyl-! 5-nitroaniline are obtained, which melt indistinctly at 280 ° C with decomposition.

By heating in 10 # soda solution, the N-acetyl protective group are split off and the free 2,4-dicyan-3,5-dimethyl-5-nitro-aniline are obtained, which is diazotized without purification and converted into the corresponding azo dyes can be.

Example of a halogen-> cyan exchange on the finished dye

13.2 parts of the dye according to Example 40 are dissolved in 500 parts of dimethyl sulfoxide (DMSO) and 3.22 parts Cu (I) CN added in 80 parts of DMSO. It will be 8 hours at 80 ° C and then stirred for 1 hour at 100 ° C. The dark red Solution gives violet crystals when poured onto ice / water (dye example 41).

Le A 14 255 - 45 -

30 ^c ) 812/1060

Claims (1)

Claims: τ 1.) Azo dyes of the formula CH ₃ CN NC - ^ A - N = NK in which K for the remainder of a coupling component and X stands for chlorine, bromine, cyano, C ₁ -C ₁₄ -AlkYlSuIfOnYl or the nitro group. 2.) Azo dyes of the formula CH, CN R * NC "Ο- ^N = ^N "<'> - ^N ' CH ₃ χ R ₂ in which R ₁ and R _{2 are} hydrogen, an alkyl radical or aralkyl radical, R _{3 is} hydrogen, halogen, an alkyl, alkoxy or represents aryloxy radical, R ₄ for hydrogen, an alkyl, alkoxy, cyano, Alkylsulfonyl, sulfamoyl, amino, acylamino or. Carbamoylamino group and X for chlorine, bromine, Cyano, methylsulforiyl or the nitro group. 3. ) Azo dyes of the formula Le A 14 235 - 46 - 3 0 9 B 3.: / 1 0 6 CH ₃ CN Rj ¹ NC - />> - N = N - <'V N J ₃ XR ₄ ¹ V in which Rj · for hydrogen, -CH ₃ , -CgH ₅ , -C ₄ H ₉ , -CH ₂ C ₆ H ₅ , -CHgCH ₂ OH, -CHgCHgCl, -CHgCHgOCOCH ₃ , -CHgCH ₂ OCOCgH ₅ , -CHgCHgOCOC ₆ H ₅ , -CHgCHgOCOCHgC ₆ H ₅ , -CHgCHgOCOCHgOC ₆ H ₅ , -CHgCHgOCOOCH ₃ , -CHgCHgOCOOCgH ₅ , -CHgCH ₂ COOCH ₃ , -CHgCHgCOOC ₂ H ₅ , -CHgCHgCN, N, -CH ₉ CH ₉ -N? , -CH ₉ CH ₉ -N / ²² UN ²² W -CHgCHgOCHgCHgOH, -CHgCHgOCHgCHgOCOOCH ₃ , -CHgCHgOCHg- CHgCN, -CHgCH ₂ -N (CH ₃ ) g, -CHgCHg-C ₆ H ₅ , - NH ₂ φ ^ ₅ φ -CHgCH ₂ -N or -CHgCHg-N (CH ₃ ) _3. · , -CHgCHg-N /, , -CHgCHg-N /%, _χ Ν _ν β. · '"" ^ N -CH ₉ CH ₉ -N Ί -CH ₉ CH ₉ -N N-CH ^, -CHpCH ₉ -N ^ ^d  \ J * ^ \ y ° * * \ _ä n or -CH ₉ CH ₉ -N f , ^^ VN-CH ₃ Le A14 235 309832/1060 R, ¹ signifies hydrogen, -CH ,, -C ₂ H ₅ , -OCH ₃ , -OC ₂ H ₅ , -OCH ₂ CH ₂ CN, -Cl. And R ₄ · hydrogen, -CH ₃ , -C ₂ H ₅ , -OCH ₃ , OC ₂ H ₅ Cl, -NHCOC _n H ₂ where η 0-4 is -NHCOCH ₂ Cl, -NHCOCH ₂ OH ^ NHCOCH ₂ OCOCh ₃ , -NHCOC ₂ H ₅ or -NHCOC ₆ H ₅ and Χ are chlorine, bromine, cyano, methyl sulfonyl or the nitro group. ' 4.) Azo dye of the formula H ₃ C CN f3
H3CI -N / CU ₂ CH, CH ₁ CH 5.) Azo dye of the formula CN NC-C ^ -N = N-e λ-N 6.) Azo dye of the formula Le Λ V \ 235 CH ₃ CN NC / C ₂ H ₅ C ₂ H ₅ 0 H C ₂ H ₄ OCCH, 309832/1060 7.) Process for the preparation of azo dyes, characterized in that one diazotized anilines of the formula H, C CN ^H 3 ^CX in which X is J.itor, bromine, cyano, nitro or C ₁ -Cw-alkylsulfonyl, combined with coupling components. B.) Process for dyeing and printing fiber materials, characterized in that azo dyes according to claim 1 used, 9.) Fiber materials, dyed and / or printed with azo dyes according to claim 1. 10.) Compound of the formula H ₃ C CN NC in which X is chlorine, bromine, cyano, nitro or C ₁ -Cj.-alkylsulphonyl. Le A \ H ay Ü iJ '"·' ■ 1 0 Ö 0 11.) Process for the preparation of compounds according to claim 10, characterized in that 2,4-dicyan-3,5-dimethylaniline - optionally after previous acylation of the free amino group - in the 6-position halogenated or nitrated, if desired subsequently the halogen atom introduced in the 6-position against a cyano, nitro or alkylsulfonyl group in a manner known per se exchanged and the optionally introduced N-acylamino protective group removed. Le A Hl 235 : i ο ο a ' / l ο 6 ο