DE2436898A1 - AZO DYES - Google Patents

Description

Bayer Aktiengesellschaft 2

Central area of patents, trademarks and licenses

509 Leverkusen, Bayerwerk

K / Schä

3 0. JuH 1974

Azo dyes

The invention relates to azo dyes free of s-sulfo groups the formula

NHR ₂

DN = NT ^ V " ^Q

^R 3 R ₄

wherein

D a by substituents with positive <a values substituted benzene radical or an optionally substituted thiazolyl-2 or benzthiazolyl-2 radical is,

R ₁ and R _{2 represent} a straight-chain, unsubstituted O, -C ^ -alkyl radical,

R ^ is alkyl, cycloalkyl, aralkyl or aryl,

R ^ is hydrogen, alkyl, cycloalkyl, aralkyl, or aryl or together with R, including the N atom, a

Le A 15 777

609800/0971

5- or 6-membered heterocycle can form and

Q stands for hydrogen, a cyano, an optionally substituted carbonamide or carboxylic acid ester group,

as well as their manufacture and use for dyeing synthetic hydrophobic materials. -.

Suitable substituents in D with positive & values are such as in H.A. Staab, "Introduction to Theoretical Organic Chemistry", Verlag Chemie, Weinheim / Bergstrasse 1970, listed are or are - in particular - electron-withdrawing nonionic substituents customary in dye chemistry and the carboxyl group.

Preferred radicals R>. and R ₂ are methyl radicals.

The alkyl radicals R ^ and R, preferably have 1 to 6 carbon atoms and can be substituted, for example, by a cyano, amino, hydroxy, C, -Cg-alkoxy or C.-Cc-alkoxycarbonyl group be.

Suitable cycloalkyl radicals are preferably cyclohexyl radicals which are substituted, for example, by 1 to 3 methyl radicals could be.

Suitable aralkyl radicals R ^ and R # are preferably benzyl and Phenyläthylreste, for example 1 to 3 times through Chlorine, C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy can be substituted.

Suitable aryl radicals R 1 and R ^ are, in particular, optionally 1-bis 3 times by C ^ -C ^ -alkyl, C ^ -C ^ -alkoxy, halogen or cyano

Le A 15 777 - 2 -

«09808/097

substituted phenyl radicals, with halogen being preferred Chlorine is to be understood.

Suitable heterocycles, the R ,. and R ^ together can form are:

Pyrrolidine, piperidine, morpholine, thiomorpholine and N-methylpiperazine, Imidazole.

Suitable radicals Q are, in addition to the preferred cyano group, especially C.-C ^ -alkoxycarbonyl radicals, the carbamoyl radical and radicals of the formula -CONT ^ T ₂ , where T ^ and T _{2 have} their meaning

correspond to that of R _x and R <. * .-

Preferred dyes are those of the formula

NHCH _x
DN = No ^> ^ ^CN II

CH _x ^X

wherein

D, R, and R ^ have the meaning given above. Particularly preferred dyes are those of the formula

Le A 15 777 - 3 -

60 9 8087 0 97

NHCH,

III

worm
X NO

₂ , CN, CONH ₂ , CONW ₃ W ₄ , COW ₃ , COOW ₄ , CP ₃ SOW

Cl, P, Br,

SO ₂ W ₃ ,

SO ₃ NW ₃ W ₄ ,

SO ₂ OW ₃ , SCN or a

is phenylazo substituted by X, Y and Z, where W is defined as R ₃ and W _{1 is} defined as R _1,

Y and Z stand for H or X,

V ₁ for straight-chain or branched C ^ -Cg-alkyl, C ₂ -C ₄ -alkylene-OH, Cj-C ^ -alkylene-OC ^ Cjj-alkyl, cyanoethyl, phenyl-C ₁ -C ₃ -alkyl, phenyl or ToIy1 and

Vp stands for the same or different V ₁ or for hydrogen or V "together with V-, including the N atom, form a pyrrolidine, piperidine or morpholine ring.

In the context of the formula III, such dyes are again preferred ,

where X = NO

Y =

SO ₂ CH,

SO ₂ C ₂ H ₅ ,

SO ₂ OCH ₅ ,

SOpOC-H,

2 » ^{o <} ^ 2 3 ' ο ^> 2_ ^ 2ι 5

SO ₂ NHCH ₃ , SO ₂ NHC ₂ H ₅ , S0 ₂ N (CH ₃ ) ₂ or

H, NO ₂ , CN, Cl, Br or CF ₃ and = H, Cl, Br, CN.

SO ₂ NH ₂ ,

Dyes of the formula III whose diazo component is derived from the following radicals are very particularly preferred:

Le A 15 777

609808/0971

a) T, O «S— (

and

wherein

Y ₁ = H, Cl, Br, NO ₂ , CN or SO ₂ W ₃ , Z ₁ = H, Cl, Br or CN and

T ₃ = methyl, ethyl, NH ₂ , NHCH ₃ , NHC ₂ H ₅ , NH-benzyl, NHC ₂ H ₄ OH, N (CH ₃ ) ₂ or N (C ₂ H ₅ J ₂ .

The new azo dyes are obtained, for example, if one diazotized Amines of the formula

D-NH ₂ IV

wherein

D has the abovementioned meaning with coupling components of the formula

NHR

^R 4

united.

Le A 15 777 - 5 -

609808/0 9 71

The coupling of the diazotized amines IV with the compounds V takes place in a manner known per se in weakly acidic, neutral or weakly alkaline, aqueous or organically aqueous medium, with the occasional addition of an acid-binding medium Means, such as sodium acetate, is recommended.

Examples of suitable diazo components of the formula IV are called:

3- or 4-amino-benzotrifluoride 2-, 3- or 4-chloroaniline 2-, 3- or 4-bromoaniline 2-, 3- or 4-nitroaniline 2-, 3- or 4-cyananiline 2,3-, 2,4-, 2,5- or. 3,4-dichloroaniline, 2,3-, 2,4-, 2,5- or 3,4-dibromaniline, 2,4,5-, 2,4,6-, 3,4,5- or 3,4,6- Trichloroaniline 4-chloro-2-amino-benzotrifluoride 5-chloro-2-amino-benzotrifluoride 5-nitro-2-amino-benzotrifluoride 2-chloro-4-nitroaniline 2-Bromo-4-nitroaniline 2-cyano-4-nitroaniline 4-chloro-2-nitroaniline 4-bromo-2-nitroaniline 4-cyano-2-nitroaniline 2,5- or 2,6-dichloro-4-nitroaniline 2-chloro-6-bromo-4-nitroaniline 2-chloro-5-bromo-4-nitroaniline 2-chloro-5-cyano-4-nitroaniline 2,5- or 2,6-dibromo-4-nitroaniline

Le A 15 777 - 6 -

60 9 808/0971

2,4-dinitroaniline

5-chloro- or 6-chloro-2,4-dinitroaniline 5-bromo or 6-bromo-2,4-dinitroaniline, 2,4,6-trinitroaniline 1 -Amino ^ -cyan ^ -chlorobenzene 4-cyano-3-nitroaniline 2,5-dichloro-4-cyano-aniline 1-amino-2,4-dicyanobenzene 1-Amino-2,6-dicyan-4-nitrobenzene 1-Amino-2,5-dicyan-4-methyl-sulfone

1 -amino ^ -chlor ^ -methyl-sulfon "

1 -Amino ^ -chlor ^ -ethyl-sulfon 1-amino-2,5-dichloro-4-methyl-sulfone 1-Amino-2,5-dichloro-4-ethyl sulfone 2-methylsulfonyl-4-nitroaniline 4-methylsulfonyl-2-nitroaniline 4-methylsulfonylaniline 4-ethylsulfonylaniline 4-butylsulfonylaniline 4-Benzylsulfonylaniline 2-, 3- or 4-amino-acetophenone 2-amino-5-nitro-acetophenone 2-, 3- or 4-amino-benzophenone 4-amino-5-nitro-benzophenone 2-, 3- or 4-amino-benzoic acid Ethyl 2-, 3- or 4-aminobenzoate, n-butyl 2-, 3- or 4-aminobenzoate 2-, 3- or 4-amino-benzoic acid cyclohexyl ester 2-, 3- or 4-amino-benzoic acid amide 2-, 3- or 4-aminobenzoic acid monomethylamide 2-, 3- or 4-aminobenzoic acid dimethylamide 2-, 3- or 4-amino-benzoic acid-ethylenimide 2-, 3- or 4-amino-benzoic acid-isopropylamide 2-, 3- or 4-amino-benzoic acid diethylamide 3-amino-cinnamic acid

4-aminophenylacetic acid

Le A 15 777 - 7 -

609808/0971

2-, 3- or 4-amino-benzoic acid-di-n-butylamide 2-, 3- or 4-amino-benzoic acid morpholide 2-, 3- or 4-aminobenzoic acid anilide 2-, 3- or 4-aminobenzoic acid-N-methylanilide 4-aminophenyl thiocyanate

2-fluoro-4-nitro-aniline

Ethyl 2-, 3- or 4-amino-benzene-sulfonic acid 2-, 3- or 4-aminobenzene sulfonic acid phenyl ester 2-, 3- or 4-amino-benzene-sulfonic acid amide 2-, 3- or 4-aminobenzenesulfonic acid monomethylamide 2-, 3- or 4-aminobenzenesulphonic acid dimethylamide 2-, 3- or 4-aminobenzenesulphonic acid ethylene imide 2-, 3- or 4-amino-benzenesulphonic acid monoethylamide 2-, 3- or 4-amino-benzenesulphonic acid diethylamide 2-, 3- or 4-aminobenzenesulfonic acid di-n-butylamide 2-, 3- or 4-aminobenzenesulfonic acid morpholide 2-, 3- or 4-aminobenzenesulfonic acid cyclohexylamide 2-, 3- or 4-aminobenzenesulfonic acid anilide 2-, 3- or 4-amino-benzenesulfonic acid-N-methyl-anilide 1-ChloΓ-2-aminobenzene-4-sulfonic acid dimethylamide 1-chloro-2-aminobenzene-5-sulfonic acid-ß-ethoxy-ethylamide 1-chloro-3-amino-benzene-4-sulfonic acid amide 1-chloro-4-amino-benzene-2-sulfonic acid dimethylaInide 1,4-dichloro-2-amino-5-benzenesulfonic acid amide 1,4-dichloro-2-amino-5-benzenesulfonic acid methylamide 1,4-dichloro-2-amino-5-benzenesulfonic acid dimethylamide 1,4-dichloro-2-amino-5-benzenesulphonic acid ethylamide 1,4-dichloro-2-amino-5-benzenesulfonic acid diethylamide 1,4-dichloro-2-amino-5-benzene sulfonic acid n-butylamide 1,4-dichloro-2-amino-5-benzenesulfonic acid morpholide 1 ^ -Dichlor ^ -amino ^ -benzenesulfonic acid-cyclohexylamide 1,4-dichloro-2-amino-5-benzenesulfonic acid benzylamide

Le A 15 777 - 8 -

6,9808 / 0971

5-nitro-2-aminothiazole 2-aminobenzothiazole

2-Amino-6-methoxy-benzothiazole 2-Amino-6-nitro-lienothiazole 2-Amino-6-chloro-benzothiazole 2-Amino-6-methylsulfonyl-benzothiazole 2-amino-6-thiocyanato-benzothiazole 4-amino-azo-benzene

Several synthetic routes are recommended for the preparation of the coupling components V.

One method is characterized in that compounds of the formula VI

VI

wherein

Q 'represents CN or a carbonamide group, by treatment with POCl, and / or PCI, - - expediently in the presence of tertiary organic bases - into the compound of formula VII

Cl

CN

VII Cl

Le A 15 777 - 9 -

6 (19808/0971

7436898 JlO

transferred, then the halogen atoms contained therein against amino groups or radicals defined in more detail above Exchanges nitrogen heterocycles and, if necessary, subsequently converts the cyano group into an amide or ester group in a manner known per se (cf. e.g. Dutch patent application 7 216 930).

The conversion of the cyano group into an amide group can also take place the compound of formula VII can be made, for example by treatment with 70-90% sulfuric acid 70 - 100 ° (see e.g. DOS 2 062 717).

The compounds of the formula VI are known (cf. Arch. Pharm. 296 , 501 (1963)). Their conversion to VII takes place at temperatures of 100-160 ^° C., if appropriate in the presence of suitable tertiary organic bases, such as pyridine and N, N-dimethylaniline.

Suitable solvents for the exchange reaction are, for example, methanol, ethanol, butanol, acetone, β-methoxyethanol, dimethyl sulfoxide, dimethylformamide or ethylene glycol dimethyl ether. The reactions can also be carried out under pressure. To bind the hydrogen chloride released during the reaction with amines, either excess amine or acid-binding agents such as Na ₂ CO- ,, NaHCO- * or MgO are used.

Another method of representing V is characterized by that pyridinium salts of the formula VIII

Le A 15 777 - 10 -

609808/097 1

ΛΑ

VIII

Cl (-)

with at least 2 equivalents of an amine HNR- ^ R ^ at temperatures of 80 "to 200 ⁰ C, preferably 120 to 150 ° C, and converts the cyano group in a manner known per se into ester or amide groups.

Suitable amines

are e.g .:

Methylamine, ethylamine, n-propylamine, i-propylamine, n-butylamine, i-butylamine, n-hexylamine, n-octylamine,

ß-methoxyethylamine, ß-ethoxyethylamine, 3-hydroxypropylamine- (l), 3-methoxypropylamine- (l), 3-ethoxypropylamine- (l), 3-butoxypropylamine- (1), 3-aminopropyl-2-ethyl-hexyl ether, 4-hydroxybutylamine- (1), 4-ethoxybutylamine- (l),
1,4-diaminobutane, 1-amino-4-dimethylaminobutane,

Dimethylamine, diethylamine, di-i-propylamine ,, di-n-propylamine, Di-n-butylamine, methylbutylamine, ethylbutylamine, methylhexylamine, Pyrrolidine, piperidine, morpholine, N-methylpiperazine,

Cyclohexylamine, 4-amino-l-methylcyclohexane, aminomethylcyclohexane,

Aniline, o-, m- or ρ-aminotoluene,

Benzylamine, 1-amino-1-phenylethane, 1-amino-2-phenylethone.

Le A 15 777

- 11 -

60 9 808/097

The reaction of VIII with these amines takes place either in excess amine or in the presence of an inert one Solvents such as chloroform, acetonitrile, tetrahydrofuran and others - optionally under pressure.

The pyridinium salts VIII are partly from Angew. Chemie 84 , 1184 (1972) known or obtainable by the process described there.

Suitable coupling components V are, for example, the general compounds listed in the table below Formula IX:

Le A 13 777 - 12 -

609808/0971

CHg-

(ix)

Cix) H R ₆ CH ₃ ι) H ^C 2 ^Η 5 2) H C ₃ H ₇ 5) H C ₄ H ₉ 4) H CH ₂ phenyl 5) H CH ₂ -CH ₂ -phenyl 6) H CH ₂ -CH ₂ -OCHg 7) H CBg-CH ₂ -OCgH ₅ 8th) H CH ₂ -CHg-OC ₄ H ₉ 9) H CH ₂ -CH ₂ -CH ₂ -OCHg 10) H CH ₂ -CHg-CHg-OC ₂ H ₅ H) H CHg-CBg-CHg-OC ₄ H ₉ 12) H - (CH ₂ ) ₃ -0-CH (C ₂ H ₅ ) - (CBg) ₄ -CHg 13) H -CH ₂ -CH ₂ -CH ₂ -OH 14) Ξ -CH ₂ -CH ₂ -CH ₂ -CH ₂ -OH 15) H CH ₂ -CH ₂ -CH ₂ -CN 16) H CH ₂ -CH ₂ -CH ₂ -CB ₂ -NBg 17) H CB ₂ -CBg-CH ₂ -NHCH ₃ 18) H CH ₂ -CBg-OCOCH, 19)

Le A 15 777

- 13 -

60 9808/09

IX R ₅ R ₆ 20) H CH ₂ -CH ₂ -CH ₂ -OCOC ₂ H ₅ 21) H CH ₂ -COOCH ₃ 22) H CH ₂ -CH ₂ -COOCHg 23) H CH ₂ -CHg-COOC ₂ H ₅ 24) H CH ₂ -CH ₂ -COOH 25) H Cyclohexyl 26) H CH ₂ cyclohexyl 27) CH ₅ CHj 28) C ₂ H ₅ C ₂ H ₅ .29) C ₃ H ₇ C ₃ H ₇ 30) C ₄ H ₉ C ₄ H ₉ 31) CHg C ₄ H ₉ 32) CHg CH ₂ -CH ₂ -CH ₂ -OCHg 33) ■■ CIL - ~ GiL> "™ CHg ■■ CSg" " 34) -CH ₂ - (CH ₂ ) g -CH ₂ - 35) -CH ₂ -CH ₂ -0-CH ₂ -CH ₂ -

Le A 15 777

- 14 -

«09808/0971

-CB ₂ -CB ₂ -NCB ₃ -CH ₂ -CB ₂ -

-CH = N-CH = CH-

'Le A 15

609808/09

The new dyes or their mixtures with one another or with other dyes are very suitable for dyeing and printing structures made of synthetic hydrophobic materials, such as polyolefins, polyvinyl compounds, Cellulose 2 1/2 acetate and especially cellulose triacetate and polyester materials. They then produce yellow to red dyeings using the usual dyeing and printing processes. and prints with good fastness properties, in particular good lightfastness and sublimation fastness. The good thing is still to be emphasized Drawability and build-up capacity of the dyes when dyeing polyester fiber materials from aqueous liquor in the exhaust process.

Le A 15 777 - 16 -

609 8 08/0371

Al

Preparation of the starting compounds (VI) - ″ or (VIl); Example 1;

2,4 »6-trihydroxy-nicotinic acid nitrile (Χ)

To a solution of 11.5 parts of sodium in 400 parts by volume of absolute ethanol are added 40 parts of diethyl malonate, 28.2 parts of ethyl cyanoacetate and 4> 25 parts of ammonia (as an approximately 25% ethanolic solution) and the mixture is heated in a for 8 to 10 hours autoclave at 110-120 ⁰ C. After cooling, the reaction product is filtered off and dissolved in water. The reaction product is precipitated by adding hydrochloric acid to the aqueous solution. After filtering off with suction and drying, 29 parts (77.5% of theory) of crude 2,4,6-trihydroxynicotinonitrile (x) which is sufficiently pure for further processing to 2,4,6-trichloronicotinonitrile (Xl) are obtained. A sample purified according to the information provided by EE Schulte and R. Mang (Arch. Phar. 296 (1963) 509) was found to be identical to the product obtained by the same authors from diethyl malonate and cyanoacetamide in the presence of sodium ethylate. '

Example 2;

2,4,6-trichloronicotinic acid nitrile (-Xl)

304 parts of 2,4,6-trihydroxy-nicotinonitrile (X) are heated together with 2,000 parts by volume of phosphorous oxychloride in an autoclave for 6 hours at 150 ⁰ C to give not allowed to rise atm by venting the hydrogen chloride formed the pressure on 10th The phosphorus oxychloride is then distilled off as far as possible from the clear brown solution under reduced pressure and the residue is then poured into ice water. The mixture is then stirred for 2 to 3 hours until the phosphorus compounds are completely hydrolyzed, the temperature of the aqueous suspension not being allowed to rise above 25 ° by occasionally throwing in ice. The crystalline precipitated substance is then filtered off with suction and washed thoroughly with water. After drying in vacuo, 331 parts of crude 2,4,6-trichloro-nicotinonitrile (XI) (80% of theory) of melting point '110-115 ⁰ C obtained which can be purified by reprecipitation from about 3ooo parts by volume of mineral spirits. Yield after dissolving with work-up of the mother liquor: 304 parts ($ 70 of theory). Le A 15 777 - 17 _

6098.087097t -

Light brown crystals with a melting point of 112-115 ° C (literature: 112 °, 117 °)

Production of the coupling components (V); Example 5;

20.75 parts of 2,4,6-trichloro-nicotinonitrile (XI) are added in 150 parts by volume of dimethylformamide gradually with 16 parts of diethylamine to give ensures by external cooling that the temperature of the reaction mixture does not exceed 4O ⁰ C increases. Stirring is continued at this temperature until thin layer chromatography (silica gel, flow agent methyl chloride, observation under UV light, wavelength 254 nm) no longer shows any starting product. The reaction mixture is then poured into ice water and filtered off with suction. After drying, 21 parts of a crude product, which melts at 106-116 ⁰ C is obtained approximately. By reprecipitation from methanol obtained therefrom 17 parts of a melt at 124-126 ⁰ C Compound of the probable formula (XIL).

(XII)

The mother liquor contains small amounts of the isomeric compounds

Cl

CN

and

(C ₂ Hs) ₂ N ^ F

24.4 parts of 2-diethylamino-3-cyano-4,6-dichloropyridine (Xil) are suspended in 250 parts of 30 $ aqueous methylamine solution and heated for 5 hours at 140-15O ⁰ C in an autoclave. It is then cooled to about 0 ⁰ C, suction filtered the yellow crystal mass, and 19 parts, after drying approximately a compound of the probable formula (XIII),
Le A 15 777 -18-

6 0 9 8 0 8/0371

(XIII)

which melts after recrystallization from ethanol at 130-152 ⁰ C with decomposition.

Example 4;

23.3 parts of 2-chloro-3-cyano-4-methylamino-6-amino-lί-methyl-pyridinium chloride (represented by AL Cossey et al., Angew. Chem. 84 "II84 (1972)) are dissolved in about 100 Parts of benzylamine entered and ^{heated to 130 0} C for 3-4 hours. After cooling to approx. 50 ^° C., the solution is added to approx. 300 parts of ice water, a yellowish oil separating out and slowly crystallizing. It is filtered off with suction, washed with water, dried and 19-20 parts of the compound (XIV) are obtained,

(XIY) CH ₃ -I

after recrystallization from ethanol at 148-153 ° C with decomposition melts.

Example 5;

23.3 parts of 2-chloro-3-cyano-4-niethylamino-6-amino-li-methyl-pyridinium chloride are heated in 250 parts of 30 $ aqueous methylamine solution in an autoclave for 5 hours at 13O ⁰ C.

Then cooled the reaction mixture to 0 ⁰ C, filtered off under suction, the weakly colored brown crystals, washed with a little water and 12 after drying approximately - 13 parts of the compound of formula (XV),

Le A 15 777 - 19 -

98087

IQ

(XV)
CH ₃ -I

after recrystallization from ethanol at 153-154 ⁰ C melts (dec.).

Example 6;

23.3 parts of 2-chloro-3-cyano-4-methylamino-6-amino-ll-methyl-pyridinium chloride in 100 parts of γ-Athoxypropylamin 4 hours to 120 125 ^° C heated. The excess γ-ethoxypropylamine is then distilled off in vacuo and the pale yellow oil that remains is taken up in approx. 200 parts of aqueous acetic acid. According to analytical determination, the solution contains approx. 23 parts of the compound of the formula (XVl)

(XVI)
CH ₃ -ΝΗ '^ · ϊΚ ^ ΪΓΗ- · σΗ ₂ -CH ₂ -CH ₂ -0-C ₂ B ₅

and is used for further reactions without purification.

Example 7:

23.3 parts of 2-chloro-3-cyano-4-πlethylamino-6-amino-lί-methyl-pyridinium chloride are suspended in 150 parts of pyrrolidine and heated for 5 hours at 150 ⁰ C in an autoclave. Then distilled the excess pyrrolidine as completely as possible from, are added to the still hot, oily-brown residue about 100 parts of ethanol, heated to boiling for about 10 minutes, cooled to -18 ⁰ C, suction filtered yellowish crystal and washed with a lot of water. After drying, about 19 parts of the obtained compound (XVIl) as a pale yellowish powder, mp. I6I 164 ⁰ C (dec.).

Le A 15 777 - 20 -

6098 0 8/0 9

(XVIl)

Example 8;

23.3 parts of 2-chloro-3-cyano-4-niethylamino-6-amino-] ir-methyl-pyridiniunichlorid are heated to 120-128 ° C. in 100 parts of morpholine for about 2 hours. It is cooled to 0 ^° C., the pale yellow precipitate is filtered off, washed with plenty of water and, after drying, about 8 parts are obtained
a compound that is probable according to the mass and NMR spectrum
Formula (XVIIl)

(XVIIl)

their formation by demethylation of the "normal" reaction product (iXX) can be explained.

The piltrate obtained after the separation of (XVIIl) becomes dry evaporated and the remaining brown-viscous oil in about 150 parts Glacial acetic acid added. According to analytical determination, this solution contains approx. 14 parts of the connection (iXX),

NHGB ₃

CH ₃ which can be used for further reactions without purification.

Le A 15 777 - 21 -

80 8 / 09-71

Preparation of the dyes (i); Example 9;

26.9 parts of 1,4-dichloro-2-amino-5-benzenesulfonic acid-lI-ethylamide are diazotized with nitrosylsulfuric acid in a known manner in ^ Obeyx sulfuric acid and treated with a solution of 23.1 parts of 2-pyrrolidino-3-cyano- 4,6-bis (methylamino) pyridine (XVIl) combined in about 200 parts of glacial acetic acid. To complete the coupling, the pH of the reaction mixture is increased to about 3-4 by adding aqueous sodium acetate solution and the precipitated dye of the formula (XX) is then filtered off,

(XX)

washes with water and dries. You get about 47 parts of a reddish one Powder that colors polyester materials in golden yellow tones.

Example 10;

16.3 parts of 2-cyano-4-nitro-aniline are in a known manner in glacial acetic acid / Propionic acid is diazotized with nitrosylsulfuric acid at 0 - 5 ° C. The diazonium salt solution is added to a solution of 26.3 parts of 2- (γ-ethoxypropylamino) -3-cyano-4,6-bis (methylamino) pyridine (XVl) in approx. 150 parts of glacial acetic acid, increases the pH by adding aqueous Sodium acetate solution to 3 to 4 », after the coupling has ended, the precipitated dye of the formula (XXl) is filtered off,

(XXI) -CH ₂ -CH ₂ -OC ₂ H ₅

Le A 15 777 -ZZ-

washes with water and after drying contains approx. 40 parts a dark red powder that dyes polyester materials in strong scarlet shades. \ ■

Example 11;

17.1 parts of 4-methylsulfonylaniline are suspended in a known manner in about 200 parts of aqueous hydrochloric acid solution at 0 ⁰ C and diazotized with 30 ^ aqueous sodium nitrite solution. The diazonium salt solution is added to a solution of 26.7 parts of 2-benzylamino-3-cyano-4-bis (methylamino) pyridine (XIV) in about 200 parts of glacial acetic acid and the pH of the solution is increased by adding aqueous solution Sodium acetate solution to approx. 3 - "4 · The precipitated dye of the formula (XXII)

CH ₃ -

is suction filtered, washed with water and dried. You get approx. 42 parts of a reddish powder that strengthens polyester materials in yellow tones.

In the table below there are other dyes in accordance with the present invention Invention and the color tones of the dyeings and prints obtainable therewith on polyester materials.

Le A 15 777 - 23 -

NHCB ₃

CB ₃ -N

No. 4-chlorophenyl "4 H Benzyl H -CHg- ( H CH ₂ -CHg-CH ₂ -OCH ₃ Hue on
polyester ι) 4-nitrophenyl H Benzyl H H C ₄ H ₉ yellow 2) 4-cyanophenyl H Benzyl H H CBg-CBg-CH ₂ -OC ₂ Bg orange 3) 2,5-dichlorophenyl H C ₄ H ₉ H H Benzyl yellow 4) 2-trif] xxamethyl-4-
nitro-phenyl H C ₄ H ₉ H CH ₂ ) g-CH ₂ - yellow 5) 2-chloro-4-nitrophenyl -CH ₂ - (CBg) ₂ -CH ₂ - H C ₄ H ₉ orange 6) 2-methylsulfonyl-4-
nitro-phenyl H CHg-CH ₂ -CH ₂ -OC ₂ H ₅ Scarlet fever 7) 2-cyano-4-nitro-6-bromo
phenyl C ₂ H ₅ Benzyl Red 8th) 2-bromo-4-nitrophenyl C ₂ H ₅ Benzyl Red 9) 2,4-mcyanophenyl H C ₄ H ₉ Red 10) 2,5-dichloro-4-nitro-
phenyl H C ₄ H ₉ Scarlet fever 11) 2-chloro-4-nitro-6-
cyanphenyl H CH ₂ -CH ₂ -OCH ₃ Red 12) 2,4-dinitrophenyl C ₂ H ₅ Red 13) 4-ethylsulfonylphenyl C ₂ H ₅ Red 14) 4-butylsulfonylphenyl C TJ
C ₄ H ₉ yellow 15) 4-benzylsulfonylphenyl Benzyl yellow 16) 2,5-dichloro-4-methyl-
sulfonylphenyl C ₄ H ₉ yellow 17) 4-methylsulfonyl-2-
nitro-phenyl orange 18) 4-sulfonami dophenyl orange 19) 2-chloro-4-sulfonamido-
phenyl yellow 20) 2-chloro-4-N-ethylsul-
phonamido-phenyl yellow 21) 2,5-dichloro-4-sulfone
amidophenyl yellow 22) 2,5-Bichlor-4-N-
methyl sulfonamido
phenyl yellow 23) yellow

Le A 15 777

- 24 -

DS8Oß / 097 1

Where. D. H -CBg H . ^R 4 Hue on
polyester 24) 2,5-dichloro-4-N-
ethyl sulfonamido
phenyl -CB ₂ H ' CBg-CB ₂ -OCBg yellow 25) 2,5-Mchlor-4-N, N-
dimethyl sulf on
amidophenyl H -CB ₂ -O-CBg-CBg-
- - - yellow 26) 2,5-Mchlor-4-N, N-di-
ethyl sulfonamido
phenyl H ■ - (CBg) ₂ -CBg- yellow 27) Thiazolyl-2 C ₂ H ₅ C ₄ B ₉ yellow 28) Benzthiazolyl-2 ^C 2 ^H 6 Benzyl orange 29) 6-chloro-benz-
thiazolyl-2 H CH ₂ -CBg-CB ₂ -OCB ₃ Scarlet fever 50) 6-nitro-benzthia-
zolyl-2 H CBg-CH ₂ -CH ₂ -OCHg Scarlet fever 31) 2-chloro-5-trifluoro-
methylphenyl H C ₂ H ₅ yellow 32) 2-cyano-5-chlorophenyl H C ₂ V yellow 33) 2,5-dichloro-4-cyano
phenyl CE ₂ -CB ₂ -CH ₂ -OCH ₃ orange 34) 4-carboethoxyphenyl Benzyl yellow 35) 4-phenylphenyl C ₄ H ₉ ■; ■■ Scarlet fever 36) 2,4,6-trichlorophenyl CH ₂ -CBg-OC ₂ H ₅ golden yellow

Le A 15 777

Claims (1)

2436B9B 7S $ Patent claims : 1. Sulpho group-free azo dyes of the formula NHR ₂ D-N = N ' wherein D is a benzene radical substituted by substituents with positive £ values or an optionally substituted thiazolyl-2 or benzthiazolyl-2 radical is, R ₁ and R _{2 represent} a straight-chain unsubstituted C ^ -C ^ -alkyl radical, R-z optionally substituted alkyl, cycloalkyl, aralkyl or is aryl, I R ₁ is hydrogen, optionally substituted alkyl, cycloalkyl, aralkyl or aryl, or together with R, can form a 5- or 6-membered heterocycle including the N atom, and Q stands for hydrogen, a cyano, an optionally substituted carbonamide or carboxylic acid ester group. 2. Sulpho group-free azo dyes according to claim of the formula Le A 15 777 - 26 - δ: Q 9 6 0 8/0971 NHCH ₃
CN D, R, and R ^ have the meaning given in claim 1. 3. Sulpho group-free azo dyes according to claim 1 and 2, wherein D is one by substituents with positive £ values substituted benzene radical. P. 4. Sulpho group-free azo dyes according to Claim 1 of the formula NHCH ₃ wherein X NO ₂ , CN, CONH ₂ , CONW ₃ W ₄ , COW, COOW ₄ , CP ,, Cl, P, Br, SO ₂ W ₃ , SOW, SO ₂ NH ₂ , SO ₂ NW W ₄ , SO ₂ OW ₃ , SCN or substituted by X, Y and Z is phenylazo, wherein W ₃ as R ₃ and W ₄ are as defined R _4, Y and Z stand for H or X, V ^ for straight-chain or branched C ₁ -Cg -AlkVl, C ₃ -C ₄ -alkylene-OH, C ₂ -C ₄ -alkylene-OC ₁ -C ₄ -alkyl, cyanoethyl, phenyl-C ₁ -C ₃ -alkyl , Phenyl or tolyl and V ₂ stand for identical or different V ₁ or for hydrogen or V_ together with V ₁ including the N atom can form a pyrrolidine, piperidine or morpholine ring. Le A 15 777 - 27 - 6 Π 9 ί! Ο β / 0971 5. Azo dyes free of sulfo groups according to claim 4, wherein χ = NO ₂ , SO ₂ CH ₃ , SO ₂ C ₂ H ₅ , SO ₂ OCH ₃ , SO ₂ OC ₆ H ₅ , SO ₂ NH ₃ , SO ₂ NHCH ₃ , SO ₂ NHC ₂ H ₅ , SO ₂ N (CH ₃ ) ₂ or SO ₂ N (C ₂ H ₅ ) ₂ Y = H, NO ₂ , CN, Cl, Br or CF ₃ and Z = H, Cl, Br, CN. 6. Azo dyes free of sulfo groups according to claim of the formula NHCH, N = Y ₁ = H, Cl, Br, NO ₂ , CN or SO ₃ W, Z ₁ = H, Cl, Br or CN and V ₁ and V _{2 have} the meaning given in claim 4. 7. Sulpho group-free azo dyes according to Claim 1 of the formula NHCH, N = T ₃ O ₂ S * 3 ^V 2 T ₃ = methyl, ethyl, NH ₂ , NHCH ₃ , NHC ₂ H ₅ , NH-benzyl. NHC ₂ H ₁₁ OH, N (CH ₃ J ₂ or Le A 15 - 28 - fi fi 9 80B / 0971 Al the radicals V ^, V ₂ , have meaning. and Z _{1 mentioned} in claim 6 Azo dye according to Claim 1 of the formula 9. Azo dye according to Claim 1 of the formula CH ₃ - - CH ₂ 10. A process for the preparation of sulfo-free azo dyes, characterized in that one diazotized Amines of the formula D - NH wherein D has the meaning given in claim 1, with coupling components of the formula NHRo R ₁ mr ^ N ^ -N Le A 15 777 - 29 - 8 / 0-9 7 1 where R ₁ , R ₂ , R- ^, R ^ and Q have the meaning given in claim 1, combined. 11. Process for dyeing and / or printing synthetic Fiber materials, characterized in that sulfo group-free azo dyes according to Claim 1 are used. 12. Synthetic fiber materials, dyed and / or printed with azo dyes according to claim 1. Le A 15 777 - 30 - € 09808/0971