DE2733577A1 - AZO DYES - Google Patents

Description

Bayer Aktiengesellschaft

Central area of patents, trademarks and licenses

Azo dyes

5090 Leverkusen, Bayerwerk Jo-My-kl

The present invention relates to azo dyes in the form of the free acid of the formula

N = N

(SO ₃ H)

(D

R.

(SO ₃ H) ₀ , in which

R ₁ = H or a substituent, R ₂ = alkyl, aryl, R ₃ = H, alkyl, cycloalkyl, aralkyl, R ₄ = H or a substituent η = 1, 2 or 3,

o = 0 or 1; ρ = O or 1 and 0 + ρ = 1 or 2; their manufacture and use for dyeing natural

and synthetic fiber materials.

The alkyl, cycloalkyl, aralkyl and aryl radicals can optionally be further substituted .

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Suitable substituents R ₁ or R ₄ are all radicals which can be linked to aromatics, such as fluorine, chlorine, bromine, cyano, nitro, trifluoromethyl, alkyl, aryl, alkoxy, alkoxycarbonyl, alkylcarbonyl, arylcarbonyl, alkylsulfonyl, arylsulfonyl, alkylcarbonylamino, arylcarbonylamino, with below Alkyl and alkoxy are preferably those radicals with 1-4 carbon atoms and aryl is preferably to be _{understood as meaning phenyl radicals optionally substituted by F, Cl, Br, nitro, C 1} -C ₄ -alkyl and C.-C.-alkoxy.

Suitable radicals R ₂ are in particular C 1 -C 4 -alkyl, especially methyl and phenyl. Suitable alkyl radicals R ₃ are in particular those with 1-5 carbon atoms. They can be straight-chain or branched, optionally partially unsaturated and further substituted, for example by hydroxy, O-C.-C.-alkyl, O-acyl, F, Cl, Br, I, cyano, aryl as defined above, carboxy, carbo -C.-C ₄ -AlkOXy, carbonamido with optionally one or two C ₁ -C ₄ -alkyl substituents on the amide nitrogen, aminoacyl, aminodi-C ₁ -C ₄ -alkyl.

A suitable acyl of the O-acyl and the aminoacyl groups is formyl, optionally _{C.-C 4 -alkylcarbonyl monosubstituted by chlorine, bromine, C 1} -C ₄ -AIkOXy, phenyl or methylphenyl, optionally C ₂ -C ₄ -alkenylcarbonyl monosubstituted by bromine, C.-C ₄ -alkoxycarbonyl, phenoxycarbonyl, cyclopentylcarbonyl, optionally substituted by alkyl cyclohexylcarbonyl, optionally mono- or disubstituted or given by Cj-C.-alkyl

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if aminocarbonyl monosubstituted by cyclohexyl, C 1-4 alkylcyclohexyl, phenyl, C 1-4 alkylphenyl, chlorophenyl, bromophenyl or trifluoromethyl, optionally by C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, hydroxy, C ₁ -C ₄ -Alkylcarbonyloxy, chlorine, bromine, nitro, trifluoromethyl-substituted benzoyl, naphthylcarbonyl, thenoyl, furoyl, pyridoyl, C ₁ -C ₄ -AlkYlSuIfOnYl, optionally by fluorine, chlorine, bromine, trifluoromethyl, C ₁ -C ₄ -AlkYl , C ₁ -C ₄ -AlkOXy, nitro or C ₁ -C ₄ -alkylcarbonylamino substituted benzenesulphonyl, naphthylsulphonyl, cyclohexylsulphonyl or C ₁ -C.-dialkylaminosulphonyl.

Preference is given to dyes of the formula (I) in which R ₁ = H or a substituent with a greater electron refinity than carbon, such as fluorine, chlorine, bromine, cyano, nitro, trifluoromethyl, alkoxycarbonyl, alkylcarbonyl, arylcarbonyl, alkylsulfonyl and arylsulfonyl, where among Alkyl and alkoxy are preferably those radicals with C.-C ₄ -Atarnen and under aryl are preferably phenyl radicals optionally substituted by F, Cl, Br, nitro, C ₁ -C ₄ -AlkYl and C ₁ -C _{4 -AlkOXy;}

R- = CH ₃ or phenyl,

R, ^{= have} the meanings given above; R ₄ = H, C ₁ -C ₄ alkYl

and n = 1; o = 0.1; p = 0.1 and ο + ρ = 1.

Those dyes which are in the form of the free acid of the formula are particularly preferred

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CN

"- N = N - '^ ν --ο (II)

SO ₃ H ^R 6 correspond to, wherein

R, - H, chlorine or bromine,

R, methyl or phenyl,

R ₇ H or methyl and

R _fi H, C ₁ -C ₄ alkyl, benzyl.

Very particularly preferred dyes are those which are in the form of the free acid of the formula

R ₅ nc-t 'yN = N-

3

correspond to where

R ₁ -, R, and Ro have the meaning given. Dyes of the formula are also particularly preferred

(CN) _n ,

^m / \ (IV)

^R 9

in which

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R ₉ = H, Cl, Br, CH ₃

and m = 1 or 2 and

R, and R _{0 have} the meaning given above.

D O

The new dyes are obtained by adding amines of the formula

CN

(V) (SO ₃ H) ₀

where η, ο and R _{1 have} the meaning already mentioned, diazotized in a known manner and in an acidic to neutral medium with coupling components of the formula

(VI)

where p, R- »R ₃ and R. have the meaning already given, coupling in an aqueous, aqueous-organic or purely organic medium.

The coupling components of the formula (VI) are known. They are obtained by the methods described in the literature.

The diazo components of the formula (V) are also known or can be prepared by known processes.

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Surprisingly, the aminoaldehyde also succeeds formula

O = CH-C V-NH.

(VI)

SO ₃ H

in concentrated formic acid with hydroxylamine at temperatures between 50 and 110 ° C without formylation of the amino group into the nitrile of the formula

-NH.

to convert. If this method is applied to amino aldehydes free of sulfo groups, such as 4-aminobenzaldehyde or 5-amino-2-chlorobenzaldehyde on, the formylaminobenzonitriles are always obtained.

When applying the method to substituted sulfoaminobenzaldehydes the corresponding substituted amino-sulfo-benzonitriles are obtained.

The present invention also relates to nitriles of the formula

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in which R ₁ and η have the meaning given above, as well as their salts, in particular the alkali metal salts (Na, K).

The new dyes of the formula (I) are suitable for dyeing and printing natural and synthetic fiber materials, in particular fiber materials containing nitrogen atoms such as wool, silk, leather and polyamide fibers, polyamide fibers in particular those made from synthetic polyamides such as polycaprolactam or condensation products are understood from adipic acid and hexamethylenediamine.

The dyes are absorbed well on polyamide fibers from a neutral to weakly acidic dye bath and deliver yellow dyeings with very good levelness with very good wet fastness properties and excellent light fastness properties.

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example 1

19.8g of 5-amino-2-cyanobenzenesulfonic acid are dissolved in 100 ml H-O dissolved, mixed with 30 ml of concentrated hydrochloric acid and at 0 - 5 ° C with 70 ml of 10 percent sodium nitrite solution diazotized. After removing a small excess of nitrite with aminosulfonic acid, the Diazo solution with stirring to a solution of 19.3 g of 2-phenylindole in 200 ml of acetone. The one that occurs immediately Coupling is accelerated by blunting the pH to 4-5. The deposited dye the formula

is suctioned off, washed and dried after the coupling is complete. 38.5 g of a light brown powder are obtained, the polyamide has a strong yellowish orange color and is characterized by high color strength and excellent lightfastness excels.

Table 1 lists other valuable dyes that are obtained when 5-amino-2-cyanobenzenesulfonic acid is used couples to the indicated indoles.

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Table 1

example Coupling component Color on polyamide reddish
yellow 2 1-methyl-2-phenylindole Some ] 3 1- (2-cyanoethyl) -2-phenylindole reddish gel reddish
yellow 4th 1- (2-hydroxyethyl) -2-phenylindole Reddish yellow 5 2-methylindole Some 6th 1,2-dimethylindole yellow 7th 1- (2-cyanoethy1) -2-methylindole Some reddish
yellow 8th 1- (2-hydroxyethyl) -2-methylindole yellow reddish
yellow 9 1- (2-chloroethyl) -2-methylindole yellow reddish
yellow 10 1- (2-hydroxybutyl) -2-methylindole yellow reddish
yellow 11 1- (2-hydroxy-2-methylpropyl) -2-
methylindole Some reddish
yellow 12th 1- (2-hydroxy-2-methyl-3-
butenyl) -2-methylindole Some 13th 1- (2-hydroxy-3-phenoxy) -2-
methylindole Some reddish
yellow 14th 1- (2-chloro-3-phenoxy) -2-
methylindole Some 15th 1- (2-hydroxy-2-phenylethyl) -2-
methylindole Some 16 1-butyl-2-methylindole yellow Some

17 1- (2-dimethylaminoethyl) -2- yellow methylindole

18 1- (3-acetaminopropyl) -2-methyl-yellow indole

19 1- (3-Benzaminopropyl) -2-methyl-yellow indole

20 1- (3-phenylaminocarbonylamino-yellow propyl) -2-methylindole

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Table 1 continued Example of a coupling component Color on polyamide

21 1- (3-toluenesulfonamidopropyl) -2-methylindole

22 1- (2-butylaminocarbonyloxypropyl) -2-methylindole

23 2,5-dimethylindole

24 5-chloroacetaminomethyl-2-methylindole

25 5-chloroacetaminomethyl-2-phenylindole

26 5-chloroacetaminomethyl-i, 2-d ime thylindol

27 5-chloroacetaminomethyl-1- (2-cyanoethyl) -2-methylindole

28 2-methyl-5-nitroindole

29 5-nitro-2-phenylindole

30 1-benzyl-2-phenylindole

31 1-ethyl-2-phenylindole

32 1-Benzyl-2-methylindole

33 1- (4-chlorobenzyl) -2-methylindole

34 1- (4-methylbenzyl) -2-phenylindole

35 2-methyl-5-indolesulfonic acid

36 2-phenyl-5-indolesulfonic acid

37 5-acetamino-2-methylindole

38 5-acetamino-1,2-dimethylindole

39 2,7-dimethylindole

40 1-ethyl-2,7-dimethylindole

yellow

Somewhat reddish yellow

Yellow yellow

Reddish yellow

yellow

yellow

Reddish yellow Orange Reddish yellow Reddish yellow Yellow Yellow Red-tinged yellow Yellow-tinged orange Orange Red-tinged yellow Red-tinged yellow Yellow yellow

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The amine used in Examples 1-40 can be obtained in the following ways:

a) 211 g of 75.2% strength 5-amino-2-formylbenzenesulfonic acid are dissolved in 650 ml of formic acid (98% strength) and 63 g of hydroxylamine hydrochloride and 200 g of sodium formate are added at 90 ° C. in the course of 2 hours. After 10 hours at 90 ° C is cooled to 30 ⁰ C. After pouring in 640 g of 38% H ₃ SO ₄ and cooling in an ice bath, the hydrochloride of 5-amino-2-cyanobenzenesulfonic acid crystallizes out. After suctioning off and drying, 117 g of a 74% strength product are obtained, which can be used directly. (M.p. 310 ⁰ C). Nitrilabsorption in the IR spectrum at 2260 cm The sodium salt melts at 236-241 ° C.

b) 185 g of sodium formate, 139.5 g of hydroxylamine sulfate and 295 g of 75.2 are added to 1198% formic acid % 2-amino-2-formylbenzenesulfonic acid heated under reflux for 1 hour. The solvent is distilled and receives 500 g of 39.6% strength 5-amino-2-cyanobenzenesulfonic acid, which is used in this form can be.

This is in contrast to the analogous reaction of a sulfonic acid-free aminobenzaldehyde: 125 g of sodium formate, 94.5 g of hydroxylammonium sulfate and 155.5 g of 5-amino-2-chlorobenzaldehyde are heated to 90 ° C. in 11 of 98% formic acid for 7 hours. It is poured onto ice and 92 σ 2-chloro-5-formylamino-benzonitrile is filtered off with suction with a melting point of 147 ° C. (decomp.). In addition to the nitrile absorption at 2230 cm, the IR spectrum shows a carbonyl oscillation at 1680 cm " ¹ .

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The 5-amino-2-cyanobenzenesulfonic acid shown above can be halogenated in the 4-position by processes described in the literature, for example in glacial acetic acid in the presence of sodium acetate. The sodium salt of the bromine compound melts above 300 ° C; in the IR spectrum (KBr) the nitrile absorption occurs at 2230 cm ", in the H-NMR spectrum the signals for the two aromatic protons are 7.23 6 (singlet) and 7.68O * (singlet) in D ₃ O with TMS as internal standard.

The data for the analogously represented 5-amino-4-chloro-2-cyanobenzenesulfonic acid are: Melting point: _ * 300 C;

C = N absorption in the IR spectrum 2240 cm, aromatic protons

¹ H-NMR spectrum as singlets at 7.22 and 7.75 '<?.

The following halogenated cyanaminosulphonic acids listed in Table 2 can be prepared in a very similar manner: 4-Amino-5-chloro-3-cyanobenzenesulphonic acid (~ f _nmKt 2250 cm) 4-Amino-5-bromo-3-cyanobenzenesulphonic acid (^ _{C = N} 2250 cm) 2-Amino-3-bromo-5-cyanobenzenesulfonic acid (; f _C = _N 2270 cm .

2-Amino-3-bromo-5-cyanobenzenesulphonic acid (X " _Ca " 2260 cm 4-Amino-5-chloro-2-cyanobenzenesulphonic acid hfr, _{= M} 2260 cm) 4-Amino-5-bromo-2-cyanobenzenesulphonic acid (ν - 2240 cm).

Another production possibility consists in the sulfonation of cyananilines according to processes described in the literature. This method was used to produce 4-amino-2-chloro-5-cyanobenzenesulfonic acid (γ ~ -, _ΞΝ 2240 cm) 2-amino-5-cyanobenzenesulfonic acid (, ^ _r z _N 2240 cm) 4-amino-2-cyanobenzenesulfonic acid ( χ _ 2260 cm) 2-amino-3,5-dicyanobenzenesulphonic acid (ΡΓρΞμ ²²⁴ ° ^and 2260 cm) 2-amino-3-cyano-5-nitrobenzenesulphonic acid ( % ~ _rmK 2270 cm 4-amino-2,5-dicyanobenzenesulphonic acid (V ^ _c - _N 2230 and 2280 cm)

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By nucleophilic exchange of halogens in Halonitrobenzonitrilen with sulfite and subsequent reduction of the nitro group were
J-amino-4-cyanobenzenesulfonic acid (y "_ 2230 cm) and

-i i- N Λ

2-Amino-4-cyanobenzenesulphonic acid () f _r - _N 2230 cm) taken.

3-Amino-5-cyanobenzenesulfonic acid (T _C = _N 2230 cm) was obtained by reducing the 3-nitro-5-cyanobenzenesulfonic acid.

The amines _ ₁

2-Amino-3-cyano-5-acetaminobenzolsulfonsäure _{((f c} r _N ° ^m 2-Amino-3-cyano-5-benzaminobenzolsulfonsäure (\ _"r ~ _N 2230 cm. Were after reduction of the nitro group in the above-mentioned 2- Amino-3-cyano-5-nitrobenzenesulfonic acid and subsequent acetylation or benzoylation shown at room temperature.

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Example 41

33.3 g of 83% strength 5-amino-4-bromo-2-cyanobenzenesulfonic acid become Dissolve in 100 g of water alkaline with soda, dissolved with 7 g of NaNO / in 20 g of water, added and at 0 - 5 C in 40 ml concentrated hydrochloric acid and 200 g of ice were added dropwise. The diazonium salt soon separates out of the initially clear solution away. For coupling, the nitrite-free suspension of the diazonium salt is poured into an ethanolic solution of 13.1 g of 2-methylindole, blunt to accelerate the Reaction reduces the pH to 4-5 and sucks the deposited dye off after the coupling has ended. To washing and drying give 38.4 g of the dye of the formula

N-H

as a brown powder. It dyes polyamide in reddish yellow. The coloring is characterized by high color strength and very good light and wet fastness.

Table 2 lists other valuable dyes that can be obtained after diazotization of halogen-containing cyanaminobenzenesulfonic acids and coupling with the indicated indoles is obtained.

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Table 2

Example diazo component

Coupling component

Color on polyamide

5-Amino-4-bromo-2- 2-phenylindole cyanobenzenesulfonic acid

3 5-Amino-4-bromo-2-i-methyl-2-phenylcyanobenzenesulfonic acid indole

5-amino-4-bromo-2-1,2-dimethylindole cyanobenzenesulfonic acid

5-Amino-4-bromo-2- 1- (2-cyanoethyl) -2-cyanobenzenesulfonic acid phenylindole

5-Amino-4-bromo-2-1-butyl-2-phenylcyanobenzenesulfonic acid indole

5-Amino-4-bromo-2-1-butyl-2-methylcyanobenzenesulfonic acid indole

5-Amino-2-bromo-2- 1- (2-acetaminoprocyanobenzenesulfonic acid pyl) -2-methylindole

5-Amino-4-bromo-2- 1- (2-chloro-3-phencyanobenzenesulfonic acid oxy) -2-methylindole

5-Amino-4-bromo-2-1-benzyl-2-phenylcyanobenzenesulfonic acid indole

5-amino-4-bromo-2- 2,5-dimethylindole cyanobenzenesulfonic acid

5-Amino-4-bromo-2- 2-methyl-5-indole cyanobenzenesulfonic acid sulfonic acid

5-Amino-4-chloro-2- 2-phenylindole cyanobenzenesulfonic acid

5-Amino-4-chloro-2- 2-methylindole cyanobenzenesulfonic acid

Yellowish orange

orange

yellow

Reddish yellow

Reddish yellow

yellow

yellow

yellow

Yellowish orange

yellow

orange

Yellowish orange

Reddish yellow

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Table 2 continued

Example diazo component

Coupling component color on polyamide

5-Amino-4-chloro-2- 2-phenyl-5-indole cyanobenzenesulfonic acid sulfonic acid

4-Amino-5-chloro-3-2-methylindole cyanobenzenesulfonic acid

4-Amino-5-chloro-3-2-phenylindole cyanobenzenesulfonic acid

4-Amino-5-bromo-3-1-methyl-2-phenylcyanobenzenesulfonic acid indole

4-Amino-5-bromo-3-2-methylindole cyanobenzenesulfonic acid

2-Amino-3-chloro-5- 2-methylindole cyanobenzenesulfonic acid

2-Amino-3-chloro-5- 2-phenylindole cyanobenzenesulfonic acid

2-Amino-3-bromo-5- 2-phenylindole cyanobenzenesulfonic acid

2-Amino-3-bromo-5- 2-methylindole cyanobenzenesulfonic acid

2-amino-3-bromo-5-1,2-dimethylindole cyanobenzenesulfonic acid

2-Amino-3-bromo-5- 1- (2-carbonamidocyanobenzenesulfonic acid ethyl) -2-methyl-

indole

4-Amino-5-chloro-2- 2-methylindole cyanobenzenesulfonic acid

4-Amino-5-chloro-2- 1- (1-cyanoethyl) -cyanobenzenesulfonic acid 2-methylindole

orange

yellow

orange

Reddish yellow

Reddish yellow

yellow

Yellowish orange

Yellowish orange

yellow

yellow

yellow

Reddish yellow

Reddish yellow

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Table 2 continued

Example diazo component

Coupling component color

on polyamide

68 4-amino-5-chloro-2-
cyanobenzenesulfonic acid 2-phenylindole orange 69 4-amino-5-chloro-2-
cyanobenzenesulfonic acid 1- (2-cyanoethyl) -
2-phenylindole Rotstichi
full yellow 70 4-amino-5-bromo-2-
cyanobenzenesulfonic acid 2-methylindole Rotstichi
full yellow 71 4-amino-5-bromo-2-
cyanobenzenesulfonic acid 2-phenylindole orange 72 4-amino-2-chloro-5-
cyanobenzenesulfonic acid 2-methylindole Rotstichi
full yellow 73 4-amino-2-chloro-5-
cyanobenzenesulfonic acid 1,2-dimethylindole Rotstichi
full yellow 74 4-amino-2-chloro-5-
cyanobenzenesulfonic acid 1- (2-cyanoethyl) -2-
methylindole Rotstichi
full yellow 75 4-amino-2-chloro-5-
cyanobenzenesulfonic acid 1- (propyl) -2-me-
thylindol Rotstichi
full yellow 76 4-amino-2-chloro-5-
cyanobenzenesulfonic acid 1- (2-hydroxy-2-me-
thylbutenyl) -2-me-
thylindol Rotstichi
full yellow 77 4-amino-2-chloro-5-
cyanobenzenesulfonic acid 2-phenylindole orange 78 4-amino-2-chloro-5-
cyanobenzenesulfonic acid 1-methyl-2-phenyl-
indole Yellow sticks
chiges
orange

Other valuable dyes are obtained when the aminocyanbenzenesulfonic acids listed in Table 3 are used.

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Tabel

Example diazo component

Coupling component

Color on polyamide

2-amino-5-cyanobenzene-2-methylindole sulfonic acid

2-amino-5-cyanobenzene-1,2-dimethylindole sulfonic acid

2-amino-5-cyanobenzene-2,5-dimethylindole sulfonic acid

2-amino-5-cyanobenzene sulfonic acid

2-amino-5-cyanobenzenesulfonic acid 1-butyl-2-methylindole

- (3-acetaminopropyl) -2-methylindole

Reddish yellow

Reddish yellow

Reddish yellow

Reddish yellow

Rotstichiqps yellow

84 85 86 87 88 89 90 91

2-Amino-5-cyanobenzenesulfonic acid - (2-bromobutyl) -2-methylindole

2-amino-5-cyanobenzene-2-phenylindole sulfonic acid

2-amino-5-cyanobenzenesulfonic acid

2-amino-5-cyanobenzenesulfonic acid 1-methyl-2-phenylindole

- (2-chloropropyl) -2-phenylindole

4-Amino-3-cyanobenzene-2-methylindole sulfonic acid

4-Amino-3-cyanobenzene-1,2-dimethylindole sulfonic acid

4-amino-3-cyanobenzene-2,5-dimethylindole sulfonic acid

4-amino-3-cyanobenzenesulfonic acid 1-butyl-2-methylindole

Reddish yellow

orange

Reddish yellow

Reddish yellow

Reddish yellow

Reddish yellow

Reddish yellow

Reddish yellow

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Continuation of Table 3 Example of a diazo component

Coupling component color on polyamide

4-amino-3-cyanobenzenesulfonic acid

4-amino-3-cyanobenzenesulfonic acid

4-amino-3-cyanobenzenesulfonic acid

1- (3-acetaminopropyl) -2-methylindole

1- (2-bromobutyl) -2-methylindole

2-phenylindole

Reddish yellow

Reddish yellow

orange

95 4-amino-3-cyanobenzene
sulfonic acid 1-methyl-2-phenyl-
indole Yellow tones
full yellow 96 4-amino-3-cyanobenzene
sulfonic acid 1- (2-chloropropyl) -
2-phenylindole Yellow tones
full orange 97 4-amino-2-cyanobenzene
sulfonic acid 2-methylindole yellow 98 4-amino-2-cyanobenzene
sulfonic acid 1,2-dimethylindole yellow 99 4-amino-2-cyanobenzene
sulfonic acid 2,5-dimethylindole yellow 100 4-amino-2-cyanobenzene
sulfonic acid 1-butyl-2-methyl
indole yellow 101 4-amino-2-vanbenzene 1- (3-acetaminoDro- A little red

sulfonic acid

pyl) -2-methylindole

pungent yellow

4-amino-2-cyanobenzenesulfonic acid

1- (2-bromobutyl) -2-methylindole

Somewhat reddish yellow

4-amino-2-cyanobenzenesulfonic acid

4-amino-2-cyanobenzenesulfonic acid

2-phenylindole

1-methyl-2-phenylindole

Strong yellowish orange

Reddish yellow

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Table 3 continued

example Diazo component Coupling component hue
on poly
amide 105 4-amino-2-cyanobenzene
sulfonic acid 1- (2-chloropropyl) -
2-phenylindole Rotsti
chiges
yellow 106 4-amino-2-cyanobenzene
sulfonic acid 1- (2-cyanoethyl) -2-
phenylindole 107 4-amino-3,5-dicyanobenzene
sulfonic acid 2-methylindole Rotsti
chiges
yellow 108 2-amino-3,5-dicyano-4,6-
dimethylbenzenesulfonic acid 2-methylindole Rotsti
chiges
yellow 109 2-amino-3-cyano-5-nitro-
benzenesulfonic acid 2-methylindole orange 1 10 2-amino-3-cyano-5-acet-
aminobenzenesulfonic acid 2-methylindole Rotsti
chiges
yellow 111 2-amino-3-cyano-5-benz-
aminobenzenesulfonic acid 2-methylindole Rotsti
chiges
yellow 112 2-amino-3-cyano-5-benz-
aminobenzenesulfonic acid 2-methylindole orange 113 4-amino-2,5-dicyanobenzene
sulfonic acid 2-methylindole Yellow sticks
chiges
orange 1 14 4-amino-2,5-dicyanobenzene
sulfonic acid 2-phenylindole orange 115 3-amino-4-cyanobenzene
sulfonic acid 2-methylindole Rotsti
chiges
yellow

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Continuation of table 3

example Diazo component Coupling component hue
on
polyamide 116 3-amino-4-cyanobenzene
sulfonic acid 1,2-dimethylindole Rotsti
chiges
yellow 117 3-amino-4-cyanobenzene
sulfonic acid 2,5-dimethylindole Rotsti
chiges
yellow 118 3-amino-4-cyanobenzene
sulfonic acid 1-butyl-2-methyl-
indole Rotsti
chiges
yellow 1 19th 3-amino-4-cyanobenzene
sulfonic acid 1- (3-acetamino-
propyl) -2-methyl-
indole Strong
rotsti
chiges
yellow 120 3-amino-4-cyanobenzene
sulfonic acid 1- (2-bromobutyl-2-
methylindole Strong
rotsti
chiges
yellow 121 3-amino-4-cyanobenzene
sulfonic acid 2-phenylindole Yellow sticks
chiges
orange 122 3-amino-4-cyanobenzene
sulfonic acid 1-methyl-2-phenyl-
indole Yellow sticks
chiges
orange 123 3-amino-4-cyanobenzene
sulfonic acid 1- (2-chloropropyl) -
2-phenylindole Yellow sticks
chiges
orange 124 2-amino-4-cyanobenzene
sulfonic acid 2-methylindole yellow 125 2-amino-4-cyanobenzene
sulfonic acid 1,2-dimethylindole yellow

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Continuation of table 3

example Diazo component Coupling component hue
on
polyamide 126 2-amino-4-cyanobenzene
sulfonic acid 2,5-dimethylindole yellow 127 2-amino-4-cyanobenzene
sulfonic acid 1-butyl-2-methyl
indole yellow 128
129 2-amino-4-cyanobenzene
sulfonic acid
2-amino-4-cyanobenzene
sulfonic acid 1 - (3-acetamino-
propyl) -2-methyl-
indole
1- (2-bromobutyl) -2-
methylindole yellow
yellow 130 2-amino-4-cyanobenzene
sulfonic acid 2-phenylindole orange 131 2-amino-4-cyanobenzene
sulfonic acid 1-methyl-2-phenyl-
indole Rotsti
chiges
yellow 132 2-amino-4-cyanobenzene
sulfonic acid 1- (2-chloropropyl) -
2-phenylindole Rotsti
chiges
yellow 133 3-amino-5-cyanobenzene
sulfonic acid 2-methylindole yellow 134 3-amino-5-cyanobenzene
sulfonic acid 1,2-dimethylindole yellow 135 S-amino-S-cyanobenzene-
sulfonic acid 2,5-dimethylindole yellow 136 3-amino-5-cyanobenzene
sulfonic acid 1-butyl-2-methyl-
indole yellow 137 3-amino-5-cyanobenzene
sulfonic acid 1- (3-acetamino-
propyl) -2-methyl-
indole yellow

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Continuation of table 3

example Diazo component Coupling component hue
on
polyamide 138 3-amino-5-cyanobenzene
sulfonic acid 1- (2-bromobuty1-2-
methylindole yellow 139 3-amino-5-cyanobenzene
sulfonic acid 2-phenylindole Yellow sticks
chiges
orange 140 3-amino-5-cyanobenzene
sulfonic acid 1-methyl-2-pheny1-
indole Rotsti
chiges
yellow 141 3-amino-5-cyanobenzene
sulfonic acid 1- (2-chloropropy1) -
2-phenylindole Rotsti
chiges
yellow

Example 142

11.8 g of 4-aminobenzonitrile are thoroughly triturated with 50 ml of HCl 1: 1. The resulting suspension is treated dropwise at 0-5 ° C. with 70 ml of 10% sodium nitrite solution and stirred for a further 30 minutes. After removing a slight excess of nitrite with sulfamic acid, the diazo solution is poured into an aqueous solution of 24.9 g of 84.6% strength 2-methylindole-5-sulfonic acid with stirring. The coupling is accelerated by raising the pH to 4-5, and the dye of the formula

SO ₁ H

N = C-

/ Vn = N

can be vacuumed after salting out with a little common salt. To

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drying gives 28.3 g of a yellow powder which gives the polyamide a neutral yellow color and which has a high coloring strength and very good fastness properties.

If, instead of the above-mentioned diazo component, those listed in Table 4 are used, other similar ones are obtained Dyes.

Table 4

example Diazo component Color on polyamide 143 3-aminobenzonitrile yellow 144 2-aminobenzonitrile Reddish yellow 145 4-aminophthalic acid dinitrile Yellowish tinge
orange 146 4-amino-2,6-dimethyl-isophthal-
acid dinitrile Yellowish tinge
orange 147 2-aminoterephthalic acid dinitrile Yellowish tinge
orange 148 2-amino-5-chloro-terephthalic acid
dinitrile Yellowish tinge
orange 149 2-amino-5-bromoterephthalic acid
dinitrile Yellowish tinge
orange 150 2-amino-4-chlorobenzonitrile Reddish yellow 151 4-amino-2,5-dichlorobenzonitrile Yellowish tinge
orange 152 2-amino-5-acetaminobenzonitrile orange 153 2-amino-5-benzoylaminobenzonitrile orange 154 2-amino-5-phenylsulfonylamino
benzonitrile Reddish
orange

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Continuation of table 4 Example diazo component color shade on polyamide

155 2-Amino-5-phenylaminocarbo- yellowish orange nyl aminobenzonitrile

If you work in accordance with Example 142 with 2-phenyl-5-indolesulfonic acid as a coupling component, the diazo components listed in Table 5 are used to obtain more very valuable yellow dyes.

Table 5 Example diazo component color shade on polyamide

156 4-aminobenzonitrile reddish yellow

157 3-aminobenzonitrile Reddish yellow

158 2-aminobenzonitrile Reddish yellow

159 4-aminophthalic acid dinitrile orange

160 4-Amino-2,6-dimethyl-isophthalic acid dinitrile

161 2-aminoterephthalic acid dinitrile orange

162 2-Amino-5-chloro-terephthalic acid dinitrile

163 2-Amino-5-bromoterephthalic acid dinitrile

164 2-Amino-4-chlorobenzonitrile Orange

165 4-Amino-2,5-dichlorobenzonitrile orange

166 2-Amino-5-acetaminobenzonitrile Reddish orange

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Table 5 continued

Example diazo component color shade on polyamide

167 2-Amino-5-benzoylaminobenzo-Reddish orange nitrile

168 2-Amino-5-phenylsulfonylamino reddish orange benzonitrile

169 2-Amino-5-phenylaminocarbonyl- reddish orange aminobenzonitrile

Staining example

0.04 g of the dye obtained according to Example 1 are dissolved with 100 g of hot water. 5 ml of ammonium acetate solution are used added and diluted with cold water to 500 g. 10 g of polyamide textile material, heated, are placed in this dyebath to the boil within 20 minutes, add 4 g of 10% acetic acid and keep it at boiling temperature for 1 hour. After that, will the dyed polyamide material is removed from the dyebath, rinsed with hot water and dried at 70 - 80 ° C. Man receives a strongly yellowish orange colored polyamide fabric.

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Claims (9)

Claims 1. Dyes in the form of the free acid of the formula CN correspond in which R ₁ = H, substituent, R ₂ = alkyl, aryl, R ^ = H, alkyl, cycloalkyl, aralkyl, R ₄ = H, substituent, η = 1,2 or 3, ο = 0 or 1, ρ = 0 or 1, ο + ρ = 1 or 2. 2. Dyes of claim 1, wherein R ₁ = H, F, Cl, Br, CN, NO ₂ , CF ₃ , C, -C ^ alkoxycarbonyl, C ₁ -C ₄ ~ alkylcarbonyl, arylcarbonyl, arylsulfonyl, C ₁ -C ₄ -alkylsulfonyl, R ₃ = H, alkyl, cycloalkyl, aralkyl, R ₄ = H, C ₁ -C ₄ -AlJCyI, η = 1, Le A 18 265 - 27 - 809886/0185 ORIGINAL INSPECTED ο = 0 or 1, ρ = 0 or 1, ο + ρ = 1. 3. Dyes in the form of the free acid of the formula R. R. correspond to where R ₅ = H, Cl, Br, R ₆ = CH ₃ , C ₆ H ₅ , R ₇ = H, CH ₃ , Rg = H, C ₁ -C ₄ AlJCyI, benzyl. 4. Dyes in the form of the free acid of the formula R V- / -N = N - (^ ^ N-Rg I SCKH R -> D in which R ₅ , R ₆ and R "have the meanings given in claim 3. Le A 18 265 - 28 - 8098 86/0185 5. Dyes in the form of the free acid of the formula SO _n H (CN)
πι correspond to where R ₉ = H, Cl, Br, CH ₃ , m = 1 or 2 and R, and R "those specified in claim 3 Have meaning. 6. Use of the dyes of claims 1-5 for dyeing natural or synthetic nitrogenous fiber materials, especially synthetic polyamides. 7. Natural or synthetic nitrogenous fiber material dyed with the dyes of claims 1-5 . 8. Amino-cyanobenzenesulfonic acids of the formula and their salts, especially the alkali salts, in which Le A 18 265 - 29 - 8 0 9 8 8 6/0185 R ₁ = H or substituent, η = 1, 2 or 3. 9. Use of the amino-cyanobenzenesulfonic acids of claim 8 for the production of azo dyes. Le A 18 265 - 30 - 809886/0185