CH632292A5 - Water-insoluble azo dyes and preparation thereof - Google Patents

Description

The present invention relates to the water-insoluble azo dyes of the formula I defined in claim 1.

From DE-OS 1 901 711 monoazo dyes are known which, as the rest of a coupling component, for. B. Derivatives of 4-alkyl-3-cyano-6-hydroxy-pyrid-2-one contain, which on the pyridon nitrogen z. B. are substituted by an aminocarbonylethyl radical, dime, thylaminocarbonylethyl radical or acetylamino radical. Compared to these known dyes, the dyes according to the invention have improved properties.

The cycloalkyl radicals in R3 and R4 contain, for example, 3 to 8, preferably 5 or 6, carbon atoms and can be substituted once or twice by halogen, in particular chlorine, optionally branched alkyl having 1 to 4 carbon atoms or optionally branched alkoxyl having 1 to 4 carbon atoms.

All alkyl or alkoxy groups can be straight-chain or branched.

The alkyl groups Rs and Re can, together with the N atom to which they are attached and optionally form the following 5- or 6-membered ring groups via a further heteroatom: 1-pyrrolidinyl, 1-piperazinyl, morpholino, thio-morpho-5 linos, piperidino . The 1-piperazinyl radical can also be substituted in the 4-position by alkyl having 1 to 4 carbon atoms, so that, for. B. 4-methyl-1-piperazinyl or 4-ethyl-1-piperazinyl residues are also suitable.

The new dyes are produced by the method defined in claim 10 4.

With regard to the formation of the disperse dyes or with regard to their color yield, it may be advantageous to diazotize a mixture of two or more amines of the formula II and with one or more 3-cyano-6-15 hydroxy-2-pyridones of the formula III couple or couple a diazo-tated amine of formula II with two or more 3-cyano-6-hydroxy-2-pyridones of formula III.

It is possible that the dyes of the formula I according to the invention and the starting compounds of the formula III are present in tau-20 tomeric forms. In the context of the present invention, the dyes I according to the invention and the starting compounds III are also taken to mean the possible tautomers.

The invention also relates to the coupling components of the formula III defined in claim 25 8.

The production of coupling components III can e.g. B. analogously, according to the information provided by Bobbitt and Scola - J. Org. Chem. 25,560 ff (1960) by condensation of a β-keto-carboxylic acid ester with a suitable N-substituted 30 cyanoacetamide in the presence of alkali metal hydroxide, such as, for. As potassium hydroxide, in an alkanol, such as. As methanol or ethanol, at a higher temperature, for example reflux temperature. Glycol ethers such as. B. methyl glycol come into consideration and instead of the alkali hydro-35 xyds can also be an alkali alcoholate, such as. B. sodium methylate or sodium methylglycolate can be used. The alkali salts of the coupling components of the formula III are formed in this production process. These alkali salts can be used directly for the coupling reaction.

4o The coupling components can also be produced by other different processes, as described, for example, in the monograph by Klingsberg "Pyridine and its Derivatives, Part Three", in particular on p. 525 ff. This monograph was published in the series “The Chemistry of Heterocyclic Compounds” by Arnold 45 Weissberger and published by Interscience Publishers, New York-London, 1962.

The N-substituted cyanoacetamides of For-50 mei VIII required for the preparation of the coupling components of the formula III can be prepared, for example, in the following way:

H

iv

/ Rp hn xco-r3

R ^ Rq / 1/2

ho-ch-n

\

co-r-

h + nc-ch2-co-nhp

. 7 "

3-h2o vi

2nd

ck CIL co nh cii-r n-r2 oc-r

3rd

VIII

wherein Ri, R2 and R3 have the meaning given above. An aldehyde of the formula IV is reacted with an appropriately substituted amide of the formula V in the presence of an alkali metal hydroxide.

e.g. As potassium hydroxide, melted together at temperatures of 40 to 140 ° C. The resulting compound of formula VI is with cyanoacetamide in the presence of a

632292

4th

Acid such as As phosphoric acid, sulfuric acid or hydrochloric acid, and in an organic solvent such as. B. methylene chloride, ethylene chloride, toluene, is suitable for azeotropic distillation of the water of reaction formed. After the azeotropic distillation of the water of reaction and possibly distillation of the organic solvent, the N-substituted cyanoacetamide of the formula VIII can be isolated.

The residues D of the diazo components can be substituted, for example, once, twice or three times with the following substituents:

Halogen, especially chlorine; Cyan; Nitro; Trifluoromethyl; Hydroxyl; Alkyl, in particular with 1 to 6 carbon atoms; Alkoxy, in particular with 1 to 6 carbon atoms; Aryloxy, e.g. B. phenoxy; Acyl, in particular with 1 to 7 carbon atoms (acyl is understood to mean the alkylcarbonyl radical formed from a carboxylic acid by removing the OH group; the alkylcarbonyl or acyl radical with 1 carbon atom is the formyl radical), acyloxy, in particular with 2 to 7 Carbon atoms; Benzoyl; Phenoxycarbonyl; Alkoxycarbonyl, in particular with 2 to 8 carbon atoms; optionally N-mono or N, N-disubstituted carboxylic acid or sulfonic acid amide, alkyl substituents with 1 to 8 C atoms or phenyl residues being particularly suitable as substituents; Alkylsulfonyl, in particular with 1 to 4 carbon atoms; Alkyl-sulfonylalkyl, in particular with 2 to 8 carbon atoms; Alkylsulfonyloxy, in particular with 3 to 8 carbon atoms; Arylsulfonyloxy; N-substituted and N, N-disubstituted aminosulfonyloxy, where in particular alkyl radicals with 1 to 6 carbon atoms are suitable as substituents; optionally substituted phenylazo.

Examples of suitable amines of the formula II are:

aniline

2-, 3- or 4-aminotoluene

2-, 3- or 4-amino-benzyl-dimethylamine 4-amino-phenethyl-β-dimethylamine 4-amino-benzyl-N-piperidine

3-amino-trifluoromethyl-benzene

3- or 4-amino-l, 2-dimethyl-benzene

4-amino-n-butyl-benzene 4-amino-n-hexyl-benzene

2-, 4- or 5-amino-l, 3-dimethyl-benzene

4-amino-l, 3,5-trimethyl-benzene

2-, 3- or 4-aminophenol

2-, 3- or 4-amino-anisoI

2-, 3- or 4-aminophenetol

2-, 3- or 4-amino-n-butoxy-benzene

4-amino-iso-octyl-oxy-benzene

2-, 3- or 4-amino-diphenyl ether

2-amino-1,4-dimethoxy-benzene

2-amino-1,4-diethoxy-benzene

2-amino-1,4-di-isopropoxy-benzene

2-, 3- or 4-chloroaniline

2-, 3- or 4-bromoaniline

2,3-, 2,4-, 2,5- or 3,4-dichloroaniline

2,5-dibromaniline

2-, 3- or 4-amino-dimethylamino- or -diethylamino-benzene

2.4.5-, 2,4,6-, 3,4,5- or 3,5,6-trichloroaniline

3-, 4-, 5- or 6-chloro-2-aminotoluene

4-chloro-3-aminotoluene 2-chloro-4-aminotoluene

5-chloro-2-amino-trifluoromethyl-benzene 4,5- or 4,6-dichloro-2-amino-toluene 2,5- or 4,6-dichloro-3-amino-toluene 2,5- or 3,5-dichloro-4-amino-toluoI

4.5.6-Trichloro-2-aminotoluene 4-chloro-2-amino-l, 3-dimethyl-benzene 2-, 3- or 4-amino-benzyl-methylsulfone 4-amino-phenyl-propyl-methylsulfone

6-chloro-3-amino-anisole 2-chloro-4-amino-anisole

2-chloro-4-amino-n-hexoxy-benzene

3-chloro-4-amino-anisole 2-, 3- or 4-nitraniline

2-nitro4-aminotoluene

3-nitro-4-aminotoluene

4-nitro-2-amino-toluoI

2-ethyl-4-nitro-aniline

5-N itro-2-aminotoluene

5-nitro-4-amino-l, 3-dimethyl-benzene

6-nitro-3-amino-anisole

3-nitro-4-amino-anisole 3-nitro-4-amino-n-butoxy-benzene 5-nitro-2-aminophenethol

2-nitro-4-aminophenethol

3-nitro-4-aminophenethol 5-nitro-2-amino-l, 4-dimethoxy-benzene

5-nitro-2-amino-l, 4-diethoxy-benzoI 2-chloro-4-nitraniline 2-bromo4-nitraniline

4-chloro-2-nitraniline 4-bromo-2-nitraniline 4,6-dichloro-2-nitraniline 2,6-dichloro-4-nitraniline 2-chloro-6-bromo4-nitraniline 2,6-dibromo-4-nitraniline 2, 4-dinitraniline

6-chloro-2,4-dinitraniline 6-bromo-2,4-dinitraniline 2,4,6-trinitraniline

2-, 3- or 4-amino-benzonitrile

1-amino-2-cyan-5-chlorobenzene

2-cyano-4-nitraniline 2-cyano-6-bromo4-nitraniline 4-cyano-3-nitraniline l-amino-2,4-dicyanobenzene l-amino-2,6-dicyan4-nitro-benzene

1-amino-2-chloro-4-methylsulfonyI-benzene

2-methylsulfonyl-4-nitraniline 2-iso-butylsulfonyl4-nitraniline 4-methylsulfonyl-2-nitraniline 4-allylsulfonyl-2-nitraniline 4-phenylsulfonyl-2-nitraniline

2-, 3- or 4-amino-benzaldehyde

2-, 3- or 4-amino-diphenyl ether

2-Amino4-chloro or 4,4'-dichloro-diphenyl ether

2-, 3- or 4-amino-ß-dimethylamino- or -ß-diethylamino-ace-

tophenon

2-, 3- or 4-amino-acetophenone

4-amino-n-butyrophenone

4-amino-n-caprophenone

4-amino-a-ethyl-n-caprophenone

2-amino-5-nitro-acetophenone

2-, 3- or 4-amino-benzophenone

2-, 3- or 4-amino4'-methyl-, 4'-isopropyl-, 4'-n-butyl- or

-4'-n-hexyl-benzophenone

2-, 3- or 4-amino-2 ', 4'-dimethyl-benzophenone

2-, 3- or 4-amino4'-methoxy-benzophenone

2-, 3- or 4-amino4'-chloro-benzophenone

4-amino-5-nitro-benzophenone

2-, 3- or 4-amino-benzoic acid methyl or ethyl 2-, 3- or 4-amino-benzoic acid n-butyl ester 2-, 3- or 4-amino-benzoic acid n- decyl ester 2-, 3- or 4-amino-benzoic acid iso-octyl ester

1-Amino-benzene-3,5-dicarboxylic acid dimethyl or diethyl ester

Phenyl 2-, 3- or 4-amino-benzoate

2-, 3- or 4-amino-benzoic acid-4'-tert.butyl- or 4'-isohexyl-

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

5

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phenyl ester

2-, 3- or 4-amino-benzoic acid cyclohexyl ester

2-, 3- or 4-amino-benzoic acid benzyl esters

2-, 3- or 4-amino-benzoic acid-ß-methoxy-ethyl ester

2-, 3- or 4-amino-benzoic acid-ß-ethoxy-ethyl ester

2-, 3- or 4-amino-benzoic acid-ß-butoxy-ethyl ester

2-, 3- or 4-amino-benzoic acid methyl diglycol esters

Ethyl diglycol ester of 2-, 3- or 4-amino-benzoic acid

2-, 3- or 4-amino-benzoic acid methyl triglycol esters

Ethyl triglycol ester of 2-, 3- or 4-amino-benzoate

2-, 3- or 4-amino-benzoic acid-ß-hydroxy-ethyl ester

2-, 3- or 4-amino-benzoic acid-β-acetoxy-ethyl ester

2-, 3- or 4-amino-benzoic acid-ß- (ß'-hydroxy-ethoxy) -ethyl-

ester

2-, 3- or 4-amino-benzoic acid-β-hydroxy-propyl ester

2-, 3- or 4-Amino-benzoic acid-y-hydroxypropyl ester

2-, 3- or 4-amino-benzoic acid, 8-hydroxy-butyl ester

2-, 3- or 4-amino-benzoic acid-co-hydroxy-hexyl ester

4-nitro-anthranilic acid methyl ester

4-nitro-anthranilic acid iso-butyl ester

4-nitro-anthranioleic acid methyl diglycol ester

4-nitro-anthranilic acid-ß-methoxyethyl ester

4-nitro-anthranilic acid-ß-butoxyethyl ester

4-nitro-anthranilic acid methyl diglycol ester

2-, 3- or 4-amino-benzoic acid amide

20th

3- or 4-amino-benzoic acid monomethylamide

3- or 4-amino-benzoic acid iso-octylamide

3- or 4-amino-benzoic acid dimethylamide

3- or 4-amino-benzoic acid ethylene imide

3- or 4-amino-benzoic acid iso-propylamide 30

3- or 4-amino-benzoic acid-n-hexylamide

3- or 4-amino-benzoic acid diethylamide

3- or 4-amino-benzoic acid di-n-butylamide

3- or 4-amino-benzoic acid morpholide

3- or 4-amino-benzoic acid anilide 35

3- or 4-Amino-benzoic acid N-methylanilide

3- or 4-amino-benzoic acid-N, N-dimethylhydrazide

3- or 4-amino-benzoic acid (y-dimethylaminopropylamide)

3- or 4-amino-phenyl-benzoic acid esters

3- or 4-Amino-phenyl4'-tert-butyl-benzoic acid ester 40

3- or 4-aminophenyl-2 ', 4', 6'-trimethylbenzoic acid ester

3- or 4-aminophenyl-methyl-sulfonic acid esters

3- or 4-amino-phenyl-ethyl sulfonic acid ester

3- or 4-amino-phenyl-ß-chloroethyl-sulfonic acid ester

3- or 4-aminophenyl butyl sulfonic acid ester 45

3- or 4-aminophenyl-n-hexylsulfonic acid ester

3- or 4-amino-phenyl-iso-octyl-sulfonic acid ester

3- or 4-amino-phenyl-phenyl-sulfonic acid esters

3- or 4-amino-phenyl- (4'-methyl-phenyl) -sulfonic acid ester

3- or 4-amino-phenyl- (4'-n-butyl-phenyl) -sulfonic acid ester 50

3- or 4-aminophenyl- (4'-methoxyphenyl) sulfonic acid -

2-2 2-2-2-2-2-2-2-2-2 2-2-2-2-2-2-2-2 2 2 2 2-2-2-2 esters

2-, 3- or 4-aminophenyl- (4'-chlorophenyl) sulfonic acid esters

Phenyl 2-, 3- or 4-amino-benzenesulfonate

2-, 3- or 4-amino-benzene-sulfonic acid, 4'-methylphenyl ester

2-, 3- or 4-amino-benzene-sulfonic acid 4'-n-butylphenyl ester

2-, 3- or 4-amino-benzene-sulfonic acid, 4'-methoxyphenyl ester

2-, 3- or 4-amino-phenyl-ß-ethoxy-ethyl-sulfamic acid ester

2-, 3- or 4-aminophenyldimethylsulfamic acid esters

2-, 3- or 4-amino-phenyl-ethyI-sulfamic acid esters

2-, 3- or 4-aminophenyldiethylsulfamic acid esters

2-, 3- or 4-amino-phenyl-di-n-butyl-sulfamic acid esters

2-, 3- or 4-aminophenyl-cyclohexyl-sulfamic acid esters

4-aminophenyl methyl sulfone

4-aminophenyl-n-butyl sulfone

4-aminophenyl iso-octyl sulfone

4-amino-diphenyl sulfone

2-, 3- or 4-amino-benzene-sulfonic acid amide

55

60

65

2-, 3- or 4-amino-benzenesulfonic acid monomethylamide

2-, 3- or 4-amino-benzenesulfonic acid iso-octylamide

2-, 3- or 4-amino-benzenesulfonic acid dimethylamide

2-, 3- or 4-amino-benzenesulfonic acid ethyleneimide

2-, 3- or 4-amino-benzenesulfonic acid diethylamide

2-, 3- or 4-amino-benzenesulfonic acid di-n-butylamide

2-, 3- or 4-amino-benzenesulfonic acid morpholide

2-, 3- or 4-amino-benzenesulfonic acid cyclohexylamide

2-, 3- or 4-amino-benzenesulfonic acid anilide

2-, 3- or 4-amino-benzenesulfonic acid-N-methyl-anilide l-methyl-2-amino-benzen-4-sulfonic acid amide l-methyl-2-amino-benzen-4-sulfonic acid-n-hexylamide l- Methoxy-2-amino-benzene-4-sulfonic acid amide l-methoxy-2-amino-benzene-4-sulfonic acid dimethylamide l-methoxy-2-amino-benzene-4-sulfonic acid di-n-butylamide l-methoxy-2-amino -benzene-4-sulfonic acid-N-methylanilide 1-chloro-2-amino-benzene-4-sulfonic acid-dimethylamide 1-chloro-2-amino-benzene-5-sulfonic acid-β-ethoxy-ethylamide 1-chloro-3-amino-benzene- 4-sulfonic acid amide

1-chloro-4-amino-benzene-2-sulfonic acid dimethylamide 4-amino-benzene-phenyl urethane

2-, 3- or 4-amino-acetaniIid

2-, 3- or 4-amino-phenoxyacetanilide 2-, 3- or 4-amino-N-methyl-acetanilide 1-amino-anthraquinone

1-amino-4- or -5-benzoylamino-anthraquinone 1-amino-4-chloro-anthraquinone

1-amino-naphthalene 1-amino-5-ethoxy-naphthalene 8-chloro-l-amino-naphthalene

2-amino-naphthalene

2-amino-naphthalene-6-sulfonic acid dimethylamide

4-amino-azobenzene

4-amino-4'-hydroxy-azob enzole

2 ', 3-dimethyl-4-amino-azobenzene

2,3'-Dimethyl4-amino-azobenzene

2,5-dimethyl4-amino-azobenzene

2-methyl-5-methoxy4-amino-azobenzene

2 ', 3-dimethoxy-4-amino-azobenzene

4'-nitro-2,5-dimethoxy-4-amino-azobenzene

4'-nitro-2-methyl-5-methoxy4-amino-azobenzene

1-phenylazo-4-amino-naphthalene

2-amino-5-nitro-thiazole

2-amino-4-methyl-5-nitro-thiazole

2-amino-6-nitro-benzothiazole

2-amino-5-phenyl-1.3.4-thiadiazole

3-phenyl-5-amino-1.2.4-thiadiazole

4-amino-benz-1,2,3-triazole

2-amino-1.3.5-thiadiazol4-methylthioether

3-amino-5-nitro-2.1-benzisothiazole 3-amino-5-nitro-7-chloro-2.1-benzisothiazole

3-amino-7-nitro-2,1-benzisothiazole

4-amino-7-nitro-1,2-benzisothiazole 4-amino-1,2-benzisothiazole 3-amino-5-nitro-1,2-benzisothiazole

Suitable coupling components of the formula III can be, for example, hydrogen in the X position or a methyl, ethyl, n- or iso-propyl, n-, iso-, sec. Or tert-butyl group, in the Hydrogen or a methyl, ethyl, n-propyl, n, sec or iso-butyl group, in the Rî position hydrogen, a methyl, ethyl, n or iso-propyl group, n, iso, sec. or tert-butyl group, further also the n or iso-amyl, n-hexyl or iso-octyl group, in the R3 position hydrogen, a methyl , Ethyl, n- or iso-propyl, n-, iso-, sec. Or tert-butyl group, and also the n- or iso-amyl, n-hexyl, a-ethyl contain -n-pentyl or the cyclohexyl group.

The coupling components of formula III can be in the Rj position z. B. also contain the following groups: methoxy,

632292

6

Ethoxy, n- or iso-propoxy, n- or iso-butoxy, n- or iso-pentyloxy, n- or iso-hexyloxy, iso-octyloxy, cyclohexyloxy, dimethylamino, diethylamino, methylethylamino, di-n-pro- pylamino, di-n-butylamino, morpholino, piperidino.

Dyes and dye mixtures of the formula I in which X is a methyl group R 1 are hydrogen are preferred

Rz is hydrogen or a methyl group

R3 is hydrogen, a methyl or ethyl group or the radicals

A

-OR4 or -1] v ', where R4, Rs and Re have the meaning

10th

R

D

have a methyl, ethyl or n-butyl group.

Dyes and dye mixtures of the formula I in which D is one are also preferred

3-nitraniline

2-M ethyl-4-nitraniline,

4-M ethyl-2-nitraniline,

3-amino-phenyl-phenyl-sulfonic acid ester,

3-amino-phenyl- (4'-methyl-phenyl) -sulfonic acid ester-,

4-Amino-benzophenone, 4-amino-4'-methoxy-benzophenone or 3-amino-phenyl-dimethylsulfamic acid ester residue.

Of particular technical interest are dyes of the formula I in which both D and X, R 1, R 2 and R 3 have the preferred meanings indicated above. Representatives of preferred dyes are e.g. B .:

20th

25th

30th

ch3

- -N = Nt ^ v- cn

/ 9

HO-C 0

f-a 1 ^

c = o c v '

V '-! • -? - i.

.ch.

CH0 1 ^ iM-CH 1

C-0

i

CH ~

-s02-0

The dyes according to the invention are particularly suitable for dyeing and printing structures made of synthetic materials, such as, for example, polyolefins, polyvinyl compounds, cellulose ^ A acetate, cellulose triacetate and in particular polyester materials, for. B. polyethylene glycol terephthalate or analogous polymers. They then deliver strong yellow to red dyeings and prints with very good fastness properties using the usual dyeing and printing processes.

In addition to the very good fastness to light and heat setting, the dyes according to the invention have a very high color strength, a very good build-up capacity and a high pH resistance, and also very good fastness properties when washing at 95 ° C., against peroxides, sweat acidic and in particular alkaline, nitrogen oxides / exhaust gases, alkali, in soda fastness, in hypochlorite bleaching fastness under heavy use, in rubbing fastness and in coratrone fastness.

50 The dyeing of the said fiber material with the dyes according to the invention is expediently carried out from an aqueous suspension in the presence of carriers between 80-100 ° C, in the absence of carriers between 110-140 ° C and according to the so-called heat setting process at 180-230 ° C. The printing of the materials mentioned can be carried out in such a way that the goods printed with the new dyes are steamed in the presence of a carrier at temperatures between 80-110 ° C or in the absence of a carrier at 110-140 ° C or according to the so-called Ther -60 mofixing process is treated at about 180-230 ° C.

The dyes according to the invention are also suitable for dyeing the hydrophobic materials listed above from organic solvents and for dyeing in bulk.

65 Example 1

a) 15.2 parts by weight of 2-methyl-4-nitraniline in 300 parts by weight of water with the addition of 36 parts by weight of 30% hydrochloric acid at 0 to +5 ° C with a solution of 7.7

7

632292

Parts by weight of sodium nitrite di-azotoped in 50 parts by weight of water. The filtered, clear diazo solution is then dissolved in a solution of 26.7 parts by weight of the sodium salt of 1- (N-methylformamido) -methylene-3-cyano-4-methyl-6-hydroxy-2-pyridone of the formula

CR-,

HO

II

"" "Previous year

, _. ce

Lo ben. Now the water and finally the toluene is distilled off azeotropically. It remains N-cyanoaceto-N'-methyl-N'-formyl-diamino-methane of the formula in

"O-

cho-c0-nh-ch,

c. c

/ •H\

ch "

, 0

r-

'\

H

2nd

K-CH.

u

0

in 400 parts by weight of water, 16.6 parts by weight of sodium hydroxide solution 33 ° Bé and 24.6 parts by weight of sodium acetate and the reaction temperature during the coupling by adding 500 parts by weight of ice at 0 to +5 ° C. The resulting dye is filtered off after the coupling has been completed, washed neutral with water and dried. It 25 is a reddish yellow powder that dissolves with reddish yellow paint in concentrated sulfuric acid.

b) 1.0 part by weight of the finely dispersed dye of the formula thus obtained

30th

PTJ ^^ 7

as a light yellow oil.

15 For the solution of 155.0 parts by weight of N-cyanoaceto-N'-methyl-N'-formyl-diamino-methane in 140.0 parts by weight of ethyl acetate, the solution of 30.0 parts by weight of sodium is stirred at 60 ° C. added in 1000.0 parts by weight of methyl glycol. The mixture is stirred at 60 ° C. for 4 hours and then the methyl glycol and the ethyl alcohol originating from the reaction are distilled off. The residue is stirred with 480.0 parts by weight of acetone and the resulting sodium salt of l- (N-methylformamido) -methylene-3-cyano-4-methyl-6-hydroxy-2-pyridone of the formula paragraph a) is suctioned off .

Example 2

a) 24.9 parts by weight of 3-amino-phenyl-phenylsulfonic acid ester of the formula

7

■ -WSX,

-s ° 2- °

1

r-u! <; - n-ch, Ì ~ ÜJ

II

can be stirred into 2000 parts by weight of water, adjusted to a pH of 5 with acetic acid and mixed with 4.0 parts by weight of ammonium sulfate and 2.0 parts by weight of a commercial dispersant based on a naphthalene-sulfonic acid-formaldehyde condensate.

In the dyeing liquor obtained in this way, z. B. Introduce 100 parts by weight of a polyester fabric based on polyethylene glycol terephthalate and dye at 130 ° C within 1 h.

After subsequent rinsing, reductive aftertreatment with a 0.2% alkaline sodium dithionite solution for 15 minutes at 70-80 ° C, rinsing and drying, a strong greenish yellow color is obtained with very good coloristic properties, in particular very good fastness to light and heat setting .

c) The coupling component required for the production of the dye according to paragraph a) can be produced in the following way:

195.0 parts by weight of para-formaldehyde, 342.0 parts by weight of N-methylformamide and 0.3 part by weight of caustic potash are stirred at 90 ° C. for 3 hours. A clear melt of N-methyl-N-methylol-formamide is obtained. 1750.0 parts by weight of toluene, 420.0 parts by weight of cyanoacetamide and 5.2 parts by weight of 30% strength saline solution are mixed with this melt.

are, as described in Example la), with the addition of 108.0 parts by weight of 30% hydrochloric acid and coupled with 26.1 parts by weight of l- (N-methoxycarbonyl) -amino-methylene-3-cyan-4-methyl-6- hydroxy-2-pyridone of the formula

45

50

55

ch.

r ^^ V-CN

110

il

1

ch

0

65

1 2 nh c0-0ch-

with the addition of 16.6 parts by weight of sodium hydroxide solution 33 ° Bé and 73.8 parts by weight of sodium acetate.

The resulting dye is a reddish yellow powder that dissolves with reddish yellow paint in concentrated sulfuric acid.

b) 30.0 parts by weight of the dye of the formula thus obtained

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8th

fi Vi50, .- 0 \ - / ^!

\ _n = n

HO — 1st

2 Ï? FI3

_ cn are diazotized in 150 parts by weight of glacial acetic acid with 34.2 parts by weight of nitrosylsulfuric acid, 41.3% with external cooling at +15 ° C. The clear diazo solution is then run into a solution of 26.7 parts by weight of l- (acetyl-5 amino) -methylene-3-cyano-4-methyl-6-hydroxy-2-pyridone of the formula

10th

co-och,

3rd

can be incorporated in a fine distribution of a printing paste containing 45.0 parts by weight of locust bean gum, 6.0 parts by weight of 3-nitro-15 benzene-sulfonic acid sodium and 3.0 parts by weight of citric acid per 1000 parts by weight. With this printing paste you get e.g. B. on a polyester fabric after printing, drying and fixing in a heat-setting frame for 45 seconds at 215 ° C, rinsing and ready 20 position, as described in Example lb), paragraph 3, a strong greenish yellow print of very good coloristic properties, especially a very good light and thermo-fix fastness.

c) The above printing paste provides z. B. on a triacetate fabric after printing, drying and fixing by pressure damping for 15 minutes at 1.5 atm, rinsing and completion, as described in Example lb), paragraph 3, a greenish yellow print of very good fastness properties.

d) The coupling component required for producing the dye according to paragraph a) can be produced in the following way:

375.0 parts by weight of methyl carbamate, 160.0 parts by weight of para-formaldehyde and 0.1 part by weight of caustic potash are stirred at 35 120 ° C. for 2 hours. A clear melt is obtained. For this purpose, 1750.0 parts by weight of toluene, 420.0 parts by weight of cyanoacetamide and 5.7 parts by weight of 30% hydrochloric acid are added and the water is then distilled off azeotropically. Upon cooling, the resulting 40 N-cyanoaceto-N'-methoxycarbonyl-diaminomethane of the formula crystallizes

NC-ch2-CO-NH-ch2-NH-CO-OCH3

in colorless needles. 45

To a solution of 35.0 parts by weight of N-cyanoaceto-N'-methoxycarbonyl-diamino-methane in 26.0 parts by weight of ethyl acetoacetate and 160.0 parts by weight of methanol, the solution of 120.0 parts by weight of caustic potash in 80.0 parts by weight of methanol is slowly added under reflux dripped. A clear yellow solution is formed. The methanol is distilled off, the residue is dissolved in water, the solution is acidified with hydrochloric acid and the l- (N-methoxycarbonyl) amino-methylene-3-cyano-4-methyl-6-hydroxy-2-pyridone of the formula paragraph a ) suctioned off. 55

Example 3

a) 21.6 parts by weight of 3-amino-phenyl-dimethylsulfame acid reester of the formula in 400.0 parts by weight of water and 120 parts by weight of sodium hydroxide solution 33 ° Bé. The reaction temperature is kept at 0 to +5 ° G during the coupling by adding about 500 parts by weight of ice. The resulting dye is suctioned off after the coupling has been completed, washed with water and dried. It is a reddish yellow powder that dissolves in reddish yellow color in concentrated sulfuric acid.

1 b) A fabric made of polyethylene glycol terephthalate can be padded on the pad at 30 ° C. with a liquor containing 30 parts by weight of the dye of the formula which has been finely divided

CH,

0-02s -> <J l_ 2 ch5 cn3

■ —h - n — r "" * —cm ho

? H2

nh-c0-ch

-ch,

0-0ps-n <;

~ NH,

CU7

3rd

65

Contains 1.0 part by weight of polyacrylamide with a K value of 120 and 0.5 part by weight of a polyglycol ether of oleyl alcohol and 968.5 parts by weight of water. After drying, it can be fixed in the heat setting frame at 210 ° C for 60 seconds. After subsequent rinsing and completion, as described in Example lb), paragraph 3, a strong greenish yellow color is obtained which has very good fastness properties, in particular very good fastness to light and heat setting.

c) The coupling component required for the preparation of the dye can be prepared analogously to the information in Example 1, paragraph c), by using an equimolar amount of acetamide instead of the N-methylformamide.

100 parts by weight of polyester material can be treated for 30 minutes at 121 ° C. 1500 parts by weight of tetrachlorethylene, in which 2.0 parts by weight of the dye described in Example 2a) are dissolved.

632292

After rinsing with warm and cold tetrachlorethylene, a strong greenish yellow color with very good coloristic properties is obtained.

Also greenish yellow colorations of very good coloristic properties are obtained if the polyester material is replaced by 100 parts by weight of triacetate or 21/2 acetate material and dyed for 45 minutes at 110 ° C or 45 minutes at 80 ° C .

The table below shows further dyes according to the invention prepared by coupling according to the rules of Examples 1 to 3, which give strong yellow to red colorations or prints on polyester materials with very good coloristic properties.

X

fit

U - M ~ ^ -t ridi. t, J ^ .0

oo

J

Ii.-,

15 D, X, Ri, R2 and R3 have the meaning given above.

No. D

X

R "

RP.

R-

4th

no2 //

N0?

2 1

cn

3 - \ T ^ ° 2

cn

-C4Hg (n)

-CH, 3rd

-CH.

CH

.K Y n t

-CH

-H

■ CH-

-H

~ h

-ch3 -ch3

-C3H? (N) -CH3 -H

-H -C4Hg (n) -CH3

J— \, C0Hc

-c XVch0-N (2 5 -ch

V = _ / "C ^ H

h "" "3 2 5

/ CH3

o-o9s-n <-ch7 'ch3 j

-H -C ^ Hg (iso) -H

-H

-H

-H

7

Br

-CHV 3

-CH3 -C3H? (N) -CH3

8 _ / -S02- ° CH3 -CH3 -II -CH3 -CH3

No.

9

10th

11

12th

13

14

15

16

17th

18th

19th

20th

21st

io

D

x

R "

r,

r-

o n ° 2

CN

NO,

-CH3 -C4H9 (n) -CH3 -CH3

-ch3 "H -C3H? (n) -H

-ch3 -h -c ^ h11 (iso) -h

-C3H? (N) -H -CH3 -CH3

-CH3 -H -C ^ i ^ Cn) -CH3

-ch3 -ch3

-C3H7 (iso) -H

-ch-, 3rd

0 ° 2

C0-0C4Hg (n)

-C4Hg (iso)

-CH-

CN

-C4Hg (iso)

-ch-, 3rd

-H

-H

-H

-ch-

-H

-H

-C ^ Uso) -CH3

-c2h5 -ch3

-c2ii5 -c2h5

-h -h

-H

- <> 02 _ch3 -ch3 -cii3 -ch3

-c \ cN -C4Hg (n) -H -CH3 -C3H7 (n)

11

632292

No.

D

X

R.

R ~

'j

22

23

24th

■ {=, N02

Cl no2

25 - ^^ CN

26

N0o

-Cli-

-II

-CH, -H

3rd

■ C6H13 (n) -CH.,

-CH, -C3II7 (n)

-CH ,. -CH3 -II -C4Hg (tert.)

-C3H? (N) -C2H5 -C4H9 (n) -CHj

-CH., -CH. 3:

-CH,

27th

-O "o2

28

Cl

'-NO,

CN

■ 'Q

30th

-N0o

CN

-CH, -C ^ Hc 3 c- J

-H

-H

-CH, -CH, -Cli, -N:

• C-, H „(n)

0 1

-ch-

-H

■ C2H5

c2ir5

-H

-H

-H -C6li13 (n) -CH-

31 - (_JH; 0-0C10 !! 21 (n)

-CH-

/ -tf T

- LJl-r

-CH3 -0C4H-q (tert.)

32 - <^ ~ ^ -CO-OC2H3 -CH- -CH3 -CH3 -OC ^^ iso)

-H -CH, -OCH,

3 3

632292

12th

No. D

A 'R ^ R-2 RJ

36

37

-CH-

-CH-

• H -CH3 -OCH3

-H -CH3 -0C4Hg (n)

-H -CH, -OCH,

3 3

■ H -CH, -CH,

3 3

-CH, -H -CH, -CH.

-CH

3 -Ii -CH3 -C3H? (N)

-CH, -CH-

• c6h13

-CH.

41 l / ^ - S02-CH3 -C4Hg (n) -H

-CH, -CH-

42

43

44

- <0Kco-CH3

Cl

- ^} - No2 W CH,

-CH, -H

-C4H9 (iso) -CH3

-CH, -H -CH

3 -OC ^ H ^ i ^ (iso)

■ CH

3 -CH3 -CH3 -C ^ Hg (tert.)

45 _ <(3 ^ n02 _CH3

-CH-

CH,

-CH, -N ^ 0

3 CH,

3rd

(east) ^ hzd- (u) 6hf / 0- çezd- £ h0-

\\ //

LÇ

(east) 5 | -hz0- ÇH0- (east) ^ h ^ o- ÇHZD ~

\\ 0

$ 9

Vo £> ~

ho h-

-ho- £ ho- (u) 6h ^ do - ^^) - s5

h "¥ d- £ hd- (îtss) 6h ^ o- ^ hoo -> - ^

h- (u) £ i, h9d- £ h0- cho- ^

(u) h 00 "ho ho-

H-

h- (n) 6h + 70- ^ ho-

■ ho- "ofk y se

'° H /> - ^

m h- slo- vo ~ (east) zh ^ o ~

W //

OS

(OST) 1 ^ 00-

"IIO"

ç Ç

ho- h0 ~

'on -h ■ 6 ^ 7

(• ^ .jc0q.) 6h ^ o- h-

ç-

ho-

êh0-

'on

8 + 7

no h-

H-

5?

h ° 0 "

: h0-

Vd fiZ) ^ '

bH60

1 * 1

I.

H-

H-

h- (east) 6h1? 0-

C.

"H

"h x

a * aN

z6z z £ 9

£ 1

632292

No. D

X

14

R

1

R,

R-

58 3 -CH ^ -CH3

-CH, -CH,

3 3

59 ^ J> -Br

-C, Hr, (iso) -H 3 /

CN

61 - <f ~ VN02 -C4H9 (sec) -II

-CH3 -OC ^^ iso)

-C6H13 (n) -CH3

• C3H7 (n) -C2H5

Cl I

62 -Çpo,

-CH-

-CH-

-H

-H

ch0-ch0-ch, -H -I <223

ch2-ch2-ch3

63

// A

CH

3 -CH3 -CH3 -CqH17 (ìso). -CH3

64 CN

65 -TW

13 -CH-

-CH-

-CH

-CH.

-CH-

-CH3 -C3Hy (n)

c, h rj (iso) -h -N \ 0 1

C3H7 (iso)

3 -H -C6H13 (n) -CH3

67 - ('> N02 -C2H5

■ CH3 -C4Hg (iso)

68

- <^ y0-S02-C4Hg (n) -CH3 -CH3 -CH ^ -OC6H13 (n)

69

V%

-CH3 -ÇH-CH2-CH3 -C / {Hg (n) -C2H5 CH,

15

632292

No. D

R ..

R,

R-

C1

70 - ^ | C1

Cl

71

72

73

74

CN

75

76 - ^ 3-N02

77

78

Cl CN

79

80

£> -2

-CH-

-CH

3 -H -C4H9 (n)

-C4I-Ig (n) -H -CH,

-H

\ = / <) CH3

-ch3 -ch3

-chj -chj

-h -n

C4H9 (n) C4Hg (n)

-C3H? (N) -CH:

-C4Hg (tert) -H -H -H

-CH5 -CH3

-H

-C3H7 (n)

-CH

3rd

-H -C8H17 (iso) -H

• C4Hg (sec) -CH3 -C2H5 -H

-CH

3 ~ C4H9 (n) -C5H? (Iso) -C7H15 (iso)

-C.H

3 -CH3 "c4H9 (n) ~ CH3

-CH

3 _c4Hg (n) ~ C2H5 ~ h

632292

16

No. D

X

FL

R,

R-

CF-

81

82

V

-CH3 ~ C4Hg (iso) -CH3 -H

Cl

• CH7 3

-CH3 -H -0- ^ h ^ -Cl

-o- / hVc:

83 -v> C0-0ÇH2

CH2-0CH3

CN

84 -Ö-2

CH-

-ch3 -ch3 -oc6h13 (xi)

-CH, -CH-

-H -N

/ CH2 "f 2

X CH2 -CII2

85

O

■ / CH3 H9-CH9-N \ 0

* CH,

-CH, -CH,

3 3

-H -N

/ CH3

\

ch,

86

87

88

W "N02

-CH, -CH.

CH9-CH9 -C, Hp (n) -1 <I

4 y ch2-ch2

-CH, -CH, -CH,

■ CH3 -C4H9 (n) -CH3

ch9-chp

-N <^ ^ 0

CH2 ^ -CH2

-H

NO,

89

• ch3 -ch3 -c ^ hgctert) -h

90

NO,

-ch3 -ch3 -ch3 -oc8h17 (ìso)

91

-C / (Hg (sec) -H

-CQHiy (iso) -CH3

92

CN

2nd

-CH,

-CH, -CH,

-C3Hy (n)

(east) ^ h ^ o- êho-

(OST) ^ h ^ Q- ^ HD-

Ç. £?

* ho- * ho- com

^ HO- ^ HD-

(u) £ ,, H90- (osi) UH ^ 0- ~ HQ- £ H0 ~

\\ A

ZOl

(east) z1-h800- £ ho- £ ho ~ £ ho-

H-

H-

H- (^^ yq-) 6Ht? 0-

: ho- (l..to ^) 6hl73- lì- ('"ho-

(w) 6H ^ O- (OST) ZI-H80- SiO- ^ HO-

00 L

£ hd- (> l "5s) 6h170- h" ~ h3 ~

(u) 6! ^ - ^> z.6

: h0- (east ^ hs- kh0- sîo ~ çu

■ hd

(oc 1) ^. 0 "

H-

r

"hd-" hd-

96

£ 6

'oh h- rh0-

£

£ m "£, | o> h" Sh3 "° H '/

^ 6

• 110-

(u) Z'H ^ o- Ç}] 0- £ HO ~

h jizirj \ 7 / h £ 6

m

'H' X

a * jn z6z z £ 9

ZI

632292

18th

No. D

X R1 R2 R3

105

106

Cl

-CH3 -CH3 -CH3 -C3H7 (iso)

-CH3 -CH3 -CH3 -C4H9 (tert)

107

108

109

110

■ NO,

CN

^> 2

CN CN

-CH3 -CH3 -CH3 -C7Hl4 (iso)

-CH3 -CH3 -C5H11 (iso) -CH3

• CH3 -CH3 -CqH17 (ìso) -CH3

-CH3 -C3Hy (n) -C4Hg (n) -CH ^

m -C4Hg (sec) -H -CH,

113

114

-H

112 7 ~ N02 ~ CIi3 ~ ch3 -H

-OCqH ^ rj (iso)

-CH

3 - -C4Hg (iso) -CH3 -C6H13 (n)

CN

-CH, -CH

3 ~ CH3 "C6H13 (n)

115

116

2 -CH, -CH, -CH-

C1

^> - ° 2

N <c4H9 (n)

C4Hg (n)

-CH.

-CH, -CH, .r \ -CH

v_y

19 632292

No. D X R1 R2 R5

117 ~ \ / ~ N02 -CH3

• h -h

-H

"CH.

_ / ~ VcH -WCH3 -C4H9 (sec) _

H -H

-H

120

121

122

123

124

125

126

Cl

-b-,

O

Cl

^> ° 2

cn

-ch5

-CH, 3rd

-ch3 -c ^ hy (iso)

-ch3 -ch3

-H

, ch0-ch0

-nC no \ / ch2-ch2

■ n0o -ch, -ch-

-ch, -h

-ch, -h

-ch, -h

-ch5 -CH3

-c8h17 (.1so) -ch3

-CgH17 (iso) -CH3

-ch 3 ~ c2h5

-ch, -ch, -h -n

, chn-ch

\

n0o -ch-

~ C2H5

-H

2 2 \ <

ch2-ch ^ 1

-H

127

128

-ch, -h

-CH3 -C3Hy (n)

-ch, -h -ch, -0-

H

632292

No.

D

20th

X R

1

R,

R-

129 o-

2 -ch3 -h

130 / -NO,

-ch3 -h

-ch.

-CH-

131

132

ch,) \

è *>

wo2.

0ch, \ p chv -n \ j ch3

O

mo -

cl 2 \

■ nh2

h>

wo2.

ch, -n <3

ch3

133

134 <> 2-nh-,

-ch3 -h

-ch3 -h

-ch3 -h h3 -ch3 -h

-h -0ch-

-high-

-h -0ch-

-h -0ch-

135

-ch, -h 3

-h -0ch-

136

'/ \\

-ch3 -ch3 -ch3 -c6h13 (ii)

137

'/ \\

-ch3 -ch3 -ch3 -0c6h13 (ii)

138

-CH3 -CH3 -CH "3 -0C8H17 (iso)

-ch3 -ch3 -ch3 -ch3

21st

No.

d x ryj r2 r3

-CH3 -C3H? (N) -CH3 -H

141 <> 0-02S-NC- -C0H

C0Er "2 5 2 5

-H

142

143

// \ v_so2-CH3

Cl

147 ^^ o2-ch3

-CH, -h

■ ch, -h

-ch, -h

-ch, -h

-C / + Hg (sec) -CH3

• h -c3h7 (n)

-ch, -i-i -ch, -h

-ch, -h -ch,

-C2H5

-CH3 _C4Hg (n)

-CH3 -C4Hg (iso)

"CH ^ -C4Hg (sec)

150 - {3-0-0C- (3rd

-ch3 -c3h7 (n) -ch3 -h

-ch3 -cii3 -ch3 -ch3

-c2h5 -cii3 -c8ii17 (iso) -h

151 -0- ° 2-6H13 (n) -CH3 -CH3 -CH3 -CgH ^ Cn ')

632 292 22

Mr. D X 'R. R0 R,

I ^ D

152 -m vo ~ (^ 'v-och ^ _ch -ch, -h -och-

153

^ H (n) S0oN \ ^ y J C4H9 (n)

-ch, -h

154 -

so2-h h

-ch3

-H

-ch, -h 3

~ ch3 -h

155 - (3 ^ 02-nh- <2)

-ch3 -h

-ch3 -h

156 -V Vso2-nh-t s -ch3 -h -cii3 -h

Cl

157 - <^ ~ vsvch3

ch3

158

-ciï3 -ch3 -h

-IQN-C2H5

-ch3 -h -h -c6h13 (n)

159 <W>

Ä

160 -r Vch3

ch,

ch -ch ^

-ch, -ch, -h -n \ ^ ^ nh

^ ^ ch2-ch2

-CH3 -CH3 -C3Hy (iso) -CyH ^ (iso)

CK

i

161

162

-NO

2nd

SO "-CH, l 2?

NO,

-CH-

-H -C ^ Hg (iso) -CH3

-ch, -ch-

ch2-ch ^

■ h -n \ ^ x0

ch2-CH ^

No.

D

23

X Fi

632292

1

R-

163

164

165

cn I

// \\

no,

-CH, -CH,

3 3

-H -N

/ C4Hg (n) XC4H9 (n)

-C4Hg (tert) -H -CH ^ -H

-C4Hg (iso) -CH3 -H -CH3

166 -CH3 -CH3 -H -OC2H5

167

n ^> -ch3

-CH-

169

171

172

173

ch-

168 -C> € 0-KH-CH2-CH2-CH2-n (_ch3

dl

CN

170 7-N0

CN

^ CN

Cl

'2

Cl

NO,

N02

-CH3 CH3

~ CH, -CH, 3 3

-c0hc -ch, 2 5 3

-H -OC2H5

-H

-oc2H5

-CH3 -C4Hg (n)

-CH, -CH-

—CII3 —C4Hg (n) —H —H

• CH3 -C4Hg (iso) -C2H5 -CH3

-CH, -CH, -H -N

\

CH0-CH0v

2 h

CH2-CH ^

No.

174

175

176

177

178

179

180

181

182

183

184

185

D

24th

X, R

1

R2 Ü

C5H? (N) -H

C0-0CH-

-ch, -ch.

-ch, -ch,

-ch, -ch,

-ch, -ch,

-ch, -ch,

-ch3 -h

-CH3 -OC ^ Hy (il)

-CH3 -OC ^ Hy (n)

• H -CjH ^ Cn)

C-Hq (ìso) • H -N <4 y

C4Hg (iso)

-high,

2 -CHj -h -C3Hy (iso) -CH3

-TVcO-H <f2

w ch2

co-nh-ch-

CoH

CO-N

0 \\

2 5

c2h5

CO-l / H p

-ch, -h

-C4H9 (sec) -CH3

-ch, -ch, -ch, -och-

-ch, -ch, -ch, -oçh,

-ch, -ch, -ch, -och,

V \\

-CH3 -h -C3Hy (iso) -CyH15 (iso)

25th

632292

No.

D

R "K '

R-

186

■ CH3 -H -CH3 -C ^ E ^ (n)

187

188

189

190

NO

NO

Cl

- <^ ~ ^) - N0,

-ch, -ch-

-CH, -CH-

-c2h5

-CH-

CH.-CH ^ ■ H -N <^ ^ XNH ch2-CH ^

■ ch3 -oc2h5

-CH3 -CH3 -CH3 -OC3H? (N)

-CH3 -N \

CH, / 3

CH,

191 vj ^ 0- ° - (ch2-ch2 ~ 0vch3 _ch3

-ch-

D

-H

■ OC ^ Hy (iso)

192

^ Ko-o-ch2-ch2-oh -ch3 -ch3 -H -oc3hy (iso)

193

// \ N

194

0-0-CH2-CH2-0-0C-CH3 -CH,

c0-0- (ch2-ch2-0) 3-c2h5

'! W

-ch, -h

■ 0C4Hg (n)

-CH3 -CH3 -H -0C3Hy (iso)

195

co-o-ch2-choh-ch3

-CH,

-CH, -H

3rd

-OC4Hg (n)

co-o- (ch ^ -ch2-ch2-o) 2-ch3

196 _ / v

-CH,

-ch3 -h

-0C4Hg (n)

26

left

D

X

R,

R,

£

Fs

197

198 -

co-oc2h5

o-oc2h5

199

co-o-

//

-CH-

-ch3 -h -ch3

-CH3 -C4Hg (sec) -CH3

-CH3 -CH3 -C5H11 (iso) -CH3

-C3H? (N) -C4Hg (n) -CH3 -CH3

ch3

200 - (^ 0-a ^ c (ch3 -ch3-ch3

CH-

J / Vco-o— <H> - (

-CH3 -CH3

201 ^ -Cü-Q- ^ H ^ -C4Hg (sec) -CH3 -CH3 -CH3

202 - ^^ - CO-O-HgC- ^ ^

ch,

203

-C ^ Hg (tert)

-ck-, -ch, -ch, 3 3 3

-CH, -H

-H -C? H15 (iso)

204 - ^ ty ^ co-cgh ^ n) -ch3

-CH, -H -H

3rd

H-

0 = c

205 -K \ J »3

206

// V

o = .c ^ ~ ^ -qch3

207 -

-CH3 -C3H7 (n) -H -H

-CH3 -CH3 -H -0C4Hg (sec)

-ch3

-ch3 -h -0C4Hg (sec)

27th

No.

D

x r1 r2 r3

r y ch.

212 -

213

214

J

ch-

■ a;

-CH3 -CH3 -CH3 -C ^^ n)

-CH3 -C3H? (N) -H -CH-

-CH3 -H -CH3 -H

-ch

3 -ch3 -ch3 -cyh ^ 3 (n)

-ch3 -h -ch

-CH-

-CH3 -H

-C3H? (N) -CH3

3rd

-ch, -h -ch.

N09 -CH3 -H -H

OCH-

-h -ch3 - (h

-CHj - ^. C ^ W

-n

/ c4H9 (sec) VC4H9 (sec)

■ H

-H

-CH, -CH,

3 3

-ch3 -h

-C / + Hg (tert) -CH3

-H

-C4Hg (n)

No.

220

221

222

223

224

225

226

227

228

229

D

28

X 'R1 ft2 R3

CH, -CH, -H

Cl

■ £>,

Cl Cl

- £> ° 2 -C2H5

CN

-C2H5

CN

2nd

^ v \ _Cl CH-

ïïr

cn

-CH

3rd

■ CH.

* J0o -CH-

■ H -0C4H9 (n)

-H -CH3 -H

-H -CH3 -H

-H -H -OCH,

ch3

-H -CdH „(n) -N \

a ~ CH,

-CH, -H

-H -C4Hg (n)

Cl -CH, -H -H

-C4Hg (iso)

-H -H -CjH ^ tn)

-H -H -N

ch3

\

CH-

7 "N02 -CH3 -CH3 -CjH ^ Cn) -CH ^

-CH.

Cl

-H -H ^) - ci

No.

231

232

233

234

235

236

237

238

239

240

241

29

632292

D

X R1 ■ R2 R3

NO

• CH3 -H -C6H13 (n)

-CH-

C1

2nd

NO

2nd

-CH3 -C4Hg (iso) -CH3 -H

■ CH3 -CH3 -H -C7H15 (n)

■ CH3 -CH3 -H -C4Hg (iso)

Cl

0 <u '

W CH,

-CH3 -CH3 ~ CH3 -C4Hg (sec)

-NO

2 -C3H? (N) -CH3 -H

CN

-NO,

Br

Cl

2nd

-Oh.

-C3H7 (n) -CH3 -H -N ^

CH,

X 3

ch-

■ CH3 -C4Hg (iso) -CH3 -CH3

-CH-

ch2-CH ^ -CH3 -CH3 -N ^% IH

ch2-ch2

• CH

3 -C4Hg (iso) -H

-OCH-

-CH3 -C4Hg (iso) -H -N

-C2H5

\

C2H5

30th

No; D

X R / j R2

242 - ^ 3yKN02

-CH3 -CH3 -C4Hg (sec) -H

243

244

v_

CH-

-CH3 -CH3 -C4H9 (tert) -H

-CH3 -CH3 -CH3 -C4H9 (iso)

245

246

247

248

249

250

ch3

"0-CH3

cn

^ yN ° 2

cn

-t> ™ 2

cn cn

2nd

• CH3 -CH3 -CH3 -C4Hg (sec)

-ch3 -h -h -h

~ ch3 -h -h -ch3

-CH, -H -H -0CH-

■ CH, -H -H -N

\

ch-

ch-

-C3H7 (n) -CH3 -CH3 -C? H15 (iso)

AHz

251 - ^ J /> ~ S ° 2 "NVh" ~ CH3 -C3H? (N) -CH:

-H

Br

252 -0-, ° 2 -CH3 -C4Hg (iso) -CH3

Br

-H

31

632292

No.

d x r2 ■

cn

253 <> - MO.

CN

• ch ^ -h -h -c ^ hgcsek)

-ch3 -h

-C3H7 (iso)

■ CH3 -CH, -C4Hg (n)

-ch-

~ c2h5

ch3 -ch3 -c ^^ n) -ch,

/ - \ / CH3

257 On <

co-ch,

-ch, -ch-

3rd

• CH3 -C4Hg (sec)

258 -o-ch, 302-ch3 -c3h7 (iso) -h ~ cp ^

OÇ2H5

259

Mc2H5

Oh

260

-ch3 -h -ch3

~ c2h5

-C4hg (tert) -h -ch3 -ch,

-H

261 -f> OH

-ch,

-h -ch3 -h

262

0-C8H17 (iso)

• ch3 -h -h

-och-

263 _CH;

-h -h -och-

c2h5

264 - (3-co - (3-c1

-ch3 -ch3 -ch3

-H

632292

Kr.

D

32

X R1 R2 R?

265 - ^ ~ y-C0-0-C8H17 (n)

-ch, -ch, -ch, -h 3 3 3

266 -C VcO-NH-C8H17 (iso)

• CH, -CH-

-CH, -H 3

ch3

267 -O-o-oc -Ç) ^ n3

ch3

-ch, -h ch2-ch

-H -N

\ / ch2-chj

268 -V> S02-0-C8H17 (rx)

269

o-o2s-

270

271

272

) - ° 2S ^> cl o-O2S- (3 ^ H3

0-02S - (^ 0CH3

-ch, -ch-

-CH-

-ch3 -ch3

-ch3 -ch3 -h -0cah9 (ii)

-CH3 -CH3 -H -0C4Hg (n)

-CH3 -CH3 -H -0C4Hg (n)

-CH3 -H -0C4Hq (n)

273 - <^> - S02-C4Hg (n)

-ch, -h -ch, -h 3 3

274 - ^ ~~ ^) - S02-C8H17 (iso) -CH3

-H -CH3 -H

// \\

275

-CH3 -H -CH3 -H

\\ //

33

No.

D

X R1 R2 R3

no,

CH ^

VX S09-N ^ 3

CH, 3rd

-CH3 -H ~ CH3 -H

-CH3 -CH3 -H -OC4H9 (n)

-CH, -H -CH, -H

279

280

281

no,

282

-CH3 -H -CH3 -H

-CH, -H -CH, -CH

3 W13

-ch3 -ch3 -ch3 -och

-CH, -H -H -N

CH,

/ 3 \

CH,

283

0-02S-NH2

■ ch3

-H

-ch3

284

o-o2s-n <;

, / C4H9 (n)

C4H9 (n)

-H

-CH, -H -H -CH.

c2h5

-CH, -H -CH, -OCH-

C2H5

-CI-I3 -CH3 -CH3 -CH

632292

No. D

34

X

R / | R2 R ^

C H (n)

o-o2s-n <d '

287

C3Hy (n)

-ch3 -ch3 -h -n <^

288

o-o2s-ch3

C2H5

C2H5

-ch, -h -ch, -h 5 d

289

0-02S — C10H21 (n)

• ch, -h -h -ch,

3 3

290

0-02S-C3H7 (iso)

-ch3 -h -ch3 -och3

291 ~ \ / ~ 0- ° 2S ~ cl2H25 ^ n ^ ~ CH3 "CH3 ~ CH3 ~ 0CH3

292

0-0pS-C / Hg (n) 293 i

-ch3 -h -ch3

-ch3 -h -ch3

-H

-H

294 -0-N = N- {3 -CHj -H -CH3 -H

295 VN-N-C VH -CH, -H -CH, -CH.

ch3 ch3 297 - ^ ^ ~ N = N ~ <^

-ch, -h -ch, -h

-CH3 -CH3 -CH3 -CH,

No. D

35 632292

X R ^ j R2 R3

-ch, -ch-

299 -O-N = N-O-N02 .CHj

3 °° ^ -N = N y -CH ^

-ch-

301

302

303

-ch7

3rd

-CH, -H

-CH3 -CH3

-ch3 -ch3

-H -0ch-

-H -CH, ~ H

-CH3 ~ H -CH, -H

-CH3 -H -CH, -H

-CH, -H

CH ^ -H -H -OCH-

13 r V

306

NO,

-CH-

-CH, -CH, -CH-

j ')

632292

Ut.

d

36

x r

1 * 2 R3

307

308

NO,

2nd

^ .ci],

o /

HC II

-ch, -ch3 -ch3 -ch3

-ch3 -ch3 -ch3 -ch3

309 0on-cl o c-

c- O

-ch3 -h -ch3 -h

310

h, c n

3 11 left

° 2N-CXs.C-

-ch, -h -ch, -h

3 3

311

312

-ch3 -h -ch3 -h

-ch, -h -h -n ch,

/ 5

N.

ch,

n— n Il n

313

rw

-ch, -h

-h -0c4h9 (n)

314

h, c-s-c— n

3 n n n c-

-ch3 -h -h -0c4hg (n)

OoN

315

_c-ii

ß

-ch, -h ch3 -ch3

316

c— n il II n c-

-ch, -h -ch, -ch. 3 3:

37 632292

Abstract Ci_8alkyl or optionally substituted cycloalkyl and rs

The new dyes correspond to the formula and rs is C ^ alkyl or rs and re directly or via one

Heteroatoms are closed to form a 5- or 6-membered ring. The new dyes are particularly suitable for dyeing and printing hydrophobic synthetic X 5

JL materials in high color strength with excellent fastness

D-N = N-fj -CN ten. The preparation is carried out by diazotization of amines jjq H I-q of the formula D-nh2 which have no ionogenic groups and coupling with 3-cyano-6-hydroxy-2-pyridones of the formula i 10

CH- ^ X

^ -R2 frS ~ CN

c = o i5 hoAn> o

R- I

3 CH-R.

I.

wherein D is a group free of water-solubilizing groups,

optionally substituted phenyl, naphthyl, anthraquinone, nyl or heterocyclic radical, X and Ri = H or Ci_4alkyl, r2 = H or Ci.8Älkyl, R3 = H, Ci_7alkyl, optionally substituted

C = 0 I

r3

tuiert Cycloalkyl, -OR4 or, where R4 for 25 also represent the new compounds.

r6

Claims (9)

632292 2. Water-insoluble azo dye according to claim 1, 10 characterized in that in the formula I X is a methyl group Ri hydrogen R2 is hydrogen or a methyl group R3 is hydrogen, a methyl or ethyl group or a radical Rc -OR4 or -N \ , where R4, R5 and Re the meaning Rc a residue OR4 or -N: , in which R4 for an alkyl group with 1 to 8 carbon atoms or an optionally substituted cycloalkyl group and Rs and Rfj for an alkyl group with 1 to 4 carbon atoms, where the alkyl groups Rs and Ró can also be closed directly or via a heteroatom to form a five- or six-membered ring, stand mean. 2-methyl-4-nitraniline, 2nd PATENT CLAIMS 1. Water-insoluble azo dye of the formula X D - N = N HO - (I) CH-R. I 1 N - R0 l 2 C = 0 I. R3 wherein D is an optionally substituted phenyl, naphthyl, anthraquinonyl or heterocyclic radical free of water-solubilizing groups, X and Ri, identical or different, are hydrogen or an alkyl group having 1 to 4 carbon atoms, R2 is hydrogen or an alkyl group with 1 to 8 carbon atoms, R3 is hydrogen, an alkyl group having 1 to 7 carbon atoms, an optionally substituted cycloalkyl group or R5 3rd 632292 R3 is hydrogen, an alkyl group having 1 to 7 carbon atoms, an optionally substituted cycloalkyl group or / R5 a residue -OR4 or -N ^, where r6 R <for an alkyl group with 1 to 8 carbon atoms or an optionally substituted cycloalkyl group, and Rs and Re for an alkyl group with 1 to 4 carbon atoms, the alkyl groups Rs and Re also being closed directly or via a hetero atom to form a five- or six-membered ring can mean stand. 3-nitraniline, (Iii) NO, C = 0 R, wherein X and Ri, identical or different, are hydrogen or an alkyl group having 1 to 4 carbon atoms, R2 is hydrogen or an alkyl group with 1 to 8 carbon atoms, 3 60 couples. 3-amino-phenyl- (4'-methyl-phenyl) -sulfonic acid ester, 3-aminophenylphenylsulfonic acid ester, 3-nitraniline, 25 2-methyl-4-nitraniline, 3. Water-insoluble azo dye according to claim 1 or 2, characterized in that in the formula ID one of 3-amino-phenyl- (4'-methyl-phenyl) -sulfonic acid ester, 5 4-amino-benzophenone, 3-aminophenylphenylsulfonic acid ester, 4-amino-benzophenone, 30 4-amino-4'-methoxy-benzophenone or 3-amino-phenyl-dimethylsulfamic acid ester is derived residue. 4-methyl-2-nitraniline, 4. A process for the preparation of water-insoluble azo dyes according to claim 1, characterized in that at least one amine of the formula free of ionogenic groups Have a methyl, ethyl or n-butyl group, mean. 4-amino-4'-methoxy-benzophenone or 3-amino-phenyl-dimethylsulfamic acid ester used. 4-methyl-2-nitraniline, 5. The method according to claim 4, characterized in that a mixture of different amines of the formula II is diazotized and coupled with one or more 3-cyano-6-hydroxy-2-pyridone (s) of the formula III. 65 5 ° 0 i (III) CH-R, I 1 55 NO" I 2 C = 0 J Ro 6. The method according to claim 4, characterized in that as an amine of formula II 7. The method according to claim 4, characterized in that a 3-cyano-6-hydroxy-2-pyridone of the formula III, wherein 35 X is a methyl group, Ri hydrogen, R2 is hydrogen or a methyl group, R3 is hydrogen, a methyl or ethyl group or a radical -OR4 or ~ N - * r ^ R5 -R6 means, where R4, Rs and Re mean the D-NH2 (II) 45 diazotized and with at least one 3-cyan-6-hydroxy-2-pyridone of the formula X have a methyl, ethyl or n-butyl group used. 8. Means for carrying out the method according to claim 4, consisting of a compound of the formula 9. Composition according to claim 8, characterized in that in formula III X is a methyl group, Ri hydrogen, R2 is hydrogen or a methyl group, R3 is hydrogen, a methyl or ethyl group or a radical -OR4or -n Rq \, where R4, Rs and Re mean Rc have a methyl, ethyl or n-butyl group.