DE4020768A1 - New triazolo-pyridine azo dyes - esp. for dyeing cellulose acetate and polyester fibres - Google Patents

Abstract

Azo dyes of formula (I) are new: (where R1 = (a) opt. substd. 1-20C alkyl opt. interrupted by one or more O atoms, or (b) opt. substd. phenyl; R2 = CN, CONH2, COOH or 2-5C alkoxycarbonyl; R3 = OH, NY1Y2 or the residue of a CH-acidic cpd.; Y1 and Y2 = H or 1-4C alkyl, or NY1Y2 is a 5- or 6-membered satd. heterocyclic gp.; D = the residue of an aniline-series diazo component). (I) are prepd. by diazotising DNH2 and coupling with a 5-methyl-(1,2,4) trizolo(1,5-a) pyridine deriv. of formula (II): Cpds. (II) are described in DE3926770. USE - (I) are esp. useful for dyeing cellulose ester or polyester fibres, but may also be used to dye polyamides or polyester/cellulose blends.

Description

The present invention relates to new triazolopyridine azo dyes Formula I.

in the
R¹ C₁-C₂₀-alkyl, which is optionally substituted and can be interrupted by one or more oxygen atoms, or optionally substituted phenyl,
R² cyano, carbamoyl, carboxyl or C₁-C₄ alkoxycarbonyl and
R³ is hydroxy, the radical -NY¹Y², where Y¹ and Y² are the same or different and each independently represent hydrogen or C₁-C₄-alkyl or together with the nitrogen atom connecting them represent a 5- or 6-membered saturated heterocyclic radical, or the rest of one CH-acidic compound and
D is the remainder of a diazo component from the aniline series.

From the older German patent application P 39 26 770.9 [1,2,4] Triazolo [1,5-a] pyridines known.

The object of the present invention was now to develop new azo dyes To provide in which these triazolopyridines as a coupling component are included.

Accordingly, the triazolopyridine azo dyes specified in the introduction of formula I found.  

The dyes of the formula I can occur in several tautomeric forms, all of which are encompassed by the claim. For example, the Dyes with R³ = Hydroxy u. a. occur in the following tautomeric forms:

If R¹ in formula I is a substituted C₁-C₂₀ alkyl group, so can as substituents such. B. phenyl, phenoxy, carboxyl or C₁-C₂₀ alkoxycarbonyl, whose alkyl chain optionally by 1 to 4 oxygen atoms interrupted and / or substituted by phenyl or phenoxy, in Come into consideration.

When R 1 in formula I represents an alkyl group represented by oxygen atoms is interrupted, such alkyl radicals are preferred which are 1 to 4 oxygen atoms, in particular 1 to 2 oxygen atoms, are interrupted.

If R 1 in formula I represents a substituted phenyl radical, then as substituents e.g. B. C₁-C₄ alkyl, C₁-C₄ alkoxy, halogen, in particular Chlorine or bromine, nitro or carboxyl come into consideration.

If R³ in formula I means a residue of a CH-acidic compound, so can this rest z. B. of nitromethane, nitroethane or of compounds of the formulas V to X

derive, whereby
X¹ cyano, nitro, C₁-C₄-alkanoyl, optionally substituted by C₁-C₄-alkyl, C₁-C₄-alkoxy or halogen-substituted benzoyl, C₁-C₄-alkylsulfonyl, optionally by C₁-C₄-alkyl, C₁-C₄-alkoxy or halogen substituted phenylsulfonyl, carboxyl, C₁-C₄-alkoxycarbonyl, phenoxycarbonyl, carbamoyl, C₁-C₄-mono- or dialkylcarbamoyl, optionally substituted by C₁-C₄-alkyl, C₁-C₄-alkoxy or halogen, phenylcarbamoyl, optionally by C₁-C₄-alkyl, C₁-C₄ alkoxy, halogen or nitro substituted phenyl, benzthiazol-2-yl, benzimidazol-2-yl, 5-phenyl-1,3,4-thiadiazol-2-yl or 2-hydroxyquinoxalin-3-yl,
X² C₁-C₄-alkyl or C₁-C₄-alkoxy,
X³ C₁-C₄ alkoxycarbonyl, phenylcarbamoyl or benzimidazol-2-yl,
X⁴ is hydrogen or C₁-C₆ alkyl,
X⁵ is hydrogen, C₁-C₄ alkyl or phenyl and
X⁶ C₁-C₄ alkyl.

CH-acidic compounds of the formulas V, VI and VIII should be mentioned in particular, where
X¹ cyano, acetyl, benzoyl, C₁-C₄-alkoxycarbonyl, phenoxycarbonyl, C₁-C₂-monoalkylcarbonyl, phenylcarbamoyl, phenyl, benzimidazol-2-yl, benzthiazol-2-yl or 5-phenyl-1,3,4-thiadiazol-2 -yl,
X² C₁-C₂ alkoxy,
X³ C₁-C₂ alkoxycarbonyl or phenylcarbamoyl and
X³ is methyl.

The rest D in the dyes according to the invention is derived from a Diazo component from the aniline series.

Suitable diazo components D-NH₂ obey, for example, the formula II or III

in which
L¹, L², L³ are the same or different and are each independently hydrogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, halogen, nitro, cyano, C₁-C₄-alkanoylamino, C₁-C₄-alkoxycarbonyl, which is optionally substituted by phenyl or the radical CO-NY¹Y², in which Y¹ and Y² each have the abovementioned meaning.

R¹ are z. B. hydrogen, methyl, ethyl, propyl, isopropyl, butyl, Isobutyl, sec-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, Heptyl, 1-ethylpentyl, octyl, isooctyl, 2-ethylhexyl, nonyl, isononyl, Decyl, isodecyl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, Pentadecyl, Hexadecyl, Heptadecyl, Octadecyl, Nonadecyl, Eicosyl (Die Above names are isooctyl, isononyl, isodecyl and isotridecyl Trivial names and derive from those obtained after oxo synthesis Alcohols - cf. also Ullmann's encyclopedia of technical chemistry, 4th edition, volume 7, pages 215 to 217, and volume 11, pages 435 and 436.), 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-isopropoxyethyl, 2-butoxyethyl, 2- or 3-methoxypropyl, 2- or 3-ethoxypropyl, 2- or 3-propoxypropyl, 2- or 3-butoxypropyl, 2- or 4-methoxybutyl, 2- or 4-ethoxybutyl, 2- or 4-propoxybutyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 4,8-dioxanonyl, 3,7-dioxaoctyl, 3,7-dioxanonyl, 4,7-dioxaoctyl, 4,7-dioxanonyl, 2- or 4-butoxybutyl, 4,8-dioxadecyl, 3,6,9-trioxadecyl, 3,6,9- Trioxaundecyl, 3,6,9,12-tetraoxatridecyl, 3,6,9,12-tetraoxatetradecyl, 2-carboxyethyl, 2-methoxycarbonylethyl, benzyl, 1- or 2-phenylethyl, 3-benzyloxypropyl, phenoxymethyl, 6-phenoxy-4-oxahexyl, 8-phenoxy-4-oxaoctyl, 2-, 3- or 4-methylphenyl, 2-, 3- or 4-methoxyphenyl, 2-, 3- or 4-chlorophenyl, 2-, 3- or 4-nitrophenyl or 2-, 3- or 4-carboxylphenyl.

R² are z. B. methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, Butoxycarbonyl, isobutoxycarbonyl or sec-butoxycarbonyl.

R³ are z. B. amino, mono- or dimethylamino, mono- or diethylamino, Mono- or dipropylamino, mono- or diisopropylamino, mono- or Dibutylamino, pyrrolidino, piperidino, morpholino, piperazino or N- (C₁-C₄-alkyl) piperazino.

Examples of diazo components D-NH₂ are:

Aniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-chloroaniline, 3,5-dichloroaniline, 2-methoxyaniline, 4-methoxyaniline, 2,5-dimethoxyaniline, 3-acetylaminoaniline, 4-acetylaminoaniline, 2-methoxy-4-acetylaminoaniline,  3-methoxy-4-acetylaminoaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2,5-dinitroaniline, anthranilic acid methyl ester, anthranilic acid ethyl ester, 3-aminobenzoic acid methyl ester, 3-aminobenzoic acid ethyl ester, 3-aminobenzoic acid benzyl ester, 3-aminobenzoic acid (2-phenylethyl) ester, Anthranilic acid amide, 3-aminobenzamide, 4-aminobenzamide, 3-amino-2-methoxybenzamide, 2-dimethylcarbamoylaniline, 3-dimethylcarbamoylaniline, 4-dimethylcarbamoylaniline, 2-cyanoaniline, 3-cyanoaniline, 4-cyanoaniline, 2-cyano-4-nitroaniline, 4-phenylazoaniline, 4-phenylazo-2-methylaniline, 4- (2-methylphenylazo) aniline, 4- (2-methylphenylazo) -2-methylaniline, 2-chloro-4-nitroaniline, 2,6-dichloro-4-nitroaniline, 2-bromo-4,6-dinitroaniline, 2-cycano-4,6-dinitroaniline, 2,6-dicyano-4-nitroaniline or 4-methoxy-2- nitroaniline.

Triazolopyridineazo dyes of the formula I in which R 2 is cyano are preferred means.

Triazolopyridineazo dyes of the formula I in which R³ is hydroxy or the radical -NY¹Y², where Y¹ and Y² are each has the above meaning.

Triazolopyridineazo dyes of the formula I in which R¹ is C₁-C₁₀ alkyl.

Triazolopyridineazo dyes of the formula I in which R¹ is C₁-C₈ alkyl, R² is cyano and R³ is hydroxy.

The triazolopyridine azo dyes of the formula I can can be produced by methods known per se. For example one known per se a diazo component of the formula II, III or IV diazotize and with a coupling component of formula V

in which R¹, R² and R³ each have the abovementioned meaning, couple.

As already mentioned at the beginning, the coupling components of the formula V are known and z. B. in the older German patent application P 39 26 770.9 described.  

The triazole pyridineazo dyes according to the invention are particularly advantageous Way of dyeing textile fibers, especially fibers Cellulose esters or polyesters, but also made of polyamides, or of blended fabrics made of polyester and cellulose fibers.

This gives dyeings with high light fastness and good Wet fastness properties.

The following examples are intended to explain the invention in more detail.

Example 1 a) Diazotization

13.8 g of 4-nitroaniline were 1 hour at 50 ° C in 180 ml of 17 wt .-% Hydrochloric acid and 1 g of a dispersant based on oxyethylated Oleylamine stirred. The mixture was then cooled to -5 to 0 ° C. with 300 g of ice. At this temperature, 32 ml of aqueous sodium nitrite solution (23% by weight) are added and then 2 hours at max. 5 ° C stirred. The excess nitrite present was then treated with 1 g of amidosulfonic acid destroyed.

b) clutch

45.4 g of 6-cyano-2-heptadecyl-7-hydroxy-5-methyl [1,2,4] triazolo [1,5-a] pyridine was dissolved in 1000 ml of N, N-dimethylformamide (DMF) and 1000 ml N-methylpyrrolidone stirred and then with 2 g of an alkyl polyethylene glycol ether and 2000 g of ice added. The diazonium salt solution prepared under a) was then within 40 minutes at max. + 5 ° C added. Subsequently, the pH was brought to a pH of 400 g with sodium acetate. Value from 5 to 6 and stirred for 2 hours at 0 to 5 ° C. You let the reaction mixture warm to room temperature, sucked the formed Precipitate, washed it and dried it at 40 ° C under reduced Print.

59.8 g of the dye of the formula were obtained

λ _max = 455 nm (CH₂Cl₂)

The dye dyes polyester fabric in a yellow tone.  

The dyes listed in the following table are used in an analogous manner of the formula

receive.

table

Claims (3)

1. Triazolopyridine azo dyes of the formula I. in the
R¹ C₁-C₂₀ alkyl, which is optionally substituted and can be interrupted by one or more oxygen atoms, or optionally substituted phenyl,
R² cyano, carbamoyl, carboxyl or C₁-C₄ alkoxycarbonyl,
R³ is hydroxy, the radical -NY₁Y₂, where Y¹ and Y² are the same or different and each independently represent hydrogen or C₁-C₄-alkyl or together with the nitrogen atom connecting them represent a 5- or 6-membered saturated heterocyclic radical, or the rest of one CH-acidic compound and
D is the remainder of a diazo component from the aniline series. 2. Triazolopyridines according to claim 1, characterized in that R² cyano means. 3. Use of the triazolopyridine azo dyes according to claim 1 for Dyeing textile fibers.