DE4208535A1 - New sulpho-heterocyclyl benzene azo di:hydro-thiadiazine di:one dyestuff cpds. - used for dyeing textile, leather or paper or in ink - Google Patents

Abstract

New azo dyestuffs are 4-(sulpho-heterocyclyl)-benzene (1-azo-4) 1,6-dihydro-1,2,6- thiadiazine-2,2-dione cpds. of formula (I) or tautomers. Z = N or CH; W = N or C; X = O, S or NR1; R = H, (substd.) 1-6C alkyl or 1-4C alkoxy, halogen, NO2, -CN, -NHR1, -NH-acyl, phenoxy, -COOH, -COOR1, -CONHR1 or (substd.) phenyl; R1-3 each = H, (substd.) 1-6C alkyl or (substd.) phenyl; Y1-2 each = =O, =NH or =N-(1-6C)-alkyl; M = H(+), Li(+), Na(+), K(+), NH4(+) or the protonated form of a 4-12C trialkylamine, 4-12C diamine or 2-12C alkanolamine; A = a (substd.) carbocyclic or N-heterocyclic aromatic gp.; B = (substd.) 1,4-phenylene. USE/ADVANTAGE - (I) are for dyeing and printing textiles, leather and esp. paper (partic. tissue paper) and for making inks (e.g., ball pen ink and printing ink). Suitable textiles include cotton, wool, silk and polyamides. (I) are very readily soluble in water, giving highly concn. aq. solns. They have good textile affinity, good exhaustion and good build-up and give brilliant yellow to yellow-green dyeing with good fastness, esp. to light and wet.

Description

The invention relates to new azo dyes, processes for their preparation and their Use for dyeing textile materials, leather, inks and especially paper.

The invention relates to azo dyes of the formula

or their tautomeric forms, in which:
ZN or CH,
WN or C,
XO, S or NR₁, wherein
R₁ is hydrogen, optionally substituted C₁-C₆-alkyl or optionally substituted phenyl,
R is hydrogen, optionally substituted C₁-C₆-alkyl or C₁-C₄-alkoxy, halogen, nitro, -CN, -NHR₁, -NH-acyl, phenoxy, -COOH, COOR₁, -CONHR₁ or optionally substituted phenyl,
R₂ and R₃ independently of one another are hydrogen, optionally substituted C₁-C₆-alkyl or optionally substituted phenyl,
Y₁ and Y₂ independently of one another = O, = NH or = N-C₁-C₆-alkyl,
MH⊕, Li⊕, Na⊕, K⊕, NH₄⊕ or the protonated form of a C₄-C₁₂-trialkylamine, C₄-C₁₂-diamine or C₂-C₁₂-alkanolamine,
A is a carbocyclic or nitrogen-containing aromatic radical, which is optionally further substituted, and
B is an optionally further substituted 1,4-phenylene radical.

R, R₁, R₂ or R₃ represent an optionally substituted C₁-C₆ alkyl group, so is including as generally in this application e.g. B. a methyl, ethyl, n- or iso-propyl, n-, sec- or tert-butyl, a straight-chain or branched pentyl or hexyl or a To understand cyclohexyl radical, the single or multiple z. B. by -OH, C₁-C₄ alkoxy or C₁-C₄ hydroxyalkoxy may be substituted.

Examples of suitable substituted C₁-C₆ alkyl radicals are: Methoxymethyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, n-propoxymethyl, iso-propoxymethyl, butoxymethyl, butoxyethyl, butoxypropyl, ethoxybutyl, Methoxybutyl, ethoxypentyl and 2-hydroxyethoxypentyl.

R, R₁, R₂ or R₃ are optionally substituted phenyl, it can be unsubstituted or single or multiple with the same or different residues act substituted phenyl. Such residues come e.g. B. in question: C₁-C₄-alkyl, including in this application generally methyl, ethyl, n- or iso-propyl or n-, sec.- or tert-butyl is to be understood, C₁-C₄ alkoxy, which in this application in general Methoxy, ethoxy, n- or iso-propoxy or n-, sec- or tert-butoxy, halogen such as fluorine, chlorine or bromine, nitro or sulfo.

Preferably, R, R₁, R₂ or R₃ as phenyl is unsubstituted or phenyl substituted with 1 to 3 C₁-C₄-alkyl, chlorine or methoxy groups, where in particular the meaning of unsubstituted phenyl is preferred.

R, R₁, R₂ and R₃ are preferably hydrogen or C₁-C₄-alkyl and especially preferred for hydrogen.

Y₁ and / or Y₂ are preferably the functional group = O or = NH, where it it is also preferred that Y₁ and Y₂ are the same. Y₁ and Y₂ are particularly preferred equal and each mean = O.

In the dyes of the formula (1), R is hydrogen, optionally substituted C₁-C₆-alkyl, C₁-C₄-alkoxy, halogen, nitro, CN, -NHR₁, -NH-acyl, phenoxy, -COOH, -COOR₁, -CONHR₁ or optionally substituted phenyl, 1 to 3 of these radicals, which may be the same or different, are present.

If R represents a radical -NHR₁, -COOR₁ or -CONHR₁, then apply to R₁ before  indicated meanings and preferences.

R is -NH-acyl, it can be in the acyl group such. B. a C₂-C₆ alkanoyl or act as a benzoyl residue. Examples of suitable C₂-C₆ alkanoyl radicals are acetyl, Propionyl, butyryl, isobutyryl, valeryl, isovaleryl or pivaloyl.

The benzoyl may optionally be as previously described for phenyl continue to be substituted.

R is preferably -NH-acyl -NH-C₁-C₄-alkanoyl or -NH-benzoyl, which is unsubstituted or with 1 to 3 C₁-C₄-alkyl, chlorine or Methoxy groups is substituted.

If R is phenoxy, this can be unsubstituted or previously phenyl described be further substituted; preferably the phenoxy is not further substituted.

R preferably represents hydrogen, C₁-C₄-alkoxy, acylamino, C₁-C₆-alkyl or Sulfophenyl.

Particularly preferred meanings of R are hydrogen, C₁-C₄ alkoxy or C₁-C₄ alkyl.

In a particularly preferred embodiment of the azo dyes according to the invention R means hydrogen or methyl.

If X has the meaning -NR₁-, the meanings described above apply to R₁ and Favors.

X is preferably NH and particularly preferably O or S.

Z preferably has the meaning N.

The preferred meaning of W is C.

When A is a fused aromatic residue, it can e.g. B. a benzene,  Act naphthalene, anthracene or phenanthrene residue, each with the exception of SO₃M and R can be further substituted with the usual substituents.

Among usual substituents in this context, for. B. halogen such as fluorine, Bromine and especially chlorine, nitro, -CN, C₁-C₄-alkoxy or C₁-C₄-alkyl to understand.

A is preferably an optionally further substituted benzene or Naphthalene radical and particularly preferred for a benzene radical which has no substituents except -SO₃M and R.

A as a condensed nitrogen-containing heterocyclic radical is, for. B. a quinoline residue and especially a pyridine residue. A represents a pyridine residue represents, the N atom in each of the four conceivable positions L₁, L₂, L₃ or L₄ in Structural element of the azo dyes according to the invention shown below

be arranged while the remaining three positions are occupied by carbon atoms and X, W and Z have the meaning given above. The N atom preferably takes the Position L₁ in the above structural element.

A can pass through as a heterocyclic nitrogen-containing radical and in particular as a pyridine radical the usual substituents such. B. halogen, C₁-C₄-alkyl or C₁-C₄-alkoxy further substituted be, but preferably carries no other substituents other than -SO₃M and R.

In the preferred azo dyes of the formula (1), A has the meaning of optionally further substituted benzene or pyridine residues. It is particularly preferred here that the benzene or pyridine residue is not further substituted.

A is particularly preferably the meaning of a not further substituted Benzene residues.  

In a preferred embodiment of the azo dyes according to the invention, A is a unsubstituted benzene radical, X O or S, Z -N = and R hydrogen.

The 1,4-phenylene radical B can optionally be replaced by the usual substituents such as sulfo, C₁-C₄-alkyl, C₁-C₄-alkoxy, halogen such as fluorine, chlorine, bromine, nitro or -CN simple or be substituted several times. B is preferably an unsubstituted one or 1,4-phenylene radical substituted with chlorine, methyl or in particular with sulfo; B particularly preferably represents a 1,4-phenylene radical which is not further substituted.

At M in the meaning of a protonated C₄-C₁₂ trialkylamine it can be, for. B. um protonated N-ethyldimethylamine, N, N-diethylmethylamine, tri-n-propylamine, tri-n-butylamine, Tri-isobutylamine and especially triethylamine or tri-isopropylamine act; Mixtures of different protonated amines are also suitable.

M has the meaning protonated C₄-C₁₂ diamine, it is z. B. an ethylenediamine or 1,3-diaminopropane, in which one or both N atoms additionally with one or two C₁-C₄ alkyl radicals, preferably methyl or ethyl radicals, are substituted. M preferably represents an N, N-dialkylethylenediamine or N, N-dialkyl-1,3-diaminopropane Examples are: N-ethylethylenediamine, N, N-dimethylethylenediamine, N, N'-dimethylethylenediamine, N, N-diethylethylenediamine, 3-dimethylamino-1-propylamine or 3-diethylamino-1-propylamine.

M stands for a protonated C₂-C₁₂ alkanolamine, it can, for. B. the protonated Form of a monoalkanol, dialkanol, monoalkanol dialkyl, dialkanolalkyl or trialkanolamine or a mixture of different protonated alkanolamines. Examples are protonated 2-aminoethanol, di- (2-hydroxyethyl) amine, N- (2-hydroxyethyl) dimethylamine, N- (2-hydroxyethyl) diethylamine, N, N-di- (2-hydroxyethyl) methylamine, N, N-di- (2-hydroxyethyl) ethylamine or tri- (2-hydroxyethyl) amine, 2-aminoethoxyethanol or diethylaminopropylamine.

M is preferably Na⊕, Li⊕ or protonated C₄-C₆-alkanolamine, where in the C₄-C₆ alkanolamines tri- (2-hydroxyethyl) amine, di- (2-hydroxyethyl) amine or a mixture of these two amines is preferred.

A preferred embodiment of the invention relates to azo dyes of the formula (1), wherein R is hydrogen, C₁-C₄-alkyl or C₁-C₄-alkoxy, X is O, S or -NH  is, Z is N, W is C, R₂ and R₃ are independently hydrogen or Are C₁-C₄-alkyl, Y₁ and Y₂ are the same and each represent = O or = NH, M H⊕, Na⊕, K⊕, NH₄⊕ or protonated C₂-C₆ alkanolamine, A is a benzene radical and B represents a 1,4-phenylene radical which is unsubstituted or with sulfo, chlorine, methoxy or Methyl is substituted.

In a particularly preferred embodiment of the azo dyes of the formula (1), R Is hydrogen or C₁-C₄-alkyl, X is O or S, W is C, Z is N, Y₁ and Y₂ each mean = O, M is Li⊕, Na⊕ or protonated C₄-C₆ alkanolamine, A is a Benzene radical and B is a 1,4-phenylene radical which is not further substituted.

Azo dyes of the formula are particularly preferred

wherein n is 0 or 1, X O or S, Y₁ and Y₂ independently of each other = O or = NH and M Li⊕, Na⊕ or protonated C₄-C₆ alkanolamine mean.

The azo dyes of the formula (1) are prepared in a manner known per se and Wise, for example in such a way that an amine of the formula

diazotized and with a coupling component of the formula

couples, for the symbols R, M, X, W, Z, A, B, Y₁, Y₂, R₂ and R₃ the previously indicated meanings and preferences apply.

The amines of the formula (4) and the coupling components of the formula (5) are known or can be produced by methods known per se. The diazotization and Coupling reactions are also known and take place under normal conditions.

The desired cation M is in the azo dyes of the invention Formula (1), for example, introduced so that the z. B. by filtration and Wash out isolated and purified diazonium salt of the amine of formula (7) into one aqueous mixture which contains the coupling component and a basic Lithium, sodium, potassium or ammonium salt or hydroxide, a C₄-C₁₂ trialkylamine or C₂-C₁₂ alkanolamine or mixtures of various alkylamines or alkanolamines contains.

The new compounds of formula (1) are used primarily as dyes for Dyeing and printing of textile materials, paper, leather and for the preparation of inks.

The dyes of the formula (1) are very readily water-soluble, so that they are highly concentrated have aqueous solutions prepared.

Are the azo dyes according to the invention used for dyeing and printing textile materials, so come from z. B. cotton, wool, silk or polyamide materials in question. The new dyes have a good draw on these textile materials, a good degree of exhaustion and structure, and the colorations obtained have good Fastness properties, especially good wet fastness properties and light fastness properties.

The preferred use of the dyes of the formula (1) according to the invention is in the application for dyeing and printing paper of all kinds, especially bleached and sized lignin-free paper.

The dyes of the invention draw very well on these substrates, the Waste water - even with deep nuances (up to 1/1 RT = standard depth) - practically colorless remains, which is an eminent technical and ecological advantage. The good degree of exhaustion is also advantageous for good reproducibility of the shade. The colors are  wet fast, d. H. They show no tendency to bleed when colored paper is wet Condition is brought into contact with damp white paper. This property is especially desired for so-called "tissues", where it is foreseeable that the colored paper when wet (e.g. soaked with water, alcohol, surfactant solution etc.) comes into contact with other surfaces such as textiles, paper and the like must be protected against pollution.

The yellow to green-yellow colors are brilliant and have very good fastness properties lightfastness.

The dyes of the formula (1) are also used for dyeing leather materials according to the various application processes, such as spraying, brushing and dipping and for preparation of inks of all kinds such as for ballpoint pens and printing inks.

The following examples illustrate the invention without limiting it. The temperatures are given in degrees Celsius, parts (T) mean parts by weight, and % Figures are percentages by weight.

example 1

64 parts of the diazo component of the formula

are suspended in 1000 parts of distilled water and with 30% aqueous NaOH solution (approx. 8 parts) adjusted to pH 7 to 7.5. You give 400 parts of ice cream and one Solution of 15 parts of NaNO₂ in 50 parts of water. 48 parts are made within 5 minutes 32% hydrochloric acid stirred in and the resulting lemon yellow suspension for 1 hour stirred, the temperature being maintained at 0 to 5 ° C. After that the excess nitrite destroyed with sulfamic acid.

33 parts of the coupling component of the formula  

- Made according to I. Alkorta et al., J. Chem. Soc. Perkin Trans I, 1988, 1272 - are suspended in 2000 parts of saturated sodium acetate solution and by adding Ice cooled to 0 to 5 ° C. Now the above-mentioned diazo suspension becomes within 15 minutes stirred in; an orange precipitate forms. Stir for another 2 hours 0 to 5 ° C further, adds 1000 parts of 25% sodium chloride solution, stirring for 15 minutes continues and sucks off. After drying, 88 parts of the compound of the formula are obtained

in the form of a yellow-orange powder.

The dye is very soluble in water and dyes paper in very yellow shades good fastness properties.

Example 2

64 parts of the diazo component of the formula

are, as described in Example 1, diazotized.

This suspension is analogous to Example 1 in a suspension of 41 parts of Coupling component of the formula  

stirred in 2000 parts of saturated sodium acetate solution. The processing takes place likewise analogous to example 1. The compound of the formula is obtained

in the form of an orange powder.

The dye is very soluble in water and dyes paper in very yellow shades good fastness properties and shows an excellent structure.

The coupling component used is obtained in the following way: 59 parts of potassium metal are portioned into 600 parts of anhydrous water with cooling Given isopropanol. After a while the evolution of hydrogen subsides; one doses anhydrous methanol slowly so that a steady, not too violent Hydrogen development occurs. After the potassium has dissolved, the cooling bath is removed, and then 72 parts of sulfamide dissolved in 700 parts of anhydrous methanol, stirred in, forming a white suspension. 100 parts are now within 4 hours Diethyl malonate, dissolved in 300 parts of anhydrous methanol, added and then stirred for a further 16 hours.

The resulting white precipitate is filtered off, washed with a little methanol and dissolved in 2500 parts of water. By adding glacial acetic acid to the solution pH set at 5 and then to a quarter of the original volume constricted. After adding 1200 parts of ethanol, a white precipitate is formed. Man dissolve this in as little water as possible and make the solution by adding 0.1 N HCl  to a pH of 2.5. After vacuuming off the precipitation and Drying gives the compound of the formula

in the form of white crystals.

Examples 3-13

The procedure is as described in Example 1, but uses that in the table below diazo components listed under (A) and the coupling components mentioned under (B), this gives azo dyes, the paper in the shades given in column 4 dye with good fastness properties.  

Example 18

By dissolving 1.0 g of the dye compound of Example 2 in 500 ml of water prepares a dye stock solution. Then 10 ml of this solution become a suspension of 4.0 g (dry weight) bleached sulfide fibers in 300 ml of water, and the stock suspension is then stirred at room temperature for 10 minutes. Then it will be added the sizing agent, which consists of 1.5 ml of 4 percent tree resin solution and 3 ml 4 percent aluminum sulfate solution. The pH value of the dye bath is too at this point about 4.5. Stirring is continued for 15 minutes before the colored one Mass is filtered on a sieve. The paper is in a very intense, brilliant, lightfast yellow shade. The degree of exhaustion is <90%.

Claims (20)

1. Azo dyes of the formula or their tautomeric forms, in which:
ZN or CH,
WN or C,
XO, S or NR₁, wherein
R₁ is hydrogen, optionally substituted C₁-C₆-alkyl or optionally substituted phenyl,
R is hydrogen, optionally substituted C₁-C₆-alkyl or C₁-C₄-alkoxy, halogen, nitro, -CN, -NHR₁, -NH-acyl, phenoxy, -COOH, COOR₁, -CONHR₁ or optionally substituted phenyl,
R₂ and R₃ independently of one another are hydrogen, optionally substituted C₁-C₆-alkyl or optionally substituted phenyl,
Y₁ and Y₂ independently of one another = O, = NH or = N-C₁-C₆-alkyl,
MH⊕, Li⊕, Na⊕, K⊕, NH₄⊕ or the protonated form of a C₄-C₁₂-trialkylamine, C₄-C₁₂-diamine or C₂-C₁₂-alkanolamine,
A is a carbocyclic or nitrogen-containing aromatic radical, which is optionally further substituted, and
B is an optionally further substituted 1,4-phenylene radical. 2. azo dyes according to claim 1, characterized in that R is hydrogen, Is C₁-C₆ alkyl, C₁-C₄ alkoxy, NH-acyl or sulfophenyl. 3. azo dyes according to claim 2, characterized in that R is hydrogen, Is C₁-C₄ alkoxy or C₁-C₄ alkyl.   4. Azo dyes according to claim 3, characterized in that R is hydrogen or Is methyl. 5. Azo dyes according to claim 1 to 4, characterized in that X is NH or especially for O or S. 6. Azo dyes according to one of claims 1 to 5, characterized in that Z N is. 7. Azo dyes according to one of claims 1 to 6, characterized in that W stands for C. 8. Azo dyes according to one of claims 1 to 7, characterized in that A for is a benzene radical or pyridine radical which is optionally further substituted. 9. Azo dyes according to claim 8, characterized in that A is a benzene radical or pyridine radical and R is hydrogen. 10. Azo dyes according to one of claims 1 to 9, characterized in that A is a benzene radical and X is O or S, Z N and R is hydrogen. 11. Azo dyes according to one of claims 1 to 10, characterized in that the 1,4-phenylene radical B is not further substituted. 12. Azo dyes according to any one of claims 1-11, characterized in that R₁, R₂ and R₃ are each independently hydrogen or C₁-C₄ alkyl, especially hydrogen, mean. 13. Azo dyes according to any one of claims 1-12, characterized in that Y₁ and Y₂ each independently represent O or NH. 14. Azo dyes of formula (1) according to claim 1, wherein R is hydrogen, C₁-C₄ alkyl or C₁-C₄ alkoxy, X is O, S or -NH, Z is N, W is C, R₂ and R₃ are independently hydrogen or C₁-C₄ alkyl, Y₁ and Y₂ are the same and each represent O or NH, M H⊕, Na⊕, K⊕, NH₄⊕ or protonated C₂-C₆ alkanolamine A is a benzene radical and B is a 1,4-phenylene radical which is unsubstituted  or substituted with sulfo, chlorine, methoxy or methyl. 15. Azo dyes according to claim 14, wherein R is hydrogen or C₁-C₄ alkyl, X is is O or S, W is C, Z is N, R₂ and R₃ are each H, Y₁ and Y₂ are each = O, M is Li⊕, Na⊕ or protonated C₄-C₆ alkanolamine, A is a benzene radical and B is a unsubstituted 1,4-phenylene. 16. Azo dyes according to claim 1 of the formula wherein n is 0 or 1, XO or S, Y₁ and Y₂ independently of one another each O or NH and M Li⊕, Na⊕ or protonated C₄-C₆ alkanolamine. 17. A process for the preparation of azo dyes of the formula (1) according to claim 1, characterized in that one of an amine of the formula diazotized and with a coupling component of the formula couples, where the meanings given in claim 1 apply to the symbols R, M, X, W, Z, A, B, Y₁, Y₂, R₂ and R₃. 18. Use of the compounds of formula (1) according to claim 1 as dyes for Dyeing and printing of textile materials, paper, leather and for the preparation of inks. 19. Use according to claim 18 for dyeing and printing paper of all types. 20. The paper dyed with dyes of the formula (1) according to claim 1.