CZ300680B6 - Metal complex azo dyes based on citrazinic acid, process of their preparation and method of dyeing animal and synthetic substrates - Google Patents

Abstract

In the present invention, there are disclosed metal complex azo dyes based on citrazinic acid (2,6-dihydroxypyridine-4-carboxylic acid; 2,6-dihydroxyisonicotinic acid) of the general formula I, in which the group X is on the aromatic system Ar in ortho position relative to the azo group and X = O, NH, C(=O)O; Z denotes Fee2+ and n = 2, or Z denotes Fee3+ or Coe3+ and n=1; Me=H, Li, Na, K, NHi4; Me+ = Lie+, Nae+, Ke+, NHi4e+; Ri1, Ri2 represent independently on each other H, F, Cl, Br, I, SOi3Me, C(=O)OMe, POi3Mei2, OR, OH, NHi2, NHR, NRi2, SH, SOi2NHi2, CONHi2, NOi2, CN, SOi2R, SOi2NHR or CONHR; R represents alkyl containing 1 to 8 carbon atoms; Ar denotes and aromatic system containing 6 to 10 carbon atoms, whereby is includes at a temperature ranging from one aromatic nucleus. There is also disclosed a process of their preparation from a starting azo dye and a metal salt, further a method of dyeing animal and synthetic substrates using these dyes as well as process of their preparation in situ on an animal substrate.

Description

(57)

A compound of the formula I wherein the X group is on the aromatic Ar in ortho position to the azo group and X = O, NH, Q-Ό) O Citrazinic metal-complex azo dyes (2,6-dihydroxypyridine-4-carboxylic acids; 2,6-dihydroxyisonicotinic acid); ; Z is Fe ²⁺ and n = 2, or Z is Fe 2 or Co ³⁺ and n-4; Me-H, Li, Na, K, NH <M ⁺ = Li ⁺ , Na ⁺ , K ⁺ , NH 4 ⁺ ; R 1, R 2j are independently H, F, Cl, Br, 1, SO 3 Me, C (= O) OMe, PCLMe OR, OH, NH ₂ , NHR, NR ₂ , SH, SO ₂ NH ₂ , CONH _2> NO _CN, SO ₂ R or CONHR SOjNHR; R = C 1-6 alkyl; Ar is an aromatic system containing 6 to 10 carbon atoms and contains at least one aromatic ring. A method for their preparation from azo dye and a metal salt, a method for dyeing animal and synthetic substrates with these dyes and a method for their in situ execution on an animal substrate.

Metallic complex azo dyes based on citrazic acid, process of their preparation and method of dyeing animal and synthetic substrates

Technical field

The invention relates to metal complex acid and mordant organic azo dyes, to a process for their preparation and to a process for dyeing animal substrates and synthetic substrates.

BACKGROUND OF THE INVENTION

The metal-composite azo dyes used for dyeing animal substrates (e.g., wool, silk, leather) are those where the chromophore as a color carrier is bonded as a multi-valent ligand to a transition metal, usually Cr ³⁺ , Co ³⁺ , Fe ^{2 + / 3 +} , Al3 ⁺ . Metal complex dyes are further divided into so-called pre-metallized dyes, where the metal complex dye is prepared by the dye manufacturer (acid dyes class) and this dye is then used to dye the substrate or so-called mordant, where the metal complex dye is prepared on the fiber in the chromophores dyeing sequence and then by the so-called metallization of metal salts in the dyeing bath. Dyes used for the preparation of pre-metallized dyes and used as mordant dyes have functional (nucleophilic) groups (OH and O, NH ₂ , COOH and COO, respectively) capable of forming metal-complex bonds with heavy transition metal ions in their molecule,

Pre-metallized azo dyes are divided into so-called 1: 1 and 1: 2 metal-complex dyes according to the number of ligands (or starting chromophores) bound to the central metal ion.

The structure of these dyes is usually described in the literature in the form of an azo, without distinction of the trans (Eforma) / cw (Z-form) isomerism, although the starting dyes having an OH group ortho to the azo group predominantly hydrazone and trans ( Yagi Y, Bull, Chem Soc Jpn, 37 (12), 1881, 1964, Schetty G., Steiner E., Helvetica Chimica Acta, 57 (7), p.2149, 1974).

In metal-complex dyes the situation is disproportionately more complex, bound ligands are usually ligand trans form (Lyčka A., Holeček J., Dyes and Pigments 57, 115-119, 2003; Lyčka A., Jirman J., Cee A., MRC 28 408-413 (1990). The broad absorption bands of these metal-complex dyes suggest that the fiber is most likely a mixture of isomers.

Pre-metallized dyes fall into the class of acid dyes and the dyeing of substrates with these dyes is performed from an acidic water dye bath at 80-100 ° C, the pH of the dyeing bath is 3-5. For use of heavy metal pre-metallized dyes (Cr ³ *) , Co ³⁺ , Cu ² \ and the like) there are strict rules concentrated eg in standard 2002/3 71 / EC.

Process for dyeing mordant dyes are traditionally carried out by first animal substrate (this technique is dyed wool fiber) stained wood grain starting dyes, because of the acidic aqueous dyeing bath at 80 to 100 ⁱⁿ C. Thereafter, the goods are in the so-seas. Chromační bath (water, pH dyeing bath 3 to 5, 80 to 100 ° C) with sodium or potassium chromate or dichromate. Wool (generally an animal substrate) has reducing properties, so that Cr ⁶⁺ to Cr ³ * is reduced, where the trivalent chromium cation forms a complex with the dye and the fiber, which has excellent coloristic properties, ie. high fastness, both wet fastness and high light fastness.

On the other hand, hexavalent chromium compounds have been found to be particularly hazardous (labeled T +), which poses considerable hygiene and environmental problems. Dyes are usually superior to pre-metallized dyes because the starting mordant dye (ligand) has a smaller molecule (as compared to pre-metallized dye), so that it better penetrates deep into the fiber. Pickling then usually produces 1: 2 complexes within the fiber (Race et al., J. Soc. Dyers Color. 62, 372, 1946). In dyeing terminology, the colors are calm, deep and stable. When using a pre-metallized dye, it can occur that only the surface of the fiber is colored, the coloring being so-called restless and not very stable, e.g.

However, in some cases, hexavalent chromium also oxidizes the starting stain 5 (if this reaction is carried out on a fiber or in a bath, it is not clear) to form a dye which additionally

-O and OH groups, and which, when complexed with Cr ^3t, give a substantially bathochromically shifted color on the fiber. The mordant dyes are mainly used for the preparation of black coloring high permanent oxidation dye and complexation can sCr ⁱⁿ "in situ" on the fiber also be performed using hydrogen peroxide together with a chromic salt (Hero Radim et al., CZ 293 743 B6).

The mordant dyes can be stained on the wool fiber with trivalent chromium salts as well as with salts of other metals (eg Al ¹ ), but this technique is practically not used in the dyeing industry.

Some authors believe that metal-complex dyes, whether applied to a fiber as a reprocessed or mordanted, have high laundering properties because, for example, the following general structures form on the fiber during dyeing (pickling):

NH ₂ , C00.0 where B represents the functional groups of the substrate (eg B = O, S, NH ₂ ). This structure would be indicative of high wash stability since the dye is caught on the fiber by a coordinating bond. In addition, high light fastnesses are indirect proof. For example, it is known that if the amount of the so-called free amine (-NH ₂ ) groups in the wool fiber is reduced, the light fastness will increase. On synthetic polyamides, this phenomenon is described, for example, in PC Miranda, LM Rodrigues, MST Goncalves, SPG Costa, R. Hrdina, AMF Oliveira-Campos: Synthesis, Washing and Light Fastness of Azo Dyes Derived frotn Ν, Diet-Diethylanilines. Advances in Color

Science and Technology, Vol.4, Num.1, University of Leeds, 2001. However, increased light fastness is also due to the presence of a metal ion. Anyway, direct evidence of the existence of the above structure is lacking.

Metal-complex dyes derived from peracetic acid and heterocyclic diazonium components are described in U.S. Pat. No. 2,857,372, chromocomplex dyes with the residue of peracetic acid are described in Czech Patent Certificate CS-216 607.

Acidic and reactive monoazo dyes with citrazinic acid in the molecule are the subject of the Czech invention (CS 216 606), the protection covering the coloring of cellulose in greenish-yellow hues35.

Metal-complex azo dyes derived from peracetic acid and its analogues and 2-aminobenzoic acid as primary components are also spectroscopically described in Mamdouh SM et al., Spectrochimica Acta, Part A, 60 (2004), 2807-2817, but the structure of the complexes is completely unrealistic ( the metal ion is bound to the functional groups of the heterocycles) than is actually the case. One example of this publication is as follows.

O w υπ

Moreover, the authors erroneously assume that the cobalt ion is divalent in this complex.

The chemistry of cobalt compounds is quite complicated because, with two exceptions, there are no 5 cobalt-free salts. Although it was possible to prepare cobalt fluoride and cobalt sulphate (Co ₂ (SO ₄ ) ₃ .18 H ₂ O), they hydrolyze rapidly in water (especially alkaline) and are converted to cobalt salts by the action of acids. Conversely, complex cobalt compounds are stable even in aqueous solutions.

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SUMMARY OF THE INVENTION

The present invention provides metal-complex azo dyes based on citrazic acid (2,6-dihydroxypyridine-4-carboxylic acid; 2,6-dihydroxy-sonicotinic acid) of the general formula:

MeOOC n-

COOMe group X is on the aromatic Ar in ortho position to the azo group and X = O, NH, C (-O) O;

Z is Fe ²⁺ and n = 2 or Z is Fe ³⁺ or Co ³⁺ and n = 1;

Me = H, Li, Na, K, NH ₄ ;

R ₂ are independently H, F, Cl, Br, I, SO 2 Me, C (= O) OMe, PO ₃ Me ₂ , OR, OH, NH ₂ , NHR, NR ₂ , SH, SO ₂ NH ₂ , CONH ₂ , NO ₂ , CN, SO ₂ R, SO ₂ NHR, or CONHR;

R = C ₁₈ alkyl;

_ 2 _

Ar is an aromatic system containing 6 to 10 carbon atoms and contains at least one aromatic nucleus (aromatic system of the benzene or naphthalene type).

The present invention further provides a process for the preparation of pre-metallized dyes of formula (5), which comprises mixing a starting dye of formula (II) in water.

wherein the X group on the aroma Ar is ortho to the azo group and

X = O, NH, C (= O) O;

R 1, R ₂ are independently H, F, Cl, Br, I, SO ₃ Me, C (= O) OMe, PO ₃ Me ₂ , OR, OH, NH ₂ , NHR, NR ₂ , SH, SO ₂ NH ₂ , CONH ₂ , NO ₂ , CN, SO ₂ R, SO ₂ NHR or CONHR;

Me - H, Li, Na, K, NH ₄ ;

R = alkyl C _1-8 ;

Ar is an aromatic system having 6 to 10 carbon atoms and containing at least one aromatic nucleus (aromatic system of the benzene or naphthalene type), with an alkali followed by a water-soluble iron or cobalt salt, and the reaction mixture is heated to a temperature of 40 to 140 ° The alkali causes deprotonation of the starting dye II, and the resulting nucleate 25 is then reacted with an electrophilic metal ion particle. The resulting product of formula (I) is then isolated from the reaction mixture.

It is a feature of the invention that the alkali used is NaOH, KOH, LiOH or NH ₄ OH.

It is also a feature of the invention that the water-soluble metal salt is an iron, iron, cobalt or cobalt salt, preferably a salt selected from the group consisting of, in particular, FeSO ₄ .7H ₂ O, FeCl ₂ , FeCl ₂ .6H ₂ O, FeCl ₂ .4H ₂ O, Fe ₂ (SO ₄ ) ₃ .9H ₂ O, Fe ₂ (SO ₄ ) ₃ , FeCl ₃ , FeCl ₃ .6H ₂ O, (CH ₃ COO) ₂ Fe, FeBr ₂ , FeBr ₃ , FeF ₂ , FeF ₂ .4H ₂ O, FeF ₃ , FeF ₃ .3H ₂ O, Fe (NO ₃ ) ₃ .9H ₂ O, Fe (C ₂ O ₄ ) .2H ₂ O,

Fe ₂ (C ₂ O ₄ ) ₃ .6H ₂ O, FePO ₄ .2H ₂ O, FePO ₄ .4H ₂ O, CoSO ₄ .7H ₂ O, (CH ₃ COO) ₂ Co, (CH ₃ COO) ₂ Co .4H ₂ O, CoCl ₂ .6H ₂ O, CoF ₂ .4H ₂ O, Co (NO ₃ ) ₂ .6H ₂ O, CoC ₂ O ₄ .2H ₂ O, Co ₃ (PO ₄ ) ₂ .

In an embodiment of the invention where the metal salt is a cobalt salt, the reaction is carried out under oxidation conditions and at a temperature in the range of 80 to 140 ° C. The oxidation conditions are formed, for example, by introducing air or oxygen into the reaction during the reaction. Intensive mixing in an open reaction vessel is sufficient in smaller amounts.

It is a feature of the invention that the resulting product of formula (I) is isolated from the reaction mixture by salting out.

The synthesis of the above-mentioned iron complex dyes of the general formula I (Z = F ²⁺ , Fe ³⁺ ) is carried out by the process according to the invention by mixing in water an unmetatized dye with alkali and then with a water-soluble ferrous or ferric salt. at a temperature of 40 to 140 ° C (autoclave). During the reaction, the reaction pH is maintained by addition of alkali at a pH of 5 to 12, preferably pH 8. NaOH, KOH, LiOH,

NH 4 OH. As the water-soluble divalent iron salt, for example, FeSO ₄ .7H ₂ Cl, FeCl ₃ and the like can be used. As the water-soluble trivalent iron salt, for example, Fe ₂ (SO ₄ ) 3, FeCl ₃ and the like can be used.

From the analogy of the aforementioned complex dyes, where the central ion is a Co ³⁺ ion, it can be assumed that the ligand in the iron complex dye is rather in the azide form. Brown shades are caused by the presence of two broad absorption bands in the visible spectrum (14-15 singlets, transitions), where one band is always in the yellow spectrum. Quantum-chemical calculations show that the absorption spectrum is given by a number of (d, ft *) transitions (transition of electrons from the central iron ion from orbital to the ligand binding orbital) supplemented by (π-π *) transitions in the ligand. These calculations were performed using Gaussian 03W, where the complex molecule was first optimized for geometry (DFT, Density Functional Theory) and then constructed by the Gaussum routine. In addition, the non-brilliant, hazy shades are also due to the mixture of isomers of individual complexes. We have also found that complexing of divalent iron salts produces two 1: 2 complexes, one with a central Fe ² cation and one with Fe ³⁺ . This means that during the complexation Fe ^{2+ ->} Fe ³⁺ oxidation occurs.

The synthesis of the above cobalt complex dyes of the formula I (Z = Co ') is carried out by the process according to the invention by mixing in water an initial unmetallized dye with an alkali and then with a water-soluble usually cobalt salt in a 2: 1 molar ratio. 80 to 140 ° C (autoclave at temperatures above 100 ° C). During the reaction, air (or oxygen) is introduced into the reaction mixture by bubbling the reaction mixture through, or by very vigorous stirring (chemically oxidizing the cobalt salt to cobaltity). During the reaction, the reaction pH is maintained by addition of alkali at a pH of 5 to 12, preferably pH 8. NaOH, KOH, LiOH, NH ₄ OH can be used as the alkali for neutralization. As the water-soluble salts of divalent cobalt, for example, CoSO ₄ .7H ₂ O, (CH ₃ COO) ₂ Co can be used.

It can be deduced from NMR spectroscopy that the ligand in the dye is rather in the azide form, as opposed to the 30 monoaz dye which is predominantly hydrazone in polar environments. This method convincingly demonstrates that the cobalt ion has a coordination number of 6 and that the ligand is tridentally bound to one nitrogen of the azo group, to the functional group of the aromatic residue Ar and to the hydroxyl group of the citrazic acid residue,

¹ H and ¹³ C NMR spectra were recorded on a Bruker Avance 500 spectrometer (500.13 MHz for 1 H and 125.76 MHz for ¹³ C) in DMSO-db. 1 H and ³ C chemical shifts were relative to internal TMS (δ = 0.0). Proton spectra were assigned using the gradient selected technique (gysy-COZY, protonated carbons by gs-HMQC and quaternary carbons were assigned based on gs-HMBC spectrum analysis. Only one set of signals was observed in the 1 H and ¹³ C NMR spectra,

which means that both ligands are equivalent (at least on the NMR time scale). The 1 H and ³ C chemical shifts are shown in the following table:

H / C 1 2 3 4 5 6 7 δ? Η) 11.74 - - 5.83 - - 0 ( ^l3 C) - and 114.7 (B) 104.2 and 167.4 H / C r 2 ' 3 ' 4 ' 5 ' 6 ' - - 6.70 7.00 6.70 8.03 δ (' ³ ο 145.8 168.8 117.3 128.9 114.4 114.6 ^and 148.7 or 148.3, ^b signal was not observed data for 5 'chloro derivative H / C 1 2 3 4 5 6 7 δ ('Η') 11.39 - - - 5.48 - - 8 ( ^,! C) - and 114.8 (B) 101.8 and 166.8 H / C r 2 ' 3 ' 4 ' 5 ' 6 ' δ ('Η') - - 6.65 6.93 - 7.93 O ( ^'3 C) 147.1 169.9 117.7 127.5 118.3 114.8

149.8 or 147.1, no signal was observed

The present invention further provides a process for dyeing animal and synthetic substrates comprising the use of a pre-metallized metal-complex azo dye of the formula I as a dye and dyeing in an acid to neutral bath at a pH of 2 to 7 at 10 ° C. in the range of 30 to 100 ° C. The coloring of animal substrates (vertebrate fur, natural silk and leather) and substrates based on synthetic polyamides (eg polyamide 6, polyamide 6,6) excel in high wet and light fastnesses.

The present invention further provides a process for preparing the metal complex azo dyes of the formula (I) in situ on an animal substrate which comprises coloring the animal substrate from an acid to neutral aqueous dyeing bath (pH 2-7) at a temperature of 30-100 ° C. dye of general formula II (so-called mordant dye)

MeQOC

wherein the X group on the aroma Ar is ortho to the azo group and

X = O, NH, C (= O) O;

R 1, R ₂ are independently H, F, Cl, Br, I, SO ₃ Me, C (= O) OMe, PO ₃ Me ₂ , OR, OH, NH ₂ , NHR,

NR ₂ , SH, SO ₂ NH ₂ , CONH ₂ , NO ₂ , CN, SO ₂ R, SO ₂ NHR or CONHR;

Me = H, Li, Na, K, NH ₄ ;

R = alkyl C _1-8 ;

Ar is an aromatic system having 6 to 10 carbon atoms and containing at least one aromatic core (aromatic system of the benzene or naphthalene type), and then pickling is carried out on an animal substrate in a metallization bath with water-soluble iron or cobalt in water at metallization factor 0; 1 to 0.7, a bath ratio of 1: 10 to 30 (weight of the dyed substrate: weight of the bath), at a pH in the range of 2 to 7, at a temperature in the range of 80 to 100 ° C and a pickling time of 20 to 120 minutes to form a metal complex The achieved dyeing usually achieves 1 to 2 degrees of more favorable stability values than with the application of pre-metallized ferrous and / or non-metallized iron. ferric, respectively. cobalt complex dyes.

In addition, the dyeing exhibits a slight bathochromic shift, again compared to the pre-metallized dye (at the same chromophore).

The water-soluble metal salt may be selected from the group consisting of ferrous, ferric, cobalt and cobalt salts, especially salts selected from the group consisting of FeSO ₄ .7H ₂ O, FeCl ₂ , FeCl _2, 6H ₂ O,

FeCl ₂ .4H ₂ O, Fe ₂ (SO ₄ ) ₃ .9H ₂ O, Fe ₂ (SO ₄ ) ₃ , FeCl ₃ , FeCl ₃ .6H ₂ O, (CH ₃ COO) ₂ Fe, FeBr ₂ , FeBr ₃ , FeF ₂ , FeF ₂ .4H ₂ O, FeF ₃ , FeF ₃ .3H ₂ O, Fe (NO ₃ ) ₃ .9H ₂ O, Fe (C ₂ O ₄ ) .2H ₂ O, Fe ₂ (C ₂ O ₄ ) ₃ .6H ₂ O, FePO ₄ .2H ₂ O, FePO ₄ .4H ₂ O, CoSO ₄ .7H ₂ O, (CH ₃ COO) ₂ Co, (CH ₃ COO) ₂ Co ₄ H ₂ O, CoCl ₂ , 6H ₂ O, CoF ₂ .4H ₂ O, Co (NO ₃ ) ₂ .6H ₂ O, CoC ₂ O ₄ .2H ₂ O, Co ₃ (PO ₄ ) _2, and CoF ₃ .

The metallization is preferably carried out in a new (fresh) bath at pH 3, bath ratio 1: 20 (weight of dyed substrate: bath weight), at 100 ° C, for 45 minutes, with the addition of a water-soluble iron salt or The cobalt in dissolved form from the stock solution in an amount guaranteeing a metallization factor was 0.35. Using the metallization factor we determine the amount of salt corresponding to the cation needed for metallization (pickling). E.g. for 2% of the coloration, the corresponding amount of salt is: 2 x 0,35 - 0,7 = salts of the corresponding cation from the weight of the dyed substrate,

Metallization (pickling) can also be carried out in the old bath (after dyeing) by the same procedure as in the new bath (fresh).

The invention is further illustrated by the following examples without being limited thereto.

BRIEF DESCRIPTION OF THE DRAWINGS

Fig. 1 shows the absorption spectra of the metal-complex dye of Example 1 in water and dimethyl sulfoxide (DMSO).

Giant. 2 shows the absorption spectra of the metal complex dye of Example 2 in water and dimethyl sulfoxide (DMSO).

Giant. 3 shows the absorption spectra of the metal-complex dye of Example 3 in water and dimethylsulfoxide (DMSO);

Giant. 4 shows the absorption spectra of the metal complex dye of Example 9 in water and dimethyl sulfoxide (DMSO).

Giant. 5 shows the absorption spectra of the metal complex dye of Example 10 in water and di5 methylsulfoxide (DMSO).

Giant. 6 shows the absorption spectra of the metal-complex dye of Example 11 in water and dimethylsulfoxide (DMSO).

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DETAILED DESCRIPTION OF THE INVENTION

Methods

Test for color fastness in potting (boiling water declaration)

Potting stability was tested according to ISO 105 E09. The pooled sample (dyed wool sample with two wool / cotton backing fabrics) wound on a glass rod was boiled under reflux for one hour in distilled water. In all cases, the color change of the test sample and the embedding in the accompanying fabrics are evaluated using a five-stage gray scale (1-worst, 5-best). Stability in potting was determined at the Department of Polymer Materials at the University of Pardubice in the Department of Fiber Materials and Textile Chemistry.

Test for color fastness to washing at 60 ° C without perborate

Wash stability was tested according to ISO 105 EO 6. Combined sample (sample dyed wool fabrics with two flanking wool / cotton) were washed in 50 ml solution containing 4 g.dm ^"3 standard detergents and g.dm 1 ^'3 of anhydrous sodium carbonate. Staining was performed isothermally at 60 ° C for 30 min. After washing, the sample was rinsed with distilled and water and dried according to ISO standards. The color change of the test sample and embedding in the accompanying fabrics was evaluated using a five-stage gray scale (1-worst, 5-best).

Washing stability at 60 ° C without perborate was determined at the Department of Polymer Materials of the University of Pardubice at the Department of Fiber Materials and Textile Chemistry.

Lightfastness (Xenotest)

The light fastnesses were determined at Xenotest 450 (Hanau, Germany) in Aliachem a.s., Synthesia Division, SBU Pigments and Dyes, Semtín 103, 532 17 Pardubice according to ISO 105 B02 (method 2 - normal climatic conditions). The staining of the sample is assessed on an eight-membered blue scale (1-worst, 8-best). The samples are exposed to xenon lamp radiation, whose spectral composition corresponds to daylight. The color fastness of the sample is given by the standard number on the blue scale, which shows the same shade change as the test sample.

ESI-MS Mass Spectroscopy - Electrospray Ionization

Mass spectra were measured at the Department of Analytical Chemistry of the University of Pardubice using an Esquire 3000 with an ion trap (Bruker, Daltonics, Bremen, Germany). The samples were dissolved in water-acetonitrile (1: 1) and analyzed by direct infusion at a flow rate of 3 μΙ / min. Mass spectra were recorded in the range of m / z 50 to 1000 using electrospray ionization (ESI) to record negative ions. Nitrogen pressure was 10 psi and a flow of 4 dm ^"3 .min ^-1. The isolation width of the precursor ion for MS ⁿ measurements was m / z = 4.

Absorption spectroscopy

Hewlett Packard 8453 absorption spectrophotometer (HP, Germany) was used to measure UV / VIS absorption spectra. A cuvette with an optical path length of 1 cm was used to measure the spectra.

The dye spectra were measured in distilled water or dimethylsulfoxide at room temperature.

Nuclear Magnetic Resonance Imaging The samples were dissolved in deuterated DMSO. ³ C NMR and 1 H NMR spectra were measured on a BRUKER AMX-360 MHz instrument at the Research Institute of Organic Synthesis as Pardubice.

Example 1

Cl

NaOOC

(L-l)

NaOOC

COON (K-1)

The starting dye of formula L1 (C ₁₂ H ₇ N ₃ O ₅ ClNa, 0.04 mol) was dissolved in 240 cm ^{3 of} water and 6.4 cm ^{3 of} 5M NaOH was added and the solution was heated to 60 ° C. Then a solution of 5.62 g (0.02 mol) of CoSO ₄ .7H ₂ O in 50 cm ^{3 of} water was added. The reaction mixture was vigorously stirred, bubbled with air and heated to 60 ° C for 10 minutes, the reaction pH adjusted to 9 by further addition of 5M NaOH, and then the reaction mixture was heated and stirred in an autoclave at 130 ° C for 4 hours. . After completion of the reaction, the reaction mixture was cooled to room temperature (25 ° C). The resulting 1: 2 ^CoI complex K1 was isolated by salting out by adding 24 g of NaCl to the final reaction mixture. Thereafter, the dye was filtered off and dried at 80 C. Yield ^Ù barvívaje quantitative. Control of the complexation was performed by TLC (ALUGRAM SIL G / UV 254 solid phase, mobile phase: propane-I-O / NH 4 OH (35%) = 2/1 by volume). The resulting dye of formula K1 has a brilliant red hue, where the spectra in dimethylsulfoxide and water are shown in Figure 1.

Λ

The structure of the dye was confirmed by NMR spectroscopy.

ŽŽ ί ~ 2 3 4 ~ Š 6 7 ~ o ('D) ~9 ~ 5 ^ 8' ~

8 ( ^I3 C) - a 114.8 b 101.8 and 166.8 h T r

8 ('H)': 6/55 6 $ 3 ~ 793

5 ( ⁱ³ C) 147.1 169.9 117.7 127.5 118.3 114.8 '149.8 or 147.1, ⁶ signal not observed

Mass spectrometry confirmed the structure and presence of the following fragments in the spectrum.

m / z Fragment structure 673 Cl HOOC O ^ O ^ - ^ - W = N - OH Cl HOOC

330 She N = N- 0 -OH 4 3C Cl HQ ( - OH O -7 ) —N 308 ( y — n = n- -OH = / cl HOOC - - She 0 V N 286 < y — N = N- -OH = / \ = Cl - - OH 0 -7 264 < -OH = / \ = / Cl - - - Vv _Z OH 110 in -

Example 2

NaOOC

COON (K-2)

The starting dye of formula II ₍₂ C ₇ H 7 N ₃ O ₅ boat, 0.04 mol) were dissolved in 240 cm ³ of water and thereto was added 6.4 cm ³ of 5M NaOH and the solution was heated to 60 ° C. A solution of 5.56 g (0.02 mol) of FeSO ₄ .7H ₂ O in 50 cm ^{3 of} water was then added. The reaction mixture was stirred and heated to 100 ^° C for 4 hours. The reaction pH was maintained at 8 by the addition of 5M NaOH. After completion of the reaction, the reaction mixture was cooled to room temperature (25 ° C). The resulting 1: 2 Fe-complex was isolated by salting out by adding 24 g of NaCl to the final reaction mixture. The dye was then filtered off and dried at 80 ° C. The yield is quantitative. Control of complexation was performed by TLC (ALUGRAM SIL G / UV254 solid phase, mobile phase: propan-1-ol)

NH 4 OH (35%) = 2/1 by volume). The resulting dye of formula K-2 is gray-green in high black concentration. The spectra in dimethyl sulfoxide and water are shown in Figure 2.

Mass spectrometry confirmed the structure and presence of the following fragments in the spectrum.

m / z Fragment structure 760 Cl NaOOC N = N — OH ONa O from ^Fe O NaO ^^ - N = N — ^ 2 ^ - ° ^H Cl NaOOC ⁷ +

330 She H-n = n- O -OH DC Cl HOÍ | - - OH Q -7 Y — N 308 < Vn = n- < -OH y = / Cl HOOC - - - She 0 -7 ) —N 286 ( y-N = N- < 7 -OH = / j of Cl - - OH O -7 ϊ— N 264 ( y — N = N- -OH \ = J of Cl - - O N _Z OH r tl 110 at

Other fragments correspond to a complex dye where the central cation is trivalent iron (see the following example). It follows that during the assembly two complexes are formed, one with Fe "'and one with Fe ¹ ',

Example 3

NaOOC

COON (K-3)

The starting dye of formula L1 (C 1 H 3 N 2 O 2 OClNa, 0.04 mol) was dissolved in 240 cm ^{3 of} water and 6.4 cm ^{3 of} 5M NaOH were added and the solution was heated to 60 ° C. Then a solution of 5.62 g io (0.01 mol) Fe ₂ (SO 4) 3 in 25 cm ^{3 of} water was added. The reaction mixture was stirred and heated to 100 ° C for 4 hours. The reaction pH was maintained at 8 by the addition of 5M NaOH. After completion of the reaction, the reaction mixture was cooled to room temperature (25 ° C). The resulting 1: 2 Fe ^{1 L} complex was isolated by salting out by adding 24 g of NaCl to the final reaction mixture. The dye was then filtered off and dried at 80 ° C. The yield of the reaction was 12.34 g of the complex of formula K-3, which represents

76.6% of theory. Control of the complexation was performed by TLC (ALUGRAM SIL G / UV 254 solid phase, mobile phase: propan-1-ol / NH ₄ OH (35%) = 2/1 v / v). The resulting dye of formula K-3 is gray-green (λ _ΜΑΧ = 455 nm, ε _ΜΑΧ = 8 556 dm ³ ), in high black concentration, where the spectra in dimethylsulfoxide and water are shown in Figure 3.

Mass spectrometry confirmed the structure and presence of the following fragments in the spectrum.

Cl ooc 2- 1 312.4 AND Vn -OH ° \ z ° X 0 0 Γ p — N = N— C -OH Cl - ON a 0 - 330 ff y — N-N · JT • N ► — OH Cl HOOC OH 0 - 308 / V-N = N- —OH Cl HOOC ⁷ - She 0 - 286 V-N = N- Jr N -OH Cl - OH 0 - 264 / y— n = n- N -OH Cl - Yy .OH - 110 in -

Example 4

NaOOC

OH

NaO ₃ S (L-2)

Using four equivalents of the starting monoaz dye of formula L-2 and one equivalent of ferric sulfate, a dye of formula K-4 is obtained which is brown in color (λ max = 446 nm, λ max = 9,891 dm ³ · mol · 1). cm ^-1 , measured in water).

Example 5

Cl

NaO ₃ S

NaOOC

(L-3)

also using four equivalents of the starting monoazového dye of formula L-3 and one equivalent of ferric sulfate formed as described in Example 3, the dye of formula K-5, which has a brown hue (.lambda.max = 459 nm, _M max ⁼ 8424 dm ³ .mor ^l .cm ^'!, measured in water).

Example 6

I -τ

Using four equivalents of the starting monoaz dye of formula L-4 and one equivalent of ferric sulfate, a dye of formula K 6 is obtained as described in Example 3 which has a brown shade (λ _ΜΑ χ = 444 nm, λ max 10 894 dm \ mol '.cm -1). ¹ , measured in water).

Example 7

Using four equivalents of the starting monoaz dye of formula L-5 and one equivalent of ferric sulphate, the dye of formula K.-7 is obtained as described in Example 3, which has a brown io shade (λ _ΜΑ χ ~ 467 nm, e _M ax ⁼ 16 567 dm ³ .mol ¹ .cm ^-1 , measured in water).

Example 8

NaOOC

(L-6)

NaOOC

COON (κ-e>

Using two equivalents of the starting monoaz dye of formula L-6 and one equivalent of ferrous sulfate heptahydrate, a dye of formula K-8 is obtained as described in Example 3 which has a brown shade (λ _ΜΛΧ = 430 nm, ε _ΜΑ χ = 12 680 dm ³ .mol) " ¹ .cm" ¹ , measured in water).

nh ₄

Example 9

NaO ₃ S

(L'2

(k-9;

Prepared using two equivalents of the starting monoaz dye of formula L-2 and one equivalent of cobalt sulfate heptahydrate using the procedure described in Example 1, but using NH ₄ OH instead of NaOH to give a red-brown dye of formula K-9 (Xmax ~ 471) nm, ε _ΜΑ χ - 44433 dm ³ .mor ¹ .cm ^-1 , measured in water). The spectrum in water is shown in Figure 4.

Example 10

H ₂ NO ₂ S

(L-7) 10

In the preparation using two equivalents of the starting monoaz dye of formula L-7 and one equivalent of cobalt sulfate heptahydrate, the procedure described in Example 1 is used, but LiOH is used instead of NaOH to give a dye of formula K-10 which is reddish-brown (λ _ΜΑ) χ471 nm, ε _ΜΑ χ ⁼ 44343 dm ³ .mord “ ¹ , measured in water). The spectrum in water is shown in Figure 5.

IO.

Example 11

h ₃ man ₂ s (L-8)

(K-II)

In the preparation using two equivalents of the starting monoaz dye of formula L-8 and one 5 equivalents of cobalt sulfate heptahydrate, the procedure described in Example 1 is used, but instead

NaOH, KOH is used, and a dye of formula K-II, which is reddish-brown (.lambda.max = 472 nm, Smax - 42,562 dm ³ .mol ^"1 .cm ^-1, measured in water). The spectrum in water is shown in Figure 6.

io Example 12

Dyeing wool with metal-complex dye

Into a 200 cm ³ bath (distilled water) was placed 10 g of wool fabric sample and 0.04 g of dye 15 of formula I, the pH of the dye bath was adjusted to 3 by the addition of concentrated acetic acid (98%). raised to 100 ° C and held under stirring for 45 minutes. After cooling the bath to normal temperature (25 ° C), the stained sample was removed, rinsed with distilled water and then dried. Linitest staining equipment (Hanau, Germany) was used for staining.

Color test results

Color fastness Dye Potting Wash 60 ° C K-l 2 / 1,4 * 1/3, 3 * K-2 2 / 1,4 * 1/3, 3 * K-3 3 / t, 3-4 * 1-2 / 5.2 *

shade change / embedded in wool, embedded in cotton

Example 13

Staining method of dyeing wool - preparation of dye „in situ“

In a 200 ml bath (distilled water) was placed 10 g of wool sample and 0.04 g of dye of formula II, the pH of the dye bath was adjusted to 3 by addition of concentrated acetic acid (98%). ° C and maintained under stirring for 45 minutes. After cooling the bath to room temperature (25 ° C), the stained sample was removed and placed in a pickling bath. Linitest staining equipment (Hanau, Germany) was used for staining.

A 100 ml bath (distilled water) was charged with 5 g of a stained wool sample. The pH was adjusted to 3 with concentrated acetic acid and after addition of iron salts (Fe ²⁺ and Fe ³⁺ , or cobalt (Co ²⁺ and Co ')) the temperature was raised to 100 ° C and maintained at this value for 30 minutes. stock solutions FeSO ₄ .7H ₂ O, Fe ₂ (SO ₄ ) ₃ , CoSO ₄ .7H ₂ O and CoF _{3 were used} .

From the stock solution was pipetted under these given conditions for a graduated cm ³ of solution. The concentration of the solutions was as follows: FeSO4. 7H 2 O = 13.34 g / 100 cm ³ ; Fe 2 (SO ₄ ) ₃ = 19.23 g / 100 cm ³ ; CoSO 4 .7H 2 O = 13.5 g / 100 cm ³ ; CoF3 = 5.6 g / 100 cm ^{T The} metallization factor was 0.35.

Mordant dye Structure L-2 NaOOC OH NaO ₃ S L-7 NaOOC OH N = <VoH Η 2ΝΟ2Ξ ⁷ L-8 NaOOC CH3HNO2S

The following tables summarize the results of dye withdrawal from the dyeing bath and shades obtained by dyeing wool fibers.

4% coloring % draw Dye L-2 66.47 Dye L-7 59.51 Dye L-8 96.03

4% coloring Pickled with salts Color change after pickling Dye L-2 without pickling buff Fe ²⁺ dark brown Fe ³ * Brown Dye L-7 without pickling yellow-red-brown Fe ² * dark brown Fe ³⁺ Brown Dye L-8 without pickling red-yellow-brown Fe ²⁺ darkbrown Fe ³⁺ dark brown

The following table shows the results of the color test.

4% coloring Washing stability 60 ° C Light state Pickling solemi Change shade Embedded in the wave Embedded in the baylny Dye L-2 without pickling 2 1 5 3 Fe ²⁺ 3 2-3 4 4-5 Fe ³⁺ 3 1 4 4 Dye L-7 without pickling 3 1 4-5 2-3 Fe ² * 3-4 3 4 4-5 Fe ³ * 3-4 1 4 4-5 Dye L-8 without the sea 2 1 3-4 2-3 Fe ²⁺ 3 1 3-4 5-6 + fn iX ³ 1 3-4 5-6

The results of coloristic tests show that the stain dyes L-2, L ~ 7 and L 8 have good wet fastness and slightly above average fastness.

It has been found in the wash stability that all three dyes are quite embedded in pure wool and hardly embedded in pure cotton. Dyes stained with ferrous salt provide the best light fastness. Often, the desired deep black shades achieve when staining was L-8 stained salts of Fe ² 'and ^{Fe? +.}

Example 14

Mesh-like method of dyeing wool - in-situ dye preparation

Following the procedure of Example 13 above, L-7 and L-8 dyeing was dyed in 4% dyeing and stained.

Results of colorist tests of dye L-7

Salt pickling Wash 60 ° C Potting Lightfastness Without pickling 1 / 2-3,4-5 * 1 / 2.3 * 1 Co ²⁺ 2-3 / 5.4-5 * 4 / 1,4 * 6 Co ³⁺ 3 / 5,4-5 * 4 / 1,4-5 * 6 * shade change / embedded in wool, embedded d o cotton

Results of coloristic tests of dye L-8

Salt pickling Wash 60 ° C Potting Lightfastness Without pickling 1 / 3,4-5 * 1 / 1,3 * 1-2 Co ²⁺ 2-3 / 5.4-5 * 4 / 1,4-5 * 6 Co ³⁺ 3 / 5,4-5 * 4 / 1,4-5 * 6 * shade change / embedded in wool, embedded c o cotton

The results show that the best coloring is achieved with cobalt salt pickling, including high light fastness.

Claims (11)

PATENT CLAIMS What is claimed is: 1. A compound of formula (I) of the formula (I) wherein X is on the aromatic Ar in ortho position to the azo group and 25 X = O, NH, C (= O) O; Z is Fe ^{2+ and} n = 2 or Z is Fe ³⁺ or Co ³⁺ and n = 1 Me = H, Li, Na, K, NH ₄ ; M @ ⁺ = Lf, Na ^{@ 4} , K ^@ NH); Ri, R? are independently H, F, Cl, Br, 1, SO ₃ Me, C (= O) OMe, PO ₃ Me ₂ , OR, OH, NH 2, NHR, NR 2, SH, SO 2 NH 2, CONH ₂ , NO ₂ , CN, SO 2 R, SO 2 NHR or CONHR; 5 R-alkyl C ₁₈ ; Ar is an aromatic system containing 6 to 10 carbon atoms and contains at least one aromatic nucleus. 2. A process for the preparation of pre-metallized dyes of formula (I), characterized in that the starting dye of formula (II) is mixed in water. MeOOC XH (H di), where 15, the X group on the aroma Ar is ortho to the azo group and X - O, NH, C (= O) O; R _b R 2 are independently H, F, Cl, Br, I, SO ₃ Me, C (= O) OMe, PO ₃ Me ₂ , OR, OH, NH ₂ , NHR, 20 NR 2, SH, SO ₂ NH ₂ , CONH ₂ , NO 2, CN, SO ₂ R, SO ₂ NHR or CONHR; Me = H, Li, Na, K, NH ₄ ; R = alkyl C _'8; Ar is an aromatic system of 6 to 10 carbon atoms, containing at least one aromatic ring, with alkali followed by a water-soluble iron or cobalt salt, and the reaction mixture is heated to a temperature in the range of 40 to 140 ° C, during which the pH maintaining the additions of alkali in the range of 5 to 12, preferably to a pH of 8, and the resulting product of formula (I) is then isolated from the reaction mixture. Process according to Claim 2, characterized in that NaOH, KOH, LiOH or NH ₄ OH is used as the alkali. 35 Method according to claim 2, characterized in that the water-soluble salt of iron or cobalt is a salt selected from the group consisting of ferrous, ferric, cobalt or cobalt salts, preferably a salt selected from the group consisting in particular of FeSO ₄ .7H ₂ O, FeCl _2. , FeCl ₂ .6H ₂ O, FeCl ₂ .4H ₂ O, Fe ₂ (SO ₄ ) ₃ .9H ₂ O, Fe ₂ (SO ₄ ) ₃ , FeCl ₃ , FeCl ₃ .6H ₂ O, (CH ₃ COO) ₂ Fe, FeBr ₂ , FeBr ₃ , FeF ₂ , FeF ₂ .4H ₂ O, FeF ₃ , FeF ₃ .3H ₂ O, Fe (NO ₃ ) ₃ .9H ₂ O, Fe (C ₂ O ₄ ). ₂ H ₂ O, Fe? (C ₂ O ₄ ) ₃ .6H ₂ O, FePO ₄ .2H? O, 40 FePO ₄ .4H ₂ O, CoSO ₄ .7H ₂ O, (CH ₃ COO) ₂ Co, (CH ₃ COO) ₂ Cu ₄ H ₂ O, CoCl ₂ .6H ₂ O, CoF ₂ .4H ₂ O, Co (NO ₃ ) ₂ .6H ₂ 0, CoCl _{2 4} .2H ₂ 0, Co ₃ (PO ₄ ) ₂ . A process according to claim 4, wherein, when the metal salt is a cobalt salt, the reaction is carried out under oxidation conditions and at a temperature in the range of 80 to 140 ° C. Process according to Claim 2, characterized in that the resulting product of formula (I) is isolated from the reaction mixture by salting out. Method for dyeing animal and synthetic substrates, characterized in that the dye is a metal complex azo dye of the formula I according to claim 1, wherein the dyeing is carried out in an acid to neutral bath at a pH of 2 to 7 at a temperature of 30 to 100 ° C. 5 8. A process for the preparation of metal-complex azo dyes of the formula I in situ on an animal substrate, characterized in that the animal substrate is dyed from an acid to neutral aqueous dyeing bath of pH 2 to 7 at a temperature of 30 to 100 [deg.] C. MeOOC R1 = N = OH R ₂ -Ar-N VN X H ^H O (Π) _ζ wherein the X group on the aroma Ar is ortho to the azo group and X = O, NH, C = -O) 0; R 1, R ₂ are independently H, F, Cl, Br, I, SO ₃ Me, C (= O) OMe, PO ₃ Me ₂ , OR, OH, NH ₂ , NHR, NR ₂ , SH, SO ₂ NH ₂ , CONH ₂ , NO ₂ , CN, SO ₂ R, SO ₂ NHR or CONHR; Me = H, Li, Na, K, NH ₄ ; 20 R = alkyl C _1-8 ; Ar is an aromatic system containing 6 to 10 carbon atoms and containing at least one aromatic ring, 25 and then pickling on an animal substrate in a metallization bath with a water-soluble iron or cobalt salt in water, at a metallization factor of 0.1 to 0.7, a bath ratio of 1: 10 to 30, expressed as mass of dyed substrate: bath weight, at pH in the range of 2 to 7, at a temperature in the range of 80 to 100 ° C and a pickling time of 20 to 120 minutes. 30 The method according to claim 8, characterized in that the water-soluble iron or cobalt salt is selected from the group consisting of ferrous, ferric, cobalt and cobalt salts, preferably a salt selected from the group consisting in particular of FeSO ₄ .7H ₂ O, FeCl ₂ , FeCl _2. .6H ₂ O, FeCl ₂ .4H ₂ O, Fe ₂ (SO ₄ ) ₃ .9H ₂ O, Fe ₂ (SO ₄ ) ₃ , FeCl ₃ , FeCl ₃ .6H ₂ O, (CH ₃ COO) ₂ Fe, FeBr ₂ , FeBr ₃ , FeF ₂ , FeF ₂ .4H ₂ O, FeF ₃ , FeF ₃ .3H ₂ O, Fe (NO ₃ ) ₃ .9H ₂ O, Fe (C ₂ O ₄ ) .2H ₂ O, Fe ₂ (C ₂ O ₄ ) ₃ .6H ₂ O, FePO ₄ .2H ₂ O, FePO ₄ .4H ₂ O, 35 CoSO ₄ .7H ₂ O, (CH ₃ COO) ₂ Co, (CH ₃ COO) ₂ Co ₄ H ₂ O, CoCl ₂ .6H ₂ O, CoF ₂ .4H ₂ O, Co (NO ₃ ) ₂ .6H ₂ O, CoC ₂ O ₄ .2H ₂ O, Co ₃ (PO ₄ ) ₂ and CoF ₃ . Method according to claim 8, characterized in that the pickling is carried out in a new bath at pH 3, a bath ratio of 1:20, expressed as mass of the dyed substrate: bath weight, at a temperature of 40 ° C, for 45 minutes, with the addition of a water-soluble iron or cobalt salt in dissolved form from the stock solution in an amount guaranteeing a metallization factor of 0.35. Method according to claim 8, characterized in that the pickling is carried out in a bath after dyeing at pH 3, a bath ratio of 1:20, expressed as the weight of the substrate to be dyed: 45 ° C, for 45 minutes, with the addition of a water-soluble iron or cobalt salt in dissolved form from the stock solution in an amount guaranteeing a metallization factor of 0.35,