CS202524B2 - Method of preparing complex of azo compounds with heavy metals - Google Patents

Abstract

1340270 Metallized azo dyes CIBA-GEIGY AG 6 May 1971 [6 May 1970] 13429/71 Heading C4P New metal complexes of azo dyes containing, as the diazo component radical, a heterocyclic radical wherein three ring atoms and the azo group have, in one of the mesomeric or tautomeric limiting forms, a system of structure wherein one of X and Y is a N atom and the other a N or C atom and, as the coupling component radical, a halogeno-2,3-dihydroxypyridine are described. The dyes are prepared by coupling a diazotized amine, for example of the quinoline, thiadiazole, pyrazole, phenylazoquinoline, indazole, benzthiazole or benztriazole series with a halo-2,3-dihydroxypyridine and metallizing the dyes obtained. Copper, nickel, cobalt and chromium complexes are specified in examples. The dyes are used to colour nitrogenous fibres, in particular synthetic polyamides, in blue shades.

Description

The present invention relates to complexes of azo compounds with heavy metals which, as the remainder of the diazocomponent, have a heterocyclic radical having a comlexing site separated by one or two atoms from the azo group and as the remainder of the halogen-2,3-dihydroxypyridine copolymer.

As kornplexotvorná sites suitable ionisovatelné complexing groups such napMk Uydrro ¹ ^ ^ - carboxylic ^b 01 y ^χ, alcoholic ^ - ^b of not AMNOTE group and ^L R E ^P neiin evěÍI ^{d e e} Зsovte Ne coordination sites as · are, for example, nitrogen atoms.

Atom or two atoms to separate! may be in the ring or attached to the ring and may be heteroatoms such as oxygen or sulfur or preferably carbon atoms. Especially important are - azo compound complexes where 3 heterocyclic diazoisoornonone atoms? these together with the a-bridge form one of the possible (mesorneric or tautomeric) form forms of the conjugated ⁴ double bond system of structure Ia, wherein one of X 'and Y is one nitrogen and the other is the other nitrogen or carbon.

As comforming metals you come! for example, iron, cobalt, chromium and in particular both nickel and nickel. The co-mít lexes may have one or two molecules on the complex-forming metal atom (1: 1 and 1: 2 codes). In the 1: 2 complex, both ligands of 202524 '

202524 2 match the above definition. 1: 1 complexes with media and nickel are particularly preferred according to the present invention.

Heterocyclic diazocomponents are especially 5- or 6-membered heterocyclic radicals. These radicals may contain two or more heteroaooms, in particular nitrogen atoms, such as in imidazole, thiadiazole or triazole, or they may contain a fused benzene ring, such as quinoline.

The azo group may be directly bonded to a heterocycle or may be bonded to a residue which does not contain heteroatoms. The diazo component may contain other substituents, such as, for example, halogen, nitro, alkyl, alkoxy, aryls, phenyl, acylamino, carboxy, or arylazo, and especially sulfo and reactive moieties, especially bonded via amino, reactive or reactive atoms groups of atoms containing aliphatic carboxylic acid residues such as alpha, beta-dibromopropioinfl, or alpha-benzylcyl.

A preferred coupling component residue is the 5-bromo-2,3-dihydric additive residue.

Of interest are the complexes of heavy metals and azo compounds of formula (II)

(II),

Br

Where D is the quinoline moiety bound at the 8-position, and the complexes of heavy metals and azo compounds of formula III are of particular interest

(III), wherein Z is a halogen atom, for example a chlorine or bromine atom, a sulfo group or an acylamino group having 2 to 4 carbon atoms, such as. is an acetyl or phenylazo group which may be substituted with a glass-reactive and acylamino group having 2 to 4 carbon atoms, such as the disazo compound of formula IV

NHCOCHBrCH ₂ Br Br (IV) '

The residues which form the structure in (corresponding to formula Ia) need not contain any of the conventional complexing groups such as hydro, carbonyl or alkoxy because the metal atom is coordinatively bonded except for the hydroxyl group of the remainder of the coupling component bonded in the ortho-position to the azo group, also to the azo group and to the lone electron pair of the nitrogen atom contained in the heterocyclic residue of the diazocomponent.

In this way, one five-membered and one six-membered ring is formed from one metal atom, for example a molecule of formula III, and from one metal atom o. two molecules of formula III are formed in the same way. two five-membered circles and two six-membered circles, which are structures that showed a stabbling stabblity. The charge of the ion at the metal atom depends on the acid groups, especially the sulfo groups, or the basic groups, such as the quaternary ammonium groups.

The structures of formula I, wherein X is a nitrogen atom and Ϊ is a carbon atom, have been found therein, for example, in the so-called compounds which have the remainder of the 2-aminothiazole

The corresponding ascompound wherein X and Ϊ are nitrogen atoms contain, for example, a residue

5-amino-2-phenyl-1,1,4-thiadiazole.

N — N

The case where X is a carbon atom and Ϊ is a nitrogen atom is realized in compounds containing a B-aminoquinoline residue,

which, in the mesomeric boundary form contemplated above, also contains the formulas I with the two double-conjugated double bonds.

Among the heavy metal complexes of the present invention are also those compounds which do not have a complexity. no water solubility groups, such as, in particular, sulfo or carboxy groups. In particular, the compounds may contain one or more reactive moieties, which are particularly contained in.

Suitable reactive radicals are groups reacting with hydroxy-cellulose or amino groups of polyamides to form a covalent chemical bond. Such a group represents, for example, a low-alkenyl, alkenyl or alkenyl or alkenyl or alkenyl or alkenyl or alkenyl group. a heterocyclic four-membered, five-membered or six-membered moiety, substituted by an atom or a leaving group bonded via a carbonyl group not a sulfonyl group, or a triazine or pyrrolidine residue bonded directly by a carbon atom or group. Preferred reactive radicals are aliphatic, saturated or unsaturated, preferably halogen-containing, acyl-containing halogen atoms bonded via the -Ni-group, in particular an alpha, beta-dibloepropnonyloxy or a β-broeakeacylyl radical.

The preparation of the compounds of the present invention is accomplished by reacting an azo compound of the type described with a metal releasing agent to form a metal complex containing a light atom-bound metal atom per azo compound. The meta -aising is therefore preferably carried out with those metal-forming agents and according to those methods which capture compounds of this composition.

The preparation of the 1: 2 complexes is carried out in one step by reacting 1 mole of the compound ρos] k ^{, the} melting heavy metal. 2 moles of the corresponding azo compound or can be carried out gradually. In this case, an additive compound, for example a compound of formula III, is reacted with a metal releasing reagent to form a 1: 1 complex, and the complex is then treated with an equivalent amount of the corresponding metal-free azo compound to form a 1: 2 complex.

This method is particularly useful when 1: 2 chromium complexes are prepared which contain unequal ligands, but both must meet the above definition.

Instead of reacting the complex compound 1: 1 with chromium with a suitable second component as described above, in a 1: 1 molar ratio, nonmetallized azo compounds in a 1: 1 molar ratio in a solvent mixture may also be used as starting compounds while using a release agent. metal, so-called mixed metallization.

The reaction with the heavy metal releasing agent is carried out in a conventional manner, depending on the solubility of the components in the solvent, such as water, ethanol, formamide, glycoether, pyridine, etc., or the reaction is carried out at elevated temperature in a mildly acidic to alkaline medium.

The reaction is preferably carried out under heat, often under pressure, optionally in the presence of a suitable complexing agent such as salts of organic acids or bases.

Especially valuable complex compounds are obtained using copper and nickel salts as metal-providing agents.

For example, salts containing a cation such as copper (II) sulfate or copper (II) acetate can be used as the currency releasing sensor. In many cases, it is preferred to use complex copper compounds, for example in the form of copper-amine complexes, such as tetrammonium sulfate prepared from copper sulfate and ammonia, pyridine or monoethanolamine, or compounds having complex bound copper, for example complex aliphatic alkali salts. aminocarboxylic acids, hydroxycarboxylic acids or dicarboxylic acids such as glycols, glycolic acid, lactic acid, oxalic acid, and in particular a complex compound of tartaric acid, such as monosodium tetrate, aliphatic tricarboxylic acids, such as citric acid or aromatic oxycarboxylic acids, such as acid salicylová.

The reaction with the liberating agents is carried out by known methods, for example at room temperature when starting from a readily metallizable starting compound or by heating to temperatures between 50 and 120 ° C in an open vessel, for example by refluxing or optionally in a closed for example, the acidic reaction is carried out using copper sulphate and alkaline when using tetramium sulphate.

in

Alternatively, solvents such as alcohol, dimethylformamide and the like can be used in the metallization.

In the reaction to the metal complexes, the azo compounds are preferably used as starting compounds. <

The preparation of the azo compounds used as starting material is accomplished by coupling diazotized primary heterocyclic amines with halogen-2,3 dihydroxypyridine.

The diazotization of heterocyclic amines is carried out by known methods, for example hydrochloric acid and sodium nitrite. Coupling with the halogen 2,3-dihydroxypyridines is also carried out by known methods in an acid to alkaline environment. Upon completion of the coupling reaction, the metallization compounds may be filtered from the coupling mixture. They are preferably used in the form of filter cakes without further drying. In many cases, it is also possible to carry out the reaction by adding a metal releasing agent directly to the coupling mixture.

The diazocomponents may be further substituted, for example, by chlorine, bromine, nitroacids, cyano, lower alkyl, preferably methyl, lower alkoxy, preferably. methoxylyl, lower alkylsulfonyl, such as methylsulfonyl or ethylsulfonyl, sulfo, carboxy, sulfonamido, substituted sulfonamido, for example N-lower alkylsulfonamido and N-lower hydroxyalkylsulfonamido, e.g. N-methyl, beta-hydroxyethyl) sulfonamido and N, N-di- (beta-hydroxymethyl) sulfonamido, substituted or unsubstituted phenylazo, naphthyloxy, acylamino, such as formylamino, aminomethylamino, benzoylamino, benzenesulfonylamino, methanesulfonamino, p-toluenesulfonamino, p-toluenesulfonamino , carboisopropoxyamino, as well as reactive groups.

Examples of primary heterocyclic amines used for the preparation of azo compounds are:

2-aminopyridine,

2-Aminoquinoline.

2-aminobenzthiazole,

2-amino-6-methoxybenzthiazole,

2-amino-6-nitrobenzothiazole,

3-aminoindazole,

3-amino-6-chloroindazole,

- ami no - 6-methoxy i nd a z ol,

7-aminoindazole,

7-amino-4-nitroindazole,

5-aminotriazole-3-carboxylic acid,

3-Amino-4-phenyl-5-methylpyrazole

4-aminobenztriazole,

7-amino-5-chlorobenzimidazole,

4-amino-5-chlorobenzothiazole,

2-aminothiazole, -

2-amino-4-methylthiazole,

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

5-amino-1,2,4-triazole;

1-phenyl-2,3-dimethyl-4-aminopyrazol-5-one;

5-amino-2-phenyl-1,3,4-thiadiazole,

5-amino-3-phenyl-1,2,4-thiadiazole

8-Aminoquinoline

8-Aminoquinoline-5-sulfonic acid

5-chloro-8-aminoquinoline,

5-acetylamino-8-aminoquinoline,

2-Methyl-8-aminoquinoline

4-aminoacridine,

1-aminocarbazole,

2-amino-5-nitrothiazole,

5-amino-3-pyridyl-1,2,4-thiadiazole

4-amino-3-methylpyrazol-5-one,

.7-dibromo-8-aminoquinoline

8-amino-5 '(4'-sulfophenylazo) -quinoline,

5- C2 * -sulfo-5 * -alpha, tert -dibromopropionylimino-1 * -phenylazo) -8-aminoquinoline,

2-amino-5-methylthio-1,3,4-thiadiazole

2-amino-5-ethylthio-1,3,4-thiadiazole,

2-amino-5-phenylthio-1,3,4-thiadiazole, 2-amino-5-cycloheylthio-1,3,4-thiadiazole,

2-amino-5-methylsulfonyl-1,3,4-thiadiazole,

202525 6 · ', I

2-amino-5-methyl-1,3,4-thiadiazole,

2-amino-5-asylamino-1,3,4-thiadiazole,

2-amino-5-phenylsulfonyl-1,3,4-thiadiazole, 2-amino-5-chloro-1,3,4-thiadiazole,

2-amino-5-carbomethoxyethyl-1,3,4-thiadiazole,

3-Amino-2,1-benzisothiazole

3-amino-5-methyl-2,1-benzisothiazole

3-amino-4-ethyl-2,1-benzisothiazole

3-amino-4,7-; dimethyl-2,1-benzisothiazole,

3-amino-4-methoxy- ^to 2,1-benzisothiazole,

3-amino-5-, -6- or -7-chloro-2,1-benzisothiazole,

_3-Amino-5), 7-dichloro- or dibromo-2,1-benzisothiazole,

3-amino-4-, -5-, -6- or -7-bromo-2,1-benzisothiazole,

3-amino-5- or -6-cyano-2,1-benzisothiazole, 3-amino-4,6-dichloro-5-cyano-2,1-benzisothiazole, 3-amino-7-chloro-5-cyano- 2,1-benzisothiazole, 3-amino-5-chloro-7-cyano-2,1-benzisothiazole, 3-amino-4-methyl-6-cyano-2,1-benzisothiazole, 3-amino-4-, - 5-, -6- or -7-nitro-2,1-benzisothiazole, 3-amino-5,7-dinitro-2,1-benzisothiazole, 3-amino-5-nitro-7-chloro-2,1- benzisothiazole,

3-Amino-5-nitro-7-bromo-2,1-benzisothiazole

3-Amino-5- (N-methylsulfonamido) -2,1-benzisothiazole,

3-amino-5- (N, N-dimethylsulfonamido) -2,1-benzisothiazole, 3-amino-5-methylsulfonyl-2,1-benzisothiazole,

Suitable coupling components are 5-bromo-2,3-dihydroxypyridine and 5-chloro-2,3-dihydroxypyridine.

Heavy metal complexes containing one or more reactive groups can be prepared by using diazo components which already contain reactive groups. In many cases it is also possible to ^four reactive groups additionally to introduce azo compound. This introduction can be carried out after coupling or metallization. Of particular interest are those compounds which contain a six-membered heterocyclic ring or an aliphatic reactive radical containing no more than three amino atoms bonded via an amino group.

The introduction of the reactive moieties is preferably carried out by acylating the corresponding azo compounds containing the acylated amino group or the corresponding diazocomponent which, in addition to the amino group for diazotization, contains another acylated amino group or a group which can be reduced or saponified to an acylated amino group such as nitro.

Particular mention may be made of heterocyclic diazo components which contain aminoarylazo groups, such as:

5- (3'-amino-4'-sulfophenylazo) -8-aminoquinoline,

5- (4'-amino-2'-sulfophenylazo) -8-aminoquinoline or

5- (4 * -amino-2 *, 5 * -disulfophenylazo) -8-aminoquinoline, which by acylation of the phenyl-linked amino group can be converted to reactive diazo components.

Suitable azo compounds to which the reactive residues can be introduced (i.e., after coupling or metallization respectively) are the coupling products of the aforementioned diazo components with halogen-2,3-dihydroxypyridine. It depends on the starting compound or also on the complex with the heavy metal whether there is one or more reactive groups in the final compound.

As' acylating agents, which contain, in addition to the acylation site, &quot; one more reactive moiety, in particular, halides or anhydrides of organic acids containing easily exchangeable atoms or groups of atoms.

Acylating agents containing a reactive moiety include, for example:

Chloro- or bromoacetyl chloride, beta-chloro- or beta-bromo-bromo-piperidine chloride, alpha-beta-dichloro- or alpha-beta-1-chloro-propionyl chloride, chloride of chloroformic acid, carbyl stearate;

aki ^^^ Lů ^dd ^h-oirid, beta-chloro- or beta-chloroactyl chloride, alpha-chloro- or alpha-bromoacrylotl-chloride, alpha, beta-dichloro-or dibromocyclyl L-lehoride, trichloroacryloyl chloride _J . ,

3,5-diitro-4-chlorobutyl-sULfPilla or -carbidyllide;

3-Iitro-4-chlorobenzisulfosyl- or acarbonyl chloride;

2.2.3.3-tetrofluorocyclobutyl-L-carboxylic acid, n-tert-chloroethylsulfanyl-indomethylene-cyclohexylcarbonyl chloride, acrylsulfonylbutylindomethyllekoxyhexane and carboxylic acid derivatives, in particular carboxylic acids, and the like; , 2-Chlorobenzylcarbolyl- or sulfonyl sulfide, and in particular the following reagents containing as hetero atoms, at least two nitrogen atoms in the small ring:

4.5- dieUltra1-phenylpyridazoicarbtnyl- or sulphtriylchloride _>

4,5-diehltrpyridaztipгopPoni · lchuride, -, 4-diclorophthalazocarbonyl or -sulfonyl chloride,

2.3- dichloeuhtnouinLinkaгionybtneao tbtlasuyloiloeUdO,

2.4- dichloгeUiiaztliikýrbt: nyla or -sulphthylhide,

2-meta-fluorophenyl-4-chloro-6-methylpyrimidium, from tttracUL.trpyridazine,

2,4- bis-methaniLUftJiУ-a6ametylpyrimidine,

2.4.6- tri- or 2,4,5,6-tetrachloropyrimidium ,.

2.4.6- three- or 2,4,5,6-ettabbommpyrimidine,

Amethhniujfooil-4 ₂₎ 5-6-dieUltr mttUylpyгimidii,

2,4-Dichloropyrimidin-5-sulfonyl acid,

5-nitro- or 5-cyclohexyl-, 4,6-trichloropyrimidine,

2.6- bibimethahaulfontipypimine-i · ~ kakboboicllL ^oг i <r, ·

2,4-Difluoro-5-chloromethyl-6-methyl-pyrimidine.

2,4-dibromo-5-methyl-6-methylpyrimidine,

2.4- diehltra6acUlormttUylpyrimidii,

2,4-dibrtm-5-brtmeehhlppugimidine,

2.5.6- trichloro-4-methylpyrimidium,

2.6- dicheultratriieUotrletttulpyrirliěin n ene o ezmémé ‘

2,4-Dimethyl-5-chloro-6-methylpyrimidium,

2,4,6-Trimethyl-phosphoril-1,3,5-triae.

2.4- diehLtrpyrimidii, - «,

3.6- dicheurtypiclazan,

3,6-dicuropyridae-5-carbonyl] chloride.

2,6- Dichloro- or 2,6adibгoma4acarboethtxypyгimidine ,,

2,4,5-trichloropyrimidii,

2,4-Dichloropyrimidium-6-carbonamide.

2,4-diehltrpyrimidii-5-kaгbtlirlc1h.oгid

2,6hdoc-2-r- or 2,6-dibromomethyl-4- or 5-carbonyl or -sulfomylsmid, respectively;

-4- or -5-sulphonyl chloride: Loride,

202524 8,

2.4.5.6- tetrachloropyridazl-n, ´

5-bromo-2,4,6-trichloropyrididine,

5-acetyl-2,4,6-trichlorparimidine,

5-nitro-6-methyl-2,6-di-chloropyrimidine.

2-chlorobenzthiazole-6-carbohydrate.

2-Cyclobenzothiazole-6-sulfonyl chloride.

5-nitro-6-methyl-2,4-dihydropyrimidine,

2.4.6- trtflur-5-chlorpprimiminj

2.4.5.6- tetrifluorpyrimidine,

2.4.5- tгlfUrorpirimidiz,. . .,

2.4. ⁶ - tricMorC-triboom- or tricks -) - ¹ ^ i ^ trffzin-and 4,6-di ^ d chlorocyclopentane or oGm- · - ^^ ^ 11) - 1,3,5- ^ 18 ^ 1 ^. are in position 2 subbSituovány aryl or alkyl, e.g. enyl, · methyl or ethyl, or an aliphatic or aromatic residue through a sulfur atom bonded meekapPo81ouδenini respectively bonded through oxygen hydroxyз1ruδenini, or in particular with NH ₂ -group or via · radical of an aliphatic, heterocyclic or aromatic amine compounds bonded via a nitrogen atom, As such compounds; the trihalogeptrizene reaction residues bind to the 2-position of the triazine nucleus, for example: aliphatic or aromatic mercapto- or hydrocompounds, such as β-β-β-ols, threegylic acid, threezoic, alkoxyalkanols, methyl, methyl, ethoxy, ethyl, methoxyl, ethanol, methyl, ethoxy and the like; rsrprrpyla1krhol · kysMina glycol, phenol, chloro or zitrrftzr1i, and sulfonic 1tnr1karioxy1ové ky3611 ^^ ^^ 81, na1tr1su1ronové acid, etc., but especially ammonia and amine-containing compounds acylatable · as hydroxylamine, hydrazine, 1ezillydraziz, 1ezy1hynгatrnsulfonrvé acid _{(glykrlmorzrakyiθther,} meethy.-, ethyl-, isoprrpyi-, eeth02qrietui.-, metur: propyypropylaein, diήθΜΙ-!! -, methyl-, meethy.feiny.-, ethyl enphenyl amine, ^ 1 ^ μ11! 1 (μ1ζ, ttanoanolamine, propanolamines , benzylamine, cyclohexylamine, eoof10in, piperidine, piperidine, ammonium carbonate ester, microfluorocarboxylic acid, aminotransulphonic acid, N-methylaminoethanesulfonic acid, but in particular aromatic amines, such as aniline, N-meehuianirin, triline, xylidine, · chloronailine, β-resp, ε-εalinzocethaneZrine, animooenols, anisidine, phenetidine, and especially acidic groups, including aniline, suanil, meehanil, · orthaniline · anionic acid, aminobenzylsulphonic acid, aminobenzylsulphonic acid, azrizine-ω-methazsulphonic acid, aeinobenzordecarboxylic acid, naphthalizoleoso-, -di- and -trsunfonic acid, amisopropyrimidic acids, as well as 2-hydroxy compounds, compound with the character of the dye, e.g., 4-ΜΛ ™ -4 -aminorti1iendisu1fonrvá acid, 2-nitro44 * -ιeinrdi1tzy1eeino ^4,3-tf -stiitzndisu1ronrvá acid, 2-nitůÓ44 * aeшioddi.r 1ezy1aeinr 4 _·> 3 * -disu1fonové acid and in particular amoazo dyes or amizoin glutahizos or tarocyazis which contain at least one reactive,

The introduction of the sub-primers at the 2-position of the triazine residue can be accomplished by condensation with the starting diamine or the reaction of the invention to form the compound.

In addition to the acylation of the fiber-reactive irradiating residues, the introduction of a vinyl sulfone group, a beta-sulphate or a thiol sulphate, may be contemplated for the first time a group of beta, thiofluoropropanol, a first group, an acetic acid, a sulfonic acid or a sulfonic acid or sulfonic acid group. beta-sulpharroylHallo-first groups which, for example, can be introduced via an ester nsbo thirester ester group on a diazocomponent,

Compounds which contain a reactive moiety which is not melt-acylated in which the fiber-reactive moiety is also preferably not bonded via an amino group but is directly bonded to a benzene moiety include, but are not limited to, the following sulfones:

1-amyl-2-meth10'-i - (- leia-hl ^< У ^Γ0 t0 ^г eieyliL)

1-Aminobenzyl-3- or -4-diethynylpyrrolidylsulphine; ·

-emino-2-meetui1iezzen5-bita-l'h _l rylnoylχ'ietu ^r isul1rn,

1-amino-4- (beta-hydroxyethylsulfonylpropionylaminomethyl) -benzene, 1-amino-4 '(beta-hydroxyethylsulfonylamino) -benzene, as well as the corresponding methylols containing reactive compounds such as:

1-amino-4-chloroacetylaniinomethylbenzene or

1-Amino-3-chloroacetylaminomethylbenzene-6-sulfonic acid.

The condensation with acid halides or anhydrides or with heterocyclic halogen compounds is preferably carried out in the presence of an acid binding agent such as sodium carbonate or sodium hydroxide and under conditions such that one more unsaturated bond or a replaceable halogen atom remains in the final product. for example by performing in organic solvents or at relatively low temperatures in an aqueous environment.

к - ** '

1: 1 complexes with heavy metals, especially complexes of the compounds of the present invention with cobalt 1: 1, can be stabilized by adding more, especially three organic residues, via a nitrogen atom to the metal atom. ·

For residues that form a metal chelate complex through a primary, secondary or tertiary nitrogen atom, at least two, preferably all three, of one and the same preferably aliphatic polyamine are present, with three or preferably two additional atoms between the individual nitrogen atoms , so that the formed chelate complex forms a six- or five-membered ring under the influence of a metal atom. Examples of such polyamines are: diaminoalkylenes, wherein the alkylene bridge consists of three or preferably two carbon atoms, optionally the corresponding C-alkyl, N-aino-alkyl or C-amino-alkyl derivatives, for example ethylenediamine, 1,2 or 1,3- diaminopropane, 1,2- or 1,3-diamino-n-butane, beta- (methylamino) -ethylamine, beta- (ethylamino) -e thylamine, betar (dimethyl amino) -e thylamine, N- (beta-hydroxyethyl) -ethylenediamine, Ν, Ν-dimethylethylenediamine, Ν, Ν *, N ** -trimethylethylenediamine, N ** -tetramethylethylenediamine, especially but diethylenetriamines, triethylenetetramines, 4-tetraethylenepentamines, dipropylenetriamines and the like, such as amines of the formulas:

1Ш ₂ - ^СН 2 ^С Н ^{2-1Щ-СН2-С} Н ^{С Н2} 2 NH ₂ -CH ₂ -CH ₂ -NH-CH ₂ -CH ₂ -NH-CH ₂ -CH ₂ -NH ₂ N? - CH-C-NH-C ^ -C-NH-CH₂-CH₂-NH-CH₂-CH₂-NH ₂ NHG -0¾ _{-CH2-CH2-NH-CH} 2 -C H ₂ -CH ₂ -NH ₂ .

In the case of the use of a diamine, the third ligand bound to the metal atom complex is ammonia or a primary or secondary or tertiary amine, for example methylamine, ethylamine, mono- and diethanolamine, dimethylamine, diethylamine, benzylamine, aniline, triethanolamine, piperidine or pyridine.

The preparation of the novel compounds is preferably carried out by metallising a mixture of azo compound and amines, respectively, in the case of metal complexes, in particular. amine with a metal releasing agent, wherein the reaction is practically immediate. If alkoxyl is adjacent to the azo group, it is converted to the hydroxy group (so-called dealkylation metallization) in the usual way (intermediate) during metallization.

Alternatively, the amine is first reacted with a metal releasing agent and the 1: 2 cobalt-amine complex obtained is converted to the desired complex by reaction with a metallable azo compound. In the case of chromium complexes, the preparation is preferably carried out by first preparing a 1: 1 complex of the azo compound for chromium and then reacting with the amine or amines, respectively.

In the first step of the above process, the metal releasing agent, the azo compound and the amine, respectively, are generally employed. The amines are mixed in stoichiometric amounts as is consistent with the composition of the final product. Proceed further so that metallization

R0 is carried out in a slightly acidic to alkaline environment. Metal releasing agent. is preferably a single cobalt salt such as cobalt sulfate or freshly precipitated cobalt hydroxide. With these . With the simple cobalt salts, the reaction according to the invention can also be carried out in a slightly acidic medium

Conversion to the cobalt compound complications is preferably carried out under boiling, often under pressure, for example at the boiling point of the reaction mixture, optionally in the presence. suitable addition, for example in the presence of salts of organic acids or bases, organic solvents, such as glycol monomethyl ether, ethanol or n-butanol or other complexing agents. . ·.

Surprisingly, these complexes exhibit amines which do not contain an amine compound)! neither a sulfo group nor a carboxy group, not only good solubility in alcohol but also good solubility in water.

The azo compounds containing heavy metal, in particular copper or nickel, prepared according to the present process and their variations are novel for dyeing and printing various substances, in particular for dyeing animal materials such as silk, leather and in particular wool, but also for dyeing and printing of synthetic fibers of superpolyemides or superpolyurethane, acrylic poles and the like.

If no sulfo group is present in the complex metal compounds of the present invention, the water solubility is reduced. Instead, the solubility in organic solvents is substantially improved.

If no solubilizing substituents such as sulfonamido or nitro groups are present, the solubility in organic solvents is only mild.

«. '

The complexes with one or more sulfo groups are particularly suitable as dyes for vLOu, silk, leather and especially polyamides. Compexes containing sulfonamido groups are suitable for lacquering purposes and the like. dyes for dyeing polyamides in the spinning material The obtained comi-pips having fiber reactive groups of two or more sulphide groups can be used as conventional reactive dyes if they are completely defective! sulfo groups, suitable as reactive disperse dyes. .

The heavy metal complexes of the present invention which contain no cationic charge are particularly suitable for coloring polyacrylonitrile fibers. The novel dyes are suitable for dyeing nitrogenous fibers, such as wool, for example from an acetic acid bath to a neutral bath, optionally using only water-soluble dyes with the addition of a suitable dispersant. Especially when water-soluble dyes, i.e., azo-dyes, are used. in a complex of two or more sulfo groups, dyeing is carried out using conventional auxiliary agents.

Further, the nitrogen fibers, in particular wool, can advantageously be dyed with the dye prepared according to the present invention such that the dyeing is carried out in a continuous manner, for example by blowing, whereby the fibers are continuously fed into an aqueous preparation containing wool dye and an auxiliary agent which can form with water; with optional additives, a two-liquid system with a gap, whereby the water or additives, if any, and the auxiliary agent come into contact with or near the gap, the gap being formed with sufficient auxiliary content and a large proportion of the gap forming the auxiliary phase and then subjecting the aqueous preparation material to heat treatment. ,

The dyeings and prints obtained using the new dyes generally exhibit wall-to-wall density with acid and alkaline stability, good light fastness and good abrasion fastness, and generally hardly change the appearance in artificial light and partially deteriorate very much.

1 interesting and valuable shades. Particularly pure shades are obtained when new dyes are used for dyeing polyamide articles, in particular when dyeing nylon 6,6 material.

In the following example, parts and percentages are by weight and temperatures are in degrees Celsius. There are the same relationships between weight and volume parts as between gram and cubic centimeter.

Example

22.4 parts of 8-aminoquinoline-5-sulfonic acid is diazotized in an indirectly known manner and then coupled with 19 parts of 2,3-dioxy-5-bromopyridine. Obtained mono dye constitution

Br was isolated from the coupling mixture by salting with sodium chloride, filtered and dried under vacuum.

8.5 parts of the dye obtained are dissolved in 200 parts of water at 80 ° under neutral reaction.

After addition of a solution of 5 parts of copper sulfate pentahydrate and 5 parts of crystalline sodium acetate in 50 parts of water, the mixture is stirred at 80 ° for 30 minutes. The original red-violet starting dye turns to a clear 1: 1 blue solution of the complex, precipitates by addition of sodium chloride, filtered and dried. .

Polyamide fibers are dyed from a slightly acid bath to a pure red-blue shade with good fastness.

In the same process, 6 parts of nickel sulfate heptahydrate and 3 parts of cobalt sulfate heptahydrate are used instead of copper sulfate to form a corresponding 1: 1 complex with nickel and nickel, respectively. 1: 2 complex with cobalt, by which the polyamide fibers are dyed from a slightly acidic bath to a greenish-blue tint.

6.5 parts of the above dyes are mixed in 20 parts of water at 80 ° together with 20 parts by volume of 1 N sodium hydroxide solution. After the addition of 30 parts by volume of a sodium disalicylate-lactate solution in the presence of 3 wt. % Cr ^ O ^ ^mixture so long maintained at reflux until no detectable starting dye.

The resulting water soluble 1: 2 chromium complex is recovered from the solution after evaporation and stains the polyamide fibers from a slightly acid bath to a steady blue-green shade.

The following table lists diazocomponents and coupling components from which, as described above, the corresponding azo compounds are obtained, which are complexed with the metals mentioned in the next column and in the last column the shades of the dyes obtained on the polyamide are shown.

Diazocomponent No

Azokomponenta Metal  Tint to polyamide ^c, OH-OH  ιηδδ blue

δ. Diažokomponenta

Azokomponenta

Shade on polyamide

Cl-R y-OH —Он nickel OH ^ N ^ OH cobalt ^Вг 'пГ ^ч г ~ ^он • 4 _ν Λ-οη currency Br — гИЧ — ОН он nickel Br-тИу-ОН 4 _Ν ^ -ΟΗ cobalt ’Χ ^ chrome α-χχ-οΗ ХХон currency ^α χ = ο ^Η Η 1 nickel 'Xr ™ cobalt

gray-blue green-blue blue green-blue green-blue gray-blue blue green-blue blue, violet

C.

1

Diazokomponenta

Azokomponenta Metal Shade on polyamide вг— (ГЧ— ^OH * 1 _Ν Λ- он copper claret

nickel.

ruby

green-blue

Br

OH OH

nickel cyan cobalt green copper blue

_NH-CO-0-CH

II ²

Br Br

Br

OH OH

nickel green-blue

No. Diazocomponent

Azokomponenta

Metal

NH — COCH — CH

Br Br

Br

OH OH cobalt

Tint on green polyamide

violet

Red - violet blue blue green - blue blue green - blue • 202524

Diazocomponent No

Azokomponenta

Br

OH OH

Br

OH

OH »31

COCH ₃

nh ₂

COCH ₃

^COCH 3

OqC-NH3

Br

OH OH

Br

OH

OH

Metal Shade Polyamide Cobalt Blue-Green Copper Blue Nickel Green-Blue Cobalt Blue-Green <

cobalt violet currency violet nickel red violet

.1,

Diazocomponent No

Azokomponehta нЛ-

Br

OH OH

Metal • Polyamide cobalt violet

Prescription for dyeing woolen fabric _t ,

Claims (7)

Prescription for dyeing woolen fabric, in a dye bath consisting of 300 parts water, 5 parts 40% acetic acid, 10 parts sodium sulfate, 2 parts ethylene oxide adduct, the preparation of which is described below and 1 part · 1: 2 complex with the cobalt prepared in Example 1, is dyed at. temperature 50 60 ° 100 parts of wool fabric. Then, the bath is heated to boiling for half an hour and dyed for another hour. After washing and drying, a uniform green-blue color develops. The preparation of the ethylene adduct is carried out as follows: 100 parts of technical deylemine are heated with 1 part of finely divided sodium to 140 ° and then ethylene oxide is introduced at 135-140 °. Once the ethylene oxide is consumed rapidly, the temperature is not allowed to drop to 120-125 ° and the reaction is continued until the consumption of 113 parts of ethylene oxide is introduced. The reaction product thus obtained is dissolved in water to a practically clear solution. Prescription for dyeing. In a dye bath of 3000 L of water, 5 parts of 40% acetic acid, 10 parts of sodium sulfate and 1 part of copper complex, 100 parts of nylon 6.6 fabric are dyed at 50-60 °. The bath is then heated to boiling for half an hour and the fabric is dyed for an additional hour. After washing and drying, a uniform green-blue color is obtained. ,. Prescription for dyeing wool knitting yarns For a dye bath consisting of 3000 parts. water, 5 parts of ammonium sulfate and 1 part of the 1: 2 chromium complex described in the example are added 100 parts of wool knitting yarn. The bath is heated to boiling for half an hour and then dyed for one hour after boiling. After rinsing and drying, a 100 mm green-blue color is obtained. ’. BEFORE THE INVENTION 1. A process for the preparation of complexes of azo compounds with heavy metals derived from azo compounds of formula I ' D - H = N- (I) Wherein H is a halogen atom and D is a 5- or 6-membered heterocyclic radical and one or two nitrogen atoms optionally containing one fused benzene ring and wherein the three atoms of the heterocyclic diazo component are together with an a-bridge. one of the possible mesomeric or tautomeric boundary forms of the structure of structure Ia -YX = O-N = N- (Ia) wherein one of X and Y is nitrogen and the other nitrogen or carbon, wherein the azo compound of formula I is reacted with a metal releasing agent to form a complex with a heavy metal containing one or two azo compound molecules per complexing metal atom, and optionally, if the metal complex contains an acylatable amino group, it is reacted with an acylating agent. 2. The process according to claim 1, wherein the starting material is 5-bromo-2,3-dihydroxypyridine. 3. A process according to claim 1, wherein the azo compound of the formula II is used HO OH where D is the 8-position quinoline residue attached. 4. A process according to any one of claims 1 to 3, wherein Z is chloro or bromo, sulfo, acylamino of 2 to 4 carbon atoms or phenylazo, which may be substituted by sulfo and acylamino of 2. up to 4 carbon atoms reactive with the fiber. 5. A process according to any one of claims 1 to 4, wherein the process is based on a copper or nickel releasing agent. ‘ 6. A process according to any one of claims 1 to 5, characterized in that it is based on azo compounds which contain reactive residues or that hay-finished metal complexes introduce reactive residues. Sfvfrogrefia. n. p- plant 7. Mozt