DE1444688C - Process for the production of formazan dyes containing cobalt - Google Patents

Description

The present invention relates to the production of new, cobalt-containing formazan dyes which are used for Dyeing and printing of natural or synthetic polyamide-containing textile material. Use Find.

It has been found that valuable formazan dyes containing cobalt are obtained if 1 mol a formazan compound which has no acidic dissociating, salt-forming group and no sulfamide group, with the exception of arylsulfamide groups, and corresponds to the general formula (I)

X-A-N = N-C = N-NH-B

(QL-i
(O) _n SZ

in which A is an aromatic radical, B an aromatic radical which does not contain any metallizable groups in the o-positions to the nitrogen bond, X a hydroxyl group in the o-position to the nitrogen bond of A, Q a bridge member, Z an optionally substituted, lower, aliphatic hydrocarbon group, W an optionally substituted, saturated or unsaturated aliphatic, an optionally substituted cycloaliphatic or aromatic hydrocarbon radical or a heterocyclic radical free of ring nitrogen atoms or the nitro or cyano group and «" and m the numbers t or 2, η preferably 2, mean, or a mixture of formazan compounds of the formula (I) with a less than 1 mol of cobalt-releasing agent to a compound which contains 2 molecules of formazan compounds of the formula (I) for 1 atom of cobalt.

By definition, water-dissociating, water-solubilizing groups that dissociate in water, such as the (I) 15 - SO ₃ H or the - COOH group, and, as sulfamide groups, the - SO2NH2 group, on the amide nitrogen atom are mono- and disubstituted sulfamide groups by optionally substituted lower aliphatic groups and sulfonic acid amide groups substituted by two nitrogen substituents together with the amide nitrogen atom to form a heterocycle.

The new formazan dyes containing cobalt correspond to the general formula (II)

^N \

B ₁ -Nn

Co Xi

(0) _Bl

X, '

^ NB ₂

NCW ₂ Y ⁺

(Π)

In this Ai, A2, Bi, B2, Qi, Q2, Zi, Z2, Wi, W2, "ι, -" 2, m \ and mi mean that for the symbols A, B, Q, Z, W, η or m under formula (I), X'i and X'2 denote divalent oxygen which is in the o-position to the nitrogen bond of Ai or A2, Y ⁺ is an equivalent of a cation, in particular an alkali metal ion, e.g. B. the sodium or potassium ion. .

A and B in formula (I) belong, for example, to the naphthalene series or, advantageously, to the benzene series. The aromatic radicals A, B and possibly also W (W meaning an optionally substituted aromatic hydrocarbon radical or a heterocyclic radical free of ring nitrogen atoms) can be further substituted within the scope of the definition. They can contain nonionic substituents, for example halogens such as fluorine, chlorine or ₄ bromine, aliphatic, cycloaliphatic, araliphatic or aromatic groups such as methyl, ethyl, trifluoromethyl or hydroxyethyl, cyclohexyl, benzyl, optionally substituted phenyl groups, furthermore Alkoxy, cycloalkoxy, aralkoxy or aryloxy groups or even cyano, nitro, alkyl and arylsulfonyl, alkyl and arylsulfoxyl, alkyl or aryl-carbonyl, such as acetyl or benzoyl, carboxamide groups, including the N -mono- and Ν, Ν-disubstituted carbamyl groups or acylamino groups. Preferred acylamino groups are carbacylamino groups, particularly lower alkanoylamino and N-alkyl-N-alkanoylamino groups, such as the acetylamino and propionylamino groups. or N-methyl-N-acetylamino group, or lower carbalkoxyamino groups, such as the carbomethoxyamino or carbethoxyamino group, or lower alkylsulfonylamino and N-Al-. alkyl-N-alkylsulphonylamino groups, for example the methylsulphonylamino, ethylsulphonylamino or N-methyl-N-methylsulphonylamino groups.

W denotes an optionally substituted, saturated or unsaturated aliphatic Hydrocarbon radical is, for example, the methyl, the trichloromethyl, the ethyl, the n-propyl, the Propylene or the n-butyl group. W denotes an optionally substituted cycloaliphatic Hydrocarbon radical is, for example, the cyclohexyl group, and the meaning of an optionally substituted aromatic hydrocarbon radical is in particular the phenyl, the 1- or the 2-naphthyl group. Is W a. heterocyclic radical free of ring nitrogen atoms, then means he z. B. the furyl (2) or the thienyl (2) radical. Nitrogen-containing heterocyclic rings are not suitable because of their basicity they tend to form salt with a change in color. .

W is preferably the phenyl, 1- or 2-naphthyl group, since these are particularly lightfast Result in dyes. . .

Z in the meaning of an optionally substituted, lower aliphatic hydrocarbon group preferably having 1 to 4 carbon atoms represents z. B. the methyl, chloromethyl, ethyl, propyl or butyl group.

Z is preferably the - CHs group, since the dem

- CH3 corresponding - SO ₂ CH3 group gives particularly good solubility in water.

- The group .

O Lt ■ ■ ......

■ ν '?' ■) * ■■ '■ ■■ ⁽⁰⁾ "■' -. '· Can at best also be bonded to the aromatic radical A via a bridge member Q. Q is, for example, phenylethylene, phenylenoxy, phenylenethio, phenylenemethylene, Sulfonic acid phenylene amide, sulfonic acid - N - alkyl - N - phenylene amide, carboxylic acid - phenylene amide, phenylene carbonyl - amino, phenylene sulfonyl, phenylene carbonyl, phenylene sulfamyl or a phenylene carbamyl group.

Valuable, easily accessible formazan dyes containing cobalt, which are characterized by good dyeing properties are derived from: '

of formazan compounds of the formula (I) in which A is a radical of the benzene series containing the hydroxyl group in the o-position to the nitrogen bond, B is a radical of the benzene or naphthalene series free of metallizable groups in the o-positions to the nitrogen bond and W is an optionally substituted phenyl - or naphthyl radical; of formazan compounds of the formula (I) in which A is a radical of the benzene series containing the hydroxyl group in the o-position to the nitrogen bond, B is a radical of the benzene series free of metallizable groups in the o-positions to the nitrogen bond, and W is an optionally substituted phenyl group and η 2 is, or

of formazan compounds of the formula (I) in which Z denotes the methyl group, «2 and m denotes 1.

Particularly valuable cobalt-containing formazan dyes of this preferred class according to the invention derive from formazan compounds of the formula (III),

OH

A subgroup of preferred formazans according to the invention contains compounds of the formula (IV):

OH

= N-C = N-NH

O ₂ SZ

(IV)

O ₂ SZ

in which Q is a bridge member, such as phenylene-sulfonyl, N-phenylenamino-sulfonyl or N-alkyl-N-phenylenamino-sulfonyl, Z is an optionally substituted lower aliphatic hydrocarbon group, W is the phenyl or a nonionogenically substituted phenyl group and m is the number 1 or 2 and in which the benzene nuclei A and B can contain further nonionic substituents within the scope of the definition, preferably chlorine, methyl or nitro groups. These dyes produce on textile material containing polyamide groups, in particular on mixtures of different wool qualities, very level, good light, rub,. Alkaline, milled, washable and seawater-proof, opaque gray, olive, navy blue to black colors.

in which Z denotes the - CH ₃ , - C ₂ H ₅ - or - CH ₂ - Cl group and W denotes the phenyl or a nonionogenically substituted phenyl group and in which the benzene nuclei A and B contain further nonionic substituents within the scope of the definition be able.

The formazan compounds of the formula (I) are obtained by processes known per se. For example, an aldehyde is condensed with the hydrazine from an amine A - NH ₂ and the hydrazone obtained is coupled with a diazonium compound from an amine B - NH ₂ , where A and B have the meanings given under formula (I), or advantageously a hydrazine condensed from an amine B - NH ₂ with an aldehyde and the hydrazone obtained is coupled with a diazonium compound from an amine A - NH _2. Or you couple z. B. one equivalent of a diazonium compound from an amine A, - NH ₂ and B - NH ₂ with a twofold couplable methylene or methine compound with elimination of one or two easily removable groups or groups converted into such easily removable groups, e.g. B. formyl, acetyl, carboxylic acid, carboxylic acid ester, amide or nitrile groups.

In both processes, the components are to be selected so that the end product has at least one the benzene nucleus A or a substituent according to the definition bonded to a bridge member connected to A-

- S —Z

Il

(0) "
contains.

Amines A - NH ₂ and B - NH _{2 which} can be used for this purpose are e.g. B. 2-amino-1-hydroxy or aminobenzene compounds or o-hydroxyamino or aminonaphthalene compounds, which can be substituted within the scope of the definition, e.g. by halogen or nitro, alkyl, aryl, alkyl or aryl carbonyl , Acylamino, alkylsulfonyl, arylsulfonyl or alkylsulfoxy groups _v alsp for example 2-amino-1-hydroxybenzene or 1-aminobenzene or 2-amino-1-hydroxy- or 1-amino, -4- or -5-chlorine -, -4- or -5-bromo-, -4,6-dichloro- or -4,6-dibromo-, -4-chloro-6-nitro-, -6-chloro-4-nitro-, -4 - Or -5-methylsulfonyl-, -4- or -5-methylsulfoxyl-, -4- or -5-ethylsulfonyl-; -4- or -5-chloromethylsulfonyl-, -4- or -5-propylsulfonyl-, -4- or -5-butyIsulfonyl-, -4- (3'-methylsulfonylphenyl) -sulfonyl-benzene or 5 - amino - 6 - hydroxybenzoxathiol - S - dioxide or 2-amino-1-hydroxynaphthalene, 1-amino-2-hydroxynaphthalene or 1- or 2-aminonaphthalene.

Examples of aldehydes that can be used for implementation with Arylhydrazines that can be used are aliphatic aldehydes, such as acetaldehyde, trichloroacetaldehyde, Propionaldehyde, butyraldehyde, crotonaldehyde, oenanthaldehyde, cycloaliphatic aide

hyde, such as hexahydrobenzaldehyde, aromatic aldehydes, such as benzaldehyde and its core substitution products, such as alkyl, halogen, nitro, alkoxy, alkylsulfonyl, arylsulfonylbenzaldehyde, or optionally Nuclear-substituted naphthaldehydes, such as 1- or 2-naphthaldehyde, also heterocyclic aldehydes, such as furfural or thiophene-2-aldehyde.

As a double-couplable methylene or methine compound for the second type of production Formazans of the formula (II) are used, for. B. cyanoacetic acid ester, nitroacetic acid ester or phenyl formyl acetic acid ester and the corresponding nitrile, · Alkylphenylformylessigsäureester,. Phenylcyanoacetic acid or dinitrophenyl acetic acid, its esters and amides, naphthyl formyl acetic acid esters, z. B. a-Naphthyl-formyl acetic acid ester.

As cobalt-releasing compounds with which the inventive conversion of the formazans of the formula (I) is carried out in their cobalt complexes of the formula (II) by methods known per se, if water-soluble simple or complex salts of divalent or trivalent cobalt are used, it is advantageous Cobalt (II) salts of organic or inorganic acids. When using cobalt Introductory salts of mineral acids are expediently carried out in the presence of a mineral acid blunt Means, such as alkali hydroxide or -car-. bonate or alkali salts of lower fatty acids, for example Alkali acetates or alkali salts of polybasic oxygen acids of phosphorus.

As a polyamide-containing textile material, which with the cobalt-containing formazan dyes according to the invention can be colored or printed, artificial polyamides come, but in particular natural polyamides such as silk, leather and especially wool are in question. This is dyed textile material Kind advantageous with dyes according to the invention. You pull on these materials already from neutral until weakly acidic bath. '; . '·

If necessary, the water solubility of such dyes is increased by adding anionic active substances or non-ionic wetting or dispersing agents as

Coupage favors. -. :. '· ■.' ·

The textile dyeings obtained with the dyes according to the invention are brown, gray, sometimes with a bluish cast. or greenish gray to olive, navy blue or black. They are particularly characterized by the good light and rub fastness and very good wet fastness, z. B. good washing, alkali, fulling and Seawater fastnesses. Compared to previously known copper complexes that per mole of formazan dye contain a metal atom, the dyes according to the invention are usually characterized in that they dye mixtures of different wool qualities more evenly. -

In the following examples, unless expressly stated otherwise, parts are parts by weight. The temperatures are given in degrees Celsius. Parts by weight are related to parts by volume as grams to cubic centimeters.

example 1

N - / ^ V-SO ₂ CH ₃

Λ: ο ^ οΑ /

CH, O, S-L J N

ν /

Na®

18.7 parts. ^ Methylsulfonyl ^ -amino-1-hydroxybenzene are dissolved in 100 parts of hot water with 17.5 parts of concentrated hydrochloric acid, to 5 ° cooled and diazotized with a sodium nitrite solution (corresponding to 6.9 parts of sodium nitrite). Through Addition of sodium bicarbonate makes the reaction mixture neutral. The brownish yellow diazonium suspension is produced at 0 to 3 ° in a suspension of 19.7 parts of benzaldehyde phenylhydrazone ( by condensation of benzaldehyde and phenylhydrazine) in 250 parts by volume of glycol monomethyl ether touched.

At 0 to 5 °, the coupling mixture is brought to a pH of.

9.5 to 10. After the formation of the dye has ended, it is filtered by adding 1000 parts by volume saturated sodium chloride solution precipitated dye. It is washed with a dilute sodium chloride solution, suspend it in 600 parts of water, add 60 parts by volume of cobalt acetate solution (corresponding to 3.54 parts of cobalt) and heat the mixture to 80 to 85 ° until the cobalt complex dye is formed. The dye suspension is then made clearly phenolphthalein-alkaline Addition of anhydrous sodium carbonate, and separates the dye by adding 60 parts Sodium chloride. The cobalt-containing dye is filtered off and washed with dilute sodium chloride solution

washed out. After drying, it is a dark powder, the wool from neutral to weakly acidic bath colors in even, true blue-gray tones.

Similar dyes are obtained if, instead of the diazo component used in the example, a

the diazonium compounds listed in the following table column II and in place of the used Hydrazone used one of the hydrazones indicated in column III. Column IV 5 indicates the shade of the corresponding cobalt complex on wool.

I. Diazonium compound from III Hydrazine aldehyde IV example Hydrazone off Phenylhydrazine Benzaldehyde Nuance of
cobalt 4-chloromethylsulfonyl-2-amino- complex
on wool .2. 1-hydroxybenzene the same the same Gray 4-trifluoromethylsulfonyl-2-amino- 3 1-hydroxybenzene the same the same Gray 5-methylsulfonyl-2-amino-1-hydroxy- 4th 'benzene the same the same Gray 4-methylsulfonyl-6-acetylamino- 5 2-amino-1-hydroxybenzene the same the same Gray 4-methylsulfonyl-6-carbomethoxy- 6th amino-2-amino-1-hydroxybenzene the same the same Gray 4-methylsulfonyl-6-propionylamino 7th 2-amino-1-hydroxybenzene the same the same Gray 4-methylsulfonyl-6-methylsulfonyl- 8th amino-2-amino-1-hydroxybenzene the same the same Gray 4-ethylsulfonyl-2-amino-1-hydroxy 9 benzene. the same the same Gray 4-butylsulfonyl-2-amino-l-hydroxy- 10 benzene the same the same Gray 5-nitro-4-ethylsulfonyl-2-amino- 11th l-hyd, roxybenzene the same the same olive green 6-nitro-4-methylsulfonyl-2-amino- 12th 1-hydroxybenzene the same the same olive green 4,6-dimethylsulfonyl-2-amino- 13th 1-hydroxybenzene 4-chlorophenyl the same olive green also: hydrazine 14th 4-methylphenyl the same olive green Phenylsulfonyl-2-amino-1-hydrpxy- hydrazine ' 15th benzene-3'-methylsulfone ' 4-methoxyphenyl- the same Gray 2-amino-1-hydroxybenzene-4-sulfone hydrazine 16 acid-phenylamide-4'-methylsulfone 4-ethoxyphenyl- the same Gray 2-amino-1-hydroxybenzene-4-sulfone hydrazine 17th acid-N-ethyl-N-phenylamide- Gray 4'-methyl sulfone Phenylhydrazine 2-methoxy 4-methylsulfonyl-2-amino-1 -hydroxy- 1-naphthaldehyde 18th benzene, the same 1-naphthaldehyde Gray the same 1-naphthyl
Hviirii7in Benzaldehyde M9 the same Phenylhydrazine 4-methylbenzene Gray 20th 4-methylsulfonyl-2-amino-1-hydroxy aldehyde Olive gray 21 benzene the same 4-methoxybenzene Gray the same 4-nitrophenyl
VivHrfl7in Benzaldehyde 22nd the same XL V \ AL ** 'Λ''
3-nitrophenyl
1 * 1 vfl rii 7i η the same Gray 23 the same the same the same Olive green. 24 4-chloromethylsulfonyl-2-amino- Gray olive 25th 1-hydroxybenzene 2,5-dichlorophenyl 2,6-dichlorobenzene olive green 4-methylsulfonyl-2-amino-1-hydroxy- - hydrazine aldehyde 26th . . benzene. the same Benzaldehyde violet the same 27 Gray violet

209 632/34

Example 28

38.4 parts of formazan dye (obtained by coupling equimolecular amounts of diazotized ^ methylsulfonyl ^ -amino-1-hydroxybenzene with the hydrazone of phenylhydrazine and furfural) are suspended in 600 parts of water and at 80 to 85 ° with 60 parts by volume of cobalt acetate solution (corresponding to 3, 54 parts cobalt) stirred until the cobalt-containing dye has formed. Sodium carbonate is then added until the dye ^{suspen- sion SO CH I0 s} ' ^{on has a} clearly phenolphthalein alkaline reaction.
³ . The cobalt-containing dye falls after the addition of

Sodium chloride. It is filtered off, washed out with dilute sodium chloride solution and dried. The dry dye is a dark powder, the wool from weakly acidic to neutral Bath colors in real gray shades.

Similar dyes are obtained if 4-methylsulfonyl-2-amiho-1-hydroxybenzene is used in the above example by equimolecular parts of 4-ethylsulfonyl-2-amino-1-hydroxybenzene or 4-chloromethylsulfonyl-2-amino-1-hydroxybenzene or 4-methylsulfoxide-2-amino-1-hydroxybenzene replaced.

B is ρ ie 1 C ₃ H ₇

SO ₂ CH ₃

50 parts of formazan dye (obtained by coupling equimolecular amounts of diazotized 4 - phenylsulfonyl - 2 - amino -1 - hydroxybenzene - 3 '- methylsulfone with the hydrazone of phenylhydrazine and butyraldehyde) are 400 parts of formamide dissolved at 50 ° and stirred with 15 parts of cobalt acetate (corresponding to 3.54 parts of cobalt) until the cobalt-containing dye has formed. By adding saturated sodium chloride solution is the cobalt-containing dye precipitated. It is then filtered off with dilute sodium chloride solution washed out and dried.

After drying, it is a dark powder, the wool from neutral to slightly acidic Bath dyes in real reddish gray shades.

Similar dyes are obtained if, in the above example, instead of the hydrazone, one obtains from phenylhydrazine and butyraldehyde is the equimolecular amount of the hydrazone from phenylhydrazine or p-bromophenylhydrazine and crotonaldehyde or des Hydrazone from phenylhydrazine and hexahydrobenzaldehyde is used.

Staining instructions

4 parts of the cobalt-containing dye according to Example 5 of the table are dissolved in 4,000 parts of water, and 100 parts of well-wetted wool are added to the dyebath at 40 ° to 50 °. Heat it to the boil within half an hour, keep it ^{boiling for} k hours, rinse the wool with cold water and dry it. The gray coloration obtained is very good alkali, wet, rub and lightfast.

Claims (4)

Patent claims: 1. A process for the production of formazan dyes containing cobalt, characterized in that that one mole of a formazan compound that does not dissociate acidic in water contains a salt-forming group and no sulfamide group, with the exception of arylsulfamide groups and corresponds to the general formula I. X-A-N = N-C = N-NH-B (I) (O) _n SZ corresponds in which A is an aromatic radical, B is an aromatic radical which is in the o-positions _(for nitrogen bond no metallisable groups holds, X a hydroxyl group in o-position to the nitrogen bond of A, Q a bridge member, Z an optionally substituted, lower aliphatic hydrocarbon group, W an optionally substituted, saturated or unsaturated aliphatic, an optionally substituted cycloaliphatic or aromatic hydrocarbon radical or one of Ring nitrogen atoms free heterocyclic radical or the nitro or cyano group and η and m denote the number 1 or 2, or a mixture of formazan compounds of the formula (I), with a cobalt-releasing agent less than 1 mole to form a compound which has 1 atom of cobalt Contains 2 molecules of formazan dye. 2. The method according to claim 1, characterized in that that the formazan compound of the formula (I) used is one in which A one the hydroxyl group in o-position to the stick Substance bond-containing radical of the benzene series, B one in the o-positions to the nitrogen bond radical of the benzene or naphthalene series free of metallizable groups and W an optionally mean substituted phenyl or naphthyl group. 3. Process according to Claims 1 and 2, characterized in that the formazan compound of the formula I used is one in which A is a radical of the benzene series containing the hydroxyl group in the o-position to the nitrogen bond, B one in the o-positions to the nitrogen bond radical of the benzene series free of metallizable groups and W denotes an optionally substituted phenyl group and in which η is 2. 4. Process according to Claims 1 to 3, characterized in that the formazan compound of the formula I used is one in which Z is the methyl group, η 2 and m 1.