DE1114961B - Process for the production of chromium-containing azo dyes - Google Patents

Description

In the patent application G 21368 IVc / 22a are Azo dyes containing heavy metals are described which are attached to a coordinatively hexavalent heavy metal atom contain a mono- and a disazo dye bound. These heavy metal complex compounds are suitable for coloring organic materials of the most varied kinds and in particular because of the deep shades and the good fastness properties of the textile dyeings achieved therewith valuable. The dyes according to the invention are prepared by coordinating dicyclically to one Azo dye, which contains one coordinatively hexavalent heavy metal atom per dye molecule, one dicyclic metallizing azo dye attaches and thereby selects the dyes so that the reaction product contains a mono- and a disazo dye complexed on the heavy metal atom. as Dicyclic metallizing disazo dyes are only mentioned which have the two azo groups contain a single aromatic radical, namely attached to a benzene or naphthalene ring.

In the further processing of the subject matter of the invention it has now been found that one is also very valuable dyes are obtained if disazo dyes are used as dicyclic metallizing in the process described Compounds used which correspond to the following formula II and thereby are characterized in that they consist of a metallizable monoazo dye, which has a divalent Bridge member contains a non-metallizable monoazo dye bound.

The chromium-containing azo dyes are obtained by adding a metallizable monoazo dye to the general formula

A ₁ - N = N - B ₁

(I)

and a metallizable disazo dye of the general formula

(A ₈ - N = "N - B ₈ ) - X - (Y - N = N ·

Process for the production of chromium-containing azo dyes

Addition to patent application G 21368 IVc / 22 a (Auslegeschrift 1 111 318)

Applicant: J. R. Geigy A.-G., Basel (Switzerland)

Representative: Dr. F. Zumstein,

Dipl.-Chem. Dr. rer. nat. E. Assmann

and Dipl.-Chem. Dr. R. Koenigsberger,

Patent Attorneys, Munich 2, Bräuhausstr. 4th

Claimed priority: Switzerland of April 14, 1958 (No. 58 295)

Dr. Walter Biedermann, Dr. Fabio Beffa and Dr. Guido Schetty, Basel (Switzerland), have been named as inventors

wherein A ₁ and A _{2 are} the residues of diazo components of the benzene and naphthalene series which contain a metallizable group in the o-position to the diazo bond, B ₁ and B _{2 are} the residues of azo components coupled to a hydroxyl group, X is a divalent bridge member from the Series of carbonylamino, sulfonylamino and sulfonyloxy groups and Y - N = N - Z mean the radical of a non-metallizable monoazo compound, with one another or in succession with a chromating agent under such conditions that one molecule of the monoazo dye is reacted with one molecule of chromium of the disazo dye.

The characteristic divalent bridge member X of the disazo dye of the general formula II conducts

109 708/351

3 4

preferably differ from a sulfonic acid group as well as their further substituted in the aryl nucleus and then consists of either a sulfonic acid compound and finally acylacetylaminobenzenes amide or a sulfonic acid ester group; but it can and naphthalenes. Monoazo compounds from such can also be derived from a carboxyl group and diazo and azo components are known per se, then consists of a carboxamide group. 5 They are widely used starting compounds for

To make this asymmetric 1: 2 chromium production of heavy metal complex dyes for There are two process modes in complex compounds - wool and wool-like materials. In the present fications available. Either one can come up with a process primarily the o, o'-dihydroxy equimoleculars Mixture of metal-free mono-monoazo dyes in question.

and disazo dyes in neutral to alkaline io In the disazo agents which can be used according to the invention in the heat a little more than the equimolecular dyes of the general formula II corresponds to the Act amount of a chromium-releasing compound. metallizable component of the monoazo dye It is most likely that general formula I will be created first. The one above for this one a so-called 1: 1 metal complex compound, dyes given definition and explanation meets which on a molecule of the dye a whole atom 15 accordingly also for this proportion of the disazo-chromium contains. This then occurs with further metal dyes. The non-metallizable part Free dye to the 1: 2 complex connection to Y - N = N - Z can be of the most varied together. Or you first include one of the two components, for example components Azo dyes, preferably the monoazo dye, from the benzene, naphthalene, pyrazole and quinolone groups 1: 1 complex compound over and leaves thereupon 20 or acylacetic acid arylamide series. You can use the in act on the second, metal-free azo dye. Azo dyes customary, sub-these listed above The addition process allows the manufacture to contain substituents. The carbonyl and sulfonyl specials more uniform and pure 1: 2 chromium group of the bridge link X can either be attached to a complex compounds and is therefore the preferred component of the metallizable or one of the manufacturing method according to the invention. The first non-metallizable component of the disazo dye named procedure is a simplified execution-bound to be.

form of the attachment procedure; Production of the For the production of the inventively

1: 1 chromium complex compound and addition of a turned disazo dye are mainly two second dye molecule are considered in the presence of the method. One is that one Starting materials carried out. 3 ° one metallizable and one non-metallizable

In textile dyes according to the invention, von bare monoazo dyes each containing at least one reactive group of the two coordinated azo dyes which react with one another to combine a sulfonyl linkage increasing the water solubility, substituted under suitable conditions. As such, sulfonic acid groups come to act on one another. Such reactive sulfonic acid amide groups or low molecular weight groups are the amino or hydroxyl groups of an alkylsulfonyl group. The finished dye on the one hand and, for example, the carboxylic acid or sulphonic substance, however, advantageously contains no more than one acid halide group on the other hand.
Sulfonic acid group. The second, often more advantageous, method is

The metallizable ones which can be used according to the invention can be achieved by using either a diazo or azo-compo-monoazo dyestuff of the general formula I are 4 ° nents and a monoazo dye, each of which is one of the Coupling products of diazonium compounds of the aforementioned groups which can be linked to one another Benzene and naphthalene series, which are contained in the o-position, can act on one another and then with it to the diazo group one to the metal complex formation of the remaining component to the disazo dye qualified or transferable to such a group.

Containing substituents with in the vicinity of 45. According to the one preferred embodiment a hydroxyl group coupling azo moieties. this second procedure condenses an acyl-AIs The carboxyl oxynaphthalenesulfonic acid chloride does not come with a metallizable group and hydroxyl groups and as amino or hydroxymonoazo coloring reaction which can be metallized during the metallization in the latter transferable z. B. fabric, saponifies the acyloxy group and couples the Methoxy and ethoxy groups in question. The dyes 50 Hydroxynaphthalinsulfonsäureamid or can be removed further substituting esters customary in azo dyes in an alkaline medium with a contain tuenten, for example halogen, alkyl, o-carboxy or o-hydroxybenzene or -naphthalene-alkoxy, Aryloxy, nitro, cyano, acyl and acyl diazonium compounds to the disazo dye. As acylamino, Alkyl and arylsulfonyl groups, and geoxynaphthalinsulfonsaurechlori.de come in particular 55 further substituted on the nitrogen atom are the acyl, ζ. B. Carbomethoxy or toluene carboxamide and sulfonic acid amide groups. As sulfonyl derivatives of the known 1-hydroxy-diazo components for naphthalene-3- or -4-sulfonic acid chlorides which can be used according to the invention and the Monoazo dyes are accordingly optionally 2-hydroxynaphthalene-4,5-6- or -7-sulfonic acid mentioned above Substituent-containing o-carboxy, chlorides in question. As non-metallizable amino and O-alkoxy and o-hydroxydiazobenzene and -diazo-60 hydroxymonoazo dyes are advantageously used naphthalene compounds question. The easily accessible 4-amino and 4-hydroxy used as azo components one primarily 4-alkyl or 2,4-diazobenzenes. The ones available with these components alkyl or 2-acylamino-4-alkyl-1-hydroxybenzenes, disazo dyes are therefore the o- (arylazo) -ferner Hydroxynaphthalenes, such as 1- and 2-hydroxynaphthalenesulfonic acid - 4 '- benzolazophenylnaphthalene, 1,5-, 2,6- and 2,7-Dihydroxynaphthaline 65 amide and the o- (Arylazo) -hydroxynaphthalinsulfon- or their appropriately substituted derivatives, then acid 4'-benzene-azophenyl ester. With 2-hydroxy or Pyrazolones, such as l-aryl-3-alkyl-5-pyrazolones, I-aryl-2-acyloxynaphthalene-3-carboxylic acid chloride are on 5-pyrazolone-3-carboxylic acids and -3-carboxamides, the same way the corresponding 1 -arylazo-2-hydroxy-

5 6

naphthalene - 3 - carboxylic acid - 4'-benzolazophenylamide 2: 1 chromium complex compounds by salting out

easily accessible. and from alcoholic solution by precipitation with

Disazo dyes according to the invention, which the water or by distilling off the organic

Gain sulfonyl group of the bridge member to the diazo solvent.

component of the metallizable constituent gel 5 The chromium-containing azo color according to the invention

contain bonds, you get z. B. by condensate substances are suitable for coloring organic materials

sation of Benzoxazolonsulfonsäurechloriden with the most different kinds in orange, brown, olives,

4-Aminoazobenzene or its substitution products, blue, gray to purple tones. The water-

Cleavage of the oxazolone ring in an alkaline medium, insoluble dyes are mainly used for

Diazotization of the amino group and coupling of the dyeing of paints and varnishes, of paper, of

Diazomonoazo compound with a metallizable viscose, polyamide, cellulose ether and cellulose

Azo component. In this way z. B. the 2-aryl ester spinning masses and polyester condensates.

azo-1-hydroxybenzene-4- or -5-sulfonic acid-4'-benzene- The water-soluble ones are mainly textile dyes

azophenylamides available. and are particularly suitable for dyeing wool,

Disazo dyes, which are the carbonyl or casein, polyamide and polyurethane fibers

Sulphonyl group of the bridge member X in the non-metallic and also for dyeing leather and furs. The color

Containable constituent, one obtains example substances can also be used for printing the mentioned

serve wisely by condensation of azobenzene-4-carbon materials. For textile dyeing is special

acid or sulfonic acid chloride with a primary valuable that is not only the alkylsulfonyl and

or containing secondary amino groups and containing sulfonic acid amide groups in 20, but also the

o-position to the hydroxyl group coupling hydroxy containing a sulfonic acid group according to the invention

benzene or hydroxynaphthalene and coupling of the moderate 1: 2 chromium complex dyes by a good

Mark the condensation product with an o-carboxy or neutral drawability on wool. the

o-Hydroxydiazobenzene or -diazonaphthalene- wool dyeings are very even and show

binding. 25 is characterized by a remarkable lightfastness, very

For the properties of the finished dyes it is good wet fastness properties, for example the very good ones advantageous if wash, fulling and sea water fastness properties that contain sulfonic acid amide groups, and many disazo dyes the amide nitrogen is further characterized by its good alkali fastness. Besubstituted are. For this purpose one goes to note is also the good to very good sulfur weder of the fastness of the wool dyeings corresponding to the amino group.

substituted amino monoazo dyes from or of the dyes according to the invention are in

treats the secondary amide groups containing primarily those valuable for which as monoazo

Dyes with alkylating agents, for example with a dye of the general formula I sulfated

Dialkyl sulfates or alkyl halides. o-Hydroxybenzolazo-o'-hydroxynaphthalene- or a

Salts of the trihydroxyazonaphthalene compound are used as chromating agents valuable chromium, for example chromium sulfate, chromium was. With coupling products from in 6-position chloride, chromium fluoride, chromium acetate or chromium - optionally nitrated 1-diazo-2-hydroxynaphformate, into consideration. Furthermore, in the case of alkali-unempthalene-4-sulfonic acid and 1- or 2-hydroxynaphthalene Sensitive dyes and salts of the hexavalent are obtained especially with regard to the deep ones Chromium, such as alkali dichromates, can be used. 40 shades of valuable dyes. In the same way The presence of a reducing substance is the metalhable component of the disazo dye like glucose, necessary. Finally, an o-hydroxybenzolazo-o'-hydroxynaph chromium complex compounds, such as chromsalicylic acid thalinrest, which contains the carbonyl or sulfonyl group, ammonium or alkali salts. For the production of the bridge link on the hydroxynaphthalene residue which contains 1: 1 chromium complex compounds for 45 bonds. The bridge member is a sulfonic acid preferred addition method treats one amide group, then it is good in terms of the dyes expediently with compounds of the three-alkali fastness of the dyes with advantage a sulfonylvalent Chromium in excess in acidic medium. N-alkylamide group.

Sulphated dyes are advantageously chrome-plated in comparison with the German patent specification aqueous solution or suspension and unsulphated 50 963 898, Table Example 11, known chromium-comine higher-boiling alcohols or in the melt of plex compounds, obtained by mixed metallization, amides of low molecular weight fatty acids. Azobenbei l'-temperature process is carried out of the disazo dye 3-Ammo-4-hydroxy-l, from 90 to 150 ⁰ C and, if necessary zol-3'-sulfonic acid amide - »- 2-hydroxynaphthalene with pressurized. Particularly uniform 1: 1 chromium demonazo-2-amino-1-hydroxy-4-nitrobene complex compounds are obtained above all with 55 zol - »- 1-acetylamino-7-hydroxynaphthalene, shows the sulfated monoazo dyes. chromium complex compound according to the method obtained

The addition of the metal-free azo dyes by mixed metallization of the disazo dye

the 1: 1 chromium complex compounds occur in 2-amino-4- (4'-benzolazobenzoylamino) -l-hydroxy-

weakly acidic, neutral or alkaline agent benzene -> 2-hydroxynaphthalene with the monoazo-

at a slightly elevated temperature, for example 40 to 60 dye 2-amino-1-hydroxy-4-nitrobenzene-v 7-Hy-

95 ⁰ C. It is expedient to work in aqueous or droxynaphthalene-1-sulfonic acid amide, a better leveling

aqueous-alcoholic agent and with advantage in pouring power.

Presence of mineral acid dulling or details are from the following examples alkaline agents such as sodium acetate, sodium. In these examples, unless they mean nothing carbonate, sodium hydroxide or the corresponding 65 other expressly stated, the parts by weight potassium or ammonium compounds. The proportions. These relate to parts by volume like grams In most cases, storage occurs quickly and in cubic centimeters. The temperatures are in constantly on. The degrees Celsius can be specified from aqueous solutions.

HO.

/ -N = N

Cr

^ N = N

so.

Cl

CH, -

■ y

N = N-

HO, S -

/ X

example 1

10 parts by volume of 2 η sodium hydroxide solution and 5.72 parts of the disazo dye are added to 150 parts of water, obtained by domes of diazotized! 4-chloro-2-amino-1-hydroxybenzene with 1-hydroxynaphthalene-3-sulfonic acid-N-methyl-4'-benzolazophenylamide, added. The chromium complex compound of type 1 chromium to 1 dye is added to this mixture, which is 0.52 parts of chromium and 3.94 parts of the monoazo dye from l-diazo-2-hydroxynaphthalene-4-sulfonic acid and 2-hydroxynaphthalene. Man the mixture is heated to 90 to 95 ° until the starting compounds have disappeared. The one containing chromium Addition dye is precipitated by adding sodium chloride. It is filtered off and dries him. After drying it is a dark powder, the wool made from neutral or weakly acidic Bath colors in wet, reddish-tinged navy blue tones.

4 parts of this chromium-containing dye are dissolved in 4,000 parts of water and, at 40 ° to 50 °, with 100 parts of pre-wetted wool, they enter the dyebath. It is heated to boiling within about half an hour, maintained for _^3/4 hour boiling the wool rinsed with cold water and dried. The navy blue dyeing obtained shows good wet fastness properties.

A dye with similar properties is obtained if, instead of the disazo, one obtains from diazotized 4-chloro-2-amino-1-hydroxybenzene and 1-hydroxynaphthalene-S-sulfonic acid-N-methyl ^ '- benzene-azo-phenylamide 6.06 parts of the disazo dye from 4-chloro-2-amino-1-hydroxybenzene and 1-hydroxynaphthalene - 3 - sulfonic acid -N- methyl - 4 '- (4 "- chlorobenzolazo) -phenylamide used.

Example 2

L N = N

,O

Cr

O'

SO ₂ -

Cl

5.59 parts of the disazo dye are added to 150 parts of Waeeer from diazotized 4-chloro-2-amino-1-hydroxybenzene and l-hydroxynaphthalene-3-sulfonic acid 4'-benzene-azophenyl ester, also 4.44 parts of the chromium complex compound of the type 1 chromium to 1 dye, which contains 0.52 parts of chromium and 3.94 parts Monoazo dye made from l-diazo-2-hydroxynaphthalene-4-sulfonic acid and corresponds to 2-hydroxynaphthalene, and add 1.8 parts of sodium carbonate. One heats up the mixture to 60 to 65 ° until the starting compounds have disappeared. The resulting Chromium complex compound is precipitated by adding sodium chloride, filtered off and dried. After drying, it is a dark powder that wool from neutral or weakly acidic baths contains shades of reddish navy blue. The wool dye is characterized by good wet fastness properties.

Example 3

HO ₃ SI

10 parts by volume of 2η sodium hydroxide solution and 5.37 parts of the disazo dye are added to 150 parts of water from diazotized! 2-Amino-1-hydroxybenzene-5-sulfonic acid-N-methyl-4'-benzene-azo-phenylamide and 2-hydroxynaphthalene. The chromium complex compound of type 1 chromium is also added to 1 dye to which 0.52 parts of chromium and 3.94 parts of the dye from l-diazo ^ -hydroxynaphthalene ^ -sulfone-

35 acid and 2-hydroxynaphthalene. The mixture is heated to 90 to 95 ° and kept at this temperature until the starting compounds have disappeared. The chromium-containing dye is precipitated by adding sodium chloride; it is filtered off and dried. After drying, it is a dark powder that dyes wool from neutral or weakly acidic baths in a real gray-blue.

Example 4 SO ₃ H

Cl

NO

I— N = N - {

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5.7 parts of the disazo dye from diazotized 5-nitro-2-amino-1-hydroxybenzene are suspended in 150 parts of water and l-hydroxynaphthalene-3-sulfonic acid-4'-benzolazophenyl ester, also 4.28 parts of the chromium complex compound of the type 1 chromium to 1 dye, which is 0.52 parts of chromium and 3.79 parts Monoazo dye from ^ CMor ^ -amino-1-hydroxybenzene and corresponds to 2-hydroxynaphthalene-6-sulfonic acid, and 1.8 parts of sodium carbonate. One heats up the mixture to 60 to 65 ° and holds it at this temperature until the starting compounds have disappeared are. The chromium-containing dye is precipitated by adding sodium chloride; one filtered it off and dries it. After drying it is a dark powder, the wool of neutral or weak acid bath colors in blue tones. The dyeings show good fastness properties.

Example 5

HOoS

- CO -NH

1-N = N

Cl

To 200 parts of aqueous 50% ethanol are added 2 parts of crystallized sodium acetate and 5.22 parts of the disazo dye from diazotized 4-chloro-2-amino-1-hydroxybenzene and 2-hydroxynaphthalene - 3 - carboxylic acid - 4 '- benzene azo phenylamide. Furthermore, one adds the chromium complex compound from Type 1 chromium to 1 dye made up of 0.52 parts of chromium and 3.94 parts of the monoazo dye

1 - diazo - 2 - hydroxynaphthalene - 4 - sulfonic acid and Corresponds to 2-hydroxynaphthalene. The mixture is heated to 70 to 75 ° until the starting compounds Have disappeared. The alcohol is then distilled off and the reaction mixture is evaporated to dryness. The dye is a dark one Powder. It dyes wool from neutral or weakly acidic baths really gray.

Example 6

Cl

Cl

, -N = N

SO, H

1.8 parts of sodium carbonate and 6.39 parts of the disazo dye are added to 150 parts of water diazotized! 4-chloro-2-amino-1-hydroxybenzene and 1 - hydroxynaphthalene - 3 - sulfonic acid - 4 '- (4 "- sulfobenzolazo) phenyl ester. Then the chromium complex compound of type 1 chromium is added to 1 dye, which is 0.52 parts of chromium and 3.99 parts of the monoazo dye from 4-chloro-2-amino-1-hydroxybenzene and 2-hydroxynaphthalene. Man The mixture is heated to 60 to 65 ° and is kept at this temperature until the starting compounds have disappeared are. The chromium-containing dye is precipitated by adding sodium chloride and how usually isolated. After drying it is a dark powder, the wool in violet-blue tones is good Dyes fastness properties.

Example 7

NO,

25th

Example 8

HO

O ₃ N

CH

N = N

Cl

5.83 parts of the disazo dye are added to 150 parts of water from diazotized 6-nitro-2-amino-4-methyl-1-hydroxybenzene and 1-hydroxynaphthalene-3-sulfonic acid-4'-benzolazophenyl ester, also 4.44 parts of the chromium complex compound of the type 1 chromium to 1 dye, which 0.52 parts chromium and 3.94 parts of monoazo dyes obtained from 1-diazo-2-hydroxynaphthalene-4-sulfonic acid and corresponds to 2-hydroxynaphthalene, and 1.8 parts of sodium carbonate. This mixture is heated to 60 to 65 ° until the starting compounds Have disappeared. The resulting chromium complex compound is by adding

N = N

In 150 parts of water are added 10 parts by volume 2-η sodium hydroxide solution and 5.72 parts of the disazo dyes of diazotized 4-chloro-2-amino-l-hydroxybenzene and 2 - hydroxynaphthalene - 6 - sulfonic acid - N - methyl-4'-benzolazophenylamid. The chromium complex compound of type 1 chromium is then added to 1 dye, which contains 0.52 parts of chromium and 4.09 parts of the monoazo dye from 4-nitro-2-amino-1-hydroxybenzene-6-sulfonic acid and 4-amyl -1 - corresponds to hydroxybenzene. The mixture is heated to 90 to 95 ° and kept at this temperature until the starting compounds have disappeared. The chromium-containing addition dye is precipitated by adding sodium chloride. It is filtered off and dried. After drying, it is a dark powder that dyes wool from neutral or weakly acidic baths really brown.

Sodium chloride precipitated, filtered off and dried. When dry it is a dark powder that Wool from neutral or slightly acidic baths in wet-fast blue tones with good lightfastness colors.

4 parts of this chromium-containing dye are dissolved in 4,000 parts of water and, at 40 ° to 50 °, with 100 parts of well-moistened wool, they are added to the dyebath. One adds thereto 2 parts of 40% strength acetic acid ^e added, it is heated to boiling within a half hour and maintained for _^3/4 hour at boiling temperature. The wool is then rinsed with cold water and dried. The navy blue wool dye has good fastness properties.

A wool dyeing with good properties is also obtained if you use a Glauber's salt containing liquor colors.

Example 9

CO - CH,

O ₅ N-,

6.05 parts of the sodium salt of the disazo dye from diazotized δ-nitro ^ -methyl ^ -amino-1-hydroxybenzene and 1 - hydroxynaphthalene - 3 - sulfonic acid 4'-benzolazophenyl ester, also 5.27 parts of the sodium salt of the monoazo dye from diazotized 3,4,6-trichloro - 2 - amino -1 - hydroxybenzene and 1 - hydroxy-8-acetylaminonaphthalene-5-sulfonic acid are dissolved in 200 parts of ethylene glycol and the solution after the addition of 40 parts of a solution of chromsalicylic acid Sodium (corresponding to 0.84 parts of chromium oxide) for so long at a temperature of 100 to 105 ° held until the metal complex formation has ended. The chromium-containing dye is by adding Sodium chloride solution precipitated, filtered off and dried. It's a dark powder made from wool weakly acidic bath stains in navy blue tones.

example

SO.CB

N = N-Y V-CO-NH-1

N = N

2 parts of crystallized sodium acetate and 5.15 parts of the disazo dye are added to 150 parts of ethanol from diazotized 2-aminobenzene-1-carboxylic acid and 2-hydroxynaphthalene-3-carboxylic acid-4'-benzene-azo-phenylamide. The chromium complex compound of type 1 chromium is also added to 1 dye, which contains 0.52 parts of chromium and 4.07 parts of the monoazo dye from 2-amino-1-hydroxybenzene-4-methyl-

sulfone and l- (3'-chloro) -phenyl-3-methyl-5-pyrazolone. The mixture is heated to 70 to 75 ° in this way long until the original connections have disappeared. The alcohol is then distilled off and the reaction mixture evaporates to dryness. The dye is a powder that is made of neutral wool or weakly acidic bath colors in real brown-orange tones.

Example 11

NO

C _K H.

HO ₃ S

N = N-A-N-CO

To 200 parts of aqueous 50% ethanol are added until the starting compounds have disappeared, 2 parts of crystallized sodium acetate and 5.24 parts are added. The alcohol is then distilled off and the disazo dye from diazotized 4-nitro-2-amino- the reaction mixture is evaporated to dryness. The 1-hydroxybenzene and 4-methyl-2- (4'-benzolazobenzoyl-N-ethylamino-1-hydroxybenzene
the chromium complex compound of type 1 to chromium
1 dye to which 0.52 parts of chromium and 4.09 parts of 45
of the monoazo dyes from 4-nitro-2-amino-l-hydroxy-

benzene-6-sulfonic acid and 4-amyl-1-hydroxybenzene is equivalent to. The mixture is heated to 70 to 75 °

Dye is a dark powder. It really dyes wool from neutral or weakly acidic baths Brown.

The following table contains further dyes according to the invention, which one when using the obtained in the present examples described procedures.

Tabel

No. Monoazo dyes the same Disazo dyes Coloring on wool 1 l-diazo ^ -hydroxynaphthalene ^ -sulfone- 5-nitro-2-amino-1-hydroxybenzene Gray-blue acid - »· 2-hydroxynaphthalene - * - l-hydroxynaphthalene-3-sulfone- (3.94 parts) acid 4'-benzene azo phenyl ester the same (5.7 parts) 2 4-chloro-2-amino-1-hydroxybenzene Navy blue - + ■ l-hydroxynaphthalene-3-sulfone- acid-4'-naphthalene- (1 ") -azophenyl- ester (6.09 parts) 3 4-chloro-2-amino-1-hydroxybenzene Navy blue '-> l-hydroxynaphthalene-3-sulfone- acid-4'-naphthalene- (2 ") - azo- phenyl ester (6.09 parts)

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5> ₄ "f If

19th 20th Disazo dye ■■ - - No. Monoazo dye Coloring on wool S-Nitro ^ aminOrl-hiydroxybenzoi.
-> - iTHydroxynaphtiiälin-SrSulfon-
acid-.4 '-: naphthalia .- (l. ") - azo-
phenyl ester (6.19 parts) 4th l-DiazQ ^ -hydroxynaphthalene ^ sulfone-
acid— > ■ 2-hydroxynaphthalene
(3.94 parts) S-nitro-1-amino-1-hydroxybenzene
-> ■ i-hydroxynaphthalene-3-sulfone-
acid-4'-naphthalene- (2 ") -azophenyl-
ester (6.19 parts) Gray-blue 5 the same 4-chloro-2-amino-1-hydroxybenzene
- * - l-HydroxynaphthaUn-3-suhOn-
acid-4 '- (4 "-chlorbenzolazo) -phenyl-
ester (5.93 parts) Gray-blue 6th the same 4-chloro-2-amino-1-hydroxy, benzoi.
- * - l-Hydroxynaphthaün ^ S-suhOn-
acid-4 - '(4 "-methoxybenzolazo) -
phenyl ester (5.89 parts) Navy blue 7th the same 4-chloro-2-amino-1-hydroxybenzene
-> - l-hydroxynaphthalene-3-sutfon-
acid-4 '- (2 "-methylbenzolazo) -
phenyl ester (5.73 parts) Navy blue 8th the same 4-chloro-2-amino-i-hydroxybenzene
- »- l-hydroxynaphthalene-S-sulfone-
acid-4 '- (2 ", 6" -dimethylbenzolazo) -
phenyl ester (5.87 parts) Navy blue 9 the same 5-nitro-2-amino-1-hydroxybenzene
-> - 2-IIydroxynaρhthalin-3-carbon-
acid 4'-benzene azo phenylamide
(5.32 parts) Navy blue 10 the same 6-nitro-4-methyl-2-amino-1-hydroxy-
benzene _; t> - 2-HydrpxynapHthaIin-
3-carboric acid-4'-benzolazόpίleήyi-
amide (5.46 parts) Gray 11 the same 4-Chlorr2-ammo-lτh.y.dr, oxybenzene, - -
-> - 2-Hydroxynaphthalene-: 3-carbQn-.
acid-H-metnyl ^ '- benzolazophenyl-
amide (5.36 parts) Gray 12th the same - »- 7-Hydroky-l- (4'-benzölaz6-
benzoylamino) naphthalene
(5.22 TeUe) Gray 13th Äesgl the same Gray 14th 4-chloro-2-amίno-l-hydroxybenzene-
6-sulfonic acid - * - 1-acetylamino-
7-hydroxynaphthalene (4.36 parts) S-Nitro ^ -amno-l-hydrQxyljenzql.,.
- * - l-hydroxynaphthiialine-3-sulfone-
acid-N-methyl-4'-b'enzoiazo-
phenylamide (5.82 TeU) Greenish gray 15th l-diazo ^ -hydroxynaphthalene - ^ - sulfone-
acid -> - 2-Hyäroxyhäphthälin
(3.94 parts) 4-chloro-2-amino-1-hydroxybenzene
r> - i-hydroxynaphthalene-3-sühOn-
acid 4'-benzene azo phenyl ester
(5.59 TeUe) Gray-blue 16 o-nitro-l-diazo ^ -hydroxynaphthalene-
4-sulfonic acid - * - 2-hydroxy-
naphthalene (4.39 parts) 4-Nitro12-amino-1-hydroxybenzene
r * - 2-hydroxynaph.thalene-6-sulfone-
acid 4'-benzene azo phenyl ester
(5.7 parts) Violet-tinged
gray 17th 4-nitro-2-amino-1-hydroxybenzene
6-sulfonic acid -rhi 4-Ai $ yi -, -.
I-hydroxybenzene (4.09 file) Brown

21 the same 22nd Disazo dye Coloring on wool No. Monoazo dyes 4-chloro-2-amino: 1-hydroxybenzene ... Brown 18th 4-nitrq-2-amino-1-hydroxybenzene- -y 2-Hydroxynaphthalinr6-_siilfon- 6-sulfonic acid * i4-amyl- ... acid 4'-benzene azo phenyl ester 1-hydroxybenzene (4.09 parts) the same (5.59 TeUe) 4-chloro-2-amino-1-hydroxybenzene Brown 19th the same -v 2r-hydroxynaphthalene-6-sulfone- acid-N-ethyl-4'-benzolazophenyl- o-methyl - ^ - amino-1 -hydroxybenzene- amide (5.86 parts) 4-sulfonic acid - * 2-hydroxy 4-chloro-2-amino-1-hydroxybenzene Blue-gray 20th 6-Nitro-4-arn.ylTl.-liydrDxybenzol _i .. - naphthalene (3.58 parts) -> - 2-hydroxynaphthalene-3-carbon- - * - 2-.Hydrox-yaaphthalene-4-sulfone- acid 4'-benzene azo phenylamide acid (4.59 parts) 3,4, GrTnChIOr ^ aHUnP.-; 1-hydroxy (5.22 teüe) benzene -> - .lrHydroxy-rS-acetyl- 4-Chloro-2-amiiiQrl-Hydroxybenzol.,. Blue-gray 21 the same aminonaphthalene-5-sulfonic acid - »- 2-hydroxynaphthalene-: 3-carbon- (5.05 parts) acid-4'-naphthalene- (l .'-) - azo- l-diazo-2-hydroxyxiaphthalene-r4-sulfone- phenylamide (5.72 parts) acid - * - 2-hydroxynaphthalene 4-chloro-2-amino-1-hydroxybenzoL. Reddish. 22nd l-: Biaz9-2-hydBQxynaphthalene-4-sulfone- (3.94 parts) .-> ■ 2-hydroxynaphthalene-6isulfone- navy blue acid - »- 2-hydroxynaphthalene acid-N-methyW-benzolazo- (3.94 parts) phenylamide (5.72 TeU) S-nitro ^ -amino-1-hydroxyhenzoL ,. ί
black 23 4-chloro-2-amino 1 -hydroxybenzene - * - l-hydroxynaphthalene-8-sulfone- -v 2-hydroxynaphthalene acid.-3-sulfonic acid. N-methyl.,; .. ■ _ (3.99 TeU) 4'-benzolazophenylamide (6.62 parts) 4-chloro-2-amino-1-hydroxybenzene Blue violet 24 2-amino-1-hydroxybenzene-4-sulf one- -> - l-hydroxynaphthalene-3-sulfone- acid - * - 5,8-dichloro-l-hydroxy- acid 4'-benzene azo phenyl ester naphthalene (4.13 parts) (5.59 pieces) 4-chloro-2-amino-1-hydroxybenzene. Blue violet 25th the same - + ■ l-hydroxynaphthalene-3-sulfone- acid-4 '- (2' '-ethoxybenzolazo) - phenyl ester (6.03 tea) 6-chloro-4-nitrQ ^ 2rapiino-l-Jay (iroxy- Gray 26th l-diazo ^ -hydroxynaphthalene ^ -sulfone- benzene - * - 1-hydroxynaphthalene-. acid - + ■ 2-hydroxynaphthalene 3-sulfonic acid-4! ^ Benzene-azophenyl- (3.94TeUe) ester (6.04 parts) 4-chloro-2-amin.o- ^ rhydroxybenzene .. Navy blue 27 -> - l-HydroxynaphthaHn-ä-sulfoflfc- acid-N-ethyl-: 4'-benzolazophenyl- amide (5.86 parts) 2-AmiiijO- l-hydroxybenzold-phenyl- Red-stiched gray 28 sulfop -> - l-HydEoxynaphihalinT .. 3-sulfonic acid-4'-benzene-azophenyl- ester (6.64 teüe) 4-chloro-2-amino-1-hydroxybenzene Reddish 29 -> - l-hydroxynaphthalene-3-sulfone- navy blue acid 4'-benzene azo phenyl ester (5.59 pieces) 2-amino-1-hydroxybenzoWrphenyl- Reddish 30th sulfone -> - 1-hydroxynaprithalin- violet 3-sulfonic acid-4'-benzölazophenyl- ester (6.64 parts) 2-aminobenzene-1-carboxylic acid, Reddish 31 -> - 2-hydroxynaphthalene-3-carbon- black acid 4'-benzene azo phenylamide (5.15 parts)

23 24 Disazo color Coloring on wool " No. Monoazo dye 2-aminobenzene-1-carboxylic acid
- -> - 2-hydroxynaphthalene-3-carbon-
acid 4'-benzene azo phenylamide
(5.15 parts) Bordo red 32 I-diazo ^ -hydroxynaphthalene ^ -sulfone-
acid -ν l-phenyl-3-methyl-
5-pyrazolone (4.24 parts) 4-chloro-2-amino-1-hydroxybenzene
- * - 2-HydroxynaphthaHn-3-carbon-
acid 4'-benzene azo phenylamide
(5.22 parts) dull purple 33- the same 2-amino-1-hydroxybenzene-4-phenyl-
sulfone -> - 1 -hydroxynaphthalene-
S-sulfonic acid ^ '- benzolazophenyl-
. ester (6.64 parts) Bluish bordo 34 the same the same Red-brown 35 2-amino-1-hydroxybenzene-4-phenyl-
sulfone-3'-sulfonic acid
-> l- (3'-chloro) -phenyl-3-methyl-
5-pyrazolone (5.49 parts) 6-nitro-4-methyl-2-amilιo- 1-hydroxy-
benzoil -> - 1-hydroxynaphthalene- ^
3-sulfonic acid-4'-benzene-azophenyl-
phenyl ester (5.83 parts) Yellowish olive 36 2-aminobenzene-1-carboxylic acid
-> - l- (4'-sulfonic acid) -phenyl-
3-methyl-5-pyrazolone (4.02 parts) 4-nitro-2-amino-1-hydroxybenzene
-> - 4-methyl-2- (4'-benzolazo-
benzoylamino) -l-hydroxybenzene
(4.96 TeUe) Brown 37 ^ Nitro-2-amino-l-hydroxybenzene
6-sulfonic acid - »- 4-amyl-l-
hydroxybenzene (4.09 parts) 4-nitro-6-chloro-2-amino-1-hydroxy-
benzene + ■ 4-methyl-2- (4'-benzene-
azobenzoylamino) -l-hydroxybenzene
(5.31 TeUe) Brown 38 the same 2-amino-l-hydroxybenzene-5-snlfon-
acid-N-ethyl-4'-benzolazophenyl-
amide -> - 2-hydroxynaphthalene
(5.51 TeUe) Gray-blue 39 l-diazo ^ -hydroxynaphthalene ^ -sulfone-
acid - * - 2-hydroxynaphthalene
(3.94 parts) o-nitro ^ -methyl ^ -amino-1-hydroxy-
benzene -y 1-hydroxynaphthalene-
S-sulfonic acid ^ '- benzolazophenyl-
ester (5.83 parts) Red-brown 40 2-amino-1-hydroxybenzene-4 ~ phenyl-
sulfone-3'-sulfonic acid
-> - l- (3'-chloro) -phenyl-3-methyl-
5-pyrazolone (5.49 parts) 2-amino-1-hydroxybenzene-5-sulfone
acid-N-methyl ^ '- benzolazophenyl-
amide -> ■ l-phenyl-S-methyl-S-pyr-
azolone (5.67 TeU) Reddish orange 41 2-amino-1-hydroxybenzene-4-sulfone
acid -> - l- (3'-chloro) -phenyl-
3-methyl-5-pyrazolone (4.09 parts) 4-chloro-2-amino-1-hydroxybenzene
-v 2-hydroxynaphthalene-6-suKon-
acid 4'-benzene azo phenyl ester
(5.59 TeUe) Reddish blue 42 l-diazo ^ -hydroxynaphthalene ^ -sulfone-
acid -> - 2-hydroxynaphthalene
(3.94 parts) 4-chloro-2-amino-1-hydroxybenzene
-v 2-hydroxynaphthalene-6-sulfone-
acid-N-methyl-4 '- (2 "-methoxy) -
benzolazophenylamide (6.02 parts) Reddish blue 43 the same 4-chloro-2-amino-1-hydroxybenzene
-> - 2-hydroxynaphthaün-6-sulfone-
acid-N-ethyW-benzolazophenyl-
amide (6.16 TeUe) Reddish blue 44 the same 6-nitro-4-methyl-2-amino-1-hydroxy-
benzene - * - 2-hydroxynaphthalene-
o-sulfonic acid-i'-benzene-azophenyl-
ester (6.05 TeU) blue 45 the same

No. Monoazo dye Disazo dye Coloring on wool 46 2-amino-1-hydroxybenzene-4-methyl-
sulfone - »■ l-phenyl-3-methyl-
5-pyrazolone (3.72 parts) 2-amino-1-hydroxybenzene-4-phenyl-
sulfone - * - 1-hydroxynaphthalene-
S-sulfonic acid ^ '- benzolazophenyl-
ester (6.64 parts) Red-brown 47 2-amino-1-hydroxybenzene-4-sulfone
acid amide -> - l-phenyl-3-methyl-
5-pyrazolone (3.73 parts) the same Red-brown 48 2-amino-1-hydroxybenzene-4-methyl-
sulfone -> - 2-hydroxynaphthalene
(3.42 parts) 2-aminobenzene-1-carboxylic acid
5-sulfonic acid amide -> - 2-hydroxy-
naphthalene-3-carboxylic acid-4'-benzene-
azophenylamide (5.94 parts) Brown purple

Claims (7)

PATENT CLAIMS: 1. A process for the preparation of chromium-containing azo dyes, characterized in that there is a metallizable monoazo dye of the general formula A ₁ - N = N - B ₁ (I) and a metallizable disazo dye of the general formula (A ₂ -N = NB ₂ ) -X- (Y = N-Z) (Π) wherein A ₁ and A _{2 are} the residues of diazo components of the benzene and naphthalene series which contain a metallizable group in the o-position to the azo bond, B ₁ and B _{2 are} the residues of azo components coupled to a hydroxyl group, X is a divalent bridge member from the Series of carbonylamino, sulfonylamino and sulfonyloxy groups and Y - N = N - Z denote the radical of a non-metallizable monoazo compound, with one another or successively with a chromating agent under such conditions that one molecule of the monoazo dye through one atom of chromium with one molecule of the disazo dye. 2. The method according to claim 1, characterized in that the azo dyes are chosen so that at least one of the two contains a sulfonyl substituent which increases the solubility in water. 3. The method according to claim 1 and 2, characterized by the use of o, o'-dihydroxyazo compounds. 4. The method according to claim 1 to 3, characterized in that one first of the monoazo dye of the general formula produces a chromium complex compound which acts on a molecule of the dye contains an atom of chromium and attaches the metal-free disazo dye to it. 5. The method according to claim 1 to 4, characterized in that the monoazo dye is a Contains sulfonic acid group. 6. The method according to claim 1 to 5, characterized in that the remainder (A ₂ -N = N - B ₂ ) -X - is an ο - hydroxybenzolazo - o '- hydroxynaphthalenecarbonyl or sulfonyl radical. 7. The method according to claim 1 to 6, characterized in that the remainder (Y - N = N - Z) is an azobenzene or benzolazonaphthalene radical. Considered publications:
German patent specification No. 963 898. A coloring table with explanations has been laid out at the time of the announcement. © 109 708/351 10.