DE2417943A1 - TETRAKIS AZO COMPOUNDS, THE PROCESS FOR THEIR PRODUCTION AND THEIR USE FOR COLORING LEATHER - Google Patents

Description

Dr. E. IV-ettm-T
IMpL-In ₁₅ . H.-IM «i:« r 2 Λ 1

Dr. IU. IU-rt: niH * · * τ «

DB Munich 80 Αττρχΐ 1974

Dr. Be / ib

WILLIAMS (HOHtTSLOW) LIMITED, Greville House, Hibernia Road, Hounslow, Middlesex, England

Letrakis azo compounds, process for their preparation and their "use for the I-dyeing of leather.

The invention relates to tetrakis azo compounds which can be used as dyes for dyeing and printing leather. The invention also relates to Process for the production of these compounds and the dyeing and printing of leather with such compounds.

Tetrakis azo compounds used for dyeing leather are known per se, but most of these compounds contain the benzidine nucleus (e.g. the black dyes Color Index Nos. 73, 85 and 94). Some of these compounds contain the core of 1-amino-8-hydroxy-; 5,6- or -4,6-naphthalene disulfonic acid.

The preparation of these compounds, which contain the benzidine nucleus, requires the use of benzidine. It has recently been found, however, that benzidine is a carcinogenic substance on health grounds Raises difficulties for manufacturers of compounds derived therefrom.

4098U / 0913

British patent specification 456 768 describes one Series of tetrakis and pentakis azo compounds, the Benzidine that is attached to an i-amino-8-hydroxy naphthalene-3,6- or -4,6-disulfonic acid is coupled, as well as a certain number of compounds in which the benzidine nucleus is represented by a single benzene nucleus is replaced, although in the examples given, all dyes that do not contain benzidine are pentakis azo compounds represent. In this patent specification represents the benzidine nucleus or the individual benzene nucleus that contains it replaced, a coupled resorcinol.

In particular, Example 7 of British Patent 456 768 describes the preparation of the dye:

OH

OH

■ ■ '-COr''"

SO ₅ H

OH

SO ^ H

IT =

UO,

409844/0913

Diazotized p-uritroaniline is used for its production with the liatrium salt of 1, O-Arainonaphtcl ^ jö-disulfonic acid coupled. Diazotized aniline-4-si.-lfonic acid is then to the monoazo dye obtained under alkaline conditions Conditions coupled. The ITitro group is then reduced to an amino group, diazotized and the obtained diazonium diazo compound coupled with resorcinol. The amino compounds 4-nitroaniline-2-sulfonic acid and p-nitroaniline are then in turn attached to the resorzine nucleus coupled to form the above pentakis azo dye. As this procedure explains, the Manufacture of the dye involves the use of resorcinol, which is a common characteristic for the manufacture of all compounds in British Patent 456,768.

The e _r-making creates a tetrakis-azo compound, the dye can be used of good quality when applied to leather as! And which can be produced without using Bensidin as an intermediate.

The dye has excellent properties with respect to the wash resistance and lightfastness and gives good permanent color tints on leather.

Possess the tetrakis azo compounds according to the invention the general formula:

409844/0913

X X

R,

IT =

H = H

in which A is a benzene or ITaphta linker, R _{1 is} a halogen atom, a methyl group or a sulfonic acid group, η has the value O, 1, 2 or 3 and, if η is greater than 1, each group R .. is the same, or can be different, X denotes an amino group on one ring and a hydroxyl group on the other ring, B is a uaphthalene nucleus which is substituted in positions 5.6 or 4.6 with respect to the amino group X by 2 sulfonic acid groups, C a benzene nucleus Rp is optionally present and a chlorine or bromine atom or an Ilethyl, methoxy or sulfonic acid group is te lit, D: a STaphthalene nucleus which is substituted by a sulfonic acid group, R ^ is optionally present and is a hydroxyl group , E is a benzene nucleus, R. is optionally present and a

- 5 -409844/0913

Amino or hydroxyl group means, R ₁ - a hydroxyl or amino group or a substituted amino group
and Rg is optionally present and denotes an ethyl group or a carbonyl or sulfonic acid group, these being shown in the Pail in which substituents on an ITaphthalene nucleus are represented
don't necessarily sit on the ring, see which one
the guideline leads.

Such compounds can according to the invention after a
A method can be prepared comprising the following known steps:

(a) Coupling of a diazo compound of one of the amines of
following formulas II or III

^ 2

C> ITH ₂ (II)

(RJn

jr-Λ

(III)

in which A, C, R ^, R ₂ and η have the meaning mentioned and T is a nitro or acylamino group, in an acidic medium, with 1-amino-8-naphthol-3 »6- or 4 5 6-disulfonic acid, whereby a monoazo compound is formed
will,

- 6 409844/0 913

(b) Coupling of the resulting lionoazo compound in the alkaline Medium with a diazo compound of the other of the amines mentioned to form a bisazo compound, wherein steps (a) and (b) are carried out in any order,

(c) converting the group Y of the bisaso compound into an amino group either by reduction, if Y is a nitro group, or by hydrolysis, if Y is acylamino group,

(d) diazotizing the amino group to form a diazotized bisazo compound,

this method being characterized in that it comprises the following further steps, namely

(e) Coupling of the diazotized bisazo compound with a FaphiiiyLarainsulfonäure of the formula

in the D and R ^ have the meaning mentioned below Formation of a trisazo compound,

(f) Diazotizing the amino group which is a substituent on the core D to form a diazotized irisazo compound and

40984-47,913

(g) Coupling of the obtained diazotized trisazoverbin dung with a hydroxyl- or amino-substituted benzene of the formula

R,

in which R, R ₁ - and Rg have the stated meaning with formation of the tetrakis-azo compound of the formula (I).

The coupling of said diazotized bisazo compound with aminonaphthalene sulfonic acid (IY) can be carried out in an alkaline, neutral or acidic medium, depending on the particular constitution of aminonaphthalene sulfonic acid (IV).

The pH value at which the coupling reaction of the diazotized irisazo compound with the hydroxyl- or amino-substituted benzene (Y) is preferably carried out depends on the nature of the substituents R ₀ , R ₁ , R 1 - and Rg and the position in the E nucleus on which coupling is to be carried out (if coupling is possible in more than one such position).

Preferred amines of the formula II which are used in the process are the m- and p-nitrotoluidines, 4-l-nitroaniline-2-sulfonic acid, 2-amino-3- and ^ 'nitrophenol, 2-methoxy-3- and 4- nitroaniline, and the m- and p-aminoacetanilides.

40984AV0913

Preferred amines of the formula III are aniline, toluidines, Xylidines, their chlorine derivatives, such as 2,5-dichloroaniline and their sulfonated derivatives such as sulfanilic acid, etanilic acid and LTaphthionic acid.

Preferred ITaphthylamin sulfonic acids of the formula IY are Cleves acids (i-ITaphthylamin-OE and 7-sulfonic acids), J acid (2-I7aplithylamin-5-liydrozy-7-sulfonic acid), and "fi ^ -acid -ITaphthylamin-e It is particularly preferred to use a mixture of the two Cleves acids.

Preferred hydroxyl- or amino-substituted benzenes of the formula V are resorcinol, m- and p-phenylenediamine, 2,5-diaminotoluene, 2,4-diaminotoluene, m-aminophenol, 2,4-dihydroxybenzene sulfonic acid, 2,4 ~ dihydroxybenzoic acid, Phenol and m-hydroxy-diphenylamine.

So far there have been many blue to black azo dyes used for dyeing leathers derived from benzidine, e.g. B. the black acidic dyes Color Index ITr. 73, 85 and 94. Benzidine, however, is a carcinogen and is therefore the manufacturer of it derived dyes face health problems. By using a method according to the invention the use of benzidine is avoided, but it is still possible to use a tetrakis azo compound for use as a dye to produce the dyeings on leather which are washable and lightfast are.

- 9 -409844/0913

Such dyes can be different Types of leather are used, e.g. B. Chrome wholegrain leather, Full chrome tanned suede and with vegetable Fabrics tanned! Leather. Particularly good results can be obtained with chrome leather, in particular full chrome-tanned split suede.

The invention thus also relates to the use of the tetrakis-azo compounds in general Formal I in a process for dyeing or printing leather, the leather, in particular chrome leather, is colored or printed with a letrakis azo compound of the general formula I. the Dyeing conditions can be those for dyeing leather, especially chrome leather with acidic Azo dyes are known per se and the dyeing is carried out in an aqueous medium, which can be neutral, but usually by means of an inorganic or organic acid, in particular Formic acid, which is made sauezj. The intrusion of the dye in the leather can be enhanced by removing the dye from its aqueous Solution is allowed to penetrate before staining / is carried out.

Methods within the invention are now further illustrated by the following examples. Here, parts are based on weight, unless otherwise stated, and the ratio of Parts by weight to parts by volume corresponds to the ratio of kilograms to liters.

- 10 4098U / 0913

- ίο -

example 1

It was a solution of 7 parts of liatrium nitrite in 30 parts by volume of cold! Kegs to a well-stirred one Suspension of 13.8 parts of p-ltitroaniline in a mixture of 200 parts by volume of ice water and 25 parts by volume of hydrochloric acid (32 ° Tv /). That The mixture was stirred until a clear solution of the diazonium chloride was obtained. To the Diazolösun ^ became a solution of 36.3 parts of disodium-1-amino-8-naphthol-3,6-disulfonic acid given in 200 parts by volume of cold water.

After coupling, a solution of the diazo compound, which had been prepared by dissolving 9.3 parts of aniline in a mixture of 25 parts by volume of hydrochloric acid (32 ° Tw) and 100 parts by volume of ice water and diazotizing with 7 parts of sodium nitrate, was added. The mixture was then stirred and sufficient alkali was added that the pH of the total mixture was 9.0 when all of the biazobenzene was coupled. To the, mixture, which contained the HITRO-bisazo compound obtained, 36 parts of hydrated ITatrium sulfide was added and the whole was heated to 15-50 C, preferably 30 - 50 ⁰ C and kept at this temperature for up to 2 hours to complete the reduction to complete the liitro group. Sufficient sodium chloride was added to form a 20 % strength brine and the entire mixture was acidified to a weakly acidic pH when virtually all of the amino-bisazo compound had precipitated. The compound is filtered off, washed with saturated brine,

40984 ^ / 0913

to replace the mother liquor, and as dry as possible pressed.

The amino-bisazo compound obtained was then slurried in 500 parts by volume of cold water and 25 parts by volume of hydrochloric acid (32 ° Tv /) were added. The compound was then diazotized with 7 parts of hatriian rite dissolved in 30 yolura parts of cold water. After complete diazotization, a solution of 22.3 parts of a mixture of 1,6- and 1,7-Cleves acids, which had been dissolved in 100 parts by volume of water with the addition of a sufficient amount of caustic soda solution, was added the solution was slightly alkaline to brilliant yellow paper. The mixture of the diazotized amino-bisazo compound and the alkaline solution of the Oleves acids, which had a pH of 3.5-4.0, was brought to pH 6.5 by adding caustic soda and then brought to a complete pH Clutch stirred. The temperature was adjusted to 20 ⁰ C and 20 Volumtei-Ie hydrochloric acid (32 ° Tv /) was added.

The diazotization was then by adding 7 parts of sodium nitrate in solution with stirring over half a causes up to 1 hour. 10.95 parts of resorcinol dissolved in 30 parts by volume of water were now converted into this trisazo compound added and by adding sodium carbonate solution coupled to a pH of 7.5. The batch was stirred for about half an hour. Of the obtained dye was salted out, filtered and dried. The product is a mixture of dyes the probable formulas of:

- 12 409844/0913

// ν

and

Έ =

SO ₃ H

F = F - / \.

So ₃ H

F = ff

SO ₃ H

The dye mixture obtained dyed Yollchrom split suede to a nozzle-soot-like black "shade with excellent] arbors from the dye liquor and had good lightfastness.

- 13 -

4098U / 0913

A full chrome buckskin leather was made with this dye colored as follows:

It was left for 1 kg of dried Wild split leather half an hour in a drum in a dye bath, 50 g of dye is dissolved in 250 1 of water at 70 ⁰ C which existed. Then 25 g of formic acid, which had been diluted with 300 l of water at 65 ° C., were added and the leather was left in the drum for a further 3/4 hour. Another solution containing 50 g of dye was added and the leather was drummed for a further hour.

According to an alternative and preferred embodiment, the leather is removed from the first dyeing drum and transferred to a second drum which contains a further solution of 50 g of dye in 600 1 of water at 65 ^° C. and is treated in the drum for half an hour. A further 40 g of formic acid are added and the leather is treated in the drum for a further hour. The leather is washed, dried, beaten and brushed, a good, firmly adhering black shade being obtained.

Example 2

16.2 parts of 2,5-dichloroaniline were dissolved in 20 parts of water and 20 parts by volume of hydrochloric acid (32 ⁰ parts) with heating and the mixture was cooled with 50 parts of ice with vigorous stirring. The suspension obtained was diazotized by adding 7 parts of sodium nitrate in aqueous solution. A solution of 36.3 was added to this diazonium salt solution

- 14 409844/0913

-U-

Share disodium 1-amino-8-napfrthol-3,6-disulfonai; added and the mixture was stirred until coupling was complete. There were 15 ropes p-aminoacetanilide in 150 parts by volume of water with 25 parts by volume of hydrochloric acid (32 ° Tw) and sodium nitrate at 0 ⁰ C by the addition of 7 parts, dissolved in 30 parts by volume of water diazotised. The resulting diazo solution was added to the monoazo compound solution obtained by the first coupling, and sufficient sodium hydroxide solution was added to bring the reaction mixture to pH 9.0.

Stirring was continued until coupling was complete. The acetylamino-bisazo compound formed is salted out of the solution and filtered off. The filter cake was slurried with a mixture of 140 parts by volume of water and 60 parts by volume of concentrated sulfuric acid. The slurry was heated to boiling and kept boiling for 2 hours until hydrolysis of the acetylamino group was complete. The mixture was then stirred while cooling ^{to 10 0 O from the outside.} The amino-bisaso compound obtained was salted out, filtered off, washed with saturated salt solution and pressed off. The amino-bisazo compound is then diazotized by adding 7 parts of sodium nitrate and treated with 22.3 parts of a mixture of 1,6- and 1,7-Cleves acids, dissolved in 100 parts by volume of water, and a sufficient amount of caustic soda solution so that the solution is opposite Brilliant yellow paper reacted weakly alkaline, coupled. The mixture of the diazotized amino-bisazo compound and the alkaline compound of Cleves acids, which had a pH of 3.5-4.0, was adjusted to pH 6.5 by adding caustic soda and until the coupling was complete touched. The temperature was set to 20 ° C. and 20 parts by volume of hydrochloric acid (32 ° Tw) were added.

409844/0913

- 15 -

The diazotization was effected by adding 7 parts of sodium nitrite in aqueous solution. That The reaction mixture was stirred for 1/2 hour to 1 hour until diazotization was complete. to the resulting trisazo-diazo compound was now 10.95 parts of resorcinol dissolved in 30 parts by volume Water, added and the coupling effected by adding sodium carbonate solution up to a pH value of 7.5. After stirring for about 1/2 hour, the dye obtained was salted out and filtered off and the filter cake dried. The product dyed chrome leather in a jet black-black shade.

Example 3

The procedure of Example 1 was carried out with the exception that 4 parts of phenol were used as coupling component S _{1 instead of resorcinol.} The product stained chrome leather to a green-black hue.

Example 4

The procedure of Example 1 was carried out with the exception that as the final coupling component m-phenylenediamine (10.8 parts) instead of resorcinol were used. The product dyed full chrome buckskin leather to a purple-black hue.

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409844/0913

Example 5

The procedure of Example 1 was carried out with the exception that the last coupling component a solution of 18.5 parts of m-hydroxydphenylamine, dissolved in 7 parts of aluminum hydroxide solution in 500 parts by volume ¥ ater were used. The product stained chrome leather to a bluish black hue.

Example 6

The procedure according to Example 1 was carried out with the exception that the last coupling component a solution of 10.9 parts of m-aminophenol was used and coupled in acidic medium. That Product colored full chrome buckskin leather to a purple-black color.

Example 7

The procedure of Example 6 was followed with the exception that the m-aminophenol was in alkaline Medium was coupled. The earbone on chrome leather was greenish-black.

- patent claims -

- 17 -

409844/0913

Claims (18)

Claims
1. Tetrakis-azo compounds of the general formula in which A is a benzene or naphthalene nucleus, R ^ is a halogen atom, a methyl group or a sulfonic acid group, η has the value 0, 1, 2 or 3 and, if η is greater than 1, each group R .. may be identical or different X is an amino group on one ring and a hydroxyl group on the other ring of B, B is a faphthalene nucleus which is substituted by 2 sulfonic acid groups in the 3,6- or 4-6 positions with respect to the amino group of X, G is a benzene nucleus represents, Rg is optionally present and represents a chlorine or bromine atom or a methyl, methoxy or sulfonic acid group, D is an ITaphthalene nucleus which is substituted by a sulfonic acid group, R. is optionally present and represents a hydroxyl group, E is a benzene nucleus, R is optionally present and represents an amino or hydroxyl group, R ₁ - denotes a hydroxyl or amino group or a substituted amino group and Rg is optionally present and a - 1 Methyl group or a carboxyl or sulfonic acid group represents, wherein substituents on an ITaphthalene nucleus are not necessarily on the Ring to which the guide line leads. 2. Tetrakis-aζoverbindungen according to claim 1, characterized characterized in that in the general formula I D is derived from a compound which has an amino substituent in the nucleus and is capable of attaching to a diazonium group be coupled au and then diazotized and to be coupled again. 3. A compound according to claim 2 of the formula X T in the R r r ^, χ, a, B, C, D and η have the meaning given in claim 1. 4. Dye from a mixture of compounds of the formulas OH ITH ₂ OH HO f \ - M and - 19 - 409844/0913 OH HO In = IT H = H SO ₃ H according to claim 5. Parstoff from a mixture of Yerbindungen the por- to melt OH ITH ₂ OH Eq IT = I SO ₃ H and ITH ₂ OH Cl SO ₃ H SO ₃ H after request 6. Parstoff from a mixture of compounds of the Pormula ITH ₂ OH 40 9 8 44 £ 0 9-1 3 and HO— / ~ \ _F = F ₉ OH SO ₃ H after. claim 7. Dye from a mixture of compounds of the formulas FH. H ₂ F - / ^ \ _ F =: FH ₂ OH and OH F = F O ₃ H according to claim 8. Dye from a mixture of compounds of the formulas FH ₀ OH .ν Γ> SO, H 3 - 21 -409844/0913 and OH OH H = 1 " lT = I SO'H S0, H SO ₅ H according to claim 9. Dye from a mixture of compounds of the formulas, OH HHo OH and oh ITH ₂ OH according to claim 10. Dye from a mixture of compounds of the formulas N = IT - 22 - 409844/0913 and X = J according to claim. 1. 11. A process for the preparation of a tetrakis-azo compound of the general formula 1 according to claim. 1, in which A, B, C, D, Ξ, R ₁ , R ₃ , R ₃ , R ₄ , R ₅ , Rg, T and η have the meaning given in claim 1 (a) Coupling of a diazo compound of one of the amines of formula II or III HH, (II) and (HI) in which A, C, B ^, R ₂ and η have the meaning mentioned and Y represent a nitro or acylamino group, in an acidic medium with i-amino-S-naphthol-3,6- or 4,6-disulfonic acid, (b) Coupling of the monoaso compound obtained in the alkaline Medium with a diazo compound of the other of the amines of the formulas II or III, the steps (a) and (b) can be performed in any order, 409844/0313 - 23 - (c) Conversion of the group Y in the bisazo bond obtained into an araino group either by reduction, if Y is a nitro group, or by hydrolysis, if Y is an acylamino group, (d) diazotizing the amino group to give a diazotized bisazo compound, characterized in that that the following steps are carried out: (e) the diazotized bisazo compound with an ITaphthylamine sulfonic acid the Eormel (IY) in the D and IL, which have the meaning mentioned, to one Irisazo connection is coupled, the amino group substituted on the core D is diazotized and (g) the obtained diazotized trisazo connection with a hydroxyl- or amino-substituted benzene of the formula ^R 4 (Y) in which R., R, - and Rg have the meaning mentioned, to the tetrakis azo compound of formula I is coupled - 24 4098U / 0913 12. The method according to claim 11, characterized in that the diazo compound des Amine of the formula II and the diazo compound of the amine of the formula III in the acidic or alkaline form Medium with 1-amino-8-naphthol-3,6- or 4,6-disulfonic acid gekuppelt'und carried out the coupling reactions in any desired order will. 13. The method according to claim 11, characterized in that the diazo compound des Amine of the formula II and the diazo compound of the amine of the formula III in the alkaline or acidic Medium with 1-Amina-8-naphthol-3,6- or 4,6-disulfonic acid are coupled, these coupling reactions in any desired order take place. 14. Process according to Claim 11, 12 or 13, characterized in that the 1-amino-8-naphthol-disulfonic acid an i-amino-8-naphthol-3,6-disulfonic acid represents. 15. The method according to any one of claims 11-14, characterized characterized in that the naphthylamine sulfonic acid a mixture of i-faphthylamine-6 and 1 represents naphthylamine-7-sulfonic acid. 16. The method according to any of claims 11-15, thereby characterized in that the amine of the formula II is p-nitroaniline or p-aminoacetanilide. 409844/0913 17. The method according to any one of claims 11-16 characterized ze ichnet that the amine of lormel III is aniline. 18. Use of a tetrakis azo compound of Formula I according to Claim 1 for dyeing or printing leather. . 403844/0913