WO1981000111A1

WO1981000111A1 - Mono-azo reactants for fibers,production process thereof and utilization thereof

Info

Publication number: WO1981000111A1
Application number: PCT/CH1980/000075
Authority: WO
Inventors: R Mislin; H Uehlinger; M Oppliger
Original assignee: Sandoz Ag
Priority date: 1979-06-26
Filing date: 1980-06-25
Publication date: 1981-01-22
Also published as: FR2459821A1; FR2459821B1; IT8049047A0; JPS568460A; GB2053261A; DE3022927A1; GB2053261B

Abstract

Mono-azo reactants for fibers, having the formula: (FORMULA) wherein the different meanings of the symbols R1 to R6, Hal, m and n are given in claim 1, with the conditions that: a) n can not be zero and must be zero when R2 is -NHCOOR10; b) the group -NHR5 and the azo group are in ortho position one with respect to the other and are in the positions 1 and 2 and respectively 2 and 1 of the naphtalen ring, and c) when n equals 1, m equals 1 and the azo group is in position 1 of the naphtalen ring, then either R6 in the position 8 of the ring is not a group OH or the sulphonic group is in a position other than position 4 of the ring, comprising at least two sulphonics groups per molecule, the mixture and the salts thereof. The compounds are obtained by coupling of the corresponding starting products and prior or subsequent condensation with the triazinic compound. They are used as dyes for the coloration or impression of substrates comprising nitrogen-containing groups or OH groups, such as for example natural or regenerated cellulose or natural or synthetic polyamides, particularly wool. Easily combinable, they are appropriate as elements for the trichromatic process, for example with coloring anthraquinonic acids.

Description

Fiber reactive monoazo compounds, process for their manufacture and use

The invention relates to fiber-reactive monoazo compounds which contain a (1-4C) alkoxytriazine residue, processes for their preparation and their use as dyes.

The compounds according to formula I

wherein

R ₁ (1-4C) alkyl, HaL halogen, So ₃ H; ; -So ₂ (1-4C) alkyl;

-SO ₂ NR ₈ R ₉ or -NHCOOR ₁₀ mean that the triazinylaimino group can be in position 4 or 5, but is in position 4 if R _{2 means} -NHCOOR ₁₀ ,

R _{3 is} hydrogen, (1-4C) alkyl or (1-4C) alkoxy,

R _{4 is} hydrogen or (1-4C) alkyl,

R _{5 is} hydrogen, (1-4C) alkyl; cyclohexyl which is unsubstituted or substituted by 1 to 3 (1-4C) alkyl groups; Phenyl or phenyl, hydrogen or hydroxy substituted by 1 or 2 substituents from the series halogen, (1-4C) alkyl and (1-4C) alkoxy, with the proviso that R- is not hydroxy if R _{2 is} -NHCOOR ₁₀ means hydrogen, (1-4C) alkyl or (1-4C) alkoxy, hydrogen, (1-4C) alkyl or (2-4C) hydroxyalkyl with the hydroxy group in position 2, 3 or 4, R _{9 is} hydrogen, (1-4C) alkyl, (2-4C) hydroxyalkyl with the hydroxy group in position 2, 3 or 4; Cyclohexyl, phenyl or phenyl substituted by 1 or 2 substituents from the series halogen, (1-4C) alkyl, (1-4C) alkoxy, sulfo and carboxy,

R ₁₀ (1-6C) alkyl, m 1 or 2, n 0 or 1 and p 0 or 1 mean with the proviso that a) n only stands for 0 and must be 0 if

R _{2 represents} -NHCOOR ₁₀ ; b) the group -NH R ₅ and the azo group are ortho to each other and are in 1- and 2- resp. are in the 2- and 1-position of the naphthalene ring; and c) when n is 1 and m is 1 and the azo group is in position 1 of the naphthalene ring, either

R _{6 has} a different meaning than hydroxy in position 8 or the sulfo group is different from position 4 of the

Naphthalene ring, and there are at least 2 sulfo groups per molecule, mixtures of compounds of formula I and their salts.

Halogen generally means fluorine, chlorine or bromine; bound to the triazine ring it preferably means fluorine or chlorine and in particular chlorine; as a phenyl substituent, it preferably means chlorine or bromine and in particular chlorine.

Alkyl groups can generally be straight-chain or branched.

R ₁ preferably represents (1-3C) alkyl and particularly preferably methyl.

R ₃ as alkyl preferably represents methyl or ethyl, in particular methyl; as alkoxy it is preferably methoxy or ethoxy, especially methoxy.

R ₃ preferably denotes R ^ as hydrogen, methyl, ethyl, methoxy or ethoxy; more preferably R "as hydrogen, methyl or methoxy and particularly preferably for hydrogen. R ₄ as alkyl preferably means methyl.

R ₄ preferably represents hydrogen or methyl and especially

Hydrogen.

R ₅ as alkyl is preferably methyl or ethyl; R ₅ as substituted cyclohexyl preferably represents cyclohexyl substituted by 1-3 methyl groups; as substituted phenyl it is preferably phenyl substituted by 1 or 2 substituents from the series chlorine, methyl, ethyl, methoxy and ethoxy, in particular phenyl substituted by chlorine, methyl or methoxy.

R ₅ preferably represents R ' ₅ as hydrogen, methyl, ethyl, cyclohexyl, phenyl; phenyl monosubstituted by chlorine, methyl or methoxy; more preferably for R " ₅ as hydrogen, methyl or phenyl; in particular for hydrogen.

R ₇ as alkyl or alkoxy preferably contains 1 or 2 carbon atoms and is preferably methyl or methoxy.

R ₇ preferably represents R ₇ 'as hydrogen, methyl or methoxy; more preferably for R " ₇ as hydrogen or methyl and especially for hydrogen.

R ₈ resp. R ₉ as alkyl preferably denotes methyl or ethyl; preferred as hydroxyalkyl (2 or 3C) hydroxyalkyl, especially 2-hydroxyethyl.

R ₉ as substituted phenyl preferably carries 1 or 2 substituents from the series chlorine, (1-2C) alkyl, (1-2C) alkoxy, sulfo and carboxy, in particular 1 or 2 substituents from the series methyl and sulfo.

R ₈ preferably represents R ₈ 'as hydrogen, methyl, ethyl or 2- or

3-hydroxy (2-3C) alkyl; more preferably for R " ₈ as methyl, ethyl or

2-hydroxyethyl.

R ₉ preferably represents R ' ₉ as methyl, ethyl, 2- or 3-hydroxy (2-3C) alkyl, cyclohexyl, phenyl or by 1 or 2 substituents from the

Chlorine, (1-2C) alkyl series, (1-2C) alkoxy, sulfo and carboxy substituted phenyl; further preferred for R " ₉ as methyl, ethyl, 2-hydroxyethyl, phenyl or phenyl substituted by 1 or 2 substituents from the series methyl and sulfo.

R ₁₀ preferably represents (1-4C) alkyl and particularly preferably methyl or ethyl. R ₂ as -SO ₂ (1-4C) alkyl preferably means -SO ₂ (1-2C) alkyl. '

R ₂ preferably denotes R _2a or R _2b , where R _{2a is} SO ₃ H,

-SO ₂ CH ₃ , -SO ₂ C ₂ H ₅ or

and R _{2b is} -NHCOO (1-4C) alkyl. R _2a is more preferably SO ₃ H,

-SO ₂ CH ₃ , -SO ₂ C ₂ H ₅ or - more preferred

for R ₂ " _a as SO ₃ H or and especially before

moves for SO ₃ H. R _2b more preferably stands for as -NHCOOC H ₃ or

-NHCOO C ₂ H ₅ .

The compounds of formula I preferably contain 2 sulfo groups. If R _{6 is} hydroxy, m is preferably 1.

The substituents in the naphthalene radical are preferably in the following positions, a) for n = 1:

- Group -NHR ₅ in position 1, R ₆ = H a sulfo group (m = 1) in position 4; two sulfo groups (m = 2) in positions 3.6; 3.8 or 4.6 and especially in positions 3.6 or 4.6;

- Group -NH R ₅ in position 2, R ₆ = H a sulfo group (m = 1) in position 5, 6 or 7; two sulfo groups (m = 2) in positions 3.6 or 5.7;

- Group -NH R ₅ in position 2, R ₆ = OH preferably in position 8 with m preferably for 1 and the sulfo group in position 6;

b) for n = 0 and m = 2:

- With the azo group in position 1, the two sulfo groups are in positions 3.6; 3.8; 4,6 or 4,8; - With the azo group in position 2, the two sulfo groups are in positions 3.6; 4.8; 5.7 or 6.8.

The group -NH R ₅ is preferably in position 2 of the naphthalene ring.

Preferred compounds of the formula I are those in which

(1) n is 1, R _{2 is} R _2a and shark is fluorine or chlorine and there are a total of 2 sulfo groups;

(2) those of (1), wherein R _{3 is} and R _{4 is} hydrogen or

Stand methyl;

(3) those of (1) or (2) wherein R _{5 is} R ₅ ';

(4) those corresponding to the formula Ia,

wherein m is 1 or 2 but is 1 when R _{6 is} hydroxy;

(5) those of (4), wherein is hydrogen;

(6) those of (4) or (5), in which and in particular for

SO ₃ H;

(7) those of (4), (5) or (6), in which R _{1 is} (1-3C) alkyl and in particular methyl.

(8) those corresponding to the formula Ib,

wherein Hal 'is fluorine or chlorine; (9) those of (8), wherein R _2b is;

(10) those of (8) or (9), wherein and R _{4 is} hydrogen, Hal '

represent chlorine and R _{1 represents} (1-3C) alkyl, especially methyl.

The compounds according to the invention are prepared by, for the preparation of compounds of the formula I in which n is 1, the diazonium compound of the amine of the formula II,

wherein R _{3 has the} above meaning, one of the meanings of R ₂ except the group -NHCOOR ₁₀

has and

X is in position 4 or 5 and means NO ₂ or -NR ₄ Z ₁ , where R _{4 is} as defined above and Z ₁ for one

Protecting group, the rest (a) or (b)

-

Hal is as defined above, or a mixture thereof with the compound of the formula III,

wherein R ₅ , R ₆ and m have the above meaning, or couples a mixture thereof, in the case that Z _{1 represents} the radical (a), with the compound R ₁ OH; in the event that X denotes a nitro group, then reduces it, or that Z _{1 stands} for a protective group, cleaves it off and then in each case with cyanuric halide and then with the compound R ₁ OH or with a condensation product of cyanuric halide and R ₁ OH of the formula ( c)

implements; or for the preparation of compounds of the formula I in which n is 0, the compound of the formula IV,

wherein R ₃ , R ₄ and R _{10 have the} above meaning, or a mixture thereof with cyanuric halide and then with the compound R ₁ OH or with a compound of formula (c).

The use of the condensation product of the formula (c) is preferred over the reaction with cyanuric halide and subsequent reaction with R ₁ OH in any case.

The compound of formula IV is obtained by using the diazonium compound of the amine of formula V

with a compound of formula VI

couples.

The individual condensation steps on the cyanuric halide are carried out according to methods known per se; the coupling reaction is also carried out in a manner known per se, expediently in an acidic medium at a preferred pH of 2.0-4.5.

After the reaction has ended, the compounds of the formula I obtained can be isolated from the reaction mixture in a manner known per se.

Depending on the reaction and isolation conditions, the compounds of the formula I are obtained in salt form, and any non-chromophoric cation which is customary in the field of reactive dyes can be present as the neutralizing cation; it is preferably an alkali metal ion such as lithium, sodium or potassium, of which sodium is particularly preferred.

The compounds of formula II, III, V and VI used as starting material are known or they can be prepared in a manner known per se or analogously to a manner known per se.

The compounds of the formula I according to the invention and mixtures thereof are reactive dyes; they are suitable for dyeing and printing organic substrates containing hydroxy groups and nitrogen. The preferred substrates are leather and textile materials which consist of or contain natural or regenerated cellulose, such as cotton, viscose or cellulose, and in particular natural and synthetic polyamides, such as wool, silk or nylon, of which particularly preferably wool.

The compounds of the formula I can be used for cellulose in dyeing liquors or in printing pastes by all dyeing and printing processes customary for reactive dyes. The exhaust dyeing process is used in particular for polyamides. The dyeings and prints obtained show good fastness to use, such as, in particular, very good fastness to wetness (washing, water, sweat, fulling) and light fastness.

Furthermore, the dyes of the formula I are particularly suitable as combination elements, in particular as easily combinable wool reactive dyes, with other dyes containing sulfo groups and carrying a comparable reactive system, such as, for example, anthraquinone reactive dyes, in the form of mixtures of two or three, with particular emphasis being given to the possibility of forming perfect trichromes is. The same dyeing and printing processes are used as for the individual dyes.

A preferred combination element is, for example, a dye of the formula

in which R _{1 is} (1-4C) alkyl, in particular in salt form, the cation mentioned above being suitable.

Compounds of formula VII can be prepared by using an amino compound of formula

or their salt with the compound of the formula

where R _{1 has the} above meaning.

A good combination of two preferably contains the dye of the formula as constituents

and the dye of the formula

or the dye of the formula

and the dye of the formula VIIa as a blue component in any mixing ratio depending on the desired shade. A very good trichrome preferably contains the individual components

Dye of the formula Ic (orange) Dye of the formula Id (red) and dye of the formula VIIa (blue) in any possible mixing ratio depending on the desired shade. A wide range of mixed colors (such as gray, brown, olive, beige) can be achieved.

The individual components of the combination of two and three are available in salt form.

These combination dyeings are characterized by a surprisingly good levelness, especially on wool, whose degree of chippiness is significantly lower than one would normally expect. In addition, these tone-on-tone dyeings show remarkable light fastness without catalytic fading and the general wet fastnesses are also good.

In the following examples, parts are parts by weight and percentages are percentages by weight; the temperatures are given in degrees Celsius.

example 1

23 parts of 4-acetylamino-2-aminobenzenesulfonic acid are dissolved in 80 parts of water with 33 parts of 20% sodium carbonate solution at pH 8 and 6.9 parts of sodium nitrite in 25 parts of water are added. This solution is added dropwise within 60 minutes at 0-5 ° to 25 parts of 30% hydrochloric acid. After a further 60 minutes, the pH is adjusted to 3 with 6.6 parts of sodium acetate. A solution of 22.3 parts of 2-aminonaphthalene-5-sulfonic acid in 100 parts of water and 10 parts of 30% sodium hydroxide solution is added dropwise to the resulting diazo solution at 0-5 ° within 45 minutes. During the coupling, the pH is kept at 2.8-3.2 by adding 12 parts of sodium acetate. After 2 hours, the pH is adjusted to 8.5 with 14 parts of 30% sodium hydroxide solution and the mixture is warmed briefly to 80 °. 33 parts of sodium chloride are added to the clear solution, then the mixture is filtered at 40 °. To split off the acetyl group, the paste obtained is stirred in 300 parts of water with 63 parts of 30% sodium hydroxide solution for 75 minutes at 90 °. Then it is adjusted to pH 9 with 53 parts of 30% hydrochloric acid, 36 parts of sodium chloride are added at 70 ° and the aminoazo dye is then filtered off at room temperature.

The paste of the dye is dissolved in 600 parts of water at pH 6.8 and 18 parts of 2,4-dichloro-6-methoxy-1,3,5-triazine are added at room temperature. The pH is kept at 6.7 by adding 13 parts of sodium bicarbonate. The mixture is stirred at 30-40 ° for 60 minutes, filtered and the reaction product is dried in vacuo. The dye according to the formula

is obtained in the form of the sodium salt; it dyes polyamides and especially wool in orange tones; the dyeings show excellent wet fastness and very good light fastness.

Example 2

23 parts of 4-acetylamino-2-aminobenzenesulfonic acid are diazotized as indicated in Example 1. The coupling is carried out by adding the diazo solution dropwise at 0-5 ° within 35 minutes to a suspension of 23.9 parts of 7-amino-1-hydroxynaphthalene-3-sulfonic acid in 140 parts of water, the pH being adjusted by adding 31 parts Sodium acetate kept at 3.3-3.5. 60 minutes after the addition of the diazo solution, the temperature is allowed to rise to 20 °, the mixture is then left to stir at room temperature for a further 60 minutes and filtered off.

To saponify the acetylamino group, the paste obtained is stirred in 120 parts of water, 80 parts of ethanol and 80 parts of 30% hydrochloric acid for 14 hours at 90 ° and then filtered at room temperature. The aminoazo dye paste is suspended in 1000 parts of water at pH 7, then 18 parts of 2,4-dichloro-6-methoxy-1,3,5-triazine are added within about 15 minutes. The pH is kept at 6.8 by adding 32 parts of sodium bicarbonate. The mixture is stirred at room temperature overnight, then filtered and the product is dried in vacuo. The dye according to the formula

is isolated as sodium salt, it dyes polyamides and especially wool in a red shade; the dyeings show excellent wet fastness and very good light fastness.

Example 3

23 parts of 5-acetylamino-2-aminobenzenesulfonic acid are dissolved in 200 parts of water by adding 42 parts of 20% sodium carbonate solution at pH 7, and 6.9 parts of sodium nitrite in 25 parts of water are added. This solution is added dropwise within 30 minutes at a temperature of 0-5 ° to a mixture of 80 parts of ice and 28 parts of 30% hydrochloric acid. After 15 minutes of stirring, the reaction is complete and the diazo compound is in the form of a white suspension.

34.3 parts of 2- (2 ', 6'-dimethylphenyl) amino-8-hydroxynaphthalene-6-sulfonic acid are dissolved in 180 parts of water by adding 8 parts of 30% sodium hydroxide solution at room temperature and by dropping 8.5 parts 30% hydrochloric acid precipitated again in finely divided form at pH 3.0. The above diazo suspension is added over the course of half an hour, the pH being kept between 2.0 and 3.0 by dropwise addition of 30% sodium hydroxide solution. The coupling begins at the moment and is complete at the end of the dropwise addition of the diazo suspension. To isolate the monoazo compound, the pH is adjusted to 7 by adding 30% sodium hydroxide solution and the mixture is filtered off. To saponify the acetylamino group, the paste obtained is stirred in 500 parts of water with 100 parts of 30% sodium hydroxide solution for 45 minutes at 95 °. The dissolved aminoazo compound is salted out by adding 140 parts of sodium chloride and filtered off at 60 °

The aminoazo compound paste is dissolved in 1200 parts of water at pH 6.0. 18 parts of 2,4-dichloro-6-methoxy-1,3,5-triazine are added over a period of 15 minutes at room temperature, the pH being between 5.5 and 6.0 by dropwise addition of 30 parts of 20% sodium carbonate solution is held. The completely precipitated dye is filtered off and dried in vacuo; it will be according to the formula

obtained as sodium salt and dyes polyamides and especially wool in a burgundy shade; the dyeings show very good wet fastness and very good light fastness.

Example 4

40.6 parts of 1-amino-2-p-toluenesulfonyl-4- (2'-chloro-4'-methoxy-1,3,5-triazinyl) aminobenzene are dissolved in 600 parts of a water-acetone mixture with 25 parts of 30 % hydrochloric acid and then diazotized with ice cooling with 7 parts of sodium nitrite in 50 parts of water. The reaction mixture is diluted with 900 parts of water, allowed to stir at 0-5 ° for one hour and excess nitrous acid is destroyed with aminosulfonic acid.

The diazo suspension is then added dropwise at 0-5 ° to a solution of 30.3 parts of 2-aminonaphthalene-3,6-disulfonic acid in 600 parts of water the reaction mixture is kept at pH 4.0-4.5 by adding 75 parts of sodium acetate. The dye suspension obtained is diluted with 600 parts of acetone, the temperature is allowed to rise to 20 °, the pH is adjusted to 8.0 and the mixture is filtered off. The dye dried in vacuum, which of the formula

corresponds and is isolated as sodium salt, dyes polyamide and especially wool in scarlet tones; the dyeings show very good wet fastness and very good light fastness.

Analogously to Examples 1 to 4, further compounds of the formula I can be prepared. In the following Table 1 are for dyes that have the general formula

correspond to the variables K, R ₁ , R ₂ and Hal in the individual columns, where K can mean the naphthalene radicals (K ₁ ) to (K ₁₅ ) given below:

These dyes, which are present as sodium salts depending on the production and isolation conditions, can also be isolated in the form of other salts by conventional measures.

The dyes can be used to dye and print cellulose and polyamides, in particular wool, by one of the processes known to be suitable; Dyes and prints show good light and wet fastness.

In the last column of Table 1 the shade of color obtained on wool is given; it means a = orange; b = scarlet; c = red; d = burgundy.

Example 67

30.3 parts of 2-aminonaphthalene-6,8-disulfonic acid are stirred in 180 parts of water, 100 parts of ice and 14 parts of 30% hydrochloric acid and within one hour at a temperature of 0-5 ° by adding a solution of 6.9 parts Sodium nitrite diazotized in 25 parts of water. The reaction is ended by stirring for 15 minutes.

18.4 parts of 1-aminobenzene-3-carbamic acid ethyl ester are stirred in 150 parts of water. The above diazo compound is added to this suspension within half an hour, the pH being kept between 4.0 and 4.5 by dropwise addition of 20 parts of 30% sodium hydroxide solution. The coupling is complete when the addition of diazo is complete, and the dissolved dye is then precipitated by adding 85 parts of sodium chloride and filtered off. The aminoazo color paste thus obtained The substance is condensed analogously to Example 3 with iδ parts of 2,4 dichloro-6-methoxy-1,3,5-triazine. When the reaction has ended, 100 parts of sodium chloride are added, the precipitated dye is filtered off and dried in vacuo; the dye according to the formula

is isolated as sodium salt, it dyes polyamides and especially wool in a golden yellow shade; the dyeings show very good light and wet fastness properties.

Analogously to Example 67, further compounds of the formula I can be prepared; they correspond to the general formula

for which the variables D, R ₁₀ and R _{1 are} listed in the individual columns in Table 2 below. Because of the way in which they are prepared, these dyes are obtained in the form of the sodium salts, but they can also be converted into other salts by conventional reaction. These dyes can be used to dye and print cellulose and polyamides, in particular wool, using customary processes; this results in dyeings and prints of good light and wet fastness properties.

In the last column of Table 2 the shade of wool is indicated; it means e = yellow and f = golden yellow.

Analogously to Examples 1 or 2, the following Examples 80 and 81 can also be prepared by using appropriate starting materials. Example 80

as sodium salt; the dye dyes wool in an orange shade;

Example 81

as sodium salt; the dye dyes wool in a red shade.

Example 82

49.4 parts of 1-amino-4- (4'-aminophenylamino) anthraquinone-2,3'-disulfonic acid (100%) are dissolved at 40 ° in 300 parts of water at a pH of 7.0 brought. Then 18.1 parts of 2,4-dichloro-6-methoxy-1,3,5-triazine are also sprinkled into the solution within 40 minutes at 40 °; the pH of the reaction mass is kept between 7.5 and 8.5 by the simultaneous dropwise addition of a 20% sodium hydroxide solution. When the reaction is complete, the dye is salted out with 10 parts of sodium chloride, the suspension obtained is stirred for a further 30 minutes and then filtered. The dye obtained, which is dried at 40 ° in vacuo, corresponds to the formula

and is isolated as the sodium salt; it can be used very well for dyeing or printing wool. This creates brilliant blue dyeings of a high level of authenticity.

If, in the above example, the corresponding 6-ethoxy derivative is used instead of 2,4-dichloro-6-methoxy-1,3,5-triazine, a dye is obtained which dyes polyamide in blue tones, dyeings with excellent wet fastness and very good light fastness results.

The following examples illustrate possible uses of the dyes according to the invention.

Coloring example A

1 part of the dye from Example 1 or 2 is dissolved in 250 parts of demineralized water. 5 parts of unchlorinated wool cable yarn are added to the dyebath, the temperature is set to 40 °. 5 parts of Glauber's salt (calcined), 1.5 parts of glacial acetic acid and 1 part of a commercially available leveling agent are then added; the mixture is heated to boiling temperature within 90 minutes and kept boiling for a further 60 minutes. The evaporated water is replaced every 15 minutes during the entire dyeing process. At the end of the dyeing process, the dyed woolen material is first washed under running hot, then under running cold water for about 3 minutes and dried at about 70 °. After drying, an orange or red color is obtained with very good light and wet fastness properties. Synthetic polyamides can also be dyed in an analogous manner. It is also possible to dye with the dyes of Examples 3-82. Coloring example B

A dye mixture consisting of

0.94 part of the dye from Example 1, 0.22 part of the dye from Example 2 and 0.84 part of the dye from Example 82 are dissolved in 250 parts of demineralized water and 5 parts of wool gabardine are added. The mixture is heated to 40 ° and 5 parts of Glauber's salt (calcined), 2 parts of acetic acid and 1 part of a commercially available leveling agent are added to the dyebath. The mixture is then heated to boiling temperature within 90 minutes and kept boiling for a further 60 minutes. The water evaporated during the dyeing process is replaced every 15 minutes. The resulting color is first rinsed hot, then rinsed cold and dried at approx. 70 °. After drying, a dyeing of olive-colored tint is obtained, which is characterized in particular by high light fastness and a good other level of fastness.

Claims

1. Compounds of the formula I

wherein

(1-4C) alkyl,

R ₁

Shark halogen, SO ₃ H; -SO ₂ (1-4C) alkyl;

—SO ₂ NR ₈ R ₉ or —NHCOOR ₁₀ mean that the triazinylamino group can be in position 4 or 5, but is in position 4 if R _{2 means} —NHCOOR ₁₀ ,

Hydrogen, (1-4C) alkyl or (1-4C) alkoxy,

R ₃ R _{4 is} hydrogen or (1-4C) alkyl,

R _{5 is} hydrogen, (1-4C) alkyl; cyclohexyl which is unsubstituted or substituted by 1 to 3 (1-4C) alkyl groups; Phenyl or phenyl substituted by 1 or 2 substituents from the series halogen, (1-4C) alkyl and (1-4C) alkoxy, R _{6 is} hydrogen or hydroxy with the proviso that R _{6 is} not hydroxy if R _{2 is} -NHCOOR ₁₀ , R _{7 is} hydrogen, (1-4C) alkyl or (1-4C) alkoxy, R _{8 is} hydrogen, (1 -4C) alkyl or (2-4C) hydroxyalkyl with the hydroxy group in position 2, 3 or 4,

R _{9 is} hydrogen, (1-4C) alkyl, (2-4C) hydroxyalkyl with the hydroxy group in position 2, 3 or 4; Cyclohexyl, phenyl or phenyl substituted by 1 or 2 substituents from the series halogen, (1-4C) alkyl, (1-4C) alkoxy, sulfo and carboxy,

R ₁₀ (1-6C) alkyl, m 1 or 2, n 0 or 1 and p 0 or 1 mean that a) n is only 0 and must be 0 if R _{2 is} -NHCOOR ₁₀ ; b) the group -NHR ₅ and the azo group are ortho to each other and are in 1- and 2- resp. are in the 2- and 1-position of the naphthalene ring; and c) when n is 1 and m is -1 and the azo group is in position 1 of the naphthalene ring, either R _{6 has} a meaning other than hydroxy in position 8 or the sulfo group is in position other than position 4 of the naphthalene ring, and there are at least 2 sulfo groups per molecule, mixtures of compounds of the formula I and their salts.

2. Compounds according to claim 1, wherein R _{2 is} SO ₃ H, R _{3 is} hydrogen, m is 1 and the sulfo group is in the 5- or 6-position, R ₆ for hydrogen or hydroxy in the 8-position, R ₅ represent hydrogen, n represents 1 and the -NH ₂ group is in the 2-position.

3. Mixtures containing a compound of the formula I according to claim 1 or 2 or a mixture of these compounds and additionally a compound of the formula VII,

wherein R _{1 is} (1-4C) alkyl, which is in salt form.

Mixtures according to claim 3 containing (a) a compound of formula Ic,

in salt form and / or

(b) a compound of the formula Id,

in salt form and (c) a compound of the formula VIIa,

in salt form.

5. A process for the preparation of compounds of the formula I according to claim 1 or mixtures thereof, characterized in that for the preparation of compounds of the formula I in which n is 1, the diazonium compound of the amine of the formula II,

wherein R _{3 has the} above meaning, has one of the meanings of R ₂ except the group -NHCOOR ₁₀ and

X is in position 4 or 5 and is NO ₂ or -NR ₄ Z ₁ , where R _{4 is} as defined above and Z ₁ for a protective group, the remainder (a) or (b)

< ^b > R

wherein R ₅ R ₆ and m have the above meaning, or couples a mixture thereof, in the case that Z _{1 represents} the radical (a), with the compound R ₁ OH; in the event that X denotes a nitro group, then reduces it, or that Z _{1 stands} for a protective group, splits it off and then in each case with cyanuric halide and then with the compound R ₁ OH or with a condensation product of cyanuric halide and R ₁ OH of the formula ( c)

6. The method according to claim 5, characterized in that one uses a compound of formula (c).

7. Use of the compounds according to any one of the preceding claims 1-4 for dyeing or printing leather.

8. A process for dyeing or printing leather, characterized in that for this purpose dyeing liquors or printing pastes containing a compound according to one of the preceding claims 1-4 are used.