CH643580A5 - ANIONIC DISAZO COMPOUNDS, THEIR PRODUCTION AND USE AS DYES. - Google Patents

Description

The invention relates to disazo compounds of the formula I

15

20th

A - N = N

N = N - K

NHR "

wherein

25th

K

a - n = n n • = n - k,

Yes

Ri 30 R,

NHR,

wherein A, Ri and R2 are as defined in claim 1 and Ki is the residue of a coupling component of the phenol series, characterized in that the diazo compound of a monoazoamine of the formula II

a - n = 'n-

II

couples to a phenolic coupling component of the formula Kj-H.

3. Process for the preparation of disazo compounds of the formula Ib,

r ..

a - n = n-

n = n - k,

Ib nhr "

where A, R! and R2 are as defined in claim 1 and K2 is the remainder of a coupling component from the phenol series, the free hydroxyl group of which is etherified, characterized in that the free hydroxyl group is etherified in claim 2 as defined in claim 2.

4. Process for the preparation of compounds of formula Ic

R1

the remainder of a sulfo-containing diazo component from the aniline series or naphthylamine series,

the rest of a coupling component from the phenol series, the free hydroxy group of which may be etherified or acylated,

Hydrogen, (1-4C) alkoxy, (1-4C) alkyl or by halogen monsubstitutreries (1-4C) alkyl and (1-4C) alkyl, -CO (1-6C) alkyl, -COO (1-6C) alkyl , -CONH2, -CONH- (1-6C) alkyl, -CON [(1-6C) alkyl] 2, -CONH (2-6C) hydroxyalkyl or-CON [(2-6C) hydroxyalkyl] 2

mean which carry the only sulfonic acid group contained in the residue A 35, in the form of the free acid or in salt form, processes for their preparation and their use as dyes.

Ri as alkoxy is preferably (1-2C) alkoxy, especially methoxy; as alkyl it is preferably (1-2C) alkyl, 40 in particular methyl and as halogen-substituted alkyl it is preferably monochloro (1-2C) alkyl.

Ri preferably denotes R'j as hydrogen, methyl, ethyl, methoxy or ethoxy; more preferably R "i as hydrogen, methyl or methoxy and very particularly preferably hydrogen.

R2 as (1-4C) alkyl preferably contains 1 or 2C atoms, in particular it stands for methyl. A (1-6C) alkyl group defined for R2, which via -CO-, -COO- or -CON

(H)

50 is bonded, preferably contains 1-4, preferably 1 or 2 carbon atoms and in particular preferably represents methyl; a (2-6C) hydroxyalkyl group preferably means 2-hydroxyethyl or 2- or 3-hydroxypropyl.

R2 preferably represents R'2 as -CO (1-4C) alkyl, -COO-55 (1-4C) alkyl or-CONH2; further preferred for R "2 as -CO- (1-2C) alkyl, -COO (l-2C) alkyl or-CONH2; particularly preferred for R" "2 as -COOH3, -COOCH3 or-CONH2 and in particular for - COCH3.

A is preferably a radical of the formula (a) or (b), 60 or r,

a - n = n-

3P-

r,

n = n - k "

ic so3h so3h nhr "

(a)

(b)

wherein

R3 is hydrogen, halogen, (1-4C) alkyl, halogen-substituted (1-4C) alkyl, (1-4C) alkoxy, mono- (1-6C) alkylamino, di- (1-6C) alkylamino , Alkyl (1-6C) -carbonyla-mino or alkoxy (1-12C) carbonylamino and R4 is hydrogen, halogen, (1-4C) alkyl or (1-4C) alkoxy.

K preferably represents a radical of the formulas (c) or (d),

or

OR,

'5 a

R,

'6 a

(c) (d)

wherein

R5a and R5b are hydrogen, (1-4C) alkyl, (2-4C) hydroxyalkyl,

-CORg, -COOR8 or -SO <ö> R8 one

(1-12C) alkyl- or phenyl- (1-4C) alkyl or (1-4C) A1-koxy,

R6a is a hydrocarbon radical from the aliphatic, cycloaliphatic, aromatic or araliphatic series, Ha- "logen, (1-4C) alkoxy, -NHCO (1-4C) alkyl or" -NHCOO (1-6C) alkyl,

Ret, hydrogen, (1-4C) alkyl, (1-4C) alkoxy, halogen,

-NHCO (1-6C) alkyl or -NHCOO (1-6C) alkyl and R7 is hydrogen, halogen, (1-4C) alkyl or (1-4C) alkoxy.

Halogen generally stands for fluorine, chlorine or bromine. Halogen as a phenyl substituent is preferably chlorine or bromine, in particular chlorine; Halogen as an alkyl substituent is preferably fluorine or chlorine, especially chlorine.

R3 as unsubstituted or substituted alkyl preferably contains 1 or 2 carbon atoms, in particular 1 carbon atom; preferably R3 represents an unsubstituted alkyl group. R4 as alkyl preferably represents methyl or ethyl, in particular methyl. R3 or R4 as alkoxy preferably represents methoxy or ethoxy, in particular methoxy.

A monoalkylamino group defined for R3 preferably contains a methyl or ethyl and particularly preferably a methyl radical; a dialkylamino group preferably contains methyl and / or ethyl radicals, in particular methyl radicals. The alkyl (1-6C) carbonylamino group is particularly preferably an acetamino group; an alkoxy (1-12C) -carbonylamino group preferably represents methoxy- or ethoxycarbonylamino and also alkoxy (8-12C) -carbonylamino.

R3 preferably represents R'3 as hydrogen, halogen, (1-4C) alkyl, (1-4C) alkoxy or acetylamino; more preferably for R "3 as hydrogen, chlorine, (1--2C) alkyl, (1--2C) alkoxy or acetylamino; more preferably for R" 3 as hydrogen, chlorine, methyl, methoxy or acetylamino and particularly preferably for hydrogen.

R4 preferably represents R'4 as hydrogen, halogen, (1-2C) alkyl or (1-2C) alkoxy; more preferably for R'4 as hydrogen, chlorine, methyl or methoxy and particularly preferably for hydrogen. R4 is preferably hydrogen if R3, R'3, R "3 or R '" 3 is acetylamino.

If R3 and R4 are both hydrogen, the sulfo group is preferably in the 3- or 4-position to the azo group; if, in addition to the sulfo group, a further R3 or R4 radical other than hydrogen is added, then positions 2,4,2,5 or 3,4 are preferred and are particularly preferred

643,580

positions 2.4 or 2.5 are occupied; if, in addition to the sulfo group, two further radicals R3 and R4 with a different meaning than hydrogen are present, the three substituents preferably take the positions 2,3,5,2,4,5 or 2,4,6 and very particularly preferably the positions 2 , 4,5 or 2,4,6, the sulfo group preferably being in the o- or p-position to the azo group.

The radical of the formula (a) particularly preferably contains R3 and R4 in the meaning of hydrogen and the sulfo group in position 3 or 4 or a further radical R3 or R4 in the meaning of chlorine, methyl or methoxy in addition to the sulfo group, preferably in the 2nd position , 4 or 2.5 or an acetylamino group in position 4 or 5 in addition to the sulfo group in position 2 or two further radicals R3 and R4 in the meaning of methyl, methoxy and / or chlorine with the sulfo group in the preferred positions 2,4,5 or 2,4,6, the sulfo group preferably being in the o- or p-position to the azo group.

If the naphthyl radical of the formula (b) is bonded in the 1-position, the sulfo group is preferably in the 4,5,6,7 or 8 position, particularly preferably in the 4 or 5 position; if it is bound in the 2-position, the sulfo group is preferably in position 1,5,6,7 or 8, particularly preferably in position 1,5 or 6.

The radical (b) is preferably (fy) as 4- or 5-sulfonaphthyl-1 or as 1-, 5- or 6-sulfonaphthyl-2.

R5a or R5b as unsubstituted or substituted alkyl is preferably unbranched and is preferably methyl or ethyl or 2-hydroxyethyl or 2- or 3-hydroxypropyl. As group -COR8 or -COORs, it preferably contains the radical R's in the meaning of (1-4C) alkyl or phenyl- (1-3C) alkyl, in particular the radical R "8 as methyl, ethyl or benzyl. As

Residue -S02- <'O / ^ 9 contains it as substituent R9 in the

Significance of halogen, in particular chlorine, meaning alkyl, preferably methyl or ethyl, especially methyl, and alkoxy, preferably methoxy or ethoxy.

R5a preferably represents R'5a as hydrogen, methyl, ethyl, 2-hydroxyethyl, -COOR'g, phenylsulfonyl or tosyl; more preferably for R "5a as hydrogen, methyl, ethyl or -COOR" s; in particular for R ″ ″ 5a as hydrogen or methyl and very particularly preferably for hydrogen.

R5b preferably represents R'5b as hydrogen, methyl, ethyl, 2-hydroxyethyl, -COOR'8, phenylsulfonyl or tosyl; more preferably for R "5b as hydrogen, methyl, ethyl, phenylsulfonyl or tosyl; more preferably for R" 5b as methyl, ethyl, phenylsulfonyl or tosyl and in particular for methyl or ethyl.

Röa as a hydrocarbon radical can contain common substituents such. B. from the series halogen (fluorine, chlorine, bromine), (1-4C) alkyl or (1-4C) alkoxy and, especially for an aliphatic radical, also carry hydroxyl or cyano groups.

Re as an aliphatic hydrocarbon radical is preferably an unsubstituted, unbranched or branched (1-10 Qalkyl radical, which more preferably contains 1-6C atoms and in particular 1-4C atoms; as a cycloaliphatic radical it preferably contains 5-7C atoms; as a radical the aromatic or araliphatic series, it preferably represents an unsubstituted phenyl or phenyl (1-4C) alkyl radical.

Rga as halogen preferably represents chlorine; as alkoxy, preferably for methoxy or ethoxy.

R6a as -NHCOalkyl or -NHCOOalkyl preferably contains (1-4C) -, in particular (1 or 2C) -alkyl radicals.

R (îa preferably denotes R'6a as unbranched or branched (1-6C) alkyl, (5-7C) cycloalkyl, phenyl, benzyl, chlorine, methoxy, ethoxy or acetylamino; more preferably for R "6a as unbranched or branched (l -4C) alkyl, benzyl, chlorine, methoxy or ethoxy, especially for R "'6a as (1-4C) alkyl or chlorine.

3rd

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

643,580

4th

R7 as halogen preferably denotes chlorine; as alkyl it is preferably methyl or ethyl, especially methyl; preferred as alkoxy for methoxy or ethoxy, especially methoxy.

R7 preferably represents R'7 as hydrogen, chlorine, methyl, ethyl, methoxy or ethoxy; more preferably for R "7 as hydrogen, chlorine, methyl or methoxy and in particular for hydrogen.

R6b as halogen preferably denotes chlorine or bromine; as alkyl it is preferably methyl or ethyl, especially methyl; as alkoxy preferably for methoxy or ethoxy, especially for methoxy.

R6b as -NHCOalkyl or -NHCOOalkyl preferably contains an (1-4C) alkyl group, in particular the methyl radical.

R6b preferably denotes R'6b as hydrogen, chlorine, bromine, methyl, ethyl, methoxy, ethoxy or acetylamino; more preferably R "gb as hydrogen, chlorine, methyl or methoxy and particularly preferably hydrogen.

A preferably represents the radical (aj) with R3 and R4 in the meaning of R'3 and R'4 or the radical (bj); more preferably for the radical (a2) with R3 and R4 in the meaning of R "3 and R'4 or for the radical (bt); more preferably for the radical (a3) with R3 in the meaning of R" '3, in particular as hydrogen, and with R4 in the meaning of R'4, in particular as hydrogen, the substituents in the respective radicals (aj) to (a3) being in the positions indicated above as preferred.

K preferably represents the radical (q) with R5a as R'5a, Rga as R'ea and R7 as R'7 or for the radical (dj.) With R5b as R'5b and R ', as R'6b; more preferred for the rest (c2) with R5a as R '"5a, Rfe as R"' 6a and R7 as R "7 or for the rest (d2) with R5b as R" 5b and R6b as R "6b; more preferred for the rest (d2); particularly preferably for the rest (d3) with R5b as R '' '5b, in particular as methyl or ethyl, and R6b as hydrogen.

Preferred compounds of the formula I are those in which

(1) A represents the residue (aj) or (bx);

(2) A represents the residue (a2) or (b ^;

(3) Rt is R'i and R2 is R'2;

(4) K represents the remainder fo) or (dt);

(5) K represents the remainder (dj);

(6) those corresponding to the formula Id,

The nature of the cation of the sulfo group is not a critical factor, but it can be any non-chromophoric cation common in anionic dye chemistry, for example an alkali metal ion or an unsubstituted or substituted ammonium ion. Examples of suitable cations are lithium, sodium, potassium, ammonium, mono-, di-, tri- and tetramethylammonium, triethylammonium and mono-, di- and triethanolammonium. Preferred cations are the alkali metal ions including ammonium, of which sodium is particularly preferred. The disazo compounds of the formula I can be prepared by: a) preparing disazo compounds of the formula Ia,

15

VA - N

N = N - K,

Yes

NHR,

20th

wherein A, Ri and R2 are as defined above and Kt is the residue of a coupling component of the phenol series, the diazo compound of a monoazoamine of the formula II

25th

AT

30th

II

couples to a phenolic coupling component of the formula Kj-H;

b) for the preparation of disazo compounds of the formula Ib,

35

AT

N - K "

-Ib

40

NHR,

A- - N =

= N ~ (O) -N = N -

K,

Id in which A, Ri and R2 are as defined above and K2 denotes the residue of a coupling component from the phenol series, the free hydroxyl group of which is etherified, the free hydroxyl group is etherified in a compound of the formula Ia;

c) for the preparation of disazo compounds of the formula Ic,

where A2 is the remainder (a2)

T? "

3 '

R4

50

AT

N - K_

Ic

NHR,

S03H

and K4 the rest (di)

0K5b wherein A, Rj and R2 are as defined above and K3 is the residue of a coupling component from the phenol series, the free hydroxyl group of which is acylated, the free hydroxyl group is acylated in a compound of the formula Ia.

So compounds of formula Ie,

60

R6b means;

(7) those of (6) wherein A2 is (a3);

(8) those of (6), in which K4 denotes the radical (d2) and in particular (d3);

(9) those of (6), in which R 'i is R "i, in particular hydrogen and R" 2 is R' "2, in particular -COCH3.

A ^ - N = N

■ N = N - Kr

Ie

NHR,

65

where Ax is the radical (a) or (b) and K5 is the radical (c) or (d) and R! and R2 are as defined above, made by

5

643,580

a) for the preparation of the compounds of the formula Ix,

K = K "Ix

NHR "

A1 - N = N

where K5x is the rest of the formulas (ax) or (bx) OH

speed of the reaction conditions in the form of their salts. If desired, conversion into the free acid or even salting-out can be carried out by methods known per se.

5 The compounds of the formula II are known or they can be neutralized in a manner known per se by weakly acidic bjs

Coupling of the diazo compound of an amine of the formula A-NH2 to the corresponding aniline of the formula xo

15

R

(ax>

6b

NHR "

to a phenol of the formula purple or Illb

R? purple

H

OH

R

6b couples or b) for the preparation of compounds of formula Ie, wherein R5a or. R5b has a meaning other than hydrogen, etherifies or acylates a compound of the formula Ix.

The diazotization of a monoazoamine of the formula II or IIa is carried out according to methods known per se.

The coupling reaction is carried out in an alkaline medium in a manner known per se. Likewise, etherification or acylation of a compound of the formula Ia or Ix are carried out according to a conventional method.

The etherification is preferably carried out with the corresponding dialkyl sulfate or alkylene oxide in an aqueous, alkali-alkaline medium, preferably at a pH between 9 and 11, and at a temperature of 30 to 90 ° C., preferably 40 to 70 ° C.

The acylation is preferably carried out with the corresponding acid chloride in an aqueous soda-alkaline medium, preferably at pH values from 8 to 10, and at temperatures between 30 to 90 ° C., preferably between 60 and 70 ° C.

The compounds of formula I obtained can be isolated from the reaction mixture in a manner known per se. The compounds of the formula I are usually dependent on

iy

NHR "

means the diazo compound of a monoazoamine of the formula IIa

IIa

35

Illb "0

20 or its derivative reacted with co-methanesulfonic acid. Anilines of the formula IV as well as the phenols of the formula lilac or IHb are either known or they can be obtained analogously to methods known per se.

The compounds of the formula I are anionic dyes 25 and can be used for dyeing, padding and printing any substrates which can be dyed with anionic dyes. Suitable substrates include materials which consist of or contain natural and synthetic polyamides, leather, basic modified polyolefins or polyurethanes 30.

However, the dyes are particularly advantageously used for dyeing, padding and printing fiber material which consists of or contains natural and synthetic polyamides such as wool, silk and in particular nylon, and also particularly advantageously in carpet printing.

The compounds of the formula I or mixtures thereof can be used as such or in the form of liquid or solid preparations.

Processing into stable liquid, for example concentrated aqueous or solid coloring preparations can be carried out in a generally known manner, e.g. by dissolving in suitable solvents such as water, if appropriate with the addition of customary auxiliaries, for example a solvent such as urea, or then by grinding or granulating.

Such preparations can be obtained, for example, according to the information in French patents 1572030 or 1581900.

It is also possible to use the compounds in the form of cold-dispersible preparations. For this who-50 the z. B. the dyes are subjected to mechanical comminution in the presence of one or more conventional anionic dispersants and, where appropriate, other conventional auxiliaries by dry or wet grinding with the dispersion medium water and, if appropriate, subsequently dried by atomization. The preparations prepared in this way are dispersed again in finely dispersed form when introduced into cold water and are therefore easy to handle.

The fiber material can be dyed by any suitable method, in particular by the padding process or exhaust process, the latter of which is preferred, since the compounds of the formula I are neutralizing dyes. Use in space dyeing is also suitable.

Furthermore, the dyes of the formula I have good solubility, good drawability combined with good build-up capacity, good migrability and they level out well, in particular streak-coloring nylon-covering colorations can be achieved. The colorations achieved with the dyes of the formula I or mixtures thereof show remarkable lightfastness

45

643,580

Ness; in addition, the dyeings have other good general fastness properties, such as good wet fastness properties, especially fastness to washing, milling and sweating.

The dyes of the formula I according to the invention have good combinability with other neutral dyes, especially in important trichromes, the good properties of the dyeings being retained; in particular, the colorations show no catalytic fading.

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

P> -n =

oh

SO ^ Na nhcoch,

10th

example 1

17.3 parts of l-aminobenzene-3-sulfonic acid as the sodium salt are dissolved in 80 parts of water, 6.9 parts of sodium nitrite are added and the mixture is allowed to run in slowly with stirring to a mixture of 50 parts of ice and 28 parts of hydrochloric acid at 30%. After an hour at 5-10 °, excess nitrous acid is decomposed with a little amidosulfonic acid. The suspension of the diazonium salt obtained is added to a solution of 18.7 parts of 3-aminoacetanilide as the hydrochloride and 5 parts of calcined soda in 150 parts of water and 100 parts of ice with stirring at 0-5 °, the pH being increased by adding calcined soda is held at 6-7. The reaction mixture is stirred for an hour; the monoazo compound obtained is then precipitated with sodium chloride and, after filtration, washed with 5% sodium chloride solution.

The paste of the monoazo compound thus prepared is dissolved in 170 parts of water at 60 ° and mixed with 6.9 parts of sodium nitrite. This solution is slowly added dropwise to a mixture of 60 parts of ice and 28 parts of hydrochloric acid; the temperature is kept at 5-10 ° by adding ice. After two hours, excess nitrous acid is decomposed by sulfamic acid. The suspension of the diazonium compound is slowly added to a solution of 9.5 parts of phenol and 13 parts of 30% sodium hydroxide solution in 140 parts of water at room temperature, after 15 minutes the coupling is complete. The dye is precipitated by adjusting the pH to 9 and salting out with table salt; is isolated by filtration, washed with 5% sodium chloride solution and dried. The dye corresponds to the formula

15

20th

n = n - n = n - ^ - oh

S03 Well

25th

30th

35

it dyes natural and synthetic polyamides in reddish yellow tones, the dyeings show good lightfastness and good wetfastness.

If, instead of l-aminobenzene-3-sulfonic acid, a mixture of l-aminobenzene-3- and -4-sulfonic acid (approximately in a ratio of 1: 1) is used in Example 1, the corresponding disazo dye mixture, which is also etherified according to Example 2, is obtained can be. This dye mixture (both with a free hydroxyl group and with a methoxy group) is particularly suitable because of its good solubility for dyeing natural and synthetic polyamides, dyeings of reddish yellow tones and good light and wet fastness properties being achieved.

Analogously to Examples 1 and 2, further compounds of the formula I can be prepared; for these dyes that the formula

■ n = n-

correspond, the variables are given in Table 1; for other dyes of the formula

40

n = n

45

S03 Well

0r "

nhr "

correspond, the variables are given in Table 2; for other dyes of the formula

NHCOCH,

50

it dyes natural and synthetic polyamides in reddish yellow tones. The dyeings show good light fastness and good wet fastness.

Example 2

The etherification of the free hydroxy group in the disazo dye of Example 1 is carried out as follows. For this purpose, the filtered and washed disazo dye of Example 1 is dissolved as a paste in water at 45-50 ° with 10 parts of 30% sodium hydroxide solution. 25 parts of dimethyl sulfate are added to this solution with vigorous stirring. At the same time, the pH is kept at 10.5-11.0 by adding 30% sodium hydroxide solution. Methylation is complete after four hours; sprinkling of table salt completes the precipitation of the dye. It is filtered, washed with 5% sodium chloride solution and dried. The disazo dye obtained corresponds to the formula

55

60

a - n - n —— n = n nhr,

correspond, the variables are given in Table 3.

The hue of the dyeings achieved with these dyes of Examples 3-70 on natural and synthetic polyamides is given in the last column N; it means a = reddish yellow b = orange 65 c = yellowish red d = red e = brownish red The colorations show good light and wet fastness.

7

643,580

Table 1

example

Position r3

r4

rJ

or5

R6

r7

N

No.

S03 Well

3rd

4th

H

H

H

OH (4)

H

H

a

4th

4th

H

H

H

OCH3 (4)

H

H

a

5

4th

H

H

H

OH (2)

Cl (5)

H

a

6

4th

H

H

H

OCH3 (2)

do.

H

a

7

3rd

H

H

H

OH (2)

do.

H

a

8th

3rd

H

H

H

OCH3 (2)

do.

H

a

9

3rd

H

H

och3

OH (4)

H

H

c

10th

3rd

H

H

do.

OCH3 (4)

H

H

c

11

3rd

H

H

do.

OH (2)

Cl (5)

H

e

12

3rd

H

H

do.

OCH3 (2)

do.

H

d

13

4th

H

H

do.

OCH3 (4)

H

H

c

14

4th

H

H

do.

OC2H5 (4)

H

H

c

15

3rd

H

H

ch3

OH (2)

tert. Butyl (5)

H

b

16

3rd

H

h och3

do.

do.

CH3 (3)

d

17th

3rd

H

h do.

OC2H5 (2)

CH3 (5)

H

d

18th

4th

H

h do.

OCH3 (2)

Isopropyl (5)

H

d

19th

4th

H

H

ch3

OH (2)

CH3 (5)

H

b

20th

4th

H

H

H

-O Tosyl (4)

H

H

a

21st

3rd

H

H

och3

OCH3 (4)

-NHCOCH3 (5)

H

c

22

3rd

H

H

do.

OC2H5 (4)

do.

H

c

23

3rd

H

H

ch3

do.

-NHCOCH3 (6)

H

d

24th

4th

H

H

och3

OCH3 (4)

do.

H

d

25th

2nd

-NHCOCH3 (4)

H

H

OH (4)

H

H

a

26

2nd

do.

H

H

OCH3 (4)

H

H

a

27th

4th

ch3

H

och3

do.

H

H

c

28

4th

do.

H

ch3

do.

H

H

a

29

4th

do.

H

do.

OC2H5 (4)

H

H

a

30th

5

CH3 (2)

H

H

OCH3 (4)

H

H

b

31

5

do.

H

h do.

CH3 (2)

h b

32

2nd

CH3 (4)

H

och3

do.

H

H

c

33

6

CH3 (2)

CH3 (4)

do.

OC2H5 (4)

H

H

c

34

5

OCH3 (2)

H

H

do.

H

H

b

35

2nd

Cl (4)

H

H

OCH3 (4)

H

H

a

36

2nd

do.

H

H

-O Tosyl (4)

H

H

a

37

5

Cl (2)

H

H

OCH3 (4)

H

H

a

38

2nd

Cl (5)

CH3 (4)

ch3

do.

h h

a

39

4th

Cl (2)

Cl (5)

och3

do.

H

H

c

40

4th

do.

H

H

do.

H

H

a

Table 2 Table 3

Example position R3 Rj R2 R5 N

No.

S03 Well

41

3rd

h h

-coc2h5

ch3

a

• Example no.

A

ri r2

or5

r «

N

42

4th

h h

do.

do.

a

43

4th

h och3

do.

Q> h5

c

.57

4-sulfonaphthyl-1 h

-COCH3

oh (4)

H

C.

44

3rd

h h

do.

do.

a

'58

do.

h do.

och3 (4) h c

45

3rd

h h

do.

Tosyl a

59

5-sulfonaphthyl-1 h

do.

do.

h c

46

5

cl (2)

H

-cooch3

ch3

a

60

do.

H

-COQH5 do.

h c

47

5

do.

ch3

do.

do.

a

61

do.

H

-conh2

do.

h c

48

2nd

ch3 (4)

och3

do.

do.

c

62

do.

H

-coch3

oh (2)

Cl (5)

c

49

2nd

do.

h do.

do.

a

63

6-sulfonaphthyl-2

h do.

oh (4)

h b

50

2nd

do.

h do.

QH5

a

64

do.

H

do.

OCH3 (4) H

b

51

5

OCH3 (2)

h do.

ch3

b

65

do.

ch3

do.

do.

H

c

52

4th

H

H

do.

c, h5

a

66

do.

och3

do.

do.

H

d

53

4th

H

H

-COOC2H5

ch3

a

.67

do.

H

do.

OCH3 (2) Cl (5)

b

54

3rd

H

och3

-conh2

do.

c

68

5-sulfonaphthyl-2

H

do.

OH (4)

H

b

55

4th

H

do.

do.

do.

c

69

do.

H

do.

OCH3 (4) H

b

56

4th

H

H

do.

Tosyl a

70

l.Sulfonaphthyl-2

ch3

do.

do.

H

c

643,580

Depending on the reaction and isolation conditions, the dyes of Examples 1 and 2 and Tables 1-3 can also be used in the form of the free acid or in another salt form, for example with one of the cations further described in the description, instead of in the form of the sodium salt. getting produced.

Staining instructions

In a dyeing tape consisting of 4000 parts of water, 10 parts of anhydrous sodium sulfate and 2 parts of the dye from Example 2, 100 parts of pre-wetted synthetic polyamide fabric, e.g. Nylon 66, a.

The dyeing liquor is heated to boiling temperature over the course of 30 minutes, kept at this temperature for 1 hour, 4 parts of glacial acetic acid are added and the dyeing is ended by heating to boiling temperature for a further 30 minutes. The evaporated water is constantly replaced during dyeing. Then you take the reddish yellow nylon cloth from the fleet, rinse it with water and dry it. Wool can also be dyed using the same procedure.

The same procedure can be used to dye with the dyes from Examples 1 and 3-70 or with a mixture of two or more dyes from Examples 1-70.

The dyeings have good lightfastness and good wet fastness.

Printing instruction 5 Polyamide is printed with a printing paste of the following composition:

30 parts of dye according to Example 2 50 parts of urea

50 parts of a solubilizer (e.g. thiodiethylene glycol) 10 290 parts of water

500 parts of a suitable thickener (e.g. based on locust bean gum)

20 parts of an acid dispenser (e.g. Ammontartrat)

60 parts of thiourea 15 The printed fabric is steamed for 40 minutes at 102 ° (saturated steam), then rinsed cold, then washed for 5 minutes at 60 ° with a dilute solution of a commercially available detergent and rinsed again cold. A reddish yellow print of good wet fastness and light fastness is obtained.

In an analogous manner, draping pastes can be produced which contain as a constituent a dye from Examples 1 or 3-70 or a mixture of two or more dyes from Examples 1-70.

M

Claims (2)

643,580 2nd Claims 1. Disazo compounds of the formula I, A - N = N - N = N - K NHR " where A, R! and R2 are as defined in claim 1 and K3 is the remainder of a coupling component from the phenol series, the free hydroxyl group of which is acylated, characterized in that in a compound of the formula Ia defined in claim 5, the free hydroxyl group is acylated. 5. A process for dyeing or printing leather, characterized I characterized in that dyeing or printing with a compound of formula I defined in claim 1 or mixtures thereof. 10th wherein A is the remainder of a sulfo-containing diazo component from the aniline series or naphthylamine series, K the rest of a coupling component from the phenol series, the free hydroxyl group of which may be etherified or acylated, Rj is hydrogen, (1-4C) alkoxy, (1-4C) alkyl or halogen monosubstituted (1-4C) alkyl and R2 (1-4C) alkyl, -CO (1-6C) alkyl, -COO (1-6C ) Alkyl, -CONH2, -CONH- (1-6C) alkyl, -CON [(1-6C) alkyl] 2, -CONH (2-6C) hydroxyalkyl or-CON [(2-6C) hydroxyalkyl] 2 mean, which carry as the only sulfonic acid group contained in the radical A, in the form of the free acid or in salt form. 2. Process for the preparation of disazo compounds of the formula Ia,