CH667465A5 - UNBALANCED 1: 2 chromium complex dyes. - Google Patents

Description

667 465

2nd

PATENT CLAIMS 1. 1: 2 chromium complex dyes of the formula

O.N 2 \ / \

2 3

Y1 ï t

\ A A

mm • • •

1 11 M V 1 11 1

• • —N - N— • • •

s / r \ / \ s

1/1

^: cr

0/0

1/1

A 'A

"-N = CH-" • I D II 1 II

• v • •

* 5 / ^ /

• •

I.

e.g.

0

Ka

©

in which R1 is chlorine or, in particular, hydrogen, Ar 'is a benzene or naphthalene radical which is unsubstituted or substituted by chlorine, nitro, sulfo, Ci-Ct-alkyl, Ci-Ct-alkoxy, phenylzo, sulfophenylazo, naphthylazo or sulfonaphthylazo, R2 is hydrogen, nitro, sulfo, chlorine or methyl, m 2 or 3, Ka® potassium or sodium and one of the substituents X2 and X3 is an SCb group and the other is hydrogen.

- (SO © Ka®) 3 i

10th

(x),

DESCRIPTION The invention relates to 1: 2 chromium complex dyes of the formula ## STR1 ## in which R is hydrogen, chlorine or methyl, Z is hydrogen or a group -N = N-Ar, where Ar is an optionally substituted aryl or heteroaryl radical, n is an integer from 1 to 4, Ka® is a cation and one of the substituents X1, X2 and X3 is an SCh group and the other two are hydrogen, it being possible for the ring D to carry further substituents.

2. Dyes according to claim 1, wherein R is chlorine or in particular hydrogen.

3. Dyes according to one of claims 1 or 2, wherein one of the substituents X2 or X3 is an SC> 3 group and the other is hydrogen.

4. Dyes according to any one of claims 1 to 3, wherein the ring D is unsubstituted or substituted once or twice by sulfo, nitro, halogen, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-alkylsulfonyl or sulfonamide.

5. Dyes according to claim 4, wherein the ring D is an 1-hydroxy-2-aminobenzene which is substituted by nitro and optionally also by a further nitro group, by sulfo, chlorine or methyl.

6. Dyes according to one of claims 1 to 5, wherein Z represents a group of the formula -N = N-Ar, where Ar represents the residue of an optionally substituted aromatic amine.

7. Dyes according to claim 6, wherein Ar is a benzene or naphthalene radical which is unsubstituted or substituted by chlorine, nitro, sulfo, Ci-C4-alkyl, Ci-Gt-alkoxy, phenylazo, sulfophenylazo, naphthylazo or sulfonaphthylazo.

8. Dyes according to claim 7, wherein Ar represents the unsubstituted or substituted by chlorine, nitro, methyl, methoxy or sulfo phenyl group or the unsubstituted or substituted by naphthyl group.

9. Dyes according to one of claims 1 to 8, which carry 2 or 3 sulfo groups.

10. Dyes according to claim 1 of the formula

25th

30th

?

° 2 \ À • •

I II

V

I.

()

0 '

I.

/ \.

I D II% /

■ N = N-

J

^ Cr- /

¥ f

A A • •

i n i vv

1

0

■ N = CH- «

0

1

A.

n

V *

i z

0

Ka

©

- (SO © Ka®) 3 n

(d r

2 3

ï ï

° 2N \ A A A • • • • •

1 11 M - M 'M'

v / ~ VV

i / h

.Cr:

X «-N = CH-« 5 ^ NO —I— Il 1 II

2 • • • »•

2 / V V

R I

N = N-Ar '

® © Ka

- (SO ®Ka®) 3 m in which R is hydrogen, chlorine or methyl, Z is hydrogen or a group -N = N-Ar, where Ar is an optionally substituted aryl or heteroaryl radical, n is an integer from 1 to 4, Ka ® is a cation and one of the substituents X1, X2 and X3 is an SCh group and the other two are hydrogen, ring D being able to carry further substituents.

In preferred dyes of the formula I, R is chlorine or in particular hydrogen.

40 Of the substituents X1, X2 and X3, one is an SO3 group and the other two are hydrogen. Preferred dyes are those in which one of the substituents X2 or X3 is an SCb group and the other is hydrogen. In the azomethine dye of the 1: 2 chromium complexes of the formula I given above, the ring D can carry further substituents.

The ring D is preferably unsubstituted or substituted once or twice by sulfo, nitro, halogen, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-alkylsulfonyl or sulfonamide. 50 The radical D is derived, for example, from the following amines: 2-amino-l-hydroxybenzene,

4-chloro- and 4,6-dichloro-2-amino-l-hydroxybenzene,

4- or 5-nitro-2-amino-l-hydroxybenzene,

4-chloro and 4-methyl-6-nitro-2-amino-l-hydroxybenzene, 55 6-acetylamino and 6-chloro-4-nitro-2-amino-l-hydroxybenzene,

4-sulfonamido-2-amino-1-hydroxybenzene, 4-methylsulfonyl-2-amino-1-hydroxybenzene, 4-methoxy-2-amino-1-hydroxybenzene, 60 4-methoxy-5-chloro-2-amino-1 -hydroxybenzene, 4-methyl-2-amino-1-hydroxybenzene,

4-chloro and 4-methyl-5-nitro-2-amino-1-hydroxybenzene, 3,4,6-trichloro-2-amino-1-hydroxybenzene, 4,6-dinitro-2-amino-1-hydroxybenzene , 65 2-amino-l-hydroxybenzene-4- or 5-sulfonic acid,

2-amino-1-hydroxybenzene-4,6-disulfonic acid, 4-nitro-2-amino-1-hydroxybenzene-6-sulfonic acid, (II) »6-nitro-2-amino-l-hydroxybenzene-4-sulfonic acid,

3rd

667 465

6-chloro-2-amino-1-hydroxybenzene-4-sulfonic acid, 4-chloro-2-amino-l-hydroxybenzene-6-sulfonic acid, 4-methylsulfonyl-5-nitro-2-amino-l-hydroxybenzene, 4- Methylsulfonyl-6-nitro-2-amino-1-hydroxybenzene, 6-methyl-2-amino-1-hydroxybenzene-4-sulfonic acid. • In particularly preferred dyes, the ring D is one

1-Hydroxy-2-aminobenzene, which is substituted by nitro and optionally also further substituted by a further nitro group, by sulfo, halogen, such as bromine or especially chlorine or methyl.

Comes as aldehyde for the azomethine dye

2-hydroxybenzaldehyde in question or preferably 2-hydroxybenzaldehyde, which has a group -N = N-Ar in the p-position to the hydroxy group.

Ar denotes the remainder of an optionally substituted heterocyclic or carbocyclic aromatic amine, the substituents being e.g. Halogen, e.g. Bromine or especially chlorine, nitro, sulfo, Ci-C4-alkyl, Ci-C4-alkoxy, phenylazo, sulfophenylazo, naphthylazo or sulfonaphthylazo come into consideration.

Ar preferably denotes a benzene or naphthalene radical which is unsubstituted or substituted by the substituents listed above.

Particularly preferred groups Ar are the unsubstituted or chlorine, nitro, methyl, methoxy or sulfo-substituted phenyl group and the unsubstituted or sulfo-substituted naphthyl group.

The 1: 2 chromium complexes of the formula (I) carry 1 to 4, in particular 2 or 3, sulfo groups.

Ka® represents a cation, for example an alkali application, such as lithium or preferably potassium or sodium. Furthermore, Ka® can be an ammonium cation or the ammonium salt of an organic amine.

The 1: 2 chromium complex dyes of the formula are of particular importance because of their good coloring properties

° 2N \ A

2 3

f? .A.A.

1 11 »M '11 1

V, * - N - N - *> •, •

/ Ì

. Cr:

0

1

.A.

0

1

.A_

NO -4- I * N CH_i I]

2 * v • • »•

2Ä 'V

R 7

N = N-Ar '

© © Ka

- (SO © Ka ©) 3 m io

15

25th

Chromium III salts carried out. The 1: 1 chromium complex is then converted to the 1: 1 chromium complex in weakly acidic, neutral or weakly alkaline medium.

The new metal complex dyes of the formula I obtainable by the above process are isolated in the form of their salts, in particular alkali metal salts, especially sodium or lithium salts, or also ammonium salts or salts of organic amines with a positively charged nitrogen atom and are suitable for dyeing and printing various substances , optionally in the presence of a leveling agent, but especially for dyeing and printing nitrogen-containing materials, such as silk, wool, and also for synthetic fibers made of polyamides or polyurethanes and in particular for furs or leather.

Brown olive, olive or olive green dyeings are obtained with good fastness properties, in particular light and wet fastness properties.

The preferred use of the dyes according to the invention is in dyeing furs or leather, all types of leather being suitable, e.g. Chrome leather, retanned leather or suede from goat, beef or pork. The dyestuffs according to the invention are particularly suitable for dyeing suede, since they equalize well and penetrate well.

The following examples serve to illustrate the invention without restricting it. Parts mean parts by weight and percentages percent by weight. The temperatures are given in degrees Celsius.

30th

example 1

35

(II),

40

45

50

° 2 \ A Ü f

V

i

0 ^

-N = N-

_ ^ CrC.

•• vV-

V

? ° 3

/ V \

i n i

• v •

V V

i

"0

^ 0 I

A_

• v •

V

I.

N = N-

Ï1

/ \

in %/"

, ©

3Na

©

wherein R1 is chlorine or in particular hydrogen, Ar 'is a benzene or naphthalene radical which is unsubstituted or substituted by chlorine, nitro, sulfo, Ci-C4-alkyl, Ci-C4-alkoxy, phenylazo, sulfophenylazo, naphthylazo, or sulfonaphthylazo, R2 Is hydrogen, nitro, sulfo, chlorine or methyl, m 2 or 3, Ka® potassium or sodium and one of the substituents X2 and X3 is an SCh group and the other is hydrogen.

The dyes according to the invention can be prepared by methods known per se, for example by preparing the 1: 1 chromium complex of the azo dye and then reacting it with the azomethine or arylazo-azomethine dye or preferably with a mixture of the corresponding amine and aldehyde.

The 1: 1 chromium complex is prepared using methods known per se, preferably in acidic solution

The 1: 1 chromium complex, which contains 38.9 parts of the dye from diazotized 5-nitro-2-amino-l-hydroxybenzene and 1-hydroxynaphthalene-4-sulfonic acid and 5.2 parts of chromium, is introduced into 500 parts of water and with 23.4 parts of 4-nitro-2-amino-l-hydroxybenzene-6-sulfonic acid and 26 parts of the monoazo dye from diazotized 2-chloro-l-aminobenzene and salicylaldehyde.

The reaction mixture is then heated to 80 to 85 °, adjusted to pH 7 with sodium hydroxide and kept at this temperature and constant pH until the starting products are no longer detectable. After the addition reaction has ended, the dye is precipitated by adding 65% sodium chloride and filtered. After drying, a dark powder is obtained which dissolves in water with a green color and dyes leather in green olive tones of good fastness properties.

55

60

667 465

4th

Example 2

° 2N \ A

? ° 3

s \ A • • •

I II I

11 1 V - M

•. «- N = N-« •

^ y \ y

: Cr "

0/0

1 / 'A' s' \

N-N = N-r

II I

V

N0 "

II

V

A =

1, 0

Ï

/ \ A_

i u i

• v • J *

\

'SO.

3Na

0

Example 3

10th

20th

91

° i \ A

n

? ° 3

/ v \

I II I

j-N = N - v,

\ s i \ y \ ^

i

0 ^

U '

: cr:

0/0

1/1 A's

• «-N = CH-« • II I I II

\ y

V

Ä = N

À A • • •

I II I •. • _ •

w \ y \

so"

43.9 parts of the complex chromium compound of the 1 atom chromium type: 1 molecule of dye which contains 5.2 parts of chromium and 38.9 parts of mono-azo dye from diazotized 5-nitro-2-amino-1-hydroxybenzene are suspended in 500 parts of water and contains l-hydroxynaphthalene-4-sulfonic acid, with 15.4 parts of 4-nitro-2-amino-l-hydroxybenzene and with 35.6 parts of the monoazo dye from diazotized 1-amino-naphtha-lin-6-sulfonic acid and salicylaldehyde. The reaction mixture is then heated to 80 to 85 °, the pH is adjusted to 7 to 7.5 with 5N sodium hydroxide solution and the reaction mixture is kept at this temperature and constant pH until the starting products have disappeared. After the addition reaction has ended, the dye is isolated by evaporation. A dark powder is obtained which dissolves in water with an olive green color and dyes leather in real green olive tones.

The 1: 1 chromium complex, which contains 42.4 parts of the dye from diazotized 5-nitro-4-chloro-2-amino-l-hydroxybenzene and l-hydroxynaphthalene-5-sulfonic acid as well as 5.2 parts of 25 chromium, is in 500 parts of water are added and 15.4 parts of 4-nitro-2-amino-l-hydroxybenzene and 35.6 parts of the monoazo dye from diazotized 1-aminonaphthalene-6-sulfonic acid and salicylaldehyde are added. The reaction mixture is then heated to 80 to 85 °, adjusted to pH 7 to 7.5 with sodium hydroxide and kept at this temperature and constant pH 7 to 7.5 until the starting products can no longer be detected. After the addition reaction has ended, the dye is isolated by evaporation. After drying, a dark powder is obtained, 35 which dissolves in water with an olive-green color and dyes leather in olive-green tones with good fastness properties.

Examples 4 to 29

If one works as described in Examples 1 to 3, 40 however uses the 1: 1 chromium complex of the azo dye listed in column 2 in the following table and sets this with the azomethine dye listed in column 3 or with the amine and aldehyde forming it um, you get brown olive, olive or olive green 1: 2 Chromkom-45 complexes, which dye leather with good fastness properties.

N °

Azo dye

Azomethine dye

4th

<j) H <j> H • • •

left II II 1

o / v yv

S03H

<j) H <j> H II II II

V V

Ào2 Â = N -. /

V *

5

do

<j) H <j) H

A / \ lì no «Y, •

V \ /. ? 3rd

| j0o Ä = N - «^

2 1 II 1

• v • i *

V V

io3H

5

667 465

N °

Azofarbscoff

Azomequin dye

6

do

(j) H (j) H

\ -N = CH - * ^ \ »I l H

V V '¥ 3

5 ° 2 Â = N- / \

V

7

do

<j) H <j) H

Il II II

• •

À02 Â = N -. / \

V

Ì03H

8th

do

<j) H <j) H

y ^ • -N = CH - * ^ \

Il I I II \ ^ ^ /

bo2 ^ N-.7 N.

V 'NS03H

9

<j) H <j) H

«XT -A

• • -N = N— • • • Il II II I

• y * •, •

o / V V V

S03H

(j) H (j) H

• / ^ • -N = CH - «^ \

Il I I II • • •

• • f bo2 À = N -. / \

YX

S03H

10th

do

<j) H (j) H / \ -s, c »- / \

V V

ho2 À = N -. / \

Y still

S03H

11

<j) H <j) H

/ ^ ^ \ y \ h i l m i o / vv-vv-

(pH <j) H /%

.7 rN = CH "î .i

\ /% /? 3 • / •

Ào2 À = N -. / Nj |

V *

12

do

OH OH H03SN A A

h YN = CHY ff

• #V •

V V

Âo2 À = IjI

/ \

II 1

V *

667 465

6

N °

Azo dye

Azomethine dye

13

<j> H <j) H

/ ^ v f N / ^ • • -N = N— • • •

II 1 1 II 1

o / v v y

S03H

do

14

<j) H <pH

/% „„ S \ /%

m • —N = N "" • • •

II II II 1

• • •. •, m

0y v v y

S03H

<j) H <j) H Il II II

• 9/9

V V

Ào2 Â = y

A /% • • •

i n i

VV \ o3h

15

<j> H <j) H

/% M A /%

• • —W = N— • • •

Il II II l

•, + ®v •

"V y v y

Cl S03H

<j) H (j) H

/% A

•. -N-CH-. •

V * V! 3rd

NO2 Â = N- / n »

V

16

do lj) H (j) H

/% A

n.-N = CH- * •

Il II II

\ / "v *..

lo A = n- / S

1 2 1 II 1 »• •

X «/ X * / NS03H

17th

do

(j) H (pH

• / ^ »- NCH - * ^ Ns * Il II II • §. •

o / y y

Cl N = N

A / S03h • •

1 II

V

18th

do

OH OH

HO S

3 \ / ^ 4 \

• n «-N = CH-» '• Il II II

•. • •, •

V V

À02 À = IjI / \

1 II

• v •

V

7

667 465

N °

Azo dye

Azomethine dye

19th

<j) H <j) H

A .... A A

• • —N = N— • • • Il II II 1

• y * * »•

o y v y v

äOjH

OH OH

H03S \ A A

• • -N = CH- »• Il I I II

\ / V

bo2 Â = iji

A • •

i u

V

20th

do

OH OH

H03S \ A A i * * N CH r n v v

° 2

V

îl

21st

do

OH OH

h ° 3VwA

Il I I 11

v v x. .

NO2 b = N-y \

V \ i

22

do

OH OH

H03S \ A A

y Yn = chY »• •. •

V V

Ào A = N

/ V "» *

II 1 • / •

V

23

do

OH OH

H03S \ A A

• • -N = CH- * • Il II II

•, * * v •

V V

À02 À = ljJ

.A.

Il [

V NS03H

24th

(pH <j) H

• v * v

/ ^ ^ \ ^ • • —N = N— • • • il il n i

0 / v * V V

Ì03H

OH OH

H03S \ A A

Y YH-chy x. • • •

v v x.

Ä02 À = N - »/ X»

VNo ^

667 465

8th

N °

Azo dye

Azomethine dye

25th

<j) H (j) H

• v * v

/ ^ MM ^ \ ^ • • —N = sN— • • •

Il i l 11 1

o v Y Y v

Cl S03H

OH OH

H03SN A A n Î-N = CH "T n

• y® * v •

V V

Äo2 A = îjî

/ V \

1 II 1 • • •

x «7 X« x NS03H

26

do

OH OH

H03S \ A A

ii rN = CH-r ì

V v. Î ° 3h h

• v •

V V

£ O3H

27th

do

<j> H <j> H

• v •

/ ^ s \

m «-N = CH-« • Il II II

• «V •

V V

À02 A = IjI

/ v \

1 II 1

VV

S03H

28

<j) H <j> H

/ # ^ VT M / S

• • —N = N— • • * Il II II I

• * v • y *

o / v y v so3h

OH OH

ho3 \ A._B.CH..A.

Il I I II

'y * * v •

\ S \ /

• •

Âo2 À = ljl

/ V \

i! i i

V V XS03H

29

do

OH OH

H03S \ A A, 1. T «Y H / V #? 3 io2 I-N- / Y \

VV

âo3H

9

667 465

Dyeing instructions for leather

100 parts of suede clothing (dry weight) are rolled on at 50 ° in a solution of 1000 parts by volume of water and 2 parts of ammonia 24% for 2 hours and then at 60 ° in a solution of 1000 parts of water, 2 parts of ammonia 24% and 6 parts Dye from Example 1 colored for 1 hour. Then a solution of 40 parts by volume of water and 4 parts of 85% formic acid is added and the dyeing is continued for a further 30 minutes. Then the leather is rinsed well and optionally treated with 2 parts of a dicyandiamide formaldehyde condensation product for 30 minutes at 50 °.

Other suede and glove leather can be dyed in the same way.

The green olive dyeings obtained in this way are distinguished by good fastness properties and good hiding power.

Dyeing instructions for polyamide

100 parts of polyamide knitting yarn are introduced at 50 ° into a dyebath which contains 2 parts of the dye of the example, 4.4 parts of ammonium sulfate and 2 parts of a leveling aid per 4000 parts of water. The liquor is brought to the boil over the course of 45 minutes and kept at the boiling temperature for a further 5 45 minutes. The material to be dyed is then removed, thoroughly rinsed with cold water and dried. A green olive colored polyamide with good fastness properties is obtained.

io dyeing instructions for wool

100 parts of wool knitting yarn are introduced at 50 ° into a dyebath containing 2 parts of dye of the example, 4.4 parts of 80% acetic acid and 2 parts of a leveling agent per 4000 parts of water. The liquor is brought to the boil over the course of 45 to 15 minutes and kept at the boiling temperature for 45 minutes. The material to be dyed is then removed, thoroughly rinsed with cold water and dried. A green olive-colored wool with good fastness properties is obtained.

G