CH664763A5 - UNBALANCED CHROME COMPLEX DYES. - Google Patents

Description

DESCRIPTION Unsymmetrical 1: 2 chromium complexes of two azo dyes, one of which has 6-amino-2-naphthol-4-sulfonic acid as coupling component, are already known from EP-A 0 027 950 as intermediates for the production of reactive dyes.

The present invention relates to asymmetrical 1: 2 chromium complex dyes of the formula (1)

20th

wherein

Z nitrogen or a CH group,

25 A and D independently of one another each a residue of the benzene or naphthalene series which, in the o-position to the azo or azomething group, bears a hydroxyl or carboxy group,

B the rest of a coupling component if Z is nitrogen, the coupling component in the o or a position to the azo group containing the group X, or the rest of an o-hydroxyaldehyde if Z represents the CH group,

X is oxygen or, if Z is nitrogen, also a group of the formula -NR-, in which R is hydrogen or a C | -C4-35 alkyl group,

Y is hydrogen or a group of the formula -S02-Q or -CO- (O) nQ, where n is zero or 1 and Q is Cj-C5-alkyl or phenyl, the phenyl group being represented by nitro, halogen, C, - C5- Alkyl or alkoxy may be substituted 40,

p and q are each independently zero or 1 and Ka® is a cation, with the proviso that Y is not hydrogen when Z is nitrogen.

The dyes according to the invention are 45 asymmetrical 1: 2 chromium complexes. If A and D and p and q are identical, the coupling component B in one azo dye must not be identical to the coupling component in the other azo dye.

In the chromium complex dyes according to the invention of the formula (1) above, the radicals A and D can also carry one or more further substituents, e.g. low molecular weight alkyl or alkoxy, halogen, e.g. Chlorine or bromine, nitro, cyano, sulfo, carboxy, phosphono, alkylsulfonyl, e.g. Methylsulfonyl, sulfamides such as e.g. Sulfamide 55 or N-methylsulfamide, acylamino, phenylazo, sulfophenylazo or methoxyphenylazo. In this application, low molecular weight alkyl or alkoxy groups are generally to be understood as meaning those having 1 to 6, preferably 1 to 2, carbon atoms and “acylamino” means low molecular weight Al-60 kanoylamino, alkylsulfonylamino and alkoxycarbonylamino residues as well as aroylamino and aryloxycarbonylamino - and Arylsulfonylaminoreste called.

The residues A and D are derived, for example, from the following amines: anthranilic acid, 4- or 5-chloroanthranil-65 acid, 4- or 5-sulfoanthranilic acid, 2-amino-3-napthoic acid, 2-amino-1-hydroxybenzene, 4-chloro and 4,6-di-chloro-2-amino-1-hydroxybenzene, 4- or 5-nitro-2-amino 1-hydroxybenzene, 4-chloro, 4-methyl and 4-acetylamino-6 -

664 763

nitro -2-amino-l-hydroxybenzene, 6-acetylamino and 6-chloro-4-nitro-2-amino-1-hydroxybenzene, 4-cyano-2-amino-l-h \ droxybenzene. 4-sulfonamido-2-amino-1-hydroxybenzene, 1-hydroxy-2-aminobenzene-4-sulfoanthranilide, 4-meth-oxy-2-amino-1-hydroxybenzene, 4-methoxy-5-chloro-2-amino- l-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 , 6-acetylamino-4-chloro-2-amino-1-hydroxybenzene, 4,6-dinitro-2-amino-1-hydroxybenzene, 2-amino-1-hydroxybenzene-4 or 5-sulphonic acid. 4-nitro-2-amino-1-hydroxybenzene -6-sulfonic acid, 6-nitro-2-amino -1-hydroxybenzene-4-sulfonic acid, 4-chloro-2-amino-1-hydroxybenzene-6-sulfonic acid, l- Amino-2-hydroxy-naphthalene -4-sulfonic acid, l-amino-2-hydroxy-6-nitronaphthalene -4-sulfonic acid, l-amino-2-hydroxy-6-chloronaphthalene

4-sulfonic acid, l-amino-2-hydroxynaphthalene -4,6-disulfonic acid. 2-amino-l-hydroxybenzene -4,6-disulfonic acid.

Instead of the amines with hydroxyl groups mentioned above, suitable methoxy compounds or corresponding compounds whose hydroxyl group has been tosylated, such as anisidine, 4- or

5-chloroanisidine. 4- or 5-nitroanisidine, anisidine-4- or -5-sulfonic acid, or tosylated l-hydroxy-2-aminobenzene, the methoxy or O-tosyl group being converted into an OH group before or during the metallization. Connections with these groups are mainly used then. if the corresponding l-hydroxy-2-amino compounds couple poorly.

In preferred dyes of the formula (1), A and D represent the residue of an l-hydroxy-2-aminobenzene, which is optionally substituted by halogen, nitro, sulfo or low molecular weight alkyl or alkoxy, or the residue of an l-amino-2-hydroxy -4-sulfonapthalene, which is optionally substituted in the 6-position by halogen, such as bromine or in particular chlorine, nitro or sulfo.

Of the dyes of the formula (I), those in which Z is nitrogen are preferred.

The radical B is preferably derived from the following groups of coupling components: phenols optionally substituted by low molecular weight alkyl or alkoxy, dialkylamino or acylamino and coupling in the o-position, acylamino being C | -C4-alkanoylamino, Cj-C4-alkylsul-fonylamino- , C] -C4-alkoxycarbonylamino, aroylamino or arylsulfonylamino residues; Naphthols which are optionally substituted by C 1 -C 4 -alkyl or alkoxy, chlorine, amino, acylamino or sulfo, where acylamino has the same meaning as given above; 5-pyrazolo-ne or 5-aminopyrazoles, preferably those which have a phenyl or naphthyl radical which is optionally substituted by chlorine, nitro, C 1 -C 4 -alkyl or alkoxy groups or sulfo groups in the 1-position and in the 3-position a C 1 -C 4 alkyl or carboxy group. in particular have a methyl group; Naphthylamine, optionally with sulfo. Sulfonamido or sulfone groups are substituted; Acetoacetic acid amides, especially acetoacetic acid anilides, and benzoylacetic acid anilides, which may be substituted in the anilide core with chlorine, bromine, nitro, Ci-C4-alkyl or alkoxy or sulfo groups; 6-hydroxy-3-cyano or 6-hydroxy-3-carbonamido-4-alkyl-2-pyridones, which are in the 1-position by optionally substituted C 1 -C 4 -alkyl. e.g. Methyl, isopropyl, ß-hydroxyethyl, ß-aminoethyl or γ-isopropoxypropyl or substituted by phenyl, and in the 4-position can carry a C 1 -C 4 -alkyl group, in particular methyl, or hydroxyquinolines.

Examples of such coupling components are: 2-naphthol. 1-naphthol. l-acetylamino-7-naphthol, 1-propionyl-amino-7-naphthol, 1-carboxymethoxyamino-7-naphthol, 1-carboethoxyamino-7-naphthol, 1-carbopropoxyamino-7-

naphthol, 6-acetyl-2-naphthol, 2-naphthol-3-, -4-, -5-, -6-, -7- or -8-sulfonic acid, l-naphthol-3-, -4- or - 5-sulfonic acid, l-naphthol-3,6- or -4,8-disulfonic acid, 2-naphthol-6,8-disulfonic acid, 4-methyl-l-naphthol, 4-methoxy-l-naphthol, 4- Acetyl-l-naphthol, 5,8-dichloro-l-naphthol, 5-chloro-l-naphthol, 2-naphthylamine, 2-naphthylamine-l-sulfonic acid, l-naphthylamine-4- or -5-sulfonic acid, 2- Aminonaphthalene-6-sulfonic acid, 2-amino-naphthalene-5-sulfonic acid, 6-methyl-sulfonyl-2-aminonaphthalene, l-phenyl-3-methyl-pyrazol-5-one, l-phenyl-5-pyrazolon-3- carboxamide, l- (2'-, 3'- or 4'-methylphenyl) -3-methylpyrazo -5-one, l- (2 ', 3'- or 4'-sulphophenyl) -3-methylpyrazole-5 -on, l- (2'-chloro-5 '-sulfophenyl) -3-methyl-pyrazole -5-one, l- (2'- or 4'-methoxyphenyl) -2-methyl-pyrazole -5- on, l- (2'-, 3'- or 4'-chlorophenyl) -3-methylpyrazole -5-one, l- (2'-, 3'- or 4'-nitrophenyl) -3-methylpyrazole - 5-one, l- (2'-, 5'-or 3 ', 4'-dichlorophenyl) -3-methyl-pyrazol-5-one, l- (2', 5'-dichloro-4'-sulfophenyl) -3-methylpy -razol-5-one, l- (2'-, 3'- or 4'-sulfophenyl) -3-methyl-5-aminopyrazole, l-phenyl-3-methyl-5-aminopyrazole, l- (2nd '-Chlor-5'-sulfophenyl) -3-methyl-5-aminopyrazole, acetoacetanilide, acetoacetanilide-4-sulfonic acid, acetoacet-o-anisideide, aceto-acet-o-toluidide, acetoacet-o-chloroanilide, acetoacet-m- xyli-did, tetralol, 4-methylphenol, 3-dialkylaminophenols, especially 3-dimethylamino and 3-diethylaminophenol, 4-butylphenol, preferably 4-tert-butylphenol, 4-amylphenol, in particular 4-t-amylphenol , 2-isopropyl-4-methylphenol, 2- or 3-acetylamino-4-methylphenol, 2-methoxycarbonylamino-4-methylphenol, 2-ethoxycarbonylamino-4-methylphenol and 3,4-dimethylphenol, l-methyl- 3-cyano-4-ethyl-6-hydroxypyridone, l-methyl-3-cyano-4-methyl-6-hydroxypyridone, l-phenyl-3-carbonamido-4-methyl-6-hy-hydroxypyridone, l-ethyl -4-hydroxy-2-quinolone, 2,4-dihydroxyquinoline or 3-methylpyrazol-5-one.

Coupling component B is preferably 1-or 2-naphthol, optionally substituted by amino and / or sulfo, optionally 1- or 2-naphthylamine, optionally substituted by sulfo, p-alkyl- (C 1 -C 6) -phenol, 1-phenyl-3 -methyl-5-pyrazolone or acetoacetic anilide, it being possible for the phenyl group in the latter two compounds to be substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, chlorine, nitro or sulfo.

If Z is the CH group, B represents the residue of an o-hydroxyaldehyde, preferably an o-hydroxybenzaldehyde or o-hydroxynaphthaldehyde, which is substituted by low molecular weight alkyl, halogen, sulfo, phenylazo, sulfophenylzo, naphthylazo or sulfonaphthylazo can. Suitable aldehydes are, for example: 2-hydroxy-1-naphthaldehyde, I-hydroxy-2-naphthaldehyde, 2-hydroxy-benzaldehyde, 3-and 5-methyl-2-hydroxybenzaldehyde, 3,5-dimethyl-2-hydroxybenzaldehyde, 5- Butyl-2-hydroxybenzaldehyde, 5-chloro- or 5-bromo-2-hydroxybenzaldehyde, 3-chloro-2-hydroxybenzaldehyde, 3,5-dichloro-2-hydroxybenzaldehyde, 5-sulfo-2-hydroxybenzaldehyde, 3 -Methyl-5-chloro-2-hydroxybenzaldehyde, 5- (phenylazo) -2-hydroxybenzaldehyde, 5- (2'-, 3'- or 4'-sulfophenylazo) -2-hydroxybenzaldehyde, 5- (6 ' -Sulfonaphthyl-l'-azo) -2-hydroxybenzaldehyde or 5- (4 "-Sulfo -4'-phenylazo) -phenylazo- 2-hydroxybenzaldehyde.

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

Suitable radicals Y in the dyes of the formula (1)

Examples include: hydrogen, acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl, pivaloyl, capronyl, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, n-pentoxycarbonyl, methylsulfonyl, ethylsulfonyl, butylsulfonyl, phenylsulfonyl, benzoyl or phenoxy

4th

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

5

664 763

Phenyl groups in the latter three compounds may be substituted, e.g. by nitro, halogen, such as bromine or especially chlorine, Q-Q-alkyl or alkoxy.

Y is preferably hydrogen, acetyl, methoxycarbonyl, benzoyl, phenylsulfonyl or methylphenylsulfonyl and in particular hydrogen, methoxycarbonyl or acetyl.

Particularly preferred dyes according to the invention correspond to the formula (2)

produces and then this with the dye of formula (4)

/ ^ / \

SO,

.0

2Ka

©

OH 1

(C0) p d - n = n oh I

I II / ^ / \

»A K

A - N = Z (co> q oh

- b I

xh

(4)

10 or a mixture of the amine of the formula (5)

a -I

eco)

I.

oh nh

(5)

(2) and the aldehyde of formula (6) v '20

ii so3h

V

I.

n-h i

HO-B-CHO

(6)

V

'/ \

V

wherein

A 'and D' independently of one another each the residue of an l-hydroxy-2-aminobenzene, which is optionally substituted by halogen, nitro, sulfo, low molecular weight alkyl or alkoxy, or the residue of an l-amino-2-hydroxy-xy-4 sulfonaphthalene, which is optionally substituted in the 6-position by nitro or sulfo,

B 'a 1- or 2-naphthol optionally substituted by amino and / or sulfo, optionally 1- or 2-naphthylamine substituted by sulfo, p-alkyl (Ci-C6) phenol, l-phenyl-3-methyl-5-pyrazolone or acetoacetic anilide, where the phenyl group in the latter two compounds can be substituted by C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, chlorine, nitro or sulfo,

Y 'is methoxycarbonyl or acetyl and Ka® is a cation.

The dyes of the formula (1) according to the invention can be prepared by methods known per se, for example by using the 1: 1 chromium complex of the azo dye of the formula (3-)

to the 1: 2 chromium complex, or by preparing the 25 l: 1 chromium complex of a dye of the formula (4) and then reacting it with the dye of the formula (3).

A, B, D, Z, X, Y, p and q have the meaning given under formula (1).

The new metal complex dyes obtainable by the above processes are advantageously isolated in the form of their salts, in particular alkali metal salts, such as lithium, potassium salts, but above all sodium salts, or also ammonium salts. They are suitable for dyeing a wide variety of natural or synthetic materials 35 containing nitrogen groups, such as polyamides, polyurethanes, wool or, above all, leather.

The dyes of the formula (1) which have 1-2 sulfo groups are particularly suitable for dyeing wool or synthetic polyamide. The dyeings obtained are 40 uniform and have good fastness properties, such as fastness to light, washing, water, hot water, perspiration, rubbing, flexing, decaturing and carbonization.

Dyes with 2 to 5 sulfo groups are preferably used for dyeing leather. These dyes are 45 strong in color and cover well. They have good drawability and good acid and alkali stability and give dyeings with good fastness properties, such as diffusion, light, acid and alkali fastness. The good build-up ability on various types of leather deserves special mention, both on leather tanned only with chromium salts and on leather retanned with vegetable or synthetic tanning agents. You get olive, brown, blue or gray to black shades.

In the following examples, the parts, unless otherwise indicated, are parts by weight and the percentages are percentages by weight. The temperatures are given in degrees Celsius.

(3)

664 763

6

example 1

no2

.À. ° 3SV \ / \

U i- n = N - • i Ì

o3s / y / y v \ h2

/ ^ / \

so.

4 © 4 Na

©

7.5 and the reaction mixture kept at this temperature and constant pH until the starting dyes have disappeared. After the addition reaction has ended, the dye is precipitated by adding potassium chloride, filtered and dried. After drying, it is a dark powder that dissolves in water with a gray color and dyes leather in very real gray tones.

Example 3

(7)

NH-COCH "

The 1: 1 chromium complex, the 48.4 parts of the dye from diazotized 4-nitro-2-amino-1-hydroxybenzo-6-sulfonic acid and 2-amino-8-hydroxynaphthalene -6-sulfonic acid and 5.2 parts Contains chromium, is added to 600 parts of water and mixed with 44.6 parts of the monoazo dye from dia-zotiert 4-nitro-2-amino-1-hydroxy-benzene and 2-acetyl-amino-6-hydroxynaphthalene -8-sulfonic acid. The reaction mixture is then heated to 80-85 °, 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 reaction has ended, the dye is isolated by evaporation. A dark powder is obtained which dissolves in water with a gray color and dyes leather in very light gray shades.

NO "

/ \

Example 2

° 3S \ A A

'S' \ h "

/ ^ y \

so.

NH-COCH,

S ©

5 Na ©

25th

30th

° 3S \ ./>_/

(9)

48.9 parts of the complex chromium compound of the 1 atom chromium: 1-molecular dye type, which contains 5.2 parts of chromium and 43.9 parts of monoazo dye from diazotized 6-nitro-1-amino-2-hydroxynaphthalene, are suspended in 600 parts of water Contains -4-sulfonic acid and 2-hydroxynaphthalene 35, with 43.9 parts of the monoazo dye from diazo-tied 6-nitro-4-methyl-2-amino-1-hydroxybenzene and 2-acetylamino-6-hydroxynaphthalene-8-sulfonic acid. The reaction mixture is then heated to 80-85 ", the pH is adjusted to 7 to 7.5 with 5N sodium hydroxide 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 becomes precipitated by the addition of potassium chloride, filtered and dried, and after drying it is a dark powder which dissolves in water with a blue color and dyes leather in blue shades of good fastness properties.

The 1: 1 chromium complex of the 48.4 parts of the dye from diazotized 4-nitro-2-amino-1-hydroxybenzene -6-sulphonic acid and 2-amino-8-hydroxynaphthalene -6-sulfonic acid and 5.2 parts of chromium contains, is introduced into 600 parts of water and mixed with 52.6 parts of the monoazo dye from diazotized 4-nitro-2-amino-1-hydroxybenzene -6-sulfonic acid 55 and 2-acetylamino-6-hydroxynaphthalene -8-sulfonic acid. The reaction mixture is then heated to 80-85, and the pH is brought to 7 to 5N with sodium hydroxide

4Na

©

(10)

7

664 763

The 1: 1 chromium complex, the 48.4 parts of the dye from diazotized 4-nitro-2-amino-1-hydroxybenzene-6-sulfonic acid and 2-amino-6-hydroxynaphthalene-8-sulfonic acid as well as 5.2 parts Contains chromium, is introduced into 600 parts of water and mixed with 15.4 parts of 4-nitro-2-amino-1-hydroxybenzene and 30.6 parts of the monoazo dye from diazotized l-aminobenzene-2 -sulfonic acid and salicylaldehyde.

The reaction mixture is then heated to 80-85, adjusted to pH 7 with sodium hydroxide and kept at this temperature and constant pH until the starting products can no longer be detected. After the addition reaction has ended, the dye is isolated by evaporation. A dark powder is obtained, which dissolves in water with an olive color and dyes leather in genuine olive tones.

Example 5

NO 1

oO

° 3S \ A A c "£>

... 5N ^

KT - m «*

.1- N = N - • • .1

/ V V N »

° 3svV I.,.

H l ti I

^ ^ y \ / \ f

; • •

D i

V

I.

NO "

0oS

nhcoch3 p

3Ncï

I j I

/ y,., y sî

/ v'v i

NO "

II I

V

I.

nhcoch3

no I

.A

./% ° 3s \ A.A.

V "N = f" VVv nhcoch,

.0

4 na

©

(H)

48.4 parts of the monoazo dye from diazotized 4-nitro-2-amino-1-hydroxybenzene-6 sulfonic acid and 2-amino-8-hydroxynaphthalene-6 sulfonic acid and 44.6 parts of the monoazo dye from diazotized 4-nitro 2-amino-2-hydroxybenzene and 2-acetylamino-6-hydroxynaphthalene-8 -sulfonic acid are stirred in 400 parts of water and after the addition of 300 parts by volume of a solution of chromium salicylic acid sodium (corresponding to 6.25 parts of chromium) so long at reflux cooked until the starting dyes have disappeared. After chroming is complete, the mixture of the chromium-containing dyes is precipitated by adding potassium chloride and filtered. After drying, a dark powder is obtained, which dissolves in water with a gray color and dyes leather in very real gray tones.

If the procedure is as described in Examples 1-5, but using the 65 azo or azomethine dyes listed in the following table, 1: 2-chromium complex dyes are obtained which have the nuances indicated in the last column and leather with good Color fastness.

664 763

Table No.

501

Oh

/ ^

0 n- * • -

2 II I • •

ch,

Oh

• n-n-V \

V

nh-co-ch,

Oh oh

À}

ho "s- * n" -n = n-® / \

J U 1 in

®> # -

V

no,

O ©

/ v /

II

W a

\ ^

Nuance gray-blue

502

Oh

I •

/ ^

° 2n "II r • •

v ch,

Oh

^ \

• n = n- * •

i Ü

{Y xso3h

V

Oh oh

I ^ \

• c - n— • •

/ ^ f \ Il h03s ~ m * ~ n = n ~ c \ 1 ® \ / • ® c = n no,

I.

ch,

brown nh-co-ch,

503

Oh

/ ^

° 2n- «T? • •

v ch,

oh I.

t \

-n = n- «•

(Y • •

Oh

I ®

/ ^

@ ®

! 1 1

© o \ #

c

I.

no_

Oh

-n = n-c.

/ "n-

\

7

| Q C

\ = n l I

ch,

so3H

brown nh-co-ch,

504

Oh

/%

° 2n-. > • •

V

-n = n-

oh I.

ch,

• •

/ ^ / \

II

s03h

V

I.

nh-co-ch,

Oh

0 "n-o * -n = n-c oh

I •

£ _ N_./ \ V I II

I.

89 @

®

I.

s03h

\ = n ch,

brown

505

Oh oh

0 "n - * / x» -n = n- *; ' 2 II II m

V / V \ o h

I II I 3

ch3 \ /

nh-co-ch "

oh oh I

9

J \

/ '^

° 9n ~ m f "n = n-«

2 'i i 1 II

• • O a

^ / • © ©

I II I

@ @

so.h \ ^ 3 ®

blue

Table (continued)

No.

506

OH

OH

I.

/% ^ \ 0oN ~ ì? Xr-N = N "7 lì

V

I.

ch "

l Ü

• 7 v so 11 11 3

OH

I.

OH I

/ \ / r \ / ^

ho3s-. n.-n - »- r •; -nh2

V

no,

/ v v so3h

664 763

Shade blue-gray nh-co-ch-

507

° 2N-.I

oh I.

A

V *

I.

ch_

• -n = n- *

oh 1st

A_

{Y No3H

V

i nh-co-ch.

Oh oh

.ArN, N ../ y

\ / A.A./

i so "h no,

blue-gray

508

o2n-

oh I.

A,

vw

I.

ch "

| -n = n- *

Oh

A.

/ Y \ o3h

V

• i nh-co-ch,

oh I.

/%

• -n = n-c.

9H /

no,

\

-n

A.

C = N I

ch "

V

brown

509

oh 1st

Oh

S \ S \

0 "n_ * • -n = n - * / •

V

i

CH.

"7 V No3H V"

1

nh-co-ch "

Oh oh

(YN = NY V / V

s03h violet blue

510

oh oh 1

/% A

o n— • • -n = n ~ * • 2 11 II 11

V ./ V N

I II I

so3h

CH.

V

- I

nh-co-ch,

oh I.

Oh

«Vii7 v -» - f Y ^

V / Wk i s03h 2

no,

blue

664 763

10th

Table (continued)

No.

nuance

511

512

Oh oh

ì i o2n-. yn-ny îî

V / VVH

1 II I 3

ch v I

nh-co-ch "

Oh oh

I I

• •

° 2 »Y Yn = nY x5

* y * / vVa

1 11 1 3

ch3 y nh-c0-ch "

OH

I.

/%

? -N = N— •

9,

OH

I.

• •

^ \ / V

blue-gray ho „s

/ V \ / V V v

V

I.

. S03H

no oh I

/ \

V

1

no "

• -n = n- *

2nd

Oh

I.

©

/ ^ / • •

I I • •

OK '

violet-colored black

513

514

515

oh I.

.A

oh I.

• -n = n -? ^ N

V

no "

Oh

(Y Xs03h

I.

nh

A

I I • •

V

I.

NO,

Oh

• -n = n-r

2nd

oh I.

A.

y v

/ Y \ o3h v

i nh

oh I.

^ \

II

• •

• -n = n- *

no,

i'YV V

I.

nh "

Oh oh

I I

• ©

• • —n = ch— • • i i i ii

\ ^

I.

no2

Oh

I •

/ ^ • «

II I

V

I.

no "

^ /

'a

»-N = ch-

Oh

I.

©

y \

ii

V

1 A

n = n- * •

i ii ® •

V

sooh oh oh e

/ ^

• n «-n = CH-

• •

V

I.

no_

©

^ /

S © •

1 ii

\ A

vc1

s03h olive olive olive

Tahcllc (continued)

No.

516

oh I.

/%

Oh

V

I.

no,

I.

6 \ • -n = n- "•

I I II

■

V

I.

nh "

11

Oh oh

• / ^ .- N = CH - »^ X <

il i

V *

I.

NO "

V

1 A

n = n- * •

/% / "

• • •>

\ *

I.

so3h

664 763 Nuance olive

517

oh I.

/%

II

Oh

I •

^ \ • -n = n ~ * •

V

no,

{Y >> = • •

nh "

OH. I.

.A

II

NO "

• -n = ch-f oh I

A_

V

I.

n = n-

^ \ • •

I II

% y *

brown

518

OH I

/ ^

; .- N = N- *

oh I.

A.

V

I.

NO,

II

/ \

'S03H

V

I.

nh "

oh I.

0 /

./ \ _M =

II I

.-N = CH ~ »

oh I.

A.

so3h

V

i

N = N-

II

• •

/ V •>

Y

so3h brown

519

HO S

OH

\ -N = N II

OH

V

I.

NO,

l il

/ NS0 H il I 3

V

I.

NH "

OH I

II

-N = CH

V

I.

N0 "

oh I.

A - • •

II

V

I.

CI

olive

664 763

Tahcllc (continued)

No.

Oh oh

I I

520 "03s- / \ -m.k-.A.

V / / ^ / \

I II

no2 \ /

nh "

so3H

12

Oh oh

«I> o

/ ^ S \

e ®-N = rH-o »li i I il

\ /% / C1

no,

i w

^ \ n = n-® ® I II

Ci ©

ice olive oh oh I

5 ,, H03 \ A / X • • • •

/ ^ / \, • • ®

li no2 \ y \

nh,

• '' SO, H

Oh oh

© O

/ ^ fi \

© Q - ^ J = Cì ^ —O O

NI II!

© ©

i i no

SO H

^ \

2 n = n ~ ® •

0 9

V \

'ci olive oh oh oh so3h oh

"2" »vY Y» -Y x; • • • •

\ ^ ^ / \

• • N »cn u

I II I 3

no \ /

2 •

nh,

O O

/ ^ fi \

\ /

n02 n = n-

v

© 0

I II © ©

\> ch,

olive so3H

523

OH 0H

l •

HO »S. j ^

3 \ / X.-N = N- * il

\) / ^ / NojH

I}

80 2 V.

NH,

Oh

OH

/ ^ ^ \

• ° _N = CH-® •

. 1 1 'i SO, H

\ y ^ /, 3

t no,

| ® ^ \

n = n ~ ® • I II

© a

\O.

olive

OH

oh ho3 \ A A

524, •.

• • • •

\ ^ / ^ / \

• • N «Qf) 1y

I II I 3

no2 \ t /

nh,

oh I.

.A

II

• c

\ s

? -N = CH-

'OH I

A

■ © ®

in the • "

COOH

no. n = n-® ^ \

1 I II

® *

V /

olive

13

664 763

Tahcllc (continued)

No.

525

OH

OH

H03S \ À À

Y Î * Î "

\ / .A Ago h i n i 3 NO \ /

I.

NH.

OH

OH

OH

I.

OH

c \ A A

• «-N = CH- *. •

11 1 i 'i en h

\ .y, 3

I.

NO,

OH

^ \

m = N- «• 1 I II

V

OH

s ° 3h

Nuance olive

HO.S / \ # x.

3 N / ^ .- N = N • u 526 11 l i •

'V • / V SV

* 1>

no 2

{v »<- cH.yx, - • • •. •

rf2v brown

NH,

528

OH I

OH

H03S \ A A

527 Y Yn = N-. fi

\ / / V \ 0 H I II I 3

N02

NH

OH

HC \ Sv À

2 OH

3S \ A N ".A

iì rN = N * r fi

•. , • .v • -

\

■ / s V V

I H I

NO \ /

I.

NH "

H

OH

A / N = CH-

• •

II I

* 6 \ '

OH

OH I

.A.

I II • •

V

1 A

N = N- * •

OH I

• / ^ «- n = ch -» ^ n. «;

'J l i li SO H

V I 3

I II • •

N = N-

brown brown

OH

H01SV V

3 \ / ^ S \

5 "> 9 n.-N = N - * / •

J i »l 41" I II

OH

il i LU

V / V \ 0, H

I II I S

no \ y

NH,

OH

OH

• 7 ^ • -N = CH - * ^ X »'J l l" SO H

/ \ ^ ^ /, 3

No y f i

2 ^ \

N = N- * •

I II • •

V

I.

S03H

brown

664 763

14

Tahcllc (continued)

No.

OH

h03s \ à li I

î t

530

-n = n-

OH

I.

.A.

no,

II

I. I

./ V x

II I

t •

so3h

OH

I.

oh I.

/ ^ fi \

- • -n = ch- * •

il li

\ ^ /

NO,

Nuance olive nh,

Oh

531

532

H03S \ A ""

oh I.

A.

V

1

n02 oh

II

• •

/ ^ \ »•

I I • •

V

I.

nh2 oh s03h h03s \ A A

n YN = NY • • • • •

\ S / \ / \

r, i r S03h no,

V

I.

nh "

oh I.

A

• I

II I

• •

V

I.

'no.

-n = ch '

oh I.

. A - © •

I II »•

V

1 A

n = n- * • • •

Oh oh

I I

• ®

/ ^ 4 \

•? -N = ch-® • II II I!

I • o •

V

I.

no "

so3H

S \ N-N-f '•

brownish olive olive

533

Oh oh

I.

A.

Il h03s \ A „„ /

-N-N-

II I I II

Y fYV

no \ s I

nh "

Oh oh

I I

«®

»• -n = ch-® •

V

no,

V

I.

n = n-r

^ \

• •

V /

so3h olive oh oh oh Oh

534

h03s \ A n n A

h rN-B ~ i; • • © •

\ S / \ / \

s03h no2 \ s nh,

e »-n = ch-f ■

• •

®

1

n0 "

o ©

9

1

^ \ n = n- »•

olive

V \ o3H

15

664 763

Table (continued)

No.

535

OH

h03s \ A

• -n = n-?

OH

I.

A.

V

no,

/ ^ / \

11

V

1

nh,

• so3h oh 1

.A

II

V

I.

no "

• -n = ch-r

OH

I.

A.

Il

• •

so-h I

A

f I! • •

V

i s03h

Nuance olive

536

Oh

1

/ ^

s x.-n = n-

OH

.A.

il i i "

• • #v / V

V / V x:

I II I

m no2 \ /

'so3H

nh-co-och,

ho3s oh oh n /% r-N - "- i 'li

/ / V

.A.

Il II

V V

I.

no "

Gray

537

Oh oh

• / ^ .- n = N - * ^ II I I IJ

xso "h

1 'i 1 3

no \ /

I.

nhcooch_

oh 1st

.A.

II I

V

• I

no,

-n = n oh

А A / h2

I II I

/ v v so h gray

538

539

oh oh h03s \ À À

j x.-n = n-ì •

V

I.

n02 oh

II

7 ^ XS03H

V

I.

nh-cooch3 oh ho, s

3 \ '\ -N-N- / \

\ / / y \ o, H

I II I 3

no,

z I

nh-cooch_

oh oh h03S \ À 'À A / H2

Y i "n = n ~ * r. R n rn 1 i n i \ / / v

's03h gray

I.

no,

oh I.

.A

• -n = n-r oh

А A / h2

II I §rau

V

no,

so,

664 763

Table (continued)

No.

16

nuance

540

Oh

H03SS À

• -n = n- *

oh I.

A_

l no.

/ ^ / \

s03h

nh-co-?

Oh

H03SX À

© —n = n - °

• \ y

©

I.

no "

Oh

Ay \ / H2 il r

/ \ y so3h

Gray

541

oh h03s \ à • «

II I • «

V

I.

n0 "

-n = n-

oh I.

.A

/ ^ \

I.

S03H

\ y oh I

A

o ©

II I

0 0

\ /

I.

N0o

-n = n-?

Oh

A.A / h2 n Î

® ©

S03H

gray nh-co-?

S \

v /

542

oh I.

Oh

HO, S • «

3 \ ^ \ ^ \

r rN-B "r s v

no,

/ ^

• •

II I

• •

50 h nh-so2- «

v / \

ch,

oh ho s i 3 \ / ^

© ~ N = N "°

\ y

I.

no "

Oh

© © MU

^ \ / \ / 2 m?

Gray

/ V V

so3h

543

544

oh h03s \ a

• -n = n-

?H

.A_

V

I.

NO.

/ v / \

• so3h

\ y nh-s02- «

^ y \

ch3

oh I.

.A

'V

in O"

II

• ~ n = n- *

oh I.

A

/ ^ / \

n

50 h

V

I.

nh-coch,

Oh oh

©

y ^

? -n = n-

©

I.

no "

S \ z ^

»9 tons

II I © © ©

/ V \ / so3h

/ H2

Oh

I ©

y ^

• -n = n-f oh I

A

n ho3s

■ W «■

/ \ y \

© •

n n © ©

V V

I.

n0 "

gray gray-black

17th

664 763

Tahcllc (continued)

No.

545

OH

I.

II

y-N = N-r

OH

A.

V

i

NO,

II

/ ^ / \

II I I

NH-COCH

50 3H

OH

H03S \ À

OH

/% ^ \ 5 r ^ -r «

'i i v. •

v v

1 ">

NO

Nuance gray-black

546

OH

OH

• / \ -n = N -. ^ N i l! I

XS0 H I II [3rd

NO \ /

I.

NH-COCH,

OH

OH

H03S \ À

- "» -N = N-C,

S \

^ jC - N- * • brown

I I • •

V

I.

• N0 "

\ = N V

I.

CH,

547

OH I

• -N = N-f

OH

A.

• •

NO,

v

OH

OH

/ ^ 4 \ / ^

0oN-.T> -N «N-r ^ • •

2 II I

»R

V

I.

NO,

s / \ S

so3H

grey black

NH-COCH,

548

OH I

.A

I.

V "

I.

NO,

.-N = N-f

OH I

A.

n

*

v '

i

NH-COCH,

Il I SO3H

OH I

/%

*

II

V

I.

SO.H

OH I

/ \

N = N_ * yy • •

./ V

V

navy blue

549

OH

OH I

A

.-N = N-. .

V

I.

N0 "

/ ^ / \

50- H

V

I.

NH-COCH,

OH

O ^ -j / ^ pN = N-r

OH I

A.

Il

/ "V / -

II

so3H \ S

grey black

664 763

Table (continued) OH

No

550

OH

/ N;

«• •

/ VSO H

li I 3

V

I.

NO "

V

I.

NH-COCH,

18th

OH I

A

II

? -N = N- »

OH I

• •

^ \

HO SX N »^ X * X ^ NH,

3 I II SO H i

• • 3

V

NO,

Nuance gray-black

551

OH I

.A

I.

V

I.

NO,

• -N = N-

OH I

s \

/ \ / \

S03H

V

I.

NH-COCH,

OH

OH [

—N = N-C, I •

£ - N- »

^ Y

II I • «

V

. I.

NO,

\

C = N I

CH,

S03H

brown

553

OH

OH

55 ° / ^ f \

. > -N = N-f

Il I I II

\ / .A.AS0 H

I li I V

NO,

• •

V

I.

NH-COCH,

OH OH

s Vn-N- / \

Y / Y'V

NO,

i

NH-COCH3

OH I

/ \

II I • •

V

I.

NO,

OH

H03SS À

• i

II I

• 4

• \ ^

NO,

OH

-N = N-C.

/ "N-f a.

7

1 * *

NC = N I

CH,

OH

# \ —M = N— © o i n

® ®

©

i

W

brown brown

554

OH

H03S \ A • •

Il 1

-N = N-r

OH I

A.

Il

V

I.

NO,

/ ^ / \

S03H

V

I.

NH-COCH,

OH

H03SX K • •

II I • •

I.

NO,

-N = N-C,

OH

; - H-/\

f i i «

\ = N V

CH,

brown

19th

664 763

Tahcllc (continued)

No.

555

OH

OH

H03S \ A A

•> -N = N-r •

II

V

I.

no "

II

A / \

n

S03H

V

I.

NH-COCH,

nuance

OH

I.

A

i •

il i • «

V

• i

N0o

OH

I.

-N = N-C,

\

£ - N-I »

s v

II brown

C = N I

CH "

S03H

556

OH

H03SX À

V

I.

NO "

-N = N-r

OH I

A.

{y xso3H • •

i

NH-COCH.

II

OH I

A

V

i

NO.

r-N = N-c;

OH

£ - N-f ^ N »,

7, I II brown I • •

C = N N »

CH,

557

HO.S

OH ['

3 "\ .A

V

I.

NO,

• -N = N-?

OH

A.

• •

V

i

NH-COCH.

OH I

• .A

• -N = N-f

OH I

A.

ho3s

I.

* v •

/ W \ / A /

• •

i n n • • •

NO,

Gray

558

OH

H03S \ À

II

-N = N-

OH I

.A.

V

i

NO "

II

/ ^ / \

S03H

V

NH-COCH,

559

OH

H03S \ À

V

OH I

A

-N = N- * • • •

/ ^ / \

II

s03h

NO,

V

NH-COCH,

OH

H03S \ À

II

.-N = N-f

OH

A.

V

i

NO "

II

/ V

I 1 • •

V

Gray

OH 1

.A.

• V

—N = N— •

OH I

A

n

./ v /

Gray

NO,

V

664 763

20th

Tahcllc (continuation)

No.

560

Ott

OH

ho s • •

3 \ / ^ ^ \

• • —N = N — o «

n i l n

\ s i

NO "

/ ^ / \

ii

• so3h

V

I.

NH-COCH,

OH

OH

0 "N,

| N ® ®

2 \ / ^ ^ \

© o —M = M— o ©

h i i n o o o ®

W / ^ /

<is »ea so3h o ©

V

Shade gray

561

OH

H03SX A

II

? -N = N ~?

OH

^ Y

V

I.

NO,

/ ^ / \,

'SO H

I.

NH-COCH,

OH OH

I.

G

/ ^

/ "VX / _V V \ H

^ \ / ^

o-n = N ~ g • ® gray II II II I

H03S I II SO H

• \ / 3

NO,

562

563

OH

OH

I «

^ Y

, .7 ^ r-N = K-. ' .

\ / / V \ 0 H

I II I 3

NO,

NH-COCH

OH

H03SN À

• I

II I

• «

V

I.

NO,

-N = N- »

3rd

OH I

/ y

• •

y Y / \

50 h

«M n

oh I.

O

/ ^

0

1

no.

Q N = N ©

02N

OH I

/ \

5 ©

n

-N = CH-r

OH

I ©

^ \

M

'v'

W

OH

I «

II

O

V

©

i

N

brown brown

NH,

N I

y v xso3h

Fcirheviir.schrift für Leder

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 by volume of water, 2 parts of ammonia 24% and 1.5 parts of dye 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 more is colored

60 30 minutes. Then the leather is rinsed well and optionally treated with 2 parts of a dicyandiamide formaldehyde condensation product at 50 for 30 minutes.

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

The gray colorations obtained in this way are distinguished by good fastness properties and good hiding power.

Dyeing instructions for wool

100 parts of wool knitting yarn are introduced at 50 into a dyebath which contains 2 parts of the dye of Example 1, 3 parts of ammonium sulfate and 2 parts of a leveling aid per 4000 parts of water. The fleet is in the course of

664 763

Boiled for 45 minutes and held at cooking temperature for 45 minutes. The material to be dyed is then removed, thoroughly rinsed with cold water and dried. A dark gray wool with 5 good fastness properties is obtained.

21st

C.

Claims (12)

664 763 1 P D - N ,O 2 Ka ©. (i) (2) II I 2. Dyes according to claim 1, wherein A and D each independently of one another the residue of an l-hydroxy-2-amino-benzene, which is optionally substituted by halogen, nitro, sul-fo, low molecular weight alkyl or alkoxy, or the residue of a -Amino-2-hydroxy-4-sulfonaphthalene, which is optionally substituted in the 6-position by nitro or sulfo. 2 Ka © co where Z nitrogen or a CH group, A and D independently of one another each have a radical of the benzene or naphthalene series which bears a hydroxyl or carboxy group in the o-position to the azo or azomething group, B the rest of a coupling component when Z is nitrogen, the coupling component in the o- or a-position to the azo group contains the group X, or the rest of an o-hydroxyaldehyde if Z represents the CH group, X is oxygen or, if Z is nitrogen, also a group of the formula -NR-, where R is hydrogen or a C 1 -C 4 -alkyl group, Y is hydrogen or a group of the formula -S02-Q or -C0- (0) "- Q, where n is zero or 1 and Q is C | -C5 alkyl or phenyl, the phenyl group being represented by nitro. Halogen, Q-Cj-alkyl or alkoxy may be substituted, p and q are each independently zero or 1 and Ka® is a cation, with the proviso that Y is not hydrogen when Z is nitrogen. 2nd PATENT CLAIMS 1. Unsymmetrical 1: 2 chromium complex dyes of the formula (1) V '< . © (3) S ~ {X | j A7 Xso3h converts to the 1: 2 chromium complex, where A, B, D, Z, X, Y, p and q have the meaning given under formula (1). 3rd 664 763 to the 1: 2 chromium complex, where A, B, D, Z, X, Y, p and q have the meaning given under formula (1). (3) 60 65 produces and this then with the dye of formula (4) A - N = Z - B (CO) I 'OH XH Dyes according to claim 1 or 2, wherein Z is nitrogen. (4) produces and then this with the azo dye of the formula (3) OH 1 (CO) (4) 4. Dyes according to any one of claims 1 to 3, wherein Z is nitrogen and B is a 1- or 2-naphthol optionally substituted by amino and / or sulfo, optionally 1- or 2-naphthylamine substituted by sulfo, p-alkyl (C | -Q) -phenol, l-phenyl-3-methyl-5-pyrazolone or acetic acetic anilide, the phenyl group in the latter two compounds being Q-C4-alkyl, Q-C4-alkoxy. Chlorine, nitro or sulfo can be substituted. (5) and the aldehyde of formula (6) HO-B-CHO (6) starts. 5. Dyes according to claim 1 or 2, wherein Z represents a -CH group and B represents the residue of an o-hydroxy benzaldehyde, which can be substituted by phenylazo, sulfphenylazo, naphthylazo or sulfonaphthylazo. A '- N = N - B1 / ^ / \ I A < SO. , 0 2Ka © 6. Dyes according to claim 1, wherein Y is hydrogen, acetyl, methoxycarbonyl, benzoyl, phenylsulfonyl or methylphenylsulfonyl. 7. Dyes according to claim 6, wherein Y is hydrogen 5 or acetyl. 8. Dyes according to claim 1 of the formula (2) 9 9 V V wherein 30 A 'and D' independently of one another each the residue of an l-hydroxy-2-aminobenzene, which is optionally substituted by halogen, nitro, sulfo, low molecular weight alkyl or alkoxy, or the residue of an l-amino-2-hydro-xy- 4-sulfonapthalene, which is optionally substituted in the 6-position 35 by nitro or sulfo, B 'is a 1- or 2-naphthol optionally substituted by amino and / or sulfo, optionally 1- or 2-naphthylamine substituted by sulfo, p-alkyl (QC ^ phenol, l-phenyl-3-methyl-5-pyrazolone or Acetoacetic anilide 40 means, where the phenyl group in the latter two compounds can be substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, chlorine, nitro or sulfo, Y 'methoxycarbonyl or acetyl and Ka ® means a cation. 45 9. A process for the preparation of dyes of the formula (1), characterized in that the 1: 1 chromium complex of the azo dye of the formula (3) OH 50 I. (CO) I P D - N 55 = N-® ?H A " / y \ o3h ®. © 10. A process for the preparation of dyes of the formula (I), characterized in that the l.i-chromium complex of a dye of the formula (4) A - N = Z - B (CO) I «OH XH 11. The method according to claim 9 or 10, characterized in that instead of the dye of the formula (4), a mixture of the amine of the formula (5) A - (CO) I 'OH NH " 12. dye mixture containing at least one dye of the formula (1) according to claim 1.