CH616444A5 - Process for the preparation of asymmetric 1:2 cobalt complex azo compounds - Google Patents

Description

The present invention relates to a process for the preparation of asymmetric 1: 2 cobalt complexes of the formula ## STR1 ## in which X is hydrogen or nitro,

Ri and R2 independently of one another hydrogen, (1-4C) 25 alkyl or (1-4C) alkoxy, chlorine, bromine or nitro or R, hydrogen, chlorine or nitro and R2 -S02NR3R4, where the sulfonamide group or the radical R, the Occupy positions 4 and 5,

R3 is hydrogen or optionally substituted (1-4C) 1,1 alkyl ",

R4 is hydrogen or an optionally substituted (1-4C) alkyl, (5-6C) cycloalkyl or phenyl radical or

R3 and R4 together with the N atom bound to them, optionally with the inclusion of a further heteroatom, 35 form a non-aromatic 5- or 6-membered hetero ring,

B is the divalent radical of a coupling component of the 1- or 2-naphthol series which couples in the 2- or 1-position ortho to the hydroxy group and which is bonded to the cobalt atom via the oxygen atom, 4.1

D is the divalent residue of a coupling component of the 2-naphthylamine series, which couples in the 1-position ortho to the amino function, or the 5-aminopyrazole series, which couples adjacent to the C atom carrying the amino group, the cobalt atom in each case being bound via the amino function 45 and

M is hydrogen, an alkali metal ion or unsubstituted ammonium ion and

M 'is an alkali metal ion or unsubstituted ammonium ion, where the molecule contains a single sulfonic acid group 50 and can additionally carry only one sulfonamide group as the radical R2 or in D, or mixtures of compounds of the formula (I), characterized in that a 1: 1-cobalt complex compound in the form of the free acid of formula 55

m'O3S

©

M

B

HC ^ S-

CII)

(I),

where X is hydrogen or nitro,

R! and R2 independently of one another hydrogen, (1-4C) alkyl or (1 ^ 4C) alkoxy, chlorine, bromine or nitro or R [hydrogen, chlorine or nitro and R2 -S02NR3R4, where the sulfonamide group or the radical R, the positions 4 and occupy 5,

R3 is hydrogen or optionally substituted (1-4C) alkyl,

R4 is hydrogen or an optionally substituted (1-4C) alkyl, (5-6C) cycloalkyl or phenyl radical or

R3 and R4 together with the N atom bound to them, optionally with the inclusion of a further heteroatom, form a non-aromatic 5- or 6-membered hetero ring, B the divalent residue of a coupling component of the

1- or 2-naphthol series which couples in the 2- or 1-position ortho to the hydroxyl group and which is bonded to the cobalt atom via the oxygen atom,

D the double-bonded rest of a coupling component of the

2-naphthylamine series, which couples in the 1-position ortho to the amino function, or the 5-aminopyrazole series, which couples adjacent to the C atom carrying the amino group, the cobalt atom in each case being bound via the amino function and

M is hydrogen, an alkali metal ion or unsubstituted ammonium ion and

3rd

616444

M 'is an alkali metal ion or unsubstituted ammonium ion, where the molecule contains a single sulfonic acid group and can additionally carry only one sulfonamide group as radical R2 or in D, the compounds of the formula (I) prepared by the process or mixtures of compounds of the formula (I) and their use as dyes.

Swiss Patent No. 317 120 discloses the preparation of 1: 2 mixed metal complexes of two monoazo dyes, one of which carries a sulfo group, the other a sulfone or sulfonamide group. Mostly disclosed are chromium complexes with double o, o'-dihydroxyazoformation, as well as with o-hydroxy-o'-aminoazoformation in the sulfo group-containing monoazo dye and o, o'-dihydroxy azo grouping in the sulfo group-free monoazo dye. However, the 1: 2 cobalt complexes produced contain, in addition to an asymmetrical component, a high proportion of the two possible symmetrical complexes.

The 1: 2 cobalt complexes known from Swiss Patent No. 427 095 have an o, o'-dihydroxyazoformation in the sulfo group-containing dye, but the diazo component of this monoazo dye differs by the presence of a halogen atom in position 6 instead of hydrogen or nitro. These 1: 2 cobalt complexes also represent a mixture of asymmetrical and symmetrical complexes due to the way they are produced.

The preparation of the asymmetric 1: 2 cobalt complex compounds of the formula (I) or mixtures thereof is carried out according to the invention by using a 1: 1 cobalt complex compound in the form of the free acid of the formula

(II)

corresponds to

where L! and L2 each represent monodentate ligands with a compound of the formula

N »N -

H

1

D

(III)

or a mixture of compounds of the formula (III) or that a mixture of compounds of the formula (II) is reacted with a compound of the formula (III) in a neutral to alkaline medium.

s In complexes of the formula (I), the substituents which are mentioned as possible for the radicals R3 and R4 are those which are customary in azochemistry.

If R or R2 stands for alkyl, this preferably means methyl or ethyl and particularly preferably methyl; if R, 10 or R2 is alkoxy, this preferably means methoxy or ethoxy.

If R3 or R4 is an unsubstituted alkyl radical, this can be linear or branched and preferably contains 1 [5 to 3 carbon atoms, particularly preferably it is methyl, ethyl or isopropyl.

R3 or R4 in the meaning of a substituted alkyl radical represents straight-chain or branched-chain alkyl groups which preferably contain halogen such as chlorine or bromine, 20 hydroxy, cyano, (1-4C) alkoxy, in particular methoxy or ethoxy, or the phenyl radical can, with hydroxy, methoxy or ethoxy being particularly preferred as substituents, and in particular only a single substituent being present.

25 R4 as cycloalkyl means in particular cyclohexyl. A substituted cycloalkyl radical is preferably substituted by 1 to 3 methyl groups. R4 as a substituted phenyl radical is preferably substituted by halogen such as fluorine, chlorine or bromine, nitro, (1-4C) alkyl or (1-4C) alkoxy and indeed of 30 of the substituents listed, the phenyl radical is preferably by chlorine, nitro, methyl, methoxy or ethoxy monosubstituted or disubstituted by two methyl, methoxy or ethoxy groups. The phenyl radical is particularly preferably unsubstituted.

15 If R3 and R4 form a hetero ring together with the N atom bound to them, this preferably represents a pyrrolidino, piperidino or morpholino radical.

R3 is preferably hydrogen, (1-3C) alkyl or 2-40 or 3-hydroxy- (2-3C) alkyl and particularly preferably hydrogen; R4 preferably represents R'4 in the meaning of hydrogen, (1-3C) alkyl, 2- or 3-hydroxy (2-3C) alkyl, an RnO- (CH2) n radical, in which Rj is [methyl or ethyl and n is 2, 3 or 4, preferably 2 or 3, unsubstituted phenyl, phenyl monosubstituted by chlorine, nitro, methyl, methoxy or ethoxy or by two methyl,

Methoxy or ethoxy groups disubstituted phenyl, particularly preferably for R "4 in the meaning of methyl, ethyl, isopropyl, 2-hydroxyethyl, -CH2-CH (OH) -CH3, 50 - (CH2) 3-OCH3 or phenyl and still further preferred for R "'4 in the meaning of methyl, - (CH2) 3-OCH3 or phenyl.

R is preferably R't as hydrogen, methyl, chlorine 55 or nitro and particularly preferably hydrogen, chlorine or nitro and R2 is R'2 as chlorine or nitro or, if R 'is hydrogen, -S02NHR " 4 and particularly preferred for-S02NHR "'4.

The double-bonded radical B is preferably a radical of the formula 60

616 444

4th

v

(a)

1

(b)

or dar,

wherein Y [represents hydrogen (1-2C) alkyl or (1-2C) alkoxy, preferably methyl or methoxy, chlorine or bromine.

Y! for Y *! in the meaning of hydrogen, methyl or methoxy.

B is preferably a divalent radical of the formula (a), (b ') as the radical (b) with Y'b (c) or (c'V

The double-bonded residue D preferably represents t! no ?? your formula

NO

wherein

15 R12 is hydrogen, (1-4C) alkyl, preferably (1-2C) alkyl and particularly preferably methyl, (1-2C) alkoxy, methoxy being preferred, or phenyl and

R13 is hydrogen, (1-4C) alkyl, preferably (1-2C) alkyl, phenyl (1-4C) alkyl, preferably phenyl (1-2C) alkyl, 2d cyclohexyl or optionally substituted phenyl

Z1

(e)

dar,

wherein R5 is hydrogen, (1-4C) alkyl or a radical of the formula

R,

one of the radicals R6 and R7 is hydrogen, the other is hydrogen, chlorine, bromine, (1-2C) alkyl or (1-2C) alkoxy, methyl or methoxy being preferred, or trifluoromethyl, Rg hydrogen or methyl and R9 methyl or R8 hydrogen and R9 chlorine or bromine,

Y2 is hydrogen or, if the substituent R? does not stand for -S02NR3R4, also the rest -SO2NHR] 0 in position 5 or 6 and

R10 is hydrogen, (1-4C) alkyl or hydroxy (2-4C) alkyl or a radical of the formula

Zj hydrogen and

Z2 hydrogen, fluorine, chlorine, bromine, (1-4C) alkyl, preferably 30-wise (1-2C) alkyl, (1-2C) alkoxy, nitro or trifluoromethyl in all possible positions or

Zt = Z2 chlorine, bromine, methyl or methoxy, where if Z ^ Z ^ = chlorine, the two chlorine atoms in the positions

2.3; 2.4; 2.5; 2.6; or 3,4;

15 Z1 = Z2 = bromine, the two bromine atoms in the positions

2.4 or 3.5,

Z [= Z2 = methyl, the two methyl groups in positions 2,3; 2.4; 2.5; 2.6; or 3.5; and

Zi = Zj2 = methoxy, the two methoxy groups can be in the 40 positions 3,4 or

Z1 = Z2 mean 3-chloro-2-methyl, 4-chloro-2-methyl, 5-chloro-2-methyl, 4-bromo-2-methyl or 5-chloro-2-methoxy.

Z] and Z2 preferably independently represent hydrogen, chlorine or methyl.

R5 in the rest of the formula (e) as alkyl preferably represents methyl or ethyl. R5 stands for a rest

50

of the formula

preferably one of the radicals R6 and R7 is hydrogen, the other is hydrogen, chlorine, methyl or methoxy and particularly preferably hydrogen, chlorine or methyl.

55

NH I

C —N

I.

C —N I

R12

13

If R5 is a radical of the formula, Rs is preferably hydrogen or methyl and R9 is methyl or R8 is hydrogen and R9 is chlorine.

(f)

65

R5 preferably represents hydrogen, phenyl,

:H

CI with the chlorine atom in position 2, 3 or 4,

with methyl in

5

616 444

Position 2 or 4 or

, particularly preferably for hydrogen or phenyl and very particularly preferably for phenyl.

R10 as alkyl preferably contains 1 or 2 carbon atoms and particularly preferably means methyl; as hydroxyalkyl it preferably contains 2 or 3 carbon atoms with a 2- or 3-position hydroxyl group.

R10 preferably represents R'i0 in the meaning of hydrogen, methyl or 2-hydroxy (2-3C) alkyl.

Y2 is preferably hydrogen, in particular if R5 is not hydrogen, or -SO2NHR'10, in particular if R5 is hydrogen, and particularly preferably hydrogen.

The radical of the formula (e) preferably represents a radical of the formula, particularly preferably Z and Z2 independently of one another being hydrogen, chlorine or methyl. D preferably denotes the rest of the formula (e) and particularly preferably the rest of the formula (e ").

5 M and M 'are, independently of one another, preferably a lithium, sodium, potassium or ammonium ion.

Particularly noteworthy 1: 2 cobalt complex compounds correspond to the formula s ° 2nhR-0

(e ")

with -SO2NHR'I0 in position 5 or 6 or

(e ")

and very particularly preferably for the rest of the formula (e ") - R12 in the rest of the formula (f) is preferably methyl.

R [3 preferably represents the rest of the formula -1

Z2

In particular, the rest of the formula (f) represents the rest of the formula

WH I

C.

C = N I

CH_

(f)

m'03S

-Ó ~ h e

fi

35

50

55

(la),

wherein R'j is hydrogen, methyl, chlorine or nitro and particularly preferably hydrogen, chlorine or nitro and

R'2 chlorine or nitro or

R ', hydrogen and

R'2 -S02NHR "4 and particularly preferably -S02NHR '" 4 in position 4 or 5 and B' represent a double-bonded radical of the formula (a), (b '), (c) or (d).

To produce the asymmetrical 1: 2 cobalt complexes, stoichiometric amounts of a 1: 1 cobalt complex of the formula (II), in which the monodentate ligands Lj and L2 represent, for example, colorless inorganic or organic molecules which contain an oxygen or nitrogen grouping with electron donor properties , and in particular water molecules, and one or more metal-free monoazo dyes of the formula (III) in aqueous solution and / or in an organic solvent, for example a low molecular weight aliphatic carboxamide such as formamide or its derivatives or glycols such as ethylene glycol, di- or triethylene glycol or their ether, implemented. The reaction is carried out in neutral or alkaline medium and is complete after conversion of the entire 1: 1 cobalt complex used. The 1: 2 cobalt complex compound can then be isolated in a manner known per se, for example by salting out or weakly acidifying, and, after washing with brine, collected and dried.

The reaction is carried out analogously, starting from a mixture of compounds of the formula (II) with a compound of the formula (III).

The asymmetrical 1: 2 cobalt complex compounds of the formula (I) obtained in this way are distinguished by a very high purity; they contain the possible symmetrical 1: 2 cobalt complexes to a surprisingly small extent.

The 1: 1 cobalt complexes of the formula (II) used as starting material can, for example, be prepared by adding 1 mol of a compound of the formula

H

N = N - B

(IV)

616 444

6

at least 1 mole of a cobalt donating compound, such as cobalt (II) sulfate, acetate, formate or chloride, in the presence of an inorganic nitrite such as lithium, sodium, ammonium or potassium nitrite in a ratio of 2 to 6 moles of nitrite per gram atom of cobalt. This 1: 1 cobalting is carried out analogously to a manner known per se.

The dyes produced according to the invention and their mixtures are suitable for dyeing or printing organic nitrogen-containing substrates, in particular natural and synthetic polyamides such as e.g. Wool, silk or nylon, or of polyurethanes and for dyeing or printing leather, red and particularly gray or black, possibly reddish tones being obtained. The dye complexes can also be used for dyeing metals, in particular anodically produced oxide layers on aluminum metal.

The dyes can be used as such or in the form of liquid or solid preparations.

The dyeings obtained with the asymmetrical 1: 2 cobalt complexes produced according to the invention have very good properties, in particular very good light and wet fastness properties. They are also rub-fast and show good resistance to carbonization, ironing, wool chlorination and acids such as alkalis. Thanks to their asymmetrical nature, the new 1; 2 cobalt complex compounds are drawn onto polyamide fibers from a neutral medium and have the desired property of being the same tone. In the one-bath dyeing process, they also show the same build-up capacity on wool and on nylon. In addition, they are characterized by very good solubility in printing, whereby permanent printing pastes are obtained which build up well on all types of polyamide.

In the following examples, parts mean parts by weight, parts by volume relate to parts by weight in the ratio of liters to 5 kg. The temperatures are given in degrees Celsius.

example 1

In 600 parts of water and 300 parts of ethanol, 45 parts of the dye obtained by acid coupling of diazotized 2-amino-4,6-dinotro-l-hydroxybenzene to 2- (3'-chlorophenyl) aminonaphthalene and the paste of 44 Parts of the monoazo dye l-amino-2-hydroxy-6-nitronaphthalene-4-sulfonic acid, - »2-hydroxynaphthalene obtained 1: l-cobalt-l 5 complex, the preparation of which is described below, stirred in and added to pH 11 by adding sodium hydroxide solution , 0-11.5 set. The mixture is then heated to 30 ° and stirred at this temperature for 24 hours. If starting products are still detectable after this stirring time, the temperature is raised to 80 ° within 2 hours and stirring is continued until both starting compounds have completely disappeared. The pH must be kept at 11.0-11.5 during the entire reaction. The chromatogram of the asymmetrical 1: 2 cobalt complex formed in this way must no longer or only slightly show the 25 metal-free dye and the 1: 1 cobalt complex at all. The dye is salted out by adding sodium chloride, filtered off, washed with a 5% sodium chloride solution and dried. M It corresponds to the formula e

N / A

©

and is characterized by a high degree of purity (a maximum of 5% of the monoazo dyes used have been converted into the symmetrical 1: 2 complexes). The dye dissolves very well in water and dyes natural and synthetic polyamide fibers such as wool and nylon in a gray or black shade, whereby the dye from neutral bai absorbs very well and in the same tone. The dyeing has very good general wet fastness and excellent light fastness, and also good fastness to rubbing.

f, o The 1: 1 cobalt complex used as the starting material can be produced as follows:

28 parts of cobalt (II) sulfate are placed in a beaker. 7H20 and 28 parts of sodium nitrite dissolved in 500 parts of water. Then, with thorough stirring, 44 parts of the monoazo dye “5-substance l-amino-2-hydroxy-6-nitronaphthalene-4-sulfonic acid” 2-hydroxynaphthalene are introduced. The pH is adjusted to 5.6-6.0 during and after the addition of the monoazo dye and for about 20 hours therein

7

616 444

Keep area until the starting dye is completely converted into the 1: 1 cobalt complex. The temperature must be maintained between 20 and 30 ° during metallization. The 1: 1 cobalt complex is precipitated by salting out with sodium chloride, filtered off and washed with a 20% sodium chloride solution until the filtrate runs off cobalt-free. The paste of the 1: 1 cobalt complex obtained can be used directly for the conversion to the asymmetrical 1: 2 cobalt complex.

The following table shows the structure of other dyes; they can be prepared according to the information given in Example 1. For those with these

Dyes achieved dyeings on polyamide which have good light fastness and good wet fastness properties, the shade is given in column I,

s where a stands for black b for reddish black c for greenish black d for bluish black e for brown m f for reddish brown g for bordeaux and h for ruby.

Example Compound (s) of Formula (IV) Compound (s) of

N0. (used as 1: 1 co-complex) formula (III) (metal-free)

2 1 - Amino-2-hydroxy-6-nitronaphthalene-2-amino-4-chloro-1-hydroxy-6-nitroben-4-sulfonic acid - »■ 2-hydroxy naphthalene zol -» 2-phenylaminonaphthalene

3 do. 2-amino-4,6-dinitro-l-hydroxybenzene— »

2-aminonaphthalene

4 do. 2-amino-4,6-dinitro-l-hydroxybenzoli

2-phenylaminonaphthalene

5 do. 2-Amino-1-hydroxybenzene - »2-phenylaminonaphthalene

6 do. 2-amino-l-hydroxy-4-methyl-6-nitro

benzene - »2 - ('4-chlorophenyl) aminonaphthalene

7 th. 2-amino-l-hydroxy-4-methoxybenzoI - »

2-phenylaminonaphthalene

8 do. 2-amino-l-hydroxybenzene-4-sulfonic acid

reamide - »2- (2 ', 6'-dimethylphenyl) ami-nonaphthalene

9 th. 2-amino-l-hydroxybenzene-4-N- (3'-me-

thoxypropyl) sulfonic acid amide - »2-phenyl-aminonaphthalene

10 do. 2-amino-1-hydroxybenzene-4-N-phenyl

sulfonic acid amide - »2-phenylaminonaphthalene

11 do. 2-amino-1-hydroxybenzene-5-N-methyl

sulfonic acid amide -> 2- (4'-methylphenyl) aminonaphthalene

12 do. 2-amino-l-hydroxybenzene-4-N- (2'-hy-

droxypropyl) sulfonic acid amide - »2-phenylaminonaphthalene

13 do. 2-amino-4-chloro-l-hydroxybenzene-5-sul-

fonsäureamid - »2-phenylaminonaphthalene

14 do. 2-amino-4,6-dinitro-1-hydroxy benzene

2-aminonaphthalene-6-N- (2'-hydroxypropyl) sulfonic acid amide

15 do. 2-amino-4,6-dinitro-l-hydroxybenzene ->

2-Ethylaminonaphthalene

16 do. 2-amino-l-hydroxy-5-nitrobenzene - »3-

Methyl-1-phenyl-5-aminopy razole

616 444

8th

Example No. Compound (s) of Fortnel (IV) (used as a 1: 1 co-complex)

Compound (s) of the formula (III) (metal-free)

17th

18th

19th

20th

21st

22

23

l-amino-2-hydroxy-6-nitronaphthalene-4-sulfonic acid - * 2-hydroxynaphthalene l-amino-2-hydroxy-6-nitronaphthalene-4-sulfonic acid - * 2-hydroxynaphthalene and l-amino-2-hydroxynaphthalene-4 -sulfonic acid— »2-hydroxynaphthalene l-amino-2-hydroxynaphthalene-4-sulfonic acid - * 2-hydroxynaphthalene do.

do.

do.

do.

2-amino-4,6-dinitro-l-hydroxybenzene-3-methyl-1-phenyl-5-aminopyr azole

2-amino-4,6-dinitro-l-hydroxybenzene-2- (3'-chlorophenyl) aminonaphthalene do.

2-amino-4,6-dinitro-1-hydroxybenzene -> 2-phenylaminonaphthalene and 2-amino-4,6-dichloro-1-hydroxybenzene - s 2-phenylaminonaphthalene

2-amino-4,6-dinitro-1-hydroxybenzene - »2-aminonaphthalene

2-amino-4,6-dinitro-1-hydroxybenzene - »2-phenylaminonaphthalene

2-Amino-l-hydroxybenzene-4-N-phenylsulfonic acid amide - »2-phenylaminonaphthalene

24th

25th

26

27th

do.

do.

l-amino-2-hydroxy-6-nitronaphthalene-4-sulfonic acid -> l-hydroxy-4-methoxy-naphthalene l-amino-2-hydroxy-6-nitronaphthalene-4-sulfonic acid -> l-hydroxy-4-methylnaph -thaline

2-amino-1-hydroxy-5-nitro benzene -> 3

Methyl-l- (2 ', 5'-dichlorophenyl) -5-

aminopyrazole

2-amino-4,6-dinitro-l-hydroxybenzene

3-methyl-1-phenyl-5-aminopyrazole

2-amino-4,6-dinitro-l-hydroxybenzene-2-phenylaminonaphthalene

2-amino-l-hydroxybenzene-4-sulfonic acid morpholide - »2-phenylaminonaphthalene

28

29

30th

31

32

33

do.

l-amino-2-hydroxynaphthalene-4-sulfonic acid -> l-hydroxy-4-methoxynaphthalene l-amino-2-hydroxynaphthalene-4-sulfonic acid - * l-hydroxy-4-methylnaphthalene l-amino-2- hydroxynaphthalene-4-sulfonic acid - * l-hydroxy-5-chloronaphthalene l-amino-2-hydroxynaphthalene-4-sulfonic acid -> l-hydroxy-5,8-dichloronaphthalene do.

2-amino-1-hydroxybenzene-4-N-phenylsulfonic acid -> 3-methyl-1-phenyl-5-aminopyrazole

2-amino-4,6-dinitro-1-hydroxybenzene -> 2-phenylaminonaphthalene

2-amino-6-chloro-4-nitro-l-hydroxybenzene - »2-phenylaminonaphthalene

2-amino-4,6-dinitro-l-hydroxybenzoI-> 2-phenylaminonaphthalene

2-amino-4,6-dinitro-1-hydroxybenzene - »2-ethylaminonaphthalene

2-amino-1-hydroxybenzene-4-N, N-di-ethylsulfonic acid amide - »2-phenylaminonaphthalene

34 do.

2-amino-4-chloro-6-nitro-l-hydroxybenzene - * 3-methyl-l- (4'-methylphenyl) -5-aminopyrazole

616 444

Example No. Compound (s) of formula (IV) compound (s) of

(used as 1: 1-Co complex) formula (III) (metal-free)

35 1 -Amino-2-hydroxy-6-nitronaphthalene-4-sulfonic acid - »1-hydroxy-5,8-dichloro-naphthalene

36 1-amino-2-hydroxy-6-nitronaphthalene-4-sulfonic acid - »1-hydroxy-5,8-dichloro-naphthalene

37 do.

38 l-amino-2-hydroxy-6-nitronaphthalene-4-sulfonic acid -> 1-hydroxynaphthalene

39 1 -Amino-2-hydroxy-6-nitronaphthalene-4-sulfonic acid -> 2-hydroxynaphthalene

40 do.

41 do.

42 do.

43 do.

44 do.

45 do.

46 1 - Amino-2-hydroxynaphthalene-4-sulfonic acid - * 2-hydroxynaphthalene

47 do.

48 do.

49 do.

50 do.

2-amino-4,6-dichloro-l-hydroxybenzene - »b 2-phenylaminonaphthalene

2-amino-4,6-dinitro-1-hydroxybenzene -> a 2- (3'-chlorophenyl) aminonaphthalene

2-amino-4,6-dichloro-1-hydroxybenzene - »f

3-Methyl 1- 1 - (3'-chloropheny 1) -5 - aminopy-razole

2-amino-4-chloro-1-hydroxy-5-nitrobenzene - »2-phenylaminonaphthalene do. d d

2-amino-4-chloro-l-hydroxy-5-nitrobenzene - »2-aminonaphthalene

2-amino-4-chloro-1-hydroxy-5-nitrobene-zole -> 3-methyl-l-phenyl-5-aminopyrazole

2-amino-1-hydroxy-5-nitrobenzene - »2- d phenylaminonaphthalene

2-Amino-1-hydroxy-5-nitrobenzene - »2- d (3'-chlorophenyl) aminonaphthalene

2-amino-1-hydroxy-5-nitrobenzene - »2- d

Aminonaphthalene-6-N- (2'-hydroxypro-

pyl) sulfonic acid amide

2-amino-4-chloro-1-hydroxy-5-nitrobenzene - »2-phenylaminonaphthalene

2-Amino-4-chloro-1-hydroxy-5-nitrobenzole - »3-methyl-l-phenyl-5-aminopy-razole

2-amino-1-hydroxy-5-nitrobenzene - »2- d phenylaminonaphthalene

2-amino-1-hydroxy-5-nitrobenzene -> 3 - g methyl-l-phenyl-5-aminopyrazole

2-amino-1-hydroxy-5-nitrobenzene -> 2- d aminonaphthalene

2-amino-4-chloro-1-hydroxy-5-nitrobenzene -> 2- (3'-chlorophenyl) aminonaphthalene

Dyeing instruction

0.03 g (to obtain a gray shade) or 0.15 g (to obtain a black shade) of the dye obtained according to Example 1 is dissolved in 300 parts of water and 0.2 g of ammonium sulfate are added. Then you go into the bath with the material used (5 g wool gabardine or 5 g nylon satin) and heat up within 30 minutes

Cooking temperature. The water evaporated during 30 minutes of cooking is added and further stained for 30 minutes while boiling, then rinsed. After drying, h5 has a gray or black color with very good light and wet fastness properties.

The dyes of Examples 2 to 50 can be used for dyeing in an analogous manner.

616 444

Printing instruction

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

50 parts of dye according to table example 4 50 parts of urea 50 parts of a solubilizer (e.g. thiodiethylene glycol)

300 parts of water

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

60 parts of an acid donor (e.g. Ammontartrate) 60 parts of thiourea.

10th

The printed textile 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. You get a black print with very good wet and light fastness.

Printing pastes can be prepared in an analogous manner which contain the dyes of Examples 1, 2, 3 or 5 to 50 as a constituent.

C.

Claims (3)

616 444 2nd PATENT CLAIMS 1. Process for the preparation of asymmetric 1: 2 cobalt complexes of the formula © corresponds, in which L, and L2 each denote monodentate ligands, with a compound of the formula m'O3S D N = N - HI D (III) & or a mixture of compounds of the formula (III) or that a mixture of compounds of the formula (II) is reacted with a compound of the formula (III) in a neutral to alkaline medium. 15 2. The compounds of formula (I) or mixtures thereof prepared by the process according to claim 1. 3. Use of the compounds of formula (I) according to claim 2 or their mixtures for dyeing leather. (I),