DE2520123A1 - PROCESS FOR THE PRODUCTION OF FORMAZAN METAL COMPLEX DYES - Google Patents

Description

CIBA-GEIGY AG, CH-4002 Basel

Case 1-9399 / + Germany

Attorney file 25 968

LiBA

^ 94T Ϊ * * *

DR. BERG DIPL.-ING. STAPF Di; L-ING. SCHWABS TUE. CR. SANDMAIR

PATENTANWÄLTE B MÖNCHEN 80 · MAUERKIRCHERSTR. 4ί

May 6, 1975

Method of making formazan metal complex paint

fabrics

The invention relates to a new process for the preparation of formazan metal complex dyes formula

0 0

Me B N

(D

wherein A and B are each an aromatic bonded in the ortho position Radical, R is an aromatic, aliphatic or heterocyclic radical and Me is a copper or nickel atom. The process is characterized in that an o-alkoxy-ο'-hydroxy-formazan of the formula

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OR-. HO

wherein A, B and R have the meanings given under formula (1), and R, a low molecular weight alkyl radical, in particular methyl, is reacted with an agent donating the metal atom Me in an alkaline medium, and that if necessary, the formazan complex dye obtained, if it has acylatable groups, acylated with an acylating agent.

As radicals A, B and R in formula (1) and (2), in particular radicals of the benzene and naphthalene series come in Consideration; in a preferred embodiment, A, B and R are benzene radicals. The residues A, B and R can be the in Azo or formazan compounds contain the usual substituents, e.g. sulfonic acid groups, carboxy, halogen, nitro, Cyano, hydroxy, amino, N-monosubstituted and N, N-disubstituted (alkyl, aryl, aralkyl) amino, heterocyclic substituted amino, low molecular weight alkyl, low molecular weight alkoxy, alkylsulfonyl, arylsulfonyl, sulfamoyl, N-monosubstituted and N, N-disubstituted sulfonic acid (alkyl, aryl, aralkyl) amide, heterocyclic N-substituted sulfonic acid amide, alkoxycarbonyl, aryloxycarbonyl, Acyloxy and acylamino.

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. 3 If the formazan metal complex dye obtained,

if it has acylatable groups, is acylated with an acylating agent, this happens in particular for the purpose of introducing a fiber-reactive radical. In this case, the obtained formazan metal complex dye becomes with an acylating agent that is a fiber-reactive radical contains, acylated.

Fiber-reactive residues are to be understood as meaning those with the hydroxyl groups of cellulose or with the amino groups of natural or synthetic polyamides able to react with the formation of covalent chemical bonds.

In a preferred embodiment of the method one leads the implementation of the o-alkoxy-ο'-hydroxy-formazane of formula (2) with the metal donor in alkaline solution in the presence of a complexing agent. as Complexing agents come into consideration such compounds, the Cu and Ni ions through in alkaline solution Able to keep complex formation in solution, e.g. containing ammonia, pyridine, ethylenediamine and chelating groups Compounds such as ethylenediaminetetraacetic acid and nitrilotriacetic acid, and especially aliphatic Hydroxydi- and tricarboxylic acids are considered, e.g. tartronic acid, malic acid, tartaric acid and citric acid. A preferred one The complexing agent is tartaric acid or potassium sodium tartrate (Seignette salt).

- 3a -

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Sodium hydroxide and potassium hydroxide are particularly suitable as alkali.

If the implementation of the o-alkoxy-o'-hydroxyformazans is carried out of formula (2) with the metal donor in aqueous solutions of ammonia or of organic Bases such as ethylenediamine or diethylenetetramine, which Copper or nickel ions are able to hold complex in solution and at the same time have an alkaline effect, so they can Compounds likewise, i.e. without additional alkali such as sodium or potassium hydroxide, the demethylation of the Effect o-alkoxy-ο'-hydroxy-formazane of the formula (2).

Instead of an o-alkoxy-ο'-hydroxy-formazan of the formula (2) Reacting with an agent donating the metal atom Me in an alkaline medium, one can also use an o-alkoxy-o'-hydroxy-formazan of formula (2) with an agent donating the metal atom Me to form an intermediate of the formula

A Me B

wherein A, B, R and R have the meanings given under formula (2) have, implement, isolate the intermediate of the formula (3) and, in the second stage, by treatment with Alkali in one

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Convert formazan metal complex dye of the formula (1). In this procedure, too, the reaction of the o-alkoxy-ο ¹ -hydroxy-formazane of the formula (2) with the agent donating the metal atom Me and in particular the splitting off of the alkyl radical R- caused by alkalis from the intermediate product of the formula ( 3), preferably carried out in the presence of a complexing agent.

Preferred starting materials are o-alkoxy-o'-hydroxyformazanes of formula (2), which water-solubilizing groups, in particular sulfonic acid groups, and one or two Contain amino or acylamino groups, which, optionally after saponification, with an acylation agent, the one contains fiber-reactive radical, can be acylated.

Such a reactive fiber residue represents in particular a low molecular weight atom which can be split off or a removable group-substituted alkanoyl or alkylsulfonyl radical, a low molecular weight, optionally by a removable atom or a removable group substituted alkenoyl or alkenesulfonyl radical, one above a carbonyl or sulfonyl group, by a removable atom or a removable group substituted carbo- or heterocyclic 4-, 5- or 6-ring containing radical or a radical bonded directly via a carbon atom, represents a triazine or pyrimidine radical substituted by a removable atom or a removable group, or contains one.

The reactive radical is preferably a six-membered group which is bonded via an amino group and contains halogen atoms heterocyclic radical, such as a halotriazine or halopyrimidine radical.

In particular, the fiber reactive radical is a radical of the formula -N (R-) -Z, where R. is a low molecular weight alkyl radical or preferably a hydrogen atom and Z a 4,6-dihalo-s-

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triazinyl (2) radical or a 4-halo-6-amino (alkoxy, phenoxy, alkylmercapto or arylmercapto) -s-triazinyl- (2) radical. Under low molecular weight alkyl radicals are in this context AlkyIreste with up to four carbon atoms to understand how the methyl, ethyl, propyl, isopropyl or butyl radical.

The radical R-, in the o-alkoxy-ο'-hydroxy-formazans of formula (2) or in the intermediates of formula (3) is preferably the methyl group.

The starting materials of the formula (2) are known or can be produced by known methods.

In the process according to the invention, preference is given to formazan metal complex dyes of the formula

Y 0 0

HO ^ S-h I Cu

Il

prepared in which one Y is a radical of the formula -NH-X, and the other Y are hydrogen atoms and / or sulfonic acid groups, and X is a fiber reactive group.

The production takes place, for example, in such a way that an o-alkoxy-ο'-hydroxy-formazan of the formula

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OR, HO I

XX,

HO, S-

J νχττυ Ν ^{/ Ν /} ' ^Ν Υ

where R _{1 is} a low molecular weight alkyl radical, one Y is the IL ^ N group or an acylatnino group and the other Y are hydrogen atoms and / or sulfonic acid groups, in alkaline solution

in the presence of a complexing agent with a copper-releasing agent, optionally with simultaneous saponification of the acylamino group, and the formazan copper complex dye obtained with a fiber reactive radical X containing Acylating agent acylated.

The halides or anhydrides, in particular, are used as acylating agents which contain a reactive fiber radical organic acids that contain easily exchangeable atoms or groups of atoms.

Examples of acylating agents containing a reactive fiber radical are the following: chlorine or bromoacetyl chloride,
β-chloro- or ß-bromopropionyl chloride,
α, β-dichloro- or α, ß-dibromopropionyl chloride, chloromaleic anhydride,
Carbyl sulfate,
Acrylic chloride,

AjS-dichloro-l-phenylpyridazone carbon or sulfonic acid chloride, 4,5-dichloropyridazonopropionic acid chloride,

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l ^ -Dichlorphthalazine carbon or sulfonic acid chloride, 2,3-dichloroquinoxaline carbonic or sulfonic acid chloride, 2,4-dichloroquinazoline carbonic or sulfonic acid chloride, 2-methanesulfonyl-4-chloro-6-methylpyrirnidine, 2,4-bis-methanesulfonyl-6-methylpyrimidine, 2,4,6-tri- or 2,4,5,6-tetrachloropyrimidine, 2,4,6-tri- or-2,4,5,6-tetrabrorapyrimidine, 2-methanesulfonyl-4,5-dichloro-6-methylpyrimidine, 2,4,6-trichloro-5-bromopyrimidine, 2,4,5,6-tetrafluoropyrimidine, 4,6-difluoro-5-chloropyrimidine, 2,4,6-trifluoro-5-chloropyrimidine, 2,4,5-trifluoropyrimidine,

2,4,6-trichloro or tribromo-l, 3,5-triazine, and _s 4J6-dichloro- or dibromo-1,3,5-triazines which are substituted in the 2-position by an aryl or

Alkyl radical, e.g. a phenyl, methyl or ethyl radical, or by the remainder of an aliphatic or aromatic mercapto bonded via the sulfur atom or via the oxygen atom

Bound hydroxyl compound or in particular by a

NH ^ group or through the remainder of one via the nitrogen atom bound aliphatic, heterocyclic or aromatic

Amino compound.

The acylations with the fiber-reactive acylating agents and the condensations with compounds, which one over contain a reactive hydrogen atom bonded to a hetero atom, one leads regularly using acid-binding agents Agents, such as sodium carbonate or sodium hydroxide, and under

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such conditions that in the finished product are still interchangeable Halogen atoms, unsaturated bonds or the like remain in the fiber reactive radical, i.e. e.g. in organic solvents or at relatively low temperatures in an aqueous medium.

An example of a formazan metal complex dye of the formula (4) is the dye of the formula

(6)

called, which is produced according to the invention in that the o-methoxy-ο'-hydroxy-formazan of the formula

NH-COCH ₃ OCH HO I

/ χ

in an alkaline solution in the presence of potassium sodium tartrate reacted with a copper-releasing agent, the acetyl group being split off at the same time, and the formazan copper complex dye obtained acylated with 2,4-dichloro-6-isopropoxy-s-triazine.

According to the present procedure and its

Formazan metal complex dyes available in variants are mostly new and suitable

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for dyeing and printing a wide variety of materials, such as silk, leather, wool, synthetic fibers made of super polyamides, Super-polyurethanes, polyhydroxylated materials, such as cellulosic materials with a fibrous structure, such as Linen, cellulose, regenerated cellulose, cotton and the like.

The water-soluble formazan metal complex dyes are of particular importance as dyes.

Most important are the formazan metal complex dyes,

at least /

which contain a fiber reactive radical and / a sulfonic acid group. These dyes are preferably used for dyeing nitrogen-containing fibers, such as super polyamides, super polyurethanes, Silk, leather and especially wool, e.g. from weakly acidic, neutral or weakly alkaline baths, if necessary with the addition of the usual auxiliaries, e.g. ethylene oxide condensation products of high molecular weight amines, and especially of cellulose materials, especially cotton, e.g. after the Exhaust process from long liquor, from alkaline, possibly highly salty, aqueous bath and especially after the foul ardffarben ever drive, after which the goods with watery and optionally also salt-containing dye solutions is impregnated, and the dyes after an alkali treatment or in Presence of alkali, optionally fixed under the action of heat, used.

The water-soluble fiber reactive dyes are also suitable for printing, in particular on cotton, but also for Printing on nitrogen-containing fibers, e.g. wool, silk or mixed fabrics containing wool «,

The dyeings and prints are characterized by inter-

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essential and valuable, very pure and brilliant nuances. The dyeings and prints show good acid and alkali resistance as well as good resistance to synthetic resin finishing agents, good lightfastness and, in particular, Cotton, excellent wet fastness. Furthermore, the high degree of fixation and the good removability are not worth mentioning fixed dye components.

In order to improve the wet fastness properties, it is advisable to give the dyeings and prints a thorough one Rinse with cold and hot water, optionally with the addition of a dispersing agent and the diffusion of the not subject to fixed proportions of promoting agent.

In the following examples, unless otherwise stated, parts are parts by weight and percentages Percentages by weight and temperatures are given in degrees Celsius. The same exists between parts by weight and parts by volume Ratio as between grams and cubic centimeters.

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example 1

A neutral solution of the sodium salt of 24.6 parts of 6-acetylamino-2-aminophenol-4-sulfonic acid becomes in the usual way with the addition of 30 parts by volume of conc. Hydrochloric acid and 25 parts by volume of 4N sodium nitrite solution are diazotized. The suspension of the diazo compound is added to an aqueous solution of 38.6 parts of the hydrazone from 2-methoxy-5-sulfophenyl hydrazine and benzaldehyde-2-sulfonic acid in water at p "12 to 13 is added and the p "value of the coupling mixture is added kept at 12 to 13 by sodium hydroxide solution. After the coupling has ended, a solution is added to the resulting oxy-methoxy-formazane previously prepared solution of 25 parts of copper sulfate pentahydrate, 33.5 parts of seignette salt (potassium sodium tartrate tetrahydrate) and 63 parts of 407oig sodium hydroxide solution in 250 parts by volume of water. The resulting violet dye solution now becomes demethylating Metallization and simultaneous saponification of the acetylamino group kept boiling under reflux for 5 hours, the solution gradually turns dark blue.

10% of the volume of table salt and potassium chloride are added, the mixture is allowed to cool, and then by adding dropwise conc. Hydrochloric acid to p "0.5 and finally sucks in the deposited Aminoformazan dye.

The moist suction filter is slurried in water, adjusted to p "7 by adding sodium hydroxide solution, and the resulting Solution at 0 ° with 18.5 parts of freshly precipitated cyanuric chloride offset. The p "value of des is maintained during the condensation Reaction mixture by adding dropwise sodium hydroxide solution at 5 to 6.

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After the condensation has ended, 25 parts by volume of conc.
aqueous ammonia solution added. The temperature is raised to 35
and holds at this temperature for 3 hours. The formazan dye of the formula is isolated by evaporating the resulting solution in vacuo

Cl

C-NH 0 0 '

\ κ

Cu

V ^X I

-SO ₅ H

as a blue-black powder. He dyes cotton fabrics
in real navy blue tones.

If you replace the 33.5 parts of Seignette salt in this example

35.1 parts of ethylenediaminetetraacetic acid, respectively. Parts of aqueous ammonia solution (25%), respectively.

34.6 parts of n-butylamine, respectively.

14.2 parts of ethylenediamine, respectively. 25.1 parts of diethylenetriamine

and performs demethylation and saponification as well
Isolation of the Formaζankomplexes under the reaction conditions described above and sets the isolated

- 12a -

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Complex with cyanuric chloride and ammonia, the same formazan dye is also obtained.

If the hydrazones listed in column II of table I with the diazonium salts listed in column III o-aminophenols and the resulting o-methoxy-ο'-hydroxy-1,3,5-triarylformazan dyes with Copper salts under conditions analogous to those set out in Example 1, a demethylating Subject to complex formation, the tricyclic o, o'-dihydroxy-1,3,5-triaryl-formazan copper complexes listed in column IV are obtained. If you carry out a reaction with these complexes with those in dye chemistry generally known reactive components, they react via their free amino group to form reactive dyes, which, for example, carry the reactive radicals listed in column V and those listed in column VI Dye shades on cellulose fibers.

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Table I.

Example no. Hydrazone I. dito o-aminophenol Pormazan complex reactive rest nuance (State of charge not on cellulose dito considered) fibers NH ₂ . • A / 1 dito α JLJL / C ^ s X_JL 2 · · Navy blue _f . dito dito Navy blue ■ . 4th dito dito Navy blue • α 5 dito dito -CO-CH CH ₀ Navy blue ir Br " (on wool)

Table I (continued)

Example no

Hydrazone

O-aminopheno2

Formazan complex

(State of charge not taken into account )

reactive rest

nuance

on cellulose fibers

σα,

N *

A "

V Ö

NH ₁

V Ö

Navy blue

dito

dito

Navy blue

It £

dito

"OK

dito

Dark blue

Table I (continued)

Example no

Hydrazone

o-aminophenol

Formazan complex

(State of charge not

considered)

Reactive rest

nuance

on cellulose fibers

Ct

iy-s: iN

Navy blue

cn ο co oo

10

NN

dito

SO ₁ H

dito

Cl

greenish blue

11

12th

HOi NH ₂

wrt "'■"

dito

HO, S

dito

dito

CCV

greenish blue

dito

(2 reactive residues per molecule of formazankupfeij J complex)

greenish blue

Example no.

Table I (continued;

For rna zank omol ex

Hydrazone

o-aminophenol

(State of charge not
considered)

reactive rest

nuance

on cellulose fibers

■ CC »i

DS

.Navy blue

cn (3 CQ co ** »co • ^ O CD cn

14th

CCH,

dito

Cu

• cooH

Navy blue

m
-a
m

15th

NH

dito

DT *

C)

reactive
Leftovers per mole
kül Formazankomnlex)

Navy blue

16

-ecu.

HO.S '

N'iK

CLW,

'SCM

SO.H

or

Navy blue

Table I (continued;

Example no.

Hydrazone

o-aminophenol

Formazan Complcx

(Charge level not

considered)

reactive rest

nuance

on cellulose fibers.

cn ο co co

17th

• IS

CCHr

NH

V ⁰

Cu

so, H

JQ

"SO ₃ H

CCH ₇

NHCOCH-,

Cl

greenish blue

Navy blue

19th

ecu.

dito

Cl

Navy blue

20th

OQf ₇

⁴ Va

CO-

C)

Navy blue

cn O ro

Example no ..

Hydrazone

o-aminophenol

Pormazan complex

(State of charge not

considered)

reactive rest

nuance

on cellulose fibers

21

HO

• NH

Cl

SO ₂ CIf ₃

greenish blue

cn ο ca oo

σ co cn

22nd

dito

dito

dito

CO-CH CH ₀

Γ ²

Br Br

greenish

Blue (on wool)

dito

Cu

'SQ,

CH:

greenish blue

24

dito

* df ^ "¥ ^H

SO ₂ . CH ₂

Cl

-V ¹ -

greenish blue

Table I (continued)

. ■ Example no,

Hydrazone

o-aminophynol

.. · Formazan complex
(State of charge not
considered)

reactive rest

nuance

on cellulose
fibers

CCH,

NU ^N

NHCOCH

OCH ₃

greenish blue

26th

H ₂ N

OÜK

Nit

HP

SO ₂ H

SOjH

greenish blue

27

NH ₂ .

Cl

CCH ₁

■ bluish green

28

OCH ₁

NH

Cu

Qk

■ wtl

bluish ο

green

Example no,

Hydraζon

Table I (continued)

o-aminophenol

Pormazan complex
(State of charge not
considered)

reactive rest

nuance

on cellulose fibers

29

AM I

O _n 0

■ ^1γ οΤ

Navy blue

30th

MH

OW

dito

Dark blue

31

HO.

dito

Navy blue

32

OCIl,

NU

dito

H ₄ NO ₁ S

V ⁰

WH ₁

dito

if

greenish blue

Example no.

Hydrazone

Table o-aminopheno]]

I (port setting)

Formazan complex (State of charge not taken into account)

reactive res

nuance

on cellulose fibers

33

ocn.

so

SO ₁ H

Navy blue

34

dito

dito

reddish
■ blue

35

OCH,

dito

NU,

dito

Navy blue

cn ro ο

36

dito

Ca '

dito

greenish
blue

Example no.

Hydrazine

Table I (continued) o-AminoDhenol

Formazar.complex

(State of charge not

considered)

reactive rest

nuance

on cellulose fibers

37

OCH,

MH

Ho

NHCOCH ₃

Cl

' ^ Ctti

greenish blue

cn ο co co

NH-CCCH-,

HO.,

■ γΝ
CK-2.

Cl

greenish navy blue

OCH-7

N; NH-,

dito

Cl

Navy blue

OCH ₁

dito

Cl

WH

greenish blue

Table I (continued;

Example no,

Hydrazone

o-aminophenol

■ Pormazan grain complex

(State of charge not

considered)

reactive rest

nuance

on cellulose fibers

41

OOK

¹ ^ T

\ P

ever!

blue

Lc

dito

NIH ₂ .

Cl

greenish navy blue

WIT ₂

dito

Cl

greenish blue

44

M ₁

dito

Cl

Green cast blue

Example 45

The aqueous solution of 64.3 parts of the metal-free oxy-methoxy-formazane described in Example 1 is produced. This is mixed with a solution of 28.1 parts of nickel sulfate heptahydrate, 33.5 parts of Seignette salt and 63 parts of 407% sodium hydroxide solution in 250 parts by volume of water, and the mixture is stirred for 8 hours at room temperature and 5 hours under reflux. The blue-violet solution is then mixed with 207 _{o of} the volume of table salt, cooled to 10 after the salt has dissolved and acidified with conc. Hydrochloric acid to p "0.5. The unusual dye of the formula

o o

-SO H

is suctioned off, the filter cake is dissolved in water with sodium hydroxide solution neutralized and the solution to isolate the dye finally evaporated to dryness.

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Example 46

18.8 parts of 2-Arainophenol-4-sulfonsäurearaid become diazotized according to the usual method and the diazo solution after destruction of the excess nitrite with sulfamic acid Adding sodium hydroxide solution set to p "6.0. This diazo solution now becomes an aqueous suspension adjusted to p "6.5 of 38.5 parts of the hydrazone of the formula given in column 2 of Example 7 (see Table I) collapsed at 0 to 5 °. Immediately thereafter, a solution of 25 parts of copper sulfate pentahydrate in 100 parts of water is added dropwise within 20 minutes, whereby the p "is kept between 6.5 and 7.0 by the simultaneous addition of sodium hydroxide solution (conc.). The coupling sets in immediately, producing a dark blue solution which is stirred for 15 hours at 20 and at a constant p "of 6.5 will. The resulting copper complex of the formula

O O

_N0 _o SN NS0 _o NH _o 2 2 "j 2 2

-SO ₃ H

is separated by adding 107 _{0 of} the volume of common salt, suctioned off and pressed well.

The moist press cake is slurried in 200 parts of water. The suspension is made with 10 parts of sodium hydroxide (solid) added, heated to 95 ° and stirred for about 5 hours at this temperature, the initially red-violet solution color

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changes to a deep blue. The formation of the tricyclic complex is followed by paper electrophoresis. Included migrates the tricyclic blue formazan complex of the ο, ο'-dioxy type faster to the anode than the purple-colored copper complex of the o-oxy-o'-methoxy type isolated as an intermediate. the The resulting deep blue solution is cooled to 40 ° after complete demethylation with 0.1 part of animal charcoal and 0.1 parts of filter earth added and through a carriage clarified. The filtrate is at 20 by the dropwise addition of conc. Hydrochloric acid set to p "7.0 and the dye of the formula

OO
\ /

Cu

■ / \ tAA _SO j _E

-SO ₅ H

isolated by completely evaporating the water. on animal fibers or polyamides, such as nylon 6, nylon 66 and the polyurethanes applied, results in the product level, washable and lightfast, lively blue tones.

If, in the demethylation of the methoxy-hydroxy complex isolated in this example, the 10 parts of sodium hydroxide (solid) by

100 parts of aqueous ammonia solution (25%), respectively. 20 parts of ethylenediamine

replaced, the same o, o ¹ -dihydroxyformazan dye is obtained with otherwise the same reaction procedure.

609848/0358

- γι -

Example 47

24.6 parts of o-acetylamino - ^ - aminophenol - ^ - sulfonic acid are diazotized in the manner described in Example 1. The suspension of the diazo compound is on p "5 to 6 and at 0 to 5 ° to a neutral aqueous solution of 30.6 parts of the hydrazone of the formula below fell.

Then an aqueous solution of 25 parts of copper sulfate pentahydrate is allowed to run in within 10 minutes, where the p "is due to the simultaneous addition of sodium hydroxide solution (conc.) is kept at 6.5 to 7. To complete the coupling, the mixture is stirred for 2 hours at 0 ° to 5 ° and 15 hours continue at room temperature. The solution is then mixed with 45 parts of sodium hydroxide (solid) and 33.5 parts of Seignette salt (Potassium sodium tartrate tetrahydrate) and stirred for 8 hours at 95 to 100 °. After cooling to room temperature is used with conc. Hydrochloric acid set to p "5.5 and mixed with 160 parts of sodium chloride, whereby the Formaζankomplex precipitates as a blue-black precipitate and is isolated by suction.

13.4 parts 1,4-phenylenediamine-2,5-disulfonic acid

are dissolved in 1000 parts of water at p "6 and

rl

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- as -

at 0 to 2 ° with 19 parts of freshly precipitated cyanuric chloride offset. The hydrochloric acid released is neutralized by the gradual addition of dilute sodium hydroxide solution and falls after 2 hours at 0 to 5 ° 88.8 parts of the above isolated formazan complex. The temperature is allowed to rise to 20 within an hour and is set again Constantly neutral through the controlled addition of dilute sodium hydroxide solution. The condensation will be at 35 to 40 completed over 3 hours and the reactive dye of the formula below isolated after a clear filtration by evaporating the solution to dryness.

The dye dyes cotton fabrics in real navy blue tones.

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Si

Example 48

18.9 parts of 2-aminophenol-4-sulfonic acid are diazotized by a customary method. The diazo component is adjusted to p _H 5 and rushing up to a neutral solution of 36.3 parts of ITydrazons the formula below.

OCH ₃
NU- ti = CH- / "V-KHCOCH ₃

If you carry out the coupling and demethylation of the intermediate product in the manner described in Example 47, the formazan complex of the formula below is obtained, which is precipitated by neutralizing the solution and adding salt and isolated by suction.

K) H ₁

We-d this formazan complex in aqueous solution at 0 to 5 reacted with acetyl chloride, the hydrochloric acid released being continuously neutralized, so one obtains after evaporation of the solution, a dye which dyes wool in blue-green shades with good fastness properties. Be the other 86.1 parts of the formazan isolated in this example

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- 30 complex rait dem from 19 parts cyanuric chloride and

15.9 parts of 2,6-diaminonaphthalene-4,8-disulfonic acid prepared by the procedure described in Example 47 Intermediate reacted, one obtains the formazan dye of the formula below, which according to the Implementation precipitates as a blue-black precipitate and is isolated. The dye dyes cotton in real blue-green tones.

SO ₃ H

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- 24 -

F'drbe examples '

1. In a bath which, in 500 parts of water, contains 0.5 part of Glauber's salt, 0.4 part by volume of acetic acid and 0.2 part of dye Contains according to Example 22, one goes at 40 ° with 10 parts of wool flannel. The temperature is increased within 30 minutes evenly until boiling and colors the wool flannel for another hour at boiling temperature. The dyed material is then rinsed and finished as usual. A very uniform, pure blue color is obtained.

. If you use the same amount of sulfuric acid instead of acetic acid and dye as indicated in the example, so a blue coloration with the same properties is obtained.

2. One goes at 40 with 10 parts of a synthetic polyamide fabric in a dye bath, which in 500 parts Water 0.40 part of 40% acetic acid, 0.25 part of sulfonate des Ricinoleic acid butyl ester and 0.20 parts of the dye of Example 23 contains. The temperature is increased evenly within 30 minutes to the boiling point and continues to color for an hour at low boiling point. The fabric is then rinsed and dried. A uniform, streak-free blue dyeing is obtained, which is washfast and lightfast

having.

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3. 2 parts of the dye obtained in Example 21 are with the addition of 0.5 parts of m-nitrobenzenesulfonic acid Sodium dissolved in 100 parts of water. With the solution obtained, a cotton fabric is impregnated so that it is around 75% of his Weight increases, and then dried. .

Then you impregnate the fabric with a 20 warm A solution containing 5 grams of sodium hydroxide and 300 grams of sodium chloride per liter squeezes to a 757o weight gain, dampens the color for 60 seconds at 100 to 101 °, rinses, soaps for a quarter of an hour in a 0.3% boiling Solution of an ion-free detergent, rinses and dries. A blue color is obtained.

4. 2 parts of the dye obtainable in Example 1 are dissolved in 100 parts of water.

The solution is added to 3900 parts of cold water, 80 parts of sodium chloride are added and 100 parts of one are added Cotton fabric into this dye bath.

The temperature is increased to 80 in 45 minutes, 40 parts of trisodium phosphate and again after 30 minutes 80 parts of sodium chloride are added. The temperature is kept at 80 ° for 30 minutes, and the dyeing is then rinsed and soaped during 15 minutes in a 0.3% boiling solution of an ion-free detergent, rinses and dries. The result is a washable and lightfast blue color.

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5. 2 parts of the dye prepared according to Example 4 are mixed with rapid stirring in 100 parts of a stock thickening containing 45 parts of 5% sodium alginate thickening, 32 parts Water, 20 parts of urea, 1 part of m-nitrobenzenesulfonic acid Sodium and 2 parts of sodium carbonate sprinkled in.

The printing paste thus obtained is used to print a cotton fabric on a double-sided printing machine and steamed obtained printed fabric for 2 to 4 minutes at 100 in saturated steam. The printed fabric is then in cold and rinsed thoroughly with hot water, whereby the non-chemically fixed parts are very easily removed from the fiber leave, and then dried. A blue print is obtained.

6. In a dyebath containing 10 parts of crystallized sodium sulfate, 6 parts of 407o acetic acid in 3000 parts of water, 0.5 part of the adduct of oleylamine and ethylene oxide described below and 2 parts of that in Example 5 Contains the dye described, one goes at 50 to 80 with 100 parts of woolen knitting yarn. In the course of half an hour the bath is heated to boiling temperature and then stained at the boil for an hour. The wool is then rinsed and dried. A uniform blue color is obtained.

Production of the ethylene oxide addition product

100 parts techn. Oleylamine are mixed with 1 part of finely divided sodium and heated to 140 °, whereupon one Introduces ethylene oxide at 135 to 140 °. As soon as the ethylene oxide

509848/0958

is absorbed quickly, the reaction temperature is lowered to 120 to 125 and the introduction of the ethylene oxide is continued continued until 113 parts of ethylene oxide were absorbed. The reaction product obtainable in this way is practically clear in water soluble.

S03848 / G958

Claims (16)

Claims 1. Process for the preparation of formazan metal complex dyes of the formula A Me B wherein A and B are each an aromatic bonded in the ortho position shear radical, R is an aromatic, aliphatic or heterocyclic radical and Me is a copper or nickel atom, characterized in that one o-alkoxy-ο'-hydroxy- formazan of the formula _{nr> TTr} , / ^OR 1 ^H0 \ AB wherein A, B and R have the meanings given under formula (1), and R, a low molecular weight alkyl radical, in particular Methyl, is reacted with an agent that donates the metal atom Me in an alkaline medium and that, if necessary, the obtained formazan metal complex dye, if he has acylatable groups, acylated with an acylating agent. 2. The method according to claim 1, characterized in that that the formazan complex dye obtained, if it has acylatable groups, for the purpose of introducing a fiber-reactive radical with an acylating agent which contains a fiber-reactive radical, acylated. 509848/0958 3. The method according to claim 1, characterized in that that the starting materials are ο-Aikoxy-o'-hydroxy-formazane of the formula (2) used, in which A, B and R are benzene radicals, as further substituents sulfonic acid groups, carboxy, Hydroxy) /
Halogen, nitro, cyano, / amino, N-monosubstituted and N, N-disubstituted (alkyl, aryl, aralkyl) amino, heterocyclic, substituted amino, low molecular weight alkyl, low molecular weight alkoxy, alkylsulfonyl, arylsulfonyl, sulfamoyl, N- monosubstituted and Ν, Ν-disubstituted sulfonic acid (alkyl, aryl, aralkyl) amide, heterocyclic N-substituted sulfonic acid amide, alkoxycarbonyl, aryloxycarbonyl, acyloxy and acylamino may contain. 4. The method according to claim 1, characterized in that that you can implement the o-alkoxy-ο'-hydroxyformazans of formula (2) with the metal donor in alkaline solution in the presence of a complexing agent. 5. The method according to claim 1, characterized in that that you have an o-alkoxy-ο'-hydroxy-formazan of the formula (2) with an agent donating the metal atom Me to an intermediate of the formula A> Ie B (3) V ₃ J / V _n / 5G9848 / Ö958 wherein Λ, B, R and R have the meanings given in claim 1 have reacted, isolated the intermediate of formula (3) and then by treatment with alkali in a formazan metal complex dye converted to formula (1). 6. The method according to claim 5, characterized in that the alkaline treatment of the o-alkoxy-o'-hydroxyformazans of formula (3) in the presence of a complexing agent. 7. The method according to claim 1, characterized in that that one o-alkoxy-ο'-hydroxy-formazane of the formula (2), which Contain amino or / suIfönsMure groups and one or two / acylamino residues, used as raw materials. 8. The method according to claim 2 for the preparation of formazan metal complex dyes of the formula wherein one Y is a radical of the formula -NH-X, and the other Y are hydrogen atoms and / or sulfonic acid groups, and X is fiber-reactive radical is characterized in that one is an o-alkoxy-ο'-hydroxy-formazan of the formula 509848/0958 (5) Y L-I-Y wherein R, is a low molecular weight alkyl radical, one Y is the H ₉ N group or acylamino group, and the other Y is hydrogen atoms and / or sulfonic acid groups, in alkaline solution in Opposite a complexing agent with a copper releasing agent, optionally with simultaneous saponification of the acylamino group, and the formazan copper complex dye obtained acylated with an acylating agent containing the fiber reactive radical X. 9 _m 'Process according to claim 8 for the preparation of the formazan copper complex dye of the formula (6) characterized in that the o-methoxy-o'-hydroxyformazan the formula 509848/0958 NH-COCHo OCH HO ' ^ό HO ₅ O- \ _{ΝΗ Ν} / DU ₅ Xi ( ₇ ) -SO H in alkaline solution in the presence of potassium sodium tartrate with a copper releasing agent and the formazan copper complex fax material obtained with 2,4-DiChIOr-O-XSOpX-OpOXys-triazine acylated. 10. · Procedure according to the examples given. 11. The compounds obtainable according to claims 1 to 9. -j_2. Use of those obtainable according to claims 1 to 9 Compounds as dyes. 13. A process for dyeing and printing using the dyestuff according to claim 12. 14. The method according to claim 13 for dyeing Cellulosefasex-n. 15. Dyeing and printing preparations which contain dyes according to Claims 1 to 9. 16. The colored or printed material obtained according to claims 12 to 15. 509848/0958