CH647797A5 - Organic dyes and preparation and use thereof - Google Patents

Abstract

The new sulpho-free di-metal complex-containing 1:1 copper, cobalt, iron, nickel, manganese or zinc complex compounds of symmetrical or asymmetrical dis- or polyazo compounds of the formula <IMAGE> where the symbols are each as defined in Claim 1, are suitable in particular for dyeing leather or paper.

Description

647797 2

PATENT CLAIMS plex connections of symmetrical or asymmetrical

1. Sulphonic acid group-free di-metal complex-containing 1: 1 dis or polyazo compounds of the formula copper, cobalt, iron, nickel, manganese or zinc com-

R,

^ • C-O-tfe-O

• C-N = N

b;

O-Me-O-Cv, ■

: 2

-(Y Z)

n

(I)

bliss

Me each have a copper, cobalt, iron, nickel, manganese or zinc atom,

Y is the direct bond or a (1-4C) alkylene radical, a bridge member of the formula

O

II

-C-NH- (CH2) m * -, -NH-CO- (CH2) m * - or

-s02-n- (ch2) m * -,

R4

m each 1, 2, 3 or 4,

R] and R2 independently of one another are a divalent radical necessary to complete an aromatic or heterocyclic coupling component, n is a number of at least 2,

Z is a radical of the formula -N (CH3) 2, -®N (CH3) 3 Ae,

-®N (CH3) 2 Ae or ch2-ch2-oh /

^ <CVP

p 0.1 or 2,

R4 is hydrogen or a (1-4C) -alkyl radical and Ae is an anion,

X for Xi the direct bond,

X2 is a straight-chain or branched alkylene radical having 1 to 4 carbon atoms,

x3 -c-; x4 -nh-c -nh-; x5 -s-; x6 -0-;

o s x7-ch = ch-;

xg-s-s-;

x9-s02-;

x10-nh-,

x ,, -nh-c-,

II O

Xp-n — c-,

i II CH3O

x13 ^ c-.

x17-so2-nh-

15 x, 8-s02-nh - ^) - nh-so, -,

x, 9 -n -c - (ch2) m-c -n -, I II II I

R4 O O R4

20 x20 -n -c -ch = ch-c -n -, I II II I

R4 O O R4

x2] -n — c — n-, 25 I II I R4 O R4

30th

X22-C-NH-NH-C-, II II

o o x23 -ch2-c -nh-nh-c -ch, -,

II Ii o o

35

X24 -CH = CH-C -NH-NH-C -CH = CH-II II

o o

40

X25-N

.ch2-ch2

ch2-ch2 "

n.

n-

45

_, ch2-ch2 p.

x26-o-c-n <"J> n-c-o-

11 ^ ch2-CH2 o 2,

I!

O

50

X] 4-C-NH- ^ 5-NH-C-,

II

O

O

X.v-C

CNH- @ v o f r3.

nh-c-II O

55

60

65

xi6 -nh-c —ß> - c -nh-

II II

o o n n

II II

c-

o x28-o-c-o-,

II

o x29-c-o-,

II

O

X3o ~ C-C-,

o o

X31-0- (CH2) m-0-,

647 797

X30-n-c c-n-, "II II I-r4 n n r4

Qf

I.

Rev

.N.

^ \

x, 3-oc c-o-,

I II n n

Nc

I.

r7

x, 4 -c — n-r6-n— c-

II 'I 11

o r4 r4 o x35 -c —n - (ch2) m-0- (ch2) m-n —c -

o r4

I II

r4 o x36 -c -n - (ch2) m-n - (ch2) m-n -c -, II I I I II

o r4 ch3 r4 o x37 -C — N .- (CH2) m-0- (CH2) m-0- (CH2) m-N -C-, II I I II

o r4 r4 o x38-ch2-c-n-

II I O R4

x39-ch = ch-c-n-,

II I

o r4

x40-n = n-x41 -so-,

x42-ch2-s-ch2-,

x43-ch2-so-ch2-,

x44-ch2-s02-ch2-

R5 halogen, a (1-4C) alkyl or alkoxy radical, R6 each a straight-chain or branched (1-4C) -20 alkylene radical and

R7 is halogen, -NH-CH2-CH2-OH or -N (CH2-CH2-OH) 2, and the aromatic rings B and B] are each independently of one another by halogen and / or (1-4C) -alkyl- and / or (1-4C) -alkoxy may be substituted and 25 the C atom marked with * is bound to the N atom of the basic or quaternary ammonium groups.

2. A process for the preparation of compounds of the formula (I) according to claim 1, characterized in that a compound of the formula

30th

10th

15

- / "■" C-O-R R, ti 20

^ C-N = N—

R -0 20

- ° ° ~ R20

R, -0-C \

20 "> 2

N = N-C

-Or-z).

(x)

4. The leather or paper dyed or printed by the process according to claim 3.

where R20 is hydrogen or a (1-4C) -alkyl radical 40

indicates with copper, cobalt, iron, nickel, manganese or

zinc-releasing compounds treated that bimetallic

Complex compounds of the formula according to claim 1 are subject of the invention are kept free of sulfonic acid groups. Di-metal complex containing 1: 1 copper, cobalt, iron, Nik

3. Process for dyeing or printing leather or 45 kel, manganese or zinc complex compounds from symme paper, characterized in that compounds of the trical or asymmetrical dis- or polyazo compound formula I are used. against the formula

C-O-Me-O

\ «/ ^ -C-N = l

"0-Me-0-C

-N = N-C '

J2

-(Y Z)

(I)

wherein

Me each a copper, cobalt, iron, nickel, resistance to an aromatic or heterocyclic gan or zinc atom, coupling component necessary divalent radical,

Y is the direct bond or a (1-4C) alkylene radical, an n is a number of at least 2,

Bridge member of the formula

O

II

-C -NH- (CH2) m * -, -NH-CO- (CH2) m * - or

-S02-N- (CH2) m * -,

I.

R4

m each 1, 2, 3 or 4,

R] and R2 independently of one another to complete

60

Z is a radical of the formula '-n (ch3) 2, -®n (ch3) 3 ae, -®n (ch3) 2 a®

ch2-ch2-oh or _ © n ^ Ae,

65

H (CH.) 3 p

647797

4th

pO, l or 2,

R4 is hydrogen or a (1-4C) -alkyl radical and Ae is an anion,

X for Xi the direct bond,

X2 is a straight-chain or branched alkylene radical with s 1-4 carbon atoms,

X3-C-,

, ch -, - ch2>

x25-n <^ j> n-,

• ch2-ch '

o x4 -nh-c -nh-,

s

X5-s-,

xfi-o-, x7-ch = ch-xg-s-s-,

x9-soz-,

x10-nh-x "-nh-c-

O

CH3O

X, 3 pC-,

Cs)

X14-C-NHHgr ": o nh-c -

I!

O

X.s-C-NH-O-Rj.

0 nh-c-

If O

xi6-nh-c - @ - c-nh-,

o Ò

xi7-so2-nh-

x18 -so2-nh- (g) - nh-so2-,

x19-n-c- (ch2) m-c-n-,

1 II II I r4 or r4

X20 -n -c -ch = ch-c -n -, I II II I

r4 o or r4

x21-n— c — n-,

I II I

r4 or r4

x ^ -c -nh-nh-c -,

II II

o o x23 -ch2-c -nh-nh-c -ch2-

II II

o o x24 -ch = ch-c -nh-nh-c -ch = ch-

II II

o o

10th

15

25th

30th

35

40

45

50

55

60

65

"Ch2-ch,. x26-0-c-nc "> n-c-o-,

ch2-ch2 11

II

o o

n n

• II II X27 ~ C ^ C. -,

o x28-o-c-o-,

o x29-c-o-,

II

O

X30-c-c-,

II II

o o

X31 - {0- (ch2) r-0) -t,

y \

x32-n-c- c-n-

II I! I R4N n r,

^ C ^

I.

r7

. NL

f / \

x33-a-c c-Q-,

1 11

n 'n ^ /

nc

I.

r7

x34-c — n-r6-n — c-,

II I I II

o r4 r4 o

X35 -c-n - (ch2) m-0- (ch2) m-n -c -,

II I I II

o r4 r4 o x36 -c -n - (ch2) m-n - (ch2) m-n -c -,

II I I I II

o r4 ch3 r4 o x37 -c-n- (ch2) ra-0- (ch2) m-q- (ch2) m-n -c-

I.

o r4

x38-ch2-c-n-,

II I O R,

x> "- ch = ch-c-n-,

r4 o

O R4

5

647797

(Continuation)

X40 -N = N-X41 -SO-,

x42-ch2-s-ch2-x43-ch2-so-ch2-,

X44-CH2-S02-CH2-

R5 is halogen, a (1-4C) alkyl or alkoxy radical, R6 is in each case a straight-chain or branched (1-4C) alkylene radical and

R7 are halogen, -NH-CH2-CH2-OH or -N (CH2-CH2-OH) 2, and the aromatic rings B and each independently of one another by halogen and / or (1-4C) -alkyl and / or ( 1-4C) -alkoxy can be substituted and the C atom marked with * is bound to the N atom of the basic or quaternary ammonium groups.

Particularly suitable compounds correspond to the formula

10th

15

2ae 21

CH

«Äf3) p, 3

or the formula

30th

(III)

C = 0

m-lCHjn-Z

or the formula

C = 0

Z- (CH-) -NH 2. m

(iv)

(v),

35

4G

45

50

55

60

20th

X45-NH-C-NH-,

o x45 — C — NH NH-C -,

o o x47-C-NH - ^) V-R5a

0 NH-C-

ii o

X48 -NH-C -CH2-CH2-C -NH-,

II II

o o

X49 -NH-C -CH = CH-C -NH-,

II II

o o

X50 -NH-C - (CH2) 4-C -NH-,

o o x51 -n -c -ch2-ch2-c -n-, I II II I

ch3o o ch3

x52 -n — c-ch = ch-c —n-

I II II I

ch3o o ch3

C53-N — C — N-,

I II I

ch3o ch3

x54-n — c c-n-,

II II I

ch3n n ch3

V

i

R-7a

.n

S \

x55nh-c c-nh-

I II n n

V

r

• 7a x56-ch2-

x57-ch2-ch2-x58-ch2-ch2-ch2-

X59 - <ch2) 4-

xgo -c -nh- (ch2) 2-nh-c -

wherein

V each represents hydrogen or a (1-4C) alkoxy radical, W each denotes -NH-CO- (CH2) mZ, -CO-NH- (CH2) mZ, -CH2-Z or -SO2-NH- (CH2) mZ , where p'Oor 1,

R8 each represent hydrogen, CH3 or -CH2-CH2-OH and

Xa for X], X5, X6, Xc, Xjo, Xu, X12, X) 6, X22, X25, X26, X27, X30 or for o

o x6i -c-nh- (ch2) 3-nh-c -,

II II

o o x62-c-nh- (ch) 24-nh-c -

II II

o o

647797

(Continuation)

X63-C-N- (CH2) -N-C-,

o ch3 ch3o x64-c-nh-ch2-c h-nh-c -II I II

o ch3 o

R5a is hydrogen, chlorine, methyl or methoxy and R7a are each chlorine, -NH-CH2-CH2-OH or -N (CH2-CH2-OH) 2.

^ _c-n = n

Very particularly suitable sulfonic acid group-free compounds correspond to the formulas (III), (IV), (V) where xa is xb and xb is x ,, xu, xi2, x27, X45, X45, x48, X49, x50, x51, x52, 5 X54, X57, x60, x63 or x54 is available.

The process for the preparation of these compounds, which are free of sulfonic acid groups, is characterized in that a compound of the formula

10th

o-r

20th

—A-z)

r "-0-cn

20 H> 2

—N = n ~ c

11

(x)

bliss

20th

v

OH

C = CH

= C - CH,

couples, where xa for x], x5, xß, x7, x10, x „, x12, xi6, x22, x25, x26, x27, 30 x30 or for ii o

R20 in each case denotes hydrogen or a (1-4C) -alkyl radical, preferably hydrogen or CH3, treated with copper-, co-balt-, iron-, nickel-, manganese- or zinc-releasing compounds that dimethyl-containing complex compounds of the formula (I) according to Claim 1 can be obtained.

In the above formulas, n is mainly 2;

p mainly for p ';

R5 for R5a;

R7 for R7a.

In the basic compounds of formula (I) the anion Ae can be exchanged for other anions, e.g. with x45 -NH-C -NH with the help of an ion exchanger or by reaction with Sai- 11

zen or acids, optionally in several stages, e.g. about O

the hydroxide or over the bicarbonate or according to the 35 x46 -C -NH (F)) NH C -deutsche Offenlegungsschriften 2 001 748 or 2 001 816. 11 \ - '\ \

As anion Ae come those in the basic Dye-O

my usual question, mainly not suitable

mophore anions. X47 -C-NH— (0> - R

Anion Ae includes both organic and inorganic 40 n '

see ions to understand, e.g. Halogen, such as chloride or O

Bromide, also sulfate, bisulfate, methyl sulfate, aminosulfonate, perchlorate, lactate, succinate, tartrate, malate, methanesulfonate or benzoate ions or complex anions,

such as that of double chlorine zinc, and also the anions of the 45 X48 -NH-C -CH2-CH2-C -NH-, the following acids: boric acid, citric acid, glycolic acid, Jl 11

Diglycolic acid or adipic acid or addition products from ® O

ortho-boric acid with polyalcohols or cis-polyols.

The starting compounds, i.e. the non-metal-containing x49 -NH-C -CH = CH-C -NH-, compounds that have at least four to the metal complex bil 50 II II

containing enabling substituents are mostly O O

known, with the exception of the metal-free starting compounds of the formula (V) or can be prepared by methods known per se x50 -NH-C - (CH2) 4-C -NH-, e.g. if you take 1 mole of a Te II II

trazo component from a diamine with 2 moles of the same 55 O O

Coupling component or with 2 moles of a mixture of different coupling components. The diamines are also known or can be prepared by methods known per se.

The metal-free starting compounds of the formula V can be obtained if 1 mol of a tetrazo compound is obtained from a diamine of the formula

IX

v5a

NH-C-ii o

60

X51 -n -c -ch2-ch2-c -n-, I II II I

ch3o o ch3

X «-n —c-ch = ch-c —n -

h2n

1- "2

with 2 moles of a coupling component of the formula

VIII

CH30

65 cs3-n-c-n-i ii i ch3o ch3

ii i

0 ch3

(Continuation)

X54-N ~ C C-N-,

I! II I

ch3n n ch3 c /

I.

R7a n

x55 NH-C / c-NH-

i II N N

V

I.

R7a x56-ch2-x57-ch2-ch2-,

x58-ch2-ch2-ch2-x59- (ch2) 4-, •

x60 -c -nh- (ch,), - nh-c -,

II "II

o o x61 -c -nh- (ch,) 3-nh-c -,

I! II

o o x6-> -c -nh- (ch) -> 4-nh-c - "M" II

o o x63 -c -n- (ch2) -n —c -,

II I I II

o ch3 ch3o xM -c-nh-ch2-c h-nh-c -,

II I II

o ch3 o

R5a is hydrogen, chlorine, methyl or methoxy and R7a are each chlorine, -NH-CH2-CH2-OH or -N (CH2-CH2-OH) 2, and

Rio represents hydrogen or an unsubstituted (1-4C) -alkyl radical, preferably methyl.

The metallization is advantageously carried out by allowing at least two equivalents of a metal-donating agent to act on 1 equivalent of azo compound.

The 1: 1 metallization is carried out according to methods known per se, preferably in aqueous media or in mixtures of water and water-miscible organic solvents, such as, for example, acetone, low molecular weight alcohols, dimethylformamide, formamide, glycols or acetic acid and at a pH from about 3.5 to 8.0, preferably at pH 5 to 7 instead; wherein the metallization can be carried out at room temperature up to the boiling temperature of the solvent. The metallization can also be carried out in an organic solvent alone, e.g. in dimethylformamide. The cobaltization, for example, is advantageously allowed to act in the presence of an inorganic nitrite, such as lithium, sodium, ammonium or potassium nitrite, in the ratio of 2 to 6 moles of nitrite per gram atom of cobalt.

Suitable cobalt-releasing compounds are cobalt (II) sulfate, acetate, formate or chloride.

Suitable copper compounds are cuprisulfate, cupri

7 647 797

formate, cupriacetate or cuprichloride. Nickel formate, nickel acetate or nickel sulfate are used as nickel compounds.

As manganese, iron or zinc compounds serve e.g. Manganese, iron or zinc formate, acetate or sulfate. 5 Preferred compounds according to the invention are those whose cationic or basic molecular weight without the metal atoms is 400-1200, in particular 450-1000 and in particular 500-950;

The compounds according to the invention are dyes and are used for dyeing, padding or printing textile material, such as cellulose material, e.g. of natural or regenerated cellulose, for example cotton, mercerized cotton, leached cotton,

Hemp, sisal, jute and flax fabrics, etc.

15 Dyeing is carried out using the exhaust process, e.g. from long or short liquors, at room temperature to boiling temperature, optionally under pressure, the liquor ratio being from 1: 1 to 1: 100 and preferably from 1:20 to 1:50. If you dye from a short liquor, the liquor ratio is 1: 5 to 1:15; the pH of the dye liquors fluctuates mainly between 3 and 10.

The exhaust dyeing can be carried out in the presence of electrolytes, but it is advantageous to dye in the absence of electrolytes, i.e. of additional electrolyte, which tends not to come from dye production, or in the presence of a small amount of electrolyte; dyeing mainly in the presence of 0-20 g / 1 or 0-10 g / 1 or 0-5 g / 1 or 0-2 g / 1 liquor of an electrolyte added to the dyebath, e.g. in the presence of alkali metal or alkaline earth metal 30, for example sodium chloride or in particular sodium sulfate.

The printing with the dyes according to the invention takes place by impregnation with a printing paste which contains a dye, water, optionally an organic acid, e.g. 35 contains acetic acid, formic acid and, if appropriate, an electrolyte and a thickening agent and subsequent fixing to the fiber.

The printing paste is printed on by means of stencils or rollers, the printing is optionally dried 40 and the dye, e.g. by steaming, e.g. fixed at temperatures around 100 ° C and the printing finished.

The dye can be fixed by the pad-steam process or by the thermosol process or the pad roll process, temperatures above 200 ° C. being avoided.

The dyeing or printing is worked up by methods known per se. The dyes according to the invention are mainly important because they have a high substantivity to cellulose.

dyeing, padding or printing, in particular, dyes according to the invention which, expressed as a percentage, correspond to the following pull-up conditions or the “degree of pull-out” or the “pull-out quotient”: after 90 minutes at cooking temperature, the dyes should be in an electrolyte-free bath with a liquor ratio of 1:20 dyed in 1/1 standard strength on mercerized cotton (yarn strand dyeing), a draw-up quotient (ratio between extracted dye to dye in the bath) of 50-100%, or 70-100%, or 80- 100% or 90-100%. The 1 / 1-60 standard strength is according to standard DIN 54 000, respectively. ISO standard RIOS / I, 1959, Part 1, defined.

The dyes have on cellulose fibers, e.g. Cotton, dyed good light fastness and wet fastness, e.g. Water, wash, sweat, peroxide and chlorine fastness. 65 The new dyes or their preparations practically or only slightly stain the wastewater during paper production, which is particularly beneficial for keeping the water clean. They do not mottle and are colored on paper

647797

largely insensitive to pH. The dyeings on paper are characterized by good lightfastness properties. After prolonged exposure, the shade changes tone-on-tone. The colored papers are wet-fast, not only against water, but also against milk, fruit juices and sweetened mineral water and, due to their good alcohol fastness, also resistant to alcoholic beverages.

The dyes have good shade stability when dyed on paper.

The new compounds can be converted into coloring preparations. Processing into stable, liquid dyeing preparations can be carried out in a generally known manner, advantageously by dissolving in suitable solvents, optionally with the addition of an auxiliary, e.g. a stabilizer; for example, according to the information in French Patent No. 1,572,030.

The new dyes are also suitable for dyeing paper, e.g. for the production of colored, sized and unskilled paper. However, they can also be used for dyeing paper after the immersion process. The dyeing of paper is carried out according to known methods.

The dyes are also suitable for dyeing or printing leather using known methods.

The dyes can also be used for dyeing, padding or printing fibers, threads or textiles made therefrom, which consist of synthetic polyamides modified by acidic groups or synthetic polyesters which are modified by acidic groups. be used.

The dyeing of this textile material can, as is customary with basic dyes, advantageously take place from acidic or neutral, aqueous liquor in liquor ratios from 1: 3 to 1:80 and at temperatures from 60 ° C. to 100 ° C. or under pressure at above 100 ° C. The dyeing can be carried out with the addition of the usual auxiliaries, e.g. Dodecyldimethyl-benzylammonium chloride as a retarder or as e.g. Stearyl alcohol with 50 moles of ethylene oxide as a non-ionic aid or e.g. Benzyloxypropionitrile as a color accelerator.

CO,

, 0-Cu 0

i I

n = n-c = c

Acid-modified polyamides are described, for example, in US Pat. Nos. 3,039,990 and 3,454,351. When dyeing leather or when dyeing base-dyeable polyamide or base-dyeable polyester 5, the information about the "pull-out quotient" or the molecular weight as stated when dyeing cellulose does not apply. Acid-modified polyesters are known from Belgian patent 549 179 and from US patent 2,893,816.

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

example 1

15 24.4 parts of dianisidine base are tetrazotized by a known method in hydrochloric acid aqueous medium and to 65 parts of the coupling component of the formula

20th

oh i

C.

hc i c = n

25 I

©

N ~~ © —N-C-CH -N (CH) Cl *

= N— H 2 3 3

e ch "

(a)

30th

coupled at a pH of 4. A red dye is obtained.

34.4 parts of this dye (a) are dissolved or suspended in 400 parts of dimethylformamide, 42 parts of diethanolamine and 13.3 parts of copper acetate and the mixture is stirred at 90 ° for 4 hours. The reaction mass is concentrated in a rotary evaporator to half the reaction volume and the reaction solution is precipitated in 3000 parts of acetone. The red copper dye of the formula is obtained

40

I ^ N — N-Ç-CH -N (CH_)

©

h3c-c = n h

B

3 3

2 cl

©

The dye has a high substantivity on cotton and paper and has good fastness properties.

Example 2

10.9 parts of 2-amino-1-hydroxybenzene are diazo-treated in known hydrochloric acid aqueous medium and coupled to 3-pyridinium-pyridone-6 at a pH of 3-4. After coupling, the brown dye suspension is filtered at pH 9, washed and dried.

The dye of the formula

<Public transport * = N

oh oh "n ch, 0

dissolves in aqueous acetic acid solution with orange color.

9.5 parts of the dye (b) are dissolved in 92 parts of 92% sulfuric acid at room temperature. At a temperature of 20-25 °, 1.34 parts of formaldehyde in the form of a 37% solution are added dropwise to this solution. The reaction mixture is stirred for 6 hours and is cooled to 1000 parts of acetone with ice cooling. The orange suspension of the product of the formula obtained

6e

-ch

CH3-COO0 (b)

65

^ 3

2CH3C00

©

(c)

9

647797

is suctioned off and washed with acetone.

9.1 parts of the compound of formula (c) are stirred in 100 parts of water at 60 ° and a pH of 4. 6.25 parts of copper sulfate, dissolved in 30 parts of water, are added dropwise to this reaction mixture, the pH being kept between 4 and 5 by adding sodium acetate. The mixture is left to react for 7 hours, the reaction mixture is precipitated into 1000 parts of acetone, the dye obtained is filtered and worked up by known methods.

The dye of the formula

1

-h2c-

H

O-Cu-O. .N CiL

2ch3c00

15

nh- (ch2) 3-n (ch3) 2

that dyes cotton and paper in blue tones with good fastness properties. It has a high substantivity on both substrates.

The structural structure of further dyes, as can be obtained according to the information in Example 1, is given in Table I below. They correspond to the formula

20th

dyes cotton and paper in a brown-red shade with high substantivity and good fastness properties.

Example 3

Dianisidine is coupled to 3-pyridinium-pyridone-6 by a known method (see German Offenlegungsschrift 2,627,680).

15.2 parts of this known dye are dissolved in 200 parts of dimethylformamide and 25.2 parts of diethanolamine, and 8 parts of copper acetate are added to the solution. The mixture is heated to 80 ° for 6 hours and stirred. The reaction mixture is concentrated in a rotary evaporator and then precipitated into 3000 parts of acetone. The brown suspension is filtered off and the residue is dried. The dye of the formula

25th

-X

e

2ch3coo dyes cotton and paper in a brown-violet shade. Examples

81 parts of the dye of the formula described in Swiss patent 760 329

30 where Wx, V, Q, Me and XQ have the meaning given in the corresponding columns.

Anions are those listed in the description.

The symbol Q can stand for any of the residues Q listed in Tabel-35 le A. These groupings can easily be replaced by another of the specified groups in each individual dye.

Table A 40 Qi means -N (CH3) 2 Q2do. -N® (CH3) 3A ©

Q3do. -N® (CH3) 2A ©

I.

45

Q4do.

Qs do.

CH2-CH2-OH A9

-®n

50

/

ch3

CH,

O

N = N

OCH,

nh- (ch2) 3 ~ n (CH3) 2 i 2

Q6do.

Ae

A ©

55

ch,

are dissolved in 1000 parts of dimethylformamide and 126 parts of diethanolamine, and the mixture is mixed with 40 parts of copper acetate and then stirred at 90 ° for 4 hours. Working up is carried out as described in Example 1. The dye of the formula is obtained

The symbol Wx can stand for any of the residues Wx listed in Table B. These groupings can easily be replaced in this way in each individual dye by another of the specified groupings.

Table B

1 means -CH2-

2 do. -NH-CO-CH2- «3 do. -S02-NH- (CH2) 2

4 do. -S02-NH- (CH2) 3-

5 do. -CO-NH- (CH2) 2-

6 do. -CO-NH- (CH2) 3-

647797

10th

Table I

Example No.

x0

Me

V

q wx

5

x,

Cu, Co, Ni, Fe, Zn, Mn

H

qr-qs

1-6

6

x7

Cu

H

qz

1-6

7

x "

Cu, Co, Ni, Fe

H

q1.q2

1-6

8th

xi2

Cu

H

q2, q3

1-6

9

x27

Cu

H

q2, q5j qs

1-6

10th

X45

Cu, Co, Ni, Fe

H

q1-Q3

1-6

11

x46

Cu

H

q2

1-6

12

x48

Cu

H

q2

1-6

13

X49

Cu

H

q2, q3, q4

1-6

14

X51

Cu

H

q2

1-6

15

X52

Cu

H

q2

1-6

16

x55

Cu

H

q2

1-6

17th

x56

Cu, Co, Ni, Fe

H

q1-q6

1-6

18th

x57

Cu, Co, Ni, Fe

H

qi-qs

1-6

19th

x «

Cu

H

q2

1-6

20th

x63

Cu

H

q2

1-6

21st

x «

Cu

H

q2

1-6

22

x,

Cu, Ni

OCH3

qi_q4

1-6

23

'x7

do.

do.

do.

1-6

24th

x "

do.

do.

do.

1-6

25th

X12

do.

do.

do.

1-6

26

x27

do.

do.

do.

1-6

27th

X45

do.

do.

do.

1-6

28

x46

do.

do.

do.

1-6

29

x48

do.

do.

do.

1-6

30th

X49

do.

do.

do.

1-6

31

x5,

do.

do.

do.

1-6

32

X52

do.

do.

do.

1-6

33

X55

do.

do.

do.

1-6

34

x56

Cu, Ni

OCH3

q1-q4

1-6

35

x60

do.

do.

do.

1-6

36

x63

do.

do.

do.

1-6

37

x «

do.

do.

do.

1-6

The dyes of Examples 5 to 37 give a reddish-yellow to bluish-red shade when dyed on cotton or paper.

Table II below shows the structural structure of further dyes, as can be obtained according to the information in Example 2. They correspond to the formula oo

2A

©

42

X27

Cu

0

43

X45

Cu

0.1

40 44

x46

Cu

0

45

x48

Cu

0.1.2

46

X49

Cu

0

47

X5,

Cu

0.1.2

48

X52

Cu

0

45 49

X55

Cu

0

50

X56

Cu, Co, Fe, Ni

0.1.2

51

X57

Cu, Co, Fe, Ni

0.1.2

52

X «,

Cu

0.1

53

X63

Cu

0.1.2

50 54

XM

Cu

0.1.2

wherein

P, Me and X00 have the meanings given in the corresponding columns.

Anion Ae are those listed in the description.

The dyes of Examples 38 to 54 dye cotton and paper in a reddish brown shade.

The following table III shows the structural structure of 55 further dyes as can be obtained according to the information in Example 4. They correspond to the formula

Tables

Example No.X00 Me

38 X,

39 X7

40 X "

41 X12

Cu, Co, Ni, Fe, Zn, Mn 0.1.2

Cu 0.1.2

Cu 0.1.2

Cu 0.1.2

60

65

O-Me-O

CH2 (CH2) t-Q

n where

11

647 797

Q has the meanings given in Table A, t represents 2 or 3 and

Me and Xn have the meanings given in the corresponding columns.

Anion Ae are those listed in the description.

Table III

Example No.

Xn

Me

Q

55

x,

Cu, Co, Ni, Fe, Zn, Mn

Qi-QÔ

56

x7

Cu, Co

Qb Q2

57

x "

Cu, Co, Ni, Fe

Qi> Q2

58

X, 3rd

Cu

Qi, Q2

59

x27

Cu

Qi-Q6

60

x45

Cu, Co, Ni, Fe

Qi-Q6

61

X46

Cu

Qb Q2

62

X48

Cu

Qi> Q2

63

X49

Cu

Qi, Q2

64

X5,

Cu

Q., Q2

65

X52

Cu

Ql, Q2

66

X55

Cu

Qb Q2

67

X56

Cu, Co, Ni, Fe

Qi-Qfi

68

x57

Cu, Co, Ni, Fe

QrQe

69

X «,

Cu

Qi, Q2

70

X63

Cu

QbQ2

71

Xm

Cu

Qi, Q2

The dyes of Examples 55 to 71 give blue and red to blue shades when dyed on cotton and paper.

Staining instructions A

In a Dutch company, 70 parts of chemically bleached sulfite cellulose (from softwood) and 30 parts of chemically bleached sulfite cellulose (from birch wood) are ground in 2000 parts of water. 0.2 part of the dye described in Example 1 is sprinkled into this mass. After 20 minutes of mixing, paper is made from this mass. The absorbent paper obtained in this way is colored red. The wastewater is practically colorless.

Dyeing Instructions B

0.5 part of the dye from Example 1 is dissolved in 100 parts of hot water and cooled to room temperature. This solution is added to 100 parts of chemically bleached sulfite cellulose, which has been ground in a Dutchman with 2000 parts of water. After 15 minutes of mixing, sizing takes place. Paper made from this fabric has a red shade of medium intensity with good wet fastness properties.

Staining instructions C

An absorbent paper web made from unsized paper is drawn at 40-50 ° through a dye solution of the following composition:

0.5 part of the dye from Example 1, 0.5 part of starch and 5 99.0 parts of water.

The excess dye solution is pressed off by two rollers. The dried paper web is colored red.

The same good paper dyeings are obtained if, in the dyeing instructions A, B and C above, 10 equivalent amounts according to Example a (liquid preparation) or Example b (granulate preparation) are added.

Dyeing Instructions D

2 parts of the dye according to Example 1 are dissolved in 4000 15 parts of softened water at 40 °. 100 parts of pre-wetted cotton fabric are introduced into the bath and the bath is heated to boiling temperature in 30 minutes. The bath is kept at the cooking temperature for one hour and the evaporated water is replaced from time to time. The dye is then removed from the liquor, rinsed with water and dried. The dye absorbs the fiber practically quantitatively; the dye bath is practically colorless. A red color is obtained with good light fastness and good wet fastness properties.

25th

Dyeing Instructions E

Acid-modified polyamide fibers are placed at 20 ° C in a liquor ratio of 1:80 in an aqueous bath containing 3.6 g of sodium bisulfate 0.7 g of disodium hydro-30 g sulfate, 1 g of an auxiliary, such as e.g. contains a reaction product of a phenol with excess ethylene oxide and 0.15 g of the dye described in Example 1 (or the corresponding amount of a solid or liquid preparation of this dye). The mixture is heated to boiling in about 30 minutes and the bath is kept at this temperature for 60 minutes. After rinsing and drying, a red color is obtained with good fastness properties. Dyes 2-89 give similarly good colorations. Acid-modified polyester can be dyed similarly.

40

Staining instructions F

100 parts of freshly tanned and neutralized chrome grain leather are drummed in a liquor of 250 parts of 55 ° and 0.5 part of the dye prepared according to Example 1 for 45 30 minutes in the dyeing drum, in the same bath with 2 parts of an anionic fat liquor based on sulfonated tran base for a further one Treated for 30 minutes and the leather dried and trimmed in the usual way. You get leather of any color in a red shade. Dyes 2-89-50 hold similarly good leather colors.

Calf suede, lamb leather (chrome-vegetable tanned) and cow leather can also be dyed using known methods.

55