CH639120A5 - WATER-SOLUBLE DYES, METHOD FOR THE PRODUCTION THEREOF. - Google Patents

Description

The present invention further relates to heavy metal complex dyes of the abovementioned formula I, in which one or both R, represent a hydroxyl group and bind the metal complex with the hydroxyl groups of the coupling component (s). These are preferably heavy metal complex dyes in which two heavy metal equivalents are each bound to a molecule of the formula I in a complex manner, namely to the hydroxyl groups R, and those of the aminonaphthol disulfonic acid residues. The copper, cobalt and chromium complex dyes of the formula I according to the invention, in particular the copper complex dyes, are preferred as heavy metal complex dyes.

The present invention further relates to a process for the preparation of the new dyes of the formula I, in which 65 2 mol of the diazonium compound of one or two aromatic amines, preferably one and the same aromatic amine of the formula II

Ri x --so- - d - n = n "- k.

I '

r_

written in the form of the free acids in which R], R2, D and X have the meanings given above and K3 one of the radicals of the following formulas ho nh eo3s ho

° sh, h03s- j s0, e,

bo3s i5l,

639 120

1tcl, see above

ho3S

so3h

] iii2 cder ho 1ïh,

s0, h and K4 one of the residues of the following formulas ilOgS

ho, s

O

ho nb,

oh oh

HOaS

oaer

SOsH

E03S

so3h, or two moles of their heavy metal complex compounds with Rj equal to the hydroxyl group, preferably the 1: 1 copper complex compounds, or 1 mole of these heavy metal complex compounds of the formula IV or V and 1 mole of the metal-free compound of the formula V or IV with a halogen -s-triazine compound of formula VI

Hal

Y

n '^' N

■ shark

CED,

in which Y has the abovementioned meaning and Hai represents a chlorine, bromine or fluorine atom, condenses and, if appropriate, then subsequently reacted with an agent which gives off a heavy metal cation in a manner known per se, if appropriate in the presence of an oxidizing agent. These reactions are preferably carried out in aqueous solution, if appropriate in the presence of organic solvents at room temperature (15-25 ° C.) or elevated temperature (up to 120 ° C.) according to known processes in an analogous manner and familiar to the person skilled in the art. If the heavy metal complex dyestuffs according to the invention are prepared by subsequent metallization, as indicated here, one or both of the radicals may have the meaning of a hydrogen atom, a hydroxyl group or a lower alkoxy group.

It is furthermore possible in the manner according to the invention to convert a heavy metal complex dye of the formula I into a heavy metal dye according to the invention having another heavy metal central atom by analogously to the known methods [s. e.g. B. Angew. Chem. 64,397 (1952)] cleaves the original heavy metal atom from the complex dye and the resulting o, o'-dihydroxy-azo dye with an agent which supplies the other heavy metal atom.

35 sets. For example, copper complex dyes of the formula I can be converted into the corresponding chromium or cobalt complex dyes of the formula I.

Those dyes of the formula I and their heavy metal complexes according to the invention in which D represents a benzene nucleus are preferred, furthermore those in which D represents a naphthalene nucleus in which the azo group is bonded in the β position of this naphthalene nucleus. Furthermore, dyes according to the invention are preferred, in which Y denotes a halo atom, preferably a chlorine atom. Furthermore, those dyes are particularly important in which Ki for the above-mentioned bivalent radical 1-amino-naphthol- (8) -3,6-disulfonic acid, l-amino-naphthol- (8) -4,6-disulfonic acid or 2-amino-naphthol- (5) -7-sulfonic acid and so K2 for the above-mentioned bivalent radical of 2-amino-naphthol- (8) -6-sulfonic acid or 2-amino-naphthol- (5) -7-sulfonic acid.

In addition to the halogen atoms and the sulfonic acid group mentioned, the following individual groups are to be emphasized for the substituent Y in the triazine ring of the dyestuffs 55 of the formula I or of the compounds of the formulas III and VI:

-0-chg, -0-c2hs, -0-ch2-ch2-ch3, -oh, -o-chc ^, -0/3 '

<5 - f

-s ~ ch2-ce2-oh, -s ~ c

-s-ch - c00h, -s - // \] t0

2 »

--0

J7

'O

-soah

-m2,

-nrc2hs,

"NHC3 E ~,

"ch5

-mH-CFI

^ CE,

639 120 10

-k:! - ch2-ch2-ch, -eh ~ ch2-ce2-0s03e, -iîh-ch2-ch2-0-

^ H2-CHjj

/ "* £ 7

° --3 f

-ïîe-ce

ch2 -ce2

P-z

-CE- -Cïï "

X ^ "p.2

-K>, -K

CEg-Cn2

X °;

il-,

• ch3

nk-ce2-cïi2-s05h, -ke ~ ce2-c0c3, -nhcj? 2

ch coojì

F- G ^

C 3 7

<;: • --o ■ i-o ■

C "Hr ch5

-kh ^ ■ -iï ~ ce2-ce2-s03h,

OOS

<? * s05ïï

-i mHQr $ o, E

so3h

so.

e

-NB-NE- ^ V>, -KE-CE2- ^ J ^,

-ne-ch2-ce2

"ö .-» 3 ■

-nh fi so3h so3h

45

50

The formula radical Y preferably denotes a chlorine, bromine or fluorine atom or a sulfo, amino, methylamino, dimethylamino, β-hydroxyethylamino, β-methoxyethylamino, β-sul-fatoethyl amino-, ß-sulfoethyl-amino-, N-methyl-N-ß-sulfo-ethyl-amino-, carboxymethyl-amino-, N-ß-carboxyethyl-amino-no-, N- (carboxyphenyl) -amino-, N- (sulfophenyl) amino, N- (disulfophenyl) amino, N- (sulfonaphthyl (l)) amino, N-methyl-anilino, morpholino, iso-propoxy, phenoxy - or the ß-hydroxyethylthioether group.

Also to be mentioned as preferred are compounds of the formula I in which D is a benzene nucleus and R], R2, K ,, K2, Y and X have one of the abovementioned, in particular the preferred, meanings, and furthermore compounds of the formula I, in which D represents a naphthalene nucleus which is bonded in the 2-position to the azo group, R represents a hydrogen atom and R2 represents the sulfo group in the 6-position of the naphthalene nucleus or R] denotes the sulfo group and R2 represents hydrogen and K ^ Kt, Y and X are one of the above, especially the preferred meanings.

Furthermore, particular preference is given to compounds of the formula I in which D represents a benzene nucleus in which the group -S02-X is in the meta or para position to the azo group, or in which D represents a naphthalene nucleus bonded in the 2 position to the azo group means that contains the group -S02-Xin 6- or 8-position, and R ,, R2, K), K2, Y and X has one of the abovementioned, in particular the preferred, meanings 65.

The aromatic amines of the formula II are known, for example from DE-PS1278041,1276842,1150163,

55

60

./13a

1126542 and 1153029, from DE-OS 2154943,2100080, 2049664,2142728,2034591 and 1943904 or from DE-AS 1204666.

Aromatic amines of the formula II which may be mentioned in particular are the following compounds:

Aniline-3-ß-sulfatoethylsulfone

Aniline-4-ß-sulfatoethylsulfone

2-amino-toluene-4-ß-sulfatoethylsulfone

2-amino-anisole-4-ß-sulfatoethylsulfone

2-amino-anisole-5-ß-sulfatoethylsulfone

2-amino-4-ß-sulfatoethylsulfonyl-benzoic acid

2-methoxy-5-methyl-aniline-4-ß-sulfatoethylsulfone

2.5-Dimethoxy-aniline-4-ß-sulfatoethylsulfone 2,4-dimethoxy-aniline-5-ß-sulfatoethylsulfone 4-aminoanisole-2-ß-sulfatoethylsulfone 4-aminotoluene-2-ß-sulfatoethylsulfone

4-ß-sulfatoethylsulfonyl-aniline-2-sulfonic acid

5-ß-sulfatoethylsulfonyl-aniline-2-sulfonic acid 2-chloroaniline-4-ß-sulfatoethylsulfone 2-chloroaniline-5-ß-sulfatoethylsulfone 2-bromaniline-4-ß-sulfatoethylsulfone

2,6-dichloroaniline-4-ß-sulfatoethylsulfone 2,6-dimethyl-aniline-4-ß-sulfatoethylsulfone 2,6-dimethyl-aniline-3-ß-sulfatoethylsulfone 2-amino-phenol-4-ß-sulfatoethylsulfone 2-amino- phenol-5-ß-sulfatoethylsulfone

6-bromo-2-amino-phenol-4-ß-sulfatoethylsulfone 6-chloro-2-amino-phenol-4-ß-sulfatoethylsulfone

11

639 120

6-nitro-2-aminophenol-4-ß-sulfatoethylsulfone

4-methyl-2-aminophenol-5-ß-sulfatoethylsulfone

2-naphthylamine-5-ß-sulfatoethylsulfone

2-Naphthylamine-B-ß-sulfatoethylsulfone

8-ß-sulfatoethylsulfonyl-2-amino-naphthalene-6-sulfonic acid

6-ß-sulfatoethylsulfonyl-2-amino-naphthalene-l-sulfonic acid

2-NaphthyIamin-6-ß-sulfatoäthyIsuIfon and the corresponding vinylsulfonyl, ß-thiosulfatoethylsulfonyl and ß-chloroethylsulfonyl compounds.

The coupling components of the formula III are also known and are described, for example, in German Patent 5 436179. Examples of possible coupling components of the formula III are:

HO., S

H0a S

OH

^ 03K

ho3s

, iî® p lïH ~

ho3s ho3s

Y

ri

"So3H

w

HO

hoôs

ÇH

i

S0ÖH

H03S

HOaS

0, E

Y

HO

S03H

^ o3H

ÇH.

^ 503K

HO, S

S03H

639 120

12

hogs

/ "kh"

A

EN

S03iî HO, S

^ so3E

ho3s

N- with m "V1

so3h ira sosh o5h ho

ÏÏ03S

y oh so3h oh ho5s

<y so5h so5h

A

hn "

ho5s so3h oh so, h so3h o5h so5h hoßs

A

hn qs s0, h

'5- so5h ho nh

A

HO,

sosh so3e

where Y has one of the meanings mentioned above.

The aromatic amines of the formula II can be diazotized by generally known methods. However, it should be noted that these aromatic amines and the diazonium salts obtained therefrom are not subjected to more alkaline conditions during processing.

The coupling of the diazotized amines with the coupling components of the formula III is preferably carried out in a pH range between 3 and 7 at temperatures between -5 ° C and + 30 ° C.

The transfer of the dyes to the heavy metal complex dyes takes place in the presence of a hydroxyl group at all times to the azo bridges in the residues of the diazo components, that is to say in the case where Rj = OH in formula I, by adding a heavy metal donor to the dye solution or the dye suspension and optionally an acid-binding agent and optionally treatment at elevated temperature (the reaction can generally be carried out at 0-120 ° C.) until it is completely converted into the desired heavy metal complex dye.

Examples of possible heavy metal releasing agents are: salts of copper, such as copper sulfate, copper chloride, copper acetate or copper carbonate, salts of chromium such as chromium formate, chromium acetate, chromium sulfate, potassium-chromium alum or chromium salicylic acid, or salts of cobalt, such as cobalt sulfate, cobalt chloride or a Cobalt-tartaric acid complex.

Alkali metal salts of weaker inorganic or organic acids, such as sodium carbonate, sodium bicarbonate or sodium acetate, are preferably used as acid-binding agents in the conversion into the heavy metal complex dyes.

Is R | in formula I an alkoxy group, preferably a methoxy group, this can be converted into the hydroxy group by known methods during the conversion into the heavy metal complex dye, preferably the copper complex dye, and these can participate in the complex formation.

If Ri in formula I is a hydrogen atom, this can be done under the conditions of oxidative copper plating [Angew. Chem. 70, 232-238 (1958)] for a hydroxyl group, while including the latter in the complex assembly. Descendants of hydrogen peroxide, such as sodium peroxide, salts of peroxysulfuric acid or salts of perboric acid, but preferably hydrogen peroxide itself, are advantageously used as oxidizing agents. Favorable reaction conditions are generally at 20-100 ° C and pH values between 7 and 3.

The starting dyes of the formulas IV and V can be prepared by known methods, for example by the processes described in German Auslegeschrift 1126542.

The dyes of the formula I or their heavy metal complex compounds are deposited, for example, according to generally known methods, either by precipitation from the reaction medium by means of electrolytes, such as sodium chloride or potassium chloride, or by evaporation of the reaction solution, for example by spray drying.

If the latter type of dye isolation is chosen, it is often advisable to remove any sulfate present in the solutions by precipitation as gypsum and separation by filtration before evaporation. In some cases it may also be desirable to add the dye solution directly to the dyeing use as a liquid preparation, if appropriate after adding buffer substances.

The dyes according to the invention can be used for dyeing and printing cellulose and polyamide fiber materials.

Baum13 639 120 is the preferred cellulose fiber material

wool and regenerated cellulose, but also other plant fibers, such as linen, hemp, jute, understood. Polyamide fibers are to be understood as meaning both native and synthetic origins, e.g. both wool and other 5 animal hair as well as silk as well as polyamide-6.6, polyamide-6, poly-amide-11 or polyamide-4.

The dyes according to the invention can be applied to the substrates mentioned using the application techniques known for reactive dyes. They are characterized by clear 10 shades and high color strength.

So you get very good color yields on cellulose fibers by pulling out from a long liquor using a wide variety of alkali additives.

According to the padding process, 15 excellent color yields are also obtained on cellulose fibers, which can be fixed by staying at room temperature, by steaming or with dry heat. Dye components that are not fixed can be easily washed out.

Also according to the usual printing processes for cellulose fa-20 sera, - single-phase in the presence of sodium carbonate or other acid-binding agents in the printing ink and subsequent steaming at 101-103 ° C, or two-phase, printed with neutral or weakly acidic printing ink and then either by a hot one led electrolytic alkaline bath or 25 but padded with an alkaline electrolyte-containing padding liquor and then developed by lingering, steaming or dry heat, - you get strong colored prints with good contours and a clear white background. The failure of the prints is only slightly dependent on changing fixing conditions. 30 The dyeings on polyamide fibers are usually carried out from an acidic environment. For example, acetic acid or acetic acid and ammonium acetate can be added to the dyebath in order to obtain the desired pH. In order to achieve a useful levelness of the dyeings, it is advisable to add conventional leveling agents, for example based on a reaction product of cyanuric chloride with three times the molar amount of an aminobenzenesulfonic acid and / or an aminonaphthalenesulfonic acid and / or on the basis of a reaction product of stearylamine with ethylene oxide. The 40 dyeings can be carried out both at boiling temperature and at 110-120 ° C.

For the coloristic behavior of the dyes according to the invention, it should be emphasized in particular that they have a very good drawability from a long liquor, a good color structure 45 according to the customary dyeing and printing processes, and an equal depth of color when dyeing on cotton and regenerated cellulose fibers A level product image of the dyeings and prints produced with them and also characterized by an even failure of the dyeings from a long liquor with the addition of 50 different amounts of electrolytes, such as sodium sulfate or sodium chloride.

The fastnesses of the dyeings and prints obtained with the dyes according to the invention, in particular those on cellulose fibers, are remarkable. Nevertheless, this applies to the 55 most important manufacturing and usage fastnesses. Particularly noteworthy are the light fastness, the wet fastness, such as wash fastness, walking fastness, water fastness, sea water fastness, over-dyeing fastness and sweat fastness as well as pleating fastness, ironing fastness and rubbing fastness. 60 The following examples serve to explain the invention. The parts by weight given there relate to parts of the room like the kilogram to the liter.

example 1

65 281 parts by weight of aniline-4-ß-sulfatoethylisulfone are suspended in 1400 parts by volume of water and 600 parts by weight of ice and dissolved by adding 62.5 parts by weight of calcined soda, a pH of 6.0-6.5 being established.

639 120

14

Then 205 parts by weight of 5N sodium nitrite solution are added, 10 parts by weight of diatomaceous earth are stirred in and the solution is clarified. The filtrate can be run into a mixture of 1500 parts by weight of ice and 282 parts by weight of 31% hydrochloric acid at 0-5 ° C. The mixture is stirred for one hour at 0-5 ° C., then the excess nitrous acid is destroyed using amidosulfonic acid and the resulting diazonium salt solution is then adjusted to pH 6.0 by introducing about 45 parts by weight of sodium carbonate. This solution is left within 15 min in a solution of the secondary condensation product of! 4 mol of cyanuric chloride and 1 mol of 1-amino-8-naphthol-3,6-disulfonic acid and 2-amino-5-naphthol-7-sulfonic acid shrink, which is produced as follows:

92.5 parts by weight of cyanuric chloride are dissolved in 300 parts by volume of acetone and then allowed to flow into 2500 parts of the water with good stirring. A solution of 159.5 parts by weight of l-amino-8-naphthol-3,6-disul-

fonic acid and 60.5 parts by weight of 33% sodium hydroxide solution in 700 parts by volume of water and stirred for 10 minutes, whereupon a solution of 119.5 parts by weight of 2-amino-5-naphthol-7-sulfonic acid, 46 parts by weight of 33% sodium hydroxide solution and 150 parts by weight of crystallized Sodium acetate in 1000 parts of water was added and stirring continued for 1 h. After the diazonium salt solution and the solution of the coupling component are combined, the mixture is stirred at about 20 ° C. for several hours, the pH being kept at 5.5-6.0 by adding a total of about 161 parts by weight of sodium carbonate in portions. After the coupling reaction has ended, the dye solution is clarified and then the dye is precipitated by adding about 4000 parts by weight of potassium chloride. After cooling to 8-10 ° C, the dye is filtered off and dried in a vacuum 15 at 60 ° C. A red powder is obtained which really colors cotton in the presence of acid-binding agents in red tones. The dye has the following constitution:

Cl oh

0os

ho nh nh '

ch0! ^ ch "

I.

0s03b so3H

so I

ch I

ch!

oso3h

Example 2 e; ne solution of 113.5 parts by weight of 2-amino-5-naphthol-7-

251 parts by weight of 2-naphthylamine-8-ß-hydroxyethylsulfone sulfonic acid and 45 parts by weight of 33% sodium hydroxide solution in 1000

are added to 6 room parts of 20% oleum 35 room parts of water over a period of 20 minutes and then 150 parts by weight are added, the temperature rising to 60 ° C. It will be sprinkled in 4 hours of crystallized sodium acetate. Then

held at 65-70 ° C, then allowed to cool to 30 ° C and added to one of the 86 parts by weight of aniline-3-sulfonic acid and on

Mixture of 2500 parts by weight of ice and 100 parts by volume of water heated to 90-95 ° C, the pH value by adding sodium

given. The mixture is then kept at pH 6.5-7.0 at 0-5 ° C. by adding 200 bicarbonate. It'll be a few hours

Parts of the room diazotized 5n sodium nitrite solution, stirred for one hour at 40 at the temperature mentioned and pH 6.5-7.0, then on

Stirred 0-5 ° C and then allowed to cool by adding 1184 weight room temperature.

share calcium carbonate adjusted to pH = 5.0. After the diazonium solution and the solution of the coupling agent have been combined to form a lung component within a few minutes, several solutions of the tertiary condensation product from Vi mol cyan hours are stirred at about 20 ° C., the pH value being increased by portionwise addition chloride, 1 mol of 2-amino-5-naphthol-7-sulfonic acid and Vi mol 45 be of a total of about 64 parts by weight of sodium bicarbonate in aniline-3-sulfonic acid, which was prepared as follows: 5.3-6.2 is maintained. After the clutch has ended,

92.5 parts by weight of cyanuric chloride are heated in 300 parts of the room at 60-65 ° C., suctioned off from the precipitated gypsum, this acetone is dissolved and then washed with good water in 2500 with hot water and the filtrate is spray-dried. Parts of the room poured water. Then, at about 20 ° C, a reddish brown dye powder is obtained, which is used in solution of 119.5 parts by weight of 2-amino-5-naphthol-7-sulfone-50 acid-binding agents based on cellulose fiber material acid and 45 parts by weight of 33% sodium hydroxide solution in 1000 Raumlien can get purple hues and prints. Water was added to the paint and stirred for 10 minutes, after which the following constitution occurred:

Examples 3-138

Dyes obtained from the diazo described in Examples 1 and 2 in the table below, and the coupling components can be dyed in a manner analogous to that of cotton in the specified shades.

15

639 120

Example diazo component

Coupling component

Color on BW

. Moles of aniline-4-ß-sulfatoethylsulfone

4 2 moles of aniline-3-ß-sulfatoethylsulfone

5 2 moles of aniline-3-ß-thiosulfatoethylsulfone

6 2 moles of aniline-4-ß-chloroethylsulfone

7 2 moles of aniline-4-vinyl sulfone

8 2 moles of 2-aminoanisole-4-ß-sulfatoethylsulfone

9 2 moles of 2-aminoanisole-5-ß-sulfatoethylsulfone

10 2 mol of 2-aminotoluene-4-β-sulfatoethylsulfone

11 2 moles of 2,5-dimethoxyaniline-4-ß-sulfatoethyl-sulfone

12 2 moles of 2-methoxy-5-methyl-2-aniline-4-ß-sulfa-toethylsulfone

13 2 moles of 4-amino-anisole-2-ß-sulfatoethylsulfone

14 2 moles of 4-aminotoluene-2-ß-sulfatoethylsulfone

15 2 moles of 4-ß-sulfatoethyIsulfonylanilin-2-sulfonic acid

16 2 moles of 5-ß-sulfatoethylsulfonylaniline-2-sulfonic acid

17 2 moles of 2-chloroaniline-4-ß-sulfatoethylsulfone

18 2 moles of 2-chloroaniline-5-ß-sulfatoethylsulfone

19 2 moles of 2-bromoaniline-4-ß-sulfatoethylsulfone

20 2 moles of 2,6-dichloroaline-4-ß-sulfatoethylsulfone

21 2 moles of 2,6-dimethylaniline-4-ß-sulfatoethylsulfone

22 2 moles of 2,6-dimethylaniline-3-ß-sulfatoethylsulfone

23 2 moles of 2-naphthylamine-5-ß-suIfatoäthyIsulfon

24 2 moles of 2-naphthylamine-6-ß-sulfatoethylsulfone

25 2 moles of 8-ß-sulfatoethylsulfonyl-2-aminonaphthalene-6-sulfonic acid

26 2 moles of 6-β-sulfatoethylsulfonyl-2-aminonaphthalene-1-sulfonic acid

27 2 moles of aniline-3-ß-sulfatoethylsulfone

28 2 moles of aniline-4-ß-thiosulfatoethylsulfone

29 2 moles of aniline-4-ß-chloroethylsulfone

30 2 moles of aniline-4-vinyl sulfone

31 2 moles of 2-aminoanisole-4-ß-sulfatoethylsulfone

32 2 moles of 2-methoxy-5-methyl-aniline-4-ß-sulfato-ethyl sulfone

33 2 moles of 2,5-dimethoxyaniline-4-ß-sulfatoethyl-sulfone

Condensation product from 1 mol of cyanuric chloride and 1 mol of 1-amino-8-naphthol-3,6-disulfonic acid and

2-Amino-8-naphthol-6-suifonic acid ditto ditto ditto ditto ditto ditto ditto ditto ditto ditto ditto ditto ditto ditto ditto ditto dittit

Condensation product from 1 mol of cyanuric chloride and 1 mol of 1-amino-8-naphthol-3,6-disulfonic acid and

2-Amino-5-naphthol-7-sulfonic acid ditto ditto ditto ditto ditto red yellow, red yellow, red red red red blue, red blue, red bordo blue, red blue, red red red red red red red red red red blue , red blue, red blue, red blue, red red red red red red blue, red ruby

34 2 moles of 8-β-sulfatoethylsulfonyl-2-amino-naphthalene-6-sulfonic acid

35 2 moles of 6-ß-sulfatoethylsulfonyl-2-amino-naphthalene-l-sulfonic acid

36 2 moles of aniline-4-ß-sulfatoethylsulfone

37 2 moles of 2-aminoanisole-4-ß-sulfatoethylsulfone

38 2 moles of 6-ß-sulfatoethylsulfonyl-2-amino-naphthalene-l-sulfonic acid

39 2 moles of aniline-4-ß-sulfatoethylsulfone

40 2 moles of aniline-3-ß-sulfatoethylsulfone

41 2 mol of aniline-4-ß-thiosulfatoethylsuIfon

42 2 moles of aniline-4-ß-chloroethylsulfone

43 2 moles of aniline-4-ß-sulfatoethylsulfone

Condensation product from 1 mole of cyanuric chloride and 1 mole each of 1-amino-8-naphthol-3,6-disulfonic acid and 2-amino-5-naphthol-7-sulfonic acid

Condensation product of 1 mol of cyanuric chloride and 1 mol of 1-amino-8-naphthol-3,6-disulfonic acid,

2-amino-5-naphthol-7-sulfonic acid and aniline-3-sul-

fonic ditto ditto

Condensation product from 1 mol of cyanuric chloride, each with 1 mol of l-amino-β-naphthol-3,6-disulfonic acid,

2-amino-5-naphthol-7-sulfonic acid and ammonia ditto ditto ditto

Condensation product of 1 mol of cyanuric chloride with 1 mol of l-amino-8-naphthol-3,6-disulfonic acid, 2-amino-5-naphthol-7-sulfonic acid and sodium biosulfite blue, red blue, red red red blue, red red red red red red

639 120

16

Example diazo component

Coupling component

Color on BW

44 2 moles of aniline-4-ß-sulfatoethylsulfone

45 2 mol of AniIin-4-ß-sulfatoethylsulfone

46 2 moles of aniline-3-ß-thiosulfatoethylsulfone

47 2 moles of 2,5-dimethoxyaniline-4-ß-sulfatoethyl-sulfone

48 2 moles of 2-methoxy-5-methyl-aniline-4-ß-sulfato-ethyl sulfone

49 2 moles of aniline-4-ß-sulfatoethylsulfone

50 2 moles of aniline-3-vinyl sulfone

51 2 moles of 2-aminoanisole-4-ß-thiosulfatoethylsulfone

52 2 moles of aniline-4-ß-sulfatoethylsulfone

53 2 moles of aniline-3-ß-sulfatoethylsulfone

54 2 moles of aniline-4-ß-sulfatoethylsulfone

55 2 moles of 2-methoxy-5-methyl-aniline-4-β-sulfato-ethyl sulfone -

56 2 moles of aniline-4-ß-sulfatoethylsulfone

57 2 moles of aniline-4-ß-thiosulfatoethylsulfone

58 2 moles of aniline-4-vinyl sulfone

59 2 moles of 2-aminoanisole-4-ß-sulfatoethylsulfone

60 2 moles of aniline-4-ß-chloroethylsulfone

61 2 moles of aniline-4-ß-sulfatoethylsulfone

62 2 moles of aniline-4-ß-sulfatoethylsulfone

63 2 moles of aniline-3-ß-sulfatoethyl-sulfone

64 2 moles of 2-aminoanisoI-4-ß-sulfatoethylsulfone

65 2 moles of 2-methoxy-5-methyl-aniline-4-β-sulfato-ethyl sulfone

66 2 moles of 2,5-dimethoxy-aniline-4-ß-sulfatoethyl-sulfone

67 2 moles of 8-β-sulfatoethylsulfonyl-2-amino-naphthalene-6-sulfonic acid

68 2 moles of 6-β-sulfatoethylsulfonyl-2-amino-naphthalene-l-sulfonic acid

Condensation product per 1 mole of 1-amino-2-amino-5-naphthol-7-i ethanol

Condensation product per 1 mole of 1-amino

2-amino-5-naphthol-7-:

taurine ditto

Condensation product per 1 mole of 1-amino

2-amino-5-naphthol-7-

taurine ditto

Condensation product per 1 mol of 1-amino-2-amino-5-naphthol-7-: ditto

Condensation product per 1 mol of 1-amino-2-amino-5-naphthol-7 condensation product per 1 mol of 1-amino-2-amino-5-naphthol-7-: acetic acid

Condensation product per 1 mol of 1-amino 2-amino-5-naphthol-7-methylaniline condensation product per 1 mol of 1-amino-2-amino-8-naphthol-6-dito from 1 mol of cyanuric chloride with S-naphthol-3,6- disulfonic acid, sulfonic acid and 2-amino

from 1 mol of cyanuric chloride and 8-naphthol-3,6-disulfonic acid, sulfonic acid and N-methyl

from 1 mol of cyanuric chloride and ■ 8-naphthol-3,6-disulfonic acid, sulfonic acid and N-methyl

from 1 mol of cyanuric chloride and 8-naphthol-3,6-disulfonic acid, sulfonic acid and morpholine from 1 mol of cyanuric chloride and • 8-naphthol-3,6-disulfonic acid, sulfonic acid and morpholine from 1 mol of cyanuric chloride and 8-naphthol-3,6- disulfonic acid, sulfonic acid and mercapto

from 1 mol of cyanuric chloride and 8-naphthol-3,6-disulfonic acid, sulfonic acid and N-co-sulfo

from 1 mol of cyanuric chloride and ■ 8-naphthol-3,6-disulfonic acid, sulfonic acid and methylaniline

Condensation product from 1 mol of cyanuric chloride and 1 mol of l-amino-8-naphthol-3,6-disulfonic acid, 2-amino-8-naphthol-6-sulfonic acid and ß-sulfato-ethylamine ditto

Condensation product of 1 mol of cyanuric chloride and 1 mol of 1-amino-8-naphthol-4,6-disulfonic acid, 2-amino-8-naphthol-6-sulfonic acid and aniline-2,5-disulfonic acid

Condensation product from 1 mol of cyanuric chloride and 1 mol of 1-amino-8-naphthol-4,6-disulfonic acid and 2-amino-8-naphthol-6-sulfonic acid. Condensation product of 1 mol of cyanuric chloride and 1 mol of l-amino-8-naphthol -4,6-disulfonic acid, 2-amino-8-naphthol-6-sulfonic acid and 4-aminobenzoic acid ditto

Condensation product of 1 mol of cyanuric chloride and 1 mol of 1-amino-8-naphthol-4,6-disulfonic acid and

2-amino-5-naphthol-7-sulfonic acid ditto ditto ditto

Condensation product from 1 mole of cyanuric chloride and 1 mole each of l-amino-8-naphthol-4,6-disulfonic acid and 2-amino-5-naphthol-7-sulfonic acid ditto ditto red red red ruby blue, red red red red red red red blue , red red red red red red red red yellow, red red red ruby blue, red red

17th

639 120

Example diazo component

Coupling component

Color on BW

69 2 moles of aniline-4-ß-suifatoäthyIsulfon

70 2 moles of aniline-3-vinyl sulfone

71 2 moles of 2-aminoanisole-4-β-thiosulfatoethylsulfone

72 2 moles of aniline-4-ß-sulfatoethylsulfone

73 2 moles of aniline-3-ß-sulfatoethylsulfone

74 2 moles of 2-aminoanisole-4-ß-sulfatoethylsulfone

75 2 moles of 8-ß-sulfatoethylsulfonyl-2-amino-naphthalene-6-sulfonic acid

76 2 moles of 6-ß-sulfatoethylsulfonyl-2-amino-naphthalene-l-sulfonic acid

77 2 moles of aniline-4-ß-sulfatoethylsulfone

78 2 moles of 2-methoxy-5-methyl-aniline-4-ß-suIfato-ethyl sulfone

79 2 moles of 2,5-dimethoxy-aniline-4-ß-sulfatoethyl-sulfone

80 2 moles of aniline-4-ß-sulfatoethylsulfone

81 2 moles of 2,6-dimethylaniline-4-ß-sulfatoethylsulfone

82 2 moles of aniline-4-ß-sulfatoethylsulfone

83 2 moles of aniline-3-ß-thiosulfatoethylsulfone

84 2 mol of 2-aminoanisole-4-β-thiosulfate ethyl sulfone

85 2 moles of 4-ß-sulfatoethylsulfonylaniline-2-sulfonic acid

86 2 moles of 5-ß-sulfatoethylsulfonylaniline-2-sulfonic acid

87 2 moles of 4-ß-sulfatoethylsulfonylaniline-2-sulfonic acid

88 2 moles of 5-ß-sulfatoethylsulfonylaniline-2-sulfonic acid

89 2 moles of aniline-3-ß-thiosulfatoethylsulfone

90

91

92

93

94

95

96

97

98

99

100

101

2 moles of aniline-4-ß-thiosulfatoethylsulfone 2 moles of 5-ß-sulfatoethylsulfonylaniline-2-sulfone-

acid

2 moles of aniline-4-ß-thiosulfatoethylsulfone 2 moles of aniline-4-ß-sulfatoethylsulfone

2 moles of aniline-3-ß-sulfatoethylsulfone 2 moles of 2-aminoanisole-4-ß-sulfatoethylsulfone 2 moles of 2-methoxy-5-methylaniline-4-ß-sulfato-ethylsulfone

2 moles of 2,5-dimethoxy-4-ß-sulfatoethylsulfone 2 moles of 8-ß-sulfatoethylsulfony I-2-amino-naphthalene-6-sulfonic acid

2 moles of 6-ß-sulfatoethylsulfonyl-2-amino-naphthalene-l-sulfonic acid

2 moles of 2-naphthylamine-8-ß-sulfatoethylsulfone 2 moles of aniline-4-ß-thiosulfatoethylsulfone

Condensation product from 1 mol of 2,4,6-trifluoro-1,3,5-triazine, each with 1 mol of l-amino-8-naphthol-4,6-disulfonic acid and 2-amino-5-naphthol-7-sulfonic acid as above

Condensation product from 1 mole of cyanuric chloride and

2 mol of 2-amino-5-naphthol-7-sulfonic acid same as above

Condensation product from 1 mole of cyanuric chloride and

2 mol of 2-amino-5-naphthol-7-sulfonic acid ditto

Condensation product from 1 mole of cyanuric chloride and

2 mol of 2-amino-5-naphthol-7-sulfonic acid same as above

Condensation product from 1 mol of cyanuric chloride and 2 mol of 2-amino-5-naphthol-7-sulfonic acid and 1 mol of dimethylamine as above

Condensation product from 1 mol of cyanuric chloride and 1 mol each of 2-amino-8-naphthol-6-sulfonic acid and

2-amino-5-naphthol-7-sulfonic acid same as above

Condensation product of 1 mole of cyanuric chloride and 1 mole each of 2-amino-8-naphthol-6-sulfonic acid, 2-amino-5-naphthol-7-sulfonic acid and ß-methoxyethyl-amine as red yellow, red red orange orange red. orange yellow, red red. orange orange yellow, red red orange orange orange orange red. orange orange orange red

102 2 moles of aniline-3-ß-thiosulfatoethylsulfone

Condensation product from 1 mol of cyanuric chloride and 2 mol of l-amino-8-naphthol-4-sulfonic acid ditto red

Condensation product of 1 mole of cyanuric chloride and yellow, red 1 mol each of 1-amino-8-naphthol-4-sulfonic acid and 2-amino-8-naphthol-6-sulfonic acid ditto yellow, red

Condensation product of 1 mol of cyanuric chloride and yellow, red 1 mol each of 1-amino-8-naphthol-4-sulfonic acid and 2-amino-5-naphthol-7-sulfonic acid ditto yellow, red

Condensation product of 1 mol of cyanuric chloride and red 1 mol each of l-amino-8-naphthol-4-sulfonic acid and l-amino-8-naphthol-3,6-disulfonic acid ditto red ditto blue, red ditto blue, red ditto bordo ditto blue, red ditto blue, red ditto blue, red

Condensation product of 1 mol of cyanuric chloride and red 1 mol of l-amino-8-naphthol-4-sulfonic acid, 1-amino-8-naphthol-3,6-disulfonic acid and 2-mercapto-ethanol ditto red

639 120

18th

Example diazo component

Coupling component

Color on BW

103 2 moles of 2-aminoanisole-4-ß-thiosulfatoethylsulfone

104 2 moles of aniline-4-ß-sulfatoethylsulfone

105 2 mol of aniline-4-β-sulfatoethylsulfone

106 2 moles of 2,5-dimethoxyaniline-4-ß-sulfatoethyl-sulfone

107 2 moles of 2-methoxy-5-methyl-aniline-4-β-sulfato-ethyl sulfone

108 2 moles of aniline-4-ß-sulfatoethylsulfone

109 2 moles of aniline-3-ß-sulfatoethylsulfone

110 2 moles of aniline-4-ß-sulfatoethylsulfone

111 2 moles of aniline-3-ß-sulfatoethyl sulfone

112 2 moles of aniline-4-β-sulfatoethyIsulfone

113 2 moles of 2-aminoanisole-4-ß-thiosulfatoethylsulfone

114 2 moles of aniline-4-ß-sulfatoethylsulfone

115 2 moles of aniline-3-ß-sulfatoethylsulfone

116 2 mol of aniline-4-β-sulfatoethylsulfone

117 2 moles of 2,5-dimethoxyaniline-4-ß-sulfatoethyl-sulfone

118 2 moles of AniIm-4-ß-sulfatoethylsulfone

119 2 moles of aniline-3-ß-sulfatoethylsulfone

120 2 moles of 2-aminotoluene-4-ß-sulfatoethylsulfone

121 2 moles of aniline-4-ß-sulfatoethylsulfone

122 2 moles of 2,6-dimethylaniline-4-ß-sulfatoethylsulfone

123 2 moles of 2,6-dimethylaniline-5-ß-sulfatoethylsulfone

124 2 moles of aniline-4-ß-sulfatoethylsulfone

125 2 mol of 2-chloroaniline-5-ß-sulfatoethylsuIfon

126 2 moles of aniline-4-β-sulfatoethylsulfone

Condensation product of 1 mol of cyanuric chloride and 1 mol of 1-amino-8-naphthol-4-sulfonic acid, 1-amino-8-naphthol-3,6-disulfonic acid and methylamine ditto

Condensation product of 1 mol of cyanuric chloride and 1 mol of 1-amino-8-naphthol-4-sulfonic acid, 1-amino-8-naphthol-4,6-disulfonic acid and taurine as above

Condensation product from 1 mole of cyanuric chloride and 1 mole each of l-amino-8-naphthol-4-sulfonic acid, 1-amino-8-naphthol-4,6-disulfonic acid and ß-aminopropionic acid

Condensation product from 1 mol of cyanuric chloride and 1 mol of 1-amino-8-naphthol-3,6-disulfonic acid and 2-amino-8-naphthol-3,6-disulfonic acid

Condensation product from 1 mol of cyanuric chloride and 1 mol of 1-amino-8-naphthol-3,6-disulfonic acid and 2-amino-5-naphthol-1, 7-disulfonic acid ditto

Condensation product from 1 mol of cyanuric chloride and 1 mol of 1-amino-8-naphthol-4,6-disulfonic acid and 2-amino-8-naphthol-3,6-disulfonic acid as above

Condensation product from 1 mole of cyanuric chloride and 1 mole each of l-amino-8-naphthol-4,6-disulfonic acid and 2-amino-5-naphthol-l, 7-disulfonic acid ditto

Condensation product of 1 mol of cyanuric chloride and 1 mol of 2-amino-8-naphthol-6-sulfonic acid, 2-amino

no-8-naphthol-3,6-disulfonic acid and a-amino acetic acid

acid ditto ditto

Condensation product from 1 mole of cyanuric chloride and 1 mole each of 2-amino-8-naphthol-6-sulfonic acid, 2-amino-5-naphthol-l, 7-disulfonic acid and isopropyl alcohol ditto ditto

Condensation product of 1 mol of cyanuric chloride and 1 mol of 2-amino-8-naphthol-3,6-disulfonic acid, 2-amino-5-naphthol-7-sulfonic acid, 2-amino-5-na-phthol-7-sulfonic acid and ß -Mercaptoethanol ditto

Condensation product of 1 mol of cyanuric chloride and 1 mol of 2-amino-8-naphthol-3,6-disulfonic acid, 2-amino-5-naphthol-l, 7-disulfonic acid and phenol red red red blue, red blue, red red red yellow , red yellow, red yellow, red red yellow, red yellow, red yellow, red red orange orange orange orange orange orange orange orange orange orange

127

2 mol of aniline-4-ß-thiosulfatoethylsulfone same as orange

128

2 moles of aniline-4-ß-sulfatoethylsulfone

Condensation product from 1 mol of cyanuric chloride and 2 mol of 2-amino-8-naphthol-3,6-disulfonic acid orange

129

2 moles of aniline-3-ß-sulfatoethylsulfone same as orange

130

2 moles of 2-aminotoluene-4-ß-sulfatoethylsulfone

Condensation product from 1 mol of cyanuric chloride and 2 mol of 2-amino-8-naphthol-3,6-disulfonic acid orange

131

2 moles of aniline-4-ß-sulfatoethylsulfone

Condensation product of 1 mol of cyanuric chloride and 1 mol of 2-amino-5-naphthol-l, 7-disulfonic acid and 2-amino-5-naphthol-7-sulfonic acid orange

132

2 moles of 2,5-dimethoxyaniline-4-ß-sulfatoethyl-sulfone ditto red

19th

639 120

Example diazo component

Coupling component

Color on BW

133

2 moles of aniline-4-ß-sulfatoethylsulfone

Condensation product of 1 mol of cyanuric chloride, 2 mol of 2-amino-5-naphthol-l, 7-disulfonic acid and 1 mol of l-naphthylamine-6-sulfonic acid orange

134

2 mol of aniline-3-ß-thiosulfatoethylsulfone same as orange

135

2 moles of 2-aminoanisole-4-ß-sulfatoethylsulfone

Condensation product of 1 mol of cyanuric chloride and 1 mol of 1-amino-8-naphthol-4-sulfonic acid and 2-amino-8-naphthol-3,6-disulfonic acid red

136

2 moles of 2-methoxy-5-methyl-aniline-4-ß-sulfato-ethyl sulfone ditto red

137

2 moles of aniline-4-ß-sulfatoethylsulfone

Condensation product of 1 mol of cyanuric chloride and 1 mol of 1-amino-8-naphthol-4-sulfonic acid and 2-amino-5-naphthol-1, 7-disulfonic acid orange

138

2 moles of 2,5-dimethoxy-aniline-4-ß-sulfatoethyl-sulfone

Condensation product of 1 mol of cyanuric chloride and 1 mol of 1-amino-8-naphthol-4-sulfonic acid and 2-amino-5-naphthol-1, 7-disulfonic acid red

Example 139

297 parts by weight of 2-aminophenol-4-ß-sulfatoethylsulfone are suspended in a mixture of 1400 parts by volume of water and 600 parts by weight of ice and then neutralized with about 76 parts by weight of anhydrous sodium carbonate. Then 205 parts by volume of 5N sodium nitrite solution are added and, after clarification, the filtrate is dripped onto a mixture of 250 parts by volume of 31% hydrochloric acid and 1500 parts by weight of ice. The mixture is then stirred for one hour at 0-5 ° C., a little excess nitrous acid is destroyed with a little amidosulfonic acid and then adjusted to pH 5.5-6.0 with about 130 parts by weight of sodium carbonate. This solution is allowed to run to a solution of the secondary condensation product of Vi mol cyanuric chloride, each with Vi mol l-amino-8-naphthol-3,6-disulfonic acid and 2-amino-8-naphthol-6-sulfonic acid, which is prepared as follows :

92.5 parts by weight of cyanuric chloride are dissolved in 300 parts of acetone with heating and poured into 2500 parts of water at 15-20 ° C. A solution is then applied at about 20 ° C

20th

25th

30th

35

159.5 parts by weight of l-amino-8-naphthol-3,6-disulfonic acid and 60.5 parts by weight of 33% sodium hydroxide solution in 750 parts by volume of water and stirred for 10 minutes, whereupon a solution of 119.5 parts by weight of 2-amino- 8-naphthol-6-sulfonic acid and 47.5 parts by volume of 33% sodium hydroxide solution in 1000 parts by volume of water and then 150 parts by weight of crystallized sodium acetate are added. The mixture is stirred at 20-25 ° C for 90 min. After the diazonium salt solution has been added, coupling is carried out at 10-20 ° C. for about 15 hours, the pH being kept at 5.5-6.0 by adding about 69 parts by weight of sodium carbonate in portions. When coupling is complete, 300 parts by weight of sodium acetate (crystalline) and 247 parts by weight of crystallized copper sulfate are introduced, adjusted to pH = 5.0 with a little 5N-acetic acid and kept at 50-55 ° C. for one hour. The dye is then precipitated by adding 4000 parts by weight of potassium chloride, filtered off and dried at 60 ° C in a vacuum. A dark powder is obtained which can be used to produce violet dyeings and prints on cotton fabric. The dye has the following constitution:

CU \

T ^ "*" 0 nh '- H03S

CH2-CH2-0S03H

so3h

CH2-CH2-0S03H

Example 140

243 parts by weight of 6-β-hydroxyethylsulfonylbenzoxazolone are introduced at 80-100 ° C. into a mixture of 225 parts by weight of 100% sulfuric acid and 225 parts by weight of 95.5% sulfuric acid and then stirred for 4-5 hours at 142-147 ° C. After the mixture has cooled to about 80 ° C., a mixture of 1500 parts by weight of ice and 500 parts by volume of water is added and then diazotized at 0-5 ° C. by slowly adding 200 parts by volume of 5N sodium nitrite solution. The mixture is stirred at 0-5 ° C. for 1 h, then excess nitrous acid is destroyed with a little amidosulfonic acid and the pH is adjusted to 5.5-6.0 by adding about 445 parts by weight of chalk. It is coupled with the coupling solution described in Example 139.

55

The mixture is stirred at room temperature for 16 h, the pH being kept at 5.6-6.1 by adding about 108 parts by weight of calcium carbonate in portions. Then is warmed to 70-80 ° C and suctioned off from the calcium sulfate formed. This 60 is washed with hot water, then 300 parts by weight of crystallized sodium acetate and 248 parts by weight of crystallized copper sulfate are added to the filtrate and the dye is coppered at 40-45 ° C and pH 5.0-5.5 for 2 hours. It is precipitated by adding potassium chloride, suction filtered and dried. A dark dye powder is obtained, with which purple dyeings and prints of excellent fastness properties are obtained on cotton materials. The dye has the following constitution:

639 120

20th

° 2

Example 141

251 parts by weight of 2-aminonaphthalene-8-β-hydroxyethylsulfone are introduced into 660 parts by volume of 20% oleum in the course of 20 minutes and then heated to 65-70 ° C. for 4 hours. It is then cooled to 25-30 ° C. and the reaction mixture is allowed to flow into a mixture of 2500 parts by weight of ice and 1000 parts by volume of water. Subsequently, 5N sodium nitrite solution is diazotized with 200 parts of the room at 0-5 ° C., stirred for one hour at the temperature mentioned and then a little excess nitrous acid is destroyed using amidosulfonic acid. The diazonium salt solution is then adjusted to pH 5.0-5.5 by adding 1200 parts by weight of calcium carbonate and combined with the coupling solution described in Example 139. It is coupled for 20 h at room temperature, the pH being reduced by portions20

25th

30th

wise addition of about 90 parts by weight of calcium carbonate is kept at 5.5-6.0. The mixture is then warmed to 70-80 ° C. and suctioned off from the calcium sulfate formed, washed with hot water and then 300 parts by weight of crystallized sodium acetate and 247 parts by weight of crystallized copper sulfate are added to the filtrate. A mixture of 228 parts by weight of 30% hydrogen peroxide and 1000 parts by volume of water is then added dropwise at 35-41 ° C. in the course of 40 min and the mixture is stirred at 35-41 ° C. for 4 h. The dye is then precipitated by adding potassium chloride, suction filtered and dried. A dark powder is obtained, with which one obtains reddish blue dyeings and prints on cotton materials. The dye has the following constitution:

Example 142

325 parts by weight of 2-methoxy-5-methyl-aniline-4-ß-sulfato-ethylsulfone are suspended in 1500 parts by volume of water and 500 parts by weight of ice and brought into solution by adding about 64 parts by weight of calcined soda, the pH between 6. 0 and 6.5. 203 parts by volume of 5N sodium nitrite solution and 15 parts by weight of diatomaceous earth are added and the solution is clarified. The filtrate is run into a mixture of 1500 parts by weight of ice and 282 parts by weight of 31% hydrochloric acid at 0-5 ° C. After stirring for one hour at 0-5 ° C, excess nitrous acid is destroyed with amidosulfonic acid and then the diazonium salt solution obtained is adjusted to pH = 6 by introducing about 40 parts by weight of sodium bicarbonate. This solution couples

Cl under the coupling solution described in Example 139 and stirred at 18-22 ° C for several hours, the pH 45 is kept at 5.3-6.2 by adding sodium bicarbonate in portions. After the coupling has ended, a solution of 346 parts by weight of crystallized copper sulfate, 483 parts by weight of crystallized sodium acetate and 318 parts by weight of glacial acetic acid in 1475 parts by volume of water is added and the mixture is boiled for 20 hours at 50 reflux. After cooling, the dye solution is clarified and then the dye is precipitated by adding potassium chloride, suction filtered and dried. A blue-black powder is obtained, which can be used to dye cotton materials in violet shades. The dye has the following constitution:

f ° 2 ch3 CH,

I l ch -0s03h

SO-I 2 ch0 I 2 ch »I 2 0s03h

21st

639 120

Example 143 with which ruby-red dyeings can be replaced on cotton materials. Example 139 replaces the solution of the clutch compo and prints. The dye has the following content through the solution described in Example 2 and works constitution:

otherwise the same, you get a dark brown dye powder,

0

- Cu \

"t

0

J

so. I,

h ° 3s ro

NH

0 '

.Cu h

0

■ 4 ^ n =

I! Nv nh s03h ch2-0s03h

\

so"

i 2 ch "

l 2 '

ch -0s03h

20th

Example 144

The unmetallized dye is produced, raised to the boiling point in the example and boiled under reflux for 6 hours. The 139 described. When the coupling is complete, the coupling dye solution is clarified and spray dried. The solution is heated to 55-60 ° C and at this temperature 320 a dark gray dye powder, with which one

Parts by weight of crystallized sodium acetate and 250 parts by weight of 25 wool fabric can produce gray-violet prints. The dye le potassium chrome alum added. Then the temperature has the following constitution:

Cr /.

n = n

Cl

| n o nh n ^ nh

Cr /.

n = n ch2-oso3h

S ° 9 I 2 ch_

1 2

ch -oso h

Example 145

The unmetallized dye is made as described in Example 140. After separation from the calcium sulfate, 300 parts by weight of crystallized sodium acetate and 295 parts by weight of crystallized cobalt sulfate are added to the dye solution and the mixture is then heated to 60-65 ° C. for 2 hours. The dye solution

43 is clarified and then evaporated to dryness in vacuo. A dark dye powder is obtained which can be used to obtain violet prints of excellent fastness properties, which are covered on cotton materials. The dye has the following constitution:

ch2-oso3h

Examples 146-185 The heavy metal complex dyes listed in the following table can be obtained in a manner similar to that described in Examples 139-145. In the “Diazo component” column, these are described as they are after the metallic

oso3h

65 are present, that is to say optionally with a hydroxyl group formed from a methoxy group by demethylating metallization or with a hydroxyl group introduced by oxidative coppering.

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639 120

Example diazo component

Coupling component

Color on BW

183 2 moles of 2-aminophenol-4-β-sulfatoethyl isulfone

184 2 moles of 2-aminophenol-5-ß-sulfatoethylsulfone

185 2 moles of 4-methyl-2-aminophenol-5-ß-sulfato-ethyl sulfone

Condensation product from 1 mole of cyanuric chloride and 1 mole each of l-amino-8-naphthol-3,6-disulfonic acid, 2-amino-5-naphthol-7-sulfonic acid and ß-amino-propionic acid as above

Copper purple

Copper copper violet violet

Example 186,531 parts by weight of the dye of the formula h0_s0-choch

15

r ° 2sO ~

n = n

H ° 3S

nh,

are dissolved in 3700 parts of water, the pH being stirred at 55 ° C. for 1 h. The dye is adjusted to 6.4-6.7 using potassium chloride in the solution. It is then allowed to precipitate, suction filtered and dried in vacuo at 60 ° C. He dye solution a solution of 92.3 parts by weight of cyanuric 25 corresponds to the dye listed in Example 72, dropwise drop of chloride in 300 parts by volume of acetone, the temperature being 20-22 ° C. The mixture is stirred for 15 minutes, then the pH example 187 value of the reaction mixture is adjusted to 6.4-6.8 306 parts by weight of the dye of the formula with sodium carbonate, 150 parts by weight of sodium acetate are added and then

30th

ho3so-ch2ch2-o2s

- <^) - N

ho nh,

water is dissolved in 1800 parts of the room and the pH is then stirred. The pH is now adjusted to 6.5-6.7 by adding sodium bi-the solution. This carbonate solution is then adjusted to 6.4-6.8 and stirred again for 15 minutes, a solution of 92.25 parts by weight of cyanuric chloride in 300 and then a solution of 266 parts by weight of the dye

Parts of acetone were added dropwise and at 18-21 ° C for 15 to 20 min 40 of the formula ho3so-ch2ch2 ~ o2s - ^^ - n = n ho3s.

nh,

in 2000 room parts of water and 150 parts by weight of the first reaction crystallized at 40-45 ° C and the second reaction

Added sodium acetate and stirred at 55-60 ° C for 1 h. The 50 cooking temperature, each carried out at pH 5.8-6.5, so

Dye is precipitated by adding potassium chloride, a dye is obtained which is suctioned off from the dye of the example and dried at 60 ° C. in vacuo. It corresponds to 56 corresponds.

the dye listed in Example 3. In a manner similar to that described in Examples 186 to 188, those in Examples 1 and 2.4 to 55.57 to 71 can be

Example 188 55 and 73 to 138 dyes also prepared.

Are the solutions of the two aminomonoazo dyes from Example 187 instead of cyanuric chloride with an aqueous Example 189

Solution of the primary condensation product from Vi mol cyan 345 parts by weight of the dye of the formula urchlorid reacted with Vi mol ß-sulfatoethylamine, the

HO3so-CH2CH2-O2 & x_

639 120

24th

are dissolved in 3000 room parts of water, whereby the pH is adjusted to 6.4-6.8 with a little sodium bicarbonate. A solution of 92.5 parts by weight of cyanuric chloride in 300 parts by volume of acetone is added dropwise to this dye solution at 15-25 ° C. and then stirred for 30 minutes at the temperature indicated. The pH of the reaction mixture is then adjusted to pH 6.4-6.8 again with a little sodium bicarbonate and stirred again for 15 minutes. Now a solution of 305 parts by weight of the dye of the formula

.cu.

ho3so-

-ch2ch2o2s nh,

in 300 parts by volume of water and 150 parts by weight of crystallized sodium acetate and then stirred for 2 hours at 50-55 ° C. After 15 cooling to 18-20 ° C, the dye is precipitated with potassium chloride, suction filtered and dried at 60 ° C in a vacuum. It corresponds to the dye mentioned in Example 140.

Example 190 20

If the solutions of the two aminomonoazo dyes from Example 189 are reacted not with cyanuric chloride but with an aqueous solution of the primary condensation product of Vi mol cyanuric chloride and Vi mol taurine, the first 25

Reaction at 40-45 ° C and the second reaction at cooking temperature, each at pH = 5.8-6.5, a dye is obtained which corresponds to that listed in Example 176.

The copper complex dyes listed in Examples 140, 141 to 143 and in the examples in the second table can also be prepared in a manner similar to Examples 189 and 190.

Example 191 306 parts by weight of the dye of the formula h03s0-ch2ch2-02st © —n =

ho nh2

ho3s so3H

If water is dissolved in 2000 parts of the room, the pH tone is added dropwise. The reaction mixture is warmed to 35-40 ° C. of the solution with a little sodium bicarbonate at 6.4-6.8 and 45 min by adding sodium bi-

adjusted and then held in the dye solution a solution 35 carbonate at pH 6.3-6.7. Then a solution of 92.5 parts by weight of cyanuric chloride in 300 parts by volume of Ace-266 parts by weight of the dye of the formula

"n = n h03s0-ch2 ~ ch2-s02 h03s

45

in 2000 parts of water, which had previously been adjusted to pH = 6.4-6.8, and the reaction mixture was heated to 60-65 ° C., the pH being adjusted to pH 6.3-6 by adding sodium bicarbonate in portions , 7 was held After no starting dye can be detected in the paper chromatogram, the dye solution is clarified and the

Dye isolated by spray drying. A red powder is obtained, with which red dyeings and prints can be produced on cotton in the presence of acid-binding agents. The dye has the following constitution in form-free acid:

? H2- ° 2S - © -N

ch2

0s03h

0s03h

Example 192

Instead of the first dye solution in Example 191

25 639 120

a solution of 344 parts by weight of the dye of the formula

^ o nh, H0 ^ S0-CH2CH2-02 "S- <J ^) ~ --n -

water in 2000 parts of the room and otherwise does the same, so can. The dye comes in the form of the free acid, which gives you a dark dye powder, with which you have the following constitution:

Color and print wool materials in brown-violet tones

/ CU \

? H2- ° 2S-CK =

Cl

—J'v OH

ch "I 2

0s03h h03s so3h

so3H

so-l 2

ch I 2

ch2-0s03h

Examples 193-199 include, for example, the following dyes

In a manner similar to that shown in Examples 191 and 192, prepare 30 containing two different diazo components.

E.g.

constitution

Color on BW

193 ° 2s ~ c ^ ~ n =

ch, I 2

SO ~ CH2 bluish.

red ch „I 2

0s03h

Cl

N

__ ho nh ^^^ nh-

194 0 „s - // \) - n = k.J.

\ ^ /

ÏH2 HO, Ef ^ CH2 S03H

0s03h

0s03h

.n = n - ^>

Xj:

s ° 3h

Cl

195 ch ~ 02s - ^) - n = ch "

so"

! 2nd

ch "

I 2

ch ,.

I 2

oso ii.

N - N - // V

red orange h03s

50-, h oso3h so.

ch "I 2

ch ,.

0s03h

639 120

26

196

O / O NH-

/ / j j

U Vn = n ^ A

V- «h XÓCh = n ^ -

cho-s0o ho_s i 2 2 3

ch0 I 2 0s03h s03h

SORCH "

Zl 2

ch "

brown-violet

so3h

0s03h

. Cu \

.0 ^ o

197

0-f

ci oh

■ N = N

chn-s0 "h0o s

^ / L $

2nd

I.

CH I

0s03h

NH

NH

N = N

"ö-t so3h so.

ch "

I 2

ch "I ^

0s03h brown-violet

Cu fr x?

"8 02f-O-N"

CH,

(2nd

ch "y 2

0s03h ho3s

Cl

NH

N

TT II

NH

OH

TO

so3H

s0 "I 2

ch "

i 2

ch9 I 2

oso h brown nh

199

fH2- ° 2S0-N = N

Çh2 H03

0s03h

0s03h red

M

Claims (24)

639 120 2nd PATENT CLAIMS 1. Water-soluble dyes of the formula I. F1 x - Ö7S - D - N i R_ Y N N = N - Kl— R. K9-N = N- D- SO-, - X I. R. (I)> in which the different formula residues have the following meanings K and K2 are the same or different, where have: K, for one of the remnants of the formulas ho wiho, s S0BH BOaS OH NH- BOjS Oh <4+ NH- nh- so3n kt for one of the residues of the formulas or OH lffl- S03H and -BN OH 1 03h or stand; D is a benzene or naphthalene nucleus; R] is in the ortho position to the azo group and means a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a hydroxyl, carboxy or a sulfonic acid group; R2 is a hydrogen atom, a halogen atom, a lower one Alkyl group, a lower alkoxy group, a nitro group R3 or a sulfonic acid group, wherein Ri and Ri can be the same or different from each other; X stands fordieß-thiosulfatoethyl, ß-chloroethyl group, ß- R4 sulfatoethyl or vinyl group; Y is a chlorine, fluorine or bromine atom or a sulfonic acid group or a group of the formula -S-R 'or -0-R ", in which ~ hn S03H S0öH so3h 55 R ' R " 60 y 65 is a substituent from the group lower alkyl, substituted lower alkyl, phenyl, naphthyl, substituted phenyl, substituted naphthyl or 2-benzothiazolyl and denotes a hydrogen atom or has the meaning of R 'other than 2-benzothiazolyl, or is an amino group of the formula -NR3R4, in which is a hydrogen atom, an optionally substituted lower aliphatic radical, an optionally substituted araliphatic radical or a cycloaliphatic radical and for a hydrogen atom, an optionally substituted lower aliphatic radical or for an optionally substituted aromatic radical or for an optionally substituted araliphatic radical or for a hydroxy or a lower alkoxy group or for 3rd 639 120 an optionally substituted amino group or in which R, and R4 together with the nitrogen atom form a ring containing lower alkylene radicals and optionally heteroatoms; or their salts and their heavy metal complex compounds, where one or both R] stand for a hydroxyl group. 2. alkali metal or alkaline earth metal salts, preferably sodium, potassium or calcium salts of the compounds of formula I according to claim 1. 3. Dyes of the formula I according to claim 1 or 2, in which D, Ri, R2, K ,, K2 and X have the meanings given in claim 1 and Y is chlorine, bromine or fluorine or a sulfo, amino, methylamino -, dimethylamino, ß-hydroxy-ethyl-amino, ß-methoxyethyl-amino, ß-sulfatoethyl-amino-, ß-sulfoethyl-amino-, N-methyl-N-ß-sulfoethyl-amino-, carbo- oxymethyl-amino-, N-ß-carboxyethyl-amino, N- (carboxyphenyl) amino, N- (sulfophenyl) amino, N- (disulfophenyl) amino no, N- (sulfonaphthyl (l)) - amino, N-methyl-anilino, morpholino, iso-propoxy, phenoxy or the ß-hydroxyethylthioether group. 4. Dyes of the formula I according to claim 1 or 2 with D, Rj, R2, K |, K2 and X of the meaning given therein, in which Y represents a chlorine atom. Dyes of formula I according to one of claims 1 to 4, with Y, R], R2, K), K2 and X of the meanings given there, in which D is a benzene nucleus. 10th Dyes of formula I according to one of claims 1 to 4 with Y, Kj, K2 and X of the meanings given therein, in which D is the naphthalene nucleus which is bonded to the azo group in the 2-position, R represents a hydrogen atom and R2 represents the sulfo group is in the 6-position of the naphthalene nucleus or R) the sulfo group and R2 is a hydrogen atom. 7. Dyes of the formula I according to claim 5 with the meanings given therein, in which the group -S02-X is in the meta or para position to the azo group. 8. Dyes of the formula I according to one of claims 1 to 4 or 6 with the meanings given therein, in which D contains a naphthalene nucleus of the group -S02-X bonded in the 6- or 8-position in the 2-position to the azo group. 15 9. Dyes of the formula I according to any one of claims 1 to 8, characterized in that X represents the vinyl or ß-sulfato-ethyl radical. 10. Dyes of the formula I according to one of claims 1 to 9, characterized in that K] for the bivalent radical of the 1- 20 amino-naphthol- (8) -3,6-disulfonic acid is 1-amino-naphthol- (8) -4,6-disulfonic acid or 2-amino-naphthol- (5) -7-sulfonic acid. 11. Dyes of the formula I according to one of claims 1 to 9, characterized in that K2 for the bivalent radical of the 2- 25 amino-naphthol- (8) -6-sulfonic acid or the 2-amino-naphthol- (5) -7-sulfonic acid. 12. Dye according to claim 1 or 2 of the formula oso3h cu2-osoyi oso3h 639 120 4th and its salts. 14. The copper, chromium or cobalt complex dyes of the dyes according to claim 1 or 2. 15. A process for the preparation of the dyes of the formula I according to claim 1, characterized in that one mole of the diazonium compound of one or two aromatic amines of the formula II wherein K |, K2 and Y have the meanings given in claim 1, couples. 16. A process for the preparation of the dyes of the formula I 5 according to claim 1, characterized in that one mole each of the monoazo compounds of the formulas IV and V 1 1 X - SO-, - D - NH0 I 2 R " (ii), 10 X - 0-.S -D-N = N-K, 2! 3rd R " (IV) wherein 15 D, R (, R2 and X have the meanings given in Claim 1 and Ri is ortho to the amino group, with 1 mol of a coupling component of the formula III Y N M H-K. -N ^ —K2-H (iii), 25th V X - S02 - D - N = N - K4 (V), R " written in the form of the free acids, in which Ri, R2, D and X have the meanings given in claim 1 and K3 one of the residues of the following formulas ho hh- BO JfflL 0ah, ho, s SO ^ H BO ^ S oh nh2 ho and h ho3s K4 one of the residues of the following formulas oh HO ^ S , ho, s sosh OH or ^ fll. ho nh ho nh, I S0ÄH Oh B05S hb. SO ^ H or HO ^ S s0ôh mean with a halogen-s-triazine compound of the formula VI Hal y Hal (VI), 5 639 120 wherein Y has the meaning given in claim 1 and shark represents a chlorine, bromine or fluorine atom, condensed. 17. A process for the preparation of the heavy metal complex dyes of the formula I as claimed in claim 1, in which both R are a hydroxyl group, characterized in that one mole each of the heavy metal complex compounds of the formula IV and V R-i i X - 02S - D - N = N - K, (IV) i R " R I1 X - S0o - D - N = N - K, 2 i 4 R ~ 10th (V), written in the form of free acids, in which R2, D and X have the meanings given in claim 1 Ri means hydroxy and K3 one of the residues of the following formulas ho kïl ho nh, VSOaH Oh HOaS " nh, ho HO.S ^^ So, and h K4 is one of the residues of the following formulas so3H or ho nh, soah oh ÜO ^ S Oh "in the. ho nh. so5h HO ^ S so ^ H or mean with a halogen-s-triazine compound of the formula VI Shark y A XJ ro5S Shark sosh (VI), wherein is hydroxy group, characterized in that one Y has the meaning given in claim 1 and mol of a heavy metal complex compound of the formula IV or Shark represents a chlorine, bromine or fluorine atom, 60 V, in which R denotes hydroxyl, and 1 mol of the metal-free is condensed. Compound of the formula V or IV, wherein Ri is the one in claim 1 18. Process for the preparation of the heavy metal complex color has the meaning given, Substances of formula I according to claim 1, wherein a Ri for an R -j i x - o2s -d-n = n-k3 R ^ (iv) 639 120 6 r I1 x - so-, - d - n I. = N - K, (v), written in the form of free acids, in which and R, D and X have the meanings given in Claim 1, K, one of the radicals of the following formulas b0ôs ho kh HO3S bo kb. soab bo3s oh NB2 BOaS and K4 one of the residues of the following formulas ho3s. so3b NB2 or ho nh bo3s HOjS oh oh nb. so3h or mean with a halogen-s-triazine compound of the formula VI hal- y so3h Shark (vi), ho nhj I SOaH wherein Y has the meaning given in claim 1 and shark represents a chlorine, bromine or fluorine atom, condensed. 19. A process for the preparation of the copper complex dyes of the formula I according to claim 1, wherein both Rt stand for a hydroxyl group, characterized in that, according to the process according to claim 18, heavy metal complex dyes of the formula I, wherein one R stands for a hydroxyl group and the other R represents a hydrogen atom, a hydroxyl group or a lower alkoxy group, and this with a copper cation-donating agent and in the event that one starts from a compound of the formula I in which one R, a hydroxyl group and the other R represent a hydrogen atom, in the presence of an oxidizing agent. 60 20. A process for the preparation of heavy metal complex dyes 55 of the formula according to Claim 1, in which one or both of the Ri are a hydroxyl group, characterized in that the metal-free dyes of the formula I according to Claim 1, in which one Ri is a hydroxyl group and the other R) represents a hydrogen atom, a hydroxyl group or a lower alkoxy group, is reacted with a heavy metal cation-donating agent. 21. A process for the preparation of the copper complex dyes of the formula I according to claim 1, in which one or both R [stand for a hydroxyl group, characterized in that the 65 metal-free dyes of the formula I according to claim 1, wherein one or both of R 1 is a hydrogen atom, a hydroxyl or a lower alkoxy group, with a copper cation donating agent and in the event that one of a compound of 7 639 120 Formula I starts, in which at least one R, a hydrogen atom With the present invention new water-soluble means, in the presence of an oxidizing agent. Dyes of the formula I. R, X - OS - D- N = N-K, z I I r, N N Y J <* - R " ■ K2 - N = N - • D - S02 - X R. (X) and their heavy metal complex compounds found. use for dyeing and printing fiber materials The new dyes of the formula I can be found in the form of the free 15 lines. Acid as well as in the form of their salts. They are preferred in the above formula I, the various formula radicals in the form of the salts, in particular the alkali metal and alkaline earth metal, have the following meaning: salts, in particular in the form of sodium, potassium and also Ki and K2 are the same or different, wherein Calcium salts. They can preferably be in the form of the alkali metal salt K, for one of the radicals of the formulas ho nh- ho j-ÏÏÏ- HOsS 05h ho5s s0sh H05S B0sS S05n and K2 for one of the residues of the formulas 0h "XCv,, -hh ho, or -MR or raised oh oh no ^ 03H SOsH -ni? ~ hn "oh 60 stand; D is a benzene or naphthalene nucleus; Ri is ortho to the azo group and means a hydrogen atom, a halogen atom, preferably a chlorine or bromine atom, a lower alkyl group, preferably a methyl group, a lower alkyl group, preferably a methoxy group, a hydroxyl, carboxy or a sulfonic acid group, R2 is a hydrogen atom, a halogen atom, preferably a Chlorine or bromine atom, a lower alkyl group, preferred R ' Ri X 65 y a methyl group, a lower alkoxy group, preferably a methoxy group, a nitro group or a sulfonic acid group, and R2 can be identical or different from one another; stands for the ß-thiosulfatoethyl or ß-chloroethyl group, preferably for the ß-sulfatoethyl or vinyl group; is a chlorine, fluorine or bromine atom or a sulfonic acid group or a group of the formula -S-R 'or -O-R ", in which a substituent from the group lower alkyl, 639 120 io 15 h-k ized lower alkyl, phenyl, naphthyl, substituted phenyl. substituted naphthyl or 2-benzthiazolyl, such as by substituents from the group Hydro- X - SC ^ - xy, lower alkoxy, sulfato, sulfo, carboxy, phenyl, Naphthyl, substituted phenyl and substituted naphthyl 5-substituted lower alkyl or, for example, phenyl or naphthyl substituted by substituents from the group nitro, sulfo and carboxy, and R "denotes a hydrogen atom or the meaning of R ' other than ß-benzthiazolyl, or Y is an amino group of the formula -NR3R4, in which R; is a hydrogen atom, an optionally substituted lower aliphatic radical or an optionally substituted araliphatic radical or a cycloaliphatic radical, such as, for example, a lower alkyl radical represented by one or two substituents from the group hydroxyl, sulfato, lower alkoxy, sulfo, carboxy and phenyl may be substituted, or is a cyclohexyl radical, and R4 represents a hydrogen atom, an optionally substituted lower aliphatic radical, such as, for example, a lower alkyl radical which is substituted by hydroxyl, lower alkoxy, Sulfato, sulfo and carboxy may be substituted, or for an optionally substituted aromatic radical, such as for example a phenyl or naphthyl radical which is substituted by one or two substituents from the group hydroxyl, Carboxy, sulfo, lower alkyl and lower alkoxy may be substituted, or for an optionally substituted araliphatic radical, such as for example a lower alkyl radical which may be substituted by phenyl or naphthyl, or for a hydroxyl or a lower alkoxy group or for an optionally substituted amino group, such as the amino or a phenylamino or lower alkylamino group, or in which R3 and R4 together with the nitrogen atom form a lower alkylene radical and optionally contain heteroatoms, such as a nitrogen or oxygen atom, such as a morpholine, Piperidine or piperazine ring. The two formula residues X - 1 D i r, - nh, ° 9 in which D, Rj, R2 and X have the meanings given above and Rj is in the ortho position to the amino group, with 1 mol of a coupling component of the formula III practices) 25th 30th 35 in which Ki, K2 and Y have the meanings given above. Furthermore, the present invention relates to processes for the preparation of the heavy metal complex dyes of the above formula I, as specified in claims 19-21. The metal-free dyes of the formula I in which R] represents a hydrogen atom, a hydroxyl or lower alkoxy group can, if appropriate, be used immediately following the above-mentioned procedure for the preparation of these metal-free dyes of the formula I in a manner known per se, if appropriate in the presence of an oxidizing agent, react with a metal-donating agent. However, the metal-free dyes of the formula I or their heavy metal complexes can also be prepared in a manner according to the invention in such a way that one mole each of the monoazo compounds of the general formulas IV and V 1 R! - d 40 02s 1 d - n i R " = n - k3 az) s0o - x r, 45 50 55 in formula I can have the same or different meaning; preferably they have the same meaning. The expression “lower” used in the definitions above means here and below that the alkyl or alkylene radical contained in the group consists of 1-4 carbon atoms.