CA1106839A - Water-soluble dyestuffs - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
The novel water-soluble disazo dyestuffs consists of two monoazo dyestuff moleties each containing as diazo component an amine of the benzene or naphthalene series and as coupling component an amino-naphthol-mono- or disulfonic acid. The two moieties are bonded to each other via a triazine radical carrying a halogen atom, a sulfonic acid group or a thio ether or oxygen ether group and is bound to the amino groups of the coupling components and the diazo components contain a fiber-reactive radical of the vinyl sul-fone series. To produce the dyestuffs 2 mols of the diazo component carrying the fiber-reactive radical of the vinyl sulfone series is coupled with 1 mol of a bivalent coupling component consisting of 2 radicals of the aminonaphthol bound to the triazine ring via the amino groups, or two monoazo dyestuffs each synthesized from the aforesaid diazo component and an aminonaphthol coupling component are reacted with a 1,3-dihalogeno-triazine containing in 5-position a further halogen atom, a sulfonic acid group, a thio ether, or an oxygen ether group. The metal-free dyestuffs, can be transformed into the correspond-ing heavy metal complex dyestuffs, preferably copper, cobalt and chromium com-plex dyestuffs, by treatment with an agent donating a heavy metal cation. The novel dyestuffs are excellently suitable for dyeing and printing fiber mate-rial of natural and regenerated cellulose and natural, regenerated and synthet-ic polyamides. They are distinguished by clear shades, high tinctorial strength, a very good uptake from a long liquor and a good color-build up.
The dyeings obtained therewith have a high fastness to processing and in use.

Description

With the prsent invention, novel water-soluble dyestuffs of the general formula (1) y X - 02S - D - N = N - Kl ¦ ~ ~ ~ K2 ~ N = N - D - SO2-X ( ) and their heavy metal complex compounds have been found.
The novel dyestuffs of the formula (1) can be in the form of the free acid or in the form of their salts. They are preferably in the form of -the salts, especially the alkali metal and alkaline earth metal salts and in particular in the form of the sodium, potassium and calcium salts. They are preferably used in -the form of the alkali metal salts for dyeing and printing fiber materials.
In the above formula (1), the various radicals in the formula have the following meaning: Kl and K2 are identical or different and Kl represents one of the radicals of the formulae H~ NH- HO NH-HO3S SO3H 3 ~

~H OH

3 NH- HO3S ~ ~ SO H

,OH OH NH-HO3S ~ ~ NH- ~ and C ~

.

a nitrogen atom or oxygen atom, such as, for example a morpholine, piperidine or piperazine ring.
The two radicals ~1 can be identical or different in the general formula (l); prefer-ably they are identical.
Here and in the text which follows, the term "lower" used in the definitions denotes that the alkyl or alkylene radical contained in the group consists of 1 - 4 C atoms.
The present invention also relates to heavy metal complex dyestuffs of the abovementioned formula (1), in which one or both of the Rls represent a hydroxy group and withthe hydroxy groups of the coupling component or com-ponents bond the metal as a complex. The heavy metal complex dyestuffs are preferably those in which two heavy metal equivalents are each bonded in com-plex form to one molecule of the formula (1), specifically in each case to the hydroxy groups Rl and those of the aminonaphthol-disulfonic acid radicals.
Preferred heavy metal complex dyestuffs are the copper, cobalt and chromium complex dyestuffs of the formula (1) according to the invention, especially the copper complex dyestuffs.
The present invention also relates to a process for the manufacture of the novel dyestuffs of the formula (1), which comprises reacting 2 moles of the diazonium compound of one or two aromatic amines, preferably a single aromatic amine of the general formula (2) C

:. ,, . : .
. ' X - S02 - D - NH2 (2) in which D, Rl, R2 and X are as defined above and Rl is in the ortho-position relative to the amino group, with 1 mole of a coupling component of the gen-eral formula (3) N ~ N ~3) H-Kl ~ " L _ - K -H
in which Kl, K2 and Y are as defined above.
The present invention also relates to a process for the manufacture of the heavy metal complex dyestuffs of the above mentioned general formula (1), which comprises reacting the metal-free dyestuffs of the formula (1) in which Rl represents a hydrogen atom or a hydroxy or lower alkoxy group, if desired immediately following the above mentioned procedure, according to the invention, for the manufacture of these metal-free dyestuffs of the for-mula (1), in a manner which is in itself known, if appropriate in the pres-ence of an oxidizing agent, with a metal donor.
The metal-free dyestuffs of the formula (1) or their heavy metal complexes can, however, also be manufactured in a manner according to the invention by subJecting one mole of each of the monazo compounds of the gen-eral formulae(4) and (5) Il X _ 02S ~ D - ~ = N - K3 (4) ' . ~ ~

X _ S2 ~ D - N = N - K4 (5) descri.bed in the form of the free acids, in which Rl, R2, D and X are as de-fined above and K3 denotes one of the radicals of the following formulae H035 503H 3 ~03H 3 N~2 HO Hp H NH2 ~ H2 ~ ~
H03S J ~ S03H H03 ~ NH2 or ~ 03H

and K4 denotes one of the radicals O-r the following formulae OH OH Hn N
~ 2 H03 ~ 3 ~ ~ NH2 ~

U~ _NH2 or ~OH

H03S S03H H03S ~ NH2 or two moles of their heavy metal complex compounds in which Rl is a hydroxy group, preferably the 1:1 copper complex compo~mds, or 1 mole of these heavy metal complex compounds of the formula (4) or (5) and 1 mole of the metal-free compound of the formula (5) or, respectively, (4) to a condensation re-action with a halogeno-s-triazine compound of the formula (6) C

6~

N ~ N
l-lal ~ ~ ~ llal in which Y is as defined above and Hal represents a chlorine, bromine or fluorine atom, and, if desired, subsequently reacting the product in a man-ner which is in itself known, if appropriate in the presence of an oxidizing agent, with an agent which donates a heavy metal cation. These reactions are preferably carried out in aqueous solution, optionally in the presence of organic solvents, at room temperature (15-25 C) or elevated temperature (up to 120 C) in accordance with known processes in an analogous manner well known to those skilled in the art. If the heavy metal complex dyestuffs ac-cording to the invention are manufactured by subsequent metallization, asindicated here, one or both of the Rls can be a hydrogen atom, a hydroxy group or a lower alkoxy group.
It is also possible, in a manner according to the invention, to convert a heavy metal complex dyestuff according to formula (1) into a heavy metal dyestuff according to the invention which contains a different heavy metal central atom, by splitting the original heavy metal atom from the com-plex dyestuff analogously to the known methods (see, for example, Angew.
Chem. 64, 397 (1952)) and reacting the resulting o,o'-dihydroxy-azo dyestuff with an agent which supplies the other heavy metal atom. Thus, for example, copper complex dyestuffs of the formula (1) can be converted to the corre-sponding chromium or cobal-t complex dyestuffs of the formula (1).
Preferred dyestuffs, according to the invention, of the formula (1) and their heavy metal complexes are those in which D represents a benzene nucleus and also those in which D represents a naphthalene nucleus, in which the azo group is bonded in the ~-position of this naphthalene nucleus. Fur-ther preferred dyestuffs according to the invention are those in which Y

C

P6~

denotes a halogen atom, preferably a chlorine atom. Furthermore, dyestuffsof particular importance are those in which Kl represents the above men-tioned divalent radical of l-amino-naphthol(8)-3,6-disulfonic acid, l-amino-naphthol(8)-4,6-disulfonic acid or 2-amino-naphthol-(5)-7-sulfonic acid and K2 represents the above mentioned divalent radical of 2-amino-naphthol(8)-6-sulfonic acid or 2-amino-naphthol(5)-7-sulfonic acid.
In addition to the said halogen atoms and the sulfonic acid group, the following individual groups are to be singled out for the substituent Y
in the triazine ring of the dyestuffs of the formula (1) or of the compounds Of the formulae (3) and (6):

_O-CH3, -O-C2H5, O CH2 CH2 3, -OH, D -o~ -S-CH2-CH2-OH ~ s c ~ ~

-S-CH2-COOH' -S ~ No2 ~ -O ~ -S3H ' -NH2, N2 ~ H3 -NH-CH3, -NHC2H5, -NHC3~7, -NH-CH
~13 -NH-CH2-CH2-OH, NH-CH2-CH2-OSO3H, -NH-cH2-cH2-o-cH3, ~ CH2-CH2~
-~H-CH2 CH2~ -NH-CH2-CH2-S03H, -NH-CH2-COOH, -NHCH2 / CH2-CH ~ / CH3 / C2 5 ¦ -N O , -N \ , -N ~

CH2COOH, \ CH2-CH2 C~3 C2H5 C

.:

H3lC CH3 N ~ -N ~ , -NH ~ , 1 CH2 CH2 SO3H

. SO3H

~NH ~ COOH -NH ~ ~SO3H , -NH

OH
-NH ~ 3 ~NH ~ - COOH , -NH-OH , _NH_NH2 -NH-NH ~ , _NH_CH2 ~ -NH-CH2-CH2 ~ , NH ~ 503H -NH ~

, :, .
.
, ' ' ' ' 6~

Preferably, the radical Y in the formula denotes a chlorine~
bromine or fluorine atom or a sulfo, amino, me-thyl-amino, dimethylamino, ~-hydroxyethyl-amino, ~-methoxyethylamino, ~-sulfatoethyl-amino, ~-sulfo-ethyl-amino, N-methyl-N-~ -sulfoethyl-amino, carboxymethyl-amino, N-~-carboxyethylamino, N-(carboxyphenyl)-amino, N-(sulfophenyl)-amino, N-(disulfo-phenyl)-amino, N-(sulfonaphthyl(l))-amino, N-methylanilino, mor-pholino, isopropoxy, phenoxy or ~-hydroxyethylthioether group.
Further compounds of the formula (1) which should be mentioned as being preferred are those in which D is a benzene nucleus and R1, R2, Kl, K2, Y and X have one of the above mentioned meanings, especially the preferred meanings, and also compounds of the formula (1) in which D de-notes a naphthalene nucleus which is bonded in the 2-position to the-azo group, Rl represents a hydrogen atom and R2 represents the sulfo group in the 6-position of the naphthalene nucleus, or Rl is sulfo and R2 is hydrogen, and Kl, K2, Y and X have one of the above mentioned meanings, especially the preferred meanings.
Further compounds which are particularly preferred are those of the formula (1) in which D represents a benzene nucleus, in which the group -S02-X is in the meta-position or para-position relative to the azo group, or in which D denotes a naphthalene nucleus which is bonded in the 2-posi-tion to the azo group and which contains the group -S02-X in the 6-position or 8-position, and Rl, R2, K , K2, Y and X have one of the above mentioned meanings, especially the preferred meanings.
The aromatic amines of theformula (2) are known, for example from German Patent Specifications 1,278,041, 1,276,842, 1,150,163, 1,126,542 and 1,153,029, from German Offenlegungsschriften 2,154,943, 2,100,080, 2,o49,664,

2,142,728, 2,034,591 and 1,943,904 or from German Auslegeschrift 1,204,666.
Aromatic amines of the formula (2) which may be mentioned are, in ':

particu]ar, the fol:l.owing compounds: aniline-3-~-su:Lfatoethylsulfone, ani]ine-4-~sulfatoethylsulfone, 2-amino-toluene-4-~-sulfatoethylsulfone, 2-aminoanisole-4-~sul.fatoethylsulfone, 2-amino-anisole-5-~suLratoe-thyl-sulforle, 2-amino-4-~-suLfatoethylsulfonyl-benzoic acid, 2-methoxy-5-methyl-aniline-4-~ suLfatoethylsulfone, 2,5-dimethoxy-aniline-4-~-sulfatoethyl-sulfone, 2,4-dimethoxyaniline-5-~-sulfatoethylsulfone, 4-aminoanisole-2-~-su~LfatoethylsfuLfoneg 4-aminotoluene-2-~-sulfatoethylsulfone, 4-~ sulfato-ethylsuLfonyl-aniline-2-su~Lfonic acid, 5-~ sulfatoethylsulfonyl-aniline-2-sulfonic acid, 2-chLoroaniline-4-~- sulfatoethylsulfone, 2-chloroaniline-5-B-sulfatoethylsulfone, 2-bromoaniline-1~-sulfatoethylsulfone, 2,6-dichloro-aniline-4-B-sulfatoethylsulfone, 2,6-dimethyl-aniline-4-~- sulfatoethyl-sulfone, 2,6-dimethyl-aniline-3 ~-sulfatoethylsulfone, 2-amino-phenol-4 -~-sulfatoethylsulfone, 2-amino-phenol-5~- sulfatoethylsulfone, 6-bromo-2-amino-phenol-4-~-sulfatoethylsulfone, 6-chloro-2-amino-phenol-4-B-sulfato-ethylsulfone, 6-nitro-2-amino-phenol-4-~ sulfatoethylsulfone, 4-methyl-2-amino-phenol-5-B-sulfatoethylsulfone, 2-naphthylamine-5-~ sulfatoethylsul-fone, 2-naphthylamine-8-~-su~Lfatoethylsulfone, 8-~ sulfatoethylsulfonyl-2-amino-naphthalene-6-su~Lfonic acid, 6-~-sulfatoethylsulfonyl-2-amino-naphthalene 1-sulfonic acid, 2-naphthylamine-6-~-sulfatoethylsulfone and the corresponding vinylsulLfonyl~ B-thiosulfatoethylsulfonyl and ~-chloro-ethylsulfonyl compounds.
The coupling components of the formula (3) are also known and are described, for example, in ~erman Patent Specifica-tion 436,179. Coupling components of theformula (3) which can be used are, for example:
C

) ~ ~ S03H

H03S 3 ~

Y OH
N ~ N ~ ~ ' ~
~ ~ 3 / 503H ~ ~ rL

HO y OH Y OH
N ~ N ~ N ~ N
~ ~ ~ N ~ ~ ~ ~ H ~

3 3 ~ S03H

OH y WH

1) -10-I OH

D HO S ~ H035 ~

" ~ NH ~ NH ~ S03H

N ~ N OH

~ HO3S ~ S031~

N ~ N

HO S~ 03H HO S ~ 503H

Y OH

HO35 ~\NH 1N;~NH ~SO H

' ~' ' ' :

,. ` .., ~, . ' ' ' ' ~h~

HO3S I NH N NH ~ SO3H NH 1 N

OH Y OH

HO S / ~ NH N WH ~ 3 53H

y N ~ N
/ ~ ~ OH Y
HO NH NH \ ~ N N OH

3H ~ ~ 3 3 ~ H SO3H
N N ~
/~N ~ J`~

3 ~ 3 y S 3 )`N~ HO NH ~N HN OH
H S/~ NH OH HO3~,~ o3H

in which Y has one of the above mentioned meanings.
The diazotization of the aromatic amines of the formula (2) is carr-ied out by generally known methods. However, care must be taken that these aromatic amines, and the diazonium salts obtained therefrom, are not subjected to strongly alkaline conditions during processing.
The coupling of the diazotized amines with the coupling components of the formula (3) is preferably carried out in a pH range between 3 and 7, at temperatures between -5 and +30C.
If a hydroxy group is present in the o-position relative to the azo bridges in the radicals of the diazo components, that is to say if Rl = OH in the formula (1), the dyestuffs are converted to the heavy metal complex dye-stuffs by adding a heavy metal donor to the dyestuff solution or the dyestuff suspension, if necessary with an acid-binding agent and if necessary by treat-ment at elevated temperature (in general the reaction can be carried out at 0 - 120C) until the conversion to the desired heavy metal complex dyestuff is complete.
Examples of heavy metal donors which can be used are: copper salts, such as copper sulfate, copper chloride, copper acetate or copper carbonate, chromium salts, such as chromium formate, chromium acetate, chromium sulfate, potash/chrome alum or chromium/salicyclic acid, or cobalt salts, such as cobalt sulfateS cobalt chloride or a cobalt/tartaric acid complex.
Acid-binding agents used when converting the dyestuffs to the heavy metal complex dyestuffs are preferably alkali metal salts of weak inorganic or organic acids, such as sodium carbonate, sodium bicarbonate or sodium acetate~
If Rl in formula (1) is an alkoxy group, preferably a methoxy group, this can be converted by known methods~ during the reaction to convert the dye-stuff to the heavy metal complex dyestuff, preferably the copper complex dye-stuff, to a hydroxy group and the latter can participate in the formation of C

the complex.
If Rl in formula (1) is a hydrogen atom, this can be replaced by ahydroxy group under the conditions of oxidative coppering [Angew. Chem. 70, 232-238 (1958)], with simultaneous incorporation of the said hydroxy group into the complex compound. The oxidizing agents used are advantageously derivatives of hydrogen peroxide, such as sodium peroxide, salts of peroxysulfuric acid or salts of perboric acid, but preferably hydrogen peroxide itself. Advantageous reaction conditions in general lie at 20 - 100C and pH values between 7 and 3.
The starting dyestuffs of the formulae ~4) and (5) can be manufac-tured by known methods, for example by the processes described in GermanAuslegeschrift 1,126,542.
The resulting dyestuffs of the formula ~1) or their heavy metal com-plex compounds are separated off by generally known methods either by precipit-ating from the reaction medium by means of electrolytes, such as, for example, sodium chloride or potassium chloride, or by evaporating the reaction solution, for example by spray-drying. If the latter method of isolating the dyestuff is chosen, it is advisable, before evaporating, to remove any amounts of sulfate which may be present in the solution by precipitating these as gypsum and separating them off by filtration. In some cases, it can also be desirable to supply the dyestuff solution direct, if appropriate after adding buffer sub-stances, as a liquid preparation for use in dyeing.
The present invention also relates to the dyeing and printing of cellulose and polyamide fiber materials with the dyestuffs according to the invention.
Cellulose fiber materials are understood as meaning preferably cotton and regenerated cellulose, but also other vegetable fibers, such as linen, hemp and jute. Polyamide fibers are to ke undexstood as meaning both those of natural origin and those of synthetic origin, that is to say both wool and other animal hairs and silk and also polyamide 6,6,polyamide 6, polyamide 11 or polyamide 4.
The dyestuffs according to the invention can be applied to the said substrates by the application techniques known for reactive dyestuffs. They are distinguished by clear shades and high tinctorial strength.
Thus, with these dyestuffs very good color yields are ob-tained on cellulose fibers by the exhaustion method from a long liquor, using very di-verse alkali addi-tives.
Excellent color yields are also obtained on cellulose fibers by the pad method, and the dyes can be fixed by a residence time at room temperature, by steaming or with dry heat. ~on-fixed portions of the dyestuff can be washed out easily.
Intense prints with outlines in a good state and a clear white ground are also obtained by the conventional printing processes for cellulose fibers - in a single phase in the presence of sodium bicarbonate or other acid-binding agents in the printing paste with subsequent steaming at 101 -103C or in two phases, printing with a neutral or weakly acid printing paste and then either passing through a hot electrolyte-containing alkaline bath or over-padding with an alkaline electrolyte-containing padding liquor and then developing by means of a residence time, steaming or dry heat. The appearance of the prints is only slightly dependent on changing fixing conditions.
The dyeings on polyamide fibers are usually carried out from an acid medium. Thus, for example, acetic acid or acetic acid and ammonium acetate an be added to the dyebath in order to obtain the desired pH value.
In order to obtain a uaable levelness of the dyeings, it is advisable to add conventional levelling agents, for example those based on a reaction product of cyanuric chloride with three times the molar amount of an aminobenzene-' C

sulfon:ic acid and/or of an aminonaphthalenesulfonic acid and/or those based on a reaction product of stearylamine with ethylene oxide. The dyeings can be carried out either at the boil or at 110-120C.
With regard to the coloristic properties of the dyestuffs according to the invention, it must be emphasized in particular that these dyestuffs are distinguished by a very good uptake from a long liquor, by good color build-up by the conventional dyeing and printing processes, by an identical depth of shade when dyeing on cotton and regenerated cellulose fibers, by levelness of the dyeings and prints produced therewith and also by a uniform appearance of the dyeings from a long liquor in the presence of different amounts of electro-lytes such as sodium sulfate or sodium chloride.
The fastness properties of the dyeings and prints obtained with the aid of the dyestuffs according to the invention, especially those on cellulose fibers, are appreciable. This equally applies in the case of the most import-ant fastness to processing and in use. The fastness to light, the fastness to wet processing, such as fastness to washing, fastness to milling, fastness to water, fastness to seawater, fastness to cross-dyeing and fastness to perspira-tion, and also the fastness to pleating, fastness to ironing and fastness to rubbing should be mentioned in particular.
The Examples which follow serve to illustrate the invention. The relationship between the parts by weight and parts by volume is the same as thatbetween kilogram and liter. The percentages are by weight unless otherwise stated.
Example 1 281 parts by weight of aniline-4-~-sulfatoethylsulfone are suspended in 1,400 parts by volume of water and 600 parts by weight of ice and dissolved by adding 62.5 parts by weight of calcined sodium carbonate, whereupon a pH value of 6.0-6.5 results. 205 parts by weight of aqueous 5N sodium ~ 16 -f~

nitrite solution are then added, 10 parts by weight of kieselguhr are stirred in and the solution is clarified. The filtrate is allowed to run at 0-5 C into a mixture of 1,500 parts by weight of ice and 282 parts by weight of aqueous 31% strength hydrochloxic acid. The mixture is stirred for one hour at 0-5C, the excess nitrous acid is then destroyed by means of amidosulfonic acid and the pH of the resulting diazonium salt solution is then adjusted to 6.0 by introducing about 45 parts by weight of sodium bicarbonate. This solution is allowed to run, in the course of 15 minutes, into a solution of the secondary condensation product of ~ mole of cyanuric chloride and ~ mole of l-amino-8-naphthol-3,6-disulfonic acid and ~ mole of 2-amino-5-naphthol-7-sulfonic acid, which is prepared as follows:
92.5 parts by weight of cyanuric chloride are dissolved in 300 parts by volume of acetone and the solution is then allowed to run into 2,500 parts by volume of water, with good stirring. A solution of 159.5 parts by weight of 1-amino-8-naphthol-3,6-disulfonic acid and 60.5 parts by weight of aqueous 33%
strength sodium hydroxide solution in 700 parts by volume of water is then added at about 20C and the mixture is stirred for 10 minutes, after which a solution of 119.5 parts by weight of 2-amino-5-naphthol-7-sulfonic acid, 46 parts by weight of aqueous 33% strength sodium hydroxide solution and 150 parts by weight of crystalline sodium acetate in 1,000 parts by volume of water is added and the resulting mixture is stirred for a further 1 hour. After the diazonium salt solution and the solution of the coupling component have been combined, the mixture is stirred at about 20C for several hours, the pH value being kept at 5.5 - 6.0 by adding a total of about 161 parts by weight of sodium bicarbonate in portions. After the coupling reaction has ended, the dye-stuff solution is clarified and the dyestuff is then precipitated by adding about 4,000 parts by weight of potassium chloride. After cooling to 8-10C, the dyestuff is filtered off and C

dried in vacllo at 60C. This gives a red powder which dyes co-tton in fast red shades in the presence of acid-binding agents. The dyestuff has the following constitution:

N ~ ~ ~ 21 2 HO NH~J\N}I ~so3H CH
CH2 CH2 02S ~N===N ~ 1SO3H

Example 2 251 parts by weight of 2-naphthylamine-8-~-hydroxyethylsulfone are introduced in the course of 20 minutes into 660 parts by volume of 20%
strength oleum, the -temperature rising to 60 C. The mixture is kept at 65-70C for 4 hours and is then allowed to cool to 30C and is added to a mix-ture of 2,500 parts by weight of ice and 1,000 parts by volume of water. The diazotization reaction is then carried out at 0-5C by adding 200 parts by ~rolume of aqueous 5N sodium nitrite solution, the reaction mixture is stirred for a further 1 hour at 0-5C and the pH is then adjusted to 5.0 by adding 1,184 parts by weight of calcium carbonate.
This suspension is added in the course of a few minutes to a solu-tion of the tertiary condensation product of 1/2 mole of cyanuric chloride, 1 mole of 2-amino-5-naphthol-7-sulfonic acid and 1/2 mole of aniline-3-sul-fonic acid, which has been prepared as follows:
92.5 parts by weight of cyanuric chloride are dissolved in 300 parts by volume of acetone and the solution is then poured into 2,500 parts by volume of water, with good stirring. A solution of 119.5 parts by weight of 2-amino~5-napthol-7-sulfonic acid and 45 parts by weight of aqueous 33%
strength sodium hydroxide solution in 1,000 parts by volume of water is then added at about 20 C and the mixture is stirred for 10 minutes, after which a C

further solution of 113.5 parts by weight of 2-amino-5-naphthol-7-sulEonic acid and 45 parts by weight of aqueous 33% strength sodium hydroxide solution in 1,000 parts by volume of water is added and 150 parts by weight of crys-talline sodium acetate are then sprinkled in. 86 parts by weight of aniline-3-sulfonic acid are then added and the mixture is heated to 90-95C, the pH
value being kept at pH 6.5 - 7.0 by adding sodium bicarbonate. The mixture is stirred for several hours at the said temperature and at pH 6.5 - 7.0 and is then allowed to cool to room temperature.
After the diazonium solution and the solution of the coupling com-ponent have been combined, the mixture is stirred for several hours at about 20C, the pH value being kept at 5.3 - 6.2 adding a total of about 64 parts by weight of sodium bicarbonate in portions. After the coupling reac-tion has ended, the mixture is warmed to 60 - 65, the gypsum whichhas ~re-cipitated is filtered off and washed with hot water and the filtrate is spray-dried. This gives a red-brown dyestuff powder with which violet dyeings and prints can be obtained on cellulose fiber materials in the presence of acid-binding agents. The dyestuff has the following constitution:

C 2 3 ~ SO3H CH2-OSO3H

~ N=== ~ ~ ~ ~ N===N ~ ~ ~

HO3 ~ 3 ll 1`N ~ HN ~ ~ SO3H ~ SO3H

In a manner analogous to that described in Examples l and 2, dye-stuffs can be obtained from the diazo components and coupling components listed in the table which follows: these dyestuffs dye and print cotton in the indicated color shades.

~ I ~d c~ C ~ a~ ,c a) a) a) a~
.C o u~ h u2 h rd ~rd h h h u~ +~ a~ hh C ~ ~ ~ ~ ,C r~
,~ o h O (V O a) u~ C) u~ C) O c~ ~I bD ~I hO ~ 0 h O C ~1 ,&~ ~1 ,C ~ ,C~ R t~ ~ ~C
V O ~ ~ ~ ~ ,~ ~ ,Q +~O ,Q +~

+' ~ O
c a) o ;~
& ~1 o o a~
O tQ N ~
O ~1 ~3-rl rl q~ C~
q~ O ~d &' O ~D ~
r~ 1, 0~ ~
O O O ~ ~I r~ _ = _ _ _ _ _ - _ .
~ p~ C I
C

+~ h co rl O
~ ~ O ~ +~
(I) ~ P~
-&
O q~ O I
O ~1 ~1 co O O O ~
+~
,~ ?
+' ~ +~ C
(1~ , +~ o u~
~ $ +~ ~ o~ :rL ~n cn ,i , O ~ Q h ~1 q l q-, o ou~ ~t IA ~ rl,S:~
O ~ ~ ,C ~ I I I ,C,1~
t.l I I I Y ~1 0 0 C) O cn cnC~ c~ o N I ~-~rl ~-1 ,C I O
td ~ ~ ~) ~t ~ C C O
O +O ~ a~ XO
h ~ C ~ O ,5~

~ N R N ~ N ~ N ~ N

4~ o ~ 4~ q~ o q I oq, o ~~ +~
O O O ~,~ O O q~ q~ ~1 +' a~ & ~ &~ ~ aJ & ~ +~
O q~ 0 4~ ~0 ~ ~0 q~ ~0 ~0 ~ ~0 ~ ~ "
~ ,Cj ~,C
N U~ N ui N a) N ~ N N C) N a) N O N 11~ N ~t H a~

lÇi o ~ ~ L~ ~0 ~ cO CJ~ O ~ N
~;

a~ a) ~
~ s~ ~
.c: O
U~ ~ U~
O c) ~1 O ~ ,D ~ 5~ h 5~ h ,~
o ~rl ~
q~ ~ R
o a~
~1 ~ r~ I
O ~0 ~o ~ o o~ 4~
cl O ~ O n3 b~ +' ~ ~1 ~
c~ ~ co ~rl O ~ ~ R - _ - - - - ~ _ _ _ ::~
o ~ h~o V

~d o ~ ~0 c~
U7 ~rl ~ rl R S~ ~ a) R
R ~ o R ~ R ~ ~1 v ~co ~ ~
I ~ ~ r ~ O O
R c~ ~ CQ CQ
a) C~ ~ u\ I R ~rl ,1 R I cu ~1 ~1 1 1 ~ ~rl ~ ~
~1 ~ ~ 3 R R a~ ~rl R R R
~3 O R ~ +~ R
o U2 ~ a) ~ ~ rd ~ ~1 ~rl ~ ~1 ~1 C~ ~ O~i~ O~
O
R ~ O o ~ ~ R ~ ~ R
~,~ ~ o R ~ rl o O O O ~1 o ~rl o ~rl o ~rl o R I o ~ O ~ o, ~ ~ q~
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~ ~ ~ ~ 0~ ~ ~e ~ ~ O
O .~
~ ~ e ~
O
O ~ ~~ O ~ O ~H ~ ~ O ~ ~ ~ ~
0 4~ 0 ~0 4~ o 4~ o ~ O ~ O ~d O ~' v~ ~ v~ ~ ~ ~ ~ ~ ~ rd ~ ~ V) ~ u~ O
6 ,~: e ~ 6 ~? e ~ e ~ ,e ~ e '' e 4~

`D ~ 00 ~) O ~I N
X o ~, ~ , 1 T-~ r~l -1 ~1 ' Ul Z;

f~

r rd r~ o n ~ rD bD ~ ~ ~ rd r~l O ~ ~ S O 0 50 0 r~ o ~ r r~
d I o r r r--l r~ ~ o r--l O ~ r--l ~Q CH
r-l ~ R ~; rO r~ R R 1~ r~O
r r~ r~ IA r-l ~ n u~ r~

r~ ~ rd I rd ~rl rd ~0 ~ rd r rd rd ~ o C~l cd ,I rd aJ ~I C~J d ~ o O
d Sl ~r-l ~ ~ O d : ~ s~ ~ r r-l F~ h ,s~ O ~r r ~ ho ~ r~ rO
@1 O ~ ~ r~ ) O r~ cd r l ~r~ r;~
o ~ co ~ ~1 ~ +, co ~ t ~ r~ r~ I
u~ r1 O r--l I rd rn r~ O r-l ^ H rn ~ O
C~ $1 ~ 1~ C~ R h 5~ r-l O R ~ ~
I h ~ F~ ~ ~ r--l a) Cd ~ rd rd -r~ 0 ~3 c~ rd rd rl o r-l ~: r. c ~rl o ~ I c, ,5~ 1 ~ I Cd ~ ~ ~ I r~d s:~ ~ O r--l O rl O ~ O ~
~ t rH ~ rH rtH
,~ ~ ~ r r ~ ~ 1 ~ s 9 ii o cd to tH ~ rO rO r~ rO ri~ ~O r~ o r~
rn a) ~ o rn O U~ u~ n n ,r r-l tO r-l rrd r tO rl ~ r~ ~ r~ r1 rt ~
C~ rn C~ rn C\l rn C\J r~ 1) ~ rH

~ ~i ~ U~ ~ CO ~ O

.

r~
c3 C~
C O
u~ ~ a) a) a h O bD bD
O C) r, rl r~ r~
O C h a) h h a> tl) h C~
O O h O O h h O h qO .c~ ~,,, c) ~, c r-l Ir\ O ~ r~ I O r o r~
ul o O u~ O C~ O C) rlrl ~ r~ ~rl ~ ~ ~ 'rd ~ ~ ,~ r d t~ ~ .c u~
o~ C~ O ~ R ~0 r ~ ~ r~ r ~ rJ C G~
c~ ~ rl +~ r i ~ ~rl ~ q~ ri R a ~ ~ R O ~ ~ ~ o u I

O rl c) I r i t~ rl ~rl- ~ r~ ~ ~rl ~rl O r~ rl rl O r~ ~1 ~d O I r~ r~ h Lr~ R ~,r r~ r~
~o R~ ,~ R R ~ ~r ~ c u~ ~ ~R O

O ~ O q~ r c~ ~ O q~ O ~ ~ ~ ~
~> o C~ > O O ~ R ~ o o c~ R

a~
I ,~ ~ r,~ 4~ ~ ~r 4-1 ~r~ 4~ 0 I r~ ~

R '~ , X R
oR ~ o I ~ rt ,cl ~ ~ r 0 a) O ~ O +~
O R J 4-1 ~rl R ~,rRI 4o~ C ~ ,rR~
O ,1 1 ~ ,1 ,i R ~ rr~
t~ Ct 0 N r l ~ C\l r~ ,J~ td 0 ~1 0 ~r 4 R41 ~ 40t d 4~40 ,~? 40 ~j~ 41 qO rt ~ O ~ ~ 0 ~
~ rl 4 rl ~rl ~) r rl rl rl r rt C\J ~ Q CU ~C\l qt C\l Ul C`J ~d C~ a a) rl rl C~J X ~ (~ 1 r rt X O

' .

Example 139 297 parts by weight of 2-aminophenol-4-~-sulfatoethylsulfone are suspencled in a mixture of 1,400 parts by volume of water and 600 parts by weight of ice and the suspension is then neutralized with about 76 parts by weight of anhydrous sodium carbonate. 205 parts by volume of aqueous 5N
sodium nitrite solution are then added and, after clarifying, the filtrate is allowed to run dropwise onto a mixture of 250 parts by volume of 31% strength hydrochloric acid and 1,500 parts by weight of ice. The resulting mixture is then stirred for 1 hour at 0-5C, a little excess nitrous acid is destroyed with a little amidosulfonic acid and tlle pH is then adjusted to 5.5 - 6.0 with about 130 parts by weight of sodium bicarbonate. This solution is allowed to run into a solution of the secondary condensation product of 1/2 mole of cyanuric chloride with 1/2 mole of 1-amino-8-naphthol-3,6-disulfonic acid and 1/2 mole of 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 by vol-ume of acetone with warming and the solution is poured at 15-20C into 2,500 parts by volume of water. A solution of 159.5 parts by weight of 1-amino-8-naphthol-3,6-disulfonic acid and 60.5 parts by weight of aqueous 33% strength sodium hydroxide solution in 750 parts by volume of water is then added at about 20C and the resulting mixture is stirred for 10 minutes, after which a solution of 119.5 parts by weight of 2-amino-8-naphthol-6-sulfonic acid and 47.5 parts by volume of aqueous 33% strength sodium hydroxide solution in 1,000 parts by volume of water and then 150 parts by weight of crystalline sodium acetate are added. The mixture is stirred for a further 90 minutes at 20-25C. After the diazonium salt solution has been added, the coupling re-action is carried out for about 15 hours at 10-20C, the pH value being kept at 5.5 - 6.0 by adding about 69 parts by weight of sodium bicarbonate in por-tions. After the coupling reaction has ended, 300 parts by weight of sodium r~

æ~

acetate (crystalllne) and 247 parts by weight of crystalline copper sulfate are introduced, the pH is adjusted to 5.0 with a little 5N acetic acid and the mixture is kept at 50-55C for 1 hour. The dyestuff is then precipitated by adding 4,000 parts by weight of potassium chloride and is filtered off and dri~ed in vacuo at 60C. This gives a dark powder with which violet dyeings and prints can be produced on cotton fabric. The dyestuff has the following constitution:
Cl 0 ~ -0 NH ~ ~ NH ~N==-N

Ho353 S03H ~

Example 140 243 parts by weight of 6-~-hydroxyethylsulfonylbenzoxazolone are introduced at 80-100C into a mixture of 225 parts by weight of 100% strength sulfuric acid and 255 parts by weight of 95.5% strength sulfuric acid and the mixture is then stirred for 4 - 5 hours at 142 - 147C. After the mixture has been cooled to about 80C, it is added to a mixture of 1,500 parts by weight of ice and 500 parts by volume of water and the diazotization reaction is then carried out at 0-5C by slowly adding 200 parts by volume of aqueous 5N sodium nitrite solution. The reaction mixture is stirred for l hour at 0-5C, a trace of excess n~trous acid is then destroyed with a little amido-sulfonic acid and the pH value is then adjusted to 5.5 - 6.0 by adding about 445 parts by weight of calcium carbonate. The diazonium salt is coupled with the coupling solution described in Example 139.

The reaction mixture is stirred at room temperature for 16 hours, r~
.

the pH value being kept at 5.6 - 6.1 by adding about 108 parts by weight of calcium carbonate in portions. The mixture is then warmed to 70 - 80C and the gypsum is filtered off. The latter is washed with hot water, 300 parts by weight of crystalline sodium acetate and 248 parts by weight of crystalline copper sul-fate are then added to the filtrate and coppering is carried out at 40 - 45C
and a pH value of 5.0 - 5.5 for 2 hours. The dyestuff is precipitated by adding potassium chloride and is filtered off and dried. A dark dyestuff powder is obtained with which violet dyeings and prints with excellent fastness properties are obtained on cotton materials. The dyestuff has the following constitution:
Cl D ~ i1`o NH N NH / ~:,~ N-==N
~ N===N ~,~ ~
CH2-025~J HO3S SO3H S03H S02CH2CH20S03H

Example 141 251 parts by weight of 2-aminonaphthalene-8-~-hydroxyethylsulfone are introduced into 660 parts by volume of 20% strength oleum in the course of 20 minutes and the mixture is then warmed at 65-70C for 4 hours. The reaction mixture is then cooled to 25-30C and allowed to run into a mixture of 2,500 parts by weight of ice and 1,000 parts by volume oE water. The diazotization is then carried out at 0-5C with 200 parts by volume of aqueous 5N sodium nitrite solution, stirring the reaction mixture for 1 hour at 0-5C, and a little ex-cess nitrous acid is then destroyed by means of amidosulfonic acid. The pH of 20 the diazonium salt solution is then adjusted to 5.0 - 5.5 by adding 1,200 parts by weight of calcium carbonate and the solution is combined with the coupling solution described in Example 139. The coupling ' C

reaction is carried out at room temperature for 20 hours, the pEI value being kept at 5.5 - 6.0 by adding about 90 parts by weight of calcium carbonate in portions. The mixture is then warmed to 70 - 80C and the gypsum is filtered off and washed with hot water, and 300 parts by weight of crystalline sodium acetate and 247 parts by weight of crystalline copper sulfate are then added to the filtrate. A mixture of 228 parts by weight of aqueous 30% strength hydrogen peroxide and 1,000 parts by volume of water is then added dropwise at 35-41C in the course of 40 minutes and the resulting mixture is stirred for 4 hours at 35-41C. The dyestuff is then precipitated by adding potas-sium chloride-and is filtered off and dried. This gives a dàrk powder with which reddish-tinged blue dyeings and prints are obtained on cotton mate-rials. The dyestuff has the following constitution:

CH2OSO3H Cl Cu IH2 02S O ~ ~ O NH ~ N ~ H ~ ~

E103 ~O~S SO3H SO3H ~ SO3H

Example 142 325 parts by weight of 2-methoxy-5-methyl-aniline-4-J~-sulfatoethyl-sulfone are suspended in 1,500 parts by volume of water and 500 parts by weight of ice and dissolved by adding about 64 parts by weight of calcined sodium carbonate, the resulting pH value being between 6.0 and 6.5. 203 parts by volume of aqueous SN sodium nitrite solution and 15 parts by weight of kieselguhr are added and the solution is clarified. The filtrate ia allowed to run at 0-5C into a mixture of 1,500 parts by weight of ice and 282 parts by weight of aqueous 31% strength hydrochloric acid. After the mixture has been stirred for 1 hour at 0-5C, excess nitrous acid is destroyed with amidosulfonic acid and the pll of the resulting diazonium salt solution is then adjusted to 6 by introducing about 40 parts by weight of sodium bicar-bonate. Tllis solution is coupled with the coupling solution described in Example 139 and the reaction mixture is stirred at 18-22C for several hours, the pH value being kept at 5.3 - 6.2 by adding sodium bicarbonate in portions.
After the coupling reaction has ended~ a solution of 346 parts by weight of crystalline copper sulfate, 483 parts by weight of crystalline sodium acetate and 318 parts by weight of glacial acetic acid in 1,475 parts by volume of water is added and the resulting mixture is then boiled under reflux for 20 hours. After cooling, the dyestuff solution is clarified and the dyestuff is then precipitated by adding potassium chloride and is filtered off and dried. This gives a blue-black powder with which cotton materials can be dyed in violet color shades. The dyestuff has the following constitution:

O ~ ~ H~IH~===N~S02CH2CH20S02H
CH2-CH2-2-5 ~ ;N ~ S03H S03H CH3 Example 143 If, in Example 139, the solution of the coupling component is re-placed by the solution described in Example 2 and in other respects the same procedure is followed, a dark brown dyestuff powder is obtained with which ruby-red dyeings and prints can be produced on cotton materials. The dye-stuff has the following constitution:

~.~

t~`3~

Cu Nll / Cu llO NH N HN S03H ~
S~)2 3 ISO2 Cl~2 CIH2 Example 144 The non-metallized dyestuff is prepared as described in Example 139. After the coupling reaction has ended,the coupling solution is warmed to 55-60C and, at this temperature, 320 parts by weight of crystalline sod-ium acetate and 250 parts by weight of chromiuTn potassium sulfate are added.
The temperature is then raised to the boiling point and the mixture is boiled under reflux for 6 hours. The dyestuff solution is clarified and spray-dried.
This gives a dark grey dyestuff powder with which grey-violet prints can be produced on cotton fabric. The dyestuff has the following constitution:

C ' ~¢~5 ~i C~l2-OS03~l Example 145 The non-metallized dyestuff is prepared as described in Example 140.

After separating off the gypsum, 300 parts by weight of crystalline sodium r~
~,. ~

acetate and 295 parts by weight of crystalline cobalt sulfate are added to the dyestuff solution and the mixture is then warmed at 60 - 65C for 2 hours. The dyestuff solution is clarified and then evaporated to dryness in vacuo. This gives a dark dyestuff powder with which opaque violet prints with excellent fastness properties can be obtained on cotton materials. The dyestuff has the following constitution:

Cl / C/2 ~ ~ N ",Co/2 0 O NH N 1 Nll ~ N===N ~

The heavy metal complex dyestuffs listed in the table which follows can be obtained in a manner similar to that described in Examples 139 - 145.
In the "diazo component" column, the said components are described in the form in which they are present after metallization, that is to say in some cases with a hydroxy group formed from a methoxy group by demethylating metal-lization or with a hydroxyl group introduced by oxidative coppering.

. .~

h ~ O E ~3 O ~ ~ 3 ~ ~ ~ .,1 ~ ~ ~ , r~ ~ ~) O O O O h O O O O
O ~ O h F;l D ' ' ' ~~

~ ~ E~

E ~: D .~ . E

a) ~ o ~ O; ~
~,5 O ~ ~4~ 0 ~ ~ 3 ~ O ~1 40 t~O ~ ~ ~
~ h,~ I ~ h S
C~ h ~ O h O ~ 1~ ~ O t~

E E ~ o ~0 ~1 41 ~0 E3 0 4 O 0 4~ O O
~L I I I
d- U) S ~ S S
1:: ~ O S o ~ ~ S ~1 ~ o ~ 0 4~ ~; ~
O rl ~ O ~ ~ O r~ ~
N ~ h 4~ ~ I C ~ ~ ~?
td ~ ~ cd .-1 D ~ e S ~ S ~ V) 4~ ~ ~40 ,s, o U~ ,-~
td ~ O
. ~ ~ ~ ~ ~ o~ ~ ~ O ~ O ~ ~ U~
o ~ ~ ~ 2 ~H e ~ ~
a~
D ~ ~ ~D I~oo a~ O ~ ~1 ~d X O
E~ ~ Z

.

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f~

h C> o ~ 3 r-l 3 r~
r1 C~ ~ O O O O O O O O O O O O
O ~ O ~h ,D r ~ , r . r r ~ ~ . r r X ~ ~) rl ~ h h r-l . r~ r-l ~3 r1 C) a> Ei r~
h ~P~ ~ h ~ ~
O O O ~ O O O ~: O ~ O
~ t~ I o r1 ~ g r1 0 Vl 6 N r r~ I; ~ I
g ~o '3 1` ~0 ~ t"
r~ 1) 0 ~ ~1 C~ O r-l rl t~ ~ h ~ - h ~
~: h r~ ~P h r~
r 1 1~
O t_~ I O ~
O .rl rl O .rl .r~ O r~
n~ ~ ~ hr O

O ~ 0 4~ 4~ 0 O O ~d ~ O o 4~ u~

a L In r-l r~ r1 r-l r I
F F F F F F

~ r Ei r _ ~ r ~ r _ _ E~ r _ a ~o o ~ ~0 ~ 40 s 40 ~
o ~ o tn o o o 0 4~ ~0 ~ 0 4~

~ V

r-1 ~ t~
U~ U') U~ ~ U'~ U~ U~
_l ~ ~ ~ ~ ~ ~ ~1 Z

3 5 ~
h ~ O , ,~
1:: ~ O O ~ ,D h o ~ O h h O .C O . ~ . . ~ ~ ~ O h O O

t~l X ~ h ~ h ~ h r~ ~ h rl ~ o ~ ~ ~ ~ O ~ O

I O
0 ~ O ~
~`D ~ ~ ~ ~ ~ ~0 O ~O ~d o 3 ~P ~- o o ~ a> o (~
O ~ ~ _ _ ~ h ,S O ~
bl) O O P~ ~1 ~ O O P~ O
h ~ t ~1 ~,5~ U) ~.C
O rl ~ O ~ ~1 ~0 ~ I
h ~
~ 0 ~ I ~ N ~
~ O 0 4~ O O ~
~ I ~
O I I I I I
O

~ O t~ N .~I .Ç I ,~ ~ ~>
S: ~ .C I ~ N ~ N ~ ~ ~
O ~ ~ ~ S ~ h ~ ~ O R
O ~ 6 ~ ~ ~ 5 4 ~ _l U~ ~ ~ C~ O
V~ -~ n U) IUl I U~ I 11) 0 U~ O
o ~ o ~ ~ ~o ~ a~ ~o ~ c) ~o 41 ~
F~ S ~ e ~
~ S ~~ 4~

~ ~ ~ ~ ~ ~ ~ ~ ~`
O
Z;

. .

~6~g g O ~ ~> O O ~ OO o O ~ O ~d O O
O ~ O h ~ ~1 h ~1h rl ,1 h rl ~.,~
ul ~ ~ 0 ~ O :~ ~ h ' _I ~ h ~ ~ ~ h ~ ~ h h p., ~ O cd ~ O ~d O ~ ~ ~ .C '9P' ~ ~ ~4 a> ~
~ E~ O I ~ E3 ~ ~
O ~ ~ O rl 'I ~ O
O 3, ~ t~ 0 3 1 ,C ~ _ _ _ _ _ h rC O ~ ~ h ~ ~ 4 ~:: ~ R 4 O t~ g ~
O rl r~ O ~ I~ r~ rl O ~ ~

rl ~ E3 g 4~ ~ t.~ ~ 0 41 ~H ~0 ~
O O ~ O 0 4~ 00 ~1 ~, ~L ~ I ~_1 ,J ,5 ~ O, O~ ~ O ~

~ Cll R ~ 2 ~ ~ o ~o ~ ~ ~o ~ ~o ~ ~o ' ~o ~ ~
~ ~ ~R ~ o ~ ~ R

n ~ I~ oo a~ o ~X o ~ ~ ~ I~ ~ ~ ~ ~ _I
~Ll Z

r~
. ~

O ~ ~ ~ ~ ~
o ~ o o o o o o ~ o h h h h h h O O
O ~ V
a~
~ _~ ~1 ~1 ~
G~ O ~ > O ~ I ~ rl o ~ o ~ 3 g ~ ~ ~ ~ N ~ 0 3 ~ ~ t~ a O ~ ~ ~ ~ O
d h ~ ~1 ~
C: p,"~ h .C ~ ~ 5 'E;

O ~ O ~ rl O ~ ~
C~ ~ h ~ 0 4-1 e o 0 4~ O 0 4 C~ ~ ~ O
' N ~
~ ~O ~ ~ O
Ei ~ 6 1~1 ~ ~1 ~ ~1 ~ ~ N ~1 ~ u ~1 O ~ O ~O ~ O ~ O I
U~ O U~ o U7 o tl~ o U~, a) ~ 1 0 0 4~ 0 ~H 0 4~ 0 4~ 0 S::
N U~ ~ Vl ~ v~ ~ Ul ~1 p~

~ ~
X

:

.
.

3~
Example 186 531 parts by weight of the dyestuff of the formula OH
HO3SO CH2CH2 2 ~ N===N ~ ~ ~

are dissolved in 3,700 parts by volume of water, the pH value of the solution being adjusted to 6.4 - 6.7. A solution of 92.3 parts by weight of cyanuric chloride in 300 parts by volume of acetone is then allowed to run dropwise ::
into this dyestuff solution, the temperature being 20-22C. The reaction mix-ture is stirred for 15 minutes, the pH value is then adjusted to 6.4 - 6.8 with sodium bicarbonate, 150 parts by weight of sodium acetate are added and the resulting mi.xture is then stirred for 1 hour at 55C. The dyestuff is precipitated using potassium chloride and is filtered off and dried in vacuo at 60C. It corresponds to the dyestuff listed under Example 72 in Table 1.
Example 187 306 parts by weight of the dyestuff of the formula H35-CHzCHz~25 ~rN=- N ~`503H

are dissolved in 1,800 parts by volume of water and the pH value of the solu-tion is then adjusted to 6.5 - 6.7. A solution of 92.25 parts by weight of cyanuric chloride in 300 parts by volume of acetone is then added dropwise to this solution and the resulting mixture is stirred for 15 to 20 minutes at 18-21C. The pH value is now adjusted to 6.4 - 6.8 by adding sodium bicar-bonate and the mixture is again stirred for 15 minutes, a solution of 266 parts by weight of the dyestuff of the formula ,C

OH
~io3so-cH2cH2-o2s ~ ,~

in 2,000 parts by volume of water and 150 parts by weight of crystalline sodium acetate are then added and the resulting mixture is stirred for 1 hour at 55-60C. The dyestuff is precipitated by adding potassium chloride and is filtered off and dried in vacuo at 60C. It corresponds to the dyestuff listed under Example 3 in Table 1.
Exampl.e 188 If the solutions of the two aminomonoazo dyestuffs of Example 187 are reacted with an aqueous solution of the primary condensation product of 1/2 mole of cyanuric chloride with 1/2 mole of ~-sulfatoethylamine instead of with cyanuric chloride and the first reaction is carried out at 40-45C and the second reaction is carried out at the boil, the pH being 5.8 - 6.5 for both reactions, a dyestuff is obtained which corresponds to that listed in Example 56 of Table 1.
The dyestuffs listed in Examples 1 and 2, 4 to 55, 57 to 71 and 73 to 138 can also be prepared in a manner similar to that described in Examples 186 to 188.
Example 189 345 parts by weight of the dyestuff of the formula ''~' ~ O H
B0 HO SO-CH CH -U2S ~ N===N ~
~ HO3S S03H

are dissolved in 3,000 parts by volume of water, the pH value being adjusted to 6.4 - 6.8 with a little sodium bicarbonate.` A solution of 92.5 parts by l~

weight of cyanuric chloride in 300 parts by volume of acetone is allowed to run dropwise at 15-25C into this dyestuff solution and the mixture is then stirred for 30 minutes at the indicated temperature. The p}l value of the re-action mixture is then again adjusted to pl-l 6.4 ^ 6.8 with a little sodium bicarbonate and the ~ixture is stirred for a furtherl5 minutes. A solution of 305 parts by weight of the dyestuff of the formula O ~Cu Ho3so-cH2cH2 2 ~ N-==N ~ ~ 2 in 3,000 parts by volume of water and also 150 parts by weight of crystalline sodium acetate are now added and the mixture is then stirred for 2 hours at 50 - 55C. After cooling to 18 - 20 C, the dyestuff is precipitated with potassium chloride and is filtered off and dried in vacuo at 60C. It cor-responds to the dyestuff indicated under Example 140.
Example 190 If the solutions of the two aminomonoazo dyestuffs of Example 189 are reacted not with cyanuric chloride but with an aqueous solution of the primary condensation product of 1/2 mole of cyanuric chloride and 1/2 mole of taurine and the first reaction is carried out at 40 - 45C and the second reaction is carried out at the boil, the pH being 5.8 - 6.5 in both reactions, a dyestuff is obtained which corresponds to that listed lmder Example 176 in Table 2.
The copper complex dyestuffs further listed in Examples 140, 141 to 143 and in Table 2 can also be prepared in a manner similar to that in Ex-ample 189 and 190.
Example 191 306 parts by weight of the dyestuff of the formula I r~

1-103SO-cl12cH2-o2s~ ~
ilo3s SO3H

are dissolved in 2,000 parts by volume of water, the pH value of the solu-tion :is then adjusted to 6.4 - 6.8 with a little sodium bicarbonate and a solution of 92.5 parts by weight of cyanuric chloride in 300 parts by volume of acetone is then added dropwise to the dyestuff solution. The reaction mixture is warmed to 35-40C and kept at a pH of 6.3 - 6.7 for 45 minutes by adding sodium bicarbonate in portions. A solution of 266 parts by weight of the dyestuff of the formula ~ N===N ~ ~ NH2 in 2,000 parts by volume of water, the pH of which has previously been ad-justed to 6.4 - 6.8, is then added and the reaction mixture is warmed to 60-65C, thepH value being kept at pH 6.3 - 6.7 by adding sodium bicarbonate in portions. When no further starting dyestuff can be detected in a paper chromatogram, thedyestuff solution is clarified and the dyestuff is isolated by spray-drying. This gives a red powder with which red dyeings and prints can be produced on cotton in the presence of acid-binding agents. In the form of the free acid, the dyestuff has the following constitution:

N ~ N
HO NH ~ N ~ NH
~ I ~Y~' ~ ~N===N ~
H03SO 2 2 2 ~ ===N ~ I ~ ~ SO3H SO2CH2CH2 - 52 _ ; ~

3~

Example 192 If a solution of 344 parts by weight of the dyestuff of the formula O ~ ~ o NH

H03SO-CH2CH2 2 ~ N===N

HO S

in 2,000 parts by volume of water is used in place of the first dyestuff so-lution in Example 191 and in other respects the same procedure is followed, this gives a dark dyestuff powder with which cotton materials can be dyed and printed in brown-violet shades. In the form of the free acid, the dyestuff has the following constitution:

OH2CH2-025 ~ N==-N ~ ~ N~ N-==N ~

Dyestuffs which contain two different diazo components, for ex-ample those indicated in the table which follows, can be prepared in a con-trolled manner by a method similar to that indicated in F.xamples l91 and 192.

C

68~

a~
O h C ~ ~ h :C N o cN
~N O ~ ~ V~

~_ Z o~ O
0~
~ $ z~

. ~ Z~
o~ o~

Z o~ Z~ o~

O ~ O ~" O :C
~ o ~ ~ O

~ ~
~ ~ z ~; ~

a~
~ o v~ ~
~ ~ r, ,, o o~
:~
~ ~ o ~
x x u) ~) ~-- ~--0 N
O
U~

11 X Z;
11 ~ 11 X

,C:

~ ZX ZX;
7=( x , 7~=~

X_4~ Z

''\r\~Z, x / ~
0~ \r\ '' x ~ O ~0~
N N O
U--~--O

æ ~ c~

a~
rc o h O 3 O O h 3~
O O
T'~

Z o~ ~Z

Z

/~ ~
\ \ Z Z
~ , ~
0~ :C O ~::
I ~ I
' X~ ~ U
O ~ O

~ o~
Z O~

Claims (17)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A water-soluble dyestuff which in the form of the free acid has the general formula (1) (1) in which K1 and K2 are identical or different and K1 is the radical of the formula or and K2 is the radical of the formula , , or D is the benzene or naphthalene nucleus;
R1 is in the ortho-position relative to the azo group and is hydrogen, halogen, lower alkyl, lower alkoxy, hydroxy, carboxy or sulfo and R2 is hydrogen, halogen, lower alkyl, lower alkoxy, nitro or sulfo, R1 and R2 being identical or different from one another;
X is .beta.-thiosulfatoethyl, .beta.-chloroethyl, .beta.-sulfatoethyl or vinyl;
Y is chlorine, fluorine or bromine or sulfonic acid or a group of the formula -S-R' or -O-R", in which R' is a substituent selected from the group consisting of (a) lower alkyl unsubstituted or substituted by hydroxy, lower alkoxy, sulfato, sulfo, carboxy, phenyl, phenyl substituted by nitro, sulfo or carboxy, naphthyl and naphthyl substituted by nitro, sulfo or car-boxy, (b) phenyl unsubstituted or substituted by nitro, sulfo or carboxy, (c) naphthyl unsubstituted or substituted by nitro, sulfo or carboxy, and (d) 2-benzthiazolyl, and R" is hydrogen or has the meaning of R' with the except-ion of 2-benzthiazolyl, or Y is an amino group of the formula -NR3R4, in which R3 is (a) hydrogen, (b) a lower alkyl unsubstituted or substituted by one or two substituents selected from the group of hydroxy, sulfato, lower alkoxy, sulfo, carboxy and phenyl, (c) an araliphatic radical or (d) a cyclo-aliphatic radical and R4 is (a) hydrogen, (b)lower alkyl, unsubstituted or substituted by hydroxy, lower alkoxy, sulfato, sulfo, carboxy, phenyl, phenyl substituted by nitro, sulfo or carboxy, naphthyl and naphthyl substituted by nitro, sulfo or carboxy, (c) an aromatic radical, (d) an araliphatic rad-ical, (e) hydroxy, (f) lower alkoxy, (g) amino, (h) phenylamino or (i) lower alkylamino, or in which R3 and R4 together with the nitrogen atom form a ring containing a lower alkylene and optionally a nitrogen or oxygen atom; and a heavy metal complex compound of a compound of formula (1) defined above, in which case one or both of the R1s are hydroxy.

2. A dyestuff according to claim 1 in which D, R1, R2, K1, K2 and X are as defined in claim 1 and Y is chlorine, bromine, fluorine, sulfo, amino, methylamino, dimethylamino, .beta.-hydroxyethyl-amino, .beta.-methoxyethyl-amino, .beta.-sulfatoethyl-amino, .beta.-sulfoethyl-amino, N-methyl-N-.beta.-sulfoethyl-amino, carboxymethyl-amino, N- .beta.-carboxyethyl-amino, N-(carboxyphenyl)-amino, N-(sulfophenyl)-amino, N-(disulfophenyl)-amino, N-sulfonaphthyl(1)-amino, N-methyl-anilino, morpholino, iso-propoxy, phenoxy or .beta.-hydroxyethyl-thioether.

3. A dyestuff according to claim 1 wherein D, R1, R2, K1, K2 and X are defined as in claim 1 and Y is chlorine.

4. A dyestuff according to claim 1, 2 or 3, wherein Y, R1, R2, K1, K2 and X are defined as in claim 1, 2 or 3 and D is a benzene nucleus.

5. A dyestuff according to claim 1, 2 or 3, wherein Y, K1, K2 and X are defined as in claim 1, 2 or 3 and D is naphthalene bonded in the 2-position to the azo group, R1 is hydrogen and R2 is sulfo in the 6-position of the naphthalene nucleus, or R1 is sulfo and R2 is hydrogen.

6. A dyestuff according to claim 1, 2 or 3 wherein Y, R1, R2, K1, K2 and X are as defined in claim 1, 2 or 3, D is a benzene nucleus, and the group -SO2-X is in the meta-position or para-position relative to the azo group.

7. A dyestuff according to claim 2 or 3 wherein D is the naphthalene nucleus bonded in the 2-position to the azo group and contains the group -SO2-X bonded in the 6-position or 8-position.

8. A dyestuff according to claim 1, 2 or 3, wherein Y, K1, K2 and X
are defined as in claim 1, 2 or 3 and D is naphthalene bonded in the 2-pos-ition to the azo group, and contains the group -SO2-X bonded in the 6-pos-ition or 8-position, R1 is hydrogen and R2 is sulfo in the 6-position of the naphthalene nucleus, or R1 is sulfo and R2 is hydrogen.

9. A dyestuff according to claim 1, wherein X is vinyl or .beta.-sulfatoethyl.

10. A dyestuff according to claim 1, wherein K1 is bivalent 1-amino-naphthol(8)-3,6-disulfonic acid, 1-amino-naphthol(8)-4,6-disulfonic acid or 2-amino-naphthol(5)-7-sulfonic acid.

11. A dyestuff according to claim 1, wherein K2 is bivalent 2-amino-naphthol(8)-6-sulfonic acid or 2-amino-naphthol(5)-7-sulfonic acid.

12. The dyestuff according to claim 1 and a salt thereof.

13. A dyestuff according to claim 1 and a salt thereof.

61 Process for the manufacture of the dyestuffs as claimed in claim 1, which comprises coupling 2 moles of the diazonium compound of one or two aromatic amines of the general formula (2) (2) in which D, R1, R2 and X are as defined in claim 1 and R1 is in the ortho-position relative to the amino group, with 1 mole of a coupling component of the general formula (3) (3) in which K1, K2 and Y are as defined in claim 1, and, if desired, in order to convert the metal-free disazo dyestuff into its heavy metal complex compound, reacting this dyestuff with an agent which donates a heavy metal cation, or which comprises subjecting one mole of each of the monoazo compounds of the general formulae (4) and (5) (4) (5) described in the form of the free acids, in which R1, R2, D and X are as defined in claim 1 and K3 denotes one of the radicals of the following formulae , , , or and K4 denotes one of the radicals of the following formulae , or or two moles of their heavy metal complex compounds in which R1 is a hydroxy group, or 1 mole of this heavy me$al complex compound of the formula (4) or (5) and 1 mole of the metal-free compound of the formula (5) or, respectively, (4) to a condensation reaction with a halogeno-s-triazine compound of the formula (6) in which Y is as defined in claim 1 and Hal represents a chlorine, bromine or fluorine atom, and where required, subsequently reacting the product with an agent which donates a heavy metal cation.

15. Fiber materials of natural or regenerated cellulose or natural, regenerated or synthetic polyamide fiber materials which have been dyed with a dyestuff as claimed in claim 1.

16. The copper, chromium or cobalt complex dyestuff of a dyestuff according to claim 1.

17. A process for dyeing and printing a fiber material, which comprises applying a dyestuff of the formula (1), defined in claim 1, in an aqueous medium by a conventional dyeing or printing process to the fiber material and then fixing the dyestuff to the fiber by a conventional fixing method, pref-erably in the presence of an alkali-binding agent.