DE1227588B - Process for the production of dyes of the azo and anthraquinone series - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

C09b

German class: 22a-l

Number: 1227 588

File number: S 77461IV c / 22 a

Filing date: January 9, 1962

Opening day: October 27, 1966

The present invention is a process for the preparation of dyes of the azo and anthraquinone series, which is characterized in that 1 mol of a dye is used Azo or anthraquinone series, which has at least one exchangeable one bound to an aromatic nucleus Contains hydrogen atom, in the presence of an acidic condensing agent with at least 1 mol of a nitrile of the formula

R-CN

where R is a halogen-containing, saturated or unsaturated aliphatic radical, and at least 0.5 mol of a symmetrical dihalodimethyl ether and optionally the obtained Dye converted into a water-soluble dye by sulfonation and / or sulfation.

A modification of this process for the production of azo dyes of the type described above is characterized in that 1 mole of an azo component which contains at least one of an aromatic, an exchangeable bonded core bearing one or more positive substituents Contains hydrogen atom, in the presence of an acidic condensing agent with at least 1 mole of one Nitrile of the formula

R-CN

wherein R has the abovementioned meaning, and at least 0.5 mol of a symmetrical dihalodimethyl ether converts and the reaction product obtained by reaction with the other azo dye component converted into a water-soluble azo dye.

A particularly interesting embodiment of the process is that the nitrile is used as the formula

R-CN

the -chloro- or α-bromo-ß-hydroxypropionitrile used and carrying out the reaction so that the / 5-hydroxy group is converted into the sulfuric acid ester will.

The method is suitable for all dyes of the azo and anthraquinone series, which at least one contain exchangeable hydrogen atom bonded to an aromatic nucleus. If you use as starting substances compounds which are insoluble in water, these must be replaced by subsequent Sulphonation and / or by simultaneous or subsequent sulphation if the compound and / or The nitrile an alcoholic primary or secondary process for the production of dyes the azo and anthraquinone series

Applicant:

SANDOZ A. G., Basel (Switzerland) Representative:

Dr. W. Schalk, Dipl.-Ing. P. Wirth, Dipl.-Ing. G. E. M. Dannenberg and Dr. V. Schmied-Kowarzik, patent attorneys, Frankfurt / M., Große Eschenheimer Str. 39

Named as inventor:

Dr. Francois Benguerel,

Dr. Ulrich Blass, Basel;

Dr. Wolfgang Schoenauer,

Dr. Walter Wehrli, Riehen (Switzerland)

Claimed priority:
Switzerland of January 10, 1961 (246), July 7, 1961 (8012)

Contains hydroxyl group, are converted into water-soluble dyes.

As anthraquinone compounds with at least one exchangeable hydrogen atom, which particularly suitable for the preparation of the anthraquinone dyes according to the invention fall, for. B. into consideration:

l-amino-4-arylamino-anthraquinones, l-Amino-l-methyl ^ -arylamino-anthraquinones, l-Amino ^ -halogen ^ -arylamino-anthraquinones, l-amino-2-alkoxy-4-arylamino-anthraquinones, l-amino-2-aryloxy-4-hydroxy-anthraquinones, l-amino ^ -arylamino-anthraquinone ^ -sulfonic acids,

1,4-diamino-2-aryloxy-anthraquinone, l-amino-4-arylamino-anthraquinone-2,5 - (- 6,7-

or -8 -) - disulfonic acids,
1,4-diarylamino-anthraquinones, l, 5-diamino-4,8-dihydroxy-2-hydroxyphenylanthraquinones,

anthraquinones,
!, S-Diamino ^^ - dihydroxy ^ -aryloxyphenyl-

anthraquinones,
!, S-dihydroxy ^ -amino-S-arylamino-

anthraquinones,
1,5-dihydroxy-4-nitro-8-arylaminoanthraquinones.

609 705/356

3 4

As azo dyes with at least one interchangeable 3. The use of nitriles permits a substantial

capable hydrogen atom in the molecule come e.g. B. lent savings in working time through an »

those in the diazo or Kupp-pot process, d. H. the mere coexistence

solution component unsulfonated aryl radicals of the benzene mixtures of the starting products with a

or naphthalene series. 5 suitable temperature, usually room temperature.

The both for the azo as for the anthraquinone, on the other hand, must be used for the reaction of

dyes eligible aryl radicals are z. B. Unicorn needed carboxylic acid N-hydroxyme-

the following: 3- and 4-methylphenyl; 2-, 3- and thylamides are often freshly made and

-4-Methoxy- or -Äthoxyphenyl, 2,3- or 3,4-Tetra- are cleaned and must be cleaned with special

methylenphenyl, 2,4- and 2,5- and 2,6-dimethyl- io care in the mostly sulfuric acid environment

phenyl, 2-methyl-4-isopropyl- and -4-n-butylphenyl, as otherwise undesirable

2,4- and 2,5-dimethoxy- or diethoxyphenyl, side reactions appear.

2-Metb.oxy- or 2-Ethoxy-5-methylphenyl 2-Me- _{4 Those mentioned in the present} description

thyl-4-or-5-methoxy- or -ethoxyphenyl, 2-meth- _{Bd ide von dyes} ^ scalable

oxy-4-methylphenyl, 2,4,6-methylphenyl 2 4-di-15 hydroxy-acylamidomethyl groups such as

methyl-6-ethylphenyl, 2,4-diethyl-6-methylphenyl, ^{J JJ} j & w

2,6-Dimethyl-6-n-butylphenyl, 4-chloro-2,5-dimeth- HOCH ₂ - CH (Cl) - CO - NH - CH ₂ -
oxy- or diethoxyphenyl, 4-chloro-2-methoxy-5-me-

thylphenyl, 2-chloro- or 2-bromo-4,6-dimethylphenyl, could so far only by way of the

2-Bromo-6-methyl-4-ethyl- or -4-n-butylphenyl, 20 nitriles are obtained.
2,3,5,6-tetramethylphenyl, 2- and 4-methoxynaphthyl.

The coupling components to be used according to the invention In some cases, the same color components can be used must receive at least one flavoring substance using a similar process, in table, unsulfonated, one or more positive ones instead of dihalodimethyl ether four end, d. H. nucleophilic substituents-bearing 25 formaldehyde solution or paraformaldehyde is used Interchangeable hydrogen atom bound to the nucleus.

The dyes which can be prepared according to the invention are preferably low-molecular alkyl groups, cyclo- hold at least one group, as positive substituents
alkyl groups, hydroxyl and ether groups, preferably low molecular weight alkoxy groups. 30 R - CO - NH - CH ₂ -

The halogen-containing, saturated or unsaturated

Aliphatic nitriles are preferably low molar where R has the meaning given above, and

kular (with e.g. 2 to 4 carbon atoms), are for the most part already known. However, receives

Nitriles of this type are z. B. chlorine or bromine new dyes with very interesting properties

acetonitrile, <x- and / J-chloro- or bromopropionitrile, 35 shafts if the nitrile R - CN oc-chlorine-

oi- or / I-chloro- or bromobutyronitrile, α-chloro- or α-bromo- / 3rhydroxypropionitril uses. The

or a-bromo-jS-hydroxypropionitrile, α, β-dichloro or standing dyes with a group of the formula -Dibromopropionitrile, -chloro- or α-bromoacrylonitrile

and further substituted representatives of this class. HO - CH ₂ - CH - CO - NH - CH ₂ -

The symmetrical dihalodimethyl ethers are 40 | .

the dibromodimethyl ether and preferably the. Shark
To name dichloride methyl ether.

■ '- The reaction is carried out in an acidic medium in which Hal is chlorine or bromine, can easily be carried out, where z. B. sulfuric acid with a sulfur concentration of 70 to 100% used as a condensation agent at the same time as a solution 45 acid in the acidic sulfuric acid ester
■ and condensation agent can serve. To avoid sulfonation and other secondary HO - SO ₂ --O - CH ₂ --CH - CO - NH - CH ₂ - reactions and for activation or regulation

The turnover will turn out depending on the reaction shark
Partners add acetic acid or water than 50

cheap. The reaction can preferably be carried out at. This sulfation is already occurring

Carry out temperatures between 0 and 6O ⁰ C. Each with a sulfuric acid concentration of "93%>

according to temperature and reactants claimed preferably 95 to 96% »and at temperatures

the conversion has a duration of a few minutes up to from about 0 to 25 ^° C., preferably 15 to 25 ^° C.,

several days. 55 while for sulfonation (introduction of an

Compared to the method of the French patent - an aromatic nucleus directly bound - SO ₃ H-

script 1222195, in which chloroacetic acid N-methyl groups) stricter conditions, e.g. 98%

olamide is used, the sulfuric acid or oleum according to the invention has about 1 to 2% free

Procedure has several advantages, e.g. E.g .: SO ₃ and temperatures from 10 to 25 ⁰ C, preferably

-i T ^ - λτ ·. -1 · τ. /- mid.ι ο 1 j .60 wise about 20 ⁰ C, must be applied.

1. The nitriles, such as "-Chlor - ^ - hydroxypropio- _{The sulphated dyes have} a good nitrile and are often more easily accessible than their _{solubility in water; even if they don't} know. Sulfonic calculating N-hydroxymethylcarboxamides; _sä included. This is particularly important the "-Chlor ^ -hydroxy-N-hydroxymethyl-pro ^ ^ _F ^ _{maQ ak starting products color} . pionsauramide z. B. is unknown. _{65 fabrics} ^^ _wdche ^ _{ß a} ^S _ode ⁸ _r several tetra-

2. The nitriles are often cheaper than the corresponding methylphenyl groups with only one aromatic N-hydroxymethylamides, e.g. B. acrylonitrile, Pro-bound exchangeable hydrogen atom ent pionitrile, benzyl cyanide. keep. ,

The dyes obtained are suitable for dyeing, padding and printing fibers of animal origin, z. B. wool, silk, synthetic polyamide fibers, leather, natural cellulose fibers, e.g. B. Cotton, linen and regenerated cellulose fibers, ζ. B. Viscose and copper rreyon or Spun rayon, as well as mixtures and / or structures made from these fibers. The optimal application conditions vary according to the type of fiber and the dyes used.

Animal fibers and synthetic polyamide fibers are preferably made in acidic, neutral or dye and print or fix in a weakly alkaline medium, e.g. B. in the presence of acetic acid, Formic acid, sulfuric acid, ammonium sulfate, sodium metaphosphate, etc. You can also in the presence of leveling agents, e.g. B. polyoxyethylated fatty amines or mixtures thereof with alkyl polyglycol ethers, Color acetic acid to neutral and at the end of the color the bath by adding small amounts of an alkaline reacting agent, e.g. B. ammonia, sodium bicarbonate, soda, etc., or compounds which react alkaline when exposed to heat, e.g. B. hexamethylenetetramine, urea, blunt to a neutral or slightly alkaline reaction. This is followed by thorough rinsing and acidified with a little acetic acid if necessary. The dyeings and prints obtained generally have good fastness to light, washing, fulling, water, perspiration, rubbing and dry cleaning.

The dyeing, padding and printing or fixing of the dyes on cellulose fibers is advantageously carried out in an alkaline medium, e.g. B. in the presence of sodium bicarbonate, sodium carbonate, caustic soda, Potash lye, sodium metasilicate, sodium borate, trisodium phosphate, ammonia, etc. Zur Reduction phenomena are avoided when dyeing, padding or printing the fibers mild oxidizing agents, such as 1-nitrobenzene-3-sulfonic acid, are often advantageous Sodium, added. The fixation of the dyes also takes place in the case of cellulose fibers usually in the warmth.

The dyeings and prints on cellulose fibers are particularly notable for their excellent wet fastness properties the end. These are in the process of forming a stable chemical bond between the dye molecule and the cellulose molecule. Often times, not all of the dye takes on the chemical Implementation with the fiber part. The proportion of the unreacted dye is carried through in these cases suitable operations, such as rinsing and / or soaps, if necessary using higher temperatures, removed from the fiber, synthetic detergents such as. B. Alkylarylsulfonate, Sodium lauryl sulfate, sodium lauryl polyglycol ether sulfate, optionally carboxymethylated alkyl polyglycol ethers and also mono- and dialkylphenyl polyglycol ethers, use. One obtains light, Wash, water, perspiration, rubbing and dry cleaning fast dyeings and prints.

The parts mentioned in the examples are parts by weight and the percentages are percentages by weight. The temperatures are given in degrees Celsius.

example 1

9.1 parts of 1-amino-4- (2 ', 4', 6'-trimethylphenylamino) anthraquinone-2-sulfonic acid are carried in 145 parts of 96% strength sulfuric acid at 10 to 15 ° Add sodium and stir until everything is dissolved. 1.9 parts of chloroacetonitrile are then carried at 0 ° to 5 ° in about 10 minutes and then allows 1.45 parts of dichlorodimethyl ether to be added dropwise at the same temperature. The mixture is stirred at 15 to 20 ° for 24 hours and then the reaction mass is poured onto 400 parts of ice. Of the The resulting precipitate is filtered off and washed neutral with a dilute sodium chloride solution. Of the The filter cake is suspended in water and adjusted to pH 7 by adding dilute sodium hydroxide solution posed. Then you precipitate the dye with table salt, nitrate it, wash it with a diluted one Saline and dry it. It dyes wool from a weakly acidic bath blue. The colorations are lightfast and wetfast, especially washfast and millfast. 2 parts of the above dye, 0.8 parts of an oxethylated one Fatty amine and 0.5 part of an oleyl polyglycol ether are dissolved in 5000 parts of water and mixed with 2 parts of glacial acetic acid. This dye liquor is heated to 40 to 50 °, whereupon 100 parts Wool enters and brings the bath to the boil within 30 minutes. Cook for 45 minutes whereupon the material is rinsed and dried. So you get a level, very light and wet fast blue coloring. The dye liquor is then neutralized with ammonia after the dyeing process and treating the material to be dyed in it for 20 minutes at 90 °, you get something else more wet-fast dyeing. The same effect can also be achieved by treating the material to be dyed in a new one Bath of 5000 parts of water and 3 parts of hexamethylenetetramine at 90 to 95 ° for 20 to Achieve 30 minutes.

Example 2

In 145 parts of 96% ^it will be at 15 to 20 °, 9.5 parts of sulfuric acid l, 4-di- (2 ', 4', 6'-trimethylphenylamino) anthraquinone dissolved with stirring. This is done within 10 minutes at 0 to 5 °

3.8 parts of chloroacetonitrile and then leaves

2.9 parts of dichlorodimethyl ether at the same temperature drip. The mass is stirred for 24 hours at 15 to 20 °. Then you pour it on 400 parts of ice, stirred for a short time and then filtered off the precipitate, washed neutral with water and dries it. After reacting with 20% oleum for several hours at 15 to 20 ° a dye is obtained which dyes wool blue. The dyeings are very washable and washable.

A mercerized cotton fabric is printed with a printing paste of the following composition:

20 parts of the information given above

obtained dye,
100 parts urea,
397 parts of water,

450 parts of 3% sodium alginate ^he ig,
10 parts of sodium 3-nitrobenzenesulfonate,
20 parts of sodium carbonate,
3 parts of 30% sodium hydroxide solution.

1000 Teüe The fabric is dried and steamed for 10 minutes at 102 to 104 °. Then it will

7 8

Rinsed cold and boiling for 10 minutes with example 6
100 ° with a 0.3% strength solution in distilled ^en Soap

Soaped with water, rinsed again cold and hot and 36 parts of 2- (2 ', 4', 6'-trimethylphenyl) -amino-8-hy-

dried. A vivid blue print is obtained. Hydroxynaphthalene-6-sulfonic acid is obtained at 0 ° in

with excellent wet fastness properties. 5,350 parts of 96% sulfuric acid dissolved and added dropwise with 60 parts by volume of the stock solution of

Example 3 game4 offset. The mixture is 2 to 3 hours

stirred at 15 to 20 ° and then on

In 145 parts of 96% strength ^he be cast at 1000 parts of ice sulfuric acid. The reaction product falls from 0 to 5 ° 15 parts of chloroacetonitrile dissolved. On this io immediately. It is filtered off and, at the same temperature, within water with the required amount of sodium, 12 parts of dichlorodimethyl ether are added dropwise in 500 parts of hydroxide to a neutral coupling solution and the mixture is stirred for 24 hours at 15 ° to 20 °. In works. The latter is added at 25 to 30 ° in a fresh 145 parts of 96% strength sulfuric acid at 10 to ^he be prepared aqueous diazo solution of 17 parts of 1-amino-20 °, 9.1 parts of the sodium salt of 1-amino-2-benzene 15 sulfonic acid and accelerates the coupling 4- (2 ', 4', 6'-trimethylphenylamino) -anthraquinone-2-sul- by adding sodium acetate. Finally, fonsäure dissolves. For this purpose, the pH is adjusted to 5 to 6 parts of the aforementioned sulfuric acid within one hour with sodium hydroxide solution and 22 parts of the coupling product is precipitated with sodium chloride. The solution is added dropwise and the mass is stirred while it is filtered off and at a maximum of 40 ° in vacuo for 24 hours at 10 to 15 °. Then you pour them to 20 dry. A red dye is obtained which contains 400 parts of ice. The resulting precipitate is filtered off wool from a weakly acidic bath and cotton and washed neutral with a dilute sodium chloride solution from alkaline printing pastes in bluish-tinted red. The filter cake is dyed in water shades of very good wet and light fastness, suspended and by adding dilute ". .
Sodium hydroxide solution adjusted to pH 7. Then 25 example /
the dyestuff is removed with sodium chloride, filtered off, 9.5 parts 1,4-di-mesidino-anthraquinone are dried in 145 parts of 96% sulfuric acid and washed with a dilute sodium chloride solution from 15 to 20 °. A similar color solution is obtained. At 0 ° to 5 °, one adds to this solution as in Example 1. Other 5.1 parts / 3-hydroxy-a-chloro-propionitrile and. ■ 30 2.8 parts of dichlorodimethyl ether, the tempe-

Example 4 _{Rature to 15 to 20} ° and stir the mass

In 920 parts of 96% strength sulfuric acid, the mixture is left at this temperature for 24 hours. then 10 to 20 ° with thorough stirring 100 parts of chloroacetone are poured onto 250 parts of saturated sodium chloride nitrile drop in and stir the mixture for a further 2 hours of solution and 250 parts of ice. The precipitate obtained den at 20 °. Then left at 10 to 15 ° in 35 is filtered off, in 400 parts of 10% sodium about 77 parts of dichlorodimethyl ether monochloride solution are taken back to pH 7 for 30 minutes flow and stir the reaction mixture, exactly neutralized for 15 hours, again filtered off with suction and dried, at 15 to 20 °. 600 parts by volume of stock are obtained. A dye is obtained which contains two sulfur solutions, contains acid ester groups and wool washable and

47.7 parts of the dye (in the form of sodium 40 waterfast blue,
salt), which can be obtained by alkaline coupling of. .
l-diazo-2,5-dimethylbenzene on l- (2 ', 5'-dichlorophe- Example 8
nyl) -3-methyl-5-pyrazolone-4'-sulfonic acid is obtained, in 145 parts of 96% sulfuric acid in the at 0 to 10 ° in 400 parts of 96% sulfuric acid 15 to 20 ° 9.1 parts of Sodium salt of 1-amino, dissolved. At 5 °, 60 parts by volume of the above-mentioned 4-mesidino-anthraquinone-2-sulfonic acid are dissolved. When the stock solution is set to 0, it is added dropwise to 5 ° over the course of 30 minutes, 2.6 parts are added to this solution in succession and the mixture is stirred at room temperature / S-hydroxy-a-chloropropionitrile and 1.45 parts of di-15 hours. Then it is poured into 1000 parts of chlorodimethyl ether and the mass is stirred while ice and the precipitated yellow dye is filtered off at 10 ° to 20 ° for 24 hours. Then you pour it on. He is once again from water with table salt 50 400 parts of ice. The resulting precipitate is filtered off with simultaneous neutralization with and with a dilute sodium hydroxide solution. Washed neutral by vacuum drying at 40 °. The filter cake is obtained in water to obtain a dye that is weakly suspended from the wool and adjusted to pH 7 by adding a dilute acidic bath in bright yellow shades of sodium hydroxide solution. Then there is excellent wet and light fastness dyes. 55 you remove the dye with common salt, filter it,

. . washes it with dilute saline and

Example 5 dries it. This is how you get one

40.8 parts of the dye are in the form of the sodium dye that dyes wool blue. The dyeings are salt (salt), which can be obtained by alkaline coupling of very good wash and water fastness.
l-diazo-2,5-dimethylbenzene on l-phenyl-3-methyl-60 The following table! contains anthraquinone-5-pyrazolone-3'-sulfonic acid, high dyes, which are dissolved in 500 parts of 75% sulfuric acid according to the invention at least 30 °, method and in particular according to the details of the 60 parts by volume of the stock solution from Example 4 Examples 1 to 3 and 7 and 8 are obtainable and are added dropwise in about 30 minutes and stirred through the dye structure, the aryl radical or radicals, for 15 hours. By working up the reactive component as in 65, if necessary from Example 4, a reddish-tinged yellow dye-leading aftertreatment and the color of the fabric are obtained, which gives excellent light- and wet-fast wool dyeings on wool or cotton. are drawn.

9 Dye framework 1 227 588 Aryl Reactive component 10 hue the coloring
on wool (D Table I. (Π) (III) or cotton l-amino-4-arylamino- 2,4,6-trimethylphenyl Chloroacetonitrile To
treatment (V) No. anthraquinone blue the same 2,4,5,6-tetramethyl a-chloro-ß-hydroxy- (IV) phenyl propionitrile Sulfonating blue 9 l-amino-2-methyl- 2,5-dimethoxyphenyl / 3-chloropropionitrile 4-arylamino-anthra- Sulfating blue 10 chinone l-amino-2-bromo- 2,5-dimethylphenyl «, ^ - dichloropropio- Sulfonating 11 4-arylamino-anthra- nitrile blue chinone l-amino-2-methoxy- 2,4-dimethylphenyl oc-chloroacrylonitrile Sulfonating 12th 4-arylamino-anthra- violet chinone l-amino-2-aryloxy- the same Bromoacetonitrile Sulfonating 13th 4-hydroxy-anthra- Red chinone 1,4-diamino-2-aryloxy 2,5-dimethylphenyl Chloroacetonitrile Sulfonating 14th anthraquinone violet l-amino-4-arylamino- 2,4,6-trimethyl the same anthraquinone-2,6-di- phenyl Sulfonating blue 15th sulfonic acid the same 2,3-tetramethylene the same - 16 phenyl blue l-amino-4-arylamino- 2-methoxy-5-methyl- the same anthraquinone phenyl - blue 17th 2,5 (8) -disulfonic acid the same 2,3,5,6-tetramethyl the same - 18th phenyl blue 1,4-diarylamino 2,4-dimethylphenyl «, JS-dichloropropio- anthraquinone nitrile - green 19th the same 2-bromo-4,6-di- «-Chlor-jö-hydroxy- methylphenyl propionitrile Sulfonating blue 20th the same 4-methoxynaphthyl jS-bromopropionitrile l, 5-dihydroxy-4,8-di- 4-hydroxyphenyl the same Sulfating green 21 amino-2-aryl-anthra- blue chinone Sulfonating 22nd the same 4-methoxyphenyl Chloroacetonitrile Sulfonating 23 the same 4-phenoxyphenyl the same blue l, 5-dihydroxy-4-amino- 4-j8-hydroxy the same blue 8-arylamino-anthra- ethoxyphenyl Sulfonating blue 24 chinone Sulfonating 25th 1,5-dihydroxy-4-nitro 4-methoxyphenyl the same Sulfating 26th 8-arylamino-anthra- blue chinone l-amino-4-arylamino- 2,4-diethoxyphenyl the same Sulfonating 27 anthraquinone-2-sulfone- blue acid the same the same / J-chloropropionitrile - 28 the same 2,4,6-trimethyl Λ-chloroacryhiitrile blue phenyl blue 1,4-diarylamino-anthra- . 2-methyl-4,6-di- «-Chlor-jö-hydroxy- - 29 chinone ethylphenyl propionitrile - blue 30th the same 2-methyl-4-ethyl the same 6-bromophenyl Sulfating Reddish blue 31 the same 2-methyl-4-n-butyl- the same 6-bromophenyl Sulfating Reddish blue 32 Sulfating 609 708/356 33

In the following Table II azo dyes are listed, which according to the invention Process and in particular according to the information in Examples 4 and 5 (Examples 34 to 49) and 6 (Examples 40 to 49) are available and through the diazo and

Coupling components, the reactive component, any aftertreatment to be carried out and the color of the dyeings on wool or cotton are indicated.

Table II

Diazo component -ι '> - Coupling component Reaction component TsYes _n u • Sulfating -. hue Red '\ t ": l-Amino-4-met ^ .yl -,., treatment the coloring Red-brown No. © benzene-2-sulfonic acid (ID (HD - on WoUe l-amino-2,4-dimethyl- 1- (2 ', 5'-dichlorophenyl> α, / 3-dichloropropionitrile (IV) cotton benzene 3-methyl-5-pyrazolone - (V). 34 4'-sulfonic acid yellow l-amino-2,4,6-tri- the same. "., ... _{/ r} l- (2'-chlorophenyl) - a-chloro-ß-hydroxy- Red Λ'ί ·. methylbenzene the same -. _{: i} , 3-methyl-5-pyrazolone propionitrile 35 l-amino-2,5-di- the same 1-hydroxynaphthalene the same Yellowj methylbenzene the same 3-sulfonic acid ■ - '■ —τ' 36 the same. ■ "· the same l- (2 ', 5'-dichloroph6nyl) - «, / S-dibromopropionitrile -. - orange ., the same S-methyl-S-pyrazolone- I. Red 37 the same 4-sulfonic acid - Yellow ^[p the same 1-hydroxynaphthalene Chlofacetonitrile - ■] 4,6-disulfonic acid t -, ί - 38 l-amino-4-methoxy- 2-acetylamino-8-hy- the same Schaflach Red j benzene droxynaphthalene .jt Red Red j 39 6-sulfonic acid - Red ! Red j '■' " 1-aminobenzene 2- (4'-methoxyphenyl- the same ■ red 2-sulfonic acid amino) -5-hydroxy- •Red 40 ■ naphthalene-7-sulfone acid (alkaline coupling) -. - ■ the same 2- (4'-methylphenyl- the same amino) -8rhydroxy- 41 naphthalene-6-sulfone acid. (acidic coupling) - - 2- (2 ', 4', 6'-trimethyl _r , ; «R, Chlpr- / 3-hydroxy- - ■,. phenylaminep) -8-hy- propionitrile "■ - ■ - ' 42 droxy naphthalene .— 6-sulfonic acid ■■ - '^ * · - * -ί ■ (acidic coupling) _, the same α-bromo-butyronitrile the same ·. ..... öc-chloroacryhiitrile 43 the same «, ^ Dichloropropionitil 44 the same a, j3-dibromopropionitrile 45 the same Ä-Bromopropionitrile 46 the same Bromoacetonitrile 47 2- (2 ', 4'-dimethyl- Chloroacetonitrile 48 phenylamino) -8-hy- 49 droxynaphthalene 6-sulfonic acid (acidic coupling)

Claims (3)

Patent claims: 1. Process for the preparation of dyes of the azo and Änthraquinone series, thereby characterized in that 1 mol of a dye of the .'Azo or anthraquinone series, of at least one to an aromatic nucleus bound exchangeable hydrogen amid. contains, in the presence of an acidic condensation agent with at least 1 mol of a nitrile formula R-CN wherein R is a halogen-containing, saturated or is an unsaturated aliphatic radical, and at least 0.5 mol of a symmetrical dihalodimethyl ether converts and optionally converts the dye obtained into a water-soluble dye by sulfonation or sulfation convicted. 2. A process for the preparation of azo dyes of the type obtainable according to claim 1 in Modification of the method according to claim 1, characterized in that 1 mole of one Diazo or azo component which has at least one aromatic, one or more positive substituent-bearing core contains bonded exchangeable hydrogen atom, in the presence of an acidic condensing agent with at least 1 mole of a nitrile formula R-CN wherein R has the abovementioned meaning, ao and at least 0.5 mol of a symmetrical dihalodimethyl ether is reacted and the obtained Reaction product by reaction with the other azo dye component into one water-soluble azo dye transferred. 3. Process according to Claims 1 and 2, characterized in that the nitrile of the formula R-CN the Λ-chloro-ß-hydroxypropionitrile used and carries out the reaction in such a way that the hydroxyl group is converted into the sulfuric acid ester. Considered publications:
French patent specification No. 1 222 195. Legacy Patents Considered:
German Patent No. 1192 761. When the application was announced, a coloring table with explanations was laid out. 609 708/356 10.66 ® Bundesdruckerei Berlin