DE1216460B - Process for the preparation of water-insoluble monoazo dyes - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

C 09b

German AI: 22 a -1

Number: 1 216 460

File number: F 33566IV c / 22 a

Filing date: April 1, 1961

Opening day: May 12, 1966

It has been found that valuable water-insoluble, particularly solvent-fast monoazo dyes can be obtained the general formula

R-NH-CO

HO

CO-NH

HN

NH

in which the group R - NH - CO - is in the m- or p-position to the azo group, R is a hydrogen atom, denotes an alkyl or aryl radical, the benzene nucleus A by alkyl, alkoxy groups or halogen atoms and the benzene nucleus B may be substituted by alkyl groups or halogen atoms, if the diazonium compounds of amines of the general formula

R-NH-CO

NH ₂

in which the group R - NH - CO - is in the m- or p-position to the amino group, R is a hydrogen atom, denotes an alkyl or aryl radical, and the benzene nucleus A by alkyl, alkoxy groups or Halogen atoms can be substituted with 4- (2 ', 3'-Oxynaphthoylamino) -benzimidazolonen, which may be substituted in the benzene nucleus of the benzimidazolone radical by alkyl groups or halogen atoms, couples. The dyes can be produced in bulk, on the fiber or on another substrate.

As diazo components 3- or 4-aminobenzoic acid amides come into consideration, such as. B. 3-aminobenzoic acid amide, 3-aniino-benzoic acid diethylamide, 3-amino-benzoic acid anilide, 3-amino-4-methyl-benzoic acid amide, 3 - amino - 4 - chloro - benzoic acid amide,

3 - Amino - 4 - methoxy - benzoic acid amide, 3 - Amino-4-methoxy-benzoic acid anilide, 3-Amino-4-methoxybenzoic acid - 2'- methyl - 3'- chloro - anilide, 3 - amino

4-methoxy-benzoic acid- 2'- chloro-anilide, 3-amino-4-methoxy-benzoic acid-2 ', 5'-dichloro-anilide, 4-aminobenzoic acid amide, 4-amino-benzoic acid methylamide or 4-amino-benzoic acid anilide.

Process for the preparation of water-insoluble monoazo dyes

Applicant:

Farbwerke Hoechst Aktiengesellschaft

formerly Master Lucius & Brüning,

Frankfurt / M.

Named as inventor:

Dr. Günther Semler,

Heppenheim (a. D. Bergstrasse);

Dr. Karl Schilling, Frankfurt / M.-Höchst

The amino compounds are made in a known manner

so diazotized and in alkaline, but preferably in neutral to weakly acidic medium with the 2 ', 3'-oxynaphthoyl compound of 4-amino-benzimidazolone coupled. Instead of the 2 ', 3'-oxynaphthoyl compound of the 4-amino-benzimidazolone can also use the corresponding ones in the benzene nucleus of the benzimidazolone radical by alkyl groups or halogen atoms substituted derivatives, such as. B. 4- (2 ', 3'-Oxynaphthoylamino) -6-methylbenzimidazolone or 4- (2 ', 3'-oxynaphthoylamino) -6-chlorobenzimidazolone can be used. For the manufacture of the pigments it proves Sometimes it is advantageous to carry out the coupling in such a way that the diazo and azo components are used at the same time allowed to run into an acetic acid-sodium acetate buffer mixture.

The azo components used to prepare the monoazo dyes by the process of the invention can by known processes, for example by reacting 2-oxy-3-naphthoic acid chloride with 4-amino-benzimidazolone or a derivative thereof in one for this reaction suitable solvent, such as. B. toluene or pyridine.

The dyes obtained according to the process are often of hard grain and have to be produced the full color strength can be subjected to an aftertreatment. The application of organic solvents, such as. B. o-Dichlorbenzoi, pyridine, dimethylformamide or phosphoric acid trisdimethylamide, optionally at elevated temperature, proven to be particularly expedient. This aftercare can be avoided if you the coupling in the presence of anion-active,

609 568/494

3 4

cationic or nonionic emulsifiers, or the coupling mixture is heated by introducing it

Carries out emulsifier mixtures or with increased steam to 95 to 100 ° C, filters the dye

Temperature decouples or the dye after finished, washes with water free of pyridine and dries at

Coupling in aqueous suspension with organic 80 ° C. This is obtained without further aftertreatment

Solvents for some time, possibly in the car - 5 23 parts by weight of a grainy brown paint

klav heated. substance of high color strength and good light and

The new dyes are suitable for making solvent fastness.
of printing inks and for the preparation of colored lacquers. You can also use it for the coloring of chewing Example 3
chuk and plastics, especially polyvinyl io

chloride, can be used. They have good to very 10.6 parts by weight of 3-amino-benzoic anilide are

good light and solvent fastness. the 15 hours at 20 ⁰ C in 33 parts by volume of 5N salt

Loading the acid from German Patent 1,041,463 and stirred for 200 parts by volume of water and ankannten azo dyestuff obtained from diazotised 1-amino-closing at 5 to 10 ⁰ C with 50 parts by volume of In-Na-2-methoxybenzene-5-sulfonic acid n-butylamide and 6- (2 ', 15 diazotized trium nitrite solution. This diazo solution is 3'-oxynaphthoylamino) -3-chloroindazole are those containing 100 parts by volume of 2N sodium acetate solution, 50 parts by volume of 2N acetic acid and 10 parts by volume of a barer constitution in the bleed fastness of the poly 10 ° / ₀ aqueous solution of an emulsifier added, vinyl chloride staining, the obtained in the overspraying fastness by reaction of oleyl alcohol with nitrocellulose lacquer dyes and the solvent fastness ao ethylene oxide.

far superior. The solution of

_{R. .J 1} 16.7 parts by weight 4- (2 ', 3'-oxynaphthoylamino) -

^pl 6-methyl-benzimidazolone in 50 parts by volume 2 n-soda

6.8 parts by weight of 3-amino-benzoic acid amide are alkaline and 150 parts by volume of water in about 1 hour

in 33 parts by volume of 5 η-hydrochloric acid and 200 parts by volume of ² 5 are added dropwise with vigorous stirring. The clutch is

Dissolved water and terminated immediately at 5 to 10 ⁰ C with 50 parts by volume. Then the clutch mix

Diazotized in sodium nitrite solution. This solution can be ^{heated to 95 to 100 0} C and filtered. The dye

it is washed at the same time with a solution of 16% by weight and ^{dried at 8O 0} C,

divide 4- (2 ', 3'-oxynaphthoylamino) -benzimidazolone into 25 parts by weight of a weakly colored,

50 parts by volume of 2N sodium hydroxide solution and 150 parts by volume of 30 grain-hard pigment, which is

Water to a mixture of 50 parts by volume of 2N acetic your with 100 parts by volume of pyridine at 20 ⁰ C in the

acid, 100 parts by volume of 2N sodium acetate solution and strongly colored and grainy form is transferred.

10 parts by volume of a 10% strength aqueous solution of the resulting 20 parts by weight of a bluish-tinged red

Reaction product of 1 mole of oleyl alcohol with dye.

30 moles of ethylene oxide are added within 30 minutes. If the 3-amino-benzene-

drops. The coupling is immediately after the addition of acid anilide by 10.6 parts by weight of 4-amino-benzene-

the diazo and azo components ended. Then acid anilide and the rest of the procedure is exactly the same as

heated to the coupling mixture by introducing described above, one obtains 25 Gewichtsvon steam at 95 to 100 ⁰ C, filtered, the dye parts of a very soft grain, red dye of

off, washes thoroughly with water and dries 40 high color strength,

at 80 ° C. 23 parts by weight of a grain Example 4 are obtained
hard, weakly colored pigment.

If this product is treated in 8.5 parts by weight of 3-amino-4-chlorobenzamide for 1 to 2 hours

150 parts by volume of dimethylformamide at boiling temperature according to the information in Example 3 and diazotized with

ratur, then diluted with twice the 45 16.7 parts by weight 4- (2 ', 3'-oxynaphthoylamino) -

Volume of water, filtered and washed the remaining 6-methyl-benzimidazolone coupled. You get 25 ge

Dimethylformamide with water, you get parts of a grain hard and weak color

after drying at 80 ° C. 16 parts by weight of a substance. For conversion into the strongly colored form

grainy brown dye of high color- the product in 100 parts by volume of phosphoric acid tris-

starch and good light and solvent fastness. 5 ° dimethylamide stirred for 4 hours at 100 ° C, the

. · Ι ₀ suspension with twice the volume of water

ß e 1 s ρ 1 e 1 2 diluted, filtered off, the dye washed well

7.5 parts by weight of 3-amino-benzoic acid methylamide and dried at 8O ⁰ C. 22 parts by weight are obtained in 33 parts by volume of 5N hydrochloric acid and 200 parts by volume of a strongly bluish-tinged red pigment in parts by volume of water and at 5 to 10 ° C. with 50 parts by volume, particularly good solvent fastness.
Circumferentially diazotized in sodium nitrite solution. These

Solution is left at the same time as a solution from Example 5
16.7 parts by weight of '4- (2', 3'-oxynaphthoylamino) -

6-methyl-benzimidazolone in 50 parts by volume 2n-Na- 16 parts by weight 4- (2 ', 3'-oxynaphthoylamino) -benz-

Sodium hydroxide solution and 150 parts by volume of water to form a 60 imidazolone in 50 parts by volume of 2N sodium hydroxide solution

Mixture of 50 parts by volume of 2N acetic acid, 100 parts by volume and 150 parts by volume of water dissolved. The clear solution

divide by volume 2N sodium acetate solution and 10 vol-

solution of a 10 ° / ₀ aqueous solution of the reaction and 10 parts by volume of a 10 ⁰ / o aqueous

Product of 1 mole of oleyl alcohol with 30 moles of ethyl solution of the reaction product of 1 mole of oleyl

Add lenoxyd dropwise within 1 hour. To the Kupp- 65 alcohol with 30 moles of ethylene oxide and falls the azolation reaction to accelerate, add 50 parts by volume of 2n-

the run-in time 50 parts by volume of pyridine to the template. Finely divided acetic acid. For this one gives The coupling is terminated practically immediately. Then at 15 to 20 ° C the diazo solution, which consists of 8.3 weight

5 6

divide 3-amino-4-methoxy-benzoic acid amide, 33 by volume, the mixture to 95 to 100 ° C, filtered, washed by volume of 5N hydrochloric acid, 150 parts by volume of ice water and drying at 80 ° C. 36 parts by weight are obtained and 10 parts by volume of 5N sodium nitrite solution at 5 to of a strongly colored pigment that is in his 10 ° C was prepared in the course of 30 minutes. Properties the Pro-Nach described in Example 6 After stirring for 15 minutes, the coupling corresponds to 5 ducts.

completed. The coupling mixture _{R is} then heated. · Ι ο

by introducing steam to 95 to 100 ° C and example S.

filters off the dye. It is washed with water 16.7 parts by weight 4- (2 ', 3'-oxynaphthoylamino) -

and dried at 80 ° C. 24 parts by weight of 6-methyl-benzimidazolone are obtained in 50 parts by volume

a grain-hard, weakly colored pigment. 10 2N sodium hydroxide solution and 150 parts by volume of water dissolved.

To achieve the full tinctorial strength stirring the clear solution is mixed with 100 parts by volume of the product 2 hours with 200 parts by volume of pyridine 2n-sodium acetate solution and 10 parts by volume of at boiling, then ° / ₀ aqueous solution diluted with the double-10 of the reaction product-coupled volume Water and filter off the dye. of 1 mole of oleyl alcohol with 30 moles of ethylene oxide and After thorough washing with water and drying 15, the azo component precipitates by adding 50 volumes at 80 ° C. to obtain 21 parts by weight of a very partial 2N acetic acid in finely divided form. To this end, a clear bluish-tinged red pigment of high color is added at 20 ° C. to the diazo solution, which has a strength of 14.5 and very good fastness properties. parts by weight of 3-amino-4-methoxy-benzoic acid-2'-me-

If the 3-amino-4-methoxy-benzoic acid-ethyl-3'-chloro-anilide is prepared in the usual way amide has been increased by 7.5 parts by weight of 3-amino-4-methyl-ben-20 over the course of 30 minutes. The cupzoic acid amide, This is how you get after treatment is practically finished immediately. Then you heat it up The coupling mixture, which is initially obtained in a weakly colored form, is caused by the introduction of steam Dye with hot dimethylformamide 20 Ge to 95 to 100 ° C and filtered off the dye. To parts by weight of a very solvent-fast pigment - washing and drying gives you 30 parts by weight of dye which is not quite as bluish as 25 parts of a grain-hard, weakly colored pigment. To the product described above. Conversion into the strongly colored form is treated

the dye with 250 parts by volume of pyridine for 3 hours

Examples at boiling point and removed after cooling

most of the pyridine by filtration, the

12.1 parts by weight of 3-amino-4-methoxy-benzoic acid, remainder by steam distillation. The dye anilide in 33 parts by volume of 5N hydrochloric acid and is filtered off with suction, washed and dried. Man 150 parts by volume of ice water dissolved and with 10 parts by volume, 23 parts by weight of a very strong, share 5 n-sodium nitrite solution diazotized. This, necessary clear bluish-tinted red dye, which is through Diazo solution, if necessary clarified by filtration, fails to have very good light and solvent fastness properties within 30 minutes along with the 35 draws.

Solution of 16 parts by weight of 4- (2 ', 3'-oxynaphthoyl- If the 4- (2', 3'-oxy-

amino) -benzimidazolone in 50 parts by volume of 2η-sodium naphthoylamino) -6-methyl-benzimidazolone by lye and 150 parts by volume of water in a mixture of 18.6 parts by weight of 4- (2 ', 3'-oxynaphthoylamino) -50 parts by volume of 2n-acetic acid 100 parts by volume of 2n-Na-6-chlorobenzimidazolone, 23 parts by weight of trium acetate solution are obtained, 10 parts by volume of a 10% strength 40 parts of a bluish-tinted red pigment dye of aqueous solution of the reaction product of oleyl-like properties,
alcohol with ethylene oxide and 150 parts by volume of a

10% aqueous solution of paraffinsulfamido- Example 9

acetic acid sodium (the underlying paraffin - 13.8 parts by weight of 3-amino-4-methoxy-benzoic acid-

the rest corresponds to a hydrocarbon fraction of 45 2'-chloroanilide are added dropwise in 33 parts by volume of 5N hydrochloric acid (boiling range 180 to 210 ° C). The coupling and 150 parts by volume of ice water, stirred for 2 hours, ended immediately. The coupling mixture is then heated and then n-sodium nitrite solution is diazotized at 5 to 10 ° C. with 10 parts by volume by passing in steam for 1 hour. The obtained Susauf 90 ° C, filtered, washed with water and dried board is allowed within 1 hour together with at 8O ⁰ C. were obtained in this way 32 parts by weight of 50 of the solution of 16 parts by weight 4- (2 ', 3'-Oxynapheines Grain-soft, strongly colored red pigment dyestuff (thoylamino) benzimidazolone in 50 parts by volume of 2N substance of very good fastness properties. tron lye and 150 parts by volume of water to form a Ge

Mix of 50 parts by volume of 2 n-acetic acid, 100 parts by volume

Example 7 divide 2N sodium acetate solution and 10 parts by volume

55 of a 10 ° / ₀ aqueous solution of the reaction

10 parts by volume of aluminum sulfate containing water of crystallization from 1 mole of oleyl alcohol and 30 moles are dissolved in 100 parts by volume of water and added dropwise with ethylene oxide. After the coupling is complete, 40 parts by volume of 2N soda solution are precipitated. The resulting mixture is heated by introducing steam. The alumina substrate is filtered off, washed with water, to 95 to 100 ^° C. and filtered off with suction. The press cake, which is still moist, made into a paste and washed to a mixture of 50 parts by volume of 60 water, is slurried in 1000 parts by volume of 2N acetic acid, 100 parts by volume of 2N sodium acetate parts of water, then a suspension solution and 10 parts by volume of a 10 ° / ₀ igen aqueous sion of 200 parts by volume of water, 50 parts by volume of solution of the emulsifier obtainable by reacting oleyl alcohol and dichlorobenzene and 15 parts by volume of paraffin sulfamido-ethylene oxide. Sodium acetic acid (the paraffin on which this suspension is based is allowed to add the remainder according to the data 65 corresponds to a hydrocarbon fraction of the solutions prepared in Example 6 in the azo range and boiling range 180 to 210 ° C.) and the Ge diazo component is added within 30 minutes - mixed heated to 90 to 95 ° C for 1 hour. After the drip. The coupling is terminated immediately. Then heated, customary work-up, 28 parts by weight are obtained

of a grain-soft, strongly colored pigment of a similar shade and properties as that product described in example 6.

In this example, the 3-amino-4-methoxy-benzoic acid-2'-chloroanilide is replaced by 15.5 parts by weight of 3-amino-4-methoxy-benzoic acid-2 ', 5'-dichloroanilide, one obtains 32 parts by weight of a substantial one yellowish dye with otherwise similar properties.

B e i s ρ i e 1 10

6.8 parts by weight of 4-amino-benzoic acid amide are diazotized as described in Example 2 and coupled with 16.7 parts by weight of 4- (2 ', 3'-oxynaphthoylamino) -6-methyl-benzimidazolone. Obtained 24Ge- * 5 weight parts of a grain hard and weakly colored pigment which is stirred 2 hours by 250 parts by volume of dimethylformamide at 2O ⁰ C in order to obtain the full color strength. The thick suspension is then diluted with twice the volume of water and the dye is filtered off, washed and dried. 21 parts by weight of a bluish-tinged red pigment dye are obtained.

If in this example the 4-amino-benzoic acid amide is replaced by 7.5 parts by weight of 4-amino-benzoic acid methylamide, in this way, after coupling and the usual work-up, 24 parts by weight of one are obtained weakly colored and grain-hard pigment, which can be used for 1 hour to achieve a higher color strength Treated 200 parts by volume of boiling dimethylformamide. 18 parts by weight of a red pigment are obtained, which is significantly more bluish than the product described above.

Example 11

Primer bath

15 g of 4- (2 ', 3'-oxynaphthoylamino) -6-methyl-benzimidazolone are made into a paste with 50 g of denatured ethyl alcohol and, after adding 15.5 ecm of sodium hydroxide solution 38 ⁰ Be, dissolved in about 11 boiling water and adjusted to 11.

Developing bath

8.3 g of l-amino ^ -methoxybenzene-S-carboxamide or 12.1 g of l-amino-l-methoxybenzene-S-carboxylic acid phenylamide or 14.5 g of l-amino-2-methoxybenzene-5-carboxylic acid - 3 '- Chlor - 2 '- methylphenylamide are diazotized in a known manner in the cold with 20.5 ecm hydrochloric acid 20 ° Be and 4 g sodium nitrite dissolved in water. After completion of the diazotisation is with 15 g of sodium acetate and dissolved in water g of a commercially available 20 ° / ₀ by weight condensation product of 1 mole of dodecyl alcohol and 30 moles of ethylene oxide at 11 a.

The blue-tinged red dyeings obtained have very good fastness properties to organic solvents.

Claims (2)

Patent claims: 1. A process for the preparation of water-insoluble monoazo dyes, characterized in that that the diazonium compounds of amines of the general formula -NH. R — NH-CO ' 35 Cotton yarn is treated at a liquor ratio of 1:20 for 45 minutes at 35 ° C. in the primer bath described below, squeezed off, dried and dyed in the developing bath mentioned below at 20 ° C. It is then squeezed off and, after 1 minute of air passage, treated for 5 seconds with water at 70 to 80 ° C. and for 5 seconds in a bath containing 3 ecm of hydrochloric acid 2O ⁰ Be per liter. The dyeings obtained in this way are soaped and rinsed in the usual way. R-NH-CO in which the group R - NH - CO - is in the m- or p-position to the amino group, R a Hydrogen atom, an alkyl or aryl radical, and the benzene nucleus A by alkyl, Alkoxy groups or halogen atoms may be substituted with 4- (2 ', 3'-oxynaphthoylamino) benzimidazolones, which can be substituted in the benzene nucleus of the benzimidazolone radical by alkyl groups or halogen atoms, in substance on the Fiber or on another substrate to form water-insoluble monoazo dyes the general formula HN HO CO -NH NH in which the group R - NH - CO - is in the m- or p-position to the azo group, R is a hydrogen atom, denotes an alkyl or aryl radical, the benzene nucleus A by alkyl, alkoxy groups or Halogen atoms and the benzene nucleus B can be substituted by alkyl groups or halogen atoms, clutch. 2. The method according to claim 1, characterized in that the coupling is in neutral to weakly acidic medium. Considered publications:
German interpretative document No. 1 041 463. When the registration was announced, two staining tables with explanations were laid out. 609 568/494 5.66 © Bundesdruckerei Berlin