DE1203895B - Process for the production of anthraquinone dyes - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. CL:

Number:
File number:
Registration date:
Display day:

C09b

German class: 22 b -3/02

1 203 895
C19339IVc / 22b
3rd July 1959
October 28, 1965

It has been found that valuable new anthraquinone dyes can be obtained from L-oxy-4-arylaminoanthraquinones free of nitro groups the formula

OH

Process for the preparation of anthraquinone dyes

O NH-aryl

wherein aryl means an optionally substituted benzene residue, treated with formaldehyde in 75 to 9O ° / cent sulfuric acid at temperatures between 10 and 40 ⁰ C.

The starting materials for the present process are in particular those 1-oxy-4-arylaminoanthraquinones, which contain an optionally substituted benzene radical as the aryl radical. Possible substituents include, for example Methyl groups or, advantageously, acylamino groups are suitable, that is to say preferably dyes of the formula

OH

Applicant:

CIBA Aktiengesellschaft, Basel (Switzerland)

Representative:

Dr.-Ing. Dr. jur. F. Redies,
Dr. rer. nat. B. Redies, Dr. rer. nat. D. Turk
and Dipl.-Ing. Ch. Gille, patent attorneys,
Opladen, Rennbaumstr. 27

Named as inventor:

Dr. Paul Grossmann, Binningen (Switzerland)

Claimed priority:
Switzerland from July 4, 1958

II

O NH

NHCOR ₂

where R2 stands for a Η atom or an alkyl radical, containing at most 11 carbon atoms, for example a methyl, ethyl, propyl, octyl, undecyl or Isopropyl group.

When carrying out the process according to the invention, one generally already obtains with 1 mole of formaldehyde per mole of l.-oxy-4-arylaminoanthraquinone very good results. In certain cases, however, you can use an excess of formaldehyde, for example 10 mol and 1 mol of the anthraquinone compound, of advantage be. The formaldehyde can be used as a concentrated aqueous solution or in polymeric form, for example as Paraformaldehyde, can be added. Instead of formaldehyde, formaldehyde-releasing agents can also be used Use agents such as hexamethylenetetramine.

The reaction is _o acetic, preferably performed at 10 to 40 ⁰ C, preferably at 10 to 30 ⁰ C, in 75 to 90 ° / in 80 to 85% sulfuric acid.

The reaction time depends on the concentration of sulfuric acid and the temperature.

The work-up is advantageously carried out by cycling ¹ Pour the reaction mixture on a water-ice mixture, wherein the process product precipitates and can be separated by filtration. The dye is expediently washed with water until it is free from sulfuric acid.

For the time being, nothing definite can be said about the type of implementation, it is assumed that that oxymethyl groups are introduced into the molecule of the starting material. The dyes obtained are characterized by a significantly better drawability for fiber materials compared to the starting materials from cellulose esters, for example cellulose acetate or cellulose triacetate, or by better ones Sublimation fastness on polyethylene terephthalate fibers. Valuable red-blue ones appear on these fibers to green-blue colorations obtained.

In many cases, mixtures of dyes obtained according to the process produce stronger colors than obtained with the individual dyes, especially with mixtures of dyes that are differ by the substituent in the benzene residue.

509 719/314

Compared to the 1-oxy-4- (m-oxymethylphenyl) -aminoanthraquinone obtainable according to Example 3 of US Pat. No. 2,353,108 the dyes obtainable according to the invention show the advantage of dyeing on acetate silk with better exhaust gas fastness to surrender.

In the following examples, unless otherwise stated, the parts mean parts by weight, the percentages by weight and the temperatures are given in degrees Celsius.

example 1

6 parts of paraformaldehyde are introduced into 85 parts of 85% strength sulfuric acid at 20 ³ . When the solution is complete, 9 parts of 1-oxy-4-phenylamino- '5 anthraquinone are added and the mixture is stirred for about 4 hours at 20 to 25 °. Then it is poured onto ice, filtered, washed neutral and ground with a suitable dispersant.

In contrast to the starting material, the dye colors polyethylene glycol terephthalate in sublimation properties red-blue tones.

Example 2

The procedure of Example 1 is followed, but 9 parts of l-oxy-4- (p-acetylamino) phenylaminoanthraquinone are used. The dye dyes acetate silk in blue-violet and dacron in red-blue tones.

Used instead of l-oxy-4- (p-acetylamino) phenylaminoanthraquinone the l-oxy-4- (p-formylamino) phenylaminoanthraquinone is obtained Strong blue-violet colorations on acetate silk as well.

Example 3

The procedure of Example 1 is followed, but 9 parts of 1 - oxy - 4 - (ρ - butyrylamino) phenylaminoanthraquinone are used. The dye dyes acetate silk and polyethylene glycol terephthalate in reddish blue Tones.

Similar shades are obtained with 1 - Oxy-4- (p-acrylylamino) - and I-oxy-4- (p-propionylamino) -phenylaminoanthraquinone, while with the caprylyl and lauryl derivatives, slightly less reddish tones are obtained.

Example 4 Example 5

In 17 parts of 85% sulfuric acid and 34 parts of 100% sulfuric acid, 10 parts are added below 20 ° a 40% aqueous formaldehyde solution and then carries 6 parts of l-oxy ^ -phenylaminoanthraquinone a. The mixture is stirred for 4 hours at 20 to 25 °, and the dye is separated off and dispersed, as in Example 4 described. A considerable increase in the drawability is obtained compared with the starting product on acetate silk.

Claims (6)

Patent claims: 1. Process for the production of anthraquinone dyes, characterized in that 1-oxy-4-aryIaminoanthraquinones free of nitro groups the formula 40 1.2 parts of paraformaldehyde are divided into 76 parts 80 ° / () strength sulfuric acid entered at 10 to 15 °, whereupon 6 parts of l-oxy-4-phenylaminoanthraquinone added and stirred for 15 hours at 10 to 15 °. It is discharged onto ice, filtered and washed neutral and ground with a suitable dispersant. The dye dyes acetate silk in contrast to Starting material in strong purple tones with very good exhaust gas and lightfastness. If, instead of l-oxy-4-phenylaminoanthraquinone, l-oxy-4- (m-methyl) - or l-oxy-4- (o, p-dimethyl) -phenylaminoanthraquinone is used, a strong increase in the drawability f is also obtained , ₀ and purple dyeings on acetate silk. O OH O NH-aryl wherein aryl means an optionally substituted benzene radical, with formaldehyde in 75 to 90% sulfuric acid at temperatures between 10 and 40 ⁰ C treated. 2. The method according to claim 1, characterized in that one of l-oxy-4- (4'-acylamino) phenylaminoanthraquinones goes out. 3. The method according to claim 2, characterized in that one of compounds of formula OH O NH NHCOR ₂ starts out, where R2 is a Η atom or at most Means an alkyl radical containing 11 carbon atoms. 4. The method according to claim 1, characterized in that one of l-oxy-4-phenylaminoanthraquinone goes out. 5. Process according to Claims 1 to 4, characterized in that 80 to 85% strengths are used Sulfuric acid is used. 6. Process = according to Claims 1 to 5, characterized in that temperatures between 10 and 30 ⁰ C are used. Considered publications:
Belgian Patent No. 552 173;
U.S. Patent No. 2,353,108. When the application was announced, a coloring table provided with explanations was displayed. 505 7 W3U 10.65 Q Bundesdruckerei Berlin