DE1201933B - Process for the preparation of 1,8-dihydroxy-anthraquinonyl-5-thioethers - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. α .:

Number:
File number:
Registration date:
Display day:

C09b

German class: 22 b-3/17

1201933
F38493IVc / 22b
7th December 1962
September 30, 1965

Belgian patent 609 673 describes the preparation of aryl mercapto-anthraquinones by reacting anthraquinones, which _{contain exchangeable groups such as NO 2} , halogen, SO ₃ H, in the α-position with thiophenols in the presence of alkali metal hydroxide in alcohols at elevated temperature will. In a special case, 4,8-dinitro-1,5-dihydroxy-anthraquinone is obtained by replacing both nitro groups with 4,8-diphenylmercapto-1,5-dihydroxy-anthraquinone.

It has now been found that 1,8-dihydroxyanthraquinonyl-5-thioether obtained in a simple manner if one, 8-dihydroxy-4,5-dinitro-anthraquinone in the presence of amines with aromatic mercaptans and the nitro groups of the reaction products are optionally reduced to amino groups.

Examples of aromatic mercaptans are thiophenol and its substitution products, e.g. B. the by halogen, such as chlorine or bromine, or by alkyl, such as methyl or ethyl groups, or alkoxy, such as methoxy groups, or nitro or carbon ester groups substituted thiophenols.

The inventive method is preferably carried out at room temperature or slightly lower temperatures, e.g. B. in the temperature range from -20 to +20 ⁰ C carried out. It is preferred to work in inert solvents, e.g. B. alcohols or acid amides, such as glycol, dimethylformamide or N-methylpyrrolidone.

Examples of the amines used according to the invention are ethanolamine, diethylamine, triethylamine, tributylamine, Triethanolamine or dimethylaniline. The amines are expediently in equimolar Quantities or in excess are added in order to ensure that the reaction proceeds as smoothly as possible.

The 1,8-dihydroxy-5-aryl mercaptoanthraquinones obtained can be converted by known methods the corresponding amines are reduced. The new compounds are suitable as dye intermediates as well as for dyeing synthetic fibers, such as polyamide, polyester, cellulose acetate and polyacrylonitrile fibers. On polyester they deliver strong violet shades of good sublimation and color Lightfastness. The 1,8-Dioxy-4-nitro-5-arylmercaptoanthraquinones pull on polyester material with sublimation rights red tones.

From the Belgian patent specification 600 960 are already Anthraquinone dyes have become known which contain phenyl mercapto groups. According to the invention obtained dyes differ from the closest dyes of this patent by Process for the preparation of 1,8-dihydroxyanthraquinonyl-5-thioethers

Applicant:

Paint factories Bayer Aktiengesellschaft,

Leverkusen

Named as inventor:
Dr. Hans-Samuel Bien, Burscheid;
Dr. Klaus Wunderlich, Leverkusen;
Dr. Fritz Baumann, Opladen

better fastness to sublimation and also through a different shade.

The parts and percentages given in the examples are weight units.

example 1

OH O

OH

17 g of triethylamine are added to a suspension of 19.8 g of 1,8-dihydroxy-4,5-dinitro-anthraquinone in 100 ecm of glycol and 20 g of thiophenol are added dropwise at room temperature. The blue reaction mixture was, after all works Dinitroazin has disappeared, in 750 cc of 1% strength sodium carbonate solution and ^it is washed with the same solution until the washings are colorless. The filter material is suspended in 600 ecm water and mixed with 60 ecm sodium sulfhydrate solution. V is kept _{at 90 to 95 ° C. for 2} hours, the crystalline reaction product is filtered off with suction at 90 ° C. and washed with hot water until it is colorless. The residue is boiled with dilute acid, filtered off with suction and washed neutral.

Das!, S-Dihydroxy ^ -amino-S-thiophenyl-anthraquinone pulls on polyester material in strong purple tones. Chlorobenzene or toluene turn purple Needles received.

509 689/332

3 4

10 parts of strand material made from cellulose triacetate are used. The product can be recrystallized in glacial acetic acid in a liquor containing 400 parts of water, 0.2 parts of the product.
of a mixture of o-, m-, p-cresotinic acid methyl- A similar result is obtained in 2-methyl ester and containing 0.6 parts of an emulsifier, according to 5 dihydro-2,3-indole7 "V ' ^r ■; _"'
Adjustment of the pH with formic acid to 4.5 1 hour .- - '.>"= · \ ■■ _R. - ^. ,, - ^ s \
colored at 96 to 98 ^{° C.} A violet dyeing example D is obtained

To a mixture of 14.8 parts of 1,8-dioxy

Analysis: C ₂₀ H ₁₃ O ₄ NS 4,5-dinitro-anthraquinone and 4.4 parts of diethylamine

Calculates · "be ^{in 100s} il ^en N-methylpyrrolidone at 2O ⁰ C.

C 66.2, H 3.6, O 17.6, N 3.9, S 8.8%; J · ⁶ tales of thiophenol added. After diluting with

Methanol and suction is the same as in Example 3

Found: received the same product.

C 66.0, H 3.8, O 15.9, N 4.0, S 8.8%. ^ _{At Stdle yon D} i _äthy i _arain 3.8 parts can also be used

* 5 ethanolamine or 11.1 parts tributylamine used

Example 2 will be.

In a mixture of 100 ecm of glycol and 5.4 g of bis ρ ie 1 6
Triethylamine is added at room temperature 6.6 g. A mixture of 9.9 parts of 1,8-dihydroxyl, 8-dihydroxy-4,5-dinitro-anthraquinone. 50 parts of dimethylformamide are added at 20 4,5-dinitro-anthraquinone, room temperature in 2 hours, 3.5 g 4-chloro _an d 2.3 parts of triethanolamine are added at 20 to thiophenol to. After completion of the reaction is 25 ° C and 3.8 parts of 2-methylthiophenol and stirred until reaction mixture in 750 cc of 1 ° / _o sodium carbonate solution _to complete _the reaction (optionally chromatographic. The mixture is heated to 80 ° C and washed with 1% pursuit of Implementation). The reaction mixture of hot soda solution and then added _{to 750 parts of water with water up to 25 w} j _r d, acidified, to the colorless drain. The red 1,8-dihydroxy sucked and washed neutral. One obtains in quantitative 4 - nitro - 5 - [p - chlorophenylmercapto] - anthraquinone relative yield, the 5 (2-methylphenylmercapto) is dissolved in 20 ecm of pyridine and then in 80 ecm of 4-nitro-1,8-dihydroxy-anthraquinone . The substance poured out of water. One reduces with 20 ecm 20% iger keeps below 5% of the corresponding 4,5-dithioether. Natriumsulfhydratlösung at 95 ° C, V stops a ₂ hour 30 Polyester fibers, for example Polyäthylenglykolteredie temperature, filtered off with suction at 70 ⁰ C and washed with phthalatfasern arise bluish-red colorations of hot water. The filtered material was slurried in _V on good sublimation and lightfastness.
Water, acidifies, sucks off at 90 ^° C. and washes the filter residue of 5 (2-methylphenylmercapto) neutral with hot water. 4-nitro-1,8-dihydroxy-anthraquinone is made with 300 parts

10 parts of strand material made of polyethylene glycol ₃₅ water and mixed with 30 parts of 18% sodium

terephthalate are reduced in a liquor of 400 parts of sulfhydrate solution at 90 to 95.degree. Man sucks

Water, 0.1 part of the finely distributed hot water and washes with hot water until it is colored

Dye, 3.4 parts of a mixture of o-, m-, loose drain, Das5 (2-methylphenylmercapto) -4-amino-

p-cresotinic acid methyl ester and 0.6 parts of an emul 1,8-dihydroxy-anthraquinone is 90% strength

gators obtained after the addition of sulfuric acid up to the booty 40 and provides blue-

setting a pH of 4.5 2 hours at 96 to 98 ° C pale violet colorations with good heat setting and

colored. It is then rinsed and dried. Lightfastness.

A bluish violet coloration is obtained. Similar dyes are obtained if instead of

good thermosetting and lightfastness. _of 2-methylthiophenol, 3- or 4-methylthiophenols

An analogous dye is obtained with m-chlorine- ₄₅ . The implementation is also accessible

thiophenol. 4-tert-butylthiophenol.
Example 3

To a mixture of 19.8 parts of 1,8-dioxy

4,5-dinitro-anthraquinone, 100 parts Dimethylform- ₅₀ at -15 ° C is allowed to a mixture of amide and 4.6 parts of triethanolamine in drops at _{9j9 Te} ueen!, S-dihydroxy- ^ S-dinitro-anthraquinone in 20 ^° C. to 6.6 parts of thiophenol. After completion of 50 parts of trimethylpyridine 3.3 parts of thiophenol addition, the batch is added dropwise with 120 parts of methanol. After a reaction time of 20 hours, the mixture is diluted. _{The red crystals which crystallize in red cubes are filtered off with suction and washed} with methanol-1,8-dioxy-4-nitro-anthraquinone-5-thiophenyl ether. After reduction with sodium sulfhydrate, it is filtered off with suction. solution (according to example 1) is the example 1

10 parts of a rag made of polyethylene glycol-identical product.

terephthalate are made in a liquor with a pH of 4.5 The trimethylpyridine can also be replaced by 2-methyl-

400 parts of water and 0.1 part of finely divided dihydro- (2,3) -indole or replaced by isoquinoline

present dye for 2 hours at 120 to 130 ⁰ C 60,
colored. After rinsing and drying, one obtains

a sublimation and lightfast red coloration. Example 8

Example4 _T. > »· T. _n η - ^ ι ίο τ ^ ι j

^r In a mixture of 9.9 parts of 1,8-dihydroxy

To a suspension of 19.8 parts of 1,8-dioxy-65 4,5-dinitro-anthraquinone, 50 parts of glycol and 8.2 parts

4,5-dinitro-anthraquinone in 100 parts of Dimethylanilin len triethylamine is allowed at 20 ⁰ C 4.8 parts of m-chlorine

6.6 parts of thiophenol are added at room temperature. add dropwise thiophenol within an hour and

After the reaction has ended, the mixture is stirred in hydrochloric acid until the reaction is complete. Of the

The batch is poured into 375 parts of water, and 3.8 parts of soda are added. The mixture is heated to 80 ° C, filtered hot with suction and washing with l% r ^e tig sodium carbonate solution after. The filter residue is stirred in 100 parts of water, mixed with 40 parts Natriumsulf hydrate solution and reduced at 80 ⁰ C 5. V is _{allowed to stir for 2} hours, filtered off with suction and washed neutral with hot water. The dye obtained stains the polyester material in bluish violet shades.

Instead of m-chlorothiophenol, p-methoxythiophenol can also be used.

Claims (1)

Claim: Process for the preparation of 1,8-dihydroxyanthraquinonyl-5-thioethers, characterized in that 1,8-dihydroxy-4,5-dinitro-anthraquinones reacts in the presence of amines with aromatic mercaptans and optionally the nitro groups of the reaction products reduced to amino groups. Considered publications:
Belgian patent specification No. 600 960. When the application was announced, a coloring table with explanations was laid out. 509 689/332 9.65 © Bundesdruckerei Berlin