DE1267361B - Process for the preparation of anthraquinone derivatives - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

C09b

German KL: 22 b-3/17

Number: 1 267 361

File number: P 12 67 361.9-43

Filing date: May 16, 1964

Open date: May 2, 1968

The invention relates to a process for the preparation of l, 5-diamino-4,8-dihydroxy-anthraquinones, which in at least one / ^ - position an optionally substituted aryl radical and in at least another // position contain the remainder of a thiol or thioether group.

Preferred compounds of this type are those of the general formula

Process for the preparation of anthraquinone derivatives

HO O NH-R ₁

(D

OH

where Ri, Rs and Ri are independently of one another Hydrogen atom or optionally substituted hydrocarbon radicals and R2 one optionally substituted aryl radical.

Compounds of the formula I are particularly suitable as disperse dyes if one of the radicals Ri or R -. \ Is a hydrogen atom and the other is a hydrogen atom or an alkyl radical having 1 to 4 carbon atoms, R> is a phenyl or naphthyl radical substituted by an optionally etherified hydroxyl group and Ri denotes an alkyl radical having 1 to 4 carbon atoms or an aryl radical, both the anthraquinone nucleus and the substituents mentioned being able to be substituted as desired by non-water-solubilizing substituents. Substituents which do not make water-solubility are understood as meaning all of the atoms and groups of atoms customary in disperse dyes. If the hydroxyl group of the aryl radical R2 is etherified, it is preferably an alkoxyphenyl radical or alkoxynaphthyl radical, which can be substituted in the manner indicated.

French Patent 1,317,459 and U.S. Patent 2,672,464 are structural similar dyes are described. However, these known dyes have compared to those according to the invention dyes produced on polyester material have a lower thermal resistance.

The new anthraquinone derivatives are made by adding a //-Aryl-l.S-diamimM.S-dihydroxy-anthraquinone-p'-sulfonic acid with carbonization hydrogen or one of its derivatives and, if necessary, then the one thiol group containing compounds is converted into thioethers in a manner known per se.

20 applicants:

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, 6000 Frankfurt, Große Eschenheimer Str. 39

Named as inventor:

Dr. Paul Bücheier, Reinach (Switzerland)

Claimed priority:

Switzerland of May 22, 1963 (6405)

In order to obtain the preferred compounds of the formula I, a sulfonic acid of the formula is used

HO O NH

HO ₃ S

_R:, - HN O OH

35 a.

Particularly preferred starting materials are acids of the formula

40

45

R ₁ -HN

OH

which are allowed to react with hydrogen sulfide or one of its derivatives.

With sodium sulfide as a derivative of hydrogen sulfide one obtains dyes with a thiol group in position, which can be found in a manner known per se, z. B. with the help of alkyl or aryl compounds, with reactive halogen atom with the help of

809 574 Vl

Alkyl esters, ζ. B. dimethyl sulfate, or with the help of compounds with a reactive double bond, z. B. with derivatives of acrylic acid or methacrylic acid to convert to thioethers.

The reaction with sodium sulfide is particularly useful in an aqueous solution at boiling point stirred.

Mercaptans can also be used as derivatives of hydrogen sulfide. These too Implementation is most convenient at elevated temperatures, e.g. B. at 90 to 105 C, in aqueous Solution and with the addition of basic compounds, such as. B. Sodium Hydroxide, Potassium Hydroxide, Sodium carbonate, potassium carbonate or trisodium phosphate, stirred.

You can, however, the reaction participants in an inert organic solvent, z. B. in chlorobenzene, di- or trichlorobenzenes or nitrobenzene, react. In this case it is favorable at temperatures above 100 ° C. and up to approximately 180 ° C. and in particular at 130 to 150 C to work. The addition of sodium or potassium acetate is also beneficial.

Mercaptans particularly suitable for the implementation are, for. B. methyl mercaptan, ethyl mercaptan. 2-hydroxyethyl mercaptan, thiophenol, thiocresol. Thioglycolic acid methyl ester or thioglycolic acid ethyl ester.

The anthraquinone derivatives obtained in this way can, if they are free of water-solubilizing groups are obtained by filtering the aqueous reaction mixture. Often you will in the Neutralize all or part of the alkali contained in the reaction mixture before filtering. If the Reaction is carried out in an organic solvent, this can be done particularly easily remove by distillation with steam. Then the anthraquinone derivative lets through Gain filtration of the aqueous phase.

The new compounds are blue and dissolve in common organic solvents with a blue color. When free of sulfonic acid and carboxyl groups, they are excellent disperse dyes for hydrophobic high molecular weight organic substances, e.g. B. for linear, aromatic polyesters such as polyethylene glycol terephthalate, cellulose esters, such as. B. Cellulose ^ ¹ '»acetate and cellulose tri-acetate. and synthetic polyamides, e.g. B. Poly-f-caprolactam. Poly-ci-aminoundecanoic acid and polycondensates of dicarboxylic acids and diamines, e.g. B. from adipic acid and hexamethylenediamine. Before using the new dyes in this way, they are processed in the usual way with the addition of dispersants, such as. B. dinaphthylmethandisulfonsaurem sodium, lignosulfonates, thickeners or other common auxiliaries for coloring preparations. These preparations can be used to make dye baths, padding baths or printing pastes. The hydrophobic substances mentioned are dyed in blue tones with excellent fastness properties. Particular mention should be made of the good wet fastness properties, e.g. B. water, sea water and wash fastness, also perspiration. Dry cleaning, dyeing, heat setting, pleating, sublimation and lightfastness.

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

23.5 parts of 1,5-diamino-3 - (4'-methoxyphenyl) -4,8-dihydroxy-anthraquinone-7-sulfonic acid Sodium, 15 parts of potassium acetate, 15 parts of sodium carbonate, 195 parts of 1,2-dichlorobenzene and 15 parts of 2-mercaptoethanol are stirred at 140 for 3 hours. Then the 1,2-dichlorobenzene is distilled off with steam and the remaining suspension is brought to a pH of 7 with acetic acid. Of the Precipitate is filtered off, washed with water and dried. 19 parts of a powder are obtained, which dissolves in chlorobenzene with a blue color.

B e i s ρ i e I 2

23.5 parts 1,5-diamino-3 - (4'-methoxyphenyl) -4,8-dihydroxy-anthraquinone-7-sulfonic acid Sodium, 25 parts of 2-mercaptoethanol, 60 parts of 30% sodium hydroxide solution and 250 parts of water are stirred at 95 to 100 for 24 hours. Then 7 (K) parts of water are added and the pH value is set to 9 with acetic acid. The resulting precipitate is filtered off, washed with water and dried. This gives 20 parts of the same dye as in Example I.

Example 3

45 parts of 1,5-diamino-3- (4'-ethoxyphenyl) -4.8-dihydroxy-anthraquinone-7-sulfonic acid, 4 (K) parts Water. 13 parts of 30% sodium hydroxide solution and 50 parts of 60% sodium sulfide are used during Heated to boiling under reflux for 24 hours. The reaction mass is poured into 1000 parts of water, heated to 80 and added at this temperature with about 50 parts of sodium bicarbonate, so that their pH is 10.5. The solution is mixed with 150 parts of sodium chloride and stirred, until their temperature is 40. The resulting precipitate is suctioned off and washed with it 2000 parts of 10% sodium chloride solution. The precipitate is stirred in 1000 parts of water. The pH of this suspension is 9.3. He is 40 ° oiger. aqueous acetic acid adjusted to 3.2. The precipitate is filtered off with suction. washes it with water until the filtrate is colorless and neutral runs out and dries it. The dye thus obtained dissolves in chlorobenzene with a blue color. He solves in water with the addition of alkalis, e.g. B. ammonia solution, with a greenish blue color.

Example 4

22 parts of 1,5 - diamino - 3 - (4 '- hydroxyphenyl) -4.8-dihydroxy-anthraquinone-7-sulfonic acid Sodium. 30 parts of propyl mercaptan. 75 parts of 30 "sodium hydroxide solution and 300 parts of water are stirred under reflux at boiling temperature for 24 hours. 700 parts are added to the reaction mass Water and adjust the pH to 9 with acetic acid. The precipitate is filtered off and with Water washed. The dried dye dissolves in chlorobenzene with a blue color.

Example 5

23 parts 1.5 - diamino - 3 - (4 '- hydroxyphenyl) -4.8 - dihydroxy - anthraquinone - 7 - sulfonic acid and 23 parts of 1,5-diamino-3- (4'-methoxyphenyl) -4.8-dihydroxy - anthraquinone - 7 - sulfonic acid. 400 parts of water. 15 parts sodium hydroxide solution 30 "nig

and 60 parts of 60% sodium sulfide are heated to boiling under reflux for 24 hours. The reaction mass is stirred into 800 parts of 80 water. The pH is adjusted to 10.5 with sodium bicarbonate. 150 parts of sodium chloride are added to the solution and the mixture is allowed to cool to 40; The precipitate is filtered off with suction and washed with 100% aqueous sodium chloride solution until the filtrate no longer contains any sulfide ions. The precipitate is then mixed in 500 parts of 50 water. 1 part of pyridite is added to the solution and 24 parts of dimethyl sulfate are added dropwise over the course of 90 minutes, the pH of the reaction mass being kept at 10 with sodium hydroxide solution. The precipitate obtained is filtered off with suction and washed with water until the filtrate runs off neutral. The precipitate is stirred in 1500 parts of water. The suspension is heated to 80 and acidified at this temperature with 20 parts of 30% hydrochloric acid. The precipitate is filtered off with suction, washed neutral with water and dried. The dye dissolves in chlorobenz oil with a blue color.

Dyeing prescription

6 parts of the dye obtained according to Example 1 or 2. 14 parts of sodium dinaphthylmethanedisulphonic acid and 180 parts of water are ground to a fine dispersion. 20 parts of this dispersion are placed in a dyebath consisting of 3 (XX) parts of water and 10 parts of 2-hydroxy-II-di phenyl. 100 parts of polyester fibers are introduced into this dyebath at 60. The dyebath is heated to boiling temperature within 20 minutes and held at 100 for 60 minutes. It is then rinsed with water and dried. The polyester fibers are colored in a beautiful blue tone. The dyeing is very fast to wet, light and heat-setting.

Instead of the polyester fibers, any type of textile product made therefrom can be dyed will.

If a dye from Examples 3, 4 or 5 is used instead of the dye from Examples 1 or 2, then is obtained on fibers. Threads or textiles made from them made from linear, aromatic polyesters. Dyes with the same good properties.

Claims (1)

Claim: Process for the production of anthraquinone derivatives, characterized in that, that one / <- aryl-l, 5-diamino-4,8-dihydroxyanthraquinone - // - sulfonic acid is reacted with hydrogen sulfide or one of its derivatives and optionally then the compounds having a thiol group in per se known way converts to thioether. Considered publications: French Patent No. 1 317 459: U.S. Patent No. 2,672,464. When the application was announced, a coloring table provided with explanations was displayed.