DE1285078B - Process for the preparation of dyes of the anthraquinone series which are free from water-solubilizing groups - Google Patents

Description

German patent specification 1,133,055 relates to a method of manufacture of cyan derivatives, in which alkali metal cyanides are added to anthraquinone acridones in inert solvents, Anthrapyridones and ring systems with higher condensation on non-anthraquinone-like quinones and the addition compounds thus obtained by treatment with oxidizing agents converted into the cyan derivatives.

It has now been found that the addition of alkali metal cyanides to derivatives of anthraquinone with fused ring systems can also be carried out, but that 1-aminoanthraquinones substituted in the 2-position are also suitable as starting products for this reaction. The invention relates to a process for the preparation of dyes of the anthraquinone series which are free from water-solubilizing groups, in which a water-insoluble 1-aminoanthraquinone derivative of the general formula is used wherein R and R 'denote hydrogen atoms, alkyl or aryl radicals and X represents an organic radical which via the to an aldehyde, keto, acid amide or belonging carbon atom, which in the latter case can also be part of a heterocyclic ring, is bonded to the anthraquinone nucleus, the latter being able to contain further simple substituents, condensed with an alkali metal cyanide at elevated temperature in an inert organic solvent, the addition compound obtained in this way by oxidation in a cyano compound is converted and the cyano group is optionally saponified in a known manner to give a carbonamide group.

The dyes which can be prepared according to the invention are distinguished from one another the anthraquinone derivatives used as starting materials by their significant higher color strength. Depending on the type of substituents, they represent vat dyes, Disperse dyes or pigment dyes and can also be used as intermediates can be used to build up other dyes.

The condensation of the 2-substituted a-aminoanthraquinones with the Alkali cyanide is in an inert organic solvent, such as in particular dimethylformamide, Dimethyl sulfoxide, N-methylpyrrolidone, performed. As a reaction medium are still for example polyhydric alcohols and amino alcohols are suitable. The preferred temperature range for the condensation is between 60 and 200 ° C, especially at temperatures over 100'-C. The addition compounds obtained in the condensation are leuco-alkali salts that by treatment with a conventional oxidizing agent, such as Bichromate-acetic acid or chlorine lye or by air oxidation in the. appropriate Cyan derivatives. can be transferred.

As starting products for the claimed process are also suitable the 1-aminoanthraquinones correspondingly substituted in the 2-position also the derivatives of 1,4-diaminoanthraquinones, of 1-dialkylaminoanthraquinones, such as in particular Methyl and ethyl derivatives, the 1-arylaminoanthraquinones, such as in particular the 1-phenylamino-anthraquinone, the 1-tolylamino-anthraquinones and 1,4-ditolylamino-anthraquinones.

Suitable substituents for the 2-position of the amino-anthraquinone are the aldehyde group, the methyl or phenylcarbonyl radical and, for. B. residues of the following constitution -CH = N-aryl -CH = NN = CH - CO-NHZ or -CO-NH-NH-- CO - NH - aryl - CH = NOH -CH = NH-NHZ -CH = N-NH-aryl Vat dyes of the anthraquinone series common substituents, such as, in particular, halogen atoms, e.g. B. chlorine or bromine, alkoxy groups such as methoxy, ethoxy groups, amino groups, hydroxyl groups or nitro groups, but no water-solubilizing groups such as carboxyl or sulfonic acid groups.

The anthraquinone derivatives obtained after the introduction of the cyano group can be converted in the usual way by converting the cyano group into a carbonamide group, for example with concentrated sulfuric acid, saponify.

Example 1 28 g of 1,4-diamino-2-acetyl-anthraquinone are in 280 ccm Dissolved dimethylformamide at 120 ° C and with a solution of 10g Na2Nmcyanid in 15 ccm of water added. Subsequently, the mixture obtained is so long. at 120 ° C stirred until the vat color of the starting product changed from green to brilliant red is. For working up, the reaction mixture is then poured into 1 l of water and blown out with air. The dyestuff separated out is sucked off, thoroughly washed with water and dried. You get one that intense blue anthraquinone dye; for example textile materials based on Polyethylene glycol terephthalate in brilliant colors using the so-called thermosol process Shades of blue.

By treatment with warm 90 ° ("iger sulfuric acid the in the Anthraquinone dye introduced cyano group in a known manner to a carbonamide group to be saponified. The dye obtained in this way is suitable as a vat dye and supplies blue dyeings on cotton.

Example 2 32.6 g of 1-amino-anthraquinone-2-aldehyde-anil are briefly heated to the boil in 330 cc of ethylene glycol together with 15 g of potassium cyanide. After the reaction mixture has been poured into water and blown out with air, the precipitated dye is filtered off with suction, washed and dried. The cyan derivative obtained can be recrystallized from o-dichlorobenzene. The dye produces orange-brown tones on polyester fibers.

Example 3 34.2 g of 1,4-diamino-2-benzoyl-anthraquinone are dissolved in 350 cc of dimethyl sulfoxide and 15 g of sodium cyanide in 25 cc of water are added. The reaction mixture is kept at a temperature of 150 ° C. for 25 minutes and then worked up as in Example 1.

The blue dye obtained is suitable as a pigment for Coloring of plastic bodies. According to the information in Example 1, the introduced cyano group can be converted into a carbonamide group, with also a blue dye suitable for coloring plastics is obtained.

Is used as the starting product in place of 1,4-diamino-2-benzoyl-anthrachirons 37.6 g of 1,4 - diamino - 2 - (p - clilorbenzoyl) - anthraquinone or 39.2 g of des 1,4-diamino-2-naphthoyl-anthraquinones, this also gives blue pigments, which differ from the anthraquinone derivatives used as starting materials distinguish their significantly better migration fastness.

Example 4 35.5g of an anthraquinone derivative of the formula are dissolved in 350 cc of dimethylformamide and reacted with 10 g of sodium cyanide as described in Example 1. After working up and isolation, a blue dye is obtained which is particularly suitable as a pigment dye for spin dyeing viscose rayon. Example s 54.2g of an anthraquinone derivative of the formula are, after fine grinding, suspended in 540 cc of N-methylpyrrolidone, 10 g of sodium cyanide dissolved in 25 cc of water are added and the mixture is stirred at 150.degree. C. for 1 hour. The reaction product is then precipitated by adding 550 ccm of water and blowing in air, filtered off with suction and washed thoroughly. After drying, a blue dye powder is obtained.

The dye powder thus obtained is stirred at 45 ° C. for a long time in 90% sulfuric acid, an anthraquinone dye is obtained in which the initially introduced cyano group is converted into a carbonamide group. The isolation the dyestuff containing carboxamido groups is carried out by pouring in the sulfuric acid Dissolve in water, suction off the deposited precipitate, wash and dry.

The dye thus obtained is suitable after grinding with a dispersant as a vat dye for dyeing and printing cotton. The dye delivers here blue colorations or prints, which are characterized by a rich nuance and very good Distinguish authenticity properties.

A dye of a similar shade can be obtained if one takes the place of the oxdiazole derivative used as starting material above from the corresponding one N, N'-di- (1,4-diamino-anthraquinone-2-carboxylic acid) hydrazide starts out.

The dyes obtained in this way are also suitable as pigment dyes for coloring plastic materials, such as synthetic resins, and for pigmentation of paints.

Example 6 46 g of 1,4-di- (p-tolylamino) -2-acetyl-anthraquinone are as indicated in Example 1, reacted with 10 g of sodium cyanide. After oxidation of the Addition product by blowing out with air gives a green anthraquinone dye, which dyes textile materials based on polyamides in green shades.

Beispie17 24.9g of an anthraquinone derivative of the formula Weiden suspended in 250 cc of dimethylformamide and mixed with a solution of 10 g of sodium yanide in 15 cc of water. The mixture is then heated to boiling under reflux until an intensely blue suspension has formed. The reaction product is, as indicated in Example 1, isolated. A brown dye is obtained in this way, which dyes cotton with a brown shade from a yellow-brown vat. The dye obtained is also suitable as an intermediate for the production of other anthraquinone dyes.

Claims (1)

Claim: Process for the preparation of dyes of the anthraquinone series which are free of groups which make water soluble, characterized in that a water-insoluble 1-aminoanthraquinone derivative of the general wherein R and R 'denote hydrogen atoms, alkyl or aryl radicals and X represents an organic radical which via the to an aldehyde, keto, acid amide or. belonging carbon atom, which in the latter case can also be part of a heterocyclic ring, is bonded to the antbrachinone nucleus, the latter being able to contain further simple substituents, condensed with an alkali metal cyanide at elevated temperature in an inert organic solvent, the addition compound obtained in this way by oxidation in a cyano compound is converted and the cyano group is optionally saponified in a known manner to give a carbonamide group.