CH508013A - Greenish/blue-violet anthraquinone dyes for wool, polyamides - etc - Google Patents

Abstract

Greenish/blue-violet anthraquinone dyes for dyeing/printing wool, silk, hair, synth. polyamides and polyurethanes and leather shades fast to wetting, rubbing, dry-cleaning and light, have the formula: (where Y is sulphonated arylthio, arylalkylthio or arylalkoxy; the ring B may carry an F, Cl or Br atom or sulphonic acid gp. in one of the beta-posns., or Cl atoms in both beta-pos.). Cpds. are prepd. by reacting 1 mol. of a cpd. of formula: (where Z is Br or sulphonic acid gp.) with 1 mol. of a cpd. of formula Y1-H (where Y1 is arylthio, arylalkylthio or arylalkoxy) and sulphonating the reaction product.

Description

  

  
 



  Process for the preparation of anthraquinone compounds
The subject of the main patent No. 489 565 is a process for the preparation of anthraquinone compounds of the formula
EMI1.1
 wherein R is a sulfonated aryl radical and the
Ring B can carry a fluorine, chlorine or bromine atom or a sulfonic acid group in one of the / S positions, or chlorine atoms in both positions.



   This process is characterized in that one mole of a compound of the formula
EMI1.2
 in which Z is a bromine atom or a sulfonic acid group, is reacted with 1 mol of a compound of the formula R1 C) H in which R1 is an aryl radical, and sulfonated.



   It has now been found that valuable anthraquinonl compounds of the formula
EMI1.3
 wherein Y is a sulfonated, arylthio, arylalkylthio or arylalkoxy group, obtained when 1 mol of an anthraquinone compound of the formula (II) with 1 mol of a compound of the formula Y1-H, wherein Y1 is an arylthio, arylalkylthio, or arylalkoxy group stands, and the reaction product is sulfonated.



   Of the compounds of the formula Y1-H, for. B. the following are mentioned:
EMI2.1
 wherein R2 is a hydrogen or halogen atom or a
1 to 9 carbon atoms containing alkyl or
Alkoxy radical, and m is 1 or 2.



   The reaction of the compounds of formula (II) with the compounds of formula Y1-H is expediently carried out at an elevated temperature, e.g. B. at 50 "to 200 ° C., preferably at 50 to 150 ° C. and especially at 609 to 120 ° C. in the presence of acid-hindering agents such as alkali metal carbonates and whydroxi, de. It is advantageous to work in an inert solvent, e.g.

  B. in an alcohol such as ethanol, IBIutanol, cyclohexanol or in an ether alcohol such as 2-methoxy-, 2-ethoxy- or 2-butoxyethanol, 2- (2'-methoxy-. 2- (2'-ethoxy- or 2 - (2'Butoxyethoxy) -ethanol, or in an ether such as dioxane, or in a hydrocarbon such as cyclohexane, toluene, chlorobenzene or, if the compounds of formula (II) carry a sulfonic acid group, even in water an excess of the thiol compounds can also be used as the solvent. Suitable solvents for the reaction with the hydroxy compounds are, for example

  Pyridine, a pyridine base mixture, quinoline, nitrobenzene, 2,6a-di-tert.butyl-4; mlethylphenol or an excess of the hydroxy compounds themselves.



  Any water present or formed is removed before or during the reaction. For the reaction of the 2-position bromine atom, the addition of a copper catalyst, e.g. B. copper-I chloride, be advantageous. The reaction products are in a known manner, for. B. by diluting with a lower alcohol or, if water-soluble or alkali-soluble compounds are used, also with water or with alkali metal hydroxide solutions, deposited, filtered off with suction, washed and dried.



   The sulfonation can be carried out with SO3 (as a gas, e.g. diluted with air or as an addition compound with pyridine or with dioxane) or with chlorosulfonic acid in an inert solvent such as chloroform, 1,2z-dichloroethane, nitrobenzene at temperatures from 0 to 50 ° C., preferably at 15-30 0C. Usually, however, one works with concentrated, about 96 to 100 above sulfuric acid or with oleum with up to about 15% SOs content at the temperatures given above. The benzene nuclei of the radical Y1 are sulfonated in the process. For the sulfonation at 10 to 20 C, it is appropriate to use oleum with z. B. 5 to 10% 603 content to be used. The sulfonated dyes can e.g.

  B. by pouring in water or in a salt solution and optionally salting out, isolated.



   The compounds of formula (II) used as starting compounds can, for. B. by reacting 1 mole of 3,5,5-trimethylcyclohexylamine with 1 mole of a compound of the formula
EMI2.2
 where X is a halogen atom and Z and B have the meanings given above.



   Suitable compounds of the formula (IV) are, for. B.



  1-amino-2,4-dibromo-anthraquinone, 1-amino-4; bromo-, 1-amino-4,6- or 4,7-dibromo, 1-amino-4-bromo-4-chloro- or -7-chloro, 1-amino-4 bromine -6- or -7-fluoro-, I-amino-4-bromo-6,7-dichloroanthraquinone-2-sulfonic acid, 1-amino-4-bromoanthraquinone, 2,6- or -2,7-disulfonic acid.



   The reaction of 3,5,5-trimethylcyclohexylamine with the compounds of the formula (IV) can be carried out at temperatures from 40 to 220.degree.



  The water-soluble anthraquinone compounds are advantageously in aqueous or aqueous-organic Me oleum, z. B. at temperatures of 450 to 100 ° C., preferably 450 to 85 ° C. for the compounds of the formula. (IV), in which Z is SOsH, the water-insoluble ones in an organic medium, e.g. B. at temperatures of 80 to 200 ° C., preferably at temperatures of 100 to 150 ° C., in particular at 110-130 ° C., for the compounds of the formula (IV) in which Z is a bromine atom, reacted.

  The aqueous-organic media used are mixtures of water and one or more at least partially water-soluble solvents which are indifferent to the reactants, e.g. B. lower alcohols (methanol, ethanol, isopropanol, butanol, ethylene glycol), ethers (dioxane, 1,2-dimethoxy or 1,2-diethoxyethane), ether alcohols (2-methoxy- or 2-ethoxyethanol, 2 (2 ') -Methoxyethoxy) or 2- (2'-ethoxyethoxy) -ethanol), ketones (methyl ethyl ketone), amides (dimethylformamide, dimethylacetamide), sulfoxides and sulfones (dimethyl sulfoxide, sulfolane-tetramethylene sulfone 3. The amount of these solvents is advantageously up to 25%, preferably 5 to 15%, of the mixture.

 

   It is expedient to work in the presence of acid-binding agents which have a pH value of at least 11 (pH value of the saturated aqueous solution of 3,5,5-trimethylcyclohexylamine), preferably alkali metal hydroxides (sodium or potassium hydroxide) and from a copper catalyst (copper powder, copper (I) oxide, copper (I) chloride, copper (II) oxide). In order to achieve a faster reaction, it is advantageous to use an excess of 3,5,5-trilmethylcyclohexylamine, for. B. 1.3 to 3 mol, preferably 1.5 to 2 mol, to use per mole of the haloanthraquinone compound.



   For the reaction in an organic medium, the 3,5,5-trimethylcydohexylamine itself is used as a solvent and optionally as an acid-binding agent or a high-boiling agent which is indifferent to 3,5,5-trimethylcyclohexylamine, e.g. B. at temperatures of 130 to 220 C boiling solvent, z. B. mono- and dichlorobenzene, dimethylformamide, dimethyl acetamide, dimethyl sulfoxide, glycol ethers and especially nitrobenzene; as acid-binding agents come z.

  B. consider an excess of the amine, a tertiary low volatility in which is more basic than 3,5,5-trimethylcyclohexylamine, a basic metal salt, e.g. B. sodium or potassium carbonate or an alkali metal hydroxide. If necessary, the copper catalysts mentioned above are used. The reaction products can in the usual way, for. B. by steaming, preferably under reduced pressure, steam distillation or dilution with a suitable agent (e.g.

  B. with water in the case of water-soluble solvents, with a lower alcohol such as methanol, ethanol, isopropanol or with a hydrocarbon such as petroleum ether, ligroin) separated, filtered off with suction, optionally washed and dried.



   The water-soluble dyes of the formula (with) containing at least one -SO3H group are used for dyeing, padding or printing wool, silk, hair, synthetic polyamide and polynrethane fibers and leather. The dyeings and prints obtained have good to very good wet fastness properties (wash, milled, sweat, water, sea water fastness) and good rub and dry cleaning fastness. The lightfastness is very good on synthetic polyamide fibers and better than on wool.



   In the following examples, the parts are parts by weight and the percentages are percentages by weight; the temperatures are given in degrees Celsius.



   example 1
A mixture of 23.2 parts of sodium 1-amino4- (3 ', 5', 5'-trimethylcyclohexylamino) anthraquinone-2-sulfonate, 13.5 parts of 300% sodium hydroxide solution, 100 parts of water and 22 parts of 4-methyl -1-mercaptobenzene is refluxed to 95-100 for 24 hours. 120 parts of ethanol are then added, the mixture is allowed to cool, the precipitated reaction product is filtered off, washed with ethanol and then with water and dried. 10 parts of the dyestuff base obtained in this way are dissolved in 50 parts of 100% sulfuric acid at 15 20C.

  15 parts of 25% oleum are then added dropwise and the whole is stirred until a sample is completely soluble in water, poured onto ice, the precipitate is sucked off, taken up again in 200 parts of water, neutralized and salted out. After filtering off with suction, washing, drying and grinding, a dark powder is obtained which dyes wool and synthetic polyamide fibers in greenish blue, lightfast and wetfast shades.



   You can also prepare the same dye as follows: 11.1 parts of 1-amino-2-bromo-4- (3 ', 5', 5'trimethylcyclohexylamino) anthraquinone, 50 parts of 2 (2'-methoxyethoxy) ethanol, 2 parts of anhydrous sodium carbonate and 5 parts of 4-methyl-1-meroaptobenzene are heated to 80-85 until the starting product is no longer detectable. The precipitate separated out with 40 parts of ethanol is filtered off with suction, washed with ethanol and with water and dried. The sulfonation is carried out in the manner described above.



  Dyeing instructions:
2 parts of the dye prepared according to Example 1 are dissolved in 6000 parts of 405 water and 4 parts of ammonium sulfate are added. 100 parts of synthetic polyamide (nylon 66) yarn are placed in this dyebath, heated to boiling within 30 minutes and kept at boiling temperature for another hour. Finally the yarn is rinsed and dried. The fibers are brilliantly greenish blue and real colored.

 

   Examples 2 l> is 5
The procedure given in Example I is followed, except that thiophenol, benzylthiol, benzyl alcohol or IS-phenylethanol are used and, after sulfonation or sulfation, the dyes of the formula are obtained
EMI3.1
  
EMI4.1
 dye the wool and synthetic polyamide fibers in real shades of green to violet.

 

Claims (1)

PATENT CLAIM Process for the preparation of anthraquinone compounds of the formula EMI4.2 wherein Y is a sulfonated arylthio, arylalkylthio or Arylalkoxy group, and ring B can carry a fluorine, chlorine or bromine atom or a sulfonic acid group in one of the 15 positions or chlorine atoms in both 15 positions, characterized in that. that one mole of a compound of the formula EMI4.3 wherein Z is a bromine atom or a sulfonic acid group, with 1 mole of a compound of the formula Y1-H converts, where Y1 is an arylthio, arylalkylthio or arylalkoxy group, and sulfonated the reaction product.