CH491171A - Process for the preparation of anthraquinone dyes - Google Patents

Description

  

  Process for the preparation of anthraquinone dyes The invention relates to a process for the preparation of anthraquinone dyes of the formula
EMI0001.0004
    wherein <B> R </B> is a substituted or unsubstituted aryl radical,

            Ri denotes hydrogen or a substituted or unsubstituted alkyl or cycloalkyl radical and R_ denotes the radical A or a substituted or unsubstituted alkyl or cycloalkyl radical, and ring B can be further substituted.

   A process is characterized by the fact that one has a compound of the formula
EMI0001.0022
         wherein R3 denotes the radical A, or a substituted or unsubstituted alkyl or cycloalkyl radical, sulfonated.



  The alkyl or alkoxy radical contains in each case 1 to 12 and preferably 1 to 6 carbon atoms.



  The Alkylen2, radical can be straight-chain, branched or substituted; B. substituted by a cyclohexyl or phenyl radical. It preferably stands for - (CH.) "-, where n stands for a number from 1 to 8 and preferably for 1 to 6, e.g. -CH2-, - (CH2) 2-,
EMI0001.0040
    The arylene radical R mainly represents a phenylene radical; it can also be a naphthylene or tetrahydronaphthylene radical.

   In addition to the sulfonic acid group, it can be substituted by further substituents, for example by an optionally substituted sulfonic acid amide, alkyl or arylsulfonyl group, an optionally substituted alkyl or alkoxy radical having 1 to 12 and preferably 1 to 6 carbon atoms. The alkyl radicals can be halogen atoms, e.g. B.

    Chlorine, or bromine, the hydroxyl or the cyano groups carry, z. B. chloromethyl, chloroethyl, hydroxymethyl, hydroxyethyl, cyanoethyl, etc .;

   the arylene radical can also be substituted by halogen atoms, preferably chlorine, bromine, but also by an optionally substituted amino group or by hydroxylphenyl, phenoxy, cyano, nitro, etc.

       R, can stand for hydrogen, but can also mean an optionally substituted alkyl radical, for example a methyl, ethyl, propyl, chloromethyl, chloroethyl, hydroxymethyl, hydroxyethyl, cyanoethyl or benzyl radical, etc .; but it can also be an optionally substituted cycloalkyl radical, preferably a cyclohexyl radical or an alkyl, z.

   B. Methylcyclohexylrest. R: can stand for the radical A or mean an optionally substituted alkyl or cycloalkyl radical, where the alkyl or cycloalkyl radical can have the same structure as the radical Ri.



  The ring B can be substituted by halogen, such as chlorine or bromine, or by hydroxyl.



  Good dyes are obtained by using a compound of the formula
EMI0002.0023
    in which the phenyl radical E can be further substituted, sul foniert.



       Similar good dyes are obtained by using a compound of the formula
EMI0002.0026
    or if you have a compound of the formula
EMI0002.0027
         sulfonated. The sulfonation is advantageously carried out in sulfuric acid monohydrate or in 5 to 10 mol oleum or in chlorosulfonic acid at temperatures between 0 and 40 ° C., preferably between 20-25 ° C.



  The new dyes are used to dye, pad or print fibers of animal origin, e.g. B. of wool or silk, synthetic polyamide fibers and leather, and cellulose fibers such. B. cotton or linen, and fibers from regenerated cellulose, z. B. Viscose rayon, copper rayon or rayon, of mixtures and / or structures made of these fibers.



  The wetting, leveling, thickening and other textile or leather auxiliaries commonly used can be used for dyeing, padding or printing.



  The dyes can be colored from an acidic or neutral medium at temperatures of 70-100 ° C., preferably at boiling temperature. They have good build-up properties on these substrates and level off extremely well.



  The dyeings or prints obtained are of excellent brilliance, between red-tinged and green-tinged blue, and have very good lightfastness, especially on wool and synthetic polyamides. They dye streaky nylon excellently; The wet fastness properties, such as washing, fulling, water, seawater, perspiration and soda boiling fastness, as well as the rub and dry cleaning fastness are good.



  As synthetic polyamide fibers, for. B. into consideration: the condensation products of 1,6-hexamethylenediamine with adipic acid or sebacic acid, the polymerization products of e-caprolactam or the polycondensation products of cu-aminoundecanoic acid and mixed condensation products, e.g.

   B. from 1,6-hexamethylenediamine, adipic acid and e-caprolactam.



  Some of the compounds of the formula (II) can be prepared from the corresponding 1-amino-4-alkyl or 4-cyclohexylamino-anthraquinones by addition of unsaturated aliphatic carboxylic acids or their functional derivatives, such as acid nitriles or acid amides , e.g.

   B. acrylic acid, methacrylic acid, crotonic acid or by condensation with halogenated aliphatic carboxylic acids or their lactones z. B.

   Halobutyric acid, halopropionic acid, halo valeric or halo isovaleric acid, halocaproic acid, haloenanthic acid, butyrolactone, valerolactone, caprolactone, etc., on or with the 1-amino group and conversion by known methods into the arylamide compound.



  Other compounds of formula (II) can be made forth if 1,4-dihydroxyanthraquinone is reacted with the corresponding amino acids, e.g. B. with aminoacetic acid, α- or i3-aminopropionic acid, α-aminobutyric acid- α-aminoisobutyric acid, aminovaleric acid, z.

   B. w-aminovaleric acid, amino-caproic acid, etc., and converted into the arylamide compounds by known methods. From US Pat. No. 3,247,229, the use of the dye of the formula
EMI0003.0002
    known for dyeing polyamide fibers.



  It is surprising that the dyes of the formula (1), likewise dyed on polyamide fibers, have an improved build-up capacity.



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



  <I> Example 1 </I> In 75 parts of sulfuric acid monohydrate, 11.7 parts of 1- (2'-carbophenylamido) -ethylamino-4-cyclohexylamino-anthraquinone, prepared according to the details of the French patent specification number, are added at 14-18 1 470 597 registered. 8 parts of weak oleum are added and the mixture is stirred at 18-20 for 5 hours. The reaction product is poured into 150 parts of water and 50 parts of ice, filtered and the residue is washed with a 10% aqueous sodium chloride solution.

    It is kneaded with lithium carbonate up to a constant pH value of 7.5 and dried at 100. The dye dyes synthetic polyamide fibers from a weakly acidic bath in vivid blue tones. The dyeing is wetfast and has excellent lightfastness. Striped material is colored regardless.



  <I> Example 2 </I> In 50 parts of sulfuric acid monohydrate, 6.7 parts of 1,4-di- (2'-carbophenylamido) -ethylamino-anthraquinone, prepared according to the information in French Patent No. 1 390 833 registered. 4 parts of 250% oleum are added and the mixture is stirred for 5 hours at 20-25.



  The reaction product is poured onto 200 parts of ice and 100 parts of water, filtered and the residue with a 20o; Wash o aqueous sodium chloride solution. It is then kneaded with sodium carbonate and dried at 100. The dye dyes wool and synthetic polyamide fibers from a weakly acidic bath in lively reddish blue tones. The dyeings on synthetic polyamide fibers are particularly waterfast and extremely lightfast. Strong nuances can be achieved and streaky material is colored equally.

    <I> Dyeing example </I> A dyebath is prepared from 4000 parts of water, 4 parts of ammonium sulfate and 4 parts of the dye from Example 1 and heated to 40. At this temperature you go with 100 parts of fabric made of synthetic polyamide fibers. The bath is heated to boiling temperature in the course of 30 minutes and colored for 60 minutes. After 30 minutes the evaporated water is replaced and 2 parts of glacial acetic acid are added. After dyeing, the fabric is rinsed with cold water and dried.



  If you dye wool by the same method, you get a dye with similarly good properties.



  <I> Example 3 </I> In 80 parts of sulfuric acid monohydrate, 12 parts of 1- (2'-carbophenylamido) -a-methyl-ethyl-amino-4-cyclohexyl-aminoanthraquinone are introduced at 15-20. 8 parts are added Add oleum and stir for 5 hours at 20. The mass is poured onto 150 parts of water and 50 parts of ice, filtered and the residue is washed with a 50/10% aqueous sodium chloride solution. It is kneaded with lithium hydroxide to a constant pH value of 7.5 to 8 and dried.

   The dye dyes wool and synthetic polyamide fibers from a weakly acidic bath in vivid blue tones.



  The dyeings are wet-fast and have high lightfastness on wool and very high lightfastness on synthetic polyamide. Synthetic polyamide material with a streaky color is dyed evenly.



  The following table shows the structural build-up of further dyes which can be obtained according to the information in Examples 1 to 3. They correspond to the formula
EMI0003.0047
         wherein alkylene, B, R, Ri and Ra have the meanings given in the table.
EMI0004.0001
    
EMI0005.0001
    
EMI0006.0001
    
EMI0007.0001
    
EMI0008.0001
    
EMI0009.0001
    
EMI0010.0001
    
EMI0011.0001


 

Claims (1)

PATENT CLAIM Process for the production of anthraquinone dyes of the formula EMI0012.0005 wherein R is a substituted or unsubstituted arylene radical R, Hydrogen or a substituted or urisubstituted alkyl or cycloalkyl radical and R2 is the radical A or a substituted or urisubstituted alkyl or cycloalkyl radical and the ring B can be further substituted, characterized in that a compound of the formula EMI0012.0017 where R3 denotes the radical Az or a substituted or unsubstituted alkyl or cycloalkyl radical, sulphated. SUBClaims 1. The method according to claim, characterized in that compounds of the formula EMI0012.0026 in which the phenyl radical E can be further substituted, sulphonated. 2. The method according to claim, characterized in that dyes of the formula (I) are produced in which ralkylene represents -CH2-, - (CH2) 2-, EMI0012.0037 or EMI0012.0038 stands. Note from <B> the </B> Federal <B> Office </B> for intellectual property: Should parts of the description not be consistent with the definition of the invention given in the claim, it should be remembered that according to Art. 51 of the Patent Act, the patent claim is decisive for the material scope of the patent.