DE2140069A1 - Green - red anthraquinone dyes prepn - products used for dyeing wool, silk, leather and cellulosics - Google Patents

Abstract

Green, blue, violet and red reactive anthraquinone dyes for dyeing wool, silk, synthetic, polyamides, leather also cellulosics shades fast to light, water, washing and rubbing have the formula:- (AQ-CH2 NHCOCH2N(R')CORX)-(SO3H)n (where AQ is the residue of an anthraquinone dye combining via an O or N. atom with an aromatic ring contg. a replaceable H atom; R is opt. satd. lower alphatic hydrocarbon; R' is H or lower alkyl; X is Cl, Br; n is 1-4) and are prepd. by condensing an anthraquinone dye combining via an O or N atom with an aromatic ring contg. a replaceable H atom, with a reactive substance of formula: Y. CH2NHCOCH2N(R')CORX (where Y is halogen or OH). and sulphonating the resulting product if required.

Description

"Anthraquinone reactive dyes and process for their preparation The present invention relates to the preparation of anthraquinone reactive dyes of the general formula (I) where AQ is an antraquinone dye radical which is linked via an N or O atom to an aromatic nucleus which has a displaceable hydrogen, R is a saturated or unsaturated lower aliphatic hydrocarbon radical, Rt is a hydrogen atom or a lower alkyl group, X is a chlorine or bromine atom and n is an integer from 1 to 4.

The dyes of the present invention are made according to the following produced by both methods.

(1) An antraquinone dye which is connected via an N or O atom to an aromatic nucleus containing a displaceable hydrogen atom is combined with a reactive substance of the following general formula (11) in which Y is a halogen atom or a hydroxyl group and R, R 'and X have the meanings given above, reacted and then, if necessary, the product is sulfonated.

(2) The antraquinone dye, which is connected via an N or O atom to an aromatic nucleus which has a displaceable hydrogen atom, is combined with a reactive substance of the following general formula (III) wherein R, R 'and X have the same meanings as above and are reacted with a formaldehyde or a compound which forms a formaldehyde, and then the product is sulfonated if necessary.

The antraquinone dyes used in the present invention are for example 1-amino-4-arylaminoantraquinone-2-sulfonic acid, 1 .4-bisarylaminoantraquinone, 1-amino-2-aryloxy-4-arylaminoantraquinone, 1-alkylamino-4-arylaminoantraquinone, 1-hydroxy-4-arylaminoantraquinone, 4-arylamino-1. 9-antrapyridone, 4.4'-bisarylaminodiantrimide, 1.4-diamino-2.3-diphenoxyantraquinone, i-Amino-2-methyl-4-arylaminoantraquinone, 1-amino-2-halogen-4-arylaminoantraquinone, 1 .4-diamino-2-aryloxyantraquinone, 1.5-dihydroxy-4-nitro-8-arylaminoantraquinone, 1.5-dihydroxy-4-amino-8-arylaminoantraquinone, 1.5-diamino-4,8-dihydroxy-2-hydroxyphenylantraquinone, 1,5-diamino-4,8-dihydroxy-2-alkoxy phenylanetrachinone, etc. and it is preferred that they have an alkyl and / or alkoxy group in an aryl group of these compounds exhibit.

The reactive substance corresponding to the general formula (II) is obtained by using the reactants corresponding to the general formula (III) substance treated with leomaldehyde in a weakly alkaline solution or that one can dissolve the same reactive substance in sulfuric acid with a Substance that forms formaldehyde, such as synmetric dihalodimethyl ether or 'araformaldehyde, can react and it is used in the form of the sulfonic acid solution, The reactive substance of the general formula (III) is produced by that one Glycinalkylester or Sulcocinalkylester with the halide of a halogenated Fatty acids such as chloroacetyl chloride, chloropropionyl chloride, dibromoacrylic bromide, etc. acylated and then converts the resulting ester into the amide.

The method (1) of the present invention is preferably like is carried out as follows: The condensation reaction of the anthraquinone dye with a reactive substance of general formula (II) is in a dehydrating acidic condensing agent, preferably sulfuric acid, in a concentration of 80 to 90% carried out at 0 ° to 50 ° C for several to a little over 10 hours. To The reaction mixture is poured into ice water to form a precipitate poured, the precipitate being separated off, neutralizing the adhering acid ull (l then the product is filtered.

The method (2) of the present invention can be carried out as follows be: The specified antraquinone dye is used together with a reactive Substance of formula (II) dissolved in sulfuric acid and synmetric halodimethyl ether or paraformaldehyde is added at a lower temperature and the reaction carried out under slow heating.

In the case of the product having a reactive group does not have a sulfonic acid group or that the introduction of a sulfonic acid group into the Desired product becomes fuming after the condensation reaction has ended Sulfuric acid is added to the reaction mixture or the product is separated off and dried and then sulfonated with 100% sulfuric acid or fuming sulfuric acid and a post-treatment, as indicated above, subjected, whereby the dye of the present invention.

The dye thus obtained is for dyeing wool, silk, synthetic Polyamide fibers and leather in a bright color shade with good fastness properties suitable for light, water, rubbing and washing. Furthermore, this gives Dye as well as cellulose fibers or cellulose acetate fibers are lightfast and washable color tint Pad treatment in an alkaline medium.

The present invention is illustrated by the following examples.

Example 1 4.4 parts of the sodium salt of a dye of the general formula which is obtained by condensing 1 mole of 1-amino-4-bromoanetrachinone-2-sulfonic acid with 1 mole of 2,6-xylidine, are dissolved in 60% sulfuric acid at 100.degree. 2.1 parts of N-methylolchloroacetylglycine amide are added to this solution and stirred for 16 hours at 100 to 1500 and then this solution is poured into water and the precipitated dye is separated by filtration. The separate dye cake thus obtained is suspended in water and a dilute solution of sodium hydroxide is added to adjust the pil value to 5.0. After the dye is thoroughly dissolved, sodium chloride is added to precipitate the dye as the sodium salt. This dye, which has the following general formula is a dark blue powder and dyes wool permanently blue in a weakly acidic dye bath.

If 2.3 parts of N-methylolchloroacetylsulcosinamide are used in place of N-methylolchloroacetylglycine amide in this example, a similar dye of the following formula is obtained Example 2 4.6 parts of the sodium salt of a dye represented by the following general formula are dissolved in 60 parts pointer sulfuric acid at 1000 or below. 1.7 parts of chloroacetylglycine amide and 0.36 part of paraformaldehyde are added to this solution and the mixture is stirred at 100 to 1500 for 16 hours. This mixture is poured into ice water and a dye separated according to the procedure of Example 1. This dye, which has the following formula, dyes wool in a weakly acidic dye bath, color-fast, blue.

If, in this example, 2.0 parts of 2-chloroacryloylsulcosinamide are used instead of 1.7 parts of chloroacetylglycine amide, a permanent blue dye of the following formula is obtained.

Example 3 4.74 parts of a dye of the general formula are dissolved in 60 parts of a sulfuric acid under 1000 and 3.4 parts of chloroacetylglycine amide are added. After the solution has been cooled to below 50 ° C., 14 parts of dichlorodimethyl ether are added and the mixture is slowly warmed to 1000 and stirred at 10 to 1500 for 16 hours. The solution is poured into ice water, the precipitate obtained is separated off by filtration and washed until the filtrate is neutral and getrockne.t under vacuum.

The dye obtained is disulfonated by adding it to 50 parts of 10.60 fuming sulfuric acid are added at 10 to 1500 and 2 hours sulfonated at 15-1800. The reaction mixture is poured into ice water and then the dye is separated off, neutralized, salted out, filtered and dried under vacuum.

The dye thus obtained corresponds to the following formula and dyes wool in a weakly acidic bath blue.

The dyes corresponding to the formulas below can be prepared by similar methods.

violet violet Green The color given for each dye is obtained when dyeing wool. Even when the materials colored with any of these dyes are immersed in a goat pyridine solution, the dye is hardly released.

Reference example Method for producing N-methylolchloroacetylglycine.

28 parts of a hydrochloride of glycine ethyl ester are in -300 parts Dissolved water and while the solution with an acid binder to pH 6 to 7 holds, 15 parts of chloroacetyl chloride are added dropwise below 50C, the precipitate is separated by filtration and dried under vacuum. That way it gets to 24 parts of Ohloracetylglycinäthylester 60 parts of aqueous ammonia with a specific Weight of 0.9 are chilled below 500, 1.8 parts of oxaloacetyl glycine ethyl ester are added and this solution is stirred for 30 minutes at the same temperature. Finally, the precipitated chloroacetylglycine amide is separated off by filtration and dried under vacuum.

Then 35% formalin is made weakly alkaline with potassium carbonate, an equivalent amount of chloroacetylglycine amide was added and the mixture was stirred at 60 ° C. for 30 minutes.

The entire solution is dried under vacuum and IV methylolchloroacetylglycine amide obtained as a powder.

-Patent claims-

Claims (3)

Claims 1. A process for the preparation of anthraquinone-xeactive dyes of the general formula (I) wherein AQ is an antraquinone dye radical which is linked via a ~ or 0 atom to an aromatic nucleus which has a displaceable hydrogen, R is a saturated or unsaturated lower aliphatic hydrocarbon radical, R 'is a hydrogen atom or a lower alkyl group, X is a chlorine or Bromine atom and n is an integer from 1 to 4, characterized in that an anthraquinone dye which is connected via an N or O atom to an aromatic nucleus which has a displaceable hydrogen atom is connected to a reactive substance of the following general formula (II) wherein Y is a halogen atom or a hydroxyl group, R, R 'and X have the same meaning as above, condensed and, if necessary, the product is sulfonated. 2. Process for the preparation of anthraquinone reactive dyes of the general formula (I), dadurchge -kennze ic hnet that an anthraquinone dye which is connected via an N or O atom to an aromatic nucleus which has a displaceable hydrogen atom is, with a reactive substance of the following general formula (III) wherein R, R 'and X have the same meaning as above, and with formaldehyde or a compound which forms formaldehyde, and, if necessary, sulfonated the product. 3. Anthraquinone reactive dye dadurchge -kennzeic hnet that it has the general formula (I) wherein AQ is an antraquinone dye radical which is linked via an N or O atom to an aromatic nucleus which has a displaceable hydrogen, R is a saturated or unsaturated lower aliphatic hydrocarbon radical, R 'is a hydrogen atom or a lower alkyl group, X is a chlorine or bromine atom and n is an integer from 1 to 4.