DE2121525A1 - Anthraquinone dyes - contg sulphite ester gps with increased thermal stability - Google Patents

Abstract

Title dyes of formula: (in which X is hydroxyl or amino, Y is H, hydroxyl, amino, N-aryl sulphonamido, or 2-4 C acyl amino, R1 is hydrogen or 1-4 C alkyl and m is 0 or 1), are prepd. by reacting the corresp. dihydroxy cpd. with at >=1 mol. thionyl chloride in inert organic solvent. The dyes are suitable for dyeing and printing synthetic fibres and plastics esp. linear polyester fibres, for mass colouring of plastics, spin dyeing and esp. for colouring of linear polyester fibres from solvents.

Description

Anthraquinone dyes with a sulfurous acid ester group The invention relates to new, thermally very stable anthraquinone dyes of the formula in which X is a hydroxyl or an amino group, Y is hydrogen, a hydroxyl, an amino, an N-arylsulfonamido or an aliphatic acylamino group with 2 to 4 C atoms in the acyl radical, R1 is hydrogen or an alkyl group with 1 to 4 C Atoms and m mean the values 0 or 1.

Of the new dyes, because of their colouristic properties, such special meaning, which differs from 1-amino-4-hydroxy-anthraquinone (X = -NH2, Y = OH) and quinizarine (Xs and Y = OH).

Besides hydrogen, the methyl, ethyl, n- or i-propyl, n- or i-butyl group into consideration.

The new dyes of the formula I are advantageously prepared by reacting ß-alkoxy derivatives of the formula II with thionyl chloride, which contain two hydroxyl groups in the d or ß position to one another in the alkoxy group: At least 1 mole of thionyl chloride, advantageously 1.2 to 2 moles per mole of compound II, is used for the reaction.

The reaction of (II) with the thionyl chloride takes place in inert solvents such as benzene, toluene, xylene, chlorobenzene, dichlorobenzene, nitrobenzene or anisole expediently at temperatures between 50 and 100,000, preferably between 60 and 90,000.

The starting compounds - the ones required for the preparation of (I) 2-alkoxy-anthraquinone derivatives are known in a manner by reaction of -2-alkoxy or preferably of 2-aryloxyanthraquinone derivatives with polyalcohols in the presence alkaline agents, optionally in the presence of inert solvents such as dimethyl sulfoxide, Dimethylformamide or N-methylpyrrolidone obtained in the heat.

Examples of 2-alkoxy or 2-aryloxyanthraquinone derivatives are 1-amino-4-hydroxy-2-methoxyanthraquinone, 1,4-dihydroxy-2-methoxy-anthraquinone, 1-Amino-4-hydroxy-2-phenoxy- or 2- (4'-chlorophenoxy) anthraquinone, 1,4-H) ihydroxy-2-phenoxy- or 2- (4'-chlorophenoxy) anthraquinone.

The anthraquinone derivatives can also be in the anthraquinone nucleus due to chlorine and / or bromine may be substituted, so that there are correspondingly substituted dyes receives.

As polyalcohols, for. B. glycerol, trimethylolpropane or trimethylolbutane to call.

The new dyes are suitable for dyeing and printing synthetic Fibers and plastics, in particular fibers made from linear polyesters. The dyes are also used to color plastics in bulk, as spinning dyes and particularly suitable for dyeing fibers made of linear polyesters from solvents.

Strong, brilliant pink to orange colorations are produced on polyester fibers obtained both with dyeing with the help of carriers and by the HT process.

Compared to the 2-alkoxy and 2-hydroxyalkoxy derivatives of the amino-hydroxy-anthraquinones the new dyes of the invention have increased thermal stability.

The parts mentioned below are based on weight.

Example 1 20 parts of 1-amino-2- (2,2-bis-hydroxymethyl-butoxy) -4-hydroxy Anthraquinone and 5 parts of thionyl chloride are in 80 parts of dry toluene for 5 hours heated to 80 to 90 0C. After cooling, it is filtered off with suction and washed with methanol and water and dries.

21 parts of dye are obtained which have a brilliant pink color on polyester gives. Mp. 229 to 230 ° C. (from propanol).

Example 2 15 parts of 2- (2,2-bis-hydroxymethyl-butoxy) -quinizarine and 5 parts of thionyl chloride in 80 parts of dry toluene for 4 hours to 80 heated to 90 0C. The work-up is carried out as in Example 1.

13.5 parts of dye are obtained which have strong orange colorations on polyester gives. Mp. 190 to 191 ° C (from xylene).

Example 3 30 parts of 1-amino-4-hydroxy-2- (2. 3-dihydroxypropoxy) -anthraquinone in 100 parts of dry toluene with 20 parts of thionyl chloride Heated to 80 to 90 ° C for 1.5 hours. After cooling, you vacuum off, wash with Methanol and then neutral with water and dry.

26.5 parts of dye (pp. 204 to 205 ° C., from chlorobenzene) are obtained, which delivers real, particularly lightfast pink colors on polyester.

Example 4 36 parts of 1-amino-4- (p-toluenesulfonamido) -2- (2.2bis-hydroxymethyl-butoxy) -anthraquinone and 24 parts of thionyl chloride in 100 parts of dry toluene Heated to 80 to 90 ° C for 9 hours. After cooling, the filtrate is filtered off with suction and recrystallizes the toluene-moist residue from benzene; Mp 190 to 191 00. The dye gives pink dyeings to polyester material with good fastness properties.

Example 5 a) 10 parts of 1,4-diamino-2-g of 2,2-bis (hydroxymethyl) propoxy ~ anthraquinone with 25 parts of acetic anhydride and 2 parts of pyridine for 1 hour Stirred 20 to 40 ° 0. After decomposition with 50 parts of methanol, it is distilled under reduced pressure (bath temperature 70 ° C.), the residue boils with 50 parts Methanol and then stirred at room temperature after adding 2 parts KOH 1 hour after.

The precipitate is filtered off with suction, washed with methanol and water and dried. Yield 11 parts.

b) 5 parts of product (a) above are stirred in 30 parts of dry toluene with 5 parts of thionyl chloride for 4 hours at room temperature. After filtering off with suction and washing with benzene, methanol and cyclohexane, 4 parts of the dye of the formula are obtained which melts at 240 to 248 to 249 oC (from chlorobenzene).

Fiber material made from linear polyesters comes in shades of pink with good Stained fastness properties.

EXAMPLE 6 If the acetic anhydride used in Example 5a is replaced by the equivalent amount of propionic anhydride and the procedure described in Examples 5a and 5b is used, 4 parts of the dye of the formula are obtained which melts at 212 to 213 OG (recrystallized from toluene).

The dye gives a pink color to fiber material made of linear polyester with good fastness properties.

Claims (2)

Claims 1. Thermally stable anthraquinone dyes of the formula in which X is a hydroxyl or an amino group, Y is hydrogen, a hydroxyl7 is an amino, an N-arylsulfonamido or an aliphatic acylamino group with 2 to 4 carbon atoms in the acyl radical, 1 hydrogen or an alkyl group with 1 to 4 carbon atoms and m is 0 or 1. 2. Process for the preparation of thermally stable anthraquinone dyes of the formula in which X is a hydroxyl or an amino group, Y is hydrogen, a hydroxyl, an amino, an N-arylsulfonamido or an aliphatic acylamino group with 2 to 4 C atoms in the acyl radical, R1 is hydrogen or an alkyl group with 1 to 4 C Atoms and m denote the values 0 or 1, characterized in that nan the compound in which R1, Y and m have the abovementioned meaning, is reacted with at least 1 mole of thionyl chloride in an inert organic solvent.