CH495403A - Anthraquinone dyes for addn to spinning masses for - Google Patents

Abstract

Water insoluble anthraquinone dyes have the formula (I):- n = 1 or 2; X1 = OH or -NHR2; X2 = OH or -NHR3; R1 = H or opt. substd. alkyl; B1 and B2 = H, halogen, or opt. substd. alkyl; R = aryl, which is substd. in at least one o- or p-position relative to the anthraquinone group by acyloxy, aryloxy, hydroxyl or alkoxy, or a condensed heterocyclic 5- or 6-ring bonded to the p-position by an S or O atom; and Ac = an acyl group, pref. the acyl group of an monocarboxylic or sulphonic acid group.

Description

  

  
 



  Process for the preparation of new water-insoluble anthraquinone derivatives
The present invention relates to a process for the preparation of valuable, new water-insoluble anthraquinone dyes of the formula
EMI1.1
 or mixtures thereof, in which n is 1 or 2, preferably 1., X1 is a hydroxyl group or preferably a radical of the formula -NHR2 and X2 is a radical of the formula -NHR3 or preferably a hydroxyl group, R1, R2 and R3 are hydrogen atoms or possibly by e.g. Hydroxy, alkoxy, acyloxy or aryl groups represent substituted alkyl radicals.

  B1 and B represent optionally substituted alkyl radicals, halogen atoms or, in particular, hydrogen atoms, R represents a preferably substituted aryl radical, in particular a benzene radical which has at least one acyloxy, aryloxy, hydroxyl or alkoxy group in o- or p-position to the anthraquinone radical or a fused-on group contains heterocyclic 5- or 6-membered ring, which is bonded to the p-position by a sulfur or oxygen atom, and Ac is an acyl radical, preferably the acyl radical of a monocarboxylic or sulfonic acid, which is characterized in that the anthraquinone compounds of the formula
EMI1.2
 wherein X1, X, R1, R, R;

   and R have the same meaning as above, in the presence of an acylating derivative of an organic acid, especially an aliphatic one. cycloaliphatic, araliphatic. aromatic or heterocyclic monocarboxylic or sulfonic acid. preferably the carboxylic acid anhydride or halide and the sulfonic acid halide. or subjected to the Friedel-Crafts reaction in the presence of the free acid itself and a Friedel Craft catalyst.



   The following dihydroxyanthraquinones may be mentioned as examples of starting anthraquinones: 1,5-dihydroxy-4,8-diamino-2- (4'-hydroxyphenyl) anthraquinone, 1,5-dihydroxy-4,8-diamino-2- (4'-hydroxy-3 'chlorophenyl) anthraquinone, 1,5-dihydroxy-4,8-diamino-2- or -3- (4'-methoxyphenyl) anthraquinone, 1,5-dihydroxy-4, 8-diamino-2- or -3- (4'-hydroxy-3'-methylphenyl) -anthraquinone, 1,5-dihydroxy-4,8-diamino-2- or -3- (4'-hydroxy-2 ' -methyl-phenyl) -anthraquinone, 1,5-dihydroxy-4,8-diamino-2- or -3- (2'-hydroxy-5'-methyl-phenyl-anthraquinone, 1,5-dihydroxy-4,8 -diamino-2- or -3- (2'-hydroxy-5'-ethyl-phenyl) -anthraquinone, 1,5-dihydroxy-4,8-diamino-2- or -3- (4'-hydroxy-3 '-amyl-phenyl) -anthraquinone, 1,5-dihydroxy-4,8-diamino-2- or -3- (2'-hydroxy-5'-amyl-phenyl) -anthraquinone,

   1,5-dihydroxy-4,8-diamino-2- or -3- (2'-hydroxy-5'-octyl-phenyl) -anthraquinone, 1,5-dihydroxy-4,8-diamino-2- or - 3- (2'-hydroxy-5'-cyclohexyl-phenyl) -anthraquinone, 1,5-dihydroxy-4,8-diamino-2- or -3- (4'-hydroxy-3'-phenyl-phenyl) - anthraquinone, 1,5-dihydroxy-4,8-diamino-2- or -3- (2'-hydroxy-5'-phenyl-phenyl) -anthraquinone, 1,5-dihydroxy-4,8-diamino-2- or -3- (4'-hydroxy-3 ', 5'-dimethyl-phenyl) -anthraquinone, 1,5-dihydroxy-4,8-diamino-2- or -3- (3', 4'-dimethoxy- phenyl) anthraquinone, 1,5-dihydroxy-4,8-diamino-2- or -3- (2 ', 5'-dimethoxyphenyl) -anthraquinone, 1,5-dihydroxy-4,8-diamino-2 - or -3- (4'-benzyloxy-pheny) -anthraquinone, 1,5-dihydroxy-4,8-diamino-2- or -3- (4'-hydroxy-3'methoxyphenyl) -anthraquinone 1, 5-dihydroxy-4,8-diamino-2- or -3- (3'-4'-dihydroxy-phenyl) -anthraquinone, 1,5-dihydroxy-4,8-diamino-2- or -3- (2 ', 4'-dihydroxyphenyl) anthraquinone,

   1,5-dihydroxy-4,8-diamino-2- or -3- (2 ', 5'-dihydroxy-phenyl) -anthraquinone, 1,5-dihydroxy-4,8-diamino-2- or -3- (2 ', 4', 6'-trihydroxyphenyl) -anthraquinone, 1,5-dihydroxy-4,8-diamino-2- or -3- (4'-phenoxyphenyl) -anthraquinone, 1,5- Dihydroxy-4,8-diamino-2- or -3- (2'-hydroxynaphthyl-1 ') -anthraquinone, 1,5-dihydroxy-4,8-diamino-2- or -3- (4'-hydroxynaphthyl- 1 ') - anthraquinone, 1,5-dihydroxy-4-amino-8-methylamino-2- or -3- (4'-hydroxyphenyl) -anthraehinone, 1,5-dihydroxy-4,8-dimethylamino-2 - or -3- (4'-hydroxyphenyl) anthraquinone, 1,5-dihydroxy-4-amino-8-hydroxyethylamino-2- or -3- (4'-hydroxyphenyl) anthraquinone, 1,5 -Dihydroxy-4-amino-8-acetocyäthylamino-2- or -3- (4'-methoxyphenyl) -anthraquinone, 1,5-dihydroxy-4-amino-8-benzoyloxyethylamino-2 or -3- (4'- hydroxy-phenyl) -anthraquinone,

   1,5-dihydroxy-4,8-diamino-6- or -7-bromo-2 or -3- (4'-hydroxyphenyl) anthraquinone, 1,5-dihydroxy-4,8-diamino-6 or -7-bromo-2 or -3- (4'-methoxyphenyl) -anthraquinone, 1,5-dihydroxy-4,8-diamino-2- or -3- (4'-hydroxy-3 'or -2' -bromo-phenyl) -anthraquinone, 1,5-dihydroxy-4,8-diamino-2- or -3- (4'-methoxy-3 'or -2'-bromophenyl) -anthraquinone, 1,5- Dihydroxy04,8-diamino-6 or -7-bromo-2 or -3- (4'-methoxy-3'- or -2-bromophenyl-anthraquinone, also 1,5-dihydroxy-4,8-diamino-anthraquinones, the in the 2- or 3-position the remainder of a 2,3-dihydrobenzothiophene bonded in the 5-position, 2,2-dimethyl-3-hydrobenzofuran, 2-methyl-2,3-dihydrobenzofuran, 2,5- or 2,7- Dimethyl-2,3-dihydrobenzofurans or 2-methyl-7-chloro-2,3-dihydrobenzofurans,

   or the remainder of a 2,2,3 or 2,2,4-trimethylchroman, 2,2,4-trimethyl-3,4-dehydrochroman or 2,3-benz-1,4- or -l bonded in the 6-position Contain 5-dioxane.



   These compounds can e.g. B. can be obtained by addition of hydroxy or alkoxybenzenes to the conc. Boric acid ester of 1,5-dihydroxy-4,8-diaminoanthraquinone-2,6-disulfonic acid dissolved in sulfuric acid according to German patent specification 445 269, cooking the addition product in acidic aqueous solution or heating in alkaline solution to 20 to 60 ° C., with a sulfonic acid group is split off, according to German patent specification 446 563, and reductive elimination of the sulfonic acid group still present and, if necessary, treatment of the 1,5 dihydroxy-4,8-diamino-2-phenyl-anthraquinones obtained with alkylating and / or acylating agents such as ethyl bromide, ethyl chloride, Ethylene chlorohydrin, benzyl chloride, also alkyl sulfonic acid esters,

   such as methyl p-toluenesulfonate, alkyl sulfates, such as dimethyl or diethyl sulfate, aldehydes, in particular formaldehyde, alkylene oxides, such as ethylene oxide, chloroformic acid ethyl ester, chloroformic acid ss-chloroisopropyl ester, chloroformic acid 1-phenyl-2-chloroacetyl chloride or benzoic anhydride or epichlorohydrin . Compounds in which the aryl radical is bonded in the 3-position can be obtained according to Belgian patent 627 010.



   Suitable Friedel-Crafts catalysts are Lewis acids, such as. B. aluminum trichloride, aluminum tribromide, antimony pentachloride, iron trichloride, titanium tetrachloride, tin tetrachloride, zinc chloride, Eisenentribro midl also sulfuric acid, phosphoric acid, chlorosulfonic acid, trichloroacetic acid, boron trifluoride and its complexes, such as, in particular, phosphorus ethers, alcohols or acids such as phosphorus, such as phosphorus, such as phosphorus, such as phosphorus, such as phosphorus and phosphorus chlorides how they z. B. in the work of G.A.Olah aFriedel-
Crafts and Related Reactions, Volume III, New York
1964.



   Carboxylic acid halides suitable as starting materials for the reaction according to the invention are aliphatic acid chlorides, such as acetyl chloride, propionyl chloride, n-butyl acryl chloride, crotonic acid chloride, 2-methyl mercaptopropionyl chloride, 4-chlorobutyryl chloride, araliphatic carboxylic acid halides, such as phenylacetyl chloride, cyclo-chloro-chlorides such as phenylacetyl chloride, cyclo-chloro-chlorochloride or p-nitrophenylacetyl chloride. 5-norbornene-2-carboxylic acid chloride, aromatic carboxylic acid chlorides, such as benzoyl chloride, o-, m- and p-methyl- and ethylbenzoyl chloride, o-, m- and p-methoxy- and ethoxybenzoyl chloride, 1- or 2-naphthalenecarboxylic acid chloride,

   3,4-dinitrobenzoyl chloride, 2,4- or 3,4-dichlorobenzoyl chloride, p-phenylazobenzoyl chloride, 2-anthraquinone carboxylic acid chloride, heterocyclic carboxylic acid halides, such as furan-2-carboxylic acid chloride, 2-thienyl carboxylic acid chloride, 2-thienyl acetyl chloride and nicotinic acid chloride.



   Suitable carboxylic anhydrides are acetic anhydride, n-butyric anhydride, isobutyric anhydride, cyclobutanecarboxylic anhydride, benzoic anhydride, p-chlorobenzoic anhydride, 2-furancarboxylic anhydride and nicotinic anhydride.



   Mixed anhydrides can also be used, such as 8. the anhydrides of acetic acid and benzoic acid or ß-naphthoic acid, which usually result in mixtures of dyes.



   If necessary, one can also start from the free acids. when the acid halide or the anhydride are difficult to access.



   Sulfonic acid halides suitable as starting materials for the reaction according to the invention are benzene sulfonic acid chloride, o- and p-toluenesulfonic acid chloride.



  2,4-, 2,5- or 3,5-dimethyl-benzenesulfonic acid chloride, 3,4,5- or 2,4,6-trimethyl-benzenesulfonic acid chloride, tetralin-7-sulfonic acid chloride. p-nitrobenzenesulfonic acid chloride, 2-methyl-5-chlorobenzenesulfonic acid chloride, 5-methyl-thiophene-2-sulfonic acid chloride and methanesulfonyl chloride.



   Instead of the chlorides, the fluorides can optionally also be used. Bromides or iodides of the acids can be used.



   If in the t-standing groups. in particular if these represent free amino groups and acyl groups are also bound in the course of the Friedel-Crafts reaction, these are, if desired, split off again by alkaline saponification.



   The alkylation or acylation is conveniently carried out by heating in an inert organic solvent, for example halogenated hydrocarbons such as carbon tetrachloride, 1,2-ethylene chloride, chlorobenzene, o-dichlorobenzene, nitrohydrocarbons such as nitrobenzene or nitronaphthalene. as well as carbon disulfide.



   The reaction can take place at Zinmer temperature. or below, but also at a slightly elevated temperature.



  z. B. be carried out at 40 to 60 C.



   The new acylated aminoanthraquinone compounds or their mixtures are valuable products that can be used for. B. can be used as dyes or dye intermediates. As dyes, they are suitable for dyeing a wide variety of materials. Those.



  which are insoluble in organic solvents and water are used as pigments. Those. those in organic solvents. such as esters and especially alcohol and are soluble in acetone, can be used for coloring natural or artificial resins, waxes, lacquers and plastic masses, eg. 8. from cellulose ethers or esters. for example for spin-dyeing acetate silk, as well as for dyeing natural or synthetic polymers or condensation products. In particular, they have excellent drawability for polyester fibers. especially for polyethylene terephthalate fibers and dye them in pure blue to greenish blue tones with excellent lightfastness and sublimation fastness.

  The new dyes also have a good structure and a good cotton reserve.



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



   example 1
3.77 parts of 1,5-dioxy-4,8-siamino-2- (4'-methoxyphenyl) anthraquinone are finely suspended in 80 parts by volume of nitrobenzene and this suspension is saturated at 5 to 1 () with hydrogen chloride gas, the Colors changes to reddish brown. 1.57 parts of acetyl chloride are added dropwise and then at 1 (1- 2.67 parts of anhydrous aluminum chloride are added in portions, with a slight increase in temperature. The reaction mixture is stirred at room temperature overnight. Finally, water is added, the nitrobenzene is driven off by steam,

   the suspension is filtered and the product is dried. 3.6 parts of a reddish-tinged blue dye of the formula are obtained
EMI3.1
 which attaches well to polyethylene terephthalate fibers and has very good light and sublimation fastness.



      Color code t.-
1 part of dye is wet-ground with 2 parts of a 50% strength aqueous solution of the sodium salt of dinaphthylmethanedisulfonic acid and dried.



   This dye preparation is stirred up with 4 parts of a 10% strength aqueous solution of the sodium salt of N benzyl-heptadecyl-benzimidazole disulfonic acid and 4 parts of a 40% strength acetic acid solution are added.



  A dye bath of 4 (10 (1 parts) is then prepared by diluting with water.



   This bath is filled with 1 (1 (1 part of a purified polyethylene terephthalate fiber material at 5 ()). The temperature is increased to 120 to 1300 in half an hour and dyed for one hour in a closed vessel at this temperature. This is followed by thorough rinsing a reddish blue coloring of excellent lightfastness and sublimation fastness.



   Example 2
3.77 parts of 1,5-dioxy-4,8-diamino-2- (4'-methoxyphenyl) anthraquinone are finely suspended in 100 parts by volume of nitrobenzene. 10 parts by volume of methanesulfonyl chloride are added to this suspension and the whole is heated to 80 with stirring. 15 parts of finely powdered aluminum chloride are introduced in portions and the mixture is then stirred for 6 hours at the same temperature.



  After this time, the reaction mixture is reduced to a mixture of conc. Hydrochloric acid and ice discharged. The nitrobenzene is removed by steam distillation. It is filtered, washed neutral and dried. 4.3 parts of a dye which colors polyethylene terephthalate in blue shades are obtained.



   The analysis gives a sulfur content of 7.6% and the infrared spectrum shows the absorption bands characteristic of sulfones at 1115 cm-1 and 1345 cm-1.



   Example 3
If 3.77 parts of 1.5 dioxy-48-diamino-2- (4'-hydroxyphenyl) anthraquinone are used as the starting product and the procedure is exactly as in Example 2, a dye is also obtained here. the polyethylene terephthalate colors in blue tones.



   Example 4
If the procedure is exactly as in Example 2, but instead of methanesulfonyl chloride, 23 parts of nicotinic acid chloride are used, 3.1 parts of a blue one are obtained
Dye.



   Example 5
The procedure is exactly as in Example 2, but instead of methanesulfonyl chloride, 18.05 parts of benzoyl chloride are used. this gives 7.2 parts of a red-violet dye, which is concentrated in 60 parts by volume. Sulfuric acid enters at 20. The mixture is stirred for 60 hours at this temperature, poured onto ice, filtered, washed neutral and dried. 5.4 parts of a blue dye are obtained.

 

   Example 6
7.56 parts of 1,5-dioxy-4,8-diamino-2- (4'-methoxyphenyl) -anthraquinone are finely suspended in 200 parts by volume of nitrobenzene. 0.070 part of ferribromide is added to this suspension and the mixture is heated to 80 ". 2.5 parts of bromine are added dropwise and the temperature is maintained for 2
Hours held. Then you add 20 parts by volume of methanesulfonyl chloride and carry. still at the same temperature, a portion of 30 parts of aluminum chloride. The mixture is stirred for a further 6 hours at the same temperature. Finally the reaction mixture is reduced to conc. Hydrochloric acid and Els discharged and the nitrobenzene removed by steam distillation.



  It is filtered, washed neutral and dried.



   10.6 parts of a blue dye mixture are obtained.

 

Claims (1)

PATENT CLAIM Process for the preparation of water-insoluble anthraquinone dyes of the formula EMI4.1 or mixtures thereof, in which n is the number 1 or 2, X1 is a hydroxyl group or a radical of the formula -NHR. and X. is a radical of the formula -NHR or a hydroxyl group, R1, R. and Rg represent hydrogen atoms or optionally substituted alkyl radicals, B1 and B represent optionally substituted alkyl radicals, halogen atoms or hydrogen atoms, R represents a substituted aryl radical and Ac is an acyl radical , characterized in that the anthraquinone compounds of the formula EMI4.2 where X1, X-), R1, R, Rs and R have the same meaning as above, subjects the Friedel-Crafts reaction in the presence of an acylating derivative of an aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic acid, or in the presence of the free acid itself, and a Friedel-Crafts catalyst. SUBCLAIMS 1. The method according to claim, characterized in that anthraquinones are produced. in which the radical R is a benzene radical which contains at least one acyloxy, aryloxy, hydroxy or alkoxy group in the o- or p-position to the anthraquinone radical or a fused-on heterocyclic 5- or 6-ring which is connected to the p-position is a sulfur or oxygen atom. 2. The method according to claim or dependent claim 1, characterized in that one starts from those anthraquinones in which R is a preferably substituted benzene radical and at least one of the substituents B1 and B is hydrogen. 3. The method according to dependent claim 2, characterized in that one starts from those anthraquinones in which X1 is an amino group and X9 is a hydroxyl group. 4. The method according to dependent claim 2, characterized in that one starts out from anthraquinones which only have unsubstituted amino and hydroxyl groups in the o-position. 5. The method according to dependent claim 4, characterized in that acylation is carried out with aliphatic monocarboxylic acid halides. 6. The method according to dependent claim 4, characterized in that acylation is carried out with aromatic monocarboxylic acid halides. 7. The method according to dependent claim 4, characterized in that acylation is carried out with aromatic monosulfonic acid halides.