DE1644518C3 - 12/28/66 Switzerland 18777-66 Anthraquinone dyes insoluble in water - Google Patents

Description

where η is the number 2 or preferably the number 1, R is a substituted phenyl or naphthyl radical, in particular a phenyl radical which has at least one acyloxy, phenoxy, hydroxyl or alkoxy group or a fused-on at least one o- or p-position to the anthraquinone radical contains heterocyclic 5- or 6-membered ring which is bonded to the p-position by a sulfur or oxygen atom, R ₁ and R _{2 are} hydrogen atoms or alkyl radicals optionally substituted by hydroxy, alkoxy or phenyl groups, R _{3 is} a hydrogen atom , an optionally substituted alkyl, cycloalkyl, phenalky! or phenyl group and R ₄ a hydrogen atom, an optionally substituted alkyl, cycled alkyl or phenalkyl group, the radicals R ₃ and R ₄ also together with the nitrogen atom being a heterocyclic group Can form a ring, and B ₁ and B ₂ denote optionally substituted alkyl radicals, halogen atoms or, in particular, hydrogen atoms.

2. Dyestuffs according to claim 1, characterized in that in the formula given in claim 1, R is a phenyl or naphthyl radical bonded in the 2-position, which is at least one hydroxy, alkoxy, phenoxy in the o- or p-position to the anthraquinone radical - or acyloxy group, R ₁ and R _{2 represent} hydrogen atoms or optionally substituted alkyl radicals as indicated in claim 1 and η is 2 or 1 and that in the R ₃ R ₄ N · SO, groups only R _{3 can represent} a hydrogen atom.

3. Dyestuffs according to Claim 1, characterized in that in that specified in Claim 1 Formula R denotes a phenyl radical.

4. Dyes according to Claims 1 and 2, characterized in that in the form specified in Claim 1! R ₁ and R _{2 represent} hydrogen atoms.

It has been found that the new ^v ihin.dungen represent fully water-insoluble anthraquinone dyes of formula " ₃₅ .

The dyes according to the invention are obtained

B, -

NHR

.M

SO, N

HO O NHR

or mixtures thereof, in which / 1 denotes the number 2 or preferably the number 1, R is preferably bonded in the 2-position and is a substituted phenyl or naphthyl radical. in particular a Phcnyl-. rest, the at least one standing in o- or p-position to the anthraquinone residue acyloxy. Contains phenoxy, hydroxyl or alkoxy group or a fused-on heterocyclic 5- or 6-membered ring which is bonded to the p-position through a sulfur or oxygen atom. represents. R, and R ₂ hydrogen atoms or optionally by hydroxy. Alkoxy. Acyloxy or phenyl groups represent substituted alkyl radicals, R represents a hydrogen atom. an optionally substituted alkyl, cycloalkyl, phenalkyl or phenyl group and R _{4 is} a hydrogen atom, preferably an optionally substituted alkyl, cycloalkyl or phenalkyl group, the radicals R ₃ and R ₄ also forming a heterocyclic ring together with the nitrogen atom can, and B, and B, optionally substituted alkyl radicals. Halogen atoms or especially hydrogen atoms are of particular value when using a compound of the formula

4b

45

SO ₂ X) ₁ ,

HO O NHR

or mixtures thereof, in which X is a halogen atom, with one or more amines of the formula NHR ₁ R ₄ .
Sulfonic acid chlorides are preferably used as process starting materials. These can be obtained by reacting the corresponding 1,5-dihydroxy-4,8-diamino-2-aryl, in particular -2-phenylanthraquinone, with chlorosulfonic acid. The following dihydroxydiaminoanthraehinones may be mentioned as examples of the reaction with chlorosulfonic acid:

l, 5-dihydroxy-4,8-diamino-2 or

3- (4'-hydroxy-phenyI) -anlhraehinone.
l, 5-dihydroxy-4,8-diamino-2 or

3- (4'-hydroxy-3'-ch! Orphcnyl) -anthraquinone,

l, 5-dihydroxy-4,8-diamino-2 or
3- (4'-methoxyphenyl) anthraquinone.

o ^ - or

3- (4'-hydroxy-3'-methylphenyl) -anthraquinone,, S-dihydroxy- ^ S-diamino-1- or

3- (4'-hydroxy-2'-methylphenyl) -anthraquinone, 1,5-dihydroxy-4,8-diamino-2- or 3- (2'-hydroxy-5'-methylphenyI) -anthraquinone,, S-dihydroxy ^ S-diamino-I- or

3- (2'-hydroxy-5'-ethylphenyl) anthraquinone, !, S-dihydroxy- ^ S-diamino ^ - or

3- (4'-hydroxy-3'-amylphenyl) anthraquinone. !, S-dihydroxy ^ S-diamino ^ - or

3- (2'-hydroxy-5'-amylpheny]) anthraquinone. l, 5-dihydroxy-4,8-diamino-2 or

S - ^ '- hydroxy-S'-octylphenylj-anthraquinone, l, 5-dihydroxy-4,8-diamino-2 or

3- (2'-hydroxy-5'-cyclohexylphenyl) anthraquinone,
I, S-dihydroxy ^ S-diamino ^ - or

3- (4'-hydroxy-3'-phenylphenyl) -anthraquinone, lS-dihydroxy ^ S-diamino-I- or 3- (2'-hydroxy-5'-phenylphenyl) -anthraquinone, .S-dihydroxy ^ S- diamino ^ - or 3- (4'-hydroxy-3 ', 5'-dimethylpheny!) - anthraquinone,
IS-dihydroxy-AS-diamino ^ - or

3- (3'.4'-dimethoxyphenyl) anthraquinone, 1,5-dihydroxy-4,8-diamino-2- or

3- (2'.5'-dimethoxyphenyl) anthraquinone. l, 5-dihydroxy-4,8-diamino-2 or 3- | 4-benzyloxy) -phynylanthraquinone,

l, 5-dihydroxy-4,8-diamino-2- or 3- (4'-hydroxy-3'-methoxyphenyl) -anthraquinone,
.S-dihydroxy ^ S-diamino ^ - or 3- (3 ', 4'-dihydroxy-phenyl) -anthraquinone.

I.S-DihydroxyAS-diamino ^ - or

? - (2.-I'-dihydroxy-phcnylj-anthraquinone. , S-dihydroxy ^ S-diamino ^ - or

3- (2 ', 5'-dihydroxyphenyl) anthraquinone. l.S-dihydroxy ^ .S-diamino ^ - or

3- (2 ', 4', 6'-trihydroxyphenyl) ~ anthraquinone, 1, S-dihydroxyÄS-diamino ^ - or 3- (4'-phenoxyphenyl) -anthraq ^; non,, S-dihydroxy ^ S-diamino ^ - or 3- (2'-hydroxynaphthyl-1> anthraquinone, .S-dihydroxy ^ S-diamino ^ - or 3- (4'-hydroxynaphthyl-1 ') -anthraquinone, , S-dihydroxy ^ -amino-S-methylamino ^ - or

3- (4'-hydroxyphenyl) anthraquinone, 1,5-dihydroxy-4,8-dimethylamino-2- or

3- (4'-hydroxy-phenyl) -anthraquinone,!, S-dihydroxy ^ -amino-S-hydroxyäthylamino ^ -

or 3- (4'-hydroxyphenyl) -anthraquinone,!, S-dihydroxy ^ -hydroxyäthylamino-S-amino ^ - or 3- (4'-hydroxy-phcnyl) -anthraquinone,

!, S-dihydroxy ^ -amino-ü-acetoäthylamino ^ -

or 3- (4'-methoxy-phenyl) -anthraquinone,!, S-dihydroxy ^ -amino-S-benzoyloxyethylamino-2- or 3- (4'-hydroxyphenyl) anthraquinone,

1,5-dihydroxy-4,8-diamino-6 (or 7) -bromo-2-

or 3- (4'-hydroxy-phenyl) -anthraquinone, l, 5-dihydroxy-4,8-diamino-6 (or 7) -bromo-2-

or 3- (4'-methoxyphenyl) anthraquinone. !, S-dihydroxy ^ S-diiimino ^ - or 3- (4'-hydroxy-3 '(or 2') -bromo-phenyl) -anthraquinone,

^^ - or 3- (4'-methoxy-3 '(or 2') -bromo-pheny]) -

anthraquinone,
l, 5-dihydroxy-4,8-diamino- (iH (or 7) -bromo-2- or 3- (4'-methoxy-3 '(or 2'-bromophenyl) -

anthraquinone, furthermore
US-Dihydroxy ^ S-diamino-anthraquinones, which in 2- or 3-position the remainder of a bonded in 5-position

2,3-dihydro-benzothiophene, 2,2-dimethyl-3-hydrobenzofurans, 2-methyl-2,3-dihydroben / ofurans, 2,5- or 2,7-dimethyl-2,3-dihydrobenzofurans

or
2-methyl-7-chloro-2,3-dihydrobenzofuran or the remainder of a 2,2,3- bonded in the 6-position

or 2,2,4-trimethylchroman, 2,2,4-trimethyl-3,4-dehydrochroman or 2,3-benz-1,4 or 1,5-dioxane.

These compounds can e.g. B. obtained by adding hydroxyl or alkoxybenzenes to the boric acid ester dissolved in concentric sulfuric acid, S-dihydroxy ^ .S-diaminoanthraquinone-2,6-disulfonic acid according to German patent 4 45 269, boiling the adduct in acidic aqueous solution or Heating in an alkaline solution to 20 to 60 ^° C., during which a sulphonic acid group is split off, according to German patent specification 4,46,563, and reductive splitting off of the sulphonic acid group still present and, if necessary, treatment of the 1,5-dihydroxy-4,8-diamino-2- phenyl-anthraquinones with alkylating and / or acylating agents, such as ethyl bromide, ethyl chloride, ethylene chlorohydrin, benzyl chloride, and also alkyl sulfonic acid esters, such as methyl p-toluenesulfonate, alkyl sulfals. such as dimethyl or diethyl sulfate, aldehydes, especially formaldehyde, alkylene oxides, such as ethylene oxide, chloroethyl chloroformate, chloro-isopropyl chloroformate, phenyl-P-chloroacetyl chloroformate or epichlorohydrin, acetic anhydride or benzoyl chloride. Compounds in which the 3-aryl chloride is bound, can be obtained according to the Belgian patent 6 27 010 * earth.

Another way to get to process starting materials / u is the implementation of 1,5 - dihydroxy - 4,8 - diamino - 2 - aryl - anthraquinone-6-sulfonic acids with phosphorus pentachloride or chlorosulfonic acid.

The sulfonic acid halides mentioned are to be reacted with ammonia or amines of the formula HNR ₁ R ₊ , for example with

Methylamine.

Ethylamine.

Ethanolamine,

Propylamine,

Butylamine.

('yclohexylamine,

Benzylamine,

Aniline.

Dimethylamine.

Diethylamine,

Dibutylamine.

N-methylaniline,

Pyrrolidine.

Piperidine.

Moipholin,

2-cyanoethylamine,
Bis- (2-cyanoethyl) -ainine,

Diethanolamine (the hydroxyl group can still be acylated after the reaction), ethyleneimine, >

N, N-dimethylpropylenediamine (1,3),
N-methyl-aniline,
Bis (2-methoxyethyl) amine,
Diisopropylamine,

N-methylpiperazine, ^{| 0}

N-hydroxyethylpiperazine.

The sulfohalides are reacted with the amines, for example, in organic solvents such as nitrobenzene, alkylene chloride or pyridine or in excess dialkylamine, but preferably in aqueous suspension or with the addition of acetone. In order to avoid saponification of the sulfonic acid halide groups, the condensation is expediently carried out at relatively low temperatures, for example between 0 and 80.degree. In certain cases it is advantageous to condense below 0 ⁿ C.

In order to get to the particularly valuable dye mixtures, you can either manufacture them Mixing dyes or the mixtures by reacting a mixture of sulfochlorides of different of the anthraquinone aurine dyes described above and or by employing a mixture produce various amines in situ.

The new dihydroxy-diaminoanthraquinones and mixtures thereof are valuable dyes. which has excellent drawability for polyester fibers, especially polyethylene terephthalate fibers, and these in pure blue to greenish blue tones of excellent light and Fastness to sublimation colors. The new dyes also have a good structure and a good cotton reserve on.

For dyeing, the new dyes are expediently used in finely divided form and under-dyeing Addition of dispersants such as soap. Sulphite cellulose liquor or synthetic detergents, or one Combination of different wetting and dispersing agents. As a rule, it is useful to use the dyes before dyeing in a dye preparation containing a dispersant and finely dispersed dye in such a form that when the dye preparations are diluted with water a fine dispersion arises. Such dye preparations can be used in a known manner, for. B. by falling over of the dye from sulfuric acid and grinding the slurry thus obtained with sulphite waste liquor, if necessary also by grinding the dye in highly effective grinding devices in dry or wet form be obtained with or without the addition of dispersants during the milling process.

The new dyes are also suitable for dyeing by the so-called heat-setting process, according to which the fabric to be dyed with an aqueous dispersion of the dye, which /.weckweise 1 to 50% ^ o Lamines and thickeners, especially sodium alginate, contains, preferably impregnated at temperatures at most 60 "C and squeezed off as usual wild. It is expedient to squeeze in such a way that the impregnated goods have 50 to 100% of their initial f <s retains weight of dye liquid.

To fix the dye, the fabric impregnated in this way is expediently dried after prior drying, e.g. B. in a warm air stream, heated to temperatures of over 10C ⁰ C, for example between 180 and 220 ° C.

The dyeings obtained are expediently subjected to an aftertreatment, for example by heating with an aqueous solution of an ion-free detergent.

Instead of being impregnated, the dyes can also be applied by printing. To this Purpose one uses z. B. a printing ink, which in addition to the usual aids in printing, such as network and thickeners ^ the finely dispersed dye, optionally in admixture with one of the abovementioned Cotton dyes, optionally in the presence of urea and / or an acid-binding agent Means, contains.

The new dyes can also be used for spin dyeing polyamides, polyesters and polyolefins use. The polymer to be colored is expediently in the form of powder, grains or chips, as a finished spinning solution or in the molten state mixed with the dye, which in the dry State or in the form of a dispersion or solution in an optionally volatile solvent is introduced. After homogeneous distribution of the dye in the solution or melt of the polymer the mixture is made into fibers in a known manner by pouring, pressing or extruding, Yarns. Monofilaments, films, etc. processed.

The new dyes are also suitable for the production of paints and inks, in particular ballpoint pen inks.

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

example 1

2 parts of 1.5-dihydroxy-4,8-diamino-2- (4'-methoxyphenyl) anthraquinone are dissolved in 50 Volumtei.'en freshly distilled chlorosulfonic acid. The mixture heats up to 35 and turns green. The stirring is continued overnight at room temperature. The reaction mixture is then poured onto 1 kg of ice, filtered and washed until neutral. That still moist product is introduced into 20 parts by volume of a 40% aqueous methylamine solution and that Keep simmering for a full 30 minutes. Then it is diluted with water and filtered, the filler residue washed and dried. 2.3 parts of a dye are obtained which dyes polyester fibers blue and is excellent Has light and sublimation fastness.

Staining instructions

I part of the dye obtained in accordance with paragraph I is mixed with 2 parts of a 5% strength aqueous solution Grind wet from sulphite culluloscablaugc and dry.

This dye preparation is mixed with 40 parts of a K) "11 strength aqueous solution of a condensation product stirred from octadecyl alcohol with 20 mol of ethylene oxide and 4 parts of a 40% acetic acid solution admitted. A dye bath of 400 parts is prepared from it by diluting it with water.

This bath is entered at 50 "with parts of a cleaned polyester fiber cloth, and the temperature is increased in half an hour to 120 to 130 and stains for 1 hour in a closed vessel at this temperature

temperature. Then it is well rinsed. You get a pure blue color of excellent lightfastness and sublimity fastness.

15 e i s ρ i e I 2

The procedure is as in Example I, but instead of the methylamine solution, an equimolar amount of a 40% strength aqueous n-bulylamine solution is used. The N-bulylsulfonamide of 1,5-dihydroxy-4,8-diamino- 2 - (4'-mclhoxy-phenyl) -anthraquinone is obtained. This dye is even resistant to sublimation at 210 °, it has very good lightfastness, is also suitable for the thermal fixation process and dyes polyester fibers blue.

Analysis:

Calculated ... N = 8.2. S = 6.2%;
found .... N = 7.8, S = 6.3%.

Example 3

The procedure is as in Example 1. except that 18.75 parts of 1,5-dihydroxy-4,8-diamino-2- (4'-methoxyphenyl) anthraquinone are used and 94.3 parts by volume of chlorosulfonic acid were used. The one that is still damp and washed neutrally Filter cake is poured into a mixture of 250 parts by volume of acetone and 11.3 parts of N-methylcyclohexylamine given and refluxed for 1 hour in the presence of 4 parts of sodium bicarbonate. After filtering, washing colorlessly and drying, 13.7 parts of a dye are obtained which gives blue dyeings with very good fastness properties on polyester fibers.

Example 4

The procedure is as in Example 3, but an equimolar amount is used in place of the N-methylcyclohcxylamine used by 2-chloro-p-phenylenediamine. A dye is obtained which dyes polyester fibers blue.

Example 5

The procedure is as in Example 3, but instead of N-methylcyclohexylamine, an equimolar amount is used N-hydroxyethyl pipcrazine used. A dye is also obtained, which polyester fibers are blue colors.

Example 6

The procedure is as in Example 3, but instead of the N-methyl-cyclohexylamine, an equimolar amount is used used by aniline. A dye is obtained which dyes polyester fibers blue.

Example 7

The procedure is as in Example 3, but instead of N-methyl-eyclohcxylamine, an equimolar Amount of N-methyl-pipcrazin used. A dye is obtained which dyes polyester fibers blue.

Example 8

1 part 1,5-dihydroxy-4,8-diamino-3- (4'-methoxy) -phenylanlhraquinone are chlorosulfonic acid in 40 parts by volume - 10 'solved. This reaction mixture was at a temperature between - 10 and - 5 " Stirred for 4 hours. After this time, a mixture of 600 parts of ice and 80 parts of sodium chloride was added and 100 parts of water. The filtered, neutral washed product was with 50 parts by volume Boiled n-butylamine under reflux for 1 hour. Subsequently it was diluted with water, the excess amine was driven off with steam, acidified and filtered. The filter cake was washed out and dried. 1.2 parts of a dye were obtained Dyes polyester fibers in blue tones with good fastness properties.

Example 9

If you proceed as in Example 8, but a!, S-dihydroxy ^ S-diaminoanthraquinone as the starting material used, which in the 2-position is the remainder of a 2 ', 2'.4'-trimethylchroman bound in the 6-position contains, a dye is obtained with properties similar to those in Example 8.

Example 10

5.1 parts of a dye obtained according to Example 3, in its preparation instead of N-methylcyclohexylamine Cyclohexylamine was used, 30 parts of nitrobenzene and a spatula tip of iron (III) bromide a solution of 1.6 parts of bromine in 20 parts of nitrobenzene is added dropwise at 50 °. It is then stirred for 3 more hours at the same temperature and then the nitrobenzene removed by steam distillation. The residue, which is insoluble in water, is filtered off and dried. 5.4 parts of a blue dye are obtained which have a bromine content of 12.5%.

<6O9 612/68

709

Claims (1)

Patent claims: 1. Water-insoluble anthraquinone dyes formula SO, N B, - HO O NHR