DE1160125B - Process for the production of water-soluble dyes of the anthraquinone series - Google Patents

Description

GERMAN

PATENT OFFICE

INTERNAT. KL C 09 b

B 56843 IVc / 22b

REGISTRATION DATE: FEBRUARY 27, 1960

NOTICE
THE REGISTRATION
AND ISSUE OF
EDITORIAL: DECEMBER 27, 1963

It has been found that new valuable dyes of the anthraquinone series containing at least one ionogenic water-solubilizing group are obtained if (a) acylating agents which release the rest of the sulfuric acid with anthraquinone dyes or their precursors which contain at least one via oxygen, sulfur, a Imino group or a - SO ₂ group bonded ^, y-dihydroxypropyl radical, or acylating agents that give off the residue of an organic sulfonic acid, with ionogenic water-solubilizing groups containing anthraquinone dyes or their precursors, which have at least one via oxygen, sulfur, an imino group or a - SO ₂ group-bound / ?, γ-dihydroxypropyl radical, converted to dihydroxypropyl derivatives esterified in the γ-position and, in the case of the use of the precursors mentioned, the anthraquinone dye containing at least one ionogenic water-solubilizing group is completed in the usual manner.

It has also been found that the above-mentioned dyes of the anthraquinone series are also obtained if (b) at least one anthraquinone dyes or their precursors, the corresponding groups, bonded via oxygen, sulfur, an imino group or an - SO2 group, containing γ-epoxypropyl radical carry, with the help of stoichiometric amounts of sulfuric acid, or at least one ionic water-solubilizing group and at least one _{anthraquinone dyes bonded via oxygen, sulfur, an imino group or an - SO 2} group / containing y-epoxypropyl radical or their precursors which carry corresponding groups, with the aid of stoichiometric amounts of organic sulfonic acids to form esterified ^, γ-dihydroxypropyl derivatives in the} 'position and in the case of the use of the process for the preparation

of water-soluble dyes

the anthraquinone series

Applicant:

Aniline & Soda Factory in Baden
Aktiengesellschaft, Ludwigshafen / Rhein

Dr. Hermann Weissauer, Dr. Günter Lange,

Ludwigshafen / Rhine,

and Dr. Helmut Steuerte, Heidelberg,

have been named as inventors

mentioned precursors completes the anthraquinone dye in the usual way.

The invention accordingly relates to a process for the preparation of water-soluble dyes of the anthraquinone series which, bonded via oxygen or sulfur, or via an imino group or a - SC> 2 group, contain at least one β, γ-ΌΊ- hydroxypropyl radical, which in y- Position is esterified with sulfuric acid or an organic sulfonic acid, preferably to a process for the preparation of dyes of the general formulas

(X) «- A -

CH ₂ -CH-CH ₂

OH O SO ₂ 0®Z®jp I

(X) ₇₁ - A - [Y - CH ₈ • CH - CH ₂

OH O • SO ₂ • R

II

where A is the residue of an anthraquinone dye, R is an organic residue, ζ. Β. an optionally substituted aliphatic or aromatic radical, X an ionic water-solubilizing group, Y oxygen, sulfur, an imino group or a - SOa group, Z® a cationic radical, ζ. Β. a hydrogen cation, an ammonium cation or an alkali metal cation such as a sodium or a potassium cation, m an integer from 0 to 4, η an integer from 1 to 4, ρ an integer from 1 to 3 and q an integer from 1 to 3 means. The water-soluble dyes of the anthraquinone series obtainable according to the invention, which contain a β, γ-Dihy droxypropylrest, which is in the y-position with

309 770/332

Sulfuric acid or an organic sulfonic acid is esterified, are of particular technical Interest.

As ionogenic water-solubilizing groups are in particular sulfonic acid groups, carboxyl groups, Phosphonic acid groups and / or HO · SO2 · O groups mentioned.

Acylating agents containing the remainder of the sulfuric acid or the remainder of an organic sulfonic acid are for example sulfuric acid, alkyl sulfonic acids, such as low molecular weight saturated or unsaturated alkyl sulfonic acids, and aryl sulfonic acids, such as arylsulfonic acids, which contain up to two 5- or 6-membered rings, in the form of the free acids or their derivatives, such as their halides or their anhydrides. The following are acylating agents in detail Agents of the aforementioned type mentioned as examples: methanesulphonic acid chloride, propanesulphonic acid chloride, Butanesulphonic acid chloride, vinylsulphonic acid chloride, / g-chloroethylsulphonic acid chloride, benzenesulphonic acid chloride or bromide, p- or o-chlorobenzenesulphonic acid chloride, p-toluenesulphonic acid chloride or bromide, p-toluenesulfonic anhydride, Chlorosulphonic acid, sulfuric acid and their acidic sulphates such as potassium hydrogen sulphate and pyrosulphates, such as potassium or sodium pyrosulfate.

As organic sulfonic acids, aliphatic or aromatic sulfonic acids of those mentioned above can be used Called kind.

The new anthraquinone dyes can be derived from the anthraquinone itself or from more highly condensed ones Anthraquinone derivatives, such as those of the benzanthrone, dibenzanthrone, isodibenzanthrone, Derive violanthrone, isoviolanthrone, pyrazolanthrone or anthrapyrimidine series.

Anthraquinone dyes which optionally carry ionogenic water-solubilizing groups and which, bonded via oxygen, sulfur, an imino group or an - SO2 group, contain at least one β, γ-ΌΊ- hydroxypropyl radical or at least one / ?, γ-epoxypropyl radical, are obtained by conventional methods by Reaction of anthraquinone derivatives which may carry ionogenic water-solubilizing groups and which contain one or more sulfamic acid residues or sulfhydryl groups or, in particular, one or more acylatable hydroxyl or amino groups, with epihalohydrins such as epichlorohydrin or epichlorohydrin, or with dihalohydrins of glycerol and conversion of the halohydrin derivatives initially obtained Epoxy derivatives from which the corresponding dihydroxy compounds can optionally be obtained.

It is easier to obtain these starting dyes for the process according to the invention if one optionally ionogenic water-solubilizing groups carrying anthraquinone derivatives, the one or more sulfinic acid residues or sulfhydryl groups or in particular one or more acylatable Containing hydroxyl or amino groups, with glycid or with halopropyl / 5, γ-dihydroxy compounds implements. This creates the ^, y-dihydroxypropyl groups directly containing anthraquinone derivatives. As halopropyl / 8, γ-dihydroxy compounds For example, 1-chloro-, 1-bromo- or 1-iodine-2,3-dihydroxypropane are suitable.

The following compounds may be mentioned as anthraquinone derivatives which contain one or more sulfinic acid residues or sulfhydryl groups, in particular one or more acylatable hydroxyl or amino groups: 1,4-, 1,5- and 1,8-diaminoanthraquinone, 1,4-, 1 , 5- and 1,8-dihydroxyanthraquinone, 1-amino-i-hydroxyanthraquinone ^ -sulfonic acid, 1-amino ^ -mercaptoanthraquinone, 1-amino-4 - hydroxy - 2 - mercaptoanthraquinone, 1 - amino-4-j8-hydroxyethylaminoanthraquinone, 1,4-bis- / 3-hydroxyethylaminoanthraquinone, 1 - amino - 4 - methylaminoanthraquinone, 1,4 - diamino - 5 - nitroanthraquinone, 1-amino-4- (4-aminoanilino) anthraquinone, 1,4-diaminoanthraquinone - 2 - sulphonic acid, 1,4-diaminoanthraquinone - 2,5 - and - 2,6 - disulphonic acid, 1,5-diaminoanthraquinone-2-sulphonic acid, which is formed by reaction of the l-amino-4-bromoanthraquinone-2-sulx5 fonic acid, l- Amino ^ -bromoanthraquinone ^ -carboxylic acid or l-amino-4-bromoanthraquinone-2,5- or -2,6-disulfonic acid with aromatic diamines, such as 1,3- and 1,4-diaminobenzene, 1,3-diaminobenzene-4 - sulfonic acid, 1,4 - diaminobenzene - 2 - sulfonic acid, 4,4 '- diaminodiphenyl sulfide - 2,2' - disulfonic acid, 4,4 '- diaminostilbene - 2,2' - disulfonic acid, 4, 4'-diaminodiphenyl-2,2'-disulfonic acid, 4,4'-diaminodiphenylamine, 4,4'-diaminodiphenyl-3-sulfonic acid, or aliphatic diamines, such as ethylenediamine and propylenediamine, or aminophenols, such as 1-amino-3-hydroxybenzene or I - amino -A- hydroxybenzene or dihydroxybenzenes, such as resorcinol or hydroquinone, available compounds, and the 4-diaminoanthraquinone by reaction of leuco-l, or leuco l, 4-dihydroxyanthraquinone with aromatic diamines such as 1,3- and 1,4-diaminobenzene, 1,3- and 1,4-diaminobenzenesulfonic acid, or aminophenols, such as l-amino-3-hydroxybenzene and 1-amino-4-hydroxybenzene, are available. Compounds of the benzanthrone, isodibenzanthrone, dibenzanthrone, violanthrone and isoviolanthrone series which carry amino, hydroxyl and sulfhydryl groups may also be mentioned.

Starting dyes for the new process can also be obtained by converting them with hydroxyl groups or with at least one hydrogen atom-bearing amino groups Anthraquinone derivatives containing residues with alcohols, phenols or with primary or secondary aliphatic or aromatic amines condensed which contain at least one ^, y-dihydroxypropyl radical or at least one //, y-epoxypropyl radical contain.

Anthraquinone derivatives which contain radicals capable of reacting with hydroxyl groups or with at least one hydrogen atom-bearing amino groups are, for example, reactive halogen atoms, such as chlorine or bromine atoms, sulfonic acid or carboxylic acid halide groups, halomethyl groups, carboxylic acid anhydride groups or carboxylic acid anhydride groups, or containing anthraquinone derivatives containing dihydroxy acid derivatives. The following may be mentioned in detail: 1-Aminoanthraquinone-2-carboxylic acid chloride, 1-amino-4-nitroanthraquinone-2-carboxylic acid chloride, 1,9-anthrapyrimidine-2-carboxylic acid chloride, BzI-benzanthrone-carboxylic acid chloride, 1-amino-4-bromoanthraquinone -2 - sulfonic acid, 1 - amino - 4 - bromoanthraquinone - 2 - carboxylic acid and l-amino-4-bromoanthraquinone-2,5- (or -2,6) -disulfonic acid, 1,4 - diaminoanthraquinone - 2,3 - dicarboxylic anhydride or . -imide and leuco-1,4-dihydroxy- or -diaminoanthraquinone. Continue to be

5 6

Sulfonic acid chloride groups, halomethyl groups As optionally ionogenic, water-soluble

or dye precursors which carry reactive halogen atoms and carry 1,4 forming groups 1,5- or 1,8-bisarylamino or bisarylthio or for anthraquinone dyes that, via oxygen,

Bisaryloxyanthraquinones and the corresponding group sulfur, an imino group or an SO2 group

pen or benzanthrones carrying halogen atoms, 5 bound, at least one ^, y-dihydroxypropyl

Benzacridones, pyranthrones, violanthrones, isoviol residues are, for example, the following

anthrones and pyrenequinones mentioned. Furthermore, bonds may be mentioned individually: 4-aminophenyl- ( _J ö, y-di-

at this point the binary condensation products hydroxypropyl) - ether, 3 - aminophenyl - (β, γ - dihy-

of cyanuric acid chloride, dichloropyrimidine, droxypropyl) - ether, 2 - aminophenyl - (β, γ - dihy-

Trichloropyrimidine, tetrachloropyrimidine, io droxypropyl) ether, 2-chloro-5-aminophenyl - (/ ?, y-di-

Dichlorophthalazine, dichloroquinazoline, trihydroxypropyl) ether, 2,4-dichloro-5-aminophenyl

chloroquinazoline, tetrachloroquinazoline or {β, γ - dihydroxypropyl) ether, 4 - methyl - 5 - amino-

Phenyldichlorotriazines with aminoanthraquinones or phenyl - (β, γ - dihydroxypropyl) - ether, 2 - methoxy-

called with aminoanthraquinone sulfonic acids. 5-aminophenyl (^, y-dihydroxypropyl) ether, 3-nitro

As alcohols, phenols or primary or secondary 15 6-aminophenyl- (^, y-dihydroxypropyl) -ether, 3-Me-

där aliphatic or aromatic amines, the methylsulfonyl-4-aminophenyl- (jS, y-dihydroxypropyl) -

at least one / 3, y-dihydroxypropyl radical or min- ether, 2-aminophenylene - 1,4-bis - (/ S, y-dihydroxy-

contain at least one ß, y-epoxypropyl radical, come propyl) -ether, N-methyl- or -ethyl-N- (2,3-epoxy-

For example, the following compounds are considered: propyl) -1 - aminobenzene and - 1 -aminonaphthalene,

l-aminopropanediol- (2,3), 1-N-methyl- or -ethyl- 20 N- (2,3-epoxypropyl) -l-aminobenzene and -1-amino-

aminopropanediol - (2,3), imino - dipropanediol - (2,3), naphthalene, 1 - (2,3-epoxypropylamino) -3-hydroxy-

1- (2-, 3- or 4-aminophenoxy) -propanediol- (2,3), benzene or (3-aminophenyl) -2,3-epoxypropyl ether.

N- (2-aminoethyl- or 3-aminopropyl) -N-methyl- dye precursors for anthraquinone dyes,

or -äthylaminopropanediol - (2,3), 1 - (3 - amino- die, at least once via oxygen, sulfur,

4-methylphenoxy) propanediol (2,3), 1- (3-amino- 25 an imino group or an —SCV group

6-methoxyphenoxy) -propanediol- (2,3), 1- (4-amino bonds, contain a / 3, γ-epoxypropyl radical

5-methoxyphenoxy) -propanediol- (2,3), 1- (3-Amino- man prepared by, for example, a

6 - chlorophenoxy) - propanediol - (2,3), 1 - (2 - amino- amino-mercapto-benzene with an epihalogen-

5 - nitrophenoxy) - propanediol - (2,3), 1 - (4 - aminohydrin in the presence of at least stoichiometric

5 - methylsulfonylphenoxy) - propanediol - (2,3), 1- (3-30 amounts of acid-binding agents

or 4 - aminophenylsulfonyl) - propanediol - (2,3), the reaction of the epihalohydrin takes place with

1 - (3 - or 4 - aminophenylmercapto) - propanediol- the sulfhydryl group much faster than with the

(2,3), l- (3- or 4-aminophenylamino) propanediol primary amino group, and one obtains amino

(2,3), l- (3- or 4-aminophenylsulfonic acid amido) - benzenes, which, bonded via a sulfur atom, form a

Propanediol- (2,3), 2-aminophenylene-1,4-bis (2,3-di- 35 ^, y-epoxypropyl radical. Particularly advantageous

hydroxypropyl) ether, l- (6-amino-3-sulfonaphtho- it is, however, acylated on the amino group, ins-

ylene) - (2,3-dihydroxypropyl) ether, 1- [N-methyl-N- special acetylated or formylated compounds

(3- or 4-aminobenzyl)] - aminopropanediol (2,3), as starting materials for the production of epoxy

Dye precursors containing N-methyl- or -ethyl-N- (2,3-epoxypropyl) -l-amipropyl groups

nobenzene and -1-aminonaphthalene, N- (2,3-epoxy- 40 to choose. If one puts such compounds, the

propyl) -1-aminobenzene and -1-aminonaphthalene, at least one hydroxyl, sulfhydryl, amino

1 - (2,3 - Epoxypropylamino) - 3 - hydroxybenzene, or carry sulfamic acid group, with epihalogen

(3 - aminophenyl) - 2,3 - epoxypropyl ether, glycerol hydrines, e.g. B. l-chloro-2,3-epoxypropane or 1-bromo

or l- (2-, 3- or 4-hydroxyphenoxy) propanediol 2,3-epoxypropane in the presence of at least stoichio-

(2,3). 45 metric quantities of acid-binding agents around,

The reaction of the water-soluble, if appropriate, gives the ^, y-epoxypropyl compounds.

Anthraquinone-making, group-bearing anthraquinones for the deposition of the epihalohydrins in

vates that contain one or more sulfinic acid residues or the presence of at least stoichiometric quantities

Sulfhydryl groups or, in particular, one or more acid-binding agents to aromatic compounds

several acylatable hydroxyl or amino groups 50 bonds, e.g. B. compounds of benzene or

contain, with glycid or with halopropyl naphthalene series, one preferably chooses temperature

/ 3, y-dihydroxy compounds or the condensation temperatures between 10 and 100 ⁰ C. This is you

the reaction with hydroxyl groups or with expediently stoichiometric amounts of

at least one amino reactant carrying hydrogen atom, or one uses the

anthraquinone-55 epihalohydrins and / or the acid-binding residues containing groups

derivatives with primary or secondary aliphatic agents in excess. It is advantageous to store them

or aromatic amines, which contain at least one epihalohydrin in the presence of

/ 3, y-Epoxypropylrest or at least one β, γ-Όΐ- means, z. B. water or alcohols such as methanol

containing hydroxypropyl radical, takes place in organic, or ethanol, or mixtures of alcohols with

organic-aqueous or in aqueous liquid, 60 water each.

according to the nature of the radicals capable of conversion, but it is also of interest, aminonitrobenzenes normal temperature, if necessary below and -naphthalenes first with epihalohydrins Cooling or at an elevated temperature and in the presence of at least stoichiometric amounts if necessary to implement in the presence of acid-binding agents and acid-binding agents, for example, from alkali metal, such as sodium, the nitro groups to primary amino groups trium, or potassium, or ammonium, or earth, to reduce for the present process to win alkali metal, such as calcium or barium, -carbo- suitable dye precursors. on nates, hydroxides, bicarbonates, or acetates. this way you can z. B. the ^, y-dihydroxypropyl

4-aminophenylamine and the corresponding isomers, in which the two amino groups are in the ortho or meta position, obtained.

Furthermore, aminohydroxybenzenes and naphthalenes can advantageously serve as starting materials for the preparation of dye precursors which carry β, γ-Έρ-oxypropyl groups. When they are reacted with epihalohydrins in the presence of at least catalytic amounts of acid-binding agents, epihalohydrins in most cases attach to the nitrogen atom of the amino group. However, if the amino group of the aminohydroxybenzenes or naphthalenes is protected from addition, for example by acylation, the isomeric compounds are obtained which result from addition of the epihalohydrins to the oxygen of the hydroxyl groups.

The esterification of the starting materials used in the invention is carried out depending on the type of acid, generally at temperatures between -20 and + 150 ⁰ C in the presence or in the absence of solvents and / or diluents and at ordinary or reduced pressure, optionally in the presence of acid-binding agents . Examples of solvents and / or diluents are as tertiary amines such as pyridine, amides such as N ₅ N-dimethylacetamide, lactams such as N-methylpyrrolidone, ethers such as dioxane, esters such as ethyl acetate, methyl propionate or n-butyl acetate, chlorinated hydrocarbons , such as di- and trichlorethylene or tetrachloroethane, or simple benzene derivatives such as toluene, chlorobenzene or trichlorobenzene, into consideration. Acid binding agents are e.g. B. inorganic agents such as sodium acetate, potassium acetate or sodium bicarbonate, and organic agents such as pyridine, quinoline, Ν, Ν-dimethylformamide or N-methylpyrrolidone. Since the primary hydroxyl group in the y-position in the / ?, y-dihydroxypropyl compounds differs from the secondary hydroxyl group in the ^ -position by its significantly greater reactivity, the esterification with one equivalent of acid per beta, y-dihydroxypropyl group is practically obtained exclusively the γ, γ-dihydroxypropyl derivatives esterified in the y position. The acylating agents which give off the remainder of the sulfuric acid or the remainder of an organic sulfonic acid are therefore advantageously used in stoichiometric amounts with an excess of up to 10%. In some cases, for example if dilute acids, such as 80 to 96% sulfuric acid, are used for the esterification of the β, γ-Όϊ- hydroxypropyl compounds, dihydroxypropyl derivatives esterified in the y position are also obtained when working with excess amounts of acid.

In detail, the esterification can be carried out, for example, as follows: A dye precursor such as 4-aminophenyl (β, γ-dihydroxypropyl) ether is dissolved together with the calculated amount of sulfuric acid in water and the solution is heated to 100 to 160 in vacuo ⁰ C until all water is removed. In the production of dye precursors which have a primary amino group and contain at least one γ-dihydroxypropyl radical bonded via oxygen, for example in the production of 4-aminophenyl (/ S, γ-dihydroxypropyl) ether from 4-acetylaminophenol one often starts with the corresponding N-acyl derivatives. In this case, therefore, it is advantageous to split off the acyl radicals and to esterify the β, γ-dihydroxypropyl groups in the γ position with sulfuric acid in one and the same operation.

The action of the acids used according to the invention to the dye precursors, or on the finished anthraquinone takes place depending on the nature of the acid at temperatures between -20 and + 120 ⁰ C, preferably is selected to temperatures between +10 and + 3O ⁰ C. This is you expediently from stoichiometric amounts of the reaction participants. Depending on the type of acid used, it is also advantageous to use the acid in excess. The acids mentioned can act on the γ-epoxypropyl compounds in the absence or, preferably, in the presence of solvents and / or diluents. Examples of solvents and / or diluents are water or organic agents such as tetrahydrofuran, ethyl acetate or acetic acid, or low molecular weight alcohols, e.g. B. methanol or ethanol, or low molecular weight ketones, e.g. B. acetone, or their mixtures are called.

The dye precursors converted by the present process are more customary Way to anthraquinone dyes completed by, for example, hydroxyl groups or At least one hydrogen atom containing amino groups bearing precursors in the above Way with anthraquinone derivatives which have radicals capable of this conversion. Such Pre-products are z. B. aminopropanediol (2,3-sulfuric acid ester (3), N-methylaminopropanediol - (2,3) - sulfuric acid ester - (3), 1 - (2 -, 3 - or 4 - aminophenoxy - propanediol - (2,3) - sulfuric acid ester- ^), 1 - (3-Amino-4-methylphenoxy) -propanediol- (2,3 - sulfuric acid ester - (3), 1 - (3 - amino - 6 - chloro- or -4,6-dichlorophenoxy) propane diol (2,3) sulfuric acid ester (3), 1 - (3-amino-4-methylphenoxy) propane diol - (2,3) - toluenesulfonic acid ester - (3), 1 - (4 - aminophenylsulfonyl) - propanediol - (2,3) - sulfuric acid ester - (3), 1 - (4 - aminophenylmercapto) - propanediol- (2,3) - sulfuric acid ester - (3) or 1 - [N - methyl -N- (4 - aminobenzyl)] - aminopropanediol - (2,3) - sulfuric acid ester- ^).

The dyeings produced with the dyes obtainable by the present process and prints on cotton are stronger in color than those with N- (4-sulfatobutyl) sulfonamide groups containing dyes, as they are known from French patent specification 976 047, obtained will.

Dyes with ß- hydroxy γ- chloropropyl ether groups, as they are known from Belgian patents 578 746 and 581 359, and the dyes to be used by the method of British patent 733 471 which contain / J-sulfatoethylsulfone groups are by the Process of the invention obtainable dyes in the stability in alkaline dyebaths and in alkaline printing pastes exceeded.

The dyes obtainable according to the invention are suitable for dyeing and / or printing Forms such as foils, films and textiles, e.g. B. fibers, threads, flakes, woven and knitted fabrics from natural and / or synthetic carboxylic acid

substances containing amide groups, such as leather, wool, natural silk or linear polyamides, e.g. B. Polycaprolactam or linear condensation products from adipic acid and hexamethylenediamine. Especially however, the new dyes for true dyeing and / or printing are excellent of structures of the aforementioned type made of native and / or regenerated cellulose, such as cotton, Linen, viscose, hemp or jute are suitable.

When dyeing with the new dyestuffs, one can proceed, for example, by padding textiles made of cellulose with a solution of the dyestuffs according to the invention, if necessary with the addition of electrolytes, and, expediently after drying, passing through a bath containing an alkaline agent such as sodium hydroxide or - carbonate or bicarbonate or potassium hydroxide or carbonate, and expediently contains electrolytes, whereupon the dye is fixed on the fiber by brief steaming. Instead of steaming, treatment with air at temperatures between 20 and 200 ^° C., preferably at 70 to 130 ^° C., can also occur. The alkaline agent can also be added to the pad bath. It is also possible to use the dyes with the addition of alkaline agents and optionally electrolytes, e.g. B. sodium chloride or sodium sulfate, ^{to color at 20 to 30 0} C and fix the dyes by gradually increasing the bath temperature. Finally, textiles made of cellulose can be pretreated with a solution of alkaline agents, dried and then dyed with a dye of the type mentioned and then fixed.

When printing structures made of cellulose, the dyes are advantageously applied to the fibers together with a thickening agent such as sodium alginate or tragacanth, optionally with one of the customary printing auxiliaries and an alkaline agent, and at temperatures between 20 and 200 ^° C., preferably between 50 and 105 ^° C, dried and steamed briefly. You can also apply the dye together with a thickener and one of the usual printing auxiliaries

O NH ₂

SO3K

Print fabric, drying, result in the tissue by a-fed with alkaline agents bath and then dry the temperatures between 20 and 200 ° C or attenuate at 105 ⁰ C. Finally, as with dyeing, the dyestuffs can be printed on a fabric treated with alkaline agents together with thickeners and printing aids and then dried or steamed.

Unless otherwise stated, the parts and percentages given are units of weight. The parts by volume relate to the parts by weight like that measured under normal conditions Liter to kilogram.

example 1

A solution of 20.8 parts of l-amino-4-anilinoanthraquinone-2-sulfonic acid in 210 parts of chlorosulfonic acid for 2 hours at room temperature and stirred for 2 hours at 40 to 5O ⁰ C. The cooled mixture is then poured onto a mixture of 1000 parts of ice and 350 parts of sodium chloride, the precipitate is filtered off, washed with cold sodium chloride solution and the filter material is slurried with 150 parts of ice water. A solution of 13 parts of 1- (4-aminophenoxy) propanediol- (2,3) in 16 parts of 20% strength aqueous hydrochloric acid is added to this slurry, the pH of the solution is gradually brought to 7 and the mixture is stirred after the addition of 6.2 parts of sodium acetate for 48 hours at room temperature. The dye is now precipitated by adding excess potassium chloride, filtered off, purified by redissolving it in water and precipitation with potassium chloride and drying it under reduced pressure.

20 parts of the compound obtainable in this way are at 5 to 10 ° C in 200 parts of 85% sulfuric acid dissolved and stirred for 5 hours at this temperature. The solution is then poured onto ice, separates the dye of the formula

O NH

by adding potassium chloride, filter it and wash it with dilute potassium chloride solution after. The new dye dissolves in water with a blue color and can be removed with the help of alkaline Fix agent on cotton in wet-fast reddish blue tones.

Example 2

183 parts of 4-aminophenyl (y9, y-dihydroxypropyl) ether are dissolved in 100 parts of water together with 100 parts of concentrated sulfuric acid. This solution is first evaporated to an oily consistency in a vacuum at approximately 20 mm of mercury and then ^{heated to 120 °} C. for 15 hours in a vacuum at approximately 20 mm of mercury. This gives the one in the y-position with OH
SO ₂ NH - / V- OCH ₂ CHCH ₂ OSO ₃ K

Sulfuric acid esterified 4-aminophenyl _(J 3, y-dihydroxypropyl) ether in the form of a hard, slightly soluble in water mass having an acid number 243rd

20.8 parts of 1-amino-4-anilinoanthraquinone-2-sulfonic acid are mixed with 210 parts of chlorosulfonic acid as in Example 1 converted to the sulfonic acid chloride and separated off. The filter material is now with 150 parts Ice water slurried and mixed with a solution of 19.7 parts of the, as described in the first paragraph, available compound of the formula

60 H ₂ N-

-O-CH ₂ -CH-CH ₂ -O · SO ₃ H OH

mixed in 60 parts of water. Under vigorous

309 770/332

Stirring at 0 to 5 ° C then brings the pn the Solution to the value 7 in the course of 2 hours and the mixture is stirred after the addition of 6.2 parts Sodium acetate continued for 48 hours. The dye is then added by adding excess Potassium chloride precipitated, filtered off and dried under reduced pressure. He's with the im Example 1 identical dye described.

Example 3 »°

A solution of 21 parts of l-amino-4- (2,6) -dimethylphenylamino) - anthraquinone - 2 - sulfonic acid in 210 parts of chlorosulfonic acid is stirred for 2 hours at room temperature and for 2 hours at 40 to 50 ⁰ C and then to a Poured mixture of 1000 parts of ice and 350 parts of sodium chloride. The sulfonic acid chloride which has separated out is then filtered off, the filter material is washed out with ice water and it is added to a solution of 40 parts of 1 - N - methylaminopropanediol - (2,3) in 80 parts of ice water. With vigorous stirring, the temperature of the mixture is then allowed to rise to room temperature by itself, the mixture is stirred for 18 hours at this temperature and then for a further 1 hour at 60 ° C. After cooling, the dye is obtained by adding a 10% aqueous solution of excess hydrochloric acid separated off, filtered off, washed with highly dilute aqueous sodium chloride solution and purified by dissolving in dilute aqueous ammonia solution and separating with the aid of dilute aqueous hydrochloric acid. 20 parts of the dyestuff thus obtained and dried are esterified by stirring in 200 parts of 85% strength sulfuric acid at 10 to 15 ° C. for 5 hours. The solution is then poured onto ice and the dye of the formula is separated

O NH ₂

SO ₃ K

CH ₃ OH
SO ₂ N - CH ₂ CHCH ₂ OSO ₃ K

CH ₃

by adding excess potassium chloride and drying it under reduced pressure. The new dye dyes cotton in the presence of alkaline agents in wet-fast reddish blue tones.

Example 4

26 parts of the reaction of 1,4-bis (p-toluidino) anthraquinone with dichlorodimethylether obtainable bischloromethyl compound are dissolved in 100 parts of N-methylpyrrolidone and after Addition of 31.5 parts of 1-N-methylaminopropanediol- (2,3) Heated to 75 ° C for 6 hours. Then the solution is diluted with water, the deposited The reaction mixture was filtered off, washed out with water and dried at 80.degree.

20 parts of the compound thus obtainable are dissolved at 0 ⁰ C in 200 parts of 9O ° / cent sulfuric acid and stirred for 2 hours at this temperature. The temperature of the mixture is then allowed to rise to 20.degree. C. by itself. The mixture is then poured onto ice, the reaction material is filtered off and washed acid-free with dilute aqueous sodium chloride solution. The dye of the formula thus obtained

CH ₃ OH

O NH

CH ₂ NCH ₂ CHCH ₂ OSO ₃ Na

CH ₃

O NH

CH ₃

OH

CH ₂ NCH ₂ CHCH ₂ OSO ₃ Na
CH ₃

dissolves in water with a green color and delivers on cotton in the presence of alkaline agents excellent wetfast green colorations.

A dye with very similar properties can be obtained if you add the appropriate amount 1 - N - ethylaminopropanediol - (2,3) used in place of 1 -N-methylaminopropanediol- (2,3).

Example 5

In a solution of 100 parts of concentrated sulfuric acid in 400 parts of water one carries under Stir 225 parts of 3-acetylaminophenyl (^, γ-dihydroxypropyl) ether a. The slurry is then heated to the boil. Thereby the ether goes

gradually in solution. The solution is then refluxed for 3 hours and evaporated to an oily consistency under reduced pressure. The reaction material is then heated for 15 hours in a vacuum at approximately 15 mm of mercury to 120 ^° C. The material becomes very viscous. It solidifies to a glassy mass on cooling. The 3-aminophenyl (jS, γ-dihydroxypropyl) ether thus obtained and esterified in the y-position with sulfuric acid has an acid number of 248.

To prepare an aqueous solution of 3-aminophenyl (/ 3, γ-dihydroxypropyl) ether esterified in the y-position with sulfuric acid, the following procedure can advantageously be used: To a solution of 3-aminophenyl (β, γ- dihydroxypropyl) ether 13.2 parts of chlorosulfonic acid are gradually added ^{at 0 to 5 °} C. in 100 parts of N-methylpyrrolidone. The reaction mixture is then stirred for 3 hours at this temperature, it is applied to approximately 200 parts of ice and the mixture is carefully neutralized. The aqueous solution thus obtained contains about 29 parts in the y-position

Sulfuric acid esterified 3-aminophenyl (/ S, γ-dihydroxypropyl) ether.

A solution of 18.4 parts of cyanuric acid chloride in 150 parts of tetrahydrofuran is added to a mixture of 300 parts of ice and 300 parts of water. Then, into the mixture over one hour at 0 to +5 ⁰ C, a solution of 53.3 parts of the disodium salt of l-amino-4- (3-sulfo-4-aminophenylamino) -anthraquinone-2-sulfonic acid in 1000 parts of

ίο water entered in small proportions. Well stir if the reaction mixture is followed for 15 minutes, an aqueous solution of 28.9 parts of the, as in first paragraph indicated, available, esterified in y-position with sulfuric acid 3-aminophenyl (jö, y-dihydroxypropyl) ethers or the solution prepared in accordance with paragraph 2 is added, the temperature of the mixture increases by itself to room temperature and after adding a solution of 16.4 parts of sodium acetate in 50 parts of water, the mixture is stirred For 18 hours.

Adding excess potassium chloride turns the dye of the formula

O NH ₂

SO ₃ K

O NH

OH
OCH ₂ CHCH ₂ OSO ₃ K

deposited, filtered off and dried under reduced pressure. He goes out on textiles Fix cotton with the help of alkaline agents in wet-fast greenish blue tones.

Dyes with similar properties are obtained, _4. > If one starts from corresponding amounts of 3-amino-4-methylphenyl- (β, γ -dihydroxypropyl) -ether esterified in the y-position with methanesulphonic acid or 4-methylbenzenesulphonic acid or if one starts out from corresponding amounts to 1-amino

4 - (3 - sulfo - 4 - aminophenylamino) - anthraquinone-2 - sulfonic acid or 1 - amino - 4 - (3 - sulfo - 4 - aminophenylamino) -anthraquinone-2,5- or -2,6-disulfonic acid or 1 - amino - 4 - (3 - amino - 4 - sulfophenylamino) - anthraquinone - 2,5 - or 2,6-disulfonic acid or 1,4 - diaminoanthraquinone - 2,6 - disulfonic acid instead of l-amino-4- (3-sulfo-4-aminophenylamino) - anthraquinone - 2 - sulfonic acid as the starting material used.

An aqueous solution of the 3-amino-4-methylphenyl (/ f, γ-dihydroxypropyl) ether esterified in the y-position with methanesulfonic acid can be made as follows:

To a solution of 100 parts of 1-formylamino-2-methyl-5-hydroxybenzene and 30 parts of sodium hydroxide in 1000 parts of water are added to 100 parts of epichlorohydrin. The mixture is then stirred

5 hours at room temperature, the precipitated brown oil is separated off, washed with water, diluted it with the same volume of methanol and stir the mixture for 2 to 3 hours at room temperature. The 2,3-epoxypropyl (3 - formylamino - 4 - methylphenyl) ether crystallizes in fine form Crystal flakes off. The crystals are filtered off with suction and washed with a little methanol.

21 parts of the compound thus obtained are suspended in 100 parts of acetone. One gives now 10 parts of methanesulfonic acid are added and the mixture is stirred for 1 hour at room temperature. then the acetone is distilled off under reduced pressure and the remaining syrupy mass added with cooling in 50 parts of aqueous hydrochloric acid with a density of 1.195. The after The solution obtained after stirring for 3 hours contains approximately 27 parts of the compound of the formula

H ₃ C

NH ₂

O-CH ₂ -CH-CH ₂ -O SO ₂ CH ₃

OH

The one in the y-position with 4-methylbenzenesulfonic acid Esterified 3-amino-4-methylphenyl - (^, y-dihydroxypropyl) ether can be obtained as follows:

21 parts of 2,3-epoxypropyl (3-formylamino-4-methylphenyl) ether are introduced into a solution of 17.2 parts of p-toluenesulfonic acid in 50 parts of acetone. After standing for 4 hours at room temperature, the clear solution is poured into 500 parts of water. The reaction material which separates out in the form of a viscous mass is then separated off and dissolved in 50 parts of aqueous hydrobromic acid with a density of 1.51. This solution is then left to ^{stand at 0 °} C. for several days. The gradually crystallizing hydrobromide of the 3-amino acid esterified in the y-position with 4-methylbenzenesulfonic acid

4 - methylphenyl - (β, γ - dihydroxypropyl) - ether is then filtered off with suction, washed with a little ice-cold water and dried.

Example 6 '■

33.8 parts of 1- (4-acetylaminophenoxy) propanediol (2,3) are heated to boiling with 34 parts of 20% strength aqueous hydrochloric acid for about an hour. The resulting solution of the l- (4-aminophenoxy) -propane- μ diols- (2,3) is neutralized by adding about 115 parts of 10% aqueous sodium hydroxide solution and then to a mixture of 40.4 parts of the sodium salt of the l- Amino-4-bromoanthraquinone-2-sulfonic acid, 24 parts of sodium carbonate, 2 parts of copper sulfate and 1285 parts of water are added. The mixture is then warmed to 40 ^° C. for 1 hour and, after cooling, excess concentrated aqueous hydrochloric acid and solid potassium chloride are added. The deposited dye a.> Is filtered off and washed free of acid with aqueous potassium chloride solution.

48 parts of the compound obtainable in this way are dissolved at 5 to 10 ^° C. in 480 parts of 85% strength sulfuric acid. The solution is then stirred at this temperature for 5 hours and poured onto ice. Then one drops the dye of the formula

O NH ₂

SO ₃ Na

O NH

OH OCH ₂ CHCH ₂ OSO ₃ Na

by adding excess sodium chloride, filter it off, wash it with saturated aqueous solution Sodium chloride solution, filtered off and washed with saturated aqueous sodium chloride solution acid-free and dries it under reduced pressure. The new dye can be used on cotton fix with the help of alkaline agents in wet-fast blue-green tones.

Similar blue dyes are obtained if, instead of l- (4-aminophenoxy) -propanediol- (2,3) corresponding amounts of l- (3- or 4-aminophenylsulfonyl) -propanediol- (2,3) or 1- (3- or 4-aminophenylmercapto) -propanediol- (2,3) or 1- (3- or 4-aminophenylamino) -propanediol- (2,3) or 1- (3- or 4-aminophenylsulfonic acid amido) -propanediol- (2,3) or l- [N-methyl-N- (3- or -4-aminobenzyl)] - aminopropanediol- (2,3) be used.

Other valuable blue dyes can be obtained from the reaction of l-amino-4-bromoanthraquinone-2-sulfonic acid intermediate substances obtainable with the amines mentioned can be prepared by converting the sulfonic acid group therefrom in the usual manner reductively split off and the sulfonic acid group-free compounds then with 85% sulfuric acid esterified.

Example 7

A solution of 20 parts of Violanthron in 200 parts of chlorosulfonic acid is ^{heated to 120 to 130 °} C. for 2 hours. The cooled solution is then poured onto ice, the reaction material is filtered off and washed acid-free with cold water. The wet filtered material is then added (2.3) in 100 parts of water with gentle cooling to a solution of 50 parts of 1-N-Methylaminopropandiol- and the mixture stirred for 24 hours at room temperature and then for 1 hour at 6O ⁰ C. After Zugabe_ of 10% aqueous hydrochloric acid in excess of the deposited dye is filtered off, washed free of acid with water and dried at 100 ⁰ C.

30 parts of the compound obtainable ^{in this way are dissolved in 400 parts of 90% strength sulfuric acid at 5 to 10 °} C. and stirred at this temperature until a sample is clearly soluble in dilute aqueous alkalis. The solution is then poured onto ice, the deposited dye is filtered off, washed acid-free with water and dried under reduced pressure. The dye dyes cotton fabrics with the help of alkaline agents in wet-fast purple tones.

Further, in the usual way by sulfochlorination of the starting dyes, reaction with 1-N-methylaminopropanediol (2,3) The following table shows the dyes obtainable and esterified with sulfuric acid:

Starting dye 35 M-di-u-naphthylaminoanthraquinone hue Aminoviolanthrone 1 ^ -Di-p-toluidinoanthraquinone Gray Isoviolanthrone 1,4-di- (2,4,6-trimethylanilino) - violet 2,2'-dibenzanthronyl anthraquinone Yellowish tinge 1,4-Di-jÖ-tetrahydronaphthylamino- green anthraquinone green 1,4-di (2,4-dimethylanilino) - green anthraquinone blue 45 l, 4-di- (2,6-dimethylanilino) - anthraquinone blue 1-Oxy-4-p-toluidinoanthraquinone 1,5-diamino-2,6-dibromo-4,8-di-p- blue toluidinoanthraquinone ^s 4-p-toluidino-N-methylanthrapyridone blue 1,4-di (4-phenyl) anilinoanthraquinone violet 4-anilino-N-methylanthrapyridone blue Bluish tint Red green Yellowish tinge Red

The new dyes dye textiles made of rayon in the shades given in the table.

Example 8

175 parts 1,4-bis (γ-chloro / 3-hydroxypropylamino) anthraquinone (available from 1,4-diaminoanthraquinone and epichlorohydrin) are in 875 parts "5 dissolved dioxane. 88 parts are added to this solution Add finely powdered potassium hydroxide and stir the mixture for 15 hours at ordinary temperature. The mixture is then poured into 3000 parts

Water, soaks up the deposited dye of the formula

O NH _{- CH 2} - CH - CH ₂

O NH-CH ₂ -CH-CH ₂

\ r »/

wash it off with water and dry it.

92 parts of this compound are dissolved in 200 parts by volume of cold 60% sulfuric acid and after one hour poured into 4000 parts by volume of acetone with cooling. After standing for 2 hours Ordinary temperature, the new dye is filtered, washed with acetone and at room temperature dried. It dissolves in water with a blue color and can be used on cotton fabrics or from polyamides based on adipic acid and hexamethylenediamine in wet-fast fix blue tones. The dye due to its gross composition is likely to have the following Structure:

O NH-CH ₂ -CH-CH ₂ OSO ₃ H

OH

O NH _{- CH 2} - CH - CH ₂ OSO ₃ H

OH

Example 9

6 parts of leuco-1,4-diaminoanthraquinone and 5 parts of 1-aminopropanediol (2,3) in 100 parts of anhydrous pyridine are heated to boiling for 5 hours. A stream of dry air is then passed through the solution at 90 ^° C., the liquid volume being kept constant by adding anhydrous pyridine. A blue solution is obtained which contains 1,4 - bis - (β, γ - dihydroxypropylamino) - anthraquinone. As soon as the leuco compound can no longer be detected in the solution, it is cooled down. At 0 to 10 ^° C., 9.0 parts of chlorosulfonic acid are slowly added dropwise to this solution, the mixture is stirred for a further hour and the pyridine is removed therefrom by decanting off or by vacuum distillation. The residue is dissolved in 95 parts of methanol and the dye is precipitated as the sodium salt by adding 18 parts of anhydrous sodium acetate. The suspension is stirred for 1 hour. The dye is filtered off with suction, with a little methanol

O NH

O NH

washed and air dried. The dye largely agrees with that obtainable according to Example 8 Dye match.

Example 10

22 parts of the veresterten4-aminophenyl in y-position with sulfuric acid _(/ ö, y-dihydroxypropyl) dissolved -äthers of melting point 254-255 ⁰ C, and 3 parts of sodium bicarbonate are dissolved in 600 parts of water. A neutral solution is obtained into which 20.2 parts of the sodium salt of 1-amino-4-bromoanthraquinone-2-sulfonic acid, 0.3 part of copper sulfate pentahydrate, 0.3 part of copper (I) chloride and 34 parts of sodium bicarbonate are introduced. The mixture is stirred for 1 hour at 40 ^° C. and then filtered through a folded filter. The dye is precipitated from the filtrate by adding 160 parts of potassium chloride. The dye is separated off, dissolved in 500 parts of water and separated from this solution again with 90 parts of potassium chloride. The supernatant solution is decanted off and the dye is air dried. It is identical to the dye obtainable according to Example 6.

The pure γ-sulfuric acid ester of 4-aminophenyl (| ö, γ-dihydroxypropyl) ether used here is obtained from the crude ester described in Example 2 by the following purification operation: 132 parts of this crude product are dissolved in 66 parts of water, and the solution is inoculated little crystallized product and stirred for 15 hours at room temperature. The residue is then filtered off with suction and the crystals are dried in air. 44.5 parts of pure sulfuric acid ester with a melting point of 254 to 255 ^° C. are obtained.

Example 11

A solution of 54 parts of l, 4-bis (4-phenylanilino) anthraquinone in 465 parts of chlorosulfonic acid for 2 hours at 0 to 5 ⁰ C, then 20 hours at room temperature and then 1 hour at 75 to 85 ° C stirring. After cooling to room temperature, the solution is poured onto a mixture of 1500 parts of ice and 150 parts of sodium chloride. The dye is suctioned off and washed with Congo-neutral ice water. The filter cake is stirred in 2000 parts of water and, after addition of 34.2 parts of aminopropanediol- (2,3) -sulfuric acid ester- (3), the pH of the mixture is adjusted to 8 with 10% sodium carbonate solution. The mixture is then stirred While maintaining this pH for a further 2 hours at room temperature, 330 parts of pyridine are added and, after a further 2 hours, the new dye of the probable formula is precipitated by the addition of sodium chloride and concentrated hydrochloric acid

SO ₃ H

SO ₂ NHCh ₂ CHOHCH ₂ OSO ₃ H

SO ₃ H

SO ₂ NHCh ₂ CHOHCH ₂ OSO ₃ H

309 770/332

the end. The dye is filtered off with suction, washed neutral with dilute sodium chloride solution and dried. It can be converted into wet-fast green shades by the methods customary for reactive dyes Fix cotton.

The aminopropanediol- (2,3) -sulfuric acid ester- (3) can be obtained as follows:

196 parts of 50% strength sulfuric acid are added dropwise to 91 parts of 1-aminopropanediol (2,3) with cooling. Removed from the Gemsich it under reduced pressure all the water and heated it for 15 minutes in a vacuum to 120 ⁰ C. It 172 parts of a glassy solidified matter is obtained, which is readily soluble in water. The crude product is dissolved in 86 parts of water and the solution is seeded with a little crystallized product. The mixture is stirred for 15 hours at room temperature. The crystals are then suctioned off and dried in the air. 37 parts of aminopropanediol (2,3) sulfuric acid ester (3) with a melting point of 161 to 162 ° C. are obtained. After stirring for 24 hours, 51 parts of ester with a melting point of 160 to 170 ^° C. can be obtained from the filtrate by adding 160 parts of ethanol.

Further, by reacting the starting dyes with epichlorohydrin, conversion of the intermediate substances Dyes obtainable in epoxies and reaction of the epoxy compounds with sulfuric acid the following table shows the same type:

30th

35 The new dyes dye textiles made of rayon or polycaprolactam in the Table specified tones.

Claims (1)

PATENT CLAIM: Process for the preparation of water-soluble dyes of the anthraquinone series, characterized in that (a) acylating agents which release the remainder of the sulfuric acid with anthraquinone dyes or their precursors which have at least one bonded via oxygen, sulfur, an imino group or an —SO2 group / fy-Dihydroxypropylrest, or acylating agents that release the remainder of an organic sulfonic acid, with ionogenic water-solubilizing groups containing anthraquinone dyes or their precursors, which contain at least one bonded via oxygen, sulfur, an imino group or an - SCV group / S, γ-dihydroxypropyl radical , converted to dihydroxypropyl derivatives esterified in the y-position and, in the case of the use of the precursors mentioned, the anthraquinone dye containing at least one ionogenic water-solubilizing group is completed in the customary manner, or that (b) at least one via oxygen, sulfur, an imino group or anthraquinone dyes containing an —SCV group bonded ßy-epoxypropyl radical or their precursors, which carry corresponding groups, with the aid of stoichiometric amounts of sulfuric acid or at least one ionic water-solubilizing group and at least one bonded via oxygen, sulfur, an imino group or an - SO2 group, Anthraquinone dyes containing y-epoxypropyl radical or their precursors which carry corresponding groups are converted with the aid of stoichiometric amounts of organic sulfonic acids to y-esterified fty-dihydroxypropyl derivatives and, if the precursors mentioned are used, the anthraquinone dye is completed in the customary manner. Considered publications:
French Patent No. 976 047;
British Patent No. 733,471;
Belgian patents nos. 578 746, 581 359. When the application was announced, two coloring tables with explanations were laid out. Starting dye hue 1 ^ -Diamino-S-nitroanthraquinone blue l-amino-4- (4-aminoanilino) -
anthraquinone Blue green 1-amino-4-jS-hydroxyethylamino-
anthraquinone Reddish
blue l-methylamino-4-aminoanthraquinone blue 1 -Methylamino-4- (4-aminoanilino) -
anthraquinone Blue green 1,4,5,8-tetraaminoanthraquinone Blue green Bz2, Bz2'-dihydroxyviolanthrone Greenish
blue 45 309 770332 12.63