CS230596B2 - Method of production of water-soluble monoazocompounds - Google Patents

Abstract

1. Water-soluble monoazo compounds corresponding to the general formula (1) in which : see diagramm : EP0078024,P21,F1 R**1 is a hydrogen atom, a lower alkyl group, a lower alkoxy group or a chlorine atom ; R**2 is a hydrogen atom, a lower alkyl group or a lower alkoxy group ; R**3 is a hydrogen atom or a lower alkyl group which can be substituted by a hydroxy group, a lower alkanoylamino group, a sulfato group, a carboxy group or a sulfo group ; R is a hydrogen atom, the sulfomethyl group, the carbamoyl group, the cyano group or the sulfo group ; D is the m- or p-phenylene radical which are substituted by one or two sulfo groups or by one or two sulfo groups and one lower alkyl group ; X is a monosulfophenoxy group ; Y is the vinyl group, or an ethyl group which, in the beta-position, contains a radical capable of being eliminated under alkaline conditions as an anion ; the formula moieties R**1, R**2, R**3 and R have meanings which are identical to or different from one another.

Description

The invention relates to a process for the production of water-soluble moonozoes, i.e., a technical field of fiber-reactive azo dyes.

Japanese-published Sho-56-037379 and German-published 20 50 901 disclose azo compounds having fiber-reactive dye properties containing a pyridone coupling component.

We have now found new valuable water-soluble mono-isolates which correspond to the general formula 1

In which case a hydrogen atom, an alkyl group having 1 to and in particular a methyl group, an alkoxy group having in particular a methoxy column, or a chlorine atom, represents a hydrogen atom, an alkyl group having 1 to carbon atoms such as up to 4 carbon atoms,

R ² carbons such as ethyl, and especially methyl, or C 1 -C 4 alkoxy, such as ethoxy, and especially methoxy, ethyl, such as ethoxy

R @ 1 represents a hydrogen atom or a C1 -C4 alkyl group such as methyl or propyl, and in particular ethyl substituted by hydroxy, C2 -C5 alkanoylamino, such as propionylamino and in particular acetylamino, stfatosktpinot (of the formula -OSO2M), carboxy (of formula -COOM), or sulfo (of formula -SO4M), and in these formulas

M 'represents a hydrogen atom or the equivalent of a monovalent, divalent or trivalent metal, in particular an alkali metal or an alkaline earth metal such as sodium, potassium or calcium,

R represents a hydrogen atom, a sulfomethyl group (of the formula -CHg-SO4M and M as defined above) or a carbonyl group, or preferably a cyano group, or particularly preferably a sulfo group,

D represents a meta- or para-phenylene group which is substituted by one or two sulfo groups or one or two sulfo groups and one alkyl group having from 1 to 4 carbon atoms, such as ethyl and in particular methyl,

X is loyoylfufyphenoxy, preferably m-sulfophenoxy, and especially p-aulfophenoxy,

Y represents a vinyl group or an ethyl group which contains a beta-linked radical which is an alkali-eliminable anion, such as a beta-thiosulfatoethyl group (corresponding to the formula -C ^-CHH-S-SOje M as defined above), beta-phosphatoethyl a group (reflecting the general formula -CHg-CHg-OPOMg with M as defined above), a beta-chloroattyloxy group, a botanyloxyattyl group, and preferably a beta-sulfatoethyl group (corresponding to the general formula -CHg-CHg-OSO2); M with M as defined above).

General symbols R ', R, R ^J and R may be mutually the same or different meanings.

Besides the already mentioned preferred compounds of formula 1 may be emphasized are those ngvíc azosloučenity ^p ccording inventions dim ^R '= a ^{and magnesium, R} is a methyl group or metboxyskupinu preferably věak is hydrogen and -SOg group Y is bonded in mees- position, particularly preferably at position 1 to the amino group. It is to be emphasized that the azo compounds according to the invention are those in which D represents a ta- or para-phenylone group substituted by one or two sulfo groups. Also preferred are. compounds according to the invention in which Y represents a vinyl group, in particular a beta-sulfatoethyl group. If ^YM was substiuuovanou R3 is n-Butyl tulle Stopnete ^{1 and} 3 atoms UHN-this group "preferably subst ^^ carburised sulfo, carboxyl or acyloxy, ^ jlkjnoylalinoskuoinou with 2-5 carbon atoms.

The data below used throughout the specification indicates that the alkyl or alkylene moiety contained in the group consists of 1 to 4 carbon atoms.

The novel azo compounds may be present both in the acid form and in the form of their salts. Preference is given to these compounds in the form of salts, in particular in the form of alkaline salts. and alkaline earth metals, and are also preferably used in the form of these salts for dyeing (here and in the prior art is understood to be in general shear and including - printing) materials containing hydroxyl and / or carboxemido groups, in particular fibrous lajeas. |

It is an object of the present invention to provide a process for the preparation of the aforementioned and defined compounds of formula (1) by reacting a compound of formula (II).

(II)

in which

A represents a hydrogen atom or a group of formula (a) or (b)

X

AA ^CI (b) a

2

D, R, R, X and Y have the meanings given above, in the case of an amine of formula II in which A is a group (a) after its diazotization to the diazonium salt with a compound of formula III

(III) in which:

В a li ³

Mají are as defined above and are hydrogen or (b *) or (c *)

Cb ')

Cc ') where

D and X have the meanings given above, whereby a known L A hydrogen atom then В represents a group of formula (c *), if A represents a group of formula (а) then В represents a hydrogen atom and if A represents a group of formula (b) , then V represents a group of formula (b ').

The process according to the invention can be further elucidated by the following specific embodiments, in which the diazonium compound of the amine of formula 2

NH — NHX

d-nh ₂ (2) wherein

2

Ж, R, D, X and Ϊ are as defined above, coupling with a pyridone derivative of the general formula 3 wherein:

B and B ³ have the meanings given above

(3) or an amino compound of formula 4

R ³ (4) wherein

D, R and r3 are as defined above, reacted with a monochlortriazine derivative of formula 5

X - ^ x _N ^ CI CI wherein

2

R, R, X and Y have the above meanings.

(5)

In the starting compounds of formulas (2) and (5), Y may also be a beta-hydroxyethyl group. The compounds of the formula I in which I can be prepared according to the invention, in which I is a beta-hydroryethyl group, can be converted into the compounds of the formula I according to the invention by means of the corresponding esterification or acylating agent analogously to known methods. wherein Y is an ethyl group that is substituted in the beta-pn2cse with an ester group.

It is preferable to use such as aesthetic sulphation, i.e. converting a beta-hydroxyethyl group to a beta-sulfaethylethyl group analogously to numerous procedures known in the literature, with sulfuric acid or sulfuric acid containing sulfuric acid being preferably used as the sulfating agent. The sulphation reaction can be carried out in a temperature range between -5 ° C and + 50 ° C, preferably at a temperature between 0 to 10 ° C,

The amines of the formula (2) which serve as starting materials can be prepared analogously to known processes, for example by reacting the monochlonetriolio derivative of the formula (5) with a diamino compound of the formula H ₂ ND-NHg defined above,

Thus, compounds of the general formula (5) which serve as starting materials can be prepared analogously to known processes by condensation of the dihenylthiazine derivatives of the general formula (6).

in which

2

Y, R, and R are as defined above, with phenolsulfonic acid, preferably m- or p-phenolsulfonic acid.

The preparation of the starting compounds of the formula (6) is also carried out analogously to known methods by reacting amines of the formula (7)

17) in which i

Y, R, and R are as defined above, with cyanuric chloride (2,4,6-trichloro-1,3,5-triazine).

The reaction of the cyanuric chloride with the aminoazo compound of formula 7 to form the compound of formula 6 can be carried out in an organic or aqueous organic medium. It is preferably carried out in an aqueous medium with the addition of acid-binding agents, such as alkali metal or alkaline earth metal carbonates, alkali metal or alkaline earth metal bicarbonates or alkali metal or alkaline earth metal hydroxides or alkali metal acetates, the alkali metals and alkaline earth metals are preferably sodium, potassium or calcium. Acid binding agents are also tertiary amines such as pyridine or triethylamine or quinoline. These condensation reactions are carried out at a temperature between -10 ° C and * 40 ° C, preferably between -10 ° C and * 30 ° C, particularly preferably at a temperature between 0 ° C and * 10 ° C, as well as at a pH between 1 , 0 and 7.0, preferably between 3.5 and 5.

The condensation of the dichlorotriazinyl derivatives of formula 6 with phenylenediaminosulfonic acids can also be carried out in an organic or aqueous organic medium. Preferably, however, it is carried out in an aqueous medium, with the addition of an acid-binding agent, if necessary. The condensation of phenolsulfonic acids with monochlortriazine derivatives is carried out at a temperature between 10 and 60 ° C, preferably between 25 and 40 ° C, and at a pH between 5 and 8.5, in particular between 6.5 and 8.

The reaction of the monochlortriazine derivatives of the formula 5 with the amines of the above-defined formula H, N-D-NH4 or the aminoazo compounds of the formula 4 can also be carried out in an organic or aqueous organic medium. Preferably, however, it is carried out in an aqueous medium, optionally adding an acid binding agent such as the above. The reaction of these amino compounds β with these monochlorotriazinylderivatives is carried out preferably at a temperature between 20 and 80 ° C, preferably between 30 and 70 ° C, and at a pH between 2 and 8, in particular between 3 and 6.5.

The diazotization of the amino compounds of formula (2) is carried out analogously to known procedures, for example in an aqueous organic and especially in an aqueous, acidic environment by treating nitric acid such as at pH values between 0.5 and 3 and at temperatures between -5 ° C and * 15 ° C. . The reaction of the diazonium compounds with the pyridone derivatives of the general formula (3) is likewise carried out analogously to known methods, for example in aqueous-organic, but mostly aqueous, in a slightly acidic to neutral or in a very weakly alkaline range.

pH values, such as pH values between 4 and 7.5, read between 5 and 7, and at 5 and ° C.

The amino compounds of the general formula (7) which serve as starting materials for the preparation of the compounds according to the invention are represented, for example, by the following compounds:

1-amino-3- (beta-sulfatoethylsulfonyl) pool,

1-amino-2-methoxy-5- (beta-sulfatoethylsulfonyl) benzene,

1-Amino-2-methoxy-4- (beta-sulfatoethylsulfonyl) benzene,

1-amino-2-methyl-5- (beta-sulfatoethylsulfonyl) benzene,

1-amino-2-methyl-4- (beta-sulfatoethylsulfonyl) benzene,

1-amino-4-methoxy-5- (beta-sulfatoethylsulfonyl) benzene,

1-amino-4-methyl-5- (beta-sulfatoethylsulfonyl) benzene,

1-amino-2-methoxy-5-methyl-4- (beta-sulfatoethylsulfonyl) benzene,

1-amino-2,5-dimethoxy-4- (beta-sulfatoethylsulfonyl) benzene,

1-Amino-2,4-dimethoxy-5- (beta-sulfatoethylsulfonyl) benzene,

1-Amino-2-methyl-5-methoxy-4- (beta-sulfatoethylsulfonyl) benzene

2-chloro-1-amino-5- (beta-sulfatoethylsulfonyl) benzene,

4-chloro-1-amino-3-methyl-3- (beta-sulfatoethylsulfonyl) benzene,

5-chloro-1-amino-2-methoxy-4- (beta-sulfatoethylsulfonyl) benzene, as well as optionally the corresponding butylthiosulfatoethylsulfonyl, beta-phosphatoethylsulfonyl, beta-chloroethylsulfonyl, beta-acetoxyethyleulfonyl and vinylsulfonyl derivatives and optionally the beta-hydroxyethylsulfonyl derivatives of these beta-sulfatoethylsulfonyl compounds, further preferably 1-amino-4- (beta-sulfatoethylsulfonyl) benzene and its corresponding thlosulfatoethyl-, phosphatoethyl-, chloroethyl-, acetoxyethyl- and vinyl-derivatives and optionally beta-hydroxyethyl derivatives.

The pyridone derivatives corresponding to the general formula 3 which serve as starting materials for the preparation of the azo compounds according to the invention are, for example, the following compounds:

4-Methyl-6-hydroxy-2-pyridone

1,4-dimethyl-6-hydroxy-2-pyridone,

1-ethyl-4-methyl-6-hydroxy-2-pyridone,

3-Cyano-4-methyl-6-hydroxy-2-pyridone

1,4-dimethyl-3-cyano-6-hydroxy-2-pyridone,

1-ethyl-3-cyano-4-methyl-6-hydroxy-2-pyridone,

3-carbamoyl-4-methyl-6-hydroxy-2-pyridone,

1-methyl-3-carbamoyl-4-methyl-6-hydroxy-2-pyridone,

1-ethyl-3-carbamoyl-4-methyl-6-hydroxy-2-pyridone,

4-Methyl-6-hydroxy-2-pyridone-3-sulfonic acid

1,4-dimethyl-6-hydroxy-2-pyridone-3-sulfonic acid, 1-ethyl-4-methyl-6-hydroxy-2-pyridone-3-sulfonic acid, 3-sulfomethyl-4-methyl-6-hydroxy- 2-pyridone,

3-sulfomethyl-1,4-dimethyl-6-hydroxy-2-pyridone,

1-ethyl-3-sulfomethyl-4-methyl-6-hydroxy-2-pyridone,

1- (beta-hydroxyethyl) -3- (alpha-sulfoethyl) -4-methyl-6-hydroxy-2-pyridone

- (beta-hydroxyethyl) -4-methyl-6-hydroxy-2-pyridone,

1- (beta-hydroxyethyl) -3-cyene-4-methyl-6-hydroxy-2-pyridone

1- (beta-hydroxyethyl) -3-carbamoyl-4-Mithcah ^1- 6-hydroxy-2-pyridone,

1- (beta-hydroxyethyl) -4-methyl-6-hydroxy-2-pyridone-3-sulfonic acid,

- (beta-sulfatoethyl) -4-methyl-6-hydroxy-2-pyridone,

1- (beta-sulfatoethyl) -3-cyano-4-methyl-6-hydroxy-2-pyridone

- (beta-sulfatoethyl) -3-carbamoyl-4-methyl-6-hydroxy-2-pyridine,

1- (beta-sulfatoethyl) -4-methyl-6-hydroxy-2-pyridone-3-sulfonic acid,

1- (BE ^<ta-sul ^ f ^ l ^ ceítly) -4 m ^ ei ^ ^i, yl - <- 4 ^ j ^ d ^] ^ C ^ XY2 _pyri-don)

1- (beta-sulOoettyl) зЗ-кагЬашоуХ ^ -тегЬуХ-б- ^ агоху-г-ругЗ.аоп,

1- (beta-Eulloethyl-4-methyl-6-lydroxy-2-pyridone) -3- (2-carboxylic acid),

-carbaxymethyl-N-imideih-γ-hydroxy-1 H -pyridone,

4kai ^ b ^ oxy ^ etety ^ y-3 - ^ ^ 1 ^ - ^ 4 ^ - ^^ eeih ^ y ^ -6-h ^ <^ i ^ <^ 2X ^ - ^ 1 ^ - ^ 1 ^ : ^ y ^: idon

1-carboxynaehly-6-carbamooy-4-methyl-6-hydroxy-4-pyridone,

4karboxymaeřiyy ^{ineehyy-4-H-6-r-droixy4} ppyidon-3-sulfonic acid. 1- (beta-4-carboxyethyl) -4-alkyl-4-hydroxy-4-pyridone,

1- (beta-carbonyl) 4-cyano-444-methyl-4-hydroxy-1-pyridone;

- (beta-carboxyethyl) -3-haloamoyl-4-methyl-6-yyroxy-4-pyridone,

1- (Beta-4-methyl-ethyl) -4-methyl-6-hydroxy-pyrimidone-3-sulfononic acid,

1- (beta-acetylaminoethyl) -4-methyl-6-hydroxy-4-pyridone,

1- (beta-Acetaminoethylisazin-4-methyl-4-methyl-4-hydroxy-4-pyridone), 14- (4-methyl-4-ethyl-4-methoxyl) 434carbamooy-4-meethrl-6-hydroxy-pyridone,

14 (beta-acetyl-aminoethyl) -4-methyl-6-hydroxy-4-pyridone-3-sulfonic acid,

14 (beta4-acetyllaainopropyl) 44-methyl-4-hydroxy-pyridone,

1- (beta-acetylamino-propyl) -3-cyano-4-methyl-4-hydroxy-γ-2-pyridone,

1- (beta-aceyyaaminopropyl) -3-cabamoyl-4-methyl-64-hydroxy-pyrimidone and

-1- (beta-acetylaminopropyl) -1,4-methyl-4-hydroxy-piperidone-3-sulfonic acid.

The diamino compounds corresponding to the aforementioned general formula Hgtf-D-KH which may serve as training substances for the production of the azo compounds of the invention are, for example, 1,34-diiminobenzene-44sulfonic acid, _1β -diaminobenzene-5-εulfonic acid, 1 ₉ 4-diaminobens®. n-2-auOfonovou acid - 44diaminotoluen "5- sulOonovou acid - 6-44dlЁminotoluen вulOonovou acid, - _5-di-S inotoluen444 uiOonovou acid 1.34 -diaminoЪ®nszn _4-9-б disulfononou acid and 1,4 '4iaainobenzene' 2 _{9 with} 5-4isulfononic acid.

The de-coupling and isolation of the compounds of formula (1) produced by the process according to the invention can be carried out by generally known methods, such as by drying the reaction mixture. by means of electrolytes, such as sodium chloride or potassium chloride, by evaporating the reaction solution, for example by spray drying, and a coupling agent can be added to the reaction solution or solution.

The compounds of the formula I according to the invention are fiber-reactive and have very good properties as bamboo. Thus, they can be used for dyeing (including printing) materials containing hydroxyl groups and / or carboxamido sulfins. It is also possible to use solutions which are used in the synthesis of the compounds according to the invention, optionally after addition of the pures and, optionally, after concentration, which are directly fed as a liquid dye preparation for use in baroque use.

Accordingly, the present invention also relates to the use of the compounds of the formula I according to the invention for dyeing (including printing) materials containing hydroxyl groups and / or carboxamido groups or methods for their use on such substrates.

These materials are suitable in the form of fibrous molars, in particular in the form of textile fibers such as yarns, windings and fabrics. The process may be analogous to known methods by applying the moleo compound of the formula (1) in dissolved form to or impregnating the substrate, and then fixing it to the material or material, optionally with heat or and / or optionally by treatment with an alkaline active agent.

The hydroxyl group-containing materials are those of natural or synthetic origin, such as fibrous cellulose materials or regenerated cellulose materials and polyvinyl alcohols. The cellulosic fibrous material is preferably cotton, but also other vegetable fibers, such as flax, hemp, jute, and ramie fibers. The regenerated cellulose fibers are, for example, viscose staple and viscose rayon.

Carboxamido-ringing materials are, for example, synthetic and natural polyamides and polyurethanes, particularly in the form of fibers, for example wool, and other animal fibers, silk, leather, polyamide-6,6, polyamide-6, polyamide-11 and polyamide-4.

The compounds of general formula (I) produced by the process of the invention can be applied and fixed to said substrates, in particular to said fibrous rattrials, by application techniques known for water-soluble dyes, in particular for water-soluble and fiber-reactive dyes. Such dyeing and fixing procedures are described in numerous places.

Thus, with these dyes, very good dye yields, as well as color compositions, are obtained on the cellulose fibers by long bath extraction processes using a variety of acid-binding agents and optionally neutral salts such as sodium chloride or sodium sulfate. The dyeing is preferably carried out in a water bath at temperatures between 60 ° C and 105 ° C, optionally at 50 ° C. at temperatures of up to 120 ° C under pressure and optionally in the presence of conventional dyeing preparations.

In this case, the material can be introduced into a warm bath and the bath is slowly heated to the desired dyeing temperature and the dyeing process is completed at this temperature. Neural salts which inhibit dye withdrawal may also be added to the bath even after the dye has been reached. temperature at which the actual dyeing is carried out.

The dyeing process also achieves excellent dye yields and very good color compositions on the cellulosic fibers, and fixation can be carried out by dwelling at room temperature or at elevated temperature, for example up to about 60 ° C, by steaming or dry heat in the usual manner.

Also according to conventional printing processes for cellulose fibers, which can be carried out in one phase, for example by printing with a printing paste containing sodium hydrogencarbonate or other acid binding agent and subsequent steaming at temperatures of 100 to 103 ° C, or biphasic, for example by printing neutral. or a weakly acidic ink and subsequent fixation by guiding the printed material with a hot alkaline bath containing electrolyte, or by overprinting the printed material with an electrolyte, followed by a delay or by steaming or by applying dry heat to the overloaded material. they receive color-intensive prints with good contour status and clear white fund. Kvaita of these prints remains virtually unaffected due to currency fixing conditions.

For fixing with dry heat according to the usual thermofixation procedures, hot air at a temperature of 120 to 200 ° C is used. Preheated steam and pressurized steam at temperatures up to 160 ° C can also be used in a conventional water vapor at a temperature of 101 to 103 ° C.

Acid binding agents and agents for fixing the compound of Formula 1 to cellulose fibers are, for example, water-soluble alkali metal and optionally alkaline earth metal salts of inorganic or organic acids, or compounds which release alkali in the heat.

Mention may in particular alkali metal hydroxides and alkali metal salts derived from ^'of weak to medium inorganic or organic acids, wherein the compounds of the alkali metals include preferably sodium compounds and potassium compounds. Such acid binding agents are, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium formate, sodium phosphate, sodium phosphate, sodium trisodium acetate, water glass or sodium phosphate.

By treating the compounds of the invention with acid binding agents, optionally under the effect of heat, the compounds of the invention (dyes) chemically bind to cellulose fibers. In particular, the dyeings on the cellulose fibers exhibit excellent wet centuries after the usual rinsing action to remove unfixed dye portions and, moreover, unfixed dye portions can be easily washed off due to their good cold water solubility.

The dyeing of polyurethane and / or natural or synthetic polyamide fibers is usually carried out from an acid medium. Thus, for example, acetic acid and / or ammonium sulfate and / or acetic acid and ammonium acetate or sodium acetate can be added to the dyeing bath to achieve the desired pH. In order to achieve a uniform color uniformity, it is recommended to add conventional auxiliary leveling agents, such as those based on the reaction product of cyanogen chloride with triple molar amounts of amnobenzenesulfonic acid and / or aminonothalenesulfonic acid or on the basis of the reaction product, for example, with stearyllamine with ethylene.

As a rule, the dyeing material is introduced into the bath at a temperature of about 40 DEG C., where it is kept in motion for some time, and the dyeing bath is then treated. to the desired weak acid pH, preferably by the addition of acetic acid and the actual dyeing is carried out at temperatures between 60 and 98 ° C. The dyeing can also be carried out at the boiling point of the dyeing bath, i.e. at temperatures up to 120 ° C (from pressure).

The dyeings and prints obtained using the compounds of the formula I according to the invention are generally characterized by bright greenish tones over reddish-yellow to yellowish-orange shades and a high dyeing intensity. In particular, dyeing and printing on cellulose fiber mattrials have very good light fastness and good to very good wet fastness, such as underwear fastness, washboard fastness, water fastness, seawater fastness, color fastness. and fastness to sweat, good pleating, ironing and abrasion.

Of particular importance is my use of the compounds of formula (I) according to the invention also for dyeing wool while reacting to fibers. In particular, non-felting or low-felting wool can also be dyed (cf., for example, H. Rath, Lehrbuch der Textilchemie, Springer-Verlag, 3rd ed. / 1972 //, pp. 295-299), in particular wool treated with so-called &quot; By the method according to the second method (page 298), J. Soc., Drers and Coloorrsts 1972. 93-99, and 1975. 33-34) with very good stability.

The dyeing of the wool is carried out by a conventional and known dyeing method by applying the fiber-reactive compound of the formula I preferably first from an acid dye bath having a pH of from about 3.5 to 5.5 under pH control by the drawing procedure and at the end of dyeing The pH is shifted to the neutral and possibly weakly alkaline pH up to a pH of 8.5, in order to achieve a complete reactive bond between the dye of formula 1 and the fiber, in particular when the desired hue is achieved. At the same time, the non-vigorously bound portion of the dye is released.

Described here. The method also applies to dyeing fibrous materials of other natural polyamides - or synthetic polyamides and polbureehtoes. The dyeing is carried out at temperatures from 60 to 100 ° C, but can also be carried out in closed dyeing devices at temperatures up to 106 ° C. Since the water solubility of the compounds of formula I is very good, they can also be used advantageously in conventional continuous dyeing processes. The dyeing density achieved in the desert is very high.

The compounds of the compounds on the fibrous materials, particularly in the reactive dyeing of wool, have bright, greenish reddish yellow to yellowish-orange tints. A high degree of bath depletion can be found at temperatures of 100 to 106 ^° C in dyeing.

In the case of the dyeing obtained by the compounds of the general formula (1) according to the invention, the otherwise customary additional action of ammonia on the dyeing article can be avoided. In comparison with the structurally similar known dyes, the dyes according to the invention surprisingly show a very good color composition, while achieving brilliant shades even in saturated tones.

In addition, they have a very good ability to combine with other fiber-reactive dyestuffs, which allows a surprisingly uniform coloring of the fibers. Likewise, the oattrial of wool fibers of different provenance can be uniformly colored with the compounds according to the invention. Optional leveling aids such as N-meethllaurin may be added to improve egality.

Using conventional dyeing agents which have fiber affinity, the compounds of the present invention also provide uniform dyeing on wool with a non-felting finish or a low felting finish.

In light and even medium shades, even without additional ammonia treatment, a very good level of wet fastness can be achieved, but if necessary, additional ammonia treatment can be advantageously used. In addition to the high light fastness of these wool dyes, very good wet fastness, in particular excellent sweat fastness under alkaline conditions and very good fastness in linen at a temperature of &lt; 60 ° C, should also be mentioned, even with high shade intensities.

The following examples serve to illustrate the invention. Parts are by weight, parts% by weight unless otherwise stated. Heoothermal parts are proportional to parts by volume as kg per liter.

The compounds described in the examples by formulas are given in the form of free acids. In general, these compounds are prepared and isolated in the form of their salts, especially in the form of sodium or potassium salts, and in the form of salts, these compounds are also used for dyeing. Likewise, the starting materials mentioned in the following examples, in particular in the table summarized examples, can be used in the synthesis in the form of the free acid, as such or in the form of their salts, preferably salts with alkali metal such as sodium or potassium salts. .

Example 1

a) A non-European aqueous solution of 56 parts of 4- (methyl-1-ethanoethyl-1-phoyl) and in 300 parts of water is allowed to flow into a suspension of 38.6 parts of cyanide * brick and 1 part of commercially available diluent in 50 parts of water and 200 parts under vigorous stirring. . The pH between 2 and 4 is maintained with sodium hydrogen acetate during the acylation reaction; the temperature is initially 0 ° C, 10 ° C. While heating to 25 ° C, 35 parts of p-penoic acid are now added as a concentrated aqueous solution and the pH is adjusted to 7.5 with sodium carbonate; and until the end of the second condensation reaction, the reaction mixture is further stirred under these conditions. ,

(b) The solution obtained under (a) is added dropwise to a neutral aqueous solution of 37.5 parts of 1,3-phenylenediaein-4-sulfonic acid at 50 ° C. After completion of this third acylation reaction, the reaction mixture is cooled and added to the reaction mixture. parts of ice and 50 parts of a 31% aqueous hydrochloric acid solution, and then diazotization is carried out with an aqueous solution of 12.5 parts of sodium nitrite.

c) To a solution of the diazonium salt solution prepared in accordance with b) is added 39.5 parts of 1,4-diethyl-6-hydroxy-η 1 -2-pyridoo-3-sulfonic acid; during this coupling reaction, the pH is maintained between 5 and 5.5 with sodium hydroxide.

The thus prepared eoontha compound of the invention is isolated in a customary manner, for example by evaporation of a neutral solution, spray drying or salting out with the aid of a salt. electrolyte salts such as potassium chloride. A yellow powder is isolated which contains the sodium or potassium salt of the compound of formula

This atro-compound of the invention, when dissolved in water, has a maximum pH of 418 nm in the absorption spectrum.

As a dye, it has very good properties and provides on the materials described in the description, such as, in particular, cellulosic fibrous materials, for example cotton, by application and fixation methods customary in the art, especially for fiber reactive dyes, greenish yellow dyeings and prints and good stability in light and with good wet fastness, especially with good fastness to dust, washboard, discoloration, chlorine water and number.

Example 2

a) A neutral solution of 54 parts of 1,4-pheryleidino-2,5-distonic acid in 200 parts of water is diazotized with an aqueous solution of 14 parts of sodium nitrite after addition of 200 parts of ice and 70 parts of 319S hydrochloric acid. 52 parts of 1- (bromo-methyl) -3-cyano-4-methyl-6-hydroxy-2-pyridine are added for coupling and the pH is maintained at 5 to 6 during the coupling reaction.

b) The amine chain produced according to a), preferably in the form of its aqueous reaction solution, is added to a solution of the double acylation product of 4- (bromotrifluorosulfonyl) Daniline, cyanoxuchloride and p-frsulfonic acid which has been produced. according to example-1a). In order to carry out the third ecylation reaction, the temperature of the reaction mixture is raised to 60 [deg.] C. and the pH is maintained during the reaction by sodium hydrogen carbonate between

5,5 and 6.

The urea compound thus produced is isolated in the usual manner, for example by spray drying or potassium chloride salting. A dark yellow powder is obtained which contains the sodium or potassium salt of the compound of the formula

SOjH

This azo compound of the invention, dissolved in water, exhibits an absorption maximum at 439 nm over a wide range of absorption spectra. As a dye, it exhibits very good properties, in particular very good fiber-reactive dye properties, and provides on the materials described herein, such as, in particular, cellulosic fibrous materials, such as cotton, by application and fixation methods conventional in the art. which are described and used for fiber-reactive bervatives, color-intensive, bright reddish-yellow coloring and prints with good fastness and good wet fastness, in particular good fastness in underwear, washboard, sweat and varnish.

Example 3

In order to prepare the monoazo compound of the invention, the procedure described in Example 1 was followed, but in step (a), 4- (beta-sulfethylmethylsulfooyl) with an equivalent amount of 4- (beta-thiosulfazolylethylsulfonyl) was substituted.

After working up the reaction solution and isolating, a powder is obtained which, in addition to the electrolyte

I contains a salt of a compound of the following. alkali metal formulas

CH ₂

O

CH3

SO3H

This azo compound of the invention exhibits an absorption maximum at 418 nm in aqueous solution. It also has very good dyeing properties and provides, for example, on cotton by application and fixation methods customary in the art, in particular those used for fiber-reactive dyes, color-intensive, green-yellow coloring and prints with good fastness to light and good wet fastness, such as good fastness to underwear, washboard and varnish, as well as good fastness to sweat.

Example 4

For the preparation of the azo compound according to the invention, the procedure described in Example 1 is followed, but substituting the process described in (a) herein for an aqueous solution of 4- (beta-sulfatoethylsulfonyl) aniline with a solution of 39 parts of sulfonyl ailine in 200 parts by volume of acetone.

After the usual treatment of the reaction solution and isolation, a powder is obtained which, in addition to the electrolyte, contains a salt of a compound of the following formula with an alkali metal, such as a sodium salt of the formula

NH — NH

O

SO ₂

Sat ₃ H ^H0 1

CH ₃

SO3H

This compound has a maximum at 419 nm in the aqueous solution over the visible absorption spectrum. It also exhibits very good fiber-reactive dye properties as a dye and provides, by application and fixation methods common in the art, for example, cotton, intense, greenish-yellow dyeing and prints with good fastness to light and good wet fastnesses with the same keenness the quality of the dyeings and prints obtained with the azo compound of the invention of Example 1.

Example 5.

For the preparation of the azo compound of the invention, the procedure of Example 1 is followed, but substituting the aqueous solution of 4- (beta-trifluoromethylsulfonyl) aniline with 46 parts of 4- (tert-chloroethyl) sulfone; ).

After working up the reaction solution and isolating, a powder is obtained which, in addition to the electrolyte, contains an alkali metal salt of the compound of the following formula.

CH ₃

SO3H

This compound also has an absorption maximum in an aqueous solution at 418 nm. As a dye, this compound has very good properties and provides, for example, on cotton using fiber-fixing and fiber-fixing dyes with color-intensive, greenish-yellow hues in bloom which is the same as that of the dyeings and prints obtained using the azo compound of the invention of Example 1.

Examples 6 to 78

In the following examples, which are summarized in the table, further monoazo compounds are described correspondingly. of formula (1) by means of their components to which they are built along with the remainder of the cyanuride. These compounds can be prepared from these amino compounds and cyanoborohydride and from the coupling components according to the method of the invention, such as according to one of the process variants described in Examples 1-5 above.

These compounds are preferably isolated in the form of their alkali metal salts, such as sodium or potassium salts. The starting components for these compounds are reported when they contain an acidic group, in the form of the free acid.

The monoalcohol compounds according to the invention of Examples 6 to 78 also exhibit very good fiber-reactive and poaltyte-dye properties on the materials mentioned in the description, such as, in particular, cellulosic fibrous materials such as cotton, color intensive dyeings and prints with good fastness to the shade shown for dyeing on cotton for each example in the table.

In the examples 6 to 78 mm, the symbols Z, '' to Zg are the successor meanings (where #, when they contain an acid group, are given in the form of the free acid):

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Example Anine of formula 7 X Diamino compound Pyridone derivative Color number of formula 3 h ₂ nd-nh ₂

MD XD XJ MU

► ► ► ► 0 0 0 0 β >> ЗЧъ O* Φ P Φ P 0 P 0 P H 0 rH 3 rH 3 H 5 ®H Φ rH Φ rH 0 rH MM MM NM MM

XD XD ΜΦ ► ► 0 0 0 £ >> Φ P Φ P 0 P rH 0 rH 3 rH 5 0 r-l Φ rH Φ rH MM MM MM

i >> 40 ΧΒ >> ► and ι >> '* 0 » >> 40 K t> X Ο X> X 5 » X ► O o Ο β ο 0 Ο Ο ο ο fa β Ρ Ο fa β fa β fa β 0 O «Β * 4 0 Ο 0 Ο 0 Ο MS >> Wh Λ Η t 3 i w i 3 i 3 i 0 SO W so i i ΓΠ \ O 0 u> ω SO 0 t i rH ΓΟ rH A —I Η ^r H Α whose whose >> 1 Λ β whose Whose P o Ρ ο Ρ ο Ρ ο Ρ ο Φ0 0 φ 0 '0 Φ 0 0 Φ0 Φ Φ 0 Φ θΗ β 0-H β S · Η β Θ · Η β θ Η β Η PH • r fa-Η • Η | fa · Η • Η fa · Μ Η Η fa · Η • β> rH 0 >> rH 0 >> rH 0 >> «Η 0 >> «Η i ΛΦ i Ο.Φ i Ο. Φ i 0. Φ ι α φ I «0 'Φ ι w Μ 1 0 0 * i 0 1- 1 0 --7 £ «OJ >> - i 44 -7 £ «OJ>» - t -7 £

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Example Aminine of Formula 7 X diamine compound Pyridone derivative Color number of Formula 3 hue

Xl) XD

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Application Example 1 parts of the compound of the invention (in the form of the sodium salt) of Example 1 was dissolved together with 50 parts of urea in 300 parts of water. The solution obtained is stirred at a temperature below 40 DEG C. in 400 parts of non-wiping, aqueous 4 * alginate suction. 10 parts of sodium carbonate are then added and the 4% aqueous alginate thickener is added to a total of 1000 parts. The mixture is mixed well and the cotton fabric is printed with a crushed printing paste, which, after being stiffened at 60 ° C, is treated for 5 minutes with saturated steam at 100 and 103 ° C in a commercially available steaming aggregate. The printing is then completed by rinsing in cold and hot water, washing with neutral detergent, and rinsing again in water. After drying, the color-intensive green-colored printing 8 is obtained with very good light fastness and very good wet fastness.

Application example 2

The fabric with mflercerised cotton is covered with a 20 ° C water dye bath at bath consumption. 80% by weight of the goods, with the dye bath containing 20 g of the sodium salt of aststyl according to the invention of Example 1, as well as 18 g of 33% sodium hydroxide per liter. Let 8 holin at mild temperature. *

The dyeing is then completed by rinsing in cold water, followed by treatment with an aqueous bath containing milk of sodium acetate and rinsing again in cold water and hot water. After drying, a color-intensive greenish dye with very good light fastness and very good wet fastness is obtained.

Application example 3 ♦ ϊ

100 parts of mercerized cotton fabric are treated for 10 minutes at 10 ° C in 3,000 parts by volume of an aqueous dye bath containing 5 parts of the sodium salt of the compound of Example 1 as well as 150 parts of anhydrous sodium salt. 15 parts of anhydrous sodium carbonate are added. and 4 parts of 33% sodium hydroxide. The dyeing is continued for 60 minutes at 60 ° C. Thereafter, the reddish process of the dyed fabric is completed in a conventional manner, for example as described in Application Example 2. A color-intensive, greenish-colored dyeing with very good light fastness and very good wet fastness is obtained.

Application Example 4

100 parts of wool fabric are placed in an aqueous barding bath at 40 ° C consisting of 3,000 parts of water, 2 parts of sodium salt of the compound of the invention described in Example 1, 0.15 parts of the editorial product 12 moles ethylene oxide β 1 mol steary laminate 2 parts of ammonium acetate and 2 parts of 60% aqueous acetic acid. The dyeing bath temperature was raised to boiling point for 30 minutes and dyeing was continued at 100 ° C for 60 minutes. After the usual manufacturing and finishing of the obtained vloy dyeing, this wool fabric exhibits a color-intensive, greenish-dense color shade with a very good fastness to light and a very good wet fastness.

Applying Example 5

It is dyed as described in Application Example 4, but the woolen fabric is replaced with 100 parts of .beta.-polycaprolacaao fiber. Color-intensive, sele-rich coloring with good durability is also obtained.

According to the above-mentioned application examples, other compositions of the present invention may also be used in the dyeing and printing processes described herein in the Examples illustrating the production process, as well as in the Examples summarized in tabular form.

A ^ i ^ logi ^ i ^ i ^ m way! For example, the films of these dyeing and printing methods, which are required in Application Examples 1 to 5, are obtained with some other dyes of the present invention also very color intensive dyes and prints having good fastness to light and good wet fastness to color shades. , which are given for the respective examples or examples summarized in the table.

Claims (10)

SUBJECT TO THE INVENTION 1. Method. - the production of oonoazolefins soluble in water (1) therein. . ^R1 represents a ^d i ^{K u} altylovou group having 1 ⁴ carbon atom e ^{F y} ^ гИк ^ and ^L ^ ^k ox ^{y P} inu SKU ¹ -C 4 carbon atoms or chlorine atoms, R @ 1 represents a hydrogen atom, a C1 -C4 alkyl group or a C1 -C4 alkoxy group, ^R @ 3 represents a hydrogen atom or a C1 -C4 alkyl group optionally substituted by a hydroxyl group, a C2 -C5 alkalooylallooostopinyl group tolio, a sulfato group of the formula -OSO ^ M, a carbystystopioyl of the formula -COOM or a sulfo group of the formula -SO ^ M », and in these formulas M - represents a hydrogen atom or the equivalent of a monovalent, divalent or trivalent metal, in particular an alkali metal or an alkaline earth metal, R @ 2 - represents a hydrogen atom, a sulfmethyl group, a carbamyl group, a cyano group or a sulfostopine, D is m- or p-phenylan which is substituted by one or two sulfo groups or one or two sulfostopines and one alkyl group having 1 to 4 carbon atoms, X stands for loynoйJfofeoyχystopia, Y represents a vinyl group or an ethyl group containing a beta-linked residue in the beta-position which is alkali-allyl-lithium as the anion, 12 3. wherein R -, R, R - and R may have the same or different meanings, characterized by reacting a compound of formula II wherein:. A represents a hydrogen atom or a group of formula (a) or (b) (a) (II) and 1 2 D, R, R, X and Y have the above meanings, in the case of an amine of the general formula II in which A represents a group (a) after its diazotization to the diazonium salt, with a compound of formula III (III) have the meanings given above, and B represents a hydrogen atom or a group of formula (b *) or (c ') (b') (c ') wherein D and X are as defined above, and when A is hydrogen then B is a group of formula (O when A is a group of formula (a) then B is hydrogen and if A is a group of formula (b) then B is a group of formula (b ') _e AND 2. A process according to claim 1, wherein the starting materials used are the corresponding compounds of the formulas II and III to give compounds of the formula I in which R @ 1 is hydrogen, R @ 2 is hydrogen or methoxy or methyl, -SO ^ -i represents beta-sulfatoet yrlsulfanylovou group or a vinyl sulfonate oiylovou * · 3 group bonded in m- or p-position to the amino group not benzene nucleus, R ^J is hydrogen or alkyl having 1 to 4 carbon atoms, which is optionally substituted by carboxyl, sulfo or acetyleeiaosktoiaou or ^г ooionylaeinoskupinou, R represents sulloskupinu or cyano group, D is meta- or para-phenylene alkylene group, which is substituted by one or two sulfo, and M and X have the meanings given in point 1 »» 3. The process according to item 1 for the preparation of the compounds of the formula I as defined in item 1, in which A is an ethyl group which is in the beta position of the 8-substituted ester group, preferably a sulliculin, characterized in that The compounds of the formula II and III in which out is a beta-hydroxyethyl group, and the resulting compound corresponding to the formula 1 but in which Ϊ is a β-hydroxycarbonyl group, are reacted with or with a trifluoroethyl agent. an agent, preferably a sulphating agent. 4. The method of item 1 or. 2, enforced by that. The corresponding compounds of formulas (II) and (III) are treated as starting materials to give compounds of formula (1) wherein ^R is hydrogen. 5. A method according to claim 1 or 2, vyznnačoudící in that as the starting material after it pdpcjoíddajcí ^ compounds of the formulas II and III to give compounds of formula ¹ wherein R is and verifies ^lkyl group having ¹ to 3 carbon ^Cart thl ^y t ^which is pH-ga-substituted sulfoskuoinou. . 6. Process according to claim 1, 4 or 5, characterized in that the corresponding compounds of the formulas II and III are used as starting materials to give the compounds of the formula 1 wherein R is sulfo or cyano. 7. A process according to any one of claims 1, 4 or 5, wherein the corresponding compounds of formulas (II) and (III) are used as starting materials to form compounds of formula (1) in which D is a meta- or para-pherylene group. which is reduced by one or two sulfo groups. 8. A process according to any one of claims 1, 4, 5, 6 or 7, wherein the compounds of formulas (II) and (III) are used as starting materials to form compounds of formula (1) in which the group -SO2- ! means a beta-phenylethyl group or a vinyl group bonded in each case in the meta- or para-position to the aminostapine on the benzene ring. 1 * 9. A process according to claim 1, wherein the corresponding compounds of the formulas II-III are used as starting materials to form a compound of the formula CH ₃ SO _and H / ff HÓC ^T H, SO 3 H or an alkali metal salt of this compound. 10. The process of claim 1, wherein the corresponding compounds of formulas II and III are used as starting materials to form a compound of formula