CS227045B2 - Method of preparing monoazo compounds - Google Patents

Abstract

1. Compounds of the general formula (1) see diagramm : EP0064721,P12,F2 wherein M is a hydrogen atom or the equivalent of a metal, R is a hydrogen atom or the methyl, ethyl, methoxy or ethoxy group, and the vinylsulfonyl group in the benzene nucleus is in the meta- or para-position relative to the acylated amino group, and the second group of the formula -SO3 M in the naphthalene nucleus is bound in the meta-position relative to the acylated amino group.

Description

The invention relates to the technical field of fiber-reactive dyes.

From German Patent Specification 1,265,698, azo dyes are known which contain a monochlorotriazinyl fiber-reactive moiety and as a further fiber-reactive moiety contain a p-sulfatoethylsulfonyl group. These dyes, however, have some drawbacks in technical application, so that some requirements cannot be fully met.

We have now found new, valuable, water-soluble azo compounds of formula (1)

in which

M represents a hydrogen atom or an equivalent of a metal, in particular an alkali metal or an alkaline earth metal such as sodium, potassium, lithium and calcium,

R represents a hydrogen atom or a methyl group, an ethyl group, a methoxy group or an ethoxy group, and the vinylsulfonyl group on the benzene ring is in the meta- or para- position of the acylated amino group, and the second group -SO3M on the naphthalene ring is bonded

The dichloro-thiazmylamino-azo compounds of formula 2 can be prepared analogously to known methods by reacting the aminoazo compound of formula 4 in meta- or panaposition to an acylated amino group.

The novel azo compounds can exist both in acid form and in the form of their salts. Preferably, the compounds are in the form of salts, in particular in the form of alkali metal and alkaline earth metal salts, and are also preferably used in the form of these salts for dyeing (herein and in the following general description and including printing) containing materials. hydroxyl groups and / or carboxamido groups, in particular fibrous materials.

The present invention relates to a process for the preparation of the aforementioned and defined azo compounds of the general formula (1).

in which

M is as defined above and the second group of formula -SO3M on the naphthalene nucleus. Yippee . bonded in meta- or parapolysis to an acylated amino group, acts. an aromatic amine of formula 3

(3) in which

R is as defined above and the vinylsulfonyl group on the benzene ring is bonded in meta- or paraposition to the amino group.

The dichlortriazinylamino compound of formula 2 can be prepared analogously to known methods by coupling the diazonium salt of aniline-2-sulfonic acid with 1- (2 ', 4'-dichloro-1', 3 ', 5'-triazin-6'-yl) amino- 8-hydroxynaphthalene-3,6- or -4,6-disulfonic acid.

in which

M is as defined above, and the second group of formula -SO3M on the naphthalene core is bonded in meta- or parapolysis to the acylated amino group, with an equimolar amount of trichlortriazine (cyanuric chloride).

: Azo compound. 4 can be prepared analogously to the known process by coupling the diazonium compound of aniline-2-sulfonic acid with 1-acetylamino-8-naphthol-3,6 or -4,6-disulfonic acid followed by hydrolysis of the acetylamino group to the aminoazo compound under acidic or alkaline conditions .

The reaction of the dichlorotriazyl derivatives of the general formula 2 with the corresponding amino compounds can be carried out analogously to the known process. Such reactions are described, for example, in W. F. Beech, Fiber-reactive.Dyes, London 1970, p. 148 et seq.

The coupling reaction is preferably carried out in a pH range of 4. 7 and at a temperature between 0 and. '30 ^at C. The condensation reaction with amino dichlortriazinylderivátů is generally carried out in an aqueous medium, optionally in conjunction with an organic solvent at a temperature between 0 ° C and 70 °; preferably between' 20 degrees Celsius and 70 ° C and at a pH of preferably between 4 and 7.

The hydrochloric acid liberated in the condensation reaction is bound with acid binding agents such as sodium hydroxide or potassium hydroxide, sodium carbonate or potassium carbonate, sodium bicarbonate or potassium bicarbonate, sodium acetate or basic sodium phosphate.

The compounds of the formula I according to the invention can also be prepared according to the invention by reacting to the compound of the formula 6 (6):

OSO ₃ M

in which

R and M are as defined above, acting cautiously with an acid binding agent such as sodium carbonate or sodium hydroxide in a neutral to slightly alkaline, aqueous environment at a pH between 7 and 8.5 and at a temperature between 30 and 45 ° C. The conversion of the sulfuric acid ester compounds of the formula 6 into the vinyl derivatives of the formula 1 can also be carried out according to the invention by adding an equivalent amount of an acid binding agent to their reaction solution after the synthesis of the compounds of formula 6 and evaporating the reaction solution, such as by spray drying.

The separation of the compounds of the formula 1 produced by the process of the invention from the reaction mixture can be carried out by generally known methods, such as either by precipitation from the reaction mixture by electrolytes such as sodium chloride or potassium chloride, or as already mentioned for the synthesis variant of the invention by evaporating the reaction solution, for example by spray drying, and a buffering agent may be added to the reaction solution.

The compounds of formula (1) produced by the process of the invention have fiber reactive properties and have very good dye properties. They can therefore be used for dyeing (including printing) materials containing hydroxyl groups and / or carboxamido groups, and solutions of the compounds according to the invention which are formed during the synthesis, optionally after addition of a buffer or also after concentration, can also be used directly as liquid preparations for dyeing 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 materials, in particular in the form of textile fibers such as yarns, coils and fabrics.

Materials containing hydroxyl groups are materials of natural or synthetic origin, such as e.g.

cellulosic fibrous or cellulosic regenerated materials and polyvinyl alcohols. The cellulosic fibrous materials are 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-containing materials are, for example, synthetic and natural polyamides and polyurethanes, in particular 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 the formula (1) produced by the process of the invention can be applied and fixed to said substrates, in particular to said fibrous materials, by application techniques known for water-soluble dyes, especially water-soluble dyes and fiber-reactive dyes.

Thus, with these dyes, very good dye yields, as well as excellent color compositions, are obtained on the cellulose fibers by a long bath extraction process 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 and 105 ° C, optionally at temperatures up to 120 ° C under pressure and optionally in the presence of conventional dyeing aids. This can be done by placing the material in a warm bath and slowly heating the bath to the desired dyeing temperature and completing the dyeing process at this temperature. Neutral salts which accelerate dye uptake can only be added to the bath, possibly also after reaching the temperature at which the 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 by dry heat in the usual manner.

Also, according to conventional printing processes for cellulose fibers, which may be carried out in a single phase, for example by printing with a printing paste containing sodium bicarbonate or other acid-binding agent and subsequent steaming at temperatures of 100 to 103 ° C or biphasic, for example by printing with neutral or weakly acidic ink; subsequent fixation by passing the printed material through an electrolyte-containing hot alkaline bath or by overprinting the printed material, using an electrolyte-containing alkaline bath, followed by a delay or steaming, or by applying dry heat thereto, produces color-intensive prints with good contour status and bright white pool. The quality of these prints remains virtually unaffected by changing fixation conditions.

Dry heat fixation according to conventional thermofixation procedures uses hot air at a temperature of 120 to 200 ° C. In addition to the usual water vapor at a temperature of 101 to 103 ° C, superheated steam and pressure vapor at temperatures up to 160 ° C can also be used.

The acid binding agents and agents for fixing the compound of Formula 1 to cellulosic fibers are, for example, water-soluble alkali metal and optionally alkaline earth metal salts of inorganic or organic acids or compounds which liberate alkali warmly. Particular mention should be made of alkali metal hydroxides and alkali metal salts derived from mild to moderate inorganic or organic acids, with sodium and potassium compounds being preferred. Such acid binding agents are, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium formate. acid sodium phosphate, medium sodium phosphate, sodium trichloroacetate, 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; on these fibrous materials, they have a very high fixation yield using dyeing and printing processes. The dyeings on cellulose fibers exhibit excellent wet fastness after the usual rinsing action to remove unfixed dye fractions and, moreover, unfixed dye fractions are readily washable due to their good solubility in cold water.

The dyeing of polyurethane and polyamide fibers is usually carried out from an acid medium. Thus, for example, acetic acid and / or ammonium sulfate or acetic acid and ammonium acetate or sodium acetate may be added to the dyeing bath to achieve the desired pH. It is recommended to add conventional leveling aids such as those based on the reaction product of cyanuric chloride with a triple molar amount of amino benzenesulfonic acid and / or aminonaphthalenesulfonic acid or based on the reaction product, such as stearylamine with ethylene oxide, in order to achieve a viable color uniformity. As a rule, the material to be stained. is introduced into the bath at a temperature of about 40 ° C, kept there for some time, the dyeing bath is then adjusted to the desired weakly acidic, preferably by addition of acetic acid with a slightly acidic pH, and the dyeing is carried out at a temperature between 60 and 98 ° C. Deň: 32 ° C. The dyeing can also be carried out at boiling temperatures of up to 120 degrees Celsius (under pressure).

The dyeings and prints obtained by using the compounds of the general formula (1) according to the invention are highly distinguished. bright shades. In particular, the dyeing and printing on cellulosic fibrous materials have good light fastness and very good wet fastness, such as underwear, washboard fastness, water fastness, sea water fastness, dye fastness and sweat fastness; good pleating, ironing and abrasion resistance. In particular, it is necessary to emphasize the stability in sweat under alkaline conditions and the stability in underwear.

Of particular interest is the use of the compounds of formula I according to the invention. also for wool dyeing using fiber reactivity. In particular, it is also possible to dye wool with a non-felt treatment or a wool with a slight non-felt treatment (cf., for example, H. Rath, Lehrbuch. Der Textilchemie, Springer, Verlag, 3rd edition (1972), pp. 295-299). Hercosette procedure (page 298), J. Soc. Dyers and Colourisis 1972, 93-99, and 1975, 33-44) with very good stability.

The method of dyeing wool is carried out in a conventional and known dyeing process 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 control of the pH by the extraction procedure and at the end of time dyeing, the pH is shifted to a neutral and possibly slightly alkaline range up to a pH of 8.5 in order to achieve a complete reactive bond between this dye of formula 1 and the fiber, particularly when the desired high color saturation is desired. At the same time, the non-reactively bound portion of the dye is released.

The method described herein also applies to dyeing fibrous materials of other natural polyamides or of synthetic polyamides and polyurethanes. The dyeing is carried out at temperatures from 60 to 100 ° C, but can also be carried out in closed dyeing equipment at temperatures up to 106 ° C. Since the water solubility of the compounds of the formula I is very good, they can also be used advantageously in customary continuous dyeing processes. Color saturation achieved using the compounds of formula (1) of the invention. is very high. These 227045 compounds provide very bright, yellowish to bluish-red shades on fibrous materials, particularly in reactive wool dyeing. A high degree of bath depletion can be found at temperatures of 100 to 10 ° C for dyeing. In the case of the dyeing obtained with the compounds of the general formula (1) according to the invention, the otherwise usual additional effect of ammonia on the dyed goods can be dispensed with. In comparison with the structurally similar known dyes, the dyes according to the invention have, in a surprising manner, a very good color composition, while achieving a brilliant color. even in rich tones. In addition, they exhibit a very good ability to combine with other fiber-reactive dye wool, which allows surprisingly uniform coloring of the fibers. It is also possible to uniformly dye wool fiber materials of different provenance with the compounds of the invention. Optionally, leveling aids such as N-methyltaurine can optionally be added to improve egality.

Using conventional dyeing aids which have a fiber affinity, the compounds of the invention also provide uniform dyeing on wool with a non-felt or a weak non-felt. In light to medium color shades, a very good level of wet fastness can be achieved even without additional ammonia treatment, but optionally, if desired, an additional level of wet fastness can be achieved. treatment with ammonia. In addition to the high light fastness of these wool dyes, it has to be mentioned as very good wet fastness, in particular excellent sweat fastness under alkaline conditions and very good fastness in linen at 60 [deg.] C., even with high shade intensities.

The following examples serve to illustrate the invention. Parts and percentages are by weight unless otherwise indicated. Parts by weight are parts by volume in the ratio of kg: liter.

Example 1

a] Under stirring, 319 parts of 1-amino-8-naphthol-3,6-disulfonic acid as a dry ground mass was added to a suspension of 190 parts of cyanuric chloride, 2000 parts of water and 400 parts of ice. The reaction mixture was further stirred for a further 3 hours while maintaining the temperature between 12-16 ° C and maintaining the pH between 1.8 and 2.3 by adding about 160 parts of sodium bicarbonate. After this time, the reaction is complete and the presence of free amine can no longer be detected.

(b) Separately prepare the diazonium salt of the glazing component:

173 dP of aniline-2-sulfonic acid is suspended in 1800 parts of ice water. Then 130 parts by volume of concentrated aqueous hydrochloric acid are added and diazotization is then carried out by mixing 130 parts by volume of aqueous, 40% sodium nitrite solution at a temperature between 0 ° C and 5 ° C. The reaction mixture was then stirred for a further 30 minutes and the excess nitrous acid was then quenched with a small amount of amidosulfonic acid.

c) The solution or suspension of the diazonium salt produced according to b) is added to the reaction mixture produced according to a), i.e. the dichlorotriazinyl derivative. The pH is adjusted to 4 to 4.5 by addition of sodium bicarbonate. Within this pH range and at a temperature between 15 to 18 ° C, the reaction mixture was further stirred for 2 hours.

d) Separately, a suspension of 4-vinylsulfonylaniline is prepared for the second condensation reaction:

300 parts of 4 -3-sulfaatettaylsulfonvlaniline are dissolved in 2000 parts of water with the addition of 105 parts of bicarbonate. sodium to neutral solution. 30 volumes of aqueous 33% sodium hydroxide solution are slowly added over a period of 30 minutes at 20 ° C. The reaction mixture was stirred at 20 ° C for 30 minutes.

e) The suspension of 4-vinylsulfonylamine produced according to d) is stirred into a solution of the dichlorotriazmylaminonaphthalazobenzene derivative produced according to c). To carry out the condensation reaction, the reaction mixture is stirred for one hour at a pH between 5 and 5.5 and at a temperature between 25 and 30 ° C. Thereafter, the reaction temperature is slowly raised to 50 ° C over a period of 2 hours, maintaining the pH between 6.0 and 6.5 by adding sodium bicarbonate. Thereafter, the reaction mixture is slowly cooled to room temperature with stirring, with 350 parts of sodium chloride added at a temperature between 35-40 ° C. The precipitated compound is filtered off, washed three times with 500 parts by volume of aqueous 15% sodium chloride solution and then well mixed with 40 parts of sodium monohydrogen phosphate. The wet mass is dried under reduced pressure at 60 ° C in an oven and then the mixture is ground. About 1000 parts of red powder are obtained. containing an electrolyte (predominantly sodium chloride) containing a sodium salt of the compound of formula

These dyes have very good properties and provide, according to the application and fixation methods customary in the art, for fiber reactive dyes, for example, on wool, including wool with a weak non-felting finish, brilliant red dyes and prints with very good wet fastness. especially excellent stability in sweat, under alkaline conditions and very good underwear stability at 60 ° C. Coloring is further characterized by high saturation of color shades.

Example 2

In order to produce the compound of the invention, the procedure of Example 1 is followed, but in the second condensation step of step e) the same amount of 3-vinylsulfonylaniline is used instead of 4-vinylsulfonylaniline, which was produced according to the data of Example 1d. - / Tsulfatoethylsulfonylaniline.

About 1000 parts of an electrolyte-containing red powder is obtained which contains the sodium salt of the compound of formula

These dyes have very good fiber-reactive dye properties and dye according to conventional and known methods, for example cellulose and cotton fiber materials in intense red color shades with good fastness.

Example 3

Under stirring, 319 parts of 1-amino-8-naphthol-4,6-disulfonic acid as dry ground product are added to a suspension consisting of 190 parts of cyanuric chloride, 2000 parts of water and 900 dP of ice. The reaction mixture is further stirred for a further 3 hours while maintaining the temperature between 0 ° C and 5 ° C and maintaining the pH of the reaction mixture above 1.8 by the addition of sodium bicarbonate, preferably at a pH between 2 and 2.5. After this time, the reaction in the first condensation step is complete and the presence of free amine can no longer be detected.

This reaction mixture is reacted with dichlorotriazinylaminone naphtholder derivative according to the data described in Examples 1b) to 1e) to form a compound of the invention of the formula

-so ₂ -ch = ch

which is isolated in the form of the sodium salt. This compound also exhibits very good fiber-reactive dye properties and provides, for example, on wool, including wool with a weak non-tacky finish, brilliant yellowish-red coloration with very good wet fastness, of which the excellent perspiration fastness under alkaline conditions is particularly emphasized. The dyes obtained with this compound of the invention are further characterized by a high initial color shade.

Examples 4 to 9

In the following examples, which are summarized in the table, further compounds of formula (I) of the invention are described as the free acid. These compounds are preferably in the form of alkali metal salts.

These compounds also have very good fiber-reactive dye properties and preferably dye the cellulosic fibrous material and particularly preferably the wool in said color shades with very good fastnesses. These azo compounds or their salts according to the invention described in the examples summarized in the following table can be prepared by the process according to the invention, for example in analogy to the methods described in the previous examples using starting materials of the formulas.

TABLE EXAMPLE Compound corresponding to formula (1) the color shade of a yellowish red wave

SO ₂ -CH = CH ₂

N = N yellowish red

SO-CH = _CH2

OCH3 red

HO ₃ S

SO ₃ H

N = N yellowish 'red

H ₃ CO

HO3S example number

Compound corresponding to the general formula 1: color shade on the wool

HIM

HO ₃ S

N = N

Cl

N ^ N ^nh ~ Sm ^ ^nh ~ J ^ J ^-s ° ^{2CH = ch} 2 so ₃ H ^H 3 <^ red red

SO ₂ CH = CH ₂

0CH3

SO3H

Application Example 1:

100 parts of wool combs are prewashed in a conventional manner and then placed at 3000 ° C in 3000 parts of an aqueous dye bath containing as an auxiliary preparation 1 part of the fatty amine oxethylation product and 2 parts of ammonium acetate. The pH is adjusted to between 4.8 and 5.0 with acetic acid and the substrate is treated in this bath for 5 minutes. Then, 4 parts of the compound of the invention described in Example 1 dissolved in a small amount of water are added. The dyeing bath is heated at boiling point for 30 minutes and the wool material is dyed in the bath at this temperature for 60 minutes. The material is then removed from the dye bath, rinsed in water, then treated with a bath containing a small amount of acetic acid in aqueous solution, rinsed again in water, and dried.

The wool color obtained exhibits a brilliant, intense red tone of neutral shade with perfect uniformity and very good wet fastness, such as very good sweat fastness under alkaline conditions.

Application Example 2:

100 parts of wool yarn are prewashed as usual and then placed in 3000 parts of an aqueous dyeing bath at 40 ° C, the dyeing bath containing 2 parts of ammonium acetate and adjusted to pH 5.5 with acetic acid. The material is left in this bath for 5 minutes. Then 2 parts of the dye according to the invention described in Example 1 and dissolved in a small amount of water are added. The dyeing bath is then heated to boiling for 30 minutes and the goods are left in the bath for 45 minutes at this temperature. The yarn is removed, washed with water, then placed in an aqueous bath containing a small amount of acetic acid, washed again with water and dried.

This gives a wool material with a brilliant red hue and a very good wet fastness, especially excellent sweat fastness under alkaline conditions.

Application Case 3:

The dyeing process described in Application Example 1 is followed, but 4 parts of the compound of the invention are used as dyes. which . is described in Example 2. A brightly colored wool comb with a bright red hue is obtained. .Wet stability, in particular perspiration stability under alkaline conditions,. they are delicious.

Application Example 4:

100 parts of wool flakes are prewashed as usual and then placed in 3000 parts of a 40 ° C aqueous dye bath containing 2 parts of ammonium acetate and adjusted to pH 5.5 with acetic acid. The material was treated with this bath for 5 minutes. Then, 3 parts of the compound of the invention described in Example 2 and dissolved in a small amount of water are added. The dyeing bath is heated to boiling point for 30 minutes and discolored for 45 minutes at this temperature. The material was then removed, washed with water and placed in a bath containing a small amount of acetic acid, then rinsed again with water and dried.

Uniformly colored wool flakes are obtained which have a bright red shade with high color saturation and very good wet fastness, in particular excellent sweat fastness under alkaline conditions.

Application Example 5:

100 parts of wool flakes, which have been treated in a conventional and known manner with a non-woven fabric, are placed in an aqueous dyeing bath at 40 ° C containing 2 parts of ammonium ootane and adjusted to pH 6 with acetic acid. act for 5 minutes. Then 3 parts of the compound of the invention described in Example 3 and dissolved in a small amount of water are added. The dyeing bath is heated to boiling for 30 minutes and the goods are dyed in the bath for 45 minutes at this temperature. The dyed article is then removed, washed with water, then with a bath containing acetic acid and then again with water and dried.

A bright yellowish-red color is obtained and with very good wet fastness.

Claims (1)

OBJECT OF THE INVENTION A process for the preparation of the monoazo compounds of the general formula 1 wherein: M represents a hydrogen atom or a metal equivalent R represents a hydrogen atom or a methyl group, an ethyl group, a methoxy group or an ethoxy group and a vinylsulfonyl group on the benzene ring being in the meta- or para-acylated amino position, and the other -SOsM group on the naphthalene ring an amino group, characterized in that the compound of formula (2) is: M is as defined above and the second group of formula -SO 3 M on the naphthalene nucleus is bound in the meta- or parapo? A compound of formula (3), wherein the compound is an acylated amino group, is reacted with an aromatic amine of formula (3) wherein: R is as defined above and the vinylsulfonyl group on the benzene ring is bonded in meta- or parapolysis to the amino group.