DE1289205B - Process for the preparation of monoazo dyes - Google Patents

Description

1 2

The present invention relates to a process b) an amino monoazo dye of the formula

for the production of monoazo dyes, the there- H- A N = N R

is characterized by that one either

a) a diazo compound of an amine of the formula with a compound donating the radical Y condensate

_v . , .rjj, _1λ 5, where m, A, B and Y are those mentioned under a)

Ym -A-NH ₂ (1) have meaning, or

wherein Y is a fiber-reactive aliphatic acyl radical c) in an acylamino dye of the formula

with unsaturated bond, m a divalent _{v,. M} .. _R

Nitrogen bridge and A the remainder of the formula ^{Y m Λ N} ~ ^{N ö}

io wherein m, A and B have the meaning given under a)

/ \ _ and where Y 'is an aliphatic / J-halo-

__ | _ j denoted acyl radical means removing hydrogen halide

Y / splits, where in each case monoazo dyes of the formula

■ y _m a χι --— · \\ r>

means, in which X is a hydrogen atom, a 15

Sulphonic acid group or a carboxyl group, arise in which Y, m, A and B gemit under a) a compound of the formula H - B couples have mentioned meaning.

wherein B is the remainder of the formula The invention preferably relates to the

Production of new valuable Monoazofarb- ₂₀ substances which are obtained by coupling of diazo compounds of amines of the formula

Xv

NH ₂

(2) ν /

Y ^y

wherein X represents a hydrogen atom, a sulfonic acid group or a carboxyl group and Y represents an acrylic, wherein Z represents a sulfonic acid amide group, /; an amino, chloroacrylamino, bromoacrylamino or positive integer with a value of at most 2 and ρ 30 denotes propiolylamino, with 2-amino-8-hyeine represents those of at most 3, or contains hydroxynaphthalene-6-sulfonic acid amides.

The invention also relates primarily to the preparation of dyes of the formula

SO ₃ H

N = Nx s ₍₃₎

correspond, where Z is a preferably on stick aniline and the corresponding carbon and ins-

material atom alkylated and / or arylated sulfonic acid 45 special sulfonic acids, preferably the 1,4-di-

amide group, a Y 'is a hydrogen atom and the aminobenzene-2-sulfonic acid and the 1,3-diamino

other Y 'one via a preferably unsubstituted benzene-4-sulfonic acid or its to which the sulfonic acid

tuierte amino bridge bonded aliphatic acid group distant nitrogen atom monosub-

«, / I-unsaturated acyl radical with a maximum of 3 carbon-substituted derivatives, e.g. B. the methyl, ethyl,

Substance atoms, such as B. the propiolyl or especially ₅ o propyl or isobutyl compounds.

special acrylic or halogen acrylic residue and /; a As starting products for the production of

is an integer with a value of at most 3, amines of the formula (2) are suitable compounds

by condensation of the corresponding coloring to name those which are easily acylable

substances in which a Y 'is a hydrogen atom and the amino group, e.g. B. a monoalkylamino group,

other Y 'denotes an acylatable amino group, 55 and next to it a less readily acylatable primary

with anhydrides or chlorides of aliphatic amino group or a nitro group, which

«, // - unsaturated and not more than 3 carbon atoms diazotized or reduced after acylation and

containing carboxylic acids, the radicals of which can be diazotized with the. As less easily acylated

Fiber can enter into a chemical reaction. bare amino groups are primarily those

As amines of the formula (2), for example, 60 should be mentioned, which are in the position adjacent to an acidic

called: the condensation products from 1 MoI group, e.g. B. a sulfonic acid group,

of an anhydride or chloride of acrylic acid, As in the process according to the invention for

Coupling components used are chloroacrylic acid, dichloroacrylic acid, chloromalein application

acid, dichloromaleic acid, propiolic acid, croton-2-amino-8-hydroxynaphthalene-6-sulfonic acid amides

acid, chlorocrotonic acid, bromoacrylic acid, dibromo- 65 or 2-aminonaphthalene-6-sulfonic acid amides

acrylic acid, bromomaleic acid, dibromomaleic acid, which couple in the 1-position, like the primary one

or bromerotonic acid with 1 mol of m- or p-phenylene sulfonic acid amide, sulfonic acid-N-monoalkylamides,

diamine, m- or p-N-alkyl- or -N-arylamino- especially the -monomethyl-, -monoethyl-, -mono-

I 289 205

propyl or monoisobutyl amide, as well as sulfonic acid-N-dialkylamides containing the same or different types of such alkyl radicals, also sulfonic acid-N-arylamides, such as sulfonic acid-N-phenylamide or sulfonic acid-N-2 ', 6'-dimethylphenylamide, or with advantage z. B. sulfonic acid-N-methyl-N-phenylamide, sulfonic acid-N- / i-hydroxyethyl-N-phenylamide, Sulfonic acid - N - methyl - N - 2 '- carboxyphenylamide or sulfonic acid N-morpholide; beyond are still the corresponding 6-sulfonic acid amides of 2-N-methyl or -äthylamino-8-hydroxynaphthalins or 2-N-methyl- or -äthylaminonaphthalins as to name suitable coupling components.

The diazotization of the amines used as starting materials in the process according to the invention can according to methods known per se, for. B. with the help of mineral acids, especially hydrochloric acid, and sodium nitrite, or according to the known ones commonly used for compounds that are difficult to diazotize Methods, for example with the help of nitrosylsulfuric acid, take place. It is in the last mentioned Often expedient, the diazo compounds z. B. by diluting the diazotization mixture with Separate water, filter it off and thus couple it. The coupling takes place in acidic, for example weakly Congo acidic to acetic acidic agent. It is often recommended that the resulting free mineral acid z. B. with To blunt sodium acetate. In the diazotization, coupling and isolation of the resulting dyes it is of course necessary to proceed in such a way that the reactive, unsaturated acylamino group is retained.

The preparation of the amino monoazo dyes of the formula (3) to be used as starting materials can by saponification of corresponding acylamino monoazo dyes or by reducing the corresponding nitromonoazo dyes, which can be obtained by coupling the aforementioned Coupling components with diazotized acylamino- or nitroanilines or diazotized Acylamino or nitroaniline sulfonic or carboxylic acids obtained. The condensation according to the invention Such aminomonoazo dyes with the acid derivatives mentioned are carried out according to known ones Methods by, expediently in the presence of acid-binding agents, such as sodium acetate, sodium hydroxide or sodium carbonate, and under such conditions that the reactive to be introduced Rest is retained, that is, z. B. in the presence of organic solvents or at relatively low to moderately elevated temperatures in aqueous media.

A preferred embodiment of the process according to the invention consists in that dyes of the formula _Kiri

ΙΝΓΊ2

where X is a hydrogen atom, a sulfonic acid group or a carboxyl group, η is a positive integer not exceeding 2, Z is a sulfonic acid amide group, in particular a sulfonic acid-N-alkyl-N-arylamide group, and Ya is a / J-chloropropionylamino group, a «, / i -Dichloropropionylamino group or a «, / i-dibromopropionylamino group means treated with agents which split off hydrogen halide. The starting materials mentioned can be produced according to the principle of the first two production processes mentioned, ie by coupling or condensation.

To split off hydrogen halide by the process according to the invention, the

! O mentioned dyes, preferably those that have one / i-halopropionylamino or a «, / i-dihalopropionylamino group have, expediently with alkali or alkaline earth hydroxide, carbonate or -hydrogen carbonate at low to moderately elevated temperatures or with alkali or alkaline earth acetate treated at elevated temperature.

In the case of the latter two manufacturing processes, too, of course, is involved in the various operations and in the subsequent isolation of the dyes to ensure that the fiber reactive residue preserved.

The dyes obtained according to the invention are preferably isolated at low temperatures by salting out and filtering. The isolated dyes can optionally after addition are dried by coupage agents or stabilizers; drying is preferred carried out at not too high temperatures and under reduced pressure. By spray drying of the entire preparation mixture, dry preparations can in certain cases be used directly, i. H. without intermediate isolation of the dyes, produce. According to this method, new valuable dry preparations are obtained, which can be used for production from stock solutions or dye baths, possibly also from printing pastes.

The dyes obtained by the process according to the invention are new. You are valuable Compounds suitable for dyeing and printing a wide variety of materials, especially polyhydroxylated Materials with a fibrous structure such as cellulose-containing materials, both synthetic Fibers, e.g. B. from regenerated cellulose, or natural materials, e.g. B. pulp, linen or especially cotton.

However, the dyes which can be prepared according to the invention are very particularly suitable for dyeing of nitrogen-containing fibers such as super polyamides, super polyurethanes, silk, leather and above all wool, e.g. B. from weakly acidic, neutral or weakly alkaline bath, optionally under Addition of the usual aids, e.g. B. with the addition of Äthylenoxydkondensationsprodukte high molecular weight Amines. In this way, even, full dyeings with good light and lightness are obtained on wool Rubbing fastness and good wet fastness properties as well as excellent levelness.

Compared to the next comparison known from the German interpretative documents 1 058 467 and 1 092 144

6c bar dyes show those obtained according to the invention Dyes which have a chloroacrylic group instead of a chloropropionylamino group, the advantage of producing dyeings of significantly better millfastness on wool.

& 5 In the following examples, the parts unless otherwise indicated, parts by weight, percentages percentages by weight, and temperatures are given in degrees Celsius.

example 1

A neutral solution of 139.5 parts of 4- / i-chloropropionylamino - 2 - aminobenzene -1 - sulfonic acid in 1000 parts of water is mixed with 125 parts of 30% Hydrochloric acid is added and at 10 to 15 in the usual way with 125 parts by volume of a 4N sodium nitrite solution diazotized. The obtained nitrous acid-free diazo compound becomes a slurry poured, which is obtained by dissolving 172 parts of 2-amino-8-hydroxynaphthalene-6-sulfonic acid-N-methyl-N-phenylamide in 500 parts by volume of an n-sodium hydroxide solution and acidification with 500 parts by volume 2 has received η-acetic acid. The mixture is stirred at 20 to 25 ° until the coupling has ended, added then the coupling mixture with 550 parts by volume of a 10 N sodium hydroxide solution and stirred during about 3 hours at about 40, with the / i-chloropropionyl group is converted to the acrylic group. The dye suspension treated in this way then becomes 30% strength with about 200 parts by volume Hydrochloric acid neutralized except for a weakly alkaline reaction (pH value approx. 8), filtered, the dye Washed thoroughly with 2% sodium chloride solution and dried at 80 to 90 in vacuo. A red powder is obtained, which dissolves in hot water, and wool or fibers made from super polyamides Dyes in wet-fast, scarlet tones.

The elimination of hydrogen chloride can also be done in such a way that the coupling mixture with about 300 parts by volume of a 10 N sodium hydroxide solution weakly alkaline (pH 8 to 9) after adding 750 parts by volume of a 2N sodium carbonate solution for 30 minutes 80 stirred, filtered, the residue was washed with a 2% sodium chloride solution and in vacuo dries.

Dyeing prescription

2 parts of the dye obtainable in accordance with paragraph 1 are dissolved in 4000 parts of water and 10 parts are used crystallized sodium sulfate and goes with 100 parts of well-wetted wool at 40 to 50 in the dye bath thus obtained. Then you add 2 parts of 40% acetic acid, bring within half an hour to boil and color% boiling hours. Finally, the wool is treated with cold Rinsed with water and dried. The wool is in washable, scarlet red tones and has good lightfastness colored.

Similar dyes, the wool from neutral or acetic acid bath in the specified in column III Coloring shades is obtained by using the diazo mentioned in columns I and II. and azo components according to the above example and the resulting mono- or dihalopropionylamino dyes by splitting off hydrogen halide into the corresponding acrylic or monohaloacrylic dyes.

I. II III Neutral or Diazo component from Azo component acetic acid coloring
on wool 1 4- / i-chloropropionylamino-2-amino- 2-amino-8-hydroxynaphthalene-6-sulfone Scarlet fever benzene-1-sulfonic acid acid anilide 2 the same 2-amino-8-hydroxynaphthalene-6-sulfone Scarlet fever acid-N-methyl-N-benzylamide 3 the same 2-amino-8-hydroxynaphthalene-6-sulfone Scarlet fever acid-2 ', 6'-dimethylphenylamide 4th the same 2-amino-8-hydroxynaphthalene-6-sulfone Scarlet fever acid-N- / i-hydroxyethyl-N-phenylamide 5 the same 2-amino-8-hydroxynaphthalene-6-sulfone Scarlet fever acid-N-ethyl-N-phenylamide 6th the same 2-aminonaphthalene-6-sulfonic acid Yellow orange methylamide 7th 5-a, / i-dichloropropionylamino-2-amino- 2-aminonaphthalene-6-sulfonic acid orange benzene-l-sulfonic acid N-methyl-N-phenylamide 8th S-n ^ -Dibromopropionylamino ^ -amino- the same orange benzene-1-sulfonic acid 9 S-zJ-Chlorpropionylamino ^ -amino- 2-amino-8-hydroxynaphthalene-6-sulfone Red benzene-1-sulfonic acid acid-N-methyl-N-phenylamide

Example 2

A neutral solution of 121 parts of 4-acrylamino-2-aminobenzene-1 -sulfonic acid in 1000 parts of water is mixed with 125 parts of 30% hydrochloric acid and diazotized at 10 to 15 in the usual way with 125 parts by volume of a 4N sodium nitrite solution. The resulting nitrous acid-free diazo compound is poured into a slurry, which is by dissolving 172 parts of 2-amino-8-hydroxynaphthalene-6-sulfonic acid-N-methyl-N-phenylamide in 500 parts by volume of an n-sodium hydroxide solution and acidification with 500 parts by volume of 2 n-acetic acid had received. The mixture is stirred at 20 to 25 until the coupling has ended, then the coupling mixture is added with about 250 parts by volume of a

10 n-sodium hydroxide solution up to the weakly alkaline Reaction. The practically completely precipitated dye is filtered with 2% sodium chloride solution washed thoroughly and dried in vacuo at 80 to 90. You get a red one Powder that dissolves in hot water and dyes wool or fibers made from super polyamides in wet-fast, scarlet shades. The received The dye is identical to the product obtained according to Example 1, Paragraph 1.

Example 3

40.2 parts of 4-a, / i-dibromopropionylamino-2-aminobenzene-1-sulfonic acid are in a mixture of 25 parts of u-naphthalenesulfonic acid and 500 parts Water well stirred and slowly by adding dropwise an aqueous solution of 6.9 parts of sodium nitrite diazotized.

The resulting clear, nitrous acid-free diazo compound is poured into a slurry, which is obtained by dissolving 35.8 parts of 2-amino-8-hydroxynaphthalene-6-sulfonic acid-N- β- hydroxyethyl-N-phenylamide in 200 parts by volume of a 1N- Sodium hydroxide solution and acidification with 200 parts by volume of 2 η-acetic acid. Stir at 20-25. until the coupling is complete, 40 parts by volume of K) n sodium hydroxide solution are then added to the coupling mixture and the mixture is stirred for a further 10 minutes, during which the «, // - dibromopropionyl group is converted into the bromoacrylic group. The dye suspension treated in this way is then neutralized with 30% hydrochloric acid to a weakly acidic reaction (pH about 6), filtered, the dye washed with 2% sodium chloride solution and dried in vacuo at 80 to 90. A red powder is obtained which dissolves in hot water and dyes wool or fibers made from superpolyamides in wet-fast, yellowish-red shades.

If, in place of the 4 - "./ i-dibromopropion3 '! Amino-2-aminobenzene-1-sulfonic acid, the 5-'i, _i >' - dibiOmpropionylamino-2-aminobenzene-1-sul-ibic acid is used. this gives a similar dye that dyes wool and fibers made from superpolyamides in slightly more bluish red tones.

Example 4

40.2 parts of 4 - </./ f-dibromopropionylamino-2-aminobenzene-1-sulfonic acid are, as indicated in Example 3, diazotized and poured into a slurry, which is obtained by dissolving 34.2 parts of 2 - N - methylamino - 8 - hydroxynaphthalene - 6 - sulfonic acid-N-methyl-N-phenylamide in 200 parts by volume of a 1N sodium hydroxide solution and acidification mn 200 parts by volume of 2N-ethyl acetate. The mixture is stirred at 20 to 25 until the coupling has ended. 40 volumes of 10N sodium hydroxide solution are then added to the coupling mixture, and the mixture is stirred for a further 10 minutes, during which the «, / i-dibromopropionyl group is converted into the bromoacrylic group. The dye suspension treated in this way is then neutralized with 30% hydrochloric acid to a weakly acidic reaction (pH about 6), filtered, the dye washed with 2% sodium chloride solution and dried in vacuo at 80 to 90. A red powder is obtained which dissolves in hot water and dyes wool or fibers made from superpolyamides in wet-fast, bluish-tinged red shades.

If you use 5-u, jl- dibromopropionylamino-2-aminobenzene-1-sulfonic acid instead of 4 - «, / i-dibromopropionylamino - 2 - aminobenzene -1 - sulfonic acid, you get a similar dye, the wool and fibers ajis Super polyamides in strongly bluish red tones.

Example 5
57.1 parts of the dye of the formula

NH ₂

SO ₃ H

'5 HOOC

NH,

are neutralized with 2N sodium hydroxide solution in 500 parts of water, and 16.4 parts of anhydrous sodium acetate are added. With vigorous stirring, a solution of 25 parts of α, β-Ό'ι- bromopropionyl chloride in 100 parts of acetone is added dropwise at 0 to 5 in the course of 30 minutes. After a short time the amino group is completely acylated. The dye suspension thus obtained is mixed with 30 parts of 10N sodium hydroxide solution, stirred for a short time and then neutralized by adding about 10 parts of 10N hydrochloric acid. The dye is then deposited by adding sodium chloride, filtered and dried. The dye obtained in this way dyes wool from a neutral to acetic acid bath in wet and lightfast red shades.

Claims (5)

Patent claims: 1. Process for the production of monoazo dyes, thereby characterized. that one either a) a diazo compound of an amine of the formula Y - m - A - NHj wherein Y is a fiber-reactive aliphatic acyl radical with an unsaturated bond, m is a divalent one Nitrogen bridge and A the remainder of the formula represents where X represents a hydrogen atom, a sulfonic acid group or a carboxyl group is coupled with a compound of the formula H - B, wherein B is the remainder of the formula NH is where Z a sulfonic acid amide group, 909 507/1564 SO ₃ H NH- where one Yi denotes a hydrogen atom, the other Yi denotes an acylatable amino group, Z denotes a sulfonic acid amide group and ρ denotes an integer of at most 3, with anhydrides or chlorides of aliphatic α, / i-unsaturated carboxylic acids having at most 3 carbon atoms, their radicals with the fiber can enter into a chemical reaction, condenses. IO η represents a positive integer with a value of at most 2 and ρ one of at most 3, or b) an amino monoazo dye of the formula H-m-A-N = N-B condensed with a compound releasing the remainder of Y, where m, A, B and Y are the under a) have the meaning mentioned, or c) in an acylamino dye of the formula Y '- m - A - N = N - B in which m, A and B have the meaning given under a) and in which Y 'is an aliphatic / i-halogenated acyl radical means hydrogen halide splits off, in each case monoazo dyes of the formula Y-m-A-N = N-B arise, in which Y, m, A and B have the meaning given under a). 2. The method according to claim 1, characterized in that one dyes of the formula 20th 35 40 3. The method according to claim 1, characterized in that one diazo compounds of amines of the formula XV-NH ₂ X / wherein X is a hydrogen atom, a sulfonic acid group or a carboxyl group and Y is Acrylamino, chloroacrylamino, bromoacrylamino or propiolylamino group means with 2-amino - 8 - hydroxynaphthalene - 6 - sulfonic acid amides. 4. The method according to claim 1, characterized in that one dyes of the formula NH, wherein X represents a hydrogen atom, a sulfonic acid group or a carboxyl group, / 2 an integer positive number with a value of at most 2, Z a sulfonic acid amide group and Ya a / i-chloropropionylamino group ^ iner ^ / f-dichloropropionylamino group or a «, / i-dibromopropionylamino group means treated with agents that split off hydrogen halide. 5. The method according to claim 4, characterized in that there is used as starting materials Monoazo dyes used in which Z is a sulfonic acid-N-alkyl-N-arylamide group.