DE1544598C3 - Process for the preparation of water-insoluble sulfonic acid and carboxylic acid group-free monoazo dyes n - Google Patents

Description

ι Z

B-W

(C ₂ H ₄ O) ₁₁₁ -X

IO is used, where B, W, X, Y and Z have the meanings given in claim 1 and m is 2 to 4.

3. The method according to claim 1, characterized in that one of the coupling component formula

B — W '

(C ₂ H ₄ O) ,, X

is used, where Y, Z, B, X and η have the meanings given in claim 1 and W 'stands for - CN, phenoxy or a lower carboalkoxy group.

3 ° The monoazo dyes which can be prepared by the process according to the invention, as described in claim 1, are suitable for dyeing synthetic textiles. Compared to the dyes of DT-PS 10 69 313, the dyes which can be prepared according to the invention produce dyeings on aromatic polyester textiles which are much more fast than dry heat treatments. Compared to the dyestuffs of GB-PS 9 33 160, the dyestuffs according to the invention produce much stronger colorations on aromatic polyester textiles when they are applied from a dyebath with a weakly acidic pH. In comparison with the dyes according to GB-PS 4 34 126, FR-PS 1103 481 and US-PS 23 59 305, the dyes according to the invention produce colorations in an aromatic polyester textile material which have better fastness properties when treated in dry heat.

As examples of the halogen atoms represented by Y or Z, chlorine or bromine atoms should be mentioned will.

Examples of the lower alkyl groups represented by Y or Z should include ethyl, propyl, butyl and preferably methyl groups, and as examples of those represented by Y or Z. lower alkoxy groups should mention ethoxy, propoxy, butoxy and preferably methoxy groups will.

The acyl groups represented by X are the following: acyl groups derived from aliphatic carboxylic acids, in particular of lower aliphatic carboxylic acids, such as. B. formic acid, acetic acid, Propionic acid and butyric acid, and of the substituted lower aliphatic carboxylic acids chloroacetic acid, Methoxyacetic acid and / i-acetoxypropion-

acid derived; Acyl groups derived from aliphatic sulfonic acids, especially lower alkanesulfonic acids, such as. B. methanesulfonic acid and ethanesulfonic acid come from; Acyl groups derived from the monocyclic aromatic carboxylic acids benzoic acid, methoxybenzoic acid, p-nitrobenzoic acid and toluic acid; Acyl groups derived from the monocyclic aromatic sulfonic acids benzenesulfonic acid and toluenesulfonic acid; and acyl groups derived from lower aliphatic or monocyclic aromatic carboxylic or carbamic acids such as e.g. B. methoxycarbonyl, phenoxycarbonyl, aminocarbonyl, methylaminocarbonyl or phenylaminocarbonyl groups. However, the acyl groups present are preferably the acyl groups of the formula - COX ', where X' is a hydrogen atom or a lower alkyl group.
As examples of alkylene radicals represented by B and V, methylene, propylene, trimethylene, tetramethylene and, above all, ethylene groups should be mentioned. In the case of the alkylene groups represented by V in the formula - (V - O -) "- X, they do not necessarily need to be the same as each other when η is 2 or more. If η is 2, then z. B. one group V be the ethylene group and the other the trimethylene group.

As specific examples of the types given by —B - W The following groups should be mentioned:

ß-cyanoethyl,

fJ-phenoxyethyl,

/ 5-formyloxyethyl,

/ f-acetoxyethyl,

y-acetoxypropyl,

ß-propionyloxyethyl,

/ 5-carbomethoxyethyl,

/ J-carboethoxyethyl and

ß- phenoxycarbonylethyl.

35

40

As specific examples of the by
- (C ₂ H ₄ -OLX

The following groups should be mentioned:

/ 9 - (/? '- Hydroxyethoxy) ethyl,

/; - [/ i '- (/ f "-Hydroxyethoxy) ethoxy] ethyl,

/? - {^ '- [/ S "- (/?"' - Hydroxyethoxy) ethoxy] -

ethoxy} ethyl,
/? - (/? '- Acetoxyethoxy) ethyl,
. ß - (/ S'-propionyloxyethoxy) ethyl,
/? - 0? '- Formyloxyethoxy) ethyl,
/ i - [/ f '- (/ i "-Acetoxyethoxy) ethoxy] ethyl,
/ M / * '- [/ <"- (/ f"' - acetoxyethoxy) ethoxy] -

ethoxy} ethyl,

ß - [/ f '- (p-nitrobenzoyloxy) ethoxy] ethyl,
/ f - (/ i'-methylsulfonylethoxy) ethyl,
/ H / i'-Methoxycarbonyloxyäthoxy) äthyl and
/ M / i'-methylaminocarbonyloxyethoxyKithyl.

The process according to the invention can advantageously be carried out in that an aqueous Solution or suspension of the diazotized primary amine in a solution of the coupling component in a dilute solution of an acid such as e.g. B. hydrochloric acid and the resulting mixture

55 is preferably stirred at a pH between 3 and 7 to form the azo dye, whereupon the azo dye is isolated in a manner known per se.

As specific examples of the primary amines of the general formula given in claim 1 the following should be mentioned:

p-nitroaniline,

2,4-dinitroaniline,

2,4-dinitro-6- (chloro- or -bromo) -aniline,

5-nitro-2-anisidine,

2,6-di (chloro- or -bromo) -4-nitroaniline,

2-chloro- or bromine) -4-nitroaniline,

5-nitromethyl anthranilate,

2-amino-5-nitrophenylmethylsulfone,

2-amino-3- (chloro- or -bromo) -5-nitrophenyl-

methylsulfone and
Methyl-2-amino-3- (chlorine or bromo) -

5-nitrobenzoate.

The coupling components in which X is a hydrogen atom can be prepared by that the corresponding secondary amine of the general formula

B-W

wherein B, W, Y and Z have the meanings given in claim 1, with the necessary molecular fraction of an alkylene oxide such as ethylene oxide or with a chloro- or bromoalkanol of the general formula

Cl- (V —O—) "—H or Br- (V — O—)" —H,

in which η and V have the meanings given in claim 1, is reacted, or by hydrolyzing the corresponding compounds in which X is an acyl radical.

The coupling components where X is a

of the above acyl groups can be prepared by the fact that the corresponding Coupling component of the formula given in claim 1, in which X is a hydrogen atom, acylated is or that the corresponding secondary amine with an acylated chlorine or as mentioned above Bromoalkanol of the formula

or.

Cl- (V-Ο -) .- acyl
Br - (VOJ _n -acyl,

wherein η and V have the meanings given in claim 1, is treated. The coupling components in which X is one of the acyl groups mentioned can also be prepared by reacting the corresponding primary amine with a molecular portion of the acylated chloro- or bromoalkanol, the desired - B - W group being incorporated into the resulting secondary amine is introduced in a manner known per se.

The following should be mentioned as specific examples of the coupling components mentioned:

N - (// - cyanoethyl) -N-l / ^ - [/) '' - (/ j "-hydroxyethoxy) -

ethoxy] ethyl} -m-toluidine,
N - (/ i-cyanoethyI) -N - {/ i - [/ i '- (/>"- hydroxyethoxy) -

ethoxy] ethyl} -m-chloroaniline,
N - (/ * - cyanoethyl) -N- [ß - (/ i'-hydroxyethoxy) -

ethyl] aniline,
3- {N - (/ i-cyanoethyl) -N - [/ H / ^ '- hydroxyethoxy) -

ethyl] amino} acetanilide,
N - (/ i-cyanoethyl) -N - [/ i - (// '- acetoxyethoxy) -

ethyl] aniline,
N - (/ - i-cyanoethyl) -N -! / ^ - [/ i '- (/ j "-acetoxyethoxy) -

ethoxy] ethyl} aniline,
N - (/ i-cyanoethyl) -N - (/ y- | / i '- [/ i "- (/ i'" - acetoxy-

ethoxy) ethoxy] ethoxy} ethyl) aniline,
N - (/ i-cyanoethyl) -N - [> (/ i'-acetoxyethoxy) -

ethyl] -m-bromoaniline,
N - ^ - Methoxycarbonylathyli-N-fjH / i'-acetoxy-

ethoxy) ethyl] aniline,
N- (ß-phenoxyethyl) -N - [/ Hß'-hydroxyethoxy) -

ethyl] aniline,
N-ethoxycarbonylmethyl-N - [/ i - (// - hydroxy-

ethoxy) ethyl] aniline,
N - (/ y-methoxycarbonylethyl) -N - [/ H / ^ '- hydroxy-

ethoxy) ethyl] aniline,
N - (/ ^ - phenoxycarbonylethyl) -N - [/ i - (/ V'-hydroxy-

ethoxy) ethyl] aniline,
N-Ci-AcetoxypentylJ-N-fj ^ ß'-acetoxy-

ethoxy) ethyl] aniline,
N - (/ * - acetoxyethyl) -N - [/ i - (/ <'- hydroxyethoxy) -

ethyl] aniline,
2-methoxy-5-acetamido-N - (/ i-acetoxyethyl) -

N - [/ i - (/ i'-acetoxyethoxy) ethyl] aniline,
2-ethoxy-5-acetamido-N - (/ f-acetoxyethyl) -

N - {/ i - [/ y '- (/; "- acetoxyethoxy) ethoxy] ethyl} -

aniline,
Ni / i-acetoxyethyl ^ -IiC / H / i'-acetoxyethoxy) -

ethyl] -2-methoxy-5-methylaniline and
N - (/ i-cyanoethyl) -N - [/ i - (/ i'-hydroxyethoxy) -

ethyl] -m-trifluoromethylaniline.

The azo dyes prepared according to the invention are useful as dyes for, for example, the following synthetic ones Fabrics very useful: cellulose acetate fabrics such as secondary cellulose acetate and cellulose triacetate fabrics, Polyamide fabrics, such as polyhexamethylene adipamide fabrics, and preferably aromatic polyester fabrics such as polyethylene terephthalate fabrics. Such fabrics can be in the form of loose threads, yarn, or woven or knitted fabric. The synthetic Textiles can also be in the form of mixtures with other textile fibers, such as. B. Mixtures of polyester and cotton fibers and of polyester and wool fibers.

Such fabrics can be conveniently dyed with the new azo dyes by dipping the fabric in a dyebath consisting of an aqueous dispersion of one or more of the dyes and preferably containing a nonionic, cationic and / or anionic surface-active agent, after which the dyebath heated to an appropriate temperature for a while. In the case of secondary cellulose acetate textile fabrics, the dyeing process is preferably carried out at a ^{temperature between 60 and 85 °} C .; In the case of cellulose triacetate or polyamide textile fabrics, the dyeing process is preferably carried out at a ^{temperature between 95 and 100 °} C .; In the case of aromatic polyester textiles, the dyeing process can either take place at a temperature between 90 and 100 ° C, preferably in the presence of a carrier, such as. B. diphenyl or o-hydroxydiphenyl, carried out or at a temperature above 100 ° C, preferably at a temperature between 120 and 130 ⁰ C, below

ίο overpressure can be created.

However, it is also possible to proceed in such a way that the aqueous dispersion of the dye mentioned is applied to the textile material by a padding or printing process, after which the textile material is heated or treated with steam. In such processes, the aqueous dispersion of said azo dye preferably contains a thickening agent such as gum tragacanth, gum arabic or sodium alginate.
At the end of the dyeing process, the dyed fabric is preferably rinsed with water or briefly treated with soapy water before it is finally dried. For aromatic polyester fabrics, the dyed fabric is preferably subjected to a treatment with an alkaline aqueous solution of sodium hydrogen sulfite before being treated with soapy water to remove loosely bound dye from the surface of the fabric.
The azo dyes have an excellent affinity and an excellent build-up capacity on synthetic textiles, in particular the aromatic polyester textiles, so that dark shades can be achieved. The resulting color tones are yellow to blue and have excellent fastness to light, wet treatments and especially dry heat treatments such as those used at high temperatures for pleating. The dyes also have excellent affinity for cellulose acetate fabrics.

The dyes according to the invention can optionally be combined on synthetic fabrics can be applied with other disperse dyes. The invention is explained below on the basis of exemplary embodiments explained in more detail, all quantities being based on weight.

example 1

A solution of 2.76 parts of 4-nitroaniline in a mixture of 27 parts of acetic acid and 10 parts of a concentrated aqueous hydrochloric acid ^{solution is cooled to 5 °} C., and a solution of 1.38 parts of sodium nitrite in 10 parts of water is added with stirring, whereupon the mixture is stirred for 15 minutes. The diazo solution, which then arises, is in a solution of 4.8 parts of N - (/ f-cyanoethyl) -N - [/ H / i'-hydroxyäthoxy) ethyi] aniline in a mixture of 100 parts of acetone and 110 parts of a added aqueous 0.2 N hydrochloric acid solution at 5 ° C, whereupon the mixture is stirred for 5 minutes. A solution of 10 parts of sodium acetate in 50 parts of water is then added and the mixture is stirred at 20 ° C. for 18 hours. The dye that precipitates is filtered off, washed with water and then dried.

Dispersion of the dye in an aqueous medium is useful in dyeing polyethylene terephthalate fabrics deep red-orange hues.

which are very resistant to dry heat treatments.

The N - (ß - cyanoethyl) -N - [/ '- (Ii' - hydroxyethoxy) ethyl] aniline used was produced by reacting N - (/ ^ - cyanoethyl) aniline with 2 molecular fractions of ethylene oxide at 170 ° C was brought. The resulting product boiled at 192 to 196 ° C under a pressure of 0.125 mm of mercury.

B e i s ρ i e 1 2

IO

1.63 parts of 2-amino-5-nitrobenzonitrile are added to a nitrosylsulfuric acid solution prepared by dissolving 0.7 parts of sodium nitrite in 15 parts of sulfuric acid, and the resulting mixture is stirred at 20 to 25 ° C. for 2 hours. The mixture is then slowly added to a solution of 2.92 parts of N - (^ - cyanoethyl) -N - {/ ^ - [/ r - (^ "- hydroxyethoxy) ethoxy] ethyl} -m-toluidine in a mixture of 50 parts Acetone and 100 parts of an aqueous hydrochloric acid solution are added, ice is also added in order to keep the temperature between 5 and 10 ° C. Sodium acetate is then added until the mixture is no longer acidic to Congo stirred to 10 ⁰ C, and the precipitated dye is filtered off, washed with water and then dried.

A dispersion of the dye in an aqueous medium results in the dyeing of polyester fabrics ruby red shades that are very resistant to dry heat treatments.

The N - (β - cyanoethyl) - N - {/ * - Iß ' - (fi "- hydroxyethoxy) ethoxy] ethyl} -m-toluidine was produced by N- (β-cyanoethyl) -m-toluidine with 3 molecular proportions of ethylene oxide was reacted at 150 ⁰ C to the reaction. The resulting product was boiling from 190 to 195 ° C under a pressure of 0.1 mm of mercury.

The table below shows further examples of the preparation of the monoazo dyes of the invention indicated by, as in Examples 1 and 2, those indicated in the 2nd column of the table Amines are each diazotized and the resulting diazonium compounds each with the Coupling components specified in the 3rd column are coupled. In the 4th column of the table will be indicated the shades that arise when dyeing polyethylene terephthalate fabrics.

example Amine 3 2-chloro-6-bromo-4-nitroaniline 4th
5 2-cyano-4-nitro-6-bromoaniline
2-cyano-4-nitro-6-bromoaniline 6th 4-nitro-2-cyanoaniline 7th
8th
9 2-cyano-4-nitro-6-bromoaniline
p-nitroaniline
2-cyano-4-nitro-6-bromoaniline 10 2-chloro-4-nitroaniline 11
12th
13th 2,6-dichloro-4-nitroaniline
2-amino-5-nitrobenzonitrile
p-nitroaniline 14th p-nitroaniline 15th 4-nitro-2-methylsulfonylaniline 16
17th 4-nitro-2-methoxycarbonylaniline
2-chloro-4-nitroaniline 18th the same 19th the same 20th the same 21 the same 22nd the same

Coupling component. ■ Color tint

N - (/ i-cyanoethyl) -N - {/ ^ - [/ i '- (/ f-hydroxyethoxy) - orange-

ethoxy] ethyl} -m-toluidine brown

also violet

3- {N - (^ - cyanoethyl) -N - [/ ^ - (// - hydroxyethoxy) - purple
ethyl] amino} acetanilide

N - (/ ^ - cyanoethyl) -N - {/ i - [^ '- (//% hydroxyethoxy) - red

ethoxy] ethyl} -m-chloroaniline

also ruby red

also orange

N- (ß-cyanoethyl) -N - [/ H / * '- hydroxyethoxy) - ruby red

ethyl] aniline

N - (/ ^ - cyanoethyl) -N - [^ - (/ i'-acetoxyethoxy) - scarlet fever

ethyl] aniline

also yellow-brown

also blue-red

N - (^ - cyanoethyl) -N - {/ i - [; / - (/ i "-acetoxyethoxy) - red-orange

propoxy] ethyl} aniline

N - (/ i-cyanoethyl) -N - [(/ i-acetoxyethoxy) methyl] - red orange
aniline

N - ^ - CyanoäthyO-NC / H / ^ '- acetoxyäthoxyJäthyl] - red
aniline

likewise scarlet fever

N - (/? - cyanoethyl) -N- [y - (/ - acetoxypropoxy) - orange

propyl] -3-bromoaniline

N- (ß-Carbomethoxyethyl) -N - [/ i / - (/ f-acetoxyethoxy) - yellow-red
ethyl] -m-anisidine

N - (/ i-Phenoxyethyl) -N - [/ H / i '- (/? "- hydroxyethoxy) - ruby red
ethoxy} ethyl] -m-toluidine

N - (/ i-Carboethoxypropyl) -N - [/ ^ - (/; '- acetoxyethoxy) - yellow-red

ethyl] aniline

N - (^ - acetoxyethyl) -N - [/ H / <'- acetoxyethoxy) - yellow-red

ethyl] aniline

N - (/ i-cyanoethyl) -N - {^ - [/ i '- (/ i "-acetoxyethoxy) - scarlet fever

ethoxy] ethyl} aniline 609 620/29

Continuation of the example of Amin

Coupling component

10

Color tone;

N - [/; - Phenuxycarbonylethyl] -N - [// - (/ -; '- acetoxy- scarlet ethoxy) ethyl] aniline

N - [/ MMethoxycarbonyloxy) ethyl] - scarlet fever

N- [p '- (p "-acetoxyethoxy) ethyl] aniline

N - (/ j'-Phenoxyethoxy) -N - [/) - (// '- acetoxyethoxy) - bluish red

ethyljaniline

N - (/; - cyanoethyl) -N - [/; - (// - propionyloxyethoxy) - bluish red ethyl] aniline

N-i / V-CyanoathyO-N-QH / ^ - methanesulfonyloxy- red

ethoxy) ethyl] aniline

N - (/ ^ - cyanoethyI) -N - [/ ^ - (p "-benzoyloxyethoxy) - bluish red

ethyl] aniline

N - (// - cyanoethyl) -N - [/; - (/ <"- p-toluoyloxyethoxy) - blue-red ethyllaniline

N - (/) '- Cyanoethyl) -N - [/) - (/) "- ^ m-methoxy- bluish red

benzoyloxy} ethoxyethyl] aniline

N - (/) - cyanoethyl) -N - [/; - (/ 7'- | N'-phenylcarbamoyl} - bluish red ethoxyethyl] aniline

The table below gives further examples of the water-insoluble azo dyes in general formula

23 2-chloro-4-nitroaniline 24 the same 25th the same 26th 2-cyano-4-nitroaniline 27 the same 28 the same 29 the same 30th the same 31 the same

A-N = N

B-W

(V - O—) "- X

again, the symbols each having the meanings given in the corresponding columns of the table and where the shades obtained during dyeing are given in the last column of the table are.

These dyes can, according to Examples 1 and 2, by diazotizing the corresponding amines of the general formula A - NH ₂ and coupling the diazonium compounds formed with the corresponding coupling components of the general formula

B W

be generated.

At a Z Y B. W. X V η Color game tint

32 2-chlorine
4-nitrophenol H 33 the same H 34 the same H 35 2-cyano
4-nitrophenyl H 36 the same -CH ₃ 37 the same -Cl 38 the same H 39 2-chlorine
4-nitrophenyl H 40 the same -CH ₃

-C ₂ H, - -CN

H -QH ₄ - -CN H -C ₂ H, - - CN H -C ₂ H ₄ - - CN H -QH, - - CN H -QH, - - CN CH ₃ -QH, - - CN QH ₅ -QH, - - CN

-COCH ₃

-C ₂ H, - 4 scarlet

COCH ₃ QH, 6th Scarlet fever COCH ₃ -QH, - 10 Scarlet fever CO ■ OCH ₃ -QH, - 2 blue red COCH ₃ QH, 3 Ruby red COCH ₃ -QH ₄ - 3 Red COCH ₃ QH, 7th blue red COCH ₃ -C ₂ H ₄ - 2 Scarlet fever

-Cl -C ₂ H ₄ - -COOCH ₃ -COCH ₃

-C ₂ H ₄ - 2 red

continuation A. Z Y H B. C ₂ H ₄ W. X V η Color at tint game 2-cyano - NHCOCH., H -CH ₂ - - CN -COCH ₃ -C ₂ H ₄ - 3 red-violet 41 4-nitro-
6-bromophenyl 2-chlorine -CH ₃ H c ti
L ₂ H ₄ - CN -COCH ₃ -C ₂ H _4-2 Scarlet fever 42 4-nitrophenyI H C ₂ H ₄ the same -NHCOCH ₃ -OCH ₃ -C ₂ H ₄ - -COOCH ₃ -COCH ₃ -C ₂ H _4-2 blue red 43 the same - NHCOCH (CH ₃ ) ₂ -COOCH ₃ -COCH ₃ -C ₂ H _4-2 blue red 44 2,4-dinitro -NHCOCH ₃ -OC ₂ H ₅ C ₂ H ₄ -COOCH ₃ -COCH ₃ -C ₂ H _4-2 greenish 45 6-bromophenyl -OCH ₃ / ~> DD
C ₂ H ₄ Navy blue the same -NHCOCH ₃ -OCH ₃ -C ₂ H ₄ - -COOCH ₃ -COCH ₃ -C ₂ H _4-2 greenish
• Navy blue 46 the same -CH ₃ -COOCH ₃ -COCH ₃ -C ₂ H _4-2 blue-violet 47 2,4-dinitro -NHCOCH ₃ -OCH ₃ -C ₂ H ₄ - -COOCH ₃ -COCH ₃ -C ₂ H _4-2 greenish 48 6-chlorophenyl Navy blue 2-cyano -NHCOCH ₃ -OCH ₃ -C ₂ H ₄ - -COOCH ₃ -COCH ₃ C ₂ H ₄ 2 reddish 49 4-nitrophenyl Navy blue 2-cyano -NHCOCH ₃ -COOCH ₃ -COCH ₃ - C ₂ H ₄ I. green Blue 50 4-nitro- 6-bromophenyl

The 3 - {N - (ß- cyanoethyl) -N - [ß - (ß ' - hydroxyethoxy) ethyl] amino} acetanilide was obtained by reacting 3- [N- (ß-cyanoethyl) amino] acetanilide with 2 Molecular proportions of ethylene oxide generated at 70 ° C. The resulting product had a bp 260 to 270 under a pressure of 0.2 mm mercury.

The N - (ß - cyanoethyl) -N - {ß - W - \ ß "- acetoxyethoxy) propoxy] ethyl} aniline was produced by condensing <v / -Dichloropropane with 2 molecular fractions of the sodium salt of ethylene glycol and that the resulting β - [/ - (/ i "-Hydroxyethoxy) propoxy] ethanol was converted into the dichloro compound and treated with sodium acetate to replace one of the chlorine atoms with an acetoxy group, whereupon the product was condensed with N-β-cyanoethylaniline.

The N- (ß-cyanoethyl) - N - \ _ (ß - acetoxyethoxy) methyl] aniline used in the examples was obtained by reacting / if- (chloromethoxy) ethanol with acetic anhydride with subsequent condensation with N - (/? - cyanoethyl) aniline generated.

The coupling components used in Examples 32, 33, 34 would by condensation of N- (ß-cyanoethyl) aniline with 4, 6 or 10 molecular fractions of ethylene oxide with subsequent acetylation generated by means of acetic anhydride.

Claims (2)

Patent claims: 1. Process for the preparation of water-insoluble sulfonic acid and carboxylic acid group-free Monoazo dyes of the general formula N = N B-W (VOJ _n -X wherein P stands for a hydrogen, chlorine or bromine atom or a cyano, nitro, lower alkylsulfonyl, lower alkoxy or lower carbalkoxy group, Q stands for a hydrogen, chlorine or bromine atom, Y stands for a hydrogen or halogen atom or a lower alkyl or lower alkoxy group, Z door is a hydrogen or halogen atom or a lower alkyl, lower alkoxy, trifluoromethyl or acylamino group of the formula - NHCOX ¹ , where X ^{1 is} a lower alkyl group, η is 2 to 10, X Door is a hydrogen atom or an acyl group of the type defined in the description, which is derived from an aliphatic carboxylic acid, an aliphatic sulfonic acid, a monocyclic aromatic carboxylic acid, a monocyclic aromatic sulfonic acid or a lower aliphatic or monocyclic aromatic carboxylic or carbamic acid, V for a Is an alkylene group having 1 to 4 carbon atoms, B is an alkylene group having 1 to 4 carbon atoms tomen, W represents a cyano, phenyloxy, lower carboalkoxy, phenyloxycarbonyl or acyloxy group of the formula - OX, where X has the meaning given above, and the lower alkyl groups and lower alkoxy groups each contain 1 to 4 carbon atoms, characterized in that that a diazotized primary amine of the general formula NH, in which P and Q have the meanings given, with a coupling component of the general formula B-W (V - O—) "- X in which B, V, W, n, X, Y and Z have the meanings given, the amine and the coupling component are free from sulfonic acid and carboxylic acid groups. 2. The method according to claim 1, characterized in that one of the coupling component formula