DE2304202C2 - Disperse monoazo dyes, process for their preparation and their use - Google Patents

Description

NO ₂

NH ₂

Formula II

diazotized and the diazo compound obtained with a coupling component of the formula

R ¹

Formula III

couples, where Y, Z, V, W, R ¹ and R ^{2 have} the meanings given in claim 1 and the amine and the coupling component are free of carboxylic acid and sulfonic acid groups.

3. Use of the dyestuffs according to Claim 1 for dyeing synthetic organic textile materials, especially those made from aromatic ones Polyesters.

The invention relates to disperse monoazo dyes, a process for their preparation and their use for dyeing synthetic organic dyes Textile materials according to the preceding claims.

Similar monoazo dyes are known from DE-AS 1079 759, which differ from 2-amino-3-nitrothiophenes with an acyl group in the 5-position as Derive diazo component. Furthermore, similar monoazo dyes are known from US-PS 28 27 45p, which are derived from 2-aminothiophenes which have a nitro or Q_4-alkylsulfonyl group in the 3-position and in the 5-position a Ci_4-Alkylsulfonyl or a Contain sulfonyl Ci-4-alkylamido group. The dyes according to the invention have over these Dyes have the advantage that they have a much greater color strength.

Throughout this description, the terms "nicdrigalkyl" and "lower alkoxy" mean alkyl or Alkoxy radicals, having 1 to 4 carbon atoms.

Examples of five or one-membered nitrogen-containing heterocyclic rings which are obtained by combining R ¹ , R ² and the nitrogen atom N are pyridine, pyrrolidine, piperidine and morpholine rings.

The process for the preparation of the new monoazo dyes can be carried out by the usual measures will. For example, the method according to the invention can expediently be carried out in that one sodium nitrite to a solution or dispersion of the Amine in a strong inorganic acid or an aqueous solution thereof is added, or that one preferably the amine is stirred with nitrosylsulfuric acid and that the resulting solution or dispersion the diazo component to form a solution of the coupling component in water or in a mixture of Water and a water-miscible organic liquid is added, if necessary to adjust the pH of the mixture Facilitation of the coupling reaction adjusts and finally the resulting dye by usual Measures isolated

The amines of the formula (II) can in turn by

ίο customary procedures are obtained for (T ¹ each

Production of thiophene derivatives can be used. For example, a 2-halothiophene can be nitrated

whereupon the halogen atom in the 2-position by treatment with ammonia into an amino group

is convicted. Alternatively, the 2-aminothio pher.e, which contain electron withdrawing groups, produced from the thiophenes by conventional methods obtained by the methods described in

Chemical Reports, Volume 98 at page 3571 (1965) and Volume 99 on page 94 (1966).

Specific examples of amines of formula (II) are 2-amino-3,5-dinitrothiophene, 2-amino-3,4p-trinitrothiophene, 3-nitro-5- (carbonamido- or -methoxycarbonyl ^ -aminothiophene,

3,5-Dinitro-4-methyl-2-aminothiophene and 3,5-Dinitro ~ 4- {methoxy- or

-ethoxy-carbcnylj-a-aminothiophene. The preferred amine for use in this process is 2-amino-3,5-dinitrothiophene.

Examples of coupling components of the formula (III) are

2,5-dimethoxyaniline, Ν, Ν-diethylaniline, NJ> i-Di (^ - ace'.oxyethyl) -m-toluidine,

N-ethyl-N- (ß-hydroxyethyl) -m-aminoacetanilide, N, N-Di (/} - methoxycarbonylethyl) aniIin, N-ethyl-N- (0-cyanoethyI) aniline, N, N-Di (/? - acetoxyethyl) -m-chloroaniline, N J ^ -DiÖS-hydroxyäthyl) -1 -naphtylamine, 1,2,3,4-tetrahydroquinoline, N-m-tolylpyrrolidine, N-ethyl-N- (P-butoxycarbonylethyl) aniline, N-0- (0'-methoxyethoxycarbonyl) ethyl -m-toluidine and

N-0- (0'-hydroxyethoxycarbonyl) ethyl

-m-aminoacetanilide.

A preferred class of dyes according to the invention are the dyes in which Y is hydrogen and Z stands for nitro

A second preferred class of dyes according to the invention are the dyes of the formula

O ₂ N

R ⁴

wherein R ^{3 is} hydrogen or an optionally substituted lower alkyl radical; R ^{4 represents} an optionally substituted lower alkyl radical; V ^{2 is} hydrogen, lower alkyl or lower alkoxy and W ^{2 is} hydrogen, chlorine, bromine, lower alkyl, lower alkoxy or trifluoromethyl. The optionally substituted lower alkyl radicals represented by R ³ and R ⁴ are any

Radicals mentioned above for the symbols R 'and R ² .

The azo dyes according to the invention are suitable for dyeing synthetic organic textile materials and in particular of textile materials secondary cellulose acetate or cellulose triacetate, made of polyamide, such as. B. polyhexamethylene adipamide, and in particular from aromatic polyesters, such as. B. Polyethylene Terephthalate These materials can be in the form of threads, fibers or woven or have knitted materials.

The azo dyes mentioned can be applied to the synthetic textile materials by processes are commonly used for applying disperse dyes to such textile materials will. So the dyes in the form of aqueous dispersions by dyeing, padding, or Printing using the conditions and other additives specified in the Performing such procedures are common. Alternatively, the dyes can be applied to synthetic textile materials be applied by solution dyeing methods, for example by applying a solution or Dispersion of the dye in perchlorethylene, which optionally contains a smaller amount of water on the textile material, preferably with one increased temperature is used.

The dyes can also be used to dye synthetic polymers by melt dyeing in particular by a late injection technique. The colored polymers can then are spun in fibers or threads. Alternatively, the dyes can be used for dyeing synthetic Textile materials are applied by transfer dye printing.

If the dyes according to the invention are applied to synthetic textile materials, then they result in red to green colorations that are extremely fast to light and to have wet and dry heat treatments both before and after heat setting. The dyes also have a high coloring power, exhaust well and have excellent coloring, Leveling, temperature range and structure properties on synthetic textile materials, in particular aromatic polyester textile materials, which enables very deep color tones to be achieved

example 1

7.6 parts of sodium nitrite are added to 90 parts of sulfuric acid, the temperature increasing 30 "C is allowed to rise. The mixture is then cooled to 5 ° C, and a mixture of 50 parts of propionic acid and 300 parts of acetic acid is slowly added, the temperature rising to 15 ° C is left and then held at that temperature. The solution is then cooled to 0 ° C 18.9 parts of 2-amino-3,5-dinitrothiophene over 30 minutes added, and the mixture is then stirred for 30 min at 0 ° C. The resulting solution becomes a solution of 273 parts of NJ »l-di (jS-acetoxyethyl) aniline in 300 parts Water containing 30 parts of concentrated aqueous hydrochloric acid and 350 parts of ice was added. The mixture will Stirred for 50 min at 0 ° C. and the precipitated dye is filtered off, washed with water and dried.

When the dye is applied to aromatic polyester textile materials from an aqueous dispersion then it gives blue shades with excellent fastness properties.

If the above coupling component by an equivalent amount of N, N-Di (/? - acetoxyethyl) -m-tohudin is replaced, then a dye is obtained which greenish-blue on aromatic polyester textile materials Color tones

The 2-amino-3,5-dinitrothiophene used in the above example was obtained by reacting the sodium salt of cyanoacetic acid with the dimer of

in mercaptoacetaldehyde in aqueous medium at 80 ° C, cooling to 20 ⁰ C, the addition of acetic anhydride while maintaining the pH of the mixture 6-7, acidifying and isolating the 2-Acetylaminothiophen-3-carboxylic acid. This was then dinitriert in medium containing sulfuric acid at 0 ⁰ C, and the resulting 2-acetylamino-3,5-dinitrothiophene was isolated and then deacylated by heating in aqueous sulfuric acid

Example 2

2.03 parts of 2-amino-3,5-dinitro-4-riethylthiophene become to 3.8 parts of a W ^ igen solution of Nitrosylsulfuric acid in sulfuric acid, which is 9.6 Parts of acetic acid, 1.6 parts of propionic acid and 6 parts of sulfuric acid has been added, and that The mixture is stirred at 0 ° C. for 1 hour. Excess nitrous acid is then removed by adding Destroyed urea, and the resulting mixture is added to a solution of 2.79 parts of NJM-Ditf-acetoxyäthyl) -

m-toluidine in a mixture of 50 parts of water, 25 Parts of ice and 6 parts of 2N aqueous hydrochloric acid were added. The pH of the mixture is then through The addition of sodium acetate is adjusted to 3 and the dye which has precipitated is filtered off with water

j5 washed and dried '

When the dye is applied from an aqueous dye tape to aromatic polyester textile materials then it gives blue tones with excellent Authenticity properties.

The 2-amino-3,5-dinitro-4-methylthiophene was get yourself as follows:

Chloroacetone was with ■ sodium hydrosulfide in aqueous methanol reacted, and the resulting solution containing the reaction product was

treated with ethyl cyanoacetate in the presence of triethylamine at boiling point by adding water 2-Amino-3-ethoxycarbonyI-4-methyIthiophene precipitated, which was reacted with acetic anhydride To produce 2-AcetyIamino-3-ethoxycarbonyl-4-methylthiophene, which upon hydrolysis with an aqueous Solution of sodium hydroxide in 2-acetylamino-4-methylthiophene-3-caibonic acid was convicted. This was done by heating in Ν, Ν-diethylaniline at 220'C decarboxylated, and the 2-acetylamino-4-methy «th; ophen was dinitrated in sulfuric acid medium at -5 ° C. The product obtained was then in a aqueous sulfuric acid solution heated around the N-acetyl group to remove.

Example 3

Instead of the 18.9 parts of 2-amino-3,5-dinitrothiophene from Example 1, 23.4 parts of 2-amino-3A5-trinitrothiophene are used used to obtain a similar dye.

The 2-amino-3,4,5-trinitrothiophene was obtained by reacting 2-bromo-3,4,5-trinitrothiophene (Journal of Organics Chemistry 1957, page 1588) with ammonia in tetrahydrofuran.

Example 4

Instead of the 18.9 parts of 2-amino-3,5-dinitrothiophene, which were used in Example 1, 27.6 parts of 2-amino-3-nitro-5- (N, N-diethylcarbamoyl) thiophene is used to obtain a similar dye.

This thiophene compound was obtained by that 2-bromo-3-nitrothiophene-5-carboxylic acid (Chemical Abstracts 1963, page 3860 h) with thionyl chloride in Treated toluene in the presence of dimethylformamide and then reacted with diethylamine and then treated with ammonia to replace the bromine atom with an amino group.

Example 5

Instead of the 18.9 parts of 2-amino-3,5-dinitrothiophene from Example 1, 20.2 parts of 2-amino-3-nitro-5-methoxycarbonylthiophene are used is used to obtain a similar dye.

The above thiophene compound was obtained by esterifying 2-bromo-3-nitrothiophene-5-carboxylic acid by treatment with a 9% strength sulfuric acid solution in methanol and treating the bromine ester with a concentrated aqueous ammonia solution in the presence of dimethylformamide.

Example 6

2-Amino-3-nitro-5-cyanothiophene is diazotized by the procedure of Example 1 and treated with N -ethyl-N - (/ I-hydroxyathylI-m-toluidine coupled to obtain a dye, the aromatic polyester fabrics dyes in blue shades with excellent fastness properties

The 2-amino-3-nitro-5-cyanothiophene itself was obtained as follows:

The oxime of 2-acetylamino-5-formylthiophene (Journal of the Chemical Society 1955, page 1701) was converted to 2-acetylamino-5-cyanothiophene by treatment with acetic anhydride at the boiling point. The compound obtained was ^{nitrated at 40 °} C. in a mixture of acetic acid and acetic anhydride, and the nitro compound was deacetylated by heating in a solution of sodium hydroxide in aqueous methanol

In Table I further examples of the dye according to the invention are given, which the following formula

where the symbols have the values given in the corresponding columns of the table. the Shades of the dyeings obtained when the π dyes are applied to an aromatic polyester textile material are given in the last column of the table.

The dyes in this table were obtained by diazotizing the corresponding amines of the formula

NO ₂

NH ₂

and coupling with the corresponding coupling component lh .; formula

similar procedures to Examples 1 and 2 were used.

The amines of the above formula were obtained by procedures similar to those in the previous ones Examples for the preparation of 2-amino-3-nitrothiophene are described, but of the corresponding Intermediate products was assumed.

Table I.

Example Y

W ¹

hue

7th H 8th H 9 H 10 H 11th H 12th H 13th H 14th H 15th H 16 H 17th H 18th H 19th H 20th H 21 H 22nd H 23 H 24 H 25th H 26th H 27 H 28 H

Nitro H Nitro H Nitro H Nitro H Nitro H Nitro H Nitro H Nitro H Nitro H Nitro H Nitro H Nitro H Nitro H Nitro H Nitro H Nitro H Nitro H Nitro H Nitro H Nitro H Nitro H Nitro H

Nitro

H H H H H H H H H H H H H H H H H H H H H H

methyl

ethyl jö-Hydroxyiithyl grür.Jichblau 1
I. ¹ X) KJ ' O methyl methyl greenish blue ο! ethyl ethyl greenish blue H ethyl blue KJ
O H , / J-hydroxyethyl blue KJ H jö-acetoxyäi: hyl blue ß-nB uty rloxyäthy 1 jß-n-Butyrlo: iyäthyl blue jS-isobutyrloxyethyl jff-Isobutyrkixyäthyl blue ethyl jö-cyanoethyl blue jö-cyanoethyl iJ-cyanoethyl violet jö-Cyancathyl jiH / f-MethoxyäthoxycarbunyOäthyl violet ethyl / -Methoxycarbonylethyl greenish blue ethyl jo-acetoxyethyl greenish blue / -Methoxycarbonylethyl jS-methoxycarbonylethyl blue jS-ethoxycarbonylethyl jo-Athoxycai-bonylathyl blue ethyl ff-methyl-j3-; methoxycarbonyl) ethyl greenish blue ethyl jS-methyl-j8-i'butoxycarbonyl) ethyl greenish blue ethyl / i-chloroethyl greenish blue ethyl y-chloro - ^ - hydroxypropyl greenish blue ethyl ^ -Oy-Cyanoiithoxyjathyl greenish blue ethyl X / F-methoxycarbonylethylthioethyl greenish blue ethyl jS-Oy-AthoxxarbonylathoxyJathyl greenish blue ethyl / '\
-CH ₂ CH CH ₂
\ / greenish blue CH ₂ -S

continuation 1 Y 2 V ¹ W ¹ R ¹ R ^: hue K) KJ Example H Nitro H chlorine ^ 3-acetoxyethyl jj-acetoxyethyl reddish blue O 30th H Nitro H H jff-methoxyethyl jS-methoxy / lithium greenish blue 31 H Nitro H methyl jö-hydroxyethyl jS-hydroxyethyl bluish green K)
O 32 H Nitro Methoxy Methoxy jS-acetoxyethyl ./3-acetoxyethyl green K) 33 H Nitro H Methoxy ethyl ethyl green 34 H Nitro H bromine ethyl ethyl blue 35 H Nitro M. H ethyl ^ - (chloroacetoxyethyl greenish blue 36 H Nitro H methyl ethyl jtf - ^ - Methcixypropionyloxyiathyl greenish blue 37 H Nitro Methoxy Methoxy FI H greenish blue 38 H Nitro methyl Methoxy FI Fl greenish blue H Nitro Methoxy methyl ethyl ethyl green 40 H Nitro Fi methyl ethyl (y-Hydroxyl) utyl bluish green 41 H Nitro FI Fl ethyl ω-acetoxybutyl greenish blue 42 H Nitro methyl methyl FI jS-hydroxyiithyl greenish blue 43 H Nitro Fl FI n-dodecyl jö-HydroxyHthyl greenish blue 44 H Nitro Fl H ^ - (p-Bromobinzoyl-
oxyethyl ^ - (p-bromocibenzoyloxy) ethyl blue 45 H Nitro methyl Fl / J-FI hydroxyethy! / i-Flydroxyiithyl greenish build 46 H Nitro chlorine Fl ^ -Flydroxyethyl ^ -Hydroxyethyl blue 47 II Nitro H H ethyl fl- ( Cyanomethoxy carbonv 1 ethyl blue 48 H Nitro FI FI H yi-methoxycarbonylethyl blue 49 H Nitro H H jö-hydroxyethyl > Phenylethyl blue 50 H Nitro chlorine H j3-acetoxyethyl > Acetoxyithyl blue 51 H Nitro H FI jS - (/ f-methoxyethoxy-
carbonyl) ethyl jÖ - (/ T-methoxyalhoxycarbonyl) ethyl blue 52 H Nitro FI methyl ^ -Formyloxyiithyl / j-formylotylethyl blue 53

continuation H Z V ¹ W ¹ R ¹ R ² hue K) Example Y II Nitro H methyl ^ - (ethoxycarbonyl-
methylaminocarbonyl
oxyethyl ./f- ETHoxycarbonylmethylaminocarbonyl-
oxy) ethyl blue CO 54 H Nitro H methyl ethyl jo-acetylethyl greenish blue O
■ Ji »
K) 55 H Nitro H H ethyl ω-hydroxypentyI greenish blue K) 56 H Nitro H H ethyl ^ -Chloro-y-i p -chlorophenoxy) propyl greenish biau 57 H Nitro H methyl XMethylsullbnyl-
oxy) ethyl j »- (methylsulfonyloxy) ethyl blue 58 H Nitro H methyl jö-cyanoethyl j8-phenoxyethyl blue 59 H Nitro H Ethoxy
carbonylmethyl ethyl ethyl greenish blue 60 H Nitro H Methd v methyl ethyl ethyl «Greenish blue 61 H Nitro Ethoxy
carbonyl
mcthoxy Ethoxy
atrbonyl
methoxy II H greenish blue 62 H Nitro methyl Ethylthio ethyl ethyl greenish blue 63 H Nitro II Ethoxycarbonyl ethyl Ethy! blue 64 H Nitro H H ethyl jß- (ethoxycirbonyloxy) ethyl greenish blue 65 II Nitro H Benzoyloxy ethyl ethyl bluish green 66 H Nitro H Methyl-
sulfonyloxy ethyl ethyl greenish blue 67 H Nitro H H ethyl a ^ -DKäthoxycarbonynäthyl greenish blue 68 Nitro H Methoxy
carbonyl
methylthio ethyl ethyl greenish blue 59 H H H Nitro H H ethyl p-methoxycirbonylbenzyl greenish blue 70 H Nitro H H ethyl Phenyl greenish blue 71 H Nitro H Acetyl H Cyclopentyl blue η Nitro H O-acetoxyethyl ./J- acetoxyethyl blue '3

continuation

Example Y

V ¹

R ¹

hue

74 75 76 77 78 79 80

Sl 82

H H H H H H H

H H

Nitro Nitro Nitro Nitro Nitro Nitro Nitro

Nitro nitro

H H H H H H H

H H

83 H Nitro H 84 H Nitro H 35 methyl Nitro H 36 methyl Nitro H 37 methyl Nitro H 88 methyl Nitro H . 89 methyl Nitro methyl 90 methyl Nitro H 91 methyl Nitro H 92 p-nitrophenyl Nitro H 93 H Methoxy
carbonyl H ro 94 H Methoxy
carbonyl H 30 238/97 95 H jS-methoxy-
ethoxy
carbonyl H

Methylsulfonyl H ethyl violet Ul to cn Cyano ethyl ethyl blue methyl ethyl jS-Gff-MethoxyathoxycarbonyloxyJathyl greenish blue - &> ■ Trifluoromethyl H > Cyanoethyl blue K)
^^ H H .Ä / 8-dimethylethyl blue K) N-ethylsulfonyl ethyl ethyl violet N-ethyl
carbamoyl ethyl methyl bluu H methyl N-methylsulfonyl-jS-p-anisidinoethyl greenish blue methyl ethyl j!? - [/ J'-Oß "-Methoxyethoxy) ethoxycarbonyl] -
ethyl greenish blue H ethyl m-methylsuironylbenzyl greenish blue methyl j8-phenoxyethyl - CJH4OCONHCH2COOM, greenish blue methyl jS-acetoxyutyl jif-acetoxyethyl blue H H j8-cyanoal; hyl violet II H Cyclopenlyl blue H jö-cyanoethyl j8- (m-methoxyphenoxycarbonyl) ethyl violet Methoxy H H blue chlorine ^ -Methoxycarbonyl-
ethyl ./J- methoxycarbonylethyl violet H H ./J-OfF-AcetoxyathoxyJathyl blue methyl ^ -Acetoxyethyl jS-acetoxyethyl bluish green methyl jJ-acetoxyethyl jß-acetoxyethyl violet methyl ethyl j? -Cyanoethyl Red methyl ethyl ethyl violet

continuation

example

96 H Cyano M. 97 M. Cyano H 98 H Cyano H 99 U Cyano H 00 11th Carbamoyl H 01 H N-phenyl-
carbamoyl H 02 H N-ethyl
carbamoyl H 03 p-nitrophenyl Isopropyl H 04 p-nitrophenyl 2-nitro
4-methyl-
phenyl H

Methyl methyl

Methyl methyl methyl

methyl

H
H

methyl ./J- methoxycarbonylethyl ethyl ^ -Actitoxyethyl X / C-methoxyethoxy-
carbonyl) ethyl .//-(/f-MethoxyäthoxycarbonyOäthyl jCt-acetoxyethyl jo-acetoxyethyl jff-acetoxyethyl jff-acetoxyethyl jff-acetoxyethyl ^ -Acetoxyiithyl j8-acetoxyethyl ^ S-acetoxyethyl ^ -Acetoxyethyl / '- acetoxyethyl ^ O-hydroxyethyl ethyl

hue

bluish red

violet

violet

violet violet violet

violet

blue
blue

Table II shows further dye examples according to the invention, which are obtained by diazotizing 2-amino-3,5-dinitrothiophene and coupling the resulting diazo compound with the coupling components indicated in the second column of the table, using processes similar to

can be used in Example I. The third column of the table shows the color shades that are obtained with these dyes when they are applied to an aromatic polyester textile material.

Table II Coupling component hue at game N-0n-toly!) Pyrrolidine greenish 105 blue N- (m-Tolyl) morpholine greenish 106 blue N-phenylthiamorphon greenish 107 blue N - (/? - cyanoethyl) -3-hydroxy-l, 2,3,4- greenish 108 letra-hydroquinoline blue 2,3-dimethyl-N-ethyl-N - (/ - acetoxy- greenish- 109 äthy!) - aniline blue N - {/ - hydroxyethyl) - «- naphthylamine blue UO

Claims (2)

Patent claims: 1. Disperse monoazo dyes which are free from sulfonic and carboxylic acid groups and which formula R ¹ 10 13th Formula I. have, in which Y for hydrogen, nitro, lower alkyl, phenyl, Tolyl, anisyl, chlorophenyl, bromophenyl, nitrotolyl or nitrophenyl; Z for lower alkyl, phenyl, tolyl, anisyl, chlorophenyl, bromophenyl, nitrotolyl, nitrophenyl, Nitro, cyano, lower alkoxycarbonyl, hydroxy lower alkoxycarbonyl, lower alkoxy-low-alkoxycarbcny !, Cyanonicdrigaikoxycarbonyi, Chloro-lower alkoxycarbonyl or carbonamido of the formula: - CON 30th whereby T ^{1 is} hydrogen, lower alkyl or phenyl and T ^{2 is} hydrogen or lower alkyl; V for hydrogen, chlorine, lower alkyl, hydroxy lower alkyl, lower alkoxy lower alkyl, lower alkoxycarbonyl lower alkyl, lower alkoxy, Hydroxy-lower alkoxy or lower alkoxycarbonyl-lower alkoxy; W for hydrogen, chlorine, bromine, lower alkyl, hydroxy lower alkyl, lower alkoxy lower alkyl, lower alkoxycarbonyl lower alkyl, lower alkoxy, hydroxy lower alkoxy, lower alkoxycarbonyl lower alkoxy, lower alkylthio, Lower alkoxycarbonyl-lower alkylthio, lower alkoxycarbonyl, carbonamides of the formula: 50 - CON whereby T ¹ and T ^{2 have} the meanings given above own. Sulphonamides of the formula: -SO ₂ N 4th \ 60 whereby T ¹ and T ^{2 have} the meanings given above, Lower alkylcarbonyl, lower alkylsulphonyl, lower alkylsulphonyloxy, cyano, trifluonnethyl, Lower alkylcarbonyloxy, benzoyloxy or SuI-phamato of the formula: -OSO ₂ N whereby T ¹ and T ^{2 have} the meanings given above own, stands; and R ¹ and R ² each independently represent hydrogen, lower alkyl, n-dodecyl, hydroxy lower alkyl, ω-hydroxypentyl, cyano lower alkyl, chloro lower alkyl; Lower alkoxy-lower alkyl, lower alkylcarbonyloxy-lower alkyl, ß- (chloroacetoxy) ethyl, Phenyiniedrigaikyi, p-methoxycarbonylbenzyl, m-methylsulfonylbenzyl, / J-phenoxyethyl, Lower alkoxy-lower alkoxy-lower alkyl, Hydroxy-lower alkoxy-lower alkyl, lower alkoxycarbonyl-lower alkyl, Hydroxy-lower alkoxycarbonyl-lower alkyl, lower alkoxy-lower alkoxycarbonyl- lower alkyl, Cyano-lower alkoxycarbonyl-lower alkyl, lower alkoxy-lower alkoxy-lower alkoxy- carbonyl-lower alkyl, Hydroxy-lower alkoxy-lower alkoxycarbonyl lower alkyl, Lower alkylcarbonyloxy-medrigalkoxycarbonyl- lower alkyl, y-chloro-ß-hydroxypropyl, ^ - (P'-cyanoethoxy) ethyl, (X ^ -Di (ethoxycarbonyl) ethyl, ^ H (MethylaminosulfonyI) äthyl, ^ '- Äthoxycarbonyläthoxy) äthyl, /? - (P'-MethoxycarbonyläthyIthio) ethyl, ^ - (J3'-methoxypropionyloxy) ethyl, j9- (p-bromobenzoyloxy) ethyl, / Ϊ-formyloxyethyl, jJ-acetylethyl, j? - (ethoxycarbonyloxy) ethyl, ^ '- Acetoxyethoxy) ethyl, ^ - (m-Methoxyphenoxycarbonyl) ethyl, jJ - ^ '- MethoxyäthoxycarbonyloxyJäthyl, ^ - {Metb-lsulfony! Oxy) ethyl, ^ - (Ethoxycarbonylmethylaminocarbonyl oxy) ethyl, ^ -Chloro-y-fp-chlorophenoxyjpropyl, N-methylsulfonyl - ^ - anisidinoethyl, ^ • (methoxycarbonylmethylaminocarbonyl oxy) ethyl, Cyclopentyl, phenyl, tolyl, anisyl, chlorophenyl, bromophenyl, 2 »pyridyl, 4-pyridyl or 1,4-oxathien-2-on-6-yl-methyl, or R ¹ and R ² together with the nitrogen atom represent a pyridine or pyrrolidine -, piperidine, morpholine or thiomorpholine ring or R ¹ can be combined with V if it is in the o-position to the amino group, with a tetrahydro quinoline nucleus is formed, or V and W if they are in o-position to each other, too may be united with each other to form a group having 4 carbon atoms, so that a Naphthalene core is formed 2. Process for the preparation of the dyes according to claim t, characterized in that one is in on is known to be an amine of the formula