DE2140278A1 - Water-soluble dyes and dye intermediates - Google Patents

Abstract

Dye intermediates are of formula D-R-N-CH2CH2CH2SO3M (where R is an aryl group with 1 or 2 aromatic rings, D is an H atom linked to the nuclear carbon of R in the p-position to the N atom; R1 is a residue linked by an alkyl C atom to the N atom, and M is H, Na, K or NH4). The intermediates are used to prepare water-soluble dyes of the formula A-N=N-R-N-CH2CH2CH2CH2SO3M (where A-N=N- is the coupling residue of a diazotised aromatic or heterocyclic amine or of a diazotised amino-monoazo intermediate. The alkali metal or ammonium salts of (I) have surface-active props. inaqs. soln. The dyes (II) can be used on synth. or natural polyamides and sec. cellulose acetate rayon; certain of the dyes show very good resistant to light and washing.

Description

R e ctio n s pertaining to: "Dyes and processes for their Manufacture "The invention relates to water-soluble acidic dyes for natural and synthetic polyamide fibers and for secondary cellulose acetate fibers.

The new acidic dyes according to the invention have the general formula: in which AN = N- denotes the radical of a diazotized aromatic amine, a diazotized heterocyclic amine or a diazotized aminomonoazo intermediate after coupling, R is an aryl radical with 1 or 2 aromatic rings and the radical AN = N- after coupling over the carbon atom, which is located in the ring in the para position to the nitrogen atom, is bonded and where R1 denotes a radical which is bonded to the nitrogen atom via an alkyl carbon atom and Id denotes a laser, sodium or potassium atom or an ammonium group .

These dyes are generally water-soluble acidic dyes with a wide range of shades. While the dyes of the formula I have other water-solubilizing groups apart from the sulfonic acid group of the propanesulfonic acid residue it is generally preferable to use the water-solubilizing agents Groups to those supplied by the propanesulfonic acid to restrict to such Achieve solubility characteristics of the dye as they are for good exhaustion from neutral and alkaline baths on polyamides or secondary cellulose acetate rayon required are.

The dyes of the formula I are prepared by diazotizing a primary aromatic imine, a primary diazotizable heterocyclic amine or a primCres aminomonoazo intermediate and the diazonium salt with a compound of formula II in which R is an aryl radical with one or two aromatic rings, D is a hydrogen atom on the carbon atom of the ring R, which is in the para position to the nitrogen atom, R1 is a radical bonded to the nitrogen atom via an alkyl carbon atom and M is hydrogen or sodium or a potassium atom or an ammonium group, couples and optionally converted into the desired salt by appropriate acidification and / or neutralization.

A special group of dyes, which are produced from the above-mentioned intermediates, has the general formula: in which A1-N = N- the residue of a diazotized aromatic amine, a diazotized heterocyclic amino or a diazotized aminomonoazo intermediate after coupling, one of the groups: and R1 is an alkyl radical with 1 to 8 carbon atoms, a benzyl, cyclohexyl, -CH2CH2CN- radical, R2 a hydrogen atom, a lower alkyl group with 1 to 4 carbon atoms, a halogen atom, a lower O-alkyl group with 1 to 4 carbon atoms or the group -NHCOR4, R a hydrogen atom, a lower alkyl group with 1 to 4 carbon atoms, eille lower O-alkyl group with 1 to 4 carbon atoms or the group -NHCOR4 and B.4 denote a lower alkyl group with 1 to + carbon atoms, a tolyl, phenyl or halogenophenyl group.

The special group of barbs includes acidic I; ionoazo- and Disazo dyes.

Certain particularly suitable dyes for polyamides and secondary cellulose acetate tatrayon can be found in a nonoazo subgroup of the formula III, in which A1 the group: is, in which R5 is a hydrogen or halogen atom or a nitro, cyano, lower alkyl group with 1 to 12 carbon atoms, lower alkoxy, trifluoromethyl, alkylsulfonyl, acetyl, carboxamido, N-alkylcarboxamido, carbalkoxyl, Sulfonamido, N-alkylsulfonamido or N, N-dialkylsulfonamido group, R6 is a hydrogen or halogen atom, an ITitro, cyano, lower alkyl or lower alkoxy group and R7 is a hydrogen or halogen atom or a lower alkyl or mean lower alkoxy group.

Dyes of this subgroup can be prepared by diazotized aromatic amines with the new intermediates described above of formula I couples. Aromatic amines suitable for this purpose are e.g. aniline, toluidines, Xylidines, mesidine, dodecylaniline, anisidines, phenetidines, monochloranilines, dichloranilines, Trichloroaniline, ljononitroaniline, trifluoromethylaniline, chlorotrifluoromethylaniline, Chlornitroaniline, 2,4-dinitroaniline, chloronitroaniline, 6-bromo-2,4-dinitroaniline, Fluordinitroaniline, Cyanonitroaniline, Cyanodinitroaniline, Cyanoaniline, Chlorcyanoaniline, Chlorodicyanoaniline, aminoacetophenone, methylsulfonylaniline, 2,4-dinitro-6-methylsulfonylaniline, 2-bromo-6-chloro-4-nitroaniline, 2-alkylsulfinyl-4-nitroaniline, cyclohexl-4-aminobenzoate, 6-bromo-4-nitro-2-cyanoaniline, methyl anthranilate, aminoacetanilide, aminobenzanilide, Aminohalobenzanilides, Aminobenzene sulfonamides, N'-methylaminobenzene sulfonamides, N ', N'-dimethyl-aminobenzene sulfonamides, 2-amino-4-nitroanisole, 2-amino-5-nitroanisole, nitrotoluidines, nitrooxylidines, 1-methoxy-2-aminobenzene-4-sulfonamide, N ', N'-dimethyl-3-amino-4'-methylbenzenesulfonamide, p-aminobenzamide, m-aminobenzamide, o-aminobenzamide, N '- (2-hydroxyethyl) -2-aminobenzamide, N'-butyl-4-aminobenzamide, etc.

Preferred dyes of this subgroup have the structure: .in A1 and R1 is a lower alkyl group having 1 to 8 carbon atoms, a -CH2CH2C-N-, a -CH2CH20H-, cyclohexyl or benzyl group, R2 is a hydrogen atom or a methyl group and M is a hydrogen, sodium or potassium atom or an ammonium group.

This preferred subgroup includes yellow to red acidic dyes, some of which have a particularly good lightfastness and washfastness, an excellent one Solubility in water, excellent substance for cellulose acetate rayon and nylon and can be manufactured economically from commercially available intermediates can.

It has been stated so far (Chemical Abstracts, 52, 10918a - 1958) that when coupling a compound of the structure similar to the compounds used according to the invention: With a melting point of 225 to 227 ° C with diazotized p-nitroaniline a red dye is formed which has favorable dyeing properties (apart from washing fastness) on acetatrayon. These results are not reproducible since the compound formed in the synthesis of a compound of the formula C had a melting point of 261 to 262.5 ° C. and the dye obtained from this compound by coupling with diazotized p-ITitroaniline was more orange than red owned. It dyed acetatrayon from salt baths well in shades of orange, as shown in Example 2, had poor lightfastness and good ashfastness.

As is also shown in Example 2, the dye of the formula B according to the invention colors: Acetatrayon and nylon in scarlet shades with very good lightfastness on nylon and excellent lightfastness on acetatrayon. This dye also has particularly good wash fastness on acetatrayon, which has been stated as a disadvantage in the case of the corresponding dye which has been prepared from intermediate product C.

Other particularly valuable acidic monoazo dyes can be found in another subgroup of formula III, in A1 Y1 is a hydrogen or halogen atom or an NO2, SO2CH3, CH3 or a lower O-alkyl group with 1 to 4 carbon atoms, Y2 is a hydrogen or halogen atom or a nitro group, Y3 is a hydrogen or halogen atom, a lower alkyl or nitro group and Y4 denotes a hydrogen atom or a lower alkyl group.

The dyes in this subgroup dye nylon and acetatrayon in a wide range of just true tones, such as red, purple, and blue.

They can be made by coupling diazotized heterocyclic ones Amines, vvie z .. 2-amino-6-methylbenzothiazole, 2-amino-6-methoxybenzothiazole, 2-amino-6-ethoxybenzothiazole, 2-amino-6-chlorobenzothiazole, 2-amino-6-bromobenzothiazole, 2-amino-6-methyl-sulfonylbenzothiazole, 2-amino-5,6-dichlorobenzothiazole, 2-amino-4-nitro-6-methxlsulfonylbenzothiazole, 2-amino-4,6-dinitrobenzothiazole, 2-amino-5-methyl-6-methylsulfonylbenzothiazole, 2-amino-5-nitrothiazole, 2-amino-4- or 5-alkylthiazoles, 2-amino-4- or 5-chlorothiazoles and 2-amino-4,5-dialkylthiazoles.

The invention also relates to a particularly valuable group of disazo dyes of the formula I, in which A is a group of the general formula: B1 - N = N-B2-, in which B1 is a benzene ring or a substituted benzene ring, the substituents of which are halogen atoms, nitro, Cyano, lower alkyl, lower alkoxy, trifluoromethyl, alkylsulfonyl, acetyl, carboxyamido, sulfonamido, N-alkylsulfonamide-o-, N, N-dialkylsulfonamido, N-alkylcarboxamido and / or carbalkoxy groups; B2 is a 1,4-naphthylene group or a 1,4-phenylene group of the formula: denotes in which R8 is a hydrogen atom, a lower alkyl, lower alkoxy or -gECOR4 group, R9 is a hydrogen or halogen atom, a lower alkyl, lower alkoxy, -NHCOR4 or -NHSO2R4 group and R4 is a lower one Denote an alkyl group having 1 to 4 carbon atoms, a phenyl, tolyl or halogenophenyl group.

Diazo carbides of the general formula given above can be prepared are made by coupling different anilines, such as aniline, toluidines, anisidines, xylidines, Phenetidine, 2-chloro-4-nitroaniline, nitroaniline, cyanoaniline, chlorocyanoaniline, Nitrocyanoaniline, 2,6-dichloro-4-nitroaniline, 4-aminomethylsulfone, 4-aminoacetophenone, 2-amino-5-nitro-toluene, 2-amino-5-nitroanisole, 3-nitro-4-aminotoluene, 2,4-dichloroaniline, 2,5-dichloroaniline, 2-trifluoromethylaniline, 2-trifluoromethyl-4-chloroaniline, 2,4-dinitro-6-bromaniline, 2-cyano-4,6-dinitroaniline, nitrocresidin, 2-amino-5-nitrobenzoic acid methyl ester, 3-ritro-4-aminobenzoic acid butyl ester, 4-aminobenzoic acid methyl ester, 4-aminoacetanilide, 3-aminobenzanilide 4-aminobenzenesulfonamide, N ', N'-dimethyl-4-aminobenzene-sulfonamide etc. with 1-naphthylamine, aniline or an aniline derivative which is p-position to the NH2 group is unsubstituted, vJie o-toluidine, m-toluidine, o-anisidine, m-anisidine, o-phenetidine, cresidine, 2,5-dimethoxyaniline, 2,5-diethoxyniline, m-aminoacetanilide, 4-acetylamino-2-aminotoluene, monobenzoylm-phenylenediamine, 2-amino-4-acetylaminoanisole, 2-Amino-4-acetylamino-phenetol, m-chloroaniline, m-bromoaniline, or monomethane-sulfonyl-m-phenylene-diamine. These amines are all known compounds. The one formed with the first clutch zr-aminomonoazo intermediate is then diazotized again and with another Compound of the formula II coupled in aqueous solution, preferably at pH 2 to 7.

A preferred subgroup of disazo dyes has the formula I, in which R or R1 is a lower alkyl group with 1 to 8 carbon atoms, a CN2CH2CN, CH2CH2OH, cyclohexyl or benzyl group, A and R10 and R11 each represent a hydrogen atom or a methyl group.

The disazo dyes of this preferred subgroup can be prepared are by diazotization of 4-aminoazobenzene, 4-aminoazotoluene or a 4-amino-methyl-azobenzene and coupling with another compound of the formula II, in the R1 is a lower alkyl radical with 1 to 8 carbon atoms, a CH2CH2CN-, CH2CH20H-, Means cyclohexyl or benzyl group.

From an economic point of view, ie because of the cost and the availability of the starting compounds, it is preferred to use a compound of the formula: in which R1 is a methyl or ethyl group, R2 is a hydrogen atom or a methyl group and M is a hydrogen, sodium or potassium atom or an ammonium group, it should be assumed that these are obtained by reacting N-ethyl-m-toluidine or N-methylaniline with propanesulfone will.

These compounds of the formula IV are preferred for the preparation of technically valuable dyes (especially those like those below and are described in the examples), which by coupling of diazotized 4-ETitroaniline, 3-chloroaniline, 2,5-dichloroaniline or 4-iuiiinoazobenzol can be produced. in the This particular group of dyes is described below as dyes according to the invention called type IV.

So far there was a pronounced lack of acidic dyes, which were readily soluble in water and which were applied to secondary cellulose acetate fibers to obtain colors with good lightfastness and wetfastness. The usual water-insoluble dispersed dyes generally used for dyeing of cellulose acetate are used, are known to have no strength opposite to the "." ash or other wet treatment. Many so far available acidic dyes that color cellulose acetate from salt baths other disadvantages. They have a bad affinity for the fiber, a low one Lightfastness or are uneconomical because they are manufactured at high cost must or have a low coloring value.

The type IV dyes according to the invention, especially those which color in yellow, orange or red tones, the disadvantages indicated above because they are economical to manufacture, Acetatrayon in luminous light to dark tones colors, a very good lightfastness and a good to have excellent wet strength and particularly good water solubility.

In addition, these dyes of the In type have proven to be technically suitable proven for dyeing and printing nylon fabrics, with uniform lightfast Yellow, orange and red tones are created. Due to their unusually good solubility in water, combined with the good lightfastness, the neutral / alkaline affinity and the Uniform dyeing properties come from those that occur in the textile dyeing industry Meeting requirements.

This unusual combination of properties, especially the high one .7 water solubility, combined with the good neutral - alkaline affinity and piling on ("pile-on") to deep shades of color, like many of these dyes from Type IV, peculiar to itself, allows its use in cases where there is a high (short ratio) ratio Dye to liquid is required, such as ben jigger - dye and padding and while printing.

The following examples serve to illustrate the preparation of representative dyes, the use of the dyes for dyeing Polw-amiden and cellulose acetate secondary fibers and the one made with it new colorations.

In these examples, unless otherwise specified, with parts and percent always mean parts by weight or% by weight.

Examples For example, 13.8 parts of p-nitroaniline were diazotized and the resulting clear solution at 00C to a solution of 26 Parts of N-ethyl-N- (m-tolyl) -3-aminopropanesulfonic acid (sodium salt) in 150 parts Water was added together with 25 parts of sodium acetate and the mixture was cooled to 50C. the Coupling was quick and a red precipitate formed. The pH of the After 1 h, the suspension was increased by adding a sodium hydroxide solution of 5 9.4 and the product was filtered off and dried. 40 parts were obtained a dark red solid, the nylon from neutral or alkaline dye baths in chestnut brown tones and cellulose acetate in beautiful red tones from dye baths, containing sodium chloride colored. The colorations of acetate were light and light washable.

The product had the structure: In 8 »iel 2 For comparison, dyes of the structure: by coupling diazotized p-nitroaniline with the intermediates of the structure: 't manufactured.

The dyes A and B were obtained from aqueous dye baths containing 20% sodium chloride contained, applied to secondary cellulose acetate. Dye A gave one yellow-orange color, which after only 10 h in a fade-0-meter became much more palpable. The dye B gave scarlet shades, which did not after 10 h and after 40 h only slightly faded.

Both dyes gave sufficient colorations on cellulose acetate Washfastness possessed.

Following the general procedure given in Example 29, additional acidic monoazo dyes of the general structure were made: manufactured. X These examples are given in Table IV below.

TABLE IV Example amine that was diazotized to R1 R2 R3 coloring on the group AN = N Acetate nylon 66 No. 3 aniline methyl HH yellow yellow 4 aniline sec-butyl HH "" 5 aniline 2-ethylhexyl HH ""6 aniline cyclohexyl HH""7 aniline benzyl HH""8 aniline 2-hydroxyethyl HH""9 aniline ethyl H CH3""10 aniline 2-hydroxyethyl H CH3""11 aniline 2-cyanoethyl CH3 H""12 aniline ethyl CH3 H "" 13 p-toluidine methyl HH "" 14 p-toluidine sec-butyl HH "" 15 p-toluidine 2-ethylhexyl HH "" H 16 p-toluidine cyclohexyl H "" H 17 p-toluidine benzyl H "" 18 p-toluidine 2-hydroxyethyl HH "" 19 p-toluidine ethyl H CH3 "" 20 p-toluidine 2-hydroxyethyl H CH3 "" 21 p-toluidine 2-cyanoethyl CH3 H "" continued TABLE IV: continued to TABLE IV example amine that was diazotized to R1 R2 R3 coloring on the group AN = N acetate nylon 66 No. 22 p-toluidine ethyl CH3 H yellow yellow 23 o-anisidine methyl HH "" 24 o-anisidine cyclohexyl HH ""25 o-anisidine ethyl CH3 H yellow-orange yellow-orange 26 o-aminobenzot rifluorid ethyl CH3 H orange orange yellow-orange 27 m-chloroaniline methyl HH yellow-orange 28 m-chloroaniline sec-butyl HH "" 29 m-chloroaniline cyclohexyl HH "" m-chloroaniline benzyl H 30 H yellow yellow m-chloroaniline 2 -Hydroxyäthyl HH yellow-orange yellow-orange 31 m-chloroaniline 2-cyanoethyl CH3 H "" 32 m-chloroaniline ethyl CH3 H orange orange 33 p-nitroaniline methyl HH red red 34 p-nitroaniline sec-butyl HH red red 35 p -Nitroaniline cyclohexyl HH red red 36 p-nitroaniline benzyl HH scarlet scarlet 37 p-nitroaniline 2-hydroxyethyl HH "" 38 p-nitroaniline ethyl H CH3 "" 39 p-nitroaniline 2-hydroxyethyl H CH3 "" 40 p-nitroaniline 2- Cyanoethyl CH3 H "" 41 cont. TABLE IV: cont. To TABLE IV with amine that was diazotized to R1 R2 R3 coloring on the group AN = N acetate nylon 66 No. 42 p-nitroaniline ethyl OCH3 OCH3 bluish- red bluish-red 43 2,5-dichloroaniline methyl HH yellowish-orange yellowish-orange 44 2,5-dichloroaniline ethyl CH3 H orange orange 45 o-chloro-p-nitroaniline methyl HH red cas tan-brown 46 o-chloro-p-nitroaniline ethyl CH3 H red violet 47 o-chloro-p-nitroaniline methyl HH red bluish-red 48 o-chloro-p-nitroaniline sec.-butyl HH red bluish-red 49 o-chlorine- p-nitroaniline cyclohexyl HH red bluish-red 50 o-chloro-p-nitroaniline benzyl HH red red 51 o-chloro-p-nitroaniline 2-hydroxyethyl HH red bluish-red 52 o-chloro-p-nitroaniline ethyl H CH3 red red 53 6-bromo-2,4-dinitroaniline ethyl CH3 H violet blue 54 2-amino-5-nitrobenzo-ethyl CH3 H violet violet nitrile 55 2-bromo-6-chloro-4-ethyl CH3 H violet violet nitroaniline 56 2- Bromo-6-chloro-4- 2-hydroxyethyl HH red bluish-red nitroaniline 57 methyl anthranilate ethyl CH3 H yellow yellow 58 p-aminoacetanilide methyl HH yellow yellow Continued TABLE IV: Continued to TABLE IV In the case of amine, which to R1 R2 R3 coloring based on the group AN = N acetate nylon-66 no. Was diazotized 59 p-aminobenzamide methyl HH yellow yellow 60 N'-N'-dimethyl-3-amino-4'-methylbenzene-ethyl CH3 H orange orange sulfonamide 61 1-Methoxy-2-amino-methyl HH yellow yellow ben zol-4-sulfonamide 62 2-Amino-5-nitroanisole ethyl CH3 H red red 63 N '- (2-hydroxyethyl) ethyl CH3 H yellow yellow 2-aminobenzamide 64 p-nitroaniline ethyl OCH3 CH3 bluish-red bluish-red 65 p-Nitroaniline Ethyl Cl H red red 66 2,4-Dinitroaniline Ethyl CH3 H violet violet 67 2,4-Dinitroaniline Methyl CH3CONH OCH2CH3 blue blue Following the general procedure of Example 29, further monoazo dyes of the general formula: made. These examples are given in Table V.

T A B E L L E V Bei- amine, which is part of the acetate-rayon nylon-66 game A-N = N group di no. aniline yellow yellow 69 p-oluidine yellow yellow 70 o-anisidine was azotized orange orange 71 m-chloroaniline orange orange 72 p-nitroaniline red bluish-red 13 o-chloro-p-nitroaniline violet violet 74 2,4-dinitroaniline green-blue blue B e i 5 p i e 1 75 -A solution of 4.9 g of 2-amino-6-nitrobenzothiazole in 50 ml of 85% Phosphoric acid was cooled to 0 ° to -5 ° C. with an ice-salt bath. While the Temperature was kept within these limits, 1.52 g of sodium nitrite in 5 ml Water added within 20 minutes. The mixture then became an additional 75 Stirred min at about -5 ° C.

A solution of 8 g of N-ethyl-N- (m-tolyl) -3-aminopropanesulfonic acid (as Potassium salt) in 50 ml of cold water was prepared and 150 g of ice were added to this The diazonium salt solution in phosphoric acid was added to the coupling component with stirring added, a precipitate of the monoazo dye formed. After 30 minutes the solid precipitate filtered off. It became a paste again with 50 ml of water triturated and the pH adjusted to 9 to 10 with 50% NaOH solution. That The sodium salt of the dye was filtered off and dried.

It was a dark solid that was soluble in water and secondary oil-acetatrayone from dye baths containing sodium chloride and colored nylon from acid, neutral, or alkaline dye baths in violet shades. Ethyl N- (m-tolyl) -3-aminopropanesulfonic acid prepared according to the general procedure of Example 103 are shown in Table VI. The dyes have the general formula: TABLE TABLE VI Amine-Diazotized and Tint-on-Play Coupled Amine Acetate-Rayon Nylon-66 No.

76 2-aminobenzothiazole-6- bluish-red bluish-red methyl-sulfone p7 2-aminobenzothiazole red red 78 2-amino-6-methyl-red red benzothiazole 79 2-amino-6-methoxyrot red benzothiazole 80 2-amino-6 -chlor- red red benzothiazole 81 2-amino-5,6-dichloro-violet violet benzothiazole B ebeispiel ## 23.3 parts of 4-aminoazobena hydrochloride were suspended in 125 parts of water and 15 parts of 32% hydrochloric acid. After stirring for 1 hour, the mixture was diluted to 375 parts by volume at 1200 with ice and water. A solution of 8.3 parts of sodium nitrite in 25 parts of water was added at 1200 over the course of 45 minutes. The mixture was stirred for an additional hour at 12-1600 and ice was added to a temperature of 1000. A portion of filter aid was added to the solution and filtered, thereby removing a small proportion of insoluble substances. The resulting diazonium salt solution, after a small excess of nitrous acid had decomposed by adding sulfamic acid, was added with thorough stirring to 185 parts of the solution prepared according to Example 11 in which 25 parts of sodium acetate had been dissolved and which had been cooled to 5 ° C. with ice. After 45 minutes, the pH was increased to 5 by adding a 20% strength sodium hydroxide solution and, after a further two hours, to 8.7 by adding more sodium hydroxide. The red crystalline product was then filtered off and dried. A reddish-brown solid with the structure was obtained: This compound dyed nylon and other polyamide fibers from alkaline, neutral and weakly acidic baths in even red tones with good lightfastness and washfastness. It also dyed secondary cellulose acetate fibers from aqueous baths containing 20% (owf) sodium chloride in shades of red with excellent washfastness and good lightfastness.

Following the general procedure of Example 110, additional disazo dyes with similar coloring and fastness properties were prepared by diazotizing 4-aminoazobenzene or aminoazotoluene and coupling with a compound of the structure: The resulting dyes had the structure: These dyes are given in Table VII.

TABEL T A B E L L E VII Bei- amine that goes to the R1 R2 R3 shade on nylon game A-N = N-GRuppe di- or acetate no 83 4-Aminoazobenzene -CH3 H H scarlet 84 4-Aminoazotoluene -CH3 H H "85 4-Aminoazobenzene -CH-CH2CH3 H H "CH3 86 4-Aminoazobenzene -Cyclohexyl H H" 87 4-Aminoazobenzene -CH2CH2OH H H "88 4-Aminoazobenzene -CH2CH3 H -CH3" 89 4-Aminoazobenzene -CH2CH3 -CH3 H red 90 4-Aminoazobenzene -CH2CH2CN -CH3 H red 91 4-Aminoazobenzene -CH2CH3 Cl H scarlet 92 4-Aminoazobenzene -CH2CH3 -NHCOCH3 H maroon 93 4-Aminoazobenzene -CH2CH3 -CH3 -OCH3 "94 4-aminoazobenzene -CH2CH3 -OCH3 -OCH3" 3 e i s p i e 1 e 95-102 34.6 parts of 2-chloro-4-nitroaniline were in 200 parts of water and 60 parts of concentrated hydrochloric acid triturated to a paste and directly at 10 Diazotized to 1500 by adding 16 parts of sodium nitrite as an aqueous solution.

After 1 h, the diazo solution was filtered and excess nitrous Acid destroyed with sulfamic acid. To the clear solution, which had cooled to OOC, 30.6 parts of 2,5-dimethoxyaniline in 50 parts of water and 25 parts became more concentrated Hydrochloric acid added. The mixture was stirred at 10-1500 for 15 minutes. After this Time the clutch was complete. Then within 10 min at 15 to 2000 a solution of 16 parts of sodium nitrite and 40 parts of concentrated hydrochloric acid was added. The aminoazo intermediate was dissolved after the diazotization. After about 1 hour Stirring crystallized out the diazonium salt and was filtered off. The paste was redissolved in 500 parts of water, resulting in an orange-red solution which was filtered in order to filter off a small proportion of non-diazotized material. The solution was divided into eight equal portions and one portion to each Coupling components indicated in Table VIII were added, in a 0.03 molar Amount dissolved in 50 parts of water and 5 parts of sodium acetate and then cooled to OOC had been. The products precipitated quickly and were filtered off after the pH had been raised to 9.5 and dried. They were all dark solids with a slightly lower solubility in water, but the nylon from alkaline Colored baths in the specified tones.

T A B E L L E VIII When- used coupling component color play nylon er.

95 N-methyl-N-phenyl-3-aminopropane-marine sulfonic acid 96 N-cyclohexyl-N-phenyl-3-aminopropanesulfonic acid 97 N-benzyl-N-phenyl-3-aminopropane reddish- marine sulfonic acid L 98 N- (2-hydroxyethyl) -N-phenyl-3-aminopropanesulfonic acid 99 N-ethyl-N- (m-tolyl) -3-aminopropanesulfonic acid greenish marine 100 N-ethyl-N- (1- naphthyl) -3-aminopropanesulfonic acid reddish-marine 101 ET-ethyl-N- (2,5-dimethoxyphenyl) -3 aminopropanesulfonic acid green-gray 102 N-ethyl-N- (m-chlorophenyl) -3- aminopropanesulfonic acid 3 ei 5 piie 1 1Q3 The p-nitroaniline from Example 29 was replaced with 13.5 parts of mesidine, ie 2,4,6-trimethylaniline, using otherwise the same procedure. The monoazo coupling product was a water soluble solid that colored nylon and acetatrayon in shades of yellow. It had the structure: B ei 5 pie 1 104 The p-nitroaniline of Example 29 was replaced by 26.1 parts of p-dodecylaniline using otherwise the same procedure. The monoazo coupling product was a solid that was sparingly soluble in water. He dyed nylon from neutral to alkaline baths in shades of yellow.

B e i 5 p i e 1 105 @ 9.1 parts of 2-methoxy-4-nitro-5-methylaniline were mixed with 50 parts of water and 15 parts of concentrated hydrochloric acid to form a paste and diazotized at 15 to 20 ° C by adding a solution of 3.7 parts of sodium nitrite.

The diazo solution was filtered off after 30 minutes and a slight excess destroyed by nitrous acid with sulfamic acid. A solution became to this solution from 7 parts of cresidine in 50 parts of water and 6 parts of hydrochloric acid were added. To After stirring for 18 hours, the coupling was almost complete. The aminomonoazo intermediate was filtered off, with 250 parts of water and 15 parts of concentrated hydrochloric acid triturated again to a paste and triturated at 25 ° C. by adding a solution of 3.7 parts Sodium nitrite diazotized. The diazonium salt crystallized as a golden solid from, which was filtered off after 30 min. The paste was added to 500 parts of water 2500 dissolved and after filtering to a solution of 16 parts of the potassium salt of N-ethyl-N- (m-tolyl) -3-aminopropanesulfonic acid in 50 parts of water and 5 parts Sodium acetate g g and the solution cooled to OOC. The coupling was quick and a dark solid precipitate was obtained, containing 50% sodium hydroxide made alkaline, filtered off and dried. He had limited water solubility, but dyed nylon from alkaline baths in dull purple tones.

PATENT CLAIMS

Claims (14)

Claims 1. Dyes of the general formula in the AN = N- the residue of a diazotized, aromatic amine, a diazotized, cyclic amine or a diazotized amino-monoazo intermediate after coupling, R is an aryl group with 1 to 2 aromatic rings, on which the group AN = N- is in the para position to the nitrogen atom, R1 is a radical bonded to the nitrogen atom via an alkyl carbon atom and M is a hydrogen, sodium or potassium atom or an ammonium group. 2. Dyestuffs according to claim 1, characterized in that they are e k e n n -z e i o h n e t that pure alkyl group with 1 to 8 carbon atoms, a benzyl, cyclohexyl, -CH2CH2OH, -CH-CH2OH, -CH2CH-CH2OH or -CH2CH2C # N - group. CH3 OH 3. Dyes according to Claims 1 or 2, characterized in that R is a group means in which R2 is a hydrogen or halogen atom, a lower alkyl group with 1 to 4 carbon atoms, a lower O-alkyl group with 1 to 4 carbon atoms or an -NHCOR4 group, R3 is a hydrogen atom, a lower alkyl group with 1 to 4 carbon atoms, an -NHCOR4 group or a lower O-alkyl group having 1 to 4 carbon atoms, and R4 is a lower alkyl group having 1 to 4 carbon atoms, an olyl, phenyl or halogenophenyl group. 4. Dye according to claim 1 to 3, characterized -zeic li net that A is the group denotes in which R5 is a hydrogen or halogen atom, a nitro, cyano, an alkyl group having 1 to 12 carbon atoms, a lower alkoxy group, a trifluoromethyl, alkylsulfonyl, acetyl, 1-alkyl-carboxamido or N, N -Dialkyl-sulfonamido group, R6 is a hydrogen or halogen atom, a nitro, cyano, lower alkyl or lower alkoxy group, and R7 is a hydrogen or halogen atom or a lower alkyl or lower alkoxy group. 5. * 6. Dye according to claim 1 to 5, characterized in that A is a group in which Y1- is a hydrogen or halogen atom or a nitro, -SO2CH3-, methyl or lower O-alkyl group with 1 to 4 carbon atoms, Y2 is a hydrogen or halogen atom or a nitro group, Y3 is a hydrogen or halogen atom, represents a lower alkyl or a nitro group, and a hydrogen atom or a lower alkyl group. 7. Dye according to claim 1, dedurch-g ekenn that R is a group and R1 is a lower alkyl group having 1 to 6 carbon atoms, a CH2OH2C = N or -CH2CH20H- group. 8. Dye according to claim 1 to 6, characterized in that g e k e n n -z e i c h n e t that the molecule contains only one sulfonic acid group. 9. Dyestuff according to claim 8, characterized in that g e k e n n -z e i c h n e t that R1 R1 denotes a methyl or ethyl group. 10. Dye according to claim 8, characterized in that A is a Group means. 11. Dye according to claim 8, characterized in that A is a Means group in which R10 and R11 each represent a hydrogen atom or a methyl group. 12. Dyes according to claim 1, characterized in that they have the formula own. 13. Process for the preparation of dyes according to Claims 1 to 12, characterized in that an aromatic amine, a heterocyclic amine or an aminomonoazo-Zv) ishen product is diazotized and the diazo compound is diazotized with a compound of the formula in which D is a hydrogen atom in the p-position on the ring R and R, R1 and M have the meanings given above, couples and isolates the dye in the desired salt form [ 14. Use of the compound according to claim 1 - 12 for dyeing polyamide fibers, wherein the fibers with an aqueous solution of these compounds, if necessary containing an inorganic salt, brings together 0 * 5. Connections according to claim 4, characterized in that R1 denotes a methyl or ethyl group.