DE2156545A1 - Azo dyes - from 2,6-diaminopyridine derivatives - Google Patents

Abstract

New dyes have the formula (I): where D is the residue of a diazo component of the benzene, naphthalene, diphenyl, azobenzene, thiophene, benz(iso)thiazole, thiazole, (benz)triazole, indazole, pyrazole or anthraquinone series, X is CN or CONH2, R is H, 1-8C alkyl, alkyl substd. by OH, 1-8C alkoxy, COOH, 2-6C carbalkoxy, 1-10C acyloxy or is not >8C alkylamino or interrupted by O, phenyl (opt. substd. by Cl, CH3, C2H5, OHCH2CH2, CH3O or C2H5O), cyclohexyl, benzyl, phenylethyl or omega-N-pyrrolidonyl-alkyl with 2-3C in the alkyl gp., R1 is H, 1-8C alkyl, alkyl substd. by OH, 1-8C alkoxy, or is not 8C alkylamino, R and R1 together with the N atom represent the residue of pyrrolidine, piperidine, morpholine or (N-methyl)-piperazine, R2 is as in R, R3 is as in R1, and R2 + R3 are as in R + R1. The dyes are yellow to greenish-blue, and are suitable for dyeing or printing polyacrylonitrile, polyamides, cellulose esters and polyesters. Strong dyeings with good resistance, esp. to thermo-fixing and light are obtd.

Description

Azo dyes from 2,6-Diamiho-pyridine-Derivat en addition to patent. ... ... (Patent application P 20 62 717.2) Subject matter of the patent. ... ... (patent application P 20 62 717.2) are dyes of the general formula in D the remainder of a diazo component of the benzene, naphthalene, diphenyl-azobenzene, benzthiazole, benzisothiazole, thiazole, thiadiazoN, triazole, benzriazole, indazole, pyrazole or anthraquinone series, X cyano or carboxamide, R is hydrogen, alkyl with 1 to 8 carbon atoms, optionally substituted with hydroxy, alkoxy with 1 to 8 carbon atoms or alkylamino with a total of up to 8 carbon atoms, alkyl, phenyl, optionally with chlorine, methyl, ethyl, β-hydroxyethyl , Methxy or ethoxy substituted phenyl, cyelobexyl, benzyl, phenylethyl or # -N-pyrrolidonylalkyl with 2 or 3 carbon atoms in the alkyl radical, R1 is hydrogen, alkyl with 1 to 8 carbon atoms, optionally by hydroxy, alkoxy with 1 to 8 carbon atoms -Atoms or alkylamino with a total of up to 8 carbon atoms substituted alkyl, R and R1 together with the nitrogen denote the remainder of pyrrolidine, piperiaine, morpholine, piperazine or N-methylpiperazine, independently of one another having the same meaning as R, R3 having the same meaning as R1 and nd R2 and R3 have the same meaning as R + R1.

It has now been found that dyes of the formula (1) in which D and X have the meanings given for formula I and, independently of one another, A1 and A2 are hydrogen, alkyl with 1 to 8 carbon atoms, alkoxyalkyl with a total of 3 to 7 carbon atoms, phenyl, optionally with chlorine, methyl, ethyl, ß -Hydroxyethyl, methoxy or ethoxy substituted phenyl, cyclohexyl, benzyl, phenylethyl, carboxyalkyl, carbalkoxyalkyl with a total of 2 to 15 carbon atoms or acyloxyalkyl with a total of up to 15 carbon atoms, where the substituted alkyl chains can be interrupted by oxygen atoms and one of the Rests A1 or A2 represents a carbalkoxyalkyl or acyloxyalkyl group, also have the valuable properties specified in the main patent.

In addition to those mentioned in the main patent, radicals A1 or A2 are, for example: (CH2) O (CH2) 4OH, (CH2) 3OC2H4OCH3, (CH2) OC2H4OC6H5, CH2CHOHC6H5, Acyloxyalkyl radicals are, for. ß. : Aoyl acid residues are, for example: - CO-CH2-O-CH3, -CO-CH2-S-CH3, -CO-CH2-SO2-CH3, carboxyalkyl radicals are for example

CH2COOH, C2H4COOH, (CH2) 3COOH or (CH2) 5COOH.

Examples of carbalkoxyalkyl groups are: -CH2-COO-Y, -CH -CH -COO-Y, -CH2-CH2-CH2-COO-Y, -CH2-CH2-CH2-CH2-CH2-COO-Y or -CH2-CH2-O-CO-CH2-CH2-COO- Y, where Y is alkyl, cycloalkyl, aralkyl, hydroxy-, alkoxy- or aroxyalkyl.

Specifically, for Y, for example, methyl, ethyl, propyl, butyl, Cyclohexyl, benzyl, hydroxyethyl, hydroxybutyl, hydroxyhexyl, methoxyethyl, methoxypropyl, Called ethoxypropyl, phenoxyethyl or hydroxyethoxyethyl.

Of particular technical importance are dyes of the formula (1) with acyloxyalkyl groups, the alkyl radicals preferably of the formula CH2 -CH2-, -CH2-CH-CH3, -CH2-CH2-CH2- or -CH2 CH2 OCH2CH2 - correspond. Preferred acyl bristles: Formyl, Acetyl, acetoacetyl, phenoxyacetyl or phenylacetyl.

Dyes with 2 formyl groups should be emphasized.

The information in the main patent applies to further emphasis.

X is preferably cyan.

With regard to the further meanings and explanations, the information applies of the main patent accordingly.

The compounds of the formula (1) are also prepared in principle according to the procedure specified in the main patent, provided that the ester group (s) is (are) already contained in the coupling component.

The dyes of the present invention can also be obtained when the acyl radicals are introduced into the finished azo dye of the general formula (1). The free acids on which the acyl radicals are based are suitable for this purpose whose Anhydrides, chlorides or esters, the reactions expediently in the presence inert diluents or solvents, such as mono-, di- or trichlorobenzene, tetrahydrofuran, Dioxane, dimethylformamide, N-methylpyrrolidone or pyridine can be carried out.

It can be an advantage when using the free acids for esterification be to add inorganic or organic acids as catalysts, e.g. HCl gas or toluenesulfonic acid. The resulting water can from the reaction mixture e.g. be removed by evaporation.

If acid anhydrides or chlorides are used for esterification, so can in special cases the associated acids serve as solvents. So can For example, reactions are carried out with acetic anhydride in glacial acetic acid as a solvent will.

When using acid chlorides as esterifying agents, it is It is advantageous to add acid-binding agents to the reaction mixture, e.g.

Sodium carbonate or acetate, magnesium oxide or pyridine.

In addition to the esterifying agents mentioned, there are also diketene in particular and isocyanates, such as methyl or phenyl isonate, mentioned.

It is of course also possible to add the carbalkoxy groups subsequently Esterification of the dyes containing earbQxyl groups. to be introduced according to known methods.

example 1 20 parts of the product obtained by coupling 4-nitro-1-aminobenzene to 2,6-dihydroxyethylamino-3-cyano-4-methylpyridine are introduced as a dry powder into 250 parts of formic acid with stirring.

The mixture is stirred at 800 for a few hours until thin-layered matographically complete esterification is achieved. The crystallized after / cooling The dye is filtered off with suction, washed with cold methanol and dried at 800 m. Han receives a yellowish red powder that is dissolved in acetone or dimethylformamide orange / colors solves. Orange colorations appear on partial structures made of polyester obtained with excellent fastness properties.

According to this Yerfahren, the following alkyl acid esters were obtained with the same coupling component: 3eisp. The spontaneous hue of the color on polyester CR3 2 ° 2§B3s2 orange Cl 3 02 scarlet fleisp. Diazo component shade of the coloring on polyester Cl 4 O, BQ scarlet CN 5 2 4 2 red NO2 6 2 4 2 red N02 7 O½H½l2 red NO 2 8 02R- red Z ON 9 O2NNH2 ruby C1 ON 10 ° 2J 4F ruby flr NO 11 02H> 2 ruby ON w | lei rI>. Diazo component shade of the coloring on polyester CN 12 6 2 yellow CN 13 4 2 yellow S02-CH3 14 6 2 yellow cF3 15 Cl 4 MH2 yellow 16 5 = -Q-orange CE3 CI 17 6 N = X4F orange ClN = N> 2 scarlet Cb . Br 19 t N = N 4 NH2 scarlet Br Example diazo component color shade of the coloring on polyester Br 20 O2NNH2 scarlet Br - Br 21 2 4 2 scarlet 22 N scarlet NH 23 02N 2 blue-violet 24 X red-violet Example 25 If 20 parts of the coupling product from 4-nitro-2-cyano-1-aminobenzene and 2,6-di - @ - hydroxypropylamino-3-cyano-4-methylpyridine are esterified with formic acid as described in Example 1, then a Obtained red dye that dyes polyester in clear red shades, which have excellent lightfastness and @hermofixierefastheit.

If dyes with the same diaminopyridine derivative as coupling component are reacted with formic acid to an analogous extent, the following esters result: Example slide component color shade of the coloring on polyester 26 02H.NR, orange '' i1. s 7 02NtX orange 2t) scarletO ff l scarlet scarlet 29 t \ scarlet scarlet c "1 Br 30 2 4 N RL ~ scarlet icep. Diazo component shade of the color burlg on polyester 31 O2NNH2 s charl ach flr S02-NH-C4R9 32 2 4 2 red , JOOC2H5 25th 33 2 <2 rof NO2 34 2 4 2 red NO 2 35 Oeff-I red Cl NO2 36 o, a-RH2 red Br ON 37 9 ruby Cl nSisp. Slide couponent shade of Au8 fbrng sf from polyeater CN 38 PH2 ruby 3s O, I. rPbirr CI 40 C1 4JH2 yellow 41 (3 JE2 orange 42 02Nt so 02.S, scarlet 43 02B $ blaJlvioltt 44 023! 1 21IH2 ruby Example 45 In 100 room parts 98 percent. Formic acid is taught 20 parts of the unesterified starting dye for 4 hours at 600. The reaction product which crystallizes out at room temperature is isolated and dried. The dark red powder dissolves in a bordo color in dimethylformamide and produces ruby dyes with excellent fastness properties on polyester.

If the following diazo components are used, the corresponding dyes are obtained: I3eisp. Diazo component shade CN 46 02N 4 NH2 red Red 47 02N-r-NH2 2 scarlet 48 2 4 2 orange 49 t N = NNH2 orange 50 O2NNSN112 scarlet 51 () 2N 4 New2 ruby C1 Example 52 In 100 parts by volume of glacial acetic acid, 20 parts of the starting dye free from acetyl groups are dissolved at the reflux temperature. The mixture of 20 parts by volume of glacial acetic acid and 16 parts of acetic anhydride is then gradually added. After stirring for five hours at 115 ° C., the dyestuff is filtered off with suction after cooling and dried. It dyes polyester fabric in clear red tones, which have excellent fastness properties.

By the same procedure, dyes with similar properties are obtained with the following diazo components. Example slide component color tone 53 02N Nff2 orange Cl 54 02N 4 Never2 - - scarlet Example lei8p. | Diazo component j hue | 55 | ° 2 scarlet fever Ci 56 56 ° 2§ 4 ruby Ci 57 57 | ° 2J N / ruby Example 58 13 parts of the dried coupling product of diazotized 4-asinoazobenzene and 2,6-di-hydroxyethylamino-3-cyano-4-methylpyridine are stirred at 1000 for one hour in 150 parts by volume of acetic anhydride. The reaction product crystallized out of the reaction solution after cooling is filtered off with suction and washed with methanol. The compound, which appears as a red powder after drying, dissolves in dimethylformamide with a yellowish red color. On polyester fibers you get red-orange tones that have excellent smoothness.

Dyes with similar coloristic behavior are obtained in an analogous manner with the diazo components listed in the following table: Example, diazo components shade 59 042J> 2 orange OCH 60 ° 2X L scarlet cl 61 02X4XH2 w scarlet Cx 62 02J41112 red CX 63 O2IiMH2 ruby Cl.

Example 64 To the mixture of 18 parts of the unesterified starting dyestuff and 500 parts by volume of propionic acid, 15 parts of propionic anhydride are added at 1000 ° C. and the reaction mixture is stirred at 115 ° C. until complete conversion can be demonstrated. The paraffin ester which crystallizes out after / cooling is filtered off with suction, washed with methanol and dried. The red powder obtained in this way dissolves in 80 percent. Acetone with a yellowish red color. Real scarlet tones are achieved on polyester fabric.

Example 65 To a mixture of 200 parts by volume of glacial acetic acid and 20 parts of the dried coupling product of 3-aminophthalic acid-2-hydroxyethylimide and 2,6-di-'ß-hydroxyethylamino-3-cyano-4-methylpyridine, 20 parts of acetic anhydride, diluted with the same Amount of glacial acetic acid, added. The reaction mixture is stirred at the reflux temperature until complete esterification is achieved. The dye, an orange powder, which crystallizes out and is isolated after cooling, produces golden yellow dyeings with excellent fastness properties on polyester fabrics.

Example 66 The mixture of 250 parts by volume of monochlorobenzene, 12.5 parts of phenoxyacetic acid, 2.5 parts of p-toluenesulfonic acid and 21 parts of the coupling product of 4-nitro-2-cyananiline and 2- (13-ethoxyethyl amino) -6- (2 @ -hydroxy-äthylamino) -3-cyano-4-methylpyridine 2 hours at 1000, what is achieved with complete conversion. The reaction product, which crystallizes out after cooling, gives a red powder after drying, which dissolves in dimethylformamide with a red color. True, clear red tones are preferably obtained on polyester fibers according to the high-temperature dyeing method at .1300.

According to this process, the following dye esters are obtained with the same coupling component: hue Example: diazo component color 67 WITHOUT2 orange C113 68 Z 4 2 orange OCH 69 02Ng2 scarlet 69 5 charl ach Cl 70 O2NiH2 scarlet COO-CH2-C12-O-C113 71 Q2N 4 BE2 red NO2 72 02N 6 ME2 red NO2 73 | ° 2§ red Cl Example: diazo component color CN 74 02N TH2 ruby CN 75 O2NNH2 ruby ON 76 HB, yellow CN 77 ClNR2 yellow 78 $ NH2 yellow CH2-CR2-C112-O-CH3 Example 79 cies The mixture of 16 parts of unesterified starting dye, 9 parts of phenoxyacetic acid, 2 parts of p-toluenesulphonic acid, 50 parts by volume of monochlorobenzene and 100 parts by volume of dichloroethane is gradually heated to 1200 while distilling off the solvent and water of reaction and stirred at this temperature until complete esterification is achieved which can be detected by means of a thin-layer chromatogram. 100 parts by volume of alcohol are then added, this is kept for a short time at the reflux temperature and the dyestuff ester is then isolated after cooling. After drying, a yellow powder is obtained, which is 80 percent. Acetone dissolves with a yellow color and produces yellow colorations with excellent fastness properties on polyester textile material. Polyamide fabrics are dyed in real, yellow tones.

The dyes with the following diazo components are produced using the same process: Example: diazo component color CN 80 CN yellow 81 e 2 yellow S02-CH3 82 C1 4 NES yellow Example: diazo component color CF3 83 Cl- b F3H2 yellow 84 2 e 2 orange OCH3 e5cNH2 scarlet Cl 86 2 4 2 scarlet Cl 87 02N- scarlet fever He 88 02N 4 NE2 red NO2 89 02N NH2 red NO2 90 ° 2 s Cl2 2 red Cl SO2-N (CH) 2 91 02N 4 NH2 red Example: diazo component color CN 92 2 4 2 red CN 93 4 NH2 ruby NO2 CN 94 O2NNH2 2 ruby Cl Ci 95 ° 2ff O2NNH2 ruby 96 02N) $ 'NH2 ruby Ss) 3r 97 O2iNH2 red-violet iH2 98> 23 bl au-violet 99 tX scarlet EXAMPLE 100 Sufficient diketene is added dropwise to the mixture of 100 parts by volume of pyridine and 21 parts of the unesterified starting dye with stirring at 50 ° C. until the ester has formed completely. For isolation, 100 parts of water are added at room temperature, the precipitated dye is filtered off with suction and washed with methanol. The red powder obtained after drying dissolves in dimethylformamide with a yellowish red color and produces real scarlet tones on polyester fabrics.

Example 101 At 50 ° C., 5 parts of bensoyl chloride are gradually added to the mixture of 30 parts by volume of pyridine and 5 parts of unesterified starting coloring material C. The red powder obtained in this way produces scarlet tones with good fastness properties on polyester fibers.

Example 102 des 5 parts of chloroacetyl chloride are slowly added at 60.degree. C. to the mixture of 5 parts / unesterified coupling product, 50 parts by volume of glacial acetic acid and 5 parts of anhydrous sodium acetate. After esterification has taken place, it is filtered off with suction while cold, washed with methanol and dried.

The red powder dyes polyester fabric in real scarlet colors Tones.

Example 103 The mixture of 21 parts / unesterified starting dyes, 75 parts by volume of pyridine and 20 parts of succinic anhydride is stirred at 500 until complete esterification is achieved. The reaction product is filtered off with suction after cooling, washed with a little ethanol and dried at 80 °. The red powder thus obtained is soluble in dimethylformamide with a red color. Clear red tones with anticipatory fastness properties are thus obtained on polyester fibers.

Example 104 The mixture of 5 parts of starting dye and 5 parts of maleic anhydride is reacted in 30 parts of pyridine at 50 ° C. until the dye has been completely esterified. For isolation / the reaction mixture is mixed with the solution of 50 parts of water, 50 parts by volume of alcohol and 50 parts by volume of glacial acetic acid. The dyestuff, a red powder, which is sucked off and dried, gives scarlet dyeings with good fastness properties on polyester fabrics.

Example 105 The mixture of 5 parts of starting dye, 3 parts of cyclohexanecarboxylic acid and 0.5 part of p-toluenesulfonic acid is stirred at 100 ° C. until esterification is complete. The dye, which is isolated after / cooling, gives real and clear red tones on polyester fibers.

Example 106 If 5 parts of the starting dye are reacted with 5 parts of nicotinic acid in 10 parts by volume of N-methylpyrrolidone as in Example 79, the result is a red reaction product which produces red shades of excellent fastness properties on polyester fabric.

Example 107 First 5 parts of starting dye and then 5 parts of ethyl succinic chloride are introduced into 15 parts of pyridine, and the reaction mixture is then stirred at 50 ° until the reaction has ended. The cold-isolated dye, a red powder after drying, produces real and clear red tones on polyester thread.

Example 108 5 parts of phenyl isocyanate are gradually introduced into the mixture of 5 parts of starting dye and 50 parts of monochlorobenzene at 1000C. After the reaction has taken place, the reaction product is filtered off with suction while hot, washed with alcohol and dried. With the red dye powder thus obtained, pure red tones with excellent fastness properties are obtained on polyester fabrics.

Example 109 The mixture of 20 parts of the starting dye (R = H), 8.5 and parts of phenylacetic acid / 2 g of p-toluenesulfonic acid in 150 parts by volume of monochlorobenzene is stirred at 100 °, then 100 parts of 1,2-dichloroethane are added and this is distilled for the purpose Drainage slowly from again until a temperature ton 1200 is reached. The whole thing is kept at this temperature until no more starting dye can be detected by thin-layer chromatography. After cooling to room temperature, the dye ester crystallized out Sucked off, washed with a little alcohol and dried. The dark red powder dissolves in dimethylformamide with a deep red color and produces red tones with excellent fastness properties on polyester fabrics.

Example 110 4.7 parts of 2-cyano-1-aminobanzole are stirred with 100 parts of water and 10 parts by volume of 30% strength hydrochloric acid. Then 120 parts of ice and 12 parts by volume of 23% sodium nitrite solution are added. After tubes for two hours at 0 ° to 50 ° C., any excess nitrous acid present is destroyed as usual and filtered in 450 parts of water and 10 parts by volume of 30% strength hydrochloric acid. The mixture is stirred for 1 hour and 50% strength sodium acetate solution is then added until the pH of the coupling mixture is 3.

When the coupling is complete, the dye has the formula Sucked off, washed neutral with water and dried. A yellow powder is obtained which dyes the polyethylene terephthalate fabric in strong yellow shades by the Carrier and RT processes.

True yellow tones are obtained on polyamide fibers with the dye.

Preparation of the coupling component for Example 110: 160 parts of the compound of the formula are refluxed for 3 hours with 500 parts by volume of glacial acetic acid and 65 parts by volume of acetic anhydride. After about 150 vinegar has been distilled off, the mixture is allowed to cool to 80 ° C. and the mixture is stirred in 1500 parts of water is filtered off, washed with water and dried. 150 parts of a colorless powder which melts at 78-80 ° C. are obtained.

Example 111 14 parts of the dye of the formula are suspended in 100 parts by volume of chlorobenzene. 6 parts of 2-ethylhexanoic acid chloride and 4 parts of pyridine are added and the mixture is stirred for 10 hours at 80-10,000. After cooling, 300 parts by volume of methanol are added and the dyestuff of the formula which has precipitated out is sucked off off, washes first with methanol and then with water.

A dark red powder is obtained, which dissolves in dimethylformamide with bluish red paint dissolves and polyethylene terephthalate fabric in dark red tones colors with very good lightfastness.

According to the above examples, the following dyes were obtained: Beisp, Dil; o-CKu ,, ZuWskamanents Parbtan auf Polyestsr CH GH, C 112 24 AH-ca, ruby RN-OHrCOCOCpRs ON OH CN 113 02KQ-- CH-CFlcpCH.I ruby RN-OHOHG-C () (R5 ON CR3 ON 114 ° p H- (CH2-CEp-o) 2COCH7COCH ruby Br HN- (CR) 30OH (OH3) p Example: Diasc + coupling component color shade on polyester Ci CH to CN 15 - (CH, -CO), COCECOCa, ruf ion . Br HN- (CN) 3-a2H5 Ci CH3 Ci 11C 02e6-e ---- nibin UICH-CR-CH o: o: a -C4H C2 102 CR3 Ci 117 O / <RzS <CN-CNO) COCNCOC5 red Br HN- (C) 3H (C 2 ao, CR3 Ci 118 o24 aill9DH- (CH2) 3-OCOCH2COCH3 red O1ç- (CE) Ci CR3CONH 119 02411ÇJ9JOC 3H7 (n) red BIL (CH2) 2-S2> ca C! CN 120 0245s NH-CH3 red ENZ2-CH2-OC O-Cv2-COCH3 W, C] A O2'4ICCiNN, CiNHH2H red 121 () c red Example: Diazo + coupling component color on polyester CN CM, CM 122 ° p 4, N $ t NE ~ CH2 'H2 ~ CH2 W OCH2-COCH3 red HN-CH2-CH2-CH2-CH3 S ° 2 ^> 3CN 123 O <"N N-CH3 CH3 red HN-CH2-C3H-O-CO-CH2 C3 CH3 Br CR3 ON 124 02BLd [(CB3-CII-o), Co-CH, -CcltHj scarlet HN- (CH) 3-OCE <CH3) 2 Br CH CN 125 O 4 nu toOPFNH- (CH, -CH, -o) -CeCH2-COCH scarlet red . HN-CHp-CH2-C N OCH3 Br CH, CN 12C 02 4 N <NH (CN -CE2 °) 2 CO CH2 COCH3 scarlet red HNC 6H1 3 (n) Br CH3CN 127 O4N = N9EXH3 scarlet HN-CH2-CH2-OCO-C, H, L / CH 128 O 4,> 1 3 scarlet red HN-CH- <HO-COH CH3 Example Di3zc + coupling component color shade on polyester C1 CB 1 9 0N <% ffiNNß $,) - NHCHCHoC0-CH -CO- scarlet H 4CHN - 0-OH I. CiCH3CN 130 Cp to CH7-OwCO-C 5 scarlet H -'- CH3 Cl CCN 131 0319-1d "(-aGH3 red HN- (2-CH-O-COH-CO-CK3 Cl OH ON 132 ° 2 CH2-O ~ CO-CH2-GO-OCH2O-.CR3 5 scarlet 3 C1 CH3CN 133 02N 4N CN) 3-0-CH3 scarlet HN-CH2OH-CO-C2 34 ° 2 <W "E> CH2-0-COwCH3 orange 3 HE CE2-CI N OLC ° CH3 (acetate: golden yellow) HN-CR212OCO-CH3 CH 3 OCH3 CH3 ON 35 ° 2 4N N 4 MH-CH2-C N -OwCO-CH2 <scarlet H-§-CH2-CO-CH3 Example Diaz + coupling component color shade on polyester CH, CB 135 CL- sy 13C Cl 4ff H (CE2 ffi -O32COLCE2 C HTN- (CN O-C2> (polyamide: golden yellow) Br CE CX 37 o W NE CS2-O-CO Tialatt 1 'HN- (CH) 3-O-CH3 COOCE OH OH 138 02 4 N zuN 9 RE (CH2) zu.-ee-cBIeerr, red H-NCE-CR2 - () CR3 Example 139 In the diazonium salt solution obtained in the usual way from 17 parts of 2-chloro-4-nitroaniline are added at 0 - FO 350 parts by volume of a 0.3 molar aqueous solution of urid then 200 room parts of a 50 percent. Sodium acetate solution. After the coupling has ended, it is filtered off with suction, washed with water and dried.

The mixture of 20 parts of the coupling product thus obtained, 500 Parts by volume of ethanol and 1 part of p-toluenesulfonic acid is distilled off as long as it is the alcohol-water mixture is stirred at the boiling point until complete esterification is achieved.

The reaction product is filtered off with suction while cold, washed with alcohol and dried.

The red powder obtained in this way dissolves in 80 percent. Acetone with a yellowish tinge red color. Polyester fabric dyes it in real scarlet tones.

Dyes with similar properties are obtained after esterification if the following compounds are used as coupling components: Bei8pLe1 Xipolung8kowtonente Eat on > CJ 140 8-CHi-COOH soharlach §-CE2-COOR 2 141 Ca noharlach 141 t - CB2COOH ahsrlh CH-CC (> OH cR3Ci 142> ffi4 8cbarlach (Cri2) 5-COOH Example 143 The mixture of 15 parts of the coupling product obtained according to Example 139, paragraph 1, 100 parts by volume of 2-ethoxyethanol and 3 parts of p-toluenesulfonic acid is stirred at 105 ° C. until complete conversion is achieved. After cooling, the reaction product is filtered off with suction and washed with alcohol. The red powder obtained after drying, finely divided in the FErbath, gives clear scarlet dyeings of excellent fastness properties on polyester.

Example 144 20 parts of the unesterified starting dye obtained analogously to Example 139, paragraph 1, are esterified with ethanol as described in Example 139, paragraph 1. The isolated reaction product gives real orange colors on polyester fabric.

Example 145 If 20 parts of the coupling product obtained analogously to Example 139, Paragraph 1, are reacted in accordance with Example 143 with 2-ethoxyethanol, the result, after isolation and drying, is a red powder which gives true scarlet colorations on polyester threads.

Following the procedures of the preceding examples, the following dyes were obtained: Example No. 0 II 146 CE3-0-c- CH2-CH2-S CR2 N orange NN N-CH2CH2 HN-CH2-CH2-O-CHO 147 OH ON blavtic 147 qr W -CH2-CH2-OCE £ -C2 (-CHO 9 CH 4 »013 J- ° = 2-gv ° ratirs LN yt rt -0-CH o C-0-NR2 149 ~ - RA-CH, -CH, -O-CH tlausbici HE ~ ÇH2 ~ CEe ~ O ~ CH2 ~ CE2 ~ 0 ~ COCH3 W02 150 <ß blue b ~ r 5 CE 151 02E ~ .1 purple Br S02-CR3 152 02N 4ff 5t ruby No. CH3 ON OH 153 N s N s -CH2-CH-O-CO-CH2-0 4 scarlet 2 CN CH3 ON 154 02N 4 N toN v NNH-CH2-CH2-O-CO-CH2-0 scarlet 2 COO-CH2-CH2- ° -CH3 OH3 CN 155 02N b N = N <NH-CH2-CH2-Q-CH3 red III CH2 CH2 0 CH2 CH2 0 CO CH2 ° e Cl CH3 ON 156 02N 4 N o2a-da-CH2-CH2-O-CHJ scarlet -CH3-CH, -O-CO-CH2-CB2-COOH CN OH CN 157 02N 4 N = N i NH- (CH2) 3-0-CO-CH2-CO-CH) red - (CH2) 3-0-CO-CE2-Co-CH3

Claims (3)

Patent claims 1. Dyes according to patent. ... ... (patent application P 20 62 717.2) of the general formula in the D the remainder of a diazo component of the benzene, naphthalene, diphenyl-azobenzene, benzothiazole. Benzisothiazole, thiazole, thiadiazole, triazole, rentriazole, indazole, pyrazole or anthraquinone series, X Oyan or carboxamide, R hydrogen, alkyl with 1 to 8 carbon atoms, optionally by hydroxy, alkoxy with 1 to 8 carbon atoms or alkylamine with a total of up to 8 carbon atoms substituted alkyl, phenyl, optionally phenyl, cyclohexyl, benzyl, phenyl ethyl or # -N-pyrrolidonylakyl with chlorine, methyl, ethyl, ß-hydroxyethyl, methoxy or ethoxy substituted 2 or 3 carbon atoms in the alkyl radical, R1 is hydrogen, alkyl with 1 to 8 0 atoms, optionally substituted by hydroxy, alkoxy with 1 to 8 carbon atoms or alkylamino with a total of up to 8 carbon atoms, R and R1 together with nitrogen denotes the remainder of pyrrolidine, piperidine, moroholine, piperazine or N-methylpiperazine, independently of one another having the same meaning as R, the same interpretation as R1 and and R3 have the same meaning as R + R1, here characterized by the fact that they have the formula (1) ent @@@@ en, in which @ @@@ @ have the meanings given for formula I and regardless of other A1 and A2 hydrogen, alkyl with 1 to 8 carbon atoms, Al @ xyalkyl @dt a total of 3 to 7 carbon atoms, phenyl, if necessary by @@@@, methyl, ethyl, ß-hydroxyethyl, methoxy or ethoxy substituted @@ envl, cyclohexyl, benzyl, phenylethyl, carbalkoxyalkyl with @@@@ mt 2 @@ 15 C- Atoms or acyloxyalkyl with a total of up to 15 carbon atoms be - @@@ th, where the substituted alkyl chains can be replaced by oxygen atoms under - @@@@ @@@@ and @ one of the rows A1 or A2 is a carbalkoxyalkyl or @ @@ represents a loxyalkyl group. @@@ @@@@@ n zur @ er @ lellung @@ on dyes according to Ansopruch 1, thereby @@@@ eichnet that diazo compounds of amines of the formula DNH2 with coupling components of the formula converts and optionally also esterifies the dyes. 3. The use of the dyes according to claim 1 for dyeing Textilmat @ rial made of acrylonitrile polymers, polyamides, cellulose esters or polyesters.