CH625822A5 - Process for preparing hydrazone dyes - Google Patents

Description

The invention relates to a process for the preparation of new hydrazone dyes of the general formula I.

45

'- 50

K-CH = N-N- ^ ~ ^^

On in K. for a remainder of the formula

K = CH-N = N-

R.

(IX)

60

or in which K and Ri have the above meanings, with an alkylating agent R-X, in which X represents an anionically removable radical and R has the above meanings.

2. The method according to claim 1, characterized in that hydrazone dyes of the general formula VII

65

0

3 y3

stands, and

(I)

(II)

(III)

3rd

625822

R is an alkyl radical which is optionally substituted by a hydroxyl group,

R 1 and R 2 are hydrogen, halogen, an alkyl, cycloalkyl, alkoxy, nitro, carbalkoxy, cyano, acyl, acylamino, aryl or aralkyl radical,

R3 is an alkyl radical,

R4 is hydrogen, an alkyl or aryl radical and An is an anion,

and in which at least one of the substituents R, Ri, R2 and Rj is a radical of the formula

-A-0- (B-0) p-E (IV)

-A-0-C0-F-0- (B-0) p-E (V)

or

-A- (0-F) q-C0-0- (B-0) p-E (VI)

means or is substituted by such a radical in which A represents an optionally substituted alkylene radical or an alkenylene radical or a direct bond,

B for an optionally substituted alkylene or alkenylene radical,

E for an optionally substituted alkyl, alkenyl, cycloalkyl, formyl, alkylcarbonyl, alkenylcarbonyl or cycloalkylcarbonyl radical, hydrogen, an optionally substituted phenylcarbonyl, phenylalkylcarbonyl, phenoxyalkylcarbonyl or phenylalkyl radical,

F represents an optionally substituted alkylene radical,

p stands for 1 to 5 and q stands for 0 or 1,

which is characterized in that azobases of the general formula XI

K = CH-N = N

wherein K and Ri have the above meanings, with an alkylating agent R-X, where X is an anionically removable radical, and R has the above meanings.

The above-mentioned alkyl and alkylene radicals preferably contain 1 to 6 carbon atoms and the alkenyl and alkenylene radicals contain 2 to 6 carbon atoms and can be straight-chain or branched. Cycloalkyl stands in particular for cyclopentyl and cyclohexyl optionally substituted by methyl. Aryl or aralkyl are preferably phenyl or naphthyl or benzyl, phenylethyl or phenylpropyl- (2.2), the aromatic rings e.g. B. can be substituted by 1 or 2 Ci-Ct-alkyl or Ci-Ci-alkoxy radicals or halogen atoms.

Halogen is z. B. fluorine, chlorine or bromine understood.

Carbalkoxy stands in particular for carbo-Ci-Ct-alkoxy.

The acyl radicals can be derived from aliphatic or aromatic carboxylic or sulfonic acids. Particularly suitable acyl radicals are acetyl, propionyl, toluyl or benzoyl.

Suitable acylamino radicals are formylamino, acetylamino, n-propionylamino, benzoylamino, 4-chloro-benzoyl-amino and 4-methyl-benzoylamino.

The organic and inorganic anions customary for basic dyes come into consideration as anionic radicals, examples being: chloride, bromide, CH3SO4-, C2H5SO4-, p-toluenesulfonate, HSCV, SO4-, benzenesulfonate, p-chlorobenzenesulfonate, Dihydrogen phosphate, phosphate,

Acetate, chloroacetate, formate, propionate, oxalate, lactate, itaconate, crotonate, tartrate, citrate, NO3, perchlorate, ZnCb and the anions of saturated and unsaturated aliphatic diacarboxylic acids such as maleic acid, succinic acid, glutaric acid, adipic acid and suberelic acid, pimelic acid. Colorless anions are preferred; Anions which do not impair the water solubility of the dye too much are preferred for dyeing from an aqueous medium. Anions which promote the solubility of the dye in organic solvents or at least do not negatively influence the dye, for example tetrapropylenebenzenesulfonate, dodecylbenzenesulfonate and the anion of tetradecanecarboxylic acid and that of ethylhexylcarboxylic acid, are often preferred for dyeing from organic solvents.

The radicals (IV) - (VI) can be bonded to a nitrogen atom or to a ring carbon atom.

The alkyl radicals mentioned under E can be substituted, for example, by cyano, halogen or Ci-Ci-alkoxy. The phenyl radicals can be substituted, for example, by 1 or 2Ci-Cj-alkyl or Ci-Ci-alkoxy radicals or halogen atoms. The alkylene radicals mentioned under A, B and F can, for. B.

be substituted by hydroxy or chlorine. Preferred radicals (IV) - (VI) are those of the formulas

-Ai-0- (Bi-0) pi-egg (IVa)

-Ai-0-C0-Fi-0- (Bi-0) p, -Ei (Va) and -Ai- (0-Fi) qi-C0-0- (Bi-0) p, -Ei (Via)

wherein

Ai for a direct bond or a Cz-Ct alkylene radical, Bi for a Ca-Ci alkylene radical,

Ei for a Ci-C »alkyl or C2-Ci-alkenyl radical which is optionally substituted by halogen or cyano or a Ci-C4-alkylcarbonyl or C2-Ct-alkenylcarbonyl radical which is optionally substituted by halogen, cyano or Ci-Ct-alkoxy or a Formyl radical,

Fi for a Ci or Ci alkylene radical,

pi stands for 1 to 3 and qi stands for 0 or 1.

Among these, preference is again given to those in which Ai for C2H4 or a direct bond, Bi for C2H4 and E for a Ci-Ct-alkyl, C2-Ct-alkenyl, Ci-Ct-alkylcarbonyl, formyl or C2- C4-Alkenylcarbonylrest stand. Among these, preference is given to those which stand for type IVa and in which Ei denotes a C 1 -C 4 -alkyl radical.

A preferred group within the dyes which can be prepared according to the invention is that of the general formula VII

CH7 1 year

"Cj-CH

R2

VCH = N-N

wherein

Ri and R '3 independently of one another are a Ci-Gt-alkyl radical, R' 1 and R'2 independently of one another are hydrogen, chlorine, a Ci-Gi-alkyl, Ci-Ci-alkoxy or acetylamino radical and

An is an anion, and in which at least one of the two radicals R '1 and R' 2 corresponds to a radical of the formula IVa, Va or Via, or can be substituted by such a radical.

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

625 822

4th

Another preferred group within the dyes according to the invention corresponds to the general formula VIII

R3

R

o ti

L 'nCH = N-N

-W

(VIII)

An in which the radicals R ', R' i, R 'i and An have the same meaning as in formula VII and R'4 is hydrogen, Ci-C4-alkyl or phenyl and in which either R' i is a radical of the formula IVa. Va or Via corresponds or R'j can be substituted by such a radical.

The starting materials for the new hydrazone dyes of the formula I which can be prepared according to the invention can be prepared by amines of the formula which are known per se

H.

(IX)

diazotized and with compounds of the formula

K = CH2

(X)

couples, in which Ri and K have the same meaning as in formula I, the coupling product obtained by treatment with alkali in a manner known per se into the azobase of the formula

K = € H-N = N- ^ ~ y

*1

(XI)

transferred. According to the invention, this azobase of the formula XI is reacted with an alkylating agent R-X to give the hydrazone dyes. X denotes a radical which can be split off as an anion. B. halogen, methyl or ethyl sulfate, benzene or toluenesulfonate.

Examples of amine components of the formula IX which may be mentioned are:

4-methoxy-ethoxy-ethoxy-aminobenzoI, 4-butoxy-ethoxy-aminobenzene, 4-ethoxy-ethoxy-ethoxy-aminobenzene, 4-amino-benzoic acid-methoxy-ethoxy-ethyl ester, 4-amino-benzoic acid-re-ethyl ether ethoxy-ethyl ester, 4-aminobenzoic acid-butoxy-ethoxy-ethyl, 4-amino-methoxy-ethoxybenzene, 4-amino-ethoxy-ethoxy-benzene, 4-amino-butoxy-ethoxy-benzoI, 4-aminoben- zoic acid methoxy ethyl ester,

Ethyl 4-amino-benzoate, ethyl butoxy-4-aminobenzoate, ethyl 4-aminomethoxy-ethoxy-ethoxybenzene. 4-amino-hydroxy-ethoxy-benzene, 4-amino- (3'-methoxy-2'-hydroxypropoxy) -benzene, aniline, p-toluidine, o-toluidine, p-chloroaniline, o-chloroaniline, 2-anisidine, 4-anisidine, 4-amino-acetanilide, 2,4-dimethoxy-aminobenzene, 2,5-dimethoxy-amino-benzene, aminophenoxyacetic acid, methylglycol ester, methoxy-ethoxy-acetic acid, 4-amino-phenyl ester.

As coupling components of the formula X come z. B. Consider:

1,3,3-trimethyl-2-methylene-2,3-dihydroindole 1,3,3,5-tetramethyl-2-methylene-2,3-dihydroindole 1,3,3-trimethyl-5-chloro-2- methylene-2,3-dihydroindole l, 3,3-trimethyl-5-methoxy-2-methylene-2,3-dihydroindole 1.3,3-trimethyl-5-carbomethoxy-2-methylene-2,3-dihydroindole l, 3,3 Trimethyl-5-carbäthoxy-2-methylene-2,3-dihydroindole 1,3,3-trimethyl I-5-cyclohexyl-2-methylene-2,3-dihydroindole 1,3,3-trimethyl I-5-benzyl-2 -methylene-2,3-dihydroindole 1,3,3-trimethyl-5-nitro-2-methylene-2,3-dihydroindole 5 l, 3,3-trimethyl-7-methyl-2-methylene-2,3- dihydroindole 1,3,3-trimethyl-5-trifluoromethyl-2-methylene-2,3-dihydroindole l, 3,3-trimethyl-7-methoxy-2-methylene-2,3-dihydroindole l, 3,3- Trimethyl-7-chloro-2-methylene-2,3-dihydroindoI l-ethyl-3,3-dimethyl-2-methylene-2,3-dihydroindoI io 1-ethyl-3,3,5-trimethyl-2-methylene -2,3-dihydroindole l-ethyl-3,3-dimethyl-5-chloro-2-methylene-2,3-dihydroindole l-ethyl-3,3-dimethyl-5-methoxy-2-methylene-2,3-dihydroindole l-ethyl-3,3-dimethyl-5-carbomethoxy-2-methylene-2,3-dihydroin-dol

15 l-ethyl-3,3-dimethyI-5-carbethoxy-2-methylene-2,3-dihydroindole l-ethyl-3,3,7-trimethyl-5-cyclohexyl-2-methylene-2,3-dihydroin- dol l-ethyl-3,3-dimethyl-5-benzyl-2-methylene-2,3-dihydroindole l-ethyl-3,3-dimethyl-5-nitro-2-methylene-2,3-dihydroindole 20 1 - Benzyl-3,3-dimethyl-2-methylene-2,3-dihydroindoI l-phenyl-3,3-dimethyl-2-methylene-2,3-dihydroindoI 1,3,3-trimethyl-5-methoxy-ethoxy -2-methylene-2,3-dihydroindole 1,3,3-trimethyl-5-ethoxy-ethoxy-2-methylene-2,3-dihydroindole 1,3,3-trimethyl-5-butoxy-ethoxy-2 -methylene-2,3-dihydroindole 25 1,3,3-trimethyl-5-methoxy-ethoxy-ethoxy-2-methylene-2,3-dihy-droindole 1,3,3-trimethyl-5-ethoxy-ethoxy -ethoxy-2-methylene-2,3-dihy-droindole

1,3,3-trimethyI-5-butoxy-ethoxy-ethoxy-2-methyIen-2,3-dihy-30 droindole

1,3,3-trimethyl-5-hydroxy-ethoxy-2-methylene-2,3-dihydroindole 1,3,3-trimethyl-5- (3'-methoxy-2'-hydroxypropoxy) dihydroin dol

1,3,3-trimethyl-5-methoxy-ethoxy-ethoxy-ethoxy-2-methylene-35 2,3-dihydroindole

1,3,3-trimethyl-2-methylene-2,3-dihydroindole-5-carboxylic acid - methoxyethyl ester 1, 3,3-trimethyl-2-methylene-2,3-dihydroindole-5-carboxylic acid ethyl oxyethyl ester

40 1,3,3-trimethyl-2-methylene-2,3-dihydroindole-5-carboxylic acid butoxyethyl ester

1,3,3-trimethyl-2-methylene-2,3-dihydroindole-5-carboxylic acid - methoxyethoxyethyl ester 1,3,3-trimethyl-2-methylene-2,3-dihydroindole-5-carboxylic acid ether-45 oxy-ethoxyethyl ester l, 3,3-trimethyl-2-methylene-2,3-dihydroindole-5-carboxylic acid butoxy-ethoxyethyl ester l, 3,3-trimethyl-2-methylene-2,3-dihydroindole-5-carboxylic acid- methoxy-ethoxy-ethoxy-ethyl ester so 1,3,3-trimethyl-7-methoxy-ethoxy-2-methylene-2,3-dihydroindoI l-ethyl-3,3-dimethyl-2-methylene-2,3- dihydroindole-5-carboxylic acid re-methoxy-ethyl ester.

The alkylation can be carried out by dissolving or slurrying a compound in an inert medium with the alkylating agent

60-150 ° C, preferably 80-120 ° C, heated. To this end, the alkylating agent can also be used in excess as a solvent.

Suitable inert media are e.g. B. organic liquids 60 such as gasoline, ligroin, cyclohexane, benzene, toluene, chlorobenzene and dichlorobenzene, nitrobenzene, tetralin, dioxane and dimethylformamide.

Suitable alkylating agents are e.g. Dimethyl sulfate, di-ethyl sulfate, di-n-butyl sulfate, di-iso-amyl sulfate, dimethylpyrosul-65 fat, methyl benzenesulfonate, ethyl, n-propyl, isopropyl and isobutyl esters, toluene sulfonic acid methyl -, ethyl, n-propyl, isopropyl and isobutyl ester, methyl iodide, ethyl iodide, n-butyl bromide, allyl bromide, 2-chloro and 2-bromo-diethyl ether and

5

625 822

Chloro and bromoacetic acid esters such as ethyl chloro and bromoacetate, ethylene oxide.

The alkylation can also be carried out in the presence of alkaline agents such as MgO and especially in the presence of tertiary amines which are substituted in a space-filling manner on the N atom, in accordance with Belgian Patent No. 735,565. Triisopropanolamine is particularly suitable as a space-filling substituted amine.

The new products which can be produced according to the invention are valuable dyes which can be used, for example, for dyeing and printing materials made of leather, tannic cotton, cellulose, synthetic superpolyamides and superpolyurethane, and for dyeing lignin-containing fibers such as coconut, jute, sisal. They are also suitable for the production of writing fluids, stamping inks, ballpoint pen pastes and can also be used in rubber printing.

Flakes, fibers, threads, tapes, fabrics or knitted fabrics made from polyacrylonitrile or from copolymers of acrylonitrile with other vinyl compounds such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinyl acetate, vinyl pyridine, vinyl imidazole, vinyl alcohol are particularly suitable for dyeing with the basic dyes of the above general formula , Acrylic and methacrylic acid esters and amides, as. Dicyanoethylene, or flakes, fibers, threads, tapes, fabrics or knitted fabrics made from acid-modified polyester or polyamide fibers. Acid-modified aromatic polyesters are, for example, poly-condensation products of sulfoterephthalic acid and ethylene glycol, i.e. H. Polyethylene glycol terephthalates containing sulfonic acid groups (type Dacron 64 from E.I. DuPont de Nemours and Company), as described in Belgian patent no. 549 179 and U.S. Patent 2,893,816.

The dyeing can be carried out from a weakly acidic liquor, the dye bath advantageously being taken at 40-60 ° C. and then dyeing at the boiling temperature. You can also dye under pressure at temperatures above 100 ° C. Furthermore, the dyes can usually be added to spinning solutions for the production of polyacrylonitrile-containing fibers or can also be applied to the undrawn fiber.

The dyeings on acrylonitrile-containing material are generally distinguished by very good light, wet, rubbing and sublimation fastness.

Compared to known hydrazone dyes, the new dyes which can be prepared according to the invention have, for example, a considerably better solubility in water, so that concentrated solutions of these dyes can be prepared without the addition of organic solvents.

5 In addition, a large number of these dyes are usually characterized by particularly good migration properties.

example 1

io 21.1 parts by weight of 4-methoxy-ethoxy-ethoxy-aniline are dissolved in 150 parts by volume of water and 22 parts by volume of concentrated hydrochloric acid and mixed with a solution of 7.3 parts by weight of sodium nitrite in 25 parts by volume. Parts of water diazotized at 0-5 ° C. The reaction mixture is left to stir at 0-5 ° C. for an hour, 15 excess nitrite is destroyed by adding amidosulfonic acid and the diazonium solution thus obtained is filtered into a solution of 17.3 parts by weight of 1,3,3-trimethyl-2- methylene-2,3-dihydroindole in 100 parts by volume of 10% hydrochloric acid. By gradually adding 100 parts by weight of sodium acetate, the coupling is completed, the dye suspension is allowed to stir overnight, the dye formed is suctioned off and washed with 500 parts by volume of 10% sodium chloride solution. The moist residue is stirred with 300 parts by volume of water and made alkaline with 15 parts by volume of 10% sodium hydroxide solution, the 25 color salt being converted into the azobase. The suspension is left to stir overnight, then heated to 30 ° C. and left to stir at 30 ° C. for 3 hours. Then you suck off the azobase and wash it neutral with water.

Yield: 37.7 parts by weight, melting point: 90-92 ° C. 3o 37.7 parts by weight of the azo base thus obtained are heated with 100 parts by volume of chlorobenzene and with 6 parts by weight of triisopropanolamine on a boiling water bath for 10 minutes. After cooling to 70 ° C., 13.2 parts by weight of dimethyl sulfate are added dropwise. After 3 hours of stirring at 80-85 ° C., another 6.6 parts by weight of dimethyl sulfate are added, and the reaction mixture is left to stir at 80-85 ° C. for a further 2 hours.

Then chlorobenzene is distilled off with steam, the dye solution is clarified by adding activated carbon, filtered and the dye is salted out after cooling to room temperature. 40 After recrystallization from water and salting out with sodium chloride, 33.8 parts by weight of the dye of the formula are obtained

Op

-CH ^

• CH ~ N- N - ^^ - OC ^ OCgH ^ OCHj

CH,

CH,

Cl of polyacrylonitrile materials stains golden yellow with excellent fastness properties.

Dyes with similarly good properties are obtained if the 55 diazo and coupling components listed in the following table are used and the procedure is as described in Example 1.

625 822

6

Diazo component

Coupling component

Color on polyacrylic tril

4-A mino-ethoxy-ethoxy-benzene

4-amino-hydroxyethoxy-benzene

4-amino-ethoxy-ethoxy-benzene

4-amino-ethoxy-ethoxy-benzoI

4-amino-methoxy-ethoxy-ethoxy-benzene

4-amino-methoxy-ethoxy-ethoxy-benzene

4-amino-ethoxy-ethoxy-ethoxy-benzene

4-amino-ethoxy-ethoxy-ethoxy-benzene

4-aminobenzoic acid methoxy

ethoxy-ethyl ester

4-amino-benzoic acid methoxy

ethoxy-ethyl ester

aniline

4-anisidine

1,3,3-trimethyI-2-methylene-2,3-dihy-golden yellow droindol

1,3,3-trimethyl-2-methylene-2,3-dihy- golden yellow droindol l, 3,3-trimethyl-5-chloro-2-methylene-2,3-golden yellow dihydroindole

1,3,3,5-tetramethyl-2-methylene-2,3-golden yellow dihydroindole

1,3,3,5-tetramethyl-2-methylene-2,3-golden yellow dihydroindole

1,3,3-trimethyl-5-nitro-2-methylene-2,3-yellow, dihydroindole orange

1,3,3-trimethyl-5-carbomethoxy-2-yellow. methylene-2,3-dihydroindole orange

1,3,3-trimethyl-5-nitro-2-methyl orange-2,3-dihydroindole

1,3,3-trimethyl-2-methylene-2,3-golden yellow dihydroindole

1,3,3-trimethyl-5-nitro-2-methy-orange len-2,3-dihydroindole l, 3,3-trimethyl-2-methylene-2,3- golden yellow dihydroindole-5-carboxylic acid meth-

oxyethyl ester

1,3,3-trimethyl l-2-methylene-2,3-yellow.

dihydroindole-5-carboxylic acid-meth-orange oxy-ethyl ester

Example 2

21.1 parts by weight 4-amino-methoxy-ethoxy-ethoxy-benzene are dissolved in 150 parts by volume of water and 22 parts by volume of concentrated hydrochloric acid, cooled to 0 ° C. and mixed with a solution of 7.3% by weight . Parts of sodium nitrite in 25 parts by volume of water diazotized at 0-5 ° C. The diazonium solution is allowed to stir for a further hour at 0-5 ° C., excess nitrite is destroyed by adding amidosulfonic acid and filtered into a hydrochloric acid solution of 15.2 parts by weight of 1,3,4-trimethyl-6-methylene-dihydropyrimidone-2 a. The coupling is completed by adding 100 parts by weight of sodium acetate, the suspension of the azo dye is left to stir overnight, it is filtered off with suction and washed with 500 parts by volume of 20% sodium chloride solution. The color salt is mixed with 300 parts by volume of water and made alkaline with 40 parts by volume of 10% sodium hydroxide solution, the azobase precipitating. The suspension of the azobase is left

Stir overnight, then warm it to 40 ° C for 3 hours, vacuum it and wash it neutral with water.

Yield: 27.8 parts by weight, melting point: 102-104 ° C. 13.9 parts by weight of the color base thus obtained are stirred with 3 parts by weight of triisopropanolamine in 50 parts of chlorobenzene for 10 minutes in a boiling water bath and after cooling to 80 ° C 6.1 parts by weight of dimethyl sulfate added dropwise. The reaction mixture is then stirred for 3 hours at 80-85 ° C. and the progress of the methylation is monitored in a thin-layer chromatogram. Then the chlorobenzene is distilled off using steam, the dye solution is mixed with activated charcoal, filtered and, after cooling to room temperature, the solution is salted out with 90 parts by weight of sodium chloride. The dye is left to stir overnight, suction filtered, washed with 150 parts by volume. Saline and dry it in vacuo at 50 ° C. 12.8 parts by weight of the dye of the formula are obtained

40

45

0 II

CH., - ^. ✓'C

CH ^^ CH ^ CH-N - ^ - ^^ - OC ^ OC ^ OCHj cl *

CH ^

which stains polyacrylonitrile materials in a yellowish orange with excellent lightfastness.

The dye is characterized by a very good ability to migrate.

Instead of the one used in the example above

Diazo component The diazo components given below with the same coupling component and otherwise do the same in the same way, so you also get valuable dyes that dye polyacrylonitrile in a yellowish orange with excellent fastness properties and which also have good migratory properties.

7

625 822

4-amino-methoxy-ethoxy-benzene

4-amino-ethoxy-ethoxy-benzene

4-amino-ethoxy-butoxy-benzene

4-amino-ethoxy-ethoxy-ethoxy-benzene

4-amino-butoxy-ethoxy-ethoxy-benzene

4-Amino-benzoic acid-methoxy-ethyl ester

Ethyl 4-amino-benzoate

4-Amino-benzoic acid-butoxy-ethyl ester

4-Amino-benzoic acid-methoxy-ethoxy-ethyl ester

Ethyl 4-amino-benzoate

4-Amino-benzoic acid-butoxy-ethoxy-ethyl ester

4-amino-benzoic acid-methoxy-ethoxy-ethoxy-ethyl ester

Example 3

12.5 parts by weight of the azobase prepared according to Example 2 are heated with 50 parts by weight of p-toluenesulfonic acid methyl ester for 3 hours on a boiling water bath. The reaction mixture is discharged onto 500 parts by volume of water, heated to boiling for 10 minutes, activated carbon is added, filtered and, after cooling to room temperature, the dye is salted out with 50 parts by weight of sodium chloride. The same dye as described in Example 2 is obtained.

Example 4

12.5 parts by weight of the azobase prepared according to Example 2 are heated with 100 parts by volume of chlorobenzene on the boiling water bath for 10 minutes and then mixed with 10.2 parts by weight of diethyl sulfate and the reaction mixture is kept at 120 ° C. for 24 hours . The chlorobenzene is then distilled off with steam. The mixture is filtered in the presence of activated carbon, after cooling it is salted out with 50 parts by weight of sodium chloride, stirred overnight, filtered off with suction and the dye is washed with 500 parts by volume of 10% aqueous sodium chloride solution.

The dye dyes polyacrylonitrile in a yellowish orange with very good lightfastness.

Example 5

Polyacrylonitrile fibers are introduced at 40 ° C. in a liquor ratio of 1:40 into an aqueous bath containing 0.75 parts by weight of 30% acetic acid, 0.38 parts by weight of sodium acetate and 5 0.15 parts by weight of one per liter Contains dye, the preparation of which was described in Example 2. The mixture is heated to boiling within 20-30 minutes and the bath is kept at this temperature for 30-60 minutes. After rinsing and drying, a yellowish-orange color is obtained with very good fastness properties.

Example 6

A fabric made of polyacrylonitrile is printed with a printing paste which was produced in the following manner: 15 30 parts by weight of the dye described in Example 2, 50 parts by weight of bis-cyanoethyl formamide and 30 parts by weight of 30% acetic acid are poured with 330 parts by weight of hot water and the solution obtained is added to 500 parts by weight of crystal gum (gum arabic as a thickener). 20 Finally, 30 parts by weight of zinc nitrate solution are added. The pressure obtained is dried, steamed for 30 minutes and then rinsed. A yellowish-orange print with very good fastness properties is obtained.

25 Example 7

Acid-modified polyglycol terephthalate fibers are introduced at 20 ° C. in a 1:40 liquor ratio into an aqueous bath containing 3-10 parts by weight of sodium sulfate, 15 parts by weight of dimethylbenzyldodecylammonium chloride and 0.15 30 parts by weight. Contains parts of the dye described in Example 2 and was adjusted to pH 4-5 with acetic acid. The mixture is heated to 100 ° C. in the course of 30 minutes and the bath is kept at this temperature for 60 minutes. The fibers are then rinsed and dried. A yellow coloration of 35 very good fastness properties is obtained.

G

Claims (2)

625822 2nd PATENT CLAIMS 1. Process for the preparation of new hydrazone dyes of the general formula I K-CH — N-N - / ^ in the K for a remainder of the formula At -CH- or stands, and R is an alkyl radical which is optionally substituted by a hydroxyl group, Rt and Ri are hydrogen, halogen, an alkyl, cycloalkyl, alkoxy, nitro, carbalkoxy, cyano, acyl, acylamino, aryl or aralkyl radical, Ri is an alkyl radical, R-i is hydrogen, an alkyl or aryl radical and An is an anion, and in which at least one of the substituents R, Ri, R> and R4 is a radical of the formula -A-0- (B-0) p-E -A-0-C0-F-0- (B-0) p-E IV V 10th (VII) At what R 'and R'3 independently of one another are a Ci-C4-alkyl radical, 15 R' 1 and R 'i independently of one another hydrogen, chlorine, a Ci-Gi-alkyl, Ci-Ci-alkoxy or acetylamino radical and An represents an anion, and in which at least one of the two radicals R '1 and R'2 corresponds to a radical of the formula IVa, Va or Via, or can be substituted by such a radical. 3. The method according to claim 1, characterized in that hydrazone dyes of the general formula VIII 25th *1 R3 \ ^ C ^ n_r, (Vju) An in which the radicals R ', R' t, R '3 and An have the same meaning as in Claim 2 and R'4 is hydrogen, Ci-Gi-alkyl or 35 phenyl, and in which either R' 1 is a radical corresponds to the formula IVa, Va or Via or R'4 can be substituted by such a radical. or - A- (0- F) q-C0-0- (B-0) p-E VI means or is substituted by such a radical in which A represents an optionally substituted alkylene radical or an alkenylene radical or a direct bond, B for an optionally substituted alkylene or alkenylene radical, E for an optionally substituted alkyl, alkenyl, cycloalkyl, formyl, alkylcarbonyl, alkenylcarbonyl or cycloalkylcarbonyl radical, hydrogen, an optionally substituted phenylcarbonyl, phenylalkylcarbonyl, phenoxyalkylcarbonyl or phenylalkyl radical, F represents an optionally substituted alkylene radical, up to 5 and q represents 0 or 1, characterized in that azobases of the general formula XI