DE2502024A1 - Novel azomethine dyes free of sulphonic acid groups - suitable for leather, natural and synthetic fibres, paper and inks - Google Patents

Abstract

Novel SO3H-free basic azomethine cpds. of formula: R1 is 1-4C alkyl or 1-4C, alkoxy, R2 is e.g. -NO2, -CN, -CF3, phenyl-(1-4C alkyloxy), naphthyl-(1-4C alkyloxy), phenyl, naphthyl, phenyl(1-4C alkyl), naphthyl-(1-4C alkyl), (5-6C cycloalkyl), -O2C-(1-4C alkyl) carbonyloxy, naphthyl-(1-4C alkyl) -carbonyloxy, phenylazo, naphthylazo, (1-4C)alkonoyl(sulphonyl)amino, benzoylamino etc. R3 is halogen, R5 and R5 are each (1-4C) alkyl opt. substd. by halogen, cyano, hydroxy, (1-4C) alkoxy, phenyloxy, naphthyloxy, phenyl or naphthyl gps. or are 5-6C cycloalkyl or together form a satd. 5-6-membered ring, R6 is phenyl, naphthyl, 5-6C cycloalkyl, allyl or (1-6C) alkyl opt. substd. by halogen, cyano, hydroxy, (1-4C) alkoxy, phenyloxy, naphthyloxy, phenyl, naphthyl or carboxamido gps. R7 is (1-6C) alkyl opt. substd. by halogen, cyano, carboxamido, hydroxy, (1-4C) alkoxy, phenyloxy, naphthyloxy, phenyl or naphthyl gps. a 5-6C cycloalkyl gp. or allyl, R8 is halogen, (1-4C) alkyl or (1-4C) alkoxy, R9 is one of the R2 gps., R10 is H, (1-4C) alkyl or (1-4C) alkoxy, hydroxy or phenyl gps. A- is an anion, m is 0-3 (pref. 0-2), n is 0 or 1, k is 0-3 (pref. 0 or 1) y is 0-3 and x is 0 or 1 wherein, when k=1, Z is not = naphthyl, y=1-3 and x=1, k+m+n =3 and arom. carboxylic rings or partially unsatd. carbocyclic rings may be condensed onto the arom. rings B and D) are made opt. contg. nonionic substituents by N-alkylating with R7-A. The azomethines may be used as dyes for leather, natural, lignin-contg. fibres, mercerised cotton, paper and, esp. (co)polyacrylonitrile fibres, acid-mod. polyesters or acid-mod. polyamides. They are also used in (ballpoint) inks/pastes and in polyacrylonitrile spinning solns.

Description

Process for the production of Basic azomethine compounds free from sulfonic acid groups The invention relates to a process for the preparation of basic azomethine compounds free from sulfonic acid groups of the formula where Z R1 is a (1-4C) -alkyl or (1-4C) -alkoxy radical, R2 -N02, -CN, -CF3, phenyl- (1-4C) -alkyloxy, naphthyl- (1-4C) -alkyloxy, phenyl , Naphthyl, phenyl- (1-4C) -alkyl, naphthyl- (1-4C) -alkyl, (5 or 6C) -cycloalkyl, -Alkyl, benzoyloxy, naphthoyloxy, phenyl- (1-4C) -alkylcarbonyloxy, naphthyl- (1-4C) -alkylcarbonyloxy, phenylazo, naphthylazo or a (1-4C) -alkanoylamino-, (1-4C) -alkylsulfonylamino-, Benzoylamino, naphthoylamino, phenylsulfonylamino, naphthylsulfonylamino, N- (1-4C) -alkylcarbamoyl-, N, N-di- (1-4C) -alkylcarbamoyl-, N- (1-4C) -alkyl-N- phenyl-carbamoyl-, N- (1-4C) -alkyl-N-naphthyl-carbamoyl-, N- (1-4C) -alkylsulfamoyl-, N, N-di- (1-4C) -alkyl-sulfamoyl-, (1-4C) -A1-kylsulfonyl-, phenylsulfonyl-, naphthylsulfonyl-, benzoyl-, naphthoyl-, (1-4C) -alkylcarbonyl, phenyloxy-, naphthyloxy-, (1-4C) -alkyl-, (1-4C ) -Alkoxy, halophenoxy, (1-4C) -alkoxycarbonyl, phenyloxycarbonyl, naphthyloxycarbonyl, phenyl- (1-4C) -alkyloxycarbonyl or naphthyl- (1-4C) alkyl-oxycarbonyl group, R3 halogen, R4 and R5 independently of one another in each case a straight-chain or branched one, optionally through a halogen atom or a cyano, hydroxyl, (1-4C) -alkoxy, phenyloxy, naphthyloxy, phenyl or naphthyl group pe substituted (l-4C) -alkyl radical or a cyclo (5 or 6C) -alkyl radical or the radicals R4 and R5 together with the carbon atom attached to them can form a saturated 5- or 6-membered ring, R6 phenyl, Naphthyl, (5- or 6C) -cycloalkyl, allyl or a group optionally substituted by a halogen atom or a cyano, hydroxyl, (1-4C) -alkoxy, phenyloxy, naphthyloxy, phenyl, naphthyl or carboxamido group ( 1-6C) -alkyl radical, R7 is a (1-6C) group optionally substituted by a halogen atom or a cyano, carboxamido, hydroxyl, (1-4C) alkoxy, phenyloxy, naphthyloxy, phenyl or naphthyl group - Alkyl radical or a (5 or '- 6C) cycloalkyl radical or the allyl radical, R8 halogen, a (1-4C) -alkyl or (1-4C) -A1-koxy radical, Rg one of the radicals of R2, Rlo hydrogen, a (1-4C) -alkyl or (1-4C) -alkoxy radical, alkylene a straight-chain or branched alkylene radical, optionally substituted by a (1-40) -alkoxy group or by a hydroxyl or phenyl group est with 2 to 6 carbon atoms, an anion, m 0, 1, 2 or 3, n 0 or 1, k 0, 1, 2 or 3, y 0, 1, 2 or 3 and x 0 or 1, where for the case that k = 1 and Z is different from naphthyl, y must stand for 1, 2 or 3 or x for 1 and the sum of k + m + n is a maximum of 3 and the sum of x + y is a maximum of 3 and further aromatic-carbocyclic rings or partially unsaturated carbocyclic rings, which may contain nonionic substituents, can be fused onto the aromatic rings B and / or D, characterized in that a compound of the formula (R1) R sL m, 4 CR (R2) n 0 5 O-alkylene-OZ (11) CH-N = N QB 6 < Rlo on the N atom adjacent to the ring B with a compound which introduces the radical R7 N-alkylated.

Preferred compounds of the formula (I) are those in which n = 0 or 1, m for 0, 1 or 2 or k for 0 or 1 and the sum of k + m stands for 0, 1 or 2 and the sum for x + y stands for 0, 1 or 2.

The compounds of the formula (I) can advantageously be obtained if one a compound of the formula (II) on the nitrogen atom adjacent to the ring B with a Reacts compound of the formula R7 - A (III), in which A is a cleavable as anion # Rest means.

Compounds of the formula are important where R2 -N02 -CN, -OF3, or a (1-4C) -alkanoylamino-, benzoylamino, (1-4C) -alkylsulfonyl-, phenylsulfonyl-, (1-4C) -alkylcarbonyl-, benzoyl-, benzoyloxy-, phenoxy-, para-chlorophenoxy-, (1 -4C) -Alkoxycarbonyl-, N, N-di- (1-4C) -alkylsulfamoyl-, (1-4C) -alkyl or (1-4C) -alhoxy group, R3 chlorine or bromine R4 'and R5' a ( 1-4C) -alkyl radical, R6 'a (1-4C) -alkyl radical, 2-hydroxy- (2-4C) -alkyl, 2-carboxamidoethyl or allyl, R7' a (1-4C) -alkyl radical, 2-hydroxy - (2-4C) -alkyl, 2-carboxamidoethyl, benzyl or allyl, R11 hydrogen or one of the two R11 for hydrogen and the other R11 for (1-4C) -alkyl, one of the radicals of R2, m '0, 1 or 2 n 0 or 1, k' O, 1 or 2 and y1 0, 1 or 2, where in the event that k = 1 and Z1 is different from naphthyl 'y' must stand for 1, 2 or 3 or x for 1, the rings B1 and D1 contain no further substituents in addition to the substituents mentioned and the sum of n + m '+ k' must be a maximum of 2 and the sum of x + y ' is a maximum of 2.

Among the compounds of the formula (IV) are in particular those of importance in which n = 0 or 1, m 'for 0 or 1, or k' for 0 or 1 and the sum of k '+ m' stands for 0 or 1 and the sum of x + y 'for 0 or 1 stands.

Compounds of the formula are of particular importance wherein R2 "-NO2, (1-4C) -alkoxycarbonyl, N, N-di- (1-4C) -alkylsulfamoyl, (1-4C) -alkyl, (1-4C) -alkoxy, Phenoxy or para-chlorophenoxy, R3 chlorine, R "a (1-4C) -alkyl radical, 2-hydroxypropyl or 6-2-carboxamidoethyl, R7" a (1-4C) -alkyl radical, 2-hydroxypropyl or 2-carboxamidoethyl, R81 is chlorine, bromine, (1-4C) -alkyl or (1-4C) -alkoxy, m "0 or 1, k" 0 or 1 and y "0 or 1, with the case that k" = 1 means and Z2 is different from naphthyl, y "must stand for 1 and the sum of n + m" + k "is a maximum of 2.

Compounds of the formula are of very particular importance wherein R "'(1-4C) -alkyl, (1-4C) -alkoxy, phenoxy, para-2 chlorophenoxy, benzyl or benzyloxy, or in particular of the formula wherein R2 "" methyl, ethyl, methoxy, ethoxy, R6 "'methyl or ethyl, R7" methyl or ethyl, R10' hydrogen, methyl, ethyl, methoxy or ethoxy, R11 'hydrogen or one of the two radicals R11' hydrogen and the other radicals R1,1 denote methyl.

Particularly good compounds correspond to the formula where R1o is hydrogen, methyl or methoxy and 10 R8 is chlorine, methyl or methoxy, or in particular of the formula Cycloalkyl radicals are unsubstituted or can, for example

be substituted by (1-4C) alkyl groups, such as by 1, 2 or 3 Methyl groups.

Halogen can in any case include bromine, fluorine or iodine, in particular but understand chlorine. Carbocyclic radicals condensed onto rings B and / or D. can be, in each case substituents, in particular those which do not make water soluble, dwh. carry non-ionic substituents; they preferably carry halogen atoms, alkyl or alkoxy groups.

In the above-mentioned substituents, the alkyl radicals contain 1 to 6 and advantageously 1 to 3 carbon atoms; the alkoxy radicals contain 1 to 3 carbon atoms.

Alkylsulfonyl stands, for example, for methyl or ethylsulfonyl; Alkylsulfamoyl stands for example for methyl or ethylsulfamoyl and dialkylsulfamoyl for N, N-dimethyl or N, N-diethylsulfamoyl.

e Anion A includes both organic and inorganic ions understand, such as halogen, such as chloride, bromide or iodide, sulfate, bisulfate, Methyl sulfate, aminosulfonate, perchlorate, carbonate, bicarbonate, phosphate, phosphomolybdate, Phosphotungstate, phosphotungstamolybdate, benzenesulphonate, naphthalenesulphonate, 4-chlorobenzenesulfonate, oxalate, maleate, acetate, propionate, lactate, succinate, Chloroacetate, tartrate, malate, methanesulfonate or benzoate ions or complexes Anions, such as that of zinc chloride double salt.

The alkylation can be carried out in such a way that one solutions, Suspensions or slurries of a compound of the formula (II) in an inert Medium with the alkylating agent heated to 60-1500C, preferably 80-1200C. For this purpose, the alkylating agent can also be used in excess as a solvent.

Suitable inert media are e.g. organic liquids such as gasoline, Ligroin, cyclohexane, benzene, toluene, chloroform, chlorobenzene and dichlorobenzene, Nitrobenzene, tetralin, dioxane, acetonitrile and dimethylformamide.

Suitable alkylating agents, e.g. of the formula (III), are e.g. dimethyl sulfate, Diethyl sulfate, di-n-butyl sulfate, di-iso-amyl sulfate, dimethyl pyrosulfate, benzenesulfonic acid methyl, ethyl, n-propyl, iso-propyl and isobutyl esters, toluenesulfonic acid methyl, ethyl, -n-propyl-, -iso-propyl- and -iso-butyl ester, methyl iodide, ethyl iodide, n-butyl bromide, Allyl bromide, 2-chloro and 2-bromo diethyl ether. The alkylation can also be carried out in the presence alkaline agents, especially in the presence of tertiary amines, according to Belgian patent specification 735,565 are carried out.

The compounds of the formula (II) are new; they can be prepared by using the diazo compound from a known amine of the formula H2N O-alkylene-OZ (X) R10 in a manner known per se with a compound of the formula couples and the coupling products obtained are treated with an alkali metal hydroxide in a manner known per se. The coupling of the diazo compound from an amine of the formula (X) with a compound of the formula (XI) can be carried out in an aqueous, acidic or neutral medium at temperatures from -5 "to 30 ° C., if appropriate in the presence of a buffer.

2,3-Dihydro-2-methyleneindoles of the formula which are suitable according to the invention (XI) are known e.g. from the French patent specification 2,102,335.

The new products are valuable dyes that are used for dyeing and printing of materials made of leather, tannin cotton, as well as for dyeing lignin-containing materials Fibers like coconut, jute and sisal can be used. You are still suitable for the production of writing fluids, stamp inks, ballpoint pen pastes and can also be used in rubber printing. They are also used to color paper.

Suitable for dyeing with the basic dyes of the general formula in particular flakes, fibers, threads, tapes, woven or knitted fabrics made of polyacrylonitrile ~ or from copolymers of acrylonitrile with others.

ren vinyl compounds such as vinyl chloride, vinylidene chloride, vinyl fluoride, Vinyl acetate, vinyl pyridine, vinyl imidazole, vinyl alcohol, acrylic and methacrylic acid esters and -amides, as. Dicyanethylene, or flakes, fibers, threads, tapes, woven or knitted fabrics made of acid-modified aromatic polyesters, as well as acid-modified polyamide fibers. Acid modified aromatic polyesters are, for example, polycondensation products from sulfoterephthalic acid and ethylene glycol, d. H. polyethylene glycol terephthalates containing sulfonic acid groups (Type DACRON 64 of E.I. Du Pont de Nemours and Company), as used in the Belgian U.S. Patent No. 549,179 and U.S. Patent Nos. 2,893,816 and 3,379,723 are. Acid modified polyamide fibers are e.g. from the Belgian patent 706.104 known.

The dyeing can be done from a weakly acidic liquor Dyebath expediently enters at 40-600C and then dyes at boiling temperature. You can also dye under pressure at temperatures above 100C. Furthermore let the dyes spinning solutions for the production of polyacrylonitrile-containing fibers add or apply to the undrawn fiber.

The dyeings on polyacrylonitrile, acid-modified polyesters and acid modified polyamide are characterized by good light, wet, rubbing and Fastness to sublimation and characterized by a high affinity for the fiber. The dyes have good cooking temperature stability and are quick-setting in combination with other basic dyes, they also have good salt tolerance and good pH stability. The dyes form with anionic precipitants such as Clay, tannin, phosphotungstic (molybdenum) acids lightfast pigments that are beneficial can be used in paper printing. The dyes can be used individually or in mixtures be applied.

In the compounds of the formula (I), the anion can be replaced by others Exchange anions, e.g. with the help of an ion exchanger or by reaction with salts or acids, optionally in several stages, e.g.

via the hydroxide or via the bicarbonate.

The new compounds can be converted into coloring preparations. the Processing, e.g. into stable, liquid or solid dye preparations, can be based on general known manner, e.g., by grinding or granulating, or then by dissolving in suitable solvents, optionally with the addition of an auxiliary, e.g. a stabilizer or solubilizer such as urea.

Such preparations can, for example, according to the information in French patents 1,572,030 and 1,581,900.

In the following examples the parts mean parts by weight which Percent weight percent; the temperatures are given in degrees Celsius.

Example 1 22.9 parts of 4- (2'-phenoxy) -ethoxy-aniline are mixed with 40 parts Water and 25.2 parts of 30% hydrochloric acid were stirred to form a homogeneous paste. the The slurry cooled to 0-30 is mixed with a solution consisting of 7.25 parts Sodium nitrite diazotized in 20 parts of water.

It is stirred for 30 minutes with a slight excess of nitrite, and then the excess nitrite is destroyed by adding sulfamic acid. At 10-200 it becomes a solution stirred under a stream of nitrogen from 17.3 parts of 1,3,3-trimethyl-2-methylene-2,3-dihydroindole in 100 parts of water and 10.6 parts of 30% hydrochloric acid within the diazonium salt solution prepared above added dropwise an hour. The pH of the mixture is maintained by simultaneously Add dropwise 20.2 parts of 30% sodium hydroxide solution as close as possible to 4-5. The orange-yellow suspension is then stirred at 40 ° for 12 hours; afterward is adjusted to a pH of 10 with 0.5 to 1.5 parts of sodium hydroxide and 1 hour stirred for a long time at 400. The coupling product precipitated in orange-yellow crystals is first with weakly alkaline water (0.5% sodium hydroxide content) of 300 washed, then washed neutral at 300 and dried under vacuum at 600. Yield: 38.6 parts; Mp: 145-6 ° (uncorrected).

For the alkylation, 38.6 parts of the azo base are dissolved in 400 parts of chlorobenzene with the addition of 4 parts of triisopropanolamine. At 80-850, 50 parts of chlorobenzene are distilled off, then 17.1 parts of dimethyl sulfate are added dropwise at 800 and the mixture is stirred for 10 hours at the same temperature, then 20 parts of water are added and the mixture is stirred for 2 hours at 80 ". The chlorobenzene is removed by steam distillation; the The yellow dye obtained in crystalline form on cooling is washed with 5% sodium chloride solution and dried at 600. It corresponds to the formula and dyes polyacrylonitrile and basic dyeable polyester fibers in yellow shades with good light and wet fastness.

In the following Table I the structure of further dyes is given, as they can be obtained according to the information in Example 1. They correspond to the formula R12 CH3 \ CH-NN W CH - R16 CN βNRi CH = NN, 0CR1H17% 18019 anion A. e 13 3 14 15 in which R12-R19 have the meanings given in the columns. In a further column X, the shade of the coloring on polyacrylonitrile is indicated. Those listed in the description are suitable as anions.

Table I. Example RRRRRRRR x No. 12 13 14 15 16 17 18 19 X Ti Ti xuno d X ~ I mi mA t mA 3 -CH3 g do. zgk HHH do. 4 & CQ20 H do. m vc H mm H do. 5 -OCH3 H do. do. HHHH red yellow 6 mm H mm HHHH do. 7 mmm -CH3 m HH m gOt1Stihi Whom 9 HH mmm: cmxmm U) 10 CH3O-C- m do. dc. H m HH do. XO 0 ON 6 0 0 0 0 w U aaauuaaa lll 11 F3C- n dc. do. H In 1 n , imooommooo A; U ggg CS CS U gtg around IU ~, mmmmmmu 'mmm on it m eq = = m U 5: U -o U «, I 1 u? io mm cJ m O n Around. ffi fi Sk N ns D ba O ~ I \ Briß.Ps R12 R13 R14 R15 R16 R17 R18 R19 x b> 12 HH -CH3 -CH3 fl -CH3 HH reddish xunu rl rl tn R b bQ R 13 HH do. dc. 4 rl -C2H5 HH do. 0 0 0 0 0 0 0 0 0 0 m H mmmm E 3 ° U 54 u kh H dc. dc. k S4 -C2H, 5 H dc. rd rd (d (U atu aa E 16 m H mu U> imm: c: m XXX 17 HH dc. dc. HHH para-C3 reddish yellow cu XC mme ce me ll n u, X 19 mm do. dc. O m H vc m dc. ur tn ~, ::; ooooooooo 21 H g dc. dc. HHH mea-C3 oo ~ i tC ooooooooo po, iU ggggggggg x, mmmmm 5: esss wi mm: x Q Bq. s: O - fi z ~ i ~ i H ~ H ~ i «N a) z mi Example R12 R13 R14 R15 R16 R17 R18 R19 x No. xu H -CH3 -CH3 HHH para-Cl yellow rnA o O oooooooo 23> HH dc. do. HHH pra-Br dc. aaaaaada m CI 24 at dc. dc. H -CH3 H o 1 r I 0 0 0 i Im I daaad kkk kU kU rd m (d rd rd I rd I 25 HH dc. there. H QxU-O QtV = O tn m td 26 Ii H dc. dc. H m Ú mmm 27 nm rc mmx to XXX m X P: UU 28 H r 3: mmm ::: era- 29 HH dc. dc. HHH CüCH3 dc. 0 3: 0 0 6 0 0 0 0 0 30 H do. dc. gaaa -C2 H: oooooooo ruggggggge e t: mm ffii Ai evi v uw vo F aw O aJ>; (S (YNN O4 N VS «ss" In the following Table II the structural structure of further dyes is given, as they can be obtained according to the information in Example 1. They correspond to the formula R12 CH3 R16 <H = NN W -CH-CH3R, 17R, 1821 13 R14 15 CH-0 R15 / 13 14 15 in which R12-R18 have the meaning given in the columns. The point of attachment of the oxygen atom to the naphthalene nucleus (1 or 2) is indicated in a further column Y; in the last column X the shade of the coloring on polyacrylonitrile is given. Suitable anion Ag are those listed in the description.

T able II BSPr: R12 R13 R14 R15 R16 R17 R18 YX 31 HH -CH3 -CH3 HHH 1 rctsti- chig yellow 4Y 32 bs dc. dc. HHH 2 o do. aaaaaaaaa 0 6 Q) h U b ri N rl rt CV CV rl rl cV > 4 HNHNHNHHN oO X «<M dc. dc. HHH 2 do. 36 -0 H dc. do. HHH 1 dc. <mmm U mmmmmmm 38 m -CH3 dc. mmm mn m: nm r4 XXXXX mxxxx U) n. . . . .- -. 40 Cl dc. ooo HHH o dc. IU aaaaaaaaa m Cl n <moooooooooo XU ggggg rU mmmmmt: nm 'm m- m N mX Q X1 < <mmmu «mmuu «Uomoo IIYI g AS HN nv @ b O o < m Z E.g. R12 R13 R14 R15 R16 R17 R18 YX No. 42 Br H -CH3 -CH3 HHH 1 reddish yellow 43 HH do. -C2H5 HHH 2 do. 44 -OCH3 -OCH3 do. -CH3 HHH 1 do. 45 do. do. do. do. HHH 2 do. 46 HH do. do. -CH3 HH 1 do.

Dyeing instructions A 20 parts of the dye salt described in Example 1 and 80 parts of dextrin are ground in a powder mill for 4 hours. The same Dyestuff mixture can also be made by pasting in 100 parts of water and gain subsequent spray drying. 1 part of the preparation thus obtained made into a paste with 1 part of 40% acetic acid, the porridge with 200 parts of demineralized Poured over water and briefly boiled. Dilute with 7000 parts of demineralized Water, adds 2 parts of glacial acetic acid and goes at 60 ° with 100 parts of polyacrylonitrile fabric. into the bathroom. You can do the material beforehand for 10-15 minutes at 600 in one Pretreat the bath consisting of 8000 parts of water and 2 parts of glacial acetic acid.

The mixture is heated to 98-1000 within 30 minutes and cooked for 1 1/2 hours long and rinse. A yellow dyeing with good lightfastness and good fastness is obtained Wet fastness properties.

You can also use 10 parts of the dye salt mentioned in Example 1, according to a known method from the corresponding dye halide or perchlorate can be prepared, dissolve in 60 parts of glacial acetic acid and 30 parts of water. You get a stable concentrated solution of the dye with a dye content of about 10%, according to the above dyeing instructions for dyeing polyacrylonitrile can be used.

Dyeing instruction B 20 parts of the dye from Example 1 are mixed with 80 parts of dextrin mixed in a ball mill for 48 hours; 1 part of the so The preparation obtained is made into a paste with 1 part of 40% acetic acid, the pulp with Pour over 200 parts of demineralized water and boil briefly. With this Starnmlösung is colored as follows: a) Dilute with 7000 parts of demineralized Water, puts 21 parts of calcined sodium sulfate, 14 parts of ammonium sulfate, 14 parts Formic acid and 15 parts of a carrier based on reaction products of Ethylene oxide with dichlorophenols and goes at 600 with 100 parts of polyester fabric, which is modified by acidic groups, in the bath, you can use the material before 10-15 min.

long at 60 ° in a bath, consisting of 8000 parts of water and 2 Pre-treat parts of glacial acetic acid.

The mixture is heated to 98-100 ° within 30 minutes and cooked for one hour long and rinse. A level yellow dyeing with good wet fastness properties is obtained.

b) Dilute with 3000 parts of demineralized water, place 18 Parts of calcined sodium sulfate and 6 parts each of ammonium sulfate and formic acid and goes at 60 ° with 100 parts of polyester fabric, which by acidic groups is modified in the bathroom. It is heated in a closed vessel within 45 minutes at 110 °, keeps this Temperature while shaking 1 Hour at, cools. then within 25 minutes to 60 ° and rinses the dyed goods. A level yellow dyeing with good wet fastness properties is obtained.

c) Proceed in the same way as in b), but heat the closed one Vessel at 1200 for 1 hour.

Dyeing instruction C 20 parts of the dye from Example 1 are mixed with 80 parts of dextrin mixed in a ball mill for 48 hours.

1 part of the preparation obtained in this way is mixed with 1 part of 40% acetic acid made into a paste, pour 200 parts of demineralized water over the porridge and briefly boiled up. This solution is added to the dye liquor prepared below: The solution is diluted with 7000 parts of demineralized water, and 21 parts are added calcined sodium sulfate, 14 parts ammonium sulfate, 14 parts formic acid and 15 Parts of a carrier based on reaction products of ethylene oxide Dichlorophenols and buffers the liquor with an acidic buffer solution to one pH value of 6, and goes at 250th with 100 parts of polyamide fabric, which through anionic groups are modified, in the bath, with a liquor ratio of 1:80 a. The bath is heated within 45 Minutes to 980, boil for an hour and rinse under running water from 700-800 and then under cold water. The tissue can be centrifuged and then dried for drying be ironed.

A yellow dyeing with good fastness properties is obtained.

Claims (8)

Claims I. Process for the preparation of sulfonic acid group-free basic azomethine compounds of the formula where Z R1 is a (1-4C) -alkyl or (1-4C) -alkoxy radical, R2 -N02, -CN, -CF3, phenyl- (1-4C) -alkyloxy, naphthyl- (1-4C) -alkyloxy, phenyl , Naphthyl, phenyl- (1-4C) -alkyl, naphthyl- (1-4C) -alkyl, (5 or 6C) -cycloalkyl, -Alkyl, benzoyloxy, naphthoyloxy, phenyl- (1-4C) -alkylcarbonyloxy, naphthyl- (1-4C) -alkylcarbonyloxy, phenylazo, naphthylazo or a (1-4C) -alkanoylamino-, (1-4C) -alkylsulfonylamino-, Benzoylamino, naphthoylamino, phenylsulfonylamino, -naphthylsulfonylamino, N- (1-4C) -alkylcarbamoyl-, N, N-di - ((1-4C) -alkylcarbamoyl-, N- (1-4C) -alkyl- N-phenyl-carbamoyl-, N- (1-4C) -alkyl-N-naphthyl-carbamoyl-, N- (1-4C) -alkylsulfamoyl-, N, N-di- (1-4C) -alkyl-sulfamoyl -, (1-4C) -A1-kylsulfonyl-, phenylsulfonyl-, naphthylsulfonyl-, benzoyl-, naphthoyl-, (1-4C) -alkylcatnyl, phenyloxy-, naphthyloxy-, (1-4C) -alkyl-, (1 -4C) -Aloxy-, halophenoxy-, (1-4C) -alkoxycarbonyl-, phenyloxycarbonyl-, naphthyloxycarbonyl- phenyl- (1-4C) -alkyloxycarbonyl- or naphthyl- (1-4C) -alkyl-oxycarbonylgurppe, R3 halogen, R4 and R5, independently of one another, are each a straight-chain or branched one, optionally through a halogen atom or a cyano, hydroxyl, (1-4C) alkoxy, phenyloxy, naphthyloxy, phenyl or naphthylg group-substituted (1-4C) -alkyl radical or a cyclo (5 or 6C) -alkyl radical or the radicals R4 and R5 together with the carbon atom attached to them can form a saturated 5- or 6-membered ring, R6 phenyl, Naphthyl, (5 or 6C) cycloalkyl, allyl or a group optionally substituted by a halogen atom or a cyano, hydroxyl, (1-4C) alkoxy, phenyloxy, naphthyloxy, phenyl, naphthyl or carboxamido group (l -6C) -alkyl radical, R7 a (1-6C) -alkyl radical optionally substituted by a halogen atom or a cyano, carboxamido, hydroxyl, (1-4C) alkoxy, phenyloxy, naphthyloxy, phenyl or naphthyl group or a (5 or 6C) cycloalkyl radical or the allyl radical, R8 halogen, a (1-4C) -alkyl or (1-4C) -A1-koxy radical, R9 one of the radicals of R2, Rlo hydrogen, a (1-4C ) -Alkyl or (1-4C) -alkoxy radical, alkylene is a straight-chain or branched alkylene radical which is optionally substituted by a (1-4C) alkoxy group or by a hydroxyl or phenyl group st with 1 to 6 carbon atoms, an anion, m 0, 1, 2 or 3, n 0 or 1, k 0, 1, 2 or 3, y 0, 1, 2 or 3 and x 0 or 1, where for the case that k = 1 and Z is different from Naphthyl7 y must stand for 1, 2 or 3 or x for 1, and the sum of k + m + n is a maximum of 3 and the sum of x + y is a maximum of 3 and further aromatic-carbocyclic rings or partially unsaturated carbocyclic rings, which may contain nonionic substituents, can be fused onto the aromatic rings B and / or D, characterized in that a ver. binding the formula (R1, R4 2) nt g S O-alkylene-OZ (11) (R3) k R R10 on the N atom adjacent to the ring B with a compound which introduces the radical R7 N-alkylated. II. Process for the preparation of sulfonic acid group-free azomethine compounds of the formula (I) according to claim I, characterized in that a compound of the formula (II) on the nitrogen atom adjacent to the ring B with a compound of the formula R7 - A (III) converts, in which A is a radical which can be split off as anion A. Dependent claims 1. Method according to claim I, characterized in that that compounds of the formula (I) are prepared in which n = 0 or 1, m for 0, 1 or 2, resp. k stand for 0 or 1 and the sum of k + m stands for 0, 1 or 2 and the sum for x + y stands for 0, 1 or 2. 2. The method according to claim I, characterized in that compounds of the formula where R2 -N02, -CN, -CF3, or a (1-4C) -alkanoylamino-, benzoylamino, (1-4C) -alkylsulfonyl-, phenylsulfonyl-, (1-40) -alkylcarbonyl-, benzoyl-, benzoyloxy-, phenoxy-, para-chlorophenoxy-, (1 -4C) -Alkoxycarbonyl-, N, N-di- (1-4C) -alkylsulfamoyl-, (1-4C) -alkyl or (1-4C) -alkoxy group, R3, chlorine or bromine R4 and R 'a ( 1-4C) -alkyl radical, 5 R6 'is a (1-4C) -alkyl radical, 2-hydroxy- (2-4C) -alkyl, 2-carboxamidoethyl or allyl, R7' is a (1-4C) -alkyl radical, 2- Hydroxy- (2-4C) -alkyl, 2-carboxamidoethyl, benzyl or allyl, R11 hydrogen or one of the two R11 for hydrogen and the other R11 for (1-4C) -alkyl, R 'is one of the radicals of m' O, 1 or 2, n is 0 or 1, k 'is O, 1 or 2 and y' is O, 1 or 2, where k is 1 and Z1 is different of naphthyl, y 'must stand for 1, 2 or 3 or x for 1, the rings B1 and D1 contain no further substituents in addition to the substituents mentioned and the sum of n + m' + k 'a maximum of 2 and the sum of x + y 'is a maximum of 2. 3. The method according to claim I and dependent claim 2, thereby characterized in that compounds of the formula (IV) are prepared in which n = 0 or 1 means, ml stands for 0 or 1, or k 'stands for 0 or 1 and the sum of k' + m 'stands for 0 or 1 and the sum of x' + y 'stands for 0 or 1. 4. The method according to claim I, characterized in that compounds of the formula wherein R2 -NO2, (1-4C) -alkoxycarbonyl, N, N-di- (1-4C) -alkylsulfamoyl, (1-4C) -alkyl, (1-4C) -alkoxy, Phenoxy or para-chlorophenoxy, chlorine, R6 is a (1-4C) -alkyl radical, 2-hydroxypropyl or 2-carboxamidoethyl, R "is a (1-4C) -alkyl radical, 2-hydroxypropyl or 7-2-carboxamidoethyl, R8 'is chlorine, bromine, (1-4C) -alkyl or (1-4C) -alkoxy, m "0 or 1, k" 0 or 1 and y "0 or 1, where k" = 1 means and Z2 is different from naphthyl, y "must stand for 1 and the sum of n + m" + k "is a maximum of 2. 5. The method according to claim I, characterized in that compounds of the formula wherein R2 "'is (1-4C) -alkyl, (1-4C) -alkoxy, phenoxy, para-chlorophenoxy, benzyl or benzyloxy. 6. The method according to claim I, characterized in that compounds of the formula wherein R2 "" methyl, ethyl, methoxy, ethoxy, R6 'methyl or ethyl, 6 R7 "methyl or ethyl, 7 R10' hydrogen, methyl, ethyl, methoxy or ethoxy, R11 'hydrogen or one of the two radicals R11' hydrogen and the other radical R; is methyl. 7. The method according to claim I, characterized in that compounds of the formula where R "is hydrogen, methyl or methoxy and R8 is chlorine, methyl or methoxy. 8. The method according to claim I, characterized in that compounds of the formula manufactures. III. The azomethine compounds of formula (I). IV. Process for dyeing or printing fibers, threads or therefrom Textiles produced from homopolymers or copolymers of acrylonitrile or as.-Dicyanäthylens exist or contain such, thereby gekennzeicnnet, that one uses dyes of the formula (I) according to claim III. V. Process for dyeing or printing fibers, threads or therefrom manufactured textiles made of synthetic polyamides or synthetic polyesters, which are modified by acidic groups, exist or contain such, thereby characterized in that dyes of the formula (I) according to claim III are used. VI. Use of the dyestuff according to claim III for dyeing of plastics and leather. VII. Use of the dyestuffs according to claim III for dyeing of paper. VIII. The materials colored according to claims IV and V. IX. The materials colored according to claims VI and VII.