CH516628A - Bistyryl dyestuff prepn - contg water-insol dyestuff, for dyeing polyesters greenish-yellow - Google Patents

Abstract

Dyestuff prepn. contains water-insol. styryl dyestuff of formula: NC-C(Y1)=CH-A1-N(R1)-R3-Z-R4-N(R2)-A2-CH=C(Y2)-CN (in which R1 and R2 are opt. substd. alkyl, opt. forming ring with A1 or A2; R3 is opt. substd. alkylene; R4 is direct bond or opt. substd. alkylene; Y1 and Y2 are cyano, carbalkoxy or arylsulphonyl; A1 and A2 are opt. substd. p-phenylene; Z is direct bond or -SO2- free colourless bridge) and dispersant(s). This prepn. is used for dyeing/printing hydrophobic (semi)synthetic fibres, e.g. cellulose acetate and esp. aromatic polyesters; also copolymers of propylene oxide and unsatd. epoxides and PVC fibres. It gives pure, strong, greenish-yellow dyeing, with excellent light- and sublimation fastness.

Description

  

  
 



  Dye preparations containing water-insoluble styryl dyes
The present application relates to new valuable dye preparations which are characterized in that they contain water-insoluble styryl dyes of the formula
EMI1.1
 where R1 and R2 optionally substituted alkyl groups, which together with the radicals A1 and A2 can each be connected to form a ring, R3 an optionally substituted alkylene group, R4 a direct bond or preferably an optionally substituted alkylene group, Y1 and U2 cyano, carbalkoxy or arylsulfonyl groups, A1 and A2 denote p-phenylene groups and Z denote a direct bond or a colorless bridge free of -SO2 groups, and contain at least one dispersant. The dyes used in the preparations can be, for. B.



  obtained by using either a) the dyes of the formulas
EMI1.2
 where X1 and X2 represent a group containing at least one reactive hydrogen atom, preferably an amino, mercapto or hydroxyl group or their reactive derivatives, and R1, R2, R3 and R4 are optionally substituted alkyl or

  Are alkylene groups and At, Ad, Y1 E and Y have the same meaning as above, with a bifunctional compound free of SO.2 groups to form the dyes of the formula (1) according to the invention, or b) the dialdehyde of the formula
EMI1.3
  or its aldimine with a cyano compound of the formula
EMI2.1
 in a molar ratio of 1:

  : 2 condensed, or c) the monostyryl dyes of the formula which have a reactive hydrogen atom bonded to an amino group
EMI2.2
 with a bifunctional compound of the formula
Y'l- (R3) nlZ- (R4) nl, where n is an integer of 1 or 2 and Y'1, and Y's, when n = 2, is a reactive negative radical, preferably a halogen atom , and when n = 1, Y'1 and Y's together with Z form an addition-friendly diepoxy compound.



   During production, the same components A1, A2, R1 and R2 as well as Rs and R4 can be used, so that symmetrical bis-styryl dyes are obtained, as well as starting materials in which one or more of these components are different from one another, so that leads to asymmetrical styryl dyes.



   Examples of the radicals A1 and As are 1.4 phenylene groups in the I formulas
EMI2.3
 called, where c1, ce, d, and d2 are hydrogen atoms,
Halogen atoms, especially chlorine or bromine atoms, lower alkyl groups such as methyl or ethyl groups, lower alkoxy groups such as methoxy or ethoxy groups, thiophenoxy or phenoxy groups.



   The groups cl and c2 are preferably bonded in the ortho position to the C =C double bond and, in addition to the preferred groups mentioned above, can also contain a trifluoromethyl group, an alkylsulfonyl group, preferably a methylsulfonyl group, and an optionally alkylated on the nitrogen atom, e.g. B. methylated, acylamino group in which the acyl radical is the remainder of an organic monocarboxylic acid, an organic b-monosulfonic acid, such as methane, ethane or p-toluene monosulfonic acid, or the
Residue of a carbamic acid or a colloidal acid monoester or monoamide, such as phenoxycarbonyl,
Methoxycarbonyl and aminocarbonyl.



   The groups d1 and d2 are preferably bonded in the orttho position to the coupling-directing amino group.



   The groups R1 and R2 can both hydrogen atoms, alkyl groups or substituted alkyl groups, such as. B. halogenated alkyl groups such as s-chloroethyl, ss, ss, ss-trifluoroethyl, ss, γ-dichloropropyl, ss-cyanoethyl, alkoxyalkyl such as ss-ethoxyethyl or # -methoxybutyl, hydroxyalkyl - such as ss-hydroxyethyl, ss,?

  ; -Dihydroxypropyl, nitroalkyl, such as ss-nitroethyl, carbalkoxy, such as ss-carbo (methoxy, ethoxy or propoxy) ethyl (with the terminal alkyl group in the # 'position cyano, carbalkoxy, acyloxy -, and can carry amino groups, or t.-Carbo (methoxy or ethoxy) propyl, acylaminoalkyl, such as ss- (acetyl or formyl) amino-ethyl, acyloxyalkyl, such as p-acetyloxyethyl , ss,?

  ; -Diacetoxypropyl-, ss- (alkyl- or aryl) -sulfon ylalkyl- such as ss-methanesulfonylethyl, ss-ethanesulfonylethyl, or ss- (p-chlorobenzenesulfonyl) ethyl, alkyl or arylcarbamoyloxyalkyl, such as ss- Methylcarbamyloxyäthyl, and ss-Phenylcarbamyloxyäthyl-, Alkyloxy-carbonyloxyalkyl-, like ss- (methoxy-, ethoxy- or -isopropyloxy) -carbonyloxy- ethyl-, γ-acetamidopropyl-, ss- (p-nitrophenoxy) ät , ss- (p-hydroxyphenoxy) -ethyl-, ss- (ss'-acetyl ethoxycarbonyl) -ethyl-, ss- [ss' - (cyano-, hydroxy-, methoxy- or acetoxy) -ethoxycarbonyl] -ethyl-, Cyanoalkoxyalkyl-, ss-carboxyethyl, ss-acetyl, ethyl,?

  Aminopropyl, fl-diethyiaminoethyl, ss- cyanoacetoxyethyl and -ss-benzoyl-ss- (p-alkoxy or phenoxybenzoyl-oxyethyl groups. Groups R1 and R2 generally contain at least 2 carbon atoms and not more than eight , preferably no more than six carbon atoms.



   If the groups R1 and / or R2 are to form a hydrogenated heterocyclic ring with the adjacent phenylene groups A1 or A2, z. B. of tetrahydroquinoline derivatives or benzomorpholine derivatives as components of the formulas
EMI2.4
  out. Possible are e.g. B. 2,2,4,7-tetramethyl1,2,3,4-tetrahydroquinoline, 7-methyl-1,2,3,4-tetrahydroquinoline, etc.



   The groups R3 and R4 are optionally substituted alkylene groups with preferably at least two carbon atoms, such as. B. unsubstituted ethylene groups or, according to a particular embodiment of the invention, alkylene groups which are hydroxylated in the ss position to the amino group and which can also be part of an alicyclic ring system. The latter arise z. B. in the bilateral conversion of diepoxides, especially diglycidyl compounds, the at least one reactive hydrogen atom-bearing components H-A1-NHR1 and H-A2-NHR2, or the corresponding styryl dyes.

  The hydroxyl groups formed in the ss position can be substituted, the substituents together with the oxyethyl groups leading to the N atom having the same meaning as the groups R1 and R2 defined above, provided they are derived from an N-oxyethyl group starting from the N atom .



   For the colorless Brüdkenglled Z, which is preferably an oxygen atom, an imino group or, in particular, a colorless divalent organic radical, groups of the following formulas are particularly suitable:
EMI3.1
 -O-CH2-CH2-NH-CH2-CH2-O-, or -R5-O-, where R5 is a divalent aliphatic, araliphatic or aromatic radical whose carbon chain can be interrupted by heteroatoms, in particular oxygen atoms, preferably a radical the formula
EMI3.2
 and especially the groups of the formulas -OCO-, -OCOO-, -OCOCOO-, -NHCO-, -CONH-, -CONHCO-, -CONHNHCO-, -NHCOCONH-, and the colorless link of the formula -X ', containing acyl radicals CO-R6-COX'-, where X 'is an oxygen atom,

   is a sulfur atom or an -NHO group and R6 is an aliphatic, aromatic or heterocyclic radical, the colorless link of the formula -X'-CO-NH-R7-NH-CO-X-, where X 'is an oxygen atom, a sulfur atom or an NH group and R7 an aliphatic, aromatic or heterocyclic radical of a diisocyanate, preferably an ethylene, hexamethylene, phenylene or toluylene radical, a radical of the formula
EMI3.3
 is, the colorless link of the formula -OCOX'-R8-X'-OCO-, where X 'has the same meaning as above and R8 is a divalent organic radical,

   is in particular an aliphatic, araliphatic, aromatic or heterocyclic radical which can be interrupted by groups X '; when X 'is an NH group, R8 has the same meaning as R7 and the colorless link of the formula -X "SO2-R9-SO2X" -, where X "is an oxygen atom or an optionally substituted nitrogen atom and R9 is an aliphatic or aromatic one Rest is.



  Organic bridge members Z are those which have at least one carbon atom in the main chain.



     To introduce the link, proceed as follows:
The linkage via dicarboxylic acid esters takes place by known methods. In addition to the purely organic acid chlorides, the organophosphorus alkanephosphoric acid dichlorides, such as ethane or cyclohexane phosphonic acid dichloride, can also be used. To prepare the dicarbamic acid esters, if the group X is a hydroxyl group, diisocyanates are reacted with.



   The class of organic acid chlorides also includes phosgene, with which the carbonates are obtained.

 

   If X is an amino group with at least one active hydrogen atom, the corresponding dicarboxamides are preferably obtained by reaction with dicarboxylic acid halides, and the corresponding dicarboxamides when reacting with alkanephosphoric acid dichlorides.



  corresponding phosphoric acid diamides. The corresponding ureas are obtained by reaction with diisocyanates. If the dye component is allowed to react with an equimolar amount of a bis-chlorocarbonic acid ester, the corresponding biscarbamic acid ester is obtained.



   If Z is the radical a: dicarboxylic acid, the following free acids, their halides and anhydrides (if the acid is capable of forming anhydrides) or their esters with volatile alcohols, come into consideration as the bifunctional reaction components for group X:

  : Oxalic acid, succinic acid, malonic acid, pimelic acid, adipic acid, methyladipic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, allyl succinic acid, dodecyl succinic acid, diglycolic acid, methylene-bis-thioglycolic acid, trajectoic acid, tetrahydrophthalic acid, tetrahydrophthalic acid, tetrahydrophthalic acid, tetrahydrophthalic acid, tetrahydrophthalic acid, 2,3-dibromosuccinic acid, tetrahydrophthalic acid, tetrahydrophthalic acid, tetrahydrophthalic acid, tetrahydrophethomethrophthalic acid, tetrahydrophthalic acid, sebacic acid, sebacic acid, azelaic acid. Hexachlorendomethylenetetrahydrophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, 2,5-thiophenedicarboxylic acid, furandicarboxylic acid, the dicarboxylic acids of the formulas
EMI4.1

The halides of aliphatic and, above all, aromatic disulfonic acids are suitable for linking with the acyl radical of a disulfonic acid.



   As diisocyanate components Z ', which are obtained by reaction with 2 mol of the dye component of the formula
EMI4.2
 where X is an amino, mercapto or hydroxyl group that form the colorless link Z, aliphati cal, cycloaliphatic, araliphatic, aromatic or heterocyclic diisocyanates are suitable.

  For example:
Hexamethylene diisocyanate,
N, N'-bis (4-methyl-3-isocyanato-phenyl) urea,
Cyclohexane-1,4-diisocyanate,
1,2,3,4,5,6-hexahydro-diphenylmethane-4,4'-diisocyanate and aromatic diisocyanates such as toluene-2,4- or -2,6-diisocyanate or a mixture thereof,
Phenylene 1,4'-diisocyanate, diphenyl4,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, diphenyl-dimethylmethane-4,4'-diisocyanate, stilbene-4,4'-diisocyanate, benzophenone-4,4'-diisocyanate, diphenyl ether - Or diphenyl sulfide diisocyanate, and their substitution products, eg by alkyl, alkoxyl, halogen or nitro groups substituted derivatives, such as. B. 3,3'-dimethyl or 3,3'kdimethoxy or 3,3 'dichloro-diphenyl methane-4,4'-diisocyanate.

  Diisocyanates of the naphthalene series, such as naphthylene-1,5 diisocyanate, or heterocyclic IDiisocyanates, e.g. 13th of
Benzofurans or urea and uretdione groups u, - pointing diisocyanates, such as 1,3-bis- (4'-methyl-3'-isocyanato-phenyl-furetdione, are mentioned as examples.



   Symmetrical diisocyanates such as diphenyl-4,4'- or diphenylmethane-4,4'-diisocyanate are preferably used.



     The .Diisocyanates can optionally also be prepared in situ, e.g. by reacting bischloromethylbenzenes and sodium or lead cyanate in active solvents.



   To produce carbonates, if X is a hydroxyl group, one can either react directly with phosgene, optionally in the presence of quaternary ammonium bases or salts, to form the carbonate, or then first produce the chloroformic acid ester of a styryl dye radical and either the same or one another styryl dye residue containing a free hydroxyl group to convert to the carbonate. On the other hand, 2 moles of the chloroformic acid ester, preferably in the presence of a hydrogen chloride acceptor such as pyridine, can be reacted with one mole of a diol, a diamine or a dithiol to give the diurethane, bis (thiourethane) or bis-urea compound.



   Suitable divalent aliphatic, cycloaliphatic, araliphatic or aromatic hydroxyl compounds, the hydrocarbon structure of which is optionally interrupted by heteroatoms, include, for example, the following hydroxyl compounds:

  : 1,2- or 1,3-dihydroxyethane, 1,2- or 1,3- or 1,4- or 2,3-dihydroxybutane, 1,2- or 1,3- or 1 , 4- or 1-, 5- or 2,3- or 2,4-dihydroxypentane, the corresponding dihydroxyhexanes, -heptanes, -octanes, -nonanes, -decanes, -undecanes, -dodecanes, -hexadecanes, octadecanes, 1, 4 dihydroxybutane, 1.5;

  ; Dihydroxy-2,2-dimethylpentane, di- (ss-hydroxy-ethyl) -thioether, di- (ss-hydroxy-ethyl) -ether (diglycol), triglycol, cyclohexanediol-1,2- or -1,3 or 1,4, 4,4'-dihydroxydicyclohexylmethane, 4,4'-dihydroxydicyclohexyldimethylmethane, 4-hydroxybenzyl alcohol, 1,4-di (ss-hydroxy-ethoxy) -benzene, 1,2- or 1,3- or 1,4-dihydroxybenzene, 1-methyl-2,4- (or 2,3- or 3,4- or 2,6 or 2,5- or 3,5-) dihydroxybenzene, 1,4-dimethyl-2, 5-dihydroxybenzene, 1-ethyl-2,4-dihydroxybenzene, 1-isopropyl-2,4-dihydroxybenzene, 4,4'-dihydroxyazobenzene, 2,4- or

   4,4'-dihydroxydiphenyl ether, 2,2'-dihydroxyethylene glycol diphenyl ether, 2,6- or 2,7-dihydroxynaphthalene, 4,4'-dihydroxydiphenylamine, 2,4'- or 4,4'-dihydroxydiphenyl, 4,4'- Dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyldimethylmethane, 1,1'-di- (4-hydroxyphenyl) -cyclohexane, 4,4'-dihydroxydiphenyl- (di) -sulfide, 4,4'-dihydroxydiphenylsulfonyl or mixtures of such diols.



   Instead of diols, dithiols, in particular aliphatic, araliphatic and aromatic dithiols, can also be used, e.g. 1,2-ethanedithiol, 1,3-propanedithiol, 1,6-hexanedithiol, 3, 4-toluene dithiol and p-xylylene dithiol.



   Suitable amines with 2 primary or secondary nitrogen atoms, which with 2 mol of the styryl dye cbioroformate t of the formula
EMI5.1
 can be implemented are 1, 2-diaminoethane, 1,2- or 1,3-diaminopropane,
1,2- or 1,3- or 1,4- or 2,3-diaminobutane
1,2- or 1,3- or 1,4- or 1,5- or 2,3 or 2,4-diaminopentane, the corresponding diaminohexanes, -heptanes, -octanes, -nonanes, jdecanes, -undecanes, - dodecane, hexadecane, octadecane, 1,4oiaminobutene,
1,5-diamino-2,2-dimethylpentane, di (ss-aminoethyl) thioether, di (y-aminopropyl) ether, butylene glycol dipropyl ether,

   diamine,
N, N'-dimethyldiaminoethane-1,2,
N, N'-diethyldiaminoethane-1, 2-,
1 amino-3-methylaminopropane, isophoronediamine,
Piperazine,
N-2-aminoethyl-piperazine, w, w 'diamino-1,3- (or -1, 4) -dimethylbenzene, w, w'-diamino-1,4- (or -1,2) -dimethylcyclohexane, w , w ';

  ; Diamino-1, 4-diethyllbenzene, w, w'-diamino-1,4- (or -1, 5) -dimethylnaphthalene, 1,2- or 1,3- or 1,4-diaminocyclohexane, 1 -methyl- 2,4-diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, 4,4'-diaminodicyclohexyldimethylmethane, 4,4'-diamino-2,2'-dimethyldicyclohexylmethane, 4-aminobenzylamine, 3- (3'- or 4'-aminophenyl) -1-aminopropane, tetrahydronaphthylenediamine-1,5- or 1,4, hexahydrobenzidine-4,4'-diamine, hexahydrodiphenylmethane-4,4'-diamine, 1,2-, 1,3-, 1,4-diaminobenzene, 1-methyl-2,4- (or 2,3- or 3,4- or 2,6 or 2,5- or 3,5) -diaminobenzene, 1,4-dimethyl-2,5-diaminobenzene, 1- Isopropyl-2,4-diaminobenzene, diisopropyl-diaminobenzene, 1-chloro-2,4-diaminobenzene, 2,4- (or

   -4,4 ') - diaminodiphenyl ether, ethylene glycol diphenyl ether-2,2'-diamine, diethylene glycol diphenyl ether-2,2'-diamine, N-methylphenylenediamine-1,4, 2,6- or 2,7-naphthylenediamine, 4,4' -Diaminodiphenyl, 3, 3'-dimethyl-4,4'-diaminodiphenyl, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyldimethylmethane, 3,3'-diaminabenzophenone, 2,4-diaminodiphenylethane-1,2,4, 4'-diamino-2,2 ', 5,5'-tetramethyltriphenylmethane, fluoroendiamine-2,7,2,6-diaminoanthraquinone, 9-ethylcarbazole-3,6-diamine, chrysene-2,8-diamine, benzidine sulfone-4 , 4'-diamine, diphenyl disulfide-4,4'-diamine, diphenylsulfone-4,4'-diamine, diphenylmethanesulfone-4,4'-diamine, 4,4'-dimethoxy-3,3'-diaminobenzenethioethylene glycol and 3,3 '-Dimethoxy-4,4'-diaminodibenzyl sulfone.

 

   In addition to dialcohols, dithiols and diamines, it is also possible to use difunctional compounds which have two different functions mentioned.



   The introduction of ether bridges or the radical -O-R5-O- takes place z. B. by reacting aqueous or alcoholic solutions of alkali phenolates with dihalides. If dichlorides are used as the starting point, dihalides with active chlorine atoms can also be used. Suitable dihalides are e.g. B. 1,4-dichlorobutene. Di-, t-chloroethyl ether, dichloroethyl formal und the isomers of bisXchloromethyl) benzene.



   If you put the dyes of the formulas
EMI6.1
 wherein X1 and X2 jc are reactive hydroxyl, thiol, carboxyl or, in particular, amino groups. with a diepoxyd. the terminal groups of the bridge member Z are ethyl, thioether, ester or imido bridges. at the same time in the ss-position to the two terminal carbon atoms a hydroxyl group is given, which is formed by the opening of the epoxy rings.



   A particularly preferred way of preparing the group -R3-Z-R4- consists in the mutual linkage of the at least one active styryl dye of the formulas having at least one active hydrogen atom on the coupling-directing nitrogen atom
EMI6.2
 p-Amino-phenylene radical of the formulas H-A1-NH-R1 and H-A @ -NH-R2 with a diepoxy compound, as it is e.g.

  B. be used commercially in epoxy resin chemistry. If a DiglyciZdyl connection is used. a compound is obtained in which the symbols of the group -R3-Z-R4- have the following meaning: R: i and R4 are propylene groups. which have a hydroxyl group in the ss-position to the nitrogen atom in para-position and Z is the remainder of a diglycidyl compound freed from the glycidyl groups.



   The invention accordingly preferably relates to bisstyl-yl dyes of the formula (I). which are characterized in that the group -R3-Z-R4 has been obtained by addition of a diepoxide to two coupling components or azo dye radicals having at least one active hydrogen atom on the coupling-directing nitrogen atom.



   The hydroxyl groups formed by the opening of the 1,2-epoxy rings can be substituted subsequently. in particular are acylated; together with the ethylene bond of the formula shown above leading to the nitrogen atom in the para position, they can have the same substituents. like the alkyl groups R1 and R ,. c <ie are derived from an N-ii-hydroxyethyl group. however, especially the residues of aliphatic carboxylic acids. such as acetic acid, propionic acid, etc. the residues of aromatic carboxylic acids such as benzoic acid. and alkyl or arylcarbamyl radicals, such as ethylcarbamyl or phenylcarbamyl radicals.



   From the well-known class of epoxy resins, the following are mentioned in heisriel:
Bifunctional compounds with two terminal epoxy groups. corresponding representatives of the class of epoxy resin z. B. butadiene diepoxyd, the diglycidyl ether of dihydric alcohols, such as glycol diglycidyl ether, the diglycidyl ether of dihydric phenols, such as 4,4 'dihydroxydiphenylmethane, -dimethylmethane or -sul fon, the diglycidyl ether from polyhydric thiols, such as
Bis (mercaptomethyl) benzenes, the N, N'-diglycidyl compounds, e.g.

  B. of N, N'-dimethyl-4,4 '> diamlinodiphenylmethane, ethylene urea or oxamide, and the
Diglycidyl esters of aliphatic, cycloaliphatic or aromatic dicarboxylic acids, such as phthalic acid,
Hexahydrophthalic acid, tetrahydrophthalic acid or
Succinic acid.



     The dye preparations according to the invention are extremely suitable for dyeing and printing hydrophobic synthetic and semi-synthetic fibers, for example made from cellulose acetate, but especially aromatic polyesters. Even the hydrophobic ones
Fibers made from copolymers of propylene oxide and unsaturated epoxides and fibers based on polyvinyl chloride can be colored with the new dyes.



   It is obtained on hydrophobic fibers, in particular on polyester fibers, by the usual dyeing processes, e.g. B. from a dye liquor, which is a fine dispersion of the
Dyestuff and suitably a dispersant ent holds at temperatures up to close to 100 C, if necessary with the addition of a swelling agent, or at
Temperatures above 100 ° C. with the use of excess pressure, pure, strong, greenish yellow colorations, which are characterized by excellent light and sublimation fastness. The dye preparations also have the advantage of only slightly staining wool and other fibers in the dyebath. They are therefore well suited for dyeing polyester wool or z. B.



      Polyester-triacetate blend fabrics.



   The dye preparations are also suitable for dyeing by the so-called thermosol process, according to which the goods to be dyed with an aqueous dispersion of the
Dye, which suitably contains 1 to 50% urea and a thickener, in particular sodium alginate, is preferably impregnated at temperatures of at most 60 ° C. and squeezed off as usual. It is expedient to squeeze in such a way that the impregnated product retains 50 to 100,010 of its initial weight of dyeing liquid. To fix the dye, the fabric impregnated in this way is wilted after prior drying, e.g. B. in a warm air stream, heated to temperatures of over 100 C, for example between 180 and 210 C.



   The above-mentioned thermosol process for dyeing blended fabrics made of polyester fibers and cellulose fibers, in particular cotton, is of particular interest. In this case, in addition to the dye according to the invention, the padding liquid also contains dyes suitable for dyeing cotton, for example vat dyes. If the latter is used, the padded fabric must be treated after the heat treatment with an aqueous alkaline solution of a reducing agent customary in vat dyeing.



   In the following examples, unless otherwise stated, parts are parts by weight, percentages are percentages by weight, and temperatures are given in degrees Celsius.



   example 1
48.8 parts of N-ethyl-N- (ß-oxyethyl) -m-toluidine in 30 parts by volume of dry benzene are stirred with 11 parts of sodium metal for 15 hours while refluxing. Excess sodium is removed and then 53.8 parts of N-ethyl-N (p-chloroethyl) -moluidine in 50 parts by volume of dry benzene and 4 parts of sodium iodide are added. The mixture is refluxed for a long time with stirring, then diluted with dry benzene. The sodium chloride and sodium iodide formed are filtered off, the filtrate is concentrated and distilled. It boils between 185 to 195 at 0.1 torr. The amine thus obtained corresponds to the formula
EMI7.1
 Analysis: Calculated: C 77.6% H 9.5% N 8.2% Found: C 77.9% H 9.7% N 8.3%.



  The same amine was also obtained by reacting 2,2'z-dichloro diethyl ether with N ethyl-! M-toluidine.



   10.2 parts of this amine are introduced into a mixture of 11.1 parts by volume of dimethylformamide and 9.4 parts by volume of phosphorus oxychloride at 15, with stirring, and the mixture is then stirred at 60 for 6 hours. The reaction product is poured onto ice, then chloroform is added and the mixture is neutralized with the addition of ice at room temperature with concentrated sodium hydroxide solution. The chloroform phase is washed once with water, then dried with NajSOo. After the chloroform has been distilled off, the crude dialdehyde of the formula remains
EMI7.2
 as dark oil.

 

   1.6 parts of malodinitrile and 0.2 parts by volume of piperidine are added to 4 parts of this dialdehyde in 25 parts by volume of absolute ethanol, and the mixture is refluxed for 5 hours. On cooling to room temperature, a dark oil is obtained, which becomes crystalline on standing.



  After recrystallization, the fine, orange-yellow crystals of the dye of the formula are obtained
EMI7.3
 Analysis: N calculated 17.1%, N found 17.1%.



   It dyes polyester fibers in pure greenish yellow tones with excellent light and sublimation fastness.



  Staining instructions
1 part of the dye obtainable according to Example 1 is wet-ground with 2 parts of a 50% strength aqueous solution of the sodium salt of dinaphthylmethanedisulfonic acid and dried.



   This dye preparation is mixed with 40 parts of a 0% strength aqueous solution of the sodium salt of N 3enzyl-, c-heptadecyl-benzimidazole disulfonic acid and 4 parts of a 4% strength acetic acid solution are added. By diluting with water, it is prepared in a dye bath of 400 () parts.



   100 parts of a purified polyester fiber material are added to this bath at 50 °, the temperature is increased to 120 to 1300 in half an hour and dyeing is carried out in a closed vessel at this temperature in one hour. It is then rinsed well. A greenish yellow dyeing of excellent lightfastness and sublimation fastness is obtained.



   Example 2
If the starting material used is the dialdehyde of the formula
EMI8.1
 If the procedure is as indicated in Example 1, zone dye is obtained. the polyester fibers also dyes in greenish yellow shades of very good lightfastness and sublimation fastness.



   Example 3
4 parts of the dialdehyde described in Example 1 are refluxed for 4 hours in 25 parts by volume of ethanol with 2.4 parts of cyanoacetate and 0.2 parts of piperidine. On cooling, 3.5 parts of an orange powder of the molding material of the formula are obtained
EMI8.2
   With this, silane creates green-tinged @clbe dyeings with good fastness properties on polyester materials.



   The following table I contains a number of other valuable dyes of the general formula
EMI8.3
 Velche can be obtained in a manner analogous to that in Example 1. TABLE I.
EMI9.1


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<tb> <SEP> ri <SEP> 2H <SEP> i <SEP> iD <SEP> T <SEP>? n <SEP> '<SEP> I
<tb> <SEP> 4 <SEP> chig-geib
<tb> At <SEP> 2H5 <SEP> 0 <SEP> 2H5 <SEP> 0 <SEP> 2H4- <SEP> 3 <SEP> 2 <SEP> NH2 <SEP> 0
<tb> <SEP> t <SEP> T
<tb> <SEP> 1 <SEP> II
<tb> <SEP> C <SEP> 2H40C0H'3 <SEP> 2H40CCH3 <SEP> -c <SEP> 2H4- <SEP> T <SEP> - <SEP> =;

  <SEP> ml <SEP> T <SEP> T <SEP> T
<tb> <SEP> I <SEP> I <SEP> L
<tb> <SEP> tH <SEP> T <SEP> 2H5 <SEP> -a2H4- <SEP> T <SEP> T <SEP> T <SEP> t <SEP> W <SEP> T
<tb> <SEP> chig-geib
<tb> T <SEP> -a2H5 <SEP> m <SEP> 2H5 <SEP> -C2H4 <SEP> H <SEP> m <SEP>> <SEP> me <SEP> me <SEP> m
<tb> <SEP> T <SEP> Ql <SEP> T <SEP> T <SEP> T <SEP> Ql.

  <SEP> T
<tb> <SEP> Mn <SEP> Sct <SEP> me <SEP> mç <SEP> Cde <SEP> t <SEP> te <SEP> Z
<tb> <SEP> V <SEP> tM <SEP> N <SEP> N <SEP> N <SEP> tM <SEP> N
<tb> <SEP> &verbar; <SEP> '? <SEP> tlD <SEP> T <SEP> T <SEP> T <SEP> tlD
<tb> <SEP> n <SEP> o = v <SEP> ffi <SEP>
<tb> <SEP> ç <SEP> \ / <SEP> m <SEP> x <SEP> o <SEP> m <SEP> m
<tb> <SEP> N <SEP> m <SEP> I <SEP> N <SEP> CM <SEP> + <SEP> N <SEP> N
<tb> <SEP> $ <SEP> N <SEP> OJ <SEP> Q <SEP> Q <SEP> 2 <SEP> tD <SEP> V
<tb> <SEP> T <SEP> tD <SEP> l <SEP> l <SEP> tD <SEP> l <SEP> l
<tb> <SEP> mn
<tb> <SEP> 2 <SEP> tD
<tb> <SEP>,

   <SEP> mn <SEP> y <SEP> m <SEP> mn <SEP> O <SEP> m
<tb> <SEP> M <SEP> 7 <SEP> mtM <SEP> T <SEP> TN <SEP> sn <SEP> T
<tb> <SEP> I <SEP> Ho
<tb> <SEP> <SEP> P4 <SEP> <<SEP> N <SEP> t <SEP> + <SEP> WW <SEP> w <SEP> F
<tb> <SEP> Sa <SEP> tn
<tb>
Example 4
30 g of N-ethylaniline, 17.1 g of ss, γ, ss ', γ' - diepoxy tripropylamine (manufactured according to French patent no.



   1137 175) and 30 g of chlorobenzene are heated to about 140 ° C. for 24 hours, then the solvent is removed in vacuo and the residue is distilled in a high vacuum. One obtained p, KDihydroxy-y, γ'-di- (N-phe.



   nyl-N-ethyl-) amino-tripropylamine.



  Calculated: C 72.60%, H 9.51%, N 10.16% found: C 72.3%, H 9.7 e / o, N 10.2%.



   41.3 g of ss, ss'-dihydroxy- γ, γ'-di- (N-phenyl-N-ethyl-) amino-tripropylamine and 25 g of acetic anhydride are heated to 130 ° C. for three hours, then the glacial acetic acid formed in vacuo removed and the residue is distilled in a high vacuum. SS, SS'-diacetoxy- γ, γ'-di- (N-phenyl-N-ethyl-) amino-tripropylamine were obtained: calculated:

  C 69.99% H 8.71 / o N 8.44% found: C 69.6 ele H 8.8 Oio N 8.6%
If this amine is formylated according to Vilsmeier and the dialdehyde is condensed with malonitrile analogously to the procedure of Example 1, the bisstyryl dye of the formula is obtained
EMI10.1
 It colors acetate, polyester and polyacrylonitrile materials in greenish-yellow tones. The dialdehyde can also be obtained analogously to the examples in German Auslegeschrift 1 206 879.



  Staining instructions
1 part of the dye obtained above is dissolved in 5000 parts of water with the addition of 2 parts of 40% acetic acid. At 60, 100 parts of dried polyacrylonitrile staple fiber yarn are entered into this dyebath, the temperature is increased to 100 within half an hour and dyeing is carried out for one hour at boiling temperature. Then the dye is rinsed well and dried. An orange dyeing with very good fastness to light, sublimation and washing is obtained.



   Example 5
30 g of N-ethylaniline, 20.2 g of butanediol diglycidyl ether and 50 g of chlorobenzene are heated to approx.



     140 ° C., then the solvent was removed in vacuo and the residue was distilled in a high vacuum. Butanediol di [d-hydroxy-y- (N-phenyl-N-ethyl) amino] propyl ether is obtained.



  Calculated: C 70.23% H 9.07% N 6.30% found: C 70.0 r / o H 8.9 / o N 6.3 / o.



   44.4 g of butanediol di [ss-hydroxy- γ- (N-phenyl-N-ethyl) amino] propyl ether and 25 g of acetic acid hydride are heated to 130 ° C. for three hours, then the glacial acetic acid formed is removed in vacuo. Butanediol di- [β-acetoxy- γ-N-phenyl-N-ethyl-) amino-] propyl ether is obtained. The residue can be used directly or it can be distilled in a high vacuum.

 

   If this amine is formylated and the dialdehyde is condensed with malononitrile analogously to the procedure of Example 1, the bis-styryl dye of the formula is obtained
EMI10.2

The following Table II contains a number of other valuable dyes which dye polyester fibers in greenish yellow shades and which are obtained analogously to the instructions in Examples 4 and 5. The substituents and indices have the same meaning as above.



     TABLE II
EMI11.1


<tb> <SEP> a> <SEP> = C <SEP> .rYp <SEP> f <SEP> j
<tb> <SEP> P <SEP> IP <SEP> IP <SEP> I
<tb> <SEP> k <SEP>: <SEP> d <SEP> ro
<tb> <SEP> h <SEP> U <SEP> d <SEP> ct <SEP> a) <SEP> d <SEP> O <SEP> rI <SEP> d <SEP> c) <SEP> .o
<tb> <SEP> F, <SEP> k <SEP> -r <SEP> O <SEP> k <SEP> k <SEP> -P <SEP> 4 <SEP> t;

  <SEP> t
<tb> <SEP> 90y¯ <SEP> tO <SEP> oi <SEP> ¯¯ <SEP> tD <SEP> ro
<tb> <SEP> X <SEP> Q <SEP> O
<tb> <SEP> I
<tb> <SEP> M
<tb> <SEP> N <SEP> CJ <SEP> CJ
<tb> <SEP> X <SEP> X <SEP> M
<tb> <SEP> R1 <SEP> R2 <SEP> R3 <SEP> ¯¯¯
<tb> <SEP> cu <SEP> Y <SEP> Y <SEP> O
<tb> <SEP> H <SEP> Z
<tb> 1 <SEP> a2H4oaaH3 <SEP> a2H4oaaH3 <SEP> aH2- <'H-aH <SEP> O <SEP> T <SEP> -aH-aH <SEP> T <SEP> T
<tb> <SEP> 2 <SEP> 2 <SEP> 2- <SEP> 1 <SEP> tichi
<tb> <SEP> do <SEP> QaQaH3 <SEP> T <SEP> N <SEP> yellow
<tb> <SEP> M
<tb> <SEP> "<SEP> M <SEP> X <SEP> M
<tb> <SEP> v <SEP> 9 <SEP> yellow
<tb> <SEP> M
<tb> <SEP> rl <SEP> X
<tb> <SEP> P
<tb> <SEP> n <SEP> n <SEP> 3 <SEP> 3 <SEP> 2 <SEP> 4
<tb> <SEP> TI <SEP> H <SEP> oaoa <SEP> m <SEP> s1c1
<tb> <SEP> 25 <SEP> 25 <SEP> yellow
<tb> <SEP> u <SEP> P
<tb> <SEP> I
<tb> <SEP> m
<tb> 4 <SEP> -a2H4aN <SEP> -a2H4N <SEP> HFaHaH2 <SEP> H2aHH2- <SEP>

   H3 <SEP> I <SEP> N <SEP> cz04
<tb> <SEP> U <SEP> I,
<tb> <SEP> V <SEP> C) <SEP> V <SEP> n <SEP>> <SEP> IH <SEP> yellow
<tb> <SEP> X <SEP> lo <SEP> Y "
<tb> <SEP> uXu <SEP> o
<tb> <SEP> U- <SEP> O <SEP> U <SEP> -O <SEP> YNO <SEP> m <SEP> u
<tb> <SEP> O <SEP> C) <SEP> v <SEP> 9
<tb> <SEP> n
<tb> <SEP> m
<tb> <SEP> O <SEP> V <SEP> D <SEP> n <SEP> O <SEP> O <SEP> .U
<tb> <SEP> eq <SEP> A <SEP> o <SEP> A <SEP> o
<tb> <SEP> X <SEP> 9o <SEP> Oo <SEP> Oo <SEP> Oo
<tb> <SEP> 1N <SEP> lod <SEP> IOJ
<tb> <SEP> m <SEP> m <SEP> m <SEP> m
<tb> <SEP> C) <SEP> C7 <SEP> C) <SEP> D
<tb> <SEP> n
<tb> <SEP> o = <SEP> o <SEP> mn <SEP> L
<tb> <SEP> M <SEP> m <SEP> S <SEP> C) <SEP> (M
<tb> <SEP> CxJ <SEP> N <SEP> &verbar; <SEP> t;)
<tb> <SEP> O <SEP> v
<tb> <SEP> l <SEP> l
<tb> <SEP> to
<tb> <SEP> P:

  <SEP> n
<tb> <SEP> U <SEP> t <SEP> ti
<tb> <SEP> 0 = D <SEP> V <SEP> O
<tb> <SEP> O <SEP> O <SEP> U) <SEP> +
<tb> <SEP> r1 <SEP> e <SEP> e <SEP> t <SEP> m
<tb> <SEP> Pa <SEP> m <SEP> m <SEP> CM <SEP> W
<tb> <SEP> (M <SEP> C \ l <SEP> D <SEP> O
<tb> <SEP> 7 <SEP> 7
<tb> <SEP> H
<tb>
EMI12.1


<tb> <SEP> u- <SEP> cl <SEP> 1 <SEP> ¯d
<tb> <SEP> x
<tb> 5 <SEP> c2H5- <SEP> 2H5- <SEP> cH2aHcH- <SEP> X <SEP> H3 <SEP> I
<tb> <SEP> 2 <SEP> H2aHaH2 <SEP> thoxy <SEP> äthoxy <SEP> O
<tb> <SEP> N <SEP> eD <SEP> O <SEP> SZ <SEP> CH
<tb>>., <SEP> H <SEP> HCH <SEP> HCHCH- <SEP> 51 <SEP> H <SEP> T
<tb> <SEP> Ud
<tb> <SEP> 2 <SEP> 2 <SEP> 21.2
<tb> <SEP> i <SEP> P <SEP> s <SEP> O <SEP> 5ei
<tb> <SEP> s <SEP> OCOCH3 <SEP> CH3
<tb> <SEP> Q <SEP>:

  : <SEP> e.g.
<tb> <SEP> II <SEP> II
<tb> 7 <SEP> 2H40CNHC2H5 <SEP> 2H40CNH02H5 <SEP> H2CIHCH2 <SEP> -pri ----
<tb> <SEP> X
<tb> <SEP> cu <SEP> X <SEP> Tn <SEP> T <SEP> T <SEP>
<tb> <SEP> rI <SEP> c
<tb> <SEP> ¯¯¯p¯ <SEP> 21 <SEP> 2
<tb> <SEP> 21 <SEP> 2
<tb> <SEP> 0CoOH3 <SEP> OCOOH3
<tb> <SEP> <SEP> IN <SEP> = <SEP> <M <SEP> m <SEP> N <SEP> i
<tb> <SEP> N <SEP> N <SEP> N <SEP> N
<tb> <SEP>: n <SEP> m <SEP> a:

  <SEP> m
<tb> <SEP> T <SEP> T <SEP> T <SEP> T
<tb> <SEP> uo
<tb> <SEP> mN
<tb> <SEP> n <SEP> n <SEP> I <SEP> ca <SEP> I <SEP> n
<tb> <SEP> P <SEP> U <SEP> m <SEP> N <SEP>>:
<tb> <SEP> W: n <SEP> m <SEP> o <SEP> m <SEP> o <SEP> E <SEP> o <SEP> R <SEP> o
<tb> <SEP> vo <SEP> ezo <SEP> c) o <SEP> C) o
<tb> <SEP> N <SEP> N <SEP> N <SEP> N
<tb> <SEP> m <SEP> m <SEP>:

  : n
<tb> <SEP> N
<tb> <SEP> 1 <SEP>> <SEP> mn <SEP> i <SEP>>
<tb> <SEP>> <SEP> O <SEP> = <SEP> ev <SEP> d
<tb> <SEP> C \ l <SEP> (M <SEP> I <SEP> O <SEP> x
<tb> <SEP> X <SEP> S '<SEP> N <SEP> T
<tb> <SEP> N
<tb> <SEP> I <SEP> R
<tb> <SEP> mn <SEP> n <SEP> o <SEP> = r <SEP> ti
<tb> <SEP> 1 <SEP> N <SEP> m <SEP> o <SEP> *
<tb> <SEP> O <SEP> vD <SEP> F <SEP>
<tb>
Example 6
73 parts of adipic acid are converted into the adipic acid chloride with 168 parts of SQCl2, excess SOCl is removed in vacuo and the acid chloride is dissolved in 250 parts by volume of benzene. A solution of 176 parts of N-ethyl-N-ss-oxyaethyl-m-toluidine is added dropwise to this solution over the course of one hour and the mixture is then refluxed for 2 hours with stirring.

  After cooling, the precipitated chlorohydrate is filtered off with suction and washed with benzene and dried at 500 ° in a vacuum drying cabinet. The product is suspended in water and the suspension is adjusted to pH 8 with sodium hydroxide solution; the suspension is then filtered off with suction and the residue is washed well with water.

  After drying, 215 parts (92%) of the product of the formula remain
EMI13.1
 150 parts of this product are dissolved in 190 parts by volume of dimethylformamide and. 109 parts by volume of phosphorus oxychloride are added dropwise to this solution at 15 to 20 ° C. with stirring, stirred at 95 for 1 hour and discharged hot with stirring onto 2500 parts of ice-water, an emulsion first formed from which a greasy product precipitates over time which gradually becomes completely hard. This product is suspended in water, filtered off with suction and washed neutral with water.

  After drying in a vacuum oven at 60 to 70, 146.2 parts (88%) of the dialdehyde of the formula are obtained
EMI13.2
 Analysis: Calculated: C 58.6% H 7.7 O / o N 5.3% Found: C 58.0% H 7.7 / o N 5.6 ovo 28 parts of this dialdehyde are obtained with stirring at a bath temperature of 95 in 300 parts by volume of isopropanol with 7.4 parts of malonic acid dinitrile and 15 drops of piperidine heated for 3 hours, then slowly cooled to room temperature with stirring, after 4 hours, heated again for 1 hour with stirring in a bath at 95 C, the The resulting orange precipitate is filtered off with suction and washed with a little isopropanol.

  After drying at 60 to 70, there remain 31.4 parts (95.5 / o) of the dye of the formula
EMI13.3
 It dyes acetate and polyester materials in brilliant, greenish yellow tones with excellent light and sublimation fastness.



   Example 7
The following dialdehyde was prepared analogously to the procedure of Example 6:
EMI13.4
   This compound was condensed with a mixture of one molar equivalent each of malononitrile and cyanoacetate in methanol with catalytic amounts of piperidine, the main product being the dye of the formula
EMI14.1
 was obtained as an olive powder. It also dyes acetate and polyester materials in greenish-yellow nuances with excellent fastness properties.



   The following Table III comprises a number of other valuable bis-styryl dyes obtained by esterifying 2 mol of the N-ssxyaethyl-amines listed in column II with 1 mol of the dicarboxylic acid chlorides listed in column III, formylation according to Vilsmeier and condensation of the dialdehydes with 2 mol a compound CN-CH2-Y (where Y = Y2) analogous to the preparation instructions given in Example 6.



     TABLE III
EMI15.1

 II <SEP> III <SEP> Y (Y1 = Y2) <SEP> COLOR
<tb> 1 <SEP> N-ethyl-N-ss-hydroxy- <SEP> succinic acid- <SEP> -CN <SEP> greenish yellow
<tb> ethyl aniline <SEP> dichloride
<tb> 2 <SEP> N-butyl-N-ss-hydroxyethyl- <SEP> terephthalic acid- <SEP> -CN <SEP> greenish yellow
<tb> aniline <SEP> dichloride
<tb> 3 <SEP> N-ethyl-N-ss-hydroxy- <SEP> terephthalic acid- <SEP> -CN <SEP> greenish yellow
<tb> ethyl-3-methyl-aniline <SEP> dichloride
<tb> 4 <SEP> N-ethyl-N-ss-hydroxy- <SEP> phthalic acid- <SEP> -CN <SEP> greenish yellow
<tb> ethyl aniline <SEP> dichloride
<tb> 5 <SEP> N-ethyl-N-ss-hydroxy- <SEP> phthalic acid- <SEP> -COOC2H5 <SEP> greenish yellow
<tb> ethyl aniline <SEP> dichloride
<tb> 6 <SEP> N-Aethyl-N-ss-hydroxy- <SEP> oxalyl chloride <SEP> -CN <SEP> greenish yellow
<tb> ethyl-3-methylaniline
<tb> 7 <SEP> N-ethyl-N-ss-hydroxy- <SEP>

   Cyclohexane-1,2-digit yellow
<tb> ethyl-3-methylaniline <SEP> carboxylic acid dichloride <SEP> -CN
<tb> 8 <SEP> N-Aethyl-N-ss-hydroxy- <SEP> maleic acid- <SEP> -CONH2 <SEP> greenish-yellow
<tb> ethyl-3-methylaniline <SEP> chloride
<tb>
EMI16.1

  <SEP> II <SEP> III <SEP> Y (Y <SEP> = Y <SEP>) <SEP> COLOR
<tb> <SEP> n <SEP> n <SEP> n <SEP> n <SEP> n <SEP> n <SEP> n
<tb> <SEP> H <SEP> H <SEP> H <SEP> H <SEP> H <SEP> H <SEP> H
<tb> <SEP> o <SEP> N-Aethyl-N- (3-hydroxy- <SEP> a, <SEP> a, <SEP> a, <SEP> a, <SEP> a,

   <SEP> a) <SEP> Q
<tb> <SEP> 4u <SEP> o <SEP> to <SEP> o <SEP> o <SEP> o
<tb> <SEP> bD <SEP> bD <SEP> bD <SEP> bD <SEP> bD <SEP> chloride
<tb> <SEP> o <SEP> so <SEP> 40 <SEP> o <SEP> t \ o <SEP> 40 <SEP> o
<tb> <SEP> ri <SEP> ri <SEP> ri <SEP> ri <SEP> ri <SEP> ri
<tb> pi <SEP> To <SEP> zuw <SEP> -CN <SEP> greenish-yellow
<tb> <SEP> ethyl-3-methylaniline <SEP> ro <SEP> v,

   <SEP> rn <SEP> rss
<tb> <SEP> for <SEP> 'ft <SEP> F <SEP> k <SEP> k <SEP> k <SEP> k
<tb> <SEP> 11 <SEP> N-Aethyl-B - hydroxy- <SEP> glutaric acid- <SEP> 40 <SEP> greenish yellow
<tb> t <SEP> X
<tb> 12 <SEP> N-methyl-N - hydroxy- <SEP> iglycolic acid- <SEP> -ON <SEP> greenish yellow
<tb> II <SEP> I <SEP> V <SEP> A1 <SEP> V <SEP> C)
<tb> <SEP>, I <SEP> I <SEP> u <SEP> u <SEP> u <SEP> w <SEP> u <SEP> u
<tb> <SEP> o <SEP> I <SEP> I <SEP> I <SEP> I
<tb> Hi
<tb> <SEP> 4 <SEP> | <SEP> I <SEP> I
<tb> <SEP> o
<tb> <SEP> 14 <SEP> N-Aethyl-N - hydroxy- <SEP> thiophene-2,5-di- <SEP> rl <SEP> rl
<tb> <SEP> t) <SEP> <<SEP> I <SEP> I <SEP> rd <SEP> c <SEP> I <SEP> rd <SEP> I <SEP> zd <SEP> I
<tb> <SEP> ethyl-aniline <SEP> carboxylic acid di
<tb> <SEP> k
<tb> <SEP> m <SEP> a> <SEP> k <SEP> k <SEP>: d <SEP> k
<tb> H <SEP> m <SEP> I <SEP> I <SEP> I
<tb> H <SEP> cd <SEP> ri <SEP>: cd <SEP> d <SEP>:

  : cd <SEP> E: <SEP>: cd <SEP> d <SEP>: d
<tb> 15 <SEP> Zue <SEP>, 4 <SEP> k <SEP> 'd <SEP> o) <SEP> rd <SEP> o <SEP> vd <SEP> O <SEP> X <SEP> 'd <SEP> O <SEP> Q <SEP> rd <SEP> d <SEP> F: rl
<tb> <SEP> hydroxyethyl-aniline <SEP> carboxylic acid di <SEP> ar <SEP> -e <SEP> O <SEP> O-P <SEP> O <SEP> OP <SEP> O <SEP> OP <SEP> O
<tb> <SEP> o <SEP> c) <SEP> cQ <SEP> rI <SEP> bD <SEP> = 1 <SEP> vi <SEP> h <SEP> 1 <SEP> -rl <SEP> h <SEP> = 1 <SEP>, <SEP> h <SEP> = 1
<tb> <SEP> H <SEP> t <SEP> X, <SEP> C) <SEP> t <SEP> C) <SEP> n <SEP> C) <SEP> EQ <SEP> C) <SEP > C) <SEP> E <SEP> I <SEP> D <SEP> C> <SEP> E <SEP> f <SEP> D <SEP> C)
<tb> <SEP> I <SEP> I <SEP> I <SEP> i <SEP> I <SEP> U
<tb> <SEP> x <SEP>, 4 <SEP> x <SEP> rd <SEP> x <SEP> H <SEP> 8 <SEP> H <SEP> x <SEP> <
<tb> <SEP> o <SEP> H <SEP> o <SEP> H <SEP> o <SEP> H <SEP> o <SEP> H <SEP> o <SEP>,

   <SEP> or similar
<tb> <SEP>, 4 <SEP> r <SEP> I <SEP>, 4 <SEP>, 9 <SEP> h <SEP>, <SEP> h <SEP>, <SEP> h <SEP> U <SEP> h <SEP> m <SEP> U
<tb> <SEP> t <SEP> U <SEP> t <SEP> U <SEP> rd <SEP> U <SEP> 'd <SEP> U <SEP>' d <SEP> U <SEP> rd < SEP> T-, 8
<tb> <SEP> S <SEP> U <SEP> S <SEP> U <SEP> X <SEP> U <SEP> X <SEP> U <SEP> X <SEP> I <SEP> X <SEP> t <SEP> H
<tb> <SEP> <<SEP> r <SEP> rQ <SEP> rJg <SEP> 1 <SEP> rq
<tb> <SEP> I <SEP> S <SEP> I <SEP> X <SEP> I <SEP> S <SEP> I <SEP> h <SEP> i <SEP> S <SEP> I <SEP> rd <SEP> g
<tb> <SEP> I <SEP> w <SEP> &verbar; <SEP> J9 <SEP> 1 <SEP> +) <SEP> I <SEP> rH <SEP> i <SEP> 49 <SEP> 1 <SEP> rd <SEP> =
<tb> H <SEP> I <SEP> Fg <SEP> I <SEP> F3 <SEP> I <SEP> C) <SEP> I <SEP> e.

  <SEP> I <SEP> approx
<tb> H <SEP> rH <SEP> I <SEP> rH <SEP> i <SEP> r¯l <SEP> I <SEP> rwl <SEP> I <SEP> rX <SEP> I <SEP> ' <SEP> approx
<tb> <SEP> +3 <SEP> rH <SEP> v <SEP> rQ <SEP> w <SEP> rQ <SEP> w <SEP> rl <SEP> 4) <SEP> <<SEP> w < SEP> rQ
<tb> <SEP> O <SEP> SJ <SEP>;) <SEP> rX <SEP> <<SEP>) <SEP> X <SEP> I <SEP> X
<tb> <SEP> I <SEP> w <SEP> 1 <SEP> 4 <SEP> 1 <SEP> +) <SEP> I <SEP> &num; <SEP> I <SEP> + z <SEP> I <SEP> w <SEP> I <SEP> h
<tb> <SEP> ti <SEP>:

  <<SEP> d
<tb> <SEP> I
<tb> <SEP> 5> <SEP> 0 <SEP> rH
<tb> <SEP> H <SEP> r <SEP> 1 <SEP> rH <SEP> rQ <SEP> r
<tb>
EMI17.1


<tb> <SEP> P <SEP> P <SEP> P <SEP> P <SEP> P <SEP> P
<tb> <SEP> rl <SEP> rl <SEP> rl <SEP> rl <SEP> r (
<tb> <SEP> Q> <SEP> a> <SEP> a, <SEP> a, <SEP> a,
<tb> <SEP> to <SEP> o <SEP> tlo <SEP> o <SEP> ts <SEP> ho
<tb> <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I
<tb> <SEP> w <SEP> o <SEP> o <SEP> tlo <SEP> ho <SEP> o
<tb> M <SEP> -Aethyl-N-hydroxy- <SEP> thiop, hen-2, -di- <SEP> ON <SEP> d <SEP> d <SEP> 6 <SEP> C; t
<tb> <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0
<tb> <SEP> ethyl-3-diethyl-aniline <SEP> carboxylic acid
<tb> <SEP> dichloride
<tb> <SEP> d
<tb> 17 <SEP> k <SEP> cyanoethyl-Nss <SEP> -hy- <SEP> thiophene-2, <SEP> 5-di- <SEP> -ON <SEP> k
<tb> <SEP> bD <SEP> in <SEP> bhD <SEP> iz4D <SEP> b4D <SEP> bhD
<tb> <SEP>.
<tb>



  18 <SEP> -Aethyl-N <SEP> -hydroxy- <SEP> thiophene-2, <SEP> 5-di- <SEP> -ON <SEP> greenish yellow
<tb> <SEP> cu <SEP> uz
<tb> <SEP> S <SEP> t
<tb> <SEP> II <SEP> i <SEP> i <SEP> cil
<tb> <SEP> rl <SEP> U <SEP> U <SEP> U <SEP> U <SEP> X
<tb> <SEP> I <SEP> I <SEP> I <SEP> O <SEP> cu <SEP> k
<tb> <SEP> y <SEP> 0 <SEP> 0 <SEP> 0
<tb> <SEP> 3- (<SEP> U <SEP> v2 <SEP> u
<tb> 19 <SEP> -Aethyl-N - hydroxy- <SEP> thiophene-2,5-di- <SEP> -aooc <SEP> H <SEP> greenish yellow
<tb> <SEP> I <SEP> carboxylic acid- <SEP> 2 <SEP> 5
<tb> <SEP> di <SEP> chloride
<tb> 20 <SEP> -Aethyl-N - hydroxy- <SEP> thiophene-2,5-di- <SEP> ri <SEP> ri <SEP> ri <SEP> ri <SEP> ri
<tb> <SEP> t <SEP> t <SEP> r <SEP> gd <SEP> rd <SEP> r <SEP> Id <SEP> rt
<tb> <SEP> N <SEP>, 4 <SEP> or <SEP> z <SEP> N <SEP> z <SEP> ^ <SEP> oJ <SEP>, 4 <SEP> oJ <SEP> z < SEP> cd <SEP> e.g.
<tb> <SEP> H <SEP> I <SEP> j <SEP> a <SEP> I <SEP> -i

   <SEP> a <SEP> I <SEP> a <SEP> I <SEP> d <SEP> I <SEP> d
<tb> <SEP> H <SEP> d <SEP>: d <SEP> ri <SEP> d <SEP>: <SEP> ri <SEP> d <SEP>: d <SEP> ri <SEP> d < SEP>: cd <SEP> rl <SEP> d <SEP>: id <SEP> rl
<tb> H <SEP> to <SEP> a) <SEP> Thiophene-2,5-di- <SEP> a) <SEP> co <SEP> z <SEP> a) <SEP> tn <SEP> z -CONH
<tb> <SEP> = <SEP> ¯ <SEP> O <SEP> = <SEP> ¯ <SEP> O <SEP> t <SEP> ¯ <SEP> O <SEP> <<SEP> ¯ <SEP> O <SEP> <<SEP> rq <SEP> o <SEP> <<SEP> <<SEP> O
<tb> <SEP> 7i <SEP> O <SEP> ri <SEP> A <SEP> O <SEP> rl <SEP> A <SEP> O <SEP> rt <SEP> PI <SEP> O <SEP> rl <SEP> 4 <SEP> 2 <SEP> O <SEP> rhl
<tb> <SEP> o <SEP> P <SEP> d <SEP> o <SEP> P <SEP> 1 <SEP> O <SEP> P <SEP> O <SEP> P <SEP> C; I < SEP> O <SEP> e <SEP> r;

  ; l <SEP> o <SEP> P <SEP> 1
<tb> <SEP> rl <SEP> k <SEP> o <SEP> rl <SEP> k <SEP> O <SEP> rf <SEP> k <SEP> O <SEP> k <SEP> O <SEP> rl <SEP> k <SEP> O <SEP> r (<SEP> k <SEP> U
<tb> <SEP> di <SEP> tt <SEP> vri <SEP> <<SEP> U <SEP> ri <SEP> <<SEP> td <SEP> d <SEP> t <SEP> d <SEP> ri <SEP>! <SEP> fl <SEP> d <SEP> chloride
<tb> <SEP> Eq <SEP> d <SEP> EQ <SEP> d <SEP> Eq <SEP> d <SEP> EQ <SEP> D <SEP> rd <SEP> EQ <SEP> C) <SEP > rd <SEP> E- <SEP> d
<tb> <SEP> I <SEP> H
<tb> <SEP> X-ri <SEP> h <SEP> h <SEP> X <SEP>>> <SEP> X
<tb> <SEP> X <SEP> rw <SEP> X <SEP> X <SEP> X
<tb> <SEP> O <SEP> ri <SEP> I <SEP> O <SEP> O <SEP> O <SEP> O
<tb> <SEP> 4 <SEP> - <SEP> rD <SEP> - <SEP> h <SEP> 4 <SEP> h <SEP> 4
<tb> <SEP> rd <SEP> (t <SEP> I <SEP> rl <SEP> rd <SEP> rd <SEP> od <SEP> rd
<tb> <SEP> S <SEP> I <SEP> S !; <SEP> rd <SEP> h <SEP> S <SEP> b <SEP> X
<tb> <SEP>, s:

  <SEP> r &verbar; <SEP> I <SEP> ri <SEP> t <SEP> t <SEP> = 1 <SEP> <
<tb> <SEP> I <SEP> &commat; <SEP> <<SEP> I <SEP> 5 <SEP> ri <SEP> I <SEP> r <SEP> l <SEP> I <SEP> r <SEP> I <SEP> ri
<tb> <SEP> H <SEP> Z; <SEP> a) <SEP> +5 <SEP> rH <SEP> t; <SEP> rd <SEP> ti <SEP> rd <SEP> t <SEP> ri <SEP> t <SEP> r <SEP> l
<tb> <SEP> H <SEP> 1 <SEP> E <SEP> I <SEP> ri <SEP> I <SEP> r <SEP> I <SEP> ri <SEP> I <SEP> ri
<tb> <SEP> r <SEP> A <SEP> rd <SEP> r <SEP> rd <SEP> rw <SEP> rS
<tb> <SEP> 2 <SEP> ± \ <SEP> tt <SEP> 3 <SEP> rX <SEP> t <SEP>> <SEP> U
<tb> <SEP> I <SEP> S <SEP> U <SEP> <
<tb> <SEP> 4:

  : 5 <SEP> rd <SEP> V <SEP> b <SEP> rd <SEP> 4 <SEP> rel <SEP> <<SEP> r <SEP> rl
<tb> <SEP> O <SEP> X <SEP> I <SEP> X <SEP> t) <SEP> X <SEP> (D <SEP>>> <SEP> Q) <SEP> X <SEP> Q) <SEP> rX
<tb> <SEP> <<SEP>, <SEP> r <SEP> O <SEP> ° <SEP> <<SEP> eg <SEP> t <SEP> <<SEP> <<SEP> et <SEP> <
<tb> <SEP> I <SEP> 4 <SEP> L,

   <SEP> I <SEP> V <SEP> 1 <SEP> 42
<tb> <SEP>> <SEP> d <SEP> t <SEP> tt
<tb> <SEP> <) <SEP>> <SEP> O <SEP> ç <SEP> O <SEP> rl
<tb> <SEP> rt <SEP> rwl <SEP> rl <SEP> rl <SEP> (\ 1 <SEP> t
<tb>
EMI18.1

  <SEP> IL <SEP> III <SEP> Y (Y1 = Y2) <SEP> FARE
<tb> 22 <SEP> -Aethy1-N-by- <SEP> pyridine-2,5-i- <SEP> -CN <SEP> i'üntichi-elb
<tb> <SEP> hydroxyethyl-aniline <SEP> carboxylic acid-i <SEP> P <SEP> P <SEP> P <SEP> P
<tb> <SEP> 0
<tb> 23 <SEP> -Aethyi-N43-hydrox <SEP> II
<tb> <SEP> rl <SEP> r (<SEP> CCl <SEP> -CN <SEP> gruntichig-elb
<tb> <SEP> w <SEP> 6 <SEP> 6 <SEP> C <SEP> C
<tb> <SEP> g <SEP> u <SEP> o <SEP> o <SEP> o <SEP> o
<tb> <SEP> coa <SEP> Y <SEP> Y <SEP> v
<tb> <SEP> x <SEP> 01 <SEP> 0a <SEP> GQ <SEP> 0a <SEP>%
<tb> 24 <SEP> NyarCoYxyT1ätthyYilanNin <SEP> II <SEP> -CN <SEP> k <SEP> k
<tb> <SEP> o¸ccl
<tb> <SEP> cocl
<tb> 25 <SEP> N-Ethy1-N-hydrox <SEP> -

   <SEP> green-yellow
<tb> <SEP> ethyl-3-methyl- <SEP> 5-nitro-isophthalene <SEP>
<tb> <SEP> II <SEP> chloride
<tb> <SEP> r <SEP> U <SEP> u <SEP> u <SEP> U <SEP> U
<tb> w <SEP> l <SEP> -Cyanäty1-N-- <SEP> 5-nitro-ophthalmic- <SEP> I <SEP> I <SEP> I <SEP> I
<tb> <SEP> e, <SEP> 8 <SEP> h
<tb> <SEP> 01 <SEP> ax
<tb> <SEP> 1 1 <SEP> H <SEP> H <SEP> ri
<tb> <SEP> I <SEP> t <SEP> t) <SEP> c> <SEP> ed <SEP> fES
<tb> <SEP> S <SEP> &num; d <SEP> O <SEP> ¯ <SEP> c) <SEP> O <SEP> = <SEP> C> <SEP> S <SEP> rN
<tb> <SEP> e <SEP> x: J <SEP> I <SEP> I <SEP> p <SEP> S
<tb> <SEP> I <SEP> t <SEP> X
<tb> <SEP> H <SEP> CM <SEP> [<SEP> I <SEP> o <SEP> 01
<tb> <SEP> Ft <SEP> I: <SEP> t <SEP> t <SEP> e <SEP> d
<tb> <SEP> t-t <SEP>; <SEP> e <SEP> I <SEP> I <SEP> I <SEP> d <SEP> I <SEP> i
<tb> <SEP> ri <SEP> ° rt <SEP> t:

  <SEP> O <SEP> 8 <SEP> O <SEP> h <SEP> O <SEP> h
<tb> <SEP> o <SEP> o <SEP> r4 <SEP> <<SEP> O <SEP> S <SEP> <SEP>; <SEP> <SEP> 9 <SEP> O
<tb> <SEP> ¯ <SEP> I <SEP> U
<tb> <SEP> X <SEP>; <SEP> X <SEP> S;
<tb> <SEP> O <SEP> I <SEP> rt <SEP> O <SEP> I <SEP> hH
<tb> <SEP> .C <SEP> h <SEP> "<SEP> rl <SEP> h <SEP> <SEP> r4
<tb> <SEP> I <SEP> rl <SEP> t <SEP> T <SEP> t <SEP> I <SEP> rt
<tb> <SEP>>> <SEP> rQ <SEP> px <SEP> I <SEP> Z <SEP> °
<tb> <SEP> S <SEP> riF <SEP> 5 <SEP> rJ
<tb> <SEP> tF <SEP> + <SEP> rC <SEP> X <SEP> &verbar;<SEP>; <SEP> rl4
<tb> <SEP> z <SEP> H <SEP> z <SEP> e) <SEP> <<SEP> S
<tb> <SEP> e <SEP> <
<tb> <SEP> r2,2:

  <SEP> r-4 <SEP>} <SEP> 4 <SEP> &verbar; <SEP> gt.al
<tb> <SEP> 9 <SEP> s:
<tb> <SEP> H <SEP> X <SEP>>> <SEP> ç <SEP> 9 <SEP> rl <SEP> O <SEP> O <SEP> + <SEP> H <SEP> ç <SEP > U <SEP> O
<tb> <SEP> (D <SEP> X <SEP> o
<tb> <SEP> <<SEP> o <SEP> ° <SEP>, st <SEP> ra <SEP> <SEP> $ <SEP> H <SEP> n <SEP> e
<tb> <SEP> I <SEP>} ", <SEP> 1 <SEP> 4M <SEP> a <SEP> I <SEP> b <SEP> I <SEP> 9 <SEP> a <SEP> I < SEP> X
<tb> <SEP> l; 5 <SEP> t <SEP> rz;

  <SEP>>! <SEP> U <SEP> Z <SEP> S <SEP>> <SEP> d <SEP> <SEP> s
<tb> <SEP> CM
<tb> <SEP> OJ <SEP> N <SEP> N <SEP> C \ t <SEP> CQ
<tb>
Example 8
A dye identical to that described in Example 1 (Table III) could also be prepared in the following manner: 4.82 parts (0.02 mol) of the dye of the formula
EMI19.1
 a solution of 1.1 parts by volume of succinic acid dichloride in 10 parts by volume of benzene was slowly added to 20 parts by volume of benzene with stirring, and the mixture was then refluxed for 1 hour with stirring and poured onto ice-water; It was extracted with chloroform, and the chloroform phase was extracted with 10% sodium carbonate solution and then with 2N hydrochloric acid, washed neutral with water, dried with sodium sulfate and evaporated.

  The remaining oil was dissolved in hot methanol / ethyl acetate.



  After some time, 3 parts of the dye which has already been described in Example 1, Table III, crystallize out as an orange product.



  Analysis: Calculated: C 68.1% H 5.7% N 14.9% Found: C 67.8% H 5.7% N 14.7%.



   Example 9
In a 750 ml sulfonation flask, 30 ml of Phos.



  Gen submitted, 100 ml of dry chlorobenzene added and at a temperature of -30 to -70 CC 1/1 (mol N-ss-hydroxyethyl-N-ss-cyanoethyl-aniline in 50 m: dry chlorobenzene. It is added with 50 m chlorobenzene rinsed, allow to warm to room temperature, and then slowly heated to 80 to 85 ° C. and phosgene passed through until a clear solution has formed, then the excess phosgene is removed with nitrogen, to solution 1/1 (mol N-ethyl-N -ss-hydroxyethyl-1,3-toluidine and heated under reflux for three days with stirring.After cooling, the solution is treated with dilute hydrochloric acid.



  re extracted, washed neutral, dried and the solvent removed in vacuo. After standing for a long time, the product begins to crystallize, is then triturated well with cold ether, filtered and dried at 40 ° C. in vacuo. The product of the following formula is obtained
EMI19.2

If this product is formylated according to Vilsmeier and the dialdehyde is condensed with malonitrile analogously to the procedure of Example 6, the dye of the following formula is obtained as an olive powder
EMI19.3

Example 10
To 100 parts of chlorobenzene saturated with phosgene, 19 parts of N-oxyethylN-fl-cyantnethyl aniline in 100 parts of chlorobenzene are added dropwise at 0 ° C.

  The mixture is stirred for 3 hours at this temperature with continuous introduction of phosgene. Then it is heated to approx.



  50 to 55 ° C., stirred for about 30 minutes at this temperature and then heated to 80 to 85 ° C. At this temperature, phosgene is passed in with stirring until a clear solution has formed.



  The excess phosgene is then blown out with nitrogen and the hot solution is filtered. This solution is added to 19 parts of N-ß-oxyethyl-N-ß-cyanoethylaniline and refluxed with stirring for 24 hours. Then the solvent is completely removed in vacuo, and 10 ml of ethanol are added to the residue. After two to three days, most of the residue has solidified.

  After filtering off, the residue is triturated with cold ethanol and filtered off again. After recrystallization, a product of the formula is obtained
EMI19.4

Analysis: Calculated: C 67.96% H 6.45% N 13.79% Found: C 68.21% H 6.37% N 13.56%
4.1 parts of this product are introduced into a mixture of 9.2 parts by volume of dimethylformamide and 14.2 parts by volume of phosphorus oxychloride at 15 ° to 20 ° C. with stirring and then stirred for 6 hours at 60 ° C., poured onto ice, chloroform added @ and the mixture neutralized with sodium hydroxide solution.

  The chloroform phase is washed out with saline, dried with sodium sulfate and concentrated, 4.7 parts of the dialdehyde remaining as an oil.



  This is dissolved in hot methanol, 1.4 parts of malodinitrile and 0.1 parts by volume of piperidine are then added and the mixture is refluxed for 4 hours. The dye of the formula falls on cooling
EMI20.1
 as oil, which solidifies after a while. It is ground in a mortar with a little methanol, filtered off with suction and washed with petroleum ether. After drying at 70 ° C. 3.2 parts of a brown-yellow powder remain.



   Example 11
36 parts of N-ethyl-N- (s-oxyethyl) -m-toluidine are slowly heated to 1700 in an oil bath with 12.5 parts of diethyl carbonate and 0.2 parts of sodium, with ethanol being distilled off. After some time, it is allowed to cool, the residue is taken up in benzene and extracted with water. The benzene phase is dried, the benzene is evaporated and the crude product is distilled. 18.2 parts of a light yellow oil with a boiling point of 195 ° to 205 ° C. at 0.02 Torr are obtained, which has the formula
EMI20.2
 Has.



  Analysis: Calculated: C 71.8% H 8.4% N 7.3% Found: C 72.3% H 8.4% N 7.2 e / o.



   7.7 parts of these carbonic acid esters are introduced into a Vilsmeier mixture of 18.6 parts by volume of dimethylformamide and 28.6 parts by volume of phosphorus oxychloride at 15 to 20 ° C. with stirring and then stirred at 600 for 5 hours, on ice-water discharged, adjusted to pH 7 with sodium hydroxide solution, taken up in chloroform, the chloroform phase washed with sodium chloride solution, dried with sodium sulfate, concentrated. There remain 8 parts of the dialdehyde of the formula
EMI20.3

21 parts of the dialdehyde are refluxed for 4 hours in 300 parts by volume of methanol with 7 parts of malodinitrile and 0.5 parts of piperidine, an orange crystalline precipitate soon forming.

  After cooling to room temperature the product has the formula
EMI20.4
 Aspirated and washed with alcohol. After this
17.4 parts of the dye remain when dry. He colors
Acetate and polyester materials in pure greenish yellow tones with excellent fastness properties and good build-up capacity.



  Analysis: Calculated: C 69.40 /. H 6.0 0 / o, N 15.7% found: C 69.1 s /. H 6.0'10 N 15.5 / o.



   Example 12
50 parts of N-ethyl-N (β-oxyethyl) aniline and 26 parts of toluene-2,4-diisocyanate are heated at 90 to 95 in 50 parts of dry benzene in a bath. On cooling, 73.5 parts of the crude product crystallize out as colorless crystals Ivom, melting point 108 to 115. After one recrystallization from methanol, the melting point is 113 to 116 ° C.



   The product has the formula
EMI21.1
 Analysis: Calculated: C 69.0% H 7.2% N 11.1% found: C 69.1% H 6.9% N 11.5 / o.



  10 parts of this diurethane are formylated with a mixture of 18.6 parts by volume of dimethylformamide and 28.6 parts by volume of POCl8. The dialdehyde of the formula is obtained
EMI21.2
 2.8 parts of this dialdehyde are heated under reflux for 4 hours in 50 parts by volume of ethanol with 0.7 parts of malononitrile and 0.1 part of piperidine. The dye of the formula falls on cooling
EMI21.3
 as oil, which solidifies over time. It is triturated with ethanol in the mortar, suction filtered and washed with petroleum ether. After drying at 60 ° C., 1.5 parts of an orange powder remain.



   Example 13
If 54 parts of N-ethyl-N- (s-oxyethyl) m-toluidine, 25 parts of 1,6-hexamethylene diisocyanate and 50 parts of benzene are used and the procedure as in Example 12 is used, 80 parts of ethyl alcohol are added after Cooling 46 parts of a crude product with melting point 58 to 600. After recrystallization once from methanol, the melting point is 60 to 62. The product has the formula
EMI21.4
 Analysis: Calculated: C 68.4% H 8.8% N 10.6% Found: C 68.4% H 8.6% N 10.5%.



  If 10.4 parts of this diurethane are formylated with a mixture of 18.6 parts by volume of dimethylformamide and 28.6 parts by volume of phosphorus oxychloride and the procedure described in Example 12 is used, 11 parts of the dialdehyde of the formula are obtained
EMI22.1
 as a light brown semi-solid crystal mass.



   5.8 parts of this product are refluxed for 5 hours in 60 parts by volume of absolute alcohol and 30 parts by volume of dimethylformamide with 1.4 parts of malononitrile and 0.15 parts of piperidine and this solution is then poured into 1000 parts of water with stirring , acidified and the fancy brown-orange product of the formula
EMI22.2
 Aspirated and washed with water. After drying, 4 parts of the dye remain.



   The following Table IV includes a number of other valuable bis-styryl dyes which are obtained by condensation of 2 mol of the N ß-oxyethyl amines listed in column II with 1 mol of the bis-isocyanates listed in column 111, formylation according to Vilsmeier and condensation of the dialdehydes with a compound CN <H = X, analogously to the instructions of Example 13.

  The dyes dye acetate and especially polyester materials in greenish yellow shades with excellent fastness properties. TABLE IV
EMI23.1

 II <SEP> III <SEP> X <SEP> COLOR
<tb> N-ethyl-N-ss-hydroxy- <SEP> toluylene-2,4- <SEP> -CN <SEP> yellowish green
<tb> 1 <SEP> ethyl-3-methyl-aniline <SEP> diisocyanate
<tb> 2 <SEP> N-Aethyl-N-ss-hydroxy- <SEP> Touylen-2,4- <SEP> -COOC2H5 <SEP> yellowish green
<tb> ethyl-3-methyl-aniline <SEP> diisocyanate
<tb> 3 <SEP> N-Aethyl-N-ss-hydroxy- <SEP> hexane-1,6-diiso- <SEP> -CN <SEP> yellowish green
<tb> ethyl aniline <SEP> cyanate
<tb> 4 <SEP> N-methyl-N-ss-hydroxy- <SEP> hexane-1,6-diiso- <SEP> -CN <SEP> yellowish green
<tb> ethyl aniline <SEP> cyanate
<tb> 5 <SEP> N-methyl-N-ss-hydroxy- <SEP> phenylene-1,4-diiso- <SEP> -CN <SEP> yellowish green
<tb> ethyl aniline <SEP> cyanate
<tb> 6

   <SEP> N-methyl-N-ss-hydroxy- <SEP> phenylene-1,4-diiso- <SEP> -COOC2H5 <SEP> yellowish green
<tb> ethyl aniline <SEP> cyanate
<tb> 7 <SEP> N-Aethyl-N-ss-hydroxy- <SEP> phenylene-1,4-diiso- <SEP> -CN <SEP> yellowish green
<tb> ethyl aniline <SEP> cyanate
<tb>
EMI24.1


<tb> <SEP> bO <SEP> & <SEP> qO <SEP> b <SEP> Z
<tb> <SEP> bO <SEP> 40 <SEP> 40 <SEP> 00 <SEP> ba
<tb> <SEP> II <SEP> III <SEP> d
<tb> <SEP> C <SEP> rd <SEP> F <SEP> rC <SEP> A
<tb> <SEP> 0 <SEP> O <SEP> U <SEP> O <SEP> 0
<tb> <SEP> d <SEP> rl <SEP> rl <SEP> rt
<tb> <SEP> 8 <SEP> rheny1en-l, 4-iiso- <SEP> 0a <SEP> Q1 <SEP> 01-CN <SEP> yellow-green
<tb> <SEP> call <SEP> cyanate
<tb> <SEP> v <SEP> &commat;;
<tb> <SEP> drochinol <SEP> in
<tb> <SEP> wN
<tb> <SEP> X
<tb> <SEP> z <SEP> N-AethyI-N - bydroxy <SEP> OCNHNCO <SEP> z <SEP> 1 <SEP> elbstici ± -rUn
<tb> pi
<tb> <SEP>
<tb> <SEP> a <SEP> a <SEP> o <SEP> o
<tb> <SEP> Ii <SEP> cz <SEP> tyI-X - hydroxy <SEP> OCNCH2NCO <SEP> c) <SEP> v
<tb> <SEP> ä <SEP> a <SEP> a
<tb> <SEP> I
<tb> <SEP> m <SEP> i <SEP> 3: <SEP> 3;
<tb> <SEP> o <SEP> o <SEP> o <SEP> o <SEP> o
<tb> <SEP> X <SEP> &verbar;; <SEP> F <SEP> ¯ <SEP> r <SEP>
<tb> <SEP> o <SEP> oB <SEP> ov <SEP> oH
<tb> <SEP> X <SEP> 5 <SEP> h <SEP> g:

  <SEP> h
<tb> <SEP> <<SEP> I <SEP> xl <SEP> e <SEP> cb
<tb> <SEP> 4 <SEP> I <SEP> &verbar; <SEP>> <SEP> I <SEP> b <SEP> I <SEP> A
<tb> <SEP>: td <SEP> h <SEP> e <SEP> ° <SEP> aL, C <SEP> ax <SEP> n <SEP> o
<tb> <SEP> Yp <SEP> n <SEP> I <SEP> d <SEP> I <SEP> z <SEP> I <SEP> &commat; <SEP> I <SEP> H
<tb> <SEP> K <SEP> &commat; <SEP> <<SEP> z <SEP> rt <SEP> Si <SEP> aa <SEP>: z; <SEP> X <SEP>> <SEP> $
<tb> <SEP> o <SEP> 4s
<tb> 9 <SEP> 9 <SEP> I <SEP> o <SEP> H <SEP> W;

  <SEP> <<SEP> I <SEP> H <SEP> I <SEP> H <SEP> I
<tb> H <SEP> w1 <SEP> + <SEP> <
<tb> <SEP> atCs <SEP> O <SEP> <<SEP> C <SEP> ° <SEP> eC <SEP> <SEP>, C
<tb> <SEP> r <SEP> h <SEP> I <SEP> w <SEP> 1 <SEP> 4v
<tb> <SEP> ao <SEP> o <SEP> N
<tb> <SEP> H <SEP> H <SEP> H
<tb>
Example 14
0.2 parts of sodium are dissolved in 35.8 parts of N-ethyl-N-ß-oxyethyl-m-toluidine with heating, then 41.4 parts of N-ethyl-N-ß-carbomethoxyethylaniline are added and slowly up to 250 with stirring 0C heated, with methanol distilled off. The residue is distilled under high vacuum. You get the product: the formula
EMI25.1
 as a colorless oil, Kpo, 185 to 195.

 

  Analysis: C calculated: 74.5% H calculated: 8.5 0 / o C found: 74.4 / o H found: 8.3 / o This amine is formylated according to Vielmeier and the dialdehyde is condensed with malodinitrile analogously to Regulations of Example 6, the dye of the formula is obtained
EMI25.2
 which dyes acetate and polyester materials in greenish yellow tones with very good fastness properties.

 

Claims (1)

PATENT CLAIM Dye preparations, characterized in that they contain water-insoluble styryl dyes of the formula EMI25.3 wherein R1 and R2 are optionally substituted alkyl groups, which together with the radicals A1 and A2 can each be linked to form a ring, R3 is an optionally substituted alkylene group, R4 is a direct bond or an optionally substituted alkylene group, Y1 and Y2 are cyano, carbalkoxy or Arylsulfonyl groups, A1 and A2 optionally substituted p-phenylene groups and Z denote a direct bond or a colorless bridge free of -SO2- groups and contain at least one dispersant. UNDER CLAIMS 1. Dyestuff preparations according to claim, characterized in that they contain bisstyryl dyestuffs in which the group Z is an oxygen atom or an imino group and R4 is an alkylene group. 2. Dyestuff preparations according to claim, characterized in that they contain bisstyryl dyestuffs in which the group Z is an organic group and R4 is an alkylene group. 3. Dyestuff preparations according to dependent claim 2, characterized in that they contain bisstyryl dyestuffs in which the group Z is an organic radical which contains at least one heteroatom. 4. Dye preparations according to dependent claim 2, characterized in that they contain bisstyryl dyes in which the divalent radical Z contains at least one, but preferably 2 acyl groups or a diacyl radical as connecting divalent groups in the main chain which connects the styryl dyestuff radicals. 5. Dyestuff preparations according to dependent claim 4, characterized in that they contain bisstyryl dyes in which Z is a radical of the formula where X 'is an oxygen atom, a sulfur atom or an imino group and Z' is the diacyl radical of an organic bifunctional acid. 6. Dyestuff preparations according to dependent claim 5, characterized in that they contain Bisstyrylfarbstof.fe in which Z 'is the diacyl radical of an aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic dicarboxylic acid. 7. Dyestuff preparations according to dependent claim 5, characterized in that they contain bisstyryl dyes in which Z 'is the diacyl radical of an aliphatic, cydoaliphatic, araliphatic, aromatic or heterocyclic dicarbamic acid. 8. Dyestuff preparations according to dependent claim 5, characterized in that they contain bisstyryl dyestuffs in which Z 'is the diacyl radical of an aliphatic or aromatic disulphonic acid. 9. Dye preparations according to dependent claim 4, characterized in that they contain bisstyryl dyes in which Z means a radical of the formula -OCO-X'-R5-X'-OCO, in which Rs is a divalent organic radical and X 'is an oxygen atom Is a sulfur atom or an imino group. 10. Dyestuff preparations according to the patent claim, characterized in that they contain bisstyryl dyes. contain, in which the divalent bridge Z is formed by two-sided addition of a para amine group with at least one active hydrogen atom to an epoxy compound, and the groups R3 and R4 represent the N-hydroxylethylene groups formed by opening the oxirane rings. 11. Dyestuff preparations according to dependent claim 10, characterized in that they contain bisstyryl dyestuffs in which the hydroxyl groups formed by opening the oxirane rings are substituted. 12. Dyestuff preparations according to dependent claim 10, characterized in that they contain bisstyryl dyestuffs in which the hydroxyl groups formed by opening the oxirane rings are esterified. 13. Dyestuff preparations according to patent claim, characterized in that they contain bisstyryl dyes in which the radical Z contains an aromatic radical. 14. Dyestuff preparations according to patent claim, characterized in that they contain bisstyryl fibers in which Z is one of the groups or atoms of the formulas EMI26.1 -O-CH2-CH2-NH-CH2-CH2-O or -O-R5-O-, where Rs is a divalent aliphatic, araliphatic or aromatic radical whose carbon chain can be interrupted by heteroatoms. 15. Dyestuff preparations according to dependent claim 14, characterized in that they contain bisstyryl dyestuffs in which the radical R5 can be interrupted by oxygen atoms. 16. Dyestuff preparations according to dependent claim 14, characterized in that they contain bisstyryl dyes in which R5 is a radical of the formulas EMI26.2 <tb> <SEP> OH2 <tb> -OH2-OH2-, <tb> <SEP> ICH3 <tb> <SEP> <} CE2 {}, <SEP> CH- <SEP> (r) -, <SEP> - <Zt <SEP> -c --- <SEP> is. <tb> <SEP> CH3 <tb> 17. Dyestuff preparations according to claim, characterized in that they contain bisstyryl dyes in which Z is a radical of the formulas -O-CO-, -CO-O-, -O-CO-O, -O-CO-CO-O NHCO- , -CONH -CONHCO-, -c (> -NH-NH-Co or -NH-CO-CO-NH.