CH522721A - Reactive dyestuffs capable of chemical bonding to - Google Patents

Abstract

Reactive dyes, which are esp. useful for dyeing polymeric materials having rective hydrogens e.g. cellulosics such as rayon and cotton, superpolyamides such as nylon, natural proteinaceous materials such as wool, silk, casein and hair and synthetic resins such as the phenolics, have formula:- (in which D is an organic dye residue, preferably the residue of an anthraquinone, phthalocyanine, azo or anthrone dye; Y is a covalent bond or a divalent bridging gp. i.e. (alkylene) sulphonyl, alkyleneoxy, alkylenethio, (alkylene)carbonyl, or alkylene gp. the alkylene radicals having 1 or 2 C atoms; R = H or C1-C4 alkyl gp. and R' = H or CH2OR and n = 1 or 2.

Description

  

  
 



  Process for the production of substrate-reactive dyes or optical brighteners
The invention relates to a process for the production of substrate-reactive dyes or optical brighteners.



   It is known that dyes can be applied to polymeric materials in a reactive manner, in contrast to physical application in which the attraction of the dye to the polymer does not arise from any chemical bond. Various attempts to solve the problem of finding suitable methods for chemically applying the dye to a substrate are known. These methods are of course determined by the reactivity of the polymeric substrate to be colored. For substrates that are characterized by regularly recurring reactive hydrogen atoms, such as B. cellulose (either natural or regenerated), the dye should be chemically able to enter into a condensation reaction. A known reactive group for the connection of dye residues with cellulose is the 2,4-dichlorotriazinyl residue.

  The chemical binding of such dyes to cellulose is obtained by bringing the substances into contact with one another under such conditions that hydrogen chloride is split off.



   Another reactive group that has been studied is the methylol group. If a methylol-containing dye is brought into contact with cellulose under suitable conditions, water is split off and the dye is bound to the cellulose structure via an ether group. Such known reactive dyes have not yet found widespread technical application, perhaps because in practice the bond obtained with the fiber was not as stable as would be desirable for practical purposes.



   The present invention relates to the field of methylolated reactive dyes. It is based on the discovery that the reactivity of the methylol group with active hydrogens of the polymer substrate is significantly improved by the fact that an activating bond, as defined below, is inserted between the aromatic dye component and the reactive methylol radical.



  The basic concept of an activated bond is not completely new, but the special bond according to the invention is remarkably better able to fulfill the activating function than was previously thought possible. By modifying the dye according to the invention, an increased degree of reactivity of the dye with the polymeric substrate is obtained and, once the reaction has taken place, a stronger bond with the substrate.

  Colorings of polymeric substrates which have been obtained with the modified chemically reactive dyes according to the invention have a much better wet fastness than if the dye component was applied by physical application methods. Surprisingly, the dyes according to the invention are much more firmly and permanently bonded to polymer substrates than even very similar methylol-modified dyes. which lack the special activating bond according to the invention.

  Another advantage of the invention is reading therein. that the dyes can be produced here with a mild reaction hed; nounoen. so that there is minimal damage to the chromonhoric or fluoronhoric character of the exfoliating material. This fact contributes to making the dyes according to the invention technically attractive.



   The activating bond. which forms the basis of the present invention. can be expressed by the following formula:
EMI2.1
 where Y is a bridging group, such as a covalent bond, a sulfonyl (SOr), alkylene sulfonyl (-alk-SO-), alkyleneoxy- (-alk-Q-), alkylene thio- (-5-alkylene-), carbonyl- (CO ), carbonyl (-alkCO-) or alkylene group.



  The alkylene radical should contain either one or two carbon atoms.



   The process according to the invention for the preparation of substrate-reactive dyes or optical brighteners of the formula:
EMI2.2
 where D is an organic dye residue or the residue of an optical brightener, Y is a covalent bond or a divalent bridging group, R is hydrogen, R 'is hydrogen or a group CH> OH and n is the number 1 or 2, is characterized in that one is a dye or optical brightener of the formula:
EMI2.3
 methylolated. The methylol group or the methylol groups can then be acylated or alkylated.



   The number of methylol (or alkoxymethyl) groups can be 1 to 4. At least one such group must be present in order for the advantages according to the invention to be obtained. Up to 4 can be present with excellent results, but such complete methylolation is sometimes difficult to obtain and often unnecessary since about 2 methylol groups give very suitable reactivity with a more polymeric substrate. The methylolation step, which leads to the dyes or optical brighteners of the formula I, can result in a reaction product which contains mixtures of monomethylolated, dimethylolated, trimethylolated and tetramethylolated molecules. If such mixtures appear in the following, they are indicated by the average methylolation of the product.

  This mean is sometimes represented by a fractional number.



   Compounds of the formula I are particularly suitable for coloring or optically brightening polymers which have a reactive hydrogen atom with which they can react. These include cellulose and its derivatives (natural cellulose such as cotton and paper, and synthetic cellulose derivatives such as rayon, acetate, etc.), polyamides (natural polyamides such as wool and synthetic polyamides such as nylon) and polyurethanes. At the current stage of polymer technology, the dyes or optical brighteners of the formula I are best suited for use in paper and cotton.



   As indicated above, the invention is generally applicable regardless of the particular structure of the dye or optical brightener. The dyes or optical brighteners can be acridine, anthraquinone, azine (e.g. pyridine and quinoline), azo (mono- or poly, metallized or non-metallic siebe azo), azomethine, cyanine, Di ary1meth an-, indamin-, indophenol-, indigo-, keto-, amino- or hydroxy-, lactone-, methine- or polymethine-, nitro-, nitroso-, oxazine-, oxazole- (benzo- or naphtho-) , triazole (benzo and naphtho), phthalocyanine (and metal derivatives), quinoline, quinone (benzo or naphtho), stilbene, sulfur, thiazine, thiazole, triarylmethane, xanthine and benzidine sulfone derivatives .

  The aromatic components of these dyes or optical brighteners can be substituted by the usual chromophoric and auxochromic radicals known to the person skilled in the art, and the latter are completely inert with regard to the reactivity of this component imparted by the invention. Most often, the residue D will be the residue of an antraquinone, azo, nitro, phthalocyanine or triarylmethane dye, as these classes are most popular due to the range of colors in which they are available.



   In preferred cases, the dyes or



  optical brightener solubilizing groups. These are either non-ionizing or ionizing groups. If they are non-ionizing, such groups can be hydrophilic radicals such as hydroxyalkyl (including the methylol groups themselves), polyhydroxyalkyl, carbamyl, sulfamyl, alkylsulfonyl, phosphonamyl, sulfinamyl, sulfenamyl and the like. In the case of ionizing groups, the solubilizing groups can be sulfonic, carboxyl, phosphonic and the like in the form of the free acids or in the form of an alkali (e.g. sodium or potassium) or ammonium salt. The ionizing groups can also be quaternary ammonium or phosphonium or ternary sulfonium groups in the form of salts with chlorine, iodine, methosulfate, tosylate or other anions.

 

   The dyes or optical brighteners of the formula II can be produced by introducing at least one iminobispropionamide group into a dye or optical brightener or into an intermediate product used to produce the same and converting the intermediate product into the dye or optical brightener.



     3,3'-Iminobispropionamide and its sulfur and phosphoric acid addition salts can be prepared by hydrolyzing ß, ß-iminobispropionitrile in the presence of sulfuric or phosphoric acid and recovering the acid addition salt and, if necessary, neutralizing it.



   The remainder D can e.g. B. the remainder of an azo, anthraquinone (or other vat dye), phthalocyanine, anthrone (e.g. anthrapyridone and anthrapyrimidone), indigo, xanthene, triaryl methane, diaryl methane, nitro , Nitroso, azine, acridine, thiazine or oxazine dye. Since those dyes are preferred according to the invention in which the group D is the radical of an azo, anthraquinone, anthrapyridone or phthalocyanine dye, these are described in more detail.



   The azo dye residues for the new dyes according to the invention are derived from various aromatic diazo components and coupling components. The components can contain at least one methylolizable reactive bond or an immediate precursor therefor, or the methylolizable reactive bond can be introduced into the dye after coupling.



   Examples of diazotizable amines which contain the methylolatable group which can be used to form the diazo components are: 3,3 '- (metanilylimino) bispropionamide; 3-amino-4-methoxy-N, N-bis (2-carbamylethyl) benzenesulfonamide; o-Amino-N, N-bis (2-carbamylethyl) -benzenesulfonamide; p-amino-N, N-bis- (2-carbamylethyl) -benzenesulfonamide; 4-chloro-3-nitro-N, N- (2-carbamylethyl) -benzenesulfonlamid; 3,3 '- (p-aminophenvlimino) bispropionamide; m-amino-N, N-bis (2-carbamylethyl) benzamide; 3,3 '- {[2- (N-Ethyl-m-toluidino) ethyl] imino} bispropionamide.



   Amines can be diazotized and used in the invention. even if they do not contain the activating methylolatable bond. Atnines of this type can be coupled with coupling components which can be methylolated.

  Optionally, the binding can also be attached. when the coupler does not have the activated bond. Examples of amines that do not have a metholable activating bond and can be used to produce the diazo components are:

  : Aniline, o-nitroaniline, m-nitroaniline, p-nitroaniline, o-, m- and p-chloroaniline, 2-nitro-4-chloroaniline, 2-amino-5-nitrotoluene, 4-amino-3-nitrotoluene, 2- Amino-4-nitrotoluene, 2-amino-5-chlorotoluene, 2-amino-4-chlorotoluene, 2-amino-6-chlorotoluene, 2,5-dichloroaniline, 3,4-dichloroanline, 3-amino-4-chlorotoluene, o-m - and p-anisidine, 3-nitro-4-methoxyaniline, 4-nitro-2-methoxvaniline, 2-nitro-4-ethoxyaniline, dianisidine, 1-amino-2,5-diethoxy-4-benzoylaminobenzene, 4-amino-1- benzo ylamino-2,5-dimethoxy-benzene, benzidine (incl.



  of monoacyl derivatives), tolidine. 4-chloro-2-methoxyaniline, 1,5-dimethoxy-2-amino-4-chlorobenzene. 1 methoxy-2-benzoylamino-4-chloro-5-aminobenzene, 1 naphthylamine, 1-aminoanthraquinone, 1-amino-3chloranthraquinone, 3-amino-4-methoxybenzenesulfone diethylamide, 4-methoxy-2-aminophenylethylsulfone, 4-benzoylamino amino-m-xylidine, 4-methoxy4'-aminodiphenylamine, 4-aminodiphenylamine, 4 chloro-2-aminodiphenyl ether, 4,4'-dichloro-2-aminodiphenyl ether, o-aminodiphenylamine, 2,6,4'-trimethyl- 3'-nitro-4-aminaazobenzene, 5-methyl-4-methoxy-2-amino-2'-chloro-4'-nitroazobenzene, phenyl-azo-1-naphthylamine, m- and p-aminoacetanilid, N-benzoyl-m- and p-phenylenediamine, sulfanilamide, methanilamide, orthansilamide, m- and p-amino- N-methylacetanilide, o-,

   m- and p-aminobenzamide, 4- and 5-aminosalicylamide, 2-aminophenol-4-sulphonic acid, 6-amino-4-nitrophenol-2-sulphonic acid, 2-aminophenol-5-sulphonamide, 2-amino-2 ' -methyldiphenylether-4-sulfonic acid, 4-aminoazobenzene, 4-aminoazobenzene-4'-sulfonic acid, 4-aminoazobenzene-3,4'-disulfonic acid, orthanilic acid, meta nilinic acid, sulfanilic acid, 6-methylmetanilinic acid, 2-amino-5-chloro -4-methyl-benzenesulfonic acid, 5-chlorothanilic acid, aniline-2,5-disulfonic acid, 4-chloro-5-methylorthanilic acid, 4-methoxy-orthanilic acid, 2,4-dimethylaniline-6-sulfonic acid, 2-amino-4- trifluoromethylbenzenesulfonic acid, 3,4-dichloroaniline-6-sulfonic acid, 3,5-dichloroaniline-6-sulfonic acid, 3-methoxyaniline-6-sulfonic acid, 4-methylaniline-2-sulfonic acid, dehydrothiotoluidinesulfonic acid, 2-amino-naphthalene-4,8- disulfonic acid,

   2-aminonaphthalene-6-sulfonic acid, 2-aminonaphthalene-6,8-disulfonic acid, 2-amino-1-naphthol-4-sulfonic acid, 1-aminonaphthalene-4-, 5-, 6- and 8-sulfonic acid, 2-aminonaphthalene-5 , 7-disulfonic acid, 2-aminonaphthalene-7-sulfonic acid, 2-aminonaphthalene-1-sulfonic acid, p-phenylenediamine-2-aminonaphthalene-1,5-disulfonic acid, 3,3 'dichlorobenzidine, benzidine-3,3'-disulfonic acid, 2,2'-dichloro-3,3'-dimethoxy-4,4'-diaminodiphenyl, 4-aminopyridine, 2-aminopyridine-N-oxide, 3-aminopyridine, 2-aminobenzothiazole, -4, 5- or 6-aminoquinoline.



   The coupling components which can be used with the above-mentioned diazo components for the preparation of azo dyes according to the invention can contain the methylolatable bond or a precursor. But they can also be used with diazo compounds that have such bonds. Optionally, as indicated above, the methylolatable bond can be attached to an existing azo dye which was formed from components which had no methylolatable bonds.



   Examples of methylolatable compounds. which can be used as coupling components are: 3,3 '- (Phenylimino) bispropionamide, 3,3' [(6-Amino-2-naphthyl) sulfonylimino] dipropionamide, 3, 3 '[(5-hydroxy- 1-naphthyl) sulfonylimino] dipropionamide, 3,3 '- [p- (5-Hydroxy-3-methyl-1-pyrazolyl) phenylsulfonylimino] dipropionamide, 8 - {{6 {m [bis (2-carbamylethyl ) -sulfamyl] -anilino} -4-hydroxy-s-triazin-2-yl 5 -aminol -l -n, aphthol-3-, 6-disulfonic acid, N, N-bis- (2-carbamylethyl) -p- (5-hydroxy-3 -methyl-1-pyrazolyl) -benzamide, N, N-bis (2-carbamylethyl) -5-hydroxy-1-naphthamide, 6-amino-N, N-bis- (2-carbamylethyl) -2-naphthamide, 1 Acetamido-8-naphthol-3,6-disulfonic acid, 1-benzamido-8-naphthol-3,6-disulfonic acid. 3-Acetamido5-naphthol-7-sulfonic acid, 2- or 3-benzamido5-naphthol-7-sulfonic acid,

   2-aminonaphthalene-6,8-disulfonic acid and 2-aminonaphthalene-6-sulfonic acid.



   Examples of non-methylolizable compounds that can be used as coupling components are: aniline, o-toluidine, m-toluidine, 2,5-xylidine, o anisidine, m-anisidine, 2-methoxy-5-methylaniline, 2, 5-dimethoxyaniline, N-methylaniline, N-methyl-otoluidine, N-methyl-m-toluidine, N-ethyl-o-toluidine, N-methyl-2-methoxy-5-methylaniline, N-ethyl2-methoxy-5- methylaniline, N-methyl-m-anisidine, l-amino-8-naphthol-6-sulfonic acid, l-amino-8-naphthol-3,6-disulfonic acid, 1-amino-8-naphthol-4,6-disulfonic acid, l-methylamino-8-naphthol-6-sulphonic acid, 2- or 3-amino-5-naphthol-7-sulphonic acid, 2-methylamino-5-naphthol-7-sulphonic acid, 1-amino-8-naphthol- 2,4-disulfonic acid, 1-amino-8naphthol-4-sulfonic acid, 3-methyl-5-pyrazolone, 1 phenyl-3-methyl-5-pyrazolone, 1- (4-sulfonphenyl) 3-methyl-5-pyrazolone,

   1- (4-chlorophenyl) -3-methyl-5-pyrazolone, 1-phenyl-3-carbethoxy-5-pyrazolone, acetoacetanilide, 4'-sulfo-acetoacetanilide, bis-acetoacetbenzidide, bis-acetoacettolidide, acetoacettolidide, m- and p-Aminoacetanilide, mund p-Amino-N-methylacetanilide, 1-naphthol-6-sulfonic acid, 3-hydroxy-2-naphthamide, 3-carbamyl-2-naphthol-1,6-disulfonic acid, N- [2-aminoethyl] -N ethyl-m-toluidine, beta hydroxynaphthoic acid, arylides of various napthoic acids, such as. B.



  2-hydroxy-3-naphthanilide, 2-hydroxynaphthyltoluidine and the like. Many other coupling components and diazo components are known and can be used. In order to obtain the preferred azo dye residues, the coupling and / or the diazo component should contain a solubilizing group.



   A particularly preferred group of azo dye residues are the monoazo compounds which contain 1-3 sulfonic acid groups.



   The various anthraquinone and other polyquinone structures. known by the general name vat dyes can be used. Kipen dye residues with solubilizing groups. z. B. free sulfonic or carboxylic acid substituents are preferred.



   Examples of anthraquinone compounds which can be used to prepare the dyes according to the invention are: 1-amino-4- (4'-aminoanilino) -anthraquinone-2,3'-disulfonic acid, 1-methylamino-4- (4'- aminoanilino) anthraquinone-2,3'-disulfonic acid, 1-amino-4- (4'aminoanilino) -anthraquinone-6,3'-disulfonic acid, 1-amino-4- (4'-aminoanilino) -anthraquinone-2,3 ', 5'-trisulfonic acid, 1-methylamino-4- (4'-aminoanilino) -anthraquinone-6-sulfonic acid, 1-methyl-amino4- (4'-aminoanilino) -anthraquinone-6,3'-disulfonic acid, 1-cyclohexylamino -4- (4'-aminoanilino) -6sulfonic acid, 1-methylamino-4- (3'-aminoanilino) anthraquinone-6-sulfonic acid, 1-amino-4- (3'-aminoanilino) -anthraquinone-2,5-disulfonic acid , 1-Amino 4- (4 '- [4 "-aminophenylazo] -anilino) -anthraquinone-2,5" -trisulfonic acid, 1-Amino-4- (4' - [4 "aminophenyl] -anilino) -anthraquinone- 2,5,3 "-trisulfonic acid,

   1-Amino-4- (4'-aminoanilino) -anthraquinone-3'-sulfonic acid, 1-amino-4- (3'-aminoanilino) -anthraquinone-4'-sulfonic acid, 1-amino-4- (4'amino -anilino) -anthraquinone-2-sulfonic acid 1-amino-4- (3'-amino-4'-methylanilino) -anthraquinone-2-sulfonic acid, 1-amino-4- (4'-amino-3'-methylani lino) - anthraquinone-2-sulfonic acid, 1-amino-4- (3'-amino-4 ', 6'-dimethylanilino) -anthraquinone-2-sulfonic acid, 1-amino-4- (4'-aminoanilino (-anthraquinone-3' -sulphonic acid diethylamide, 1-amino-4-bromoanthraquinone-2-sulphonic acid, 1-amino-4-bromoanthraquinone-2,5-disulphonic acid, 1-amino-4-bromoanthraquinone-2,6-disulphonic acid, 1-amino-4 -bromoanthraquinone-2,7-disulfonic acid and 1-amino-2,4-dibromoanthraquinone.



   Among these, the preferred class can be represented by the following formula:
EMI4.1
 wherein Y is a hydrogen atom or a sulfonic acid group and R is an aryl radical which may be substituted, in particular with soluble groups, such as. B.



  Sulfo or carboxyl groups.



   The class of anthroric dyes is derived from the class of anthraquinones by cyclization in the 1.9 position. These dyes represent a highly specialized class, which are characterized by their color shade range from orange to red and their general good lightfastness. Many substituted anthrone dyes can be used as starting materials for the invention.

  These include, for example, the following: pyrazole anthrones such as 3,3'-disulfo-5- (4'-aminoanilino) pyrazole anthrone and 2-methyl-4 ', 8-disulfo-5- (3'-aminoanilino) pyrazole anthrones; Anthrapyrimidines such as 4,3'-disulfo-6- (4'-aminoanilino) anthrapyrimidines; Anthrapyrimidones such as 3-methyl-4,4'-disulfo-6- (3'-aminoanilino) anthrapyrimidone and 3-ethyl-8,3'-disulfo-6- (4'-aminoanilino) anthrapyrimidone; and anthrapyridazones such as the 2- (4'-sulfophenyl) -6- (4 "-sulfo-3" -aminoanilino) anthrapyridazones.



   A preferred class of anthrone dyes are the anthrapyridones, which are light-fast, light red dyes. This preferred class can be represented by the following structural formula:
EMI4.2
  where Y is hydrogen or the sulfonic acid group, R is an alkyl, aryl or acyl radical, R 'is a hydrogen atom or an alkyl radical and Ar is an alkyl radical which can be substituted, in particular with groups that make it soluble, such as sulfo or carboxyl groups .



   The phthalocyanine group is a particularly stable and strongly colored chemical structure. Various amino-substituted phthalocyanines, including many that are sulfonated, carboxylated, or otherwise substituted with an acidic group. can be used. Amino groups can be attached directly to the
Phthalocyanine rings or sit in a side chain.



   e.g. in the form of an aminomethyl group. Such
Products can be made from phthalocyanine itself by treatment with methylolphthalimide and sulfuric acid as described in US Pat. No. 2,761,868. The sulfonation can take place simultaneously under favorable conditions, and up to 4
Aminomethyl groups can easily be introduced as well as up to 4 sulfonic acid groups. Phthalocyanine carboxylic acids can also be amino methylated in the same way. Similarly, phthalocyanines such as. B. those, which 1 to 4
Contain chlorine atoms, are sulfonated or aminomethylated. The total number of substituents on one
Phthalocyanine molecule should not exceed 9.

  The
Phthalocyanines are used either as metal-free phthalocyanines or in the form of their copper, cobalt, nickel or other metal complexes. The copper phthalocyanine radicals containing 2 or 3 sulfo groups are preferred.



   The dyes of the present invention differ from known dyes in that 1 or 2 hydrogen atoms of a known dye or optical brightener are replaced by the remainder:
EMI5.1
 are replaced, where R is hydrogen, an acyl group or an alkyl group having 1 to 4 carbon atoms and R "is hydrogen or OR.



   The methylolatable bond, viz
EMI5.2
 or the predecessor bond
EMI5.3
 can be attached to any of the above-mentioned components by reacting iminobispropionamide or iminobispropionitrile with dye precursors or dyes which have radicals, such as. B. have an acyl (e.g. sulfo, carboxy or triazinyl) or an acyl halide (e.g. halosulfonyl, halocarbonyi or halotriazinyl) radical or a reactive halogen, mercapto or phenolic hydroxyl group , be appended.



   The dyes according to the invention are produced in various alternative ways in which an iminobispropionitrile or iminobispropionamide function is linked to the dye component or a part thereof. In the case. that an iminobispropionitrile function is attached, the nitrile radicals are then hydrolyzed to amido radicals. The final step consists in the reaction of the amido functions with formaldehyde or a formaldehyde-releasing agent in order to introduce at least one methylol group on the amidofinction.

  The first step in the overall preparation is the reaction of iminobispropionitrile or iminobispropionamide with a dye or a dye precursor or an intermediate which contains an acylating or alkylating group by which the iminobispropionitrile or iminobispropionamide function is substituted. Examples of such alkylating or acylating groups are: chlorosulfonyl, chlorocarbonyl, carboxylic acid anhydride, halomethylaryl, activated haloaryl (e.g. o- or n-nitrohaloaryl), activated vinyl (e.g. vinylarylsulfone), mono- and dihalo-s-triazinyl etc.



   This reaction can be carried out under conventional conditions, e.g. B. in an aqueous or non-aqueous medium in the presence of an acid binder, such as. B. of alkali carbonate, alkali hydroxide or a tertiary organic amine. It is not necessary that the acylating or alkylating group be a complete dye molecule. It can be provided by part of a dye residue, e.g. by a coupling or diazonium component which is suitable for the production of azo dyes or a mono- or dihalotriazinyl structure. Optionally, the iminobispropionitrile or iminobispropionamide radical can be introduced into a dye or dye precursor by direct cyanoethylation, provided that the dye or dye precursor contains an amino function that can be cyanoethylated.

  Examples of such functional groups are the sulfamyl, carbamyl and amino groups.



   If a bispropionitrile results from the aforementioned reactions, it will lead to over; the cyano groups in amido groups hvdrolysiert. De Xvdrolvse is applied in an aqueous medium in the presence of an acid such as e.g. B. sulfuric acid, and carried out at room temperature, or by treatment with alkaline hydrogen peroxide. If preferred, the hydrolysis stage can be preceded by other stages. which are necessary. to convert a coupling or diazo component into an azo dye.

 

   The tsminobis-dronionamide intermediate products obtained in the hydrolysis reaction are easily converted into the finished dyes according to the invention.



  by treating them with at least 2 moles of formaldehyde and preferably with an excess at temperatures in the range of 20-90 "C and preferably in the range of 20-65" C at a pH above neutral, e.g. at pH 7.2 to about 10 until methylolation is complete. The methylol groups can be converted into alkoxymethyl groups by treatment with an alkanol in a strongly acidic medium.



   With a suitable choice of solvents, the above synthetic steps can equally successfully be used for the synthesis of dyes which do not contain any water-solubilizing groups. The dyes obtained can be applied to silk, nylon and wool by the usual dyeing methods and give dyeings with superior color fastness.



   As stated above, the compounds obtainable according to the invention are particularly suitable for coloring polymeric substances which are characterized by a content of reactive hydrogen atoms. They show extraordinarily high color yield when properly applied and can be used either alone or simultaneously with textile auxiliaries to impart both color and crease resistance in one step.



   Among the polymeric materials which are particularly favorably treated with the dyes according to the invention are the cellulose derivatives, such as rayon and cotton, superpolyamides such as nylon, natural proteinaceous substances such as wool, silk, casein, zein and hair, and synthetic resins such as these Phenolic resins.



   The method of application to non-textile material for the dyes according to the invention follows the usual techniques for using known methylolated dyes. The dye is dissolved in an aqueous medium with an acidic catalyst and the polymeric material is immersed therein. After a sufficient period of immersion, the material is removed, dried and then heated to fix the dye on the substrate. Various suitable application techniques are illustrated in the following examples.



   The following examples further illustrate the invention.



   example 1
EMI6.1
 A. m-Nitro-N, N-bis (2-cyanoethyl) -benzenesulfonamide
EMI6.2

10.0 g (0.045 m) m-nitrobenzenesulfonylochloride, followed by 5.6 g (0.045 m) 3,3'-iminodipropionitrile are added to 50 moles of stirred pyridine, the temperature being maintained at 15-20 "C. The solution is then heated to 50 ° C. for 2 hours. Then it is concentrated under reduced pressure until a precipitate begins to appear and is finally poured into 400 ml of a well-stirred ice-water mixture.

  The precipitate is filtered off, washed with 1.5 liters of ice water and dried in vacuo at ambient temperature, 13.1 g (94 lo of theory) of m-nitro-N, N-bis- (2-cyanoethyl) - benzene sulfonamide obtained from F 137-138 C.



  B.3, 3 '- [(m-Nitrobenzenesul! Onyl) -irninoTbispmpionamide
EMI6.3

77.8 g (0.253 m) of m-nitro-N, N-bis (2-cyanoethyl) benzenesulfonamide are added in portions to 250 ml of stirred concentrated sulfuric acid at temperatures below 20 ° C. After the addition is complete, the solution is stirred for 5 hours at room temperature, poured onto 2 liters of well-stirred ice-water mixture, filtered and the filtrate is adjusted to pH 8 by adding concentrated ammonium hydroxide at 15-20 ° C.

  The precipitate is filtered off, washed with 500 ml of water and dried in the air, 75.5 g (87% of theory) of 3,3'- [(-nitrobenzenesulfonyl) -iminoj-bispropionamide in the form of a light beige powder received from F = 199-200 C @.



  C. 3,3'-Metanilyliminobispropionamide
EMI7.1

A well-stirred mixture of 600 ml of water, 58.1 g (1.04 m) of iron powder and 12 ml of glacial acetic acid is heated to 70 ° C. and then in parts 131.1 g (0.38 m) of 3.3 '- [( m-nitrobenzenesulfonyl) imino] bispropionamide was added. At the end of the addition, the temperature is 90 ° C. and the mixture is then stirred at 90-95 ° C. for a further 45 minutes. The mixture is then cooled to 75% C and 250 ml of hot ethanol are added, followed by so much solid sodium carbonate that the soluble iron salts precipitate. Then activated charcoal is added and the warm mixture is filtered through diatomaceous earth and the filtrate is cooled to 0-5 ° C. for one hour. The resulting precipitate is filtered off, washed with 500 ml of ice water and dried in vacuo at 55 ° C.



  Yield 106.6 g (89% of theory) 3,3'-metanilyliminobispropionamide in the form of very light tan crystals of F 182-183.5 C.
EMI7.2




   To 200 ml of water 1.98 g of cuprous chloride, 16.88 g (0.30 mol) of sodium bicarbonate, 29.58 g (0.56 mol) of 93.4% sodium 1-amino-4-bromo-anthraquinone 2-sulfonate and 28.30 g (0.09 mol) 3,3'-metanilylimino bispropionamide were added. The mixture is stirred slowly and heated to 80 ° C. within 1 hour. After 1 hour at 80 ° C., 100 ml of water are added. The mixture is then stirred at 79-91 ° C. for 2 hours. After the reaction has ended, the product is filtered off while hot and washed with 400 ml of water at 50 ° C. The moist filter cake is slurried again in 2.5 liters of water at 87 ° C., 20 ml of ammonium hydroxide are added and the mixture is heated to 95 ° C. To the resulting solution, 30 g of salt is added to precipitate the dye product. The product is isolated and washed with water.

  Then it is redissolved in 2.5 liters of water at 95 C and 20 ml of ammonium hydroxide are added. 30 g of salt are gradually added to the solution and the whole is stirred at room temperature and filtered. The moist cake is slurried again in acetone, sucked dry and dried in vacuo at 55 ° C. Yield 21.40 g of a dark blue solid.
EMI7.3




  Sulfonation and methylolation
10 ml of 30% strength fuming sulfuric acid are added to 10 ml of cooled 99.5% sulfuric acid and the mixture is cooled to 0.degree. Then 2.0 g of the product from stage D are added over the course of 10 minutes with stirring. After stirring in an ice bath for 2 hours, the mixture is allowed to come to room temperature and stirred for a further 3 hours at 7: mmertemDeratur. The reaction mixture is then poured onto 100 g of ice, filtered and sucked dry. The moist cake is dissolved in 10 ml of water with the addition of Sn sodium hydroxide solution up to pH 9.5. To this end, 15 ml of 37% formaldehyde solution, which was previously buffered to DH 9.5, are added with stirring.

  The mixture is stirred, stirred for 6 hours at pH 9.5 at a temperature of 60-62 ° C. and then poured into 500 ml of isopropanol. The product is filtered off, washed with acetone and dried in vacuo at room temperature. Yield 2.30 g of a dark blue product.



   When cotton is dyed in a 1.5 Q'o shade by padding using the procedure described below with 20% maonesium chloride.



     based on the weight of the dye (OWD) as acid catalyst, with H 4, a red-blue color is obtained. The coloring is very moisture-proof, washable and perspiration-proof. The fixation of the dye on the cotton Q is about 75 0/0.



  Process for staining blocks
A 1.5 o / o tint based on the weight of the fabric (OWF) is obtained using 0.75 g of dye per 50 ml of water. A 2 O / o tint is obtained using 1 g / 50 ml OWF.



   The dye is pasted with water until it goes into solution. It is then made up to 100 ml and the pH is adjusted to 47, if necessary by adding an acid, usually hydrochloric acid.



   One of the following a. Magnesium chloride b. Ammonium chloride c. Ammonium sulfate d. Ammonium gluconate e. Triethanolamine hydrochloride added, the amount being 10 to 40% based on the weight of the solid dye, preferably 10 to 20% of the catalyst OWD (i.e. based on the weight of the dye).



   The dye solution is padded onto a yard of 7 inch (17.8 cm) wide 80 square cotton using a dip and a pinch. The padded cotton is then net getrock.



   The dry, padded cotton is then thermally set for 5 minutes to 30 seconds at 135 to 190 ° C., preferably for 11/2 minutes at 177 ° C. Then it is soaped at the boil for 5 minutes, rinsed and dried.



   The amount of dye fixed on the fiber is then quantified using one of the following two methods:
1. Comparison of the spectrophotometric reflectance curve of the dyed cotton before and after soaping.



   2. Extract the dye from the tissue by dissolving the stained tissue in concentrated sulfuric acid, diluting with ice water and measuring the spectrophotometric transmission of the solution.



   A comparison of the curve of the dyed cotton before and after soaping is expressed as the percentage fixation of the dye on the cotton.



   Example 2
EMI8.1

The cold aqueous diazonium solution, which is obtained from 15.72 g (0.05 M) 3,3'-metanilyliminobispropionamide, is converted into a solution of 12.72 g (0.05 M) 3-methyl-1-p-sulfophenylpyrazolin-5-one in 300 ml of water containing 20.8 g (02 M) sodium carbonate, stirred. The reaction mixture is stirred at room temperature for 2 hours, the pH is adjusted to 6.9 with dilute hydrochloric acid, then heated to 50 ° C., with stirring, pure salt is added to precipitate the dye, and the slurry is dissolved in an ice water bath 5 0C cooled.

  The product is filtered off, washed three times with 50 ml of 15% strength salt solution, then with 10 mol of water and dried in vacuo at 55 ° C. Yield 32.0 g of an orange dye of 80% purity (85% theoretical yield) .



   A solution of 12.03 g of the above dye in 100 ml of water is adjusted to pH 9.5, and then 32.43 g of 37% aqueous formaldehyde, the pH of which was previously adjusted to 9.5, are added.



  The mixture is stirred at 65 ° C. for 6 hours, the pH value being kept at 9.5, then it is cooled and poured into 2.0 liters of stirred isopropyl alcohol.



  The precipitate is filtered off with 500 ml of isopropyl alcohol. washed followed by 700 ml of ethyl ether and dried in vacuo at room temperature, wherein
12.24 g of a yellow dye are obtained.



   Pad dyeing on cotton in a 1.5% tint using 20% magnesium chloride OWD gives a light green-yellow. The fixation at pH 6.1 is 900/0, at pH 4.0 95 0/0. Both dyeings have excellent resistance to wet pressing, washing and perspiration.



   Example 3
EMI8.2
  
The cold, aqueous diazonium solution, which is obtained from 15.72 g (0.05 M) of o-amino-N, N-bis (2-carbamylethyl) benzenesulfonamide, is dissolved in a solution of 12.72 g (0.05 M) 3-methyl-1-p-sulfophenylpyrazolin-5-one in 300 ml of water containing 20.8 g (0.2 M) of sodium carbonate, stirred. The solution is stirred for 45 minutes at room temperature, then the pH is adjusted to 6.5 with dilute hydrochloric acid and the solution is filtered through diatomaceous earth. The filtrate is heated to 50 ° C., and 162 g of salt are then added in portions with stirring. The precipitate is filtered off, washed twice with 100 ml of 20% salt solution above and then with 50 ml of 10% salt solution and dried at 55 ° C. in vacuo.



  Yield 43.3 g of an orange powder.



   A solution of 12.03 g of the above dye in 150 ml of water is adjusted to pH 9.5, and then 32.43 g of the above 37 aqueous formaldehyde solution of pH 9.5 are added. The reaction mixture is kept for 6 hours at pH 9.5 and 65 ° C., then cooled to 25 ° C., filtered through diatomaceous earth, and the filtrate is poured into 3 l of well-stirred isopropyl alcohol. The precipitate is filtered off, washed with isopropyl alcohol and ether and dried in vacuo at room temperature. Yield 6.80 g of an orange powder.



   Cotton is dyed with the product by padding it in a 2% shade. When using 10 0 / o OWD ammonium chloride at pH 6.1, the fixation is 83 0/0. When using 20 O / o OWD magnesium chloride at pH 4, the fixation is 86 O / o. In both cases, a light, green-yellow hue is obtained on the cotton.



   Example 4
EMI9.1

By slurrying 27.38 g (0.085 M) 3 methyl 1- (2,5-dichloro-4-sulfophenyl) pyrazolin-5-one in 600 ml water, adjusting the pH to 7.0 and adding A coupling solution is prepared 36.04 g (0.34 M) solid sodium carbonate. A cold diazonium solution obtained from 26.73 g (0.085 M) 3,3'-metanilyliminobispropionamide is added to this. The reaction mixture is stirred at room temperature for 2 hours, heated to 50 ° C., and then salt is added to precipitate the product, which is filtered off, washed five times with 50 ml of the above salt solution each time and dried at 60 ° C. in an atmosphere oven. Yield 83.2 g of a yellow dye.



   A solution of 75.27 g of the above dye in 200 ml of water is adjusted to pH 9.5, and then 120 g (1.48 M) 37% of the above aqueous formaldehyde, the pH of which was previously adjusted to 9.5.

 

  admitted. The mixture is stirred for 6 hours at 65 ° C., the pH value being kept at 9.5, then cooled and poured into 3.0 l of well-stirred isopropyl alcohol. The precipitate is filtered off and dried in vacuo at room temperature , 63 g of a yellow dye are obtained.



   Pad dyeing on cotton gives a light, green-yellow shade of 2 ovo dyeing, 20% OWD magnesium chloride at pH 4 as an acid catalyst gives a dyeing of excellent resistance to wet pressing, washing and perspiration and good resistance to abrasion. The fixation was 83%.



   Example 5
EMI9.2
  
If 3-amino-4-methoxy-N, N-bis- (2-carbamylethyl) -benzoisulfonamide is used in the process of Example 2 (prepared from 3,3-nitro-4-methoxybenzenesulfonyl chloride by the process of Examples 1A, 1B and 1C), a product is obtained with an actual dye content of 80% and a total formaldehyde content of 4.5%. It dyes cotton pale yellow with pad dyeing in a 2 O / o shade using 10 O / o OWD ammonium chloride at pH 5.6. The fixation is 88 0/0. The coloring is very real to wet pressing, washing and perspiration.



   Example 6
EMI10.1

To a slurry of 15.97 g (0.05 M) of H-acid in 225 ml of water, as much as 20 of the above aqueous sodium hydroxide solution is added until phenolphthalein indicator paper shows a positive reaction, and the solution obtained is as much as 20% The above acetic acid is added so that blue laughing mousse paper indicates a positive reaction. The solution is cooled to 14 ° C. in an ice water bath, and then 9 ml of acetic anhydride are added all at once, the temperature rising to 17 ° C. taking place. The ice bath is removed, the solution is stirred for 1 hour and then sufficient solid sodium carbonate is added that the reaction against phenolphthalein indicator paper is positive.

  The solution is then heated to 45 ° C. for half an hour, cooled, and the pH value is adjusted to 9.9 with sodium carbonate. An aqueous diazonium solution, which was obtained from 15.72 g (0.05 M) 3,3'-metanilylimino-propionamide, prepared according to Example 1C, and the reaction mixture is then stirred into this solution of acetyl H-acid in the cold is 1/2 hour



  touched. The solution is adjusted to pH 6.5, stirred with activated charcoal for 15 minutes, filtered through diatomaceous earth, and the filtrate is poured into 3.0 l of well-stirred isopropyl alcohol. The precipitate is filtered off, washed with a mixture of 500 ml of isopropyl alcohol and 100 ml of water and dried in vacuo at 55 ° C. Yield 46.7 g of a brownish-red dye. A solution of 18.74 g of the above dye in 100 ml of water is adjusted to pH 9.5, and then 32.43 g of a 37% aqueous formaldehyde solution of pH 9.5 are added. The reaction mixture is stirred for 6 hours at 65 ° C., the pH being kept at 9.5 is then filtered warm and the filtrate poured into 3.0 l of well-stirred isopropyl alcohol.



  The precipitate is filtered off, washed with 500 ml of isopropyl alcohol and then with 700 ml of ethyl ether and dried in vacuo at room temperature.



  Yield 19.01g dye.



   When cotton is dyed in a 2% shade using 20% OWD magnesium chloride and a pH of 6.5, a brownish-red shade is obtained which has very good fastness to wet pressing, washing and perspiration.



   Example 7
EMI10.2

Sufficient solid sodium carbonate is added to a solution of 18.66 g (0.05 M) acetyl-H acid (pH 7.0) in 300 ml water to bring the pH to 9.9. A cold, aqueous diazonium solution, which was obtained from 15.72 g (0.05 M) o-amino-N, N-bis (2-carbamylethyl) -benzenesulfonamide, is then stirred into this solution, and the reaction mixture becomes stirred for half an hour. The solution is adjusted to pH 7.4 with dilute hydrochloric acid, heated to 50 ° C., and 440 g of sodium chloride are added with stirring. The slurry is cooled to room temperature and the precipitate is filtered off, washed with 200 ml of 20% brine and air dried.

  The crude dye is placed in 500 ml of dimethylformamide, stirred for half an hour at 50 ° C., filtered, and the filtrate is poured into 3 l of well-stirred isopropyl alcohol. The resulting precipitate is filtered off, washed with 500 ml of isopropyl alcohol and dried at 55 ° C. in vacuo.



  Yield 11.99 g of a dark red-brown powder.



   A solution of 11.44 g of the above dye in 150 ml of water is adjusted to pH 9.5, and then 32.43 g (0.4 M) of the above aqueous formaldehyde solution of pH 9.5 are added. The solution is stirred at 65 "C and pH 9.5 for 6 hours, cooled to 25" C, filtered through diatomaceous earth, and the filtrate is poured into 3 liters of well-stirred isopropyl alcohol. The precipitate is filtered off, washed with 250 ml of isopropyl alcohol and dried in vacuo at room temperature. Yield 9.05 g of a dark red powder.



   When the product is pad-dyed on cotton in a 2 / o OWF shade using 10 O / o OWD ammonium chloride, a shade of brownish-red-orange shade is obtained. The fixation is 86 0/0.



   Example 8
EMI11.1

If 17.20 g (0.05 M) of 3-amino4-methoxy-N, N-bis (2-carbamylethyl) -benzenesulfonamide are used in Example 7, a yield of 75.7 g of a red dye of 47 O is obtained ! o real dye content.



  The methylolation of a sample of 30.42 g yields 26.36 g of a red dye with a dye content of 47%, which contains 2.49% formaldehyde and dyes cotton in light blue shades of red.



   When pad dyeing cotton, a strong blue-red shade is obtained. The fixation is 92% when 100% ammonium chloride is used as a catalyst at pH 4. The fixation is 90/0 when 20% magnesium chloride is used as a catalyst at pH 6.0. The resistance to damp pressing, washing and perspiration is excellent.

 

   Example 9
EMI11.2

If you get 12.03 g of the dye obtained by coupling diazotized 3-amino-4-methoxy-N, N-bis (2-carbamylethyl) -benzenesulfonamide in an alkaline solution of 5-hydroxynaphthalene-1-sulfonic acid if methylolated by the usual method, 6.05 g of a dye are obtained which gives a red tint on cotton.



   The block dyeing of cotton in a 2 0/0 shade results in a brick-red shade. The fixation is 80% when 10% ammonium chloride is used as a catalyst at pH 4. The authenticity to moist pressing, washing and perspiration is excellent.



   Example 10
EMI11.3
  
9.4 g (0.03 mol) of p-amino-N, N-bis (2-carbamyl ethyl) -benzenesulfonamide are dissolved in a mixture of 100 ml of water and 20 ml of concentrated hydrochloric acid. The solution is cooled to 0 ° C. with ice, stirred, and then a solution of 2.31 g (0.033) sodium nitrite in 30 ml of water is added. The mixture is stirred for half an hour, the solution being kept cold by the periodic addition of ice. Excess nitrous acid is destroyed with sulfamic acid, 225 ml of diazo solution being obtained.



   9.58 g (0.03 M) H-acid are dissolved in 100 ml of water with 5N sodium hydroxide. This solution is ice-cooled and 10 ml of acetic anhydride is added. The solution is stirred for half an hour and then 31.6 g (0.3 M) sodium carbonate is added. The diazonium compound obtained above is added rapidly with stirring. The coupling takes place immediately. The solution is stirred for half an hour, heated to 40 ° C., and 100 g of salt are added.



  The mixture is then cooled to room temperature, filtered, washed with 15 0 / above salt solution and dried in a vacuum oven at 60 ° C. and then at 100 ° C. 21 g of dye are obtained in this way.



   20 g of the above dye are mixed with 100 ml of water, the pH of the slurry is adjusted to 9.5, 33 g of 37 0 / above formaldehyde solution are added, and the mixture is stirred for 6 hours at 65 ° C., the pH -Value is kept at 9.3 to 9.5. 2000 ml of isopropanol are then added, the solution is filtered off and the dyes are washed with 300 ml of isopropanol. The product is dried in a vacuum oven at room temperature.



   Example 11
EMI12.1

To a solution of 31.5 (0.11 m) sodium 4amino-diphenylamine-2-sulfonate in 500 ml of water, which contained 16.4 g (0.2 m) of sodium acetate, a solution of 37.9 g (0 , 10 m) 4-chloro-3-nitro-N, N- (2carbamylethyl) -benzenesulfonamide in 75 ml of water and 100 ml of dioxane were added. The partial solution obtained is heated to 90 ° C. within three hours, kept at 90 ° C. for one hour, cooled to 60 ° C. and filtered through diatomaceous earth. The filtrate is heated again to 60 ° C. and sodium chloride is added so that the product precipitates.

  The filtered product is washed with 200 ml of 10% salt solution above and dried in an atmosphere oven at 55 ° C. Yield 43.6 g of a yellowish brown powder.



   A solution of 12.58 g of the above powder in 150 ml of water is adjusted to pH 9.5, and 32.43 g of an above aqueous formaldehyde solution of pH 9.5 are added. The solution is kept at pH 9.5 and 65 ° C. for 6 hours, then cooled to 25 ° C., filtered through diatomaceous earth and the filtrate is poured into 3 l of well-stirred isopropyl alcohol. The precipitate is filtered off, washed with 500 mol of isopropyl alcohol and dried in vacuo at room temperature. Yield 10.61 g of a yellow-brown pul.



  verse.



   The product dyes cotton with a brownish-yellow tint of good fastness to moisture soils,
Example 12
EMI12.2

To 70 ml of chlorosulfonic acid, while stirring and cooling so that the temperature does not exceed 30 ° C., 11.5 g (0.02 m) copper phthalocyanine are added and the reaction mixture is then heated to 135 ° C. and kept at 135-137 ° C. for two hours, cooled, stirred at room temperature for 16 hours and poured into a well-stirred mixture of 165 ml of water, 94 g of sodium chloride and 150 g of ice.



  The precipitate is filtered off and washed with 500 ml of ice water. The moist sulfonyl chloride is slurried with 100 g of ice and 100 ml of water and the pH is adjusted to 6.5. A cooled mixture of 19.25 g (0.06 m) of 3,3'-metanilyliminobispropionamide in 100 ml of acetone and 100 mol of water is then added all at once. The reaction mixture is stirred for 11/2 hours at room temperature and for one hour at 43 ° C., the pH value being constantly kept at 6.5, and then enough sodium chloride is added that the dye precipitates. The precipitate is filtered off, washed with 100 ml of saturated saline solution and dried in vacuo at room temperature. Yield 30.46 g of a green-blue dye.



  The crude dye is placed in 750 ml of water, the pH is adjusted to 7.5 and the solution is heated to 50 ° C., filtered through diatomaceous earth and the filtrate is poured into 20.0 l of well-stirred isopropyl alcohol. The precipitate is filtered off, washed with a mixture of 200 ml of water and 800 ml of isopropyl alcohol, followed by 250 ml of isopropyl alcohol, and dried in vacuo at 55 ° C. Yield 19.37 g of the green-blue dye.



   A solution of 18.26 g of the above dye in 100 ml of water is adjusted to pH 9.5 and then 97.29 g of a 37% above aqueous formaldehyde solution of pH 9.5 are added. The reaction solution is stirred for 6 hours at 65 cC, the pH value being kept at 9.5, cooled and poured into 3.0 l of well-stirred isopropyl alcohol. The precipitate is filtered off, washed with 500 ml of isopropyl alcohol, followed by 400 ml of ethyl ether, and dried in vacuo at Zinnertem- temperature. Yield 18.91 g of a green-blue powder which contains 5.06 O / u of bound formaldehyde.



   Block-dyeing the product in the 20 / above shade on cotton gives a turquoise shade of excellent fastness to wet pressing. 90% fixation is obtained by using 10% ammonium sulfate OWD as an acid catalyst at pH 5.7.



   Example 13
EMI13.1

A solution of 7.85 g (0.021 m) of 4,4'-diaminostilbene-2,2'-disulfonic acid in 75 mol of water, 50 ml of acetone and 8 ml of 20% sodium hydroxide solution at 0-5 ° quickly becomes a solution of 7.85 g (0.042 m) of cyanuric chloride in 70 ml of acetone were added. After half an hour the pH is adjusted to 6.5 with NaOH and then a slurry of 3.38 g (0.042 m) of 3,3'-metanilyliminobispropionamide in 75 ml of water and 50 ml of acetone is added. During the addition, the pH is kept at 6-7 and the temperature below 10 ° C. After one hour the temperature is increased to 30 ° C. maintaining a pH of 6.5 at all times.

  4.37 g (0.047 m) aniline are then added and the reaction mixture is heated to reflux for 21 /: hours at 78 ° C., cooled to 25 ° C. and the product is filtered off, washed with 50 ml water and dried in an atmosphere oven at 55 ° C. Yield 28.3 g of a yellow powder.



   A solution of 26.8 g (0.02 m) of the above material in 150 ml of water of pH 9.5 is treated with 32.43 g (0.4 m) of a 37% aqueous formaldehyde solution of pH 9.5 and the resulting solution is treated The mixture is heated to 65 ° C. for 6 hours while stirring, the pH value being constantly kept at 9.5. The solution is cooled to 25 ° C., filtered through diatomaceous earth and the filtrate is poured into 3.5 l of well-stirred isopropyl alcohol. The precipitate is collected by filtration, washed with 1.5 liters of isopropyl alcohol followed by 300 ml of ether and dried in vacuo at room temperature. Yield 27.86 g of a product with a content of 3.18% formaldehyde (1.74 methyl groups).

 

   The compound has a high affinity for cotton even at room temperature and can be applied from a detergent bath of a nonionic or anionic detergent or by the pad dyeing process. When exposed to ultraviolet light, it emits a blue fluorescence.



   Example 14
EMI13.2
  
A slurry of 60.1 g (0.1 m) of the hydrochloride salt of alkali blue monosulfonyl chloride in 11% of ice and water is adjusted to pH 6.0 and treated with a solution of 28.6 g (0.1 m) 3.3 '- ( p-aminophenylimine) bispropionamide hydrochloride is added to 100 ml of water at 0-5 "C. The mixture is slowly warmed to 45" C, whereby a pH value of 6.0 is maintained, held at 45 "C for two hours, filtered through diatomaceous earth and the filtrate is treated with sodium chloride at 25 ° C. The slurry is cooled to 25 ° C., filtered and the residue is washed with 200 ml of 10% saline solution and dried at 55 ° C. Yield 61.3 g of a blue powder.



   A solution of 16.30 g of the above powder in 150 ml of water is adjusted to pH 7.5 and then 32.43 g of a 37% above aqueous formaldehyde solution of pH 7.5 are added. The solution is kept at room temperature (25-30 "C) and pH 7.5 for 24 hours, then filtered through diatomaceous earth and the pH of the filtrate is carefully adjusted to 6.5. The filtrate is then poured into 3 liters of well-stirred isopropyl alcohol and the precipitate is filtered off, washed with 500 ml of isopropyl alcohol and dried in vacuo at room temperature, yielding 14.3 g of a dark blue powder.



   When pad dyeing cotton, red-blue shades of good fastness to wet pressing are obtained.



   Example 15
EMI14.1

11.0 g (0.035 mol) of m-amino-N, N-bis (2-carbamylethyl) benzenesulfonamide are added to 50 ml of water, 20 ml of concentrated hydrochloric acid and 55 g of ice with stirring. A solution of 2.45 g (0.035 mol) of sodium nitrite in 15 ml of water is then added.



   The mixture is stirred for half an hour at 0 to 5 "C and excess nitrous acid is destroyed with sulfamic acid. The diazo solution is added to a cooled slurry of 5.58 g (0.0175 m) of H acid in 150 ml of water and the stirred To the mixture, 20 g of anhydrous sodium acetate are added in small portions within 5 minutes.



  The mixture is then stirred at 5 to 7 ° C. for a further half an hour. The mixture is warmed to room temperature, the pH is adjusted to 8.0 with 20% sodium hydroxide solution and the solution is saturated with salt. The dye precipitates as tar and solidifies quickly. The precipitate is filtered off, redissolved in 400 ml of water at 45 ° C., 120 g of salt are added and the mixture is cooled to room temperature. The dye precipitates on addition of the salt and becomes solid. The solid is filtered off and dried at 51 ° C. 15.8 g of product being obtained.



   15 g (0.0148 mol) of the above product are dissolved in 50 ml of water and the pH is adjusted to 9.5. To this end, 50 g of 37 formaldehyde solution, the pH of which had previously been adjusted to 9.5, are added. The mixture is stirred, heated for 6 hours at 64-65 ° C., poured hot into 600 ml of isopropanol, filtered, washed with acetone and dried in vacuo at room temperature.



   Example 16
EMI14.2
 A. m-Nitro-N, N-bis (2-cyanoethyl) benzamide
EMI14.3

92.8 g are added to a cooled solution of 61.60 g (05 m) 3,3 'iminodipropionitrile and 39.55 g (0.5 m) pyridine in 500 ml dioxane at such a rate that the temperature is 17-19 ° C. (0.5 m) m-nitrobenzoyl chloride in 100 ml of dioxane was added dropwise.



  After the addition is complete, the solution is stirred for one hour at room temperature and then for another half hour at 50.degree. Then activated charcoal is added, the warm solution is filtered through a diatomaceous earth filter and the filtrate is poured into 2.5 liters of well-stirred ice-water mixture. The precipitate is filtered off. washed with 1.0 l of water and dried at 65 0C in an atmospheric oven. From loot 111.9g: (81.9 O / o of theory) m-Nitro-N, N-bis (2-cyanoäthvl) -benzamide in the form of pale beige crystals from F 118119.5 CC.



  B. m-nitro-N, N-bis (2-carbamylethyl) benzamide
EMI15.1

124.6 g (0.456 m) m of nitro-N, N-bis (2-cyanoethyl) benzamide are added to 500 ml of concentrated sulfuric acid at 0-5 C with stirring. When the addition is complete, the mixture is stirred for 5 hours at room temperature, poured into 2 l of well-stirred ice-water mixture and the dark solution is filtered through a diatomaceous earth filter. The filtrate is adjusted to pH 7 by adding concentrated ammonium hydroxide at 10-20 ° C. and the resulting precipitate is filtered off, the filter cake is washed with 31% water and dried at 45 ° C. in vacuo. Yield 111.5 g (78.6% of theory) of m nitro-N, N-bis (2-carbamylethyl) benzamide in the form of pale beige crystals from F 172.5-1735 C.



  C. m-Amino-N, N-bis (2-carbamylethyl) benzamide
EMI15.2

A stirred mixture of 500 ml of water, 52.5 g (0.94 n) of iron powder and 6 ml of glacial acetic acid is heated to 75 ° C. and then in parts 104.8 g (0.34 m) of m-nitro-N, N-bis (2-cyanoethyl) benzamide added.



  The temperature is allowed to rise to 90 ° C. during the addition and the mixture is kept at 9095 ° C. for 15 minutes after the addition has ended.



  The mixture is then cooled to 70 ° C., enough solid sodium carbonate is added that the soluble iron salts precipitate and the warm mixture is filtered through diatomaceous earth. The filtrate is evaporated to dryness under reduced pressure at 40-45 C and the residue is taken up in 300 ml of hot ethanol, which contains activated carbon and diatomaceous earth, and the ethanol solution is filtered hot. The filtrate is poured into well-stirred dioxane and ethyl ether is added to complete the precipitation. The precipitate is filtered off, washed with 11 ethyl ether and dried in vacuo at room temperature. Yield 97.3 g of m-amino-N, N-bis (2carbamylethyl) benzamide in the form of pale beige crystals which decompose at 109 C with foaming.

  A portion recrystallized from isopropyl alcohol decomposes at 162 ° C and is analyzed as sesquihydrate.
EMI15.3




   A cold aqueous diazonium solution obtained from 13.92 g (0.05 m) m-amino-N, N-bis (2- carbamvläthyl) benzamide is poured into a solution of 12.72 g (0.05 m) 3-methyl-1- p-sulfophenvl-pyrazolin-5-one in 300 ml of water containing 20.8 g (0.2 m) of sodium carbonate, stirred. The reaction mixture is stirred for 3 hours at room temperature. filtered off. the filtrate is heated to 50 ° C. and the pH is adjusted to 7.0, whereupon sodium chloride is added to precipitate the dye while stirring.

  The mixture is cooled to 25 ° C. and filtered. the filter cake is filled with 100 ml of 20% salt solution from 100 ml of 10% salt solution. washed and dried in vacuo at 50.degree. Yield 40.4 g of an orange powder (yield 89% of theory).



   A solution of 32.31 g of the above powder in 150 ml of water is adjusted to pH 9.5 and then 60 g of 37 above aqueous formaldehyde solution, the pH of which has been adjusted to 9.5, are added. The reaction mixture is stirred for 6 hours at 65 ° C., the pH value being kept at 9.5, cooled, diluted with isopropyl alcohol to precipitate the dye and the isopropyl alcohol is then decanted off.

 

  The residue is extracted with ether, filtered, the filter cake is washed with ether and dried in vacuo at room temperature. Yield 2-7.8 g of a yellow dye.



   When the cotton is dyed in blocks, a light green-yellow shade is obtained with excellent fastness to wet pressing, washing and acidic perspiration. Using 20% magnesium chloride OWD, the fixation is 85% at pH 4 and 80% at pH 6.5. The resistance to alkaline perspiration and the abrasion fastness are good.



   Example 17
EMI15.4
   A. 3,3'-s [2-fN-thyl-m-toluidino) -äthylyimino} -dipropionitrite
EMI16.1

89 g of N-ethyl-N- (2-aminoethyl) -m-toluidine are dissolved in 500 ml of t-butanol and 5 drops of 5N sodium hydroxide. 53 g of acrylonitrile are added dropwise to the stirred solution at normal temperatures in half an hour. The reaction mixture is then stirred at normal temperatures for 60 hours. The product is then isolated from the reaction mixture by vacuum distillation. In this way, 94 g of 3,3 '{[2- (N-ethyl-m-toluidino) -ethyl] -imino} -dipropionitrile are obtained in analytically pure form with a boiling point of 155-156 ° C. at 0.1 mm.



  B. 3,3 '- {[2- (N-ethyl-m-toluidino) -ethyl] -imino} bispropionamide
EMI16.2

28.4 g of 3,3 '- {[2- (N-ethyl-m-toluidino) -ethyl] -imino} dipropionitrile are added in small portions to 100 ml of concentrated sulfuric acid with stirring at 30-40 ° C. within half an hour . The reaction mixture is then stirred for a further 3 hours. The reaction mixture is then poured onto 1000 g of ice and made strongly alkaline by adding concentrated ammonium hydroxide. The product is suction filtered, washed with water and dried in an atmosphere oven at 50 ° C.



   This gives 30.6 g of 3,3 '- {[2- (N-ethyl-m-toluidino) -ethyl] -imino} bispropionamide with a melting point of 78-79 ° C.
EMI16.3




   22.7 g of 7-aminonaphthalene-1,3-disulfonic acid who eat diazotized and the aqueous suspension of the diazotized salt is dissolved in a solution of 24 g of 3,3 '{[2- (N-ethyl-m-toluidino) -ethyl] imino} bis-propionamide, which were prepared according to Example 17 B and stirred in 20 parts by volume of concentrated hydrochloric acid in 300 ml. Then 62 parts of sodium acetate hydrate are added all at once. After the coupling reaction has ended, the reaction mixture is stirred for half an hour. Then 1600 ml of ethanol are added and the whole mixture is stirred for another half an hour. The dye is then filtered off, washed with ethanol and dried in an atmosphere oven at 50 ° C. 47.5 g of an orange-red solid are obtained in this way.



  Purification and methylolation 47.5 g of the above solid are leached with 300 g of water for half an hour. Then the dye is dissolved in 1000 ml of water with a sufficient amount of concentrated ammonium hydroxide to achieve the solution. 150 ml of glacial acetic acid are added to the clarified dye solution and the whole mixture is diluted to 4000 ml with ethanol. After stirring for one hour, the dye is filtered off, washed with ethanol and dried at 50 ° C. in an atmosphere oven.



   20 g of the above dye are added to 100 ml of a 37 formaldehyde solution, the pH of which has been previously adjusted to 9.0. The reaction mixture is stirred for 24 hours at room temperature, the pH being kept at 9.0, if necessary, by adding 5N sodium hydroxide solution. Then the reaction mixture is poured into 2000 ml of acetone.



  The precipitated dye is filtered off with suction, washed with 300 ml of acetone and dried over calcium chloride in vacuo at normal temperature. This gives 21.7 g of analytically pure dye.



   When the cellulose fibers are block-dyed, the product has an orange shade.



   Example 18
EMI16.4
   A. 3,3 '- (Phenylimino) bispropionamide
EMI17.1

To 200 ml of concentrated sulfuric acid, which is kept at 0 ° C., 22.0 g (0.094 m) of 3,3 '- (phenylimino) dipropionitrile are added with stirring, and when the addition is complete, the solution is stirred at room temperature for 5 hours Pour ice and then slowly add concentrated ammonium hydroxide (approximately 700 ml) at 10-15 C up to pH 9. The white precipitate is filtered off, washed with water and dried in an atmosphere oven at 60.degree. This gives 16.8 g (76% of theory) 3,3 '- (phenylimino) bis-propionamide of F 153.2-153.4 C.
EMI17.2




   42.7 g (0.1 mol) of the above aminonaphthalene-1,3-disulfonic acid are added to 300 ml of water and 25 ml (0.3 mol) of hydrochloric acid. It is then cooled to 10 ° C. with ice and the whole is diazotized with 7.0 g (0.1 mol) of NaNO in 25 ml of water, stirred for 1 hour and treated with sulfuric acid. The diazo solution is added to a solution of 24.4 g (0.104 mol) of 3,3'-phenylimino-bispropionamide in 500 ml of water and 30 ml of concentrated hydrochloric acid at 10.degree. To this end, 82 g (1.0 mol) of sodium acetate are added in small proportions. After the coupling has ended (about 10 minutes), the whole is filtered off and washed with 30% strength salt solution. The moist cake is slurried again in 1000 ml of water, 40 ml (0.2 M) of 5N sodium hydroxide solution are added and the whole is stirred for 1 hour. The product is filtered off and dried.

  It is then dissolved in 500 ml of water, 1250 ml of isopropanol are added, the mixture is heated to boiling, cooled, filtered off and the product is washed with isopropanol and dried. The yield of crude product is 73.2 g, and 58.5 g when recrystallized.



   A solution of 100 ml 37 01 formaldehyde is adjusted to pH 9.0 with Sn sodium hydroxide solution. For this purpose the above product is given. A solution is obtained by stirring at 27-28 ° C. for 1 hour and then heating to 45 ° C. After cooling to 29-30 ° C. and stirring for a further 4 hours at pH 9.0, the whole is poured into 1500 ml of acetone.



  The product is isolated by decanting, 400 ml of isopropanol are added and the mixture is stirred for 1 hour.



  The slurry is filtered and the product washed with isopropanol and dried over CaCl2 in a vacuum oven. Yield 20.31g.



   The pad dyeing of cotton in a 2.0 shade OWF with 20% magnesium chloride OWD results in a light orange shade with excellent wash fastness and wet press fastness.



   Example 19
EMI17.3
 A. 3,3 '- (N-p -nitrophenylimino) bispropionamide
EMI17.4

6.11 g (0.025 m) 3,3 '- (p-nitrophenvlimino) - dinropionitrile are slowly added to 53 ml of concentrated sulfuric acid with stirring at 0 ° C. and after the addition is complete, the resulting solution is stirred for 5 hours at room temperature. Poured onto ice and the solution is filtered through a diatomaceous earth filter. The filtrate is adjusted to pH 8 by adding concentrated ammonium hydroxide with stirring at 10-15 ° C. and the resulting precipitate is filtered off, washed with 100 ml of water and dried in vacuo at 60 ° C.

  6.64 g (95% de ThPnriP) 3 3 '- (n-Nitronhenv1irnino) - hisoronionamid are obtained in the form of light yellow crystals of F 209-210 C.



  B. 3,3 '- (p-Aminophenylimino) bispropionamide hydrochloride
EMI18.1

A well-stirred mixture of 400 ml of water, 27.9 g (0.5 m) of iron powder and 3 ml of glacial acetic acid is heated to 70 C and then 50.2 g (0.18 m) of 3,3 '- (p-nitrophenylimino) are added in portions -bispropionamide added. During the addition, the temperature rises and at the end is about 90 ° C. The mixture is stirred at 90-95 ° C. for half an hour after the addition has ended, cooled to 75 ° C. and then enough sodium carbonate is added to remove all dissolved iron salts. Then activated charcoal is added and the mixture is filtered while hot through a diatomaceous earth filter. The filtrate is acidified with concentrated hydrochloric acid against Congo red indicator paper and cooled to 0 C.

  The precipitate obtained is filtered off and dried at 40 ° C. in vacuo.



  Yield 36.1 g (70.3 o / o of theory) 3,3 '- (p-aminophenylimino) - bispropionamide hydrochloride in the form of pink crystals from F 203-204 C.
EMI18.2




   The cold aqueous diazonium solution, which was obtained from 14.34 g (0.05 m) 3,3 '- (p-aminophenylimino) bispropionamide hydrochloride, prepared according to part B, is poured into a well-stirred solution at 15 ° C. ml water, 20.8 g (0.2 M) sodium carbonate and 11.51 g (0.05 M). Sodium 3-hydroxynaphthalene-6sulfonate consists. The solution is allowed to come to room temperature and then heated to 50 ° C., whereupon sodium chloride is added to precipitate the dye. The precipitate is filtered off and washed with 400 ml of 20% saline solution. The moist cake is dissolved in 500 ml of water at 60 ° C., the solution is filtered through diatomaceous earth and the filtrate is poured into 3 l of isopropyl alcohol.

  The precipitate is filtered off, washed with isopropyl alcohol and then with ethyl ether and dried in vacuo at 45.degree. Yield 14.01g.



   A solution of 10.15 g of the above product in 150 ml of water is adjusted to pH 9.5 and then 30 g of 37% strength aqueous formaldehyde, the pH of which was previously adjusted to 9.5, is added.



  The solution is stirred for 6 hours at 65 ° C., the pH value being kept at 9.5, and then poured into a mixture of 3 l of isopropyl alcohol and 800 ml of ether. The mother liquor is decanted from the precipitate and this is dissolved in 55 ml of water for application to the fiber.



   A pad solution is prepared by mixing 20 ml of the above dye solution with 1.5 ml of 10% magnesium chloride solution and making up to 50 ml with water. The solution is padded onto 8 square cotton, air dried and fixed for 11/2 minutes at 177 ° C. (350 ° C.). The fixed dye is soaped at the boil and dried. An attractive red-brown color is obtained in this way. This dye shows excellent fastness (5) in the 3A cotton wash test, acid and alkaline perspiration fastness and wet press fastness. The fixation of the dye is 95/0, as shown by the sulfuric acid extraction and the spectrophotometric measurement of the dye solution.



   Example 20
EMI18.3

The following substances are added to 150 ml of stirred water in the following order: 1.13 R (0.0045 m of powdered cupric sulfate nentahvdrat.



  16.88 g (0.31 m) sodium bicarbonate and 27.62 4 (0.056 m) sodium 1-amino-4-bromoanthraquinone-2-sulfonate. Then a slurry of 22.62 g (0079 m) 3.3 '- (p-aminophenylimino) - bispropionamide hydrochloride, the nH value of which was previously adjusted to 5.5 with solid sodium bicarbonate, is added with slow stirring. The reaction mixture is stirred at room temperature for half an hour and the precipitate is filtered off and washed with 100 ml of 10% strength salt solution. The wet cake is slurried in 1] water and the slurry is heated to 40 ° C. with stirring, whereupon just enough 5N sodium hydroxide solution is added to effect dissolution.

  Then activated charcoal and diatomaceous earth are added, the mixture is heated to 50 ° C. and filtered through diatomaceous earth. The filtrate is heated to 45 ° C. and then 5N hydrochloric acid is slowly added dropwise until the precipitation of the dye is complete. The precipitate is filtered off, washed twice with 100 ml of water each time and then with 200 mol of 10% salt solution and dried at 45 ° C. in vacuo.



  Yield 14.71 g of a blue solid (42% of theory).



   A solution of 11.03 g of the blue solid in 150 ml of water is adjusted to pH 9.5 and then 30 g (0.37 m) of 37% aqueous formaldehyde are added, the pH of which is previously set to 9. 5 has been discontinued. The solution is stirred for 6 hours at 65 ° C., the pH value being kept at 9.5, and then poured into a mixture of 31 isopropyl alcohol and 1.61 ethyl ether. The precipitate is filtered off, washed with ethyl ether and dried in vacuo at room temperature. Yield 9.24 g of a blue dye.



   A pad bath is produced by mixing 0.75 g of the blue dye with water, adding 1.5 ml of 10% strength ammonium sulfate solution, making up to 50 ml with water and letting it stand. Then 7 ml of alcohol are added and padded onto 80 square cotton. The padded cotton is set for 11/2 minutes at 177 ° C. (350 ° C.), soaped at the boil, rinsed and dried. The cotton is then dyed with a gray-blue tint, which has excellent authenticity when wet pressing, washing and sweating. Fixation is 82%.



   Example 21
EMI19.1

8.71 g (0.015 m) of copper phthalocyanine are added to 45 ml of chlorosulfonic acid with stirring and cooling so that the temperature does not exceed 30 ° C. and the reaction mixture is heated to 140 ° C. and held at this temperature for two hours. Then it is cooled to room temperature, poured into a well-stirred mixture of 75 ml of water, 450 g of ice and 42 g of sodium chloride and the resulting precipitate is filtered off and washed with 100 ml of ice water. The moist sulfonyl chloride cake is then slurried in ice water, the pH is adjusted to 5.5 and then a slurry of 8.4 g (0.03 m) 3,3 '- (p-aminophenylimino) bispropionamide in 40 ml of ice water is made pH 5.5 added.

  The reaction mixture is stirred at 0-5 C for one hour, the pH being kept at 6.5, filtered off and the cake is washed with 50 ml of water and dried in vacuo at 45 0C. Yield 16.9 g of a solid.



   A solution of 12.97 g of the above dye in 150 mol of water is adjusted to pH 9.5 and then 32.4 g of 37% aqueous formaldehyde, the pH of which has previously been brought to 9.5, is added. The reaction mixture is heated to 65 ° C. for 6 hours, the pH value being kept at 9.5, then filtered and the filtrate is poured into 3 l of well-stirred isopropyl alcohol. The precipitate is filtered off, washed with 250 ml of ethyl ether and dried in vacuo at room temperature. Yield 12.61 g of a green-blue dye.

 

   The pad dyeing of cotton in a 1.5% OWF shade at pH 6.7 using 10% OWD ammonium sulfate gives a turquoise coloration with 96% fixation. At the same dye concentration at nH 6.6 and 20% OWD ammonium sulfate, 95% fixation is obtained.



   Example 22
EMI19.2
  
A solution of 13.34 g (0.025 m) of the blue dye, which is obtained from the condensation of bromamic acid and m-phenyldiaminesulfonic acid, is cooled to 0-5 GC and then with stirring with a solution of 4.61 g (0.025 m ) Cyanuric chloride is added to 50 ml of acetone, the pH being kept at 5.5. The solution is kept at 0-5 ° C. and a slurry of 15.77 g (0.055 m) of 3,3 '(p-aminophenylimino) dipropionamide hydrochloride in 50 ml of water, which has a pH of 5.5, becomes admitted. The temperature is then increased to 90-92 "C within 1.5 hours and held for one hour, the pH being kept constant at 6.0.

  The solution is cooled to room temperature, filtered through diatomaceous earth and the filtrate is poured into 1.5 liters of well-stirred isopropyl alcohol. The precipitate is filtered off, washed with 1.5 l of isopropyl alcohol and dried in an atmosphere oven at 55 ° C. Yield 24.8 g of a blue powder. A sample of this powder is recrystallized from a dimethylformamide-isopropyl alcohol mixture.



   16.63 g of the above powder are dissolved in 150 ml of water, the pH is adjusted to 9.5 and then 48.64 g of a 37% above aqueous formaldehyde solution of pH 9.5 are added. The mixture is heated to 65 ° C. for 6 hours, the pH value being kept constant at 9.5 by adding 20% of the above NaOH solution, if necessary, cooled to room temperature, filtered through diatomaceous earth and the filtrate stirred well in 3 liters Poured isopropyl alcohol. The precipitate obtained is filtered off, washed with 500 ml of isopropyl alcohol and dried in vacuo at room temperature. Yield 16.67 g of blue dye.



   Example 23
3 g of the dye from Example 12 are dissolved in 11 ml of water and added to an emulsion obtained by homogenizing the following ingredients:
20 g granulated sodium alginate, mixed with 545 ml water to form a paste; 10g of sodium fatty acid amide sulfonate as a surfactant and
455 grams of a petroleum based solvent having a boiling point between 160 "C and 198" C (321-388 "F).



   6 ml of the above ammonium chloride solution are added to this. It is then used to print 7 inch (17.8 cm) wide 80 square cotton. The print is dried for 5 minutes at 71 ° C. It is then acid-aged in an acetic acid / steam mixture for 21/2 minutes.



  This is followed by setting for 11/2 minutes at 177 ° C. (350 "F), followed by soaking for five minutes with boiling and drying. A brilliant turquoise print is obtained in this way.



   Example 24
EMI20.1

A suspension of 15.97 g (0.05 m) of H-acid in 300 ml of water is adjusted to pH 6.5 by adding 20 of the above sodium hydroxide solution and the resulting solution is clarified with activated charcoal and diatomaceous earth, filtered and the filtrate is with 8.20 g (0.1 m) of anhydrous sodium acetate. A cold aqueous diazonium solution, which was obtained from 15.72 g (0.05 m) of 3,3'-metanilyliminobispropionamide, is added to this coupling component solution all at once with stirring at room temperature. The pH of the mixture obtained is brought from 1.7 to 3.5 by adding solid anhydrous sodium acetate and then to 5.0 with 20% aqueous sodium hydroxide solution.



  The reaction mixture is then stirred for two hours, the pH value is adjusted to 5.0 with the above aqueous sodium hydroxide solution, and then sufficient solid sodium carbonate is added that a pH value of 9.9 is obtained. Finally, a cold aqueous diazonium salt solution obtained from 6.91 g (0.05 m) p-nitroaniline is added alternately with solid sodium carbonate in order to keep the pH at 8.0. The reaction mixture is stirred for two hours at pH 8.0 and then the pH is adjusted to 7.0 with 5N hydrochloric acid and stirred for several hours.



  The product is filtered off, washed twice with 250 ml of 20% aqueous sodium chloride solution and then partially dried at 55 ° C. in an atmosphere oven. The crude dye is dissolved in 500 ml of dimethyl form'amide at 60 "C, the solution is filtered and the filtrate is poured into 5 liters of well-stirred isopropyl alcohol. The precipitate is filtered off, washed with 500 ml of isopropyl alcohol, followed by 500 ml of acetone and with Dried at 60 ° C. Yield 26.42 g (63% of theory) of a shiny bronze, blue-black dye.



   A solution of 20.94 g (0.025 m) of the above dye in 200 ml of water is adjusted to pH 10.0 and then 32.43 g (0.4 m) of 37% aqueous formaldehyde solution are added. The mixture is stirred for 6 hours at 65 ° C., the pH value being kept at 9.5, then filtered while hot through diatomaceous earth and the filtrate is poured into 3 l of well-stirred isopropyl alcohol. The precipitate is filtered off, washed with 250 ml of isopropyl alcohol followed by 200 ml of ether and dried in vacuo at room temperature.



  Yield 17.24 g of a blue-black dye of 70% purity, which contains 8.27% of bound formaldehyde (2.43 methylol groups).



   Block dyeing on cotton in a 2% tint with 10% ammonium chloride OWD as a catalyst gives a deep blue-black color with 75-80% above fixation.



  Example 25
EMI21.1

Just enough 5N sodium hydroxide solution is added to a slurry of 15.97 g (0.05 m) H acid to effect solution and then the solution is treated with activated charcoal and diatomaceous earth, filtered and the filtrate is cooled to 0 C and to 5 , 5 set. Then a filtered solution of 9.22 g (0.05 m) of cyanuric acid chloride in
100 ml of acetone were added dropwise. The pH is kept at 5.5 throughout the addition by adding Sn sodium hydroxide solution, if necessary. The reaction mixture is stirred for 30 minutes at 0-5 "C and then a slurry of 15.72 g (0.05 m) of 3,3'-metanilyliminobispropionamide in 50 ml of water and 150 ml of acetone is added all at once.

  The ice bath is removed and the temperature is increased to 60 ° C. within 21/2 hours, the pH value being maintained at 5.5. After 11 !. stirring at 60 ° C. for hours, the solution is treated with activated charcoal and heated through
Diatomaceous earth filtered. The filtrate is poured into 3 l of well-stirred isopropyl alcohol and the precipitate is filtered off and mixed with 500 ml of isopropyl alcohol. followed by 500 ml of acetone. The semi-dry triazinyl intermediate product obtained is placed in 300 ml of water, the pH is adjusted to 7.0 and then sufficient solid sodium carbonate is added. that the DH value is 9.9.

  A cold aqueous diazonium solution, which was obtained from 8.66 g (0.05 m) of orthanilic acid, is added to the coupling component solution thus prepared. The reaction mixture is stirred for several hours at room temperature and then heated to 60-65 ° C. The pH is adjusted to 7.0 to 7.5 with dilute hydrochloric acid and partially solid sodium chloride is added with stirring. The salted out dye is filtered off, washed with 250 ml of 20% aqueous sodium chloride solution above and dried at 65 ° C. in an atmosphere oven. Yield 39.81 g of a red product (true base).



   A solution of 45.59 g of the red dye prepared as above in 350 ml of water is adjusted to pH 9.5 and then 81.1 g (1.0 m) of a 37% aqueous formaldehyde solution of pH 9.5 admitted. The mixture is stirred for 6 hours at 65.degree. C., the pH being kept at 9.5, then filtered hot through diatomaceous earth, and the filtrate is poured into well-stirred isopropyl alcohol. The precipitate is filtered off, washed with 500 ml of isopropyl alcohol followed by 30 () ml of ether and dried in vacuo at room temperature. Yield 32.0 g of a red dye containing 5.72 O / o bound formaldehyde.

 

   A 20% dyeing on cotton with 10% ammonium chloride OWD as a catalyst gives a bright red with a blue shade with a fixation of 90%.



   Example 26
EMI21.2

If 0.05 m of the diazonium salt is used in the process of Example 2, which is obtained from 3,3'-r (m-aminobenzyl) -sulfonyliminoj -dipropionamide (prepared from 3-nitrobenzylsulfonyl chloride in a manner analogous to the amine from Example 1 C) is derived, a product is obtained which dyes cotton in a blue-red shade, which has very good fastness to washing and perspiration.



   Example 27
EMI21.3
  
If you use the azo dye in the process of Example 9, which is obtained when coupling diazotized 3,3 '- (p-aminophenethylimino) - dipropionamide in an alkaline solution of 5-hydroxynaphthalene-1-sulfonic acid, one arrives at one Dye that provides orange-red dyeings of high wet fastness on cotton. The amine used as the diazonium component is prepared by adding 2 moles of acrylonitrile to 3- (p-nitrophenyl) ethylamine and then reducing the nitro group.



   Example 28
EMI22.1

If in the process of Example 16 D 0.05 m of the diazonium salt is used, which is derived from m-amino-N, Nbis (2-carbamylethyl) - hydrocinnamic acid amide [prepared from ss- (3-nitrophenyl) propionyl chloride in a manner analogous to the amine of Example 16 C] is derived, the result is a dye which gives cotton a yellow coloration with somewhat less green shading and which is just as resistant to pressing, washing and perspiration.



   Example 29
EMI22.2

A solution of 5.0 g of the dye prepared in Example 2 in 150 ml of methanol is heated to reflux with stirring and then enough concentrated hydrochloric acid is added dropwise that the pH is 6.0. The solution is refluxed for 15 minutes, then rapidly cooled to 30 ° C. and poured into 3 l of well-stirred isopropyl alcohol. The product is filtered off, washed with 500 mol of acetone and dried in vacuo at room temperature. Yield 5.9 g of yellow dye. When applied to cotton by the usual methods, this product produces bright yellow dyeings of superior wash and perspiration fastness.



   Example 30
EMI22.3

2.2 g (0.06 m) sodium hydroxide and 2.9 g (0.03 m) sodium carbonate (each dissolved in a minimal amount of water) are added to a mixture of 500 ml of methanol and 500 ml of dioxane, followed by 14.5 g (0.055 m) 3-Hvdroxv-2-nanhthanilid added. The solution is cooled to 10 ° C. and then a cold, aqueous diazonium solution is added which is derived from 15.7 g (0.05 m) 3.3 '- (methanilvlimino) bispropionamide atb. If necessary, alternate with the addition of diazonium. Sodium carbonate added to keep DH at 8.0.

  After stirring for t / 2 hours, the precipitate is filtered off. washed with 1.0 l of water and dried in vacuo at room temperature. Yield 23.5 g (80 / o of theory) of an orange dye.



   A solution of 16.1 g (0.027N) of the above dye in 200 ml of ethanol is treated with 50.1 g (0.062) m) of a 37% aqueous formaldehyde solution of pH 9.5. The reaction mixture is stirred for 6 hours at 65 ° C., the pH value being kept at 9.0-9.5 by adding dilute aqueous sodium hydroxide solution, if necessary, then cooled to 30 ° C. and poured into 2.5 liters of water. The precipitate is filtered off, washed with 1.0 l of water and dried in vacuo at 25 ° C. Yield 16.0 g (100% of theory) of an orange colored substance with a content of 2.09 methylol groups.



   If nylon, silk and wool or acrylonitrile vinylpyrrolidone mixed polymers are dyed with this dye using the dyeing processes customary for these fibers, bright orange colorations with superior fastness properties are obtained.



  Example 31 3,3 '- {[N3- (4,6-dichloro-s-triazin-2-yl) -metanilyl] imino} bispropionamide
EMI23.1

A. A solution of 13.83 g (0.075 mol) of cyanuric acid chloride in 400 ml of acetone is treated at 0-5 C with 23.58 g (0.075 mol) of 3,3'-metanilyliminobispropionamide. A solution of 6.30 g (0.075 mol) of sodium bicarbonate in 60 ml of cold water is then added over the course of 15 minutes. After half an hour, the precipitate is filtered off, washed with 450 ml of cold water and dried at 25 ° C. in vacuo. Yield 32.8 g (94.5% of theory) of a cream-colored powder of F 220-222 C (foaming).



  Analysis: Calculated: C 38.97 H 3.71 N 21.21 S 6.94 Cl 15.34
Found: 38.50 3.86 20.74 7.08 15.17
B. If 47.16 g (0.15 mol) of 3,3'-metanilyliminobispropionamide are used in the process of A and the temperature is increased from 0 to 70 ° C., the following compound is obtained:
EMI23.2
 Example 32
EMI23.3

A mixture of 11.6 g (0.025 mol) of the azo dye, which was obtained by coupling diazotized amino-G acid with m-toluidine, 11.55 g (0.025 mol) 3,3 '- {[N3- (4, 6-dichloro-s-triazin-2-yl) methanilyl @ imino} bispropionamide and 100 ml of water are heated to 83 ° C. with stirring, the pH being maintained at 6.0. As soon as the test for primary aromatic amino groups is negative. the mixture is cooled to 25 ° C., filtered and the filtrate is poured into stirred ethanol.

  The precipitate is filtered off, washed with ethanol and dried at 60.degree. Yield 20 g of an orange dye of 91% purity (89% of theory).



   A solution of 10.0 g of the above dye in 100 ml of water is adjusted to pH 9.5 and then 20.0 g of an aqueous formaldehyde solution above, the pH of which had previously been adjusted to 9.5, are added. The mixture is stirred for 6 hours at 65 ° C. while maintaining a pH of 9.5, then cooled, filtered off and the filtrate is poured into 31 stirred isopropyl alcohol. The precipitate is filtered off, washed with isopropyl alcohol and dried in vacuo at room temperature. Yield 7.5 g of an orange powder with a content of 1.71 methylol groups per mole.

 

   When dyeing or printing cotton in a 2% tint using 10% OWD NHoCl, a reddish-yellow coloration of very good wet press, wash and abrasion fastness is obtained.



   Example 33 3,3'-Iminodipropionamide Sulphate
EMI24.1

39.34 g (0.319 mol) of ss, ss'-iminobis- (propionitrile) are added within 25 minutes to a stirred mixture of 14 ml of water and 102 ml of concentrated sulfuric acid, the temperature being kept below 30 ° C. and then the Stirred for 24 hours at 20-30 ° C. The reaction mixture is then poured into 1.6 l of stirred ethanol at 5 ° C. and after 11/2 hours the precipitate is filtered off, washed with 2.5 l of ethanol and dried at 50 ° C. in vacuo. This gives 76.6 g (94/0 of theory) white crystals of F 158 C.



  Analysis: Calculated: C 28.01 H 5.88 N 16.33 SO4 37.34
Found: 27.38 5.74 15.18 37.85
Example 34
2 .N, N-bis (2-carbnylethyl) amino-4, o-dichloro-s-triazine zin
EMI24.2

A. A solution of 25.7 g (0.1 mol) of 3,3'-iminodipropionamide sulfate in 60 ml of water is neutralized to pH 6.9 with 5N NaOH and then within 15 minutes at 0-5 C with a solution treated of 9.22 g (0.05 mol) of cyanuric acid chloride in 40 ml of acetone, maintaining a pH of 6.5 1 0.4.



  After stirring for a further hour at 0-5 ° C., the precipitate is filtered off, washed with 500 ml of cold water, sucked dry and further dried in vacuo at 50 ° C. Yield 14 g (90% of theory) of the product from F 201 C (decomposition).



   B. If 51.4 g (0.2 mol) of 3,3'-iminodipropionamide are used in process A above and the reaction mixture is heated from 0-65 ° C., the following compound is obtained:
EMI24.3

Example 35
If 0.025 mol of 2-N, N bis (2-carbamylethyl) amino-4,6-dichloro-s-triazine is used as the triazine component in Example 32 above, a dye is obtained which contains 2.95 O / o formaldehyde and Similar colorations result when dyeing or printing cotton.
EMI24.4




  Example 36
EMI24.5
  
To a cold aqueous diazonium solution derived from 15.72 g (0.05 mol) of 3,3'-metanilyliminobispropionamide is added 10.46 g (0.055 mol) of anilinomethanesulfonic acid (anilinomega salt) followed by 32.8 g of anhydrous sodium acetate , the mixture is stirred for 2 hours at 25 ° C., heated to 50 ° C. and salted out. After cooling to 25 ° C., the mixture is filtered off and the moist cake is dissolved in 700 ml of water containing 6 ml of concentrated NH4OH and 10 ml of 5N NaOH. The solution is with
Activated charcoal clarified and then stirred for 24 hours at 25 CC.

  After heating to 80 ° C., the mixture is cooled to 25 ° C. and filtered, 9.4 g of a brown-orange powder of F 171.5 ° C. being obtained after drying.



   A solution of 12.8 g (0.022 mol) G-acid (dipotassium salt) and 200 ml water is adjusted to pH 7.0, 10.6 g (0.1 mol) Na2CO: are added and then with the cold aqueous diazonium solution which is obtained from 9.30 g (0.022 mole) of the above monoazo dye. After stirring for half an hour, the solution is salted out at 55 ° C. and filtered and the cake is dried at 60 ° C. Yield 25.0 g of a light red powder.



   A solution of 3.5 g of the above dye in
100 ml of water is methylolated in the usual way for 6 hours at 65 ° C. and pH 6.5 and gives a yield of 3.34 g of a dye which contains 2.23% bound formaldehyde.



   When used on cotton with 100 / o OWD NHACl, the above dye provides bright scarlet red dyeings of high wet press and wash fastness.



   Example 37
When m-toluidine is used in place of the anilinomega salt in the procedure of Example 36, a monoazo dye intermediate product having a melting point of 200-203 C (dec.) Is obtained. After completion of the subsequent steps, a dye of the formula below is obtained which contains 1.35% methylol groups and, in the presence of 10% OWD NHCl, dyes the cotton in a scarlet red with a slightly less yellow shade than the dye of Example 36.
EMI25.1




  Example 38
EMI25.2

A solution of 21 34 g (0.04 moles) of the blue
Dye, which is obtained in the condensation of bromamic acid and m-phenylenediaminesulfonic acid, is cooled to 0-5 ° C., the pH is adjusted to 4.5 and then a solution of 7.38 g (0.04 mol) of cvanuric acid chloride in 75 is added with stirring ml of acetone added. the pH value is kept at 5.3-5.5 with aqueous Na / CO2. The solution is kept for a further half an hour at 0-5 ° C. and pH 5.5 and then a cold solution of 22.64 g (0.088 mol) of 3.3'-iminodioropionamide sulfate in 50 ml is given to it all at once
Water of pH 5.2 (adjusted with 50% NaOH) was added.

  The mixture is then heated to 76 ° C. for 40 minutes and kept at 7779 ° C. for half an hour, a pH of 5.3-5.5 being maintained. Then the solution is clarified. heated to 70 ° C. and salted in, and after cooling to 25 ° C., filtering, washing and drying at 60 ° C., 33.4 g of a blue dye are obtained. The crude dye is purified from dimethylformamide / isopropanol and gives 258 g of a blue dye. The analysis shows. that it contains a chlorine atom and an iminobispropionamide residue.



     8.75 g of purified dye are methylolated in the usual way at 65 ° C. and pH 9.5 for 6 hours and yield 7.10 g of a blue dye which contains 1.8 methylol groups.



   A 20% dyeing of the above dye on cotton with a 10% OWD NH4Cl catalyst results in reddish blue dyeings of high wash and wet press fastness.



   Example 39
EMI26.1

If, in Example 38, instead of 3,3'-iminobispropionamide sulfate, 27.66 g (0.088 mol) of 3,3'-metanilylimino-bispropionamide are used, the above dye, which contains 2.4 methylol groups, is obtained. When dyeing cotton with NH4Cl, it provides bright brown dyeings with a slightly greener shade than the above dye, with the same wash and wet press fastness
Example 40
The dye obtained according to Example 1 can also be prepared by following the procedure of Example 1, but replacing 3,3'-metanilyliminobispropionamide in Part D of Example 1 with aminobenzenesulfonamide and then ethylation with cyano by reaction with acrylonitrile, hydrolysis and methylolation continues.

 

   Example 41
The dye prepared in Example 2 can also be obtained by following the procedure of Example 2. if one uses m-aminobenzenesulphonamide as the diazo component and continues after coupling with cyano ethylation by reaction with acrylonitrile, hydrolysis and methylolation.

 

Claims (1)

PATENT CLAIM Process for the production of substrate-reactive dyes or optical brighteners of the formula: EMI26.2 wherein D is an organic dye residue or the residue of an optical brightener, Y is a covalent bond or a divalent bridging group, R 'is hydrogen or a group -CHeOH and n is the number 1 or 2, characterized in that a dye or optical brightener of the formula : EMI26.3 SUBSCRIBED 1. The method according to claim, characterized in that the methylol group or methylol groups formed are acylated or alkylated. 2. The method according to claim 1, characterized in that the dyes of the formula II are methylolated by treatment with formaldehyde at a temperature between 20 and 90 ° C and a pH above 7.